JPH1180587A - Colored metallic powdery pigment and coating material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject pigment, rich in kinds of color tones by interference colors, having high masking properties, excellent in processability and useful for coating materials or the like by coating a metallic powder with a hydrolyzate of a specific metallic compound and then heating the coated metallic powder at a high temperature below the melting point of the metallic powder. SOLUTION: This colored metallic powdery pigment is obtained by hydrolyzing a substance represented by the formula [M is a metallic atom; R is an alkyl; (n) is an integer of 1-40] (e.g. tetra-n-butyl titanate), coating the surface of a metallic powder (e.g. aluminum) with the resultant product in an amount so that the product prepared by hydrolyzing the substance represented by the formula is present within the range of 1-360 mg, based on 1 m' surface area of the metallic powder and expressed in terms of the metal, and then heating the coated powder at >=400 deg.C and a temperature below the melting point of the metallic powder. The resultant pigment is rich in kinds of color tones by interference colors, has high masking properties, is excellent in processability and is useful for a coating material composition or the like capable of imparting color flop properties to a coating film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention mainly relates to automobiles,
Various inks such as paints, printing inks, writing inks, copying inks, specialty inks, resin compounds, ceramic products, cosmetics, etc. for bicycles, toys, home appliances, buildings, vehicles, industrial machines and their parts. Colored metal powder pigment which is a kind of pigment used and a method for producing the same,
And a coating composition using the pigment.

[0002]

2. Description of the Related Art Conventionally, as a method for obtaining a colored metallic coating film, a method in which a metal powder and a colored organic and / or inorganic pigment are used together as a pigment component in a coating material is known. Since the pigment is added, the process is complicated, and there is a problem that the tint is changed due to a delicate difference of each compounding ratio.

Therefore, as a method for solving the above problems, a pigment having both metallic luster and coloring power has been devised. One is a method using a metal pigment, a method of using a colored metal pigment, or a method of coloring the metal pigment itself as desired, and the other is different from the metal luster itself, In this method, a pigment having a pearly luster is used.

[0004] For example, as a method for obtaining a gold-colored metallic coating film, small pieces of brass may be used as a pigment. However, the material brass is expensive and harmful to the human body, so its application range is narrow, and in addition, there is a problem that discoloration and gloss deterioration are remarkable depending on the environment. On the other hand, as a method for coloring the surface of a highly safe and inexpensive metal to a desired color, there is a method of treating the surface of an aluminum powder with a coloring substance (Japanese Patent Publication No. 53-4004 and Japanese Patent Application Laid-open No. Sho 53-4004). JP-A-60-50176, JP-A-60-72969, JP-B-6-92
546, JP-A-7-228797, JP-A-8-85765, JP-A-1-31176, JP-A-8-209024, JP-A-8-333
602).

[0005] That is, in Japanese Patent Application Laid-Open No. 53-4004, after the aluminum powder is subjected to boehmite treatment as required, the aluminum powder is immersed in a weak alkaline solution containing a metal salt and an organic compound having a chelating ability, so that the surface of the aluminum powder is Discloses a method of forming a chelate to obtain a colored metallic aluminum powder. However, in this method, there is a problem that the aluminum powder reacts with the alkali during the alkali treatment to cause gelation or generation of hydrogen gas, so that it is difficult to obtain a coating film having a metallic luster.

In Japanese Patent Application Laid-Open Nos. 60-50176 and 60-72969, hexavalent or trivalent chromium is obtained by treating aluminum powder with chromic anhydride, dichromic acid, and fluoride. Although a method of obtaining a gold aluminum powder by adsorbing chromium compounds on the surface is disclosed, the use of a chromium compound as a treating agent requires environmental and economical considerations such as safety during treatment and the necessity of taking measures against pollution of waste liquid. There is a problem.

Japanese Patent Publication No. Hei 6-92546 discloses a method in which a color pigment is chemically adsorbed on the surface of a metallic pigment, and the surface is coated with a resin to protect the easily removable color pigment. In such a case, the process becomes complicated, and there is a problem that the color of the formed metallic coating is not much different from that of the conventional method. JP-A-7-22879
No. 7, JP-A-8-85765 discloses a method in which aluminum powder is treated with an organic titanium and then treated with a color developer, but this method is intended for chemical stabilization of the aluminum surface. No interference color appears.

JP-A-1-31176 discloses a method of coating titanium oxide on the surface of an aluminum pigment using titanium tetrachloride vapor and water vapor.
No. 24 discloses a method of obtaining a pigment having an interference color by a method in which coating layers having different refractive indexes are coated on a flaky metal substrate in a multilayer manner. In particular, JP-A-8-209024 discloses a method for obtaining a pigment having a different color tone depending on the viewing angle (hereinafter referred to as color flop property), as in the present invention. However, these methods have disadvantages in that the steps are complicated, the pigments are easily aggregated, and it is difficult to use as a paint.

Japanese Patent Application Laid-Open No. 8-333602 discloses a method of producing a flake-like titanium powder and oxidizing the surface thereof to obtain a colored pigment having an interference color. There is a problem that it is difficult to manufacture at low cost. Further, pigments having a pearly luster, which is different from the metallic luster, have been devised. This is a thin piece of a high-refractive-index substance or a thin film of a high-refractive-index substance formed on a colorless and transparent inorganic substrate, and both are colored pigments utilizing the interference color of the thin film.

As these pearlescent pigments, for example, guanine crystals extracted from scales of herring are famous.
This has a problem that it is expensive because it can be obtained in a small amount in a natural product. An alternative to this is basic lead carbonate,
Bismuth acid chloride crystal fragments have been developed but are not widely used at present due to their toxicity. Thus, for example, Japanese Patent Publication No. 35-5367 discloses a method of imparting pearl luster by coating a transparent flaky substance with titanium dioxide generated from titanium alcoholate. A method of coating a transparent mica substance with titanium dioxide generated from titanium tetrachloride. Japanese Patent Publication No. 43-25644 discloses a method of coating a metal oxide such as titanium dioxide, zirconium dioxide, iron oxide, and chromium oxide with a non-opaque mica. The method of forming on a piece each obtains a pigment giving an interference color.

However, as described above, all of these pearlescent pigments exhibit an interference color by forming a high refractive index layer on a colorless and transparent substrate, and necessarily have a low hiding power. , Is strongly affected by the underlayer when forming the coating film. Accordingly, the number of undercoating steps is increased (Japanese Unexamined Patent Publication No. 59-160).
571, JP-A-59-215857) or a complicated step of mixing and using a pigment having a high hiding power such as aluminum powder. Also, to use natural products such as mica as the substrate,
It is difficult to adjust the particle size distribution and shape of the substrate to desired conditions, and it is difficult to arbitrarily adjust various design properties resulting therefrom.

On the other hand, Japanese Patent Application Laid-Open No.
Japanese Patent Application Laid-Open No. 110568 discloses a method for producing a color pigment exhibiting an interference color by providing a product obtained by hydrolyzing a metal alcoholate on the surface of aluminum, but it is possible to obtain a color pigment having a color flop property. I didn't.

[0013]

SUMMARY OF THE INVENTION The present invention provides a metal powder pigment having a wide variety of color tones due to interference colors, high concealing properties, and excellent workability, and a method for producing the same. It is an object of the present invention to provide a coating composition which exhibits excellent color flop properties and obtains a novel metallic coating film without aggregation.

[0014]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors hydrolyzed a substance represented by the following general formula (1) and coated the surface with the product. It has been found that the object can be achieved by using a metal powder as a coating composition, and the present invention has been accomplished.

That is, the present invention is as follows. 1) After hydrolyzing a substance represented by the following general formula (1) and coating the surface of the metal powder with the product,
A colored metal powder pigment obtained by heating at a temperature lower than the melting point of the metal powder.

[0016]

Embedded image

Wherein M is a metal atom, R is an alkyl group,
n represents an integer of 1 to 40. 2) 1 mg of a product obtained by hydrolyzing the substance represented by the general formula (1) (hereinafter also referred to as a hydrolyzate of metal alcoholate) as 1 mg of metal per 1 m ² of surface area of the metal powder.
2. The colored metal powder pigment according to the above item 1, which is present in an amount of 360 mg or less. 3) The colored metal powder pigment as described in 1 or 2, wherein the metal atom M is titanium or zirconium.

4) The above 1 wherein the metal powder is aluminum
Or a colored metal powder pigment according to 2. 5) A coating composition containing the colored metal powder pigment described in 1, 2, 3 or 4 as at least a part of a pigment component. 6) A coating composition containing a colored metal powder pigment exhibiting an interference color coated with a coating containing a metal oxide, and capable of imparting color flop to the coating.

7) A coating film using the coating composition described in 6 above. 8) hydrolyzing the substance represented by the general formula (1), coating the surface of the metal powder with the product, and then heating at a temperature of 400 ° C. or higher and lower than the melting point of the metal powder. 5. The method for producing a colored metal powder pigment according to any one of the above 1 to 4. Hereinafter, the present invention will be described in more detail.

In the present invention, the substance represented by the general formula (1) is a so-called metal alcoholate. Examples of the metal atom M include titanium, zirconium, silicon, tantalum, aluminum, calcium, sodium, boron, lanthanum, and zinc. Titanium and zirconium are particularly preferable because those having a high refractive index are desirable.

As the alkyl group, methyl, ethyl, propyl, butyl, octyl, stearyl and the like are used, and those from an ethyl group to an octyl group are particularly preferable. The reason is that the higher the molecular weight of the alkyl group is, the slower the hydrolysis is, while the higher the molecular weight is, the higher the molecular weight is, it becomes waxy and the solvent that can be uniformly dispersed is limited. In particular, when the reaction rapidly occurs in a monomer (n = 1 in the above general formula) and a large amount of floating particles are generated, a dimer (n = 2), a trimer (n = 3), It is desirable to use a condensate such as a tetramer (n = 4). Generally, n = 1 to 4
Although it is 0, if the number of n is too large, the viscosity of the metal alcoholate itself increases, and it becomes difficult to dissolve in the solvent.
Up to about 4 is desirable. These metal alcoholates may be used alone or in combination of two or more.

Specific examples of the metal alcoholate used in the present invention include tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-sec-butyl titanate, tetra-tert-
Butyl titanate, tetra-2ethylhexyl titanate, tetraethyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate, tetra-2ethylhexyl zirconate, etc. These condensates are mentioned.

The hydrolysis reaction in the present invention is carried out by adding a metal alcoholate and water in an amount capable of hydrolyzing the metal alcoholate in a state where the metal powder is suspended in a solvent.
This hydrolyzate is deposited on the surface of the metal powder particles. For example, when n = 1 in the general formula (1), a reaction represented by a reaction formula of M (OR) ₄ + 2H ₂ O → MO ₂ + 4ROH generally occurs, and the metal oxide is formed by hydrolysis. It is considered to be formed on the particle surface of the powder.

The method of adding the metal alcoholate and water may be a batch addition method or a method of dividing the mixture into small steps in small amounts. Further, a continuous addition method may be used. Each order of addition may be such that water is added to the place where the metal alcoholate is dissolved or suspended in the solvent first, or the metal alcoholate is added after the water is dissolved or suspended in the solvent first. And may be added simultaneously little by little or alternately. However, in general, when the reaction is carried out gently, the generation of floating particles tends to be reduced. Therefore, it is desirable to add the solution little by little as necessary in a state where the concentration is reduced with a solvent.

The solvent generally used in the present invention is
Although not particularly limited, those which dissolve metal alcoholates, such as alcohols, mineral spirits, solvent naphtha, benzene, toluene, xylene, and petroleum benzine, are desirable. These can be used alone or as a mixture of two or more. In the step of hydrolyzing the metal alcoholate in the present invention, water is added in an amount required for hydrolysis. When water is added later, it is desirable to add it little by little or to dilute it with a solvent before use. Also, if the addition amount is small, the reaction takes too long or the metal alcoholate tends to condense linearly,
Three-dimensional cross-linking does not occur on the surface of the metal powder, and it is difficult to form a uniform coating film. On the other hand, if there is too much water, gelation is likely to occur, agglomeration of the metal powder occurs, and reacts with the metal powder,
Hydrogen gas may be generated, and the amount of addition is desirably about several times the number of moles of the metal alcoholate. However, when alcohol is used as the solvent, the alcohol acts as an inhibitor of the reaction and the reaction is slowed down. Then remove the water. In this case, if a catalyst such as hydrogen chloride is used, it is not necessary to use a large amount of water.

The reaction temperature is such that hydrolysis occurs at room temperature,
If the reaction is too rapid, cooling is desirable. Further, in order to slow the hydrolysis rate, the metal alcoholate may be diluted with a solvent and added at a low concentration, or a reaction inhibitor such as diethanolamine may be added. Further, alcohol is by-produced by the addition of water in the hydrolysis reaction of the metal alcoholate, so that alcohol can be used as a polymerization rate regulator.

In the present invention, the hydrolyzate of metal alcoholate and the metal powder are thought to be bonded via the hydroxyl group present on the surface. However, when the bonding force is weak and a large number of floating particles are formed, the anchor site is used as the anchor site. A hydrolyzate of a metal alcoholate such as a carboxyl group or an amino group, or a metal powder, and a compound (for example, dicarboxylic acid or the like) having a hydrogen bond or an ion bond at both ends may be added.

The amount of coating is such that the hydrolyzate of metal alcoholate is 1 metal as a metal content per 1 m ² of the surface area of the metal powder.
Desirably, the amount is not less than mg and not more than 360 mg. 1m
If it is less than g, the coloration becomes weak, and if it exceeds 360 mg, the interference color becomes weak and the number of floating particles tends to increase.
As the metal powder used in the present invention, aluminum,
Copper, zinc, iron, nickel, and / or alloys thereof are used, and a preferable example is aluminum. Although the shape of the metal powder is not particularly limited, it is preferable that the surface is smooth and scaly in view of utilizing the interference of the parallel thin film. For example, 0.01 to 5 μm
Are preferred, and have a length or width in the range of 1 to 100 μm. The aspect ratio is 10
It is desirably in the range of 250. Here, the aspect ratio is a comparison between the major diameter of the metal powder and the thickness of the metal powder.

The metal powder coated as described above is
By heating at 0 ° C. or higher and lower than the melting point of the metal powder, a colored metal powder pigment exhibiting a strong color can be obtained. In the present invention, the hydrolyzate of metal alcoholate formed on the surface of the metal powder usually has a small refractive index because it is in an amorphous state, and therefore has a weak light interference effect.
Therefore, in order to cause the interference effect of light to occur more strongly,
It is necessary to crystallize the coating film made of the hydrolyzate by heating to increase the refractive index. The above object can be achieved by heating a metal oxide obtained by hydrolyzing the metal alcoholate used in the present invention at a temperature of 400 ° C. or higher.

Specific examples in the case of using titanium alcoholate, which is a preferable example in the present invention, are shown below. When the heating temperature is lower than 400 ° C., the structure of the coating film formed by hydrolysis is anatase-type titanium oxide having a low crystallinity as a result of analysis by X-ray diffraction. On the other hand, when the heating temperature is 400 ° C. or higher, the structure of the coating film is an anatase-type titanium oxide having a relatively high crystallinity or, depending on conditions, a mixture of anatase-type titanium oxide and rutile-type titanium oxide. In the example of JP-A-1-110568, the heating temperature is at most 250 ° C.

When comparing the crystal forms of titanium oxide, the rutile type has a higher refractive index than the anatase type, and for the same anatase type, the higher the crystallinity, the higher the refractive index.
In other words, the refractive index of the coating film whose heating temperature is 400 ° C. or higher is
Since the heating temperature is higher than the case where the heating temperature is 350 ° C. or lower, a clear color flop property is exhibited when a film is formed.

The transition from the anatase type to the rutile type generally requires a temperature of about 700 ° C. or higher. However, among the metal substrates, for example, the melting point is 66 as in aluminum.
When the temperature is 0 ° C., usually, the crystal structure of the coated titanium oxide is an anatase type, but by mixing a small amount of soot oxide or chromium oxide with the titanium oxide composition, or by using carbon dioxide gas as an atmosphere gas to be heated and fired, A rutile phase can be generated even at a temperature lower than the melting point of aluminum.

As described above, by coating a metal powder with a coating containing a metal oxide, a colored metal powder pigment having a wide variety of color tones due to interference colors, high concealing properties, and excellent workability can be obtained. By using it as a paint pigment, it was possible to obtain a coating film, printed matter, molded article, etc. having a colorless flop property and having a novel metallic feeling without pigment aggregation.

The term "color flop property" as used in the present invention refers to the spectral reflection obtained when the color tone changes depending on the angle observed by visual observation and the light receiving angle with respect to the incident angle is changed with a spectrophotometer. The one in which the pattern of the rate curve changes and the one in which the brightness simply changes are excluded. Paint (including ink) using colored metal powder pigment of the present invention
The composition can be used as a solvent-type paint, a water-based paint, a powder paint, and the like. These are mainly composed of two basic components, ie, (a) a paint resin and (b) a colored metal powder pigment. In the case of paints and water-based paints, the third component further contains (c) a diluent.

As the coating resin for the solvent type coating, any of the coating resins conventionally used in metallic coatings can be used. As such a resin,
For example, acrylic resin, alkyd resin, oil-free alkyd resin, vinyl chloride resin, urethane resin, melamine resin, unsaturated polyester resin, urea resin, cellulose resin, epoxy resin, silicone resin, cumarone resin, cumarone-indene resin, xylene Resins, phenolic resins, ketone resins, fluororesins, and the like can be used, and these may be used alone or as a mixture. Also,
Especially when used as a top coating for automobiles, resins for acid rain countermeasures that have recently become a problem, for example,
It is also possible to use a combination of a polymer having an acid group and a polymer having an epoxy group.

The most commonly used combination in the coating composition of the present invention is an acrylic resin / melamine resin combination. In this case, the melamine resin acts as a cross-linking agent for the acrylic resin. For example, as the acrylic resin, acrylic acid and its derivative monomers (methyl acrylate, ethyl acrylate, etc.), methacrylic acid and methacrylic acid derivative monomers (methyl methacrylate, ethyl methacrylate, etc.) as main components, and, if necessary, acrylamide And those obtained by copolymerizing acrylonitrile, styrene-vinyltoluene, vinyl acetate and the like. As the melamine resin, methylol melamine, methylated methylol melamine, butylated methylol melamine and the like are used. As a resin used in combination with the acrylic resin, a polyester resin, an alkyd resin, a fluororesin, or the like is generally used.

The colored metal powder pigment used in the solvent type paint is 0.1 parts by weight to 1 part by weight based on 100 parts by weight of the resin for the paint.
00 parts by weight. It is particularly preferable to use 1 part by weight to 50 parts by weight. When the content of the colored metal powder pigment is less than 0.1 part by weight, the coloring effect is insufficient, and when the content is more than 100 parts by weight, the amount of the metal powder pigment in the paint becomes too large, and The workability deteriorates, and the physical properties of the coating film are poor, which is not practical. The colored metal powder pigment may be pasted with a solvent-type paint diluent, if necessary, in order to facilitate dispersion.

Examples of the diluent in the solvent type paint include aromatic compounds such as toluene and xylene, aliphatic compounds such as hexane, heptane, octane and mineral spirit, alcohols such as ethanol and butanol, ethyl acetate and acetic acid. Examples thereof include esters such as butyl, ketones such as methyl ethyl ketone, chlorine compounds such as trichloroethylene, and cellosolves such as ethylene glycol monoethyl ether. These diluents are used alone or in combination of two or more. The composition is determined in consideration of solubility in a coating resin, coating film forming properties, coating workability, and the like.

[0039] Flake pigments, coloring pigments, dyes, photochromic substances, lubricants, wetting agents, dispersants, anti-separation agents, leveling agents, slip agents, anti-skinning agents commonly used in the paint industry. And additives such as a gelling inhibitor, an antifoaming agent, a curing catalyst, an ultraviolet absorber, an antioxidant, a surface conditioner, an anti-sagging agent, a thickener, and a microgel.

Particularly, specific examples of the coloring-related materials referred to in the present invention include aluminum flake, plate-like iron oxide, phthalocyanine flake, graphite, titanium dioxide-coated mica, and colored mica. Color pigments include azo lake pigments, phthalocyanine pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, graphite, and yellow oxide. Iron, red iron oxide, carbon black, titanium dioxide, etc., and dyes include azo dyes, anthraquinone dyes, indigoid dyes, sulfur dyes, triphenylmethane dyes, pyrazolone dyes, stilbene dyes, nitro dyes, etc., and photochromic substances As Azobe Zen acids, spiropyrans, spirooxazines, phenothiazines, and the like.

Further, since the orientation and the like of the pigment in the coating composition of the present invention affect the colorability, the lubricant and the dispersant are also one factor related to the coloration. , Stearic acid, palmitic acid, oleic acid,
Fatty acid-based lubricants such as linoleic acid, linolenic acid, etc., and dispersing agents include polyacrylic acid partial alkyl ester, polyalkylene polyamine, formalin condensate of naphthalene sulfonate, polystyrene sulfonate, polyacrylate , A salt of a copolymer of a vinyl compound and a carboxylic acid monomer, carboxymethyl cellulose,
Polyvinyl alcohol. The lubricant and the dispersant may be provided directly on the surface of the pigment in the composition of the present invention, or may be added to the composition.

In particular, when a pearl mica pigment is used in a mixture with the colored metal powder pigment used in the present invention at an arbitrary ratio, or when an arbitrary coating composition (for example, pearl By providing a mica layer or the like), an interference color reflecting soft light is observed at the same time as an interference color having a metallic appearance, so that the color depth is increased and the design effect is further enhanced. In particular, when used as a top coat for automobiles, the particle size of the colored metal powder pigment is 1 to 50 μm, preferably 5 to 4 μm.
0 μm, more preferably in the range of 5 to 20 μm,
The particle size of the pearl mica pigment is 1 to 44 μm, preferably 5 to 44 μm.
Adjust to a range of ４０40 μm. The sharper the particle size distribution of each pigment, the higher the saturation.

The coating composition containing the colored metal powder pigment of the present invention can also be used for water-based coatings. In this case, the water concentration in the coating is adjusted so that the metal and water do not react to generate hydrogen gas. It is necessary to prevent the generation of hydrogen gas by lowering or adding a reaction inhibitor such as a phosphate ester. As the resin for the water-based paint, a water-soluble resin or a water-dispersible resin, or a single or mixture thereof can be used.
The type varies depending on the purpose and application, and is not particularly limited. Generally, acrylic resin, amide group-containing acrylic resin, acrylic / cellulose acetate butyrate mixed resin, epoxy resin, alkyd resin, nitrocellulose Resins, polyamide resins, polyester resins, polyurethane resins, epoxy-modified alkyd resins, and the like, as well as the aforementioned resins for acid rain countermeasures. These resins, alone or melamine resin,
It can be used in combination with a curing agent such as a urea resin, an isocyanate compound and a blocked isocyanate compound.

The colored metal powder pigment used in the water-based paint is 0.1 to 1 part by weight based on 100 parts by weight of the resin for the paint.
00 parts by weight. It is particularly preferable to use 1 part by weight to 50 parts by weight. When the content of the colored metal powder pigment is less than 0.1 part by weight, the coloring effect is insufficient, and when the content is more than 100 parts by weight, the amount of the metal powder pigment in the paint becomes too large, and the coating workability is increased. And the physical properties of the coating film deteriorate, which is not practical.

The various additives may be those usually used in the art, such as the above-mentioned additives and other organic solvents, water, etc., and may be those which do not impair the effects of the present invention. If added, it may be added. The coating composition using the colored metal powder pigment in the present invention can be used for powder coating, but in order to obtain a coating film having excellent appearance and the like, the insulating material such as a silicon compound is coated with the colored metal powder pigment. Or to provide a film thereof, or to coat the colored metal powder pigment with a resin in advance, or to coat another colored pigment with the resin after attaching the other colored pigment to the colored metal powder pigment. You can also.

Examples of the resin used in the powder coating include acrylic resin, alkyd resin, polyester resin, polyurethane resin, polyvinyl acetate resin, polyvinyl chloride resin, epoxy resin, nitrocellulose resin, and fluororesin. The compounding amount of the coloring metal powder pigment is 0.1 to 100 parts by weight, based on 100 parts by weight of the coating resin powder,
Preferably, 1 to 50 parts by weight is appropriate. If the amount is too small, a sufficient decorative effect cannot be obtained, and if the amount is too large, the physical properties of the powder coating film tend to decrease.

When a coating film is prepared using the coating composition of the present invention, the substrate to be coated may be a metal such as iron, aluminum, copper or an alloy thereof, or an inorganic material such as glass, cement or concrete. , Polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer,
Acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyacryl, polyester, ethylene-polyvinyl alcohol copolymer, vinyl chloride resin, vinylidene chloride resin,
Examples include resin molded products such as polycarbonate and polyurethane, plastic materials such as various FRPs, wood, and fiber materials. It is optional to apply an appropriate undercoat or precoat treatment to these substrates in advance.

The coating composition (including ink) of the present invention comprises:
Spray painting, brush painting, dip painting, roll painting,
Painting and printing can be performed by a conventionally known coating method, printing method, and the like such as flow coating, relief printing, planographic printing, intaglio printing, gravure printing, and stencil printing. For example, in the coating of automobiles, undercoating or intermediate coating with an electrodeposition paint or the like is usually performed after surface chemical conversion treatment, and then overcoating is performed after the coating film is cured. In this case, the coating operation is performed by air spray coating, electrostatic coating or the like using an atomizing type coating machine. The top coat usually comprises a base coat and a top coat layer thereon, and the coating composition of the present invention is generally used as the above base coat. The coating film of the base coat is preferably formed in a dry film thickness range of 10 to 25 μm. If the film thickness is less than 10 μm, the underlying concealing property is reduced, causing color unevenness. Next, a clear top coat is applied as a top coat on the base coat.

Even if a clear coat layer is applied to a base coat film prepared by using the coating composition of the present invention, the interference color is not impaired, so that it can be used without any problem. As the clear coat paint composition, one that is usually used in combination with the base paint is used, but is not particularly limited. Furthermore, in order to obtain design properties, a coating film prepared using the colored metal powder pigment of the present invention may be provided on a coating film containing a known coloring pigment or dye, or conversely, the pigment of the present invention may be provided. A coating film containing a known coloring pigment or dye may be provided on the coating film produced by using the method.

The coating composition using the colored metal powder pigment of the present invention can be kneaded with a resin to create a molded product having a novel design. The resin material is not particularly limited, and may be any resin material that can be subjected to general molding such as injection molding and transfer molding. The paint composition of the present invention is applicable to various kinds of inks such as paints, printing inks, writing inks, copying inks, and specialty inks for automobiles, bicycles, toys, home appliances, buildings, vehicles, industrial machines, and parts thereof. And it can be used for resin compounds, ceramic products, cosmetics and the like.

[0051]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples are shown below, but the present invention is not limited to these. The production of the metallic coated plate and the evaluation of the color tone are as follows. (1) Preparation of metallic coated plate 3 parts by weight of colored metal powder pigment, 72 parts by weight of thinner (toluene / ethyl acetate / butyl cellosolve = 7/2/1 [weight ratio]), Acrydic 47-712 (Dainippon Ink Chemical Co., Ltd.) 32) parts by weight, Super Beckamine J-820
(Dai Nippon Ink Chemical Co., Ltd.)
The mixture was stirred and mixed with a paint shaker for 30 minutes to prepare a coating composition of the present invention.

An aluminum plate (1 × 70 × 150) was applied to the coating composition by air spray coating so that the film thickness became 15 μm.
mm). After allowing to stand at room temperature for 30 minutes, a top clear having the following composition was applied thereon by air spray coating so that the film thickness became 35 μm. [Top clear composition (parts by weight)] 220 parts by weight of xylene, 200 parts by weight of Acrydic 44-179 (manufactured by Dainippon Ink and Chemicals, Inc.), Super Beckamine J-82
0 (manufactured by Dainippon Ink and Chemicals, Inc.) 50 parts by weight.

After leaving at room temperature for 1 hour,
For a minute to obtain a metallic coated plate. (2) Evaluation of color tone The color tone and color flop of the metallic coated plate were evaluated as follows. Judgment by visual observation (comparing whether the highlight color near the regular reflection angle of the incident light and the shade color at the angle where the incident light is hardly reflected change). Colorimetry using a multi-angle spectrophotometer (Macbeth, CE-740) (measured the spectral reflectance at positions shifted by 20 degrees and 45 degrees from the specular reflection angle of incident light, and compare the obtained spectral reflectance curves) ).

[0054]

Example 1 Specific surface area 2.4 m ^{2 /} g (BET
Method) aluminum paste (MG-21, Asahi Kasei Corporation)
Was washed with petroleum benzene / acetone, filtered by suction, dried at 50 ° C. for 2 hours, and 50 g was taken.
After suspending in 500 ml of butanol, while maintaining that state,
12.75 g of tetra-n-butyl titanate was added. Then, while stirring was continued, a solution obtained by diluting 6.75 g of water into 120 g of n-butanol was used for 1.
Added at a rate of 5 g / min. Next, 100 g of water was added at a rate of 1 g / min by the same metering pump so that the amount of butanol in the system became saturated with water. After this slurry was washed with butanol, the slurry was washed with Nutsche. Suction filtration was carried out using filter paper No. 6 and then taken out.

This powder had a golden color. Further, when this powder was heated at 400 ° C. for 15 minutes, a colored aluminum powder having a stronger golden color was obtained. Using the obtained colored aluminum powder pigment, a metallic coated plate was prepared according to the method described above, and the color flop property was evaluated. As a result, the highlight was gold and the shade was purple. As shown in FIGS. 1 and 2, the measurement results of the multi-angle spectrophotometer have a high reflectance around 550 to 700 nm (yellow to red) at 20 degrees, but around 420 nm (purple) at 45 degrees. The portion having a high reflectance moved, which confirmed the result of the visual judgment.

[0056]

Example 2 Example 1 was repeated except that the amount of tetra-n-butyl titanate added was 31.85 g, and the amount of water that was initially mixed with n-butanol and gradually added was 16.88 g. A colored aluminum powder pigment was obtained in the same manner as in Example 1. Next, as in Example 1, the powder was heated at 400 ° C. for 1 hour.
A metallic coated plate was prepared using the colored aluminum powder pigment obtained by heating for 5 minutes, and the color flop property was evaluated.

As a result, the highlight became red and the shade became gold. The measurement result of the multi-angle spectrophotometer is 400 nm at 20 degrees as shown in FIGS.
(Purple) and high reflectance around 680 nm (red).
0 nm (blue) is low, but at 45 degrees, 400 nm
The pattern changed such that the change in reflectance other than nm (purple) generally decreased, confirming the result of the visual judgment.

[0058]

Example 3 The procedure of Example 2 was repeated, except that the firing temperature was 600 ° C. instead of 400 ° C.
A metallic coated plate was prepared, and the color flop property was evaluated. As a result, the highlight is red, the shade is golden and 4
It became the same tendency as 00 ° C, but the degree of change was 600 ° C
Became bigger. This is shown in FIGS.
00 ° C (Example 3) is 4 times higher than 400 ° C (Example 1).
This is supported by the fact that the reflection intensity at 5 degrees is increased.

[0059]

Example 4 A pigment obtained by blending the colored aluminum powder pigment obtained in Example 2 with Pearl Mica (Pearl Glaze 90-30R, manufactured by Nippon Koken Co., Ltd.) at a weight ratio of 1: 1 was used as a pigment. A metallic coated plate was produced. As a result, in addition to the interference color from the colored aluminum powder pigment having a metallic appearance, an interference color derived from pearl mica that reflects soft light was also observed at the same time, and a metallic coated plate having a deep color was obtained.

[0060]

Comparative Example 1 The procedure of Example 1 was repeated, except that the firing temperature was 250 ° C. instead of the firing temperature of 400 ° C.
A metallic coated plate was prepared, and the color flop property was evaluated. As a result, although the coating film of the product baked at 250 ° C. developed a strong reddish gold color, there was no change in color between highlights and shades, and only lightness was changed. The measurement results of the multi-angle spectrophotometer are shown in FIGS.
As shown in FIG. 7, only the reflection intensity was weakened, and the curve pattern did not change.

[0061]

Comparative Example 2 A metallic coating film was prepared using pearl mica (Pearl Glaze 90-30R, manufactured by Nippon Koken Co., Ltd.) alone as a pigment. As a result, although the interference color and the color flop property were confirmed, the hiding property was insufficient and the underlying aluminum plate was clearly observed.

[0062]

Comparative Example 3 Friend Color F500GL, a commercially available green metallic pigment (Showa Aluminum Powder Co., Ltd.)
Was used as a pigment to prepare a metallic coated plate. As a result, although a green metallic coating film was obtained, there was not much difference from the color tone obtained by simply blending a conventional green pigment with aluminum. Also, the color of the highlight and shade remained green, only the brightness changed. Further, as shown in FIGS. 1 and 2, the spectral reflectance curves also showed only a change in the reflection intensity, and there was no change in the pattern and peak position in the graph.

[0063]

Comparative Example 4 A metallic coated plate was prepared using a commercially available orange pigment, Paliochrome (manufactured by BASF) as a pigment. As a result, aggregation of the pigment was observed, and a clean metallic coating film could not be produced. Similarly to Comparative Example 3, the obtained coating film only changed in lightness, and no change in color was observed.

[0064]

Example 5 Colored aluminum powder pigment 2 obtained in Example 1
4.5 parts by weight, acrylic resin emulsion (dispersant) 1
1.5 parts by weight, 48.0 parts by weight of water, and 16.0 parts by weight of propylene glycol were blended and mixed by stirring with a homomixer for 5 minutes to obtain an aqueous gold pigment ink.

The resulting ink exhibited a vivid gold color due to interference colors. Using this ink, a gravure coater (K
PRINTING PROOFER, RK Pri
nt-Coat Instruments Ltd.
Gravure printing. In the obtained printed matter, the highlight was golden and the shade was purple, similarly to the coating film of Example 1, and the color flop property was confirmed.

[0066]

Comparative Example 5 The procedure of Example 4 was repeated, except that bronze powder BS-607 (manufactured by Toyo Aluminum Co., Ltd.) was used instead of the colored aluminum powder pigment obtained in Example 1 used in Example 4. In the same manner as in Example 4, an aqueous gold pigment ink was obtained. As a result, it exhibited a dull, slightly reddish gold color. As a result of performing gravure printing using this ink in the same manner as in Example 4, almost no interference color derived from pearl mica was observed, and no color change was observed as in Comparative Examples 3 and 4.

[0067]

Example 6 Colored aluminum powder pigment 4 obtained in Example 1
96 parts by weight of a non-colored polyester resin coating powder (average particle diameter 35 μm) were mixed with a universal mixing stirrer to prepare a powder coating. Using this paint, it was applied at an applied voltage of 100 V by a corona charging type electrostatic powder coating machine MPSI-C (manufactured by Matsuo Sangyo Co., Ltd.) and baked at 180 ° C. for 20 minutes. The highlight of the obtained coating film exhibited a bright gold color due to the interference color, and the shade became purple.

[0068]

Comparative Example 6 The procedure of Example 5 was repeated, except that bronze powder 3L7 (manufactured by Fukuda Metal Foil & Powder Co., Ltd.) was used instead of the colored aluminum powder pigment obtained in Example 1. A powder coating film was prepared in the same manner as in Example 5. The obtained coating film was dull gold, and color unevenness was observed.

[0069]

Industrial Applicability The colored metal powder pigment of the present invention is a metal powder pigment having a wide variety of color tones due to interference colors, high concealing properties and excellent workability. A new metallic coating film free from aggregation can be obtained.

[Brief description of the drawings]

FIG. 1 is a spectral reflectance curve at 20 degrees of an example and a comparative example.

FIG. 2 is a spectral reflectance curve at 45 degrees of an example and a comparative example.

Claims (8)

[Claims] 1. After hydrolyzing a substance represented by the following general formula (1) and coating the surface of a metal powder with the product,
A colored metal powder pigment which is heated at a temperature of 0 ° C. or higher and lower than the melting point of the metal powder. Embedded image (Wherein, M is a metal atom, R is an alkyl group, n is 1 to 40)
Represents an integer. ) 2. A product obtained by hydrolyzing a substance represented by the general formula (1) in an amount of 1 mg or more and 360 mg or less as a metal per 1 m ² of the surface area of the metal powder.
The colored metal powder pigment of the above. 3. The colored metal powder pigment according to claim 1, wherein the metal atom M is titanium or zirconium. 4. The method according to claim 1, wherein the metal powder is aluminum.
Or the colored metal powder pigment according to 2. 5. A coating composition containing the colored metal powder pigment according to claim 1, as at least a part of a pigment component. 6. A coating composition comprising a colored metal powder pigment exhibiting an interference color coated with a coating containing a metal oxide, and capable of imparting a color flop property to the coating. 7. A coating film using the coating composition according to claim 6. 8. After hydrolyzing the substance represented by the general formula (1) and coating the surface of the metal powder with the product, the product is heated at 400 ° C.
The method for producing a colored metal powder pigment according to any one of claims 1 to 4, wherein the heating is performed at a temperature lower than the melting point of the metal powder.