JPH01287211A - Manufacture of silver fine oarticle - Google Patents
Manufacture of silver fine oarticleInfo
- Publication number
- JPH01287211A JPH01287211A JP11530988A JP11530988A JPH01287211A JP H01287211 A JPH01287211 A JP H01287211A JP 11530988 A JP11530988 A JP 11530988A JP 11530988 A JP11530988 A JP 11530988A JP H01287211 A JPH01287211 A JP H01287211A
- Authority
- JP
- Japan
- Prior art keywords
- particle size
- silver
- particles
- silver nitrate
- reducing agent
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000004332 silver Substances 0.000 title claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 55
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000010419 fine particle Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract 3
- 239000010946 fine silver Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 abstract 2
- 238000004448 titration Methods 0.000 abstract 2
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 abstract 1
- 239000002151 riboflavin Substances 0.000 abstract 1
- 229960002477 riboflavin Drugs 0.000 abstract 1
- 235000019192 riboflavin Nutrition 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- SGSVWAYHEWEQET-SCRDCRAPSA-N 1,5-dihydroriboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2NC2=C1NC(=O)NC2=O SGSVWAYHEWEQET-SCRDCRAPSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229960003180 glutathione Drugs 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000004701 malic acid derivatives Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、微細な銀粒子の製造方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing fine silver particles.
（従来技術とその問題点）
従来、銀微粒子の製造方法としては、硝酸銀水溶液に水
酸化す） ＩＪウムを加えて酸化銀を作り、これをホル
マリンで還元する方法が用いられてきた。(Prior Art and its Problems) Conventionally, as a method for producing silver fine particles, a method has been used in which silver oxide is produced by adding hydroxide to an aqueous solution of silver nitrate, and this is reduced with formalin.
ところが、この方法では析出した微粒子量子が引き寄せ
合って、凝集した粒度分布の幅の広い銀粒子しか得られ
ず、粒径のコントロールが難しいという欠点を有してい
た。However, this method has the disadvantage that the precipitated fine particle quanta are attracted to each other, resulting in only aggregated silver particles with a wide particle size distribution, and that it is difficult to control the particle size.
（発明の目的）
本発明は、上記の欠点を解消せんがために、なされたも
のであり、分散した、粒度分布の幅の狭い微細な銀粒子
の粒径コントロール可能な製造方法を提供せんとするも
のである。(Objective of the Invention) The present invention has been made in order to eliminate the above-mentioned drawbacks, and it is an object of the present invention to provide a method for producing dispersed fine silver particles with a narrow particle size distribution, in which the particle size can be controlled. It is something to do.
（問題点を解決するための手段）
本発明は、硝酸銀水溶液を還元して銀微粒子を製造する
方法において、還元剤のＰＨを調整することにより、還
元剤の酸化還元電位を、−１０００ｍＶ〜＋５００ｍ１
／の範囲に調整し、さらに硝酸銀水溶液のＰ Ｈを０．
１≦ＰＨ≦７、反応温度を１００℃以下に保つことに
よって、粒径が均一で、しかも単分散した、銀微粒子を
得ることを特徴とするものである。(Means for Solving the Problems) The present invention provides a method for producing silver fine particles by reducing an aqueous silver nitrate solution, in which the redox potential of the reducing agent is adjusted from -1000 mV to +500 m
The pH of the silver nitrate aqueous solution was adjusted to within the range of /0.
By maintaining 1≦PH≦7 and the reaction temperature at 100° C. or lower, fine silver particles having a uniform particle size and monodisperse can be obtained.
而して、本発明の製造方法において、還元剤のＰＨを調
整することにより、還元剤の酸化還元電位を、−１００
０ｍＶ〜＋５００ｍＶの範囲に調整する理由は、この酸
化還元電位が硝酸銀水溶液を還元するのに適当であると
同時に、粒径が均一で単分散した粒子を析出させる働き
があるためであり、電位が、−１０００ｍＶより低いと
、反応は非常に速く、析出した粒子の一次粒子は細いが
、二次凝集してスポンジ状となってしまう。Thus, in the production method of the present invention, by adjusting the pH of the reducing agent, the redox potential of the reducing agent can be adjusted to -100.
The reason for adjusting the range from 0 mV to +500 mV is that this redox potential is appropriate for reducing the silver nitrate aqueous solution, and at the same time has the effect of precipitating monodispersed particles with uniform particle size. , -1000 mV, the reaction is very fast and the primary particles of the precipitated particles are thin, but they are secondary agglomerated and become spongy.
また、＋５００ｍＶより高いと、析出した粒子は不定形
で、凝集したものとなってしまうためである。On the other hand, if the voltage is higher than +500 mV, the precipitated particles will be amorphous and aggregated.
また、硝酸銀水溶液のＰＨを０．１≦Ｐ Ｈ≦７にする
理由は、ＰＨが０１より低いと還元剤が分解したり、粒
子が凝集しやすくなり、７より高いと反応が遅くなり、
工業的生産の場合に酸化物が生じ易くなるためである。In addition, the reason why the pH of the silver nitrate aqueous solution is set to 0.1≦PH≦7 is that when the pH is lower than 0.1, the reducing agent tends to decompose and particles tend to aggregate, and when the pH is higher than 7, the reaction slows down.
This is because oxides are likely to be produced during industrial production.
また、反応温度を１００℃以下に保つ理由は、１００℃
を超えると銀微粒子が凝集してくるとともに、粒度分布
の幅が広くなってしまうためである。Also, the reason why the reaction temperature is kept below 100℃ is that 100℃
This is because if it exceeds this, the silver particles will aggregate and the width of the particle size distribution will become wider.
ここで、本発明の実施例について説明する。Examples of the present invention will now be described.
〔実施例・１〕
硝酸銀結晶２ｇを水に溶解し、３１の水溶液とした後、
希硝酸を加えてそのＰＨを４に調整する。[Example 1] After dissolving 2 g of silver nitrate crystals in water to make an aqueous solution of 31,
Adjust its pH to 4 by adding dilute nitric acid.
また、還元型リボフラビン１ｇを水に溶解し、３１の水
溶液とした後、２８％アンモニア水を加えてＰＨ＝７に
調整する。Further, 1 g of reduced riboflavin was dissolved in water to make an aqueous solution of 31, and then 28% ammonia water was added to adjust the pH to 7.
この還元型リボフラビン溶液の酸化還元電位を測定する
と、＋２００ｍＶであった。When the redox potential of this reduced riboflavin solution was measured, it was +200 mV.
ここで、この２液の温度を２０℃に保ち、硝酸銀水溶液
を攪拌しながら、還元型リボフラビン溶液を添加し、４
分間反応させる。Here, while maintaining the temperature of these two liquids at 20°C and stirring the silver nitrate aqueous solution, the reduced riboflavin solution was added,
Let it react for a minute.
得られた銀微粒子は、濾過、洗浄して粒度分布測定及び
電子顕微鏡観察を行った。The obtained silver particles were filtered, washed, and subjected to particle size distribution measurement and electron microscopy observation.
その結果、この銀微粒子は球形で単分散しており、平均
粒径が０．５虜、粒度分布は、０．４８〜０．５２屑に
７０％が入る狭いもので、非常に均一な粒子が得られた
。As a result, these fine silver particles were spherical and monodisperse, with an average particle diameter of 0.5 mm and a narrow particle size distribution of 0.48 to 0.52 particles, with 70% of the particles falling into the particle size range, making them extremely uniform particles. was gotten.
〔実施例・２〕
硝酸銀結晶１．５ｇを水に溶解し、１１の水溶液とした
後、希硝酸を加えて、そのＰＨを３に調整する。[Example 2] After dissolving 1.5 g of silver nitrate crystals in water to make an aqueous solution of No. 11, dilute nitric acid was added to adjust the pH to 3.
また、２−グルタチオン１ｇを水に溶解し、１１の水溶
液とした後、２８％のアンモニア水を加えてＰ Ｈ＝
７に調整する。Further, 1 g of 2-glutathione was dissolved in water to make an aqueous solution of 11, and then 28% ammonia water was added to make P H=
Adjust to 7.
この２−グルタチオン溶液の酸化還元電位を測定すると
、−４０ｍＶであった。When the redox potential of this 2-glutathione solution was measured, it was -40 mV.
ここで、この２液の温度を３０℃保ち、硝酸銀水溶液を
攪拌しながら、２−グルタチオン溶液を添加し、５分間
反応させる。Here, the temperature of these two liquids is maintained at 30° C., and while stirring the silver nitrate aqueous solution, the 2-glutathione solution is added and allowed to react for 5 minutes.
得られた銀微粒子は、濾過、洗浄して、粒度分布測定及
び電子顕微鏡観察を行った。The obtained silver particles were filtered, washed, and subjected to particle size distribution measurement and electron microscope observation.
その結果、この銀微粒子は球形で単分散しており、平均
粒径が０．７虜、粒度分布は、０．６８〜０．７２虜に
７０％が入る狭いもので、非常に均一な粒子が得られた
。As a result, these fine silver particles were spherical and monodispersed, with an average particle size of 0.7mm and a narrow particle size distribution with 70% falling between 0.68 and 0.72mm, making them extremely uniform particles. was gotten.
〔実施例・３〕
硝酸銀結晶３ｇを水に溶解し、１１の水溶液とした後、
希硝酸を加えて、そのＰ Ｈを５に調整する。[Example 3] After dissolving 3 g of silver nitrate crystals in water to make an aqueous solution of 11,
Adjust the pH to 5 by adding dilute nitric acid.
また、リンゴ酸３ｇを水に溶解し、１１の水溶液とした
後、２８％のアンモニア水を加えてＰＨ＝７に調整する
。Further, 3 g of malic acid was dissolved in water to make an aqueous solution of No. 11, and then 28% aqueous ammonia was added to adjust the pH to 7.
このリンゴ酸溶液の酸化還元電位を測定すると＋１０２
ｍＶであった。The redox potential of this malic acid solution is +102
It was mV.
ここで、この２液の温度を１５℃保ち、硝酸銀水溶液を
攪拌しながら、リンゴ酸溶液を添加し、６分間反応させ
る。Here, the temperature of these two liquids is maintained at 15° C., and the malic acid solution is added while stirring the silver nitrate aqueous solution, and the mixture is allowed to react for 6 minutes.
得られた銀微粒子は、濾過、洗浄して、粒度分布測定及
び電子顕微鏡観察を行った。The obtained silver particles were filtered, washed, and subjected to particle size distribution measurement and electron microscope observation.
その結果、この銀微粒子は球形で単分散しており、平均
粒径が０． ３ｔｉｍ、粒度分布は、０．２８〜０．３
２虜に７０％が入る狭いもので、非常に均一な粒子が得
られた。As a result, the silver particles were spherical and monodispersed, with an average particle size of 0. 3tim, particle size distribution is 0.28-0.3
Very uniform particles were obtained, with 70% of the particles contained within the two cells.
硝酸銀結晶１５ｇを３０−の水に溶解し、これに４８％
の水酸化ナトリウム水溶液を加え、酸化銀の粒子を沈澱
させ、この粒子をホルマリンで還元して銀粒子を作った
。Dissolve 15g of silver nitrate crystals in 30% water and add 48%
An aqueous solution of sodium hydroxide was added to precipitate silver oxide particles, and the particles were reduced with formalin to produce silver particles.
得られた銀微粒子は、濾過、洗浄して、粒度分布測定及
び電子顕微鏡観察を行った。The obtained silver particles were filtered, washed, and subjected to particle size distribution measurement and electron microscope observation.
その結果、この銀粒子は不定形で凝集しており、平均粒
径は６．２虜で、粒度分布は０．５〜１０即と幅が広く
、非常に不均一なものであった。As a result, the silver particles were irregularly shaped and aggregated, the average particle size was 6.2 mm, the particle size distribution was wide from 0.5 to 10 mm, and was extremely non-uniform.
（発明の効果）
上記の説明で明らかなように、本発明の製造方法は、硝
酸銀水溶液を還元して、銀微粒子を製造する方法におい
て、還元剤のＰ Ｈを調整することにより、還元剤の酸
化還元電位を、−１０００ｍＶ〜＋５００ｍＶの範囲に
調整し、さらに硝酸銀水溶液のＰ Ｈを０．１≦ＰＨ≦
７、反応温度を１００℃以下に保つことにより、従来法
では得られなかった、単分散した均一で粒度分布の幅の
狭い、微細な銀粒子を、粒径をコン）・ロールして製造
できるので、従来の製造方法にとって代わることのでき
る画期的なものである。(Effects of the Invention) As is clear from the above explanation, the production method of the present invention is a method for producing silver fine particles by reducing an aqueous silver nitrate solution, by adjusting the pH of the reducing agent. The redox potential was adjusted to a range of -1000mV to +500mV, and the pH of the silver nitrate aqueous solution was adjusted to 0.1≦PH≦
7. By keeping the reaction temperature below 100℃, it is possible to produce monodisperse, uniform, fine silver particles with a narrow particle size distribution, which cannot be obtained by conventional methods, by controlling the particle size. Therefore, it is an epoch-making method that can replace conventional manufacturing methods.
出願人 田中貴金属工業株式会社Applicant: Tanaka Kikinzoku Kogyo Co., Ltd.
Claims (1)
おいて、還元剤のＰＨを調整することにより、還元剤の
酸化還元電位を、−１０００ｍＶ〜＋５００ｍＶの範囲
に調整し、さらに硝酸銀水溶液のＰＨを０．１≦ＰＨ≦
７、反応温度を１００℃以下に保つことによって、粒径
が均一で、しかも単分散した、銀微粒子を得ることを特
徴とする銀微粒子の製造方法。1. In the method of producing silver fine particles by reducing an aqueous silver nitrate solution, the oxidation-reduction potential of the reducing agent is adjusted to a range of -1000 mV to +500 mV by adjusting the pH of the reducing agent, and the pH of the aqueous silver nitrate solution is further adjusted. 0.1≦PH≦
7. A method for producing fine silver particles, which is characterized by obtaining fine silver particles having a uniform particle size and monodisperse by maintaining the reaction temperature at 100° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11530988A JPH01287211A (en) | 1988-05-12 | 1988-05-12 | Manufacture of silver fine oarticle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11530988A JPH01287211A (en) | 1988-05-12 | 1988-05-12 | Manufacture of silver fine oarticle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01287211A true JPH01287211A (en) | 1989-11-17 |
Family
ID=14659434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11530988A Pending JPH01287211A (en) | 1988-05-12 | 1988-05-12 | Manufacture of silver fine oarticle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01287211A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513543A (en) * | 2011-12-06 | 2012-06-27 | 上海工程技术大学 | Microwave heating reduction technology for preparing superfine silver powder |
| JP2020143322A (en) * | 2019-03-05 | 2020-09-10 | 国立大学法人 宮崎大学 | Separation recovery method of precious metal and precious metal fine particle recovered by the method |
-
1988
- 1988-05-12 JP JP11530988A patent/JPH01287211A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513543A (en) * | 2011-12-06 | 2012-06-27 | 上海工程技术大学 | Microwave heating reduction technology for preparing superfine silver powder |
| JP2020143322A (en) * | 2019-03-05 | 2020-09-10 | 国立大学法人 宮崎大学 | Separation recovery method of precious metal and precious metal fine particle recovered by the method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS63307206A (en) | Production of fine silver particles | |
| JPH01287210A (en) | Manufacture of silver fine particle | |
| JPH01287211A (en) | Manufacture of silver fine oarticle | |
| JPS63179009A (en) | Production of fine silver particles | |
| JPH0211709A (en) | Production of silver colloid | |
| JPH01104338A (en) | Manufacture of silver colloid | |
| JPH07107168B2 (en) | Method for producing fine copper particles | |
| JPH11189812A (en) | Manufacture of granular silver powder | |
| JPH0211707A (en) | Production of silver fine particle | |
| JPS63179012A (en) | Production of fine silver particles | |
| JPH0211706A (en) | Production of silver fine particle | |
| JPS63179010A (en) | Production of fine silver particles | |
| JPS63186805A (en) | Production of fine copper particles | |
| JPH01225708A (en) | Production of fine palladium particles | |
| JPS63179011A (en) | Production of fine silver particles | |
| JPH01104340A (en) | Manufacture of silver colloid | |
| JPS63186809A (en) | Production of fine copper particles | |
| JPH01225706A (en) | Production of fine copper particles | |
| JPH07107169B2 (en) | Method for producing fine copper particles | |
| JPH01104337A (en) | Manufacture of silver colloid | |
| JPS63186807A (en) | Production of fine copper particles | |
| JPH04321523A (en) | Production of tricobalt tetroxide | |
| JPH01225707A (en) | Production of fine palladium particles | |
| JPH01225710A (en) | Production of fine palladium particles | |
| JPS63186810A (en) | Production of fine copper particles |