WO2015056609A1 - Composition pour la formation de film conducteur transparent, conducteur transparent et procédé de production de conducteur transparent - Google Patents

Composition pour la formation de film conducteur transparent, conducteur transparent et procédé de production de conducteur transparent Download PDF

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WO2015056609A1
WO2015056609A1 PCT/JP2014/076876 JP2014076876W WO2015056609A1 WO 2015056609 A1 WO2015056609 A1 WO 2015056609A1 JP 2014076876 W JP2014076876 W JP 2014076876W WO 2015056609 A1 WO2015056609 A1 WO 2015056609A1
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conductive film
transparent conductive
transparent
composition
group
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PCT/JP2014/076876
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Japanese (ja)
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藤田　貴史
隆裕 櫻井
康功 久留島
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ナガセケムテックス株式会社
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Priority to JP2015542584A priority Critical patent/JPWO2015056609A1/ja
Publication of WO2015056609A1 publication Critical patent/WO2015056609A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

  • the present invention relates to a transparent conductive film-forming composition, a transparent conductor provided with a transparent conductive film comprising the transparent conductive film-forming composition, and a method for producing the transparent conductor.
  • the transparent conductor has a structure in which a transparent conductive film is formed on a transparent substrate using a composition containing a conductive polymer. Such a transparent conductive film is required to have high transparency and conductivity.
  • Patent Document 1 proposes a composition containing a conductive polymer and metal nanowires as a composition having excellent transparency and conductivity when formed into a transparent conductive film.
  • the transparent conductive film obtained by curing the composition described in Patent Document 1 still has a problem that transparency and conductivity are not sufficient.
  • a protective film is required, and there is a problem that the contact resistance with the circuit becomes too large.
  • An object of this invention is to provide the composition for transparent conductive film formation which has the characteristic that it is excellent in transparency and electroconductivity, when it is set as a transparent conductive film.
  • this invention is a transparent conductor provided with the transparent conductive film which consists of a composition for transparent conductive film formation of this invention, and the manufacturing method of a transparent conductor using the composition for transparent conductive film formation of this invention. The purpose is to provide.
  • the present inventors have obtained a composition obtained by blending (C) a conductivity improver into a mixture comprising (A) metal nanowires, (B) a conductive polymer and (D) a binder. Based on the combination of (A) metal nanowires and (C) conductivity improver, it has been found that when it is a transparent conductive film, it has a characteristic that it is excellent in transparency and conductivity. And based on these knowledge, the present inventors completed the composition for transparent conductive film formation of this invention, the transparent conductor of this invention, and the manufacturing method of the transparent conductor of this invention.
  • the composition for forming a transparent conductive film of the present invention is (A) metal nanowires, (B) a conductive polymer; (C) a conductivity improver, and (D) contains a binder,
  • the solid content of the (D) binder is 0.1 to 1000 weights with respect to 100 parts by weight of the total content of the solid content of the (A) metal nanowire and the solid content of the (B) conductive polymer. It is a part.
  • the conductive polymer (B) is a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid, and has a content of 0.01 S / cm or more. It preferably has electrical conductivity.
  • the (D) binder is preferably at least one selected from the group consisting of polyester, polyurethane, acrylic resin, alkyl silicate, and polyolefin.
  • composition for forming a transparent conductive film of the present invention further contains (E) a surfactant,
  • the (E) surfactant is preferably a siloxane compound or a fluorine compound.
  • composition for forming a transparent conductive film of the present invention further contains (F) a water-soluble antioxidant,
  • the (F) water-soluble antioxidant is preferably a compound having a lactone ring substituted with two hydroxyl groups or a compound having two or more phenolic hydroxyl groups.
  • the (C) conductivity improver is (I) a compound having a boiling point of 60 ° C. or higher and having at least one ketone group in the molecule; (Ii) a compound having a boiling point of 100 ° C. or higher and having at least one ether group in the molecule; (Iii) a compound having a boiling point of 100 ° C. or higher and having at least one sulfinyl group in the molecule; (Iv) a compound having a boiling point of 100 ° C. or higher and having at least one amide group in the molecule; (V) a compound having a boiling point of 50 ° C.
  • the boiling point is preferably at least one selected from the group consisting of compounds having a boiling point of 100 ° C. or higher and having at least one lactam group in the molecule.
  • the transparent conductor of the present invention is a transparent conductor comprising a transparent substrate and a transparent conductive film laminated on at least one surface of the transparent substrate,
  • the said transparent conductive film is a film
  • the method for producing a transparent conductor of the present invention comprises: (I) an application step of applying the transparent conductive film-forming composition of the present invention to at least one surface of a transparent substrate; and (II) By heat-treating the transparent base material on which at least one surface obtained in the coating step (I) is coated with the composition for forming a transparent conductive film under a temperature condition of 150 ° C. or lower, It includes a forming step of forming a transparent conductive film on at least one surface.
  • the transparent conductor of the present invention and the transparent conductor obtained by the transparent conductor manufacturing method of the present invention are a touch panel, a transparent electrode for driving a liquid crystal, a transparent electrode for driving an EL, and a transparent electrode for driving an electrochromic element. It is preferably used for an electromagnetic shielding material, a transparent heating element, or an electrolytic plating primer.
  • the composition for forming a transparent conductive film of the present invention contains (C) a conductivity improver in addition to (A) a metal nanowire, (B) a conductive polymer, and (D) a binder. In addition, it has the characteristics of excellent transparency and conductivity. Therefore, the composition for forming a transparent conductive film of the present invention can be used very suitably for forming a transparent conductive film in a transparent conductor.
  • the transparent conductor of the present invention comprises a transparent conductive film formed using the composition for forming a transparent conductive film of the present invention having the characteristics that it is excellent in transparency and conductivity when made into a transparent conductive film, Excellent transparency. Moreover, the transparent conductive film with which the transparent conductor of this invention is provided is excellent in transparency and electroconductivity.
  • a transparent conductive film is formed on a transparent substrate using the composition for forming a transparent conductive film of the present invention.
  • the transparent conductor excellent in transparency in which the excellent transparent conductive film was formed can be manufactured suitably.
  • the composition for forming a transparent conductive film of the present invention comprises: (A) metal nanowires, (B) a conductive polymer; (C) a conductivity improver, and (D) contains a binder,
  • the solid content of the (D) binder is 0.1 to 1000 weights with respect to 100 parts by weight of the total content of the solid content of the (A) metal nanowire and the solid content of the (B) conductive polymer. It is a part.
  • (A) metal nanowire what consists of a metal simple substance or a metal containing compound is mentioned.
  • the metal simple substance is not particularly limited, and examples thereof include silver, copper, iron, cobalt, nickel, zinc, ruthenium, rhodium, palladium, cadmium, osmium, iridium, platinum, and the metal-containing compound. Although it does not specifically limit, For example, what contains these metals is mentioned.
  • These (A) metal nanowires may be used alone or in combination of two or more.
  • the (A) metal nanowire is preferably at least one selected from the group consisting of silver nanowires, copper nanowires, and gold nanowires. The reason is that the free electron concentration is high and the conductivity is high compared to other (A) metal nanowires.
  • the diameter of the metal nanowire (A) is not particularly limited, but is preferably 1 to 1000 nm, and more preferably 1 to 100 nm. When the diameter of the metal nanowire (A) is less than 1 nm, the wire itself may be easily cut, and when it exceeds 1000 nm, the haze value of the coating film may be increased.
  • the length of the metal nanowire (A) is not particularly limited, but is preferably 1 to 1000 ⁇ m, and more preferably 1 to 100 ⁇ m. When the length of the (A) metal nanowire is less than 1 ⁇ m, the conductivity of the coating film may be lowered, and when it exceeds 1000 ⁇ m, the stability of the metal nanowire dispersion may be deteriorated.
  • the aspect ratio of the metal nanowire (A) is not particularly limited, but is preferably 50 to 10,000, and more preferably 70 to 7000. This is because if the aspect ratio of the metal nanowire (A) is less than 50, the conductivity of the coating film is lowered, and if it exceeds 10,000, the stability of the metal nanowire dispersion is deteriorated.
  • an aspect ratio represents ratio of the length with respect to the diameter of (A) metal nanowire.
  • the (B) conductive polymer is a compound for imparting conductivity to the transparent conductive film.
  • the (B) conductive polymer is not particularly limited, and a conventionally known conductive polymer can be used. Specific examples thereof include polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, and derivatives thereof. And a composite of these and a dopant. These may be used alone or in combination of two or more.
  • the conductive polymer (B) is preferably a conductive polymer containing at least one thiophene ring in the molecule. The reason is that a molecule having high conductivity is easily formed by including a thiophene ring in the molecule.
  • the conductive polymer (B) is more preferably poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and polyanion. This is because it is extremely excellent in conductivity and chemical stability. Further, when the composition for forming a transparent conductive film contains poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and polyanion, By using the composition for forming a conductive film, a transparent conductive film can be formed in a short time at a low temperature, and the productivity is excellent.
  • poly (3,4-disubstituted thiophene) poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) is particularly preferable.
  • poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) include the following formula (I):
  • R1 and R2 each independently represent a hydrogen atom or a C1-4 alkyl group, or when R1 and R2 are bonded, each represents a C1-4 alkylene group.
  • the C1-4 alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.
  • the C1-4 alkylene group is not particularly limited, and examples thereof include a methylene group, 1,2-ethylene group, 1,3-propylene group, 1,4- Examples include butylene, 1-methyl-1,2-ethylene, 1-ethyl-1,2-ethylene, 1-methyl-1,3-propylene, and 2-methyl-1,3-propylene. . Among these, a methylene group, 1,2-ethylene group, and 1,3-propylene group are preferable, and a 1,2-ethylene group is more preferable. A part of hydrogen of the C1-4 alkyl group and the C1-4 alkylene group may be substituted.
  • the polythiophene having a C1-4 alkylene group is particularly preferably poly (3,4-ethylenedioxythiophene).
  • the poly anion forms a complex by forming an ion pair with the polythiophene (derivative), and the polythiophene (derivative) can be stably dispersed in water.
  • the poly anion is not particularly limited.
  • carboxylic acid polymers for example, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.
  • sulfonic acid polymers for example, polystyrene sulfonic acid, polyvinyl sulfonic acid, poly Isoprene sulfonic acid, etc.
  • carboxylic acid polymers and sulfonic acid polymers are also copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as aromatic vinyl compounds such as acrylates, styrene, vinyl naphthalene, etc. It may be. Among these, polystyrene sulfonic acid is particularly preferable.
  • the polystyrene sulfonic acid has a weight average molecular weight of more than 20000 and preferably 500,000 or less, more preferably 40,000 to 200,000. If polystyrene sulfonic acid having a molecular weight outside this range is used, the dispersion stability of the polythiophene conductive polymer in water may be lowered.
  • the weight average molecular weight is a value measured by gel permeation chromatography (GPC). For the measurement, an ultrahydrogel 500 column manufactured by Waters was used.
  • the conductive polymer (B) is preferably a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid because it is particularly excellent in transparency and conductivity.
  • the conductivity of the conductive polymer (B) is not particularly limited, but is preferably 0.01 S / cm or more and 0.05 S / cm or more from the viewpoint of imparting sufficient conductivity to the transparent conductive film. It is more preferable that
  • the (B) conductive polymer is a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid, and preferably has a conductivity of 0.01 S / cm or more.
  • the reason for this is that the composition for forming a transparent conductive film obtained using such a conductive polymer (B) is particularly excellent in transparency and conductivity when used as a transparent conductive film.
  • the weight ratio of the content of the (A) metal nanowire and the (B) conductive polymer is not particularly limited, but is preferably 100: 1 to 1: 100, and 20: 1 to 1:10. It is more preferable. The reason is that when the ratio of (A) metal nanowires is higher than 100: 1, the film formability of the coating film becomes worse, and when the ratio of (B) conductive polymer is higher than 1: 100. This is because the surface resistivity may increase.
  • the content of the polythiophene conductive polymer in the composition for forming a transparent conductive film is not particularly limited. However, when the transparent conductive film is formed, an amount of 0.01 to 50.0 mg / m 2 is preferable, and 0.1% An amount of ⁇ 10.0 mg / m 2 is more preferred. If it is less than 0.01 mg / m 2, the proportion of the conductive polymer (B) in the transparent conductive film decreases, and the conductivity of the transparent conductive film may not be sufficiently secured. This is because if it exceeds m2, the proportion of the conductive polymer (B) in the transparent conductive film increases, which may adversely affect the strength and film formability of the coating film.
  • the said (C) electroconductivity improver is added in order to improve the electroconductivity of the transparent conductive film formed using the composition for transparent conductive film formation.
  • the (C) conductivity improver evaporates by heating when forming a transparent conductive film, and (B) improves the conductivity of the transparent conductive film by controlling the orientation of the conductive polymer. It is estimated to be.
  • the said (C) electroconductivity improver compared with the case where the said (C) electroconductivity improver is not used, there are few compounding quantities of (B) electroconductive polymer, maintaining surface resistivity. As a result, there is an advantage that transparency can be improved.
  • the (C) conductivity improver is at least one selected from the group consisting of the following (i) to (vii) from the viewpoint of ensuring the conductivity necessary for the use of the transparent conductive film. Is preferred.
  • (I) a compound having a boiling point of 60 ° C. or more and having at least one ketone group in the molecule ii) a compound having a boiling point of 100 ° C. or more and having at least one ether group in the molecule (iii) a molecule having a boiling point of 100 ° C. or more
  • Compound (iv) having at least one sulfinyl group in it (iv) Compound having a boiling point of 100 ° C.
  • Examples of the compound (i) having a boiling point of 60 ° C. or higher and having at least one ketone group in the molecule include isophorone, propylene carbonate, ⁇ -butyrolactone, ⁇ -butyrolactone, 1,3-dimethyl-2-imidazolidinone, etc. Is mentioned. These may be used alone or in combination of two or more.
  • Examples of the compound (ii) having a boiling point of 100 ° C. or more and having at least one ether group in the molecule include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, 2-phenoxyethanol, dioxane, morpholine, 4-acryloylmorpholine, Examples thereof include N-methylmorpholine N-oxide, 4-ethylmorpholine, 2-methoxyfuran and the like. These may be used alone or in combination of two or more.
  • Examples of the compound (iii) having a boiling point of 100 ° C. or higher and having at least one sulfinyl group in the molecule include dimethyl sulfoxide and the like.
  • Examples of the compound (iv) having a boiling point of 100 ° C. or more and having at least one amide group in the molecule include N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-ethylacetamide N-phenyl-N-propylacetamide, benzamide and the like. These may be used alone or in combination of two or more.
  • Examples of the compound (v) having a boiling point of 50 ° C. or more and having at least one carboxyl group in the molecule include acrylic acid, methacrylic acid, methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, and octane.
  • Acid decanoic acid, dodecanoic acid, benzoic acid, p-toluic acid, p-chlorobenzoic acid, p-nitrobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, oxalic acid, malonic acid,
  • succinic acid, adipic acid, maleic acid, fumaric acid and the like may be used alone or in combination of two or more.
  • Examples of the compound (vi) having a boiling point of 100 ° C. or more and having two or more hydroxyl groups in the molecule include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, ⁇ -thiodiglycol, triethylene glycol, and tripropylene.
  • Glycol 1,4-butanediol, 1,5-pentanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerin, erythritol, glycerin, immutol , Lactitol, maltitol, mannitol, sorbitol, xylitol, sucrose and the like. These may be used alone or in combination of two or more.
  • Examples of the compound (vii) having a boiling point of 100 ° C. or more and having at least one lactam group in the molecule include N-methylpyrrolidone, ⁇ -lactam, ⁇ -lactam, ⁇ -lactam, ⁇ -caprolactam, laurolactam and the like. Can be mentioned. These may be used alone or in combination of two or more.
  • the (C) conductivity improver When the boiling point of the (C) conductivity improver is equal to or higher than a specific temperature, the (C) conductivity improver gradually volatilizes by heating during the formation of the transparent conductive film. It is considered that the orientation of the conductive polymer (B) is controlled to an orientation advantageous for conductivity, and as a result, the conductivity is improved. On the other hand, if the boiling point of the (C) conductivity improver is less than a specific temperature, the (C) conductivity improver suddenly evaporates, so the orientation of the (B) conductive polymer is It is considered that the conductivity is not sufficiently controlled because of insufficient control.
  • the SP value refers to Hansen's solubility parameter, and the solubility of a substance is expressed by three parameters: a dispersion term ⁇ D, a polar term ⁇ H, and a hydrogen bond term ⁇ P.
  • a conductivity improver having an SP value within the above range it is considered that (B) the conductive polymer is pseudo-dissolved and the alignment is promoted in the evaporation process.
  • the (C) conductivity improver having an SP value outside the above range is less likely to interact with the (B) conductive polymer, it is not possible to obtain a sufficient conductivity improvement effect by controlling the arrangement. Sometimes.
  • the (C) conductivity improver having an SP value within the above range has high affinity with (B) the conductive polymer, the stability of the (B) conductive polymer dispersion can be improved.
  • (B) conductive polymer, particularly polyanion, in the dispersion is considered to contribute to the dispersion stability of (A) metal nanowires depending on its polarity, and (C) by adding a conductivity improver (B) In addition to the conductive polymer, the dispersion stability of (A) metal nanowires can also be improved.
  • the blending amount of the (C) conductivity improver is not particularly limited, but is preferably 5 to 2000 parts by mass and more preferably 10 to 1500 parts by mass with respect to 100 parts by mass of the (B) conductive polymer.
  • the blending amount of the (C) conductivity improver is less than 5 parts by mass, the conductivity improving effect due to the addition of the (C) conductivity improver may not be fully enjoyed.
  • the amount exceeds 2000 parts by mass the blending amount of (A) metal nanowire and (B) conductive polymer in the composition for forming a transparent conductive film is relatively small, and sufficient conductivity is obtained when a transparent conductive film is obtained. Sexuality may not be obtained.
  • (D) Binder Although it does not specifically limit as said (D) binder, for example, polyester, a polyurethane, an acrylic resin, an alkyl silicate, polyolefin, a silane coupling agent etc. are mentioned. These may be used alone or in combination of two or more.
  • the (D) binder is preferably at least one selected from the group consisting of polyester, polyurethane, acrylic resin, alkyl silicate and polyolefin. The reason is that the compatibility with (B) conductive polymer and (A) metal nanowire is good.
  • the polyester is not particularly limited as long as it is a polymer compound obtained by polycondensation of a compound having two or more carboxyl groups in the molecule and a compound having two or more hydroxyl groups.
  • polyethylene Examples include terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. These may be used alone or in combination of two or more.
  • the polyurethane is not particularly limited as long as it is a polymer compound obtained by copolymerizing a compound having an isocyanate group and a compound having a hydroxyl group.
  • ester / ether polyurethane, ether polyurethane, polyester polyurethane , Carbonate polyurethane, acrylic polyurethane and the like may be used alone or in combination of two or more.
  • acrylic resin for example, (meth) acrylic-type resin, vinyl ester-type resin, etc. are mentioned.
  • acrylic resins for example, a polymer containing a polymerizable monomer having an acid group such as a carboxyl group, an acid anhydride group, a sulfonic acid group, or a phosphoric acid group as a constituent monomer may be used. Examples thereof include a single or copolymer of a polymerizable monomer having a group, a copolymer of a polymerizable monomer having a acid group and a copolymerizable monomer, and the like. These may be used alone or in combination of two or more.
  • the (meth) acrylic resin may be polymerized with a copolymerizable monomer as long as it contains a (meth) acrylic monomer as a main constituent monomer (for example, 50 mol% or more).
  • a copolymerizable monomer for example, 50 mol% or more.
  • at least one may have an acid group.
  • Examples of the (meth) acrylic resin include (meth) acrylic monomers having the above acid group [(meth) acrylic acid, sulfoalkyl (meth) acrylate, sulfonic acid group-containing (meth) acrylamide, etc.] or The copolymer, the (meth) acrylic monomer optionally having an acid group, and another polymerizable monomer having an acid group [other polymerizable carboxylic acid, polymerizable polyvalent carboxylic acid Or anhydride, vinyl aromatic sulfonic acid, etc.] and / or the above copolymerizable monomers [for example, (meth) acrylic acid alkyl ester, glycidyl (meth) acrylate, (meth) acrylonitrile, aromatic vinyl monomer, etc.
  • (meth) acrylic resins (meth) acrylic acid- (meth) acrylic acid ester polymers (acrylic acid-methyl methacrylate copolymer, etc.), (meth) acrylic acid- (meth) acrylic acid An ester-styrene copolymer (such as acrylic acid-methyl methacrylate-styrene copolymer) is preferred.
  • alkyl silicate For example, a methyl silicate, an ethyl silicate, a propyl silicate, a butyl silicate, a methyl silicate oligomer, an ethyl silicate oligomer, a propyl silicate oligomer, a butyl silicate oligomer etc. are mentioned. These may be used alone or in combination of two or more.
  • polystyrene resin examples include, but are not limited to, polyethylene, polypropylene, chlorinated polypropylene, maleic anhydride-modified polypropylene, maleic anhydride-modified chlorinated polypropylene, and the like. These may be used alone or in combination of two or more.
  • silane coupling agent For example, what has a vinyl group, an epoxy group, a methacryl group, an acryl group, a mercapto group, a sulfide group, an isocyanate group etc. as an organic functional group is mentioned. These may be used alone or in combination of two or more.
  • the solid content of the (D) binder is 0.1 to 1000 weights with respect to 100 parts by weight of the total content of the solid content of the (A) metal nanowire and the solid content of the (B) conductive polymer. Part.
  • the solid content of the (D) binder is 5 to 500 parts by weight with respect to 100 parts by weight of the total content of the solids of the (A) metal nanowires and the (B) conductive polymer. Preferably there is.
  • the content of the solid content of the (D) binder is less than 0.1 parts by weight, the strength of the transparent conductive film may be weakened.
  • (A ) The ratio of metal nanowires and (B) conductive polymer is relatively small, and the conductivity of the transparent conductive film may not be sufficiently ensured.
  • ⁇ Optional component> In the composition for forming a transparent conductive film of the present invention, in addition to (A) the metal nanowire, (B) the conductive polymer, (C) the conductivity improver, and (D) the binder described above, other components are optionally added. You may contain. Examples of the other components include (E) a surfactant and / or a leveling agent, (F) a water-soluble antioxidant, (G) a solvent, (H) a crosslinking agent, and (I) a catalyst.
  • the uniform transparent conductive film can be obtained by forming a transparent conductive film using the composition for forming a transparent conductive film.
  • one compound may correspond to both a surfactant and a leveling agent.
  • the surfactant is not particularly limited as long as it has an effect of improving leveling properties, and specific examples thereof include, for example, polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethyl Siloxane compounds such as siloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing polydimethylsiloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane; Fluorine-containing organic compounds such as fluoroalkyl carboxylic acid and perfluoroalkyl polyoxyethylene ethanol; polyoxyethylene alkyl phenyl ether, propylene ether Polyether compounds such as side polymers and ethylene oxide polymers; carboxylic acids such as coconut oil fatty acid
  • These surfactants may be used alone or in combination of two or more.
  • siloxane compounds and fluorine-containing organic compounds are preferable, and polyether-modified polydimethylsiloxane is more preferable.
  • the reason is that the siloxane-based compound and the fluorine-containing organic compound have good compatibility with the (A) metal nanowire, have excellent dispersion stability when used as a composition for forming a transparent conductive film, and can easily form a uniform coating film. It is because it can be.
  • surfactant Commercially available products can be used as the surfactant, and specific examples thereof include BYK-301, BYK-302, BYK-307, BYK-331, BYK-333, BYK-337, and BYK-341. , BYK-375, BYK-378, BYK-380N, BYK-340, BYK-DYNWET800 (all manufactured by Big Chemie Japan Co., Ltd.), NIKKOL AM-101, NIKKOL AM-301, NIKKOL AM-3130N (all Japanese surfactant) Kogyo Co., Ltd.), Asahi Guard AG-8025, Asahi Guard MA-91 (both by Meisei Chemical Industry Co., Ltd.), Amipol AS-8 (Nikka Chemical Co., Ltd.), Amorgen AOL, Amorgen CB-C, Amorgen CB -H, Amorgen LB-C, Mogen No.
  • Amorgen S Amorgen SH (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Amphithol Series (manufactured by Kao Corporation), ANFOLEX 35N, ANHOLEX 50, ANHOLEX 50-SF (all are Miyoshi oils and fats) Co., Ltd.), Plus Coat RY-2 (manufactured by Kanayo Chemical Co., Ltd.), Energy Coal C-30 B (manufactured by Lion Co., Ltd.), Obazolin 662N, Kachinal AOC (both manufactured by Toho Chemical Co., Ltd.), Offnon D (Manufactured by Yushiro Chemical Co., Ltd.), Crink A-27 (manufactured by Yoshimura Oil Chemical Co., Ltd.), Genagen B 1566 (manufactured by Clariant Japan Co., Ltd.), KF-6011, KF-6012 (both manufactured by Shin-Etsu Silicone Co., Ltd.
  • the content is not particularly limited, but in terms of solid content, with respect to 100 mass parts of the solid content of the conductive polymer (B). 0.001 to 2300 parts by mass is preferable, and 0.01 to 500 parts by mass is more preferable. If the content of the surfactant is less than 0.001 part by mass, it may be difficult to make the film thickness of the transparent conductive film uniform. On the other hand, if the content exceeds 2300 parts by mass, The ratio of the (A) metal nanowire and (B) conductive polymer is reduced, and the conductivity of the transparent conductive film may not be sufficiently ensured.
  • the leveling agent is not particularly limited.
  • polyether-modified polydimethylsiloxane polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing Siloxane compounds such as polydimethylsiloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; fluorine-containing organic materials such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethyleneethanol Compound: Polyether compound such as polyoxyethylene alkylphenyl ether, propylene oxide polymer, ethylene oxide polymer Carboxylic acids such as coconut oil fatty acid amine salt and gum rosin; castor oil sulfate
  • leveling agent Commercially available products can be used as the leveling agent. Specific examples thereof include BYK-325, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-UV3500, BYK-381, BYKETOL-AQ, BYKETOL-WS (all manufactured by Big Chemie Japan Co., Ltd.), Polyflow WS, Polyflow WS-30, Polyflow WS-314 (all manufactured by Kyoeisha Chemical Industry Co., Ltd.) and the like.
  • the content is not particularly limited, but in terms of solid content, with respect to 100 mass parts of the solid content of the conductive polymer (B). 0.001 to 2300 parts by mass is preferable, and 0.01 to 500 parts by mass is more preferable.
  • the content of the leveling agent is less than 0.001 part by mass, it may be difficult to make the film thickness of the transparent conductive film uniform.
  • the content exceeds 2300 parts by mass, The presence ratio of (A) metal nanowire and (B) conductive polymer decreases, and the conductivity of the transparent conductive film may not be sufficiently ensured.
  • the (F) water-soluble antioxidant is not particularly limited, and examples thereof include a reducing water-soluble antioxidant and a non-reducing water-soluble antioxidant.
  • examples of the reducing water-soluble antioxidant include L-ascorbic acid, sodium L-ascorbate, potassium L-ascorbate, D ( ⁇ )-isoascorbic acid (erythorbic acid), sodium erythorbate, and erythorbic acid.
  • non-reducing water-soluble antioxidant examples include oxidation of phenylimidazolesulfonic acid, phenyltriazolesulfonic acid, 2-hydroxypyrimidine, phenyl salicylate, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, and the like. Examples include compounds that absorb ultraviolet rays that cause deterioration. These (F) water-soluble antioxidants may be used alone or in combination of two or more.
  • a compound having a lactone ring substituted with two hydroxyl groups or a compound having two or more phenolic hydroxyl groups is preferable, and D (-)-isoascorbic acid, tannic acid, or Sanmerin (registered trademark) is preferable. Y-AF is more preferred.
  • the reason is that when (A) the metal nanowire is blended, the bleedout phenomenon in which (F) the water-soluble antioxidant emerges on the surface of the coating film with the passage of time becomes remarkable, but it was substituted with two hydroxyl groups.
  • the content is not particularly limited, but is 0.001 with respect to 100 parts by mass of the (B) conductive polymer. Is preferably 500 parts by mass, more preferably 0.01 to 250 parts by mass, and even more preferably 0.05 to 100 parts by mass.
  • the content of the water-soluble antioxidant (F) is less than 0.001 part by mass, the heat resistance and moist heat resistance of the transparent conductive film formed using the composition for forming a transparent conductive film are sufficiently improved.
  • the proportion of (A) metal nanowires and (B) conductive polymer in the transparent conductive film formed using the composition for forming a transparent conductive film decreases. In some cases, sufficient conductivity of the transparent conductive film cannot be ensured.
  • the solvent (G) is not particularly limited.
  • water alcohols such as methanol, ethanol, 2-propanol, 1-propanol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, etc.
  • the (G) solvent is preferably water or a mixture of water and an organic solvent.
  • the content of water is not particularly limited, but relative to 100 parts by mass of the solid content of the conductive polymer (B). 20 to 1000000 parts by mass is preferable, and 200 to 500000 parts by mass is more preferable. If the water content is less than 20 parts by mass, the viscosity may increase and handling may be difficult. If the content exceeds 1000000 parts by mass, the concentration of the solution becomes too low and the thickness of the transparent conductive film can be adjusted. It can be difficult.
  • the organic solvent is preferably methanol, ethanol, or 2-propanol.
  • the content of the organic solvent is not particularly limited, and is preferably 20 to 700000 parts by mass and more preferably 200 to 350,000 parts by mass with respect to 100 parts by mass of the solid content of the conductive polymer (B).
  • the ratio of water to the organic solvent is preferably 100: 0 to 5:95, more preferably 100: 0 to 30:70.
  • the said (G) solvent does not remain in the transparent conductive film formed using the said composition for transparent conductive film formation.
  • a component that completely dissolves all the components of the composition for forming a transparent conductive film ie, “solvent”
  • a component that disperses insoluble components ie, “dispersion medium”. Both are described as “solvent” without particular distinction.
  • (H) Crosslinking agent By adding the (H) crosslinking agent to the transparent conductive film forming composition of the present invention, the strength of the transparent conductive film formed using the transparent conductive film forming composition is further improved. be able to. This is because the (D) binder can be crosslinked by using the (H) crosslinking agent in combination with the (D) binder.
  • crosslinking agents such as a melamine type, a polycarbodiimide type, a polyoxazoline type, a polyepoxy type, a polyisocyanate type, are mentioned. These (H) crosslinking agents may be used alone or in combination of two or more.
  • the content is not specifically limited, In solid content conversion, with respect to 100 mass parts of solid content of the said (B) conductive polymer. 0.1 to 17000 parts by mass is preferable, and 1 to 1000 parts by mass is more preferable.
  • the content of the (H) crosslinking agent is less than 0.1 parts by mass, the strength of the transparent conductive film may be insufficient.
  • the content exceeds 17000 parts by mass, (A ) The presence ratio of metal nanowires and (B) conductive polymer is reduced, and the conductivity of the transparent conductive film may not be sufficiently ensured.
  • composition for forming a transparent conductive film of the present invention contains the (H) crosslinking agent, as the catalyst for crosslinking the (D) binder, an acidic group of a dopant may be used, or a new one.
  • An organic acid or an inorganic acid may be added.
  • the catalyst (I) is not particularly limited, and examples thereof include a photopolymerization initiator and a thermal polymerization initiator.
  • a photoinitiator it is preferable to use as said (I) catalyst.
  • the photopolymerization initiator is not particularly limited, and examples thereof include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl- 1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, benzophenone, 1- ⁇ 4- (2-hydroxyethoxy) -phenyl ⁇ -2-hydroxy-2-methyl-1-propane-1 -One, oxy-phenyl-acetic acid 2- ⁇ 2-oxo-2-phenyl-acetoxy-ethoxy ⁇ -ethyl ester + oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, 2- Methyl 1- ⁇ 4- (ethylthio) phenyl ⁇ -2-morpholinopropan-1-one, -Benzyl-2-dimethylamino-1- (4-morpholinophenyl)
  • the thermal polymerization initiator is not particularly limited.
  • the content thereof is not particularly limited, but is 0.01 to 100 parts by weight with respect to 100 parts by weight of the (D) binder.
  • the amount is preferably 0.1 to 10 parts by weight.
  • the content of the catalyst (I) is less than 0.01 parts by weight, the function as a catalyst may be insufficient.
  • the content exceeds 100 parts by weight, (A) the metal nanowire and (B) the conductive polymer. This is because there is a case where the existence ratio of the conductive film decreases and the conductivity of the transparent conductive film cannot be sufficiently ensured.
  • the composition for forming a transparent conductive film of the present invention contains (C) a conductivity improver in addition to (A) a metal nanowire, (B) a conductive polymer, and (D) a binder. In addition, it has the characteristics of excellent transparency and conductivity. Therefore, the composition for forming a transparent conductive film of the present invention can be used very suitably for forming a transparent conductive film in a transparent conductor.
  • the transparent conductor of the present invention is a transparent conductor comprising a transparent substrate and a transparent conductive film laminated on at least one surface of the transparent substrate,
  • the said transparent conductive film is a film
  • the “transparent substrate” refers to a substrate having a total light transmittance of 60% or more.
  • the material of the transparent substrate is not particularly limited as long as it is transparent.
  • examples thereof include glass, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate, and modified polyester, polyethylene (PE) resin, and polypropylene (PP).
  • PET polyethylene terephthalate
  • PE polyethylene naphthalate
  • PP polypropylene
  • Resins polystyrene resins, polyolefin resins such as cyclic olefin resins, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin, polysulfone (PSF) resin, polyether sulfone (PES) Examples thereof include resins, polycarbonate (PC) resins, polyamide resins, polyimide resins, acrylic resins, and triacetyl cellulose (TAC) resins.
  • PEEK polyether ether ketone
  • PSF polysulfone
  • PES polyether sulfone
  • PC polycarbonate
  • PC polyamide resins
  • polyimide resins polyimide resins
  • acrylic resins acrylic resins
  • TAC triacetyl cellulose
  • the thickness of the transparent substrate is not particularly limited, but is preferably 10 to 10000 ⁇ m, and more preferably 25 to 5000 ⁇ m. Further, the total light transmittance of the transparent substrate is not particularly limited as long as it is 60% or more, but is preferably 70% or more, and more preferably 80% or more.
  • the said transparent conductive film is a film
  • the transparent conductive film may include a non-conductive portion and a conductive portion.
  • the conductive portion can be a conductor pattern.
  • the transparent conductive film having a non-conductive portion and a conductive portion is subjected to (III) patterning step in addition to (I) coating step and (II) forming step in the transparent conductive film manufacturing method of the present invention described later. Can be obtained.
  • the non-conductive portion and the conductive portion satisfy the requirements (1) to (3) below, while maintaining a good appearance. It is preferable because of the performance required to act as (1)
  • the ratio of the surface resistivity of the non-conductive portion to the surface resistivity of the conductive portion is 10,000 or more; (2)
  • the difference between the total light transmittance of the non-conductive portion and the total light transmittance of the conductive portion is within ⁇ 10%; and (3)
  • the ratio of the haze value of the non-conductive portion to the haze value of the conductive portion is 95 to 105%. .
  • the surface resistivity of the transparent conductive film (the surface resistance value of the conductive portion in the case where a non-conductive portion and a conductive portion are provided) is not particularly limited, but is preferably 1000 ⁇ / ⁇ or less, preferably 900 ⁇ / ⁇ or less. More preferably, it is 800 ⁇ / ⁇ or less.
  • the surface resistivity exceeds 1000 ⁇ / ⁇ , the conductivity required for the transparent conductive film may not be ensured.
  • the minimum is not specifically limited, For example, it is 0.1 ohm / square.
  • the total light transmittance of the transparent conductor is not particularly limited, but is preferably 50% or more, more preferably 60% or more, and further preferably 80% or more.
  • the use of the transparent conductor is not particularly limited as long as transparency and conductivity are required.
  • various display devices such as liquid crystal, plasma, field emission, and various electronic devices such as mobile phones.
  • the said transparent conductor can also be used for uses, such as a transparent electrode in a solar cell, an electromagnetic wave shielding material, electronic paper, an electroluminescent light control element, a transparent heating element, and an electroplating primer.
  • it is preferably used for a transparent electrode for driving a liquid crystal, a transparent electrode for driving an EL, a transparent electrode for driving an electrochromic element, an electromagnetic shielding material, a transparent heating element, or an electrolytic plating primer.
  • the transparent conductor of the present invention comprises a transparent conductive film formed using the composition for forming a transparent conductive film of the present invention having the characteristics that it is excellent in transparency and conductivity when made into a transparent conductive film, Excellent transparency. Moreover, the transparent conductive film with which the transparent conductor of this invention is provided is excellent in transparency and electroconductivity.
  • the method for producing the transparent conductor of the present invention is as follows: (I) a coating step of applying the composition for forming a transparent conductive film of the present invention to at least one surface of a transparent substrate; and (II) By heat-treating the transparent base material on which at least one surface obtained in the coating step (I) is coated with the composition for forming a transparent conductive film under a temperature condition of 150 ° C. or lower, It includes a forming step of forming a transparent conductive film on at least one surface.
  • a method for applying the composition for forming a transparent conductive film of the present invention to at least one surface of a transparent substrate is not particularly limited, and a known method can be used.
  • a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method and the like can be used.
  • the manufacturing method of the transparent conductive film of this invention you may perform the said (I) application
  • the surface treatment include corona treatment, plasma treatment, itro treatment, and flame treatment.
  • the heat treatment in the forming step (II) is not particularly limited, and may be performed by a known method, for example, using a blowing oven, an infrared oven, a vacuum oven, or the like.
  • coating process contains the said (G) solvent, the said (G) solvent is removed by the said heat processing.
  • the heat treatment is performed under a temperature condition of 150 ° C. or lower.
  • the type of base material to be used is limited.
  • base materials generally used for transparent electrode films such as PET film polycarbonate film and acrylic film cannot be used.
  • the temperature of the heat treatment is preferably 50 to 140 ° C., more preferably 60 to 130 ° C.
  • the treatment time for the heat treatment is not particularly limited, but is preferably 0.1 to 60 minutes, and more preferably 0.5 to 30 minutes.
  • a calendar is used for the purpose of increasing the contact between the metal nanowires in the transparent conductive film and improving the conductivity of the transparent conductive film. Processing sometimes occurred.
  • a calender treatment is not particularly excluded, but the present invention has the characteristics of being excellent in transparency and conductivity when formed into a transparent conductive film. Since the transparent conductive film forming composition is used, the demand for further improving the conductivity of the transparent conductive film is not so strong. Therefore, from the point that the number of processes can be reduced and a transparent conductor can be easily manufactured, and the occurrence of variation in surface resistivity due to uneven pressure during calendering can be suppressed. It is preferable not to perform.
  • a patterned protective resist is formed on top of the transparent conductive film formed in the (II) formation step, and then is not protected with the protective resist of the transparent conductive film using an inactivating agent.
  • a patterning step for making the region non-conductive may be performed.
  • a method for forming a protective resist patterned on the transparent conductive film formed in the (II) forming step is not particularly limited, and a known method can be used. Then, after applying a positive or negative composition for forming a protective resist on the transparent conductive film, it is exposed through a photomask patterned in a desired shape, and the exposed or unexposed portion is exposed using a developer. Examples thereof include a method of removing the composition for forming a protective resist.
  • the deactivator is brought into contact with a region not protected by the protective resist of the transparent conductive film, whereby the (B) conductive polymer ⁇ contained in the transparent conductive film is contacted.
  • the conjugate bond is cut, and the region of the transparent conductive film that is not protected by the protective resist is made nonconductive.
  • the deactivator is not particularly limited as long as it breaks the ⁇ -conjugated bond of the conductive polymer (B), and examples thereof include an oxidizing agent, a peroxide, a strong acidic liquid, and a strong basic liquid. Can be mentioned. These deactivators may be used alone or in combination of two or more.
  • the deactivator is preferably an oxidizing agent.
  • the conductivity can be inactivated without fading the color of the conductive polymer (B).
  • a transparent conductive film is formed on a transparent substrate using the composition for forming a transparent conductive film of the present invention.
  • the transparent conductor excellent in transparency in which the excellent transparent conductive film was formed can be manufactured suitably.
  • Binder polyester manufactured by Nagase ChemteX Corporation, Gabsen ES-210, solid content 25%
  • Polyurethane (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 300, solid content 30%)
  • Acrylic resin (Toagosei Co., Ltd., Jurimer SEK301, solid content 40%)
  • Methyl silicate oligomer (Mitsubishi Chemical Corporation, MKC silicate MS57, solid content 100%)
  • Polyolefin Toyobo Co., Ltd., Hardren EZ-2001, solid content 30%)
  • Synthesis Example 1 Preparation of Composition A
  • A 100 parts by weight of Ag nanowire (manufactured by Seiko PMC Co., Ltd., T-YP808, aspect ratio 230, solid content 1.0%) as metal nanowire
  • B conductivity Poly (3,4-ethylenedioxythiophene) polystyrenesulfonic acid (manufactured by Heraeus Co., Clevios PH1000, conductivity 0.48 S / cm, solid content 1.0%) as a conductive polymer
  • D polyester (manufactured by Nagase ChemteX Corporation, Gabsen) ES-210, solid content 25%) 7.2 parts by weight
  • E surfactant and / or leveling agent polysurfact
  • compositions A to T, R 1 to R 7, A 1 to A 7, U to Z and U 1 prepared in Synthesis Examples 1 to 41 are described in the following 3-6.
  • the dispersion stability was evaluated by the method described in 1). The results are shown in Table 1.
  • Example / Comparative Example It was obtained in Synthesis Example 1 on one surface of a transparent substrate made of polyethylene terephthalate (PET) (manufactured by Toray Industries, Lumirror T60, length 150 mm ⁇ width 100 mm ⁇ thickness 188 ⁇ m, total light transmittance 87.7%).
  • Composition A was No. After coating with a thickness of 18.5 ⁇ m using a 16 bar coater, a transparent conductive film was formed on one surface of the transparent substrate by heat treatment at 130 ° C. for 5 minutes using a blower oven. Got.
  • Example 2 A transparent conductor was obtained in the same manner as in Example 1 except that the heat treatment temperature was set to 100 ° C.
  • Examples 3 to 35 A transparent conductor was obtained in the same manner as in Example 1 except that the compositions B to T, R1 to R7, and A1 to A7 obtained in Synthesis Examples 2 to 34 were used in place of the composition A.
  • Comparative Example 9 A glass transparent substrate (Sekiya Rika Co., Ltd. blue plate, 100 ⁇ 100 ⁇ 2 mm, total light transmittance 91.0%) was used in place of the PET transparent substrate, and heat treatment A transparent conductor was obtained in the same manner as in Comparative Example 5 except that the conditions were 200 ° C. and 20 minutes.
  • the transparent conductors obtained in Examples 1 to 35 and Comparative Examples 1 to 9 were measured for total light transmittance and evaluated for adhesion. Moreover, about the transparent conductive film of the obtained transparent conductor, the measurement of surface resistivity, heat resistance evaluation, calculation of electrical conductivity, and evaluation of the bleed-out characteristic were performed. The results are shown in Table 2 below.

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Abstract

La présente invention concerne une composition pour former un film conducteur transparent, ayant pour caractéristiques une transparence et une conductivité électrique excellentes lorsqu'elle est transformée en un film conducteur transparent. La présente invention concerne également un conducteur transparent ayant un film conducteur transparent comprenant cette composition pour former un film conducteur transparent ; et un procédé de production d'un conducteur transparent, qui utilise cette composition pour former un film conducteur transparent. Cette composition pour former un film conducteur transparent se caractérise en ce qu'elle contient (A) des nanofils de métal, (B) un polymère électriquement conducteur, (C) un agent améliorant la conductivité, et (D) un liant. La quantité de fraction solide de liant (D) contenue est de 0,1 à 1000 parties en poids par rapport à la quantité contenue totale de 100 parties en poids de fraction solide de nanofils de métal (A) et de fraction solide de polymère électriquement conducteur (B).
PCT/JP2014/076876 2013-10-18 2014-10-08 Composition pour la formation de film conducteur transparent, conducteur transparent et procédé de production de conducteur transparent WO2015056609A1 (fr)

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