JP7808974B2 - colored metallic pigments - Google Patents

Description

The present invention relates to colored metallic pigments.

Metallic pigments such as aluminum pigments have been used for a long time to achieve a cosmetic effect that emphasizes a metallic look in metallic paints, printing inks, plastic blends, etc. In recent years, colored aluminum pigments that exhibit a variety of metallic color tones have also been developed.
As such colored aluminum pigments, those having a resin layer containing a colored pigment formed on the surface of the aluminum pigment are generally known.
For example, Patent Document 1 discloses a colored aluminum pigment in which a colored pigment is chemically adsorbed onto the surface of an aluminum pigment via a carboxylic acid having one or more double bonds and two or more carboxyl groups, which is obtained by thermally polymerizing a carboxylic acid having a double bond.
Furthermore, Patent Document 2 discloses a colored aluminum pigment obtained by adhering a colored pigment that has been surface-treated with an amino compound having two amino groups in the molecule but no carboxyl group to basic particles such as aluminum flakes.

JP 01-315470 Public Relations JP 09-124973 Public Relations

However, in recent years, there has been an increasing demand for colored metal (e.g., aluminum) pigments, which are required to have not only high gloss, high saturation, and adhesion to resins, but also excellent orientation in coating films and ink layers.
In view of the above-mentioned problems of the prior art, the present invention aims to provide a colored metallic pigment that has high gloss, high saturation, and adhesion to resins, and also has excellent orientation in coating films and ink layers.

As a result of extensive research into solving the above-mentioned problems, the present inventors have found that by forming a reaction product of an organic acid and an organic base, which contains (B) a resin compound on the surface of (A) a metallic pigment, and further contains (C) a coloring pigment on top of (B), the coloring metallic pigment has a strong adhesion state between the metallic pigment and the layer containing the coloring pigment, and has high gloss, high saturation, and adhesion to the resin, and also has a surface layer of the metallic pigment that is highly smooth, thereby having excellent orientation in the coating film and ink layer, and have completed the present invention.
That is, the present invention is as follows.

[1]
A colored metallic pigment comprising (A) a metallic pigment surface, (B) a resin compound, and (C) a reaction product of an organic acid and an organic base on the (B) resin compound,
the (B) resin compound contains (D) a polymer of a radical polymerizable monomer and/or oligomer,
(D) the radical polymerizable monomer and/or oligomer contains 85% by mass or more of a radical polymerizable unsaturated carboxylic acid having 10 or less carbon atoms,
The reaction product of the organic acid and the organic base (C) is
A colored metallic pigment containing (E) a colored pigment, which is a reaction product of (F) a saturated fatty acid having one carboxyl group and (G) an alicyclic amine having one amino group.
[2]
(A) Metal Pigment: per 100 parts by mass
The (B) resin compound: 0.1 to 5 parts by mass,
The colored metallic pigment according to [1],
[3]
(A) Metal Pigment: per 100 parts by mass
(F) saturated fatty acid having one carboxyl group: 0.6 to 30 parts by mass,
The colored metallic pigment according to [1] or [2], further comprising (G) an alicyclic amine having one amino group: 0.4 to 20 parts by mass.
[4]
(A) Metal Pigment: per 100 parts by mass
(E) color pigment: 5 to 150 parts by mass,
The colored metallic pigment according to any one of [1] to [3],
[5]
The colored metallic pigment according to any one of [1] to [4], wherein the saturated fatty acid having one carboxyl group (F) is at least one saturated fatty acid selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enamentic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, and stearic acid.
[6]
The colored metallic pigment according to any one of [1] to [5], wherein the (G) alicyclic amine having one amino group is at least one alicyclic amine having one amino group selected from the group consisting of cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, N-cyclohexylmethylamine, cyclohexyldimethylamine, cyclohexanemethylamine, and dicyclohexylamine.
[7]
The color metallic pigment according to any one of [1] to [6], wherein a protective layer is formed on the outermost surface layer.
[8]
The colored metallic pigment according to any one of [1] to [7], wherein the metallic pigment (A) is an aluminum pigment.
[9]
A paint containing the colored metallic pigment according to any one of [1] to [8].
[10]
[1] to [8]. An ink containing the colored metallic pigment according to any one of [1] to [8].
[11]
A colored product containing the colored metallic pigment according to any one of [1] to [8].

The colored metallic pigment (composition) of the present invention has the excellent effect of having the colored pigment adhere firmly to the metallic pigment, exhibiting high gloss, high saturation, and adhesion to the resin, and having a highly smooth metallic pigment surface layer, which results in excellent orientation in the coating film and ink layer.

The following describes in detail the form for carrying out the present invention (hereinafter referred to as the "present embodiment"). The following present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out with appropriate modifications within the scope of its gist.

((A) Metallic pigment)
The metallic pigment used in the colored metallic pigment of the present invention (preferably, the resin compound-adhered aluminum pigment) is preferably a "flake-shaped aluminum powder," and is suitable for use with a metallic pigment having the surface properties, particle size, and shape required for the pigment, such as surface gloss, whiteness, and brilliance.
The particles may be in various shapes such as granules, plates, blocks, flakes, etc., but a scale shape is preferred in order to impart excellent metallic appearance and brightness to the coating film.
The flaky aluminum powder preferably has a thickness in the range of 0.001 μm to 1 μm and a particle size in the range of 1 μm to 100 μm.
The aspect ratio of the flaky aluminum powder is preferably in the range of 10 to 20,000.
Here, the aspect ratio is a value obtained by dividing the average particle size of the flaky aluminum powder by the average thickness of the flaky aluminum powder.
The purity of the flaky aluminum powder is not particularly limited, but it is preferable that the purity of the flaky aluminum powder used for coating materials is 99.5% or more.
The flaky aluminum powder can be obtained by a known method, for example, the production method described in WO 99/54074, but products that are usually commercially available in the form of aluminum paste from aluminum paste manufacturers can also be used.

((B) Resin compound)
The resin compound (B) used in the color metallic pigment of this embodiment is a polymer obtained by polymerizing a radically polymerizable monomer and/or oligomer (D).
The radically polymerizable monomer and/or oligomer contains more than 85 mass% of radically polymerizable unsaturated carboxylic acids having 10 or less carbon atoms, thereby achieving both adhesion and hiding power between (A) the scaly metal pigment, (B) the resin compound on the surface of (A), and (C) the reaction product of an organic acid and an organic base containing a coloring pigment.
The content of the radically polymerizable unsaturated carboxylic acid having 10 or less carbon atoms in the radically polymerizable monomer and/or oligomer is preferably 87.5% by mass or more, and more preferably 92.5% by mass or more.

The radically polymerizable unsaturated carboxylic acid having 10 or less carbon atoms includes, but is not limited to, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, and half esters of dibasic acids such as itaconic acid, maleic acid, and fumaric acid. Of these, acrylic acid is preferred from the viewpoint of adhesion.
From the viewpoint of reactivity, the radical polymerizable monomer and/or oligomer preferably has one or more double bonds in the molecule.

A radical polymerizable monomer and/or oligomer other than the radical polymerizable unsaturated carboxylic acid having 10 or less carbon atoms may also be used, and the type thereof is not particularly limited, and conventionally known monomers and/or oligomers may be used. The amount used is not particularly limited, and for example, the amount used may be 1 to 50 mass % of the total amount of the radical polymerizable monomer and/or oligomer.
Examples of the vinyl monomer include, but are not limited to, acrylic acid esters, methacrylic acid esters, aromatic vinyl compounds, vinyl cyanides, amide group-containing vinyl monomers, hydroxyl group-containing vinyl monomers, epoxy group-containing vinyl monomers, carbonyl group-containing vinyl monomers, anionic vinyl monomers, mono- or diesters of phosphoric acid or phosphonic acid, and vinyl monomers having a silyl group.
In this specification, (meth)acrylic is a simple expression for methacrylic or acrylic.
Examples of the (meth)acrylic acid ester include, but are not limited to, (meth)acrylic acid alkyl esters having 1 to 50 carbon atoms in the alkyl moiety, and (poly)oxyethylene di(meth)acrylates having 1 to 100 ethylene oxide groups.
Examples of (meth)acrylic acid esters include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, and dodecyl (meth)acrylate.
Examples of (poly)oxyethylene di(meth)acrylates include, but are not limited to, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, diethylene glycol methoxy(meth)acrylate, and tetraethylene glycol di(meth)acrylate.
Other examples include trimethylolpropane tri(meth)acrylate, tetramethylolpropane tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-pentaerythritol hexa(meth)acrylate, di-pentaerythritol penta(meth)acrylate, and di-pentaerythritol penta(meth)acrylate monopropionate.
Furthermore, cyclic unsaturated compounds (e.g., cyclohexene) and aromatic unsaturated compounds (e.g., styrene, α-methylstyrene, vinyltoluene, divinylbenzene, cyclohexene vinyl vinyl monoxide, divinylbenzene monoxide, vinyl acetate, vinyl propionate, allylbenzene, or diallylbenzene) can also be suitably used.

The hydroxyl group-containing vinyl monomer may include, but is not limited to, hydroxyalkyl esters of (meth)acrylic acid such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; di-2-hydroxyethyl fumarate; mono-2-hydroxyethyl monobutyl fumarate; allyl alcohol; (poly)oxyethylene mono(meth)acrylate having 1 to 100 ethylene oxide groups; (poly)oxypropylene mono(meth)acrylate having 1 to 100 propylene oxide groups; and even "Placcel FM and FA Monomers" (trade names for caprolactone addition monomers manufactured by Daicel Chemical Industries, Ltd.) and other hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids.

Examples of the (poly)oxyethylene mono(meth)acrylate include, but are not limited to, ethylene glycol (meth)acrylate, ethylene glycol methoxy(meth)acrylate, diethylene glycol (meth)acrylate, diethylene glycol methoxy(meth)acrylate, tetraethylene glycol (meth)acrylate, and tetraethylene glycol methoxy(meth)acrylate.

In addition, examples of (poly)oxypropylene mono(meth)acrylates include, but are not limited to, propylene glycol (meth)acrylate, propylene glycol methoxy(meth)acrylate, dipropylene glycol (meth)acrylate, dipropylene glycol methoxy(meth)acrylate, tetrapropylene glycol (meth)acrylate, and tetrapropylene glycol methoxy(meth)acrylate.

Furthermore, examples of the epoxy group-containing vinyl monomer include, but are not limited to, glycidyl (meth)acrylate, allyl glycidyl ether, and allyl dimethyl glycidyl ether.

Furthermore, examples of the mono- or diester of phosphoric or phosphonic acid include, but are not limited to, 2-methacryloyloxyethyl phosphate, di-2-methacryloyloxyethyl phosphate, tri-2-methacryloyloxyethyl phosphate, 2-acryloyloxyethyl phosphate, di-2-acryloyloxyethyl phosphate, tri-2-acryloyloxyethyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dioctyl-2-acryloyloxyethyl phosphate, 2-methacryloyloxypropyl phosphate, bis(2-chloroethyl)vinylphosphonate, diallyl dibutyl phosphonosuccinate, 2-methacryloyloxyethyl phosphate, and 2-acryloyloxyethyl phosphate.

In addition, examples of the vinyl monomer having a silyl group include, but are not limited to, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltri-n-propoxysilane, 3-(meth)acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and 2-trimethoxysilylethyl vinyl ether.

Other monomers and/or oligomers used to obtain resin compounds include, but are not limited to, olefins such as (meth)acrylamide, ethylene, propylene, and isobutylene; dienes such as butadiene; haloolefins such as vinyl chloride, vinylidene chloride vinyl fluoride, tetrafluoroethylene, and chlorotrifluoroethylene; vinyl carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl p-t-butylbenzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate, and vinyl laurate; and isopropenyl carboxylic acid esters such as isopropenyl acetate and isopropenyl propionate. Examples of suitable resin compounds include esters; vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, and cyclohexyl vinyl ether; aromatic vinyl compounds such as styrene and vinyl toluene; allyl esters such as allyl acetate and allyl benzoate; allyl ethers such as allyl ethyl ether and allyl phenyl ether; and 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meth)acrylate, perfluoropropyl (meth)acrylate, perfluoropropylmethyl (meth)acrylate, vinylpyrrolidone, and allyl (meth)acrylate. These resin compounds may be used alone or in combination of two or more.

The color metallic pigment of this embodiment contains 100 parts by mass of the above-mentioned (A) metallic pigment and 0.1 to 5 parts by mass of the (B) resin compound.
The content of the resin compound (B) is set to 0.1 parts by mass or more from the viewpoint of adhesion, and 5 parts by mass or less from the viewpoint of gloss and saturation.
The content of the (B) resin is preferably 0.5 to 3.5 parts by mass per 100 parts by mass of the (A) metallic pigment.

<Polymerization initiator>
When producing the color metallic pigment of this embodiment, it is preferable to use a polymerization initiator such as a peroxide or azo compound that does not become fixed on the surface of the flaky aluminum powder.
The method for producing the colored metallic pigment of this embodiment will be described later (i.e., see the section titled "Production Method of Colored Metallic Pigment").
The polymerization initiator is generally known as a radical generator, and the type thereof is not particularly limited.
Examples of the polymerization initiator include, but are not limited to, peroxides such as benzoyl peroxide, lauroyl peroxide, and bis-(4-t-butylcyclohexyl)peroxydicarbonate, and azo compounds such as 2,2'-azobis-isobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile.
The amount of the polymerization initiator used is not particularly limited as it is adjusted depending on the reaction rate of the radical polymerizable monomer and/or oligomer, but is preferably in the range of 0.1 parts by mass or more and 25 parts by mass or less per 100 parts by mass of the flaky aluminum powder.

<Other ingredients>
As will be described later, in the color metallic pigment of this embodiment, after dispersing the flaky aluminum powder in a predetermined organic solvent, a chain transfer agent may be added together with the above-described radical polymerizable monomer and/or oligomer for the purpose of controlling the molecular weight of the reaction product.
Examples of the chain transfer agent include, but are not limited to, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecylbenzyl mercaptan; thiocarboxylic acids such as thiomalic acid or salts thereof, or alkyl esters thereof, polythiols, diisopropyl xanthogen disulfide, di(methylene trimethylolpropane) xanthogen disulfide, and thioglycol, as well as allyl compounds such as α-methylstyrene dimer.
The amount of these chain transfer agents used is preferably in the range of 0.001% by mass to 30% by mass, more preferably 0.05% by mass to 10% by mass, based on the resin.

((C) Reaction products of organic acids and organic bases)
<(E) Coloring Pigment>
As the color pigment constituting the color metallic pigment of this embodiment, any conventionally known pigment can be used without any particular limitation, and for example, blue pigments, red pigments, yellow pigments, etc. can be used.

The metallic pigments of this embodiment primarily have the effect of imparting metallic luster and are often achromatic. Here, chromatic coloring pigments have the effect of imparting color to metallic pigments. However, they are not limited to chromatic colors, and may also have the effect of imparting achromatic colors such as black or white.

Examples of color pigments include organic pigments such as phthalocyanines, perylenes, threnes, linked azos, isoindolinones, quinacridones, quinophthalones, dioxazines, perinones, and diketopyrrolopyrroles, as well as inorganic pigments such as carbon black, iron oxide, and titanium oxide.

Particularly preferred color pigments from the standpoint of adhesion to metal pigments, weather resistance, and coloring strength include phthalocyanine blue, perylene maroon, anthrapyrimidine yellow, quinacridone gold, phthalocyanine green, quinacridone red, dioxazine violet, and ultrafine titanium oxide.

The primary particle size of the color pigment is not particularly limited, but is preferably in the range of 0.01 to 0.8 μm, and more preferably 0.05 to 0.5 μm. A primary particle size of 0.05 to 0.5 μm allows for good dispersion of the raw material and allows it to adhere uniformly to the metal pigment surface.

The amount of color pigment attached is preferably 5 to 150 parts by mass per 100 parts by mass of metallic pigment. It is more preferably 10 to 100 parts by mass. If the amount attached is less than 5 parts by mass, the color metallic pigment will not have sufficient saturation, and if the amount attached is more than 150 parts by mass, the brilliance of the color metallic pigment will decrease.

<(F) Saturated Fatty Acid (Organic Acid) Having One Carboxyl Group>
As the saturated fatty acid having one carboxyl group as the organic acid used in the color metallic pigment of this embodiment, any conventionally known saturated fatty acid having one carboxyl group can be used without any particular limitation.

Specific examples include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enamentic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, and stearic acid.

<(G) Alicyclic amine (organic base) having one amino group>
The alicyclic amine having one amino group as the organic base used in the color metallic pigment of this embodiment can be any conventionally known saturated fatty acid having one carboxyl group, without any particular limitation.

Specific examples include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, N-cyclohexylmethylamine, cyclohexyldimethylamine, cyclohexanemethylamine, and dicyclohexylamine.

The organic acid and organic base that make up the colored metallic pigment of this embodiment are a saturated fatty acid having one carboxyl group and an alicyclic amine having one amino group, respectively. By reacting such an organic acid and organic base, the colored pigment adheres to the surface of the resin compound-adhered metallic pigment (the components (A) and (B)).

The amount of saturated fatty acid with one carboxyl group contained in the colored metallic pigment varies depending on the specific surface area of the metallic pigment used and the amount of colored pigment used, but is preferably 0.6 to 30 parts by mass, and more preferably 1.0 to 20 parts by mass, per 100 parts by mass of metallic pigment. If the amount is less than 0.6 parts by mass, the colored pigment cannot be sufficiently adhered to the surface of the metallic pigment, and if the amount is more than 30 parts by mass, there will be no change in the effect and it will be economically disadvantageous.

Furthermore, from the viewpoint of reactivity with the fatty acid, the amount of alicyclic amine having one amino group contained in the colored metallic pigment is preferably 0.4 to 20 parts by mass, and more preferably 0.7 to 14 parts by mass, per 100 parts by mass of the metallic pigment. If the amount is less than 0.4 parts by mass, the colored pigment cannot be sufficiently adhered to the surface of the metallic pigment, and if the amount exceeds 20 parts by mass, there is no change in this effect and it is economically disadvantageous.

<Protective layer>
The color metallic pigment of this embodiment preferably has a protective layer formed on the outermost surface. Densely coating the color metallic pigment with the protective layer further improves adhesion between the color metallic pigment and the reaction product layer of saturated fatty acid and alicyclic amine, which contains the color metallic pigment, and also provides alkali resistance and water resistance. Here, alkali resistance refers to the process of suppressing corrosion of the color metallic pigment by an alkaline solution when a coating film containing the color metallic pigment is immersed in the alkaline solution. Furthermore, water resistance refers to the process of suppressing gas generation when the color metallic pigment is blended into an aqueous paint or ink and comes into contact with water.
The protective layer is preferably composed of a resin compound obtained by reacting (polymerizing) one or more radically polymerizable monomers and/or oligomers, or an oxide or hydroxide of at least one element selected from the group consisting of Si, Ti, Al, Cr, Zr, Ce, and Mo. The protective layer may also be composed of a resin compound and an oxide or hydroxide. In this case, the order of forming the resin compound and the oxide or hydroxide layers is not particularly limited.
The amount of the protective layer contained in the color metallic pigment varies depending on the specific surface area of the metallic pigment used and the amount of the color metallic pigment used, but can be 0.01 to 20 parts by mass, or 0.1 to 5 parts by mass, per 100 parts by mass of the metallic pigment. If the amount is less than 0.01 part by mass, it may be difficult to fully exert the effect of the protective layer, and if it exceeds 20 parts by mass, the original properties of the color metallic pigment may be impaired.

[Method for producing colored metallic pigments]
The colored metallic pigment of this embodiment can be produced by dispersing an untreated metallic pigment in an organic solvent, heating the mixture, and adding (D) a radically polymerizable monomer and/or oligomer and a polymerization initiator while stirring, allowing the mixture to react. Thereafter, (E) a colored pigment, (F) a saturated fatty acid having one carboxyl group, and (G) an alicyclic amine having one amino group are added, and the resulting dispersion is reacted while being subjected to a vibrational external action (for example, by irradiating the dispersion with ultrasonic waves using an ultrasonic generator).
The organic solvent may be any solvent that is inactive to the (A) metal pigment, and includes, but is not limited to, aliphatic hydrocarbons such as hexane, heptane, octane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, and solvent naphtha; ethers such as tetrahydrofuran and diethyl ether; alcohols such as ethanol, 2-propanol, and butanol; esters such as ethyl acetate and butyl acetate; and cellosolves such as ethylene glycol monoethyl ether.

The mass concentration of the metal pigment (A) in the organic solvent is preferably 0.1 to 40 mass %, more preferably 1 to 35 mass %.
From the viewpoint of reaction rate, the content is preferably 0.1% by mass or more, and from the viewpoint of dispersibility, the content is preferably 40% by mass or less.

When dispersing the untreated (A) metal pigment in an organic solvent, heating the mixture, and adding the (D) radical polymerizable monomer and/or oligomer while stirring, it is preferable from the viewpoint of productivity to add the radical polymerizable unsaturated carboxylic acid having 10 or less carbon atoms in the first step, and then add the (D) radical polymerizable monomer and/or oligomer other than the radical polymerizable unsaturated carboxylic acid having 10 or less carbon atoms in the second step.
In addition, the second stage may contain a radically polymerizable unsaturated carboxylic acid having 10 or less carbon atoms, and conversely, if the resin compound is composed only of a radically polymerizable unsaturated carboxylic acid having 10 or less carbon atoms, the second stage is not necessary.

When a polymerization initiator is used in the polymerization reaction of the radical polymerizable monomer and/or oligomer (D), the timing of adding the polymerization initiator is not particularly limited, but it is preferable to add the polymerization initiator simultaneously with and/or after the radical polymerizable monomer and/or oligomer (D).
The temperature at which the polymerization initiator is added is not particularly limited as long as it allows the polymerization reaction of the radically polymerizable monomer and/or oligomer (D) to occur, but is preferably 60° C. to 150° C. In order to increase the reaction efficiency, it is preferable to add and react the initiator in an inert gas atmosphere such as nitrogen or helium.

(D) A radical polymerizable monomer and/or oligomer and a polymerization initiator are added and reacted, and then (E) a color pigment and (F) a saturated fatty acid having one carboxyl group are added successively, and stirring is continued for 30 minutes to 3 hours.
After the above treatment, (G) an alicyclic amine having one amino group is added, and a further reaction is carried out for 30 minutes to 3 hours to attach the color pigment to the metal pigment.

In addition, during the reaction of (D) the radical polymerizable monomer and/or oligomer, and the reaction of (F) the saturated fatty acid having one carboxyl group and (G) the alicyclic amine having one amino group, which contain (E) the color pigment, a solvent can be added or replaced as necessary.

When producing the colored metallic pigment of this embodiment, it is preferable to use a combination of a shear external action and a vibration external action as the external action.
The shear external action refers to the action of applying high shear force to promote physical dispersion when dispersing a metal pigment in an organic solvent and when adding a monomer to the dispersion.One method for this is to disperse the metal pigment and monomer using a disperser.
The vibrational external action refers to an action of promoting physical dispersion by using a vibration generator, ultrasonic generator, or the like to strongly vibrate the dispersion liquid or the mixed solution during the polymerization reaction.
Examples of the mode of adding the vibrational external action include a mode of adding it intermittently during the polymerization reaction, a mode of adding it continuously during the polymerization reaction, and a mode of combining intermittent addition and continuous addition during the polymerization reaction.
Further, methods of applying a vibrational external action include a method in which an external action is indirectly applied to the reactor by applying vibrations and irradiating ultrasonic waves from a vibration generator and an ultrasonic vibrator, a method in which the external action is directly applied to the treatment dispersion in the reactor, and a method in which the treatment dispersion is circulated in an external circulation type container and a vibrational external action is applied indirectly or directly to the external circulation type container.
The vibration caused by the external action such as a vibration generator preferably has a frequency of 10 Hz or more and 24 kHz or less.
Ultrasonic waves generated by external action such as an ultrasonic generator are a type of elastic vibration that propagates through an elastic body, and are usually longitudinal waves that propagate compression and expansion in the direction of wave propagation, but transverse waves may also exist on the reactor wall and its contact surfaces. Note that, in terms of technical definition, ultrasonic waves also include sound waves that are not intended to be heard directly, and all sound waves that propagate through the surface or interior of a liquid or solid are also included. Ultrasonic waves with a frequency of 15 kHz to 10,000 kHz and an output of 5 W or more can be preferably used.

[Use of colored metallic pigments]
The colored metallic pigment of this embodiment can be used as a pigment in colored materials such as paint compositions, ink compositions, etc. As the paint compositions and ink compositions, either solvent-based or water-based can be used.
When the colored metallic pigment of this embodiment is used in a solvent-based paint or ink, the paint resin or ink resin may be a paint or ink resin that has been conventionally used in metallic paints and metallic inks.
Examples of the resin for paint or ink include, but are not limited to, acrylic resin, alkyd resin, oil-free alkyd resin, vinyl chloride resin, urethane resin, melamine resin, unsaturated polyester resin, urea resin, cellulose-based resin, epoxy resin, and fluororesin.
These may be used alone or in combination of two or more.

When the colored metallic pigment of this embodiment is used as a pigment for solvent-based paints and inks, the amount of the colored metallic pigment used is preferably 0.1 to 300 parts by mass, and more preferably 0.2 to 200 parts by mass, per 100 parts by mass of the paint or ink resin. From the viewpoint of metallic gloss, an amount of 0.1 part by mass or more is preferred, and from the viewpoint of coating film properties, an amount of 300 parts by mass or less is preferred.

Examples of diluents for solvent-based paints and inks include, but are not limited to, aromatic compounds such as toluene and xylene; aliphatic compounds such as hexane, heptane, and octane; alcohols such as ethanol and butanol; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone; chlorine compounds such as trichloroethylene; and cellosolves such as ethylene glycol monoethyl ether. These diluents may be used alone or in combination.
The composition of the diluent may be determined appropriately taking into consideration the solubility in the paint and ink resins, film forming properties, coating workability, and the like.

Additionally, paints and inks may contain additives commonly used in the paint industry, such as pigments, dyes, wetting agents, dispersants, color-shift inhibitors, leveling agents, slip agents, anti-skinning agents, anti-gelling agents, and defoamers.

Furthermore, the paints and inks can also be used as water-based paints by using a resin for water-based paints.
However, when using colored metallic pigments, there is a possibility that they may react with water in water-based paints and inks, and in such cases, it is necessary to add a reaction inhibitor.
Here, the resin for aqueous paint is a water-soluble resin or a water-dispersible resin, and may be a single type or a mixture of two or more types. The type may be appropriately selected depending on the purpose and application, and is not particularly limited, but for paints, general examples include acrylic, acrylic-melamine, polyester, polyurethane, and other aqueous paint resins, and among these, acrylic-melamine resins are the most widely used.

When used as a water-based paint or ink, the amount of colored metallic pigment of this embodiment used is preferably 0.1 to 300 parts by mass, and more preferably 0.2 to 200 parts by mass, per 100 parts by mass of the water-based paint resin. From the perspective of achieving metallic luster, an amount of 0.1 part by mass or more is preferred, and from the perspective of coating film properties, an amount of 300 parts by mass or less is preferred.

Additives that are commonly used in the relevant field and do not impair the effects of the present invention can be used, such as dispersants, thickeners, anti-sagging agents, anti-mold agents, UV absorbers, film-forming aids, surfactants, other organic solvents, and water. Additionally, it is preferable to add these additives in amounts that do not impair the effects of the present invention.

[Painting method]
As a coating method using the paint or ink containing the colored metallic pigment of this embodiment, a known method can be applied.
For example, spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, flexographic printing, etc. may be mentioned.
After coating, if desired, it is also possible to carry out heat treatment, preferably at 20 to 500°C, more preferably at 40 to 250°C, ultraviolet irradiation, etc. It is also possible to apply the coating material to a substrate heated to 40 to 250°C.

[Application]
The color metallic pigment of this embodiment can be used for coatings for automobiles, general home appliances, and information appliances such as mobile phones, or for predetermined printing applications.
These can be applied to substrates made of specific materials such as metals such as iron and magnesium alloys, or plastics, and can be printed on to achieve high color development and design.

The present invention will be explained in detail below using specific examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1]
209.5 g of flaky aluminum powder paste GX-40A (manufactured by Asahi Kasei Corporation, average particle size 19 μm, non-volatile content 74%) was placed in a 2 L ultrasonic dissolution/dispersion tank (GSC50AG: manufactured by Sonic Technology Corporation), 410.6 g of mineral spirits was added, and the mixture was stirred while introducing nitrogen gas. The temperature in the system was raised to 70° C. and stirring was continued for 1 hour.
Next, a solution consisting of 7.38 g of acrylic acid, 0.39 g of trimethylolpropane trimethacrylate, 1.16 g of 2,2'-azobis-2,4-dimethylvaleronitrile, and 15 g of mineral spirit was prepared and added all at once to the ultrasonic dissolution and dispersion tank. After the addition, the first polymerization step was carried out for 3 hours while maintaining the temperature in the system at 70°C.
Next, at the end of the first polymerization step of 3 hours, a solution consisting of 1.16 g of bis-(4-t-butylcyclohexyl) peroxydicarbonate and 5 g of mineral spirits was prepared and added all at once. The temperature in the system was maintained at 70°C, and the second polymerization step was carried out for 1 hour.
Next, 23.30 g of formic acid was added all at once to the system, and after stirring for 30 minutes, 440 g of mineral spirits as a solvent and 77.65 g of a blue pigment (Fastogen Blue AE-8: manufactured by DIC Corporation) were added all at once, followed by a third treatment step for 30 minutes.
Next, 15.53 g of N-cyclohexylmethylamine was added all at once to the system, and a fourth reaction treatment step was carried out for 30 minutes to 1.5 hours at 70° C. By carrying out the fourth reaction treatment step, a slurry was obtained containing the color pigment (blue pigment) attached to the resin compound formed on the surface of the aluminum pigment, together with the reaction product of the organic acid (formic acid) and the organic base (N-cyclohexylmethylamine).

Subsequently, a solution consisting of 1.55 g of acrylic acid, 7.77 g of trimethylolpropane trimethacrylate, 1.16 g of 2,2'-azobis-2,4-dimethylvaleronitrile, and 99.34 g of mineral spirit was added all at once to the colored aluminum pigment-containing slurry obtained above. After the addition, the fifth polymerization step was carried out for 3 hours while maintaining the temperature in the system at 70°C.
From the first polymerization step to the fifth polymerization step, the mixture in the ultrasonic dissolving and dispersing apparatus GSC50AG was irradiated with ultrasonic waves at an output of 30 W.
After the fifth polymerization step was completed, the filtrate was sampled and analyzed by gas chromatography to determine the amount of unreacted trimethylolpropane trimethacrylate. It was found that 99% or more of the added amount had reacted.
After the polymerization was completed, the mixture was naturally cooled and the slurry was filtered to obtain a colored aluminum pigment having a protective layer made of a resin compound formed on the surface thereof.
The non-volatile content of this paste (according to JIS-K-5910) was 50.2% by mass.

[Example 2]
A colored aluminum pigment was obtained in the same manner as in Example 1, except that the organic acid was changed from 23.30 g of formic acid to 23.30 g of caprylic acid, and the organic base was changed from 15.53 g of N-cyclohexylmethylamine to 15.53 g of cyclohexylamine. The nonvolatile content of this paste according to JIS-K-5910 was 50.9 mass%.

[Example 3]
A colored aluminum pigment was obtained in the same manner as in Example 1, except that the organic acid was changed from 23.30 g of formic acid to 23.30 g of acetic acid, and the organic base was changed from 15.53 g of N-cyclohexylmethylamine to 15.53 g of dicyclohexylamine. The nonvolatile content of this paste according to JIS-K-5910 was 50.5 mass%.

[Example 4]
A colored aluminum pigment was obtained in the same manner as in Example 1, except that 77.65 g of the blue pigment used as the color pigment was changed to 85.10 g of a red pigment (Paliogen Maroon L3920: manufactured by BASF Japan Ltd.) The nonvolatile content of this paste according to JIS-K-5910 was 50.1 mass%.

[Example 5]
A colored aluminum pigment was obtained in the same manner as in Example 1, except that 77.65 g of the blue pigment used as the color pigment was changed to 75.50 g of a yellow pigment (Irgazin Yellow L0800, manufactured by BASF Japan Ltd.) The nonvolatile content of this paste according to JIS-K-5910 was 50.5% by mass.

[Comparative Example 1]
Except for not carrying out the first and second polymerization steps, a colored aluminum pigment was obtained in the same manner as in Example 1. The nonvolatile content of this paste according to JIS-K-5910 was 62.5% by mass.

[Comparative Example 2]
A colored aluminum pigment was obtained in the same manner as in Example 1, except that 23.30 g of formic acid was changed to 23.30 g of acrylic acid as the organic acid. The nonvolatile content of this paste according to JIS-K-5910 was 40.9 mass%.

[Comparative Example 3]
A colored aluminum pigment was obtained in the same manner as in Example 1, except that 15.53 g of N-cyclohexylmethylamine was changed to 15.53 g of dibutylamine as the organic base. The nonvolatile content of this paste according to JIS-K-5910 was 60.7 mass%.

[Methods for measuring physical properties]
A coating composition was prepared by dispersing 5.0 g of each of the colored aluminum pigments obtained in Examples 1 to 5 and Comparative Examples 1 to 3 in 97.0 g of a commercially available acrylic lacquer (Acrylic #2000 Clear, manufactured by Kansai Paint Co., Ltd.). The coating composition was applied to double-sided art paper using a 9-mil applicator to prepare a coated plate.
<Glossiness (G60)>
The gloss of each of the coated plates obtained above was measured at 60 degrees (both the incident angle and the reflection angle were 60 degrees) using a gloss meter (digital variable angle gloss meter UGV-5D, manufactured by Suga Test Instruments Co., Ltd.). The higher the gloss value, the higher the gloss. The results are shown in Table 1.

<Saturation value>
The chroma of each of the coated panels obtained above was measured using a multi-angle spectrophotometer (X-Rite MA-94, manufactured by X-Rite). The chroma value (C*) was calculated using the a* and b* values measured at an incident angle of 45° and an offset angle of 15° according to the following formula. A higher chroma value (C*) indicates higher chroma. The results are shown in Table 1.

<Adhesion>
To a 50 ml screw cap bottle, 1.0 g of each colored aluminum pigment obtained in Examples 1 to 5 and Comparative Examples 1 to 3 and 30 g of acetone were added, and the mixture was shaken well to disperse. The mixture was then left to stand for 3 hours, and the state of dissolution of the colored pigment in the colored aluminum pigment was observed and evaluated. If the adhesion between the aluminum pigment and the colored pigment is insufficient, the supernatant liquid will be colored by the eluted colored pigment. On the other hand, if the adhesion is good, the supernatant liquid will be transparent. The evaluation criteria were as follows, with ○ representing a pass and × representing a fail, taking practicality into consideration. The results are shown in Table 1.
Evaluation: ◯: The supernatant is colorless and transparent. ×: The supernatant is opaque and colored.

<Orientation in the coating film>
The orientation in the coating film was evaluated by the graininess of each coated panel obtained above. The graininess was measured using a metallic coating brightness measuring device (BYK-mac i: manufactured by BYK Japan). The lower the graininess value, the better the orientation in the coating film. The results are shown in Table 1.

As is clear from Table 1, the colored aluminum pigments of each example have better gloss and higher saturation than the colored aluminum pigments of the comparative examples, and also have better orientation in the coating film. They also have excellent adhesion between the aluminum pigment and the colored pigment. Therefore, it has been confirmed that the colored aluminum pigment of this embodiment exhibits the excellent effects of strong adhesion between the aluminum pigment and the colored pigment, good orientation in the coating film, and good gloss and high saturation.

The embodiments and examples disclosed herein should be considered in all respects to be illustrative and not restrictive. The scope of the present invention is indicated by the claims, not the above description, and is intended to include all modifications equivalent to and within the scope of the claims.

The colored metallic pigment of this embodiment has industrial applicability in paints for the automotive industry (including motorcycles), aircraft industry, home appliance industry, etc., such as paints for various parts for automobiles and aircraft and various parts for information appliances such as general home appliances and mobile phones, or in inks for the printing industry, such as printing inks. Specifically, it has industrial applicability in paint and ink applications for substrates such as metals, such as iron and magnesium alloys, or plastics.

Claims (11)

A colored metallic pigment comprising (A) a metallic pigment surface, (B) a resin compound, and (C) a reaction product of an organic acid and an organic base on the (B) resin compound,
the (B) resin compound contains (D) a polymer of a radical polymerizable monomer and/or oligomer,
(D) the radical polymerizable monomer and/or oligomer contains 85% by mass or more of a radical polymerizable unsaturated carboxylic acid having 10 or less carbon atoms,
The reaction product of the organic acid and the organic base (C) is
A colored metallic pigment containing (E) a colored pigment, which is a reaction product of (F) a saturated fatty acid having one carboxyl group and (G) an alicyclic amine having one amino group. (A) Metal Pigment: per 100 parts by mass
The (B) resin compound: 0.1 to 5 parts by mass,
2. The colored metallic pigment according to claim 1, comprising: (A) Metal Pigment: per 100 parts by mass
(F) saturated fatty acid having one carboxyl group: 0.6 to 30 parts by mass,
3. The colored metallic pigment according to claim 1, further comprising: (G) an alicyclic amine having one amino group: 0.4 to 20 parts by mass. (A) Metal Pigment: per 100 parts by mass
(E) color pigment: 5 to 150 parts by mass,
The colored metallic pigment according to any one of claims 1 to 3, comprising The colored metallic pigment according to any one of claims 1 to 4, wherein the saturated fatty acid (F) having one carboxyl group is at least one saturated fatty acid selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enamentic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, and stearic acid. The colored metallic pigment according to any one of claims 1 to 5, wherein the (G) alicyclic amine having one amino group is at least one alicyclic amine having one amino group selected from the group consisting of cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, N-cyclohexylmethylamine, cyclohexyldimethylamine, cyclohexanemethylamine, and dicyclohexylamine. The colored metallic pigment according to any one of claims 1 to 6, wherein a protective layer is formed on the outermost surface. The colored metallic pigment according to any one of claims 1 to 7, wherein the metallic pigment (A) is an aluminum pigment. A paint containing the colored metallic pigment according to any one of claims 1 to 8. An ink containing the colored metallic pigment described in any one of claims 1 to 8. A colored product containing the colored metallic pigment according to any one of claims 1 to 8.