JP3481360B2 - Surface-treated colored pigment, colored substrate particles and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is mainly applied to metallic paint finish of automobiles, decorative finish of plastic,
The present invention relates to colored substrate particles used for printing ink and the like and a method for producing the same.

[0002]

2. Description of the Related Art Aluminum flakes have been conventionally used for metallic paint finishes, plastic decorative finishes, or printing inks. When the aluminum flakes are used after being colored, a coloring pigment is mixed with the aluminum flakes. In this case, the color of the achromatic aluminum flake is emphasized, and it is difficult to obtain a clear color tone.

Colored flake pigments using inorganic flakes such as mica instead of aluminum flakes are also used. In this case as well, although a characteristic pearly color tone is obtained, the color is limited. There are problems such as poor hiding power and difficulty in obtaining a metallic luster. Also,
The same problem occurs when a metallic pigment is kneaded into a resin to obtain a decorative effect.

In order to solve the above-mentioned problems, a method has been proposed in which a pigment or the like is attached to each aluminum flake by a resin coating method or the like to color it (for example, JP-A-5-508424 and JP-B-6-92546). No.)
However, it was not possible to obtain a clear color tone because it was difficult to attach a sufficient amount of pigment. Further, even if the amount of the pigment attached can be increased, there are problems that the pigment is likely to come off and the process is complicated.

[0005]

The main object of the present invention is to:
In order to improve the saturation, which is the drawback of conventional metallic pigments,
A color pigment is attached to base particles such as aluminum flakes to provide base particles colored with high saturation.

[0006] A further object of the present invention is the problem of discoloration, insufficient saturation, which has been a problem in the conventional methods for coloring metallic pigments.
It is an object of the present invention to solve problems such as complication of processes and provide an optimal colored substrate particle for paint / ink or resin kneading and a method for producing the same.

In order to achieve the above-mentioned object, it is necessary to attach a coloring pigment to the entire surface of each individual substrate particle, and if there is a substrate particle to which no pigment is attached, the light from the particle is emitted. The vividness of the color tone is impaired by the direct reflection of the pigment, and even when it is used for paints and inks or for kneading resins, the pigments fall off in the process of manufacturing them and When it occurs, the vividness of the color tone is impaired.

[0008]

SUMMARY OF THE INVENTION The first subject of the present invention is to coat the surface of a color pigment with a monobasic aromatic carboxylic acid to improve the adhesion of the color pigment to substrate particles. It relates to a surface-treated colored pigment which is improved and suitable for colored substrate particles.

According to the present invention, the color pigment is not particularly limited, and any of organic and inorganic pigments can be used.
Specific examples of pigments that can be used include those listed below. A pigment having a primary particle size of 0.01 to 1 μm, preferably 0.02 to 0.1 μm is suitable.

Phthalocyanine, halogenated phthalocyanine, quinacridone, diketopyrrolopyrrole, isoindolinone, azomethine metal complex, indanthrone, perylene, perinone, anthraquinone, dioxazine, benzimidazolone, condensed azo, triphenylmethane, quinophthalone, anthra. Pyrimidine, titanium oxide, iron oxide, carbon black.

Particularly preferred pigments in terms of adhesion and coloring power are phthalocyanine blue, phthalocyanine green, quinacridone maroon, quinacridone gold, diketopyrrolopyrrole, isoindolinone orange, isoindolinone yellow, dioxazine violet and perylene maroon. , Azomethine copper complex, ultrafine particle titanium oxide, transparent iron oxide, and carbon black.

Examples of the monobasic aromatic carboxylic acid that can be used in the present invention include benzoic acid, vinyl benzoate, salicylic acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 3-amino-4-methylbenzoic acid, p-aminosalicylic acid, 1-naphthoic acid, 2-naphthoic acid, naphthenic acid, 3-amino-2-naphthoic acid, cinnamic acid, aminocinnamic acid.

Among these, benzoic acid, aminobenzoic acid (anthranilic acid, etc.), aminohydroxybenzoic acid (aminosalicylic acid, etc.), naphthoic acid (2-naphthoic acid, etc.), aminonaphthoic acid (3-amino-2-, etc.) Naphthoic acid, etc.), cinnamic acid, and aminocinnamic acid are preferable because they are particularly excellent in the adhesion of the surface-treated color pigment when the base particles are coated.

The amount of the monobasic aromatic carboxylic acid added is 0.2 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the pigment. If the addition amount of the monobasic aromatic carboxylic acid is too small, it becomes difficult to attach the surface-treated color pigment to the base particles, while if the addition amount is too large, the surface-treated color pigment is attached to the base particles. The pigment cannot be sufficiently fixed to the base particles even if the resin is subsequently coated.Excessive monobasic aromatic carboxylic acid increases the viscosity of the paint when the colored base particles are mixed in the paint or the paint film. Inconveniences such as causing problems such as deterioration of weather resistance occur.

The surface of the surface-treated color pigment of the present invention may be further coated with an aluminum or titanium chelate compound. These chelate compounds have the effect of improving the dispersibility of the color pigment in the non-polar solvent, whereby the color pigment can be uniformly and finely adhered to the substrate particles.

Examples of the chelate compound which can be used in the present invention are: dialkoxyaluminum alkyl acetoacetate, aluminum trialkyl acetoacetate, aluminum triacetyl acetonate, aluminum acetyl acetonate bisethyl acetoacetate and aluminum. Isopropoxide alkyl phosphate alkylacetoacetate, titanium tetraacetylacetonate, dialkoxytitanium bisacetylacetonate, dialkoxybistriethanolamine titanate.

The amount of the chelate compound added is 100 for the color pigment.
0.1 to 50 parts by weight, more preferably 0.
5-2 parts by weight is suitable. If the amount of chelate compound added is too large, the pigment cannot be sufficiently fixed to the base particles by coating the resin after adhering the color pigment to the base particles. When the colored base particles are blended in the paint or coating film. In addition, the excessive chelate compound causes problems such as thickening of the paint and deterioration of the weather resistance of the coating film. On the other hand, when the addition amount is too small, it is possible to uniformly and finely adhere the color pigment to the base particles. It is not possible to obtain vivid colors.

The second subject of the present invention relates to colored substrate particles in which the above-mentioned surface-treated coloring pigment is adhered to the substrate particles.

According to the present invention, the substrate particles serving as a substrate are not particularly limited, and metal flakes such as aluminum, zinc, copper, bronze, nickel, titanium and stainless, or inorganic flakes such as mica and glass are suitable. . Among them, aluminum flakes are particularly preferable because they are excellent in metallic luster and concealing power, are inexpensive, and have a low specific gravity, and are easy to handle. It is preferable that the flake substrate particles have a thickness of 0.1 to 5 μm and an average particle size of 5 to 100 μm, and that the shape factor obtained by dividing the average particle size by the thickness is in the range of about 5 to 100.

In addition to these flake-shaped substrate particles, granular particles (metals such as aluminum and stainless steel, ceramics such as alumina and glass) having a particle size of 5 to 1000 μm
Those having a degree, preferably 10 to 100 μm, can be used as the base particles. The colored substrate particles using these granular particles are suitably used for applications such as decorative spherical particles and spacers for liquid crystal reflectors. Further, the colored granular base particles using carbon black as the pigment can be used as the conductive filler.

The amount of the surface-treated color pigment to be attached is 0.01 to 0.5 g, and more preferably 0.03 to 0.3 g, per 1 m ² of the surface area of the substrate particles. If the amount of the surface-treated color pigment attached is too small, the surface-treated color pigment cannot be sufficiently colored. On the other hand, if the amount is too large, the surface-treated color pigment tends to fall off.

The method for producing colored substrate particles in the present invention is a dispersion of a surface-treated color pigment by dispersing the color pigment in a non-polar solvent in the presence of a monobasic aromatic carboxylic acid and optionally a chelate compound. After preparing the above, the base particles are added and further dispersed.
At this time, almost all of the coloring pigment adheres to the base particles, and almost no pigment remains in the solvent. A preferred method for dispersing the color pigment is a dispersing method using a grinding medium such as a ball mill, a bead mill, a sand mill or the like. As the dispersion method after adding the base particles, in addition to the above-described dispersion method using the grinding medium, stirring with a stirrer or a disper is also suitable.

As the non-polar solvent which can be used in the present invention, an aliphatic hydrocarbon or aromatic hydrocarbon having a boiling point of about 100 to 250 ° C. and a mixture thereof are suitable.
Specific examples include normal paraffin, isoparaffin, toluene, xylene, solvent naphtha, kerosene, mineral spirits, petroleum benzine and the like. Further, if necessary, an alcohol or ester solvent may be added in a small amount (about 5% or less) as an auxiliary solvent for dispersing the pigment.

As is apparent from the scanning electron micrograph (see FIG. 1) of the colored substrate particles (aluminum flakes) to which the surface-treated colored pigment has been attached in this way, the pigment is finely and uniformly attached to the surface of the colored substrate particles. Therefore, the colored substrate particles show a vivid color tone and are excellent in metallic luster.

The adhesion of the colored pigment to the substrate particles can be improved by coating the resin with a resin from above the pigmented layer of the colored substrate particles. Here, the resin penetrates into the gap between the color pigment and the surface of the base particles and plays a role of immobilization.
Ensure that the color pigment adheres to the substrate particles.

The amount of resin coated is such that the colored substrate particles 10
0.5 to 40 parts by weight with respect to 0 parts by weight, more preferably 5
-20 parts by weight is suitable. If the resin coating amount is too small, sufficient adhesion cannot be obtained, while if it is too large, the gloss of the colored substrate particles is impaired.

The resin to be coated is, for example, synthesized from the following polymerizable monomers: acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, acrylic. Cyclohexyl acid, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2-methoxyethyl acrylate, acrylic acid 2
-Diethylaminoethyl, 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, tetramethylolmethane tetraacrylate, 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, divinylbenzene monooxide.

The method of coating the colored substrate particles with a resin is carried out by adding the above-mentioned polymerizable monomer and a polymerization initiator (benzoyl peroxide, isobutyl peroxide, azobisisobutylnitrile, etc.) to a dispersion of colored substrate particles dispersed in a solvent. A method is preferred in which the monomer is polymerized by heating with stirring to synthesize the polymer, and the polymer is deposited on the surface of the colored substrate particles. As the dispersion of the colored base particles, the dispersion obtained in the step of adhering the surface-treated color pigment to the base particles may be used as it is, or the dispersion may be once solid-liquid separated to form a paste or powder. You may use what dispersed the base particle in the solvent once again. The polymerization reaction is preferably carried out in an oxygen-free atmosphere, for example, an inert gas such as nitrogen or argon. The reaction temperature is preferably 50 to 150 ° C, more preferably 70 to 100 ° C. If the reaction temperature is too low, the polymerization reaction does not occur efficiently, and if it is too high, the reaction proceeds rapidly, so that the resin cannot be deposited on the surface of the colored substrate particles. Reaction time is 0.5-2
About 4 hours is suitable. If the reaction time is too short, the monomer cannot be sufficiently polymerized, and the reaction time is 2
There is no particular advantage if it is longer than 4 hours.

When the colored substrate particles are used in a coating system in which an ester solvent or a ketone solvent is present, a silane coupling agent or titanium coupling agent having an amino group in the molecule is further coated on the resin. It is desirable to form a coating layer of This is because the coating layer made of the coupling agent prevents the resin from eluting into the solvent and further improves the adhesion of the pigment. Examples of the silane coupling agent that can be used in the present invention include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane and N-.
Examples include β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane and the like. Further, examples of the titanium coupling agent include isopropyl tri (N-aminoethyl aminoethyl) titanate and dibutoxybistriethanolamine titanate.

The resin-coated substrate particles are treated with a coupling agent by adding the coupling agent and water if necessary to a dispersion prepared by dispersing the resin-coated substrate particles in a solvent, and heating the mixture while stirring to perform hydrolysis. Then, a method of depositing and adhering the coupling agent on the resin-coated colored substrate particles or a method of forming a paste comprising the resin-coated colored substrate particles and a non-polar solvent and adding the coupling agent in the kneading process is preferable. It is considered that the resin-coated colored substrate particles thus treated are coated with a silane coupling agent or a titanium coupling agent which is hydrolyzed and condensed.

The colored substrate particles of the present invention are used as a resin composition blended in paints, inks, resin moldings and the like. The resin composition mentioned here includes a paint and its coating film, an ink and its printed matter, a resin molded product, and pellets as a raw material thereof. When used in the resin composition, the blending amount of the colored substrate particles is 0.1 to 30 relative to the composition.
Weight percent is suitable. If the blending amount of the colored substrate particles is too small, a sufficient decorative effect cannot be obtained. On the other hand, if the blending amount is too large, the physical properties of the resin composition such as weather resistance, corrosion resistance and mechanical strength are adversely affected.

The paint / ink is composed of the following components: 1) Resin: acrylic, alkyd, polyester, polyurethane, polyvinyl acetate, nitrocellulose, fluororesin 2) Pigment: In addition to the colored substrate particles according to the present invention The following coloring pigments or extender pigments or dyes may be used in combination.

Phthalocyanine, quinacridone, isoindolinone, perylene, azo lake, iron oxide, yellow lead, carbon black, titanium oxide, pearl mica, etc. 3) Additives: solvent, surfactant, curing agent, ultraviolet absorber, static eliminator Agents, adhesives, etc.

The resin molding is composed of the following components: 1) Resin: polyethylene, polypropylene, polybutadiene, polycarbonate, ABS, polyvinyl chloride, etc. 2) Pigment: In addition to the colored substrate particles according to the present invention, Such coloring pigments or extender pigments or dyes may be used in combination.

Phthalocyanine, quinacridone, isoindolinone, perylene, azo lake, iron oxide, yellow lead, carbon black, titanium oxide, pearl mica, etc. 3) Additives: coupling agents, plasticizers, curing agents, etc.

[0036]

By using the surface-treated pigment of the present invention, the coloring pigment can be finely and uniformly adhered to the base particles, so that the base particles having excellent saturation can be obtained.
Further, by coating with a polymer synthesized from a polymerizable monomer or a coating agent with the polymer and a coupling agent having an amino group, the color pigment is fixed to the base particles, and the adhesion of the pigment can be improved. .

Since the range of color pigments that can be used in the present invention is wide, it is possible to obtain colored substrate particles having any color.

The present invention can be widely applied as a method for uniformly and efficiently adhering fine particles to the surface of base particles having a relatively large particle diameter.

[0039]

【Example】

<Examples and Comparative Examples> (Example 1) 1 g of a commercially available diketopyrrolopyrrole red pigment (IRGAZIN DPPRED BO of Ciba-Geigy Co., Ltd.), 0.5 g of benzoic acid (50 parts by weight per 100 parts by weight of pigment),
10g of mineral spirits was added, 200g of glass beads with a diameter of 1mm was inserted, diameter of 5cm, internal volume of 300c
Ball mill dispersion was carried out for 24 hours with the pot mill of c. Then, 11.4 g (10 g as metal content) of commercially available aluminum paste (Made by Toyo Aluminum Co., Ltd., Miraglo 1000-70% metal content, average particle size 1.4 m ² / g) and 20 g of mineral spirit were put into this pot mill. The mixture was added and dispersed by a ball mill for another hour. The resulting slurry was washed with 70 g of mineral spirits to separate it from the glass beads, and allowed to stand for a while to precipitate aluminum flakes. The supernatant of the slurry was transparent. When the solvent was removed from this slurry and the aluminum flakes were observed with an optical microscope, red pigments were attached to the individual aluminum flakes. The pigment deposition amount of this aluminum flake is 0.07 g / m ²
Met.

(Example 2) 0.1 g of dialkoxyaluminum alkyl acetoacetate (Planeact ALM, Ajinomoto Co., Inc.) as a chelate compound in addition to benzoic acid
The red pigment was adhered to the aluminum flakes in the same manner as in Example 1 except that (10 parts by weight based on 100 parts by weight of the pigment) was added. When the obtained aluminum flakes were observed with an optical microscope, the red pigment was uniformly attached to each aluminum flake. A scanning electron micrograph of the aluminum flakes is shown in FIG. 1. The pigment was finely and uniformly adhered to the surface of the flakes.

(Examples 3 to 12 and Comparative Examples 1 to 5) The same as Example 1 except that the type and amount of the monobasic aromatic carboxylic acid and the type and amount of the chelate compound were changed as shown in Table 1. Then, colored substrate particles of Examples 3 to 12 and Comparative Examples 1 to 5 were prepared.

Table 1 also shows the results of five-stage evaluation of the pigment adhesion state observed by optical microscope observation and scanning electron microscope. In the table, the addition amounts of the monobasic aromatic carboxylic acid and the chelate compound are parts by weight based on 100 parts by weight of the base particles.

(Examples 13 to 24, Comparative Examples 6 to 7) Examples 13 to 24 and Comparative Example 6 were performed in the same manner as in Example 2 except that the type of base particles and the type and amount of color pigments were changed.
~ 7 colored substrate particles were obtained. Table 2 shows the conditions under which these pigments were prepared and the state of adhesion of the pigments. In the table, the amount of the pigment added is parts by weight based on 100 parts by weight of the base particles.

(Example 25) Colored substrate particles 1 of Example 2
0.25g of methyl methacrylate in a slurry containing 0g,
0.25 g of 1,6 hexanediol diacrylate, 0.25 g of styrene, and 0.25 g of acrylic acid (total of monomers: 10 parts by weight to 100 parts by weight of colored substrate particles) were added, and the mixture was stirred at 80 ° C. in nitrogen. The monomer was polymerized by heating and adding 0.05 g of azobisisobutyl nitrile as a polymerization initiator and reacting for 12 hours to deposit on the surface of the colored substrate particles. After the treatment, the slurry was solid-liquid separated into a paste having a solid content of 50%.

(Example 26) Colored substrate particles 1 of Example 4
To a slurry containing 0 g, 0.5 g of acrylic acid, 0.5 g of ditrimethylolpropane tetraacrylate, 0.5 g of diethylaminoethyl methacrylate, 0.5 g of vinyltoluene (total monomer: 20 parts by weight based on 100 parts by weight of colored substrate particles). Then, 0.1 g of azobisisobutylnitrile was added as a polymerization initiator while heating and stirring in nitrogen at 80 ° C. to polymerize the monomer, and the monomer was deposited on the surface of the colored substrate particles. After the treatment, the slurry is separated into solid and liquid,
It was made into a paste having a solid content of 50%.

Example 27 1.0 g of methacrylic acid, 1.0 g of trimethylolpropane triacrylate, 1.0 part by weight of butyl acrylate, 1.0 part of divinylbenzene were added to a slurry containing 10 g of the colored substrate particles of Example 17. Monomer total: 40 parts by weight with respect to 100 parts by weight of the colored substrate particles), and while heating and stirring in nitrogen at 80 ° C.,
0.3 g of benzoyl peroxide was added as a polymerization initiator to polymerize the monomer and deposit it on the surface of the colored substrate particles. After the treatment, the slurry was solid-liquid separated into a paste having a solid content of 50%.

Example 28 A slurry containing 10 g of the colored substrate particles of Example 13 was added to 0.3 g of acrylic acid, 0.3 g of ditrimethylolpropane tetraacrylate, 0.3 part by weight of glycidyl methacrylate, and 0.3 g of styrene (monomer). Total: 12 parts by weight based on 100 parts by weight of colored substrate particles), and 0.05 g of azobisisobutylnitrile as a polymerization initiator while heating and stirring at 80 ° C. in nitrogen.
Was added to polymerize the monomer to deposit it on the surface of the colored substrate particles. Then, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.1 was added to the slurry.
g (1 part by weight with respect to 100 parts by weight of the colored substrate particles) was added, and the mixture was further reacted in the air for 1 hour. After the treatment, the slurry was solid-liquid separated into a paste having a solid content of 50%.

(Example 29) To 16 g of the colored substrate particles of Example 26, 0.08 g of dibutoxybistriethanolamine titanate (1 part by weight per 100 parts by weight of colored substrate particles) and 1 g of butyl alcohol were added.

(Comparative Example 8) 10 g of substrate particles (MG1000 manufactured by Toyo Aluminum Co., Ltd.) (in terms of metal content) and a diketopyrrolopyrrole red pigment (IRC Japan Geiba Ltd. IR)
GAZIN DPP RED BO) was dispersed in 100 ml of mineral spirit to prepare a slurry. To the slurry was added 0.25 g of methyl methacrylate, 0.25 g of 1,6 hexanediol diacrylate, 0.25 g of styrene, and 0.25 g of acrylic acid (total of monomers: 10 parts by weight based on 100 parts by weight of colored substrate particles). While heating and stirring in nitrogen at 80 ° C., 0.05 g of azobisisobutylnitrile was added as a polymerization initiator to polymerize the monomer, and the monomer was deposited on the surface of the base particles together with the pigment. After the treatment, the slurry was solid-liquid separated into a paste having a solid content of 50%.

(Comparative Example 9) Substrate particles 10 prepared in Example 2 with the addition amount of the chelate compound (dialkoxyaluminum alkyl acetoacetate) being 0.6 g.
g slurry containing 0.3 g of acrylic acid, 0.3 g of ditrimethylolpropane tetraacrylate, 0.3 part by weight of glycidyl methacrylate, 0.3 g of styrene (total amount of monomers: 12 parts by weight per 100 parts by weight of colored substrate particles). Was added, and 0.05 g of azobisisobutylnitrile as a polymerization initiator was added while heating and stirring in nitrogen at 80 ° C.
Was added to polymerize the monomer to deposit it on the surface of the colored substrate particles. After processing, the slurry is separated into solid and liquid, and the solid content is 50
% Of paste.

(Comparative Example 10) In Example 2, 1.2 g of the monobasic aromatic carboxylic acid agent (benzoic acid) was added.
0.3 g of acrylic acid, 0.3 g of ditrimethylolpropane tetraacrylate, 0.3 part by weight of glycidyl methacrylate, in a slurry containing 10 g of colored substrate particles prepared as (100 parts by weight of color pigment).
0.3 g of styrene (total of monomers: 100 particles of colored substrate)
(12 parts by weight relative to 1 part by weight), and while heating and stirring in nitrogen at 80 ° C., 0.05 g of azobisisobutylnitrile as a polymerization initiator is added to polymerize the monomer,
It was deposited on the surface of the colored substrate particles. After the treatment, the slurry was solid-liquid separated into a paste having a solid content of 50%.

(Test 1) Examples 25 to 29 and Comparative Example 8
With respect to the color tone of the colored substrate particles obtained in Nos. 10 to 10, the color saturation and the metallic luster of the coated plate prepared by coating the pigment with this pigment were evaluated by visual evaluation on a 5-grade scale. The paint was prepared by adding 100 parts by weight of an automobile repair varnish (Auto Clear manufactured by Nippon Paint Co., Ltd.) to 10 parts by weight of the colored substrate particles, and dispersing with a homomixer. The obtained coating material was applied onto a double-sided art paper with a 225 μm (9 mill) doctor blade to prepare a coated plate.

A similar test was conducted on commercially available colored substrate particles.

(Test 2) 0.3 g of each of the colored aluminum flakes obtained in Examples 25 to 29 and Comparative Examples 8 to 10 was added to 30 g of each of four kinds of solvents of toluene, isopropyl alcohol, ethyl acetate and methyl ethyl ketone with a homomixer. Was dispersed at a rotation speed of 3200 RPM for 3 minutes, the obtained dispersion was allowed to stand for 24 hours, and then the supernatant liquid was observed to evaluate the degree of pigment loss.

A similar test was conducted on commercially available colored substrate particles.

The results of tests 1 and 2 are shown in Table 3.

(Example 30) 20 g of the colored substrate particles obtained in Example 26 were sampled, and 80 g of a commercially available thermosetting acrylic resin varnish (Acridic A-322, Dainippon Ink and Chemicals, Inc.) and melamine were used. Resin varnish (Dainippon Ink and Chemicals Co., Ltd. Super Beckamine L-117-6
0) 17 g was added and dispersed by a disper to prepare a red metallic paint. Apply this metallic paint to thinner (ethyl acetate: butyl acetate: xylene: cellosolve acetate: solveso # 100 = 15: 6: 20: 9: 12).
Dilute with 100 g and coat with air spray on a mild steel plate, and from there, further commercially available thermosetting acrylic resin varnish (ACRIDIC A-345, Dainippon Ink and Chemicals, Inc.) 5
6 g, 22 g of melamine resin varnish (Dainippon Ink and Chemicals Co., Ltd. Super Beckamine L-117-60),
A clear paint consisting of 70 g of thinner (the above composition) was applied by air spray. The coated plate thus obtained was baked at 140 ° C. to obtain a 2-coat 1-bake metallic coating film. The coating film obtained had a bright red color and was excellent in metallic luster.

(Comparative Example 11) A metallic paint was prepared in the same manner as in Example 27 except that 14.3 g of the base particles (solid content 70%) prepared under the conditions of Comparative Example 2 was used as the pigment. A coat 1 bake metallic coating film was prepared. The obtained coating film was inferior in color vividness to the coating film obtained in Example 27.

(Example 31) 3 g of the colored substrate particles obtained in Example 26 was sampled as an aluminum content, and was mixed with 100 g of polyethylene resin to prepare a molded product by injection molding. The obtained molded product had a bright red metallic appearance.

Comparative Example 12 A molded article was prepared in the same manner as in Example 23 except that 3 g of the base particles obtained in Comparative Example 2 was used as the pigment as the aluminum component. The obtained molded product had a metallic appearance, but a very vivid color was not obtained.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[Brief description of drawings]

FIG. 1 is a scanning electron micrograph showing the particle structure of colored substrate particles of the present invention.

Front page continued (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09C 3/68 C09C 1/64 C09C 3/10 C09C 3/12

Claims (8)

(57) [Claims] 1. Surface area of a surface-treated coloring pigment is 1
It is a colored substrate particle formed by adhering 0.01 to 0.5 g per m ² , and the surface-treated colored pigment is 100
0.2 to 100 parts by weight of monobasic aromatic carboxylic acid, or 0.2 to 100 parts by weight of color pigment.
~ 100 parts by weight of monobasic aromatic carboxylic acid and 0.1 to
The colored base particles, wherein the surface of the color pigment is coated with 50 parts by weight of an aluminum or titanium chelate compound. 2. The monobasic aromatic carboxylic acid is benzoic acid,
The colored substrate particles according to claim 1, wherein the colored substrate particles are at least one selected from aminobenzoic acid, aminohydroxybenzoic acid, naphthoic acid, aminonaphthoic acid, cinnamic acid, and aminocinnamic acid. 3. The surface of a polymer synthesized from a polymerizable monomer is coated on the surface of the polymer.
Or the colored substrate particles described in 2. 4. A silane coupling agent having an amino group and / or a titanium coupling agent having an amino group are attached to the surface of the silane coupling agent.
The colored substrate particles according to [4]. 5. A. The color pigment is dispersed in a non-polar solvent in the presence of a monobasic aromatic carboxylic acid, or in the presence of a monobasic carboxylic acid and an aluminum or titanium chelate compound, to give a monobasic aromatic group on the surface of the color pigment. Forming a coating layer made of a carboxylic acid or a coating layer made of a monobasic aromatic carboxylic acid and an aluminum or titanium chelate compound to form a dispersion of a surface-treated color pigment, b. A method for producing colored substrate particles, which comprises a step of adding substrate particles to a dispersion of the surface-treated color pigment and mixing them to deposit the surface-treated color pigment on the surface of the substrate particles. 6. After the steps a and b, c. Adding a polymerizable monomer and a polymerization initiator, and d. The method according to claim 5, characterized in that the method comprises heating with stirring to synthesize a polymer from the polymerizable monomer, and having the positive effect of precipitating the polymer on the surface of the colored substrate particles. 7. After the steps c and d, further e. Adding a silane coupling agent having an amino group and / or a titanium coupling agent having an amino group, and f. A silane coupling agent having the amino group and / or
The method according to claim 6, further comprising the step of hydrolyzing the titanium coupling agent having an amino group. 8. A resin composition comprising 0.1 to 30% by weight of the colored substrate particles according to any one of claims 1 to 4.