CN102002372B

CN102002372B - Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, compound and manufacture method of the compound

Info

Publication number: CN102002372B
Application number: CN201010259631.7A
Authority: CN
Inventors: 内山克博; 秋池利之; 平井刚
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2009-08-28
Filing date: 2010-08-19
Publication date: 2014-01-08
Anticipated expiration: 2030-08-19
Also published as: KR101626796B1; KR20110023735A; TWI485182B; JP5556395B2; TW201120098A; JP2011070160A; CN102002372A

Abstract

The invention provides a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, a compound and a manufacture method of the compound. The liquid crystal aligning agent can form the liquid crystal aligning film capable of keeping good liquid crystal aligning performance and electric character and good weathering resistance even though after long time continuous driving and also preventing the residual DC voltage from increasing. The liquid crystal aligning agent contains (A) at least one polymer selected from a group consisting of a polyamic acid and a polymide and (B) a compound represented by the formula (1).

Description

The manufacture method of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, compound and this compound

Technical field

The present invention relates to the manufacture method of a kind of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, compound and this compound.More specifically, the present invention relates to a kind of liquid crystal aligning good, even and the long-time continuous driving, performance is the liquid crystal orientation film of variation seldom also, and can carry out high-quality demonstration, even and, when long-time the driving, image retention is eliminated also short liquid crystal display device of time.

Background technology

Liquid crystal display device, have the advantages such as little, the easy miniaturization of power consumption and flattening due to it, therefore be widely used in the liquid crystal indicators such as mobile telephone, LCD TV.Display mode as this liquid crystal indicator, according to the variation of liquid crystal molecular orientation state, the liquid crystal display device of the liquid crystal cells such as switch type (IPS type), vertical orientating type (VA type) in have twisted nematic (TN type), super-twist nematic (STN type), face is disclosed.In arbitrary display mode, the state of orientation of liquid crystal molecule is controlled by liquid crystal orientation film, so liquid crystal orientation film and the characteristic that had by the formed liquid crystal aligning agent of this liquid crystal aligning mould material, and the characteristic performance of liquid crystal display device has been produced to impact.

Material as liquid crystal aligning agent, known have resin materials such as polyamic acid, polyimide, polymeric amide, polyester, particularly by the formed liquid crystal orientation film of the liquid crystal aligning agent that contains polyamic acid or polyimide, because of thermotolerance, physical strength, good with the affinity of liquid crystal etc., therefore for most liquid crystal display device (with reference to patent documentation 1～6).Known this liquid crystal display device is for the TV purposes etc., and long-time continuous is while driving, and liquid crystal orientation film is because being exposed to for a long time the light and heat variation, and the display quality variation.

Therefore, as when long-time continuous drives, the technology that display quality can variation yet, studying use and can give the material of crosslinking structure (with reference to patent documentation 7).Yet, use the liquid crystal display device of this material, although the degree of the electric properties deteriorate such as its voltage retention is less, when driving time is elongated, has the residual DC magnitude of voltage and become large defect.

In view of this situation, even wish to develop a kind of can formation when carrying out the long-time continuous driving, also can maintain good liquid crystal aligning performance and electrical characteristic, there is good weathering resistance simultaneously, and suppress the liquid crystal aligning agent of the liquid crystal orientation film of residual DC voltage increase.

[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

No. 5928733 patent of [patent documentation 5] U.S.

[patent documentation 6] Japanese kokai publication sho 62-165628 communique

[patent documentation 7] TOHKEMY 2008-216985 communique

Summary of the invention

The present invention In view of the foregoing makes, even its objective is that providing a kind of can form when carrying out the long-time continuous driving, also can maintain good liquid crystal aligning performance and electrical characteristic, there is good weathering resistance simultaneously, and suppressed the manufacture method of liquid crystal aligning agent, liquid crystal orientation film, the liquid crystal display device with liquid crystal orientation film, compound and the compound of the liquid crystal orientation film that residual DC voltage increases.

For the invention that addresses the above problem, be a kind of liquid crystal aligning agent, it contains [A] and is selected from least one polymkeric substance in the group that polyamic acid and polyimide form, and the represented compound of [B] following formula (1).

In formula (1), the alkoxy methyl that R is 2～7 for hydrogen atom, methylol, carbonatoms independently of one another ,-CH ₂oY or-CH ₂oZ.Y is the group with ring-type the structure of hindered amine.Z is the group with hindered phenol structure.But at least one R is the group with ring-type the structure of hindered amine or hindered phenol structure.

This liquid crystal aligning agent, by containing [A] polymkeric substance and [B] compound, even can form when carrying out the long-time continuous driving, also can maintain good liquid crystal aligning performance and electrical characteristic, there is good weathering resistance simultaneously, and suppressed the liquid crystal orientation film that residual DC voltage increases.

Ring-type the structure of hindered amine that above-mentioned Y has is preferably following formula (2 ^a) represented group, the hindered phenol structure that Z has is preferably following formula (3 ^a) represented group.

Formula (2 ^a) in, R ⁱfor hydrogen atom, the carbonatoms alkyl that is 1～6, the aryl that carbonatoms is 6～20, aralkyl or 1, the 3-dioxo butyl that carbonatoms is 7～13.

R ^iI～R ^vthe aralkyl that the aryl that the alkyl that is 1～6 for carbonatoms independently of one another, carbonatoms are 6～12 or carbonatoms are 7～13.

X ¹for singly-bound, carbonyl or ^*-CONH-.But, with the connecting key of *, with piperidine ring, be connected.

X ²～X ⁵be independently of one another singly-bound, carbonyl, ^*-CH ₂-CO-or ^*-CH ₂-CH (OH)-.But, with the connecting key of *, with piperidine ring, be connected.

X ⁶for singly-bound ,-alkylidene group that CO-, methylene radical or carbonatoms are 2～6.

Formula (3 ^a) in, R ^vIfor the carbonatoms alkyl that is 4～16.R ^vIIfor hydrogen atom or the carbonatoms alkyl that is 1～16.X ⁷for singly-bound ,-alkylidene group that CO-, methylene radical or carbonatoms are 2～6.The integer that n is 0～3.

Ring-type the structure of hindered amine or hindered phenol structure, by having above-mentioned ad hoc structure, can maintain electrical characteristic, and further improve weathering resistance.

Contained [B] compound of this liquid crystal aligning agent is preferably the resultant of reaction of the represented compound of (b 1) following formula (1x) and (b2) following formula (2) and/or the represented compound of formula (3).

In formula (1x), R ^xthe alkoxy methyl that is 2～7 for hydrogen atom, methylol or carbonatoms independently of one another.But, at least one R ^xfor methylol or the carbonatoms alkoxy methyl that is 2～7.

Y-OH (2)

In formula (2), Y is above-mentioned formula (2 ^a) represented group.

Z-OH (3)

In formula (3), Z is above-mentioned formula (3 ^a) represented group.

Above-mentioned by making (b1) compound reacts with (b2) compound, can obtain at an easy rate [B] compound.

Above-mentioned Y is preferably the following formula (2 that is selected from ^a-1)～(2 ^a-2) at least one in the group that represented group forms, Z is preferably the following formula (3 that is selected from ^a-1)～(3 ^a-2) at least one in the group that represented group forms.

Because [B] compound has above-mentioned specific group, so the increase of the stability of liquid crystal orientation film, and weathering resistance is better.

The usage ratio of [B] compound, be preferably below above 100 mass parts of 0.1 mass parts with respect to 100 mass parts [A] polymkeric substance.[B] compound by containing above-mentioned specified quantitative, can further improve weathering resistance.

By the formed liquid crystal orientation film of this liquid crystal aligning agent and liquid crystal display device with this liquid crystal orientation film, also suitably comprised in the present invention.This liquid crystal display device, can be suitably for various devices, display unit such as clock and watch, portable game machine, word processor, notebook computer, auto-navigation system, camcorder, portable data assistance, digital camera, mobile telephone, various indicating meter, LCD TV.

The present invention comprises the represented compound of following formula (1).

This compound can be suitably as the composition of the liquid crystal aligning agent that forms liquid crystal orientation film etc.

The manufacture method that the present invention comprises this compound, the method has the operation that the represented compound of following formula (1x) and following formula (2) and/or (3) represented compound are reacted.

Y-OH (2)

In formula (2), Y is the group with ring-type the structure of hindered amine.

Z-OH (3)

In formula (3), Z is the group with hindered phenol structure.

In addition, above-mentioned R ⁱaralkyl, R that the aryl that represented carbonatoms is 6～20, carbonatoms are 7～13 ^iI～R ^vthe part or all of hydrogen atom that the aralkyl that the aryl that the alkyl that represented carbonatoms is 1～6, carbonatoms are 6～12 and carbonatoms are 7～13 has also can be substituted.

According to the present invention, even can provide a kind of can form when carrying out the long-time continuous driving, also can maintain good liquid crystal aligning performance and electrical characteristic, there is good weathering resistance simultaneously, and suppressed the manufacture method of liquid crystal aligning agent, liquid crystal orientation film, the liquid crystal display device with liquid crystal orientation film, compound and the compound of the liquid crystal orientation film that residual DC voltage increases.Therefore, liquid crystal display device of the present invention can carry out high-quality demonstration, even and when long-time the driving, display performance is variation seldom also, therefore can be effective to various devices, such as being suitable for the display unit such as clock and watch, portable game machine, word processor, notebook computer, auto-navigation system, camcorder, portable data assistance, digital camera, mobile telephone, various indicating meter, LCD TV.

Embodiment

Below, embodiments of the present invention are described in detail.

Liquid crystal aligning agent of the present invention, contain [A] be selected from least one polymkeric substance in the group that polyamic acid and polyimide form (below, be called " [A] polymkeric substance "), and the represented compound of [B] above-mentioned formula (1) (below, also referred to as " [B] compound ").In addition, only otherwise damage effect of the present invention, this liquid crystal aligning agent can contain any composition.Below, for [A] polymkeric substance, [B] compound and any composition, described in detail.

<[A] polymkeric substance >

Polyamic acid as [A] polymkeric substance can obtain by making tetracarboxylic dianhydride and diamine reactant, and polyimide can obtain by making this polyamic acid dehydration closed-loop.Below, for tetracarboxylic dianhydride and diamines, described in detail.

[tetracarboxylic dianhydride]

As the tetracarboxylic dianhydride, 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-bis-is chloro-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-, six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, 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 acid anhydride, 3,5,6-, tri-carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-dioxa, three ring [5.3.1.0 ^2,6] undecane-3,5,8, the 10-tetraketone, following formula (T-1), the represented compound of formula (T-2), pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide compound dianhydride, to phenylene-bis-(triphenyl phthalic acid) dianhydride, metaphenylene-bis-(triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-phenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-ditan dianhydride, ethylene glycol-bis-(dehydration trimellitate), propylene glycol-bis-(dehydration trimellitate), BDO-bis-(dehydration trimellitate), 1,6-hexylene glycol-bis-(dehydration trimellitate), 1,8-ethohexadiol-bis-(dehydration trimellitate), the compound that 2,2-bis-(4-hydroxyphenyl) propane-bis-(dehydration trimellitate) and following formula (T-3)～(T-6) are represented etc.These tetracarboxylic dianhydrides can be used singly or in combination of two or more.

In above-mentioned formula, R ¹and R ³independently of one another for thering is the divalent organic group of aromatic nucleus.R ²and R ⁴be hydrogen atom or alkyl independently of one another.

As above-mentioned formula (T-1) and (T-2) represented compound, can enumerate for example represented compound of following formula (T-1-1)～(T-2-1).

In these tetracarboxylic dianhydrides, use and be selected from the butane tetracarboxylic acid dianhydride, 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 acetic acid dianhydride, 1,3,3a, 4,5,9b-, six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, 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 acid anhydride, 3,5,6-, tri-carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-dioxa, three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4, at least one in the group that the represented compound of 5,8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-1-1)～(T-1-3) and formula (T-2-1) forms (below, be called " specific tetracarboxylic dianhydride "), from the viewpoint that can show good liquid crystal aligning, considering, is preferred.

As specific tetracarboxylic dianhydride, be preferably and be selected from 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic basic ring amyl group acetic acid 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)-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 acid anhydride, 3, 5, 6-tri-carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8, at least one in the group that the represented compound of 10-tetraketone, pyromellitic acid dianhydride and above-mentioned formula (T-1-1) forms.

As specific tetracarboxylic dianhydride's usage ratio, with respect to whole tetracarboxylic dianhydrides, be preferably more than 50 % by mole, more preferably, more than 60 % by mole, be particularly preferably more than 80 % by mole, and most preferably only use specific tetracarboxylic dianhydride.

[diamines]

As diamines, 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, 4,4 '-diaminobenzene formylaniline, 4,4 '-diaminodiphenyl oxide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 3,3 '-bis-(trifluoromethyl)-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, 4,4 '-diamino benzophenone, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] sulfone, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 1,3-bis-(4-amino-benzene oxygen) benzene, 1,3-bis-(3-amino-benzene oxygen) benzene, 9,9-bis-(4-aminophenyl)-10-hydrogen anthracene, 2,7 diamin of luorene, 9,9-dimethyl-2,7 diamin of luorene, 9,9-bis-(4-aminophenyl) fluorenes, 4,4 '-methylene radical-bis-(2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-bis-is chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to the phenylene isopropylidene) two (aniline), 4,4 '-(metaphenylene isopropylidene) two (aniline), 2,2 '-bis-[4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 4,4 '-bis-[(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, 3,5-diaminobenzoic acid, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, and following formula (D-1)～represented aromatic diamines such as compound of formula (D-5),

In formula (D-4), the integer that y is 2～12.In above-mentioned formula (D-5), the integer that z is number of repeat unit 1～5.

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

2,3 diamino pyridine, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 5,6-diamino-2,3-dicyano pyrazine, 5,6-diamino-2, the 4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazines, Isosorbide-5-Nitrae-bis-(3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazines, 2,4-diamino-6-methoxyl group-1,3,5-triazines, 2,4-diamino-6-phenyl-1,3,5-triazines, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazines, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2,6-diaminopurine, 5,6-diaminostilbene, the 3-dimethyl uracil, 3,5-diaminostilbene, 2,4-triazole, 6,9-diamino-2-oxyethyl group acridine lactate, 3,8-diamino-6-phenylphenanthridineand, Isosorbide-5-Nitrae-diamino piperazine, 3,6-proflavin, two (4-aminophenyl) aniline, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-dimethyl-p-diaminodiphenyl, the compound that the compound that following formula (D-6) is represented and following formula (D-7) are represented etc. has the diamines of the nitrogen-atoms beyond two primary aminos and this primary amino in molecule,

In formula (D-6), R ⁵for thering is 1 valency organic group of the nitrogen atom ring texture in the group that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine formation.X ^aorganic group for divalent.

In formula (D-7), R ⁶for thering is the divalent organic group of the nitrogen atom ring texture in the group that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine formation.X ^bbe the organic group of divalent independently of one another.

The represented substituted benzene diamines such as compound of following formula (D-8);

In formula (D-8), R ⁷for-O-,-COO- ^*,-OCO- ^*,-NHCO- ^*,-CONH- ^*or CO-.But, with connecting key and the R of * ⁸connect.R ⁸for skeleton or 1 valency organic group of group or the alkyl that carbonatoms is 6～30 in the group with the steroid backbone of being selected from, trifluoromethyl, Trifluoromethoxyphen-l and difluorophenyl formation.

The diamino organo-siloxanes such as the compound that following formula (D-9) is represented etc.These diamines can be used singly or in combination of two or more.

In formula (D-9), R ⁹the alkyl that is 1～12 for carbonatoms independently of one another.P is 1～3 integer independently of one another.The integer that q is 1～20.

Above-mentioned aromatic diamine, the diamines that has the nitrogen-atoms beyond two primary aminos and this primary amino in molecule and the phenyl ring that single-substituted diamines has, the alkyl (being preferably methyl) that can be also 1～4 by one or more carbonatoms replaces.In addition, the steroid backbone in above-mentioned formula (D-8), refer to one or more skeleton for two keys in pentamethylene base-formed skeleton of perhydro-phenanthrene nucleus or its C-C.

In these diamines, preferably contain and be selected from Ursol D, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino-diphenyl thioether, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 9,9-bis-(4-aminophenyl) fluorenes, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 4,4 '-(to the phenylene diisopropylidene) two (aniline), 4,4 '-(metaphenylene diisopropylidene) two (aniline), Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene radical two (hexahydroaniline), 1,3-bis-(amino methyl) hexanaphthene, above-mentioned formula (D-1)～(D-5) is represented compound separately, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-tolidine, the represented compound of following formula (D-6-1) in the represented compound of above-mentioned formula (D-6), the represented compound of following formula (D-7-1) in the represented compound of above-mentioned formula (D-7), dodecyloxy-2 in the represented compound of above-mentioned formula (D-8), the 4-diaminobenzene, pentadecane oxygen base-2, the 4-diaminobenzene, n-Hexadecane oxygen base-2, the 4-diaminobenzene, octadecane oxygen base-2, the 4-diaminobenzene, dodecyloxy-2, the 5-diaminobenzene, pentadecane oxygen base-2, the 5-diaminobenzene, n-Hexadecane oxygen base-2, the 5-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene and the represented compound of following formula (D-8-1)～(D-8-9), in the represented compound of above-mentioned formula (D-9) 1, at least one in the group that 3-bis-(3-aminopropyl)-tetramethyl disiloxane forms (below, be called " specific diamines ").

As the usage quantity of above-mentioned specific diamines used during polyamic acid in synthetic this liquid crystal aligning agent, with respect to whole diamines, be preferably more than 50 % by mole, more preferably, more than 60 % by mole, be particularly preferably more than 80 % by mole.And most preferably only use specific diamines.

[synthesizing of polyamic acid]

Polyamic acid in this liquid crystal aligning agent, can obtain by making above-mentioned tetracarboxylic dianhydride and diamine reactant.Supply with the tetracarboxylic dianhydride of polyamic acid building-up reactions and the usage ratio of diamines, with respect to the 1 equivalent amino closed in diamines, tetracarboxylic dianhydride's anhydride group is preferably 0.2 equivalent～2 equivalents, and 0.3 equivalent～1.2 equivalents more preferably.

The building-up reactions of polyamic acid is preferably implemented in organic solvent, as temperature of reaction, is preferably-20 ℃～150 ℃, and more preferably 0～100 ℃.As the reaction times, be preferably 0.1 hour～24 hours, and more preferably 0.5 hour～12 hours.As organic solvent, can enumerate such as non-proton property polar solvent, phenol and derivative thereof, alcohol, ketone, ester, ether, halon, hydrocarbon etc.

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

As above-mentioned amphyl, can enumerate such as a sylvan, xylenol, halogenated phenol etc.;

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

As above-mentioned ketone, can enumerate such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.

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

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

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

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

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

As mentioned above, can obtain dissolving the formed reaction soln of polyamic acid.This reaction soln, can directly supply with the modulation of liquid crystal aligning agent, also polyamic acid contained in reaction soln can be separated to the modulation of rear supply liquid crystal aligning agent, or resupply the modulation of liquid crystal aligning agent after isolated polyamic acid can also being made with extra care.The polyamic acid dehydration closed-loop is formed to the occasion of polyimide, above-mentioned reaction soln directly can be supplied with to the dehydration closed-loop reaction, also polyamic acid contained in reaction soln can be separated to rear supply dehydration closed-loop reaction, or resupply the dehydration closed-loop reaction after 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, then the method for this precipitate of drying under reduced pressure, or the method for using vaporizer that the decompression of the organic solvent in reaction soln is distillated and carrying out.In addition, can then with poor solvent, make its method of separating out by this polyamic acid is dissolved in organic solvent again, or the method for the operation of using once or several times vaporizer to reduce pressure to distillate, refining polyamic acid.

[synthesizing of polyimide]

The polyimide that can contain in this liquid crystal aligning agent, can obtain by making the resulting polyamic acid dehydration closed-loop of tetracarboxylic dianhydride and diamine reactant carry out imidization.

As can be for the synthesis of tetracarboxylic dianhydride and the diamines of polyimide, can enumerate with can be for the synthesis of tetracarboxylic dianhydride and the identical compound of diamines of polyamic acid.Kind and the usage ratio of preferred tetracarboxylic dianhydride and diamines are identical during with synthesizing polyamides acid.

Above-mentioned polyimide, can be the amido acid structure fully dehydrating closed loop that the polyamic acid as raw material is had and the complete imide compound obtained, or can be also the amido acid structure that only a part of dehydration closed-loop in the amido acid structure obtained and imide ring structure the part imide compound of depositing.Imide rate as polyimide in this liquid crystal aligning agent, be preferably more than 30%, and more preferably more than 40%.Above-mentioned imide rate is to mean the value of imide ring structure number with respect to the total proportion of the amido acid structure number of polyimide and imide ring structure number with percentage.At this moment, the part of imide ring can be also different imide ring.The imide rate, can be by polyimide ¹h-HMR is known.In addition, the imide rate in this specification sheets, be that polyimide at room temperature fully after drying under reduced pressure, is dissolved in the deuterate dimethyl sulfoxide (DMSO), and usings tetramethylsilane as primary standard, at room temperature measures ¹h-NMR, by this measurement result, (2) are obtained according to the following equation.

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

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

Dehydration closed-loop for the synthesis of the polyamic acid of above-mentioned polyimide, can be by the method for (i) heating polyamic acid, perhaps (ii) is dissolved in polyamic acid in organic solvent, to adding dewatering agent and dehydration closed-loop catalyzer in this solution, and the method for heating as required and carrying out.

As the temperature of reaction in (i) method, be 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.As the reaction times, be preferably 1.0 hours～24 hours, and more preferably 1.0 hours～12 hours.

In the method for (ii), as dewatering agent, can enumerate acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride etc.As the usage quantity of dewatering agent, with respect to the repeating unit of 1 mole of polyamic acid, be preferably 0.01 mole～20 moles.

As the dehydration closed-loop catalyzer, can enumerate tertiary amines such as pyridine, collidine, two picolins, triethylamine.As the usage quantity of dehydration closed-loop catalyzer, with respect to 1 mole of dewatering agent used, be preferably 0.01 mole～10 moles.As can be for the organic solvent of dehydration closed-loop reaction, can enumerate as organic solvent used in polyamic acid synthetic and illustrative organic solvent.Temperature of reaction as the dehydration closed-loop reaction, be preferably 0 ℃～180 ℃, and more preferably 10 ℃～150 ℃.As the reaction times, be preferably 1.0 hours～120 hours, and more preferably 2.0 hours～30 hours.

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

The polyamic acid that can contain in this liquid crystal aligning agent or polyimide can be the polymkeric substance that has carried out the end modified type of molecular-weight adjusting.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 synthesizing polyamides when acid, to adding molecular weight regulator in polymerization reaction system, carries out.As molecular weight regulator, can enumerate such as single acid anhydride, monoamine compound, monoisocyanates compound etc.

As above-mentioned single acid anhydride, can enumerate such as maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.

As above-mentioned monoamine compound, can enumerate such as aniline, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, Pentadecane amine, n-hexadecane amine, n-heptadecane amine, Octadecane amine, NSC 62789 amine etc.

As above-mentioned monoisocyanates compound, can enumerate such as phenylcarbimide, isocyanic acid naphthyl ester etc.

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

As above the polyamic acid of gained or polyimide, when forming the solution that concentration is 10 quality %, preferably have the soltion viscosity of 20mPas～800mPas, and more preferably have the soltion viscosity of 30mPas～500mPas.In addition, the soltion viscosity of the polymkeric substance in this specification sheets (mPas), the polymers soln for 10 % by weight concentration of good solvent (such as gamma-butyrolactone, the METHYLPYRROLIDONE etc.) modulation that adopts this polymkeric substance, the value of using E type rotational viscosimeter to measure under 25 ℃.

As [A] polymkeric substance in this liquid crystal aligning agent, preferably only use polyimide or mix and use polyimide and polyamic acid.Imide rate when only using polyimide as [A] polymkeric substance, be preferably below 70%, and more preferably 30%～60%.On the other hand, the average imide rate when mix using polyimide and polyamic acid as [A] polymkeric substance, be preferably below 70%, and more preferably 10%～60%, and be particularly preferably 15%～55%.This average imide rate, be the amido acid structure number (PA-A) of imide ring structure number (PI-I), amido acid structure number (PI-A) and the polyamic acid of polyimide contained in liquid crystal aligning agent, and calculate the value obtained according to following formula (1).

<[B] compound >

[B] compound in this liquid crystal aligning agent is by the represented compound of above-mentioned formula (1).R in formula (1), have ring-type the structure of hindered amine or hindered phenol structure, and the R number as replacing, be preferably 1～3.

In the present invention, the structure of hindered amine, refer on two carbon atoms of the nitrogen-atoms adjacency with the cyclic amine structure, has a plurality of substituent structures that demonstrate the steric barrier effect.

As this substituting group that demonstrates the steric barrier effect, can enumerate the aralkyl that alkyl that for example carbonatoms is 1～6, aryl that carbonatoms is 6～12 or carbonatoms are 7～13.

The alkoxy methyl that R in above-mentioned formula (1) is 2～7 for hydrogen atom, methylol, carbonatoms independently of one another ,-CH ₂oY or-CH ₂oZ.Y is the group with ring-type the structure of hindered amine.Z is the group with hindered phenol structure.But at least one R is the group with ring-type the structure of hindered amine or hindered phenol structure.The structure of hindered amine had as above-mentioned Y, be preferably above-mentioned formula (2 ^a) represented group.

As above-mentioned formula (2 ^a) in R ⁱthe alkyl that represented carbonatoms is 1～6, can be the straight chain shape or branched in any, and can enumerate such as methyl, ethyl, propyl group, butyl, amyl group etc.

As above-mentioned formula (2 ^a) in R ⁱthe aryl that represented carbonatoms is 6～20, can enumerate such as phenyl, 3-fluorophenyl, 3-chloro-phenyl-, 4-chloro-phenyl-, 4-isopropyl phenyl, 4-n-butylphenyl, the chloro-4-aminomethyl phenyl of 3-, 4-pyridyl, 2-phenyl-4-quinolyl, 2-(4 '-tert-butyl-phenyl)-4-quinolyl, 2-(2 '-sulfur phenenyl)-4-quinolyl etc.

As above-mentioned formula (2 ^a) in R ⁱthe aralkyl that represented carbonatoms is 7～13, can enumerate such as benzyl, styroyl etc.

As above-mentioned formula (2 ^a) in R ⁱand X ¹combination (that is, R ⁱ-X ¹-part); can enumerate for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-, the tertiary butyl, formyl radical, ethanoyl, phenyl, benzyl, 1; group that 3-dioxo butyl, 4-pyridyl carbonyl, benzoyl, 2-phenyl-4-quinolyl, 2-(4 '-tert-butyl-phenyl)-4-quinolyl, 2-(2 '-sulfur phenenyl)-4-quinolyl, formula-CONH-Ph (still, Ph is the chloro-4-aminomethyl phenyl of phenyl, 3-fluorophenyl, 3-chloro-phenyl-, 4-chloro-phenyl-, 4-isopropyl phenyl, 4-n-butylphenyl or 3-) are represented etc.

As above-mentioned formula (2 ^a) R ^iI～R ^vthe alkyl that represented carbonatoms is 1～6, can enumerate as above-mentioned R ⁱthe illustrated group of the alkyl that represented carbonatoms is 1～6.

As above-mentioned formula (2 ^a) R ^iI～R ^vthe aryl that represented carbonatoms is 6～12; the group that the alkoxyl group that to be preferably part or all of hydrogen atom that the aromatic nucleus of aryl has be 1～4 by formyl radical or carbonatoms replaces; it can enumerate for example phenyl, 4-formyl radical phenyl, 3,4,5-trimethoxyphenyl etc.

As above-mentioned formula (2 ^a) R ^iI～R ^vthe aralkyl that represented carbonatoms is 7～13, the group that the alkoxyl group that the part or all of hydrogen atom that the aromatic nucleus of aralkyl has can be 1～4 by formyl radical or carbonatoms replaces, it can enumerate for example benzyl.

As above-mentioned formula (2 ^a) in R ^iIand X ², R ^iIIand X ³, R ^iVand X ⁴, R ^vand X ⁵combination (that is, R ^iI-X ²-, R ^iII-X ³-, R ^iV-X ⁴-or R ^v-X ⁵-part); can enumerate for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, 2-butyl, isobutyl-, the tertiary butyl, phenyl, benzyl, benzoyl, 4-formyl radical benzoyl, 2-hydroxyl-2-phenylethyl, 2-oxo-2-(3; 4,5-trimethoxyphenyl) ethyl etc.

As above-mentioned formula (2 ^a) represented compound, preferably R ⁱfor hydrogen atom, R ^iI～R ^vbe all methyl, X ¹～X ⁵it is all the compound of singly-bound.

In addition, in the present invention, there is hindered phenol structure, refer in formula (1), on the ortho position of phenolic hydroxyl group (2 and/or 6), demonstrate the steric barrier effect.

As this substituting group that demonstrates the steric barrier effect, can enumerate such as the tertiary butyl, 1-methyl pentadecyl, octyl group thiomethyl etc.In addition, when substituting group is positioned at 2 and 6 these two places, its substituting group each naturally independently.

The hindered phenol structure had as above-mentioned Z, be preferably above-mentioned formula (3 ^a) represented group.As preference, can enumerate the compound had containing the structure of (3,5-di-tert-butyl-hydroxy phenyl) group.

As above-mentioned formula (3 ^a) middle R ^vIthe alkyl that represented carbonatoms is 4～16, be preferably the tertiary butyl, 1-methyl pentadecyl, octyl group thiomethyl, and the tertiary butyl more preferably.

As above-mentioned formula (3 ^a) middle R ^vIIthe alkyl that represented carbonatoms is 1～16, be preferably the tertiary butyl, 1-methyl pentadecyl, octyl group thiomethyl, and the tertiary butyl more preferably.

Above-mentioned formula (3 ^a) in R ^vIand R ^vIIbe preferably placed at the ortho position (2 and 6) of phenolic hydroxyl group.

As above-mentioned formula (3 ^a) in X ⁷, be preferably methylene radical.

[B] compound, be preferably the resultant of reaction of 1 molar part (b 1) compound and x molar part (b2) compound (still, x meets 0<x<n).But, the number that n is the methylol that has of 1 molecule above-mentioned (b 1) compound or the carbonatoms alkoxy methyl that is 2～7.

As R in the above-mentioned formula (1x) of (b 1) compound ^xthe alkyl that represented carbonatoms is 1～6, be preferably the alkyl that carbonatoms is 1～4, more preferably methyl, ethyl, normal-butyl, isobutyl-, and be particularly preferably methyl.As this compound (b 1), can enumerate for example N, N, N ', N ', N ", N " the alkoxy methyl melamine such as-six (alkoxy methyl) melamine.As commercially available product, can enumerate サィメ Le 300, サィメ Le 301, サィメ Le 303, サィメ Le 350, サィメ Le 370, サィメ Le 325, サィメ Le 327, サィメ Le 703, サィメ Le 712, マィコ mono-ト 715, サィメ Le 701, サィメ Le 285, サィメ Le 232, サィメ Le 235, サィメ Le 236, サィメ Le 238, サィメ Le 211, サィメ Le 254, マィコ mono-ト 212, サィメ Le 202, マィコ mono-ト 508 (MITSU-CYTEC society) etc.

As operable organic solvent in above-mentioned reaction, can enumerate organic solvent used while synthesizing as above-mentioned polyamic acid and illustrative organic solvent.Wherein, preferred non-proton organic solvent, can enumerate for example METHYLPYRROLIDONE, acetonitrile, dimethyl sulfoxide (DMSO), N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N, N '-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA, tetrahydrofuran (THF) etc.As the usage ratio of organic solvent, with respect to the total weight of the compound in reaction soln (b1) and compound (b2), be preferably the above ratio of 1 quality %, and the ratio of 5 quality %～50 quality % more preferably.

Temperature during as reaction, be preferably 20 ℃～250 ℃, and more preferably 50 ℃～180 ℃.As the reaction times, be preferably 0.1 hour～72 hours, and more preferably 0.5 hour～48 hours.

So, can obtain containing the preferably solution of [B] compound.This solution, can directly supply with the modulation of this liquid crystal aligning agent, or can from reaction soln, after separation and purification [B] compound, supply with the modulation of this liquid crystal aligning agent.As the method for separation and purification from reaction soln [B] compound, can enumerate such as liquid-liquid extraction, column chromatography, distillation method, recrystallize etc.

As preferred [B] compound, a part that is the methylol that has of compound (b 1) or the carbonatoms alkoxy methyl that is 2～7 is reacted with compound (b2), and has the alkoxy methyl that the methylol that comes from compound (b1) or carbonatoms are 2～7 simultaneously and come from the radicals R of compound (b2) ⁱ.Therefore, this liquid crystal aligning agent this by containing [B] compound, even can form when long-time continuous drives, also can maintain good liquid crystal aligning performance and electrical characteristic, suppressed the liquid crystal orientation film that residual DC voltage increases simultaneously.

As the more preferably example of [B] compound, above-mentioned Y more preferably is selected from above-mentioned formula (2 ^a-1)～(2 ^a-2) in the group that represented group forms at least one, Z more preferably is selected from above-mentioned formula (3 ^a-1)～(3 ^a-2) in the group that represented group forms at least one.As the usage ratio of [B] compound in this liquid crystal aligning agent, with respect to 100 mass parts [A] polymkeric substance, be preferably 0.1 mass parts～100 mass parts, 0.5 mass parts～50 mass parts more preferably, and be particularly preferably 1 mass parts～30 mass parts.

This liquid crystal aligning agent, contain [A] polymkeric substance and [B] compound, and can contain as required the compound that there is at least one epoxy group(ing) in other polymkeric substance, molecule (below, be called " epoxy compounds "), the composition arbitrarily such as functional silanes compound, multifunctional (methyl) acrylate, melamine compound (still, except [B] compound).Below, each composition is described in detail.

[other polymkeric substance]

Above-mentioned other polymkeric substance, can be for improving solution properties and electrical characteristic.As other polymkeric substance, can enumerate such as poly amic acid ester, polyester, polymeric amide, polysiloxane, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc.

As the usage ratio of other polymkeric substance in liquid crystal aligning agent of the present invention, with respect to 100 mass parts [A] polymkeric substance, be preferably below 100 quality %, more preferably below 80 quality %, and be particularly preferably below 30 quality %.Preferably be preferably and do not contain other polymkeric substance.

[epoxy compounds]

Consider with respect to the viewpoint of the cementability of the liquid crystal orientation film substrate surface formed from further raising, can use above-mentioned epoxy compounds.As preferred epoxy compounds, can enumerate for example ethylene glycol diglycidylether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-bis-(N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl hexanaphthene etc.As the mixing ratio of epoxy compounds, with respect to 100 mass parts [A] polymkeric substance, be preferably below 40 mass parts, and 0.1 mass parts～30 mass parts more preferably.

[silane compound]

Consider from the viewpoint of the printing of further this liquid crystal aligning agent of raising, can use above-mentioned functional silanes compound.As the functional silanes compound, can enumerate for example 3-TSL 8330, APTES, 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-APTES, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilicane alkyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, N-bis-(oxo ethylidene)-3-TSL 8330, N-bis-(oxo ethylidene)-APTES etc.As the usage ratio of functional silanes compound, with respect to 100 mass parts [A] polymkeric substance, be preferably below 2 mass parts, and 0.02 mass parts～0.2 mass parts more preferably.

[multifunctional (methyl) acrylate]

Consider from the viewpoint of the weathering resistance of further this liquid crystal aligning agent of raising, can use above-mentioned multifunctional (methyl) acrylate.As multifunctional (methyl) acrylate, can enumerate for example glycol diacrylate, ethylene glycol dimethacrylate, 1,6 hexanediol diacrylate, HDDMA, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, tetraethylene glycol diacrylate, the TEG dimethacrylate, polypropyleneglycol diacrylate, polypropylene glycol dimethacrylate, two phenoxyethyl alcohol fluorenes diacrylates, two phenoxyethyl alcohol fluorenes dimethacrylates, Viscoat 295, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, Dipentaerythritol five acrylate, Dipentaerythritol pentamethyl-acrylate, dipentaerythritol acrylate, Dipentaerythritol hexamethyl acrylate, three (2-acryloxy ethyl) phosphoric acid ester, three (2-methacryloxyethyl) phosphoric acid ester etc.

As commercially available product, for example can enumerate ァロニッ Network ス M-210, ァロニッ Network ス M-240, ァロニッ Network ス M-6200, ァロニッ Network ス M-309, ァロニッ Network ス-400, ァロニッ Network ス-402, ァロニッ Network ス-405, ァロニッ Network ス-450, ァロニッ Network ス-1310, ァロニッ Network ス-1600, ァロニッ Network ス-1960, ァロニッ Network ス-7100, ァロニッ Network ス-8030, ァロニッ Network ス-8060, ァロニッ Network ス-8100, ァロニッ Network ス-8530, ァロニッ Network ス-8560, ァロニッ Network ス-9050, ァロニッ Network ス TO-1450 (more than, society is synthesized in East Asia), KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, MU-2100, MU-4001, KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARADDPCA-120, KAYARAD MAX-3510 (more than, Japanese chemical drug society), PVC スコ mono-ト 260, PVC スコ mono-ト 312, PVC スコ mono-ト 335HP, PVC スコ mono-ト 295, PVC スコ mono-ト 300, PVC スコ mono-ト 360, PVC スコ mono-ト GPT, PVC スコ mono-ト 3PA, PVC スコ mono-ト 400 (more than, Osaka organic chemistry industry society), ニュ mono-Off ロ Application ティァ R-1150 (more than, the first industrial pharmacy society), KAYARAD DPHA-40H (more than, Japanese chemical drug society) etc.As the usage ratio of multifunctional (methyl) acrylate, with respect to 100 mass parts [A] polymkeric substance, be preferably below 100 mass parts, and more preferably below 50 mass parts.

[melamine compound (still, except [B] compound)]

As above-mentioned melamine compound, can enumerate for example above-mentioned (b 1) compound.As the usage ratio of melamine compound, with respect to 100 mass parts [A] polymkeric substance, be preferably below 100 mass parts, and more preferably below 50 mass parts.

The modulator approach of<liquid crystal aligning agent >

This liquid crystal aligning agent, as by above-mentioned [A] polymkeric substance, [B] compound, and any composition as required, the solution shape composition be preferably dissolved in organic solvent is modulated.

As organic solvent, can enumerate for example METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, the 4-hydroxy-4-methyl-2-pentanone, n-Butyl lactate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, the glycol monomethyl isopropyl ether, ethylene glycol mono-n-butyl ether (ethylene glycol butyl ether), 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 can use separately, or are used in combination.

The solid component concentration of this liquid crystal aligning agent (the total quality of removing the composition beyond organic solvent in liquid crystal aligning agent accounts for the ratio of liquid crystal aligning agent total mass), consider viscosity, volatility etc. and suitably select, and be preferably 1 quality %～10 quality %.This liquid crystal aligning agent is being coated on to substrate surface, and remove organic solvent and while forming filming of being formed by liquid crystal orientation film, when solid component concentration during less than 1 quality %, to occur that this thickness of filming is too small and be difficult to obtain the situation of good liquid crystal orientation film, on the other hand, when solid component concentration surpasses 10 quality %, to occur that coating thickness is blocked up and be difficult to equally obtain the situation of good liquid crystal orientation film, or will occur that the viscosity of liquid crystal aligning agent increases the situation that causes the coating characteristics variation.

As preferred solid component concentration scope, method used during according to coating of liquid crystalline alignment agent on substrate and difference.For example, when adopting spin-coating method, be preferably the scope of 1.5 quality %～4.5 quality %.When adopting print process, be preferably the scope of 3 quality %～9 quality %, and, as soltion viscosity, be preferably the scope of 12mPas～50mPas.When adopting ink jet method, be preferably the scope of 1 quality %～5 quality %, and, as soltion viscosity, be preferably the scope of 3mpas～15mpas.

Temperature during as this liquid crystal aligning agent of modulation, be preferably 10 ℃～50 ℃, and more preferably 20 ℃～30 ℃.

The manufacture method of<liquid crystal orientation film, its formation method, liquid crystal display device and liquid crystal display device >

By the formed liquid crystal orientation film of this liquid crystal aligning agent, also preferably be contained in the present invention.Liquid crystal orientation film of the present invention, by this liquid crystal aligning agent is coated on substrate, then heats coated face and be formed on substrate.In addition, liquid crystal display device of the present invention has this liquid crystal orientation film.Below, the formation method of liquid crystal orientation film of the present invention and the manufacture method of liquid crystal display device are described in detail.

(1-1) when manufacturing TN type, STN type or VA type liquid crystal display device, two substrates that make to be provided with the nesa coating that forms pattern are paired, and preferably by offset printing method, spin-coating method or ink jet printing method, respectively liquid crystal aligning agent of the present invention is coated on transparent conducting film formation face separately, then heat each coated face, formation is filmed.As substrate, can use glass such as float glass, soda-lime glass herein; Polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, 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.

As the method for the nesa coating that obtains forming pattern, after can enumerating and for example forming patternless nesa coating, by photoengraving form the method for pattern, when forming nesa coating, use the method for the mask with desirable pattern etc.When the coating of liquid crystalline alignment agent, for the cementability that makes substrate surface and nesa coating and film is better, can be embodied in substrate surface and form on the face of filming, be coated with in advance the pre-treatment of functional silanes compound, functionality titanium compound etc.

After being coated with this liquid crystal aligning agent, for the situation such as prevent that liquid from dripping, preferably implement to preheat (prebake).As the prebake temperature, be preferably 30 ℃～200 ℃, more preferably 40 ℃～150 ℃, and be particularly preferably 40 ℃～100 ℃.As the prebake time, be preferably 0.1 minute～10 minutes, and more preferably 0.5 minute～5 minutes.

Then, in order to remove desolventizing fully, and make as required the polyamic acid hot-imide, implement to burn till (curing afterwards).As rear stoving temperature, be preferably 80 ℃～300 ℃, and more preferably 120 ℃～250 ℃.As after cure the time, be preferably 5 minutes～200 minutes, and more preferably 10 minutes～100 minutes.Although this liquid crystal aligning agent forms by remove organic solvent after coating filming of consisting of liquid crystal orientation film, but contained polymkeric substance is polyamic acid or has the imide ring structure and during the polyimide of amido acid structure simultaneously in this liquid crystal aligning agent, also can after filming, formation further heat, carry out the dehydration closed-loop reaction, and form filming of imidization more.

The thickness of filming as forming, be preferably 0.001 μ m～1 μ m, and 0.005 μ m～0.5 μ m more preferably.

(1-2) when manufacturing IPS type liquid crystal display device, preferably by offset printing method, spin-coating method or ink jet printing method, respectively liquid crystal aligning agent of the present invention is coated on comb teeth-shaped and is provided with on the conducting film formation face of substrate of the nesa coating that forms pattern, and do not arrange on the one side of subtend substrate of conducting film, then heat each coated face, formation is filmed.At this moment substrate, the material of nesa coating, the patterning method of nesa coating, the pre-treatment of substrate and the heating means after the coating of liquid crystalline alignment agent used are identical with above-mentioned (1-1).The preferred thickness of filming formed is identical with above-mentioned (1-1).

(2) when liquid crystal display device that the liquid crystal display device by method manufacturing of the present invention is the VA type, can will directly be used as liquid crystal orientation film as above-mentioned formed filming, but also can supply with according to hope use after carrying out milled processed described below.On the other hand, during liquid crystal display device beyond manufacturing the VA type, by as above-mentioned formed filming implement milled processed and form liquid crystal orientation film.

Milled processed, can by use reeled the roller of the formed cloth of fiber such as nylon, artificial silk, cotton on certain orientation to as above-mentioned formed coated surface rubbed and implemented.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 to liquid crystal orientation film shown in Japanese kokai publication hei 6-222366 communique for example or Japanese kokai publication hei 6-281937 communique, thereby the processing that the pre-tilt angle that makes the liquid crystal orientation film subregion changes, or as shown in Japanese kokai publication hei 5-107544 communique form etchant resist on the part on liquid crystal orientation film surface after, carry out milled processed in the milled processed from previous on different direction, then remove the processing of etchant resist, make liquid crystal orientation film there is different liquid crystal aligning abilities on each zone, thereby can improve the field-of-view characteristics of the liquid crystal display device of gained.

(3) prepare two substrates that form this liquid crystal orientation film, and configure liquid crystal between two substrates of subtend configuration, manufacture liquid crystal cell.Herein, when to filming, carrying out milled processed, by two substrate subtend configurations, the grinding direction in making respectively to film is mutually the angle of regulation, for example quadrature or antiparallel.In order to manufacture liquid crystal cell, can enumerate for example following two kinds of methods.

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

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

In the situation that adopt above-mentioned either method, all wishes further to as the liquid crystal cell of above-mentioned manufacturing, be heated to the temperature that liquid crystal used is isotropic phase, then slowly cool to room temperature, the flow orientation while removing thus the injection liquid crystal.Then, by the polaroid of fitting, can obtain this liquid crystal display device thus on the outer surface of liquid crystal cell.

As sealing agent, can enumerate such as containing as the alumina balls of separator and the epoxy resin that contains solidifying agent etc.

As liquid crystal, can enumerate such as nematic liquid crystal and dish shape type liquid crystal etc.Preferred nematic liquid crystal wherein.When VA type liquid crystal cell, the nematic liquid crystal that preferably there is negative dielectric anisotropy.As this liquid crystal, can enumerate such as dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal etc.When TN type liquid crystal cell or STN type liquid crystal cell, the nematic liquid crystal that preferably there is positive dielectric anisotropy.As this liquid crystal, can enumerate such as biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cubane-like liquid crystal etc.In addition, can also add the chirality agent that such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate etc. sold as cholesteryl liquid crystal (メ Le Network company, " C-15 ", " CB-15 ") in above-mentioned liquid crystal; To oxygen base α-tolylene-Ferroelectric liquid Crystals such as amino-2-methyl butyl laurate etc. are used in the last of the ten Heavenly stems.

As the polaroid of fitting on the liquid crystal cell outside surface, can enumerate with the rhodia protective membrane and clamp when making the polyvinyl alcohol stretch orientation 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 and form.

Compound of the present invention, meaned by above-mentioned formula (1).This compound, can be preferably used as the compositions such as liquid crystal aligning agent that form liquid crystal orientation film.For the detailed description of the manufacture method of this compound and compound, owing to being illustrated in the descriptive item of contained [B] compound at this liquid crystal aligning agent, therefore omit herein.

Embodiment

Below, describe the present invention in detail based on embodiment, but the present invention can't help the description of this embodiment and carry out determinate explanation.

The synthesis example of<[A] polymkeric substance >

[synthesis example 1]

Will be as tetracarboxylic dianhydride's 98g (0.50 mole) 1,2,3,4-tetramethylene tetracarboxylic dianhydride and 110g (0.50 mole) pyromellitic acid dianhydride, with the 200g (1.0 moles) 4 as diamines, 4 '-diaminodiphenyl-methane, be dissolved in 230g METHYLPYRROLIDONE and the formed mixed solvent of 2100g gamma-butyrolactone, carry out reaction in 3 hours under 40 ℃, then append the 1350g gamma-butyrolactone, obtain the solution that contains 10 quality % polyamic acids (PA-1).The soltion viscosity of this solution is 125mpa.s.

[synthesis example 2]

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

[synthesis example 3]

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2, 3, 5-tricarboxylic basic ring amyl group acetic acid 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 94g (0.87 mole) Ursol D as diamines, 25g (0.10 mole) 1, 3-bis-(3-aminopropyl) tetramethyl disiloxane and 9.6g (0.015 mole) 3, 6-bis-(4-amino-benzene acyloxy) cholestane, and as 8.1g (0.030 mole) octadecylamine of monoamine, be dissolved in the 960g METHYLPYRROLIDONE, carry out reaction in 6 hours under 60 ℃, obtain the solution that contains polyamic acid.The take a morsel polyamic acid solution of gained, add METHYLPYRROLIDONE wherein, forms the solution that polyamic acid concentration is 10 quality %, and the soltion viscosity of its mensuration is 60mPas.

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

[synthesis example 4]

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2, 3, 5-tricarboxylic basic ring amyl group acetic acid 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 95g (0.88 mole) Ursol D as diamines, 32g (0.10 mole) 4, 4-diamino-2, 2-bis-(trifluoromethyl) biphenyl and 6.4g (0.010 mole) 3, 6-bis-(4-amino-benzene acyloxy) cholestane, and as 8.1g (0.03 mole) octadecylamine of monoamine, be dissolved in the 960g METHYLPYRROLIDONE, carry out reaction in 9 hours under 60 ℃, obtain the solution that contains polyamic acid.The take a morsel polyamic acid solution of gained, add METHYLPYRROLIDONE wherein, forms the solution that polyamic acid concentration is 10 quality %, and the soltion viscosity of its mensuration is 58mPas.

Then, in the polyamic acid solution of gained, append the 2730g METHYLPYRROLIDONE, and further add 400g pyridine and 410g diacetyl oxide, carry out 4 hours dehydration closed-loops under 110 ℃.After dehydration closed-loop reaction, with new gamma-butyrolactone, the solvent in system is carried out to solvent exchange, obtain containing the solution that the 15 quality % imide rates of having an appointment are about 95% polyimide (PI-2).The take a morsel polyimide solution of gained, add gamma-butyrolactone, forms the solution that polyimide concentration is 10 quality %, and the soltion viscosity of its mensuration is 69mPas.

[synthesis example 5]

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, with 43g (0.40 mole) Ursol D and the 52g (0.10 mole) 3 (3 as diamines, 5-diaminobenzene acyloxy) cholestane, be dissolved in the 830g METHYLPYRROLIDONE, carry out reaction in 6 hours under 60 ℃, obtain the solution that contains polyamic acid.The take a morsel polyamic acid solution of gained, add METHYLPYRROLIDONE wherein, forms the solution that polyamic acid concentration is 10 quality %, and the soltion viscosity of its mensuration is 60mPas.

Then, in the polyamic acid solution of gained, append the 1900g METHYLPYRROLIDONE, and further add 40g pyridine and 51g diacetyl oxide, carry out 4 hours dehydration closed-loops under 110 ℃.After dehydration closed-loop reaction, with new METHYLPYRROLIDONE, the solvent in system is carried out to solvent exchange, obtain containing the solution that the 15 quality % imide rates of having an appointment are about 50% polyimide (PI-3).The take a morsel polyimide solution of gained, add METHYLPYRROLIDONE, forms the solution that polyimide concentration is 10 quality %, and the soltion viscosity of its mensuration is 47mPas.

[synthesis example 6]

Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, with 49g (0.45 mole) Ursol D and the 26g (0.05 mole) 3 (3 as diamines, 5-diaminobenzene acyloxy) cholestane, be dissolved in the 750g METHYLPYRROLIDONE, carry out reaction in 6 hours under 60 ℃, obtain the solution that contains polyamic acid.The take a morsel polyamic acid solution of gained, add METHYLPYRROLIDONE wherein, forms the solution that polyamic acid concentration is 10 quality %, and the soltion viscosity of its mensuration is 58mPas.

Then, in the polyamic acid solution of gained, append the 1800g METHYLPYRROLIDONE, and further add 40g pyridine and 51g diacetyl oxide, carry out 4 hours dehydration closed-loops under 110 ℃.After dehydration closed-loop reaction, with new METHYLPYRROLIDONE, the solvent in system is carried out to solvent exchange, obtain containing the solution that the 15 quality % imide rates of having an appointment are about 50% polyimide (PI-4).The take a morsel polyimide solution of gained, add METHYLPYRROLIDONE, forms the solution that polyimide concentration is 10 quality %, and the soltion viscosity of its mensuration is 69mPas.

Synthesizing of<[B] compound >

[embodiment 1]

After 320g formalin, 8mL 1N sodium hydroxide, 20g melamine are dissolved under 35 ℃, at room temperature place diel, attract to filter the hexamethylol melamine crystal of separating out, then use methanol wash, carry out again vacuum-drying, obtain the refining thing of 48g hexamethylol melamine.Then, add 250mL tetrahydrofuran (THF), the following compound of 120g (B 1-1) in this hexamethylol melamine, and be heated to 70 ℃, then add the reaction of 1mL 0.5N aqueous hydrochloric acid after 8 hours, with the neutralization of 0.5N aqueous sodium hydroxide solution, reaction is finished.Then, in 2L water, inject reaction solution, filter the precipitation of gained, and use and take refining this precipitation of silicon post that chloroform/ethanol is developing solvent, the compound (B-1) that the average substitution degree that obtains compound (B1-1) is 2.Average substitution degree is analyzed by GPC.

[embodiment 2]

Except using the following compound of 43g (B2-1) to replace compound (B1-1), and synthesis example B1 operated equally, the compound (B-2) that the average substitution degree that obtains having the group of steroid skeleton is 1.

The modulation of<liquid crystal aligning agent >

[embodiment 3]

Mix and contain polyamic acid (PA-1) as the solution of [A] polymkeric substance and the solution that contains polyimide (PI-1), make polyamic acid (PA-1): polyimide (PI-1)=80: 20 (mass ratio), and add wherein gamma-butyrolactone, METHYLPYRROLIDONE and ethylene glycol-mono-n-butyl ether, again with respect to the total of 100 mass parts polymkeric substance, with wherein contained [B] compound, convert, add 10 mass parts to contain the solution of compound (B-1) as [B] compound, and fully stir, the formation solvent composition is gamma-butyrolactone: METHYLPYRROLIDONE: ethylene glycol-mono-n-butyl ether=71: 17: 12 (mass ratio), the solution that solid component concentration is 6.0 quality %.Use the strainer that aperture is 1 μ m to filter this solution, the modulation liquid crystal aligning agent.In addition, use N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane is as epoxy compounds.

[embodiment 4～7 and comparative example 1～5]

Except kind and the usage quantity of the compound that makes to coordinate, be respectively beyond the kind and amount that table 1 puts down in writing, and embodiment 3 operated equally the modulation liquid crystal aligning agent.In addition, the F-1 in table 1 means hexa methoxy methylol melamine (サィメ Le C300, MITSUI-CYTEC company).In addition, "-" means not use composition.

[embodiment 8]

To containing polyimide (PI-3) as in the solution of [A] polymkeric substance, add METHYLPYRROLIDONE and ethylene glycol-mono-n-butyl ether, again with respect to the total of 100 mass parts polymkeric substance, with wherein contained [B] compound, convert, add 10 mass parts to contain the solution of compound (B-1) as [B] compound, and fully stir, the formation solvent composition is METHYLPYRROLIDONE: ethylene glycol-mono-n-butyl ether=50: 50 (mass ratio), the solution that solid component concentration is 6.0 quality %.Use the strainer that aperture is 1 μ m to filter this solution, the modulation liquid crystal aligning agent.

[embodiment 9～12 and comparative example 6～10]

Except kind and the usage quantity of the compound that makes to coordinate, be respectively beyond the kind and amount that table 1 puts down in writing, and embodiment 8 operated equally the modulation liquid crystal aligning agent.In addition, the E-1 in table 1 means the mixture (ァロニッ Network ス M402, East Asia Synesis Company) of Dipentaerythritol five acrylate and dipentaerythritol acrylate.

The manufacture of<liquid crystal display device >

Use liquid crystal orientation film printing press (Japan description printing firm), the liquid crystal aligning agent that embodiment 3～7 and comparative example 1～5 are modulated is coated on the transparent electrical pole-face with the glass substrate by the formed transparency electrode of ITO film, and heating 1 minute (prebake) removes desolventizing on the hot plate of 80 ℃, then heat 10 minutes (curing afterwards) on the hot plate of 200 ℃, the formation average film thickness is

film.Use has the shredder of the roller of the artificial silk cloth of having reeled, and take the roller rotation number as 500rpm, and test portion platform translational speed is 3cm/ second, and it is 0.4mm that fine hair is clamp-oned length, carries out grinding process, gives the liquid crystal aligning energy.Then, carry out 1 minute ultrasonic washing in ultrapure water, then in 100 ℃ of cleaning ovens dry 10 minutes, obtain having the substrate of liquid crystal orientation film.Repeat these operations, obtain the substrate that a pair of (two) have liquid crystal orientation film.Then, have in above-mentioned a pair of substrate on each outer rim of liquid crystal orientation film, after coating has added the epoxy resin adhesive of the alumina balls that diameter is 5.5 μ m, make the liquid crystal aligning face relative, carry out overlapping pressing, and caking agent is solidified.Then, by liquid crystal injecting port between a pair of substrate, fill nematic liquid crystal (メ Le Network company, MLC-6221) after, with acrylic acid series light-curing adhesive encapsulated liquid crystals inlet, manufacture thus liquid crystal cell.

Use liquid crystal orientation film printing press (Japan description printing firm), the liquid crystal aligning agent that embodiment 8～12 and comparative example 6～10 are modulated is coated on the transparent electrical pole-face with the glass substrate by the formed transparency electrode of ITO film, and heating 1 minute (prebake) removes desolventizing on the hot plate of 80 ℃, then heat 10 minutes (curing afterwards) on the hot plate of 200 ℃, the formation average film thickness is

film.Repeat this operation, obtain the substrate that a pair of (two) have liquid crystal orientation film.Then, have in above-mentioned a pair of substrate on each outer rim of liquid crystal orientation film, after coating has added the epoxy resin adhesive of the alumina balls that diameter is 5.5 μ m, make the liquid crystal aligning face relative, carry out overlapping pressing, and caking agent is solidified.Then, by liquid crystal injecting port between a pair of substrate, fill nematic liquid crystal (メ Le Network company, MLC-6608) after, with acrylic acid series light-curing adhesive encapsulated liquid crystals inlet, manufacture thus liquid crystal cell.

<estimate

Liquid crystal display device for the liquid crystal aligning agent manufacturing of using modulation, carry out following evaluation.The result merging is shown in table 1.

[evaluation of weathering resistance]

For liquid crystal cell, under 70 ℃, after applying the voltage of 5V with the application time of 60 microseconds, the interval of 167 milliseconds, by Dongyang テ Network ニ power company " VHR-1 ", measured from applying the voltage retention (initial stage voltage retention (VHR removing 167 milliseconds _iN)).Then, for the liquid crystal cell of having measured the initial stage voltage retention, use and to using carbon arc and carry out the rayed of 5000 hours as the weather resistance test device of light source.For the liquid crystal cell after rayed, use method same as described above again to measure voltage retention (voltage retention (VHR after rayed _aF)).Be that 90% weathering resistance when above is judged as well by the sustainment rate of voltage retention, be judged as bad by the weathering resistance less than 90% time.

[evaluation of residual DC voltage]

For the liquid crystal cell as above-mentioned manufacturing, by flicker disappearance method, measure the DC voltage value (initial stage DC voltage) in liquid crystal cell.Then, to this liquid crystal cell, apply the voltage of 20 hours direct current 17V under 100 ℃.For the liquid crystal cell applied after voltage, after discharging direct supply, after 15 minutes, again by flicker disappearance method, measure the DC voltage value in liquid crystal cell.At this moment, the DC voltage value after applying voltage deducts the value of initial stage DC voltage value gained as residual DC voltage.By the residual DC magnitude of voltage, less than the average evaluation of 500mV, being "+", is "-" by the average evaluation more than 500mV.

From table 1 result clearly, liquid crystal aligning agent of the present invention can form the electrical characteristic that remained good, has good weathering resistance simultaneously, and has suppressed the liquid crystal orientation film that residual DC voltage increases.

Industrial applicibility

Claims

1. a liquid crystal aligning agent, it contains [A] and is selected from least one polymkeric substance in the group that polyamic acid and polyimide form, and the represented compound of [B] following formula (1),

In formula (1), the alkoxy methyl that R is 2～7 for hydrogen atom, methylol, carbonatoms independently of one another ,-CH ₂oY or-CH ₂oZ; Y is the group with ring-type the structure of hindered amine; Z is the group with hindered phenol structure, and still, at least one R is the group with ring-type the structure of hindered amine or hindered phenol structure.

2. liquid crystal aligning agent as claimed in claim 1, ring-type the structure of hindered amine that wherein above-mentioned Y has is following formula (2 ^a) represented group, the hindered phenol structure that Z has is following formula (3 ^a) represented group,

Formula (2 ^a) in, R ⁱfor hydrogen atom, the carbonatoms alkyl that is 1～6, the aryl that carbonatoms is 6～20, aralkyl or 1, the 3-dioxo butyl that carbonatoms is 7～13;

R ^iI～R ^vthe aralkyl that the aryl that the alkyl that is 1～6 for carbonatoms independently of one another, carbonatoms are 6～12 or carbonatoms are 7～13;

X ¹for singly-bound, carbonyl or ^*-CONH-, still, be connected with piperidine ring with the connecting key of *;

X ²～X ⁵be independently of one another singly-bound, carbonyl, ^*-CH ₂-CO-or ^*-CH ₂-CH (OH)-, still, with the connecting key of *, with piperidine ring, be connected;

X ⁶for singly-bound ,-alkylidene group that CO-, methylene radical or carbonatoms are 2～6,

Formula (3 ^a) in, R ^vIfor the carbonatoms alkyl that is 4～16; R ^vIIfor hydrogen atom or the carbonatoms alkyl that is 1～16; X ⁷for singly-bound ,-alkylidene group that CO-, methylene radical or carbonatoms are 2～6; The integer that n is 0～3.

3. liquid crystal aligning agent as claimed in claim 2, wherein [B] compound is

(b1) the represented compound of following formula (1x) and

(b2) resultant of reaction of the represented compound of following formula (2) and/or formula (3),

In formula (1x), R ^xthe alkoxy methyl that is 2～7 for hydrogen atom, methylol or carbonatoms independently of one another, still, at least one R ^xfor methylol or the carbonatoms alkoxy methyl that is 2～7,

Y-OH (2)

In formula (2), Y is above-mentioned formula (2 ^a) represented group,

Z-OH (3)

In formula (3), Z is above-mentioned formula (3 ^a) represented group.

4. liquid crystal aligning agent as claimed in claim 2 or claim 3, wherein above-mentioned Y is for being selected from following formula (2 ^a-1)～(2 ^a-2) at least one in the group that represented group forms, Z is for being selected from following formula (3 ^a-1)～(3 ^a-2) at least one in the group that represented group forms,

。

5. liquid crystal aligning agent as described as claim 1～3 any one, wherein the usage ratio of [B] compound, be below above 100 mass parts of 0.1 mass parts with respect to 100 mass parts [A] polymkeric substance.

6. by the formed liquid crystal orientation film of the described liquid crystal aligning agent of claim 1～3 any one.

7. the liquid crystal display device that there is liquid crystal orientation film claimed in claim 6.