CN103339064A - 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 PDFInfo
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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 800 C 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 1,000 C.
Description
Technical field
Even the present invention relates to the excellent heat resistance also few black powder of variation of degree of blackness at high temperature.
Background technology
Now, black pigment is used as various coloured materials.As black pigment, known have carbon black, a magnetite (Fe
3O
4) etc.These pigment be it is hard to tell excellent heat resistance.
In addition, as having stable on heating black pigment, the known composite oxides that Cr system is arranged etc. still owing to contain Cr, the high problem of carrying capacity of environment occurs.
Therefore, demand is constituted and is had the black pigment of high heat resistance by harmless element.
Now, various improvement (patent documentation 1～3) have been carried out to having stable on heating black pigment.
Technical literature formerly
Patent documentation
Patent documentation 1: Japanese kokai publication hei 10-279314 communique
Patent documentation 2: Japanese Patent Publication 47-30085 communique
Patent documentation 3: Japanese kokai publication hei 5-221653 communique
Summary of the invention
The technical problem that invention will solve
Even do not obtain at present the excellent heat resistance yet few black pigment of variation of degree of blackness at high temperature as yet.
That is, use the composite oxides that contain Fe and Mn as black pigment though put down in writing in the patent documentation 1～3, not talkative excellent heat resistance at high temperature.
Even the object of the present invention is to provide a kind of excellent heat resistance at high temperature form and aspect (degree of blackness) change also few black powder.
The means of technical solution problem
Above-mentioned purpose is finished by following the present invention.
Namely, the present invention is a kind of thermotolerance black powder, it is the thermotolerance black powder that comprises the composite oxides that contain Fe, Mn and metallic element M, described thermotolerance black powder is characterised in that: metallic element M be selected among Al, Mg and the Ca more than a kind, being changed to below 0.5 of the form and aspect of the oven test during 800 ℃ of thermotolerance black powder, and magnetization value is 2.0Am
2Below/the kg, in the X-ray diffraction spectrum of this thermotolerance black powder, with respect to the strength ratio 100 of (104) face of rhombohedral iron ore phase, the strength ratio of (222) face of bixbite phase is 45～250(the present invention 1).
In addition, as the present invention's 1 described thermotolerance black powder, the content of metallic element M is 0.01～5.0 weight %.
In addition, as the present invention 1 or 2 described thermotolerance black powders, Fe/Mn(mol ratio) be 1.0～10.0(the present invention 3).
In addition, as each described thermotolerance black powder among the present invention 1～3, degree of blackness (L* value) is (the present invention 4) below 25.0.
In addition, the present invention is a kind of manufacture method of thermotolerance black powder, it is the manufacture method of each described thermotolerance black powder among the present invention 1～4, iron cpd and the manganic compound that will contain the metallic element M of 0.01～5.0wt% are 1.0～10.0 mixing with Fe/Mn than (mol ratio), and the mixture that obtains is fired (the present invention 5) 830～1000 ℃ temperature range.
In addition, the present invention is a kind of manufacture method of thermotolerance black powder, it is the manufacture method of each described thermotolerance black powder among the present invention 1～4, comprise: the operation of mixing the compound of iron cpd, manganic compound and metallic element M, with the operation that the mixture that will obtain is fired 830～1000 ℃ temperature range, in above-mentioned mixed processes, Fe/Mn is 1.0～10.0 than (mol ratio), be under the situation of Al at metallic element M, according to aluminum compound with Al
2O
3Blending ratio (the Al of meter
2O
3The amount/(iron cpd+manganic compound+aluminum compound)) be that 0.01～10.0wt% mixes, be under the situation of Mg at metallic element M, according to magnesium compound with MgCO
3Blending ratio (the MgCO of meter
3The amount/(iron cpd+manganic compound+magnesium compound)) be that 0.01～10.0wt% mixes, be under the situation of Ca at metallic element M, according to calcium cpd with CaCO
3Blending ratio (the CaCO of meter
3Amount/(iron cpd+manganic compound+calcium cpd)) be that 0.01～10.0wt% mixes (the present invention 6).
In addition, the present invention is for constituting the coating (the present invention 7) that is combined with each described thermotolerance black powder among the present invention 1～4 in the base material at coating.
In addition, the present invention is for using the painted resin combination (the present invention 8) of each described thermotolerance black powder among the present invention 1～4.
The invention effect
Thermotolerance black powder of the present invention, excellent heat resistance even the variation of degree of blackness at high temperature is also few, thereby is suitable as the coloured material of coating or resin combination.
Description of drawings
The X-ray diffractogram of the thermotolerance black powder that Fig. 1 obtains for embodiments of the invention 1-1.
Fig. 2 is for the diffraction angle among Fig. 1 being the figure of 20～40 ° scope amplification.
The X-ray diffractogram of the thermotolerance black powder that Fig. 3 obtains for embodiments of the invention 2-1.
Embodiment
Followingly in more detail formation of the present invention is described.
At first, thermotolerance black powder of the present invention is described.
Thermotolerance black powder of the present invention comprises the composite oxides that contain Fe, Mn and metallic element M.Metallic element M is selected from more than one of Al, Mg and Ca.
The content of the metallic element M of thermotolerance black powder of the present invention is preferably 0.01～5.0 weight %.Under the situation that contains quantity not sufficient 0.01 weight % of metallic element M, the thermotolerance of black powder reduces, and degree of blackness changes under the high temperature.Content at metallic element M surpasses under the situation of 5.0 weight %, and degree of blackness reduces (the L* value increases), is difficult to be called black pigment.More preferably the content of metallic element M is 0.01～4.0 weight %, more preferably 0.05～3.0 weight %.
The Fe/Mn(mol ratio of thermotolerance black powder of the present invention) is preferably 1.0～10.0.In the Fe/Mn(mol ratio) under the situation of less than 1.0, the b* value increases, and is difficult to be called the black powder, and the thermotolerance of black powder reduces sometimes, degree of blackness changes under the high temperature.In the Fe/Mn(mol ratio) surpass under 10.0 the situation, rhombohedral iron ore increases mutually, and the a* value increases, and is difficult to be called the black powder.More preferably Fe/Mn(mol ratio) be 1.2～9.0, more preferably 1.5～8.5.
Thermotolerance black powder of the present invention, the variation of the form and aspect of the oven test in the time of 800 ℃ is below 0.5.Variation in above-mentioned form and aspect surpasses under 0.5 the situation, and thermotolerance is low, and is not preferred.More preferably being changed to below 0.4 of form and aspect, more preferably 0.01～0.35.
The magnetization value of thermotolerance black powder of the present invention is 2.0Am
2Below/the kg.Surpass 2.0Am at magnetization value
2Under the situation of/kg, because spinel existence in a large number mutually, so the thermotolerance reduction, not preferred.More preferably magnetization value is 1.8Am
2Below/the kg, 0.01～1.5Am more preferably
2/ kg.
In the X-ray diffraction spectrum of thermotolerance black powder of the present invention, with respect to the strength ratio 100 of (104) face of rhombohedral iron ore phase, the strength ratio of (222) face of bixbite phase is 45～250.Under the situation of above-mentioned strength ratio less than 45, the ratio of rhombohedral iron ore phase increases, and a* value (redness) strengthens.Surpass under 250 the situation in above-mentioned strength ratio, degree of blackness reduces (the L* value increases) sometimes.More preferably strength ratio is 45～245, further preferred 50～240.Wherein, among the present invention, as long as rhombohedral iron ore satisfies above-mentioned scope mutually with bixbite mutually, also can contain a spot of spinel phase.
Thermotolerance black powder of the present invention is that degree of blackness (L* value) is at the thermotolerance black powder below 25.0.Surpass under 25.0 the situation at degree of blackness (L* value), be not suitable as black pigment.More preferably degree of blackness (L* value) is below 24.5, and further preferred 20～24.
The a* value of thermotolerance black powder of the present invention is preferably-2～+ 5.The a* value is difficult to be called black pigment under above-mentioned extraneous situation.More preferably-1～+ 2.
The b* value of thermotolerance black powder of the present invention is preferably-5～+ 5.The b* value is difficult to be called black pigment under above-mentioned extraneous situation.More preferably-4～+ 2.
The chroma c* value of thermotolerance black powder of the present invention is preferably below 2.5, and more preferably 0.1～2.0.
Thermotolerance black powder of the present invention contains metallic element M, namely contains more than one that are selected from Al, Mg and Ca, and therefore, a* value, b* value, c* value are lower, are the black pigment near Achromatic color.
The median size of thermotolerance black powder of the present invention is preferably 0.02～5.0 μ m.Median size at the black powder surpasses under the situation of 5.0 μ m, and particle size is excessive, so tinting strength reduces.Under the situation of median size less than 0.02 μ m, be difficult to sometimes in vehicle, disperse.More preferably 0.025～4.0 μ m, more preferably 0.04～2.0 μ m.
The BET specific surface area of thermotolerance black powder of the present invention is preferably 1～50m
2/ g.At the not enough 1m of BET specific surface area
2Under the situation of/g, particle is thick, forms the particle that sintering takes place to each other for particle and particle, and tinting strength reduces.On the other hand, surpass 50m in the BET specific surface area
2Under the situation of/g, increase because the miniaturization of particle causes intermolecular forces, condense easily, therefore, be difficult to utilize surface treatment agent that particle surface is coated processing uniformly.1.5～25m more preferably
2/ g, more preferably 1.8～15m
2/ g.
The coating of particles of thermotolerance black powder of the present invention is not defined as specific shape, can use the elongated piece of granular particle, needle-like, spindle shape, grain of rice shape etc. of spherical, granular, octahedra shape, hexahedron shape, polyhedral etc. and plate-like particles etc.Consider the dispersiveness of the black pigment that obtains, preferred spherical particle and granular particle.
In thermotolerance black powder of the present invention, can enough Si of being selected from, Al, more than one compound or the various surface treatment agents of organic class surface treatment agent etc. among Zr, Ti, Zn, the P coat the surface of powder and re-use.
Then, the manufacture method to thermotolerance black powder of the present invention describes.
Thermotolerance black powder of the present invention, iron cpd by will containing 0.01～5.0wt% metallic element M and manganic compound are 1.0～10.0 to mix with Fe/Mn than (mol ratio), and the mixture that obtains is fired and obtained 830～1000 ℃ temperature range.
In addition, thermotolerance black powder of the present invention, the operation of the compound by mixing iron cpd, manganic compound and metallic element M and the operation that the mixture that obtains is fired 830～1000 ℃ temperature range obtain.In above-mentioned mixed processes, Fe/Mn is 1.0～10.0 than (mol ratio), is under the situation of Al at metallic element M, according to aluminum compound with Al
2O
3Blending ratio (the Al of meter
2O
3The amount/(iron cpd+manganic compound+aluminum compound)) be that 0.01～10.0wt% mixes, be under the situation of Mg at metallic element M, according to magnesium compound with MgCO
3Blending ratio (the MgCO of meter
3The amount/(iron cpd+manganic compound+magnesium compound)) be that 0.01～10.0wt% mixes, be under the situation of Ca at metallic element M, according to calcium cpd with CaCO
3Blending ratio (the CaCO of meter
3Amount/(iron cpd+manganic compound+calcium cpd)) be that 0.01～10.0wt% mixes.
As the iron cpd that contains 0.01～5.0wt% aluminium, magnesium, calcium, can be by when iron cpd is synthetic, adding the method for aluminium, magnesium, calcium, the method manufacturing that coats or adhere to all cpds of aluminium, magnesium, calcium at iron cpd.
As iron cpd, manganic compound, aluminum compound, magnesium compound and calcium cpd, can from the oxide compound of each element, oxyhydroxide, carbonate, nitrate, vitriol, muriate etc., suitably select.
As long as the mixing of initial feed can evenly mix, be not particularly limited, can also can mix for dry type for wet mixing.Can also be synthetic for wet type.
The heating firing temperature is preferably 830～1000 ℃, more preferably 850～950 ℃.The heating atmosphere is not particularly limited, and can implement in atmosphere.
Powder after the heating as required, is washed, is pulverized and get final product according to usual method.
In the present invention, for the ratio of strength ratio with the strength ratio of (222) face of bixbite phase of (104) face of the rhombohedral iron ore phase of controlling composite oxides, need the ratio of components of control element and according to forming control heating firing temperature.When the heating firing temperature reduces, have that rhombohedral iron ore increases mutually, the tendency that reduces mutually of bixbite relatively.On the other hand, at the heating firing temperature when increasing, have that magnetite increases mutually, the tendency that reduces mutually of bixbite relatively.Fire by adding aluminum compound, magnesium compound and calcium cpd, can suppress the generation of spinel phase, can be with high-temperature firing.
In the present invention, can utilize the compound more than a kind or 2 kinds that is selected among Si, Al, Zr, Ti, Zn, the P to coat the particle surface of thermotolerance black powder.Surface treatment method gets final product according to the usual method of wet type or dry method etc., for example, wet method is: in the slurry of the thermotolerance black powder that wet type is disperseed, on one side regulate pH with acid or alkali, add, mix be selected from method that soluble compound a kind or 2 kind or more in Si, Al, Zr coat on one side.Dry method is: in the device of Henschel mixer etc., utilize the coupling agent more than a kind or 2 kinds that is selected among Si, Al, Zr, the Ti etc. thermotolerance black powder to be coated the method for processing.
Then, the coating that cooperates thermotolerance black powder of the present invention is described.
The cooperation ratio of the thermotolerance black powder in the coating of the present invention, the coating formation base material with respect to 100 weight parts uses in the scope of 0.5～100 weight part.Consider the operability of coating, be preferably 1.0～100 weight parts.
Constitute base material as coating, can cooperate resin, solvent, can cooperate grease, defoamer, pigment extender, dry promotor, tensio-active agent, curing catalyst, auxiliary agent etc. as required.
As resin, solvent or aqueous coating solvent, using solvent is normally used getting final product in coating usefulness or the oiliness printing ink.
Then, the resin combination that contains thermotolerance black powder of the present invention is described.
The cooperation ratio of the thermotolerance black powder in the resin combination of the present invention, with respect to the resin of 100 weight parts, use in the scope of 0.01～200 weight part, consider the operability of resin combination, be preferably 0.05～150 weight part, more preferably 0.1～100 weight part.
As the formation base material of resin combination of the present invention, can cooperate thermotolerance black powder and known thermoplastic resin, and can cooperate the additive of lubricant, softening agent, antioxidant, UV light absorber, various stablizers etc. as required.
As resin, use normally used resin to get final product.
Resin combination of the present invention, in advance resin raw material and thermotolerance black powder are fully mixed, then, use mixing roll or forcing machine, under heating, apply strong shearing action, destroy the aggregate of thermotolerance black powder, make after thermotolerance black powder evenly disperses in resin combination, forming process is purpose shape and then use.
And resin combination of the present invention can obtain via master batch material.
Master batch material of the present invention is by following method manufacturing: will be as grafting material resin, above-mentioned thermotolerance black powder and the various additive of the formation base material of resin combination, in mixing machine, mix as required, utilize known single screw mixing forcing machine or twin-screw mixer forcing machine etc. to carry out cutting off after mixing, the moulding afterwards; Perhaps obtain mixing thing with said mixture is mixing in Banbury, pressurization kneader etc., with the mixing thing pulverizing that obtains or moulding, cut-out.
Grafting material resin and thermotolerance black powder can ratio according to the rules be distinguished weight feed to the supply of mixing roll, also can supply with both mixtures.
Master batch material of the present invention, average major diameter be 1～6mm scope, be preferably the scope of 2～5mm.Average minor axis is 2～5mm, be preferably 2.5～4mm.Under the situation of the not enough 1mm of average major diameter, the operability when pellet is made is bad, not preferred.Surpassing under the situation of 6mm, big with the difference of the size of grafting material resin with dilution, be difficult to abundant dispersion.In addition, its shape can be different shape, can be for amorphous and sphere etc. granular, cylindrical, laminar etc.
As the grafting material resin that uses in the master batch material of the present invention, can use and the above-mentioned resin combination identical resin of resin.
Wherein, the composition of the grafting material resin in the master batch material can use and dilutes with the identical resin of grafting material resin, also can use different resins, but under the situation of using different resins, consider all characteristics that determined by the intermiscibility between the resin and determine.
The amount of the thermotolerance black powder that cooperates in the master batch material is preferably 1～200 weight part with respect to 100 weight part grafting material resins.
Embodiment
Below, by embodiment the present invention is described in further detail, but the present invention is not subjected to the restriction of following embodiment.The evaluation method of using in embodiment, the comparative example is as follows.
The crystalline texture of thermotolerance black powder, measure by " X-ray diffraction device RINT2500 type " (Liue electrical machinery Industrial Co., Ltd's manufacturing), utilize subsidiary program to carry out the revisal of smoothing, removal background, removal K α etc., carry out peak-seeking, obtain d value and peak intensity.With respect to the strength ratio 100 of rhombohedral iron ore phase (104) face, obtain the strength ratio of (222) face of bixbite phase and the strength ratio of spinel (311) face mutually.
The content of the metallic element of thermotolerance black powder (Fe, Mn, Al, Mg, Ca), the content of the Al in the Fe raw material, Mg, Ca uses ICP Emission Spectrophotometer device iCAP-6500DUO(Themoelectron Co., Ltd. to make) obtain.And be scaled mol ratio, obtain Fe/Mn than (mol ratio).
The form and aspect of thermotolerance black powder (L* value, a* value, b* value), utilize Hu Fu formula shredder with 0.5g sample and the mixing formation paste of 0.5ml Viscotrol C, in this cream, add jaqan 4.5g, carry out mixing, coatingization, use 150 μ m(6mil) applicator be coated on the cast-coated paper, make coated sheet (coating thickness: about 30 μ m).For coated sheet, use " color colour-difference meter CR-300 " (manufacturing of Konicaminolta Sensing Co., Ltd.) to measure, according to the regulation of JIS Z8729, represent with chromaticity index (L* value, a* value, b* value).And, calculate c* value (chroma) based on following formula.The c* value is more near 0, more near Achromatic color.
C* value={ (a* value)
2+ (b* value)
2}
1/2
As described below the obtaining of thermotolerance of thermotolerance black powder: the 10g sample is put into magnetic crucible processed, use electric furnace, carry out 2 hours heat treated at 800 ℃, put cold after, measure the form and aspect of sample powder, by measure before the heat treated and after the variation of form and aspect obtain, be benchmark with the mensuration look before the heat treated, represent with the Δ E shown in the following formula.E is more little for Δ, and the expression foxy more less, thermotolerance is more excellent.
ΔE={（ΔL）
2+（Δa）
2+（Δb）
2}
1/2
Wherein, Δ L: the L* value between the sample that compares poor
Δ a: the a* value between the sample that compares poor
Δ b: the b* value between the sample that compares poor
Magnetization value utilizes " sample oscillating mode magnetometer BHV-35 " (Riken Densi K. K.'s manufacturing) to apply external magnetic field 796kA/m(10kOe), with the value representation that records.
The specific surface area value representation that records by the BET method.
Embodiment when embodiment 1-1～1-9 shown below is to use Al as metallic element M, comparative example 1-1～1-7 are the comparative examples of relative embodiment 1-1～1-9.
Embodiment 1-1:
Mixing 453g(75.5wt%) the Al amount that contains is the magnetite of 0.23wt% (Toda Kogyo Corp. produces MAT-305) and trimanganese tetroxide 147g(24.5wt%), fired 2 hours at 920 ℃ with electric furnace.Burned product is pulverized, obtained the black powder.
In the powder that obtains, with respect to rhombohedral iron ore phase 100, be bixbite 143 strength ratio mutually.In addition, measure by ICP, contain the Al amount and be 0.15wt%, Fe/Mn(mol ratio)=3.0.
The magnetization value of the powder that obtains is 0.9Am
2/ kg, specific surface area is 2.4m
2/ g.And with the form and aspect of the coated sheet of jaqan coatingization, L* value is 23.5, the a* value is 1.2, the b* value is 0.2, the c* value of conversion is 1.2, is the black powder.
With the powder that the obtains form and aspect with the powder of 800 ℃ of heating after 2 hours in electric furnace, the L* value is 23.5, the a* value is 1.1, the b* value is 0.1, and thermotolerance Δ E is 0.1, is the black powder of excellent heat resistance.
Embodiment 1-2～1-7:
Change iron material composition, size, with blending ratio and the firing temperature of trimanganese tetroxide, in addition operation similarly to Example 1 obtains the black powder.
Embodiment 1-8:
Do not containing the magnetite 457g(75.4wt% of Al) and trimanganese tetroxide 143g(23.6wt%) in mixed aluminium oxides 5.7g(1.0wt%, purity 99.7wt%), fired 2 hours at 990 ℃ with electric furnace.Burned product is pulverized, obtained the black powder.
Embodiment 1-9:
Change blending ratio and the firing temperature of the magnetite do not contain Al, trimanganese tetroxide, aluminum oxide, in addition operate equally with embodiment 1-8, obtain the black powder.
Comparative example 1-1:
Change the iron material do not contain Al, size, with blending ratio and the firing temperature of trimanganese tetroxide, in addition operate equally with embodiment 1-1, obtain powder.
In the powder that obtains, with respect to rhombohedral iron ore phase 100, be bixbite 15 strength ratio mutually.And with the form and aspect of the coated sheet of jaqan coatingization, the L* value is 25.5, the a* value is 5.0, the b* value is that 3.0, c* value is 5.9, thermotolerance Δ E is 1.5, is to be difficult to be called also low powder of black, thermotolerance.
Comparative example 1-2～1-6:
Change iron material kind, size, with blending ratio and the firing temperature of trimanganese tetroxide, in addition operate equally with comparative example 1-1, obtain powder.
Comparative example 1-7:
Change blending ratio and the firing temperature of the magnetite do not contain Al, trimanganese tetroxide, aluminum oxide, in addition operate equally with embodiment 1-8, obtain the black powder.
Creating conditions of thermotolerance black powder is shown in table 1, and all characteristics of the thermotolerance black powder that obtains are shown in table 2.
[table 1]
[table 2]
Embodiment when embodiment 2-1～2-8 shown below is to use Al as metallic element M, comparative example 2-1～2-2 are the comparative examples of relative embodiment 2-1～2-8.
Embodiment 2-1:
At 452g(75.3wt%) magnetite (Toda Kogyo Corp.'s production) and trimanganese tetroxide 147g(24.5wt%) in mixed calcium carbonate 1.4g(0.24wt%, purity 99wt%), fired 2 hours at 990 ℃ with electric furnace.Burned product is pulverized, obtained the black powder.
In the powder that obtains, with respect to rhombohedral iron ore phase 100, be bixbite 147 strength ratio mutually.And, measure by ICP, contain the Ca amount and be 0.09wt%, Fe/Mn(mol ratio)=3.0.
The magnetization value of the powder that obtains is 0.7Am
2/ kg, specific surface area is 1.7m
2/ g.And with the form and aspect of the coated sheet of jaqan coatingization, the L* value is 24.6, the a* value is 0.6, the b* value is-0.3, and the c* value of conversion is 0.6, is the black powder.
With the form and aspect of electric furnace at the powder of 800 ℃ of heating after 2 hours, the L* value is 24.6, the a* value is 0.8, the b* value is-0.2 with the powder that obtains, and thermotolerance Δ E is 0.2, is the black powder of excellent heat resistance.
Embodiment 2-6:
At 437g(72.9wt%) magnetite (Toda Kogyo Corp.'s production) and trimanganese tetroxide 142g(23.7wt%) in mixed carbonic acid magnesium 20g(3.4wt%, purity 99.9wt%), fired 6 hours at 940 ℃ with electric furnace.Burned product is pulverized, obtained the black powder.
In the powder that obtains, with respect to rhombohedral iron ore phase 100, be bixbite phase 71, spinel 6 strength ratio mutually.And, measure by ICP, contain the Mg amount and be 0.77wt%, Fe/Mn(mol ratio)=3.0.
The magnetization value of the powder that obtains is 1.9Am
2/ kg, specific surface area is 2.0m
2/ g.And with the form and aspect of the coated sheet of jaqan coatingization, L* value is 24.4, a* value is 0.7, the b* value is-0.2, the c* value of conversion is 0.7, and thermotolerance Δ E is 0.3, is the black powder.
Embodiment 2-2～2-5,2-7,2-8:
Change blending ratio and the firing temperature of magnetite, trimanganese tetroxide, calcium carbonate, magnesiumcarbonate, in addition operate equally with embodiment 2-1,2-6, obtain the black powder.
Embodiment 2-9:
Be 0.28 μ m in median size, contain the Al amount for 0.23wt%, contain the Mg amount and be the magnetite 442g(73.8wt% of 0.15wt%) and trimanganese tetroxide 143g(23.8wt%) in mixed calcium carbonate 14g(2.3wt%, purity 99wt%), fired 8 hours at 980 ℃ with electric furnace.Burned product is pulverized, obtained the black powder.
In the powder that obtains, with respect to rhombohedral iron ore phase 100, be bixbite 163 strength ratio mutually.And, measure the Fe/Mn(mol ratio by ICP)=3.0, contain the Ca amount for 0.96wt%, contain the Mg amount for 0.10wt%, contain the Al amount and be 0.15wt%.
The magnetization value of the black powder that obtains is 1.6Am
2/ kg, specific surface area is 1.9m
2/ g.And with the form and aspect of the coated sheet of jaqan coatingization, L* value is 24.2, a* value is 0.7, the b* value is-0.4, the c* value of conversion is 0.8, and thermotolerance Δ E is 0.3, is the black powder.
Comparative example 2-1:
Change iron material, size, with blending ratio and the firing temperature of trimanganese tetroxide, in addition operate equally with embodiment 2-1, obtain powder.
In the powder that obtains, with respect to rhombohedral iron ore phase 100, be bixbite 15 strength ratio mutually.And with the form and aspect of the coated sheet of jaqan coatingization, the L* value is 25.5, the a* value is 5.0, the b* value is 3.2, the c* value is 5.9, and thermotolerance Δ E is 1.5, is to be difficult to be called also low powder of black, thermotolerance.
Comparative example 2-2:
Change iron material kind, size, with blending ratio and the firing temperature of trimanganese tetroxide, in addition operate equally with comparative example 2-1, obtain powder.
Creating conditions of thermotolerance black powder is shown in table 3, and all characteristics of the thermotolerance black powder that obtains are shown in table 4.
[table 3]
[table 4]
Utilizability on the industry
Thermotolerance black powder of the present invention even the excellent heat resistance variation of form and aspect (degree of blackness) at high temperature is also few, thereby is suitable as the coloured material of coating or resin combination.As use, be mainly used in the various coating that require thermotolerance and aesthetic appearance of the outer heating installation within doors, incinerator, chimney, kitchen machine, rocket launching pad etc. of sourdine, bonnet, the mechanical means of automobile or cart.
Claims (8)
1. thermotolerance black powder, it is the thermotolerance black powder that comprises the composite oxides that contain Fe, Mn and metallic element M, described thermotolerance black powder is characterised in that:
Metallic element M be selected among Al, Mg and the Ca more than a kind, being changed to below 0.5 of the form and aspect of the oven test during 800 ℃ of thermotolerance black powder, and magnetization value is 2.0Am
2Below/the kg, in the X-ray diffraction spectrum of this thermotolerance black powder, with respect to the strength ratio 100 of (104) face of rhombohedral iron ore phase, the strength ratio of (222) face of bixbite phase is 45～250.
2. thermotolerance black powder as claimed in claim 1 is characterized in that:
The content of metallic element M is 0.01～5.0 weight %.
3. thermotolerance black powder as claimed in claim 1 or 2 is characterized in that:
The Fe/Mn(mol ratio) be 1.0～10.0.
4. as each described thermotolerance black powder in the claim 1～3, it is characterized in that:
Degree of blackness (L* value) is below 25.0.
5. the manufacture method of a thermotolerance black powder, it is the manufacture method of each described thermotolerance black powder in the claim 1～4, this manufacture method is characterised in that:
Iron cpd and the manganic compound that will contain the metallic element M of 0.01～5.0wt% are 1.0～10.0 mixing with Fe/Mn than (mol ratio), and the mixture that obtains is fired 830～1000 ℃ temperature range.
6. the manufacture method of a thermotolerance black powder, it is the manufacture method of each described thermotolerance black powder in the claim 1～4, this manufacture method is characterised in that:
Comprise the operation of the compound that mixes iron cpd, manganic compound and metallic element M and the operation that the mixture that obtains is fired 830～1000 ℃ temperature range,
In described mixed processes, Fe/Mn is 1.0～10.0 than (mol ratio),
Be under the situation of Al at metallic element M, according to aluminum compound with Al
2O
3Blending ratio (the Al of meter
2O
3Amount/(iron cpd+manganic compound+aluminum compound)) be that 0.01～10.0wt% mixes,
Be under the situation of Mg at metallic element M, according to magnesium compound with MgCO
3Blending ratio (the MgCO of meter
3Amount/(iron cpd+manganic compound+magnesium compound)) be that 0.01～10.0wt% mixes,
Be under the situation of Ca at metallic element M, according to calcium cpd with CaCO
3Blending ratio (the CaCO of meter
3Amount/(iron cpd+manganic compound+calcium cpd)) be that 0.01～10.0wt% mixes.
7. coating that in coating constitutes base material, is combined with each described thermotolerance black powder in the claim 1～4.
8. a right to use requires the painted and resin combination that obtains of each described thermotolerance black powder in 1～4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
| JP2011-078397 | 2011-03-31 | ||
| 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 |
Publications (2)
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| CN103339064A true CN103339064A (en) | 2013-10-02 |
| CN103339064B CN103339064B (en) | 2016-01-20 |
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|---|---|
| JP (1) | JP5822058B2 (en) |
| KR (1) | KR20130140837A (en) |
| CN (1) | CN103339064B (en) |
| WO (1) | WO2012133646A1 (en) |
Cited By (1)
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|---|---|---|---|---|
| CN113121228A (en) * | 2017-06-15 | 2021-07-16 | 中岛产业株式会社 | Black mixed oxide material and method for producing same |
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| JP5915853B2 (en) * | 2012-03-30 | 2016-05-11 | 戸田工業株式会社 | Heat-resistant black powder and method for producing the same, paint and resin composition using the heat-resistant black powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009215384A (en) * | 2008-03-07 | 2009-09-24 | Ishihara Sangyo Kaisha Ltd | Black pigment and method of manufacturing the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3518093A1 (en) * | 1985-05-21 | 1986-11-27 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF BLACK IRON-BASED PIGMENTS |
| DE3636156A1 (en) * | 1986-10-24 | 1988-04-28 | Basf Ag | PLAIN-SHAPED PIGMENTS OF THE GENERAL FORMULA MN (DOWN ARROW) X (DOWN ARROW) -AL (DOWN ARROW) Y (DOWN ARROW) FE (DOWN ARROW) 2 (DOWN ARROW) (DOWN ARROW) (ARROW DOWN) (DOWN ARROW) (DOWN ARROW) X (DOWN ARROW) (DOWN ARROW) + (DOWN ARROW) (DOWN ARROW) Y (DOWN ARROW) (DOWN ARROW)) (DOWN ARROW) O (DOWN ARROW) 3 (DOWN ARROW) |
| DE4121789A1 (en) * | 1991-07-02 | 1993-01-07 | Bayer Ag | TEMPERATURE-STABLE BLACK PIGMENT, PROCESS FOR ITS PRODUCTION AND USE THEREOF |
| JP3781804B2 (en) * | 1995-06-28 | 2006-05-31 | チタン工業株式会社 | Resin composition |
| JPWO2010146776A1 (en) * | 2009-06-15 | 2012-11-29 | 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 the same |
-
2011
- 2011-03-31 JP JP2011078397A patent/JP5822058B2/en active Active
-
2012
- 2012-03-29 CN CN201280006983.9A patent/CN103339064B/en not_active Expired - Fee Related
- 2012-03-29 WO PCT/JP2012/058352 patent/WO2012133646A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009215384A (en) * | 2008-03-07 | 2009-09-24 | Ishihara Sangyo Kaisha Ltd | Black pigment and method of manufacturing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121228A (en) * | 2017-06-15 | 2021-07-16 | 中岛产业株式会社 | Black mixed oxide material and method for producing same |
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| KR20130140837A (en) | 2013-12-24 |
| JP2012211059A (en) | 2012-11-01 |
| CN103339064B (en) | 2016-01-20 |
| WO2012133646A1 (en) | 2012-10-04 |
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