CN102051185B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element Download PDFInfo
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- CN102051185B CN102051185B CN 200910212066 CN200910212066A CN102051185B CN 102051185 B CN102051185 B CN 102051185B CN 200910212066 CN200910212066 CN 200910212066 CN 200910212066 A CN200910212066 A CN 200910212066A CN 102051185 B CN102051185 B CN 102051185B
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Abstract
The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film formed by the same and a liquid crystal display element containing the liquid crystal alignment film, and particularly provides the liquid crystal alignment agent with no blur image and good voltage holding ratio, the liquid crystal alignment film formed by the same and the liquid crystal display element containing the liquid crystal alignment film. The liquid crystal alignment agent comprises a polymer (A) obtained through the reaction of a tetracarboxylic dianhydride compound and a diamine compound, an epoxy-group-containing compound (B) and an organic solvent (C); the liquid crystal alignment agent is coated on a glass substrate and heated for 15 minutes at a temperature of 220 DEG C to enable the liquid crystal alignment agent to form a hardened film, the hardened film is extracted with acetone at a temperature of 60 DEG C for 72 hours to obtain an extraction liquid; and the epoxy valence of the extraction liquid is set to be O, the parts by weight which the epoxy-group-containing compound (B) accounts for is set to be W on the basis of 100 parts by weight of the solid content in the liquid crystal alignment agent, wherein O and W meet the relation in the specification, i.e. [O/W*10<3>] is less than or equal to 0.55.
Description
Technical field
The present invention relates to a kind of LCD alignment agent and the liquid crystal orienting film that forms thereof, and the liquid crystal display device with this liquid crystal orienting film.Particularly providing a kind of does not have ghost, the good LCD alignment agent of voltage retention, and the liquid crystal orienting film that forms, and the liquid crystal display device with this liquid crystal orienting film.
Background technology
General liquid crystal display device, lie on the substrate surface with nesa coating, use polymkeric substance such as polyamic acid polymer, polyimide polymer as the LCD alignment agent, and with this LCD alignment agent after coating, heating and orientation are handled, form a liquid crystal orienting film, in order to as the used for liquid crystal display element substrate, at last with two substrates that are provided with the orientation face in opposite directions, in both gaps, form liquid crystal layer and get.
General liquid crystal display device is main flow to use nematic (Nematic) liquid crystal display device, in this nematic liquid crystal display element, by the type concrete example of practice as: the LCD alignment direction of (1) one side group plate and the LCD alignment direction of opposite side substrate are twisted nematic (TN, TwistedNematic) the type liquid crystal display device of an angle of 90 degrees degree; The LCD alignment direction of (2) one side group plates and the LCD alignment direction of opposite side substrate are that 180 degree are with STN Super TN (STN, Super Twisted Nematic) the type liquid crystal display device of upper angle; (3) use thin-film electro crystal (TFT, Thin Film Transistor) type liquid crystal display device.
Yet, above-mentioned existing liquid crystal orienting film wear resistant (rubbing) is not good, and then cause the stability of tilt angle (pretilt) angle poor, therefore for promoting the wear resistant of alignment film, can in the orientation agent, add and contain epoxy compounds, disclose as openly speciallyying permit communique for Japanese kokai publication hei 07-234410 number, with the compound that has 2 above epoxy group(ing) in a part as LCD alignment agent additive.Yet these contain in the alignment film of epoxy compounds after the back is roasting, easily remained unreacted contain epoxy compounds, cause the ghost problem.
Summary of the invention
The object of the present invention is to provide does not a kind ofly have ghost, the good LCD alignment agent of voltage retention, and the liquid crystal orienting film that forms, and the liquid crystal display device with this liquid crystal orienting film.
This LCD alignment agent comprises: the polymkeric substance (A) that tetracarboxylic dianhydride's compound and diamine compound reaction obtain, the compound (B) that contains epoxy group(ing), and organic solvent (C); Wherein, this LCD alignment agent is coated on the glass substrate, with 220 ℃ of heating 15 minutes, made this LCD alignment agent form a cured film, this cured film is extracted down in 60 ℃ with acetone obtained extraction liquid in 72 hours; The epoxy valency that makes this extraction liquid is O, and based on LCD alignment agent solid 100 weight parts, making this contain the shared weight part of epoxy compounds (B) is W, and this O and W meet following relationship:
[O÷W×10
3]≤0.55
Following formula [O ÷ W * 10
3] be not 0.
Below one by one each composition of the present invention is described in detail:
In the LCD alignment agent of the present invention, by the reaction of tetracarboxylic dianhydride's compound and diamine compound polymkeric substance (A) to comprise polyamic acid polymer (A-1) and/or polyimide polymer (A-2) and/or polyimide be block copolymer (A-3); Wherein, this polyimide is that block copolymer (A-3) comprises polyamic acid block copolymer (A-3-1) and/or polyimide block copolymer (A-3-2) and/or polyamic acid-polyimide block copolymer (A-3-3).
[tetracarboxylic dianhydride's compound]
Tetracarboxylic dianhydride's compound used in the present invention such as aliphatics tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic acid's dianhydride etc.
Aliphatics tetracarboxylic dianhydride's concrete example such as ethane tetracarboxylic dianhydride, butane tetracarboxylic acid dianhydride etc.
Alicyclic tetracarboxylic dianhydride's concrete example is as 1,2, and 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, suitable-3,7-dibutyl suberyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic dianhydride, 3,4-dicarboxyl-1,2,3,4-naphthane-1-succsinic acid dianhydride, 1,3,3a, 4,5,9b-, six hydrogen-5-(tetrahydrochysene-2,5-two side oxygen base-3-furyls)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-two side oxygen base-3-furyls)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-two side oxygen base-3-furyls)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-two side oxygen base-3-furyls)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-two side oxygen base-3-furyls)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-two side oxygen base-3-furyls)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-two side oxygen base-3-furyls)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-, six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-two side oxygen base-3-furyls)-naphtho-[1,2-c]-furans-1, the 3-diketone, 5-(2,5-, two side oxygen base tetrahydrofuran bases)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid dianhydride, two ring [2.2.2]-Xin-7-alkene-2,3,5,6-tetracarboxylic dianhydride and following constitutional formula (I-1) and (I-2) shown in compound:
(in the following formula, R
1And R
3For containing the divalent organic radical of aromatic nucleus, R
2And R
4Be hydrogen atom or alkyl, the R that exists with plural number
2And R
4Can be identical or different respectively.)
The concrete example of aromatic tetracarboxylic acid's dianhydride such as pyromellitic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 '-4,4 '-diphenylethane 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 (3,4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3,4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two phthalic acid dianhydrides, 3,3 ', 4,4 '-phenylbenzene tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide compound dianhydride, p-stretches phenyl-two (triphenylbenzene diacid) dianhydride, m-stretches phenyl-two (triphenylbenzene diacid) dianhydride, two (triphenylbenzene diacid)-4,4 '-diphenyl ether dianhydride, two (triphenylbenzene diacid)-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), compounds such as aromatic tetracarboxylic acid's dianhydride class shown in two (4-hydroxyphenyl) propane-two (dehydration trimellitate) of 2,2-and following constitutional formula (1)～(4).These tetracarboxylic dianhydride's compounds tetracarboxylic dianhydride can independent a kind of use or the use of mixing plural number kind.
In above-mentioned tetracarboxylic dianhydride's compound, with 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 3,4-dicarboxyl-1,2,3,4-naphthane-1-succsinic acid dianhydride, shown in the previous constructions formula (I-1) in the compound shown in following constitutional formula (5)～(7) compound, shown in the previous constructions formula (I-2) in the compound shown in following constitutional formula (8) compound, pyromellitic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, and 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride is preferable.
[diamine compound]
The diamine compound of diamine compound used in the present invention such as aliphatics or alicyclic diamine compound, aromatic series or other diamine compounds etc.
The concrete example of aliphatics or alicyclic diamine compound is as 1,3-two amido propane, 1,4-two amido butane, 1,5-two amido pentanes, 1,6-two amido hexanes, 1,7-diamines base heptane, 1,8-two amido octanes, 1,9-two amido nonanes, 4,4-two amido heptamethylene diamines, 1,4-diamines basic ring hexane, isophorone diamine, tetrahydrochysene Dicyclopentadiene (DCPD) diamines, six hydrogen-4,7-first bridge are stretched hydrogen indenyl dimethylene diamines, three ring [6.2.1.0
2,7]-undecylene dimethyl diamines, 4,4 '-methylene-bis (cyclo-hexylamine).
The concrete example of aromatic diamine compound such as p-phenylenediamine, between-phenylenediamine, ortho-phenylene diamine, 4,4 '-two amido ditans, 4,4 '-two amido diphenylethanes, 4,4 '-two amido diphenylsulfide, 4,4 '-two amido sulfobenzides, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-two amido benzanilides, 4,4 '-two amido diphenyl ethers, 1,5-two amido naphthalenes, 2,2 '-dimethyl-4,4 '-benzidine, 5-amido-1-(4 '-aminocarbonyl phenyl)-1,3,3-trimethylammonium hydrogen indenes, 6-amido-1-(4 '-aminocarbonyl phenyl)-1,3,3-trimethylammonium hydrogen indenes, 3,4 '-two amido diphenyl ethers, 3,3 '-two amido benzophenone, 3,4 '-two amido benzophenone, 4,4 '-two amido benzophenone, 2, two [4-(the 4-amido phenoxy group) phenyl] propane of 2-, 2, two [4-(the 4-amido phenoxy group) phenyl] HFC-236fa of 2-, 2, two (4-aminocarbonyl phenyl) HFC-236fa of 2-, 2, two [4-(the 4-amido phenoxy group) phenyl] sulfones of 2-, 1, two (the 4-amido phenoxy group) benzene of 4-, 1, two (the 4-amido phenoxy group) benzene of 3-, 1, two (the 3-amido phenoxy group) benzene of 3-, 9, two (4-the aminocarbonyl phenyl)-10-hydrogen anthracenes of 9-, 2,7-, two amido Fluorene, two (4-aminocarbonyl phenyl) Fluorene of 9,9-, 4,4 '-methylene radical-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-, 4,4 '-two amidos-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-(right-stretch phenyl isopropylidene) dianiline, 4,4 '-(-stretch phenyl isopropylidene) dianiline, 2,2 '-two [4-(4-amido-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-two amidos-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amido-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl.
The concrete example of other diamine compounds is as 2, the 3-diamino pyridine, 2, the 6-diamino pyridine, 3,4-diamino pyridine, 2,4-, two amine pyrimidines, 5,6-two amidos-2,3-dicyano pyrazine, 5,6-, two amidos-2, the 4-dihydroxy-pyrimidine, 2,4-two amidos-6-dimethyl amido-1,3,5-triazine, two (3-aminocarbonyl propyl) piperazines of 1,4-, 2,4-two amidos-6-isopropoxy-1,3,5-triazine, 2,4-, two amidos-6-methoxyl group-1,3, the 5-triazine, 2,4-, two amidos-6-phenyl-1,3, the 5-triazine, 2,4-two amidos-6-methyl-s-triazine, 2,4-, two amidos-1,3, the 5-triazine, 4,6-two amidos-2-vinyl-s-triazine, 2,4-, two amidos-5-phenyl thiazole, 2,6-, two amido purine, 5,6-two amidos-1, the 3-dimethyl uracil, 3,5-, two amidos-1,2, the 4-triazole, 6,9-two amidos-2-oxyethyl group acridine lactate, 3,8-, two amidos-6-phenyl coffee pyridine, 1,4-, two amido piperazines, 3,6-two amido acridines, compound shown in two (4-aminocarbonyl phenyl) phenyl amine and following constitutional formula (II-1) reach (II-2), namely intramolecularly contains two amines of two one-level amidos and this one-level amido nitrogen-atoms in addition etc.
(in the following formula, R
5Be any monovalent organic radical of the nitrogen atom ring texture that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, X is the organic radical of divalence.)
(in the following formula, R
6Be the divalent organic base of the nitrogen atom ring texture that is selected from pyridine, pyrimidine, triazine, piperidines and piperazine, X is the organic radical of divalence, with the X that plural number exists, can be identical or different.) and following constitutional formula (II-3)～(II-5) shown in compound,
(in the following formula, R
7For be selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-divalent organic base of CO-, R
8To contain steroid class (steroid) skeleton, trifluoromethyl and fluorine-based any monovalent organic radical or carbonatoms be 6～30 alkyl in order to be selected from.)
(in the following formula, R
9For be selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-divalent organic base of CO-, X
1And X
2For being selected from aliphatics ring, aromatic ring and heterocycle, R
10Be that 3～18 alkyl, carbonatoms are that 3～18 alkoxyl group, carbonatoms are that 1～5 fluoroalkyl, carbonatoms are 1～5 Fluoroalkyloxy, cyano group and halogen atom for being selected from carbonatoms.)
(in the following formula, R
11For carbonatoms is 1～12 alkyl, the R that exists with plural number
11Can be identically or different, p is 1～3 integer, and q is 1～20 integer.)
And the compound shown in following constitutional formula (9)～(13) etc., these diamine compounds can be used alone or mixing plural kinds of use.
(in the following formula, t is 2～12 integer, and u is 1～5 integer.)
In the above-mentioned diamino compound, with p-phenylenediamine, 4,4 '-two amido ditans, 4,4 '-two amido diphenylsulfide, 1,5-two amido naphthalenes, 2,7-two amido Fluorene, 4,4 '-two amido diphenyl ethers, 2, two [4-(the 4-amido phenoxy group) phenyl] propane of 2-, 9, two (4-aminocarbonyl phenyl) Fluorene of 9-, 2, two [4-(the 4-amido phenoxy group) phenyl] HFC-236fa of 2-, 2, two (4-aminocarbonyl phenyl) HFC-236fa of 2-, 4,4 '-(right-stretch phenyl isopropylidene) dianiline, 4,4 '-(-stretch phenyl isopropylidene) dianiline, 1,4-diamines basic ring hexane, 4,4 '-methylene-bis (cyclo-hexylamine), 1, two (the 4-amido phenoxy group) benzene of 4-, 4,4 '-two (4-amido phenoxy group) biphenyl, 2, the 6-diamino pyridine, 3, the 4-diamino pyridine, 2,4-two amine pyrimidines, 3,6-two amido acridines, compound shown in above-mentioned constitutional formula (9)～(13), shown in the above-mentioned constitutional formula (II-1) in the compound shown in following constitutional formula (14) compound, shown in the above-mentioned constitutional formula (II-2) in the compound shown in following constitutional formula (15) compound, shown in the above-mentioned constitutional formula (II-3) in the compound shown in following constitutional formula (16)～(24) compound, shown in the above-mentioned constitutional formula (II-4) in the compound shown in following constitutional formula (25)～(27) compound, and the liquid crystal liquid crystal property diamino compound is preferable shown in following constitutional formula (28)～(39).
(in the following formula, v is 3～12 integer.)
[polyamic acid polymer A-1's is synthetic]
In the polymkeric substance of the present invention, polyamic acid polymer (A-1) is to be got through polycondensation reaction by tetracarboxylic dianhydride's compound and diamino compound.Wherein, the usage ratio of tetracarboxylic dianhydride's compound and diamino compound, for amido 1 equivalent of diamino compound, the anhydride group of tetracarboxylic dianhydride's compound is generally 0.2～2 equivalent, is preferably 0.3～1.2 equivalent.
In the polycondensation reaction of polyamic acid polymer (A-1), tetracarboxylic dianhydride's compound and the diamino compound temperature of reaction in organic solvent is generally-20～150 ℃, is preferably 0～100 ℃.Wherein, organic solvent is if solubilized reactant and resultant namely are not particularly limited.The concrete example of organic solvent is as N-N-methyl-2-2-pyrrolidone N-, N, N-N,N-DIMETHYLACETAMIDE, N, the non-proton of dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, 4-methyl urea, hexamethylphosphoric acid triamide etc. is polar solvent, and between-the phenol series solvent of cresols, xylenol, phenol, halogenation phenols etc.
In the above-mentioned organic solvent, in the scope that the polymkeric substance that generates is not separated out, can and with an amount of lean solvent as alcohols, ketone, ester class, ethers, halogenated hydrocarbons, hydro carbons etc.The concrete example of lean solvent is as methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, triethylene glycol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, oxalic acid diethyl ester, diethyl malonate, Anaesthetie Ether, Ethylene Glycol Methyl ether, glycol ethyl ether, the ethylene glycol n-propyl ether, the ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, the glycol ethyl ether acetic ester, diethylene glycol dimethyl ether, tetrahydrofuran (THF), methylene dichloride, 1, the 2-ethylene dichloride, 1,4-dichlorobutane, trichloroethane, chlorobenzene, neighbour-dichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene etc.
The polyamic acid polymer of above-mentioned gained (A-1) reaction soln is poured in a large amount of lean solvents, and the precipitate of gained is via drying under reduced pressure, this precipitate or with vaporizer with the reaction soln underpressure distillation, can get polyamic acid polymer (A-1).In addition, this polyamic acid polymer (A-1) is dissolved in the organic solvent again, with lean solvent it is separated out then, or with the vaporizer underpressure distillation, via repeating once or for several times above-mentioned operation the polyamic acid polymer that can make with extra care (A-1).
[polyimide polymer A-2's is synthetic]
Polyimide polymer of the present invention (A-2) is that the further dehydration closed-loop (imidization) of polyamic acid polymer (A-1) is handled and got.
The imidization treatment process of polyamic acid polymer (A-1) is for example: polyamic acid polymer (A-1) is dissolved in the organic solvent, and in the presence of dewatering agent and imidization catalyst, the dehydration closed-loop reaction is carried out in heating.The Heating temperature that imidization is handled is generally 40～200 ℃, is preferably 80～150 ℃.
If the temperature of reaction that imidization is handled is when being lower than 40 ℃, and the dehydration closed-loop reaction can't be carried out fully; If temperature of reaction is when surpassing 200 ℃, and the molecular weight of gained polyimide polymer (A-2) reduces.
On the other hand, in above-mentioned polyamic acid polymer (A-1) solution, the concrete example of the dewatering agent that uses as: anhydrides compounds such as acetic anhydride, propionic anhydride, trifluoro-acetic anhydride, based on 1 mole of polyamic acid polymer (A-1), the usage quantity of dewatering agent is good with 0.01～20 mole.And the concrete example of employed imidization catalyst as: tertiary amines such as pyridine, trimethylpyridine, lutidine, triethylamine, based on 1 mole of dewatering agent, the usage quantity of imidization catalyst is good with 0.5～10 mole.Employed solvent phase does not repeat them here together in the concrete example of the imidization processing solvent that uses and the polycondensation reaction of aforementioned polyamic acid polymer (A-1).In addition, for the reaction soln of gained like this, by with the process for purification of polyamic acid polymer in the identical operations mode, can make with extra care polyimide polymer (A-2).
[polyimide is the synthetic of block copolymer (A-3)]
In the LCD alignment agent constituent of the present invention, polyimide is that block copolymer (A-3) comprises polyamic acid block copolymer (A-3-1) and/or polyimide block copolymer (A-3-2) and/or polyamic acid-polyimide block copolymer (A-3-3).Be in the building-up reactions of block copolymer (A-3) in polyimide, will be selected from aforementioned polyamic acid polymer (A-1), polyimide polymer (A-2), tetracarboxylic dianhydride's compound, diamino compound further polycondensation reaction and getting in organic solvent.For example: 2 kinds of terminal group are different and construct different polyamic acid polymer (A-1); 2 kinds of terminal group are different and construct different polyimide polymer (A-2); Terminal group is different and construct different polyamic acid polymer (A-1) and polyimide polymer (A-2); Polyamic acid polymer (A-1) and tetracarboxylic dianhydride's compound and diamino compound, wherein tetracarboxylic dianhydride's compound and diamino compound at least a when polyamic acid polymer (A-1) condensation reaction employed tetracarboxylic dianhydride's compound and diamino compound structure different; Polyimide polymer (A-2) and tetracarboxylic dianhydride's compound and diamino compound, wherein tetracarboxylic dianhydride's compound and diamino compound at least a when polyimide polymer (A-2) condensation reaction employed tetracarboxylic dianhydride's compound and diamino compound structure different; Polyamic acid polymer (A-1) and polyimide polymer (A-2) and tetracarboxylic dianhydride's compound and diamino compound, wherein tetracarboxylic dianhydride's compound and diamino compound at least a during with polyamic acid polymer (A-1) and polyimide polymer (A-2) condensation reaction employed tetracarboxylic dianhydride's compound and diamino compound structure different; 2 kinds of polyamic acid polymer (A-1) and tetracarboxylic dianhydride's compound and diamino compounds that structure is different; 2 kinds of polyimide polymer (A-2) and tetracarboxylic dianhydride's compound and diamino compounds that structure is different; 2 kinds of terminal group are anhydride group and construct different polyamic acid polymer (A-1) and diamino compound; 2 kinds of terminal group are amido and construct different polyamic acid polymer (A-1) and tetracarboxylic dianhydride's compound; 2 kinds of terminal group are anhydride group and construct different polyimide polymer (A-2) and diamino compound; 2 kinds of terminal group are amido and construct different polyimide polymer (A-2) and tetracarboxylic dianhydride's compound etc.
Polyimide is in the polycondensation reaction of block copolymer (A-3), and temperature of reaction is generally 0～200 ℃, is preferably 0～100 ℃.In the polycondensation reaction of the concrete example of the solvent that uses and aforementioned polyamic acid polymer (A-1) the solvent phase that uses with, do not repeat them here.
In addition, the polyimide that reaction obtains is that block copolymer (A-3) reaction soln can be as the operation of aforementioned polyamic acid polymer (A-1) process for purification, and the polyimide that further processing can be made with extra care is block copolymer (A-3).
[end is repaiied Ornaments type polymkeric substance]
Used polyamic acid polymer and polyimide polymer among the present invention also can be to have carried out the end modified type polymkeric substance after the molecular-weight adjusting.By using end modified type polymkeric substance, can under the prerequisite of the effect of the present invention that do not detract, improve the character such as coating characteristics of LCD alignment agent.The manufacture of this type of end modified type polymkeric substance can be by when the building-up reactions of polyamic acid polymer, for example adds simple function compound such as monobasic acid anhydrides, monoamine compound, monoisocyanates compound and synthesize in reaction system.Wherein, monobasic acid anhydrides concrete example is as: maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.Monoamine compound concrete example such as aniline, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, Pentadecane amine, n-hexadecane amine, n-heptadecane amine, Octadecane amine, NSC 62789 amine etc.Monoisocyanates compound concrete example such as phenylcarbimide, isocyanic acid naphthyl ester etc.
[compound (B) that contains epoxy group(ing)]
Based on LCD alignment agent solid 100 weight parts, the shared weight part of compound (B) that contains epoxy group(ing) among the present invention is generally 0.1～45 weight part, is preferably 1～40 weight part, is more preferred from 2～35 weight parts.When containing the shared weight part of epoxy compounds (B) and be lower than 0.1 weight part, then formed liquid crystal orienting film voltage retention reduces, takes place easily ghost; When containing the shared weight part of epoxy compounds (B) and be higher than 45 weight parts, then the thermotolerance of formed liquid crystal orienting film reduces.
Of the present invention contain that epoxy compounds (B) comprises tool polycyclic aliphatic structure contain epoxy compounds (B-1), its concrete example is as the bicyclic oxygen compound of Dicyclopentadiene (DCPD) epoxide (Dicyclopentadienediepoxide), three cyclopentadiene epoxide (Tricyclopentadiene diepoxide), Fourth Ring pentadiene epoxide (Tetracyclopentadiene diepoxide), five rings pentadiene epoxide polycyclic aliphatic structures such as (Pentacyclopentadiene diepoxide).Wherein, preferable with Dicyclopentadiene (DCPD) epoxide, three cyclopentadiene epoxide, be more preferred from the Dicyclopentadiene (DCPD) epoxide.
The compound (B) that contains epoxy group(ing) of the present invention except above-claimed cpd (B-1), requires in the purpose rerum natura scope not detracting, and can optionally further add other and contain epoxy compounds (B-2).
Other compound (B-2) concrete examples that contain epoxy group(ing) are as the ethylene glycol bisthioglycolate glycidyl ethers, polyoxyethylene glycol diepoxy propyl ether, propylene glycol diepoxy propyl ether, tripropylene glycol diepoxy propyl ether, polypropylene glycol diepoxy propyl ether, neopentyl glycol diepoxy propyl ether, 1,6-hexylene glycol diepoxy propyl ether, glycerol diepoxy propyl ether, 2,2-dibromoneopentyl glycol diepoxy propyl ether, 1,3,5,6-Fourth Ring oxygen propyl group-2, the 4-hexylene glycol, N, N, N ', N '-Fourth Ring oxygen propyl group-m-xylenedimaine, two (the N of 1,3-, N-diepoxy propyl group aminomethyl) hexanaphthene, N, N, N ', N '-Fourth Ring oxygen propyl group-4,4 '-two amido ditans, 3-(N-allyl group-N-epoxypropyl) aminocarbonyl propyl Trimethoxy silane, 3-(N, N-diepoxy propyl group) aminocarbonyl propyl Trimethoxy silane etc.
In addition, LCD alignment agent of the present invention requires in the purpose rerum natura scope not detracting, and can add to contain the functional silanes compound, in order to improve the adherence to substrate surface.These concrete examples that contain the functional silanes compound are as 3-aminocarbonyl propyl Trimethoxy silane, 3-aminocarbonyl propyl triethoxyl silane, 2-aminocarbonyl propyl Trimethoxy silane, 2-aminocarbonyl propyl triethoxyl silane, N-(2-amido ethyl)-3-aminocarbonyl propyl Trimethoxy silane, N-(2-amido ethyl)-3-aminocarbonyl propyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane (3-ureidopropyltrimethoxysilane), 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-aminocarbonyl propyl Trimethoxy silane, N-ethoxy carbonyl-3-aminocarbonyl propyl triethoxyl silane, N-tri-ethoxy silylpropyl three is stretched the second triamine, N-Trimethoxy silane base propyl group three is stretched the second triamine, 10-Trimethoxy silane base-1,4,7-three a word used for translation decane, 10-triethoxysilicane alkyl-1,4,7-three a word used for translation decane, 9-Trimethoxy silane base-3,6-two a word used for translation nonyl acetic esters, 9-triethoxysilicane alkyl-3,6-two a word used for translation nonyl acetic esters, N-phenmethyl-3-aminocarbonyl propyl Trimethoxy silane, N-phenmethyl-3-aminocarbonyl propyl triethoxyl silane, N-phenyl-3-aminocarbonyl propyl Trimethoxy silane, N-phenyl-3-aminocarbonyl propyl triethoxyl silane, two (the ethylene oxide)-3-aminocarbonyl propyl Trimethoxy silanes of N-, two (the ethylene oxide)-3-aminocarbonyl propyl triethoxyl silanes of N-etc.
[organic solvent (C)]
Can be used as the organic solvent (C) of LCD alignment agent of the present invention, 1-Methyl-2-Pyrrolidone for example, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, the glycol monomethyl methyl ether, n-Butyl lactate, butylacetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, Ethylene Glycol Methyl ether, glycol ethyl ether, the ethylene glycol n-propyl ether, the ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diglycol monotertiary methyl ether, carbiphene, the glycol ether monomethyl ether acetate, diethylene glycol monoethyl ether acetate etc.
[LCD alignment Elixirs]
LCD alignment agent of the present invention generally is with polymkeric substance (A), contains epoxy compounds (B), and other additives are dissolved in the organic solvent (C) and combine.
The refining temperature of LCD alignment agent of the present invention is preferably 0～200 ℃ for good, is more preferred from 20～60 ℃.
Solid concentration in the LCD alignment agent of the present invention is according to character such as viscosity, volatility and adjusted.Be generally 1～15 weight %, be preferably 2～15 weight %, be more preferred from 3～15 weight %.That is, substrate surface is coated in LCD alignment agent of the present invention, when forming liquid crystal orienting film and filming, when solid content in the LCD alignment agent during between 1～15 weight %, then the coating characteristics of LCD alignment agent is preferable.
LCD alignment agent of the present invention is coated on the glass substrate, with 220 ℃ of heating 15 minutes, make this LCD alignment agent form a cured film, this cured film was obtained extraction liquid in 72 hours with acetone extraction under 60 ℃, the epoxy valency that makes this extraction liquid is O, and based on LCD alignment agent solid 100 weight parts, making this contain the shared weight part of epoxy compounds (B) is W, meets following relationship:
[O÷W×10
3]≤0.55
Above-mentioned relation formula [O ÷ W * 10
3] numerical value be preferably≤0.50; Be more preferred from≤0.45.If this relational expression [O ÷ W * 10
3] numerical value＞0.55, then the voltage retention of the liquid crystal orienting film that is formed is low, and problems such as ghost take place easily.
[formation of liquid crystal orienting film]
Being provided with on the substrate one side of nesa coating, LCD alignment agent of the present invention is coated on the substrate with roller coating method, method of spin coating, print process, ink jet method methods such as (ink-jet), its formation is filmed the coated face heating then.
The aforesaid base plate concrete example is as the plastic transparent substrate that is used for the glass of non-alkali glass, soda-lime glass, hard glass (Pai Lesi glass), silica glass etc. of liquid crystal indicator etc. or polyethylene terephthalate, polybutylene terepthatlate, polyethersulfone, polycarbonate etc.Substrate is simultaneously gone up set nesa coating and can be used by stannic oxide (SnO
2) constitute
Film (
The registered trademark that has for U.S. PPG company), by Indium sesquioxide-stannic oxide (In
2O
3-SnO
2) the ITO film that constitutes etc.
When coating of liquid crystalline orientation agent, improve for making the intermembranous adherence of substrate surface and electrically conducting transparent, can on the surface of substrate, coating in advance contain the functional silanes compound, contain the functionality titanium compound.
The heat treated of formation alignment film comprises the heat treated in advance (pre-bake) after the LCD alignment agent coating, and post-heating is handled (post-bake), heat treated can make organic solvent volatilize to form alignment film and be coated with rete in advance, and the heat treated temperature is generally 30～120 ℃, is preferably 40～110 ℃, is more preferred from 50～100 ℃ in advance.
In addition, after this orientation agent formation alignment film is coated with rete, further carries out post-heating again and handle, can carry out dehydration closed-loop (imidization) reaction formation imidization alignment film and be coated with rete.The post-heating treatment temp is generally 150～300 ℃, is preferably 180～280 ℃, is more preferred from 200～250 ℃.
The thickness that the alignment film that forms is coated with rete is preferably 0.001～1 μ m, is more preferred from 0.005～0.5 μ m.
Formed alignment film is coated with rete, the cloth of making according to fibers such as needing available nylon, artificial silk, cotton class is wrapped on the cylinder, carry out orientation with certain orientation friction and handle, make the orientation of liquid crystal molecule can give being coated with and constitute liquid crystal orienting film on the rete.In addition, the adding method of the orientation energy of liquid crystal molecule, reach as forming shape for lugs (protrusion) or formation pattern form at least one plate base that forms alignment film, this method is celebrated with MVA (Multi-domain Vertical Alignment) or PVA (Patterned Vertical Alignment).
[liquid crystal display device]
Produce 2 with the above-mentioned substrate that is formed liquid crystal orienting film, (structure cell at interval to get involved the gap between 2 plate bases, cell gap) does the subtend configuration, around 2 plate bases fit with sealing agent in the position, liquid crystal is injected in filling in the gap that substrate surface and sealing agent are distinguished, and seals filling orifice and constitutes liquid crystal structure cell (cell).Then, at the outside surface of liquid crystal structure cell, that is constitute on other sides of each substrate of liquid crystal structure cell applying Polarizer and make liquid crystal display device.
The sealing agent material can use general epoxy resin stiffening agent, and interval body (spacer) material can use granulated glass sphere, plastic cement pearl, or photosensitivity Resins, epoxy etc.Liquid crystal for example as: nematic liquid crystal, concrete example as: Schiff's base (Shiff Base) is that liquid crystal, azoxy (Azoxy) are that liquid crystal, biphenyl (Biphenyl) are that liquid crystal, Santosol 360 (Phenylcyclohexane) are that liquid crystal, ester (Ester) are that liquid crystal, terphenyl (Terphenyl) are that liquid crystal, cyclohexyl biphenyl hexane (Biphenylcyclohexane) are that liquid crystal, pyrimidine (pyrimidine) are that liquid crystal, dioxan (Dioxane) are that liquid crystal, bicyclooctane (Bicyclooctane) are that liquid crystal, cubane (Cubane) are liquid crystal etc.In the above-mentioned liquid crystal, can add and use as the cholesterol liquid crystal of cholesteryl chloride (Cholesteryl Chloride), Cholesteryl pelargonate (Cholesteryl Nonanoate), cholesterol carbonic ether (CholesterylCarbonate) etc., and with commodity " C-15 ", " CB-15 " (Merck ﹠ Co., Inc.'s manufacturing) quilt by name sold to slapping (chiral) agent etc.In addition; the Polarizer of fitting on the outside surface of liquid crystal structure cell; for example: polyvinyl alcohol is extended the light polarizing film that makes it absorb iodine when orientation is handled and be known as the H film, with the cellulose acetate protective membrane with its Polarizer of clamping or the formed Polarizer of H film itself etc.
Embodiment
Below, carry out more specific description via the present invention of embodiment, but the present invention is not limited to these embodiment.In following examples and comparative example, in accordance with the following methods LCD alignment agent and the liquid crystal display device modulated are estimated.
Synthesis example 1
Four cervical vertebra bottles 500 milliliters of volumes arrange nitrogen inlet, agitator, well heater, prolong and thermometer, and importing nitrogen, adding the feed composition thing comprises: compound (hereinafter to be referred as the VEDA) 2.82g (0.005mole) shown in the constitutional formula (22), p-phenylenediamine (hereinafter to be referred as PDA) 4.87g (0.045mole), and organic solvent N-methyl pyrrole junket alkane ketone (hereinafter to be referred as NMP) 80g, under room temperature, be stirred to dissolving.Add pyromellitic dianhydride (hereinafter to be referred as PMDA) 10.91g (0.05mole) and NMP 20g again, reaction is 2 hours under room temperature, after reaction finishes, polyamic acid polymer solution poured in the 1500ml water polymkeric substance is separated out, the polymkeric substance of filtration gained repeats with washed with methanol and filters three times, insert in the vacuum drying oven, carry out drying with 60 ℃ of temperature after, get final product polyamic acid polymer (A-1-1).
Synthesis example 2
Four cervical vertebra bottles 500 milliliters of volumes arrange nitrogen inlet, agitator, well heater, prolong and thermometer, and importing nitrogen, adding the feed composition thing comprises: VEDA 2.82g (0.005mole), 4,4 '-two amido ditan (hereinafter to be referred as DDM) 8.92g (0.045mole), and organic solvent NMP 80g, under room temperature, be stirred to dissolving.Add tetramethylene tetracarboxylic dianhydride (hereinafter to be referred as CBTA) 9.81g (0.05mole) and NMP 20g again, reaction is 2 hours under room temperature, after reaction finishes, polyamic acid polymer solution poured in the 1500ml water polymkeric substance is separated out, the polymkeric substance of filtration gained repeats with washed with methanol and filters three times, insert in the vacuum drying oven, carry out drying with 60 ℃ of temperature after, get final product polyamic acid polymer (A-1-2).
Synthesis example 3
Four cervical vertebra bottles 500 milliliters of volumes arrange nitrogen inlet, agitator, well heater, prolong and thermometer, and importing nitrogen, adding the feed composition thing comprises: VEDA 5.65g (0.01mole), PDA 4.33g (0.04mole), and organic solvent NMP 68g, be warming up under 60 ℃ and be stirred to dissolving, add 3 again, 4-dicarboxyl-1,2,3,4-naphthane-1-succsinic acid dianhydride (hereinafter to be referred as TDA) 15.01g (0.05mole) and NMP 30g, reaction is 6 hours under room temperature, can get the reaction soln of polyamic acid polymer.Add NMP 97g, acetic anhydride 5.61g again, and pyridine 19.75g, be warming up to 60 ℃ of lasting stirrings and carried out imidization in 2 hours, after reaction finishes, the reaction soln of polyimide polymer poured in the 1500ml water polymkeric substance is separated out, filter the gained polyimide polymer and repeat with washed with methanol and filter three times, insert in the vacuum drying oven, after carrying out drying with 60 ℃ of temperature, get final product polyimide polymer (A-2-1).
Synthesis example 4
Four cervical vertebra bottles 500 milliliters of volumes arrange nitrogen inlet, agitator, well heater, prolong and thermometer, and importing nitrogen, adding the feed composition thing comprises: VEDA 5.65g (0.01mole), 4,4 '-two amido diphenyl ether (hereinafter to be referred as ODA) 8.01g (0.04mole), and organic solvent NMP 68g, be warming up under 60 ℃ and be stirred to dissolving, add TDA 15.01g (0.05mole) and NMP30g again, reaction is 6 hours under room temperature, can get the polyamic acid polymer reaction soln.Add NMP 97g, acetic anhydride 5.61g again, and pyridine 19.75g, be warming up to 60 ℃ of lasting stirrings and carried out imidization in 2 hours, after reaction finishes, the reaction soln of polyimide polymer poured in the 1500ml water polymkeric substance is separated out, filter the gained polyimide polymer and repeat with washed with methanol and filter three times, insert in the vacuum drying oven, after carrying out drying with 60 ℃ of temperature, get final product polyimide polymer (A-2-2).
Synthesis example 5
Four cervical vertebra bottles 500 milliliters of volumes arrange nitrogen inlet, agitator, well heater, prolong and thermometer, and importing nitrogen, adding the feed composition thing comprises: VEDA 2.82g (0.005mole), 2,2 '-two [4-(4-amido phenoxy group) phenyl] propane (hereinafter to be referred as BAPP) 18.47g (0.045mole), and organic solvent NMP 100g, under room temperature, be stirred to dissolving.Add 3 again, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (hereinafter to be referred as BTDA) 15.95g (0.0495mole) and NMP 205.42g, reaction is 2 hours under room temperature, after reaction finishes, polyamic acid polymer solution poured in the 1500ml water polymkeric substance is separated out, filter resulting polymers and repeat with washed with methanol and filter three times, insert in the vacuum drying oven, after carrying out drying with 60 ℃ of temperature, get final product polyamic acid polymer.
Four cervical vertebra bottles 500 milliliters of volumes arrange nitrogen inlet, agitator, well heater, prolong and thermometer, and importing nitrogen, adding the feed composition thing comprises: above-mentioned gained polyamic acid polymer 3g, and organic solvent NMP 17g are stirred to dissolving under room temperature.Add gained polyamic acid polymer (A-1-1) 3g and NMP 17g in the synthesis example 1 again, reacted 6 hours down in 60 ℃, then polymers soln is poured in the 1500ml water polymkeric substance is separated out, the filtration resulting polymers repeats with washed with methanol and filters three times, insert in the vacuum drying oven, after carrying out drying with 60 ℃ of temperature, get final product polyamic acid block copolymer (A-3-1).
Synthesis example 6
Four cervical vertebra bottles 500 milliliters of volumes arrange nitrogen inlet, agitator, well heater, prolong and thermometer, and importing nitrogen, adding the feed composition thing comprises: VEDA 2.82g (0.005mole), DDM 8.92g (0.045mole), and organic solvent NMP 100g, under room temperature, be stirred to dissolving.Add BTDA 15.95g (0.0495mole) and NMP 205.42g again, reaction is 6 hours under room temperature, add NMP 94.02g, acetic anhydride 15.15g again, and pyridine 11.73g, be warming up to 110 ℃ of lasting stirrings and carried out imidization in 2 hours, after reaction finishes, polyimide polymer solution poured in the 1500ml water polymkeric substance is separated out, the filtration resulting polymers repeats with washed with methanol and filters three times, insert in the vacuum drying oven, after carrying out drying with 60 ℃ of temperature, get final product polyimide polymer.
Four cervical vertebra bottles 500 milliliters of volumes arrange nitrogen inlet, agitator, well heater, prolong and thermometer, and importing nitrogen, adding the feed composition thing comprises: above-mentioned gained polyimide polymer 3g, and organic solvent NMP 17g are stirred to dissolving under room temperature.Add gained polyamic acid polymer (A-1-1) 3g and NMP 17g in the synthesis example 1 again, reacted 6 hours down in 60 ℃, then polymers soln is poured in the 1500ml water polymkeric substance is separated out, the polymkeric substance of filtration gained repeats with washed with methanol and filters three times, insert in the vacuum drying oven, after carrying out drying with 60 ℃ of temperature, get final product polyamic acid-polyimide block copolymer (A-3-3).
[embodiment of LCD alignment agent and comparative example]
Embodiment 1
Polyamic acid polymer (A-1-1) and the 20 weight part Dicyclopentadiene (DCPD) epoxide (Dicyclopentadiene diepoxide) of getting above-mentioned synthesis example 1 gained of 80 weight parts (B-1-1) are dissolved under room temperature in the cosolvent of NMP 1350 weight parts/ethylene glycol n-butyl ether (hereinafter to be referred as BC) 350 weight parts, gained orientation agent solution, be coated with at ITO (indium-tin-oxide) glass substrate with printing press (Nissha Printing Co., Ltd's system, model S15-036).Afterwards on hot-plate, bake (pre-bake) in advance with 100 ℃ of temperature, 5 minutes time, and in the circulation baking oven, carry out back roasting (post-bake) with 220 ℃ of temperature, 30 minutes time.Measure thickness about 800 ± 200 with elcometer (KLA-Tencor system, model Alpha-step 500)
In film surface, carry out orientation with liquid crystal orienting film board (the meal natural pond makes made, model RM02-11), platform translational speed 50mm/sec, fine hair is given as security into amount 0.3mm during friction, and unidirectional friction is once.With two obtained liquid crystal orienting film glass substrates of above-mentioned steps, a slice glass substrate is coated with hot pressing glue, another sheet glass substrate is spilt gap (spacer) of 4 μ m, two sheet glass are fitted along orientation vertical direction each other, impose the pressure of 10kg again with thermocompressor, carry out hot pressing for 150 ℃ in temperature.With liquid crystal implanter (Shimadzu Seisakusho Ltd.'s system, model ALIS-100X-CH) carrying out liquid crystal injects, seal liquid crystal injecting port with UV-light (UV) sclerosis glue again, make it sclerosis with the ultra-violet lamp irradiation, in baking oven, carry out the liquid crystal temper with 60 ℃ of temperature, 30 minutes time, namely can be made into structure cell (cell).
[evaluation method]
(1) epoxy valency
With the LCD alignment agent with printing press (Nissha Printing Co., Ltd's system, model S15-036) coat glass substrate after, heated 15 minutes down at 220 ℃, form a cured film, this cured film is scraped from glass substrate, extraction is after 72 hours down in 60 ℃ with 10g acetone to get the cured film that 0.5g scrapes, and extraction liquid carries out the epoxy valency with following step and measures:
1, smart scale 0.5～0.6g extraction liquid covers in the Erlenmeyer flask in 100ml, records smart scale value S (unit: g).
2, adding 20ml acetic acid/benzene (volume ratio 1/1) solution fully dissolves.
3, add 3 1% phenolphthalein indicators.
4, add 5 Viola crystallinas (crystal-violet) indicator.
5, with 0.1N hydrogen bromide/acetum titration.
6, when solution colour change into dark green by purple and keep 30 seconds constant, be titration end point, write down titer V (unit: ml).
The epoxy valency O of extraction liquid (unit: the g equivalents of epoxy group(ing)/100g) try to achieve according to following note calculating formula.
The epoxy valency (O) of extraction liquid=[(V-B) * F * 0.16]/S
S: the weight of test portion (g)
V: titer (ml)
B: the required titer of blank test (ml)
F: the factor of hydrogen bromide/acetimetry solution
The factor of hydrogen bromide/acetimetry solution demarcates:
1, smart scale 0.1g yellow soda ash (Na
2CO
3) (handling in 1 hour with 600 ℃ of oven dry in advance) cover in the Erlenmeyer flask in 100ml, notes down smart scale value w (unit: g).
2, add 20ml acetic acid/benzene (volume ratio 1/1) solution.
3, add 10 Viola crystallinas (crystal-violet) indicator.
4, with 0.1N hydrogen bromide/acetum titration.
5, color is changed into dark greenly by purple, is titration end point, writes down titer A (unit: ml).
6, factor=yellow soda ash weight (w)/(0.0053 * A)
(2) voltage retention
Prepared liquid crystal structure cell (cell) is with electric measurement board (TOYO Corporation system, model Model 6254) measuring voltage conservation rate.With the application time of 4 volts of voltage 120 microseconds, after 16.67 milliseconds span applies, measure and apply the voltage retention of having removed after 16.67 milliseconds.And estimate according to following benchmark:
Zero: voltage retention＞96%.
△: voltage retention 94～96%.
*: voltage retention＜94%.
(3) ghost
Prepared liquid crystal structure cell with 10 volts volts DS, applied 48 hours after, when removing this voltage, have or not ghost to take place with visual observation display frame.
Zero: no ghost phenomena takes place.
*: there is ghost phenomena to take place.
Embodiment 2
With the working method of embodiment 1, difference is the consumption that changes polymkeric substance (A), and the consumption that contains the compound (B) of epoxy group(ing), and its detail file and evaluation result are stated from table one.
Embodiment 3
With the working method of embodiment 1, difference is kind and the consumption that changes polymkeric substance (A), and the consumption that contains epoxy compounds (B), and its detail file and evaluation result are stated from table one.
Embodiment 4
With the working method of embodiment 1, difference is kind and the consumption that changes polymkeric substance (A), contains the consumption of epoxy compounds (B), the consumption of organic solvent (C), and the program of omitting follow-up orientation engineering, and its detail file and evaluation result are stated from table one.
Embodiment 5
With the working method of embodiment 1, difference is kind and the consumption that changes polymkeric substance (A), contains the consumption of epoxy compounds (B), the consumption of organic solvent (C), and the program of omitting follow-up orientation engineering, and its detail file and evaluation result are stated from table one.
Embodiment 6
With the working method of embodiment 1, difference is kind and the consumption that changes polymkeric substance (A), contains kind and the consumption of epoxy compounds (B), and organic solvent (C) consumption, and its detail file and evaluation result are stated from table one.
Embodiment 7
With the working method of embodiment 1, difference is to change polymkeric substance (A) kind and consumption, contains the consumption of epoxy compounds (B), and the consumption of organic solvent (C), and its detail file and evaluation result are stated from table one.
Embodiment 8
With the working method of embodiment 1, difference is kind and the consumption that changes polymkeric substance (A), and changes kind and the consumption that contains epoxy compounds (B), and its detail file and evaluation result are stated from table one.
Comparative example 1
With the working method of embodiment 1, difference is to change the kind that contains epoxy compounds (B), and its detail file and evaluation result are stated from table one.
Comparative example 2
With the working method of embodiment 4, difference is to change the kind that contains epoxy compounds (B), and its detail file and evaluation result are stated from table one.
Comparative example 3
With the working method of embodiment 6, difference is to change the kind that contains epoxy compounds (B), and its detail file and evaluation result are stated from table one.
Comparative example 4
With the working method of embodiment 7, difference changes the kind that contains epoxy compounds (B), and its detail file and evaluation result are stated from table one.
Comparative example 5
With the working method of embodiment 1, difference is the consumption that changes polymkeric substance (A), and interpolation contains epoxy compounds (B), and its detail file and evaluation result are stated from table one.
The above person of thought, only for the present invention's preferred embodiment, when the scope that can not limit the invention process with this, namely the simple equivalent of doing according to the present patent application claim and description of the invention content generally changes and modifies, and all should still belong in the patent covering scope of the present invention.
Shown in table 1 content vides infra, wherein:
B-1-1: Dicyclopentadiene (DCPD) epoxide (Dicyclopentadiene diepoxide)
B-1-2: three cyclopentadiene epoxide (Tricyclopentadiene diepoxide)
B-2-1:N, N, N ', N '-Fourth Ring oxygen propyl group-4,4 '-two amido ditans (N, N, N ', N '-tetraglycidyl-4,4 '-diaminodiphenylmethane)
B-2-2:N, N, N ', N '-Fourth Ring oxygen propyl group-m-xylenedimaine (N, N, N ', N '-tetraglycidyl-m-xylenediamine)
Claims (6)
1. LCD alignment agent comprises following component:
The polymkeric substance (A) that tetracarboxylic dianhydride's compound and diamine compound reaction obtain,
The compound (B) that contains epoxy group(ing), and
Organic solvent (C);
It is characterized in that, this compound (B) that contains epoxy group(ing) be tool polycyclic aliphatic structure contain epoxy compounds (B-1); This LCD alignment agent is coated on the glass substrate, with 220 ℃ of heating 15 minutes, make this LCD alignment agent form a cured film, this cured film was obtained extraction liquid in 72 hours with acetone extraction under 60 ℃, the epoxy valency that makes this extraction liquid is O, and the solid based on the LCD alignment agent is 100 weight parts, and making the shared weight part of this compound that contains epoxy group(ing) (B) is W, and this O and W meet following relationship: [O ÷ W * 10
3]≤0.55.
2. LCD alignment agent according to claim 1 is characterized in that, described relational expression [O ÷ W * 10
3]≤0.50.
3. LCD alignment agent according to claim 1 is characterized in that, described relational expression [O ÷ W * 10
3]≤0.45.
4. LCD alignment agent according to claim 1 is characterized in that, when the solid of described LCD alignment agent was 100 weight parts, the described compound (B) that contains epoxy group(ing) accounted for 0.1～45 weight part.
5. a liquid crystal orienting film is characterized in that, this liquid crystal orienting film is formed by the described LCD alignment agent of claim 1.
6. a liquid crystal display device is characterized in that, has the described liquid crystal orienting film of claim 5.
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| CN103718093B (en) * | 2011-08-04 | 2016-11-23 | 日产化学工业株式会社 | The aligning agent for liquid crystal of light orientation position logos and use the liquid crystal orientation film of this aligning agent for liquid crystal |
| US9850347B2 (en) * | 2012-08-01 | 2017-12-26 | Toray Industries, Inc. | Polyamic acid resin composition, polyimide film using same, and method for producing said polyimide film |
| JP6347917B2 (en) * | 2013-05-27 | 2018-06-27 | 株式会社ジャパンディスプレイ | Liquid crystal display device and manufacturing method thereof |
| TWI644945B (en) * | 2015-12-31 | 2018-12-21 | 奇美實業股份有限公司 | Liquid crystal alignment agent and uses thereof |
| WO2018159284A1 (en) * | 2017-02-28 | 2018-09-07 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, method for producing same, liquid crystal element and polymer |
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| CN1637526A (en) * | 2003-12-24 | 2005-07-13 | 奇美电子股份有限公司 | Directional film and liquid crystal display device using the same directional film |
| CN1712491A (en) * | 2004-06-24 | 2005-12-28 | Jsr株式会社 | Veertical liquid crystal orienting agent and vertical liquid crystal display element agent |
| CN1718674A (en) * | 2004-07-06 | 2006-01-11 | Jsr株式会社 | Liquid crystal orientating agent and liquid crystal display element |
| CN101470302A (en) * | 2007-12-27 | 2009-07-01 | 智索株式会社 | Liquid crystal tropism agent, liquid crystal tropism film and liquid crystal display element |
-
2009
- 2009-11-03 CN CN 200910212066 patent/CN102051185B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1637526A (en) * | 2003-12-24 | 2005-07-13 | 奇美电子股份有限公司 | Directional film and liquid crystal display device using the same directional film |
| CN1712491A (en) * | 2004-06-24 | 2005-12-28 | Jsr株式会社 | Veertical liquid crystal orienting agent and vertical liquid crystal display element agent |
| CN1718674A (en) * | 2004-07-06 | 2006-01-11 | Jsr株式会社 | Liquid crystal orientating agent and liquid crystal display element |
| CN101470302A (en) * | 2007-12-27 | 2009-07-01 | 智索株式会社 | Liquid crystal tropism agent, liquid crystal tropism film and liquid crystal display element |
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