WO2011080973A1 - Pigment métallique et composition durcissable par uv le contenant - Google Patents

Pigment métallique et composition durcissable par uv le contenant Download PDF

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Publication number
WO2011080973A1
WO2011080973A1 PCT/JP2010/071025 JP2010071025W WO2011080973A1 WO 2011080973 A1 WO2011080973 A1 WO 2011080973A1 JP 2010071025 W JP2010071025 W JP 2010071025W WO 2011080973 A1 WO2011080973 A1 WO 2011080973A1
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metal
metallic
metal particles
mass
coating
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PCT/JP2010/071025
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English (en)
Japanese (ja)
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貴之 中尾
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東洋アルミニウム株式会社
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Publication of WO2011080973A1 publication Critical patent/WO2011080973A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/38—Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
    • 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
    • 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
    • C09C1/627—Copper
    • 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
    • C09C1/66—Copper alloys, e.g. bronze
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/45—Aggregated particles or particles with an intergrown morphology
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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

Definitions

  • the present invention relates to a metal pigment capable of improving stability with time and obtaining a good metallic feeling when blended in an ultraviolet curable composition, and an ultraviolet curable composition blended with the metal pigment.
  • the coating film formed using the metallic paint reflects the incident light from the outside with a scaly metallic pigment (that is, a metal pigment) contained in the coating film, and exhibits a sparkling design.
  • metallic pigments composed mainly of metal particles, typically aluminum flakes, are used in metallic designs in general automotive paint finishes, plastic paint finishes, printing inks, resin moldings, and the like.
  • VOC Volatile Organic Compound
  • UV paints and UV inks using an ultraviolet curable resin that is advantageous in terms of high-speed curability, low pollution, and energy saving without using an organic solvent is increasingly used. Therefore, the demand for metal pigments including aluminum flakes that can be suitably blended in UV paints and UV inks is also increasing.
  • UV metallic paints and UV metallic inks containing the metal pigments are known as UV metallic paints and UV metallic inks, respectively.
  • an aluminum pigment is used as a metal pigment used in paints or UV metallic inks, an aluminum pigment in which the surface of the aluminum flake is coated with a higher saturated or unsaturated fatty acid such as stearic acid or oleic acid and its derivatives has been used. It was.
  • an aluminum pigment has a problem in that it has poor storage stability when it is blended in a UV metallic paint or a UV metallic ink and causes gelation.
  • the monomer and oligomer components in UV metallic paints and UV metallic inks are activated by aluminum ions on the surface of aluminum pigments during storage, and radical polymerization is promoted. Therefore, problems such as the gelation or solidification of the paint or ink in the container have occurred.
  • Such a problem has also occurred in metal pigments other than aluminum pigments. For this reason, in the field of UV metallic paints and UV metallic inks, generally, metal pigments such as aluminum pigments are hardly used.
  • Patent Document 1 is suitable for UV metallic ink or UV metallic paint containing metal flakes and nitrocellulose as essential components.
  • Metallic pigment compositions have been proposed. Although the gelation can be suppressed to some extent by the proposal, further improvement in stability over time is required. In addition, the nitrocellulose used according to the proposal easily ignites and explodes, and is dangerous in the production of the metallic pigment composition. Therefore, its use is restricted from the viewpoint of safety.
  • the nitrocellulose in the above proposal is considered to prevent gelation by coating the surface of the metal flakes.
  • materials for coating the surface of metal pigments including aluminum pigments for example, various resins , Coupling agent, phosphoric acid compound, molybdenum compound, chromic acid compound, silica (Japanese Patent Application Laid-Open No. 2003-147226 (Patent Document 2), International Publication No. 2004/096921 (Patent Document 3)), and combinations thereof Etc. are known.
  • the surface of the metallic pigment In order to solve the gelation problem that occurs when a metallic pigment is blended with a UV metallic paint or UV metallic ink, it is conceivable to coat the surface of the metallic pigment with another substance.
  • materials for coating the surface of the metal pigment for example, various resins, coupling agents, phosphoric acid compounds, molybdenum compounds, chromic acid compounds, silica, and combinations thereof are known as described above.
  • various resins are expected to generate gelation similar to the above, as the unreacted monomer component contained therein reacts with the monomer component or oligomer component in the UV metallic paint or UV metallic ink. Is done.
  • coupling agents, phosphoric acid compounds, molybdenum compounds, and chromic acid compounds cannot sufficiently cover the surface of the metal pigment with a continuous film, and therefore, the influence of metal ions existing on the surface of the metal pigment is affected. It is considered that the occurrence of gelation cannot be sufficiently prevented since it cannot be sufficiently suppressed.
  • the coating of a metal pigment with silica is originally intended to improve the stability of the metal pigment in an aqueous medium, the metal pigment coated with silica is excellent in dispersibility in an aqueous medium, but UV It was considered difficult to disperse in oily media such as metallic paints or UV metallic inks. Moreover, since silica has a high affinity with water and the surface is thought to be hydrated, the effect of moisture and the residual hydrolysis catalyst used during the synthesis of silica hinders the curing of UV curable resins. It is also expected.
  • the present invention has been made under such circumstances, and even when blended with an ultraviolet curable composition such as a UV metallic coating composition or a UV metallic ink composition, the occurrence of gelation can be suppressed.
  • An object of the present invention is to provide a metal pigment that can be produced and does not involve dangers such as ignition and explosion.
  • the present inventor has conducted extensive studies to solve the above-mentioned problems, and has obtained a surprising finding that a favorable result can be obtained with a metal pigment coated with silica contrary to the conventional expectation. As a result of repeated studies, the present invention has finally been completed.
  • the metal pigment of the present invention is a metal pigment for blending into an ultraviolet curable composition, and includes metal particles and a first film that covers the surface of the metal pigment. It is characterized by comprising crystalline silica.
  • the surface of the first coating is preferably treated with a silane coupling agent.
  • the metal pigment preferably contains silicon in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the metal particles.
  • the present invention also relates to an ultraviolet curable composition containing the above-mentioned metal pigment, and the ultraviolet curable composition is preferably a UV metallic paint composition or a UV metallic ink composition.
  • the metal pigment of the present invention can suppress the occurrence of gelation even when blended with an ultraviolet curable composition such as a UV metallic paint composition or a UV metallic ink composition, and has a risk of ignition and explosion. It has an excellent effect of not being accompanied.
  • the ultraviolet curable composition in the present invention is a composition that is cured by ultraviolet rays to produce a resinous product (that is, a film or a molded product). Specifically, a conventionally known so-called UV monomer or UV oligomer is used. First, it is a composition containing a photopolymerization initiator and various additives.
  • ultraviolet curable composition examples include a UV metallic paint composition and a UV metallic ink composition.
  • the metal pigment of the present invention is for blending in the ultraviolet curable composition as described above, and includes metal particles and a first film that covers the surface of the metal particle. It is characterized by comprising amorphous silica.
  • the metal pigment of the present invention has this first coating, when this is blended with the UV curable composition, the UV monomer or UV oligomer in the UV curable composition is in direct contact with the surface of the metal pigment. Therefore, the monomers and oligomers are not activated during storage of the ultraviolet curable composition, and radical polymerization is not promoted, so that the ultraviolet curable composition during storage gels or solidifies. There is no problem.
  • the metal pigment of the present invention contains components other than the metal pigment contained in the ultraviolet curable composition (particularly a resin cured by ultraviolet rays) and the metal. The effect of improving the adhesion with the pigment is obtained.
  • Such a metal pigment of the present invention is usually added in an ultraviolet curable composition in an amount of 0.1 to 50% by mass, preferably 1 to 30% by mass, and more preferably 3 to 20% by mass.
  • Metal particles constituting the metal pigment of the present invention include aluminum, zinc, copper, silver, nickel, titanium, stainless steel, or metal particles made of an alloy containing at least one of these metals.
  • metal particles aluminum particles, copper particles, and alloy particles of copper and zinc are particularly suitable because they are excellent in metallic luster and are inexpensive and relatively easy to handle.
  • the shape of such metal particles is not particularly limited and may take various shapes such as granular, plate-like, massive, and flake-like (scale-like), but gives excellent metallic feeling and brightness to the coating film and printed matter. For this purpose, a flake shape is preferred.
  • the average particle diameter of the metal particles is preferably in the range of 0.1 to 100 ⁇ m, and more preferably in the range of 0.5 to 60 ⁇ m.
  • the average particle diameter of the metal particles is 0.1 ⁇ m or more, the metallic feeling or the glitter feeling is good.
  • the average particle size of the metal particles is 100 ⁇ m or less, the metal particles can be prevented from sticking out to the surface of the coating film or the ink film, and there is little risk that the smoothness or sharpness of the surface is lowered. This is also advantageous in terms of cost.
  • the average particle diameter of such metal particles can be obtained by calculating the volume average from the particle size distribution measured by the laser diffraction method.
  • the average thickness of the metal particles is preferably in the range of 0.001 to 5 ⁇ m, and more preferably in the range of 0.005 to 2 ⁇ m.
  • the average thickness of the metal particles is 0.001 ⁇ m or more, since the metal particles have sufficient strength, the workability during the manufacturing process is good.
  • the average thickness of the metal flakes is 5 ⁇ m or less, there is little risk that the smoothness or sharpness of the coating film or ink film is lowered, and it is advantageous in terms of production cost.
  • a metal powder as a raw material and a grinding aid are usually used in an organic solvent using a grinding device having grinding media such as a ball mill or an attritor.
  • a grinding device having grinding media such as a ball mill or an attritor.
  • the grinding aid suppresses unnecessary oxidation of the metal flake surface and has an effect of improving gloss.
  • the grinding aid is not particularly limited, and conventionally known ones can be used.
  • fatty acids such as oleic acid and stearic acid, fatty acid amines, fatty acid amides, aliphatic alcohols, ester compounds and the like are preferable. Can be used.
  • the organic solvent used at the time of grinding with the metal powder and the grinding aid is not particularly limited, and conventionally known ones can be used.
  • hydrocarbon solvents such as mineral spirits, solvent naphtha, alcohols, etc.
  • Ether solvents and ester solvents can be used.
  • a hydrocarbon solvent with a high boiling point is suitably used in consideration of safety problems such as the flash point of the solvent during grinding.
  • the material to be ground is passed through a screen to remove coarse powder, and then the organic solvent and metal particles are separated into solid and liquid using a filter press or the like to obtain a flake having a metal content of about 50 to 80% by mass.
  • a paste of metal-like metal particles is obtained.
  • the content of the organic solvent in the paste is preferably as small as possible from the viewpoint of ensuring high-speed curability of the coating film or ink film.
  • the first film of the present invention is made of amorphous silica.
  • the first coating covers the surface of the metal particles, but may be formed so as to be in direct contact with the surface of the metal particles, or may be formed via an underlayer described later. In the present invention, even when the first film is formed through the underlayer (that is, on the underlayer) as described above, it is expressed as “cover the surface of the metal particles”.
  • the amorphous silica means amorphous silica having no crystal structure, specifically, siloxane (H 3 SiO (H 2 SiO) m SiH 3 ), silica hydrate (SiO 2 .mH). 2 O), silica hydroxide (SiO n (OH) 4-2n ) and the like.
  • m represents an arbitrary positive integer
  • n represents a number in the range of 0 ⁇ n ⁇ 2.
  • Amorphous silica has a very dense layer structure and is very stable with respect to UV monomers and UV oligomers contained in the ultraviolet curable composition. Further, the metal particles are formed from the amorphous silica.
  • the metal pigment of the present invention is very stable in the ultraviolet curable composition because it is completely covered with the first coating.
  • the first coating film of the present invention does not need to be a film made of only amorphous silica, and may contain other additives and impurities as long as the effects of the present invention are not impaired. That is, in the present invention, “consisting of amorphous silica” includes not only the case of consisting of amorphous silica but also the case of including other components in this way.
  • a method of hydrolyzing the organosilicon compound to deposit the first coating on the surface of the metal particles or the surface of the underlayer can be exemplified, but is not limited thereto, and any known method A method may be used.
  • the method of adjusting the pH value of the dispersion solution is as described above.
  • the method is not limited only to the method of adding a hydrolysis catalyst to the solution, and the pH of the dispersion solution may be adjusted using other acidic compounds and / or alkaline compounds.
  • organosilicon compound is a concept including both an organosilicon compound and a condensate of an organosilicon compound.
  • the organosilicon compound used in the present invention is not particularly limited, and by adjusting the pH of a dispersion solution containing metal particles having or not having an underlayer, the organosilicon compound, and a hydrolysis catalyst, A known organosilicon compound and its condensate that can hydrolyze the organosilicon compound to form the first film on the surface of the metal particles or the surface of the underlayer can be mentioned.
  • organosilicon compounds include tetraethoxysilane, tetramethoxysilane, tetraisopropoxysilane, and their condensates. These organosilicon compounds may be used alone or in combination of two or more.
  • the hydrolysis catalyst used in the present invention is not particularly limited, and by adjusting the pH of a dispersion solution containing metal particles with or without a base layer, an organosilicon compound, and the hydrolysis catalyst, the hydrolysis catalyst is used.
  • a known hydrolysis catalyst that hydrolyzes the organosilicon compound by the action of the decomposition catalyst and forms the first film on the surface of the metal particles or the surface of the underlayer can be used.
  • hydrolysis catalyst examples include monoethanolamine, diethanolamine, triethanolamine, ammonia, ethylenediamine, t-butylamine, 3-aminopropyltriethoxysilane, n-2-aminoethyl-3-aminopropyltrimethyl.
  • Basic hydrolysis catalysts such as ethoxysilane, n-2-aminoethyl-3-aminopropylmethyldimethoxysilane, urea, sodium silicate, sodium hydroxide, and acidic acids such as oxalic acid, acetic acid, nitric acid, sulfuric acid, phosphoric acid, phosphonic acid Examples include hydrolysis catalysts.
  • a basic hydrolysis catalyst rather than an acidic hydrolysis catalyst.
  • triethanolamine, ammonia, ethylenediamine, 3-aminopropyltriethoxysilane, and the like are particularly preferable from the standpoint of quality.
  • a hydrophilic solvent as the solvent of the dispersion solution containing the metal particles with or without the base layer, the organosilicon compound, and the hydrolysis catalyst.
  • a hydrophilic solvent include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, n-butyl alcohol, isobutyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol.
  • Monopropyl ether, acetone, or the like can be used, but in particular, when aluminum particles are used as the metal particles, it is preferable in that an abnormal reaction between the aluminum particles and water is avoided.
  • these hydrophilic solvents may contain water.
  • the content of water in the hydrophilic solvent is particularly preferably 20% by mass or less from the viewpoint of avoiding an abnormal reaction between the aluminum particles and water.
  • the dispersion solution containing the metal particles with or without the underlayer, the organosilicon compound, and the hydrolysis catalyst 100 parts by mass of the metal particles (in the present invention, only the metal particles are included even when the underlayer is provided).
  • the content of the organosilicon compound is preferably 2 parts by mass or more, and more preferably 5 parts by mass or more.
  • content of this organosilicon compound is 200 mass parts or less, and it is more preferable if it is 100 mass parts or less.
  • the first coating tends to be insufficiently formed to cover the surface of the metal particles, and the content of the organosilicon compound exceeds 200 parts by mass. Then, there is a tendency that the aggregation of the metal particles and the reduction of the glitter feeling become remarkable.
  • the content of the hydrolysis catalyst is 0.1 parts by mass or more with respect to 100 parts by mass of the metal particles. It is preferable that it is 0.5 mass part or more.
  • the content of the hydrolysis catalyst is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.
  • the content of the hydrolysis catalyst is less than 0.1 parts by mass, the amount of precipitation of the amorphous silica constituting the first film tends to be insufficient, and the content of the hydrolysis catalyst is 20 masses. When it exceeds the part, the aggregation of the metal particles tends to be remarkable.
  • the content of the hydrophilic solvent is 500 parts by mass or more with respect to 100 parts by mass of the metal particles. It is more preferable that it is 1000 parts by mass or more. Further, the content of the hydrophilic solvent is preferably 10,000 parts by mass or less, and more preferably 5000 parts by mass or less.
  • 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.
  • the content of the hydrophilic solvent exceeds 10,000 parts by mass, the treatment liquid is recovered, Regeneration costs tend to increase.
  • the temperature of the dispersion solution in the step is preferably 20 ° C. or higher, and 30 ° C. or higher. More preferably. Moreover, it is preferable that the temperature of the dispersion solution in this process is 90 degrees C or less, and it is more preferable if it is 80 degrees C or less.
  • the reaction time is preferably 1 hour or longer, more preferably 3 hours or longer.
  • the reaction time is preferably 48 hours or shorter, more preferably 24 hours or shorter. When this reaction time is less than 1 hour, the formation of the first film tends to be insufficient, and when this reaction time exceeds 48 hours, the processing cost tends to increase.
  • the pH value of the dispersion solution changes during the reaction, and therefore it is necessary to adjust the pH value appropriately. is there.
  • the pH of the solution may be adjusted.
  • the pH is preferably 7 or more when the basic hydrolysis catalyst is used. .5 or more is more preferable. Further, the pH of this dispersion solution is preferably 11 or less, and more preferably 10 or less.
  • the step of forming the first film on the surface of the metal particles having or not having the base layer it is more amorphous to use a basic hydrolysis catalyst than to use an acidic hydrolysis catalyst. This is preferable because the formation rate of silica is fast and the productivity is good.
  • the pH is preferably 1.5 or more when the acidic hydrolysis catalyst is used. Two or more are more preferable.
  • the pH of the dispersion is preferably 4 or less, and more preferably 3 or less.
  • the pH of the dispersion is less than 1.5, the risk of runaway reaction tends to increase. If the pH of the dispersion in this process exceeds 4, the deposition rate of amorphous silica increases. There is a tendency to become smaller.
  • the thickness of the first coating of the present invention is preferably in the range of 1 to 500 nm. In the case of 1 nm or less, it becomes difficult to suppress the reaction to the UV monomer and UV oligomer in the ultraviolet curable composition, and the storage stability is lowered. On the other hand, when the thickness is 500 nm or more, the color tone of the coating film is lowered and the hiding power is lowered. A more preferable thickness of the first coating is 10 to 350 nm, and a more preferable thickness is 20 to 200 nm.
  • the thickness of the first coating can be measured by observation with a TEM (transmission electron microscope), but when the thickness is 50 nm or less, it should be measured by XPS (X-ray photoelectron spectroscopy). Is preferred.
  • the surface of the first coating can be treated with a silane coupling agent. That is, the surface of the first coating of the present invention may be treated with a silane coupling agent.
  • the silane coupling agent By treating the surface of the first film with the silane coupling agent in this manner, the reactivity with respect to the monomer and oligomer in the ultraviolet curable composition can be further suppressed, and adhesion (metal pigment and resin and Various effects can be expected, such as improvement of physical properties of the coating film such as adhesion of the resin and adhesion to the object to be coated, improvement of dispersibility in the ultraviolet curable composition, and improvement of the orientation of the metal particles.
  • the surface of the first coating When the surface of the first coating is treated with a silane coupling agent, the surface of the first coating may be in a state where it is coated with a single coating made of a silane coupling agent.
  • the ring agent reacts with the amorphous silica constituting the first coating or the organosilicon compound remaining in the first coating to form a composite coating of the first coating and the silane coupling agent. It may be in such a state.
  • Such a treatment with a silane coupling agent is generally considered to be performed by hydrolyzing the silane coupling agent and reacting with a hydroxyl group in the amorphous silica constituting the first coating.
  • silane coupling agents include methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, 3-aminopropyl-trimethoxysilane, n-methyl-3- Aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-tris (2-methoxy-epoxy-silane), n-aminoethyl-3-aminopropyltrimethoxysilane, n-aminoethyl- 3-aminopropyl-methyl-dimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-methacryloxypropyl
  • Particularly preferable silane coupling agents include the following compounds.
  • R A an alkyl group having 2 to 18 carbon atoms, an aryl group, or an alkenyl group
  • R B an alkyl group having 1 to 3 carbon atoms
  • the following compounds are exemplified.
  • Examples include n-propyltrimethoxysilane, isobutyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, and the like.
  • the method of treating the surface of the first coating of the present invention with a silane coupling agent is almost the same as the method of forming the first coating, and can be performed by hydrolyzing the silane coupling agent. And a silane coupling agent will react with the hydroxyl group in the amorphous silica normally contained in a 1st film.
  • the organosilicon compound and the silane coupling are adjusted by adjusting the pH of the dispersion solution containing the metal particles with or without the base layer, the organosilicon compound, the silane coupling agent, and the hydrolysis catalyst.
  • the agent is hydrolyzed to form a first coating on metal particles with or without a base layer, and the surface is treated with a silane coupling agent.
  • the silane cup is formed after the first film is once formed by hydrolysis. It is preferable to treat the surface of the first film with a silane coupling agent by adding a ring agent and further hydrolyzing it.
  • reaction solvent for processing with a silane coupling agent various conditions, such as the reaction solvent for processing with a silane coupling agent, temperature, a hydrolysis catalyst, are the same as the conditions at the time of forming the said 1st film.
  • the amount of the silane coupling agent is 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the metal particles.
  • the amount of the silane coupling agent is less than 0.1 parts by mass, the desired effect tends not to be obtained.
  • the amount exceeds 20 parts by mass the amount of unreacted silane coupling agent increases and the physical properties of the coating film decrease. Tend to.
  • the dispersion solution is prepared using the above hydrophilic solvent not containing water. After washing, it is preferable to remove water and unreacted substances from the cake containing the metal pigment of the present invention by filtration using a filter.
  • the cake containing the metal pigment of the present invention may be heat-treated at a temperature in the range of 100 to 500 ° C.
  • the step of forming the base layer, the step of forming the first coating, and the step of treating with the silane coupling agent may be performed in different dispersion solutions on the surface of the metal particles, or It is also possible to carry out continuously after appropriately adjusting the components in the same dispersion solution.
  • the metal pigment of the present invention preferably contains silicon in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the metal particles.
  • the silicon content (parts by mass) indicates the amount of silicon element contained in the first film (ie, contained in the amorphous silica), but the surface of the first film is silane. In the case of being treated with a coupling agent, the amount of silicon element contained in the silane coupling agent is also added.
  • the silicon content is more preferably 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the metal particles.
  • the stability of the metal pigment in the ultraviolet curable composition tends to decrease, and when the silicon content exceeds 100 parts by mass.
  • the metal pigment aggregates, the concealability is lowered, and the color tone such as metallic luster is impaired.
  • the metal pigment of the present invention can form a base layer on metal particles, and can form a first coating on the base layer.
  • This underlayer has a function of accelerating the formation of the first film as a nucleus for the deposition of the first film when the first film is formed. Thereby, the thickness of the first coating becomes uniform, and the reaction with the UV monomer or UV oligomer contained in the ultraviolet curable composition can be more sufficiently suppressed.
  • a layer made of a single film or a mixture film composed of at least one of oxides, hydroxides, and hydrates containing molybdenum hereinafter referred to as “a layer containing molybdenum”.
  • a layer containing molybdenum examples thereof include layers containing metal element oxides constituting metal particles, but are not limited thereto.
  • the method for forming a layer containing molybdenum as the underlayer on the metal particle surface is not particularly limited, examples of preferred methods include the following methods. That is, a metal particle and a solution containing a molybdenum compound as described below are mixed in a slurry state or a paste state and stirred or kneaded to form a hydrated film containing molybdenum on the surface of the metal particle, and then heated. The method of using an oxide film is mentioned.
  • a method for forming such a layer containing molybdenum a conventionally known method disclosed in, for example, Japanese Patent Application Laid-Open No. 09-328629 can be employed.
  • Molybdenum compounds used for forming a layer containing molybdenum include a composition formula Mo x O y ⁇ mH 2 O 2 ⁇ nH 2 O (where x is 1 or 2, y is an integer of 2 to 5, m and n are Examples thereof include polymolybdic acid peroxide, ammonium molybdate, phosphomolybdic acid and the like represented by any arbitrary positive number).
  • polymolybdenum peroxide can be prepared by dissolving metal molybdenum powder, molybdenum oxide, or the like in an aqueous hydrogen peroxide solution (concentration 5 to 40% by mass).
  • molybdenum compounds are methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, n-butyl alcohol, isobutyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene Dissolve in a hydrophilic solvent such as glycol monopropyl ether or acetone to obtain a treatment solution.
  • the treatment solution may contain water.
  • the amount of molybdenum in the layer containing molybdenum is preferably 0.01 to 3.0 parts by mass, more preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the metal particles.
  • the amount of molybdenum is desirably changed according to the specific surface area of the metal particles to be treated. It is preferable that the amount of molybdenum is increased for metal particles having a large specific surface area and decreased for metal particles having a small specific surface area.
  • the amount of molybdenum is 0.01 parts by mass or more with respect to 100 parts by mass of the metal particles, the thickness uniformity of the first coating and the chemical stability of the metal particles when forming the first coating are good. Yes, when it is 3.0 parts by mass or less, for example, the color tone of metal particles such as metallic luster and the like are prevented from agglomerating and the coating film properties such as moisture resistance, adhesion and weather resistance are good. Maintained.
  • a method for forming a layer containing an oxide of a metal element constituting a metal particle as a base layer on the surface of the metal particle is not particularly limited.
  • the surface of the metal particle is treated with hydrogen peroxide.
  • the method of forming the said oxide can be mentioned.
  • the fatty acid adsorbed on the surface of the metal particle is removed, and the surface of the metal particle is oxidized to include an oxide of a metal element constituting the metal particle.
  • a layer is formed. As a result, the surface of the metal particles is brought into a surface state in which the first film is easily grown starting from the layer.
  • the metal particles constituting the metal particles are included on the surface of the metal particles.
  • examples thereof include a method of forming a hydrated film and then converting the hydrated film into an oxide film by heating.
  • aluminum particles are used as metal particles and the aluminum particles and a solution containing hydrogen peroxide are mixed in a slurry state or a paste state and stirred or kneaded, a hydrated film containing aluminum is formed on the surface of the aluminum particles, By further heating this, an oxide film such as an aluminum oxide film or a boehmite film is formed.
  • a solution obtained by dissolving hydrogen peroxide in a solvent can be typically used.
  • the solvent in addition to water, alcohol, glycol, glycol ether, ketone organic solvents and the like can be used, and a mixed solvent of water and organic solvent can also be used.
  • the concentration of hydrogen peroxide in the solution is preferably in the range of 0.0001 to 45% by mass.
  • the metal pigment of this invention is for mix
  • the present invention relates not only to such a metal pigment but also to an ultraviolet curable composition containing the metal pigment. And it is preferable that the ultraviolet curable composition of this invention is a UV metallic coating composition or a UV metallic ink composition.
  • the metal pigment of the present invention When the metal pigment of the present invention is blended with an ultraviolet curable composition, the UV monomer or UV oligomer in the ultraviolet curable composition is not activated, and radical polymerization is not accelerated. There is no problem of gelation or solidification.
  • the components of the UV metallic coating composition and the UV metallic ink composition are mainly composed of a resin component, a photopolymerization initiator, and the like.
  • the UV metallic ink composition is mainly composed of a component that does not contain an organic solvent and solidifies 100% in principle.
  • a UV metallic coating composition may use 10 to 20% of a diluent to lower the viscosity due to leveling problems.
  • the metal pigment of the present invention is blended in the UV metallic paint composition and the UV metallic ink composition so as to fall within the range of 0.1 to 50% by mass. Is preferred.
  • the compounding amount of the metal pigment is 0.1% by mass or more, a sufficient metallic effect is obtained, and when it is 50% by mass or less, the physical properties and weather resistance of the UV metallic coating composition and the UV metallic ink composition. There is little risk of adversely affecting performance, corrosion resistance, mechanical strength, etc.
  • the resin component of the UV metallic paint composition and the UV metallic ink composition those that are cured by ultraviolet rays are generally used.
  • the resin component that is cured by ultraviolet rays include those composed of reactive monomers (that is, UV monomers) and reactive oligomers (that is, UV oligomers). These monomers and oligomers are cured (polymerized) by ultraviolet rays to become resinous, but the UV metallic coating composition and the UV metallic ink composition may contain a polymer.
  • the reactive monomer is not particularly limited, and examples thereof include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acryloyl phosphate, tetrahydrofurfuryl acrylate, and acrylates of tetrahydrofurfuryl derivatives.
  • Monofunctional monomers dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dipentaerythritol hexaacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, Diethylene glycol diacrylate, neopentyl glycol diacrylate, hydroxybivalate ester neopentyl glycol di Acrylate, bifunctional monomers such as tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, include trifunctional monomers such as dipentaerythritol hexaacrylate.
  • examples of the reactive oligomer include polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate (for example, diglycerin polyglycidyl ether acrylate) and the like.
  • the polymer is not particularly limited.
  • an acrylic resin, an alkyd resin, a polyester resin, a polyurethane resin, a polyvinyl acetate resin, a nitrocellulose resin, a fluororesin, and the like having an unsaturated double bond. can be suitably used.
  • UV curable water-soluble resins and emulsion resins may be used as the resin component, but they may be contained.
  • a diluent solvent
  • a phthalic acid compound, a monomer, etc. are illustrated.
  • phthalic acid compounds phthalic acid monomethyl ester, phthalic acid monoethyl ester, phthalic acid monophenyl ester, phthalic acid monobenzyl ester, phthalic acid monocyclohexyl ester, phthalic acid dimethyl ester, phthalic acid diethyl ester, phthalic acid methyl ethyl ester Phthalic acid dibutyl ester, phthalic acid dioctyl ester, phthalic acid dihexadecyl ester, phthalic acid dicyclohexyl ester, phthalic acid diphenyl ester, phthalic acid di- ⁇ -naphthyl ester, phthalic acid dibenzyl ester and the like.
  • Monomers include monofunctional monomers such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acryloyl phosphate, tetrahydrofurfuryl acrylate, and acrylates of tetrahydrofurfuryl derivatives, dicyclopentenyl Acrylate, dicyclopentenyloxyethyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, hydroxybivalic acid Bifunctional monomers such as ester neopentyl glycol diacrylate and tripropylene glycol diacrylate, Chi triacrylate, pentaerythritol triacrylate, include trifunctional monomers such as dipentaerythritol hexaacrylate
  • examples of the photopolymerization initiator include radical photopolymerization initiators, but are not particularly limited.
  • examples of the radical photopolymerization initiator include the following.
  • an alkylphenone photopolymerization initiator 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one, 2-methyl-1- (4-tylthiophenyl) -2-morpholinopropan-1-one, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -
  • photopolymerization initiators are oxime ester compounds such as 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) or oxyphenylacetic acid ester compound 2- [2-oxo-2-phenylacetoxyethoxy] ethyl Examples thereof include esters and oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester. In general, these radical photopolymerization initiators are usually mixed and used, and sometimes used in combination with benzophenone or the like.
  • the UV metallic coating composition and the UV metallic ink composition of the present invention include, as necessary, organic pigments such as quinacridone red, phthalocyanine blue, phthalocyanine green, isoindolinone yellow, carbon black, perylene, azo lake, oxidation Inorganic pigments such as iron, titanium oxide, cobalt blue, zinc white, ultramarine, chromium oxide, mica, yellow lead, anti-settling agent, thickener, static eliminating agent, dispersant, antioxidant, polish, surface activity Agents, synthetic preservatives, lubricants, fillers (reinforcing agents), waxes, antifoaming agents, leveling agents, stabilizers and the like may be added. Furthermore, an acidic phosphate ester, nitrocellulose, a carbodiimide compound, or the like may be added.
  • organic pigments such as quinacridone red, phthalocyanine blue, phthalocyanine green, isoindolinone yellow, carbon black, perylene, azo lake, oxid
  • Examples of the method of applying or painting using the UV metallic coating composition include a method of applying with a brush, a doctor blade, a roll coater, a bar coater or the like, a method of applying with a spray or the like.
  • Examples of the printing method using the UV metallic ink composition include known printing methods such as intaglio printing such as gravure printing, offset printing (transfer printing), screen printing, flexographic printing, other letterpress printing, and lithographic printing. Etc.
  • the UV metallic ink composition of the present invention can also be suitably used for inkjet printing.
  • blends the metal pigment of this invention may be formed on the undercoat layer or intermediate coating layer by electrodeposition coating etc.
  • a top coat layer may be formed on the film.
  • the top coat layer may be of any type, such as UV, solvent, and water.
  • the thickness of the coating film is not particularly limited, but in a general embodiment, it is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more.
  • the thickness is preferably 100 ⁇ m or less, more preferably 30 ⁇ m or less.
  • the thickness is less than 1 ⁇ m, the concealing effect of the base by the ink or paint tends to be insufficient, and when the thickness exceeds 100 ⁇ m, the transmission of ultraviolet rays becomes insufficient, and the site is weakly cured in the coating film. There is a risk of occurrence. In addition, since drying becomes difficult, defects such as armpits and sagging tend to increase.
  • Example 1 A solution obtained by reacting hydrogen peroxide with metallic molybdenum by adding 0.3 g of metallic molybdenum powder little by little to 3 g of hydrogen peroxide containing 30% by mass of hydrogen peroxide is isopropyl alcohol (hereinafter abbreviated as IPA). ) Dissolved in 500 g. Furthermore, 40 g of aluminum particles (trade name: “5422NS”, manufactured by Toyo Aluminum Co., Ltd., solid content: 75 mass%, average particle size: 19 ⁇ m) as metal particles were added to this solution as a slurry, This slurry was stirred and mixed at 75 ° C. for 1 hour to form an underlayer, which is a layer containing molybdenum, on the metal particles.
  • IPA isopropyl alcohol
  • TEOS tetraethoxysilane
  • a powdery metal pigment (aluminum pigment) in which the surface of the metal particles having the base layer was coated with amorphous silica (first coating) was obtained (solid content: 100 parts by mass).
  • the silicon content was 15.7 parts by mass with respect to 100 parts by mass of the metal particles (aluminum particles). Moreover, it was about 60 nm when the thickness of the 1st film was measured by direct observation by TEM.
  • a UV metallic coating composition was prepared according to “Formulation of UV metallic coating composition” described later, and storage stability was evaluated. The results are shown in Table 1.
  • Example 2 In the same manner as in Example 1, a slurry in which an underlayer that is a layer containing molybdenum was formed on metal particles was obtained. Monoethanolamine was added to this slurry to adjust the pH value of the slurry to 8.5.
  • a slurry prepared by dissolving 40 g of TEOS in 40 g of IPA was stirred dropwise at 50 ° C. for 6 hours in a slurry whose pH was adjusted.
  • 2 g of decyltrimethoxysilane was added to the slurry, and the mixture was further stirred at 50 ° C. for 4 hours.
  • the pH value of the slurry was checked every 2 hours along the way, and the pH value was adjusted to 8.5 by adding monoethanolamine.
  • the slurry is subjected to solid-liquid separation with a filter, and the resulting slurry containing the metal pigment is dried at 120 ° C. for 12 hours, whereby the surface of the metal particles having the base layer is made of amorphous silica (first And a surface of the first film was treated with a silane coupling agent to obtain a powdered metal pigment (aluminum pigment) (solid content: 100 parts by mass).
  • aluminum pigment solid content: 100 parts by mass.
  • the silicon content was 14.5 parts by mass with respect to 100 parts by mass of the metal particles (aluminum particles).
  • a UV metallic coating composition was prepared according to “Formulation of UV metallic coating composition” described later, and storage stability was evaluated. The results are shown in Table 1.
  • commercially available aluminum particles (trade name: “5422NS”, manufactured by Toyo Aluminum Co., Ltd., solid content: 75% by mass, average particle size: 19 ⁇ m) were used, according to “Composition of UV metallic coating composition” described later. UV metallic coating compositions were prepared and evaluated for storage stability. The results are shown in Table 1.
  • a UV metallic paint composition is prepared and stored in accordance with “Composition of UV metallic paint composition” described later. Stability was evaluated. The results are shown in Table 1. ⁇ Formulation of UV metallic coating composition> Ingredient Mass part Oligomer (EA-5720) 30 2. DPHA 20 3. TMPTA 30 4). Irgacure 184 3 5. Irgacure 754 2 6). Irgacure 819 1 7). Metal pigment (solid content) 14 Details of each component during the blending are as follows.
  • Oligomer (EA-5720) trade name “NK Oligo EA-5720” (diglycerin polyglycidyl ether acrylate), manufactured by Shin-Nakamura Chemical Co., Ltd. 2.
  • DPHA dipentaerythritol hexaacrylate, manufactured by Kyoeisha Chemical Co., Ltd. 3.
  • TMPTA trimethylolpropane triacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. 4.
  • Irgacure 184 hydroxycyclohexyl phenyl ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.
  • Irgacure 754 Mixture of oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester, manufactured by Ciba Specialty Chemicals Co., Ltd. 6.
  • Irgacure 819 Phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide, manufactured by Ciba Specialty Chemicals Co., Ltd.
  • Metal pigment Metal pigment obtained in Examples and Comparative Examples In the above, 1 is a UV oligomer, 2 and 3 are UV monomers, and 4 to 6 are photopolymerization initiators.
  • paint dispersibility is a visual evaluation of the dispersibility immediately after production of the UV metallic paint composition.
  • the evaluation criteria are as follows. A: The metal pigment is well dispersed in the paint and the paint surface has a strong metallic luster. B: The metal pigment is dispersed in the paint, and the paint surface has a metallic luster. C: The metal pigment is temporarily dispersed in the paint, but it is not so familiar and the paint surface has no metallic luster. D: The metal pigment does not completely match the paint, and the paint surface has a gray color. That is, “A” indicates the best dispersibility, and “D” indicates the worst dispersibility.
  • “60 ° C. ⁇ 3 days” and “60 ° C. ⁇ 7 days” are both evaluations of the storage stability of the UV metallic coating composition, and at 60 ° C. for 3 days and 60 ° C. after the production, respectively. The result when stored (stored) for 7 days is shown.
  • Solidification refers to a state in which “gelation” further proceeds and does not exhibit fluidity at all.
  • the metal pigments of Examples 1 and 2 according to the present invention exhibit better storage stability than the comparative metal pigments, and can be applied without any problem even after storage for a certain period of time. / I was able to paint.
  • the metal pigment of the present invention can suppress the occurrence of gelation even when blended with an ultraviolet curable composition such as a UV metallic paint composition or a UV metallic ink composition, and can be used as a nitrocellulose. It is clear that it has an excellent effect of not involving danger such as ignition and explosion because it does not contain dangerous substances.

Abstract

Pigment métallique pouvant être utilisé dans une composition durcissable par UV. Ledit pigment métallique est caractérisé en ce qu'il contient des particules métalliques et un premier film qui recouvre les surfaces des particules métalliques. Le pigment métallique est, en outre, caractérisé en ce que ce premier film comprend une silice amorphe.
PCT/JP2010/071025 2009-12-28 2010-11-25 Pigment métallique et composition durcissable par uv le contenant WO2011080973A1 (fr)

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JP2013159645A (ja) * 2012-02-01 2013-08-19 Seiko Epson Corp 紫外線硬化型インクジェット用組成物および記録物
JP2013159646A (ja) * 2012-02-01 2013-08-19 Seiko Epson Corp インクジェット用組成物および記録物
EP2692806A1 (fr) * 2012-08-02 2014-02-05 Seiko Epson Corporation Composition d'encre durcissable par rayonnement ultraviolet destinée à être utilisée dans un procédé à jet d'encre et objet enregistré
JP2014065527A (ja) * 2012-09-26 2014-04-17 Du Pont Mitsui Polychem Co Ltd 樹脂容器
EP2738228A1 (fr) * 2012-12-03 2014-06-04 Seiko Epson Corporation Composition d'encre durcissable par rayonnement ultraviolet destinée à être utilisée dans un procédé à jet d'encre et objet imprimé
EP2738227A1 (fr) * 2012-12-03 2014-06-04 Seiko Epson Corporation Composition d'encre durcissable par rayonnement ultraviolet destinée à être utilisée dans un procédé à jet d'encre et objet imprimé
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US9321928B2 (en) 2011-05-17 2016-04-26 Seiko Epson Corporation Metal powder, ultraviolet ray curable ink jet composition and recorded object
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JP5874405B2 (ja) * 2012-01-18 2016-03-02 セイコーエプソン株式会社 紫外線硬化型インクジェット用組成物
WO2014014199A1 (fr) * 2012-07-20 2014-01-23 주식회사 퍼스트칼라 Procédé de fabrication de pigment organique revêtu par de la silice ayant une bonne résistance à la lumière et une bonne résistance à la chaleur
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JP6056933B2 (ja) * 2015-10-07 2017-01-11 セイコーエプソン株式会社 紫外線硬化型インクジェット組成物および記録物の製造方法
JP6278139B2 (ja) * 2017-04-04 2018-02-14 セイコーエプソン株式会社 紫外線硬化型インクジェット用組成物および記録物
WO2022092272A1 (fr) * 2020-10-30 2022-05-05 株式会社Ｄｎｐファインケミカル Composition d'encre
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JP4358897B1 (ja) * 2009-02-27 2009-11-04 株式会社システム・トート 表面被覆アルミニウム顔料の製造方法

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