JP5779384B2 - Colorant - Google Patents

Description

  The present invention relates to a colorant used for metallic paint finishing of automobiles, plastic decorative finishing, printing inks and the like. In particular, the present invention relates to a colorant having a base particle of a metal pigment, more preferably an aluminum pigment. Furthermore, it is related also with the coating composition formed by mix | blending the coloring agent.

  Generally, a color pigment such as an organic pigment or an inorganic pigment is used as the colorant. For the purpose of imparting concealability or metallic feeling to these colorants, colorants in which a color pigment is adhered to base particles such as metal pigments, particularly aluminum pigments, have been developed.

  A colorant in which a color pigment is attached to a metal pigment has excellent performance in that a vivid color tone is obtained and the concealability of a base color is good. These colorants include diketopyrrolopyrrole, quinacridone, dioxazine, isoindolinone, condensed azo, selenium, perinone, perylene, quinophthalone, phthalocyanine and other organic pigments and iron oxides, Inorganic pigments such as carbon black are used.

  For example, Japanese Patent Application Laid-Open No. 58-141248 (Patent Document 1) discloses a colored metallic pigment in which a colored pigment is uniformly attached to the surface of the metallic pigment by a polymer composed of a monomer having a polymerizable double bond. Japanese Patent No. 508424 (Patent Document 2) discloses a colored pigment comprising a combination of a flake which is a metal in particular and a polymer matrix which is held thereon and encapsulates a solid colored metal pigment, Japanese Patent Application Laid-Open No. 01-315470. In the publication (Patent Document 3), a carboxylic acid having one or more double bonds and two or more carboxyl groups obtained by thermally polymerizing one or more carboxylic acids having a double bond on the surface of a metallic pigment. In Japanese Patent Laid-Open No. 09-040885 (Patent Document 4), a colored metallic pigment obtained by chemically adsorbing a colored pigment via a pigment A surface-treated colored pigment obtained by coating 0.2 to 100 parts by weight of a monobasic aromatic carboxylic acid on the surface of a colored pigment, Japanese Patent Application Laid-Open No. 09-059532 (Patent Document 5) includes: In a colored metal flake pigment having a vapor-deposited layer of an organic coloring pigment on its surface, Japanese Patent Application Laid-Open No. 09-124973 (Patent Document 6), two in a molecule of 0.2 to 100 parts by weight with respect to 100 parts by weight of the coloring pigment. A surface-treated colored pigment characterized by coating the surface of a colored pigment with an amino compound having the amino group and having no carboxyl group has been proposed.

JP 58-141248 A JP 05-508424 gazette Japanese Patent Laid-Open No. 01-315470 JP 09-040885 A JP 09-059532 A JP 09-124973 A

  In each of the above proposals, it may be difficult to sufficiently and uniformly attach the color pigment to the base particles, and there has been a problem in obtaining a colorant having particularly high saturation. In addition, there is a tendency that the colored pigment is partly free or aggregates on the base particles, and when such a colorant is dispersed in a paint or a solvent, the colored pigment is likely to fall off.

  The present invention has been made in view of the current situation as described above, and an object of the present invention is to provide a colorant that has high saturation and reduced color pigment dropout.

  As a result of various studies on the above problems, the present inventors have found that if there is a base particle to which no colored pigment is attached to the surface, the saturation is lowered by direct reflection of light from the base particle. . For this reason, the present inventors have found that the above-mentioned problems can be solved if the colored pigment can be uniformly attached to the surface of each substrate particle and the dropping of the colored pigment once attached can be reduced. The present invention has been completed through further research.

  That is, the colorant of the present invention comprises base particles, an organic phosphate compound layer formed on the surface of the base particles, and a color pigment attached to the surface of the organic phosphate compound layer.

  Here, the organic phosphoric acid compound layer is preferably composed of an organic phosphoric acid compound having at least one polymerizable double bond, and is composed of an organic phosphoric acid compound having at least two polymerizable double bonds. It is more preferable.

  The base particles are preferably a metal pigment, and more preferably an aluminum pigment. The colorant of the present invention preferably further has a resin coating layer formed on the color pigment.

  The present invention also relates to a coating composition comprising the above colorant.

  The colorant of the present invention has an excellent effect of having high saturation and reducing the dropout of the color pigment by having the above-described configuration.

Hereinafter, the present invention will be described in more detail with reference to embodiments.
<Colorant>
The colorant of the present invention has a basic structure including a base particle, an organic phosphate compound layer formed on the surface of the base particle, and a color pigment attached to the surface of the organic phosphate compound layer. Hereinafter, each component will be described in more detail.

<Substrate particles>
Examples of the base particles constituting the colorant of the present invention include metal pigments, mica, flaky glass, metal oxides (alumina, silica, etc.), non-oxide ceramics (graphite, silicon carbide, silicon nitride, etc.), resins ( PET, polyethylene, etc.). Among these, metal pigments are preferable, and aluminum pigments are particularly preferable.

  Examples of the metal pigment include metal pigments composed of metals such as aluminum, zinc, copper, silver, iron, bronze, nickel, titanium, and stainless steel, and metal pigments composed of alloys containing these metals.

  Among these metal pigments, aluminum pigments made of aluminum are particularly suitable because they are highly reflective and excellent in metallic luster, are inexpensive and easy to handle because of their low specific gravity. In addition, in such a metal pigment, particles that have a metallic feeling by forming a metal film on the surface of inorganic compound particles (glass, mica, ceramic particles such as alumina or titania) by plating or the like. Is also included.

  Hereinafter, an aluminum pigment particularly suitable as such a metal pigment will be described. Here, as a composition of the aluminum pigment used for this invention, it may be comprised only from aluminum, and may be comprised from the aluminum base alloy, The purity of aluminum is not specifically limited.

  Moreover, the shape of the aluminum pigment used for this invention can use the thing of various shapes, such as granular form, plate shape, block shape, flake shape (flaky shape), but gives the metallic feeling and brightness | luminance which were excellent in the coating film. For this purpose, a flake shape is preferred.

  And although the average particle diameter of the aluminum pigment used for this invention is not specifically limited, It is preferable that it is 1 micrometer or more, and if it is especially 5 micrometers or more, it is more preferable. The average particle diameter is preferably 100 μm or less, more preferably 50 μm or less.

  When the average particle size is 1 μm or more, the handling in the manufacturing process is easy, and the aluminum pigment tends to hardly aggregate. When the average particle size is 100 μm or less, the surface of the coating film is used when used as a paint. Roughening can be prevented and a preferable design can be realized.

  Furthermore, the average thickness of the aluminum pigment used in the present invention is not particularly limited, but is preferably 0.02 μm or more, and more preferably 0.1 μm or more. The average thickness is preferably 5 μm or less, more preferably 2 μm or less. When this average thickness is 0.02 μm or more, it is advantageous in terms of ease of production process, and when the average thickness is 5 μm or less, it is advantageous in terms of the appearance of a coating composition such as a coating film.

  Here, the average particle size of the aluminum pigment used in the present invention is obtained by calculating the volume average based on the particle size distribution measured by a known particle size distribution measurement method such as a laser diffraction method. The average thickness is calculated from the hiding power and density of the aluminum pigment.

  Further, a grinding aid may be attached to the surface of the aluminum pigment used in the present invention. As such a grinding aid, conventionally known ones can be used without any particular limitation.

  Further, the method for obtaining the aluminum pigment used in the present invention is not particularly limited. For example, in the presence of a grinding medium in a ball mill or an attritor mill, the raw aluminum powder is ground using a grinding aid such as a fatty acid. Alternatively, it may be produced by grinding or may be obtained by crushing an aluminum-deposited foil in which aluminum is deposited on a film. As said grinding | pulverization medium, mineral oil of high flash point, such as a mineral spirit and solvent naphtha, can be used.

In addition, the above description is the same also about metal pigments other than an aluminum pigment.
<Organic phosphate compound layer>
The organophosphate compound layer of the present invention is composed of an organophosphate compound and is formed on the surface of the substrate particles. This organic phosphoric acid compound layer adheres firmly to the color pigment, and thus has the effect of adhering the color pigment uniformly and firmly onto the substrate particles. Therefore, the colorant of the present invention has an excellent effect of having high chroma and reducing the dropout of the colored pigment mainly by the action of the organic phosphoric acid compound layer.

  Such an organic phosphate compound layer is presumed to be formed by chemically or physically adsorbing the organic phosphate compound on the surface of the substrate particles. In addition, the organic phosphoric acid compound layer may be formed in a state where the organic phosphoric acid compound is layered on the surface of the base particle, or may be formed in a state where the organic phosphoric acid compound is scattered on the surface instead of the layered state. . That is, the organic phosphoric acid compound layer in the present invention is not limited to the case where the organic phosphoric acid compound is present in the form of a continuous layer on the surface of the base particle, but the organic phosphoric acid compound does not form a layer and is scattered on the surface of the base particle. It also includes the case where it exists. In short, the organic phosphoric acid compound layer in the present invention only needs to be present in an amount corresponding to the amount of the color pigment to be attached later, and the presence state is not limited. Therefore, in the present invention, even in a state where the organic phosphoric acid compound is scattered in this way, it is expressed as an organic phosphoric acid compound layer.

  The organic phosphoric acid compound constituting such an organic phosphoric acid compound layer means a compound having a structure in which part of the OH group of phosphoric acid is substituted with an organic substituent. Such an organic phosphate compound is not particularly limited, and examples thereof include organic phosphate esters. Examples of the organic phosphate ester include stearyl acid phosphate, myristyl acid phosphate, palmityl acid phosphate, lauryl acid phosphate, polyoxyethylene alkylphenyl ether acid phosphate, n-decyl acid phosphate, 2-ethylhexyl acid phosphate, oleyl acid phosphate, Examples include hexyl acid phosphate, butyl acid phosphate, and ethylene glycol acid phosphate.

  Such an organic phosphate compound layer is preferably composed of an organic phosphate compound having at least one polymerizable double bond. Examples of such a compound include at least one polymerizable double bond. And organic phosphoric acid esters having Examples of the organic phosphate ester having at least one polymerizable double bond include oleyl acid phosphate, mono (2-acryloyloxyethyl) acid phosphate, mono (2-methacryloyloxyethyl) acid phosphate, and 2-acryloyloxy. Ethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, (2-hydroxyethyl) methacrylate acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, diphenyl-2-methacryloyloxyethyl Acid phosphate, diphenyl-2-acryloyloxyethyl acid phosphate, dibutyl-2-methacryloyloxyethyl acid phosphate Polymerization of dibutyl-2-acryloyloxyethyl acid phosphate, dioctyl-2-methacryloyloxyethyl acid phosphate, dioctyl-2-acryloyloxyethyl acid phosphate, 2-methacryloyloxypropyl acid phosphate, etc. An organic phosphoric acid compound having one ionic double bond.

  In addition, the organic phosphoric acid compound layer of the present invention is preferably composed of an organic phosphoric acid compound having at least two polymerizable double bonds, since it can adhere a colored pigment more firmly. Examples thereof include organic phosphates having at least two polymerizable double bonds. Examples of the organic phosphate ester having at least two polymerizable double bonds include bis (2-chloroethyl) vinylphosphonate, di-2-methacryloyloxyethyl acid phosphate, and tri-2-methacryloyloxyethyl acid phosphate. Organic phosphate compounds having two or more polymerizable double bonds such as fete, di-2-acryloyloxyethyl acid phosphate, tri-2-acryloyloxyethyl acid phosphate, diallyl dibutylphosphonosuccinate be able to.

  In the present invention, it is preferable to use a compound having at least one polymerizable double bond as the organic phosphate compound constituting the organic phosphate compound layer, and use a compound having at least two polymerizable double bonds. It is more preferable. This is because the adhesion of the color pigment is particularly good.

  Although the usage-amount of an organic phosphoric acid compound is not specifically limited, It is 0.1 to 10 mass parts with respect to 100 mass parts of base particles, More preferably, it is 0.5 to 5 mass parts. If it is 0.1 part by mass or more, it is advantageous in terms of adhesion of the color pigment, and if it is 10 parts by mass or less, the film performance of a coating film such as a coating film using a colorant (if too much, adhesion, weather resistance) This is advantageous in that the properties and the like are reduced).

  In the colorant of the present invention, the presence of such an organic phosphate compound layer can be specified by detection and quantification of P (phosphorus) by ICP (Inductively Coupled Plasma) analysis or the like.

<Coloring pigment>
The colored pigment of the present invention adheres to the surface of the organic phosphate compound layer. In the present invention, the above-mentioned substrate particles mainly have a function of concealing the base color or imparting a metallic luster, and are often achromatic in color. However, the present invention is not limited to this. For example, it may have an action of imparting an achromatic color such as white or black.

  Such coloring pigments can be used without any particular limitation on conventionally known pigments. For example, the following can be illustrated.

  That is, diketopyrrolopyrrole, quinacridone, dioxazine, isoindolinone, condensed azo, selenium, perinone, perylene, quinophthalone, phthalocyanine, halogenated phthalocyanine, azomethine metal complex, indones Organic pigments such as ron, anthraquinone, benzimidazolone, triphenylmethane, anthrapyrimidine, iron oxide, carbon black, ultramarine, bitumen, cobalt blue, chrome green, bismuth vanadate, complex oxide calcined pigment And inorganic pigments such as titanium black, titanium oxide, and ultrafine titanium oxide.

  Specifically, phthalocyanine, halogenated phthalocyanine, quinacridone, diketopyrrolopyrrole, isoindolinone, azomethine metal complex, indanthrone, perylene, perinone, anthraquinone, dioxazine, benzimidazolone, condensed azo, triphenylmethane, quinophthalone, Examples include anthrapyrimidine, iron oxide, ultramarine blue, bitumen, cobalt blue, chromium green, bismuth vanadate, composite oxide calcined pigment, carbon black, titanium black, titanium oxide, and ultrafine titanium oxide.

  Particularly preferred pigments from the viewpoint of adhesion to substrate particles, weather resistance and coloring power include phthalocyanine blue, phthalocyanine green, quinacridone red, quinacridone maroon, quinacridone gold, diketopyrrolopyrrole, isoindolinone yellow, and isoindolinone orange. , Anthrapyrimidine yellow, dioxazine violet, perylene maroon, azomethine copper complex, transparent iron oxide, carbon black, ultrafine titanium oxide and the like.

  The primary particle diameter of such a colored pigment is not particularly limited, but a pigment having a primary particle diameter of preferably 0.01 to 1 μm, more preferably 0.02 to 0.1 μm can be used. When the primary particle size is 0.01 μm or more, there is less risk of dispersion of the pigment, and when the primary particle size is 1.0 μm or less, it is difficult to uniformly adhere to the substrate particle surface There is little nature.

  The adhesion amount of the coloring pigment is 1 part by mass or more and 200 parts by mass or less, more preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the base particles on which the organic phosphoric acid compound layer is formed. The amount of adhesion is preferably adjusted as appropriate according to the specific surface area of the substrate particles. When the adhesion amount is less than 1 part by mass, sufficient saturation cannot be obtained with respect to the finally obtained colorant. When the adhesion amount exceeds 200 parts by mass, when the substrate particles are metal pigments, The brightness of the resulting colorant is reduced.

  In addition, it is more preferable that the surface of the color pigment is treated with the following compound in order to improve adhesion.

  That is, examples of such compounds include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, , 12-diaminododecane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,8-diaminonaphthalene, 1,2-diaminocyclohexane, stearylpropylenediamine, N-β- (aminoethyl) -γ- Aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, benzoic acid, vinyl benzoate, salicylic acid, anthrani Acid, m-aminobenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 3-amino-4-methylbenzoic acid, p-aminosalicylic acid, 1-naphthoic acid, 2-naphthoic acid, naphthenic acid, 3- Examples thereof include amino-2-naphthoic acid, cinnamic acid, aminocinnamic acid, and the like, but are not limited thereto.

<Resin coating layer>
In the colorant of the present invention, it is preferable that a resin coating layer is further formed on the color pigment attached to the surface of the organic phosphate compound layer. By forming this resin coating layer, the colored pigment adheres more firmly.

  The composition of the resin coating layer is not particularly limited, but it is preferably composed of, for example, a radical polymerizable resin. This is because the resin coating layer becomes a denser layer with excellent solvent resistance, so that the color pigments are less likely to fall off or change in quality.

  When the resin coating layer is formed from such a radical polymerizable resin, the amount of the radical polymerizable resin is suitably 0.5 to 100 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the base particles. It is. The amount of the radical polymerizable resin can be appropriately determined in consideration of the thickness of the target resin coating layer, the specific surface area of the metal pigment, the density of the radical polymerizable resin to be coated, and the like.

  In addition, the thickness of the resin coating layer composed of such radically polymerizable resin is not particularly limited. However, if the thickness is 5 nm or more and 200 nm or less, the adhesion of the colored pigment can be strengthened without inconvenience. preferable. The thickness can be measured by observing the colorant with a scanning electron microscope or the like.

  A specific method for coating the surface of the colored pigment attached to the base particles with such a radical polymerizable resin is that the base particles attached with the colored pigment are coated with a hydrocarbon or alcohol solvent (preferably a hydrocarbon solvent). A monomer and / or oligomer and a polymerization initiator such as benzoyl peroxide, isobutyl peroxide or azobisisobutyronitrile are added to the dispersed dispersion, and the monomer and / or oligomer are radically polymerized by heating while stirring. And a method of depositing on the surface of the colored pigment is preferable.

  In this case, the addition amount of the polymerization initiator is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the monomer and / or oligomer. The polymerization reaction is desirably performed in an oxygen-free atmosphere, for example, an inert gas such as nitrogen or argon. The reaction temperature is suitably 50 to 150 ° C, more preferably 70 to 100 ° C. The reaction time is preferably 30 minutes or longer and 30 hours or shorter.

Examples of the monomer and / or oligomer include the following.
That is, acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, acrylic acid 2-methoxyethyl, 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, tetramethylolmethane tetraacrylate, pentaerythris Tall triacrylate, trisacryloxyethyl phosphate, ditrimethylolpropane tetraacrylate, styrene, α-methylstyrene, vinyl toluene, 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, mono (2-acryloyloxyethyl) acid phosphate, mono (2-methacryloyloxyethyl) acid phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, (2-hydroxyethyl) Methacrylate acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, diphenyl-2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl acid phosphate, dibutyl- 2-methacryloyloxyethyl acid phosphate, dibutyl-2-acryloyloxyethyl acid phosphate, dioctyl-2-methacryloyloxyethyl acid phosphate, dioctyl-2-acryloyloxyethyl acid phosphate, 2-methacryloyl Roxypropyl acid phosphate, bis (2-chloroethyl) vinyl phosphonate, di-2-methacryloyloxyethyl acid phosphate, Li-2-methacryloyloxyethyl acid phosphate, di-2-acryloyloxyethyl acid phosphate, tri-2-acryloyloxyethyl acid phosphate, diallyldibutylphosphonosuccinate, acrylic modified polyester (degree of polymerization 2 ˜20), acrylic modified polyether (degree of polymerization of about 2 to 20), acrylic modified urethane (degree of polymerization of about 2 to 20), acrylic modified epoxy (degree of polymerization of about 2 to 20), acrylic modified spyrane (degree of polymerization of 2 to 2). The present invention is not limited to these.

  In particular, when a monomer and / or oligomer having two or more polymerizable double bonds is used as the monomer and / or oligomer, a resin coating layer composed of a three-dimensionally cross-linked radically polymerizable resin is formed. Is advantageous.

  In the case where the organic phosphoric acid compound layer is composed of an organic phosphoric acid compound having at least one polymerizable double bond, a part of the monomer or oligomer constituting the resin coating layer is formed at the time of forming the resin coating layer. It may be reacted with a part of the organic phosphoric acid compound.

  In the colorant of the present invention, whether or not the resin coating layer is composed of a radical polymerizable resin can be identified by mass spectrometry, analysis of a polymerization initiator residue by NMR or the like, more simply molecular weight. , Molecular weight distribution, glass transition point, solubility in organic solvents, and the like.

<The manufacturing method of the coloring agent of this invention>
The colorant of the present invention can be produced by the following method, but is not limited thereto.

<Organic phosphate compound layer forming step>
First, an organic phosphate compound layer is formed on the surface of the substrate particles. Examples of the method for forming the organic phosphate compound layer on the surface of the substrate particles include a method of adsorbing the organic phosphate compound on the surface of the substrate particles. For example, it can be executed by the following method.

  That is, the organic phosphoric acid compound can be adsorbed on the surface of the base particle by bringing the base particle into contact with a solution in which the organic phosphoric acid compound is dissolved in a solvent exemplified below and dispersing it at a predetermined temperature for a predetermined time.

  Examples of the solvent include methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, s-butanol, t-butanol, glycerin, allyl alcohol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol. Examples include monomethoxymethyl ether, diethylene glycol, propylene glycol monobutyl ether, acetone, acetylacetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, diacetone alcohol, methyl isobutyl ketone, methyl-n-butyl ketone, methyl-n-propyl ketone, dimethyl sulfoxide and the like. .

  In addition, as a method of bringing the substrate particles into contact, a method of processing in a slurry state, a method of kneading in a paste state, or the like can be adopted, but is not limited thereto. Further, the treatment temperature is not limited, but it is preferably performed at 5 ° C. or higher and 100 ° C. or lower, preferably 30 ° C. or higher and 70 ° C. or lower. Also, the treatment time is not particularly limited, but it is preferably 1 minute to 180 minutes, preferably 10 minutes to 60 minutes.

<Coloring pigment adhesion process>
Subsequently, a color pigment is adhered to the surface of the organic phosphoric acid compound layer formed on the surface of the base particle as described above. This adhesion method can be executed by the following method, for example.

  That is, as a first step, a colored pigment is dispersed in a solvent, preferably a nonpolar solvent, to prepare a colored pigment dispersion (slurry). At this time, as described above, the specific compound may be added to the dispersion for the purpose of treating the surface of the color pigment with a specific compound such as ethylenediamine in order to improve the adhesion of the color pigment. . Moreover, you may add dispersing agents, such as surfactant and a chelate compound, in this dispersion as needed.

  Here, as the nonpolar solvent, aliphatic hydrocarbons, aromatic hydrocarbons having a boiling point range of about 100 to 250 ° C., mixed solvents thereof, and the like can be suitably used. Specific examples include normal paraffin, isoparaffin, toluene, xylene, solvent naphtha, kerosene, mineral spirit, and petroleum benzine, but are not limited thereto. If necessary, an alcohol or ester solvent may be added in a small amount as an aid for dispersion of the color pigment.

  The method for dispersing the color pigment is not particularly limited, and examples thereof include a dispersion method using a grinding medium such as a ball mill, a bead mill, and a sand mill. Although the dispersion time is not particularly limited, it is within the range of 30 minutes to 30 hours because of the designability of the colorant (decrease in designability at 30 minutes or less) and productivity (productivity is poor at 30 hours or more). Is preferred. Moreover, the temperature at the time of dispersion | distribution is not specifically limited, What is necessary is just in the range of 0 to 100 degreeC.

  Next, as a second step, the base particles on which the organic phosphoric acid compound layer is formed are added to the dispersion of the colored pigment prepared above and further dispersed, and the colored pigment is adhered to the surface of the organic phosphoric acid compound. As a dispersion method in this case, stirring with a stirrer or a disper is also suitable in addition to the above-described dispersion method.

  The dispersion time in the second stage is not particularly limited, but is within the range of 30 minutes to 30 hours. The dispersion degree of the color pigment (the pigment cannot be sufficiently dispersed in 30 minutes or less) and the productivity (productivity in 30 hours or more). This is preferable for the reason of (decrease). Moreover, the temperature at the time of dispersion | distribution is not specifically limited, What is necessary is just in the range of 0 to 100 degreeC.

  By such a method, the colorant of the present invention in which a color pigment adheres to the surface of the organic phosphoric acid compound layer of the substrate particles can be obtained. As is clear from the above description, the adhesion of the color pigment to the surface of the organic phosphate compound layer is considered to be physical adsorption or chemical adsorption.

  In the above description, the first stage and the second stage have been described separately. However, there is no reason why the first stage and the second stage should be performed in this order. Also, a method of adding and dispersing all the components used in the second stage at a time can be adopted as long as the effect of the present invention is not impaired.

<Resin coating layer forming step>
If desired, the colorant of the present invention can further form a resin coating layer on the above-mentioned color pigment. This resin coating layer can be formed by the method already described in the section of the resin coating layer.

<Coating composition>
The present invention also relates to a coating composition comprising the colorant described above. Such a coating composition usually contains a colorant, a resin component, and a solvent.

  The blending amount of the colorant in the coating composition of the present invention is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the resin component. . If the colorant is less than 0.1 parts by mass, the intended designability cannot be obtained, and if it is more than 50 parts by mass, the sharpness of the coating film decreases.

  The blending amount of the solvent in the coating composition of the present invention is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin component. When the amount of the solvent is less than 1 part by mass, the dispersibility of the colorant in the coating composition becomes insufficient. When the amount is more than 100 parts by mass, environmental pollution due to the solvent that evaporates when the coating composition is dried and cured becomes a problem. .

  Although the resin component mix | blended with the coating composition of this invention does not have limitation in particular, For example, thermosetting acrylic resin / melamine resin, thermosetting acrylic resin / CAB (cellulose acetate butyrate) / melamine resin, thermosetting type Examples include polyester (alkyd) resin / melamine resin, thermosetting polyester (alkyd) / CAB / melamine resin, isocyanate curable urethane resin / room temperature curable acrylic resin, water-diluted acrylic emulsion / melamine resin, and the like.

  Although the solvent mix | blended with the coating composition of this invention is not specifically limited, Hydrophilic solvent (For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl), such as water, alcohol type, glycol type, ketone type, ester type, etc. Alcohol, t-butyl alcohol, n-butyl alcohol, isobutyl alcohol, ethyl cellosolve, butyl cellosolve, butyl carbitol, propylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, acetone, ethyl acetate , Propyl acetate, etc.), aromatic solvents, alicyclic solvents, hydrocarbon solvents, etc. (eg benzene, toluene, xylene, hexane, heptane, cyclohexane) Sun, can be used octane, mineral spirits, etc.).

  In addition, such a coating composition may contain additives such as a pigment dispersant, an antifoaming agent, an anti-settling agent, a curing catalyst, and other colored pigments as necessary.

  Specific examples of such a coating composition include paints, inks, coating films, and the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

<Example 1>
<Organic phosphate compound layer forming step>
A commercially available aluminum pigment was used as the base particles. This aluminum pigment has a paste-like form by washing the paste containing it (trade name: “TCR2060”, manufactured by Toyo Aluminum Co., Ltd., average particle size 18 μm) with mineral spirit and then filtering. there were. The non-volatile component (aluminum pigment) of the paste after filtration was 70% by mass (the balance was mineral spirit).

  The aluminum pigment was washed with propylene glycol monomethyl ether. Then, 200 g (in terms of solid content) of the washed aluminum pigment was dissolved in 400 g of propylene glycol monobutyl ether with 2 g of di-2-methacryloyloxyethyl acid phosphate (1% by mass with respect to the base particles) as an organic phosphate compound. The obtained solution was added and stirred at 75 ° C. for 1 hour to obtain a slurry. The obtained slurry was subjected to solid-liquid separation, and an organic phosphoric acid compound was adsorbed on the surface of the base particles to obtain a colorant precursor paste (solid content: 70% by mass) on which an organic phosphoric acid compound layer was formed.

<Coloring pigment adhesion process>
Commercially available phthalocyanine blue pigment (trade name: “Lionol Blue PM7185” (primary average particle size 0.02 μm), Toyo Ink Co., Ltd. 20 g, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane (2.5% by mass with respect to the colored pigment) and 30 g of mineral spirit are added, and the colored pigment is dispersed by a ball mill for 24 hours. did.

  Thereafter, 42.9 g of colorant precursor paste (30 g as a solid content) and 30 g of mineral spirit that were subjected to the organic phosphoric acid compound layer forming step were added to the pot mill, and further dispersed by a ball mill for 1 hour. By this step, the color pigment was adhered to the surface of the organic phosphoric acid compound layer of the colorant precursor.

  By washing the slurry thus obtained with 500 g of mineral spirits, the glass beads and the target product are separated, and then filtered to form a surface of the organic phosphate compound layer formed on the surface of the base particles. The colorant of the present invention having the color pigment adhered thereto was obtained.

<Resin coating layer forming step>
In a slurry obtained by dispersing 20 g (as a solid content) of the colorant obtained above in 200 g of mineral spirit, 0.3 g of acrylic acid, 0.3 g of trimethylolpropane triacrylate, 0.3 g of styrene, 0.3 g of epoxidized polybutadiene Then, 0.05 g of azobisisobutylnitrile as a polymerization initiator is added as a polymerization initiator while radically polymerizing these monomers while heating and stirring in nitrogen at 80 ° C., whereby the coloring pigment of the colorant obtained above is obtained. A resin coating layer composed of a radical polymerizable resin was formed thereon.

  After this treatment, the slurry was subjected to solid-liquid separation, whereby the colorant of the present invention in which a resin coating layer was formed on a color pigment was obtained in a paste state (solid content 60 mass%).

  By dispersing 2.5 g (as a solid content) of the colorant of the present invention thus obtained in 50 g of a commercially available acrylic lacquer (trade name: “Autoclear”, manufactured by Nippon Paint Co., Ltd.), A coating composition of the present invention was prepared. A coating plate was prepared by applying this coating composition to double-sided art paper using a 250 μm doctor blade. The obtained coated plate exhibited an extremely high blue color.

<Example 2>
<Organic phosphate compound layer forming step>
A commercially available aluminum pigment was used as the base particles. This aluminum pigment has a paste-like form by washing the paste containing it (trade name: “TCR2060”, manufactured by Toyo Aluminum Co., Ltd., average particle size 18 μm) with mineral spirit and then filtering. there were. The non-volatile component (aluminum pigment) of the paste after filtration was 70% by mass (the balance was mineral spirit).

  The aluminum pigment was washed with propylene glycol monomethyl ether. Then, 200 g (in terms of solid content) of the washed aluminum pigment was dissolved in 400 g of propylene glycol monobutyl ether with 2 g of mono (2-methacryloyloxyethyl) acid phosphate (1% by mass with respect to the base particles) as an organic phosphate compound. The solution was added and stirred at 75 ° C. for 1 hour to obtain a slurry. The obtained slurry was subjected to solid-liquid separation, and an organic phosphoric acid compound was adsorbed on the surface of the base particles to obtain a colorant precursor paste (solid content: 70% by mass) on which an organic phosphoric acid compound layer was formed.

<Coloring pigment adhesion process>
Commercially available diketopyrrolopyrrole pigment (trade name: “Irgazine DPP Rubin TR” (particle size: 0.02 μm), manufactured by BASF) in a pot mill having a diameter of 5 cm and an internal volume of 500 cc with 500 g of glass beads having a diameter of 1 mm inserted. 20 g, 0.5 g of o-aminobenzoic acid (2.5% by mass with respect to the colored pigment) and 30 g of mineral spirit were added, and the colored pigment was dispersed by a ball mill for 24 hours.

  Thereafter, 42.9 g of colorant precursor paste (30 g as a solid content) and 30 g of mineral spirit that were subjected to the organic phosphoric acid compound layer forming step were added to the pot mill, and further dispersed by a ball mill for 1 hour. By this step, the color pigment adhered to the surface of the organic phosphate compound layer of the colorant precursor.

  By washing the slurry thus obtained with 500 g of mineral spirits, the glass beads and the target product are separated, and then filtered to form a surface of the organic phosphate compound layer formed on the surface of the base particles. The colorant of the present invention (solid content 60% by mass) to which the color pigment was adhered was obtained.

  By dispersing 2.5 g (as a solid content) of the colorant of the present invention thus obtained in 50 g of a commercially available acrylic lacquer (trade name: “Autoclear”, manufactured by Nippon Paint Co., Ltd.), A coating composition of the present invention was prepared. A coating plate was prepared by applying this coating composition to double-sided art paper using a 250 μm doctor blade. The obtained coated plate exhibited an extremely high red color.

<Example 3>
Example 1 is the same as Example 1 except that a commercially available green pigment (trade name: “L8730”, manufactured by BASF) was used as a coloring pigment instead of the commercially available phthalocyanine blue pigment. Thus, the colorant of the present invention (which also formed a resin coating layer) was obtained.

  By dispersing 2.5 g (as a solid content) of the colorant of the present invention thus obtained in 50 g of a commercially available acrylic lacquer (trade name: “Autoclear”, manufactured by Nippon Paint Co., Ltd.), A coating composition of the present invention was prepared. A coating plate was prepared by applying this coating composition to double-sided art paper using a 250 μm doctor blade. The obtained coated plate exhibited an extremely high green color.

<Example 4>
For Example 1, except that 2 g of oleyl acid phosphate was used instead of 2 g of di-2-methacryloyloxyethyl acid phosphate as the organic phosphoric acid compound, the same procedure as in Example 1 was carried out. The colorant of the invention (which also formed a resin coating layer) was obtained.

  By dispersing 2.5 g (as a solid content) of the colorant of the present invention thus obtained in 50 g of a commercially available acrylic lacquer (trade name: “Autoclear”, manufactured by Nippon Paint Co., Ltd.), A coating composition of the present invention was prepared. A coating plate was prepared by applying this coating composition to double-sided art paper using a 250 μm doctor blade. The obtained coated plate exhibited an extremely high blue color.

<Example 5>
In contrast to Example 2, all the other examples were used except that a commercially available flaky glass (trade name: “M2025PS”, manufactured by Nippon Sheet Glass Co., Ltd.) was used as the base particle instead of the commercially available aluminum pigment. In the same manner as in No. 2, the colorant of the present invention (without the resin coating layer) was obtained.

  By dispersing 2.5 g (as a solid content) of the colorant of the present invention thus obtained in 50 g of a commercially available acrylic lacquer (trade name: “Autoclear”, manufactured by Nippon Paint Co., Ltd.), A coating composition of the present invention was prepared. A coating plate was prepared by applying this coating composition to double-sided art paper using a 250 μm doctor blade. The obtained coated plate exhibited an extremely high red color.

<Example 6>
For Example 1, except that 2 g of lauryl acid phosphate was used instead of 2 g of di-2-methacryloyloxyethyl acid phosphate as the organic phosphoric acid compound, the same procedure as in Example 1 was carried out. The colorant of the invention (which also formed a resin coating layer) was obtained.

  By dispersing 2.5 g (as a solid content) of the colorant of the present invention thus obtained in 50 g of a commercially available acrylic lacquer (trade name: “Autoclear”, manufactured by Nippon Paint Co., Ltd.), A coating composition of the present invention was prepared. A coating plate was prepared by applying this coating composition to double-sided art paper using a 250 μm doctor blade. The obtained coated plate exhibited a highly saturated blue color.

<Comparative Example 1>
For Example 1, except that the organic phosphoric acid compound layer was not formed, everything else was obtained in the same manner as in Example 1 to obtain a colorant (which also formed a resin coating layer, solid content 60 mass%). .

  A coating composition which is a paint is obtained by dispersing 2.5 g (as a solid content) of the colorant thus obtained in 50 g of a commercially available acrylic lacquer (trade name: “Autoclear”, manufactured by Nippon Paint Co., Ltd.). A product was prepared. A coating plate was prepared by applying this coating composition to double-sided art paper using a 250 μm doctor blade. The obtained coated plate exhibited a blue metallic color, but the saturation was poor.

<Comparative Example 2>
For Example 2, except that the organic phosphoric acid compound layer was not formed, everything else was the same as Example 2 except that the colorant (no resin coating layer was formed, solid content 60% by mass). Obtained.

  A coating composition which is a paint is obtained by dispersing 2.5 g (as a solid content) of the colorant thus obtained in 50 g of a commercially available acrylic lacquer (trade name: “Autoclear”, manufactured by Nippon Paint Co., Ltd.). A product was prepared. A coating plate was prepared by applying this coating composition to double-sided art paper using a 250 μm doctor blade. The obtained coated plate exhibited a red metallic color, but the saturation was inferior.

<Comparative Example 3>
For Example 3, except that the organic phosphoric acid compound layer was not formed, everything else was the same as Example 3 to obtain a colorant (which also formed a resin coating layer, solid content 60 mass%). .

  A coating composition which is a paint is obtained by dispersing 2.5 g (as a solid content) of the colorant thus obtained in 50 g of a commercially available acrylic lacquer (trade name: “Autoclear”, manufactured by Nippon Paint Co., Ltd.). A product was prepared. A coating plate was prepared by applying this coating composition to double-sided art paper using a 250 μm doctor blade. The obtained coated plate exhibited a green metallic color, but the saturation was inferior.

About the above Examples 1-6 and Comparative Examples 1-3, the following tests were done.
<Test 1>
The saturation value of each coated plate produced in Examples 1 to 6 and Comparative Examples 1 to 3 was measured using a multi-angle spectrocolorimeter (trade name: “X-Rite MA-68II”, manufactured by X-Rite). did. The saturation value (C *) was calculated by the following equation using a * value and b * value which are measured values at an incident angle of 45 ° and an offset angle of 15 °. The saturation value (C *) indicates that the higher the numerical value, the higher the saturation. The results are shown in Table 1.

Saturation value (C *) = (a * ² + b * ² ) ^1/2
<Test 2>
To a 20 ml test tube, 0.2 g and 20 g of ethyl acetate were added as solids to the colorants obtained in Examples 1 to 6 and Comparative Examples 1 to 3, and the mixture was shaken well and dispersed for 3 hours. The elution state of the colored pigment was observed. In this test, when the adhesion of the colored pigment is insufficient, the supernatant liquid is colored by the eluted color pigment, and when the adhesion is good, the supernatant liquid becomes transparent. The transparency of the supernatant liquid was visually evaluated and indicated in the following four stages. The closer the supernatant liquid is to colorless and transparent, the more the coloring pigment is more easily removed. The results are shown in Table 1.
A: It is colorless and transparent.
B: Transparent but slightly colored.
C: Transparent but colored.
D: Opaque and colored.

  As can be seen from Table 1, it was confirmed that the colorant of this example had higher chroma and reduced color pigment shedding compared to the colorant of the comparative example.

  Although the embodiments and examples of the present invention have been described as described above, it is also planned from the beginning to appropriately combine the configurations of the above-described embodiments and examples.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

Claims (7)

  A colorant comprising substrate particles, an organic phosphate compound layer formed on the surface of the substrate particles, and a color pigment attached to the surface of the organic phosphate compound layer.   The colorant according to claim 1, wherein the organic phosphoric acid compound layer is composed of an organic phosphoric acid compound having at least one polymerizable double bond.   The colorant according to claim 1, wherein the organic phosphoric acid compound layer is composed of an organic phosphoric acid compound having at least two polymerizable double bonds.   The colorant according to claim 1, wherein the base particle is a metal pigment.   The colorant according to claim 1, wherein the base particle is an aluminum pigment.   The colorant according to any one of claims 1 to 5, wherein a resin coating layer is further formed on the color pigment.   The coating composition formed by mix | blending the coloring agent in any one of Claims 1-6.