CN100569907C - Liquid crystal orientating agent and liquid crystal display device - Google Patents
Liquid crystal orientating agent and liquid crystal display device Download PDFInfo
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- CN100569907C CN100569907C CNB2005100797768A CN200510079776A CN100569907C CN 100569907 C CN100569907 C CN 100569907C CN B2005100797768 A CNB2005100797768 A CN B2005100797768A CN 200510079776 A CN200510079776 A CN 200510079776A CN 100569907 C CN100569907 C CN 100569907C
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Abstract
The invention provides and to realize that vertical orientation, voltage retention are good, even contrast gradient inequality, display defect can not take place when under high humidity environment, placing yet, have the high vertical orientation type liquid crystal display device of reliability and be used for wherein liquid crystal orientating agent.This vertical orientation type liquid crystal orientating agent contains the compound that the intramolecularly of the polyamic acid that is obtained by the reaction of tetracarboxylic dianhydride and diamine compound of 100 weight parts and/or its imide amination polymer and 0.01～100 weight part has 2 or 2 above epoxy group(ing).
Description
Technical field
The present invention relates to liquid crystal orientating agent and liquid crystal display device.In more detail, relate to the liquid crystal orientating agent of the liquid crystal orientating membrane that can realize that vertical orientation, voltage retention and wet fastness are good and have above-mentioned liquid crystal orientating membrane, liquid crystal display device that reliability is high.
Background technology
At present, as liquid crystal display device, known have, be provided with on the substrate surface of nesa coating, the liquid crystal orientating membrane that formation is made up of polyamic acid, polyimide etc., as the used for liquid crystal display element substrate, with its 2 subtend settings, form the layer of nematic liquid crystal betwixt in the crack with positivity dielectric anisotropy, form the liquid crystal cells of sandwich structure, the major axis of liquid crystal molecule is turned round the TN type liquid crystal display device of so-called TN (Twisted Nematic) the type liquid crystal cells that turn 90 degrees continuously towards the opposite side substrate from the substrate of a side.In addition, compare contrast gradient height, STN (Super Twisted Nematic) type liquid crystal display device that view angle dependency is little and vertical orientation type liquid crystal display device with TN type liquid crystal display device also in research and development.This STN type liquid crystal display device uses the nematic liquid crystal of having sneaked into as the chiral reagent of optically active substance as liquid crystal, utilizes the birefringence effect that produces at the state of turning round continuously between substrate more than the turnback by the major axis that forms liquid crystal molecule.
On the other side, proposed to be called the vertical orientation type liquid crystal display device of MVA (Multi domain Vertical Alignment) mode and PVA (Patterned Vertical Alignment) mode.The liquid crystal display device of these MVA modes and PVA mode is good aspect angle of visibility, contrast gradient, can not carry out grinding process in the formation of liquid crystal orientating membrane, also is good aspect manufacturing process.As the liquid crystal orientating membrane that is fit to MVA mode and PVA mode, require to have good vertical orientation.
Again further, recently, as high performance display element, liquid crystal display device has been obtained obvious improvement at aspects such as maximization, lightweight, low consumption electrifications, correspondingly to the desired performance of liquid crystal orientating membrane also increasingly stringent.Particularly for the low voltage drive type liquid crystal display device that turns to purpose with low consumption electric power, to its voltage retention with at high temperature to add the requirement of reliability test of long-time voltage more and more stricter, in addition, also exist in the manufacturing processed to produce directed uneven problem owing to oriented film absorbs airborne moisture, this problem presses for and is resolved.Yet, as the liquid crystal orientating membrane that is fit to MVA mode and PVA mode up to now, for example in the directing agent structure, have epoxy group(ing) in patent documentation 1, the patent documentation 2, can show good vertical orientation and electrology characteristic, but do not solve the problem of moisture absorption.In view of this situation, expectation is developed and a kind ofly can be provided the liquid crystal orientating agent that does not damage the good liquid crystal orientating membrane of voltage retention and electrology characteristic and wet fastness.
[patent documentation 1] spy opens the 2002-323701 communique
[patent documentation 2] spy opens the 2004-94179 communique
Summary of the invention
The object of the present invention is to provide a kind of liquid crystal orientating agent that can realize the liquid crystal orientating membrane that vertical orientation, voltage retention and wet fastness are good.
Another object of the present invention is to provide liquid crystal display device with above-mentioned liquid crystal orientating membrane.
By the following description, can understand further aim of the present invention and advantage.
Among the present invention, above-mentioned purpose of the present invention and advantage the 1st are to contain by it is characterized in that: (A) polyamic acid (hereinafter referred to as " particular polymers I ") that obtains by tetracarboxylic dianhydride and diamine compound reaction of 100 weight parts and/or its imide amination polymer (hereinafter referred to as " particular polymers II ") and
(B) compound of the intramolecularly of 0.01～100 weight part with 2 or 2 above epoxy group(ing) realized.
Among the present invention, above-mentioned purpose of the present invention and advantage the 2nd are by it is characterized in that: the vertical orientation type liquid crystal display device that possesses the liquid crystal orientating membrane that is formed by above-mentioned liquid crystal orientating agent of the present invention is realized.
By liquid crystal orientating agent of the present invention, can be produced on vertical orientation, the voltage retention aspect is good, even and also contrast gradient inequality, display defect can not occur when under high humidity environment, placing, have the vertical orientation type liquid crystal display device of reliability.
Vertical orientation type liquid crystal display device of the present invention can be advantageously used in the various devices, for example can perform well in the display unit such as desk-top computer, wrist-watch, desk-top clock, word processor, PC, LCD TV.
Embodiment
Below explain the present invention.
Polyamic acid and imide amination polymer thereof
Among the present invention, use the polyamic acid and/or its imide amination polymer that obtain by tetracarboxylic dianhydride and diamine compound reaction.
As the tetracarboxylic dianhydride who uses among the present invention, for example can enumerate aliphatics tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic acid's dianhydride.
As the aliphatics tetracarboxylic dianhydride, can enumerate for example butane tetracarboxylic acid dianhydride.
As alicyclic tetracarboxylic dianhydride, for example can enumerate 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 '-bicyclohexane tetracarboxylic dianhydride, suitable-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-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 naphtho-[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)-naphtho-[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)-naphtho-[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 naphtho-[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)-naphtho-[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)-naphtho-[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)-naphtho-[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)-naphtho-[1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofuran (THF))-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid dianhydride, dicyclo [2,2,2]-7-octene-2,3,5, the 6-tetracarboxylic dianhydride, following formula (a) and (b) shown in compound etc.
(in the formula, R
1And R
4Expression has the divalent organic radical of aromatic nucleus, R
2And R
3Expression hydrogen atom or alkyl, a plurality of R
2And R
3Can be identical or different respectively.)
In addition, as aromatic tetracarboxylic acid's dianhydride, for example can enumerate, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3, ' 4,4 '-diphenylsulfone acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-phenyl ether 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) diphenyl sulfide dianhydride, 4,4 '-two (3,4-dicarboxyl phenoxy group) diphenyl sulfone dianhydride, 4,4 '-two (3,4-dicarboxyl phenoxy group) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two O-phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phenylphosphine oxide 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, two (4-hydroxyphenyl) propane-two (dehydration trimellitate) of 2-, aromatic tetracarboxylic acid dianhydrides such as compound shown in following formula (1)～(4) respectively.These can use a kind or make up more than 2 kinds or 2 kinds and to use separately.
From the angle of voltage retention, in these tetracarboxylic dianhydrides, preferred 50 moles of % or 50 moles of % are above to be alicyclic tetracarboxylic dianhydride's polyamic acid and imide amination polymer thereof.As preferred alicyclic tetracarboxylic dianhydride, can enumerate 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, 5-(2,5-dioxo tetrahydrofuran (THF) methylene radical)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid dianhydride, suitable-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[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 naphtho-[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)-naphtho-[1,2-c]-furans-1, the 3-diketone, dicyclo [2,2,2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, compound in the compound shown in compound in the compound shown in the above-mentioned formula (a) shown in following formula (5)～(7) and the above-mentioned formula (b) shown in following formula (8).As particularly preferred, can enumerate 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-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)-naphtho-[1,2-c]-furans-1, the 3-diketone, suitable-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the compound shown in 3-diketone and the following formula (5).
As the diamine compound that uses among the present invention, for example can enumerate, Ursol D, mphenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4,-diamino diphenylethane, 4,4,-diamino diphenyl sulfide, 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formylaniline, 4,4 '-diaminodiphenyl oxide, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] sulfones of 2-, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-the aminophenyl)-10-hydrogenation anthracenes of 9-, 2, the 7-diamino-fluorene, 9, two (4-aminophenyl) fluorenes of 9-, 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, 1,4,4 '-(to the phenylene isopropylidene) dianiline, 4,4 '-(metaphenylene isopropylidene) dianiline, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, aromatic diamines such as 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group)] octafluoro biphenyl;
1,1-m-xylene diamine, 1, the 3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine, heptamethylene diamines, eight methylene diamine, nine methylene diamine, 4,4-diamino heptamethylene diamines, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydro-dicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0
2.7]-undecylene dimethyl diamines, 4,4 '-methylene-bis aliphatics or ester ring type diamines such as (cyclo-hexylamine);
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-diamino pyrazine, 5,6-diamino-2, the 4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazines, 1, two (3-aminopropyl) piperazines of 4-, 2,4-diamino-6-isopropoxy-1,3,5-triazines, 2,4-diamino-6-methoxyl group-1,3, the 5-triazine, 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, 2,4-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) phenyl amine and to have the diamines of the nitrogen-atoms beyond 2 primary aminos and this primary amino in the compound equimolecular shown in the following formula (I)～(II);
(in the formula, R
5Expression is selected from 1 valency organic radical of the ring structure with nitrogen atom of pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the divalent organic radical.)
(in the formula, R
6Expression is selected from the divalent organic radical of the ring structure with nitrogen atom of pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the divalent organic radical, and a plurality of X can be identical or different.)
Single-substituted two amines shown in the following formula (III); Diamino organo-siloxane shown in the following formula (IV);
(in the formula, R
7Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic radical of CO-, R
8Expression has and is selected from steroid structure, trifluoromethyl and the fluorine-based 1 valency organic radical or the alkyl of carbonatoms 6～30.)
(in the formula, R
9The alkyl of expression carbonatoms 1～12, a plurality of R
9Can be identical or different respectively, p is 1～3 integer, q is 1～20 integer.)
Can enumerate the compound shown in following formula (9)～(13) etc.These diamine compounds can use separately or make up more than 2 kinds or 2 kinds and use.
(in the formula, y is 2～12 integer, and z is 1～5 integer.)
Wherein, preferred Ursol D, 4,4 '-diaminodiphenylmethane, 4,4,-diamino diphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl oxide, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 4,4 '-(to the phenylene isopropylidene) dianiline, 4,4 '-(metaphenylene isopropylidene) dianiline, 1, the 4-cyclohexanediamine, 4,4 '-methylene-bis (cyclo-hexylamine), 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, compound shown in above-mentioned formula (9)～(13), 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, compound shown in the following formula (14) in the compound shown in the above-mentioned formula (I), compound shown in the following formula (15) in the compound shown in the above-mentioned formula (II), compound shown in following formula (16)～(21) in the compound shown in the above-mentioned formula (III).
Diamines usage quantity with performance pre-tilt angle composition preferably accounts for 2.5～50 moles of % in all diamines.
The particular polymers I that uses among the present invention obtains by tetracarboxylic dianhydride and diamine compound reaction.This is reflected in the organic solvent, preferably at 0～150 ℃.More preferably under 0～100 ℃ temperature condition, carry out.
As reaction soln, as long as can dissolve for example synthetic polyamic acid, just have no particular limits, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, methyl-sulphoxide, gamma-butyrolactone, tetramethyl-urea, hexamethyl phosphoric triamide etc. are non-proton to be polar solvent; Meta-cresol, phenol series solvents such as xylenol, phenol, halogenated phenol.In addition, the usage quantity of organic solvent (α) is generally, and makes the total amount (β) of tetracarboxylic dianhydride and diamine compound reach the amount of 0.1～30 weight % of the total amount (alpha+beta) of reaction soln.
The usage ratio of tetracarboxylic dianhydride and diamine compound is, with respect to the amino in the 1 equivalent diamine compound, preferably makes tetracarboxylic dianhydride's anhydride group reach 0.2～2 equivalent, more preferably reaches 0.3～1.4 equivalent.
The particular polymers II that uses among the present invention by heat above-mentioned particular polymers I or in the presence of dewatering agent and imidization catalyst imidization obtain.Temperature of reaction when carrying out imidization by heating is preferably 60～200 ℃, more preferably 100～170 ℃.60 ℃ of temperature of reaction less thaies then reaction are made slow progress, if surpass 200 ℃ then the molecular weight of soluble polyimide reduce greatly.In addition, in the presence of dewatering agent and imidization catalyst, during imidization, can in aforementioned organic solvent, carry out.Temperature of reaction is preferably 0～200 ℃, more preferably 60～150 ℃.As dewatering agent, for example can use acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.In addition, as imidization catalyst, can use for example tertiary amines such as pyridine, collidine, lutidine, triethylamine.But be not limited to these.The consumption of dewatering agent is that the repeating unit of relative 1 mole of particular polymers I is 1.6～20 moles.In addition, the consumption of imidization catalyst is with respect to 1 mole of employed dewatering agent, to be preferably 0.5～10 mole.
The value of its logarithm viscosity (η In) separately of particular polymers I that obtains thus and particular polymers II is 0.05～10dl/g preferably, is more preferably 0.05～5dl/g.
The value of the logarithm viscosity among the present invention (η In) is to use the N-N-methyl-2-2-pyrrolidone N-as solvent, is that the solution of 0.5g/100 milliliter carries out viscosimetric analysis at 30 ℃ to concentration, and (I) obtains according to following formula.
In addition, in aforementioned organic solvent, in the scope that the polymkeric substance that generates is not separated out, can be used in combination alcohols, ketone, ester class, ethers, halogenated hydrocarbons and hydro carbons as lean solvent.As the object lesson of this lean solvent, can enumerate for example methyl alcohol, ethanol, Virahol, hexalin, 4-hydroxy-4-methyl-2 pentanone (Pyranton), ethylene glycol, propylene glycol, 1, the alcohols of 4-butyleneglycol, triglycol, ethylene glycol monomethyl ether; Acetone for example, the ketone of methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone; The ester class of ethyl lactate, n-Butyl lactate, methyl acetate, ethyl acetate, butylacetate, methyl methoxy base propionic ester, ethyl ethoxy-c acid esters, oxalic acid diethyl ester, diethyl malonate for example; The ethers of diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, glycol monomethyl isopropyl ether, ethylene glycol mono-n-butyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, tetrahydrofuran (THF) for example; Methylene dichloride, 1 for example, 2-ethylene dichloride, 1,4-dichlorobutane, trichloroethane, chlorobenzene, the halogenated hydrocarbons of adjacent chlorobenzene; Hydro carbons of hexane, heptane, octane, benzene,toluene,xylene etc. for example.
In measuring by FT-IR at 1381cm
-1Neighbouring absorption (absorption of C-N-C flexural vibration=imide bond) and 1503cm
-1Near the peak area ratio of absorption (imide acid bonded absorbs) calculates the imidization rate by following formula.
Imidization rate={ α 1/ (α 1+ α 2) } * 100 (%)
α 1:1,381cm
-1Near absorption peak area
α 2:1,503cm
-1Near absorption peak area
In addition, α 2 for will on 300 ℃ hot-plate, heat 10 minutes film 1 503cm
-1The value of the peak area that near absorption is tried to achieve as 0.
The epoxy compounds that uses among the present invention contains epoxy group(ing) more than 2 at intramolecularly.As this epoxy compounds, preferably has part-structure (i), (ii) or compound (iii).
(wherein, R represents 1 valency organic radical of hydrogen or carbonatoms 1～20, and k represents 1～3,1 expression 1～3, and m represents 1～4, n represents 1～20 integer)
As the compound with part-structure (i), for example can enumerating, phenolic aldehyde is an epoxy compounds.For example the commodity of ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) manufacturing are called EPIKOTE-152, EPIKOTE-154, EPICURE-MP402FPY, EPICURE-YLH129B65 etc.As having part-structure compound (ii), for example can enumerate 1,12,2-four (hydroxyphenyl) ethane type solid epoxy resin, EPIKOTE-1031S etc.As having part-structure compound (iii), for example can enumerate 3, commodity セ ロ キ サ イ De 2021-A, セ ロ キ サ イ De 2021-P by name etc. that 4-oxirane ring hexene methyl-3 ', 4 '-oxirane ring hexene carboxylicesters, ダ イ セ Le chemical industry (strain) are made.These epoxy compoundss can use a kind or make up more than 2 kinds or 2 kinds and to use separately.
In addition, the epoxy compounds of enumerating here mostly is high molecular weight material greatly, but the epoxy compounds that uses among the present invention is not to the molecule quantitative limitation.
Liquid crystal orientating agent of the present invention can advantageously be prepared by for example adding epoxy compounds in the solution that contains particular polymers I and/or particular polymers II.As the solvent that at this moment uses, can enumerate and aforesaid solvent phase solvent together.
The usage ratio of epoxy compounds is, with respect to 100 weight part particular polymers I and/or particular polymers II, is 0.01～100 weight part.
Liquid crystal orientating agent of the present invention contains particular polymers I and/or particular polymers II, for the molecular weight to these particular polymers is realized optimum screening characteristics through the substrate that overregulates, can add monoamine when reaction.
As the monoamine that use this moment, 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 base amine, dodecyl amine, n-tridecane base amine, n-tetradecane base amine, Pentadecane base amine, n-hexadecyl amine, n-heptadecane base amine, Octadecane base amine, NSC 62789 base amine etc.
Liquid crystal orientating agent of the present invention is used for, and the substrate that forms at least one side of liquid crystal cells has the vertical orientation type liquid crystal display device of shape for lugs or pattern form.Above-mentioned shape is as the orientation restriction means of element.As this liquid crystal display device, can enumerate for example liquid crystal display device of MVA mode.The MVA mode is meant as " liquid crystal Vol.3No.2117 (1999) " and special opening as shown in the flat 11-258605 communique, has put down in writing the vertical orientation pattern of projection as directed restriction means.Projection and pattern can form in TFT substrate-side and colored filter side respectively, for example have projection, have pattern etc. in the TFT side in the colored filter side, also can have these two kinds directed restriction means simultaneously.
The liquid crystal display device that uses liquid crystal orientating agent of the present invention to obtain for example can be by following method manufacturing.
(1) seize on both sides by the arms on the one side of substrate at the liquid crystal that is provided with the nesa coating that forms pattern, apply liquid crystal orientating agent of the present invention by for example methods such as rolling method, spin-coating method, print process, then, by the heating applicator surface, formation is filmed.Heating temperature behind the coated with liquid crystal directing agent, is more preferably 120～250 ℃ by preferably 80～300 ℃.In addition, liquid crystal orientating agent of the present invention forms and becomes filming of oriented film by removing organic solvent after coating, carries out dehydration closed-loop by heating again, can form filming of imidization.
Formed thickness of filming is 0.001～1 μ m preferably, preferably 0.005～0.5 μ m.
In order to improve the connectivity between particular polymers I and/or particular polymers II and the substrate, liquid crystal orientating agent of the present invention also can contain the functional silane compound that contains.
In liquid crystal orientating agent of the present invention, in the scope of not damaging target properties,, can contain the functional silane compound that contains from improving fusible angle to substrate surface.As this functional silane compound that contains, can enumerate for example 3-aminopropyl trimethoxysilane, the 3-aminopropyl triethoxysilane, the 2-aminopropyl trimethoxysilane, the 2-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea propyl trimethoxy silicane, 3-urea propyl-triethoxysilicane, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4, the 7-three ammonia decane of mixing, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl triethoxysilane, two (the oxyethylene group)-3-aminopropyl trimethoxysilane of N-, two (the oxyethylene group)-3-aminopropyl triethoxysilanes of N-etc.
(2) as 2 substrates that formed liquid crystal orientating membrane of above-mentioned making, gap subtend configuration (unitary gap) in this 2 plate base clamping, use the periphery of 2 pieces of substrates of sealing agent applying, in the unitary gap of dividing by substrate surface and sealing agent, inject and fill nematic liquid crystal, the sealing filling orifice constitutes liquid crystal cells.Then, at the outside surface of liquid crystal cells, that is,, thereby obtain liquid crystal display device at the another side side applying polaroid of each substrate that constitutes liquid crystal cells.
,, for example can use herein, contain solidifying agent and as Resins, epoxy of the alumina balls of spacer etc. as sealing agent.
As liquid crystal, can enumerate for example nematic liquid crystal and smectic liquid crystal.Preferred especially nematic liquid crystal, for example can use Schiff's base is that liquid crystal, azoxy are that liquid crystal, biphenyl are that liquid crystal, Santosol 360 are that liquid crystal, ester are that liquid crystal, terphenyl are that liquid crystal, cyclohexyl biphenyl hexane are that liquid crystal, pyrimidine are that liquid crystal, diox are that liquid crystal, bicyclooctane are liquid crystal, cube methane series liquid crystal etc.In addition, in these liquid crystal, also can add cholesteric liquid crystal such as cholesterol chlorine, n-nonanoic acid cholesterol ester, carbonic acid cholesterol ester for example or with commercially available chirality agent of trade(brand)name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and use.Can also use oxygen base benzylidene-in the last of the ten Heavenly stems amino-forceful electric power Jie property liquid crystal such as 2-first butyl laurate.
In addition; as the polaroid on the outside surface that is fitted in liquid crystal cells; can enumerate making polyvinyl alcohol extend orientation on one side, with rhodia protective membrane clamp the polarization film that be called H film that absorb iodine and the polaroid that form, perhaps polaroid itself that by H film constitute on one side.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention is not subjected to the restriction of these embodiment.The assessment item and the evaluation method of the liquid crystal orientating agent of preparing in following embodiment and the comparative example are as follows.
(vertical orientation of liquid crystal molecule)
For the vertical orientation of vertical orientation type liquid crystal display device, observe when voltage OFF with exchange 12V (peak is to the peak) under liquid crystal display device, judging in the situation that does not have magnetic anomaly is " well ".
(anti-moisture test of liquid crystal display device)
For the wet fastness of vertical orientation type liquid crystal display device, place it in (90%RH) under room temperature, the high humidity environment, will work as the situation note that magnetic anomaly does not take place when making voltage ONOFF and do good in liquid crystal cells.
(reliability test of liquid crystal display device)
Reliability for liquid crystal orientating agent, be add under 70 ℃ the temperature environment 167 hours exchange (peak is to the peak) overlapping 30Hz that forms, 3.0V square wave by 6.0V direct current, 6.0V after, make voltage OFF, after the image retention cancellation, whether Visual Confirmation does not have deviation, vertical orientation equably.
(voltage retention)
When on liquid crystal display device, adding the voltage of 3V under 40 ℃ the temperature with time that adds of 60 microseconds, 167 milliseconds interval, mensuration is from removing the sustaining voltage behind the 3V impressed voltage to 167 millisecond, the VHR-1 that makes with (strain) Dongyang テ Network ニ カ measures, and obtains voltage retention.At this moment use minus MLC-2038 (manufacturing of Merek company) as liquid crystal.
Synthesis example 1
2.3g 2,3, the Ursol D of 5-tricarboxylic basic ring penta acetate dianhydride, 0.88g and the diamine compound of 1.1g shown in above-mentioned formula (9) are dissolved in the N-N-methyl-2-2-pyrrolidone N-of 16.8g, 60 ℃ of down reactions 5 hours.Then, reaction mixture is injected excessive greatly methyl alcohol, and make the reaction product precipitation.Use methanol wash then, under reduced pressure, obtain 55.6g particular polymers Ia in 40 ℃ of dryings 15 hours.
The particular polymers Ia that obtains in the synthesis example 1 is dissolved in the N-N-methyl-2-2-pyrrolidone N-of 39.0g, adds 0.88g pyridine and 1.13g diacetyl oxide, under 110 ℃, carry out 4 hours imidization.Similarly make the reaction solution precipitation with synthesis example 1 then, obtain the particular polymers IIa of 53.0g intrinsic viscosity 0.63dL/g.The imidization rate of the particular polymers IIa that obtains is as shown in table 1.
Synthesis example 2
Except with 2 of 1.89g, 3, beyond the Ursol D of 5-tricarboxylic basic ring penta acetate dianhydride, 0.55g and the diamine compound of 1.76g shown in above-mentioned formula (9) were dissolved in the N-N-methyl-2-2-pyrrolidone N-of 16.8g, all the other were according to obtaining 55.7g particular polymers Ib with the same method of synthesis example 1.
The particular polymers Ib that obtains in the synthesis example 2 is dissolved in the N-N-methyl-2-2-pyrrolidone N-of 39.0g, adds 0.73g pyridine and 0.95g diacetyl oxide, under 110 ℃, carry out 4 hours imidization.Similarly make the reaction solution precipitation with synthesis example 1 then, obtain the particular polymers IIb of 52.1g intrinsic viscosity 0.5dL/g.
Synthesis example 3
Except with 2 of 2.9g, 3, beyond the Ursol D of 5-tricarboxylic basic ring penta acetate dianhydride, 1.1g and the diamine compound of 0.6g shown in above-mentioned formula (9) were dissolved in the N-N-methyl-2-2-pyrrolidone N-of 16.8g, all the other were according to obtaining 54.1g particular polymers Ic with the same method of synthesis example 1.
In the N-N-methyl-2-2-pyrrolidone N-that particular polymers Ic, 1.32g pyridine, 1.70g diacetyl oxide is dissolved in 39.0g, all the other obtain the particular polymers IIc of 52.5g intrinsic viscosity 0.32dL/g according to similarly carrying out imidization with synthesis example 1.
Synthesis example 4
Except with 2 of 2.9g, 3, beyond the Ursol D of 5-tricarboxylic basic ring penta acetate dianhydride, 1.1g and the diamine compound of 0.6g shown in above-mentioned formula (9) were dissolved in the N-N-methyl-2-2-pyrrolidone N-of 16.8g, all the other were according to obtaining 54.6g particular polymers Id with the same method of synthesis example 1.
In the N-N-methyl-2-2-pyrrolidone N-that particular polymers Id, 1.76g pyridine, 2.27g diacetyl oxide is dissolved in 39.0g, all the other obtain the particular polymers IId of 52.1g intrinsic viscosity 0.48dL/g according to similarly carrying out imidization with synthesis example 1.
Synthesis example 5
Except with 2 of 4.6g, 3, beyond the pyromellitic acid dianhydride of 5-tricarboxylic basic ring penta acetate dianhydride, 1.5g, the Ursol D of 2.2g and the diamine compound of 3.6g shown in above-mentioned formula (9) were dissolved in the N-N-methyl-2-2-pyrrolidone N-of 48.0g, all the other were according to obtaining the particular polymers Ie of 54.0g intrinsic viscosity 0.45dL/g with the same method of synthesis example 1.
[table 1]
| Synthesis example | Polymkeric substance | Intrinsic viscosity dL/g | The imidization rate |
| 1 | IIa | 0.63 | 52％ |
| 2 | IIb | 0.50 | 50％ |
| 3 | IIc | 0.32 | 60％ |
| 4 | IId | 0.48 | 80％ |
| 5 | Ie | 0.45 | 0％ |
Embodiment 1～9 and comparative example 1～5
Embodiment 1
The particular polymers IIa that 3.88g is obtained in synthesis example 1 and be dissolved in the N-N-methyl-2-2-pyrrolidone N-of 0.58g as the エ ピ コ-ト 154 of epoxy compounds, form the solution of solid component concentration 3.5 weight %, strainer with aperture 1 μ m filters this solution, preparation liquid crystal aligning agent solution.On the one side of the glass substrate of thickness 1mm, be provided with by ITO on the film formed nesa coating, with spreadometer coated with liquid crystal directing agent,, 200 ℃ of dryings 1 hour, form dry film thickness 600 then 80 ℃ of dryings 1 minute
Film.
Make 2 substrates that as above form liquid crystal orientating membrane, on the outer edge of each substrate, added the epoxy resin binder of alumina balls by the coating of thick thin,tough silk print process after, will leave with gap configuration relatively in the middle of 2 plate bases, each outer edge of crimping is solidified tackiness agent.Injecting in the unitary gap of being divided by substrate surface and sealing agent and fill nematic liquid crystal, is the adhesive seal filling orifice with epoxy then, makes vertical orientation type liquid crystal display device.
Vertical orientation as the vertical orientation type liquid crystal display device of above-mentioned making is good, shows that voltage retention is 97%, and voltage retention is 89 when not adding additive, can further improve by adding additive.Even when under the high humidity environment of 90%RT, placing in addition, also demonstrate the good result that does not observe the directed inequality that produces owing to moisture absorption.Thereby, can confirm that the liquid crystal display device of making by present embodiment the contrast gradient inequality can not occur good aspect vertical orientation, the voltage retention yet under high humidity.
Embodiment 2～9
According to the proportioning shown in the following table 2, (the particular polymers Ie that obtains in IIb～IId), the synthesis example 5 mixes with epoxy compounds, makes 3.5% solution similarly to Example 1 with the particular polymers II that obtains in the synthesis example 2～4 respectively.At this moment, except using compd A among the embodiment 2～5 as epoxy compounds, use compd B, C respectively among the embodiment 6,7, in embodiment 8,9, use respectively beyond 10 parts, 40 parts the compd A with respect to 100 parts by weight polymer, make liquid crystal cells similarly to Example 1, carry out various evaluations, the result is shown in following table 3.
Comparative example 1～5
According to the proportioning shown in the following table 2, the particular polymers II that obtains in only using synthesis example 1～4 is (the particular polymers Ie that obtains in IIb～IId), the synthesis example 5, make liquid crystal cells similarly to Example 1, carry out various evaluation tests, the result is shown in following table 3.
[table 2]
| Polymkeric substance | Epoxy compounds | Addition | |
| Embodiment 1 | IIa | A | 20 |
| Embodiment 2 | IIb | A | 20 |
| Embodiment 3 | IIc | A | 20 |
| Embodiment 4 | IId | A | 20 |
| Embodiment 5 | IIe | A | 20 |
| Embodiment 6 | IId | B | 20 |
| Embodiment 7 | IId | C | 20 |
| Embodiment 8 | IIa | A | 10 |
| Embodiment 9 | IIa | A | 40 |
| Comparative example 1 | IIa | - | 0 |
| Comparative example 2 | IIb | - | 0 |
| Comparative example 3 | IIc | - | 0 |
| Comparative example 4 | IId | - | 0 |
| Comparative example 5 | IIe | - | 0 |
* addition: additive is with respect to the weight part of 100 parts by weight polymer
A：エピコ-ト154
B：エピコ-ト1031S
C：セロキサイド2021
[table 3]
| The directional property of liquid crystal molecule | Anti-moisture test | Reliability test | Voltage retention (%) | |
| Embodiment 1 | Well | Well | 0.K | 97 |
| Embodiment 2 | Well | Well | 0.K | 97 |
| Embodiment 3 | Well | Well | 0.K | 96 |
| Embodiment 4 | Well | Well | 0.K | 96 |
| Embodiment 5 | Well | Well | 0.K | 96 |
| Embodiment 6 | Well | Well | 0.K | 95 |
| Embodiment 7 | Well | Well | 0.K | 96 |
| Embodiment 8 | Well | Well | 0.K | 96 |
| Embodiment 9 | Well | Well | 0.K | 95 |
| Comparative example 1 | Well | Bad | 0.K | 89 |
| Comparative example 2 | Well | Bad | 0.K | 87 |
| Comparative example 3 | Well | Bad | 0.K | 88 |
| Comparative example 4 | Well | Bad | 0.K | 85 |
| Comparative example 5 | Well | Bad | 0.K | 83 |
Claims (2)
1. vertical orientation type liquid crystal orientating agent, contain:
(A) polyamic acid and/or its imide amination polymer that obtain by the reaction of tetracarboxylic dianhydride and diamine compound of 100 weight parts, and
(B) intramolecularly of 10～40 weight parts has the compound of two above epoxy group(ing),
It is characterized in that at least a part-structure that the compound that described intramolecularly has two above epoxy group(ing) has from following formula (i), select (ii) reaching (iii):
Wherein, n represents 1～20 integer.
2. vertical orientation type liquid crystal display device is characterized in that: possess the liquid crystal orientating membrane that the liquid crystal orientating agent by claim 1 record forms.
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| JP5170372B2 (en) * | 2006-06-02 | 2013-03-27 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| JP5061709B2 (en) * | 2006-06-29 | 2012-10-31 | Ｊｎｃ株式会社 | Composition for liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element |
| JP5120047B2 (en) * | 2007-05-02 | 2013-01-16 | Ｊｓｒ株式会社 | Vertical alignment type liquid crystal aligning agent and liquid crystal display element |
| JP5077583B2 (en) * | 2008-03-26 | 2012-11-21 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| JP5041169B2 (en) * | 2008-09-11 | 2012-10-03 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| TWI392935B (en) | 2009-10-02 | 2013-04-11 | Chi Mei Corp | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN102051185B (en) * | 2009-11-03 | 2013-07-17 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| KR101439496B1 (en) * | 2009-12-22 | 2014-09-12 | 에스케이이노베이션 주식회사 | Polyamic acid composition, method for preparing the same and polyimide metal clad laminate the same |
| US8730437B2 (en) | 2010-04-14 | 2014-05-20 | Chi Mei Corporation | Method for making a treated polymer for a liquid crystal alignment agent, the treated polymer made thereby, and liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element containing the treated polymer |
| JP5668577B2 (en) * | 2010-05-06 | 2015-02-12 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, and polyorganosiloxane compound |
| TWI401252B (en) | 2010-06-22 | 2013-07-11 | Chi Mei Corp | Liquid-crystal alignment formulation, and liquid-crystal aligning film and liquid-crystal display element prepared by using the same |
| TWI427104B (en) | 2010-10-26 | 2014-02-21 | Chi Mei Corp | Liquid crystal alignment agent, liquid crystal alignment film and a liquid crystal display comprising said liquid crystal alignment film |
| TWI448790B (en) | 2011-05-13 | 2014-08-11 | Chi Mei Corp | Liquid crystal alignment film and liguid crystal display element |
| KR101973192B1 (en) * | 2017-06-29 | 2019-04-26 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
| KR102030079B1 (en) | 2017-06-30 | 2019-10-08 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
| KR101994430B1 (en) | 2017-06-30 | 2019-09-24 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
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| JP2002323701A (en) * | 2001-04-25 | 2002-11-08 | Jsr Corp | Homeotropic alignment type liquid crystal aligning agent |
| JP3767419B2 (en) * | 2001-05-28 | 2006-04-19 | ソニー株式会社 | Liquid crystal display element |
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| JP2007121991A (en) * | 2005-09-29 | 2007-05-17 | Sony Corp | Liquid crystal orientated film and liquid crystal display element |
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| US11630350B2 (en) | 2016-06-21 | 2023-04-18 | Lg Chem, Ltd. | Liquid crystal alignment composition, method for preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
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