WO2004096921A1 - アルミニウム顔料、その製造方法および樹脂組成物 - Google Patents
アルミニウム顔料、その製造方法および樹脂組成物 Download PDFInfo
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- WO2004096921A1 WO2004096921A1 PCT/JP2003/005484 JP0305484W WO2004096921A1 WO 2004096921 A1 WO2004096921 A1 WO 2004096921A1 JP 0305484 W JP0305484 W JP 0305484W WO 2004096921 A1 WO2004096921 A1 WO 2004096921A1
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- aluminum
- coating
- molybdenum
- silane coupling
- film
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
- C09C1/642—Aluminium treated with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
- C09C1/648—Aluminium treated with inorganic and organic, e.g. polymeric, 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Definitions
- the present invention relates to an anolememi-pigment, a method for producing the same and a resin composition.
- the present invention relates to an aluminum pigment. More specifically, the present invention relates to an aluminum pigment, a method for producing the same, and a resin composition containing the same, which is suitably used for an aqueous paint or an aqueous ink. Background art
- the coating film formed by using the metallic paint reflects the incident light from the outside by the scale-like metallic pigment contained in the coating film, and exhibits a glittering design.
- Aluminum is excellent in metallic luster, inexpensive, and easy to handle because of its low specific gravity. Therefore, aluminum is generally used for metallic finishes such as automotive paint finishes, plastic paint finishes, printing inks, and resin moldings. Metallic pigments containing mainly aluminum flakes (hereinafter simply referred to as "aluminum pigments”) are used.
- the surface of aluminum-flakes is treated with a saturated or unsaturated fatty acid such as oleic stearate and its derivatives, and the surface is treated with an interface.
- Aluminum pigments which have been added with an activator to impart water dispersibility have generally been provided.
- these water-dispersible aluminum pigments have problems such as low storage stability and poor weather resistance after coating when incorporated into an aqueous paint.
- the water-based paint containing these water-dispersible aluminum pigments deteriorates the dispersibility of the aluminum pigment during storage, so that the properties of the paint are remarkably deteriorated due to the occurrence of blemishes.
- aluminum since aluminum generally has a natural oxidation protection film on its surface, it is stable in the atmosphere containing oxygen and has excellent corrosion resistance to electrolytes in neutral water.
- the natural oxidation protection film of aluminum may not dissolve sufficiently in an acidic or alkaline aqueous solution and may be dissolved.
- metallic paints containing aluminum pigments due to the occurrence of acid rain, etc. are often exposed to harsh environments under acidic conditions, and it is not enough to protect aluminum pigments from corrosion by using a natural oxidation protection film alone. It is a difficult situation.
- Japanese Patent Publication No. Hei 154 386 discloses a method for treating an anolemmium pigment with coumic acid. According to this method, the chemical stability of the aluminum-pigment is improved, but the reactivity of the treatment solution is too strong to process fine aluminum pigment. Another drawback is that environmental problems are significant.
- Japanese Patent Application Laid-Open No. Sho 59-72401 discloses a method of treating an aluminum pigment with ammonium vanadate. Regarding this treatment, the change in the color tone of the aluminum pigment due to the treatment is large, and it has not been put to practical use.
- Japanese Patent Application Laid-Open No. 55-158202 discloses a method of coating an aluminum pigment with an acidic phosphoric acid ester. This method requires color and chemical stability Is good, but when a two-coat one-bake or two-coat two-bake coating is made, the treatment agent has an unfavorable effect on the adhesion between the aluminum pigment and the resin, and the base metallic coating)] Delamination between the topcoat layer and the topcoat layer is a major problem.
- Japanese Patent Application Laid-Open No. Hei 4-318181 discloses a method of treating an aluminum pigment with a treatment liquid containing an oxidizing agent such as molybdic acid and a phosphate ion and an alkaline earth metal ion.
- an oxidizing agent such as molybdic acid and a phosphate ion and an alkaline earth metal ion.
- aluminum pigments with excellent chemical stability can be prepared by this method, phosphate ions and alkaline earth metal ions contained in the processing solution tend to reduce the moisture resistance and other physical properties of the coating film.
- US Pat. No. 5,296,032 discloses a method of treating an aluminum pigment with a polyadione such as molybdic acid. The chemical stability of the pigment is not obtained.
- Japanese Patent Application Laid-Open No. 6-57171 discloses a method in which after treatment with ammonium molybdate, a molybdate or the like is added to further stabilize the aluminum pigment. .
- this method it is possible to obtain an aluminum pigment having excellent chemical stability, and there is no problem with the physical properties of the coating film, but there is a problem that the production process is complicated.
- U.S. Patent Nos. 2,885,366 disclose a method of coating various core materials with an amorphous silicon layer, and also show an example using aluminum powder as a core material. ing.
- this silica coating is performed in a strongly alkaline aqueous solution, aluminum powder reacts during the treatment process and may generate a large amount of hydrogen gas, which is extremely dangerous.
- this patent discloses a method of providing an intermediate layer of a basic salt of anoremium-chromium on a core material in order to efficiently coat the amorphous silica layer. It was difficult to provide a uniform coating on the pigment.
- Japanese Patent Application Laid-Open No. Hei 7-31885 discloses a method for producing an aluminum pigment having excellent corrosion resistance by coating an aluminum facial surface with siloxane and further coating a synthetic resin.
- the synthetic resin When the synthetic resin is coated on the coating, the thickness of the aluminum pigment becomes thicker, and the appearance and gloss due to protrusion from the coating film are low.
- adverse effects such as a decrease in concealment properties also occur.
- the object of the present invention is to provide excellent dispersibility and stability, no generation or aggregation of hydrogen gas during storage, and excellent design of the coating film appearance.
- An object of the present invention is to provide an aluminum pigment which can be suitably used by being incorporated into a paint or a water-based ink.
- Another object of the present invention is to provide a water-based paint or a water-based ink, which is excellent in dispersibility and stability, does not generate or coagulate hydrogen gas during storage, and has an excellent design of the coating film appearance. It is an object of the present invention to provide a method for producing an aluminum-pigment that can be suitably used by being blended with a pigment.
- Another object of the present invention is to provide a water-based paint which is excellent in dispersibility and stability, does not generate hydrogen gas during storage, and does not agglomerate aluminum pigments, and has excellent design of the coating film appearance.
- Another object of the present invention is to provide a resin composition that can be suitably used as an aqueous ink.
- Another object of the present invention is to provide excellent dispersibility and stability without generating hydrogen gas during storage and without agglomeration of aluminum-pigment, To provide a water-based paint and a water-based ink having excellent water resistance.
- the present inventors have set the surface of the aluminum particles to have poor reactivity with the aqueous solution, not to impair the design of the coating film, and to prevent hydrogen gas or the like during storage. Based on the idea that coating with a film having the property of preventing the generation is sufficient, we conducted experiments on coating the surface of aluminum particles with coatings of various compositions, and conducted intensive studies.
- the surface of the aluminum particles was coated with a molybdenum coating made of molybdenum oxide and / or molybdenum hydrate. It has been found that the surface of the film may be coated with a silicic film made of amorphous silica and a film obtained from a silane coupling agent. Furthermore, it has been found that when both the silica film and the film obtained from the silane coupling agent are formed, a sufficient effect can be obtained without forming a molybdenum film on the surface of the aluminum particles.
- the present inventors have also studied what manufacturing method is suitable for coating the surface of the aluminum particles with a molybdenum coating, a silica coating, or a coating formed from a silane coupling agent. We studied diligently. Then, after examination, they found that the aluminum pigment could be efficiently produced by using a specific production method, and completed the present invention.
- the aluminum pigment of the present invention comprises aluminum particles, a molybdenum coating made of molybdenum oxide and / or molybdenum hydrate covering the surface of the aluminum particles, and amorphous silica further covering the molybdenum coating. And a film formed from a silica coating and / or a silane coupling agent.
- another aluminum pigment of the present invention is formed from aluminum particles, a silica coating made of amorphous silica covering the surface of the aluminum particles, and a silane coupling agent further coating the silicic coating. And a coating to be formed.
- the content of molybdenum is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of aluminum particles, and Regardless of the presence or absence of the molybdenum coating, the silicon content is preferably in the range of 1 to 20 parts by mass.
- the silane coupling agent used in the present invention is preferably at least one selected from compounds having the following structures.
- RA an alkyl, aryl, or alkenyl group having 2 to 18 carbon atoms
- R B C 1-3 alkyl group
- a dispersion solution containing aluminum particles and a molybdenum compound is agitated so that a surface of the aluminum particles is Forming a molybdenum film comprising a molybdenum oxide and z or molybdenum hydrate; and forming a molybdenum film having a molybdenum film and a dispersion solution containing aluminum particles having the molybdenum film, an organosilicon compound and / or a silane coupling agent and a hydrolysis catalyst.
- the organosilicon compound and / or the silane coupling agent is hydrolyzed, so that the surface of the molybdenum film of the aluminum particles is coated with a silica force coating made of amorphous silica and Z or silane coupling ⁇ . Forming a film formed from.
- another method for producing an aluminum pigment of the present invention is a method of producing a molybdenum coating comprising molybdenum oxide and / or molybdenum hydrate on a surface of the aluminum particles by stirring a dispersion solution containing aluminum particles and a molybdenum compound. Forming a molybdenum coating, and adjusting the pH of the dispersion solution containing the anoremium particles having the molybdenum coating, the organosilicon compound, and the hydrolysis catalyst to hydrolyze the organosilicon compound to form a molybdenum coating of the aluminum particles.
- a silica coating made of amorphous silica on the surface Forming a silica coating made of amorphous silica on the surface, and adjusting the J) H of the dispersion solution containing the aluminum particles having the silica coating, the silane coupling agent, and the hydrolysis catalyst, to thereby form a silane cap.
- the ring agent is hydrolyzed to form a silane cut on the surface of the silica coating And forming a coating film formed from the ring agent.
- another method for producing the aluminum pigment of the present invention comprises adjusting the pH of a dispersion solution containing aluminum particles, an organic silicon compound, a silane coupling agent, and a hydrolysis catalyst, whereby the organosilicon compound and the silane coupling agent are adjusted.
- another method for producing an aluminum pigment of the present invention is to adjust the pH of a dispersion solution containing aluminum particles, an organosilicon compound, and a hydrolysis catalyst to hydrolyze the organosilicon compound, Forming a silicide film made of amorphous silica on the surface of -silver particles, and adjusting the pH of a dispersion solution containing the anoreminium particles having the silicide film, a silane coupling agent, and a hydrolysis catalyst. Forming a film formed from the silane coupling agent on the surface of the silica coating of the aluminum particles by hydrolyzing the silane coupling agent.
- the step of forming a molybdenum film on the surface of the aluminum particles it is preferable to use one or more selected from the group consisting of polymolybdic peroxide, ammonium molybdate, and phosphomolybdic acid as the molybdenum compound.
- the silica coating it is desirable to use tetraethoxysilane and / or tetramethoxysilane as the organic silicon compound.
- a basic catalyst is used as a hydrolysis catalyst, and the pH is adjusted to a range of 7.0 to 11.0. Adjustments are recommended.
- the hydrolysis catalyst comprises triethanolanolamine, ammonia, ethylenediamine, and 3-aminopropyltriethoxysilane. It is preferable to use one kind or two or more kinds selected from
- an acidic catalyst is used as a hydrolysis catalyst, and the pH is adjusted to a range of 1.5 to 4.0. Is also good.
- the present invention includes a resin composition containing the aluminum pigment of the present invention and a resin.
- the resin composition of the present invention contains 0.1 to 30 mass of the aluminum pigment of the present invention. / 0 is preferably contained.
- the aluminum pigment of the present invention is suitably used in a water-based coating together with a binder and a hydrophilic solvent. Further, the aluminum pigment of the present invention is suitably used by being blended into an aqueous ink together with a binder and a hydrophilic solvent.
- FIG. 1 is a diagram illustrating an example of the method for producing an aluminum pigment of the present invention.
- FIG. 2 is a diagram illustrating an example of another method for producing the aluminum pigment of the present invention.
- FIG. 3 is a diagram illustrating an example of another method for producing the aluminum pigment of the present invention.
- FIG. 4 is a diagram illustrating an example of still another method for producing the aluminum pigment of the present invention.
- the aluminum pigment of the present invention includes aluminum particles and a coating (hereinafter referred to as a “molybdenum coating”) of molybdenum oxide and / or molybdenum hydrate covering the surface of the aluminum particles.
- a coating hereinafter referred to as a “molybdenum coating”
- sica coating An amorphous silica coating for covering the molybdenum coating (hereinafter referred to as “silica coating”); and a coating formed from Z or a silane coupling agent.
- another aluminum pigment of the present invention is formed from anoreminium particles, a silica coating made of amorphous silica covering the surface of the aluminum particles, and a silane coupling agent further coating the silica coating. And a coating.
- the aluminum pigment of the present invention is based on aluminum particles.
- the aluminum particles used in the present invention may be composed of only aluminum or an aluminum-based alloy, and the purity thereof is not particularly limited.
- the shape of the aluminum particles used in the present invention may be various shapes such as a granular shape, a plate shape, a lump shape, a flake shape (scale shape), and the like. Is preferably in the form of flakes.
- the average particle size of the aluminum particles used in the present invention is not particularly limited, but is preferably 2 m or more, and more preferably 5 / m or more.
- the average particle size is preferably 40 ⁇ or less, and more preferably 30 ⁇ m or less. If the average particle size is less than 2 / m, handling in the manufacturing process is difficult, and the particles tend to aggregate, and the average particle size exceeds 40 ⁇ As a result, the surface of the coating film may be rough when used as a paint, and a desirable design may not be realized.
- the aluminum particles used in the present invention preferably have a shape factor obtained by dividing the average particle size by the average thickness (referred to as “aspect ratio” in the present specification) of 5 or more, particularly preferably 15 or more. Is particularly preferred.
- the aspect ratio is preferably not more than 1,000, and more preferably not more than 50,000. When the paste ratio is less than 5, the glitter tends to be insufficient, and when the aspect ratio exceeds 1,000, the mechanical strength of the flakes decreases and the color tone becomes unstable. There is.
- the average particle size of the aluminum particles used in the present invention is calculated by calculating the volume average from the particle size distribution measured by a known particle size distribution measuring method such as a laser diffraction method, a mesh opening sieve method, and a Coulter counter method. It is determined by calculation.
- the average thickness is calculated from the hiding power and density of the metal flake pigment.
- a grinding aid may be attached to the surface of the aluminum particles used in the present invention.
- Unsaturated fatty acids are usually used as grinding aids. Examples of the unsaturated fatty acid used here include oleic acid, linoleic acid, linoleic acid, ricinoleic acid, elaidic acid, somalic acid, gadolinic acid, and erlic acid.
- One of the aluminum pigments of the present invention has a molybdenum coating covering the surface of aluminum particles.
- the molybdenum film is a film made of molybdenum oxide and / or molybdenum hydrate.
- Molybdenum oxide specifically means Mo 0 3 , Mo 2 ⁇ 3 , etc.
- Japanese specifically refers to ⁇ ⁇ 3 ⁇ ⁇ 20 , ⁇ ⁇ 3 ⁇ ⁇ 20 2 ⁇ ⁇ 20 .
- the coating serves as a nucleus for precipitation, and the formation of a silicon coating that further covers the surface of the molybdenum coating is facilitated.
- the aluminum pigment having the molybdenum coating improves the corrosion resistance.
- molybdenum coatings can be formed from silica coatings and / or silane coupling agents. It also has the effect of preventing an abnormal reaction between the treatment solution (a solution containing water and a strongly alkaline or acidic solution) and the aluminum particles covered with the molybdenum film during the film formation process.
- the amount of Mo contained in the molybdenum film formed on the surface of the aluminum particles used in the present invention is preferably at least 0.01 part by mass with respect to 100 parts by mass of the aluminum particles. It is more preferable that the amount be 5 parts by mass or more. Further, the amount of Mo is preferably 5.0 parts by mass or less, more preferably 2.0 parts by mass or less. It is desirable that the amount of Mo be changed according to the specific surface area of the aluminum particles to be treated. It is preferable to increase the amount of Mo for aluminum particles having a large specific surface area, and to decrease the amount for small aluminum particles.
- the amount of Mo is less than 0.01 parts by mass, the chemical stability tends to decrease. If the amount of Mo exceeds 5.0 parts by mass, the decrease in the color tone (metallic luster) of the aluminum pigment increases. In some cases, inconveniences such as agglomeration of the aluminum pigment and deterioration of physical properties of the coating film may occur.
- the molybdenum film does not need to be a film composed only of molybdenum oxide and / or molybdenum hydrate, and may contain other additives and impurities as long as the properties of the present invention are not impaired. .
- the silicic coating applied to the aluminum face of the present invention may further cover the surface of the molybdenum coating or may directly cover the aluminum surface together with the coating formed from the silane coupling agent.
- the silica coating is a coating made of amorphous silica, and the amorphous silica is specifically a siloxane [H 3 S i O (H 2 S i ⁇ ) n S i H 3 ], S i 0 2 , S i O 2 -n H 2 ⁇ , etc.
- n represents any positive integer.
- the aluminum pigment of the present invention having a silica coating covering the surface of the molybdenum coating of aluminum particles has more excellent corrosion resistance than having only the molybdenum coating.
- amorphous silica has a hydrophilic surface
- the amorphous silica of the present invention having a silica coating Noreminium pigments can be easily dispersed in aqueous paints and inks.
- amorphous silica is very stable in an aqueous solution
- the aluminum pigment of the present invention having a silica coating is very stable in an aqueous solution.
- silica coating of the aluminum pigment of the present invention another corrosion inhibitor may be added for the purpose of further improving the corrosion resistance of the aluminum pigment.
- the corrosion inhibitor to be added is not particularly limited, and a known corrosion inhibitor can be used in a blending amount that does not impair the effects of the present invention. Examples thereof include acids, organic phosphorus compounds, and metal salts of molybdic acid.
- the above-mentioned silica film does not need to be a film consisting of only amorphous silica, and may contain other additives and impurities as long as the characteristics of the present invention are not impaired. Description of film formed from silane coupling agent>
- the aluminum pigment of the present invention by providing a film formed from a silane coupling agent on a molybdenum film or a silica film, reactivity to water can be further suppressed, and adhesion and moisture resistance can be further reduced.
- Various effects can be expected, such as improvement of coating film properties such as water resistance and weather resistance, improvement of dispersibility in paint, and improvement of orientation of aluminum pigment.
- the film obtained from the silane coupling agent is obtained by hydrolyzing the following silane coupling agent and reacting with the hydroxyl groups in the silica film on the surface of the aluminum particles.
- RA an alkyl, aryl, or alkenyl group having 2 to 18 carbon atoms
- R B C 1-3 alkyl group
- Examples include n-propyltrimethoxysilane, isobutynoletrimethoxysilane, octynoletriethoxysilane, decyltrimethoxysilane, otadecyltriethoxysilane, fueltrimethoxysilane, fueltriethoxysilane, and diphenylethoxysilane.
- the total content of silicon contained in the silica film provided by the present invention and the film formed from the silane coupling agent is preferably at least 1 part by mass with respect to 100 parts by mass of the anorememim particles. More preferably, it is 2 parts by mass or more. Further, the content of silicon is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less. If the silicon content is less than 1 part by mass, corrosion resistance, water dispersibility, stability and the like tend to decrease. If the silicon content exceeds 20 parts by mass, aluminum pigments Problems such as agglomeration, loss of hiding power, and impaired color tone such as metallic luster may occur.
- FIG. 1 is a diagram showing an example of the method for producing an aluminum pigment of the present invention.
- a molybdenum coating film made of molybdenum oxide and / or molybdenum hydrate is formed on the surface of the aluminum particles by stirring a dispersion solution containing aluminum particles and a molybdenum compound.
- FIG. 2 is a diagram illustrating an example of another method for producing the aluminum pigment of the present invention.
- Another method for producing the aluminum pigment of the present invention is to form a molybdenum coating made of molybdenum oxide and Z or molybdenum hydrate on the surface of the aluminum particles by stirring a dispersion solution containing anoremium particles and a molybdenum compound.
- the silane coupling agent is hydrolyzed by adjusting the pH of the dispersion solution containing it, and the surface of the silica coating of aluminum particles (S205) forming a film formed from a silane coupling agent.
- FIG. 3 is a diagram illustrating an example of another method for producing the aluminum pigment of the present invention.
- Still another method for producing the aluminum pigment of the present invention comprises the steps of: By adjusting the pH of the dispersion solution containing the silicon compound, the silane coupling agent, and the hydrolysis catalyst, the organic silicon compound and the silane coupling agent are hydrolyzed to form amorphous silica on the surface of the anolemminium particles. Forming a film formed from a silica film made of a silane coupling agent (S301).
- FIG. 4 shows an example of still another method for producing the aluminum pigment of the present invention.
- still another method for producing the aluminum pigment of the present invention is to adjust the pH of a dispersion solution containing aluminum particles, an organosilicon compound, and a hydrolysis catalyst to hydrolyze the organosilicon compound, Forming a silica coating made of amorphous silica on the surface of the aluminum particles (S401); and adjusting the pH of the dispersion solution containing the aluminum particles having the silica coating, the silane coupling agent and the hydrolysis catalyst ′.
- One method for producing the aluminum pigment of the present invention includes a step of forming a molybdenum film on the surface of the aluminum particles by stirring a dispersion solution containing anolemem particles and a molybdenum compound.
- the method of forming the molybdenum coating on the surface of the aluminum particles is not particularly limited, and any method may be used as long as the dispersion solution containing the aluminum particles and the molybdenum compound can be uniformly stirred.
- the stirrer used in the step of stirring the dispersion solution containing the aluminum particles and the molybdenum compound is not particularly limited, and a known stirrer capable of efficiently and uniformly stirring the dispersion solution containing the aluminum particles and the molybdenum compound is used.
- a known stirrer capable of efficiently and uniformly stirring the dispersion solution containing the aluminum particles and the molybdenum compound is used.
- Specific examples include an eder, a kneader, a rotating vessel stirrer, a stirrer type reaction vessel, a V-type stirrer, a double-cone type stirrer, a screw mixer, a sigmami 484
- Examples include a mixer, a flash mixer, a gas stirrer, a ball mill, and an edge runner. '
- the molybdenum compound used in the present invention is not particularly limited, and a known molybdenum compound that can form a molybdenum film by adding to a dispersion solution containing aluminum particles and stirring can be used.
- specific examples include polymolybdic peroxide, ammonium molybdate, and phosphomolybdic acid.
- the molybdenum compounds may be used alone or in combination of two or more.
- polymolybdenum peroxide is a compound generally represented by the following composition formula (1), which dissolves metal molybdenum powder, molybdenum oxide, and the like in an aqueous solution of hydrogen peroxide having a concentration of 5 to 40%. Thus, it can be easily prepared.
- X is 1 or 2
- y is an integer of 2 to 5
- m and n are any positive integers.
- a hydrophilic solvent as a solvent for the dispersion solution containing the aluminum particles and the molybdenum compound.
- a hydrophilic solvent Specifically, methyl alcohol, ethyl alcohol, isopropynole alcohol, n-propyl alcohol, t-butyl alcohol, n-butynoleanol, isobutynoleanol, etinolesanolosenole, butylace solvent Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, acetone, and the like.
- the hydrophilic solvent may contain water, or water may be used alone as the hydrophilic solvent. Further, it is more preferable to use the hydrophilic solvent and water in a mixture than to use the hydrophilic solvent alone. By using a mixture of the hydrophilic solvent and water, the contact efficiency between the aluminum particles and the molybdenum compound can be further improved. Further, when referred to as “hydrophilic solvent” in the present specification, the term includes the hydrophilic solvent, water, and a mixture of the hydrophilic solvent and water.
- the content of the molybdenum compound is preferably at least 0.02 parts by mass, more preferably at least Q.1 parts by mass, based on 100 parts by mass of the aluminum particles.
- the content of the molybdenum compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
- the treatment effect tends to be insufficient, and when the content of the molybdenum compound exceeds 20 parts by mass, the luster of the aluminum pigment is increased. Tend to be short.
- the content of the hydrophilic solvent is preferably at least 50 parts by mass, and more preferably 100 parts by mass with respect to 100 parts by mass of the aluminum particles. The above is more preferable. Further, the content of the hydrophilic solvent is preferably not more than 5,000 parts by mass, more preferably not more than 2,000 parts by mass.
- the content of the hydrophilic solvent is less than 50 parts by mass, the molybdenum compound is unevenly distributed and aggregation of the aluminum particles tends to be remarkable, and the content of the hydrophilic solvent is 50,000 parts by mass. If it exceeds, the effect of treating the aluminum particles with the molybdenum compound tends to be insufficient.
- the temperature of the dispersion solution during the stirring step is preferably 10 ° C or higher, and may be 30 ° C or higher. Is more preferable. Further, the temperature of the dispersion solution during the stirring step is preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
- the temperature of the dispersion solution during this stirring step is lower than 10 ° C, the reaction time for obtaining a sufficient treatment effect tends to be long, and the temperature of the dispersion solution during this stirring step is 10 ° C. Above ° c, the risk of runaway reaction tends to increase.
- the stirring time is preferably at least 0.5 hour, more preferably at least 1.0 hour.
- the stirring time is preferably 10 hours or less, and more preferably 5 hours or less.
- the stirring time is less than 0.5 hours, the treatment effect tends to be insufficient. If the stirring time exceeds 10 hours, the treatment cost tends to be large.
- the dispersion solution is washed with the hydrophilic solvent containing no water, and then filtered using a filter to obtain a molybdenum coating film. It is preferable to remove ice and unreacted substances from a cake containing aluminum particles having the following formula.
- One example of the method for producing the aluminum pigment of the present invention is to adjust the pH of a dispersion solution containing aluminum particles having or not having a molybdenum coating, an organosilicon compound, and a hydrolysis catalyst.
- the method for forming the silica coating is not particularly limited, and may be adjusted by adjusting the pH of a dispersion solution containing aluminum particles with or without a molybdenum coating, an organosilicon compound, and a hydrolysis catalyst. Any known method may be used as long as the method can hydrolyze the organosilicon compound to form a silica film on the surface of the aluminum particles or the surface of the molybdenum film.
- an organosilicon compound to a dispersion solution containing aluminum particles having or not having a molybdenum film, and further adding a hydrolysis catalyst to adjust the pH value of the dispersion solution
- a method is preferred in which the organosilicon compound is hydrolyzed to form a silicic coating on the surface of the aluminum particles or the surface of the molybdenum coating.
- the components are uniformly dispersed or dissolved in the above-mentioned dispersion solution by stirring at an appropriate speed.
- the pH value of the dispersion and solution by adding a hydrolysis catalyst for simplification of the production process, but the pH value of the dispersion solution is adjusted.
- the method is not particularly limited to the method of adding a hydrolysis catalyst, and the pH of the dispersion solution may be adjusted using another acidic and / or alkaline compound.
- organic silicon compound includes an organic silicon compound and a condensate of the organic silicon compound.
- the organic silicon compound used in the present invention is not particularly limited.
- the organosilicon compound is hydrolyzed by adjusting the pH of a dispersion solution containing aluminum particles having or not having a butene coating, the organosilicon compound, and a hydrolysis catalyst, so that the surface of the aluminum particles or the molybdenum coating is formed.
- a known organic silicon compound and a condensate thereof capable of forming a silicic film on the surface thereof can be used.
- organosilicon compound examples include tetraethoxysilane, tetramethoxysilane, tetraisopropoxysilane, and the like, and condensates thereof.
- these organic silicon compounds may be used alone, or two or more thereof may be used with stirring.
- the hydrolysis catalyst used in the present invention is not particularly limited, and by adjusting the pH of a dispersion solution containing aluminum particles having or not having a molybdenum coating, an organosilicon compound, and the hydrolysis catalyst, A known hydrolysis catalyst that hydrolyzes an organosilicon compound by the action of the hydrolysis catalyst and forms a silica coating on the surface of the aluminum particles or the surface of the molybdenum coating can be used.
- organic silicon compound hydrolysis catalyst examples include monoethanolamine, diethanolamine, triethanolamine, ammonia, ethylenediamine, t-butylamine, 3-aminopropyltriethoxysilane, n- Basic hydrolysis catalysts such as 2-aminopropyl-3-aminopropyltriethoxysilane, n-2-aminoethyl-3-aminopropylmethyldimethoxysilane, urea, sodium silicate and sodium hydroxide, oxalic acid, acetic acid, Examples include acidic hydrolysis catalysts such as nitric acid, sulfuric acid, phosphoric acid, and phosphonic acid.
- a basic hydrolysis catalyst rather than an acidic hydrolysis catalyst.
- triethanolamine, ammonia, ethylenediamine, 3-aminopropyltriethoxysilane, and the like are particularly preferable from the viewpoint of quality and the like.
- a hydrophilic solvent is used as a solvent for a dispersion solution containing aluminum particles having or not having a molybdenum film, an organosilicon compound, and a hydrolysis catalyst.
- a hydrophilic solvent is used as a solvent for a dispersion solution containing aluminum particles having or not having a molybdenum film, an organosilicon compound, and a hydrolysis catalyst.
- Specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, n-butylinoreanolone, isobutinoleanolecone, etinoleserosonolep, butinole Use of cellosonorep, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, acetone or the like is preferable in that an abnormal reaction between aluminum particles and water is avoided.
- water may be contained in these hydrophilic solvents.
- the content of water in these hydrophilic solvents is preferably 20% by mass or less from the viewpoint of avoiding an abnormal reaction between aluminum particles and water.
- the content of the organic silicon compound is 2 parts by mass with respect to 100 parts by mass of the anorenium particles.
- the amount is preferably at least, and more preferably at least 5 parts by mass.
- the content of the organosilicon compound is preferably at most 200 parts by mass, more preferably at most 100 parts by mass.
- the treatment effect tends to be insufficient, and when the content of the organosilicon compound exceeds 200 parts by mass, aggregation of the anoremi-pum particles is performed. And the decrease in glitter tends to be remarkable.
- the organic silicon compound When the organic silicon compound is added, it may be added gradually or all at once.
- the content of the hydrolysis catalyst was 0.1 with respect to 100 parts by mass of the aluminum particles.
- the amount is preferably at least 0.5 part by mass, more preferably at least 0.5 part by mass.
- the content of the hydrolysis is preferably 20 parts by mass or less, more preferably 10 parts by mass or less. If the content of the hydrolysis catalyst is less than 0.1 part by mass, the amount of the silica layer deposited tends to be insufficient, and if the content of the hydrolysis catalyst exceeds 20 parts by mass, aluminum There is a tendency that aggregation of the memory particles becomes remarkable.
- the aluminum particles 10 The content of the hydrophilic solvent is preferably at least 500 parts by mass, more preferably at least 1,000 parts by mass, based on 0 parts by mass. Further, the content of the hydrophilic solvent is preferably at most 10,000 and more preferably at most 5,000.
- the content of the hydrophilic solvent is less than 500 parts by mass, the viscosity of the slurry tends to be high and stirring tends to be difficult, and the content of the hydrophilic solvent is 100,000 parts by mass. If the temperature exceeds the limit, the cost of recovering and regenerating the processing solution tends to increase.
- the temperature of the dispersion solution in the step is preferably 20 ° C. or more, and 30 ° C. The above is more preferable.
- the temperature of the dispersion solution during the stirring step is preferably 90 ° C. or lower, more preferably 80 ° C. or lower.
- the temperature of the dispersion solution during this stirring step is lower than 20 ° C, the formation speed of the silica layer tends to be slow and the processing time tends to be long. If the temperature exceeds 90 ° C, the risk of runaway reaction tends to increase.
- the reaction time is preferably at least 1 hour, more preferably at least 3 hours.
- the stirring time is preferably 48 hours or less, and more preferably 24 hours or less.
- the stirring time is less than 1 hour, the treatment effect tends to be insufficient, and if the stirring time exceeds 48 hours, the treatment cost tends to be large.
- the pH value of the dispersion solution changes during the reaction, so it is necessary to appropriately adjust the pH value. There is. At this time, it is desirable to adjust the pH value by adding a hydrolysis catalyst, but as long as the properties of the aluminum pigment of the present invention are not impaired, a dispersion solution using another acidic and / or alkaline compound is used. May be adjusted.
- the basic hydrolysis catalyst is used.
- the pH is preferably 7 or more, and more preferably 7.5 or more. Further, the pH of this dispersion solution is preferably 11 or less, more preferably 10 or less.
- the silica layer formation rate tends to be low. If the pH of the dispersion in the stirring step exceeds 11, if the pH of the dispersion is more than 11, the aggregation and luminosity of the aluminum particles will occur. There is a tendency for the deterioration of the property to be large.
- a basic hydrolysis catalyst it is more preferable to use a basic hydrolysis catalyst than to use an acidic hydrolysis catalyst in the step of forming a silica coating. This is preferable because the forming speed is high and the productivity is good. Nevertheless, using an acidic hydrolysis catalyst does not make much of a difference in terms of quality from using a basic hydrolysis catalyst.
- ⁇ : should be 1.5 or more. Is preferred, and more preferably 2 or more. Further, the pH of this dispersion solution is preferably 4 or less, and more preferably 3 or less.
- a method for forming a film formed from a silane coupling agent is the same as a method for forming a silica film. And forming a film.
- the coating formed from the silane coupling agent is formed on the molybdenum coating or on the silica coating. It is formed by reacting with hydroxyl groups.
- the aluminum particles having a molybdenum coating When a film formed from a silane coupling agent is directly provided on the aluminum particles having a molybdenum coating, the aluminum particles having a molybdenum coating By adjusting the pH of the dispersion solution containing the silane coupling agent and the hydrolysis catalyst, the silane coupling agent is hydrolyzed to form a film formed from the silane coupling agent on the surface of the molybdenum film.
- a dispersion solution containing aluminum particles with or without a molybdenum film, an organosilicon compound, a silane coupling agent, and a hydrolysis catalyst may be used.
- the organosilicon compound and the silane coupling agent are hydrolyzed to form a film formed from the silane coupling agent on the silicon film.
- the silane coupling agent is formed after the formation of the silicic acid coating by hydrolysis in order to form the silicic acid coating by hydrolysis of the organic silicon compound and the film formation by hydrolysis of the silane coupling agent stepwise. May be added and further hydrolyzed to form a film formed from a silane coupling agent.
- Conditions such as a reaction solvent, a temperature, and a hydrolysis catalyst for forming a film formed from a silane coupling agent are the same as those for forming a silicic film.
- the amount of the silane coupling agent is 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the aluminum particles. If the amount is less than this, the desired effect tends not to be obtained. If the amount is too large, the amount of unreacted silane coupling agent increases, and the physical properties of the coating film tend to deteriorate.
- the dispersion solution is washed with the above-mentioned hydrophilic solvent containing no water. It is preferable to remove water and unreacted substances from the cake containing the aluminum pigment of the present invention by filtering using a filter.
- the cake containing the aluminum pigment of the present invention may be subjected to heat treatment at a temperature in the range of 100 to 500 ° C.
- the step of forming a molybdenum film on the surface of the aluminum particles and the step of forming a film formed from a silica film and / or a silane coupling agent on the surface of the molybdenum film of aluminum particles are performed in different dispersion solutions. It may be performed continuously, after adjusting the components in the same dispersion solution as appropriate. It is possible.
- the resin composition of the present invention is characterized by containing the aluminum pigment of the present invention and a resin.
- the resin that can be blended in the resin composition of the present invention is not particularly limited, and examples thereof include an acrylic resin, an alkyd resin, a polyester resin, a polyurethane resin, a polyvinyl acetate resin, a nitrocellulose resin, Fluororesins and the like can be suitably used.
- the coloring pigments other than the aluminum pigment of the present invention that can be blended with the resin composition of the present invention are not particularly limited.
- phthalocyanine, quinatalidone, isoindolinone, perylene, azo lake, oxidized Examples include iron, graphite, carbon black, titanium oxide, and pearl mai power.
- additives that can be added to the resin composition of the present invention are not particularly limited, but include surfactants, curing agents, ultraviolet absorbers, static electricity removers, thickeners, extenders, Dyes, corrosion inhibitors and the like.
- the resin composition of the present invention may contain water, a hydrophilic solvent, an organic solvent, and the like, in addition to the above components.
- the content of the aluminum pigment of the present invention in the resin composition of the present invention is preferably at least 0.1% by mass, more preferably at least 1.0% by mass, based on the whole resin composition.
- the content of the aluminum pigment of the present invention was 30% by mass. / 0 or less, preferably 20 mass. / 0 or less is more preferable.
- the decorative (metallic) effect tends to decrease
- the content of the aluminum pigment of the present invention is more than 30% by mass, the resin
- the properties (weather resistance, corrosion resistance, mechanical strength, etc.) of the composition may be insufficient.
- the resin composition of the present invention containing the aluminum pigment of the present invention can be suitably used by being blended in paints, inks, and the like.
- the paints and inks when they are blended in water-based paints and water-based inks, they can be used particularly preferably.
- the resin composition of the present invention may be used alone or not as a paint or ink. Even when kneaded and molded into a rubber composition or a plastic composition, it has a good appearance with excellent metallic feeling and excellent weather resistance and stability, so that it can be suitably used as it is.
- the aluminum pigment of the present invention can be suitably blended in a water-based paint and a water-based ink together with a binder and a hydrophilic solvent.
- the binder used for the water-based paint and water-based ink containing the aluminum pigment of the present invention is not particularly limited, and examples thereof include acrylic resin, alkyd resin, polyester resin, polyurethane resin, and polyurethane resin. Resins such as butyl acetate resin, nitrocellulose resin, and fluororesin can be suitably used.
- the binder used for the water-based paint and the water-based ink containing the aluminum pigment of the present invention is generally used as a binder for the water-based paint or the water-based ink, and can be solidified after coating to form a good coating film. If it is, a binder other than resin can be used. Specific examples include polymer compositions other than resins, such as rubber compositions, plastic compositions, and natural polymer compositions.
- color pigments other than the aluminum pigment of the present invention which can be mixed with the water-based paint and the water-based ink containing the aluminum pigment of the present invention, are not particularly limited.
- phthalocyanine, quinatalidone examples include indolinone, perylene, azo lake, iron oxide, graphite, carbon black, titanium oxide, and pearl myriki.
- Additives that can be mixed with the water-based paints and water-based inks containing the aluminum pigment of the present invention are not particularly limited, but include surfactants, curing agents, ultraviolet absorbers, antistatic agents, Examples include a thickener, an extender pigment, and a dye.
- the hydrophilic solvent that can be added to the water-based paint and water-based ink containing the aluminum pigment of the present invention is not particularly limited.
- the hydrophilic solvent may contain water, or water may be used alone as the hydrophilic solvent.
- the above-mentioned hydrophilic solvents can be used by stirring one kind or two or more kinds depending on the use.
- the content of the aluminum pigment of the present invention in the aqueous paint and the aqueous ink containing the aluminum pigment of the present invention is preferably at least 0.1% by mass based on the binder content. It is more preferable that the content be 0% by mass or more. Further, the content of the aluminum pigment of the present invention is preferably 30% by mass or less, more preferably 20% by mass or less, based on the binder content.
- the content of the aluminum-pigment of the present invention is 0.1 mass. /.
- the decorative (metallic) effect of the coating film of the water-based paint and the water-based ink tends to decrease.
- the characteristics (weather resistance, corrosion resistance, mechanical strength, etc.) of the coating film may be insufficient.
- the content of the hydrophilic solvent in the aqueous paint and the aqueous ink containing the aluminum pigment of the present invention is 20% by mass with respect to the content of the binder. / 0 or more, preferably 50 mass. / 0 or more is more preferable. Further, the content of the hydrophilic solvent is preferably 200% by mass or less, more preferably 100% by mass or less, based on the binder content.
- the content of the hydrophilic solvent is less than 20% by mass, the viscosity of the paint or ink tends to be high, and the handling tends to be difficult, and the content of the hydrophilic solvent exceeds 200% by mass. In this case, the viscosity of paints and inks tends to be too low, and film formation tends to be difficult.
- the application of the aluminum pigment of the present invention to water-based paints and water-based inks is not limited, and paints containing organic solvents, inks containing organic solvents, powder paints, rubber compositions It can be suitably used even when it is combined with a plastic composition, a natural polymer composition, or the like.
- the coating method or printing method of the water-based paint and the water-based ink containing the aluminum-pigment of the present invention is not particularly limited, and the form of the water-based paint or water-based ink used, the surface shape of the substrate, etc.
- a method for applying the water-based paint containing the aluminum pigment of the present invention there are a spray method, a roll coater method, a brush coating method, a doctor blade method and the like, and a printing method of the water-based ink containing the aluminum pigment of the present invention. Examples include gravure printing and screen printing.
- the coating film of the water-based paint or water-based ink containing the aluminum pigment of the present invention may be formed on an undercoat layer or an intermediate coating layer by electrodeposition coating or the like.
- a topcoat layer may be formed on a coating film containing a water-based paint or a water-based ink. .
- the next coating layer may be applied after coating and curing or drying each coating layer, or after coating each coating layer by so-called wet-on-wet coating, without curing or drying.
- the following coating layer may be applied.
- a coating layer made of an aqueous paint or an aqueous ink containing the anoreminium pigment of the present invention. It is preferred to paint the paint.
- the method for curing the coating composition of each coating layer may be, for example, thermal curing or room temperature curing.
- the method for drying the coating composition of each coating layer may be, for example, hot air or natural drying at room temperature.
- the thickness of the coating layer formed by the aqueous paint or the aqueous ink containing the aluminum pigment of the present invention is not particularly limited, but is preferably 2 m or more in a general embodiment. , 5 m or more is more preferable.
- the thickness of the coating layer is preferably 100 m or less, more preferably 50 ⁇ m or less.
- the thickness of the coating layer is less than 2 zm, the effect of concealing the base by ink or paint tends to be insufficient, and when the thickness of the coating layer exceeds 100 m, drying becomes difficult. There is a tendency for defects such as blemishes, marks, and sauces to increase.
- TEOS tetraethoxysilane
- the slurry was subjected to solid-liquid separation with a filter, and the obtained slurry containing the aluminum pigment was dried at 105 ° C for 3 hours to obtain a powdered aluminum-pigment.
- the slurry was subjected to solid-liquid separation with a filter, and the obtained slurry containing the aluminum pigment was dried at 105 ° C for 3 hours to obtain a powdered aluminum-pigment.
- Example 10 First, hydrogen peroxide 30. /. 0.5 g of metallic molybdenum powder was added little by little to 10 g of a hydrogen peroxide solution containing water, and the solution obtained by the reaction was dissolved in 600 g of isopropyl alcohol. Further, a commercially available aluminum pigment (Toyo Aluminum 153.8 g (100 g of aluminum) of -640 mm NS (solid content: 65%) was added, and the mixture was stirred and stirred at 50 ° C for 1 hour.
- Toyo Aluminum 153.8 g (100 g of aluminum) of -640 mm NS (solid content: 65%) was added, and the mixture was stirred and stirred at 50 ° C for 1 hour.
- the slurry was subjected to solid-liquid separation with a filter, and the obtained slurry containing an aluminum pigment was added to a slurry. After drying at C for 3 hours, a powdered aluminum pigment was obtained.
- Example 6 Example 7
- Example 8 Example 9
- Trietano must monoetano-lua monoetanolu hydrolysis catalyst
- H 2 0 2 30 % aq represents an aqueous solution containing H 2 O 2 30% by weight.
- IPA represents isopropyl alcohol.
- MFDG represents dipropylene glycol monomethyl ether.
- TEOS represents tetraethoxysilane.
- DTMS represents desinoletrimethoxysilane.
- PTES represents fuel triethoxysilane.
- the content of Mo and Si in the aluminum pigment was determined by using a calibration curve using the Mo and Si standard solution of the liquid extracted by the alkali dissolution extraction method using ICP S-8000 manufactured by Shimadzu Corporation. And quantified by plasma emission analysis.
- Anoremi-pum pigment (Examples 1 to 8, Comparative Example 1, Comparative Example 3) 30 g (solid content)
- the metallic glossiness of the metallic coated plate obtained as described above was evaluated on a five-point scale based on the following criteria. The higher the number, the better.
- the directionality refers to the property that the lightness changes depending on the viewing angle.
- the coated plate obtained in the above (iV) was allowed to stand at 40 ° C. and 100% humidity for a day, and then subjected to an adhesion test according to JIS K5600 5-6: 1999. Tables 4 to 6 show the obtained results. The results were indicated by the following five-level evaluation.
- the aluminum pigment of the present invention is excellent in dispersibility and stability, does not generate or coagulate hydrogen gas during storage, and has excellent design properties of the coating film appearance. Suitable for incorporation in paints or water-based inks.
- the dispersibility and stability are excellent, hydrogen gas is not generated or coagulated during storage, and the design of the coating film appearance is excellent. Therefore, it is possible to obtain an aluminum pigment suitable for blending in an aqueous paint or an aqueous ink.
- the resin composition of the present invention has excellent dispersibility and stability, does not generate hydrogen gas during storage, and does not cause aggregation of the anorememim pigment, and has excellent design of the coating film appearance.
- the water-based paint and water-based ink containing the aluminum pigment of the present invention have excellent water dispersibility and stability, do not generate hydrogen gas during storage, and do not cause aggregation of the aluminum pigment. Excellent design.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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PCT/JP2003/005484 WO2004096921A1 (ja) | 2003-04-28 | 2003-04-28 | アルミニウム顔料、その製造方法および樹脂組成物 |
DE60336269T DE60336269D1 (de) | 2003-04-28 | 2003-04-28 | Aluminiumpigment, verfahren zu dessen herstellung sowie harzzusammensetzung |
JP2004571299A JP4027938B2 (ja) | 2003-04-28 | 2003-04-28 | アルミニウム顔料、その製造方法および樹脂組成物 |
EP20030720982 EP1619222B1 (en) | 2003-04-28 | 2003-04-28 | Aluminum pigment, process for production thereof and resin composition |
CNB038251426A CN1333017C (zh) | 2003-04-28 | 2003-04-28 | 铝颜料、制备铝颜料的方法以及树脂组合物 |
US10/525,068 US8088211B2 (en) | 2003-04-28 | 2003-04-28 | Aluminum pigment, process for production thereof and resin composition |
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PCT/JP2003/005484 WO2004096921A1 (ja) | 2003-04-28 | 2003-04-28 | アルミニウム顔料、その製造方法および樹脂組成物 |
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EP (1) | EP1619222B1 (ja) |
JP (1) | JP4027938B2 (ja) |
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Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2008059839A1 (en) * | 2006-11-14 | 2008-05-22 | Asahi Kasei Chemicals Corporation | Metal pigment composition |
JP2008127416A (ja) * | 2006-11-17 | 2008-06-05 | Showa Aluminum Powder Kk | 複合被覆アルミニウム顔料及びその製造方法 |
EP1953195A1 (en) * | 2005-10-13 | 2008-08-06 | Toyo Aluminium Kabushiki Kaisha | Coated metal pigment, method for production of the pigment, and coating composition comprising the pigment |
WO2008139917A1 (ja) * | 2007-05-09 | 2008-11-20 | Toyo Aluminium Kabushiki Kaisha | アルミニウム顔料およびその製造方法ならびに該アルミニウム顔料を含む水性メタリック塗料組成物 |
JP2010508378A (ja) * | 2006-10-31 | 2010-03-18 | エッカルト ゲゼルシャフト ミット ベシュレンクテル ハフツング | 陰極電着塗装において使用するための金属効果顔料、その製造方法および使用方法、ならびに電着塗料 |
WO2011040640A1 (en) | 2009-10-02 | 2011-04-07 | Kansai Paint Co., Ltd. | Aqueous coating composition |
WO2011080973A1 (ja) * | 2009-12-28 | 2011-07-07 | 東洋アルミニウム株式会社 | 金属顔料およびそれを配合した紫外線硬化型組成物 |
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US20060150864A1 (en) | 2006-07-13 |
CN1333017C (zh) | 2007-08-22 |
JPWO2004096921A1 (ja) | 2006-07-13 |
EP1619222A4 (en) | 2009-06-10 |
EP1619222B1 (en) | 2011-03-02 |
US8088211B2 (en) | 2012-01-03 |
DE60336269D1 (de) | 2011-04-14 |
JP4027938B2 (ja) | 2007-12-26 |
EP1619222A1 (en) | 2006-01-25 |
CN1694929A (zh) | 2005-11-09 |
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