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    • 专利摘要:
    The present invention provides a polyamic acid and / or an imidized polymer thereof obtained by reacting a dianhydride of tetracarboxylic acid represented by the following general formula (1) with a diamine compound, and an dianhydride of tetracarboxylic acid represented by the following general formula (2); It relates to a polyamic acid obtainable by reacting a diamine compound and / or an imidized polymer thereof. In said formula, R <1> represents a methyl group or an ethyl group, R <2> represents a hydrogen atom, a methyl group, or an ethyl group, and a is an integer of 1-4.
    公开号:KR19980063947A
    申请号:KR1019970067134
    申请日:1997-12-09
    公开日:1998-10-07
    发明作者:미찌노리 니시까와；겐고 와까바야시；야스오 마쯔끼
    申请人:마쯔모또에이찌；제이에스알가부시끼가이샤；
    IPC主号:
    专利说明:

    Liquid crystal aligning agent
    This invention relates to the liquid crystal aligning agent used for forming the liquid crystal aligning film of a liquid crystal display element, More specifically, it provides a liquid crystal aligning film with favorable liquid crystal alignability, and short afterimage erasing time of a liquid crystal display element, and also a liquid crystal display element. It is related with the liquid crystal aligning agent which provides the liquid crystal aligning film which brings the outstanding long-term reliability to the.
    Conventionally, a nematic liquid crystal layer having positive dielectric anisotropy is formed between two substrates on which a liquid crystal alignment layer is formed on the surface via a transparent conductive film to form a sandwich cell, and the long axis of the liquid crystal molecules is from one substrate to the other. TN type liquid crystal display elements having a so-called twisted nematic (TN) type liquid crystal cell, which are continuously bent at 90 degrees toward the substrate, have been known.
    In liquid crystal display elements, such as this TN type liquid crystal display element, the orientation of a liquid crystal molecule is implement | achieved by the liquid crystal aligning film to which the orientation ability of the liquid crystal molecule was normally given by the rubbing process. Here, as a material of the liquid crystal aligning film which comprises a liquid crystal display element, the imidation polymer which dehydrated and closed polyamic acid and polyamic acid is known conventionally, and since these are excellent in heat resistance, affinity with a liquid crystal, mechanical strength, etc., many liquid crystals It is used as a display element.
    However, in the liquid crystal display element manufactured using the liquid crystal aligning agent containing the conventionally known polyamic acid and / or imidation polymer, afterimages generate | occur | produce on the display screen after removing an applied voltage, and until this afterimage is erased. Because of the long time, there was a problem that sufficient contrast could not be obtained. Moreover, when the said liquid crystal display element is used for a long time, the white uneven display defect may generate | occur | produce, and thus the reliability as a liquid crystal display element was impaired.
    This invention is made | formed in view of the above circumstances.
    A first object of the present invention is to provide a liquid crystal aligning agent capable of producing a liquid crystal display device having a short time (hereinafter referred to as "afterimage erasing time") from the removal of the applied voltage until the afterimage is erased.
    The 2nd object of this invention is to provide the liquid crystal aligning agent which can provide a high reliability to a liquid crystal display element, without a display defect occurring in a liquid crystal display element even if it uses for a long time.
    The 3rd object of this invention is to provide the liquid crystal aligning agent which can form the liquid crystal aligning film excellent in liquid crystal aligning property.
    The liquid crystal aligning agent of this invention is a polyamic acid (henceforth "a polyamic acid (A)", and / or its imidation which can be obtained by making the dianhydride of tetracarboxylic acid and a diamine compound represented by following General formula (1) react. Polyamic acid (henceforth "polyamic acid (C)") obtained by making a polymer (henceforth "imidized polymer (B)") and the dianhydride and tetraamine compound represented by following General formula (2) react with a diamine compound. And / or its imidized polymer (hereinafter, referred to as "imidized polymer (D)").
    Formula 1
    Formula 2
    In said formula, R <1> represents a methyl group or an ethyl group, R <2> represents a hydrogen atom, a methyl group, or an ethyl group, and a is an integer of 1-4.
    Embodiment of the invention
    Hereinafter, the present invention will be described in detail.
    At least one polymer selected from polyamic acid (A) and imidized polymer (B) and at least one polymer selected from polyamic acid (C) and imidized polymer (D) are essential to the liquid crystal aligning agent of the present invention. It is contained as a component.
    The polyamic acid (A) is a tetracarboxylic dianhydride and a diamine compound containing a dianhydride (hereinafter referred to as "specific tetracarboxylic dianhydride (i)") represented by the formula (1). It can obtain by making it react, and an imidation polymer (B) can be obtained by dehydrating and closing the said polyamic acid (A).
    The polyamic acid (C) is a tetracarboxylic dianhydride and a diamine compound containing a dianhydride of the tetracarboxylic acid represented by the formula (2) (hereinafter referred to as "specific tetracarboxylic dianhydride (ii)"). It can obtain by making it react, and an imidation polymer (D) can be obtained by dehydrating and ring-closing the said polyamic acid (B).
    Specific tetracarboxylic dianhydride (i)
    Specific examples of the specific tetracarboxylic dianhydride (i) used to obtain the polyamic acid (A) include 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5 , 9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione and 1,3 , 3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1 And 3-dione, and the like, and these may be used alone or in combination of two or more thereof. Among them, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -Furan-1,3-dione is particularly preferred.
    Specific tetracarboxylic dianhydride (ii)
    The specific tetracarboxylic dianhydride (ii) used to obtain the polyamic acid (C) is 2,3,5-tricarboxycyclopentyl dianhydride.
    Combined tetracarboxylic dianhydride
    As the tetracarboxylic dianhydride for obtaining the polyamic acid (A) and the polyamic acid (C), specific tetracarboxylic dianhydride (i) and specific tetracarboxylic dianhydride ( Tetracarboxylic dianhydride other than ii) can be used together.
    As tetracarboxylic dianhydride which can be used together, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Water, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane 2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetra Hydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5- Ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydro Fural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -octo-7-ene-2,3,5,6-tetracarboxyl Aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride, such as an acid dianhydride and the compound represented by following formula (3-4);
    Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furanthtetracarboxylic Acid dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydrides, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4 '-Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride , m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride , Ethylene glycol -bis (anhydrotrimelitate), propylene glycol -bis (anhydrotrimelitate), 1,4-butanediol-bis (anhydrotrimelitate), 1,6-hexanediol-bis (an Hydrotrimelitate), 1,8-octanediol-bis (anhydro trimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimelitate), the following formulas 5 to 8 Aromatic tetracarboxylic dianhydrides, such as a compound represented by these, are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

    In said formula, R <3> and R <5> represents the divalent organic group which has an aromatic ring, and R <4> and R <6> represent a hydrogen atom or an alkyl group. Two or more R <4> and R <6> may be same or different, respectively.


    Of these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride Water, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3 -Dione, bicyclo [2,2,2] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'- Benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, represented by the formula (3) Of the compounds represented by the following formulas (9) to 11 and the compound represented by the formula (4) of the compound represented by the following formula 12 is a good liquid crystal It is preferable from a viewpoint which can express orientation, and it is especially preferable as a 1, 2-, 3, 4- cyclobutane tetracarboxylic dianhydride, 1, 3- dimethyl- 1, 2, 3, 4- cyclobutane tetracarboxylic Acid dianhydrides, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1 And 3-dione, pyromellitic dianhydride and the compound represented by the following general formula (12).


    The ratio of use of specific tetracarboxylic dianhydride (i) in tetracarboxylic dianhydride for obtaining polyamic acid (A) and specific tetracarboxylic acid in tetracarboxylic dianhydride for obtaining polyamic acid (C) The use ratio of acid dianhydride (ii) is usually 30 mol% or more, preferably 50 mol% or more, and more preferably 70 mol% or more.
    Diamine compounds
    The diamine compound for obtaining the polyamic acid (A) and the polyamic acid (C) is not particularly limited, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4 , 4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenylether , 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-amino Phenoxy) phenyl] sulfone, 1,4-bi (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10 -Hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5 '-Tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4, 4'-diaminobiphenyl, 1,4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4 Aromatic diamines such as' -bis [(4-amino-2-trifluoromethyl) phenoxy) -octafluorobiphenyl;
    1,1-methaxylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1 , 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo [6,2,1,0 2.7 ] -undecylene Aliphatic and alicyclic diamines such as dimethyldiamine and 4,4'-methylenebis (cyclohexylamine);
    2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5, 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-dia Mino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthrizine, 1,4-diaminopiperazine, Two primary subgroups, such as 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, and the compounds represented by the following formulas (13) to (14) Compound which has nitrogen atom other than nitrogen atom which comprises a mino group and the said primary amino group in a molecule | numerator;
    Mono-substituted phenylenediamines represented by the following formula (15); Diaminoorganosiloxane represented by the following formula (16);
    The compound etc. which are represented by following formula (17-21) are mentioned. These diamine compounds can be used individually or in combination of 2 or more types.
    In the above formula, R 7 represents a divalent organic group, and R 8 represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine.
    In said formula, R <9> represents a divalent organic group and two or more R <9> may be same or different. R 10 represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine.
    In the formula, R 11 represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH- and -CO-, R 12 represents a steroid skeleton, a trifluoromethyl group and Monovalent organic group which has at least 1 group chosen from a fluoro group, or a C6-C30 alkyl group is represented.
    In said formula, R <13> represents a C1-C12 hydrocarbon group and two or more R <13> may be same or different, respectively. p is an integer of 1-3, q is an integer of 1-20.


    In said formula, y is an integer of 2-12, z is an integer of 1-5.
    Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4 , 4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4 -(4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4, 4 '-(m-phenylenediisopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] sulphone, 1,4-bis (4-aminophenoxy) benzene, 1, 4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-diaminobenzanilide, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis ( 4-aminophenoxy) biphenyl, the compound represented by Formula 17 to 21, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoa Creedin Among the compounds represented by Formula 13, the compound represented by the following Chemical Formula 22, the compound represented by the following Chemical Formula 23 among the compounds represented by the following Chemical Formula 14, the compound represented by the following Chemical Formulas 24 to 29 among the compounds represented by the following Chemical Formula 15 This is preferred.




    Polyamic acid
    In the synthesis reaction of the polyamic acid [olyamic acid (A) and polyamic acid (C)] which comprises the liquid crystal aligning agent of this invention, the use ratio of tetracarboxylic dianhydride and a diamine compound is 1 equivalent of the amino group contained in a diamine compound. The ratio of the acid anhydride group of the tetracarboxylic dianhydride to 0.2 to 2 equivalents is preferable, and more preferably 0.3 to 1.2 equivalents.
    The synthesis reaction of the polyamic acid constituting the liquid crystal aligning agent of the present invention is usually carried out at an reaction temperature of 0 to 150 ° C, preferably 0 to 100 ° C, over 1 to 48 hours in an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid (A) produced in the reaction. Specifically, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea, hexamethyl phosph Aprotic polar solvents such as fortriamide; and phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenol. As for the usage-amount of an organic solvent, the quantity in which the total amount of tetracarboxylic dianhydride and a diamine compound becomes 0.1-30 weight% with respect to whole quantity of a reaction solution is preferable normally.
    In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of the polyamic acid, can be used in combination without causing precipitation of the polyamic acid. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, acetone, methyl ethyl ketone, cyclohexanone, acetic acid Methyl, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monophenyl ether, ethylene glycol methyl phenyl ether, ethylene glycol ethyl phenyl ether, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether Acetate, 4-hydroxy-4-methyl-2 -Pentanone, 2,4-pentanedione, 2,5-hexanedione, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid Ethyl, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, Ethyl pyruvate, hydroxymethyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methylmethoxybutanol, ethylmethoxybutanol, methylethoxybutanol, ethylethoxybutanol, tetrahydrofuran, tetrahydrofurfuryl alcohol, tetrahydro-3 -Furanmethanol, 1,3-dioxolane, 1,3-dioxane, 4-methyl-1,3-dioxolane, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloro Ethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene It can be given. These can be used individually or in combination of 2 or more types.
    The reaction solution which melt | dissolves a polyamic acid by the above synthesis reaction can be obtained. And a polyamic acid can be obtained by putting this reaction solution in a large quantity of poor solvents, obtaining a precipitate, and drying this precipitate under reduced pressure. Moreover, polyamic acid can be refine | purified by dissolving a polyamic acid again in an organic solvent and then performing a process which precipitates in a poor solvent once or several times.
    Imidized polymer
    The imidized polymer [imidized polymer (B) and imidized polymer (D)] which comprises the liquid crystal aligning agent of this invention can be prepared by dehydrating and ring-opening the said polyamic acid [olyamic acid (A) and polyamic acid (C)]. Can be. The dehydration ring closure of the polyamic acid is carried out by (a) heating the polyamic acid or (b) dissolving the polyamic acid in an organic solvent and adding a dehydrating agent and a dehydration ring closure catalyst to the solution and heating it as necessary. .
    The reaction temperature in the method of heating the polyamic acid of said (a) is 50-200 degreeC normally, Preferably it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, but when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall.
    On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of said polyamic acid (b), acid anhydrides, such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride, can be used as a dehydrating agent, for example. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of repeating units of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, coridine, lutidine, triethylamine and the like can be used, but the present invention is not limited thereto. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. Moreover, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid as an organic solvent used for dehydration ring-closure reaction is mentioned. And the reaction temperature of a dehydration ring-closure reaction is 0-180 degreeC normally, Preferably it is 10-150 degreeC. Moreover, the imidation polymer can be refine | purified by performing the same operation as the purification method of polyamic acid about the reaction solution obtained in this way.
    A terminally modified polymer
    The polymer (polyamic acid (A), imidation polymer (B), polyamic acid (C), and imidation polymer (D)) which comprise the liquid crystal aligning agent of this invention may be terminal modified form in which molecular weight was adjusted. By using this terminal modified polymer, the effect of this invention is not impaired, and the application | coating characteristic of a liquid crystal aligning agent, etc. can be improved. Such terminal modified form can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound, or the like to the reaction system when synthesizing the polyamic acid. Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and the like. . As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n- Eicosylamine, etc. are mentioned. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.
    Logarithmic viscosity of the polymer
    The value of the logarithmic viscosity ((eta) 1n) of the polymer which comprises the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0.05-10 dl / g, More preferably, it is 0.05-5 dl / g. Here, the value of the logarithmic viscosity (η1n) is measured using a N-methyl-2-pyrrolidone as a solvent and the viscosity at 30 ° C with respect to a solution having a polymer concentration of 0.5 g / 100 ml. It was saved.
    Liquid crystal aligning agent
    The liquid crystal aligning agent of this invention is an at least 1 sort (s) of polymer chosen from a polyamic acid (A) and an imidation polymer (B), and at least 1 sort (s) of polymer chosen from a polyamic acid (C) and an imidization polymer (D). It consists of the solution (polymer solution) contained in the organic solvent. Although the compounding ratio of each polymer in the liquid crystal aligning agent of this invention can be suitably selected, at least 1 sort (s) of polymer chosen from a polyamic acid (A) and an imidation polymer (B) with respect to polymer whole quantity becomes like this. Preferably it is 10-90 weight It is preferable that at least 1 sort (s) of polymer chosen from%, a polyamic acid (C), and an imidation polymer (D) is mix | blended preferably 10 to 90 weight%. The liquid crystal aligning agent of this invention is apply | coated to the surface of a board | substrate by a printing method, a spin coat method, etc., for example, and a thin film which is an oriented film material is formed by drying a coating film and removing a solvent.
    The content ratio of the polymer in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, and the like, preferably in the range of 0.1 to 20% by weight, more preferably 1 to 10% by weight of the liquid crystal aligning agent. When the content ratio of the polymer is less than 0.1% by weight, the film thickness of the formed thin film may be too small to obtain a good liquid crystal alignment film. When the content is more than 20% by weight, the film thickness of the thin film is too large to obtain a good liquid crystal alignment film. It is difficult, and the viscosity of a liquid crystal aligning agent may increase and inferior a coating characteristic.
    The organic solvent for dissolving the polymer is not particularly limited as long as it can dissolve the polyamic acid and the imidized polymer, and examples thereof include solvents exemplified as those used in the synthesis reaction and the dehydration ring closure reaction of the polyamic acid. Moreover, the poor solvent illustrated as what can be used together in the synthesis reaction of polyamic acid can also be selected suitably, and can be used together.
    The functional silane containing compound and the epoxy group containing compound may be mix | blended with the liquid crystal aligning agent of this invention from a viewpoint of improving the adhesiveness of the thin film (polymer) with respect to a board | substrate surface. As such a functional silane containing compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidepropyltrimethoxysilane, 3-ureidepropyltrier Methoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-tri Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl- 3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-ben Jyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltri Methoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. are mentioned. As the epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether , Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5 , 6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'- diaminodiphenylmethane, etc. are mentioned as a preferable thing. The compounding ratio of these functional silane containing compounds and epoxy group containing compounds is 40 weight part or less normally with respect to 100 weight part of polymers, Preferably it is 0.1-30 weight part.
    Liquid crystal display element
    The liquid crystal display element obtained using the liquid crystal aligning agent of this invention can be manufactured, for example by the following method.
    (1) The liquid crystal aligning agent of this invention is apply | coated to the transparent conductive film side of the board | substrate with which the patterned transparent conductive film was installed, for example by methods, such as a roll coater method, a spinner method, and a printing method, and a thin film is formed by heating a coating surface then. . As the substrate, for example, a transparent substrate made of glass such as float glass or soda glass, plastic film such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or the like can be used. As the transparent conductive film provided on one surface of the substrate, an NESA film made of SnO 2 , an ITO film made of In 2 O 3 -SnO, or the like can be used, and a photo-etching method and a mask in advance are used for patterning these transparent conductive films. Method and the like can be used.
    In application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate, a transparent conductive film, and a thin film more favorable, you may apply | coat a functional silane containing compound, titanate, etc. on a board | substrate and a transparent conductive film beforehand. Moreover, as for heating temperature, 80-250 degreeC is preferable, More preferably, it is 120-200 degreeC. The film thickness of the formed thin film is usually 0.001 to 1 mu m, preferably 0.005 to 0.5 mu m.
    (2) The formed thin film is subjected to a rubbing treatment of rubbing in a predetermined direction with a roll wound around a cloth made of synthetic fibers such as nylon to impart alignment ability of liquid crystal molecules to the thin film, thereby forming a liquid crystal alignment film. Moreover, a liquid crystal aligning film can also be formed by the method of irradiating polarized ultraviolet-ray to the surface of a thin film in addition to the method by a rubbing process, and providing a thin film by the uniaxial stretching method, the Langmuir project method, etc. In addition, it is preferable to wash the formed liquid crystal aligning film with isopropyl alcohol or the like in order to remove the fine powder (foreign substance) generated during the rubbing treatment and to wash the surface. Moreover, the process which changes a pretilt angle by partially irradiating an ultraviolet-ray to the liquid crystal aligning film formed by the liquid crystal aligning agent of this invention, for example as Unexamined-Japanese-Patent No. 6-222366 and 6-281937. Alternatively, as shown in Japanese Patent Application Laid-open No. Hei 5-107544, a resist film is partially formed on the rubbed liquid crystal alignment film and subjected to a rubbing treatment in a direction different from the preceding rubbing treatment, and then the resist film is removed to obtain a liquid crystal alignment film. It is possible to improve the clock characteristic of a liquid crystal display element by performing the process which changes an orientation ability.
    (3) Two board | substrates with a liquid crystal aligning film were produced as mentioned above, and two board | substrates were opposed through a gap (cell gap) so that the rubbing direction in each liquid crystal aligning film may be orthogonal or antiparallel, The periphery of the substrate is bonded with a sealant, the liquid crystal is filled in the cell gap partitioned by the substrate surface and the sealant, and the filling hole is sealed to form a liquid crystal cell. And a liquid crystal display element can be obtained by bonding the polarizing plate to the outer surface of the liquid crystal cell, ie, the other surface side of each substrate constituting the liquid crystal cell, so that its polarization direction is coincident with or perpendicular to the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate. have.
    As the sealant, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used.
    As said liquid crystal, a nematic liquid crystal and a smectic liquid crystal are mentioned, for example. Especially, a nematic type liquid crystal is preferable, for example, a Schiff base type liquid crystal, an azo key clock liquid crystal, a biphenyl type liquid crystal, a phenyl cyclohexane type liquid crystal, an ester type liquid crystal, a terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimi Din type liquid crystal, a dioxane type liquid crystal, a bicyclo octane type liquid crystal, a cuban type liquid crystal, etc. can be used. Moreover, it is marketed by these liquid crystals as cholesteric liquid crystals, such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and brand names "C-15", "CB-15" (made by Merck), for example. It is also possible to add and use a chiral agent. Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.
    Moreover, as a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate which interposed the polarizing film called H film which absorbed iodine while extending | stretching polyvinyl alcohol through the cellulose acetate protective film, the polarizing plate which consists of H film itself, etc. are mentioned. .
    Example
    Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.
    In addition, the measuring method and the evaluation method about the liquid crystal display element produced by the following example and the comparative example are as follows.
    [Orientation of Liquid Crystal]
    The presence or absence of the abnormal domain in the liquid crystal cell at the time of turning on and off the voltage to a liquid crystal display element was observed with the polarization microscope, and it judged that the case where there was no abnormal domain was "good".
    [Afterimage erasing time]
    After applying a DC voltage of 7 V to the liquid crystal cell for 5 hours, the application of the voltage was canceled and the display screen was visually observed to measure the time from when the voltage was released until the afterimage was removed from the screen. It was.
    [Reliability Test (Presence or Absence of Display Defects) of Liquid Crystal Display Element]
    Under the high temperature and high humidity environment (temperature 70 degreeC, relative humidity 80%), the liquid crystal display element was driven by the square wave of 5V and 60Hz, and after 1500 hours, the presence or absence of the white defect display defect was observed with the polarization microscope.
    Synthesis Example 1
    1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1 314.30 g (1.00 mol) of, 3-dione, 86.51 g (0.80 mol) of p-phenylenediamine and 84.48 g (0.20 mol) of the diamine compound of formula 28 were dissolved in 1500 g of N-methyl-2-pyrrolidone and The solution was reacted at 40 ° C. for 6 hours. The reaction solution obtained was then placed in a large excess of pure water to precipitate the reaction product. Thereafter, the solid was separated, washed with pure water, and dried at 40 ° C. for 15 hours under reduced pressure to obtain a polyamic acid (A) having a logarithm viscosity (η 1 n) of 1.12 dl / g, which is referred to as "polymer (A-1)". 451.3 g Got.
    Synthesis Example 2
    30.0 g of the polymer (A-1) obtained in Synthesis Example 1 was dissolved in 570 g of γ-butyrolactone, and 33.3 g of pyridine and 25.8 g of acetic anhydride were added and dehydrated and closed for 3 hours at 50 ° C. Subsequently, the reaction product is precipitated, separated, washed and dried in the same manner as in Synthesis example 1 to give an imidized polymer (B) having a logarithmic viscosity (η 1 n) of 1.14 dl / g (this is referred to as "polymer (B-2)"). 28.3 g was obtained.
    Synthesis Example 3
    Synthesis example except that 75.70 g (0.70 mol) of p-phenylenediamine, 39.65 g (0.20 mol) of 4,4'- diaminodiphenylmethane, and 42.24 g (0.10 mol) of the diamine compound of Formula 28 were used as a diamine compound. In the same manner as in 1, 439.1 g of a polyamic acid (A) having a logarithmic viscosity (η 1n) of 1.01 dl / g was obtained. Thereafter, an imidized polymer (B) having a logarithmic viscosity (η 1 n) of 1.05 dl / g was used in the same manner as in Synthesis Example 2, except that 30.0 g of polymer (A-3) was used instead of polymer (A-1). (B-4) ”] 27.9 g was obtained.
    Synthesis Example 4
    Algebraic viscosity (η1n) 0.87 dl / in the same manner as in Synthesis Example 1, except that 86.51 g (0.80 mol) of p-phenylenediamine and 104.16 g (0.20 mol) of 3,5-diaminobenzoic acid cholesterol were used as the diamine compound. 469.6 g of g polyamic acid (A) [this was referred to as "polymer (A-5)"] was obtained. Thereafter, an imidized polymer (B) having a logarithmic viscosity ( 1n) of 0.90 dl / g was used in the same manner as in Synthesis Example 2, except that 30.0 g of polymer (A-5) was used instead of polymer (A-1). (B-6) ”] 28.4 g was obtained.
    Synthesis Example 5
    Polyamic acid having a logarithmic viscosity (η 1n) of 0.99 dl / g was used in the same manner as in Synthesis Example 1, except that 86.51 g (0.80 mol) of p-phenylenediamine and 74.48 g (0.20 mol) of the diamine compound represented by Chemical Formula 29 were used as the diamine compound. A) 442.0 g of [this is referred to as "polymer (A-7)" were obtained. Thereafter, an imidized polymer (B) having a logarithmic viscosity ( 1n) of 0.99 dl / g was used in the same manner as in Synthesis Example 2, except that 30.0 g of polymer (A-7) was used instead of polymer (A-1). (B-8)]] 28.3 g was obtained.
    Synthesis Example 6
    As tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 Using 251.44 g (0.80 mole) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 44.83 g (0.20 mole) of, 2-c] furan-1,3-dione In the same manner as in Synthesis example 1, 434.3 g of a polyamic acid (A) having a logarithmic viscosity (η 1n) of 0.92 dl / g was obtained. Thereafter, an imidized polymer (B) having a logarithmic viscosity (η 1 n) of 0.96 dl / g was used in the same manner as in Synthesis Example 2, except that 30.0 g of polymer (A-9) was used instead of polymer (A-1). (B-10)] 28.1 g was obtained.
    Synthesis Example 7
    Synthesis except that 224.17 g (1.00 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride was used as tetracarboxylic dianhydride and 108.14 g (1.00 mol) of p-phenylenediamine was used as a diamine compound. In the same manner as in Example 1, 309.0 g of a polyamic acid (C) having a logarithmic viscosity (η 1n) of 1.68 dl / g was referred to as “polymer (C-11)”. Thereafter, an imidized polymer (D) having a logarithmic viscosity (η 1 n) of 1.73 dl / g was used in the same manner as in Synthesis Example 2, except that 30.0 g of polymer (C-11) was used instead of polymer (A-1). (D-12)]] 28.5 g was obtained.
    Synthesis Example 8
    Polyamic acid having a logarithmic viscosity ( 1n) of 1.58 dl / g in the same manner as in Synthesis Example 7 except that 432.50 g (1.00 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone was used as the diamine compound. 610.7 g of (C) [Make this a "polymer (C-13)") were obtained.
    Synthesis Example 9
    Except for using 179.34 g (0.80 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 43.62 g (0.20 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride, Polyamic acid (C) having a viscosity (η 1 n) of 1.75 dl / g was obtained. 307.8 g was obtained as “polymer (C-14)”.
    Example 1
    2.0 g of the polymer (A-1) obtained in Synthesis Example 1 and 8.0 g of the polymer (C-11) obtained in Synthesis Example 7 were dissolved in N-methyl-2-pyrrolidone to give a solution having a solid content of 4% by weight, This solution was filtered with the filter of 1 micrometer of pore diameters, and the liquid crystal aligning agent of this invention was prepared.
    This liquid crystal aligning agent was apply | coated to the said transparent electrode surface of the glass substrate with which the transparent electrode which consists of an ITO film | membrane was used using the aligning agent coating printer, and it dried for 20 minutes on a 180 degreeC hotplate, and dried the thin film of 0.05 micrometers in dry film thickness Formed.
    The rubbing process was performed using the rubbing machine which has the roll which rolled up the cloth of the rayon agent with respect to the surface of the thin film formed in this way, The orientation ability of liquid crystal molecules was provided to the said thin film, and the liquid crystal aligning film was formed. The rubbing process conditions were made into the rotation speed of 500 rpm of the roll, the movement speed of a stage of 1 cm / sec, and the length of the pushed hair of 0.4 mm.
    Two board | substrates with a liquid crystal aligning film were produced as mentioned above, and after apply | coating the epoxy resin containing aluminum oxide sphere of 17 micrometers in diameter to the outer edge part of each board | substrate by the screen printing method, in each liquid crystal aligning film, Two board | substrates were opposingly arranged through the clearance gap so that a rubbing direction might become antiparallel, the outer edge parts were abutted, they were crimped | bonded, and the adhesive agent was hardened. Subsequently, nematic liquid crystal "ZLI-4792" (manufactured by Merck Co., Ltd.) was filled in the cell gap partitioned by the adhesive on the surface of the substrate and the outer edge portion, and then the injection hole was sealed with an epoxy adhesive to constitute a liquid crystal cell. Next, the liquid crystal display element was produced by bonding a polarizing plate to the outer surface of the liquid crystal cell, ie, the other surface of each board | substrate which comprises a liquid crystal cell so that a polarization direction may correspond with the rubbing direction of the liquid crystal aligning film formed in one surface of the said board | substrate.
    When the liquid crystal aligning property was investigated about the liquid crystal display element produced as mentioned above, when the voltage was turned on and off, the abnormal domain was not confirmed in the liquid crystal cell, and it was confirmed that it had the outstanding orientation. In addition, the afterimage erasing time was very short for 0.7 second. Moreover, even if it used for a long time under high temperature, high humidity, the display defect of white unevenness was high reliability which was not recognized. The above result was shown in Table 1.
    Examples 2-11
    According to the prescription shown in Table 1, the polyamic acid (A) or the imidized polymer (B) and the polyamic acid (C) or the imidized polymer (D) were dissolved in N-methyl-2-pyrrolidone to give a solid content of 4 weights. A liquid crystal aligning agent of the present invention was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent was prepared to form a thin film and a liquid crystal aligning film to prepare a liquid crystal display element. Thus, the orientation of liquid crystal was evaluated about the produced liquid crystal display element, the afterimage erase time was measured, and the reliability test was done. The results are shown in Table 1.
    Comparative Examples 1 and 2
    Example 1 except that each of the polymer (B-2) and the polymer (C-11) was dissolved in N-methyl-2-pyrrolidone according to the prescription shown in Table 1 to prepare a solid concentration of 4% by weight. A liquid crystal aligning agent for comparison was prepared in the same manner as above, and a thin film and a liquid crystal aligning film were formed to prepare a liquid crystal display element. Thus, the orientation of liquid crystal was evaluated about the produced liquid crystal display element, the afterimage erase time was measured, and the reliability test was done. The results are shown in Table 1.
    polymerOrientationAfterimage Clearing Time (sec)Reliability Test (Presence of Display Defect) KindsUsage ratio (% by weight)KindsUse ratio (% by weight) ExampleOneA-120C-1180Good0.7none 2B-220C-1180Good0.7none 3A-150C-1150Good0.8none 4A-180C-1120Good1.3none 5B-420C-1180Good0.7none 6B-620C-1180Good0.8none 7B-820C-1180Good0.8none 8A-1020C-1180Good0.7none 9B-220D-1280Good1.4none 10B-220C-1380Good0.5none 11B-220C-1480Good0.6none Comparative exampleOneB-2100--Good11.3none 2--C-11100Good0.4Smear
    According to the liquid crystal aligning agent of this invention, the liquid crystal display element with a short residual image erasing time can be manufactured.
    Moreover, according to the liquid crystal aligning agent of this invention, even if it uses for a long time, a display defect does not generate | occur | produce in a liquid crystal display element, and high reliability can be provided to the said liquid crystal display element.
    Moreover, according to the liquid crystal aligning agent of this invention, the liquid crystal aligning film excellent in liquid crystal aligning property can be formed.
    The liquid crystal display element provided with the liquid crystal aligning film formed by the liquid crystal aligning agent of this invention is not only a TN type liquid crystal display element but STN (Super Twisted Nematic) type liquid crystal display element, SH (Super Homeotropic) type liquid crystal display element, IPS It can be used suitably as various liquid crystal display elements, such as an (In-Plane-Switching) type | mold liquid crystal display element, a ferroelectric liquid crystal display element, and an antiferroelectric liquid crystal display element. The liquid crystal display element can be effectively used in various devices, and can be suitably used as a display device such as a table calculator, a wrist watch, a table clock, a counting plate, a word processor, a personal computer, a liquid crystal television, or the like.
    权利要求:
    Claims (1)
    [1" claim-type="Currently amended] A polyamic acid and / or an imidized polymer thereof obtained by reacting a dianhydride of tetracarboxylic acid represented by the following general formula (1) with a diamine compound and a dianhydride and a diamine compound of tetracarboxylic acid represented by the following general formula (2) A polyamic acid obtainable by reaction and / or its imidation polymer are contained, The liquid crystal aligning agent characterized by the above-mentioned.
    Formula 1

    Formula 2

    In said formula, R <1> represents a methyl group or an ethyl group, R <2> represents a hydrogen atom, a methyl group, or an ethyl group, and a is an integer of 1-4.
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    同族专利:
    公开号 | 公开日
    JPH10183120A|1998-07-14|
    KR100487047B1|2005-09-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-12-27|Priority to JP96-349392
    1996-12-27|Priority to JP34939296A
    1997-12-09|Application filed by 마쯔모또에이찌, 제이에스알가부시끼가이샤
    1998-10-07|Publication of KR19980063947A
    2005-09-08|Application granted
    2005-09-08|Publication of KR100487047B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP96-349392|1996-12-27|
    JP34939296A|JPH10183120A|1996-12-27|1996-12-27|Liquid crystal orientating agent|
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