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    • 专利摘要:
    Provided is a method for producing an amine adduct of a conductive composite, which comprises adding an amine compound to a dispersion liquid of a conductive polymer containing water and a conductive composite comprising a π-conjugated conductive polymer and a polyanion at a mass ratio of π-conjugated conductive polymer to the polyanion from 1: 3 to 1: 7.5 to precipitate an amine adduct of the conductive composite.
    公开号:BE1025000B1
    申请号:E2017/5679
    申请日:2017-09-26
    公开日:2018-09-17
    发明作者:Sou Matsubayashi；Takanori Suzuki
    申请人:Shin-Etsu Polymer Co., Ltd.；Nissin Chemical Industry Co., Ltd.；
    IPC主号:
    专利说明:

    PATENT OF THE INVENTION
    Priority date: 30/09/2016
    International classification: C08J 3/03
    Registration number: BE2017 / 5679
    Registration date: 26/09/2017
    Owner:
    SHIN-ETSU POLYMER CO., LTD.
    101-0041, TOKYO
    Japan
    NISSIN CHEMICAL Industry Co., Ltd.
    915-0802, FUKUI
    Japan
    Inventor:
    MATSUBAYASHI Sou 331-0811 SAITAMA-SHI Japan
    SUZUKI Takanori 915-0802 FUKUI Japan
    METHOD FOR PRODUCING AN AMINE ADDUCT OF A CONDUCTIVE
    COMPOSITE, METHOD FOR PRODUCING AN AMINE ADDUCT LIQUID OF A CONDUCTIVE COMPOSITE, AND METHOD FOR PRODUCING A CONDUCTIVE FILM
    There is provided a method of making an amine adduct of a conductive composite which includes: adding an amine compound to a conductive polymer dispersion liquid containing water and a conductive composite containing a π-conjugated conductive polymer and a polyanion at a mass ratio of the π-conjugated contains conductive polymer to the polyanion from 1: 3 to 1: 7.5 to precipitate an amine adduct of the conductive composite.
    BELGIAN INVENTION PATENT
    FÖD Wirtschaft, K.M.B., Mittelstand & Publication number: 1025000 Energy Filing number: BE2017 / 5679
    Office of Intellectual Property Boarding. Classification: C08J 3/03
    Date of issue: 17/09/2018
    The Minister for Enterprise
    Due to the Paris Treaty of March 20, 1883 for the protection of industrial property;
    Introduced under the Act of March 28, 1984 on Inventive Patents, Article 22, for applications prior to September 22, 2014;
    Based on Title I “Invention Patents” of Book XI of the Economic Code, Article XI.24, introduced for applications from September 22, 2014;
    Based on the royal decree of December 2, 1986 on the registration, granting and maintenance of patents for invention, Article 28;
    Based on the protocol, taken on 26/09/2017 at the Intellectual Property Office.
    Considering that for patent applications that fall within the scope of Title 1, Book XI, of the Economic Code, in accordance with Article XI.19, Section 4, second paragraph, of the Economic Code, if the patent application is the subject of a search report in which a lack of unity of invention within the meaning of paragraph 1 is mentioned, and if the applicant does not limit his application and does not file a divisional application in accordance with the search report, the granted patent will be limited to the claims for which the search report was created.
    DECIDES:
    Article 1. - An invention patent is granted to:
    SHIN-ETSU POLYMER CO., LTD., 1-9 Kanda - Sudacho Chiyoda-ku, 101-0041 TOKYO Japan;
    NISSIN CHEMICAL Industry Co., Ltd., 17-33, Kitago 2 - chôme Echizen-shi, 915-0802 FUKUI Japan;
    represented by :
    FRENNET Pierre-Paul, Center Monnet - Avenue Jean Monnet 1, 1348, LOUVAIN-LA-NEUVE;
    for a period of 20 years, subject to the payment of the annual patent fees mentioned in Article XI.48, Section 1 of the Economic Code, for: PROCESS FOR PRODUCING AN AMINADUCT
    CONDUCTIVE COMPOSITE, METHOD FOR PRODUCING ONE
    AMINE ADDUCT LIQUID OF A CONDUCTIVE COMPOSITE AND METHOD FOR
    MAKE A CONDUCTIVE FILM.
    INVENTOR:
    MATSUBAYASHI Sou, Shin-Etsu Polymer Co., Ltd. 1-406-1 Yoshino-cho Kita-ku, 331-0811, SAITAMA-SHI;
    SUZUKI Takanori, NISSIN CHEMICAL INDUSTRY CO., LTD. 17-33, Kitago 2-chome ,, 915-0802, FUKUI;
    PRIORITIES) :
    30/09/2016 JP 2016-193967;
    SEPARATION:
    Partial application of the previous application: Date of filing of the previous application:
    Article 2. - This patent is granted without any prior examination of the patentability of the invention, without guaranteeing the merit of the invention or the accuracy of its description, and at the own risk of the patent applicant (s).
    Brussels, 17/09/2018, in special representation:
    BE2017 / 5679
    description
    METHOD FOR PRODUCING AN AMINE ADDUCT OF A CONDUCTIVE COMPOSITE, METHOD FOR PRODUCING AN AMINE ADDUCT LIQUID OF A CONDUCTIVE COMPOSITE, AND METHOD FOR PRODUCING A CONDUCTIVE FILM
    BACKGROUND OF THE INVENTION
    Field of the Invention The present invention relates to a process for producing an amine adduct of a conductive composite containing a conjugated conductive polymer, a process for producing an amine adduct liquid of a conductive composite, and a process for producing a conductive film.
    Priority is claimed on Japanese Patent Application No. 2016193967 filed on September 30, 2016, the contents of which are incorporated herein by reference.
    Description of the Related Art As a coating material for forming a conductive layer on a base film, an aqueous conductive polymer dispersion liquid obtained by doping poly (3,4-ethylenedioxythiophene) with polystyrene sulfonic acid is occasionally used.
    Since a surface of a base film made of plastic is typically hydrophobic, the aqueous dispersion liquid of a conductive polymer serving as an aqueous coating material tends to have poor wettability with respect to the base film. Therefore, the adhesion of the conductive layer to be formed on the base film is not excellent in some.
    Further, since the time for drying water serving as a dispersion medium of the aqueous dispersion liquid of a conductive polymer is longer than that for an organic solvent, the
    BE2017 / 5679
    Drying process is a limiting factor for the process of forming the conductive layer.
    For the purpose of improving the wettability and reducing the drying time as described above, an organic solvent dispersion liquid of a conductive polymer is used in some cases by substituting water as a dispersion medium of an aqueous dispersion liquid of a conductive polymer serves, is obtained with an organic solvent. As the organic solvent dispersion liquid of a conductive polymer, there was known one obtained by freeze-drying an aqueous dispersion liquid of a conductive polymer containing a conductive composite formed by a π-conjugated conductive polymer and a polyanion to obtain a dried product. and adding an organic solvent and an amine compound to the dried product (Patent Document 1).
    Patent Document [Patent Document 1] Japanese Unexamined Patent Application, First Publication No. 2011-032382
    SUMMARY OF THE INVENTION The conductive composite contained in the dried product described in Patent Document 1 is hydrophilic, but changes to be lipophilic when an amine compound is added. In this case, an amine adduct liquid can be obtained which is formed by dissolving or dispersing the amine adduct of the conductive composite in the organic solvent. However, there is a problem that a solid precipitates in the amine adduct liquid in a case where the amine adduct liquid is made and stored before use. Since the base film cannot be coated with the amine adduct liquid in which a large amount of solid has precipitated, it is necessary to reduce the precipitation of the solid during storage.
    BE2017 / 5679 The present invention has been made in consideration of the above-described circumstances, and it is an object thereof to provide a method for producing an amine adduct liquid of a conductive composite having an excellent storage stability; to provide a method for producing an amine adduct of a conductive composite, which is a material of the amine adduct liquid, and a method for producing a conductive film obtained using the amine adduct liquid.
    [1] A method of producing an amine adduct of a conductive composite, which comprises: adding an amine compound to a conductive polymer dispersion liquid containing water and a conductive composite containing a π-conjugated conductive polymer and a polyanion at a mass ratio of Contains π-conjugated conductive polymer to the polyanion from 1: 3 to 1: 7.5 to precipitate an amine adduct of the conductive composite.
    [2] A method for producing an amine adduct of a conductive composite according to [1], which further comprises: adding an organic solvent to the dispersion liquid of a conductive polymer.
    [3] A method for producing an amine adduct of a conductive composite according to [1] or [2], which further comprises: collecting the precipitated amine adduct by filtration.
    [4] A method for producing an amine adduct of a conductive composite according to [3], which further comprises: washing the collected amine adduct with an organic solvent.
    [5] The method for producing an amine adduct of a conductive composite according to [2], wherein the organic solvent added to the dispersion liquid of a conductive polymer is isopropanol.
    [6] The method for producing an amine adduct of a conductive composite according to [4], wherein the organic solvent for washing the amine adduct is acetone.
    [7] A process for producing an amine adduct of a conductive composite according to any one of [1] to [6], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
    BE2017 / 5679 [8] A process for producing an amine adduct of a conductive composite according to any one of [1] to [7], the polyanion being a polystyrene sulfonic acid.
    [9] A process for producing an amine adduct of a conductive composite according to any one of [1] to [8], wherein the amine compound is trioctylamine or tributylamine.
    [10] A method of producing an amine adduct liquid of a conductive composite, which comprises: obtaining an amine adduct of the conductive composite by the manufacturing method according to any one of [1] to [9]; and dissolving or dispersing the amine adduct of the conductive composite in an organic solvent.
    [11] A method of producing an amine adduct liquid of a conductive composite according to [10], wherein the organic solvent is isopropanol or methyl ethyl ketone.
    [12] A method of producing an amine adduct liquid of a conductive composite according to [10] or [11], which further comprises: adding a binder component.
    [13] A method for producing an amine adduct liquid of a conductive composite according to [12], wherein the binder component is curable with active energy rays.
    [14] A method of manufacturing a conductive film, comprising: a step of obtaining an amine adduct liquid of the conductive composite by the manufacturing method according to any one of [10] to [13]; a coating step of coating at least one surface of a base film with the amine adduct liquid of the conductive composite; and a drying step of drying the applied amine adduct liquid.
    [15] A method of manufacturing a conductive film according to [14], wherein the amine adduct liquid contains a binder component which is curable with active energy rays, and the method further comprises an active energy radiation irradiation step of irradiating a coated film of the dried amine adduct liquid with active energy rays after the drying step.
    BE2017 / 5679 In the amine adduct liquid of the conductive composite obtained by the manufacturing method of the present invention, the solid that precipitates during storage is reduced and that
    Storage stability is excellent.
    When the amine adduct of the conductive composite obtained by the manufacturing method of the present invention is used as a material of the amine adduct liquid, excellent storage stability is obtained.
    According to the method for producing a conductive film of the present invention, since an amine adduct liquid with fewer precipitates is used, a conductive layer with excellent adhesiveness and conductivity can be easily formed. Furthermore, the time for the drying step can be reduced because the dispersion medium of the amine adduct liquid is an organic solvent.
    DETAILED DESCRIPTION OF THE INVENTION << Method for Producing Amine Adduct of Conductive Composite >>
    According to a first embodiment of the present invention, there is provided a method of producing an amine adduct of a conductive composite which includes: adding an amine compound to a conductive polymer dispersion liquid containing water and a conductive composite containing a π-conjugated conductive polymer and a polyanion at a mass ratio of the π-conjugated conductive polymer to the polyanion of from 1: 3 to 1: 7.5 to precipitate an amine adduct of the conductive composite.
    In the present specification, the amine adduct of a conductive composite is simply referred to as an “amine adduct” in some cases. Furthermore, the amine adduct denotes an amine compound that is coordinated or bound to some excess anion groups in the polyanion of the conductive composite. The excess anion groups denote anion groups which do not contribute to doping the π-conjugated conductive polymer. The amount of
    BE2017 / 5679 excess anion groups is preferably in a range from 1 mol% to 99 mol% and more preferably in a range from 10 mol% to 90 mol% with respect to 100 mol% of all anion groups in the polyanion. The amount of the anion groups to which an amine compound is coordinated or bound is preferably in a range from 1 mol% to 99 mol%, and more preferably in a range from 10 mol% to 90 mol% with respect to 100 mol% of all excess anion groups.
    <Conductive polymer dispersion liquid>
    The conductive polymer dispersion liquid contains a conductive composite containing a π-conjugated conductive polymer and a polyanion; and an aqueous dispersion medium that disperses the conductive composite.
    The π-conjugated conductive polymer is not particularly limited as long as the polymer is an organic polymer whose main chain is formed of a π-conjugated system and exhibits the effects of the present invention, and examples thereof include a polypyrrole-based conductive polymer , a polythiophene-based conductive polymer, a polyacetylene-based conductive polymer, a polyphenylene-based conductive polymer, a polyphenylene-vinylene-based conductive polymer, a polyaniline-based conductive polymer, a polyacene-based conductive polymer, a polythiophene-vinylene-based conductive polymer, and their copolymers. From the standpoint of stability in air, a polypyrrole-based conductive polymer, polythiophenes and a polyaniline-based conductive polymer are preferred. From the viewpoint of transparency, a polythiophene-based conductive polymer is more preferred.
    [0012] Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propyl-thiophene), poly (3-butylthiophene), poly (3-hexylthiophene), poly ( 3heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-iodothiophene), Poly (3-cyanothiophene), poly (3phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (37
    BE2017 / 5679 ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene),
    Poly (3-heptyloxythiophene), decyloxythiophene), octadecyloxythiophene), dimethoxythiophene), dipropoxythiophene), dihexyloxythiophene),
    Poly (3-octyloxythiophene), Poly (3Poly (3-dodecyloxythiophene), Poly (3Poly (3,4-dihydroxythiophene), Poly (3,4Poly (3,4-diethoxythiophene), Poly (3,4Poly (3,4- dibutoxythiophene), poly (3,4-poly (3,4-diheptyloxythiophene), poly (3,4-dioctyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), Poly (3,4-propylenedioxythiophene), poly (3,4-butylenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene) ), Poly (3-methyl-4-carboxyethylthiophene) and poly (3-methyl-4-carboxybutylthiophene).
    Examples of the polypyrrole-based conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), poly (3-butylpyrrole), poly (3 -octylpyrrole), poly (3decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), Poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), Poly (3-hexyloxypyrrole) and poly (3-methyl-4hexyloxy pyrrole).
    Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2aniline sulfonic acid) and poly (3-aniline sulfonic acid).
    Among the examples of the π-conjugated conductive polymers described above, poly (3,4-ethylenedioxythiophene) is particularly preferred from the viewpoints of conductivity, transparency and heat resistance.
    The π-conjugated conductive polymer can be used alone or in a combination of two or more kinds thereof.
    The polyanion is a polymer with two or more monomer units which contain an anion group in one molecule. The anion group of this polyanion acts as a dopant
    BE2017 / 5679 the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer.
    As the anion group of the polyanion is a sulfo group or one
    Carboxy group preferred.
    Specific examples of such a polyanion include a polymer containing a sulfonic acid group, such as polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polyacrylic sulfonic acid, polymethacrylic sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene sulfonic acid, polysulfoethyl methacrylate or poly (methacrylate) benzyl sulfonic acid; and a polymer containing a carboxylic acid group such as polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly (2-acrylamido-2-methyl propane carboxylic acid), polyisoprene carboxylic acid or polyacrylic acid. These homopolymers or two or more copolymers can be used.
    Among the examples of the polyanion described above, from the viewpoint of further improving the conductivity, a polymer containing a sulfonic acid group is preferred, and polystyrene sulfonic acid is more preferred.
    The polyanion can be used alone or in combination of two or more kinds thereof.
    The weight average molecular weight of the polyanion is preferably in a range from 20,000 to 1,000,000, and more preferably in a range from 100,000 to 500,000.
    The weight average molecular weight in the present specification is measured using gel permeation chromatography and is a value obtained by setting polystyrene as a standard substance.
    The mass ratio of the π-conjugated conductive polymer to the polyanion is in a range from 1: 3 to 1: 7.5, preferably in a range from 1: 3.5 to 1: 7.0, more preferably in one Range from 1: 4 to 1: 6.5 and more preferably in a range from 1: 4.5 to 1: 6.
    BE2017 / 5679
    In a case where the mass ratio is greater than or equal to the lower limit described above, the conductivity is satisfactorily maintained and the storage stability of the amine adduct liquid of the conductive composite formed by dissolving or dispersing the amine adduct of the conductive composite in an organic solvent is obtained further improved. Therefore, the generation of precipitates during storage can be reduced.
    In a case where the mass ratio is less than or equal to the upper limit described above, the conductivity is satisfactorily maintained and the storage stability of the amine adduct liquid of the conductive composite formed by dissolving or dispersing the amine adduct of the conductive composite in an organic solvent is obtained further improved. Therefore, gel formation during storage can be reduced.
    (Method for Making Dispersion Liquid of a Conductive Polymer)
    According to a method of preparing a conductive polymer dispersion liquid containing the conductive composite having the specific mass ratio described above, the conductive polymer dispersion liquid is obtained by applying chemical oxidative polymerization to a monomer containing the π-conjugated conductive polymer in an aqueous solution Polyanions forms. By allowing the polyanion having the mass ratio described above with the π-conjugated conductive polymer formed in the reaction solution to be contained in the aqueous solution, a conductive composite can be obtained in which the mass ratio is set as desired .
    During chemical oxidative polymerization, an oxidizing agent such as ammonium persulfate or sodium persulfate can be used as a catalyst.
    Furthermore, commercially available products can be used as the aqueous dispersion liquid of the conductive polymer.
    The π-conjugated conductive polymer is coordinated and doped with the polyanion to form a conductive composite. Here
    In BE2017 / 5679 the π-conjugated conductive polymer is not doped with all anion groups of the polyanion and excess anion groups which do not contribute to the doping are present. The hydrophilicity of the conductive composite is shown satisfactorily by the excess anion groups.
    [0017] The aqueous dispersion medium that disperses the conductive composite is water or a mixed solution of water and an organic solvent.
    The water content is preferably in a range of 60 mass% to 100 mass%, more preferably in a range of 70 mass% to 100 mass% and still more preferably in a range of 80 mass% to 100 mass%. % with respect to the total mass (100 mass%) of the aqueous dispersion medium. In a case where the content of water in the aqueous dispersion medium is greater than or equal to the lower limit described above, the dispersibility of the conductive composite in the dispersion liquid of the conductive polymer is further improved.
    Examples of the organic solvent which may be contained in the aqueous dispersion medium include an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an ester-based solvent and an aromatic hydrocarbon-based solvent.
    These organic solvents can be used alone or in combination of two or more kinds thereof.
    Examples of the alcohol-based solvent include methanol, ethanol, isopropanol n-butanol, t-butanol and allyl alcohol.
    Examples of the ether-based solvent include diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, and propylene glycol dialkyl ether.
    Examples of the ketone-based solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone and diacetone alcohol.
    BE2017 / 5679
    Examples of the ester-based solvent include ethyl acetate, propyl acetate and butyl acetate.
    Examples of the aromatic hydrocarbon-based solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene and isopropylbenzene.
    [0019] In the present embodiment, an amine adduct of the conductive composite can be precipitated by adding an amine compound to the conductive polymer dispersion liquid containing the conductive composite and water.
    According to the mechanism of the precipitation, the precipitation of the amine adduct is believed to occur due to the addition of the added amine compound to the excess anion groups of the conductive composite to reduce the hydrophilicity thereof.
    [0020] The amine compound added may be one of a primary amine, a secondary amine, a tertiary amine and a quaternary ammonium salt. The amine compound can be used alone or in combination of two or more kinds thereof.
    Examples of the hydrocarbon group which may be contained in the amine compound include a linear or branched alkyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, an aralkylene group having 7 to 12 carbon atoms and an oxyalkylene group having 2 to 12 carbon atoms.
    Examples of the substituent which the amine compound may contain on the hydrocarbon group include a hydroxyl group, an ester group and an ether group.
    [0021] Examples of the primary amine include aniline, toluidine, benzylamine and ethanolamine.
    Examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine and dinaphthylamine.
    BE2017 / 5679
    Examples of the tertiary amine include triethanolamine,
    Trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine,
    Triphenylamine, tribenzylamine and trinaphthylamine.
    Examples of the quaternary ammonium salt include a tetramethylammonium salt, a tetraethylammonium salt, a tetrapropylammonium salt, a tetraphenylammonium salt
    Tetrabenzylammonium salt and a tetranaphthylammonium salt. Examples of an anion to be paired with ammonium include hydroxide ions.
    Among the amine compounds, the tertiary amine is preferred from the viewpoint of facilitating the precipitation of the amine adduct, and tributylamine and trioctylamine are more preferred.
    The amount of the amine compound to be added can be set, for example, in a range of 100 parts by mass to 3,000 parts by mass with respect to 100 parts by mass of the conductive composite. The amount thereof is preferably in a range of 150 parts by mass to 2,000 parts by mass, more preferably in a range of 200 parts by mass to 1,500 parts by mass, and still more preferably in a range of 300 parts by mass to 1,000 parts by mass.
    In a case where the amount thereof is greater than or equal to the lower limit described above, the amine adduct can be more easily precipitated.
    In a case where the amount thereof is less than or equal to the upper limit described above, it is possible to prevent the conductivity of the amine adduct from deteriorating due to the addition of an excessive amount of the amine compound to the amine adduct.
    In the present embodiment, it is preferable that an organic solvent is further added to the dispersion liquid of the conductive polymer. The method for adding an organic solvent can be carried out before, after or simultaneously with the addition of the amine compound to the dispersion liquid of the conductive polymer.
    Examples of the organic solvent to be further added to the dispersion liquid of the conductive polymer include
    BE2017 / 5679
    Alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an ester-based solvent and an aromatic hydrocarbon-based solvent. Specific examples of these organic solvents include those described as specific examples of the organic solvent which may be contained in the above-described aqueous dispersion medium. It is preferable that the organic solvent added to precipitate the amine adduct differs from the organic solvent contained in the above-described aqueous dispersion medium.
    Among the examples of the organic solvent described above, an alcohol-based solvent is preferred from the viewpoint of facilitating precipitation of the amine adduct, and isopropanol is more preferred. The organic solvent to be added to precipitate the amine adduct can be used alone or in combination of two or more kinds thereof.
    The amount of the organic solvent to be added to precipitate the amine adduct can be set, for example, in a range of 10 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the dispersion liquid of the conductive polymer. The amount thereof is preferably in a range of 30 parts by mass to 800 parts by mass, more preferably in a range of 50 parts by mass to 500 parts by mass, and still more preferably in a range of 70 parts by mass to 200 parts by mass.
    In a case where the amount thereof is greater than or equal to the lower limit described above, the amine adduct can be more easily precipitated.
    In a case where the amount thereof is less than or equal to the upper limit described above, it is possible to prevent separation of the amine compound from the amine adduct.
    (Process for Precipitation of Amine Adduct)
    The amine adduct formed by adding an amine compound to the conductive composite can be added by adding one
    BE2017 / 5679
    Amine compound and an optional organic solvent to the
    Dispersion liquid of the conductive polymer can be precipitated.
    The content of the conductive composite contained in the dispersion liquid of the conductive polymer immediately before the addition of the amine compound may range, for example, from 0.1% by mass to 10% by mass with respect to the total mass of the dispersion liquid of the conductive Polymers can be adjusted. The content thereof is preferably in a range of 0.5% by mass to 5% by mass, more preferably in a range of 1.0% by mass to 4% by mass, and still more preferably in a range of 1.5% by mass % to 3 mass%.
    In a case where the content thereof is greater than or equal to the lower limit described above, the amine adduct can be more easily precipitated in a short time. In a case where the content thereof is lower than or equal to the upper limit described above, it is possible to prevent the precipitation of the conductive composite material to which an amine has not been added because the conductive composite material in the precipitation of other amine adducts that are previously formed is involved.
    The order of adding the amine compound and the organic solvent to the dispersion liquid of the conductive polymer is not particularly limited.
    The organic solvent can be added after the addition of the amine compound. The amine compound can be added after the addition of the organic solvent. Alternatively, a mixed solution previously formed by mixing the amine compound and the organic solvent may be added to the dispersion liquid of the conductive polymer. Of these, from the viewpoint that the amine compound and the organic solvent can be uniformly and rapidly added to the dispersion liquid of a conductive polymer, the method of adding the mixed solution to the dispersion liquid of the conductive polymer is preferred.
    BE2017 / 5679 The amine adduct naturally precipitates in the dispersion liquid of the conductive polymer, to which the amine compound and the optional organic solvent have been added, by allowing the dispersion liquid to stand or the dispersion liquid to be stirred gently. The temperature of the dispersion liquid during the precipitation can be set to a value in the range, for example, from 5 ° C. to 80 ° C. The time required to complete the precipitation of the amine adduct can be expected to range from, for example, 5 minutes to 240 minutes.
    (Method for Collecting Amine Adduct)
    As the method for collecting the precipitated amine adduct of the conductive composite from the dispersion medium, methods for collecting a product known in the field of organic synthesis, such as filtration, precipitation or extraction, can be used.
    Filtration is preferred among these collection methods. In addition, it is preferred to use a coarse mesh filter to the extent that the polyanion used to form the conductive composite passes through with the filtrate. According to this filtration method, while the precipitated amine adduct is collected, the amine adduct and excess polyanions which are not used for the formation of the conductive composite can be separated by leaving the excess anions on the filtrate side. The conductivity of the amine adduct can be improved by removing the excess polyanions.
    As the filter used for the filtration, a filter paper used in the field of chemical analysis is preferred. For example, the filter paper is a filter paper (manufactured by Advantech Co., Ltd.) with a retention particle diameter of 7 µm. Here, the retention particle diameter of the filter paper is an indication of the coarseness of the sieve widths and is obtained from the leakage particle diameter used when barium sulfate or the like specified by JIS P 3801 [filter paper (for chemical
    BE2017 / 5679
    Analysis)] is naturally filtered. The retention particle diameter of the
    Filter paper can be set in a range from 2 pm to 10 pm.
    From the point of view of simply separating the excess
    Passing polyanions, the retention particle diameter is preferably in a range of 5 pm to 10 pm.
    It is preferred that the collected amine adduct is washed with at least one of water and an organic solvent.
    During the washing, excess components collected with the amine adduct, such as the polyanion and the amine compound, are washed off, and therefore the conductivity of the amine adduct can be improved.
    Examples of the organic solvent used for washing include an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an ester-based solvent and an aromatic hydrocarbon-based solvent as described above. Among them, a ketone-based solvent is preferred, and acetone is particularly preferred. When acetone is used, the excess components described above can be easily washed off and a decrease in the amine adduct due to washing can be suppressed.
    According to the method for producing an amine adduct of a conductive composite as described above, about 120 parts by mass to 1000 parts by mass of the amine adduct can be obtained with respect to 100 parts by mass of the conductive composite contained in the dispersion liquid of the conductive polymer.
    According to the method for producing an amine adduct of a conductive composite of the present invention, it is preferred that the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene), the polyanion is polystyrene sulfonic acid, and the amine compound is trioctylamine or tributylamine.
    According to the method for producing an amine adduct of a conductive composite of the present invention, it is preferred that the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene) which
    BE2017 / 5679
    Polyanion is polystyrene sulfonic acid, the amine compound trioctylamine or
    Is tributylamine and the amount of the amine compound to be added in one
    Range is 100 to 3000 parts by mass with respect to 100 parts by mass of the conductive composite.
    It is preferable that the method for producing an amine adduct of a conductive composite of the present invention includes a process of adding an organic solvent to the dispersion liquid of the conductive polymer, and that the organic solvent is isopropanol.
    According to the method for producing an amine adduct of a conductive composite of the present invention, it is preferable that the amine compound is added to the dispersion liquid of the conductive polymer in the form of a mixed solution of the amine compound and an organic solvent, and that the organic solvent is isopropanol .
    [0035] << Process for producing amine adduct liquid from conductive composite >>
    According to a second embodiment of the present invention, a process for producing an amine adduct liquid includes obtaining an amine adduct according to the production process of the first embodiment and dissolving or dispersing the obtained amine adduct in an organic solvent. Here, the amine adduct liquid denotes a solution of a dispersion liquid of an amine adduct.
    The amine adduct can be easily dissolved or dispersed in an organic solvent. Examples of the organic solvent that forms the amine adduct liquid include an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an ester-based solvent and an aromatic hydrocarbon-based solvent. Specific examples of these organic solvents include those previously described as the specific examples of the organic solvent that may be previously contained in the above-described aqueous dispersion medium.
    BE2017 / 5679
    Among the examples of the organic solvent described above, from the viewpoint of excellent dispersibility of the amine adduct, an alcohol-based solvent or a ketone-based solvent is preferred, and isopropanol or methyl ethyl ketone is more preferred. The organic solvent that dissolves or disperses the amine adduct can be used alone or in combination of two or more kinds thereof.
    The amount of the organic solvent that dissolves or disperses the amine adduct is preferably in a range of 100 to 1,000,000 parts by mass, and more preferably in a range of 1,000 to 100,000 parts by mass with respect to 100 parts by mass of the amine adduct.
    The concentration of the amine adduct dissolved or dispersed in the organic solvent can be set, for example, in a range of 0.1 mass% to 10 mass% with respect to the total mass of the amine adduct liquid.
    In a case where the concentration thereof is greater than or equal to the lower limit described above, a conductive layer formed by coating with the amine adduct liquid can have excellent conductivity.
    In a case where the concentration thereof is less than or equal to the upper limit described above, the coatability of the amine adduct liquid with respect to a base film is improved so that the surface to be coated can be uniformly and easily coated with the amine adduct liquid without unevenness.
    A method for dissolving or dispersing the amine adduct in the organic solvent is not particularly limited. A known method for dissolving or dispersing a conductive polymer or a typical synthetic resin in an organic solvent is used. From the viewpoint of improving the dispersibility, it is preferable to use a pressurizable high pressure homogenizer.
    [0040] The amine adduct liquid may contain a binder component, a highly conductive agent and other additives.
    [Binder component]
    BE2017 / 5679
    The binder component is a component that differs from the conjugated conductive polymer, the polyanion, and the amine compound and that improves the mechanical strength or hardness of the conductive layer formed by coating with the amine adduct liquid.
    Examples of the binder component include resins, thermosetting compounds and active energy radiation curable compounds. In a case where a thermosetting compound is used, it is preferable that the amine adduct liquid also contains a thermal polymerization initiator. In a case where an active energy radiation curable compound is used, it is preferable that the amine adduct liquid also contains a photopolymerization initiator.
    Examples of the resins that can be used as the binder component include an acrylic resin, a polyester resin, an epoxy resin, an oxetane resin, a polyurethane resin, a polyimide resin, a melamine resin, a silicone resin and a vinyl acetate resin.
    Examples of the thermosetting compound and the active energy-curable compound include a compound containing a vinyl group, a compound containing an epoxy group, and a compound containing an oxetane group. These can be monomers or oligomers.
    Among the examples of the binder components described above, from the viewpoints of easy dispersing or dissolving in the organic solvent and ease of curing, an active energy ray curable acrylic compound is preferred. The active energy radiation-curable acrylic compound is an acrylic compound which is radically polymerized and cured by irradiation with active energy rays (ultraviolet rays, electron beams and visible light beams).
    Examples of the active energy ray curable acrylic compound include acrylate, methacrylate, (meth) acrylamide, vinyl ether and vinyl carboxylate. Furthermore, the active energy radiation curable acrylic compound may be a monofunctional monomer having only one vinyl group
    BE2017 / 5679, a polyfunctional monomer containing two or more vinyl groups, or a combination of a monofunctional monomer and a polyfunctional monomer.
    Examples of the acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobornyl acrylate, tetrahydrofurfury acrylate, dipropylene glycol diacrylate,
    Tripropylene glycol diacrylate, polyethylene glycol diacrylate, 1,6 hexanediol diacrylate, bisphenol A ethylene oxide modified diacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate,
    Dipentaerythritol pentaacrylate, dipentaerythritol monohydroxypentaacrylate, trimethylolpropane triacrylate and glycerol propoxy triacrylate.
    Examples of the methacrylate include n-butyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, allyl methacrylate, 2-hydroxyethyl methacrylate, lauryl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, diethylene glycol, methacrylate dimethacrylate, butyl methacrylate,
    Phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, tetraethylene glycol dimethacrylate, 1,31,6-hexanediol dimethacrylate and
    2-chloroethyl vinyl ether, hydroxybutyl vinyl ether,
    Trimethylolpropane trimethacrylate.
    Examples of the (meth) acrylamide include methacrylamide, 2-hydroxyethylacrylamide, N-methylacrylamide, N-t-butylacrylamide, Nisopropylacrylamide, N-phenylacrylamide, N-methylolacrylamide,
    Dimethylamino-propylacrylamide, dimethylaminopropyl methacrylamide,
    Diacetone acrylamide, Ν, Ν-dimethylacrylamide, N-vinylformamide,
    Acryloylmorpholine and Acryloylpiperidine.
    Examples of the vinyl ether include cyclohexyl vinyl ether, ethyl vinyl ether,
    Isobutyl vinyl ether and triethylene glycol vinyl ether.
    Examples of the carboxylic acid vinyl ester include vinyl butyrate, vinyl monochloroacetate and vinyl pivalate.
    Furthermore, the active energy radiation curable acrylic compound may be polyfunctional acrylate obtained by reacting an acrylic monomer and another compound such as epoxy acrylate, urethane acrylate, polyester acrylate and polyacrylic acrylate.
    BE2017 / 5679
    The active energy radiation curable acrylic compound can be used alone or in
    Combination of two or more types of it can be used.
    The content of the binder component is preferably in a range of 1,000 parts by mass to 100,000 parts by mass, and more preferably in a range of 3,000 parts by mass to 50,000 parts by mass with respect to 100 parts by mass of the conductive composite. In a case where the content of the binder component is greater than or equal to the lower limit described above, the strength and hardness of the conductive layer to be obtained can be satisfactorily improved. In a case where the content thereof is less than or equal to the upper limit described above, the conductivity can be ensured satisfactorily.
    The total concentration of the solid content (non-volatile content) in the binder component to be added to the amine adduct liquid is preferably in a range of 100 parts by mass to 100,000 parts by mass, more preferably in a range of 1,000 parts by mass to 50,000 parts by mass, and even more preferably in a range from 5000 parts by mass to 20,000 parts by mass with respect to 100 parts by mass of the amine adduct.
    In a case where the total concentration thereof is greater than or equal to the lower limit described above, the mechanical strength or the hardness of the conductive layer to be formed can be satisfactorily improved.
    In a case where the total concentration thereof is less than or equal to the upper limit described above, the conductivity of the conductive layer to be formed can be satisfactorily obtained.
    (Highly conductive agent)
    The highly conductive agent that may be contained in the amine adduct liquid is a chemical agent that improves the conductivity of the amine adduct except for the amine compound, the conjugated conductive polymer, the polyanion and the binder component.
    It is preferred that the highly conductive agent is at least one compound selected from the group consisting of
    BE2017 / 5679
    Saccharides, a nitrogen-containing aromatic cyclic compound, a compound containing two or more hydroxyl groups, a compound containing a hydroxyl group and one or more carboxy groups, a compound containing an amide group, a compound containing an imide group, one Lactam compound and a compound containing a glycidyl group.
    The highly conductive agent can be used alone or in combination of two or more kinds thereof.
    [0046] Examples of the nitrogen-containing aromatic cyclic compound include pyridines containing one nitrogen atom and derivatives thereof, imidazoles containing two nitrogen atoms, and derivatives thereof, pyrimidines and derivatives thereof, pyrazines and derivatives thereof, and triazines containing three nitrogen atoms , and derivatives thereof. From the viewpoint of solubility in a solvent, pyridines and derivatives thereof, imidazoles and derivatives thereof and pyrimidines and derivatives thereof are preferred.
    Specific examples of the pyridines and derivatives thereof include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, N-vinylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 3-cyano -5methylpyridine, 2-pyridinecarboxylic acid, 6-methyl-2-pyridinecarboxylic acid, 4pyridinecarboxyaldehyde, 4-aminopyridine, 2,3-diaminopyridine, 2,6diaminopyridine, 2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 4pyridinemethanol, 2 , 6-dihydroxypyridine, 2,6-pyridine dimethanol, methyl 6-hydroxynicotinate, 2-hydroxy-5-pyridine methanol, ethyl 6-hydroxynicotinate, 4-pyridine methanol, 4-pyridine ethanol, 2-phenylpyridine, 3-methylquinoline, 3-ethylquinoline, quinolinol, 2 , 3-cyclopentenopyridine, 2,3-cyclohexanopyridine, 1,2-di (4-pyridyl) ethane, 1,2-di (4-pyridyl) propane, 2-pyridinecarboxyaldehyde, 2-pyridinecarboxylic acid, 2-pyridinecarbonitrile, 2,3 -Pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid and 3-pyridinesulfonic acid.
    [0048] Specific examples of the imidazoles and derivatives thereof include imidazole, 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, N-vinylimidazole, N-allylimidazole, 1- (2-hydroxyethyl) imidazole N-hydroxyethylimidazole), 2-ethyl-423
    BE2017 / 5679 methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2ethyl-4-methylimidazole, 2-phenyl-4,5 -dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazole-dicarboxylic acid, dimethyl-4,5-imidazole dicarboxylate, benzimidazole, 2-amino-benzimidazole, 2-aminobenzimidazole-2-sulfonic acid, 2-amino-1-methylbenzimidazyl (2-hydroxydidyl), 2-hydroxydidylol benzimidazole.
    [0049] Specific examples of the pyrimidines and derivatives thereof include 2-amino-4-chloro-6-methylpyrimidine, 2-amino-6-chloro-4-methoxypyrimidine, 2-amino-4,6-dichloropyrimidine, 2-amino-4 , 6-dihydroxypyrimidine, 2-amino4,6-dimethylpyrimidine, 2-amino-4,6-dimethoxypyrimidine, 2Aminopyrimidine, 2-amino-4-methylpyrimidine, 4,6-dihydroxypyrimidine, 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4 , 6-triaminopyrimidine, 2,4-dimethoxypyrimidine, 2,4,5-trihydroxypyrimidine and 2,4-pyrimidinediol. Specific examples of the pyrazines and derivatives thereof include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, pyrazine carboxylic acid, 2,3pyrazine dicarboxylic acid, 5-methylpyrazine carboxylic acid, pyrazinamide, 5methylpyrazine amide, 2-cyanopyrazine, aminopyrazine, aminopyrazine -2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine and 2,3-diethylpyrazine.
    Specific examples of the triazines and derivatives thereof include 1,3,5-triazine, 2-amino-l, 3,5-triazine, 3-amino-l, 2,4-triazine, 2,4-diamino-6phenyl -l, 3,5-triazine, 2,4,6-triamino-l, 3,5-triazine, 2,4,6-tris (trifluoromethyl) -l, 3,5-triazine, 2,4,6-tri- 2-pyridine-l, 3,5-triazine, 3- (2-pyridine) -5,6-bis (4-phenylsulfonic acid) -l, 2,4-triazine disodium, 3- (2-pyridine) -5,6-diphenyl- l, 2,4-triazine, 3- (2-pyridine) -5,6-diphenyl-l, 2,4-triazinρ, ρ'-disulfonic acid disodium and 2-hydroxy-4,6-dichloro-l, 3, 5-triazine.
    Examples of the compound containing two or more hydroxyl groups include polyhydric aliphatic alcohols such as propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, D-glucose, D-glucitol, isopropylene glycol, dimethylol propionic acid, butanediol, 1 , 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, thiodiethanol, glycose, tartaric acid, D-glucaric acid and glutaconic acid; Polymer alcohol, such as
    BE2017 / 5679 such as cellulose, polysaccharides and sugar alcohol; aromatic
    Compounds such as 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 2,3dihydroxy-l-pentadecylbenzene, 2,4-dihydroxyacetophenone, 2,5dihydroxyacetophenone, 2,4-dihydroxybenzophenone,
    2,6-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 2,4'-dihydroxydiphenyl sulfone, 2,2 ', 5,5'-tetrahydroxydiphenyl sulfone, 3,3', 5,5'-tetramethyl-4,4 '-dihydroxydiphenylsulfone,
    Hydroxy-quinonecarboxylic acid and salts thereof, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 1,4-hydroquinone sulfonic acid and salts thereof, 4,5- Hydroxybenzene-1,3-disulfonic acid and salts thereof, 1,5-dihydroxy-naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene,
    2.7-dihydroxy-naphthalene, 2,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene-2,6-dicarboxylic acid, 1,6-dihydroxynaphthalene-2,5-dicarboxylic acid, 1,5-dihydroxy-naphthoic acid, 1,4-di hydroxy-2-naphthoic acid phenyl ester, 4 , 5-dihydroxy-naphthalene-2,7-disulfonic acid and salts thereof, l, 8-dihydroxy-3,6-naphthalene-disulfonic acid and salts thereof, 6,7-dihydroxy-2-naphthalenesulfonic acid and salts thereof, 1,2, 3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene, 5-methyl-l, 2,3-trihydroxybenzene, 5-ethyl-l, 2,3-trihydroxybenzene, 5-propyl-1,2,3trihydroxybenzene, trihydroxybenzoic acid, trihydroxyachenophenone , Trihydroxybenzoaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetrahydroxy-p-benzoquinone,
    Tetrahydroxyanthraquinone, methyl gallate and ethyl gallate; and potassium hydroquinone sulfonate.
    Examples of the compound containing one or more hydroxy groups and one or more carboxy groups include tartaric acid, glyceric acid, dimethylolbutanoic acid, dimethylolpropanoic acid, DGlucaric acid and glutaconic acid.
    The compound containing an amide group is a monomolecular compound having an amide bond represented by -CO-NH- (the CO residue is a double bond) in one molecule. In other words, examples of the amide compound include a compound containing a functional group at both ends of the bond
    BE2017 / 5679
    Compound formed by a cyclic compound forming a
    End of the bond is bound, and urea and a urea derivative in which the functional group is hydrogen at both ends.
    Specific examples of the amide compound include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-furamide, formamide, N-methylformamide, propionamide, propiolamide, butyramide, isobutyramide, paliamide , Oxamide, glutaramide, adipamide, cinnamamide, glycolamide, lactamide, glyceramide, tartaramide, citramid, glyoxylamide, pyruvamide, acetoacetamide, dimethylacetamide, benzylamide, anthranilamide, ethylenediaminetetraacetamide, diacetamide, triacetamide, dibenzamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, tribetamide, dibenzamide, , Biuret, butyl urea, dibutyl urea, 1,3-dimethyl urea, 1,3-diethyl urea and derivatives thereof.
    [0055] Furthermore, acrylamide can be used as an amide compound. Examples of the acrylamide include N-methyl acrylamide, NMethyl methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N, ND dimethylacrylamide, Ν, Ν-dimethyl methacrylamide, N, N-diethylacrylamide, Ν, Ν-diethyl methacrylamide, 2-hydroxyethylacrylamide, 2-hydroxymethyl acrylamide, 2-hydroxymethyl acrylamide NMethylol methacrylamide.
    The molecular weight of the amide compound is preferably in a range from 46 to 10,000, more preferably in a range from 46 to 5,000 and particularly preferably in a range from 46 to 1,000.
    [0056] As the amide compound, a monomolecular compound having an imide bond (hereinafter referred to as an imide compound) is preferred from the viewpoint of excellent conductivity. Examples of the imide compound based on the skeleton thereof include phthalimide and a phthalimide derivative, succinimide and a succinimide derivative, benzimide and a benzimide derivative, maleimide and a maleimide derivative and naphthalimide and a naphthalimide derivative.
    Furthermore, the imide compound is converted into aliphatic imide, aromatic imide and the like based on the kind of functional group
    BE2017 / 5679 classified both ends. From the viewpoint of solubility, aliphatic imide is preferred.
    Furthermore, an aliphatic imide compound is classified into a saturated aliphatic imide compound which has no unsaturated bond between carbons in one molecule and an unsaturated aliphatic imide compound which has an unsaturated bond between carbons in one molecule.
    The saturated aliphatic imide compound is a compound represented by R ^ -CO-NHCO-R 2 (R 1 and R 2 represent saturated hydrocarbon). Specific examples thereof include cyclohexane1.2-dicarboxyimide, allantoin, hydantoin, barbituric acid, alloxan, glutarimide, succinimide, 5-butylhydantoic acid, 5,5-dimethylhydantoin, 1methylhydantoin, 1,5,5-trimethylhydantoin, 5-hydantoin acetic acid, NHydroxy-5 norbornene-2,3-dicarboxyimide, semicarbazide, a, a-dimethyl-6methylsuccinimide, bis [2- (succinimidoxycarbonyloxy) ethyl] sulfone, a-methyl-propylsuccinimide and cyclohexylimide.
    The unsaturated aliphatic amide compound is a compound represented by R X -CONH-CO-R 2 (one or both of R 1 and R 2 are one or more unsaturated bonds). Include specific examples of these
    1.3- Dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, NHydroxymaleimid, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 1,8-bismaleimidoctane and N-carboxyheptylmaleimide.
    The molecular weight of the imide compound is preferably in a range from 60 to 5000, more preferably in a range from 70 to 1000 and particularly preferably in a range from 80 to 500.
    The lactam compound is an intramolecular cyclic amide of an aminocarboxylic acid and is a compound in which part of the cycle is -CO-NR- (R represents hydrogen or an optional substituent). One or more carbon atoms in the ring may be unsaturated or substituted with heteroatoms.
    Examples of the lactam compound include pentane-4-lactam, 4-pentane lactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexane-6lactam and 6-hexane lactam.
    BE2017 / 5679 Examples of the compound containing a glycidyl group include
    Glycidyl compounds such as ethyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether,
    Glycidylphenyl ether, bisphenol A, diglycidyl ether, acrylic acid glycidyl ether and methacrylic acid glycidyl ether.
    The content of the highly conductive agent is preferably in a range of 1 to 1000 times, and more preferably in a range of 2 to 100 times, the total mass of the amine adduct. In a case where the content of the highly conductive agent is greater than or equal to the lower limit described above, the effect of improving the conductivity can be brought about satisfactorily by adding the highly conductive agent. In a case where the content thereof is less than or equal to the upper limit, the deterioration in conductivity caused by the decrease in the concentration of the conjugated conductive polymer can be prevented.
    (Other additives)
    The amine adduct liquid can contain known additives.
    The additives are not limited as long as the scope of the present invention is not impaired, and examples thereof include a surfactant, an inorganic conductive agent, a defoaming agent, a coupling agent, an antioxidant and an ultraviolet absorbing agent. The additives here are compounds which differ from the amine compound, the conjugated conductive polymer, the polyanion, the binder component and the highly conductive agent.
    Examples of the surfactant include nonionic surfactants, anionic surfactants and cationic surfactants. Nonionic surfactants are preferred from the viewpoint of storage stability. A polymer-based surfactant such as polyvinylpyrrolidone can also be added.
    Examples of the inorganic conductive agent include metal ions and conductive carbon. In addition, the metal ions can be generated by dissolving metal salts in water.
    BE2017 / 5679
    Examples of the defoaming agent include a silicone resin,
    Polydimethylsiloxane and silicone oil.
    Examples of the coupling agent include a silane coupling agent containing a vinyl group, an amino group, an epoxy group and the like.
    Examples of the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and saccharides.
    Examples of the ultraviolet absorbent include a benzotriazole-based ultraviolet absorbent, a benzophenone-based ultraviolet absorbent, a salicylate-based ultraviolet absorbent, a cyanoacrylate-based ultraviolet absorbent, an oxanilide-based ultraviolet absorbent hindered amine-based ultraviolet absorbent and a benzoate-based ultraviolet absorbent.
    In a case where the amine adduct liquid contains the additives described above, the content thereof is appropriately determined according to the kind of the additive. For example, the content thereof can be set in a range of 0.001 parts by mass to 5 parts by mass with respect to 100 parts by mass of the solid content (non-volatile content) in the conductive composite.
    In a case where the amine adduct liquid is stored in a temperature range of 20 ° C to 28 ° C for 1 week, it is preferable that the precipitation of the solid is not visually noticed. According to the method for producing an amine adduct liquid of a conductive composite of the present invention, it is preferred that the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene), which is polyanion, polystyrene sulfonic acid, the amine compound is trioctylamine or tributylamine, and that organic solvent which dissolves or disperses the amine adduct, isopropanol or methyl ethyl ketone.
    According to the method for producing an amine adduct liquid of a conductive composite of the present invention, it is preferable to
    BE2017 / 5679 that the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene), the polyanion is polystyrene sulfonic acid, the amine compound is trioctylamine or tributylamine, the organic solvent which dissolves or disperses the amine adduct, isopropanol or methyl ethyl ketone and the amount of the organic solvent to be added, which dissolves or disperses the amine adduct, is in a range of 1,000 to 100,000 parts by mass with respect to 100 parts by mass of the amine adduct. << Process for making conductive film >>
    According to a third embodiment of the present invention, a method of manufacturing a conductive film includes a step of obtaining an amine adduct liquid according to the manufacturing method of the second embodiment, a coating step of coating at least one surface of a base film with an amine adduct liquid, and a drying step of drying the applied amine adduct liquid.
    The conductive film produced is suitable for applications of an antistatic film and the like.
    In a case where the amine adduct liquid contains an active energy ray curable binder component, the method may include an active energy radiation step of irradiating the dried coated film with active energy rays after the drying step. When the method includes the active energy irradiation step, the speed of forming the conductive layer can be increased, so that the productivity of the conductive film is improved.
    The conductive film obtained by the manufacturing method described above includes a base film and a conductive layer formed on at least one surface of the base film. The conductive layer contains the amine adduct of the third embodiment.
    The average thickness of the conductive layer is preferably in a range from 10 nm to 20,000 nm, more preferably in a range from 20 nm to 10,000 nm and even more preferably in a range from 30 nm to 5000 nm. In one case, where the average thickness of the conductive layer is greater than or equal to the lower limit described above,
    BE2017 / 5679 can demonstrate high conductivity satisfactorily. In a case where the average thickness of the conductive layer is less than or equal to the upper limit described above, the conductive layer can be easily formed. The average thickness of the conductive layer is a value obtained by measuring the thickness of the conductive layer at optional 10 locations using a thickness meter and taking the average of the measured values.
    As the base film used during the coating step of the present embodiment, for example, a plastic film can be used.
    Examples of the resin for a base film which forms a plastic film include an ethylene-methyl methacrylate copolymer resin, an ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate,
    Polybutylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, a styrene-based elastomer, a polyester-based elastomer, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, polyimide, cellulose triacetate and cellulose acetate propionate. Among these resins for a base film, polyethylene terephthalate and cellulose triacetate are preferred from the viewpoints of low cost and excellent mechanical strength.
    The resin for a base film can be amorphous or crystalline.
    Furthermore, the base film may not be stretched or stretched.
    Further, in order to improve the adhesiveness of the conductive layer to be formed from the conductive polymer dispersion liquid, the base film may be subjected to a surface treatment such as a corona discharge treatment, a plasma treatment or a flame treatment.
    The average thickness of the base film is preferably in a range from 10 pm to 500 pm and more preferably in a range from 20 pm to 200 pm. In a case where the average thickness of the base film is greater than or equal to the lower limit described above, the film is unlikely to break. In a case where the average thickness of the base film
    BE2017 / 5679 is less than or equal to the upper limit, the base film can ensure satisfactory flexibility.
    The thickness of the base film is a value obtained by measuring the thickness of the base film at optional 10 locations using a thickness meter and taking the average of the measured values.
    Examples of the method for coating the film with the amine adduct liquid include a coating method using a coater such as an gravure coater, a roller coater, a curtain flow coater, a rotary coater, a bar coater, a reverse coater, a kiss coater, a fountain coater, a rod coater, an airdoctor coater, a knife coater, a knife coater, a cast coater, or a screen coater; a spraying method using a sprayer such as an air sprayer, an airless sprayer, or a rotor damper; and an immersion method such as immersion.
    In a case of commercially available bar coaters, numbers are given to knife coaters for each type, and the liquid can be applied thicker as the number of knife coaters increases.
    The amount of the amine adduct liquid to be applied to the base film is not particularly limited, but is preferably in a range of 0.1 g / m 2 to 2.0 g / m 2 as the solid content (non-volatile content).
    Examples of the drying process during the drying step include natural drying, drying by hot air, drying by heating, and drying in vacuo. As the drying by heating, a typical method such as heating by hot air or heating by using infrared rays can be used.
    The heating temperature for drying by heating is appropriately set according to the kind of the organic solvent contained in the coating film, and can be set, for example, in a range from 50 ° C to 150 ° C. Here is the
    BE2017 / 5679
    Heating temperature is a set temperature of a drying device. The
    Drying time can range for example from 30 seconds to
    Minutes can be set.
    In a case where the method includes the active energy ray irradiation step, examples of the active energy rays to be used include ultraviolet rays, electron rays and visible light rays. Among the examples of active energy rays, ultraviolet rays are preferred from a general point of view. For example, light sources such as an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used during exposure to ultraviolet rays.
    The irradiance during the irradiation with ultraviolet rays is preferably in a range from 100 mW / cm 2 to 500 mW / cm 2 . In a case where the irradiance is greater than or equal to 100 mW / cm 2 , the active energy radiation curable binder component can be cured satisfactorily. Furthermore, the integrated light intensity is preferably in a range from 50 mJ / cm 2 to 1000 mJ / cm 2 . In a case where the integrated light intensity is greater than or equal to 50 mJ / cm 2 , the binder component can be crosslinked satisfactorily. Furthermore, the irradiance and the integrated light intensity described above are values measured using UVR-Tl (industrial UV checker, photodetector: UD-T36, measurement wavelength range: 300 nm to 390 nm, peak sensitivity wavelength: approximately 355 nm, manufactured by TOPCON CORPORATION).
    The average thickness of the conductive layer to be formed on the base film can be set, for example, in a range from 10 nm to 100 pm. Here, the average thickness of the conductive layer is a value obtained by measuring the thickness of the conductive layer at optional 10 locations using a thickness meter and taking the average of the measured values. In a case where the average thickness of the conductive layer is greater than or equal to that above
    BE2017 / 5679 described lower limit, excellent conductivity can be obtained. In a case where the average thickness thereof is less than or equal to the upper limit described above, the conductive layer can be easily formed.
    According to the method for producing a conductive film, since the dispersion medium of the amine adduct liquid is an organic solvent, the wettability with respect to the base film is excellent. Therefore, a conductive film with excellent adhesiveness to the conductive layer and the base film can be obtained.
    According to the method for producing a conductive film of the present invention, it is preferred that the base film is a PET film which is π-conjugated conductive polymer poly (3,4-ethylenedioxythiophene), which is polyanion, polystyrene sulfonic acid, and the amine compound Is trioctylamine or tributylamine.
    According to the method for producing an amine adduct of a conductive composite of the present invention, since a conductive composite is used in which the mass ratio of the π-conjugated conductive polymer to the polyanion has been adjusted to be in a range of 1: 3 to 1: 7 To be 5, the storage stability of the amine adduct to be obtained is improved. The mechanism is unclear, but the shape with excellent storage stability is believed to be obtained by binding part of anion groups derived from the polyanion contained in the conductive composite to the amine compound.
    [Examples] (Production Example 1)
    206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion exchange water, 1.14 g of oxidizing ammonium persulfate solution, which was previously dissolved in 10 ml of water, was added dropwise to the solution for 20 minutes while stirring the solution at 80 ° C, and the resulting solution was stirred for 12 hours.
    1000 mL of sulfuric acid diluted at a concentration of 10 mass% was added to the resulting solution containing sodium styrene sulfonate, about 1000 mL of
    BE2017 / 5679
    The solution containing polystyrene sulfonic acid was removed by an ultrafiltration method, 2000 ml of ion exchange water was added to the residual liquid, and approximately 2000 ml of the solution was removed by the ultrafiltration method. The ultrafiltration operation described above was repeated three times. Furthermore, about 2000 ml of ion exchange water was added to the obtained filtrate, and about 2000 ml of the solution was removed by the ultrafiltration method. The ultrafiltration operation described above was repeated three times.
    Water in the obtained solution was removed under reduced pressure, whereby polystyrene sulfonic acid (average molecular weight of 200,000) was obtained in the form of a colorless solid. Next, the polystyrene sulfonic acid obtained was dissolved in water to obtain a 10% aqueous polystyrene sulfonic acid solution.
    (Production Example 2)
    206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion exchange water, 0.76 g of oxidizing ammonium persulfate solution, which was previously dissolved in 10 ml of water, was added dropwise to the solution for 20 minutes while stirring the solution at 80 ° C, and the resulting solution was stirred for 12 hours.
    1000 mL of sulfuric acid diluted at a concentration of 10 mass% was added to the obtained sodium styrene sulfonate-containing solution, about 1000 mL of the polystyrene sulfonic acid-containing solution was removed by an ultrafiltration method, 2000 mL of ion exchange water was added to the residual liquid, and about 2000 mL of Solution was removed by the ultrafiltration process. The ultrafiltration operation described above was repeated three times. Furthermore, about 2000 ml of ion exchange water was added to the obtained filtrate, and about 2000 ml of the solution was removed by the ultrafiltration method. The ultrafiltration operation described above was repeated three times.
    Water in the obtained solution was removed under reduced pressure, whereby polystyrene sulfonic acid (average molecular weight of
    BE2017 / 5679
    300,000) was obtained in the form of a colorless solid. Next, the polystyrene sulfonic acid obtained was dissolved in water to obtain a 10% aqueous polystyrene sulfonic acid solution.
    (Production Example 3)
    0.5 g of 3,4-ethylenedioxythiophene and a solution obtained by dissolving 15 g of the aqueous polystyrene sulfonic acid solution of Production Example 1 in 137.6 ml of ion exchange water were mixed at 20 ° C.
    0.3 g of ammonium persulfate dissolved in 13.6 ml of ion exchange water and an oxidation catalyst solution containing 1.1 g of ferric sulfate were slowly added to the mixed solution obtained in the manner described above while maintaining the temperature of the mixed solution at 20 ° C and the solution was stirred. Furthermore, the resulting solution was stirred and reacted for 3 hours.
    7.0 g of a cation exchange resin was added to the obtained reaction solution, the solution was stirred for 1 hour, and the cation exchange resin was removed by filtration, whereby 1.2% by mass of an aqueous polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) dispersion liquid (aqueous PEDOT -PSS dispersion liquid) was obtained.
    (Production Example 4)
    0.5 g of 3,4-ethylenedioxythiophene and a solution obtained by dissolving 15 g of the aqueous polystyrene sulfonic acid solution of Preparation Example 2 in 137.6 ml of ion exchange water were mixed at 20 ° C.
    0.3 g of ammonium persulfate dissolved in 13.6 ml of ion exchange water and an oxidation catalyst solution containing 1.1 g of ferric sulfate were slowly added to the mixed solution obtained in the manner described above while maintaining the temperature of the mixed solution at 20 ° C and the solution was stirred. Furthermore, the resulting solution was stirred and reacted for 3 hours.
    7.0 g of a cation exchange resin was added to the obtained reaction solution, the solution was stirred for 1 hour, and the cation exchange resin was removed by filtration, thereby
    BE2017 / 5679
    1.2% by mass of an aqueous polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) dispersion liquid (aqueous PEDOT-PSS
    Dispersion liquid) was obtained.
    (Production Example 5)
    0.5 g of 3,4-ethylenedioxythiophene and a solution obtained by dissolving 25 g of the aqueous polystyrene sulfonic acid solution of Production Example 1 in 127.6 ml of ion exchange water were mixed at 20 ° C.
    0.3 g of ammonium persulfate dissolved in 13.6 ml of ion exchange water and an oxidation catalyst solution containing 1.1 g of ferric sulfate were slowly added to the mixed solution obtained in the manner described above while maintaining the temperature of the mixed solution at 20 ° C and the solution was stirred. Furthermore, the resulting solution was stirred and reacted for 3 hours.
    7.0 g of a cation exchange resin was added to the obtained reaction solution, the solution was stirred for 1 hour, and the cation exchange resin was removed by filtration, thereby
    1.8% by mass of an aqueous polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) dispersion liquid (aqueous PEDOT-PSS dispersion liquid) was obtained.
    (Production Example 6)
    0.5 g of 3,4-ethylenedioxythiophene and a solution obtained by dissolving 25 g of the aqueous polystyrene sulfonic acid solution of Production Example 2 in 127.6 ml of ion exchange water were mixed at 20 ° C.
    0.3 g of ammonium persulfate dissolved in 13.6 ml of ion exchange water and an oxidation catalyst solution containing 1.1 g of ferric sulfate were slowly added to the mixed solution obtained in the manner described above while maintaining the temperature of the mixed solution at 20 ° C and the solution was stirred. Furthermore, the resulting solution was stirred and reacted for 3 hours.
    7.0 g of a cation exchange resin was added to the obtained one
    Reaction solution added, the solution was stirred for 1 hour and
    BE2017 / 5679 the cation exchange resin was removed by filtration, thereby
    1.8% by mass of an aqueous polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) dispersion liquid (aqueous PEDOT-PSS
    Dispersion liquid) was obtained.
    (Production Example 7)
    0.5 g of 3,4-ethylenedioxythiophene and a solution by dissolving
    37.5 g of the aqueous polystyrene sulfonic acid solution of Preparation Example 1 obtained in 115.1 mL ion exchange water were mixed at 20 ° C.
    0.3 g of ammonium persulfate dissolved in 13.6 ml of ion exchange water and an oxidation catalyst solution containing 1.1 g of ferric sulfate were slowly added to the mixed solution obtained in the manner described above while maintaining the temperature of the mixed solution at 20 ° C and the solution was stirred. Furthermore, the resulting solution was stirred and reacted for 3 hours.
    7.0 g of a cation exchange resin was added to the obtained reaction solution, the solution was stirred for 1 hour, and the cation exchange resin was removed by filtration, whereby 2.55 mass% of an aqueous polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) dispersion liquid (aqueous PEDOT -PSS dispersion liquid) was obtained.
    (Production Example 8)
    0.5 g of 3,4-ethylenedioxythiophene and a solution by dissolving
    37.5 g of the aqueous polystyrene sulfonic acid solution obtained in Preparation Example 2 in 115.1 mL ion exchange water were mixed at 20 ° C.
    0.3 g of ammonium persulfate dissolved in 13.6 ml of ion exchange water and an oxidation catalyst solution containing 1.1 g of ferric sulfate were slowly added to the mixed solution obtained in the manner described above while maintaining the temperature of the mixed solution at 20 ° C and the solution was stirred. Furthermore, the resulting solution was stirred and reacted for 3 hours.
    7.0 g of a cation exchange resin was added to the obtained one
    Reaction solution added, the solution was stirred for 1 hour and
    BE2017 / 5679 the cation exchange resin was removed by filtration, thereby
    2.55% by mass of an aqueous polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) dispersion liquid (aqueous PEDOT-PSS
    Dispersion liquid) was obtained.
    (Production Example 9)
    0.5 g of 3,4-ethylenedioxythiophene and a solution obtained by dissolving 10 g of the aqueous polystyrene sulfonic acid solution of Preparation Example 1 in 142.6 ml of ion exchange water were mixed at 20 ° C.
    0.3 g of ammonium persulfate dissolved in 13.6 ml of ion exchange water and an oxidation catalyst solution containing 1.1 g of ferric sulfate were slowly added to the mixed solution obtained in the manner described above while maintaining the temperature of the mixed solution at 20 ° C and the solution was stirred. Furthermore, the resulting solution was stirred and reacted for 3 hours.
    7.0 g of a cation exchange resin was added to the obtained reaction solution, the solution was stirred for 1 hour, and the cation exchange resin was removed by filtration, whereby 0.9 mass% of an aqueous polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) dispersion liquid (aqueous PEDOT -PSS dispersion liquid) was obtained.
    (Production Example 10)
    0.5 g of 3,4-ethylenedioxythiophene and a solution obtained by dissolving 10 g of the aqueous polystyrene sulfonic acid solution of Preparation Example 2 in 142.6 ml of ion exchange water were mixed at 20 ° C.
    0.3 g of ammonium persulfate dissolved in 13.6 ml of ion exchange water and an oxidation catalyst solution containing 1.1 g of ferric sulfate were slowly added to the mixed solution obtained in the manner described above while maintaining the temperature of the mixed solution at 20 ° C and the solution was stirred. Furthermore, the resulting solution was stirred and reacted for 3 hours.
    7.0 g of a cation exchange resin was added to the obtained one
    Reaction solution added, the solution was stirred for 1 hour and
    BE2017 / 5679 the cation exchange resin was removed by filtration, thereby
    0.9% by mass of an aqueous polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) dispersion liquid (aqueous PEDOT-PSS
    Dispersion liquid) was obtained.
    (Production Example 11)
    0.5 g of 3,4-ethylenedioxythiophene and a solution obtained by dissolving 50 g of the aqueous polystyrene sulfonic acid solution of Production Example 1 in 102.6 ml of ion exchange water were mixed at 20 ° C.
    0.3 g of ammonium persulfate dissolved in 13.6 ml of ion exchange water and an oxidation catalyst solution containing 1.1 g of ferric sulfate were slowly added to the mixed solution obtained in the manner described above while maintaining the temperature of the mixed solution at 20 ° C and the solution was stirred. Furthermore, the resulting solution was stirred and reacted for 3 hours.
    7.0 g of a cation exchange resin was added to the obtained reaction solution, the solution was stirred for 1 hour, and the cation exchange resin was removed by filtration, thereby
    3.3% by mass of an aqueous polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) dispersion liquid (aqueous PEDOT-PSS dispersion liquid) was obtained.
    (Production Example 12)
    0.5 g of 3,4-ethylenedioxythiophene and a solution obtained by dissolving 50 g of the aqueous polystyrene sulfonic acid solution of Preparation Example 2 in 102.6 ml of ion exchange water were mixed at 20 ° C.
    0.3 g of ammonium persulfate dissolved in 13.6 ml of ion exchange water and an oxidation catalyst solution containing 1.1 g of ferric sulfate were slowly added to the mixed solution obtained in the manner described above while maintaining the temperature of the mixed solution at 20 ° C and the solution was stirred. Furthermore, the resulting solution was stirred and reacted for 3 hours.
    7.0 g of a cation exchange resin was added to the obtained one
    Reaction solution added, the solution was stirred for 1 hour and
    BE2017 / 5679 the cation exchange resin was removed by filtration, thereby
    3.3% by mass of an aqueous polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) dispersion liquid (aqueous PEDOT-PSS
    Dispersion liquid) was obtained.
    (Preparation Example 13) g UN-904M resin (manufactured by Negami Chemical Industrial Co., Ltd., urethane acrylate), 20 g pentaerythritol triacrylate, 15 g diacetone alcohol and 1.2 g IRGACURE 127 (manufactured by Ciba Specialty Chemicals Inc.) were mixed, thereby producing a coating material.
    [Example 1]
    A mixed solution of 10.6 g trioctylamine and 100 g
    Isopropanol was added to 100 g of the aqueous PEDOT-PSS
    Dispersion liquid obtained in Preparation Example 3 was added and a trioctylamine adduct of PEDOT-PSS was precipitated. The precipitated trioctylamine adduct of PEDOT-PSS was collected by filtration, washed with 100 g of water and further washed with 100 g of acetone, and the trioctylamine adduct of PEDOT-PSS was extracted in the form of a solid. Filter paper (manufactured by Advantech Co. Ltd.) with a retention particle diameter of 7 pm was used for the filtration.
    0.6 g of the obtained trioctylamine adduct of PEDOT-PSS was added to 100 g of isopropanol and dispersed therein using a high pressure homogenizer to obtain an isopropanol solution with the trioctylamine adduct of PEDOT-PSS at a concentration of 0.6%. The state of the solution after storage at room temperature for 1 week is listed in Table 1.
    Next, a PET film (manufactured by Toray Industries, Inc., LUMIRROR T-60) was coated with the obtained solution using a # 4 bar coater to have a film thickness of about 9.1 µm, and then was at 120 ° C dried for 1 hour. The measurement result of the surface resistance of the obtained film is listed in Table 1.
    BE2017 / 5679
    Next, 53.8 g of the obtained solution was mixed with 46.2 g of the coating material of Production Example 13, and a PET film (manufactured by Toray Industries, Inc., LUMIRROR T-60) was mixed with the mixed solution using a # 12 bar coater coated to have a film thickness of approximately 27 pm, dried at 120 ° C. for 1 hour and irradiated with 400 mJ ultraviolet rays. The measurement result of the surface resistance of the obtained film is listed in Table 1.
    [Example 2]
    The measurement was carried out in the same manner as in Example 1, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 3 was changed to the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 4. The measurement results are listed in Table 1.
    [Example 3]
    The measurement was carried out in the same manner as in Example 1, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 3 was changed to the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 5. The measurement results are listed in Table 1.
    [Example 4]
    The measurement was carried out in the same manner as in Example 1, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 3 was changed to the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 6. The measurement results are listed in Table 1.
    [Example 5]
    The measurement was carried out in the same manner as in Example 1, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 3 was changed to the aqueous PEDOT-PSS dispersion liquid used in the
    BE2017 / 5679
    Production Example 7 was obtained. The measurement results are listed in Table 1.
    [Example 6]
    The measurement was carried out in the same manner as in Example 1, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 3 was changed to the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 8. The measurement results are listed in Table 1.
    [Example 7]
    A mixed solution of 5.6 g of tributylamine and 100 g of isopropanol was added to 100 g of the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 5, and a tributylamine adduct of PEDOT-PSS was precipitated. The precipitated tributylamine adduct of PEDOT-PSS was collected by filtration, washed with 100 g of water and further washed with 100 g of acetone, and the tributylamine adduct of PEDOT-PSS was extracted in the form of a solid. With the exception of the procedures described above, the measurement was carried out in the same manner as in Example 1. The measurement results are listed in Table 1.
    [Example 8]
    A mixed solution of 5.6 g of tributylamine and 100 g of isopropanol was added to 100 g of the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 6, and a tributylamine adduct of PEDOT-PSS was precipitated. The precipitated tributylamine adduct of PEDOT-PSS was collected by filtration, washed with 100 g of water and further washed with 100 g of acetone, and the tributylamine adduct of PEDOT-PSS was extracted in the form of a solid. With the exception of the procedures described above, the measurement was carried out in the same manner as in Example 1. The measurement results are listed in Table 1.
    [Example 9]
    A mixed solution of 10.6 g trioctylamine and 100 g isopropanol became 100 g of the aqueous PEDOT-PSS
    BE2017 / 5679
    Dispersion liquid obtained in Preparation Example 5 was added and a trioctylamine adduct of PEDOT-PSS was precipitated. The precipitated trioctylamine adduct of PEDOT-PSS was collected by filtration, washed with 100 g of water and further washed with 100 g of acetone, and the trioctylamine adduct of PEDOT-PSS was extracted in the form of a solid. Filter paper (manufactured by Advantech Co. Ltd.) with a retention particle diameter of 7 pm was used for the filtration.
    0.6 g of the obtained trioctylamine adduct of PEDOT-PSS was added to 100 g of methyl ethyl ketone and dispersed therein using a high pressure homogenizer to obtain a methyl ethyl ketone solution with the trioctylamine adduct of PEDOT-PSS at a concentration of 0.6%. The measurement was carried out using this solution in the same manner as in Example 1. The measurement results are listed in Table 1.
    [Comparative Example 1]
    The measurement was carried out in the same manner as in Example 1, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 3 was changed to the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 9. The measurement results are listed in Table 1.
    [Comparative Example 2]
    The measurement was carried out in the same manner as in Example 1, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 3 was changed to the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 10. The measurement results are listed in Table 1.
    Comparative Example 3
    The measurement was carried out in the same manner as in Example 1, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 3 was changed to the aqueous PEDOT-PSS dispersion liquid used in the
    BE2017 / 5679
    Production Example 11 was obtained. The measurement results are listed in the table.
    [Comparative Example 4]
    The measurement was carried out in the same manner as in Example 1, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 3 was changed to the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 12. The measurement results are listed in Table 1.
    [Comparative Example 5]
    The measurement was carried out in the same manner as in Example 7, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 5 was changed to the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 9. As a result, since the mixture could not be dispersed even when a high pressure homogenizer was used and separated into two phases, the measurement was stopped.
    [Comparative Example 6]
    The measurement was carried out in the same manner as in Example 7, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 5 was changed to the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 11. As a result, since the solid could not be collected due to the clogging of the tributylamine adduct of PEDOT-PSS by the filter paper during the filtration, the measurement was stopped.
    [Comparative Example 7]
    The measurement was carried out in the same manner as in Example 9, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 5 was changed to the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 9. The measurement results are listed in Table 1.
    2017/5679
    BE2017 / 5679 [Comparative Example 8]
    The measurement was carried out in the same manner as in Example 9, except that the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 5 was changed to the aqueous PEDOT-PSS dispersion liquid obtained in Production Example 11. The measurement results are listed in Table 1.
    The abbreviations in Table 1 are as follows.
    TOA: trioctylamine
    TBA: tributylamine IPA: isopropanol MEK: methyl ethyl ketone
    2017/5679
    BE2017 / 5679
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    2017/5679
    BE2017 / 5679
    60 + 30'Z. 1.0E + 12 or more Z.0 + 30'6 1.0E + 12 or more Ζ0 + 30'9 ο+LUΓΠ _c ΦE 00 i_ LD 00 LD LD ο Φ O ο Ο Ο + TJ + + + + LU O LU LU 1 1 LU LU Ο O Ο Ο Ο r — 1 Γ Ι m LU O r — 1 c C. C. (Ό (Ό (Ό . Tt Φ tfc 00 00 φ 8 = 00 00 o 00 O C. C. 00 o C. C -H C -H ZJ ZJ C -Η ZJ Meimds Meimds picture picture Meimds picture Φ Φ Φ Φ Φ Φ Φ φ Φ ί-ο outFr (ü (ü outFr 13 i_ 00 00 00 < < < < < < Û_ Û_ Û_ Û_ Û_ Û_ a < < < < < < < < O O O O 0Û 0Û ο ο I- 1- 1- 1- 1- 1- 1- 1- ΓΝ ΓΝ 10th 10th Γ Ι 10th Γ Ι 10th r — I r — 1 r — 1 r — 1 τ-1 τ-1 τ-1 τ-1 r — I ΓΝ m LT) LO Γ * · * 00 Φ Φ φ Φ Φ Φ Φ Φ Q_ Q_ Q_ Q_ Q_ Q_ Ο. Ο. σι σι σι σι σι σι σι σι Φ Φ Φ Φ Φ Φ Φ Φ _Q _Q _Q _Ω _Ω _Ω _Ω _Ω σι σι σι σι σι σι σι σι _C _C _C _C _C _C _C _C Ο Ο Ο Ο Ο Φ Φ Φ φ φ φ φ φ 00 00 00 00 00 00 00 00 i_ i_ i_ i_ i_ i_ Φ Φ Φ φ φ φ φ φ > > > > > > > >
    BE2017 / 5679 [considerations>
    As shown in the results described above, in each of the amine adducts of Examples 1 to 9 in which the weight ratio of the conductive polymer to the polyanion was 1: 3 to 1: 7.5, the storage stability when the amine adduct was formed in a solution was excellent, and the surface resistance of the conductive film formed by coating a film with only the liquid or as a coating material and drying the film was also excellent. Regarding the mass ratio range described above, the storage stability was probably excellent when the mass ratio of the polyanion was higher.
    Meanwhile, in each of the amine adducts of Comparative Examples 1, 2, and 7, in which the mass ratio of the polyanion was low, the storage stability when the amine adduct was formed into a solution was unsatisfactory, and a large amount of foreign matter was precipitated. The component of this foreign substance was unclear, but there is a possibility that the component was formed by reprecipitation of part of the amine adduct. It is also believed that the mass ratio of the polyanion can be problematic because the value was extremely low regardless of the type of solvent that forms the solution.
    Further, in each of the amine adducts of Comparative Examples 3, 4 and 8 in which the mass ratio of the polyanion was extremely high, the storage stability when the amine adduct was formed in a solution was unsatisfactory, and the entire solution underwent gelation. The mechanism of this gel formation is unclear, but it is believed that the mass ratio of the polyanion can be problematic because the value was extremely high regardless of the type of solvent that the solution forms.
    Further, in Comparative Example 5, in which the mass of the polyanion was low, and in Comparative Example 6, in which the mass of the polyanion was extremely high, the tributylamine adduct itself showed physical properties that were difficult to handle.
    BE2017 / 5679
    As described above, it is evident that the amine adduct of the conductive composite obtained by the manufacturing method of the present invention, in a case where the amine adduct is formed in a solution, has excellent storage stability and exhibits excellent conductivity as a conductive film.
    [Industrial Applicability] According to the present invention, it is possible to provide a method for producing an amine adduct of a conductive composite that has excellent storage stability. Further, according to the present invention, it is possible to easily form a conductive layer with excellent adhesiveness and conductivity since an amine adduct liquid with less precipitations is used, and to provide a method for producing a conductive film which is capable of reducing the time for the drying step , since the dispersion medium of the amine adduct liquid is an organic solvent.
    While preferred embodiments of the invention have been described and illustrated above, it is to be understood that these are exemplary of the invention and, therefore, should not be considered limiting. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit or scope of the present invention. Accordingly, it is not to be understood that the invention is limited by the foregoing description, and is only limited by the scope of the appended claims.
    BE2017 / 5679
    权利要求:
    Claims (15)
    [1]
    PATENT CLAIMS
    1. A method of making an amine adduct of a conductive composite comprising:
    Add an amine compound to a conductive polymer dispersion liquid containing water and a conductive composite containing a π-conjugated conductive polymer and a polyanion at a mass ratio of the π-conjugated conductive polymer to the polyanion of 1: 3 to 1: 7.5 contains to precipitate an amine adduct of the conductive composite.
    [2]
    2. The method for producing an amine adduct of a conductive composite according to claim 1, further comprising:
    Add an organic solvent to the dispersion liquid of a conductive polymer.
    [3]
    3. A method of producing an amine adduct of a conductive composite according to claim 1 or 2, further comprising:
    Collect the precipitated amine adduct by filtration.
    [4]
    4. The method for producing an amine adduct of a conductive composite according to claim 3, further comprising:
    Wash the collected amine adduct with an organic solvent.
    [5]
    5. The method for producing an amine adduct of a conductive composite according to claim 2, wherein the organic solvent added to the dispersion liquid of a conductive polymer is isopropanol.
    BE2017 / 5679
    [6]
    6. The method for producing an amine adduct of a conductive composite according to claim 4, wherein the organic solvent for washing the amine adduct is acetone.
    [7]
    7. A method for producing an amine adduct of a conductive composite according to any one of claims 1 to 6, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
    [8]
    8. A method of making an amine adduct of a conductive composite according to any one of claims 1 to 7, wherein the polyanion is polystyrene sulfonic acid.
    [9]
    9. A method for producing an amine adduct of a conductive composite according to any one of claims 1 to 8, wherein the amine compound is trioctylamine or tributylamine.
    [10]
    10. A method of making an amine adduct liquid of a conductive composite comprising:
    Obtaining an amine adduct of the conductive composite by the manufacturing process according to any one of claims 1 to 9; and
    Dissolving or dispersing the amine adduct of the conductive composite in an organic solvent.
    [11]
    11. The method for producing an amine adduct liquid of a conductive composite according to claim 10, wherein the organic solvent is isopropanol or methyl ethyl ketone.
    [12]
    12. A method for producing an amine adduct liquid of a conductive composite according to claim 10 or 11, further comprising:
    Add a binder component.
    BE2017 / 5679
    [13]
    13. A method for producing an amine adduct liquid of a conductive composite according to claim 12, wherein the binder component is curable with active energy rays.
    [14]
    14. A method of making a conductive film comprising:
    a step of obtaining an amine adduct liquid of the conductive composite by the manufacturing method according to any one of claims 10 to 13;
    a coating step of coating at least one surface of a base film with the amine adduct liquid of the conductive composite; and a drying step of drying the applied amine adduct liquid.
    [15]
    The method of manufacturing a conductive film according to claim 14, wherein the amine adduct liquid contains a binder component curable with active energy rays, and the method further comprises an active energy beam irradiation step of irradiating a coated film of the dried amine adduct liquid with active energy rays after the drying step.
    2017/5679
    SUMMARY
    BE2017 / 5679
    A method is provided for producing an amine adduct of a conductive composite which includes: adding an amine compound
    5, a conductive polymer dispersion liquid containing water and a conductive composite containing a π-conjugated conductive polymer and a polyanion at a mass ratio of the π-conjugated conductive polymer to the polyanion of 1: 3 to 1: 7.5 to precipitate an amine adduct of the conductive composite.
    Europ & ïsificî ftn «nt Office üH-îçsï κ · [, κςΐί> έ <ϊί>) Îrî. brevets
    REGHERGHENBER1CHT according to Artikei XJ.S3., §2 and §3 of the Belgian Commercial Code
    Number of supplicants
    SO 11539 BE 201/05679
    RELEVANT DOCUMENTS
    Identification of the document with details, as far as required, of the file AffectsAnSfXüöh CLASSIFICATION DE Ft REGISTRATION {(PC) XXXÄ US 7 317 048 32 (DU PONT [US])January 8, 2008 {2008-01-08}* Claims 1-4; Example 1 *EP 2 949 706 Al (SHINETSU POLYMER CO [UP]; SHINETSU CHEMICAL C0 [UP])December 2, 2015 (2015-12-02)* Paragraphs [0056], [0087], [0094],[0139] *WO 2004/063277 Al (DU PONT DE NEMOURS & C0 E 1} July 29, 2004 (2004-07-29)* Claims 1,3,27,37 *KÎM U Y ET AL: ENHANCEMENT OF ELECTRICAL CONDUCTIVITY OFP0LY (3,4-ETBYLENEDIQXYTHI0PHENE) / P0LYf4-ST YRENESULFONATE) SY A CHANGE OF SOLVENTS, SYNTHETIC METALS, ELSEVIER SEQUOIA, LAUSANNE, CH,Vol. 126, No. 2/03,February 1, 2002 (2002-02-01), pages 311-316, XP001189321,ISSN: 0379-6779, DOI:10.1016 / S0379 ~ 67 9 (01) 00576-8* 2nd experiment * 1-151.7-91.7-91-15 1 NV.C08J3 / Q3 HSCHERÇHæRTe SAÇMGëDIETÉ (IPO) · CÔ8J March 12, 2018 Schweissguth, Martin CATEGORY OF OUR DOCUMENTS T cd ^ r Effindcny based û & g & rsdft Theonen cutei principles£ ’& ihofe & Patenutokdtneni, but not until thenX / of special Becteuiiing old üoüäöhlet after the Anrnewedaturn veröüentuchtwüi'dön isV von msüMdtfïoi * Meaning in connection with a D 'document mentioned in the applicationand ^ r ^ n V «räfömffa> hun $ d & roütt> & n Kategcun L. äuä öndamn reasons cited DotomaniA: technical background. ............................. ..................... ......................................O n ^ hteohnthch® Off®fÄ »r« rts &: Mrtgttettctergtetdhen Patenttamtöe. CdCfèinstirnmendei;P: £ w <& ohenhter »tur document
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    法律状态:
    2018-11-12| FG| Patent granted|Effective date: 20180917 |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2016193967A|JP6941423B2|2016-09-30|2016-09-30|A method for producing an amine adduct of a conductive composite, a method for producing an amine adduct liquid for a conductive composite, and a method for producing a conductive film.|
    JP2016-193967|2016-09-30|
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