WO2016140331A1 - Infrared reflective black pigment, coating material using the infrared reflective black pigment, and resin composition - Google Patents

Infrared reflective black pigment, coating material using the infrared reflective black pigment, and resin composition Download PDF

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Publication number
WO2016140331A1
WO2016140331A1 PCT/JP2016/056693 JP2016056693W WO2016140331A1 WO 2016140331 A1 WO2016140331 A1 WO 2016140331A1 JP 2016056693 W JP2016056693 W JP 2016056693W WO 2016140331 A1 WO2016140331 A1 WO 2016140331A1
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WO
WIPO (PCT)
Prior art keywords
black pigment
infrared reflective
reflective black
mol
infrared
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PCT/JP2016/056693
Other languages
French (fr)
Japanese (ja)
Inventor
伸介 丸山
耕三 渡部
一光 島根
藤井　泰彦
Original Assignee
戸田工業株式会社
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Application filed by 戸田工業株式会社 filed Critical 戸田工業株式会社
Priority to JP2017503722A priority Critical patent/JP6721867B2/en
Publication of WO2016140331A1 publication Critical patent/WO2016140331A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds

Definitions

  • the present invention relates to an infrared reflective black pigment that does not contain harmful elements and that can provide a heat-shielding paint having excellent infrared reflectivity.
  • roofs of outdoor buildings are often dark to black in order to make the dirt inconspicuous, and in the case of buildings and automobiles etc. whose exterior paint has a dark to black color, it is a pale color.
  • sunlight is more easily absorbed, and the indoor temperature tends to rise remarkably. It is not preferable that the temperature of the interior becomes high during transportation and storage of the article.
  • black pigments Although several black pigments have been developed as black pigments that do not contain harmful elements and have excellent infrared reflectivity as described above, these pigments are not necessarily sufficient, and further improvements are required. Yes.
  • Patent Documents 1 to 3 describe black pigments containing various elements, do not contain harmful elements, and have excellent infrared reflectivity. However, it is difficult to say that the reflectance in the infrared region wavelength of 1500 nm is sufficiently high. Patent Document 3 describes that a mixture of cupric oxide and an extender pigment or a white pigment is used as an infrared reflecting pigment, but it is difficult to say that the mixture has desired characteristics in the state of the mixture.
  • An object of the present invention is a composite oxide mainly composed of Cu, Zn and Si or a composite oxide mainly composed of Cu, Zn, Si and Al, which is black and has excellent infrared reflectivity. It is to provide an infrared reflective black pigment.
  • the infrared reflective black pigment of the present invention does not contain harmful elements such as Cr 6+ and Co.
  • the present invention is an infrared reflective black pigment made of a composite oxide containing Cu, Zn and Si, and the black pigment has a Cu content of 20 to 98.5 mol% with respect to all metal elements.
  • the present invention also relates to an infrared reflective black pigment made of a composite oxide containing Cu, Zn, Si, and Al, wherein the black pigment has a Cu content of 20 to 98 mol% with respect to all metal elements.
  • the Zn content is 1 to 70 mol% with respect to all metal elements
  • the Si content is 0.5 to 60 mol% with respect to all metal elements
  • the Al content is 0.00 with respect to all metal elements.
  • An infrared reflective black pigment characterized by being 5 to 60 mol% (Invention 2).
  • this invention is the black pigment of this invention 1 or 2 whose blackness (L * ) of the said black pigment is 29 or less (this invention 3).
  • the present invention is the infrared reflective black pigment according to any one of the present inventions 1 to 3, wherein the black pigment has a near infrared reflectance of 43% or more (Invention 4).
  • the present invention is the infrared reflective black pigment according to any one of the present inventions 1 to 4, wherein the acid resistance of the black pigment is 1000 ppm or less (Invention 5).
  • the surface of the infrared reflective black pigment is surface-treated with a compound containing one or more elements selected from Si, Al, Zr, Ti, Zn, and P, or an organic surface treatment agent. 5.
  • the infrared reflective black pigment according to any one of 1 to 5 (Invention 6).
  • present invention is a paint in which the infrared reflective black pigment according to any one of the present inventions 1 to 6 is blended (present invention 7).
  • the present invention is a resin composition colored using the infrared reflective black pigment according to any one of the present inventions 1 to 6 (present invention 8).
  • the infrared reflective black pigment according to the present invention is a complex oxide containing Cu, Zn and Si or a complex oxide containing Cu, Zn, Si and Al, and contains harmful elements such as Cr 6+ and Co. It is a safe black pigment that does not have an excellent infrared reflectivity and is excellent in acid resistance, and is therefore suitable as an infrared reflective black pigment.
  • the infrared reflective black pigment according to the present invention is a complex oxide containing Cu, Zn and Si or a complex oxide containing Cu, Zn, Si and Al, and does not contain expensive elements such as Co. Therefore, it is suitable as an inexpensive infrared reflective black pigment.
  • the infrared reflective black pigment according to the present invention is a complex oxide containing Cu, Zn and Si
  • the Cu content is 20 to 98.5 mol% and the Zn content with respect to all metal elements in the black pigment. Is 1 to 70 mol%
  • the Si content is 0.5 to 60 mol%
  • the total amount of Cu, Zn and Si is 100 mol%.
  • the Cu content is within the above range, the blackness and the near infrared reflectance can be increased.
  • the Zn content is within the above range, the amount of Cu dissolved by the acid resistance test can be suppressed.
  • the Si content is within the above range, the true specific gravity can be easily reduced to 6.5 g / cm 3 or less, which is advantageous for coating.
  • the preferable Cu content is 24 to 94 mol%, more preferably 28 to 93 mol%.
  • the preferable Zn content is 1 to 59 mol%, more preferably 3 to 58 mol%.
  • the preferable Si content is 1 to 59 mol%, more preferably 3 to 58 mol%.
  • the infrared reflective black pigment according to the present invention is a complex oxide containing Cu, Zn, Si, and Al
  • the Cu content is 20 to 98 mol% and the Zn content is based on the total metal elements in the black pigment. Is 1 to 70 mol%
  • the Si content is 0.5 to 60 mol%
  • the Al content is 0.5 to 60 mol%
  • the total amount of Cu, Zn, Si and Al is 100 mol%.
  • the Cu content is within the above range, the blackness and the near infrared reflectance can be increased.
  • the Zn content is within the above range, the amount of Cu dissolved by the acid resistance test can be suppressed.
  • the true specific gravity can be easily reduced to 6.5 g / cm 3 or less, which is advantageous for coating.
  • the preferable Cu content is 24 to 96 mol%, more preferably 28 to 95 mol%.
  • the preferable Zn content is 1 to 59 mol%, more preferably 3 to 57 mol%.
  • the preferable Si content is 1 to 59 mol%, more preferably 2 to 58 mol%.
  • the preferable Al content is 1 to 59 mol%, more preferably 2 to 58 mol%.
  • the infrared reflective black pigment according to the present invention is obtained by firing a mixture of various raw materials, and a desired effect cannot be obtained only by mixing various metal element compounds.
  • the infrared reflective black pigment according to the present invention does not need to be a single phase by the identification of the constituent phase by X-ray diffraction as long as it is a composite oxide obtained by firing a raw material mixture, and is formed from a plurality of constituent phases. It may be.
  • the infrared reflective black pigment according to the present invention may inevitably contain impurities derived from various raw materials.
  • the average particle diameter of the infrared reflective black pigment according to the present invention is preferably 0.02 to 5.0 ⁇ m.
  • the average particle diameter of the black pigment exceeds 5.0 ⁇ m, the particle size is too large, and the coloring power is reduced.
  • the average particle size is less than 0.02 ⁇ m, dispersion in the vehicle may be difficult.
  • a more preferable average particle diameter is 0.025 to 4.0 ⁇ m, and still more preferably 0.04 to 2.0 ⁇ m.
  • the BET specific surface area of the infrared reflective black pigment according to the present invention is preferably 1 to 100 m 2 / g.
  • the BET specific surface area is less than 1 m 2 / g, the particles are coarse or the particles are sintered between the particles and the coloring power is reduced.
  • the BET specific surface area exceeds 100 m 2 / g, the dispersibility is lowered because aggregation tends to occur due to an increase in intermolecular force due to finer particles.
  • a more preferred BET specific surface area is 1.5 to 75 m 2 / g, and even more preferably 1.8 to 65 m 2 / g.
  • the blackness of the infrared reflective black pigment according to the present invention is represented by lightness (L * ), it is preferably 29 or less. When the lightness (L * ) is outside the above range, it is difficult to say that it is a black pigment.
  • the lightness (L * ) is preferably 28 or less, more preferably 26 or less.
  • the a * of the infrared reflective black pigment according to the present invention is preferably -2 to +10. When a * is outside the above range, it is difficult to say a black pigment. More preferably, it is -1 to +5.
  • the b * of the infrared reflective black pigment according to the present invention is preferably ⁇ 5 to +10.
  • b * is outside the above range, it is difficult to say a black pigment. More preferably, it is ⁇ 4 to +5.
  • the lightness (L * ), a * , and b * of these infrared reflective black pigments can be adjusted to be in the above range depending on the composition of the black pigment, firing conditions, and pulverization conditions.
  • the near infrared reflectance of the infrared reflective black pigment according to the present invention is preferably 43% or more when the lacquer color sample coating film is measured according to JIS K5602. If the near infrared reflectance is less than 43%, it cannot be said that the near infrared reflectance is sufficiently high. A more preferable near infrared reflectance is 45% or more, and even more preferably 46% or more.
  • the near-infrared reflectance can be adjusted to be in the above range depending on the composition of the black pigment, the firing conditions, and the pulverization conditions.
  • the true specific gravity of the infrared reflective black pigment according to the present invention is preferably 4.5 to 6.3 g / cm 3 .
  • the more preferable true specific gravity is 4.6 to 6.2 g / cm 3 , and still more preferably 4.7 to 6.1 g / cm 3 .
  • the true specific gravity can be adjusted to be in the above range depending on the composition of the black pigment.
  • the acid resistance of the infrared reflective black pigment according to the present invention is preferably 1000 ppm or less with respect to the amount of dissolved Cu measured by the evaluation method described later. When the amount of Cu dissolved exceeds 1000 ppm, Cu is easily dissolved and the pigment is altered. A more preferable Cu dissolution amount is 800 ppm or less, and even more preferably 500 ppm or less.
  • the acid resistance can be adjusted to be in the above range depending on the composition of the black pigment, the firing conditions and the grinding conditions.
  • the shape of the particles of the infrared-reflective black pigment according to the present invention is not limited to a specific shape, and is spherical, granular, octahedral, hexahedral, polyhedral, etc., acicular, spindle, rice, etc. Needle-like particles and plate-like particles can be used. Considering the dispersibility of the resulting black pigment, spherical particles and granular particles are preferred.
  • the infrared reflective black pigment according to the present invention covers the surface of an infrared reflective black pigment using one or more compounds selected from Si, Al, Zr, Ti, Zn, and P or an organic surface treatment agent. Can do. The effect of improving dispersibility can be easily obtained by the surface coating.
  • One or more compounds selected from Si, Al, Zr, Ti, Zn, and P include aluminum compounds such as aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride, and aluminum nitrate, and aluminates such as sodium aluminate. Examples include alkali salts. Examples of the silicon compound include No. 3 water glass, sodium orthosilicate, sodium metasilicate, and the like.
  • zirconium salts such as zirconium acetate, zirconium sulfate, zirconium chloride, and zirconium nitrate can be used.
  • titanium salts such as titanium acetate, titanium sulfate, titanium chloride, and titanium nitrate
  • zinc compound zinc salts such as zinc acetate, zinc sulfate, zinc chloride, and zinc nitrate can be used.
  • phosphorus compound phosphates such as sodium hydrogen phosphate, sodium ammonium hydrogen phosphate, potassium phosphate, sodium polyphosphate, sodium hexametaphosphate and the like can be used.
  • Organic surface treatment agents include stearic acid or salts thereof, rosin, alkoxysilanes, fluoroalkylsilanes, silane coupling agents, organosilicon compounds such as organopolysiloxanes, titanates, aluminates, and zirconates. Examples thereof include a ring agent, a low molecular or high molecular surfactant, and a phosphoric acid compound.
  • organosilicon compound examples 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, heptadecafluorodecyltri Fluoroalkylsilanes such as toxisilane and tridecafluorooctyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxy
  • 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, bis (dioctylpyrophosphate) ethylene titanate, and the like.
  • aluminate coupling agent examples include acetoalkoxyaluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate and the like.
  • zirconate coupling agent examples 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.
  • phosphoric acid compounds include organic phosphorus compounds such as phosphoric acid esters, phosphorous acid esters, acidic phosphoric acid esters, and phosphonic acids.
  • the surface treatment is usually performed in the range of 0.1 to 10% by weight, preferably 0.3 to 8.0% by weight with respect to the black pigment, although it depends on the type of treatment agent used.
  • the infrared reflective black pigment made of the composite oxide according to the present invention can be obtained by mixing and firing various raw materials.
  • the starting material oxides, hydroxides, carbonates, nitrates, sulfates and the like of the respective metal elements can be used.
  • the mixing of the starting materials is not particularly limited as long as it can be uniformly mixed, and may be wet mixing or dry mixing. Also, wet synthesis may be used.
  • the equipment used for mixing and stirring the starting materials is preferably an apparatus that can apply a shearing force to the powder layer, and an apparatus that can simultaneously perform shearing, spatula and compression, for example, a wheel-type kneader, It is preferable to use a ball-type kneader, a blade-type kneader, or a roll-type kneader. 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.
  • As the ball kneader there is a vibration mill.
  • Examples of the blade type kneader include a Henschel mixer, a planetary mixer, and a nauta mixer.
  • As the roll type kneader there is an extruder.
  • the heating and firing temperature is preferably 500 to 1100 ° C, more preferably 550 to 1050 ° C.
  • the heating atmosphere is air.
  • the powder after heating may be washed and pulverized according to a conventional method.
  • the particle surface of the infrared reflective black pigment may be coated with one or more compounds selected from Si, Al, Zr, Ti, Zn, and P.
  • the surface treatment method may be performed according to a conventional method such as a wet method or a dry method.
  • a wet method one or two or more soluble compounds selected from Si, Al, and Zr are added to and mixed with a slurry of a wet-dispersed infrared reflective black pigment while adjusting the pH with an acid or an alkali.
  • the dry method is a method in which an infrared reflective black pigment is coated with one or more coupling agents selected from Si, Al and Zr in an apparatus such as a Henschel mixer.
  • an apparatus that can apply a shearing force to the powder layer is preferable, and an apparatus that can simultaneously perform shearing, spatula and compression, for example, It is preferable to use a wheel-type kneader, a ball-type kneader, a blade-type kneader, or a roll-type kneader.
  • 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.
  • As the ball kneader there is a vibration mill.
  • Examples of the blade type kneader include a Henschel mixer, a planetary mixer, and a nauta mixer.
  • As the roll type kneader there is an extruder.
  • the blending ratio of the infrared reflective black 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, taking into account the handleability of the paint. For example, it is preferably 1.0 to 100 parts by weight.
  • paint constituting base material resin, solvent, and if necessary, fats and oils, antifoaming agent, extender pigment, drying accelerator, surfactant, curing accelerator, 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, fluorine resins, etc. be able to.
  • water-soluble acrylic resins 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 in water-based paints and water-based inks Resins, water-soluble polyester resins, water-soluble fluororesins, 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 such as ethyl acetate, butyl acetate, and amyl acetate
  • 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
  • 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.
  • 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
  • diethylene glycol diethylene glycol
  • Oxyethylene or oxypropylene addition polymer 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.
  • boil oils obtained by processing dry oils such as sesame oil, cutting 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.
  • the paint containing the infrared reflective black pigment of the present invention is excellent in dispersibility.
  • the redispersibility according to the evaluation method described in the examples is excellent, it is evaluated that the paint stabilization is easy (uniformly dispersed).
  • the blending ratio of the infrared reflective black 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 the handling property of the resin composition is taken into consideration.
  • the amount is preferably 0.05 to 150 parts by weight, more preferably 0.1 to 100 parts by weight.
  • an additive such as a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, and various stabilizers, if necessary, together with an infrared reflective black pigment and a known thermoplastic resin. Is blended.
  • the resin examples include polyolefins such as polyethylene, polypropylene, polybutene, 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 resin, phenol resin, epoxy resin, polyester resin, Silicone resin, rosin ester, rosin, natural rubber, synthetic rubber and the like can be used.
  • polyolefins such as polyethylene, polypropylene, polybutene, polyisobutylene, polyvinyl chloride,
  • the amount of the additive may be 50% by weight or less based on the sum of the infrared reflective black 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 prepared by mixing a resin raw material and an infrared reflective black pigment in advance, and then applying a strong shearing action under heating using a kneader or an extruder to produce an infrared reflective black pigment.
  • the aggregate is broken and the infrared reflective black pigment is uniformly dispersed in the resin composition, and then molded into a shape suitable for the purpose.
  • the resin composition according to the present invention can also be obtained via a master batch pellet.
  • the master batch pellet in the present invention requires a binder resin as a constituent substrate of the paint and the resin composition and the infrared reflective black 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.
  • 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. Kneaded with a well-known single-screw kneading extruder or twin-s
  • the supply of the binder resin and the infrared reflective black pigment to the kneader may be quantitatively supplied at a predetermined ratio or a mixture of both.
  • the master batch pellet in 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.
  • the average major axis is less than 1 mm, the workability at the time of producing the pellet is poor, which is not preferable.
  • 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.
  • the shape can be various, and can be indefinite and spherical, cylindrical, flakes, and the like.
  • the same resin as the resin for resin composition can be used.
  • 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 infrared reflective black pigment blended in the master batch pellet is 1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the binder resin. .
  • 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 and mixing of the infrared reflective black pigment.
  • the amount exceeds 200 parts by weight since there is little binder resin for the infrared reflective black pigment, good dispersion and mixing of the infrared reflective black pigment is difficult, and the resin composition can be changed by a slight change in the addition amount of the master batch pellet. Since the content of the infrared-reflective black pigment blended in the product greatly changes, it is difficult to prepare the desired content, which is not preferable. Also, mechanical wear is severe and not suitable.
  • a typical embodiment of the present invention is as follows.
  • the average particle diameter of the particles was measured by an air permeation method (Fischer method).
  • the specific surface area is indicated by a value measured by the BET method.
  • the true specific gravity indicates a value measured with a “dry automatic densimeter Accupick II-1340” (manufactured by Micromeritics).
  • the content of the metal element of the infrared reflective black pigment was measured using a “fluorescence X-ray analyzer 3063M type” (manufactured by Rigaku Denki Kogyo Co., Ltd.) according to “General X-ray fluorescence analysis rules” of JIS K0119.
  • the hue (L * value, a * value, b * value) of the infrared reflective black pigment was prepared by mixing 0.5 g of a sample and 0.5 ml of castor oil with a Hoover type Mahler to form a paste. .5 g was added, kneaded and converted into a paint, and an application piece (coating thickness: about 30 ⁇ m) applied on cast-coated paper using a 150 ⁇ m (6 mil) applicator was produced. The coating piece was measured using a “color difference meter CR-300” (manufactured by Konica Minolta Sensing Co., Ltd.), and the color index (L * value, a * value, b * value) according to JIS Z 8729. ).
  • the reflectance of the wavelength of the black pigment for infrared reflection in the visible light region and the near infrared region is determined by “spectrophotometer U-4100” (Hitachi High-Technologies Corporation) for the coating piece prepared for measuring the above hue. ) And the reflectance (%) at a wavelength of 250 to 2500 nm was measured. The reflectance in the wavelength range of 780 to 2500 nm was calculated as the near infrared reflectance according to JIS K 5602.
  • the acid resistance of the infrared reflective black pigment was evaluated in accordance with JIS K5101-8 “Pigment Test Method Part 8: Chemical Resistance”. Add 2 g of pigment and 20 ml of 5% sulfuric acid to the test tube, seal and shake well. Let stand for 15 minutes, and after resting, seal again and shake and leave for 30 minutes. After allowing to stand, the amount of dissolved Cu was measured for the solution after separation by filtration using “ICP emission spectroscopic analyzer iCAP-6500DUO” (manufactured by Thermo Electron Co., Ltd.).
  • the dispersibility of the paint containing the infrared reflective black pigment was evaluated in the following manner.
  • mayonnaise bottle internal volume 140 ml
  • 90 g of glass beads, 10 g of black pigment, 16.0 g of amino alkyd resin (clear), 6.0 g of solvent were blended and dispersed for 40 minutes with a paint conditioner.
  • 50 g of (clear) it was dispersed with a paint conditioner for 5 minutes and separated from glass beads. Thereafter, the mixture was allowed to stand for 24 hours to precipitate the black pigment.
  • the redispersibility when the paint containing the precipitate was stirred with a stirrer was observed to evaluate the ease and difficulty of stabilizing the paint.
  • the easy stabilization of the paint is that the pigment is uniformly dispersed in the paint, and the difficulty is that the pigment is settled and separated (color separation).
  • Example 1 Various raw material compounds were weighed and mixed so as to have the contents shown in Table 1 below, and baked at 900 ° C. for 1 hour using an electric furnace. The fired product was pulverized to obtain an infrared reflective black pigment. As a result of X-ray diffraction, the obtained infrared reflective black pigment is a composite oxide containing Cu, Zn and Si, and is a black pigment having a BET specific surface area of 4.0 m 2 / g and an average particle diameter of 1.5 ⁇ m. It was.
  • This pigment was coated with a lacquer color to prepare a color sample sample, and the reflectance was measured in the wavelength range of 250 nm to 2500 nm using a U-4100 Hitachi spectrophotometer. As a result, the near infrared reflectance at a wavelength of 780 to 2500 nm was 60.3%.
  • Example 2 Various raw materials were dissolved in an acidic aqueous solution, neutralized with an aqueous alkaline solution, a precursor was synthesized by a wet method, and then a black pigment was obtained in the same manner as in Example 1 except that the precursor was fired at 800 ° C. for 2 hours. .
  • Examples 3 and 4 A black pigment was obtained in the same manner as in Example 1 except that the raw material composition and the firing temperature were changed.
  • Example 5 A black pigment was obtained in the same manner as in Example 1 except that the raw material composition and the firing temperature were changed. Next, the obtained black pigment was wet-dispersed in water, adjusted to pH 7 with hydrochloric acid and sodium hydroxide and maintained for 1 hour while dropping 1.0 wt% of water glass into a slurry of black pigment kept at 70 ° C. Thereafter, it was washed with water, dehydrated, dried and pulverized.
  • Examples 6, 7, and 8 A black pigment was obtained in the same manner as in Example 1 except that the raw material composition and the firing temperature were variously changed and various surface treatment agents were dry-mixed.
  • Comparative Examples 1 to 3 In Comparative Example 1, copper oxide NB manufactured by Nisshin Chemco was used. Comparative Example 2 is a mixture of copper oxide NB and ZnCO 3 of Comparative Example 1, Comparative Example 3 is a mixture of copper oxide NB, ZnCO 3 and SiO 2 of Comparative Example 1, and Comparative Example 4 is a comparative example. 1 is a mixture of copper oxide NB, ZnCO 3 , SiO 2 and Al (OH) 3 .
  • Table 1 shows the production conditions of the infrared reflective black pigment
  • Table 2 shows the properties of the obtained infrared reflective black pigment
  • Table 3 shows the properties of the paint and the coating film.
  • the infrared reflective pigment according to the present invention has an excellent near infrared reflectance when the base such as cast-coated paper is white.
  • the infrared reflective black pigment according to the present invention is suitable as a safe infrared reflective black pigment because it is excellent in infrared reflectivity and does not contain harmful elements such as Cr 6+ and Co.
  • the resin composition containing the infrared reflective black pigment according to the present invention is excellent in infrared reflectivity, the resin composition is used in the following applications by making it into a sheet or film by a known method. be able to.
  • the sheet obtained from the resin composition containing the infrared-reflective black pigment according to the present invention is black, if it is used for an agricultural multi-sheet, it is possible to prevent the generation and growth of weeds. Since it is excellent in reflectivity, it is possible to suppress an increase in the temperature of the ground, and it can be suitably used as a black agricultural multi-sheet.
  • seat obtained from the resin composition containing the infrared reflective black pigment which concerns on this invention can be used suitably for the back seat
  • the front and back surfaces of a plurality of solar cell elements are protected by a cover material.
  • the back sheet that protects the back surface of the solar cell element is preferably a back sheet having high reflectivity in terms of power conversion efficiency and black in terms of design.
  • the power generation efficiency decreases as the temperature of the solar cell element increases.
  • seat obtained from the resin composition containing the infrared reflective black pigment which concerns on this invention is fully equipped with the characteristic required as a solar cell backsheet, and is preferable as a solar cell backsheet.

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Abstract

The invention provides a black pigment free of harmful elements such as Cr6+ wherein the infrared reflective black pigment has excellent acid resistance together with excellent infrared reflectivity. A black pigment comprising of a composite oxide containing Cu and Zn and Si or a composite oxide containing Cu and Zn and Al and Si wherein the infrared reflective black pigment has a blackness (L*) of the black pigment of 29 or lower and near infrared reflectance of 43% or higher, and a coating material and resin composition using the infrared reflective black pigment.

Description

赤外線反射性黒色顔料、該赤外線反射性黒色顔料を用いた塗料及び樹脂組成物Infrared reflective black pigment, paint and resin composition using the infrared reflective black pigment
　本発明は、有害な元素を含有せず、しかも、優れた赤外線反射性を有する熱遮蔽性塗料を得ることができる赤外線反射性黒色顔料に関するものである。 The present invention relates to an infrared reflective black pigment that does not contain harmful elements and that can provide a heat-shielding paint having excellent infrared reflectivity.
　屋外で用いられている道路、建築物、備蓄タンク、自動車、船舶等は、太陽の日射によって内部温度が上昇するため、建築物及び自動車等の外観塗装を白色から淡色にすることで太陽光を反射させ、ある程度熱遮蔽効果を高めることが行われている。 Roads, buildings, stockpile tanks, automobiles, ships, etc. used outdoors increase the internal temperature due to solar radiation, so sunlight is reduced by changing the exterior paint of buildings and automobiles from white to light. It is reflected to increase the heat shielding effect to some extent.
　しかしながら、屋外建築物の屋根などは、汚れを目立たなくするために、濃彩色から黒色を呈している場合が多く、外観塗装が濃彩色から黒色を有する建築物及び自動車等の場合には、淡色から白色の外観塗装を有する建築物及び自動車等に比べて太陽光を吸収しやすく、屋内の温度が著しく上昇する傾向にある。物品の輸送、保存に当たって、内部が高温になることは好ましいものではない。 However, roofs of outdoor buildings are often dark to black in order to make the dirt inconspicuous, and in the case of buildings and automobiles etc. whose exterior paint has a dark to black color, it is a pale color. As compared with buildings and automobiles having a white appearance coating, sunlight is more easily absorbed, and the indoor temperature tends to rise remarkably. It is not preferable that the temperature of the interior becomes high during transportation and storage of the article.
　そこで、地球温暖化防止のためのエネルギー節約という観点からも、濃彩色から黒色の外観を有する建築物及び自動車等の内部温度の上昇を抑制することが強く望まれている。 Therefore, from the viewpoint of energy saving to prevent global warming, it is strongly desired to suppress the rise in internal temperature of buildings and automobiles having a dark to black appearance.
　従来より、濃彩色から黒色の外観塗装を有する建築物及び自動車等の内部温度の上昇を低減するために、熱遮蔽性黒色塗料が知られている（例えば、特許文献１～３参照）。 Conventionally, heat-shielding black paints are known in order to reduce the rise in internal temperature of buildings and automobiles having dark to black exterior paint (see, for example, Patent Documents 1 to 3).
特開２００７－１９７５７０号公報JP 2007-197570 A 特開２０１０－６５２０１号公報JP 2010-65201 A 特開２０１０－１５０３５４号公報JP 2010-150354 A
　上記の通り有害な元素を含有せず、しかも優れた赤外線反射性を有する黒色顔料としていくつかの黒色顔料が開発されているものの、これら顔料は必ずしも十分とは言えず、さらなる改良が求められている。 Although several black pigments have been developed as black pigments that do not contain harmful elements and have excellent infrared reflectivity as described above, these pigments are not necessarily sufficient, and further improvements are required. Yes.
　特許文献１～３には、各種元素を含有する黒色顔料が記載されており、有害な元素を含有せず、しかも優れた赤外線反射性を有する。しかしながら、赤外線領域波長１５００ｎｍの反射率が十分に高いとは言い難いものである。特許文献３には、酸化第二銅と体質顔料又は白色顔料との混合物を赤外線反射顔料として用いることが記載されているが、混合物の状態では所望の特性を有するとは言い難いものである。 Patent Documents 1 to 3 describe black pigments containing various elements, do not contain harmful elements, and have excellent infrared reflectivity. However, it is difficult to say that the reflectance in the infrared region wavelength of 1500 nm is sufficiently high. Patent Document 3 describes that a mixture of cupric oxide and an extender pigment or a white pigment is used as an infrared reflecting pigment, but it is difficult to say that the mixture has desired characteristics in the state of the mixture.
　本発明の目的は、Ｃｕ、Ｚｎ及びＳｉを主成分とした複合酸化物又はＣｕ、Ｚｎ、Ｓｉ及びＡｌを主成分とした複合酸化物であって、黒色であって、優れた赤外線反射性を有する赤外線反射性黒色顔料を提供することである。本発明の赤外線反射性黒色顔料はＣｒ６＋やＣｏなどの有害な元素を含有しない。 An object of the present invention is a composite oxide mainly composed of Cu, Zn and Si or a composite oxide mainly composed of Cu, Zn, Si and Al, which is black and has excellent infrared reflectivity. It is to provide an infrared reflective black pigment. The infrared reflective black pigment of the present invention does not contain harmful elements such as Cr 6+ and Co.
　前記目的は、次の通りの本発明によって達成できる。 The above object can be achieved by the present invention as follows.
　即ち、本発明は、ＣｕとＺｎとＳｉとを含有する複合酸化物からなる赤外線反射性黒色顔料であって、該黒色顔料はＣｕ含有量が全金属元素に対して２０～９８．５ｍｏｌ％であり、Ｚｎ含有量が全金属元素に対して１～７０ｍｏｌ％であり、Ｓｉ含有量が全金属元素に対して０．５～６０ｍｏｌ％であることを特徴とする赤外線反射性黒色顔料である（本発明１）。 That is, the present invention is an infrared reflective black pigment made of a composite oxide containing Cu, Zn and Si, and the black pigment has a Cu content of 20 to 98.5 mol% with respect to all metal elements. And an infrared reflective black pigment characterized in that the Zn content is 1 to 70 mol% with respect to all metal elements and the Si content is 0.5 to 60 mol% with respect to all metal elements ( Invention 1).
　また、本発明は、ＣｕとＺｎとＳｉとＡｌとを含有する複合酸化物からなる赤外線反射性黒色顔料であって、該黒色顔料はＣｕ含有量が全金属元素に対して２０～９８ｍｏｌ％であり、Ｚｎ含有量が全金属元素に対して１～７０ｍｏｌ％であり、Ｓｉ含有量が全金属元素に対して０．５～６０ｍｏｌ％であり、Ａｌ含有量が全金属元素に対して０．５～６０ｍｏｌ％であることを特徴とする赤外線反射性黒色顔料である（本発明２）。 The present invention also relates to an infrared reflective black pigment made of a composite oxide containing Cu, Zn, Si, and Al, wherein the black pigment has a Cu content of 20 to 98 mol% with respect to all metal elements. The Zn content is 1 to 70 mol% with respect to all metal elements, the Si content is 0.5 to 60 mol% with respect to all metal elements, and the Al content is 0.00 with respect to all metal elements. An infrared reflective black pigment characterized by being 5 to 60 mol% (Invention 2).
　また、本発明は、前記黒色顔料の黒色度（Ｌ＊）が２９以下である本発明１又は２記載の黒色顔料である（本発明３）。 Moreover, this invention is the black pigment of this invention 1 or 2 whose blackness (L * ) of the said black pigment is 29 or less (this invention 3).
　また、本発明は、前記黒色顔料の近赤外反射率が４３％以上である本発明１～３のいずれかに記載の赤外線反射性黒色顔料である（本発明４）。 Further, the present invention is the infrared reflective black pigment according to any one of the present inventions 1 to 3, wherein the black pigment has a near infrared reflectance of 43% or more (Invention 4).
　また、本発明は、前記黒色顔料の耐酸性が１０００ｐｐｍ以下である本発明１～４のいずれかに記載の赤外線反射性黒色顔料である（本発明５）。 Further, the present invention is the infrared reflective black pigment according to any one of the present inventions 1 to 4, wherein the acid resistance of the black pigment is 1000 ppm or less (Invention 5).
　また、本発明は、赤外線反射性黒色顔料の表面を、Ｓｉ、Ａｌ、Ｚｒ、Ｔｉ、Ｚｎ、Ｐから選ばれる一種以上の元素を含む化合物又は有機系表面処理剤で表面処理されている本発明１～５のいずれかに記載の赤外線反射性黒色顔料である（本発明６）。 In the present invention, the surface of the infrared reflective black pigment is surface-treated with a compound containing one or more elements selected from Si, Al, Zr, Ti, Zn, and P, or an organic surface treatment agent. 5. The infrared reflective black pigment according to any one of 1 to 5 (Invention 6).
　また、本発明は、本発明１～６のいずれかに記載の赤外線反射性黒色顔料を配合した塗料である（本発明７）。 Further, the present invention is a paint in which the infrared reflective black pigment according to any one of the present inventions 1 to 6 is blended (present invention 7).
　また、本発明は、本発明１～６のいずれかに記載の赤外線反射性黒色顔料を用いて着色した樹脂組成物である（本発明８）。 In addition, the present invention is a resin composition colored using the infrared reflective black pigment according to any one of the present inventions 1 to 6 (present invention 8).
　本発明に係る赤外線反射性黒色顔料は、Ｃｕ、Ｚｎ及びＳｉを含有する複合酸化物又はＣｕ、Ｚｎ、Ｓｉ及びＡｌを含有する複合酸化物であり、Ｃｒ６＋やＣｏなどの有害な元素を含有しない安全な黒色顔料であって、優れた赤外線反射性を有するとともに、耐酸性にも優れるので赤外線反射性黒色顔料として好適である。 The infrared reflective black pigment according to the present invention is a complex oxide containing Cu, Zn and Si or a complex oxide containing Cu, Zn, Si and Al, and contains harmful elements such as Cr 6+ and Co. It is a safe black pigment that does not have an excellent infrared reflectivity and is excellent in acid resistance, and is therefore suitable as an infrared reflective black pigment.
　本発明の構成をより詳しく説明すれば次の通りである。 The configuration of the present invention will be described in more detail as follows.
　先ず、本発明に係る赤外線反射性黒色顔料について述べる。 First, the infrared reflective black pigment according to the present invention will be described.
　また、本発明に係る赤外線反射性黒色顔料は、Ｃｕ、Ｚｎ及びＳｉを含有する複合酸化物又はＣｕ、Ｚｎ、Ｓｉ及びＡｌを含有する複合酸化物であり、Ｃｏなどの高価な元素を含有しないので、安価な赤外線反射性黒色顔料として好適である。 The infrared reflective black pigment according to the present invention is a complex oxide containing Cu, Zn and Si or a complex oxide containing Cu, Zn, Si and Al, and does not contain expensive elements such as Co. Therefore, it is suitable as an inexpensive infrared reflective black pigment.
　本発明に係る赤外線反射性黒色顔料がＣｕ、Ｚｎ及びＳｉを含有する複合酸化物である場合、黒色顔料中の全金属元素に対して、Ｃｕ含有量は２０～９８．５ｍｏｌ％、Ｚｎ含有量は１～７０ｍｏｌ％であり、Ｓｉ含有量は０．５～６０ｍｏｌ％であり、Ｃｕ、Ｚｎ及びＳｉの合計量が１００ｍｏｌ％となる。Ｃｕ含有量が前記範囲内であることによって、黒色度及び近赤外反射率を高くすることができる。また、Ｚｎ含有量が前記範囲内であることによって、耐酸性試験によるＣｕ溶解量を抑制することができる。また、Ｓｉ含有量が前記範囲内であることによって、容易に真比重を６．５ｇ／ｃｍ３以下とすることができ塗料化に有利である。好ましいＣｕ含有量は２４～９４ｍｏｌ％であり、より好ましくは２８～９３ｍｏｌ％である。また、好ましいＺｎ含有量は１～５９ｍｏｌ％であり、より好ましくは３～５８ｍｏｌ％である。また、好ましいＳｉ含有量は１～５９ｍｏｌ％であり、より好ましくは３～５８ｍｏｌ％である。 When the infrared reflective black pigment according to the present invention is a complex oxide containing Cu, Zn and Si, the Cu content is 20 to 98.5 mol% and the Zn content with respect to all metal elements in the black pigment. Is 1 to 70 mol%, the Si content is 0.5 to 60 mol%, and the total amount of Cu, Zn and Si is 100 mol%. When the Cu content is within the above range, the blackness and the near infrared reflectance can be increased. Moreover, when the Zn content is within the above range, the amount of Cu dissolved by the acid resistance test can be suppressed. Moreover, when the Si content is within the above range, the true specific gravity can be easily reduced to 6.5 g / cm 3 or less, which is advantageous for coating. The preferable Cu content is 24 to 94 mol%, more preferably 28 to 93 mol%. The preferable Zn content is 1 to 59 mol%, more preferably 3 to 58 mol%. The preferable Si content is 1 to 59 mol%, more preferably 3 to 58 mol%.
　本発明に係る赤外線反射性黒色顔料がＣｕ、Ｚｎ、Ｓｉ及びＡｌを含有する複合酸化物である場合、黒色顔料中の全金属元素に対して、Ｃｕ含有量は２０～９８ｍｏｌ％、Ｚｎ含有量は１～７０ｍｏｌ％であり、Ｓｉ含有量は０．５～６０ｍｏｌ％であり、Ａｌ含有量は０．５～６０ｍｏｌ％であり、Ｃｕ、Ｚｎ、Ｓｉ及びＡｌの合計量が１００ｍｏｌ％となる。Ｃｕ含有量が前記範囲内であることによって、黒色度及び近赤外反射率を高くすることができる。また、Ｚｎ含有量が前記範囲内であることによって、耐酸性試験によるＣｕ溶解量を抑制できる。また、ＡｌとＳｉ含有量が前記範囲内であることによって、容易に真比重を６．５ｇ／ｃｍ３以下とすることができ塗料化に有利である。好ましいＣｕ含有量は２４～９６ｍｏｌ％であり、より好ましくは２８～９５ｍｏｌ％である。また、好ましいＺｎ含有量は１～５９ｍｏｌ％であり、より好ましくは３～５７ｍｏｌ％である。また、好ましいＳｉ含有量は１～５９ｍｏｌ％であり、より好ましくは２～５８ｍｏｌ％である。また、好ましいＡｌ含有量は１～５９ｍｏｌ％であり、より好ましくは２～５８ｍｏｌ％である。 When the infrared reflective black pigment according to the present invention is a complex oxide containing Cu, Zn, Si, and Al, the Cu content is 20 to 98 mol% and the Zn content is based on the total metal elements in the black pigment. Is 1 to 70 mol%, the Si content is 0.5 to 60 mol%, the Al content is 0.5 to 60 mol%, and the total amount of Cu, Zn, Si and Al is 100 mol%. When the Cu content is within the above range, the blackness and the near infrared reflectance can be increased. Moreover, when the Zn content is within the above range, the amount of Cu dissolved by the acid resistance test can be suppressed. In addition, when the Al and Si contents are within the above ranges, the true specific gravity can be easily reduced to 6.5 g / cm 3 or less, which is advantageous for coating. The preferable Cu content is 24 to 96 mol%, more preferably 28 to 95 mol%. The preferable Zn content is 1 to 59 mol%, more preferably 3 to 57 mol%. Further, the preferable Si content is 1 to 59 mol%, more preferably 2 to 58 mol%. The preferable Al content is 1 to 59 mol%, more preferably 2 to 58 mol%.
　本発明に係る赤外線反射性黒色顔料は各種原料の混合物を焼成して得られるものであり、各種金属元素の化合物を混合しただけでは所望の効果は得られない。本発明に係る赤外線反射性黒色顔料は原料混合物を焼成して得られた複合酸化物であればＸ線回折による構成相の同定によって単一相である必要はなく、複数の構成相から形成されていてもよい。 The infrared reflective black pigment according to the present invention is obtained by firing a mixture of various raw materials, and a desired effect cannot be obtained only by mixing various metal element compounds. The infrared reflective black pigment according to the present invention does not need to be a single phase by the identification of the constituent phase by X-ray diffraction as long as it is a composite oxide obtained by firing a raw material mixture, and is formed from a plurality of constituent phases. It may be.
　また、本発明に係る赤外線反射性黒色顔料は、各種原料由来の不純物が不可避的に混入してもよい。 Further, the infrared reflective black pigment according to the present invention may inevitably contain impurities derived from various raw materials.
　本発明に係る赤外線反射性黒色顔料の平均粒子径は、０．０２～５．０μｍが好ましい。黒色顔料の平均粒子径が５．０μｍを超える場合には、粒子サイズが大きすぎるため、着色力が低下する。平均粒子径が０．０２μｍ未満の場合には、ビヒクル中への分散が困難となる場合がある。より好ましい平均粒子径は０．０２５～４．０μｍ、更により好ましくは０．０４～２．０μｍである。 The average particle diameter of the infrared reflective black pigment according to the present invention is preferably 0.02 to 5.0 μm. When the average particle diameter of the black pigment exceeds 5.0 μm, the particle size is too large, and the coloring power is reduced. When the average particle size is less than 0.02 μm, dispersion in the vehicle may be difficult. A more preferable average particle diameter is 0.025 to 4.0 μm, and still more preferably 0.04 to 2.0 μm.
　本発明に係る赤外線反射性黒色顔料のＢＥＴ比表面積は、１～１００ｍ２／ｇが好ましい。ＢＥＴ比表面積が１ｍ２／ｇ未満の場合には、粒子が粗大であったり、粒子及び粒子相互間で焼結が生じた粒子となっており、着色力が低下する。一方、ＢＥＴ比表面積が１００ｍ２／ｇを超える場合には、粒子の微細化による分子間力の増大により凝集を起こしやすいため、分散性が低下する。より好ましいＢＥＴ比表面積は１．５～７５ｍ２／ｇ、更により好ましくは１．８～６５ｍ２／ｇである。 The BET specific surface area of the infrared reflective black pigment according to the present invention is preferably 1 to 100 m 2 / g. When the BET specific surface area is less than 1 m 2 / g, the particles are coarse or the particles are sintered between the particles and the coloring power is reduced. On the other hand, when the BET specific surface area exceeds 100 m 2 / g, the dispersibility is lowered because aggregation tends to occur due to an increase in intermolecular force due to finer particles. A more preferred BET specific surface area is 1.5 to 75 m 2 / g, and even more preferably 1.8 to 65 m 2 / g.
　本発明に係る赤外線反射性黒色顔料の黒色度を明度（Ｌ＊）で示した場合、２９以下が好ましい。明度（Ｌ＊）が前記範囲外の場合には、黒色顔料とは言い難い。好ましい明度（Ｌ＊）は２８以下、より好ましくは２６以下である。 When the blackness of the infrared reflective black pigment according to the present invention is represented by lightness (L * ), it is preferably 29 or less. When the lightness (L * ) is outside the above range, it is difficult to say that it is a black pigment. The lightness (L * ) is preferably 28 or less, more preferably 26 or less.
　本発明に係る赤外線反射性黒色顔料のａ＊は、－２～＋１０が好ましい。ａ＊が前記範囲外の場合には、黒色顔料とは言い難い。より好ましくは－１～＋５である。 The a * of the infrared reflective black pigment according to the present invention is preferably -2 to +10. When a * is outside the above range, it is difficult to say a black pigment. More preferably, it is -1 to +5.
　本発明に係る赤外線反射性黒色顔料のｂ＊は、－５～＋１０が好ましい。ｂ＊が前記範囲外の場合には、黒色顔料とは言い難い。より好ましくは－４～＋５である。 The b * of the infrared reflective black pigment according to the present invention is preferably −5 to +10. When b * is outside the above range, it is difficult to say a black pigment. More preferably, it is −4 to +5.
　なお、これらの赤外線反射性黒色顔料の明度（Ｌ＊）、ａ＊、ｂ＊は、黒色顔料の組成、焼成条件及び粉砕条件によって上記の範囲となるように調整できる。 The lightness (L * ), a * , and b * of these infrared reflective black pigments can be adjusted to be in the above range depending on the composition of the black pigment, firing conditions, and pulverization conditions.
　本発明に係る赤外線反射性黒色顔料の近赤外反射率は、ラッカー色見本塗膜をＪＩＳ　Ｋ　５６０２に従い測定したときの近赤外反射率が４３％以上が好ましい。近赤外反射率が４３％未満では、近赤外反射率が十分に高いとは言えない。より好ましい近赤外反射率は４５％以上であり、更により好ましくは４６％以上である。近赤外反射率は、黒色顔料の組成、焼成条件及び粉砕条件によって上記の範囲となるように調整できる。 The near infrared reflectance of the infrared reflective black pigment according to the present invention is preferably 43% or more when the lacquer color sample coating film is measured according to JIS K5602. If the near infrared reflectance is less than 43%, it cannot be said that the near infrared reflectance is sufficiently high. A more preferable near infrared reflectance is 45% or more, and even more preferably 46% or more. The near-infrared reflectance can be adjusted to be in the above range depending on the composition of the black pigment, the firing conditions, and the pulverization conditions.
　本発明に係る赤外線反射性黒色顔料の真比重は４．５～６．３ｇ／ｃｍ３が好ましい。真比重を前記範囲に制御することによって、塗料の安定性がより向上する。より好ましい真比重は４．６～６．２ｇ／ｃｍ３、更により好ましくは４．７～６．１ｇ／ｃｍ３である。真比重は、黒色顔料の組成によって上記の範囲となるように調整できる。 The true specific gravity of the infrared reflective black pigment according to the present invention is preferably 4.5 to 6.3 g / cm 3 . By controlling the true specific gravity within the above range, the stability of the paint is further improved. The more preferable true specific gravity is 4.6 to 6.2 g / cm 3 , and still more preferably 4.7 to 6.1 g / cm 3 . The true specific gravity can be adjusted to be in the above range depending on the composition of the black pigment.
　本発明に係る赤外線反射性黒色顔料の耐酸性は、後述する評価方法によって測定したＣｕ溶解量について１０００ｐｐｍ以下が好ましい。Ｃｕ溶解量が１０００ｐｐｍを超える場合には、Ｃｕが溶解しやすく、顔料が変質する。より好ましいＣｕ溶解量は８００ｐｐｍ以下であり、更により好ましくは５００ｐｐｍ以下である。耐酸性は、黒色顔料の組成、焼成条件及び粉砕条件によって上記の範囲となるように調整できる。 The acid resistance of the infrared reflective black pigment according to the present invention is preferably 1000 ppm or less with respect to the amount of dissolved Cu measured by the evaluation method described later. When the amount of Cu dissolved exceeds 1000 ppm, Cu is easily dissolved and the pigment is altered. A more preferable Cu dissolution amount is 800 ppm or less, and even more preferably 500 ppm or less. The acid resistance can be adjusted to be in the above range depending on the composition of the black pigment, the firing conditions and the grinding conditions.
　本発明に係る赤外線反射性黒色顔料の粒子の形状は、特定の形状に限定されず、球状、粒状、八面体状、六面体状、多面体状等の粒状粒子、針状、紡錘状、米粒状等の針状粒子及び板状粒子等を使用することができる。得られる黒色顔料の分散性を考慮すれば、球状粒子及び粒状粒子が好ましい。 The shape of the particles of the infrared-reflective black pigment according to the present invention is not limited to a specific shape, and is spherical, granular, octahedral, hexahedral, polyhedral, etc., acicular, spindle, rice, etc. Needle-like particles and plate-like particles can be used. Considering the dispersibility of the resulting black pigment, spherical particles and granular particles are preferred.
　本発明に係る赤外線反射性黒色顔料は、Ｓｉ、Ａｌ、Ｚｒ、Ｔｉ、Ｚｎ、Ｐから選ばれる１種以上の化合物又は有機系表面処理剤を用いて赤外線反射性黒色顔料の表面を被覆することができる。表面被覆により、容易に分散性向上の効果が得られる。 The infrared reflective black pigment according to the present invention covers the surface of an infrared reflective black pigment using one or more compounds selected from Si, Al, Zr, Ti, Zn, and P or an organic surface treatment agent. Can do. The effect of improving dispersibility can be easily obtained by the surface coating.
　Ｓｉ、Ａｌ、Ｚｒ、Ｔｉ、Ｚｎ、Ｐから選ばれる１種以上の化合物としては、アルミニウム化合物として、酢酸アルミニウム、硫酸アルミニウム、塩化アルミニウム、硝酸アルミニウム等のアルミニウム塩や、アルミン酸ナトリウム等のアルミン酸アルカリ塩等が挙げられる。ケイ素化合物として、３号水ガラス、オルトケイ酸ナトリウム、メタケイ酸ナトリウム等が挙げられる。ジルコニウム化合物として、酢酸ジルコニウム、硫酸ジルコニウム、塩化ジルコニウム、硝酸ジルコニウム等のジルコニウム塩等が使用できる。チタン化合物として、酢酸チタニウム、硫酸チタニウム、塩化チタニウム、硝酸チタニウム等のチタニウム塩等が使用できる。亜鉛化合物として、酢酸亜鉛、硫酸亜鉛、塩化亜鉛、硝酸亜鉛等の亜鉛塩等が使用できる。りん化合物として、リン酸水素ナトリウム、リン酸水素アンモニウムナトリウム、リン酸カリウム、ポリリン酸ナトリウム、ヘキサメタリン酸ナトリウム等のリン酸塩等が使用できる。 One or more compounds selected from Si, Al, Zr, Ti, Zn, and P include aluminum compounds such as aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride, and aluminum nitrate, and aluminates such as sodium aluminate. Examples include alkali salts. Examples of the silicon compound include No. 3 water glass, sodium orthosilicate, sodium metasilicate, and the like. As the zirconium compound, zirconium salts such as zirconium acetate, zirconium sulfate, zirconium chloride, and zirconium nitrate can be used. As the titanium compound, titanium salts such as titanium acetate, titanium sulfate, titanium chloride, and titanium nitrate can be used. As the zinc compound, zinc salts such as zinc acetate, zinc sulfate, zinc chloride, and zinc nitrate can be used. As the phosphorus compound, phosphates such as sodium hydrogen phosphate, sodium ammonium hydrogen phosphate, potassium phosphate, sodium polyphosphate, sodium hexametaphosphate and the like can be used.
　有機系表面処理剤としては、ステアリン酸又はその塩、ロジン、アルコキシシラン、フルオロアルキルシラン、シラン系カップリング剤及びオルガノポリシロキサン等の有機ケイ素化合物、チタネート系、アルミネート系及びジルコネート系などのカップリング剤、低分子あるいは高分子界面活性剤、リン酸化合物等が挙げられる。 Organic surface treatment agents include stearic acid or salts thereof, rosin, alkoxysilanes, fluoroalkylsilanes, silane coupling agents, organosilicon compounds such as organopolysiloxanes, titanates, aluminates, and zirconates. Examples thereof include a ring agent, a low molecular or high molecular surfactant, and a phosphoric acid compound.
　有機ケイ素化合物としては、具体的には、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、エチルトリエトキシシラン、プロピルトリエトキシシラン、ブチルトリエトキシシラン、イソブチルトリメトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン及びデシルトリエトキシシラン等のアルコキシシラン、トリフルオロプロピルトリメトキシシラン、トリデカフルオロオクチルトリメトキシシラン、ヘプタデカフルオロデシルトリメトキシシラン、トルフルオロプロピルトリエトキシシラン、ヘプタデカフルオロデシルトリエトキシシラン及びトリデカフルオロオクチルトリエトキシシラン等のフルオロアルキルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－メタクロイルオキシプロピルトリメトキシシラン、Ｎ－（β－アミノエチル）－γ－アミノプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジメトキシシラン、γ－クロロプロピルトリメトキシシラン等のシラン系カップリング剤、ポリシロキサン、メチルハイドロジェンポリシロキサン、変性ポリシロキサン等のオルガノポリシロキサン等が挙げられる。 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, heptadecafluorodecyltri Fluoroalkylsilanes such as toxisilane and tridecafluorooctyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane Silane-based 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.
　チタネート系カップリング剤としては、イソプロピルトリステアロイルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、イソプロピルトリ（Ｎ－アミノエチル・アミノエチル）チタネート、テトラオクチルビス（ジトリデシルホスフェイト）チタネート、テトラ（２－２－ジアリルオキシメチル－１－ブチル）ビス（ジトリデシル）ホスフェイトチタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）エチレンチタネート等が挙げられる。 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, bis (dioctylpyrophosphate) ethylene titanate, and the like.
　アルミネート系カップリング剤としては、アセトアルコキシアルミニウムジイソプロピレート、アルミニウムジイソプロボキシモノエチルアセトアセテート、アルミニウムトリスエチルアセトアセテート、アルミニウムトリスアセチルアセトネート等が挙げられる。 Examples of the aluminate coupling agent include acetoalkoxyaluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate and the like.
　ジルコネート系カップリング剤としては、ジルコニウムテトラキスアセチルアセトネート、ジルコニウムジブトキシビスアセチルアセトネート、ジルコニウムテトラキスエチルアセトアセテート、ジルコニウムトリブトキシモノエチルアセトアセテート、ジルコニウムトリブトキシアセチルアセトネート等が挙げられる。 Examples of the zirconate coupling agent include zirconium tetrakisacetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tetrakisethylacetoacetate, zirconium tributoxymonoethylacetoacetate, zirconium tributoxyacetylacetonate and the like.
　低分子系界面活性剤としては、アルキルベンゼンスルホン酸塩、ジオクチルスルホンコハク酸塩、アルキルアミン酢酸塩、アルキル脂肪酸塩等が挙げられる。高分子系界面活性剤としては、ポリビニルアルコール、ポリアクリル酸塩、カルボキシメチルセルロース、アクリル酸－マレイン酸塩コポリマー、オレフィン－マレイン酸塩コポリマー等が挙げられる。 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.
　リン酸化合物としては、リン酸エステル、亜リン酸エステル、酸性リン酸エステル、ホスホン酸等の有機リン化合物等が挙げられる。 Examples of phosphoric acid compounds include organic phosphorus compounds such as phosphoric acid esters, phosphorous acid esters, acidic phosphoric acid esters, and phosphonic acids.
　表面処理は、用いる処理剤の種類にもよるが、通常、黒色顔料に対し、０．１～１０重量％、好ましくは０．３～８．０重量％の範囲で行う。 The surface treatment is usually performed in the range of 0.1 to 10% by weight, preferably 0.3 to 8.0% by weight with respect to the black pigment, although it depends on the type of treatment agent used.
　次に、本発明に係る赤外線反射性黒色顔料の製造法について述べる。 Next, a method for producing an infrared reflective black pigment according to the present invention will be described.
　本発明に係る複合酸化物からなる赤外線反射性黒色顔料は、各種原料を混合、焼成して得ることができる。出発原料は、前記各金属元素の酸化物、水酸化物、炭酸塩、硝酸塩、硫酸塩などを用いることができる。 The infrared reflective black pigment made of the composite oxide according to the present invention can be obtained by mixing and firing various raw materials. As the starting material, oxides, hydroxides, carbonates, nitrates, sulfates and the like of the respective metal elements can be used.
　出発原料の混合は、均一に混合することができれば、特に限定されるものではなく、湿式混合でも乾式混合でもよい。また湿式合成であってもよい。 The mixing of the starting materials is not particularly limited as long as it can be uniformly mixed, and may be wet mixing or dry mixing. Also, wet synthesis may be used.
　乾式方法において、出発原料の混合撹拌に使用する機器としては、粉体層にせん断力を加えることのできる装置が好ましく、せん断、へらなで及び圧縮が同時に行える装置、例えば、ホイール型混練機、ボール型混練機、ブレード型混練機、ロール型混練機を用いることが好ましい。ホイール型混練機がより効果的に使用できる。 In the dry method, the equipment used for mixing and stirring the starting materials is preferably an apparatus that can apply a shearing force to the powder layer, and an apparatus that can simultaneously perform shearing, spatula and compression, for example, a wheel-type kneader, It is preferable to use a ball-type kneader, a blade-type kneader, or a roll-type kneader. A wheel-type kneader can be used more effectively.
　前記ホイール型混練機としては、エッジランナー（「ミックスマラー」、「シンプソンミル」、「サンドミル」と同義語である）、マルチマル、ストッツミル、ウエットパンミル、コナーミル、リングマラー等があり、好ましくはエッジランナー、マルチマル、ストッツミル、ウエットパンミル、リングマラーであり、より好ましくはエッジランナーである。前記ボール型混練機としては、振動ミルがある。前記ブレード型混練機としては、ヘンシェルミキサー、プラネタリーミキサー、ナウタミキサーがある。前記ロール型混練機としては、エクストルーダーがある。 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. As the ball kneader, there is a vibration mill. Examples of the blade type kneader include a Henschel mixer, a planetary mixer, and a nauta mixer. As the roll type kneader, there is an extruder.
　加熱焼成温度は５００～１１００℃が好ましく、５５０～１０５０℃がより好ましい。加熱雰囲気は大気中である。 The heating and firing temperature is preferably 500 to 1100 ° C, more preferably 550 to 1050 ° C. The heating atmosphere is air.
　加熱後の粉末は、常法に従って、水洗、粉砕を行えばよい。 The powder after heating may be washed and pulverized according to a conventional method.
　本発明においては、赤外線反射性黒色顔料の粒子表面をＳｉ、Ａｌ、Ｚｒ、Ｔｉ、Ｚｎ、Ｐから選ばれる１種又は２種以上の化合物によって被覆しておいてもよい。表面処理方法は、湿式あるいは乾式方法等の常法に従って行えばよい。例えば、湿式方法は湿式分散した赤外線反射性黒色顔料のスラリーに、Ｓｉ、Ａｌ、Ｚｒから選ばれる１種又は２種以上の可溶性化合物を、酸又はアルカリでｐＨ調整しながら添加・混合して被覆する方法、乾式方法はヘンシェルミキサーなどの装置中で赤外線反射性黒色顔料にＳｉ、Ａｌ、Ｚｒから選ばれる１種又は２種以上のカップリング剤などにより被覆処理する方法である。 In the present invention, the particle surface of the infrared reflective black pigment may be coated with one or more compounds selected from Si, Al, Zr, Ti, Zn, and P. The surface treatment method may be performed according to a conventional method such as a wet method or a dry method. For example, in the wet method, one or two or more soluble compounds selected from Si, Al, and Zr are added to and mixed with a slurry of a wet-dispersed infrared reflective black pigment while adjusting the pH with an acid or an alkali. The dry method is a method in which an infrared reflective black pigment is coated with one or more coupling agents selected from Si, Al and Zr in an apparatus such as a Henschel mixer.
　乾式方法において、黒色顔料と表面処理剤との混合撹拌に使用する機器としては、粉体層にせん断力を加えることのできる装置が好ましく、せん断、へらなで及び圧縮が同時に行える装置、例えば、ホイール型混練機、ボール型混練機、ブレード型混練機、ロール型混練機を用いることが好ましい。ホイール型混練機がより効果的に使用できる。 In the dry method, as an apparatus used for mixing and stirring the black pigment and the surface treatment agent, an apparatus that can apply a shearing force to the powder layer is preferable, and an apparatus that can simultaneously perform shearing, spatula and compression, for example, It is preferable to use a wheel-type kneader, a ball-type kneader, a blade-type kneader, or a roll-type kneader. A wheel-type kneader can be used more effectively.
　前記ホイール型混練機としては、エッジランナー（「ミックスマラー」、「シンプソンミル」、「サンドミル」と同義語である）、マルチマル、ストッツミル、ウエットパンミル、コナーミル、リングマラー等があり、好ましくはエッジランナー、マルチマル、ストッツミル、ウエットパンミル、リングマラーであり、より好ましくはエッジランナーである。前記ボール型混練機としては、振動ミルがある。前記ブレード型混練機としては、ヘンシェルミキサー、プラネタリーミキサー、ナウタミキサーがある。前記ロール型混練機としては、エクストルーダーがある。 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. As the ball kneader, there is a vibration mill. Examples of the blade type kneader include a Henschel mixer, a planetary mixer, and a nauta mixer. As the roll type kneader, there is an extruder.
　次に、本発明に係る赤外線反射性黒色顔料を配合した塗料について述べる。 Next, the paint containing the infrared reflective black pigment according to the present invention will be described.
　本発明に係る塗料中における赤外線反射性黒色顔料の配合割合は、塗料構成基材１００重量部に対して０．５～１００重量部の範囲で使用することができ、塗料のハンドリング性を考慮すれば、好ましくは１．０～１００重量部である。 The blending ratio of the infrared reflective black 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, taking into account the handleability of the paint. For example, it is preferably 1.0 to 100 parts by weight.
　塗料構成基材としては、樹脂、溶剤、必要により油脂、消泡剤、体質顔料、乾燥促進剤、界面活性剤、硬化促進剤、助剤等が配合される。 As the paint constituting base material, resin, solvent, and if necessary, fats and oils, antifoaming agent, extender pigment, drying accelerator, surfactant, curing accelerator, auxiliary agent and the like are blended.
　樹脂としては、溶剤系塗料用や油性印刷インクに通常使用されているアクリル樹脂、アルキッド樹脂、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、アミノ樹脂、塩化ビニル樹脂、シリコーン樹脂、ガムロジン、ライムロジン等のロジン系樹脂、マレイン酸樹脂、ポリアミド樹脂、ニトロセルロース、エチレン－酢酸ビニル共重合樹脂、ロジン変性フェノール樹脂、ロジン変性マレイン酸樹脂等のロジン変性樹脂、石油樹脂、フッ素樹脂等を用いることができる。水系塗料用としては、水系塗料用や水性インクに通常使用されている水溶性アクリル樹脂、水溶性スチレン－マレイン酸樹脂、水溶性アルキッド樹脂、水溶性メラミン樹脂、水溶性ウレタンエマルジョン樹脂、水溶性エポキシ樹脂、水溶性ポリエステル樹脂、水可溶性フッ素樹脂等を用いることができる。 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, fluorine resins, etc. be able to. 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 in water-based paints and water-based inks Resins, water-soluble polyester resins, water-soluble fluororesins, and the like can be used.
　溶剤としては、溶剤系塗料用に通常使用されている大豆油、トルエン、キシレン、シンナー、ブチルアセテート、メチルアセテート、メチルイソブチルケトン、メチルセロソルブ、エチルセロソルブ、プロピルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のグリコールエーテル系溶剤、酢酸エチル、酢酸ブチル、酢酸アミル等のエステル系溶剤、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素系溶剤、シクロヘキサン等の脂環族炭化水素系溶剤、ミネラルスピリット等の石油系溶剤、アセトン、メチルエチルケトン等のケトン系溶剤、メチルアルコール、エチルアルコール、プロピルアルコール、ブチルアルコール等のアルコール系溶剤、脂肪族炭化水素等を用いることができる。 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.
　水系塗料用溶剤としては、水と水系塗料用に通常使用されているエチルアルコール、プロピルアルコール、ブチルアルコール等のアルコール系溶剤、メチルセロソルブ、エチルセロソルブ、プロピルセロソルブ、ブチルセロソルブ等のグリコールエーテル系溶剤、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール等のオキシエチレン又はオキシプロピレン付加重合体、エチレングリコール、プロピレングリコール、１，２，６－ヘキサントリオール等のアルキレングリコール、グリセリン、２－ピロリドン等の水溶性有機溶剤とを混合して使用することができる。 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 polymer 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.
　油脂としては、あまに油、きり油、オイチシカ油、サフラワー油等の乾性油を加工したボイル油を用いることができる。 As the fats and oils, boil oils obtained by processing dry oils such as sesame oil, cutting oil, sea lion oil, safflower oil and the like can be used.
　消泡剤としては、ノプコ８０３４（商品名）、ＳＮデフォーマー４７７（商品名）、ＳＮデフォーマー５０１３（商品名）、ＳＮデフォーマー２４７（商品名）、ＳＮデフォーマー３８２（商品名）（以上、いずれもサンノプコ株式会社製）、アンチホーム０８（商品名）、エマルゲン９０３（商品名）（以上、いずれも花王株式会社製）等の市販品を使用することができる。 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.
　本発明の赤外線反射性黒色顔料を含有する塗料は分散性に優れる。実施例に記載の評価方法に従った再分散性が優れている場合、塗料安定化が容易（均一に分散）と評価される。 The paint containing the infrared reflective black pigment of the present invention is excellent in dispersibility. When the redispersibility according to the evaluation method described in the examples is excellent, it is evaluated that the paint stabilization is easy (uniformly dispersed).
　次に、本発明に係る赤外線反射性黒色顔料を含有する樹脂組成物について述べる。 Next, the resin composition containing the infrared reflective black pigment according to the present invention will be described.
　本発明に係る樹脂組成物中における赤外線反射性黒色顔料の配合割合は、樹脂１００重量部に対して０．０１～２００重量部の範囲で使用することができ、樹脂組成物のハンドリング性を考慮すれば、好ましくは０．０５～１５０重量部、更に好ましくは０．１～１００重量部である。 The blending ratio of the infrared reflective black 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 the handling property of the resin composition is taken into consideration. Thus, the amount is preferably 0.05 to 150 parts by weight, more preferably 0.1 to 100 parts by weight.
　本発明に係る樹脂組成物における構成基材としては、赤外線反射性黒色顔料と周知の熱可塑性樹脂とともに、必要により、滑剤、可塑剤、酸化防止剤、紫外線吸収剤、各種安定剤等の添加剤が配合される。 As a constituent substrate in the resin composition according to the present invention, an additive such as a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, and various stabilizers, if necessary, together with an infrared reflective black pigment and a known thermoplastic resin. Is blended.
　樹脂としては、ポリエチレン、ポリプロピレン、ポリブテン、ポリイソブチレン等のポリオレフィン、ポリ塩化ビニル、ポリメチルペンテン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリスチレン、スチレン－アクリル酸エステル共重合体、スチレン－酢酸ビニル共重合体、アクリロニトリル－ブタジエン－スチレン共重合体、アクリロニトリル－ＥＰＤＭ－スチレン共重合体、アクリル系樹脂、ポリアミド、ポリカーボネート、ポリアセタール、ポリウレタン等の熱可塑性樹脂、ロジン変性マレイン酸樹脂、フェノール樹脂、エポキシ樹脂、ポリエステル樹脂、シリコーン樹脂、ロジン・エステル、ロジン、天然ゴム、合成ゴム等を用いることができる。 Examples of the resin include polyolefins such as polyethylene, polypropylene, polybutene, 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 resin, phenol resin, epoxy resin, polyester resin, Silicone resin, rosin ester, rosin, natural rubber, synthetic rubber and the like can be used.
　添加剤の量は、赤外線反射性黒色顔料と樹脂との総和に対して５０重量％以下であればよい。添加剤の含有量が５０重量％を超える場合には、成形性が低下する。 The amount of the additive may be 50% by weight or less based on the sum of the infrared reflective black pigment and the resin. When the content of the additive exceeds 50% by weight, the moldability is lowered.
　本発明に係る樹脂組成物は、樹脂原料と赤外線反射性黒色顔料をあらかじめよく混合し、次に、混練機もしくは押出機を用いて加熱下で強いせん断作用を加えて、赤外線反射性黒色顔料の凝集体を破壊し、樹脂組成物中に赤外線反射性黒色顔料を均一に分散させた後、目的に応じた形状に成形加工して使用する。 The resin composition according to the present invention is prepared by mixing a resin raw material and an infrared reflective black pigment in advance, and then applying a strong shearing action under heating using a kneader or an extruder to produce an infrared reflective black pigment. The aggregate is broken and the infrared reflective black pigment is uniformly dispersed in the resin composition, and then molded into a shape suitable for the purpose.
　また本発明に係る樹脂組成物は、マスターバッチペレットを経由して得ることもできる。 The resin composition according to the present invention can also be obtained via a master batch pellet.
　本発明におけるマスターバッチペレットは、塗料及び樹脂組成物の構成基材としての結合材樹脂と前記赤外線反射性黒色顔料とを必要により、リボンブレンダー、ナウターミキサー、ヘンシェルミキサー、スーパーミキサー等の混合機で混合した後、周知の単軸混練押出機や二軸混練押出機等で混練、成形した後切断するか、又は、上記混合物をバンバリーミキサー、加圧ニーダー等で混練して得られた混練物を粉砕又は成形、切断することにより製造される。 The master batch pellet in the present invention requires a binder resin as a constituent substrate of the paint and the resin composition and the infrared reflective black 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.
　結合材樹脂と赤外線反射性黒色顔料の混練機への供給は、それぞれを所定比率で定量供給してもよいし、両者の混合物を供給してもよい。 The supply of the binder resin and the infrared reflective black pigment to the kneader may be quantitatively supplied at a predetermined ratio or a mixture of both.
　本発明におけるマスターバッチペレットは、平均長径１～６ｍｍ、好ましくは２～５ｍｍの範囲である。平均短径は２～５ｍｍ、好ましくは２．５～４ｍｍである。平均長径が１ｍｍ未満の場合には、ペレット製造時の作業性が悪く好ましくない。６ｍｍを超える場合には、希釈用結合材樹脂の大きさとの違いが大きく、十分に分散させるのが困難となる。また、その形状は種々のものができ、不定形及び球形等の粒状、円柱形、フレーク状等にできる。 The master batch pellet in 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.
　本発明におけるマスターバッチペレットに使用する結合材樹脂としては、前記樹脂組成物用樹脂と同一の樹脂が使用できる。 As the binder resin used for the master batch pellet in the present invention, the same resin as the resin for resin composition can be used.
　なお、マスターバッチペレット中の結合材樹脂の組成は、希釈用結合材樹脂と同一の樹脂を用いても、また、異なる樹脂を用いてもよいが、異なる樹脂を使用する場合には、樹脂同士の相溶性により決まる諸特性を考慮して決めればよい。 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.
　マスターバッチペレット中に配合される赤外線反射性黒色顔料の量は、結合材樹脂１００重量部に対して１～２００重量部、好ましくは１～１５０重量部、より好ましくは１～１００重量部である。１重量部未満の場合には、混練時の溶融粘度が不足し、赤外線反射性黒色顔料の良好な分散混合が困難である。２００重量部を超える場合には、赤外線反射性黒色顔料に対する結合材樹脂が少ないため、赤外線反射性黒色顔料の良好な分散混合が難しく、また、マスターバッチペレットの添加量のわずかな変化によって樹脂組成物中に配合される赤外線反射性黒色顔料の含有量が大きく変化するため所望の含有量に調製することが困難となり好ましくない。また、機械摩耗が激しく適当ではない。 The amount of the infrared reflective black pigment blended in the master batch pellet is 1 to 200 parts by weight, preferably 1 to 150 parts by weight, 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 and mixing of the infrared reflective black pigment. When the amount exceeds 200 parts by weight, since there is little binder resin for the infrared reflective black pigment, good dispersion and mixing of the infrared reflective black pigment is difficult, and the resin composition can be changed by a slight change in the addition amount of the master batch pellet. Since the content of the infrared-reflective black pigment blended in the product greatly changes, it is difficult to prepare the desired content, which is not preferable. Also, mechanical wear is severe and not suitable.
　本発明の代表的な実施例は、次の通りである。 A typical embodiment of the present invention is as follows.
　粒子の平均粒子径は空気透過法（フィッシャー法）により、測定した。 The average particle diameter of the particles was measured by an air permeation method (Fischer method).
　比表面積は、ＢＥＴ法により測定した値で示した。 The specific surface area is indicated by a value measured by the BET method.
　真比重は、「乾式自動密度計　アキュピックＩＩ－１３４０」（マイクロメリティクス製）で測定した値を示した。 The true specific gravity indicates a value measured with a “dry automatic densimeter Accupick II-1340” (manufactured by Micromeritics).
　赤外線反射性黒色顔料の金属元素の含有量は、「蛍光Ｘ線分析装置３０６３Ｍ型」（理学電機工業株式会社製）を使用し、ＪＩＳ　Ｋ０１１９の「けい光Ｘ線分析通則」に従って測定した。 The content of the metal element of the infrared reflective black pigment was measured using a “fluorescence X-ray analyzer 3063M type” (manufactured by Rigaku Denki Kogyo Co., Ltd.) according to “General X-ray fluorescence analysis rules” of JIS K0119.
　赤外線反射性黒色顔料の色相（Ｌ＊値、ａ＊値、ｂ＊値）は、試料０．５ｇとヒマシ油０．５ｍｌとをフーバー式マーラーで練ってペースト状とし、このペーストにクリアラッカー４．５ｇを加え、混練、塗料化してキャストコート紙上に１５０μｍ（６ｍｉｌ）のアプリケーターを用いて塗布した塗布片（塗膜厚み：約３０μｍ）を作製した。塗膜片について、「色彩色差計ＣＲ－３００」（コニカミノルタセンシング株式会社製）を用いて測定を行い、ＪＩＳ　Ｚ　８７２９に定めるところに従って表色指数（Ｌ＊値、ａ＊値、ｂ＊値）で示した。 The hue (L * value, a * value, b * value) of the infrared reflective black pigment was prepared by mixing 0.5 g of a sample and 0.5 ml of castor oil with a Hoover type Mahler to form a paste. .5 g was added, kneaded and converted into a paint, and an application piece (coating thickness: about 30 μm) applied on cast-coated paper using a 150 μm (6 mil) applicator was produced. The coating piece was measured using a “color difference meter CR-300” (manufactured by Konica Minolta Sensing Co., Ltd.), and the color index (L * value, a * value, b * value) according to JIS Z 8729. ).
　赤外線反射用黒色顔料の可視光領域及び近赤外線領域での波長の反射性は、上記の色相を測定するために作製した塗膜片について、「分光光度計　Ｕ－４１００」（株式会社日立ハイテクノロジーズ）を用いて測定を行い、２５０～２５００ｎｍの波長における反射率（％）を測定した。ＪＩＳ　Ｋ　５６０２に従って７８０～２５００ｎｍの波長の範囲の反射率を近赤外反射率として算出した。 The reflectance of the wavelength of the black pigment for infrared reflection in the visible light region and the near infrared region is determined by “spectrophotometer U-4100” (Hitachi High-Technologies Corporation) for the coating piece prepared for measuring the above hue. ) And the reflectance (%) at a wavelength of 250 to 2500 nm was measured. The reflectance in the wavelength range of 780 to 2500 nm was calculated as the near infrared reflectance according to JIS K 5602.
　赤外線反射性黒色顔料の耐酸性の評価は、ＪＩＳ　Ｋ５１０１－８の「顔料試験方法　第８部：耐薬品性」に従い、試験管に顔料２ｇと５％の硫酸を２０ｍｌ加え、密封して良く振り、１５分静置し、静置後、再び密封してよく振り、３０分間静置する。静置させた後、ろ過分離後の溶液について「ＩＣＰ発光分光分析装置ｉＣＡＰ－６５００ＤＵＯ」（サーモエレクトロン株式会社製）を使用して、溶解Ｃｕ量を測定した。 The acid resistance of the infrared reflective black pigment was evaluated in accordance with JIS K5101-8 “Pigment Test Method Part 8: Chemical Resistance”. Add 2 g of pigment and 20 ml of 5% sulfuric acid to the test tube, seal and shake well. Let stand for 15 minutes, and after resting, seal again and shake and leave for 30 minutes. After allowing to stand, the amount of dissolved Cu was measured for the solution after separation by filtration using “ICP emission spectroscopic analyzer iCAP-6500DUO” (manufactured by Thermo Electron Co., Ltd.).
　赤外線反射性黒色顔料を含有する塗料の分散性の評価は、次の要領で行なった。
　マヨネーズビン（内容積１４０ｍｌ）中に、ガラスビーズ９０ｇ、黒色顔料１０ｇ、アミノアルキッド樹脂（クリヤー）１６．０ｇ、溶剤６．０ｇ配合し、ペイントコンデイショナーで４０分間分散後、更にアルミアルキッド樹脂（クリヤー）５０ｇ追加後、ペイントコンデイショナーで５分分散し、ガラスビーズと分離した。その後２４時間静置し、黒色顔料を沈降させた。この沈殿物を含む塗料を撹拌機でかき混ぜたときの再分散性を観察し、塗料安定化の容易、困難を評価した。塗料安定化の容易とは、顔料が塗料内に均一に分散していることであり、困難とは、顔料の沈降及び分離（色別れ）が起きることであり、これを区別して評価した。 The dispersibility of the paint containing the infrared reflective black pigment was evaluated in the following manner.
In mayonnaise bottle (internal volume 140 ml), 90 g of glass beads, 10 g of black pigment, 16.0 g of amino alkyd resin (clear), 6.0 g of solvent were blended and dispersed for 40 minutes with a paint conditioner. After adding 50 g of (clear), it was dispersed with a paint conditioner for 5 minutes and separated from glass beads. Thereafter, the mixture was allowed to stand for 24 hours to precipitate the black pigment. The redispersibility when the paint containing the precipitate was stirred with a stirrer was observed to evaluate the ease and difficulty of stabilizing the paint. The easy stabilization of the paint is that the pigment is uniformly dispersed in the paint, and the difficulty is that the pigment is settled and separated (color separation).
実施例１
　各種原料化合物を下記表１に示す含有量となるように計量、混合し、電気炉を使用し、９００℃で１時間焼成した。焼成品を粉砕して赤外線反射性黒色顔料を得た。得られた赤外線反射性黒色顔料は、Ｘ線回折の結果、Ｃｕ、Ｚｎ及びＳｉを含む複合酸化物であり、ＢＥＴ比表面積４．０ｍ２／ｇ、平均粒子径１．５μｍの黒色顔料であった。 Example 1
Various raw material compounds were weighed and mixed so as to have the contents shown in Table 1 below, and baked at 900 ° C. for 1 hour using an electric furnace. The fired product was pulverized to obtain an infrared reflective black pigment. As a result of X-ray diffraction, the obtained infrared reflective black pigment is a composite oxide containing Cu, Zn and Si, and is a black pigment having a BET specific surface area of 4.0 m 2 / g and an average particle diameter of 1.5 μm. It was.
　この顔料をラッカー色塗りし、色見本試料を作製し、Ｕ－４１００日立分光光度計を用いて波長２５０ｎｍ～２５００ｎｍ範囲で反射率を測定した。結果は、波長７８０～２５００ｎｍにおける近赤外反射率が６０．３％であった。 This pigment was coated with a lacquer color to prepare a color sample sample, and the reflectance was measured in the wavelength range of 250 nm to 2500 nm using a U-4100 Hitachi spectrophotometer. As a result, the near infrared reflectance at a wavelength of 780 to 2500 nm was 60.3%.
実施例２
　各種原料を酸性水溶液に溶解した後、アルカリ水溶液で中和して前駆体を湿式法で合成した後、８００℃で２時間焼成した以外は前記実施例１と同様にして黒色系顔料を得た。 Example 2
Various raw materials were dissolved in an acidic aqueous solution, neutralized with an aqueous alkaline solution, a precursor was synthesized by a wet method, and then a black pigment was obtained in the same manner as in Example 1 except that the precursor was fired at 800 ° C. for 2 hours. .
実施例３、４
　原料組成及び焼成温度を変化させた以外は、実施例１と同様にして黒色顔料を得た。 Examples 3 and 4
A black pigment was obtained in the same manner as in Example 1 except that the raw material composition and the firing temperature were changed.
実施例５
　原料組成及び焼成温度を変更した以外は前記実施例１と同様にして黒色顔料を得た。次いで、得られた黒色顔料を水中に湿式分散させ、７０℃に保温した黒色顔料のスラリーに対し水ガラス１．０ｗｔ％を滴下しながら塩酸及び水酸化ナトリウムでｐＨ７に調整し１時間維持した。その後、水洗・脱水・乾燥・粉砕処理した。 Example 5
A black pigment was obtained in the same manner as in Example 1 except that the raw material composition and the firing temperature were changed. Next, the obtained black pigment was wet-dispersed in water, adjusted to pH 7 with hydrochloric acid and sodium hydroxide and maintained for 1 hour while dropping 1.0 wt% of water glass into a slurry of black pigment kept at 70 ° C. Thereafter, it was washed with water, dehydrated, dried and pulverized.
実施例６、７、８
　原料組成及び焼成温度を種々変更するとともに、種々の表面処理剤を乾式混合した以外は前記実施例１と同様にして、黒色顔料を得た。 Examples 6, 7, and 8
A black pigment was obtained in the same manner as in Example 1 except that the raw material composition and the firing temperature were variously changed and various surface treatment agents were dry-mixed.
比較例１～３
　比較例１では、日進ケムコ製　酸化銅ＮＢを用いた。比較例２は、比較例１の酸化銅ＮＢとＺｎＣＯ３との混合物であり、比較例３は、比較例１の酸化銅ＮＢとＺｎＣＯ３とＳｉＯ２の混合物であり、比較例４は比較例１の酸化銅ＮＢとＺｎＣＯ３とＳｉＯ２とＡｌ（ＯＨ）３との混合物である。 Comparative Examples 1 to 3
In Comparative Example 1, copper oxide NB manufactured by Nisshin Chemco was used. Comparative Example 2 is a mixture of copper oxide NB and ZnCO 3 of Comparative Example 1, Comparative Example 3 is a mixture of copper oxide NB, ZnCO 3 and SiO 2 of Comparative Example 1, and Comparative Example 4 is a comparative example. 1 is a mixture of copper oxide NB, ZnCO 3 , SiO 2 and Al (OH) 3 .
　赤外線反射性黒色顔料の製造条件を表１に、得られた赤外線反射性黒色顔料の諸特性を表２に、塗料及び塗膜の特性を表３に示した。 Table 1 shows the production conditions of the infrared reflective black pigment, Table 2 shows the properties of the obtained infrared reflective black pigment, and Table 3 shows the properties of the paint and the coating film.
　実施例から明らかなとおり、本発明に係る赤外線反射顔料は、キャストコート紙のような下地が白色の場合に優れた近赤外反射率を有するものであることが確認された。 As is clear from the examples, it was confirmed that the infrared reflective pigment according to the present invention has an excellent near infrared reflectance when the base such as cast-coated paper is white.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明に係る赤外線反射性黒色顔料は、赤外線反射性に優れ、かつ、Ｃｒ６＋、Ｃｏなどの有害な元素を含まないので安全な赤外線反射性黒色顔料として好適である。 The infrared reflective black pigment according to the present invention is suitable as a safe infrared reflective black pigment because it is excellent in infrared reflectivity and does not contain harmful elements such as Cr 6+ and Co.
　また、本発明に係る赤外線反射性黒色顔料を含有する樹脂組成物は、赤外線反射性に優れるので、樹脂組成物を公知の方法でシート又はフィルムとすることで、以下のような用途に利用することができる。 Moreover, since the resin composition containing the infrared reflective black pigment according to the present invention is excellent in infrared reflectivity, the resin composition is used in the following applications by making it into a sheet or film by a known method. be able to.
　本発明に係る赤外線反射性黒色顔料を含有する樹脂組成物から得られるシートは、黒色であるので農業用マルチシートに利用すれば、雑草の発生、育成を防止することが可能であり、さらに赤外線反射性に優れるので地面の温度上昇を抑えることが可能であり、黒色の農業用マルチシートとして好適に使用することができる。 Since the sheet obtained from the resin composition containing the infrared-reflective black pigment according to the present invention is black, if it is used for an agricultural multi-sheet, it is possible to prevent the generation and growth of weeds. Since it is excellent in reflectivity, it is possible to suppress an increase in the temperature of the ground, and it can be suitably used as a black agricultural multi-sheet.
　同様に、本発明に係る赤外線反射性黒色顔料を含有する樹脂組成物から得られるシートは太陽電池のバックシートに好適に使用することができる。太陽電池モジュールは、複数の太陽電池素子の表裏面がカバー材料で保護されている。太陽電池素子の裏面を保護するバックシートは、電力変換効率の点から高い反射性を有し、意匠の点から黒色を有するバックシートが好ましい。さらに太陽電池素子は高温になるほど発電効率が低下する。本発明に係る赤外線反射性黒色顔料を含有する樹脂組成物から得られるシートは、太陽電池のバックシートとして必要な特性を十分に備え、太陽電池のバックシートとして好ましい。 Similarly, the sheet | seat obtained from the resin composition containing the infrared reflective black pigment which concerns on this invention can be used suitably for the back seat | sheet of a solar cell. In the solar cell module, the front and back surfaces of a plurality of solar cell elements are protected by a cover material. The back sheet that protects the back surface of the solar cell element is preferably a back sheet having high reflectivity in terms of power conversion efficiency and black in terms of design. Furthermore, the power generation efficiency decreases as the temperature of the solar cell element increases. The sheet | seat obtained from the resin composition containing the infrared reflective black pigment which concerns on this invention is fully equipped with the characteristic required as a solar cell backsheet, and is preferable as a solar cell backsheet.

Claims (8)

  1. ＣｕとＺｎとＳｉとを含有する複合酸化物からなる赤外線反射性黒色顔料であって、該黒色顔料はＣｕ含有量が全金属元素に対して２０～９８．５ｍｏｌ％であり、Ｚｎ含有量が全金属元素に対して１～７０ｍｏｌ％であり、Ｓｉ含有量が全金属元素に対して０．５～６０ｍｏｌ％であることを特徴とする赤外線反射性黒色顔料。 An infrared reflective black pigment made of a composite oxide containing Cu, Zn and Si, wherein the black pigment has a Cu content of 20 to 98.5 mol% with respect to all metal elements, and a Zn content of An infrared reflective black pigment characterized by being 1 to 70 mol% with respect to all metal elements and having a Si content of 0.5 to 60 mol% with respect to all metal elements.
  2. ＣｕとＺｎとＳｉとＡｌとを含有する複合酸化物からなる赤外線反射性黒色顔料であって、該黒色顔料はＣｕ含有量が全金属元素に対して２０～９８ｍｏｌ％であり、Ｚｎ含有量が全金属元素に対して１～７０ｍｏｌ％であり、Ｓｉ含有量が全金属元素に対して０．５～６０ｍｏｌ％であり、Ａｌ含有量が全金属元素に対して０．５～６０ｍｏｌ％であることを特徴とする赤外線反射性黒色顔料。 An infrared reflective black pigment made of a composite oxide containing Cu, Zn, Si and Al, wherein the black pigment has a Cu content of 20 to 98 mol% with respect to all metal elements, and a Zn content of 1 to 70 mol% with respect to all metal elements, Si content is 0.5 to 60 mol% with respect to all metal elements, and Al content is 0.5 to 60 mol% with respect to all metal elements. An infrared reflective black pigment characterized by that.
  3. 前記黒色顔料の黒色度（Ｌ＊）が２９以下である請求項１又は２記載の黒色顔料。 The black pigment according to claim 1 or 2, wherein the black pigment has a blackness (L * ) of 29 or less.
  4. 前記黒色顔料の近赤外反射率が４３％以上である請求項１～３のいずれかに記載の赤外線反射性黒色顔料。 The infrared reflective black pigment according to any one of claims 1 to 3, wherein the black pigment has a near infrared reflectance of 43% or more.
  5. 前記黒色顔料の耐酸性が１０００ｐｐｍ以下である請求項１～４のいずれかに記載の赤外線反射性黒色顔料。 The infrared reflective black pigment according to any one of claims 1 to 4, wherein the acid resistance of the black pigment is 1000 ppm or less.
  6. 赤外線反射性黒色顔料の表面を、Ｓｉ、Ａｌ、Ｚｒ、Ｔｉ、Ｚｎ、Ｐから選ばれる一種以上の元素を含む化合物又は有機系表面処理剤で表面処理されている請求項１～５のいずれかに記載の赤外線反射性黒色顔料。 The surface of the infrared reflective black pigment is surface-treated with a compound containing one or more elements selected from Si, Al, Zr, Ti, Zn, and P, or an organic surface treatment agent. Infrared reflective black pigment described in 1.
  7. 請求項１～６のいずれかに記載の赤外線反射性黒色顔料を配合した塗料。 A paint comprising the infrared reflective black pigment according to any one of claims 1 to 6.
  8. 請求項１～６のいずれかに記載の赤外線反射性黒色顔料を用いて着色した樹脂組成物。 A resin composition colored with the infrared reflective black pigment according to any one of claims 1 to 6.
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