JPH1112491A - Production of heat-resistant yellow hydrated iron oxide pigment - Google Patents
Production of heat-resistant yellow hydrated iron oxide pigmentInfo
- Publication number
- JPH1112491A JPH1112491A JP18313397A JP18313397A JPH1112491A JP H1112491 A JPH1112491 A JP H1112491A JP 18313397 A JP18313397 A JP 18313397A JP 18313397 A JP18313397 A JP 18313397A JP H1112491 A JPH1112491 A JP H1112491A
- Authority
- JP
- Japan
- Prior art keywords
- iron oxide
- particles
- yellow
- hydroxide
- yellow iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、分散性が優れており、
しかも、耐熱性が向上しているとともに、耐熱性改善処
理工程の前後における色相の変化が小さい耐熱性黄色含
水酸化鉄顔料の製造法に関するものである。The present invention has excellent dispersibility,
In addition, the present invention relates to a method for producing a heat-resistant yellow iron oxide hydroxide pigment having improved heat resistance and a small change in hue before and after the heat resistance improving treatment step.
【０００２】[0002]
【従来の技術】黄色顔料は、樹脂やビヒクル中に分散さ
せて、樹脂、塗料、印刷インキ、道路アスファルトを製
造する際の着色顔料として広く使用されている。黄色は
交通上の規則や警戒を表す色であることから、殊に、道
路アスファルト用や路面表示塗料（トラフィックペイン
ト）用着色顔料としての用途が拡大している。2. Description of the Related Art Yellow pigments are widely used as color pigments in the production of resins, paints, printing inks and road asphalts by being dispersed in resins and vehicles. Since yellow is a color indicating traffic rules and cautions, its use as a coloring pigment for road asphalt and road marking paint (traffic paint) is expanding.
【０００３】黄色顔料は、作業能率の面から樹脂やビヒ
クル中における分散性が優れていることはもちろん、耐
熱性が優れていることが要求される。[0003] Yellow pigments are required not only to have excellent dispersibility in resins and vehicles but also to be excellent in heat resistance in terms of work efficiency.
【０００４】黄色顔料としては、従来から、クロム酸
鉛、クロム酸ストロンチウム、硫化カドミウム、含水酸
化鉄等が知られており、広く使用されている。[0004] As the yellow pigment, lead chromate, strontium chromate, cadmium sulfide, iron oxide hydroxide and the like have been known and widely used.
【０００５】上記クロム酸鉛、クロム酸ストロンチウ
ム、硫化カドミウム等は、耐熱性に優れているため、樹
脂、塗料、印刷インキ等の着色顔料として広く使用され
ているが、有毒性、発癌性を有することから、国民の健
康、衛生、安全性の観点から、また、環境汚染防止の観
点から代替黄色顔料が強く要求されている。[0005] Lead chromate, strontium chromate, cadmium sulfide and the like are widely used as coloring pigments for resins, paints, printing inks, etc. because of their excellent heat resistance, but they are toxic and carcinogenic. Therefore, there is a strong demand for alternative yellow pigments from the viewpoint of public health, hygiene and safety, and from the viewpoint of preventing environmental pollution.
【０００６】含水酸化鉄粒子は、無毒であり、国民の健
康、衛生、安全性の観点から、また、環境汚染防止の観
点から優れたものではあるが、耐熱性の点で劣っている
という問題がある。[0006] Hydrous iron oxide particles are non-toxic and are excellent from the viewpoint of public health, hygiene and safety, and from the viewpoint of preventing environmental pollution, but are inferior in heat resistance. There is.
【０００７】即ち、含水酸化鉄粒子は、Ｆｅ2 Ｏ3 ・ｎ
Ｈ2 Ｏで示される通り、結晶水を有しており、加熱温度
を昇温させていくと、一般に２００℃前後で脱水が開始
し始め、やがて２３０℃程度の温度で赤褐色のヘマタイ
ト（α−Ｆｅ2 Ｏ3 ）に変態する。That is, the iron oxide hydrate particles are made of Fe 2 O 3 .n
As indicated by H 2 O, it has crystallization water, and when the heating temperature is increased, dehydration generally starts around 200 ° C., and at a temperature of about 230 ° C., red-brown hematite (α- Fe 2 O 3 ).
【０００８】そのため、通常２００℃以上の高温度で成
形加工されているポリエチレン、ポリプロピレン、スチ
レン重合体、ポリアミド、ポリオレフィン、ＡＢＳなど
の熱可塑性樹脂や、施工時に２００〜２６０℃で加熱し
たり、溶融して使用される路面表示用塗料（トラフィッ
クペイント）に含水酸化鉄粒子を使用することは困難で
あった。For this reason, thermoplastic resins such as polyethylene, polypropylene, styrene polymer, polyamide, polyolefin, and ABS which are usually molded at a high temperature of 200 ° C. or higher, or heated at 200 to 260 ° C. during construction or melted. It has been difficult to use the iron oxide-containing particles as a road surface paint (traffic paint).
【０００９】そこで、含水酸化鉄粒子の耐熱性を向上さ
せるために種々の処理を施すことが行われているが、耐
熱性改善処理工程の前後で色相の変化が大きいと、着色
顔料の命ともいうべき色相面からの製品設計が困難とな
ることから、耐熱性改善処理工程の前後における色相の
変化ができるだけ小さいことが要求される。In order to improve the heat resistance of the iron oxide hydroxide particles, various treatments have been performed. However, if the change in hue is large before and after the heat resistance improvement treatment step, the life of the coloring pigment is reduced. Since it becomes difficult to design a product from the aspect of hue, a change in hue before and after the heat resistance improving process is required to be as small as possible.
【００１０】従来、含水酸化鉄粒子の耐熱性を向上させ
るための改善が種々試みられており、（１）含水酸化鉄
粒子をオートクレーブを用いて水又はアルカリ水溶液中
で水熱処理する方法（特公昭５３−２８１５８号公報
等）、（２）含水酸化鉄粒子の粒子表面をアルミニウム
化合物、ケイ素化合物等で被覆したり、含有、固溶させ
る方法（特公平６−１７２３７号公報等）、（３）上記
（１）の方法と（２）の方法を組み合わせる方法（特公
昭４９−１６５３１号公報、特公昭５４−７２９３号公
報、特公昭５５−８４６２号公報、特開昭５７−５７７
５５号公報等）等が知られている。Conventionally, various attempts have been made to improve the heat resistance of hydrated iron oxide particles. (1) A method of hydrothermally treating hydrated iron oxide particles in water or an alkaline aqueous solution using an autoclave. No. 53-28158), (2) A method of coating, containing, and forming a solid solution of the surface of the iron oxide-containing particles with an aluminum compound, a silicon compound, etc. (Japanese Patent Publication No. 6-17237), (3) A method combining the above method (1) and the method (2) (Japanese Patent Publication No. 49-16431, Japanese Patent Publication No. 54-7293, Japanese Patent Publication No. 55-8462, Japanese Patent Application Laid-Open No. 57-577)
No. 55, etc.) are known.
【００１１】[0011]
【発明が解決しようとする課題】分散性が優れており、
しかも、耐熱性が向上しているとともに、耐熱性改善処
理工程の前後における色相の変化が小さい黄色含水酸化
鉄粒子は、現在、最も要求されているところであるが、
これら諸特性を有する黄色含水酸化鉄顔料は、未だ得ら
れていない。The dispersibility is excellent,
Moreover, while the heat resistance has been improved, the yellow iron oxide hydroxide particles having a small change in hue before and after the heat resistance improvement treatment step are currently the most required,
A yellow iron oxide hydroxide pigment having these various properties has not yet been obtained.
【００１２】即ち、前出（１）の方法による処理を行っ
た黄色含水酸化鉄粒子は、耐熱性が向上したものではあ
るが、粒子の形態や粒度分布が耐熱性改善処理工程の前
後で大きく変化し、その結果、色相の変化が大きいもの
であった。That is, although the yellow iron-containing hydroxide particles treated by the method (1) have improved heat resistance, the morphology and particle size distribution of the particles are large before and after the heat resistance improving step. As a result, the change in hue was large.
【００１３】前出（２）の方法による処理を行った黄色
含水酸化鉄粒子は、色相の変化は小さいものではある
が、黄色含水酸化鉄粒子を凝集したままでアルミニウム
化合物等で被覆しているため、分散性が悪く、また、耐
熱性も不十分なものであった。The yellow iron oxide hydroxide particles treated by the method (2) have a small change in hue, but the yellow iron oxide particles are coated with an aluminum compound or the like while being aggregated. Therefore, the dispersibility was poor and the heat resistance was insufficient.
【００１４】前出（３）の方法による処理を行った黄色
含水酸化鉄粒子は、耐熱性が向上したものではあるが、
前出（１）の方法と同様に耐熱性改善処理工程の前後に
おける色相の変化が大きいものである。The yellow hydrous iron oxide particles treated according to the method (3) have improved heat resistance.
Similar to the method (1), the hue changes greatly before and after the heat resistance improving process.
【００１５】そこで、本発明は、分散性が優れており、
しかも、耐熱性が向上しているとともに、耐熱性改善処
理工程の前後における色相の変化が小さい黄色含水酸化
鉄粒子を得ることを技術的課題とする。Therefore, the present invention has excellent dispersibility,
Moreover, it is a technical object to obtain yellow iron oxide hydroxide particles having improved heat resistance and a small change in hue before and after the heat resistance improving treatment step.
【００１６】[0016]
【課題を解決する為の手段】前記技術的課題は、次の通
りの本発明によって達成できる。The above technical object can be achieved by the present invention as described below.
【００１７】即ち、本発明は、黄色含水酸化鉄粒子を含
む水分散液に該黄色含水酸化鉄粒子に対しＡｌ換算で
０．１〜１０重量％のアルミニウム化合物とＦｅ換算で
０．１〜５０重量％の第一鉄塩化合物とを添加、混合し
た後酸素含有ガスを通気して、前記黄色含水酸化鉄粒子
の粒子表面にＦｅ及びＡｌからなる複合含水酸化物を被
着させ、次いで、濾別、水洗、乾燥するこにより粒子表
面にＦｅ及びＡｌからなる複合含水酸化物が被着されて
いる黄色含水酸化鉄粒子からなる黄色含水酸化鉄粒子粉
末を得ることを特徴とする耐熱性黄色含水酸化鉄顔料の
製造法である。That is, according to the present invention, an aqueous dispersion containing yellow iron oxide hydroxide particles contains an aluminum compound in an amount of 0.1 to 10% by weight in terms of Al and 0.1 to 50% in terms of Fe with respect to the yellow iron oxide hydroxide particles. Weight percent of a ferrous salt compound was added and mixed, and then an oxygen-containing gas was ventilated to deposit a composite hydrated oxide composed of Fe and Al on the surface of the yellow hydrous iron oxide particles. Separately, by washing with water and drying, a heat-resistant yellow hydrate is obtained, wherein a yellow hydrated iron oxide particle powder composed of yellow hydrated iron oxide particles having a composite hydrated oxide composed of Fe and Al adhered to the particle surface is obtained. This is a method for producing an iron oxide pigment.
【００１８】また、本発明は、黄色含水酸化鉄粒子を含
む水分散液に該黄色含水酸化鉄粒子に対しＡｌ換算で
０．１〜１０重量％のアルミニウム化合物とＦｅ換算で
０．１〜５０重量％の第一鉄塩化合物とを添加、混合し
た後酸素含有ガスを通気して、前記含水酸化鉄粒子の粒
子表面にＦｅ及びＡｌからなる複合含水酸化物を被着さ
せ、次いで、粒子表面にＦｅ及びＡｌからなる複合含水
酸化物が被着されている前記黄色含水酸化鉄粒子を含む
水分散液のｐＨ値を１０以上又は４以下に調整した後、
アルミニウム化合物を添加、攪拌し、次いで該分散液の
ｐＨ値を５〜９の範囲に再調整して、前記Ｆｅ及びＡｌ
からなる複合含水酸化物表面にアルミニウムの水酸化物
を被着させた後、濾別、水洗、乾燥することにより粒子
表面にＦｅ及びＡｌからなる複合含水酸化物が被着さ
れ、更にその上にアルミニウムの水酸化物が被着されて
いる黄色含水酸化鉄粒子からなる黄色含水酸化鉄粒子粉
末を得ることを特徴とする耐熱性黄色含水酸化鉄顔料の
製造法である。Further, according to the present invention, an aqueous dispersion containing yellow iron oxide hydroxide particles is provided with an aluminum compound in an amount of 0.1 to 10% by weight in terms of Al based on the yellow iron oxide hydroxide particles and in an amount of 0.1 to 50% in terms of Fe. Weight percent of a ferrous salt compound was added and mixed, and then an oxygen-containing gas was ventilated to deposit a composite hydrated oxide composed of Fe and Al on the particle surfaces of the iron oxide hydroxide particles. After adjusting the pH value of the aqueous dispersion containing the yellow hydrous iron oxide particles to which the composite hydrated oxide composed of Fe and Al has been applied to 10 or more or 4 or less,
The aluminum compound was added and stirred, and then the pH value of the dispersion was readjusted to a range of 5 to 9 to obtain the Fe and Al.
After the aluminum hydroxide is deposited on the surface of the composite hydrated oxide composed of, the composite hydrated oxide composed of Fe and Al is deposited on the particle surface by filtration, washing and drying, and further thereon. A method for producing a heat-resistant yellow iron oxide hydroxide pigment, comprising obtaining yellow iron oxide hydroxide particles comprising yellow iron oxide hydroxide particles coated with aluminum hydroxide.
【００１９】次に、本発明実施にあたっての諸条件につ
いて述べる。Next, various conditions for implementing the present invention will be described.
【００２０】本発明における黄色含水酸化鉄粒子は、
第一鉄塩水溶液に当量以上の水酸化アルカリ水溶液を加
えて得られる水酸化第一鉄コロイドを含む懸濁液を、ｐ
Ｈ値が１１以上、８０℃以下の温度で酸素含有ガスを通
気して酸化反応を行うことにより針状黄色含水酸化鉄
（ゲータイト）粒子を生成する方法、第一鉄塩水溶液
と炭酸アルカリ水溶液とを反応させて得られるＦｅＣＯ
3 を含む懸濁液を、必要により熟成した後、酸素含有ガ
スを通気してｐＨ値が８〜１０の範囲で酸化反応を行う
ことにより紡錘状黄色含水酸化鉄（ゲータイト）粒子を
生成する方法、第一鉄塩水溶液に当量未満の水酸化ア
ルカリ水溶液又は炭酸アルカリ水溶液を添加して得られ
る水酸化第一鉄コロイドを含む第一鉄塩水溶液に酸素含
有ガスを通気して酸化反応を行うことにより、ｐＨが４
以下の溶液中から針状黄色含水酸化鉄（ゲータイト）核
粒子を生成させ、次いで、該針状黄色含水酸化鉄（ゲー
タイト）核粒子を含む第一鉄塩水溶液に、該第一鉄塩水
溶液中のＦｅ2+に対し当量以上の水酸化アルカリ水溶液
を添加した後、酸素含有ガスを通気して酸化反応を行う
ことにより、ｐＨ値が１１以上の溶液中で前記針状黄色
含水酸化鉄（ゲータイト）核粒子を成長させる方法、
第一鉄塩水溶液に当量未満の水酸化アルカリ水溶液又は
炭酸アルカリ水溶液を添加して得られる水酸化第一鉄コ
ロイドを含む第一鉄塩水溶液に酸素含有ガスを通気して
酸化反応を行うことにより、ｐＨ値が５以下の溶液中か
ら針状黄色含水酸化鉄（ゲータイト）核粒子を生成さ
せ、次いで、酸性乃至中性領域で前記針状黄色含水酸化
鉄（ゲータイト）核粒子を成長させる方法等により生成
することができ、生成黄色含水酸化鉄粒子は常法により
濾別、水洗、乾燥する。得られた黄色含水酸化鉄粒子
は、平均長軸径が０．１〜１．０μｍ、平均短軸径が
０．０２〜０．１０μｍ、軸比（長軸径／短軸径）が２
〜２０、ＢＥＴ比表面積が１０〜１８０ｍ2 ／ｇであっ
て、色相は、Ｌ* 値が５０〜７５、ａ* 値が５〜２５、
ｂ* 値が４０〜６０である。The yellow iron oxide hydroxide particles in the present invention are:
A suspension containing a ferrous hydroxide colloid obtained by adding an equivalent amount or more of an aqueous alkali hydroxide solution to a ferrous salt aqueous solution, p
A method for producing needle-like yellow iron oxide hydrous (goethite) particles by passing an oxygen-containing gas at a temperature of 11 or more and 80 ° C. or less to carry out an oxidation reaction. FeCO obtained by reacting
A method for producing spindle-shaped yellow iron oxide hydrous (goethite) particles by subjecting a suspension containing 3 to aging, if necessary, and then performing an oxidation reaction at a pH value of 8 to 10 by passing an oxygen-containing gas. Performing an oxidation reaction by passing an oxygen-containing gas through a ferrous salt aqueous solution containing a ferrous hydroxide colloid obtained by adding a less than equivalent amount of an aqueous alkali hydroxide solution or an aqueous alkali carbonate solution to an aqueous ferrous salt solution PH 4
From the following solution, needle-like yellow iron oxide hydrous (goethite) nucleus particles are generated, and then into the ferrous salt aqueous solution containing the needle-like yellow iron oxyhydroxide (goethite) core particles, After adding an aqueous solution of an alkali hydroxide in an amount equivalent to or more than Fe 2+ , an oxygen-containing gas is passed to carry out an oxidation reaction, whereby the needle-like yellow iron-containing hydroxide (goethite) is obtained in a solution having a pH of 11 or more. ) A method of growing nuclear particles,
An oxygen-containing gas is passed through an aqueous ferrous salt solution containing a ferrous hydroxide colloid obtained by adding a less than equivalent amount of an aqueous alkali hydroxide solution or an aqueous alkali carbonate solution to an aqueous ferrous salt solution to perform an oxidation reaction. A method in which needle-like yellow iron oxide hydroxide (goethite) core particles are generated from a solution having a pH value of 5 or less, and then the needle yellow iron oxide hydroxide (goethite) core particles are grown in an acidic to neutral region. The produced yellow iron oxide hydroxide particles are separated by filtration, washed with water and dried by a conventional method. The obtained yellow iron oxide hydroxide particles have an average major axis diameter of 0.1 to 1.0 μm, an average minor axis diameter of 0.02 to 0.10 μm, and an axial ratio (major axis diameter / minor axis diameter) of 2.
-20, the BET specific surface area is 10-180 m 2 / g, and the hue has an L * value of 50-75, an a * value of 5-25,
b * value is 40-60.
【００２１】尚、黄色含水酸化鉄粒子の色相を調整する
ことを目的として、黄色含水酸化鉄（ゲータイト）粒子
の生成反応中に、粒子粉末の長軸径、短軸径、軸比等の
諸特性を制御する為のＮｉ、Ｚｎ、Ｐ、Ｓｉ、Ａｌ等Ｆ
ｅ以外の異種元素を添加してもよく、この場合には、生
成黄色含水酸化鉄粒子中に、これらＦｅ以外の異種元素
が含有される。For the purpose of adjusting the hue of the yellow iron oxide hydroxide particles, various parameters such as the major axis diameter, the minor axis diameter, the axial ratio, etc. of the particle powder during the reaction for producing the yellow iron oxide hydroxide (goethite) particles. Ni, Zn, P, Si, Al, etc. for controlling characteristics
A different element other than e may be added. In this case, the formed yellow iron-containing hydroxide particles contain these different elements other than Fe.
【００２２】本発明において使用する黄色含水酸化鉄粒
子は、上述した反応溶液中から生成した黄色含水酸化鉄
粒子を、濾別、水洗して得られる湿ケーキ、該湿ケーキ
を水中に分散させた分散スラリー、前記湿ケーキを乾燥
した乾燥粉末、乾燥した粉末を水中に再分散させた再分
散スラリーのいずれの形態であってもよいが、前記分散
スラリーを用いるのが効率上、作業上好ましい。The yellow iron oxide hydroxide particles used in the present invention are obtained by filtering and washing the yellow iron oxide hydroxide particles produced from the above-mentioned reaction solution and washing with water, and dispersing the wet cake in water. Any of a dispersed slurry, a dried powder obtained by drying the wet cake, and a redispersed slurry obtained by redispersing the dried powder in water may be used, but the use of the dispersed slurry is preferable in terms of efficiency and work.
【００２３】尚、反応溶液中の生成黄色含水酸化鉄粒子
を常法により、濾別、水洗することにより得られる黄色
含水酸化鉄粒子は、通常、鉄原料である硫酸第一鉄塩水
溶液に由来する可溶性硫酸塩をＳＯ4 換算で通常３００
０〜１００００ｐｐｍ程度、アルカリ原料である水酸化
ナトリウムに由来する可溶性ナトリウム塩をＮａ換算で
通常１５００〜１００００ｐｐｍ程度含有している。Incidentally, the yellow iron oxide hydroxide particles obtained by filtering and washing the yellow iron oxide hydroxide particles formed in the reaction solution by a conventional method are usually derived from an aqueous ferrous sulfate salt solution which is an iron raw material. Usually 300 a soluble sulfate in terms of SO 4 to
It generally contains about 0 to 10000 ppm, and usually about 1500 to 10000 ppm of a soluble sodium salt derived from sodium hydroxide as an alkali raw material in terms of Na.
【００２４】本発明における黄色含水酸化鉄粒子の粒子
表面へのＦｅ及びＡｌからなる複合含水酸化物の被着
は、黄色含水酸化鉄粒子を含む水懸濁液に、アルミニウ
ム化合物と第一鉄塩化合物を添加、混合した後、酸素含
有ガスを通気することにより行なう。Ｆｅ及びＡｌから
なる複合含水酸化物の生成を考慮すれば、懸濁液のｐＨ
値を５以下又は１０以上に維持しながら酸素含有ガスを
通気することが好ましい。水懸濁液中の黄色含水酸化鉄
粒子の濃度は、５〜１５０ｇ／ｌ程度に調整すればよ
い。生産性を考慮すれば、１０〜１２０ｇ／ｌ程度が好
ましく、より好ましくは、２０〜１００ｇ／ｌ程度であ
る。In the present invention, the deposition of the composite hydrated oxide composed of Fe and Al on the surface of the yellow iron oxide hydroxide particles is performed by adding an aluminum compound and a ferrous salt to the aqueous suspension containing the yellow iron oxide hydroxide particles. After adding and mixing the compound, the reaction is carried out by passing an oxygen-containing gas. Considering the formation of a composite hydrated oxide composed of Fe and Al, the pH of the suspension
It is preferable to ventilate the oxygen-containing gas while maintaining the value at 5 or less or 10 or more. The concentration of the yellow iron oxide hydroxide particles in the aqueous suspension may be adjusted to about 5 to 150 g / l. In consideration of productivity, it is preferably about 10 to 120 g / l, and more preferably about 20 to 100 g / l.
【００２５】添加するアルミニウム化合物としては、ア
ルミン酸ナトリウムなどのアルミン酸アルカリや、硫酸
アルミニウム、塩化アルミニウム、酢酸アルミニウム、
硝酸アルミニウムなどのアルミニウム塩を使用すること
ができ、その添加量は、黄色含水酸化鉄粒子に対し、Ａ
ｌ換算で０．１〜１０重量％である。０．１重量％未満
である場合には、本発明の目的とする分散性改良の効果
や耐熱性向上の効果が得られない。１０重量％を越える
場合には、本発明の目的とする効果がほぼ飽和に達する
ので、必要以上に添加する意味がない。Examples of the aluminum compound to be added include alkali aluminates such as sodium aluminate, aluminum sulfate, aluminum chloride, aluminum acetate, and the like.
An aluminum salt such as aluminum nitrate can be used.
It is 0.1 to 10% by weight in terms of l. If the amount is less than 0.1% by weight, the effects of improving dispersibility and heat resistance, which are the objects of the present invention, cannot be obtained. If it exceeds 10% by weight, the desired effect of the present invention almost reaches saturation, so that there is no point in adding more than necessary.
【００２６】添加する第一鉄塩水溶液としては、硫酸第
一鉄、塩化第一鉄、硝酸第一鉄等の第一鉄塩を使用する
ことができ、その添加量は、黄色含水酸化鉄粒子に対
し、０．１〜５０重量％である。０．１重量％未満であ
る場合には、本発明の目的とする分散性改良の効果や耐
熱性向上の効果が得られない。５０重量％を越える場合
には、本発明の目的とする効果がほぼ飽和に達するの
で、必要以上に入れる意味がない。As the ferrous salt aqueous solution to be added, ferrous salts such as ferrous sulfate, ferrous chloride, and ferrous nitrate can be used. 0.1 to 50% by weight. If the amount is less than 0.1% by weight, the effects of improving dispersibility and heat resistance, which are the objects of the present invention, cannot be obtained. If it exceeds 50% by weight, the desired effect of the present invention almost reaches saturation, so it is meaningless to add more than necessary.
【００２７】添加するアルミニウム化合物と第一鉄塩水
溶液の割合は、本発明の目的である分散性改良の効果や
耐熱性向上の効果を考慮すれば、Ａｌ／Ｆｅの原子換算
で１：０．５〜１：２０の範囲が好ましく、より好まし
くは１：１〜１：１０の範囲である。The ratio of the added aluminum compound to the aqueous ferrous salt solution is 1: 0 in terms of Al / Fe atom in consideration of the effect of improving dispersibility and the effect of improving heat resistance, which are the objects of the present invention. The range is preferably from 5 to 1:20, and more preferably from 1: 1 to 1:10.
【００２８】添加したアルミニウム化合物と第一鉄塩水
溶液は、そのほとんどがＦｅ及びＡｌからなる複合含水
酸化物として黄色含水酸化鉄粒子の粒子表面に被着され
るから、該ＦｅおよびＡｌからなる複合含水酸化物にお
けるＦｅ及びＡｌの割合は、添加時の割合とほぼ同程度
である。Most of the added aluminum compound and the aqueous ferrous salt solution are deposited on the particle surface of the yellow iron oxide hydroxide particles as a composite hydrated oxide composed mainly of Fe and Al. The proportions of Fe and Al in the hydrated oxide are almost the same as the proportions at the time of addition.
【００２９】アルミニウム化合物と第一鉄塩水溶液の添
加順序は、いずれが先でもまた、同時でもよい。The order of adding the aluminum compound and the aqueous ferrous salt solution may be either earlier or simultaneously.
【００３０】酸化手段は、酸素含有ガス（例えば、空
気）を液中に通気することにより行い、また、当該通気
ガスや機械的操作等により攪拌しながら行なう。The oxidizing means is carried out by passing an oxygen-containing gas (for example, air) through the liquid, and is carried out with stirring by the passing gas or mechanical operation.
【００３１】本発明の方法により得られる粒子表面にＦ
ｅ及びＡｌからなる複合含水酸化物が被着されている黄
色含水酸化鉄粒子は、前出被処理黄色含水酸化鉄粒子の
平均長軸径、平均短軸径、軸比（長軸径／短軸径）、Ｂ
ＥＴ比表面積及び色相の各諸特性とほぼ同程度であっ
て、分散性が優れたものであり、殊に、光沢が７０〜１
１０％、好ましくは、８０〜１１０％である。しかも、
耐熱性が向上した、殊に、耐熱温度が２５５℃以上、好
ましくは２６５℃以上、さらに好ましくは２７０℃以上
であるとともに耐熱性改善処理工程の前後における色相
の変化が小さい、殊に、ΔＬが絶対値で１．０以下、好
ましくは０．５以下であって、Δａが絶対値で１．０以
下、好ましくは０．５以下であって、Δｂが絶対値で
１．０以下、好ましくは０．５以下である。The particle surface obtained by the method of the present invention has F
The yellow hydrous iron oxide particles coated with the composite hydrous oxide composed of e and Al are the average major axis diameter, average minor axis diameter, and axial ratio (major axis diameter / short axis) of the previously treated yellow iron oxide hydroxide particles. Shaft diameter), B
ET specific surface area and hue are almost the same, and have excellent dispersibility. In particular, gloss is 70 to 1
It is 10%, preferably 80 to 110%. Moreover,
The heat resistance is improved, in particular, the heat resistance temperature is 255 ° C. or higher, preferably 265 ° C. or higher, more preferably 270 ° C. or higher, and the change in hue before and after the heat resistance improving process is small. The absolute value is 1.0 or less, preferably 0.5 or less, Δa is 1.0 or less in absolute value, preferably 0.5 or less, and Δb is 1.0 or less in absolute value, preferably 0.5 or less.
【００３２】次に、本発明においては、必要により更
に、アルミニウムの水酸化物を被着させることができ
る。この場合には、粒子表面にＦｅ及びＡｌからなる複
合含水酸化物が被着されている黄色含水酸化鉄粒子を含
む水懸濁液中のｐＨ値を１０以上又は４以下に調整した
後、アルミニウム化合物を添加、攪拌し、次いで、水分
散液のｐＨ値を５〜９の範囲に再調整する。Next, in the present invention, a hydroxide of aluminum can be further adhered if necessary. In this case, after adjusting the pH value in the aqueous suspension containing the yellow hydrated iron oxide particles to which the composite hydrated oxides of Fe and Al are adhered on the particle surfaces to 10 or more or 4 or less, aluminum The compound is added and stirred, then the pH value of the aqueous dispersion is readjusted to a range of 5-9.
【００３３】アルミニウムの水酸化物で被覆するに際し
てのｐＨ値の調整は、通常使用されるアルカリ水溶液、
酸水溶液を使用すればよい。Adjustment of the pH value at the time of coating with aluminum hydroxide is performed by using a commonly used alkaline aqueous solution,
An aqueous acid solution may be used.
【００３４】アルカリ水溶液としては、水酸化ナトリウ
ム水溶液、水酸化カリウム水溶液、アンモニア水溶液等
を使用することができる。As the aqueous alkaline solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution and the like can be used.
【００３５】酸水溶液としては、塩酸、硝酸、酢酸、シ
ュウ酸、硫酸等を使用することができる。As the acid aqueous solution, hydrochloric acid, nitric acid, acetic acid, oxalic acid, sulfuric acid and the like can be used.
【００３６】アルミニウム化合物を添加する前のｐＨ値
は、ｐＨ値が１０以上又は４以下であることが必要であ
る。ｐＨ値が１０未満、ｐＨ値が４を越える場合には、
添加したアルミニウム化合物が瞬時にアルミニウムの水
酸化物として沈澱してしまい、Ｆｅ及びＡｌからなる複
合含水酸化物が被着されている黄色含水酸化鉄粒子の表
面に均一に被着することが困難となる。The pH value before the addition of the aluminum compound must be 10 or more or 4 or less. If the pH value is less than 10 and the pH value exceeds 4,
The added aluminum compound instantaneously precipitates as an aluminum hydroxide, and it is difficult to uniformly deposit the composite hydrated oxide composed of Fe and Al on the surfaces of the yellow iron-containing hydroxide particles. Become.
【００３７】アルミニウム化合物を添加した後、ｐＨ値
が１０以上又は４以下の条件下で、懸濁液の攪拌を行
う。ｐＨ値が１０未満の場合、ｐＨ値が４を越える場合
には、イオン状のアルミニウム塩が黄色含水酸化鉄粒子
を含む懸濁液中に均一に混合されにくく、Ｆｅ及びＡｌ
からなる複合含水酸化物が被着されている黄色含水酸化
鉄粒子の表面にアルミニウムの水酸化物が均一に沈澱、
被着することが困難となる。After the addition of the aluminum compound, the suspension is stirred under conditions where the pH value is 10 or more or 4 or less. When the pH value is less than 10, and when the pH value exceeds 4, the ionic aluminum salt is difficult to be uniformly mixed into the suspension containing the yellow iron oxide hydroxide particles, and Fe and Al
The hydroxide of aluminum is uniformly precipitated on the surface of the yellow iron oxide hydrate particles on which the composite hydrate consisting of
It becomes difficult to apply.
【００３８】Ｆｅ及びＡｌからなる複合含水酸化物が被
着されている黄色含水酸化鉄粒子の表面にアルミニウム
の水酸化物を沈澱、被着する時の懸濁液温度は、常温で
もよいが、均一に被着する為には、好ましくは４０℃以
上、より好ましくは６０℃以上である。The suspension temperature at the time when aluminum hydroxide is precipitated and deposited on the surface of the yellow hydrated iron oxide particles on which the composite hydrated oxide composed of Fe and Al is deposited may be normal temperature. For uniform deposition, the temperature is preferably 40 ° C. or more, more preferably 60 ° C. or more.
【００３９】Ｆｅ及びＡｌからなる複合含水酸化物が被
着されている黄色含水酸化鉄粒子の表面にアルミニウム
の水酸化物を沈着させる際の懸濁液は、攪拌後、ｐＨ値
５〜９の範囲となるように再調整する。ｐＨ値が５未満
の場合、９を越える場合は、Ｆｅ及びＡｌからなる複合
含水酸化物が被着されている黄色含水酸化鉄粒子の表面
にアルミニウムの水酸化物を沈澱、被着することが困難
となる。The suspension for depositing the aluminum hydroxide on the surface of the yellow hydrated iron oxide particles coated with the composite hydrated oxide composed of Fe and Al, after stirring, has a pH of 5-9. Readjust the range. When the pH value is less than 5, or when the pH value is more than 9, aluminum hydroxide can be precipitated and deposited on the surface of the yellow iron oxide hydroxide particles on which the composite hydroxide comprising Fe and Al is deposited. It will be difficult.
【００４０】アルミニウム化合物の添加量は、Ｆｅ及び
Ａｌからなる複合含水酸化物が被着されている黄色含水
酸化鉄粒子に対しＡｌ換算で０．１〜２０．０重量％で
ある。０．１重量％未満の場合には、Ｆｅ及びＡｌから
なる複合含水酸化物が被着されている黄色含水酸化鉄粒
子の表面にアルミニウムの水酸化物を十分、沈澱、被着
することが困難となり、本発明の目的とする分散性改良
の効果や耐熱性向上の効果が得られ難い。２０．０重量
％を越える場合にも、分散性改良の効果や耐熱性向上の
効果は得られるが、効果がほぼ飽和に達するので、必要
以上に添加する意味がない。黄色含水酸化鉄粒子の分散
性改良の効果や耐熱性向上の効果を考慮すれば、好まし
くは０．１５〜５．０重量％である。The addition amount of the aluminum compound is 0.1 to 20.0% by weight in terms of Al based on the weight of the yellow iron oxide hydroxide particles on which the composite hydrated oxide composed of Fe and Al is applied. If the amount is less than 0.1% by weight, it is difficult to sufficiently precipitate and adhere the aluminum hydroxide on the surface of the yellow iron oxide hydroxide particles on which the composite hydrous oxide composed of Fe and Al is adhered. Thus, it is difficult to obtain the effects of improving dispersibility and heat resistance, which are the objects of the present invention. If it exceeds 20.0% by weight, the effect of improving dispersibility and the effect of improving heat resistance can be obtained, but the effect almost reaches saturation, so there is no point in adding more than necessary. In consideration of the effect of improving the dispersibility of the yellow hydrous iron oxide particles and the effect of improving the heat resistance, it is preferably 0.15 to 5.0% by weight.
【００４１】添加したアルミニウムの化合物は、ほぼ全
量がアルミニウムの水酸化物となって、Ｆｅ及びＡｌか
らなる複合含水酸化物が被着されている黄色含水酸化鉄
粒子の表面に沈澱、被着される。Almost all of the added aluminum compound becomes a hydroxide of aluminum, and precipitates and adheres to the surface of the yellow hydrous iron oxide particles on which the composite hydrate of Fe and Al is adhered. You.
【００４２】本発明の方法により得られる粒子表面にＦ
ｅ及びＡｌからなる複合含水酸化物が被着され、更に、
その表面にアルミニウムの水酸化物が被着されている黄
色含水酸化鉄粒子は、前出被処理黄色含水酸化鉄粒子の
平均長軸径、平均短軸径、軸比（長軸径／短軸径）、Ｂ
ＥＴ比表面積及び色相の各諸特性とほぼ同程度であっ
て、分散性が優れたものであり、殊に、光沢が７５〜１
１５％、好ましくは８５〜１１５％である。しかも、耐
熱性が向上した、殊に、耐熱温度が２６５℃以上、好ま
しくは２７５℃以上であるとともに、耐熱性改善処理工
程の前後における色相の変化が小さい、殊に、ΔＬが絶
対値で１．０以下、好ましくは０．５以下であって、Δ
ａが絶対値で１．０以下、好ましくは０．５以下であっ
て、Δｂが絶対値で１．０以下、好ましくは０．５以下
である。The particle surface obtained by the method of the present invention has F
a composite hydrated oxide comprising e and Al is deposited,
The yellow iron oxide hydroxide particles having aluminum hydroxide adhered to the surface are the average major axis diameter, average minor axis diameter, and axial ratio (major axis diameter / minor axis) of the previously treated yellow iron oxide hydroxide particles. Diameter), B
ET specific surface area and various characteristics such as hue are almost the same and have excellent dispersibility.
It is 15%, preferably 85 to 115%. In addition, the heat resistance is improved, in particular, the heat resistance temperature is 265 ° C. or higher, preferably 275 ° C. or higher, and the change in hue before and after the heat resistance improvement process is small. In particular, ΔL is 1 in absolute value. 0.0 or less, preferably 0.5 or less, Δ
a is an absolute value of 1.0 or less, preferably 0.5 or less, and Δb is an absolute value of 1.0 or less, preferably 0.5 or less.
【００４３】[0043]
【作用】本発明において最も重要な点は、黄色含水酸化
鉄粒子を含む水分散液に該黄色含水酸化鉄粒子に対しＡ
ｌ換算で０．１〜１０重量％のアルミニウム化合物とＦ
ｅ換算で０．１〜５０重量％の第一鉄塩化合物とを添
加、混合した後酸素含有ガスを通気して、前記黄色含水
酸化鉄粒子の粒子表面にＦｅ及びＡｌからなる複合含水
酸化物を被着させた場合には、分散性が優れており、し
かも、耐熱性が向上しているとともに、耐熱性改善処理
工程の前後における色相の変化が小さいものであるとい
う事実である。The most important point in the present invention is that the aqueous dispersion containing the yellow iron oxide hydroxide particles has an A
0.1 to 10% by weight of aluminum compound and F
After adding and mixing 0.1 to 50% by weight of a ferrous salt compound in terms of e, an oxygen-containing gas is ventilated, and a composite hydrated oxide composed of Fe and Al is formed on the surface of the yellow iron oxide hydroxide particles. Is a fact that the dispersibility is excellent, the heat resistance is improved, and the change in hue before and after the heat resistance improving process is small.
【００４４】本発明においては、粒子表面にＦｅ及びＡ
ｌからなる複合含水酸化物が被着されている黄色含水酸
化鉄粒子を含む水分散液のｐＨ値を１０以上又は４以下
に調整し、次いで、アルミニウム化合物を添加、攪拌し
た後、該分散液のｐＨ値を５〜９の範囲に再調整するこ
とにより、粒子表面に更にアルミニウムの水酸化物を被
着させた場合には、分散性がより優れており、しかも、
耐熱性がより向上しているとともに、耐熱性改善処理工
程の前後における色相の変化が小さいものであるという
事実である。In the present invention, Fe and A
After adjusting the pH value of the aqueous dispersion containing the yellow hydrous iron oxide particles to which the composite hydrate of 1 is attached to 10 or more, and then adding an aluminum compound and stirring, the dispersion By re-adjusting the pH value in the range of 5 to 9, when an aluminum hydroxide is further adhered to the particle surface, the dispersibility is more excellent, and
This is the fact that the heat resistance is further improved, and the change in hue before and after the heat resistance improving process is small.
【００４５】粒子表面にＦｅ及びＡｌからなる複合含水
酸化物が被着されている黄色含水酸化鉄粒子や該粒子の
表面に更にアルミニウムの水酸化物が被着されている黄
色含水酸化鉄粒子の分散性が改良された理由については
未だ明らかではないが、本発明者は、塗布膜とした時の
光沢度が上がることや塗料化時における塗料粘度が低下
すること等から、ビヒクルとの相溶性が向上したことに
よるものと考えている。The yellow iron hydrate particles having a composite hydrate of Fe and Al deposited on the surface of the particles or the yellow iron hydrate particles having a hydroxide of aluminum further deposited on the surface of the particles. Although the reason why the dispersibility has been improved is not yet clear, the inventor of the present invention has reported that the compatibility with the vehicle is high due to the increase in glossiness when formed into a coating film and the decrease in paint viscosity when formed into a paint. It is thought that this was due to improvement.
【００４６】また、耐熱性が向上した理由について、Ｆ
ｅ及びＡｌからなる複合含水酸化物は緻密な層を形成し
やすく、しかも、Ｆｅを有していることにより、同じく
Ｆｅを有している黄色含水酸化鉄粒子の粒子表面に密着
して被着されることによるものと考えている。The reason why the heat resistance was improved was as follows.
The composite hydrated oxide composed of e and Al is easy to form a dense layer, and because it has Fe, it adheres to the surface of the yellow iron oxide hydroxide particles also having Fe and adheres to the surface. I think it is due to being done.
【００４７】必要により、表面に更にアルミニウムの水
酸化物を被着した場合、耐熱性がより向上する理由につ
いて、本発明者は、アルミニウムの水酸化物自体の優れ
た耐熱性と下層にＡｌが含有されていることから上層の
アルミニウムの水酸化物が密着して被着されることによ
るものと考えている。The reason why the heat resistance is further improved when an aluminum hydroxide is further adhered to the surface, if necessary, is that the present inventor has considered that the aluminum hydroxide itself has excellent heat resistance and that the lower layer has Al. It is believed that this is due to the fact that the aluminum hydroxide of the upper layer is adhered and adhered because it is contained.
【００４８】[0048]
【発明の実施の形態】本発明の代表的な実施の形態は、
次の通りである。DESCRIPTION OF THE PREFERRED EMBODIMENTS A typical embodiment of the present invention is as follows.
It is as follows.
【００４９】尚、粒子の平均長軸径、平均短軸径は、い
ずれも電子顕微鏡写真（×２００００）を縦方向及び横
方向にそれぞれ２倍に拡大した写真（×８００００）に
示される粒子３５０個の長軸径、短軸径をそれぞれ測定
し、その平均値で示した。The average major axis diameter and the average minor axis diameter of the particles are shown in particles 350 × shown in a photograph (× 80000) obtained by magnifying the electron micrograph (× 20000) twice in the vertical and horizontal directions, respectively. The major axis diameter and the minor axis diameter were measured, and the average value was shown.
【００５０】黄色含水酸化鉄中の可溶性硫酸塩及び可溶
性ナトリウム塩は、黄色含水酸化鉄粉末５ｇ及び純水１
００ｍｌを秤量して２００ｍｌビーカーに添加して５分
間煮沸をした後、室温まで冷却し、次いで、蒸発により
損失した量の純水を追加した後、濾別して得られる濾液
を用いて、濾液中のＳＯ4 量及びＮａ量を誘導結合プラ
ズマ発光分光分析装置ＳＰＳ４０００（セイコー電子工
業（株）製）により測定した値で示した。The soluble sulfate and the soluble sodium salt in the yellow iron oxide hydroxide were prepared by mixing 5 g of the yellow iron oxide powder and 1 pure water.
After weighing 00 ml and adding it to a 200 ml beaker, boiling for 5 minutes, cooling to room temperature, adding pure water in an amount lost by evaporation, and then using a filtrate obtained by filtration, the filtrate in the filtrate was used. The amounts of SO 4 and Na were shown by values measured by an inductively coupled plasma emission spectrometer SPS4000 (manufactured by Seiko Instruments Inc.).
【００５１】黄色含水酸化鉄粒子の粒子表面に被着して
いるＡｌ量は、蛍光Ｘ線分析により測定した。The amount of Al adhering to the surface of the yellow hydrous iron oxide particles was measured by X-ray fluorescence analysis.
【００５２】黄色含水酸化鉄顔料の耐熱性は、熱分析装
置ＳＳＣ５０００（セイコー電子工業（株）製）を用い
て被測定物の示差走査熱量測定（ＤＳＣ）を行い、得ら
れた該ＤＳＣチャート上に示されるピークを形成する２
つの変曲点のうち最初の変曲点を構成する２つの曲線の
それぞれについて接線を引き、両接線の交点に対応する
温度を読み取って、その温度で示した。The heat resistance of the yellow hydrous iron oxide pigment was measured by using a thermal analyzer SSC5000 (manufactured by Seiko Denshi Kogyo KK) to measure the differential scanning calorimetry (DSC) of the measured object. 2 forming the peak shown in
A tangent was drawn for each of the two curves constituting the first inflection point of the two inflection points, and the temperature corresponding to the intersection of the two tangents was read and indicated as the temperature.
【００５３】黄色含水酸化鉄顔料の色相（Ｌ* 値、ａ*
値及びｂ* 値）及び光沢（分散性）は、下記の方法によ
り、黄色含水酸化鉄顔料を用いた溶剤系塗料を作製し、
その塗料を冷間圧延鋼板（０．８ｍｍ×７０ｍｍ×１５
０ｍｍ）（ＪＩＳ Ｇ−３１４１）に１５０μｍの厚み
で塗布、乾燥して塗膜を形成することにより得られた測
定用試料片を用いて測定した。Hue (L * value, a *
Value and b * value) and gloss (dispersibility) were prepared by the following method to prepare a solvent-based paint using a yellow iron oxide hydroxide pigment.
The paint is applied to a cold-rolled steel plate (0.8 mm × 70 mm × 15
0 mm) (JIS G-3141) with a thickness of 150 μm and dried to form a coating film.
【００５４】溶剤系塗料は、下記のようにして製造し
た。[0054] The solvent-based paint was produced as follows.
【００５５】黄色含水酸化鉄顔料１０ｇと下記割合のア
ミノアルキッド樹脂及びシンナーとを、３ｍｍφガラス
ビーズ９０ｇとともに１４０ｍｌのガラスびんに入れペ
イントシェーカーで９０分間混合、分散し、ミルベース
を作製した。10 g of the yellow hydrous iron oxide pigment and the following ratio of aminoalkyd resin and thinner were placed in a 140 ml glass bottle together with 90 g of 3 mmφ glass beads and mixed and dispersed for 90 minutes with a paint shaker to prepare a mill base.
【００５６】 黄色含水酸化鉄顔料 １２．２重量部 アミノアルキッド樹脂 アミラックＮｏ．１０２６ １９．５重量部 （商品名：関西ペイント（株）製） シンナー ７．３重量部Yellow hydrous iron hydroxide pigment 12.2 parts by weight Amino alkyd resin Amirac No. 1026 19.5 parts by weight (trade name: manufactured by Kansai Paint Co., Ltd.) Thinner 7.3 parts by weight
【００５７】次に、上記ミルベースに下記割合のアミノ
アルキッド樹脂を配合して、更にペインシェーカーで１
５分間混合、分散し、溶剤系塗料を得た。Next, the following ratio of amino alkyd resin was blended with the above-mentioned mill base, and the mixture was further mixed with a pane shaker.
The mixture was mixed and dispersed for 5 minutes to obtain a solvent-based paint.
【００５８】 ミルベース ３９．０重量部 アミノアルキッド樹脂 アミラックＮｏ．１０２６ ６１．０重量部 （商品名：関西ペイント（株）製）Mill base 39.0 parts by weight Amino alkyd resin Amirac No. 1026 61.0 parts by weight (trade name: manufactured by Kansai Paint Co., Ltd.)
【００５９】色相を表すＬ* 値（明度）、ａ* 値（赤色
度）及びｂ* 値（黄色度）は、上記測定用試料片を用い
てＨｕｎｔｅｒのＬａｂ空間によりＬ* 値、ａ* 値及び
ｂ*値をそれぞれ測色し、国際照明委員会（Ｃｏｍｍｉ
ｓｓｉｏｎ Ｉｎｔｅｒｎａｔｉｏｎｎａｌｅ ｄｅ
ｌ’Ｅｃｌａｉｒａｇｅ、ＣＩＥ）１９７６（Ｌ* 、ａ
* 、ｂ* ）均等知覚空間に従って表示した値で示した。
尚、測色用には、多光源分光測色計（ＭＳＣ−ＩＳ−２
Ｄ、スガ試験機（株）製）Ｍｕｌｔｉ−ｓｐｃｔｒｏ−
ｃｏｌｏｕｒ−Ｍｅｔｅｒを用いた。[0059] L * value representing a hue (brightness), a * value (redness) and b * values (yellowness) is, L * value by the Lab space of Hunter by using the measurement sample piece, a * value And b * values were measured, and the International Commission on Illumination (Commi)
session Internationale de
l'Eclairage, CIE) 1976 (L * , a
* , B * ) Values indicated according to the uniform perception space.
For colorimetry, a multi-source spectrophotometer (MSC-IS-2)
D, manufactured by Suga Test Machine Co., Ltd.) Multi-spectro-
color-Meter was used.
【００６０】黄色含水酸化鉄顔料の色相の変化は、耐熱
性改善処理工程の前後における黄色含水酸化鉄粒子のＬ
* 値、ａ* 値及びｂ* 値のそれぞれを測定し、耐熱性改
善処理の前後における黄色含水酸化鉄粒子のＬ* 値、ａ
* 値及びｂ* 値のそれぞれの差をΔＬ* 、Δａ* 及びΔ
ｂ* として示した。ΔＬ* 、Δａ* 及びΔｂ* の絶対値
が小さい程、色相の変化が小さいことを意味する。The change in hue of the yellow hydrated iron oxide pigment is determined by the L of the yellow hydrated iron oxide particles before and after the heat resistance improving process.
* Value, a * value, and b * value were measured, and the L * value of yellow hydrous iron hydroxide particles before and after the heat resistance improvement treatment, a
* And b * values are represented by ΔL * , Δa * and Δ
b * . The smaller the absolute values of ΔL * , Δa *, and Δb * , the smaller the change in hue.
【００６１】光沢度は、上記測定用試料片の塗膜をデジ
タル光沢計ＵＧＶ−５Ｄ（スガ試験機（株）製）を用い
て入射角２０°で測定した時の光沢度（グロス）の値で
示した。光沢度（グロス）の値が高い程、分散性が優れ
ていることを示す。The gloss value is a value of the gloss value (gloss) when the coating film of the test sample is measured at an incident angle of 20 ° using a digital gloss meter UGV-5D (manufactured by Suga Test Instruments Co., Ltd.). Indicated by The higher the gloss value (gloss), the better the dispersibility.
【００６２】前記の方法により酸性水溶液中から得ら
れた針状黄色含水酸化鉄（ゲータイト）粒子（反応溶液
の一部を抜き取り、水洗して得られた黄色含水酸化鉄粒
子の特性は、平均長軸径０．３８μｍ、平均短軸径０．
０６３μｍ、軸比（長軸径／短軸径）６．２、ＢＥＴ比
表面積値２０．１ｍ2 ／ｇ、可溶性硫酸塩はＳＯ4 換算
で５７８０ｐｐｍ、可溶性ナトリウム塩はＮａ換算で２
５６０ｐｐｍであった。）の湿ケーキ（含水固形物）を
水に懸濁して濃度５０ｇ／ｌの懸濁液２０ｌを準備し、
次いで、高速ディゾルバーおよび縦型ビーズミルを用い
て、該懸濁液中の黄色含水酸化鉄粒子をよく分散させ
た。この時の水懸濁液のｐＨ値は５．７であった。Acicular yellow iron oxide hydroxide (goethite) particles obtained from an acidic aqueous solution by the above method (a part of the reaction solution was extracted and washed with water. Shaft diameter 0.38 μm, average short axis diameter 0.
063 μm, axial ratio (major axis diameter / minor axis diameter) 6.2, BET specific surface area value 20.1 m 2 / g, soluble sulfate 5780 ppm in terms of SO 4 , soluble sodium salt 2 in terms of Na
It was 560 ppm. ) Was suspended in water to prepare 20 l of a suspension having a concentration of 50 g / l.
Then, using a high-speed dissolver and a vertical bead mill, the yellow iron oxide hydroxide particles in the suspension were well dispersed. At this time, the pH value of the aqueous suspension was 5.7.
【００６３】この懸濁液２０リットルに０．５ｍｏｌ／
ｌの酢酸アルミニウム水溶液１４８１ｍｌ（黄色含水酸
化鉄に対してＡｌ換算で２．０重量％に相当）および
１．４ｍｏｌ／ｌの硫酸第一鉄溶液１０５８ｍｌ（添加
Ａｌ／Ｆｅ原子比＝１／２）を加え、毎分７０リットル
の空気を吹き込みながら８０℃まで加熱昇温した後、ｐ
Ｈを４．３に維持しながら３時間保持し、黄色含水酸化
鉄表面にＡｌとＦｅからなる複合含水酸化物を被着させ
た。To 20 liters of this suspension, 0.5 mol /
1481 ml of an aqueous aluminum acetate solution (corresponding to 2.0% by weight in terms of Al with respect to yellow iron oxide hydroxide) and 1058 ml of a 1.4 mol / l ferrous sulfate solution (added Al / Fe atomic ratio = 1/2) And heated to 80 ° C. while blowing air at 70 l / min.
H was maintained at 4.3 for 3 hours, and a composite hydrated oxide composed of Al and Fe was deposited on the surface of the yellow hydrous iron oxide.
【００６４】続いてプレスフィルターを用いて濾別し、
通水しながら充分水洗して湿ケーキを得た。Subsequently, the mixture was filtered using a press filter,
The wet cake was obtained by sufficiently washing with flowing water.
【００６５】上記湿ケーキの一部を１２０℃で２４時間
乾燥させた後、自由粉砕機Ｍ−Ｚ型（（株）奈良機械製
作所製）で粉砕した。得られた粒子表面にＦｅ及びＡｌ
からなる複合含水酸化物が被着されている黄色含水酸化
鉄（ゲータイト）粒子は、蛍光Ｘ線分析による測定の結
果、Ａｌ換算で１．８６重量％のアルミニウムを有して
いた。この黄色含水酸化鉄粒子は、平均長軸径が０．３
８μｍ、平均短軸径が０．０６４μｍ、ＢＥＴ比表面積
が２０．３ｍ2 ／ｇであった。また耐熱温度は２７２
℃、色相はＬ* 値６２．３、ａ* 値１７．３、ｂ* 値５
１．１であって、色相の変化はΔＬ* ＝＋０．１、Δａ
* ＝＋０．２、Δｂ* ＝−０．２であり、光沢度は８２
％であった。A part of the wet cake was dried at 120 ° C. for 24 hours, and then pulverized with a free pulverizer MZ type (Nara Machinery Co., Ltd.). Fe and Al are applied to the surface of the obtained particles.
As a result of measurement by fluorescent X-ray analysis, the yellow hydrated iron (goethite) particles to which the composite hydrate of the above was adhered had 1.86% by weight of aluminum in terms of Al. The yellow hydrous iron oxide particles have an average major axis diameter of 0.3.
8 μm, the average minor axis diameter was 0.064 μm, and the BET specific surface area was 20.3 m 2 / g. The heat-resistant temperature is 272.
° C, hue: L * value 62.3, a * value 17.3, b * value 5
1.1, and the change in hue is ΔL * = + 0.1, Δa
* = + 0.2, Δb * = − 0.2, and the gloss was 82
%Met.
【００６６】得られた前記湿ケーキを攪拌機を用いて、
水に解膠し、黄色含水酸化鉄濃度を４５ｇ／ｌに調整し
た２０ｌの懸濁液を準備した。この懸濁液を攪拌しなが
ら６０℃まで加熱昇温した後、０．１ＮのＮａＯＨをｐ
Ｈ値が１０．５になるまで添加し、攪拌を続けながら
０．５ｍｏｌ／ｌのアルミン酸ナトリウム（ＮＡ−１７
０、住友化学工業（株）製）溶液１０００ｍｌ（Ｆｅ及
びＡｌからなる複合含水酸化物が被着されている黄色含
水酸化物に対しＡｌ換算で１．５重量％に相当する。）
を加え１０分間保持した。その後、１Ｎの酢酸水溶液を
ｐＨ値が６．０になるまで添加した後３０分間維持し、
粒子表面にＡｌとＦｅからなる複合含水酸化物が被着さ
れている黄色含水酸化鉄粒子の表面に更にアルミニウム
の水酸化物を沈澱、被着させた。The obtained wet cake was stirred using a stirrer.
Twenty liters of a suspension prepared by peptizing with water and adjusting the concentration of yellow iron-containing hydroxide to 45 g / l was prepared. After heating this suspension to 60 ° C. while stirring, 0.1N NaOH was added to the suspension.
H was added until the H value reached 10.5, and 0.5 mol / l sodium aluminate (NA-17) was added while stirring was continued.
0, manufactured by Sumitomo Chemical Co., Ltd.) 1000 ml of solution (corresponding to 1.5% by weight in terms of Al with respect to the yellow hydrated oxide to which the composite hydrated oxide composed of Fe and Al is applied)
Was added and kept for 10 minutes. Thereafter, a 1N aqueous solution of acetic acid was added until the pH value reached 6.0, and then maintained for 30 minutes.
A hydroxide of aluminum was further precipitated and deposited on the surface of the yellow hydrated iron oxide particles having a composite hydrate of Al and Fe deposited on the surface of the particles.
【００６７】続いて、プレスフィルターを用いて濾別
し、通水しながら十分水洗して湿ケーキを得た。この湿
ケーキを１２０℃で２４時間乾燥させた後、自由粉砕機
Ｍ−２型（商品名：（株）奈良機械製作所製）で解砕
し、粒子表面にＡｌとＦｅからなる複合含水酸化物が被
着され、更に、その表面にアルミニウムの水酸化物が被
着されている黄色酸化鉄粒子粉末を得た。Subsequently, the mixture was separated by filtration using a press filter, and sufficiently washed with water while passing water to obtain a wet cake. After drying this wet cake at 120 ° C. for 24 hours, it is pulverized by a free pulverizer M-2 type (trade name: manufactured by Nara Machinery Co., Ltd.), and a composite hydrous oxide composed of Al and Fe is formed on the particle surface. Was adhered, and further, a yellow iron oxide particle powder was obtained on which the aluminum hydroxide was adhered.
【００６８】この黄色含水酸化鉄（ゲータイト）粒子
は、蛍光Ｘ線分析による測定の結果、Ａｌ換算で３．３
２重量％のアルミニウムを有していた。このことから、
アルミニウムの水酸化物中のアルミニウム量はＡｌ換算
で１．４６重量％（３．３２−１．８６＝１．４６）で
あった。また、この黄色含水酸化鉄粒子は、平均長軸径
が０．３９μｍ、平均短軸径が０．０６４μｍ、ＢＥＴ
比表面積値が１９．３ｍ2 ／ｇであった。また、耐熱温
度は２８４℃であって、色相はＬ* 値が６２．０、ａ*
値が１７．３、ｂ* 値が５１．６、色相の変化はΔＬ*
＝−０．２、Δａ* ＝＋０．２及びΔｂ* ＝＋０．１で
あり、光沢度は８７％であった。As a result of measurement by fluorescent X-ray analysis, the yellow iron oxide hydroxide (goethite) particles were 3.3 in terms of Al.
It had 2% by weight of aluminum. From this,
The amount of aluminum in the hydroxide of aluminum was 1.46% by weight (3.32-1.86 = 1.46) in terms of Al. The yellow hydrous iron oxide particles had an average major axis diameter of 0.39 μm, an average minor axis diameter of 0.064 μm, and a BET
The specific surface area was 19.3 m 2 / g. The heat resistance temperature is 284 ° C., the hue is L * value of 62.0, a *
The value was 17.3, the b * value was 51.6, and the change in hue was ΔL *.
= −0.2, Δa * = + 0.2 and Δb * = + 0.1, and the glossiness was 87%.
【００６９】[0069]
【実施例】次に、実施例並びに比較例を挙げる。Next, examples and comparative examples will be described.
【００７０】＜黄色含水酸化鉄粒子粉末の種類＞被処理
粒子である黄色含水酸化鉄粒子粉末として表１に示され
る被処理粒子１乃至被処理粒子３を準備した。<Types of Yellow Iron Hydroxide Hydroxide Particle Powder> The particles to be treated 1 to 3 shown in Table 1 were prepared as the yellow iron oxide hydroxide particles to be treated.
【００７１】[0071]
【表１】 [Table 1]
【００７２】実施例１〜５ 黄色含水酸化鉄粒子の種類、水懸濁液中の黄色含水酸化
鉄濃度、Ｆｅ及びＡｌからなる複合含水酸化物の被着工
程におけるｐＨ値、アルミニウム化合物の種類及び添加
量、第一鉄塩水溶液の種類及び添加量、反応温度、維持
ｐＨ、空気量、反応時間を種々変化させた以外は、前記
発明の実施の形態と同様にしてＦｅ及びＡｌからなる複
合含水酸化物被着処理を行った。Examples 1 to 5 Types of yellow iron oxide hydroxide particles, concentration of yellow iron oxide hydroxide in water suspension, pH value in the step of depositing a composite hydrous oxide composed of Fe and Al, type of aluminum compound and Except that the amount of addition, the type and amount of the aqueous ferrous salt solution and the amount of addition, the reaction temperature, the maintenance pH, the amount of air, and the reaction time were variously changed, the composite water containing Fe and Al was used in the same manner as the embodiment of the invention. An oxide deposition process was performed.
【００７３】この時の主要製造条件を表２に、諸特性を
表３に示す。The main manufacturing conditions at this time are shown in Table 2, and various characteristics are shown in Table 3.
【００７４】[0074]
【表２】 [Table 2]
【００７５】[0075]
【表３】 [Table 3]
【００７６】実施例６〜１０ 粒子表面にＦｅ及びＡｌからなる複合含水酸化物が被着
されている黄色含水酸化鉄の種類、アルミニウムの水酸
化物による被着工程における水懸濁液中の複合含水酸化
物被着含水酸化鉄濃度、添加前の懸濁液ｐＨ値、添加す
るアルミニウム化合物の種類及び量、懸濁液の最終ｐＨ
値を種々変化させた以外は、前記発明の実施の形態と同
様にして粒子表面にＦｅ及びＡｌからなる複合含水酸化
物が被着され、更に、その表面にアルミニウムの水酸化
物が被着されている黄色含水酸化鉄粒子粉末を得た。Examples 6 to 10 Kinds of yellow hydrous iron oxide having a composite hydrate of Fe and Al deposited on the surface of particles, composite in an aqueous suspension in the deposition step of aluminum hydroxide Concentration of hydrated iron oxide containing iron oxide, pH value of suspension before addition, type and amount of aluminum compound to be added, final pH of suspension
Except that the values were variously changed, a composite hydrate oxide composed of Fe and Al was adhered to the particle surface in the same manner as in the embodiment of the invention, and further, an aluminum hydroxide was adhered to the surface. Yellow powder containing hydrous iron hydroxide was obtained.
【００７７】この時の主要製造条件を表４に、表面にア
ルミニウムの水酸化物が被着されている黄色含水酸化鉄
粒子粉末の諸特性を表５に示す。Table 4 shows the main production conditions at this time, and Table 5 shows various properties of the yellow iron oxide hydroxide particles having aluminum hydroxide adhered to the surface.
【００７８】[0078]
【表４】 [Table 4]
【００７９】[0079]
【表５】 [Table 5]
【００８０】比較例１ 発明の実施の形態に記載の被処理黄色含水酸化鉄粒子と
同一の黄色含水酸化鉄粒子を用い、いずれの処理も施さ
ないで、その諸特性を測定した結果を表５に示す。Comparative Example 1 Using the same yellow iron oxide hydroxide particles as the yellow iron oxide hydroxide particles to be treated according to the embodiment of the present invention, without performing any treatment, the results of measuring various properties are shown in Table 5. Shown in
【００８１】表６に示す通り、反応溶液中から濾別、水
洗、乾燥して得られる黄色含水酸化鉄は、耐熱性が悪い
ものであった。As shown in Table 6, the yellow iron oxide hydroxide obtained by filtering, washing with water and drying from the reaction solution had poor heat resistance.
【００８２】比較例２ 発明の実施の形態に記載の被処理黄色含水酸化鉄粒子と
同一の黄色含水酸化鉄粒子を用い、Ｆｅ及びＡｌからな
る複合含水酸化物の被着処理を施すことなく、水懸濁液
中の黄色含水酸化鉄濃度を５０ｇ／ｌ、アルミン酸ナト
リウムの添加量をＡｌ換算で２．６８重量％、添加前の
懸濁液ｐＨ値を１０．０、懸濁液の最終ｐＨ値を７．０
に調整した以外は発明の実施の形態と同様にして、アル
ミニウムの水酸化物が被着されている黄色含水酸化鉄粒
子を得た。Comparative Example 2 Using the same yellow iron oxide hydroxide particles as the yellow iron oxide particles to be treated according to the embodiment of the present invention, without subjecting the composite hydrous oxide composed of Fe and Al to the adhesion treatment, The concentration of yellow iron hydroxide hydroxide in the aqueous suspension was 50 g / l, the amount of sodium aluminate added was 2.68% by weight in terms of Al, the pH of the suspension before the addition was 10.0, and the final amount of the suspension. pH value of 7.0
In the same manner as in the embodiment of the invention except that the adjustment was made, yellow iron-containing hydroxide particles coated with aluminum hydroxide were obtained.
【００８３】得られた粒子表面にアルミニウムの水酸化
物が被着されている黄色含水酸化鉄粒子の諸特性を表５
に示す。Table 5 shows the properties of the obtained yellow iron oxide hydroxide particles having aluminum hydroxide adhered to the surface of the obtained particles.
Shown in
【００８４】表５に示す通り、粒子表面にアルミニウム
の水酸化物のみを被着させた黄色含水酸化鉄粒子は、耐
熱性が未だ不十分なものであった。As shown in Table 5, the yellow iron oxide hydroxide particles having only aluminum hydroxide adhered to the particle surface had insufficient heat resistance.
【００８５】比較例３ 発明の実施の形態に記載の被処理黄色含水酸化鉄粒子と
同一の黄色含水酸化鉄粒子を用いた水懸濁液濃度が５０
ｇ／ｌの黄色含水酸化鉄スラリー２０ｌ（固形分として
１ｋｇに相当する。）に１３ＮのＮａＯＨ溶液を加えて
ｐＨ値を１３．０とした。スラリー７００ｍｌを分取
し、内容積１ｌのオートクレーブ（東洋高圧（株）製）
に入れ、撹拌しながら昇温し、２２０℃で３０分保持し
た後、冷却した。スラリーを取り出し水を用いたデカン
テーションによって濾液が中性になるまで水で十分水洗
した。次いで、ヌッチェを用いて濾別した湿ケーキを１
２０℃で２４時間乾燥した後、粉砕し、黄色酸化鉄粒子
粉末を得た。Comparative Example 3 The concentration of an aqueous suspension using the same yellow iron oxide hydroxide particles as the yellow iron oxide hydroxide particles to be treated according to the embodiment of the present invention was 50%.
To 20 l (equivalent to 1 kg as solid content) of 20 g / l of yellow iron-containing hydroxide slurry was added a 13N NaOH solution to adjust the pH value to 13.0. An autoclave (manufactured by Toyo Koatsu Co., Ltd.) having an internal volume of 1 liter was taken out of 700 ml of the slurry.
The mixture was heated with stirring, kept at 220 ° C. for 30 minutes, and then cooled. The slurry was taken out and thoroughly washed with water until the filtrate became neutral by decantation using water. Next, the wet cake filtered with Nutsche
After drying at 20 ° C. for 24 hours, it was pulverized to obtain yellow iron oxide particles.
【００８６】得られた黄色含水酸化鉄粒子粉末の諸特性
を表５に示す。Table 5 shows the properties of the obtained yellow iron oxide hydroxide particles.
【００８７】表５に示す通り、耐熱性改善処理工程の前
後での色相の変化が大きいものであった。As shown in Table 5, the change in hue before and after the heat resistance improving process was large.
【００８８】比較例４ 発明の実施の形態に記載の被処理黄色含水酸化鉄粒子と
同一の黄色含水酸化鉄粒子を用いた水懸濁液濃度が５０
ｇ／ｌの黄色含水酸化鉄スラリー２０ｌ（固形分として
１ｋｇに相当する。）に硫酸アルミニウム１５６．４ｇ
を含む水溶液２ｌを投入し、よく撹拌した。スラリー７
００ｍｌを分取し、内容積１ｌのオートクレーブ（東洋
高圧（株）製）に入れ、撹拌しながら昇温し、２２０℃
で３０分保持した後、冷却した。スラリーを取り出しヌ
ッチェを用いて濾別し、濾液が中性になるまで水洗し
た。得られた湿ケーキを１２０℃で２４時間乾燥した
後、粉砕し、黄色酸化鉄粒子粉末を得た。Comparative Example 4 The concentration of an aqueous suspension using the same yellow iron oxide hydroxide particles as the yellow iron oxide hydroxide particles to be treated according to the embodiment of the present invention was 50%.
156.4 g of aluminum sulfate was added to 20 l (corresponding to 1 kg in solid content) of 20 g / l of yellow iron-containing hydroxide slurry.
Was added and stirred well. Slurry 7
Separately, 00 ml was put into an autoclave (manufactured by Toyo Koatsu Co., Ltd.) having an internal volume of 1 liter, and the temperature was raised while stirring, and the temperature was lowered to 220 ° C.
, And then cooled. The slurry was taken out, separated by filtration using a nutsche, and washed with water until the filtrate became neutral. The obtained wet cake was dried at 120 ° C. for 24 hours and then pulverized to obtain yellow iron oxide particles.
【００８９】得られた黄色含水酸化鉄粒子粉末の諸特性
を表５に示す。Table 5 shows the properties of the obtained yellow iron oxide hydroxide-containing particles.
【００９０】表５に示す通り、耐熱性改善処理工程の前
後での色相の変化が大きいものであった。As shown in Table 5, the change in hue before and after the heat resistance improving process was large.
【００９１】比較例５ 発明の実施の形態に記載の被処理黄色含水酸化鉄粒子と
同一の黄色含水酸化鉄粒子を用いた水懸濁液濃度が４
６．７ｇ／ｌの黄色含水酸化鉄スラリーに６ＮのＮａＯ
Ｈ溶液を加えてｐＨ値を１３．０とした。スラリー７０
０ｍｌ（固形分として３２．７ｇに相当する。）を分取
し、内容積１ｌのオートクレーブ（東洋高圧（株）製）
に入れ、撹拌しながら昇温し、１８０℃で１２０分保持
した後、冷却した。取り出したスラリーに撹拌しながら
アルミン酸ナトリウム（ＮＡ−１７０：住友化学工業
（株）製）溶液４．３２ｇを加え、徐々に希硫酸を加え
てｐＨ値を６．０に調整した。水を用いたデカンテーシ
ョンによって十分に水洗した後、ヌッチェを用いて濾別
した。得られた湿ケーキを１２０℃で２４時間乾燥した
後、粉砕し、黄色酸化鉄粒子粉末を得た。Comparative Example 5 The concentration of the aqueous suspension using the same yellow iron oxide hydroxide particles to be treated as described in the embodiment of the invention was 4
6.7 g / l of yellow iron oxide hydroxide slurry was mixed with 6N NaO
H solution was added to adjust the pH to 13.0. Slurry 70
An autoclave (manufactured by Toyo Koatsu Co., Ltd.) having an internal volume of 1 liter was collected by collecting 0 ml (corresponding to 32.7 g as a solid content).
The mixture was heated while stirring, and kept at 180 ° C. for 120 minutes, and then cooled. 4.32 g of a sodium aluminate (NA-170: manufactured by Sumitomo Chemical Co., Ltd.) solution was added to the removed slurry with stirring, and the pH value was adjusted to 6.0 by gradually adding dilute sulfuric acid. After sufficiently washing with water by decantation using water, the mixture was filtered off using Nutsche. The obtained wet cake was dried at 120 ° C. for 24 hours and then pulverized to obtain yellow iron oxide particles.
【００９２】得られた黄色含水酸化鉄粒子粉末の諸特性
を表５に示す。Table 5 shows properties of the obtained yellow iron oxide hydroxide particles.
【００９３】表５に示す通り、耐熱性改善処理工程の前
後での色相の変化が大きいものであった。As shown in Table 5, there was a large change in hue before and after the heat resistance improving process.
【００９４】比較例６ 発明の実施の形態に記載の被処理黄色含水酸化鉄粒子と
同一の黄色含水酸化鉄粒子を用いた水懸濁液濃度が４
６．７ｇ／ｌの黄色含水酸化鉄スラリーに６ＮのＮａＯ
Ｈ溶液を加えてｐＨ値を１２．０とした。スラリー７０
０ｍｌ（固形分として３２．７ｇに相当する。）を分取
し、これにアルミン酸ナトリウム（ＮＡ−１７０：住友
化学工業（株）製）溶液２．８７ｇを加え、内容積１ｌ
のオートクレーブ（東洋高圧（株）製）に入れ、撹拌し
ながら昇温し、１８０℃で６０分間水熱処理した後冷却
した。取り出したスラリーを水を用いたデカンテーショ
ンによって十分に水洗した後、ヌッチェを用いて濾別し
た。得られた湿ケーキを１２０℃で４時間乾燥した後、
粉砕し、黄色酸化鉄粒子粉末を得た。Comparative Example 6 The concentration of the aqueous suspension using the same yellow iron oxide hydroxide particles as the yellow iron oxide hydroxide particles to be treated according to the embodiment of the present invention was 4%.
6.7 g / l of yellow iron oxide hydroxide slurry was mixed with 6N NaO
H solution was added to adjust the pH to 12.0. Slurry 70
0 ml (corresponding to 32.7 g as a solid content) was collected, and 2.87 g of a sodium aluminate (NA-170: manufactured by Sumitomo Chemical Co., Ltd.) solution was added thereto, and the inner volume was 1 liter.
Was placed in an autoclave (manufactured by Toyo Koatsu Co., Ltd.), heated while stirring, subjected to a hydrothermal treatment at 180 ° C. for 60 minutes, and then cooled. The removed slurry was sufficiently washed with water by decantation using water, and then filtered off using Nutsche. After drying the obtained wet cake at 120 ° C. for 4 hours,
It was pulverized to obtain yellow iron oxide particles.
【００９５】得られた黄色含水酸化鉄粒子粉末の諸特性
を表５に示す。Table 5 shows the properties of the obtained yellow iron oxide hydroxide particles.
【００９６】表５に示す通り、耐熱性改善処理工程の前
後での色相の変化が大きいものであった。As shown in Table 5, the change in hue before and after the heat resistance improving process was large.
【００９７】[0097]
【発明の効果】本発明に係る黄色含水酸化鉄粒子粉末の
製造法によれば、前出実施例に示した通り、分散性が優
れており、しかも、耐熱性が向上しているとともに、耐
熱性改善処理工程の前後における色相の変化が小さい黄
色含水酸化鉄粒子粉末を得ることができるので、黄色着
色顔料、殊に、道路アスファルト用や路面表示塗料用黄
色着色顔料として好ましいものである。According to the method for producing the iron oxide hydroxide particles containing yellow water according to the present invention, as shown in the above examples, the dispersibility is excellent, the heat resistance is improved, and the heat resistance is improved. It is preferable as a yellow coloring pigment, particularly as a yellow coloring pigment for road asphalt and road marking paint, since it is possible to obtain yellow iron-containing hydroxide particles having a small change in hue before and after the property improving treatment step.
【００９８】また、本発明に係る黄色含水酸化鉄粒子粉
末の製造法によれば、前出実施例に示した通り、オート
クレーブ等の特殊な装置を用いることなく、常圧下で耐
熱性の改良された黄色含水酸化鉄粒子粉末を得ることが
できるので、工業的、経済的に有利である。Further, according to the method for producing yellow iron oxide hydroxide particles according to the present invention, as shown in the above-described embodiment, the heat resistance is improved at normal pressure without using a special device such as an autoclave. It is industrially and economically advantageous because a yellowish iron oxide hydroxide particle powder can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 角田 博 広島県広島市中区舟入南４丁目１番２号戸 田工業株式会社創造センター内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroshi Tsunoda 4-1-2, Funariminami, Naka-ku, Hiroshima-shi, Hiroshima The inside of Toda Kogyo Co., Ltd.
Claims (2)
黄色含水酸化鉄粒子に対しＡｌ換算で０．１〜１０重量
％のアルミニウム化合物とＦｅ換算で０．１〜５０重量
％の第一鉄塩化合物とを添加、混合した後酸素含有ガス
を通気して、前記黄色含水酸化鉄粒子の粒子表面にＦｅ
及びＡｌからなる複合含水酸化物を被着させ、次いで、
濾別、水洗、乾燥することにより、粒子表面にＦｅ及び
Ａｌからなる複合含水酸化物が被着されている黄色含水
酸化鉄粒子からなる黄色含水酸化鉄粒子粉末を得ること
を特徴とする耐熱性黄色含水酸化鉄顔料の製造法。1. An aqueous dispersion containing yellow iron oxide hydroxide particles contains an aluminum compound in an amount of 0.1 to 10% by weight in terms of Al and a 0.1 to 50% by weight of an iron compound in an amount of 0.1 to 50% by weight in terms of Fe. After adding and mixing with a ferrous salt compound, an oxygen-containing gas is ventilated, and Fe particles
And a composite hydrated oxide consisting of Al and
Filtration, washing, and drying are performed to obtain a yellow iron oxide hydroxide particle powder composed of yellow iron oxide hydroxide particles having a composite hydrate oxide composed of Fe and Al adhered to the particle surface. Method for producing yellow iron oxide hydroxide pigment.
黄色含水酸化鉄粒子に対しＡｌ換算で０．１〜１０重量
％のアルミニウム化合物とＦｅ換算で０．１〜５０重量
％の第一鉄塩化合物とを添加、混合した後酸素含有ガス
を通気して、前記含水酸化鉄粒子の粒子表面にＦｅ及び
Ａｌからなる複合含水酸化物を被着させ、次いで、粒子
表面にＦｅ及びＡｌからなる複合含水酸化物が被着され
ている前記黄色含水酸化鉄粒子を含む水分散液のｐＨ値
を１０以上又は４以下に調整した後、アルミニウム化合
物を添加、攪拌し、次いで該分散液のｐＨ値を５〜９の
範囲に再調整して、前記Ｆｅ及びＡｌからなる複合含水
酸化物表面にアルミニウムの水酸化物を被着させた後、
濾別、水洗、乾燥することにより粒子表面にＦｅ及びＡ
ｌからなる複合含水酸化物が被着され、更にその上にア
ルミニウムの水酸化物が被着されている黄色含水酸化鉄
粒子からなる黄色含水酸化鉄粒子粉末を得ることを特徴
とする耐熱性黄色含水酸化鉄顔料の製造法。2. The aqueous dispersion containing yellow iron oxide hydroxide particles contains 0.1 to 10% by weight of aluminum compound in terms of Al and 0.1 to 50% by weight of Fe compound in terms of Fe with respect to the yellow iron oxide particles. After adding and mixing with a ferrous salt compound, an oxygen-containing gas is passed therethrough to deposit a composite hydrated oxide composed of Fe and Al on the particle surfaces of the iron oxide hydrate particles, and then on the particle surfaces with Fe and Al After adjusting the pH value of the aqueous dispersion containing the yellow hydrated iron oxide particles to which the composite hydrated oxide is applied to 10 or more or 4 or less, an aluminum compound is added thereto, and the mixture is stirred. After the pH value was readjusted to the range of 5 to 9 and a hydroxide of aluminum was applied to the surface of the composite hydrated oxide composed of Fe and Al,
By filtering, washing and drying, Fe and A
(1) obtaining a yellow iron oxide hydroxide particle powder comprising yellow iron oxide hydroxide particles, on which a composite hydrate consisting of 1 is deposited, and on which a hydroxide of aluminum is further deposited. Production method of iron oxide hydroxide pigment.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18313397A JP3509842B2 (en) | 1997-06-23 | 1997-06-23 | Production method of heat-resistant yellow iron hydroxide hydroxide pigment |
| US09/102,054 US6027559A (en) | 1997-06-23 | 1998-06-22 | Yellow iron oxide hydroxide particles and process for producing the same |
| CN98117205A CN1107647C (en) | 1997-06-23 | 1998-06-23 | Yellow iron oxide hydroxide particles and process for producing the same |
| DE69825681T DE69825681T2 (en) | 1997-06-23 | 1998-06-23 | Yellow iron oxide particles and process for their preparation |
| EP98304940A EP0887387B1 (en) | 1997-06-23 | 1998-06-23 | Yellow iron oxide hydroxide particles and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18313397A JP3509842B2 (en) | 1997-06-23 | 1997-06-23 | Production method of heat-resistant yellow iron hydroxide hydroxide pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1112491A true JPH1112491A (en) | 1999-01-19 |
| JP3509842B2 JP3509842B2 (en) | 2004-03-22 |
Family
ID=16130383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18313397A Expired - Fee Related JP3509842B2 (en) | 1997-06-23 | 1997-06-23 | Production method of heat-resistant yellow iron hydroxide hydroxide pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3509842B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354944A (en) * | 2000-06-16 | 2001-12-25 | Okura Ind Co Ltd | Cover film for illuminant |
| JP2009156921A (en) * | 2007-12-25 | 2009-07-16 | Shin Etsu Polymer Co Ltd | Elastic roller, fixing device for image forming device, and image forming device |
| JP2014028947A (en) * | 2012-06-28 | 2014-02-13 | Toda Kogyo Corp | Thermal resistant yellow water-containing iron oxide pigment and manufacturing method thereof, coating material and resin composition using thermal resistant yellow water-containing iron oxide pigment |
| CN112126252A (en) * | 2020-08-18 | 2020-12-25 | 江苏宇星工贸有限公司 | Production process of heat-resistant iron oxide yellow |
-
1997
- 1997-06-23 JP JP18313397A patent/JP3509842B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354944A (en) * | 2000-06-16 | 2001-12-25 | Okura Ind Co Ltd | Cover film for illuminant |
| JP2009156921A (en) * | 2007-12-25 | 2009-07-16 | Shin Etsu Polymer Co Ltd | Elastic roller, fixing device for image forming device, and image forming device |
| JP2014028947A (en) * | 2012-06-28 | 2014-02-13 | Toda Kogyo Corp | Thermal resistant yellow water-containing iron oxide pigment and manufacturing method thereof, coating material and resin composition using thermal resistant yellow water-containing iron oxide pigment |
| CN112126252A (en) * | 2020-08-18 | 2020-12-25 | 江苏宇星工贸有限公司 | Production process of heat-resistant iron oxide yellow |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3509842B2 (en) | 2004-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4676838A (en) | Lamellar iron oxide pigments, a process for the production thereof and the use thereof | |
| US4826537A (en) | Lamellar pigments of the general formula MnX -AlY Fe2-(X+Y) O3 | |
| JP2002188021A (en) | Black composite iron oxide pigment, coating material and resin composition given by using the black composite iron oxide pigment | |
| JPH0352413B2 (en) | ||
| EP1106657B1 (en) | Iron oxide hydroxide composite particles, pigment, paint and resin composition. | |
| KR20150108437A (en) | Flaky aluminum oxide and method of producing thereof | |
| US7687564B2 (en) | Black iron-based particles, and black paint and rubber or resin composition using the same | |
| JPH11323174A (en) | Iron-based black composite particle powder and its production, coating material prepared by using the iron-based black composite particle powder, and rubber resin composition colored with the iron-based black composite particle powder | |
| EP1293480A1 (en) | Process for producing granular hematite particles | |
| US5500043A (en) | Lustrous pigment and the method of producing the same | |
| US6139618A (en) | Fine yellow composite iron oxide hydroxide pigment, and paint or resin composition using the same | |
| JPH1112491A (en) | Production of heat-resistant yellow hydrated iron oxide pigment | |
| JP4446133B2 (en) | Fine yellow composite hydrous iron oxide pigment, process for producing the same, paint and resin composition using the pigment | |
| KR101782861B1 (en) | Flaky aluminum oxide and method of producing thereof | |
| US6027559A (en) | Yellow iron oxide hydroxide particles and process for producing the same | |
| JP3480485B2 (en) | Method for producing heat-resistant yellow iron-containing hydrous pigment | |
| JP3214542B2 (en) | Method for producing heat-resistant yellow iron-containing hydrous pigment | |
| JP4003026B2 (en) | Heat resistant yellow pigment and paint and resin composition using the heat resistant yellow pigment | |
| JP4862977B2 (en) | Fine green pigment, paint and resin composition using the fine green pigment | |
| JP3651919B2 (en) | Coloring of lacquers and plastics with iron oxide direct red pigment | |
| JP4336227B2 (en) | Composite black oxide particles, method for producing the same, black paint and black matrix | |
| JP3552015B2 (en) | Nonmagnetic black pigment powder, nonmagnetic black paint using the nonmagnetic black pigment powder, and black rubber / resin composition using the nonmagnetic black pigment powder | |
| JP3884526B2 (en) | Mica-based composite material and method for producing the same | |
| JP2001181533A (en) | Green pigment, and coating material and resin composition prepared by using same | |
| JP2002146231A (en) | Fine orange pigment, and coating material and resin composition prepared by using the pigment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Effective date: 20031210 Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20031223 |
|
| LAPS | Cancellation because of no payment of annual fees |