WO2022239832A1 - Multilayer coating film and method for forming multilayer coating film - Google Patents
Multilayer coating film and method for forming multilayer coating film Download PDFInfo
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- WO2022239832A1 WO2022239832A1 PCT/JP2022/020058 JP2022020058W WO2022239832A1 WO 2022239832 A1 WO2022239832 A1 WO 2022239832A1 JP 2022020058 W JP2022020058 W JP 2022020058W WO 2022239832 A1 WO2022239832 A1 WO 2022239832A1
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- Prior art keywords
- coating film
- coating
- coating composition
- parts
- pigment
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
-
- 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
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- 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
Definitions
- the present invention relates to a multilayer coating film and a method for forming a multilayer coating film.
- an undercoat coating film such as an electrodeposition coating film is formed on an object to be coated with excellent conductivity, and an intermediate coating film is formed thereon, if necessary.
- a method of sequentially forming top coat films is common. In these coating films, it is the top coating film consisting of the base coating film and the clear coating film that greatly affects the appearance and design of the coating film. In particular, in automobiles, the appearance and design of a top coat consisting of a base coat and a clear coat formed on a vehicle body are extremely important.
- the appearance of the paint film formed on the automobile greatly contributes to the appearance value of the automobile, such as its luxury appearance.
- customers who purchase automobiles tend to seek automobiles having coating films with excellent design. Due to the diversification of consumer tastes and the desire for originality, more unique designs are being sought.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2016-107427
- Patent Document 1 describes a laminated coating film in which a colored layer having translucency in which a black pigment is dispersed is laminated on a glitter layer, wherein the colored layer A multi-layer coating is described in which the black pigment has a particle size distribution with a peak in the particle size range of 200 nm or less.
- Patent Document 1 describes that the multi-layered coating film expresses vivid and shaded gray.
- Patent Document 2 discloses a metallic paint composition containing a resin component and a coloring component, wherein a transparent scale-like substrate as the coloring component reduces titanium oxide and/or titanium oxide.
- a metallic paint composition is described which is characterized by comprising a low brightness luster pigment coated with a low order titanium oxide and a transparent color pigment. It is described that the coating film formed by this metallic coating composition is a coating film having a low brightness and high chroma, and excellent depth and denseness.
- the coating film of Patent Literature 1 is a coating film recognized as gray as described in Patent Literature 1. Further, according to the invention of Patent Document 2, it is described that it is possible to form a coating film having a low brightness and a coating color excellent in depth and denseness. On the other hand, the coating film of Patent Document 2 is a coating film with high saturation.
- the present invention is a first coating film, a second coating film, and a clear coating film, which have low brightness and saturation so that they can be recognized as black coating films, but have recognizable luminance.
- An object of the present invention is to provide a multilayer coating film composed of layers.
- a multilayer coating film having a first coating film, a second coating film and a clear coating film in this order
- the first coating film is a cured coating film of a first coating composition containing a first coating film-forming resin and a bright pigment
- the second coating is a cured coating of a second coating composition containing a second coating film-forming resin and a color pigment
- the bright pigment contained in the first coating film contains a scale-like aluminum pigment
- the content of the coloring pigment contained in the second coating is in the range of 1.5 to 6 parts by mass with respect to 100 parts by mass of the resin solid content contained in the coating
- the multilayer coating film is The bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less
- the brightness intensity Si (15 °) value at an incident angle of 45 ° and a light receiving angle of 15 ° is 1 or more and 18 or less
- the film thickness of the first coating film is in the range of 3 to 13 ⁇ m
- the content of the scale-like aluminum pigment contained in the first coating film is in the range of 3 to 13 parts by mass with respect to 100 parts by mass of the resin solid content contained in the coating film.
- the multilayer coating film is The luminous intensity Si (45 °) value at an incident angle of 45 ° and a light receiving angle of 45 ° is 1 or more and 17 or less, and the L * (45 °) value at an incident angle of 45 ° and a light receiving angle of 45 ° is 2 or more and 7 or less.
- a method of sequentially coating a first coating composition, a second coating composition and a clear coating composition on an object to form a multilayer coating film The first coating composition contains a first coating film-forming resin and a bright pigment, The second coating composition comprises a second film-forming resin and a color pigment, The bright pigment contained in the first coating composition includes a scale-like aluminum pigment, The content of the color pigment contained in the second coating composition is in the range of 1.5 to 6 parts by mass with respect to 100 parts by mass of the resin solid content contained in the second coating composition,
- the multilayer coating film is The bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less, The brightness intensity Si (15 °) value at an incident angle of 45 ° and a light receiving angle of 15 ° is 1 or more and 18 or less, and the L * (25 °) value at an incident angle of 45 ° and a light receiving angle of 25 ° is 5 or more and 25 or less.
- a method for forming a multilayer coating film is a method in which the first coating composition, the second coating composition and the clear coating composition are successively applied wet-on-wet to the object to be coated to form a multilayer coating film. , The method for forming a multilayer coating film according to [4]. [6] An article having the multilayer coating film according to any one of [1] to [3].
- the inventors have been conducting research with the aim of developing paint films with excellent design properties.
- the range of black generally recognized as a high-class feeling
- brightness and saturation are low enough to be recognized as a black coating film
- luminance I have been studying the method of forming a coating film that is recognized.
- One of the methods for giving brightness to the coating film is to add luster pigments such as aluminum pigments to the coating film.
- luster pigments such as aluminum pigments
- the lightness increases due to the addition of the tint (silver) of the aluminum pigment itself.
- Such a coating film becomes a so-called metallic gray coating film.
- turbidity such as white turbidity occurs in the entire coating film, resulting in a decrease in black feeling.
- the inventors conducted research with the aim of solving the above problems. And, by combining the specific first coating film and the second coating film, it is possible to provide a multi-layer coating film that has low brightness and saturation to the extent that it can be recognized as a black coating film, but has recognizable brightness. was found by experiments, and the present invention was completed.
- the first coating composition forming the first coating film and the second coating composition forming the second coating film will be described in order.
- the first coating in the present disclosure is a cured coating of the first coating composition.
- the first coating composition is a coating composition containing a first coating film-forming resin and a bright pigment.
- the first coating composition contains a first coating film-forming resin.
- the first coating film-forming resin include acrylic resins, polyester resins, polyurethane resins, epoxy resins, fluorine resins, and silicone resins.
- the first coating composition may be a water-based coating composition or a solvent-based coating composition.
- the first coating film-forming resin examples include acrylic resin emulsions (including acrylic silicone resin emulsions, acrylic urethane resin emulsions, etc.), acrylic resin dispersions (acrylic silicone resin dispersions, acrylic urethane resin dispersions, etc.), water-soluble acrylic resins, polyester resin dispersions, polyurethane resin dispersions, epoxy resin dispersions, etc. are preferably included. These resins may be used alone or in combination of two or more. The above resin can be prepared by a method commonly used by those skilled in the art. A commercially available product may be used as the resin.
- Preferred embodiments include, for example, an embodiment using either or both of an acrylic resin emulsion and a water-soluble acrylic resin, an embodiment using an acrylic resin emulsion, a water-soluble acrylic resin and a polyester resin dispersion, an acrylic resin emulsion, a water-soluble acrylic resin and a polyurethane. Examples include a mode using a resin dispersion.
- An acrylic resin emulsion can be prepared, for example, by emulsion polymerization of a mixture of ⁇ , ⁇ -ethylenically unsaturated monomers.
- Preferable ⁇ , ⁇ -ethylenically unsaturated monomers used for preparing the acrylic resin emulsion include, for example, (meth)acrylic acid esters, ⁇ , ⁇ -ethylenically unsaturated monomers having an acid group and ⁇ , ⁇ -ethylenically unsaturated monomers having a hydroxyl group. Ethylenically unsaturated monomers can be mentioned.
- Examples of the (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylic acid.
- (meth)acrylic acid ester means both acrylic acid ester and methacrylic acid ester.
- ⁇ , ⁇ -ethylenically unsaturated monomers having an acid group include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid, ⁇ -carboxy-polycaprolactone mono(meth) Acrylates, isocrotonic acid, ⁇ -hydro- ⁇ -((1-oxo-2-propenyl)oxy)poly(oxy(1-oxo-1,6-hexanediyl)), maleic acid, fumaric acid, itaconic acid, 3 -vinylsalicylic acid, 3-vinylacetylsalicylic acid, 2-acrylamido-2-methylpropanesulfonic acid, p-hydroxystyrene, 2,4-dihydroxy-4'-vinylbenzophenone and the like.
- ⁇ , ⁇ -ethylenically unsaturated monomers having a hydroxyl group hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, allyl alcohol, methallyl alcohol, and these and ⁇ - adducts with caprolactone, and the like.
- Preferred among these are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylate, and addition of these with ⁇ -caprolactone It is a thing.
- the above ⁇ , ⁇ -ethylenically unsaturated monomer mixture may further contain other ⁇ , ⁇ -ethylenically unsaturated monomers.
- Other ⁇ , ⁇ -ethylenically unsaturated monomers include polymerizable amide compounds, polymerizable aromatic compounds, polymerizable nitriles, polymerizable alkylene oxide compounds, polyfunctional vinyl compounds, polymerizable amine compounds, ⁇ -olefins and dienes. , polymerizable carbonyl compounds, polymerizable alkoxysilyl compounds, and other polymerizable compounds.
- Various ⁇ , ⁇ -ethylenically unsaturated monomers can be selected depending on the purpose.
- the acrylic resin emulsion can be prepared by emulsion polymerization of the above ⁇ , ⁇ -ethylenically unsaturated monomer mixture.
- Emulsion polymerization is not particularly limited and can be carried out using a usual method. Specifically, for example, an emulsifier is dissolved in an aqueous medium containing water or, if necessary, an organic solvent such as alcohol, ether (e.g., dipropylene glycol methyl ether, propylene glycol methyl ether, etc.), and heated. It can be carried out by dropping the ⁇ , ⁇ -ethylenically unsaturated monomer mixture and the polymerization initiator under stirring. An ⁇ , ⁇ -ethylenically unsaturated monomer mixture pre-emulsified with an emulsifier and water may likewise be added dropwise.
- polymerization initiator and emulsifier those commonly used by those skilled in the art can be used.
- mercaptans such as lauryl mercaptan
- chain transfer agents such as ⁇ -methylstyrene dimer may be used to control molecular weight.
- the reaction temperature, reaction time and the like can be appropriately selected within the ranges commonly used by those skilled in the art.
- the acrylic resin emulsion obtained by the reaction may be neutralized with a base if necessary.
- the lower limit of the number average molecular weight of the acrylic resin emulsion is preferably 3,000. Further, the acrylic resin emulsion preferably has a hydroxyl value (solid content hydroxyl value) with a lower limit of 20 mgKOH/g and an upper limit of 180 mgKOH/g, and an acid value (solid content acid value) with a lower limit of 1 mgKOH/g and an upper limit of 80 mgKOH/g. Preferably.
- the number average molecular weight is a value determined by the GPC method using polystyrene as a standard.
- the acid value and hydroxyl value are values calculated from the composition of monomers used for preparation based on JIS regulations.
- the water-soluble acrylic resin can be prepared, for example, by solution-polymerizing a monomer mixture containing an ⁇ , ⁇ -ethylenically unsaturated monomer that can be used for the preparation of the acrylic resin emulsion, and solubilizing it with a basic compound.
- the acrylic resin dispersion is prepared, for example, by solution-polymerizing a monomer mixture containing an ⁇ , ⁇ -ethylenically unsaturated monomer that can be used for the preparation of the acrylic resin emulsion, followed by dispersion with a basic compound. be able to.
- a polyester resin dispersion can be prepared, for example, by condensing a polyhydric alcohol component and a polybasic acid component, followed by dispersion with a basic compound.
- the polyurethane resin dispersion is obtained by polymerizing, for example, a polyol compound, a compound having an active hydrogen group and a hydrophilic group in the molecule, and an organic polyisocyanate using a chain extender and a polymerization terminator if necessary. It can be prepared by dissolving or dispersing the polymer in water.
- the first coating composition is a water-based coating composition
- a curing agent that reacts with the first coating film-forming resin.
- Such curing agents are film-forming components that react with the first film-forming resin to form a film.
- melamine resins blocked isocyanate compounds, epoxy compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, metal ions, and the like can be used. These may be used alone or in combination of two or more.
- the above components can be prepared by methods commonly used by those skilled in the art. You may use a commercial item as said component. It is more preferable to use either or both of a melamine resin and a blocked isocyanate compound as a curing agent.
- a water-soluble melamine resin and/or a water-insoluble melamine resin can be used as the melamine resin.
- the melamine resin has a structure in which hydrogen atoms or substituents (alkyl ether groups, methylol groups, etc.) are bonded around a melamine nucleus (triazine nucleus) via three nitrogen atoms.
- the melamine resin is generally composed of a polynuclear body in which a plurality of melamine nuclei are bonded to each other.
- the melamine resin may be mononuclear, consisting of one melamine nucleus.
- a commercially available product may be used as the melamine resin.
- Specific examples of commercially available products include Cymel series (trade name) manufactured by Allnex, specifically Cymel 202, Cymel 204, Cymel 211, Cymel 232, Cymel 235, Cymel 236, Cymel 238, Cymel 250, Cymel 251, Cymel 254, Cymel 266, Cymel 267, Cymel 272, Cymel 285, Cymel 301, Cymel 303, Cymel 325, Cymel 327, Cymel 350, Cymel 370, Cymel 701, Cymel 703, Cymel 1141; and Mitsui Chemicals, Inc. Yuban (trade name) series manufactured by the company. These may be used alone or in combination of two or more.
- a blocked isocyanate compound can be prepared by adding a blocking agent having active hydrogen to a polyisocyanate composed of trimethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, or the like.
- the blocking agent is dissociated by heating to generate an isocyanate group, which reacts with the functional group in the resin component and is cured.
- the amount of the curing agent is preferably 10 to 80% by mass, preferably 15 to 60% by mass, based on the solid content of the coating resin (the solid content of the coating film-forming components including the coating film-forming resin and the curing agent). % is more preferred.
- the first paint composition contains a luster pigment.
- the luster pigment contained in the first coating composition contains a scale-like aluminum pigment.
- the scale-like aluminum pigment preferably has an average particle size of 4 to 25 ⁇ m, more preferably 8 to 18 ⁇ m.
- the scale-like aluminum pigment also preferably has an average thickness of 0.01 to 0.1 ⁇ m, more preferably 0.04 to 0.08 ⁇ m.
- the first coating film has a good dense feeling, thereby suitably obtaining the desired design in the multilayer coating film.
- the average particle diameter of the scale-like aluminum pigment means the average major diameter.
- the average particle size is measured by observing the scaly aluminum pigment using a shape analysis laser microscope (eg, Keyence VK-X 250, etc.), and measuring the maximum length (major diameter) of 100 arbitrarily selected pigments. can be measured by taking the number average of
- the average thickness of the scale-like aluminum pigment is obtained by forming a coating film containing the scale-like aluminum pigment, and measuring the cross section of the obtained coating film using a transmission electron microscope (TEM). It can be measured by taking an average value.
- TEM transmission electron microscope
- the scale-like aluminum pigment also preferably has an aspect ratio (average maximum diameter of pigment/average thickness of pigment) in the range of 50 to 300, more preferably in the range of 100 to 200.
- the scale-like aluminum pigment may be surface-treated as necessary.
- surface treatments that can be applied to aluminum pigments include surface treatments using metal oxide compounds, surface treatments using phosphorus compounds, surface treatments using amine compounds, and surface treatments using silane compounds. be done.
- the metal oxide compounds include metal oxides containing at least a transition metal element as a constituent metal, alkali metal salts thereof, and ammonium salts thereof. Specific examples include molybdenum trioxide, molybdic acid, alkali metal molybdate, ammonium molybdate, vanadic acid, alkali metal vanadate, and ammonium vanadate. Examples of the alkali metal include, but are not limited to, sodium and potassium. Among them, the metal oxide compound is one or more selected from the group consisting of molybdic acid, alkali metal molybdate, ammonium molybdate, vanadic acid, alkali metal vanadate and ammonium vanadate. is preferably used.
- Examples of the phosphorus compounds include organic phosphates, organic phosphites, organic phosphonic acids, and amine salts of these compounds.
- One of these phosphorus compounds may be used alone, or two or more thereof may be used in combination.
- Examples of the amine compound include linear or branched primary amines, linear or branched secondary amines, linear or branched tertiary amines, alicyclic primary amines, alicyclic secondary Examples include amines, alicyclic tertiary amines, aromatic group-containing primary amines, aromatic group-containing secondary amines, and aromatic group-containing tertiary amines. These amine compounds may have a substituent (for example, a hydroxyl group, etc.) as needed. These amine compounds may be used singly or in combination of two or more.
- silane compound examples include alkoxysilane compounds, vinyl group-containing silane coupling agents, epoxy group-containing silane coupling agents, styryl group-containing silane coupling agents, (meth)acrylic group-containing silane coupling agents, amino group-containing Examples include silane coupling agents, isocyanate group-containing silane coupling agents, ureido group-containing silane coupling agents, mercapto group-containing silane coupling agents, acid anhydride group-containing silane coupling agents, and partial condensates thereof. These silane compounds may be used singly or in combination of two or more.
- the above surface treatment can be carried out under treatment conditions commonly used by those skilled in the art. Only one kind of the surface treatment may be carried out, or two or more kinds thereof may be used in combination.
- the luster pigment contained in the first coating composition is a scaly aluminum pigment and has an average particle size of, for example, 4 to 25 ⁇ m, more preferably 8 to 18 ⁇ m
- the surface treatment is applied.
- the stability of the first coating composition is improved without impairing the coating film appearance of the formed multi-layer coating film.
- the scale-like aluminum pigment as the bright pigment, the color such as white blur and chromatic color is not felt, and it is recognized as a black coating film. It has the advantage of being able to suitably form a multi-layered coating film having a brightness and chroma as low as possible, while allowing the brightness to be recognized as a multi-layered coating film.
- a commercially available product may be used as the scale-like aluminum pigment.
- Examples include Alpaste 46 series and 97 series manufactured by Toyo Aluminum Co., Ltd., such as 0519 and 01 series, such as 01-0651; Aluminum Paste FD series manufactured by Asahi Kasei; and Metallux 4860 manufactured by Ecarto.
- the amount of the bright pigment is preferably in the range of 3 to 13 parts by mass, more preferably in the range of 8 to 11 parts by mass, based on 100 parts by mass of the resin solid content of the first coating film-forming resin. more preferred.
- the luster pigment contained in the first coating composition is, if necessary, luster pigments other than scale-like aluminum pigments, e.g., metals such as copper, zinc, iron, nickel, tin, aluminum oxide and alloys thereof luster pigments, and interference mica pigments, white mica pigments, graphite pigments, glass flake pigments, and the like.
- the content of the luster pigment other than these scale-like aluminum pigments is subject to the condition that the effects of the invention of the present disclosure are not impaired.
- the luster pigment contained in the first coating composition is preferably a scale-like aluminum pigment from the viewpoint of the design of the obtained multilayer coating film.
- the first paint composition may contain other pigments as necessary in addition to the bright pigment. However, these other pigments should be in amounts that do not impair the performance of the first coating film.
- Other pigments include, for example, coloring pigments and extender pigments. Examples of extender pigments include calcium carbonate, barium sulfate, clay, and talc.
- the pigment may further contain an antirust pigment, if desired.
- coloring pigment includes chromatic coloring pigments and achromatic coloring pigments.
- coloring pigments include black pigments such as carbon black, graphite, iron black, composite metal oxides such as iron chromium and bismuth manganese, perylene black pigments, and azomethiazol pigments; Blue pigments such as Prussian Blue, Ultramarine Blue, Cobalt Blue, Copper Phthalocyanine Blue, Indanthrone Blue; Yellows such as yellow lead, synthetic yellow iron oxide, bismuth vanadate, titanium yellow, zinc yellow, ocher, monoazo yellow, disazo yellow, isoindolinone yellow, metal complex salt azo yellow, quinophthalone yellow, and benzimidazolone yellow pigment; Red pigments such as iron oxide, transparent iron oxide, monoazo red, quinacridone red, azo lake (Mn salt), perylene red, and perylene maroon; orange pigment
- the water-based first coating composition contains additives commonly used by those skilled in the art, such as surface conditioners, viscosity control agents, thickeners, antioxidants, UV inhibitors, antifoaming agents, and the like. may contain.
- a viscosity control agent by using a viscosity control agent, thixotropy can be imparted, and coating workability can be adjusted.
- Viscosity control agents include, for example, crosslinked or non-crosslinked resin particles, swelling dispersions of fatty acid amides, amide-based fatty acids, polyamides such as phosphates of long-chain polyaminoamides, and colloidal swelling dispersions of polyethylene oxide. , organic acid smectite clay, and organic bentonite-based materials such as montmorillonite. When these additives are used, they can be used in an amount commonly used by those skilled in the art.
- the aqueous first coating composition may further contain a phosphate group-containing organic compound in addition to the above components.
- the aqueous first coating composition may contain water as a solvent, and optionally a water-soluble or water-miscible organic solvent.
- the aqueous first coating composition is produced by kneading and kneading the first coating film-forming resin, the bright pigment, the curing agent, and optionally other components, additives, and the like using a disper, homogenizer, kneader, or the like. It can be produced by a method commonly used by those skilled in the art, such as dispersing. In the above production method, for example, it is preferable to previously prepare a paste containing a luster pigment and optionally a pigment dispersant and mix the paste. A commercially available pigment dispersant or the like can be used as the pigment dispersant.
- the first coating film-forming resin examples include acrylic resins and polyester resins (including urethane-modified polyester resins, etc.). These resins may be used alone or in combination of two or more.
- the acrylic resin can be prepared, for example, by solution polymerization of a monomer mixture containing ⁇ , ⁇ -ethylenically unsaturated monomers.
- the acrylic resin preferably has a number average molecular weight of 1,000 to 20,000.
- the acrylic resin also preferably has an acid value (solid content acid value) of 1 to 80 mgKOH/g, more preferably 10 to 45 mgKOH/g.
- the hydroxyl value (solid content hydroxyl value) is preferably 10 to 200 mgKOH/g.
- a commercially available product may be used as the acrylic resin.
- Commercially available products include, for example, Dianal HR series manufactured by Mitsubishi Rayon Co., Ltd.
- the amount of the acrylic resin is preferably 30 to 80% by mass, more preferably 35 to 70% by mass, based on the solid content of the paint resin (the solid content of the coating film-forming component).
- a hydroxyl group-containing polyester resin can be used as the polyester resin.
- a hydroxyl group-containing polyester resin can be prepared by polycondensing an acid component such as a polyvalent carboxylic acid and/or an acid anhydride with a polyhydric alcohol.
- the first coating composition is a solvent-based coating composition
- a curing agent that reacts with the first coating film-forming resin.
- a melamine resin, a blocked isocyanate compound, or the like can be used as a curing agent. These may be used alone or in combination of two or more.
- the above components can be prepared by methods commonly used by those skilled in the art. You may use a commercial item as said component.
- the curing agent preferably contains melamine resin.
- the melamine resin is not particularly limited, and may be methylated melamine resin, butylated melamine resin, methyl/butyl mixed type melamine resin, or the like.
- Cymel series commercially available from Allnex, Uvan series commercially available from Mitsui Chemicals, etc. can be mentioned.
- the amount of the melamine resin is preferably 10 to 50% by mass, preferably 15 to 40% by mass, based on the solid content of the coating resin (the solid content of the coating film-forming components including the coating film-forming resin and the curing agent). % is more preferred.
- the curing agent preferably further contains a blocked isocyanate compound.
- a blocked isocyanate compound can be prepared by addition reaction of a polyisocyanate with a block compound such as a compound having an active methylene group, a ketone compound, or a caprolactam compound. You may use a commercial item as a block isocyanate compound.
- Commercially available products include, for example, the Duranate series manufactured by Asahi Kasei Corporation and the Sumidule series manufactured by Sumika Covestro Urethane.
- the amount of the blocked isocyanate compound contained in the first coating composition is 10 to 30% by mass based on the solid content of the coating resin (the solid content of the coating film-forming components including the coating film-forming resin and the curing agent). preferably 15 to 25% by mass.
- the solvent-based first coating composition contains the first coating film-forming resin and a bright pigment.
- the above luster pigments can be used in the same manner.
- the solvent-based first coating composition contains additives commonly used by those skilled in the art, such as curing catalysts, surface conditioners, ultraviolet absorbers, antioxidants, etc. Additives commonly used by those skilled in the art and so on.
- the solid content concentration and viscosity of the solvent-based first coating composition can be appropriately adjusted by diluting it with an organic solvent at the time of coating.
- Organic solvents that can be used include, for example, ester solvents, ether solvents, alcohol solvents, ketone solvents, aliphatic hydrocarbon solvents, and aromatic solvents.
- the solvent-based first coating composition may further contain a phosphoric acid group-containing organic compound in addition to the above components.
- the solvent-based first coating composition is produced by kneading and dispersing the first coating film-forming resin, curing agent, pigment, phosphoric acid group-containing organic compound, additives, and the like using a disper, homogenizer, kneader, or the like.
- a disper, homogenizer, kneader, or the like can be produced by a method commonly used by those skilled in the art. In the above production method, for example, it is preferable to previously prepare a paste containing a luster pigment and optionally a pigment dispersant and mix the paste.
- the second coating in the present disclosure is the cured coating of the second coating composition.
- the second coating composition is a coating composition containing a second coating film-forming resin and a color pigment.
- the second coating composition like the first coating composition, may be a water-based coating composition or a solvent-based coating composition. Such a second coating composition can be prepared by the same procedure as for the first coating composition.
- the same resin as the first coating film-forming resin can be used as the second coating film-forming resin.
- the first coating film-forming resin and the second coating film-forming resin may have the same resin composition or may have different resin compositions.
- the content of the coloring pigment contained in the second coating film is within the range of 1.5 to 6 parts by mass with respect to 100 parts by mass of the resin solid content contained in the coating film.
- the lower limit of the content may be 1.7 parts by mass. In one aspect, the lower limit may be, for example, 2.0 parts by mass.
- the upper limit of the content may be 5.7 parts by mass, may be 5.5 parts by mass, and may be 5 parts by mass.
- Suitable examples of the coloring pigment contained in the second coating film include, for example, carbon black, graphite, iron black, composite metal oxides such as iron chromium and bismuth manganese, and perylene-based black pigments. and black pigments such as azomethiazo pigments.
- a coloring pigment other than the black pigment may be included as necessary.
- Other coloring pigments such as Blue pigments such as cyanine blue, thren blue, cobalt blue, copper phthalocyanine blue, and indanthrone blue; Green pigments such as chlorinated phthalocyanine green and brominated phthalocyanine green; purple pigments such as dioxazine violet and perylene violet; Red pigments such as iron oxide, transparent iron oxide, monoazo red, quinacridone red, azo lake (Mn salt), perylene red, and perylene maroon; Yellows such as yellow lead, synthetic yellow iron oxide, bismuth vanadate, titanium yellow, zinc yellow, ocher, monoazo yellow, disazo yellow, isoindolinone yellow, metal complex salt azo yellow, quinophthalone yellow, and benzimidazolone yellow pigment; orange pigments such as quinacridone magenta, anthrone orange, dianthraquinonyl red, pyr
- a suitable amount of the coloring pigment contained in the second coating composition is, like the content in the second coating film, 1.5 to 6 parts per 100 parts by mass of the resin solid content contained in the second coating composition. Parts by mass are preferred.
- the lower limit of the content may be 1.7 parts by mass. In one aspect, the lower limit may be, for example, 2.0 parts by mass.
- the upper limit of the content may be 5.7 parts by mass, may be 5.5 parts by mass, and may be 5 parts by mass.
- the second paint composition may contain pigments other than the color pigments.
- Other pigments include, for example, extender pigments and rust preventive pigments exemplified in the first paint composition.
- extender pigments include calcium carbonate, barium sulfate, clay, and talc.
- the second paint composition preferably does not substantially contain a bright pigment.
- the content of the bright pigment in the second coating composition is preferably less than 0.5 parts by mass, more preferably less than 0.3 parts by mass relative to 100 parts by mass of the resin solid content, More preferably less than 0.1 part by mass.
- the multilayer coating film of the present disclosure includes a first coating film that is a cured coating film of the first coating composition, a second coating film that is a cured coating film of the second coating composition, and a clear It is a coating film having coating films in this order.
- the object to be coated with the coating composition is not particularly limited, and examples thereof include metals, plastics, and foams.
- the above coating composition can be used particularly advantageously for metals and castings, and can be particularly suitably used for metals that can be electrodeposition coated.
- metals include, for example, iron, copper, aluminum, tin, zinc, etc., and alloys containing these metals.
- These objects to be coated may be moldings. Specific examples of molded articles include automobile bodies such as passenger cars, trucks, motorcycles and buses, and parts thereof.
- the object to be coated such as the above-mentioned metal is chemically treated with a phosphoric acid-based chemical conversion treatment agent, a zirconium-based chemical conversion treatment agent, or the like before electrodeposition coating.
- the cured electrodeposition coating film is formed on the article to be coated which has been subjected to chemical conversion treatment as necessary.
- the electrodeposition coating composition used for forming the cured electrodeposition coating film both cationic and anionic types can be used. By using a cationic electrodeposition coating composition as the electrodeposition coating composition, it is possible to form a coating film having more excellent anticorrosion properties, which is preferable.
- an intermediate coating film may be formed on the cured electrodeposition coating film of the object to be coated.
- An intermediate coating composition is used to form the intermediate coating film.
- a coating composition containing a film-forming resin, a curing agent, various organic and/or inorganic coloring components, an extender pigment, and the like can be used.
- the coating film-forming resin and the curing agent are not particularly limited, and specifically, the coating film-forming resins and curing agents mentioned in the water-based coating composition can be used.
- the film-forming resin of the intermediate coating composition a combination of an acrylic resin and/or polyester resin and an amino resin and/or isocyanate is preferably used from the viewpoint of various properties of the resulting intermediate coating film.
- Examples of the coating film forming method using the first coating composition and the second coating composition include the following methods. - A method in which the first coating composition and the second coating composition are sequentially applied to an object to be coated, and then the clear coating composition is applied. In such coating, the first coating composition may be applied and cured by heating, and then the second coating composition may be coated and cured by heating. Alternatively, the first coating composition may be applied, the second coating composition may be applied wet-on-wet to the uncured coating film, and then heat-cured. In the above wet-on-wet coating, preheating may be performed between coatings, if necessary. Alternatively, the first coating composition and the second coating composition may be sequentially applied and dried at room temperature.
- the clear coating composition is applied to the second coating film obtained by applying the second coating composition to form a clear coating film.
- the first coating composition and the second coating composition can be applied to the object to be coated by a method generally used in the coating field.
- coating methods include air spray coating, airless spray coating, electrostatic spray coating, multi-stage coating (preferably two-stage coating) by air electrostatic spray coating, air electrostatic spray coating and rotary atomization type electrostatic coating machine. and the like.
- the first coating composition is preferably applied so that the thickness of the first coating film after curing is within the range of 3 to 13 ⁇ m.
- the lower limit of the film thickness may be 3.5 ⁇ m.
- the upper limit of the film thickness may be 10 ⁇ m or 8 ⁇ m.
- the second coating composition is preferably applied so that the film thickness of the second coating film after curing is in the range of 3 to 15 ⁇ m.
- the lower limit of the film thickness may be 3.5 ⁇ m.
- the upper limit of the film thickness may be 13 ⁇ m, or may be 10 ⁇ m.
- the heating temperature and time when the first coating composition and the second coating composition are applied and heat-cured are appropriately selected according to the composition of the coating composition (aqueous or solvent type) and the type of object to be coated. be able to.
- the heating temperature can be appropriately selected, for example, in the range of 80 to 180°C, preferably in the range of 100 to 160°C.
- the heating time can be appropriately selected, for example, within the range of 5 minutes to 60 minutes, preferably 10 minutes to 30 minutes.
- the above clear coating composition is not particularly limited, and includes solvent-based, water-based and powder-based clear coating compositions.
- the solvent-based clear coating composition include a combination of an acrylic resin and/or polyester resin, an amino resin and/or isocyanate, or a carboxylic acid/epoxy curing system from the viewpoint of transparency or acid etching resistance.
- water-based clear coating compositions include those containing resins obtained by neutralizing the film-forming resins listed as examples of the solvent-based clear coating compositions with a base to make them water-based. This neutralization can be done by adding tertiary amines such as dimethylethanolamine and triethylamine before or after polymerization.
- solvent-based clear coating compositions and water-based clear coating compositions preferably contain a viscosity control agent in order to ensure coating workability.
- Viscosity control agents that generally exhibit thixotropy can be used.
- the viscosity control agent for example, those mentioned in the section of the water-based coating composition can be used.
- additives generally used in the paint field may be included as necessary.
- thermosetting powder coating compositions commonly used in the coating field, such as thermoplastic powder coating compositions and thermosetting powder coating compositions, can be used.
- the thermosetting powder coating composition is preferred from the viewpoint of the physical properties of the coating film.
- Specific examples of thermosetting powder coating compositions include epoxy-, acrylic- and polyester-based clear powder coating compositions.
- the coating of the clear coating composition can be carried out using a coating method known to those skilled in the art according to the coating form of the clear coating composition.
- the dry film thickness of the clear coating film formed by applying the above clear coating composition is generally preferably 10 to 80 ⁇ m, more preferably 20 to 60 ⁇ m.
- a cured clear coating film can be formed by heating and curing an uncured clear coating film obtained by applying the clear coating composition.
- the heat-curing temperature is preferably set to 80 to 180° C., more preferably 120 to 160° C., from the viewpoint of curability and physical properties of the obtained multilayer coating film.
- the heat curing time can be arbitrarily set according to the temperature.
- the heat curing conditions include, for example, a condition of heating at a heat curing temperature of 120° C. to 160° C. for 10 minutes to 30 minutes.
- the coating composition is applied, dried at room temperature to form a coating film, and then, for example, a reaction-curing clear coating composition is applied to form a clear coating film. may be provided.
- the multilayer coating film of the present disclosure is The bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less,
- the brightness intensity Si (15 °) value at an incident angle of 45 ° and a light receiving angle of 15 ° is 1 or more and 18 or less, and the L * (25 °) value at an incident angle of 45 ° and a light receiving angle of 25 ° is 5 or more and 25 or less.
- the above lightness L* is a parameter in the L*C*h color system and can be obtained in accordance with JIS Z8729.
- This L*C*h color system is a color system defined by the International Commission on Illumination and described in Section 4.2 of CIE Publication 15.2 (1986).
- L* represents lightness
- C* represents chroma
- h represents hue angle.
- the chroma C* means that as the value increases, the substance to be measured becomes brighter, and as the value decreases, the dullness increases.
- the lightness L* means that as the numerical value increases, the brightness of the substance to be measured increases, and as the numerical value decreases, the darkness increases.
- the lightness L* can be measured using a commercially available multi-angle spectrophotometer. Examples of the multi-angle spectrophotometer include BYK-maci (manufactured by BYK).
- the incident angle and the light receiving angle are defined as follows: , means the light-receiving angle at a position 25° from the specularly reflected light in the direction of the incident angle.
- the measurement of the lightness L* of the multilayer coating film is a multilayer coating composed of a cured coating film of the first coating composition, a cured coating film of the second coating composition, and a clear coating film.
- a value measured using a membrane More specifically, a steel plate coated with a cationic electrodeposition coating composition is coated with a dark gray intermediate curing coating film, and the first coating composition is spray-coated so that the dry film thickness is 4 ⁇ m.
- the second coating composition is wet-on-wet spray-coated so that the dry film thickness is 4 ⁇ m, and then the clear coating composition is wet-on-wet spray-coated so that the dry film thickness is 35 ⁇ m, Thereafter, measurement is performed using a multi-layer coating film obtained by heating and curing the uncured three-layer coating film at 140° C. for 20 minutes.
- the L* (25°) value is 5 or more and 25 or less.
- the multi-layer coating film has an L* (25°) value within the above range, and the lightness is so low that the multi-layer coating film is recognized as a black coating film even under so-called highlight light receiving angle conditions. Let it be one of the features.
- the lower limit of the L*(25°) value is preferably 7, more preferably 10.
- the upper limit of the L*(25°) value is preferably 24.5.
- the multilayer coating film of the present disclosure preferably has an L*(45°) value of 2 or more and 8 or less at an incident angle of 45° and a light receiving angle of 45°.
- the measurement condition of the incident angle of 45° and the light receiving angle of 45° is the so-called face receiving angle condition during the transition from highlight (light receiving angle of 15 to 25°) to shade (light receiving angle of 75 to 110°).
- the lightness L* (45°) value in this measurement condition is within the above range, the lightness of the multilayer coating film viewed from the front condition is sufficiently low, and the design intended by the present disclosure is suitably obtained. Become.
- the multi-layer coating film of the present disclosure is also conditional on the brilliance intensity Si (15°) value at an incident angle of 45° and a light receiving angle of 15° being 1 or more and 18 or less.
- the brilliance intensity (Si) is an index indicating the intensity of brilliance, and the higher the value, the stronger the brilliance.
- the measured value of the brightness intensity Si refers to a value measured using a multi-layer coating film prepared in the same procedure as the measurement of the brightness L*.
- the above brightness intensity Si (15 °) value is obtained by irradiating the coating film with an LED light source at an incident angle of 45 °, and setting the position of the specularly reflected light of the light irradiated from this 45 ° angle to 0 °.
- the brightness intensity Si (45°) value at an incident angle of 45° and a light receiving angle of 45° is 1 or more and 17 or less.
- the brightness intensity Si (45 °) value is obtained by irradiating the coating film with an LED light source at an incident angle of 45 °, and setting the position of the specularly reflected light of the light irradiated from this 45 ° angle to 0 °, and this specularly reflected light is a numerical value obtained by acquiring an image by the same procedure as above at a position of 45° in the incident angle direction (45° of light receiving angle) from , and expressing it as the brightness intensity.
- the multilayer coating film of the present disclosure is also conditional that the bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less.
- the bright area Sa value is an index that numerically indicates the area (size) of the bright portion.
- the measurement of the bright area Sa value refers to the value measured using a multi-layer coating film prepared in the same manner as the measurement of the lightness L*.
- the above brilliant area Sa (45 °) value is obtained by irradiating the coating film with an LED light source at an incident angle of 45 °, setting the position of the specularly reflected light of the light irradiated from this 45 ° angle to 0 °, and this specular reflection
- the glitter area Sa (45°) value of the multilayer coating film is 8 or more and 35 or less, so that a constant area of glitter can be recognized from the multilayer coating film under the light-receiving angle condition called the so-called face. becomes.
- the multi-layer coating film of the present disclosure is recognized as having brightness, but has low brightness and saturation, and is recognized as a black coating film as a hue. It is a coating film with a unique design.
- ST styrene
- MMA methyl methacrylate
- BA n-butyl acrylate
- 2-EHA 2-ethylhexyl acrylate
- HEMA hydroxyethyl methacrylate
- an initiator solution consisting of 3.0 parts of ammonium persulfate and 500 parts of deionized water were concurrently added dropwise to the reaction vessel over 1.5 hours. After completion of dropping, aging was performed at the same temperature for 2 hours. Then, after cooling to 40 ° C. and filtering with a 400 mesh filter, 100 parts of deionized water and 1.6 parts of dimethylaminoethanol were added to adjust the pH to 6.5, the average particle size was 150 nm, the nonvolatile content was 35%, and the solid content was adjusted to 6.5.
- An acrylic resin emulsion having an acid value of 20 mgKOH/g and a hydroxyl value of 100 mgKOH/g was obtained.
- the obtained phosphate group-containing organic compound had an acid value of 105 mgKOH/g, including a phosphate value of 55 mgKOH/g, a hydroxyl value of 60 mgKOH/g, a number average molecular weight of 6000, and a non-volatile content of 63%.
- the number average molecular weight was measured using "HLC8220GPC” (trade name, manufactured by Tosoh Corporation) as a GPC device, and "Shodex KF-606M” and “Shodex KF-603” as columns (both Showa Denko KK, trade name), mobile phase: tetrahydrofuran, measurement temperature: 40°C, flow rate: 0.6 cc/min, detector: RI.
- the calculation of the acid value and the phosphate group value of the phosphate group-containing organic compound is based on the definition of acid value of JIS K5601 2-1 (neutralizing the free acid in 1 g of the sample (non-volatile matter) It was calculated based on the number of mg of potassium hydroxide (KOH) required to do so.
- the hydroxyl value is calculated based on the definition of hydroxyl value of JIS K0070 (mg of potassium hydroxide required to neutralize acetic acid bound to hydroxyl group when 1 g of sample is acetylated). I went and asked
- Example 1 Preparation of First Coating Composition Colored Pigment Dispersion Paste 6 parts of Shannin Blue G314, 4 parts of Fastgen Super Red 400RG, 20 parts of Raven 5000, which are color pigments, and Dispex® Ultra PA 4550, which is a pigment dispersant ( BASF Corporation), 36.0 parts of deionized water, and 0.5 parts of BYK-011, which is an antifoaming agent, were mixed and dispersed with a stirrer such as a disper to obtain a colored pigment dispersion paste.
- a stirrer such as a disper to obtain a colored pigment dispersion paste.
- Colored pigment dispersion paste Colored pigment Raven 5000 3 parts, pigment dispersant Dispex (registered trademark) Ultra PA 4550 (manufactured by BASF) 18.6 parts, ion-exchanged water 36.0 parts , and 0.5 parts of BYK-011 as an antifoaming agent were mixed and dispersed with a stirrer such as a disper to obtain a colored pigment dispersion paste.
- aqueous coating composition having a resin solid content concentration of 15% by mass.
- the amount of the color pigment contained in the obtained second coating composition was 1.5 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
- a cationic electrodeposition coating composition "Power Top U-50" (Nippon Paint Automotive Coatings Co., Ltd.) was applied to a dull steel plate with a thickness of 0.8 mm, length of 30 cm, and width of 40 cm, which had been treated with zinc phosphate. ) was electrodeposited so that the dry film thickness was 20 ⁇ m, and baked at 160 ° C. for 30 minutes.
- Polyester/melamine paint, 25 seconds (previously diluted to 20°C using a No. 4 Ford cup) was applied using an air spray gun W-101-132G manufactured by Anest Iwata so that the dry film thickness was 35 ⁇ m. and then cured by baking at 140° C.
- the first coating composition was air-sprayed to a dry film thickness of 4 ⁇ m under conditions of room temperature of 23° C. and humidity of 68%. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes. After preheating, the second paint composition was air-sprayed wet-on-wet under the conditions of room temperature of 23° C. and humidity of 68% so as to give a dry film thickness of 12 ⁇ m. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes.
- the coated plate After preheating after coating the second coating composition, the coated plate was allowed to cool to room temperature, and Macflow-O-1810 (a solvent-based clear coating manufactured by Nippon Paint Automotive Coatings) was applied as a clear coating to a dry film thickness of 35 ⁇ m. Air spray coating was applied so as to obtain a uniform thickness, and the setting was performed for 7 minutes. Then, the coated plate was baked in a dryer at 140° C. for 30 minutes to obtain a coated test plate having a multilayer coating film.
- Macflow-O-1810 a solvent-based clear coating manufactured by Nippon Paint Automotive Coatings
- Example 2 Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 35 parts. The amount of the color pigment contained in the obtained second coating composition was 1.7 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
- a multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
- Example 3 Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 40 parts. The amount of the color pigment contained in the obtained second coating composition was 2.0 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
- a multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
- Example 4 Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 50 parts. The amount of the color pigment contained in the obtained second coating composition was 2.5 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
- a multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
- Comparative example 1 Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 10 parts. The amount of the color pigment contained in the obtained second coating composition was 0.5 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
- a multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
- Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 160 parts. The amount of the color pigment contained in the obtained second coating composition was 8.0 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
- a multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
- Comparative example 3 Preparation of Coating Composition
- the first coating composition prepared in Example 1 was used as the coating composition.
- a cationic electrodeposition coating composition "Power Top U-50" (Nippon Paint Automotive Coatings Co., Ltd.) was applied to a dull steel plate with a thickness of 0.8 mm, length of 30 cm, and width of 40 cm, which had been treated with zinc phosphate. ) was electrodeposited so that the dry film thickness was 20 ⁇ m, and baked at 160 ° C. for 30 minutes.
- Polyester/melamine paint, 25 seconds (previously diluted to 20°C using a No. 4 Ford cup) was applied using an air spray gun W-101-132G manufactured by Anest Iwata so that the dry film thickness was 35 ⁇ m. and then cured by baking at 140° C.
- the coating composition obtained above was air-sprayed to a dry film thickness of 4 ⁇ m under conditions of room temperature of 23° C. and humidity of 68%. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes. After the above preheating, the coated plate was allowed to cool to room temperature, and MACFLO-O-1810 (a solvent-based clear paint manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was air-sprayed as a clear paint to a dry film thickness of 35 ⁇ m. , was set for 7 minutes. Then, the coated plate was baked in a dryer at 140° C. for 30 minutes to obtain a coated test plate having a multilayer coating film.
- MACFLO-O-1810 a solvent-based clear paint manufactured by Nippon Paint Automotive Coatings Co., Ltd.
- Comparative example 4 2.8 parts of HELIOGEN BLUE L6700F, 8.0 parts of EMPEROR-2000, 1.5 parts of HOSTAPERM VIOLET RL NFVP336, which are colored pigments, and Dispex® , which is a pigment dispersant. 18.6 parts of Ultra PA 4550 (manufactured by BASF), 36.0 parts of ion-exchanged water, and 0.5 parts of antifoaming agent BYK-011 are mixed and dispersed with a stirrer such as a disper to form a colored pigment dispersion paste. Obtained.
- a cationic electrodeposition coating composition "Power Top U-50" (Nippon Paint Automotive Coatings Co., Ltd.) was applied to a dull steel plate with a thickness of 0.8 mm, length of 30 cm, and width of 40 cm, which had been treated with zinc phosphate. ) was electrodeposited so that the dry film thickness was 20 ⁇ m, and baked at 160 ° C. for 30 minutes.
- Polyester/melamine paint, 25 seconds (previously diluted to 20°C using a No. 4 Ford cup) was applied using an air spray gun W-101-132G manufactured by Anest Iwata so that the dry film thickness was 35 ⁇ m. and then cured by baking at 140° C.
- the coating composition obtained above was air-sprayed to a dry film thickness of 12 ⁇ m under conditions of room temperature of 23° C. and humidity of 68%. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes. After the above preheating, the coated plate was allowed to cool to room temperature, and MACFLO-O-1810 (a solvent-based clear paint manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was air-sprayed as a clear paint to a dry film thickness of 35 ⁇ m. , was set for 7 minutes. Then, the coated plate was baked in a dryer at 140° C. for 30 minutes to obtain a coated test plate having a multilayer coating film.
- MACFLO-O-1810 a solvent-based clear paint manufactured by Nippon Paint Automotive Coatings Co., Ltd.
- the coated test panels having the multilayer coating film formed in each example and comparative example were visually observed and evaluated according to the following criteria. 2: Although the multilayer coating film is black, brightness is perceived. 1: The multilayer coating film is perceived as whitish gray instead of black, or perceived as black, but lacks brightness.
- the multilayer coating film of Comparative Example 1 is an example with a high L*(25°) value. In this example, the brightness was high under the so-called highlight acceptance angle condition, and the brightness was recognized as a whole, and the coating film was recognized as a dark gray color.
- the multilayer coating film of Comparative Example 2 is an example with a low L*(25°) value. In this example, the coating film was perceived as a black coating film, but the coating film was not perceived to be bright even under so-called high light receiving angle conditions.
- Comparative Examples 3 and 4 are examples in which an attempt was made to realize a design with brightness, low brightness and low saturation using one coating composition instead of using the first coating composition and the second coating composition. be. Since Comparative Example 3 did not have the second coating film of the present disclosure, the brightness was high under the light receiving angle condition, and the coating film as a whole was bright and recognized as a gray color. Comparative Example 4 is an example in which more color pigments are used than in Comparative Example 3, and the type of luster pigment is changed so that luminance can be recognized. In this example, although the lightness under the light receiving angle condition decreased to some extent, the brightness intensity increased, and the overall brightness was recognized, and the coating film was recognized as a dark gray color.
- the multilayer coating film of the present disclosure has both a profound feeling of black color and a feeling of brilliance due to brightness, and has excellent design properties, with brightness and chroma being so low that it can be recognized as black, while brightness is recognized. is.
- the multi-layer coating film can be suitably used as a decorative coating film for various articles (for example, automobile bodies such as passenger cars, trucks, motorcycles and buses, and parts thereof).
Abstract
The present invention provides a multilayer coating film that is formed from a first coating film, a second coating film, and a clear coating film and allows luminance to be perceived while brightness and chroma are low. The multilayer coating film includes a first coating film, a second coating film, and a clear coating film in this order. The first coating film is a cured coating film of a first coating composition including a first coating film-forming resin and a lustrous pigment, the second coating film is a cured coating film of a second coating composition including a second coating film-forming resin and a colored pigment, the lustrous pigment included in the first coating film includes a scale-like aluminum pigment, the content of the colored pigment included in the second coating film is within the range of 1.5-6 parts by mass with respect to 100 parts by mass of solid resin content included in the coating film, the multilayer film has a sparkle area Sa (45º) value of 8-35 at an incidence angle of 45º and a light reception angle of 45º, the sparkle intensity Si (15º) value at an incidence angle of 45º and a light reception angle of 15º is 1-18, and the L*(25º) value at an incidence angle of 45º and a light reception angle of 25º is 5-25.
Description
本発明は、複層塗膜および複層塗膜の形成方法に関する。
The present invention relates to a multilayer coating film and a method for forming a multilayer coating film.
自動車車体などの被塗物の表面には、種々の役割を持つ複数の塗膜を順次形成して、被塗物を保護すると同時に美しい外観および優れた意匠を付与している。このような複数の塗膜の形成方法としては、導電性に優れた被塗物上に電着塗膜などの下塗り塗膜を形成し、その上に、必要に応じた中塗り塗膜、そして上塗り塗膜を順次形成する方法が一般的である。これらの塗膜において、特に塗膜の外観および意匠を大きく左右するのは、ベース塗膜とクリヤー塗膜とからなる上塗り塗膜である。特に自動車において、車体上に形成されるベース塗膜とクリヤー塗膜とからなる上塗り塗膜の外観および意匠は、極めて重要である。
On the surface of an object to be coated such as an automobile body, multiple coating films with various roles are sequentially formed to protect the object to be coated and at the same time impart a beautiful appearance and excellent design. As a method for forming such a plurality of coating films, an undercoat coating film such as an electrodeposition coating film is formed on an object to be coated with excellent conductivity, and an intermediate coating film is formed thereon, if necessary. A method of sequentially forming top coat films is common. In these coating films, it is the top coating film consisting of the base coating film and the clear coating film that greatly affects the appearance and design of the coating film. In particular, in automobiles, the appearance and design of a top coat consisting of a base coat and a clear coat formed on a vehicle body are extremely important.
自動車に形成された塗膜の外観は、その自動車の高級感などといった外観価値に大きく関与する。また自動車を購入する顧客は、意匠性に優れた塗膜を有する自動車を求める傾向にある。消費者の好みの多様化および独自性志向により、より独特な意匠が求められている。
The appearance of the paint film formed on the automobile greatly contributes to the appearance value of the automobile, such as its luxury appearance. In addition, customers who purchase automobiles tend to seek automobiles having coating films with excellent design. Due to the diversification of consumer tastes and the desire for originality, more unique designs are being sought.
例えば特開２０１６－１０７４２７号公報（特許文献１）には、光輝性層の上に黒色顔料が分散した透光性を有する着色層が積層されてなる積層塗膜であって、上記着色層の黒色顔料は、２００ｎｍ以下の粒径範囲にピークを有する粒度分布をもつことを特徴とする積層塗膜が記載される。そして特許文献１の複層塗膜は、鮮やかな且つ陰影感のあるグレーを発現することが記載される。
For example, Japanese Patent Application Laid-Open No. 2016-107427 (Patent Document 1) describes a laminated coating film in which a colored layer having translucency in which a black pigment is dispersed is laminated on a glitter layer, wherein the colored layer A multi-layer coating is described in which the black pigment has a particle size distribution with a peak in the particle size range of 200 nm or less. Patent Document 1 describes that the multi-layered coating film expresses vivid and shaded gray.
特開２００７－１０６９２５号公報（特許文献２）には、樹脂成分及び着色成分を含むメタリック塗料組成物であって、着色成分として、透明な鱗片状基材が酸化チタン及び／又は酸化チタンを還元した低次酸化チタンで被覆された低明度光輝性顔料及び透明性着色顔料を含むことを特徴とするメタリック塗料組成物が記載される。このメタリック塗料組成物によって形成される塗膜は、低明度且つ高彩度の、深み感及び緻密感に優れた塗色の塗膜であることが記載される。
Japanese Patent Application Laid-Open No. 2007-106925 (Patent Document 2) discloses a metallic paint composition containing a resin component and a coloring component, wherein a transparent scale-like substrate as the coloring component reduces titanium oxide and/or titanium oxide. A metallic paint composition is described which is characterized by comprising a low brightness luster pigment coated with a low order titanium oxide and a transparent color pigment. It is described that the coating film formed by this metallic coating composition is a coating film having a low brightness and high chroma, and excellent depth and denseness.
上記特許文献１の発明により、鮮やかな且つ陰影感のあるグレーを発現することができると記載される。一方で特許文献１の塗膜は、特許文献１に記載される通り、グレー色として認識される塗膜である。また特許文献２の発明により、低明度であり、深み感及び緻密感に優れた塗色の塗膜を形成することができると記載される。一方で特許文献２の塗膜は、高彩度である塗膜である。
It is described that the invention of Patent Document 1 above can express a vivid and shaded gray. On the other hand, the coating film of Patent Literature 1 is a coating film recognized as gray as described in Patent Literature 1. Further, according to the invention of Patent Document 2, it is described that it is possible to form a coating film having a low brightness and a coating color excellent in depth and denseness. On the other hand, the coating film of Patent Document 2 is a coating film with high saturation.
上記特許文献に対して、本件発明は、黒色塗膜と認識されるほどに明度および彩度が低い一方で、輝度が認識される、第１塗膜、第２塗膜およびクリヤー塗膜の３層から構成される複層塗膜を提供することを課題とする。
In contrast to the above-mentioned patent document, the present invention is a first coating film, a second coating film, and a clear coating film, which have low brightness and saturation so that they can be recognized as black coating films, but have recognizable luminance. An object of the present invention is to provide a multilayer coating film composed of layers.
上記課題を解決するため、本発明は下記態様を提供する。
［１］
第１塗膜、第２塗膜およびクリヤー塗膜をこの順に有する複層塗膜であって、
上記第１塗膜は、第１塗膜形成樹脂および光輝性顔料を含む第１塗料組成物の硬化塗膜であり、
上記第２塗膜は、第２塗膜形成樹脂および着色顔料を含む第２塗料組成物の硬化塗膜であり、
上記第１塗膜中に含まれる光輝性顔料は鱗片状アルミニウム顔料を含み、
上記第２塗膜中に含まれる着色顔料の含有量は、塗膜に含まれる樹脂固形分１００質量部に対して１．５～６質量部の範囲内であり、
上記複層塗膜は、
入射角４５°受光角４５°における光輝面積Ｓａ（４５°）値が８以上３５以下であり、
入射角４５°受光角１５°における光輝強度Ｓｉ（１５°）値が１以上１８以下であり、入射角４５°受光角２５°におけるＬ＊（２５°）値が５以上２５以下である、
複層塗膜。
［２］
上記第１塗膜の膜厚は、３～１３μｍの範囲内であり、
上記第１塗膜に含まれる鱗片状アルミニウム顔料の含有量は、塗膜に含まれる樹脂固形分１００質量部に対して３～１３質量部の範囲内である、
［１］に記載の複層塗膜。
［３］
上記複層塗膜は、
入射角４５°受光角４５°における光輝強度Ｓｉ（４５°）値が１以上１７以下であり入射角４５°受光角４５°におけるＬ＊（４５°）値が２以上７以下である、
［１］または［２］に記載の複層塗膜。
［４］
被塗物に、第１塗料組成物、第２塗料組成物およびクリヤー塗料組成物を順次塗装して、複層塗膜を形成する方法であって、
上記第１塗料組成物は、第１塗膜形成樹脂および光輝性顔料を含み、
上記第２塗料組成物は、第２塗膜形成樹脂および着色顔料を含み、
上記第１塗料組成物中に含まれる光輝性顔料は鱗片状アルミニウム顔料を含み、
上記第２塗料組成物中に含まれる着色顔料の含有量は、第２塗料組成物中に含まれる樹脂固形分１００質量部に対して１．５～６質量部の範囲内であり、
上記複層塗膜は、
入射角４５°受光角４５°における光輝面積Ｓａ（４５°）値が８以上３５以下であり、
入射角４５°受光角１５°における光輝強度Ｓｉ（１５°）値が１以上１８以下であり、入射角４５°受光角２５°におけるＬ＊（２５°）値が５以上２５以下である、
複層塗膜の形成方法。
［５］
上記複層塗膜の形成は、被塗物に、第１塗料組成物、第２塗料組成物およびクリヤー塗料組成物をウェットオンウェットで順次塗装して、複層塗膜を形成する方法である、
［４］に記載の複層塗膜の形成方法。
［６］
［１］～［３］いずれかに記載の複層塗膜を有する物品。 In order to solve the above problems, the present invention provides the following aspects.
[1]
A multilayer coating film having a first coating film, a second coating film and a clear coating film in this order,
The first coating film is a cured coating film of a first coating composition containing a first coating film-forming resin and a bright pigment,
The second coating is a cured coating of a second coating composition containing a second coating film-forming resin and a color pigment,
The bright pigment contained in the first coating film contains a scale-like aluminum pigment,
The content of the coloring pigment contained in the second coating is in the range of 1.5 to 6 parts by mass with respect to 100 parts by mass of the resin solid content contained in the coating,
The multilayer coating film is
The bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less,
The brightness intensity Si (15 °) value at an incident angle of 45 ° and a light receiving angle of 15 ° is 1 or more and 18 or less, and the L * (25 °) value at an incident angle of 45 ° and a light receiving angle of 25 ° is 5 or more and 25 or less.
Multi-layer coating.
[2]
The film thickness of the first coating film is in the range of 3 to 13 μm,
The content of the scale-like aluminum pigment contained in the first coating film is in the range of 3 to 13 parts by mass with respect to 100 parts by mass of the resin solid content contained in the coating film.
The multilayer coating film according to [1].
[3]
The multilayer coating film is
The luminous intensity Si (45 °) value at an incident angle of 45 ° and a light receiving angle of 45 ° is 1 or more and 17 or less, and the L * (45 °) value at an incident angle of 45 ° and a light receiving angle of 45 ° is 2 or more and 7 or less.
The multilayer coating film according to [1] or [2].
[4]
A method of sequentially coating a first coating composition, a second coating composition and a clear coating composition on an object to form a multilayer coating film,
The first coating composition contains a first coating film-forming resin and a bright pigment,
The second coating composition comprises a second film-forming resin and a color pigment,
The bright pigment contained in the first coating composition includes a scale-like aluminum pigment,
The content of the color pigment contained in the second coating composition is in the range of 1.5 to 6 parts by mass with respect to 100 parts by mass of the resin solid content contained in the second coating composition,
The multilayer coating film is
The bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less,
The brightness intensity Si (15 °) value at an incident angle of 45 ° and a light receiving angle of 15 ° is 1 or more and 18 or less, and the L * (25 °) value at an incident angle of 45 ° and a light receiving angle of 25 ° is 5 or more and 25 or less.
A method for forming a multilayer coating film.
[5]
The formation of the multilayer coating film is a method in which the first coating composition, the second coating composition and the clear coating composition are successively applied wet-on-wet to the object to be coated to form a multilayer coating film. ,
The method for forming a multilayer coating film according to [4].
[6]
An article having the multilayer coating film according to any one of [1] to [3].
［１］
第１塗膜、第２塗膜およびクリヤー塗膜をこの順に有する複層塗膜であって、
上記第１塗膜は、第１塗膜形成樹脂および光輝性顔料を含む第１塗料組成物の硬化塗膜であり、
上記第２塗膜は、第２塗膜形成樹脂および着色顔料を含む第２塗料組成物の硬化塗膜であり、
上記第１塗膜中に含まれる光輝性顔料は鱗片状アルミニウム顔料を含み、
上記第２塗膜中に含まれる着色顔料の含有量は、塗膜に含まれる樹脂固形分１００質量部に対して１．５～６質量部の範囲内であり、
上記複層塗膜は、
入射角４５°受光角４５°における光輝面積Ｓａ（４５°）値が８以上３５以下であり、
入射角４５°受光角１５°における光輝強度Ｓｉ（１５°）値が１以上１８以下であり、入射角４５°受光角２５°におけるＬ＊（２５°）値が５以上２５以下である、
複層塗膜。
［２］
上記第１塗膜の膜厚は、３～１３μｍの範囲内であり、
上記第１塗膜に含まれる鱗片状アルミニウム顔料の含有量は、塗膜に含まれる樹脂固形分１００質量部に対して３～１３質量部の範囲内である、
［１］に記載の複層塗膜。
［３］
上記複層塗膜は、
入射角４５°受光角４５°における光輝強度Ｓｉ（４５°）値が１以上１７以下であり入射角４５°受光角４５°におけるＬ＊（４５°）値が２以上７以下である、
［１］または［２］に記載の複層塗膜。
［４］
被塗物に、第１塗料組成物、第２塗料組成物およびクリヤー塗料組成物を順次塗装して、複層塗膜を形成する方法であって、
上記第１塗料組成物は、第１塗膜形成樹脂および光輝性顔料を含み、
上記第２塗料組成物は、第２塗膜形成樹脂および着色顔料を含み、
上記第１塗料組成物中に含まれる光輝性顔料は鱗片状アルミニウム顔料を含み、
上記第２塗料組成物中に含まれる着色顔料の含有量は、第２塗料組成物中に含まれる樹脂固形分１００質量部に対して１．５～６質量部の範囲内であり、
上記複層塗膜は、
入射角４５°受光角４５°における光輝面積Ｓａ（４５°）値が８以上３５以下であり、
入射角４５°受光角１５°における光輝強度Ｓｉ（１５°）値が１以上１８以下であり、入射角４５°受光角２５°におけるＬ＊（２５°）値が５以上２５以下である、
複層塗膜の形成方法。
［５］
上記複層塗膜の形成は、被塗物に、第１塗料組成物、第２塗料組成物およびクリヤー塗料組成物をウェットオンウェットで順次塗装して、複層塗膜を形成する方法である、
［４］に記載の複層塗膜の形成方法。
［６］
［１］～［３］いずれかに記載の複層塗膜を有する物品。 In order to solve the above problems, the present invention provides the following aspects.
[1]
A multilayer coating film having a first coating film, a second coating film and a clear coating film in this order,
The first coating film is a cured coating film of a first coating composition containing a first coating film-forming resin and a bright pigment,
The second coating is a cured coating of a second coating composition containing a second coating film-forming resin and a color pigment,
The bright pigment contained in the first coating film contains a scale-like aluminum pigment,
The content of the coloring pigment contained in the second coating is in the range of 1.5 to 6 parts by mass with respect to 100 parts by mass of the resin solid content contained in the coating,
The multilayer coating film is
The bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less,
The brightness intensity Si (15 °) value at an incident angle of 45 ° and a light receiving angle of 15 ° is 1 or more and 18 or less, and the L * (25 °) value at an incident angle of 45 ° and a light receiving angle of 25 ° is 5 or more and 25 or less.
Multi-layer coating.
[2]
The film thickness of the first coating film is in the range of 3 to 13 μm,
The content of the scale-like aluminum pigment contained in the first coating film is in the range of 3 to 13 parts by mass with respect to 100 parts by mass of the resin solid content contained in the coating film.
The multilayer coating film according to [1].
[3]
The multilayer coating film is
The luminous intensity Si (45 °) value at an incident angle of 45 ° and a light receiving angle of 45 ° is 1 or more and 17 or less, and the L * (45 °) value at an incident angle of 45 ° and a light receiving angle of 45 ° is 2 or more and 7 or less.
The multilayer coating film according to [1] or [2].
[4]
A method of sequentially coating a first coating composition, a second coating composition and a clear coating composition on an object to form a multilayer coating film,
The first coating composition contains a first coating film-forming resin and a bright pigment,
The second coating composition comprises a second film-forming resin and a color pigment,
The bright pigment contained in the first coating composition includes a scale-like aluminum pigment,
The content of the color pigment contained in the second coating composition is in the range of 1.5 to 6 parts by mass with respect to 100 parts by mass of the resin solid content contained in the second coating composition,
The multilayer coating film is
The bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less,
The brightness intensity Si (15 °) value at an incident angle of 45 ° and a light receiving angle of 15 ° is 1 or more and 18 or less, and the L * (25 °) value at an incident angle of 45 ° and a light receiving angle of 25 ° is 5 or more and 25 or less.
A method for forming a multilayer coating film.
[5]
The formation of the multilayer coating film is a method in which the first coating composition, the second coating composition and the clear coating composition are successively applied wet-on-wet to the object to be coated to form a multilayer coating film. ,
The method for forming a multilayer coating film according to [4].
[6]
An article having the multilayer coating film according to any one of [1] to [3].
本開示によれば、黒色塗膜と認識されるほどに明度および彩度が低い一方で、輝度が認識される複層塗膜を形成することができる。
According to the present disclosure, it is possible to form a multi-layer coating film that has low brightness and chroma to the extent that it can be recognized as a black coating film, while having recognizable brightness.
本件発明者らは、意匠性に優れる塗色の塗膜の開発を目的として研究を行ってきた。この中で、一般に高級感があると認識される黒色の範囲で、特異的な外観を有する塗膜の開発を目的として、黒色塗膜と認識されるほどに明度および彩度が低い一方で輝度が認識される塗膜を形成する手法を検討してきた。
The inventors have been conducting research with the aim of developing paint films with excellent design properties. Among these, in the range of black generally recognized as a high-class feeling, with the aim of developing a coating film with a unique appearance, brightness and saturation are low enough to be recognized as a black coating film, but luminance I have been studying the method of forming a coating film that is recognized.
塗膜に輝度を持たせる手法の１つとして、例えばアルミニウム顔料などの光輝性顔料を塗膜に加える手法がある。しかしながら、塗膜に単にアルミニウム顔料を加える場合は、アルミニウム顔料自体の色味（銀色）が加わることにより明度が高くなってしまう。このような塗膜は、いわゆるメタリック調といわれるグレー色の塗膜となる。一方で、例えば光輝性顔料としてマイカを塗膜に加える場合は、塗膜全体に白濁のような濁りが生じてしまい、黒色感が低下してしまう。このように、黒色塗膜において輝度が視認できる塗膜を形成することは困難であった。
One of the methods for giving brightness to the coating film is to add luster pigments such as aluminum pigments to the coating film. However, when simply adding an aluminum pigment to a coating film, the lightness increases due to the addition of the tint (silver) of the aluminum pigment itself. Such a coating film becomes a so-called metallic gray coating film. On the other hand, for example, when mica is added as a bright pigment to the coating film, turbidity such as white turbidity occurs in the entire coating film, resulting in a decrease in black feeling. As described above, it was difficult to form a coating film in which the luminance can be visually recognized in the black coating film.
本発明者らは、上記課題を解決することを目的として研究を行った。そして、特定の第１塗膜および第２塗膜を組み合わせることにより、黒色塗膜と認識されるほどに明度および彩度が低い一方で輝度が認識される複層塗膜を提供することができることを、実験により見出し、本件発明を完成するに至った。以下、第１塗膜を形成する第１塗料組成物、第２塗膜を形成する第２塗料組成物について順次記載する。
The inventors conducted research with the aim of solving the above problems. And, by combining the specific first coating film and the second coating film, it is possible to provide a multi-layer coating film that has low brightness and saturation to the extent that it can be recognized as a black coating film, but has recognizable brightness. was found by experiments, and the present invention was completed. Hereinafter, the first coating composition forming the first coating film and the second coating composition forming the second coating film will be described in order.
第１塗料組成物
本開示における第１塗膜は、第１塗料組成物の硬化塗膜である。上記第１塗料組成物は、第１塗膜形成樹脂および光輝性顔料を含む塗料組成物である。 First Coating Composition The first coating in the present disclosure is a cured coating of the first coating composition. The first coating composition is a coating composition containing a first coating film-forming resin and a bright pigment.
本開示における第１塗膜は、第１塗料組成物の硬化塗膜である。上記第１塗料組成物は、第１塗膜形成樹脂および光輝性顔料を含む塗料組成物である。 First Coating Composition The first coating in the present disclosure is a cured coating of the first coating composition. The first coating composition is a coating composition containing a first coating film-forming resin and a bright pigment.
上記第１塗料組成物は第１塗膜形成樹脂を含む。第１塗膜形成樹脂として例えば、アクリル樹脂、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、フッ素樹脂、シリコーン樹脂などが挙げられる。上記第１塗料組成物は、水性塗料組成物であってもよく、溶剤型塗料組成物であってもよい。
The first coating composition contains a first coating film-forming resin. Examples of the first coating film-forming resin include acrylic resins, polyester resins, polyurethane resins, epoxy resins, fluorine resins, and silicone resins. The first coating composition may be a water-based coating composition or a solvent-based coating composition.
上記第１塗料組成物が水性塗料組成物である場合は、第１塗膜形成樹脂として例えば、アクリル樹脂エマルション（アクリルシリコーン樹脂エマルション、アクリルウレタン樹脂エマルションなども含む）、アクリル樹脂ディスパージョン（アクリルシリコーン樹脂ディスパージョン、アクリルウレタン樹脂ディスパージョンなども含む）、水溶性アクリル樹脂、ポリエステル樹脂ディスパージョン、ポリウレタン樹脂ディスパージョン、エポキシ樹脂ディスパージョンなどを含むのが好ましい。これらの樹脂は１種のみを単独で用いてもよく、２種またはそれ以上を併用してもよい。上記樹脂は、当業者において通常用いられる方法により調製することができる。上記樹脂として市販品を用いてもよい。
When the first coating composition is a water-based coating composition, examples of the first coating film-forming resin include acrylic resin emulsions (including acrylic silicone resin emulsions, acrylic urethane resin emulsions, etc.), acrylic resin dispersions (acrylic silicone resin dispersions, acrylic urethane resin dispersions, etc.), water-soluble acrylic resins, polyester resin dispersions, polyurethane resin dispersions, epoxy resin dispersions, etc. are preferably included. These resins may be used alone or in combination of two or more. The above resin can be prepared by a method commonly used by those skilled in the art. A commercially available product may be used as the resin.
好ましい態様として例えば、アクリル樹脂エマルションおよび水溶性アクリル樹脂のうちいずれかまたは両方を用いる態様、アクリル樹脂エマルション、水溶性アクリル樹脂およびポリエステル樹脂ディスパージョンを用いる態様、アクリル樹脂エマルション、水溶性アクリル樹脂およびポリウレタン樹脂ディスパージョンを用いる態様などが挙げられる。
Preferred embodiments include, for example, an embodiment using either or both of an acrylic resin emulsion and a water-soluble acrylic resin, an embodiment using an acrylic resin emulsion, a water-soluble acrylic resin and a polyester resin dispersion, an acrylic resin emulsion, a water-soluble acrylic resin and a polyurethane. Examples include a mode using a resin dispersion.
アクリル樹脂エマルションは、例えば、α，β－エチレン性不飽和モノマー混合物の乳化重合によって調製することができる。アクリル樹脂エマルションの調製に用いられる好ましいα，β－エチレン性不飽和モノマーとして、例えば、（メタ）アクリル酸エステル、酸基を有するα，β－エチレン性不飽和モノマーおよび水酸基を有するα，β－エチレン性不飽和モノマーが挙げられる。
An acrylic resin emulsion can be prepared, for example, by emulsion polymerization of a mixture of α,β-ethylenically unsaturated monomers. Preferable α,β-ethylenically unsaturated monomers used for preparing the acrylic resin emulsion include, for example, (meth)acrylic acid esters, α,β-ethylenically unsaturated monomers having an acid group and α,β-ethylenically unsaturated monomers having a hydroxyl group. Ethylenically unsaturated monomers can be mentioned.
上記（メタ）アクリル酸エステルとして、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸フェニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ｔ－ブチルシクロヘキシル、（メタ）アクリル酸ジシクロペンタジエニル、（メタ）アクリル酸ジヒドロジシクロペンタジエニルなどが挙げられる。なお、本明細書において（メタ）アクリル酸エステルとはアクリル酸エステルとメタアクリル酸エステルとの両方を意味するものとする。
Examples of the (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylic acid. t-butyl acid, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butyl (meth)acrylate cyclohexyl, dicyclopentadienyl (meth)acrylate, dihydrodicyclopentadienyl (meth)acrylate and the like. In this specification, (meth)acrylic acid ester means both acrylic acid ester and methacrylic acid ester.
酸基を有するα，β－エチレン性不飽和モノマーとして、アクリル酸、メタクリル酸、クロトン酸、２－アクリロイルオキシエチルフタル酸、２－アクリロイルオキシエチルコハク酸、ω－カルボキシ－ポリカプロラクトンモノ（メタ）アクリレート、イソクロトン酸、α－ハイドロ－ω－（（１－オキソ－２－プロペニル）オキシ）ポリ（オキシ（１－オキソ－１，６－ヘキサンジイル））、マレイン酸、フマル酸、イタコン酸、３－ビニルサリチル酸、３－ビニルアセチルサリチル酸、２－アクリルアミド－２－メチルプロパンスルホン酸、ｐ－ヒドロキシスチレン、２，４－ジヒドロキシ－４’－ビニルベンゾフェノンなどが挙げられる。
α,β-ethylenically unsaturated monomers having an acid group include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid, ω-carboxy-polycaprolactone mono(meth) Acrylates, isocrotonic acid, α-hydro-ω-((1-oxo-2-propenyl)oxy)poly(oxy(1-oxo-1,6-hexanediyl)), maleic acid, fumaric acid, itaconic acid, 3 -vinylsalicylic acid, 3-vinylacetylsalicylic acid, 2-acrylamido-2-methylpropanesulfonic acid, p-hydroxystyrene, 2,4-dihydroxy-4'-vinylbenzophenone and the like.
水酸基を有するα，β－エチレン性不飽和モノマーとして、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、アリルアルコール、メタリルアルコール、および、これらとε－カプロラクトンとの付加物などが挙げられる。これらの中で好ましいものは、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ヒドロキシエチル、および、これらとε－カプロラクトンとの付加物である。
As α,β-ethylenically unsaturated monomers having a hydroxyl group, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, allyl alcohol, methallyl alcohol, and these and ε - adducts with caprolactone, and the like. Preferred among these are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylate, and addition of these with ε-caprolactone It is a thing.
上記α，β－エチレン性不飽和モノマー混合物はさらに、その他のα，β－エチレン性不飽和モノマーを用いてもよい。その他のα，β－エチレン性不飽和モノマーとしては、重合性アミド化合物、重合性芳香族化合物、重合性ニトリル、重合性アルキレンオキシド化合物、多官能ビニル化合物、重合性アミン化合物、α－オレフィン、ジエン、重合性カルボニル化合物、重合性アルコキシシリル化合物、重合性のその他の化合物を挙げることができる。上記α，β－エチレン性不飽和モノマーは目的に併せて、必要に応じて種々選択することができる。
The above α,β-ethylenically unsaturated monomer mixture may further contain other α,β-ethylenically unsaturated monomers. Other α,β-ethylenically unsaturated monomers include polymerizable amide compounds, polymerizable aromatic compounds, polymerizable nitriles, polymerizable alkylene oxide compounds, polyfunctional vinyl compounds, polymerizable amine compounds, α-olefins and dienes. , polymerizable carbonyl compounds, polymerizable alkoxysilyl compounds, and other polymerizable compounds. Various α,β-ethylenically unsaturated monomers can be selected depending on the purpose.
アクリル樹脂エマルションは、上記α，β－エチレン性不飽和モノマー混合物を乳化重合して調製することができる。乳化重合は、特に限定されず、通常の方法を用いて行うことができる。具体的には、例えば、水、または必要に応じてアルコール、エーテル（例えば、ジプロピレングリコールメチルエーテル、プロピレングリコールメチルエーテルなど）などのような有機溶媒を含む水性媒体中に乳化剤を溶解させ、加熱撹拌下、上記α，β－エチレン性不飽和モノマー混合物および重合開始剤を滴下することにより行うことができる。乳化剤と水とを用いて予め乳化したα，β－エチレン性不飽和モノマー混合物を同様に滴下してもよい。
The acrylic resin emulsion can be prepared by emulsion polymerization of the above α,β-ethylenically unsaturated monomer mixture. Emulsion polymerization is not particularly limited and can be carried out using a usual method. Specifically, for example, an emulsifier is dissolved in an aqueous medium containing water or, if necessary, an organic solvent such as alcohol, ether (e.g., dipropylene glycol methyl ether, propylene glycol methyl ether, etc.), and heated. It can be carried out by dropping the α,β-ethylenically unsaturated monomer mixture and the polymerization initiator under stirring. An α,β-ethylenically unsaturated monomer mixture pre-emulsified with an emulsifier and water may likewise be added dropwise.
上記重合開始剤、乳化剤は、当業者に通常使用されているものを用いることができる。必要に応じて、ラウリルメルカプタンのようなメルカプタンおよびα－メチルスチレンダイマーなどのような連鎖移動剤を用いて分子量を調節してもよい。反応温度、反応時間などは、当業者に通常用いられる範囲で適宜選択することができる。反応により得られたアクリル樹脂エマルションは、必要に応じて塩基で中和してもよい。
As the polymerization initiator and emulsifier, those commonly used by those skilled in the art can be used. If desired, mercaptans such as lauryl mercaptan and chain transfer agents such as α-methylstyrene dimer may be used to control molecular weight. The reaction temperature, reaction time and the like can be appropriately selected within the ranges commonly used by those skilled in the art. The acrylic resin emulsion obtained by the reaction may be neutralized with a base if necessary.
上記アクリル樹脂エマルションは、数平均分子量の下限が３０００であることが好ましい。また、上記アクリル樹脂エマルションは、水酸基価（固形分水酸基価）が下限２０ｍｇＫＯＨ／ｇ上限１８０ｍｇＫＯＨ／ｇを有することが好ましく、酸価（固形分酸基価）が下限１ｍｇＫＯＨ／ｇ上限８０ｍｇＫＯＨ／ｇであることが好ましい。
The lower limit of the number average molecular weight of the acrylic resin emulsion is preferably 3,000. Further, the acrylic resin emulsion preferably has a hydroxyl value (solid content hydroxyl value) with a lower limit of 20 mgKOH/g and an upper limit of 180 mgKOH/g, and an acid value (solid content acid value) with a lower limit of 1 mgKOH/g and an upper limit of 80 mgKOH/g. Preferably.
本明細書において数平均分子量は、ポリスチレンを標準とするＧＰＣ法において決定される値である。本明細書において酸価および水酸基価は、ＪＩＳの規定に基づいて、調製に用いられるモノマー組成から算出される値である。
As used herein, the number average molecular weight is a value determined by the GPC method using polystyrene as a standard. As used herein, the acid value and hydroxyl value are values calculated from the composition of monomers used for preparation based on JIS regulations.
水溶性アクリル樹脂は、例えば、上記アクリル樹脂エマルションの調製に用いることができるα，β－エチレン性不飽和モノマーを含むモノマー混合物を溶液重合し、塩基性化合物により水溶化することにより調製することができる。アクリル樹脂ディスパージョンは、例えば、上記アクリル樹脂エマルションの調製に用いることができるα，β－エチレン性不飽和モノマーを含むモノマー混合物を溶液重合し、塩基性化合物でディスパージョン化することにより、調製することができる。
The water-soluble acrylic resin can be prepared, for example, by solution-polymerizing a monomer mixture containing an α,β-ethylenically unsaturated monomer that can be used for the preparation of the acrylic resin emulsion, and solubilizing it with a basic compound. can. The acrylic resin dispersion is prepared, for example, by solution-polymerizing a monomer mixture containing an α,β-ethylenically unsaturated monomer that can be used for the preparation of the acrylic resin emulsion, followed by dispersion with a basic compound. be able to.
ポリエステル樹脂ディスパージョンは、例えば、多価アルコール成分と多塩基酸成分とを縮合し、塩基性化合物でディスパージョン化することにより、調製することができる。ポリウレタン樹脂ディスパージョンは、例えば、ポリオール化合物と、分子内に活性水素基と親水基を有する化合物と、有機ポリイソシアネートとを、必要により鎖伸長剤および重合停止剤を用いてポリマー化し、得られたポリマーを水中に溶解または分散することによって、調製することができる。
A polyester resin dispersion can be prepared, for example, by condensing a polyhydric alcohol component and a polybasic acid component, followed by dispersion with a basic compound. The polyurethane resin dispersion is obtained by polymerizing, for example, a polyol compound, a compound having an active hydrogen group and a hydrophilic group in the molecule, and an organic polyisocyanate using a chain extender and a polymerization terminator if necessary. It can be prepared by dissolving or dispersing the polymer in water.
上記第１塗料組成物が水性塗料組成物である場合は、上記第１塗膜形成樹脂に対して反応する硬化剤を用いるのが好ましい。このような硬化剤は、上記第１塗膜形成樹脂と反応して塗膜を形成する、塗膜形成成分である。硬化剤として、メラミン樹脂、ブロックイソシアネート化合物、エポキシ化合物、アジリジン化合物、カルボジイミド化合物、オキサゾリン化合物、金属イオンなどを用いることができる。これらは１種のみを単独で用いてもよく、２種またはそれ以上を併用してもよい。上記成分は、当業者において通常用いられる方法により調製することができる。上記成分として市販品を用いてもよい。硬化剤として、メラミン樹脂およびブロックイソシアネート化合物のいずれかまたは両方を用いるのがより好ましい。
When the first coating composition is a water-based coating composition, it is preferable to use a curing agent that reacts with the first coating film-forming resin. Such curing agents are film-forming components that react with the first film-forming resin to form a film. As curing agents, melamine resins, blocked isocyanate compounds, epoxy compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, metal ions, and the like can be used. These may be used alone or in combination of two or more. The above components can be prepared by methods commonly used by those skilled in the art. You may use a commercial item as said component. It is more preferable to use either or both of a melamine resin and a blocked isocyanate compound as a curing agent.
メラミン樹脂は、水溶性メラミン樹脂および／または非水溶性メラミン樹脂を用いることができる。メラミン樹脂は、メラミン核（トリアジン核）の周囲に３個の窒素原子を介して水素原子または置換基（アルキルエーテル基、メチロール基など）が結合した構造を含む。上記メラミン樹脂は、一般的には、複数のメラミン核が互いに結合した多核体により構成されるものである。一方で上記メラミン樹脂は１個のメラミン核からなる単核体であってもよい。
A water-soluble melamine resin and/or a water-insoluble melamine resin can be used as the melamine resin. The melamine resin has a structure in which hydrogen atoms or substituents (alkyl ether groups, methylol groups, etc.) are bonded around a melamine nucleus (triazine nucleus) via three nitrogen atoms. The melamine resin is generally composed of a polynuclear body in which a plurality of melamine nuclei are bonded to each other. On the other hand, the melamine resin may be mononuclear, consisting of one melamine nucleus.
上記メラミン樹脂として市販品を用いてもよい。市販品の具体例として、例えば、Ａｌｌｎｅｘ社製のサイメルシリーズ（商品名）、具体的には、サイメル２０２、サイメル２０４、サイメル２１１、サイメル２３２、サイメル２３５、サイメル２３６、サイメル２３８、サイメル２５０、サイメル２５１、サイメル２５４、サイメル２６６、サイメル２６７、サイメル２７２、サイメル２８５、サイメル３０１、サイメル３０３、サイメル３２５、サイメル３２７、サイメル３５０、サイメル３７０、サイメル７０１、サイメル７０３、サイメル１１４１；および、三井化学社製のユーバン（商品名）シリーズなどが挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。
A commercially available product may be used as the melamine resin. Specific examples of commercially available products include Cymel series (trade name) manufactured by Allnex, specifically Cymel 202, Cymel 204, Cymel 211, Cymel 232, Cymel 235, Cymel 236, Cymel 238, Cymel 250, Cymel 251, Cymel 254, Cymel 266, Cymel 267, Cymel 272, Cymel 285, Cymel 301, Cymel 303, Cymel 325, Cymel 327, Cymel 350, Cymel 370, Cymel 701, Cymel 703, Cymel 1141; and Mitsui Chemicals, Inc. Yuban (trade name) series manufactured by the company. These may be used alone or in combination of two or more.
ブロックイソシアネート化合物は、トリメチレンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネートなどからなるポリイソシアネートに、活性水素を有するブロック剤を付加させることによって、調製することができる。このようなブロックイソシアネート樹脂は、加熱によりブロック剤が解離してイソシアネート基が発生し、上記樹脂成分中の官能基と反応して硬化する。
A blocked isocyanate compound can be prepared by adding a blocking agent having active hydrogen to a polyisocyanate composed of trimethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, or the like. In such a blocked isocyanate resin, the blocking agent is dissociated by heating to generate an isocyanate group, which reacts with the functional group in the resin component and is cured.
硬化剤の量は、塗料樹脂固形分質量（上記塗膜形成樹脂および硬化剤を含む塗膜形成成分の固形分質量）を基準にして１０～８０質量％であるのが好ましく、１５～６０質量％であるのがより好ましい。
The amount of the curing agent is preferably 10 to 80% by mass, preferably 15 to 60% by mass, based on the solid content of the coating resin (the solid content of the coating film-forming components including the coating film-forming resin and the curing agent). % is more preferred.
上記第１塗料組成物は、光輝性顔料を含む。そして本開示においては、第１塗料組成物に含まれる光輝性顔料は鱗片状アルミニウム顔料を含む。
The first paint composition contains a luster pigment. In the present disclosure, the luster pigment contained in the first coating composition contains a scale-like aluminum pigment.
上記鱗片状アルミニウム顔料は、平均粒子径が４～２５μｍであるのが好ましく、８～１８μｍであるのがより好ましい。上記鱗片状アルミニウム顔料はまた、平均厚さが０．０１～０．１μｍであるのが好ましく、０．０４～０．０８μｍであるのがより好ましい。鱗片状アルミニウム顔料の平均粒子径および平均厚さが上記条件を満たすことによって、第１塗膜に良好な緻密感がもたらされ、これにより、複層塗膜において目的とする意匠を好適に得ることができる利点がある。
The scale-like aluminum pigment preferably has an average particle size of 4 to 25 µm, more preferably 8 to 18 µm. The scale-like aluminum pigment also preferably has an average thickness of 0.01 to 0.1 μm, more preferably 0.04 to 0.08 μm. When the average particle size and average thickness of the scale-like aluminum pigment satisfy the above conditions, the first coating film has a good dense feeling, thereby suitably obtaining the desired design in the multilayer coating film. There are advantages that can be
上記鱗片状アルミニウム顔料の平均粒子径は、平均長径を意味する。平均粒子径の測定は、鱗片状アルミニウム顔料を、形状解析レーザーマイクロスコープ（例えばキーエンス社製 ＶＫ－Ｘ ２５０など）を用いて観察し、任意に選択した１００個の顔料の最大長さ（長径）の数平均値を求めることによって測定することができる。
The average particle diameter of the scale-like aluminum pigment means the average major diameter. The average particle size is measured by observing the scaly aluminum pigment using a shape analysis laser microscope (eg, Keyence VK-X 250, etc.), and measuring the maximum length (major diameter) of 100 arbitrarily selected pigments. can be measured by taking the number average of
上記鱗片状アルミニウム顔料の平均厚さは、上記鱗片状アルミニウム顔料を含む塗膜を形成し、得られた塗膜の断面を、透過型電子顕微鏡（ＴＥＭ）を用いて測定して、測定値の平均値を求めることによって測定することができる。
The average thickness of the scale-like aluminum pigment is obtained by forming a coating film containing the scale-like aluminum pigment, and measuring the cross section of the obtained coating film using a transmission electron microscope (TEM). It can be measured by taking an average value.
上記鱗片状アルミニウム顔料はまた、アスペクト比（顔料の最大径の平均／顔料の厚みの平均）が５０～３００の範囲内であるのが好ましく、１００～２００の範囲内であるのが好ましい。
The scale-like aluminum pigment also preferably has an aspect ratio (average maximum diameter of pigment/average thickness of pigment) in the range of 50 to 300, more preferably in the range of 100 to 200.
上記鱗片状アルミニウム顔料は、必要に応じて表面処理が施されていてもよい。アルミニウム顔料に施すことができる表面処理として、例えば、金属酸化物系化合物を用いた表面処理、リン化合物を用いた表面処理、アミン化合物を用いた表面処理、シラン化合物を用いた表面処理などが挙げられる。
The scale-like aluminum pigment may be surface-treated as necessary. Examples of surface treatments that can be applied to aluminum pigments include surface treatments using metal oxide compounds, surface treatments using phosphorus compounds, surface treatments using amine compounds, and surface treatments using silane compounds. be done.
上記金属酸化物系化合物として、例えば、構成金属として少なくとも遷移金属元素を含む金属酸化物及びそのアルカリ金属塩並びにそのアンモニウム塩などが挙げられる。具体的には、三酸化モリブデン、モリブデン酸、モリブデン酸アルカリ金属塩、モリブデン酸アンモニウム塩、バナジン酸、バナジン酸アルカリ金属塩、バナジン酸アンモニウム塩等が挙げられる。なお、前記アルカリ金属としては、特に限定されるものではないが、例えばナトリウム、カリウム等が挙げられる。中でも、前記金属酸化物系化合物としては、モリブデン酸、モリブデン酸アルカリ金属塩、モリブデン酸アンモニウム塩、バナジン酸、バナジン酸アルカリ金属塩及びバナジン酸アンモニウム塩からなる群より選ばれる１種または２種以上の金属酸化物系化合物が用いられるのが好ましい。
Examples of the metal oxide compounds include metal oxides containing at least a transition metal element as a constituent metal, alkali metal salts thereof, and ammonium salts thereof. Specific examples include molybdenum trioxide, molybdic acid, alkali metal molybdate, ammonium molybdate, vanadic acid, alkali metal vanadate, and ammonium vanadate. Examples of the alkali metal include, but are not limited to, sodium and potassium. Among them, the metal oxide compound is one or more selected from the group consisting of molybdic acid, alkali metal molybdate, ammonium molybdate, vanadic acid, alkali metal vanadate and ammonium vanadate. is preferably used.
上記リン化合物として、例えば、有機リン酸エステル、有機亜リン酸エステル、有機ホスホン酸、およびこれらの化合物のアミン塩などが挙げられる。これらのリン化合物は１種を単独で用いてもよく、２種またはそれ以上を併用してもよい。
Examples of the phosphorus compounds include organic phosphates, organic phosphites, organic phosphonic acids, and amine salts of these compounds. One of these phosphorus compounds may be used alone, or two or more thereof may be used in combination.
上記アミン化合物として、例えば、直鎖状または分枝状一級アミン、直鎖状または分枝状二級アミン、直鎖状または分枝状三級アミン、脂環式一級アミン、脂環式二級アミン、脂環式三級アミン、芳香族基含有一級アミン、芳香族基含有二級アミン、芳香族基含有三級アミンなどが挙げられる。これらのアミン化合物は、必要に応じて置換基（例えば水酸基など）を有してもよい。これらのアミン化合物は、１種を単独で用いてもよく、２種またはそれ以上を併用してもよい。
Examples of the amine compound include linear or branched primary amines, linear or branched secondary amines, linear or branched tertiary amines, alicyclic primary amines, alicyclic secondary Examples include amines, alicyclic tertiary amines, aromatic group-containing primary amines, aromatic group-containing secondary amines, and aromatic group-containing tertiary amines. These amine compounds may have a substituent (for example, a hydroxyl group, etc.) as needed. These amine compounds may be used singly or in combination of two or more.
上記シラン化合物として、例えば、アルコキシシシラン化合物、ビニル基含有シランカップリング剤、エポキシ基含有シランカップリング剤、スチリル基含有シランカップリング剤、（メタ）アクリル基含有シランカップリング剤、アミノ基含有シランカップリング剤、イソシアネート基含有シランカップリング剤、ウレイド基含有シランカップリング剤、メルカプト基含有シランカップリング剤、酸無水物基含有シランカップリング剤、およびこれらの部分縮合物などが挙げられる。これらのシラン化合物は、１種を単独で用いてもよく、２種またはそれ以上を併用してもよい。
Examples of the silane compound include alkoxysilane compounds, vinyl group-containing silane coupling agents, epoxy group-containing silane coupling agents, styryl group-containing silane coupling agents, (meth)acrylic group-containing silane coupling agents, amino group-containing Examples include silane coupling agents, isocyanate group-containing silane coupling agents, ureido group-containing silane coupling agents, mercapto group-containing silane coupling agents, acid anhydride group-containing silane coupling agents, and partial condensates thereof. These silane compounds may be used singly or in combination of two or more.
上記表面処理は、当業者において通常用いられる処理条件により行うことができる。上記表面処理は１種のみを行ってもよく、２種またはそれ以上を併用してもよい。
The above surface treatment can be carried out under treatment conditions commonly used by those skilled in the art. Only one kind of the surface treatment may be carried out, or two or more kinds thereof may be used in combination.
特に、上記第１塗料組成物に含まれる光輝性顔料が鱗片状アルミニウム顔料であり、そして平均粒子径が例えば４～２５μｍ、より好ましくは８～１８μｍである場合は、上記表面処理が施されていることによって、形成される複層塗膜の塗膜外観を損なうことなく、第１塗料組成物の安定性がより良好となるなどの利点がある。より具体的には、本開示の複層塗膜において、光輝性顔料として上記鱗片状アルミニウム顔料を用いることにより、白ぼけおよび有彩色などの色味が感じられず、黒色塗膜と認識されるほどに明度および彩度が低く、その一方で複層塗膜として輝度が認識できる、複層塗膜を好適に形成することができる利点がある。
In particular, when the luster pigment contained in the first coating composition is a scaly aluminum pigment and has an average particle size of, for example, 4 to 25 μm, more preferably 8 to 18 μm, the surface treatment is applied. There is an advantage that the stability of the first coating composition is improved without impairing the coating film appearance of the formed multi-layer coating film. More specifically, in the multi-layer coating film of the present disclosure, by using the scale-like aluminum pigment as the bright pigment, the color such as white blur and chromatic color is not felt, and it is recognized as a black coating film. It has the advantage of being able to suitably form a multi-layered coating film having a brightness and chroma as low as possible, while allowing the brightness to be recognized as a multi-layered coating film.
上記鱗片状アルミニウム顔料として市販品を用いてもよい。市販品として例えば、
東洋アルミニウム社製アルペースト４６シリーズ、９７シリーズのうち例えば０５１９、０１シリーズのうち例えば０１－０６５１など；旭化成社製アルミペーストＦＤシリーズなど；エカルト社製Ｍｅｔａｌｌｕｘ ４８６０など；が挙げられる。 A commercially available product may be used as the scale-like aluminum pigment. As a commercial product, for example,
Examples include Alpaste 46 series and 97 series manufactured by Toyo Aluminum Co., Ltd., such as 0519 and 01 series, such as 01-0651; Aluminum Paste FD series manufactured by Asahi Kasei; and Metallux 4860 manufactured by Ecarto.
東洋アルミニウム社製アルペースト４６シリーズ、９７シリーズのうち例えば０５１９、０１シリーズのうち例えば０１－０６５１など；旭化成社製アルミペーストＦＤシリーズなど；エカルト社製Ｍｅｔａｌｌｕｘ ４８６０など；が挙げられる。 A commercially available product may be used as the scale-like aluminum pigment. As a commercial product, for example,
Examples include Alpaste 46 series and 97 series manufactured by Toyo Aluminum Co., Ltd., such as 0519 and 01 series, such as 01-0651; Aluminum Paste FD series manufactured by Asahi Kasei; and Metallux 4860 manufactured by Ecarto.
上記光輝性顔料の量は、第１塗膜形成樹脂の樹脂固形分１００質量部に対して３～１３質量部の範囲内であるのが好ましく、８～１１質量部の範囲内であるのがより好ましい。
The amount of the bright pigment is preferably in the range of 3 to 13 parts by mass, more preferably in the range of 8 to 11 parts by mass, based on 100 parts by mass of the resin solid content of the first coating film-forming resin. more preferred.
上記第１塗料組成物に含まれる光輝性顔料は、必要に応じて、鱗片状アルミニウム顔料以外の光輝性顔料、例えば、銅、亜鉛、鉄、ニッケル、スズ、酸化アルミニウムおよびこれらの合金などの金属製光輝性顔料、および、干渉マイカ顔料、ホワイトマイカ顔料、グラファイト顔料、ガラスフレーク顔料など、を含んでもよい。但しこれらの鱗片状アルミニウム顔料以外の光輝性顔料の含有量は、本開示の発明の効果が損なわれない範囲であることを条件とする。本開示の発明においては、上記第１塗料組成物に含まれる光輝性顔料は、鱗片状アルミニウム顔料であるのが、得られる複層塗膜の意匠性の点から好ましい。
The luster pigment contained in the first coating composition is, if necessary, luster pigments other than scale-like aluminum pigments, e.g., metals such as copper, zinc, iron, nickel, tin, aluminum oxide and alloys thereof luster pigments, and interference mica pigments, white mica pigments, graphite pigments, glass flake pigments, and the like. However, the content of the luster pigment other than these scale-like aluminum pigments is subject to the condition that the effects of the invention of the present disclosure are not impaired. In the invention of the present disclosure, the luster pigment contained in the first coating composition is preferably a scale-like aluminum pigment from the viewpoint of the design of the obtained multilayer coating film.
上記第１塗料組成物は、上記光輝性顔料以外にも、必要に応じた他の顔料を含んでもよい。但しこれらの他の顔料は、上記第１塗膜の性能を損なわない量であることを条件とする。他の顔料として、例えば、着色顔料、体質顔料などが挙げられる。体質顔料として、例えば、炭酸カルシウム、硫酸バリウム、クレー、タルクなどを挙げることができる。上記顔料はさらに、必要に応じて防錆顔料を含んでもよい。
The first paint composition may contain other pigments as necessary in addition to the bright pigment. However, these other pigments should be in amounts that do not impair the performance of the first coating film. Other pigments include, for example, coloring pigments and extender pigments. Examples of extender pigments include calcium carbonate, barium sulfate, clay, and talc. The pigment may further contain an antirust pigment, if desired.
着色顔料として、各種無機着色顔料および有機着色顔料を用いることができる。なお本明細書において「着色顔料」は、有彩色の着色顔料および無彩色の着色顔料を含む。
着色顔料として、例えば、カーボンブラック、黒鉛（グラファイト）、鉄黒（アイアンブラック）、鉄クロムやビスマスマンガン等の複合金属酸化物、ペリレン系黒色顔料、アゾメチアゾ系顔料などの黒色系顔料；
紺青、群青、コバルトブルー、銅フタロシアニンブルー、インダンスロンブルーなどの青色系顔料；
黄鉛、合成黄色酸化鉄、ビスマスバナデート、チタンイエロー、亜鉛黄（ジンクエロー）、オーカー、モノアゾイエロー、ジスアゾイエロー、イソインドリノンイエロー、金属錯塩アゾイエロー、キノフタロンイエロー、ベンズイミダゾロンイエローなどの黄色系顔料；
酸化鉄、透明酸化鉄、モノアゾレッド、キナクリドンレッド、アゾレーキ（Ｍｎ塩）、ペリレンレッド、ペリレンマルーンなどの赤色系顔料；
キナクリドンマゼンタ、アンサンスロンオレンジ、ジアンスラキノニルレッド、ピラゾロンオレンジ、ベンズイミダゾロンオレンジ、ジケトピロロピロールクロムバーミリオンなどの橙色系顔料；
塩素化フタロシアニングリーン、臭素化フタロシアニングリーンなどの緑色系顔料；
ジオキサジンバイオレット、ペリレンバイオレットなどの紫色系顔料；
２酸化チタンなどの白色系顔料；
などを挙げることができる。 Various inorganic coloring pigments and organic coloring pigments can be used as the coloring pigment. As used herein, the term “coloring pigment” includes chromatic coloring pigments and achromatic coloring pigments.
Examples of coloring pigments include black pigments such as carbon black, graphite, iron black, composite metal oxides such as iron chromium and bismuth manganese, perylene black pigments, and azomethiazol pigments;
Blue pigments such as Prussian Blue, Ultramarine Blue, Cobalt Blue, Copper Phthalocyanine Blue, Indanthrone Blue;
Yellows such as yellow lead, synthetic yellow iron oxide, bismuth vanadate, titanium yellow, zinc yellow, ocher, monoazo yellow, disazo yellow, isoindolinone yellow, metal complex salt azo yellow, quinophthalone yellow, and benzimidazolone yellow pigment;
Red pigments such as iron oxide, transparent iron oxide, monoazo red, quinacridone red, azo lake (Mn salt), perylene red, and perylene maroon;
orange pigments such as quinacridone magenta, anthrone orange, dianthraquinonyl red, pyrazolone orange, benzimidazolone orange, diketopyrrolopyrrole chromium vermilion;
Green pigments such as chlorinated phthalocyanine green and brominated phthalocyanine green;
purple pigments such as dioxazine violet and perylene violet;
White pigments such as titanium dioxide;
etc. can be mentioned.
着色顔料として、例えば、カーボンブラック、黒鉛（グラファイト）、鉄黒（アイアンブラック）、鉄クロムやビスマスマンガン等の複合金属酸化物、ペリレン系黒色顔料、アゾメチアゾ系顔料などの黒色系顔料；
紺青、群青、コバルトブルー、銅フタロシアニンブルー、インダンスロンブルーなどの青色系顔料；
黄鉛、合成黄色酸化鉄、ビスマスバナデート、チタンイエロー、亜鉛黄（ジンクエロー）、オーカー、モノアゾイエロー、ジスアゾイエロー、イソインドリノンイエロー、金属錯塩アゾイエロー、キノフタロンイエロー、ベンズイミダゾロンイエローなどの黄色系顔料；
酸化鉄、透明酸化鉄、モノアゾレッド、キナクリドンレッド、アゾレーキ（Ｍｎ塩）、ペリレンレッド、ペリレンマルーンなどの赤色系顔料；
キナクリドンマゼンタ、アンサンスロンオレンジ、ジアンスラキノニルレッド、ピラゾロンオレンジ、ベンズイミダゾロンオレンジ、ジケトピロロピロールクロムバーミリオンなどの橙色系顔料；
塩素化フタロシアニングリーン、臭素化フタロシアニングリーンなどの緑色系顔料；
ジオキサジンバイオレット、ペリレンバイオレットなどの紫色系顔料；
２酸化チタンなどの白色系顔料；
などを挙げることができる。 Various inorganic coloring pigments and organic coloring pigments can be used as the coloring pigment. As used herein, the term “coloring pigment” includes chromatic coloring pigments and achromatic coloring pigments.
Examples of coloring pigments include black pigments such as carbon black, graphite, iron black, composite metal oxides such as iron chromium and bismuth manganese, perylene black pigments, and azomethiazol pigments;
Blue pigments such as Prussian Blue, Ultramarine Blue, Cobalt Blue, Copper Phthalocyanine Blue, Indanthrone Blue;
Yellows such as yellow lead, synthetic yellow iron oxide, bismuth vanadate, titanium yellow, zinc yellow, ocher, monoazo yellow, disazo yellow, isoindolinone yellow, metal complex salt azo yellow, quinophthalone yellow, and benzimidazolone yellow pigment;
Red pigments such as iron oxide, transparent iron oxide, monoazo red, quinacridone red, azo lake (Mn salt), perylene red, and perylene maroon;
orange pigments such as quinacridone magenta, anthrone orange, dianthraquinonyl red, pyrazolone orange, benzimidazolone orange, diketopyrrolopyrrole chromium vermilion;
Green pigments such as chlorinated phthalocyanine green and brominated phthalocyanine green;
purple pigments such as dioxazine violet and perylene violet;
White pigments such as titanium dioxide;
etc. can be mentioned.
水性第１塗料組成物は、上記成分に加えて、当業者において通常用いられる添加剤、例えば、表面調整剤、粘性制御剤、増粘剤、酸化防止剤、紫外線防止剤、消泡剤などを含んでもよい。例えば粘性制御剤を用いることによって、チクソトロピー性を付与することができ、塗装作業性を調整することができる。粘性制御剤として、例えば、架橋あるいは非架橋の樹脂粒子、脂肪酸アマイドの膨潤分散体、アマイド系脂肪酸、長鎖ポリアミノアマイドのリン酸塩などのポリアマイド系のもの、酸化ポリエチレンのコロイド状膨潤分散体などのポリエチレン系などのもの、有機酸スメクタイト粘土、モンモリロナイトなどの有機ベントナイト系のものなどを挙げることができる。これらの添加剤を用いる場合は、当業者において通常用いられる量で用いることができる。
In addition to the above components, the water-based first coating composition contains additives commonly used by those skilled in the art, such as surface conditioners, viscosity control agents, thickeners, antioxidants, UV inhibitors, antifoaming agents, and the like. may contain. For example, by using a viscosity control agent, thixotropy can be imparted, and coating workability can be adjusted. Viscosity control agents include, for example, crosslinked or non-crosslinked resin particles, swelling dispersions of fatty acid amides, amide-based fatty acids, polyamides such as phosphates of long-chain polyaminoamides, and colloidal swelling dispersions of polyethylene oxide. , organic acid smectite clay, and organic bentonite-based materials such as montmorillonite. When these additives are used, they can be used in an amount commonly used by those skilled in the art.
上記水性第１塗料組成物は、必要に応じて、上記成分に加えてさらにリン酸基含有有機化合物を含んでもよい。
If necessary, the aqueous first coating composition may further contain a phosphate group-containing organic compound in addition to the above components.
上記水性第１塗料組成物は、溶媒として、水、そして必要に応じた水溶性または水混和性有機溶媒を含んでもよい。
The aqueous first coating composition may contain water as a solvent, and optionally a water-soluble or water-miscible organic solvent.
上記水性第１塗料組成物の製造は、第１塗膜形成樹脂、光輝性顔料、硬化剤、そして必要に応じた他の成分、添加剤などを、ディスパー、ホモジナイザー、ニーダーなどを用いて混練・分散するなどの当業者において通常用いられる方法で製造することができる。上記製造方法において、例えば、光輝性顔料および必要に応じた顔料分散剤を含むペーストを予め調製し、混合するのが好ましい。顔料分散剤として、市販の顔料分散剤などを用いることができる。
The aqueous first coating composition is produced by kneading and kneading the first coating film-forming resin, the bright pigment, the curing agent, and optionally other components, additives, and the like using a disper, homogenizer, kneader, or the like. It can be produced by a method commonly used by those skilled in the art, such as dispersing. In the above production method, for example, it is preferable to previously prepare a paste containing a luster pigment and optionally a pigment dispersant and mix the paste. A commercially available pigment dispersant or the like can be used as the pigment dispersant.
上記第１塗料組成物が溶剤型塗料組成物である場合は、第１塗膜形成樹脂として例えば、アクリル樹脂、ポリエステル樹脂（ウレタン変性ポリエステル樹脂なども含む）などが挙げられる。これらの樹脂は１種のみを単独で用いてもよく、２種またはそれ以上を併用してもよい。
When the first coating composition is a solvent-based coating composition, examples of the first coating film-forming resin include acrylic resins and polyester resins (including urethane-modified polyester resins, etc.). These resins may be used alone or in combination of two or more.
アクリル樹脂は、例えば、α，β－エチレン性不飽和モノマーを含むモノマー混合物を、溶液重合を行うことにより調製することができる。上記アクリル樹脂は、数平均分子量が１０００～２００００であるのが好ましい。上記アクリル樹脂はまた、酸価（固形分酸価）が１～８０ｍｇＫＯＨ／ｇであるのが好ましく、１０～４５ｍｇＫＯＨ／ｇであるのがより好ましい。また、水酸基価（固形分水酸基価）が１０～２００ｍｇＫＯＨ／ｇであるのが好ましい。
The acrylic resin can be prepared, for example, by solution polymerization of a monomer mixture containing α,β-ethylenically unsaturated monomers. The acrylic resin preferably has a number average molecular weight of 1,000 to 20,000. The acrylic resin also preferably has an acid value (solid content acid value) of 1 to 80 mgKOH/g, more preferably 10 to 45 mgKOH/g. Also, the hydroxyl value (solid content hydroxyl value) is preferably 10 to 200 mgKOH/g.
アクリル樹脂として市販品を用いてもよい。市販品として、例えば、三菱レイヨン社製のダイヤナールＨＲシリーズなどが挙げられる。
A commercially available product may be used as the acrylic resin. Commercially available products include, for example, Dianal HR series manufactured by Mitsubishi Rayon Co., Ltd.
アクリル樹脂の量は、塗料樹脂固形分質量（塗膜形成成分の固形分質量）を基準にして３０～８０質量％であるのが好ましく、３５～７０質量％であるのがより好ましい。
The amount of the acrylic resin is preferably 30 to 80% by mass, more preferably 35 to 70% by mass, based on the solid content of the paint resin (the solid content of the coating film-forming component).
上記ポリエステル樹脂として、例えば水酸基含有ポリエステル樹脂を用いることができる。水酸基含有ポリエステル樹脂は、多価カルボン酸および／または酸無水物などの酸成分と多価アルコールとを重縮合することによって調製することができる。
For example, a hydroxyl group-containing polyester resin can be used as the polyester resin. A hydroxyl group-containing polyester resin can be prepared by polycondensing an acid component such as a polyvalent carboxylic acid and/or an acid anhydride with a polyhydric alcohol.
上記第１塗料組成物が溶剤型塗料組成物である場合は、上記第１塗膜形成樹脂に対して反応する硬化剤を用いるのが好ましい。硬化剤として、メラミン樹脂、ブロックイソシアネート化合物などを用いることができる。これらは１種のみを単独で用いてもよく、２種またはそれ以上を併用してもよい。上記成分は、当業者において通常用いられる方法により調製することができる。上記成分として市販品を用いてもよい。
When the first coating composition is a solvent-based coating composition, it is preferable to use a curing agent that reacts with the first coating film-forming resin. A melamine resin, a blocked isocyanate compound, or the like can be used as a curing agent. These may be used alone or in combination of two or more. The above components can be prepared by methods commonly used by those skilled in the art. You may use a commercial item as said component.
上記硬化剤は、メラミン樹脂を含むのが好ましい。メラミン樹脂としては、特に限定されるものではなく、メチル化メラミン樹脂、ブチル化メラミン樹脂、メチル・ブチル混合型メラミン樹脂などを用いることができる。例えばＡｌｌｎｅｘ社から市販されているサイメルシリーズ、三井化学社から市販されているユーバンシリーズなどが挙げられる。メラミン樹脂の量は、塗料樹脂固形分質量（上記塗膜形成樹脂および硬化剤を含む塗膜形成成分の固形分質量）を基準にして１０～５０質量％であるのが好ましく、１５～４０質量％であるのがより好ましい。
The curing agent preferably contains melamine resin. The melamine resin is not particularly limited, and may be methylated melamine resin, butylated melamine resin, methyl/butyl mixed type melamine resin, or the like. For example, Cymel series commercially available from Allnex, Uvan series commercially available from Mitsui Chemicals, etc. can be mentioned. The amount of the melamine resin is preferably 10 to 50% by mass, preferably 15 to 40% by mass, based on the solid content of the coating resin (the solid content of the coating film-forming components including the coating film-forming resin and the curing agent). % is more preferred.
上記硬化剤はさらに、ブロックイソシアネート化合物を含むのが好ましい。ブロックイソシアネート化合物は、ポリイソシアネートに、活性メチレン基を有する化合物、ケトン化合物またはカプロラクタム化合物などのブロック化合物を付加反応させることによって調製することができる。ブロックイソシアネート化合物として市販品を用いてもよい。市販品として、例えば、旭化成社製のデュラネートシリーズ、住化コベストロウレタン社製のスミジュールシリーズなどが挙げられる。
The curing agent preferably further contains a blocked isocyanate compound. A blocked isocyanate compound can be prepared by addition reaction of a polyisocyanate with a block compound such as a compound having an active methylene group, a ketone compound, or a caprolactam compound. You may use a commercial item as a block isocyanate compound. Commercially available products include, for example, the Duranate series manufactured by Asahi Kasei Corporation and the Sumidule series manufactured by Sumika Covestro Urethane.
第１塗料組成物に含まれるブロックイソシアネート化合物の量は、塗料樹脂固形分質量（上記塗膜形成樹脂および硬化剤を含む塗膜形成成分の固形分質量）を基準にして１０～３０質量％であるのが好ましく、１５～２５質量％であるのがより好ましい。
The amount of the blocked isocyanate compound contained in the first coating composition is 10 to 30% by mass based on the solid content of the coating resin (the solid content of the coating film-forming components including the coating film-forming resin and the curing agent). preferably 15 to 25% by mass.
溶剤型第１塗料組成物は、上記第１塗膜形成樹脂および光輝性顔料を含む。光輝性顔料として、上記光輝性顔料を同様に用いることができる。溶剤型第１塗料組成物は、上記成分に加えて、当業者において通常用いられる添加剤、例えば、硬化触媒、表面調整剤、紫外線吸収剤、酸化防止剤など、当業者において通常用いられる添加剤などを含んでもよい。
The solvent-based first coating composition contains the first coating film-forming resin and a bright pigment. As the luster pigment, the above luster pigments can be used in the same manner. In addition to the above components, the solvent-based first coating composition contains additives commonly used by those skilled in the art, such as curing catalysts, surface conditioners, ultraviolet absorbers, antioxidants, etc. Additives commonly used by those skilled in the art and so on.
溶剤型第１塗料組成物は、塗装時に、有機溶剤を用いて希釈することによって、固形分濃度および粘度を適宜調整することができる。用いることができる有機溶媒として、例えば、エステル系溶剤、エーテル系溶媒、アルコール系溶媒、ケトン系溶媒、脂肪族炭化水素系溶剤、芳香族系溶剤などが挙げられる。
The solid content concentration and viscosity of the solvent-based first coating composition can be appropriately adjusted by diluting it with an organic solvent at the time of coating. Organic solvents that can be used include, for example, ester solvents, ether solvents, alcohol solvents, ketone solvents, aliphatic hydrocarbon solvents, and aromatic solvents.
上記溶剤型第１塗料組成物は、必要に応じて、上記成分に加えてさらにリン酸基含有有機化合物を含んでもよい。
If necessary, the solvent-based first coating composition may further contain a phosphoric acid group-containing organic compound in addition to the above components.
上記溶剤型第１塗料組成物の製造は、第１塗膜形成樹脂、硬化剤、顔料、リン酸基含有有機化合物および添加剤などを、ディスパー、ホモジナイザー、ニーダーなどを用いて混練・分散するなどの当業者において通常用いられる方法で製造することができる。上記製造方法において、例えば、光輝性顔料および必要に応じた顔料分散剤を含むペーストを予め調製し、混合するのが好ましい。
The solvent-based first coating composition is produced by kneading and dispersing the first coating film-forming resin, curing agent, pigment, phosphoric acid group-containing organic compound, additives, and the like using a disper, homogenizer, kneader, or the like. can be produced by a method commonly used by those skilled in the art. In the above production method, for example, it is preferable to previously prepare a paste containing a luster pigment and optionally a pigment dispersant and mix the paste.
第２塗料組成物
本開示における第２塗膜は、第２塗料組成物の硬化塗膜である。上記第２塗料組成物は、第２塗膜形成樹脂および着色顔料を含む塗料組成物である。第２塗料組成物は、上記第１塗料組成物と同様に、水性塗料組成物であってもよく、溶剤型塗料組成物であってもよい。このような第２塗料組成物は、第１塗料組成物と同様の手順により調製することができる。 Second Coating Composition The second coating in the present disclosure is the cured coating of the second coating composition. The second coating composition is a coating composition containing a second coating film-forming resin and a color pigment. The second coating composition, like the first coating composition, may be a water-based coating composition or a solvent-based coating composition. Such a second coating composition can be prepared by the same procedure as for the first coating composition.
本開示における第２塗膜は、第２塗料組成物の硬化塗膜である。上記第２塗料組成物は、第２塗膜形成樹脂および着色顔料を含む塗料組成物である。第２塗料組成物は、上記第１塗料組成物と同様に、水性塗料組成物であってもよく、溶剤型塗料組成物であってもよい。このような第２塗料組成物は、第１塗料組成物と同様の手順により調製することができる。 Second Coating Composition The second coating in the present disclosure is the cured coating of the second coating composition. The second coating composition is a coating composition containing a second coating film-forming resin and a color pigment. The second coating composition, like the first coating composition, may be a water-based coating composition or a solvent-based coating composition. Such a second coating composition can be prepared by the same procedure as for the first coating composition.
第２塗膜形成樹脂として、上記第１塗膜形成樹脂と同様の樹脂を用いることができる。上記第１塗膜形成樹脂および第２塗膜形成樹脂は、同一の樹脂組成であってもよく、異なる樹脂組成であってもよい。
As the second coating film-forming resin, the same resin as the first coating film-forming resin can be used. The first coating film-forming resin and the second coating film-forming resin may have the same resin composition or may have different resin compositions.
本開示の複層塗膜において、上記第２塗膜中に含まれる着色顔料の含有量は、塗膜に含まれる樹脂固形分１００質量部に対して１．５～６質量部の範囲内であることを条件とする。上記含有量の下限値は１．７質量部であってよい。上記下限値は、ある態様において、例えば２．０質量部であってよい。上記含有量の上限値は５．７質量部であってよく、５．５質量部であってよく、さらには５質量部であってよい。
In the multilayer coating film of the present disclosure, the content of the coloring pigment contained in the second coating film is within the range of 1.5 to 6 parts by mass with respect to 100 parts by mass of the resin solid content contained in the coating film. provided that there is The lower limit of the content may be 1.7 parts by mass. In one aspect, the lower limit may be, for example, 2.0 parts by mass. The upper limit of the content may be 5.7 parts by mass, may be 5.5 parts by mass, and may be 5 parts by mass.
上記第２塗膜中に含まれる着色顔料の好適な例として、例えば、カーボンブラック、黒鉛（グラファイト）、鉄黒（アイアンブラック）、鉄クロムやビスマスマンガン等の複合金属酸化物、ペリレン系黒色顔料、アゾメチアゾ系顔料などの黒色系顔料が挙げられる。
Suitable examples of the coloring pigment contained in the second coating film include, for example, carbon black, graphite, iron black, composite metal oxides such as iron chromium and bismuth manganese, and perylene-based black pigments. and black pigments such as azomethiazo pigments.
第２塗膜中に含まれる着色顔料として、必要に応じて、上記黒色系顔料以外の着色顔料を含んでもよい。他の着色顔料として、例えば、
シアニンブルー、スレンブルー、コバルトブルー、銅フタロシアニンブルー、インダンスロンブルーなどの青色系顔料；
塩素化フタロシアニングリーン、臭素化フタロシアニングリーンなどの緑色系顔料；
ジオキサジンバイオレット、ペリレンバイオレットなどの紫色系顔料；
酸化鉄、透明酸化鉄、モノアゾレッド、キナクリドンレッド、アゾレーキ（Ｍｎ塩）、ペリレンレッド、ペリレンマルーンなどの赤色系顔料；
黄鉛、合成黄色酸化鉄、ビスマスバナデート、チタンイエロー、亜鉛黄（ジンクエロー）、オーカー、モノアゾイエロー、ジスアゾイエロー、イソインドリノンイエロー、金属錯塩アゾイエロー、キノフタロンイエロー、ベンズイミダゾロンイエローなどの黄色系顔料；
キナクリドンマゼンタ、アンサンスロンオレンジ、ジアンスラキノニルレッド、ピラゾロンオレンジ、ベンズイミダゾロンオレンジ、ジケトピロロピロールクロムバーミリオンなどの橙色系顔料；
などが挙げられる。 As the coloring pigment contained in the second coating film, a coloring pigment other than the black pigment may be included as necessary. Other coloring pigments such as
Blue pigments such as cyanine blue, thren blue, cobalt blue, copper phthalocyanine blue, and indanthrone blue;
Green pigments such as chlorinated phthalocyanine green and brominated phthalocyanine green;
purple pigments such as dioxazine violet and perylene violet;
Red pigments such as iron oxide, transparent iron oxide, monoazo red, quinacridone red, azo lake (Mn salt), perylene red, and perylene maroon;
Yellows such as yellow lead, synthetic yellow iron oxide, bismuth vanadate, titanium yellow, zinc yellow, ocher, monoazo yellow, disazo yellow, isoindolinone yellow, metal complex salt azo yellow, quinophthalone yellow, and benzimidazolone yellow pigment;
orange pigments such as quinacridone magenta, anthrone orange, dianthraquinonyl red, pyrazolone orange, benzimidazolone orange, diketopyrrolopyrrole chromium vermilion;
etc.
シアニンブルー、スレンブルー、コバルトブルー、銅フタロシアニンブルー、インダンスロンブルーなどの青色系顔料；
塩素化フタロシアニングリーン、臭素化フタロシアニングリーンなどの緑色系顔料；
ジオキサジンバイオレット、ペリレンバイオレットなどの紫色系顔料；
酸化鉄、透明酸化鉄、モノアゾレッド、キナクリドンレッド、アゾレーキ（Ｍｎ塩）、ペリレンレッド、ペリレンマルーンなどの赤色系顔料；
黄鉛、合成黄色酸化鉄、ビスマスバナデート、チタンイエロー、亜鉛黄（ジンクエロー）、オーカー、モノアゾイエロー、ジスアゾイエロー、イソインドリノンイエロー、金属錯塩アゾイエロー、キノフタロンイエロー、ベンズイミダゾロンイエローなどの黄色系顔料；
キナクリドンマゼンタ、アンサンスロンオレンジ、ジアンスラキノニルレッド、ピラゾロンオレンジ、ベンズイミダゾロンオレンジ、ジケトピロロピロールクロムバーミリオンなどの橙色系顔料；
などが挙げられる。 As the coloring pigment contained in the second coating film, a coloring pigment other than the black pigment may be included as necessary. Other coloring pigments such as
Blue pigments such as cyanine blue, thren blue, cobalt blue, copper phthalocyanine blue, and indanthrone blue;
Green pigments such as chlorinated phthalocyanine green and brominated phthalocyanine green;
purple pigments such as dioxazine violet and perylene violet;
Red pigments such as iron oxide, transparent iron oxide, monoazo red, quinacridone red, azo lake (Mn salt), perylene red, and perylene maroon;
Yellows such as yellow lead, synthetic yellow iron oxide, bismuth vanadate, titanium yellow, zinc yellow, ocher, monoazo yellow, disazo yellow, isoindolinone yellow, metal complex salt azo yellow, quinophthalone yellow, and benzimidazolone yellow pigment;
orange pigments such as quinacridone magenta, anthrone orange, dianthraquinonyl red, pyrazolone orange, benzimidazolone orange, diketopyrrolopyrrole chromium vermilion;
etc.
第２塗料組成物に含まれる着色顔料の好適量は、第２塗膜中における含有量と同様に、第２塗料組成物中に含まれる樹脂固形分１００質量部に対して１．５～６質量部であるのが好ましい。上記含有量の下限値は１．７質量部であってよい。上記下限値は、ある態様において、例えば２．０質量部であってよい。上記含有量の上限値は５．７質量部であってよく、５．５質量部であってよく、さらには５質量部であってよい。好適に用いられる上記黒色系顔料が上記第２塗料組成物に上記含有量で含まれることによって、本開示において目的とする、黒色塗膜と認識されるほどに明度および彩度が低い一方で輝度が認識される意匠の複層塗膜を好適に形成することができる利点がある。
A suitable amount of the coloring pigment contained in the second coating composition is, like the content in the second coating film, 1.5 to 6 parts per 100 parts by mass of the resin solid content contained in the second coating composition. Parts by mass are preferred. The lower limit of the content may be 1.7 parts by mass. In one aspect, the lower limit may be, for example, 2.0 parts by mass. The upper limit of the content may be 5.7 parts by mass, may be 5.5 parts by mass, and may be 5 parts by mass. By including the preferably used black pigment in the second coating composition in the above content, the brightness and saturation are low enough to be recognized as a black coating film, which is the object of the present disclosure. There is an advantage that it is possible to suitably form a multilayer coating film with a design that is recognized.
上記第２塗料組成物は、上記着色顔料以外の他の顔料を含んでもよい。他の顔料として例えば、上記第１塗料組成物において例示した、体質顔料、防錆顔料などが挙げられる。体質顔料として、例えば、炭酸カルシウム、硫酸バリウム、クレー、タルクなどを挙げることができる。
The second paint composition may contain pigments other than the color pigments. Other pigments include, for example, extender pigments and rust preventive pigments exemplified in the first paint composition. Examples of extender pigments include calcium carbonate, barium sulfate, clay, and talc.
本開示において、第２塗料組成物は、光輝性顔料を実質的に含まないのが好ましい。例えば、第２塗料組成物における光輝性顔料の含有量は、樹脂固形分１００質量部に対して０．５質量部未満であるのが好ましく、０．３質量部未満であるのがより好ましく、０．１質量部未満であるのがさらに好ましい。
In the present disclosure, the second paint composition preferably does not substantially contain a bright pigment. For example, the content of the bright pigment in the second coating composition is preferably less than 0.5 parts by mass, more preferably less than 0.3 parts by mass relative to 100 parts by mass of the resin solid content, More preferably less than 0.1 part by mass.
複層塗膜形成
本開示の複層塗膜は、上記第１塗料組成物の硬化塗膜である第１塗膜、上記第２塗料組成物の硬化塗膜である第２塗膜、およびクリヤー塗膜を、この順で有する塗膜である。 Multilayer coating film formation The multilayer coating film of the present disclosure includes a first coating film that is a cured coating film of the first coating composition, a second coating film that is a cured coating film of the second coating composition, and a clear It is a coating film having coating films in this order.
本開示の複層塗膜は、上記第１塗料組成物の硬化塗膜である第１塗膜、上記第２塗料組成物の硬化塗膜である第２塗膜、およびクリヤー塗膜を、この順で有する塗膜である。 Multilayer coating film formation The multilayer coating film of the present disclosure includes a first coating film that is a cured coating film of the first coating composition, a second coating film that is a cured coating film of the second coating composition, and a clear It is a coating film having coating films in this order.
本開示の複層塗膜の形成において、上記塗料組成物を塗装する対象である被塗物は、特に限定されず、例えば、金属、プラスチック、発泡体などを挙げることができる。上記塗料組成物は、特に金属および鋳造物に有利に用いることができ、電着塗装可能な金属に対して特に好適に用いることができる。このような金属としては、例えば、鉄、銅、アルミニウム、スズ、亜鉛などおよびこれらの金属を含む合金が挙げられる。これらの被塗物は、成型物であってもよい。成型物の具体例として、例えば、乗用車、トラック、オートバイ、バスなどの自動車車体およびその部品などが挙げられる。上記金属などの被塗物は、電着塗装する前に、予めリン酸系化成処理剤、ジルコニウム系化成処理剤などで化成処理するのがより好ましい。必要に応じた化成処理がなされた被塗物上に硬化電着塗膜が形成されているのが好ましい。硬化電着塗膜の形成に用いられる電着塗料組成物として、カチオン型およびアニオン型の何れも使用することができる。電着塗料組成物としてカチオン電着塗料組成物を用いることによって、より防食性に優れた塗膜を形成することができるため好ましい。
In the formation of the multilayer coating film of the present disclosure, the object to be coated with the coating composition is not particularly limited, and examples thereof include metals, plastics, and foams. The above coating composition can be used particularly advantageously for metals and castings, and can be particularly suitably used for metals that can be electrodeposition coated. Such metals include, for example, iron, copper, aluminum, tin, zinc, etc., and alloys containing these metals. These objects to be coated may be moldings. Specific examples of molded articles include automobile bodies such as passenger cars, trucks, motorcycles and buses, and parts thereof. It is more preferable that the object to be coated such as the above-mentioned metal is chemically treated with a phosphoric acid-based chemical conversion treatment agent, a zirconium-based chemical conversion treatment agent, or the like before electrodeposition coating. It is preferable that the cured electrodeposition coating film is formed on the article to be coated which has been subjected to chemical conversion treatment as necessary. As the electrodeposition coating composition used for forming the cured electrodeposition coating film, both cationic and anionic types can be used. By using a cationic electrodeposition coating composition as the electrodeposition coating composition, it is possible to form a coating film having more excellent anticorrosion properties, which is preferable.
上記被塗物はさらに必要に応じて、硬化電着塗膜の上に中塗り塗膜が形成されてもよい。中塗り塗膜の形成には中塗り塗料組成物が用いられる。中塗り塗料組成物として、例えば、塗膜形成性樹脂、硬化剤、有機系および／または無機系の各種着色成分および体質顔料などを含む塗料組成物を用いることができる。塗膜形成性樹脂および硬化剤は、特に限定されるものではなく、具体的には、上記水性塗料組成物で挙げた塗膜形成性樹脂および硬化剤などを用いることができる。中塗り塗料組成物の塗膜形成樹脂として、得られる中塗り塗膜の諸性能などの観点から、アクリル樹脂および／またはポリエステル樹脂と、アミノ樹脂および／またはイソシアネートとの組み合わせが好適に用いられる。
If necessary, an intermediate coating film may be formed on the cured electrodeposition coating film of the object to be coated. An intermediate coating composition is used to form the intermediate coating film. As the intermediate coating composition, for example, a coating composition containing a film-forming resin, a curing agent, various organic and/or inorganic coloring components, an extender pigment, and the like can be used. The coating film-forming resin and the curing agent are not particularly limited, and specifically, the coating film-forming resins and curing agents mentioned in the water-based coating composition can be used. As the film-forming resin of the intermediate coating composition, a combination of an acrylic resin and/or polyester resin and an amino resin and/or isocyanate is preferably used from the viewpoint of various properties of the resulting intermediate coating film.
上記第１塗料組成物および第２塗料組成物を用いた塗膜形成方法として、例えば以下の方法が挙げられる。
・被塗物に、上記第１塗料組成物をおよび第２塗料組成物を順次塗装し、次いでクリヤー塗料組成物を塗装する方法。このような塗装において、第１塗料組成物を塗装し加熱硬化させ、次いで第２塗料組成物を塗装し加熱硬化させてもよい。また、第１塗料組成物を塗装し、塗装した塗膜が未硬化の状態で、第２塗料組成物をウェットオンウェットで塗装し、次いで加熱硬化させてもよい。なお上記ウェットオンウェット塗装においては、塗装間に、必要に応じてプレヒートを行ってもよい。また、第１塗料組成物および第２塗料組成物を順次塗装して、常温で乾燥させてもよい。そして、第２塗料組成物を塗装して得られた第２塗膜に対してクリヤー塗料組成物を塗装して、クリヤー塗膜を設ける。
・被塗物に、第１塗料組成物、第２塗料組成物およびクリヤー塗料組成物をウェットオンウェットで順次塗装する方法。この塗装は詳しくは、第１塗料組成物、第２塗料組成物およびクリヤー塗膜をウェットオンウェットで順次塗装することにより、未硬化の第１塗膜、第２塗膜およびクリヤー塗膜を形成し、これらの未硬化の塗膜を一度に加熱硬化させる方法である。上記ウェットオンウェット塗装においては、塗装間に、必要に応じてプレヒートを行ってもよい。 Examples of the coating film forming method using the first coating composition and the second coating composition include the following methods.
- A method in which the first coating composition and the second coating composition are sequentially applied to an object to be coated, and then the clear coating composition is applied. In such coating, the first coating composition may be applied and cured by heating, and then the second coating composition may be coated and cured by heating. Alternatively, the first coating composition may be applied, the second coating composition may be applied wet-on-wet to the uncured coating film, and then heat-cured. In the above wet-on-wet coating, preheating may be performed between coatings, if necessary. Alternatively, the first coating composition and the second coating composition may be sequentially applied and dried at room temperature. Then, the clear coating composition is applied to the second coating film obtained by applying the second coating composition to form a clear coating film.
- A method in which the first coating composition, the second coating composition and the clear coating composition are sequentially applied wet-on-wet onto an object to be coated. More specifically, the first coating composition, the second coating composition and the clear coating film are successively applied wet-on-wet to form an uncured first coating film, second coating film and clear coating film. Then, these uncured coating films are heated and cured at once. In the wet-on-wet coating, preheating may be performed between coatings, if necessary.
・被塗物に、上記第１塗料組成物をおよび第２塗料組成物を順次塗装し、次いでクリヤー塗料組成物を塗装する方法。このような塗装において、第１塗料組成物を塗装し加熱硬化させ、次いで第２塗料組成物を塗装し加熱硬化させてもよい。また、第１塗料組成物を塗装し、塗装した塗膜が未硬化の状態で、第２塗料組成物をウェットオンウェットで塗装し、次いで加熱硬化させてもよい。なお上記ウェットオンウェット塗装においては、塗装間に、必要に応じてプレヒートを行ってもよい。また、第１塗料組成物および第２塗料組成物を順次塗装して、常温で乾燥させてもよい。そして、第２塗料組成物を塗装して得られた第２塗膜に対してクリヤー塗料組成物を塗装して、クリヤー塗膜を設ける。
・被塗物に、第１塗料組成物、第２塗料組成物およびクリヤー塗料組成物をウェットオンウェットで順次塗装する方法。この塗装は詳しくは、第１塗料組成物、第２塗料組成物およびクリヤー塗膜をウェットオンウェットで順次塗装することにより、未硬化の第１塗膜、第２塗膜およびクリヤー塗膜を形成し、これらの未硬化の塗膜を一度に加熱硬化させる方法である。上記ウェットオンウェット塗装においては、塗装間に、必要に応じてプレヒートを行ってもよい。 Examples of the coating film forming method using the first coating composition and the second coating composition include the following methods.
- A method in which the first coating composition and the second coating composition are sequentially applied to an object to be coated, and then the clear coating composition is applied. In such coating, the first coating composition may be applied and cured by heating, and then the second coating composition may be coated and cured by heating. Alternatively, the first coating composition may be applied, the second coating composition may be applied wet-on-wet to the uncured coating film, and then heat-cured. In the above wet-on-wet coating, preheating may be performed between coatings, if necessary. Alternatively, the first coating composition and the second coating composition may be sequentially applied and dried at room temperature. Then, the clear coating composition is applied to the second coating film obtained by applying the second coating composition to form a clear coating film.
- A method in which the first coating composition, the second coating composition and the clear coating composition are sequentially applied wet-on-wet onto an object to be coated. More specifically, the first coating composition, the second coating composition and the clear coating film are successively applied wet-on-wet to form an uncured first coating film, second coating film and clear coating film. Then, these uncured coating films are heated and cured at once. In the wet-on-wet coating, preheating may be performed between coatings, if necessary.
上記第１塗料組成物および第２塗料組成物は、塗料分野において一般的に用いられる手法によって、被塗物に対して塗装することができる。塗装方法として例えば、エアスプレー塗装、エアレススプレー塗装、静電スプレー塗装、エアー静電スプレー塗装による多ステージ塗装（好ましくは２ステージ塗装）、エアー静電スプレー塗装と回転霧化式の静電塗装機とを組み合わせた塗装などが挙げられる。
The first coating composition and the second coating composition can be applied to the object to be coated by a method generally used in the coating field. Examples of coating methods include air spray coating, airless spray coating, electrostatic spray coating, multi-stage coating (preferably two-stage coating) by air electrostatic spray coating, air electrostatic spray coating and rotary atomization type electrostatic coating machine. and the like.
上記第１塗料組成物は、硬化後の第１塗膜の膜厚が３～１３μｍの範囲内となるように塗装するのが好ましい。上記膜厚の下限値は３．５μｍであってよい。また、上記膜厚の上限値は１０μｍであってよく、８μｍであってよい。
また、第２塗料組成物は、硬化後の第２塗膜の膜厚が３～１５μｍの範囲内となるように塗装するのが好ましい。上記膜厚の下限値は３．５μｍであってよい。また、上記膜厚の上限値は１３μｍであってよく、１０μｍであってよい。 The first coating composition is preferably applied so that the thickness of the first coating film after curing is within the range of 3 to 13 μm. The lower limit of the film thickness may be 3.5 μm. Also, the upper limit of the film thickness may be 10 μm or 8 μm.
Moreover, the second coating composition is preferably applied so that the film thickness of the second coating film after curing is in the range of 3 to 15 μm. The lower limit of the film thickness may be 3.5 μm. Moreover, the upper limit of the film thickness may be 13 μm, or may be 10 μm.
また、第２塗料組成物は、硬化後の第２塗膜の膜厚が３～１５μｍの範囲内となるように塗装するのが好ましい。上記膜厚の下限値は３．５μｍであってよい。また、上記膜厚の上限値は１３μｍであってよく、１０μｍであってよい。 The first coating composition is preferably applied so that the thickness of the first coating film after curing is within the range of 3 to 13 μm. The lower limit of the film thickness may be 3.5 μm. Also, the upper limit of the film thickness may be 10 μm or 8 μm.
Moreover, the second coating composition is preferably applied so that the film thickness of the second coating film after curing is in the range of 3 to 15 μm. The lower limit of the film thickness may be 3.5 μm. Moreover, the upper limit of the film thickness may be 13 μm, or may be 10 μm.
上記第１塗料組成物、第２塗料組成物を塗装して加熱硬化させる場合における加熱温度および時間は、塗料組成物の組成（水性または溶剤型）および被塗物の種類に応じて適宜選択することができる。加熱温度は例えば８０～１８０℃の範囲、好ましくは１００～１６０℃の範囲などで適宜選択することができる。加熱時間は、例えば５分～６０分、好ましくは１０分～３０分の範囲などで適宜選択することができる。
The heating temperature and time when the first coating composition and the second coating composition are applied and heat-cured are appropriately selected according to the composition of the coating composition (aqueous or solvent type) and the type of object to be coated. be able to. The heating temperature can be appropriately selected, for example, in the range of 80 to 180°C, preferably in the range of 100 to 160°C. The heating time can be appropriately selected, for example, within the range of 5 minutes to 60 minutes, preferably 10 minutes to 30 minutes.
上記クリヤー塗料組成物は、特に限定されず、溶剤型、水性型および粉体型のクリヤー塗料組成物を挙げることができる。
The above clear coating composition is not particularly limited, and includes solvent-based, water-based and powder-based clear coating compositions.
上記溶剤型クリヤー塗料組成物の好ましい例としては、透明性あるいは耐酸エッチング性などの点から、アクリル樹脂および／またはポリエステル樹脂と、アミノ樹脂および／またはイソシアネートとの組み合わせ、あるいはカルボン酸／エポキシ硬化系を有するアクリル樹脂および／またはポリエステル樹脂などを挙げることができる。
Preferred examples of the solvent-based clear coating composition include a combination of an acrylic resin and/or polyester resin, an amino resin and/or isocyanate, or a carboxylic acid/epoxy curing system from the viewpoint of transparency or acid etching resistance. acrylic resins and/or polyester resins having
水性型クリヤー塗料組成物の例としては、上記溶剤型クリヤー塗料組成物の例として挙げた塗膜形成性樹脂を、塩基で中和して水性化した樹脂を含有するものが挙げることができる。この中和は重合の前または後に、ジメチルエタノールアミンおよびトリエチルアミンのような３級アミンを添加することにより行うことができる。
Examples of water-based clear coating compositions include those containing resins obtained by neutralizing the film-forming resins listed as examples of the solvent-based clear coating compositions with a base to make them water-based. This neutralization can be done by adding tertiary amines such as dimethylethanolamine and triethylamine before or after polymerization.
これらの溶剤型クリヤー塗料組成物そして水性型クリヤー塗料組成物は、塗装作業性を確保するために、粘性制御剤を含むのが好ましい。粘性制御剤は、一般にチクソトロピー性を示すものを用いることができる。粘性制御剤の例として、例えば、水性塗料組成物のところで挙げたものを用いることができる。併せて、塗料分野において一般的に用いられる添加剤を必要に応じて含んでもよい。
These solvent-based clear coating compositions and water-based clear coating compositions preferably contain a viscosity control agent in order to ensure coating workability. Viscosity control agents that generally exhibit thixotropy can be used. As examples of the viscosity control agent, for example, those mentioned in the section of the water-based coating composition can be used. In addition, additives generally used in the paint field may be included as necessary.
粉体型クリヤー塗料組成物としては、例えば、熱可塑性粉体塗料組成物、熱硬化性粉体塗料組成物などの、塗料分野において一般的に用いられる粉体塗料組成物を用いることができる。これらの中でも、塗膜物性などの点から、熱硬化性粉体塗料組成物が好ましい。熱硬化性粉体塗料組成物の具体例として、エポキシ系、アクリル系およびポリエステル系の粉体クリヤー塗料組成物などが挙げられる。
As the powder-type clear coating composition, powder coating compositions commonly used in the coating field, such as thermoplastic powder coating compositions and thermosetting powder coating compositions, can be used. Among these, the thermosetting powder coating composition is preferred from the viewpoint of the physical properties of the coating film. Specific examples of thermosetting powder coating compositions include epoxy-, acrylic- and polyester-based clear powder coating compositions.
クリヤー塗料組成物の塗装は、クリヤー塗料組成物の塗装形態に従った、当業者に公知の塗装方法を用いて行うことができる。上記クリヤー塗料組成物を塗装することによって形成されるクリヤー塗膜の乾燥膜厚は、一般に１０～８０μｍが好ましく、２０～６０μｍであることがより好ましい。
The coating of the clear coating composition can be carried out using a coating method known to those skilled in the art according to the coating form of the clear coating composition. The dry film thickness of the clear coating film formed by applying the above clear coating composition is generally preferably 10 to 80 μm, more preferably 20 to 60 μm.
クリヤー塗料組成物の塗装によって得られた未硬化のクリヤー塗膜を加熱硬化させることによって、硬化したクリヤー塗膜を形成することができる。クリヤー塗料組成物を、未硬化の第２ベース塗膜の上に塗装した場合は、加熱させることによって、これらの未硬化塗膜が加熱硬化することとなる。加熱硬化温度は、硬化性および得られる複層塗膜の物性の観点から、８０～１８０℃に設定されていることが好ましく、１２０～１６０℃に設定されていることがさらに好ましい。加熱硬化時間は、上記温度に応じて任意に設定することができる。加熱硬化条件として、例えば、加熱硬化温度１２０℃～１６０℃で１０分～３０分間加熱する条件などが挙げられる。
なお、塗料組成物の種類に応じて、上記塗料組成物を塗装した後、常温で乾燥させて塗膜を形成し、次いで、例えば反応硬化型クリヤー塗料組成物を塗装して、クリヤー塗膜を設けてもよい。 A cured clear coating film can be formed by heating and curing an uncured clear coating film obtained by applying the clear coating composition. When the clear coating composition is applied on the uncured second base coating film, the uncured coating film is heat-cured by heating. The heat-curing temperature is preferably set to 80 to 180° C., more preferably 120 to 160° C., from the viewpoint of curability and physical properties of the obtained multilayer coating film. The heat curing time can be arbitrarily set according to the temperature. The heat curing conditions include, for example, a condition of heating at a heat curing temperature of 120° C. to 160° C. for 10 minutes to 30 minutes.
Depending on the type of coating composition, the coating composition is applied, dried at room temperature to form a coating film, and then, for example, a reaction-curing clear coating composition is applied to form a clear coating film. may be provided.
なお、塗料組成物の種類に応じて、上記塗料組成物を塗装した後、常温で乾燥させて塗膜を形成し、次いで、例えば反応硬化型クリヤー塗料組成物を塗装して、クリヤー塗膜を設けてもよい。 A cured clear coating film can be formed by heating and curing an uncured clear coating film obtained by applying the clear coating composition. When the clear coating composition is applied on the uncured second base coating film, the uncured coating film is heat-cured by heating. The heat-curing temperature is preferably set to 80 to 180° C., more preferably 120 to 160° C., from the viewpoint of curability and physical properties of the obtained multilayer coating film. The heat curing time can be arbitrarily set according to the temperature. The heat curing conditions include, for example, a condition of heating at a heat curing temperature of 120° C. to 160° C. for 10 minutes to 30 minutes.
Depending on the type of coating composition, the coating composition is applied, dried at room temperature to form a coating film, and then, for example, a reaction-curing clear coating composition is applied to form a clear coating film. may be provided.
本開示の複層塗膜は、
入射角４５°受光角４５°における光輝面積Ｓａ（４５°）値が８以上３５以下であり、
入射角４５°受光角１５°における光輝強度Ｓｉ（１５°）値が１以上１８以下であり、入射角４５°受光角２５°におけるＬ＊（２５°）値が５以上２５以下である、
ことを条件とする。 The multilayer coating film of the present disclosure is
The bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less,
The brightness intensity Si (15 °) value at an incident angle of 45 ° and a light receiving angle of 15 ° is 1 or more and 18 or less, and the L * (25 °) value at an incident angle of 45 ° and a light receiving angle of 25 ° is 5 or more and 25 or less.
provided that
入射角４５°受光角４５°における光輝面積Ｓａ（４５°）値が８以上３５以下であり、
入射角４５°受光角１５°における光輝強度Ｓｉ（１５°）値が１以上１８以下であり、入射角４５°受光角２５°におけるＬ＊（２５°）値が５以上２５以下である、
ことを条件とする。 The multilayer coating film of the present disclosure is
The bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less,
The brightness intensity Si (15 °) value at an incident angle of 45 ° and a light receiving angle of 15 ° is 1 or more and 18 or less, and the L * (25 °) value at an incident angle of 45 ° and a light receiving angle of 25 ° is 5 or more and 25 or less.
provided that
上記明度Ｌ＊は、Ｌ＊Ｃ＊ｈ表色系におけるパラメータであり、ＪＩＳ Ｚ８７２９に準拠して求めることができる。このＬ＊Ｃ＊ｈ表色系は、国際照明委員会により定められた表色系であり、Ｓｅｃｔｉｏｎ ４．２ ｏｆ ＣＩＥ Ｐｕｂｌｉｃａｔｉｏｎ １５．２（１９８６）に記載されている。Ｌ＊Ｃ＊ｈ表色系において、Ｌ＊は明度を表し、Ｃ＊は彩度を表し、ｈは色相角度を表す。彩度Ｃ＊は、その数値が増加するに従い被測定物質のあざやかさが増し、その数値が小さくなるに従いくすみが増すことを意味する。明度Ｌ＊は、その数値が増加するに従い被測定物質の明るさが増し、その数値が小さくなるに従い暗さが増すことを意味する。上記明度Ｌ＊は、市販の多角度分光測色計を用いて測定することができる。多角度分光測色計として、例えばＢＹＫ－ｍａｃｉ（ＢＹＫ社製）などが挙げられる。
The above lightness L* is a parameter in the L*C*h color system and can be obtained in accordance with JIS Z8729. This L*C*h color system is a color system defined by the International Commission on Illumination and described in Section 4.2 of CIE Publication 15.2 (1986). In the L*C*h color system, L* represents lightness, C* represents chroma, and h represents hue angle. The chroma C* means that as the value increases, the substance to be measured becomes brighter, and as the value decreases, the dullness increases. The lightness L* means that as the numerical value increases, the brightness of the substance to be measured increases, and as the numerical value decreases, the darkness increases. The lightness L* can be measured using a commercially available multi-angle spectrophotometer. Examples of the multi-angle spectrophotometer include BYK-maci (manufactured by BYK).
上記入射角４５°受光角２５°の明度Ｌ＊（２５°）において、入射角および受光角は詳しくは、硬化塗膜の４５°の角度から照射した光の正反射光の位置を０°とし、この正反射光から入射角方向へ２５°の位置の受光角を意味する。
In the lightness L* (25°) at the incident angle of 45° and the light receiving angle of 25°, the incident angle and the light receiving angle are defined as follows: , means the light-receiving angle at a position 25° from the specularly reflected light in the direction of the incident angle.
本明細書において、複層塗膜の明度Ｌ＊の測定は、上記第１塗料組成物の硬化塗膜、上記第２塗料組成物の硬化塗膜、およびクリヤー塗膜から構成される複層塗膜を用いて測定した値をいう。より具体的には、カチオン電着塗料組成物を塗装した鋼板に、ダークグレー系硬化中塗り塗膜を形成した塗板上に、上記第１塗料組成物を乾燥膜厚が４μｍとなるようにスプレー塗装し、次いで上記第２塗料組成物を乾燥膜厚が４μｍとなるようにウェットオンウェットでスプレー塗装し、次いでクリヤー塗料組成物を乾燥膜厚が３５μｍとなるようにウェットオンウェットでスプレー塗装し、その後、未硬化の３層の塗膜を１４０℃で２０分間加熱硬化させて得られた複層塗膜を用いて測定する。
In this specification, the measurement of the lightness L* of the multilayer coating film is a multilayer coating composed of a cured coating film of the first coating composition, a cured coating film of the second coating composition, and a clear coating film. A value measured using a membrane. More specifically, a steel plate coated with a cationic electrodeposition coating composition is coated with a dark gray intermediate curing coating film, and the first coating composition is spray-coated so that the dry film thickness is 4 μm. Then, the second coating composition is wet-on-wet spray-coated so that the dry film thickness is 4 μm, and then the clear coating composition is wet-on-wet spray-coated so that the dry film thickness is 35 μm, Thereafter, measurement is performed using a multi-layer coating film obtained by heating and curing the uncured three-layer coating film at 140° C. for 20 minutes.
本開示の複層塗膜において、上記Ｌ＊（２５°）値は５以上２５以下であることを条件とする。上記複層塗膜は、Ｌ＊（２５°）値が上記範囲内であり、いわゆるハイライト受光角条件下においても、複層塗膜が黒色塗膜と認識されるほどに明度が低いことを特徴の１つとする。上記Ｌ＊（２５°）値の下限値は７であるのが好ましく、１０であるのがより好ましい。また、上記Ｌ＊（２５°）値の上限値は２４．５であるのが好ましい。
In the multilayer coating film of the present disclosure, the L* (25°) value is 5 or more and 25 or less. The multi-layer coating film has an L* (25°) value within the above range, and the lightness is so low that the multi-layer coating film is recognized as a black coating film even under so-called highlight light receiving angle conditions. Let it be one of the features. The lower limit of the L*(25°) value is preferably 7, more preferably 10. Also, the upper limit of the L*(25°) value is preferably 24.5.
本開示の複層塗膜は、入射角４５°受光角４５°におけるＬ＊（４５°）値が２以上８以下であるのが好ましい。入射角４５°受光角４５°の測定条件は、ハイライト（受光角１５～２５°）からシェード（受光角７５～１１０°）に移行する間の、いわゆるフェースと言われる受光角条件である。この測定条件における明度Ｌ＊（４５°）値が上記範囲内であることによって、正面条件から見た複層塗膜の明度が十分に低く、本開示が目的とする意匠を好適に有することとなる。
The multilayer coating film of the present disclosure preferably has an L*(45°) value of 2 or more and 8 or less at an incident angle of 45° and a light receiving angle of 45°. The measurement condition of the incident angle of 45° and the light receiving angle of 45° is the so-called face receiving angle condition during the transition from highlight (light receiving angle of 15 to 25°) to shade (light receiving angle of 75 to 110°). When the lightness L* (45°) value in this measurement condition is within the above range, the lightness of the multilayer coating film viewed from the front condition is sufficiently low, and the design intended by the present disclosure is suitably obtained. Become.
本開示の複層塗膜はまた、入射角４５°受光角１５°における光輝強度Ｓｉ（１５°）値が１以上１８以下であることを条件とする。上記光輝強度（Ｓｉ）は輝きの強さを示す指標であり、数値が高いほど輝きが強いことを意味する。
The multi-layer coating film of the present disclosure is also conditional on the brilliance intensity Si (15°) value at an incident angle of 45° and a light receiving angle of 15° being 1 or more and 18 or less. The brilliance intensity (Si) is an index indicating the intensity of brilliance, and the higher the value, the stronger the brilliance.
本明細書において、上記光輝強度Ｓｉの測定値は、上記明度Ｌ＊の測定と同様の手順で作成した複層塗膜を用いて測定した値をいう。上記光輝強度Ｓｉ（１５°）値は、ＬＥＤ光源を入射角４５°で塗膜に対して照射し、この４５°の角度から照射した光の正反射光の位置を０°とし、この正反射光から入射角方向へ１５°の位置（受光角１５°）に配置したＣＣＤチップで画像を取得し、取得した画像を、明るさレベルのヒストグラムを用いた画像解析アルゴリズムで解析し、２次元分析を行うことによって、光輝度パラメータを計算し、光輝強度（Ｓｐａｒｋｌｅ ｉｎｔｅｎｓｉｔｙ＝Ｓｉ値）として表した数値である。
In this specification, the measured value of the brightness intensity Si refers to a value measured using a multi-layer coating film prepared in the same procedure as the measurement of the brightness L*. The above brightness intensity Si (15 °) value is obtained by irradiating the coating film with an LED light source at an incident angle of 45 °, and setting the position of the specularly reflected light of the light irradiated from this 45 ° angle to 0 °. An image is captured by a CCD chip placed at a position 15° from the light in the direction of the incident angle (15° light receiving angle), and the captured image is analyzed by an image analysis algorithm using a brightness level histogram, followed by two-dimensional analysis. is a numerical value expressed as a sparkle intensity (Sparkle intensity=Si value) calculated by performing the above.
複層塗膜の光輝強度Ｓｉ（１５°）値が１以上１８以下であることにより、いわゆるハイライト受光角条件下において、複層塗膜から一定強度の光輝感が認識されることとなる。
When the brightness intensity Si (15°) value of the multilayer coating film is 1 or more and 18 or less, a constant intensity of brightness is recognized from the multilayer coating film under the so-called highlight light receiving angle condition.
本開示の複層塗膜においてはさらに、入射角４５°受光角４５°における光輝強度Ｓｉ（４５°）値が１以上１７以下であるのが好ましい。光輝強度Ｓｉ（４５°）値は、ＬＥＤ光源を入射角４５°で塗膜に対して照射し、この４５°の角度から照射した光の正反射光の位置を０°とし、この正反射光から入射角方向へ４５°（受光角４５°）の位置で、上記と同様の手順により画像取得し光輝強度として表した数値である。複層塗膜の光輝強度Ｓｉ（４５°）値が１以上１７以下であることにより、いわゆるフェースと言われる受光角条件下においても複層塗膜から一定強度の光輝感が認識される、意匠上の利点がある。
Further, in the multilayer coating film of the present disclosure, it is preferable that the brightness intensity Si (45°) value at an incident angle of 45° and a light receiving angle of 45° is 1 or more and 17 or less. The brightness intensity Si (45 °) value is obtained by irradiating the coating film with an LED light source at an incident angle of 45 °, and setting the position of the specularly reflected light of the light irradiated from this 45 ° angle to 0 °, and this specularly reflected light is a numerical value obtained by acquiring an image by the same procedure as above at a position of 45° in the incident angle direction (45° of light receiving angle) from , and expressing it as the brightness intensity. A design in which the glitter intensity Si (45°) value of the multilayer coating film is 1 or more and 17 or less, so that a constant intensity of glitter can be recognized from the multilayer coating film even under the light-receiving angle condition called the so-called face. There are advantages above.
本開示の複層塗膜はまた、入射角４５°受光角４５°における光輝面積Ｓａ（４５°）値が８以上３５以下であることを条件とする。光輝面積Ｓａ値は、輝く部分の面積（大きさ）を数値として示す指標である。上記光輝面積Ｓａ値の測定は、上記明度Ｌ＊の測定と同様の手順で作成した複層塗膜を用いて測定した値をいう。上記光輝面積Ｓａ（４５°）値は、ＬＥＤ光源を入射角４５°で塗膜に対して照射し、この４５°の角度から照射した光の正反射光の位置を０°とし、この正反射光から入射角方向へ４５°の位置（受光角１５°）に配置したＣＣＤチップで画像を取得し、取得した画像を、明るさレベルのヒストグラムを用いた画像解析アルゴリズムで解析し、２次元分析を行うことによって、光輝度パラメータを計算し、光輝面積（Ｓｐａｒｋｌｅ ａｒｅａ＝Ｓａ値）として表した数値である。
The multilayer coating film of the present disclosure is also conditional that the bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less. The bright area Sa value is an index that numerically indicates the area (size) of the bright portion. The measurement of the bright area Sa value refers to the value measured using a multi-layer coating film prepared in the same manner as the measurement of the lightness L*. The above brilliant area Sa (45 °) value is obtained by irradiating the coating film with an LED light source at an incident angle of 45 °, setting the position of the specularly reflected light of the light irradiated from this 45 ° angle to 0 °, and this specular reflection An image is acquired by a CCD chip placed at a position of 45° in the incident angle direction from the light (light receiving angle of 15°), and the acquired image is analyzed by an image analysis algorithm using a brightness level histogram, and two-dimensional analysis. is a numerical value expressed as a bright area (Sparkle area=Sa value), which is obtained by calculating a brightness parameter by performing the above.
複層塗膜の光輝面積Ｓａ（４５°）値が８以上３５以下であることにより、いわゆるフェースと言われる受光角条件下において、複層塗膜から一定量面積の光輝感が認識されることとなる。
The glitter area Sa (45°) value of the multilayer coating film is 8 or more and 35 or less, so that a constant area of glitter can be recognized from the multilayer coating film under the light-receiving angle condition called the so-called face. becomes.
本開示の複層塗膜は、上述の通り、輝度が認識される一方で、明度および彩度が低く、色相としては黒色塗膜と認識されるという、黒色でありながら輝度が認識できる独創的な意匠の塗膜である。
As described above, the multi-layer coating film of the present disclosure is recognized as having brightness, but has low brightness and saturation, and is recognized as a black coating film as a hue. It is a coating film with a unique design.
以下の実施例により本発明をさらに具体的に説明するが、本発明はこれらに限定されない。実施例中、「部」および「％」は、ことわりのない限り、質量基準による。
The present invention will be described more specifically with the following examples, but the present invention is not limited to these. In the examples, "parts" and "%" are based on mass unless otherwise specified.
製造例１ アクリル樹脂エマルション（塗膜形成樹脂）の製造
反応容器に脱イオン水６３３部を加え、窒素気流中で混合撹拌しながら８０℃に昇温した。次いで、スチレン（ＳＴ）７５．６５質量部、メチルメタクリレート（ＭＭＡ）１７８．９６質量部、ｎ－ブチルアクリレート（ＢＡ）７５．９４質量部、２－エチルヘキシルアクリレート（２－ＥＨＡ）６４．４５質量部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）１０５．００質量部、の１段目のモノマー混合物、アクアロンＨＳ－１０（ポリオキシエチレンアルキルプロペニルフェニルエーテル硫酸エステル、第一工業製薬社製）２５．００部、アデカリアソープＮＥ－２０（α－［１－［（アリルオキシ）メチル］－２－（ノニルフェノキシ）エチル］－ω－ヒドロキシオキシエチレン、旭電化社製）２５．００部、および脱イオン水４００部からなるモノマー乳化物と、過硫酸アンモニウム１．２部、および脱イオン水５００部からなる開始剤溶液とを１．５時間にわたり並行して反応容器に滴下した。滴下終了後、１時間同温度で熟成を行った。
さらに、８０℃で、スチレン（ＳＴ）５３．６５質量部、メチルメタクリレート（ＭＭＡ）１７８．９６質量部、ｎ－ブチルアクリレート（ＢＡ）７５．９４質量部、２－エチルヘキシルアクリレート（２－ＥＨＡ）６４．４５質量部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）１０５．００質量部、アクリル酸２２質量部の２段目のモノマー混合物と、アクアロンＨＳ－１０ １０部および脱イオン水２５０部からなるモノマーの乳化物と、過硫酸アンモニウム３．０部および脱イオン水５００部からなる開始剤溶液とを１．５時間に渡り併行して、反応容器に滴下した。滴下終了後、２時間同温度で熟成を行った。
次いで、４０℃まで冷却し、４００メッシュフィルターで濾過した後、脱イオン水１００部およびジメチルアミノエタノール１．６部を加えｐＨ６．５に調整し、平均粒子径１５０ｎｍ、不揮発分３５％、固形分酸価２０ｍｇＫＯＨ／ｇ、水酸基価１００ｍｇＫＯＨ／ｇのアクリル樹脂エマルションを得た。 Production Example 1 Production of Acrylic Resin Emulsion (Coating Film-Forming Resin) 633 parts of deionized water was added to a reaction vessel, and the temperature was raised to 80° C. while mixing and stirring in a nitrogen stream. Then, styrene (ST) 75.65 parts by mass, methyl methacrylate (MMA) 178.96 parts by mass, n-butyl acrylate (BA) 75.94 parts by mass, 2-ethylhexyl acrylate (2-EHA) 64.45 parts by mass , Hydroxyethyl methacrylate (HEMA) 105.00 parts by mass, the first-stage monomer mixture, Aqualon HS-10 (polyoxyethylene alkylpropenyl phenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 25.00 parts, Adekaria Soap NE-20 (α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω-hydroxyoxyethylene, manufactured by Asahi Denka Co., Ltd.) 25.00 parts and deionized water 400 parts A monomer emulsion and an initiator solution consisting of 1.2 parts of ammonium persulfate and 500 parts of deionized water were added dropwise to the reaction vessel over 1.5 hours in parallel. After completion of dropping, aging was performed at the same temperature for 1 hour.
Furthermore, at 80 ° C., styrene (ST) 53.65 parts by mass, methyl methacrylate (MMA) 178.96 parts by mass, n-butyl acrylate (BA) 75.94 parts by mass, 2-ethylhexyl acrylate (2-EHA) 64 .45 parts by mass, 105.00 parts by mass of hydroxyethyl methacrylate (HEMA), 22 parts by mass of acrylic acid, a second-stage monomer mixture, and a monomer emulsion consisting of 10 parts of Aqualon HS-10 and 250 parts of deionized water. , an initiator solution consisting of 3.0 parts of ammonium persulfate and 500 parts of deionized water were concurrently added dropwise to the reaction vessel over 1.5 hours. After completion of dropping, aging was performed at the same temperature for 2 hours.
Then, after cooling to 40 ° C. and filtering with a 400 mesh filter, 100 parts of deionized water and 1.6 parts of dimethylaminoethanol were added to adjust the pH to 6.5, the average particle size was 150 nm, the nonvolatile content was 35%, and the solid content was adjusted to 6.5. An acrylic resin emulsion having an acid value of 20 mgKOH/g and a hydroxyl value of 100 mgKOH/g was obtained.
反応容器に脱イオン水６３３部を加え、窒素気流中で混合撹拌しながら８０℃に昇温した。次いで、スチレン（ＳＴ）７５．６５質量部、メチルメタクリレート（ＭＭＡ）１７８．９６質量部、ｎ－ブチルアクリレート（ＢＡ）７５．９４質量部、２－エチルヘキシルアクリレート（２－ＥＨＡ）６４．４５質量部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）１０５．００質量部、の１段目のモノマー混合物、アクアロンＨＳ－１０（ポリオキシエチレンアルキルプロペニルフェニルエーテル硫酸エステル、第一工業製薬社製）２５．００部、アデカリアソープＮＥ－２０（α－［１－［（アリルオキシ）メチル］－２－（ノニルフェノキシ）エチル］－ω－ヒドロキシオキシエチレン、旭電化社製）２５．００部、および脱イオン水４００部からなるモノマー乳化物と、過硫酸アンモニウム１．２部、および脱イオン水５００部からなる開始剤溶液とを１．５時間にわたり並行して反応容器に滴下した。滴下終了後、１時間同温度で熟成を行った。
さらに、８０℃で、スチレン（ＳＴ）５３．６５質量部、メチルメタクリレート（ＭＭＡ）１７８．９６質量部、ｎ－ブチルアクリレート（ＢＡ）７５．９４質量部、２－エチルヘキシルアクリレート（２－ＥＨＡ）６４．４５質量部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）１０５．００質量部、アクリル酸２２質量部の２段目のモノマー混合物と、アクアロンＨＳ－１０ １０部および脱イオン水２５０部からなるモノマーの乳化物と、過硫酸アンモニウム３．０部および脱イオン水５００部からなる開始剤溶液とを１．５時間に渡り併行して、反応容器に滴下した。滴下終了後、２時間同温度で熟成を行った。
次いで、４０℃まで冷却し、４００メッシュフィルターで濾過した後、脱イオン水１００部およびジメチルアミノエタノール１．６部を加えｐＨ６．５に調整し、平均粒子径１５０ｎｍ、不揮発分３５％、固形分酸価２０ｍｇＫＯＨ／ｇ、水酸基価１００ｍｇＫＯＨ／ｇのアクリル樹脂エマルションを得た。 Production Example 1 Production of Acrylic Resin Emulsion (Coating Film-Forming Resin) 633 parts of deionized water was added to a reaction vessel, and the temperature was raised to 80° C. while mixing and stirring in a nitrogen stream. Then, styrene (ST) 75.65 parts by mass, methyl methacrylate (MMA) 178.96 parts by mass, n-butyl acrylate (BA) 75.94 parts by mass, 2-ethylhexyl acrylate (2-EHA) 64.45 parts by mass , Hydroxyethyl methacrylate (HEMA) 105.00 parts by mass, the first-stage monomer mixture, Aqualon HS-10 (polyoxyethylene alkylpropenyl phenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 25.00 parts, Adekaria Soap NE-20 (α-[1-[(allyloxy)methyl]-2-(nonylphenoxy)ethyl]-ω-hydroxyoxyethylene, manufactured by Asahi Denka Co., Ltd.) 25.00 parts and deionized water 400 parts A monomer emulsion and an initiator solution consisting of 1.2 parts of ammonium persulfate and 500 parts of deionized water were added dropwise to the reaction vessel over 1.5 hours in parallel. After completion of dropping, aging was performed at the same temperature for 1 hour.
Furthermore, at 80 ° C., styrene (ST) 53.65 parts by mass, methyl methacrylate (MMA) 178.96 parts by mass, n-butyl acrylate (BA) 75.94 parts by mass, 2-ethylhexyl acrylate (2-EHA) 64 .45 parts by mass, 105.00 parts by mass of hydroxyethyl methacrylate (HEMA), 22 parts by mass of acrylic acid, a second-stage monomer mixture, and a monomer emulsion consisting of 10 parts of Aqualon HS-10 and 250 parts of deionized water. , an initiator solution consisting of 3.0 parts of ammonium persulfate and 500 parts of deionized water were concurrently added dropwise to the reaction vessel over 1.5 hours. After completion of dropping, aging was performed at the same temperature for 2 hours.
Then, after cooling to 40 ° C. and filtering with a 400 mesh filter, 100 parts of deionized water and 1.6 parts of dimethylaminoethanol were added to adjust the pH to 6.5, the average particle size was 150 nm, the nonvolatile content was 35%, and the solid content was adjusted to 6.5. An acrylic resin emulsion having an acid value of 20 mgKOH/g and a hydroxyl value of 100 mgKOH/g was obtained.
製造例２ リン酸基含有有機化合物の製造
攪拌機、温度調整器、冷却管を備えた１リットルの反応容器にエトキシプロパノール４０部を仕込み、これにスチレン４部、ｎ－ブチルアクリレート３５．９６部、エチルヘキシルメタアクリレート１８．４５部、２－ヒドロキシエチルメタクリレート１３．９２部、メタクリル酸７．６７部、エトキシプロパノール２０部に、ホスマーＰＰ（ユニケミカル社製アシッドホスホオキシヘキサ（オキシプロピレン）モノメタクリレート）２０部を溶解した溶液４０部、およびアゾビスイソブチロニトリル１．７部からなるモノマー溶液１２１．７部を１２０℃で３時間滴下した後、１時間さらに攪拌を継続した。得られたリン酸基含有有機化合物は、酸価１０５ｍｇＫＯＨ／ｇ、うちリン酸基価５５ｍｇＫＯＨ／ｇ、水酸基価６０ｍｇＫＯＨ／ｇ、数平均分子量６０００、不揮発分が６３％であった。 Production Example 2 Production of an Organic Compound Containing a Phosphate Group A 1-liter reaction vessel equipped with a stirrer, a temperature controller and a cooling pipe was charged with 40 parts of ethoxypropanol, 4 parts of styrene, 35.96 parts of n-butyl acrylate, 18.45 parts of ethylhexyl methacrylate, 13.92 parts of 2-hydroxyethyl methacrylate, 7.67 parts of methacrylic acid, 20 parts of ethoxypropanol, Phosmer PP (acid phosphooxyhexa(oxypropylene) monomethacrylate manufactured by Unichemical) 20 and 121.7 parts of a monomer solution consisting of 1.7 parts of azobisisobutyronitrile and 121.7 parts of azobisisobutyronitrile were added dropwise at 120° C. for 3 hours, and then stirring was continued for 1 hour. The obtained phosphate group-containing organic compound had an acid value of 105 mgKOH/g, including a phosphate value of 55 mgKOH/g, a hydroxyl value of 60 mgKOH/g, a number average molecular weight of 6000, and a non-volatile content of 63%.
攪拌機、温度調整器、冷却管を備えた１リットルの反応容器にエトキシプロパノール４０部を仕込み、これにスチレン４部、ｎ－ブチルアクリレート３５．９６部、エチルヘキシルメタアクリレート１８．４５部、２－ヒドロキシエチルメタクリレート１３．９２部、メタクリル酸７．６７部、エトキシプロパノール２０部に、ホスマーＰＰ（ユニケミカル社製アシッドホスホオキシヘキサ（オキシプロピレン）モノメタクリレート）２０部を溶解した溶液４０部、およびアゾビスイソブチロニトリル１．７部からなるモノマー溶液１２１．７部を１２０℃で３時間滴下した後、１時間さらに攪拌を継続した。得られたリン酸基含有有機化合物は、酸価１０５ｍｇＫＯＨ／ｇ、うちリン酸基価５５ｍｇＫＯＨ／ｇ、水酸基価６０ｍｇＫＯＨ／ｇ、数平均分子量６０００、不揮発分が６３％であった。 Production Example 2 Production of an Organic Compound Containing a Phosphate Group A 1-liter reaction vessel equipped with a stirrer, a temperature controller and a cooling pipe was charged with 40 parts of ethoxypropanol, 4 parts of styrene, 35.96 parts of n-butyl acrylate, 18.45 parts of ethylhexyl methacrylate, 13.92 parts of 2-hydroxyethyl methacrylate, 7.67 parts of methacrylic acid, 20 parts of ethoxypropanol, Phosmer PP (acid phosphooxyhexa(oxypropylene) monomethacrylate manufactured by Unichemical) 20 and 121.7 parts of a monomer solution consisting of 1.7 parts of azobisisobutyronitrile and 121.7 parts of azobisisobutyronitrile were added dropwise at 120° C. for 3 hours, and then stirring was continued for 1 hour. The obtained phosphate group-containing organic compound had an acid value of 105 mgKOH/g, including a phosphate value of 55 mgKOH/g, a hydroxyl value of 60 mgKOH/g, a number average molecular weight of 6000, and a non-volatile content of 63%.
なお本明細書実施例において、数平均分子量の測定は、ＧＰＣ装置として「ＨＬＣ８２２０ＧＰＣ」（商品名、東ソー（株）製）、カラムとして「Ｓｈｏｄｅｘ ＫＦ－６０６Ｍ」、「Ｓｈｏｄｅｘ ＫＦ－６０３」（いずれも昭和電工（株）製、商品名）の４本を用いて、移動相：テトラヒドロフラン、測定温度：４０℃、流速：０．６ｃｃ／分、検出器：ＲＩの条件で行なった。
また本明細書実施例において、リン酸基含有有機化合物の酸価およびリン酸基価の算出は、ＪＩＳ Ｋ５６０１ ２－１の酸価の定義（試料（不揮発物）１ｇ中の遊離酸を中和するのに要する、水酸化カリウム（ＫＯＨ）のｍｇ数）に基づいて計算を行って求めた。また水酸基価の算出は、ＪＩＳ Ｋ００７０の水酸基価の定義（試料１ｇをアセチル化させたとき、水酸基と結合した酢酸を中和するのに必要とする水酸化カリウムのｍｇ数）に基づいて計算を行って求めた。 In the examples of the present specification, the number average molecular weight was measured using "HLC8220GPC" (trade name, manufactured by Tosoh Corporation) as a GPC device, and "Shodex KF-606M" and "Shodex KF-603" as columns (both Showa Denko KK, trade name), mobile phase: tetrahydrofuran, measurement temperature: 40°C, flow rate: 0.6 cc/min, detector: RI.
In addition, in the examples of the present specification, the calculation of the acid value and the phosphate group value of the phosphate group-containing organic compound is based on the definition of acid value of JIS K5601 2-1 (neutralizing the free acid in 1 g of the sample (non-volatile matter) It was calculated based on the number of mg of potassium hydroxide (KOH) required to do so. The hydroxyl value is calculated based on the definition of hydroxyl value of JIS K0070 (mg of potassium hydroxide required to neutralize acetic acid bound to hydroxyl group when 1 g of sample is acetylated). I went and asked
また本明細書実施例において、リン酸基含有有機化合物の酸価およびリン酸基価の算出は、ＪＩＳ Ｋ５６０１ ２－１の酸価の定義（試料（不揮発物）１ｇ中の遊離酸を中和するのに要する、水酸化カリウム（ＫＯＨ）のｍｇ数）に基づいて計算を行って求めた。また水酸基価の算出は、ＪＩＳ Ｋ００７０の水酸基価の定義（試料１ｇをアセチル化させたとき、水酸基と結合した酢酸を中和するのに必要とする水酸化カリウムのｍｇ数）に基づいて計算を行って求めた。 In the examples of the present specification, the number average molecular weight was measured using "HLC8220GPC" (trade name, manufactured by Tosoh Corporation) as a GPC device, and "Shodex KF-606M" and "Shodex KF-603" as columns (both Showa Denko KK, trade name), mobile phase: tetrahydrofuran, measurement temperature: 40°C, flow rate: 0.6 cc/min, detector: RI.
In addition, in the examples of the present specification, the calculation of the acid value and the phosphate group value of the phosphate group-containing organic compound is based on the definition of acid value of JIS K5601 2-1 (neutralizing the free acid in 1 g of the sample (non-volatile matter) It was calculated based on the number of mg of potassium hydroxide (KOH) required to do so. The hydroxyl value is calculated based on the definition of hydroxyl value of JIS K0070 (mg of potassium hydroxide required to neutralize acetic acid bound to hydroxyl group when 1 g of sample is acetylated). I went and asked
実施例１
第１塗料組成物の調製
着色顔料分散ペースト
着色顔料であるシャニンブルーＧ３１４ ６部、ファストゲンスーパーレッド４００ＲＧ ４ 部、ラーベン５０００ ２０部、および、顔料分散剤であるＤｉｓｐｅｘ（登録商標）Ｕｌｔｒａ ＰＡ ４５５０（ＢＡＳＦ社製） １８．６部、イオン交換水３６．０部、消泡剤であるＢＹＫ－０１１ ０．５部をディスパーなどの撹拌機で混合分散して、着色顔料分散ペーストを得た。 Example 1
Preparation of First Coating Composition Colored Pigment Dispersion Paste 6 parts of Shannin Blue G314, 4 parts of Fastgen Super Red 400RG, 20 parts of Raven 5000, which are color pigments, and Dispex® Ultra PA 4550, which is a pigment dispersant ( BASF Corporation), 36.0 parts of deionized water, and 0.5 parts of BYK-011, which is an antifoaming agent, were mixed and dispersed with a stirrer such as a disper to obtain a colored pigment dispersion paste.
第１塗料組成物の調製
着色顔料分散ペースト
着色顔料であるシャニンブルーＧ３１４ ６部、ファストゲンスーパーレッド４００ＲＧ ４ 部、ラーベン５０００ ２０部、および、顔料分散剤であるＤｉｓｐｅｘ（登録商標）Ｕｌｔｒａ ＰＡ ４５５０（ＢＡＳＦ社製） １８．６部、イオン交換水３６．０部、消泡剤であるＢＹＫ－０１１ ０．５部をディスパーなどの撹拌機で混合分散して、着色顔料分散ペーストを得た。 Example 1
Preparation of First Coating Composition Colored Pigment Dispersion Paste 6 parts of Shannin Blue G314, 4 parts of Fastgen Super Red 400RG, 20 parts of Raven 5000, which are color pigments, and Dispex® Ultra PA 4550, which is a pigment dispersant ( BASF Corporation), 36.0 parts of deionized water, and 0.5 parts of BYK-011, which is an antifoaming agent, were mixed and dispersed with a stirrer such as a disper to obtain a colored pigment dispersion paste.
第１塗料組成物
製造例１のアクリル樹脂エマルション１８２部、ジメチルアミノエタノール２．２部、サイメル３２７（混合アルキル化型メラミン樹脂、Ａｌｌｎｅｘ社製、固形分９０％）を４０部、上記着色顔料分散ペーストを１２２部、アルミペーストＳＢ－１０（粉砕型アルミニウム光輝顔料、旭化成社製、平均粒子径１０μｍ、平均厚さ０．０６μｍ、有効成分６５％）を樹脂固形分１００質量部に対して１０．２部、製造例２のリン酸基含有有機化合物５部、ラウリルアシッドフォスフェート０．４部、ブチルセロソルブ５０部、ノイゲンＥＡ－２０７Ｄ（両親媒性化合物、第一工業製薬社製、数平均分子量４２００、固形分５５％） ５．５部（固形分換算で３部）、リノール酸（キシダ化学社製）３部を均一分散してｐＨが８．１となるようジメチルアミノエタノールを添加し、脱イオン水で希釈して、樹脂固形分濃度１２質量％である水性塗料組成物を調製した。 182 parts of the acrylic resin emulsion of First Coating Composition Production Example 1, 2.2 parts of dimethylaminoethanol, 40 parts of Cymel 327 (mixed alkylated melamine resin, manufactured by Allnex, solid content 90%), and the above-mentioned color pigment dispersion 122 parts of paste, aluminum paste SB-10 (pulverized aluminum bright pigment, manufactured by Asahi Kasei Corporation, average particle diameter 10 μm, average thickness 0.06 μm, active ingredient 65%) is added to 100 parts by mass of resin solid content. 2 parts, 5 parts of the phosphoric acid group-containing organic compound of Production Example 2, 0.4 parts of lauryl acid phosphate, 50 parts of butyl cellosolve, Neugen EA-207D (amphiphilic compound, Daiichi Kogyo Seiyaku Co., Ltd., number average molecular weight 4200 , solid content 55%) 5.5 parts (3 parts in terms of solid content), 3 parts of linoleic acid (manufactured by Kishida Chemical Co., Ltd.) are uniformly dispersed, dimethylaminoethanol is added so that the pH becomes 8.1, and desorption is performed. By diluting with ionized water, a water-based coating composition having a resin solid content concentration of 12% by mass was prepared.
製造例１のアクリル樹脂エマルション１８２部、ジメチルアミノエタノール２．２部、サイメル３２７（混合アルキル化型メラミン樹脂、Ａｌｌｎｅｘ社製、固形分９０％）を４０部、上記着色顔料分散ペーストを１２２部、アルミペーストＳＢ－１０（粉砕型アルミニウム光輝顔料、旭化成社製、平均粒子径１０μｍ、平均厚さ０．０６μｍ、有効成分６５％）を樹脂固形分１００質量部に対して１０．２部、製造例２のリン酸基含有有機化合物５部、ラウリルアシッドフォスフェート０．４部、ブチルセロソルブ５０部、ノイゲンＥＡ－２０７Ｄ（両親媒性化合物、第一工業製薬社製、数平均分子量４２００、固形分５５％） ５．５部（固形分換算で３部）、リノール酸（キシダ化学社製）３部を均一分散してｐＨが８．１となるようジメチルアミノエタノールを添加し、脱イオン水で希釈して、樹脂固形分濃度１２質量％である水性塗料組成物を調製した。 182 parts of the acrylic resin emulsion of First Coating Composition Production Example 1, 2.2 parts of dimethylaminoethanol, 40 parts of Cymel 327 (mixed alkylated melamine resin, manufactured by Allnex, solid content 90%), and the above-mentioned color pigment dispersion 122 parts of paste, aluminum paste SB-10 (pulverized aluminum bright pigment, manufactured by Asahi Kasei Corporation, average particle diameter 10 μm, average thickness 0.06 μm, active ingredient 65%) is added to 100 parts by mass of resin solid content. 2 parts, 5 parts of the phosphoric acid group-containing organic compound of Production Example 2, 0.4 parts of lauryl acid phosphate, 50 parts of butyl cellosolve, Neugen EA-207D (amphiphilic compound, Daiichi Kogyo Seiyaku Co., Ltd., number average molecular weight 4200 , solid content 55%) 5.5 parts (3 parts in terms of solid content), 3 parts of linoleic acid (manufactured by Kishida Chemical Co., Ltd.) are uniformly dispersed, dimethylaminoethanol is added so that the pH becomes 8.1, and desorption is performed. By diluting with ionized water, a water-based coating composition having a resin solid content concentration of 12% by mass was prepared.
第２塗料組成物の調製
着色顔料分散ペースト
着色顔料であるラーベン５０００ ３部、顔料分散剤であるＤｉｓｐｅｘ（登録商標）Ｕｌｔｒａ ＰＡ ４５５０（ＢＡＳＦ社製） １８．６部、イオン交換水３６．０部、消泡剤であるＢＹＫ－０１１ ０．５部をディスパーなどの撹拌機で混合分散して、着色顔料分散ペーストを得た。 Preparation of the second coating composition Colored pigment dispersion paste Colored pigment Raven 5000 3 parts, pigment dispersant Dispex (registered trademark) Ultra PA 4550 (manufactured by BASF) 18.6 parts, ion-exchanged water 36.0 parts , and 0.5 parts of BYK-011 as an antifoaming agent were mixed and dispersed with a stirrer such as a disper to obtain a colored pigment dispersion paste.
着色顔料分散ペースト
着色顔料であるラーベン５０００ ３部、顔料分散剤であるＤｉｓｐｅｘ（登録商標）Ｕｌｔｒａ ＰＡ ４５５０（ＢＡＳＦ社製） １８．６部、イオン交換水３６．０部、消泡剤であるＢＹＫ－０１１ ０．５部をディスパーなどの撹拌機で混合分散して、着色顔料分散ペーストを得た。 Preparation of the second coating composition Colored pigment dispersion paste Colored pigment Raven 5000 3 parts, pigment dispersant Dispex (registered trademark) Ultra PA 4550 (manufactured by BASF) 18.6 parts, ion-exchanged water 36.0 parts , and 0.5 parts of BYK-011 as an antifoaming agent were mixed and dispersed with a stirrer such as a disper to obtain a colored pigment dispersion paste.
第２塗料組成物
製造例１のアクリル樹脂エマルション１８２部、ジメチルアミノエタノール２．２部、サイメル３２７（混合アルキル化型メラミン樹脂、Ａｌｌｎｅｘ社製、固形分９０％）を４０部、上記手順で調製した着色顔料分散ペースト３０部、製造例２のリン酸基含有有機化合物５部、ラウリルアシッドフォスフェート０．４部、ブチルセロソルブ５０部、ノイゲンＥＡ－２０７Ｄ（両親媒性化合物、第一工業製薬社製、数平均分子量４２００、固形分５５％） ５．５部（固形分換算で３部）、リノール酸（キシダ化学社製）３部を均一分散してｐＨが８．１となるようジメチルアミノエタノールを添加し、脱イオン水で希釈して、樹脂固形分濃度１５質量％である水性塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して１．５質量部であった。 182 parts of the acrylic resin emulsion of Second Coating Composition Production Example 1, 2.2 parts of dimethylaminoethanol, and 40 parts of Cymel 327 (mixed alkylated melamine resin, manufactured by Allnex, solid content 90%), prepared by the above procedure. 30 parts of the colored pigment dispersion paste, 5 parts of the phosphoric acid group-containing organic compound of Production Example 2, 0.4 parts of lauryl acid phosphate, 50 parts of butyl cellosolve, Noigen EA-207D (amphiphilic compound, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. , number average molecular weight 4200, solid content 55%) 5.5 parts (3 parts in terms of solid content), 3 parts of linoleic acid (manufactured by Kishida Chemical Co., Ltd.) are uniformly dispersed in dimethylaminoethanol so that the pH becomes 8.1. was added and diluted with deionized water to prepare an aqueous coating composition having a resin solid content concentration of 15% by mass.
The amount of the color pigment contained in the obtained second coating composition was 1.5 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
製造例１のアクリル樹脂エマルション１８２部、ジメチルアミノエタノール２．２部、サイメル３２７（混合アルキル化型メラミン樹脂、Ａｌｌｎｅｘ社製、固形分９０％）を４０部、上記手順で調製した着色顔料分散ペースト３０部、製造例２のリン酸基含有有機化合物５部、ラウリルアシッドフォスフェート０．４部、ブチルセロソルブ５０部、ノイゲンＥＡ－２０７Ｄ（両親媒性化合物、第一工業製薬社製、数平均分子量４２００、固形分５５％） ５．５部（固形分換算で３部）、リノール酸（キシダ化学社製）３部を均一分散してｐＨが８．１となるようジメチルアミノエタノールを添加し、脱イオン水で希釈して、樹脂固形分濃度１５質量％である水性塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して１．５質量部であった。 182 parts of the acrylic resin emulsion of Second Coating Composition Production Example 1, 2.2 parts of dimethylaminoethanol, and 40 parts of Cymel 327 (mixed alkylated melamine resin, manufactured by Allnex, solid content 90%), prepared by the above procedure. 30 parts of the colored pigment dispersion paste, 5 parts of the phosphoric acid group-containing organic compound of Production Example 2, 0.4 parts of lauryl acid phosphate, 50 parts of butyl cellosolve, Noigen EA-207D (amphiphilic compound, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. , number average molecular weight 4200, solid content 55%) 5.5 parts (3 parts in terms of solid content), 3 parts of linoleic acid (manufactured by Kishida Chemical Co., Ltd.) are uniformly dispersed in dimethylaminoethanol so that the pH becomes 8.1. was added and diluted with deionized water to prepare an aqueous coating composition having a resin solid content concentration of 15% by mass.
The amount of the color pigment contained in the obtained second coating composition was 1.5 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
複層塗膜の形成
リン酸亜鉛処理した厚み０．８ｍｍ、縦３０ｃｍ、横４０ｃｍのダル鋼板に、カチオン電着塗料組成物である「パワートップＵ－５０）」（日本ペイント・オートモーティブコーティングス社製）を、乾燥膜厚が２０μｍとなるように電着塗装し、１６０℃で３０分間焼き付けた塗板に、中塗り塗料組成物「ＯＰ－３０Ｐ ミドルグレー」（日本ペイント・オートモーティブコーティングス社製、ポリエステル・メラミン系塗料、２５秒（Ｎｏ．４フォードカップを使用し、２０℃で測定）に予め希釈）を、アネスト岩田製エアスプレーガンＷ－１０１－１３２Ｇを用いて乾燥膜厚３５μｍとなるようにエアスプレー塗装し、次いで１４０℃で３０分間焼き付け硬化させて、明度が６０である硬化中塗り塗膜を形成した。
次いで、第１塗料組成物を、室温２３℃、湿度６８％の条件下で乾燥膜厚４μｍになるようにエアスプレー塗装した。４分間のセッティングを行った後、８０℃で５分間のプレヒートを行った。
プレヒート後に、第２塗料組成物を、室温２３℃、湿度６８％の条件下で乾燥膜厚１２μｍになるように、ウェットオンウェットでエアスプレー塗装した。４分間のセッティングを行った後、８０℃で５分間のプレヒートを行った。
第２塗料組成物塗装後のプレヒート後に、塗装板を室温まで放冷し、クリヤー塗料としてマックフロー－Ｏ－１８１０（日本ペイント・オートモーティブコーティングス社製溶剤型クリヤー塗料）を、乾燥膜厚３５μｍとなるようにエアスプレー塗装し、７分間セッティングした。ついで、塗装板を乾燥機で１４０℃、３０分間焼き付けを行うことにより、複層塗膜を有する塗装試験板を得た。 Formation of multi-layer coating film A cationic electrodeposition coating composition "Power Top U-50" (Nippon Paint Automotive Coatings Co., Ltd.) was applied to a dull steel plate with a thickness of 0.8 mm, length of 30 cm, and width of 40 cm, which had been treated with zinc phosphate. ) was electrodeposited so that the dry film thickness was 20 μm, and baked at 160 ° C. for 30 minutes. Polyester/melamine paint, 25 seconds (previously diluted to 20°C using a No. 4 Ford cup) was applied using an air spray gun W-101-132G manufactured by Anest Iwata so that the dry film thickness was 35 μm. and then cured by baking at 140° C. for 30 minutes to form a cured intermediate coating film with a brightness of 60.
Then, the first coating composition was air-sprayed to a dry film thickness of 4 μm under conditions of room temperature of 23° C. and humidity of 68%. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes.
After preheating, the second paint composition was air-sprayed wet-on-wet under the conditions of room temperature of 23° C. and humidity of 68% so as to give a dry film thickness of 12 μm. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes.
After preheating after coating the second coating composition, the coated plate was allowed to cool to room temperature, and Macflow-O-1810 (a solvent-based clear coating manufactured by Nippon Paint Automotive Coatings) was applied as a clear coating to a dry film thickness of 35 μm. Air spray coating was applied so as to obtain a uniform thickness, and the setting was performed for 7 minutes. Then, the coated plate was baked in a dryer at 140° C. for 30 minutes to obtain a coated test plate having a multilayer coating film.
リン酸亜鉛処理した厚み０．８ｍｍ、縦３０ｃｍ、横４０ｃｍのダル鋼板に、カチオン電着塗料組成物である「パワートップＵ－５０）」（日本ペイント・オートモーティブコーティングス社製）を、乾燥膜厚が２０μｍとなるように電着塗装し、１６０℃で３０分間焼き付けた塗板に、中塗り塗料組成物「ＯＰ－３０Ｐ ミドルグレー」（日本ペイント・オートモーティブコーティングス社製、ポリエステル・メラミン系塗料、２５秒（Ｎｏ．４フォードカップを使用し、２０℃で測定）に予め希釈）を、アネスト岩田製エアスプレーガンＷ－１０１－１３２Ｇを用いて乾燥膜厚３５μｍとなるようにエアスプレー塗装し、次いで１４０℃で３０分間焼き付け硬化させて、明度が６０である硬化中塗り塗膜を形成した。
次いで、第１塗料組成物を、室温２３℃、湿度６８％の条件下で乾燥膜厚４μｍになるようにエアスプレー塗装した。４分間のセッティングを行った後、８０℃で５分間のプレヒートを行った。
プレヒート後に、第２塗料組成物を、室温２３℃、湿度６８％の条件下で乾燥膜厚１２μｍになるように、ウェットオンウェットでエアスプレー塗装した。４分間のセッティングを行った後、８０℃で５分間のプレヒートを行った。
第２塗料組成物塗装後のプレヒート後に、塗装板を室温まで放冷し、クリヤー塗料としてマックフロー－Ｏ－１８１０（日本ペイント・オートモーティブコーティングス社製溶剤型クリヤー塗料）を、乾燥膜厚３５μｍとなるようにエアスプレー塗装し、７分間セッティングした。ついで、塗装板を乾燥機で１４０℃、３０分間焼き付けを行うことにより、複層塗膜を有する塗装試験板を得た。 Formation of multi-layer coating film A cationic electrodeposition coating composition "Power Top U-50" (Nippon Paint Automotive Coatings Co., Ltd.) was applied to a dull steel plate with a thickness of 0.8 mm, length of 30 cm, and width of 40 cm, which had been treated with zinc phosphate. ) was electrodeposited so that the dry film thickness was 20 μm, and baked at 160 ° C. for 30 minutes. Polyester/melamine paint, 25 seconds (previously diluted to 20°C using a No. 4 Ford cup) was applied using an air spray gun W-101-132G manufactured by Anest Iwata so that the dry film thickness was 35 μm. and then cured by baking at 140° C. for 30 minutes to form a cured intermediate coating film with a brightness of 60.
Then, the first coating composition was air-sprayed to a dry film thickness of 4 μm under conditions of room temperature of 23° C. and humidity of 68%. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes.
After preheating, the second paint composition was air-sprayed wet-on-wet under the conditions of room temperature of 23° C. and humidity of 68% so as to give a dry film thickness of 12 μm. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes.
After preheating after coating the second coating composition, the coated plate was allowed to cool to room temperature, and Macflow-O-1810 (a solvent-based clear coating manufactured by Nippon Paint Automotive Coatings) was applied as a clear coating to a dry film thickness of 35 μm. Air spray coating was applied so as to obtain a uniform thickness, and the setting was performed for 7 minutes. Then, the coated plate was baked in a dryer at 140° C. for 30 minutes to obtain a coated test plate having a multilayer coating film.
実施例２
第２塗料組成物の調製
第２塗料組成物の調製において、顔料分散ペーストの量を３５部に変更したこと以外は、実施例１と同様の手順により、第２塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して１．７質量部であった。 Example 2
Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 35 parts.
The amount of the color pigment contained in the obtained second coating composition was 1.7 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
第２塗料組成物の調製
第２塗料組成物の調製において、顔料分散ペーストの量を３５部に変更したこと以外は、実施例１と同様の手順により、第２塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して１．７質量部であった。 Example 2
Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 35 parts.
The amount of the color pigment contained in the obtained second coating composition was 1.7 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
複層塗膜の形成
上記より得られた第２塗料組成物を用いたこと以外は、実施例１と同様の手順により、複層塗膜を形成した。 Formation of multi-layer coating film A multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
上記より得られた第２塗料組成物を用いたこと以外は、実施例１と同様の手順により、複層塗膜を形成した。 Formation of multi-layer coating film A multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
実施例３
第２塗料組成物の調製
第２塗料組成物の調製において、顔料分散ペーストの量を４０部に変更したこと以外は、実施例１と同様の手順により、第２塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して２．０質量部であった。 Example 3
Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 40 parts.
The amount of the color pigment contained in the obtained second coating composition was 2.0 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
第２塗料組成物の調製
第２塗料組成物の調製において、顔料分散ペーストの量を４０部に変更したこと以外は、実施例１と同様の手順により、第２塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して２．０質量部であった。 Example 3
Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 40 parts.
The amount of the color pigment contained in the obtained second coating composition was 2.0 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
複層塗膜の形成
上記より得られた第２塗料組成物を用いたこと以外は、実施例１と同様の手順により、複層塗膜を形成した。 Formation of multi-layer coating film A multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
上記より得られた第２塗料組成物を用いたこと以外は、実施例１と同様の手順により、複層塗膜を形成した。 Formation of multi-layer coating film A multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
実施例４
第２塗料組成物の調製
第２塗料組成物の調製において、顔料分散ペーストの量を５０部に変更したこと以外は、実施例１と同様の手順により、第２塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して２．５質量部であった。 Example 4
Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 50 parts.
The amount of the color pigment contained in the obtained second coating composition was 2.5 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
第２塗料組成物の調製
第２塗料組成物の調製において、顔料分散ペーストの量を５０部に変更したこと以外は、実施例１と同様の手順により、第２塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して２．５質量部であった。 Example 4
Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 50 parts.
The amount of the color pigment contained in the obtained second coating composition was 2.5 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
複層塗膜の形成
上記より得られた第２塗料組成物を用いたこと以外は、実施例１と同様の手順により、複層塗膜を形成した。 Formation of multi-layer coating film A multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
上記より得られた第２塗料組成物を用いたこと以外は、実施例１と同様の手順により、複層塗膜を形成した。 Formation of multi-layer coating film A multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
比較例１
第２塗料組成物の調製
第２塗料組成物の調製において、顔料分散ペーストの量を１０部に変更したこと以外は、実施例１と同様の手順により、第２塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して０．５質量部であった。 Comparative example 1
Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 10 parts.
The amount of the color pigment contained in the obtained second coating composition was 0.5 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
第２塗料組成物の調製
第２塗料組成物の調製において、顔料分散ペーストの量を１０部に変更したこと以外は、実施例１と同様の手順により、第２塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して０．５質量部であった。 Comparative example 1
Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 10 parts.
The amount of the color pigment contained in the obtained second coating composition was 0.5 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
複層塗膜の形成
上記より得られた第２塗料組成物を用いたこと以外は、実施例１と同様の手順により、複層塗膜を形成した。 Formation of multi-layer coating film A multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
上記より得られた第２塗料組成物を用いたこと以外は、実施例１と同様の手順により、複層塗膜を形成した。 Formation of multi-layer coating film A multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
比較例２
第２塗料組成物の調製
第２塗料組成物の調製において、顔料分散ペーストの量を１６０部に変更したこと以外は、実施例１と同様の手順により、第２塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して８．０質量部であった。 Comparative example 2
Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 160 parts.
The amount of the color pigment contained in the obtained second coating composition was 8.0 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
第２塗料組成物の調製
第２塗料組成物の調製において、顔料分散ペーストの量を１６０部に変更したこと以外は、実施例１と同様の手順により、第２塗料組成物を調製した。
得られた第２塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して８．０質量部であった。 Comparative example 2
Preparation of Second Coating Composition A second coating composition was prepared in the same manner as in Example 1, except that the amount of the pigment dispersion paste was changed to 160 parts.
The amount of the color pigment contained in the obtained second coating composition was 8.0 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
複層塗膜の形成
上記より得られた第２塗料組成物を用いたこと以外は、実施例１と同様の手順により、複層塗膜を形成した。 Formation of multi-layer coating film A multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
上記より得られた第２塗料組成物を用いたこと以外は、実施例１と同様の手順により、複層塗膜を形成した。 Formation of multi-layer coating film A multi-layer coating film was formed in the same manner as in Example 1, except that the second coating composition obtained above was used.
比較例３
塗料組成物の調製
塗料組成物として、実施例１で調製した第１塗料組成物を用いた。 Comparative example 3
Preparation of Coating Composition The first coating composition prepared in Example 1 was used as the coating composition.
塗料組成物の調製
塗料組成物として、実施例１で調製した第１塗料組成物を用いた。 Comparative example 3
Preparation of Coating Composition The first coating composition prepared in Example 1 was used as the coating composition.
複層塗膜の形成
リン酸亜鉛処理した厚み０．８ｍｍ、縦３０ｃｍ、横４０ｃｍのダル鋼板に、カチオン電着塗料組成物である「パワートップＵ－５０）」（日本ペイント・オートモーティブコーティングス社製）を、乾燥膜厚が２０μｍとなるように電着塗装し、１６０℃で３０分間焼き付けた塗板に、中塗り塗料組成物「ＯＰ－３０Ｐ ミドルグレー」（日本ペイント・オートモーティブコーティングス社製、ポリエステル・メラミン系塗料、２５秒（Ｎｏ．４フォードカップを使用し、２０℃で測定）に予め希釈）を、アネスト岩田製エアスプレーガンＷ－１０１－１３２Ｇを用いて乾燥膜厚３５μｍとなるようにエアスプレー塗装し、次いで１４０℃で３０分間焼き付け硬化させて、明度が６０である硬化中塗り塗膜を形成した。
次いで、上記より得られた塗料組成物を、室温２３℃、湿度６８％の条件下で乾燥膜厚４μｍになるようにエアスプレー塗装した。４分間のセッティングを行った後、８０℃で５分間のプレヒートを行った。
上記プレヒート後に、塗装板を室温まで放冷し、クリヤー塗料としてマックフロー－Ｏ－１８１０（日本ペイント・オートモーティブコーティングス社製溶剤型クリヤー塗料）を、乾燥膜厚３５μｍとなるようにエアスプレー塗装し、７分間セッティングした。ついで、塗装板を乾燥機で１４０℃、３０分間焼き付けを行うことにより、複層塗膜を有する塗装試験板を得た。 Formation of multi-layer coating film A cationic electrodeposition coating composition "Power Top U-50" (Nippon Paint Automotive Coatings Co., Ltd.) was applied to a dull steel plate with a thickness of 0.8 mm, length of 30 cm, and width of 40 cm, which had been treated with zinc phosphate. ) was electrodeposited so that the dry film thickness was 20 μm, and baked at 160 ° C. for 30 minutes. Polyester/melamine paint, 25 seconds (previously diluted to 20°C using a No. 4 Ford cup) was applied using an air spray gun W-101-132G manufactured by Anest Iwata so that the dry film thickness was 35 μm. and then cured by baking at 140° C. for 30 minutes to form a cured intermediate coating film with a brightness of 60.
Then, the coating composition obtained above was air-sprayed to a dry film thickness of 4 μm under conditions of room temperature of 23° C. and humidity of 68%. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes.
After the above preheating, the coated plate was allowed to cool to room temperature, and MACFLO-O-1810 (a solvent-based clear paint manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was air-sprayed as a clear paint to a dry film thickness of 35 μm. , was set for 7 minutes. Then, the coated plate was baked in a dryer at 140° C. for 30 minutes to obtain a coated test plate having a multilayer coating film.
リン酸亜鉛処理した厚み０．８ｍｍ、縦３０ｃｍ、横４０ｃｍのダル鋼板に、カチオン電着塗料組成物である「パワートップＵ－５０）」（日本ペイント・オートモーティブコーティングス社製）を、乾燥膜厚が２０μｍとなるように電着塗装し、１６０℃で３０分間焼き付けた塗板に、中塗り塗料組成物「ＯＰ－３０Ｐ ミドルグレー」（日本ペイント・オートモーティブコーティングス社製、ポリエステル・メラミン系塗料、２５秒（Ｎｏ．４フォードカップを使用し、２０℃で測定）に予め希釈）を、アネスト岩田製エアスプレーガンＷ－１０１－１３２Ｇを用いて乾燥膜厚３５μｍとなるようにエアスプレー塗装し、次いで１４０℃で３０分間焼き付け硬化させて、明度が６０である硬化中塗り塗膜を形成した。
次いで、上記より得られた塗料組成物を、室温２３℃、湿度６８％の条件下で乾燥膜厚４μｍになるようにエアスプレー塗装した。４分間のセッティングを行った後、８０℃で５分間のプレヒートを行った。
上記プレヒート後に、塗装板を室温まで放冷し、クリヤー塗料としてマックフロー－Ｏ－１８１０（日本ペイント・オートモーティブコーティングス社製溶剤型クリヤー塗料）を、乾燥膜厚３５μｍとなるようにエアスプレー塗装し、７分間セッティングした。ついで、塗装板を乾燥機で１４０℃、３０分間焼き付けを行うことにより、複層塗膜を有する塗装試験板を得た。 Formation of multi-layer coating film A cationic electrodeposition coating composition "Power Top U-50" (Nippon Paint Automotive Coatings Co., Ltd.) was applied to a dull steel plate with a thickness of 0.8 mm, length of 30 cm, and width of 40 cm, which had been treated with zinc phosphate. ) was electrodeposited so that the dry film thickness was 20 μm, and baked at 160 ° C. for 30 minutes. Polyester/melamine paint, 25 seconds (previously diluted to 20°C using a No. 4 Ford cup) was applied using an air spray gun W-101-132G manufactured by Anest Iwata so that the dry film thickness was 35 μm. and then cured by baking at 140° C. for 30 minutes to form a cured intermediate coating film with a brightness of 60.
Then, the coating composition obtained above was air-sprayed to a dry film thickness of 4 μm under conditions of room temperature of 23° C. and humidity of 68%. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes.
After the above preheating, the coated plate was allowed to cool to room temperature, and MACFLO-O-1810 (a solvent-based clear paint manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was air-sprayed as a clear paint to a dry film thickness of 35 μm. , was set for 7 minutes. Then, the coated plate was baked in a dryer at 140° C. for 30 minutes to obtain a coated test plate having a multilayer coating film.
比較例４
塗料組成物の調製
着色顔料分散ペースト
着色顔料であるＨＥＬＩＯＧＥＮ ＢＬＵＥ Ｌ６７００Ｆ ２．８部、ＥＭＰＥＲＯＲ－２０００ ８．０部、ＨＯＳＴＡＰＥＲＭ ＶＩＯＬＥＴ ＲＬ ＮＦＶＰ３３６ １．５部、そして、顔料分散剤であるＤｉｓｐｅｘ（登録商標）Ｕｌｔｒａ ＰＡ ４５５０（ＢＡＳＦ社製） １８．６部、イオン交換水３６．０部、消泡剤であるＢＹＫ－０１１ ０．５部をディスパーなどの撹拌機で混合分散して、着色顔料分散ペーストを得た。 Comparative example 4
2.8 parts of HELIOGEN BLUE L6700F, 8.0 parts of EMPEROR-2000, 1.5 parts of HOSTAPERM VIOLET RL NFVP336, which are colored pigments, and Dispex® , which is a pigment dispersant. 18.6 parts of Ultra PA 4550 (manufactured by BASF), 36.0 parts of ion-exchanged water, and 0.5 parts of antifoaming agent BYK-011 are mixed and dispersed with a stirrer such as a disper to form a colored pigment dispersion paste. Obtained.
塗料組成物の調製
着色顔料分散ペースト
着色顔料であるＨＥＬＩＯＧＥＮ ＢＬＵＥ Ｌ６７００Ｆ ２．８部、ＥＭＰＥＲＯＲ－２０００ ８．０部、ＨＯＳＴＡＰＥＲＭ ＶＩＯＬＥＴ ＲＬ ＮＦＶＰ３３６ １．５部、そして、顔料分散剤であるＤｉｓｐｅｘ（登録商標）Ｕｌｔｒａ ＰＡ ４５５０（ＢＡＳＦ社製） １８．６部、イオン交換水３６．０部、消泡剤であるＢＹＫ－０１１ ０．５部をディスパーなどの撹拌機で混合分散して、着色顔料分散ペーストを得た。 Comparative example 4
2.8 parts of HELIOGEN BLUE L6700F, 8.0 parts of EMPEROR-2000, 1.5 parts of HOSTAPERM VIOLET RL NFVP336, which are colored pigments, and Dispex® , which is a pigment dispersant. 18.6 parts of Ultra PA 4550 (manufactured by BASF), 36.0 parts of ion-exchanged water, and 0.5 parts of antifoaming agent BYK-011 are mixed and dispersed with a stirrer such as a disper to form a colored pigment dispersion paste. Obtained.
塗料組成物
製造例１のアクリル樹脂エマルション１８２部、ジメチルアミノエタノール２．２部、サイメル３２７（混合アルキル化型メラミン樹脂、Ａｌｌｎｅｘ社製、固形分９０％）を４０部、上記手順で調製した着色顔料分散ペースト４８部、ＡＳＴＲＯＳＨＩＮＥ ＵＣ－６６００（アルミニウム光輝性顔料、日本防湿工業社製、平均粒子径２２μｍ）３．５部、製造例２のリン酸基含有有機化合物５部、ラウリルアシッドフォスフェート０．４部、ブチルセロソルブ５０部、ノイゲンＥＡ－２０７Ｄ（両親媒性化合物、第一工業製薬社製、数平均分子量４２００、固形分５５％） ５．５部（固形分換算で３部）、リノール酸（キシダ化学社製）３部を均一分散してｐＨが８．１となるようジメチルアミノエタノールを添加し、脱イオン水で希釈して、樹脂固形分濃度２６質量％である水性塗料組成物を調製した。
得られた塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して２．９質量部であった。 182 parts of the acrylic resin emulsion of Coating Composition Production Example 1, 2.2 parts of dimethylaminoethanol, 40 parts of Cymel 327 (mixed alkylated melamine resin, manufactured by Allnex, solid content 90%), coloring prepared by the above procedure Pigment dispersion paste 48 parts, ASTROSHINE UC-6600 (aluminum bright pigment, manufactured by Nippon Moisture Industry Co., Ltd., average particle size 22 μm) 3.5 parts, phosphoric acid group-containing organic compound of Production Example 2 5 parts, lauryl acid phosphate 0 .4 parts, butyl cellosolve 50 parts, Neugen EA-207D (amphiphilic compound, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., number average molecular weight 4200, solid content 55%) 5.5 parts (3 parts in terms of solid content), linoleic acid (manufactured by Kishida Chemical Co., Ltd.) 3 parts are uniformly dispersed, dimethylaminoethanol is added so that the pH becomes 8.1, diluted with deionized water, and an aqueous coating composition having a resin solid content concentration of 26% by mass is prepared. prepared.
The amount of the color pigment contained in the obtained coating composition was 2.9 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
製造例１のアクリル樹脂エマルション１８２部、ジメチルアミノエタノール２．２部、サイメル３２７（混合アルキル化型メラミン樹脂、Ａｌｌｎｅｘ社製、固形分９０％）を４０部、上記手順で調製した着色顔料分散ペースト４８部、ＡＳＴＲＯＳＨＩＮＥ ＵＣ－６６００（アルミニウム光輝性顔料、日本防湿工業社製、平均粒子径２２μｍ）３．５部、製造例２のリン酸基含有有機化合物５部、ラウリルアシッドフォスフェート０．４部、ブチルセロソルブ５０部、ノイゲンＥＡ－２０７Ｄ（両親媒性化合物、第一工業製薬社製、数平均分子量４２００、固形分５５％） ５．５部（固形分換算で３部）、リノール酸（キシダ化学社製）３部を均一分散してｐＨが８．１となるようジメチルアミノエタノールを添加し、脱イオン水で希釈して、樹脂固形分濃度２６質量％である水性塗料組成物を調製した。
得られた塗料組成物中に含まれる着色顔料の量は、塗料組成物中の樹脂固形分１００質量部に対して２．９質量部であった。 182 parts of the acrylic resin emulsion of Coating Composition Production Example 1, 2.2 parts of dimethylaminoethanol, 40 parts of Cymel 327 (mixed alkylated melamine resin, manufactured by Allnex, solid content 90%), coloring prepared by the above procedure Pigment dispersion paste 48 parts, ASTROSHINE UC-6600 (aluminum bright pigment, manufactured by Nippon Moisture Industry Co., Ltd., average particle size 22 μm) 3.5 parts, phosphoric acid group-containing organic compound of Production Example 2 5 parts, lauryl acid phosphate 0 .4 parts, butyl cellosolve 50 parts, Neugen EA-207D (amphiphilic compound, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., number average molecular weight 4200, solid content 55%) 5.5 parts (3 parts in terms of solid content), linoleic acid (manufactured by Kishida Chemical Co., Ltd.) 3 parts are uniformly dispersed, dimethylaminoethanol is added so that the pH becomes 8.1, diluted with deionized water, and an aqueous coating composition having a resin solid content concentration of 26% by mass is prepared. prepared.
The amount of the color pigment contained in the obtained coating composition was 2.9 parts by mass with respect to 100 parts by mass of the resin solid content in the coating composition.
複層塗膜の形成
リン酸亜鉛処理した厚み０．８ｍｍ、縦３０ｃｍ、横４０ｃｍのダル鋼板に、カチオン電着塗料組成物である「パワートップＵ－５０）」（日本ペイント・オートモーティブコーティングス社製）を、乾燥膜厚が２０μｍとなるように電着塗装し、１６０℃で３０分間焼き付けた塗板に、中塗り塗料組成物「ＯＰ－３０Ｐ ミドルグレー」（日本ペイント・オートモーティブコーティングス社製、ポリエステル・メラミン系塗料、２５秒（Ｎｏ．４フォードカップを使用し、２０℃で測定）に予め希釈）を、アネスト岩田製エアスプレーガンＷ－１０１－１３２Ｇを用いて乾燥膜厚３５μｍとなるようにエアスプレー塗装し、次いで１４０℃で３０分間焼き付け硬化させて、明度が６０である硬化中塗り塗膜を形成した。
次いで、上記より得られた塗料組成物を、室温２３℃、湿度６８％の条件下で乾燥膜厚１２μｍになるようにエアスプレー塗装した。４分間のセッティングを行った後、８０℃で５分間のプレヒートを行った。
上記プレヒート後に、塗装板を室温まで放冷し、クリヤー塗料としてマックフロー－Ｏ－１８１０（日本ペイント・オートモーティブコーティングス社製溶剤型クリヤー塗料）を、乾燥膜厚３５μｍとなるようにエアスプレー塗装し、７分間セッティングした。ついで、塗装板を乾燥機で１４０℃、３０分間焼き付けを行うことにより、複層塗膜を有する塗装試験板を得た。 Formation of multi-layer coating film A cationic electrodeposition coating composition "Power Top U-50" (Nippon Paint Automotive Coatings Co., Ltd.) was applied to a dull steel plate with a thickness of 0.8 mm, length of 30 cm, and width of 40 cm, which had been treated with zinc phosphate. ) was electrodeposited so that the dry film thickness was 20 μm, and baked at 160 ° C. for 30 minutes. Polyester/melamine paint, 25 seconds (previously diluted to 20°C using a No. 4 Ford cup) was applied using an air spray gun W-101-132G manufactured by Anest Iwata so that the dry film thickness was 35 μm. and then cured by baking at 140° C. for 30 minutes to form a cured intermediate coating film with a brightness of 60.
Next, the coating composition obtained above was air-sprayed to a dry film thickness of 12 μm under conditions of room temperature of 23° C. and humidity of 68%. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes.
After the above preheating, the coated plate was allowed to cool to room temperature, and MACFLO-O-1810 (a solvent-based clear paint manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was air-sprayed as a clear paint to a dry film thickness of 35 μm. , was set for 7 minutes. Then, the coated plate was baked in a dryer at 140° C. for 30 minutes to obtain a coated test plate having a multilayer coating film.
リン酸亜鉛処理した厚み０．８ｍｍ、縦３０ｃｍ、横４０ｃｍのダル鋼板に、カチオン電着塗料組成物である「パワートップＵ－５０）」（日本ペイント・オートモーティブコーティングス社製）を、乾燥膜厚が２０μｍとなるように電着塗装し、１６０℃で３０分間焼き付けた塗板に、中塗り塗料組成物「ＯＰ－３０Ｐ ミドルグレー」（日本ペイント・オートモーティブコーティングス社製、ポリエステル・メラミン系塗料、２５秒（Ｎｏ．４フォードカップを使用し、２０℃で測定）に予め希釈）を、アネスト岩田製エアスプレーガンＷ－１０１－１３２Ｇを用いて乾燥膜厚３５μｍとなるようにエアスプレー塗装し、次いで１４０℃で３０分間焼き付け硬化させて、明度が６０である硬化中塗り塗膜を形成した。
次いで、上記より得られた塗料組成物を、室温２３℃、湿度６８％の条件下で乾燥膜厚１２μｍになるようにエアスプレー塗装した。４分間のセッティングを行った後、８０℃で５分間のプレヒートを行った。
上記プレヒート後に、塗装板を室温まで放冷し、クリヤー塗料としてマックフロー－Ｏ－１８１０（日本ペイント・オートモーティブコーティングス社製溶剤型クリヤー塗料）を、乾燥膜厚３５μｍとなるようにエアスプレー塗装し、７分間セッティングした。ついで、塗装板を乾燥機で１４０℃、３０分間焼き付けを行うことにより、複層塗膜を有する塗装試験板を得た。 Formation of multi-layer coating film A cationic electrodeposition coating composition "Power Top U-50" (Nippon Paint Automotive Coatings Co., Ltd.) was applied to a dull steel plate with a thickness of 0.8 mm, length of 30 cm, and width of 40 cm, which had been treated with zinc phosphate. ) was electrodeposited so that the dry film thickness was 20 μm, and baked at 160 ° C. for 30 minutes. Polyester/melamine paint, 25 seconds (previously diluted to 20°C using a No. 4 Ford cup) was applied using an air spray gun W-101-132G manufactured by Anest Iwata so that the dry film thickness was 35 μm. and then cured by baking at 140° C. for 30 minutes to form a cured intermediate coating film with a brightness of 60.
Next, the coating composition obtained above was air-sprayed to a dry film thickness of 12 μm under conditions of room temperature of 23° C. and humidity of 68%. After setting for 4 minutes, preheating was performed at 80° C. for 5 minutes.
After the above preheating, the coated plate was allowed to cool to room temperature, and MACFLO-O-1810 (a solvent-based clear paint manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was air-sprayed as a clear paint to a dry film thickness of 35 μm. , was set for 7 minutes. Then, the coated plate was baked in a dryer at 140° C. for 30 minutes to obtain a coated test plate having a multilayer coating film.
上記実施例および比較例で形成した複層塗膜などを用いて、下記評価を行った。評価結果を下記表に示す。
The following evaluations were performed using the multilayer coating films formed in the above examples and comparative examples. The evaluation results are shown in the table below.
複層塗膜の光輝強度（Ｓｉ）および光輝面積（Ｓａ値）の測定
各実施例および比較例で形成した複層塗膜を有する塗装試験板を用いて、入射角４５°受光角１５°および４５°における光輝強度Ｓｉ値、入射角４５°受光角４５°における光輝面積Ｓａ値を、ＢＹＫ社製のＢＹＫ－ｍａｃ ｉ（マルチアングル（６角度）測色、光輝感・粒子感測定器）を用いて測定した。 Measurement of brilliance intensity (Si) and brilliance area (Sa value) of multi-layer coating film The brightness intensity Si value at 45° and the brightness area Sa value at an incident angle of 45° and a light receiving angle of 45° were measured by BYK-mac i (multi-angle (6 angles) colorimetry, brightness/graininess measuring instrument) manufactured by BYK. was measured using
各実施例および比較例で形成した複層塗膜を有する塗装試験板を用いて、入射角４５°受光角１５°および４５°における光輝強度Ｓｉ値、入射角４５°受光角４５°における光輝面積Ｓａ値を、ＢＹＫ社製のＢＹＫ－ｍａｃ ｉ（マルチアングル（６角度）測色、光輝感・粒子感測定器）を用いて測定した。 Measurement of brilliance intensity (Si) and brilliance area (Sa value) of multi-layer coating film The brightness intensity Si value at 45° and the brightness area Sa value at an incident angle of 45° and a light receiving angle of 45° were measured by BYK-mac i (multi-angle (6 angles) colorimetry, brightness/graininess measuring instrument) manufactured by BYK. was measured using
複層塗膜の明度Ｌ＊の測定
各実施例および比較例で形成した複層塗膜を有する塗装試験板を用いて、入射角４５°受光角２５°および４５°における明度Ｌ＊値を、多角度分光測色計ＢＹＫ－ｍａｃｉ（ＢＹＫ社製）を用いて測定した。 Measurement of lightness L* of multi-layer coating film Using a coated test plate having a multi-layer coating film formed in each example and comparative example, the lightness L* value at an incident angle of 45° and an acceptance angle of 25° and 45° It was measured using a multi-angle spectrophotometer BYK-maci (manufactured by BYK).
各実施例および比較例で形成した複層塗膜を有する塗装試験板を用いて、入射角４５°受光角２５°および４５°における明度Ｌ＊値を、多角度分光測色計ＢＹＫ－ｍａｃｉ（ＢＹＫ社製）を用いて測定した。 Measurement of lightness L* of multi-layer coating film Using a coated test plate having a multi-layer coating film formed in each example and comparative example, the lightness L* value at an incident angle of 45° and an acceptance angle of 25° and 45° It was measured using a multi-angle spectrophotometer BYK-maci (manufactured by BYK).
複層塗膜の外観評価
各実施例および比較例で形成した複層塗膜を有する塗装試験板を目視観察し、下記基準により評価した。
２：複層塗膜が黒色でありながら輝度が感じられる
１：複層塗膜が黒色ではなく白みがかかったグレー色に感じられるか、または、黒色に感じられる一方で輝度が感じられない Evaluation of Appearance of Multilayer Coating Film The coated test panels having the multilayer coating film formed in each example and comparative example were visually observed and evaluated according to the following criteria.
2: Although the multilayer coating film is black, brightness is perceived. 1: The multilayer coating film is perceived as whitish gray instead of black, or perceived as black, but lacks brightness.
各実施例および比較例で形成した複層塗膜を有する塗装試験板を目視観察し、下記基準により評価した。
２：複層塗膜が黒色でありながら輝度が感じられる
１：複層塗膜が黒色ではなく白みがかかったグレー色に感じられるか、または、黒色に感じられる一方で輝度が感じられない Evaluation of Appearance of Multilayer Coating Film The coated test panels having the multilayer coating film formed in each example and comparative example were visually observed and evaluated according to the following criteria.
2: Although the multilayer coating film is black, brightness is perceived. 1: The multilayer coating film is perceived as whitish gray instead of black, or perceived as black, but lacks brightness.
実施例の複層塗膜はいずれも、輝度が認識される一方で、明度および彩度が低く、色相としては黒色塗膜と認識される複層塗膜であることが確認された。
比較例１の複層塗膜は、Ｌ＊（２５°）値が高い例である。この例では、いわゆるハイライト受光角条件下の明度が高く、全体として明るさが認識されており、濃グレー色と認識される塗膜であった。
比較例２の複層塗膜は、Ｌ＊（２５°）値が低い例である。この例では、黒色塗膜と感じられる一方で、いわゆるハイライト受光角条件下においても輝度が感じられない塗膜であった。
比較例３、４は、第１塗料組成物および第２塗料組成物を用いるのではなく、１つの塗料組成物を用いて、輝度、低明度および低彩度の意匠の実現を試みた例である。比較例３は、本開示の第２塗膜を有しないことから、ハイライト受光角条件下の明度が高くなり、塗膜全体として明るく、グレー色と認識される塗膜であった。
比較例４は、比較例３と比べて着色顔料を多くした上で、輝度を認識できるよう光輝性顔料の種類を変更した例である。この例では、ハイライト受光角条件下の明度はある程度下がったものの、光輝強度が高くなり、全体として明るさが認識され、濃グレー色と認識される塗膜であった。 It was confirmed that all of the multi-layered coating films of Examples had brightness, but had low brightness and chroma, and were recognized as black coating films in terms of hue.
The multilayer coating film of Comparative Example 1 is an example with a high L*(25°) value. In this example, the brightness was high under the so-called highlight acceptance angle condition, and the brightness was recognized as a whole, and the coating film was recognized as a dark gray color.
The multilayer coating film of Comparative Example 2 is an example with a low L*(25°) value. In this example, the coating film was perceived as a black coating film, but the coating film was not perceived to be bright even under so-called high light receiving angle conditions.
Comparative Examples 3 and 4 are examples in which an attempt was made to realize a design with brightness, low brightness and low saturation using one coating composition instead of using the first coating composition and the second coating composition. be. Since Comparative Example 3 did not have the second coating film of the present disclosure, the brightness was high under the light receiving angle condition, and the coating film as a whole was bright and recognized as a gray color.
Comparative Example 4 is an example in which more color pigments are used than in Comparative Example 3, and the type of luster pigment is changed so that luminance can be recognized. In this example, although the lightness under the light receiving angle condition decreased to some extent, the brightness intensity increased, and the overall brightness was recognized, and the coating film was recognized as a dark gray color.
比較例１の複層塗膜は、Ｌ＊（２５°）値が高い例である。この例では、いわゆるハイライト受光角条件下の明度が高く、全体として明るさが認識されており、濃グレー色と認識される塗膜であった。
比較例２の複層塗膜は、Ｌ＊（２５°）値が低い例である。この例では、黒色塗膜と感じられる一方で、いわゆるハイライト受光角条件下においても輝度が感じられない塗膜であった。
比較例３、４は、第１塗料組成物および第２塗料組成物を用いるのではなく、１つの塗料組成物を用いて、輝度、低明度および低彩度の意匠の実現を試みた例である。比較例３は、本開示の第２塗膜を有しないことから、ハイライト受光角条件下の明度が高くなり、塗膜全体として明るく、グレー色と認識される塗膜であった。
比較例４は、比較例３と比べて着色顔料を多くした上で、輝度を認識できるよう光輝性顔料の種類を変更した例である。この例では、ハイライト受光角条件下の明度はある程度下がったものの、光輝強度が高くなり、全体として明るさが認識され、濃グレー色と認識される塗膜であった。 It was confirmed that all of the multi-layered coating films of Examples had brightness, but had low brightness and chroma, and were recognized as black coating films in terms of hue.
The multilayer coating film of Comparative Example 1 is an example with a high L*(25°) value. In this example, the brightness was high under the so-called highlight acceptance angle condition, and the brightness was recognized as a whole, and the coating film was recognized as a dark gray color.
The multilayer coating film of Comparative Example 2 is an example with a low L*(25°) value. In this example, the coating film was perceived as a black coating film, but the coating film was not perceived to be bright even under so-called high light receiving angle conditions.
Comparative Examples 3 and 4 are examples in which an attempt was made to realize a design with brightness, low brightness and low saturation using one coating composition instead of using the first coating composition and the second coating composition. be. Since Comparative Example 3 did not have the second coating film of the present disclosure, the brightness was high under the light receiving angle condition, and the coating film as a whole was bright and recognized as a gray color.
Comparative Example 4 is an example in which more color pigments are used than in Comparative Example 3, and the type of luster pigment is changed so that luminance can be recognized. In this example, although the lightness under the light receiving angle condition decreased to some extent, the brightness intensity increased, and the overall brightness was recognized, and the coating film was recognized as a dark gray color.
本開示の複層塗膜は、黒色と認識されるほど明度および彩度が低い一方で輝度が認識される、黒色の重厚感および輝度による輝き感の両方を伴う、意匠性に優れた塗膜である。上記複層塗膜は、各種物品（例えば、乗用車、トラック、オートバイ、バスなどの自動車車体およびその部品など）の意匠性塗膜として好適に用いることができる。
The multilayer coating film of the present disclosure has both a profound feeling of black color and a feeling of brilliance due to brightness, and has excellent design properties, with brightness and chroma being so low that it can be recognized as black, while brightness is recognized. is. The multi-layer coating film can be suitably used as a decorative coating film for various articles (for example, automobile bodies such as passenger cars, trucks, motorcycles and buses, and parts thereof).
Claims (6)
- 第１塗膜、第２塗膜およびクリヤー塗膜をこの順に有する複層塗膜であって、
前記第１塗膜は、第１塗膜形成樹脂および光輝性顔料を含む第１塗料組成物の硬化塗膜であり、
前記第２塗膜は、第２塗膜形成樹脂および着色顔料を含む第２塗料組成物の硬化塗膜であり、
前記第１塗膜中に含まれる光輝性顔料は鱗片状アルミニウム顔料を含み、
前記第２塗膜中に含まれる着色顔料の含有量は、塗膜に含まれる樹脂固形分１００質量部に対して１．５～６質量部の範囲内であり、
前記複層塗膜は、
入射角４５°受光角４５°における光輝面積Ｓａ（４５°）値が８以上３５以下であり、
入射角４５°受光角１５°における光輝強度Ｓｉ（１５°）値が１以上１８以下であり、入射角４５°受光角２５°におけるＬ＊（２５°）値が５以上２５以下である、
複層塗膜。 A multilayer coating film having a first coating film, a second coating film and a clear coating film in this order,
The first coating film is a cured coating film of a first coating composition containing a first coating film-forming resin and a bright pigment,
The second coating is a cured coating of a second coating composition comprising a second coating film-forming resin and a color pigment,
The bright pigment contained in the first coating film includes a scale-like aluminum pigment,
The content of the coloring pigment contained in the second coating is in the range of 1.5 to 6 parts by mass with respect to 100 parts by mass of the resin solid content contained in the coating,
The multilayer coating film is
The bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less,
The brightness intensity Si (15 °) value at an incident angle of 45 ° and a light receiving angle of 15 ° is 1 or more and 18 or less, and the L * (25 °) value at an incident angle of 45 ° and a light receiving angle of 25 ° is 5 or more and 25 or less.
Multi-layer coating. - 前記第１塗膜の膜厚は、３～１３μｍの範囲内であり、
前記第１塗膜に含まれる鱗片状アルミニウム顔料の含有量は、塗膜に含まれる樹脂固形分１００質量部に対して３～１３質量部の範囲内である、
請求項１に記載の複層塗膜。 The film thickness of the first coating film is in the range of 3 to 13 μm,
The content of the scale-like aluminum pigment contained in the first coating film is in the range of 3 to 13 parts by mass with respect to 100 parts by mass of the resin solid content contained in the coating film.
The multilayer coating film according to claim 1. - 前記複層塗膜は、
入射角４５°受光角４５°における光輝強度Ｓｉ（４５°）値が１以上１７以下であり入射角４５°受光角４５°におけるＬ＊（４５°）値が２以上７以下である、
請求項１または２に記載の複層塗膜。 The multilayer coating film is
The luminous intensity Si (45 °) value at an incident angle of 45 ° and a light receiving angle of 45 ° is 1 or more and 17 or less, and the L * (45 °) value at an incident angle of 45 ° and a light receiving angle of 45 ° is 2 or more and 7 or less.
The multilayer coating film according to claim 1 or 2. - 被塗物に、第１塗料組成物、第２塗料組成物およびクリヤー塗料組成物を順次塗装して、複層塗膜を形成する方法であって、
前記第１塗料組成物は、第１塗膜形成樹脂および光輝性顔料を含み、
前記第２塗料組成物は、第２塗膜形成樹脂および着色顔料を含み、
前記第１塗料組成物中に含まれる光輝性顔料は鱗片状アルミニウム顔料を含み、
前記第２塗料組成物中に含まれる着色顔料の含有量は、第２塗料組成物中に含まれる樹脂固形分１００質量部に対して１．５～６質量部の範囲内であり、
前記複層塗膜は、
入射角４５°受光角４５°における光輝面積Ｓａ（４５°）値が８以上３５以下であり、
入射角４５°受光角１５°における光輝強度Ｓｉ（１５°）値が１以上１８以下であり、入射角４５°受光角２５°におけるＬ＊（２５°）値が５以上２５以下である、
複層塗膜の形成方法。 A method of sequentially coating a first coating composition, a second coating composition and a clear coating composition on an object to form a multilayer coating film,
The first coating composition comprises a first coating film-forming resin and a bright pigment,
The second coating composition comprises a second film-forming resin and a color pigment,
The bright pigment contained in the first coating composition includes a scale-like aluminum pigment,
The content of the coloring pigment contained in the second coating composition is in the range of 1.5 to 6 parts by mass with respect to 100 parts by mass of the resin solid content contained in the second coating composition,
The multilayer coating film is
The bright area Sa (45°) value at an incident angle of 45° and a light receiving angle of 45° is 8 or more and 35 or less,
The brightness intensity Si (15 °) value at an incident angle of 45 ° and a light receiving angle of 15 ° is 1 or more and 18 or less, and the L * (25 °) value at an incident angle of 45 ° and a light receiving angle of 25 ° is 5 or more and 25 or less.
A method for forming a multilayer coating film. - 前記複層塗膜の形成は、被塗物に、第１塗料組成物、第２塗料組成物およびクリヤー塗料組成物をウェットオンウェットで順次塗装して、複層塗膜を形成する方法である、
請求項４に記載の複層塗膜の形成方法。 The formation of the multi-layer coating film is a method of sequentially applying the first coating composition, the second coating composition and the clear coating composition to the object to be coated in a wet-on-wet manner to form a multi-layer coating film. ,
The method for forming a multilayer coating film according to claim 4. - 請求項１～３いずれかに記載の複層塗膜を有する物品。 An article having the multilayer coating film according to any one of claims 1 to 3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140346A (en) * | 1997-11-05 | 1999-05-25 | Nippon Paint Co Ltd | Brilliant coating composition and method for forming brilliant composite coating film |
| JP2000271536A (en) * | 1999-03-25 | 2000-10-03 | Nippon Paint Co Ltd | Method for forming metallic coating film |
| JP2000301057A (en) * | 1999-04-16 | 2000-10-31 | Nippon Paint Co Ltd | Formation of metallic coating |
| JP6805401B1 (en) * | 2019-11-22 | 2020-12-23 | 関西ペイント株式会社 | Multi-layer coating film forming method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11140346A (en) * | 1997-11-05 | 1999-05-25 | Nippon Paint Co Ltd | Brilliant coating composition and method for forming brilliant composite coating film |
| JP2000271536A (en) * | 1999-03-25 | 2000-10-03 | Nippon Paint Co Ltd | Method for forming metallic coating film |
| JP2000301057A (en) * | 1999-04-16 | 2000-10-31 | Nippon Paint Co Ltd | Formation of metallic coating |
| JP6805401B1 (en) * | 2019-11-22 | 2020-12-23 | 関西ペイント株式会社 | Multi-layer coating film forming method |
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