WO2010032654A1 - 樹脂被覆メタリック顔料、それを含有する水性塗料、それが塗布された塗装物、およびその製造方法 - Google Patents
樹脂被覆メタリック顔料、それを含有する水性塗料、それが塗布された塗装物、およびその製造方法 Download PDFInfo
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- WO2010032654A1 WO2010032654A1 PCT/JP2009/065629 JP2009065629W WO2010032654A1 WO 2010032654 A1 WO2010032654 A1 WO 2010032654A1 JP 2009065629 W JP2009065629 W JP 2009065629W WO 2010032654 A1 WO2010032654 A1 WO 2010032654A1
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- resin
- metallic pigment
- coated metallic
- outermost layer
- layer
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
- C09C1/644—Aluminium treated with organic compounds, e.g. polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
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- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/62—L* (lightness axis)
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
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- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/301—Thickness of the core
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- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/307—Thickness of an outermost protective layer
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- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/40—Interference pigments comprising an outermost surface coating
- C09C2200/402—Organic protective coating
- C09C2200/405—High molecular weight materials, e.g. polymers
- C09C2200/406—High molecular weight materials, e.g. polymers comprising additional functional groups, e.g. -NH2, -C=C- or -SO3
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- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/50—Interference pigments comprising a layer or a core consisting of or comprising discrete particles, e.g. nanometric or submicrometer-sized particles
- C09C2200/505—Inorganic particles, e.g. oxides, nitrides or carbides
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- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/50—Interference pigments comprising a layer or a core consisting of or comprising discrete particles, e.g. nanometric or submicrometer-sized particles
- C09C2200/507—Organic particles, e.g. polymers or dyes
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- C09C2220/00—Methods of preparing the interference pigments
- C09C2220/20—PVD, CVD methods or coating in a gas-phase using a fluidized bed
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2998—Coated including synthetic resin or polymer
Definitions
- the present invention relates to a resin-coated metallic pigment, a water-based paint containing the same, a coated product on which the resin-coated metallic pigment is applied, and a method for producing the same. More specifically, the present invention relates to a resin-coated metallic pigment formed with a coating layer exhibiting excellent water resistance (wet) when it is made into a coating with an aqueous paint while maintaining the chemical resistance of the coating, The present invention relates to a water-based paint to be contained, a coated product to which it is applied, and a method for producing the same.
- the chemical resistance of a coating film refers to the property that various properties such as color tone are not easily changed even when the coating film is immersed in an aqueous solution of a chemical such as acid, alkali, or salt.
- a coating film containing a metallic pigment this chemical resistance mainly depends on the performance of the metallic pigment.
- Patent Document 1 describes trimethylolpropane triacrylate and / or trimethylolpropane triacrylate.
- Metal pigments have been proposed which are coated with a copolymer of methacrylate and a small amount of acrylic acid and / or methacrylic acid.
- Patent Document 2 discloses a radically polymerizable unsaturated carboxylic acid and / or a phosphoric acid mono- or diester having a radically polymerizable double bond and 3 or more radically polymerizable double bonds.
- the resin is strongly adhered and surface-coated by a highly three-dimensional resin generated from the monomer having, and ⁇ E, which is evaluated for alkali resistance, is 1.0 or less, and does not substantially aggregate in the heat stability test A resin-coated metal pigment characterized by the above has been proposed.
- Patent Document 3 discloses a copolymer obtained by reacting at least two selected from the group consisting of an oligomer having at least one polymerizable double bond and a monomer. Aluminum flakes that are uniformly coated and have a microscopically smooth surface have been proposed.
- JP-A-2005-146111 Patent Document 4 discloses that the surface of a raw material aluminum pigment has a monomer having a polymerizable double bond, a monomer having one polymerizable double bond and one benzene ring, and ( There has been proposed a resin-coated aluminum pigment coated with a copolymer obtained by polymerizing (meth) acrylic acid.
- Patent Document 5 JP 2007-119671 A discloses that a phosphate ester having a radical polymerizable double bond is brought into contact with a metal pigment to adsorb the phosphate ester, and then has a polymerizable double bond.
- Metal pigments in which a resin coating layer is formed by polymerization of monomers have been proposed.
- the water resistance (humidity) of a coating film means that the coating film can be applied even if the coating film is kept in water at a temperature relatively higher than room temperature (about 40 to 50 ° C.) or in a wet state with a relative humidity of 98% or more. It refers to the property of maintaining anticorrosion performance that prevents alteration of the color tone of the film. In a coating film containing a metallic pigment, this water resistance (humidity) also depends mainly on the performance of the metallic pigment.
- JP-A-2004-131542 discloses a hydrolytic condensate of a compound having a siloxane bond.
- An aluminum pigment coated with is proposed.
- JP 2007-204692 A discloses a hydrolyzed condensate of a compound having a siloxane bond, a radical polymerizable unsaturated carboxylic acid, and / or a phosphoric acid having a radical polymerizable double bond.
- an aluminum pigment coated with at least one selected from phosphonic acid mono- or diesters and a resin composed of a monomer having two or more radical polymerizable double bonds has been proposed.
- Patent Document 8 is a metallic pigment in which aluminum particles are used as base particles and a single layer or a multi-layer coating layer covering the surface of the aluminum particles is formed.
- a metallic pigment is proposed in which the outermost layer of the coating layer includes a polymer obtained by polymerizing a monomer having a basic group and at least one polymerizable double bond.
- Metallic pigments having a material layer have also been proposed.
- the coating layer is formed for the purpose of further imparting corrosion resistance to the metallic pigment (paragraph 0042 of patent document 8)
- the surface modifier layer that is the outermost surface layer of the coating layer is also the same. It is understood that it is formed in layers according to the wording.
- the outermost layer located directly below the surface modifier layer contains a polymer obtained by polymerizing a monomer having a basic group and at least one polymerizable double bond.
- a basic point serving as an adsorption site for the phosphate group of the surface modifier layer on the surface of the outermost layer the surface modifier layer and the outermost layer due to the acid-base interaction are thereby formed. Strong adsorption with the outer layer becomes possible (same paragraph).
- such a configuration has the advantage that it is possible to maintain good corrosion resistance when the metallic pigment is used in a powder coating, but when this metallic pigment is blended in an aqueous coating, The chemical resistance is similarly good, but the water resistance (humidity) has not reached a practically sufficient level. Therefore, it has been required to further improve the water resistance (humidity) while maintaining the chemical resistance.
- JP-A-62-081460 Japanese Patent Laid-Open No. 62-253668 Japanese Patent Application Laid-Open No. 64-040565 JP 2005-146111 A JP 2007-119671 A JP 2004-131542 A JP 2007-204692 A International Publication No. 2006/064652 Pamphlet
- the present invention has been made on the basis of such knowledge, and practically sufficient water resistance (humidity) of a coating film obtained by blending with a water-based coating material while maintaining the chemical resistance of the coating film. It is an object of the present invention to provide a resin-coated metallic pigment improved to a standard, a water-based paint containing the same, a coated product on which the resin-coated metallic pigment is applied, and a method for producing the same.
- the present invention relates to a resin-coated metallic pigment in which a single-layer or multi-layer coating layer is formed on the surface of a substrate particle, and the outermost layer of the coating layer is a monomer or oligomer having two or more polymerizable double bonds The outermost layer surface portion is treated with a surface modifier that is a compound having one polymerizable double bond.
- the resin is a polymer that includes one or more compounds selected from The present invention relates to a resin-coated metallic pigment.
- the surface modifier is preferably an ester of an unsaturated carboxylic acid. Further, it is preferable that the surface modifier is contained at a ratio of 0.1 to 10 parts by mass with respect to 100 parts by mass of the base particles.
- the substrate particles are preferably aluminum particles, and are preferably colored aluminum particles obtained by attaching an inorganic pigment or an organic pigment to the surface of the aluminum particles.
- the substrate particles are preferably interference-colored aluminum particles having one or more inorganic compound layers or metal layers exhibiting interference action on the surfaces of the aluminum particles.
- the resin-coated metallic pigment is preferably used for an aqueous paint
- the present invention also relates to an aqueous paint containing the resin-coated metallic pigment.
- the present invention relates to a coated product to which the above water-based paint is applied.
- the present invention also relates to a method for producing a resin-coated metallic pigment in which a single-layer or multi-layer coating layer is formed on the surface of a base particle, wherein two or more polymerizable double layers are formed on the surface of the base particle.
- a step of forming an outermost layer of the coating layer by polymerizing one or more compounds selected from monomers and oligomers having a bond, and a surface portion of the outermost layer having one polymerizable double bond.
- a step of treating with a surface modifier that is a compound having a resin-coated metallic pigment is a compound having a resin-coated metallic pigment.
- the step of treating with the surface modifier comprises reacting the polymerizable double bond remaining on the surface portion of the outermost layer with the polymerizable double bond contained in the surface modifier, A surface modifier is preferably bonded to the surface portion of the outermost layer.
- the water resistance (humidity) of the obtained coating film when used in an aqueous paint while maintaining the chemical resistance of the coating film using the resin-coated metallic pigment having the configuration of the present invention can be improved to a practically sufficient level.
- the present invention provides a resin-coated metallic pigment having such a structure, a water-based paint containing the same, a coated product on which the resin-coated metallic pigment is applied, and a method for producing the same.
- the resin-coated metallic pigment of the present invention has a structure in which a single-layer or multi-layer coating layer is formed on the surface of a base particle. Each configuration will be described below.
- base particles of the resin-coated metallic pigment of the present invention any conventionally known base particles can be used as long as they become base particles of this type of metallic pigment, and are not particularly limited.
- metal particles or inorganic compound particles can be used as such base particles.
- the metal particles include metal particles such as aluminum, zinc, copper, bronze, nickel, titanium, and stainless steel, and alloy particles thereof.
- aluminum particles are particularly suitable because they are excellent in metallic luster, inexpensive and easy to handle because of their low specific gravity.
- examples of the inorganic compound particles include ceramic particles such as glass, mica, alumina, and titania.
- the shape of the substrate particles in the present invention is not particularly limited, and various shapes such as a granular shape, a plate shape, a lump shape, and a flake shape (scale shape) can be adopted. In order to give, it is preferable that it is flaky.
- the average particle size of the base particles is usually preferably about 1 to 100 ⁇ m, more preferably 3 to 60 ⁇ m. If the average particle size of the substrate particles is less than 1 ⁇ m, it tends to be difficult to handle in the production process and tends to aggregate, and if the average particle size exceeds 100 ⁇ m, it is applied when used as a paint. In some cases, the film surface becomes rough and a preferable design cannot be realized.
- the average thickness is not particularly limited, but is preferably 0.005 ⁇ m or more, particularly 0.02 ⁇ m or more. More preferred.
- the average thickness is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
- the average thickness of the substrate particles is less than 0.005 ⁇ m, handling in the manufacturing process is difficult and tends to aggregate, and when the average thickness exceeds 5 ⁇ m, the particle feeling of the coating film (unevenness) ) May be conspicuous or the concealment power may be insufficient, and a desirable design may not be realized.
- the average particle size of the base particles as described above is obtained by calculating a volume average from a particle size distribution measured by a known particle size distribution measurement method such as a laser diffraction method, a micromesh sieve method, or a Coulter counter method.
- the average thickness can be calculated from the hiding power and density of the base particles.
- metal particles having a flake shape as described above can be used as the base particle, and such a flake-shaped metal particle can be obtained by, for example, using a metal powder as a raw material as a ball mill or the like. Can be obtained by grinding.
- the grinding aid added at the time of grinding may be adsorbed on the surface of the metal particles.
- the grinding aid include fatty amines such as oleic acid and stearic acid, aliphatic amines, aliphatic amides, aliphatic alcohols, ester compounds, and the like. These have the effect of suppressing unnecessary oxidation on the surface of the metal particles and improving the gloss.
- the adsorption amount of the grinding aid is preferably less than 2 parts by mass with respect to 100 parts by mass of the metal particles. When the amount is less than 2 parts by mass, it is advantageous in that the surface gloss is hardly lowered and the coating layer easily adheres.
- the aluminum particles when used as the metal particles, can be colored aluminum particles having inorganic pigments or organic pigments attached to the surfaces thereof, and furthermore, inorganic particles exhibiting interference action on the surfaces of the aluminum particles. Interference-colored aluminum particles having one or more compound layers or metal layers can also be used. By using such colored aluminum particles or interference-colored aluminum particles as substrate particles, it is possible to form a coating film having a unique design.
- the inorganic pigment or organic pigment used for forming the colored aluminum particles is not particularly limited, and examples thereof include quinacridone, diketopyrrolopyrrole, isoindolinone, indanthrone, perylene, perinone, anthraquinone, Dioxazine, benzimidazolone, triphenylmethanequinophthalone, anthrapyrimidine, yellow lead, pearl mica, transparent pearl mica, colored mica, interference mica, phthalocyanine, halogenated phthalocyanine, azo pigment (azomethine metal complex, condensed azo, etc.), titanium oxide Carbon black, iron oxide, copper phthalocyanine, condensed polycyclic pigments, and the like.
- Such an inorganic pigment or an organic pigment can be attached to the surface of the aluminum particles by, for example, coating the pigment with a dispersant and then stirring and mixing with the aluminum particles in a nonpolar solvent.
- the method of forming one or more inorganic compound layers or metal layers having an interference action on the surface of the aluminum particles is not particularly limited.
- sol-gel method solution precipitation method, Electroless plating, chemical vapor deposition, physical vapor deposition, or the like can be used.
- the chemical substance used at that time is not particularly limited.
- metal such as gold, silver, copper, nickel, cobalt, titanium, aluminum, silicon, or an alloy thereof (metal) Or an oxide thereof (becomes an inorganic compound layer).
- the number of layers of the inorganic compound layer or metal layer is not particularly limited, and may be only one layer or a plurality of layers. Note that the thickness of such an inorganic compound layer or metal layer is preferably 5 to 200 nm, and more preferably 10 to 150 nm.
- an inorganic compound layer having an interference action on the surface of the aluminum particles may be provided in advance on the surface of the aluminum particles as a pretreatment.
- a single-layer or multiple-layer (two or more layers) coating layer is formed on the surface of the substrate particles.
- a single-layer coating layer is formed, only the outermost layer described later is the coating layer.
- the layers other than the outermost layer are not particularly limited as long as the outermost layer is included, and any layer may be included.
- the layer other than the outermost layer examples include a metal layer (similar to the metal layer in the interference color aluminum particles), a metal oxide layer (crystalline or amorphous), and a metal hydroxide layer. , Metal hydrate layers, resin layers, and the like.
- the thickness of the coating layer is not particularly limited, but is preferably 5 to 150 nm, and more preferably 10 to 100 nm.
- the outermost layer of the coating layer constituting the resin-coated metallic pigment of the present invention is a polymer containing one or more compounds selected from monomers and oligomers having two or more polymerizable double bonds as its structural unit. It consists of resin. That is, the resin constituting the outermost layer is obtained by polymerizing one or more compounds selected from monomers and oligomers having two or more polymerizable double bonds. In this polymerization, only one or more compounds selected from monomers and oligomers having two or more polymerizable double bonds may be polymerized, or the one or more compounds and another 1 or 2 may be polymerized. It may be obtained by polymerizing the above compound.
- a polymer containing one or more compounds selected from monomers and oligomers having two or more polymerizable double bonds as a constituent unit is a monomer or oligomer having two or more polymerizable double bonds. It does not mean only a polymer obtained by polymerizing only one or more compounds selected from the above, but a polymer obtained by polymerizing the one or more compounds and one or more other compounds Is also meant.
- this outermost layer By forming this outermost layer, good chemical resistance is imparted to the resin-coated metallic pigment of the present invention. This is because the resin constituting the outermost layer is obtained by polymerizing one or more compounds selected from monomers and oligomers having two or more polymerizable double bonds. This is because the chemical resistance is improved by the crosslinking action of the heavy bond.
- examples of the monomer having two or more polymerizable double bonds include unsaturated carboxylic acid esters (specifically, tetramethylolmethane tetraacrylate, tetramethylolmethane triacrylate, trimethylolpropane triacrylate, trimethylol Ethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nanonediol diacrylate, pentaerythritol triacrylate, ethylene glycol dimethacrylate, glycerin dimethacrylate, diethylene glycol dimethacrylate , Triethylene glycol dimethacrylate, tetramethylol methane trimethacrylate, trimethylol propane trimethacrylate, 1,4-butanedio Dimethacrylate, hexanediol dimethacrylate 1,6, 1,9 Nanon diol dimethacrylate
- oligomers having two or more polymerizable double bonds include epoxidized 1,2-polybutadiene, acrylic-modified polyester, acrylic-modified polyether, acrylic-modified urethane, acrylic-modified epoxy, and acrylic-modified spirane (all of them).
- the degree of polymerization is about 2 to 20).
- acrylic-modified polyester and epoxidized 1,2-polybutadiene having a polymerization degree of 3 to 10 are preferred.
- Use of such an oligomer is preferable in that the polymerization reaction proceeds gradually and the reaction efficiency becomes very high.
- first compound a compound other than one or more compounds selected from monomers and oligomers having two or more polymerizable double bonds
- first compound a compound other than one or more compounds selected from monomers and oligomers having two or more polymerizable double bonds
- second compound capable of forming the outermost layer by doing so
- a cyclic unsaturated compound for example, cyclohexene
- Unsaturated compounds for example, styrene, ⁇ -methylstyrene, vinyl toluene, cyclohexene vinyl monoxide, vinyl acetate, vinyl propionate or diallylbenzene
- the amount of one or more compounds selected from monomers and oligomers having two or more polymerizable double bonds is the base material. Although it varies depending on the kind and characteristics of the particles, it is generally preferred that the amount is 1 to 40 parts by mass with respect to 100 parts by mass of the base particles. If the amount used is less than 1 part by mass, the chemical resistance may be reduced, and if it exceeds 40 parts by mass, the concealability and surface gloss may be reduced.
- the thickness of such an outermost layer varies depending on the type and characteristics of the substrate particles, but is preferably 5 to 150 nm, and more preferably 10 to 100 nm. If the thickness is less than 5 nm, the chemical resistance may be reduced, and if it exceeds 150 nm, the concealability and surface gloss may be reduced.
- the present invention is characterized in that the surface portion of the outermost layer is treated with a surface modifier which is a compound having one polymerizable double bond.
- a surface modifier which is a compound having one polymerizable double bond.
- the surface portion of the outermost layer is treated with the surface modifier, which means that the polymerizable double bond remaining on the surface portion of the outermost layer (the monomer or oligomer constituting the resin serving as the outermost layer has not been processed).
- the surface modifier is bonded to the surface portion of the outermost layer by the reaction of one polymerizable double bond contained in the surface modifier with one polymerizable double bond contained in the surface modifier.
- the mechanism of this processing operation is based on the inventor's consideration. That is, as described above, the resin constituting the outermost layer is composed of a polymer produced by polymerizing one or more compounds selected from monomers and oligomers having two or more polymerizable double bonds.
- this polymer is presumed that unreacted polymerizable double bonds remain even after the completion of the polymerization reaction. Since this unreacted polymerizable double bond is highly reactive, it easily reacts with various substances and also reacts with the varnish component in the water-based paint. It is considered that the film performance is not exhibited and the water resistance (wet) is a main factor that is impaired, and this tendency is particularly caused when the unreacted polymerizable double bond remains on the surface of the outermost layer. It is thought that it becomes remarkable. Therefore, by reacting the unreacted polymerizable double bond remaining on the surface portion of the outermost layer with one polymerizable double bond contained in the surface modifier, the surface modifier becomes the outermost layer.
- the highly reactive polymerizable double bond disappears or decreases in the surface portion of the outermost layer.
- a chemically stable outermost layer surface that is, a coating layer surface
- the resin-coated metallic pigment of the present invention is used in an aqueous paint, the original coating film performance is exhibited without inhibiting the hardening of the varnish component in the aqueous coating, and the water resistance (humidity) performance of the coating is improved. It is thought to do.
- the surface portion of the outermost layer is not yet removed.
- the amount of the surface modifier used (the amount for treating the surface portion of the outermost layer) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the base particles, More preferably, the content is ⁇ 5 parts by mass.
- the amount of the surface modifier used is less than 0.1 parts by mass, sufficient water resistance (humidity) tends not to be exhibited.
- the usage-amount of this surface modifier exceeds 10 mass parts, coating-film performance, for example, water resistance (wet) property, may not fully be acquired.
- the surface modifier of the present invention is a compound having one polymerizable double bond.
- the compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, crotonic acid, itacone). Acid, citraconic acid, etc.), esters thereof (for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, lauryl acrylate, stearyl acrylate, butoxy acrylate, dimethylaminoethyl acrylate, diethylamino Ethyl acrylate, 2-hydroxybutyl acrylate, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, Sidyl acrylate, cyclohexyl acrylate, methyl methacrylate,
- ester of the unsaturated carboxylic acid it is preferable to use the ester of the unsaturated carboxylic acid. This is because an ester of an unsaturated carboxylic acid easily polymerizes with a polymer having an unreacted polymerizable double bond, and a surface modification effect is easily obtained.
- the surface modifier layer in Patent Document 8 described above forms a layer, whereas the surface modifier used in the present invention has one polymerizable double bond contained in the outermost layer.
- the surface modifier is interspersed with the surface portion of the outermost layer and never forms a layer by itself because it reacts with the polymerizable double bond remaining on the surface of .
- any unreacted surface modifier remains in any way, resulting in a highly reactive polymerizable double bond. (Derived from the unreacted surface modifier) remains in the surface modifier layer.
- the polymer when a coating layer containing a polymer obtained by polymerizing a monomer having a basic group and at least one polymerizable double bond is formed as in the outermost layer in Patent Document 8, the polymer includes Monomers and / or oligomers other than the monomer having a basic group and at least one polymerizable double bond are also included as components.
- the surface since an unreacted polymerizable double bond remains on the surface of the outermost layer in Patent Document 8, the surface is not chemically stable. Therefore, when this is used for a water-based paint, a desired effect (particularly water resistance (wet) resistance) cannot be achieved.
- the coating layer is formed only with a polymer obtained by polymerizing a monomer having a basic group and at least one polymerizable double bond as in the outermost layer of Patent Document 8, formation of the layer is performed.
- the formation of free polymer particles that were not used in the process may cause a sudden increase in viscosity and coagulation of the entire system.
- the method for producing a resin-coated metallic pigment according to the present invention is a method for producing a resin-coated metallic pigment in which a single-layer or multi-layer coating layer is formed on the surface of a base particle, and two on the surface of the base particle.
- the step of treating with the surface modifier comprises reacting the polymerizable double bond remaining on the surface portion of the outermost layer with the polymerizable double bond contained in the surface modifier, A surface modifier is preferably bonded to the surface portion of the outermost layer.
- the manufacturing method of this invention can include the arbitrary processes which form layers other than those outermost layers.
- forming the outermost layer on the surface of the substrate particles means that the outermost layer is formed on a layer other than the outermost layer.
- outermost layer forming step for example, after dispersing the base particles in a solvent, two or more polymerizable two-components are dispersed in the dispersion. One or more compounds selected from monomers and oligomers having a heavy bond can be added to cause a polymerization reaction. Thereby, the outermost layer can be formed on the surface of the substrate particles.
- the timing and the number of times of addition of one or more compounds (first compounds) selected from monomers and oligomers having two or more polymerizable double bonds are: It does not specifically limit, The whole quantity may be added at once and may be added in several steps.
- the aforementioned second compound in addition to these first compounds, can be added.
- Preferred examples of the solvent used in the polymerization reaction include aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, and mineral spirits, and aromatic hydrocarbons such as benzene, xylene, and toluene.
- Halogenated hydrocarbons such as chlorobenzene, trichlorobenzene, perchlorethylene, trichloroethylene, alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, s-butanol, t-butanol, acetone , Ketones such as acetylacetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl-n-butyl ketone, methyl-n-propyl ketone, esters such as ethyl acetate, propyl acetate, tetrahydride Furan, diethyl ether, ethers such as ethyl propyl ether and the like can be exemplified.
- a polymerization initiator is preferably used, and in particular, a radical initiator generally known as a radical generator can be used.
- a radical initiator generally known as a radical generator
- Specific examples of the polymerization initiator include peroxides such as benzoyl peroxide, lauroyl peroxide, isobutyl peroxide, and methyl ethyl ketone peroxide, and azo compounds such as AIBN (azobisisobutyronitrile).
- the blending amount of the polymerization initiator for carrying out the polymerization reaction is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the first compound. Moreover, it is preferable that this compounding quantity is 30 mass parts or less, and it is more preferable that it is 20 mass parts or less especially.
- the blending amount of the polymerization initiator is 0.5 parts by mass or more, it is preferable in that the polymerization reaction can surely proceed and an expected outermost layer can be easily formed.
- the blending amount is 30 parts by mass or less, the rapid progress of the polymerization can be prevented, the produced polymer can be surely adsorbed to the base particles, and the viscosity of the entire system due to the production of free polymer particles. This is preferable in that rapid rise and solidification can be prevented.
- the temperature of the polymerization reaction is defined by the type of polymerization initiator used.
- the half-life of the polymerization initiator is uniquely determined by the temperature, and is preferably a temperature at which the half-life of the polymerization initiator is 5 minutes or more, more preferably a temperature at which it is 15 minutes or more.
- this temperature is preferably such that the half-life of the polymerization initiator is 20 hours or less, and more preferably 10 hours or less.
- a more preferable temperature range is 70 to 90 ° C.
- the polymerization reaction is carried out at a temperature at which the half-life of the polymerization initiator is 20 hours or less, it is preferable in that the problem that the polymerization reaction does not proceed easily is generated, and the half-life of the polymerization initiator is 5 minutes or more.
- the surface portion of the outermost layer is treated with a surface modifier that is a compound having one polymerizable double bond (
- the resin-coated metallic pigment of the present invention is produced by simply performing “surface modifying agent treatment step”).
- This surface modifier treatment step comprises reacting the polymerizable double bond remaining on the surface portion of the outermost layer with the polymerizable double bond contained in the surface modifier, thereby It is preferable to bond to the surface portion of the outermost layer.
- Such a surface modifier treatment step is, for example, a surface modification which is a compound having one polymerizable double bond by dispersing the base material particles on which the outermost layer is formed in a solvent after the outermost layer forming step.
- the surface modifier can be bonded to the surface portion of the outermost layer by adding a quality agent and reacting appropriately with a radical initiator or the like.
- the surface modifier treatment step is not limited to such a method, and any method may be used as long as it is after the outermost layer forming step.
- the surface modifier treatment step is performed after removing the unreacted monomer or oligomer for forming the outermost layer by washing the base particles on which the outermost layer is formed using the solvent used in the outermost layer forming step. May be.
- the substrate particles may be slurried with the solvent used for washing without passing through the drying step after washing, and the surface modifier treatment step may be performed, or the substrate particles may be washed after washing.
- the powder is pulverized through a drying process, it may be dispersed again using a solvent to perform the surface modifier treatment process.
- the surface of the base material particles having the outermost layer formed in the outermost layer forming step is continuously washed in the solvent in which the base material particles having undergone such outermost layer forming step are dispersed without washing with the solvent used in the polymerization reaction.
- the surface modifier treatment step may be performed by adding a modifier. Considering the point that the surface modifier is tightly bonded to the outermost layer formed on the surface of the base particle and the simplification of the process and economic efficiency, the base material particle that has formed the outermost layer in the outermost layer forming step is polymerized. It is particularly preferable to carry out the surface modifier treatment step by continuously adding the surface modifier without washing again with the solvent used in the above.
- the solvent used in the surface modifier treatment step is not particularly limited, but a solvent similar to the solvent used in the outermost layer forming step is preferably used.
- the surface modifier treatment step it is preferable that all of the monomers or oligomers for outermost layer formation used in the outermost layer formation step undergo a polymerization reaction, but in the case of industrial production, The polymerization reaction requires a long reaction time. Therefore, if 80% by mass or more of the monomer or oligomer added in the outermost layer forming step undergoes a polymerization reaction, the base material particles that have undergone the outermost layer forming step are dispersed even if the unreacted monomer or oligomer remains.
- the surface modifier treatment step may be performed by subsequently adding the surface modifier to the solvent.
- a polymerization initiator In order to efficiently and surely react the polymerizable double bond remaining on the surface portion of the outermost layer and the polymerizable double bond contained in the surface modifier, it is preferable to use a polymerization initiator.
- the kind of polymerization initiator to be used is not particularly limited, a polymerization initiator similar to the polymerization initiator used for the polymerization reaction in the outermost layer forming step is preferably used.
- the blending amount of the polymerization initiator for reacting the surface modifier is preferably 0.5 parts by mass or more, particularly 1 part by mass or more with respect to 100 parts by mass of the surface modifier. Is more preferable. Moreover, it is preferable that this compounding quantity is 30 mass parts or less, and it is more preferable that it is 20 mass parts or less especially.
- the blending amount of the polymerization initiator is 1 part by mass or more, the reaction is allowed to proceed reliably, and most of the polymerizable double bonds remaining on the outermost layer surface are surface modifiers (polymerizable double bonds contained in). It is preferable at the point which couple
- the blending amount is 30 parts by mass or less, the rapid progress of the reaction can be prevented and the bonding between the surface modifiers can be prevented, so that the surface modifier is reliably left on the surface of the outermost layer. It is preferable in that it can be combined with a double bond, and further, a rapid increase in the viscosity of the entire system and solidification due to the formation of a polymer formed by bonding surface modifiers can be prevented.
- the reaction temperature is defined by the type of polymerization initiator used in the same manner as in the outermost layer formation step.
- the half-life of the polymerization initiator is uniquely determined by the temperature, and is preferably a temperature at which the half-life of the polymerization initiator is 5 minutes or more, more preferably a temperature at which it is 15 minutes or more.
- this temperature is preferably such that the half-life of the polymerization initiator is 20 hours or less, and more preferably 10 hours or less.
- a more preferable temperature range is 70 to 90 ° C.
- the reaction is carried out at a temperature at which the half-life of the polymerization initiator is 20 hours or less, it is preferable that the reaction does not easily proceed, and the half-life of the polymerization initiator is 5 minutes or longer.
- the rapid progress of the reaction can be prevented and the bonding between the surface modifiers can be prevented, so that the surface modifier can be reliably left on the surface of the outermost layer and It is preferable in that it can be combined, and further, rapid increase in viscosity and coagulation of the entire system due to generation of a polymer formed by combining surface modifiers can be prevented.
- the surface modifier treatment step it is advantageous to carry out the polymerization reaction in an inert gas atmosphere such as nitrogen, helium or argon in order to increase the reaction efficiency.
- an inert gas atmosphere such as nitrogen, helium or argon
- the resin-coated metallic pigment of the present invention obtained with the solvent used for the reaction is washed to remove unreacted monomers or oligomers and the surface modifier.
- such a surface modifier treatment process can be performed using 1 type, or 2 or more types of surface modifiers.
- the resin-coated metallic pigment of the present invention is preferably used for an aqueous paint.
- the present invention also relates to an aqueous paint containing the resin-coated metallic pigment, and further relates to a coated product to which the aqueous paint is applied.
- the resin-coated metallic pigment of the present invention can be used by blending it with a known and common water-based paint.
- aqueous paint include an aqueous paint containing the resin-coated metallic pigment of the present invention and a binder (varnish). These paints may be used in a mixture of two or more liquids as well as one liquid, or may be accompanied by a reaction.
- the aqueous paint containing the resin-coated metallic pigment of the present invention can contain other pigments and dyes in accordance with the target hue. However, it is desirable to use other pigments as long as the metallic feeling of the resin-coated metallic pigment of the present invention is not impaired.
- the binder is not particularly limited as long as it is a commonly used binder, but an emulsion binder can be preferably exemplified.
- an emulsion binder various natural or synthetic polymers, oligomers, prepolymers and the like can be used.
- These paints can contain various additives as required. Examples of the additives include surfactants, stabilizers, rust preventives, plasticizers, pigment wetting agents, pigment dispersants, flow regulators, leveling agents, fungicides, and ultraviolet absorbers.
- the object to be coated with the water-based paint of the present invention is not particularly limited as long as such a water-based paint can be applied.
- Composition I 61 g, 2.1 g of melamine compound (Cymel327 manufactured by Mitsui Cytec), 2.79 g of butyl glycol, 0.31 g of surfactant (Byk-347 manufactured by Big Chemie Japan), thickener (manufactured by Nichigo Movinyl Co., Ltd.) Viscolex HV30) 0.56 g, ion-exchanged water 13.96 g, and 10% dimethylethanolamine aqueous solution 3.04 g, which was stirred and mixed for 30 minutes or more, is referred to as Composition I.
- ⁇ Preparation method of coated plate> The aqueous paint prepared as described above was spray-coated on a metal plate.
- the obtained spray coated plate was set at room temperature for 5 minutes or more, and then the spray coated plate was dried at 80 ° C. for 3 minutes. Thereafter, the spray coated plate was set at room temperature for 10 minutes or more, and then a clear coat was further applied to the spray coated plate by spraying. After setting the clear coat, it was set at room temperature for 10 minutes or more and then baked at 130 ° C. for 30 minutes to obtain a spray-coated coated plate.
- the coating conditions of the coating plate were adjusted when the spray coating was performed so that the water-based paint film had a thickness of 14 to 18 ⁇ m and the clear coat film had a thickness of 35 to 40 ⁇ m.
- the coated plate was washed with water, dried, and then subjected to colorimetry by the above-described method to determine the color difference of the coating film before and after immersion.
- the evaluation was “excellent”: ⁇ E * 45 was less than 3, “possible”: ⁇ E * 45 was 3 to less than 7, and “impossible”: ⁇ E * 45 was 7 or more.
- the gloss of the coating film was measured by using a gloss meter (Gloss Meter VG2000, manufactured by Nippon Denshoku Industries Co., Ltd.). The measured value of the 20-degree gloss of the coated plate before immersion was G1, the measured value of the 20-degree gloss of the coated plate after immersion was G2, and the gloss retention rate R was determined by the following equation.
- R (%) (G2 / G1) ⁇ 100
- excellent R was 90% or more
- possible R was 80% or more to less than 90%
- impossible R was less than 80%.
- Example 1 First, a paste of flaky aluminum particles (trade name: 5422NS, particle size: 19 ⁇ m, pasting agent: mineral spirit, manufactured by Toyo Aluminum Co., Ltd.), which is a base particle, was washed with mineral spirit and then filtered. The non-volatile component (aluminum particles) in the paste after filtration was 74% by mass (the balance being mineral spirit).
- flaky aluminum particles trade name: 5422NS, particle size: 19 ⁇ m, pasting agent: mineral spirit, manufactured by Toyo Aluminum Co., Ltd.
- “Number of polymerizable double bonds” indicates the number of polymerizable double bonds per individual monomer or oligomer. Thus, in the present invention, the number of polymerizable double bonds refers to the number per individual monomer or individual oligomer.
- Examples 2 to 6 glycidyl methacrylate (symbol “F” in Table 1), dimethylaminoethyl methacrylate (symbol “G” in Table 1), diethylaminoethyl acrylate (in Table 1) were used as surface modifiers, respectively.
- Symbol “H”), 2-ethylhexyl acrylate (symbol “I” in Table 1), and hydroxyethyl acrylate (symbol “J” in Table 1) were each 3.0 g (1 part per 100 parts by weight of nonvolatile components).
- Example 2 Except for the use of (mass parts), the same treatment as in Example 1 was performed, and the resin-coated metallic pigment of the present invention was obtained in a paste state. The obtained resin-coated metallic pigment was subjected to a chemical resistance test and a water resistance test in the same manner as in Example 1. The results are shown in Table 2.
- Example 7 to 10 the addition amount of lauryl methacrylate (symbol “E” in Table 1), which is a surface modifier, was 0.15 g, 0.6 g, 15 g, and 45 g (nonvolatile components (aluminum particles) 100 mass), respectively. Except that it was 0.05, 0.2, 5, and 15 parts by mass), the same treatment as in Example 1 was performed, and the resin-coated metallic pigment of the present invention was obtained in a paste state. . The obtained resin-coated metallic pigment was subjected to a chemical resistance test and a water resistance test in the same manner as in Example 1. The results are shown in Table 2.
- Example 11 A slurry for performing the outermost layer forming step was prepared in the same manner as in Example 1.
- Example 12 to 16 flake-shaped colored aluminum particles (aluminum flakes manufactured by Toyo Aluminum Co., Ltd. (trade name: 5422NS, particle size: 19 ⁇ m)) were used as base particles in Example 1 of JP-A-9-124973, respectively.
- the resin-coated metallic pigment of the present invention was obtained in a paste state, except that the same treatment as in Example 1 was performed.
- the obtained resin-coated metallic pigment was subjected to a chemical resistance test and a water resistance test in the same manner as in Example 1. The results are shown in Table 2.
- Example 1 In Example 1, except that the surface modifier treatment step was not performed, the same treatment as in Example 1 was performed, and a resin-coated metallic pigment was obtained in a paste state. The obtained resin-coated metallic pigment was subjected to a chemical resistance test and a water resistance test in the same manner as in Example 1. The results are shown in Table 2. This comparative example corresponds to the one in which only the outermost layer forming step is performed to produce a resin-coated metallic pigment.
- the obtained resin-coated metallic pigment was subjected to a chemical resistance test and a water resistance test in the same manner as in Example 1. The results are shown in Table 2.
- This comparative example also corresponds to the one in which only the outermost layer forming step is performed to produce the resin-coated metallic pigment.
- Example 4 A chemical pigment test and a water resistance test were conducted in the same manner as in Example 1 on a metallic pigment paste (trade name: 5422NS, particle size: 19 ⁇ m, manufactured by Toyo Aluminum Co., Ltd.), which is a paste of commercially available flaky aluminum particles. The results are shown in Table 2. This comparative example corresponds to the base particle itself which does not have the outermost layer forming step and the surface modifier treatment step.
- the water resistance (humidity) of the obtained coating film is improved to a practically sufficient level. It is possible to provide a resin-coated metallic pigment, a water-based paint containing the same, a coated product on which the resin-coated metallic pigment is applied, and a method for producing the same.
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Abstract
Description
本発明の樹脂被覆メタリック顔料は、基材粒子の表面に単層または複層の被覆層を形成した構成を有する。以下、各構成について説明する。
本発明の樹脂被覆メタリック顔料の基材粒子としては、この種のメタリック顔料の基材粒子となるものであれば従来公知の基材粒子をいずれも用いることができ、特に限定されるものではない。たとえば、このような基材粒子として金属粒子または無機化合物粒子を使用することができる。金属粒子としては、アルミニウム、亜鉛、銅、ブロンズ、ニッケル、チタン、ステンレスなどの金属粒子およびそれらの合金粒子が挙げられる。これらの金属粒子の中でもアルミニウム粒子は金属光沢に優れ、安価な上に比重が小さいため扱いやすく、特に好適である。一方、無機化合物粒子としては、ガラス、マイカ、アルミナまたはチタニアなどのセラミックス粒子が挙げられる。
本発明の樹脂被覆メタリック顔料は、基材粒子の表面に単層または複層(2層以上)の被覆層が形成されている。単層の被覆層が形成される場合は、後述する最外層のみが被覆層となる。一方、複層の被覆層が形成される場合は、当該最外層が含まれる限り最外層以外の層は特に限定されず、いずれの層が含まれていても差し支えない。
本発明の樹脂被覆メタリック顔料を構成する被覆層の最外層は、2個以上の重合性二重結合を有するモノマーおよびオリゴマーから選ばれた1種以上の化合物をその構成単位として含む重合体である樹脂からなるものである。すなわち、該最外層を構成する樹脂は、2個以上の重合性二重結合を有するモノマーおよびオリゴマーから選ばれた1種以上の化合物を重合させて得られるものである。なお、かかる重合は、2個以上の重合性二重結合を有するモノマーおよびオリゴマーから選ばれた1種以上の化合物のみを重合させてもよいし、当該1種以上の化合物と他の1または2以上の化合物とを重合させたものであってもよい。すなわち、2個以上の重合性二重結合を有するモノマーおよびオリゴマーから選ばれた1種以上の化合物をその構成単位として含む重合体とは、2個以上の重合性二重結合を有するモノマーおよびオリゴマーから選ばれた1種以上の化合物のみを重合させて得られる重合体のみを意味するものではなく、当該1種以上の化合物と他の1または2以上の化合物とを重合させて得られる重合体をも意味するものである。
本発明は、上記最外層の表面部が1個の重合性二重結合を有する化合物である表面改質剤により処理されていることを特徴とする。これにより、本発明の樹脂被覆メタリック顔料に優れた耐水(湿)性能が付与され、以って上述の通りの最外層自体が有する耐薬品性の向上作用と相俟って、耐薬品性と耐水(湿)性とを高度に両立させることが可能となったものである。したがって、本発明の樹脂被覆メタリック顔料を用いた塗膜の耐薬品性を維持したままで、水性塗料に用いた場合、得られる塗膜の耐水(湿)性を実用上十分な水準に向上させることが可能となった。
本発明の樹脂被覆メタリック顔料の製造方法は、基材粒子の表面に単層または複層の被覆層を形成した樹脂被覆メタリック顔料の製造方法であって、上記基材粒子の表面に、2個以上の重合性二重結合を有するモノマーおよびオリゴマーから選ばれた1種以上の化合物を重合反応させることにより、該被覆層の最外層を形成する工程と、該最外層の表面部を1個の重合性二重結合を有する化合物である表面改質剤により処理する工程とを含むことを特徴とする。
上記被覆層の最外層を形成する工程(単に「最外層形成工程」とも記す)においては、たとえば、基材粒子を溶媒中に分散させた後、その分散液中に2個以上の重合性二重結合を有するモノマーおよびオリゴマーから選ばれた1種以上の化合物を加えて重合反応させることができる。これにより、基材粒子の表面に最外層を形成することができる。ここで、このように最外層を形成するには、2個以上の重合性二重結合を有するモノマーおよびオリゴマーから選ばれた1種以上の化合物(第1化合物)を添加するタイミングや添加回数は特に限定されず、1回で全量を添加してもよく、数回に分けて添加してもよい。なお、本発明の最外層形成工程においては、これらの第1化合物に加え、前述の第2化合物を加えることも可能である。
上記の最外層形成工程により基材粒子の表面に最外層を形成した後、1個の重合性二重結合を有する化合物である表面改質剤により、この最外層の表面部を処理する工程(単に「表面改質剤処理工程」とも記す)を実行することにより本発明の樹脂被覆メタリック顔料は製造される。この表面改質剤処理工程は、該最外層の表面部に残存する重合性二重結合と該表面改質剤に含まれる重合性二重結合とを反応させることにより、該表面改質剤を該最外層の表面部に結合させるものであることが好ましい。
本発明の樹脂被覆メタリック顔料は、好ましくは水性塗料に用いられる。この点、本発明は、この樹脂被覆メタリック顔料を含有してなる水性塗料にも関し、さらに上記水性塗料が塗布された塗装物にも関する。
以下、本発明を実施例および比較例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、本実施例および比較例に用いたモノマーおよびオリゴマーを表1に示す。
アクリルディスパージョン(Neuplex社製Setaqua6802)を31.48g、ポリウレタンディスパージョンA(住化バイエルウレタン社製バイヒドロールXP2621)を18.89g、ポリウレタンディスパージョンB(住化バイエルウレタン社製バイヒドロールPT241)を4.61g、メラミン化合物(三井サイテック社製Cymel327)を2.1g、ブチルグリコールを2.79g、界面活性剤(ビッグケミー・ジャパン社製Byk-347)を0.31g、増粘剤(ニチゴー・モビニール社製ビスカレックスHV30)を0.56g、イオン交換水を13.96g、および10%ジメチルエタノールアミン水溶液を3.04g、30分以上攪拌混合したものを組成物Iとする。
上記のようにして調製した水性塗料を金属板にスプレー塗装した。得られたスプレー塗板を5分以上常温でセッティングした後、該スプレー塗板を80℃にて3分間乾燥した。その後スプレー塗板を10分以上常温でセッティングした後、該スプレー塗板にさらにクリヤーコートをスプレーにて塗布した。クリヤーコートを塗布後10分以上常温にてセッティングした後、130℃にて30分間焼き付けを行なうことによりスプレー塗装された塗板を得た。この塗板における塗膜の厚みは、水性塗料膜が14~18μm、クリヤーコート膜が35~40μmになるように上記スプレー塗装を行なう際に塗装条件を調整した。
上記で得られた塗板の色調を特定するために、変角測色計(X-Rite社製「X-Rite MA-68II」)を用いて観測角θが45度(塗膜法線方向にて受光)における、塗板に形成された塗膜の、L* 45、a* 45、b* 45の値を測定した。また、以下に述べる各種試験(性能テスト)の前後における塗膜の色差ΔE* 45は、試験前後に測定されたそれぞれのL* 45、a* 45、b* 45値より算出した。
得られたメタリック顔料(以下の実施例では本発明の樹脂被覆メタリック顔料)4.88質量部と、ワニス(アクリディックA-165、大日本インキ化学工業(株)製)35.0質量部と、シンナー62.5質量部とを混ぜて、プラスチック板にスプレー塗装した。得られたスプレー塗板を10分間常温でセッティングした後、該スプレー塗板を50℃にて20分間加熱して塗膜を硬化させた。得られた塗板(予め上記の方法と同様の方法により測色を実施した)を、それぞれ0.1N水酸化ナトリウム水溶液と0.1N硫酸水溶液とに55℃で4時間浸漬した。その後、塗板を水洗、乾燥し、次いで上記の方法で測色することにより、浸漬前後での塗膜の色差を求めた。評価としては、「優」:ΔE* 45が3未満、「可」:ΔE* 45が3以上~7未満、「不可」:ΔE* 45が7以上とした。
上記の「塗板の作製方法」により得られた塗板を40℃に保持された水槽に10日間浸漬した。その後、塗膜の光沢保持率、色差および密着性を評価した。なお、この耐水性試験は、本発明でいう耐水(湿)性を評価するものである。
塗膜の光沢は、光沢計(日本電色工業(株)製、Gloss Meter VG2000)を用いて20度光沢を測定した。浸漬前の塗板の20度光沢の測定値をG1、浸漬後の塗板の20度光沢の測定値をG2とし、光沢保持率Rを下式によって求めた。
評価としては、「優」:Rが90%以上、「可」:Rが80%以上~90%未満、「不可」:Rが80%未満とした。
上記の「塗板の作製方法」により得られた塗板について、上記浸漬前後のΔE* 45を上記の測色法で求めた。評価としては、「優」:ΔE* 45が3未満、「可」:ΔE* 45が3以上~7未満、「不可」:ΔE* 45が7以上とした。
上記の「塗板の作製方法」により得られた塗板について、上記の浸漬後の塗板の塗膜上に幅2cm、長さ2cmにわたって2mm間隔で碁盤目状に切れ目を入れ、セロテープ(登録商標:ニチバン(株)製、CT-24)を塗膜に密着させ、45度の角度で引っ張り、該塗膜(メタリック顔料粒子)の上記碁盤目状部分の剥離度合いを目視で観察した。観察結果に応じて、「優」:剥離なし、「可」:やや剥離あり、「不可」:剥離あり、と評価した。
まず、基材粒子であるフレーク状のアルミニウム粒子のペースト(商品名5422NS、粒径:19μm、ペースト化剤:ミネラルスピリット、東洋アルミニウム(株)製)をミネラルスピリットで洗浄し、次いで濾過した。濾過後のペーストの不揮発成分(アルミニウム粒子)は74質量%(残部はミネラルスピリット)であった。
実施例2~6は、表面改質剤として、それぞれグリシジルメタクリレート(表1中の記号「F」)、ジメチルアミノエチルメタクリレート(表1中の記号「G」)、ジエチルアミノエチルアクリレート(表1中の記号「H」)、2-エチルヘキシルアクリレート(表1中の記号「I」)、ヒドロキシエチルアクリレート(表1中の記号「J」)を、各3.0g(不揮発成分100質量部に対して1質量部)を使用したことを除き、他は実施例1と同様な処理を施し、本発明の樹脂被覆メタリック顔料をペースト状態で得た。得られた樹脂被覆メタリック顔料について、実施例1と同様にして耐薬品性試験および耐水性試験を実施し、その結果をそれぞれ表2に示した。
実施例7~10は、表面改質剤であるラウリルメタクリレート(表1中の記号「E」)の添加量をそれぞれ0.15g、0.6g、15g、45g(不揮発成分(アルミニウム粒子)100質量部に対してそれぞれ0.05、0.2、5、15質量部)としたことを除き、他は実施例1と同様な処理を施し、本発明の樹脂被覆メタリック顔料をペースト状態で得た。得られた樹脂被覆メタリック顔料について、実施例1と同様にして耐薬品性試験および耐水性試験を実施し、その結果をそれぞれ表2に示した。
最外層形成工程を実施するスラリーを実施例1と同様にして調製した。
実施例12~16は、基材粒子として、それぞれフレーク状の着色アルミニウム粒子(東洋アルミニウム(株)製アルミニウムフレーク(商品名5422NS、粒径:19μm)を特開平9-124973号公報の実施例1に準じた方法で予め着色処理を行なったもの)、干渉色アルミニウム粒子(東洋アルミニウム(株)製アルミニウムフレーク(商品名5422NS、粒径:19μm)を国際公開第2007/094253号パンフレットの実施例1に準じた方法で予め干渉色の着色処理を行なったもの)、フレーク状のステンレス粒子(市販品、粒径:20μm、金属粒子に相当)、フレーク状のアルミナ粒子(市販品、粒径:6μm、無機化合物粒子に相当)、フレーク状のマイカ粒子(市販品、粒径:15μm、無機化合物粒子に相当)を使用したことを除き、他は実施例1と同様な処理を施し、本発明の樹脂被覆メタリック顔料をペースト状態で得た。得られた樹脂被覆メタリック顔料について、実施例1と同様にして耐薬品性試験および耐水性試験を実施し、その結果をそれぞれ表2に示した。
実施例1において、表面改質剤処理工程を実施しないことを除き、他は実施例1と同様な処理を施し、樹脂被覆メタリック顔料をペースト状態で得た。得られた樹脂被覆メタリック顔料について、実施例1と同様にして耐薬品性試験および耐水性試験を実施し、その結果を表2に示した。本比較例は、最外層形成工程のみを実施して樹脂被覆メタリック顔料を製造したものに該当する。
最外層形成工程を実施するスラリーを実施例1と同様にして調製した。
最外層形成工程を実施するスラリーを実施例1と同様にして調製した。
市販のフレーク状のアルミニウム粒子のペーストであるメタリック顔料ペースト(商品名5422NS、粒径:19μm、東洋アルミニウム(株)製)について、実施例1と同様にして耐薬品性試験および耐水性試験を実施し、その結果を表2に示した。本比較例は、最外層形成工程および表面改質剤処理工程を有しない基材粒子自体に該当する。
Claims (11)
- 基材粒子の表面に単層または複層の被覆層を形成した樹脂被覆メタリック顔料であって、
前記被覆層の最外層は、2個以上の重合性二重結合を有するモノマーおよびオリゴマーから選ばれた1種以上の化合物をその構成単位として含む重合体である樹脂からなり、
前記最外層の表面部は、1個の重合性二重結合を有する化合物である表面改質剤により処理されている樹脂被覆メタリック顔料。 - 前記表面改質剤は、不飽和カルボン酸のエステルである請求の範囲1に記載の樹脂被覆メタリック顔料。
- 前記基材粒子100質量部に対して前記表面改質剤を0.1~10質量部の割合で含む請求の範囲1に記載の樹脂被覆メタリック顔料。
- 前記基材粒子は、アルミニウム粒子である請求の範囲1に記載の樹脂被覆メタリック顔料。
- 前記基材粒子は、アルミニウム粒子の表面に無機顔料または有機顔料を付着させた着色アルミニウム粒子である請求の範囲1に記載の樹脂被覆メタリック顔料。
- 前記基材粒子は、アルミニウム粒子の表面に干渉作用を示す無機化合物層または金属層を1層以上有する干渉色アルミニウム粒子である請求の範囲1に記載の樹脂被覆メタリック顔料。
- 前記樹脂被覆メタリック顔料は、水性塗料に用いられるものである請求の範囲1に記載の樹脂被覆メタリック顔料。
- 請求の範囲1に記載の樹脂被覆メタリック顔料を含有してなる水性塗料。
- 請求の範囲8に記載の水性塗料が塗布された塗装物。
- 基材粒子の表面に単層または複層の被覆層を形成した樹脂被覆メタリック顔料の製造方法であって、
前記基材粒子の表面に、2個以上の重合性二重結合を有するモノマーおよびオリゴマーから選ばれた1種以上の化合物を重合反応させることにより、前記被覆層の最外層を形成する工程と、
前記最外層の表面部を、1個の重合性二重結合を有する化合物である表面改質剤により処理する工程と、を含む樹脂被覆メタリック顔料の製造方法。 - 前記表面改質剤により処理する工程は、前記最外層の表面部に残存する重合性二重結合と前記表面改質剤に含まれる重合性二重結合とを反応させることにより、前記表面改質剤を前記最外層の表面部に結合させるものである請求の範囲10に記載の樹脂被覆メタリック顔料の製造方法。
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EP2410024A1 (en) * | 2010-07-20 | 2012-01-25 | Silberline Manufacturing Company, Inc. | Film-forming pigments and coating system including the same |
US8642681B2 (en) | 2009-05-25 | 2014-02-04 | Toyo Aluminium Kabushiki Kaisha | Surface-coated metallic pigment, water base paint containing the same, and coated product to which water base paint has been applied |
US8815982B2 (en) | 2010-07-20 | 2014-08-26 | Silberline Manufacturing Company, Inc. | Colored system |
JP7390412B2 (ja) | 2022-01-28 | 2023-12-01 | 阪神高速技術株式会社 | 防錆塗料、防錆方法及び塗膜 |
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US8642681B2 (en) | 2009-05-25 | 2014-02-04 | Toyo Aluminium Kabushiki Kaisha | Surface-coated metallic pigment, water base paint containing the same, and coated product to which water base paint has been applied |
KR101735852B1 (ko) | 2009-05-25 | 2017-05-15 | 도요 알루미늄 가부시키가이샤 | 표면 피복 메탈릭 안료, 그것을 함유하는 수성 도료 및 그것이 도포된 도장물 |
EP2410024A1 (en) * | 2010-07-20 | 2012-01-25 | Silberline Manufacturing Company, Inc. | Film-forming pigments and coating system including the same |
CN102337052A (zh) * | 2010-07-20 | 2012-02-01 | 星铂联制造公司 | 成膜颜料和包含该成膜颜料的涂覆体系 |
US8815982B2 (en) | 2010-07-20 | 2014-08-26 | Silberline Manufacturing Company, Inc. | Colored system |
US8912252B2 (en) | 2010-07-20 | 2014-12-16 | Silberline Manufacturing Company, Inc. | Film-forming pigments and coating system including the same |
CN102337052B (zh) * | 2010-07-20 | 2015-03-04 | 星铂联制造公司 | 成膜颜料和包含该成膜颜料的涂覆体系 |
JP7390412B2 (ja) | 2022-01-28 | 2023-12-01 | 阪神高速技術株式会社 | 防錆塗料、防錆方法及び塗膜 |
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Publication number | Publication date |
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KR20110066918A (ko) | 2011-06-17 |
EP2325267A4 (en) | 2011-08-31 |
KR101624372B1 (ko) | 2016-05-25 |
US20110195244A1 (en) | 2011-08-11 |
EP2325267A1 (en) | 2011-05-25 |
US8530049B2 (en) | 2013-09-10 |
CN102159652A (zh) | 2011-08-17 |
EP2325267B1 (en) | 2019-07-31 |
JP2010070617A (ja) | 2010-04-02 |
CN102159652B (zh) | 2015-08-12 |
JP5196432B2 (ja) | 2013-05-15 |
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