WO2010073633A1 - Infrared ray-reflecting black pigment, method for producing the same, and paint and resin composition using the same - Google Patents

Infrared ray-reflecting black pigment, method for producing the same, and paint and resin composition using the same Download PDF

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Publication number
WO2010073633A1
WO2010073633A1 PCT/JP2009/007136 JP2009007136W WO2010073633A1 WO 2010073633 A1 WO2010073633 A1 WO 2010073633A1 JP 2009007136 W JP2009007136 W JP 2009007136W WO 2010073633 A1 WO2010073633 A1 WO 2010073633A1
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Prior art keywords
black pigment
infrared reflective
reflective black
cupric oxide
core particles
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PCT/JP2009/007136
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French (fr)
Japanese (ja)
Inventor
真田和俊
丸山伸介
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戸田工業株式会社
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Filing date
Publication date
Priority claimed from JP2008328860A external-priority patent/JP5455148B2/en
Priority claimed from JP2008328859A external-priority patent/JP2010150353A/en
Application filed by 戸田工業株式会社 filed Critical 戸田工業株式会社
Publication of WO2010073633A1 publication Critical patent/WO2010073633A1/en

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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/004—Reflecting paints; Signal paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • the present invention relates to an infrared-reflective black pigment that does not contain harmful elements, contains cupric oxide, has excellent acid resistance, and can provide a heat-shielding paint having excellent infrared reflectivity.
  • the roofs of outdoor buildings are often dark to black in order to make the dirt inconspicuous, and in the case of buildings and automobiles whose exterior paint has a dark to black color.
  • buildings and automobiles having a light-to-white appearance paint it is easier to absorb sunlight, 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.
  • Patent Document 1 describes a black calcined pigment having a spinel structure composed of CoO, Cr 2 O 3 and Fe 2 O 3 , which contains Cr and also has an infrared wavelength range of 780 to 2500 nm. The average reflectance was less than 30%, and it was difficult to say that it had a sufficient heat shielding effect.
  • Patent Document 2 describes a black pigment composed of a calcined pigment containing Fe 2 O 3 as an essential component and containing Cr 2 O 3 , Mn 2 O 3, or NiO, but contains Cr. This is not preferable.
  • Patent Document 3 describes a black complex oxide composed of rare earth elements, alkaline earth metals and iron, but it is difficult to say that it has a sufficient heat shielding effect.
  • Patent Document 4 describes a strontium iron oxide perovskite having excellent blackness, and has an average reflectance of 10% or less in a visible light region wavelength of 250 to 780 nm and an infrared region wavelength of 780. Since the average reflectance at ⁇ 2500 nm is less than 30%, a sufficient heat shielding effect is not obtained.
  • Patent Document 5 describes a magnesium-aluminum-containing spinel with excellent blackness, but has an average reflectance of 10% or less at a visible light region wavelength of 250 to 780 nm and an infrared region wavelength of 780. Since the average reflectance at ⁇ 2500 nm is less than 30%, a sufficient heat shielding effect is not obtained.
  • Patent Document 6 CuO is excellent in blackness and heat shielding properties as a black pigment, but has a problem in acid resistance.
  • pigments mainly composed of CuO—Cr 2 O 3 have low solar reflectance and near infrared reflectance.
  • an infrared reflective black pigment that does not contain harmful elements and has excellent infrared reflectivity, and has already filed a patent application (see Patent Document 7).
  • This black pigment contains Fe, Co, and Al, and further includes a composite oxide containing one or more metal elements selected from Mg, Ca, Sr, Ba, Ti, Zn, Sn, Zr, Si, and Cu.
  • An infrared reflective black pigment having an average particle size of 0.02 to 2.0 ⁇ m, and containing no harmful elements and having excellent infrared reflectivity Have However, it cannot be said that the reflectance in the infrared region wavelength of 1500 nm is sufficiently high.
  • CuO as a black pigment other than the black pigment.
  • CuO is excellent in blackness and heat shielding properties, it has a problem in acid resistance. Furthermore, since CuO has a large specific gravity, storage stability as a paint is also a problem.
  • a black or brown pigment using CuO as a raw material has also been proposed, and a near-infrared reflective pigment containing a compound represented by the chemical formula Cu 2 MgO 3 has been disclosed (for example, see Patent Document 8).
  • 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. It has been. This applies not only to black pigments but also to greyish black gray pigments.
  • An object of the present invention is to provide an infrared reflective black pigment that does not contain harmful elements, contains cupric oxide, has excellent infrared reflectivity, and is excellent in acid resistance and paint stability.
  • the present invention is a black pigment having an average particle diameter of 0.02 to 5.0 ⁇ m obtained by coating the surface of core particles made of cupric oxide with a surface treatment agent, and the coating layer has acid resistance. It is an infrared reflective black pigment characterized by having a coating amount of 0.1 to 10% by weight based on cupric oxide (Invention 1).
  • the present invention provides the infrared reflecting property according to the first aspect, wherein the surface treatment agent for coating the surface is one or more compounds selected from Si, Al, Zr, Ti, Zn, and P, or an organic surface treatment agent. It is a black pigment (Invention 2).
  • this invention is an infrared reflective black pigment of this invention 1 or 2 whose brightness (L * ) is 30 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 having a solar reflectance of 18% or more (Invention 4).
  • the present invention also relates to an extender pigment whose core particles comprising cupric oxide are cupric oxide and a second component, a white pigment, and one or more pigments of iron oxide having a solar reflectance of 10% or more.
  • the molar ratio of the cupric oxide constituting the core particles of cupric oxide to the pigment of the second component is 0.1: 0.9 to 0.95: 0.
  • Any of the present inventions 1 to 4 which are .05 is an infrared reflective black pigment (Invention 5).
  • the present invention is the infrared reflective black pigment according to the present invention 5, wherein the lightness (L * ) is 20 or more and 50 or less (the present invention 6).
  • the present invention also includes a coating step of coating the surface of the core particles made of cupric oxide with a surface treatment agent, and the core particles made of cupric oxide coated with the surface treatment agent at a temperature of 150 to 300 ° C. It is the manufacturing method of the infrared reflective black-type pigment of this invention 1 which consists of the heat-processing process heat-processed by (this invention 7).
  • the method further includes a heat treatment step in which the core particles obtained in the mixing step are heat-treated at a temperature not higher than the melting point of the core particles before the coating step.
  • a heat treatment step in which the core particles obtained in the mixing step are heat-treated at a temperature not higher than the melting point of the core particles before the coating step.
  • the infrared reflective black pigment according to any one of the present inventions 1 to 6 or the infrared reflective black pigment obtained by the method for producing the infrared reflective black pigment according to any of the present invention 7 to 10 A paint characterized in that it is blended in a substrate (Invention 11).
  • the infrared reflective black pigment according to the present invention does not contain harmful elements, contains cupric oxide, has excellent infrared reflectivity, and is excellent in acid resistance and paint stability, so that it is an infrared reflective black pigment. It is suitable as.
  • the infrared-reflective black pigment according to the present invention has particles composed of cupric oxide as core particles, and the average particle diameter obtained by coating the surface of the core particles with a surface treatment agent is 0.02 to 5.0 ⁇ m. It is a black pigment, the coating layer has acid resistance, and the coating amount is 0.1 to 10% by weight with respect to cupric oxide.
  • the core particles may be cupric oxide particles, or any one or more of cupric oxide and an extender pigment as a second component, a white pigment, and iron oxide having a solar reflectance of 10% or more. It may be a mixture and / or composite with the above pigment.
  • the molar ratio of cupric oxide constituting the core and the pigment of the second component is 0.1: 0.9 to 1.0: 0.0, preferably Is 0.1: 0.9 to 0.95: 0.05, more preferably 0.1: 0.9 to 0.90: 0.1, and still more preferably 0.15: 0. 85 to 0.90: 0.1, particularly preferably 0.20: 0.80 to 0.90: 0.1.
  • cupric oxide molar ratio When the cupric oxide molar ratio is less than 0.1, the lightness becomes too high to be said to be a black pigment. On the other hand, when the molar ratio of cupric oxide is large, the specific gravity increases. Therefore, in applications where dispersibility in a solvent such as paint is required, a smaller specific gravity is preferable in terms of preventing sedimentation of black pigments.
  • the average particle size of the black pigment is preferably 0.025 to 4.8 ⁇ m, more preferably 0.04 to 4.5 ⁇ 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.
  • the coating layer covering the surface of the particles made of cupric oxide must have acid resistance.
  • the core particles are composed of cupric oxide particles having low acid resistance, so that the coating layer covering the core particles has acid resistance, thereby ensuring acid resistance as a pigment.
  • the coating amount is less than 0.1% by weight with respect to cupric oxide, the cupric oxide as the core particle cannot be sufficiently coated, and the chemical resistance of the pigment, particularly acid resistance is insufficient. It becomes.
  • the coating amount exceeds 10% by weight with respect to cupric oxide, the acid resistance effect is saturated, and it is uneconomical to coat more than necessary.
  • 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, aggregation is likely to occur due to an increase in intermolecular force due to particle miniaturization, so that it is difficult to uniformly coat the particle surface with a surface treatment agent. More preferably, it is 1.5 to 75 m 2 / g, and still more preferably 1.8 to 65 m 2 / g.
  • the lightness (L * ) of the infrared reflective black pigment according to the present invention is usually 50 or less.
  • the blackness is excellent and is usually 30.0 or less, more preferably 28 or less.
  • it is composed of a mixture and / or a composite of at least one of extender pigment, white pigment, and iron oxide having a solar reflectance of 10% or more, which is the second component, 40 or less is more preferable.
  • the lower limit of lightness (L * ) is usually 10. The lower limit is about 20 when the mixture is composed of an extender pigment, white pigment, and iron oxide having a solar reflectance of 10% or more and a mixture and / or composite with at least one pigment.
  • 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 that the blackness is excellent. More preferably, it is -1 to +10, and particularly preferably -1 to +5.
  • 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 that the blackness is excellent. More preferably, it is ⁇ 4 to +5, and particularly preferably ⁇ 2 to +5.
  • the infrared reflectivity of the infrared reflective black pigment according to the present invention is preferably 18% or more, more preferably 20% or more, when the lacquer color sample coating film is measured according to JIS R3106. Yes, more preferably 24% or more, particularly preferably 28% or more.
  • the content is 28% or more. If the solar reflectance is less than 18%, it cannot be said that the solar reflectance is sufficiently high.
  • the maximum value is 70%.
  • the infrared reflective black pigment according to the present invention preferably has a glossiness (GLOSS value) of 50 or more at 60 ° -60 ° when the pigment is coated.
  • glossiness GLOSS value
  • the glossiness (GLOSS value) is less than 50, sufficient glossiness cannot be obtained and it is difficult to say that the dispersibility is excellent.
  • the infrared reflective black pigment according to the present invention preferably has a true specific gravity of 3.0 to 6.0. If the true specific gravity is within the above range, excellent dispersibility is exhibited when the infrared-reflective black pigment according to the present invention is dispersed in the paint-constituting substrate. It also exhibits excellent storage stability as a paint.
  • the average particle diameter of the core particles is 0.018 to 4.80 ⁇ m, preferably 0.02 to 4.5 ⁇ m, more preferably 0.04 to 4.0 ⁇ m. .
  • the average particle diameter of the core particles is less than 0.018 ⁇ m, the intermolecular force increases due to the finer particles and aggregation easily occurs, so that it is difficult to uniformly coat the surface of the core particles with the surface treatment agent.
  • the average particle diameter exceeds 4.8 ⁇ m, the resulting infrared reflective black pigment also becomes coarse particles and the coloring power is reduced.
  • the shape of the core particle is not limited to a specific shape, but is spherical, granular, octahedral, hexahedral, polyhedral, etc., acicular, spindle, rice, etc. Can be used. Considering the dispersibility of the obtained black pigment, spherical particles and granular particles are preferable.
  • the particle shape and particle size of the infrared reflective composite black pigment according to the present invention largely depend on the particle shape and particle size of the core particle, have a particle form similar to the core particle, and slightly larger than the core particle. Have a size.
  • the BET specific surface area of the core particles is 1 to 200 m 2 / g, preferably 1.5 to 150 m 2 / g, more preferably 2.0 to 100 m 2 / g.
  • the core particles are coarse or particles are sintered between the particles, and the resulting pigment is also coarse particles, resulting in a decrease in coloring power. To do.
  • the BET specific surface area exceeds 200 m 2 / g, aggregation is likely to occur due to an increase in intermolecular force due to particle miniaturization, making it difficult to uniformly coat the surface of the core particles with a surface treatment agent.
  • cupric oxide particles are, for example, neutralized with sodium hydroxide and sulfuric acid into a copper sulfate aqueous solution in addition to commercially available products to make cupric hydroxide, washed with water, dried and heat treated You can also get it.
  • neutralizing an aqueous copper sulfate solution it can also be obtained by mixing an extender pigment, a white pigment and iron oxide in advance.
  • the core particle As the core particle, a mixture and / or a composite of cupric oxide and one or more of an extender pigment, a white pigment and iron oxide having a solar reflectance of 10% or more are used.
  • the extender pigment, white pigment and iron oxide constituting the core particles have a solar reflectance of 10% or more. If the solar reflectance of these pigments is less than 10%, an infrared reflective black pigment having a sufficiently high solar reflectance cannot be obtained.
  • extender pigments include silica fine particles such as silica powder, white carbon, fine powder silicic acid, diatomaceous earth, clay, calcium carbonate, barium carbonate, barium sulfate, gypsum, alumina white, talc, transparent titanium oxide, and satin white.
  • silica fine particles such as silica powder, white carbon, fine powder silicic acid, diatomaceous earth, clay, calcium carbonate, barium carbonate, barium sulfate, gypsum, alumina white, talc, transparent titanium oxide, and satin white.
  • white pigments examples include zinc oxide, basic lead sulfate, lead sulfate, lithopone, zinc sulfide, titanium oxide, and antimony oxide.
  • iron oxide having a solar reflectance of 10% or more examples include manganese-containing hematite containing 5 to 40% by weight of manganese with respect to hematite and manganese-containing hematite.
  • the surface treatment agent for coating the core particles uses at least one compound selected from Si, Al, Zr, Ti, Zn, and P, or an organic surface treatment agent. be able to.
  • aluminum compounds As one or more kinds of compounds selected from Si, Al, Zr, Ti, Zn, and P, as aluminum compounds, aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride, and aluminum nitrate; and aluminates such as sodium aluminate Examples include alkali salts.
  • 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 core particles are cupric oxide particles
  • the surface of the core particles is coated with a surface treatment agent.
  • the core particles are composed of cupric oxide particles and a second component pigment, any one of cupric oxide particles and an extender pigment as a second component, a white pigment, and iron oxide having a solar reflectance of 10% or more. Thoroughly mix with more than one type of pigment.
  • an apparatus capable of applying a shearing force to the powder layer is preferable, and an apparatus capable of simultaneously performing shearing, spatula and compression, for example, a wheel type kneader, a ball type kneader, a blade type It is preferable to use a 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.
  • heat treatment is performed at a temperature below the melting point of the mixture of cupric oxide particles and a second component, an extender pigment, a white pigment, and an iron oxide having a solar reflectance of 10% or more. It is preferable to do.
  • a preferable heat treatment temperature is a temperature not higher than the melting point of the mixture and not lower than 300 ° C. and not higher than 850 ° C. More preferably, the temperature is 300 ° C. or higher and 750 ° C. or lower. More preferably, the temperature is 300 ° C. or more and 600 ° C. or less.
  • the mixture can be combined by heat treatment at a temperature not higher than the melting point of the mixture. By combining the mixture, the chemical resistance becomes higher.
  • the mixture melts.
  • the heat treatment is performed at a temperature exceeding 850 ° C. even if the temperature is lower than the melting point of the mixture, the core particles become coarse and form a coating film. This is not preferable because the glossiness when it is deteriorated.
  • the surface of the core particle is coated with a surface treatment agent.
  • the infrared-reflective black pigment according to the present invention can be obtained by heat-treating the particles coated with the surface treatment agent at a temperature of 150 to 300 ° C.
  • a temperature of 150 to 300 ° C By mixing the cupric oxide particles and the surface treatment agent, an infrared-reflective black pigment coated on the particle surface can be obtained.
  • the chemical resistance, particularly acid resistance, of the coating layer is poor. It is enough.
  • the particles coated with the surface treatment agent are heat-treated at a temperature of less than 150 ° C.
  • the coating layer becomes sufficiently strong at a temperature of 300 ° C. and does not need to be heated above 300 ° C. Further, heating at a temperature higher than necessary exceeding 300 ° C. is not preferable because the specific surface area of the cupric oxide particles that are the core particles decreases.
  • the coating of the surface treatment agent on the surface of the core particles may be performed according to a conventional method such as a dry method or a wet method.
  • the core particles and the surface treatment agent may be mechanically mixed and stirred, or may be mechanically mixed and stirred while spraying the surface treatment agent on the core particles. Almost all of the added surface treatment agent is coated on the surface of the core particles.
  • the aggregation of the core particles is previously unraveled using a pulverizer.
  • an apparatus capable of applying a shearing force to the powder layer is preferable, and an apparatus capable of simultaneously performing 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 mixing and stirring conditions for the core particles and the surface treatment agent may be appropriately adjusted so that the surface treatment agent is coated on the surface of the core particles as uniformly as possible.
  • the line load is 19.6 to 1960 N / cm (2 to 2). 200 Kg / cm), more preferably 98 to 1470 N / cm (10 to 150 Kg / cm), most preferably 147 to 980 N / cm (15 to 100 Kg / cm), and the treatment time is 5 minutes to 24 hours. More preferably, the range is from 10 minutes to 20 hours, and the stirring speed is preferably from 2 to 2000 rpm, more preferably from 5 to 1000 rpm, and most preferably from 10 to 800 rpm.
  • the silane coupling agent when dry-processed with a Henschel mixer, the core particles, water, auxiliary agent, and alcohol are premixed for 1 hour at low speed. Then, it adjusts to high speed rotation and maintains at 130 degreeC for 1 hour, Then, it cools and discharges with water. Thereafter, it is heated at 150 ° C. for 1 hour.
  • one or two or more soluble compounds selected from Si, Al, Zr, Ti, Zn, and P are added to and mixed with the wet-dispersed core particle slurry while adjusting the pH with acid or alkali. What is necessary is just to coat. Thereby, the surface of a core particle can be coat
  • the organic surface treatment agent may be put on and coated on the wet-dispersed core particle slurry.
  • zirconium sulfate, sodium aluminate, sulfuric acid, and sodium hydroxide are dropped so that the pH becomes 6 to 8 while stirring the core particles in pure water. Add, maintain at 80 ° C. for 1 hour, then wash with water and filter dry. Further, it may be heated at a temperature of 180 ° C. for 1 hour.
  • the blending ratio of the infrared reflective black pigment in the paint according to the present invention can be used in a range of 0.5 to 100 parts by weight with respect to 100 parts by weight of the paint base material, and the handling property of the paint is taken into consideration.
  • the amount is preferably 1.0 to 100 parts by weight.
  • paint base material resin, solvent, and if necessary, fats and oils, antifoaming agent, extender pigment, organic 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 cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve and other glycol ether solvents, 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.
  • alcohol-based solvents usually used for water-based paints
  • alcohol-based solvents such as ethyl alcohol, propyl alcohol and butyl alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve,
  • 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.
  • organic pigment phthalocyanine blue, phthalocyanine green, perylene black and the like can be used.
  • a method of use there is a method of mixing so as to firmly adhere to the surface of the black pigment, or a method of adding at the same time when forming a paint.
  • 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. Considering it, it is preferably 0.05 to 150 parts by weight, more preferably 0.1 to 100 parts by weight.
  • an infrared reflective black pigment and a known thermoplastic resin as well as extender pigments, organic pigments, lubricants, plasticizers, antioxidants, ultraviolet absorbers, various Additives such as stabilizers are 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, phenolic 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 total 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 thoroughly 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 After destroying the pigment aggregate and uniformly dispersing the infrared-reflective black pigment in the resin composition, it is molded into a shape suitable for the purpose and used.
  • the resin composition according to the present invention can also be obtained via a master batch pellet.
  • Master batch pellets in the present invention require a binder resin as a constituent substrate of the paint and the resin composition and the infrared-reflective black pigment, mixing a ribbon blender, Nauter mixer, Henschel mixer, super mixer, etc. Kneaded by mixing with a machine, kneaded with a known single-screw kneading extruder or twin-screw kneading extruder, etc., then cut, or kneaded by kneading the mixture with a Banbury mixer, pressure kneader, etc. Manufactured by crushing, molding, or cutting an object.
  • the supply of the binder resin and the infrared-reflective black pigment to the kneader may be carried out in 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 masterbatch 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. is there.
  • the amount is less than 1 part by weight, the melt viscosity at the time of kneading is insufficient, and it is difficult to disperse and mix the infrared reflective black pigment well.
  • the infrared reflective black pigment according to the present invention is a black pigment containing cupric oxide without containing harmful elements and having excellent infrared reflectivity. This is the fact that it is excellent in acid resistance and paint stability.
  • the infrared-reflective black pigment according to the present invention has cupric oxide which is excellent in infrared reflectivity but inferior in acid resistance as a core particle, the surface of the core particle is coated with a coating layer having acid resistance. It was possible to realize excellent acid resistance while having high infrared reflectivity.
  • the infrared reflective black pigment according to the present invention contains cupric oxide which is excellent in infrared reflectivity but inferior in acid resistance and has a large true specific gravity, it is a body pigment which is a cupric oxide particle and a second component.
  • a mixture of a white pigment and one or more pigments of iron oxide having a solar reflectance of 10% or more and / or a composite is used as a core particle, and the surface of the core particle is coated with a coating layer having acid resistance By doing so, it was possible to prevent the separation of components during the dispersion of the paint and to realize excellent chemical resistance, particularly high acid resistance while having high infrared reflectivity.
  • high acid resistance could be obtained by coating the surface of the core particle with a surface treatment agent and then heat-treating it at a predetermined temperature. Furthermore, it was possible to realize better chemical resistance by heat treatment at a predetermined temperature before coating the core particles with the surface treatment agent.
  • the infrared reflective black pigment according to the present invention is any one of cupric oxide particles and extender pigments that are the second component, white pigment, and iron oxide whose solar reflectance is 10% or more. Since it consists of a mixture and / or composite with the above pigments, it becomes possible to lower the specific gravity as compared with the case where only cupric oxide particles are used as the core particles. Paint storage stability could be realized.
  • the infrared reflective black pigment according to the present invention does not contain a harmful metal element such as Cr 6+ and is a safe pigment.
  • a typical embodiment of the present invention is as follows.
  • the average particle size of the particles was measured by measuring the particle size of 350 particles shown in the electron micrograph, and the average value was shown.
  • the specific surface area is indicated by a value measured by the BET method.
  • 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. Add 4.5g, knead, paint, and apply the coated piece (coating thickness: about 30 ⁇ m) coated on cast coated paper using a 150 ⁇ m (6mil) applicator. Measurement was carried out using “total MSC-IS-2D” (manufactured by Suga Test Instruments Co., Ltd.), and the color index (L * value, a * value, b * value) was indicated according to JIS Z8729.
  • the true specific gravity (density) of the infrared reflective composite black pigment was measured according to “Pigment Test Method” of JIS K5101.
  • the solar reflectance of the infrared-reflective black pigment was measured in accordance with JIS R3106 using a “spectrophotometer UV-4100” (HITACHI) for the coating piece prepared for measuring the hue.
  • HITACHI spectrophotometer UV-4100
  • the acid resistance of the infrared-reflective black pigment was evaluated according to JIS K5101-8 “Pigment Test Method Part 8: Chemical Resistance”. Add 2 g of pigment and 20 ml of 2% sulfuric acid to the test tube, and seal it. After shaking and mixing and allowing to stand at room temperature, the amount of Cu in the solution after filtration and separation was measured by ICP, and dissolved Cu was analyzed.
  • the glossiness (GLOSS value) of the infrared reflective black pigment is 60 using a color sample obtained by measuring the color determination and the solar reflectance by using “Digital Variable Glossmeter UGV-5D” (manufactured by Suga Test Instruments Co., Ltd.). The value at ° -60 ° is shown. It shows that the dispersibility of the coating material which mix
  • the evaluation of the paint containing the infrared reflective black pigment was performed as follows. In mayonnaise bottle (internal volume 140 ml), 90 g of glass beads, 10 g of infrared reflective 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 aluminum alkyd resin (clear), it was dispersed for 5 minutes with a paint conditioner and separated from glass beads. About the coating material after 5 hours of stationary, the separation state was visually judged and stability was evaluated. Moreover, it left still for 24 hours and the black pigment was settled. Evaluation was made based on the ease and difficulty of redispersibility when the precipitate was stirred with a stirrer.
  • Examples 1 to 4 and Comparative Examples 1 to 4 show that when the core particles are made of cupric oxide particles
  • Examples 5 to 10 and Comparative Examples 5 to 9 show that the core particles are Example of the case of a mixture and / or a composite of cupric oxide particles and a second component, an extender pigment, a white pigment, and an iron oxide having a solar reflectance of 10% or more. It is.
  • Example 1 Add 2.5% by weight of silane coupling agent (1% by weight in terms of SiO 2 ), 0.25% by weight of water and 1.75% by weight of alcohol to CuO particles, and reserve for 1 hour at low speed with a Henschel mixer. Mixed. Thereafter, the Henschel mixer was adjusted to high speed rotation, maintained at 130 ° C. for 1 hour, cooled with water and discharged. Thereafter, the core particles coated with the surface treatment agent were heat-treated at 150 ° C. for 1 hour. The heat-treated product was pulverized to obtain a black pigment having an average particle size of 0.3 ⁇ m and a BET specific surface area of 9.5 m 2 / g.
  • the coating amount of the obtained black pigment was 1% by weight in terms of SiO 2 with respect to the core particles, and the solar reflectance was 25%.
  • the concentration of Cu in the solution was as low as 890 ppm, and the redispersibility after settling in the paint was also good.
  • Example 2 While stirring in pure water, 6.0% by weight of sodium aluminate (2% by weight in terms of Al 2 O 3 ) is added dropwise to CuO particles so that sulfuric acid and sodium hydroxide have a pH of 6-8. And maintained at 80 ° C. for 1 hour, then washed with water and dried by filtration. Thereafter, heat treatment was performed at a temperature of 250 ° C. for 1 hour. The heat-treated product was pulverized to obtain a black pigment having an average particle size of 0.85 ⁇ m and a BET specific surface area of 2.6 m 2 / g.
  • the coating amount of the obtained black pigment was 2% by weight in terms of Al 2 O 3 with respect to the core particles, and the solar reflectance was 28%.
  • the concentration of Cu in the solution was as small as 340 ppm, and the redispersibility after settling in the paint was also good.
  • Example 3 to Example 4 Comparative Example 1 to Comparative Example 4: A black pigment was obtained in the same manner as in Example 1 except that the surface treatment method, the surface treatment agent, the coating amount, and the heat treatment temperature after the surface treatment were changed.
  • Tables 1 and 2 show the production conditions of Examples 1 to 4 and Comparative Examples 1 to 4, the properties of the obtained infrared reflective black pigments, and the properties of the paint and the coating film.
  • Example 5 The molar ratio of CuO particles and Al 2 O 3 particles was 0.8: 0.2, and these were mixed and stirred at room temperature to obtain core particles.
  • a silane coupling agent 1% by weight in terms of SiO 2
  • 0.25% by weight of water and 1.75% by weight of alcohol are added, and the Henschel mixer is rotated at a low speed for 1 hour. Premixed. Thereafter, the Henschel mixer was adjusted to high speed rotation, maintained at 130 ° C. for 1 hour, cooled with water and discharged. Thereafter, the core particles coated with the surface treatment agent were heat-treated at 160 ° C. for 1 hour.
  • the heat-treated product was pulverized to obtain a composite black pigment having an average particle size of 0.4 ⁇ m and a BET specific surface area of 9.8 m 2 / g.
  • the coating amount of the obtained composite black pigment was 1% by weight in terms of SiO 2 with respect to the core particles, and the true specific gravity was 5.6 g / cm 3 .
  • the solar reflectance was 25%, and as a result of evaluating acid resistance, the concentration of Cu in the solution was as small as 540 ppm and was stable without separation even when used as a paint.
  • Example 6 The molar ratio of CuO particles and SiO 2 particles was 0.5: 0.5, and these were mixed and stirred at room temperature to obtain core particles. While stirring in pure water, 6.0% by weight of sodium aluminate (2% by weight in terms of Al 2 O 3 ) was added dropwise to the core particles so that sulfuric acid and sodium hydroxide would have a pH of 6-8. Add, maintain at 80 ° C. for 1 hour, then wash with water and filter dry. Thereafter, heat treatment was performed at a temperature of 180 ° C. for 1 hour. The heat-treated product was pulverized to obtain a black pigment having an average particle size of 0.09 ⁇ m and a BET specific surface area of 65 m 2 / g.
  • the coating amount of the obtained black pigment was 2% by weight in terms of Al 2 O 3 with respect to the core particles, and the true specific gravity was 4.2 g / cm 3 .
  • the solar reflectance was 28%.
  • the concentration of Cu in the solution was as low as 190 ppm, and it was stable without separation even when used as a paint.
  • Examples 7 to 10 and Comparative Examples 5 to 7 In Examples 7 to 10 and Comparative Example 6, the CuO particles and the second component particles were mixed and stirred, and then heat treatment was performed, followed by surface treatment and heat treatment. In addition, the heat treatment temperature, the surface treatment method, the surface treatment agent and the coating amount, and the heating temperature after the surface treatment were changed.
  • Comparative Example 6 the pigment settled and separated when used as a paint
  • Comparative Examples 5 and 7 CuO and the second component pigment separated and settled when used as a paint.
  • Tables 3, 4 and 5 show the production conditions of Examples 5 to 10 and Comparative Examples 5 to 7, the characteristics of the obtained infrared reflective composite black pigment, and the characteristics of the paint and the coating film.
  • the infrared reflective black pigment according to the present invention is suitable as an infrared reflective black pigment because it is excellent in infrared reflectivity, acid resistance and paint stability. Moreover, since the resin composition containing the infrared reflective composite 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. can do.
  • the sheet obtained from the resin composition containing the infrared-reflective black pigment according to the present invention is black, it is possible to prevent the generation and growth of weeds when used for agricultural multi-sheets. Since it has excellent infrared 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.
  • a solar cell backsheet 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 which protects the back surface of a solar cell element has high reflectivity from the point of power conversion efficiency, and the back sheet which has a black type from the point of a design is preferable. Furthermore, 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.
  • the film obtained from the resin composition containing the infrared reflective black pigment according to the present invention is excellent in blackness and infrared reflectiveness, it is preferably used as a colored film to be attached to a window glass of a vehicle or a building. be able to.

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Abstract

Provided is an infrared ray-reflecting black pigment having an average particle size of 0.02 to 5.0 µm that is obtained by coating the surface of core particles formed from cupric oxide using a surface treatment agent such that the coating layer is acid-resistant and the amount of coating is 0.1 to 10 wt% with respect to the cupric oxide.  Preferably the core particles formed from cupric oxide are core particles formed from a mixture and/or composite of the cupric oxide and a second component consisting of one or more pigments selected from the group comprising extender pigment, white pigment, and iron oxide having a sunlight reflectivity of 10% or greater, wherein the molar ratio of cupric oxide and the second component pigment which make up the core particles formed from cupric oxide is 0.1:0.9 to 0.95:0.5.  The infrared ray-reflecting black pigment is a black pigment that comprises cupric oxide but is free of toxic elements, and has not only excellent infrared ray reflectivity, but also excellent acid resistance and paint stability.

Description

赤外線反射性黒色系顔料、該赤外線反射性黒色系顔料の製造方法、該赤外線反射性黒色系顔料を用いた塗料及び樹脂組成物Infrared reflective black pigment, method for producing the 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、酸化第二銅を含み、耐酸性に優れると共に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系顔料に関する。 The present invention relates to an infrared-reflective black pigment that does not contain harmful elements, contains cupric oxide, has excellent acid resistance, and 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、殊に、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, in particular, the roofs of outdoor buildings are often dark to black in order to make the dirt inconspicuous, and in the case of buildings and automobiles whose exterior paint has a dark to black color. Compared to buildings and automobiles having a light-to-white appearance paint, it is easier to absorb sunlight, 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）。また、黒色度に優れたストロンチウム鉄酸化物ペロブスカイトが知られている（例えば特許文献４参照）。また、黒色度に優れたマグネシウム、アルミニウム含有酸化鉄が知られている（例えば特許文献５参照）。しかしながら次のような課題を有している。 Conventionally, heat-shielding black paints are known in order to reduce the rise in the internal temperature of buildings and automobiles having dark to black exterior paint (see, for example, Patent Documents 1 to 3). In addition, strontium iron oxide perovskite having excellent blackness is known (for example, see Patent Document 4). Further, magnesium and aluminum-containing iron oxides having excellent blackness are known (see, for example, Patent Document 5). However, it has the following problems.
　特許文献１には、ＣｏＯ、Ｃｒ２Ｏ３及びＦｅ２Ｏ３からなるスピネル構造を有する黒色焼成顔料が記載されているが、Ｃｒを含有するものであり、また、赤外線領域波長７８０～２５００ｎｍにおける平均反射率が３０％未満であり、十分な遮熱効果を有するとは言い難いものであった。 Patent Document 1 describes a black calcined pigment having a spinel structure composed of CoO, Cr 2 O 3 and Fe 2 O 3 , which contains Cr and also has an infrared wavelength range of 780 to 2500 nm. The average reflectance was less than 30%, and it was difficult to say that it had a sufficient heat shielding effect.
　また、特許文献２には、Ｆｅ２Ｏ３を必須成分とし、Ｃｒ２Ｏ３、Ｍｎ２Ｏ３又はＮｉＯを含む焼成顔料からなる黒色系顔料が記載されているが、Ｃｒを含有するものであるので好ましくない。 Patent Document 2 describes a black pigment composed of a calcined pigment containing Fe 2 O 3 as an essential component and containing Cr 2 O 3 , Mn 2 O 3, or NiO, but contains Cr. This is not preferable.
　また、特許文献３には、希土類元素、アルカリ土類金属及び鉄からなる黒色複合酸化物が記載されているが、十分な遮熱効果を有するとは言い難いものであった。 Further, Patent Document 3 describes a black complex oxide composed of rare earth elements, alkaline earth metals and iron, but it is difficult to say that it has a sufficient heat shielding effect.
　また、特許文献４には、黒色度に優れたストロンチウム鉄酸化物ペロブスカイトが記載されているが、可視光領域波長２５０～７８０ｎｍにおける平均反射率が１０％以下であって、且つ、赤外線領域波長７８０～２５００ｎｍにおける平均反射率が３０％未満であるので、十分な遮熱効果は得られていない。 Patent Document 4 describes a strontium iron oxide perovskite having excellent blackness, and has an average reflectance of 10% or less in a visible light region wavelength of 250 to 780 nm and an infrared region wavelength of 780. Since the average reflectance at ˜2500 nm is less than 30%, a sufficient heat shielding effect is not obtained.
　また、特許文献５には、黒色度に優れたマグネシウム、アルミニウム含有スピネルが記載されているが、可視光領域波長２５０～７８０ｎｍにおける平均反射率が１０％以下であって、且つ、赤外線領域波長７８０～２５００ｎｍにおける平均反射率が３０％未満であるので、十分な遮熱効果は得られていない。 Patent Document 5 describes a magnesium-aluminum-containing spinel with excellent blackness, but has an average reflectance of 10% or less at a visible light region wavelength of 250 to 780 nm and an infrared region wavelength of 780. Since the average reflectance at ˜2500 nm is less than 30%, a sufficient heat shielding effect is not obtained.
また、特許文献６には、ＣｕＯは、黒色系顔料として黒色度に優れかつ熱遮蔽性に優れるが、耐酸性に課題がある。一方でＣｕＯ－Ｃｒ２Ｏ３を主成分とする顔料は、日射反射率及び近赤外線反射率が低いとの実験データも開示されている。 In Patent Document 6, CuO is excellent in blackness and heat shielding properties as a black pigment, but has a problem in acid resistance. On the other hand, it is also disclosed experimental data that pigments mainly composed of CuO—Cr 2 O 3 have low solar reflectance and near infrared reflectance.
　上記課題を解決するため、本出願人は、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赤外線反射性黒色系顔料を開発し既に特許出願を行っている（特許文献７参照）。この黒色系顔料は、ＦｅとＣｏとＡｌを含有し、更に、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｔｉ、Ｚｎ、Ｓｎ、Ｚｒ、Ｓｉ及びＣｕから選ばれる一種以上の金属元素を含有する複合酸化物からなる黒色系顔料であって、該黒色系顔料の平均粒子径が０．０２～２．０μｍである赤外線反射性黒色系顔料であり、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えない。 In order to solve the above problems, the present applicant has developed an infrared reflective black pigment that does not contain harmful elements and has excellent infrared reflectivity, and has already filed a patent application (see Patent Document 7). . This black pigment contains Fe, Co, and Al, and further includes a composite oxide containing one or more metal elements selected from Mg, Ca, Sr, Ba, Ti, Zn, Sn, Zr, Si, and Cu. An infrared reflective black pigment having an average particle size of 0.02 to 2.0 μm, and containing no harmful elements and having excellent infrared reflectivity Have However, it cannot be said that the reflectance in the infrared region wavelength of 1500 nm is sufficiently high.
　上記黒色系顔料以外の黒色系顔料としてＣｕＯがある。ＣｕＯは黒色度に優れ、かつ熱遮蔽性に優れるものの耐酸性に課題がある。さらにＣｕＯは比重が大きいため塗料としての貯蔵安定性も問題となる。ＣｕＯを原料とした黒色又は茶色の顔料も提案されており、化学式Ｃｕ２ＭｇＯ３で表される化合物を含有する近赤外線反射顔料が開示されている（例えば特許文献８参照）。 There is CuO as a black pigment other than the black pigment. Although CuO is excellent in blackness and heat shielding properties, it has a problem in acid resistance. Furthermore, since CuO has a large specific gravity, storage stability as a paint is also a problem. A black or brown pigment using CuO as a raw material has also been proposed, and a near-infrared reflective pigment containing a compound represented by the chemical formula Cu 2 MgO 3 has been disclosed (for example, see Patent Document 8).
　銅含有複合酸化物としてＣｕＭｙＯｚがある。焼成後の色が灰色や黒色となる比較例が示されてはいるが、耐酸性に課題がある（例えば特許文献９参照）。 There is CuMyOz as a copper-containing composite oxide. Although the comparative example from which the color after baking becomes gray or black is shown, there exists a subject in acid resistance (for example, refer patent document 9).
特開２０００－７２９９０号公報JP 2000-72990 A 特開２００１－３１１０４９号公報JP 2001-311049 A 特開２００４－８３６１６号公報JP 2004-83616 A 特開２０００－２６４６３９号公報JP 2000-264639 A 特開２００３－２３８１６４号公報JP 2003-238164 A 特開２００２－３３１６１１号公報JP 2002-331611 A 特開２００７－１９７５７０号公報JP 2007-197570 A 特開２００７－２０４２９６号公報JP 2007-204296 A 特開２００５－７５６７４号公報JP 2005-75674 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系顔料としていくつかの黒色系顔料が開発されているものの、これら顔料も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。これは黒色系顔料のみならず灰色がかった黒灰色顔料にも当てはまる。 Although some 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. It has been. This applies not only to black pigments but also to greyish black gray pigments.
　本発明の目的は、有害な元素を含有せず、酸化第二銅を含み、優れた赤外線反射性を有すると共に耐酸性及び塗料安定性に優れる赤外線反射性黒色系顔料を提供することである。 An object of the present invention is to provide an infrared reflective black pigment that does not contain harmful elements, contains cupric oxide, has excellent infrared reflectivity, and is excellent in acid resistance and paint stability.
　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、酸化第二銅から成る芯粒子の表面を表面処理剤で被覆し得られる平均粒子径が０．０２～５．０μｍの黒色系顔料であって、被覆層は耐酸性を有し、被覆量が酸化第二銅に対して０．１～１０重量％であることを特徴とする赤外線反射性黒色系顔料である（本発明１）。 That is, the present invention is a black pigment having an average particle diameter of 0.02 to 5.0 μm obtained by coating the surface of core particles made of cupric oxide with a surface treatment agent, and the coating layer has acid resistance. It is an infrared reflective black pigment characterized by having a coating amount of 0.1 to 10% by weight based on cupric oxide (Invention 1).
　また、本発明は、表面を被覆する表面処理剤が、Ｓｉ、Ａｌ、Ｚｒ、Ｔｉ、Ｚｎ、Ｐから選ばれる一種以上の化合物又は有機系表面処理剤である本発明１に記載の赤外線反射性黒色系顔料である（本発明２）。 In addition, the present invention provides the infrared reflecting property according to the first aspect, wherein the surface treatment agent for coating the surface is one or more compounds selected from Si, Al, Zr, Ti, Zn, and P, or an organic surface treatment agent. It is a black pigment (Invention 2).
　また、本発明は、明度（Ｌ＊）が３０以下である本発明１又は２記載の赤外線反射性黒色系顔料である（本発明３）。 Moreover, this invention is an infrared reflective black pigment of this invention 1 or 2 whose brightness (L * ) is 30 or less (this invention 3).
　また、本発明は、日射反射率が１８％以上である本発明１～３の何れかに記載の赤外線反射性黒色系顔料である（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 having a solar reflectance of 18% or more (Invention 4).
　また、本発明は、酸化第二銅から成る芯粒子が酸化第二銅と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料との混合物及び／又は複合化物から成り、酸化第二銅から成る芯粒子を構成する酸化第二銅と第二成分の顔料とのモル比が０．１：０．９～０．９５：０．０５である本発明１～４の何れかに赤外線反射性黒色系顔料である（本発明５）。 The present invention also relates to an extender pigment whose core particles comprising cupric oxide are cupric oxide and a second component, a white pigment, and one or more pigments of iron oxide having a solar reflectance of 10% or more. The molar ratio of the cupric oxide constituting the core particles of cupric oxide to the pigment of the second component is 0.1: 0.9 to 0.95: 0. Any of the present inventions 1 to 4 which are .05 is an infrared reflective black pigment (Invention 5).
　また本発明は、明度（Ｌ＊）が２０以上５０以下である本発明５に記載の赤外線反射性黒色系顔料である（本発明６）。 Further, the present invention is the infrared reflective black pigment according to the present invention 5, wherein the lightness (L * ) is 20 or more and 50 or less (the present invention 6).
　また、本発明は、酸化第二銅から成る芯粒子の表面を表面処理剤で被覆する被覆工程と、前記表面処理剤で被覆された酸化第二銅から成る芯粒子を１５０～３００℃の温度で加熱処理する加熱処理工程とから成る本発明１に記載の赤外線反射性黒色系顔料の製造方法である（本発明７）。 The present invention also includes a coating step of coating the surface of the core particles made of cupric oxide with a surface treatment agent, and the core particles made of cupric oxide coated with the surface treatment agent at a temperature of 150 to 300 ° C. It is the manufacturing method of the infrared reflective black-type pigment of this invention 1 which consists of the heat-processing process heat-processed by (this invention 7).
　酸化第二銅粒子と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料粒子とを混合し芯粒子を得る混合工程と、前記混合工程で得られる芯粒子の表面を表面処理剤で被覆する被覆工程と、前記被覆工程で得られる表面処理剤で被覆された芯粒子を１５０～３００℃の温度で加熱する加熱処理工程とから成る本発明５に記載の赤外線反射性黒色系顔料の製造方法である（本発明８）。 A mixing step of obtaining core particles by mixing cupric oxide particles and an extender pigment as a second component, a white pigment, and one or more pigment particles of iron oxide having a solar reflectance of 10% or more; and A coating step of coating the surface of the core particles obtained in the mixing step with a surface treatment agent, and a heat treatment step of heating the core particles coated with the surface treatment agent obtained in the coating step at a temperature of 150 to 300 ° C. This is a method for producing an infrared reflective black pigment according to the present invention 5 (invention 8).
　さらに混合工程の後、被覆工程前に、混合工程で得られる芯粒子を該芯粒子の融点以下の温度で熱処理する熱処理工程を含む本発明８に記載の赤外線反射性黒色系顔料の製造方法である（本発明９）。 Furthermore, in the method for producing an infrared-reflective black pigment according to the present invention 8, the method further includes a heat treatment step in which the core particles obtained in the mixing step are heat-treated at a temperature not higher than the melting point of the core particles before the coating step. There is (Invention 9).
　熱処理工程における熱処理温度が３００℃以上８５０℃以下である本発明９に記載の赤外線反射性黒色系顔料の製造方法である（本発明１０）。 It is a manufacturing method of the infrared reflective black pigment of this invention 9 whose heat processing temperature in a heat treatment process is 300 to 850 degreeC (this invention 10).
　本発明１～６の何れかに記載の赤外線反射性黒色系顔料または本発明７～１０の何れかに記載の赤外線反射性黒色系顔料の製造方法により得られる赤外線反射性黒色系顔料を塗料構成基材中に配合したことを特徴とする塗料である（本発明１１）。 The infrared reflective black pigment according to any one of the present inventions 1 to 6 or the infrared reflective black pigment obtained by the method for producing the infrared reflective black pigment according to any of the present invention 7 to 10 A paint characterized in that it is blended in a substrate (Invention 11).
　本発明１～６の何れかに記載の赤外線反射性黒色系顔料または本発明７～１０の何れかに記載の赤外線反射性黒色系顔料の製造方法により得られる赤外線反射性黒色系顔料を用いて着色したことを特徴とする樹脂組成物である（本発明１２）。 Using the infrared reflective black pigment according to any one of the present inventions 1 to 6 or the infrared reflective black pigment obtained by the method for producing the infrared reflective black pigment according to any one of the present inventions 7 to 10. A resin composition characterized by being colored (Invention 12).
　本発明に係る赤外線反射性黒色系顔料は、有害な元素を含有せず、酸化第二銅を含み、優れた赤外線反射性を有すると共に耐酸性及び塗料安定性に優れるので赤外線反射性黒色系顔料として好適である。 The infrared reflective black pigment according to the present invention does not contain harmful elements, contains cupric oxide, has excellent infrared reflectivity, and is excellent in acid resistance and paint stability, so that it is an infrared reflective black pigment. It is suitable as.
　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系顔料について述べる。 First, the infrared reflective black pigment according to the present invention will be described.
　本発明に係る赤外線反射性黒色系顔料は、酸化第二銅から成る粒子を芯粒子とし、該芯粒子の表面を表面処理剤で被覆し得られる平均粒子径が０．０２～５．０μｍの黒色系顔料であって、被覆層は耐酸性を有し、被覆量が酸化第二銅に対して０．１～１０重量％である。 The infrared-reflective black pigment according to the present invention has particles composed of cupric oxide as core particles, and the average particle diameter obtained by coating the surface of the core particles with a surface treatment agent is 0.02 to 5.0 μm. It is a black pigment, the coating layer has acid resistance, and the coating amount is 0.1 to 10% by weight with respect to cupric oxide.
　芯粒子は、酸化第二銅粒子であってもよく、また、酸化第二銅と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料との混合物及び／又は複合化物であってもよい。芯粒子が上記混合物及び／又は複合化物の場合は、これを構成する酸化第二銅と第二成分の顔料とのモル比が０．１：０．９～１．０：０．０、好ましくは０．１：０．９～０．９５：０．０５であり、更に好ましくは０．１：０．９～０．９０：０．１であり、より更に好ましくは０．１５：０．８５～０．９０：０．１であり、特に好ましくは０．２０：０．８０～０．９０：０．１　である。酸化第二銅のモル比が０．１未満となると、明度が大きくなり過ぎ黒色系顔料とは言い難い。一方、酸化第二銅のモル比が大きい場合、比重が大きくなる。そのため、塗料などの溶剤中での分散性が要求されるような用途においては、比重の小さい方がより黒色系顔料の沈降が防げる点で好ましい。 The core particles may be cupric oxide particles, or any one or more of cupric oxide and an extender pigment as a second component, a white pigment, and iron oxide having a solar reflectance of 10% or more. It may be a mixture and / or composite with the above pigment. When the core particles are the above mixture and / or composite, the molar ratio of cupric oxide constituting the core and the pigment of the second component is 0.1: 0.9 to 1.0: 0.0, preferably Is 0.1: 0.9 to 0.95: 0.05, more preferably 0.1: 0.9 to 0.90: 0.1, and still more preferably 0.15: 0. 85 to 0.90: 0.1, particularly preferably 0.20: 0.80 to 0.90: 0.1. When the cupric oxide molar ratio is less than 0.1, the lightness becomes too high to be said to be a black pigment. On the other hand, when the molar ratio of cupric oxide is large, the specific gravity increases. Therefore, in applications where dispersibility in a solvent such as paint is required, a smaller specific gravity is preferable in terms of preventing sedimentation of black pigments.
　黒色系顔料の平均粒子径は、好ましくは０．０２５～４．８μｍ、より好ましくは０．０４～４．５μｍである。黒色系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。 The average particle size of the black pigment is preferably 0.025 to 4.8 μm, more preferably 0.04 to 4.5 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.
　酸化第二銅から成る粒子の表面を覆う被覆層は耐酸性を有することが必要である。本発明に係る赤外線反射性黒色系顔料においては、芯粒子が耐酸性の低い酸化第二銅粒子からなるため、芯粒子を覆う被覆層に耐酸性を持たせることで、顔料として耐酸性を確保する。また、被覆量が酸化第二銅に対して０．１重量％未満では、芯粒子である酸化第二銅を十分に被覆することができず、顔料の耐薬品性、特に耐酸性が不十分となる。一方、被覆量が酸化第二銅に対して１０重量％を超えると、耐酸性効果が飽和するため、必要以上に被覆することは不経済である。 The coating layer covering the surface of the particles made of cupric oxide must have acid resistance. In the infrared reflective black pigment according to the present invention, the core particles are composed of cupric oxide particles having low acid resistance, so that the coating layer covering the core particles has acid resistance, thereby ensuring acid resistance as a pigment. To do. Further, when the coating amount is less than 0.1% by weight with respect to cupric oxide, the cupric oxide as the core particle cannot be sufficiently coated, and the chemical resistance of the pigment, particularly acid resistance is insufficient. It becomes. On the other hand, if the coating amount exceeds 10% by weight with respect to cupric oxide, the acid resistance effect is saturated, and it is uneconomical to coat more than necessary.
　また本発明に係る赤外線反射性黒色系顔料の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、粒子表面への表面処理剤による均一な被覆処理が困難となる。より好ましくは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, aggregation is likely to occur due to an increase in intermolecular force due to particle miniaturization, so that it is difficult to uniformly coat the particle surface with a surface treatment agent. More preferably, it is 1.5 to 75 m 2 / g, and still more preferably 1.8 to 65 m 2 / g.
　また本発明に係る赤外線反射性黒色系顔料の明度（Ｌ＊）は、通常５０以下である。特に芯粒子が酸化第二銅から成る場合、黒色度が優れており、通常３０．０以下であり、より好ましくは２８以下である。第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料との混合物及び／又は複合化物から成る場合、４０以下がより好ましい。明度（Ｌ＊）が５０を超える場合には、黒色度に優れるとは言い難い。明度（Ｌ＊）の下限値は、通常１０である。第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料との混合物及び／又は複合化物から成る場合、下限値は２０程度である。 The lightness (L * ) of the infrared reflective black pigment according to the present invention is usually 50 or less. In particular, when the core particles are made of cupric oxide, the blackness is excellent and is usually 30.0 or less, more preferably 28 or less. When it is composed of a mixture and / or a composite of at least one of extender pigment, white pigment, and iron oxide having a solar reflectance of 10% or more, which is the second component, 40 or less is more preferable. When the lightness (L * ) exceeds 50, it is difficult to say that the blackness is excellent. The lower limit of lightness (L * ) is usually 10. The lower limit is about 20 when the mixture is composed of an extender pigment, white pigment, and iron oxide having a solar reflectance of 10% or more and a mixture and / or composite with at least one pigment.
　また本発明に係る赤外線反射性黒色系顔料のａ＊は、－２～＋１０が好ましい。ａ＊が前記範囲外の場合には、黒色度に優れるとは言い難い。より好ましくは－１～＋１０、特に好ましくは－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 that the blackness is excellent. More preferably, it is -1 to +10, and particularly preferably -1 to +5.
　また本発明に係る赤外線反射性黒色系顔料のｂ＊は、－５～＋１０が好ましい。ｂ＊が前記範囲外の場合には、黒色度に優れるとは言い難い。より好ましくは－４～＋５、特に好ましくは－２～＋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 that the blackness is excellent. More preferably, it is −4 to +5, and particularly preferably −2 to +5.
　また本発明に係る赤外線反射性黒色系顔料の赤外線反射性は、ラッカー色見本塗膜をＪＩＳ　Ｒ３１０６に従い測定したときの日射反射率が１８％以上であることが好ましく、より好ましくは２０％以上であり、より好ましくは２４％以上である、特に好ましくは２８％以上である。第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料との混合物及び／又は複合化物から成る場合、２８％以上である。日射反射率が１８％未満では、日射反射率が十分に高いとは言えない。最大値は７０％である。 The infrared reflectivity of the infrared reflective black pigment according to the present invention is preferably 18% or more, more preferably 20% or more, when the lacquer color sample coating film is measured according to JIS R3106. Yes, more preferably 24% or more, particularly preferably 28% or more. In the case of a mixture and / or a composite of at least one of the extender pigment, the white pigment, and the iron oxide having a solar reflectance of 10% or more, which is the second component, the content is 28% or more. If the solar reflectance is less than 18%, it cannot be said that the solar reflectance is sufficiently high. The maximum value is 70%.
　また本発明に係る赤外線反射性黒色系顔料は、該顔料を塗膜化した際の光沢度（ＧＬＯＳＳ値）が６０°－６０°において５０以上であることが好ましい。光沢度（ＧＬＯＳＳ値）が５０未満の場合には、十分な光沢性が得られず、分散性に優れているとは言い難い。 Further, the infrared reflective black pigment according to the present invention preferably has a glossiness (GLOSS value) of 50 or more at 60 ° -60 ° when the pigment is coated. When the glossiness (GLOSS value) is less than 50, sufficient glossiness cannot be obtained and it is difficult to say that the dispersibility is excellent.
　また本発明に係る赤外線反射性黒色系顔料は、真比重が３．０～６．０であることが好ましい。真比重が上記範囲内であれば、塗料構成基材に本発明に係る赤外線反射性黒色系顔料を分散させたとき、優れた分散性を示す。また塗料として優れた貯蔵安定性を示す。 In addition, the infrared reflective black pigment according to the present invention preferably has a true specific gravity of 3.0 to 6.0. If the true specific gravity is within the above range, excellent dispersibility is exhibited when the infrared-reflective black pigment according to the present invention is dispersed in the paint-constituting substrate. It also exhibits excellent storage stability as a paint.
　本発明に係る赤外線反射性黒色系顔料において、芯粒子の平均粒子径は、０．０１８～４．８０μｍ、好ましくは０．０２～４．５μｍ、より好ましくは０．０４～４．０μｍである。芯粒子の平均粒子径が０．０１８μｍ未満の場合には、粒子の微細化により分子間力が増大し凝集を起こしやすいため、芯粒子表面への表面処理剤の均一な被覆処理が困難となる。一方、平均粒子径が４．８μｍを超える場合には、得られる赤外線反射性黒色系顔料もまた粗大粒子となり着色力が低下する。 In the infrared reflective black pigment according to the present invention, the average particle diameter of the core particles is 0.018 to 4.80 μm, preferably 0.02 to 4.5 μm, more preferably 0.04 to 4.0 μm. . When the average particle diameter of the core particles is less than 0.018 μm, the intermolecular force increases due to the finer particles and aggregation easily occurs, so that it is difficult to uniformly coat the surface of the core particles with the surface treatment agent. . On the other hand, when the average particle diameter exceeds 4.8 μm, the resulting infrared reflective black pigment also becomes coarse particles and the coloring power is reduced.
　芯粒子の形状は、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。得られる黒色系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 core particle is not limited to a specific shape, but is spherical, granular, octahedral, hexahedral, polyhedral, etc., acicular, spindle, rice, etc. Can be used. Considering the dispersibility of the obtained black pigment, spherical particles and granular particles are preferable.
　本発明に係る赤外線反射性複合黒色系顔料の粒子形状や粒子サイズは、芯粒子の粒子形状や粒子サイズに大きく依存し、芯粒子に相似する粒子形態を有し、芯粒子よりも若干大きな粒子サイズを有している。 The particle shape and particle size of the infrared reflective composite black pigment according to the present invention largely depend on the particle shape and particle size of the core particle, have a particle form similar to the core particle, and slightly larger than the core particle. Have a size.
　芯粒子のＢＥＴ比表面積は、１～２００ｍ２／ｇ、好ましくは１．５～１５０ｍ２／ｇ、より好ましくは２．０～１００ｍ２／ｇである。ＢＥＴ比表面積が１ｍ２／ｇ未満の場合には、芯粒子が粗大であったり、粒子相互間で焼結が生じた粒子となっており、得られる顔料もまた粗大粒子となり、着色力が低下する。ＢＥＴ比表面積が２００ｍ２／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、芯粒子表面への表面処理剤による均一な被覆処理が困難となる。 The BET specific surface area of the core particles is 1 to 200 m 2 / g, preferably 1.5 to 150 m 2 / g, more preferably 2.0 to 100 m 2 / g. When the BET specific surface area is less than 1 m 2 / g, the core particles are coarse or particles are sintered between the particles, and the resulting pigment is also coarse particles, resulting in a decrease in coloring power. To do. When the BET specific surface area exceeds 200 m 2 / g, aggregation is likely to occur due to an increase in intermolecular force due to particle miniaturization, making it difficult to uniformly coat the surface of the core particles with a surface treatment agent.
　芯粒子として酸化第二銅粒子を使用する場合、酸化第二銅粒子は、市販品の他に例えば硫酸銅水溶液に水酸化ナトリウムと硫酸で中和し水酸化第二銅とし、水洗乾燥・熱処理することでも得られる。硫酸銅水溶液を中和する際に、あらかじめ体質顔料、白色顔料および酸化鉄を混合することでも得られる。 In the case of using cupric oxide particles as the core particles, cupric oxide particles are, for example, neutralized with sodium hydroxide and sulfuric acid into a copper sulfate aqueous solution in addition to commercially available products to make cupric hydroxide, washed with water, dried and heat treated You can also get it. When neutralizing an aqueous copper sulfate solution, it can also be obtained by mixing an extender pigment, a white pigment and iron oxide in advance.
　芯粒子として、酸化第二銅と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料との混合物及び／又は複合化物を使用する場合、芯粒子を構成する体質顔料、白色顔料及び酸化鉄は、日射反射率が１０％以上である。これら顔料の日射反射率が１０％未満では、十分に高い日射反射率を有する赤外線反射性黒色系顔料を得ることができない。 As the core particle, a mixture and / or a composite of cupric oxide and one or more of an extender pigment, a white pigment and iron oxide having a solar reflectance of 10% or more are used. In this case, the extender pigment, white pigment and iron oxide constituting the core particles have a solar reflectance of 10% or more. If the solar reflectance of these pigments is less than 10%, an infrared reflective black pigment having a sufficiently high solar reflectance cannot be obtained.
　体質顔料として、シリカ粉、ホワイトカーボン、微粉ケイ酸、珪藻土等のシリカ微粒子、クレー、炭酸カルシウム、炭酸バリウム、硫酸バリウム、石膏、アルミナホワイト、タルク、透明性酸化チタン、サチン白等が挙げられる。 Examples of extender pigments include silica fine particles such as silica powder, white carbon, fine powder silicic acid, diatomaceous earth, clay, calcium carbonate, barium carbonate, barium sulfate, gypsum, alumina white, talc, transparent titanium oxide, and satin white.
　白色顔料として、酸化亜鉛、塩基性硫酸鉛、硫酸鉛、リトポン、硫化亜鉛、酸化チタン、酸化アンチモンが挙げられる。 Examples of white pigments include zinc oxide, basic lead sulfate, lead sulfate, lithopone, zinc sulfide, titanium oxide, and antimony oxide.
　日射反射率が１０％以上である酸化鉄として、ヘマタイト及びマンガン含有ヘマタイトに対して５～４０重量％のマンガンを含有するマンガン含有ヘマタイトが挙げられる。 Examples of the iron oxide having a solar reflectance of 10% or more include manganese-containing hematite containing 5 to 40% by weight of manganese with respect to hematite and manganese-containing hematite.
　本発明に係る赤外線反射性黒色系顔料において、芯粒子を被覆する表面処理剤は、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使用することができる。 In the infrared reflective black pigment according to the present invention, the surface treatment agent for coating the core particles uses at least one compound selected from Si, Al, Zr, Ti, Zn, and P, or an organic surface treatment agent. be able to.
　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。 As one or more kinds of compounds selected from Si, Al, Zr, Ti, Zn, and P, as aluminum compounds, 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.
　次に、本発明に係る赤外線反射性黒色系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.
　芯粒子が酸化第二銅粒子の場合は、該芯粒子の表面を表面処理剤で被覆する。芯粒子が酸化第二銅粒子と第二成分顔料から成る場合は、酸化第二銅粒子と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料とを十分に混合する。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。 When the core particles are cupric oxide particles, the surface of the core particles is coated with a surface treatment agent. When the core particles are composed of cupric oxide particles and a second component pigment, any one of cupric oxide particles and an extender pigment as a second component, a white pigment, and iron oxide having a solar reflectance of 10% or more. Thoroughly mix with more than one type of pigment. As an apparatus used for mixing and stirring, an apparatus capable of applying a shearing force to the powder layer is preferable, and an apparatus capable of simultaneously performing shearing, spatula and compression, for example, a wheel type kneader, a ball type kneader, a blade type It is preferable to use a 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.
　さらに酸化第二銅粒子と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料からなる混合物を該混合物の融点以下の温度で熱処理することが好ましい。好ましい熱処理温度は、混合物の融点以下の温度で３００℃以上８５０℃以下の温度である。より好ましくは３００℃以上７５０℃以下の温度である。より好ましくは３００℃以上６００℃以下の温度である。混合物を該混合物の融点以下の温度で熱処理することで、複合化させることができる。混合物を複合化させることで耐薬品性がより高くなる。該混合物を該混合物の融点を超える温度で熱処理すると該混合物が溶融し、また、該混合物の融点以下の温度であっても８５０℃を越える高い温度で熱処理すると、芯粒子が粗大化し塗膜化した際の光沢性が低下するので好ましくない。次いで該芯粒子の表面を表面処理剤で被覆する。 Furthermore, heat treatment is performed at a temperature below the melting point of the mixture of cupric oxide particles and a second component, an extender pigment, a white pigment, and an iron oxide having a solar reflectance of 10% or more. It is preferable to do. A preferable heat treatment temperature is a temperature not higher than the melting point of the mixture and not lower than 300 ° C. and not higher than 850 ° C. More preferably, the temperature is 300 ° C. or higher and 750 ° C. or lower. More preferably, the temperature is 300 ° C. or more and 600 ° C. or less. The mixture can be combined by heat treatment at a temperature not higher than the melting point of the mixture. By combining the mixture, the chemical resistance becomes higher. When the mixture is heat-treated at a temperature exceeding the melting point of the mixture, the mixture melts. When the heat treatment is performed at a temperature exceeding 850 ° C. even if the temperature is lower than the melting point of the mixture, the core particles become coarse and form a coating film. This is not preferable because the glossiness when it is deteriorated. Next, the surface of the core particle is coated with a surface treatment agent.
　その後表面処理剤で被覆された粒子を温度１５０～３００℃で加熱処理することで本発明に係る赤外線反射性黒色系顔料を得ることができる。酸化第二銅粒子と表面処理剤とを混合することで、粒子表面が被覆された赤外線反射性黒色系顔料を得ることができるけれども、この状態では被覆層の耐薬品性、特に耐酸性が不十分である。表面処理剤で被覆された粒子を温度１５０℃未満の温度で加熱処理した場合も同様である。一方、被覆層は３００℃の温度で十分に強固となり３００℃を超えて加熱する必要はない。また３００℃を超えて必要以上に高い温度で加熱すると、芯粒子である酸化第二銅粒子の比表面積が低下するため好ましくない。 Thereafter, the infrared-reflective black pigment according to the present invention can be obtained by heat-treating the particles coated with the surface treatment agent at a temperature of 150 to 300 ° C. By mixing the cupric oxide particles and the surface treatment agent, an infrared-reflective black pigment coated on the particle surface can be obtained. However, in this state, the chemical resistance, particularly acid resistance, of the coating layer is poor. It is enough. The same applies when the particles coated with the surface treatment agent are heat-treated at a temperature of less than 150 ° C. On the other hand, the coating layer becomes sufficiently strong at a temperature of 300 ° C. and does not need to be heated above 300 ° C. Further, heating at a temperature higher than necessary exceeding 300 ° C. is not preferable because the specific surface area of the cupric oxide particles that are the core particles decreases.
　芯粒子表面への表面処理剤の被覆は、乾式又は湿式方法等の常法に従って行えばよい。乾式処理の場合、芯粒子と表面処理剤とを機械的に混合撹拌したり、芯粒子に表面処理剤を噴霧しながら機械的に混合撹拌すればよい。添加した表面処理剤は、ほぼその全量が芯粒子の粒子表面に被覆される。 The coating of the surface treatment agent on the surface of the core particles may be performed according to a conventional method such as a dry method or a wet method. In the case of dry processing, the core particles and the surface treatment agent may be mechanically mixed and stirred, or may be mechanically mixed and stirred while spraying the surface treatment agent on the core particles. Almost all of the added surface treatment agent is coated on the surface of the core particles.
　表面処理剤を均一に芯粒子の表面に被覆するためには、芯粒子の凝集をあらかじめ粉砕機を用いて解きほぐしておくことが好ましい。 In order to uniformly coat the surface of the core particles with the surface treatment agent, it is preferable that the aggregation of the core particles is previously unraveled using a pulverizer.
　芯粒子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。 As an apparatus used for mixing and stirring the core particles and the surface treatment agent, an apparatus capable of applying a shearing force to the powder layer is preferable, and an apparatus capable of simultaneously performing 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.
　芯粒子と表面処理剤との混合撹拌条件は、芯粒子の表面に表面処理剤ができるだけ均一に被覆されるように、適宜調整すればよく、線荷重は１９．６～１９６０Ｎ／ｃｍ（２～２００Ｋｇ／ｃｍ）が好ましく、より好ましくは９８～１４７０Ｎ／ｃｍ（１０～１５０Ｋｇ／ｃｍ）、最も好ましくは１４７～９８０Ｎ／ｃｍ（１５～１００Ｋｇ／ｃｍ）であり、処理時間は５分～２４時間が好ましく、より好ましくは１０分～２０時間の範囲であり、撹拌速度は２～２０００ｒｐｍが好ましく、より好ましくは５～１０００ｒｐｍ、最も好ましくは１０～８００ｒｐｍの範囲である。 The mixing and stirring conditions for the core particles and the surface treatment agent may be appropriately adjusted so that the surface treatment agent is coated on the surface of the core particles as uniformly as possible. The line load is 19.6 to 1960 N / cm (2 to 2). 200 Kg / cm), more preferably 98 to 1470 N / cm (10 to 150 Kg / cm), most preferably 147 to 980 N / cm (15 to 100 Kg / cm), and the treatment time is 5 minutes to 24 hours. More preferably, the range is from 10 minutes to 20 hours, and the stirring speed is preferably from 2 to 2000 rpm, more preferably from 5 to 1000 rpm, and most preferably from 10 to 800 rpm.
　例えば、シランカップリング剤をヘンシェルミキサーで乾式処理する場合、芯粒子、水、助剤、アルコールを低速度回転で1時間予備混合する。その後、高速度回転に調整し、１３０℃で１時間維持した後、水冷却し排出する。その後１５０℃で１時間加熱する。 For example, when the silane coupling agent is dry-processed with a Henschel mixer, the core particles, water, auxiliary agent, and alcohol are premixed for 1 hour at low speed. Then, it adjusts to high speed rotation and maintains at 130 degreeC for 1 hour, Then, it cools and discharges with water. Thereafter, it is heated at 150 ° C. for 1 hour.
　また、ステアリン酸亜鉛を乾式で表面処理する場合には、振動ミルで３０分間処理し、その後、乾燥機で１５０℃の温度で乾燥させる。 In addition, when the surface treatment of zinc stearate is performed by a dry method, it is treated with a vibration mill for 30 minutes and then dried at a temperature of 150 ° C. with a dryer.
　湿式方法は、湿式分散した芯粒子スラリーに、Ｓｉ，Ａｌ，Ｚｒ，Ｔｉ，Ｚｎ，Ｐ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・混合して被覆すればよい。これにより芯粒子の表面を水酸化物又は酸化物で被覆することができる。有機系表面処理剤の場合、湿式分散した芯粒子スラリーに有機系表面処理剤を投入して被覆すればよい。 In the wet method, one or two or more soluble compounds selected from Si, Al, Zr, Ti, Zn, and P are added to and mixed with the wet-dispersed core particle slurry while adjusting the pH with acid or alkali. What is necessary is just to coat. Thereby, the surface of a core particle can be coat | covered with a hydroxide or an oxide. In the case of an organic surface treatment agent, the organic surface treatment agent may be put on and coated on the wet-dispersed core particle slurry.
　例えば、芯粒子を純水中で撹拌しながら３号水ガラスと硫酸、水酸化ナトリウムをｐＨが６～８になるように滴下添加し、８０℃で１時間維持した後、水洗し乾燥する。さらにその後１５０℃の温度で１時間加熱すればよい。 For example, while stirring the core particles in pure water, No. 3 water glass, sulfuric acid and sodium hydroxide are added dropwise so that the pH is 6 to 8, maintained at 80 ° C. for 1 hour, washed with water and dried. Thereafter, heating may be performed at a temperature of 150 ° C. for 1 hour.
　また２種以上の表面処理剤を使用する場合には、芯粒子を純水中で撹拌しながら、例えば硫酸ジルコニウムとアルミン酸ナトリウムと硫酸、水酸化ナトリウムをｐＨが６～８になるように滴下添加し、８０℃で１時間維持した後、水洗、ろ過乾燥する。さらにその後１８０℃の温度で１時間加熱すればよい。 When two or more kinds of surface treatment agents are used, for example, zirconium sulfate, sodium aluminate, sulfuric acid, and sodium hydroxide are dropped so that the pH becomes 6 to 8 while stirring the core particles in pure water. Add, maintain at 80 ° C. for 1 hour, then wash with water and filter dry. Further, it may be heated at a temperature of 180 ° C. for 1 hour.
　次に、本発明に係る赤外線反射性黒色系顔料を配合した塗料について述べる。 Next, a 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系顔料の配合割合は、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 a range of 0.5 to 100 parts by weight with respect to 100 parts by weight of the paint base material, and the handling property of the paint is taken into consideration. In this case, the amount 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、有機顔料、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 base material, resin, solvent, and if necessary, fats and oils, antifoaming agent, extender pigment, organic 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 cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve and other glycol ether solvents, 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.
　有機顔料としては、フタロシアニンブルー、フタロシアニングリーン、ペリレンブラック等を使用することができる。使用方法は、黒色顔料の表面に強固に付着するように混合したり、塗料化時に同時に添加する方法がある。 As the organic pigment, phthalocyanine blue, phthalocyanine green, perylene black and the like can be used. As a method of use, there is a method of mixing so as to firmly adhere to the surface of the black pigment, or a method of adding at the same time when forming a paint.
　次に、本発明に係る赤外線反射性黒色系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系顔料の配合割合は、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. Considering it, it 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、赤外線反射性黒色系顔料と周知の熱可塑性樹脂とともに、必要により体質顔料、有機顔料、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 infrared reflective black pigment and a known thermoplastic resin, as well as extender pigments, organic pigments, lubricants, plasticizers, antioxidants, ultraviolet absorbers, various Additives such as stabilizers are 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, phenolic 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、赤外線反射性黒色系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 total 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系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、赤外線反射性黒色系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系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 thoroughly 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 After destroying the pigment aggregate and uniformly dispersing the infrared-reflective black pigment in the resin composition, it is molded into a shape suitable for the purpose and used.
　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系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。 Master batch pellets in the present invention require a binder resin as a constituent substrate of the paint and the resin composition and the infrared-reflective black pigment, mixing a ribbon blender, Nauter mixer, Henschel mixer, super mixer, etc. Kneaded by mixing with a machine, kneaded with a known single-screw kneading extruder or twin-screw kneading extruder, etc., then cut, or kneaded by kneading the mixture with a Banbury mixer, pressure kneader, etc. Manufactured by crushing, molding, or cutting an object.
　結合材樹脂と赤外線反射性黒色系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 carried out in 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系顔料の量は、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、赤外線反射性黒色系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、赤外線反射性黒色系顔料に対する結合材樹脂が少ないため、赤外線反射性黒色系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系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 masterbatch 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. is there. 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 disperse and mix the infrared reflective black pigment well. When the amount exceeds 200 parts by weight, since there is little binder resin for the infrared reflective black pigment, it is difficult to disperse and mix the infrared reflective black pigment, and a slight change in the addition amount of the master batch pellets Since the content of the infrared-reflective black pigment blended in the resin composition changes greatly, it is difficult to prepare the desired content, which is not preferable. Also, mechanical wear is severe and not suitable.
　＜作用＞
　本発明において最も重要な点は、本発明に係る赤外線反射性黒色系顔料は、有害元素を含有することなく、酸化第二銅を含む黒色系顔料であって、優れた赤外線反射性を有すると共に耐酸性及び塗料安定性に優れるという事実である。 <Action>
The most important point in the present invention is that the infrared reflective black pigment according to the present invention is a black pigment containing cupric oxide without containing harmful elements and having excellent infrared reflectivity. This is the fact that it is excellent in acid resistance and paint stability.
　本発明に係る赤外線反射性黒色系顔料は、赤外線反射性に優れるものの耐酸性に劣る酸化第二銅を芯粒子とするけれども、該芯粒子の表面に耐酸性を有する被覆層で被覆することで、高い赤外線反射性を有しながらも優れた耐酸性を実現することができた。 Although the infrared-reflective black pigment according to the present invention has cupric oxide which is excellent in infrared reflectivity but inferior in acid resistance as a core particle, the surface of the core particle is coated with a coating layer having acid resistance. It was possible to realize excellent acid resistance while having high infrared reflectivity.
　さらに、本発明に係る赤外線反射性黒色系顔料は、赤外線反射性に優れるものの耐酸性に劣りさらに真比重が大きい酸化第二銅を含むけれども、酸化第二銅粒子と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料との混合物及び／又は複合化物を芯粒子とし、該芯粒子の表面を耐酸性を有する被覆層で被覆することで、塗料分散時の成分分離を防止し、高い赤外線反射性を有しながらも優れた耐薬品性、特に高い耐酸性を実現することができた。特に芯粒子の表面を表面処理剤で被覆した後、所定温度で加熱処理することにより、高い耐酸性を得ることができた。さらに芯粒子を表面処理剤で被覆する前に所定温度で熱処理することで、より優れた耐薬品性を実現することができた。 Furthermore, although the infrared reflective black pigment according to the present invention contains cupric oxide which is excellent in infrared reflectivity but inferior in acid resistance and has a large true specific gravity, it is a body pigment which is a cupric oxide particle and a second component. A mixture of a white pigment and one or more pigments of iron oxide having a solar reflectance of 10% or more and / or a composite is used as a core particle, and the surface of the core particle is coated with a coating layer having acid resistance By doing so, it was possible to prevent the separation of components during the dispersion of the paint and to realize excellent chemical resistance, particularly high acid resistance while having high infrared reflectivity. In particular, high acid resistance could be obtained by coating the surface of the core particle with a surface treatment agent and then heat-treating it at a predetermined temperature. Furthermore, it was possible to realize better chemical resistance by heat treatment at a predetermined temperature before coating the core particles with the surface treatment agent.
　また、本発明に係る赤外線反射性黒色系顔料は、芯粒子が酸化第二銅粒子と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料との混合物及び／又は複合化物からなるので、酸化第二銅粒子のみを芯粒子とする場合に比較して比重を下げることが可能となり、これにより塗料分散時の優れた分散性及び塗料貯蔵安定性を実現することができた。 Further, the infrared reflective black pigment according to the present invention is any one of cupric oxide particles and extender pigments that are the second component, white pigment, and iron oxide whose solar reflectance is 10% or more. Since it consists of a mixture and / or composite with the above pigments, it becomes possible to lower the specific gravity as compared with the case where only cupric oxide particles are used as the core particles. Paint storage stability could be realized.
　また、本発明に係る赤外線反射性黒色系顔料は、Ｃｒ６＋などの有害金属元素を含有しておらず、安全な顔料である。 The infrared reflective black pigment according to the present invention does not contain a harmful metal element such as Cr 6+ and is a safe pigment.
　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電子顕微鏡写真に示される粒子３５０個の粒子径をそれぞれ測定し、その平均値で示した。 The average particle size of the particles was measured by measuring the particle size of 350 particles shown in the electron micrograph, and the average value was shown.
　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.
　酸化第二銅粒子、酸化第二銅粒子と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料との混合物及び／又は複合化物からなる芯粒子及び赤外線反射性黒色系顔料の内部や表面に存在するＳｉ量、Ａｌ量、Ｚｒ量、Ｔｉ、Ｚｎ及びＰ量並びに有機系表面処理剤から生成するオルガノシラン化合物又はポリシロキサンに含有されているＳｉ量のそれぞれは「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。 Mixture and / or composite of cupric oxide particles, cupric oxide particles and extender pigment as second component, white pigment and one or more pigments of iron oxide having solar reflectance of 10% or more Contained in the amount of Si, Al, Zr, Ti, Zn and P present in the core particles and infrared reflective black pigments and the organosilane compounds or polysiloxanes produced from organic surface treatment agents Each of the Si amounts measured 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.
　赤外線反射性黒色系顔料の色相（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、「多光源分光測色計ＭＳＣ－ＩＳ－２Ｄ」（スガ試験機株式会社製）を用いて測定を行い、ＪＩＳ　Ｚ８７２９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. Add 4.5g, knead, paint, and apply the coated piece (coating thickness: about 30μm) coated on cast coated paper using a 150μm (6mil) applicator. Measurement was carried out using “total MSC-IS-2D” (manufactured by Suga Test Instruments Co., Ltd.), and the color index (L * value, a * value, b * value) was indicated according to JIS Z8729.
　赤外線反射性複合黒色系顔料の真比重（密度）は、ＪＩＳ　Ｋ５１０１の「顔料試験方法」に従って測定した。 The true specific gravity (density) of the infrared reflective composite black pigment was measured according to “Pigment Test Method” of JIS K5101.
　赤外線反射性黒色系顔料の日射反射率は、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　ＵＶ－４１００」（ＨＩＴＡＣＨＩ）を用い、ＪＩＳ　Ｒ３１０６に従い測定した。 The solar reflectance of the infrared-reflective black pigment was measured in accordance with JIS R3106 using a “spectrophotometer UV-4100” (HITACHI) for the coating piece prepared for measuring the hue.
　赤外線反射性黒色系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２％の硫酸を２０ｍｌ加え、密封して５分振り混ぜ、常温に静置させた後、ろ過分離後の溶液をＩＣＰでＣｕ量を測定し、溶解Ｃｕを分析した。 The acid resistance of the infrared-reflective black pigment was evaluated according to JIS K5101-8 “Pigment Test Method Part 8: Chemical Resistance”. Add 2 g of pigment and 20 ml of 2% sulfuric acid to the test tube, and seal it. After shaking and mixing and allowing to stand at room temperature, the amount of Cu in the solution after filtration and separation was measured by ICP, and dissolved Cu was analyzed.
　赤外線反射性黒色系顔料の光沢度（ＧＬＯＳＳ値）は、色判定、日射反射率を測定した色見本を、「デジタル変角光沢計ＵＧＶ－５Ｄ」（スガ試験機株式会社製）を用いて６０°－６０°における値を示した。光沢度が高いほど、赤外線反射性黒色系顔料を配合した塗料の分散性が優れていることを示す。 The glossiness (GLOSS value) of the infrared reflective black pigment is 60 using a color sample obtained by measuring the color determination and the solar reflectance by using “Digital Variable Glossmeter UGV-5D” (manufactured by Suga Test Instruments Co., Ltd.). The value at ° -60 ° is shown. It shows that the dispersibility of the coating material which mix | blended the infrared reflective black pigment is excellent, so that glossiness is high.
　赤外線反射性黒色系顔料を含有する塗料の評価は、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、赤外線反射性黒色系顔料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。静置５時間後の塗料について、目視で分離状態を判定し安定性を評価した。また、２４時間静置し、黒色系顔料を沈降させた。この沈殿物を撹拌機でかき混ぜたときの再分散性の容易、困難で評価を行った。 The evaluation of the paint containing the infrared reflective black pigment was performed as follows. In mayonnaise bottle (internal volume 140 ml), 90 g of glass beads, 10 g of infrared reflective 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 aluminum alkyd resin (clear), it was dispersed for 5 minutes with a paint conditioner and separated from glass beads. About the coating material after 5 hours of stationary, the separation state was visually judged and stability was evaluated. Moreover, it left still for 24 hours and the black pigment was settled. Evaluation was made based on the ease and difficulty of redispersibility when the precipitate was stirred with a stirrer.
　以下の実施例および比較例において、実施例１～４及び比較例１～４は、芯粒子が酸化第二銅粒子から成る場合、実施例５～１０及び比較例５～９は、芯粒子が酸化第二銅粒子と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料との混合物及び／又は複合化物から成る場合についての例である。 In the following Examples and Comparative Examples, Examples 1 to 4 and Comparative Examples 1 to 4 show that when the core particles are made of cupric oxide particles, Examples 5 to 10 and Comparative Examples 5 to 9 show that the core particles are Example of the case of a mixture and / or a composite of cupric oxide particles and a second component, an extender pigment, a white pigment, and an iron oxide having a solar reflectance of 10% or more. It is.
　実施例１：
　ＣｕＯ粒子に対し、シランカップリング剤２．５重量％（ＳｉＯ２換算で１重量％）と水０．２５重量％、アルコール１．７５重量％を加え、ヘンシェルミキサーで低速度回転で１時間予備混合した。その後、ヘンシェルミキサーを高速度回転に調整し、１３０℃で１時間維持し、水冷却し排出した。その後、表面処理剤で被覆された芯粒子を１５０℃で１時間加熱処理した。加熱処理品を粉砕し平均粒子径０．３μｍ、ＢＥＴ比表面積９．５ｍ２／ｇの黒色系顔料を得た。 Example 1:
Add 2.5% by weight of silane coupling agent (1% by weight in terms of SiO 2 ), 0.25% by weight of water and 1.75% by weight of alcohol to CuO particles, and reserve for 1 hour at low speed with a Henschel mixer. Mixed. Thereafter, the Henschel mixer was adjusted to high speed rotation, maintained at 130 ° C. for 1 hour, cooled with water and discharged. Thereafter, the core particles coated with the surface treatment agent were heat-treated at 150 ° C. for 1 hour. The heat-treated product was pulverized to obtain a black pigment having an average particle size of 0.3 μm and a BET specific surface area of 9.5 m 2 / g.
　得られた黒色系顔料の被覆量は、芯粒子に対してＳｉＯ２換算で１重量％であり、日射反射率は２５％であった。耐酸性を評価した結果、溶液中のＣｕの濃度は８９０ｐｐｍと小さく、さらに塗料中での沈降後の再分散性も良好であった。 The coating amount of the obtained black pigment was 1% by weight in terms of SiO 2 with respect to the core particles, and the solar reflectance was 25%. As a result of evaluating acid resistance, the concentration of Cu in the solution was as low as 890 ppm, and the redispersibility after settling in the paint was also good.
　実施例２：
　ＣｕＯ粒子に対し、純水中で撹拌しながらアルミン酸ナトリウム６．０重量％（Ａｌ２Ｏ３換算で２重量％）を、硫酸、水酸化ナトリウムをｐＨが６～８になるように滴下添加し、８０℃で１時間維持した後、水洗、ろ過乾燥する。さらにその後２５０℃の温度で１時間加熱処理した。加熱処理品を粉砕し平均粒子径０．８５μｍ、ＢＥＴ比表面積２．６ｍ２／ｇの黒色系顔料を得た。 Example 2:
While stirring in pure water, 6.0% by weight of sodium aluminate (2% by weight in terms of Al 2 O 3 ) is added dropwise to CuO particles so that sulfuric acid and sodium hydroxide have a pH of 6-8. And maintained at 80 ° C. for 1 hour, then washed with water and dried by filtration. Thereafter, heat treatment was performed at a temperature of 250 ° C. for 1 hour. The heat-treated product was pulverized to obtain a black pigment having an average particle size of 0.85 μm and a BET specific surface area of 2.6 m 2 / g.
　得られた黒色系顔料の被覆量は、芯粒子に対してＡｌ２Ｏ3換算で２重量％であり、日射反射率は２８％であった。耐酸性を評価した結果、溶液中のＣｕの濃度は３４０ｐｐｍと小さく、さらに塗料中での沈降後の再分散性も良好であった。 The coating amount of the obtained black pigment was 2% by weight in terms of Al 2 O 3 with respect to the core particles, and the solar reflectance was 28%. As a result of evaluating acid resistance, the concentration of Cu in the solution was as small as 340 ppm, and the redispersibility after settling in the paint was also good.
　実施例３～実施例４、比較例１～比較例４：
　表面処理方法、表面処理剤、被覆量及び表面処理後の加熱処理温度を変化させた以外、実施例１と同様にして黒色系顔料を得た。 Example 3 to Example 4, Comparative Example 1 to Comparative Example 4:
A black pigment was obtained in the same manner as in Example 1 except that the surface treatment method, the surface treatment agent, the coating amount, and the heat treatment temperature after the surface treatment were changed.
　実施例１～４及び比較例１～４の製造条件及び得られた赤外線反射性黒色系顔料の諸特性、塗料及び塗膜の特性を表１及び表２に示した。 Tables 1 and 2 show the production conditions of Examples 1 to 4 and Comparative Examples 1 to 4, the properties of the obtained infrared reflective black pigments, and the properties of the paint and the coating film.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例５：
　ＣｕＯ粒子とＡｌ２Ｏ３粒子とをモル比で０．８：０．２とし、これらを室温下で混合撹拌し、芯粒子を得た。この芯粒子に対し、シランカップリング剤２．５重量％（ＳｉＯ２換算で１重量％）と水０．２５重量％、アルコール１．７５重量％を加え、ヘンシェルミキサーで低速度回転で１時間予備混合した。その後、ヘンシェルミキサーを高速度回転に調整し、１３０℃で１時間維持し、水冷却し排出した。その後、表面処理剤で被覆された芯粒子を１６０℃で１時間加熱処理した。加熱処理品を粉砕し平均粒子径０．４μｍ、ＢＥＴ比表面積９．８ｍ２／ｇの複合黒色系顔料を得た。 Example 5:
The molar ratio of CuO particles and Al 2 O 3 particles was 0.8: 0.2, and these were mixed and stirred at room temperature to obtain core particles. To this core particle, 2.5% by weight of a silane coupling agent (1% by weight in terms of SiO 2 ), 0.25% by weight of water and 1.75% by weight of alcohol are added, and the Henschel mixer is rotated at a low speed for 1 hour. Premixed. Thereafter, the Henschel mixer was adjusted to high speed rotation, maintained at 130 ° C. for 1 hour, cooled with water and discharged. Thereafter, the core particles coated with the surface treatment agent were heat-treated at 160 ° C. for 1 hour. The heat-treated product was pulverized to obtain a composite black pigment having an average particle size of 0.4 μm and a BET specific surface area of 9.8 m 2 / g.
　得られた複合黒色系顔料の被覆量は、芯粒子に対してＳｉＯ２換算で１重量％であり、真比重は５．６ｇ／ｃｍ３であった。また日射反射率は２５％であり、耐酸性を評価した結果、溶液中のＣｕの濃度は５４０ｐｐｍと小さく、塗料とした際も分離することなく安定していた。 The coating amount of the obtained composite black pigment was 1% by weight in terms of SiO 2 with respect to the core particles, and the true specific gravity was 5.6 g / cm 3 . The solar reflectance was 25%, and as a result of evaluating acid resistance, the concentration of Cu in the solution was as small as 540 ppm and was stable without separation even when used as a paint.
　実施例６：
　ＣｕＯ粒子とＳｉＯ２粒子とをモル比で０．５：０．５とし、これらを室温下で混合撹拌し、芯粒子を得た。この芯粒子に対し、純水中で撹拌しながらアルミン酸ナトリウム６．０重量％（Ａｌ２Ｏ３換算で２重量％）を、硫酸、水酸化ナトリウムをｐＨが６～８になるように滴下添加し、８０℃で１時間維持した後、水洗、ろ過乾燥する。さらにその後１８０℃の温度で１時間加熱処理した。加熱処理品を粉砕し平均粒子径０．０９μｍ、ＢＥＴ比表面積６５ｍ２／ｇの黒色系顔料を得た。 Example 6:
The molar ratio of CuO particles and SiO 2 particles was 0.5: 0.5, and these were mixed and stirred at room temperature to obtain core particles. While stirring in pure water, 6.0% by weight of sodium aluminate (2% by weight in terms of Al 2 O 3 ) was added dropwise to the core particles so that sulfuric acid and sodium hydroxide would have a pH of 6-8. Add, maintain at 80 ° C. for 1 hour, then wash with water and filter dry. Thereafter, heat treatment was performed at a temperature of 180 ° C. for 1 hour. The heat-treated product was pulverized to obtain a black pigment having an average particle size of 0.09 μm and a BET specific surface area of 65 m 2 / g.
　得られた黒色系顔料の被覆量は、芯粒子に対してＡｌ２Ｏ3換算で２重量％であり、真比重は４．２ｇ／ｃｍ３であった。また日射反射率は２８％であり、耐酸性を評価した結果、溶液中のＣｕの濃度は１９０ｐｐｍと小さく、塗料とした際も分離することなく安定していた。 The coating amount of the obtained black pigment was 2% by weight in terms of Al 2 O 3 with respect to the core particles, and the true specific gravity was 4.2 g / cm 3 . The solar reflectance was 28%. As a result of evaluating acid resistance, the concentration of Cu in the solution was as low as 190 ppm, and it was stable without separation even when used as a paint.
　実施例７～実施例１０、比較例５～比較例７：
　実施例７～実施例１０、比較例６では、ＣｕＯ粒子と第二成分粒子とを混合撹拌した後、熱処理を行ない、その後に表面処理及び加熱処理を行った。その他、熱処理温度、表面処理方法、表面処理剤及び被覆量、さらには表面処理後の加熱温度を変化させた。 Examples 7 to 10 and Comparative Examples 5 to 7:
In Examples 7 to 10 and Comparative Example 6, the CuO particles and the second component particles were mixed and stirred, and then heat treatment was performed, followed by surface treatment and heat treatment. In addition, the heat treatment temperature, the surface treatment method, the surface treatment agent and the coating amount, and the heating temperature after the surface treatment were changed.
　比較例６においては、塗料とした際に顔料が沈降分離し、比較例５及び７においては、塗料とした際にＣｕＯと第二成分の顔料とが分離し沈降した。 In Comparative Example 6, the pigment settled and separated when used as a paint, and in Comparative Examples 5 and 7, CuO and the second component pigment separated and settled when used as a paint.
　実施例５～１０及び比較例５～７の製造条件、得られた赤外線反射性複合黒色系顔料の諸特性、塗料及び塗膜の特性を表３、表４及び表５に示した。 Tables 3, 4 and 5 show the production conditions of Examples 5 to 10 and Comparative Examples 5 to 7, the characteristics of the obtained infrared reflective composite black pigment, and the characteristics of the paint and the coating film.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　本発明に係る赤外線反射性黒色系顔料は、赤外線反射性に優れかつ耐酸性及び塗料安定性にも優れるので赤外線反射性黒色系顔料として好適である。また本発明に係る赤外線反射性複合黒色系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。 The infrared reflective black pigment according to the present invention is suitable as an infrared reflective black pigment because it is excellent in infrared reflectivity, acid resistance and paint stability. Moreover, since the resin composition containing the infrared reflective composite 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. can do.
　本発明に係る赤外線反射性黒色系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, it is possible to prevent the generation and growth of weeds when used for agricultural multi-sheets. Since it has excellent infrared 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、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、意匠の点から黒色系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系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, it can be suitably used for a solar cell backsheet. 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 which protects the back surface of a solar cell element has high reflectivity from the point of power conversion efficiency, and the back sheet which has a black type from the point of a design is preferable. 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.
　外部から内部を見えにくくするために着色されたフィルムが車両の窓ガラス等に貼付され使用されているが、これらフィルムには室内の温度を上昇させないことも求められている。本発明に係る赤外線反射性黒色系顔料を含有する樹脂組成物から得られるフィルムは、黒色度に優れかつ赤外線反射性に優れるので、車両、建物の窓ガラスに貼付する着色フィルムとして好適に使用することができる。 着色 Colored films are stuck and used on the window glass of vehicles to make it difficult to see the inside from the outside, but these films are also required not to raise the indoor temperature. Since the film obtained from the resin composition containing the infrared reflective black pigment according to the present invention is excellent in blackness and infrared reflectiveness, it is preferably used as a colored film to be attached to a window glass of a vehicle or a building. be able to.

Claims (12)

  1. 　酸化第二銅から成る芯粒子の表面を表面処理剤で被覆し得られる平均粒子径が０．０２～５．０μｍの黒色系顔料であって、被覆層は耐酸性を有し、被覆量が酸化第二銅に対して０．１～１０重量％であることを特徴とする赤外線反射性黒色系顔料。 A black pigment having an average particle diameter of 0.02 to 5.0 μm obtained by coating the surface of core particles made of cupric oxide with a surface treatment agent, and the coating layer has acid resistance and a coating amount of An infrared reflective black pigment characterized by being 0.1 to 10% by weight based on cupric oxide.
  2. 　表面を被覆する表面処理剤が、Ｓｉ、Ａｌ、Ｚｒ、Ｔｉ、Ｚｎ、Ｐから選ばれる一種以上の化合物又は有機系表面処理剤である請求項１に記載の赤外線反射性黒色系顔料。 The infrared reflective black pigment according to claim 1, wherein the surface treatment agent for coating the surface is one or more compounds selected from Si, Al, Zr, Ti, Zn, and P, or an organic surface treatment agent.
  3. 　明度（Ｌ＊）が３０以下である請求項１又は２記載の赤外線反射性黒色系顔料。 The infrared reflective black pigment according to claim 1 or 2, having a lightness (L * ) of 30 or less.
  4. 　日射反射率が１８％以上である請求項１～３の何れかに記載の赤外線反射性黒色系顔料。 The infrared reflective black pigment according to any one of claims 1 to 3, wherein the solar reflectance is 18% or more.
  5. 　酸化第二銅から成る芯粒子が酸化第二銅と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料との混合物及び／又は複合化物から成り、酸化第二銅から成る芯粒子を構成する酸化第二銅と第二成分の顔料とのモル比が０．１：０．９～０．９５：０．０５である請求項１～４の何れかに赤外線反射性黒色系顔料。 Mixture of cupric oxide and core pigment made of cupric oxide and second component, extender pigment, white pigment, and iron oxide having solar reflectance of 10% or more, and / or mixture of at least one pigment and / or The molar ratio of the cupric oxide and the second component pigment, which are composed of the composite and constitute core particles of cupric oxide, is 0.1: 0.9 to 0.95: 0.05. Infrared reflective black pigment in any one of 1-4.
  6. 　明度（Ｌ＊）が２０以上５０以下である請求項５に記載の赤外線反射性黒色系顔料。 The infrared reflective black pigment according to claim 5, wherein the lightness (L * ) is 20 or more and 50 or less.
  7. 　酸化第二銅から成る芯粒子の表面を表面処理剤で被覆する被覆工程と、前記表面処理剤で被覆された酸化第二銅から成る芯粒子を１５０～３００℃の温度で加熱処理する加熱処理工程とから成る請求項１に記載の赤外線反射性黒色系顔料の製造方法。 A coating step of coating the surface of the core particles made of cupric oxide with a surface treatment agent, and a heat treatment for heating the core particles made of cupric oxide coated with the surface treatment agent at a temperature of 150 to 300 ° C. The method for producing an infrared reflective black pigment according to claim 1, comprising the steps of:
  8. 　酸化第二銅粒子と第二成分である体質顔料、白色顔料及び日射反射率が１０％以上である酸化鉄のいずれか１種以上の顔料粒子とを混合し芯粒子を得る混合工程と、前記混合工程で得られる芯粒子の表面を表面処理剤で被覆する被覆工程と、前記被覆工程で得られる表面処理剤で被覆された芯粒子を１５０～３００℃の温度で加熱する加熱処理工程とから成る請求項５に記載の赤外線反射性黒色系顔料の製造方法。 A mixing step of obtaining core particles by mixing cupric oxide particles and an extender pigment as a second component, a white pigment, and one or more pigment particles of iron oxide having a solar reflectance of 10% or more; and A coating step of coating the surface of the core particles obtained in the mixing step with a surface treatment agent, and a heat treatment step of heating the core particles coated with the surface treatment agent obtained in the coating step at a temperature of 150 to 300 ° C. A method for producing an infrared reflective black pigment according to claim 5.
  9. 　さらに混合工程の後、被覆工程前に、混合工程で得られる芯粒子を該芯粒子の融点以下の温度で熱処理する熱処理工程を含む請求項８に記載の赤外線反射性黒色系顔料の製造方法。 The method for producing an infrared-reflective black pigment according to claim 8, further comprising a heat treatment step in which the core particles obtained in the mixing step are heat-treated at a temperature lower than the melting point of the core particles after the mixing step and before the coating step.
  10. 　熱処理工程における熱処理温度が３００℃以上８５０℃以下である請求項９に記載の赤外線反射性黒色系顔料の製造方法。 The method for producing an infrared reflective black pigment according to claim 9, wherein the heat treatment temperature in the heat treatment step is 300 ° C or higher and 850 ° C or lower.
  11. 　請求項１～６の何れかに記載の赤外線反射性黒色系顔料または請求項７～１０の何れかに記載の赤外線反射性黒色系顔料の製造方法により得られる赤外線反射性黒色系顔料を塗料構成基材中に配合したことを特徴とする塗料。 The infrared reflective black pigment according to any one of claims 1 to 6 or the infrared reflective black pigment obtained by the method for producing an infrared reflective black pigment according to any one of claims 7 to 10 A paint characterized by being mixed in a base material.
  12. 　請求項１～６の何れかに記載の赤外線反射性黒色系顔料または請求項７～１０の何れかに記載の赤外線反射性黒色系顔料の製造方法により得られる赤外線反射性黒色系顔料を用いて着色したことを特徴とする樹脂組成物。 Using the infrared reflective black pigment according to any one of claims 1 to 6 or the infrared reflective black pigment obtained by the method for producing an infrared reflective black pigment according to any one of claims 7 to 10. A resin composition characterized by being colored.
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CN105452390A (en) * 2013-08-30 2016-03-30 户田工业株式会社 Black pigment having infrared-reflecting properties, and paint and resin composition that use said black pigment having infrared-reflecting properties
CN106574105A (en) * 2014-04-09 2017-04-19 谢珀德颜色公司 Core-shell composite inorganic metal oxides and method of preparation for prevention of thermal oxidative degradation in polymer and resin compositions
JP2020041106A (en) * 2018-09-13 2020-03-19 堺化学工業株式会社 Chlorine-containing resin composition
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CN106574105A (en) * 2014-04-09 2017-04-19 谢珀德颜色公司 Core-shell composite inorganic metal oxides and method of preparation for prevention of thermal oxidative degradation in polymer and resin compositions
JP2020041106A (en) * 2018-09-13 2020-03-19 堺化学工業株式会社 Chlorine-containing resin composition
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