JP6072461B2 - Organic inorganic composite particle powder - Google Patents

Description

  The present invention provides an organic-inorganic composite particle powder in which the detachment of the organic pigment from the particle surface of the white inorganic particle powder is suppressed and does not contain harmful elements.

  The organic-inorganic composite pigment comprising the organic-inorganic composite particle powder according to the present invention can be used as a coloring pigment for paints and resin compositions.

  As is well known, inorganic pigments and organic pigments are used as color pigments for paints, resins, printing inks, and the like depending on applications.

  Inorganic pigments are generally known to be excellent in light resistance, but have a small tinting strength and are difficult to obtain a clear hue. Some inorganic pigments have a clear hue, but many of them contain harmful metals such as lead, mercury, cadmium, and chromium as constituent elements, so hygiene, safety and From the viewpoint of preventing environmental pollution, there is a strong demand for alternative pigments that exhibit a clear hue.

  On the other hand, organic pigments are generally known to have a clear hue, but have low hiding power and poor light resistance.

  In the past, in order to obtain a pigment having excellent characteristics as a colored pigment, a technique for combining an inorganic pigment and an organic pigment has been attempted. For example, a method of coprecipitation of chrome lead and phthalocyanine blue or an inorganic pigment A method of attaching an organic pigment to the particle surface (JP-A-4-132770, JP-A-11-181329, etc.) has been proposed.

JP-A-4-132770 Japanese Patent Laid-Open No. 11-181329 JP 11-323174 A

  An organic-inorganic composite pigment composed of an organic-inorganic composite particle powder that is suppressed from detachment of the organic pigment from the surface of the white inorganic particle powder and does not contain harmful elements is currently most demanded. , Not yet obtained.

  That is, the above-mentioned method for coprecipitation of yellow lead and phthalocyanine blue is toxic because of the use of yellow lead, and the pigment obtained because it is manufactured by coprecipitation is used as a paint. In this case, it is difficult to say that the storage stability is sufficient, and using this to form a coating film is not preferable because color floating may occur.

  In addition, the method described in the above-mentioned Patent Document 1 (Japanese Patent Laid-Open No. 4-132770) is a method in which an organic pigment is precipitated in the presence of an inorganic pigment, so that it is difficult to say that the adhesion strength of the organic pigment is sufficient. It is.

  Further, the method described in the above-mentioned Patent Document 2 (Japanese Patent Application Laid-Open No. 11-181329) is prepared by dissolving organopolysiloxane in a cyclic silicone, adding an organic pigment to the resulting solution, This is a method of impregnating an oil-absorbing inorganic pigment and then volatilizing cyclic silicone, and it is difficult to say that the adhesion strength of the organic pigment is sufficient.

  In Patent Document 3 (Japanese Patent Application Laid-Open No. 11-323174), the surface of black iron oxide particles or black hydrated iron oxide particles is coated with an organosilane compound generated from alkoxysilane. Although iron-based black composite particle powder with carbon black fine particle powder adhering to the compound coating is described, this is a technique for fixing black carbon black to black inorganic particles, and a technique for obtaining a highly colored pigment. Are different.

  Accordingly, the present invention provides an organic-inorganic composite pigment comprising an organic-inorganic composite particle powder that is suppressed from detachment of the organic pigment from the particle surface of the white inorganic particle powder and does not contain harmful elements. Technical issue.

  The technical problem can be achieved by the present invention as follows.

  That is, in the present invention, the particle surface of the white inorganic particle powder is an organic silicon compound, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zirconate coupling agent, an oligomer or a polymer compound. It consists of a composite particle powder having an average particle diameter of 0.01 to 10.0 μm, which is coated with a paste selected from one or more kinds and has an organic pigment attached to the coating, and the amount of the organic pigment attached is An organic-inorganic composite particle powder characterized by being 1 to 500 parts by weight with respect to 100 parts by weight of the white inorganic particle powder (Invention 1).

  Further, the present invention provides an intermediate coating wherein the particle surface of the white inorganic particle powder of the present invention 1 is made of at least one selected from an aluminum hydroxide, an aluminum oxide, a silicon hydroxide and a silicon oxide in advance. An organic-inorganic composite particle powder characterized by being coated with a substance (Invention 2).

  Moreover, this invention is an organic inorganic composite pigment which consists of the organic inorganic composite particle powder of this invention 1 or this invention 2 (this invention 3).

  In addition, the present invention is a paint characterized in that the organic-inorganic composite pigment of the present invention 3 is blended in a paint-constituting substrate (Invention 4).

  In addition, the present invention is a resin composition characterized by being colored using the organic-inorganic composite pigment of the present invention 3 (Invention 5).

  In addition, the present invention is a pigment dispersion characterized by containing the organic-inorganic composite pigment of the present invention 3 (Invention 6).

  Moreover, this invention is a masterbatch pellet characterized by containing 1-200 weight part organic-inorganic composite pigment of this invention 3 with respect to 100 parts of resin (this invention 7).

  The organic-inorganic composite pigment composed of the organic-inorganic composite particle powder according to the present invention is suitable as a color pigment in various applications because the organic pigment adhering to the particle surface is suppressed from being detached and harmless. is there.

  The paint and the resin composition according to the present invention are suitable as a paint and a resin composition in consideration of environmental pollution because the organic inorganic composite pigment is used as a coloring pigment, and the organic pigment is prevented from being detached. is there.

  The configuration of the present invention will be described in more detail as follows.

  First, the organic-inorganic composite particle powder according to the present invention will be described.

  The organic-inorganic composite particle powder according to the present invention has an average particle size of 0. 0, which is obtained by coating the surface of white inorganic particle powder, which is a core particle powder, with a paste, and attaching an organic pigment to the paste coating. It consists of organic-inorganic composite particles of 01 to 10.0 μm.

  In addition, the organic-inorganic composite particle powder according to the present invention may be provided with a plurality of colored adhesion layers made of organic pigments on the surface of white inorganic particles that are core particles. For example, the surface of white inorganic particles is coated with a paste, and a colored adhesion layer (hereinafter referred to as “first colored adhesion layer”) in which an organic pigment is adhered to the coating is formed (hereinafter referred to as first colored adhesion). The white inorganic particles in which the layer is formed are referred to as “intermediate pigments”, and further, a colored adhesion layer (hereinafter referred to as “intermediate pigment”) in which the surface of the first colored adhesion layer is coated with a paste and the organic pigment is adhered to the coating This is a form in which a “second colored adhesion layer” is formed. If necessary, a colored adhesion layer may be further formed in the same manner. (Hereinafter, the organic-inorganic composite particle powder having two or more colored adhesion layers is referred to as “organic-inorganic composite particle powder having a plurality of colored adhesion layers”.)

  As white inorganic particles in the present invention, white pigments such as titanium dioxide and zinc oxide, pearl pigments such as titanium mica and muscovite, silica fine particles such as silica powder, white carbon, fine silicic acid, diatomaceous earth, clay, calcium carbonate, Examples include extender pigments such as barium sulfate, alumina white, talc, and transparent titanium oxide. The white inorganic particles may be selected according to required properties and applications, white pigments are preferable for applications where hiding power is required, and pearl pigments are preferable for applications where pearly luster is required, For applications where transparency is required, pearl pigments or extender pigments are preferred, and extender pigments are more preferred.

  The particle shape of the white inorganic particles may be any shape such as a spherical shape, a granular shape, a polyhedral shape, a needle shape, a spindle shape, a rice granular shape, a flake shape, a scale shape, and a plate shape.

  The average particle size of the white inorganic particle powder is 0.009 to 9.95 μm, preferably 0.014 to 9.45 μm, more preferably 0.019 to 8.95 μm.

  When the average particle diameter exceeds 9.95 μm, the resulting organic-inorganic composite particles become coarse particles, which is not preferable because coloring power is reduced. (Deleted: When the particle size is less than 0.009 μm, the particles are likely to be aggregated due to finer particles, so that it is difficult to uniformly coat the surface of the particles with a paste and uniformly apply an organic pigment. )

The BET specific surface area value of the white inorganic particle powder is 0.5 m ² / g or more. When the BET specific surface area value is less than 0.5 m ² / g, the white inorganic particles are coarse or the particles are particles that are sintered between the particles, and the resulting organic-inorganic composite particle powder Becomes coarse particles and the coloring power decreases. Considering the coloring power of the organic-inorganic composite particle powder, the BET specific surface area value is preferably 1.0 m ² / g or more, more preferably 1.5 m ² / g or more. Considering the uniform coating treatment with the paste on the particle surface of the white inorganic particle powder and the uniform adhesion treatment with the organic pigment, the upper limit is 500 m ² / g, preferably 400 m ² / g, more preferably 300 m. ² / g.

The hue of the white inorganic particle powder has an L ^* value of 70.00 or more, more preferably 75.00 or more, and a C ^* value of 18.00 or less, preferably 15.00 or less, more preferably 12. 00 or less, still more preferably 9.00 or less. When the L ^* value and the C ^* value are out of the above ranges, it is difficult to say that the hue is white, and it is difficult to obtain the organic-inorganic composite particle powder that is the object of the present invention.

In the case of a white pigment, the hiding power of the white inorganic particle powder in the present invention is preferably 600 cm ² / g or more by an evaluation method described later. In the case of pearl pigments and extender pigments, the hiding power is preferably less than 600 cm ² / g. Considering the transparency of the obtained organic-inorganic composite particle powder, the hiding power is more preferably 500 cm ² / g or less, and still more preferably 400 cm ² / g or less.

As for the light resistance of the white inorganic particle powder, the lower limit value of the ΔE ^* value is usually more than 5.0 and the upper limit value is 12.0, preferably 11.0, more preferably 10.0, according to the evaluation method described later. .

  As the sizing agent in the present invention, any material can be used as long as an organic pigment can be attached to the surface of the white inorganic particles, preferably an organosilicon compound such as alkoxysilane, fluoroalkylsilane, or polysiloxane, or a silane type. , Titanate-based, aluminate-based and zirconate-based various coupling agents, oligomers or polymer compounds. In consideration of the adhesion strength of the organic pigment to the surface of the white inorganic particles, more preferably various types of organosilicon compounds such as alkoxysilane, fluoroalkylsilane, and polysiloxane, silane, titanate, aluminate, and zirconate It is a coupling agent.

  In particular, when silica fine particles are used as the core particle powder, it is preferable to use an organosilicon compound or a silane coupling agent as the paste.

  As the organosilicon compound in the present invention, an organosilane compound formed from an alkoxysilane represented by Chemical Formula 1, a polysiloxane represented by Chemical Formula 2, a modified polysiloxane represented by Chemical Formula 3, a terminal modified polysiloxane represented by Chemical Formula 4, and A fluoroalkylsilane represented by the formula 5 or a mixture thereof can be used.

  Specific examples of the alkoxysilane include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane. Examples include methoxysilane and decyltrimethoxysilane.

  Considering the adhesion strength of the organic pigment to the particle surface of the white inorganic particles, an organosilane compound produced from methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, isobutyltrimethoxysilane, phenyltriethoxysilane is more preferable, Most preferred are organosilane compounds formed from methyltriethoxysilane, methyltrimethoxysilane and phenyltriethoxysilane.

  Considering the adhesion strength of the organic pigment to the surface of the white inorganic particles, polysiloxane having a methylhydrogensiloxane unit, polyether-modified polysiloxane, and terminal carboxylic acid-modified polysiloxane having a terminal modified with a carboxylic acid are preferable.

  Specific examples of the fluoroalkylsilane include trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, trifluoropropylethoxysilane, Examples include decafluorooctyltriethoxysilane and heptadecafluorodecyltriethoxysilane.

  Considering the adhesion strength of the organic pigment to the particle surface of the white inorganic particles, a fluorine-containing organosilane compound generated from trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane is preferable, Most preferred are fluorine-containing organosilane compounds formed from trifluoropropyltrimethoxysilane and tridecafluorooctyltrimethoxysilane.

  Among coupling agents, silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, Examples include γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-chloropropyltrimethoxysilane.

  Examples of titanate coupling agents include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, tetraoctyl bis (ditridecyl phosphate) titanate, tetra (2- Examples include 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.

  Examples of the aluminate coupling agent include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate and the like.

  Examples of the zirconate coupling agent include zirconium tetrakisacetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tetrakisethylacetoacetate, zirconium tributoxymonoethylacetoacetate, zirconium tributoxyacetylacetonate and the like.

  The oligomer preferably has a molecular weight of 300 or more and less than 10,000, and the polymer compound preferably has a molecular weight of about 10,000 or more and about 100,000. In view of uniform coating treatment on white inorganic particles, oligomers or polymer compounds that are liquid or soluble in water or various solvents are preferable.

  In the case of a coupling agent excluding a silane coupling agent, an oligomer or a polymer compound, the coating amount of the paste is preferably 0.01 to 15.0% by weight in terms of C with respect to the paste-coated white inorganic particles. Preferably it is 0.02-12.5 weight%, Most preferably, it is 0.03-10.0 weight%.

  When it is less than 0.01% by weight, it is difficult to attach 1 part by weight or more of organic pigment to 100 parts by weight of white inorganic particle powder. When the amount exceeds 15.0% by weight, 1 to 500 parts by weight of the organic pigment can be attached to 100 parts by weight of the white inorganic particle powder, so there is no meaning to cover more than necessary.

  When the white inorganic particles do not contain Si and the paste is an organosilicon compound and a silane coupling agent, the amount of the paste is 0.02 to 5 in terms of Si with respect to the paste-coated white inorganic particles. 0.0% by weight is preferable, more preferably 0.03 to 4.0% by weight, and most preferably 0.05 to 3.0% by weight.

  In the case of less than 0.02% by weight, it is difficult to attach 1 part by weight or more of organic pigment to 100 parts by weight of white inorganic particle powder. When the amount exceeds 5.0% by weight, 1 to 500 parts by weight of the organic pigment can be attached to 100 parts by weight of the white inorganic particle powder, so there is no meaning of covering more than necessary.

  As the organic pigment in the present invention, a red organic pigment, a blue organic pigment, a yellow organic pigment, a green organic pigment, an orange organic pigment, and a brown organic pigment generally used as a colorant for paints and resin compositions Various organic pigments such as pigments and purple organic pigments can be used.

  Among various organic pigments, as red organic pigments, quinacridone pigments such as quinacridone red, azo pigments such as permanent red, condensed azo pigments such as condensed azo red, and perylene pigments such as perylene red can be used. As the blue organic pigment, phthalocyanine pigments such as metal-free phthalocyanine blue, phthalocyanine blue, and fast sky blue can be used. As the yellow organic pigment, monoazo pigments such as Hansa Yellow, disazo pigments such as benzidine yellow and permanent yellow, and condensed azo pigments such as condensed azo yellow can be used. As the green pigment, a phthalocyanine pigment such as phthalocyanine green can be used.

  In addition, you may mix and use each said organic pigment according to the hue requested | required. Further, two or more kinds of similar colors may be used according to the required hue and characteristics.

  In addition, in the organic-inorganic composite particle powder having a plurality of colored adhesion layers, the organic pigment to be adhered to the first colored adhesion layer and the organic pigment to be adhered after the second colored coating layer are the same, but different in type. Either an organic pigment or a different color organic pigment may be used. Further, by selecting an organic pigment having a function such as light resistance as the organic pigment to be combined, it becomes possible to obtain organic-inorganic composite particle powder having a plurality of functions.

  The adhesion amount of the organic pigment is 1 to 500 parts by weight with respect to 100 parts by weight of the white inorganic particle powder.

  In the case of less than 1 part by weight and in the case of exceeding 500 parts by weight, it is difficult to obtain the organic-inorganic composite particle powder that is the object of the present invention. Preferably it is 3-400 weight part, More preferably, it is 5-300 weight part.

  In the organic-inorganic composite particle powder having a plurality of colored adhesion layers, the adhesion amount of the organic pigment in each colored adhesion layer does not exceed the upper limit value of the adhesion amount of the whole organic pigment according to the desired hue and characteristics. You can attach an appropriate amount.

  The particle shape and particle size of the organic-inorganic composite particles according to the present invention greatly depend on the particle shape and particle size of the white inorganic particles that are the core particles, and have a particle form similar to the core particles.

  That is, the organic-inorganic composite particle powder according to the present invention has an average particle size of 0.01 to 10.0 μm, preferably 0.015 to 9.5 μm, more preferably 0.02 to 9.0 μm.

  When the average particle diameter of the organic-inorganic composite particle powder exceeds 10.0 μm, the particle size is too large, and the coloring power is reduced. When the average particle size is less than 0.01 μm, it may be difficult to disperse in the paint vehicle or the resin composition.

The BET specific surface area value of the organic / inorganic composite particle powder is 1.0 to 500 m ² / g, preferably 1.5 to 400 m ² / g, more preferably 2.0 to 300 m ² / g. When the BET specific surface area value is less than 1.0 m ² / g, the particles are coarse or the particles are sintered between the particles and the coloring power is reduced.

  The organic pigment removal rate of the organic-inorganic composite particle powder is preferably 10% or less, more preferably 9% or less. In the case where the specific gravity of the organic pigment and the organic-inorganic composite particle is close, the degree of detachment of the organic pigment from the organic-inorganic composite particle is preferably 5 or 4 in visual observation in the later evaluation method, more preferably 5 It is. When the desorption rate of the organic pigment exceeds 10%, or when the degree of desorption of the organic pigment is 3 or less, the desorbed organic pigment causes uniform dispersion in the paint vehicle or the resin composition. In addition to being inhibited, the hue of the white inorganic particle powder in the detached part appears on the particle surface, making it difficult to obtain a uniform hue.

  The coloring power of the organic-inorganic composite particle powder according to the present invention is preferably 110% or more, more preferably 115% or more, and most preferably 120% or more according to the evaluation method described later.

Hiding power of the organic-inorganic composite particles according to the present invention, when a white pigment as the white inorganic particles, preferably at least 700 cm 2 / ^g by the evaluation method described below, more preferably 750 cm 2 / ^g or more. When using extender pigments or pearl pigments as the white inorganic particles is preferably less than 700 cm ² / g, more preferably not more than 650 cm ² / g, more preferably 600 cm ² / g or less, and most preferably 580 cm ² / g It is as follows.

The light resistance of the organic-inorganic composite particle powder is 5.0 or less, preferably 4.0 or less in terms of ΔE ^* value in the evaluation method described later. In particular, when titanium oxide, zinc oxide or the like having an ultraviolet protection effect is used as the core particle, the ΔE ^* value is preferably 3.0 or less, more preferably 2.0 or less.

  In the organic-inorganic composite particle powder according to the present invention, the particle surface of the white inorganic particle powder is selected in advance from at least one selected from aluminum hydroxide, aluminum oxide, silicon hydroxide, and silicon oxide, if necessary. It may be coated with an intermediate coating consisting of seeds, and the organic pigment detachment from the surface of the white inorganic particle powder can be further reduced and light resistance as compared with the case where the coating is not coated with the intermediate coating. Will improve.

The coating amount by the intermediate coating is preferably 0.01 to 20% by weight with respect to the white inorganic particle powder coated with the intermediate coating, Al conversion, SiO ₂ conversion, or the total of Al conversion amount and SiO ₂ conversion amount. .

  When it is less than 0.01% by weight, the effect of reducing the organic pigment desorption rate and the effect of improving light resistance cannot be obtained. Since the coating amount of 0.01 to 20% by weight can sufficiently obtain the effect of reducing the organic pigment detachment rate and improve the light resistance, it is meaningless to cover more than 20% by weight more than necessary.

The organic-inorganic composite particle powder according to the present invention coated with the intermediate coating is approximately the same particle size and BET specific surface area as the organic-inorganic composite particle powder according to the present invention not coated with the intermediate coating. , Hue (L ^* value, a ^* value, b ^* value), coloring power and hiding power. Further, the desorption rate of the organic pigment or the degree of desorption of the organic pigment is improved by coating the intermediate coating, and the desorption rate is preferably 8% or less, more preferably 5% or less. The degree is preferably 5, and the light resistance is preferably 4.0 or less, more preferably 3.0 or less in terms of ΔE ^* value.

  The organic-inorganic composite pigment according to the present invention comprises the organic-inorganic composite particle powder.

  Next, a paint containing the organic-inorganic composite pigment according to the present invention will be described.

The paint blended with the organic-inorganic composite pigment according to the present invention preferably has a storage stability of ΔE ^* value of 1.5 or less, more preferably 1.2 or less. When the coating film is used, the glossiness is 75 to 110%, preferably 80 to 110%, and the light resistance ΔE ^* value of the coating film is 5.0 or less, preferably 4.0 or less. . When an extender pigment or a pearl pigment is used as the white inorganic particle powder, the transparency of the coating film is preferably a linear absorption coefficient of 0.10 μm ⁻¹ or less, more preferably 0.09 μm ⁻¹ or less.

The paint blended with the organic-inorganic composite pigment in which the particle surface according to the present invention is coated with an intermediate coating has a storage stability of preferably 1.5 or less, more preferably 1.2 or less in terms of ΔE ^* value. When the coating film is used, the glossiness is 80 to 115%, preferably 85 to 115%, and the light resistance ΔE ^* value of the coating film is 4.0 or less, preferably 3.0 or less. When an extender pigment or a pearl pigment is used as the white inorganic particle powder, the transparency of the coating film is preferably a linear absorption coefficient of 0.10 μm ⁻¹ or less, more preferably 0.09 μm ⁻¹ or less.

The water-based paint blended with the organic-inorganic composite pigment according to the present invention preferably has a storage stability of ΔE ^* value of 1.5 or less, more preferably 1.2 or less. When the coating film is used, the glossiness is 70 to 110%, preferably 75 to 110%, and the light resistance ΔE ^* value of the coating film is 5.0 or less, preferably 4.0 or less. . In addition, when an extender pigment or a pearl pigment is used as the white inorganic particle powder, the transparency of the coating film is preferably a linear absorption coefficient of 0.11 μm ⁻¹ or less, more preferably 0.10 μm ⁻¹ or less.

The water-based paint blended with the organic-inorganic composite pigment whose particle surface is coated with an intermediate coating according to the present invention has a storage stability of ΔE of 1.5 or less, more preferably 1.2 or less. When a coating film is formed, the glossiness is 75 to 115%, preferably 80 to 115%, and the light resistance ΔE ^* value of the coating film is 4.0 or less, preferably 3.0 or less. In addition, when an extender pigment or a pearl pigment is used as the white inorganic particle powder, the transparency of the coating film is preferably a linear absorption coefficient of 0.11 μm ⁻¹ or less, more preferably 0.10 μm ⁻¹ or less.

  The blending ratio of the organic-inorganic composite pigment in the paint according to the present invention can be used in the range of 0.5 to 100 parts by weight with respect to 100 parts by weight of the paint base material. Preferably it is 1.0-100 weight part.

  As the paint constituent base material, a resin, a solvent, and if necessary, fats and oils, an antifoaming agent, an extender pigment, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent and the like are blended.

  Resins include acrylic resin, alkyd resin, polyester resin, polyurethane resin, epoxy resin, phenol resin, melamine resin, amino resin, vinyl chloride resin, silicone resin, gum rosin that are usually used for solvent-based paints and oil-based printing inks. Rosin resins such as lime rosin, maleic acid resin, polyamide resin, nitrocellulose, ethylene-vinyl acetate copolymer resin, rosin modified phenolic resin, rosin modified maleic resin and other rosin modified resins, petroleum resins and the like can be used. . For water-based paints, water-soluble acrylic resins, water-soluble styrene-maleic acid resins, water-soluble alkyd resins, water-soluble melamine resins, water-soluble urethane emulsion resins, water-soluble epoxies commonly used for water-based paints and water-based inks Resins, water-soluble polyester resins, and the like can be used.

  Solvents include soybean oil, toluene, xylene, thinner, butyl acetate, methyl acetate, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc. Glycol ether solvents, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate, aliphatic hydrocarbon solvents such as hexane, heptane, and octane, alicyclic hydrocarbon solvents such as cyclohexane, and petroleum-based solvents such as mineral spirits Solvents, ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, aliphatic hydrocarbons, and the like can be used.

  Water-based paint solvents include water and alcohol-based solvents usually used for water-based paints, such as ethyl alcohol, propyl alcohol, and butyl alcohol, methyl ether solvents such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve, and diethylene glycol. , Oxyethylene or oxypropylene addition polymers such as triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, alkylene glycol such as ethylene glycol, propylene glycol, 1,2,6-hexanetriol, glycerin, It can be used by mixing with a water-soluble organic solvent such as 2-pyrrolidone.

  As oils and fats, boil oils obtained by processing dry oils such as linseed oil, persimmon oil, sea lion oil, safflower oil and the like can be used.

  Antifoaming agents include Nopco 8034 (product name), SN deformer 477 (product name), SN deformer 5013 (product name), SN deformer 247 (product name), SN deformer 382 (product name) (all of these are San Nopco Commercially available products such as manufactured by Co., Ltd., Antihome 08 (trade name), Emulgen 903 (trade name) (all of which are manufactured by Kao Corporation) can be used.

  Next, the resin composition colored using the organic-inorganic composite pigment according to the present invention will be described.

The resin composition colored using the organic-inorganic composite pigment according to the present invention has a dispersion state by visual observation of 4 or 5, preferably 5, according to the later evaluation method, and the light resistance ΔE ^* value of the resin composition is It is 5.0 or less, preferably 4.0 or less. In addition, when an extender pigment or a pearl pigment is used as the white inorganic particle powder, the transparency of the resin composition is preferably a linear absorption coefficient of 0.10 μm ⁻¹ or less, more preferably 0.09 μm ⁻¹ or less.

The resin composition colored using the organic-inorganic composite pigment in which the particle surface according to the present invention is coated with an intermediate coating, the dispersion state by visual observation is 4 or 5, preferably 5, according to the evaluation method described later. The light resistance ΔE ^* value of the resin composition is 4.0 or less, preferably 3.0 or less. In the case where extender pigments or pearl pigments are used as the white inorganic particles, the transparency is preferably linear absorption coefficient 0.10 .mu.m ^-1 or less of the resin composition, more preferably 0.09 .mu.m ^-1 or less.

  The compounding ratio of the organic-inorganic composite pigment in the resin composition according to the present invention can be used in the range of 0.01 to 200 parts by weight with respect to 100 parts by weight of the resin, and considering the handling of the resin composition. The amount is preferably 0.05 to 150 parts by weight, more preferably 0.1 to 100 parts by weight.

  As a constituent substrate in the resin composition according to the present invention, additives such as lubricants, plasticizers, antioxidants, ultraviolet absorbers, various stabilizers, and the like, as necessary, together with organic-inorganic composite pigments and known thermoplastic resins. Blended.

  Examples of the resin include polyolefins such as polyethylene, polypropylene, polybutene, and polyisobutylene, polyvinyl chloride, polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, styrene-acrylic acid ester copolymer, styrene-vinyl acetate copolymer, Acrylonitrile-butadiene-styrene copolymer, acrylonitrile-EPDM-styrene copolymer, acrylic resin, polyamide, polycarbonate, polyacetal, polyurethane and other thermoplastic resins, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, Silicone resin, rosin ester, rosin, natural rubber, synthetic rubber and the like can be used.

  The amount of the additive may be 50% by weight or less with respect to the total of the organic-inorganic composite pigment and the resin. When the content of the additive exceeds 50% by weight, the moldability is lowered.

  The resin composition according to the present invention is obtained by thoroughly mixing a resin raw material and an organic-inorganic composite pigment in advance, and then applying a strong shearing action under heating by using a kneader or an extruder to form an aggregate of the organic-inorganic composite pigment. The organic-inorganic composite pigment is uniformly dispersed in the resin composition, and then molded into a shape suitable for the purpose.

  Next, a pigment dispersion containing the organic-inorganic composite pigment according to the present invention used in the production of a paint will be described.

  The pigment dispersion according to the present invention includes a pigment paste that is an intermediate dispersion of paint and a mill base, and the organic-inorganic composite pigment according to the present invention is added in an amount of 5 to 1000 with respect to 100 parts by weight of the pigment dispersion constituting substrate. Part by weight, preferably 10 to 800 parts by weight is contained.

  As a pigment dispersion constituting base material, a resin, a solvent and / or fats and oils, and if necessary, an antifoaming agent, an extender pigment, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent and the like are blended depending on the application. .

  As the resin, solvent, and fat used in the pigment dispersion according to the present invention, the same resin, solvent, and fat as those for the paint can be used.

  The composition of the resin in the pigment dispersion may be the same resin as the dilution resin at the time of preparing the paint, or a different resin, but if different resins are used, What is necessary is just to determine in consideration of the various characteristics determined by the compatibility.

  The pigment dispersion according to the present invention comprises a pigment and a resin, a solvent and / or fats and oils, butterfly mixer, planetary mixer, pony mixer, dissolver, tank mixer, high speed mixer, homomixer, kneader, roll mill, sand mill, attritor It can be obtained by kneading and dispersing using a dispersing machine such as a ball mill.

  The paint obtained by using the pigment dispersion according to the present invention exhibits more excellent dispersibility.

  Next, master batch pellets used in the production of paints and resin compositions will be described.

  The master batch pellet according to the present invention requires a binder resin as a constituent substrate of a paint and a resin composition and the organic-inorganic composite pigment, and a mixer such as a ribbon blender, a Nauter mixer, a Henschel mixer, a super mixer, etc. Kneaded with a well-known single-screw kneading extruder or twin-screw kneading extruder, etc., then cut, or kneaded by mixing the above mixture with a Banbury mixer, pressure kneader, etc. It is manufactured by crushing, molding or cutting.

  The binder resin and the organic / inorganic composite pigment may be supplied to the kneader in a fixed ratio, or a mixture of both may be supplied.

  The master batch pellet according to the present invention has an average major axis of 1 to 6 mm, preferably 2 to 5 mm. The average minor axis is 2 to 5 mm, preferably 2.5 to 4 mm. When the average major axis is less than 1 mm, the workability at the time of producing the pellet is poor, which is not preferable. When the thickness exceeds 6 mm, the difference from the size of the binder resin for dilution is large, and it becomes difficult to sufficiently disperse. Moreover, the shape can be various, and can be indefinite and spherical, cylindrical, flakes, and the like.

  As the binder resin used for the master batch pellet according to the present invention, the same resin as the resin for paint or resin for resin composition can be used.

  The composition of the binder resin in the masterbatch pellet may be the same resin as the diluent binder resin or a different resin, but if different resins are used, What is necessary is just to determine in consideration of the various characteristics determined by the compatibility.

  The amount of the organic-inorganic composite pigment blended in the master batch pellet is 1 to 200 parts by weight, preferably 1 to 150 parts by weight, and more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the binder resin. When the amount is less than 1 part by weight, the melt viscosity at the time of kneading is insufficient, and it is difficult to achieve good dispersion mixing of the organic-inorganic composite pigment. When the amount exceeds 200 parts by weight, since there are few binder resins for the organic-inorganic composite pigment, it is difficult to achieve good dispersion and mixing of the organic-inorganic composite pigment, and in the resin composition due to slight changes in the addition amount of the masterbatch pellets. Since the content of the organic-inorganic composite pigment blended in the composition varies greatly, it is difficult to prepare the desired content, which is not preferable. Also, mechanical wear is severe and not suitable.

  Next, a method for producing the organic-inorganic composite particle powder according to the present invention will be described.

  The organic-inorganic composite particle powder according to the present invention is obtained by mixing white inorganic particle powder and a paste, covering the particle surface of the white inorganic particle powder with a paste, and then coating the white inorganic particle powder coated with the paste. It can be obtained by mixing organic pigments.

  The white inorganic particle powder is coated on the particle surface with a sizing agent by mechanically mixing and stirring the white inorganic particle powder and the sizing agent or sizing agent solution, or by adding a sizing agent solution or sizing agent to the white inorganic particle powder. What is necessary is just to mix and stir mechanically while spraying. Almost all of the added paste is coated on the particle surface of the white inorganic particle powder.

  In addition, when alkoxysilane or fluoroalkylsilane is used as the paste, the coated alkoxysilane or fluoroalkylsilane is partly produced through a coating process, and the organosilane compound or fluorocarbon produced from alkoxysilane is generated. You may coat | cover as a fluorine-containing organosilane compound produced | generated from alkylsilane. Even in this case, the subsequent adhesion of the organic pigment is not affected.

  In order to uniformly coat the surface of the white inorganic particle powder particles with the paste, it is preferable that the aggregation of the white inorganic particle powders is previously unraveled using a pulverizer.

  As a device for mixing and stirring white inorganic particle powder and paste, and mixing and stirring organic pigment and white inorganic particle powder whose surface is coated with paste, apply shear force to the powder layer. It is preferable to use a device that can simultaneously perform shearing, spatula and compression, such as a wheel-type kneader, a ball-type kneader, a blade-type kneader, and a roll-type kneader. A kneader can be used more effectively.

  Examples of the wheel-type kneader include an edge runner (synonymous with “mix muller”, “simpson mill”, “sand mill”), multi-mal, stotz mill, wet pan mill, conner mill, ring muller, etc., preferably edge Runners, multi-mals, stocks mills, wet pan mills and ring mullers, more preferably edge runners. Examples of the ball kneader include a vibration mill. Examples of the blade-type kneader include a Henschel mixer, a planetary mixer, and a nauter mixer. Examples of the roll-type kneader include an extruder.

  The conditions at the time of mixing and stirring the white inorganic particle powder and the paste were such that the line load was 19.6 to 1960 N / cm (2 to 200 kg) so that the paste was coated as uniformly as possible on the particle surface of the white inorganic particle powder. / Cm), preferably 98 to 1470 N / cm (10 to 150 Kg / cm), more preferably 147 to 980 N / cm (15 to 100 Kg / cm), treatment time 5 minutes to 24 hours, preferably 10 minutes to 20 What is necessary is just to adjust process conditions suitably in the range of time. In addition, what is necessary is just to adjust process conditions suitably in the range of stirring speed 2-2000rpm, Preferably 5-1000rpm, More preferably, it is 10-800rpm.

  The addition amount of the paste is preferably 0.15 to 45 parts by weight with respect to 100 parts by weight of the white inorganic particle powder. With an addition amount of 0.15 to 45 parts by weight, 1 to 500 parts by weight of the organic pigment can be attached to 100 parts by weight of the white inorganic particle powder.

  After the surface of the white inorganic particle powder is coated with a paste, an organic pigment is added, mixed and stirred to adhere the organic pigment to the paste coating. If necessary, drying or heat treatment may be further performed.

  The organic pigment is added little by little over a period of 5 minutes to 24 hours, preferably 5 minutes to 20 hours, or 5 to 25% by weight with respect to 100 parts by weight of the white inorganic particles. Part of the organic pigment is preferably added in portions until the desired addition amount is reached.

  The conditions during mixing and stirring are such that the linear load is 19.6 to 1960 N / cm (2 to 200 Kg / cm), preferably 98 to 1470 N / cm (10 to 150 Kg / cm), so that the organic pigment adheres uniformly. More preferably, the processing conditions may be appropriately adjusted within a range of 147 to 980 N / cm (15 to 100 Kg / cm) and a processing time of 5 minutes to 24 hours, preferably 10 minutes to 20 hours. In addition, what is necessary is just to adjust process conditions suitably in the range of stirring speed 2-2000rpm, Preferably 5-1000rpm, More preferably, it is 10-800rpm.

  The addition amount of the organic pigment is 1 to 500 parts by weight, preferably 3 to 400 parts by weight, and more preferably 5 to 300 parts by weight with respect to 100 parts by weight of the white inorganic particle powder. When the amount of the organic pigment added is outside the above range, the desired organic / inorganic composite particle powder cannot be obtained.

  In the case of performing drying or heat treatment, the heating temperature is usually preferably 40 to 150 ° C, more preferably 60 to 120 ° C, and the heating time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 3 hours. .

  In addition, when alkoxysilane and fluoroalkylsilane are used as the paste, an organosilane compound finally produced from alkoxysilane or a fluorine-containing organosilane compound produced from fluoroalkylsilane through these steps It is covered.

  The organic-inorganic composite particle powder having a plurality of colored adhesion layers is prepared by mixing white inorganic particle powder and a paste, coating the surface of the white inorganic particle powder with a paste, and then coating the white inorganic with the paste. The particle powder and the organic pigment are mixed and the organic pigment is adhered to the paste coating to form a first colored adhesion layer (intermediate pigment). Next, the intermediate pigment formed with the first colored adhesive layer and the paste are mixed, and further, the paste-coated intermediate pigment and the organic pigment are mixed, and the organic pigment is passed through the adhesive on the first colored adhesive layer. Can be obtained. What is necessary is just to perform the mixing process with the paste in each said process and the mixing process with an organic pigment similarly to each said process. In addition, the organic-inorganic composite particle powder in which three or more colored adhesion layers are formed can be obtained by repeating coating with a paste and adhesion of an organic pigment as necessary.

  The white inorganic particle powder is, if necessary, an intermediate composed of at least one selected from an aluminum hydroxide, an aluminum oxide, a silicon hydroxide and a silicon oxide in advance of mixing and stirring with a paste. You may coat | cover with a coating.

  Coating with an intermediate coating is performed by adding an aluminum compound, a silicon compound, or both of the compounds to an aqueous suspension obtained by dispersing white inorganic particle powder and mixing and stirring, or, if necessary, after mixing and stirring. By adjusting the pH value, the particle surface of the white inorganic particle powder is an intermediate coating comprising at least one selected from aluminum hydroxide, aluminum oxide, silicon hydroxide, and silicon oxide. Cover, then filter, wash, dry and grind. If necessary, a deaeration / consolidation process may be further performed.

  As the aluminum compound, aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride, and aluminum nitrate, and alkali aluminates such as sodium aluminate can be used.

  As the silicon compound, No. 3 water glass, sodium orthosilicate, sodium metasilicate and the like can be used.

<Action>
The most important point in the present invention is that the surface of the white inorganic particle powder is coated with a paste, and the organic inorganic composite particle powder having an organic pigment attached to the coating is the particle surface of the white inorganic particle powder. This is the fact that the organic inorganic composite particle powder is suppressed from detachment of the organic pigment from the water and does not contain harmful elements.

  In the present invention, the present inventor presumes the reason why the detachment of the organic pigment from the particle surface of the white inorganic particle powder is suppressed as follows.

  First, when alkoxysilane and fluoroalkylsilane are used, the alkoxysilane and fluoroalkylsilane to which the metal element and the organic pigment contained in the white inorganic particle powder particles and the particle surface are attached A metalloxane bond (Si-OM (M is a metal particle contained in the white inorganic particles)) is formed between the alkoxy silane and the alkoxy silane to which the organic pigment is attached. It is considered that the fluorine-containing organosilane compound produced from the produced organosilane compound or fluoroalkylsilane is firmly bonded to the particle surface of the white inorganic particle powder.

  Moreover, when a coupling agent is used, it is thought that the reactive group which the coupling agent to which the organic pigment adheres has bind | bonds firmly to the particle | grain surface of a white inorganic particle.

  In addition, when polysiloxane, oligomer and polymer compound are used, various functional groups possessed by the polysiloxane, oligomer or polymer compound to which the organic pigment is attached are transferred to the particle surface of the white inorganic particle powder. It is considered to be firmly bonded.

  The paint containing the organic / inorganic composite pigment composed of the organic / inorganic composite particle powder has excellent paint stability and dispersibility, and the resin composition obtained by adding the organic / inorganic composite pigment is dispersible. Is the fact that is superior.

  Regarding the reason why the paint stability and dispersibility of the paint according to the present invention is excellent and the dispersibility of the resin composition is excellent, the present inventor stated that the organic pigment released from the particle surface of the organic-inorganic composite particle powder was suppressed. This is thought to be due to the use of an inorganic composite pigment as a colorant.

In addition, the paint obtained through the pigment dispersion according to the present invention is more excellent in paint stability and dispersion stability, and the resin composition obtained through the master batch according to the present invention is more excellent in dispersibility. It is the fact that

  In addition, the organic-inorganic composite pigment according to the present invention does not contain harmful elements and compounds, so it is excellent in hygiene and safety, and is a pigment that takes environmental pollution into consideration.

  A typical embodiment of the present invention is as follows.

  The average particle size of each particle was measured by measuring the particle size of 350 particles shown in the electron micrograph, and the average value was shown.

  The specific surface area value was indicated by a value measured by the BET method.

  For the amount of Al and Si present on the surface of the white inorganic particle powder coated with the intermediate coating, “fluorescence X-ray analyzer 3063M type” (manufactured by Rigaku Denki Kogyo Co., Ltd.) is used. The measurement was performed according to "General Rules for Optical X-ray Analysis".

  Of the coating amount of the paste coated on the particle surface of the white inorganic particle powder, when the core particle does not contain silicon and contains silicon as the paste, “fluorescent X-rays” Using “Analyzer 3063M type” (manufactured by Rigaku Denki Kogyo Co., Ltd.), the measurement was performed according to “General X-ray fluorescence analysis rules” of JIS K0119.

  In addition, among the coating amount of the paste coated on the particle surface of the white inorganic particle powder, when using particles containing silicon in the core particles, or those containing no silicon as the paste Was determined by measuring the amount of carbon using a “Horiba Metal Carbon / Sulfur Analyzer EMIA-2200 Model” (manufactured by Horiba, Ltd.).

  The coating amount of the organic pigment adhering to the organic-inorganic composite particle powder was determined by measuring the carbon amount using “Horiba Metal Carbon / Sulfur Analyzer EMIA-2200 type” (manufactured by Horiba, Ltd.).

  The desorption rate (%) of the organic pigment adhering to the organic-inorganic composite particle powder was indicated by the value obtained by the following method. The closer the organic pigment desorption rate is to 0%, the smaller the organic pigment desorption amount from the particle surface of the organic-inorganic composite particle powder.

  Put 2g of particle powder to be measured and 20ml of dibromomethane in a 50ml Erlenmeyer flask, ultrasonically disperse for 20 minutes, then let stand for 3 days, and measure particle powder and supernatant due to the difference in specific gravity between the particle powder to be measured and organic pigment. The liquid was separated. Subsequently, the light transmittance of the obtained supernatant was measured using “Self-recorded photoelectric spectrophotometer UV-2100” (Shimadzu Corporation), and the concentration and light transmittance of the organic pigment in dibromomethane calculated in advance were measured. From the calibration curve, the concentration of the desorbed organic pigment present in dibromomethane was calculated, and the value determined according to the following formula 1 was taken as the desorption rate (%) of the organic pigment.

<Equation 1>
Desorption rate of organic pigment (%) = {(Wa-We) / Wa} × 100
Wa: Organic pigment adhesion amount of organic / inorganic composite particle powder We: Organic pigment adhesion amount of organic / inorganic composite particle powder after desorption test

  In addition, when the specific gravity of the organic pigment and the organic-inorganic composite particle powder was close, the degree of desorption of the organic pigment from the organic-inorganic composite particle powder was visually evaluated in five stages by the following method. 5 indicates that the amount of the organic pigment released from the particle surface of the composite particle is small.

  2 g of the measured particle powder and 20 ml of ethanol were placed in a 50 ml Erlenmeyer flask, subjected to ultrasonic dispersion for 60 minutes, and then centrifuged at 10,000 rpm for 15 minutes to separate the measured particle powder from the solvent portion. . The obtained particle powder to be measured was dried at 80 ° C. for 1 hour, and the number of detached and re-aggregated organic pigments present in the field of view shown in the electron micrograph (× 50,000) was visually observed. The white inorganic particles and the organic pigment were evaluated in five stages as compared with the electron micrograph (× 50,000) of the mixed particle powder simply mixed without using the paste.

1: Same as when white inorganic particle powder and organic pigment are simply mixed without using a paste.
2: 30 or more and less than 50 per 100 organic-inorganic composite particle powders.
3: 10 or more and less than 30 per 100 organic-inorganic composite particle powders.
4: About 5 to 10 per 100 organic-inorganic composite particle powders.
5: Less than 5 per 100 organic-inorganic composite particle powders.

The white inorganic particle powder, the organic pigment, and the organic-inorganic composite pigment have hues of 0.5 g of a sample and 0.5 ml of castor oil, which are kneaded with a Hoover-type Mahler, and 4.5 g of clear lacquer is added to the paste. Then, a coating piece (coating thickness: about 30 μm) was prepared by applying a 150 μm (6 mil) applicator onto a cast-coated paper, and the coating piece was “multi-light source spectrocolorimeter MSC-IS-2D. ”(Suga Test Instruments Co., Ltd.)“ Multi-Spectro-color-Meter ”and“ Portable Spectral Color Meter Color Guide 45/0 ”(manufactured by Big Chemie Japan Co., Ltd.) are used for measurement and defined in JIS Z 8929 The color index was shown accordingly. The C ^* value represents saturation and can be obtained according to the following formula 2.

<Equation 2>
C ^* value = ((a ^* value) ² + (b ^* value) ² ) ^1/2

The coloring strength of the organic-inorganic composite pigment is as follows. First, each of the primary color enamel and the color development enamel prepared according to the method shown below is applied onto a cast coated paper using a 150 μm (6 mil) applicator to prepare a coated piece, About the coated piece, “Multi-light Spectrocolorimeter MSC-IS-2D” (manufactured by Suga Test Instruments Co., Ltd.) “Multi-Spectro-color-Meter” and “Portable Spectral Colorimeter Color Guide 45/0” (BIC Chemie Japan) L ^* value was measured using a product manufactured by Co., Ltd., and the difference was taken as ΔL ^* value.

Next, as a standard sample of the organic-inorganic composite pigment, a mixed pigment obtained by simply mixing the organic pigment and the white inorganic particle powder in the same proportion as the organic-inorganic composite pigment was used, and the primary color enamel and the color-enameled enamel were processed in the same manner as described above. A coated piece was prepared, the L ^* value of each coated piece was measured, and the difference was taken as the ΔLs ^* value.

The value calculated according to the following Equation 3 using DerutaLs ^* value of [Delta] L ^* value and the standard sample of the organic and inorganic composite pigments obtained are shown as the tinting strength (%).

<Equation 3>
Tinting strength (%) = 100 + {( ΔLs * value -Delta L ^* value) × 10}

Production of primary color enamel:
10 g of the above sample powder, 16 g of amino alkyd resin and 6 g of thinner were mixed and added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads, and then mixed and dispersed for 45 minutes with a paint shaker, and then 50 g of amino alkyd resin was added. Further, it was dispersed with a paint shaker for 5 minutes to produce a primary color enamel.

Production of color-enamel:
12 g of the primary color enamel and 40 g of amylac white (titanium dioxide-dispersed aminoalkyd resin) were blended and mixed and dispersed for 15 minutes with a paint shaker to produce a color-enamel.

  The hiding power of the white inorganic particle powder, the organic pigment, and the organic-inorganic composite pigment was represented by a value obtained according to the cryptometer method of JIS K 5101 8.2 using the primary color enamel obtained above.

The light resistance of the white inorganic particle powder, the organic pigment, and the organic-inorganic composite pigment is determined by using the primary color enamel prepared for measuring the coloring power as described above as a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141). ) With a thickness of 150 μm and dried to form a coating film. Half of the obtained coating for measurement is covered with a metal foil, and “I Super UV Tester” (SUV-W13 (manufactured by Iwasaki Electric Co., Ltd.)) ), The hue (L ^* value, a ^* ) of the portion irradiated with ultraviolet rays and the portion irradiated with ultraviolet rays by covering with a metal foil for 6 hours continuously with an irradiation intensity of 100 mW / cm ^{2 .} Value, b ^* value) were measured, respectively, and indicated by ΔE ^* value calculated according to the following formula 4 based on the measured value of the portion not irradiated with ultraviolet rays.

<Equation 4>
ΔE ^* value = ((ΔL ^* value) ² + (Δa ^* value) ² + (Δb ^* value) ² ) ^1/2
ΔL ^* value: difference in L ^* value of sample to be compared with UV irradiation Δa ^* value: difference in a ^* value of sample to be compared with UV irradiation Δb ^* value: b ^* value of sample to be compared with UV irradiation difference

  For each of the average major axis and the average minor axis (average diameter) of the master batch pellets, 10 pellets were measured with calipers, and the average value was indicated.

  Each color of the solvent-based paint and the water-based paint using the organic-inorganic composite pigment is a thickness of 150 μm on each cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141) prepared according to the formulation described later. About the coating piece for measurement obtained by applying and drying to form a coating film, “Multi-Spectro-color-Meter”, “Multi-light Spectrocolorimeter MSC-IS-2D” (manufactured by Suga Test Instruments Co., Ltd.) ”And“ Portable Spectral Color Meter Color Guide 45/0 ”(manufactured by Big Chemie Japan Co., Ltd.), and the color index was shown in accordance with JIS Z 8929. Moreover, the hue of the resin composition colored using the organic-inorganic composite pigment is the same as that of a colored resin plate produced by a method described later, “Multi-light source spectrocolorimeter MSC-IS-2D” (manufactured by Suga Test Instruments Co., Ltd.). ) Measurement was performed in the same manner as described above using “Multi-Spectro-color-Meter” and “Portable Spectral Colorimeter Color Guide 45/0” (manufactured by Big Chemie Japan Co., Ltd.).

  The glossiness of the coating film was shown by the glossiness at an incident angle of 60 ° using the “Glossmeter UGV-5D” (manufactured by Suga Test Instruments Co., Ltd.). It shows that the dispersibility of the coating material which mix | blended the organic inorganic composite pigment is excellent, so that glossiness is high.

The light resistance of the coating film using each paint was determined by covering half of the coating piece for measurement prepared in order to measure the hue of the above-mentioned paint with a metal foil, and using “I Super UV Tester” (SUV-W13 (Iwasaki Electric Co., Ltd.). The color of the part (L ^* ) of the part which was not irradiated with ultraviolet rays by irradiating ultraviolet rays with an irradiation intensity of 100 mW / cm ² for 6 hours using a metal foil and the part irradiated with ultraviolet rays ^. Value, a ^* value, b ^* value) were measured, respectively, and indicated by ΔE ^* value calculated according to the above equation 4 based on the measured value of the part not irradiated with ultraviolet rays.

In addition, the light resistance of each resin composition was determined by covering half of the resin plate prepared for measuring the hue of the resin composition with a metal foil and using “I Super UV Tester” (SUV-W13 (Iwasaki Electric Co., Ltd.). The color (L ^* value) between the part not irradiated with ultraviolet light and the part irradiated with ultraviolet light by covering with metal foil for 6 hours continuously after irradiation with ultraviolet light at an irradiation intensity of 100 mW / cm ^2. , A ^* value, b ^* value) were measured, and indicated by ΔE ^* value calculated according to the above equation 4 based on the measured value of the portion not irradiated with ultraviolet rays.

  The transparency of the coating film using the organic-inorganic composite pigment is determined by the “Self-recorded photoelectric spectrophotometer UV-2100” for the coating film obtained by applying a paint prepared by a method described later to a clear base film having a thickness of 100 μm. "(Linear absorption coefficient defined by the following formula 5) from the light transmittance measured using Shimadzu Corporation. The transparency of the resin composition was measured in the same manner as described above using a “self-recording photoelectric spectrophotometer UV-2100” (manufactured by Shimadzu Corporation) for a resin plate having the composition described below. The smaller the value of the linear absorption coefficient, the easier it is to transmit light and the higher the transparency.

<Equation 5>
Linear absorption coefficient (μm ⁻¹ ) = ln (1 / t) / FT
t: Light transmittance at λ = 900 nm (−)
FT: Film thickness used for measurement or thickness of resin plate (μm)

Preparation of paint for transparency evaluation:
Using 5 g of sample powder in a 250 ml glass bottle, the coating composition was blended at the following ratio, and mixed and dispersed for 120 minutes with a paint shaker together with 160 g of 3 mmφ glass beads to prepare a transparency evaluation coating.
9.9 parts by weight of sample powder,
Melamine resin (Super Peccamin J-820-60
: Product name: Dainippon Ink & Chemicals, Inc.) 9.8 parts by weight,
Alkyd resin (Beccosol 1307-60EL
: Product name: Dainippon Ink & Chemicals, Inc.) 39.6 parts by weight,
29.7 parts by weight of xylene,
Butanol 1.0 part by weight.

Preparation of water-based paint for transparency evaluation:
Using 5 g of sample powder in a 250 ml glass bottle, the coating composition was blended at the following ratio, and mixed and dispersed for 120 minutes with a paint shaker together with 160 g of 3 mmφ glass beads to prepare a transparency evaluation coating.
Sample powder 10.1 parts by weight,
9.3 parts by weight of water-soluble melamine resin,
(Product name: S-695: manufactured by Dainippon Ink & Chemicals, Inc.)
40.7 parts by weight of water-soluble alkyd resin
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
0.2 parts by weight of antifoaming agent,
(Product name: Nopco 8034: San Nopco Co., Ltd.)
28.2 parts by weight of water,
Butyl cellosolve 11.5 parts by weight.

Production of resin composition for transparency evaluation:
0.5 g of sample powder and 49.5 g of polyvinyl chloride resin powder (103EP8D: product symbol: manufactured by Nippon Zeon Co., Ltd.) are weighed and put in a 100 ml polybeaker and mixed well with a spatula to obtain a mixed powder. It was.

After adding 1.0 g of calcium stearate to the obtained mixed powder and mixing, and setting the clearance of the hot roll heated to 160 ° C. to 0.2 mm, the above mixed powder is kneaded with a roll little by little to obtain a resin composition The kneading was continued until the products were integrated, and then the resin composition was peeled from the roll and used as a colored resin plate raw material. Next, the resin composition is sandwiched between surface-polished stainless steel plates, placed in a hot press heated to 180 ° C., and press-molded at a pressure of 98,000 kPa (1 ton / cm ² ) to give a thickness of 1 mm. A colored resin plate for transparency evaluation was obtained.

The storage stability of the paint is a coating film produced by applying each paint prepared according to the formulation described later to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS-G-3141) at a thickness of 150 μm and drying. L ^* value, a ^* value, and b ^* value, and L ^* value of a coating film produced by applying the paint obtained by allowing the paint to stand at 25 ° C. for 1 week on a cold-rolled steel sheet and drying, The a ^* value and the b ^* value were measured and indicated by the ΔE ^* value obtained according to the following formula 6.

<Equation 6>
ΔE ^* value = ((ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ) ^1/2
ΔL ^* value: difference in L ^* value before and after standing of the coating film to be compared Δa ^* value: difference in a ^* value before and after standing of the coating film to be compared Δb ^* value: b before and after standing of the coating film to be compared ^* Value difference

Regarding the paint viscosity, the paint viscosity at 25 ° C. of the paint prepared according to the formulation described below is measured using an E type viscometer (cone plate type viscometer) EMD-R (manufactured by Tokyo Keiki Co., Ltd.) and a shear rate D = 1. The value at 92 sec ⁻¹ was determined.

The dispersibility of the organic / inorganic composite pigment in the resin composition was evaluated in five stages by visually determining the number of undispersed aggregated particles on the surface of the obtained colored resin plate. 5 indicates the best dispersion state.
5: Undispersed material is not recognized,
4: 1 to less than 5 per 1 cm ²
3: 5 or more and less than 10 per 1 cm ²
2: 10 to less than 50 per 1 cm ²
1: 50 or more per 1 cm ² .

<Embodiment of the Invention>
<Manufacture of organic-inorganic composite particle powder>
Titanium oxide particle powder (particle shape: granular, average particle size 0.24 μm, BET specific surface area value 11.6 m ² / g, measured by “Portable Spectral Colorimeter Color Guide 45/0”: L ^* value 94.15, a ^* value 1.06, b ^* value 2.22, C ^* value 2.46, measured value by “multi-light source spectrocolorimeter MSC-IS-2D”: L ^* value 96.31, a ^* value 1. 06, b ^* value−1.66, C ^* value 1.97, hiding power 1,490 cm ² / g, light resistance ΔE ^* value 6.86) In order to break up aggregation of 20 kg, a stirrer was used for 150 l of pure water. Further, a “TK pipeline homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.) was passed three times to obtain a slurry containing titanium oxide particle powder.

  Next, the slurry containing the titanium oxide particle powder is passed five times at a shaft rotational speed of 2000 rpm using a horizontal sand grinder “Mighty Mill MHG-1.5L” (manufactured by Inoue Seisakusho Co., Ltd.) to contain the titanium oxide particle powder. A dispersed slurry was obtained.

  The residue of the sieve at 325 mesh (aperture 44 μm) of the obtained dispersion slurry was 0%. The dispersion slurry was filtered and washed with water to obtain a cake of titanium oxide particle powder. After drying this titanium oxide particle powder cake at 120 ° C., 11.0 kg of the dry powder was put into an edge runner “MPUV-2 type” (product name, manufactured by Matsumoto Foundry Co., Ltd.), and 294 N / cm (30 Kg). / Cm) for 30 minutes to stir and agglomerate the particles lightly.

  Next, a methyltriethoxysilane solution obtained by mixing and diluting 110 g of methyltriethoxysilane (trade name: TSL8123: manufactured by GE Toshiba Silicone Co., Ltd.) with 200 ml of ethanol, the above-mentioned titanium oxide particle powder while operating an edge runner. The mixture was stirred for 30 minutes with a linear load of 588 N / cm (60 Kg / cm). The stirring speed at this time was 22 rpm.

Next, organic pigment B-1 (type: phthalocyanine pigment, particle shape: granular, average particle size 0.06 μm, BET specific surface area value 71.6 m ² / g, hiding power 240 cm ² / g, “portable spectral colorimeter Measured value by "Color Guide 45/0": L ^* value 5.20, a ^* value 9.14, b ^* value -21.84, measured value by "Multi-light source spectrocolorimeter MSC-IS-2D": L ^* Value 17.70, a ^* value 9.72, b ^* value-23.44, light resistance ΔE ^* value 10.84) 1,100 g was added over 10 minutes while running the edge runner, and 392N After mixing and stirring for 20 minutes with a linear load of 40 cm / cm (40 kg / cm), the organic pigment B-1 was deposited on the methyltriethoxysilane coating, and then heated at 105 ° C. for 60 minutes using a dryer. Organic inorganic composite particle powder I got the end. The stirring speed at this time was 22 rpm.

The organic-inorganic composite pigment comprising the obtained organic-inorganic composite particle powder was a granular particle powder having an average particle diameter of 0.24 μm. BET specific surface area value is 13.8 m ² / g, measured by “Portable Spectral Colorimeter Color Guide 45/0”: L ^* value is 64.33, a ^* value is −5.68, b ^* value is −29 .36, Measured by "Multi-light source spectrocolorimeter MSC-IS-2D": L ^* value 64.67, a ^* value 1.06, b ^* value 31.42, coloring power 138%, hiding power Was 1,520 cm ² / g, the light resistance ΔE ^* value was 2.48, and the desorption rate of the organic pigment was 2.5%. The coating amount of the organosilane compound produced from methyltriethoxysilane is 0.15% by weight in terms of Si, and the amount of adhering organic pigment is 6.04% by weight in terms of C (100% by weight of titanium oxide particle powder). Equivalent to 10 parts by weight).

  As a result of observing the electron micrograph, since almost no organic pigment B-1 was observed, it was confirmed that almost all of the organic pigment B-1 was adhered to the organosilane compound coating formed from methyltriethoxysilane. .

<Manufacture of solvent-based paints containing organic-inorganic composite pigments>
10 g of the organic / inorganic composite pigment, aminoalkyd resin and thinner were blended in the following proportions and added together with 90 g of 3 mmφ glass beads to a 140 ml glass bottle, and then mixed and dispersed in a paint shaker for 90 minutes to prepare a mill base.

12.2 parts by weight of organic / inorganic composite pigment,
19.5 parts by weight of amino alkyd resin,
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)
Thinner 7.3 parts by weight.

  Using the mill base, an amino alkyd resin was blended so as to have the following ratio, and further mixed and dispersed with a paint shaker for 15 minutes to obtain a solvent-based paint containing an organic-inorganic composite pigment.

39.0 parts by weight of mill base,
Aminoalkyd resin 61.0 parts by weight.
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)

The solvent-based paint obtained had a paint viscosity of 1,024 cP, and the storage stability of the paint was 0.83 in ΔE ^* value.

Next, the gloss of the coating film obtained by applying the solvent-based paint to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141) at a thickness of 150 μm and drying is 91%, and the hue is Measured values using “Portable Spectral Colorimeter Color Guide 45/0”: L ^* value is 67.13, a ^* value is −5.32, b ^* value is −28.64, “Multi-light source spectrocolorimeter MSC- Measurement values according to IS-2D: L ^* value 67.41, a ^* value −5.32, b ^* value −30.74, and light resistance ΔE ^* value was 2.81.

<Manufacture of water-based paint containing organic-inorganic composite pigment>
7.62 g of the organic / inorganic composite pigment and water-soluble alkyd resin were added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads at the following ratio, and then mixed and dispersed for 90 minutes with a paint shaker to prepare a mill base.

12.4 parts by weight of organic-inorganic composite pigment,
9.0 parts by weight of water-soluble alkyd resin
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
0.1 part by weight of antifoaming agent,
(Product name: Nopco 8034: San Nopco Co., Ltd.)
4.8 parts by weight of water,
Butyl cellosolve 4.1 parts by weight.

  Using the mill base, the paint composition was blended at the following ratio, and further mixed and dispersed for 15 minutes with a paint shaker to obtain an aqueous paint containing an organic-inorganic composite pigment.

30.4 parts by weight of mill base,
46.2 parts by weight of a water-soluble alkyd resin
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
12.6 parts by weight of a water-soluble melamine resin,
(Product name: S-695: manufactured by Dainippon Ink & Chemicals, Inc.)
0.1 part by weight of antifoaming agent,
(Product name: Nopco 8034: San Nopco Co., Ltd.)
9.1 parts by weight of water,
Butyl cellosolve 1.6 parts by weight.

The resulting water-based paint had a paint viscosity of 2,560 cP and a storage stability of 0.86 in ΔE ^* value.

Next, the gloss of the coating film obtained by applying the water-based paint to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141) at a thickness of 150 μm and drying is 88% and the hue is “ Measured with a portable spectral colorimeter Color Guide 45/0: L ^* value is 65.13, a ^* value is -5.63, b ^* value is -29.26, multi-light source spectral colorimeter MSC-IS- Measured value according to “2D”: L ^* value 65.44, a ^* value −5.63, b ^* value −31.33, and light resistance ΔE ^* value was 2.72.

<Manufacture of resin composition>
2.5 g of the organic / inorganic composite pigment and 47.5 g of polyvinyl chloride resin powder 103EP8D (manufactured by Nippon Zeon Co., Ltd.) were weighed, put in a 100 ml poly beaker and mixed well with a spatula to obtain a mixed powder.

  After adding 0.5 g of calcium stearate to the obtained mixed powder and mixing it, and setting the clearance of the hot roll heated to 160 ° C. to 0.2 mm, the mixed powder was kneaded with a roll little by little to obtain a resin composition The kneading was continued until the products were integrated, and then the resin composition was peeled from the roll and used as a colored resin plate raw material.

Next, the resin composition is sandwiched between surface-polished stainless steel plates, placed in a hot press heated to 180 ° C., and press-molded at a pressure of 98,000 kPa (1 ton / cm ² ) to give a thickness of 1 mm. A colored resin plate was obtained. The dispersion state of the obtained colored resin plate is 5, and the hue is measured by “Portable Spectral Colorimeter Color Guide 45/0”: L ^* value is 66.31, a ^* value is −5.84, b ^*. Value is -28.65, measured by "multi-light source spectrocolorimeter MSC-IS-2D": L ^* value 66.60, a ^* value -5.84, b ^* value -30.75, light resistance is The ΔE ^* value was 2.95.

<Production of solvent-based pigment dispersion>
The organic-inorganic composite pigment was blended together with the following pigment dispersion constituting base material at the following ratio and subjected to a dispersion treatment using a sand grinder mill to prepare a solvent-based pigment dispersion.

12.2 parts by weight of organic / inorganic composite pigment,
6.1 parts by weight of amino alkyd resin
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)
Thinner 12.2 parts by weight.

<Manufacture of solvent-based paints>
Using the solvent-based pigment dispersion, an aminoalkyd resin was blended so as to have the following ratio, and mixed and dispersed for 15 minutes with a paint shaker to obtain a solvent-based paint containing an organic-inorganic composite pigment.

30.5 parts by weight of solvent-based pigment dispersion,
Aminoalkyd resin 69.5 parts by weight.
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)

The solvent-based paint obtained had a paint viscosity of 608 cP and the storage stability of the paint was 0.84 in ΔE ^* value.

Next, the gloss of the coating film obtained by applying the solvent-based paint to a cold-rolled steel sheet (0.8 mm × 70 mm × 150 mm) (JIS G-3141) at a thickness of 150 μm and drying is 105%, and the hue is Measured value using “Portable Spectral Colorimeter Color Guide 45/0”: L ^* value is 67.72, a ^* value is −5.36, b ^* value is −28.09, “Multi-light source spectrocolorimeter MSC- Measurement value by IS-2D) The L ^* value was 67.99, the a ^* value was −5.36, the b ^* value was −30.22, and the light resistance ΔE ^* value was 2.65.

<Production of water-based pigment dispersion>
The organic-inorganic composite pigment was blended in the following proportion together with the following pigment dispersion constituting base material, and subjected to a dispersion treatment using a sand grinder mill to prepare an aqueous pigment dispersion.

17.5 parts by weight of organic / inorganic composite pigment,
3.5 parts by weight of water-soluble alkyd resin
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
0.1 part by weight of antifoaming agent,
(Product name: Nopco 8034: San Nopco Co., Ltd.)
7.5 parts by weight of water,
6.4 parts by weight of butyl cellosolve.

  Using the mill base, the paint composition was blended at the following ratio, and further mixed and dispersed for 15 minutes with a paint shaker to obtain a water-based paint.

<Manufacture of water-based paint>
35.0 parts by weight of an aqueous pigment dispersion,
30.0 parts by weight of water-soluble alkyd resin
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
10.8 parts by weight of water-soluble melamine resin,
(Product name: S-695: manufactured by Dainippon Ink & Chemicals, Inc.)
0.1 part by weight of antifoaming agent,
(Product name: Nopco 8034: San Nopco Co., Ltd.)
24.1 parts by weight of water,

The resulting water-based paint had a paint viscosity of 1,291 cP and a storage stability of 0.85 in ΔE ^* value.

Next, the gloss of the coating film obtained by applying the water-based paint to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-3141) at a thickness of 150 μm and drying is 95%, and the hue is “ Measured with a portable spectral colorimeter Color Guide 45/0: L ^* value is 65.45, a ^* value is -5.59, b ^* value is -29.38, "Multi-light source spectrocolorimeter MSC-IS -2D ": L ^* value was 65.76, a ^* value was -5.59, b ^* value was -31.44, and light resistance ΔE ^* value was 2.61.

<Manufacture of master batch pellets>
20.0 parts by weight of the above organic-inorganic composite pigment is kneaded at 160 ° C. by a biaxial kneader with 80.0 parts by weight of polyvinyl chloride resin powder 103EP8D (manufactured by Nippon Zeon Co., Ltd.). Columnar (average minor axis 3 mm, average diameter 3 mm) master batch pellets were obtained.

<Manufacture of resin composition>
As a colored resin plate raw material, 25.0 parts by weight of the master batch pellets, 74.5 parts by weight of polyvinyl chloride resin powder 103EP8D (manufactured by Zeon Corporation) and 0.5 parts by weight of calcium stearate are mixed with a ribbon blender. Using.

Next, the resin composition is sandwiched between surface-polished stainless steel plates, placed in a hot press heated to 180 ° C., and press-molded at a pressure of 98,000 kPa (1 ton / cm ² ) to give a thickness of 1 mm. A colored resin plate was obtained. The dispersion state of the obtained colored resin plate is 5, and the hue is measured by “Portable Spectral Colorimeter Color Guide 45/0”: L ^* value is 66.51, a ^* value is −5.72 and b ^*. Value is -28.92, measured value by "multi-light source spectrocolorimeter MSC-IS-2D": L ^* value is 66.80, a ^* value is -5.72, b ^* value is -31.01, The light resistance ΔE ^* value was 2.84.

  Next, examples and comparative examples are shown.

Core particles 1 to 5:
White inorganic particle powder having the characteristics shown in Table 1 was prepared as the core particle powder.

Core particle 6:
Using 20 kg of the titanium oxide particle powder of the core particle 1 and 150 l of water, a slurry containing the titanium oxide particle powder was obtained. The pH value of the redispersed slurry containing the obtained titanium oxide particle powder was adjusted to 10.5 using an aqueous sodium hydroxide solution, and water was added to the slurry to adjust the slurry concentration to 98 g / l. 150 l of this slurry was heated to 60 ° C., and 5444 ml of a 1.0 mol / l sodium aluminate solution (corresponding to 1.0% by weight in terms of Al with respect to the titanium oxide particle powder) was added to the slurry, and 30 After holding for a minute, the pH value was adjusted to 7.5 with acetic acid. After maintaining for 30 minutes in this state, filtration, washing with water, drying and pulverization were carried out to obtain titanium oxide particle powder whose particle surface was coated with aluminum hydroxide.

  The production conditions at this time are shown in Table 2, and the properties of the obtained surface-treated titanium oxide particle powder are shown in Table 3.

Core particles 7 to 10:
White inorganic particles whose particle surfaces are coated with a coating in the same manner as the core particles 6 except that the white inorganic particle powders of the core particles 2 to 5 are used and the type and amount of the surface coating are variously changed. A powder was obtained.

  The production conditions at this time are shown in Table 2, and the properties of the obtained surface-treated white inorganic particle powder are shown in Table 3.

  In the surface treatment step, the type of coating A is an aluminum hydroxide, and S represents a silicon oxide.

Organic pigment:
An organic pigment having various characteristics shown in Table 4 was prepared as the organic pigment.

Examples 1-14, Comparative Examples 1-5:
Various types of additives, amount added, edge loader treatment line load and time in paste coating process, organic pigment type, amount added, edge runner treatment line load and time in organic pigment adhesion process Except for the above, an organic-inorganic composite pigment was obtained in the same manner as in the above embodiment.

  The production conditions at this time are shown in Table 5, and various properties of the obtained organic-inorganic composite pigment are shown in Table 6.

  In Example 4, 100 g of organic pigment Y-1 was added in 20 g portions in 5 portions, and then Y-2 50 g was added in 25 g portions in 2 portions. In Example 13, 50 g of organic pigment B-1 and 50 g of organic pigment Y-2 were mixed in advance using a Henschel mixer or the like, and then 100 g of the mixed pigment was added over 200 minutes. In Example 14, 150 g of the organic pigment G-1 was added in 10 portions at 15 g.

<Organic inorganic composite particle powder having a plurality of colored adhesion layers>
Example 15:
Titanium oxide particle powder (particle shape: granular, average particle diameter 0.24 μm, BET specific surface area value 11.6 m ² / g, hue measured by “Portable Spectrocolorimeter Color Guide 45/0”: L ^* value 94. 15, a ^* value 1.06, b ^* value 2.22, C ^* value 2.46, measured value by “multi-light source spectrocolorimeter MSC-IS-2D”: L ^* value 96.31, a ^* value 1.06, b ^* value−1.66, C ^* value 1.97, hiding power 1,490 cm ² / g, light resistance ΔE ^* value 6.86) A stirrer was added to 150 liters of pure water to break up the aggregation. And passed through a “TK pipeline homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.) three times to obtain a slurry containing titanium oxide particle powder.

  Next, the slurry containing the titanium oxide particle powder is passed five times at a shaft rotational speed of 2000 rpm using a horizontal sand grinder “Mighty Mill MHG-1.5L” (manufactured by Inoue Seisakusho Co., Ltd.) to contain the titanium oxide particle powder. A dispersed slurry was obtained.

  The residue of the sieve at 325 mesh (aperture 44 μm) of the obtained dispersion slurry was 0%. The dispersion slurry was filtered and washed with water to obtain a cake of titanium oxide particle powder. After drying this titanium oxide particle powder cake at 120 ° C., 11.0 kg of the dry powder was put into an edge runner “MPUV-2 type” (product name, manufactured by Matsumoto Foundry Co., Ltd.), and 294 N / cm (30 Kg). / Cm) for 30 minutes to stir and agglomerate the particles lightly.

  Next, a methyltriethoxysilane solution obtained by mixing and diluting 110 g of methyltriethoxysilane (trade name: TSL8123: manufactured by GE Toshiba Silicone Co., Ltd.) with 200 ml of ethanol, the above-mentioned titanium oxide particle powder while operating an edge runner. The mixture was stirred for 20 minutes with a linear load of 588 N / cm (60 Kg / cm). The stirring speed at this time was 22 rpm.

Next, organic pigment B-1 (type: phthalocyanine pigment, particle shape: granular, average particle size 0.06 μm, BET specific surface area value 71.6 m ² / g, hiding power 240 cm ² / g, “portable spectral colorimeter Measured value by "Color Guide 45/0": L ^* value 5.20, a ^* value 9.14, b ^* value -21.84, measured value by "Multi-light source spectrocolorimeter MSC-IS-2D": L ^* Value 17.70, a ^* value 9.72, b ^* value-23.44, light resistance ΔE ^* value 10.84) 2,200 g were added over 20 minutes while running the edge runner, and 392N The mixture was stirred for 60 minutes with a linear load of 40 cm / cm (40 kg / cm) to obtain an intermediate pigment having phthalocyanine blue adhered on the methyltriethoxysilane coating. The stirring speed at this time was 22 rpm.

  In order to confirm the coating amount of methyltriethoxysilane and the adhesion amount of the organic pigment B-1, a part of the obtained intermediate pigment was fractionated and heat-treated at 105 ° C. for 60 minutes using a dryer. It was. The coating amount of methyltriethoxysilane is 0.15% by weight in terms of Si, and the adhesion amount of organic pigment B-1 is 10.96% by weight in terms of C (20% by weight with respect to 100 parts by weight of titanium oxide particle powder). Corresponding to the part). As a result of observing the electron micrograph, since almost no organic pigment B-1 was observed, it was confirmed that almost all of the organic pigment B-1 was adhered to the organosilane compound coating layer formed from methyltriethoxysilane. It was.

  Next, 220 g of dimethylpolysiloxane (trade name: TSF451: manufactured by GE Toshiba Silicone Co., Ltd.) is added to the intermediate pigment while the edge runner is operated, and mixed for 60 minutes with a linear load of 588 N / cm (60 Kg / cm). Stirring was performed to obtain an intermediate pigment having a surface coated with dimethylpolysiloxane. The stirring speed at this time was 22 rpm.

Next, organic pigment B-2 (type: phthalocyanine pigment, particle shape: granular, average particle diameter 0.08 μm, BET specific surface area value 56.3 m ² / g, hiding power 272 cm ² / g, “portable spectral colorimeter Measured value by “color guide 45/0”: L ^* value 6.00, a ^* value −11.60, b ^* value −23.56, measured value by “multi-light source spectrocolorimeter MSC-IS-2D”: L ^* value 17.32, a ^* value −11.60, b ^* value −26.53, light resistance ΔE ^* value 10.21) 2200 g was added over 20 minutes while running the edge runner, and 392N After mixing and stirring for 60 minutes with a linear load of 40 cm / cm (40 kg / cm) to adhere the organic pigment B-2 to the organic pigment B-1 adhesion layer via dimethylpolysiloxane, the temperature is 105 ° C. using a dryer. Heat treatment for 60 minutes Thus, organic-inorganic composite particle powder was obtained. The stirring speed at this time was 22 rpm.

The obtained organic-inorganic composite pigment was a granular particle powder having an average particle size of 0.25 μm. BET specific surface area value is 11.8 m ² / g, measured by “Portable Spectral Colorimeter Color Guide 45/0”: L ^* value 62.14, a ^* value 7.24, b ^* value −19.92, “ Measured with a multi-source spectrocolorimeter MSC-IS-2D: L ^* value is 62.67, a ^* value is 7.24, b ^* value is -23.07, coloring power is 217%, hiding power is The value of 1,810 cm ² / g, the light resistance ΔE ^* value was 2.36, and the desorption rate of the organic pigment was 6.2%. The coating amount of dimethylpolysiloxane is 0.70% by weight in terms of Si, and the total adhesion amount of organic pigment is 18.84% by weight in terms of C (corresponding to 40 parts by weight with respect to 100 parts by weight of titanium oxide particle powder). there were.

  As a result of observing the electron micrograph, since almost no organic pigment B-2 was observed, it was confirmed that almost the entire amount of the organic pigment adhered to the dimethylpolysiloxane coating layer.

  The production conditions at this time are shown in Tables 7 and 8, and the properties of the organic-inorganic composite pigment made of the obtained organic-inorganic composite particles are shown in Table 11.

Examples 16-39, Comparative Examples 6-16:
Kind of core particle, kind of glue in the adhesion process of the first colored adhesion layer, addition amount, line load and time of edge runner treatment, kind of organic pigment, addition amount, line load and time of edge runner treatment, and second Except for various changes in the type of glue, amount added, line load and time for edge runner treatment, type of organic pigment, amount added, and line load and time for edge runner treatment in the adhesion process of the colored adhesion layer In the same manner as in Example 15, an organic-inorganic composite pigment was obtained.

  Production conditions at this time are shown in Tables 7 to 10, and various properties of the obtained organic-inorganic composite particle powder are shown in Tables 11 to 13.

  In addition, the intermediate pigment 5 added 150 g of organic pigment Y-1 over 150 minutes. As the intermediate pigment 7, 100 g of organic pigment R-1 was added over 150 minutes. As the intermediate pigment 8, 150 g of organic pigment Y-1 was added in 15 g portions in 10 portions.

  In Example 20, 75 g of organic pigment B-2 was added in 25 g portions in three portions. In Example 23, 100 g of organic pigment B-2 was added over 100 minutes. In Example 24, 100 g of organic pigment R-2 was added over 100 minutes. In Example 29, 150 g of organic pigment Y-2 was added over 150 minutes. In Example 30, 80 g of organic pigment Y-1 was added in four portions of 20 g. In Example 32, 200 g of organic pigment Y-2 was added over 200 minutes.

<Solvent paint>
Examples 40-78, Comparative Examples 17-40:
A solvent-based paint was obtained in the same manner as in the above embodiment except that the kind of the organic-inorganic composite pigment was variously changed.

  Tables 14 to 18 show properties of the obtained paint and properties of the coating film.

<Solvent pigment dispersion>
Examples 79-100:
A solvent-based pigment dispersion was obtained in the same manner as in the above-described embodiment except that the kind of organic-inorganic composite pigment, the kind of resin and solvent in the pigment dispersion-constituting substrate, and the amount added were variously changed.

  The manufacturing conditions at this time are shown in Table 19.

<Solvent paint>
Examples 101-116:
A solvent-based paint was obtained in the same manner as in the above-described embodiment except that the types and addition amounts of the solvent-based pigment dispersion and the resin were variously changed.

  The production conditions at this time are shown in Table 20, and various properties of the obtained solvent-based paint and coating film are shown in Table 21.

<Water-based paint>
Examples 117-155, Comparative Examples 41-64:
A water-based paint was obtained in the same manner as in the above-described embodiment except that the kind of the organic-inorganic composite pigment was changed variously.

  Tables 22 to 26 show properties of the obtained water-based paint and properties of the coating film.

<Aqueous pigment dispersion>
Examples 156-177:
An aqueous pigment dispersion was obtained in the same manner as in the above embodiment except that the type of organic-inorganic composite pigment, the type and amount of resin, additive and solvent in the aqueous pigment dispersion-constituting substrate were variously changed. It was.

  The manufacturing conditions at this time are shown in Tables 27 and 28.

<Water-based paint>
Examples 178-193:
A water-based paint was obtained in the same manner as in the above-described embodiment except that the types and amounts of the aqueous pigment dispersion, resin, additive and solvent were varied.

  The production conditions at this time are shown in Table 29, and various characteristics of the obtained water-based paint and coating film are shown in Table 30.

<Resin composition>
Examples 194 to 232, Comparative Examples 65 to 88:
A resin composition was obtained in the same manner as in the above embodiment except that the kind of the organic-inorganic composite pigment was variously changed.

  Tables 31 to 35 show the manufacturing conditions and various properties of the obtained resin composition.

<Master batch pellet>
Examples 233-254:
Master batch pellets were obtained in the same manner as in the above-described embodiment except that the type of organic-inorganic composite pigment, the type of resin, and the amount added were variously changed.

  Table 36 shows the manufacturing conditions at this time.

<Resin composition>
Examples 255-270:
A resin composition was obtained in the same manner as in the embodiment of the present invention except that the types and amounts of the master batch pellets, resin and additives were changed.

  The production conditions at this time are shown in Table 37, and various characteristics of the obtained resin composition are shown in Table 38.

  The organic-inorganic composite pigment composed of the organic-inorganic composite particle powder according to the present invention is suitable as a color pigment in various applications because the organic pigment adhering to the particle surface is suppressed from being detached and harmless. is there.

The paint and the resin composition according to the present invention are suitable as a paint and a resin composition in consideration of environmental pollution because the organic inorganic composite pigment is used as a coloring pigment, and the organic pigment is prevented from being detached. is there.

Claims (2)

The particle surface of the white inorganic particle powder is from one or more of an organosilicon compound, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zirconate coupling agent, an oligomer or a polymer compound. It consists of a composite particle powder having an average particle diameter of 0.01 to 10.0 μm, which is coated with the selected paste and has an organic pigment attached to the coating, and the amount of the organic pigment attached is the white inorganic particle powder 100 The organic-inorganic composite particle powder, which is 1 to 500 parts by weight with respect to parts by weight, and the organic pigment release rate of the organic-inorganic composite particle powder is 8.9% or less. The particle surface of the white inorganic particle powder according to claim 1 is previously coated with an intermediate coating composed of at least one selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. An organic-inorganic composite particle powder.