JP2003012964A - Metal pigment composition, production method thereof, coating composition and ink composition containing the metal pigment composition - Google Patents

Abstract

(57) Abstract: A leafing property is imparted to a resin-coated metal pigment and a coloring metal pigment to which a coloring pigment has been adhered, to which the leafing property cannot be imparted conventionally. SOLUTION: A silane coupling agent having a CF ₃ group at a terminal and / or a hydrolysis product thereof, or a condensate thereof is added to a resin-coated metal pigment or a coloring metal pigment to which a coloring pigment is attached. A leafing metal pigment composition obtained by mixing. It is preferable to mix water and a hydrolysis catalyst with the metal pigment composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a leafing metal pigment composition, and more specifically,
The present invention relates to a leafing resin-coated metal pigment composition, a leafing colored metal pigment composition, a method for producing the same, an ink, a paint, and the like using the metal pigment composition.

[0002]

2. Description of the Related Art Conventionally, metal pigment compositions containing metal flakes such as aluminum flakes have been used for automobile parts, for the purpose of imparting aesthetic properties, reflectivity and moisture permeation resistance.
It is preferably used for industrial machinery, furniture, interior and exterior of buildings, home appliances, etc.

Generally, as the metal pigment composition, a non-leafing metal pigment composition containing metal flakes such as aluminum flakes is known and used, for example, for coating automobile bodies. Non-leafing metal pigments have a high affinity with coating resins by adsorbing unsaturated fatty acids such as oleic acid on the surface of metal pigments shaped like flake, and when formed into a coating film. In addition, the metal flakes are dispersed inside the coating film and are randomly arranged, and have a scale-like glitter feeling.

On the other hand, for example, automobile parts, home appliances,
For cosmetic containers, lighting equipment, outdoor lights, furniture parts, etc.
In many cases, it is required that the non-leafing metal pigment composition imparts a mirror-like brilliance rather than a scale-like glitter. In such a part having a mirror-like brilliance, the surface thereof is generally covered with a metal foil such as an aluminum foil, or a metal thin film is deposited and adhered on the surface by metal plating or metal deposition.

However, in the method of coating the surface with a metal foil, wrinkles are partially generated on a base material having a complicated shape having irregularities on the surface of the base material, and the base material is uniformly coated with the metal foil. There is a problem that you cannot do it. Further, in the method by metal plating, it is necessary to be limited to a conductive base material, or to form a conductive layer on the base material surface, and it is necessary to immerse the entire base material in a plating bath. The manufacturing process is complicated and there are various restrictions on equipment. In addition, in the method of depositing a metal, it is necessary to install the base material in a vacuum or a reduced pressure container, and there is a problem that it cannot be applied to a large-sized base material, and it is also necessary to reduce the pressure in the manufacturing process. There are limits to practical application.

Therefore, in order to impart a mirror-like brilliance to such articles, a method of using a leafing metal pigment composition has been developed, irrespective of a method of coating with a metal foil, metal plating, or metal deposition. It has been.

The leafing metal pigment composition is specifically, for example, aluminum flakes capable of forming a smooth flat surface by finely pulverizing a metal material such as aluminum and shaping it into a flaky shape. A metal pigment composition containing a mixture of metal flakes and a coating resin. For example, leafing aluminum paste and bronze powder. A leafing metal pigment composition is one in which a saturated fatty acid such as stearic acid is adsorbed on the surface of a metal pigment shaped like a flake to reduce the affinity with a coating resin, and when formed into a coating film. It floats on the upper layer of the coating film and is arranged in parallel with each other to form a smooth flat surface, which gives a mirror-like brilliance.

However, the adhesiveness between the saturated fatty acid adsorbed on the surface of the leafing metal pigment and the resin used in the paint or ink is generally poor, and peeling easily occurs at the interface between the coating resin and the metal pigment. Problems have occurred in terms of scratch resistance, chemical resistance, weather resistance, stain resistance, and the like. Further, when a clear resin is applied over the coating film containing the leafing metal pigment in an uncured state by a wet-on-wet method, the orientation of the aluminum flakes tends to be disturbed and the appearance tends to be deteriorated.

However, when a coating film containing a leafing metal pigment is heat-cured and then a clear resin is further applied thereon, the interlayer adhesion with the clear coating film tends to be insufficient. Therefore, when applied on a base material with a complicated surface shape, water or the like penetrates from the cracked part in the part where the clear coating film thickness is insufficient or the part where the clear coating film does not wrap around sufficiently, and the metal pigment Had a problem in terms of scratch resistance, chemical resistance, weather resistance, stain resistance, etc. Furthermore, the rust preventive power of saturated fatty acids is weak, and the rust preventive power was insufficient to prevent corrosion of metal pigments by chemicals.
The chemical resistance such as alkali resistance was also insufficient.
In addition, it has a problem of low storage stability due to a problem of leafing property after long-term storage.

Therefore, while overcoming these drawbacks of the leafing metal pigment composition and maintaining or improving the mirror-like brilliance of the coating film containing the leafing metal pigment composition, Various researches and developments have been conducted to improve the adhesion and adhesion between clear resin and metal pigment, improve scratch resistance, chemical resistance, weather resistance, stain resistance, and improve storage stability. It has been done.

For example, in order to improve the interlayer adhesion between the coating film containing a metal pigment and the clear coating film, at least one of the coating film containing the metal pigment and the clear coating film contains a zircoaluminate coupling agent. A multilayer coating system containing a leafing metallic finishing method (JP-A-1-307475), an undercoat layer containing leafing aluminum flakes, and an overcoat layer containing an acidic adhesion promoter (JP-A-1-307475). 3-95275) or a coating film containing a cured metal pigment, after applying a composition containing a polymer formed by using a phosphoric acid group-containing unsaturated monomer and a hydroxyl group-containing unsaturated monomer. , A coating film forming method of applying a clear paint (Japanese Patent Laid-Open No. 10-34069) has been proposed.

Then, in order to improve both the storage stability of the metal pigment composition and the intercoat adhesion between the coating film containing the metal pigment and the clear coating film, it is necessary to coat the aluminum flakes with an alkyl phosphate ester. A characteristic leafing metallic paint (JP-A-10-219150) has also been proposed.

Furthermore, in order to improve the storage stability of the water-based metal pigment composition, a metallic water-based coating composition characterized by mixing a leafing aluminum pigment and a non-leafing aluminum pigment (Japanese Patent Laid-Open No. 2001-2001).
11389 publication) is also proposed.

In addition, a composition containing a specific petroleum-based resin as a binder resin is used in order to obtain a deeper glittering feeling than the mirror-like glittering feeling obtained by a general leafing metal pigment composition. , Aluminum flakes are allowed to settle in the lower layer of the coating film to form a smooth flat surface (JP 2001-81359 A).
Issue).

Further, a coating composition characterized in that a non-leafing aluminum flake is mixed with a fine metal foil in order to obtain a mirror-like brilliance by using the non-leafing aluminum flake (JP 2000-219A).
No. 830), a coating film forming method in which a coating material containing non-leafing aluminum flakes and a coating material containing a fine metal foil are sequentially applied (Japanese Patent Application Laid-Open No. 2000-31857), and non-leafing property on an uncured coating surface. There is also proposed a method for forming a metallic coating film (Japanese Patent Laid-Open No. 11-90318), which comprises coating a composition containing aluminum flakes and an organic solvent and then applying a clear coating.

However, in spite of various efforts as described above, the adhesion between the coating resin and the metal pigment, the adhesion between the clear resin and the metal pigment, the scratch resistance, the chemical resistance, the weather resistance, and the stain resistance. A leafing metal pigment composition that has sufficiently satisfactory performances in terms of storage stability, is excellent in the mirror-like brilliance of the coating film, and is sufficiently profitable in terms of manufacturing cost is still obtained. Didn't.

As a highly weather-resistant fluorine-containing copolymer coating material, a coating material containing a hydroxyl-containing full olefin / vinyl ether copolymer and a polyisocyanate curing agent has been known. A metallic paint composition obtained by adding a metallic pigment such as aluminum flake to this paint is used as a paint for automobiles that is exposed outdoors by taking advantage of its high weather resistance.

Further, in a metallic coating composition applied to articles used outdoors such as automobiles, especially when the coating film formed from the metallic coating composition is the outermost layer, weather resistance and stain resistance are Often required.
As a means for improving the stain resistance of a general coating material, a method of adding a partial hydrolysis-condensation product of an alkoxysilane to the coating material (JP-A-8-176304), a fluoroolefin, a (meth) acrylic acid ester and a water A coating composition containing a fluorine-containing copolymer obtained by copolymerizing an olefinic monomer having a decomposable silyl group (JP-A-9-30
No. 2301) is proposed.

As means for improving the stain resistance and weather resistance of the metallic paint, fluoroolefin,
A metallic coating composition containing a fluorinated copolymer obtained by copolymerizing a (meth) acrylic acid ester and an olefinic monomer having a hydrolyzable silyl group, and a silane coupling agent (JP-A-2000-186234). Gazette) has been proposed. However, the invention is not intended to improve the stain resistance and weather resistance of the leafing metal pigment composition, and does not refer to chemical resistance. Further, the present invention does not mention a resin-coated metal pigment or a colored metal pigment to which a color pigment is attached.

A metallic paint containing a bright pigment and a phosphoric acid group-containing compound as a metal piece obtained by crushing a vapor-deposited metal film (JP-A-2000-178478).
(Japanese Patent Laid-Open Publication) also, it is preferable to contain a silane coupling agent, but in the present invention,
The silane coupling agent is added to enhance the adhesiveness of the metallic coating film layer, and the presence of the silane coupling agent does not necessarily mean that the bright pigment exhibits leafing properties. Further, in the present invention, there is no mention of chemical resistance, nor is there any mention of resin-coated metal pigments or colored metal pigments having colored pigments attached thereto.

[0021]

On the other hand, since the resin-coated metal pigment is excellent in adhesion to resin, acid resistance and alkali resistance, if the resin-coated metal pigment is used, the above-mentioned leafing metal pigment composition is used. Although it is considered that the drawbacks of the products can be overcome, existing resin-coated metal pigments do not exhibit leafing properties, and the color tone having a mirror-like luster characteristic of leafing metal pigment compositions cannot be obtained. Further, even if saturated fatty acids are adsorbed on the coating resin layer in order to give the leafing property, the leafing property is hardly improved. Further, in recent years, a colored metal powder pigment has been developed by a technique of adsorbing a color pigment to a metal powder pigment such as an aluminum pigment and coating a resin as necessary, but such a colored metal powder pigment also has a leafing property. Not shown.

Therefore, the above-mentioned leafing metal pigment composition has the following properties in terms of adhesion between coating resin and metal pigment, adhesion between clear resin and metal pigment, chemical resistance, weather resistance and stain resistance. In addition to overcoming the drawbacks and imparting a leafing property to the colored metal pigment, a characteristic color tone that has various colors and specular luster, scratch resistance, and chemical resistance,
In order to obtain a leafing resin-coated metal pigment composition having weather resistance, stain resistance, and storage stability at the same time, there is a strong demand for development of a technique for imparting leafing property to the resin-coated metal pigment. , It has not been realized yet.

The object of the present invention is to impart a leafing property to a resin-coated metal pigment which has been unable to provide a leafing property in the past, and has a mirror-like luster, a color tone, chemical resistance, and weather resistance. It is intended to provide a leafing resin-coated metal pigment composition having both stain resistance and a method for producing the same.

Another object of the present invention is to impart a leafing property to a colored metal pigment to which a color pigment is adhered, and to provide various colors and a mirror-like brilliance which cannot be obtained by conventional techniques. It is an object of the present invention to provide a colored metal pigment composition exhibiting a new design that also has a combination, and a method for producing the same.

[0025]

DISCLOSURE OF THE INVENTION The present inventor has imparted a leafing property to a coated metal pigment, which has hitherto been unable to impart a leafing property, and at the same time, provides a metal pigment composition with chemical resistance and weather resistance. , And stain resistance, to pay attention to the possibility that it is effective to add a fluorine-containing copolymer or a silane coupling agent, as a result of earnest research,
It was found that the object of the present invention can be achieved by using a specific silane coupling agent, and the present invention has been completed.

The present invention is a metal pigment composition containing a metal pigment and a silane coupling agent having a structural formula having a CF ₃ group at the terminal and / or a hydrolysis product thereof, or a condensate thereof. .

Here, a compound represented by the following chemical formula (1) can be used as the silane coupling agent.

[0028]

[Chemical 2]

(N is an integer of 0 to 20, m is an integer of 2 to 4, X, Y are R or OR or Cl, and R is 2 carbon atoms.
It is the following alkyl groups. Further, as the silane coupling agent, a compound in which one or more polar functional groups shown below are further introduced into the alkyl group in the chemical formula (1) can be used. -CO
O -, - COS -, - CONH -, - SO 2 NH -, -
S- Furthermore, the surface of the metal pigment may be coated with a resin. Further, the metal pigment may be colored with a coloring pigment. The content of the silane coupling agent and / or its hydrolysis product or the condensation product thereof is 100 parts by weight of the metal pigment.
It is preferably 0.1 to 20 parts by weight.

Then, the present invention includes a method for producing the metal pigment composition having the above-mentioned blending amount, characterized in that the metal pigment is mixed with the silane coupling agent represented by the chemical formula (1).

The present invention also includes a method for producing the metal pigment composition, which comprises mixing water and a hydrolysis catalyst in addition to the silane coupling agent represented by the chemical formula (1).

In the present invention, the hydrolysis catalyst is
Phosphoric acid, polyphosphoric acid, molybdic acid, phosphomolybdic acid, peroxidized polymolybdic acid, vanadic acid, chromic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphonic acid, alkylphosphonic acid, and salts thereof, and alkyl having 6 or less carbon atoms. At least one selected from the group consisting of an amine, an alkylenediamine having 6 or less carbon atoms, an alkanolamine having 6 or less carbon atoms, a silane coupling agent having an amino group, and ammonia. Including the manufacturing method of.

Further, the present invention includes a coating composition or an ink composition containing the metal pigment composition, a binder, and a solvent.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by showing embodiments.

The metal pigment composition of the present invention comprises a metal pigment and
It contains a silane coupling agent having a structural formula having a CF ₃ group at the terminal and / or a hydrolysis product thereof, or a condensate thereof.

In general, the silane coupling agent is a silicon compound having a structure represented by the chemical formula (2) and has a property of being capable of chemically bonding to both inorganic materials and organic materials which are not well compatible with each other. The silane coupling agent of the present invention also has a substituent that easily reacts with an inorganic substance at the X1, X2, and X3 positions of the chemical formula (2), and has a substituent that easily reacts with an organic substance having a CF ₃ group at the terminal. ) Y position. In the chemical formula (2), n represents an integer of 0 or more.

[0037]

[Chemical 3]

The silane coupling agent used in the present invention is preferably a silane coupling agent represented by the following chemical formula (1).

[0039]

[Chemical 4]

(N is an integer of 0 to 20, m is an integer of 2 to 4, X, Y are R or OR or Cl, and R is 2 carbon atoms.
It is the following alkyl groups. The same applies to the following sentences. ) N is preferably 0 to 20, but a particularly preferred range is 0 to 10. When n is larger than 20, the adhesion between the metal pigment and the binder such as the coating resin tends to be lowered, and a problem such as peeling is likely to occur at the interface between the coating resin and the metal pigment.

M is preferably an integer of 2 to 4. When m is less than 2, the affinity with the resin tends to decrease, and thus problems such as cissing and poor dispersibility are likely to occur when it is made into a paint. When m is greater than 4, the effect of improving the leafing property and the adhesiveness is not so much seen relative to the amount added, and there is a tendency in terms of manufacturing cost.

X and Y are R or OR or Cl.
However, in the case of Cl, R or OR is more preferable because there is a problem that hydrogen chloride gas is generated in the treatment step. R is an alkyl group having 2 or less carbon atoms. When the carbon number is 3 or more, sufficient leafing property tends not to be obtained, which is not preferable.

Examples of the silane coupling agent satisfying the above conditions include compounds having the structural formulas shown in the following chemical formulas (3) to (6).

[0044]

[Chemical 5]

[0045]

[Chemical 6]

[0046]

[Chemical 7]

[0047]

[Chemical 8]

Good results are also obtained when a silane coupling agent in which one or more of the following polar functional groups is introduced into the alkyl group of the chemical formula (1) is used.

Polar functional groups: --COO--, --COS--,-
_{CONH -, - SO 2 NH -} , - S-.

Examples of the silane coupling agent satisfying the above conditions include compounds having the structural formulas shown in the following chemical formulas (7) to (12).

[0051]

[Chemical 9]

[0052]

[Chemical 10]

[0053]

[Chemical 11]

[0054]

[Chemical 12]

[0055]

[Chemical 13]

[0056]

[Chemical 14]

Further, the silane coupling agent may be used alone or in combination of two or more, if necessary.

The silane coupling agent may be used as it is or in a completely or partially hydrolyzed state according to the following reaction formula (13).

[0059]

[Chemical 15]

(N is an integer of 0 to 20, m is an integer of 2 to 4, X, Y are R or OR or Cl, and R is 2 carbon atoms.
It is the following alkyl groups. Further, such a hydrolysis product may be in a state of being condensed with a hydroxyl group on the surface of the metal powder pigment or a hydroxyl group of another hydrolysis product, and a state of being condensed with a hydroxyl group on the surface of the metal powder pigment is particularly preferable. Therefore, a better leafing property can be obtained.

In order to cause hydrolysis, it is sufficient to add water and a hydrolysis catalyst together with the silane coupling agent, but it is necessary to disperse or dissolve them in a hydrophilic solvent in advance for uniform mixing. preferable.

The amount of water added is not particularly limited, but is preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the metal pigment. When the amount of water added is less than 0.1 parts by weight, the condensation of the silane coupling agent does not sufficiently occur, and the improving effects such as leafing properties and adhesion tend to be reduced.
If the amount of water added exceeds 5.0 parts by weight, when aluminum flakes are used as the metal pigment, the aluminum flakes may react with water, which may cause problems such as agglomeration and reduction in brightness.

As the hydrolysis catalyst, it is preferable to use at least one selected from the following group (A) or group (B).

Group (A): acidic compounds and salts thereof shown below. Phosphoric acid, polyphosphoric acid, molybdic acid, phosphomolybdic acid, silicomolybdic acid, peroxypolymolybdic acid, vanadic acid, chromic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphonic acid, alkylphosphonic acid, phosphotungstic acid, silicotungstic acid, phosphorus Tungstomolybdic acid, phosphorus vanadomolybdic acid.

Group (B): Basic compounds shown below. Alkylamine having 6 or less carbon atoms, alkylenediamine having 6 or less carbon atoms, alkanolamine having 6 or less carbon atoms, silane coupling agent having an amino group, and ammonia.

Particularly preferred hydrolysis catalysts are phosphoric acid, ammonium phosphate, ammonium molybdate, phosphomolybdic acid, polymolybdic acid peroxide, triethylamine, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, ammonia,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ
-Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane,
Are exemplified.

The addition amount of the hydrolysis catalyst is not particularly limited, but it is 0.1 to 100 parts by weight of the metal pigment.
It is preferably 5.0 parts by weight. When the addition amount of the hydrolysis catalyst is less than 0.1 part by weight, the silane coupling agent is not sufficiently hydrolyzed, and the improving effects such as leafing property and adhesiveness tend to be small. When the addition amount of the hydrolysis catalyst exceeds 5.0 parts by weight, the effect of improving the leafing property and the adhesiveness is not seen so much for the addition amount, and the production cost tends to be disadvantageous.

As the hydrophilic solvent for uniformly mixing the metal pigment composition of the present invention, alcohols having 5 or less carbon atoms, polyhydric alcohols such as butyl cellosolve, ethyl cellosolve, butyl carbitol and dipropylene bricol monomethyl ether are used. Ethers, acetone and the like can be used, and the addition amount thereof is preferably an amount sufficient to uniformly disperse or dissolve water and the hydrolysis catalyst in the metal pigment composition.

The addition amount of the silane coupling agent contained in the metal pigment composition of the present invention is not particularly limited, but it is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the metal powder pigment. It is particularly preferably 0.5 to 5 parts by weight. If the amount of the silane coupling agent added is less than 0.1 part by weight, sufficient leafing property tends not to be obtained,
If the addition amount of the silane coupling agent is 20 parts by weight or more,
The physical properties (adhesiveness, etc.) of the coating film when formed into a coating film may deteriorate.

Examples of the metallic pigment used in the metallic pigment composition of the present invention include aluminum, bronze, stainless steel, zinc, copper, titanium, iron, nickel, stainless steel and their alloy flakes. Among these pigments, aluminum flakes are particularly preferable because they have excellent metallic luster, are inexpensive, and have a low specific gravity, and are easy to handle. The average particle size is preferably 1 to 100 μm, and 3 to 5
Those of 0 μm are particularly preferable. The average thickness is 0.
It is preferably from 02 to 5 μm, particularly preferably from 0.1 to 2 μm.

Further, it is particularly preferable that the shape factor obtained by dividing the average particle diameter by the average thickness is in the range of about 5 to 100. If the average particle size exceeds 100 μm, the flake pigment tends to stick out on the surface of the coating film, and the smoothness or sharpness of the coated surface tends to deteriorate. If the average particle size is less than 1 μm, a metallic feeling is obtained. Alternatively, the luster tends to decrease. When the average thickness is more than 5 μm, the smoothness or sharpness of the coated surface tends to be deteriorated and sufficient leafing property may not be obtained. In this case, not only the strength of the metal flakes tends to decrease, but also processing during the metal flake manufacturing process may become difficult.

The average particle size of the flake pigment is determined by calculating the volume average from the particle size distribution measured by a known particle size distribution measuring method such as a laser diffraction method, a micromesh sieve method and a Coulter counter method. The average thickness is calculated from the hiding power and density of the flake metal pigment.

As the metal pigment, those coated with general fatty acids such as stearic acid and oleic acid, aliphatic amines, fatty acid amides, aliphatic alcohols, acidic phosphoric acid esters and the like can be used, but the effects of the present invention can be effectively obtained. In order to utilize it, it is preferable that a resin layer is formed on the surface of the metal pigment. By forming a resin layer on the surface of the metal pigment, it is possible to improve the coating film physical properties such as chemical resistance, adhesion, weather resistance and stain resistance of the coating film applied using the resin layer.

As a method for forming a resin layer, a monomer as shown below is added to a slurry prepared by dispersing a metal pigment in an organic solvent, and azobisisobutyronitrile, while heating in an inert gas atmosphere, A method of polymerizing the monomer by adding a polymerization initiator such as benzoyl peroxide to deposit the polymer on the surface of the metal pigment is preferable. However, the method is not limited to this.

Here, examples of the polymerizable monomer include acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, 2-acrylic acid acrylate. Hydroxyethyl, 2-hydroxybutyl acrylate, 2-methoxyethyl acrylate, 2-diethylaminoethyl acrylate, butyl methacrylate, octyl methacrylate, 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, 1, 9 nonanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate,
Pentaerythritol triacrylate, trisacryloxyethyl phosphate, ditrimethylolpropane tetraacrylate, styrene, α-methylstyrene,
Vinyltoluene, divinylbenzene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, maleic acid, crotonic acid, itaconic acid, polybutadiene, linseed oil, soybean oil, epoxidized soybean oil, epoxidized polybutadiene, cyclohexene vinyl monooxide, Examples thereof include divinylbenzene monooxide.

The amount of the resin layer formed is 100
0.1 to 50 parts by weight per part by weight is preferable, and 0.5 to
40 parts by weight are particularly preferred. When the amount of the resin layer formed is less than 0.1 parts by weight, the chemical resistance and adhesion of the coating film tend to be insufficient, and the amount of the resin layer formed is less than 50 parts by weight. If the amount is large, the metallic feeling or brightness of the coating film is lowered, which may cause a problem in the smoothness of the coating film surface.

Further, a colored metal pigment can be used in the present invention. The colored metal pigment that can be used in the present invention is not particularly limited, but it is disclosed in JP-A-58-141248, JP-A-5-508424, and JP-A-1-31547.
No. 0, JP-A-9-40885, JP-A-9-5
Those having a coloring pigment adhesion layer on the surface of each particle as described in patent publications such as 9532 and JP-A-9-124973 can be used. Further, in order to effectively utilize the effects of the present invention, it is preferable that the color pigment layer is covered with a resin layer synthesized from a polymerizable monomer as shown in the examples of the polymerizable monomer. Examples of the coloring pigment include phthalocyanine, halogenated phthalocyanine, quinacridone, diketopyrrolopyrrole, isoindolinone, azomethine metal complex, indanthrone, perylene, perinone, anthraquinone, dioxazine, benzimidazolone, condensed azo, triphenylmethane, quinophthalone. , Anthrapyrimidine, titanium oxide, iron oxide, carbon black, bismuth vanadate, and the like.

In addition to the colored metal pigment to which the color pigment is attached, a colored metal pigment of the type colored by forming an interference film or a colored thin film layer on the surface of the metal pigment is also suitable.
Examples of such colored metal pigments include titanium flakes colored by oxidation or nitriding, or aluminum colored by a colored inorganic thin film layer such as iron oxide as disclosed in Japanese Patent Publication No. 1-24182. Examples thereof include pigments.

The metal pigment composition of the present invention can be produced by simply adding and mixing the silane coupling agent to the metal pigment. The addition method is not particularly limited, but a method of adding a silane coupling agent when kneading the metal pigment with a solvent in a ribbon mixer or a kneader mixer is preferable. At this time, if water and the above-mentioned hydrolysis catalyst are added together to the metal pigment under the above-mentioned compounding amount and conditions, a metal pigment composition having better leafing properties can be obtained.

The coating composition or ink composition of the present invention contains the metal pigment composition, a binder, and a solvent. Further, if necessary, various pigments, various additives and the like can be contained.

The form of the coating composition or ink composition of the present invention is not particularly limited, and includes organic solution type, non-aqueous dispersion type, aqueous solution type, water dispersion type, high solid type,
Any form such as a powder coating type can be used.

For example, in the case of a non-aqueous dispersion type coating composition, the metal pigment composition of the present invention (including the silane coupling agent of the present invention), a binder, an organic solvent and, if necessary, additives It is prepared by adding pigments and the like.

In this case, the weight concentration (P
WC) is preferably in the range of 0.1 to 30. By increasing the PWC, the metallic feeling and whiteness of the coating film are improved. However, if the PWC is too high, the interlayer adhesion tends to decrease, so it is preferable that the PWC is within the above range.

The binder used in the coating composition is preferably a resin generally used as a film-forming resin, such as acrylic resin, vinyl chloride vinyl acetate copolymer resin, polyamide resin, urethane resin, polyester resin, melamine resin, etc. The resin is exemplified.

The solvent used in the coating composition is selected in consideration of the solvent used in the production of the metallic pigment, the top coat agent, the type of the base coating film for metallic coating, and the like. Toluene, xylene, n-hexane, cyclohexane, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl Alcohol, secondary butyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl Chromatography ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate and Solvesso 100 and Solvesso 150
(Trade names, manufactured by Esso Corporation, aromatic hydrocarbon solvents) and the like. When the bright pigment is obtained as a commercial product such as a metal powder paste, the solvent contained in the metal powder paste may be included.

If necessary, various pigments, various additives, etc. may be added to the coating composition.

For example, in order to obtain various color tones in these coating compositions or ink compositions, mica, surface-colored mica, glass flakes, surface-colored glass flakes, pearls, etc. You may add such coloring pigments.

If necessary, the coating composition or ink composition may include a surface modifier, a viscosity modifier, an ultraviolet absorber, a light stabilizer, an antioxidant, a curing catalyst, a melamine resin, and a constitution. Additives for paints such as pigments, anti-settling agents, waxes such as polyethylene wax, polypropylene wax and the like can be added.

The substrate on which the coating film of the coating composition or ink composition of the present invention is formed is not particularly limited,
For example, a plastic base material or a metal base material is used.
Specific examples of the metal substrate include iron, copper, aluminum,
These include alloys and castings such as tin and zinc.

Specific examples of such a base material include vehicle bodies and parts such as automobiles and motorcycles. In particular, a cast or forged aluminum alloy wheel or an iron wheel has a complicated surface and is a part where appearance is important. Therefore, the coating composition or the ink composition of the present invention has such a base. Especially useful for timber.
It is preferable that these metal base materials are previously subjected to chemical conversion treatment with a phosphate, a chromate or the like.

The method of coating or printing the coating composition or ink composition of the present invention is not particularly limited, and the form of the coating composition or ink composition to be used and the surface shape of the substrate are taken into consideration. Various coating methods or printing methods can be used. For example, as a coating method of the coating composition of the present invention, conventionally known coating methods such as spraying, roll coater, brush coating, electrostatic coating, gravure printing and screen printing can be adopted.

If necessary according to an embodiment of the present invention, a base coating layer, a metallic coating layer, and a top coating layer may be applied sequentially. In this case, each coating layer may be coated and then the next coating layer may be coated after curing, or after coating each coating layer by so-called wet-on-wet coating, the next coating layer may be coated without curing. May be painted. However, in order to obtain a coating film having a good mirror-like luster, it is preferable to coat the underlying coating film layer and cure it, and then coat the metallic coating film layer. The method for curing the coating composition for each coating layer may be, for example, heat curing or room temperature curing.

In this case, the thickness of the base coating film layer is not particularly limited, but in a general embodiment,
It is preferably in the range of 10 to 200 μm. Also,
The thickness of the metallic coating film layer is not particularly limited, but in a general embodiment, it is preferably in the range of 1 to 100 μm. The thickness of the top coating film layer is not particularly limited, but in a general embodiment, it is preferably in the range of 5 to 300 μm.

[0094]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Example 1 Commercially available resin-coated aluminum paste (FZ7640 manufactured by Toyo Aluminum Co., Ltd., average diameter: 17 μm, average thickness: 0.4 μm, nonvolatile content 54)
%, Coated with an acrylic copolymer resin), 1.62 g of phosphoric acid and 0.81 g of water dissolved in 10 g of ethanol were added, and then heptadecatrifluorodecyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) (KBM7803)
3.24 g was added and kneaded for 30 minutes to prepare a metal pigment composition.

The leafing number of the obtained metal pigment composition was 75 according to ASTM D480-70. The leafing number of FZ7640 (before treatment) was 0. Table 1 shows the composition of the metal pigment composition and the evaluation results of its leafing number.

Example 2 Commercially available colored aluminum paste (RE2600 manufactured by Toyo Aluminum Co., Ltd., average diameter: 18 μm, average thickness: 1.8 μm, nonvolatile content 52)
%, As a coloring pigment DPP Rubine TR (CI
(Manufactured by BA Co., Ltd.) and coated with an acrylic copolymer resin) 3
Triethanolamine 1.56 g, water 0.31 in 00 g
g was dissolved in 10 g of ethanol and added, and then 1.56 g of heptadecatrifluorodecyltrimethoxysilane (KBM7803 manufactured by Shin-Etsu Chemical Co., Ltd.) was added and added.
The mixture was kneaded for 0 minutes to prepare a metal pigment composition.

The leafing value of the obtained metal pigment composition was 67 according to ASTM D480-70. The leafing value of RE2600 (before treatment) was 0. Table 1 shows the composition of the metal pigment composition and the evaluation results of its leafing number.

<Examples 3 to 11> In the same manner as in Examples 1 and 2, the aluminum paste was treated under the conditions shown in Tables 1 to 4 to prepare metal pigment compositions. Tables 1 to 4 also show the leafing numbers of the obtained metal pigment compositions. 7640NS in the table is a non-leafing type aluminum paste (average diameter: 17μ) manufactured by Toyo Aluminum Co., Ltd.
m, average thickness: 0.36 μm, non-volatile content 65%, no coating resin, no coloring pigment), and the leafing value before treatment was 0.

Comparative Example 1 Commercially available resin-coated aluminum paste (FZ7640 manufactured by Toyo Aluminum Co., Ltd.) 3
3.24 g of stearic acid was added to 00 g and kneaded for 30 minutes to prepare a metal pigment composition. The leafing number of the obtained metal pigment composition was 5 according to ASTM D480-70, and the result was 5. Table 4 shows the composition of the metal pigment composition and the evaluation results of its leafing number.

Comparative Example 2 Commercially available colored aluminum paste (RE2600 manufactured by Toyo Aluminum Co., Ltd.) 300
1.56 g of stearic acid was added to g and kneaded for 30 minutes to prepare a metal pigment composition. The leafing number of the obtained metal pigment composition was 0 according to ASTM D480-70. Table 5 shows the composition of the metal pigment composition and the evaluation results of its leafing number.

Comparative Example 3 Commercially available resin-coated aluminum paste (FZ7640 manufactured by Toyo Aluminum Co., Ltd.) 3
Phosphoric acid 1.62 g, water 0.81 g, ethanol 1
Dissolved in 0 g and added, and then stearic acid 3.24 g
Was added and kneaded for 30 minutes to prepare a metal pigment composition. The leafing number of the obtained metal pigment composition is AST
It was 0 as a result of measurement according to MD 480-70. Table 5 shows the composition of the metal pigment composition and the evaluation results of its leafing number.

Comparative Example 4 Commercially available colored aluminum paste (RE2600 manufactured by Toyo Aluminum Co., Ltd.) 300
1.56 g of triethanolamine and 0.31 g of water were dissolved in 10 g of ethanol and added, and then 1.56 g of stearic acid was added and kneaded for 30 minutes to prepare a metal pigment composition. The leafing number of the obtained metal pigment composition was 0 according to ASTM D480-70. Table 5 shows the composition of the metal pigment composition and the evaluation results of its leafing number.

Comparative Example 5 Commercially available leafing aluminum paste (0700 manufactured by Toyo Aluminum Co., Ltd.)
M) leafing value, ASTM D4 without treatment
The result of measurement according to 80-70 was 85.

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

[Table 4]

[0109]

[Table 5]

<Performance Evaluation> Examples 1 to 11 and Comparative Examples 1 to 1
10 g of the metal pigment composition obtained in 5 was dispersed in 50 g of a commercially available petroleum resin varnish to prepare a paint. The obtained coating material was applied to a glass plate with a doctor blade of 100 μm and dried at room temperature for 1 day. For each of the obtained coating films,
Performance evaluation was performed according to the following test methods. The obtained results are shown in Table 6.

(I) Luminance measuring method Variance colorimeter (X-Rite MA6 manufactured by X-Rite)
The luminance of the coating film was evaluated by the L value at an incident angle of 45 degrees according to 8) and an offset angle of 15 degrees from the regular reflection direction. The larger the L value, the better the metallic feeling.

(Ii) Test Method for Chemical Resistance The chemical resistance of the coating film was evaluated according to JIS K5400.

(Iii) Test Method for Contamination Resistance A fingerprint was adhered to the coating film and left at 50 ° C. for 7 days, and the degree of contamination was visually evaluated by 5 grades based on the following criteria.
The larger the value, the better the stain resistance. 5: A state in which fingerprints cannot be observed at all. 4: A state in which fingerprints are hardly observable. 3: A state in which the fingerprint can be slightly observed. 2: A state in which fingerprints can be easily observed. 1: The fingerprint is white and can be clearly observed.

(Iv) Weather resistance test method Using the coating film, a 1000-hour equivalent xenon arc lamp type accelerated weather resistance test was conducted in accordance with JIS K5400-1990. Gloss (60 ° -6 before and after the test
The gloss was measured under the condition of 0 °, and the gloss retention (ratio (%) of the measured values before and after the test) was obtained to evaluate the weather resistance. The higher the gloss retention rate, the better the weather resistance.

[0115]

[Table 6]

As shown in the results of Tables 1 to 6, in the examples using the silane coupling agent of the present invention, the leafing value and the brightness were higher than those in the comparative examples using stearic acid which was used conventionally. It can be seen that is greatly improved. Further, Examples 1 to 7, Examples 9 to 11, and Comparative Examples 1 to 4 using the resin-coated metal pigment and the resin-coated colored metal pigment.
In Example 8, good chemical resistance was obtained, but in Example 8 in which the metal pigment not coated with the resin was used, it was found that good chemical resistance was not obtained.

The embodiments and examples disclosed this time must be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the above description but by the claims, and is intended to include meanings equivalent to the claims and all modifications within the scope.

[0118]

As is apparent from the above examples, according to the present invention, the leafing property can be imparted to the resin-coated metal pigment which has not been conventionally imparted with the leafing property. Then, as a result, it is possible to provide a leafing resin-coated metal pigment composition having a mirror-like luster, a chemical resistance, a weather resistance, and a stain resistance, and a method for producing the same. Therefore, the drawbacks of the conventional leafing metal pigment composition can be overcome.

According to the present invention, the leafing property can be imparted to the colored metal pigment to which the color pigment is attached. As a result, it is possible to provide a leafing color metallic pigment composition exhibiting a new design having various colors and specular luster, which cannot be obtained by conventional techniques, and a method for producing the same.

The method for producing the leafing resin-coated metal pigment composition or the leafing colored metal pigment composition according to the present invention is very simple and the production cost can be kept low.

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Claims (11)

[Claims] 1. A metal pigment composition containing a metal pigment and a silane coupling agent having a structural formula having a CF ₃ group at the terminal and / or a hydrolysis product thereof or a condensation product thereof. 2. The metal pigment composition according to claim 1, wherein the silane coupling agent is represented by the following chemical formula (1). [Chemical 1] (N is an integer from 0 to 20, m is an integer from 2 to 4, X, Y
Is R or OR or Cl, and R is an alkyl group having 2 or less carbon atoms. ) 3. The silane coupling agent is represented by a chemical formula in which one or more polar functional groups shown below are further introduced into the alkyl group in the chemical formula (1) according to claim 2. Metal pigment composition. -COO-, -CO
S -, - CONH -, - SO 2 NH -, - S- 4. The metal pigment composition according to claim 1, wherein the surface of the metal pigment is coated with a resin. 5. The metallic pigment composition according to claim 1, wherein the metallic pigment is colored with a coloring pigment. 6. The content of a silane coupling agent and / or a hydrolysis product thereof or a condensate thereof is
The metal pigment composition according to claim 1, which is 0.1 to 20 parts by weight with respect to 100 parts by weight of the metal pigment. 7. The method for producing a metal pigment composition according to claim 6, wherein the metal pigment is mixed with a silane coupling agent. 8. The method for producing a metal pigment composition according to claim 7, wherein water and a hydrolysis catalyst are mixed in addition to the silane coupling agent. 9. The hydrolysis catalyst is phosphoric acid, polyphosphoric acid, molybdic acid, phosphomolybdic acid, polymolybdic acid peroxide,
Vanadic acid, chromic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphonic acid, alkylphosphonic acid, and salts thereof, as well as
At least one selected from the group consisting of an alkylamine having 6 or less carbon atoms, an alkylenediamine having 6 or less carbon atoms, an alkanolamine having 6 or less carbon atoms, a silane coupling agent having an amino group, and ammonia. The method for producing the metal pigment composition according to claim 8. 10. A coating composition containing the metal pigment composition according to claim 1, a binder, and a solvent. 11. An ink composition containing the metal pigment composition according to claim 1, a binder, and a solvent.