JP2012162772A - Method for producing metallic nanoparticle and conductive material - Google Patents
Method for producing metallic nanoparticle and conductive material Download PDFInfo
- Publication number
- JP2012162772A JP2012162772A JP2011024284A JP2011024284A JP2012162772A JP 2012162772 A JP2012162772 A JP 2012162772A JP 2011024284 A JP2011024284 A JP 2011024284A JP 2011024284 A JP2011024284 A JP 2011024284A JP 2012162772 A JP2012162772 A JP 2012162772A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- ion
- producing
- nanoparticles
- polyhydrosiloxane
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 239000002105 nanoparticle Substances 0.000 title abstract description 19
- 239000004020 conductor Substances 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 6
- 239000002082 metal nanoparticle Substances 0.000 claims description 53
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 229910021645 metal ion Inorganic materials 0.000 claims description 38
- 239000003638 chemical reducing agent Substances 0.000 claims description 22
- -1 trifluoroacetate ion Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
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- 230000001603 reducing effect Effects 0.000 abstract description 8
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- 239000000243 solution Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 239000010419 fine particle Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
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- 239000012535 impurity Substances 0.000 description 9
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
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- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000108 ultra-filtration Methods 0.000 description 6
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- 230000000694 effects Effects 0.000 description 3
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- 125000002524 organometallic group Chemical group 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
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Abstract
Description
本発明は、溶液中で金属塩を還元して金属ナノ粒子の懸濁液を製造する方法に係り、特に、懸濁液から余剰還元剤等の夾雑物を効率よく除去して金属ナノ粒子の純度を容易に高めることが可能な金属ナノ粒子の製造方法に関する。 The present invention relates to a method for producing a suspension of metal nanoparticles by reducing a metal salt in a solution, and in particular, by removing impurities such as excess reducing agent from the suspension efficiently. The present invention relates to a method for producing metal nanoparticles capable of easily increasing the purity.
粒径がおよそ数ｎｍ〜数１００ｎｍ程度の金属の微粒子のことを金属ナノ粒子という。金属ナノ粒子は、粒径が小さいことに起因する種々の特性を有しており、従来、様々な分野で利用されている。例えば、マトリクス表示液晶ディスプレイ等においては、液晶セルに充填された液晶に金属ナノ粒子を添加することにより、液晶素子の応答が高速化することが知られている。また、金属ナノ粒子は、通常のサブミクロン以上の塊状の金属に比べて焼結温度が低いことから、配線材料としてプリント配線板と電子部品の接続等に用いられている。 Metal fine particles having a particle size of about several nanometers to several hundred nanometers are referred to as metal nanoparticles. Metal nanoparticles have various properties resulting from their small particle size and have been used in various fields. For example, in a matrix display liquid crystal display or the like, it is known that the response of the liquid crystal element is increased by adding metal nanoparticles to the liquid crystal filled in the liquid crystal cell. In addition, metal nanoparticles are used as a wiring material for connecting a printed wiring board and an electronic component because the sintering temperature is lower than that of a normal metal of submicron or more.
金属ナノ粒子の製造方法としては、例えば、坩堝に入れて加熱した原料固体から発生した蒸気に対して不活性ガスの分子等を衝突させて急冷することにより微粒子化するガス中蒸発法が知られている。この方法によれば、高濃度かつ高純度の金属ナノ粒子を得ることができる。しかしながら、原料固体から蒸気を発生させるための設備が必要であるため、金属ナノ粒子を安価に製造することができないという課題があった。そこで、このような特別な設備を必要としないものとして、溶液中で金属塩を還元して金属ナノ粒子を製造する方法が注目されている。 As a method for producing metal nanoparticles, for example, an in-gas evaporation method is known in which particles of an inert gas collide with vapor generated from a raw material solid heated in a crucible and rapidly cooled to make particles fine. ing. According to this method, high concentration and high purity metal nanoparticles can be obtained. However, since equipment for generating steam from the raw material solid is required, there is a problem that metal nanoparticles cannot be produced at low cost. Thus, as a method that does not require such special equipment, a method of producing metal nanoparticles by reducing a metal salt in a solution has attracted attention.
例えば、特開２００４−２３２０１２号公報（特許文献１）には、「高濃度金属微粒子分散液の製造方法」という名称で、有機酸の存在下で有機金属塩を還元することにより、金属微粒子分散液を製造する方法に関する発明が開示されている。この文献に開示された金属微粒子分散液の製造方法は、有機金属塩を炭素数１０以下の有機酸が有機金属塩と等モル以上含有された溶媒に溶解させて、金属換算濃度が少なくとも１質量％となるように調製された有機金属塩溶液をジオール又はヒドラジン又はヒドロキシルアミンで還元することを特徴としている。 For example, Japanese Patent Application Laid-Open No. 2004-232012 (Patent Document 1) describes a method of producing a high-concentration metal fine particle dispersion by reducing an organic metal salt in the presence of an organic acid. An invention relating to a method for producing a liquid is disclosed. In the method for producing a metal fine particle dispersion disclosed in this document, an organic metal salt is dissolved in a solvent containing an organic acid having 10 or less carbon atoms in an equimolar amount or more and the metal equivalent concentration is at least 1 mass. It is characterized by reducing the organometallic salt solution prepared to be 1% with diol, hydrazine or hydroxylamine.
上記の特許文献１に記載の製造方法によれば、高濃度の有機金属塩溶液が生成されるとともに、還元剤により、この有機金属塩溶液に対し強い還元作用が発揮される。また、還元後に金属イオンが残留し難いという作用を有する。したがって、高濃度の金属微粒子分散液を容易に製造することができる。 According to the manufacturing method described in Patent Document 1, a highly concentrated organometallic salt solution is generated, and a strong reducing action is exerted on the organometallic salt solution by the reducing agent. In addition, it has an effect that metal ions hardly remain after reduction. Therefore, a high concentration fine metal particle dispersion can be easily produced.
特開２００５−２２０４３５号公報（特許文献２）には、「金属ナノ粒子及び金属ナノ粒子分散液の製造方法」という名称で、高価な設備を必要とせずに高濃度の金属ナノ粒子分散液を簡便且つ安価に連続して得ることのできる金属ナノ粒子及び金属ナノ粒子分散液の製造方法に関する発明が開示されている。この文献に開示された金属ナノ粒子および金属ナノ粒子分散液の製造方法は、少なくとも１種の金属イオンと有機分子からなる保護剤が混合された溶液を溶媒下で還元するとともに、有機分子で保護された金属ナノ粒子集合体を沈降させて回収するものである。 Japanese Patent Application Laid-Open No. 2005-220435 (Patent Document 2) describes a high-concentration metal nanoparticle dispersion without the need for expensive equipment under the name “metal nanoparticles and a method for producing a metal nanoparticle dispersion”. An invention relating to a method for producing metal nanoparticles and a metal nanoparticle dispersion that can be obtained continuously easily and inexpensively is disclosed. In the method for producing metal nanoparticles and metal nanoparticle dispersions disclosed in this document, a solution in which a protective agent composed of at least one metal ion and an organic molecule is mixed is reduced in a solvent and protected with an organic molecule. The collected metal nanoparticle aggregate is settled and recovered.
上記の特許文献２に記載の製造方法によれば、生成された金属ナノ粒子は有機分子で保護されているため、溶媒に対する親和性が低下して集合体となって沈降するという作用を有する。これにより、金属ナノ粒子集合体を連続して回収することができる。 According to the production method described in Patent Document 2, since the generated metal nanoparticles are protected with organic molecules, the affinity for the solvent is lowered, and the resulting metal nanoparticles are precipitated as aggregates. Thereby, a metal nanoparticle aggregate | assembly can be collect | recovered continuously.
特開２００２−１８０１１０号公報（特許文献３）には、「金属コロイド溶液の製造方法」という名称で、均一な粒子径を有する金属コロイド微粒子が単分散した溶液を容易に製造可能な方法に関する発明が開示されている。この文献に開示された金属コロイド溶液の製造方法は、標準水素電極電位が−０．８〜＋１．２ｅＶの範囲にある金属塩、安定化剤及び溶媒を混合して調製した金属コロイド溶液調製用母液を、１０〜９５℃の温度に調整し、さらに、標準水素電極電位が−０．２〜＋１．５ｅＶの範囲にあり、かつ上記金属塩を構成する金属よりも標準水素電極電位が高い金属塩を添加するとともに、還元剤を用いてこれら２種類の金属塩を還元することを特徴としている。 Japanese Patent Application Laid-Open No. 2002-180110 (Patent Document 3) discloses an invention relating to a method capable of easily producing a solution in which metal colloidal fine particles having a uniform particle diameter are monodispersed under the name of “method for producing a metal colloid solution”. Is disclosed. The method for producing a metal colloid solution disclosed in this document is for preparing a metal colloid solution prepared by mixing a metal salt having a standard hydrogen electrode potential in the range of −0.8 to +1.2 eV, a stabilizer and a solvent. A metal whose mother liquor is adjusted to a temperature of 10 to 95 ° C. and whose standard hydrogen electrode potential is in the range of −0.2 to +1.5 eV and whose standard hydrogen electrode potential is higher than that of the metal constituting the metal salt. It is characterized by adding a salt and reducing these two types of metal salts using a reducing agent.
上記の特許文献３に記載の製造方法によれば、標準水素電極電位が−０．８〜＋１．５ｅＶの範囲にある金属からなる核微粒子の表面に、この核微粒子よりも標準水素電極電位が高く、かつ標準水素電極電位が−０．８〜＋１．２ｅＶの範囲にある金属が析出した複合金属微粒子が分散したコロイド溶液が生成される。そして、このコロイド溶液中には、粒径分布が狭く、大きさが揃った金属コロイド微粒子が単分散している。すなわち、本製造方法によれば、均一な粒子径を有する金属コロイド微粒子が単分散した溶液を製造することが可能である。 According to the manufacturing method described in Patent Document 3, the standard hydrogen electrode potential is higher than the nuclear fine particles on the surface of the nuclear fine particles made of a metal having a standard hydrogen electrode potential in the range of −0.8 to +1.5 eV. A colloidal solution in which composite metal fine particles in which a metal having a high and standard hydrogen electrode potential in the range of −0.8 to +1.2 eV is deposited is dispersed. In this colloid solution, metal colloidal fine particles having a narrow particle size distribution and uniform size are monodispersed. That is, according to this production method, it is possible to produce a solution in which metal colloidal fine particles having a uniform particle diameter are monodispersed.
上述の特許文献１に開示された発明においては、還元剤としてジオールを用いた場合、反応させる際の温度を１００℃以上にしなければならず、そのための設備を必要とする。また、ヒドラジンやヒドロキシルアミンは刺激臭を有するため、取扱いが容易でないという課題があった。 In the invention disclosed in Patent Document 1 described above, when a diol is used as a reducing agent, the temperature at the time of reaction must be 100 ° C. or higher, and equipment for that purpose is required. Further, since hydrazine and hydroxylamine have an irritating odor, there is a problem that handling is not easy.
また、特許文献２及び特許文献３に開示された発明においては、水素化ホウ素ナトリウムを還元剤として利用するため、夾雑物がナトリウム塩となる。この場合、ナトリウム塩を除去する操作を行うための設備が必要となり、製造コストが高くなるという課題があった。 Further, in the inventions disclosed in Patent Document 2 and Patent Document 3, since sodium borohydride is used as a reducing agent, impurities are sodium salts. In this case, there is a problem that equipment for performing an operation for removing the sodium salt is required, resulting in an increase in manufacturing cost.
本発明は、かかる従来の事情に対処してなされたものであり、安全かつ安価に金属ナノ粒子の懸濁液を製造し、この懸濁液から夾雑物を効率よく除去して高純度の金属ナノ粒子を製造する方法を提供することを目的とする。 The present invention has been made in response to such a conventional situation, and a metal nanoparticle suspension is produced safely and inexpensively, and impurities are efficiently removed from the suspension to obtain a high-purity metal. It aims at providing the method of manufacturing a nanoparticle.
上記目的を達成するため、本発明に従った金属ナノ粒子の製造方法は、金属イオンに還元剤を反応させて金属ナノ粒子を製造する方法において、金属イオンの標準酸化還元電位は０Ｖ以上であり、還元剤は一般式（１）で示されるポリヒドロシロキサン化合物であることを特徴とするものである。 In order to achieve the above object, the method for producing metal nanoparticles according to the present invention is a method for producing metal nanoparticles by reacting a metal ion with a reducing agent, wherein the standard oxidation-reduction potential of the metal ions is 0 V or more. The reducing agent is a polyhydrosiloxane compound represented by the general formula (1).
本願発明の製造方法によれば、標準酸化還元電位が０Ｖよりも小さいヒドロシラン化合物が金属イオンを還元し、金属ナノ粒子の懸濁液を生成するという作用を有する。なお、ポリヒドロシロキサン化合物はほとんど無臭であり、刺激臭がないため、安全である。また、金属イオンが還元される際に、還元剤として使用するポリヒドロシロキサンの官能基が原料の陰イオンにより変換されるという作用を有する。例えば、酢酸銀を原料に用いた場合、還元剤のケイ素−水素結合が変換されて酢酸のシリルエステルが生成する。このように金属イオンの還元反応後の夾雑物は高分子量のものとなるため、限外濾過等による操作により金属ナノ粒子と高分子量の夾雑物や余剰の還元剤とを分離することとが可能となる。さらに、ポリヒドロシロキサン化合物がナノ粒子のまわりを保護することで、より安定な粒子を得ることができる。 According to the production method of the present invention, a hydrosilane compound having a standard oxidation-reduction potential smaller than 0 V has an action of reducing metal ions and generating a suspension of metal nanoparticles. The polyhydrosiloxane compound is safe because it is almost odorless and has no irritating odor. In addition, when the metal ion is reduced, the functional group of the polyhydrosiloxane used as the reducing agent is converted by the anion of the raw material. For example, when silver acetate is used as a raw material, the silicon-hydrogen bond of the reducing agent is converted to produce silyl ester of acetic acid. As described above, the impurities after the reduction reaction of the metal ions have a high molecular weight, so it is possible to separate the metal nanoparticles from the high molecular weight impurities and the excess reducing agent by an operation such as ultrafiltration. It becomes. Furthermore, more stable particles can be obtained by protecting the periphery of the nanoparticles with the polyhydrosiloxane compound.
請求項２に記載したように、ポリヒドロシロキサン化合物に含まれる有機基は、例えば、無置換のアルキル基である。無置換のアルキル基を有機基として含むポリヒドロシロキサン化合物は製造性及び取扱い性に優れている。従って、このようなポリヒドロシロキサン化合物を還元剤として使用すれば、還元剤の調達が容易であるとともに、製造工程における作業効率が向上する。 As described in claim 2, the organic group contained in the polyhydrosiloxane compound is, for example, an unsubstituted alkyl group. A polyhydrosiloxane compound containing an unsubstituted alkyl group as an organic group is excellent in manufacturability and handleability. Therefore, when such a polyhydrosiloxane compound is used as a reducing agent, it is easy to procure the reducing agent and work efficiency in the manufacturing process is improved.
請求項３に記載したように、好ましくは、金属イオンは金属塩からの電離によって生成され、この金属塩から金属イオンともに電離する陰イオンは、酢酸イオン、トリフルオロ酢酸イオン、塩化物イオン、フッ化物イオン、硝酸イオンおよび過塩素酸イオンからなる群から選ばれる少なくとも１種である。このような製造方法においては、金属イオンが還元される際に、加水分解し難く、空気中の湿気に対して強いケイ素化合物が生成されるという作用を有する。 As described in claim 3, preferably, the metal ion is generated by ionization from the metal salt, and the anion ionized together with the metal ion from the metal salt is acetate ion, trifluoroacetate ion, chloride ion, fluorine ion. And at least one selected from the group consisting of chloride ions, nitrate ions and perchlorate ions. Such a production method has an effect that when a metal ion is reduced, a silicon compound that is hardly hydrolyzed and strong against moisture in the air is generated.
請求項４に記載の導電材料は、請求項１〜３のいずれかに記載の方法によって製造された金属ナノ粒子を利用したものである。 The conductive material according to a fourth aspect uses metal nanoparticles produced by the method according to any one of the first to third aspects.
以上説明したように、本発明の請求項１に記載の金属ナノ粒子の製造方法によれば、還元剤の取扱いが容易であるため、安全かつ効率的に製造作業を行うことができる。また、有機ケイ素化合物や余剰還元剤などの夾雑物を限外濾過等により容易に除去することができる。従って、懸濁液中の金属ナノ粒子の純度を効率よく高めることができる。 As described above, according to the method for producing metal nanoparticles according to claim 1 of the present invention, since the handling of the reducing agent is easy, the production operation can be performed safely and efficiently. Further, impurities such as an organosilicon compound and an excess reducing agent can be easily removed by ultrafiltration or the like. Therefore, the purity of the metal nanoparticles in the suspension can be increased efficiently.
本発明の請求項２に記載の製造方法によれば、材料コスト及び製造コストの削減を図ることが可能である。 According to the manufacturing method of the second aspect of the present invention, it is possible to reduce the material cost and the manufacturing cost.
本発明の請求項３に記載の製造方法によれば、製造環境を無水条件に設定する必要がないため、乾燥設備の設置等による余分な設備費用が発生しない。従って、金属ナノ粒子を安価に製造することが可能である。 According to the manufacturing method of the third aspect of the present invention, since it is not necessary to set the manufacturing environment to anhydrous conditions, no extra equipment costs are required due to the installation of drying equipment or the like. Therefore, it is possible to produce metal nanoparticles at a low cost.
本発明の実施形態に係る金属ナノ粒子の製造方法は、ポリヒドロシロキサン化合物によって金属イオンを溶液中で還元し、金属ナノ粒子の懸濁液を製造することを特徴とする。 A method for producing metal nanoparticles according to an embodiment of the present invention is characterized in that a metal ion is reduced in a solution by a polyhydrosiloxane compound to produce a suspension of metal nanoparticles.
ポリヒドロシロキサン化合物は、ケイ素原子と酸素原子が直鎖状に結合した高分子であり、ケイ素原子（Ｓｉ）の有する４つの結合手のうち、少なくとも１つの結合手に水素原子（Ｈ）が直接結合したものである。この水素原子の数によって区別され、それぞれポリモノヒドロシロキサン（Ｈが１つ）、ポリジヒドロシロキサン（Ｈが２つ）と呼ばれている。そして、ポリヒドロシロキサン化合物はほとんど無臭であり、刺激臭を伴わないため、取扱いが容易である。従って、ポリヒドロシロキサン化合物を還元剤として用いることによれば、金属ナノ粒子を安全かつ効率よく製造することができる。
このように、上記２種類のポリヒドロシロキサン化合物はいずれも還元剤として優れた特性を有している。なお、本実施例では、特に、以下の一般式（２）で示されるポリモノヒドロシロキサン化合物を用いている。
The polyhydrosiloxane compound is a polymer in which a silicon atom and an oxygen atom are linearly bonded, and a hydrogen atom (H) is directly in at least one of the four bonds of the silicon atom (Si). It is a combination. They are distinguished by the number of hydrogen atoms and are called polymonohydrosiloxane (one H) and polydihydrosiloxane (two H), respectively. The polyhydrosiloxane compound is almost odorless and has no irritating odor, and is easy to handle. Therefore, by using a polyhydrosiloxane compound as a reducing agent, metal nanoparticles can be produced safely and efficiently.
Thus, both of the two types of polyhydrosiloxane compounds have excellent characteristics as reducing agents. In this example, in particular, a polymonohydrosiloxane compound represented by the following general formula (2) is used.
一般式（２）において、ポリモノヒドロシラン化合物の製造性及び取扱い性が容易であるという理由から、有機基は無置換のアルキル基を有するものであることが望ましい。このポリモノヒドロシロキサンは他のシロキサンポリマーの原料として利用されることもあり、還元剤の調達が容易となるとともに、製造工程における作業効率が向上する。従って、材料コスト及び製造コストの削減を図ることができる。 In the general formula (2), it is desirable that the organic group has an unsubstituted alkyl group because the manufacturability and handleability of the polymonohydrosilane compound are easy. This polymonohydrosiloxane may be used as a raw material for other siloxane polymers, so that it becomes easy to procure a reducing agent and work efficiency in the manufacturing process is improved. Accordingly, the material cost and the manufacturing cost can be reduced.
なお、アルキル基とは、炭素原子が１列に結合した、いわゆる脂肪族炭化水素から１個の水素原子（Ｈ）を取り去った原子団の総称のことである。このようなアルキル基としては、メチル基（−ＣＨ３）、エチル基（−Ｃ２Ｈ５）、プロピル基（−Ｃ３Ｈ７）、ブチル基（−Ｃ４Ｈ９）、ペンチル基（−Ｃ５Ｈ１１）、ヘキシル基（−Ｃ６Ｈ１３）、フェニル基（−Ｃ６Ｈ５）、シクロヘキシル基（−Ｃ６Ｈ１１）などが例示される。なお、ケイ素化合物自体の安定性を損なわないものであれば、これらの有機基以外にも、例えば、ハロゲン原子（周期表の１７族のフッ素（Ｆ）、塩素（Ｃｌ）、臭素（Ｂｒ）、ヨウ素（Ｉ）の４元素を含む化合物の総称）、アルコキシ基（アルコールの水酸基から水素を取り除いた官能基）、シアノ基（−ＣＮ）等の各種官能基やヘテロ原子（水素と炭素以外の原子）又は不飽和結合を有するものを用いても良い。また、ハロゲン原子で置換された、フルオロメチル基（−ＣＨ２Ｆ）、クロロメチル基（−ＣＨ２Ｃｌ）、２−クロロエチル基（−Ｃ２Ｈ４Ｃｌ）等のアルキル基やアルコキシ基で置換された、メトキシメチル基（−ＣＨ２ＯＣＨ３）、メトキシエチル基（−ＣＨ２ＣＨ２ＯＣＨ３）、２−エトキシエチル基（−Ｃ２Ｈ４ＯＣ２Ｈ５）等のアルキル基を用いることもできる。 The alkyl group is a general term for an atomic group in which one hydrogen atom (H) is removed from a so-called aliphatic hydrocarbon in which carbon atoms are bonded in one row. Examples of such an alkyl group include a methyl group (—CH 3 ), an ethyl group (—C 2 H 5 ), a propyl group (—C 3 H 7 ), a butyl group (—C 4 H 9 ), and a pentyl group (— C 5 H 11 ), hexyl group (—C 6 H 13 ), phenyl group (—C 6 H 5 ), cyclohexyl group (—C 6 H 11 ) and the like are exemplified. As long as the stability of the silicon compound itself is not impaired, other than these organic groups, for example, a halogen atom (group 17 fluorine (F), chlorine (Cl), bromine (Br), Various functional groups such as iodine (I) containing four elements, alkoxy groups (functional groups obtained by removing hydrogen from alcohol hydroxyl groups), cyano groups (-CN), and hetero atoms (atoms other than hydrogen and carbon) ) Or those having an unsaturated bond may be used. In addition, substituted with an alkyl group or an alkoxy group such as a fluoromethyl group (—CH 2 F), a chloromethyl group (—CH 2 Cl), or a 2-chloroethyl group (—C 2 H 4 Cl) substituted with a halogen atom Alkyl groups such as methoxymethyl group (—CH 2 OCH 3 ), methoxyethyl group (—CH 2 CH 2 OCH 3 ), 2-ethoxyethyl group (—C 2 H 4 OC 2 H 5 ), etc. You can also.
なお、これらのポリヒドロシロキサン化合物の標準酸化還元電位はおよそ−０．４〜０Ｖである。したがって、これらのポリヒドロシロキサン化合物によって還元されるべき金属イオンは標準酸化還元電位が０Ｖ以上のものでなければならない。なお、金属塩からの電離によって生成される金属イオンの標準酸化還元電位は、サイクリックボルタンメトリー等の測定法により測定することができる。 The standard redox potential of these polyhydrosiloxane compounds is approximately −0.4 to 0V. Therefore, the metal ions to be reduced by these polyhydrosiloxane compounds must have a standard redox potential of 0 V or higher. In addition, the standard oxidation-reduction potential of the metal ion produced | generated by ionization from a metal salt can be measured by measuring methods, such as cyclic voltammetry.
金属イオンとは、単数あるいは複数の電子を失った金属原子のことであり、一般に、金属と酸の反応等の化学的な方法や電気分解等の電気的な方法あるいは金属塩を水若しくは有機溶媒に溶解させる方法によって生成される。本実施例においては、金属イオンの供給源として塩化金（ＡｕＣｌ３）等の金塩、塩化白金酸（Ｈ２ＰｔＣｌ６・６Ｈ２Ｏ）等の白金塩、酢酸パラジウム（Ｐｄ（ＣＨ３ＣＯＯ）２）、塩化パラジウム（ＰｄＣｌ２）等のパラジウム塩、酢酸銀（ＣＨ３ＣＯＯＡｇ）、トリフルオロ酢酸銀（ＣＦ３ＣＯＯＡｇ）等の銀塩等を用いている。同様に、塩化白金（ＩＶ）（ＰｔＣｌ４）の白金（ＩＶ）塩、塩化銅（Ｉ）（ＣｕＣｌ）、酢酸銅（Ｃｕ（ＣＨ３ＣＯＯ）２）等の銅塩等を用いることも可能である。 A metal ion is a metal atom that has lost one or more electrons. Generally, a chemical method such as a reaction between a metal and an acid, an electrolysis method such as electrolysis, or a metal salt in water or an organic solvent. It is produced by the method of dissolving in In the present embodiment, gold chloride as a source of metal ions (AuCl 3) a gold salt such as, platinum salts such as chloroplatinic acid (H 2 PtCl 6 · 6H 2 O), palladium acetate (Pd (CH 3 COO) 2 ), palladium salts such as palladium chloride (PdCl 2 ), and silver salts such as silver acetate (CH 3 COOAg) and silver trifluoroacetate (CF 3 COOAg). Similarly, a platinum (IV) salt of platinum (IV) chloride (PtCl 4 ), a copper salt such as copper chloride (I) (CuCl), copper acetate (Cu (CH 3 COO) 2 ), etc. can be used. is there.
これらの金属塩は溶液中で金属イオンと陰イオンに電離する。そして、金属イオンとして、パラジウムイオン（Ｐｄ２＋）、白金イオン（Ｐｔ２＋、Ｐｔ４＋）、金イオン（Ａｕ３＋）、銅イオン（Ｃｕ＋、Ｃｕ２＋）等が生成される。なお、本願発明に用いる金属イオンは、既に述べたように標準酸化還元電位が０Ｖ以上であり、ポリヒドロシロキサン化合物と還元反応するものであればよく、その元素および価数は本実施例に示す場合に限定されるものではない。とくに金属イオンに銅イオンを用いて請求項１乃至３に記載の方法によって銅ナノ粒子を製造する際、この銅ナノ粒子は極めて空気に対して不安定なため、銅イオンにパラジウムイオンを混合することが好ましい。パラジウムイオンを添加することで製造された銅／パラジウムナノ粒子は、銅ナノ粒子と比較して空気に対して安定である。銅／パラジウムナノ粒子製造について、銅イオンとパラジウムイオンの比は特に限定されるものではない。 These metal salts ionize into metal ions and anions in solution. As metal ions, palladium ions (Pd 2+ ), platinum ions (Pt 2+ , Pt 4+ ), gold ions (Au 3+ ), copper ions (Cu + , Cu 2+ ) and the like are generated. The metal ion used in the present invention may be any metal ion as long as it has a standard oxidation-reduction potential of 0 V or more as described above and can undergo a reduction reaction with the polyhydrosiloxane compound, and the element and valence are shown in this example. The case is not limited. In particular, when copper nanoparticles are produced by the method according to claims 1 to 3 using copper ions as metal ions, the copper nanoparticles are extremely unstable with respect to air, so that palladium ions are mixed with copper ions. It is preferable. Copper / palladium nanoparticles produced by adding palladium ions are more stable to air than copper nanoparticles. For copper / palladium nanoparticle production, the ratio of copper ion to palladium ion is not particularly limited.
上記金属塩から電離する陰イオンとしては、例えば、水酸化物イオン（ＯＨ−）、酢酸イオン（ＣＨ３ＣＯＯ−）、硝酸イオン（ＮＯ３ −）、トリフルオロ酢酸イオン（ＣＦ３ＣＯＯ−）、塩化物イオン（Ｃｌ−）、臭化物イオン（Ｂｒ−）、フッ化物イオン（Ｆ−）などがあげられる。これらの陰イオンは、多くの場合、ポリヒドロシロキサン化合物と反応して新たな化合物を形成する。例えば、酢酸イオン（ＣＨ３ＣＯＯ−）と金属イオンの溶液にポリヒドロシロキサン化合物を加えると、ポリヒドロシロキサン化合物のケイ素−水素結合の部位が酢酸シリルエステルに変換される。また、塩化物イオン（Ｃｌ−）を含む溶液の場合は、クロロシラン化合物が生成される。また、陰イオンとしてトリフルオロ酢酸イオン（ＣＦ３ＣＯＯ−）、臭化物イオン（Ｂｒ−）及びヨウ化物イオン（Ｉ−）を用いた場合にも、対応する化合物が生成される。しかし、臭化物イオン（Ｂｒ−）若しくはヨウ化物イオン（Ｉ−）とポリヒドロシロキサン化合物との反応によって生成されるブロモシラン又はヨードシランは加水分解性が強いため、それらの取扱いは無水状態で行う必要がある。 Examples of the anion ionized from the metal salt include hydroxide ion (OH − ), acetate ion (CH 3 COO − ), nitrate ion (NO 3 − ), trifluoroacetate ion (CF 3 COO − ), Examples include chloride ion (Cl − ), bromide ion (Br − ), and fluoride ion (F − ). These anions often react with polyhydrosiloxane compounds to form new compounds. For example, when a polyhydrosiloxane compound is added to a solution of acetate ions (CH 3 COO − ) and metal ions, the silicon-hydrogen bond sites of the polyhydrosiloxane compound are converted to silyl acetate. In the case of a solution containing chloride ions (Cl − ), a chlorosilane compound is generated. In addition, when a trifluoroacetate ion (CF 3 COO − ), a bromide ion (Br − ), and an iodide ion (I − ) are used as anions, corresponding compounds are also produced. However, since bromosilane or iodosilane produced by the reaction of bromide ion (Br − ) or iodide ion (I − ) with a polyhydrosiloxane compound is highly hydrolyzable, it must be handled in an anhydrous state. .
なお、金属イオンとモノヒドロシラン化合物を反応させる際には、溶媒や添加剤等を共存させても良い。溶媒としては、例えば、メタノール、エタノール、１−プロパノール、２−プロパノール、ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、エチレングリコール、プロピレングリコール、フェノール、シクロへキサノール等のアルコール類、ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、２−メチルテトラヒドロフラン、ジオキサン等のエーテル類、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、トリデカン、テトラデカン、シクロヘキサン、ベンゼン、トルエン、キシレン、メシチレン、ビニルベンゼン、フェニルアセチレン、トラン等の炭化水素類、フルオロベンゼンクロロベンゼン、クロロホルム、ジクロロメタン、ブロモベンゼン、ヨードベンゼン等のハロゲン化炭化水素類、トリエチルアミン、アニリン、ピリジン等のアミン類、アセトン、シクロヘキサノン、アセトフェノン等のケトン類、酢酸エチル、酢酸イソプロピル、安息香酸メチル、γ―ブチロラクトン、エチレンカーボート、プロピレンカーボネート等のエステル類等、Ｎ−メチル−２−ピロリドン、アセトアニリド等のアミド類、ベンゾニトリル、４−シアノ−４’−ペンチルビフェニル、４−シアノ−４’−ペンチルオキシビフェニル、等のニトリル化合物類、ニトロベンゼン等のニトロ化合物類、ヘキサンチオール、ヘプタンチオール、オクタンチオール等のチオール類および水等の溶媒から単独あるいは混合して用いることができる。また、カルボン酸塩、アルキルスルホン酸塩等の界面活性剤類、ポリ（Ｎ−ビニルピロリドン）、オレイン酸等のカルボン酸類等の酸類、ポリアクリル酸、ポリエチレングリコール、ポリ（ジメチルシロキサン）等の高分子類を添加しても良い。なお、本願発明で使用可能な溶媒は本実施例に示すものに限定されるものではない。すなわち、ポリヒドロシロキサン化合物による金属イオンの還元反応を阻害しないものであれば、上記溶媒以外の溶媒であっても良い。 In addition, when making a metal ion and a monohydrosilane compound react, you may coexist a solvent, an additive, etc. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, butanol, sec-butanol, tert-butanol, alcohols such as ethylene glycol, propylene glycol, phenol, cyclohexanol, diethyl ether, diisopropyl ether, Ethers such as dibutyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, cyclohexane, benzene, toluene, xylene, mesitylene, vinylbenzene, phenyl Hydrocarbons such as acetylene and tolane, fluorobenzene chlorobenzene, chloroform, dichloromethane, bromobenzene, iodo Halogenated hydrocarbons such as benzene, amines such as triethylamine, aniline, pyridine, ketones such as acetone, cyclohexanone, acetophenone, ethyl acetate, isopropyl acetate, methyl benzoate, γ-butyrolactone, ethylene carboat, propylene carbonate, etc. Esters such as N-methyl-2-pyrrolidone, amides such as acetanilide, nitrile compounds such as benzonitrile, 4-cyano-4′-pentylbiphenyl, 4-cyano-4′-pentyloxybiphenyl, nitrobenzene Nitro compounds such as hexanethiol, heptanethiol, octanethiol and the like, and solvents such as water can be used alone or in combination. Also, surfactants such as carboxylates and alkyl sulfonates, acids such as poly (N-vinylpyrrolidone) and carboxylic acids such as oleic acid, polyacrylic acid, polyethylene glycol, poly (dimethylsiloxane) Molecules may be added. In addition, the solvent which can be used by this invention is not limited to what is shown in a present Example. That is, a solvent other than the above solvent may be used as long as it does not inhibit the reduction reaction of metal ions by the polyhydrosiloxane compound.
金属イオンとポリヒドロシロキサン化合物を反応させる際に溶媒を用いる場合、反応温度は、溶媒の還流温度以下であることが望ましい。ただし、これに限定されるものではなく、溶媒の沸点以上とすることもできる。また、金属イオンとポリヒドロシロキサン化合物とを、溶媒を蒸発させながら反応させても良い。なお、金属イオンとポリヒドロシロキサン化合物とを反応させる際には、反応を均一に進行させる必要があるため、磁気攪拌子やスリーワンモーター等の攪拌機で溶液を攪拌することが好ましい。また、撹拌機は、得られる金属ナノ粒子の均一性を高めるため、せん断速度が０．５ｍ／秒以上となるように設定することが望ましい。 When using a solvent when reacting a metal ion and a polyhydrosiloxane compound, the reaction temperature is preferably not higher than the reflux temperature of the solvent. However, it is not limited to this, It can also be made more than the boiling point of a solvent. Further, the metal ion and the polyhydrosiloxane compound may be reacted while the solvent is evaporated. In addition, when reacting a metal ion and a polyhydrosiloxane compound, since it is necessary to make the reaction proceed uniformly, it is preferable to stir the solution with a stirrer such as a magnetic stirrer or a three-one motor. The stirrer is preferably set so that the shear rate is 0.5 m / second or more in order to improve the uniformity of the metal nanoparticles obtained.
金属イオンとポリヒドロシロキサン化合物との反応時間は、反応温度や溶媒等により異なるが、反応の終点についてはイオンクロマトグラフィー等で残留する金属イオンを定量することで調べることができる。なお、反応の終点は、生成される金属ナノ粒子と原料の金属イオンとで可視−紫外領域の吸収スペクトルが異なるという現象を利用することによっても調べることができる。また、金属イオンとポリヒドロシロキサン化合物を反応させるときの圧力は、特に限定されるものではないが、少なくとも反応に使用する容器の耐圧限界以下で行う必要がある。 The reaction time between the metal ion and the polyhydrosiloxane compound varies depending on the reaction temperature, the solvent, and the like, but the end point of the reaction can be examined by quantifying the remaining metal ion by ion chromatography or the like. The end point of the reaction can also be examined by utilizing the phenomenon that the absorption spectrum in the visible-ultraviolet region is different between the produced metal nanoparticles and the raw material metal ions. Moreover, the pressure at the time of making a metal ion and a polyhydrosiloxane compound react is although it does not specifically limit, It is necessary to carry out below the pressure | voltage limit of the container used for reaction at least.
金属イオンとポリヒドロシロキサン化合物との反応濃度は特に限定されるものではなく、適宜変更可能である。すなわち、金属ナノ粒子の用途に応じて、懸濁液中の金属含有量が所望の値となるように、溶媒等の添加や濃縮等で反応濃度を調整すると良い。例えば、金属ナノ粒子を液晶に添加する場合には、懸濁液中の金属含有量が１００ｐｐｍ以上１０％未満となるように反応濃度を設定し、また、金属ナノ粒子を配線材料として利用する場合には、懸濁液中の金属含有量が５％以上９５％未満となるように反応濃度を設定することが望ましい。 The reaction concentration between the metal ion and the polyhydrosiloxane compound is not particularly limited and can be changed as appropriate. That is, according to the use of the metal nanoparticles, the reaction concentration may be adjusted by adding or concentrating a solvent or the like so that the metal content in the suspension becomes a desired value. For example, when adding metal nanoparticles to the liquid crystal, the reaction concentration is set so that the metal content in the suspension is 100 ppm or more and less than 10%, and the metal nanoparticles are used as a wiring material. It is desirable to set the reaction concentration so that the metal content in the suspension is 5% or more and less than 95%.
なお、金属イオンに対するポリヒドロシロキサン化合物の添加量が少ない場合には、生成された懸濁液中の金属イオン濃度が低くなるため、本実施例においてはポリヒドロシロキサン化合物の添加量を金属イオンが完全に金属に還元される理論値の１乃至１０倍に設定している。 In addition, when the addition amount of the polyhydrosiloxane compound with respect to the metal ion is small, the metal ion concentration in the generated suspension is lowered. Therefore, in this embodiment, the addition amount of the polyhydrosiloxane compound is reduced by the metal ion. It is set to 1 to 10 times the theoretical value that is completely reduced to metal.
上記方法によって製造した金属ナノ粒子の懸濁液は、還元剤であるポリヒドロシロキサン化合物に由来するケイ素化合物が含まれている。例えば、酢酸銀（ＣＨ３ＣＯＯＡｇ）とポリ（ヒドロメチルシロキサン）（[−Ｓｉ（Ｈ）（ＣＨ３）Ｏ−]ｎ）の反応では、酢酸エステル（[−Ｓｉ（ＯＣＯＣＨ３）（ＣＨ３）Ｏ−]ｎ）が生成される。このように、還元反応後に生成されるケイ素化合物は、とくに不都合がなければ取り除く必要はないが、一般には金属ナノ粒子の高純度化のため、分離・除去する必要がある。すなわち、本願発明の金属ナノ粒子の製造方法においては、金属ナノ粒子の懸濁液中に残留する有機ケイ素化合物や余剰還元剤などの夾雑物が限外濾過によって容易に除去され得るという作用を有する。 The suspension of metal nanoparticles produced by the above method contains a silicon compound derived from a polyhydrosiloxane compound that is a reducing agent. For example, in the reaction of silver acetate (CH 3 COOAg) and poly (hydromethylsiloxane) ([—Si (H) (CH 3 ) O—] n), acetate ester ([—Si (OCOCH 3 ) (CH 3 )) O-] n) is generated. As described above, the silicon compound produced after the reduction reaction does not need to be removed unless particularly inconvenient, but generally needs to be separated and removed in order to increase the purity of the metal nanoparticles. That is, the metal nanoparticle production method of the present invention has an effect that impurities such as an organosilicon compound and an excess reducing agent remaining in the suspension of metal nanoparticles can be easily removed by ultrafiltration. .
なお、これらの夾雑物を限外濾過により除去する際の条件は、とくに限定されるものではないが、温度は０℃以上１５０℃以下にすると良い。ただし、金属ナノ粒子を高温に曝すと焼結が進行するため、温度については０℃以上１００℃以下とすることがより好ましい。 The conditions for removing these contaminants by ultrafiltration are not particularly limited, but the temperature may be 0 ° C. or higher and 150 ° C. or lower. However, since sintering proceeds when the metal nanoparticles are exposed to a high temperature, the temperature is more preferably 0 ° C. or more and 100 ° C. or less.
以上説明したように、本実施例の製造方法によれば、金属ナノ粒子を製造する過程でポリヒドロシロキサン化合物と金属塩の陰イオンの反応によって生成されるケイ素化合物及び懸濁液中に残留する余剰還元剤を限外濾過や遠心分離により安全かつ効率よく除去することが可能である。これにより、懸濁液中の金属ナノ粒子の純度を効率よく高めることができる。そして、このように懸濁液中の夾雑物を限外濾過や遠心分離によって除去することによれば、高価な設備が不要であるため、設備コストの削減を図ることができる。従って、金属ナノ粒子を安価に製造することが可能である。 As described above, according to the manufacturing method of the present embodiment, the silicon compound produced by the reaction of the anion of the polyhydrosiloxane compound and the metal salt in the process of manufacturing the metal nanoparticles and remains in the suspension. Excess reducing agent can be removed safely and efficiently by ultrafiltration or centrifugation. Thereby, the purity of the metal nanoparticles in the suspension can be increased efficiently. And by removing the impurities in the suspension by ultrafiltration or centrifugation in this way, expensive equipment is unnecessary, so that equipment costs can be reduced. Therefore, it is possible to produce metal nanoparticles at a low cost.
以下に、本発明の実施例を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。金属微粒子の粒径は、透過型電子顕微鏡、Ｘ線小角散乱法により測定を行った。金属ナノ粒子の純度は、熱重量分析装置で１分間に５℃昇温を行い、５００℃となった時点での重量減少量から金属量を求めた。導電性の評価は四探針法により測定した。 Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. The particle size of the metal fine particles was measured by a transmission electron microscope and an X-ray small angle scattering method. As for the purity of the metal nanoparticles, the temperature was raised by 5 ° C. per minute with a thermogravimetric analyzer, and the amount of metal was determined from the weight loss when the temperature reached 500 ° C. The evaluation of conductivity was measured by the four probe method.
［実施例１］
硝酸銀（ＡｇＮＯ３）１０ｇを水２０ｇに、ポリ（Ｎ‐ビニルピロリドン）（以下ＰＶＰ）６．５ｇをエタノール２０ｇに、オクチルアミン（Ｃ８Ｈ１７ＮＨ２）７．６ｇをエタノールに、ポリ（ヒドロメチルシロキサン）（[−Ｓｉ（Ｈ）（ＣＨ３）Ｏ−]ｎ）（以下ＰＭＨＳと略記する）３．５ｇをエタノールに溶解した。その後、硝酸銀水溶液とＰＶＰエタノール溶液の混合物を３０分間攪拌し、オクチルアミンエタノール溶液を追加し３０分間攪拌した。その後、ＰＭＨＳエタノール溶液を加え、室温で１時間攪拌することで銀ナノ粒子の懸濁液を得た。このとき、銀ナノ粒子の平均粒径は２５ｎｍであった。得られた銀ナノ粒子懸濁液にメタノールを添加すると銀ナノ粒子の沈殿と夾雑物が溶解した上澄み溶液に分離した。３０分放置して十分に分離したところで濾紙によって濾過を行い、銀ナノ粒子を精製した。この精製操作を３回行うことで、純度の高い銀ナノ粒子を得た。銀ナノ粒子とバインダー樹脂（積水化学製ＢＬ−２）エタノール溶液を混合し、銀含有率８０％の銀ペーストを調製し、大気中１８０℃で３０分焼成し導電性を評価したところ、抵抗率５．５μΩｃｍであった。
[Example 1]
Silver nitrate (AgNO 3 ) 10 g in water 20 g, poly (N-vinylpyrrolidone) (hereinafter PVP) 6.5 g in ethanol 20 g, octylamine (C 8 H 17 NH 2 ) 7.6 g in ethanol, poly (hydro Methyl siloxane) ([—Si (H) (CH 3 ) O—] n) (hereinafter abbreviated as PMHS) (3.5 g) was dissolved in ethanol. Then, the mixture of the silver nitrate aqueous solution and the PVP ethanol solution was stirred for 30 minutes, and the octylamine ethanol solution was added and stirred for 30 minutes. Thereafter, a PMHS ethanol solution was added and stirred at room temperature for 1 hour to obtain a silver nanoparticle suspension. At this time, the average particle diameter of the silver nanoparticles was 25 nm. When methanol was added to the obtained silver nanoparticle suspension, it was separated into a supernatant solution in which silver nanoparticle precipitates and impurities were dissolved. When it was allowed to stand for 30 minutes and sufficiently separated, it was filtered with a filter paper to purify the silver nanoparticles. By performing this purification operation three times, high-purity silver nanoparticles were obtained. Silver nanoparticles and binder resin (BL-2 manufactured by Sekisui Chemical Co., Ltd.) ethanol solution were mixed to prepare a silver paste with a silver content of 80%, and the conductivity was evaluated by baking at 180 ° C. for 30 minutes in the atmosphere. It was 5.5 μΩcm.
［実施例２〜８］
溶媒、銀塩、保護剤について条件を変更し、実施例１と同様の操作を行ったところ、銀ナノ粒子が得られた。結果を以下に示す。
[Examples 2 to 8]
When conditions were changed about a solvent, silver salt, and a protective agent, and operation similar to Example 1 was performed, the silver nanoparticle was obtained. The results are shown below.
［実施例９］
トルエン１０ｇ、オクタンチオール２ｇ、塩化金（ＩＩＩ）０．１ｇの混合物に攪拌しながらＰＭＨＳ０．５ｇを加えて室温で１時間攪拌することで、暗赤色の金微粒子懸濁液を得た。平均粒径は３．８ｎｍであった。
[Example 9]
To a mixture of 10 g of toluene, 2 g of octanethiol and 0.1 g of gold (III) chloride, 0.5 g of PMHS was added and stirred at room temperature for 1 hour to obtain a dark red gold fine particle suspension. The average particle size was 3.8 nm.
［実施例１０］
エタノール５０ｇにポリ（Ｎ−ビニルピロリドン）２．０ｇ、酢酸パラジウム０．２gを溶解し、攪拌しながらＰＭＨＳ０．５ｇを加えて室温で１時間攪拌することで、暗褐色のパラジウム微粒子懸濁液を得た。平均粒径は８．２ｎｍであった。
[Example 10]
Dissolve 2.0 g of poly (N-vinylpyrrolidone) and 0.2 g of palladium acetate in 50 g of ethanol, add 0.5 g of PMHS while stirring, and stir at room temperature for 1 hour to obtain a dark brown palladium fine particle suspension. Obtained. The average particle size was 8.2 nm.
［実施例１１］
エタノール５０ｇにポリ（Ｎ−ビニルピロリドン）２．０ｇ、塩化白金酸（ＩＶ）０．１ｇを溶解し、攪拌しながらＰＭＨＳ０．５ｇを加えて室温で１時間攪拌することで、黒色の白金微粒子懸濁液を得た。平均粒径は１０．９ｎｍであった。
[Example 11]
Dissolve 2.0 g of poly (N-vinylpyrrolidone) and 0.1 g of chloroplatinic acid (IV) in 50 g of ethanol, add 0.5 g of PMHS with stirring, and stir at room temperature for 1 hour, to suspend black platinum fine particles. A turbid liquid was obtained. The average particle size was 10.9 nm.
［実施例１２］
トルエン１０ｇ、ポリ（Ｎ−ビニルピロリドン）２．０ｇ、酢酸銅（ＩＩ）０．０５ｇ、酢酸パラジウム（ＩＩ）０．０２ｇの混合物に攪拌しながらＰＭＨＳ０．５ｇを加えて１時間還流することで、黒色の銅／パラジウム微粒子懸濁液を得た。平均粒径は２５．８ｎｍであった。
[Example 12]
By adding 0.5 g of PMHS with stirring to a mixture of 10 g of toluene, 2.0 g of poly (N-vinylpyrrolidone), 0.05 g of copper (II) acetate and 0.02 g of palladium (II), and refluxing for 1 hour, A black copper / palladium fine particle suspension was obtained. The average particle size was 25.8 nm.
［比較例１］
酢酸亜鉛１０ｇを水２０ｇに、ポリ（Ｎ‐ビニルピロリドン）（以下ＰＶＰ）６．５ｇをエタノール２０ｇに、オクチルアミン（Ｃ８Ｈ１７ＮＨ２）７．６ｇをエタノールに、ポリ（ヒドロメチルシロキサン）（[−Ｓｉ（Ｈ）（ＣＨ３）Ｏ−]ｎ）（以下ＰＭＨＳ）５ｇをエタノールに溶解後３０分間攪拌し、オクチルアミンエタノール溶液を追加し３０分間攪拌する。その後、ＰＭＨＳエタノール溶液を加え、室温で３時間攪拌したが亜鉛ナノ粒子を得ることができなかった。
[Comparative Example 1]
10 g of zinc acetate in 20 g of water, 6.5 g of poly (N-vinylpyrrolidone) (hereinafter PVP) in 20 g of ethanol, 7.6 g of octylamine (C 8 H 17 NH 2 ) in ethanol, poly (hydromethylsiloxane) ([—Si (H) (CH 3 ) O—] n) (hereinafter PMHS) 5 g is dissolved in ethanol and stirred for 30 minutes, and an octylamine ethanol solution is added and stirred for 30 minutes. Thereafter, PMHS ethanol solution was added and stirred for 3 hours at room temperature, but zinc nanoparticles could not be obtained.
［比較例２］
エチレングリコール１０ｇ、オクチルアミン３．０ｇ、酢酸銀１．０ｇの混合物にフェニルメチルシラン０．５ｇを加えて室温で１時間攪拌したところ、黒色の銀が沈殿し分散液を得ることができなかった。
[Comparative Example 2]
When 0.5 g of phenylmethylsilane was added to a mixture of 10 g of ethylene glycol, 3.0 g of octylamine and 1.0 g of silver acetate and stirred for 1 hour at room temperature, black silver was precipitated and a dispersion could not be obtained. .
本発明は、電子部品の配線材料や液晶表示装置等、各種分野で使用される金属ナノ粒子に対して適用可能である。例えば、本発明の方法によって製造された銀ナノ粒子をバインダー樹脂、溶媒等と混合することで銀ペーストを作成し、これをインクジェット印刷、スクリーン印刷等の印刷技術等によりパターンを形成し、適当な温度、適当な時間で焼成することで銀の導電パターンを形成することができる。パラジウムナノ粒子や白金ナノ粒子は燃料電池等の触媒に広く利用することができる。さらに本発明における金属微粒子の懸濁液製造方法は、特殊な製造設備を必要としないため、適用範囲が広く極めて工業的な意義が高い。
The present invention is applicable to metal nanoparticles used in various fields such as wiring materials for electronic parts and liquid crystal display devices. For example, a silver paste is prepared by mixing silver nanoparticles produced by the method of the present invention with a binder resin, a solvent, etc., and a pattern is formed by a printing technique such as ink jet printing or screen printing. A silver conductive pattern can be formed by baking at an appropriate time at a temperature. Palladium nanoparticles and platinum nanoparticles can be widely used for catalysts such as fuel cells. Furthermore, the method for producing a suspension of fine metal particles in the present invention does not require special production equipment, and therefore has a wide range of applications and is highly industrially significant.
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| WO2014054550A1 (en) * | 2012-10-01 | 2014-04-10 | Ｄｏｗａエレクトロニクス株式会社 | Method for producing fine silver particles |
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| CN104736275A (en) * | 2012-10-24 | 2015-06-24 | 日本曹达株式会社 | Production method for particles of element having standard electrode potential greater than 0v |
| JP5876936B2 (en) * | 2012-10-24 | 2016-03-02 | 日本曹達株式会社 | Method for producing particles of elements whose standard electrode potential is greater than 0V |
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