WO2012133646A1 - Heat-resistant black powder, method for producing same, and paint and resin composition using heat-resistant black powder - Google Patents

Heat-resistant black powder, method for producing same, and paint and resin composition using heat-resistant black powder Download PDF

Info

Publication number
WO2012133646A1
WO2012133646A1 PCT/JP2012/058352 JP2012058352W WO2012133646A1 WO 2012133646 A1 WO2012133646 A1 WO 2012133646A1 JP 2012058352 W JP2012058352 W JP 2012058352W WO 2012133646 A1 WO2012133646 A1 WO 2012133646A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat
black powder
resistant black
compound
metal element
Prior art date
Application number
PCT/JP2012/058352
Other languages
French (fr)
Japanese (ja)
Inventor
西本一志
好澤実
藤井泰彦
Original Assignee
戸田工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 戸田工業株式会社 filed Critical 戸田工業株式会社
Priority to CN201280006983.9A priority Critical patent/CN103339064B/en
Priority to KR1020137020042A priority patent/KR20130140837A/en
Publication of WO2012133646A1 publication Critical patent/WO2012133646A1/en

Links

Images

Classifications

    • 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
    • C09C1/0009—Pigments for ceramics
    • 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
    • C09C1/22—Compounds of iron
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C09C1/44—Carbon
    • C09C1/48—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only

Definitions

  • the present invention relates to a black powder having excellent heat resistance and little change in blackness even at high temperatures.
  • black pigments are used as various coloring materials.
  • carbon black, magnetite (Fe 3 O 4 ) and the like are known. These pigments cannot be said to be excellent in heat resistance.
  • Patent Documents 1 to 3 various improvements have been made on heat-resistant black pigments.
  • JP-A-10-279314 Japanese Patent Publication No. 47-30085 Japanese Patent Laid-Open No. 5-221653
  • Patent Documents 1 to 3 describe the use of a composite oxide containing Fe and Mn as a black pigment, but it is difficult to say that the heat resistance is excellent at high temperatures.
  • An object of the present invention is to provide a black powder having excellent heat resistance and little change in hue (blackness) even at high temperatures.
  • the present invention is a heat-resistant black powder composed of a composite oxide containing Fe, Mn and a metal element M, wherein the metal element M is one or more selected from Al, Mg and Ca.
  • the change in hue of the heat-resistant black powder at 800 ° C. in the heat resistance test is 0.5 or less and the magnetization value is 2.0 Am 2 / kg or less.
  • hematite A heat-resistant black powder characterized in that the strength ratio of the (222) plane of the bixbite phase is 45 to 250 with respect to the strength ratio of the (104) plane of the phase (Invention 1).
  • the present invention is the heat-resistant black powder according to the first invention, wherein the content of the metal element M is 0.01 to 5.0% by weight (the second invention).
  • the present invention is the heat-resistant black powder according to the first or second aspect of the present invention having a Fe / Mn (molar ratio) of 1.0 to 10.0 (Invention 3).
  • the present invention is the heat resistant black powder according to any one of the present inventions 1 to 3 having a blackness (L * value) of 25.0 or less (Invention 4).
  • the present invention also provides a method for producing a heat-resistant black powder according to any one of the present inventions 1 to 4, wherein an iron compound containing 0.01 to 5.0 wt% of the metal element M, a manganese compound, According to any one of the present inventions 1 to 4, wherein the Fe / Mn ratio (molar ratio) is mixed to be 1.0 to 10.0, and the resulting mixture is fired at a temperature range of 830 to 1000 ° C.
  • This is a method for producing heat-resistant black powder (Invention 5).
  • the present invention also relates to a method for producing a heat-resistant black powder according to any one of the present inventions 1 to 4, wherein the step of mixing an iron compound, a manganese compound and a metal element M compound and the resulting mixture It comprises a step of firing at a temperature range of 830 to 1000 ° C., and in the mixing step, when the Fe / Mn ratio (molar ratio) is 1.0 to 10.0 and the metal element M is Al, the aluminum compound is Al When the mixing ratio (Al 2 O 3 amount / (iron compound + manganese compound + aluminum compound)) as 2 O 3 is 0.01 to 10.0 wt%, when the metal element M is Mg, magnesium compound mixing ratio (MgCO 3 weight / (iron compound + manganese compound + magnesium compound)) as MgCO 3 were mixed such that 0.01 ⁇ 10.0wt%, the metal element M For a, the mixing ratio of the calcium compound is CaCO 3 (CaCO 3 weight / (iron compound + manganese compound + calcium compound)) is
  • the present invention is a paint in which the heat-resistant black powder according to any one of the present inventions 1 to 4 is blended in a paint-constituting substrate (Invention 7).
  • the present invention is a resin composition colored using the heat-resistant black powder according to any one of the first to fourth aspects of the present invention (Invention 8).
  • the heat-resistant black powder according to the present invention is suitable as a colorant for paints or resin compositions because it is excellent in heat resistance and has little change in blackness even at high temperatures.
  • FIG. 3 is an X-ray diffraction pattern of a heat-resistant black powder obtained in Example 1-1 of the present invention.
  • FIG. 2 is an enlarged view of a diffraction angle range of 20 to 40 ° with respect to FIG. 3 is an X-ray diffraction pattern of a heat-resistant black powder obtained in Example 2-1 of the present invention.
  • the heat-resistant black powder according to the present invention is composed of a composite oxide containing Fe, Mn, and a metal element M.
  • the metal element M is at least one selected from Al, Mg, and Ca.
  • the content of the metal element M in the heat-resistant black powder according to the present invention is preferably 0.01 to 5.0% by weight.
  • the content of the metal element M is less than 0.01% by weight, the heat resistance of the black powder is lowered and the blackness is changed at a high temperature.
  • the content of the metal element M exceeds 5.0% by weight, the blackness is low (L * value is high) and it is difficult to say that it is a black pigment.
  • the content of the metal element M is more preferably 0.01 to 4.0% by weight, still more preferably 0.05 to 3.0% by weight.
  • the heat-resistant black powder according to the present invention preferably has an Fe / Mn (molar ratio) of 1.0 to 10.0.
  • Fe / Mn (molar ratio) When Fe / Mn (molar ratio) is less than 1.0, the b * value is high, and it is difficult to say that it is a black powder. The heat resistance of the black powder is reduced, and the blackness may change at high temperatures. .
  • Fe / Mn (molar ratio) exceeds 10.0, the hematite phase increases and the a * value becomes high, which is difficult to say as a black pigment.
  • a more preferable Fe / Mn (molar ratio) is 1.2 to 9.0, and even more preferably 1.5 to 8.5.
  • the heat-resistant black powder according to the present invention has a hue change of 0.5 or less in a heat resistance test at 800 ° C. When the hue change exceeds 0.5, the heat resistance is low, which is not preferable. More preferably, the change in hue is 0.4 or less, and even more preferably 0.01 to 0.35.
  • the magnetization value of the heat-resistant black powder according to the present invention is 2.0 Am 2 / kg or less. When the magnetization value exceeds 2.0 Am 2 / kg, a large amount of spinel phase is present, which is not preferable because heat resistance is lowered. A more preferable magnetization value is 1.8 Am 2 / kg or less, and still more preferably 0.01 to 1.5 Am 2 / kg.
  • the intensity ratio of the (222) plane of the bixbite phase is 45 to 250 with respect to the intensity ratio of the (104) plane of the hematite phase.
  • the intensity ratio is less than 45, the ratio of the hematite phase is high and the a * value (redness) becomes strong.
  • the intensity ratio exceeds 250, the blackness may decrease (L * value increases).
  • a more preferred intensity ratio is 45 to 245, even more preferably 50 to 240.
  • a small amount of spinel phase may be contained as long as the hematite phase and the bixbite phase satisfy the above range.
  • the heat-resistant black powder according to the present invention has a blackness (L * value) of 25.0 or less.
  • the blackness (L * value) exceeds 25.0, it is not preferable as a black pigment. More preferable blackness (L * value) is 24.5 or less, and even more preferable is 20 to 24.
  • the a * value of the heat-resistant black powder according to the present invention is preferably ⁇ 2 to +5.
  • the a * value is out of the above range, it is difficult to say a black pigment. More preferably, it is ⁇ 1 to +2.
  • the b * value of the heat-resistant black powder according to the present invention is preferably ⁇ 5 to +5.
  • the b * value is out of the above range, it is difficult to say a black pigment. More preferably, it is ⁇ 4 to +2.
  • the chroma c * value of the heat-resistant black powder according to the present invention is preferably 2.5 or less, more preferably 0.1 to 2.0.
  • the heat-resistant black powder according to the present invention contains a metal element M, that is, one or more selected from Al, Mg, and Ca, so that the a * value, b * value, and c * value are relatively low, and achromatic color. It is a black pigment close to.
  • the average particle size of the heat-resistant black powder according to the present invention is preferably 0.02 to 5.0 ⁇ m.
  • the average particle diameter of the black powder 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. More preferably, it is 0.025 to 4.0 ⁇ m, and still more preferably 0.04 to 2.0 ⁇ m.
  • the BET specific surface area of the heat-resistant black powder according to the present invention is preferably 1 to 50 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 50 m 2 / g, aggregation is likely to occur due to an increase in intermolecular force due to the refinement of particles, so that it is difficult to uniformly coat the particle surface with a surface treatment agent. More preferably, it is 1.5 to 25 m 2 / g, and still more preferably 1.8 to 15 m 2 / g.
  • the shape of the particles of the heat-resistant black powder according to the present invention is not limited to a specific shape, and is spherical, granular, octahedral, hexahedral, polyhedral, etc., acicular, spindle, rice, etc. Needle-like particles and plate-like particles can be used. Considering the dispersibility of the resulting black pigment, spherical particles and granular particles are preferred.
  • the surface of the powder is coated with one or more compounds selected from Si, Al, Zr, Ti, Zn, and P or various surface treatment agents such as an organic surface treatment agent. Can be used.
  • the heat-resistant black powder according to the present invention comprises an iron compound containing 0.01 to 5.0 wt% of the metal element M and a manganese compound having a Fe / Mn ratio (molar ratio) of 1.0 to 10.0.
  • the resulting mixture can be fired in the temperature range of 830 to 1000 ° C.
  • the heat-resistant black powder according to the present invention can be obtained from a step of mixing an iron compound, a manganese compound and a compound of the metal element M and a step of firing the obtained mixture in a temperature range of 830 to 1000 ° C. .
  • the mixing ratio of the aluminum compound as Al 2 O 3 Al 2 O 3 amount / (iron compound + manganese compound + aluminum compound)
  • the mixing ratio of the magnesium compound as MgCO 3 MgCO 3 weight / ( iron compound + manganese compound + magnesium compound)
  • the mixing ratio of the calcium compound as CaCO 3 CaCO 3 weight / (iron Compound + manganese compound + calcium compound)
  • iron compounds containing 0.01 to 5.0 wt% of aluminum, magnesium and calcium a method of adding aluminum, magnesium and calcium at the time of iron compound synthesis, or coating or adhering various compounds of aluminum, magnesium and calcium to iron compounds It can manufacture by the method to make.
  • the iron compound, manganese compound, aluminum compound, magnesium compound and calcium compound may be appropriately selected from oxides, hydroxides, carbonates, nitrates, sulfates, chlorides and the like of each element.
  • the mixing of the starting materials is not particularly limited as long as it can be uniformly mixed, and may be wet mixing or dry mixing. Also, wet synthesis may be used.
  • the heating and baking temperature is preferably 830 to 1000 ° C., more preferably 850 to 950 ° C.
  • the heating atmosphere is not particularly limited, but can be performed in the air.
  • the heated powder may be washed and pulverized according to a conventional method.
  • the composition ratio of the elements is controlled and the composition is controlled. Accordingly, it is necessary to control the heating and baking temperature.
  • the baking temperature is lowered, the hematite phase increases and the bixbite phase tends to decrease relatively.
  • the magnetite phase increases and the bixbite phase tends to decrease relatively.
  • the particle surface of the heat-resistant black powder may be coated with one or more compounds selected from Si, Al, Zr, Ti, Zn, and P.
  • the surface treatment method may be performed according to a conventional method such as a wet method or a dry method.
  • a wet method one or more soluble compounds selected from Si, Al, and Zr are added to and mixed with a slurry of heat-resistant black powder that has been wet-dispersed while adjusting the pH with an acid or alkali.
  • the dry method is a method in which heat-resistant black powder is coated with one or more coupling agents selected from Si, Al, Zr, and Ti in an apparatus such as a Henschel mixer.
  • the blending ratio of the heat-resistant black powder in the paint according to the present invention can be used in the range of 0.5 to 100 parts by weight with respect to 100 parts by weight of the paint base material, taking into account the handleability of the paint. For example, it is preferably 1.0 to 100 parts by weight.
  • paint constituting base material resin, solvent, and if necessary, fats and oils, antifoaming agent, extender pigment, drying accelerator, surfactant, curing accelerator, auxiliary agent and the like are blended.
  • resin As the resin, solvent, or water-based paint solvent, those usually used for solvent-based paint or oil-based printing ink may be used.
  • the blending ratio of the heat-resistant black powder in the resin composition according to the present invention can be used in the range of 0.01 to 200 parts by weight with respect to 100 parts by weight of the resin, and the handling property of the resin composition is taken into consideration.
  • the amount is preferably 0.05 to 150 parts by weight, more preferably 0.1 to 100 parts by weight.
  • a heat-resistant black powder and a known thermoplastic resin As a constituent substrate in the resin composition according to the present invention, a heat-resistant black powder and a known thermoplastic resin, and additives such as a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, and various stabilizers as necessary. Is blended.
  • the resin a commonly used resin may be used.
  • the resin composition according to the present invention is obtained by mixing a resin raw material and a heat-resistant black powder in advance, and then applying a strong shearing action under heating using a kneader or an extruder, The aggregate is broken and the heat-resistant black powder is uniformly dispersed in the resin composition, and then molded into a shape according to the purpose and used.
  • the resin composition according to the present invention can also be obtained via a master batch pellet.
  • the binder resin as a constituent substrate of the resin composition, the heat-resistant black powder and various additives are mixed with a mixer if necessary, and then a well-known single-screw kneading extrusion. It is manufactured by kneading and molding after a kneading machine or a twin-screw kneading extruder or cutting, or by crushing or molding and cutting the kneaded material obtained by kneading the above mixture with a Banbury mixer, pressure kneader or the like.
  • the supply of the binder resin and the heat-resistant black powder to the kneader may be quantitatively supplied at a predetermined ratio, or a mixture of both may be supplied.
  • 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 bad and 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 heat-resistant black powder blended in the master batch pellet is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the binder resin.
  • the crystal structure of the heat-resistant black powder is measured with an “X-ray diffractometer RINT2500” (manufactured by Rigaku Denki Kogyo Co., Ltd.), corrected for smoothing, background removal, K ⁇ removal, etc. with the attached program. A search was performed to determine the d value and the peak intensity.
  • the intensity ratio of the (222) plane of the bixbite phase and the intensity ratio of the (311) plane of the spinel phase were determined with respect to the intensity ratio of the (104) plane of the hematite phase.
  • the content of metal elements (Fe, Mn, Al, Mg, Ca) in heat-resistant black powder, and the content of Al, Mg, Ca in the Fe raw material were determined using ICP emission spectroscopic analyzer iCAP-6500DUO (Thermo Electron Co., Ltd.) Made). Moreover, it converted into molar ratio and calculated
  • the hue (L * value, a * value, b * value) of the heat-resistant black powder was obtained by kneading 0.5 g of a sample and 0.5 ml of castor oil with a Hoover type Mahler to form a paste. 0.5 g was added, kneaded and converted into a paint, and an application piece (coating thickness: about 30 ⁇ m) applied on a cast coated paper using a 150 ⁇ m (6 mil) applicator was prepared. The coating piece was measured using a “color difference meter CR-300” (manufactured by Konica Minolta Sensing Co., Ltd.), and the color index (L * value, a * value, b * value) according to JIS Z 8729.
  • the heat resistance of the heat-resistant black powder is as follows: 10 g of a sample is put in a magnetic crucible, heat-treated at 800 ° C. for 2 hours using an electric furnace, allowed to cool, the color of the sample powder is measured, and before heat treatment It was obtained by measuring the change in hue after and was expressed by ⁇ E expressed by the following formula based on the measured color before the heat treatment. The smaller ⁇ E, the smaller the change in hue and the better the heat resistance.
  • ⁇ E ⁇ ( ⁇ L) 2 + ( ⁇ a) 2 + ( ⁇ b) 2 ⁇ 1/2
  • ⁇ L difference in L * value between samples to be compared
  • ⁇ a difference in a * value between samples to be compared
  • ⁇ b difference in b * value between samples to be compared
  • the magnetization value is a value measured by applying an external magnetic field of 796 kA / m (10 kOe) with a “sample vibration magnetometer BHV-35” (manufactured by Riken Denshi Co., Ltd.).
  • the specific surface area is indicated by a value measured by the BET method.
  • Examples 1-1 to 1-9 shown below are examples in which Al is used as the metal element M, and Comparative Examples 1-1 to 1-7 are comparative examples relative to Examples 1-1 to 1-9. It is.
  • Example 1-1 453 g (75.5 wt%) of magnetite (MAT-305 manufactured by Toda Kogyo Co., Ltd.) having an Al content of 0.23 wt% was mixed with 147 g (24.5 wt%) of trimanganese tetroxide. Baked at 2 ° C. for 2 hours. The fired product was pulverized to obtain a black powder.
  • magnetite MAT-305 manufactured by Toda Kogyo Co., Ltd.
  • the obtained powder had a magnetization value of 0.9 Am 2 / kg and a specific surface area of 2.4 m 2 / g.
  • the hue of the coated piece made of clear lacquer is a black powder having an L * value of 23.5, an a * value of 1.2, a b * value of 0.2, and a converted c * value of 1.2. It was a body.
  • the powder obtained by heating the obtained powder at 800 ° C. for 2 hours in an electric furnace has an L * value of 23.5, an a * value of 1.1, and a b * value of 0.1.
  • the property ⁇ E was 0.1, and the black powder was excellent in heat resistance.
  • Examples 1-2 to 1-7 A black powder was obtained in the same manner as in Example 1 except that the iron raw material composition, size, mixing ratio with trimanganese tetroxide, and firing temperature were changed.
  • Example 1-8 457 g (75.4 wt%) of magnetite not containing Al and 143 g (23.6 wt%) of trimanganese tetroxide were mixed with 5.7 g of aluminum oxide (1.0 wt%, purity 99.7 wt%). And baked at 990 ° C. for 2 hours. The fired product was pulverized to obtain a black powder.
  • Example 1-9 A black powder was obtained in the same manner as in Example 1-8, except that the mixing ratio of the magnetite not containing Al, trimanganese tetroxide, and aluminum oxide and the firing temperature were changed.
  • Comparative Example 1-1 A powder was obtained in the same manner as in Example 1-1 except that the iron raw material not containing Al, the size, the mixing ratio with trimanganese tetroxide and the firing temperature were changed.
  • the obtained powder had a strength ratio of the bixbite phase 15 to the hematite phase 100.
  • the hue of the coating piece made into a paint with clear lacquer has an L * value of 25.5, an a * value of 5.0, a b * value of 3.0, a c * value of 5.9, and a heat resistance ⁇ E of It was 1.5, and it was hard to say black, and it was a powder having low heat resistance.
  • Comparative Examples 1-2 to 1-6 A powder was obtained in the same manner as in Comparative Example 1-1 except that the type and size of the iron raw material, the mixing ratio with trimanganese tetroxide and the firing temperature were changed.
  • Comparative Example 1-7 A black powder was obtained in the same manner as in Example 1-8, except that the mixing ratio of the magnetite not containing Al, trimanganese tetroxide, and aluminum oxide and the firing temperature were changed.
  • Table 1 shows the production conditions of the heat-resistant black powder
  • Table 2 shows the characteristics of the obtained heat-resistant black powder.
  • Examples 2-1 to 2-8 shown below are examples in which Al is used as the metal element M, and Comparative Examples 2-1 to 2-2 are comparative examples for Examples 2-1 to 2-8. It is.
  • the obtained powder had a magnetization value of 0.7 Am 2 / kg and a specific surface area of 1.7 m 2 / g.
  • the hue of the coated piece made of clear lacquer is black with L * value of 24.6, a * value of 0.6, b * value of -0.3, and converted c * value of 0.6. It was a powder.
  • the hue of the powder obtained by heating the obtained powder in an electric furnace at 800 ° C. for 2 hours has an L * value of 24.6, an a * value of 0.8, and a b * value of ⁇ 0.2.
  • the heat resistance ⁇ E was 0.2, and the black powder was excellent in heat resistance.
  • Example 2-6 Magnetite (manufactured by Toda Kogyo Co., Ltd.) 437 g (72.9 wt%) and trimanganese tetroxide 142 g (23.7 wt%) are mixed with magnesium carbonate 20 g (3.4 wt%, purity 99.9 wt%). And baked at 940 ° C. for 6 hours. The fired product was pulverized to obtain a black powder.
  • the obtained powder had a magnetization value of 1.9 Am 2 / kg and a specific surface area of 2.0 m 2 / g.
  • the hue of the coated piece made of clear lacquer is L * value 24.4, a * value 0.7, b * value -0.2, converted c * value 0.7, heat resistance It was a black powder having a property ⁇ E of 0.3.
  • Examples 2-2 to 2-5, 2-7, 2-8 Black powders were obtained in the same manner as in Examples 2-1 and 2-6, except that the mixing ratio of magnetite, trimanganese tetroxide, calcium carbonate, and magnesium carbonate and the firing temperature were changed.
  • Example 2-9 442 g (73.8 wt%) of magnetite having an average particle size of 0.28 ⁇ m, an Al content of 0.23 wt% and an Mg content of 0.15 wt%, and 143 g (23.8 wt%) of trimanganese tetroxide 14 g (2.3 wt%, purity 99 wt%) was mixed and baked in an electric furnace at 980 ° C. for 8 hours. The fired product was pulverized to obtain a black powder.
  • the obtained powder had a strength ratio of the bixbite phase 163 to the hematite phase 100.
  • Fe / Mn (molar ratio) 3.0, Ca content 0.96 wt%, Mg content 0.10 wt%, Al content 0.15 wt%.
  • the obtained black powder had a magnetization value of 1.6 Am 2 / kg and a specific surface area of 1.9 m 2 / g.
  • the hue of the coated piece made into a clear lacquer paint is L * value 24.2, a * value 0.7, b * value -0.4, converted c * value 0.8, heat resistance It was a black powder having a property ⁇ E of 0.3.
  • Comparative Example 2-1 A powder was obtained in the same manner as in Example 2-1, except that the iron raw material, size, mixing ratio with trimanganese tetroxide, and firing temperature were changed.
  • the obtained powder had a strength ratio of the bixbite phase 15 to the hematite phase 100.
  • the hue of the coating piece made into a paint with clear lacquer has an L * value of 25.5, an a * value of 5.0, a b * value of 3.2, a c * value of 5.9, and a heat resistance ⁇ E of It was 1.5, and it was hard to say black, and it was a powder having low heat resistance.
  • Comparative Example 2-2 A powder was obtained in the same manner as in Comparative Example 2-1, except that the type and size of the iron raw material, the mixing ratio with trimanganese tetroxide and the firing temperature were changed.
  • Table 3 shows the production conditions of the heat-resistant black powder
  • Table 4 shows the characteristics of the obtained heat-resistant black powder.
  • the heat-resistant black powder according to the present invention is suitable as a colorant for paints or resin compositions because it has excellent heat resistance and little change in hue (blackness) even at high temperatures.
  • Applications include mainly automobiles and motorcycle mufflers, engine covers, plant indoor and outdoor heating facilities, incinerators, chimneys, kitchen equipment, rocket launch pads, and various paints that require heat resistance and appearance. Useful.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Ceramic Engineering (AREA)
  • Compounds Of Iron (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a heat-resistant black powder that is ideal as a paint or resin composition because heat resistance is excellent and there is little change in color (degree of black) even under a high temperature. The heat-resistant black powder is formed from a compound oxide comprising Fe, Mn, and metal element M (where M is one or more selected from Al, Mg, and Ca). The change in color in heat resistance testing at 800ºC is 0.5 or less and the magnetization value is 2.0 Am2/kg or less. The heat-resistant black powder is a heat-resistant black powder formed from a hematite phase and a bixbite phase. The heat-resistant black powder can be obtained by mixing an iron compound, a manganese compound, and a metal element M compound and baking the resulting mixture at a temperature range of 830 to 1,000ºC.

Description

耐熱性黒色粉体及びその製造方法、該耐熱性黒色粉体を用いた塗料及び樹脂組成物Heat-resistant black powder and method for producing the same, paint and resin composition using the heat-resistant black powder
　本発明は、耐熱性に優れ高温下でも黒色度の変化が少ない黒色粉体に関する。 The present invention relates to a black powder having excellent heat resistance and little change in blackness even at high temperatures.
　現在、黒色顔料は種々の着色材料として用いられている。黒色顔料としては、カーボンブラック、マグネタイト（Ｆｅ３Ｏ４）などが知られている。これらの顔料は耐熱性に優れるとは言い難いものである。 Currently, black pigments are used as various coloring materials. As black pigments, carbon black, magnetite (Fe 3 O 4 ) and the like are known. These pigments cannot be said to be excellent in heat resistance.
　また、耐熱性を有する黒色顔料としては、Ｃｒ系の複合酸化物なども知られているが、Ｃｒを含有する点において環境負荷が高いことなどが問題視されている。 Further, as a black pigment having heat resistance, Cr-based complex oxides and the like are also known, but the environmental load is high in view of containing Cr.
　そこで、無害な元素から構成され、しかも、高い耐熱性を有する黒色顔料が要求されている。 Therefore, there is a demand for black pigments composed of harmless elements and having high heat resistance.
　現在、耐熱性を有する黒色顔料について種々の改良がなされている（特許文献１～３）。 Currently, various improvements have been made on heat-resistant black pigments (Patent Documents 1 to 3).
特開平１０－２７９３１４号公報JP-A-10-279314 特公昭４７－３００８５号公報Japanese Patent Publication No. 47-30085 特開平５－２２１６５３号公報Japanese Patent Laid-Open No. 5-221653
　耐熱性に優れ高温下でも黒色度の変化が少ない黒色顔料は未だ得られていない。 Black pigments that have excellent heat resistance and little change in blackness even at high temperatures have not yet been obtained.
　即ち、特許文献１～３には、ＦｅとＭｎとを含有する複合酸化物を黒色顔料として用いることが記載されているが、高温下で耐熱性に優れるとは言い難いものである。 That is, Patent Documents 1 to 3 describe the use of a composite oxide containing Fe and Mn as a black pigment, but it is difficult to say that the heat resistance is excellent at high temperatures.
　本発明の目的は、耐熱性に優れ高温下でも色相（黒色度）の変化が少ない黒色粉体を提供することである。 An object of the present invention is to provide a black powder having excellent heat resistance and little change in hue (blackness) even at high temperatures.
　前記目的は、次のとお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、ＦｅとＭｎと金属元素Ｍとを含有する複合酸化物からなる耐熱性黒色粉体であって、金属元素ＭはＡｌ、Ｍｇ及びＣａから選択される１種以上であり、耐熱性黒色粉体の８００℃での耐熱試験の色相の変化が０．５以下で且つ磁化値が２．０Ａｍ２／ｋｇ以下であり、当該耐熱性黒色粉体のＸ線回折スペクトルにおいて、ヘマタイト相の（１０４）面の強度比１００に対し、ビクスバイト相の（２２２）面の強度比が４５～２５０であることを特徴とする耐熱性黒色粉体である（本発明１）。 That is, the present invention is a heat-resistant black powder composed of a composite oxide containing Fe, Mn and a metal element M, wherein the metal element M is one or more selected from Al, Mg and Ca. The change in hue of the heat-resistant black powder at 800 ° C. in the heat resistance test is 0.5 or less and the magnetization value is 2.0 Am 2 / kg or less. In the X-ray diffraction spectrum of the heat-resistant black powder, hematite A heat-resistant black powder characterized in that the strength ratio of the (222) plane of the bixbite phase is 45 to 250 with respect to the strength ratio of the (104) plane of the phase (Invention 1).
　また、本発明は、金属元素Ｍの含有量が０．０１～５．０重量％である本発明１記載の耐熱性黒色粉体である（本発明２）。 Further, the present invention is the heat-resistant black powder according to the first invention, wherein the content of the metal element M is 0.01 to 5.0% by weight (the second invention).
　また、本発明は、Ｆｅ／Ｍｎ（モル比）が１．０～１０．０である本発明１又は２記載の耐熱性黒色粉体である（本発明３）。 Further, the present invention is the heat-resistant black powder according to the first or second aspect of the present invention having a Fe / Mn (molar ratio) of 1.0 to 10.0 (Invention 3).
　また、本発明は、黒色度（Ｌ＊値）が２５．０以下である本発明１～３のいずれかに記載の耐熱性黒色粉体である（本発明４）。 Further, the present invention is the heat resistant black powder according to any one of the present inventions 1 to 3 having a blackness (L * value) of 25.0 or less (Invention 4).
　また、本発明は、本発明１～４のいずれかに記載の耐熱性黒色粉体の製造方法であって、金属元素Ｍを０．０１～５．０ｗｔ％含有する鉄化合物と、マンガン化合物とをＦｅ／Ｍｎ比（モル比）が１．０～１０．０となるように混合し、得られた混合物を８３０～１０００℃の温度範囲で焼成する本発明１～４のいずれかに記載の耐熱性黒色粉体の製造方法である（本発明５）。 The present invention also provides a method for producing a heat-resistant black powder according to any one of the present inventions 1 to 4, wherein an iron compound containing 0.01 to 5.0 wt% of the metal element M, a manganese compound, According to any one of the present inventions 1 to 4, wherein the Fe / Mn ratio (molar ratio) is mixed to be 1.0 to 10.0, and the resulting mixture is fired at a temperature range of 830 to 1000 ° C. This is a method for producing heat-resistant black powder (Invention 5).
　また、本発明は、本発明１～４のいずれかに記載の耐熱性黒色粉体の製造方法であって、鉄化合物、マンガン化合物及び金属元素Ｍの化合物を混合する工程および得られた混合物を８３０～１０００℃の温度範囲で焼成する工程から成り、上記混合工程において、Ｆｅ／Ｍｎ比（モル比）が１．０～１０．０であり、金属元素ＭがＡｌの場合、アルミニウム化合物がＡｌ２Ｏ３としての混合割合（Ａｌ２Ｏ３量／（鉄化合物＋マンガン化合物＋アルミニウム化合物））が０．０１～１０．０ｗｔ％となるように混合し、金属元素ＭがＭｇの場合、マグネシウム化合物がＭｇＣＯ３としての混合割合（ＭｇＣＯ３量／（鉄化合物＋マンガン化合物＋マグネシウム化合物））が０．０１～１０．０ｗｔ％となるように混合し、金属元素ＭがＣａの場合、カルシウム化合物がＣａＣＯ３としての混合割合（ＣａＣＯ３量／（鉄化合物＋マンガン化合物＋カルシウム化合物））が０．０１～１０．０ｗｔ％となるように混合する本発明１～４のいずれかに記載の耐熱性黒色粉体の製造方法である（本発明６）。 The present invention also relates to a method for producing a heat-resistant black powder according to any one of the present inventions 1 to 4, wherein the step of mixing an iron compound, a manganese compound and a metal element M compound and the resulting mixture It comprises a step of firing at a temperature range of 830 to 1000 ° C., and in the mixing step, when the Fe / Mn ratio (molar ratio) is 1.0 to 10.0 and the metal element M is Al, the aluminum compound is Al When the mixing ratio (Al 2 O 3 amount / (iron compound + manganese compound + aluminum compound)) as 2 O 3 is 0.01 to 10.0 wt%, when the metal element M is Mg, magnesium compound mixing ratio (MgCO 3 weight / (iron compound + manganese compound + magnesium compound)) as MgCO 3 were mixed such that 0.01 ~ 10.0wt%, the metal element M For a, the mixing ratio of the calcium compound is CaCO 3 (CaCO 3 weight / (iron compound + manganese compound + calcium compound)) is of the present invention 1 to 4 are mixed to give a 0.01 ~ 10.0 wt% It is a manufacturing method of the heat resistant black powder in any one (this invention 6).
　また、本発明は、本発明１～４のいずれかに記載の耐熱性黒色粉体を塗料構成基材中に配合した塗料である（本発明７）。 Further, the present invention is a paint in which the heat-resistant black powder according to any one of the present inventions 1 to 4 is blended in a paint-constituting substrate (Invention 7).
　また、本発明は、本発明１～４のいずれかに記載の耐熱性黒色粉体を用いて着色した樹脂組成物である（本発明８）。 In addition, the present invention is a resin composition colored using the heat-resistant black powder according to any one of the first to fourth aspects of the present invention (Invention 8).
　本発明に係る耐熱性黒色粉体は、耐熱性に優れ、高温下でも黒色度の変化が少ないので、塗料又は樹脂組成物の着色材として好適である。 The heat-resistant black powder according to the present invention is suitable as a colorant for paints or resin compositions because it is excellent in heat resistance and has little change in blackness even at high temperatures.
本発明の実施例１－１で得られた耐熱性黒色粉体のＸ線回折パターンである。3 is an X-ray diffraction pattern of a heat-resistant black powder obtained in Example 1-1 of the present invention. 図１について、回折角が２０～４０°の範囲を拡大した図である。FIG. 2 is an enlarged view of a diffraction angle range of 20 to 40 ° with respect to FIG. 本発明の実施例２－１で得られた耐熱性黒色粉体のＸ線回折パターンである。3 is an X-ray diffraction pattern of a heat-resistant black powder obtained in Example 2-1 of the present invention.
　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、本発明に係る耐熱性黒色粉体について述べる。 First, the heat-resistant black powder according to the present invention will be described.
　本発明に係る耐熱性黒色粉体は、ＦｅとＭｎと金属元素Ｍとを含有する複合酸化物からなる。金属元素ＭはＡｌ、Ｍｇ及びＣａから選択される１種以上である。 The heat-resistant black powder according to the present invention is composed of a composite oxide containing Fe, Mn, and a metal element M. The metal element M is at least one selected from Al, Mg, and Ca.
　本発明に係る耐熱性黒色粉体の金属元素Ｍの含有量は０．０１～５．０重量％であることが好ましい。金属元素Ｍの含有量が０．０１重量％未満の場合、黒色粉体の耐熱性が低下し高温下で黒色度が変化する。金属元素Ｍの含有量が５．０重量％を超える場合、黒色度が低くなり（Ｌ＊値が高くなり）黒色顔料とは言い難い。より好ましい金属元素Ｍの含有量は０．０１～４．０重量％であり、更により好ましくは０．０５～３．０重量％である。 The content of the metal element M in the heat-resistant black powder according to the present invention is preferably 0.01 to 5.0% by weight. When the content of the metal element M is less than 0.01% by weight, the heat resistance of the black powder is lowered and the blackness is changed at a high temperature. When the content of the metal element M exceeds 5.0% by weight, the blackness is low (L * value is high) and it is difficult to say that it is a black pigment. The content of the metal element M is more preferably 0.01 to 4.0% by weight, still more preferably 0.05 to 3.0% by weight.
　本発明に係る耐熱性黒色粉体のＦｅ／Ｍｎ（モル比）は１．０～１０．０であることが好ましい。Ｆｅ／Ｍｎ（モル比）が１．０未満の場合、ｂ＊値が高くなり、黒色粉体とは言い難く、黒色粉体の耐熱性が低下し高温下で黒色度が変化する場合がある。Ｆｅ／Ｍｎ（モル比）が１０．０を超える場合、ヘマタイト相が多くなりａ＊値が高くなり黒色顔料とは言い難い。より好ましいＦｅ／Ｍｎ（モル比）は１．２～９．０であり、更により好ましくは１．５～８．５である。 The heat-resistant black powder according to the present invention preferably has an Fe / Mn (molar ratio) of 1.0 to 10.0. When Fe / Mn (molar ratio) is less than 1.0, the b * value is high, and it is difficult to say that it is a black powder. The heat resistance of the black powder is reduced, and the blackness may change at high temperatures. . When Fe / Mn (molar ratio) exceeds 10.0, the hematite phase increases and the a * value becomes high, which is difficult to say as a black pigment. A more preferable Fe / Mn (molar ratio) is 1.2 to 9.0, and even more preferably 1.5 to 8.5.
　本発明に係る耐熱性黒色粉体は、８００℃での耐熱試験の色相の変化が０．５以下である。前記色相の変化が０．５を超える場合、耐熱性が低いものであり好ましくない。より好ましくは色相の変化が０．４以下であり、更により好ましくは０．０１～０．３５である。 The heat-resistant black powder according to the present invention has a hue change of 0.5 or less in a heat resistance test at 800 ° C. When the hue change exceeds 0.5, the heat resistance is low, which is not preferable. More preferably, the change in hue is 0.4 or less, and even more preferably 0.01 to 0.35.
　本発明に係る耐熱性黒色粉体の磁化値が２．０Ａｍ２／ｋｇ以下である。磁化値が２．０Ａｍ２／ｋｇを超える場合には、スピネル相が多量に存在するため耐熱性が低くなり好ましくない。より好ましい磁化値は１．８Ａｍ２／ｋｇ以下であり、更により好ましくは０．０１～１．５Ａｍ２／ｋｇである。 The magnetization value of the heat-resistant black powder according to the present invention is 2.0 Am 2 / kg or less. When the magnetization value exceeds 2.0 Am 2 / kg, a large amount of spinel phase is present, which is not preferable because heat resistance is lowered. A more preferable magnetization value is 1.8 Am 2 / kg or less, and still more preferably 0.01 to 1.5 Am 2 / kg.
　本発明に係る耐熱性黒色粉体のＸ線回折スペクトルにおいて、ヘマタイト相の（１０４）面の強度比１００に対し、ビクスバイト相の（２２２）面の強度比が４５～２５０である。前記強度比が４５未満の場合、ヘマタイト相の比率が高く、ａ＊値（赤み）が強くなる。前記強度比が２５０を超える場合、黒色度が低下する（Ｌ＊値が高くなる）場合がある。より好ましい強度比は４５～２４５であり、更により好ましくは５０～２４０である。なお、本発明においては、ヘマタイト相とビクスバイト相とが前記範囲を満たすものであれば、少量のスピネル相を含有しても良い。 In the X-ray diffraction spectrum of the heat-resistant black powder according to the present invention, the intensity ratio of the (222) plane of the bixbite phase is 45 to 250 with respect to the intensity ratio of the (104) plane of the hematite phase. When the intensity ratio is less than 45, the ratio of the hematite phase is high and the a * value (redness) becomes strong. When the intensity ratio exceeds 250, the blackness may decrease (L * value increases). A more preferred intensity ratio is 45 to 245, even more preferably 50 to 240. In the present invention, a small amount of spinel phase may be contained as long as the hematite phase and the bixbite phase satisfy the above range.
　本発明に係る耐熱性黒色粉体の黒色度（Ｌ＊値）が２５．０以下である耐熱性黒色粉体である。黒色度（Ｌ＊値）が２５．０を超える場合には、黒色顔料として好ましくない。より好ましい黒色度（Ｌ＊値）は２４．５以下であり、更により好ましくは２０～２４である。 The heat-resistant black powder according to the present invention has a blackness (L * value) of 25.0 or less. When the blackness (L * value) exceeds 25.0, it is not preferable as a black pigment. More preferable blackness (L * value) is 24.5 or less, and even more preferable is 20 to 24.
　本発明に係る耐熱性黒色粉体のａ＊値は、－２～＋５が好ましい。ａ＊値が前記範囲外の場合には、黒色顔料とは言い難い。より好ましくは－１～＋２である。 The a * value of the heat-resistant black powder according to the present invention is preferably −2 to +5. When the a * value is out of the above range, it is difficult to say a black pigment. More preferably, it is −1 to +2.
　本発明に係る耐熱性黒色粉体のｂ＊値は、－５～＋５が好ましい。ｂ＊値が前記範囲外の場合には、黒色顔料とは言い難い。より好ましくは－４～＋２である。 The b * value of the heat-resistant black powder according to the present invention is preferably −5 to +5. When the b * value is out of the above range, it is difficult to say a black pigment. More preferably, it is −4 to +2.
　本発明に係る耐熱性黒色粉体の彩度ｃ＊値は、２．５以下が好ましく、より好ましくは０．１～２．０である。 The chroma c * value of the heat-resistant black powder according to the present invention is preferably 2.5 or less, more preferably 0.1 to 2.0.
　本発明に係る耐熱性黒色粉体は金属元素Ｍ、すなわちＡｌ、Ｍｇ及びＣａから選択される１種以上が含有する事でａ＊値、ｂ＊値、ｃ＊値が比較的低く、無彩色に近い黒色顔料である。 The heat-resistant black powder according to the present invention contains a metal element M, that is, one or more selected from Al, Mg, and Ca, so that the a * value, b * value, and c * value are relatively low, and achromatic color. It is a black pigment close to.
　本発明に係る耐熱性黒色粉体の平均粒子径は、０．０２～５．０μｍが好ましい。黒色粉体の平均粒子径が５．０μｍを超える場合には、粒子サイズが大きすぎるため、着色力が低下する。平均粒子径が０．０２μｍ未満の場合には、ビヒクル中への分散が困難となる場合がある。より好ましくは０．０２５～４．０μｍ、更により好ましくは０．０４～２．０μｍである。 The average particle size of the heat-resistant black powder according to the present invention is preferably 0.02 to 5.0 μm. When the average particle diameter of the black powder 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. More preferably, it is 0.025 to 4.0 μm, and still more preferably 0.04 to 2.0 μm.
　本発明に係る耐熱性黒色粉体のＢＥＴ比表面積は、１～５０ｍ２／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５０ｍ２／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１．５～２５ｍ２／ｇ、更により好ましくは１．８～１５ｍ２／ｇである。 The BET specific surface area of the heat-resistant black powder according to the present invention is preferably 1 to 50 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 50 m 2 / g, aggregation is likely to occur due to an increase in intermolecular force due to the refinement of particles, so that it is difficult to uniformly coat the particle surface with a surface treatment agent. More preferably, it is 1.5 to 25 m 2 / g, and still more preferably 1.8 to 15 m 2 / g.
　本発明に係る耐熱性黒色粉体の粒子の形状は、特定の形状に限定されず、球状、粒状、八面体状、六面体状、多面体状等の粒状粒子、針状、紡錘状、米粒状等の針状粒子及び板状粒子等を使用することができる。得られる黒色顔料の分散性を考慮すれば、球状粒子及び粒状粒子が好ましい。 The shape of the particles of the heat-resistant black powder according to the present invention is not limited to a specific shape, and is spherical, granular, octahedral, hexahedral, polyhedral, etc., acicular, spindle, rice, etc. Needle-like particles and plate-like particles can be used. Considering the dispersibility of the resulting black pigment, spherical particles and granular particles are preferred.
　本発明に係る耐熱性黒色粉体において、粉体の表面を、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等の各種表面処理剤で被覆して使用することができる。 In the heat-resistant black powder according to the present invention, the surface of the powder is coated with one or more compounds selected from Si, Al, Zr, Ti, Zn, and P or various surface treatment agents such as an organic surface treatment agent. Can be used.
　次に、本発明に係る耐熱性黒色粉体の製造方法について述べる。 Next, a method for producing a heat-resistant black powder according to the present invention will be described.
　本発明に係る耐熱性黒色粉体は、金属元素Ｍを０．０１～５．０ｗｔ％含有する鉄化合物と、マンガン化合物とをＦｅ／Ｍｎ比（モル比）が１．０～１０．０となるように混合し、得られた混合物を８３０～１０００℃の温度範囲で焼成して得ることができる。 The heat-resistant black powder according to the present invention comprises an iron compound containing 0.01 to 5.0 wt% of the metal element M and a manganese compound having a Fe / Mn ratio (molar ratio) of 1.0 to 10.0. The resulting mixture can be fired in the temperature range of 830 to 1000 ° C.
　また、本発明に係る耐熱性黒色粉体は、鉄化合物、マンガン化合物及び金属元素Ｍの化合物を混合する工程および得られた混合物を８３０～１０００℃の温度範囲で焼成する工程から得ることができる。上記混合工程において、Ｆｅ／Ｍｎ比（モル比）が１．０～１０．０であり、金属元素ＭがＡｌの場合、アルミニウム化合物がＡｌ２Ｏ３としての混合割合（Ａｌ２Ｏ３量／（鉄化合物＋マンガン化合物＋アルミニウム化合物））が０．０１～１０．０ｗｔ％となるように混合し、金属元素ＭがＭｇの場合、マグネシウム化合物がＭｇＣＯ３としての混合割合（ＭｇＣＯ３量／（鉄化合物＋マンガン化合物＋マグネシウム化合物））が０．０１～１０．０ｗｔ％となるように混合し、金属元素ＭがＣａの場合、カルシウム化合物がＣａＣＯ３としての混合割合（ＣａＣＯ３量／（鉄化合物＋マンガン化合物＋カルシウム化合物））が０．０１～１０．０ｗｔ％となるようにする。 The heat-resistant black powder according to the present invention can be obtained from a step of mixing an iron compound, a manganese compound and a compound of the metal element M and a step of firing the obtained mixture in a temperature range of 830 to 1000 ° C. . In the above mixing step, when the Fe / Mn ratio (molar ratio) is 1.0 to 10.0 and the metal element M is Al, the mixing ratio of the aluminum compound as Al 2 O 3 (Al 2 O 3 amount / (iron compound + manganese compound + aluminum compound)) is 0.01 to mixing such that the 10.0 wt%, when the metal element M is Mg, the mixing ratio of the magnesium compound as MgCO 3 (MgCO 3 weight / ( iron compound + manganese compound + magnesium compound)) is mixed in a 0.01 ~ 10.0wt%, when the metal element M is Ca, the mixing ratio of the calcium compound as CaCO 3 (CaCO 3 weight / (iron Compound + manganese compound + calcium compound)) is adjusted to 0.01 to 10.0 wt%.
　アルミニウム、マグネシウム、カルシウムを０．０１～５．０ｗｔ％含有する鉄化合物としては、鉄化合物合成時にアルミニウム、マグネシウム、カルシウムを添加する方法、鉄化合物にアルミニウム、マグネシウム、カルシウムの各種化合物を被覆又は付着させる方法によって製造することができる。 As iron compounds containing 0.01 to 5.0 wt% of aluminum, magnesium and calcium, a method of adding aluminum, magnesium and calcium at the time of iron compound synthesis, or coating or adhering various compounds of aluminum, magnesium and calcium to iron compounds It can manufacture by the method to make.
　鉄化合物、マンガン化合物、アルミニウム化合物、マグネシウム化合物及びカルシウム化合物としては、各元素の酸化物、水酸化物、炭酸塩、硝酸塩、硫酸塩、塩化物等の中から適宜選択すればよい。 The iron compound, manganese compound, aluminum compound, magnesium compound and calcium compound may be appropriately selected from oxides, hydroxides, carbonates, nitrates, sulfates, chlorides and the like of each element.
　出発原料の混合は、均一に混合することができれば、特に限定されるものではなく、湿式混合でも乾式混合でもよい。また湿式合成であってもよい。 The mixing of the starting materials is not particularly limited as long as it can be uniformly mixed, and may be wet mixing or dry mixing. Also, wet synthesis may be used.
　加熱焼成温度は８３０～１０００℃が好ましく、より好ましくは８５０～９５０℃である。加熱雰囲気は特に限定されないが、大気中で実施出来る。 The heating and baking temperature is preferably 830 to 1000 ° C., more preferably 850 to 950 ° C. The heating atmosphere is not particularly limited, but can be performed in the air.
　加熱後の粉末は、必要により、常法に従って、水洗、粉砕を行えばよい。 If necessary, the heated powder may be washed and pulverized according to a conventional method.
　本発明において、複合酸化物のヘマタイト相の（１０４）面の強度比とビクスバイト相の（２２２）面の強度比との比率を制御するためには、元素の組成比を制御するとともに組成に応じて加熱焼成温度を制御する必要がある。加熱焼成温度が低くなるとヘマタイト相が増加し相対的にビクスバイト相が減少する傾向にある。一方、加熱焼成温度が高くなるとマグネタイト相が増加し相対的にビクスバイト相が減少する傾向にある。アルミニウム化合物、マグネシウム化合物及びカルシウム化合物を添加して焼成することで、スピネル相の生成を抑制して高温で焼成することが可能となる。 In the present invention, in order to control the ratio of the strength ratio of the (104) plane of the hematite phase of the composite oxide to the strength ratio of the (222) plane of the bixbite phase, the composition ratio of the elements is controlled and the composition is controlled. Accordingly, it is necessary to control the heating and baking temperature. When the baking temperature is lowered, the hematite phase increases and the bixbite phase tends to decrease relatively. On the other hand, when the baking temperature is increased, the magnetite phase increases and the bixbite phase tends to decrease relatively. By adding and baking an aluminum compound, a magnesium compound, and a calcium compound, it becomes possible to suppress the formation of a spinel phase and to perform baking at a high temperature.
　本発明においては、耐熱性黒色粉体の粒子表面をＳｉ、Ａｌ、Ｚｒ、Ｔｉ、Ｚｎ、Ｐから選ばれる１種又は２種以上の化合物によって被覆しておいてもよい。表面処理方法は、湿式あるいは乾式方法等の常法に従って行えばよい。例えば、湿式方法は湿式分散した耐熱性黒色粉体のスラリーに、Ｓｉ、Ａｌ、Ｚｒから選ばれる１種又は２種以上の可溶性化合物を、酸又はアルカリでｐＨ調整しながら添加・混合して被覆する方法、乾式方法はヘンシェルミキサーなどの装置中で耐熱性黒色粉体にＳｉ、Ａｌ、Ｚｒ、Ｔｉから選ばれる１種又は２種以上のカップリング剤などにより被覆処理する方法である。 In the present invention, the particle surface of the heat-resistant black powder may be coated with one or more compounds selected from Si, Al, Zr, Ti, Zn, and P. The surface treatment method may be performed according to a conventional method such as a wet method or a dry method. For example, in the wet method, one or more soluble compounds selected from Si, Al, and Zr are added to and mixed with a slurry of heat-resistant black powder that has been wet-dispersed while adjusting the pH with an acid or alkali. The dry method is a method in which heat-resistant black powder is coated with one or more coupling agents selected from Si, Al, Zr, and Ti in an apparatus such as a Henschel mixer.
　次に、本発明に係る耐熱性黒色粉体を配合した塗料について述べる。 Next, the paint containing the heat-resistant black powder according to the present invention will be described.
　本発明に係る塗料中における耐熱性黒色粉体の配合割合は、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 heat-resistant black powder in the paint according to the present invention can be used in the range of 0.5 to 100 parts by weight with respect to 100 parts by weight of the paint base material, taking into account the handleability of the paint. For example, it is preferably 1.0 to 100 parts by weight.
　塗料構成基材としては、樹脂、溶剤、必要により油脂、消泡剤、体質顔料、乾燥促進剤、界面活性剤、硬化促進剤、助剤等が配合される。 As the paint constituting base material, resin, solvent, and if necessary, fats and oils, antifoaming agent, extender pigment, drying accelerator, surfactant, curing accelerator, auxiliary agent and the like are blended.
　樹脂、溶剤又は水系塗料用溶剤としては、溶剤系塗料用や油性印刷インクに通常使用されているものを用いればよい。 As the resin, solvent, or water-based paint solvent, those usually used for solvent-based paint or oil-based printing ink may be used.
　次に、本発明に係る耐熱性黒色粉体を含有する樹脂組成物について述べる。 Next, the resin composition containing the heat-resistant black powder according to the present invention will be described.
　本発明に係る樹脂組成物中における耐熱性黒色粉体の配合割合は、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 heat-resistant black powder in the resin composition according to the present invention can be used in the range of 0.01 to 200 parts by weight with respect to 100 parts by weight of the resin, and the handling property of the resin composition is taken into consideration. Thus, the amount is preferably 0.05 to 150 parts by weight, more preferably 0.1 to 100 parts by weight.
　本発明に係る樹脂組成物における構成基材としては、耐熱性黒色粉体と周知の熱可塑性樹脂とともに、必要により、滑剤、可塑剤、酸化防止剤、紫外線吸収剤、各種安定剤等の添加剤が配合される。 As a constituent substrate in the resin composition according to the present invention, a heat-resistant black powder and a known thermoplastic resin, and additives such as a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, and various stabilizers as necessary. Is blended.
　樹脂としては、通常使用されているものを用いればよい。 As the resin, a commonly used resin may be used.
　本発明に係る樹脂組成物は、樹脂原料と耐熱性黒色粉体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、耐熱性黒色粉体の凝集体を破壊し、樹脂組成物中に耐熱性黒色粉体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 obtained by mixing a resin raw material and a heat-resistant black powder in advance, and then applying a strong shearing action under heating using a kneader or an extruder, The aggregate is broken and the heat-resistant black powder is uniformly dispersed in the resin composition, and then molded into a shape according to 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、樹脂組成物の構成基材としての結合材樹脂と前記耐熱性黒色粉体と種々の添加剤を、必要により、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。 In the master batch pellet in the present invention, the binder resin as a constituent substrate of the resin composition, the heat-resistant black powder and various additives are mixed with a mixer if necessary, and then a well-known single-screw kneading extrusion. It is manufactured by kneading and molding after a kneading machine or a twin-screw kneading extruder or cutting, or by crushing or molding and cutting the kneaded material obtained by kneading the above mixture with a Banbury mixer, pressure kneader or the like. The
　結合材樹脂と耐熱性黒色粉体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 heat-resistant black powder to the kneader may be quantitatively supplied at a predetermined ratio, or a mixture of both may be supplied.
　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 bad and 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耐熱性黒色粉体の量は、結合材樹脂１００重量部に対して１～２００重量部が好ましい。 The amount of the heat-resistant black powder blended in the master batch pellet is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the binder resin.
　以下、本発明を実施例によって更に詳述するが、本発明は以下の実施例に限定されない。実施例、比較例において用いた評価方法について以下に示す。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. The evaluation methods used in Examples and Comparative Examples are shown below.
　耐熱性黒色粉体の結晶構造は、「Ｘ線回折装置ＲＩＮＴ２５００型」（理学電機工業株式会社製）により測定し、付属のプログラムにより平滑化、バックグラウンド除去、Ｋα除去などの補正を行い、ピークサーチをしてｄ値とピーク強度を求めた。ヘマタイト相の（１０４）面の強度比１００に対し、ビクスバイト相の（２２２）面の強度比、また、スピネル相の（３１１）面の強度比を求めた。 The crystal structure of the heat-resistant black powder is measured with an “X-ray diffractometer RINT2500” (manufactured by Rigaku Denki Kogyo Co., Ltd.), corrected for smoothing, background removal, Kα removal, etc. with the attached program. A search was performed to determine the d value and the peak intensity. The intensity ratio of the (222) plane of the bixbite phase and the intensity ratio of the (311) plane of the spinel phase were determined with respect to the intensity ratio of the (104) plane of the hematite phase.
　耐熱性黒色粉体の金属元素（Ｆｅ、Ｍｎ、Ａｌ、Ｍｇ、Ｃａ）の含有量、Ｆｅ原料中のＡｌ、Ｍｇ、Ｃａの含有量は、ＩＣＰ発光分光分析装置ｉＣＡＰ－６５００ＤＵＯ（サーモエレクトロン株式会社製）を使用し求めた。また、モル比に換算し、Ｆｅ／Ｍｎ比（モル比）を求めた。 The content of metal elements (Fe, Mn, Al, Mg, Ca) in heat-resistant black powder, and the content of Al, Mg, Ca in the Fe raw material were determined using ICP emission spectroscopic analyzer iCAP-6500DUO (Thermo Electron Co., Ltd.) Made). Moreover, it converted into molar ratio and calculated | required Fe / Mn ratio (molar ratio).
　耐熱性黒色粉体の色相（Ｌ＊値、ａ＊値、ｂ＊値）は、試料０．５ｇとヒマシ油０．５ｍｌとをフーバー式マーラーで練ってペースト状とし、このペーストにクリアラッカー４．５ｇを加え、混練、塗料化してキャストコート紙上に１５０μｍ（６ｍｉｌ）のアプリケーターを用いて塗布した塗布片（塗膜厚み：約３０μｍ）を作製した。塗膜片について、「色彩色差計ＣＲ－３００」（コニカミノルタセンシング株式会社製）を用いて測定を行い、ＪＩＳ　Ｚ　８７２９に定めるところに従って表色指数（Ｌ＊値、ａ＊値、ｂ＊値）で示した。また、ｃ＊値（彩度）を下式に基づいて算出した。ｃ＊値が０に近い程、無彩色に近いことを示す。
ｃ＊値＝｛（ａ＊値）２＋（ｂ＊値）２｝１／２ The hue (L * value, a * value, b * value) of the heat-resistant black powder was obtained by kneading 0.5 g of a sample and 0.5 ml of castor oil with a Hoover type Mahler to form a paste. 0.5 g was added, kneaded and converted into a paint, and an application piece (coating thickness: about 30 μm) applied on a cast coated paper using a 150 μm (6 mil) applicator was prepared. The coating piece was measured using a “color difference meter CR-300” (manufactured by Konica Minolta Sensing Co., Ltd.), and the color index (L * value, a * value, b * value) according to JIS Z 8729. ). Further, the c * value (saturation) was calculated based on the following equation. The closer the c * value is to 0, the closer it is to an achromatic color.
c * value = {(a * value) 2 + (b * value) 2 } 1/2
　耐熱性黒色粉体の耐熱性は、試料１０ｇを磁製ルツボに入れ、電気炉を用いて８００℃で２時間加熱処理を行い、放冷後、試料粉体の色相を測定し、加熱処理前と後の色相の変化を測定することによって求め、加熱処理前の測定色を基準に下式で示されるΔＥで示した。ΔＥが小さい程、色相の変化が少なく、耐熱性に優れていることを示す。
ΔＥ＝｛（ΔＬ）２＋（Δａ）２＋（Δｂ）２｝１／２
但し、ΔＬ：比較する試料間のＬ＊値の差
Δａ：比較する試料間のａ＊値の差
Δｂ：比較する試料間のｂ＊値の差 The heat resistance of the heat-resistant black powder is as follows: 10 g of a sample is put in a magnetic crucible, heat-treated at 800 ° C. for 2 hours using an electric furnace, allowed to cool, the color of the sample powder is measured, and before heat treatment It was obtained by measuring the change in hue after and was expressed by ΔE expressed by the following formula based on the measured color before the heat treatment. The smaller ΔE, the smaller the change in hue and the better the heat resistance.
ΔE = {(ΔL) 2 + (Δa) 2 + (Δb) 2 } 1/2
Where ΔL: difference in L * value between samples to be compared Δa: difference in a * value between samples to be compared Δb: difference in b * value between samples to be compared
　磁化値は、「試料振動型磁力計ＢＨＶ－３５」（理研電子株式会社製）により、外部磁場７９６ｋＡ／ｍ（１０ｋＯｅ）を印加し、測定した値で示した。 The magnetization value is a value measured by applying an external magnetic field of 796 kA / m (10 kOe) with a “sample vibration magnetometer BHV-35” (manufactured by Riken Denshi Co., Ltd.).
　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.
　以下に示す実施例１－１～１－９は金属元素ＭとしてＡｌを使用した場合の実施例であり、比較例１－１～１－７は実施例１－１～１－９に対する比較例である。 Examples 1-1 to 1-9 shown below are examples in which Al is used as the metal element M, and Comparative Examples 1-1 to 1-7 are comparative examples relative to Examples 1-1 to 1-9. It is.
　実施例１－１：
　含有Ａｌ量０．２３ｗｔ％のマグネタイト（戸田工業（株）製　ＭＡＴ－３０５）　４５３ｇ（７５．５ｗｔ％）と四酸化三マンガン　１４７ｇ（２４．５ｗｔ％）とを混合し、電気炉にて、９２０℃で２時間焼成した。焼成品を粉砕し、黒色粉体を得た。 Example 1-1
453 g (75.5 wt%) of magnetite (MAT-305 manufactured by Toda Kogyo Co., Ltd.) having an Al content of 0.23 wt% was mixed with 147 g (24.5 wt%) of trimanganese tetroxide. Baked at 2 ° C. for 2 hours. The fired product was pulverized to obtain a black powder.
　得られた粉体はヘマタイト相１００に対し、ビクスバイト相１４３の強度比であった。また、ＩＣＰ測定より、含有Ａｌ量　０．１５ｗｔ％、Ｆｅ／Ｍｎ（モル比）＝３．０であった。 The obtained powder had a strength ratio of the bixbite phase 143 to the hematite phase 100. From the ICP measurement, the Al content was 0.15 wt% and Fe / Mn (molar ratio) = 3.0.
　得られた粉体の磁化値は０．９Ａｍ２／ｋｇ、比表面積は２．４ｍ２／ｇであった。また、クリアラッカーで塗料化した塗布片の色相は、Ｌ＊値が２３．５、ａ＊値が１．２、ｂ＊値が０．２、換算したｃ＊値が１．２の黒色粉体であった。 The obtained powder had a magnetization value of 0.9 Am 2 / kg and a specific surface area of 2.4 m 2 / g. In addition, the hue of the coated piece made of clear lacquer is a black powder having an L * value of 23.5, an a * value of 1.2, a b * value of 0.2, and a converted c * value of 1.2. It was a body.
　得られた粉体を電気炉にて８００℃で２時間加熱した粉体の色相は、Ｌ＊値が２３．５、ａ＊値が１．１、ｂ＊値が０．１であり、耐熱性ΔＥが０．１であり、耐熱性に優れた黒色粉体であった。 The powder obtained by heating the obtained powder at 800 ° C. for 2 hours in an electric furnace has an L * value of 23.5, an a * value of 1.1, and a b * value of 0.1. The property ΔE was 0.1, and the black powder was excellent in heat resistance.
　実施例１－２～１－７：
　鉄原料組成、サイズ、四酸化三マンガンとの混合割合及び焼成温度を変化させた以外は、実施例１と同様にして黒色粉体を得た。 Examples 1-2 to 1-7:
A black powder was obtained in the same manner as in Example 1 except that the iron raw material composition, size, mixing ratio with trimanganese tetroxide, and firing temperature were changed.
　実施例１－８：
　Ａｌを含有しないマグネタイト　４５７ｇ（７５．４ｗｔ％）と四酸化三マンガン　１４３ｇ（２３．６ｗｔ％）に酸化アルミニウム　５．７ｇ（１．０ｗｔ％、純度９９．７ｗｔ％）を混合し、電気炉にて、９９０℃で２時間焼成した。焼成品を粉砕し、黒色粉体を得た。 Example 1-8:
457 g (75.4 wt%) of magnetite not containing Al and 143 g (23.6 wt%) of trimanganese tetroxide were mixed with 5.7 g of aluminum oxide (1.0 wt%, purity 99.7 wt%). And baked at 990 ° C. for 2 hours. The fired product was pulverized to obtain a black powder.
　実施例１－９：
　Ａｌを含有しないマグネタイト、四酸化三マンガン、酸化アルミニウムの混合割合及び焼成温度を変化させた以外は、実施例１－８と同様にして黒色粉体を得た。 Example 1-9:
A black powder was obtained in the same manner as in Example 1-8, except that the mixing ratio of the magnetite not containing Al, trimanganese tetroxide, and aluminum oxide and the firing temperature were changed.
　比較例１－１：
　Ａｌを含有しない鉄原料、サイズ、四酸化三マンガンとの混合割合及び焼成温度を変化させた以外は、実施例１－１と同様にして粉体を得た。 Comparative Example 1-1
A powder was obtained in the same manner as in Example 1-1 except that the iron raw material not containing Al, the size, the mixing ratio with trimanganese tetroxide and the firing temperature were changed.
　得られた粉体はヘマタイト相１００に対し、ビクスバイト相１５の強度比であった。また、クリアラッカーで塗料化した塗布片の色相は、Ｌ＊値が２５．５、ａ＊値が５．０、ｂ＊値が３．０、ｃ＊値が５．９、耐熱性ΔＥが１．５であり、黒色とは言い難く、耐熱性も低い粉体であった。 The obtained powder had a strength ratio of the bixbite phase 15 to the hematite phase 100. In addition, the hue of the coating piece made into a paint with clear lacquer has an L * value of 25.5, an a * value of 5.0, a b * value of 3.0, a c * value of 5.9, and a heat resistance ΔE of It was 1.5, and it was hard to say black, and it was a powder having low heat resistance.
　比較例１－２～１－６：
　鉄原料の種類、サイズ、四酸化三マンガンとの混合割合及び焼成温度を変化させた以外は、比較例１－１と同様にして粉体を得た。 Comparative Examples 1-2 to 1-6:
A powder was obtained in the same manner as in Comparative Example 1-1 except that the type and size of the iron raw material, the mixing ratio with trimanganese tetroxide and the firing temperature were changed.
　比較例１－７：
　Ａｌを含有しないマグネタイト、四酸化三マンガン、酸化アルミニウムの混合割合及び焼成温度を変化させた以外は、実施例１－８と同様にして黒色粉体を得た。 Comparative Example 1-7:
A black powder was obtained in the same manner as in Example 1-8, except that the mixing ratio of the magnetite not containing Al, trimanganese tetroxide, and aluminum oxide and the firing temperature were changed.
　耐熱性黒色粉体の製造条件を表１に、得られた耐熱性黒色粉体の諸特性を表２に示した。 Table 1 shows the production conditions of the heat-resistant black powder, and Table 2 shows the characteristics of the obtained heat-resistant black powder.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　以下に示す実施例２－１～２－８は金属元素ＭとしてＡｌを使用した場合の実施例であり、比較例２－１～２－２は実施例２－１～２－８に対する比較例である。 Examples 2-1 to 2-8 shown below are examples in which Al is used as the metal element M, and Comparative Examples 2-1 to 2-2 are comparative examples for Examples 2-1 to 2-8. It is.
　実施例２－１：
　マグネタイト（戸田工業（株）製）４５２ｇ（７５．３ｗｔ％）と四酸化三マンガン１４７ｇ（２４．５ｗｔ％）に炭酸カルシウム１．４ｇ（０．２４ｗｔ％、純度９９ｗｔ％）を混合し、電気炉にて、９９０℃で２時間焼成した。焼成品を粉砕し、黒色粉体を得た。 Example 2-1
Magnetite (Toda Kogyo Co., Ltd.) 452 g (75.3 wt%) and trimanganese tetroxide 147 g (24.5 wt%) were mixed with calcium carbonate 1.4 g (0.24 wt%, purity 99 wt%) to produce an electric furnace. And baked at 990 ° C. for 2 hours. The fired product was pulverized to obtain a black powder.
　得られた粉体はヘマタイト相１００に対し、ビクスバイト相１４７の強度比であった。また、ＩＣＰ測定より、含有Ｃａ量　０．０９ｗｔ％、Ｆｅ／Ｍｎ（モル比）＝３．０であった。 The obtained powder had a strength ratio of the bixbite phase 147 to the hematite phase 100. From the ICP measurement, the Ca content was 0.09 wt% and Fe / Mn (molar ratio) = 3.0.
　得られた粉体の磁化値は０．７Ａｍ２／ｋｇ、比表面積は１．７ｍ２／ｇであった。また、クリアラッカーで塗料化した塗布片の色相は、Ｌ＊値が２４．６、ａ＊値が０．６、ｂ＊値が－０．３、換算したｃ＊値が０．６の黒色粉体であった。 The obtained powder had a magnetization value of 0.7 Am 2 / kg and a specific surface area of 1.7 m 2 / g. In addition, the hue of the coated piece made of clear lacquer is black with L * value of 24.6, a * value of 0.6, b * value of -0.3, and converted c * value of 0.6. It was a powder.
　得られた粉体を電気炉にて８００℃で２時間加熱した粉体の色相は、Ｌ＊値が２４．６、ａ＊値が０．８、ｂ＊値が－０．２であり、耐熱性ΔＥが０．２であり、耐熱性に優れた黒色粉体であった。 The hue of the powder obtained by heating the obtained powder in an electric furnace at 800 ° C. for 2 hours has an L * value of 24.6, an a * value of 0.8, and a b * value of −0.2. The heat resistance ΔE was 0.2, and the black powder was excellent in heat resistance.
　実施例２－６：
　マグネタイト（戸田工業（株）製）　４３７ｇ（７２．９ｗｔ％）と四酸化三マンガン　１４２ｇ（２３．７ｗｔ％）に炭酸マグネシウム　２０ｇ（３．４ｗｔ％、純度９９.９ｗｔ％）を混合し、電気炉にて、９４０℃で６時間焼成した。焼成品を粉砕し、黒色粉体を得た。 Example 2-6:
Magnetite (manufactured by Toda Kogyo Co., Ltd.) 437 g (72.9 wt%) and trimanganese tetroxide 142 g (23.7 wt%) are mixed with magnesium carbonate 20 g (3.4 wt%, purity 99.9 wt%). And baked at 940 ° C. for 6 hours. The fired product was pulverized to obtain a black powder.
　得られた粉体はヘマタイト相１００に対し、ビクスバイト相７１、スピネル相６の強度比であった。また、ＩＣＰ測定より、含有Ｍｇ量　０．７７ｗｔ％、Ｆｅ／Ｍｎ（モル比）＝３．０であった。 The obtained powder had a strength ratio of the bixbite phase 71 and the spinel phase 6 to the hematite phase 100. From the ICP measurement, the Mg content was 0.77 wt% and Fe / Mn (molar ratio) = 3.0.
　得られた粉体の磁化値は１．９Ａｍ２／ｋｇ、比表面積は２．０ｍ２／ｇであった。また、クリアラッカーで塗料化した塗布片の色相は、Ｌ＊値が２４．４、ａ＊値が０．７、ｂ＊値が－０．２、換算したｃ＊値が０．７、耐熱性ΔＥが０．３の黒色粉体であった。 The obtained powder had a magnetization value of 1.9 Am 2 / kg and a specific surface area of 2.0 m 2 / g. In addition, the hue of the coated piece made of clear lacquer is L * value 24.4, a * value 0.7, b * value -0.2, converted c * value 0.7, heat resistance It was a black powder having a property ΔE of 0.3.
実施例２－２～２－５、２－７、２－８：
　マグネタイト、四酸化三マンガン、炭酸カルシウム、炭酸マグネシウムの混合割合及び焼成温度を変化させた以外は、実施例２－１、２－６と同様にして黒色粉体を得た。 Examples 2-2 to 2-5, 2-7, 2-8:
Black powders were obtained in the same manner as in Examples 2-1 and 2-6, except that the mixing ratio of magnetite, trimanganese tetroxide, calcium carbonate, and magnesium carbonate and the firing temperature were changed.
　実施例２－９
　平均粒子径が０．２８μｍであって、含有Ａｌ量０．２３ｗｔ％、含有Ｍｇ量０．１５ｗｔ％のマグネタイト　４４２ｇ（７３．８ｗｔ％）と四酸化三マンガン　１４３ｇ（２３．８ｗｔ％）に炭酸カルシウム１４ｇ（２．３ｗｔ％、純度９９ｗｔ％）を混合し、電気炉にて、９８０℃で８時間焼成した。焼成品を粉砕し、黒色粉体を得た。 Example 2-9
442 g (73.8 wt%) of magnetite having an average particle size of 0.28 μm, an Al content of 0.23 wt% and an Mg content of 0.15 wt%, and 143 g (23.8 wt%) of trimanganese tetroxide 14 g (2.3 wt%, purity 99 wt%) was mixed and baked in an electric furnace at 980 ° C. for 8 hours. The fired product was pulverized to obtain a black powder.
　得られた粉体はヘマタイト相１００に対し、ビクスバイト相１６３の強度比であった。また、ＩＣＰ測定より、Ｆｅ／Ｍｎ（モル比）＝３．０、含有Ｃａ量　０．９６ｗｔ％、含有Ｍｇ量０．１０ｗｔ％、含有Ａｌ量　０．１５ｗｔ％であった。 The obtained powder had a strength ratio of the bixbite phase 163 to the hematite phase 100. From ICP measurement, Fe / Mn (molar ratio) = 3.0, Ca content 0.96 wt%, Mg content 0.10 wt%, Al content 0.15 wt%.
　得られた黒色粉体の磁化値は１．６Ａｍ２／ｋｇ、比表面積は１．９ｍ２／ｇであった。また、クリアラッカーで塗料化した塗布片の色相は、Ｌ＊値が２４．２、ａ＊値が０．７、ｂ＊値が－０．４、換算したｃ＊値が０．８、耐熱性ΔＥが０．３の黒色粉体であった。 The obtained black powder had a magnetization value of 1.6 Am 2 / kg and a specific surface area of 1.9 m 2 / g. In addition, the hue of the coated piece made into a clear lacquer paint is L * value 24.2, a * value 0.7, b * value -0.4, converted c * value 0.8, heat resistance It was a black powder having a property ΔE of 0.3.
　比較例２－１：
　鉄原料、サイズ、四酸化三マンガンとの混合割合及び焼成温度を変化させた以外は、実施例２－１と同様にして粉体を得た。 Comparative Example 2-1
A powder was obtained in the same manner as in Example 2-1, except that the iron raw material, size, mixing ratio with trimanganese tetroxide, and firing temperature were changed.
　得られた粉体はヘマタイト相１００に対し、ビクスバイト相１５の強度比であった。また、クリアラッカーで塗料化した塗布片の色相は、Ｌ＊値が２５．５、ａ＊値が５．０、ｂ＊値が３．２、ｃ＊値が５．９、耐熱性ΔＥが１．５であり、黒色とは言い難く、耐熱性も低い粉体であった。 The obtained powder had a strength ratio of the bixbite phase 15 to the hematite phase 100. In addition, the hue of the coating piece made into a paint with clear lacquer has an L * value of 25.5, an a * value of 5.0, a b * value of 3.2, a c * value of 5.9, and a heat resistance ΔE of It was 1.5, and it was hard to say black, and it was a powder having low heat resistance.
　比較例２－２：
　鉄原料の種類、サイズ、四酸化三マンガンとの混合割合及び焼成温度を変化させた以外は、比較例２－１と同様にして粉体を得た。 Comparative Example 2-2:
A powder was obtained in the same manner as in Comparative Example 2-1, except that the type and size of the iron raw material, the mixing ratio with trimanganese tetroxide and the firing temperature were changed.
　耐熱性黒色粉体の製造条件を表３に、得られた耐熱性黒色粉体の諸特性を表４に示した。 Table 3 shows the production conditions of the heat-resistant black powder, and Table 4 shows the characteristics of the obtained heat-resistant black powder.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明に係る耐熱性黒色粉体は、耐熱性に優れ高温下でも色相（黒色度）の変化が少ないので、塗料又は樹脂組成物の着色材として好適である。使用用途としては、自動車又は２輪車のマフラー、エンジンカバー、プラントの屋内外の加熱設備、焼却炉、煙突、厨房機器、ロケット発射台など耐熱性及び外観性が要求される各種塗料に主に有用である。 The heat-resistant black powder according to the present invention is suitable as a colorant for paints or resin compositions because it has excellent heat resistance and little change in hue (blackness) even at high temperatures. Applications include mainly automobiles and motorcycle mufflers, engine covers, plant indoor and outdoor heating facilities, incinerators, chimneys, kitchen equipment, rocket launch pads, and various paints that require heat resistance and appearance. Useful.

Claims (8)

  1. 　ＦｅとＭｎと金属元素Ｍとを含有する複合酸化物からなる耐熱性黒色粉体であって、金属元素ＭはＡｌ、Ｍｇ及びＣａから選択される１種以上であり、耐熱性黒色粉体の８００℃での耐熱試験の色相の変化が０．５以下で且つ磁化値が２．０Ａｍ２／ｋｇ以下であり、当該耐熱性黒色粉体のＸ線回折スペクトルにおいて、ヘマタイト相の（１０４）面の強度比１００に対し、ビクスバイト相の（２２２）面の強度比が４５～２５０であることを特徴とする耐熱性黒色粉体。 A heat-resistant black powder made of a composite oxide containing Fe, Mn, and a metal element M, wherein the metal element M is at least one selected from Al, Mg, and Ca. The change in hue in a heat resistance test at 800 ° C. is 0.5 or less and the magnetization value is 2.0 Am 2 / kg or less. In the X-ray diffraction spectrum of the heat resistant black powder, the (104) plane of the hematite phase A heat-resistant black powder characterized in that the strength ratio of the (222) plane of the bixbite phase is 45 to 250 with respect to the strength ratio of 100.
  2. 　金属元素Ｍの含有量が０．０１～５．０重量％である請求項１記載の耐熱性黒色粉体。 The heat-resistant black powder according to claim 1, wherein the content of the metal element M is 0.01 to 5.0% by weight.
  3. 　Ｆｅ／Ｍｎ（モル比）が１．０～１０．０である請求項１又は２記載の耐熱性黒色粉体であって。 The heat-resistant black powder according to claim 1 or 2, wherein Fe / Mn (molar ratio) is 1.0 to 10.0.
  4. 　黒色度（Ｌ＊値）が２５．０以下である請求項１～３のいずれかに記載の耐熱性黒色粉体。 The heat-resistant black powder according to any one of claims 1 to 3, having a blackness (L * value) of 25.0 or less.
  5. 　請求項１～４のいずれかに記載の耐熱性黒色粉体の製造方法であって、金属元素Ｍを０．０１～５．０ｗｔ％含有する鉄化合物と、マンガン化合物とをＦｅ／Ｍｎ比（モル比）が１．０～１０．０となるように混合し、得られた混合物を８３０～１０００℃の温度範囲で焼成する請求項１～４のいずれかに記載の耐熱性黒色粉体の製造方法。 The method for producing a heat-resistant black powder according to any one of claims 1 to 4, wherein an iron compound containing 0.01 to 5.0 wt% of the metal element M and a manganese compound are Fe / Mn ratio ( The heat-resistant black powder according to any one of claims 1 to 4, wherein the mixture is fired at a temperature range of 830 to 1000 ° C. Production method.
  6. 　請求項１～４のいずれかに記載の耐熱性黒色粉体の製造方法であって、鉄化合物、マンガン化合物及び金属元素Ｍの化合物を混合する工程および得られた混合物を８３０～１０００℃の温度範囲で焼成する工程から成り、上記混合工程において、Ｆｅ／Ｍｎ比（モル比）が１．０～１０．０であり、金属元素ＭがＡｌの場合、アルミニウム化合物がＡｌ２Ｏ３としての混合割合（Ａｌ２Ｏ３量／（鉄化合物＋マンガン化合物＋アルミニウム化合物））が０．０１～１０．０ｗｔ％となるように混合し、金属元素ＭがＭｇの場合、マグネシウム化合物がＭｇＣＯ３としての混合割合（ＭｇＣＯ３量／（鉄化合物＋マンガン化合物＋マグネシウム化合物））が０．０１～１０．０ｗｔ％となるように混合し、金属元素ＭがＣａの場合、カルシウム化合物がＣａＣＯ３としての混合割合（ＣａＣＯ３量／（鉄化合物＋マンガン化合物＋カルシウム化合物））が０．０１～１０．０ｗｔ％となるように混合する請求項１～４のいずれかに記載の耐熱性黒色粉体の製造方法。 The method for producing a heat-resistant black powder according to any one of claims 1 to 4, wherein the step of mixing the iron compound, the manganese compound and the compound of the metal element M and the obtained mixture at a temperature of 830 to 1000 ° C In the mixing step, when the Fe / Mn ratio (molar ratio) is 1.0 to 10.0 and the metal element M is Al, the aluminum compound is mixed as Al 2 O 3. When the ratio (Al 2 O 3 amount / (iron compound + manganese compound + aluminum compound)) is 0.01 to 10.0 wt% and the metal element M is Mg, the magnesium compound is MgCO 3 as MgCO 3 . the mixing ratio (MgCO 3 weight / (iron compound + manganese compound + magnesium compound)) is mixed in a 0.01 ~ 10.0wt%, when the metal element M is Ca, Cal The mixing ratio of Um compound as CaCO 3 (CaCO 3 weight / (iron compound + manganese compound + calcium compound)) is according to any one of claims 1 to 4, mixed in a 0.01 ~ 10.0 wt% Method for producing heat-resistant black powder.
  7. 　請求項１～４のいずれかに記載の耐熱性黒色粉体を塗料構成基材中に配合した塗料。 A paint obtained by blending the heat-resistant black powder according to any one of claims 1 to 4 in a paint constituting base material.
  8. 　請求項１～４のいずれかに記載の耐熱性黒色粉体を用いて着色した樹脂組成物。 A resin composition colored with the heat-resistant black powder according to any one of claims 1 to 4.
PCT/JP2012/058352 2011-03-31 2012-03-29 Heat-resistant black powder, method for producing same, and paint and resin composition using heat-resistant black powder WO2012133646A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201280006983.9A CN103339064B (en) 2011-03-31 2012-03-29 Thermotolerance black powder and manufacture method, the coating using this thermotolerance black powder and resin combination
KR1020137020042A KR20130140837A (en) 2011-03-31 2012-03-29 Heat-resistant black powder, method for producing same, and paint and resin composition using heat-resistant black powder

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-078397 2011-03-31
JP2011078397A JP5822058B2 (en) 2011-03-31 2011-03-31 Heat-resistant black powder and method for producing the same, paint and resin composition using the heat-resistant black powder

Publications (1)

Publication Number Publication Date
WO2012133646A1 true WO2012133646A1 (en) 2012-10-04

Family

ID=46931348

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/058352 WO2012133646A1 (en) 2011-03-31 2012-03-29 Heat-resistant black powder, method for producing same, and paint and resin composition using heat-resistant black powder

Country Status (4)

Country Link
JP (1) JP5822058B2 (en)
KR (1) KR20130140837A (en)
CN (1) CN103339064B (en)
WO (1) WO2012133646A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013209264A (en) * 2012-03-30 2013-10-10 Toda Kogyo Corp Heat-resistant black powder, method for manufacturing the same, and coating material and resin composition using the heat-resistant black powder

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6592125B2 (en) * 2017-06-15 2019-10-16 中島産業株式会社 Black pigment and method for producing the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61266314A (en) * 1985-05-21 1986-11-26 バイエル・アクチエンゲゼルシヤフト Manufacture of iron-base black pigment
JPS63112663A (en) * 1986-10-24 1988-05-17 バスフ　アクチェンゲゼルシャフト Thin plate-shaped pigment based on iron oxide and its production
JPH05221653A (en) * 1991-07-02 1993-08-31 Bayer Ag Heat resistant black pigment, manufacture thereof and utilization thereof
JPH0912768A (en) * 1995-06-28 1997-01-14 Titan Kogyo Kk Resin composition
JP2009215384A (en) * 2008-03-07 2009-09-24 Ishihara Sangyo Kaisha Ltd Black pigment and method of manufacturing the same
WO2010146776A1 (en) * 2009-06-15 2010-12-23 パナソニック株式会社 Negative electrode active material for lithium ion secondary battery, and lithium ion secondary battery using same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61266314A (en) * 1985-05-21 1986-11-26 バイエル・アクチエンゲゼルシヤフト Manufacture of iron-base black pigment
JPS63112663A (en) * 1986-10-24 1988-05-17 バスフ　アクチェンゲゼルシャフト Thin plate-shaped pigment based on iron oxide and its production
JPH05221653A (en) * 1991-07-02 1993-08-31 Bayer Ag Heat resistant black pigment, manufacture thereof and utilization thereof
JPH0912768A (en) * 1995-06-28 1997-01-14 Titan Kogyo Kk Resin composition
JP2009215384A (en) * 2008-03-07 2009-09-24 Ishihara Sangyo Kaisha Ltd Black pigment and method of manufacturing the same
WO2010146776A1 (en) * 2009-06-15 2010-12-23 パナソニック株式会社 Negative electrode active material for lithium ion secondary battery, and lithium ion secondary battery using same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013209264A (en) * 2012-03-30 2013-10-10 Toda Kogyo Corp Heat-resistant black powder, method for manufacturing the same, and coating material and resin composition using the heat-resistant black powder

Also Published As

Publication number Publication date
CN103339064B (en) 2016-01-20
JP2012211059A (en) 2012-11-01
CN103339064A (en) 2013-10-02
JP5822058B2 (en) 2015-11-24
KR20130140837A (en) 2013-12-24

Similar Documents

Publication Publication Date Title
CA2347886C (en) Infrared reflective color pigment
JP5392453B2 (en) Infrared reflective blue pigment, paint and resin composition using the infrared reflective blue pigment
JP5201401B2 (en) Infrared reflective black pigment, paint and resin composition using the infrared reflective black pigment
JP6217905B2 (en) Heat-resistant yellow hydrated iron oxide pigment and method for producing the same, paint and resin composition using the heat-resistant hydrated yellow iron oxide pigment
JP5285307B2 (en) Black pigment and method for producing the same
JP6388104B2 (en) Iron oxide particle powder, paint and resin composition using the iron oxide particle powder
WO2012133646A1 (en) Heat-resistant black powder, method for producing same, and paint and resin composition using heat-resistant black powder
JP7303481B2 (en) Aniline black and resin composition and dispersion using said aniline black
JP6106596B2 (en) Hexavalent chromium elution reduction complex oxide pigment
JP6508487B2 (en) Method for producing hematite particle powder, method for producing paint using the hematite particle powder, and method for producing resin composition
JP5201405B2 (en) Infrared reflective black pigment, paint and resin composition using the infrared reflective black pigment
JP2000264639A (en) Strontium iron oxide particle powder and its production
JP5915853B2 (en) Heat-resistant black powder and method for producing the same, paint and resin composition using the heat-resistant black powder
CA2453800C (en) High strength fe-cr brown with excellent weathering
JP5403213B2 (en) Surface-treated magnetic iron oxide particle powder, and black paint and rubber / resin composition using the surface-treated magnetic iron oxide particle powder
JP5266805B2 (en) Infrared reflective green pigment, paint and resin composition using the infrared reflective green pigment
CN112876881A (en) Cobalt blue pigment based on five-membered system and solid-phase preparation method thereof
JP3552015B2 (en) Nonmagnetic black pigment powder, nonmagnetic black paint using the nonmagnetic black pigment powder, and black rubber / resin composition using the nonmagnetic black pigment powder
JP2010150353A (en) Infrared reflective black pigment, method for producing the same, and paint and resin composition using the infrared reflective black pigment
Sanada et al. Environmentally friendly synthesis and physical and optical properties of highly reflective green–black pigments
JP2001040288A (en) Yellow coating material and yellow rubber/resin composition
JP7320691B1 (en) Cu-Cr-Zn-O composite oxide pigment
WO2024162402A1 (en) Composite iron oxide particle powder, method for producing same, and coating and resin composition using said composite iron oxide particle powder
JP2704555B2 (en) Nonmagnetic black-brown plate pigment powder and method for producing the same
JP2704538B2 (en) Nonmagnetic brown plate-like pigment powder and method for producing the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12765184

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20137020042

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12765184

Country of ref document: EP

Kind code of ref document: A1