CN102002372A

CN102002372A - Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, compound and manufacture method of the compound

Info

Publication number: CN102002372A
Application number: CN2010102596317A
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: 2011-04-06
Anticipated expiration: 2030-08-19
Also published as: KR20110023735A; TW201120098A; JP2011070160A; CN102002372B; TWI485182B; JP5556395B2; KR101626796B1

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, it is good to the present invention relates to a kind of liquid crystal aligning, 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 because it has advantages such as little, easy miniaturization of power consumption and flattening, therefore is widely used in 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 switch type (IPS type), vertical orientating type liquid crystal cells such as (VA types) in have twisted nematic (TN type), super-twist nematic (STN type), the 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 influence.

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, therefore be used for most liquid crystal display device (with reference to patent documentation 1～6) with the affinity of liquid crystal etc.Known this liquid crystal display device is being used for TV purposes etc., and long-time continuous is when driving, and liquid crystal orientation film is because of being exposed to the light and heat variation for a long time, and the display quality variation.

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

In view of this situation, even wish to develop a kind of can formation when carrying out the long-time continuous driving, also can keep good liquid crystal aligning performance and electrical characteristic, have 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 keep good liquid crystal aligning performance and electrical characteristic, have good weathering resistance simultaneously, and suppressed the manufacture method of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, compound and the compound of the liquid crystal orientation film that residual DC voltage increases with liquid crystal orientation film.

The invention that is used to address the above problem is a kind of liquid crystal aligning agent, and it contains [A] and is selected from least a polymkeric substance in the group that polyamic acid and polyimide constitute and the represented compound of [B] following formula (1).

In the formula (1), R independently of one another for hydrogen atom, methylol, carbonatoms be 2～7 alkoxy methyl ,-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,, also can keep good liquid crystal aligning performance and electrical characteristic even can form when carrying out the long-time continuous driving, have 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 had is preferably following formula (2 ^a) represented group, the hindered phenol structure optimization that Z had is following formula (3 ^a) represented group.

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

R ^II～R ^VBe that 1～6 alkyl, carbonatoms are that 6～12 aryl or carbonatoms are 7～13 aralkyl for carbonatoms independently of one another.

X ¹For singly-bound, carbonyl or ^*-CONH-.But the connecting key that has * is connected with piperidine ring.

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

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

Formula (3 ^a) in, R ^VIIt for carbonatoms 4～16 alkyl.R ^VIIIt for hydrogen atom or carbonatoms 1～16 alkyl.X ⁷For singly-bound ,-CO-, methylene radical or carbonatoms are 2～6 alkylidene group.N is 0～3 integer.

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

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

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

Y-OH (2)

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

Z-OH (3)

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

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

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

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

Also suitably comprise in the present invention by formed liquid crystal orientation film of this liquid crystal aligning agent and liquid crystal display device with this liquid crystal orientation film.This liquid crystal display device, can suitably be used for various devices, for example 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 present invention comprises the manufacture method of this compound, and this method has the operation that makes the represented compound reaction of represented compound of following formula (1x) and following formula (2) and/or (3).

Y-OH (2)

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

Z-OH (3)

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

In addition, above-mentioned R ^IRepresented carbonatoms is that 6～20 aryl, carbonatoms are 7～13 aralkyl, R ^II～R ^VRepresented carbonatoms is that 1～6 alkyl, carbonatoms are that 6～12 aryl and carbonatoms are that 7～13 the part or all of hydrogen atom that aralkyl had 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 keep good liquid crystal aligning performance and electrical characteristic, have good weathering resistance simultaneously, and suppressed the manufacture method of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, compound and the compound of the liquid crystal orientation film that residual DC voltage increases with liquid crystal orientation film.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, for example be suitable for 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 〉

Liquid crystal aligning agent of the present invention, contain [A] be selected from least a polymkeric substance in the group that polyamic acid and polyimide constitute (below, be called " [A] polymkeric substance "), and the represented compound of [B] above-mentioned formula (1) (below, be 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, describe in detail for [A] polymkeric substance, [B] compound and any composition.

＜[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, describe in detail for tetracarboxylic dianhydride and diamines.

[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-two chloro-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0 ^2,6] undecane-3,5,8, 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, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) sulfobenzide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide compound dianhydride, to phenylene-two (triphenyl phthalic acid) dianhydride, metaphenylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-phenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-ditan dianhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butyleneglycol-two (dehydration trimellitate), 1,6-hexylene glycol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2, the compound that 2-two (4-hydroxyphenyl) propane-two (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 the above-mentioned formula, R ¹And R ³Independently of one another for having 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 the represented compound of for example following formula (T-1-1)～(T-2-1).

Among these tetracarboxylic dianhydrides, use to 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 acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4,5, at least a (below, be called " specific tetracarboxylic dianhydride ") in the group that the represented compound of 8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-1-1)～(T-1-3) and formula (T-2-1) constitutes, considering from the viewpoint that can show good liquid crystal aligning, 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 acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0 ^2,6] undecane-3,5,8, at least a in the group that the represented compound of 10-tetraketone, pyromellitic acid dianhydride and above-mentioned formula (T-1-1) constitutes.

As specific tetracarboxylic dianhydride's usage ratio, with respect to whole tetracarboxylic dianhydrides, be preferably 50 moles more than the %, more preferably 60 moles more than the %, be preferably 80 moles especially more than the %, 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, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 3,3 '-two (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-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2,7 diamin of luorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene radical-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(to the phenylene isopropylidene) two (aniline), 4,4 '-(metaphenylene isopropylidene) two (aniline), 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, 3, the 5-diaminobenzoic acid, 1,4-two-(4-aminophenyl)-piperazine, and following formula (D-1)～represented aromatic diamines such as compound of formula (D-5);

In the formula (D-4), y is 2～12 integer.In the above-mentioned formula (D-5), z is the integer of 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), 1,3-two (amino methyl) hexanaphthene and 1, aliphatie diamine and ester ring type diamines such as 4-two (amino methyl) hexanaphthene;

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

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

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

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

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

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

The phenyl ring that diamines and single-substituted diamines had of above-mentioned aromatic diamine, the nitrogen-atoms beyond intramolecularly has two primary aminos and this primary amino can be that 1～4 alkyl (being preferably methyl) replaces by one or more carbonatoms also.In addition, the steroid backbone in the above-mentioned formula (D-8) is meant by 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, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(to the phenylene diisopropylidene) two (aniline), 4,4 '-(metaphenylene diisopropylidene) two (aniline), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 1, the 4-diamino-cyclohexane, 4,4 '-methylene radical two (hexahydroaniline), 1,3-two (amino methyl) hexanaphthene, the represented separately compound of above-mentioned formula (D-1)～(D-5), 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-two (4-aminophenyl)-p-diaminodiphenyl, N, N '-two (4-aminophenyl)-N, N '-tolidine, 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 a (below, be called " specific diamines ") in the group that 3-two (3-aminopropyl)-tetramethyl disiloxane constitutes.

As the usage quantity of used above-mentioned specific diamines during polyamic acid in synthetic this liquid crystal aligning agent, with respect to whole diamines, be preferably 50 moles more than the %, more preferably 60 moles more than the %, be preferably 80 moles especially more than the %.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 that is closed in the 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,, is preferably-20 ℃～150 ℃ as temperature of reaction, 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 for example non-proton property polar solvent, phenol and derivative thereof, alcohol, ketone, ester, ether, halon, hydrocarbon etc.

As above-mentioned non-proton property polar solvent, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, N, dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA etc.

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

As above-mentioned alcohol, can enumerate for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1,4-butyleneglycol, triglycol, ethylene glycol monomethyl ether etc.

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

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

As above-mentioned ether, can enumerate for example diethyl ether, ethylene glycol monomethyl ether, ethylene glycol 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, 1,4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.

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

In these organic solvents, the preferred use is selected from the group's (organic solvent of first group) that is made of non-proton property polar solvent and phenol and derivative thereof more than one, or be selected from above-mentioned first group organic solvent more than one and be selected from more than one mixture in the group's (organic solvent of second group) that constitutes by alcohol, ketone, ester, ether, halohydrocarbon and hydrocarbon.As the usage ratio of the organic solvent of second group, the total with respect to the organic solvent of first group and second group is preferably below the 50 quality %, more preferably below the 40 quality %, and is preferably especially below the 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 the reaction soln can be separated the back and supply with the modulation of liquid crystal aligning agent, resupply the modulation of liquid crystal aligning agent after perhaps isolated polyamic acid can also being made with extra care.The polyamic acid dehydration closed-loop is formed the occasion of polyimide, above-mentioned reaction soln directly can be supplied with the dehydration closed-loop reaction, also polyamic acid contained in the reaction soln can be separated the back and supply with the dehydration closed-loop reaction, resupply the dehydration closed-loop reaction after perhaps isolated polyamic acid can also being made with extra care.The separation of polyamic acid can obtain precipitate by above-mentioned reaction soln is put in a large amount of poor solvents, and the method for this precipitate of drying under reduced pressure perhaps uses vaporizer that the decompression distilled method of the organic solvent in the reaction soln is carried out again.In addition, can make its method of separating out with poor solvent then, or carry out once or several times using the vaporizer method of distilled operation that reduces pressure, refining polyamic acid by this polyamic acid is dissolved in the organic solvent once more.

[synthesizing of polyimide]

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

As tetracarboxylic dianhydride that can be used for synthesis of polyimides and diamines, can enumerate and tetracarboxylic dianhydride that can be used for synthesizing polyamides acid and the identical compound of diamines.The kind and the usage ratio of preferred tetracarboxylic dianhydride and diamines are identical during with synthesizing polyamides acid.

Above-mentioned polyimide, can be with as the amido acid structure fully dehydrating closed loop that polyamic acid had of raw material and the complete imidization thing that obtains, perhaps also can be the amido acid structure that only a part of dehydration closed-loop in the amido acid structure obtained and imide ring structure and the part imidization thing deposited.Imidization rate as polyimide in this liquid crystal aligning agent is preferably more than 30%, and more preferably more than 40%.Above-mentioned imidization rate is to represent 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 also can be different imide ring.The imidization rate, can be by polyimide ¹H-HMR is known.In addition, the imidization rate in this specification sheets is that polyimide at room temperature fully behind the drying under reduced pressure, is dissolved in the deuterate dimethyl sulfoxide (DMSO), and with tetramethylsilane as primary standard, at room temperature measure ¹H-NMR, by this measurement result, (2) are obtained according to the following equation.

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

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

The dehydration closed-loop that is used for the polyamic acid of synthetic above-mentioned polyimide, can be by the method for (i) heating polyamic acid, perhaps (ii) polyamic acid is dissolved in the organic solvent, in this solution, adds dewatering agent and dehydration closed-loop catalyzer, 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 then.As the reaction times, be preferably 1.0 hours～24 hours, and more preferably 1.0 hours～12 hours.

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

As the dehydration closed-loop catalyzer, can enumerate for example tertiary amines such as pyridine, collidine, two picolins, triethylamine.As the usage quantity of dehydration closed-loop catalyzer,, be preferably 0.01 mole～10 moles with respect to 1 mole of used dewatering agent.As the organic solvent that can be used for dehydration closed-loop reaction, can enumerate as used organic solvent in polyamic acid synthetic and illustrative organic solvent.Temperature of reaction as the dehydration closed-loop reaction is 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) preparation of liquid crystal aligning agent can directly be supplied with it by the polyimide of gained in the method, resupplies the preparation of liquid crystal aligning agent after perhaps also the polyimide of gained can being made with extra care.On the other hand, aforesaid method (ii) in, can obtain containing the reaction soln of polyimide.This reaction soln, it directly can be supplied with the preparation of liquid crystal aligning agent, also can after from reaction soln, removing dewatering agent and dehydration closed-loop catalyzer, supply with the preparation of liquid crystal aligning agent, polyimide can also be separated the preparation that liquid crystal aligning agent is supplied with in the back, resupply the preparation of liquid crystal aligning agent after perhaps isolating polyimide can also being made with extra care.From reaction soln, remove dewatering agent and dehydration closed-loop catalyzer, can adopt for example method such as solvent exchange.The separation of polyimide, refining, can by with carry out as the separating of polyamic acid, the described same operation of process for purification.

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 in synthesizing polyamides when acid, adds molecular weight regulator and carry out in polymerization reaction system.As molecular weight regulator, can enumerate for example single acid anhydride, monoamine compound, monoisocyanates compound etc.

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

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

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

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

As above the polyamic acid of gained or polyimide when formation concentration is the solution of 10 quality %, preferably has 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), be polymers soln, use E type rotational viscosimeter 25 ℃ of values of being measured down for the synthetic 10 weight % concentration of good solvent (for example gamma-butyrolactone, N-N-methyl-2-2-pyrrolidone N-etc.) that adopt this polymkeric substance.

As [A] polymkeric substance in this liquid crystal aligning agent, preferably only use polyimide or mix use polyimide and polyamic acid.Imidization rate as only using polyimide when [A] polymkeric substance is preferably below 70%, and more preferably 30%～60%.On the other hand, the average imidization rate when mix using polyimide and polyamic acid as [A] polymkeric substance is preferably below 70%, and more preferably 10%～60%, and be preferably 15%～55% especially.This average imidization rate is the amido acid structure number (PA-A) by imide ring structure number (PI-I), amido acid structure number (PI-A) and the polyamic acid of polyimide contained in the liquid crystal aligning agent, and calculates the value that gets 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 the formula (1) has ring-type the structure of hindered amine or hindered phenol structure, and the R number as replacing is preferably 1～3.

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

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

R in the above-mentioned formula (1) independently of one another for hydrogen atom, methylol, carbonatoms be 2～7 alkoxy methyl ,-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.As the structure of hindered amine that above-mentioned Y had, be preferably above-mentioned formula (2 ^a) represented group.

As above-mentioned formula (2 ^a) in R ^IRepresented carbonatoms is 1～6 alkyl, can be the straight chain shape or divides in dendritic any, and can enumerate for example methyl, ethyl, propyl group, butyl, amyl group etc.

As above-mentioned formula (2 ^a) in R ^IRepresented carbonatoms is 6～20 aryl, can enumerate for example phenyl, 3-fluorophenyl, 3-chloro-phenyl-, 4-chloro-phenyl-, 4-isopropyl phenyl, 4-n-butylphenyl, 3-chloro-4-aminomethyl phenyl, 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 ^IRepresented carbonatoms is 7～13 aralkyl, can enumerate for example 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 phenyl, 3-fluorophenyl, 3-chloro-phenyl-, 4-chloro-phenyl-, 4-isopropyl phenyl, 4-n-butylphenyl or 3-chloro-4-aminomethyl phenyl) are represented etc.

As above-mentioned formula (2 ^a) R ^II～R ^VRepresented carbonatoms is 1～6 alkyl, can enumerate as above-mentioned R ^IRepresented carbonatoms is 1～6 the illustrated group of alkyl.

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

As above-mentioned formula (2 ^a) R ^II～R ^VRepresented carbonatoms is 7～13 aralkyl, and the part or all of hydrogen atom that aromatic nucleus had of aralkyl can be the group that 1～4 alkoxyl group replaces by formyl radical or carbonatoms, and 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, the 5-trimethoxyphenyl) ethyl etc.

As above-mentioned formula (2 ^a) represented compound, preferred R ^IBe hydrogen atom, R ^II～R ^VAll be methyl, X ¹～X ⁵It all is single bonded compound.

In addition, in the present invention, have the hindered phenol structure, be meant 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 for example 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.

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

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

As above-mentioned formula (3 ^a) middle R ^VIIRepresented carbonatoms is 1～16 alkyl, is 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, (still, x satisfies the resultant of reaction of 0＜x＜n) to be preferably 1 molar part (b 1) compound and x molar part (b2) compound.But n is that 1 molecule above-mentioned (b 1) methylol that compound had or carbonatoms are the number of 2～7 alkoxy methyl.

As R in the above-mentioned formula (1x) of (b 1) compound ^xRepresented carbonatoms is 1～6 alkyl, is preferably carbonatoms and is 1～4 alkyl, more preferably methyl, ethyl, normal-butyl, isobutyl-, and be preferably methyl especially.As this compound (b 1), can enumerate for example N, N, N ', N ', N ", N " 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 one 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 one ト 212, サィメ Le 202, マィコ one ト 508 (MITSU-CYTEC society) etc.

As operable organic solvent in the above-mentioned reaction, can enumerate as above-mentioned polyamic acid used organic solvent when synthetic and illustrative organic solvent.Wherein, preferred non-proton organic solvent, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, 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 compound in the 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 is 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 solution of preferred [B] compound.This solution can directly be supplied with the modulation of this liquid crystal aligning agent, perhaps can supply with the modulation of this liquid crystal aligning agent from reaction soln behind separation and purification [B] compound.As the method for separation and purification from reaction soln [B] compound, can enumerate for example liquid-liquid extraction, column chromatography, distillation method, recrystallize etc.

As preferred [B] compound, be that the methylol that had of compound (b 1) or carbonatoms are a part and compound (b2) reaction of 2～7 alkoxy methyl, and to have the methylol or the carbonatoms that come from compound (b1) simultaneously be 2～7 alkoxy methyl and the radicals R that comes from compound (b2) ^ITherefore, this liquid crystal aligning agent this by containing [B] compound even can form when long-time continuous drives, also can be kept good liquid crystal aligning performance and electrical characteristic, has 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) at least a in the group of represented group formation, Z more preferably is selected from above-mentioned formula (3 ^a-1)～(3 ^a-2) at least a in the group of represented group formation.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 preferably 1 mass parts～30 mass parts especially.

＜any composition 〉

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

[other polymkeric substance]

Above-mentioned other polymkeric substance can be used to improve solution properties and electrical characteristic.As other polymkeric substance, can enumerate for example 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 the liquid crystal aligning agent of the present invention, with respect to 100 mass parts [A] polymkeric substance, be preferably below the 100 quality %, more preferably below the 80 quality %, and be preferably especially below the 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 that forms 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-two (N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl hexanaphthene etc.As the cooperation 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, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-3-aminopropyltriethoxywerene werene, N-tri-ethoxy silylpropyl diethylenetriamine, N-Trimethoxy silane base propyl group diethylenetriamine, 10-Trimethoxy silane base-1,4,7-three azepine decane, 10-triethoxysilicane alkyl-1,4,7-three azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxo ethylidene)-3-TSL 8330, N-two (oxo ethylidene)-3-aminopropyltriethoxywerene werene 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, the 6-hexanediyl ester, 1, the 6-hexanediol dimethacrylate, 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, tetramethylolmethane tetramethyl-acrylate, 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, Japan chemical drug society), PVC スコ one ト 260, PVC スコ one ト 312, PVC スコ one ト 335HP, PVC スコ one ト 295, PVC スコ one ト 300, PVC スコ one ト 360, PVC スコ one ト GPT, PVC スコ one ト 3PA, PVC スコ one ト 400 (more than, Osaka organic chemistry industry society), ニュ one 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 with above-mentioned [A] polymkeric substance, [B] compound, and any composition as required, the solution shape composition that is preferably dissolved in the organic solvent is modulated.

As organic solvent, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, n-Butyl lactate, butylacetate, the methoxypropionic acid methyl esters, 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, perhaps are used in combination.

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

As preferred solid component concentration scope, used method 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 is 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 〉

Also preferably be contained among the present invention by the formed liquid crystal orientation film of this liquid crystal aligning agent.Liquid crystal orientation film of the present invention by this liquid crystal aligning agent is coated on the substrate, then heats coated face and is formed on the 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 making TN type, STN type or VA type liquid crystal display device, make two substrates that are provided with the nesa coating that forms pattern paired, and preferably respectively liquid crystal aligning agent of the present invention is coated on separately the transparent conducting film formation face by offset printing method, spin-coating method or ink jet printing method, then heat each coated face, formation is filmed.As substrate, can use for example 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, can enumerate for example form patternless nesa coating after, by photoengraving form method of patterning, when forming nesa coating, use the method for mask etc. with desirable pattern.When the coating of liquid crystalline alignment agent, for the cementability that makes substrate surface and nesa coating and film is better, can be embodied on the face that formation is filmed in the substrate surface, be coated with the pre-treatment of functional silanes compound, functionality titanium compound etc. in advance.

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

Then, to desolvate in order removing fully, and to make the polyamic acid hot-imide as required, implement to burn till (afterwards curing).As the back 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.Though this liquid crystal aligning agent forms filming of being made of liquid crystal orientation film by remove organic solvent after coating, but contained polymkeric substance is polyamic acid or has the imide ring structure simultaneously and during the polyimide of amido acid structure in this liquid crystal aligning agent, also can filming in formation, the back is further heats, carry out the dehydration closed-loop reaction, and form filming of imidization more.

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

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

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

Milled processed, can by use reeled the roller of formed cloth of fiber such as nylon, artificial silk, cotton for example on certain orientation to as above-mentioned formed coated surface rub and implement.Thus, give the alignment capability of liquid crystal molecule to filming, thereby form liquid crystal orientation film.Further, for as above-mentioned formed liquid crystal orientation film, carry out a part of irradiation ultraviolet radiation shown in Japanese kokai publication hei 6-222366 communique for example or the Japanese kokai publication hei 6-281937 communique to liquid crystal orientation film, thereby the processing that the pre-tilt angle that makes the liquid crystal orientation film subregion changes, or shown in Japanese kokai publication hei 5-107544 communique after forming etchant resist on the part on liquid crystal orientation film surface, on the direction different, carry out milled processed with previous milled processed, remove the processing of etchant resist then, make liquid crystal orientation film on each zone, have different liquid crystal aligning abilities, thereby can improve the field-of-view characteristics of the liquid crystal display device of gained.

(3) prepare two substrates that form this liquid crystal orientation film, and between two substrates of subtend configuration, dispose liquid crystal, make liquid crystal cell.When carrying out milled processed,, make grinding direction in respectively filming be the angle of regulation, for example quadrature or antiparallel mutually herein, with the configuration of two substrate subtends to filming.In order to make liquid crystal cell, can enumerate for example following two kinds of methods.

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

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

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

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

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

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

＜compound 〉

Compound of the present invention is represented 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,, therefore omit herein owing in the descriptive item of contained [B] compound of this liquid crystal aligning agent, be illustrated.

Embodiment

Below, describe the present invention in detail based on embodiment, but the present invention and 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 is with the 200g (1.0 moles) 4 as diamines, 4 '-diaminodiphenyl-methane, be dissolved in 230g N-N-methyl-2-2-pyrrolidone N-and the formed mixed solvent of 2100g gamma-butyrolactone, under 40 ℃, carry out reaction in 3 hours, append the 1350g gamma-butyrolactone then, obtain containing the solution of 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 is dissolved in 370g N-N-methyl-2-2-pyrrolidone N-and the formed mixed solvent of 3300g gamma-butyrolactone, under 40 ℃, carry out reaction in 3 hours, obtain containing the solution of 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 acetate dianhydride and 160g (0.50 mole) 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, with 94g (0.87 mole) Ursol D as diamines, 25g (0.10 mole) 1,3-two (3-aminopropyl) tetramethyl disiloxane and 9.6g (0.015 mole) 3,6-two (4-amino-benzene acyloxy) cholestane, and as 8.1g (0.030 mole) the octadecane amine of monoamine, be dissolved in the 960g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 6 hours, obtain containing the solution of polyamic acid.The take a morsel polyamic acid solution of gained, to wherein adding the N-N-methyl-2-2-pyrrolidone N-, forming polyamic acid concentration is the solution of 10 quality %, the soltion viscosity of its mensuration is 60mPas.

Then, in the polyamic acid solution of gained, append 2700g N-N-methyl-2-2-pyrrolidone N-, and further add 400g pyridine and 410g diacetyl oxide, under 110 ℃, carry out 4 hours dehydration closed-loops.After the dehydration closed-loop reaction, with new gamma-butyrolactone the solvent in the system is carried out solvent exchange and (, employed pyridine and diacetyl oxide in the dehydration closed-loop reaction are expelled to outside the system by this operation.Down together.), obtain containing the solution that the 15 quality % imidization rates of having an appointment are about 95% polyimide (PI-1).The take a morsel polyimide solution of gained adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 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 acetate dianhydride and 160g (0.50 mole) 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone is with 95g (0.88 mole) Ursol D as diamines, 32g (0.10 mole) 4,4-diamino-2,2-two (trifluoromethyl) biphenyl and 6.4g (0.010 mole) 3,6-two (4-amino-benzene acyloxy) cholestane, and as 8.1g (0.03 mole) the octadecane amine of monoamine, be dissolved in the 960g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 9 hours, obtain containing the solution of polyamic acid.The take a morsel polyamic acid solution of gained, to wherein adding the N-N-methyl-2-2-pyrrolidone N-, forming polyamic acid concentration is the solution of 10 quality %, the soltion viscosity of its mensuration is 58mPas.

Then, in the polyamic acid solution of gained, append 2730g N-N-methyl-2-2-pyrrolidone N-, and further add 400g pyridine and 410g diacetyl oxide, under 110 ℃, carry out 4 hours dehydration closed-loops.After the dehydration closed-loop reaction, the solvent in the system is carried out solvent exchange, obtain containing the solution that the 15 quality % imidization rates of having an appointment are about 95% polyimide (PI-2) with new gamma-butyrolactone.The take a morsel polyimide solution of gained adds gamma-butyrolactone, and forming polyimide concentration is the solution of 10 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 acetate dianhydride, with 43g (0.40 mole) Ursol D and 52g (0.10 mole) 3 (3 as diamines, 5-diaminobenzene acyloxy) cholestane, be dissolved in the 830g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 6 hours, obtain containing the solution of polyamic acid.The take a morsel polyamic acid solution of gained, to wherein adding the N-N-methyl-2-2-pyrrolidone N-, forming polyamic acid concentration is the solution of 10 quality %, the soltion viscosity of its mensuration is 60mPas.

Then, in the polyamic acid solution of gained, append 1900g N-N-methyl-2-2-pyrrolidone N-, and further add 40g pyridine and 51g diacetyl oxide, under 110 ℃, carry out 4 hours dehydration closed-loops.After the dehydration closed-loop reaction, the solvent in the system is carried out solvent exchange, obtain containing the solution that the 15 quality % imidization rates of having an appointment are about 50% polyimide (PI-3) with new N-N-methyl-2-2-pyrrolidone N-.The take a morsel polyimide solution of gained adds the N-N-methyl-2-2-pyrrolidone N-, and forming polyimide concentration is the solution of 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 acetate dianhydride, with 49g (0.45 mole) Ursol D and 26g (0.05 mole) 3 (3 as diamines, 5-diaminobenzene acyloxy) cholestane, be dissolved in the 750g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out reaction in 6 hours, obtain containing the solution of polyamic acid.The take a morsel polyamic acid solution of gained, to wherein adding the N-N-methyl-2-2-pyrrolidone N-, forming polyamic acid concentration is the solution of 10 quality %, the soltion viscosity of its mensuration is 58mPas.

Then, in the polyamic acid solution of gained, append 1800g N-N-methyl-2-2-pyrrolidone N-, and further add 40g pyridine and 51g diacetyl oxide, under 110 ℃, carry out 4 hours dehydration closed-loops.After the dehydration closed-loop reaction, the solvent in the system is carried out solvent exchange, obtain containing the solution that the 15 quality % imidization rates of having an appointment are about 50% polyimide (PI-4) with new N-N-methyl-2-2-pyrrolidone N-.The take a morsel polyimide solution of gained adds the N-N-methyl-2-2-pyrrolidone N-, and forming polyimide concentration is the solution of 10 quality %, and the soltion viscosity of its mensuration is 69mPas.

Synthesizing of＜[B] compound 〉

[embodiment 1]

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

[embodiment 2]

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

The modulation of＜liquid crystal aligning agent 〉

[embodiment 3]

Mix and contain the solution and the solution that contains polyimide (PI-1) of polyamic acid (PA-1) as [A] polymkeric substance, make polyamic acid (PA-1): polyimide (PI-1)=80: 20 (mass ratio), and to wherein adding gamma-butyrolactone, N-N-methyl-2-2-pyrrolidone N-and ethylene glycol-single n-butyl ether, again with respect to the total of 100 mass parts polymkeric substance, convert with wherein contained [B] compound, add 10 mass parts and contain the solution of compound (B-1) as [B] compound, and fully stir, the formation solvent composition is a gamma-butyrolactone: the N-N-methyl-2-2-pyrrolidone N-: ethylene glycol-single n-butyl ether=71: 17: 12 (mass ratio), solid component concentration is the solution of 6.0 quality %.The use aperture is that the strainer of 1 μ m filters 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 the kind and the usage quantity of the compound that makes cooperation, be respectively beyond kind that table 1 puts down in writing and the amount and embodiment 3 operates the modulation liquid crystal aligning agent equally.In addition, the F-1 in the table 1 represents hexa methoxy methylol melamine (サィメ Le C300, MITSUI-CYTEC company).In addition, composition is not used in "-" expression.

[embodiment 8]

To containing polyimide (PI-3) as in the solution of [A] polymkeric substance, add N-N-methyl-2-2-pyrrolidone N-and ethylene glycol-single n-butyl ether, again with respect to the total of 100 mass parts polymkeric substance, convert with wherein contained [B] compound, add 10 mass parts and contain the solution of compound (B-1) as [B] compound, and fully stir, forming solvent composition is the N-N-methyl-2-2-pyrrolidone N-: ethylene glycol-single n-butyl ether=50: 50 (mass ratio), solid component concentration is the solution of 6.0 quality %.The use aperture is that the strainer of 1 μ m filters this solution, the modulation liquid crystal aligning agent.

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

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

The manufacturing of＜liquid crystal display device 〉

Use liquid crystal orientation film printing press (Japan description printing firm), embodiment 3～7 and 1～5 synthetic liquid crystal aligning agent of comparative example are coated on the transparency electrode face that has by the glass substrate of the formed transparency electrode of ITO film, and on 80 ℃ hot plate, heat 1 minute (prebake) except that desolvating, heat 10 minutes (afterwards curing) then on 200 ℃ hot plate, the formation average film thickness is Film.Use has the shredder of the roller of the artificial silk cloth of having reeled, and is 500rpm with the roller rotation number, 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, in ultrapure water, carry out 1 minute ultrasonic washing, 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, coating makes the liquid crystal aligning face relative after having added the epoxy resin adhesive of alumina balls that diameter is 5.5 μ m, carries 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, make liquid crystal cell thus.

Use liquid crystal orientation film printing press (Japan description printing firm), embodiment 8～12 and 6～10 synthetic liquid crystal aligning agent of comparative example are coated on the transparency electrode face that has by the glass substrate of the formed transparency electrode of ITO film, and on 80 ℃ hot plate, heat 1 minute (prebake) except that desolvating, heat 10 minutes (afterwards curing) then on 200 ℃ hot plate, 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, coating makes the liquid crystal aligning face relative after having added the epoxy resin adhesive of alumina balls that diameter is 5.5 μ m, carries 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, make liquid crystal cell thus.

＜estimate

Liquid crystal display device for using synthetic liquid crystal aligning agent manufacturing carries out following evaluation.Result's merging is shown in table 1.

[evaluation of weathering resistance]

For liquid crystal cell, under 70 ℃, apply the voltage of 5V with the application time of 60 microseconds, 167 milliseconds interval after, measure from applying the voltage retention (initial stage voltage retention (VHR that removes after 167 milliseconds by Dongyang テ Network ニ power company " VHR-1 " _IN)).Then, for the liquid crystal cell of having measured the initial stage voltage retention, 5000 hours rayed is carried out in use as the weather resistance test device of light source with carbon arc.For the liquid crystal cell after the rayed, use method same as described above to measure voltage retention (voltage retention (VHR after the rayed once more _AF)).With the sustainment rate of voltage retention is that 90% weathering resistance when above is judged as well, will be judged as bad less than 90% o'clock weathering resistance.

[evaluation of residual DC voltage]

For liquid crystal cell, by the dc voltage value (initial stage dc voltage) in the flicker disappearance method mensuration liquid crystal cell as above-mentioned manufacturing.Then, to this liquid crystal cell, under 100 ℃, apply the voltage of 20 hours direct current 17V.For the liquid crystal cell that applies behind the voltage, after discharging direct supply through 15 minutes after, measure dc voltage value in the liquid crystal cell by flicker disappearance method once more.At this moment, the dc voltage value that applies behind the voltage is deducted the value of initial stage dc voltage value gained as residual DC voltage.Is "+" with the residual DC magnitude of voltage less than the average evaluation of 500mV, is "-" with the average evaluation more than the 500mV.

The result is as can be known clear and definite by table 1, and liquid crystal aligning agent of the present invention can form has kept good electrical characteristic, has good weathering resistance simultaneously, and has suppressed the liquid crystal orientation film that residual DC voltage increases.

Industrial applicibility

According to the present invention, even can provide a kind of can form when carrying out the long-time continuous driving, also can keep good liquid crystal aligning performance and electrical characteristics, have simultaneously good weatherability, and suppressed the manufacture method of aligning agent for liquid crystal, liquid crystal orientation film, the liquid crystal display cells with liquid crystal orientation film, compound and the compound of the liquid crystal orientation film that residual DC voltage increases. Therefore, liquid crystal display cells 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 phone, various display, LCD TV.

Claims

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

In the formula (1), R independently of one another for hydrogen atom, methylol, carbonatoms be 2～7 alkoxy methyl ,-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 had are following formula (2 ^a) represented group, the hindered phenol structure that Z had is following formula (3 ^a) represented group,

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

R ^II～R ^VBe that 1～6 alkyl, carbonatoms are that 6～12 aryl or carbonatoms are 7～13 aralkyl for carbonatoms independently of one another;

X ¹For singly-bound, carbonyl or ^*-CONH-, still, the connecting key that has * is connected with piperidine ring;

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

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

Formula (3 ^a) in, R ^VIIt for carbonatoms 4～16 alkyl; R ^VIIIt for hydrogen atom or carbonatoms 1～16 alkyl; X ⁷For singly-bound ,-CO-, methylene radical or carbonatoms are 2～6 alkylidene group; N is 0～3 integer.

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 the formula (1x), R ^xBe that hydrogen atom, methylol or carbonatoms are 2～7 alkoxy methyl independently of one another, still, at least one R ^xFor methylol or carbonatoms are 2～7 alkoxy methyl,

Y-OH (2)

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

Z-OH (3)

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

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

5. as each described liquid crystal aligning agent of claim 1～3, wherein the usage ratio of [B] compound is 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 each described liquid crystal aligning agent of claim 1～3.

7. the liquid crystal display device that has the described liquid crystal orientation film of claim 6.

8. the represented compound of following formula (1),

9. the manufacture method of the described compound of claim 8, it has the operation that makes the represented compound reaction of represented compound of following formula (1x) and following formula (2) and/or (3),

Y-OH (2)

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

Z-OH (3)

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