JP2687640B2 - Ultrafine zinc oxide powder having excellent ultraviolet absorption capacity and method for producing the same - Google Patents
Ultrafine zinc oxide powder having excellent ultraviolet absorption capacity and method for producing the sameInfo
- Publication number
- JP2687640B2 JP2687640B2 JP1338485A JP33848589A JP2687640B2 JP 2687640 B2 JP2687640 B2 JP 2687640B2 JP 1338485 A JP1338485 A JP 1338485A JP 33848589 A JP33848589 A JP 33848589A JP 2687640 B2 JP2687640 B2 JP 2687640B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc oxide
- oxide powder
- ultrafine
- zinc
- transparency
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は紫外線吸収能に優れた超微粒子酸化亜鉛（Zn
O）粉末およびその製造方法に関する。より詳しくは、
膜、成形体およびペースト等に分散させて、例えば日焼
け止め化粧料、自動車、家具、光学材料等の紫外線遮断
保護膜に利用することのできる超微粒子ZnO粉末および
その製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to ultrafine zinc oxide (Zn
O) Powder and its manufacturing method. More specifically,
The present invention relates to ultrafine ZnO powder that can be dispersed in a film, a molded body, a paste, or the like and can be used as an ultraviolet protection film for sunscreen cosmetics, automobiles, furniture, optical materials, and the like, and a method for producing the same.
紫外線遮断効果を有する材料は従来からよく知られて
いる。有機系では例えばベンゾトリアゾール、ベンゾフ
ェノン等、無機系では例えば酸化チタン（TiO2）、ZnO
等がある。これらの中で有機系のものは皮膚刺激性や化
合物自身の光分解等の問題があり、また無機系のものは
粒子径が比較的大きく透明性が小さい問題がある。細
菌、有機粉体の透明性を良くするため超微粒子化するこ
とが検討され、光の散乱を小さくして透明性を向上させ
た超微粒子のTiO2、超微粒子のZnO等が市販されてい
る。しかし酸化亜鉛の粒径は殆どが0.2〜0.5μｍ程度で
あって、透明性は未だ不十分である。またZnO粉末を微
粒子化する場合、熱分解温度あるいは焼成温度を低く
し、粒子の成長を抑制して微粒子化しているが、出発原
料によっては熱分解温度を低下しても上記粒径以下の微
粒子を得られない。Materials having an ultraviolet blocking effect are well known in the art. For organic type, for example, benzotriazole, benzophenone, etc. For inorganic type, for example, titanium oxide (TiO 2 ), ZnO
Etc. Among these, the organic ones have problems such as skin irritation and photodecomposition of the compound itself, and the inorganic ones have problems that the particle size is relatively large and the transparency is small. Ultrafine particles have been studied to improve the transparency of bacteria and organic powders, and ultrafine particles of TiO 2 and ZnO that have improved transparency by reducing light scattering are commercially available. . However, most of the particle size of zinc oxide is about 0.2 to 0.5 μm, and the transparency is still insufficient. When the ZnO powder is made into fine particles, the thermal decomposition temperature or the firing temperature is lowered to suppress the growth of the particles and the particles are made fine. Can't get
このように高い透明性と紫外線吸収効果とを同時に有
する酸化亜鉛粉末は得られていないのが現状である。At present, no zinc oxide powder having both high transparency and ultraviolet ray absorbing effect has been obtained.
そこで本発明者等は、炭酸亜鉛のCO2が一次粒子の凝
集を抑制して分散性のよい超微粒子ZnO粉末を与えるこ
とに注目し、熱分解温度の低い塩基性炭酸亜鉛（265
℃）を原料として、CO2の存在下で熱分解させることに
より粒子の超微粒子化を図り、透明性と紫外線吸収能に
優れた超微粒子ZnO粉末が得られることを見出した。Therefore, the present inventors have noted that CO 2 of zinc carbonate suppresses agglomeration of primary particles to give ultrafine ZnO powder having good dispersibility, and basic zinc carbonate (265
It was found that the particles can be made into ultrafine particles by thermally decomposing them in the presence of CO 2 as a raw material, and ultrafine ZnO powders having excellent transparency and ultraviolet absorbing ability can be obtained.
本発明によれば、平均粒子径が0.01〜0.03μｍで、CO
2含有量が0.1〜3.0％である透明性と紫外線吸収能に優
れた超微粒子酸化亜鉛粉末が提供される。According to the present invention, the average particle size is 0.01 to 0.03 μm, and CO
(2) An ultrafine zinc oxide powder having a content of 0.1 to 3.0% and excellent in transparency and ultraviolet absorbing ability is provided.
また本発明によれば、炭酸アンモニウムまたは炭酸水
素アンモニウムの水溶液に、塩化亜鉛または硫酸硫酸亜
鉛の水溶液を加え、得られた析出物を水洗、濾別、乾燥
して得た塩基性炭酸亜鉛を265〜350℃の温度で熱分解す
ることにより、平均粒子径が0.01〜0.03μｍで、CO2含
有量が0.1〜3.0％である酸化亜鉛粉末を製造することを
特徴とする超微粒子酸化亜鉛粉末の製造方法が提供され
る。According to the present invention, an aqueous solution of zinc chloride or zinc sulfate sulfate is added to an aqueous solution of ammonium carbonate or ammonium hydrogen carbonate, and the resulting precipitate is washed with water, filtered and dried to obtain basic zinc carbonate 265 Of zinc oxide powder having an average particle size of 0.01 to 0.03 μm and a CO 2 content of 0.1 to 3.0% by thermal decomposition at a temperature of up to 350 ° C. A manufacturing method is provided.
本発明の超微粒子ZnO粉末は、平均粒子径が0.01〜0.0
3μｍの超微粒子である。従来のZnOは粒径が0.2〜0.5μ
ｍであって、可視光を散乱するため不透明である。発明
者等の試験結果によれば平均粒子径が0.03μｍ以上にな
ると透明性が低下する。また平均粒子径が0.01μｍ以下
では、一次粒子の凝集が生じ、この場合にも透明性が低
下する。The ultrafine ZnO powder of the present invention has an average particle size of 0.01 to 0.0.
Ultrafine particles of 3 μm. Conventional ZnO has a particle size of 0.2-0.5μ
m, which is opaque because it scatters visible light. According to the test results of the inventors, the transparency decreases when the average particle diameter is 0.03 μm or more. When the average particle size is 0.01 μm or less, the primary particles agglomerate, and in this case also the transparency is lowered.
更に本発明の超微粒子ZnO粉末は、0.1〜3.0％のCO
2（ZnCO3）を含有する。該CO2の存在により、原料の炭
酸亜鉛の熱分解時に一次粒子の擬集が防止され、分散性
に優れた上記粒径の超微粒子酸化亜鉛粉末が得られる。
ところでZnOは370nm以下の紫外線を吸収する性質を有す
るが、ZnCO3には紫外線吸収作用がなく、ZnCO3が共存す
ればZnO量が相対的に低下するが、CO2含有量（ZnCO
3量）が3.0％より少なければ良好な紫外線遮断効果を維
持できる。CO2含有量（ZnCO3量）が3.0％を越えると超
微粒子化して粒子の透明性は向上するが紫外線遮断能が
低下するので好ましくない、またCO2含有量（ZnCO3量）
が0.1％より少ないと一次粒子の凝集を抑制する効果が
不十分であり、分散性が低下するため優れた透明性を得
ることができない。Furthermore, the ultrafine ZnO powder of the present invention has a CO content of 0.1 to 3.0%.
Contains 2 (ZnCO 3 ). Due to the presence of CO 2 , primary particles are prevented from being aggregated during the thermal decomposition of zinc carbonate as a raw material, and ultrafine zinc oxide powder having the above particle size and excellent in dispersibility can be obtained.
By the way, ZnO has a property of absorbing ultraviolet rays of 370 nm or less, but ZnCO 3 does not have an ultraviolet absorbing effect, and if ZnCO 3 coexists, the ZnO content decreases relatively, but the CO 2 content (ZnCO 3
If the amount is less than 3.0%, a good UV blocking effect can be maintained. If the CO 2 content (ZnCO 3 content) exceeds 3.0%, the particles become ultrafine and the transparency of the particles is improved, but the UV blocking ability is reduced, which is not desirable. Also, the CO 2 content (ZnCO 3 content)
Is less than 0.1%, the effect of suppressing the agglomeration of primary particles is insufficient, and the dispersibility decreases, so that excellent transparency cannot be obtained.
透明性と紫外線遮断効果に優れた上記酸化亜鉛粒子
は、炭酸アンモニウムまたは炭酸水素アンモニウムの水
溶液に、塩化亜鉛または硫酸亜鉛の水溶液を加え、得ら
れた析出物を水洗、濾別、乾燥して得た塩基性炭酸亜鉛
を265〜350℃の温度で熱分解することにより製造され
る。The zinc oxide particles excellent in transparency and ultraviolet blocking effect are obtained by adding an aqueous solution of zinc chloride or zinc sulfate to an aqueous solution of ammonium carbonate or ammonium hydrogencarbonate, washing the resulting precipitate with water, filtering and drying. It is produced by pyrolyzing basic zinc carbonate at a temperature of 265 to 350 ° C.
上記塩基性炭酸亜鉛の分解温度は265℃であり、265℃
以下では炭酸亜鉛の未分解物が多量に残存し、所望の酸
化亜鉛粉末を得ることができない。また上記熱分解温度
が350℃を越えると炭酸基は殆どCO2に分解され除去され
るので粒子の凝集が進み、0.01μｍレベルの超微粒子粉
末を得ることができない。一例としてシュウ酸亜鉛を原
料に用いいると、熱分解温度が450℃と高いため、0.03
μｍ以下の超微粒子ZnO粉末を得ることは困難である。The decomposition temperature of the basic zinc carbonate is 265 ° C, 265 ° C
Below, a large amount of undecomposed matter of zinc carbonate remains, and the desired zinc oxide powder cannot be obtained. When the thermal decomposition temperature exceeds 350 ° C., most of the carbonic acid groups are decomposed and removed by CO 2 and the particles agglomerate, making it impossible to obtain ultrafine particles of 0.01 μm level. As an example, when zinc oxalate is used as the raw material, the thermal decomposition temperature is as high as 450 ℃, so 0.03
It is difficult to obtain ultrafine ZnO powder having a particle size of μm or less.
本発明においては、前述のように熱分解温度が低いの
で、炭酸基をZnO粉末中に残存させることができ、熱分
解時の粒子の凝集が充分に抑制される。なお、CO2ガス
あるいは炭酸を用いてZnOを処理する方法ではZnOの粒子
径を所望の範囲に調整することが難しく、分散性の良い
透明性に優れたZnO粉末を得ることはできない。In the present invention, since the thermal decomposition temperature is low as described above, the carbonate groups can be left in the ZnO powder, and the aggregation of particles during thermal decomposition can be sufficiently suppressed. It is difficult to adjust the particle size of ZnO to a desired range by the method of treating ZnO with CO 2 gas or carbonic acid, and it is not possible to obtain ZnO powder having good dispersibility and excellent transparency.
本発明の超微粒子酸化亜鉛粉末を用いれば、可視域で
の高い透明性と優れた紫外線遮断効果を有する塗膜を製
造することが出来る。さらに、本発明による超微粒子酸
化亜鉛粉末は日焼け止め化粧料、自動車、家具、光学材
料などの紫外線遮断保護膜に利用することが出来る。By using the ultrafine zinc oxide powder of the present invention, it is possible to produce a coating film having high transparency in the visible region and an excellent ultraviolet blocking effect. Furthermore, the ultrafine zinc oxide powder according to the present invention can be used for a sunscreen cosmetic, an ultraviolet protection film for automobiles, furniture, optical materials and the like.
本発明の実施例及び比較例を以下に示す。 Examples and comparative examples of the present invention are shown below.
実施例１ 炭酸アンモニウム水溶液（0.2mol/l）に硫酸亜鉛水溶
液（0.2mol/l）を滴下して塩基性炭酸亜鉛の沈殿を生成
させ、水洗により塩類を除去し、濾別、乾燥を行なった
後、265℃で１時間加熱分解させて酸化亜鉛の超微粒子
粉末を得た。Example 1 An aqueous solution of zinc sulfate (0.2 mol / l) was added dropwise to an aqueous solution of ammonium carbonate (0.2 mol / l) to form a precipitate of basic zinc carbonate, washed with water to remove salts, filtered and dried. Then, it was decomposed by heating at 265 ° C. for 1 hour to obtain ultrafine zinc oxide powder.
この超微粒子酸化亜鉛粉末の比表面積（BET法）は90m
2/g、一次粒子径は0.01μｍ、CO2含有量は3.0％であっ
た。The specific surface area (BET method) of this ultrafine zinc oxide powder is 90m
2 / g, the primary particle size was 0.01 μm, and the CO 2 content was 3.0%.
次いで、この超微粒子酸化亜鉛粉末を用いて第１表に
示す塗料を調合し、PETフィルム上に塗布して成膜させ
た後、分光光度計により可視領域および紫外領域の透過
率と遮断率を測定した。その結果は第１図に示したよう
に、400nmの可視領域で透過率75％、370mmの紫外領域に
おいて遮断率95％であり、優れた透明性と紫外線遮断効
果を示した。Then, using the ultrafine zinc oxide powder, the paints shown in Table 1 were prepared, coated on a PET film to form a film, and then the transmittance and blocking ratio in the visible region and ultraviolet region were measured by a spectrophotometer. It was measured. As a result, as shown in FIG. 1, the transmittance was 75% in the visible region of 400 nm and the blocking ratio was 95% in the ultraviolet region of 370 mm, showing excellent transparency and ultraviolet blocking effect.
第１表 塗料調合 （重量部） 超微粒子酸化亜鉛粉末 17 PET樹脂＊ 42 トルエン 33メチルエチルケトン(MEK) ８ PET樹脂 ＊商品名パイロナール2088（東洋紡製） 実施例２ 炭酸水素アンモニウム水溶液（0.2mol/l）に塩化亜鉛
水溶液（0.2mol/l）を滴下して塩基性炭酸亜鉛の沈殿を
生成させ、水洗、濾過、乾燥を行なった後、350℃で10
時間加熱分解させて酸化亜鉛の粉末を得た。この酸化亜
鉛粉末の比表面積は50m2/g（BET法）、一次粒子径0.02
μｍの超微粒子粉末であり、CO2含有量は0.1％であっ
た。Table 1 Paint formulation (parts by weight) Ultrafine zinc oxide powder 17 PET resin * 42 Toluene 33 Methyl ethyl ketone (MEK) 8 PET resin * Trade name Pyronal 2088 (manufactured by Toyobo) Example 2 Aqueous ammonium hydrogen carbonate solution (0.2 mol / l) Aqueous zinc chloride solution (0.2mol / l) was added dropwise to the mixture to form a precipitate of basic zinc carbonate, which was washed with water, filtered, and dried at 350 ℃.
It was thermally decomposed for a period of time to obtain zinc oxide powder. The specific surface area of this zinc oxide powder is 50 m 2 / g (BET method), primary particle size is 0.02
It was an ultrafine powder of μm and had a CO 2 content of 0.1%.
次いで、この超微粒子酸化亜鉛粉末を用い、実施例１
と同様に成膜して可視領域および紫外領域における透過
率と遮断率を測定した結果、400nmの可視領域で透過率7
0％、370nmの紫外領域において遮断率98％であり、優れ
た透明性と紫外線遮断効果を示した。Then, using this ultrafine zinc oxide powder, Example 1
A film was formed in the same manner as above, and the transmittance and blocking ratio in the visible and ultraviolet regions were measured.
The blocking rate was 98% in the ultraviolet region of 0% and 370 nm, and it showed excellent transparency and ultraviolet blocking effect.
比較例１ 実施例１と同様にして塩基性炭酸亜鉛を調製した後、
500℃で２時間加熱分解して酸化亜鉛の粉末を得た。こ
の粉末は、比表面積（BET法）30m2/g、一次粒子径0.05
μｍ、CO2含有量は0.07％であった。Comparative Example 1 After preparing basic zinc carbonate in the same manner as in Example 1,
It was heated and decomposed at 500 ° C. for 2 hours to obtain zinc oxide powder. This powder has a specific surface area (BET method) of 30 m 2 / g and a primary particle size of 0.05.
μm, CO 2 content was 0.07%.
実施例１と同様にしてこの超微粒子酸化亜鉛粉末を用
いてPETフィルム上に成膜し、可視および紫外の両領域
について透過率と遮断率を測定した結果、370nmの遮断
率は98％で優れた紫外線遮断効果を示したが、400nmの
透過率は65％であり可視領域における透明性が大幅に低
下した。The ultrafine zinc oxide powder was used to form a film on a PET film in the same manner as in Example 1, and the transmittance and blocking rate were measured in both the visible and ultraviolet regions. As a result, the blocking rate at 370 nm was excellent at 98%. Although it showed an ultraviolet blocking effect, the transmittance at 400 nm was 65%, which significantly reduced the transparency in the visible region.
比較例２ 実施例１と同様にして塩基性炭酸亜鉛を調製した後、
250℃で１時間加熱、分解して酸化亜鉛の粉末を得た。
この粉末の比表面積（BET法）は40m2/g、一次粒子径は
0.04μｍ、CO2含有量は5.0％であった。Comparative Example 2 After preparing basic zinc carbonate in the same manner as in Example 1,
It was heated at 250 ° C. for 1 hour and decomposed to obtain zinc oxide powder.
The specific surface area (BET method) of this powder is 40 m 2 / g, and the primary particle size is
The content was 0.04 μm and the CO 2 content was 5.0%.
この超微粒子酸化亜鉛粉末を用いて、実施例１と同様
の方法で、可視、紫外両領域における透過率と遮断率を
測定した結果、400nmの透過率は78％で透明性は良好で
あったが、370nmの紫外線遮断率は60％であり、紫外線
遮断率は大幅に低下した。Using this ultrafine zinc oxide powder, the transmittance and blocking ratio in both the visible and ultraviolet regions were measured by the same method as in Example 1. As a result, the transmittance at 400 nm was 78% and the transparency was good. However, the UV blocking rate at 370 nm was 60%, and the UV blocking rate was significantly reduced.
図はPETフィルム（曲線１）と、該フィルム上に本発明
の酸化亜鉛を含む紫外線遮断透明膜を形成したフィルム
（曲線２）の分光透過曲線を示すグラフである。The figure is a graph showing the spectral transmission curves of a PET film (curve 1) and a film (curve 2) on which the UV-blocking transparent film containing zinc oxide of the present invention is formed.
Claims (2)
量が0.1〜3.0％である、透明性と紫外線吸収能に優れた
超微粒子酸化亜鉛粉末。1. An ultrafine zinc oxide powder having an average particle diameter of 0.01 to 0.03 μm and a CO 2 content of 0.1 to 3.0%, which is excellent in transparency and ultraviolet ray absorbing ability.
ウムの水溶液に、塩化亜鉛または硫酸亜鉛の水溶液を加
え、得られた析出物を水洗、濾別、乾燥して得た塩基性
炭酸亜鉛を265〜350℃の温度で熱分解することにより、
平均粒子径が0.01〜0.03μｍで、CO2含有量が0.1〜3.0
％である酸化亜鉛粉末を製造することを特徴とする超微
粒子酸化亜鉛粉末の製造方法。2. A basic zinc carbonate obtained by adding an aqueous solution of zinc chloride or zinc sulfate to an aqueous solution of ammonium carbonate or ammonium hydrogencarbonate, washing the resulting precipitate with water, filtering and drying it to 265 to 350 ° C. By pyrolyzing at the temperature of
Average particle size 0.01-0.03μm, CO 2 content 0.1-3.0
% Of zinc oxide powder, and a method for producing ultrafine zinc oxide powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1338485A JP2687640B2 (en) | 1989-12-28 | 1989-12-28 | Ultrafine zinc oxide powder having excellent ultraviolet absorption capacity and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1338485A JP2687640B2 (en) | 1989-12-28 | 1989-12-28 | Ultrafine zinc oxide powder having excellent ultraviolet absorption capacity and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03199121A JPH03199121A (en) | 1991-08-30 |
| JP2687640B2 true JP2687640B2 (en) | 1997-12-08 |
Family
ID=18318599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1338485A Expired - Fee Related JP2687640B2 (en) | 1989-12-28 | 1989-12-28 | Ultrafine zinc oxide powder having excellent ultraviolet absorption capacity and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2687640B2 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9121153D0 (en) * | 1991-10-04 | 1991-11-13 | Tioxide Chemicals Ltd | Method of preparing sunscreens |
| GB9121143D0 (en) * | 1991-10-04 | 1991-11-13 | Tioxide Chemicals Limited | Dispersions |
| DE4232143A1 (en) * | 1992-09-25 | 1994-03-31 | Claus E Dr Med Lange | Topical care products or pharmaceuticals containing fine-particle transparent zinc oxide |
| JP3819069B2 (en) * | 1995-06-02 | 2006-09-06 | 三好化成株式会社 | Cosmetics |
| JP2007182382A (en) * | 1997-11-18 | 2007-07-19 | Shiseido Co Ltd | Method for producing ultraviolet-screening zinc oxide excellent in transparency |
| US6171580B1 (en) * | 1997-11-18 | 2001-01-09 | Shiseido Company Ltd. | Ultraviolet-screening zinc oxide excellent in transparency and composition containing the same |
| CN1075790C (en) * | 1998-07-24 | 2001-12-05 | 山西省稷山县福利化工厂 | Alkaline process for producing active zinc oxide |
| KR100470533B1 (en) * | 2001-12-07 | 2005-03-08 | 이주현 | A method for preparaing ZnO nanopowder |
| JP5344131B2 (en) * | 2007-11-07 | 2013-11-20 | 住友金属鉱山株式会社 | Ultraviolet shielding material fine particle manufacturing method, ultraviolet shielding material fine particle dispersion, and ultraviolet shielding material |
| JP4655105B2 (en) * | 2008-04-30 | 2011-03-23 | 住友金属鉱山株式会社 | Ultraviolet light shielding transparent resin molding and method for producing the same |
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| JP5690661B2 (en) * | 2011-06-13 | 2015-03-25 | 堺化学工業株式会社 | Zinc oxide, method for producing zinc oxide, cosmetic, coating composition, and resin composition |
| CN103626221B (en) * | 2013-11-27 | 2017-06-20 | 北京三聚环保新材料股份有限公司 | A kind of method of the useless agent regeneration co-production ammonium sulfate of zinc oxide desulfurization |
| CN104386735A (en) * | 2014-11-03 | 2015-03-04 | 苏州市泽镁新材料科技有限公司 | Preparation method of zinc oxide |
| JP5850189B1 (en) | 2015-01-30 | 2016-02-03 | 住友大阪セメント株式会社 | Zinc oxide powder, dispersion, paint, cosmetics |
| KR102547489B1 (en) | 2015-08-28 | 2023-06-23 | 스미토모 오사카 세멘토 가부시키가이샤 | Zinc oxide powders, dispersions, compositions, and cosmetics |
| JP6037080B1 (en) | 2016-06-14 | 2016-11-30 | 住友大阪セメント株式会社 | Zinc oxide powder for cosmetics, dispersions, cosmetics |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6033766B2 (en) * | 1981-06-15 | 1985-08-05 | 三菱マテリアル株式会社 | Manufacturing method of zinc oxide ultrafine powder |
| JPS6033767B2 (en) * | 1981-06-16 | 1985-08-05 | 三菱マテリアル株式会社 | Manufacturing method for skin-colored zinc oxide fine powder |
| JPS62260716A (en) * | 1986-05-08 | 1987-11-13 | Shiseido Co Ltd | Production of ultrafine powder of zinc oxide |
| JPH02311314A (en) * | 1989-05-24 | 1990-12-26 | Sumitomo Cement Co Ltd | Production of ultrafine zinc oxide powder |
-
1989
- 1989-12-28 JP JP1338485A patent/JP2687640B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH03199121A (en) | 1991-08-30 |
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