JPH09188517A - Iron-containing superfine zinc oxide, its production and use - Google Patents
Iron-containing superfine zinc oxide, its production and useInfo
- Publication number
- JPH09188517A JPH09188517A JP12096A JP12096A JPH09188517A JP H09188517 A JPH09188517 A JP H09188517A JP 12096 A JP12096 A JP 12096A JP 12096 A JP12096 A JP 12096A JP H09188517 A JPH09188517 A JP H09188517A
- Authority
- JP
- Japan
- Prior art keywords
- iron
- zinc oxide
- oxide
- weight
- ultrafine zinc
- 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.)
- Pending
Links
Landscapes
- Cosmetics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鉄含有超微細酸化
亜鉛、並びにその製造方法及びその用途に関し、詳しく
は、鉄を結晶格子内部に含む超微細な酸化亜鉛、その製
造方法及びそれを用いた日焼け止め化粧料及び紫外線遮
蔽塗料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an iron-containing ultrafine zinc oxide, a method for producing the same, and its use. The present invention relates to sunscreen cosmetics and UV-shielding paints.
【０００２】[0002]
【従来の技術】地上に到達する紫外線は、その波長によ
って、Ａ領域（波長３２０〜３８０ｎｍ）とＢ領域（波
長２９０〜３２０ｎｍ）とに区分されているが（国際照
明委員会）、近年、フロンガス等によるオゾン層の破壊
に伴い、地上に到達する紫外線量の増加が懸念されてい
る。このような事情を背景として、従来、紫外線の遮蔽
は、Ｂ領域の遮蔽が中心であったが、最近では、Ａ領域
の遮蔽も注目され始めている。このＡ領域の紫外線は、
皮膚の内奥部まで達して、組織を傷め、肌の老化を招く
からである。2. Description of the Related Art Ultraviolet rays reaching the ground are classified into an A region (wavelength 320 to 380 nm) and a B region (wavelength 290 to 320 nm) according to their wavelength (International Commission on Illumination), but in recent years, CFCs have been used. There is a concern that the amount of ultraviolet rays reaching the ground will increase with the destruction of the ozone layer due to such factors. Against such a background, in the past, the ultraviolet ray was mainly shielded in the B region, but recently, the A region is being shielded. The ultraviolet rays in this A region
This is because it reaches the inner deep part of the skin, damages the tissue, and causes skin aging.
【０００３】従来、日焼け止め化粧料や紫外線遮蔽塗料
に用いられている紫外線吸収剤は、ベンゾフェノン系や
安息香酸系の有機化合物であるが、これらの化合物の吸
収帯は、概ね、２８０〜３５０ｎｍの範囲に存在するの
で、Ａ領域の紫外線を完全に遮蔽することはできない。
更に、従来の上記有機化合物からなる紫外線吸収剤は、
安全性の面でも、問題視されるに至っている。Conventionally, ultraviolet absorbers used in sunscreen cosmetics and ultraviolet shielding paints are benzophenone-based or benzoic acid-based organic compounds, but the absorption bands of these compounds are generally 280 to 350 nm. Since it exists in the range, it is not possible to completely block the ultraviolet rays in the A region.
Furthermore, the conventional ultraviolet absorber composed of the above organic compound,
In terms of safety, it has become a problem.
【０００４】従って、最近、紫外線吸収剤として、紫外
線吸収帯のより広い無機顔料が使用されることが多くな
っており、なかでも、平均一次粒子径が0.１μｍ以下の
超微細粒子は、化粧料や塗料に配合した場合に、透明な
塗膜を形成し、自然な色合いを有することができる点で
好まれている。特に、酸化チタンは、３６０ｎｍ以下の
波長の紫外線を完全に遮蔽するので、最も多く用いられ
ている。しかし、酸化チタンは、屈折率がルチル型のも
ので、2.７と高く、隠蔽力が強いために、0.１μｍ以下
の超微細粒子にしても完全に透明とはならず、白濁感を
与える。更に、酸化チタンは、0.１μｍ以下の超微細粒
子になると、青みがかかり、例えば、このような超微細
粒子の酸化チタンを配合した日焼け止め化粧料を肌に塗
布した場合に、肌を不健康にみせる欠点がある（特公平
７−２３２９４号公報）。Therefore, recently, as an ultraviolet absorber, an inorganic pigment having a wider ultraviolet absorption band is often used, and among them, ultrafine particles having an average primary particle diameter of 0.1 μm or less are used as cosmetics. It is preferred because it can form a transparent coating film and can have a natural color when it is blended with a material or paint. In particular, titanium oxide is most often used because it completely blocks ultraviolet rays having a wavelength of 360 nm or less. However, titanium oxide, which has a rutile type refractive index, is as high as 2.7 and has a strong hiding power, so even if it is ultrafine particles of 0.1 μm or less, it will not be completely transparent and will give a cloudy feeling. give. Furthermore, titanium oxide becomes bluish when it becomes ultrafine particles of 0.1 μm or less. For example, when a sunscreen cosmetic containing such ultrafine particles of titanium oxide is applied to the skin, the skin becomes unhealthy. However, it has a drawback (Japanese Patent Publication No. 7-23294).
【０００５】そこで、現在、このような欠点をもたない
酸化亜鉛が非常に注目を集めている。酸化亜鉛は、酸化
チタンよりも広い紫外線吸収帯を有し、３７０ｎｍ以下
の波長の紫外線を完全に遮蔽し、また、屈折率も1.９〜
2.０と低いので、隠蔽力が小さく、0.１μｍ以下の超微
細粒子では、透明感が高く、酸化チタンにおけるような
白濁感もない（特公平７−２３２９４号公報）。更に、
塗料に用いる場合には、着色調合が容易であり、他方、
化粧料に用いる場合には、青みがなく、また、収斂性
（即ち、膚の引締め効果）や消炎効果を付与することが
できるほか、皮脂の吸収剤としても作用する効果を有し
ている。Therefore, zinc oxide, which does not have such drawbacks, is now drawing much attention. Zinc oxide has a wider ultraviolet absorption band than titanium oxide, completely blocks ultraviolet rays having a wavelength of 370 nm or less, and has a refractive index of 1.9 to
Since it is as low as 2.0, the hiding power is small, and the ultrafine particles of 0.1 μm or less have a high transparency and do not have the cloudiness as in titanium oxide (Japanese Patent Publication No. 7-23294). Furthermore,
When used in paints, it is easy to color and mix, while
When used in cosmetics, it has no bluishness, can impart astringency (ie, skin tightening effect) and anti-inflammatory effect, and also has an effect of acting as a sebum absorbent.
【０００６】このように、酸化亜鉛は、透明性の紫外線
遮蔽剤としてすぐれているが、紫外線のＡ領域を完全に
遮蔽するまでには至らず、しかも、酸化チタンと同様
に、粒子径が小さくなるに従って、吸収端波長が短波長
側にシフトし、粒子径0.０５μｍのとき、吸収端は３７
０ｎｍ付近になり、粒子径0.０１μｍのとき、吸収端は
３６５ｎｍ付近まで後退する。As described above, zinc oxide is excellent as a transparent ultraviolet ray shielding agent, but it does not completely block the A region of ultraviolet rays and, like titanium oxide, has a small particle size. When the particle size is 0.05 μm, the absorption edge shifts to 37 nm.
When the particle diameter is around 0 nm and the particle diameter is 0.01 μm, the absorption edge recedes to around 365 nm.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、従来の紫外
線吸収における上述したような種々の問題を解決するた
めになされたものであって、酸化亜鉛の有する透明感を
生かしつつ、紫外線のＡ領域を完全に遮蔽することがで
き、従って、日焼け止め化粧料や紫外線遮蔽塗料に用い
るに好適な鉄含有超微細酸化亜鉛を提供することを目的
とする。更に、本発明は、そのような鉄含有超微細酸化
亜鉛の製造方法とその用途、特に、日焼け止め化粧料及
び紫外線遮蔽塗料を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned various problems in the conventional ultraviolet absorption, and makes the best use of the transparency of zinc oxide while maintaining the A It is an object of the present invention to provide an iron-containing ultrafine zinc oxide which can completely shield an area and is therefore suitable for use in sunscreen cosmetics and UV-shielding paints. A further object of the present invention is to provide a method for producing such iron-containing ultrafine zinc oxide and its application, especially a sunscreen cosmetic and an ultraviolet-shielding paint.
【０００８】[0008]
【課題を解決するための手段】本発明による鉄含有超微
細酸化亜鉛は、平均一次粒子径0.０１〜0.１μｍの酸化
亜鉛であって、その結晶格子内部に鉄を0.１〜１０重量
％の範囲で有することを特徴とする。The iron-containing ultrafine zinc oxide according to the present invention is zinc oxide having an average primary particle diameter of 0.01 to 0.1 μm, and iron is contained in the crystal lattice of 0.1 to 10 μm. It is characterized by having in the range of% by weight.
【０００９】このような鉄含有超微細酸化亜鉛は、本発
明に従って、亜鉛塩と鉄塩とを含む水溶液を炭酸アンモ
ニウム又は炭酸水素アンモニウムにて中和し、得られた
沈殿を濾過、水洗、乾燥した後、酸化性雰囲気下に３０
０〜６００℃の温度で焼成することによって得ることが
できる。According to the present invention, such an iron-containing ultrafine zinc oxide is prepared by neutralizing an aqueous solution containing a zinc salt and an iron salt with ammonium carbonate or ammonium hydrogencarbonate, and filtering the resulting precipitate, washing with water and drying. And then in an oxidizing atmosphere for 30
It can be obtained by firing at a temperature of 0 to 600 ° C.
【００１０】[0010]
【発明の実施の形態】先ず、本発明による鉄含有超微細
酸化亜鉛の製造について説明する。本発明による鉄含有
超微細酸化亜鉛の製造において、亜鉛塩としては、例え
ば、塩化物、硫酸塩、硝酸塩、酢酸塩等の水溶性塩が用
いられるが、これらに限定されるものではない。また、
鉄塩としても、亜鉛塩と同様に、塩化物、硫酸塩、硝酸
塩、酢酸塩等の水溶性塩が用いられるが、これらに限定
されるものではない。亜鉛塩と鉄塩とを含む水溶液は、
亜鉛塩の水溶液と鉄塩の水溶液を別々に調製し、これら
を混合してもよく、また、亜鉛塩と鉄塩とを水に溶解さ
せて、調製してもよい。また、亜鉛塩の水溶液に鉄塩を
溶解させてもよく、この反対でもよい。First, the production of ultrafine zinc oxide containing iron according to the present invention will be described. In the production of the iron-containing ultrafine zinc oxide according to the present invention, as the zinc salt, for example, water-soluble salts such as chloride, sulfate, nitrate and acetate are used, but the zinc salt is not limited thereto. Also,
As the iron salt, water-soluble salts such as chlorides, sulfates, nitrates and acetates are used as in the case of the zinc salt, but the iron salt is not limited to these. An aqueous solution containing zinc salt and iron salt,
The zinc salt aqueous solution and the iron salt aqueous solution may be separately prepared and mixed, or the zinc salt and the iron salt may be dissolved in water to be prepared. Further, the iron salt may be dissolved in an aqueous solution of zinc salt, or vice versa.
【００１１】上記亜鉛塩と鉄塩とを含む水溶液の調製に
おいて、鉄塩は、生成される酸化亜鉛中に鉄として0.１
〜１０重量％、好ましくは、0.５〜８重量％の範囲で含
まれるように用いられる。生成される酸化亜鉛に含まれ
る鉄の量が0.１重量％よりも少ないときは、生成される
酸化亜鉛の紫外線吸収能の改善が殆どなく、他方、１０
重量％を越えるときは、生成される酸化亜鉛が深い赤味
を帯びるので、化粧料や塗料に用いた場合に自然な色合
いが損なわれることとなる。In the preparation of the above aqueous solution containing the zinc salt and the iron salt, the iron salt is added as 0.1 in the zinc oxide produced as iron.
It is used so as to be contained in the range of 10 to 10% by weight, preferably 0.5 to 8% by weight. When the amount of iron contained in the produced zinc oxide is less than 0.1% by weight, there is almost no improvement in the ultraviolet absorbing ability of the produced zinc oxide, and 10
If it exceeds 5% by weight, the zinc oxide produced has a deep reddish tint, which impairs the natural color tone when used in cosmetics and paints.
【００１２】次いで、上記亜鉛塩と鉄塩とを含む水溶液
を炭酸アンモニウム又は炭酸水素アンモニウムによって
中和し、沈殿を生成させる。ここに、中和剤として、上
記炭酸塩を用いるのは、沈殿中にアルカリ金属イオンを
含有させないためである。沈殿がアルカリ金属イオンを
含有するときは、水洗によって、アルカリ金属イオンを
沈殿から除去することが困難であり、沈殿に残存するア
ルカリ金属イオンがその焼成時に粒子の焼結を促進し、
粒子を肥大化させるので、目的とする超微細粒子を得る
ことが困難となるからである。Next, the aqueous solution containing the above zinc salt and iron salt is neutralized with ammonium carbonate or ammonium hydrogen carbonate to form a precipitate. The carbonate is used as the neutralizing agent here because alkali metal ions are not contained in the precipitate. When the precipitate contains alkali metal ions, it is difficult to remove the alkali metal ions from the precipitate by washing with water, and the alkali metal ions remaining in the precipitate promote the sintering of the particles during firing,
This is because the particles are enlarged, and it becomes difficult to obtain the target ultrafine particles.
【００１３】亜鉛塩と鉄塩とを含む水溶液を炭酸アンモ
ニウム又は炭酸水素アンモニウムによって中和するに
は、具体的には、例えば、亜鉛塩と鉄塩とを含む水溶液
を攪拌しながら、これに炭酸アンモニウム又は炭酸水素
アンモニウムを固体のままで、又はその水溶液を加え
て、中和してもよく、反対に、炭酸アンモニウム又は炭
酸水素アンモニウムの水溶液に亜鉛塩と鉄塩とを含む水
溶液を加えてもよく、特に、限定されるものではない。
また、適宜の容器中に亜鉛塩と鉄塩とを含む水溶液と炭
酸アンモニウム又は炭酸水素アンモニウムの水溶液とを
同時に加えて中和してもよい。亜鉛塩と鉄塩とを含む水
溶液を炭酸アンモニウム又は炭酸水素アンモニウムによ
って中和するには、亜鉛塩と鉄塩の合計量の１〜1.５当
量のこれら炭酸塩を用いるのが好ましい。To neutralize an aqueous solution containing a zinc salt and an iron salt with ammonium carbonate or ammonium hydrogencarbonate, specifically, for example, an aqueous solution containing a zinc salt and an iron salt is stirred and carbonated. Ammonium or ammonium hydrogencarbonate may be neutralized as it is or by adding an aqueous solution thereof, or conversely, an aqueous solution containing a zinc salt and an iron salt may be added to an aqueous solution of ammonium carbonate or ammonium hydrogencarbonate. Well, it is not particularly limited.
Alternatively, an aqueous solution containing a zinc salt and an iron salt and an aqueous solution of ammonium carbonate or ammonium hydrogen carbonate may be simultaneously added to an appropriate container for neutralization. To neutralize an aqueous solution containing a zinc salt and an iron salt with ammonium carbonate or ammonium hydrogen carbonate, it is preferable to use 1 to 1.5 equivalents of the total amount of the zinc salt and the iron salt.
【００１４】本発明において、亜鉛塩と鉄塩とを含む水
溶液や、また、炭酸アンモニウム又は炭酸水素アンモニ
ウムの水溶液は、上記中和に際して、沈殿の生成する不
均一系を均一に攪拌できる程度であればよく、特に、そ
の濃度において限定されるものではない。In the present invention, an aqueous solution containing a zinc salt and an iron salt, or an aqueous solution of ammonium carbonate or ammonium hydrogen carbonate should be such that a heterogeneous system in which a precipitate is formed can be uniformly stirred during the neutralization. However, the concentration is not particularly limited.
【００１５】このようにして、亜鉛塩と鉄塩を上記炭酸
塩にて中和して沈殿を生成させ、次いで、これを濾過
し、水洗し、乾燥する。このようにして得られる乾燥物
中の水分の量が多いときは、乾燥物の粘着性が強くな
り、後工程での取扱いが困難となるので、好ましくは、
乾燥物の水分を0.１％以下とする。このようにして得ら
れる乾燥物は、Ｘ線回折によれば、塩基性炭酸亜鉛と無
定形物の混合物である。In this way, the zinc salt and iron salt are neutralized with the above carbonate to form a precipitate, which is then filtered, washed with water and dried. When the amount of water in the dried product thus obtained is large, the tackiness of the dried product becomes strong and it becomes difficult to handle it in a subsequent step, so that it is preferable that
The water content of the dried product should be 0.1% or less. The dried product thus obtained is a mixture of basic zinc carbonate and an amorphous substance by X-ray diffraction.
【００１６】次いで、上記乾燥物をハンマーミル、エッ
ジランナーミル等により乾式粉砕して、微粉とする。乾
燥物は、通常、球状、板状、ヌードル状の塊として得ら
れるので、これを８０メツシユ全通となるように粉砕す
るのが好ましい。ここに、乾式粉砕することなく、乾燥
物を焼成すれば、結晶成長や二次凝集のために粒子径が
肥大し、目的とする酸化亜鉛の超微細粒子を得ることが
できない。他方、焼成後に乾式粉砕するときは、特に、
ハンマーミル等の衝撃性の粉砕を行なうときは、得られ
る製品の色にくすみが生じるので好ましくなく、この観
点からも、乾燥物を焼成する前に乾式粉砕することが好
ましい。Then, the dried product is dry-pulverized by a hammer mill, an edge runner mill or the like to obtain fine powder. Since the dried product is usually obtained as a spherical, plate-shaped, or noodle-shaped lump, it is preferable to grind this so that the whole amount is 80 mesh. If the dried product is calcined without dry pulverization, the particle size is enlarged due to crystal growth and secondary aggregation, and the desired ultrafine particles of zinc oxide cannot be obtained. On the other hand, when dry pulverizing after firing,
When performing impact pulverization with a hammer mill or the like, it is not preferable because the color of the obtained product is dull, and from this viewpoint, dry pulverization is also preferable before firing the dried product.
【００１７】次いで、上記乾燥物を代表的には空気中等
の酸化性雰囲気下に３００〜６００℃の範囲の温度で焼
成することによって、目的とする鉄含有超微細酸化亜鉛
を得ることができる。ここに、上記乾燥物は、通常、球
状、板状、ヌードル状の塊として得られるので、焼成の
前に、取扱いに支障をきたさない程度に乾式粉砕してお
くのが好ましい。焼成温度が３００℃よりも低いとき
は、前記塩基性炭酸亜鉛の分解に長時間を必要とし、６
００℃を越えるときは、乾燥物が焼結乃至は融着し、粒
子が肥大化して、目的とする超微細粒子を得ることが困
難である。焼成時間は、特に、限定されるものではない
が、得られる鉄含有超微細酸化亜鉛の要求物性等を考慮
して、適宜に決定される。通常、0.５〜３時間の範囲で
ある。The desired iron-containing ultrafine zinc oxide can then be obtained by calcining the dried product, typically in an oxidizing atmosphere such as air, at a temperature in the range of 300 to 600 ° C. Here, since the dried product is usually obtained as a spherical, plate-shaped, or noodle-shaped mass, it is preferable to dry-pulverize it before firing so that it does not hinder handling. When the firing temperature is lower than 300 ° C, it takes a long time to decompose the basic zinc carbonate, and
When the temperature exceeds 00 ° C, the dried product is sintered or fused and the particles are enlarged, and it is difficult to obtain the target ultrafine particles. The firing time is not particularly limited, but is appropriately determined in consideration of the required physical properties of the obtained iron-containing ultrafine zinc oxide. Usually, it is in the range of 0.5 to 3 hours.
【００１８】このようにして得られる鉄含有超微細酸化
亜鉛は、平均一次粒子径0.０１〜0.１μｍの範囲にあ
り、その結晶格子内部に鉄を0.１〜１０重量％の範囲で
含み、結晶格子内部に鉄が固溶したものである。The thus obtained iron-containing ultrafine zinc oxide has an average primary particle size of 0.01 to 0.1 μm, and iron within the crystal lattice of 0.1 to 10% by weight. It is a solid solution of iron in the crystal lattice.
【００１９】超微細酸化鉄は、透明性が高く、紫外線吸
収端を４００〜４５０ｎｍに有するので、本発明に従っ
て、酸化亜鉛の結晶格子内部に鉄を固溶させることによ
って、紫外線吸収端が、酸化亜鉛が本来、有する吸収端
よりも高波長側にシフトし、かくして、ほぼ完全にＡ領
域の紫外線を遮蔽することができる。しかも、本発明に
よる鉄含有超微細酸化亜鉛は、鉄が酸化亜鉛の結晶格子
内部に固溶しているので、酸化亜鉛と鉄成分との色分か
れを生じることなく、任意の分散媒体に均一に分散させ
ることができる。Since ultrafine iron oxide is highly transparent and has an ultraviolet absorption edge in the range of 400 to 450 nm, the ultraviolet absorption edge is oxidized by dissolving iron in the zinc oxide crystal lattice according to the present invention. Zinc shifts to a higher wavelength side than the absorption edge which zinc originally has, and thus, it is possible to almost completely block ultraviolet rays in the A region. Moreover, since the iron-containing ultrafine zinc oxide according to the present invention contains iron as a solid solution in the crystal lattice of zinc oxide, it does not cause color separation between the zinc oxide and the iron component and is uniformly dispersed in any dispersion medium. It can be dispersed.
【００２０】本発明によれば、このような鉄含有超微細
酸化亜鉛の表面に、アルミニウム、ケイ素、チタン、ジ
ルコニウム、スズ及びアンチモンから選ばれる少なくと
も１種の元素の含水酸化物又は酸化物からなる被覆を有
せしめることができる。また、本発明によれば、鉄含有
超微細酸化亜鉛の表面に、種々のカルボン酸、ポリオー
ルを含むアルコール、アミン、シロキサン等の有機物か
らなる被覆を有せしめることができる。According to the present invention, the surface of such iron-containing ultrafine zinc oxide comprises a hydrous oxide or oxide of at least one element selected from aluminum, silicon, titanium, zirconium, tin and antimony. It can have a coating. Further, according to the present invention, the surface of the iron-containing ultrafine zinc oxide can be provided with a coating made of an organic material such as alcohols including various carboxylic acids and polyols, amines, and siloxanes.
【００２１】このような酸化物被覆を有する鉄含有超微
細酸化亜鉛は、例えば、鉄含有超微細酸化亜鉛を水に分
散させてスラリーとし、必要に応じて湿式粉砕、分級処
理した後、上記元素の水溶性塩を鉄含有超微細酸化亜鉛
に対して酸化物換算にて１〜１５重量％の範囲の量で加
えた後、酸又はアルカリにて適宜に中和することによっ
て、鉄含有超微細酸化亜鉛の粒子の表面に上記元素の含
水酸化物又は酸化物を沈殿、被着させ、この後、このよ
うに処理した鉄含有超微細酸化亜鉛を濾過し、乾燥し、
粉砕することによって、目的とする酸化物被覆した鉄含
有超微細酸化亜鉛を得ることができる。The iron-containing ultrafine zinc oxide having such an oxide coating is prepared, for example, by dispersing the iron-containing ultrafine zinc oxide in water to form a slurry, and if necessary, wet pulverizing and classifying the above-mentioned elements. The water-soluble salt of is added to the iron-containing ultrafine zinc oxide in an amount in the range of 1 to 15% by weight in terms of oxide, and then appropriately neutralized with an acid or alkali to obtain an iron-containing ultrafine Precipitation and deposition of hydrous oxides or oxides of the above elements on the surface of zinc oxide particles, after which the iron-containing ultrafine zinc oxide treated in this way is filtered and dried,
By pulverizing, the target oxide-containing ultrafine zinc oxide containing iron can be obtained.
【００２２】酸化物被覆の量は、通常、鉄含有超微細酸
化亜鉛に対して、１〜１５重量％の範囲であり、好まし
くは、３〜１０重量％の範囲である。酸化物被覆の量が
鉄含有超微細酸化亜鉛に対して１重量％よりも少ないと
きは、本発明によるような超微細粒子にとって、粒子表
面を被覆するには不十分な量であり、被覆による特性の
向上が期待できない。しかし、酸化物被覆の量が１５重
量％を越えるときは、被覆によって粒子径が大きくな
り、このような粒子を含む塗料を塗膜化したとき、塗膜
の透明性が損なわれるおそれがある。The amount of oxide coating is usually in the range of 1 to 15% by weight, preferably 3 to 10% by weight, based on the iron-containing ultrafine zinc oxide. When the amount of oxide coating is less than 1% by weight, based on the iron-containing ultrafine zinc oxide, it is an insufficient amount for the ultrafine particles according to the invention to coat the particle surface, It cannot be expected to improve the characteristics. However, when the amount of the oxide coating exceeds 15% by weight, the particle size becomes large due to the coating, and when a coating material containing such particles is made into a coating film, the transparency of the coating film may be impaired.
【００２３】このように、鉄含有超微細酸化亜鉛を酸化
物で被覆することによって、分散媒体中における分散性
を高めることができ、また、鉄含有超微細酸化亜鉛を含
む被膜や塗膜の耐久性を高めることができる。As described above, by coating the iron-containing ultrafine zinc oxide with the oxide, the dispersibility in the dispersion medium can be enhanced, and the durability of the coating or the coating containing the iron-containing ultrafine zinc oxide can be improved. You can improve your sex.
【００２４】[0024]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれら実施例により何ら限定されるものではな
い。The present invention will be described below with reference to examples.
The present invention is not limited to these examples.
【００２５】実施例１ 塩化亜鉛水溶液（ＺｎＣｌ2 として６８ｇ／Ｌ）２Ｌに
３５％塩化第二鉄水溶液2.４ｍＬを加え、均一な混合溶
液とした。常温に保持しつつ、攪拌下にこの溶液に炭酸
水素アンモニウム水溶液（ＮＨ4 ＨＣＯ3 として７９ｇ
／Ｌ）2.２Ｌを約１０分を要して添加した。添加終了後
の混合物のｐＨは6.３であった。引続き、混合物を攪拌
しながら、３０分間熟成した。混合物のｐＨは6.４とな
った。このようにして得られた微紅色の中和生成物を濾
過し、水洗した後、これを含水率0.１％以下まで乾燥さ
せた。Example 1 2.4 mL of 35% ferric chloride aqueous solution was added to 2 L of zinc chloride aqueous solution (68 g / L as ZnCl 2 ) to prepare a uniform mixed solution. While maintaining the temperature at room temperature, an aqueous solution of ammonium hydrogen carbonate (79 g as NH 4 HCO 3) was added to the solution under stirring.
/ L) 2.2 L was added over about 10 minutes. The pH of the mixture after the addition was 6.3. Subsequently, the mixture was aged for 30 minutes with stirring. The pH of the mixture was 6.4. The slightly reddish neutralized product thus obtained was filtered, washed with water, and then dried to a water content of 0.1% or less.
【００２６】得られた乾燥物は、そのＸ線回折図から塩
基性炭酸亜鉛と無定形物との混合物であることが確認さ
れた。この乾燥物をコーヒーミルで１分間粉砕した後、
４００℃に保持した電気炉中で約６０分間焼成し、その
後、室温まで冷却して、鉄含有超微細酸化亜鉛を得た。
この焼成物のＸ線回折図は、酸化亜鉛であった。From the X-ray diffraction pattern, it was confirmed that the obtained dried product was a mixture of basic zinc carbonate and an amorphous substance. After crushing this dried product for 1 minute with a coffee mill,
It was baked for about 60 minutes in an electric furnace kept at 400 ° C., and then cooled to room temperature to obtain iron-containing ultrafine zinc oxide.
The X-ray diffraction pattern of this baked product was zinc oxide.
【００２７】実施例２ 実施例１において、３５％塩化第二鉄水溶液を4.８ｍＬ
用いた以外は、実施例１と同様にして、鉄含有超微細酸
化亜鉛を得た。Example 2 In Example 1, 4.8 mL of 35% ferric chloride aqueous solution was added.
An iron-containing ultrafine zinc oxide was obtained in the same manner as in Example 1 except that it was used.
【００２８】実施例３ 実施例１において、３５％塩化第二鉄水溶液を２４ｍＬ
用いた以外は、実施例１と同様にして、鉄含有超微細酸
化亜鉛を得た。Example 3 In Example 1, 24 mL of 35% ferric chloride aqueous solution was added.
An iron-containing ultrafine zinc oxide was obtained in the same manner as in Example 1 except that it was used.
【００２９】比較例１ 塩化亜鉛水溶液に３５％塩化第二鉄水溶液を加えなかっ
た以外は、実施例１と同様にして、超微細酸化亜鉛を得
た。Comparative Example 1 Ultrafine zinc oxide was obtained in the same manner as in Example 1 except that the 35% ferric chloride aqueous solution was not added to the zinc chloride aqueous solution.
【００３０】以上のようにして得られた（鉄含有超微
細）酸化亜鉛を過マンガン酸カリウム滴定法にて鉄の含
有量を、ＢＥＴ法にて比表面積を、また、１０万倍の透
過型電子顕微鏡写真にて平均一次粒子径を、それぞれ測
定した。また、得られた酸化亜鉛をニトロセルロース樹
脂中にペイントシェーカーで分散させ、得られた塗料を
ポリエチレンテレフタレートフィルム上に塗布して、乾
燥膜厚４μｍの塗膜を形成した。これを分光光度計にて
２５０〜８００ｎｍの透過曲線を測定して、紫外線吸収
端を求めた。結果を表１に示す。The (iron-containing ultrafine) zinc oxide obtained as described above was used to determine the iron content by the potassium permanganate titration method, the specific surface area by the BET method, and the transmission type of 100,000 times. The average primary particle diameter was measured with an electron micrograph. Further, the obtained zinc oxide was dispersed in a nitrocellulose resin with a paint shaker, and the obtained coating material was applied on a polyethylene terephthalate film to form a coating film having a dry film thickness of 4 μm. A 250-800 nm transmission curve of this was measured with a spectrophotometer to determine the ultraviolet absorption edge. The results are shown in Table 1.
【００３１】[0031]
【表１】 [Table 1]
【００３２】実施例４ 実施例２で得られた鉄含有超微細酸化亜鉛を濃度１００
ｇ／Ｌとなるように水中に分散させ、湿式粉砕した後、
７０℃に昇温し、攪拌しながら、これに鉄含有超微細酸
化亜鉛に対してＳｉＯ2 として５重量％のケイ酸ナトリ
ウム水溶液を加えた。次いで、硫酸を加えてｐＨを6.５
に調整し、７０℃に保持しながら、６０分間熟成した。
次いで、鉄含有超微細酸化亜鉛に対して、Ａｌ2 Ｏ3 と
して３重量％の塩化アルミニウム水溶液を加え、水酸化
ナトリウム水溶液でｐＨを8.５に調整した後、１２０分
間熟成した。Example 4 The iron-containing ultrafine zinc oxide obtained in Example 2 was added at a concentration of 100.
After being dispersed in water so as to be g / L and wet-milled,
The temperature was raised to 70 ° C., and a 5% by weight aqueous solution of sodium silicate as SiO 2 was added to the iron-containing ultrafine zinc oxide while stirring. Then add sulfuric acid to bring the pH to 6.5.
And aging for 60 minutes while maintaining at 70 ° C.
Then, a 3 wt% aluminum chloride aqueous solution as Al 2 O 3 was added to the iron-containing ultrafine zinc oxide, the pH was adjusted to 8.5 with an aqueous sodium hydroxide solution, and then the mixture was aged for 120 minutes.
【００３３】このように処理した鉄含有超微細酸化亜鉛
を濾過し、水洗し、乾燥させた後、擂潰機で粉砕して、
酸化物被覆鉄含有超微細酸化亜鉛を得た。これを用い
て、以下の処方に基づいて、日焼け止め乳液を調製し、
これを石英ガラスに膜厚２５μｍとなるように塗布した
後、２５０〜８００ｎｍの透過率を測定した。結果を表
２に示す。The iron-containing ultrafine zinc oxide treated in this way is filtered, washed with water, dried and then crushed with a crusher,
Oxide-coated iron-containing ultrafine zinc oxide was obtained. Using this, prepare a sunscreen emulsion based on the following formulation,
This was applied to quartz glass so as to have a film thickness of 25 μm, and then the transmittance of 250 to 800 nm was measured. Table 2 shows the results.
【００３４】 （日焼け止め乳液の処方） トリオクタン酸グリセリル １0.０重量％ パラメトキシ桂皮酸２−エチルヘキシル 5.０重量％ シクロヘキサシロキサン ２0.０重量％ 酸化物被覆鉄含有超微細酸化亜鉛 5.０重量％ エタノール １0.０重量％ 精製水 ５0.０重量％(Formulation of Sunscreen Emulsion) Glyceryl trioctanoate 10.0% by weight 2-Ethylhexyl paramethoxycinnamate 5.0% by weight Cyclohexasiloxane 20.0% by weight Oxide-coated iron-containing ultrafine zinc oxide 5.0% by weight % Ethanol 10.0% by weight Purified water 50.0% by weight
【００３５】比較例２ 比較例１で得られた超微細酸化亜鉛を用いて、実施例４
と同様にして日焼け止め乳液を調製した。これを石英ガ
ラスに膜厚２５μｍとなるように塗布した後、２５０〜
８００ｎｍの透過率を測定した。結果を表２に示す。Comparative Example 2 Using the ultrafine zinc oxide obtained in Comparative Example 1, Example 4
A sunscreen emulsion was prepared in the same manner as in. After applying this to quartz glass to a film thickness of 25 μm,
The transmittance at 800 nm was measured. Table 2 shows the results.
【００３６】[0036]
【表２】 [Table 2]
【００３７】実施例５ 実施例４で得られた酸化物被覆鉄含有超微細酸化亜鉛を
下記の処方で紫外線遮蔽塗料とし、これを石英ガラスに
膜厚２５μｍとなるように塗布した後、２５０〜８００
ｎｍの透過率を測定した。結果を表３に示す。Example 5 The oxide-coated iron-containing ultrafine zinc oxide obtained in Example 4 was used as an ultraviolet-shielding coating composition having the following formulation, and this coating composition was applied to quartz glass so as to have a film thickness of 25 μm. 800
The transmittance in nm was measured. The results are shown in Table 3.
【００３８】 （紫外線遮蔽塗料の処方） 酸化物被覆鉄含有超微細酸化亜鉛 ５0.０重量％ ベッコライトＭ−６６０２−６０Ｓ（大日本インキ 化学工業（株）製） ４0.０重量％ スーパーベッカミンＪ−８２０（大日本インキ化学 工業（株）製） １0.０重量％(Formulation of UV Shielding Coating) Oxide-coated iron-containing ultrafine zinc oxide 50.0% by weight Beckolite M-6602-60S (manufactured by Dainippon Ink and Chemicals, Inc.) 40.0% by weight Super Beckamine J-820 (manufactured by Dainippon Ink and Chemicals, Inc.) 10.0% by weight
【００３９】比較例３ 比較例１で得られた超微細酸化亜鉛を用いて、実施例５
と同様にして、塗料化し、これを石英ガラスに膜厚２５
μｍとなるように塗布した後、２５０〜８００ｎｍの透
過率を測定した。結果を表３に示す。Comparative Example 3 Using the ultrafine zinc oxide obtained in Comparative Example 1, Example 5 was used.
In the same manner as above, make a paint, and apply this to quartz glass to a film thickness of 25
After coating so as to have a thickness of μm, the transmittance of 250 to 800 nm was measured. The results are shown in Table 3.
【００４０】[0040]
【表３】 [Table 3]
【００４１】[0041]
【発明の効果】本発明による鉄含有超微細酸化亜鉛は、
酸化亜鉛の結晶格子内部に鉄が固溶しているので、鉄成
分の有する幅広い紫外線吸収能と超微細酸化亜鉛のもつ
透明性が同時に発現され、紫外線のＡ領域を完全に遮蔽
することができる。また、酸化亜鉛の結晶格子内部に鉄
が固溶していることから、鉄成分と酸化亜鉛との色分か
れもない。日焼け止め化粧料や紫外線遮蔽塗料に用いれ
ば、透明性にすぐれる利点もある。The ultrafine zinc oxide containing iron according to the present invention is
Since iron is solid-solved inside the crystal lattice of zinc oxide, the wide ultraviolet absorption ability of the iron component and the transparency of ultrafine zinc oxide are simultaneously expressed, and the A region of ultraviolet rays can be completely shielded. . Further, since iron is solid-solved inside the zinc oxide crystal lattice, there is no color separation between the iron component and zinc oxide. When used in sunscreen cosmetics and UV-shielding paints, it also has the advantage of excellent transparency.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 5/32 ＰＲＢ Ｃ０９Ｄ 5/32 ＰＲＢ (72)発明者 小林 恵太 福島県いわき市泉町下川字田宿110番地 堺化学工業株式会社小名浜事業所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number in the agency FI Technical display location C09D 5/32 PRB C09D 5/32 PRB (72) Inventor Keita Kobayashi Shimokawa, Izumi-cho, Iwaki, Fukushima Prefecture 110 inn, Sakai Chemical Industry Co., Ltd., Onahama Plant
Claims (6)
鉛であって、その結晶格子内部に鉄を0.１〜１０重量％
の範囲で有する鉄含有超微細酸化亜鉛。1. Zinc oxide having an average primary particle diameter of 0.01 to 0.1 μm, in which 0.1 to 10% by weight of iron is contained in the crystal lattice.
Fe-containing ultrafine zinc oxide having a range of.
ニウム又は炭酸水素アンモニウムにて中和し、得られた
沈殿を濾過、水洗、乾燥した後、酸化性雰囲気下に３０
０〜６００℃の温度で焼成することを特徴とする平均一
次粒子径0.０１〜0.１μｍの酸化亜鉛であって、その結
晶格子内部に鉄を0.１〜１０重量％の範囲で有する鉄含
有超微細酸化亜鉛の製造方法。2. An aqueous solution containing a zinc salt and an iron salt is neutralized with ammonium carbonate or ammonium hydrogencarbonate, and the obtained precipitate is filtered, washed with water and dried, and then subjected to 30 in an oxidizing atmosphere.
Zinc oxide having an average primary particle size of 0.01 to 0.1 μm, characterized by being fired at a temperature of 0 to 600 ° C., and having iron within the crystal lattice of 0.1 to 10% by weight. Method for producing iron-containing ultrafine zinc oxide.
鉛であって、その結晶格子内部に鉄を0.１〜１０重量％
の範囲で有すると共に、その粒子表面にアルミニウム、
ケイ素、チタン、ジルコニウム、スズ及びアンチモンか
ら選ばれる少なくとも１種の元素の含水酸化物又は酸化
物からなる被覆を酸化物換算で鉄含有超微細酸化亜鉛に
対して１〜１５重量％の範囲で有することを特徴とする
酸化物被覆鉄含有超微細酸化亜鉛。3. Zinc oxide having an average primary particle diameter of 0.01 to 0.1 μm, in which 0.1 to 10% by weight of iron is contained in the crystal lattice.
In addition to having in the range of, aluminum on the particle surface,
A coating containing a hydrous oxide or oxide of at least one element selected from silicon, titanium, zirconium, tin and antimony is contained in an amount of 1 to 15% by weight based on the iron-containing ultrafine zinc oxide in terms of oxide. An oxide-coated iron-containing ultrafine zinc oxide characterized by the above.
鉛であって、その結晶格子内部に鉄を0.１〜１０重量％
の範囲で有する鉄含有超微細酸化亜鉛を水に分散させて
スラリーとし、このスラリーにアルミニウム、ケイ素、
チタン、ジルコニウム、スズ及びアンチモンから選ばれ
る少なくとも１種の元素の水溶性塩を酸化物換算で上記
鉄含有超微細酸化亜鉛に対して１〜１５重量％の範囲で
加えた後、中和し、上記元素の含水酸化物又は酸化物を
前記鉄含有超微細酸化亜鉛粒子表面に被着させることを
特徴とする酸化物被覆鉄含有超微細酸化亜鉛の製造方
法。4. Zinc oxide having an average primary particle diameter of 0.01 to 0.1 μm, in which 0.1 to 10% by weight of iron is contained in the crystal lattice.
Iron-containing ultrafine zinc oxide having a range of is dispersed in water to form a slurry, aluminum, silicon,
After adding a water-soluble salt of at least one element selected from titanium, zirconium, tin and antimony in the range of 1 to 15% by weight to the iron-containing ultrafine zinc oxide in terms of oxide, it is neutralized, A method for producing oxide-coated ultrafine zinc oxide containing iron, comprising depositing a hydrous oxide or oxide of the above element on the surface of the ultrafine zinc oxide containing iron.
亜鉛を含有する日焼け止め化粧料。5. A sunscreen cosmetic containing the iron-containing ultrafine zinc oxide according to claim 1 or 3.
亜鉛を含有する紫外線遮蔽塗料。6. An ultraviolet shielding paint containing the iron-containing ultrafine zinc oxide according to claim 1 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12096A JPH09188517A (en) | 1996-01-04 | 1996-01-04 | Iron-containing superfine zinc oxide, its production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12096A JPH09188517A (en) | 1996-01-04 | 1996-01-04 | Iron-containing superfine zinc oxide, its production and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09188517A true JPH09188517A (en) | 1997-07-22 |
Family
ID=11465190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12096A Pending JPH09188517A (en) | 1996-01-04 | 1996-01-04 | Iron-containing superfine zinc oxide, its production and use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09188517A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6783855B1 (en) | 1998-12-17 | 2004-08-31 | Isis Innovation Limited | Rare-earth-activated phosphors |
| US6869596B1 (en) | 1998-05-27 | 2005-03-22 | Isis Innovation Limited | Ultraviolet light screening compositions |
| JP2005263612A (en) * | 2004-02-18 | 2005-09-29 | Nippon Shokubai Co Ltd | Metal oxide particle and its use |
| JP2005263620A (en) * | 2004-02-18 | 2005-09-29 | Nippon Shokubai Co Ltd | Metal oxide particle and its use |
| WO2005076752A3 (en) * | 2004-02-18 | 2005-10-06 | Nippon Catalytic Chem Ind | Metal oxide particle and its uses |
| JP2006514115A (en) * | 2002-12-24 | 2006-04-27 | オクソニカ リミテッド | Sunscreen |
| JP2006188386A (en) * | 2005-01-05 | 2006-07-20 | Nippon Shokubai Co Ltd | Particulate metal oxide and use of the same |
| JP2006298749A (en) * | 2005-03-22 | 2006-11-02 | Toshiba Lighting & Technology Corp | Ultraviolet cut material, ultraviolet cut filter, tube-bulb, and lighting apparatus |
| JP2007297260A (en) * | 2006-04-05 | 2007-11-15 | Sakai Chem Ind Co Ltd | Hyperfine particle zinc oxide and its production method |
| WO2008044469A1 (en) * | 2006-10-06 | 2008-04-17 | Sakai Chemical Industry Co., Ltd. | Ultrafine zinc oxide particle and process for production thereof |
| WO2010123142A1 (en) * | 2009-04-22 | 2010-10-28 | 協和化学工業株式会社 | Columnar zinc oxide particles and method for producing same |
| JP2013060375A (en) * | 2011-09-12 | 2013-04-04 | Daito Kasei Kogyo Kk | Metal oxide-zinc oxide solid solution particle, method for producing the same, spherical powder, coated spherical powder and cosmetic |
| JP2014043533A (en) * | 2012-08-28 | 2014-03-13 | Daito Kasei Kogyo Kk | Composite powder and method for manufacturing same and cosmetic |
| WO2015098992A1 (en) | 2013-12-27 | 2015-07-02 | 堺化学工業株式会社 | Zinc oxide particles, production method for same, ultraviolet ray shielding agent, and cosmetic material |
| WO2015098993A1 (en) | 2013-12-27 | 2015-07-02 | 堺化学工業株式会社 | Zinc oxide particles, production method for same, ultraviolet ray shielding agent, and cosmetic material |
| JP6183677B1 (en) * | 2016-06-02 | 2017-08-23 | エム・テクニック株式会社 | Colored UV protection agent |
| WO2017208616A1 (en) * | 2016-06-02 | 2017-12-07 | エム・テクニック株式会社 | Colorant / uv protectant |
| WO2018150477A1 (en) | 2017-02-14 | 2018-08-23 | エム・テクニック株式会社 | Silicon-doped metal oxide particles, and uv-absorbing composition containing silicon-doped metal oxide particles |
-
1996
- 1996-01-04 JP JP12096A patent/JPH09188517A/en active Pending
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8642019B2 (en) | 1998-05-27 | 2014-02-04 | Isis Innovation Limited | Ultraviolet light screening compositions |
| US6869596B1 (en) | 1998-05-27 | 2005-03-22 | Isis Innovation Limited | Ultraviolet light screening compositions |
| US6783855B1 (en) | 1998-12-17 | 2004-08-31 | Isis Innovation Limited | Rare-earth-activated phosphors |
| JP2006514115A (en) * | 2002-12-24 | 2006-04-27 | オクソニカ リミテッド | Sunscreen |
| JP2005263612A (en) * | 2004-02-18 | 2005-09-29 | Nippon Shokubai Co Ltd | Metal oxide particle and its use |
| JP2005263620A (en) * | 2004-02-18 | 2005-09-29 | Nippon Shokubai Co Ltd | Metal oxide particle and its use |
| WO2005076752A3 (en) * | 2004-02-18 | 2005-10-06 | Nippon Catalytic Chem Ind | Metal oxide particle and its uses |
| JP2006188386A (en) * | 2005-01-05 | 2006-07-20 | Nippon Shokubai Co Ltd | Particulate metal oxide and use of the same |
| JP2006298749A (en) * | 2005-03-22 | 2006-11-02 | Toshiba Lighting & Technology Corp | Ultraviolet cut material, ultraviolet cut filter, tube-bulb, and lighting apparatus |
| JP2007297260A (en) * | 2006-04-05 | 2007-11-15 | Sakai Chem Ind Co Ltd | Hyperfine particle zinc oxide and its production method |
| WO2008044469A1 (en) * | 2006-10-06 | 2008-04-17 | Sakai Chemical Industry Co., Ltd. | Ultrafine zinc oxide particle and process for production thereof |
| KR101455419B1 (en) * | 2006-10-06 | 2014-10-28 | 사까이가가꾸고오교가부시끼가이샤 | Ultrafine zinc oxide particle and process for production thereof |
| WO2010123142A1 (en) * | 2009-04-22 | 2010-10-28 | 協和化学工業株式会社 | Columnar zinc oxide particles and method for producing same |
| CN102395532A (en) * | 2009-04-22 | 2012-03-28 | 协和化学工业株式会社 | Columnar zinc oxide particles and method for producing same |
| JP5570077B2 (en) * | 2009-04-22 | 2014-08-13 | 協和化学工業株式会社 | Columnar zinc oxide particles and method for producing the same |
| JP2013060375A (en) * | 2011-09-12 | 2013-04-04 | Daito Kasei Kogyo Kk | Metal oxide-zinc oxide solid solution particle, method for producing the same, spherical powder, coated spherical powder and cosmetic |
| JP2014043533A (en) * | 2012-08-28 | 2014-03-13 | Daito Kasei Kogyo Kk | Composite powder and method for manufacturing same and cosmetic |
| WO2015098992A1 (en) | 2013-12-27 | 2015-07-02 | 堺化学工業株式会社 | Zinc oxide particles, production method for same, ultraviolet ray shielding agent, and cosmetic material |
| WO2015098993A1 (en) | 2013-12-27 | 2015-07-02 | 堺化学工業株式会社 | Zinc oxide particles, production method for same, ultraviolet ray shielding agent, and cosmetic material |
| US9775787B2 (en) | 2013-12-27 | 2017-10-03 | Sakai Chemical Industry Co., Ltd. | Zinc oxide particle, method for producing the same, ultraviolet shielding agent, and cosmetic |
| US9789037B2 (en) | 2013-12-27 | 2017-10-17 | Sakai Chemical Industry Co., Ltd. | Zinc oxide particle, method for producing the same, ultraviolet shielding agent, and cosmetic |
| TWI641557B (en) * | 2013-12-27 | 2018-11-21 | 堺化學工業股份有限公司 | Zinc oxide particles, manufacturing method thereof, ultraviolet shielding agent and cosmetic |
| TWI670235B (en) * | 2013-12-27 | 2019-09-01 | 日商堺化學工業股份有限公司 | Zinc oxide particles, methods for producing the same, ultraviolet shielding agents, and cosmetics |
| JP6183677B1 (en) * | 2016-06-02 | 2017-08-23 | エム・テクニック株式会社 | Colored UV protection agent |
| WO2017208616A1 (en) * | 2016-06-02 | 2017-12-07 | エム・テクニック株式会社 | Colorant / uv protectant |
| KR20190015352A (en) * | 2016-06-02 | 2019-02-13 | 엠. 테크닉 가부시키가이샤 | Colored anti-UV agent |
| WO2018150477A1 (en) | 2017-02-14 | 2018-08-23 | エム・テクニック株式会社 | Silicon-doped metal oxide particles, and uv-absorbing composition containing silicon-doped metal oxide particles |
| KR20190119605A (en) | 2017-02-14 | 2019-10-22 | 엠. 테크닉 가부시키가이샤 | A composition for absorbing ultraviolet rays comprising silicon dope metal oxide particles, and silicon dope metal oxide particles |
| US11591239B2 (en) | 2017-02-14 | 2023-02-28 | M. Technique Co., Ltd. | Silicon doped metal oxide particles, and composition for UV absorption comprising silicon doped metal oxide particles |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH09188517A (en) | Iron-containing superfine zinc oxide, its production and use | |
| JP4018770B2 (en) | Fan-shaped titanium oxide, method for producing fan-shaped or plate-shaped titanium oxide, and use thereof | |
| JP3520785B2 (en) | Zinc oxide particle composition with suppressed surface activity, method for producing the same, and cosmetic containing the composition | |
| ES2224104T3 (en) | ULTRAFIN PARTICLES OF TITANIUM DIOXIDE TYPE RUTILO CONTAINING IRON AND PROCEDURE FOR PREPARATION. | |
| DE3941543B4 (en) | dispersions | |
| CN105084412B (en) | Zinc oxide grains with manganese ion doping object | |
| EP1112964B1 (en) | Zinc oxide particles having suppressed surface activity and production and use thereof | |
| JP2585128B2 (en) | Colored fine particle inorganic pigment | |
| JPH07247119A (en) | Titanium dioxide aqueous dispersion | |
| JPH11193354A (en) | Silica-coated zinc oxide particle, its preparation, and composition containing it | |
| JP3534039B2 (en) | Zinc oxide particles with reduced surface activity and their production and use | |
| JP2006316107A (en) | Composite ultraviolet blocking agent, cosmetic and resin composition | |
| JP2717904B2 (en) | Iron-containing ultrafine rutile titanium dioxide and method for producing the same | |
| JP2008094917A (en) | Surface-coated zinc oxide and its manufacturing method, and ultraviolet ray-shielding composition comprising the same | |
| JP4201880B2 (en) | Butterfly-like rutile titanium oxide, method for producing the same, and use thereof | |
| JPH11256133A (en) | Ultraviolet light-screening agent and its production | |
| JP4256133B2 (en) | Method for producing acicular titanium dioxide fine particles | |
| JP3877235B2 (en) | Rutile-type titanium dioxide particles and production method thereof | |
| JP2852482B2 (en) | Iron-containing titanium dioxide and method for producing the same | |
| JP2010168254A (en) | Ultraviolet screening agent, cosmetic, and micro-acicular zinc oxide | |
| JP4256134B2 (en) | Method for producing iron-containing acicular titanium dioxide fine particles | |
| JP2002060724A (en) | Ultrasonic light-screening agent | |
| JP2003253249A (en) | Ultraviolet-shielding material | |
| JP2931180B2 (en) | Method for producing iron-containing ultrafine titanium dioxide | |
| JP2008273759A (en) | Zinc oxide and method for producing the same and ultraviolet shielding composition using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060324 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060509 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20060912 |