WO2021054352A1 - 水性白色導電性プライマー塗料組成物及びそれを用いた複層塗膜形成方法 - Google Patents
水性白色導電性プライマー塗料組成物及びそれを用いた複層塗膜形成方法 Download PDFInfo
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- WO2021054352A1 WO2021054352A1 PCT/JP2020/035048 JP2020035048W WO2021054352A1 WO 2021054352 A1 WO2021054352 A1 WO 2021054352A1 JP 2020035048 W JP2020035048 W JP 2020035048W WO 2021054352 A1 WO2021054352 A1 WO 2021054352A1
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- conductive primer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
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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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
- B05D1/045—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field on non-conductive substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
- B05D7/26—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials synthetic lacquers or varnishes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
- B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
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- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- 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
- C09D5/002—Priming paints
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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
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
- B05D2401/20—Aqueous dispersion or solution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2502/00—Acrylic polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2503/00—Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2507/00—Polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2507/00—Polyolefins
- B05D2507/01—Polyethylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
- B05D2601/24—Titanium dioxide, e.g. rutile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Definitions
- the present invention relates to an aqueous white conductive primer coating composition capable of forming a multilayer coating film having excellent conductivity and brightness on a plastic base material such as an automobile bumper, and a method for forming a multilayer coating film using the same.
- the coating of plastic base materials has been performed by spray coating such as air spray and airless spray, but in order to save energy and reduce the discharge of harmful substances to the environment, electrostatic coating with excellent coating efficiency is being considered. Has been adopted and is being adopted.
- the plastic base material generally has a high electrical resistance (generally, the surface electrical resistivity is about 1 ⁇ 10 12 to 1 ⁇ 10 16 ⁇ / ⁇ )
- the paint is directly applied to the surface of the plastic base material by electrostatic coating. It is extremely difficult to paint. Therefore, it is usually necessary to perform electrostatic coating after imparting conductivity to the plastic base material itself or its surface.
- a conductive primer when electrostatically coating a paint on a plastic base material, a conductive primer may be coated on the plastic base material in order to impart conductivity to the base material.
- a paint containing a resin component and a conductive filler is generally used.
- a water-based paint as a conductive primer paint.
- a white conductive primer paint is usually used as the conductive primer paint.
- a base paint containing a photointerfering pigment and the white primer coating film of the lower layer can be seen through is used as the base paint.
- the white primer coating film is white with high brightness. It may be required to be a coating film.
- Patent Document 1 describes (a) a resin mixture of a chlorinated polyolefin resin having a chlorine content of 10 to 40% by weight and at least one modified resin selected from the group consisting of acrylic resin, polyester resin and polyurethane resin. 100 parts by weight, (b) 5 to 50 parts by weight of the cross-linking agent, and (c) a conductive layer containing tin oxide and phosphorus on the surface of titanium dioxide particles, and containing a metal element having a valence of 4 or less as an impurity.
- a white conductive primer coating material containing 10 to 250 parts by weight of white conductive titanium dioxide powder having an amount of a specific amount or less is disclosed.
- Patent Document 2 50 to 200 parts by weight of the white pigment (c) and conductive metal oxide particles are used with respect to 100 parts by weight of the total solid content of the chlorinated polyolefin (a) and the other resin (b).
- a white conductive primer coating material containing 10 to 150 parts by weight of a pigment (d) coated with mica is disclosed.
- the white conductive primer coating described in Patent Document 1 may have insufficient weather resistance.
- the white conductive primer coating described in Patent Document 2 may have insufficient lightness or insufficient smoothness of the formed coating film.
- an object of the present invention is to provide an aqueous white conductive primer coating composition capable of forming a coating film having high brightness and sufficient conductivity on a plastic substrate.
- the present inventors are an aqueous white conductive primer coating composition containing a binder component (A) and a carbon nanotube dispersion liquid (B), and the coating film formed by the aqueous white conductive primer coating composition.
- whiteness according to the L * value is not less than 80 and an aqueous white conductive primer coating composition a surface electrical resistivity is 10 8 ⁇ / ⁇ or less based on the CIE color matching functions, it can solve the above problems , The present invention has been completed.
- an aqueous white conductive primer coating composition containing a binder component (A) and a carbon nanotube dispersion liquid (B), which is based on the CIE color matching function of a coating film formed by the aqueous white conductive primer coating composition.
- whiteness by L * value is not less than 80 and a surface electrical resistivity of 10 8 ⁇ / ⁇ aqueous white conductive primer coating composition is less.
- the acrylic resin (A1) is an acrylic resin obtained by polymerizing a polymerizable unsaturated monomer, and contains 10 to 50 parts by mass of isobornyl (meth) acrylate based on 100 parts by mass of the polymerizable unsaturated monomer.
- the aqueous white conductive primer coating composition according to 2 above which is an acrylic resin (A11). 4.
- the aqueous white conductive primer coating composition according to any one of 1 to 4 above, wherein the carbon nanotube dispersion liquid (B) is a carbon nanotube dispersion liquid (B1) satisfying the following (1) to (4).
- the carbon nanotube dispersion liquid (B) is a carbon nanotube dispersion liquid (B1) satisfying the following (1) to (4).
- the carbon nanotube (a) is a single layer, has an average outer diameter of 0.5 to 5 nm in image analysis with a transmission electron microscope, and has a specific surface area of 400 to 800 m 2 / g.
- the water-soluble resin (b) is contained in an amount of 400 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the carbon component of the carbon nanotube (a).
- the 50% particle diameter (D50 diameter) calculated by the laser diffraction type particle size distribution measurement of the carbon nanotube dispersion liquid is 1.5 to 40 ⁇ m.
- a method for forming a multi-layer coating film which comprises the following steps (1) to (4).
- a step of coating a plastic base material with the aqueous white conductive primer coating composition according to any one of 1 to 7 to form an uncured white conductive primer layer (2) The white conductive primer.
- Step of electrostatically coating the interference color base coating composition on the layer to form an uncured interference color base layer (3)
- Electrostatic coating of the clear coating composition on the interference color base layer Step of forming uncured clear layer (4) Step of simultaneously baking three layers of coating film formed by steps (1) to (3)
- the coating film having a high brightness and sufficient conductivity can be formed on a plastic substrate.
- a coating film having a low hiding power is formed as the upper layer coating film of the coating film, a multi-layer coating film having high brightness and / or high saturation can be formed.
- a top coat composition such as a colored paint and / or a clear paint can be applied onto the coating film by electrostatic coating having excellent coating efficiency, and a useless paint that does not adhere to the object to be coated can be applied. Can be reduced.
- the aqueous white conductive primer coating composition of the present invention (hereinafter, also simply referred to as “the coating composition of the present invention”) is an aqueous white conductive primer containing a binder component (A) and a carbon nanotube dispersion liquid (B).
- a coating composition, aqueous white conductive primer L * value according to the white level based on the CIE color matching functions of the coating film formed from the paint composition is not less than 80 and a surface electrical resistivity of 10 8 Omega / ⁇ Below.
- the present invention will be described in more detail.
- the binder component (A) itself has a film-forming property, and may be either a non-crosslinked type or a crosslinked type, and a crosslinked type is preferable.
- a film-forming resin known per se can be used, which has been conventionally used as a binder component for paints.
- the type of the film-forming resin examples include acrylic resin, polyolefin resin, polyester resin, alkyd resin, polyurethane resin and the like.
- the film-forming resin preferably has a crosslinkable functional group such as a hydroxyl group, a carboxyl group, or an epoxy group. These can be used individually or in combination of two or more. Among these, it is preferable to contain at least one selected from acrylic resin and polyolefin resin. Of these, it is more preferable to use an acrylic resin and a polyolefin resin in combination from the viewpoint of improving the adhesion and appearance of the coating film.
- a cross-linking agent can be used in addition to the film-forming resin.
- the film-forming resin usually has a cross-linking functional group such as a hydroxyl group, a carboxyl group, or an epoxy group, and reacts with the cross-linking agent. Therefore, a resin (base resin) capable of forming a crosslinked film can be used.
- a cross-linked coating material containing the above-mentioned substrate resin and a cross-linking agent from the viewpoint of water resistance of the formed coating film and the like.
- the type of the base resin examples include acrylic resin, polyolefin resin, polyester resin, alkyd resin, polyurethane resin and the like.
- the substrate resin is preferably a hydroxyl group-containing resin, and more preferably a hydroxyl group-containing acrylic resin.
- the blending ratio of the binder component (A) in the coating composition of the present invention can be changed according to the use and usage form of the coating composition of the present invention, but from the viewpoint of conductivity and adhesiveness, the coating composition Based on the weight of the non-volatile content of the product, it is preferably 30 to 70% by mass, more preferably 30 to 60% by mass, and further preferably 35 to 45% by mass.
- the mixing ratio of the acrylic resin and the polyolefin resin is 10 to 90% by mass for the former and 10 to 90% by mass for the latter based on the total of both from the viewpoint of improving the adhesion and appearance of the coating film. Is preferably 90 to 10% by mass, more preferably 20 to 80% by mass for the former and 80 to 20% by mass for the latter.
- the mixing ratio is based on the solid content weight.
- (meth) acrylate means acrylate or methacrylate
- (meth) acrylic acid means acrylic acid or methacrylic acid
- (meth) acryloyl means acryloyl or methacryloyl
- (meth) acrylamide means acrylamide or methacrylamide
- (meth) acrylic means "acrylic or methacrylic”.
- the acrylic resin (A1) is preferably an acrylic resin obtained by polymerizing a polymerizable unsaturated monomer, and is a hydroxyl group-containing acrylic obtained by polymerizing a hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers. It is more preferably a resin. Further, it is preferable to have a carboxyl group because of its solubility in water, dispersibility, crosslinkability and the like. As the polymerization method, a conventional method can be used.
- the hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds in one molecule.
- Examples of the hydroxyl group-containing polymerizable unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- Monoesterate of (meth) acrylic acid and divalent alcohol having 2 to 8 carbon atoms Monoesterate of (meth) acrylic acid and divalent alcohol having 2 to 8 carbon atoms; ⁇ -caprolactone modified product of monoesterate of (meth) acrylic acid and divalent alcohol having 2 to 8 carbon atoms; N -Hydroxymethyl (meth) acrylamide; allyl alcohol, (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end, and the like can be mentioned.
- Examples of other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
- Aminoalkyl (meth) acrylate acrylamide, metaacrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylol (Meta) acrylamide such as acrylamide, N-methylolacrylamide methyl ether, N-methylolacrylamide butyl ether or derivatives thereof; acrylonitrile, methacrylonitrile, vinyl acetate, beova monomer (manufactured by Shell Chemical Co., Ltd.), styrene, vinyl toluene, ⁇ -methylstyrene 2- (2'-Hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperid
- the polymerization method for polymerizing the above-mentioned polymerizable unsaturated monomer to obtain a copolymer is not particularly limited, and a polymerization method known per se, for example, a bulk polymerization method in the presence of a radical polymerization initiator.
- the solution polymerization method can be preferably used, such as a solution polymerization method and a bulk-suspension two-stage polymerization method in which suspension polymerization is carried out after bulk polymerization.
- the polymerizable unsaturated monomer is dissolved or dispersed in an organic solvent, and in the presence of the above radical polymerization initiator, usually while stirring at a temperature of about 80 ° C. to 200 ° C. A method of heating can be mentioned.
- the reaction time is usually about 1 to 24 hours.
- acrylic resin (A1) from the viewpoint of improving the appearance of the obtained coating film, isobornyl acrylate and / or isobornyl methacrylate, preferably isobornyl acrylate, is used in an amount of 100 parts by mass of a polymerizable unsaturated monomer.
- Acrylic resin (A11) containing 15 to 65 parts by mass, preferably 20 to 55 parts by mass, and more preferably 25 to 45 parts by mass as the total amount of the isobornyl acrylate and the isobornyl methacrylate is preferable.
- the acrylic resin (A11) preferably has a hydroxyl group, and more preferably has a hydroxyl group and a carboxyl group.
- the acrylic resin (A1) usually has a number average molecular weight of about 2,000 to 100,000, preferably about 10,000 to 70,000.
- the number average molecular weight and the weight average molecular weight are values calculated from a chromatogram measured by a gel permeation chromatograph based on the molecular weight of standard polystyrene.
- the gel permeation chromatograph "HLC8120GPC” (manufactured by Tosoh Corporation) was used.
- columns four columns, “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL”, and “TSKgel G-2000HXL” (all manufactured by Tosoh Corporation, trade name) are used, and a mobile phase is used.
- Tetrahydrofuran measurement temperature; 40 ° C., flow rate; 1 cc / min, detector; RI conditions.
- the acrylic resin (A1) is the hydroxyl group-containing acrylic resin
- the hydroxyl group-containing acrylic resin usually has a hydroxyl value of about 10 to 100 mgKOH / g, preferably about 30 to 70 mgKOH / g.
- the acrylic resin (A1) contains a carboxyl group
- the acrylic resin (A1) has an acid value of about 10 to 100 mgKOH / g, preferably about 20 to 50 mgKOH / g.
- polyolefin resin (A2) As the polyolefin resin used in the coating composition of the present invention, either polyolefin or modified polyolefin can be used.
- the polyolefin includes, for example, a polyolefin obtained by (co) polymerizing one or more of olefins having 2 to 10 carbon atoms such as ethylene, propylene, butylene, and hexene.
- the modified polyolefin includes an unsaturated carboxylic acid or acid anhydride modified product of the polyolefin, an acrylic modified product, a chlorinated product, and a modified polyolefin obtained by using a combination of these modifications.
- those containing propylene as a polymerization unit are particularly preferable, and the weight fraction of the propylene unit in the polyolefin is compatible with other components and the formed coating film. From the viewpoint of adhesiveness and the like, those in the range of 0.5 or more, particularly 0.6 to 1, and further particularly 0.7 to 0.95 are preferable.
- polystyrene resin those known per se can be used without particular limitation, but a single-site catalyst is used as the polymerization catalyst because the obtained polyolefin has a narrow molecular weight distribution and is excellent in random copolymerization and the like. Those produced by (co) polymerizing olefins are preferable.
- the single-site catalyst is a polymerization catalyst having a uniform active site structure (single-site), and among the single-site catalysts, a metallocene-based catalyst is particularly preferable.
- the metallocene-based catalyst is a metallocene (bis (cyclopentadienyl)) which is a transition metal compound of Group 4 to 6 or 8 of the periodic table having at least one conjugated five-membered ring ligand or a rare earth transition metal compound of Group 3. ) Metal complex and its derivative), an co-catalyst such as aluminoxane or boron system that activates the metal complex), and an organoaluminum compound such as trimethylaluminum can be prepared in combination.
- the (co) polymerization of olefins can be carried out according to a method known per se, for example, by continuously adding alkylaluminum and metallocene while supplying olefins such as propylene and ethylene and hydrogen to the reaction vessel.
- An unsaturated carboxylic acid or acid anhydride-modified polyolefin can be produced, for example, by graft-polymerizing an unsaturated carboxylic acid or an acid anhydride thereof on a polyolefin according to a method known per se.
- an unsaturated carboxylic acid or its acid anhydride that can be used for modification an aliphatic carboxylic acid having at least one, preferably one polymerizable double bond in one molecule and having 3 to 10 carbon atoms is used. It is included, and specific examples thereof include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride and the like, and maleic acid or an acid anhydride thereof is particularly preferable.
- the amount of graft polymerization of the unsaturated carboxylic acid or its acid anhydride on the polyolefin can be changed according to the physical properties desired for the modified polyolefin, but in general, it is preferably 1 to 1 based on the solid content weight of the polyolefin.
- the range of 20% by mass, more preferably 1.5 to 15% by mass, still more preferably 2 to 10% by mass is suitable.
- Acrylic-modified polyolefins can be produced by graft-polymerizing at least one acrylic unsaturated monomer with a polyolefin by a suitable method known per se.
- acrylic unsaturated monomer that can be used for this acrylic modification include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate.
- an acrylic unsaturated monomer having a reactivity with a carboxyl group in the unsaturated carboxylic acid or the acid anhydride-modified polyolefin produced as described above for example, (meth) acrylic.
- This is carried out by reacting glycidyl acid or the like to introduce a polymerizable unsaturated group into the polyolefin, and then (co) polymerizing the polymerizable unsaturated group with the acrylic unsaturated monomer alone or in combination of two or more. be able to.
- the amount of the acrylic unsaturated monomer used in the acrylic modification of polyolefin can be changed according to the physical properties desired for the modified polyolefin, but from the viewpoint of compatibility with other components and adhesion of the formed coating film. In general, it is preferably 30% by mass or less, particularly 0.1 to 20% by mass, and more preferably 0.15 to 15% by mass based on the solid content weight of the obtained modified polyolefin.
- Polyolefin chlorinated products can be produced by chlorinating polyolefins. Chlorination of polyolefin can be carried out, for example, by blowing chlorine gas into an organic solvent solution or dispersion of polyolefin or a modified product thereof, and the reaction temperature is preferably 50 to 120 ° C.
- the chlorine content of the chlorinated polyolefin (solid content) can be changed according to the physical characteristics desired for the chlorinated polyolefin, but in general, chlorine of the polyolefin is generally considered from the viewpoint of adhesion of the formed coating film. It is desirable that the content is 35% by mass or less, particularly 10 to 30% by mass, and more preferably 12 to 25% by mass based on the weight of the product.
- the polyolefin used in the present invention usually has a melting point of 30 to 120 ° C. from the viewpoints of compatibility with other components, adhesion of the formed coating film to the polyolefin base material, and interlayer adhesion to the topcoat coating film layer. , Preferably in the range of 50 to 110 ° C., more preferably 70 to 100 ° C., and a weight average molecular weight (Mw) in the range of 50,000 to 150,000, preferably 70,000 to 130,000, even more preferably 80,000 to 120,000. Is preferable.
- the polyolefin or the modified polyolefin (A) generally has a heat of fusion of 1 to 50 mJ / mg from the viewpoint of adhesion of the formed coating film to the base material and interlayer adhesion to the topcoat coating film layer. It is preferable, particularly preferably 2 to 50 mJ / mg.
- the melting point and the calorific value of melting of the polyolefin or the modified polyolefin are determined by using a differential scanning calorimetry device "DSC-5200" (manufactured by Seiko Denshi Kogyo Co., Ltd., trade name) using 20 mg of the polyolefin or the modified polyolefin and raising the temperature at 10 ° C. It was obtained by measuring the amount of heat at / minute.
- the melting point of the polyolefin or modified polyolefin can be adjusted by varying the monomer composition of the polyolefin, especially the amount of ⁇ -olefin monomer. If it is difficult to determine the amount of heat of fusion, the amount of heat can be measured by the above method after the measurement sample is once heated to 120 ° C. and then cooled to room temperature at 10 ° C./min.
- the weight average molecular weight of the polyolefin or the modified polyolefin is a value obtained by converting the weight average molecular weight measured by gel permeation chromatography based on the weight average molecular weight of polystyrene, and is referred to as "HLC / GPC150C” as a gel permeation chromatography apparatus.
- HLC / GPC150C a gel permeation chromatography apparatus.
- the polyolefin or modified polyolefin (A) used in the present invention is generally the ratio of the weight average molecular weight to the number average molecular weight (Mw /) from the viewpoint of compatibility with other components and adhesion of the formed coating film.
- Mn is preferably 1.5 to 7.0, more preferably 1.8 to 5.0, and even more preferably 2.0 to 4.0.
- the above-mentioned polyolefin can be diluted with an organic solvent and used, or can be used as an aqueous dispersion.
- organic solvent for diluting the polyolefin examples include aromatic hydrocarbon solvents such as toluene, xylene and benzene; and fats such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cyclooctane and cyclonanone.
- aromatic hydrocarbon solvents such as toluene, xylene and benzene
- fats such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cyclooctane and cyclonanone.
- Cyclic hydrocarbon solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as ethanol, isopropanol and n-butanol, etc., each of which is used alone. It can be used in combination with or in combination of two or more.
- the aqueous dispersion of the polyolefin usually uses an unsaturated carboxylic acid or an acid anhydride-modified polyolefin as a raw material, neutralizes a part or all of the carboxyl groups in it with an amine compound, and / or water-disperses with an emulsifier. It can be done by making it. From the viewpoint of improving water dispersibility, it is desirable to use both neutralization and water dispersibility with an emulsifier.
- amine compound used for neutralization examples include tertiary amines such as triethylamine, tributylamine, dimethylethanolamine and triethanolamine; secondary amines such as diethylamine, dibutylamine, diethanolamine and morpholine; and propylamine and ethanolamine.
- tertiary amines such as triethylamine, tributylamine, dimethylethanolamine and triethanolamine
- secondary amines such as diethylamine, dibutylamine, diethanolamine and morpholine
- propylamine and ethanolamine examples of the amine compound used for neutralization.
- Primary amines and the like can be mentioned.
- the amount used is preferably in the range of usually 0.1 to 1.0 molar equivalent with respect to the carboxyl group in the unsaturated carboxylic acid or acid anhydride-modified polyolefin. ..
- emulsifier examples include polyoxyethylene monooleyl ether, polyoxyethylene monostearyl ether, polyoxyethylene monolauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, polyoxyethylene nonylphenyl ether, and polyoxy.
- Nonions such as ethylene octylphenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate System emulsifiers: Anionic emulsifiers such as sodium salts such as alkyl sulfonic acid, alkyl benzene sulfonic acid and alkyl phosphoric acid, and anionic emulsifiers such as ammonium salts, and anionic groups, polyoxyethylene groups, polyoxypropylene groups, etc. in one molecule.
- Anionic emulsifiers such as sodium salts such as alkyl sulfonic acid, alkyl benzene sulfonic acid and alkyl phosphoric acid
- anionic emulsifiers such as ammonium salts, and anionic groups, polyoxyethylene groups, poly
- Examples thereof include a polyoxyalkylene group-containing anionic emulsifier having the above polyoxyalkylene group and a reactive anionic emulsifier having the anionic group and a polymerizable unsaturated group in one molecule.
- Each of these emulsifiers can be used alone or in combination of two or more.
- the above emulsifier can usually be used in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the solid content of the unsaturated carboxylic acid or acid anhydride-modified polyolefin.
- the aqueous dispersion of the unsaturated carboxylic acid or acid anhydride-modified polyolefin thus obtained emulsifies the acrylic unsaturated monomer in the presence of the water-dispersed unsaturated carboxylic acid or acid anhydride-modified polyolefin, if necessary. By polymerization, it can be further obtained as an aqueous dispersion of an acrylic-modified unsaturated carboxylic acid or acid anhydride-modified polyolefin.
- the polyester resin that can be used as the binder component (A) can usually be obtained by an esterification reaction between a polybasic acid and a polyhydric alcohol.
- a polybasic acid is a compound (including an anhydride) having two or more carboxyl groups in one molecule
- a polyhydric alcohol is a compound having two or more hydroxyl groups in one molecule. You can use the ones normally used in the field. Furthermore, it can be modified with a monobasic acid, a higher fatty acid, an oil component, or the like.
- the polyester resin may have a hydroxyl group, and a hydroxyl group can be introduced by using a divalent alcohol and a trihydric or higher alcohol in combination. Further, the polyester resin may have a carboxyl group together with a hydroxyl group, and generally has a weight average molecular weight in the range of about 1,000 to 100,000, preferably about 1,500 to 70,000. It is preferable to do so.
- the cross-linking agent is a compound capable of curing the coating composition of the present invention by reacting with a cross-linking functional group such as a hydroxyl group, a carboxyl group or an epoxy group in the base resin.
- a cross-linking functional group such as a hydroxyl group, a carboxyl group or an epoxy group in the base resin.
- examples of the cross-linking agent include polyisocyanate compounds, blocked polyisocyanate compounds, amino resins, carbodiimide group-containing compounds, epoxy group-containing compounds, oxazoline compounds, carboxyl group-containing compounds, hydrazide group-containing compounds, semicarbazide group-containing compounds and the like. Can be mentioned.
- polyisocyanate compounds capable of reacting with hydroxyl groups blocked polyisocyanate compounds and amino resins, and carbodiimide group-containing compounds capable of reacting with carboxyl groups are preferable, and blocked polyisocyanate compounds and amino resins are particularly preferable.
- the cross-linking agent can be used alone or in combination of two or more.
- the polyisocyanate compound is a compound having at least two isocyanate groups in one molecule, and is, for example, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic aliphatic polyisocyanate, an aromatic polyisocyanate, or the polyisocyanate. Can be mentioned.
- aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3.
- An aliphatic diisocyanate such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, diisocyanate dimerate, methyl 2,6-diisocyanatohexanate (common name: lysine diisocyanate); 2 , 6-Diisocyanatohexanoic acid 2-isocyanatoethyl, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1, , 8-Diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane and other aliphatic triisocyanates, etc. Can be mentioned.
- alicyclic polyisocyanate examples include 1,3-cyclopentenediisocyanate, 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, and 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (common name).
- Isophorone diisocyanate 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis (isocyanato) Alicyclic diisocyanates such as methyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, methylenebis (4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), norbornan diisocyanate; 1,3,5 -Triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 2- (3-Isocyanatopropyl) -2,
- aromatic aliphatic polyisocyanate examples include methylenebis (4,5-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ⁇ , ⁇ '-diisocyanato-.
- Arophilic aliphatic diisocyanates such as 1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof; 1,3 , 5-Arophilic aliphatic triisocyanates such as triisocyanatomethylbenzene and the like can be mentioned.
- aromatic polyisocyanate examples include m-phenylene diisocyanate, p-phenylenedi isocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, and 2,4-tolylene diisocyanate (common name: 2,4-).
- aromatic diisocyanates such as 4,4'-toluene diisocyanate, 4,4'-diphenyl ether diisocyanate; triphenylmethane-4 , 4', 4''-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene and other aromatic triisocyanates; 4,4'-diphenylmethane-2,2' , 5,5'-Tetraisocyanate and other aromatic tetraisocyanates and the like.
- polyisocyanate derivative examples include the above-mentioned polyisocyanate dimer, trimmer, biuret, allophanate, uretdione, uretoimine, isocyanurate, oxadiazine trione, and polymethylene polyphenyl polyisocyanate (Crude MDI, Polymeric MDI). , Crude TDI and the like.
- the polyisocyanate and its derivatives may be used alone or in combination of two or more.
- these polyisocyanates aliphatic diisocyanates, alicyclic diisocyanates and derivatives thereof are preferable.
- the polyisocyanate compound a prepolymer obtained by reacting the polyisocyanate and its derivative with a compound capable of reacting with the polyisocyanate under the condition of excess isocyanate group may be used.
- the compound capable of reacting with the polyisocyanate include compounds having an active hydrogen group such as a hydroxyl group and an amino group. Specific examples thereof include polyhydric alcohols, low molecular weight polyester resins, amines and water. Can be used.
- the polyisocyanate compound includes a polymer of an isocyanate group-containing polymerizable unsaturated monomer, or a polymerizable unsaturated monomer other than the isocyanate group-containing polymerizable unsaturated monomer and the isocyanate group-containing polymerizable unsaturated monomer.
- a copolymer may be used.
- the polyisocyanate compound it is preferable to use a water-dispersible polyisocyanate compound from the viewpoint of smoothness of the obtained coating film.
- the water-dispersible polyisocyanate compound can be used without limitation as long as it is a polyisocyanate compound that can be stably dispersed in an aqueous medium.
- a hydrophilic polyisocyanate compound modified to be hydrophilic and an interface with the polyisocyanate compound a polyisocyanate compound or the like which has been imparted with water dispersibility by mixing with an activator in advance can be preferably used.
- the above polyisocyanate compounds can be used individually or in combination of two or more.
- polyisocyanate compound a commercially available product can be used.
- examples of commercially available products include "Baihijour 3100” (trade name, manufactured by Sumika Covestro Urethane Co., Ltd., hydrophilic hexamethylene diisocyanurate).
- the blocked polyisocyanate compound is a compound in which the isocyanate group of the polyisocyanate compound is blocked with a blocking agent.
- the blocking agent examples include phenol-based agents such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and methyl hydroxybenzoate; Lactams such as ⁇ -butyrolactam and ⁇ -propiolactam; aliphatic alcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol and lauryl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Ether systems such as butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and methoxymethanol; benzyl alcohol, glycolic acid, methyl glycolate, ethyl glycolate, butyl glycolate, lactic acid, methyl lactate, ethy
- Alcohols such as butyl, methylol urea, methylol melamine, diacetone alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate; formamide oxime, acetoamide oxime, acetooxime, methyl ethyl ketooxime, diacetylmonooxime, benzophenone oxime, cyclohexane oxime, etc.
- Oxime-based active methylene-based such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone; butyl mercaptan, t-butyl mercaptan, hexyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thio Mercaptans such as phenol, methylthiophenol, ethylthiophenol; acidamides such as acetoanilide, acetoaniside, acetotolide, acrylamide, methacrylicamide, acetateamide, stearate amide, benzamide; succinide imide, phthalateimide, maleateimide, etc.
- active methylene-based such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylace
- azole compound examples include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3, Pyrazole or pyrazole derivatives such as 5-dimethylpyrazole, 3-methyl-5-phenylpyrazole; imidazole or imidazole derivatives such as imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole; 2-methylimidazoline , 2-Pyrazole imidazoline and other imidazoline derivatives and the like.
- preferable blocking agents include active methylene-based blocking agents, pyrazoles or pyrazole derivatives.
- a solvent can be added as needed.
- the solvent used for the blocking reaction may be one that is not reactive with the isocyanate group.
- acetone ketones such as methyl ethyl ketone, esters such as ethyl acetate, and N-methyl-2-pyrrolidone (NMP).
- NMP N-methyl-2-pyrrolidone
- the blocked polyisocyanate compound it is preferable to use a water-dispersible blocked polyisocyanate compound from the viewpoint of smoothness of the obtained coating film.
- the water-dispersible blocked polyisocyanate compound can be used without limitation as long as it is a blocked polyisocyanate compound that can be stably dispersed in an aqueous medium.
- a hydrophilic blocked polyisocyanate compound modified to be hydrophilic a blocked polyisocyanate compound to which water dispersibility is imparted by mixing a blocked polyisocyanate compound and a surfactant in advance can be preferably used.
- the blocked polyisocyanate compounds can be used alone or in combination of two or more.
- amino resin a partially methylolated amino resin or a completely methylolated amino resin obtained by reacting an amino component with an aldehyde component
- amino component examples include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like.
- aldehyde component examples include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.
- methylol group of the above-mentioned methylolated amino resin which is partially or completely etherified with an appropriate alcohol
- examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.
- a melamine resin is preferable.
- the melamine resin for example, an alkyl etherified melamine resin in which the methylol group of the partially or completely methylolated melamine resin is partially or completely etherified with the above alcohol can be used.
- alkyl etherified melamine resin examples include methyl etherified melamine resins obtained by partially or completely etherifying the methylol groups of the partially or fully methylolated melamine resin with methyl alcohol; the methylol groups of the partially or fully methylolated melamine resin. Butyl etherified melamine resin partially or completely etherified with butyl alcohol; methyl-butyl mixed etherification in which the methylol group of the partially or completely methylolated melamine resin is partially or completely etherified with methyl alcohol and butyl alcohol.
- a melamine resin or the like can be preferably used. Further, as these melamine resins, those in which an imino group coexists can also be used. These may be either hydrophobic or hydrophilic.
- the weight average molecular weight of the melamine resin is preferably in the range of 400 to 6,000, more preferably in the range of 500 to 4,000, and in the range of 600 to 2,000. Is even more preferable.
- a commercially available product can be used as the melamine resin.
- Commercially available product names include, for example, “Symel 202", “Symel 203", “Symel 238", “Symel 251", “Symel 303", “Symel 323", “Symel 324", “Symel 325", “Symel 327”, “Symel 350”, “Symel 385", “Symel 1156", “Symel 1158", “Symel 1116", “Symel 1130” (all manufactured by Ornex Japan), “Uban 120", “ Examples thereof include “Uban 20HS”, “Uban 20SE60”, “Uban 2021”, “Uban 2028”, and “Uban 28-60” (all manufactured by Mitsui Chemicals, Inc.).
- the above-mentioned melamine resins can be used individually or in combination of two or more.
- carbodiimide group-containing compound a commercially available product can be used.
- examples of commercially available products include “Carbodilite SV-02”, “Carbodilite V-02”, “Carbodilite V-02-L2”, “Carbodilite V-04”, “Carbodilite E-01”, and “Carbodilite E-02". (Both are manufactured by Nisshinbo, Inc., product names) and the like.
- the epoxy group-containing compound is a resin having two or more epoxy groups in one molecule.
- the epoxy group-containing compound is effective for cross-linking and curing an aqueous polyolefin resin, an aqueous acrylic resin, an aqueous polyester resin, an aqueous polyurethane resin, and the like having a carboxyl group.
- the oxazoline compound is a hydrophilic compound having a carboxyl group and effective for cross-linking and curing an aqueous polyolefin resin, an aqueous acrylic resin, an aqueous polyester resin, an aqueous polyurethane resin and the like.
- a hydrophilic oxazoline compound a commercially available product can be used. Examples of commercially available products include "Epocross WS-500" (manufactured by Nippon Shokubai Co., Ltd., trade name) and the like.
- the blending ratio of the base resin and the above-mentioned cross-linking agent is the total amount of both from the viewpoint of improving the smoothness and water resistance of the formed coating film.
- the former is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, still more preferably 50 to 80% by mass, and the latter is preferably 5 to 70% by mass, more preferably 10 by mass. It is preferably about 60% by mass, more preferably 20 to 50% by mass.
- the blending ratio of the carbon nanotube dispersion liquid (B) in the coating composition of the present invention is based on 100 parts by mass of the solid content of the binder component (A) from the viewpoint of conductivity and the brightness of the coating film, which will be described later.
- the content of the nanotube (a) is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.5 part by mass, and further preferably 0.03 to 0.3 part by mass. Is preferable.
- the carbon nanotube dispersion liquid (B) in the present invention is preferably a carbon nanotube dispersion liquid (B1) satisfying the following (1) to (4).
- the carbon nanotube (a) is a single layer, has an average outer diameter of 0.5 to 5 nm in image analysis with a transmission electron microscope, and has a specific surface area of 400 to 800 m 2 / g.
- the water-soluble resin (b) is contained in an amount of 400 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the carbon component of the carbon nanotube (a).
- the 50% particle diameter (D50 diameter) calculated by the laser diffraction type particle size distribution measurement of the carbon nanotube dispersion liquid is 1.5 to 40 ⁇ m.
- the carbon nanotube (a) used in the present invention may be either a single-walled carbon nanotube or a multi-walled carbon nanotube, but is preferably a single-walled carbon nanotube from the viewpoint of conductivity.
- the single-walled carbon nanotube has a shape in which flat graphite is wound in a cylindrical shape, and has a structure in which one layer of graphite is wound.
- the average outer diameter of the carbon nanotube (a) is preferably 0.5 to 5 nm, more preferably 1 to 3 nm, and even more preferably 1 to 2 nm.
- the average outer diameter of the carbon nanotube (a) is determined by observing the morphology of the carbon nanotube with a transmission electron microscope (manufactured by JEOL Ltd.), measuring the length of 100 minor axes, and using the average value of the numbers as the carbon nanotube.
- the average outer diameter (nm) is preferably 0.5 to 5 nm, more preferably 1 to 3 nm, and even more preferably 1 to 2 nm.
- the average outer diameter of the carbon nanotube (a) is determined by observing the morphology of the carbon nanotube with a transmission electron microscope (manufactured by JEOL Ltd.), measuring the length of 100 minor axes, and using the average value of the numbers as the carbon nanotube.
- the average outer diameter (nm) is preferably 0.5 to 5 nm, more preferably
- the specific surface area of the carbon nanotube (a) is preferably 400 to 800 m 2 / g, more preferably 400 to 600 m 2 / g.
- the specific surface area is preferably 400 to 800 m 2 / g, more preferably 400 to 600 m 2 / g.
- the carbon component of the carbon nanotube (a) is preferably 70 to 90%, more preferably 80 to 90%.
- the carbon component is in the range of 70 to 90%, the cohesive force of the carbon nanotubes is weak and the adsorption of the water-soluble resin (b) proceeds easily, and a carbon nanotube dispersion liquid having excellent storage stability and conductivity can be obtained.
- the carbon nanotube (a) may contain a catalyst component, and the value obtained by subtracting the catalyst component from the carbon nanotube (a) is referred to as a carbon component.
- the value of the carbon component is calculated by measuring the ash content after firing for 5 hours in the presence of 900 ° C. in the air according to the formula (1).
- Carbon component (%) of carbon nanotubes [1- ⁇ weight of ash after firing (g) / weight of carbon nanotubes before firing (g) ⁇ ] ⁇ 100 ... Equation (1)
- the carbon nanotube (a) has a 50% particle size (D50) calculated by laser diffraction particle size distribution measurement preferably 500 to 1300 ⁇ m, more preferably 800 to 1200 ⁇ m, and further preferably 900 to 1100 ⁇ m. is there.
- the 50% particle size (D50) means a value calculated by laser diffraction type particle size distribution measurement unless otherwise specified.
- Examples of such carbon nanotubes (a) include ZEONANO SG101 (outer diameter: 3 to 5 nm) manufactured by Zeon Corporation and TUBALL (80%) (outer diameter: 1 to 2 nm) manufactured by OCSiAl, as single-walled carbon nanotubes. Etc., but are not limited to these.
- the water-soluble resin (b) represents a water-soluble resin that functions as a dispersant that promotes wetting of carbon nanotubes in the dispersion step and contributes to dispersion stabilization.
- the water-soluble resin (b) is not particularly limited, but the following compounds can be exemplified as suitable examples.
- water-soluble resin (b) examples include water-soluble polymer compounds such as alginic acids, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyvinylpyrrolidone, and gum arabic; styrene-acrylic acid resin, styrene-.
- Methacrylic acid resin styrene-acrylic acid-acrylic acid ester resin, styrene-maleic acid resin, styrene-maleic acid ester resin, methacrylic acid-methacrylic acid ester resin, acrylic acid-acrylic acid ester resin, isobutylene-maleic acid resin, vinyl -Ethylate double bond-containing resins such as ester resins and rosin-modified maleic acid resins; amine-based resins such as polyallylamine, polyvinylamine and styrene imine; and the like can be mentioned.
- Examples of commercially available resin-type dispersants that can be used as the water-soluble resin (b) include Disperbyk-180, 183, 184, 187, 190, 191, 192, 193, 194, 2010, 2013, 2015, 2090, manufactured by Big Chemie. 2091, 2095, 2096, etc .; SOLPERSE-20000, 27000, 41000, 41090, 43000, 44000, 46000, 47000, 53095, 54000, etc.
- the water-soluble resin (b) is preferably ionic because of its compatibility with the binder component (A) and the high total light transmittance and conductivity of the paint, and is like a polyacrylic acid type. It is more preferable that the resin has an acidic functional group, preferably has a styrene structure, and further preferably has a styrene-acrylic structure. Further, it preferably has an acid value, and the solid content acid value is more preferably 10 to 250 mgKOH / g, and more preferably 10 to 100 mgKOH / g. This is because if it is within the above range, the dispersion stability is excellent due to the interaction with the carbon nanotube (a). Further, the water-soluble resin (b) may have an amine value.
- a preferable form of the water-soluble resin (b) is a resin having a styrene-acrylic structure and an acid value of 10 to 250 mgKOH / g. Further, as another preferable form, a resin having an acid value of 10 to 100 mgKOH / g can be mentioned.
- the solid content acid value of the water-soluble resin (b) is a value obtained by converting the measured acid value (mgKOH / g) into a solid content in accordance with the potentiometric titration method of JIS K 0070 (1992).
- the solid amine value of the water-soluble resin (b) is a value obtained by converting the measured total amine value (mgKOH / g) into a solid content in accordance with the method of ASTM D 2074 (2013).
- the carbon nanotube dispersion liquid may contain a surfactant in the dispersion liquid.
- a surfactant examples include a cationic surfactant, an amphoteric surfactant and an anionic surfactant.
- the cationic surfactant examples include alkylamine salts and quaternary ammonium salts.
- amphoteric surfactant examples include an alkyl betaine-based surfactant and an amine oxide-based surfactant.
- anionic surfactants include alkylbenzene sulfonates such as dodecylbenzene sulfonic acid, aromatic sulfonic acid-based surfactants such as dodecylphenyl ether sulfonate, monosoap-based anionic surfactants, and ether sulfates.
- alkylbenzene sulfonates such as dodecylbenzene sulfonic acid
- aromatic sulfonic acid-based surfactants such as dodecylphenyl ether sulfonate, monosoap-based anionic surfactants, and ether sulfates.
- examples thereof include based surfactants, phosphate surfactants and carboxylic acid surfactants.
- aromatic ionic surfactants are preferable because they are excellent in dispersibility, dispersion stability, and high concentration, and in particular, alkylbenzene sulfonates, dodecylphenyl ether sulfonates, and naphthalene sulfonates are preferable.
- Aromatic ionic surfactants such as acid salts are preferred.
- Nonionic surfactants include, for example, sugar ester-based surfactants such as sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester, and fatty acid ester-based surfactants such as polyoxyethylene resin acid ester and polyoxyethylene fatty acid diethyl.
- polyoxyethylene alkyl ethers polyoxyethylene alkyl phenyl ethers, ether-based surfactants such as polyoxyethylene / polypropylene glycol, polyoxyalkylene octyl phenyl ethers, polyoxyalkylene nonyl phenyl ethers, polyoxyalkyl dibutyl phenyl ethers, Examples thereof include aromatic nonionic surfactants such as polyoxyalkylstyrylphenyl ether, polyoxyalkylbenzylphenyl ether, polyoxyalkylbisphenyl ether, and polyoxyalkyl cumylphenyl ether.
- the alkyl may be an alkyl selected from 1 to 20 carbon atoms.
- a nonionic surfactant is preferable because it is excellent in dispersibility, dispersion stability, and high concentration, and polyoxyethylene phenyl ether, which is an aromatic nonionic surfactant, is particularly preferable.
- the carbon nanotube dispersion liquid (B) in the present invention is obtained by dispersing the carbon nanotubes (a) in water using the water-soluble resin (b) as a dispersant.
- the water-soluble resin (b) and the carbon nanotube (a) are added simultaneously or sequentially and mixed, so that the water-soluble resin (b) is dispersed while acting (adsorbing) on the carbon nanotube (a).
- the water-soluble resin (b) is dissolved, swollen, or dispersed in water, and then the carbon nanotube (a) is added to the liquid and mixed. Therefore, it is more preferable that the water-soluble resin (b) acts (adsorbs) on the carbon nanotubes (a).
- a disperser usually used for pigment dispersion or the like can be used.
- mixers such as disposables, homomixers, planetary mixers, homogenizers (M-Technique's “Clearmix”, PRIMIX's “Fillmix”, Sugino's “Abramix”, etc.), paint conditioners ( Red Devil), colloid mills (PUC “PUC colloid mill”, IKA “colloid mill MK”), cone mills (IKA “corn mill MKO”, etc.), ball mills, sand mills (Symmal Enterprises) "Dyno Mill” manufactured by Dyno Mill, etc.), Atwriter, Pearl Mill ("DCP Mill” manufactured by Eirich, etc.), Media type disperser such as Coball Mill, Wet Jet Mill ("Genus PY” manufactured by Genus, “Star Burst” manufactured by Sugino Machine Limited” , Nanomizer, etc.), M-Technique's "Claire SS-5", Nara Machinery's "MIC
- the 50% particle size (D50) of the carbon nanotube (a) after dispersion is preferably 1.5 to 40 ⁇ m, more preferably 4 to 40 ⁇ m, still more preferably 4 to 30 ⁇ m, and particularly preferably 4 to 20 ⁇ m. ..
- D50 the smaller the D50, the higher the dispersibility, and it is better to disperse the carbon nanotubes in isolation.
- D50 is 1.5 ⁇ m or more and 40 ⁇ m or less, conductivity and transparency can be improved.
- the content of the water-soluble resin (b) in the carbon nanotube dispersion liquid (B) is preferably 400 parts by mass or more and 2000 parts by mass or less, more preferably 800 parts by mass with respect to 100 parts by mass of the carbon component of the carbon nanotube (a). ⁇ 1200 parts by mass.
- the content of the water-soluble resin (b) is 400 parts by mass or more, the compatibility with the binder component (A) can be improved, and when it is 2000 parts by mass or less, the conductivity can be improved.
- the average length after dispersion in the carbon nanotube dispersion liquid (B) is preferably 2 ⁇ m or more and 10 ⁇ m or less, and more preferably 5 ⁇ m or more and 10 ⁇ m or less.
- the average length is 2 ⁇ m or more, the conductivity can be improved, and when it is 10 ⁇ m or less, the compatibility with the binder component (A) can be improved.
- the average length of the carbon nanotubes (a) is determined by observing the morphology of the carbon nanotubes with a transmission electron microscope (manufactured by JEOL Ltd.), measuring the lengths of 100 long axes, and using the average value of the numbers.
- the average length of carbon nanotubes is ( ⁇ m).
- the A / B is preferably 0.3 or more.
- the length of the carbon nanotube (a) is hard to change, defects in the graphene structure on the surface of the carbon nanotube (a) can be reduced, and the conductivity can be improved.
- the viscosity of the carbon nanotube dispersion liquid (B) is preferably 8,000 to 30,000 mPa ⁇ s at a B-type viscometer rotor rotation speed of 60 rpm, and more preferably 10,000 to 20,000 mPa ⁇ s.
- the concentration of carbon nanotubes in the solution in the carbon nanotube dispersion is preferably 0.1 to 1%, more preferably 0.3 to 0.7%.
- the coating composition of the present invention preferably further contains a pigment.
- the content of the pigment is preferably 50 to 250 parts by mass, more preferably 100 parts by mass, based on 100 parts by mass of the total solid content of the binder component (A) from the viewpoints of brightness, adhesiveness, water resistance, etc. of the formed coating film. It is up to 200 parts by mass, more preferably 125 to 175 parts by mass.
- the pigments include coloring pigments, extender pigments, brilliant pigments, conductive pigments and the like. Above all, it is preferable that the coating composition of the present invention contains a coloring pigment as at least one of the above pigments.
- the coloring pigment examples include titanium oxide [hereinafter, also referred to as titanium oxide pigment (C)], zinc oxide, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, and isoindolin pigment.
- titanium oxide pigment (C) examples include slene pigments and perylene pigments, and among them, the titanium oxide pigment (C) can be preferably used.
- extender pigment examples include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white, etc. Among them, barium sulfate and / or talc is preferably used.
- Glittering pigments include, for example, aluminum (including vaporized aluminum), copper, zinc, brass, nickel, aluminum oxide, mica, titanium oxide or iron oxide coated aluminum oxide, titanium oxide or iron oxide coated. Examples include mica, glass flakes, hologram pigments, etc. These bright pigments can be used alone or in combination of two or more.
- Aluminum pigments include non-leafing type aluminum and leafing type aluminum, both of which can be used.
- the conductive pigment is not particularly limited as long as it can impart conductivity to the formed coating film, and may be in the form of particles, flakes, or fibers (including whiskers).
- carbon powders such as conductive carbon black and graphite, and metal powders such as silver, nickel, copper and aluminum are exemplified, and further, antimony-doped tin oxide, phosphorus-doped tin oxide and oxidation are exemplified.
- a white pigment as a pigment, particularly a titanium oxide pigment (C), and the average particle size thereof is 0.05 to 0.05 from the viewpoint of designability and chemical resistance. It is preferably 2 ⁇ m, particularly preferably 0.1 to 1 ⁇ m.
- the content of the titanium oxide pigment (C) in the coating composition of the present invention is preferably 50 to 250 parts by mass, more preferably 100 to 200 parts by mass, based on 100 parts by mass of the solid content of the binder component (A). It is by mass, more preferably 125 to 175 parts by mass.
- the coating composition of the present invention may contain an ionic liquid.
- the ionic liquid used in the coating composition of the present invention includes a molten salt (or molten salt) that is in a liquid state at room temperature.
- Ordinary salts are generally solid at room temperature, but molten salts are ionic bonds of specific cations and anions and become liquid at room temperature.
- the room temperature means a temperature of about 20 ° C.
- the vicinity of room temperature means a temperature of about 10 to about 40 ° C.
- Such an ionic liquid contains various combinations of ionic bonds of one or more cations and one or more anions, and the cation species include, in particular, ammonium salts and phosphoniums.
- a cation having at least one onium salt structure selected from a salt and a sulfonium salt is suitable.
- the ionic liquid examples include quaternary ammonium cations having a nitrogen-containing heterocyclic structure such as imidazolium, pyridinium, pyrrolidinium, pyrazolidinium, isothiazolidinium, and isooxazolidinium having an alkyl chain, and aliphatic ammonium cations.
- organic carboxylic acids examples include those containing a combination with an anion derived from halogen or the like.
- examples of the organic carboxylic acid include lactic acid, and halogen includes fluorine, chlorine, bromine, and iodine.
- the ionic liquid examples include 1,2-dimethylimidazolium tetrafluoroborate, tetrabutylammonium bromide, hexadecyltributylphosphonium bromide, 1-butyl-3-methylimidazolium hexafluorophosphate, and N-hexyl.
- the ionic liquid it is usually desirable to use a colorless and transparent liquid, but it may be colored within a range that does not affect the color of the formed coating film.
- Some ionic liquids are soluble in water and some are sparingly soluble or insoluble in water. It is preferable to use different ionic liquids depending on the form of the coating composition of the present invention.
- the blending ratio of the ionic liquid in the coating composition of the present invention can be changed according to the use and usage form of the coating composition of the present invention, but is generally considered from the viewpoints of conductivity, adhesion, water resistance and the like. , 0.5 to 20% by mass, preferably 0.75 to 15% by mass, and more preferably 1 to 10% by mass based on the mass of the non-volatile content of the coating composition.
- each component described above is dissolved or dispersed in an organic solvent, water or a mixture thereof by a known method to adjust the solid content content to preferably 10 to 80% by mass.
- an organic solvent the one used in the production of each component may be used as it is, or may be added as appropriate.
- organic solvent examples include ketone-based organic solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester-based organic solvents such as ethyl acetate and butyl acetate; and ether-based organic solvents such as ethylene glycol monobutyl ether.
- Alcohol-based organic solvents such as isopropyl alcohol, n-butyl alcohol and isobutyl alcohol; aliphatic hydrocarbon-based organic solvents such as n-heptane and n-hexane; aromatic hydrocarbon-based organic solvents such as toluene and xylene; N- Other organic solvents such as methyl-pyrrolidone and the like can be mentioned.
- the base material for coating the coating composition of the present invention examples include various plastic base materials.
- the material of the plastic base material for example, polyolefin obtained by polymerizing at least one of olefins having 2 to 10 carbon atoms such as ethylene, propylene, butylene, and hexene is particularly preferable, but the material is not limited thereto. , Polycarbonate, ABS resin, urethane resin, nylon and the like. Further, these plastic base materials can be appropriately subjected to degreasing treatment, water washing treatment and the like in advance by a method known per se.
- the plastic base material is not particularly limited, and specific examples thereof include various plastic members used for automobile exterior parts such as bumpers, spoilers, grills, and fenders, and exterior parts of home electric appliances.
- the coating of the coating composition of the present invention can be formed by coating by a known coating method.
- the coating method include air spray coating, airless spray coating, rotary atomization coating, curtain coat coating and the like.
- the coating film thickness is usually in the range of about 10 to 50 ⁇ m, preferably about 15 to 45 ⁇ m, and more preferably about 20 to 40 ⁇ m as the cured film thickness.
- the coating film of the coating composition of the present invention allowed to stand at room temperature, by curing preheating or heating, usually, the surface electrical resistivity can form an uncured or cured coating layer is 10 8 ⁇ / ⁇ or less.
- surface electric resistivity is 10 8 Omega / ⁇ or less, on the coating film, for example, electrostatic painting of colored coating composition or / and top coating composition of the clear coating composition, etc. is possible.
- heating means can be used, for example, air blow, infrared heating, far infrared heating, induction heating, and dielectric heating. Heating and the like can be mentioned. Moreover, you may heat the plastic base material as needed.
- the coating composition of the present invention can form a coating film having a high whiteness of 80 or more as a lightness (L * value) based on the L * a * b * color system defined in JIS Z 8781-4 (2013). ..
- the L * value in the present specification is an irradiation light of 45 degrees with respect to the vertical axis of the coating film surface using a spectrophotometer CM512m3 (trade name, manufactured by Konica Minolta Co., Ltd.) with respect to the coating film surface. It is defined as a numerical value calculated from the spectral reflectance received at 90 degrees. This brightness can be measured as follows.
- Brightness (L * value) can be measured using the spectrophotometer.
- Examples of the method for forming a multi-layer coating film using the coating composition of the present invention include the following method I for forming a multi-layer coating film using 3 coats and 1 bake.
- a multi-layer coating film having high brightness and high texture can be formed on the surface of a plastic base material.
- the multi-layer coating film forming method I includes the following steps (1) to (4).
- the coating composition of the present invention is usually applied to a plastic base material.
- Step of electrostatically coating the interference color base coating composition on the white conductive primer layer to form an uncured interference color base layer Step (2) is not formed in step (1).
- An interference color base coating composition is electrostatically coated on a cured white conductive primer layer so that the cured film thickness is usually about 5 to 30 ⁇ m, preferably about 10 to 25 ⁇ m, and an uncured interference color base is applied. This is the process of forming a layer.
- the primer coating composition, the interference color base coating composition and the clear coating composition after coating the primer coating composition, the interference color base coating composition and the clear coating composition, it may be left as it is or preheated, if necessary. It is usually left at room temperature for about 1 to 20 minutes.
- the preheating is usually performed by heating at a temperature of about 40 to 120 ° C. for about 1 to 20 minutes.
- the heat curing of the three-layer coating film composed of the primer coating composition, the interference color base coating composition and the clear coating composition is usually carried out by heating at a temperature of about 60 to 140 ° C. for about 10 to 60 minutes. It can be carried out. Heat curing is preferably carried out at a temperature of about 80 to 120 ° C. for about 10 to 40 minutes.
- each coating composition after painting each coating composition, it may be left as it is or preheated, if necessary. It is usually left at room temperature for about 1 to 20 minutes.
- the preheating is usually performed by heating at a temperature of about 40 to 120 ° C. for about 1 to 20 minutes.
- any coating composition known per se as the interference color base coating for the topcoat base coat can be used.
- a coating composition obtained by dissolving or dispersing a base resin having a crosslinkable functional group, a crosslinking agent and a photocoherent pigment in water and / or an organic solvent can be preferably used.
- Examples of the crosslinkable functional group of the substrate resin include a carboxyl group and a hydroxyl group.
- Examples of the type of the base resin include acrylic resin, polyester resin, alkyd resin, urethane resin, and epoxy resin.
- Examples of the cross-linking agent include polyisocyanate compounds, blocked polyisocyanate compounds, melamine resins, urea resins and the like.
- the photointerfering pigment for example, a pigment obtained by coating a translucent base material such as natural mica, artificial mica, alumina flakes, silica flakes, and glass flakes with a metal oxide can be used.
- the metal oxide-coated mica pigment is a pigment in which natural mica or artificial mica is used as a base material and the surface of the base material is coated with a metal oxide.
- the natural mica, a scaly substrate was ground ore mica, and artificial mica, SiO 2, MgO, and Al 2 0 3, K 2 SiF 6, industrial raw materials such as Na 2 SiF 6 It is synthesized by heating, melting at a high temperature of about 1500 ° C., cooling and crystallizing, and has less impurities and a uniform size and thickness when compared with natural mica.
- fluorine-based mica, potassium tetrasilicon mica, sodium tetrasilicon mica, Na teniolite, LiNa teniolite and the like are known.
- the coating metal oxide include titanium oxide and iron oxide. Interference color can be expressed by the coating metal oxide.
- the metal oxide-coated alumina flake pigment is a pigment in which alumina flakes are used as a base material and the surface of the base material is coated with a metal oxide.
- Alumina flakes mean scaly (flaky) aluminum oxide, which is colorless and transparent. It does not have to be a single component of aluminum oxide, and may contain oxides of other metals.
- the metal oxide-coated alumina flake pigment develops an interference color due to the coated metal oxide. Examples of the coating metal oxide include titanium oxide and iron oxide.
- the metal oxide-coated silica flake pigment is scaly silica, which is a base material having a smooth surface and a uniform thickness, coated with a metal oxide having a refractive index different from that of the base material.
- the metal oxide-coated silica flake pigment expresses an interference color by the coated metal oxide.
- the coating metal oxide include titanium oxide and iron oxide.
- the metal oxide-coated glass flake pigment is a scaly glass base material coated with a metal oxide, and since the surface of the base material is smooth, strong light reflection occurs and a grainy feeling is exhibited.
- the metal oxide-coated glass flake pigment expresses an interference color due to the coated metal oxide. Examples of the coating metal oxide include titanium oxide and iron oxide.
- the coherent pigment may be surface-treated to improve dispersibility, water resistance, chemical resistance, weather resistance, and the like.
- the above-mentioned interfering pigment may be used alone or in combination of two or more.
- the coherent color-based coating composition used in the method of the present invention contains, for example, 1 to 80 parts by mass, preferably 2 to 60 parts by mass, based on 100 parts by mass of the total resin solid content of the coherent color base coating composition. It is contained in the range of parts.
- the interference color-based coating composition can further contain other pigments as long as the whiteness is not significantly reduced.
- the other pigments include titanium oxide, carbon black, zinc flower, cadmium red, molybdenum red, chromium yellow, chromium oxide, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindrin pigment, and slene pigment.
- Inorganic or organic solid color pigments such as perylene pigments and the like. The pigment may be used alone or in combination of two or more.
- the interference color-based paint composition can further contain various paint additives, if necessary.
- any coating material known per se as the coating composition for the topcoat clear coating can be used.
- a coating composition obtained by dissolving or dispersing a substrate resin having a crosslinkable functional group and a crosslinking agent in water and / or an organic solvent can be preferably used.
- Examples of the crosslinkable functional group of the substrate resin include a carboxyl group and a hydroxyl group.
- Examples of the type of the base resin include acrylic resin, polyester resin, alkyd resin, urethane resin, and epoxy resin.
- Examples of the cross-linking agent include polyisocyanate compounds, blocked polyisocyanate compounds, melamine resins, urea resins and the like.
- a coloring pigment a brilliant pigment, an extender pigment, a dye, an ultraviolet absorber, a light stabilizer, a surface conditioner, etc. can be appropriately blended in the clear paint composition to the extent that the transparency is not impaired.
- the following multi-layer coating film forming methods II to IV can be mentioned.
- the coating composition of the present invention in the lower layer it is possible to increase the brightness and expand the color options of the upper layer.
- Multi-layer coating film forming method II A method further comprising the following step (1a) between the step (1) and the step (2) in the multi-layer coating film forming method I.
- (1a) A step of coating an aqueous white non-conductive primer coating composition on the white conductive primer layer to form an uncured white non-conductive primer layer.
- the aqueous white non-conductive primer coating composition is usually coated so that the cured film thickness is about 5 to 50 ⁇ m, preferably about 10 to 40 ⁇ m.
- a primer coating composition capable of forming a film for example, a primer coating composition obtained by dissolving or dispersing a substrate resin having a crosslinkable functional group, a crosslinking agent and a white pigment in water can be preferably used.
- the L * value of the multi-layer coating film composed of the white conductive primer layer and the white non-conductive primer layer on the plastic substrate is preferably 81 or more, more preferably 85 or more, and 90 or more. Is particularly preferable.
- Multi-layer coating film forming method III A method including the following step (2a) instead of the step (2) in the multi-layer coating film forming method I.
- (2a) A step of electrostatically coating an aqueous white base coating composition on the white conductive primer layer to form an uncured white base layer.
- any paint composition known per se as the white base paint for the topcoat base coat can be used.
- a coating composition obtained by dissolving or dispersing a base resin having a crosslinkable functional group, a crosslinking agent and a white pigment in water and / or an organic solvent can be preferably used.
- the L * value of the multi-layer coating film composed of the white conductive primer layer and the white base layer on the plastic substrate is preferably 81 or more, more preferably 85 or more, and 90 or more. Is particularly preferable.
- Multi-layer coating film forming method IV A method including the following step (2b) instead of the step (2) in the multi-layer coating film forming method I. (2b) A step of electrostatically coating an aqueous high-saturation base coating composition on the white conductive primer layer to form an uncured high-saturation base layer.
- the water-based high-saturation base coating composition is usually coated so that the cured film thickness is about 5 to 50 ⁇ m, preferably about 10 to 40 ⁇ m.
- the water-based high-saturation base coating composition is a coating composition capable of forming a highly saturated coating film such as red.
- the saturation of the coating film coated with a cured film thickness of 15 ⁇ m on a white coating film having an L * value of 80 in the water-based high saturation base coating composition is 20 or more, preferably 30 or more, particularly preferably 40 or more in terms of C * value. ..
- the C * value is a chroma (C * value) based on the L * a * b * color system defined in JIS Z 8781-4 (2013).
- the C * value is measured at 45 degrees with respect to the vertical axis of the coating film surface and 90 degrees with respect to the coating film surface using a spectrophotometer CM512m3 (trade name, manufactured by Konica Minolta Co., Ltd.). It shall be defined as a numerical value calculated from the received spectral reflectance.
- Polyester resin >> The esterification reaction was carried out by a conventional method using trimethylolpropane, cyclohexanedimethanol, isophthalic acid and adipic acid. Number average molecular weight 4500, hydroxyl value 120, acid value 10.
- Block Polyisocyanate Compound (E) A compound in which hexamethylene diisocyanate is fully blocked with dimethyl malonate.
- the carbon nanotubes (a-1) and carbon nanotubes (a-2) were produced according to the following production examples.
- the 50% particle size (D50) of the carbon nanotubes used in the present invention is based on a laser diffraction type particle size distribution (“SALD-2300” manufactured by Shimadzu Corporation), and the specific surface area is a fully automatic specific surface area measuring device (“Mountech” manufactured by Mountech Co., Ltd.). HM Model-1200 ").
- Carbon Nanotube Dispersion B-1 >>> 0.5 parts of TUBALL as carbon nanotube (a), 4.7 parts of Joncryl JPD-96J as water-soluble dispersion resin (b), 0.3 parts of Surfinol 104E as defoaming agent, and 94.5 parts of purified water with a spatula.
- 200 g of zirconia beads having a diameter of 0.5 mm was charged as a dispersion medium and dispersed with a paint shaker for 4 hours to obtain a carbon nanotube dispersion liquid B-1.
- Carbon Nanotube Dispersion B-2 to B-13, B-15 to B-33 >>> Carbon nanotube dispersions B-2 to B-13, B- in the same manner as the carbon nanotube dispersion B-1, except that the type and amount of the water-soluble resin (b) shown in Table 1 and the dispersion treatment time were changed. 15-B-33 were obtained.
- Carbon Nanotube Dispersion B-14 >>> Carbon nanotubes in the same manner as carbon nanotube dispersion B-7, except that 0.04 parts of "Demor N" (manufactured by Kao Chemical Co., Ltd., sodium salt of ⁇ -naphthalene sulfonic acid formalin condensate) was added as a surfactant. Dispersion solution B-14 was obtained.
- viscosity The viscosity value was measured using a B-type viscometer (“BL” manufactured by Toki Sangyo Co., Ltd.), and the dispersion was sufficiently stirred with a spatula at a dispersion temperature of 25 ° C. and a B-type viscometer rotor rotation speed of 60 rpm. After that, I went immediately.
- the rotor used for the measurement was No. 1 when the viscosity value was less than 0.1 Pa ⁇ s. If 1 is 0.1 Pa ⁇ s or more and less than 0.5 Pa ⁇ s, No. If 2 is 0.5 Pa ⁇ s or more and less than 2.0 Pa ⁇ s, No.
- the 50% particle size (D50) was calculated from the laser diffraction type particle size distribution (“Microtrack MT300II” manufactured by Microtrack Bell).
- -Titanium oxide (C-1) Trade name "TI-PURE R-706", manufactured by The Chemours Company, rutile-type titanium oxide.
- -Titanium oxide (C-2) Trade name "JR-806", manufactured by TAYCA, rutile-type titanium oxide.
- -Conductive titanium oxide Trade name "ET-500W”, manufactured by Ishihara Sangyo Co., Ltd., white conductive titanium oxide.
- -Conductive mica Trade name "Iriotec 7310", manufactured by Merck & Co., Ltd.
- -Ionic liquid Product name "CIL-313”, manufactured by Carlit Japan Co., Ltd.
- the carbon nanotube dispersion (B) is the mass part of the solid content of the carbon nanotube (a)
- the components other than the carbon nanotube dispersion (B) are the mass parts of the solid content. (Each of them is shown), and the mixture was sufficiently stirred with a mixer to obtain various aqueous white conductive primers.
- ⁇ Preparation of test coating board> Each of the coating compositions prepared as described above was air-spray coated on a polypropylene plate (which had been degreased) so that the cured film thickness was 30 ⁇ m. The obtained coating film was left at room temperature for 3 minutes for setting, and then preheated at 60 ° C. for 3 minutes to form a white primer layer.
- ⁇ the surface electrical resistivity is 10 6 ( ⁇ / ⁇ ) below, ⁇ the surface electrical resistivity is 10 6 ( ⁇ / ⁇ ) or 10 8 (Omega / ⁇ ) or less, ⁇ the surface electrical resistivity of 10 8 ( ⁇ / ⁇ ) Indicates that it is over.
- the light was irradiated from the angle of 1 and the brightness L * value was measured for the reflected light in the direction perpendicular to the coating surface.
- ⁇ indicates that the L * value is 83 or more, ⁇ indicates that the L * value is 80 or more and less than 83, and ⁇ indicates that the L * value is less than 80.
- the coating film having high brightness and excellent conductivity was made into a plastic. It was found that it could be formed on the substrate.
Abstract
Description
1.バインダー成分(A)及びカーボンナノチューブ分散液(B)を含有する水性白色導電性プライマー塗料組成物であって、該水性白色導電性プライマー塗料組成物により形成される塗膜のCIE等色関数に基づく白色度によるL*値が80以上でありかつ表面電気抵抗率が108Ω/□以下である水性白色導電性プライマー塗料組成物。
2.前記バインダー成分(A)が、アクリル樹脂(A1)及びポリオレフィン樹脂(A2)から選ばれる少なくとも一種を含有する前記1に記載の水性白色導電性プライマー塗料組成物。
3.前記アクリル樹脂(A1)が、重合性不飽和モノマーを重合して得られるアクリル樹脂であって、該重合性不飽和モノマー100質量部を基準としてイソボルニル(メタ)アクリレートを10~50質量部含有するアクリル樹脂(A11)である前記2に記載の水性白色導電性プライマー塗料組成物。
4.前記ポリオレフィン樹脂(A2)が、重量平均分子量が50,000~150,000の範囲内であるポリオレフィン樹脂(A21)である前記2又は3に記載の水性白色導電性プライマー塗料組成物。
5.前記カーボンナノチューブ分散液(B)が下記(1)~(4)を満たすカーボンナノチューブ分散液(B1)である前記1~4のいずれか1に記載の水性白色導電性プライマー塗料組成物。
(1)カーボンナノチューブ(a)と、水溶性樹脂(b)と、水とを含有すること。
(2)カーボンナノチューブ(a)は、単層であり、透過型電子顕微鏡における画像解析における平均外径が0.5~5nmであり、比表面積が400~800m2/gであること。
(3)カーボンナノチューブ(a)の炭素成分100質量部に対して、水溶性樹脂(b)を400質量部以上、2000質量部以下含有すること。
(4)カーボンナノチューブ分散液のレーザー回折式粒度分布測定によって算出される50%粒子径(D50径)が1.5~40μmであること。
6.さらに酸化チタン顔料(C)を含有する前記1~5のいずれか1に記載の水性白色導電性プライマー塗料組成物。
7.前記酸化チタン顔料(C)の含有量が前記バインダー成分(A)の固形分100質量部を基準として、50~250質量部の範囲内である前記6記載の水性白色導電性プライマー塗料組成物。
8.以下の工程(1)~(4)を含む複層塗膜の形成方法。
(1)プラスチック基材に前記1~7のいずれか1に記載の水性白色導電性プライマー塗料組成物を塗装し、未硬化の白色導電性プライマー層を形成する工程
(2)前記白色導電性プライマー層の上に、干渉色ベース塗料組成物を静電塗装し、未硬化の干渉色ベース層を形成する工程
(3)前記干渉色ベース層の上に、クリヤー塗料組成物を静電塗装し、未硬化のクリヤー層を形成する工程
(4)工程(1)~(3)により形成された3層の塗膜を同時に焼付ける工程
以下、本発明についてさらに詳細に説明する。
バインダー成分(A)は、それ自体、成膜性を有するものであり、非架橋型及び架橋型のいずれであってもよく、なかでも架橋型であることが好ましい。該バインダー成分(A)としては、従来から塗料のバインダー成分として使用されているそれ自体既知の被膜形成性樹脂を使用できる。
アクリル樹脂(A1)は、重合性不飽和モノマーを重合して得られるアクリル樹脂であることが好ましく、水酸基含有重合性不飽和モノマー及びその他の重合性不飽和モノマーを重合して得られる水酸基含有アクリル樹脂であることがより好ましい。また、水への溶解性乃至分散性、架橋性等のために、カルボキシル基を有することが好ましい。重合方法は常法を用いることができる。
本発明の塗料組成物において使用されるポリオレフィン樹脂としては、ポリオレフィン及び変性ポリオレフィンのいずれも用いることができる。ポリオレフィンには、例えば、エチレン、プロピレン、ブチレン、ヘキセンなどの炭素数が2~10のオレフィンの1種もしくは2種以上を(共)重合せしめてなるポリオレフィンが包含される。また、変性ポリオレフィンには、該ポリオレフィンの不飽和カルボン酸もしくは酸無水物変性物、アクリル変性物、塩素化物、またこれらの変性を組合せて用いて得られる変性ポリオレフィンなどが包含される。
また、本発明の塗料組成物におけるカーボンナノチューブ分散液(B)の配合割合は、導電性及び塗膜の明度などの点から、バインダー成分(A)の固形分100質量部を基準として後記のカーボンナノチューブ(a)の含有量が、好ましくは0.01~1質量部、より好ましくは0.02~0.5質量部、さらに好ましくは0.03~0.3質量部である配合割合であることが好適である。
(1)カーボンナノチューブ(a)と、水溶性樹脂(b)と、水とを含有すること。
(2)カーボンナノチューブ(a)は、単層であり、透過型電子顕微鏡における画像解析における平均外径が0.5~5nmであり、比表面積が400~800m2/gであること。
(3)カーボンナノチューブ(a)の炭素成分100質量部に対して、水溶性樹脂(b)を400質量部以上、2000質量部以下含有すること。
(4)カーボンナノチューブ分散液のレーザー回折式粒度分布測定によって算出される50%粒子径(D50径)が1.5~40μmであること。
本発明に用いるカーボンナノチューブ(a)は、単層カーボンナノチューブ及び多層カーボンナノチューブのいずれであってもよいが、導電性の点から単層カーボンナノチューブであることが好ましい。単層カーボンナノチューブは、平面的なグラファイトを円筒状に巻いた形状を有しており、一層のグラファイトが巻かれた構造を有する。
カーボンナノチューブの炭素成分(%)=[1-{焼成後の灰分重量(g)/焼成前のカーボンナノチューブ重量(g)}]×100・・・・式(1)
水溶性樹脂(b)は、カーボンナノチューブに対して、分散工程における濡れを促進させ、分散安定化に寄与する分散剤として機能する水溶性の樹脂を表す。水溶性樹脂(b)は特に限定されないが、好適な例として以下の化合物が例示できる。
本発明におけるカーボンナノチューブ分散液(B)は、水溶性樹脂(b)を分散剤として、カーボンナノチューブ(a)を水中に分散したものである。この場合、水溶性樹脂(b)とカーボンナノチューブ(a)を同時、又は順次添加し、混合することで、水溶性樹脂(b)をカーボンナノチューブ(a)に作用(吸着)させつつ分散する。但し、カーボンナノチューブ分散液の製造をより容易に行うためには、水溶性樹脂(b)を水中に溶解、膨潤、又は分散させ、その後、液中にカーボンナノチューブ(a)を添加し、混合することで水溶性樹脂(b)をカーボンナノチューブ(a)に作用(吸着)させることが、より好ましい。
本発明の塗料組成物は、さらに顔料を含有することが好ましい。顔料の含有量は、形成塗膜の明度、付着性、耐水性などの点から、バインダー成分(A)の合計固形分100質量部を基準として、好ましくは50~250質量部、より好ましくは100~200質量部、さらに好ましくは125~175質量部である。
本発明の塗料組成物はイオン性液体を含有してもよい。本発明の塗料組成物において使用されるイオン性液体には、室温で液体状態にある融解塩(又は溶融塩)が包含される。通常の塩は一般に常温で固体であるが、融解塩は、特定のカチオンとアニオンとがイオン結合したものであり、室温で液体となる。ここで、室温とは約20℃の温度であり、また、室温付近とは約10~約40℃の温度を意味する。
本発明の塗料組成物を塗装する基材としては、各種プラスチック基材が挙げられる。プラスチック基材の材質としては、例えば、エチレン、プロピレン、ブチレン、ヘキセンなどの炭素数2~10のオレフィンの少なくとも1種を重合せしめてなるポリオレフィンが特に好適であるが、これらに限られるものではなく、ポリカーボネート、ABS樹脂、ウレタン樹脂、ナイロンなどの材質であってもよい。また、これらのプラスチック基材は、予め、それ自体既知の方法で、脱脂処理、水洗処理などを適宜行っておくことができる。
(1)プラスチック基材に本発明の塗料組成物を塗装し、未硬化の白色導電性プライマー層を形成する工程
工程(1)は、プラスチック基材に、本発明の塗料組成物を、通常、硬化膜厚で10~50μm程度、好ましくは15~45μm程度、より好ましくは20~40μm程度となるように塗装し、未硬化の白色導電性プライマー層を形成する工程である。
(2)前記白色導電性プライマー層の上に、干渉色ベース塗料組成物を静電塗装し、未硬化の干渉色ベース層を形成する工程
工程(2)は、工程(1)で形成した未硬化の白色導電性プライマー層上に、干渉色ベース塗料組成物を、通常、硬化膜厚で5~30μm程度、好ましくは10~25μm程度となるように静電塗装し、未硬化の干渉色ベース層を形成する工程である。
(3)前記干渉色ベース層の上に、クリヤー塗料組成物を静電塗装し、未硬化のクリヤー層を形成する工程
工程(3)は、工程(2)で形成した未硬化の干渉色ベース層上に、クリヤー塗料組成物を、通常、硬化膜厚で5~50μm程度、好ましくは10~40μm程度となるように静電塗装し、未硬化のクリヤー層を形成する工程である。
(4)工程(1)~(3)により形成された3層の塗膜を同時に焼付ける工程
工程(4)は、工程(1)~(3)により形成された3層の塗膜を、同時に加熱硬化する工程である。
(1a)前記白色導電性プライマー層の上に、水性白色非導電性プライマー塗料組成物を塗装し、未硬化の白色非導電性プライマー層を形成する工程。
(2a)前記白色導電性プライマー層の上に、水性白色ベース塗料組成物を静電塗装し、未硬化の白色ベース層を形成する工程。
(2b)前記白色導電性プライマー層の上に、水性高彩度ベース塗料組成物を静電塗装し、未硬化の高彩度ベース層を形成する工程。
<アクリル樹脂(A1)の調製>
<<アクリル樹脂(A11)の製造>>
メチルメタクリレート 18部
イソボルニルアクリレート 35部
n-ブチルアクリレート 10部
2-ヒドロキシエチルメタクリレ-ト 20部
アクリル酸 7部
2,2’-アゾビスイソブチロニトリル 1部
イソブチルアルコール 5部
撹拌機、温度計、還流冷却器等の備わった反応槽に、エチレングリコールモノブチルエーテル40部、イソブチルアルコール30部を仕込み、加熱撹拌し、100℃に達してから下記の単量体等の混合物を3時間かけて滴下した。
メチルメタクリレート 38部
n-ブチルアクリレート 25部
2-ヒドロキシエチルメタクリレ-ト 20部
アクリル酸 7部
2,2’-アゾビスイソブチロニトリル 1部
イソブチルアルコール 5部
・水性ポリオレフィン系樹脂(A2-1) 融点:80℃、重量平均分子量(Mw):80000
・水性ポリオレフィン系樹脂(A2-2) 融点:95℃、重量平均分子量(Mw):90000
トリメチロールプロパン、シクロヘキサンジメタノール、イソフタル酸及びアジピン酸を用いて常法によりエステル化反応せしめた。数平均分子量4500、水酸基価120、酸価10。
重量平均分子量1200、イミノ基含有メチルブチル混合エーテル化メラミン。
ヘキサメチレンジイソシアネートをマロン酸ジメチルでフルブロックした化合物。
<<カーボンナノチューブ(a)>>
・TUBALL(80%):OCSiAl社製シングルウォールカーボンナノチューブ、平均外径:1.5nm、炭素成分80%、平均長さ12μm、50%粒子径(D50)920μm、比表面積490m2/g、単層
・TUBALL(93%):OCSiAl社製シングルウォールカーボンナノチューブ、平均外径:1.5nm、炭素成分93%、平均長さ10μm、50%粒子径(D50)1010μm、比表面積850m2/g、単層
・カーボンナノチューブ(a-1):平均外径:1.5nm、炭素成分70%、平均長さ8μm、50%粒子径(D50)1190μm、比表面積750m2/g、単層
・カーボンナノチューブ(a-2):平均外径:1.5nm、炭素成分91%、平均長さ9μm、50%粒子径(D50)1350μm、比表面積1200m2/g、単層
スパッタ蒸着装置を用い、シリコンウェハー上へ厚さ1nmの鉄金属を蒸着した。これを反応炉に挿入し、アルゴン雰囲気下で800℃まで昇温させた後、アルゴン水素混合ガスを1000cc/分、エチレンガスを100cc/分中で10分間反応させ、カーボンナノチューブを回収した。さらに、ステンレス容器にカーボンナノチューブとガラスビーズを仕込み、ペイントコンディショナーで乾式粉砕処理を1時間行い、カーボンナノチューブを任意の長さに調整し、カーボンナノチューブ(a-1)を得た。
スパッタ蒸着装置を用い、シリコンウェハー上へ厚さ1nmの鉄金属を蒸着した。これを反応炉に挿入し、アルゴン雰囲気下で1000℃まで昇温させた後、アルゴン水素混合ガスを1000cc/分、エチレンガスを100cc/分中で10分間反応させ、カーボンナノチューブを回収した。さらに、ステンレス容器にカーボンナノチューブとガラスビーズを仕込み、ペイントコンディショナーで乾式粉砕処理を1時間行い、カーボンナノチューブを任意の長さに調整し、カーボンナノチューブ(a-2)を得た。
・Joncryl HPD-96J:BASFジャパン社製、スチレン-アクリル酸系、固形分酸価240mg KOH/g、不揮発分34%
・Joncryl JDX-6500:BASFジャパン社製、オールアクリル系(スチレンフリー)、固形分酸価215mg KOH/g、不揮発分29.5%
・Dispex Ultra PA 4550:BASFジャパン社製、変性ポリアクリル酸塩ポリマー、固形分酸価0mg KOH/g、固形分アミン価54mg KOH/g、不揮発分50%
・BYK-190:ビックケミー社製、スチレン系ブロック共重合、固形分酸価25mgKOH/g、不揮発分40%
・BYK-2010:ビックケミー社製、アクリルエマルション、固形分酸価50mgKOH/g、固形分アミン価50mg KOH/g、不揮発分40%
<<<カーボンナノチューブ分散液B-1>>>
カーボンナノチューブ(a)としてTUBALL 0.5部、水溶性分散樹脂(b)としてJoncryl JPD-96J 4.7部、消泡剤としてサーフィノール104E 0.3部、精製水94.5部をヘラで予備分散をした後に、直径0.5mmのジルコニアビーズ200gを分散メディアとして仕込み、ペイントシェーカーにて、4時間分散処理し、カーボンナノチューブ分散液B-1を得た。
表1に示す水溶性樹脂(b)の種類と量、分散処理時間に変更した以外は、カーボンナノチューブ分散液B-1と同様にして、カーボンナノチューブ分散液B-2~B-13、B-15~B-33を得た。
界面活性剤として「デモールN」(花王ケミカル社製、βーナフタレンスルホン酸ホルマリン縮合物ナトリウム塩)を0.04部加えたこと以外は、カーボンナノチューブ分散液B-7と同様にして、カーボンナノチューブ分散液B-14を得た。
得られたカーボンナノチューブ分散液について、以下の評価を行った。その結果を表1及び表2に示す。
粘度値の測定は、B型粘度計(東機産業社製「BL」)を用いて、分散液温度25℃、B型粘度計ローター回転速度60rpmにて、分散液をヘラで充分に撹拌した後、直ちに行った。測定に使用したローターは、粘度値が0.1Pa・s未満の場合はNo.1を、0.1Pa・s以上0.5Pa・s未満の場合はNo.2を、0.5Pa・s以上2.0Pa・s未満の場合はNo.3を、2.0Pa・s以上10Pa・s未満の場合はNo.4のものをそれぞれ用いた。得られた粘度値が10Pa・s以上の場合については、「>10」と記載したが、これは評価に用いたB型粘度計では評価不可能なほどに高粘度であったことを表す。分散直後から5時間以内に測定した粘度を、初期粘度とした。
分散液のカーボンナノチューブ(a)の粒度分布は、レーザー回折式粒度分布(マイクロトラック・ベル社製「マイクロトラックMT300II」)により、50%粒子径(D50)を算出した。
水性白色導電性プライマー塗料組成物の材料として、上記したバインダー成分(A)及びカーボンナノチューブ分散液(B)の他、下記を用いた。
・酸化チタン(C-1):商品名「TI-PURE R-706」、ケマーズ社製、ルチル型酸化チタン。
・酸化チタン(C-2):商品名「JR-806」、テイカ社製、ルチル型酸化チタン。
・導電性酸化チタン:商品名「ET-500W」、石原産業社製、白色導電性酸化チタン。
・導電性マイカ:商品名「Iriotec 7310」、メルク社製。
・イオン性液体:商品名「CIL-313」、日本カーリット社製
ポリプロピレン板(脱脂処理済)に、上記の通り作製した各塗料組成物を硬化膜厚で30μmになるようにエアスプレー塗装した。得られた塗装塗膜を、室温で3分間放置してセッティングしてから、60℃、3分間のプレヒートを施し、白色プライマー層を形成した。
上記の通り作製した各試験塗装板を下記の性能試験に供した。その結果を表2に示す。
(1)プライマー塗膜面の表面電気抵抗率
黒色のポリプロピレン板(脱脂処理済)に、上記の通り作製した各塗料組成物をそれぞれ硬化膜厚で30μmになるようにスプレー塗装して形成したプライマー塗膜を室温で3分間放置してセッティングしてから、60℃、3分間のプレヒートを施した後、各塗膜面の表面電気抵抗率(Ω/□)を「MODEL150」(TREK社製)で20℃にて測定した。◎は表面電気抵抗率が106(Ω/□)未満、○は表面電気抵抗率が106(Ω/□)以上108(Ω/□)以下、×は表面電気抵抗率が108(Ω/□)超であることを示す。
黒色のポリプロピレン板(脱脂処理済)に、上記の通り作製した各塗料組成物をそれぞれ硬化膜厚で30μmになるようにスプレー塗装して形成したプライマー塗膜を室温で3分間放置してセッティングしてから、60℃、3分間のプレヒートを施した。次いで、120℃で30分間加熱した後、各試験塗装板について、それぞれマルチアングル分光測色計「CM-512m3」(コニカミノルタ社製)を用いて、塗膜面に垂直な軸に対し45°の角度から光を照射し、反射した光のうち塗膜面に垂直な方向の光について明度L*値を測定した。◎はL*値が83以上、○はL*値が80以上83未満、×はL*値が80未満であることを示す。
前記の通り作製した各試験塗装板を、JIS K 5600-7-7に準じ、「スーパーキセノンウエザーメーター」(スガ試験機社製、耐候性試験機)を用いて、試験片ぬれサイクル:18分/2時間、ブラックパネル温度:61~65℃の条件で、促進耐候性試験を行った。次に、ランプの照射時間が1,000時間に達した時点で、試験塗装板の外観を目視で評価した。○は外観に異常が無いこと、×は外観に異常があることを示す。
本出願は、2019年9月20日出願の日本特許出願(特願2019-172015)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (8)
- バインダー成分(A)及びカーボンナノチューブ分散液(B)を含有する水性白色導電性プライマー塗料組成物であって、該水性白色導電性プライマー塗料組成物により形成される塗膜のCIE等色関数に基づく白色度によるL*値が80以上でありかつ表面電気抵抗率が108Ω/□以下である水性白色導電性プライマー塗料組成物。
- 前記バインダー成分(A)が、アクリル樹脂(A1)及びポリオレフィン樹脂(A2)から選ばれる少なくとも一種を含有する請求項1に記載の水性白色導電性プライマー塗料組成物。
- 前記アクリル樹脂(A1)が、重合性不飽和モノマーを重合して得られるアクリル樹脂であって、該重合性不飽和モノマー100質量部を基準としてイソボルニル(メタ)アクリレートを10~50質量部含有するアクリル樹脂(A11)である請求項2に記載の水性白色導電性プライマー塗料組成物。
- 前記ポリオレフィン樹脂(A2)が、重量平均分子量が50,000~150,000の範囲内であるポリオレフィン樹脂(A21)である請求項2又は3に記載の水性白色導電性プライマー塗料組成物。
- 前記カーボンナノチューブ分散液(B)が下記(1)~(4)を満たすカーボンナノチューブ分散液(B1)である請求項1~4のいずれか1項に記載の水性白色導電性プライマー塗料組成物。
(1)カーボンナノチューブ(a)と、水溶性樹脂(b)と、水とを含有すること。
(2)カーボンナノチューブ(a)は、単層であり、透過型電子顕微鏡における画像解析における平均外径が0.5~5nmであり、比表面積が400~800m2/gであること。
(3)カーボンナノチューブ(a)の炭素成分100質量部に対して、水溶性樹脂(b)を400質量部以上、2000質量部以下含有すること。
(4)カーボンナノチューブ分散液のレーザー回折式粒度分布測定によって算出される50%粒子径(D50径)が1.5~40μmであること。 - さらに酸化チタン顔料(C)を含有する請求項1~5のいずれか1項に記載の水性白色導電性プライマー塗料組成物。
- 前記酸化チタン顔料(C)の含有量が前記バインダー成分(A)の固形分100質量部を基準として、50~250質量部の範囲内である請求項6記載の水性白色導電性プライマー塗料組成物。
- 以下の工程(1)~(4)を含む複層塗膜の形成方法。
(1)プラスチック基材に請求項1~7のいずれか1項に記載の水性白色導電性プライマー塗料組成物を塗装し、未硬化の白色導電性プライマー層を形成する工程
(2)前記白色導電性プライマー層の上に、干渉色ベース塗料組成物を静電塗装し、未硬化の干渉色ベース層を形成する工程
(3)前記干渉色ベース層の上に、クリヤー塗料組成物を静電塗装し、未硬化のクリヤー層を形成する工程
(4)工程(1)~(3)により形成された3層の塗膜を同時に焼付ける工程
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Publication number | Priority date | Publication date | Assignee | Title |
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CN114133825A (zh) * | 2021-11-25 | 2022-03-04 | 紫荆花涂料(上海)有限公司 | 一种无溶剂环氧树脂涂料及其制备方法和应用 |
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Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004075735A (ja) | 2002-08-12 | 2004-03-11 | Kansai Paint Co Ltd | 白色導電性プライマー塗料及び複層塗膜形成方法 |
WO2005012449A1 (ja) | 2003-07-23 | 2005-02-10 | Kansai Paint Co., Ltd. | 白色導電性プライマー塗料組成物及び複層塗膜形成方法 |
JP2006219521A (ja) * | 2005-02-08 | 2006-08-24 | Toyota Motor Corp | 水性導電プライマー塗料組成物及び塗装物品 |
JP2006232884A (ja) * | 2005-02-22 | 2006-09-07 | Basf Coatings Japan Ltd | 白色導電性プライマー塗料組成物、それを用いた塗装方法、及び該塗装方法で塗装された塗装物品 |
WO2007046532A1 (ja) * | 2005-10-18 | 2007-04-26 | Kansai Paint Co., Ltd. | 水性プライマー組成物及びその塗装方法 |
JP2015051621A (ja) * | 2013-08-07 | 2015-03-19 | 東レ株式会社 | 積層ポリエステルフィルム、およびその製造方法 |
JP2016084423A (ja) * | 2014-10-27 | 2016-05-19 | 理想科学工業株式会社 | 活性エネルギー線硬化型帯電防止性組成物及びこれを含有する帯電防止用塗料 |
WO2016121242A1 (ja) * | 2015-01-29 | 2016-08-04 | 関西ペイント株式会社 | 水性塗料組成物 |
JP2017066321A (ja) * | 2015-10-01 | 2017-04-06 | 大日精化工業株式会社 | 導電性樹脂組成物及びその製造方法 |
JP2019172015A (ja) | 2018-03-28 | 2019-10-10 | 日立オートモティブシステムズ株式会社 | エアサスペンションシステム、および、カメラ洗浄システム |
JP2020019924A (ja) * | 2018-07-20 | 2020-02-06 | 東洋インキScホールディングス株式会社 | カーボンナノチューブ分散液およびその利用 |
JP2020180185A (ja) * | 2019-04-24 | 2020-11-05 | 石原産業株式会社 | 複合材料及びその製造方法、並びにその用途 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5601760B2 (ja) * | 2007-06-29 | 2014-10-08 | 関西ペイント株式会社 | 水性プライマー組成物、及びこの組成物を用いた塗装方法 |
CN102725360A (zh) * | 2010-02-05 | 2012-10-10 | 关西涂料株式会社 | 水性底漆组合物及使用该组合物的涂装方法 |
EP3397700A1 (en) * | 2015-12-29 | 2018-11-07 | PPG Industries Ohio, Inc. | Infrared fluorescent coating compositions |
CN107573779A (zh) | 2017-09-27 | 2018-01-12 | 芜湖春风新材料有限公司 | 一种碳纳米管静电喷涂底漆、制备方法及其应用 |
CN109777214B (zh) | 2017-11-15 | 2021-10-15 | 常州第六元素材料科技股份有限公司 | 石墨烯导静电底漆及其制备方法 |
CN109456657A (zh) | 2018-10-22 | 2019-03-12 | Ppg涂料(天津)有限公司 | 导电底漆组合物以及制备方法 |
-
2020
- 2020-09-16 WO PCT/JP2020/035048 patent/WO2021054352A1/ja unknown
- 2020-09-16 CA CA3155132A patent/CA3155132A1/en active Pending
- 2020-09-16 CN CN202080064628.1A patent/CN114402041B/zh active Active
- 2020-09-16 JP JP2021546928A patent/JP7161063B2/ja active Active
- 2020-09-16 EP EP20864620.8A patent/EP4032621A4/en active Pending
- 2020-09-16 US US17/761,034 patent/US20220340765A1/en active Pending
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004075735A (ja) | 2002-08-12 | 2004-03-11 | Kansai Paint Co Ltd | 白色導電性プライマー塗料及び複層塗膜形成方法 |
WO2005012449A1 (ja) | 2003-07-23 | 2005-02-10 | Kansai Paint Co., Ltd. | 白色導電性プライマー塗料組成物及び複層塗膜形成方法 |
JP2006219521A (ja) * | 2005-02-08 | 2006-08-24 | Toyota Motor Corp | 水性導電プライマー塗料組成物及び塗装物品 |
JP2006232884A (ja) * | 2005-02-22 | 2006-09-07 | Basf Coatings Japan Ltd | 白色導電性プライマー塗料組成物、それを用いた塗装方法、及び該塗装方法で塗装された塗装物品 |
WO2007046532A1 (ja) * | 2005-10-18 | 2007-04-26 | Kansai Paint Co., Ltd. | 水性プライマー組成物及びその塗装方法 |
JP2015051621A (ja) * | 2013-08-07 | 2015-03-19 | 東レ株式会社 | 積層ポリエステルフィルム、およびその製造方法 |
JP2016084423A (ja) * | 2014-10-27 | 2016-05-19 | 理想科学工業株式会社 | 活性エネルギー線硬化型帯電防止性組成物及びこれを含有する帯電防止用塗料 |
WO2016121242A1 (ja) * | 2015-01-29 | 2016-08-04 | 関西ペイント株式会社 | 水性塗料組成物 |
JP2017066321A (ja) * | 2015-10-01 | 2017-04-06 | 大日精化工業株式会社 | 導電性樹脂組成物及びその製造方法 |
JP2019172015A (ja) | 2018-03-28 | 2019-10-10 | 日立オートモティブシステムズ株式会社 | エアサスペンションシステム、および、カメラ洗浄システム |
JP2020019924A (ja) * | 2018-07-20 | 2020-02-06 | 東洋インキScホールディングス株式会社 | カーボンナノチューブ分散液およびその利用 |
JP2020180185A (ja) * | 2019-04-24 | 2020-11-05 | 石原産業株式会社 | 複合材料及びその製造方法、並びにその用途 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114133825A (zh) * | 2021-11-25 | 2022-03-04 | 紫荆花涂料(上海)有限公司 | 一种无溶剂环氧树脂涂料及其制备方法和应用 |
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