WO2011080973A1 - Metallic pigment and uv-curable composition containing said metallic pigment - Google Patents

Metallic pigment and uv-curable composition containing said metallic pigment

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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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Prior art keywords
coating
metallic
uv
metal
metal particles
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PCT/JP2010/071025
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French (fr)
Japanese (ja)
Inventor
中尾 貴之
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東洋アルミニウム株式会社
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/38Paints containing free metal not provided for above in groups C09D5/00 - C09D5/36
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09CTREATMENT 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
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62Metallic pigments or fillers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09CTREATMENT 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
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62Metallic pigments or fillers
    • C09C1/627Copper
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09CTREATMENT 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
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62Metallic pigments or fillers
    • C09C1/64Aluminium
    • C09C1/642Aluminium treated with inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09CTREATMENT 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
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/66Copper alloys, e.g. bronze
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • C09D7/62Additives non-macromolecular inorganic modified by treatment with other compounds
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/20Particle morphology extending in two dimensions, e.g. plate-like
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/45Aggregated particles or particles with an intergrown morphology
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K9/00Use of pretreated ingredients
    • C08K9/02Ingredients treated with inorganic substances

Abstract

Provided is a metallic pigment for use in a UV-curable composition. Said metallic pigment is characterized by containing metal particles and a first film that covers the surfaces of the metal particles. The metallic pigment is further characterized in that the first film comprises amorphous silica.

Description

Metallic pigment and an ultraviolet curable composition containing it

The present invention relates to stability over time improves, and good metallic pigment capable of obtaining a metallic effect and an ultraviolet-curable composition to which it was compounded when incorporated into UV-curable compositions.

In recent years, metallic paint and metallic inks were formulated metallic pigment, from its unique excellent design properties, including the exterior of the automobile, electrical equipment, buildings, stationery, office equipment, communication equipment, a number of fields such as cosmetics in has come to be used.

Coating film formed by using a metallic paint reflects incident light from outside flaky metallic pigment contained in the coating film (i.e., metallic pigment), it shows a design sparkling. Reflection of light, I each color coupled with the coating exhibits a unique appearance with excellent design property. These effects are the same also in the printed material formed using the metallic ink.

The aluminum is excellent in metallic luster, easily handled because the specific gravity is smaller on the cheap. Thus, typical paint finish for automobiles, finishes plastics, printing inks, the metallic resistance design, such as in the resin moldings have been used a metal pigment comprising metal particles primarily to the aluminum flakes is representative.

On the other hand, the discharge of a large amount of carbon dioxide has become a problem due to energy consumption during scattering and paints drying VOC during painting (volatile organic compounds) in the paint field. Each of these are generally well known as a substance that causes causative agent and global warming photochemical oxidant, a countermeasure is urgently. Among them without using an organic solvent, rapid curability, low-pollution properties, the use of so-called UV paint and UV ink using a preferred UV-curable resin with energy saving has become more and more. Therefore, it is becoming even larger demand for metal pigments, including suitably formulated treatable aluminum flakes UV paints and UV inks.

UV paint and UV inks thus formulated with metallic pigments, which are known as UV metallic coating and UV metallic inks, in order to meet growing such UV metallic coating and UV metallic inks demand, UV metallic when using an aluminum pigment as the metal pigment used in paints and UV metallic inks, aluminum pigments produced by coating the surfaces of the aluminum flakes with higher saturated or unsaturated fatty acids and derivatives thereof such as stearic acid or oleic acid have been used conventionally It was.

However, such aluminum pigment, the storage stability when formulated in UV metallic coating and UV metallic in the ink is poor, there is a problem of causing gelation. That, UV metallic coating and UV metallic inks formulated with aluminum pigment, monomeric and oligomeric components in UV metallic coating and UV metallic in the ink during storage is activated by an aluminum ion of the aluminum pigment surface, the radical polymerization is promoted Therefore, problems such as paint or ink is gelled or solidified in the container has occurred. Such a problem had occurred in the metal pigment other than aluminum pigment. Therefore, in the field of UV metallic coating and UV metallic inks, metallic pigments such as generally most aluminum pigment was not used.

To solve this gelling problem, International Publication No. 2005/090487 pamphlet (Patent Document 1), suitable for UV metallic ink or UV metallic coating containing a metallic flake and the nitrocellulose as essential components metallic pigment compositions have been proposed. Although it has become possible to some extent the gelled by the proposal, further improvement in stability over time has been desired. Moreover, nitrocellulose is used by the proposal has been made to easily ignited explosion, because it involves the risk at the time of manufacture of the metallic pigment composition, its use has been limited in terms of safety.

On the other hand, nitrocellulose in the proposal is believed to prevent gelation by coating the surface of the metal flake, as a material for coating the surface of metal pigments, including aluminum pigment, for example, various resins , a coupling agent, phosphoric acid compounds, molybdenum compounds, chromic acid compounds, silica (JP 2003-147226 (Patent Document 2), International Publication No. 2004/096921 pamphlet (Patent Document 3)), and combination thereof etc. have been known.

WO 2005/090487 pamphlet JP 2003-147226 JP WO 2004/096921 pamphlet

To solve the gelation problems occurring when formulated with metallic pigments in UV metallic coating or UV metallic inks, it is conceivable to coat the surface of the metal pigments by another substance. As materials for coating the surface of the metallic pigment, as described above in example various resins, coupling agent, phosphoric acid compounds, molybdenum compounds, chromic acid compounds, silica, and combination thereof and the like are known.

Among these materials, various resins, expected that the monomer component of the unreacted contained therein reacts with UV metallic coating or monomer component or oligomer component of the UV metallic in the ink, to generate a similar gelling and the It is. Further, a coupling agent, phosphoric acid compounds, molybdenum compounds, chromic acid compounds can not be sufficiently cover the surface of the metal pigment in a continuous coating, the effect of this for metal ions present on the surface of the metal pigment considered it can not be sufficiently prevent the occurrence of gelation since not be sufficiently suppressed.

On the other hand, coating of the metal pigments by silica originally because it is intended to improve the stability of the metallic pigment in the aqueous medium, metal pigments coated with silica although excellent in dispersibility in an aqueous medium, UV was thought to dispersion is difficult for an oil medium, such as a metallic coating or UV metallic inks. Moreover, the silica has high affinity with water, the surface is considered to be hydrated, the residual of the hydrolysis catalyst used during the moisture impacts and silica synthesis, the curing of the ultraviolet curable resin is inhibited Rukoto are also expected.

Thus, these materials, by coating the metal pigments in particular by silica, while satisfying the normal conditions of use of the UV metallic coating or UV metallic inks, is impossible to prevent the occurrence of gelation as described above It was thought to be.

The present invention was made under such circumstances, but also be incorporated into the ultraviolet-curable composition, such as UV metallic coating composition or UV metallic ink composition to suppress the occurrence of gelation can, and an object thereof to provide a metallic pigment without the danger of fire or explosion.

The present inventors have revealed that intensive studies in order to solve the above problems, satisfactory results are obtained surprising discovery that obtained in the metal pigment coated with silica contrary to conventional expectations, further on the basis of this finding by overlaying the investigation, which has led to be finally completed the present invention.

That is, the metal pigments of the present invention is a metal pigment for incorporation into the ultraviolet-curable composition, and the metal particles, and a first coating that covers the surface of the first coating, non It is characterized in that it consists of crystalline silica.

Here, the first coating, it is preferred that the surface has been treated with a silane coupling agent. Further, the metallic pigment, per 100 parts by mass of metal particles, silicon is preferred to be included in a range of 0.01 to 100 parts by weight.

The invention also relates to the above ultraviolet-curable composition containing a metallic pigment, the ultraviolet-curable composition is preferably a UV metallic coating composition or UV metallic ink composition.

Metallic pigment of the present invention may be incorporated into UV-curable compositions, such as UV metallic coating composition or UV metallic ink composition it is possible to suppress the occurrence of gelation, and the risk of fire or explosion It has an excellent effect that without.

Further illustrate the present invention below.
<Ultraviolet-curable composition>
The ultraviolet-curable composition of the present invention, there is provided a composition which produces a resinous product by curing (i.e. coating or molded article) by UV, specifically a known so-called UV monomer or UV oligomer First, a composition containing a photopolymerization initiator and various additives.

Specific examples of such ultraviolet-curable composition, there can be mentioned the UV metallic coating composition or UV metallic ink composition or the like.

<Metal Pigment>
Metallic pigment of the present invention is intended to be blended in the ultraviolet-curable composition as described above, and metal particles, and a first coating that covers the surface of the first coating It is characterized in that it consists of amorphous silica.

Metallic pigment of the present invention, by having the first film, when it was blended into the ultraviolet-curable composition, contacting UV monomer or UV oligomers ultraviolet curable composition directly to the surface of the metal pigment since that is prevented, without the monomer or oligomer is activated during storage of the ultraviolet-curable composition, since radical polymerization is not promoted, such as ultraviolet-curable composition during storage is solidified or gelled problem does not occur.

The metal pigments of the present invention, the when the surface of the first coating further treated with a silane coupling agent, the components other than the metal pigment contained in the ultraviolet-curable composition (in particular, a resin cured by ultraviolet light) and the metal effect that improves the adhesion to the pigment.

Metallic pigment to the present invention is usually from 0.1 to 50 mass% in the ultraviolet-curable composition is preferably 1 to 30 mass%, more preferably from Formula 3 to 20 mass%.

<Metal particles>
The metal particles constituting the metal pigments of the present invention, can be for example aluminum, zinc, copper, silver, nickel, titanium, stainless steel, or metal particles made of an alloy containing at least one kind of these metals. Then, among these metal particles, aluminum particles, copper particles, alloy particles of copper and zinc, excellent in metallic luster, because the specific gravity easily handled relatively small on inexpensive, is particularly preferred.

Such a shape of the metal particles, particularly limited not granular, tabular, lump, flake (like scale), but can take various shapes, such as to provide a metallic appearance and brightness with excellent coating film and prints the is preferably a flake form for.

The average particle size of the metal particles is preferably in the range of 0.1 ~ 100 [mu] m, and more preferably in the range of 0.5 ~ 60 [mu] m. When the average particle diameter of the metal particles is 0.1μm or more, metallic feeling or brilliance is good. In the case the average particle diameter of the metal particles is 100μm or less, it is possible to prevent the metal particles protrude on the surface of the coating film or ink film, further smoothness or sharpness of the surface is less risk of reduced manufacturing in terms of cost it is advantageous. The average particle size of such metal particles can be determined by calculating the volume average from the measured particle size distribution by laser diffraction method.

If to use a flaky metal particles, it is preferable that the average thickness of the metal particles is in the range of 0.001 ~ 5 [mu] m, and more preferably in a range of 0.005 ~ 2 [mu] m. If the average thickness of the metal particles is not less than 0.001 [mu] m, since the metal particles having a sufficient strength, is good workability during the production process. Also when the average thickness of the metal flakes is 5μm or less, other less risk of smoothness or sharpness of the coating film or ink film is reduced, which is advantageous in terms of manufacturing cost.

The thickness is determined by the following calculation.
The average thickness (μm) = 10000 / 2.7 ( g / cm 3) × WCA (cm 2 / g)
(Average thickness (μm) = 4000 / WCA ( cm 2 / g) and may be represented simply)
WCA in the above formula represents a water surface diffusion area (cm 2 / g), which can be measured in accordance with JIS K5906.

To produce the intended flaky metal particles are usually using a grinding apparatus having a grinding media such as ball mill or attritor, in an organic solvent, the metal as a raw material powder and the grinding aid DOO was wet-ground, the metal powder can be produced flaky metallic particles by flaking.該磨 aid has the effect of suppressing unnecessary oxidation of the metal flake surfaces, to improve the gloss. Grinding aid is not particularly limited, but can be used a conventionally known, for example, oleic acid, and fatty acids such as stearic acid, fatty acid amines, fatty acid amides, fatty alcohols, such as suitably ester compound it can be used.

The organic solvent used in grinding time between the metal powder and the grinding aid is not particularly limited, but can be conventionally used known ones, for example, mineral spirits, and hydrocarbon solvents such as solvent naphtha, alcohol , ether-based, and solvent of the ester type can be used. In general, taking into account the safety problems, such as the flash point of the solvent in grinding time, hydrocarbon solvents having a high boiling point is preferably used. After grinding, HiMigaku grind is passed through a screen for coarse powder removal by subsequent solid-liquid separation of the organic solvent and the metal particles using a filter press or the like, a metal content of about 50 to 80 wt% of flakes paste Jo metal particles. The content of the organic solvent in the paste is desirably small as possible from the viewpoint of ensuring high-speed curing of the coating film or ink film.

<First coating>
First coating of the present invention consists of amorphous silica. The first coating, which is to cover the surface of the metal particles, may be formed so as to contact directly with the surface of metal particles, it may be formed via an undercoat layer described later. In the present invention, even when such a first coating is via an underlying layer (i.e. on the underlying layer) formed it shall be expressed as "covering the surface of the metal particles".

Here, the amorphous silica, mean amorphous silica having no crystal structure, specifically siloxane (H 3 SiO (H 2 SiO ) m SiH 3), hydrated silica (SiO 2 · mH 2 O), silica hydroxides (SiO n (OH) 4-2n) shall include the like. The above formula m represents an arbitrary positive integer, n represents the number in the range of 0 ≦ n ≦ 2.

Amorphous silica is very highly stable to have a dense layer structure UV monomer or UV oligomer contained in the ultraviolet curing type composition, further metal particles from the amorphous silica because it is completely covered by the first coating comprising a metal pigment of the present invention is very stable in ultraviolet-curable composition.

The first coating of the present invention need not be coated comprising only amorphous silica, without impairing the effect of the present invention may contain other additives and impurities. That is, the "composed of amorphous silica" in the present invention, not only when consisting only of amorphous silica, is also included if this contains other ingredients as.

As a method for forming the first coating of the present invention, by adjusting the pH of the dispersion solution containing the later of having an underlying layer, or no metal particles and an organic silicon compound and hydrolysis catalyst, can be exemplified a method of the organic silicon compound is hydrolyzed to deposit surface on the first coating surface or underlying layer of the metal particles is not limited thereto, any of the known the method may also be used. When employing the method illustrated above, it is preferable to uniformly disperse or dissolve the components by stirring the dispersed solution at an appropriate rate.

In the above method, but preferred for the simplification of the manufacturing process by adjusting the pH value of the dispersion solution by adding a hydrolysis catalyst, a method of adjusting the pH value of the dispersion solution thus the hydrolysis catalyst is not limited only to the method of adding may be to adjust the pH of the dispersion solution using the other acid compounds and / or alkaline compounds.

In the present specification, "an organic silicon compound" is a concept including both a condensate of organic silicon compound and an organic silicon compound.

Then, as the organic silicon compound used in the present invention is not particularly limited, by adjusting the pH of the dispersion solution containing the with an underlying layer, or no metal particles and an organic silicon compound and hydrolysis catalyst, the organic silicon compound is hydrolyzed, known organic silicon compound capable of forming a first film on the surface of the surface or underlying layer of the metal particles and can be exemplified condensates thereof.

Specific examples of the organic silicon compound, tetraethoxy silane, tetramethoxysilane, etc. tetraisopropoxysilane, and the like thereof condensates. These organic silicon compounds may be used a kind of thing singly or in a combination of two or more kinds thereof.

The hydrolytic catalyst to be used in the present invention is not particularly limited, by adjusting the pH of the dispersion solution containing the with an underlying layer, or no metal particles and an organic silicon compound and a hydrolysis catalyst, the pressurized water organosilicon compounds by the action of the cracking catalyst is hydrolyzed, it may be a known hydrolysis catalyst to form a first coating on the surface of the surface or underlying layer of the metal particles.

Specific examples of the hydrolysis catalyst, monoethanolamine, diethanolamine, triethanolamine, ammonia, ethylenediamine, t-butylamine, 3-aminopropyl triethoxysilane, n-2-aminoethyl-3-aminopropyltrimethoxysilane triethoxysilane, n-2-aminoethyl-3-aminopropyl methyl dimethoxy silane, urea, sodium silicate, and basic hydrolysis catalyst such as sodium hydroxide, oxalic acid, acetic acid, nitric acid, sulfuric acid, phosphoric acid, acidic, such as phosphonic acid such as hydrolysis catalyst.

Here, from the viewpoint of the reaction rate in the hydrolysis step, it is used a basic hydrolysis catalyst than acid hydrolysis catalyst. Among the above basic hydrolysis catalyst, triethanolamine, ammonia, ethylenediamine, 3-aminopropyltriethoxysilane, and particularly preferred from the standpoint of quality.

Further, as the solvent of the dispersion solution containing the with an underlying layer, or no metal particles and an organic silicon compound and a hydrolytic catalyst, it is preferable to use a hydrophilic solvent. Specific examples 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, and the like can be used acetone, preferred from the viewpoint of avoiding abnormal reaction between the aluminum particles and water, particularly when using aluminum particles as the metal particles.

However, these hydrophilic solvents may contain water. From the viewpoint of the case of using aluminum particles as the metal particles avoid abnormal reaction between the aluminum particles and the water content of water in the hydrophilic solvent is particularly preferably at most 20 mass%.

Also, this has an underlayer, or in a distributed solution containing no metal particle and an organic silicon compound and a hydrolyzable catalyst, 100 parts by weight of the metal particles (in the present invention is only the metal particles even when having a base layer respect of the parts by weight), the content of the organic silicon compound is preferably 2 parts by mass or more, more preferably equal to 5 parts by mass or more. It is preferable that the content of the organic silicon compound is below 200 parts by mass, more preferably not more than 100 parts by mass.

If the content of the organic silicon compound is less than 2 parts by mass, there is a tendency that the first film is not sufficiently formed enough to coat the surface of the metal particles, the content of the organic silicon compound is more than 200 parts by weight If tend to decrease aggregation and luster of the metal particles becomes remarkable. Note that when adding the organic silicon compound may be gradually added may be added all at once.

Also, this has an underlayer, or in a distributed solution containing no metal particle and an organic silicon compound and a hydrolyzable catalyst, with respect to 100 parts by weight of the metal particles, the content of the hydrolysis catalyst is 0.1 parts by mass or more it is preferably, more preferably in the range from 0.5 parts by mass or more. It is preferable that the content of the hydrolysis catalyst is not more than 20 parts by mass, more preferably not more than 10 parts by mass.

When the content of the hydrolysis catalyst is less than 0.1 part by weight tend to precipitation amount of amorphous silica which constitutes the first coating is insufficient, the content of the hydrolysis catalyst 20 mass beyond parts, tend to aggregate of metal particles becomes remarkable.

Also, this has an underlayer, or in a distributed solution containing no metal particle and an organic silicon compound and a hydrolyzable catalyst, with respect to 100 parts by weight of the metal particles, the content of the hydrophilic solvent is 500 parts by mass or more it is preferable, more preferably equal to 1000 parts by mass or more. It is preferable that the content of the hydrophilic solvent is less 10000 parts by mass, more preferably not more than 5000 parts by mass.

When the content of the hydrophilic solvent is less than 500 parts by mass tends stirring increases the viscosity of the slurry becomes difficult, the content of the hydrophilic solvent is more than 10000 parts by weight, of the treatment liquid collection, there is a tendency to play cost increases.

In addition, the surface of this has an underlying layer, or no metal particles, in the step of forming the first coating, it is preferable that the temperature of the dispersion solution in the step is 20 ° C. or higher, 30 ° C. or higher The preferred more, if any. The temperature of the dispersion solution in this step is preferably 90 ° C. or less, and more preferably 80 ° C. or less.

Temperature of the dispersion solution in the process in the case of less than 20 ° C., the formation rate of amorphous silica is slow, there is a tendency that a longer processing time, the temperature of the dispersion solution in this step is higher than 90 ° C. When the reaction there is a tendency that the risk increases to runaway.

Further, the surface of this has an underlying layer, or no metal particles, in the step of forming the first coating, the reaction time period is preferably 1 hour or more, and more preferably not less than 3 hours. Further, the reaction time is preferably 48 hours or less, and more preferably not more than 24 hours. If the reaction time is less than 1 hour, there is a tendency for formation of the first coating is insufficient, the reaction time exceeds 48 hours, there is a tendency that processing cost increases.

Here, the surface of this has an underlying layer, or no metal particles, in the step of forming the first coating, the pH value of the dispersion solution is changed during the reaction, is necessary to adjust the appropriate pH value is there. At that time, it is desirable to adjust the pH value by adding a hydrolysis catalyst, within a range not to impair the effects (characteristics) of the metallic pigment of the present invention, using other acidic and / or alkaline compounds dispersed pH of the solution may be adjusted.

Then, this has the underlying layer, or in a distributed solution containing no metal particle and an organic silicon compound and a hydrolysis catalyst, in the case of using a basic hydrolysis catalyst is preferably pH at least 7, 7 more preferably equal to .5 or more. It is preferable that pH of the dispersion solution is 11 or less, more preferably equal to 10 or less.

When the pH of the dispersion solution is less than 7 tend to formation rate of amorphous silica is reduced, the pH of the dispersion solution in this step is more than 11, reduction in cohesive and brilliant metal particles it tends to be large.

On the surface of this has an underlying layer, or no metal particles, in the step of forming the first coating, is better to use a basic hydrolysis catalyst than using acidic hydrolysis catalysts, amorphous preferred for faster productivity rate of formation of silica is good.

On the other hand, in the dispersion solution containing the with the underlying layer, or no metal particles and an organic silicon compound and a hydrolysis catalyst, when using an acidic hydrolysis catalyst, preferably a pH of 1.5 or more, more preferably as long as it is two or more. It is preferable that pH of the dispersion solution is 4 or less, further preferably equal to 3 or less.

When the pH of the dispersion solution is less than 1.5, the reaction tends to risk increases to runaway, the pH of the dispersion solution in this step is more than 4, precipitation rate of the amorphous silica They tend to be small.

First coating thickness of the present invention is preferably in the range of 1 ~ 500 nm. For 1nm or less, the suppression of responses to UV monomers and UV oligomers of UV curable composition becomes difficult, the storage stability is lowered. Also, since in the case of more than 500nm which reduces the tone of coating film, also hiding power is reduced, which is undesirable. More preferred thickness of the first coating is 10 ~ 350 nm, more preferably the thickness is 20 ~ 200 nm.

Note that the first coating thickness, can be measured by observation with a TEM (Transmission Electron Microscope), and if the thickness is 50nm or less measured by XPS (X-ray photoelectron spectroscopy) It is preferred.

<Treatment with a silane coupling agent>
Metallic pigment of the present invention, it is possible to treat the surface of the first coating with a silane coupling agent. That is, the first coating of the present invention, its surface may be treated with a silane coupling agent. By such processing the surface of the first coating with a silane coupling agent, and it is possible to further suppress the reactivity to monomers and oligomers of the ultraviolet curable composition, the adhesion (metal pigment and the resin the improvement of adhesion) coating film properties such as the adhesion and Hinuri was improved dispersibility in the ultraviolet-curable composition, such as a crystal orientation improving metal particles, various effects can be expected.

When the surface of the first coating is treated with a silane coupling agent, the surface of the first coating may be a state as covered by a single film made of a silane coupling agent, silane coupling amorphous silica and the coupling agent to form a first coating, to form a composite coating of first coating and the silane coupling agent by reacting with the organic silicon compound remaining in the first in the film it may be in a state of being.

Treatment with the silane coupling agent, usually, a silane coupling agent is hydrolyzed, presumably carried out by reacting with the hydroxyl groups of amorphous silica in constituting the first coating.

Examples of the silane coupling agent, for example methyl triethoxysilane, methyl trimethoxysilane, dimethyl dimethoxysilane, trimethyl methoxy silane, dimethyl diethoxy silane, trimethyl ethoxy silane, 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 - methyl - dimethoxysilane, 3-acryloxypropyl - trimethoxysilane, 3- Glycidyl oxy propyl - trimethoxysilane, 3-glycidyloxypropyl - methyl - dimethoxysilane, 3-mercaptopropyl - trimethoxysilane, 3-mercaptopropyl - triethoxysilane, 3-mercaptopropyl - methyldimethoxysilane, vinyl trichlorosilane , vinyltrimethoxysilane, vinyltriethoxysilane, vinyl - tris (2-methoxyethoxy) silane, vinyl triacetoxy silane, 3- (3,4-epoxycyclohexyl ethyl trimethoxy) silane, .gamma.-aminopropyltriethoxysilane, N-beta-(aminoethyl)-.gamma.-aminopropyltrimethoxysilane, 3-Yu laid triethoxysilane, 3-chloropropyl trimethoxysilane, 3-anilide propyl trimethoxysilane 3- (4,5-dihydro-imidazol-triethoxy) silane, n- phenyl-3-aminopropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, trifluoropropyl trimethoxysilane , 3-isocyanate propyl triethoxysilane, p- styryltrimethoxysilane, n- propyltrimethoxysilane, isobutyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, octadecyl triethoxysilane, phenyl trimethoxysilane, phenyl tri silane, and the like diphenyl diethoxy silane.

Is the following compound as a particularly preferred silane coupling agent.
R A -Si (OR B) 3 or R A -SiR B (OR B) 2 , or R A -SiR A (OR B) 2
R A: alkyl group or an aryl group or an alkenyl group having a carbon number of 2 ~ 18 R B: Alkyl groups specifically having 1 to 3 carbon atoms, the following compounds are exemplified.

For example, n- propyltrimethoxysilane, isobutyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, octadecyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, and the like diphenyl diethoxy silane.

Method of processing a first surface of the film of the present invention with a silane coupling agent is substantially the same as the method of forming the first coating, it can be carried out by hydrolyzing a silane coupling agent. The silane coupling agent is usually will react with the hydroxyl groups of amorphous in silica contained in the first coat.

More specifically, by adjusting the pH of the dispersion solution containing the with the underlying layer, or no metal particles and an organic silicon compound and a silane coupling agent and a hydrolysis catalyst, the organosilicon compound and the silane coupling agent is hydrolyzed, with an underlying layer, or the first coating on the no metallic particles are formed, and so that the surface thereof is treated with a silane coupling agent.

In this case, in order to carry out the process by hydrolysis of the first coating formation and the silane coupling agent by hydrolysis of the organic silicon compound stepwise, silane coupling after once forming the first coating by hydrolysis was added coupling agent, by further hydrolyzing it, it is preferable to treat the surface of the first coating with a silane coupling agent.

Incidentally, the reaction solvent for the treatment with a silane coupling agent, temperature, various conditions such as hydrolysis catalyst are the same as the conditions for forming the first coating.

The amount of the silane coupling agent per 100 parts by weight of the metal particles, 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight. If the amount of the silane coupling agent is less than 0.1 part by mass tends not to obtain desired effects, the more is 20 parts by mass than the unreacted silane coupling agent, such as coating film properties decrease there is a tendency to.

The metal particles, the underlayer (if formed only), and after forming the first coating, after treatment with a silane coupling agent is completed, the dispersion solution using the above hydrophilic solvent free from water and filtered through a filter after washing, it is preferable to remove water and unreacted material from the cake containing a metal pigment of the present invention.

Further, thereafter optionally cake containing a metal pigment of the present invention may be heated at a temperature in the range of 100 ~ 500 ° C..

Incidentally, the metal particle surface, forming a base layer, forming a first coating, the step of treating with a silane coupling agent may be carried out in a different dispersing solution or it is also possible to carry out continuously after adjusting the appropriate components in the same dispersion solution.

<Silicon content>
Metallic pigment of the present invention, with respect to 100 parts by weight of the metal particles, it is preferable that silicon is contained in a range of 0.01 to 100 parts by weight. The content of the silicon (parts by weight) is included in the first coat while indicating the amount of elemental silicon (i.e. Included in amorphous silica), the surface of the first coating is a silane If it is treated with a coupling agent, it shall refer to those obtained by further adding also the amount of silicon element contained in the silane coupling agent. The content of the silicon, more preferably with respect to 100 parts by mass of the metal particles is 50 parts by mass or less than 0.1 part by weight.

When the content of the silicon is less than 0.01 part by weight tend to stability of the metal pigment in the ultraviolet-curable composition is lowered, when the content of the silicon exceeds 100 parts by weight , which may or metallic pigment aggregation, or reduced concealing property, a problem color tone such as metal gloss is impaired occurs.

<Base layer>
Metallic pigment of the present invention can be an underlying layer is formed on the metal particles to form a first coating on the underlayer. The undercoat layer has at the time of forming the first coating, at the core for the first coating is precipitated, the effect of promoting the first coating is formed. Thus, it is possible to first coat thickness becomes uniform, perform suppression of reaction between the UV monomer or UV oligomer contained in the ultraviolet-curable composition more fully.

Examples of such underlying layer, an oxide containing molybdenum, hydroxide, a layer consisting of a mono-content film or a mixture film consisting of at least one hydrate (hereinafter referred to as "layer containing molybdenum") Although the layer or the like including an oxide of metal elements constituting the or metal particles can be exemplified, but the invention is not limited thereto.

A method of forming a layer containing molybdenum as a base layer on the metal particle surface is not particularly limited, a preferred method may be a method such as the following. That is, metal particles, and a solution containing a molybdenum compound as described below, by mixing and stirring or kneading in a slurry state or a paste state, forming a hydrated film containing molybdenum metal particle surfaces, by subsequent heating how to oxide film. As the method for forming a layer containing molybdenum, for example, a conventionally known method disclosed in Japanese Patent 09-328629 discloses the like may be employed.

The molybdenum compounds used in the formation of a layer containing molybdenum, composition formula Mo x O y · mH 2 O 2 · nH 2 O ( here, x is 1 or 2, y is an integer of 2 to 5, m, n is peroxide poly molybdate represented by any showing a positive number), ammonium molybdate, can be exemplified phosphomolybdic acid. For example peroxides poly molybdate may be prepared by dissolving metallic molybdenum powder or molybdenum oxide or the like to the aqueous solution of hydrogen peroxide (concentration: 5 to 40 mass%). These molybdenum compounds, 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, and the treatment solution is dissolved in a hydrophilic solvent such as acetone. The treatment solution may contain water.

The amount of molybdenum in the layer containing molybdenum, 100 parts by mass of the metal particles to 0.01 to 3.0 parts by mass, more preferably preferably from 0.05 to 2.0 parts by mass. The amount of molybdenum, it is preferable to change depending on the specific surface area of ​​the metal particles to be treated. Increasing the amount of molybdenum with respect to large metal particles specific surface area, it is preferable to reduce for small metal particles specific surface area. If the amount of molybdenum is 0.01 part by mass or more with respect to 100 parts by mass of the metal particles, the chemical stability of the metal particles for forming the uniformity and the first coat of the first coating thickness is good There is less than or equal 3.0 parts by mass, for example with agglomeration is prevented and a decrease in the metal particles shades of metal particles such as metal gloss, humidity resistance, adhesion and coating film properties such as weather resistance good It is maintained in.

On the other hand, that the method of forming a layer containing an oxide of a metal element forming the metal particles as a base layer on the metal particle surface is not particularly limited, a preferred method is, for example, to treat the surface of the metal particles in the hydrogen peroxide and a method of forming the oxide by. By treating the surface of the metal particles in the hydrogen peroxide, with removed fatty acids adsorbed on the surface of metal particles, with the oxidized surface of the metal particles, containing an oxide of a metal element constituting the metal particles layers are formed. Thus, the surface of the metal particles, the layer becomes prone surface condition grows a first coat become a starting point.

To explain the method more specifically, by stirring or kneading the solution was mixed in a slurry state or a paste state containing metal particles and hydrogen peroxide, containing a metal element constituting the metal particles to the surface of metal particles forming a hydrated film, by subsequent heating can be exemplified a method in which the hydrated film and an oxide film. For example, if the use of aluminum particle solution containing the aluminum particles and the hydrogen peroxide is stirred or kneaded and mixed in a slurry state or a paste state as the metal particles, an aluminum particle surface hydrated film containing aluminum is formed, aluminum oxide film by which the further heating, the oxide film such as a boehmite coating is formed.

The solution containing hydrogen peroxide in the above, typically, a solution prepared by dissolving hydrogen peroxide in a solvent can be used. As the solvent, addition of water, can be used an alcohol, glycol, glycol ether, an organic solvent such as ketone, a mixed solvent such as water and organic solvents may also be used. Hydrogen peroxide concentration in the solution is preferably from 0.0001 to 45 mass%.

<Applications and the like>
Metallic pigment of the present invention is intended for incorporation into ultraviolet-curable composition. The present invention is not only related to such metallic pigments, also relates to a ultraviolet-curable composition containing the metallic pigment. The ultraviolet-curable composition of the present invention is preferably a UV metallic coating composition or UV metallic ink composition.

The metallic pigment of the present invention is blended in the ultraviolet-curable composition, UV monomer or UV oligomers ultraviolet curable composition is not activated, since radical polymerization is not promoted, the ultraviolet-curable composition during storage or gel, does not cause a problem such as coagulation.

Generally, the ingredients of the UV metallic coating composition or UV metallic ink composition consists mainly resin component, a photopolymerization initiator, and the like. Here, UV metallic ink composition is mainly being constituted by components 100% solidifying free of organic solvent as a rule. On the other hand, UV metallic coating composition may use 10 to 20 percent of diluent to lower the viscosity leveling problems.

The UV metallic coating composition and UV metallic ink composition be formulated to be in a range of 0.1 to 50% by weight metallic pigments UV metallic coating composition and UV metallic ink composition of the present invention It is preferred. Physical properties of the amount of metallic pigment sufficient metallic effect is obtained when at least 0.1 wt%, UV metallic coating composition in the case is less than 50 wt% and UV metallic ink composition, weathering sex, corrosion resistance, less pose a risk to the mechanical strength and the like.

As the resin component of UV metallic coating composition or UV metallic ink composition generally is used which cure with ultraviolet light. As the resin component which is cured by ultraviolet rays, it may be mentioned those composed of reactive monomer (i.e. UV monomer) or reactive oligomer (i.e. UV oligomers). Cure these monomers and oligomers by ultraviolet (polymerization) is but becomes resinous, the UV metallic coating composition or UV metallic ink composition, the polymer may be contained.

The reactive monomer is not particularly limited, for example, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acryloyl phosphate, tetrahydrofurfuryl acrylate, acrylate of tetrahydrofurfuryl derivatives such as monofunctional monomer, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, dipentaerythritol hexaacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, hydroxy Viva phosphoric acid ester neopentyl glycol Gia Relate, bifunctional monomers such as tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, include trifunctional monomers such as dipentaerythritol hexaacrylate.

As the reactive oligomer, for example polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates (e.g., diglycerol polyglycidyl ether acrylate) and the like. Further, as the polymer, is not particularly limited, for example, acrylic resins, alkyd resins, polyester resins, polyurethane resins, polyvinyl acetate resins, nitrocellulose resins, resins having an unsaturated double bond such as a fluorine resin It can be suitably used.

Although in recent years some cases to use a water-soluble resin or emulsion resin of ultraviolet curable as the resin component, it may contain them. Further, as a diluent (solvent) may contain a common organic solvent or water if small amounts.

The dilution agent is not particularly limited, for example, phthalates, monomers and the like. The phthalates, 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, phthalate -α- naphthyl ester, and phthalic acid dibenzyl ester. The monomer, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acryloyl phosphate, tetrahydrofurfuryl acrylate, a monofunctional monomer such as acrylate tetrahydrofurfuryl derivative, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, hydroxy Viva phosphate ester neopentyl glycol diacrylate, difunctional monomers such as tripropylene glycol diacrylate, tri Chi triacrylate, pentaerythritol triacrylate, include trifunctional monomers such as dipentaerythritol hexaacrylate.

On the other hand, as the photopolymerization initiator, for example, it can be cited a radical photopolymerization initiator is not particularly limited. The radical photopolymerization initiator, mention may be made as follows. For example, as alkyl phenone-based photopolymerization initiator, 2,2-dimethoxy-1-hydroxy - cyclohexyl - phenyl - ketone, 2-hydroxy-2-methyl-1-phenyl - propane 1-one, 1- [4- (2-hydroxyethoxy) - phenyl] -2-hydroxy-2-methyl-1-hydroxy-1- {4- [4- (2 - hydroxy-2-methyl - propionyl) - benzyl] phenyl} -2-methyl - propan-1-one, 2-methyl-1- (4-Chi thiophenyl) -2-morpholinopropan-1-one, 2 - benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butanone-1,2 (dimethylamino) -2 - [(4-methylphenyl) methyl 1- [4- (4-morpholinyl) phenyl] -1-butanone and the like, and acylphosphine oxide-based photopolymerization initiator, 2,4,6-trimethyl benzoyl - diphenyl - phosphine oxide, bis ( 2,4,6-trimethylbenzoyl) - phenyl phosphine oxide and the like, as titanocene photopolymerization initiator, bis (Ita5-2,4- cyclopentadiene-1-yl) - bis (2,6-difluoro -3-(1H-pyrrol-1-yl) - phenyl) titanium, and the like. It is an oxime ester compound as the other photopolymerization initiator 1,2-octanedione, 1- [4- (phenylthio) -, 2-(O-benzoyl oxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl] -, 1-(O-acetyl oxime) or oxyphenyl acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] ethyl oxy phenylacetic acid ester compound esters, oxy phenylacetic acid 2- (2-hydroxyethoxy) can be mentioned ethyl ester and the like. Further, usually a customary to use a mixture of these radical photopolymerization initiator, there may be used in combination such as benzophenone.

Further, the UV metallic coating composition or UV metallic ink composition of the present invention, if necessary, quinacridone red, phthalocyanine blue, phthalocyanine green, isoindolinone yellow, carbon black, perylene, organic pigments such as azo lake, oxide iron, titanium oxide, cobalt blue, zinc white, ultramarine blue, chromium oxide, mica, inorganic pigments such as chrome yellow, anti-settling agents, thickening agents, static removers, dispersants, antioxidants, polishes, surfactants agents, synthetic preservatives, lubricants, fillers (reinforcing agents), waxes, defoamers, leveling agents, stabilizers may be added or the like. Further, acidic phosphate esters, nitrocellulose, and the like may be added carbodiimide compound.

As a method for coating or painting with UV metallic coating composition, brushing, doctor blade, a roll coater, a method of coating with a bar coater or the like, and a method of coating with a spray or the like.

As a method of printing using a UV metallic ink composition, include known printing methods, for example intaglio printing gravure printing, offset printing (transfer printing), screen printing, flexographic printing, other relief, planographic printing etc. the. Further, UV metallic ink composition of the present invention can be suitably used for inkjet printing.

For by coating UV metallic coating composition or UV metallic ink compositions incorporating metal pigment of the present invention, it may be formed on the electrodeposition coating primer layer and the intermediate layer due, also the paint coating topcoat layer may be formed on the film. Paint of the top coat layer is UV, solvent, such as aqueous, it may be of any type.

The thickness of the paint coating film, is not particularly limited, in a general embodiment, preferably at 1μm or more, and more preferably equal to 5μm or more. Further, the thick optic lobe, is preferably 100μm or less, and more preferably 30μm or less.

If the thick body is less than 1μm tend to ink, the effect of hiding the underlying by coating becomes insufficient, the said thickness only exceeds 100 [mu] m, transmission of ultraviolet rays becomes insufficient, weak sites cured in the coating but there is a danger that occurs. Further, since the drying is difficult, popping tend to defects is increased, such as sauce.

The present invention will hereinafter be described by examples in more detail, the present invention is not limited thereto.

<Example 1>
By adding hydrogen peroxide to hydrogen peroxide 3g containing 30 wt% metallic molybdenum powder 0.3g little by little, abbreviated as isopropyl alcohol (hereinafter IPA solution obtained by reacting hydrogen peroxide and metallic molybdenum ) was dissolved in 500g. Moreover, commercial aluminum particles as the metal particles to the solution (trade name: "5422NS", Toyo Aluminum Co., Ltd., solid content 75 mass%, average particle size 19 .mu.m) was slurried added 40 g (30 g as aluminum content), by mixing 1 hour stirring the slurry at 75 ° C., and the underlayer is a layer containing molybdenum is formed on the metal particles.

Thereafter, the aqueous ammonia and water 80g was added to the slurry to adjust the pH of the slurry to 10. pH of the slurry was adjusted, (hereinafter referred to as TEOS) tetraethoxysilane 40g was dropped gradually those dissolved in IPA of 40g, 2 hours and stirred and mixed for a further 75 ° C.. The resulting slurry was solid-liquid separated through a filter, to remove the IPA and the ammonia addition remained, by drying 12 hours at 120 ° C. in order to carry out dehydration of hydrates in the amorphous silica the surface of the metal particles having an undercoat layer to obtain a coated powdered metal pigment with amorphous silica (first coat) (aluminum pigment) (100 parts by weight of solid content). Results silicon content of the obtained metallic pigment was determined by plasma emission analysis, with respect to 100 parts by weight of metal particles (aluminum particles), the content of silicon was 15.7 weight parts. In addition, as a result of the thickness of the first coating was measured by direct observation by TEM, was about 60 nm.

By using a metal pigment obtained in this way, the UV metallic coating composition was prepared according to "the formulation of UV metallic coating composition" later, the storage stability was evaluated. The results are shown in Table 1.

<Example 2>
In the same manner as in Example 1 to obtain a slurry of the undercoat layer was formed on the metal particles is a layer containing molybdenum. The pH value of the slurry was added the monoethanolamine to the slurry was adjusted to 8.5.

Then, the slurry was adjusted pH, the mixture was stirred for 6 hours at gradually dropped while 50 ° C. a solution obtained by dissolving TEOS40g the IPA of 40 g. Then, decyl trimethoxysilane 2g was added to the slurry and stirred for an additional 4 hours at 50 ° C.. Check the pH value of the slurry during every 2 hours, the pH value by addition of monoethanolamine was adjusted to 8.5.

After the above reaction was completed, the slurry was solid-liquid separated through a filter, and dried 12 hours at 120 ° C. a slurry containing metallic pigment obtained, amorphous silica (first surface of the metal particles having an underlayer coated with the coating), obtained by treating further the surface of the first coating with a silane coupling agent, powdered metallic pigment (aluminum pigment) was obtained (solid content 100 parts by mass). Results silicon content of the obtained metallic pigment was determined by plasma emission analysis, with respect to 100 parts by weight of metal particles (aluminum particles), the content of silicon was 14.5 weight parts. In addition, as a result of the thickness of the first coating was measured by direct observation by TEM, was about 55 nm.

By using a metal pigment obtained in this way, the UV metallic coating composition was prepared according to "the formulation of UV metallic coating composition" later, the storage stability was evaluated. The results are shown in Table 1.

<Comparative Example 1>
As the metallic pigment, a commercially available aluminum particles (trade name: "5422NS", Toyo Aluminum Co., Ltd., solid content 75 mass%, average particle size 19 .mu.m) using, in accordance with the "formulation of UV metallic coating composition" below the UV metallic coating composition was prepared and evaluated for storage stability. The results are shown in Table 1.

<Comparative Example 2>
Commercially available aluminum particles (trade name: "5422NS", Toyo Aluminum Co., Ltd., solid content 75 mass%, average particle size 19 .mu.m) with respect to 133 g (100 g as aluminum content), butyl acid phosphate 2g as a surface treatment agent It was added, subjected to mixing for 30 minutes in a kneader mixer to prepare a surface-treated aluminum paste.

The obtained surface-treated aluminum paste 135 g, nitrocellulose 10 parts by weight were dissolved in 90 parts by weight of acrylic acid 2-hydroxy-3-phenyloxypropyl solution was 30g blended mixes for 30 minutes by a kneader mixer aluminum pigment composition (metal content 60 parts by weight) was obtained.

The metal pigments, by using the obtained aluminum pigment composition (which the surface of the aluminum particles coated with nitrocellulose), a UV metallic coating composition was prepared according to "the formulation of UV metallic coating composition" below, storage stability was evaluated. The results are shown in Table 1.
<Formulation of UV metallic coating composition>
Component parts by weight 1. 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
In the above formulation, the details of each component are as follows.

1. Oligomer (EA-5720): trade name "NK Oligo EA-5720" (di-glycerol polyglycidyl ether acrylate), manufactured by Shin Nakamura Chemical Industry Co., Ltd. 2. DPHA: dipentaerythritol hexaacrylate, manufactured by Kyoeisha Chemical Co., Ltd. 3. TMPTA: trimethylol propane triacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. 4. Irgacure 184: hydroxycyclohexyl phenyl ketone, Ciba Specialty Chemicals Co., Ltd. 5. Irgacure 754: oxyphenyl acetate, 2- [2-oxo-2-phenyl-acetoxy-ethoxy] ethyl ester and oxy-phenyl acetic acid, 2-mixture of (2-hydroxyethoxy) ethyl ester, manufactured by Ciba Specialty Chemicals 6. Irgacure 819: phenyl bis (2,4,6-trimethylbenzoyl) - phosphine oxide, Ciba Specialty Chemicals Corp. 7. Metal pigment: Note metallic pigment obtained in Examples and Comparative Examples, the 1 UV oligomers, 2 and 3 are UV monomer, 4-6 photopolymerization initiator.

In Table 1, the term "paint dispersion" is obtained by visually evaluating the dispersibility immediately after the production of the UV metallic coating composition. The evaluation criteria are as follows.
A: metallic pigment is well dispersed in the paint, strong metallic luster of the paint surface.
B: metallic pigment is dispersed in the paint, there is a metallic gloss paint surface.
C: the metal pigment is tentatively dispersed in the paint, no metallic luster is poor paint surface conformability.
D: metal pigment is not completely fit with the paint, the paint surface exhibits a gray color.
In other words, "A" represents the best dispersibility, shows that most dispersibility "D" is poor.

Note that "60 ° C. × 3 days" and "60 ° C. × 7 days" are both concerned with the evaluation of the storage stability of the UV metallic coating composition, for 3 days, and 60 ° C. at 60 ° C. after manufacture, respectively 7 days, it shows the results when stored (storage). Note that the "solidification" further progress "gelled" refers to a totally state showing no flowability.

Table 1 As is apparent, the metal pigments of Examples 1 and 2 according to the present invention, compared to metal pigment of Comparative Example showed good storage stability, without problems after a certain period storage coating / it could be painted.

That is, the metal pigments of the present invention may be incorporated into UV-curable compositions, such as UV metallic coating composition or UV metallic ink composition it is possible to suppress the occurrence of gelation, and such as nitrocellulose it is clear that an excellent effect that without the danger of fire explosion since containing no hazardous substances.

Although been explained about the embodiments and examples of the present invention as described above, it is originally intended be combined as appropriate with any of the structures of the embodiments and examples described above.

Embodiments and examples disclosed herein are carried out are to be considered and not restrictive in all respects as illustrative. The scope of the invention is defined by claims rather than the above description, it is intended to include any modifications within the meaning and range of equivalency of the claims.

Claims (5)

  1. A metallic pigment for incorporation into the ultraviolet-curable composition,
    Wherein the metal particles and the first coating covering the surface,
    Wherein the first coating is composed of amorphous silica, metal pigments.
  2. Said first coating, the surface thereof is treated with a silane coupling agent, a metal pigment according claim 1, wherein.
  3. The metallic pigment, relative to the metal particles 100 parts by weight, silicon is contained in a range of 0.01 to 100 parts by weight, the metal pigment according claim 1, wherein.
  4. Ultraviolet-curable composition containing a metallic pigment ranging first claim of claim.
  5. The ultraviolet-curable composition is a UV metallic coating composition or UV metallic ink composition, ultraviolet-curable composition according claim 4.
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