JP2005220435A - Method of producing metal nanoparticle and dispersion of metal nanoparticle - Google Patents
Method of producing metal nanoparticle and dispersion of metal nanoparticle Download PDFInfo
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本発明は、金属ナノ粒子及び金属ナノ粒子分散液の製造方法に係り、詳しくは高価な設備を必要とせず平均粒径２〜３０ｎｍの金属ナノ粒子を簡便且つ安価に得られ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。 The present invention relates to a metal nanoparticle and a method for producing a metal nanoparticle dispersion, and more particularly, a metal nanoparticle and a metal that can easily and inexpensively obtain metal nanoparticles having an average particle diameter of 2 to 30 nm without requiring expensive equipment. The present invention relates to a method for producing a nanoparticle dispersion.
金属ナノ粒子は、極めて微小な粒径に起因する様々な特異な物性を示すことから、導電材料、着色材料、コンデンサー、バイオセンサー、化学センサー、蛍光材料、偏光材料、磁気メモリー材料などの種々の分野で利用されている。 Since metal nanoparticles exhibit various unique properties due to extremely small particle sizes, various kinds of materials such as conductive materials, colored materials, capacitors, biosensors, chemical sensors, fluorescent materials, polarizing materials, magnetic memory materials, etc. Used in the field.
金属ナノ粒子の合成法は、ブレイクダウン法とビルドアップ法に大別されるが、金属は展性、並びに延性に富むため主にビルドアップ法により製造されている。また、ビルドアップ法は乾式法と湿式法に区別され、多くの製造方法が開示されている。 The synthesis method of metal nanoparticles is roughly divided into a breakdown method and a build-up method, but metals are mainly manufactured by the build-up method because they are rich in malleability and ductility. Further, the build-up method is classified into a dry method and a wet method, and many manufacturing methods are disclosed.
乾式法での金属ナノ粒子製造方法としては、特許文献１には、ガス中蒸発法により金属ナノ粒子を製造する方法が開示されている。また、特許文献２には、真空蒸着法により高分子マトリクス膜上に金属を蒸着することにより金属ナノ粒子を製造する方法が開示されている。これらの方法で得られる金属ナノ粒子は大変高濃度である上に、不純物をほとんど含まれない利点を有しているが、粒度分布が広いため、金属ナノ粒子の粒径に依存する物性（サイズ効果）を利用した用途には不適であった。また、これらの方法では、金属蒸気を作製するための特別な装置が必要であるため、製造上、不利であった。 As a method for producing metal nanoparticles by a dry method, Patent Document 1 discloses a method for producing metal nanoparticles by a gas evaporation method. Patent Document 2 discloses a method for producing metal nanoparticles by depositing a metal on a polymer matrix film by a vacuum deposition method. The metal nanoparticles obtained by these methods have a very high concentration and have the advantage of containing almost no impurities. However, because of the wide particle size distribution, the physical properties (size) depend on the particle size of the metal nanoparticles. It was unsuitable for applications using (effect). Further, these methods are disadvantageous in production because a special apparatus for producing metal vapor is required.
一方、溶液中で金属イオンを還元することにより金属ナノ粒子が得られる湿式法は、特別な設備を必要とせず、スケールアップが容易である利点を有する。生成した金属ナノ粒子の凝集を防ぐため、金属ナノ粒子表面に保護層を作製することが通常である。 On the other hand, the wet method in which metal nanoparticles are obtained by reducing metal ions in a solution does not require special equipment and has the advantage of being easy to scale up. In order to prevent aggregation of the generated metal nanoparticles, it is usual to produce a protective layer on the surface of the metal nanoparticles.
しかし、上記湿式法で製造可能な金属ナノ粒子濃度は、せいぜい数ｍＭ程度であり、高濃度の金属ナノ粒子を得るためには、濃縮やデカンテーションによる沈降回収が必要であった。これは、高濃度の金属イオンが還元される場合、生成した金属ナノ粒子濃度が上昇し、保護層により金属ナノ粒子が安定される前に粒子間の凝集が進行するためである。 However, the concentration of metal nanoparticles that can be produced by the above wet method is at most about several mM, and in order to obtain high-concentration metal nanoparticles, sedimentation recovery by concentration or decantation was required. This is because when a high concentration of metal ions is reduced, the concentration of the generated metal nanoparticles increases, and aggregation between the particles proceeds before the metal nanoparticles are stabilized by the protective layer.
このような課題を解決する手法として、非特許文献１には、次の金属ナノ粒子の製造方法が開示されている。即ち、金イオンが存在する水溶液、及びテトラオクチルアンモニウムとアルカンチオールが存在する水と非混和性の有機溶媒を混合攪拌して懸濁液体となし、金イオンを水相から有機溶媒相に相間移動せしめ、その後還元剤である水素化ホウ素ナトリウム水溶液を混合し攪拌することで、水相と有機溶媒相の界面で還元剤と金イオンが接触し、金イオンの還元が進行し、金ナノ粒子が有機溶媒相中に生成する。この時、金ナノ粒子はアルカンチオールとの相互作用により保護され、有機溶媒相内で均一に分散した金ナノ粒子が得られる方法である。 As a technique for solving such a problem, Non-Patent Document 1 discloses the following method for producing metal nanoparticles. In other words, an aqueous solution containing gold ions, and water containing tetraoctylammonium and alkanethiol and an immiscible organic solvent are mixed and stirred to form a suspension, and gold ions are transferred from the aqueous phase to the organic solvent phase. Then, by mixing and stirring an aqueous sodium borohydride solution that is a reducing agent, the reducing agent and gold ions come into contact with each other at the interface between the aqueous phase and the organic solvent phase, the reduction of the gold ions proceeds, and the gold nanoparticles become Formed in the organic solvent phase. At this time, the gold nanoparticles are protected by the interaction with the alkanethiol, and gold nanoparticles dispersed uniformly in the organic solvent phase are obtained.
また、特許文献３には、金属ナノ粒子の保護剤として櫛形ブロックコポリマーを用いた金属ナノ粒子分散液の製造の方法が開示されている。櫛形ブロックコポリマーの保護能力が高いため金属イオンが高濃度で存在する場合でも、金属ナノ粒子間の凝集が抑制され、独立分散した金属ナノ粒子が得られる。それに加え、櫛形ブロックコポリマーは金属イオンの還元力を有しており、その還元能が一般に用いられる水素化ホウ素ナトリウムやヒドラジンなどの還元剤に比べて弱いため、高濃度の金属イオンが存在する溶液であっても、生成する金属ナノ粒子の凝集を起こすことなく、均一に分散した金属ナノ粒子が得られるものである。 Patent Document 3 discloses a method for producing a metal nanoparticle dispersion using a comb block copolymer as a protective agent for metal nanoparticles. Since the comb block copolymer has a high protective ability, even when metal ions are present at a high concentration, aggregation between the metal nanoparticles is suppressed, and independently dispersed metal nanoparticles can be obtained. In addition, comb-shaped block copolymers have the ability to reduce metal ions, and their reducing ability is weak compared to commonly used reducing agents such as sodium borohydride and hydrazine, so a solution containing high concentrations of metal ions is present. Even so, uniformly dispersed metal nanoparticles can be obtained without causing aggregation of the generated metal nanoparticles.
しかし、これらの方法は、水とそれに非混和性の有機溶媒からなる２相還元法を用いていることから、水溶液を除去する工程が必要となり、バッチによる金属ナノ粒子製造方法に限定される。また、金属イオンを還元する際に、有機若しくは高分子副生成物が生じる結果、金属ナノ粒子以外の不純物が有機溶媒中に存在するため、デカンテーションや遠心分離等の精製工程が必要となる。それに加え、前記方法は金属イオン濃度の上限が１００ｍＭ程度であるため、多量の金属ナノ粒子を製造するために多量の溶媒が必要となり、これは多量の廃液を産出する問題があった。 However, since these methods use a two-phase reduction method consisting of water and an organic solvent immiscible with it, a step for removing the aqueous solution is required, and the method is limited to batch production of metal nanoparticles. In addition, when reducing metal ions, organic or polymer by-products are generated, and impurities other than metal nanoparticles are present in the organic solvent, so that a purification step such as decantation or centrifugation is required. In addition, since the upper limit of the metal ion concentration in the method is about 100 mM, a large amount of solvent is required to produce a large amount of metal nanoparticles, which has a problem of producing a large amount of waste liquid.
このため、湿式法で煩雑な工程を経ることなく、高濃度の金属ナノ粒子を連続して合成可能な金属ナノ粒子製造方法が望まれている。
従って、本発明はかかる要望に応え、従来における上記した問題点を解決し、金属ナノ粒子を簡便且つ容易に得られる金属ナノ粒子及び金属ナノ粒子分散液の製造方法を提供することを目的としている。 Accordingly, the present invention has been made in response to such a demand, and aims to solve the above-mentioned problems in the prior art and to provide a metal nanoparticle and a method for producing a metal nanoparticle dispersion that can easily and easily obtain metal nanoparticles. .
本願発明は、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を混合した溶液を溶媒下で還元することにより、有機分子で保護した金属ナノ粒子集合体を沈降させて回収するものであり、また少なくとも１種の金属イオンを含有する溶液、保護剤含有溶液、そして還元剤含有溶液を溶媒に滴下して有機分子で保護した金属ナノ粒子集合体を沈降させて回収する場合や、また少なくとも１種の金属イオンと保護剤が含まれる溶液と還元剤含有溶液とを溶媒に滴下する場合も含まれる。 The present invention is a method in which a solution in which at least one metal ion and a protective agent composed of an organic molecule are mixed is reduced in a solvent to precipitate and collect the metal nanoparticle aggregate protected by the organic molecule, In addition, when a solution containing at least one metal ion, a protective agent-containing solution, and a reducing agent-containing solution is dropped into a solvent to precipitate the metal nanoparticle aggregate protected with organic molecules, or at least 1 is collected. The case where a solution containing a seed metal ion and a protective agent and a reducing agent-containing solution are dropped into a solvent is also included.
保護剤は、金属ナノ粒子と親和性を示す官能基を主鎖及び／または側鎖に有し、かつ溶媒と親和性の低い主鎖からなり、その主鎖及び／または側鎖に第一級アミノ基、第二級アミノ基、第三級アミノ基、塩基性窒素原子を有する複素塩基、チオール、カルボン酸塩基、スルホン酸塩基、フェニル基、ラウリル基、ステアリル基、ドデシル基、そしてオレイル基から選ばれた少なくとも１個の官能基を有し、かつ該主鎖及び／または側鎖が３〜５０個の炭素から構成されているものを使用することができる。 The protective agent has a functional group having an affinity for metal nanoparticles in the main chain and / or side chain, and is composed of a main chain having a low affinity for the solvent, and the main chain and / or side chain is primary. From amino groups, secondary amino groups, tertiary amino groups, heterocyclic bases with basic nitrogen atoms, thiols, carboxylate groups, sulfonate groups, phenyl groups, lauryl groups, stearyl groups, dodecyl groups, and oleyl groups Those having at least one selected functional group and having the main chain and / or side chain composed of 3 to 50 carbons can be used.
更に、他の保護剤としては、金属ナノ粒子と親和性を示す官能基を主鎖及び／または側鎖に有し、かつ溶媒と親和性の高い主鎖からなり、その主鎖及び／または側鎖に第一級アミノ基、第二級アミノ基、第三級アミノ基、塩基性窒素原子を有する複素塩基、チオール、カルボン酸塩基、シアノ基、そしてスルホン酸塩基から選ばれた少なくとも２つ以上の官能基を有し、かつ該主鎖及び／または側鎖が分子量１，０００〜１０，０００のポリエーテルから構成されているものを使用することができる。具体的には、末端ジアミンポリエチレンオキシド、ジチオール末端ポリエチレンオキシド、末端プロピオン酸ポリエチレンオキシド、トリアミン末端ポリプロピレンオキシド、ジアミン末端ポリプロピレンオキシド、そしてジチオール末端ポリプロピレンオキシドから選ばれた少なくとも１種である。 Furthermore, as another protective agent, the main chain and / or side chain has a functional group having an affinity with the metal nanoparticles and has a high affinity with the solvent. At least two or more selected from primary amino group, secondary amino group, tertiary amino group, heterocyclic base having basic nitrogen atom, thiol, carboxylate group, cyano group, and sulfonate group in the chain In which the main chain and / or the side chain is composed of a polyether having a molecular weight of 1,000 to 10,000 can be used. Specifically, it is at least one selected from terminal diamine polyethylene oxide, dithiol-terminated polyethylene oxide, terminal propionic acid polyethylene oxide, triamine-terminated polypropylene oxide, diamine-terminated polypropylene oxide, and dithiol-terminated polypropylene oxide.
また、本願請求項記載の発明では、金属イオンの金属が金、銀、白金、パラジウム、ロジウム、ルテニウム、銅、そしてインジウムから選ばれる少なくとも１種である場合や、金属イオンの金属が銀と銅の組合せからなる場合や、銀とインジウムの組合せからなる合金の金属ナノ粒子の製造方法も含んでいる。 In the invention of the present invention, the metal ion metal is at least one selected from gold, silver, platinum, palladium, rhodium, ruthenium, copper, and indium, or the metal ion metal is silver and copper. And a method for producing metal nanoparticles of an alloy composed of a combination of silver and indium.
また、本願請求項記載の発明では、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を混合した溶液を第１の溶媒下で還元することにより、有機分子で保護した金属ナノ粒子集合体を沈降させて回収し、該金属ナノ粒子集合体を第２の溶媒中に再分散した金属ナノ粒子分散液の製造方法も含んでいる。 In the invention of the present invention, the metal nanoparticle aggregate protected with organic molecules is reduced by reducing a solution in which a protective agent composed of at least one metal ion and an organic molecule is mixed in a first solvent. It also includes a method for producing a metal nanoparticle dispersion in which the metal nanoparticle aggregate is recovered by settling and redispersed in a second solvent.
また、本願請求項記載の発明では、保護剤として金属ナノ粒子と親和性を示す官能基を主鎖及び／または側鎖に有し、かつ溶媒と親和性の低い主鎖から構成されるものを使用する場合には、第１の溶媒として極性溶媒を、そして第２の溶媒として金属ナノ粒子集合体中にカルボン酸塩が含まれない場合は、非極性溶媒を使用する。 In the invention described in the claims of the present application, the protective agent has a functional group having affinity with metal nanoparticles in the main chain and / or side chain, and is composed of a main chain having low affinity with the solvent. When used, a polar solvent is used as the first solvent, and a non-polar solvent is used as the second solvent if the carboxylate is not contained in the metal nanoparticle assembly.
また、本願請求項記載の発明では、保護剤として金属ナノ粒子と親和性を示す官能基を主鎖及び／または側鎖に有し、かつ溶媒と親和性の低い主鎖から構成されるものを使用する場合には、第１の溶媒として極性溶媒を、そして第２の溶媒として金属ナノ粒子集合体中にカルボン酸塩が含まれない場合は、非極性溶媒を使用する。 In the invention described in the claims of the present application, the protective agent has a functional group having affinity with metal nanoparticles in the main chain and / or side chain, and is composed of a main chain having low affinity with the solvent. When used, a polar solvent is used as the first solvent, and a non-polar solvent is used as the second solvent if the carboxylate is not contained in the metal nanoparticle assembly.
また、本願請求項記載の発明では、保護剤として金属ナノ粒子と親和性を示す少なくとも２つ以上の官能基を主鎖及び／または側鎖に有し、かつ溶媒と親和性の高い主鎖から構成されるものを使用する場合には、第１の溶媒と第２の溶媒とともに極性溶媒を使用する。 In the invention described in the present claim, the main chain and / or side chain has at least two or more functional groups having affinity with the metal nanoparticles as a protective agent, and the main chain has high affinity with the solvent. In the case of using what is constituted, a polar solvent is used together with the first solvent and the second solvent.
このように、本願発明では、高濃度の金属イオン含有溶液、保護剤含有溶液を反応系である溶媒中に滴下し、金属イオンを還元することにより有機分子で保護された金属ナノ粒子が生成した結果、有機分子で保護された金属ナノ粒子と溶媒の親和性が低下し、有機分子で保護された金属ナノ粒子が集合体として沈降する。この結果、反応系内の金属イオン濃度が過剰になることなく、高純度の有機分子で保護された金属ナノ粒子集合体を連続して回収することができ、そして金属ナノ粒子集合体を第２の溶媒中に再分散させることで
金属ナノ粒子分散液を製造でき、ペーストとして種々の用途に使用することができる。
Thus, in this invention, the metal nanoparticle protected by the organic molecule produced | generated by dripping the high concentration metal ion containing solution and the protective agent containing solution in the solvent which is a reaction system, and reducing a metal ion. As a result, the affinity between the metal nanoparticles protected with organic molecules and the solvent decreases, and the metal nanoparticles protected with organic molecules settle as aggregates. As a result, metal nanoparticle aggregates protected with high-purity organic molecules can be continuously recovered without excessive metal ion concentration in the reaction system. The metal nanoparticle dispersion liquid can be produced by redispersion in the above solvent, and can be used for various applications as a paste.
本願発明によれば、高純度の有機分子からなる保護剤で保護された金属ナノ粒子を簡便且つ容易に製造可能であるとともに、回収した金属ナノ粒子集合体を使用した保護剤によって極性溶媒または非極性溶媒を適宜選定し、この溶媒中に再分散して高濃度の金属ナノ粒子分散液を容易に得ることができる。また、高濃度の金属イオン含有溶液、保護剤含有溶液を反応系である溶媒中に連続して滴下することで高純度の有機分子で保護された金属ナノ粒子を連続して回収することができる。もろん、合金ナノ粒子も製造することができる。 According to the present invention, metal nanoparticles protected with a protective agent composed of high-purity organic molecules can be easily and easily produced, and a polar solvent or non-protective agent can be produced by a protective agent using the recovered metal nanoparticle aggregate. A polar solvent is appropriately selected and redispersed in this solvent, whereby a highly concentrated metal nanoparticle dispersion can be easily obtained. Moreover, metal nanoparticles protected with high-purity organic molecules can be continuously recovered by continuously dropping a high-concentration metal ion-containing solution and a protective agent-containing solution into a solvent that is a reaction system. . Of course, alloy nanoparticles can also be produced.
本発明の１つの実施形態として、予め溶媒を反応容器と回収容器とをエアポンプで循環させながら、金属イオン含有溶液、有機分子含有溶液、そして還元剤含有溶液を反応器内の溶媒に連続滴下しつつ、有機分子で保護した金属ナノ粒子集合を回収容器で沈降させ連続して回収する方法がある。 As one embodiment of the present invention, the metal ion-containing solution, the organic molecule-containing solution, and the reducing agent-containing solution are continuously dropped into the solvent in the reactor while circulating the solvent in advance between the reaction vessel and the recovery vessel with an air pump. On the other hand, there is a method in which metal nanoparticle aggregates protected with organic molecules are precipitated in a recovery container and continuously recovered.
本発明においては、上記金属イオンとしては特に限定されず、例えば金、銀、白金、パラジウム、ロジウム、ルテニウム、銅、そしてインジウム等を挙げることができる。無論、これらの金属を組合せることもできる。 In the present invention, the metal ion is not particularly limited, and examples thereof include gold, silver, platinum, palladium, rhodium, ruthenium, copper, and indium. Of course, these metals can also be combined.
上記金属イオン含有溶液は、極性溶媒に可溶性の金属化合物を溶解することで調製でき、該金属化合物は特に限定されず、例えば塩化金酸／またはその塩、硝酸銀、塩化銀、酢酸銀、塩化白金酸／またはその塩、塩化パラジウム、硝酸パラジウム、酢酸パラジウム、硝酸パラジウム／またはその塩、塩化銅（２）、硝酸銅（２）、酢酸銅（２）等が挙げられる。 The metal ion-containing solution can be prepared by dissolving a metal compound soluble in a polar solvent, and the metal compound is not particularly limited. For example, chloroauric acid / or a salt thereof, silver nitrate, silver chloride, silver acetate, platinum chloride Examples thereof include acid / or salt thereof, palladium chloride, palladium nitrate, palladium acetate, palladium nitrate / or salt thereof, copper chloride (2), copper nitrate (2), and copper acetate (2).
上記金属イオン溶液の濃度は、溶媒に溶解可能な範囲であれば特に限定されず、好ましくは１００ｍＭ以上である。１００ｍＭ未満であると、十分高濃度の金属ナノ粒子が連続して得られないため、好ましくない。 The concentration of the metal ion solution is not particularly limited as long as it can be dissolved in a solvent, and is preferably 100 mM or more. If it is less than 100 mM, a sufficiently high concentration of metal nanoparticles cannot be obtained continuously, such being undesirable.
上記金属イオン溶液は２種類以上の金属イオンを含有することが可能であり、異種の金属イオンを同時に還元することで合金若しくは２種類以上の金属が１粒子中に局在化した多元系金属ナノ粒子を得ることができ、例えば銀イオンと銅イオンの組合せや、銀イオンとインジウムイオンとの組合せがある。 The metal ion solution can contain two or more kinds of metal ions, and an alloy or multi-component metal nano-particles in which two or more kinds of metals are localized in one particle by simultaneously reducing different kinds of metal ions. Particles can be obtained, for example, a combination of silver ions and copper ions, or a combination of silver ions and indium ions.
上記金属イオンを還元する方法としては、金属イオンと、有機分子を混合した保護剤含有溶液と、そして還元作用を有する化合物を溶媒に溶解した還元剤含有溶液とを反応器への連続滴下、反応器への高圧水銀灯による光照射、反応器内でのアルコール含有水溶液の加熱還流等の方法を挙げることができる。 As a method for reducing the metal ions, a metal ion, a protective agent-containing solution in which organic molecules are mixed, and a reducing agent-containing solution in which a compound having a reducing action is dissolved in a solvent are continuously dropped into a reactor and reacted. Examples of the method include irradiation of light to a vessel with a high-pressure mercury lamp and heating and reflux of an alcohol-containing aqueous solution in the reactor.
上記還元作用を有する化合物は、還元剤として一般に用いられるものを使用することができ、例えば水素化ホウ素ナトリウム、ヒドラジン化合物、クエン酸又はその塩、コハク酸又はその塩、アスコルビン酸又はその塩、ホスフィン酸又はその塩、酒石酸／またはその塩等を使用することができる。 As the compound having the reducing action, those generally used as a reducing agent can be used. For example, sodium borohydride, hydrazine compound, citric acid or a salt thereof, succinic acid or a salt thereof, ascorbic acid or a salt thereof, phosphine An acid or a salt thereof, tartaric acid / or a salt thereof and the like can be used.
上記還元作用を有する化合物を溶媒に溶解した還元剤含有溶液の濃度は、溶媒に溶解可能な範囲であれば特に限定されず、好ましくは金属イオンモル濃度に対し０．１倍以上である。０．１倍未満であると、金属イオン含有溶液の滴下量に比べ多量の還元剤含有溶液が必要となり、工業的に不利なため好ましくない。 The concentration of the reducing agent-containing solution in which the compound having the reducing action is dissolved in a solvent is not particularly limited as long as it is in a range that can be dissolved in the solvent, and is preferably 0.1 times or more with respect to the metal ion molar concentration. If it is less than 0.1 times, a larger amount of reducing agent-containing solution is required than the amount of the metal ion-containing solution added, which is not preferable because it is industrially disadvantageous.
本発明における保護剤としては、金属ナノ粒子と親和性を示す官能基を主鎖及び／または側鎖に有し、かつ溶媒と親和性の低い主鎖から構成されるもの（タイプＡ）、また金属ナノ粒子と親和性を示す官能基を主鎖及び／または側鎖に有し、かつ溶媒と親和性の高い主鎖から構成されるもの（タイプＢ）を使用することができる。 Examples of the protective agent in the present invention include those having a functional group having an affinity for metal nanoparticles in the main chain and / or side chain and comprising a main chain having a low affinity for the solvent (type A), A substance having a functional group having an affinity for metal nanoparticles in the main chain and / or side chain and composed of a main chain having high affinity with a solvent (type B) can be used.
タイプＡとタイプＢの保護剤において金属ナノ粒子と親和性を示す官能基とは、該官能基中の非共有電子対が金属ナノ粒子表面に配位することで強い吸着力を示すものをいい、例えば第一級アミノ基、第二級アミノ基、第三級アミノ基、塩基性窒素原子を有する複素塩基、チオール、カルボン酸塩基、スルホン酸塩基、フェニル基、ラウリル基、ステアリル基、ドデシル基、オレイル基等を挙げることができる。上記官能基は、主鎖末端及び／または側鎖末端に限らず、主鎖中や側鎖中に存在してもよい。また、上記金属ナノ粒子と親和性を示す官能基は、極性溶媒との親和性を示すものであり、有機分子の極性溶媒への溶解性に寄与する機能を有する。 In the type A and type B protective agents, the functional group having an affinity with the metal nanoparticle refers to a functional group having a strong adsorptive power by coordination of an unshared electron pair in the functional group to the surface of the metal nanoparticle. For example, primary amino group, secondary amino group, tertiary amino group, heterobase having basic nitrogen atom, thiol, carboxylate group, sulfonate group, phenyl group, lauryl group, stearyl group, dodecyl group And oleyl group. The functional group is not limited to the main chain terminal and / or the side chain terminal, but may be present in the main chain or the side chain. In addition, the functional group having an affinity for the metal nanoparticles has an affinity for a polar solvent, and has a function of contributing to the solubility of organic molecules in the polar solvent.
上記タイプＡの保護剤において極性溶媒と親和性の低い主鎖及び／または側鎖とは、非極性分子鎖、非極性環状分子、そして非極性分子鎖または非極性環状分子中に非共有電子対を有する原子を含むものをいい、例えば炭素鎖式化合物、炭素環式化合物、複素環式化合物等を挙げることができる。上記保護剤中の主鎖及び／または側鎖は、３〜５０個の炭素から構成されているものが好ましく、３個未満であると金属ナノ粒子の凝集を防止する能力が十分でなく、他方５０個を超えると極性溶媒に溶解しないか、または金属ナノ粒子に配位吸着した後も沈降することなく、金属ナノ粒子／保護剤の複合体として溶媒中に分散安定状態を保つことになる。より好ましくは、５〜３０個である。 The main chain and / or side chain having a low affinity with the polar solvent in the type A protective agent includes a nonpolar molecular chain, a nonpolar cyclic molecule, and a non-shared electron pair in the nonpolar molecular chain or the nonpolar cyclic molecule. Examples thereof include carbon chain compounds, carbocyclic compounds, and heterocyclic compounds. The main chain and / or side chain in the protective agent is preferably composed of 3 to 50 carbons, and if it is less than 3, the ability to prevent aggregation of metal nanoparticles is not sufficient, while the other If it exceeds 50, it will not dissolve in the polar solvent, or will not settle after coordination adsorption to the metal nanoparticles, and will maintain a dispersion stable state in the solvent as a composite of metal nanoparticles / protective agent. More preferably, it is 5-30.
上記タイプＡの保護剤の具体例としては、例えばヘキサンチオール、オクタンチオール、ドデカンチオール、ヘキサデカンチオール、ナフテン酸、メルカプトウンデカン酸、メルカプトへキサン酸、メルカプトヘキサデカン酸、メルカプトヘキサノール、メルカプトドデカノール、メルカプトヘキサデカノール、メルカプトメントン、メルカプトメチルイミダゾール、ブチルアミン、オクチルアミン、オクタデシルアミン、アミノドデカン、ココアミン、ステリアルアミン、ジステリアルアミン、トリオクチルアミン、オレイン酸アミド、ステアリン酸アミド、ナフタレンジアミン、カルボン酸アミド、ステアラニリド等を挙げることができる。 Specific examples of the type A protective agent include, for example, hexanethiol, octanethiol, dodecanethiol, hexadecanethiol, naphthenic acid, mercaptoundecanoic acid, mercaptohexanoic acid, mercaptohexadecanoic acid, mercaptohexanol, mercaptododecanol, mercaptohexahexa Decanol, mercaptomentone, mercaptomethylimidazole, butylamine, octylamine, octadecylamine, aminododecane, cocoamine, stearylamine, disterealamine, trioctylamine, oleic acid amide, stearic acid amide, naphthalenediamine, carboxylic acid amide, And stearanilide.
タイプＢの保護剤は、タイプＡの保護剤と比べ溶媒と親和性の高い主鎖からなり、保護剤中の主鎖及び／または側鎖は、分子量１，０００〜１０，０００のポリエーテルから構成されている。分子量１，０００未満では、金属ナノ粒子の凝集を防止する能力が十分でなく、他方１０，０００を超えると金属ナノ粒子に配位吸着した後も沈降することなく、金属ナノ粒子／保護剤の複合体として溶媒中に分散安定状態を保つことになる。上記保護剤としては、例えば末端ジアミンポリエチレンオキシド、末端ジプロピオン酸ポリエチレンオキシド、トリアミン末端ポリプロピレンオキシド、ジアミン末端ポリプロピレンオキシド、そしてジチオール末端ポリプロピレンオキシドを挙げることができる。 The type B protective agent is composed of a main chain having a higher affinity for the solvent than the type A protective agent, and the main chain and / or the side chain in the protective agent is composed of a polyether having a molecular weight of 1,000 to 10,000. It is configured. If the molecular weight is less than 1,000, the ability to prevent aggregation of the metal nanoparticles is not sufficient. On the other hand, if the molecular weight exceeds 10,000, the metal nanoparticles / protective agent does not settle without coordinating and adsorbing to the metal nanoparticles. As a composite, a dispersion stable state is maintained in the solvent. Examples of the protective agent include terminal diamine polyethylene oxide, terminal dipropionic acid polyethylene oxide, triamine-terminated polypropylene oxide, diamine-terminated polypropylene oxide, and dithiol-terminated polypropylene oxide.
タイプＡあるいはタイプＢの保護剤を用いる場合の金属ナノ粒子製造用の溶媒（第１の溶媒）は、極性溶媒であれば特に限定されない。この極性溶媒としては、例えばメタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、ヘプタノール、α-テレピネオールなどのアルコール類、水、ジメチルフォルムアミド、酢酸エチル、１−メチル−２−ピロリドン、酢酸ブチル等を挙げることができる。極性溶媒は単一、または複数のものを混合して用いることができる。 The solvent (first solvent) for producing metal nanoparticles when using a type A or type B protective agent is not particularly limited as long as it is a polar solvent. Examples of the polar solvent include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, α-terpineol, water, dimethylformamide, ethyl acetate, 1-methyl-2-pyrrolidone, Examples include butyl acetate. The polar solvent can be used singly or in combination.
上記金属イオン含有溶液の滴下速度は、反応器内の金属イオン濃度が１００ｍＭ以下になるように設定することが好ましい。１００ｍＭを超えると有機分子に保護されていない金属ナノ粒子濃度が増加し、金属ナノ粒子間の凝集が進み、均一に分散した金属ナノ粒子が得られない。より好ましくは、５０ｍＭ以下である。 The dropping rate of the metal ion-containing solution is preferably set so that the metal ion concentration in the reactor is 100 mM or less. When the concentration exceeds 100 mM, the concentration of metal nanoparticles not protected by organic molecules increases, aggregation between the metal nanoparticles proceeds, and uniformly dispersed metal nanoparticles cannot be obtained. More preferably, it is 50 mM or less.
上記保護剤含有溶液の滴下速度は、反応器内の保護剤濃度が金属イオン濃度に対し０．１〜１５倍になるように設定することが好ましい。０．１倍未満になると保護剤で保護されていない金属ナノ粒子濃度が増加し、金属ナノ粒子間の凝集が進み、均一に分散した金属ナノ粒子が得られない。一方１５倍を超えると、保護剤と還元剤の反応が過剰に起こり、不必要な副生成物が生成する。より好ましくは、０．３〜１０倍である。 The dropping rate of the protective agent-containing solution is preferably set so that the protective agent concentration in the reactor is 0.1 to 15 times the metal ion concentration. If it is less than 0.1 times, the concentration of the metal nanoparticles not protected by the protective agent increases, the aggregation between the metal nanoparticles proceeds, and uniformly dispersed metal nanoparticles cannot be obtained. On the other hand, when it exceeds 15 times, the reaction between the protective agent and the reducing agent occurs excessively, and unnecessary by-products are generated. More preferably, it is 0.3 to 10 times.
尚、上記保護剤は、予め金属イオン含有溶液に溶解し、有機分子／金属イオン含有溶液として滴下することもできる。 In addition, the said protective agent can also melt | dissolve in a metal ion containing solution previously, and can also be dripped as an organic molecule / metal ion containing solution.
上記還元剤含有溶液の滴下速度は、反応器内の金属イオン濃度に対し０．１〜３０倍になるように設定することが好ましい。０．１倍未満になると、金属イオンの還元速度が遅くなり、連続生産性が低下する。一方３０倍を超えると、金属イオンの還元速度が速くなりすぎるため、金属ナノ粒子間の凝集が進み、均一に分散した金属ナノ粒子が得られない。より好ましくは、０．５〜２０倍である。 The dropping rate of the reducing agent-containing solution is preferably set so as to be 0.1 to 30 times the metal ion concentration in the reactor. If it is less than 0.1 times, the reduction rate of the metal ions becomes slow, and the continuous productivity is lowered. On the other hand, if it exceeds 30 times, the reduction rate of the metal ions becomes too fast, so that aggregation between the metal nanoparticles proceeds and uniform dispersed metal nanoparticles cannot be obtained. More preferably, it is 0.5 to 20 times.
本発明におけるタイプＡの保護剤を使用した金属ナノ粒子集合体は、保護剤中の主鎖及び／または側鎖と親和性を示す溶媒（第２の溶媒）に再分散が可能になる。 The metal nanoparticle aggregate using the type A protective agent in the present invention can be redispersed in a solvent (second solvent) having an affinity with the main chain and / or side chain in the protective agent.
この場合、このタイプＡの保護剤を使用した金属ナノ粒子集合体中にカルボン酸塩が含まれない場合は、上記第２の溶媒は非極性溶媒になる。この非極性溶媒は、特に限定されないが、例えばトルエン、へキサン、シクロヘキサン、ヘプタン、シクロヘプタン、オクタン、ドデカン、ベンゼン、キシレン等を挙げることができる。非極性溶媒は単一、／または複数のものを混合して用いることができる。 In this case, when the metal nanoparticle aggregate using the type A protective agent does not contain a carboxylate, the second solvent is a nonpolar solvent. The nonpolar solvent is not particularly limited, and examples thereof include toluene, hexane, cyclohexane, heptane, cycloheptane, octane, dodecane, benzene, xylene and the like. A nonpolar solvent can be used singly or in combination.
一方、タイプＡの保護剤を使用した金属ナノ粒子集合体中にカルボン酸塩が含まれる場合は、酸性溶液で該集合体を洗浄することでカルボン酸塩をカルボキシル基で安定化し、極性溶媒（第２の溶媒）に再分散することができる。 On the other hand, when a metal nanoparticle aggregate using a type A protective agent contains a carboxylate, the carboxylate is stabilized with a carboxyl group by washing the aggregate with an acidic solution, and a polar solvent ( In the second solvent).
この場合の極性溶媒としては、特に限定されないが、例えばメタノール、エタノール、２−エトキシエタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、ヘプタノール、α-テレピネオールなどのアルコール類、水、ジメチルフォルムアミド、酢酸エチル、１−メチル−２−ピロリドン、酢酸ブチル等を挙げることができる。極性溶媒は単一または複数のものを混合して用いることができる。 The polar solvent in this case is not particularly limited. For example, alcohols such as methanol, ethanol, 2-ethoxyethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, α-terpineol, water, dimethylformamide , Ethyl acetate, 1-methyl-2-pyrrolidone, butyl acetate and the like. The polar solvent can be used singly or in combination.
また、本発明におけるタイプＢの保護剤を使用した金属ナノ粒子集合体は、該保護剤中の主鎖と親和性の高い極性溶媒（第２の溶媒）に再分散が可能になる。この極性溶媒としては、前述しているとおり金属ナノ粒子製造用の際に使用する溶媒と同じものを用いることができる。 In addition, the metal nanoparticle aggregate using the type B protective agent in the present invention can be redispersed in a polar solvent (second solvent) having a high affinity with the main chain in the protective agent. As the polar solvent, as described above, the same solvent as that used for the production of metal nanoparticles can be used.
このように、本発明によれば、以上のような有機分子で保護した金属ナノ粒子集合体、または金属ナノ粒子分散溶液を簡便に製造可能となり、また連続して製造することもでき、比較的安価に金属ナノ粒子を提供することができ、しかも金属ナノ粒子分散溶液はナノ粒子分散ペーストとして使用することができる。 As described above, according to the present invention, the metal nanoparticle aggregate protected with the organic molecules as described above, or the metal nanoparticle dispersion solution can be easily manufactured, and can be continuously manufactured. Metal nanoparticles can be provided at low cost, and the metal nanoparticle dispersion solution can be used as a nanoparticle dispersion paste.
以下、本発明を実施例に基づいて説明する。これらの例は単なる例示であって、本発明を何ら限定するものではない。 Hereinafter, the present invention will be described based on examples. These examples are merely illustrative and do not limit the present invention in any way.
実施例１
塩化金酸・四水和物をエタノールに溶解することで１．０モルの塩化金酸溶液を調整した。また、ドデカンチオールをエタノールに溶解することで１．０モルのドデカンチオール溶液を調製した。これら溶液をそれぞれ５００ｍＬ（ミリリットル）取り出し、混合、攪拌することで溶液１を作製した。次に、１．０モルの水素化ホウ素ナトリウム水溶液を５００ｍＬ調製し溶液２とした。溶液１並びに溶液２をそれぞれ１ｍＬ／ｓｅｃで溶媒である１００ｍＬのエタノールを含む反応器中に滴下した。反応器中の溶液は、エアポンプにより連続してフィルターを通過させ、黒色沈殿物を回収した。
Example 1
A 1.0 mol chloroauric acid solution was prepared by dissolving chloroauric acid tetrahydrate in ethanol. Moreover, 1.0 mol dodecanethiol solution was prepared by dissolving dodecanethiol in ethanol. 500 mL (milliliter) of each of these solutions was taken out, mixed and stirred to prepare Solution 1. Next, 500 mL of 1.0 mol sodium borohydride aqueous solution was prepared and used as Solution 2. Solution 1 and solution 2 were each dropped into a reactor containing 100 mL of ethanol as a solvent at 1 mL / sec. The solution in the reactor was continuously passed through a filter by an air pump to collect a black precipitate.
回収された黒色沈殿物は、限外濾過装置を用いてエタノールで繰り返し洗浄してドデカンチオールで保護した平均粒径約４ｎｍの金ナノ粒子集合体を得た。 The recovered black precipitate was repeatedly washed with ethanol using an ultrafiltration device to obtain an aggregate of gold nanoparticles having an average particle size of about 4 nm protected with dodecanethiol.
５０ｇのドデカンチオールで保護した金ナノ粒子集合体を５０ｍＬのトルエンに溶解させることで４５ｗｔ％の金ナノ粒子分散液を得ることができた。上記金ナノ粒子分散液を室温、大気雰囲気下で６ヶ月保管した結果、沈殿物の生成が認められず、良好な分散状態を保つことが確認された。 The gold nanoparticle aggregate protected with 50 g of dodecanethiol was dissolved in 50 mL of toluene to obtain a 45 wt% gold nanoparticle dispersion. As a result of storing the gold nanoparticle dispersion for 6 months at room temperature in an air atmosphere, it was confirmed that no precipitate was formed, and a good dispersion state was maintained.
実施例２
硝酸銀をイソプロパノールに溶解することで２．０モルの硝酸銀溶液を調製して溶液１とした。メルカプトウンデカン酸をメタノールに溶解することで１．０モルのメルカプトウンデカン酸溶液を調製して溶液２とした。エタノールを用いて１．０モルの水素化ホウ素ナトリウム溶液を５００ｍＬ調製し溶液３とした。溶液１、溶液２、そして溶液３をそれぞれ２．５ｍＬ／ｓｅｃで溶媒として１００ｍＬのブタノールを含む反応器中に滴下した。反応器中の溶液は、エアポンプにより連続してフィルターを通過させ、黒色沈殿物を回収した。
Example 2
A 2.0 molar silver nitrate solution was prepared by dissolving silver nitrate in isopropanol to obtain Solution 1. Mercaptoundecanoic acid was dissolved in methanol to prepare a 1.0 mol mercaptoundecanoic acid solution, which was designated Solution 2. 500 mL of a 1.0 molar sodium borohydride solution was prepared using ethanol to obtain Solution 3. Solution 1, Solution 2, and Solution 3 were each added dropwise at 2.5 mL / sec into a reactor containing 100 mL of butanol as a solvent. The solution in the reactor was continuously passed through a filter by an air pump to collect a black precipitate.
回収された黒色沈殿物は、限外濾過装置を用いてブタノールで繰り返し洗浄してメルカプトウンデカン酸で保護した平均粒径約７ｎｍの銀ナノ粒子集合体を得た。 The collected black precipitate was repeatedly washed with butanol using an ultrafiltration device to obtain a silver nanoparticle aggregate having an average particle diameter of about 7 nm and protected with mercaptoundecanoic acid.
１００ｇのメルカプトウンデカン酸で保護した銀ナノ粒子集合体を２００ｍＬの蒸留水に溶解することで３０ｗｔ％の銀ナノ粒子分散液を得ることができた。上記銀ナノ粒子分散液中に０．０１モルの塩酸水溶液を３０ｍＬ添加することで黒色沈殿物を得た。これは、溶液が酸性になることで、カルボン酸塩中に配位していたナトリウムが水素と置換することで、水への溶解性が失われたことによる。 The silver nanoparticle aggregate protected with 100 g of mercaptoundecanoic acid was dissolved in 200 mL of distilled water to obtain a 30 wt% silver nanoparticle dispersion. A black precipitate was obtained by adding 30 mL of 0.01 mol hydrochloric acid aqueous solution to the silver nanoparticle dispersion. This is because the solubility in water was lost by replacing the sodium coordinated in the carboxylate with hydrogen as the solution became acidic.
上記黒色沈殿物を０．０１モルの塩酸水溶液で洗浄し、その後蒸留水で繰り返し洗浄することで、不純物の除去を行った。 The black precipitate was washed with 0.01 molar aqueous hydrochloric acid and then repeatedly washed with distilled water to remove impurities.
次に、１００ｇの黒色沈殿物を５０ｍＬのエタノールに溶解させることで６０ｗｔ％の銀ナノ粒子分散液を得ることができた。上記銀ナノ粒子分散液を室温、大気雰囲気下で６ヶ月保管した結果、沈殿物の生成が認められず、良好な分散状態を保つことが確認された。 Next, 100 g of the black precipitate was dissolved in 50 mL of ethanol, whereby a 60 wt% silver nanoparticle dispersion liquid could be obtained. As a result of storing the above silver nanoparticle dispersion for 6 months at room temperature in an air atmosphere, it was confirmed that no precipitate was formed, and a good dispersion state was maintained.
実施例３
酢酸銀１．６２×１０−２モルおよび酢酸銅１．８０×１０−５モルにｎ−オクチルアミン９．００×１０−２モル、ナフテン酸１．８０×１０−１モルを添加し、メタノール１．４Ｌ中に溶解させた。金属イオン溶液を攪拌しながら０．１モル／Ｌの水素化ホウ素ナトリウムのイソプロパノール溶液２００ｍＬを１０分間で滴下し、金属イオンを還元した。
Example 3
N-octylamine 9.00 × 10 −2 mol and naphthenic acid 1.80 × 10 −1 mol were added to 1.62 × 10 −2 mol of silver acetate and 1.80 × 10 −5 mol of copper acetate, and methanol was added. Dissolved in 1.4 L. While stirring the metal ion solution, 200 mL of a 0.1 mol / L sodium borohydride isopropanol solution was added dropwise over 10 minutes to reduce the metal ions.
１時間攪拌した後、吸引濾過して沈殿物を回収し、回収した沈殿物にイソオクタンを添加した後、吸引濾過して濃い黄色透明の濾液を得た。その濾液を濃縮、乾燥し黒色の固形物にし、この固形物をイソオクタンに再分散し、透過型電子顕微鏡を用いてナノ粒子生成を確認した。卓上型蛍光Ｘ線装置にて黒色固形物から銀と銅が確認でき、銅の割合は１．５ａｔｏｍ％であった。 After stirring for 1 hour, the precipitate was collected by suction filtration, and isooctane was added to the collected precipitate, followed by suction filtration to obtain a dark yellow transparent filtrate. The filtrate was concentrated and dried to a black solid, which was redispersed in isooctane, and nanoparticle formation was confirmed using a transmission electron microscope. Silver and copper were confirmed from the black solid with a tabletop fluorescent X-ray apparatus, and the ratio of copper was 1.5 atom%.
実施例４
溶媒としてメタノールの代わりに２−プロパノールを用いて実施例３と同様に吸引濾過し沈殿物を回収した。回収した沈殿物にイソオクタンを添加した後、吸引濾過して濃い黄色透明の濾液にし、その濾液を濃縮、乾燥し黒色の固形物にし、この固形物をイソオクタンに再分散し、透過型電子顕微鏡を用いてナノ粒子生成を確認した。卓上型蛍光Ｘ線装置にて黒色固形物から銀と銅が確認でき、銅の割合は５．６ａｔｏｍ％であった。
Example 4
Using 2-propanol instead of methanol as a solvent, suction filtration was performed in the same manner as in Example 3 to collect a precipitate. After isooctane is added to the collected precipitate, suction filtration is performed to obtain a dark yellow transparent filtrate. The filtrate is concentrated and dried to a black solid, and the solid is redispersed in isooctane. Used to confirm nanoparticle formation. Silver and copper were confirmed from the black solid with a desktop fluorescent X-ray apparatus, and the copper ratio was 5.6 atom%.
比較例１
実施例３，４の条件で、溶媒にイソオクタンを使用した場合、生成したナノ粒子は溶媒に分散し、ナノ粒子のみを回収するために洗浄工程を必要とした。
Comparative Example 1
When isooctane was used as the solvent under the conditions of Examples 3 and 4, the produced nanoparticles were dispersed in the solvent, and a washing step was required to recover only the nanoparticles.
比較例２
実施例３，４の条件で保護剤であるｎ−オクチルアミン、ナフテン酸を添加しない場合、還元剤添加後に沈殿物が生成するが、沈殿物を回収して有機溶媒を添加しても沈殿物は有機溶媒に分散しなかった。
Comparative Example 2
When n-octylamine and naphthenic acid, which are protective agents, are not added under the conditions of Examples 3 and 4, a precipitate is formed after addition of the reducing agent. However, even if the precipitate is recovered and an organic solvent is added, the precipitate is generated. Was not dispersed in an organic solvent.
実施例５
酢酸銀１．６２×１０−２モルおよび酢酸銅１．８０×１０−５モルにｎ−オクチルアミン９．００×１０−２モル、ナフテン酸１．８０×１０−１モルを添加し、メタノール７０ｍＬ中に溶解させた。その後、実施例３と同様にして溶媒としてメタノールを用いて吸引濾過し沈殿物を回収した。
Example 5
N-octylamine 9.00 × 10 −2 mol and naphthenic acid 1.80 × 10 −1 mol were added to 1.62 × 10 −2 mol of silver acetate and 1.80 × 10 −5 mol of copper acetate, and methanol was added. Dissolved in 70 mL. Thereafter, in the same manner as in Example 3, suction filtration was performed using methanol as a solvent to collect a precipitate.
回収した沈殿物にイソオクタンを添加した後、吸引濾過して濃い黄色透明の濾液にし、その濾液を濃縮、乾燥し黒色の固形物を得た。得られた黒色の固形物をイソオクタンに再分散し、透過型電子顕微鏡を用いてナノ粒子生成を確認した。卓上型蛍光Ｘ線装置にて黒色固形物から銀と銅が確認でき、銅の割合は１．８ａｔｏｍ％であった。 Isooctane was added to the collected precipitate, followed by suction filtration to obtain a dark yellow transparent filtrate, and the filtrate was concentrated and dried to obtain a black solid. The resulting black solid was redispersed in isooctane, and nanoparticle formation was confirmed using a transmission electron microscope. Silver and copper were confirmed from the black solid with a desktop fluorescent X-ray apparatus, and the ratio of copper was 1.8 atom%.
実施例６
酢酸銀２．４３ｇ（グラム）および酢酸インジウム０．１３ｇにｎ−オクチルアミン２０．３ｇ、ナフテン酸２０．６ｇを添加し、メタノール１２０ｍＬに溶解させた。金属イオン溶液を攪拌しながら０．１モル／Ｌの水素化ホウ素ナトリウムのイソプロパノール溶液３２０ｍＬを１０分間で滴下し、金属イオンを還元した。１時間攪拌させた後、吸引濾過し沈殿物を回収した。
Example 6
20.3 g of n-octylamine and 20.6 g of naphthenic acid were added to 2.43 g (gram) of silver acetate and 0.13 g of indium acetate, and dissolved in 120 mL of methanol. While stirring the metal ion solution, 320 mL of a 0.1 mol / L sodium borohydride isopropanol solution was added dropwise over 10 minutes to reduce the metal ions. After stirring for 1 hour, suction filtration was performed to collect a precipitate.
回収した沈殿物にイソオクタンを添加した後、吸引濾過して濃い黄色透明の濾液にし、その濾液を濃縮、乾燥し黒色の固形物を得た。得られた黒色の固形物をイソオクタンに再分散し、透過型電子顕微鏡を用いナノ粒子生成を確認した。蛍光Ｘ線装置にて黒色固形物から銀とインジウムが確認でき、インジウムの割合は２．１ａｔｏｍ％であった。 Isooctane was added to the collected precipitate, followed by suction filtration to obtain a dark yellow transparent filtrate, and the filtrate was concentrated and dried to obtain a black solid. The resulting black solid was redispersed in isooctane, and nanoparticle formation was confirmed using a transmission electron microscope. Silver and indium were confirmed from the black solid with a fluorescent X-ray apparatus, and the ratio of indium was 2.1 atom%.
実施例７
酢酸銀２．４３ｇおよび酢酸インジウム０．１３ｇに、ｎ−オクチルアミン２０．３ｇとナフテン酸２０．６ｇを添加し、２−エトキシエタノール１２０ｍＬに溶解させた。金属イオン溶液を攪拌しながら０．１モル／Ｌの水素化ホウ素ナトリウムのイソプロパノール溶液３２０ｍＬを１０分間で滴下して金属イオンを還元した。１時間攪拌させた後、吸引濾過し沈殿物を回収した。
Example 7
20.3 g of n-octylamine and 20.6 g of naphthenic acid were added to 2.43 g of silver acetate and 0.13 g of indium acetate, and dissolved in 120 mL of 2-ethoxyethanol. While stirring the metal ion solution, 320 mL of a 0.1 mol / L sodium borohydride isopropanol solution was added dropwise over 10 minutes to reduce the metal ions. After stirring for 1 hour, suction filtration was performed to collect a precipitate.
回収した沈殿物にイソオクタンを添加した後、吸引濾過して濃い黄色透明の濾液にし、その濾液を濃縮、乾燥し黒色の固形物にした。この黒色の固形物をイソオクタンに再分散し、透過型電子顕微鏡を用いてナノ粒子生成を確認した。蛍光Ｘ線装置にて黒色固形物から銀とインジウムが確認でき、インジウムの割合は１．５ａｔｏｍ％であった。 After adding isooctane to the collected precipitate, suction filtration was performed to obtain a dark yellow transparent filtrate, and the filtrate was concentrated and dried to a black solid. This black solid was redispersed in isooctane, and nanoparticle formation was confirmed using a transmission electron microscope. Silver and indium were confirmed from the black solid with a fluorescent X-ray apparatus, and the proportion of indium was 1.5 atom%.
実施例８
酢酸銀１８．３ｇおよび酢酸銅２．２ｇにn−オクチルアミン１５５ｇ、ナフテン酸１６２ｇを添加し、メタノール１．２４Ｌ中に溶解させて金属イオン溶液を得た。この金属イオン溶液１Ｌと０．１モル／Ｌの水素化ホウ素ナトリウムのイソプロパノール溶液０．２５Ｌを容量３００ｍＬの連続槽型攪拌反応器中へそれぞれ同時に流入して金属イオンを還元し、沈殿物を含む溶液を連続的に得た。
Example 8
To 18.3 g of silver acetate and 2.2 g of copper acetate, 155 g of n-octylamine and 162 g of naphthenic acid were added and dissolved in 1.24 L of methanol to obtain a metal ion solution. 1 L of this metal ion solution and 0.25 L of 0.1 mol / L sodium borohydride isopropanol solution are simultaneously introduced into a 300 mL continuous tank stirred reactor to reduce metal ions and contain precipitates. A solution was obtained continuously.
反応器への流入は、金属イオン溶液が０．０５Ｌ／ｍｉｎ、水素化法素ナトリウムＩＰＡ溶液が０．０１３Ｌ／ｍｉｎで行ない、流出口から出てきた沈殿物を含む流出液を限外濾過し沈殿物を回収した。回収した沈殿物にイソオクタンを添加した後、限外濾過して濃い黄色透明の濾液を得た。その濾液を濃縮、乾燥し黒色の固形物を得た。得られた黒色の固形物はイソオクタンに再分散した。透過型電子顕微鏡を用いナノ粒子生成を確認した。蛍光Ｘ線装置にて黒色固形物から銀と銅が確認でき、銅の割合は３．８ａｔｏｍ％であった。 The inflow to the reactor was carried out at 0.05 L / min for the metal ion solution and 0.013 L / min for the sodium hydride IPA solution, and the effluent containing the precipitate coming out from the outlet was ultrafiltered. The precipitate was collected. Isooctane was added to the collected precipitate, and ultrafiltration was performed to obtain a dark yellow transparent filtrate. The filtrate was concentrated and dried to obtain a black solid. The resulting black solid was redispersed in isooctane. Nanoparticle formation was confirmed using a transmission electron microscope. Silver and copper were confirmed from the black solid with a fluorescent X-ray apparatus, and the ratio of copper was 3.8 atom%.
実施例９
酢酸銀１８．３ｇおよび酢酸銅２．２ｇにn−オクチルアミン１５５ｇ、ナフテン酸１６２ｇを添加し、メタノール１．２４Ｌ中に溶解させて金属イオン溶液を得た。この金属イオン溶液１Ｌと０．１モル／Ｌの水素化ホウ素ナトリウムＩＰＡ溶液０．２５Ｌを滞留時間が１分の管型反応器中へそれぞれ同時に流入して金属イオンを還元し、ナノ粒子凝集物を含む溶液を連続的に得た。
Example 9
To 18.3 g of silver acetate and 2.2 g of copper acetate, 155 g of n-octylamine and 162 g of naphthenic acid were added and dissolved in 1.24 L of methanol to obtain a metal ion solution. 1 L of this metal ion solution and 0.25 L of a 0.1 mol / L sodium borohydride IPA solution are simultaneously introduced into a tubular reactor having a residence time of 1 minute to reduce metal ions, and agglomerates of nanoparticles A solution containing was continuously obtained.
反応器への流入は、金属イオン溶液が０．０５Ｌ／ｍｉｎ、水素化ホウ素ナトリウムＩＰＡ溶液が０．０１３Ｌ／ｍｉｎで行ない、連続して流出口から出てきた流出液を限外濾過し沈殿物を回収した。回収した沈殿物にイソオクタンを添加した後、限外濾過して濃い黄色透明の濾液を得た。その濾液を濃縮、乾燥し黒色の固形物を得た。得られた黒色の固形物はイソオクタンに再分散した。透過型電子顕微鏡を用いナノ粒子生成を確認した。蛍光Ｘ線装置にて黒色固形物から銀と銅が確認でき、銅の割合は２．６ａｔｏｍ％であった。 The inflow to the reactor was carried out at 0.05 L / min for the metal ion solution and 0.013 L / min for the sodium borohydride IPA solution, and the effluent from the outlet was continuously ultrafiltered to obtain a precipitate. Was recovered. Isooctane was added to the collected precipitate, and ultrafiltration was performed to obtain a dark yellow transparent filtrate. The filtrate was concentrated and dried to obtain a black solid. The resulting black solid was redispersed in isooctane. Nanoparticle formation was confirmed using a transmission electron microscope. Silver and copper were confirmed from the black solid with a fluorescent X-ray apparatus, and the ratio of copper was 2.6 atom%.
実施例１０
酢酸銀１０．８ｇおよび酢酸銅０．５８ｇにn−オクチルアミン９０ｇ、ナフテン酸９２ｇを添加し、２−エトキシエタノール０．２８Ｌ中に溶解させて金属イオン溶液を得た。この金属イオン溶液０．５Ｌと０．１モル／Ｌの水素化ホウ素ナトリウムのイソプロパノール溶液０．７Ｌを容量３００ｍＬの連続槽型攪拌反応器中へそれぞれ同時に流入して金属イオンを還元し、沈殿物を含む溶液を連続的に得た。
Example 10
To 10.8 g of silver acetate and 0.58 g of copper acetate, 90 g of n-octylamine and 92 g of naphthenic acid were added and dissolved in 0.28 L of 2-ethoxyethanol to obtain a metal ion solution. This metal ion solution 0.5 L and 0.1 mol / L sodium borohydride isopropanol solution 0.7 L were simultaneously introduced into a 300 mL continuous tank type stirred reactor to reduce metal ions and precipitate. A solution containing was continuously obtained.
反応器への流入は金属イオン溶液が０．０２５Ｌ／ｍｉｎ、水素化ホウ素ナトリウムＩＰＡ溶液が０．０３５Ｌ／ｍｉｎで行った。流出口から出てきた沈殿物を含む流出液を限外濾過し沈殿物を回収した。回収した沈殿物にイソオクタンを添加した後、限外濾過して濃い黄色透明の濾液を得た。その濾液を濃縮、乾燥し黒色の固形物を得た。得られた黒色の固形物はイソオクタンに再分散した。透過型電子顕微鏡を用いナノ粒子生成を確認した。蛍光Ｘ線装置にて黒色固形物から銀とインジウムが確認でき、インジウムの割合は１．３ａｔｏｍ％であった。 The flow into the reactor was 0.025 L / min for the metal ion solution and 0.035 L / min for the sodium borohydride IPA solution. The effluent containing the precipitate coming out from the outlet was ultrafiltered to collect the precipitate. Isooctane was added to the collected precipitate, and ultrafiltration was performed to obtain a dark yellow transparent filtrate. The filtrate was concentrated and dried to obtain a black solid. The resulting black solid was redispersed in isooctane. Nanoparticle formation was confirmed using a transmission electron microscope. Silver and indium were confirmed from the black solid with a fluorescent X-ray apparatus, and the ratio of indium was 1.3 atom%.
実施例１１
末端ジアミンポリエチレンオキシド（数平均分子量４，９００）を５．０ｇと、２．５４×１０−２モル／Ｌの塩化金酸のエトキシエタノール溶液５０ｍＬとをエタノール５００ｍＬに溶解させた。この溶液を攪拌しながら、０．１モル／Ｌの水素化ホウ素ナトリウムのイソプロパノール溶液５０ｍＬを２０分間で滴下し、金属イオンを還元した。１時間攪拌させた後に吸引ろ過し、紫色の沈殿物を回収した。
Example 11
5.0 g of terminal diamine polyethylene oxide (number average molecular weight 4,900) and 50 mL of an ethoxyethanol solution of 2.54 × 10 −2 mol / L chloroauric acid were dissolved in 500 mL of ethanol. While stirring this solution, 50 mL of a 0.1 mol / L sodium borohydride isopropanol solution was added dropwise over 20 minutes to reduce metal ions. After stirring for 1 hour, suction filtration was performed to collect a purple precipitate.
回収した沈殿物をテトラヒドロフランによって過剰な有機分を取り除き、金属濃度が５７重量％の沈殿物を得た。沈殿物を１−メチル−２−ピロリドンに分散した。金属濃度は２０重量％であった。この分散物を透過型電子顕微鏡によって観察し、ナノ粒子生成を確認した。また、卓上型蛍光Ｘ線装置にて沈殿物から金と塩素が定性でき、金の割合は９９．７ａｔｏｍ％であった。 Excess organic components were removed from the collected precipitate with tetrahydrofuran to obtain a precipitate having a metal concentration of 57% by weight. The precipitate was dispersed in 1-methyl-2-pyrrolidone. The metal concentration was 20% by weight. This dispersion was observed with a transmission electron microscope, and nanoparticle formation was confirmed. Further, gold and chlorine could be qualitatively determined from the precipitate using a desktop fluorescent X-ray apparatus, and the gold ratio was 99.7 atom%.
実施例１２
末端ジアミンポリエチレンオキシド（数平均分子量２，０００）２０．０ｇと、５．６×１０−２モル／Ｌの塩化金酸をエトキシエタノールに分散した溶液４５ｍＬとを、８６％のエタノール１Ｌに溶解させた。この溶液を攪拌しながら、０．０３モル／Ｌの水素化ホウ素ナトリウムのイソプロパノール溶液２００ｍｌを５０分間で滴下し、金イオンを還元した。１時間攪拌させた後、加圧ろ過して金色の沈殿物を回収した。
Example 12
20.0 g of terminal diamine polyethylene oxide (number average molecular weight: 2,000) and 45 mL of a solution of 5.6 × 10 −2 mol / L chloroauric acid dispersed in ethoxyethanol were dissolved in 1 L of 86% ethanol. It was. While stirring this solution, 200 ml of 0.03 mol / L sodium borohydride isopropanol solution was added dropwise over 50 minutes to reduce gold ions. After stirring for 1 hour, pressure filtration was performed to collect a golden precipitate.
回収した沈殿物を水に分散させ、７５℃のオーブンで乾燥し、０．９ｇの固形物を得た。 収率は６６％であった。得られた固形物は１−メチル−２−ピロリドンに分散した。金属濃度は３２重量％であった。この分散物を透過型電子顕微鏡によって観察し、ナノ粒子生成を確認した。また、卓上型蛍光Ｘ線装置にて沈殿物から金と塩素が定性でき、金の割合は９５．２ａｔｏｍ％であった。 The collected precipitate was dispersed in water and dried in an oven at 75 ° C. to obtain 0.9 g of a solid. The yield was 66%. The obtained solid was dispersed in 1-methyl-2-pyrrolidone. The metal concentration was 32% by weight. This dispersion was observed with a transmission electron microscope, and nanoparticle formation was confirmed. Further, gold and chlorine could be qualitatively determined from the precipitate using a desktop fluorescent X-ray apparatus, and the gold ratio was 95.2 atom%.
実施例１３
末端ジアミンポリエチレンオキシド （数平均分子量２，０００）１２．５ｇと、酢酸銀 ０．３８７ｇとをプロパノール５００ｍＬに溶解させた。この溶液を攪拌しながら、０．０３モル／Ｌの水素化ホウ素ナトリウムのイソプロパノール溶液３５ｍＬを２０分間で滴下し、銀イオンを還元した。２時間攪拌させた後に吸引ろ過し、沈殿物を回収し、０．３ｇの固形物を得た。収率は７３％であった。
Example 13
12.5 g of terminal diamine polyethylene oxide (number average molecular weight 2,000) and 0.387 g of silver acetate were dissolved in 500 mL of propanol. While stirring this solution, 35 mL of 0.03 mol / L sodium borohydride isopropanol solution was added dropwise over 20 minutes to reduce silver ions. After stirring for 2 hours, suction filtration was performed, and the precipitate was collected to obtain 0.3 g of a solid. The yield was 73%.
得られた固形物は１−メチル−２−ピロリドンに分散した。金属濃度は２０重量％であった。この分散物を電子顕微鏡によってナノ粒子生成を確認した。また、卓上型蛍光Ｘ線装置にて沈殿物から銀とナトリウムが定性でき、銀の割合は９７．９ａｔｏｍ％であった。 The obtained solid was dispersed in 1-methyl-2-pyrrolidone. The metal concentration was 20% by weight. The dispersion was confirmed to produce nanoparticles by an electron microscope. Moreover, silver and sodium could be qualitatively determined from the precipitate with a desktop fluorescent X-ray apparatus, and the ratio of silver was 97.9 atom%.
実施例１４
末端ジチオールポリエチレンオキシド（数平均分子量３，４００）０．２５ｇと、塩化金酸 ０．０２６ｇとをプロパノール溶液２５ｍＬに溶解させた。この溶液を攪拌しながら、０．０３モル／Ｌの水素化ホウ素ナトリウムのイソプロパノール溶液５ｍＬを２０分間で滴下し、金イオンを還元した。１時間攪拌させた後に吸引ろ過し、沈殿物を回収し、０．３ｇの赤紫色の固形物を得た。
Example 14
0.25 g of terminal dithiol polyethylene oxide (number average molecular weight 3,400) and 0.026 g of chloroauric acid were dissolved in 25 mL of a propanol solution. While stirring this solution, 5 mL of 0.03 mol / L sodium borohydride in isopropanol was added dropwise over 20 minutes to reduce gold ions. After stirring for 1 hour, suction filtration was performed, and the precipitate was collected to obtain 0.3 g of a reddish purple solid.
得られた固形物を水に分散した。金属濃度は２０重量％であった。この分散物を電子顕微鏡によってナノ粒子生成を確認した。また、卓上型蛍光Ｘ線装置にて沈殿物から金、硫黄が定性でき、金の割合は３８．８ａｔｏｍ％であった。 The obtained solid was dispersed in water. The metal concentration was 20% by weight. The dispersion was confirmed to produce nanoparticles by an electron microscope. Moreover, gold | metal | money and sulfur were qualitative from a deposit with the desktop fluorescent X-ray apparatus, and the ratio of gold | metal | money was 38.8 atom%.
比較例３
実施例１３の条件で保護剤にジアミノトリオキサトリデカンを用いた場合，得られた固形物は水に再分散しなかった。
Comparative Example 3
When diaminotrioxatridecane was used as the protective agent under the conditions of Example 13, the obtained solid was not redispersed in water.
本発明に係る金属ナノ粒子及び金属ナノ粒子分散液の製造方法によれば、高濃度の金属ナノ粒子分散液を高価な設備を必要とせず簡便且つ安価に連続して得ることができ、金属ナノ粒子のペーストを用いて電気抵抗値の低い基板を製造することができる。
According to the metal nanoparticles and the method for producing a metal nanoparticle dispersion according to the present invention, a metal nanoparticle dispersion with a high concentration can be continuously obtained simply and inexpensively without requiring expensive equipment. A substrate having a low electrical resistance value can be manufactured using a paste of particles.
Claims (22)
第１の溶媒と第２の溶媒とともに極性溶媒を使用する請求項１４記載の金属ナノ粒子分散液の製造方法。 When using a protective agent composed of a main chain having at least two or more functional groups having affinity for metal nanoparticles in the main chain and / or side chain and having a high affinity for the solvent ,
The method for producing a metal nanoparticle dispersion according to claim 14, wherein a polar solvent is used together with the first solvent and the second solvent.
The polar solvent is at least selected from methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, α-terpineol, water, dimethylformamide, ethyl acetate, 1-methyl-2-pyrrolidone and butyl acetate The method for producing a metal nanoparticle dispersion according to claim 15, 16 or 18, which is one type.
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