JP5077516B2 - Heat shielding composite particle powder and heat shielding coating composition using the same - Google Patents

Description

  The present invention can obtain a heat shielding coating composition having a sharp particle size distribution and high infrared reflectivity, and has excellent dispersibility and storage stability in the heat shielding coating composition. The present invention relates to shielding composite particle powder.

  Conventionally, buildings, cars, etc. used outdoors have an internal temperature that rises due to solar radiation, so the exterior paint of buildings, cars, etc. should be made white to light using a white pigment such as titanium oxide. The solar light is reflected to obtain a certain degree of heat shielding effect.

  However, in particular, the roofs of outdoor buildings are often dark to black in order to make the dirt inconspicuous. For these buildings and automobiles whose exterior paint has a dark to black color, Compared to buildings and automobiles having a white to light-colored exterior paint, the solar heat shielding effect is low, and the indoor temperature tends to rise remarkably.

  Therefore, from the viewpoint of energy saving for cooling and prevention of global warming, reduction of the internal temperature rise of buildings and automobiles having a dark to black appearance is strongly desired.

  Currently, black pigments such as carbon black, graphite and black iron oxide, black organic pigments such as perylene black, and two- or three-color organic pigments are used as dark to black colorants such as inks, paints, rubber and plastics. Black pigments obtained by mixing are known.

  Among these black pigments, especially the most commonly used carbon black has a high blackness, but absorbs light from the visible light region to the infrared region, and therefore has a remarkable heat shielding effect. It is low. Further, since the particle size is a fine particle having an average particle size of about 0.005 to 0.05 μm, it is easy to self-aggregate, and it is difficult to disperse in the resin composition in a fine particle state, and the aggregate has a maximum particle size. In general, it is known to form coarse particles of 0.1 μm to 5 mm.

  In general, the specific gravity of the organic pigment has a width of 1.3 to 2.5, and the black pigment obtained by mixing several kinds of organic pigments appears to be black even though it looks black at first glance. From the specific gravity difference, for example, when dispersed in a paint vehicle, color separation is likely to occur due to the specific gravity difference during long-term storage.

  So far, as a method for obtaining a black pigment using a pigment other than carbon black, a heat shielding property having a black color is obtained by mixing a colored organic pigment having a solar heat radiation reflectance of a specific value or more in a region of 350 to 2100 nm. Black pigment compositions have been proposed (Patent Documents 1 to 3).

  Moreover, the heat ray shielding coating material containing the black pigment whose solar reflectance in the area | region of 780-2100 nm is 3.0% or more is proposed (patent document 4).

  In addition, for the purpose of obtaining a heat-shielding pigment having excellent infrared reflectivity and coloring power, a heat-shielding pigment in which perylene black adheres to the particle surface of white inorganic particle powder via an organosilane compound is known. (Patent Document 5).

JP-A-4-255769 JP 2000-212475 A JP 2002-20647 A JP 2000-72990 A JP 2004-10851 A

  Heat-shielding composite particles having a sharp particle size distribution and capable of obtaining a heat-shielding coating composition having high infrared reflectivity and excellent in dispersibility and storage stability in the heat-shielding coating composition Powders are currently the most demanded but have not yet been obtained.

That is, in the above-mentioned Patent Documents 1 to 3, by mixing chromatic pigments of red, orange, yellow, green, blue, and violet colors whose solar thermal radiation reflectance in the region of 350 to 2100 nm is a specific value or more. , A method for obtaining a heat-shielding black pigment composition having a black color with an L ^* value of 20 or less in the Munsell symbol (N-1) or CIE 1976 LAB is described, but the pigment deteriorates due to long-term use. There is also a problem that the color balance is lost and the color is easily changed. In addition, when dispersed in a vehicle, color separation easily occurs due to the difference in specific gravity of each organic pigment, and since only existing organic pigments having different dispersion levels are dispersed and mixed, the particle size is reduced. It tends to be non-uniform and difficult to disperse in a vehicle or resin composition.

  Further, in the aforementioned Patent Document 4, a heat ray shielding paint containing a black pigment having a solar reflectance of 3.0% or more in a wavelength region of 780 to 2100 nm is proposed, but the reflectance in an infrared wavelength region is high. Since it is low, heat is easily trapped in the coating film, and it is difficult to say that heat shielding properties are excellent.

  In the above-mentioned patent document 5, although the method of attaching perylene black to the particle | grain surface of a white inorganic particle powder through an organosilane compound is described, in a wavelength range of 900-2100 nm as shown in a following comparative example. It is difficult to say that the reflectance is less than 40% and the heat shielding property is excellent.

  Thus, the present invention can provide a heat shielding coating composition having a sharp particle size distribution and high infrared reflectivity, and is excellent in dispersibility and storage stability in the heat shielding coating composition. Another object of the present invention is to provide a heat-shielding composite particle powder that exhibits a deep color from black.

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

That is, the present invention comprises a composite particle powder in which at least two colors of organic dyes are attached to the particle surface of the inorganic particle powder, and the organic dye is a red organic dye, a blue organic dye, a yellow organic dye, green organic pigments, violet organic dyes, those selected from orange organic pigments and brown organic dye, the reflectance at the wavelength of 900~2100nm the coating film to the person the composite particles produced according JIS K 5101 It is a heat shielding composite particle powder characterized by being 40% or more (Invention 1).

The present invention also provides a composite particle powder in which the particle surface of the inorganic particle powder is coated with a surface modifier and at least two or more colors of organic dyes are attached to the particle surface of the surface modifier-coated inorganic particle. made, the are those organic dye is selected from the organic red-based pigments, organic blue-based pigments, organic yellow-based pigments, green-based organic pigments, violet-based organic pigments, orange organic pigments and brown organic dye, those wherein It is a heat-shielding composite particle powder characterized in that the coating film produced from the composite particle powder according to JIS K 5101 has a reflectance at a wavelength of 900 to 2100 nm of 40% or more (Invention 2).

Moreover, this invention is a heat-shielding coating composition characterized by containing the heat-shielding composite particle powder of this invention 1 or 2 (this invention 3 ).

  The heat-shielding composite particle powder according to the present invention has a sharp particle size distribution, can provide a heat-shielding coating composition having high infrared reflectivity, and is dispersible in the heat-shielding coating composition. And since it is excellent in storage stability, it is suitable as a colored particle powder for a heat-shielding coating composition exhibiting a dark color from black.

  Further, the heat-shielding coating composition according to the present invention is excellent in dispersibility and storage stability by using the above-mentioned heat-shielding composite particle powder, and thus is particularly suitable for applications that require long-term storage. Can be used.

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

  First, the heat shielding composite particle powder according to the present invention will be described.

  The heat-shielding composite particle powder according to the present invention is composed of composite particles in which organic pigments of two or more colors are attached to the particle surface of the inorganic particle powder that is the core particle powder.

  As the inorganic particle powder in the present invention, any of white inorganic particle powder and colored inorganic particle powder can be used. As white inorganic particle powder, white particle powder such as titanium dioxide, barium titanate, zinc oxide, pearl pigment such as mica titanium, muscovite, silica fine particles such as silica powder, white carbon, fine powder silicic acid, diatomaceous earth and clay, Examples include extender pigments such as calcium carbonate, barium sulfate, alumina white, talc, and transparent titanium oxide. Examples of the colored inorganic particles include iron oxide particles such as magnetite, goethite, and hematite, and titanium black.

  The average primary particle diameter of the inorganic particle powder is preferably 0.001 to 1.0 μm, more preferably 0.003 to 0.95 μm, still more preferably 0.005 to 0.9 μm, and the particle shape is spherical. Any shape such as granular, polyhedral, needle-shaped, spindle-shaped, rice-grained, flake-shaped, scale-shaped and plate-shaped may be used. When the average particle diameter exceeds 1.0 μm, the resulting heat-shielding composite particle powder becomes coarse particles, which is not preferable because coloring power is reduced. On the other hand, when the average particle diameter is less than 0.001 μm, It is not preferable because the agglomeration tends to cause aggregation.

  The geometric standard deviation value of the primary particle size of the inorganic particle powder is preferably 2.0 or less, more preferably 1.8 or less, and still more preferably 1.5 or less. When it exceeds 2.0, the particle size distribution of the obtained heat shielding composite particle powder is wide, and the dispersibility in the heat shielding coating composition is lowered, which is not preferable.

The BET specific surface area value of the inorganic particle powder in the present invention is preferably 0.1 m ² / g or more. When the BET specific surface area value is less than 0.1 m ² / g, the inorganic particles are coarse, or the particles are particles that are sintered between the particles, and the resulting heat shielding composite particle powder Becomes coarse particles, and coloring power and dispersibility in the heat shielding coating composition are lowered. Considering the coloring power of the obtained heat-shielding composite particle powder and the dispersibility in the heat-shielding coating composition, the BET specific surface area value is more preferably 0.5 m ² / g or more, still more preferably 1.0 m. ² / g or more. Considering the uniform coating treatment with the surface modifier and / or the uniform adhesion treatment with the organic pigment on the particle surface of the inorganic particle powder, the upper limit is about 1000 m ² / g, preferably 800 m ² / g, More preferably, it is 500 m < ² > / g.

The hue of the inorganic particle powder in the present invention is not particularly limited because it is possible to obtain dark heat-shielding composite particles from a dark color by adjusting the blending ratio of the organic dye attached to the particle surface of the inorganic particle powder. From the viewpoint of ease of toning, the saturation (c ^* value) is preferably as low as possible. Specifically, the c ^* value is preferably 18.00 or less, more preferably 15.00 or less, still more preferably 12.00 or less, and most preferably 9.00 or less.

  The heat shielding composite particle powder according to the present invention has a particle surface of an inorganic particle powder that is a core particle powder in consideration of the particle size distribution of the average primary particle size and the dispersibility and dispersion stability in the heat shielding coating composition. Are preferably composed of composite particles in which at least two or more organic dyes are attached to the surface modifier-coated inorganic particle surface.

  In the present invention, when a surface modifier is used, any material can be used as long as it can attach an organic dye to the surface of inorganic particles, and alkoxysilane, fluoroalkylsilane, silane coupling agent, and organo An organic silicon compound such as polysiloxane, a coupling agent such as titanate, aluminate and zirconate, a low molecular or high molecular surfactant, and the like can be suitably used.

  Specific examples of the organosilicon compound include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and ethyl. Alkoxysilanes such as triethoxysilane, propyltriethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane and decyltriethoxysilane, trifluoropropyltrimethoxysilane, tridecafluorooctyltri Methoxysilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltriethoxysilane, heptadecafluorodecyltrie Fluoroalkylsilanes such as xylsilane and tridecafluorooctyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane Silane cups such as γ-methacryloyloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane Examples include ring agents, organopolysiloxanes such as polysiloxane, methylhydrogen polysiloxane, and modified polysiloxane.

  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.

  Examples of the low molecular surfactant include alkylbenzene sulfonate, dioctyl sulfone succinate, alkylamine acetate, alkyl fatty acid salt and the like. Examples of the polymeric surfactant include polyvinyl alcohol, polyacrylate, carboxymethylcellulose, acrylic acid-maleate copolymer, and olefin-maleate copolymer.

  Considering the adhesion effect of organic dyes, it is preferable to use an organic silicon compound such as alkoxysilane, fluoroalkylsilane, or polysiloxane, and various coupling agents such as silane, titanate, aluminate, and zirconate.

  The coating amount with the surface modifier is preferably 0.01 to 15.0% by weight in terms of C with respect to the surface modifier-coated inorganic particle powder. By treating the surface modifier in the range of 0.01 to 15.0% by weight, the organic dye can be effectively attached to the particle surface of the inorganic particle powder. More preferably, it is 0.02-12.5 weight%, More preferably, it is 0.03-10.0 weight%.

  As the organic coloring matter in the present invention, organic pigments generally used as colorants for paints, resin compositions and rubber compositions, dyes and dyeing lakes in which dyes are insolubilized with a precipitating agent can be used. Various organic dyes such as organic dyes, blue organic dyes, yellow organic dyes, green organic dyes, orange organic dyes, brown organic dyes and purple organic dyes can be used. Considering the light resistance of the obtained heat-shielding coating composition, it is preferable to use an organic pigment or a dyed lake.

  Among organic pigments in the present invention, red organic dyes include azo pigments such as brilliant carmine and permanent red, condensed azo pigments such as condensed azo red, diaminoanthraquinonyl red, quinacridone red, thioindigo red, and perylene red. In addition, condensed polycyclic pigments such as perinone red, isoindoline red, and diketopyrrolopyrrole red, and lysole rubin BCA can be used. As the blue organic dye, phthalocyanine pigments such as metal-free phthalocyanine blue, phthalocyanine blue and fast sky blue, condensed polycyclic pigments such as indanthrone blue and indigo blue, and alkali blue can be used. Examples of yellow organic dyes include monoazo pigments such as Hansa Yellow, disazo pigments such as benzidine yellow and permanent yellow, condensed azo pigments such as condensed azo yellow, and anthrapyrimidine yellow, isoindolinone yellow, isoindoline yellow, and quinophthalone yellow. These condensed polycyclic pigments can be used. As the green organic dye, a phthalocyanine pigment such as phthalocyanine green can be used. Examples of orange-based organic dyes include azo pigments such as permanent orange, resol fast orange, pyrazolone orange, and vulcanized orange, and condensed condensation such as quinacridone, perinone orange, isoindolinone orange, isoindoline orange, and diketopyrrolopyrrole orange. Cyclic pigments can be used. As the brown organic pigment, azo pigments such as permanent brown, para brown, benzimidazolone brown, and condensed polycyclic pigments such as thioindigo brown can be used. As the purple organic dye, azo pigments such as fast violet and condensed polycyclic pigments such as unsubstituted quinacridone, dioxazine violet and perylene violet can be used. The organic pigment used in the present invention is not limited to the pigments exemplified above.

  As the dye in the present invention, a dye such as a direct dye, an acid dye, a basic dye, a mordant dye, a naphthol dye, a sulfur dye, a vat dye, a disperse dye, a reactive dye, and an oil-soluble dye can be used.

  In addition, as the dyeing rake in the present invention, one obtained by insolubilizing the above dye with a precipitating agent can be used.

  Specifically, Amaranth, Erythrosin, New Coxin, Phloxin B, Rose Bengal, Acid Red, Tartrazine, Sunset Yellow FCF, Fast Green FCF, Brilliant Blue FCF, Indigo Carmine, Risol Rubin B, Rhodamine B, Rhodamine B Acetate , Rhodamine B stearate, Tetrachlorotetrabromofluorescein, Tetrabromofluorescein, Sudan III, Herringdon pink CN, First acid magenta, Eosin YS, Eosin YSK, Phloxine BK, Rose Bengal K, Dibrom fluorescein, Orange II, Jido Fluorescein, erythrosine yellow NA, fluorescein, uranin, uranin K, quinoline yellow WS, quinoline yellow SS, alizarin cyaning N, F quinizarin green SS, pyranine conch, light green SF yellow, indigo, patent blue NA, patent blue CA, carbanthrene blue, alphazurin FG, resorcin brown, arizurin purple SS, violamine R, medicinal scarlet, ponceau SR, Ponso R, Ponso SX, Oil Red XO, Fast Red S, Orange I, Orange SS, Polar Yellow 5G, Naphthol Yellow S, Yellow AB, Yellow OB, Metanil Yellow, Fast Light Yellow 3G, Naphthol Green B, Guinea Green B, Sudan Blue B, Alizurol Purple, Naphthol Blue Black, Alkaline Blue, Turquoise Blue, Alizarin, Basic Flavin, Auramin, Rhodamine 6G, Astrafloxin, Me Known dyes such as le violet, crystal violet, victoria blue BO, victoria blue B, basic cyanine, diamond green, malachite green, magenta, quinizarin, thioflavine, phthalein, and dyed rakes obtained by rake these with aluminum, barium, zirconium, etc. Can be used. The dyes and dye lakes used in the present invention are not limited to the dyes and dye lakes exemplified above.

  The organic pigment is used in combination of two or more colors such as the above-mentioned organic pigment, dye and dyeing lake in which the dye is insolubilized with a precipitating agent, and is not particularly limited as long as it is a combination from dark to black. Are, for example, blue and yellow combinations, blue and purple combinations, blue, red and yellow combinations, blue, red, green and purple combinations.

  The amount of the organic dye attached varies depending on the surface area of the inorganic particle powder, but is preferably 0.1 to 500 parts by weight, more preferably 0.5 to 400 parts by weight, even more preferably 100 parts by weight of the inorganic particle powder. Is 1 to 300 parts by weight. When the amount is less than 0.1 parts by weight, it is difficult to obtain a heat shielding composite particle powder having high infrared reflectivity, which is an object of the present invention. On the other hand, when it exceeds 500 parts by weight, it becomes difficult to form a highly uniform organic dye adhesion layer.

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

  The particle shape of the heat-shielding composite particle powder according to the present invention may be any shape such as spherical shape, granular shape, needle shape, spindle shape, rice grain shape, flake shape, plate shape, and irregular shape.

  The particle size of the heat-shielding composite particle powder according to the present invention may be appropriately selected according to the use, but preferably the average primary particle diameter is 0.001 to 1.0 μm, more preferably 0.003 to 3. 0.95 μm, still more preferably 0.005 to 0.9 μm. When the average primary particle diameter exceeds 1.0 μm, the particle size is too large, and the coloring power is lowered, which is not preferable.

  The geometric standard deviation value of the primary particle diameter of the primary particles of the heat-shielding composite particles according to the present invention is preferably 2.0 or less, more preferably 1.8 or less, still more preferably 1.5 or less. When it exceeds 2.0, the particle size distribution of the heat shielding composite particle powder is wide, and the dispersibility in the heat shielding coating composition is lowered, which is not preferable.

The BET specific surface area value of the heat-shielding composite particle powder according to the present invention is preferably 0.1 m ² / g or more. When the BET specific surface area value is less than 0.1 m ² / g, the particles become coarse particles and the coloring power decreases. In consideration of coloring power, the BET specific surface area value is more preferably 0.5 m ² / g or more, and still more preferably 1.0 m ² / g or more. In consideration of dispersibility and dispersion stability in the heat shielding coating composition, the upper limit is about 1000 m ² / g, preferably 800 m ² / g, more preferably 500 m ² / g.

  The coloring power of the heat-shielding composite particle powder according to the present invention is usually preferably 105% or more and more preferably 110% or more according to the evaluation method described later. If the coloring power is less than 105%, it is difficult to say that the coloring power is excellent.

  The infrared reflectivity of the heat-shielding composite particle powder according to the present invention is preferably such that the reflectance at a wavelength of 900 to 2100 nm of a coating film prepared according to JIS K 5101 is 40% or more, more preferably 45% or more. is there. When the reflectance at a wavelength of 900 to 2100 nm is less than 40%, it is difficult to say that the infrared reflectivity is excellent.

In the evaluation method to be described later, the light resistance of the heat shielding composite particle powder according to the present invention is generally ΔE ^* value, preferably 5.0 or less, more preferably 4.5 or less, and still more preferably 4. 0 or less. When the ΔE ^* value exceeds 5.0, it is difficult to say that the light resistance is excellent.

The lightness (L ^* value) of the heat-shielding composite particle powder according to the present invention is 45.0 or less, preferably 40.0 or less, more preferably 35.0 or less. When the lightness exceeds 45.0, it is difficult to say dark to black.

  The heat-shielding composite particle powder according to the present invention is a heat-shielding paint that is required to prevent an increase in the internal temperature due to solar radiation, such as coating of exterior surfaces and road surfaces of outdoor buildings, automobiles, ships, and tanks. It can be used as a colorant for the composition.

  The heat-shielding coating composition according to the present invention may be either solvent-based or water-based, and comprises a heat-shielding composite particle powder, a resin and a solvent, and if necessary, oils and fats, ultraviolet absorbers, antifoaming agents, drying accelerators, It is used by blending, diluting and dispersing a surfactant, curing accelerator, auxiliary agent and the like.

  Solvents used in solvent-based heat-shielding coating compositions include soybean oil, toluene, xylene, thinner, butyl acetate, methyl acetate, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, propyl, which are commonly used for solvent-based coatings. Glycol ether solvents such as cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate, aliphatic hydrocarbon solvents such as hexane, heptane, and octane, and alicyclic carbonization such as cyclohexane Hydrogen solvent, petroleum solvent such as mineral spirit, ketone solvent such as acetone and methyl ethyl ketone, alcohol solvent such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, aliphatic hydrocarbon, etc. as required Combined and can be used.

  Solvents for water-based heat-shielding coating compositions include water and / or alcohol solvents such as ethyl alcohol, propyl alcohol, and butyl alcohol that are commonly used for water-based paints, methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve. Glycol ether solvents such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and other oxyethylene or oxypropylene addition polymers, ethylene glycol, propylene glycol, 1,2,6-hexane A water-soluble organic solvent such as alkylene glycol such as triol, glycerin and 2-pyrrolidone can be mixed and used as necessary.

  Solvent-based heat-shielding coating composition resins include acrylic resins, alkyd resins, polyester resins, urethane resins, epoxy resins, modified epoxy resins, phenolic resins, which are commonly used in solvent-based coatings and oil-based printing inks. Melamine resin, amino resin, vinyl chloride resin, silicone resin, rosin resin such as gum rosin, lime rosin, maleic acid resin, polyamide resin, nitrocellulose, ethylene-vinyl acetate copolymer resin, rosin modified phenolic resin, rosin modified maleic acid resin A rosin-modified resin such as petroleum resin, fluororesin, or the like can be used. Examples of water-based heat-shielding paint resins include water-soluble acrylic resins, water-soluble styrene-maleic acid resins, water-soluble alkyd resins, water-soluble melamine resins, and water-soluble urethane emulsions commonly used in water-based paints and water-based inks. Resins, water-soluble epoxy resins, water-soluble polyester resins, and the like can be used.

In the evaluation method described below, the heat shielding coating composition according to the present invention preferably has a dispersion stability of ΔE ^* value of 1.2 or less, more preferably 1.0 or less. Further, the reflectance in the 900-2100 nm region of the coating film obtained using the heat-shielding coating composition is 40% or more, preferably 45% or more, and the light resistance is 5.0 or less in ΔE ^* value. Is more preferable, 4.5 or less is more preferable, and still more preferably 4.0 or less.

  By using the heat-shielding composite particle powder according to the present invention, the obtained heat-shielding coating composition has improved dispersion stability, and the coating film obtained using this has excellent infrared reflectivity and Light resistance can be obtained.

  Next, a method for producing the heat shielding composite particle powder according to the present invention will be described.

  The heat-shielding composite particle powder according to the first aspect of the present invention can be obtained by attaching an organic dye to the surface of inorganic particles that are core particles.

  The method for attaching the organic dye to the particle surface of the core particle is not particularly limited as long as it satisfies the target characteristics of the present invention, and can be obtained by, for example, a wet process, a mechanochemical process or the like.

  The heat-shielding composite particle powder according to the second aspect of the present invention is a mixture of inorganic particle powder and surface modifier, and the particle surface of the inorganic particle powder is coated with the surface modifier and then coated with the surface modifier. It can be obtained by mixing inorganic particle powder and organic pigment.

  The surface of the inorganic particle powder with the surface modifier is coated by mechanically mixing and stirring the inorganic particle powder and the surface modifier or a solution of the surface modifier. What is necessary is just to mix and stir mechanically, spraying a solution or a surface modifier.

  As equipment for mixing and stirring inorganic particle powder and surface modifier, and mixing and stirring organic pigment and inorganic particle powder whose surface is coated with surface modifier, shear force is applied to the powder layer. A device that can be added is preferable, and in particular, a device capable of simultaneously performing shearing, spatula and compression, for example, a wheel-type kneader, a ball-type kneader, a blade-type kneader, and a roll-type kneader can be used. A wheel-type 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.

  After the surface modifier is coated on the particle surface of the inorganic particle powder, an organic dye is added, mixed and stirred, and the organic dye is adhered to the surface modifier-coated inorganic particle surface. Two or more organic dyes may be added separately, or may be added in advance. Depending on the amount of organic dye, the organic dye may be added in small amounts over a period of 5 minutes to 12 hours, preferably 5 minutes to 10 hours, or 100 weights of inorganic particle powder. It is preferable to add 5 to 25 parts by weight of the organic dye in divided parts until a desired addition amount is obtained.

  After attaching the organic dye to the surface of the surface modifier-coated inorganic particles, drying or heat treatment may be further performed as necessary. In the case of performing drying or heat treatment, the heating temperature is usually preferably 40 to 80 ° C, more preferably 50 to 70 ° C, and the heating time is preferably 10 minutes to 6 hours, more preferably 30 minutes to 3 hours. .

  In addition, when alkoxysilane and fluoroalkylsilane are used as surface modifiers, the fluorosilane containing organosilane compound or fluoroalkylsilane finally produced from alkoxysilane is obtained through these steps. It is coated as a silane compound.

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The most important point in the present invention is that the heat-shielding composite particle powder having organic pigments of at least two colors attached to the particle surface of the inorganic particle powder has a sharp particle size distribution and high infrared reflectivity. This is the fact that the heat-shielding coating material can be obtained and is excellent in dispersibility and storage stability in the heat-shielding coating composition.

  As the reason why the heat-shielding composite particle powder according to the present invention is excellent in dispersibility in the heat-shielding coating composition and the heat-shielding coating composition is excellent in storage stability, the present inventor estimated as follows. Yes. That is, when two or more organic dyes are simply mixed, apparently, for example, black particles can be obtained, but the dispersibility and average primary particle size of each organic dye differ from one dye to another. For this reason, it is difficult to say that the obtained mixed particles have a very large variation in particle size and have uniform dispersibility and storage stability. On the other hand, the heat-shielding composite particle powder according to the present invention uniformly adheres the organic dye to the particle surface of the inorganic particle powder. Therefore, unlike the deep-colored particles obtained by simply mixing the organic dye, the behavior particles Since the dispersibility is almost uniform, the inventor presumes that the dispersibility and the storage stability are excellent.

  Regarding the reason why the heat-shielding composite particle powder according to the present invention has a sharp particle size distribution, the present inventor usually shows, for example, black particles when simply mixing two or more organic dyes. However, since the dispersibility and average primary particle size of each organic dye are different from each other, the resulting mixed particles have a very large variation in the particle size, but the heat-shielding composite particle powder according to the present invention In this case, the organic dye is uniformly attached to the particle surface of the inorganic particle powder having a relatively uniform particle size distribution. Unlike the dark colored particles obtained by simply mixing the organic dye, the particle size distribution is sharp. I think I was able to get it.

  Hereinafter, the present invention will be described in detail with reference to examples.

  The average particle size (primary particle size) of the particles was obtained by taking a photograph using a transmission electron microscope, measuring the particle size of 350 particles shown therein, and showing the average value.

  The particle size distribution of the particle size was indicated by a geometric standard deviation value obtained by the following method.

  That is, the value measured for the particle size of the particle shown in the above enlarged photograph is calculated from the measured value and the particle size is plotted on the horizontal axis on the lognormal probability paper according to the statistical method from the actual particle size and number of particles obtained. The diameter is plotted on the vertical axis, and the cumulative number of particles belonging to each of the predetermined particle diameter sections (under the integrated sieve) is plotted as a percentage. Then, from this graph, the particle diameter values corresponding to the number of particles of 50% and 84.13% are read, and the geometric standard deviation value = particle diameter under integrated fluid 84.13% / under integrated fluid 50%. The value was calculated according to the particle diameter (geometric mean diameter). The closer the geometric standard deviation value is to 1, the better the particle size distribution of the particle diameter.

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

  The coating amount of the surface modifier coated on the surface of the inorganic particle powder and the coating amount of the organic dye attached to the heat shielding composite particle powder are “Horiba Metal Carbon / Sulfur Analyzer EMIA-2200 Model”. The amount of carbon was determined by measuring the amount of carbon using the following procedure (manufactured by Horiba, Ltd.).

  The amount of carbon per unit weight of the inorganic particle powder that is the core particle is measured in advance, and then the amount of carbon of the heat shielding composite particle powder is measured. From the amount of change in the amount of carbon per unit weight, the organic dye The adhesion amount of was determined.

The saturation (c ^* value) of the inorganic particle powder and the lightness (L ^* value) of the heat-shielding composite particle powder were determined by using 0.5% of the sample and 0.75 ml of castor oil according to JIS K 5101 Hoover type Mahler method. Kneading with a formula Mahler to form a paste, adding 4.5 g of clear lacquer to this paste, kneading and coating, applying it on cast coated paper using a 150 μm applicator to produce a coated piece. C ^* value and L ^* value were measured using a spectrocolorimeter CM-3610d (manufactured by Minolta Co., Ltd.)

The hue (L ^* value, a ^* value, b ^* value, c ^* value) of the organic dye was determined in the same manner as above according to JIS K 5101 Hoover-type Mahler method. Kneaded with a Hoover type Mahler to form a paste, added 4.5 g of clear lacquer to this paste, kneaded, made into a paint and applied onto a cast coated paper using a 150 μm applicator to produce a coated piece, L ^* value, a ^* value, b ^* value and c ^* value were measured using “Spectrocolorimeter CM-3610d” (manufactured by Minolta Co., Ltd.).

The coloring power of the heat-shielding composite particle powder is as follows. First, each of the primary color enamel and the color-enameled enamel produced according to the method shown below is applied onto a cast coated paper using a 150 μm (6 mil) applicator to produce a coated piece. For the coated piece, the L ^* value was measured using a “spectral colorimeter CM-3610d” (manufactured by Minolta Co., Ltd.), and the difference was taken as the ΔL ^* value.

Next, as a standard sample of the heat-shielding composite particle powder, mixed particles obtained by simply mixing an organic dye and an inorganic particle powder at the same ratio as the heat-shielding composite particle powder are used. Colored enamel coated pieces were prepared, the L ^* value of each coated piece was measured, and the difference was taken as ΔLs ^* value.

The value calculated according to the following Equation 1 using DerutaLs ^* value of [Delta] L ^* value and the standard sample of the heat shielding composite particles obtained showed a tinting strength (%).

<Equation 1>
Tinting strength (%) = 100 + {( ΔLs * value -Delta L ^* value) × 10}

Production of primary color enamel:
3 g of the above sample powder, 16 g of amino alkyd resin and 10 g of thinner were mixed and added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads. 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 reflectance in the region of 900 to 2100 nm of the heat-shielding composite particle powder is obtained by reflecting the coated piece prepared for measuring the above-mentioned brightness using “Spectrophotometer UV-3100PC” (manufactured by Shimadzu Corporation). The rate (%) was measured.

The dispersion stability of the heat-shielding coating composition is obtained by applying each heat-shielding coating composition prepared according to the formulation described later on cast-coated paper using a 150 μm (6 mil) applicator to produce a coated piece. L ^* value, a ^* value, and b ^* value of the coated film, and each heat-shielding coating composition obtained by allowing the heat-shielding coating composition to stand at 25 ° C. for 1 week on cast coated paper The L ^* value, a ^* value, and b ^* value of the coating film obtained by coating and drying were measured using “Spectrocolorimeter CM-3610d” (manufactured by Minolta Co., Ltd.), and obtained according to the following formula 2. It was shown by ΔE ^* value.

<Equation 2>
ΔE ^* value = ((ΔL ^* value) ² + (Δa ^* value) ² + (Δb ^* value) ² ) ^1/2
ΔL ^* value: difference in L ^* value before and after leaving the sample to be compared Δa ^* value: difference in a ^* value before and after leaving the sample to be compared Δb ^* value: difference in b ^* value before and after leaving the sample to be compared

The lightness (L ^* value) of the coating film obtained using the heat-shielding coating composition is determined by applying each heat-shielding coating composition prepared according to the formulation described later on cast-coated paper to a thickness of 150 μm and drying. About the application | coating piece for a measurement obtained by forming a coating film, L ^* value was measured using "spectral colorimeter CM-3610d" (made by Minolta Co., Ltd.).

  The reflectance in the region of 900 to 2100 nm of the coating obtained using the heat shielding coating composition is a coating piece prepared for measuring the lightness obtained using the aforementioned heat shielding coating composition. The reflectance (%) was measured using “Spectrophotometer UV-3100PC” (manufactured by Shimadzu Corporation).

The light resistance of the coating film obtained using the heat-shielding coating composition was determined by subjecting each heat-shielding coating composition prepared according to the formulation described later to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G- 3141) was coated with a thickness of 150 μm and dried to form a coating film, and a half of the coating piece for measurement was covered with a metal foil, and “I Super UV Tester” (SUV-W13 (manufactured by Iwasaki Electric Co., Ltd.) )), The hue (L ^* value, a between the portion irradiated with ultraviolet rays and the portion irradiated with ultraviolet rays by covering with metal foil for 6 hours continuously after irradiation with ultraviolet rays at an irradiation intensity of 100 mW / cm ^{2. (*} Value, b ^* value) were measured respectively, and indicated by ΔE ^* value calculated according to the above equation 3 based on the measured value of the portion not irradiated with ultraviolet rays.

<Equation 3>
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

<Example 1-1: Production of heat-shielding composite particle powder>
Inorganic particle powder (type: titanium dioxide, particle shape: spindle shape, average particle size: 0.037 μm, geometric standard deviation value: 1.25, BET specific surface area value: 37.1 m ² / g, chroma c ^* value: 4.81) 5.0 kg is introduced into the edge runner “MPUV-2 type” (product name, manufactured by Matsumoto Casting Iron Works Co., Ltd.), and then methylhydrogenpolysiloxane (trade name: TSF484: GE Toshiba Silicone Co., Ltd.) 100 g) was added to the titanium oxide particle powder while operating the edge runner, and mixed and stirred for 20 minutes at a linear load of 588 N / cm.

Next, organic dye B-1 (type: pigment blue (phthalocyanine pigment), average primary particle size: 85 nm, BET specific surface area value: 83.6 m ² / g, L ^* value: 24.45, a ^* value: 6.03, b ^* value: -12.60, c ^* value: 13.97) 3.0 kg, organic dye R-1 (type: Pigment Red (diketopyrrolopyrrole pigment), average primary particle size: 128 nm , BET specific surface area value: 81.6 m ² / g, L ^* value: 37.97, a ^* value: 43.26, b ^* value: 23.20, c ^* value: 49.09) 0.75 kg and organic Dye Y-1 (Type: Pigment Yellow (azo pigment), average primary particle size: 416 nm, BET specific surface area value: 33.7 m ² / g, L ^* value: 80.04, a ^* value: 13.13, b ^* values: 89.65, ^{c *} value: 90.61) .25 kg of the mixed dye that had been mixed well in advance was added to 100 parts by weight of the inorganic particle powder while operating the edge runner, and 100 parts by weight of the mixed dye was added in 5 parts by 20 parts by weight. Mixing and stirring were performed for 120 minutes at a linear load of 588 N / cm, and the mixed dye was adhered onto the methylhydrogenpolysiloxane coating to obtain a heat-shielding composite particle powder. The stirring speed at this time was 22 rpm.

The obtained heat-shielding composite particle powder was a granular particle powder having an average primary particle size of 0.041 μm. The geometric standard deviation value of the particle diameter is 1.27, the BET specific surface area value is 4.8 m ² / g, the infrared reflectance is 49% or more in the region of 900 to 2100 nm, and the lightness (L ^* value) is 24. The coloring power was 124%, and the light resistance was 2.70 in ΔE ^* value. The coating amount of methyl hydrogen polysiloxane was 0.82% by weight in terms of Si, and the amount of attached organic dye was 30.0% by weight in terms of C.

  As a result of observing the electron micrograph, since almost no organic dye was observed, it was confirmed that almost all of the organic dye was adhered to the methylhydrogenpolysiloxane coating.

<Example 2-1: Production of heat shielding coating composition>
10 g of the heat shielding composite particle powder, amino alkyd resin and thinner were blended in the following proportions and added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads, and then mixed and dispersed for 90 minutes with a paint shaker to prepare a mill base.

3.8 parts by weight of heat shielding composite particle powder,
Amino alkyd resin 20.3 parts by weight,
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)
Thinner 12.7 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 heat shielding coating composition.

36.7 parts by weight of mill base,
Aminoalkyd resin 63.3 parts by weight.
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)

The dispersion stability of the obtained heat-shielding coating composition was 0.77 in terms of ΔE ^* value.

Next, the lightness L ^* value of the coating film obtained by applying and drying the heat-shielding coating composition is 25.3, the infrared reflectivity (reflectance in the region of 900 to 2100 nm) is 49% or more, and light resistance The ΔE ^* value was 2.93.

  A heat shielding composite particle powder and a heat shielding coating composition were prepared according to Examples 1-1 and 2-1. Various characteristics of each production condition and the obtained heat shielding composite particle powder and heat shielding coating composition are shown.

Inorganic particles 1-5:
An inorganic particle powder having the characteristics shown in Table 1 was prepared as the inorganic particle powder.

Organic dye:
An organic dye having various characteristics shown in Table 2 was prepared as the organic dye.

Examples 1-2 to 1-7, Comparative Examples 1-1 to 1-3:
Heat shielding composite particles in the same manner as in Example 1 except that the kind and amount of additive in the coating step with the surface modifier and the kind and amount of organic dye in the organic dye adhesion step were variously changed. A powder was obtained.

  In any of the examples and comparative examples, organic dyes that had been mixed well in advance were used. In Examples 2 and 5, the mixed dye was added in an amount of 20 parts by weight every 1 hour to 100 parts by weight of the inorganic particle powder over 5 hours. In Example 3, 50 parts by weight of the mixed dye was added in 25 parts by weight to 100 parts by weight of the inorganic particle powder in two portions. In Example 6, with respect to 100 parts by weight of the inorganic particle powder, 200 parts by weight of the mixed dye was added by 25 parts by weight in 8 portions.

  The production conditions at this time are shown in Table 3, and the characteristics of the obtained heat-shielding composite particle powder are shown in Table 4.

  As for the heat-shielding composite particle powder obtained in each of Examples 1-2 to 1-7, almost no organic dye was observed as a result of electron microscopic observation. It was confirmed that it adhered to the agent-coated inorganic particles.

<Heat shielding coating composition>
Examples 2-2 to 2-7, comparative examples 2-1 to 2-3:
A heat-shielding coating composition was obtained in the same manner as in Example 2-1 except that the kind of the heat-shielding composite particle powder was variously changed.

  Table 5 shows the production conditions and various properties of the obtained heat-shielding coating composition.

  The heat-shielding composite particle powder according to the present invention has a sharp particle size distribution and can provide a heat-shielding coating material having high infrared reflectivity, and can be dispersed and stored in a heat-shielding coating composition. Since it is excellent in stability, it is suitable as a colored particle powder for a heat-shielding coating composition that exhibits a dark color from black.

  Further, the heat-shielding coating composition according to the present invention is excellent in dispersibility and storage stability by using the above-mentioned heat-shielding composite particle powder, and thus is particularly suitable for applications that require long-term storage. Can be used.

Claims (3)

It is composed of a composite particle powder in which organic dyes of at least two colors are attached to the particle surface of the inorganic particle powder, and the organic dye is a red organic dye, blue organic dye, yellow organic dye, green organic dye, purple system organic dye, those selected from orange organic pigments and brown organic dye, the reflectance at a wavelength of 900~2100nm of a coating film of those said composite particles made according to JIS K 5101 is 40% or more Heat shielding composite particle powder characterized by Made from the composite particles the particle surfaces of the inorganic particles are at least two colors or more organic pigments adheres to the particle surface of the surface modifying agent coated inorganic particles with are covered with surface modifier, the organic pigment There are those selected from the organic red-based pigments, organic blue-based pigments, organic yellow-based pigments, green-based organic pigments, violet-based organic pigments, orange organic pigments and brown organic dye, a person said composite particles JIS K 5. A heat shielding composite particle powder, wherein the coating film prepared according to 5101 has a reflectance of 40% or more at a wavelength of 900 to 2100 nm. Claim 1 or the heat-shielding paint composition characterized by containing a heat shielding composite particles as described in 2.