JP2000233932A - Fine particle red iron oxide pigment, its production, coating material using the same and resin composition - Google Patents
Fine particle red iron oxide pigment, its production, coating material using the same and resin compositionInfo
- Publication number
- JP2000233932A JP2000233932A JP26920899A JP26920899A JP2000233932A JP 2000233932 A JP2000233932 A JP 2000233932A JP 26920899 A JP26920899 A JP 26920899A JP 26920899 A JP26920899 A JP 26920899A JP 2000233932 A JP2000233932 A JP 2000233932A
- Authority
- JP
- Japan
- Prior art keywords
- iron oxide
- fine
- red iron
- oxide pigment
- particles
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、長軸径の粒度が均斉で
あるとともに短軸径の粒度が均斉であることによって、
透明性が優れている微細な赤色酸化鉄顔料を提供するも
のである。BACKGROUND OF THE INVENTION The present invention relates to a method for producing a polymer having a uniform major axis diameter and a uniform minor axis diameter.
An object of the present invention is to provide a fine red iron oxide pigment having excellent transparency.
【０００２】[0002]
【従来の技術】ヘマタイト粒子粉末は、赤色を呈してい
ることから赤色酸化鉄顔料として広く知られており、塗
料、印刷インキ、プラスチック、フィルム及び化粧品の
着色等、多くの用途を持つものである。2. Description of the Related Art Hematite particle powder is widely known as a red iron oxide pigment because of its red color, and has many uses such as coloring of paints, printing inks, plastics, films and cosmetics. .
【０００３】ヘマタイト粒子粉末の中でも、粒子径が
０．１μｍ以下の微粒子からなるものは、塗膜にした時
に可視光領域の光に対して透明な塗膜を得ることができ
るため、透明性を呈する赤色酸化鉄顔料として知られて
いる。[0003] Among hematite particle powders, those composed of fine particles having a particle diameter of 0.1 µm or less can form a coating film which is transparent to light in the visible light region when formed into a coating film. It is known as a red iron oxide pigment.
【０００４】この粒子径が０．１μｍ以下のヘマタイト
微粒子からなる赤色酸化鉄顔料（以下、「微細な赤色酸
化鉄顔料」という。）は、微粒子であるため、ビヒクル
中や樹脂組成物中の分散性が劣っており、塗膜や樹脂組
成物にした時に十分な透明性を呈するものではなかっ
た。The red iron oxide pigment composed of fine particles of hematite having a particle diameter of 0.1 μm or less (hereinafter referred to as “fine red iron oxide pigment”) is a fine particle, and therefore, is dispersed in a vehicle or a resin composition. However, when formed into a coating film or a resin composition, it did not exhibit sufficient transparency.
【０００５】即ち、微細な赤色酸化鉄顔料は、微粒子で
あるため、粉体の表面エネルギーが高く凝集を起こしや
すいために、ビヒクル中や樹脂組成物中への分散が困難
であり、これを塗布して得られた塗膜及び樹脂組成物
は、粒子が凝集して粗大な粒子となるために十分な透明
性を有さないものである。That is, since fine red iron oxide pigments are fine particles, the surface energy of the powder is high and the powder is apt to agglomerate. Therefore, it is difficult to disperse the pigment in a vehicle or a resin composition. The coating film and the resin composition thus obtained do not have sufficient transparency because the particles aggregate to form coarse particles.
【０００６】そこで、微細な赤色酸化鉄顔料のビヒクル
中や樹脂組成物中での分散性を改良することが強く要求
されている。[0006] Therefore, there is a strong demand for improving the dispersibility of fine red iron oxide pigments in vehicles and resin compositions.
【０００７】従来、微細な赤色酸化鉄顔料の分散性を向
上させる方法として、粒子粉末の粒度を改善することが
知られており、これまでに粒度の均斉なゲータイト微粒
子粉末を水溶液中で生成させ、その後の加熱脱水処理に
おいて、該粒度が均斉なゲータイト微粒子粉末の粒度を
保持させることにより、粒度の均斉なヘマタイト微粒子
粉末を得ることが既に知られている。（特開昭４９−３
４４９８号公報、特公昭５９−４８７６８号公報等）。Hitherto, as a method for improving the dispersibility of fine red iron oxide pigments, it has been known to improve the particle size of the particle powder. Until now, goethite fine particle powder having a uniform particle size has been produced in an aqueous solution. It is already known that, in the subsequent heat dehydration treatment, by maintaining the particle size of the goethite fine particle powder having a uniform particle size, a hematite fine particle powder having a uniform particle size can be obtained. (JP-A-49-3
4498, JP-B-59-48768 and the like).
【０００８】[0008]
【発明が解決しようとする課題】ビヒクル中や樹脂組成
物中への分散性を改善するために、粒度ができるだけ均
斉である微細な赤色酸化鉄顔料は、現在、最も要求され
ているところであるが、長軸径の粒度が均斉であるとと
もに短軸径の粒度が均斉である微細な赤色酸化鉄顔料
は、未だ得られていない。In order to improve dispersibility in a vehicle or a resin composition, a fine red iron oxide pigment having a uniform particle size as much as possible has been the most demanded at present. Fine red iron oxide pigments in which the major axis diameter is uniform and the minor axis diameter is uniform have not yet been obtained.
【０００９】即ち、前記公知の方法による場合は、後出
比較例に示す通り、出発原料であるゲータイト微粒子の
粒度、殊に短軸径の粒度は未だ十分均斉とは言い難く、
また、その後の加熱脱水処理工程において、ゲータイト
微粒子中に含まれるゲータイト超微粒子に起因して粒子
相互間における焼結が生じ易いので、得られる微細な赤
色酸化鉄顔料の粒度、殊に短軸径の粒度もまた十分均斉
なものとは言い難いものであった。That is, in the case of the above-mentioned known method, the particle size of the goethite fine particles as the starting material, particularly the particle size of the minor axis diameter, is still not sufficiently uniform, as shown in the comparative examples below.
Further, in the subsequent heat dehydration treatment step, since sintering between particles is likely to occur due to the goethite ultrafine particles contained in the goethite fine particles, the particle size of the obtained fine red iron oxide pigment, especially the short axis diameter Were also not sufficiently uniform.
【００１０】そこで、本発明は、長軸径の粒度が均斉で
あるとともに短軸径の粒度が均斉であることによって、
透明性が優れている微細な赤色酸化鉄顔料を得ることを
技術的課題とする。Accordingly, the present invention provides a method for producing a polymer having a uniform major axis diameter and a uniform minor axis diameter.
It is a technical object to obtain a fine red iron oxide pigment having excellent transparency.
【００１１】[0011]
【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.
【００１２】即ち、本発明は、長軸径の幾何標準偏差値
が１．５以下であって、短軸径の幾何標準偏差値が１．
３以下である平均長軸径が０．００５〜０．１μｍのヘ
マタイト微粒子からなることを特徴とする微細な赤色酸
化鉄顔料である。That is, according to the present invention, the geometric standard deviation of the major axis is 1.5 or less, and the geometric standard deviation of the minor axis is 1.
A fine red iron oxide pigment comprising hematite microparticles having an average major axis diameter of 0.005 to 0.1 μm of 3 or less.
【００１３】また、本発明は、ヘマタイト微粒子粉末が
粒子内部にＡｌ換算で０．０５〜５０重量％のアルミニ
ウムを含有している上記記載の微細な赤色酸化鉄顔料で
ある。Further, the present invention is the fine red iron oxide pigment described above, wherein the hematite fine particle powder contains 0.05 to 50% by weight of aluminum in terms of Al inside the particles.
【００１４】また、本発明は、ヘマタイト微粒子粉末の
粒子表面がアルミニウムの水酸化物、アルミニウムの酸
化物、ケイ素の水酸化物及びケイ素の酸化物の少なくと
も１種で被覆されている上記記載の微細な赤色酸化鉄顔
料である。[0014] The present invention also relates to the fine particle according to the above, wherein the particle surface of the hematite fine particle powder is coated with at least one of aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. Red iron oxide pigment.
【００１５】また、本発明は、ゲータイト微粒子粉末を
２５０〜５００℃の温度範囲で加熱脱水処理してヘマタ
イト微粒子粉末とするに当って、前記加熱脱水処理に先
立ってあらかじめ、前記ゲータイト微粒子粉末を１００
〜２００℃の温度範囲で加熱処理して、該ゲータイト微
粒子粉末に含まれているゲータイト超微粒子をゲータイ
ト微粒子に吸収させておくことを特徴とする上記記載の
微細な赤色酸化鉄顔料の製造法である。In the present invention, the goethite fine particle powder is heated and dehydrated in a temperature range of 250 to 500 ° C. to obtain hematite fine particle powder.
The method for producing a fine red iron oxide pigment according to the above description, wherein the goethite ultrafine particles contained in the goethite fine particle powder are absorbed by the goethite fine particles by performing a heat treatment in a temperature range of ~ 200 ° C. is there.
【００１６】また、本発明は、粒子内部にＡｌ換算で
０．０５〜５０重量％のアルミニウムを含有しているゲ
ータイト微粒子粉末を２５０〜５００℃の温度範囲で加
熱脱水処理してヘマタイト微粒子粉末とするに当って、
上記加熱脱水処理に先立ってあらかじめ、前記ゲータイ
ト微粒子粉末を１００〜２００℃の温度範囲で加熱処理
して該ゲータイト微粒子粉末に含まれているゲータイト
超微粒子をゲータイト微粒子に吸収させておくことを特
徴とする上記記載の微細な赤色酸化鉄顔料の製造法であ
る。The present invention also provides a hematite fine particle powder by heating and dehydrating a goethite fine particle powder containing 0.05 to 50% by weight of aluminum in terms of Al in the inside of a particle in a temperature range of 250 to 500 ° C. In doing so
Prior to the heat dehydration treatment, in advance, the goethite ultrafine particles contained in the goethite fine particle powder are subjected to a heat treatment in a temperature range of 100 to 200 ° C. to absorb the goethite ultrafine particles in the goethite fine particles. A method for producing a fine red iron oxide pigment as described above.
【００１７】また、本発明は、上記記載のいずれかの微
細な赤色酸化鉄顔料を用いることを特徴とする塗料であ
る。Further, the present invention is a paint using any one of the fine red iron oxide pigments described above.
【００１８】また、本発明は、上記記載のいずれかの微
細な赤色酸化鉄顔料を用いることを特徴とする樹脂組成
物である。Further, the present invention is a resin composition using any of the fine red iron oxide pigments described above.
【００１９】本発明の構成を詳述すれば、次の通りであ
る。The structure of the present invention will be described below in detail.
【００２０】先ず、本発明に係る微細な赤色酸化鉄顔料
について述べる。First, the fine red iron oxide pigment according to the present invention will be described.
【００２１】本発明に係る微細な赤色酸化鉄顔料は、長
軸径の幾何標準偏差値が１．５以下であって、短軸径の
幾何標準偏差値が１．３以下である平均長軸径が０．０
０５〜０．１μｍのヘマタイト微粒子粉末からなる。The fine red iron oxide pigment according to the present invention has an average major axis having a geometric standard deviation of the major axis of 1.5 or less and a geometric standard deviation of the minor axis of 1.3 or less. Diameter 0.0
It consists of a hematite fine particle powder of 0.5 to 0.1 μm.
【００２２】長軸径及び短軸径の幾何標準偏差値が上限
値を超える場合には、存在する粗大粒子によりビヒクル
中や樹脂組成物中における均一な分散が困難となり、該
赤色酸化鉄顔料を用いて得られた塗膜や樹脂組成物は、
十分な透明性を有さない。ビヒクル中や樹脂組成物中へ
の分散性及び得られる塗膜や樹脂組成物の透明性を考慮
すれば、長軸径の幾何標準偏差値は好ましくは１．４８
以下であり、より好ましくは１．４３以下であって、短
軸径の幾何標準偏差値は好ましくは１．２８以下であ
り、より好ましくは１．２５以下である。工業的な生産
性を考慮すれば、長軸径及び短軸径（以下、粒子径とす
る）の幾何標準偏差値の下限値は１．０１である。If the geometric standard deviation of the major axis diameter and the minor axis diameter exceeds the upper limit, uniform dispersion in the vehicle or resin composition becomes difficult due to the coarse particles present, and the red iron oxide pigment is The coating film and resin composition obtained by using
Does not have sufficient transparency. Considering the dispersibility in the vehicle or the resin composition and the transparency of the obtained coating film or resin composition, the geometric standard deviation of the major axis diameter is preferably 1.48.
Or less, more preferably 1.43 or less, and the geometric standard deviation value of the minor axis diameter is preferably 1.28 or less, more preferably 1.25 or less. In consideration of industrial productivity, the lower limit of the geometric standard deviation of the major axis diameter and the minor axis diameter (hereinafter, referred to as particle diameter) is 1.01.
【００２３】平均長軸径が０．００５μｍ未満の場合に
は、粒子の微細化による分子間力の増大により、ビヒク
ル中や樹脂組成物中における分散が困難となり、該赤色
酸化鉄顔料を用いて得られた塗膜や樹脂組成物は、十分
な透明性を有しているとは言い難い。０．１μｍを超え
る場合には、ビヒクル中や樹脂組成物中への分散性は良
いが、粒子が粗大となって着色力が上がり、該赤色酸化
鉄顔料を用いて得られた塗膜や樹脂組成物は、十分な透
明性を有さない。ビヒクル中や樹脂組成物中への分散性
及び得られる塗膜や樹脂組成物の透明性を考慮すれば、
平均長軸径は０．０１〜０．０９μｍが好ましく、より
好ましくは０．０１〜０．０８μｍである。When the average major axis diameter is less than 0.005 μm, dispersion in a vehicle or a resin composition becomes difficult due to an increase in intermolecular force due to finer particles. It is difficult to say that the obtained coating film or resin composition has sufficient transparency. When it exceeds 0.1 μm, the dispersibility in the vehicle or the resin composition is good, but the particles become coarse and the coloring power increases, and the coating film or resin obtained using the red iron oxide pigment is used. The composition does not have sufficient transparency. Considering the dispersibility in the vehicle and the resin composition and the transparency of the resulting coating film and resin composition,
The average major axis diameter is preferably from 0.01 to 0.09 μm, and more preferably from 0.01 to 0.08 μm.
【００２４】本発明に係る微細な赤色酸化鉄顔料の平均
短軸径は０．００２５〜０．０５μｍが好ましく、より
好ましくは０．００５〜０．０４５であって、更に好ま
しくは、０．００５〜０．０４μｍである。The average minor axis diameter of the fine red iron oxide pigment according to the present invention is preferably from 0.0025 to 0.05 μm, more preferably from 0.005 to 0.045, still more preferably from 0.005 to 0.045. ０．０0.04 μm.
【００２５】平均短軸径が０．００２５μｍ未満の場合
には、粒子の微細化による分子間力の増大により、ビヒ
クル中や樹脂組成物中における分散が困難となる。平均
短軸径が０．０５μｍを超えるものは、工業的に得るこ
とが困難である。When the average minor axis diameter is less than 0.0025 μm, dispersion in a vehicle or a resin composition becomes difficult due to an increase in intermolecular force due to finer particles. Those having an average minor axis diameter exceeding 0.05 μm are difficult to obtain industrially.
【００２６】本発明に係る微細な赤色酸化鉄顔料の粒子
形状は、針状である。ここで「針状」とは、文字通りの
針状はもちろん、紡錘状や米粒状などを含む意味であ
る。The fine red iron oxide pigment according to the present invention has a needle-like particle shape. Here, the term "needle-shaped" means not only a needle-like shape in a literal sense but also a spindle-shaped or rice-grained shape.
【００２７】本発明に係る微細な赤色酸化鉄顔料は、軸
比（平均長軸径／平均短軸径）（以下、「軸比」とい
う。）は、２０以下が好ましく、より好ましくは１５以
下、更に好ましくは１０以下であり、その下限値は好ま
しくは２以上である。また、ＢＥＴ比表面積値は、４０
〜２５０ｍ２／ｇが好ましく、より好ましくは５０〜２
２０ｍ２／ｇ、更に好ましくは、７０〜２００ｍ２／ｇ
である。The fine red iron oxide pigment according to the present invention has an axial ratio (average major axis diameter / average minor axis diameter) (hereinafter referred to as “axial ratio”) of preferably 20 or less, more preferably 15 or less. , More preferably 10 or less, and the lower limit thereof is preferably 2 or more. The BET specific surface area value is 40
２５０250 m 2 / g, more preferably 50-2
20 m 2 / g, more preferably 70 to 200 m 2 / g
It is.
【００２８】軸比が２０を超える場合には、ビヒクル中
や樹脂組成物中での粒子の絡み合いが多くなり、分散性
が悪くなったり粘度が増加するため、得られた塗膜及び
樹脂組成物は十分な透明性を有さない。軸比が２未満の
ものは工業的に得ることが困難である。When the axial ratio exceeds 20, the entanglement of the particles in the vehicle or the resin composition increases, the dispersibility deteriorates, and the viscosity increases. Does not have sufficient transparency. Those having an axial ratio of less than 2 are difficult to obtain industrially.
【００２９】ＢＥＴ比表面積値が４０ｍ２／ｇ未満の場
合には、粒子が粗大となって着色力が上がり、該赤色酸
化鉄顔料を用いて得られる塗膜や樹脂組成物は、十分な
透明性を有さない。ＢＥＴ比表面積値が２５０ｍ２／ｇ
を超える場合には、粒子の微細化による分子間力の増大
により、ビヒクル中や樹脂組成物中における分散が困難
となる。When the BET specific surface area is less than 40 m 2 / g, the particles become coarse and the coloring power increases, and the coating film and the resin composition obtained by using the red iron oxide pigment have a sufficient transparency. Has no nature. BET specific surface area value of 250 m 2 / g
In the case where the particle size exceeds, dispersion in a vehicle or a resin composition becomes difficult due to an increase in intermolecular force due to finer particles.
【００３０】本発明に係る微細な赤色酸化鉄顔料は、必
要により、粒子内部に微細な赤色酸化鉄顔料に対してＡ
ｌ換算で０．０５〜５０重量％のアルミニウムを含有し
ていてもよく、粒子内部にアルミニウムを含有していな
いものに比べて粒子自体の透明性が優れるとともに、該
微細な赤色酸化鉄顔料を用いて得られた樹脂組成物の耐
老化性が改善される。The fine red iron oxide pigment according to the present invention, if necessary, has a fine red iron oxide pigment having an A
It may contain 0.05 to 50% by weight of aluminum in terms of l, the transparency of the particles themselves is excellent as compared with those not containing aluminum inside the particles, and the fine red iron oxide pigment is The aging resistance of the obtained resin composition is improved.
【００３１】微細な赤色酸化鉄顔料の粒子内部に含有さ
れているアルミニウム量が微細な赤色酸化鉄顔料に対し
て０．０５重量％未満の場合には、透明性及び耐老化性
を改善する効果が得られない。５０重量％を超える場合
には、得られた赤色酸化鉄顔料は、十分な透明性と耐老
化性を有しているが、効果が飽和するため必要以上に含
有させる意味がない。得られる微細な赤色酸化鉄顔料の
透明性や耐老化性の向上効果及び生産性を考慮すれば、
粒子内部に含有されているアルミニウム量は、微細な赤
色酸化鉄顔料に対してＡｌ換算で０．１〜４０重量％が
好ましい。When the amount of aluminum contained in the particles of the fine red iron oxide pigment is less than 0.05% by weight based on the fine red iron oxide pigment, the effect of improving transparency and aging resistance is obtained. Can not be obtained. When the content exceeds 50% by weight, the obtained red iron oxide pigment has sufficient transparency and aging resistance, but the effect is saturated and there is no point in containing more than necessary. Considering the effect of improving the transparency and aging resistance of the obtained fine red iron oxide pigment and productivity,
The amount of aluminum contained in the particles is preferably from 0.1 to 40% by weight in terms of Al with respect to the fine red iron oxide pigment.
【００３２】粒子内部に含有されているアルミニウム
は、粒子の中心部から粒子表面に至るまでアルミニウム
が実質的に均一に含有されていることが好ましい。It is preferable that the aluminum contained in the particle contains aluminum substantially uniformly from the center of the particle to the surface of the particle.
【００３３】本発明に係る粒子内部にアルミニウムを含
有している微細な赤色酸化鉄顔料は、粒子内部にアルミ
ニウムを含有していない本発明に係る微細な赤色酸化鉄
顔料の場合とほぼ同程度の粒子サイズ、粒子径の幾何標
準偏差値、軸比及びＢＥＴ比表面積値を有している。The fine red iron oxide pigment containing aluminum inside the particles according to the present invention has almost the same degree as the fine red iron oxide pigment according to the present invention containing no aluminum inside the particles. It has a particle size, a geometric standard deviation value of a particle diameter, an axial ratio, and a BET specific surface area value.
【００３４】本発明に係る微細な赤色酸化鉄顔料は、必
要により、粒子表面がアルミニウムの水酸化物、アルミ
ニウムの酸化物、ケイ素の水酸化物及びケイ素の酸化物
から選ばれた少なくとも１種からなる表面被覆物によっ
て被覆されていてもよく、粒子表面を表面被覆物で被覆
しない場合に比べ、分散性及び得られた樹脂組成物の耐
老化性が向上する。The fine red iron oxide pigment according to the present invention, if necessary, has a particle surface made of at least one selected from the group consisting of aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. And the dispersibility and the aging resistance of the obtained resin composition are improved as compared with the case where the particle surface is not coated with the surface coating.
【００３５】前記表面被覆物の被覆量は、微細な赤色酸
化鉄顔料に対してＡｌ換算、ＳｉＯ ２換算、又はＡｌ換
算量とＳｉＯ２換算量との総和で０．０１〜２０重量％
が好ましい。表面被覆物の被覆量が０．０１重量％未満
である場合には、分散性及び耐老化性向上効果が得られ
ない。２０重量％を超える場合には、十分な分散性及び
耐老化性向上効果が得られるが、必要以上に添加する意
味がない。得られる微細な赤色酸化鉄顔料の分散性、耐
老化性向上効果及び生産性を考慮すれば、表面被覆物の
被覆量は、微細な赤色酸化鉄顔料に対してＡｌ換算、Ｓ
ｉＯ２換算又はＡｌ換算とＳｉＯ２換算との総和で０．
０５〜１５重量％が好ましい。The amount of the surface coating is fine red acid.
Al conversion for iron oxide pigment, SiO 2Conversion or Al conversion
Math and SiO20.01 to 20% by weight in total with converted amount
Is preferred. Less than 0.01% by weight of surface coating
In the case of, the effect of improving dispersibility and aging resistance is obtained.
Absent. If it exceeds 20% by weight, sufficient dispersibility and
Although the effect of improving aging resistance can be obtained,
There is no taste. Dispersibility and resistance of the obtained fine red iron oxide pigment
Considering the aging improvement effect and productivity, the surface coating
The coating amount is expressed in terms of Al for the fine red iron oxide pigment.
iO2Conversion or Al conversion and SiO2It is 0 in total with conversion.
It is preferably from 0.5 to 15% by weight.
【００３６】本発明に係る表面被覆物で被覆されている
微細な赤色酸化鉄顔料は、表面被覆物で被覆されていな
い本発明に係る微細な赤色酸化鉄顔料とほぼ同程度の粒
子サイズ、粒子径の幾何標準偏差値、軸比及びＢＥＴ比
表面積値を有している。The fine red iron oxide pigment coated with the surface coating according to the present invention has a particle size and particle size substantially equal to the fine red iron oxide pigment according to the present invention not coated with the surface coating. It has the geometric standard deviation value of the diameter, the axial ratio and the BET specific surface area value.
【００３７】次に、本発明に係る微細な赤色酸化鉄顔料
の製造法について述べる。Next, a method for producing the fine red iron oxide pigment according to the present invention will be described.
【００３８】本発明に係る微細な赤色酸化鉄顔料は、第
一鉄塩と水酸化アルカリ水溶液、炭酸アルカリ水溶液又
は水酸化アルカリ・炭酸アルカリ水溶液のいずれかの水
溶液を用いて反応して得られる鉄含有沈殿物を含む懸濁
液に空気等の酸素含有ガスを通気して得られるゲータイ
ト微粒子粉末を、２５０〜５００℃の温度範囲で加熱脱
水処理するに先立ってあらかじめ、１００〜２００℃の
温度範囲で加熱処理することにより得られる。The fine red iron oxide pigment according to the present invention is obtained by reacting a ferrous salt with an aqueous solution of an alkali hydroxide solution, an alkali carbonate solution or an alkali hydroxide / alkali carbonate solution. Prior to subjecting the goethite fine particle powder obtained by aerating an oxygen-containing gas such as air to the suspension containing the contained precipitate to heat dehydration at a temperature of 250 to 500 ° C, a temperature range of 100 to 200 ° C is set in advance. Obtained by heat treatment.
【００３９】本発明における出発原料粒子粉末として用
いるゲータイト微粒子粉末としては、通常、長軸径の幾
何標準偏差値は１．８以下であって、短軸径の幾何標準
偏差値は１．７以下であって、平均長軸径が０．００５
〜０．１μｍ、平均短軸径が０．００２５〜０．０５μ
ｍであるものを用いることが好ましい。The goethite fine particle powder used as the starting material particle powder in the present invention usually has a major axis diameter of 1.8 or less and a minor axis diameter of 1.7 or less. Having an average major axis diameter of 0.005
~ 0.1μm, average minor axis diameter 0.0025 ~ 0.05μ
Preferably, m is used.
【００４０】加熱処理温度が１００℃未満の場合、ゲー
タイト超微粒子を十分にゲータイト微粒子に吸収させる
ことが困難であり、殊に短軸径の粒度が均斉な粒子を得
ることができない。２００℃を超える場合、ゲータイト
超微粒子成分（平均長軸径０．００１μｍ以下）が存在
したままゲータイト微粒子の脱水が始まるため、粒子間
で焼結が起こり、殊に短軸径の粒度が均斉な粒子を得る
ことができない。好ましくは、１２０〜２００℃であ
る。When the heat treatment temperature is lower than 100 ° C., it is difficult to sufficiently absorb goethite ultrafine particles into the goethite fine particles, and in particular, it is not possible to obtain particles having a uniform short axis diameter. When the temperature exceeds 200 ° C., dehydration of goethite fine particles starts in the presence of ultra-fine goethite particles (average major axis diameter of 0.001 μm or less). No particles can be obtained. Preferably, it is 120 to 200 ° C.
【００４１】加熱処理の時間は、５〜６０分が好まし
い。The time of the heat treatment is preferably 5 to 60 minutes.
【００４２】１００〜２００℃の温度範囲で加熱処理し
て得られるゲータイト微粒子粉末は、長軸径の幾何標準
偏差値は１．５以下であって、短軸径の幾何標準偏差値
は１．３以下であり、平均長軸径が０．００５〜０．１
μｍ、平均短軸径が０．００２５〜０．０５μｍであ
る。The goethite fine-particle powder obtained by heat treatment in a temperature range of 100 to 200 ° C. has a geometric standard deviation of a major axis of 1.5 or less and a geometric standard deviation of a minor axis of 1. 3 or less, and the average major axis diameter is 0.005 to 0.1.
μm, and the average minor axis diameter is 0.0025 to 0.05 μm.
【００４３】加熱脱水処理の温度が２５０℃未満の場合
には、脱水反応に長時間を要する。加熱脱水温度が５０
０℃を超える場合には、脱水反応が急激に生起し、粒子
の形状が崩れやすくなったり、粒子間の焼結を引き起こ
しやすくなる。When the temperature of the heat dehydration treatment is lower than 250 ° C., a long time is required for the dehydration reaction. Heat dehydration temperature is 50
When the temperature exceeds 0 ° C., a dehydration reaction rapidly occurs, and the shape of the particles is easily broken or sintering between the particles is easily caused.
【００４４】尚、粒子内部にアルミニウムを含有する本
発明に係る微細な赤色酸化鉄顔料は、前記ゲータイト微
粒子の生成反応において、空気等の酸素含有ガスを通気
する前にアルミニウム化合物を存在させておくことによ
り得られ、粒子内部にアルミニウムを実質的に均一に含
有しているゲータイト微粒子を１００〜２００℃の温度
範囲で加熱処理した後、２５０〜５００℃の温度範囲で
加熱脱水することにより得ることができる。In the fine red iron oxide pigment according to the present invention containing aluminum inside the particles, an aluminum compound is allowed to exist before aeration with an oxygen-containing gas such as air in the above-mentioned reaction for producing goethite fine particles. Obtained by heat-treating goethite fine particles substantially uniformly containing aluminum inside the particles in a temperature range of 100 to 200 ° C., and then performing heat dehydration in a temperature range of 250 to 500 ° C. Can be.
【００４５】アルミニウム化合物の添加は、具体的に
は、第一鉄塩水溶液、アルカリ水溶液及び空気等の酸素
含有ガスを通気する前の鉄含有沈殿物を含む懸濁液のい
ずれかの溶液中に添加すればよく、第一鉄塩水溶液に添
加することが好ましい。Specifically, the addition of the aluminum compound may be carried out in any solution of a ferrous salt aqueous solution, an alkaline aqueous solution, or a suspension containing an iron-containing precipitate before passing an oxygen-containing gas such as air. What is necessary is just to add, and it is preferable to add to an aqueous ferrous salt solution.
【００４６】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
ができる。Examples of the aluminum compound to be added include alkali aluminates such as sodium aluminate, aluminum sulfate, aluminum chloride, aluminum acetate, and the like.
Aluminum salts such as aluminum nitrate can be used.
【００４７】アルミニウム化合物の添加量は、第一鉄塩
水溶液中のＦｅに対し、Ａｌ換算で０．５〜３５０ｍｏ
ｌ％が好ましい。０．５ｍｏｌ％未満である場合には、
本発明の目的とする透明性や耐老化性向上の効果が得ら
れない。３５０ｍｏｌ％を超える場合には、効果がほぼ
飽和に達するため、必要以上に添加する意味がない。The amount of the aluminum compound added is 0.5 to 350 mol in terms of Al with respect to Fe in the aqueous ferrous salt solution.
1% is preferred. If less than 0.5 mol%,
The effect of improving transparency and aging resistance, which is the object of the present invention, cannot be obtained. If it exceeds 350 mol%, the effect almost reaches saturation, and there is no point in adding more than necessary.
【００４８】本発明において、必要により更に、アルミ
ニウムの水酸化物、アルミニウムの酸化物、ケイ素の水
酸化物及びケイ素の酸化物から選ばれる少なくとも１種
以上の表面被覆物で被覆してもよい。In the present invention, if necessary, it may be coated with at least one or more surface coatings selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide.
【００４９】アルミニウム化合物の添加量は、微細な赤
色酸化鉄顔料に対してＡｌ換算で０．０１〜２０重量％
である。０．０１重量％未満である場合には、分散性及
び耐老化性の向上効果が得られるだけの十分な量のアル
ミニウムの水酸化物等を粒子表面に被覆することが困難
である。２０重量％を超える場合には、被覆効果が飽和
するため、必要以上に添加する意味が無い。The addition amount of the aluminum compound is 0.01 to 20% by weight in terms of Al with respect to the fine red iron oxide pigment.
It is. If the amount is less than 0.01% by weight, it is difficult to coat the surface of the particles with a sufficient amount of aluminum hydroxide or the like to obtain the effect of improving dispersibility and aging resistance. If it exceeds 20% by weight, the coating effect is saturated, and it is meaningless to add more than necessary.
【００５０】ケイ素化合物の添加量は、微細な赤色酸化
鉄顔料に対してＳｉＯ２換算で０．０１〜２０重量％で
ある。０．０１重量％未満である場合には、分散性及び
耐老化性の向上効果が得られるだけの十分な量のケイ素
の酸化物等を粒子表面に被覆することが困難である。２
０重量％を超える場合には、被覆効果が飽和するため、
必要以上に添加する意味が無い。The addition amount of the silicon compound is 0.01 to 20% by weight in terms of SiO 2 based on the fine red iron oxide pigment. If the amount is less than 0.01% by weight, it is difficult to coat the surface of the particles with a sufficient amount of silicon oxide or the like to obtain an effect of improving dispersibility and aging resistance. 2
If it exceeds 0% by weight, the coating effect is saturated,
There is no point in adding more than necessary.
【００５１】アルミニウム化合物とケイ素化合物とを併
せて使用する場合の添加量は、微細な赤色酸化鉄顔料に
対し、Ａｌ換算量とＳｉＯ２換算量との総和で０．０１
〜２０重量％が好ましい。When the aluminum compound and the silicon compound are used in combination, the amount of addition is 0.01 to the fine red iron oxide pigment in terms of the total amount in terms of Al and SiO 2 with respect to the fine red iron oxide pigment.
-20% by weight is preferred.
【００５２】次に、本発明に係る微細な赤色酸化鉄顔料
を用いた塗料について述べる。Next, a paint using the fine red iron oxide pigment according to the present invention will be described.
【００５３】本発明に係る微細な赤色酸化鉄顔料を用い
た塗料は、塗膜にした場合、光沢度は８０％以上であっ
て、塗膜の透明性は線吸収係数が０．１μｍ−１以下で
ある。The coating composition using the fine red iron oxide pigment according to the present invention, when formed into a coating film, has a gloss of 80% or more, and the transparency of the coating film has a linear absorption coefficient of 0.1 μm −1. It is as follows.
【００５４】本発明における微細な赤色酸化鉄顔料と塗
料構成基材との配合割合は、微細な赤色酸化鉄顔料を塗
料構成基材１００重量部に対し０．５〜１００重量部の
範囲で使用することができ、塗料のハンドリングを考慮
すれば、好ましくは１．０〜８０重量部、更に好ましく
は１．０〜５０重量部である。In the present invention, the mixing ratio of the fine red iron oxide pigment to the paint base material is such that the fine red iron oxide pigment is used in the range of 0.5 to 100 parts by weight based on 100 parts by weight of the paint base material. The amount is preferably 1.0 to 80 parts by weight, more preferably 1.0 to 50 parts by weight, in consideration of the handling of the paint.
【００５５】塗料構成基材は、樹脂及び溶剤と、必要に
より添加される消泡剤、体質顔料、乾燥促進剤、界面活
性剤、硬化促進剤、助剤等からなる。The paint-constituting base material comprises a resin and a solvent, and if necessary, an antifoaming agent, an extender, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent and the like.
【００５６】樹脂としては、溶剤系塗料用として通常使
用されるアクリル樹脂、アルキッド樹脂、ポリエステル
樹脂、ポリウレタン樹脂、エポキシ樹脂、フェノール樹
脂、メラミン樹脂、アミノ樹脂等、並びに、水系塗料用
として、通常使用される水溶性アルキッド樹脂、水溶性
メラミン樹脂、水溶性アクリル樹脂、水溶性ウレタンエ
マルジョン樹脂等を用いることができる。Resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, epoxy resins, phenolic resins, melamine resins, amino resins, etc., which are usually used for solvent-based coatings, and water-based coatings. Water-soluble alkyd resin, water-soluble melamine resin, water-soluble acrylic resin, water-soluble urethane emulsion resin and the like can be used.
【００５７】溶剤としては、溶剤系塗料用として通常使
用されるトルエン、キシレン、ブチルアセテート、メチ
ルアセテート、メチルイソブチルケトン、ブチルセロソ
ルブ、エチルセロソルブ、ブチルアルコール、脂肪族炭
化水素等、並びに、水系塗料用溶剤としては水と水系塗
料で通常使用されるブチルセロソルブ、ブチルアルコー
ル等を用いることができる。Examples of the solvent include toluene, xylene, butyl acetate, methyl acetate, methyl isobutyl ketone, butyl cellosolve, ethyl cellosolve, butyl alcohol, aliphatic hydrocarbons, etc., which are usually used for solvent-based paints. For example, butyl cellosolve, butyl alcohol and the like which are usually used in water and water-based paints can be used.
【００５８】尚、消泡剤としては、ノプコ８０３４（商
品名）、ＳＮデフォーマー４７７（商品名）、ＳＮデフ
ォーマー５０１３（商品名）、ＳＮデフォーマー３８２
（商品名）、ＳＮデフォーマー２４７（商品名）、ＳＮ
デフォーマー３８２（商品名）（以上、いずれもサンノ
プコ株式会社製）アンチホーム０８（商品名）、エマル
ゲン９０３（商品名）（以上、いずれも花王株式会社
製）等の市販品を用いることができる。As defoaming agents, Nopco 8034 (trade name), SN deformer 477 (trade name), SN deformer 5013 (trade name), SN deformer 382
(Product Name), SN Deformer 247 (Product Name), SN
Commercial products such as Deformer 382 (trade name) (both manufactured by San Nopco Co., Ltd.) AntiHome 08 (trade name) and Emulgen 903 (trade name) (both manufactured by Kao Corporation) can be used.
【００５９】次に、本発明に係る微細な赤色酸化鉄顔料
を用いた樹脂組成物について述べる。Next, a resin composition using the fine red iron oxide pigment according to the present invention will be described.
【００６０】本発明に係る微細な赤色酸化鉄顔料を用い
た樹脂組成物は、透明性は線吸収係数で０．１５μｍ
−１以下であって、分散状態は後出評価法による３以
上、好ましくは４、更に好ましくは５を有している。The resin composition using the fine red iron oxide pigment according to the present invention has a transparency of 0.15 μm in linear absorption coefficient.
-1 or less, and the dispersion state is 3 or more, preferably 4, and more preferably 5, according to the below-mentioned evaluation method.
【００６１】本発明に係る粒子内部にアルミニウムを含
有している微細な赤色酸化鉄顔料又は粒子表面を表面被
覆物で被覆されている微細な赤色酸化鉄顔料を用いた樹
脂組成物は、透明性は線吸収係数で０．１μｍ−１以下
であって、分散状態は後出評価法による４以上、好まし
くは５を有している。また、耐老化性はアルミニウムを
含有していないとともに粒子表面が表面被覆物で被覆さ
れていない微細な赤色酸化鉄顔料を用いた樹脂組成物
（耐老化性は１０分間加熱した場合、Ｓ／Ｓ０が１０％
以上である）に比べて、９０分間加熱した場合でもＳ／
Ｓ０１０％以下と改善されたものである。The resin composition according to the present invention using the fine red iron oxide pigment containing aluminum inside the particle or the fine red iron oxide pigment whose particle surface is coated with a surface coating is transparent. Has a linear absorption coefficient of 0.1 μm −1 or less, and has a dispersion state of 4 or more, preferably 5, according to the evaluation method described later. The aging resistance is a resin composition using a fine red iron oxide pigment which does not contain aluminum and whose particle surface is not coated with a surface coating (the aging resistance is S / S when heated for 10 minutes. 0 is 10%
Compared to the above), even when heated for 90 minutes, S /
S 0 is improved to 10% or less.
【００６２】本発明における微細な赤色酸化鉄顔料の配
合割合は、樹脂１００重量部に対し０．０１〜５０重量
部の範囲で使用することができ、樹脂組成物のハンドリ
ングを考慮すれば、好ましくは０．０５〜４５重量部、
更に好ましくは、０．１〜４０重量部である。The compounding ratio of the fine red iron oxide pigment in the present invention can be used in the range of 0.01 to 50 parts by weight with respect to 100 parts by weight of the resin, and is preferable in consideration of the handling of the resin composition. Is 0.05 to 45 parts by weight,
More preferably, it is 0.1 to 40 parts by weight.
【００６３】樹脂としては、天然ゴム、合成ゴム、熱可
塑性樹脂（例えば、ポリエチレン、ポリプロピレン、ポ
リブテン、ポリイソブチレン等のポリオレフィン、ポリ
塩化ビニル、スチレン重合体、ポリアミド等）等を用い
ることができ、必要により、滑剤、可塑剤、酸化防止
剤、紫外線吸収剤、各種安定剤等の添加剤が配合でき
る。As the resin, natural rubber, synthetic rubber, thermoplastic resin (eg, polyolefin such as polyethylene, polypropylene, polybutene, polyisobutylene, polyvinyl chloride, styrene polymer, polyamide, etc.) can be used. Thus, additives such as a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, and various stabilizers can be compounded.
【００６４】添加剤の量は、微細な赤色酸化鉄顔料と樹
脂との総和に対して５０重量％以下であればよい。添加
剤の含有量が５０重量％を超える場合には、成形性が低
下する。The amount of the additive may be 50% by weight or less based on the total of the fine red iron oxide pigment and the resin. When the content of the additive exceeds 50% by weight, the moldability decreases.
【００６５】本発明に係る樹脂組成物は、樹脂と微細な
赤色酸化鉄顔料をあらかじめよく混合し、次に、混練機
もしくは押出機を用いて加熱下で強いせん断作用を加え
て、微細な赤色酸化鉄顔料の凝集体を破壊し、樹脂組成
物中に微細な赤色酸化鉄顔料を均一に分散させた後、目
的に応じた形状に成形加工して使用する。The resin composition according to the present invention is obtained by mixing a resin and a fine red iron oxide pigment well in advance, and then applying a strong shearing action under heating using a kneader or an extruder to obtain a fine red iron oxide pigment. After breaking down the aggregates of the iron oxide pigment and uniformly dispersing the fine red iron oxide pigment in the resin composition, the resin composition is molded into a desired shape and used.
【００６６】[0066]
【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.
【００６７】粒子の平均長軸径及び平均短軸径は、電子
顕微鏡写真（×３０，０００）を縦方向及び横方向にそ
れぞれ４倍に拡大した写真に示される粒子約３５０個に
ついて、長軸径及び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 average minor axis diameter of the particles were determined by measuring the major axis of about 350 particles shown in an electron micrograph (× 30,000) enlarged four times in the vertical and horizontal directions, respectively. The diameter and the minor axis diameter were measured, respectively, and the average value was shown.
【００６８】粒子の軸比は平均長軸径と平均短軸径との
比を計算することによって求めた。The axial ratio of the particles was determined by calculating the ratio between the average major axis diameter and the average minor axis diameter.
【００６９】粒子の長軸径及び短軸径（以下、粒子径と
いう）の幾何標準偏差値は下記の方法により求めた値で
示した。即ち、上記拡大写真に示される粒子の粒子径を
測定した値を、その測定値から計算して求めた粒子の実
際の粒子径と個数から、統計学的手法に従って、対数正
規確率紙上の横軸に粒子径を、縦軸に所定の粒子径区間
のそれぞれに属する粒子の累積個数（積算フルイ下）を
百分率でプロットした。そしてこのグラフから粒子の累
積個数が５０％及び８４．１３％のそれぞれに相当する
粒子径の値を読み取り、幾何標準偏差値＝（積算フルイ
下８４．１３％における粒子径）／（積算フルイ下５０
％における粒子径（幾何平均径）に従って算出した値で
示した。幾何標準偏差値が１に近いほど、粒子の粒子径
の粒度が優れていることを意味する。The geometric standard deviation values of the major axis diameter and the minor axis diameter (hereinafter, referred to as particle diameter) of the particles were shown by values obtained by the following method. In other words, the value obtained by measuring the particle size of the particles shown in the above enlarged photograph, the actual particle size and the number of particles calculated from the measured values, according to a statistical method, the horizontal axis on the lognormal probability paper , And the vertical axis plots the cumulative number of particles belonging to each of the predetermined particle diameter sections (under the integrated screen) in percentage. Then, the value of the particle diameter corresponding to the cumulative number of particles of 50% and 84.13% is read from this graph, and the geometric standard deviation value = (particle diameter at 84.13% under the integrated screen) / (under the integrated screen) 50
% In accordance with the particle diameter (geometric mean diameter). The closer the geometric standard deviation value is to 1, the better the particle size of the particles is.
【００７０】比表面積値はＢＥＴ法により測定した値で
示した。The specific surface area was indicated by a value measured by the BET method.
【００７１】粒子に含有されているＡｌ量及びＳｉ量
は、「蛍光Ｘ線分析装置３０６３Ｍ型」（理学電機工業
（株）製）を使用し、ＪＩＳ Ｋ０１１９の「けい光Ｘ
線分析通則」に従って測定した。The amount of Al and the amount of Si contained in the particles were determined using “Fluorescence X-ray Analyzer 3063M” (manufactured by Rigaku Corporation) and “Fluorescent X” of JIS K0119.
It was measured in accordance with "General rules for line analysis".
【００７２】赤色酸化鉄顔料を用いた塗膜の透明性は、
後述する処法によって調製した塗料を厚さ１００μｍの
クリアベースフィルムに塗布して得られた塗布膜につい
て、樹脂組成物の透明性は後述する組成から成る樹脂プ
レートについて、「自記光電分光光度計ＵＶ−２１０
０」（（株）島津製作所製）を用いて測定した光透過率
から、次式によって定義される線吸収係数で示した。線
吸収係数は値が小さいほど光を透しやすく透明性が高い
ことを示す。 線吸収係数（μｍ−１）＝ｌｎ（１／ｔ）／ＦＴ ｔ：λ＝９００ｎｍにおける光透過率（−）The transparency of the coating film using the red iron oxide pigment is as follows:
For a coating film obtained by applying a paint prepared by the processing method described later on a clear base film having a thickness of 100 μm, the transparency of the resin composition was determined for a resin plate having a composition described later by referring to “Self-recording photoelectric spectrophotometer UV. −210
The light transmittance measured using "0" (manufactured by Shimadzu Corporation) was represented by a linear absorption coefficient defined by the following equation. The smaller the linear absorption coefficient, the higher the transmittance of light and the higher the transparency. Linear absorption coefficient (μm −1 ) = ln (1 / t) / FT t: light transmittance at λ = 900 nm (−)
【００７３】耐老化性は、後述する組成からなる赤色酸
化鉄顔料を練り込んだ着色プレート（縦１．５ｃｍ×横
１．５ｃｍ×厚み１ｍｍ）を１９０℃で加熱した時に、
変色して樹脂が劣化した部分の面積Ｓと加熱前の着色プ
レートの面積Ｓ０（１．５ｃｍ×１．５ｃｍ＝２．２５
ｃｍ２）との比Ｓ／Ｓ０を５％刻みで定量することによ
り求めた。The aging resistance was determined by heating a colored plate (1.5 cm long × 1.5 cm wide × 1 mm thick) kneaded with a red iron oxide pigment having the composition described below at 190 ° C.
The area S of the portion where the resin is deteriorated due to discoloration and the area S 0 of the colored plate before heating (1.5 cm × 1.5 cm = 2.25)
cm 2 ) was determined by quantifying the ratio S / S 0 in steps of 5%.
【００７４】即ち、（Ｓ／Ｓ０）×１００が０％の時は
劣化が無い状態を示し、（Ｓ／Ｓ０）×１００が１００
％のときは樹脂が完全に劣化した状態を示す。That is, when (S / S 0 ) × 100 is 0%, there is no deterioration, and (S / S 0 ) × 100 is 100%.
% Indicates that the resin is completely degraded.
【００７５】ビヒクル中への分散性は、後述する処法に
よって調整した塗料を用いて得られた塗布膜について、
塗布面の光沢度の大小によって調べた。The dispersibility in the vehicle was determined for the coating film obtained using the coating material adjusted by the treatment method described below.
It was examined according to the degree of glossiness of the coated surface.
【００７６】光沢度は、「グロスメーター ＵＧＶ−５
Ｄ」（スガ試験機（株）製）を用いて入射角２０°のと
きの光沢度を測定して求めた。光沢度が高いほど、ビヒ
クル中における微細な赤色酸化鉄顔料の粒子の分散性が
良いことを示す。The gloss was measured using a gloss meter “UGV-5”.
D "(manufactured by Suga Test Instruments Co., Ltd.), and the gloss was measured at an incident angle of 20 °. The higher the gloss, the better the dispersibility of the fine red iron oxide pigment particles in the vehicle.
【００７７】塗料粘度については、後述する処方によっ
て調製した塗料の２５℃における塗料粘度をＥ型粘度計
（コーンプレート型粘度計）ＥＭＤ−Ｒ（（株）東京計
器製）を用いて、ずり速度Ｄ＝１．９２ ｓｅｃ−１に
おける値を求めた。With respect to the paint viscosity, the paint viscosity at 25 ° C. of the paint prepared according to the formulation described below was measured using a E-type viscometer (cone plate viscometer) EMD-R (manufactured by Tokyo Keiki Co., Ltd.). The value at D = 1.92 sec -1 was determined.
【００７８】樹脂組成物中への分散性は、得られた樹脂
組成物表面における未分散の凝集粒子の個数を目視によ
り判定し、５段階で評価した。５が最も分散状態が良い
ことを示す。 ５： 未分散物認められず、 ４： １ｃｍ２当たりに１個以上５個未満、 ３： １ｃｍ２当たりに５個以上１０個未満、 ２： １ｃｍ２当たりに１０個以上５０個未満、 １： １ｃｍ２当たりに５０個以上。The dispersibility in the resin composition was evaluated on the basis of the number of undispersed agglomerated particles on the surface of the obtained resin composition, and evaluated in five steps. 5 indicates that the dispersion state is the best. 5: not observed undispersed material, 4: 1 cm 1 or more than five per 2, 3: 1 cm less than 10 5 or more per 2, 2: 1 cm less than 50 10 or more per 2, 1: 50 or more per 1cm 2.
【００７９】＜微細な赤色酸化鉄顔料の製造＞硫酸第一
鉄水溶液と炭酸ナトリウム水溶液とを用いて得られた針
状ゲータイト微粒子粉末のスラリーを、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た。<Production of Fine Red Iron Oxide Pigment> A slurry of acicular goethite fine particle powder obtained using an aqueous ferrous sulfate solution and an aqueous sodium carbonate solution was separated by filtration using a press filter, and water was passed through. While washing thoroughly.
【００８０】湿ケーキを１２０℃で２４時間乾燥させた
後、自由粉砕機Ｍ−２型（（株）奈良機械製作所製）で
粉砕した。得られたゲータイト微粒子粉末は、平均長軸
径０．０６８８μｍ、長軸径の幾何標準偏差値１．５
３、平均短軸径０．０１０１μｍ、短軸径の幾何標準偏
差値１．３３、軸比６．８、ＢＥＴ比表面積値１６５．
３ｍ２／ｇであった。After the wet cake was dried at 120 ° C. for 24 hours, it was pulverized with a free pulverizer M-2 (manufactured by Nara Machinery Co., Ltd.). The obtained goethite fine particle powder had an average major axis diameter of 0.0688 μm, and a geometric standard deviation of the major axis diameter of 1.5.
3. Average minor axis diameter 0.0101 μm, geometric standard deviation of minor axis diameter 1.33, axial ratio 6.8, BET specific surface area value 165.
It was 3 m 2 / g.
【００８１】得られたゲータイト微粒子粉末を金属製の
熱処理炉に入れ、１５０℃で３０分間加熱処理を行い、
ゲータイト微粒子粉末中に含まれるゲータイト超微粒子
をゲータイト微粒子に吸収させた。The obtained goethite fine particle powder was placed in a heat treatment furnace made of metal, and heat-treated at 150 ° C. for 30 minutes.
The goethite ultrafine particles contained in the goethite fine particle powder were absorbed by the goethite fine particles.
【００８２】次いで、得られたゲータイト微粒子粉末を
再度、金属製の熱処理炉に入れ、３４０℃で３０分間加
熱脱水処理を行い、ゲータイト微粒子を脱水して、微細
な赤色酸化鉄顔料を得た。得られた微細な赤色酸化鉄顔
料は、平均長軸径０．０６２０μｍ、長軸径の幾何標準
偏差値１．３３、平均短軸径０．０１０８μｍ、短軸径
の幾何標準偏差値１．１５、軸比５．７、ＢＥＴ比表面
積値１４３．８ｍ２／ｇであった。Next, the obtained goethite fine particle powder was again placed in a metal heat treatment furnace and subjected to a heat dehydration treatment at 340 ° C. for 30 minutes to dehydrate the goethite fine particles to obtain a fine red iron oxide pigment. The resulting fine red iron oxide pigment had an average major axis diameter of 0.0620 μm, a major axis diameter of geometric standard deviation of 1.33, an average minor axis diameter of 0.0108 μm, and a minor axis diameter of 1.15 μm. , The axial ratio was 5.7, and the BET specific surface area was 143.8 m 2 / g.
【００８３】＜微細な赤色酸化鉄顔料を用いた塗料の製
造＞２５０ｍｌのガラスビンに前記微細な赤色酸化鉄顔
料５ｇを用い、塗料組成を下記割合で配合して３ｍｍφ
ガラスビーズ１６０ｇとともにペイントシェーカーで１
２０分間混合分散し、ミルベースを作製した。 微細な赤色酸化鉄顔料 ９．９ 重量部、 メラミン樹脂 １９．８ 重量部、 （スーパーペッカミン Ｊ−８２０−６０：商品名：大日本インキ化学工業（ 株）製） アルキッド樹脂 ３９．６ 重量部、 （ベッコゾール １３０７−６０ＥＬ：商品名：大日本インキ化学工業（株）製 ） キシレン ２９．７ 重量部、 ブタノール １．０ 重量部。<Production of Coating Using Fine Red Iron Oxide Pigment> In a 250 ml glass bottle, 5 g of the fine red iron oxide pigment was used, and the coating composition was mixed at the following ratio to obtain 3 mmφ.
1 with a paint shaker with 160g of glass beads
The mixture was mixed and dispersed for 20 minutes to prepare a mill base. 9.9 parts by weight of fine red iron oxide pigment, 19.8 parts by weight of melamine resin, (Super Peckamine J-820-60: trade name: manufactured by Dainippon Ink and Chemicals, Inc.) 39.6 parts by weight of alkyd resin (Beccosol 1307-60EL: trade name: manufactured by Dainippon Ink and Chemicals, Inc.) 29.7 parts by weight of xylene, 1.0 part by weight of butanol.
【００８４】この塗料を透明ガラス板（０．８ｍｍ
（厚）×７０ｍｍ（幅）×１５０ｍｍ（長さ））に塗布
して得られた塗膜の光沢度は９３％、線吸収係数は０．
０５２８μｍ−１であった。This paint was applied to a transparent glass plate (0.8 mm
(Thickness) × 70 mm (width) × 150 mm (length)), the glossiness of the coating film obtained was 93%, and the linear absorption coefficient was 0.
0528 μm −1 .
【００８５】＜微細な赤色酸化鉄顔料を用いた樹脂組成
物の製造＞前記微細な赤色酸化鉄顔料０．５ｇとポリ塩
化ビニル樹脂粉末（１０３ＥＰ８Ｄ：商品記号：日本ゼ
オン（株）製）４９．５ｇとを秤量し、これらを１００
ｍｌポリビーカーに入れ、スパチュラでよく混合して混
合粉末を得た。<Production of Resin Composition Using Fine Red Iron Oxide Pigment> 0.5 g of the fine red iron oxide pigment and polyvinyl chloride resin powder (103EP8D: trade name: manufactured by Nippon Zeon Co., Ltd.) 5 g, and weigh these with 100
The mixture was placed in a ml polybeaker and mixed well with a spatula to obtain a mixed powder.
【００８６】得られた混合粉末にステアリン酸カルシウ
ムを１．０ｇ加えて混合し、１６０℃に加熱した熱間ロ
ールのクリアランスを０．２ｍｍに設定した後、上記混
合粉末を少しずつロールにて練り込んで樹脂組成物が一
体となるまで混練を続けた後、樹脂組成物をロールから
剥離して着色樹脂プレート原料として用いた。After adding 1.0 g of calcium stearate to the obtained mixed powder and mixing the mixture, the clearance of a hot roll heated to 160 ° C. was set to 0.2 mm, and the mixed powder was kneaded little by little with a roll. After the kneading was continued until the resin composition was integrated, the resin composition was peeled off from a roll and used as a colored resin plate raw material.
【００８７】次に、表面研磨されたステンレス板の間に
上記樹脂組成物を挟んで１８０℃に加熱したホットプレ
ス内に入れ、１トン／ｃｍ２の圧力で加圧成形して厚さ
１ｍｍの着色樹脂プレートを得た。得られた着色樹脂プ
レートの線吸収係数は０．０８５３μｍ−１、分散状態
は４であった。Next, the above resin composition was sandwiched between stainless steel plates whose surfaces were polished, placed in a hot press heated to 180 ° C., and pressed under a pressure of 1 ton / cm 2 to form a colored resin having a thickness of 1 mm. A plate was obtained. The obtained colored resin plate had a linear absorption coefficient of 0.0853 μm −1 and a dispersion state of 4.
【００８８】[0088]
【作用】本発明において最も重量な点は、ゲータイト微
粒子粉末を、１００〜２００℃の温度範囲で加熱処理し
た場合には、長軸径の粒度が均斉であるとともに短軸径
の粒度が均斉なゲータイト微粒子粉末を得ることができ
るという事実である。The most important point in the present invention is that when goethite fine particle powder is heat-treated in a temperature range of 100 to 200 ° C., the major axis diameter is uniform and the minor axis diameter is uniform. It is a fact that goethite fine particle powder can be obtained.
【００８９】本発明に係る粒度が均斉な微細な赤色酸化
鉄顔料が得られる理由については、本発明者は、ゲータ
イト超微粒子がゲータイト微粒子に吸収されているた
め、超微粒子成分が少なく、長軸径の粒度が均斉である
とともに短軸径の粒度も均斉であるゲータイト微粒子粉
末が得られるとともに、ゲータイト超微粒子が減少する
ことによって、その後の加熱脱水処理においてゲータイ
ト超微粒子に起因する粒子間の焼結が起こりにくいこと
により、ゲータイト微粒子の均斉な粒度を十分に保持し
た、ヘマタイト微粒子粉末を得ることができるためと考
えている。The reason why the fine red iron oxide pigment having a uniform particle size according to the present invention can be obtained is as follows. A goethite fine particle powder having a uniform particle size of the diameter and a uniform short particle size is obtained, and the decrease in goethite ultra-fine particles reduces the sintering between particles caused by the goethite ultra-fine particles in the subsequent heat dehydration treatment. It is considered that hematite fine particle powder which sufficiently retains the uniform particle size of goethite fine particles can be obtained due to the fact that hardly causing the formation.
【００９０】長軸径の幾何標準偏差値が１．５以下であ
って短軸径の幾何標準偏差値が１．３以下であるヘマタ
イト微粒子粉末からなる微細な赤色酸化鉄顔料は、長軸
径の粒度が均斉であるとともに、短軸径の粒度が均斉で
あることによってビヒクル中や樹脂組成物中での分散性
が向上するために、該微細な赤色酸化鉄顔料を用いて得
られた塗膜及び樹脂組成物は優れた分散性及び透明性を
有している。The fine red iron oxide pigment composed of fine hematite fine particles having a geometric standard deviation value of the major axis diameter of 1.5 or less and a minor axis diameter of 1.3 or less is a major axis diameter. And the dispersibility in the vehicle and the resin composition is improved by the uniform particle diameter of the minor axis diameter, and the coating obtained using the fine red iron oxide pigment is used. The film and the resin composition have excellent dispersibility and transparency.
【００９１】本発明に係る微細な赤色酸化鉄顔料の分散
性が向上する理由について、本発明者は、該微細な赤色
酸化鉄顔料の長軸径の幾何標準偏差値が１．５以下、短
軸径の幾何標準偏差値が１．３以下であることにより、
粗大な粒子や微細な粒子の存在が少ないため、ビヒクル
中や樹脂組成物中において、粗大な粒子や微細な粒子に
よる均一な分散が阻害されることがないためと考えてい
る。Regarding the reason why the dispersibility of the fine red iron oxide pigment according to the present invention is improved, the present inventor has determined that the geometric standard deviation of the major axis diameter of the fine red iron oxide pigment is 1.5 or less, When the geometric standard deviation of the shaft diameter is 1.3 or less,
It is considered that since there are few coarse and fine particles, uniform dispersion by the coarse and fine particles is not hindered in the vehicle or the resin composition.
【００９２】また、本発明に係る微細な赤色酸化鉄顔料
を用いた塗料及び樹脂組成物の透明性が向上する理由に
ついて、本発明者は、該微細な赤色酸化鉄顔料がビヒク
ル中や樹脂組成物中への分散に優れた粒子粉末であるた
め、これを塗布して得られた塗膜及び樹脂組成物は、粒
子の凝集が少なく粗大な粒子が存在しないためと考えて
いる。Regarding the reason why the transparency of the coating composition and the resin composition using the fine red iron oxide pigment according to the present invention is improved, the present inventor has argued that the fine red iron oxide pigment is contained in a vehicle or in a resin composition. It is considered that the particles and the resin composition obtained by applying the particles are small in agglomeration of the particles and no coarse particles are present because the particles are excellent in the dispersion in the particles.
【００９３】粒子内部にアルミニウムを含有している本
発明に係る微細な赤色酸化鉄顔料を用いた樹脂組成物の
耐老化性が優れている理由について、本発明者は、粒子
内部に含有されるアルミニウムにより、ヘマタイト粒子
が持つ樹脂組成物の老化に及ぼす触媒作用が抑制された
ことに加えて、粒子内部にアルミニウムを含有している
微細な赤色酸化鉄顔料は分散性に優れていることから、
樹脂組成物中に高度に分散・配合されるために光や熱に
対して優れた遮断効果が発揮されるので、光や熱の樹脂
組成物に対する影響を効果的に抑制する事ができたこと
によるものと考えている。Regarding the reason that the resin composition using the fine red iron oxide pigment according to the present invention containing aluminum in the inside of the particles has excellent aging resistance, the present inventor has considered that the resin composition is contained in the inside of the particles. Due to aluminum, in addition to suppressing the catalytic effect on the aging of the resin composition with the hematite particles, the fine red iron oxide pigment containing aluminum inside the particles is excellent in dispersibility,
Because it is highly dispersed and compounded in the resin composition, it has an excellent light- and heat-blocking effect, so the effect of light and heat on the resin composition can be effectively suppressed. I think it is due to.
【００９４】[0094]
【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.
【００９５】ゲータイト微粒子１〜５：出発原料粒子で
あるゲータイト微粒子として表１に示されるゲータイト
微粒子１乃至５を準備した。Goethite fine particles 1 to 5: Goethite fine particles 1 to 5 shown in Table 1 were prepared as goethite fine particles as starting material particles.
【００９６】[0096]
【表１】 [Table 1]
【００９７】尚、粒子内部にアルミニウムを含有してい
るゲータイト微粒子は、表１に示すアルミニウム化合物
を用いて製造した。The goethite fine particles containing aluminum inside the particles were produced by using the aluminum compounds shown in Table 1.
【００９８】ゲータイト微粒子の種類、温度及び時間を
種々変化させた以外は、前記発明の実施の形態と同様に
して加熱処理を行った。この時の主要製造条件及び加熱
処理後の被処理粒子であるゲータイト微粒子の諸特性を
表２に示す。The heat treatment was performed in the same manner as in the embodiment of the present invention except that the type, temperature and time of the goethite fine particles were variously changed. Table 2 shows the main production conditions and various properties of the goethite fine particles as the particles to be processed after the heat treatment.
【００９９】[0099]
【表２】 [Table 2]
【０１００】実施例１〜６及び比較例１〜６：被処理粒
子であるゲータイト微粒子の種類、加熱脱水処理の温度
及び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、微細な赤色酸化鉄顔料を得た。この時
の主要製造条件及び微細な赤色酸化鉄顔料の諸特性を表
３に示す。Examples 1 to 6 and Comparative Examples 1 to 6: In the same manner as in the above embodiment of the invention except that the type of goethite fine particles to be treated and the temperature and time of the heat dehydration treatment were variously changed. To obtain a fine red iron oxide pigment. Table 3 shows the main production conditions and various characteristics of the fine red iron oxide pigment.
【０１０１】[0101]
【表３】 [Table 3]
【０１０２】比較例１ ゲータイト微粒子に対して加熱処理を行わずに、加熱脱
水処理を行った。得られた赤色酸化鉄顔料の諸特性を表
３に示す。Comparative Example 1 Heat dehydration treatment was performed on goethite fine particles without performing heat treatment. Table 3 shows properties of the obtained red iron oxide pigment.
【０１０３】比較例２ ゲータイト微粒子を８０℃で加熱処理を行い、次いで、
３４０℃で加熱脱水処理を行った。得られた赤色酸化鉄
顔料の諸特性を表３に示す。Comparative Example 2 Goethite fine particles were heated at 80 ° C.
Heat dehydration treatment was performed at 340 ° C. Table 3 shows properties of the obtained red iron oxide pigment.
【０１０４】比較例３ ゲータイト微粒子に対して加熱処理を行わずに、３１０
℃で加熱脱水処理を行い、次いで、更に３４０℃で加熱
脱水処理を行った。得られた赤色酸化鉄顔料の諸特性を
表３に示す。Comparative Example 3 The heat treatment was not performed on the goethite fine particles, and
A heat dehydration treatment was performed at ℃, and then a heat dehydration treatment was further performed at 340 ° C. Table 3 shows properties of the obtained red iron oxide pigment.
【０１０５】比較例４ ゲータイト微粒子に対して１８０℃で加熱処理を行い、
次いで、６８０℃で加熱脱水処理を行った。得られた赤
色酸化鉄顔料の諸特性を表３に示す。Comparative Example 4 Heat treatment was performed on goethite fine particles at 180 ° C.
Next, heat dehydration treatment was performed at 680 ° C. Table 3 shows properties of the obtained red iron oxide pigment.
【０１０６】比較例５ （特開昭４９−３４４９８号公報 実施例１の方法で得
た赤色酸化鉄顔料）硫酸第一鉄１．３ｍｏｌ溶液１０ｌ
に苛性ソーダ６．４９Ｎ溶液４．１ｌを加え、更に水を
加えて全液量を２７．５ｌとした。該混合溶液は可及的
に酸素の混入を防止し、攪拌を行いながら、溶液温度３
３℃において１０分間水酸化第一鉄の生成反応を行っ
た。その後引き続き該水酸化第一鉄コロイド溶液に、可
及的に酸素の混入を防止し、攪拌を行いながら、重炭酸
アンモニウム０．６３ｍｏｌ溶液２２．５ｌを加え全液
量を５０ｌとし、溶液温度３３℃において３０分間炭酸
第一鉄の生成反応を行った。得られた炭酸第一鉄コロイ
ド溶液に、溶液温度３３℃において空気を１４０ｌ／分
の割合で通気した。空気通気後５０分で該炭酸第一鉄コ
ロイド溶液から黄色含水酸化鉄粒子の沈殿を得た。該黄
色含水酸化鉄粒子を水洗・濾別し、１００℃で乾燥し
て、黄色含水酸化鉄粒子粉末を得た。Comparative Example 5 (Red iron oxide pigment obtained by the method of Example 1 in JP-A-49-34498) 10 l of a 1.3 mol solution of ferrous sulfate
To this was added 4.1 l of a 6.49N solution of caustic soda, and further water was added to bring the total volume to 27.5 l. The mixed solution is mixed with the solution temperature as low as possible while preventing mixing of oxygen as much as possible.
The production reaction of ferrous hydroxide was performed at 3 ° C. for 10 minutes. Thereafter, 22.5 l of a 0.63 mol solution of ammonium bicarbonate was added to the ferrous hydroxide colloid solution while stirring to prevent mixing of oxygen as much as possible. The production reaction of ferrous carbonate was performed at 30 ° C. for 30 minutes. Air was bubbled through the obtained ferrous carbonate colloid solution at a solution temperature of 33 ° C. at a rate of 140 l / min. Fifty minutes after air ventilation, yellow iron-containing hydroxide particles were precipitated from the ferrous carbonate colloid solution. The yellow iron oxide hydroxide particles were washed with water, separated by filtration, and dried at 100 ° C. to obtain yellow iron oxide hydroxide particles.
【０１０７】得られた黄色含水酸化鉄粒子の形状は紡錘
状であり、平均長軸径は０．０１μｍ、長軸径の幾何標
準偏差値は１．８１、平均短軸径は０．００３３μｍ、
短軸径の幾何標準偏差値は１．５５、軸比は３．０、Ｂ
ＥＴ比表面積値は２５６．１ｍ２／ｇであった。The obtained yellow hydrous iron oxide particles had a spindle shape, an average major axis diameter of 0.01 μm, a geometric standard deviation of the major axis diameter of 1.81 and an average minor axis diameter of 0.0033 μm.
The geometric standard deviation of the minor axis diameter is 1.55, the axial ratio is 3.0, B
The ET specific surface area value was 256.1 m 2 / g.
【０１０８】次いで、該黄色含水酸化鉄粒子粉末を空気
中３００℃で６０分間保持して赤色酸化鉄顔料を得た。Then, the yellow iron oxide hydroxide particles were kept in the air at 300 ° C. for 60 minutes to obtain a red iron oxide pigment.
【０１０９】得られた赤色酸化鉄顔料の諸特性を表３に
示す。Table 3 shows the properties of the obtained red iron oxide pigment.
【０１１０】比較例６ （特公昭５９−４８７６８号公報 実施例１の方法で得
た赤色酸化鉄顔料）ガス吹き込み装置と攪拌機を装着し
た円筒型反応容器に炭酸ソーダ０．５６ｍｏｌ溶液６．
８ｌを入れ、窒素ガスを吹き込みながら硫酸第一鉄０．
６９ｍｏｌ溶液５．２ｌを徐々に加えた。生成した炭酸
第一鉄懸濁液のｐＨ値は８．３であった。該懸濁液に窒
素ガスを吹き込みながら室温下で２時間攪拌を行った
後、窒素ガスを空気に切り換えて５．０ｌ／分の割合で
通気した。通気２５分後に酸化が終了し、黄色含水酸化
鉄粒子の沈殿物が生成した。該沈殿物を水洗・濾別し、
１００℃で乾燥して、黄色含水酸化鉄粒子粉末を得た。Comparative Example 6 (Red iron oxide pigment obtained by the method of Example 1 in JP-B-59-48768) A 0.56 mol solution of sodium carbonate in a cylindrical reaction vessel equipped with a gas injection device and a stirrer.
8 liters and ferrous sulfate 0.1 g while blowing nitrogen gas.
5.2 l of a 69 mol solution were slowly added. The pH value of the produced ferrous carbonate suspension was 8.3. After stirring at room temperature for 2 hours while blowing nitrogen gas into the suspension, nitrogen gas was switched to air and aerated at a rate of 5.0 l / min. Oxidation was completed 25 minutes after the aeration, and a precipitate of yellow iron oxide hydroxide particles was formed. The precipitate is washed with water and filtered,
After drying at 100 ° C., yellow hydrous iron oxide particles were obtained.
【０１１１】得られた黄色含水酸化鉄粒子の平均長軸径
は０．０３８μｍ、長軸径の幾何標準偏差値は１．７
０、平均短軸径は０．００９５μｍ、短軸径の幾何標準
偏差値は１．４８、軸比は４．０、ＢＥＴ比表面積値は
２１６．５ｍ２／ｇであった。The average length of the major axis of the obtained yellow iron oxide hydroxide particles was 0.038 μm, and the geometric standard deviation of the major axis was 1.7.
0, the average minor axis diameter was 0.0095 μm, the geometric standard deviation of the minor axis diameter was 1.48, the axial ratio was 4.0, and the BET specific surface area value was 216.5 m 2 / g.
【０１１２】次いで、該黄色含水酸化鉄顔料を２８０℃
で１８０分間保持して赤色酸化鉄顔料を得た。Next, the yellow hydrous iron oxide pigment was heated at 280 ° C.
For 180 minutes to obtain a red iron oxide pigment.
【０１１３】得られた赤色酸化鉄顔料の諸特性を表３に
示す。Table 3 shows the properties of the obtained red iron oxide pigment.
【０１１４】実施例７ 実施例１の微細な赤色酸化鉄顔料のうち４５０ｇを、純
水１０ｌに攪拌機を用いて邂逅し、さらにホモミックラ
インミル（特殊機化工業（株）製）を３回通して微細な
赤色酸化鉄粒子顔料のスラリーを得た。Example 7 450 g of the fine red iron oxide pigment of Example 1 were contacted with 10 liters of pure water using a stirrer, and further homogenized with a homomic line mill (manufactured by Tokushu Kika Kogyo Co., Ltd.) three times. To obtain a slurry of fine red iron oxide particle pigment.
【０１１５】得られた微細な赤色酸化鉄顔料のスラリー
の濃度を４５ｇ／ｌに調整し、スラリーを１０ｌ採取し
た。このスラリーを攪拌しながら６０℃まで加熱し、ス
ラリーのｐＨ値を４．０に調整した。The concentration of the slurry of the obtained fine red iron oxide pigment was adjusted to 45 g / l, and 10 l of the slurry were collected. The slurry was heated to 60 ° C. with stirring to adjust the pH value of the slurry to 4.0.
【０１１６】次に、このスラリー中に１ｍｏｌ／ｌの酢
酸アルミニウム溶液１６７ｍｌ（微細な赤色酸化鉄顔料
に対してＡｌ換算で１．０重量％に相当する）を加え、
３０分間保持した後、水酸化ナトリウム水溶液を用いて
ｐＨ値を７．０に調整し、この状態で３０分間保持し
た。次いで濾過、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微細な赤色酸
化鉄顔料を得た。Next, 167 ml of a 1 mol / l aluminum acetate solution (corresponding to 1.0% by weight in terms of Al with respect to the fine red iron oxide pigment) was added to this slurry,
After holding for 30 minutes, the pH value was adjusted to 7.0 using an aqueous sodium hydroxide solution, and this state was maintained for 30 minutes. Next, the particles were filtered, washed with water, dried and pulverized to obtain a fine red iron oxide pigment having a particle surface coated with aluminum hydroxide.
【０１１７】実施例８〜１２：微細な赤色酸化鉄顔料の
種類、表面被覆物の種類、添加前ｐＨ値、添加量、最終
ｐＨ値を種々変化させた以外は、前記実施例７と同様に
して粒子表面が被覆された微細な赤色酸化鉄顔料を得
た。Examples 8 to 12: Same as Example 7 except that the type of fine red iron oxide pigment, the type of surface coating, the pH value before addition, the amount added, and the final pH value were variously changed. Thus, a fine red iron oxide pigment having a particle surface coated was obtained.
【０１１８】この時の主要製造条件を表４に、得られた
微細な赤色酸化鉄顔料の諸特性を表５に示す。The main production conditions at this time are shown in Table 4, and various characteristics of the obtained fine red iron oxide pigment are shown in Table 5.
【０１１９】[0119]
【表４】 [Table 4]
【０１２０】[0120]
【表５】 [Table 5]
【０１２１】＜微細な赤色酸化鉄顔料を用いた塗料＞ 実施例１３〜２４：微細な赤色酸化鉄顔料の種類を種々
変化させた以外は前記発明の実施の形態と同様にして塗
料を製造した。<Paints Using Fine Red Iron Oxide Pigment> Examples 13 to 24: Paints were produced in the same manner as in the embodiment of the invention except that the type of the fine red iron oxide pigment was variously changed. .
【０１２２】この時の主要製造条件及び諸特性を表６に
示す。Table 6 shows the main manufacturing conditions and various characteristics at this time.
【０１２３】[0123]
【表６】 [Table 6]
【０１２４】比較例７〜１２：赤色酸化鉄顔料の種類を
種々変化させた以外は、前記発明の実施の形態と同様に
して塗料を製造した。Comparative Examples 7 to 12: Paints were produced in the same manner as in the embodiment of the present invention except that the type of the red iron oxide pigment was variously changed.
【０１２５】この時の主要製造条件及び諸特性を表７に
示す。Table 7 shows the main manufacturing conditions and various characteristics at this time.
【表７】 [Table 7]
【０１２６】＜微細な赤色酸化鉄顔料を用いた樹脂組成
物＞ 実施例２５〜３６：微細な赤色酸化鉄顔料の種類を種々
変化させた以外は前記発明の実施の形態と同様にして樹
脂組成物を製造した。<Resin Composition Using Fine Red Iron Oxide Pigment> Examples 25 to 36: Resin composition in the same manner as in the embodiment of the present invention except that the type of fine red iron oxide pigment was variously changed. Was manufactured.
【０１２７】この時の主要製造条件及び得られた樹脂組
成物の諸特性を表８に示す。Table 8 shows the main production conditions and various properties of the obtained resin composition.
【０１２８】[0128]
【表８】 [Table 8]
【０１２９】比較例１３〜１８：赤色酸化鉄顔料の種類
を種々変化させた以外は、前記発明の実施の形態と同様
にして樹脂組成物を製造した。Comparative Examples 13 to 18: Resin compositions were produced in the same manner as in the embodiment of the invention except that the type of the red iron oxide pigment was variously changed.
【０１３０】この時の主要製造条件及び得られた樹脂組
成物の諸特性を表９に示す。Table 9 shows the main production conditions and various properties of the obtained resin composition.
【表９】 [Table 9]
【０１３１】[0131]
【発明の効果】本発明に係る微細な赤色酸化鉄顔料は、
長軸径の粒度が均斉であるとともに短軸径の粒度が均斉
であることによって透明性が優れているので、透明性を
有する赤色着色顔料として好ましいものである。The fine red iron oxide pigment according to the present invention comprises:
Since the transparency is excellent due to the uniform particle diameter of the major axis and the uniform particle diameter of the minor axis, it is preferable as a transparent red coloring pigment.
【０１３２】また、本発明に係る微細な赤色酸化鉄顔料
を用いた塗料及び樹脂組成物は、微細な赤色酸化鉄顔料
の粒子径の粒度が均斉であって透明性が優れていること
から、透明性に優れた塗料及び樹脂組成物である。The coating composition and the resin composition using the fine red iron oxide pigment according to the present invention have a uniform particle size of the fine red iron oxide pigment and excellent transparency, A paint and a resin composition having excellent transparency.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｄ 7/12 Ｃ０９Ｄ 7/12 Ｚ 201/00 201/00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09D 7/12 C09D 7/12 Z 201/00 201/00
Claims (7)
あって、短軸径の幾何標準偏差値が１．３以下である平
均長軸径が０．００５〜０．１μｍのヘマタイト微粒子
からなることを特徴とする微細な赤色酸化鉄顔料。An average major axis diameter of 0.005 to 0.1 μm, wherein the major axis diameter has a geometric standard deviation of 1.5 or less and the minor axis diameter has a geometric standard deviation of 1.3 or less. A fine red iron oxide pigment characterized by comprising hematite fine particles.
換算で０．０５〜５０重量％のアルミニウムを含有して
いる請求項１記載の微細な赤色酸化鉄顔料。2. Hematite fine particle powder contains Al inside the particles.
2. The fine red iron oxide pigment according to claim 1, which contains 0.05 to 50% by weight of aluminum in terms of aluminum oxide.
ミニウムの水酸化物、アルミニウムの酸化物、ケイ素の
水酸化物及びケイ素の酸化物の少なくとも１種で被覆さ
れている請求項１又は請求項２記載の微細な赤色酸化鉄
顔料。3. The hematite fine particle powder according to claim 1, wherein the particle surface is coated with at least one of aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. Fine red iron oxide pigment.
℃の温度範囲で加熱脱水処理してヘマタイト微粒子粉末
とするに当って、前記加熱脱水処理に先立ってあらかじ
め、前記ゲータイト微粒子粉末を１００〜２００℃の温
度範囲で加熱処理して、該ゲータイト微粒子粉末に含ま
れているゲータイト超微粒子をゲータイト微粒子に吸収
させておくことを特徴とする請求項１記載の微細な赤色
酸化鉄顔料の製造法。4. A goethite fine particle powder of 250 to 500
Prior to the heat dehydration treatment, the goethite fine particle powder was previously subjected to a heat treatment at a temperature in the range of 100 to 200 ° C. to obtain the hematite fine particle powder. 2. The method for producing a fine red iron oxide pigment according to claim 1, wherein the goethite ultrafine particles contained in the pigment are absorbed by the goethite fine particles.
量％のアルミニウムを含有しているゲータイト微粒子粉
末を２５０〜５００℃の温度範囲で加熱脱水処理してヘ
マタイト微粒子粉末とするに当って、上記加熱脱水処理
に先立ってあらかじめ、前記ゲータイト微粒子粉末を１
００〜２００℃の温度範囲で加熱処理して、該ゲータイ
ト微粒子粉末に含まれているゲータイト超微粒子をゲー
タイト微粒子に吸収させておくことを特徴とする請求項
２記載の微細な赤色酸化鉄顔料の製造法。5. A hematite fine particle powder obtained by heating and dehydrating goethite fine particle powder containing 0.05 to 50% by weight of aluminum in terms of Al in the inside of the particle at a temperature of 250 to 500 ° C. Prior to the heat dehydration treatment, the goethite fine particle powder was
The fine red iron oxide pigment according to claim 2, wherein the goethite ultrafine particles contained in the goethite fine particle powder are absorbed by the goethite fine particles by heat treatment in a temperature range of 00 to 200 ° C. Manufacturing method.
微細な赤色酸化鉄顔料を用いることを特徴とする塗料。6. A paint using the fine red iron oxide pigment according to any one of claims 1 to 3.
微細な赤色酸化鉄顔料を用いることを特徴とする樹脂組
成物。7. A resin composition using the fine red iron oxide pigment according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26920899A JP4452958B2 (en) | 1998-09-25 | 1999-09-22 | Fine red iron oxide pigment, process for producing the same, paint and resin composition using the pigment |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-271478 | 1998-09-25 | ||
| JP27147898 | 1998-09-25 | ||
| JP26920899A JP4452958B2 (en) | 1998-09-25 | 1999-09-22 | Fine red iron oxide pigment, process for producing the same, paint and resin composition using the pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000233932A true JP2000233932A (en) | 2000-08-29 |
| JP4452958B2 JP4452958B2 (en) | 2010-04-21 |
Family
ID=26548661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26920899A Expired - Lifetime JP4452958B2 (en) | 1998-09-25 | 1999-09-22 | Fine red iron oxide pigment, process for producing the same, paint and resin composition using the pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4452958B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004043208A (en) * | 2002-07-09 | 2004-02-12 | Univ Okayama | Process for preparing aluminum-substituted hematite |
| JP2004511612A (en) * | 2000-10-09 | 2004-04-15 | バイエル アクチェンゲゼルシャフト | Composite particles |
| CN100552778C (en) * | 2005-06-27 | 2009-10-21 | 同和电子科技有限公司 | Iron compound particle powder and the magnetic recording media that uses this powder |
| CN103449531A (en) * | 2013-08-19 | 2013-12-18 | 铜陵瑞莱科技有限公司 | Preparation method of iron oxide red for artificial marbles |
| CN103665953A (en) * | 2013-11-08 | 2014-03-26 | 铜陵市镜铁粉厂 | Preparation method of iron oxide red for printing ink |
| JP2017218570A (en) * | 2015-10-05 | 2017-12-14 | エム・テクニック株式会社 | Silicon oxide-coated iron oxide composition for coating containing iron oxide particles coated with silicon oxide |
| WO2018074598A1 (en) * | 2016-10-21 | 2018-04-26 | 国立大学法人 岡山大学 | Iron oxide for red pigments and method for producing same |
| WO2019123670A1 (en) * | 2017-12-20 | 2019-06-27 | 国立大学法人 岡山大学 | Iron oxide for orange pigment and method for producing same |
| JP2021532250A (en) * | 2018-07-18 | 2021-11-25 | ランクセス・ドイチュランド・ゲーエムベーハー | Hematite pigment |
-
1999
- 1999-09-22 JP JP26920899A patent/JP4452958B2/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004511612A (en) * | 2000-10-09 | 2004-04-15 | バイエル アクチェンゲゼルシャフト | Composite particles |
| JP2004043208A (en) * | 2002-07-09 | 2004-02-12 | Univ Okayama | Process for preparing aluminum-substituted hematite |
| CN100552778C (en) * | 2005-06-27 | 2009-10-21 | 同和电子科技有限公司 | Iron compound particle powder and the magnetic recording media that uses this powder |
| CN103449531A (en) * | 2013-08-19 | 2013-12-18 | 铜陵瑞莱科技有限公司 | Preparation method of iron oxide red for artificial marbles |
| CN103665953A (en) * | 2013-11-08 | 2014-03-26 | 铜陵市镜铁粉厂 | Preparation method of iron oxide red for printing ink |
| JP2017218570A (en) * | 2015-10-05 | 2017-12-14 | エム・テクニック株式会社 | Silicon oxide-coated iron oxide composition for coating containing iron oxide particles coated with silicon oxide |
| WO2018074598A1 (en) * | 2016-10-21 | 2018-04-26 | 国立大学法人 岡山大学 | Iron oxide for red pigments and method for producing same |
| JP2018070441A (en) * | 2016-10-21 | 2018-05-10 | 国立大学法人 岡山大学 | Iron oxide for red pigment and for catalyst, and method for producing the same |
| JP7038995B2 (en) | 2016-10-21 | 2022-03-22 | 国立大学法人 岡山大学 | Iron oxide for red pigments and catalysts and its manufacturing method |
| WO2019123670A1 (en) * | 2017-12-20 | 2019-06-27 | 国立大学法人 岡山大学 | Iron oxide for orange pigment and method for producing same |
| JPWO2019123670A1 (en) * | 2017-12-20 | 2020-12-10 | 国立大学法人 岡山大学 | Iron oxide for orange pigments and its manufacturing method |
| JP7074366B2 (en) | 2017-12-20 | 2022-05-24 | 国立大学法人 岡山大学 | Iron oxide for orange pigments and its manufacturing method |
| JP2021532250A (en) * | 2018-07-18 | 2021-11-25 | ランクセス・ドイチュランド・ゲーエムベーハー | Hematite pigment |
| JP7239694B2 (en) | 2018-07-18 | 2023-03-14 | ランクセス・ドイチュランド・ゲーエムベーハー | hematite pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4452958B2 (en) | 2010-04-21 |
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