JP3654413B2 - Iron-based black composite particle powder and method for producing the same, paint using the iron-based black composite particle powder, and rubber / resin composition colored with the iron-based black composite particle powder - Google Patents

Description

【０１４５】
芯粒子８
芯粒子１の凝集が解きほぐされたＭｎ含有黒色ヘマタイト粒子粉末２０ｋｇと水１５０ｌとを用いて、発明の実施の形態と同様にしてＭｎ含有黒色ヘマタイト粒子粉末を含むスラリーを得た。得られたＭｎ含有黒色ヘマタイト粒子粉末を含む再分散スラリーのｐＨ値を１０．５とした。次に、該スラリーに水を加えスラリー濃度を９８ｇ／ｌに調整した。このスラリー１５０ｌを加熱して６０℃とし、このスラリー中に１．０ｍｏｌ／ｌのＮａＡｌＯ_２溶液２７２２ｍｌ（Ｍｎ含有黒色ヘマタイト粒子粉末に対してＡｌ換算で０．５重量％に相当する）を加え、３０分間保持した後、酢酸を用いてｐＨ値を７．５に調整した。この状態で３０分間保持した後、濾過、水洗、乾燥、粉砕して粒子表面がアルミニウムの水酸化物により被覆されているＭｎ含有黒色ヘマタイト粒子粉末を得た。
【０１４６】
得られた粒子表面がアルミニウムの水酸化物により被覆されているＭｎ含有黒色ヘマタイト粒子粉末は、粒子径が０．３２μｍの粒状粒子粉末であった。また、粒子径の幾何標準偏差値は１．４７であり、ＢＥＴ比表面積値は３．８ｍ^２／ｇ、黒色度Ｌ^＊値は２２．６であった。蛍光Ｘ線分析の結果、Ｍｎ含有量は１３．０重量％、Ａｌ量は０．４９重量％であった。
【０１４７】
芯粒子９〜１４
芯粒子の種類、表面処理工程における添加物の種類、量を種々変えた以外は芯粒子１と同様にして表面処理済黒色酸化鉄粒子粉末及び表面処理済黒色含水酸化鉄粒子粉末を得た。
【０１４８】
この時の主要処理条件を表２に、得られた表面処理済芯粒子粉末の諸特性を表３に示す。
【０１４９】
【表２】

【０１５０】
【表３】

【０１５１】
実施例１〜７、比較例１〜５
黒色酸化鉄粒子粉末及び黒色含水酸化鉄粒子粉末の種類、アルコキシシラン添加の有無、種類及び添加量、アルコキシシラン被覆工程におけるエッジランナー処理条件、カーボンブラック微粒子粉末の種類及び添加量、カーボンブラック微粒子粉末の付着工程におけるエッジランナーによる処理条件を種々変えた以外は、前記発明の実施の形態と同様にして鉄系黒色複合粒子粉末を得た。実施例１〜７の各実施例で得られた鉄系黒色複合粒子粉末は、電子顕微鏡観察の結果、カーボンブラック微粒子粉末がほとんど認められないことから、カーボンブラック微粒子粉末のほぼ全量がアルコキシシランから生成するオルガノシラン化合物被覆に付着していることが認められた。
【０１５２】
使用したカーボンブラック微粒子粉末Ａ乃至Ｃの諸特性を表４に示す。
【０１５３】
【表４】

【０１５４】
この時の主要処理条件を表５に、得られた鉄系黒色複合粒子粉末の諸特性を表６に示す。
【０１５５】
【表５】

【０１５６】
【表６】

【０１５７】
実施例８
芯粒子８で得られた粒子表面がアルミニウムの水酸化物で被覆されているＭｎ含有黒色ヘマタイト粒子粉末１１．０ｋｇをエッジランナー「ＭＰＵＶ−２型」（（株）松本鋳造鉄工所製）に投入して、３０ｋｇ／ｃｍで３０分間混合攪拌を行い、粒子の凝集を解きほぐした。
【０１５８】
次に、メチルトリエトキシシラン２２０ｇを４００ｍｌのエタノールで混合希釈して得られるメチルトリエトキシシラン溶液を、エッジランナーを稼動させながら、粒子の凝集を解きほぐした粒子表面がアルミニウムの水酸化物で被覆されている上記Ｍｎ含有黒色ヘマタイト粒子粉末に添加し、引き続き６０ｋｇ／ｃｍの線荷重で３０分間混合攪拌を行った。
【０１５９】
次に、１１００ｇのカーボンブラック粒子Ａをエッジランナーを稼動させながら１０分間かけて添加し、更に７５ｋｇ／ｃｍの線荷重で３０分間、混合攪拌を行い、メチルトリエトキシシラン被覆にカーボンブラック微粒子粉末を付着させて、鉄系黒色複合粒子粉末を得た。
【０１６０】
得られた鉄系黒色複合粒子粉末を、乾燥機を用いて１０５℃で６０分間加熱処理を行い、残留している水分、エタノール等を揮散させた。この鉄系黒色複合粒子粉末は、粒子径が０．３２μｍの粒状粒子であり、幾何標準偏差値は１．４４、ＢＥＴ比表面積値は４．６ｍ^２／ｇ、黒色度Ｌ^＊値は１６．５、カーボンブラック脱着率は４．８％であり、メチルトリエトキシシランから生成するオルガノシラン化合物の被覆量はＳｉ換算で０．３１重量％であった。尚、電子顕微鏡観察の結果、カーボンブラック微粒子粉末がほとんど認められないことから、カーボンブラック微粒子粉末のほぼ全量がメチルトリエトキシシランから生成するオルガノシラン化合物被覆に付着していることが認められた。
【０１６１】
実施例９〜１４
黒色酸化鉄粒子粉末及び黒色含水酸化鉄粒子粉末の種類、アルコキシシランの種類及び添加量、アルコキシシラン被覆工程におけるエッジランナー処理条件、カーボンブラック微粒子粉末の種類及び添加量、カーボンブラック微粒子粉末の付着工程におけるエッジランナー処理条件を種々変えた以外は、前記実施例８と同様にして鉄系黒色複合粒子粉末を得た。実施例９〜１４の各実施例で得られた鉄系黒色複合粒子粉末は、電子顕微鏡観察の結果、カーボンブラック微粒子粉末がほとんど認められないことから、カーボンブラック微粒子粉末のほぼ全量がアルコキシシランから生成するオルガノシラン化合物被覆に付着していることが認められた。
【０１６２】
この時の主要処理条件を表５に、得られた鉄系黒色複合粒子粉末の諸特性を表６に示す。
【０１６３】
比較例６（特公昭５０−１３３００号公報記載の方法）
芯粒子３のマグネタイト粒子粉末（ブラック酸化鉄）を含む水懸濁液（マグネタイト粒子粉末６８．３ｇを含有する懸濁液１０００ｍｌ）を調整し、冷水で５回洗浄した。
【０１６４】
次に、カーボンブラック微粒子粉末Ｂの水性分散液（乾燥カーボンブラックＢ１．７５ｇを含有する５ｇの水分散液）を冷水で５００ｍｌに希釈した。
【０１６５】
このカーボンブラック懸濁液を攪拌しながら、上記マグネタイト粒子粉末を含む水懸濁液に５分間に亘って添加し、添加完了後、混合懸濁液を更に１０分間に亘って攪拌を続け、次いで放置した。
【０１６６】
約４時間後、得られた黒色沈殿物を常法により、水で濾別洗浄を５回繰り返した後、１００℃で空気中で乾燥した。
【０１６７】
得られた黒色粒子粉末の黒色度Ｌ^＊値は２０．２、カーボンブラック脱着率は５０．２％であり、芯粒子粉末であるマグネタイト粒子粉末の黒色度とほとんど変わらない値であった。
【０１６８】
＜溶剤系塗料の製造＞
実施例１５〜２８、比較例７〜２１
黒色粒子粉末の種類を種々変えたこと以外は、前記発明の実施の形態と同様にして溶剤系塗料を製造した。
【０１６９】
この時の主要製造条件及び塗膜の諸特性を表７及び表８に示した。
【０１７０】
【表７】

【０１７１】
【表８】

【０１７２】
＜水系塗料の製造＞
実施例２９〜４２、比較例２２〜３６
黒色粒子粉末の種類を種々変えた以外は、前記発明の実施の形態と同様にして水系塗料を製造した。
【０１７３】
この時の主要製造条件及び塗膜の諸特性を表９及び表１０に示した。
【０１７４】
【表９】

【０１７５】
【表１０】

【０１７６】
＜樹脂組成物の製造＞
実施例４３〜５６、比較例３７〜５１
黒色粒子粉末の種類を種々変えた以外は、前記発明の実施の形態と同様にして着色樹脂プレートを製造した。
【０１７７】
この時の主要製造条件及び着色樹脂プレートの諸特性を表１１及び表１２に示す。
【０１７８】
【表１１】

【０１７９】
【表１２】

【０１８０】
【発明の効果】
本発明に係る鉄系黒色複合粒子粉末は、粒子表面から脱離するカーボンブラック微粒子粉末が少ないことにより、ビヒクル中や樹脂組成物中における分散性に優れており、且つ、少ないカーボンブラック量で、カーボンブラック微粒子粉末のみを使用した場合の黒色度に比べて同等又は遜色のない黒色度を有しているとともに、該鉄系黒色複合粒子粉末を用いて得られた塗膜の耐酸性及び樹脂組成物の耐老化性が優れているので、塗料用、印刷インク用、化粧品用、ゴム・樹脂成形物用等の黒色顔料として好ましいものである。
【０１８１】
上記鉄系黒色複合粒子粉末を用いて得られる本発明に係る塗料は、少ないカーボンブラック量で、カーボンブラック微粒子粉末のみを使用した場合の塗膜の黒色度に比べて同等又は遜色のない黒色度を有しているとともに、得られた塗膜の耐酸性が優れているので、黒色塗料として好適である。
【０１８２】
上記鉄系黒色複合粒子粉末を用いて得られる本発明に係るゴム・樹脂組成物は、少ないカーボンブラック量で、カーボンブラック微粒子粉末のみを使用した場合のゴム・樹脂組成物黒色度に比べて同等又は遜色のない黒色度を有しているとともに、耐酸性が優れているので、黒色のゴム・樹脂組成物として好ましいものである。
【０１８３】
そして、本発明に係る鉄系黒色複合粒子粉末は、ビヒクル中や樹脂組成物中への分散性が優れており、取り扱いやすく作業性に優れているので、工業的及び経済的に有利である。
【０１８４】
また、カーボンブラック微粒子粉末の使用量が少ないので、安全上、衛生上からも好ましいものである。
【図面の簡単な説明】
【図１】 発明の実施の形態で使用したＭｎ含有黒色ヘマタイト粒子粉末の粒子構造を示す電子顕微鏡写真（×２００００）である。
【図２】 発明の実施の形態で使用したカーボンブラック微粒子粉末の粒子構造を示す電子顕微鏡写真（×２００００）である。
【図３】 発明の実施の形態で得られた鉄系黒色複合粒子粉末の粒子構造を示す電子顕微鏡写真（×２００００）である。
【図４】 比較のために示したＭｎ含有黒色ヘマタイト粒子粉末とカーボンブラック微粒子粉末との混合粒子粉末の粒子構造を示す電子顕微鏡写真（×２００００）である。[0001]
[Industrial application fields]
The present invention is excellent in dispersibility in vehicles and resin compositions due to the small amount of carbon black fine particle powder that is detached from the particle surface, and uses only carbon black fine particle powder with a small amount of carbon black. In addition to having the same or inferior blackness as compared to the blackness of the paint, it is possible to obtain a paint that can provide a coating film excellent in acid resistance and a resin composition excellent in aging resistance. An object is to provide iron-based black composite particle powder.
[0002]
[Prior art]
Carbon black fine particle powder and magnetite particle powder are typical black pigments, and have been widely used as colorants for paints, printing inks, cosmetics, rubber / resin compositions, etc. for a long time.
[0003]
The carbon black fine particle powder has the highest blackness among various black pigments, and the coating film and resin composition obtained using the carbon black fine particle powder are also excellent in acid resistance and aging resistance. On the other hand, since the particle size is a fine particle having an average particle size of about 0.005 to 0.05 μm, it is difficult to disperse it in a vehicle or a resin composition, and the bulk density is 0.1 g / cm.³Since the powder was bulky and bulky, handling was difficult and workability was poor. In addition, problems from safety and hygiene such as carcinogenicity have been pointed out.
[0004]
In other words, the carbon black fine particle powder tends to have better blackness as the amount used becomes larger, but when the amount used is increased, the dispersion in the vehicle or the resin composition becomes more difficult and the workability becomes worse. Also, it is not preferable from the viewpoint of safety and hygiene.
[0005]
On the other hand, the magnetite particle powder has an appropriate particle size, particularly an average particle diameter of about 0.08 to 1.0 μm, compared with the carbon black fine particle powder, and therefore dispersibility in the vehicle and the resin composition. Is excellent, easy to handle, and harmless, but on the other hand, the blackness is still insufficient and the coating film and resin composition obtained using magnetite particle powder The acid resistance and aging resistance of the product were also insufficient.
[0006]
In addition, since magnetite particle powder has magnetism, it tends to cause magnetic aggregation. From the viewpoint of improving dispersibility in a vehicle or a resin composition, manganese-based powder as iron-based black particle powder without magnetism is used. Containing hematite particle powder and manganese-containing hydrous iron oxide particle powder are known, but these are inferior to magnetite particle powder in terms of blackness.
[0007]
In recent years, improvement in various characteristics of black particle powder as a colorant has been desired. Advantageous characteristics of carbon black fine particle powder and black iron oxide particle powder such as magnetite particle powder and Mn-containing black hematite particle powder or Mn-containing black goethite There is a strong demand for black particle powder that combines the advantageous properties of black hydrated iron oxide particle powder such as particle powder.
[0008]
In particular, it is difficult to disperse in a vehicle or resin composition, workability such as handling properties is poor, and there are problems in safety and hygiene. A paint composition that has a black color that is equivalent or inferior to the blackness when only fine particle powder is used, and that can obtain a coating film excellent in acid resistance and a resin composition excellent in aging resistance. There is a strong demand for black particle powders that can be obtained and are excellent in dispersibility in vehicles and resin compositions.
[0009]
In response to these demands, various attempts have been made to obtain a black particle powder that combines the excellent characteristics of both carbon black fine particle powder and magnetite particle powder, for example, 1) precipitated from an aqueous solution. A method of adding an aqueous dispersion containing carbon black fine particle powder to an aqueous suspension containing magnetite particles, followed by mixing and stirring to adsorb the carbon black fine particle powder on the particle surface of the magnetite particle powder (Japanese Patent Publication No. 50-13300) Publication) 2) When iron-containing waste sludge in which a high molecular weight organic substance such as molasses is dissolved and hot gas containing carbon black are introduced into a spray reactor at a temperature of 450 to 850 ° C. to generate magnetite particles from iron salt At the same time, carbon black is bonded to the surface of the magnetite particles by using molasses as a binding accelerator (Japanese Patent Laid-Open No. 49). 48725) 3) Coprecipitate whose surface is coated with carbon black by suspending carbon black in an iron salt aqueous solution and then adding alkali to coprecipitate carbon black and iron trioxide. (Japanese Patent Publication No. 55-39580), 4) Carbon black or the like is deposited on the surface of the fine plate-like particles, and the carbon black or the like is treated with an anionic or cationic surfactant. Methods of immobilizing with an ionic surfactant and an organofunctional organosilane compound (JP-A-6-145556, JP-A-7-316458) and the like are known.
[0010]
[Problems to be solved by the invention]
The black particle powder that combines the advantageous characteristics of carbon black fine particle powder with the advantageous characteristics of black iron oxide particle powder and black hydrated iron oxide particle powder is currently the most demanded. However, a black particle powder that sufficiently satisfies these characteristics has not been obtained. That is, in the case of the above-mentioned known method 1), the desorption rate of the carbon black fine particle powder is high as shown in Comparative Example 6 below, and the carbon black fine particle powder is dispersed during dispersion in the vehicle or the resin composition. Due to desorption, uniform dispersion in the vehicle or the resin composition is difficult, and the blackness of the resulting paint or resin composition cannot be sufficiently improved.
[0011]
In the case of the above known method 2), in order to obtain the same or inferior blackness as compared with the case where only the carbon black fine particle powder is used, the carbon black fine particle powder is added to 100 parts by weight of the magnetite particle powder. It is necessary to use a large amount of about 280 parts by weight. Also in the case of the above known method 3), in order to obtain the same or inferior blackness as compared with the case where only the carbon black fine particle powder is used, the carbon black fine particle powder is added to 100 parts by weight of the magnetite particle powder. On the other hand, it is necessary to add about 100 to 400 parts by weight, and the carbon black fine particles adhering to the surface of the coprecipitate are easily detached. The particle powder produced by the above-mentioned known method 4) has poor blackness, and the carbon black fine particle powder is easily detached. The particle powder obtained by this method is not a black particle powder.
[0012]
Therefore, the present invention is excellent in dispersibility in a vehicle or a resin composition because there are few carbon black fine particle powders detached from the particle surface, and only the carbon black fine particle powder is contained in a small amount of carbon black. In addition to having the same or inferior blackness compared to the blackness when using a coating, it is possible to obtain a paint that can obtain a coating film excellent in acid resistance and a resin composition excellent in aging resistance. It is a technical problem to obtain iron-based black composite particle powder that can be used.
[Means for Solving the Problems]
[0013]
The technical problem can be achieved by the present invention as follows.
[0014]
That is, the present invention provides a black iron oxide particle powder or black hydrated iron oxide particle powder having an average particle size of 0.08 to 1.0 μm, and if necessary, an aluminum hydroxide, an aluminum oxide on the particle surface. Organo produced from alkoxysilane on the surface of either black iron oxide particle powder or black hydrated iron oxide particle powder coated with one or more selected from silicon hydroxide and silicon oxide Coated with silane compoundThe coating amount of the organosilane compound produced from the alkoxysilane is 0.02 to 5.0% by weight in terms of Si with respect to the alkoxysilane-coated black iron oxide particle powder or the alkoxysilane-coated black hydrated iron oxide particle powder.And an iron-based black composite particle powder having a carbon black fine particle powder having an average particle diameter of 0.005 to 0.05 μm adhered to the surface of the organosilane compound coating. 1 to 30 parts by weight with respect to 100 parts by weight of iron oxide particle powder or black hydrous iron oxide particle powder.
[0015]
Further, the present invention provides a black iron oxide particle powder or black hydrated iron oxide particle powder having an average particle diameter of 0.08 to 1.0 μm, and if necessary, an aluminum hydroxide, an aluminum oxide on the particle surface of the particle, Black iron oxide particle powder or black hydrated iron oxide particle powder coated with one or more selected from silicon hydroxide and silicon oxide and alkoxysilane are mixed and stirred using an edge runner. After coating the particle surface of the particle powder with alkoxysilane, carbon black fine particle powder having an average particle size of 0.005 to 0.05 μm with respect to 100 parts by weight of the black iron oxide particle powder or black hydrated iron oxide powder 1 to 30 parts by weight is added to obtain a mixed powder, and then the mixed powder is mixed and stirred using an edge runner, and then dried or heat-treated to obtain the above alkoxysilane. Carbon black fine particle powder is made to adhere to the organosilane compound coating | cover produced | generated from silicon, It is the manufacturing method of the said iron type black composite particle powder characterized by the above-mentioned.
[0016]
In addition, the present invention is a paint characterized in that any one of the above iron-based black composite particle powders is blended in a paint constituting base material.
[0017]
Further, the present invention is a rubber / resin composition characterized by being colored using any one of the iron-based black composite particle powders.
[0018]
The configuration of the present invention will be described in detail as follows.
[0019]
First, the iron-based black composite particle powder according to the present invention will be described.
[0020]
The particle shape and particle size of the iron-based black composite particle powder according to the present invention largely depend on the particle shape and particle size of the black iron oxide particles or black hydrous iron oxide particles as the core particles, and particles that are substantially similar to the core particles It has a morphology and has a slightly larger particle size than the core particles.
[0021]
That is, the iron-based black composite particle powder according to the present invention has a particle size of 0.082 to 1.05 μm, preferably an average particle size when granular iron oxide particles or hydrous iron oxide particles are used as core particles. When the particle diameter is 0.1 to 0.7 μm, more preferably the average particle diameter is 0.1 to 0.5 μm, and the needle-like or spindle-like iron oxide particles or hydrous iron oxide particles are used as the core particles, the average The particle diameter (major axis diameter) is 0.082 to 1.05 μm, preferably 0.1 to 0.7 μm, more preferably 0.1 to 0.5 μm, and the axial ratio (major axis diameter / minor axis diameter). ) Is 2-20, preferably 3-15, more preferably 3-10. When plate-like iron oxide particles or plate-like hydrous iron oxide particles are used as core particles, the average particle size (plate surface diameter) is 0.082 to 1.05 μm, preferably 0.1 to 0.7 μm, more preferably. Is 0.1 to 0.5 μm, and the plate ratio (plate diameter / thickness) is 2 to 50, preferably 3 to 20, and more preferably 3 to 10.
[0022]
When the average particle size is less than 0.082 μm, dispersion in the vehicle or the resin composition becomes difficult due to an increase in intermolecular force due to the refinement of the particles. If the average particle diameter exceeds 1.05 μm, uniform dispersion in the vehicle or resin composition becomes difficult as the particles become larger.
[0023]
The upper limit of the blackness of the iron-based black composite particle powder according to the present invention is L^*The value is 18. L^*When the value exceeds 18, the brightness becomes high and the blackness is not sufficient. The more preferable upper limit of the blackness is L^*The value is 17.8. The lower limit is L^*The value is about 15.
[0024]
The desorption rate of carbon black in the iron-based black composite particle powder according to the present invention is preferably 20% or less, more preferably 10% or less. When the desorption rate of carbon black exceeds 20%, the dispersed carbon black in the vehicle or the resin composition may be hindered by the desorbed carbon black during the production of the paint or the resin composition.
[0025]
The iron-based black composite particle powder according to the present invention has a BET specific surface area value of 1 to 200 m.²/ G, preferably 2 to 150 m²/ G, more preferably 2.5 to 100 m²/ G. BET specific surface area value is 1m²If it is less than / g, the particles are coarse or particles are sintered between particles, which is not preferable because it adversely affects the dispersibility in the vehicle and the resin composition. . BET specific surface area value is 200m²When exceeding / g, dispersion in a vehicle or a resin composition becomes difficult due to an increase in intermolecular force due to finer particles.
[0026]
Further, the iron-based black composite particle powder according to the present invention preferably has a geometric standard deviation value of the particle diameter of 1.8 or less. When the geometric standard deviation value exceeds 1.80, it is difficult to uniformly disperse in the vehicle or the resin composition because of the existing coarse particles. Considering uniform dispersion in the vehicle or resin composition, it is preferably 1.7 or less. Considering industrial productivity, the lower limit value of the geometric standard deviation value of the particle diameter is 1.01.
[0027]
The black iron oxide particle powder in the iron-based black composite particle powder according to the present invention is a manganese-containing hematite particle powder containing 5 to 40% by weight of manganese with respect to the magnetite particle powder and the manganese-containing hematite particle powder. The iron particle powder is a manganese-containing goethite particle powder containing 5 to 40% by weight of manganese with respect to the manganese-containing goethite particle powder.
[0028]
Black iron oxide particles and black hydrated iron oxide particles have various shapes, such as spherical, granular, octahedral, hexahedral, polyhedral, etc., acicular, spindle, rice, etc. And plate-like particles.
[0029]
As for the particle size, in the case of granular particles such as spherical, granular, octahedral, hexahedral and polyhedral, the average particle diameter is 0.08 to 1.0 μm, preferably 0.098 to 0.68 μm, more preferably Is 0.098 to 0.48 μm, and in the case of acicular particles such as needles, spindles, and rice grains, the average particle diameter (major axis diameter) is 0.08 to 1.0 μm, preferably 0.098 to It is 0.68 μm, more preferably 0.098 to 0.48 μm, and the axial ratio (major axis diameter / minor axis diameter) is 2 to 20, preferably 2 to 15, more preferably 2 to 10.
[0030]
In the case of plate-like particles, the average particle diameter (plate surface diameter) is 0.08 to 1.0 μm, preferably 0.098 to 0.68 μm, more preferably 0.098 to 0.48 μm. The ratio (plate surface diameter / thickness) is 2 to 50, preferably 2 to 20, and more preferably 2 to 10.
[0031]
The blackness of black iron oxide particle powder or black hydrated iron oxide particle powder as the core particle powder is usually L in the case of magnetite particle powder.^*The lower limit value exceeds 18 and the upper limit value is 25, preferably 24. In the case of manganese-containing hematite particles, usually L^*The lower limit value exceeds 18 and the upper limit value is 28, preferably 25. For manganese-containing goethite particles, usually L^*The lower limit of the value exceeds 18, and the upper limit is 30, preferably 28.
[0032]
L^*When the value exceeds the upper limit value, it is difficult to say that the blackness is sufficient, and it is difficult to obtain the iron-based black composite particle powder excellent in blackness, which is the object of the present invention.
[0033]
The BET specific surface area value of the black iron oxide particle powder or the black hydrated iron oxide particle powder as the core particle powder is 1 to 200 m.²/ G, preferably 2 to 150 m²/ G, more preferably 2.5 to 100 m²/ G, and the geometric standard deviation value of the particle diameter is 1.8 or less, preferably 1.7 or less. The lower limit value of the geometric standard deviation value of the particle diameter is 1.01.
[0034]
The organosilane compound (hereinafter referred to as organosilane compound) produced from the alkoxysilane in the iron-based black composite particles according to the present invention is an organosilane compound produced from the alkoxysilane represented by Chemical Formula 1 through a drying or heating process. is there.
[Chemical 1]
R_aSiX_4-a
R: -C₆H₅,-(CH₃)₂CHCH₂, -N-C_mH_{2m + 1}
X: -OCH₃, -OC₂H₅
m: an integer from 1 to 18
a: integer from 0 to 3
[0035]
Specific examples of the alkoxysilane include methyltriethoxysilane, dimethyldiethoxysilane, tetraethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, and phenyltrimethoxy. Examples include silane, diphenyldimethoxysilane, isobutyltrimethoxysilane, and decyltrimethoxysilane.
[0036]
In view of the desorption rate and adhesion effect of the carbon black fine particle powder, an organosilane compound formed from methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, isobutyltrimethoxysilane, and phenyltriethoxysilane is preferable, and methyltriethoxysilane An organosilane compound produced from methyltrimethoxysilane is most preferred.
[0037]
The coating amount of the organosilane compound produced from the alkoxysilane is 0.02 to 5.0% by weight in terms of Si with respect to the alkoxysilane-coated black iron oxide particle powder or the alkoxysilane-coated black hydrated iron oxide particle powder. preferable. More preferably, it is 0.03-2.0 weight%, More preferably, it is 0.05-1.5 weight%.
[0038]
If it is less than 0.02% by weight, it is difficult to sufficiently adhere the carbon black fine particle powder to such an extent that the blackness can be improved.
[0039]
When it exceeds 5.0% by weight, the carbon black fine particle powder can be sufficiently adhered, but there is no meaning to add more than necessary.
[0040]
As the carbon black fine particle powder in the iron-based black composite particle powder according to the present invention, commercially available furnace black, channel black or the like can be used. Specifically, MA-100, MA7, # 1000, # 2400B, # 30, MA8, MA11, # 50, # 52, # 45, # 2200B, MA600, etc. (trade name: Mitsubishi Chemical Co., Ltd.) Seast 9H, Seast 7H, Seast 6, Seast 3H, Seast 300, Seast FM, etc. (Trade name, Tokai Carbon Co., Ltd.) can be used. Considering the affinity with the organosilane compound, MA-100, MA7, # 1000, # 2400B, and # 30 are preferable. The average particle size of the carbon black fine particle powder is about 0.005 to 0.05 μm, more preferably about 0.010 to 0.035 μm.
[0041]
When it is less than 0.005 μm, the carbon black fine particle powder becomes too fine, and handling becomes difficult.
[0042]
If it exceeds 0.05 μm, the carbon black fine particle size is too large compared to the iron oxide particle or hydrous iron oxide particle as the core particle, so the adhesion strength to the alkoxysilane coating is insufficient. As a result, the desorption rate of the carbon black fine particles increases, and as a result, the dispersibility in the vehicle and the resin composition decreases.
[0043]
The ratio of the average particle size of the black iron oxide particles or black hydrated iron oxide particles to the average particle size of the carbon black fine particles is preferably 2 or more. When the particle size is smaller than 2, the particle size of the carbon black fine particles is too large with respect to the particle size of the black iron oxide particles or black hydrated iron oxide particles as the core particles, so that the adhesion strength to the alkoxysilane coating becomes insufficient, The desorption rate of the carbon black fine particles increases, and as a result, the dispersibility in the vehicle and the resin composition decreases.
[0044]
The adhesion amount of the carbon black fine particle powder is 1 to 30 parts by weight with respect to 100 parts by weight of the black iron oxide particle powder or the black hydrated iron oxide particle powder.
[0045]
When the amount is less than 1 part by weight, the amount of carbon black fine particle powder attached is insufficient, and sufficient blackness cannot be obtained.
[0046]
When the amount exceeds 30 parts by weight, sufficient blackness can be obtained, but the carbon black fine particle powder is easily detached due to the large amount of carbon black fine particle powder attached, and as a result, dispersed in the vehicle or resin composition. Sex is reduced.
[0047]
In the iron-based black composite particle powder according to the present invention, if necessary, the surface of the black iron oxide particle powder or the black hydrated iron oxide particle powder is prepared in advance with an aluminum hydroxide, an aluminum oxide, a silicon hydroxide and It may be coated with one or more selected from oxides of silicon (hereinafter referred to as “coating with aluminum hydroxide, etc.”), compared with the case where it is not coated with aluminum hydroxide, etc. , Dispersibility in the vehicle and the resin composition is improved.
[0048]
The coating amount of aluminum hydroxide, etc. is in terms of Al with respect to black iron oxide particle powder or black hydrated iron oxide particle powder, SiO₂Conversion or Al conversion amount and SiO₂The total amount with the converted amount is preferably 0.01 to 50% by weight.
[0049]
If it is less than 0.01% by weight, the effect of improving dispersibility in the vehicle or resin composition cannot be obtained.
[0050]
When it exceeds 50% by weight, the effect of improving the dispersibility in the vehicle or the resin composition can be sufficiently obtained, and there is no meaning to coat more than necessary.
[0051]
The iron-based black composite particle powder according to the present invention coated with an aluminum hydroxide or the like is approximately the same particle size as that of an iron-based black composite particle powder not coated with an aluminum hydroxide or the like, Geometric standard deviation value, BET specific surface area value, and blackness L^*Has a value.
[0052]
Next, a method for producing the iron-based black composite particle powder according to the present invention will be described.
[0053]
The granular magnetite particles, which are the core particles in the present invention, are oxidized by passing an oxygen-containing gas through a suspension containing a ferrous hydroxide colloid obtained by reacting an aqueous ferrous salt solution with an alkali hydroxide. It is obtained by a so-called wet method.
[0054]
Acicular magnetite particles and spindle-shaped magnetite particles are ferrous hydroxide colloids, ferrous carbonate and iron-containing precipitates obtained by reacting ferrous salt aqueous solutions with alkali hydroxide, alkali carbonate or alkali hydroxide / alkali carbonate. Oxygen-containing gas is passed through a suspension containing any of the substances to oxidize, so-called wet goethite particles or spindle-shaped goethite particles are produced by a so-called wet method, the goethite particles are filtered, washed with water, and then reduced. It can be obtained by heat reduction at 300 to 500 ° C. in a neutral atmosphere.
[0055]
The granular manganese-containing hematite particles, which are the core particles in the present invention, are the above-mentioned wet particles that produce particles or granular magnetite particles in which the granular magnetite particles produced by the above-mentioned wet method are coated with 8 to 150 atomic% of manganese compound based on the total Fe. In the method, the reaction is carried out in the presence of manganese to produce magnetite particles containing 8 to 150 atomic% of manganese with respect to the total Fe, and then any one of the manganese-containing magnetite particles obtained by filtering, washing with water and drying is obtained. It is obtained by heating at 750 to 1000 ° C. in air.
[0056]
Since the manganese-containing hematite particles are non-magnetic, magnetic aggregation is unlikely to occur, which is preferable from the viewpoint of dispersibility.
[0057]
Needle-like or spindle-like manganese-containing hematite particles are obtained by heating needle-like or spindle-like goethite particles containing 8-150 atomic% manganese to the total Fe obtained by the method described later at 400-800 ° C. in air. Can be obtained.
[0058]
In the wet method for producing needle-like or spindle-like goethite particles, needle-like or spindle-like goethite particles in the present invention are reacted in the presence of manganese to produce 8-150 atomic% manganese based on the total Fe. It is obtained by making it contain.
[0059]
In the present invention, the black iron oxide particle powder or black hydrated iron oxide particle powder is coated with alkoxysilane by mechanically mixing and stirring the black iron oxide particle powder or black hydrated iron oxide particle powder and the alkoxysilane solution. What is necessary is just to mix and stir mechanically, spraying an alkoxysilane solution to iron oxide particle powder or black hydrous iron oxide particle powder. Almost all of the added alkoxysilane is coated on the surface of the black iron oxide particles or black hydrated iron oxide particles.
[0060]
In order to uniformly coat the alkoxysilane with the particle surface, it is preferable that the aggregation of the black iron oxide particle powder or the black hydrated iron oxide particle powder is previously unraveled using a pulverizer. As an apparatus for mixing and stirring, an edge runner, a Henschel mixer, or the like can be used.
[0061]
The conditions at the time of mixing and stirring may be adjusted as appropriate such as the amount ratio, linear load, mixing and stirring time, etc., so that the alkoxysilane is coated as uniformly as possible on the surface of the black iron oxide particle powder or black hydrated iron oxide powder particle. The treatment time is preferably 20 minutes or longer.
[0062]
The amount of alkoxysilane added is preferably 0.15 to 45 parts by weight with respect to 100 parts by weight of black iron oxide particle powder or black hydrated iron oxide particle powder. If it is less than 0.15 parts by weight, it is difficult to sufficiently adhere the carbon black fine particle powder to such an extent that the blackness can be improved. When it exceeds 45 parts by weight, the carbon black fine particle powder can be sufficiently adhered, but there is no meaning to add more than necessary.
[0063]
Next, after adding the carbon black fine particle powder to the black iron oxide particle powder or black hydrated iron oxide particle powder coated with alkoxysilane, followed by mixing and stirring, the carbon black fine particle powder was adhered to the surface of the alkoxysilane coating. Dry or heat treatment.
[0064]
The carbon black fine particle powder is preferably added over a period of about 5 to 60 minutes while taking a small amount of time.
[0065]
The conditions during mixing and stirring may be adjusted as appropriate so that the carbon black fine particle powder uniformly adheres, such as the amount ratio, linear load, mixing and stirring time, etc. The treatment time is preferably 20 minutes or more.
[0066]
The addition amount of the carbon black fine particle powder is 1 to 30 parts by weight with respect to 100 parts by weight of the black iron oxide particle powder or the black hydrated iron oxide particle powder. When the amount is less than 1 part by weight, the amount of carbon black fine particle powder attached is insufficient, and sufficient blackness cannot be obtained. When the amount exceeds 30 parts by weight, sufficient blackness is obtained, but the amount of carbon black fine particle powder increases, so that the carbon black fine particle powder is easily detached from the particle surface. As a result, in the vehicle and the resin composition Dispersibility in the product is reduced.
[0067]
The heating temperature in the drying or heating step is usually preferably 40 to 200 ° C, more preferably 60 to 150 ° C, and the treatment time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 3 hours. Alkoxysilane becomes an organosilane compound by this drying or heating process.
[0068]
Prior to mixing and stirring with the alkoxysilane solution, the black iron oxide particle powder or the black hydrated iron oxide particle powder may have a surface of aluminum hydroxide, aluminum oxide, silicon hydroxide and You may coat | cover with 1 type, or 2 or more types chosen from the oxide of silicon.
[0069]
Coating with aluminum hydroxide or the like is performed by adding an aluminum compound, a silicon compound, or both of these compounds to an aqueous suspension obtained by dispersing black iron oxide particle powder or black hydrated iron oxide particle powder, and mixing and stirring. Or, if necessary, by adjusting the pH value after mixing and stirring, the surface of the black iron oxide particle powder or black hydrated iron oxide particle powder has aluminum hydroxide, aluminum oxide, silicon One or more selected from hydroxides and silicon oxides are deposited, and then filtered, washed with water, dried and pulverized. If necessary, a deaeration / consolidation process may be further performed.
[0070]
As the aluminum compound, aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride, and aluminum nitrate, alkali aluminates such as sodium aluminate, alumina sol, and the like can be used.
[0071]
The addition amount of the aluminum compound is 0.01 to 50.00% by weight in terms of Al with respect to the black iron oxide particle powder or the black hydrated iron oxide particle powder. When the amount is less than 0.01% by weight, it is difficult to coat the particle surface with a sufficient amount of aluminum hydroxide and the like, and an effect of improving dispersibility in a vehicle or a resin composition is obtained. Absent. If it exceeds 50.00% by weight, the coating effect is saturated, so there is no point in adding more than necessary.
[0072]
As the silicon compound, No. 3 water glass, sodium orthosilicate, sodium metasilicate, colloidal silica and the like can be used.
[0073]
The amount of silicon compound added is the amount of SiO2 added to black iron oxide particle powder or black hydrated iron oxide particle powder.₂It is 0.01 to 50.00% by weight in terms of conversion. When the amount is less than 0.01% by weight, it is difficult to coat a sufficient amount of silicon oxide or the like on the particle surface, and the effect of improving dispersibility in the vehicle or the resin composition cannot be obtained. . If it exceeds 50.00% by weight, the coating effect is saturated, so there is no point in adding more than necessary.
[0074]
When an aluminum compound and a silicon compound are used in combination, with respect to black iron oxide particle powder or black hydrated iron oxide particle powder, the amount in terms of Al and SiO₂0.01 to 50.00% by weight in total with the converted amount is preferable.
[0075]
Next, the coating material containing the iron-based black composite particle powder according to the present invention will be described.
[0076]
When the solvent-based paint containing the iron-based black composite particle powder according to the present invention is used as a coating film, the blackness L^*Since the value is 15 to 19.5, it has a blackness equivalent to or inferior to the blackness when only the carbon black fine particle powder is used with a small amount of carbon black. Further, the glossiness is 85% or more, and the acid resistance is ΔG value of 10.0 or less, ΔL^*The value is 1.0 or less. If blackness is taken into account, L^*The value is preferably 15 to 18.5, and more preferably 15 to 18. The glossiness is preferably 87% or more, and more preferably 88% or more. The acid resistance has a ΔG value of preferably 9.5 or less, and more preferably 9.3 or less. ΔL^*The value is preferably 0.9 or less, and more preferably 0.8 or less.
[0077]
When the water-based paint containing the iron-based black composite particle powder according to the present invention is formed into a coating film, L^*Since the value is 15 to 20, it has a blackness equivalent to or inferior to the blackness when only carbon fine particle powder is used with a small amount of carbon black. Further, the glossiness is 80% or more, and the acid resistance is ΔG value of 10.0 or less, ΔL^*The value is 1.0 or less. If blackness is taken into account, L^*15-19 are preferable and 15-18 are more preferable. The glossiness is preferably 83% or more, and more preferably 85% or more. The acid resistance is preferably a ΔG value of 9.5 or less, and more preferably 9.0 or less. ΔL^*The value is preferably 0.9 or less, and more preferably 0.8 or less.
[0078]
The blending ratio of the iron-based black composite particle powder in the paint according to the present invention can be used in the range of 1.0 to 100 parts by weight with respect to 100 parts by weight of the paint base material. The amount is preferably 2.0 to 100 parts by weight, more preferably 5.0 to 100 parts by weight.
[0079]
As the coating material constituting substrate, a resin, a solvent, and if necessary, an antifoaming agent, an extender pigment, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent and the like are blended.
[0080]
As the resin, acrylic resin, alkyd resin, polyester resin, polyurethane resin, epoxy resin, phenol resin, melamine resin, amino resin and the like that are usually used for solvent-based paints can be used. For water-based paints, commonly used water-soluble alkyd resins, water-soluble melamine resins, water-soluble acrylic resins, and water-soluble urethane emulsion resins can be used.
[0081]
As the solvent, toluene, xylene, butyl acetate, methyl acetate, methyl isobutyl ketone, butyl cellosolve, ethyl cellosolve, butyl alcohol, aliphatic hydrocarbons and the like that are usually used for solvent-based paints can be used.
[0082]
As a solvent for water-based paints, butyl cellosolve, butyl alcohol and the like which are usually used in water-based paints can be used in addition to water.
[0083]
Antifoaming agents include Nopco 8034 (product name), SN deformer 477 (product name), SN deformer 5013 (product name), SN deformer 247 (product name), SN deformer 382 (product name) (all of these are San Nopco Commercially available products such as manufactured by Co., Ltd., Antihome 08 (trade name), Emulgen 903 (trade name) (all of which are manufactured by Kao Corporation) can be used.
[0084]
Next, the rubber / resin composition colored with the iron-based black composite particle powder according to the present invention will be described.
[0085]
The rubber / resin composition colored with the iron-based black composite particle powder according to the present invention is L^*Since the value is from 15 to 21, it has a blackness equivalent to or inferior to the blackness when only the carbon black fine particle powder is used with a small amount of carbon black. Further, the result of visual observation of dispersibility was 4 or 5. In the aging resistance, the ratio of the discolored portion when heated at 190 ° C. for 90 minutes is 15% or less. If blackness is taken into account, L^*The value is preferably from 15 to 20, and more preferably from 15 to 19.5. The aging resistance is preferably 10% or less, and more preferably 5% or less.
[0086]
The mixing ratio of the iron-based black composite particle powder in the rubber / resin composition according to the present invention can be used in the range of 0.5 to 200 parts by weight with respect to 100 parts by weight of the constituent base material. Considering handling of the product, it is preferably 1.0 to 150 parts by weight, more preferably 2.5 to 100 parts by weight.
[0087]
As a constituent substrate in the rubber or resin composition according to the present invention, as well as iron-based black composite particle powder and rubber or a known thermoplastic resin, if necessary, a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, various stabilizing agents Additives such as agents are blended.
[0088]
The amount of the additive may be 50% by weight or less based on the total amount of the iron-based black composite particle powder and rubber or resin. When the content of the additive exceeds 50% by weight, the moldability is lowered.
[0089]
The rubber or resin composition according to the present invention is prepared by thoroughly mixing a rubber or resin raw material and iron-based black composite particle powder in advance, and then applying a strong shearing action under heating using a kneader or an extruder. The aggregate of the black composite particle powder is broken and the iron black composite particle powder is uniformly dispersed in the rubber or resin, and then molded into a shape suitable for the purpose.
[0090]
DETAILED DESCRIPTION OF THE INVENTION
A typical embodiment of the present invention is as follows.
[0091]
The average particle size of each of the black iron oxide particles, black hydrous iron oxide particles, carbon black particles, and iron-based black composite particles is a photograph obtained by enlarging the electron micrograph (× 20000) four times in the vertical and horizontal directions, respectively. The fixed direction diameter was measured for each of about 350 particles shown in FIG.
[0092]
The axial ratio is shown as the ratio of the average major axis diameter to the average minor axis diameter.
[0093]
The geometric standard deviation value of the particle diameter was indicated by the value obtained by the following method. That is, the value measured for the particle size shown in the above enlarged photograph is calculated from the measured value, and the particle size is plotted on the horizontal axis on the log-normal probability paper according to a statistical method from the actual particle size and number of particles. The diameter was plotted on the vertical axis in terms of the cumulative number of particles belonging to each of the predetermined particle diameter sections (under the cumulative sieve) as a percentage. Then, from this graph, the particle diameter values corresponding to the cumulative number of particles of 50% and 84.13% are read, and the geometric standard deviation value = (particle diameter at 84.13% under accumulated fluid) / (under accumulated fluid). The value was calculated according to the particle diameter (geometric mean diameter) at 50%, and the smaller the geometric standard deviation value, the better the particle size distribution.
[0094]
The specific surface area value was indicated by a value measured by the BET method.
[0095]
Each of the amount of Mn present in the interior and surface of black iron oxide particles, black hydrous iron oxide particles and iron-based black composite particles, Al amount, Si amount and Si amount contained in the organosilane compound produced from alkoxysilane is Using a “fluorescence X-ray analyzer 3063M type” (manufactured by Rigaku Denki Kogyo Co., Ltd.), the measurement was performed according to “General X-ray fluorescence analysis rules” of JIS K0119.
[0096]
The amount of carbon adhering to the iron-based black composite particles was measured using “Horiba Metal Carbon / Sulfur Analyzer EMIA-2200 type” (manufactured by Horiba, Ltd.).
[0097]
The desorption rate (T%) of the carbon black adhering to the iron-based black composite particles was indicated by a value obtained by the following method. The closer T (%) is to 0, the smaller the amount of carbon black desorbed from the particles.
[0098]
3 g of iron-based black composite particle powder and 40 ml of ethanol are placed in a 50 ml settling tube, subjected to ultrasonic dispersion for 20 minutes, and then left to stand for 120 minutes. separated. Next, 40 ml of ethanol was again added to the iron-based black composite particle powder, and the mixture was further subjected to ultrasonic dispersion for 20 minutes and then allowed to stand for 120 minutes to separate the iron-based black composite particle powder from the detached carbon black. This iron-based black composite particle powder is dried at 100 ° C. for 1 hour, and the amount of carbon is measured using the above-mentioned “Horiba Metal Carbon / Sulfur Analyzer EMIA-2200 type” (manufactured by Horiba, Ltd.). The obtained value was defined as the carbon black desorption rate (T%).
[0099]
T (%) = {(Wa-We) / Wa} × 100
Wa: Carbon black adhesion amount of iron-based black composite particle powder
We: Carbon black adhesion amount of iron-based black composite particle powder after desorption test
[0100]
The blackness of each of the black iron oxide particle powder, the black hydrated iron oxide particle powder, and the iron-based black composite particle powder is a paste obtained by kneading 0.5 g of a sample and 0.7 cc of castor oil with a Hoover-type Mahler. Add 4.5g of clear lacquer, knead and paint, and then apply a 6mil applicator on cast-coated paper (coating thickness: approx. 30μm). Color index L in accordance with JIS Z 8729 using total MSC-IS-2D (manufactured by Suga Test Instruments Co., Ltd.)^*The value was shown by the measured value.
[0101]
The blackness of the paint using the black particle powder is the blackness of the coating film obtained by applying the paint having the composition described later, and the blackness of the rubber / resin composition using the black particle powder is composed of the composition described later. The color index L is determined in accordance with JIS Z 8729 using the multi-light source spectral colorimeter MSC-IS-2D (manufactured by Suga Test Instruments Co., Ltd.).^*The value was shown by the measured value.
[0102]
Where L^*The value represents lightness and L^*It shows that blackness is excellent, so that a value is small.
[0103]
The dispersibility in the paint vehicle was evaluated by measuring the glossiness of a coating film produced in the same manner as in the embodiment of the invention.
[0104]
The glossiness was determined by measuring the 20 ° glossiness using “Gloss meter UGV-5D” (manufactured by Suga Test Instruments Co., Ltd.). The higher the glossiness, the better the dispersibility of the particles.
[0105]
Regarding the paint viscosity, the paint viscosity at 25 ° C. of the paint prepared according to the formulation described below is measured by using an E-type viscometer (cone plate type viscometer) EMD-R (manufactured by Tokyo Keiki Co., Ltd.) and a shear rate D = 1.92 sec^-1The value at was determined.
[0106]
The dispersibility in the resin composition was evaluated in five stages by visually determining the number of undispersed aggregated particles on the surface of the obtained resin composition. 5 indicates the best dispersion state.
[0107]
1: 1cm²More than 50 per
2: 1 cm²10 or more and less than 50 per
3: 1 cm²5 to less than 10 per
4: 1cm²1 to less than 5 per
5: Undispersed material not recognized
[0108]
The acid resistance was determined as follows.
[0109]
A sample piece having a coating film prepared by applying and drying a coating obtained by using black particle powder on a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G 3141) at a thickness of 150 μm is prepared. Measure glossiness and blackness.
[0110]
Next, a 5 wt% aqueous sulfuric acid solution is put into a 1000 cc beaker, the sample piece is hung with a thread, immersed to a depth of about 120 mm, and allowed to stand at 25 ° C. for 24 hours.
[0111]
Next, the sample piece is taken out from the acid solution, gently washed with running water, and after the water has been shaken off, the glossiness and blackness of the central portion of the sample piece are measured. And the glossiness change ((DELTA) G) before and behind immersion in the acid solution of a sample piece, and a blackness change ((DELTA) L).^*Value) was measured, and the acid resistance was evaluated based on the magnitude. ΔG and ΔL^*The smaller the value, the better the acid resistance.
[0112]
Aging resistance is defined as the area S of the portion where the colored resin plate (1.5 cm long × 1.5 cm wide × 1 mm thick) kneaded with black particle powder is discolored and the resin deteriorates when heated at 190 ° C. Surface area S of the colored plate before heating₀(1.5 × 1.5 = 2.25cm²Ratio S / S₀Was determined by quantifying in increments of 5%.
[0113]
That is, (S / S₀) × 100 is 0%, indicating no deterioration, (S / S₀) When x100 is 100%, the resin is completely deteriorated.
[0114]
<Manufacture of iron-based black composite particle powder>
Mn-containing black hematite particle powder (particle shape: granular, average particle diameter 0.30 μm, geometric standard deviation) shown in the electron micrograph (× 20000) of FIG. 1 obtained by the production method described in JP-A-4-144924 Value 1.46, BET specific surface area 3.6 m²/ G, Mn content 13.3% by weight, blackness L^*Value 22.6) In order to break up the agglomeration, 20 kg was poured into 150 liters of pure water using a stirrer, and “TK Pipeline Homomixer” (product name, manufactured by Tokushu Kika Kogyo Co., Ltd.) was used three times. A slurry containing Mn-containing black hematite particle powder was obtained.
[0115]
Subsequently, the slurry containing this Mn-containing black hematite particle powder was passed five times at a shaft speed of 2000 rpm using a horizontal sand grinder “Mighty Mill MHG-1.5L” (product name, manufactured by Inoue Seisakusho Co., Ltd.). Thus, a dispersion slurry containing Mn-containing black hematite particle powder was obtained.
[0116]
The sieve residue at 325 mesh (aperture 44 μm) of the obtained dispersion slurry containing Mn-containing black hematite particle powder was 0%. The dispersion slurry was filtered and washed with water to obtain a cake of Mn-containing black hematite particle powder. After drying this Mn-containing black hematite particle powder cake at 120 ° C., 11.0 kg of the dried powder was put into an edge runner “MPUV-2 type” (product name, manufactured by Matsumoto Foundry), and 30 kg The mixture was stirred for 30 minutes at / cm to loosen the particles agglomerate lightly.
[0117]
Next, a methyltriethoxysilane solution obtained by mixing and diluting 110 g of methyltriethoxysilane with 200 ml of ethanol was added to the Mn-containing black hematite particle powder that was released from the aggregation of particles while operating the edge runner, and subsequently The mixture was stirred for 60 minutes with a linear load of 60 kg / cm.
[0118]
Next, carbon black fine particle powder (particle shape: granular, particle diameter 0.022 μm, geometric standard deviation value 1.68, BET specific surface area value 134 m shown in the electron micrograph (× 20000) in FIG.²/ G, blackness L^*Value 16.6) 990 g was added over 10 minutes while running the edge runner, and further mixed and stirred for 60 minutes at a linear load of 60 kg / cm, and carbon black fine particle powder was coated on the methyltriethoxysilane coating. This was adhered to obtain iron-based black composite particle powder.
[0119]
The obtained iron-based black composite particle powder was subjected to a heat treatment at 105 ° C. for 60 minutes using a dryer to volatilize residual moisture, ethanol, and the like. This iron-based black composite particle powder was a granular particle powder having a particle diameter of 0.31 μm, as shown in the electron micrograph (× 20000) in FIG. The geometric standard deviation value is 1.46, and the BET specific surface area value is 9.1 m.²/ G, blackness L^*The value was 17.6, the carbon black desorption rate was 6.6%, and the coating amount of the organosilane compound produced from methyltriethoxysilane was 0.16% by weight in terms of Si. In the electron micrograph shown in FIG. 3, since almost no carbon black fine particle powder is observed, it is recognized that almost all of the carbon black fine particle powder is attached to the organosilane compound coating formed from methyltriethoxysilane. It was.
[0120]
For comparison, an electron micrograph of a treated particle powder obtained by mixing and stirring Mn-containing black hematite particle powder and carbon black fine particle powder with an edge runner without coating with methyltriethoxysilane (× 20000) Is shown in FIG. As shown in the electron micrograph of FIG. 4, the carbon black fine particle powder was not attached to the particle surface of the Mn-containing black hematite particles, and it was confirmed that both particle powders were mixed together.
[0121]
<Manufacture of solvent-based paint containing iron-based black composite particle powder>
10 g of the above iron-based black composite particle powder, aminoalkyd resin and thinner were blended in the following proportions and added together with 90 g of 3 mmφ glass beads to a 140 ml glass bottle, and then mixed and dispersed for 90 minutes with a paint shaker to prepare a mill base.
[0122]
Iron-based black composite particle powder 12.2 parts by weight
Amino alkyd resin 19.5 parts by weight
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)
Thinner 7.3 parts by weight
[0123]
Using the mill base, an amino alkyd resin was blended so as to have the following ratio, and further mixed and dispersed in a paint shaker for 15 minutes to obtain a paint containing iron-based black composite particle powder.
[0124]
Mill base 39.0 parts by weight
Aminoalkyd resin 61.0 parts by weight
(Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.)
[0125]
The gloss of the coating film produced using this paint is 89%, and the blackness of the coating film is L.^*The value was 17.4. Gloss value change ΔG value based on acid resistance test of coating film is 5.6%, lightness change ΔL^*The value was 0.6.
[0126]
<Manufacture of water-based paint containing iron-based black composite particle powder>
The above iron-based black composite particle powder (7.62 g) and water-soluble alkyd resin and the like were added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads at the following ratio, and then mixed and dispersed in a paint shaker for 45 minutes or 90 minutes to prepare a mill base. .
[0127]
12.4 parts by weight of iron-based black composite particle powder
9.0 parts by weight of water-soluble alkyd resin
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
4.8 parts by weight of defoaming agent
(Product name: Nopco 8034: manufactured by San Nopco)
4.8 parts by weight of water
Butyl cellosolve 4.1 parts by weight
[0128]
Using the above mill base, the coating composition was blended at the following ratio, and further mixed and dispersed for 15 minutes with a paint shaker to obtain a water-soluble coating.
[0129]
Mill base 30.4 parts by weight
Water-soluble alkyd resin 46.2 parts by weight
(Product name: S-118: manufactured by Dainippon Ink & Chemicals, Inc.)
12.6 parts by weight of water-soluble melamine resin
(Product name: S-695: manufactured by Dainippon Ink & Chemicals, Inc.)
Defoamer 0.1 parts by weight
(Product name: Nopco 8034: manufactured by San Nopco)
9.1 parts by weight of water
Butyl cellosolve 1.6 parts by weight
[0130]
The gloss of the coating film produced using this paint is 87%, the blackness of the coating film is L^*The value was 17.4. Gloss value change ΔG value based on acid resistance test of paint film is 5.1%, lightness change ΔL^*The value was 0.6.
[0131]
<Manufacture of resin composition>
Weigh 2.5 g of the iron-based black composite particle powder and 47.5 g of polyvinyl chloride resin powder 103EP8D (manufactured by Nippon Zeon Co., Ltd.), put them in a 100 ml poly beaker and mix well with a spatula to obtain a mixed powder. Obtained.
[0132]
After adding 0.5 g of calcium stearate to the obtained mixed powder and mixing, and setting the clearance of a hot roll heated to 160 ° C. to 0.2 mm, the above mixed powder is kneaded with a roll little by little to obtain a resin composition The kneading was continued until the products were integrated, and then the resin composition was peeled from the roll and used as a colored resin plate raw material.
[0133]
Next, the resin composition is sandwiched between surface-polished stainless steel plates, placed in a hot press heated to 180 ° C., and 1 ton / cm.²And a colored resin plate having a thickness of 1 mm was obtained. Blackness L of the obtained colored resin plate^*The value was 17.9 and the dispersion state was 5.
[0134]
Three test pieces obtained by cutting a colored resin plate into a 1.5 cm square were put in a gear oven heated to 190 ° C., and taken out one by one every 30 minutes to examine the state of resin deterioration. Deterioration degree of resin (S / S₀× 100) was 0%, the degree of resin deterioration after 60 minutes was 5%, and the degree of resin deterioration after 90 minutes was 5%.
[0135]
[Action]
In the present invention, the most important point is that the black iron oxide particle powder or the black hydrous iron oxide particle powder, and if necessary, the surface of the black iron oxide particle powder or the black hydrous iron oxide particle powder has aluminum hydroxide, aluminum Generated from alkoxysilane on the surface of black iron oxide particle powder or black hydrated iron oxide particle powder coated with one or more compounds selected from oxide, hydroxide of silicon and oxide of silicon The carbon black fine particle powder is made of an iron-based black composite particle powder coated with an organosilane compound and carbon black fine particle powder having an average particle size of 0.005 to 0.05 μm attached to the organosilane compound coating. Of iron is 1 to 30 parts by weight with respect to 100 parts by weight of the black iron oxide particle powder or black hydrated iron oxide particle powder The color composite particle powder is excellent in dispersibility in the vehicle and the resin composition due to the small amount of carbon black fine particle powder that is detached from the particle surface, and only the carbon black fine particle powder is contained in a small amount of carbon black. This is the fact that a blackness that is equal or inferior to that of blackness can be obtained.
[0136]
As for the reason why the carbon black fine particle powder desorbed from the particle surface of the iron-based black composite particle powder according to the present invention is small, the present inventor has found that the black iron oxide particle powder or the black hydrated iron oxide particle powder inside or on the particle surface. Between a metal element such as Si, Al, Fe and the like and an alkoxy group possessed by the alkoxysilane to which the carbon black fine particle powder is attached, a metallosiloxane bond (≡Si-OM (where, M is a metal atom contained in iron-based black particles such as Si, Al, Fe, etc.))) is formed, and the organosilane compound to which the carbon black fine particle powder is attached becomes black iron oxide particle powder. Alternatively, it is considered to be firmly bonded to the particle surface of the black hydrated iron oxide particle powder.
[0137]
Regarding the reason why the iron-based black composite particle powder according to the present invention is excellent in dispersibility in the vehicle or in the resin composition, the present inventor Due to the fact that the carbon black fine particle powder does not inhibit dispersion in the system, the carbon black fine particle powder adheres to the particle surface of the iron-based black composite particle powder, resulting in irregularities on the particle surface, This is thought to be because contact between particles is suppressed.
[0138]
Regarding the reason why the blackness of the iron-based black composite particle powder according to the present invention is excellent, the present inventor found that the carbon black fine particle powder that normally behaves as an aggregate is black iron oxide due to the fine particles. Since it is uniformly and densely attached to the particle surface of the particle powder or black hydrated iron oxide particle powder through an organosilane compound generated from alkoxysilane, it exists in a state of being dispersed to the vicinity of the primary particles. This is thought to be because each individual fine particle powder functions more effectively.
[0139]
And it is the fact that the coating film obtained using the said iron-type black composite particle powder is excellent in acid resistance, and the obtained resin composition is excellent in aging resistance.
[0140]
As for the reason why the acid resistance of the coating film and the aging resistance of the resin composition according to the present invention are excellent, the present inventors changed the carbon black fine particle powder excellent in acid resistance and aging resistance to black iron oxide particle powder. Alternatively, the black iron oxide particle powder or the black iron oxide powder powder inherently has an easily oxidized surface by adhering to the particle surface of the black iron oxide powder powder through an organosilane compound generated from alkoxysilane. This is considered to be due to the fact that the characteristic of high activity was canceled and the original characteristics of carbon black were exhibited.
[0141]
【Example】
Next, examples and comparative examples are given.
[0142]
Core particles 1-7
Various black iron oxide particle powders and black hydrated iron oxide particle powders obtained by a known production method were prepared, and the black iron oxide particle powder and black hydrated water that were deagglomerated in the same manner as in the above-described embodiment. An iron oxide particle powder was obtained.
[0143]
Table 1 shows the characteristics of the black iron oxide particle powder and the black hydrated iron oxide particle powder. The core particles 1 and 2 are prepared by the method described in JP-A-4-144924, the core particle 3 is prepared by the method described in JP-B-44-668, and the core particle 4 is prepared by JP-B-3-9045. The core particles 5 were obtained as needle-like goethite particles by the method described in Japanese Patent Publication No. 55-6579, and the needle-like goethite particles were heated and dehydrated at 340 ° C. in the air. The core particles 6 and 7 were obtained by the method described in JP-A-6-263449.
[0144]
[Table 1]

[0145]
Core particle 8
A slurry containing Mn-containing black hematite particle powder was obtained using 20 kg of Mn-containing black hematite particle powder in which the aggregation of the core particles 1 was unraveled and 150 l of water. The pH value of the redispersed slurry containing the obtained Mn-containing black hematite particle powder was set to 10.5. Next, water was added to the slurry to adjust the slurry concentration to 98 g / l. 150 l of this slurry is heated to 60 ° C., and 1.0 mol / l NaAlO is added to the slurry.₂2722 ml of solution (corresponding to 0.5% by weight in terms of Al with respect to Mn-containing black hematite particle powder) was added and held for 30 minutes, and then the pH value was adjusted to 7.5 using acetic acid. After being kept in this state for 30 minutes, Mn-containing black hematite particle powder whose particle surface was coated with aluminum hydroxide was obtained by filtration, washing with water, drying and pulverization.
[0146]
The obtained Mn-containing black hematite particle powder whose particle surface was coated with an aluminum hydroxide was a granular particle powder having a particle size of 0.32 μm. Further, the geometric standard deviation value of the particle diameter is 1.47, and the BET specific surface area value is 3.8 m.²/ G, blackness L^*The value was 22.6. As a result of fluorescent X-ray analysis, the Mn content was 13.0% by weight and the Al content was 0.49% by weight.
[0147]
Core particles 9-14
A surface-treated black iron oxide particle powder and a surface-treated black iron oxide hydroxide powder were obtained in the same manner as the core particle 1 except that the kind of the core particles and the kinds and amounts of additives in the surface treatment step were changed.
[0148]
Table 2 shows the main treatment conditions at this time, and Table 3 shows the characteristics of the obtained surface-treated core particle powder.
[0149]
[Table 2]

[0150]
[Table 3]

[0151]
Examples 1-7, Comparative Examples 1-5
Types of black iron oxide particle powder and black hydrated iron oxide particle powder, presence or absence of alkoxysilane addition, type and addition amount, edge runner treatment conditions in alkoxysilane coating process, type and addition amount of carbon black fine particle powder, carbon black fine particle powder An iron-based black composite particle powder was obtained in the same manner as in the embodiment of the present invention, except that the processing conditions by the edge runner in the attaching step were variously changed. In the iron-based black composite particle powders obtained in each of Examples 1 to 7, almost no carbon black fine particle powder was observed as a result of electron microscope observation. It was observed that it adhered to the resulting organosilane compound coating.
[0152]
Table 4 shows various properties of the carbon black fine particle powders A to C used.
[0153]
[Table 4]

[0154]
Table 5 shows the main treatment conditions at this time, and Table 6 shows the characteristics of the obtained iron-based black composite particle powder.
[0155]
[Table 5]

[0156]
[Table 6]

[0157]
Example 8
11.0 kg of Mn-containing black hematite particles with the surface of the core particles 8 coated with aluminum hydroxide are introduced into the edge runner “MPUV-2” (manufactured by Matsumoto Foundry) Then, the mixture was stirred for 30 minutes at 30 kg / cm to break up the aggregation of the particles.
[0158]
Next, a methyltriethoxysilane solution obtained by mixing and diluting 220 g of methyltriethoxysilane with 400 ml of ethanol was coated with aluminum hydroxide while the edge runner was operated to break up the particle aggregation. Was added to the Mn-containing black hematite particle powder, followed by mixing and stirring with a linear load of 60 kg / cm for 30 minutes.
[0159]
Next, 1100 g of carbon black particles A were added over 10 minutes while the edge runner was running, and further mixed and stirred for 30 minutes at a linear load of 75 kg / cm, so that the carbon black fine particle powder was coated on the methyltriethoxysilane coating. This was adhered to obtain iron-based black composite particle powder.
[0160]
The obtained iron-based black composite particle powder was subjected to a heat treatment at 105 ° C. for 60 minutes using a dryer to volatilize residual moisture, ethanol, and the like. This iron-based black composite particle powder is a granular particle having a particle diameter of 0.32 μm, a geometric standard deviation value of 1.44, and a BET specific surface area value of 4.6 m.²/ G, blackness L^*The value was 16.5, the carbon black desorption rate was 4.8%, and the coating amount of the organosilane compound produced from methyltriethoxysilane was 0.31% by weight in terms of Si. As a result of observation with an electron microscope, almost no carbon black fine particle powder was observed, and it was confirmed that almost all of the carbon black fine particle powder was adhered to the organosilane compound coating formed from methyltriethoxysilane.
[0161]
Examples 9-14
Types of black iron oxide particle powder and black hydrated iron oxide particle powder, type and addition amount of alkoxysilane, edge runner treatment conditions in alkoxysilane coating process, type and addition amount of carbon black fine particle powder, adhesion step of carbon black fine particle powder An iron-based black composite particle powder was obtained in the same manner as in Example 8 except that the edge runner treatment conditions in were varied. In the iron-based black composite particle powders obtained in Examples 9 to 14, since almost no carbon black fine particle powder was observed as a result of electron microscope observation, almost all of the carbon black fine particle powder was made of alkoxysilane. It was observed that it adhered to the resulting organosilane compound coating.
[0162]
Table 5 shows the main treatment conditions at this time, and Table 6 shows the characteristics of the obtained iron-based black composite particle powder.
[0163]
Comparative Example 6 (Method described in JP-B-50-13300)
A water suspension (1000 ml of a suspension containing 68.3 g of magnetite particle powder) containing magnetite particle powder (black iron oxide) of core particle 3 was prepared and washed 5 times with cold water.
[0164]
Next, an aqueous dispersion of carbon black fine particle powder B (5 g of an aqueous dispersion containing 1.75 g of dry carbon black B) was diluted to 500 ml with cold water.
[0165]
While stirring the carbon black suspension, it was added to the aqueous suspension containing the magnetite particle powder over 5 minutes. After the addition was completed, the mixed suspension was further stirred for 10 minutes, I left it alone.
[0166]
After about 4 hours, the obtained black precipitate was filtered and washed with water five times in the usual manner, and then dried in air at 100 ° C.
[0167]
Blackness L of the obtained black particle powder^*The value was 20.2, the carbon black desorption rate was 50.2%, and the values were almost the same as the blackness of the magnetite particle powder as the core particle powder.
[0168]
<Manufacture of solvent-based paints>
Examples 15 to 28, Comparative Examples 7 to 21
A solvent-based paint was produced in the same manner as in the above-described embodiment except that various kinds of black particle powder were changed.
[0169]
Tables 7 and 8 show the main production conditions and various characteristics of the coating film.
[0170]
[Table 7]

[0171]
[Table 8]

[0172]
<Manufacture of water-based paint>
Examples 29-42, Comparative Examples 22-36
A water-based paint was produced in the same manner as in the above embodiment except that various kinds of black particle powder were used.
[0173]
Tables 9 and 10 show the main production conditions and various properties of the coating film at this time.
[0174]
[Table 9]

[0175]
[Table 10]

[0176]
<Manufacture of resin composition>
Examples 43 to 56, Comparative Examples 37 to 51
A colored resin plate was produced in the same manner as in the embodiment of the present invention except that various kinds of black particle powder were changed.
[0177]
Tables 11 and 12 show the main manufacturing conditions and the characteristics of the colored resin plate at this time.
[0178]
[Table 11]

[0179]
[Table 12]

[0180]
【The invention's effect】
The iron-based black composite particle powder according to the present invention is excellent in dispersibility in the vehicle and the resin composition due to the small amount of carbon black fine particle powder that is detached from the particle surface, and with a small amount of carbon black, Acidity and resin composition of the coating film obtained by using the iron-based black composite particle powder having the same or inferior blackness compared to the blackness when using only carbon black fine particle powder Since the aging resistance of the product is excellent, it is preferable as a black pigment for paints, printing inks, cosmetics, rubber / resin molded products and the like.
[0181]
The paint according to the present invention obtained by using the above iron-based black composite particle powder has a blackness which is equal or comparable to the blackness of the coating film when only the carbon black fine particle powder is used with a small amount of carbon black. Since the obtained coating film has excellent acid resistance, it is suitable as a black paint.
[0182]
The rubber / resin composition according to the present invention obtained using the iron-based black composite particle powder is equivalent to the blackness of the rubber / resin composition when only the carbon black fine particle powder is used with a small amount of carbon black. Or it has blackness without inferiority, and since acid resistance is excellent, it is preferable as a black rubber-resin composition.
[0183]
The iron-based black composite particle powder according to the present invention has excellent dispersibility in a vehicle and a resin composition, is easy to handle and has excellent workability, and is industrially and economically advantageous.
[0184]
Moreover, since the amount of carbon black fine particle powder used is small, it is preferable from the viewpoint of safety and hygiene.
[Brief description of the drawings]
FIG. 1 is an electron micrograph (× 20000) showing the particle structure of Mn-containing black hematite particle powder used in an embodiment of the invention.
FIG. 2 is an electron micrograph (× 20000) showing the particle structure of the carbon black fine particle powder used in the embodiment of the invention.
FIG. 3 is an electron micrograph (× 20000) showing the particle structure of the iron-based black composite particle powder obtained in the embodiment of the invention.
FIG. 4 is an electron micrograph (× 20000) showing the particle structure of a mixed particle powder of Mn-containing black hematite particle powder and carbon black fine particle powder shown for comparison.

Claims (6)

An organosilane compound produced from alkoxysilane is coated on the surface of black iron oxide particle powder or black hydrous iron oxide particle powder having an average particle size of 0.08 to 1.0 μm , and the coating amount of organosilane compound produced from alkoxysilane to the alkoxysilane coated black iron oxide particles or alkoxysilane coated black iron oxide hydroxide particles, Ri 0.02 to 5.0 wt% der in terms of Si, an average particle diameter of 0.005 to the organosilane compound-coated It is composed of an iron-based black composite particle powder to which carbon black fine particle powder of 0.05 μm is adhered, and the amount of the carbon black fine particle powder adhered to 100 parts by weight of the black iron oxide particle powder or the black hydrated iron oxide particle powder 1 to 30 parts by weight of an iron-based black composite particle powder. Aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide as a lower layer on the surface of black iron oxide particle powder or black hydrated iron oxide particle powder having an average particle size of 0.08 to 1.0 μm 1 type or 2 types or more selected from the above are coated, and the upper layer is coated with an organosilane compound generated from alkoxysilane, and the coating amount of the organosilane compound generated from alkoxysilane is alkoxysilane-coated black iron oxide particles powder or alkoxy to silane coating black iron oxide hydroxide particles, Ri 0.02 to 5.0 wt% der in terms of Si, of carbon black fine particles having an average particle diameter 0.005~0.05μm to the organosilane compound coating adhesion Made of iron-based black composite particles, and the amount of carbon black fine particles adhered to the black iron oxide particles 1 to 30 parts by weight of iron-based black composite particle powder with respect to 100 parts by weight of the child powder or black hydrous iron oxide powder. Black iron oxide particle powder or black hydrous iron oxide particle powder having an average particle size of 0.08 to 1.0 μm and mixed and stirred using an edge runner with black iron oxide particle powder or black hydrous iron oxide particle powder and alkoxysilane. After coating the surface of the particles with alkoxysilane, carbon black fine particle powder having an average particle size of 0.005 to 0.05 μm with respect to 100 parts by weight of the black iron oxide particle powder or black hydrated iron oxide particle powder is 1 to 30 weights. Part is added to obtain a mixed powder, and then the mixed powder is mixed and stirred using an edge runner, followed by drying or heat treatment to adhere the carbon black fine particle powder to the surface of the organosilane compound coating formed from the alkoxysilane. The method for producing an iron-based black composite particle powder according to claim 1, wherein: The particle surface is coated with one or more selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. After the black iron oxide particle powder or black hydrated iron oxide particle powder and alkoxysilane are mixed and stirred using an edge runner, the surface of the black iron oxide particle powder or black hydrated iron oxide particle powder is coated with alkoxy run. In addition, 1 to 30 parts by weight of carbon black fine particle powder having an average particle size of 0.005 to 0.05 μm is added to 100 parts by weight of the black iron oxide particle powder or black hydrated iron oxide particle powder to obtain a mixed powder, The mixed powder is mixed and stirred using an edge runner, and then dried or heat-treated to form a catalyst on the surface of the organosilane compound coating formed from the alkoxysilane. 3. The method for producing iron-based black composite particle powder according to claim 2, wherein bon black fine particle powder is adhered. A paint comprising the iron-based black composite particle powder according to claim 1 or 2 blended in a paint-constituting substrate. A rubber / resin composition colored using the iron-based black composite particle powder according to claim 1.

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