WO2021132246A1 - Composition de revêtement, film de revêtement obtenu à partir de celle-ci, et procédé de formation d'un film de revêtement multicouche - Google Patents

Composition de revêtement, film de revêtement obtenu à partir de celle-ci, et procédé de formation d'un film de revêtement multicouche Download PDF

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Publication number
WO2021132246A1
WO2021132246A1 PCT/JP2020/047970 JP2020047970W WO2021132246A1 WO 2021132246 A1 WO2021132246 A1 WO 2021132246A1 JP 2020047970 W JP2020047970 W JP 2020047970W WO 2021132246 A1 WO2021132246 A1 WO 2021132246A1
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Prior art keywords
coating film
resin
coating composition
coating
composition according
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PCT/JP2020/047970
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English (en)
Japanese (ja)
Inventor
俊哉 池中
晋之介 河野
涼子 大西
水口　克美
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日本ペイント・オートモーティブコーティングス株式会社
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Publication of WO2021132246A1 publication Critical patent/WO2021132246A1/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • 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
    • 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
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • 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
    • 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
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/65—Additives macromolecular

Definitions

  • the present invention relates to a coating composition, a coating film using the same, and a method for forming a multi-layer coating film.
  • automotive parts may contain polyolefin resins. Further, in order to impart the strength required for automobile parts, a polyolefin resin, a carbon pigment, a carbon fiber or the like may be used in combination. Therefore, such automotive parts usually have a black appearance.
  • automobile parts need to express various colors. For example, not only the expression of blackish colors is required, but also the expression of solid whites, whites including mica, and the like is required. Therefore, in order to develop the required color, it is usually made to conceal a black base by using a coating composition containing titanium oxide for automobile parts having a black appearance.
  • Patent Document 1 describes chlorine-method titanium oxide pigments, yellow iron oxide pigments, carbon black pigments having a primary average particle size in the range of 15 nm or more and 80 nm or less, and resins that are vehicle-forming components.
  • a coating composition containing the composition is disclosed.
  • Patent Document 1 discloses a coating film forming method in which a coating composition according to Patent Document 1 is applied to an object to be coated and a color-based coating film is laminated on the obtained coating film.
  • the film thickness of the coating film formed from this coating composition is increased. There is a need. Alternatively, it is necessary to form a coating film having a high concentration of titanium oxide.
  • the concentration of titanium oxide in the coating film is increased, the moisture resistance of the formed coating film may be inferior. Further, if the film thickness of the coating film containing titanium oxide is increased, the water resistance of the obtained coating film may be inferior. Therefore, there is a demand for a coating composition that can satisfactorily conceal the color tone of the object to be coated, for example, black color, even if the concentration of titanium oxide is not high. Further, in order to increase the film thickness of the coating film containing titanium oxide, it is necessary to form the coating film in a plurality of times, and simplification of the work process is required. In addition, there is a demand for a coating composition capable of concealing the color tone of the object to be coated, for example, black, while having a thinner film thickness.
  • An object of the present invention is to solve the above-mentioned problems and to provide a coating composition capable of concealing the color tone of the object to be coated, for example, black, while having a thinner film thickness. Furthermore, the present invention provides a coating composition capable of forming a coating film having excellent adhesion, chemical resistance, water resistance, flexibility and appearance.
  • a paint composition At least one selected from the group consisting of a maleic anhydride-modified polyolefin resin (A), a glycidyl group-containing acrylic resin emulsion (B), and a urethane resin dispersion (C).
  • Resin dispersion (D) and hardener (E) Including Solubility parameter SP (A) of maleic anhydride-modified polyolefin resin (A), solubility parameter SP (B) of glycidyl group-containing acrylic resin in emulsion (B), and dissolution of resin in resin dispersion (D)
  • Solubility parameter SP (A) of maleic anhydride-modified polyolefin resin (A)
  • dissolution of resin in resin dispersion (D) The sex parameter SP (D) satisfies at least one of the following equations (1) and (2).
  • the sex parameter SP (D) satisfies at least one of the following equations (1) and (2).
  • the resin dispersion (D) is a polyester resin dispersion (D1), and the polyester resin in the polyester resin dispersion (D1) has a solubility parameter SP (D1) of 11.0. It is 12.0 or less.
  • the number average molecular weight of the polyester resin in the polyester resin dispersion (D1) is 6,000 or more and 20,000 or less.
  • the resin dispersion (D) is an acrylic resin emulsion (D2), and the acrylic resin in the acrylic resin emulsion (D2) has a solubility parameter SP (D2) of 8.0 or more 12 It is .0 or less, and the acrylic resin does not contain a glycidyl group.
  • the acrylic resin in the acrylic resin emulsion (D2) is the crosslinkable resin particles.
  • the maleic anhydride-modified polyolefin resin (A) is a maleic anhydride-modified chlorinated polyolefin resin.
  • the coating composition comprises particles selected from the group consisting of organic particles and inorganic particles.
  • the coating composition contains a coloring pigment, and the amount of the coloring pigment is 3% by mass or more and 150% by mass or less with respect to the total resin solid content of (A) to (E). .. [10]
  • the coating composition is an aqueous primer coating composition.
  • a method for forming a coating film which comprises a step of coating an object to be coated with the coating composition according to the present disclosure to form an uncured coating film, and a step of heat-curing the uncured coating film to form a coating film. I will provide a. [12] In another embodiment, the present disclosure.
  • a step of coating an object to be coated with the aqueous primer coating composition according to the present disclosure to form an uncured primer coating film A step of coating a base coating composition containing a bright pigment on an uncured aqueous primer coating composition to form an uncured base coating film.
  • the step of applying the clear coating composition on the uncured base coating film to form the uncured clear coating film, and the uncured primer coating film, the base coating film and the clear coating film are heat-cured to form a double layer.
  • a method for forming a multi-layer coating film which comprises a step of forming a layer coating film.
  • the coating composition of the present invention can form a thin film, and moreover, can form a coating film capable of hiding the color tone of the object to be coated. Further, the coating composition of the present invention can form a coating film having excellent adhesion, chemical resistance, water resistance, flexibility and appearance.
  • plastic automobile parts are used in vehicles such as automobiles.
  • Automobile parts are required to have excellent strength, impact resistance, and the like, and are usually required to develop a color tone suitable for the automobile body.
  • automobile parts containing carbon materials and polyolefin resins are often black. Therefore, in order to develop a color tone that matches the automobile body, especially a white mica color tone, a white primer coating film is formed on a black object to be coated, and a white color base coating is applied on the primer coating film. It is necessary to form a film and further, a mica-containing base coating film, and to form a clear coating film on the outermost layer.
  • the required color tone for example, the color tone of white mica
  • the thickness of the white primer coating film containing a white pigment is usually increased or white. It is necessary to form a white primer coating with an increased amount of pigment.
  • titanium oxide which is generally used as a white pigment
  • the water resistance tends to decrease. Further, if the amount of titanium oxide is reduced, it becomes necessary to increase the film thickness.
  • the present invention is a coating composition. At least one selected from the group consisting of a maleic anhydride-modified polyolefin resin (A), a glycidyl group-containing acrylic resin emulsion (B), and a urethane resin dispersion (C).
  • A maleic anhydride-modified polyolefin resin
  • B glycidyl group-containing acrylic resin emulsion
  • C a urethane resin dispersion
  • Resin dispersion (D) and hardener (E) Including Solubility parameter SP (A) of maleic anhydride-modified polyolefin resin (A), solubility parameter SP (B) of glycidyl group-containing acrylic resin in emulsion (B), and dissolution of resin in resin dispersion (D)
  • Solubility parameter SP (A) of maleic anhydride-modified polyolefin resin (A)
  • dissolution of resin in resin dispersion (D) The sex parameter SP (D) satisfies at least one of the following equations (1) and (2).
  • the haze value of a coating film having a thickness of 30 ⁇ m formed from a mixture containing at least one of the above, a resin dispersion (D), and a curing agent (E) in the same mass ratio as that of the coating composition is 15% or more. It is a coating composition.
  • the present invention Maleic anhydride-modified polyolefin resin (A), Glycidyl group-containing acrylic resin emulsion (B), Urethane resin dispersion (C), Resin dispersion (D) and hardener (E) Including Solubility parameter SP (A) of maleic anhydride-modified polyolefin resin (A), solubility parameter SP (B) of glycidyl group-containing acrylic resin in emulsion (B), and dissolution of resin in resin dispersion (D)
  • the sex parameter SP (D) satisfies at least one relationship of the following equations (1) and (2).
  • the coating composition according to the present disclosure it is possible to form a coating film which is a thin film but can hide the color tone such as black and gray of the object to be coated. Therefore, the coating composition according to the present disclosure can form a thinner coating film as compared with, for example, a coating film containing titanium oxide. Further, since the coating film formed from the coating composition according to the present disclosure may have a white appearance, the color tone of the object to be coated, for example, black or gray, can be sufficiently concealed even though it is a thin film. Therefore, the coating film formed from the coating composition according to the present disclosure is a single-layered white primer coating film containing titanium oxide and a color-based coating film arranged on the white primer coating film, which is usually used. Can be provided with the functions of and.
  • a white primer coating film is usually formed on a black object to be coated, and a white color base is formed on the primer coating film. It is necessary to form a coating film and further, a mica-containing base coating film, and to form a clear coating film on the outermost layer.
  • a coating film formed from the coating composition according to the present disclosure is formed on a black object to be coated, and further, on the coating film according to the present disclosure.
  • a mica-containing base coating film can be formed, and a clear coating film can be formed on the outermost layer.
  • the coating film formed from the coating composition according to the present disclosure has the functions of a commonly used white primer coating film containing titanium oxide and a color-based coating film arranged on the white primer coating film in a single layer. You can prepare for it. Therefore, the layer structure can be made thinner and the coating film forming step can be reduced as compared with the conventional multi-layer coating film. Furthermore, the desired white mica color tone can be expressed.
  • the coating composition according to the present disclosure can form a thin film having a high hiding property, and can shorten the coating process, coating time, etc. in automobile parts. Therefore, it is possible to reduce the environmental load such as CO 2 reduction. Moreover, it is possible to form a coating film having excellent adhesion, chemical resistance, water resistance, flexibility and appearance.
  • the coating composition according to the present disclosure will be described in more detail.
  • the coating composition according to the present disclosure is At least one selected from the group consisting of a maleic anhydride-modified polyolefin resin (A), a glycidyl group-containing acrylic resin emulsion (B), and a urethane resin dispersion (C). Resin dispersion (D) and hardener (E) including.
  • A maleic anhydride-modified polyolefin resin
  • B glycidyl group-containing acrylic resin emulsion
  • C urethane resin dispersion
  • Resin dispersion (D) and hardener (E) including.
  • the coating composition according to the present disclosure can form a thin film having excellent adhesion, chemical resistance, water resistance, flexibility and appearance. Further, it is possible to form a coating film having the coating film strength required for automobile parts.
  • the coating composition contains all of the above components (A) to (E). That is, in one embodiment, the coating composition comprises a maleic anhydride-modified polyolefin resin (A), a glycidyl group-containing acrylic resin emulsion (B), and a urethane resin dispersion (C), a resin dispersion (D), and a curing agent. (E) is included.
  • solubility parameter SP (A) of the maleic anhydride-modified polyolefin resin (A) the solubility parameter SP (B) of the glycidyl group-containing acrylic resin in the emulsion (B), and the resin dispersion (D).
  • the solubility parameter SP (D) of the resin of the above satisfies at least one of the following formulas (1) and (2).
  • at least one of equations (1) and (2) is satisfied, that is, the absolute value of SP (D) minus SP (A), and SP (D) minus SP (B).
  • the coating composition according to the present disclosure can form a coating film having a high hiding property. Therefore, the coating film formed from the coating composition according to the present disclosure is a single-layered white primer coating film containing titanium oxide and a color-based coating film arranged on the white primer coating film, which is generally used. Can be provided with the functions of and. That is, the layer structure can be made thinner and the coating film forming step can be reduced as compared with the conventional multi-layer coating film. Further, for example, even if the color tone of the coating film formed on the coating film formed by the coating composition according to the present disclosure is the color tone of white mica, the desired color tone can be sufficiently expressed.
  • a coating film having a high hiding property for example, a thin film can be formed.
  • the solubility parameter SP value for the specific resin according to the present disclosure, by setting the solubility parameter SP value to a specific condition, extremely high hiding property can be obtained without deteriorating various physical properties such as coating film strength, adhesion and hardness.
  • the coating film to have can be formed.
  • the coating film becomes cloudy without being largely dependent on the white paint such as titanium oxide, the physical characteristics of the coating film tend to be inferior.
  • the coating composition according to the present disclosure contains a specific resin under specific conditions, the coating film is phase-separated and light is diffusely reflected due to the difference in refractive index, resulting in high hiding property and excellent coating film physical characteristics. It is considered that both can be held in a well-balanced manner.
  • the coating composition according to the present disclosure is an aqueous primer coating composition, various resin components can maintain a stable dispersed state. Therefore, the stability of the coating composition is maintained, and the coating film formed from such a coating composition can also exhibit high coating film physical characteristics, and moreover, the coating film physical properties are not impaired. It is presumed to show high concealment.
  • ⁇ 1.05 May have a relationship of, for example 1.40 ⁇
  • the solubility parameter SP value of these specific resins By setting the solubility parameter SP value of these specific resins to specific conditions, a coating film having higher hiding power can be formed, and even a thin film can have sufficient hiding power.
  • the thin film means a film thickness of about (20 ⁇ m or more and 35 ⁇ m or less), but is not limited to this numerical range.
  • the solubility parameter SP value of the specific resin according to the present disclosure it is possible to form a coating film having more excellent physical properties such as coating film strength, adhesion and hardness.
  • the conditions of the SP value may be used in combination.
  • the SP value is an abbreviation for solution parameter, which is a measure of solubility.
  • the SP value can be actually measured by the following method [References: SUH, CLARKE, J. Mol. P. S. A-1, 5, 1671 to 1681 (1967)].
  • an organic solvent is weighed in a 100 ml beaker, 10 ml of acetone is added using a whole pipette, and the mixture is dissolved by a magnetic stirrer.
  • a poor solvent is added dropwise to this sample using a 50 ml burette at a measurement temperature of 20 ° C., and the point at which turbidity occurs is defined as the amount of addition.
  • the poor solvent ion-exchanged water is used as the high SP poor solvent, and n-hexane is used as the low SP poor solvent, and the turbidity point is measured.
  • the SP value ⁇ of the organic solvent is given by the following formula.
  • the haze value of the coating film having a thickness of 30 ⁇ m formed from the mixture containing the curing agent (E) and the curing agent (E) in the same mass ratio as in the coating composition is 15% or more.
  • the haze value of the coating film having a thickness of 30 ⁇ m is 30% or more.
  • the haze value of the coating film having a thickness of 30 ⁇ m is 35% or more, for example, the haze value is 40% or more. The higher the haze value, the better the hiding property. Therefore, the higher the haze value, the more preferable.
  • the color tone of the object to be coated for example, black or silver
  • the coating film can have high hiding power and can exhibit white or a color close to white
  • a commonly used white primer coating film containing titanium oxide and a color base coating film arranged on the white primer coating film are used.
  • the function of the film can be provided by a coating film formed from the coating composition according to the present disclosure. Therefore, the coating film according to the present disclosure has the functions of a commonly used white primer coating film containing titanium oxide and a color base coating film arranged on the white primer coating film. Although it is a single layer, it can be prepared. Further, the layer structure can be made thinner as compared with the conventional multi-layer coating film, and the coating film forming step can be reduced. In addition, a desired color tone, particularly a color tone of white mica, can be satisfactorily expressed.
  • the preparation of a coating film for measuring the haze of a coating film having a thickness of 30 ⁇ m can be prepared based on the following method.
  • the haze value of a coating film having a thickness of 30 ⁇ m can be measured by a method compliant with JIS K7136: 2000 using a commercially available turbidity meter (for example, ⁇ 90 color measurement system manufactured by Nippon Denshoku Kogyo Co., Ltd.).
  • the solubility parameter SP (A) of the maleic anhydride-modified polyolefin resin (A) according to the present disclosure may be, for example, 8.2 or more and 9.5 or less, and 8.3 or more and 9.3 or less. ..
  • the maleic anhydride-modified polyolefin resin (A) may be any derivative synthesized from the polyolefin resin and maleic anhydride, and is not particularly limited.
  • the maleic anhydride-modified polyolefin resin (A) may be of only one type or of two or more types.
  • the maleic anhydride-modified polyolefin resin (A) may be in an emulsion state, and such a resin (A) may be referred to as a maleic anhydride-modified polyolefin resin emulsion.
  • the maleic anhydride-modified polyolefin resin (A) means the maleic anhydride-modified polyolefin resin emulsion itself, and does not contain other emulsion resins.
  • the weight average molecular weight of the maleic anhydride-modified polyolefin resin (A) is preferably in the range of 20,000 or more and 200,000 or less, and more preferably in the range of 50,000 or more and 120,000 or less.
  • the weight average molecular weight can be calculated from the measurement result of gel permeation chromatography (GPC) using polystyrene as a standard.
  • GPC gel permeation chromatography
  • the weight average molecular weight is within such a range, for example, in the embodiment in which the coating composition according to the present disclosure is used as a primer coating composition, the strength required as a primer coating film can be maintained, and the coating material can be combined with the object to be coated. It is possible to maintain high adhesion and further suppress coagulation failure in the coating film.
  • the maleic anhydride-modified polyolefin resin (A) can be emulsified by a known method described in the present disclosure, and further, the stabilization of the coating composition can be shown. Further, for example, in the embodiment in which the polyolefin material is used for the object to be coated, the decrease in wettability can be suppressed and the adhesion of the material can be improved.
  • the maleic anhydride-modified polyolefin resin (A) may be, for example, 15% by mass or more and 40% by mass or less, and 20% by mass or more and 35% by mass or less, based on the total resin solid content in the coating composition according to the present disclosure. Good.
  • the total resin solid content in the coating composition according to the present disclosure means the total solid content of (A), (B), (C), (D) and (E).
  • the amount of the maleic anhydride-modified polyolefin resin (A) is within such a range, good adhesion can be maintained, for example, in a mode in which a polyolefin material is used for the object to be coated.
  • poor appearance can be suppressed, and for example, poor adhesion to the underlying coating film at the time of recoating can be suppressed.
  • a commonly used emulsification method such as a mechanical emulsification method, a method using an emulsifier or a basic substance, or a combination thereof can be used. It can.
  • an emulsifier When an emulsifier is used, the amount of the emulsifier can be appropriately set depending on the amount of the maleic anhydride-modified polyolefin resin (A), the basic substance, water and the like.
  • a basic substance When a basic substance is used, it can be appropriately set depending on the amount of maleic anhydride-modified polyolefin resin, water, etc., and in particular, the amount is such that the acid functional groups of the maleic anhydride-modified polyolefin resin (A) and the emulsifier are sufficiently neutralized. Further, it is preferable to set the pH of the obtained emulsion in consideration of 7 or more and 11 or less, more preferably 7.5 or more and 10.5 or less. When the pH value of the obtained maleic anhydride-modified polyolefin resin emulsion is within the above range, the stabilization of the emulsion can be maintained, for example, the release of a basic substance can be suppressed, and the water resistance can be improved.
  • the average particle size of the maleic anhydride-modified polyolefin resin in the emulsion is not particularly limited.
  • the average particle size is preferably 0.01 ⁇ m or more and 10 ⁇ m or less. Since the average particle size is within such a range, a large amount of emulsifier is not required. For example, if a large amount of emulsifier is contained, the water resistance of the coating film may be slightly inferior. On the other hand, by having the above average particle size, it is possible to suppress a decrease in water resistance of the coating film. In addition, the stability of the emulsion may be kept good.
  • the mass ratio of the structure derived from maleic anhydride (acid anhydride) in the maleic anhydride-modified polyolefin resin (A) is preferably 1% by mass or more and 10 or less by mass, more preferably. It is preferably 1.2% by mass or more and 5% by mass or less.
  • the mass ratio is within the above range, the maleic anhydride-modified polyolefin resin (A) can be appropriately emulsified, and the coating composition can be stabilized. In addition, it is possible to suppress a decrease in the water resistance of the coating film.
  • the maleic anhydride-modified polyolefin resin (A) may be a chlorinated maleic anhydride-modified polyolefin resin (A).
  • a chlorinated resin is referred to as a maleic anhydride-modified chlorinated polyolefin resin.
  • the chlorinated maleic anhydride-modified polyolefin resin (A) for example, in the embodiment of using the coating composition according to the present disclosure as a primer coating composition, the strength required as a primer coating film can be maintained, and the coating film can be coated. High adhesion with the coating can be maintained. In addition, cohesive failure in the coating film can be suppressed. In addition, it can show stabilization of the coating composition. Further, by chlorination, the melting point is lowered while maintaining the crystallinity of the crystalline polyolefin, and handling such as emulsification becomes easy.
  • the coating composition according to the present disclosure may contain a maleic anhydride-modified chlorinated polyolefin resin as a maleic anhydride-modified chlorinated polyolefin resin emulsion resin.
  • the chlorine content of the chlorinated polyolefin resin used for obtaining the maleic anhydride-modified chlorinated polyolefin resin emulsion is 15% by mass or more and 40% by mass or less, more preferably 20% by mass in the maleic anhydride-modified chlorinated polyolefin resin. % To 35% by mass or less.
  • the solubility parameter SP (B) of the glycidyl group-containing acrylic resin in the emulsion (B) may be, for example, 9.9 or more and 11.5 or less, and may be 10 or more and 11 or less.
  • hydrophilic groups are required to stabilize the resin in the aqueous medium.
  • a carboxyl group, a hydroxyl group, an amino group and the like When a large amount of such hydrophilic groups are contained, various problems occur in the water resistance test. For example, a large amount of water is absorbed, blisters are generated, and delamination with the inferior membrane and upper membrane is likely to occur due to water swelling.
  • the cohesive force of the coating film can be improved by using the glycidyl group-containing acrylic resin emulsion (B).
  • the glycidyl group-containing acrylic resin emulsion (B) for example, in the case of a white coating film or a mica coating film, yellowing deterioration of the primer coating film that can be caused by the ultraviolet rays of sunlight reaching the primer can be prevented. Can be suppressed.
  • the glycidyl group-containing acrylic resin can be obtained by copolymerizing a radically polymerizable monomer containing a glycidyl group with another radically polymerizable monomer.
  • a radically polymerizable monomer containing a glycidyl group with another radically polymerizable monomer.
  • Functional group-containing monomers such as substances, and further, as (meth) acrylic acid alkyl ester, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, isopropyl (meth) acrylic acid, N-butyl (meth) acrylic acid, T-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) )
  • Acrylic resin emulsion (B) containing a glycidyl group can be obtained by copolymerizing with lauryl acrylate to obtain an aqueous emulsion.
  • aqueous emulsion examples include a method of subjecting to solvent polymerization and then emulsion by forced stirring or using an emulsifier in water, an emulsion polymerization method of copolymerizing in water using an emulsifier, and the like.
  • the mass ratio of the structure derived from the glycidyl group-containing monomer in the glycidyl group-containing acrylic resin in the emulsion (B) is preferably 30% by mass or more and 60% by mass or less. That is, it is preferable that the radically polymerizable monomer containing a glycidyl group is 30% by mass or more and 60% by mass or less in all the monomers used for the synthesis of the glycidyl group-containing acrylic resin.
  • the glycidyl group-containing acrylic resin in the emulsion (B) is preferably 20% by mass or more and 35% by mass or less in the total resin solid content in the coating composition according to the present disclosure. Within such a range, it is possible to suppress coagulation breakage / peeling of the coating film even under conditions such as subjecting to a water resistance test and then evaluating the adhesion of the coating film. Further, it is possible to prevent the degree of cross-linking from becoming too large, for example, it is possible to suppress cross-linking strain, and it is possible to suppress delamination with other coating films and objects to be coated in the initial adhesion.
  • the coating composition according to the present disclosure may comprise a urethane resin dispersion (C).
  • a urethane resin dispersion (C) a polyfunctional isocyanate compound, a polyol having two or more hydroxyl groups in one molecule, and hydrophilicity having both hydroxyl groups and carboxylic acid groups such as dimethylolpropanediol or dimethylolbutanediol.
  • the agent is reacted in the presence of a catalyst such as dibutyltin dilaurylate in an excess of isocyanate groups to obtain a urethane prepolymer, and then carboxylic acid is added to an organic base such as amines or an inorganic base such as sodium hydroxide or potassium hydroxide.
  • a catalyst such as dibutyltin dilaurylate in an excess of isocyanate groups
  • Examples thereof include a urethane resin dispersion obtained in combination with an emulsifier, if necessary; and a urethane resin dispersion obtained in combination with an emulsifier.
  • polyfunctional isocyanate compound examples include diisocyanates such as 1,6-hexanediisocyanate, lysine diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-toluene diisocyanate.
  • diisocyanates such as 1,6-hexanediisocyanate, lysine diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-toluene diisocyanate.
  • examples thereof include compounds and polyfunctional isocyanate compounds such as adducts, burettes, and isocyanurates thereof.
  • polyol examples include polyester polyol, polyether polyol, polycarbonate polyol and the like.
  • chain extender examples include low molecular weight diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, fracidimethanol, diamine glycol, triethylene glycol and tetraethylene glycol, and ethylene oxide and propylene.
  • low molecular weight diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, fracidimethanol, diamine glycol, triethylene glycol and tetraethylene glycol, and ethylene oxide and propylene.
  • Diamine acid such as (anhydrous) succinic acid, adipic acid, (anhydrous) futaric acid
  • diamine acid such as (anhydrous) succinic acid, adipic acid, (anhydrous) futal acid, and hydroxyl group at the terminal obtained from these anhydrides
  • the urethane resin in the urethane resin dispersion (C) may be, for example, 15% by mass or more and 40% by mass or less, and 20% by mass or more and 35% by mass or less, based on the total resin solid content in the coating composition according to the present disclosure. It may be there.
  • the amount of urethane resin in the urethane resin dispersion (C) is within the above range, for example, the coating film is subjected to a water resistance test and then the adhesion of the coating film is evaluated. Aggregate destruction and peeling can be suppressed. Further, it is possible to prevent the degree of cross-linking from becoming too large, for example, it is possible to suppress cross-linking strain, and it is possible to suppress delamination with other coating films and objects to be coated in the initial adhesion.
  • the resin dispersion (D) according to the present disclosure can be appropriately selected within a range that satisfies the specific conditions according to the present disclosure, particularly the conditions relating to the solubility parameter SP value.
  • the resin dispersion (D) is a resin dispersion comprising at least one selected from the group consisting of polyester resin dispersion (D1) and acrylic resin emulsion (D2).
  • the resin dispersion (D) may be either a polyester resin dispersion (D1) or an acrylic resin emulsion (D2).
  • the resin dispersion (D) is a polyester resin dispersion (D1).
  • the coating composition according to the present disclosure contains the polyester resin dispersion (D1), it is possible to form a coating film having excellent water resistance and excellent adhesion to the object to be coated.
  • the number average molecular weight of the polyester resin in the polyester resin dispersion (D1) may be 6,000 or more and 20,000 or less, for example, 8,500 or more and 20,000 or less.
  • the number average molecular weight can be calculated from the measurement result of gel permeation chromatography (GPC) using polystyrene as a standard.
  • the polyester resin dispersion (D1) may have a solubility parameter SP (D1) of, for example, 11.0 or more and 12.0 or less, and 11.1 or more and 11.9 or less. ..
  • solubility parameter SP (D1) is within such a range, the color tone of the object to be coated, for example, black or silver, can be sufficiently concealed even though it is a thin film.
  • a coating film having a high hiding property can be formed, the functions of a commonly used white primer coating film containing titanium oxide and a color-based coating film arranged on the white primer coating film are described in the present disclosure.
  • the coating film can be provided even though it is a single layer. That is, the layer structure can be made thinner and the coating film forming step can be reduced as compared with the conventional multi-layer coating film. Furthermore, the desired white mica color tone can be expressed.
  • the glass transition temperature (Tg) of the polyester resin in the polyester resin dispersion (D1) may be, for example, 40 ° C. or higher and 80 ° C. or lower, and 55 ° C. or higher and 75 ° C. or lower. When the glass transition temperature (Tg) is within such a range, it is possible to form a coating film having excellent water resistance and excellent adhesion to an object to be coated.
  • the acid value of the polyester resin in the polyester resin dispersion (D1) may be, for example, 1 mgKOH / g or more and 10 mgKOH / g, or 1 mgKOH / g or more and 8 mgKOH / g.
  • the acid value is within such a range, a crosslinked structure can be formed by a crosslinking agent or the like, and as a result, the adhesion between the coating film and the object to be coated is arranged above the coating film according to the present disclosure. Adhesion with another coating film can be further improved.
  • the hydroxyl value of the polyester resin in the polyester resin dispersion (D1) may be, for example, 1 mgKOH / g or more and 20 mgKOH / g or less, and 1 mgKOH / g or more and 10 mgKOH / g or less.
  • the hydroxyl value is within such a range, excellent durability can be imparted to the coating film together with the curing agent (E) described later.
  • the average particle size (D50) of the polyester resin in the polyester resin dispersion (D1) may be, for example, 40 nm or more and 100 nm or less, and 50 nm or more and 90 nm or less.
  • polyester resin in the polyester resin dispersion (D1) examples include a condensate of a polybasic acid and a polyhydric alcohol.
  • the polybasic acid include phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, succinic anhydride and the like.
  • the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol and the like.
  • the polyester resin in the polyester resin dispersion (D1) preferably has a carboxy group and / or a sulfonic acid group.
  • the polyester has these hydrophilic groups, the dispersibility in water is improved, and as a result, a more uniform coating film can be formed from the coating composition containing the emulsion composition, and the coating film and the coating film can be coated. Adhesion to the coating film, and further, adhesion to other coating films arranged above the coating film can be further improved.
  • polyester resin dispersion (D1) for example, KA-5071S, KZT-8803, KT-8701, KZT-9204 (above, Unitika Ltd.), Byronal MD1200, MD1245, MD1480, MD1930, MD2000, MD1500.
  • Hi-Tech PE series such as PES-H001 (Toho Chemical Industry Co., Ltd.), New Track 2010 (Kao Co., Ltd.), Superflex 210 (Daiichi Kogyo Seiyaku Co., Ltd.), Plus Coat Z730, Z760, Z592, Z687 , Z690 (above, Goo Chemical Industry Co., Ltd.) and the like.
  • the polyester resin in the polyester resin dispersion (D1) may be, for example, 10% by mass or more and 35% by mass or less, and 15% by mass or more and 25% by mass or less in the total resin solid content in the coating composition according to the present disclosure. It may be there.
  • the resin dispersion (D) according to the present disclosure is an acrylic resin emulsion (D2).
  • the coating composition according to the present disclosure contains an acrylic resin emulsion (D2), it is possible to form a coating film having excellent water resistance and excellent adhesion to an object to be coated.
  • the acrylic resin emulsion (D2) is an emulsion of an acrylic resin that does not contain a glycidyl group.
  • the weight average molecular weight of the acrylic resin in the acrylic resin emulsion (D2) is not particularly limited, but may be generally 50,000 or more and 1,000,000 or less, for example, 100,000 or more and 800,000 or less. It may be there.
  • the weight average molecular weight can be calculated from the measurement result of gel permeation chromatography (GPC) using polystyrene as a standard.
  • the acrylic resin emulsion (D2) may have a solubility parameter SP (D2) of 8.0 or more and 12.0 or less.
  • the solubility parameter SP (D2) may be 8.3 or more and 8.9 or less, and may be 10.5 or more and 12.0 or less.
  • the solubility parameter SP (D2) is within such a range, the color tone of the object to be coated, for example, black or silver, can be sufficiently concealed even though it is a thin film.
  • a coating film having a high hiding property can be formed, the functions of a commonly used white primer coating film containing titanium oxide and a color-based coating film arranged on the white primer coating film are described in the present disclosure.
  • the coating film can be provided even though it is a single layer. That is, the layer structure can be made thinner and the coating film forming step can be reduced as compared with the conventional multi-layer coating film. Furthermore, the desired white mica color tone can be expressed.
  • the acrylic resin in the acrylic resin emulsion (D2) can be obtained by polymerizing one or more radically polymerizable monomers.
  • Functional group-containing monomers such as (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and adducts of hydroxyethyl acrylate and ⁇ -caprolactone.
  • (meth) acrylic acid alkyl ester (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid isopropyl, (meth) acrylic acid N-butyl, (meth) acrylic acid t- Selected from butyl, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate.
  • Acrylic resin emulsion (D2) can be obtained by polymerizing one or more kinds of monomers to form an aqueous emulsion.
  • aqueous emulsion examples include a method of subjecting to solvent polymerization and then emulsion by forced stirring or using an emulsifier in water, an emulsion polymerization method of copolymerizing in water using an emulsifier, and the like.
  • the glass transition temperature (Tg) of the acrylic resin in the acrylic resin emulsion (D2) may be, for example, ⁇ 10 ° C. or higher and 100 ° C. or lower, and 0 ° C. or higher and 80 ° C. or lower.
  • the glass transition temperature (Tg) of the acrylic resin may be 10 ° C. or higher and 80 ° C. or lower.
  • the glass transition temperature (Tg) is within such a range, it can be dispersed in the coating film to exhibit higher hiding power.
  • the coating composition according to the present disclosure is used in a wet-on-wet system, the interface between the object to be coated and the upper coating film formed on the coating film formed from the coating composition according to the present disclosure. It is possible to suppress familiarity with and prevent inversion.
  • the acid value of the acrylic resin in the acrylic resin emulsion (D2) is preferably 2 mgKOH / g or more and 20 mgKOH / g or less, for example, 5 mgKOH / g or more and 10 mgKOH / g or less.
  • various stability such as storage stability, mechanical stability, stability against freezing, etc. of the acrylic resin emulsion (D2) and the coating composition according to the present disclosure containing the same can be obtained.
  • the curing reaction with the curing agent (E) at the time of forming the coating film sufficiently occurs, and various strengths, chipping resistance and water resistance of the coating film are improved.
  • the hydroxyl value of the acrylic resin in the acrylic resin emulsion (D2) is preferably 5 mgKOH / g or more and 20 mgKOH / g. More preferably, it is in the range of 10 mgKOH / g or more and 20 mgKOH / g.
  • the resin has appropriate hydrophilicity, workability and stability against freezing when used as a coating composition containing a resin emulsion are increased, and the curing agent (E) is used.
  • the coating film has high mechanical properties and can form a coating film having excellent chipping resistance, water resistance and solvent resistance.
  • the pH value of the acrylic resin emulsion (D2) may be, for example, 4 or more and 8 or less, and 4 or more and 7 or less.
  • the pH value is within such a range, the adhesion between the coating film and the object to be coated and the adhesion with another coating film arranged above the coating film according to the present disclosure can be further improved.
  • the average particle size (D50) of the acrylic resin in the acrylic resin emulsion (D2) may be, for example, 40 nm or more and 300 nm or less, and 50 nm or more and 150 nm or less.
  • the acrylic resin in the acrylic resin emulsion (D2) in the present disclosure can be appropriately selected as long as the solubility parameter SP (D2) in the acrylic resin emulsion (D2) satisfies the above-mentioned predetermined conditions.
  • the acrylic resin emulsion (D2) comprises an acrylic resin having at least one of a hydroxyl group and a carboxyl group, and includes, for example, an acrylic resin having a hydroxyl group and a carboxyl group.
  • the acrylic resin in the acrylic resin emulsion (D2) is a crosslinkable resin particle, for example, an acrylic resin particle having a crosslinkable property and further having at least one of a hydroxyl group and a carboxyl group. It may be there.
  • the acrylic resin having a hydroxyl group and a carboxyl group comprises (meth) acrylic acid alkyl ester (i), a carboxyl group-containing ethylenically unsaturated monomer (ii), and a hydroxyl group-containing ethylenically unsaturated monomer (iii). It can be obtained by emulsifying and polymerizing the monomer mixture containing the mixture.
  • the compounds exemplified below as components of the monomer mixture may be used alone or in combination of two or more.
  • metal (acrylic) means both acrylic and methacryl.
  • the (meth) acrylic acid alkyl ester (i) is used to form the main skeleton of the acrylic resin emulsion.
  • (meth) acrylic acid alkyl ester (i) examples include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, n-butyl (meth) acrylic acid, and (meth) acrylic.
  • Isobutyl acid t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, ( Examples thereof include dodecyl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate.
  • the carboxyl group-containing ethylenically unsaturated monomer (ii) improves various stability of the obtained acrylic resin emulsion such as storage stability, mechanical stability, and stability against freezing, and is a curing agent (E) at the time of coating film formation. ) Can be used to accelerate the curing reaction.
  • carboxyl group-containing ethylenically unsaturated monomer examples include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, etacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, maleic anhydride and fumaric acid.
  • the hydroxyl group-containing ethylenically unsaturated monomer (iii) imparts hydrophilicity based on the hydroxyl group to the acrylic resin emulsion, which enhances workability and stability against freezing when used as a paint, and also serves as a curing agent (E). It is used to impart the curing reactivity of.
  • Examples of the hydroxyl group-containing ethylenically unsaturated monomer (iii) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-methylolacrylamide, and allyl alcohol. Examples thereof include ⁇ -caprolactone-modified (meth) acrylic monomer.
  • ⁇ -caprolactone-modified acrylic monomer examples include "Plaxel FA-1”, “Plaxel FA-2”, “Plaxel FA-3”, “Plaxel FA-4”, and “Plaxel FA” manufactured by Daicel Chemical Industries, Ltd. -5 ”,“ Praxel FM-1 ”,“ Praxel FM-2 ”,“ Praxel FM-3 ”,“ Praxel FM-4 ”,“ Praxel FM-5 ”and the like.
  • the monomer mixture may contain at least one monomer selected from the group consisting of styrene-based monomers, (meth) acrylonitrile and (meth) acrylamide as optional components, and the styrene-based monomers include ⁇ in addition to styrene. -Methylstyrene and the like can be mentioned.
  • the crosslinked monomer include ethylene glycol di (meth) acrylic acid and divinylbenzene.
  • Emulsion polymerization can be carried out by heating the monomer mixture in an aqueous liquid in the presence of a radical polymerization initiator and an emulsifier with stirring.
  • the reaction temperature is preferably about 30 to 100 ° C., and the reaction time is preferably about 1 to 10 hours.
  • the reaction temperature is adjusted by adding a monomer mixture or a monomer pre-emulsifying solution to a reaction vessel containing water and an emulsifier in a batch or dropping it for a while. It is good to do.
  • radical polymerization initiator a known initiator usually used in emulsion polymerization of an acrylic resin can be used.
  • a water-soluble free radical polymerization initiator for example, persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate are used in the form of an aqueous solution.
  • a so-called redox-based initiator in which an oxidizing agent such as potassium persulfate, sodium persulfate, ammonium persulfate, or hydrogen peroxide is combined with a reducing agent such as sodium hydrogen sulfite, sodium thiosulfite, longalite, or ascorbic acid is an aqueous solution. Used in the form of.
  • the emulsifier is an anion system selected from a micelle compound having a hydrocarbon group having 6 or more carbon atoms and a hydrophilic moiety such as a carboxylate, a sulfonate or a sulfate partial ester in the same molecule.
  • a nonionic (nonionic) emulsifier is used.
  • anionic emulsifiers alkali metal salts or ammonium salts of sulfuric acid semiesters of alkylphenols or higher alcohols; alkali metal salts or ammonium salts of alkyl or allyl sulfonate; polyoxyethylene alkylphenyl ethers, polyoxyethylenes.
  • Examples thereof include an alkali metal salt or an ammonium salt of a sulfuric acid semi-ester of an alkyl ether or a polyoxyethylene allyl ether.
  • the nonionic emulsifier include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether and polyoxyethylene allyl ether.
  • these general-purpose anion-based and nonionic-based emulsifiers they also have radically polymerizable unsaturated double bonds in the molecule, that is, acrylic-based, methacrylic-based, propenyl-based, allyl-based, allyl ether-based, and maleic acid-based.
  • Various anion-based and nonionic-based reactive emulsifiers having a group such as, etc. are also used as appropriate alone or in combination of two or more.
  • auxiliary agent chain transfer agent
  • a mercaptan compound or a lower alcohol promotes smooth and uniform formation of the coating film from the viewpoint of promoting emulsion polymerization. From the viewpoint of improving the adhesiveness to the base material, it is often preferable, and it is carried out as appropriate depending on the situation.
  • the emulsion polymerization includes a normal one-step continuous monomer uniform dropping method, a core-shell polymerization method which is a multi-step monomer feed method, and a power feed polymerization method in which the monomer composition fed during polymerization is continuously changed. It can be legal.
  • a basic compound may be added to the obtained acrylic resin emulsion (D2) in order to neutralize a part or all of the carboxylic acid and maintain the stability of the acrylic resin emulsion (D2).
  • these basic compounds ammonia, various amines, alkali metals and the like can be appropriately used.
  • the acrylic resin in the acrylic resin emulsion (D2) may be, for example, 10% by mass or more and 35% by mass or less, and 15% by mass or more and 25% by mass or less, based on the total resin solid content of the coating composition according to the present disclosure. You can.
  • the curing agent is not particularly limited.
  • melamine resin blocked isocyanate, carbodiimide resin and the like are preferable.
  • the melamine resin is not particularly limited.
  • methoxy-type melamine and methoxy-butoxy mixed-type melamine can be mentioned.
  • Butoxy-type melamine can be hydrated and used by a method using an emulsifier, an acrylic resin, an alkyd resin or the like as an emulsifier.
  • the methoxy-type melamine resin is more preferable because it can be stabilized in water without using an emulsifier or the like.
  • the blocked isocyanate compound that can be used as the curing agent (E) in the present invention will be described.
  • the starting component of the blocked isocyanate compound is a di- or poly-isocyanate compound and a mixture thereof. However, these components react with a blocking agent to obtain a blocked isocyanate compound.
  • Preferred di- or poly-isocyanate compounds are aliphatic, alicyclic, aromatic aliphatic and heterocyclic polyisocyanates.
  • Polyisocyanates produced by the heteropolymerization reaction, polyisocyanates containing an ester group, preferably diisocyanates containing a uretdione group and diisocyanates containing a urea group are also suitable.
  • di- or poly-isocyanate compound examples include the following. p-xylylene diisocyanate, 1,5-diisocyanatomethylnaphthalene, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, 1-methylbenzene 2,5-diisocyanate, 1,3 dimethylbenzene 4,6-diisocyanate , 1,4 dimethylbenzene 2,5-diisocyanate, 1-nitrobenzene 2,5-diisocyanate, 1-methoxybenzene 2,4-diisocyanate, 1-methoxybenzene 2,5-diisocyanate, 1,3-dimethoxybenzene 4,6 -Diisocyanate, azobenzene 4,4'-diisocyanate, diphenyl ether 4,4'-diisocyanate, diphenylmethane 4,4'-diisocyanate, diphenyldimethylmethane 4,4'
  • Oxime compounds acetooxime, methylethylketooxime, methylisobutylketooxime, etc.
  • lactams ⁇ -caprolactam, etc.
  • active methylene compounds diethyl malonate, acetylacetone, etc.
  • Ethyl acetoacetate, etc. phenols (phenol, m-cresol, etc.), alcohols (methanol, ethanol, n-butanol, etc.), hydroxyl group-containing ether (methyl cellsolve, butyl cell solution, etc.), hydroxyl group-containing ester (methyl lactate) , Amil lactate, etc.), mercaptans (butyl mercaptan, hexyl mercaptan, etc.), acid amides (acetanilide, acrylic amide, dimer acid amide, etc.), imidazoles (imidazole, 2-ethylimidazole, etc.), acidimides (succinic acid, etc.) Examples thereof include imides (imides of phthalates, etc.), amines (dicyclohexylamines, etc.) and mixtures of two or more of these.
  • the curing agent (E) is preferably used in the range of 5% by mass or more and 15% by mass or less in the total resin solid content of the coating composition according to the present disclosure.
  • the amount of the curing agent is within such a range, the degree of cross-linking of the coating film can be increased, and a coating film having more excellent water resistance and adhesion can be formed.
  • the coating composition according to the present disclosure comprises particles selected from the group consisting of organic particles and inorganic particles. By including such particles, it can be expected that the hiding property is further improved due to the difference in refractive index between the binder resin and the particles.
  • the organic particles and the inorganic particles are particles different from the above components (A) to (D).
  • organic particles styrene resin, acrylic-styrene copolymer resin, acrylic-acrylonitrile copolymer resin, acrylic-styrene-acrylonitrile copolymer resin, acrylonitrile-methacrylonitrile copolymer resin, acrylic-acrylonitrile-methacrylonitrile copolymer resin, Examples thereof include vinylidene chloride-acrylonitrile copolymer resin.
  • the inorganic particles include glass such as soda glass silicate, aluminosilicate glass, and sodium borosilicate glass; fly ash, alumina, zirconia / titania, silicon booxide, silas, and black stone.
  • extender pigments such as calcium carbonate, barium sulfate, clay, and talc may be used in combination.
  • the coating composition according to the present disclosure further comprises a colored pigment.
  • the coloring pigment may be contained in an amount of 3% by mass or more and 150% by mass or less with respect to the total solid content of (A) to (E) (that is, in the total resin solid content of the coating composition according to the present disclosure). ..
  • the coloring pigment within such a range, it is possible to suppress an increase in viscosity at the time of curing, and further, it is possible to suppress a decrease in flowability. As a result, a good coating film appearance can be obtained.
  • the coating composition according to the present disclosure can form a coating film having a high hiding property, a commonly used white primer coating film containing titanium oxide and a color-based coating film arranged on the white primer coating film are generally used.
  • the coating film according to the present disclosure can be provided with the function of the above even though it is a single layer. That is, the layer structure can be made thinner and the coating film forming step can be reduced as compared with the conventional multi-layer coating film. Furthermore, the desired white mica color tone can be expressed. Therefore, in the coating composition according to the present disclosure, for example, a coloring pigment may be added in order to function as a color-based coating film.
  • the coloring pigment is not particularly limited as long as it is a pigment used in ordinary paints.
  • azochelate pigments for example, from the viewpoint of obtaining a high-appearance coating film and improving weather resistance, azochelate pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, perinone pigments, perylene pigments, etc.
  • Organic coloring pigments such as dioxane pigments, quinacridone pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, metal complex pigments; titanium oxide, yellow lead, yellow iron oxide, red iron oxide, carbon Examples thereof include inorganic coloring pigments such as black.
  • the additive examples include an additive usually added in addition to the above components, for example, an ultraviolet absorber; an antioxidant; an antifoaming agent; a surface conditioner; a pinhole inhibitor and the like. These blending amounts are within the range known to those skilled in the art.
  • the coating composition according to the present disclosure is an aqueous primer coating composition. Since the aqueous primer coating composition according to the present disclosure can form a coating film having a high hiding property, it can be made thinner than a commonly used white primer coating film containing titanium oxide. Further, the coating film formed from the aqueous primer coating composition according to the present disclosure has various functions required as a primer coating film, for example, hiding property and chipping resistance of an object to be coated. Further, the primer coating film according to the present disclosure can have a function of a color-based coating film that can be arranged on the primer coating film. Therefore, the layer structure can be made thinner and the coating film forming step can be reduced as compared with the conventional multi-layer coating film.
  • the thickness of the coating film formed from the aqueous primer coating composition according to the present disclosure may be, for example, 15 ⁇ m or more and 40 ⁇ m or less, and 20 ⁇ m or more and 35 ⁇ m or less.
  • the primer coating film according to the present disclosure is such a thin film, it can satisfactorily conceal a color tone such as black color that an object to be coated may have, and in addition, it can have excellent water resistance.
  • the color tone of the coating film formed on the primer coating film is the color tone of white mica, it can be satisfactorily expressed.
  • the present disclosure comprises a step of coating an object to be coated with the coating composition according to the present disclosure to form an uncured coating film, and The step of heating and curing the uncured coating film to form a coating film is included.
  • a method for forming a coating film is provided.
  • the means for coating the coating composition according to the present disclosure is not particularly limited, and examples thereof include commonly used coating methods such as bell coating, air spray, and airless spray. These can be appropriately selected depending on the object to be coated.
  • the coating composition may be applied by an electrostatic coating machine.
  • conditions such as the discharge amount of the coating film can be appropriately set according to the required film thickness of the coating film and the like.
  • the film thickness of the coating film formed from the coating composition according to the present disclosure may be, for example, 10 ⁇ m or more and 40 ⁇ m or less, 12 ⁇ m or more and 38 ⁇ m or less, 15 ⁇ m or more and 35 ⁇ m, or 25 ⁇ m or more and 30 ⁇ m. It may be there.
  • the film thickness can be measured by the dry film thickness, and the dry film thickness can be measured by using SDM-miniR manufactured by SANKO.
  • a step of volatilizing water at a temperature of 40 ° C. or higher and 80 ° C. or lower for 1 to 10 minutes is also referred to as a preheating step.
  • baking and curing can be performed at a temperature of, for example, 80 ° C. or higher and 150 ° C. or lower, for example, 100 ° C. or higher and 130 ° C. or lower.
  • the baking curing time may be appropriately adjusted within the range of, for example, about 20 minutes to 40 minutes.
  • the present disclosure comprises a step of coating an object to be coated with the aqueous primer coating composition according to the present disclosure to form an uncured primer coating film.
  • a step of coating a base coating composition containing a bright pigment on the uncured aqueous primer coating composition to form an uncured base coating film and
  • a step of coating a clear coating composition on the uncured base coating film to form an uncured clear coating film and
  • the steps of heating and curing the uncured primer coating film, base coating film and clear coating film to form a multi-layer coating film and Provided is a method for forming a multi-layer coating film including.
  • the method for forming the multi-layer coating film will be described in more detail.
  • a preheating step of, for example, at a temperature of 40 ° C. or higher and 80 ° C. or lower for 1 to 10 minutes is performed as necessary, and an uncured primer coating film is applied.
  • the film thickness of the uncured primer coating film may be, for example, 10 ⁇ m or more and 40 ⁇ m or less, 12 ⁇ m or more and 38 ⁇ m or less, 15 ⁇ m or more and 35 ⁇ m, or 25 ⁇ m or more and 30 ⁇ m as a dry film thickness. Good.
  • an aqueous base coating composition containing a bright pigment for example, an aqueous base coating composition containing mica is coated on the obtained uncured primer coating film, and if necessary, for example, 40 ° C. or higher and 80 ° C.
  • An uncured base coating (for example, mica base coating) can be formed by performing a preheating step at the following temperature for 1 to 10 minutes. Further, the clear coating composition is applied onto the uncured base coating film to form an uncured clear coating film. After forming the uncured clear coating film, for example, at a temperature of 80 ° C. or higher and 150 ° C. or lower, for example, 100 ° C. or higher and 130 ° C. or lower, the uncured coating film and the uncured mica-based coating film according to the present disclosure. The uncured clear coating film can be baked and cured. The baking curing time may be appropriately adjusted within the range of, for example, about 20 minutes to 40 minutes.
  • the heat curing (baking) time means the time during which the surface of the base material actually keeps the target baking temperature, and more specifically, the time until the target baking temperature is reached should be taken into consideration. However, it means the time when the target temperature is reached and the temperature is maintained.
  • Examples of the heating device used to simultaneously bake the uncured film of the coating composition include a drying furnace using a heating source such as hot air, electricity, gas, or infrared rays. Further, it is preferable to use a drying oven in which two or more of these heating sources are used in combination because the drying time is shortened.
  • a coating film (a white primer coating film also used as a color base) formed from the coating composition according to the present disclosure, a mica (bright pigment) base, and a clear coating film are provided on the object to be coated.
  • Parts such as automotive parts, can be formed. Therefore, by using the coating composition according to the present disclosure for two layers of a general white primer and a color base, it is possible to show the functions of these two layers as a single layer. As a result, for example, the weight of the entire automobile part can be reduced, the painting process can be shortened, and the energy reduction (CO 2 ) can be reduced.
  • the aqueous base coating composition As the water-based base coating composition and the clear coating composition, known ones can be used.
  • the aqueous base coating composition that can be preferably used include an aqueous base coating composition containing a coating film-forming resin and a bright pigment.
  • the coating film-forming resin is not particularly limited, and examples thereof include acrylic resin, polyester resin, alkyd resin, epoxy resin, and urethane resin. From the viewpoint of pigment dispersibility and workability, a combination of an acrylic resin and / or a polyester resin and an amino resin and / or a blocked isocyanate resin as a curing agent is preferable. Only one type of the coating film-forming resin and the curing agent can be used, but two or more types can be used in order to balance the coating film performance.
  • the bright pigment is not particularly limited, and examples thereof include uncolored or colored metallic bright pigments such as metals or alloys and mixtures thereof, interfering mica, colored mica, white mica, graphite, colorless colored flat pigments, and the like. Can be done. One of these bright pigments may be used alone, or two or more thereof may be used in combination.
  • mica such as interference mica, colored mica, and white mica is preferably used. be able to.
  • the amount of the bright pigment contained in the water-based base coating composition is preferably in the range of, for example, 1 to 20% by mass with respect to 100 parts by mass of the resin solid content contained in the coating composition.
  • the film thickness of the uncured base coating film can be appropriately selected depending on the application, and for example, the dry film thickness is preferably 5 to 35 ⁇ m.
  • the film thickness of the uncured base coating film may be, for example, 8 ⁇ m or more and 15 ⁇ m or less, and 10 ⁇ m or more and 12 ⁇ m or less.
  • the clear coating composition is not particularly limited, and examples thereof include those containing a coating film-forming resin and, if necessary, a curing agent and other additives in a state of being dispersed or dissolved in a medium. ..
  • the coating film-forming resin include acrylic resin, polyester resin, epoxy resin, and urethane resin. These can be used in combination with curing agents such as amino resins and / or isocyanate resins. Further, from the viewpoint of transparency or acid etching resistance, a combination of an acrylic resin and / or a polyester resin and an amino resin, or an acrylic resin and / or a polyester resin having a carboxylic acid / epoxy curing system can also be used. ..
  • the clear coating composition can be coated by using a coating method known to those skilled in the art according to the coating form of the clear coating composition.
  • the film thickness of the uncured clear coating film is generally preferably 15 to 50 ⁇ m, more preferably 20 to 35 ⁇ m, and may be, for example, 25 ⁇ m or more and 30 ⁇ m or less.
  • a coating film formed from the coating composition according to the present disclosure can exhibit good adhesion to these water-based base coating compositions.
  • the coating film composition according to the present disclosure can form a coating film having a high hiding property, it is contained in a generally used white primer coating film containing titanium oxide and a color base coating film arranged on the white primer coating film.
  • the coating film according to the present disclosure can be provided with a function even though it is a single layer. That is, the process of forming the color-based coating film can be reduced.
  • the layer structure of the multi-layer coating film can be made thinner than that of the conventional multi-layer coating film, and even if the color tone of the coating film formed on the primer coating film is the color tone of white mica. , The desired white mica color tone can be expressed.
  • the object to be coated can be appropriately selected according to the intended use, function, and the like.
  • various objects to be coated that can be energized can be used as the object to be coated.
  • objects to be coated include cold-rolled steel sheets, hot-rolled steel sheets, stainless steel, electrogalvanized steel sheets, hot-dip galvanized steel sheets, zinc-aluminum alloy-based plated steel sheets, zinc-iron alloy-based plated steel sheets, and zinc-magnesium alloy-based plating.
  • Examples thereof include steel sheets, zinc-aluminum-magnesium alloy-based plated steel sheets, aluminum-based plated steel sheets, aluminum-silicon alloy-based plated steel sheets, and tin-based plated steel sheets.
  • These objects to be coated may be objects to be coated which have been subjected to a known chemical conversion treatment or the like. Further, these objects to be coated may be objects to be coated obtained by coating an electrodeposition coating plate with an intermediate coating paint and baking or preheating.
  • a plastic base material can be used as the object to be coated.
  • it may be a plastic base material used for automobile parts.
  • the automobile parts are not particularly limited, and examples thereof include bumpers, spoilers, grilles, and fenders.
  • the plastic base material contains polypropylene, polyolefin, or elastomer-modified polypropylene resin.
  • the elastomer-modified polypropylene resin is not particularly limited, and known commercially available ones can be used. Further, in addition to the resin, an additive may be added as needed. Further, an object to be coated made of ABS (acrylonitrile-butadiene-styrene) resin may be used.
  • % in the blending ratio means mass% unless otherwise specified.
  • the present invention is not limited to the examples described below.
  • the mixture was cooled to room temperature (25 ° C.) and filtered through a 400 mesh wire mesh to obtain a maleic anhydride-modified chlorinated polyolefin resin emulsion (A-2).
  • the non-volatile content of the emulsion was 30% by weight.
  • the solubility parameter SP (A) of the maleic anhydride-modified chlorinated polyolefin resin in the emulsion (A-2) was 9.3.
  • the SP value was measured by the method described in paragraph 0029 and paragraph 0030.
  • the reaction was carried out under reduced pressure conditions of 180 ° C. and 5 kPa or less for 2 hours to obtain a polyester having a hydroxyl group excess of 112 mgKOH / g and an acid value of 0.2 mgKOH / g.
  • 500 parts of this polyester polyol, 134 parts of dimethyl 5-sulfosodium isophthalate and 2 parts of tetrabutyl titanate were charged in another reaction vessel equipped with the same apparatus as the above reaction vessel, and in the same manner as above, The reaction vessel was set to 180 ° C.
  • a sulfonic acid group-containing polyester having a weight average molecular weight of 2117, a hydroxyl value of 53 mgKOH / g, and an acid value of 0.3 mgKOH / g.
  • 280 parts of the sulfonic acid group-containing polyester, 200 parts of polybutylene adipate, 35 parts of 1,4-butanediol, 118 parts of hexamethylene diisocyanate and 400 parts of methyl ethyl ketone were mixed with a stirring blade, a thermometer, a temperature control device, a dropping device, and a sample collection.
  • a reaction vessel with a mouth and a cooling tube was charged with nitrogen gas while stirring, and the liquid temperature was maintained at 75 ° C. to carry out a urethanization reaction to obtain a urethane polymer having an NCO content of 1%.
  • the liquid temperature in the reaction vessel was lowered to 40 ° C., and 955 parts of ion-exchanged water was uniformly dropped while sufficiently stirring to carry out phase inversion emulsification.
  • the internal temperature was lowered, and an aqueous solution of adipic acid hydrazide, which was a mixture of 13 parts of adipic acid hydrazide and 110 parts of ion-exchanged water, was added to carry out amine extension.
  • the temperature was raised to 60 ° C.
  • the acid value of the polyurethane resin in the polyurethane resin dispersion (C) was 11 mgKOH / g.
  • Polyester resin dispersion (D) Polyester resin dispersion (D1-1) MD1200 manufactured by Toyobo Co., Ltd. (resin solid content 34% by mass, number average molecular weight (Mn) 15000, acid value 1 mgKOH / g, hydroxyl value 5 mgKOH / g) was used.
  • the solubility parameter SP (D) of the polyester resin in MD1200 was 11.7.
  • the SP value was calculated by the method described in paragraph 0031.
  • Polyester resin dispersion (D1-2) BCD3120 (resin solid content 35% by mass, acid value 7 mgKOH / g, hydroxyl value 150 mgKOH / g) manufactured by DIC Corporation was used.
  • the solubility parameter of the polyester resin in BCD3120 was 10.9 for SP (D).
  • the SP value was calculated by the method described in paragraph 0031.
  • the aging reaction was carried out at 120 ° C. for 1 hour, and then a solution prepared by dissolving 0.1 part of t-butylperoxy-2-ethylhexanol in 4 parts of propylene glycol was further added for 1 hour. It was added dropwise to the reaction vessel. In each case, the internal stirring state and the liquid temperature of 120 ° C. were maintained. Then, the mixture was aged at 120 ° C. for 2 hours with stirring, then the internal temperature was cooled to 70 ° C., 9.5 parts of dimethylaminoethanol was added dropwise, and the mixture was stirred for 30 minutes. Further, while maintaining the internal temperature at 70 ° C.
  • ion-exchanged water was slowly added dropwise and cooled to room temperature (25 ° C.) to obtain a water-soluble acrylic resin solution.
  • the non-volatile content was adjusted to 30% using ion-exchanged water, and this was used as a pigment dispersion resin for a primer in the following pigment dispersion paste.
  • the pH of the obtained pigment-dispersed resin (water-soluble acrylic resin solution) was 8.2, and the weight average molecular weight of the acrylic resin was 42000.
  • the weight average molecular weight was determined in terms of polystyrene by a GPC apparatus using a TSK-gel-supermultip Albanyr HZ-M (manufactured by Tosoh Corporation) column and THF as a developing solvent.
  • Cymel 701 (nonvolatile content 82%, methylolated melamine) manufactured by Allnex was used.
  • Example 1 30 parts by mass of Aurolene S6479 (maleic anhydride-modified polyolefin resin (A-1), non-chlorinated) manufactured by Nippon Paper Co., Ltd., 15 parts by mass of the glycidyl group-containing acrylic resin emulsion (B) obtained in Production Example 2, manufactured. 25 parts by mass of the polyurethane resin dispersion (C) obtained in Example 3, 20 parts by mass of MD1200 (polyester resin dispersion (D1-1)) manufactured by Toyo Boseki, and Cymel 701 (hardener (E)) manufactured by Allnex.
  • Aurolene S6479 maleic anhydride-modified polyolefin resin (A-1), non-chlorinated) manufactured by Nippon Paper Co., Ltd.
  • Example 1 10 parts by mass were sequentially put into a stainless steel container equipped with a stirrer and mixed to obtain the coating composition of Example 1.
  • the above-mentioned compounding amount is a solid content conversion amount.
  • the SP value of Aurolen S6479 is 8.7, which is calculated by the method described in paragraph 0031.
  • Example 2 to 5 Comparative Examples 1 and 2
  • the coating compositions of Examples 2 to 5 and Comparative Examples 1 and 2 were obtained in the same manner as in Example 1 except that the constituent raw materials and the blending amounts were changed as shown in Table 2.
  • Example 1 using "Wider-71" (manufactured by Anest Iwata Co., Ltd.) on the surface of a Teflon sheet (70 mm x 150 mm x 0.1 mm) wiped with isopropyl alcohol in an environment of 25 ° C./70% RH.
  • the prepared coating composition was coated so as to have a dry film thickness of 30 ⁇ m, and dried at 60 ° C. for 5 minutes. Then, it was baked and cured at 120 ° C. for 30 minutes to form a coating film.
  • the obtained coating film was peeled off from a Teflon sheet, cut into 25 mm squares, attached to a zero-point corrected crow plate, and the haze value was measured with a turbidity meter attached to a ⁇ 90 color measuring system manufactured by Nippon Denshoku Kogyo Co., Ltd.
  • the haze value was measured in the same manner as described above. Table 2 shows the measurement results of the haze value.
  • Example 6 Titanium R960 manufactured by Dupont Co., Ltd. was added to the pigment dispersion resin of Production Example 4 to obtain a pigment paste having a PWC (Pigment Weight Concentration, pigment weight concentration) of 95%.
  • the PWC of the pigment paste means the amount of the pigment (mass of the pigment / solid content of the pigment-dispersed resin ⁇ 100) with respect to the solid content of the pigment-dispersed resin. 171 parts by mass of the pigment paste was added to 100 parts by mass of the coating composition produced in Example 1 to prepare a white primer coating having a PWC of 60%.
  • the above-mentioned compounding amount is a solid content conversion amount.
  • PWC of the white primer coating means the amount of the pigment (the mass of the pigment / the total resin solid content ⁇ 100) with respect to the total resin solid content in the white primer coating material, that is, the coating composition according to the present disclosure.
  • Examples 7 to 10, Comparative Examples 3 to 5 White primer coating materials of Examples 7 to 10 and Comparative Examples 3 to 5 were obtained in the same manner as in Example 6 except that the coating composition was changed as shown in Table 3.
  • the white primer paints of Comparative Examples 3 and 4 are the same.
  • the white primer coating material of Example 6 is applied to a black-and-white concealment test paper so that the film thickness changes stepwise, dried at 60 ° C. for 5 minutes, baked at 120 ° C. for 30 minutes, cooled, and then perpendicular to the object to be coated. The film thickness that was visually observed from the direction and indistinguishable between black and white was defined as the concealed film thickness.
  • the white primer coating materials of Examples 7 to 10 and Comparative Examples 3 to 5 were also evaluated for the concealing film thickness in the same manner as described above. The results of the concealment film thickness are shown in Table 3.
  • a new cartridge bell (new cartridge bell (trade name) manufactured by ABB) was applied to the water-based mica-based paint composition (AR-3020-1 # 7A21 manufactured by Nippon Paint Automotive Coatings) under the same environment. Using it, spray coating (dry film thickness 15 ⁇ m) was performed under coating conditions (gun distance: 200 mm, gun speed: 900 mm / s, rotation speed: 35000 rpm, shaping air pressure: 0.15 MPa). After drying at 80 ° C.
  • a clear paint composition (a mixture of R-25501 and a curing agent H-2550 manufactured by Nippon Paint Automotive Coatings Co., Ltd.) is applied onto the coating (a mixture of R-25501 and a curing agent H-2550 manufactured by Nippon Paint Automotive Coatings) using Robobel 951.
  • Spray coating (dry film thickness 25 ⁇ m) was performed under the conditions of gun distance: 200 mm, gun speed: 700 mm / s, rotation speed: 25000 rpm, shaping air pressure: 0.07 MPa). Then, after setting for 10 minutes, it was dried at 120 ° C. for 30 minutes to form the multi-layer coating film of Example 6.
  • the white primer paints of Examples 7 to 10 and Comparative Examples 3 and 4 were also subjected to the same procedure as in Example 7 except that the film thickness of the white primer paint and / or the white primer was changed as shown in Table 3.
  • a multi-layer coating film of 10 to 10 and Comparative Examples 3 to 5 was formed.
  • the water-based color-based paint composition (AR-3020-1 # 7018 manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was used in the same environment using a new cartridge bell (new cartridge bell (trade name) manufactured by ABB).
  • Spray coating (dry film thickness 20 ⁇ m) was performed under electrostatic coating conditions (gun distance: 200 mm, gun speed: 900 mm / s, applied voltage: -60 kV, rotation speed: 35000 rpm, shaping air pressure: 0.15 MPa).
  • the water-based mica-based coating composition (AR-3020-1 # 7A21 manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was spray-coated (dry film thickness 15 ⁇ m) under the same conditions as the water-based color-based coating composition.
  • a clear coating composition (a mixture of R-25501 and a curing agent H-2550 manufactured by Nippon Paint Automotive Coatings Co., Ltd.) is electrostatically charged on the clear coating composition using Robobel 951.
  • Spray coating (dry film thickness 25 ⁇ m) was performed under the conditions of coating (gun distance: 200 mm, gun speed: 700 mm / s, applied voltage: -60 kV, rotation speed: 25000 rpm, shaping air pressure: 0.07 MPa). Then, after setting for 10 minutes, it was dried at 120 ° C. for 30 minutes to form a multi-layer coating film.
  • the multi-layer coating film obtained as described above was evaluated for xylene rubbing resistance, initial adhesion, water resistance, bending resistance, and finish in the following manner. These results are shown in Table 3.
  • the multi-layer coating film was immersed in a water resistant tank at 40 ° C. for 240 hours. After the immersion was completed, the coating film taken out from the water resistant tank was subjected to a checkered cellophane tape (registered trademark) peeling test within 1 hour after being taken out in accordance with JIS K5600-5-6. 100 2 mm square grids were prepared, a cellophane tape peeling test was performed, and the number of grids that did not peel was counted.
  • the evaluation criteria are as follows. 0/100 (without peeling) was regarded as a pass ( ⁇ ), and 1/100 to 100/100 (with peeling) was regarded as a failure (x).
  • ⁇ 1/100 to 100/100 (with peeling) was regarded as a failure (x).
  • ⁇ 1/100 to 100/100 (with peeling)
  • the color difference ⁇ E of the multi-layer coating film was measured using the multi-layer coating plate prepared in the reference example as a reference plate for white mica coating color.
  • a ⁇ E of less than 1 was regarded as a pass ( ⁇ ), and a ⁇ E of 1 or more was regarded as a fail (x).
  • the coating composition according to the present disclosure With the coating composition according to the present disclosure, a coating film having excellent base hiding properties can be formed. Therefore, with the coating composition according to the present invention, the number of coatings can be reduced as compared with the conventional case, and a coating film capable of hiding the black color of the object to be coated can be formed even though the film thickness is thinner. Further, the coating composition according to the present disclosure can form a coating film having excellent adhesion, chemical resistance, water resistance, flexibility and appearance.
  • the coating films formed by using the coating compositions of Comparative Examples 1 and 2 have a low haze value, they are formed by using the white primer coatings of Comparative Examples 3 to 5 prepared from the coating compositions of Comparative Examples 1 and 2.
  • the white primer was inferior in the base hiding property.
  • the coating composition of the present invention can be suitably used in, for example, automobile vehicles and automobile parts.

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Abstract

La présente invention concerne une composition de revêtement apte à former un film de revêtement qui est fin et, malgré cela, peut cacher la couleur de l'objet revêtu et qui est excellent en termes d'adhésion, de résistance aux produits chimiques, de résistance à l'eau, de caractéristiques de flexion, et d'apparence.　Cette composition de revêtement comprend au moins un ingrédient sélectionné parmi une résine de polyoléfine modifiée avec de l'anhydride maléique (A), une émulsion de résine acrylique contenant un groupe glycidyle (B), et une dispersion de résine d'uréthane (C) et comprend en outre une dispersion de résine (D) et un durcissant (E), le (A), (B), et (C) présentant des valeurs SP de paramètre de solubilité qui satisfont une relation donnée. Dans les cas où un mélange comprenant le au moins un ingrédient, le (D), et le (E) dans les mêmes proportions en masse que dans la composition de revêtement sont appliqués pour former un film de revêtement ayant une épaisseur de 30 µm, le film de revêtement ayant un trouble de 30 % ou supérieur.
PCT/JP2020/047970 2019-12-27 2020-12-22 Composition de revêtement, film de revêtement obtenu à partir de celle-ci, et procédé de formation d'un film de revêtement multicouche WO2021132246A1 (fr)

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JP2010254816A (ja) * 2009-04-24 2010-11-11 Nippon Bee Chemical Co Ltd 水性白色導電プライマー塗料組成物および外装用プラスチック成型品への塗膜形成方法
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WO2013191104A1 (fr) * 2012-06-19 2013-12-27 関西ペイント株式会社 Composition aqueuse de revêtement et procédé de revêtement l'utilisant
JP2016023304A (ja) * 2014-07-24 2016-02-08 トヨタ自動車株式会社 内装用塗料組成物
JP2016087569A (ja) * 2014-11-07 2016-05-23 日本ペイント・オートモーティブコーティングス株式会社 複層塗膜の形成方法

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