JP6386934B2 - Method for producing metal-supported carbonate particles - Google Patents
Method for producing metal-supported carbonate particles Download PDFInfo
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- JP6386934B2 JP6386934B2 JP2015034650A JP2015034650A JP6386934B2 JP 6386934 B2 JP6386934 B2 JP 6386934B2 JP 2015034650 A JP2015034650 A JP 2015034650A JP 2015034650 A JP2015034650 A JP 2015034650A JP 6386934 B2 JP6386934 B2 JP 6386934B2
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- 239000002245 particle Substances 0.000 title claims description 38
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 57
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 27
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 229910001923 silver oxide Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 4
- 239000012798 spherical particle Substances 0.000 claims description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000010419 fine particle Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- -1 phosphoric acid compound Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
本発明は、微粒子金属が表面に担持された炭酸塩粒子の製造法に関する。 The present invention relates to a method for producing carbonate particles having fine metal particles supported on their surfaces.
銀や銅は抗菌性をもつことから、繊維材料、樹脂材料、電子材料への添加剤として用いることで微生物への抗菌効果を発揮することが期待される。特に微粒子化することで比表面積が大きくなるため、金属表面における活性酸素発生量が多くなり、抗菌効果は高くなる。
しかし、銀微粒子等は単体で使用すると、高い表面エネルギーによって凝集・焼結が起こりやすく、微粒子としての特性が活かしづらくなるだけでなく、被添加材へ均一に分散させるためのハンドリングも難しくなる。
Since silver and copper have antibacterial properties, they are expected to exert antibacterial effects on microorganisms when used as additives to fiber materials, resin materials, and electronic materials. In particular, since the specific surface area is increased by making the particles fine, the amount of active oxygen generated on the metal surface is increased and the antibacterial effect is enhanced.
However, when silver fine particles or the like are used alone, aggregation and sintering are likely to occur due to high surface energy, making it difficult to utilize the characteristics as fine particles, and handling to uniformly disperse them into the additive material becomes difficult.
このような観点から、銀等の金属を炭酸カルシウム粒子表面上に担持させる技術が報告されている。例えば、炭酸カルシウムに硝酸銀水溶液や塩化銀水溶液を含浸させる方法（特許文献１及び２）が報告されている。また、炭酸カルシウムに可溶性リン酸化合物を添加した後、金属粒子の非水分散液を接触させる方法（特許文献３）。炭酸カルシウムに硝酸銀を反応させて炭酸銀被覆炭酸カルシウムを製造した後、高温で焼成する方法（非特許文献１）が報告されている。 From such a viewpoint, a technique for supporting a metal such as silver on the surface of calcium carbonate particles has been reported. For example, methods of impregnating calcium carbonate with an aqueous silver nitrate solution or an aqueous silver chloride solution (Patent Documents 1 and 2) have been reported. Moreover, after adding a soluble phosphoric acid compound to calcium carbonate, the method of making the non-aqueous dispersion of a metal particle contact (patent document 3). There has been reported a method (Non-patent Document 1) in which silver nitrate is reacted with calcium carbonate to produce silver carbonate-coated calcium carbonate and then calcined at high temperature.
しかしながら、前記の製造法は、いずれも高温条件の焼成が必要であり、バテライト型のような球状粒子にならず、また反応工程が多く工業的に利用できない方法であった。
従って、本発明の課題は、簡便な手段で、工業的に有利に金属担持炭酸塩を製造する方法を提供することにある。
However, all of the production methods described above require firing under high temperature conditions, do not form spherical particles like a vaterite type, and have many reaction steps and cannot be used industrially.
Accordingly, an object of the present invention is to provide a method for producing a metal-supported carbonate industrially advantageously by a simple means.
そこで本発明者は、高温条件の焼成を行なうことなく炭酸塩粒子表面に銀等の金属を析出させるべく種々検討した結果、銀等の金属の酸化物と炭酸塩とをアルコール中で４０℃以上の温度で反応させれば、炭酸塩粒子の表面で金属酸化物の還元反応が生起し、炭酸塩粒子の表面に金属微粒子が担持した粒子が効率良く生成することを見出し、本発明を完成した。 Therefore, the present inventor has made various studies in order to deposit a metal such as silver on the surface of carbonate particles without firing at a high temperature condition. It was found that if the reaction was carried out at a temperature of 1, the metal oxide reduction reaction occurred on the surface of the carbonate particles, and particles carrying metal fine particles on the surface of the carbonate particles were efficiently generated, and the present invention was completed. .
すなわち、本発明は、次の〔１〕〜〔５〕を提供するものである。 That is, the present invention provides the following [1] to [5].
〔１〕炭酸第２族金属塩と、液状アルコール類と、第１１族又は第１２族金属の酸化物とを、４０℃以上液状アルコール類の沸点以下の温度で反応させること特徴とする第１１族又は第１２族金属が担持した炭酸第２族金属塩粒子の製造法。
〔２〕炭酸第２族金属塩が、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム及び炭酸ストロンチウムから選ばれるものである〔１〕記載の製造法。
〔３〕液状アルコール類が、液状１価アルコール及び多価アルコールから選ばれる１種又は２種以上である〔１〕又は〔２〕記載の製造法。
〔４〕第１１族又は第１２族金属の酸化物が、酸化銀、酸化銅又は酸化亜鉛である〔１〕〜〔３〕のいずれかに記載の製造法。
〔５〕得られる第１１族又は第１２族金属が担持した炭酸第２族塩粒子の炭酸第２族金属塩粒子が、球状粒子である〔１〕〜〔４〕のいずれかに記載の製造法。
[1] A carbon dioxide group 2 metal salt, a liquid alcohol, and an oxide of a group 11 or group 12 metal are reacted at a temperature not lower than 40 ° C. and not higher than the boiling point of the liquid alcohol. A method for producing Group 2 metal salt particles supported by a Group 12 or Group 12 metal.
[2] The process according to [1], wherein the Group 2 carbonate metal salt is selected from calcium carbonate, magnesium carbonate, barium carbonate and strontium carbonate.
[3] The process according to [1] or [2], wherein the liquid alcohol is one or more selected from liquid monohydric alcohol and polyhydric alcohol.
[4] The production method according to any one of [1] to [3], wherein the oxide of the Group 11 or Group 12 metal is silver oxide, copper oxide, or zinc oxide.
[5] The production according to any one of [1] to [4], wherein the Group 2 carbonate metal particles of the Group 2 carbonate salt particles supported by the Group 11 or Group 12 metal obtained are spherical particles. Law.
本発明方法によれば、簡易な操作かつ少ない工程で、工業的に有利に金属担持炭酸塩粒子が得られる。本発明により得られる金属担持炭酸塩粒子は、球状の形態にもすることができ、また炭酸塩粒子表面に担持した金属は微細であり、金属の表面積が大きくなるため、担持された金属の特性が十分に発揮される。 According to the method of the present invention, metal-supported carbonate particles can be obtained industrially advantageously with a simple operation and few steps. The metal-supported carbonate particles obtained according to the present invention can also have a spherical shape, and the metal supported on the surface of the carbonate particles is fine, and the surface area of the metal increases, so the characteristics of the supported metal Is fully demonstrated.
本発明の第１１族又は第１２族金属が担持した炭酸第２族金属塩粒子の製造法は、炭酸第２族金属塩と、液状アルコール類と、第１１族又は第１２族金属の酸化物とを、４０℃以上液状アルコール類の沸点以下の温度で反応させること特徴とする。 The method for producing Group 2 metal salt particles supported by Group 11 or Group 12 metal of the present invention includes a Group 2 metal salt, a liquid alcohol, and an oxide of Group 11 or Group 12 metal. Is reacted at a temperature not lower than 40 ° C. and not higher than the boiling point of the liquid alcohol.
炭酸第２族金属塩としては、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、炭酸ストロンチウムが挙げられる。このうち、炭酸カルシウム、炭酸マグネシウム、炭酸ストロンチウムが好ましく、炭酸カルシウム、炭酸マグネシウムがより好ましく、炭酸カルシウムがさらに好ましい。 Examples of the Group 2 metal carbonate include calcium carbonate, magnesium carbonate, barium carbonate, and strontium carbonate. Among these, calcium carbonate, magnesium carbonate, and strontium carbonate are preferable, calcium carbonate and magnesium carbonate are more preferable, and calcium carbonate is more preferable.
第１１族又は第１２族金属の酸化物としては、酸化銀、酸化銅、酸化亜鉛が挙げられる。このうち、金属自体抗菌作用等の活性を有する酸化銀、酸化銅がより好ましく、酸化銀がさらに好ましい。これらの金属酸化物は１種でも２種以上を混合して用いてもよい。
これらの金属酸化物の使用量は、還元後の担持粒子の凝集を抑制させる点から、炭酸第２族金属塩１質量部に対し、０．１〜０．５質量部が好ましく、０．１〜０．４質量部がより好ましく、０．１〜０．３質量部がさらに好ましい。
Examples of Group 11 or Group 12 metal oxides include silver oxide, copper oxide, and zinc oxide. Among these, silver oxide and copper oxide having activities such as antibacterial activity of the metal itself are more preferable, and silver oxide is more preferable. These metal oxides may be used alone or in combination of two or more.
The amount of these metal oxides used is preferably 0.1 to 0.5 parts by mass with respect to 1 part by mass of the Group 2 metal salt from the viewpoint of suppressing aggregation of the supported particles after reduction. -0.4 mass part is more preferable, and 0.1-0.3 mass part is further more preferable.
液状アルコール類としては、還元作用を有する常温で液体のアルコール類が好ましく、例えば、液状１価アルコール及び多価アルコールから選ばれる１種又は２種以上が挙げられる。液状１価アルコールとしては、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール等のＣ1−Ｃ6アルコールが挙げられる。多価アルコールとしては、エチレングリコール、プロピレングリコール、ブチレングリコール、液状ポリエチレングリコール、液状ポリプロピレングリコール、グリセリン等の２価又は３価のアルコールが挙げられる。
これらの液状アルコール類のうち、Ｃ1−Ｃ6アルコール、２価又は３価のアルコールがより好ましい。
液状アルコール類の使用量は、還元速度の点から、第１１族又は第１２族金属の酸化物１質量部に対して５０〜５００質量部が好ましく、１００〜５００質量部がより好ましく、１５０〜５００質量部がさらに好ましい。
The liquid alcohol is preferably a liquid alcohol at room temperature having a reducing action, and examples thereof include one or more selected from liquid monohydric alcohol and polyhydric alcohol. Examples of the liquid monohydric alcohol include C 1 -C 6 alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol. Examples of the polyhydric alcohol include divalent or trivalent alcohols such as ethylene glycol, propylene glycol, butylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, and glycerin.
Of these liquid alcohols, C 1 -C 6 alcohols, divalent or trivalent alcohols are more preferred.
The amount of the liquid alcohol used is preferably 50 to 500 parts by mass, more preferably 100 to 500 parts by mass, and more preferably 150 to 500 parts by mass with respect to 1 part by mass of the Group 11 or Group 12 metal oxide from the viewpoint of the reduction rate. More preferred is 500 parts by weight.
本発明方法を行うにあたって、炭酸第２族金属塩と、液状アルコール類と、第１１族又は第１２族金属の酸化物との３成分を反応させればよく、これらの成分の添加順序は限定されない。反応は、４０℃以上液状アルコール類の沸点以下の温度で行うことが必要である。４０℃未満の反応温度では、第１１族又は第１２族金属酸化物の還元反応が進行せず、炭酸金属塩粒子の表面に第１１族又は第１２族金属が担持されない。より好ましくは４０〜１５０℃であり、さらに好ましくは４０〜１２０℃である。
反応時間は、液状アルコール類、金属酸化物の種類によって異なるが、通常３０分〜５時間程度でよい。
In carrying out the method of the present invention, it is only necessary to react three components of a carbonate group 2 metal salt, a liquid alcohol, and an oxide of a group 11 or group 12 metal, and the order of addition of these components is limited. Not. The reaction needs to be performed at a temperature of 40 ° C. or higher and lower than the boiling point of the liquid alcohol. When the reaction temperature is less than 40 ° C., the reduction reaction of the Group 11 or Group 12 metal oxide does not proceed, and the Group 11 or Group 12 metal is not supported on the surface of the metal carbonate particle. More preferably, it is 40-150 degreeC, More preferably, it is 40-120 degreeC.
The reaction time varies depending on the type of liquid alcohols and metal oxides, but is usually about 30 minutes to 5 hours.
上記の反応により、炭酸第２族金属塩粒子の表面で第１１族又は第１２族金属酸化物の還元反応が進行し、表面に第１１族又は第１２族金属微粒子が担持された炭酸第２族金属塩粒子が得られる。この形態であることは走査型電子顕微鏡（ＳＥＭ）の反射電子像（ＢＳＥ）により確認することができる。また、第１１族又は第１２族金属塩粒子であることは、Ｘ線回折スペクトルにより確認できる。
炭酸第２族金属塩粒子表面上の第１１族又は第１２族金属は、粒子表面上の還元反応で生成するため、均一に担持され、かつ微細な粒子状である。従って、銀や銅粒子の表面積が大きく、その抗菌活性は向上する。また、亜鉛の場合には、鮮度保持機能が増大する。
また、例えば炭酸カルシウムを用いた場合、バテライト型の球状の形態の金属担持炭酸カルシウム粒子が得られる。このような球状粒子は、例えば使用感のよい化粧品材料として特に有用である。
本発明により得られる金属担持炭酸第２族金属塩粒子の粒子径は特に限定されないが、平均粒子径として０．１μｍ〜５０μｍが好ましく、０．１μｍ〜１０μｍがより好ましく、０．１μｍ〜５μｍがさらに好ましい。なお、平均粒子径は走査型電子顕微鏡により測定される粉末の最大長を粒子径とし２００個の粉末の最大長を平均したものである。
By the above reaction, the reduction reaction of the Group 11 or Group 12 metal oxide proceeds on the surface of the Group 2 metal salt particle, and the group 2 or group 12 metal fine particles are supported on the surface. Group metal salt particles are obtained. This form can be confirmed by a reflected electron image (BSE) of a scanning electron microscope (SEM). Moreover, it can confirm that it is a group 11 or a group 12 metal salt particle | grain by X-ray diffraction spectrum.
Since the Group 11 or Group 12 metal on the surface of the Group 2 metal salt particle is generated by a reduction reaction on the surface of the particle, it is uniformly supported and is in the form of fine particles. Therefore, the surface area of silver or copper particles is large, and the antibacterial activity is improved. In the case of zinc, the freshness maintaining function is increased.
For example, when calcium carbonate is used, metal-supported calcium carbonate particles having a vaterite-type spherical shape are obtained. Such spherical particles are particularly useful as, for example, a cosmetic material with a good feeling of use.
The particle diameter of the metal-supported Group 2 carbonate metal salt particles obtained by the present invention is not particularly limited, but the average particle diameter is preferably 0.1 μm to 50 μm, more preferably 0.1 μm to 10 μm, and more preferably 0.1 μm to 5 μm. Further preferred. The average particle diameter is the average of the maximum length of 200 powders, with the maximum length of the powder measured by a scanning electron microscope as the particle diameter.
次に実施例を挙げて、本発明を更に詳細に説明する。 EXAMPLES Next, an Example is given and this invention is demonstrated still in detail.
実施例１
（１）炭酸カルシウム合成工程
１．５ｍｏｌ／ＬのＣａＣｌ2水溶液を調製し「溶液Ａ」とした。一方、（ＮＨ4）2ＣＯ3を蒸留水に溶解させて「溶液Ｂ」を調製した。反応溶液全量（溶液Ａ＋溶液Ｂ）におけるＣａ濃度は１．４ｍｏｌ／Ｌ、ＣＯ3濃度は１．５ｍｏｌ／Ｌである。溶液Ａと溶液Ｂの混合、攪拌は、メカニカル制御攪拌器を用いて、攪拌回転数６００ｒｐｍにて３分間２０℃で行った。スラリーをろ過、洗浄後、１０５℃で１時間乾燥を行い、炭酸カルシウムを得た。得られた炭酸カルシウムは、バテライトであり、形状は球状であった。
Example 1
(1) Calcium carbonate synthesis step A 1.5 mol / L CaCl 2 aqueous solution was prepared and designated as “Solution A”. On the other hand, (NH 4 ) 2 CO 3 was dissolved in distilled water to prepare “Solution B”. The Ca concentration in the total amount of the reaction solution (solution A + solution B) is 1.4 mol / L, and the CO 3 concentration is 1.5 mol / L. The mixing and stirring of the solution A and the solution B were performed at 20 ° C. for 3 minutes at a stirring rotation speed of 600 rpm using a mechanically controlled stirrer. The slurry was filtered and washed, and then dried at 105 ° C. for 1 hour to obtain calcium carbonate. The obtained calcium carbonate was vaterite and had a spherical shape.
（２）金属担持工程
得られた炭酸カルシウム３．０ｇをメタノール溶媒（還元剤）１００ｍＬ中に酸化銀０．６７ｇと共に添加し、５０℃で１時間攪拌することで酸化銀を還元させ、炭酸カルシウム表面へ銀の状態で担持させた。還元・担持処理後にガラスフィルターでろ過し、試料を作製した。
(2) Metal supporting step 3.0 g of the obtained calcium carbonate was added together with 0.67 g of silver oxide in 100 mL of a methanol solvent (reducing agent), and the silver oxide was reduced by stirring at 50 ° C. for 1 hour. The surface was supported in a silver state. After the reduction / support treatment, the sample was filtered through a glass filter.
（３）結果
ＸＲＤ測定の結果、炭酸カルシウムと銀のピークのみが見られたことから（図１）、酸化銀の還元が完了していることを確認した。試料のＳＥＭ観察結果（反射電子像）を図２に示す。白く光っている箇所が銀である。粒子径１００ｎｍ以下の銀微粒子が粒子径約５００ｎｍの炭酸カルシウム上にほぼ均一に担持している。また、炭酸カルシウムは、バテライトの球状の形状を維持している。
(3) Results As a result of XRD measurement, only calcium carbonate and silver peaks were observed (FIG. 1), and it was confirmed that the reduction of silver oxide was completed. The SEM observation result (reflected electron image) of the sample is shown in FIG. The part that shines white is silver. Silver fine particles having a particle diameter of 100 nm or less are supported almost uniformly on calcium carbonate having a particle diameter of about 500 nm. Calcium carbonate maintains the spherical shape of vaterite.
比較例１（金属担持工程の還元温度が２０℃の場合）
実施例１と同様に作製した炭酸カルシウム３．０ｇをメタノール溶媒（還元剤）１００ｍＬ中に酸化銀０．６７ｇと共に添加し、２０℃で１時間攪拌することで酸化銀を還元させ、炭酸カルシウム表面に担持させた。還元処理後にガラスフィルターでろ過し、試料を作製した。
得られた試料をＸＲＤで測定した結果、炭酸カルシウムと酸化銀のピークが見られたことから（図３）、還元反応が起きていないことを確認した。
Comparative Example 1 (when the reduction temperature in the metal loading process is 20 ° C.)
The calcium carbonate prepared in the same manner as in Example 1 was added with 0.67 g of silver oxide in 100 mL of a methanol solvent (reducing agent), and the silver oxide was reduced by stirring at 20 ° C. for 1 hour, and the surface of calcium carbonate It was made to carry on. After the reduction treatment, the sample was filtered through a glass filter.
As a result of measuring the obtained sample by XRD, the peak of calcium carbonate and silver oxide was observed (FIG. 3), and it was confirmed that no reduction reaction occurred.
比較例２（炭酸カルシウムと別途作成した銀微粒子を混合した場合）
（１）銀微粒子作製工程
酸化銀をメタノールと混合し、５０℃で１ｈ攪拌した。攪拌後、反応容器壁面に付着した銀微粒子を回収した。
（２）炭酸カルシウムと銀微粒子の非水溶媒中での混合工程
実施例１と同様に作製した炭酸カルシウム粉末３．０ｇに対し、銀微粒子０．６２ｇをメタノール１００ｍＬ中で３０分間攪拌した。攪拌後、ガラスフィルターでろ過し、試料を得た。
（３）結果
試料のＳＥＭ観察結果（反射電子像）を図４に示す。白く光っている箇所が銀である。１００ｎｍ以下の銀微粒子が凝集しており、炭酸カルシウム上への均一な担持は確認できなかった。
Comparative Example 2 (when calcium carbonate and silver particles prepared separately are mixed)
(1) Silver fine particle preparation process Silver oxide was mixed with methanol, and it stirred at 50 degreeC for 1 h. After stirring, silver fine particles adhering to the reaction vessel wall surface were collected.
(2) Mixing step of calcium carbonate and silver fine particles in nonaqueous solvent For 3.0 g of calcium carbonate powder produced in the same manner as in Example 1, 0.62 g of silver fine particles were stirred in 100 mL of methanol for 30 minutes. After stirring, it was filtered through a glass filter to obtain a sample.
(3) Results FIG. 4 shows the SEM observation results (reflected electron image) of the sample. The part that shines white is silver. Silver fine particles of 100 nm or less were agglomerated, and uniform loading on calcium carbonate could not be confirmed.
Claims (4)
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