JPH04357114A - Production of zinc oxide powder of ultrafine particle - Google Patents
Production of zinc oxide powder of ultrafine particleInfo
- Publication number
- JPH04357114A JPH04357114A JP15550491A JP15550491A JPH04357114A JP H04357114 A JPH04357114 A JP H04357114A JP 15550491 A JP15550491 A JP 15550491A JP 15550491 A JP15550491 A JP 15550491A JP H04357114 A JPH04357114 A JP H04357114A
- Authority
- JP
- Japan
- Prior art keywords
- zinc oxide
- zinc
- solution
- alcohol
- oxide 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.)
- Pending
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011882 ultra-fine particle Substances 0.000 title abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 19
- 150000003751 zinc Chemical class 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000843 powder Substances 0.000 description 11
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000000475 sunscreen effect Effects 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- -1 aliphatic alcohols Chemical class 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
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 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 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は透明性および分散性に優
れた超微粒子酸化亜鉛粉末の製造方法に関する。本発明
によって得られる酸化亜鉛粉末を分散させた被膜、成形
体及びペーストは優れた透明性と紫外線遮断効果を有し
、例えば日焼け止め化粧料、自動車、家具、光学材料の
紫外線遮断保護膜として利用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing ultrafine zinc oxide powder having excellent transparency and dispersibility. The coatings, molded bodies and pastes in which zinc oxide powder is dispersed, obtained according to the present invention, have excellent transparency and UV-blocking effects, and can be used, for example, as UV-blocking protective films for sunscreen cosmetics, automobiles, furniture, and optical materials. be done.
【０００２】紫外線遮断効果を有する材料は従来から知
られており、有機系材料ではベンゾトリアゾール、ベン
ゾフェノン等があり、また無機系材料では酸化チタン、
酸化亜鉛等がある。これらのうち、有機系材料は皮膚に
対する刺激性を有し、また光分解する問題がある。一方
、従来の無機系材料は粒子径が大きく不透明である。
そこで最近、無機系材料を微細化して光の散乱を小さく
することにより透明性を向上させた超微粒子の酸化チタ
ンや酸化亜鉛が市販されている。しかし従来の製造方法
で得られた酸化亜鉛粉末は塩基性炭酸亜鉛、シュウ酸亜
鉛、水ないし酸化亜鉛等を脱水乾燥して焼成するために
凝集し易く分散性に劣るため透明性も不十分である。Materials that have an ultraviolet blocking effect have been known for a long time. Organic materials include benzotriazole and benzophenone, and inorganic materials include titanium oxide and titanium oxide.
Examples include zinc oxide. Among these, organic materials are irritating to the skin and have the problem of being photodegraded. On the other hand, conventional inorganic materials have large particle sizes and are opaque. Recently, ultrafine particles of titanium oxide and zinc oxide, which have improved transparency by miniaturizing inorganic materials and reducing light scattering, have been commercially available. However, zinc oxide powder obtained by conventional manufacturing methods tends to aggregate and has poor dispersibility because basic zinc carbonate, zinc oxalate, water, zinc oxide, etc. are dehydrated and dried, and then fired, resulting in insufficient transparency. be.
【０００３】0003
【発明の解決課題】以上のように従来の酸化亜鉛粉末は
分散性が悪く透明性に劣る問題がある。本発明はこのよ
うな従来の問題を解決し、分散性に優れ高い透明性を有
する酸化亜鉛粉末を容易に製造する方法を提供すること
を目的とする。Problems to be Solved by the Invention As described above, conventional zinc oxide powders have the problem of poor dispersibility and poor transparency. An object of the present invention is to solve such conventional problems and provide a method for easily producing zinc oxide powder having excellent dispersibility and high transparency.
【０００４】0004
【課題の解決手段：発明の構成】本発明は、亜鉛塩をア
ルコール溶液中ないしアルコールと水の混合溶液中で、
６０℃以上、最終ｐＨ９以上のアルカリ性下で加水分解
させて平均粒径０．０５μｍ以下の酸化亜鉛を沈殿させ
ることを特徴とする超微粒子酸化亜鉛粉末の製造方法を
提供する。[Means for Solving the Problems: Structure of the Invention] The present invention provides zinc salts in an alcohol solution or a mixed solution of alcohol and water.
Provided is a method for producing ultrafine zinc oxide powder, which is characterized by precipitating zinc oxide having an average particle size of 0.05 μm or less by hydrolyzing it under alkaline conditions at a temperature of 60° C. or higher and a final pH of 9 or higher.
【０００５】本発明は、亜鉛塩をアルコール溶液ないし
アルコールと水の混合溶液に溶解した溶液が用いられる
。亜鉛塩としては、例えば塩化亜鉛、硝酸亜鉛、硫酸亜
鉛等の無機酸の亜鉛塩および酢酸亜鉛、シュウ酸亜鉛等
の有機酸亜鉛塩の何れも用いることができる。アルコー
ルとしては、メチルアルコール、エチルアルコール、ｎ
−プロピルアルコール、イソプロピルアルコール等の低
脂肪族アルコールが用いられる。亜鉛塩のアルコール溶
液ないしアルコールと水の混合溶液にアルカリ溶液を添
加して最終ｐＨを９以上に調整し、亜鉛塩を加水分解し
て酸化亜鉛粉末の沈殿を生成させる。亜鉛塩のアルコー
ル溶液ないしアルコールと水の混合溶液の最終ｐＨを９
以上に調整するには、亜鉛塩の溶液をアルカリ溶液に滴
下してもよく、また逆にアルカリ溶液を亜鉛塩の溶塩に
滴下しても良い。アルカリ溶液としては水酸化カリウム
、水酸化ナトリウムなどの強アルカリをメチルアルコー
ル、エチルアルコールのアルコールに溶解した溶液また
はこれに強アルカリをアルコールと水との混合溶液に溶
解した溶液が用いられる。In the present invention, a solution in which a zinc salt is dissolved in an alcohol solution or a mixed solution of alcohol and water is used. As the zinc salt, for example, any of the zinc salts of inorganic acids such as zinc chloride, zinc nitrate, and zinc sulfate, and the zinc salts of organic acids such as zinc acetate and zinc oxalate can be used. Alcohols include methyl alcohol, ethyl alcohol, n
- Low aliphatic alcohols such as propyl alcohol and isopropyl alcohol are used. An alkaline solution is added to an alcoholic solution or a mixed solution of alcohol and water of zinc salt to adjust the final pH to 9 or more, and the zinc salt is hydrolyzed to form a precipitate of zinc oxide powder. The final pH of the alcohol solution or mixed solution of alcohol and water of zinc salt is 9.
For the above adjustment, a solution of zinc salt may be dropped into an alkaline solution, or conversely, an alkaline solution may be dropped into a molten salt of zinc salt. As the alkaline solution, a solution in which a strong alkali such as potassium hydroxide or sodium hydroxide is dissolved in alcohol such as methyl alcohol or ethyl alcohol, or a solution in which a strong alkali is dissolved in a mixed solution of alcohol and water is used.
【０００６】以上のように本発明では、亜鉛塩をアルコ
ール溶液中ないしアルコールと水の混合溶液中で加水分
解させる。反応溶液中にアルコールが存在することによ
り溶液の表面張力が低下して微細なかつ分散性の高い酸
化亜鉛の沈殿を得ることができる。平均粒径 ０．０５
μｍ以下の微細な粉末を得るにはアルコールの濃度が５
０％以上であることが好ましい。As described above, in the present invention, zinc salt is hydrolyzed in an alcohol solution or a mixed solution of alcohol and water. The presence of alcohol in the reaction solution lowers the surface tension of the solution, making it possible to obtain fine and highly dispersible zinc oxide precipitates. Average particle size 0.05
To obtain fine powder of less than μm, the concentration of alcohol is 5.
It is preferably 0% or more.
【０００７】溶液中の亜鉛塩濃度及びアルカリの濃度は
、０．１〜５ｍｏｌ／ｌが好ましく、更に０．５〜３ｍ
ｏｌ／ｌが好ましい。亜鉛塩およびアルカリの濃度が
０．１ｍｏｌ／ｌより少ないと酸化亜鉛の沈殿量が少な
く生産性が低い。またこれらの濃度が５ｍｏｌ／ｌより
大きいと酸化亜鉛の粒子径が大きくなるので好ましくな
い。The concentration of zinc salt and alkali in the solution is preferably 0.1 to 5 mol/l, more preferably 0.5 to 3 mol/l.
ol/l is preferred. The concentration of zinc salts and alkalis
When it is less than 0.1 mol/l, the amount of zinc oxide precipitated is small and productivity is low. Moreover, if these concentrations are higher than 5 mol/l, the particle size of zinc oxide becomes large, which is not preferable.
【０００８】更に本発明では、溶液の温度を６０℃以上
、最終ｐＨを９以上に調整して亜鉛塩を加水分解させる
。反応温度が６０℃未満であると、亜鉛のヒドロゾルが
酸化亜鉛沈殿中に一部混在するので純度の高い酸化亜鉛
粉末を得ることができない。また加水分解速度が遅くな
り反応効率が低下する。同様に最終ｐＨが９未満である
と亜鉛のヒドロゾルが酸化亜鉛沈殿中に一部混在するの
で好ましくない。Furthermore, in the present invention, the zinc salt is hydrolyzed by adjusting the temperature of the solution to 60° C. or higher and the final pH to 9 or higher. If the reaction temperature is less than 60°C, a part of the zinc hydrosol will be mixed in the zinc oxide precipitation, making it impossible to obtain highly pure zinc oxide powder. Moreover, the hydrolysis rate becomes slow and the reaction efficiency decreases. Similarly, if the final pH is less than 9, some of the zinc hydrosol will be mixed in the zinc oxide precipitate, which is not preferable.
【０００９】以上の方法によって得られた酸化亜鉛は平
均粒径が ０．０５μｍ以下の超微粒子粉末であり、凝
集が少なく、また溶液中にアルコールが含まれるために
溶液の表面張力が低下するので、従来の方法で製造され
る酸化亜鉛に比べて分散性が良い。更に焼成工程を必要
としないにもかかわらず従来の湿式法で得られる酸化亜
鉛に比べて高い結晶性を有する。上記超微粒子酸化亜鉛
は脱水、乾燥工程を経ることなく直接に溶媒であるアル
コールやその他の有機溶媒に分散させて塗料、ペースト
などの添加材として利用することができる。また必要に
応じて表面処理することにより更に分散性を高めること
もできる。この場合、有機溶媒中での反応であるため表
面処理を容易に行なうことができる。[0009] The zinc oxide obtained by the above method is an ultrafine powder with an average particle size of 0.05 μm or less, has little agglomeration, and contains alcohol, which reduces the surface tension of the solution. , has better dispersibility than zinc oxide produced by conventional methods. Furthermore, although it does not require a firing process, it has higher crystallinity than zinc oxide obtained by conventional wet methods. The above-mentioned ultrafine zinc oxide particles can be directly dispersed in a solvent such as alcohol or other organic solvent without going through a dehydration or drying process and used as an additive for paints, pastes, and the like. Further, the dispersibility can be further improved by surface treatment as necessary. In this case, since the reaction is carried out in an organic solvent, surface treatment can be easily carried out.
【００１０】実施例１
水酸化カリウムのエタノール溶液（１ｍｏｌ／ｌ）２２
０ｍｌを８０℃に保ち、これに酢酸亜鉛のエタノール溶
液（１ｍｏｌ／ｌ）１００ｍｌを滴下した後、３０分間
温度を保持して酸化亜鉛の沈殿を生成させ、エタノール
洗浄により塩類を除去し濾別、風乾した。この粉末の平
均粒子径は０．０２５μｍであり、分散性に優れた超微
粒子酸化亜鉛粉末が得られた。
この粉末は、図１の透過型電子顕微鏡写真に示すように
、粒子の凝集もなく分散性に優れていることが確認され
た。また、これをＸ線回析法により測定したところ、図
２に示すように亜鉛のヒドロゾルの生成もなく酸化亜鉛
の高い結晶性を示した。Example 1 Ethanol solution of potassium hydroxide (1 mol/l) 22
0 ml was kept at 80°C, 100 ml of an ethanol solution of zinc acetate (1 mol/l) was added dropwise thereto, the temperature was maintained for 30 minutes to form a precipitate of zinc oxide, salts were removed by ethanol washing, and the mixture was separated by filtration. Air dried. The average particle diameter of this powder was 0.025 μm, and an ultrafine zinc oxide powder with excellent dispersibility was obtained. As shown in the transmission electron micrograph of FIG. 1, this powder was confirmed to have excellent dispersibility without particle agglomeration. Furthermore, when this was measured by X-ray diffraction, as shown in FIG. 2, no zinc hydrosol was formed and the zinc oxide exhibited high crystallinity.
【００１１】実施例２
水酸化カリウムのエタノール溶液（１ｍｏｌ／ｌ）２２
０ｍｌを６０℃に保ち、これに塩化亜鉛のエタノール溶
液（１ｍｏｌ／ｌ）１００ｍｌを滴下した後、３０分間
温度を保持して酸化亜鉛の沈殿を生成させ、水洗により
塩類を除去し濾別、風乾した。
この粉末の平均粒子径は０．０１９μｍであり、分散性
に優れた超微粒子酸化亜鉛粉末が得られた。Example 2 Ethanol solution of potassium hydroxide (1 mol/l) 22
0 ml was kept at 60°C, and 100 ml of an ethanol solution of zinc chloride (1 mol/l) was added dropwise thereto, and the temperature was maintained for 30 minutes to form a precipitate of zinc oxide. Salts were removed by washing with water, separated by filtration, and air-dried. did. The average particle diameter of this powder was 0.019 μm, and an ultrafine zinc oxide powder with excellent dispersibility was obtained.
【００１２】実施例３
酢酸亜鉛のエタノールと水の混合溶液（エタノール：水
＝５０：５０）（１ｍｏｌ／ｌ）１００ ｍｌを１００
℃に保ち、これに水酸化ナトリウムのエタノールと水の
混合溶液（エタノール：水＝５０：５０）（１ｍｏｌ／
ｌ）２２０ｍｌを滴下した後、３０分間温度を保持して
酸化亜鉛の沈殿を生成させ、エタノール洗浄により塩類
を除去し濾別、風乾した。この粉末の平均粒子径は０．
０２７μｍであり、分散性に優れた超微粒子酸化亜鉛粉
末が得られた。Example 3 100 ml of a mixed solution of zinc acetate in ethanol and water (ethanol:water=50:50) (1 mol/l) was
℃, and add a mixed solution of sodium hydroxide in ethanol and water (ethanol:water = 50:50) (1 mol/
1) After dropping 220 ml, the temperature was maintained for 30 minutes to form a zinc oxide precipitate, salts were removed by washing with ethanol, and the mixture was filtered and air-dried. The average particle size of this powder is 0.
027 μm, and an ultrafine zinc oxide powder with excellent dispersibility was obtained.
【００１３】実施例４
水酸化ナトリウムのエタノール溶液（１ｍｏｌ／ｌ）２
２０ｍｌを４０℃に保ち、これに塩化亜鉛のエタノール
溶液（１ｍｏｌ／ｌ）１００ｍｌを滴下した後、３０分
間温度を保持して生成した沈殿を、水洗により塩類を除
去し濾別、風乾した。この粉末をＸ線回析法により測定
したところ、酸化亜鉛とともに一部亜鉛のヒドロゾルの
生成が見られたが、平均粒子径は０．０２９μｍの分散
性に優れた超微粒子酸化亜鉛粉末が得られた。Example 4 Ethanol solution of sodium hydroxide (1 mol/l) 2
20 ml was kept at 40° C., and 100 ml of an ethanol solution of zinc chloride (1 mol/l) was added dropwise thereto, and the temperature was maintained for 30 minutes to form a precipitate. Salts were removed by washing with water, filtered, and air-dried. When this powder was measured by X-ray diffraction, some zinc hydrosol was observed to be formed along with zinc oxide, but an ultrafine zinc oxide powder with an average particle diameter of 0.029 μm and excellent dispersibility was obtained. Ta.
【００１４】実施例５
水酸ナトリウムのエタノールと水の混合溶液（エタノー
ル：水＝１０：９０）（１ｍｏｌ／ｌ）２２０ｍｌを８
０℃に保ち、これに塩化亜鉛のエタノールと水の混合溶
液（エタノール：水＝１０：９０）（１ｍｏｌ／ｌ）１
００ｍｌを滴下した後、３０分間温度を保持して酸化亜
鉛を生成させ水洗により塩類を除去し濾別、風乾した。
この粉末の平均粒子径は０．０４４μｍであり、分散性
に優れた超微粒子酸化亜鉛粉末が得られた。Example 5 220 ml of a mixed solution of sodium hydroxide in ethanol and water (ethanol:water=10:90) (1 mol/l) was mixed with 8
Maintain at 0°C, and add a mixed solution of zinc chloride in ethanol and water (ethanol:water = 10:90) (1 mol/l) 1
After dropping 00 ml of the solution, the temperature was maintained for 30 minutes to generate zinc oxide, and the salts were removed by washing with water, separated by filtration, and air-dried. The average particle diameter of this powder was 0.044 μm, and an ultrafine zinc oxide powder with excellent dispersibility was obtained.
【００１５】比較例
塩化亜鉛水溶液（１ｍｏｌ／ｌ）１００ｍｌを６０℃に
保ち、これに水酸化ナトリウム水溶液（１ｍｏｌ／ｌ）
１８０ｍｌを滴下した後、３０分間温度を保持して水酸
化亜鉛を生成させ、水洗により塩類を除去し濾別、風乾
後 ５００℃で２時間焼成した。この粉末の平均粒子径
は０．２μｍであり、ここで得られた酸化亜鉛の粒子径
は、実施例と比較して大きかった。Comparative Example 100 ml of zinc chloride aqueous solution (1 mol/l) was kept at 60°C, and sodium hydroxide aqueous solution (1 mol/l) was added to it.
After dropping 180 ml, the temperature was maintained for 30 minutes to generate zinc hydroxide, the salts were removed by washing with water, the mixture was filtered, air-dried, and then calcined at 500° C. for 2 hours. The average particle size of this powder was 0.2 μm, and the particle size of the zinc oxide obtained here was larger than that of the example.
【００１６】[0016]
【発明の効果】本発明による酸化亜鉛粉末の製造方法で
は、焼成工程を経ることなく、分散性に優れた超微粒子
酸化亜鉛粉末を得ることができ、この粉末を利用すれば
、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できる。更に、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、光学材料等の紫外線遮断保護膜に利用することがで
きる。また、この粉末の分散液を用いると有機溶媒への
分散を必要とせず、直接に塗料ペーストに利用すること
ができる。[Effects of the Invention] The method for producing zinc oxide powder according to the present invention makes it possible to obtain ultrafine zinc oxide powder with excellent dispersibility without going through a firing process. A coating film with high transparency and excellent UV blocking effect can be produced. Furthermore, the ultrafine zinc oxide powder according to the present invention can be used in sunscreen cosmetics, UV-blocking protective films for automobiles, furniture, optical materials, and the like. Moreover, when a dispersion of this powder is used, dispersion in an organic solvent is not required, and it can be directly used in a paint paste.
【図１】 本発明の方法（実施例１）で得られた超微
粒子酸化亜鉛粉末の粒子構造を示す透過型電子顕微鏡写
真[Figure 1] Transmission electron micrograph showing the particle structure of ultrafine zinc oxide powder obtained by the method of the present invention (Example 1)
【図２】 図１の試料のＸ線回析図[Figure 2] X-ray diffraction diagram of the sample in Figure 1
Claims (1)
コールと水の混合溶液中で、６０℃以上、最終ｐＨ９以
上のアルカリ性下で加水分解させて平均粒径 ０．０５
μｍ 以下の酸化亜鉛を沈殿させることを特徴とする超
微粒子酸化亜鉛粉末の製造方法。Claim 1: Zinc salt is hydrolyzed in an alcohol solution or a mixed solution of alcohol and water at a temperature of 60° C. or higher and an alkaline condition with a final pH of 9 or higher to obtain an average particle size of 0.05.
A method for producing ultrafine zinc oxide powder, characterized by precipitating zinc oxide with a particle size of μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15550491A JPH04357114A (en) | 1991-05-31 | 1991-05-31 | Production of zinc oxide powder of ultrafine particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15550491A JPH04357114A (en) | 1991-05-31 | 1991-05-31 | Production of zinc oxide powder of ultrafine particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04357114A true JPH04357114A (en) | 1992-12-10 |
Family
ID=15607494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15550491A Pending JPH04357114A (en) | 1991-05-31 | 1991-05-31 | Production of zinc oxide powder of ultrafine particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04357114A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH684387A5 (en) * | 1993-04-22 | 1994-09-15 | Greiter Ag | Cosmetic or pharmaceutical product for topical application to the skin and the mucous membranes |
| JPH07232919A (en) * | 1994-02-22 | 1995-09-05 | Nippon Shokubai Co Ltd | Production of fine zinc oxide particles |
| WO1995033688A1 (en) * | 1994-06-06 | 1995-12-14 | Nippon Shokubai Co., Ltd. | Fine zinc oxide particles, process for producing the same, and use thereof |
| WO2005113427A3 (en) * | 2004-05-19 | 2007-08-02 | Texas A & M Univ Sys | Process for preparing nano-sized metal oxide particles |
| WO2008062871A1 (en) * | 2006-11-22 | 2008-05-29 | Shiseido Company Ltd. | Process for production of zinc oxide fine-particle powder and cosmetics containing the powder |
| CN100408480C (en) * | 2006-07-26 | 2008-08-06 | 中国科学院上海硅酸盐研究所 | Prepn process of nanometer Zinc oxide powder |
| WO2008117932A1 (en) * | 2007-03-28 | 2008-10-02 | Electronics And Telecommunications Research Institute | Method of manufacturing oxide-based nano-structured material |
| JP2009538264A (en) * | 2006-05-23 | 2009-11-05 | ラバー ナノ プロダクツ （プロプライエタリー） リミテッド | Nonpolar capped nano transition metal oxides and sulfides |
| WO2011023266A1 (en) | 2009-08-28 | 2011-03-03 | Basf Se | Modified nanoparticles |
| JP2011057473A (en) * | 2009-09-07 | 2011-03-24 | Univ Of Miyazaki | Method for manufacturing magnetite fine particle |
| JP2011513190A (en) * | 2008-03-10 | 2011-04-28 | タタ ケミカルズ リミテッド | Method for producing nano zinc oxide particles |
| JP4864205B2 (en) * | 1999-02-23 | 2012-02-01 | ランクセス・ドイチュランド・ゲーエムベーハー | Method for producing nano-sized zinc oxide particles |
| US8344054B2 (en) | 2007-07-24 | 2013-01-01 | The Texas A & M University System | Polymer nanocomposites including dispersed nanoparticles and inorganic nanoplatelets |
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-
1991
- 1991-05-31 JP JP15550491A patent/JPH04357114A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH684387A5 (en) * | 1993-04-22 | 1994-09-15 | Greiter Ag | Cosmetic or pharmaceutical product for topical application to the skin and the mucous membranes |
| JPH07232919A (en) * | 1994-02-22 | 1995-09-05 | Nippon Shokubai Co Ltd | Production of fine zinc oxide particles |
| WO1995033688A1 (en) * | 1994-06-06 | 1995-12-14 | Nippon Shokubai Co., Ltd. | Fine zinc oxide particles, process for producing the same, and use thereof |
| EP0893409A1 (en) * | 1994-06-06 | 1999-01-27 | Nippon Shokubai Co., Ltd. | Zinc oxide-based fine particles, process for producing the same, and use thereof |
| US6200680B1 (en) | 1994-06-06 | 2001-03-13 | Nippon Shokubai Co., Ltd. | Fine zinc oxide particles, process for producing the same, and use thereof |
| JP4864205B2 (en) * | 1999-02-23 | 2012-02-01 | ランクセス・ドイチュランド・ゲーエムベーハー | Method for producing nano-sized zinc oxide particles |
| WO2005113427A3 (en) * | 2004-05-19 | 2007-08-02 | Texas A & M Univ Sys | Process for preparing nano-sized metal oxide particles |
| JP2007537970A (en) * | 2004-05-19 | 2007-12-27 | ザ テキサス エイ・アンド・エム ユニヴァーシティ システム | Method for preparing nano-sized metal oxide particles |
| JP2009538264A (en) * | 2006-05-23 | 2009-11-05 | ラバー ナノ プロダクツ （プロプライエタリー） リミテッド | Nonpolar capped nano transition metal oxides and sulfides |
| CN100408480C (en) * | 2006-07-26 | 2008-08-06 | 中国科学院上海硅酸盐研究所 | Prepn process of nanometer Zinc oxide powder |
| EP2093193A1 (en) * | 2006-11-22 | 2009-08-26 | Shiseido Company, Limited | Process for production of zinc oxide fine-particle powder and cosmetics containing the powder |
| JPWO2008062871A1 (en) * | 2006-11-22 | 2010-03-04 | 株式会社資生堂 | Method for producing fine particle zinc oxide powder and cosmetic containing the same |
| EP2093193A4 (en) * | 2006-11-22 | 2010-04-14 | Shiseido Co Ltd | Process for production of zinc oxide fine-particle powder and cosmetics containing the powder |
| WO2008062871A1 (en) * | 2006-11-22 | 2008-05-29 | Shiseido Company Ltd. | Process for production of zinc oxide fine-particle powder and cosmetics containing the powder |
| US8168157B2 (en) | 2006-11-22 | 2012-05-01 | Shiseido Company Ltd. | Production method of fine particle zinc oxide powder and cosmetics containing the same |
| WO2008117932A1 (en) * | 2007-03-28 | 2008-10-02 | Electronics And Telecommunications Research Institute | Method of manufacturing oxide-based nano-structured material |
| US8344054B2 (en) | 2007-07-24 | 2013-01-01 | The Texas A & M University System | Polymer nanocomposites including dispersed nanoparticles and inorganic nanoplatelets |
| JP2011513190A (en) * | 2008-03-10 | 2011-04-28 | タタ ケミカルズ リミテッド | Method for producing nano zinc oxide particles |
| US8747804B2 (en) | 2008-07-18 | 2014-06-10 | Basf Se | Modified zinc oxide particles |
| WO2011023266A1 (en) | 2009-08-28 | 2011-03-03 | Basf Se | Modified nanoparticles |
| JP2011057473A (en) * | 2009-09-07 | 2011-03-24 | Univ Of Miyazaki | Method for manufacturing magnetite fine particle |
| JP2014526614A (en) * | 2011-09-09 | 2014-10-06 | カナダス ケミカル，エルエルシー | Zinc oxide purification method |
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