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    • 专利摘要:
    An object of the present invention is to provide a liquid crystal aligning agent which has good liquid crystal alignment property and is hard to cause display defects in the periphery of a liquid crystal display screen. The present invention comprises at least one polymer selected from [a] polyamic acid and an imidized polymer of polyamic acid, and [b-1] specific alcohol compound and / or [b-2] specific alkoxysilane compound. A liquid crystal aligning agent is provided.
    公开号:KR19990036935A
    申请号:KR1019980041988
    申请日:1998-10-08
    公开日:1999-05-25
    发明作者:교우유 야스다；미즈요 고바야시；야스오 마쯔끼
    申请人:마쯔모또 에이찌；제이에스알 가부시끼가이샤；
    IPC主号:
    专利说明:

    Liquid crystal aligning agent
    The present invention relates to a liquid crystal aligning agent, and more particularly, to a liquid crystal aligning agent having good printability, adhesiveness, and liquid crystal alignment property (in particular, display defects hardly occur in the periphery of the liquid crystal display screen).
    Conventionally, a nematic liquid crystal layer having positive dielectric anisotropy is formed between two substrates on which a liquid crystal alignment film 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 formed on one substrate. A TN type liquid crystal display element having a TN (Twisted Nematic) type liquid crystal cell which is continuously twisted 90 degrees toward the other substrate is known. Liquid crystal orientation in liquid crystal display elements, such as this TN type liquid crystal display element, is implement | achieved by the liquid crystal aligning film to which the orientation ability of liquid crystal molecules was provided by the rubbing process normally. Here, resins, such as a polyimide, a polyamide, and polyester, are known conventionally as a material of the liquid crystal aligning film which comprises a liquid crystal display element. In particular, polyimides are used in most liquid crystal display devices because of their excellent heat resistance, affinity with liquid crystals, mechanical strength, and the like.
    However, in the liquid crystal display element using the liquid crystal aligning film containing the conventionally known polyamic acid and the polyimide polymer which has a structure obtained by dehydrating and ring-closing it, there exists a problem that display defects arise easily in the periphery of the obtained liquid crystal display element. . This is considered to be a phenomenon caused by chemical adsorption or chemical reaction between a chemical substance such as a sealing agent for bonding a glass substrate and a sealing agent for sealing a liquid crystal injection hole and a liquid crystal alignment layer. Seems to have greatly influenced this phenomenon.
    This invention is made | formed in view of the above circumstances, The 1st objective of this invention is providing the liquid crystal aligning film which has the outstanding printing property, adhesiveness, and liquid crystal aligning property by providing the orientation ability of liquid crystal molecules reliably by a rubbing process. It is to provide a liquid crystal aligning agent.
    The 2nd object of this invention is to provide the liquid crystal aligning agent which gives a liquid crystal aligning film which a display defect does not produce in the periphery of a liquid crystal display element.
    1 is an NMR chart of a compound represented by Chemical Formula 1a used in Examples of the present invention.
    Liquid crystal aligning agent of this invention
    [a] at least one polymer selected from polyamic acid and an imidized polymer of polyamic acid,
    [b-1] It is characterized by containing a compound represented by the following formula (1) (hereinafter also referred to as "compound 1").
    (In the formulas, A 1 to A 11 each independently represent an alkyl group or a hydrogen atom.)
    Or the liquid crystal aligning agent of this invention
    [a] at least one polymer selected from polyamic acid and an imidized polymer of polyamic acid,
    [b-2] A compound having a structure represented by the following formula (2) and / or a polymer (hereinafter also referred to as "compound 2") is characterized by containing.
    (In the formula, A 12 to A 14 each independently represent an alkyl group or a hydrogen atom.)
    Hereinafter, the present invention will be described in detail.
    <(a-1) polyamic acid>
    The polyamic acid which comprises the liquid crystal aligning agent of this invention can be prepared by making tetracarboxylic dianhydride and a diamine compound react.
    As tetracarboxylic dianhydride used for the synthesis reaction of such a polyamic acid, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl, for example. -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2 , 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuranthratecarboxylic dianhydride, 1,3, 3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5- Oxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro -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, 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, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1 , 2-dicarboxylic dianhydride, bicyclo [2,2,2] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, compounds represented by the following formulas (3) and (4): Aliphatic and alicyclic tetracarboxylic dianhydrides such as;

    (In the formula, R 1 and R 4 represent a divalent organic group having an aromatic ring, R 2 and R 3 represent a hydrogen atom or an alkyl group, and a plurality of R 2 and R 3 may be the same or different from each other.)
    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-furantetracarboxylic 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 (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (anhydro Trimellitate), 1,8-octanediol-bis (anhydro trimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydro trimellitate), Aromatic tetracarboxylic dianhydrides, such as the compound shown, are mentioned. These can be used individually by 1 type or in combination of 2 or more types.


    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, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl- 3-cyclohexene-1,2-dicarboxylic 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-8-methyl-5- (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-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'-biphenylsulphate Ponte Lacarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, among the compounds represented by the formula (3) represented by the following formulas 9 to 11 and the compound represented by the formula (4) The compound represented by the formula (12) is preferable from the viewpoint of being able to express good liquid crystal alignment property, and particularly preferred is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic 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-8-methyl-5 -(Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, pyromellitic dianhydride and the compound represented by following formula (11) There is a number.


    As a diamine compound used for the synthesis reaction of a polyamic acid, p-phenylenediamine, m-phenylenediamine, 4,4'- diaminophenylmethane, 4,4'- diamino diphenylethane, 4, for example. , 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-aminophenoxy) phenyl] sulfone, 1,4- Bis (4-aminophenoxy) benzene, 1,3-bis (4- Minophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9- (4 -Aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminophenyl, 2,2'-dichloro -4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 1,4,4 '-(p-phenyleneiso Propylidene) bisaniline, 4,4 '-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoro Lopropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octa Aromatic diamines such as fluorobiphenyl;
    1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine , 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo [6,2,1,02.7] -unde Aliphatic and alicyclic diamines such as silendimethyldiamine and 4,4-methylenebis (cyclohexylamine);
    Mono-substituted phenylenediamines represented by the following formula (13); Diaminoorganosiloxane represented by the following formula (14);
    Wherein R 5 represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -CO-, and R 6 represents a steroid skeleton or a trifluoromethyl group The monovalent organic group which has is shown.)
    (In formula, R <7> represents a C1-C12 hydrocarbon group, two or more R <7> may mutually be same or different, p is an integer of 1-3, q is an integer of 1-20.)
    The compound etc. which are represented by following formula (15)-(19) are mentioned. These diamine compounds can be used individually or in combination of 2 or more types.


    (Wherein y is an integer of 2 to 12, and z is an integer of 1 to 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, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, Among the compounds represented by 4,4-bis (4-aminophenoxy) biphenyl, the above formulas 15 to 19, and the above formula 13, the compounds represented by the following formulas 20 to 25 are preferable. Such diamine may use a commercial item as it is, or may be used by re-reduction.



    The use ratio of the tetracarboxylic dianhydride and the diamine compound used in the polyamic acid synthesis reaction is 0.2 to 2 equivalents of the acid anhydride group contained in the tetracarboxylic dianhydride relative to 1 equivalent of the amino group contained in the diamine compound. The ratio which becomes is preferable, More preferably, it is the ratio which becomes 0.3 to 1.4 equivalent. In both the case where the ratio of the acid anhydride group contained in tetracarboxylic dianhydride is less than 0.2 equivalent, and when it exceeds 2 equivalent, the molecular weight of the polymer obtained may become so small that the applicability | paintability of a liquid crystal aligning agent may fall. .
    The polyamic acid which comprises the liquid crystal aligning agent in this invention is synthesize | combined by reaction of tetracarboxylic dianhydride and a diamine compound. The synthesis reaction of the polyamic acid is usually carried out in an organic solvent under temperature conditions of 0 to 150 캜, preferably 0 to 100 캜. When reaction temperature is 0 degrees C or less, the solubility to a solvent of a compound may be inferior, and when it exceeds 150 degreeC, the molecular weight of the polymer obtained may fall.
    The organic solvent used for the synthesis of the polyamic acid is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride, the diamine compound and the polyamic acid produced by the reaction. For example, γ-butyrolactone and N-methyl- 2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoryltriamide, 1, 3-dimethyl-2-imidazolidinone, etc. Aprotic polar solvents; Phenol solvents, such as m-clesol, xylenol, a phenol, and a halogenated phenol, are mentioned.
    The amount of the organic solvent (A) is preferably an amount such that the total amount (B) of the tetracarboxylic dianhydride and the diamine compound as the reaction raw material is 0.1 to 30% by weight based on the total amount of the reaction solution (A + B).
    In addition, the organic solvent may be used in a range in which polyamic acid, which is a poor solvent of polyamic acid, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, is not precipitated. 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, and methyl isobutyl Ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonic acid, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl 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, propylene glycol methyl ether, propylene Glycol ethyl ether, propylene glycol dimethyl ether Le, propylene glycol diethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, ethylene glycol ethyl ether acetate, 4-hydroxy-4-methyl-2- Pentanone, ethyl 2-hydroxypropionate, ethyl lactate, methyl lactate, butyl lactate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutanoic acid, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, 3-methyl-3-methoxybutanol, 3-ethyl-3-methoxybutanol, 2-methyl-2-methoxybutanol, 2-ethyl-2-methoxy Butanol, 3-methyl-3-ethoxybutanol, 3-ethyl-3-ethoxybutanol, 2-methyl-2-ethoxybutanol, 2-ethyl-2-ethoxybutanol, tetrahydrofuran, dichloromethane, 1 , 2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichloro Benzene, hexane, heptane, octane, benzene, toluene, xylene and the like. These can be used individually by 1 type or in combination of 2 or more types.
    By the above synthesis reaction, a polymer solution in which polyamic acid is dissolved is obtained. The polymer solution is then placed in a large amount of poor solvent to obtain a precipitate, and the precipitate can be dried under reduced pressure to obtain a polyamic acid. In addition, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent once or several times.
    <(a-2) imidized polymer>
    The imidation polymer which comprises the liquid crystal aligning agent of this invention can be prepared by the following method (1)-(3). The imidized polymer is usually polyimide and / or polyisoimide, with polyimide being preferred. Moreover, the polymer whose so-called imidation ratio which is a part of the repeating unit of polyamic acid dehydration ring-closure is not 100% is also contained in an imidation polymer, and is used suitably for the liquid crystal aligning agent of this invention. "Imidation ratio" here shows the ratio of the repeating unit which has an imide ring in all the repeating units of a polymer as a percentage.
    Method (1): A method of heating and dehydrating the polyamic acid to ring closure.
    In this method, the reaction temperature is usually 60 to 200 ° C, preferably 100 to 170 ° C. When reaction temperature is less than 60 degreeC, dehydration ring-closure reaction does not fully advance, but when reaction temperature exceeds 200 degreeC, the molecular weight of specific polymer (II) obtained may become small.
    Method (2): A method of dissolving a polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring closure catalyst to this solution, and heating as needed.
    In this method, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used. It is preferable that the usage-amount of a dehydrating agent shall be 1.6-20 mol with respect to 1 mol of repeating units of a polyamic acid. As the imidation catalyst, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used, for example, but are not limited thereto. It is preferable that the usage-amount of an imidation catalyst shall be 0.5-10 mol with respect to 1 mol of dehydrating agents to be used. Moreover, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid as an organic solvent used for imidation reaction is mentioned. And reaction temperature of imidation reaction is 0-180 degreeC normally, Preferably it is 60-150 degreeC.
    Method (3): The method of mixing and condensing tetracarboxylic dianhydride and a diisocyanate compound.
    As a specific example of the diisocyanate compound used by this method, Aliphatic diisocyanate compounds, such as hexamethylene diisocyanate; Alicyclic diisocyanate compounds such as cyclohexane diisocyanate; Diphenylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, 1 , 2-diphenylethane-p, p'-diisocyanate, 2,2-diphenylpropane-p, p'-diisocyanate, 2,2-diphenyl-1,1,1,3,3,3- Hexafluoropropane-p, p'-diisocyanate, 2,2-diphenylbutane-p, p'-diisocyanate, diphenyldichloromethane-4,4'-diisocyanate, diphenylfluoromethane-4, Aromatic diisocyanate compounds, such as 4'- diisocyanate, benzophenone-4,4'- diisocyanate, and N-phenylbenzoic acid amide-4,4'- diisocyanate, These can be mentioned individually or in combination of 2 or more types Can be used. In addition, this method does not require a catalyst in particular, and reaction temperature is 50-200 degreeC normally, Preferably it is 100-160 degreeC.
    The imidized polymer can be refine | purified by performing the same operation as the purification method of a polyamic acid with respect to the polymer solution obtained in this way.
    <Intrinsic Viscosity of Polyamic Acid and Imidized Polymer>
    The intrinsic viscosity of the polyamic acid and the imidized polymer obtained as described above (measured in N-methyl-2-pyrrolidone at 30 ° C., the same as below) is usually 0.05 to 10 dl / g, preferably 0.05 to 5 dl / g
    <Polymer of Terminal Modified Type>
    The terminal modified polymer may be sufficient as the polyamic acid and / or imidation polymer which comprise the liquid crystal aligning agent of this invention. This terminal modified polymer can improve molecular weight, and can improve the coating characteristic of a liquid crystal aligning agent, etc., without impairing the effect of this invention. The terminally modified polymer can be synthesized by adding an acid anhydride, a monoamine compound or a monoisocyanate compound to the reaction system when synthesizing the polyamic acid.
    Examples of the acid anhydride added to the reaction system when synthesizing the polyamic acid to obtain a terminally modified polymer 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 added to the reaction system, 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 alkylamines such as n-eicosylamine; 3-aminopropylmethyldiethoxysilane, 3- [N-allyl-N- (2-aminoethyl)] aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-[(3-trimethoxysilyl) propyl] diethylenetriamine, etc. are mentioned. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.
    <Compound (1)>
    By containing the compound represented by the said Formula (1), the liquid crystal aligning agent of this invention becomes the leveling property at the time of coating and baking a liquid crystal aligning agent, and can form the liquid crystal aligning film with little surface unevenness | corrugation. As a result, the liquid crystal display element obtained using the said liquid crystal aligning film will have the outstanding display characteristic which a liquid crystal defect does not generate | occur | produce.
    In Formula 1, A 1 to A 11 is to indicate an alkyl group or a hydrogen atom. Examples of the alkyl group is preferably a alkyl group having 1 to 6 carbon atoms. As a specific example of the chemical substance 1, the novel compound etc. which are obtained by adding and ring-opening-reacting ethylene glycol monoesters to (gamma) -butyrolactone are mentioned. These compounds can be used individually or in combination of 2 or more types. Moreover, the compound 1 used for the liquid crystal aligning agent of this invention has a boiling point of 200 degreeC or more at normal pressure, and the thing of 250 degreeC or more is especially preferable. If it is less than 200 degreeC at normal pressure, it may volatilize too early at the time of baking a liquid crystal aligning agent, and a leveling effect may not fully be acquired.
    <Compound 2>
    The liquid crystal aligning agent of this invention contains the compound and / or polymer which have the structure represented by living formula (2), and the adhesiveness of the liquid crystal aligning film obtained and a board | substrate improves, the film peeling at the time of rubbing is prevented, the film cutting is prevented, The liquid crystal aligning film with little unevenness | corrugation can be formed. As a result, the liquid crystal display element obtained using the said liquid crystal aligning film can be what has the outstanding display performance which a display defect does not produce.
    In said Formula (2), A <12> -A <14> represents an alkyl group or a hydrogen atom, As this alkyl group, a C1-C6 alkyl group is preferable. Specific examples of the compound 2 include 3-glycidoxypropylmethylethoxysilane, 3-glycidoxypropylmethyldiisopropenoxysilane, N-glycidyl-N, N-bis [3- (methyldimethoxysilyl) Silane compounds such as propyl] amine, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and these silane compounds The terminal modified polymer obtained by couple | bonding with the terminal of a polyamic acid or a polyimide is mentioned. Such compound 2 can be used individually or in combination of 2 or more types.
    <Liquid crystal aligning agent>
    The liquid crystal aligning agent of this invention is comprised by [a] component which consists of an imidation polymer of a polyamic acid and / or a polyamic acid, and the [b] component selected from the said compound 1 and the compound 2 dissolved and contained in an organic solvent. When the terminal modified polymer is used as the compound 2, the silane compound may be added during the synthesis of the polyamic acid and / or the imidized polymer to use a part of the polymer as the terminal modified polymer.
    The content ratio (polymer concentration) of the component [a] in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, and the like, and is preferably in the range of 0.1 to 20% by weight, more preferably 0.5 to the whole solution. To 10% by weight. If this concentration is less than 0.1% by weight, the film thickness of the coating film (coating) is too small to obtain a good liquid crystal aligning agent. On the other hand, if this concentration is more than 20% by weight, the film thickness of the coating film is excessively good liquid crystal. It is difficult to obtain an alignment film, and the viscosity of a liquid crystal aligning agent may increase, and coating characteristics may fall.
    As a content rate of the [b] component in the liquid crystal aligning agent of this invention, the ratio of the [b-1] component with respect to 100 weight part of [a] components is 0.01 to 20 weight% normally, Preferably it is 0.1 to 10 weight% to be. If it is less than 0.01 weight part, the effect of leveling may not fully appear, and when it exceeds 20 weight part, many [b-1] components remain in an orientation film, and the orientation characteristic may fall. In the case of the silane compound, the proportion of the component [b-1] is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight. In the case of the polymer in which the silane compound is introduced at the terminal, the amount of Si in the polymer is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. If it is less than 0.1 weight part, the improvement effect of adhesiveness with the obtained liquid crystal aligning film and a board | substrate may not fully appear, and when it exceeds 10 weight part, unreacted [b-2] component will elute in a liquid crystal, and the display characteristic of a liquid crystal display element may be improved. It may worsen.
    Moreover, a higher effect can be acquired by using together the compound 1 which is a [b-1] component and the compound 2 which is a [b-2] component in the liquid crystal aligning agent of this invention.
    Moreover, as an organic solvent which melt | dissolves [a] component and [b] component, if these things can be dissolved, it will not specifically limit, For example, the solvent illustrated as what is used for the synthesis | combination of a polyamic acid is mentioned. Moreover, the poor solvent illustrated as what can be used together at the time of the synthesis reaction of a polyamic acid can also be selected suitably, and can be used together.
    The liquid crystal aligning agent of this invention may contain epoxy group containing compounds other than the compound 2 for the purpose of further improving adhesiveness to a board | substrate. As such an 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, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane , 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, and the like. Among these, compounds having a tertiary nitrogen atom in the molecule are preferable, and the compounding ratio of these epoxy group-containing compounds is usually 40 parts by weight or less, preferably 0.1 to 30 parts by weight based on 100 parts by weight of the component [a].
    <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 one surface of the board | substrate with which the patterned transparent conductive film is provided, for example by methods, such as a roll coater method, a spinner method, a printing method, and then heating a coating surface. Form a film. As a board | substrate here, For example, glass, such as float glass and a soda glass; The transparent substrate which consists of plastics, such as a polyethylene terephthalate, a polybutylene terephthalate, a polyether sulfone, and a polycarbonate, can be used. Examples of the transparent conductive film provided on one side of the substrate include an NESA film made of tin oxide (SnO 2 ) (registered trademark of PPG Co., Ltd.), an ITO film made of indium tin oxide (In 2 O 3 -SnO 2 ), and the like. It can be used, and the photoetching method or the method using a preliminary mask is used for patterning such a transparent conductive film. At the time of coating the liquid crystal aligning agent, a functional silane-containing compound, a functional titanium-containing compound, or the like may be applied to the surface of the substrate in order to further improve the adhesion between the substrate surface and the transparent conductive film and the liquid crystal aligning agent film. . Moreover, heating temperature is 80-250 degreeC, Preferably it is 120-200 degreeC. The film thickness of the formed film is 0.001-1 micrometer normally, Preferably it is 0.005-0.5 micrometer. In addition, the liquid crystal aligning agent of the present invention containing a polyamic acid forms a film to be a liquid crystal alignment film by removing an organic solvent after application, and further heating may proceed to dehydration ring closure to form a partially imidized or fully imidized film. have.
    (2) The rubbing process which rubs the coating film surface formed with the liquid crystal aligning agent in the fixed direction with the roll which wound the cloth which consists of fibers, such as nylon, a rayon, a cotton, for example, is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a film, and it becomes a liquid crystal aligning film. In addition to the method by rubbing treatment, a liquid crystal alignment film may be formed by irradiating polarized ultraviolet rays, ion beams, electron beams, or the like on the surface of the resin film to impart orientation capability, or by obtaining a film by a uniaxial stretching method, a Langmuir broth method, or the like. It may be formed. Moreover, in order to remove the fine powder (foreign substance) which arises at the time of a rubbing process, and to make a surface clean, it is preferable to wash the formed liquid crystal aligning film with isopropylene alcohol etc. Moreover, the process of changing a pretilt angle by partially irradiating an ultraviolet-ray, an ion beam, an electron beam, etc. to the surface of the formed liquid crystal aligning film (for example, Unexamined-Japanese-Patent No. 6-222366, Unexamined-Japanese-Patent No. 6-281937, (See Japanese Patent Application Laid-Open No. 7-168187 and Japanese Patent Laid-Open No. Hei 8-234207), the resist film is partially formed on the surface of the formed liquid crystal alignment film, and the rubbing treatment is performed in a direction different from the preceding rubbing treatment. The viewing angle characteristic of the liquid crystal display element produced can also be improved by removing and changing the orientation ability of a liquid crystal aligning film (for example, refer Unexamined-Japanese-Patent No. 5-107544).
    (3) Two board | substrates with a liquid crystal aligning film were produced as mentioned above, and two board | substrates opposing each other through a gap (cell gap) so that the orientation processing direction, ie, a rubbing direction, in each liquid crystal aligning film may be orthogonal or reverse. It arrange | positions, two peripheral parts of a board | substrate are bonded together, a liquid crystal is injected-filled in the cell gap partitioned by the board | substrate surface and the sealing compound, and an injection hole is sealed and a liquid crystal cell is comprised. And a liquid crystal display by pasting a polarizing plate to the outer surface of a liquid crystal cell, ie, the other surface side of each board | substrate which comprises a liquid crystal cell so that the polarization direction may match or orthogonally cross orthogonally cross the rubbing direction of the liquid crystal aligning film formed in one side of the said board | substrate. The device is obtained.
    As the sealing agent, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used.
    Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable, and for example, a sieve base liquid crystal, a subfamily clock liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal and an ester liquid crystal , Terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, cuban-based liquid crystal and the like can be used. Moreover, cholesteric liquid crystals, such as cholesteryl chloride, cholesteryl nonaate, cholesteryl carbonate, or brand names "C-15", "CB-15" (made by Merck) A chiral agent sold as a compound can also be added and used. Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.
    Moreover, as a polarizing plate which affixes on the outer surface of a liquid crystal cell, the dull polarizing plate which wrapped the polarizing film called H film which absorbed iodine while extending | stretching polyvinyl alcohol, or the polarizing plate which consists of H film itself etc. can be mentioned.
    <Example>
    Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Moreover, the evaluation item and evaluation method of the liquid crystal aligning agent prepared by the following example and the comparative example are shown below.
    [Orientation of Liquid Crystal]
    When voltage was turned on and off in the liquid crystal display element, the presence or absence of an abnormal domain in the liquid crystal cell was observed under a microscope, and the case where there was no abnormal domain was determined as "good".
    Adhesion of Liquid Crystal Alignment Film
    The liquid crystal aligning film obtained after apply | coating a liquid crystal aligning agent to a board | substrate, and drying was mercy in water for 1 hour, and the film | membrane which wiped off the water droplet was evaluated by the board | substrate eye test method according to JISK-5400, and the board | substrate which was not peeled out of 100 checkerboard eyes was evaluated. The adhesion was evaluated by the number of eyes. (Circle) and 90 or less were evaluated for more than 90, (triangle | delta) and less than 70 were evaluated by three steps of x.
    [Surface Smoothness of Coating Film]
    The liquid crystal aligning agent was flexographically printed on a 30 cm square ITO solid substrate using a Nakan printing machine, and then baked at 90 ° C. for 1 minute and then at 180 ° C. for 1 hour to form a liquid crystal alignment film. The average film thickness of the film and the difference (deviation) between the maximum film thickness and the minimum film thickness were measured.
    Synthesis Example 1
    224.17 g (1 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 97.33 g (0.9 mol) of p-pentylenediamine and cholesteryl 3,5-diaminobenzoic acid (compound represented by Formula 20 above) ) 52.08 g (0.1 mol) was dissolved in 2100 g of N-methyl-2-pyrrolidone, and the solution was reacted at 40 ° C for 6 hours. Subsequently, the obtained reaction solution was poured into a large excess of acetone to precipitate the reaction product, the solid was separated, washed with acetone, and dried at 40 ° C. under reduced pressure for 15 hours. 30.0 g of the obtained polymer was dissolved in 570 g of γ-butyrolactone, and 32 g of pyridine and 24 g of acetic anhydride were added to perform a dehydration ring closure reaction at 110 ° C for 4 hours. Thereafter, the reaction product was precipitated, separated, washed, and dried to obtain 27.3 g of polyimide (hereinafter, referred to as "polymer (A)") having a logarithmic viscosity ( Ln) of 1.36 dl / g and an imidation ratio of 95%.
    Synthesis Example 2
    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 mol) of, 3-dione, 91.88 g (0.85 mol) of p-phenylenediamine and 63.36 g (0.15 mol) of the compound represented by the above Formula 24 were dissolved in 1900 g of N-methyl-2-pyrrolidone. The solution was reacted at 20 ° C. for 26 hours. Subsequently, 30.0 g of the polymer obtained by precipitation, separation, washing, and drying of the reaction product was dissolved in 270 g of γ-butyrolactone in the same manner as in Synthesis example 1, 20 g of pyridine and 45 g of acetic anhydride were added to 4 at 80 ° C. Time dehydration ring-closure reaction was performed. Subsequently, polyimide having a logarithmic viscosity (ηln) of 1.06 dl / g and an imidization ratio of 100% (hereinafter referred to as "polymer (B)") was precipitated, separated, washed and dried in the same manner as in Synthesis example 1. 28.3 g was obtained.
    Synthesis Example 3
    In Synthesis Example 2, 91.88 g (0.85 mol) of p-phenylenediamine was changed to 29.75 g (0.15 mol) of 4,4'-diaminodiphenylmethane and 75.67 g (0.7 mol) of p-phenylenediamine. In the same manner as in Synthesis example 2, 25.3 g of polyimide (hereinafter, referred to as "polymer (C)") having an algebraic viscosity (ηln) of 1.0 dl / g and an imidation ratio of 100% was obtained.
    Synthesis Example 4
    109.05 g (0.5 mol) of pyromellitic dianhydride, 98.05 g (0.5 mol) of cyclobutanetetracarboxylic anhydride and 198.27 g (1 mol) of 4,4'-diaminodiphenylmethane are N-methyl-2-pi It dissolved in 1600 g of ralidone, and this solution was made to react at 20 degreeC for 6 hours. Subsequently, 400.3 g of polyamic acid (hereinafter referred to as "polymer (D)") having a logarithmic viscosity (ηln) of 1.8 dl / g was obtained by precipitation, separation, washing and drying of the reaction product in the same manner as in Synthesis example 1.
    Synthesis Example 5
    224.17 g (1 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride and 432.5 g (1 mol) of bis [4- (4-aminophenoxy) phenyl] sulfone are dissolved in 6000 g of γ-butyrolactone The solution was reacted at 60 ° C. for 6 hours. Then, 650 g of polyamic acid (hereinafter referred to as "polymer (E)") having a logarithmic viscosity (ηln) of 1.5 dl / g was obtained by precipitation, separation, washing and drying of the reaction product in the same manner as in Synthesis example 1.
    Synthesis Example 6
    Synthesis example, except that 91.88 g (0.85 mol) of p-phenylenediamine was changed to 86.47 g (0.8 mol) of p-phenylenediamine and 19.09 g (0.05 mol) of 3-aminopropylmethyldiethoxysilane. In the same manner as in 2, 25 g of polyimide (hereinafter, referred to as "polymer (F)") having an algebraic viscosity (ηln) of 0.94 dl / g and an imidization ratio of 100% was obtained. When gas chromatography was used to examine the amount of unreacted 3-aminopropylmethyldiethoxysilane, it was not detected, and it was confirmed that 3-aminopropylmethyldiethoxysilane was in a chemically bonded state in the polymer.
    Synthesis Example 7
    In Synthesis Example 4, 198.27 g (1 mol) of 4,4'-diaminodiphenylmethane, 190.41 g (0.95 mol) of 4,4'-diaminodiphenylmethane, and 19.31 g (0.05) of 3-aminopropylmethyldiethoxysilane 410 g of polyamic acid (hereinafter, referred to as "polymer (G)") having a logarithmic viscosity (ηln) of 2.0 dl / g was obtained in the same manner as in Synthesis example 4 except for changing to mole). When gas chromatography was used to examine the amount of unreacted 3-aminopropylmethyldiethoxysilane, it was not detected, and it was confirmed that 3-aminopropylmethyldiethoxysilane was in a chemically bonded state in the polymer.
    Synthesis Example 8
    To the mixed solution of 10 g of γ-butyrolactone and 13.7 g of butyl cellosolve, 0.2 g of triethylamine was added, and the mixed solution was heated to reflux for 6 hours. Unreacted γ-butyrolactone, butyl cellosolve and triethylamine were distilled off under reduced pressure to obtain 3 g of a compound represented by the following formula (1a). The 1 H NMR chart (solvent: CDCl 3 ) of the obtained compound is shown in FIG. 1.
    <Example 1>
    100 parts by weight of the polymer (A) obtained in Synthesis Example 1, 1 part by weight of the compound represented by Formula 1a and 1 part by weight of 3-glycidoxypropylmethyldiethoxysilane were dissolved in γ-butyrolactone. It was made into the solution of 4 weight% of solid content concentration, and this solution was filtered through the filter of 1 micrometer of pore diameters, and the liquid crystal aligning agent was prepared.
    The said liquid crystal aligning agent was apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane using the printing machine for liquid crystal aligning film application | coating, dried for 20 minutes on a 180 degreeC hotplate, and the film of 900Å of dry average film thickness Formed. The difference between the maximum film thickness and the minimum film thickness was 150 mm 3, and the evaluation of adhesion was ○.
    The rubbing process was performed by the rubbing machine which has the roll which wound the cloth made from rayon to this film at the rotation speed of 500 rpm of the roll, the movement speed of 1 cm / sec of a stage, and 0.4 mm of hair indentation lengths. After immersing the said oriented film coating board | substrate in isopropylene alcohol for 1 minute, both board | substrates were dried for 5 minutes on a 100 degreeC hotplate.
    Subsequently, after screen-printing and apply | coating the epoxy resin adhesive which contained the 5.5-micrometer diameter aluminum oxide sphere to each outer edge part which has a liquid crystal aligning film of a pair of rubbing process liquid crystal aligning substrate, liquid crystal aligning film surface mutually The adhesive was cured by overlapping and compressing the rubbing directions so as to face each other.
    Subsequently, after filling a nematic liquid crystal (MLC-5081 by Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal inlet, the liquid crystal inlet is sealed with an acryl-type photocuring adhesive, and the polarizing direction of the polarizing plate has a polarizing plate on both outer sides of a board | substrate. The liquid crystal display element was produced by sticking together so that it may correspond with the rubbing direction of the liquid crystal aligning film of a board | substrate, respectively. When the liquid-crystal orientation of the obtained liquid crystal display element was evaluated, the orientation of the liquid crystal was favorable. These results are shown in Table 1.
    <Examples 2 to 12, Comparative Examples 1 to 2>
    According to the prescription shown in Table 1, the liquid crystal aligning agent was prepared like Example 1 using the polymer and the additive obtained by the synthesis examples 1-7. Next, the liquid crystal display element was produced like Example 1 using the liquid crystal aligning agent obtained in this way. About each of the obtained liquid crystal aligning agent and a liquid crystal display element, the orientation, adhesiveness of the liquid crystal, the film thickness of the alignment film, and the deviation were evaluated. The results are shown in FIG.
    Polymer (% by weight)Compound (i)Compound (ii)Other additives KindsAmountKindsAmountKindsAmount Example 1A (100)i-1Oneii-1One-- Example 2B (100)i-1Oneii-1One-- Example 3C (100)i-1Oneii-1One-- Example 4D (100)--ii-1Oneiii-120 Example 5F (100)i-10.5---- Example 6G (100)i-1Oneii-2One-- Example 7D (100)i-1Oneii-1Oneiii-120 Example 8B (20) D (80)i-1Oneii-1Oneiii-120 Example 9B (20) G (80)i-1One---- Example 10B (20) C (80)--ii-1One-- Example 11B (20) E (80)--ii-2One-- Example 12F (15) G (85)i-1One--iii-120 Comparative Example 1A (100)------ Comparative Example 2A (100)----iii-120
    Surface smoothnessAdhesionOrientation Average film thicknessDeviationCenterPeriphery Example 1900150○GoodGood Example 284080○GoodGood Example 380040○GoodGood Example 480080○GoodGood Example 580050○GoodGood Example 670050○GoodGood Example 7770100○GoodGood Example 8770100○GoodGood Example 9600100○GoodGood Example 10770100○GoodGood Example 11880120○GoodGood Example 1280080○GoodGood Comparative Example 1870280×GoodHas domain Comparative Example 2880200○GoodHas domain * The unit of addition amount is weight part.
    In the said Table 1, each additive is as follows.
    (Vi-1) a compound represented by Formula 1a
    (Ii-1) 3-glycidoxypropylmethyldiethoxysilane
    (Ii-2) N-glycidyl-N, N-bis [3-methyldimethoxysilyl) propyl] amine
    (X-1) N, N, N'N'- tetraglycidyl-4,4'- diaminodiphenylmethane
    According to the liquid crystal aligning agent of this invention, when made into a liquid crystal display element, since the smoothness and adhesiveness of the formed alignment film are excellent, it is hard to be influenced by adsorption ion. For this reason, the liquid crystal display element which does not have orientation defect can be obtained.
    The liquid crystal display element having the liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention can be suitably used for TN type and STN type liquid crystal display elements, and by selecting a liquid crystal to be used, a SH (Super Homeotropic) type and an IPS (In -Plane Switching) type, ferroelectric and antiferroelectric liquid crystal display elements can be suitably used.
    Moreover, the liquid crystal display element which has the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention can be used effectively for various apparatuses, For example, a desk calculator, a wristwatch, a table clock, a coefficient display board, a word processor, a personal computer And a display device such as a liquid crystal TV.
    权利要求:
    Claims (2)
    [1" claim-type="Currently amended] [a] at least one polymer selected from polyamic acid and an imidized polymer of polyamic acid,
    [b-1] A liquid crystal aligning agent containing a compound represented by the following formula (1).
    <Formula 1>

    (In the formulas, A 1 to A 11 each independently represent an alkyl group or a hydrogen atom.)
    [2" claim-type="Currently amended] [a] at least one polymer selected from polyamic acid and an imidized polymer of polyamic acid,
    [b-2] A liquid crystal aligning agent containing a compound having a structure represented by the following formula (2) and / or a polymer.
    <Formula 2>

    (In the above formula, A 12 to A 14 each independently represent an alkyl group or a hydrogen atom.)
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    同族专利:
    公开号 | 公开日
    JP2980080B2|1999-11-22|
    JPH11119226A|1999-04-30|
    KR100560594B1|2006-05-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-10-09|Priority to JP29353897A
    1997-10-09|Priority to JP97-293538
    1998-10-08|Application filed by 마쯔모또 에이찌, 제이에스알 가부시끼가이샤
    1999-05-25|Publication of KR19990036935A
    2000-05-18|First worldwide family litigation filed
    2006-05-25|Application granted
    2006-05-25|Publication of KR100560594B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP29353897A|JP2980080B2|1997-10-09|1997-10-09|Liquid crystal alignment agent|
    JP97-293538|1997-10-09|
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