JPH03199121A - Superfine-particle zinc oxide powder excellent in ultraviolet absorptivity and its production - Google Patents
Superfine-particle zinc oxide powder excellent in ultraviolet absorptivity and its productionInfo
- Publication number
- JPH03199121A JPH03199121A JP33848589A JP33848589A JPH03199121A JP H03199121 A JPH03199121 A JP H03199121A JP 33848589 A JP33848589 A JP 33848589A JP 33848589 A JP33848589 A JP 33848589A JP H03199121 A JPH03199121 A JP H03199121A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- carbonate
- zinc oxide
- oxide powder
- powder
- 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002245 particle Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 10
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 6
- 239000011592 zinc chloride Substances 0.000 claims abstract description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000002537 cosmetic Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- -1 hydrogen- Chemical class 0.000 abstract 1
- 239000011787 zinc oxide Substances 0.000 description 22
- 230000000903 blocking effect Effects 0.000 description 17
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000011882 ultra-fine particle Substances 0.000 description 5
- 235000004416 zinc carbonate Nutrition 0.000 description 5
- 239000011667 zinc carbonate Substances 0.000 description 5
- 229910000010 zinc carbonate Inorganic materials 0.000 description 5
- 238000004438 BET method Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000475 sunscreen effect Effects 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 101100481408 Danio rerio tie2 gene Proteins 0.000 description 1
- 101100481410 Mus musculus Tek gene Proteins 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
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)
Abstract
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、成形棒およびペースト等に分散させて、例えば日焼
は止め化粧料、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 Application Field] The present invention uses ultrafine zinc oxide (Zn) with excellent ultraviolet absorption ability.
O) Regarding powder and its manufacturing method. For more details,
The present invention relates to an ultrafine ZnO powder that can be dispersed into films, molded rods, pastes, etc. and used as ultraviolet-blocking protective films for sunscreen cosmetics, automobiles, furniture, optical materials, etc., 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（Ｔｉｅ２）、
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
。最近、無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Ｔｉｅ、 、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。Materials having a UV blocking effect are well known in the art. Organic systems include benzotriazole, benzophenone, etc.; inorganic systems include titanium oxide (Tie2), etc.
There are ZnO, etc. Among these, organic compounds have problems such as skin irritation and photodecomposition of the compound itself, while inorganic compounds have relatively large particle diameters and low transparency. Recently, consideration has been given to making inorganic powders into ultrafine particles to improve their transparency, and ultrafine particles such as Tie, ultrafine ZnO, etc. that reduce light scattering and improve transparency are commercially available. . However, most of the particle sizes of zinc oxide are 0.2~
The thickness is about 0.5 μm, and the transparency is still insufficient.
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。Furthermore, when ZnO powder is made into fine particles, the thermal decomposition temperature or calcination temperature is lowered to suppress the growth of the particles. I can't get it.
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, zinc oxide powder that has such high transparency and ultraviolet absorption effect at the same time has not 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（２６
５℃）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 focused on the fact that CO2 in zinc carbonate suppresses the agglomeration of primary particles and provides ultrafine ZnO powder with good dispersibility.
It was discovered that ultrafine ZnO powder with excellent transparency and ultraviolet absorbing ability could be obtained by thermally decomposing ZnO powder (5°C) as a raw material in the presence of CO2 to obtain ultrafine particles.
本発明によれば、平均粒子径が０．０１〜０．０３μｍ
で、ＣＯ２含有量が０．工〜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 diameter is 0.01 to 0.03 μm.
So, the CO2 content is 0. An ultrafine zinc oxide powder with an excellent 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
、ＣＯ，含有量が０．１〜３．０％である亜鉛粉末を製
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。Further, according to the present invention, basic zinc carbonate obtained by adding an aqueous solution of zinc chloride or zinc sulfate to an aqueous solution of ammonium carbonate or ammonium hydrogen carbonate, washing the obtained precipitate with water, separating it by filtration, and drying it, Zinc powder having an average particle size of 0.01 to 0.03 μm and a CO content of 0.1 to 3.0% is produced by thermal decomposition at a temperature of 350°C. A method of manufacturing particulate zinc oxide powder is provided.
本発明の超微粒子ＺｎＯ粉末は、平均粒子径が０．０１
〜０．０３μｍの超微粒子である。従来のＺｎＯは粒径
が０．２〜０．５μ履であって、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
均粒子系が０．０１μｍ以下では、−成粒子の凝集が生
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 diameter of 0.01
They are ultrafine particles of ~0.03 μm. Conventional ZnO has a particle size of 0.2 to 0.5 μm and is opaque because it scatters visible light. According to the inventors' test results, transparency decreases when the average particle diameter is 0.03 μm or more. Further, if the average particle size is 0.01 μm or less, agglomeration of particles occurs, and in this case also, transparency decreases.
更に本発明の超微粒子ＺｎＯ粉末は、０．１〜３．０％
のＣＯｚ （ＺｎＣＯｉ ）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凝集
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３７０ｎｎ＋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Ｚ
ｎＯ量が相対的に低下するが、ＣＯ□含有量（ＺｎＣＯ
，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。Furthermore, the ultrafine ZnO powder of the present invention contains 0.1 to 3.0%
of COz (ZnCOi). The presence of CO2 prevents agglomeration of primary particles during thermal decomposition of raw material zinc carbonate, and provides ultrafine zinc oxide powder having the above particle size and excellent dispersibility. By the way, ZnO has the property of absorbing ultraviolet rays of 370 nn+ or less, but ZnCO3 does not have an ultraviolet absorbing effect, and if ZnCO3 coexists, ZnO
Although the amount of nO decreases relatively, the content of CO□ (ZnCO
, amount) is less than 3.0%, a good ultraviolet blocking effect can be maintained.
ＣＯ□含有量（ＺｎＣＯ，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（ＺｎＣ
Ｏｚ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。If the CO□ content (ZnCO, amount) exceeds 3.0%, it becomes ultra-fine particles and the transparency of the particles improves, but the ultraviolet blocking ability decreases, which is undesirable.
If the amount (Oz amount) is less than 0.1%, the effect of suppressing agglomeration of primary particles will be insufficient and dispersibility will decrease, making it impossible to obtain excellent transparency.
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２
６５〜３５０℃の温度で熱分解することにより製造され
る。The zinc oxide particles mentioned above have excellent transparency and UV blocking effects.
An aqueous solution of zinc chloride or zinc 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.
It is produced by thermal decomposition at a temperature of 65-350°C.
上記塩基性炭酸亜鉛の分解温度は２６５℃であり。The decomposition temperature of the basic zinc carbonate is 265°C.
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。At temperatures below 265°C, a large amount of undecomposed zinc carbonate remains,
The desired zinc oxide powder cannot be obtained.
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
．０１μ川レベルの超微粒子粉末を得ることができない
。−例としてシュウ酸亜鉛を原料に用いると、熱分解温
度が４５０℃と高いため、０．０３μｍ以下の超微粒子
ＺｎＯ粉末を得ることは困難である。Furthermore, when the thermal decomposition temperature exceeds 350°C, most of the carbonate groups are decomposed into CO2 and removed, leading to particle aggregation and zero
．． It is not possible to obtain ultrafine powder at the 01μ river level. - For example, when zinc oxalate is used as a raw material, the thermal decomposition temperature is as high as 450°C, so it is difficult to obtain ultrafine ZnO powder of 0.03 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。In the present invention, since the thermal decomposition temperature is low as described above, carbonate groups can remain in the ZnO powder, and aggregation of particles during thermal decomposition can be sufficiently suppressed.
なお、ＣＯ□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 addition, in the method of treating ZnO using CO□ gas or carbonic acid, it is difficult to adjust the particle size of ZnO to a desired range, and it is impossible to obtain ZnO powder with 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
亜鉛粉末は日焼は止め化粧料、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 that has high transparency in the visible region and excellent ultraviolet blocking effect. Furthermore, the ultrafine zinc oxide powder according to the present invention can be used in sunscreen cosmetics, ultraviolet blocking protective films for automobiles, furniture, optical materials, etc.
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／ｆｌ）に硫酸
亜鉛水溶液（０，２ｍｏｌ／Ｑ）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 A zinc sulfate aqueous solution (0.2 mol/Q) was added dropwise to an ammonium carbonate aqueous solution (0.2 mol/fl) to form a basic zinc carbonate precipitate, salts were removed by washing with water, filtered, and dried. After this, the mixture was thermally decomposed at 265° C. for 1 hour to obtain ultrafine powder of zinc oxide.
この超微粒子酸化亜鉛粉末の比表面積（ＢＥＴ法）は９
０ポ／ｇ、−次粒子径は０．０１μｍ、ＣＯ□含有量は
３．０％であった。The specific surface area (BET method) of this ultrafine zinc oxide powder is 9
The particle diameter was 0.01 μm, and the CO□ 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％、３７０
ｎｍ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。Next, the paint shown in Table 1 was prepared using this ultrafine zinc oxide powder, and after coating it on a PET film to form a film, the transmittance and blocking rate in the visible and ultraviolet regions were measured using a spectrophotometer. It was measured. As shown in Figure 1, the results showed a transmittance of 75% in the visible region of 400 nm, and a transmittance of 370 nm.
It had a blocking rate of 95% in the nm ultraviolet region, showing excellent transparency and ultraviolet blocking effect.
第 １ 表
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（０，２ｓ＋ｏｌ／Ｑ）を滴下して塩基性
炭酸亜鉛の沈殿を生成させ、水洗１．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５０ｒｒｒ
／ｇ（ＢＥＴ法）、−次粒子径０．０２ μｔｒｒの超
微粒子粉末であり、ＣＯ２含有量は０．１％であった。Table 1 Example 2 A zinc chloride aqueous solution (0.2 s+ol/Q) was added dropwise to an ammonium hydrogen carbonate aqueous solution (0.2 mol #l) to form a basic zinc carbonate precipitate, and washed with water 1. After filtering and drying, the mixture was heated and decomposed at 350° C. for 10 hours to obtain zinc oxide powder. The specific surface area of this zinc oxide powder is 50rrr
/g (BET method), an ultrafine powder with a secondary particle size of 0.02 μtrr, and a CO2 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７０％、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。Next, using this ultrafine zinc oxide powder, a film was formed in the same manner as in Example 1, and the transmittance and blocking rate in the visible region and the ultraviolet region were measured. 98% blocking rate in the area
It showed excellent transparency and UV 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、５
００℃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）３０ｒｒｆ／ｇ、−次
粒子径０，０５μｒａ、 Ｃｏ、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,
The mixture was thermally decomposed at 00°C for 2 hours to obtain zinc oxide powder. This powder had a specific surface area (BET method) of 30 rrf/g, a secondary particle size of 0.05 μra, Co, and a Co content of 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、可視および紫外の面領域
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。A film was formed on a PET film using this ultrafine zinc oxide powder in the same manner as in Example 1, and the transmittance and blocking rate were measured in the visible and ultraviolet regions.
showed an excellent UV blocking effect with a blocking rate of 98%.
The transmittance at 400 nm was 65%, and the transparency in the visible region was significantly reduced.
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、２
５０℃で１時間加熱、分解して酸化亜鉛の粉末を得た。Comparative Example 2 After preparing basic zinc carbonate in the same manner as in Example 1, 2
The mixture was heated and decomposed at 50° C. for 1 hour to obtain zinc oxide powder.
この粉末の比表面積（ＢＥＴ法）は４０ｒｒｒ／ｇ、−
次粒子径は０．０４μｓ、 ＣＯ□含有量は５．０％で
あった。The specific surface area (BET method) of this powder is 40rrr/g, -
The secondary particle diameter was 0.04 μs, and the CO□ 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、紫外面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６部であり
、紫外線遮断率は大幅に低下した。Using this ultrafine zinc oxide powder, the transmittance and blocking rate in the visible and ultraviolet regions were measured in the same manner as in Example 1. As a result, the transmittance at 400 nm was 78%, indicating good transparency. However, the UV blocking rate at 370 nm was 6 parts, which was a significant decrease.
図はＰＵＴフィルム（曲Ａ１１）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。
図 面
減”（ｎｍ）The figure is a graph showing the spectral transmission curves of a PUT film (curve A11) and a film (curve 2) on which a UV-blocking transparent film containing zinc oxide of the present invention was formed. Figure Area reduction” (nm)
Claims (2)
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。(1) The average particle diameter is 0.01 to 0.03 μm, and CO_
Ultrafine zinc oxide powder with an excellent transparency and ultraviolet absorbing ability, with a content of 0.1 to 3.0%.
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、ＣＯ＿２含有
量が０．１〜３．０％である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) Add an aqueous solution of zinc chloride or zinc sulfate to an aqueous solution of ammonium carbonate or ammonium hydrogen carbonate, wash the resulting precipitate with water, separate it by filtration, and dry it to obtain basic zinc carbonate at a temperature of 265 to 350°C. By pyrolysis with
A method for producing ultrafine zinc oxide powder, characterized by producing zinc powder having an average particle diameter of 0.01 to 0.03 μm and a CO_2 content of 0.1 to 3.0%.
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 true JPH03199121A (en) | 1991-08-30 |
| JP2687640B2 JP2687640B2 (en) | 1997-12-08 |
Family
ID=18318599
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| 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 |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994007509A1 (en) * | 1992-09-25 | 1994-04-14 | Lange Claus E | Topical treatment agent or medicament containing finely divided transparent zinc oxide |
| US5366660A (en) * | 1991-10-04 | 1994-11-22 | Tioxide Specialties Limited | Dispersions |
| US5573753A (en) * | 1991-10-04 | 1996-11-12 | Tioxide Specialties Limited | Method of preparing sunscreens |
| US5744126A (en) * | 1995-06-02 | 1998-04-28 | Miyoshi Kasei, Inc. | Cosmetics containing silicone surface-modified particles of titanium oxide and zinc oxide |
| WO1999025654A1 (en) | 1997-11-18 | 1999-05-27 | 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 |
| WO2003048047A1 (en) * | 2001-12-07 | 2003-06-12 | Sung Park | A METHOD FOR PREPARING ZnO NANOPOWDER |
| JP2007182382A (en) * | 1997-11-18 | 2007-07-19 | Shiseido Co Ltd | Method for producing ultraviolet-screening zinc oxide excellent in transparency |
| JP2009132599A (en) * | 2007-11-07 | 2009-06-18 | Sumitomo Metal Mining Co Ltd | Method for producing ultraviolet shielding material fine particle, ultraviolet shielding material fine particle dispersion, and ultraviolet shielding body |
| EP2113528A3 (en) * | 2008-04-30 | 2009-11-18 | Sumitomo Metal Mining Co., Ltd. | Ultraviolet-shielding transparent resin molding and manufacturing method of the same |
| JP2010030819A (en) * | 2008-07-28 | 2010-02-12 | Sakai Chem Ind Co Ltd | Method for producing nitrogen-containing zinc oxide powder |
| JP2013001578A (en) * | 2011-06-13 | 2013-01-07 | Sakai Chem Ind Co Ltd | Zinc oxide, method for producing zinc oxide, cosmetic, coating composition, and resin composition |
| CN103626221A (en) * | 2013-11-27 | 2014-03-12 | 北京三聚环保新材料股份有限公司 | Method for recycling zinc oxide waste desulfurizers and co-producing ammonium sulfate |
| 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 |
| US9403691B1 (en) | 2015-01-30 | 2016-08-02 | Sumitomo Osaka Cement Co., Ltd. | Zinc oxide powder, dispersion, paint, and cosmetic material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57205319A (en) * | 1981-06-15 | 1982-12-16 | Mitsubishi Metal Corp | Manufacture of very fine zinc oxide powder |
| JPS57209824A (en) * | 1981-06-16 | 1982-12-23 | Mitsubishi Metal Corp | Preparation of skin-colored fine zinc oxide 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
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57205319A (en) * | 1981-06-15 | 1982-12-16 | Mitsubishi Metal Corp | Manufacture of very fine zinc oxide powder |
| JPS57209824A (en) * | 1981-06-16 | 1982-12-23 | Mitsubishi Metal Corp | Preparation of skin-colored fine zinc oxide 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 |
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|---|---|---|---|---|
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| US5573753A (en) * | 1991-10-04 | 1996-11-12 | Tioxide Specialties Limited | Method of preparing sunscreens |
| US5605652A (en) * | 1991-10-04 | 1997-02-25 | Tioxide Specialties Limited | Method of preparing sunscreens |
| WO1994007509A1 (en) * | 1992-09-25 | 1994-04-14 | Lange Claus E | Topical treatment agent or medicament containing finely divided transparent zinc oxide |
| US5744126A (en) * | 1995-06-02 | 1998-04-28 | Miyoshi Kasei, Inc. | Cosmetics containing silicone surface-modified particles of titanium oxide and zinc oxide |
| EP0992455A1 (en) * | 1997-11-18 | 2000-04-12 | Shiseido Company Limited | Ultraviolet-screening zinc oxide excellent in transparency and composition containing the same |
| WO1999025654A1 (en) | 1997-11-18 | 1999-05-27 | Shiseido Company, Ltd. | Ultraviolet-screening zinc oxide excellent in transparency and composition containing the same |
| AU751756B2 (en) * | 1997-11-18 | 2002-08-29 | Shiseido Company Ltd. | Ultraviolet-screening zinc oxide excellent in transparency and composition containing the same |
| JP2007182382A (en) * | 1997-11-18 | 2007-07-19 | Shiseido Co Ltd | Method for producing ultraviolet-screening zinc oxide excellent in transparency |
| CN100335413C (en) * | 1997-11-18 | 2007-09-05 | 株式会社资生堂 | Ultraviolet-screening zinc oxide excellent in transparency and composition containing the same |
| EP0992455B1 (en) * | 1997-11-18 | 2012-06-20 | Shiseido Company Limited | Ultraviolet-screening zinc oxide excellent in transparency and composition containing the same |
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| WO2003048047A1 (en) * | 2001-12-07 | 2003-06-12 | Sung Park | A METHOD FOR PREPARING ZnO NANOPOWDER |
| JP2009132599A (en) * | 2007-11-07 | 2009-06-18 | Sumitomo Metal Mining Co Ltd | Method for producing ultraviolet shielding material fine particle, ultraviolet shielding material fine particle dispersion, and ultraviolet shielding body |
| JP2009269946A (en) * | 2008-04-30 | 2009-11-19 | Sumitomo Metal Mining Co Ltd | Ultraviolet-shielding transparent resin molded body and its manufacturing method |
| 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 |
| EP2113528A3 (en) * | 2008-04-30 | 2009-11-18 | Sumitomo Metal Mining Co., Ltd. | Ultraviolet-shielding transparent resin molding and manufacturing method of the same |
| JP2010030819A (en) * | 2008-07-28 | 2010-02-12 | Sakai Chem Ind Co Ltd | Method for producing nitrogen-containing zinc oxide powder |
| JP2013001578A (en) * | 2011-06-13 | 2013-01-07 | Sakai Chem Ind Co Ltd | Zinc oxide, method for producing zinc oxide, cosmetic, coating composition, and resin composition |
| CN103626221A (en) * | 2013-11-27 | 2014-03-12 | 北京三聚环保新材料股份有限公司 | Method for recycling zinc oxide waste desulfurizers and co-producing ammonium sulfate |
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| US9403691B1 (en) | 2015-01-30 | 2016-08-02 | Sumitomo Osaka Cement Co., Ltd. | Zinc oxide powder, dispersion, paint, and cosmetic material |
| EP3252011A4 (en) * | 2015-01-30 | 2018-09-05 | Sumitomo Osaka Cement Co., Ltd. | Zinc oxide powder, dispersion, paint, cosmetic |
| KR20180044276A (en) | 2015-08-28 | 2018-05-02 | 스미토모 오사카 세멘토 가부시키가이샤 | Zinc oxide powder, dispersion, composition, and cosmetic |
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