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    • 专利摘要:
    A method for producing a liquid crystal aligning film is disclosed in which an ion beam is irradiated to an organic thin film containing a soluble polyimide polymer having an alicyclic structure formed on a substrate. The liquid crystal display element which has the liquid crystal aligning film manufactured by this invention can be used effectively for various apparatuses, For example, display apparatuses, such as a table calculator, a wristwatch, a table clock, a coefficient display board, a word processor, a personal computer, a liquid crystal television, etc. Can be used for
    公开号:KR19990062726A
    申请号:KR1019980052551
    申请日:1998-12-02
    公开日:1999-07-26
    发明作者:야스오 마쯔끼；야스아끼 무쯔가；교유 야스다
    申请人:마쯔모또 에이찌；제이에스알 가부시끼가이샤；
    IPC主号:
    专利说明:

    Manufacturing method of liquid crystal aligning film
    This invention relates to the manufacturing method of the liquid crystal aligning film of a liquid crystal display element. More specifically, the present invention relates to a method for producing a liquid crystal alignment film having a good liquid crystal alignment property and having a good alignment state even after long time driving and hardly causing an afterimage phenomenon.
    Conventionally, a layer of nematic liquid crystal having positive dielectric anisotropy is formed between two substrates on which a liquid crystal alignment film is formed on the surface through 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 TN (Twisted Nematic) type liquid crystal cells which are twisted 90 degrees continuously toward the substrate are known. Orientation of the liquid crystal in liquid crystal display elements, such as this TN type liquid crystal display element, is normally implement | achieved by the liquid crystal aligning film to which the orientation ability of the liquid crystal molecule was provided by the rubbing process. Resin, such as a polyimide, a polyamide, and polyester, is known conventionally as a material of the liquid crystal aligning film which comprises a liquid crystal display element here. 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 high-precision fine liquid crystal display device, there is a limit in removing dust in the rubbing treatment process and rubbing the display surface uniformly in the large liquid crystal display device, which causes various display failure problems. As an orientation treatment method to be substituted for rubbing, the alignment film is irradiated with a deflection ultraviolet ray as disclosed in Japanese Patent No. 260,866 or an ion beam as disclosed in Japanese Patent Application Laid-Open No. 94-130,391 or the like. It is proposed how to. However, the alignment treatment method using polarized ultraviolet rays has a problem that the alignment state is easily relaxed by heat.
    On the other hand, the ion beam method is a method of colliding the accelerated ions with the organic film, and acts on the organic film to cause ions that cause deterioration of the afterimage property, thereby causing a problem in the afterimage property and the surface change caused by ion beam irradiation. There also exists a problem that orientation defects generate locally. As an aligning agent effective for the ion beam method, although it is proposed in Unexamined-Japanese-Patent No. 96-313,912, 96-313,913, and 96-313,916, it is insufficient to solve the said problem. In addition, such an already proposed alignment agent requires a baking process at a high temperature and there is a problem in that the heat resistance of the substrate occurs.
    An object of the present invention is to provide a method for producing a liquid crystal aligning film provided with a stable alignment ability at the same level as a rubbing treatment, not by a rubbing treatment.
    Another object of the present invention is to provide a method for producing a liquid crystal alignment film having good display characteristics such as an alignment film and afterimage characteristics of liquid crystal molecules.
    Another object of the present invention is to provide a method for producing a liquid crystal alignment film that can be obtained by firing at a low temperature regardless of the heat resistance of the substrate.
    Still other objects and advantages of the present invention will become apparent from the following description.
    According to the present invention, the above objects and advantages of the present invention are achieved by a method for producing a liquid crystal alignment film characterized by irradiating an ion beam to an organic thin film containing a soluble polyimide having an alicyclic structure formed on a substrate.
    The principle of the alignment treatment by the ion beam is thought to be that fine grooves are formed on the alignment film by irradiating the ion beams on the alignment film, and the liquid crystal molecules are oriented under three-dimensional restrictions depending on the angle and direction of the grooves. Therefore, the characteristic required for the alignment film is that 1) is easily etched by the ion beam. ② The groove formed is not deformed, that is, the molecular chain is difficult to move due to external stimulation such as heat.
    In the present invention, as a result of intensive studies in consideration of the above-described required characteristics, it has been found that the polyimide having an alicyclic structure satisfies this demand, and has reached the present invention.
    EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.
    The liquid crystal aligning agent used for this invention may mix and use 2 or more types of polymers. Among these, it is preferable to contain the soluble polyimide which has alicyclic structure, or the imide structural unit which has alicyclic structure at least 10 weight% or more in solid content of a liquid crystal aligning agent, More preferably, it is 20 weight% or more. If it is less than 10 weight%, it is difficult to achieve the objective performance (especially low temperature baking) of this invention.
    The manufacturing method of the soluble polyimide which can be used for this invention is demonstrated.
    The soluble polyimide used in the present invention can be obtained by reacting a tetracarboxylic dianhydride and a diamine compound in an organic solvent to synthesize a polyamic acid, and further dehydrating and closing the polyamic acid as necessary.
    At least one of such a tetracarboxylic dianhydride and a diamine compound is preferably used, in which an acid anhydride group is directly bonded to an alicyclic structure to tetracarboxylic dianhydride.
    Tetracarboxylic dianhydride
    Examples of the tetracarboxylic dianhydride in which the acid anhydride group is directly bonded to the alicyclic structure include 1,2,3,4-cyclobutanetetracarboxylic 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, 2,3,5-tricarboxycyclopentylacetic acid Dianhydrides, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydrides, 2,3,4,5-tetrahydrofurantetetracarboxylic dianhydrides, 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- (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, vehicle [2,2,2] - loam-7-ene-2,3,5,6-tetracarboxylic acid dianhydride to, and the like can be mentioned compounds represented by the formulas (1) and (2).

    In the formula,
    R 1 and R 3 represent a divalent organic group having an aromatic ring,
    R <2> and R <4> represents a hydrogen atom or an alkyl group, and two or more R <2> and R <4> may be same or different, respectively.
    Of these, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-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-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, 1,2, , 3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-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-5-methyl-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3- Dione is particularly preferred.
    Examples of the tetracarboxylic dianhydride in which the acid anhydride group is not directly bonded in an alicyclic structure include 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'-tetraphenylsilanetetra Carboxylic acid dianhydride, 1,2,3,4-furtetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'- Bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-purple Luoroisopropylidenediphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride Water, 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 (anhydrotrimellitate), propylene glycol-bis (anhydro trimellitate) , 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2, 2-bis (4-hydroxyphenyl) propane-bis (anhydro trimellitate), the compound represented by following formula (3)-6, etc. are mentioned.


    [Diamine Compound]
    Examples of the amine compound in which the amino group is directly bonded to the alicyclic structure include 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, and hexahydro-4,7-methanoindanylenedimethylene. Diamine, tricyclo [6.2.1.0 2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine), and the like.
    Examples of the compound in which the amino group is not directly bonded in an alicyclic structure include 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-aminophenoxy) phenyl] sulfone, 1,4-bis ( 4-aminophenoxy) benzene, 1,3-bis (4-a Minophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9- (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'-bis [(4-amino-2-trifluoromethyl) phenoxy Aromatic diamines such as] -octafluorobiphenyl;
    1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine Aliphatic diamines such as;
    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 in the molecule, such as 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, and a compound represented by the following formula (7) or (8) Primary amino group and a diamine having a nitrogen atom other than the primary amino group;
    (Wherein R 5 represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X represents a divalent organic group.)
    (Wherein R 6 represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, X represents a divalent organic group, and a plurality of X may be the same or different.)
    Mono-substituted phenylenediamines represented by the following formula (9); Diaminoorganosiloxane represented by the following formula (10);
    (Wherein R 7 represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH- and -CO-, R 8 represents a steroid skeleton, a trifluoromethyl group and Monovalent organic group or group having 6 to 30 carbon atoms having a group selected from fluoro groups.)
    (In formula, R <9> represents a C1-C12 hydrocarbon group, two or more R <9> may be same or different, respectively, p is an integer of 1-3, q is an integer of 1-20.)
    And compounds represented by the following formulas (11) to (23). These diamine compounds can be used individually or in combination of 2 or more types.


    (In formula, y is an integer of 2-12, z is an integer of 1-5.)




    Among them, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, tricyclo [6.2.1.0 2,7 ]- Undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, p-phenylenediamine, 4,4 '-Diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis [4- (4-aminophenoxy ) Phenyl] propane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 9,9 -Bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminoolefin, 9,9-bis (4-aminophenyl) fluorene, 3,3'-dimethoxy-4,4'-dia Minobiphenyl, 1,4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 1,1-methaxylylenediamine, 1,3- Ropandiamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, and the compounds represented by the above formulas 11 to 23 are preferable. .
    [Synthesis of Polyamic Acid]
    Polyamic acid is manufactured by making tetracarboxylic dianhydride and a diamine compound react. At this time, at least one of the tetracarboxylic dianhydride and the diamine compound needs to contain a compound in which an acid anhydride group is directly bonded to an alicyclic structure.
    That is, as the aspect
    (Iii) The tetracarboxylic dianhydride contains tetracarboxylic dianhydride in which at least an acid anhydride group is directly bonded in an alicyclic structure. For example, tetracarboxylic dianhydride consists only of tetracarboxylic dianhydride in which an acid anhydride group is directly bonded in an alicyclic structure, or tetracarboxylic acid in which it and an acid anhydride group are not directly bonded in an alicyclic structure. Combination with dianhydrides.
    (Ii) The diamine compound contains a diamine compound in which at least an amino group is directly bonded to an alicyclic structure. For example, the diamine compound consists only of the diamine compound in which the amino group was directly bonded by the alicyclic structure, or the combination of the diamine compound and the diamine compound in which the amino group was not directly bonded by the alicyclic structure.
    The use ratio of the tetracarboxylic dianhydride and the diamine compound used in the synthesis reaction of the polyamic acid is preferably a ratio in which the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents to 1 equivalent of the amino group contained in the diamine compound. More preferably, it is the ratio which becomes 0.3 to 1.2 equivalent.
    The synthesis reaction of the polyamic acid is usually carried out in an organic solvent under a temperature condition of -20 to 150 ° C, preferably 0 to 100 ° C. The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl Aprotic polar solvents such as sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphoryltriamide; Phenol solvents, such as m-clesol, xylenol, a phenol, and a halogenated phenol, can be illustrated. In addition, the amount of the organic solvent (a) is preferably preferably an amount such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution.
    In addition, the organic solvent may be used in combination with the polyamic acid, which is a poor solvent of the polyamic acid, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are 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, ethylene glycol monomethyl ether, ethyl lactate, lactic acid Butyl, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonic acid, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol- i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, 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, Tra may be mentioned tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloro butane, as trichloroethane, chlorobenzene, o- dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.
    As described above, a reaction solution in which the polyamic acid is dissolved is obtained. The reaction solution is poured into 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.
    Synthesis of Polyimide
    Soluble polyimide used in the present invention can be produced by dehydrating and closing the polyamic acid. The dehydration ring closure of the polyamic acid is accomplished by (i) heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating it as necessary. . Moreover, the polyimide which partially dehydrated ring-reacting can also be used suitably for the liquid crystal aligning agent of this invention.
    The reaction temperature in the method of heating the polyamic acid of said (iii) is 50-200 degreeC normally, Preferably it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring | close ring does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the polyimide 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 polyamic acid of said (ii), acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoro acetic 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, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to these. 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 polyamic acid is mentioned as an organic solvent used for dehydration ring-closure reaction. In addition, the reaction temperature of a dehydration ring-closure reaction is 0-180 degreeC normally, Preferably it is 60-150 degreeC. Moreover, polyimide can be refine | purified by performing operation similar to the purification method of polyamic acid with respect to the reaction solution obtained in this way.
    [Synthesis of Terminal Linked Polymer]
    The polymer which comprises the liquid crystal aligning agent used for this invention may be the terminal connection type of which the molecular weight was controlled. By using this terminal-linked polymer, the effect of this invention is not impaired and the coating property of a liquid crystal aligning agent, etc. can be improved. Such a terminally linked polymer can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound and 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. have. 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, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyl Dimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, p- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane, N, N-bis [3- (trimethoxysilyl) propyl] Ethylene diamine, N-3- trimethoxysilylpropyl can and the like -m- phenylenediamine. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, 3-isocyanate propyl triethoxysilane, etc. are mentioned, for example.
    [Logarithmic Viscosity of Polymer]
    The value of the logarithmic viscosity ((eta) ln) of the polymer which comprises the liquid crystal aligning agent used for this invention becomes like this. Preferably it is 0.05-10 dl / g, More preferably, it is 0.05-5 dl / g. Here, the logarithmic viscosity (ηln) value is represented by the following equation by measuring the viscosity at 30 ° C for a solution having N-methyl-2-pyrrolidone as a solvent and a polymer concentration of 0.5 g / 100 milliliter. It is obtained by the formula.
    [Liquid crystal aligning agent]
    The polymer content in the liquid crystal aligning agent used in the present invention is selected in consideration of viscosity, volatility, etc., preferably in the range of 0.1 to 20% by weight, more preferably 1 to 10% by weight based on the entire liquid crystal aligning agent to be. That is, the liquid crystal aligning agent which consists of a polymer solution is apply | coated to the surface of a board | substrate by the printing method, the rotation coating method, etc., and then this is dried and the film which is an oriented film material is formed, but when the content rate of a polymer is less than 0.1 weight%, the film of this film When the thickness becomes too small, a good liquid crystal aligning film may not be obtained, and when it exceeds 20 weight%, the film thickness of a film will become excessive and it will be difficult to obtain a good liquid crystal aligning film, and the viscosity of a liquid crystal aligning agent will increase and coating property will fall. There is a case.
    In addition, the liquid crystal aligning agent used in the present invention is characterized by containing a soluble polyimide having an alicyclic structure as a polymer, and may be used by mixing a polyamic acid and / or a polyimide of another structure. Especially, when the polyamic acid and polyimide are mixed and used, the afterimage characteristic of the liquid crystal display element obtained becomes especially favorable, and it is preferable.
    The organic solvent that dissolves the polymer is not particularly limited as long as it can dissolve the polymer, and examples thereof include solvents exemplified as those used in the polyamic acid synthesis reaction or dehydration ring closure reaction. 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 functional silane containing compound or epoxy compound may be mix | blended from a viewpoint of further improving the adhesiveness of a polymer and the board | substrate surface apply | coated for the liquid crystal aligning agent used for this invention. 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-ureidopropyltrimethoxysilane, 3-ureidopropyltree Ethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N- Trimethoxysilylpropyltriethylenetriamine, 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 -Benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyl triethoxysilane, 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 diglyci Dil 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-diglycid Dylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimeth A methoxysilane, 3- (N, N- diglycidyl) aminopropyl trimethoxysilane, etc. are mentioned as a preferable thing, Among these, the compound which has a tertiary nitrogen atom in a molecule | numerator is preferable. The. The compounding ratio of such a compound is usually 40 parts by weight or less, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer.
    [Manufacture of Liquid Crystal Display Element]
    The liquid crystal display element obtained using the liquid crystal aligning agent in this invention can be manufactured, for example by the following method.
    (1) The liquid crystal aligning agent is apply | coated to the transparent conductive film side of the board | substrate with which the patterned transparent conductive film was provided, for example by methods, such as a roll coater method, a spinner method, and a printing method, and a film is formed by heating a coating surface next. 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 side of the substrate, an NESA film made of SnO 2 , an ITO film made of In 2 O 3 -SnO 2 , and the like can be used. For the patterning of the transparent conductive film, a photoetching method and a preliminary mask are used. Method and the like.
    At the time of application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate and a transparent conductive film and a coating film further favorable, you may apply a functional silane containing compound, titanate, etc. on a board | substrate and a transparent conductive film beforehand. Moreover, heating temperature becomes like this. Preferably it is 80-250 degreeC, More preferably, it is 120-250 degreeC. The film thickness of the coating film formed is normally 0.001-1 micrometer, Preferably it is 0.005-0.5 micrometer.
    The formed film is irradiated with an ion beam on the surface of the film to impart the alignment ability of the liquid crystal molecules to the film, thereby forming a liquid crystal alignment film. As an ion type of an ion beam, it is preferable to use the ion beam of inert gas, such as nitrogen, helium, argon, and neon. It is also preferable to supply electrons for ion neutralization during or after ion beam irradiation.
    Irradiation of an ion beam can be performed in the direction which the angle from a board | substrate becomes 10-80 degree | times with respect to the film on a board | substrate, for example. In that case, as acceleration voltage of an ion beam, it can be set to 50-500V, for example. The irradiation time depends on the acceleration voltage or the film thickness, but is usually about 1 to 60 seconds is sufficient.
    Moreover, it is disclosed by Unexamined-Japanese-Patent No. 96-234207, 95-168187, 94-222366, or 94-281937 to the liquid crystal aligning film formed by the said process, for example. A process of changing the pretilt angle by partially irradiating an ultraviolet ray, an ion beam, or an electron beam as present, or partially forming a resist film on the alignment-treated liquid crystal alignment film disclosed in Japanese Patent Application Laid-Open No. 93-107544 After performing the alignment treatment in a direction different from the preceding liquid crystal alignment direction, it is possible to improve the field of view characteristics of the liquid crystal display element by performing the treatment of removing the resist film and changing the alignment capability of the liquid crystal alignment film.
    (3) The two substrates in which the liquid crystal alignment film was formed as described above were prepared, and the two substrates were opposed to each other so that the direction of the pretilt angle in each liquid crystal alignment film was perpendicular or antiparallel through the gap. The periphery of two board | substrates is bonded together using a sealing agent, a liquid crystal is filled in the clearance gap partitioned by the surface of a board | substrate and a sealing agent, and a filling hole is sealed and a liquid crystal cell is comprised. And attaching the polarizing plate to the outer surface of the liquid crystal cell, that is, the outer surface side of each substrate constituting the liquid crystal cell, so that the polarization direction is coincident with or perpendicular to the liquid crystal alignment direction of the liquid crystal alignment film formed on one side of the substrate. Obtained.
    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, a smectic liquid crystal, etc. are mentioned, for example. Especially, a nematic liquid crystal is preferable, for example, a Schiff base type liquid crystal, a subfamily clock liquid crystal, a biphenyl type liquid crystal, a phenylcyclohexane type liquid crystal, an ester type liquid crystal, a terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimi Din type liquid crystals, dioxane type liquid crystals, bicyclooctane type liquid crystals, cuban type liquid crystals, etc. can be used. Moreover, it is sold to such liquid crystal as cholesteric liquid crystals, such as a cholesteryl chloride, a cholesteryl nonaate, a cholesteryl carbonate, or brand names "C-15", "CB-15" (the Merck company make), for example. The chiral agent etc. which were present 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 used on the outer side of a liquid crystal cell, the polarizing plate etc. which made the polarizing film called H film | membrane which absorbed iodine while extending | stretching polyvinyl alcohol between the cellulose acetate protective film, or the polarizing plate which consists of H film itself etc. are 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.
    The evaluation method of each liquid crystal display element manufactured by the following example and the comparative example is shown below.
    [Orientation of Liquid Crystal]
    When the voltage was turned on / 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 it was judged that it was good. Immediately after the preparation of the liquid crystal display device, the device was irradiated at two time points after being stored in an oven at 100 ° C. for one week.
    Afterimage erasing time of liquid crystal display element
    After applying DC voltage 5V to a liquid crystal display element for 24 hours, voltage was turned OFF and time until the afterimage was eliminated visually was measured.
    [Voltage retention rate of liquid crystal display element]
    After applying the voltage of 5 V to the liquid crystal display element for 60 microseconds application time and 500 milliseconds, the voltage retention after 500 milliseconds after application | release cancellation was measured. The measurement apparatus was performed at 60 degreeC using VHR-1 by Toyo Technica Corporation.
    [Pretilt Angle of Liquid Crystal Display Element]
    T. J. Schffer, et. Al., J. Appl. Phys., Vol. 19, 2013 (1980)] was measured by the crystal rotation method using a He-Ne laser light.
    Synthesis Example 1
    224.17 g (1.00 mol) of 2,3,5-tricarboxycyclopentylacetic dianhydride, 97.33 g (0.90 mol) of p-phenylenediamine and 52.08 g of 3,5-diaminobenzoic acid cholesteryl represented by the above formula (19) (0.10 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. 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 dehydrate and close the ring at 110 ° C for 4 hours. Subsequently, 27.3 g of the soluble polyimide polymer (A) having a logarithmic viscosity (ηln) of 1.36 dl / g and an imidation ratio of 95% were obtained by precipitation, separation, washing and drying of the reaction product.
    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 mole) of 3-dione, 91.88 g (0.85 mole) of p-phenylenediamine and 63.36 g (0.15 mole) of the compound represented by Formula 22 were dissolved in 1900 g of N-methyl-2-pyrrolidone. And this solution was made to react at 20 degreeC for 26 hours. Subsequently, the obtained reaction solution was poured into a large excess of acetone to precipitate the reaction product. 30.0 g of the obtained polymer was dissolved in 270 g of γ-butyrolactone, and 20 g of pyridine and 45 g of acetic anhydride were added to dehydrate and close the ring at 80 ° C for 4 hours. Subsequently, 28.3 g of soluble polyimide polymers (B) having a logarithmic viscosity (ηln) of 1.06 dl / g and an imidization ratio of 100% were obtained by precipitation, separation, washing and drying of the reaction product.
    Synthesis Example 3
    The raw materials used in the synthesis were 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] furan-1,3-dione 314.30 g (1 mol), 4,4'-diaminodiphenylmethane 29.75 g (0.15 mol), p-phenylenediamine 75.67 g (0.70 mol) and represented by formula 22 The reaction was carried out in the same manner as in Synthesis Example 2, except that 63.36 g (0.15 mol) of the compound was used to obtain 25.3 g of a soluble polyimide polymer (C) having a logarithmic viscosity (ηln) of 1.0 dl / g and an imidization ratio of 100%. .
    Synthesis Example 4
    218.1 g (1 mol) of pyromellitic dianhydride and 198.27 g (1.00 mol) of 4,4'-diaminodiphenylmethane are dissolved in 1600 g of N-methyl-2-pyrrolidone and the solution is dissolved at 20 ° C. The reaction was carried out for 6 hours. Subsequently, the obtained reaction solution was poured into a large excess of acetone, and the reaction product was precipitated, separated, washed and dried to obtain 400.3 g of a polyamic acid polymer (D) having a logarithmic viscosity (ηln) of 1.8 dl / g.
    Synthesis Example 5
    224.17 g (1.00 mol) of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 432.5 g (1.00 mol) of bis [4- (4-aminophenoxy) phenyl] sulfone were dissolved in 6000 g of γ-butyrolactone. The solution was reacted at 60 ° C. for 6 hours. Subsequently, the obtained reaction solution was poured into a large excess of acetone, and the reaction product was precipitated, separated, washed and dried to obtain 650 g of a polyamic acid polymer (E) having a logarithmic viscosity (ηln) of 1.5 dl / g.
    Synthesis Example 6
    The raw materials used in the synthesis were 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] furan-1,3-dione 314.30 g (1 mol), 86.47 g (0.8 mol) p-phenylenediamine and 63.33 g (0.15 mol) of the compound represented by the formula (22), 3-aminopropylmethyldiethoxysilane The reaction was carried out in the same manner as in Synthesis example 2, except that the concentration was 19.09 g (0.05 mol) to obtain 25 g of a soluble polyimide polymer (F) having a logarithmic viscosity (ηln) of 0.94 dl / g and an imidization ratio of 100%.
    Synthesis Example 7
    The raw materials used for the synthesis are changed to 109.14 g of pyromellitic dianhydride, 98.14 g of cyclobutanetetracarboxylic anhydride, 190.41 g of 4,4'-diaminodiphenylmethane, and 19.31 g of 3-aminopropylmethyldiethoxysilane. The reaction was carried out in the same manner as in Synthesis example 4, except that 25 g of polymer (B) having a logarithmic viscosity (ηln) of 0.94 dl / g was obtained. By drying, 410 g of polyamic-acid polymers (G) of logarithmic viscosity ((eta) ln) 1.6 dl / g were obtained.
    Synthesis Example 8
    50 g of the polymer (E) was dissolved in 900 g of γ-butyrolactone, and 30 g of pyridine and 23 g of acetic anhydride were added to dehydrate and close the ring at 110 ° C for 4 hours. Subsequently, precipitation, separation, washing and drying of the reaction product yielded 48.3 g of a soluble polyimide polymer (H) having a logarithmic viscosity (ηln) of 1.3 dl / g and an imidization ratio of 98%.
    Synthesis Example 9
    257 g of 2,3,5-tricarboxycyclopentyl acetic dianhydride, 93 g of p-phenylenediamine and 150 g of the compound represented by the formula (18) were dissolved in 2800 g of N-methyl-2-pyrrolidone, The solution was reacted at 60 ° C for 6 hours. Subsequently, the obtained reaction solution was poured into a large excess of acetone to precipitate the reaction product. 30.0 g of the obtained polymer was dissolved in 400 g of γ-butyrolactone, and 17 g of pyridine and 11 g of acetic anhydride were added to dehydrate and close the ring at 110 ° C for 4 hours. Subsequently, the reaction product was precipitated, separated, washed and dried to obtain 28.3 g of a soluble polyimide polymer (I) having a logarithmic viscosity (ηln) of 1.06 dl / g and an imidation ratio of 80%.
    Example 1
    Polymer A was dissolved in γ-butyrolactone to obtain a solution having a solid content of 4% by weight, and the solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent. This liquid crystal aligning agent was apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which used the ITO film | membrane using the printing machine for liquid crystal aligning film application, and it dried for 20 minutes on a 180 degreeC hotplate, and it has a dry average film thickness of 900 angstrom A film was formed.
    The film was irradiated with an argon ion beam for 10 seconds at an acceleration voltage of 200 V in the direction in which the angle from the substrate was 40 °.
    Subsequently, after screen-printing apply | coating the epoxy resin adhesive which contains 5.5 micrometers in diameter aluminum oxide spheres to each outer edge part which has a liquid crystal aligning film of a pair of alignment-treated liquid crystal aligning substrate, a pair of liquid crystal aligning substrate was carried out on the liquid crystal aligning film surface The adhesive was cured by overlapping and compressing so as to face each other and the ion beam irradiation direction was orthogonal.
    Subsequently, the nematic liquid crystal (MLC-5081, manufactured by Merck Co., Ltd.) was filled between the pair of substrates at an adhesive inlet, and then the liquid crystal inlet was sealed with an acrylic photocuring adhesive, and the polarizing plates were placed on both sides of the substrate outside. The fragrance was stuck together so that the direction might correspond to the ion beam irradiation direction of the liquid crystal aligning film of each board | substrate, and the liquid crystal display element was produced.
    When the liquid crystal aligning property, the pretilt angle, the voltage retention, and the afterimage erasing of the obtained liquid crystal display element were evaluated, the liquid crystal alignability was all favorable after initial stage and high temperature storage, and the afterimage erasing time was a small value as 1 minute. These results are shown in Table 1.
    Examples 2 to 10, Comparative Examples 1 to 3
    According to the prescription shown in Table 1 below, the alignment treatment was performed in the same manner as in Example 1 except that the liquid crystal aligning agent using the polymers and additives obtained in Synthesis Examples 1 to 8 were adjusted and the liquid crystal was changed to MLC-2012 in Example 7. Then, a liquid crystal display device was manufactured in the same manner as in Example 1. Each of the obtained liquid crystal display elements was evaluated for the orientation of liquid crystal, the afterimage erasing time, and the like. The results are shown in Table 1 below.
    polymerFiring temperature (℃)Film hardnessOrientation (initial)Pretilt angle (°)Voltage retention rate (%)Orientation (After High Temperature Treatment)Afterimage elimination time (minutes) Example 1Polymer A180BGood497Good6 Example 2Polymer A120BGood496Good6.5 Example 3Polymer B120HBGood697Good6 Example 4Polymer C120BGood397Good8 Example 5Polymer F120HGood697Good7 Example 6Polymer H120BGood598Good6 Example 7Polymer I120BGood9098Good4 Example 8Polymer B (30%) Polymer D (70%)1802HGood498GoodOne Example 9Polymer B (30%) Polymer E (70%)120HBGood597Good2 Example 10Polymer B (30%) Polymer G (70%)1802HGood498GoodOne Comparative Example 1Polymer D180HGood283No orientation- Comparative Example 2Polymer D120HBWith flow orientation270No orientation- Comparative Example 3Polymer D2502HGood288With orientation domain20
    ADVANTAGE OF THE INVENTION According to this invention, the orientation defect and afterimage characteristic which were conventionally a problem in the orientation processing by the ion beam method can be improved. Therefore, it becomes possible to manufacture a liquid crystal display element under the simple and clean conditions replaced with the conventional rubbing method, and the problem of the yield fall by rubbing dust is eliminated completely.
    Since the liquid crystal display device having the liquid crystal alignment film produced by the present invention exhibits the same orientation and afterimage characteristics as the rubbing method, it can be suitably used for TN and STN type liquid crystal display devices, and SH (Super) Homeotropic) and IPS (In-Plane Switching) ferroelectric and antiferroelectric liquid crystal display devices can be suitably used.
    Moreover, the liquid crystal display element which has the liquid crystal aligning film manufactured by this invention can be effectively used for various apparatuses, For example, such as a table calculator, a wristwatch, a table clock, a counting plate, a word processor, a personal computer, a liquid crystal television, etc. It can be used for a display device.
    权利要求:
    Claims (10)
    [1" claim-type="Currently amended] An ion beam is irradiated to the organic thin film containing soluble polyimide which has an alicyclic structure formed on the board | substrate, The manufacturing method of the liquid crystal aligning film characterized by the above-mentioned.
    [2" claim-type="Currently amended] The soluble polyimide having an alicyclic structure is obtained by dehydrating and closing a polyamic acid which is a reaction product of a tetracarboxylic dianhydride and a diamine compound, and at least one of the tetracarboxylic dianhydride and a diamine compound. The production method in which the acid anhydride group or amino group contains a compound in which an alicyclic structure is directly bonded.
    [3" claim-type="Currently amended] The production method according to claim 2, wherein the tetracarboxylic dianhydride contains tetracarboxylic dianhydride in which at least an acid anhydride group is directly bonded in an alicyclic structure.
    [4" claim-type="Currently amended] The tetracarboxylic dianhydride according to claim 3, wherein the tetracarboxylic dianhydride comprises tetracarboxylic dianhydride in which an acid anhydride group is directly bonded to an alicyclic structure, tetracarboxylic dianhydride in which the acid anhydride group is not directly bonded to an alicyclic structure. Method of preparation, which is a combination.
    [5" claim-type="Currently amended] The production method according to claim 2, wherein the diamine compound contains a diamine compound in which at least an amino group is directly bonded in an alicyclic structure.
    [6" claim-type="Currently amended] The production method according to claim 5, wherein the diamine compound is a combination of a diamine compound in which an amino group is directly bonded to an alicyclic structure, and a diamine compound in which the amino group is not directly bonded to an alicyclic structure.
    [7" claim-type="Currently amended] The production method according to claim 1, wherein the soluble polyimide having an alicyclic structure is linked with and sealed at its molecular terminals by a monofunctional compound selected from the group consisting of an acid anhydride, a monoamine compound, and a monoisocyanate compound.
    [8" claim-type="Currently amended] The logarithmic viscosity of the soluble polyimide having an alicyclic structure is in the range of 0.05 to 10 dl / g (measured at 30 ° C. at a concentration of 0.5 g / 100 ml in N-methyl-2-pyrrolidone). Manufacturing method in the factory.
    [9" claim-type="Currently amended] The method according to claim 1, wherein the organic thin film containing the soluble polyimide having an alicyclic structure has a thickness of 0.001 to 1 m.
    [10" claim-type="Currently amended] The production method according to claim 1, wherein the ion type of the ion beam is a water-soluble gas such as nitrogen, helium, argon or neon.
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    同族专利:
    公开号 | 公开日
    KR100554330B1|2006-05-25|
    TW591274B|2004-06-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-12-03|Priority to JP97-333199
    1997-12-03|Priority to JP33319997
    1998-12-02|Application filed by 마쯔모또 에이찌, 제이에스알 가부시끼가이샤
    1999-07-26|Publication of KR19990062726A
    2006-05-25|Application granted
    2006-05-25|Publication of KR100554330B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP97-333199|1997-12-03|
    JP33319997|1997-12-03|
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