JP2008121043A - Fine particle, fine particle dispersion, method for producing fine particle and method for producing fine particle dispersion - Google Patents
Fine particle, fine particle dispersion, method for producing fine particle and method for producing fine particle dispersion Download PDFInfo
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本発明は、微粒子、微粒子分散溶液、微粒子の製造方法、及び微粒子分散溶液の製造方法に関する。 The present invention relates to fine particles, a fine particle dispersion solution, a fine particle production method, and a fine particle dispersion solution production method.
ナノサイズ（粒径が１μｍ以下）の金属微粒子は、バルク材料にはない様々な特異な特性を持つことが知られている。そしてこの特性を生かした様々な工学的応用が、現在、エレクトロニクス、バイオ、エネルギー等の各分野で、大いに期待されている。 It is known that nano-sized metal particles (particle size of 1 μm or less) have various unique characteristics not found in bulk materials. Various engineering applications that take advantage of this property are now highly expected in fields such as electronics, biotechnology, and energy.
中でも、銅、ニッケル、コバルト、鉄、亜鉛、スズ、銀等の工業的な汎用金属及びそれらの合金からなるナノサイズの金属微粒子は、導電回路、バンプ、ビア、パッド等の実装部品の形成材料、高密度磁気記憶媒体やアンテナ用の磁性素子、ガス改質フィルタや燃料電池電極用の触媒材料として、大いに期待されている。 Among them, nano-sized metal fine particles made of industrial general-purpose metals such as copper, nickel, cobalt, iron, zinc, tin, silver, and their alloys are used to form mounting parts such as conductive circuits, bumps, vias, and pads. It is highly expected as a catalyst material for high-density magnetic storage media, magnetic elements for antennas, gas reforming filters and fuel cell electrodes.
また、最近では、金属微粒子を含有するインクを使用して、配線パターンをインクジェットプリンタにより印刷し、焼成して配線を形成する技術（インクジェット回路形成技術）が注目されている。しかし、インクジェットプリンタのインクとして、金属微粒子を含有するインクを使用する場合、インク中において分散性を長期間保つことが重要である。そのため、インク中において粒子分散性を向上させる効果を持つ保護被膜を有する金属微粒子の製造方法及びその金属微粒子分散溶液が提案されている。 Recently, a technique (inkjet circuit forming technique) in which a wiring pattern is printed by an ink jet printer using ink containing metal fine particles and baked to form a wiring (ink jet circuit forming technique) has attracted attention. However, when ink containing metal fine particles is used as ink for an ink jet printer, it is important to maintain dispersibility in the ink for a long period of time. Therefore, a method for producing metal fine particles having a protective film having an effect of improving particle dispersibility in ink and a metal fine particle dispersion solution have been proposed.
特許文献１では、銅の酸化物、水酸化物または塩をポリエチレングリコールまたはエチレングリコール（１，２−エタンジオール）溶液中で、核生成のためのパラジウムイオンと、分散性を向上させる保護被膜剤としてのポリエチレンイミンを添加して、加熱還元することにより、ポリエチレンイミンで被覆された銅微粒子を合成する方法、及びその銅微粒子分散溶液が提案されている。
In
また、特許文献２では、アルキルアミンを分散剤に使用して、アミン化合物で被覆された金属微粒子を製造する方法及びその金属微粒子分散溶液が提案されている。また、特許文献３には、セルロース誘導体を含む水溶液中で金属イオンを還元することにより、セルロース誘導体で被覆された金属微粒子を製造する方法及びその微粒子分散溶液が提案されている。
一方で、上述のインクジェット回路形成技術のように金属微粒子の焼成により導電性の金属部材を形成する場合や、微粒子焼成体をガス改質フィルタに使用する場合などには、焼成後の粒子焼成体において、微粒子自体が表面に露出して粒子同士が直接接合している必要がある。そのため、これらの技術に使用される微粒子については、その表面に被覆させた保護被膜が、熱処理時に容易に分解除去される必要があった。
上述のように、微粒子分散インクのパターニングと焼成とにより、導電性配線パターンやフィルタを形成する場合、分散性向上のために使用した保護被膜が熱処理時に容易に分解除去する必要がある。しかしながら、上述の金属微粒子では、２５０℃以上の高温で熱処理をしなければ、その保護被膜を分解除去して導電性の金属を得ることができないという問題点があった。 As described above, when a conductive wiring pattern or a filter is formed by patterning and baking fine particle dispersed ink, the protective film used for improving dispersibility needs to be easily decomposed and removed during heat treatment. However, the above-mentioned metal fine particles have a problem that unless a heat treatment is performed at a high temperature of 250 ° C. or more, the protective coating cannot be decomposed and removed to obtain a conductive metal.
また、そのような高温での熱処理を行った場合、粒子をパターニングした基板（例えば、汎用樹脂基盤）に設置されている他の製品が壊れたり、更に基板自体が溶融もしくは変形したりしてしまうという問題点もあった。さらに、これらの微粒子を用いた場合、熱処理のときに、危険で取り扱いの困難な水素ガス等の還元剤を使用しなければならないという問題点もあった。 In addition, when heat treatment at such a high temperature is performed, other products installed on a substrate (for example, a general-purpose resin substrate) on which particles are patterned are broken, or the substrate itself is melted or deformed. There was also a problem. Further, when these fine particles are used, there is a problem that a reducing agent such as hydrogen gas, which is dangerous and difficult to handle, must be used during heat treatment.
一方で、これら保護被膜で被覆されていない、分散性の悪い微粒子の分散溶液を使用した場合、熱処理時に粒子同士が不均一に凝集して焼結性が不均一になるという問題があった。また、さらに分散溶液中で互いに凝集した微粒子がインクジェットプリンタのノズルに詰まるという問題もあった。 On the other hand, when a dispersion solution of fine particles with poor dispersibility that is not coated with these protective coatings is used, there is a problem that the particles are agglomerated non-uniformly during heat treatment and the sinterability becomes non-uniform. Further, there is a problem that fine particles aggregated with each other in the dispersion solution are clogged with the nozzles of the ink jet printer.
本発明は、以上のような問題点を解決するためになされたもので、分散液中での分散性が高く、さらに低温焼成することが可能な微粒子、その微粒子を分散した微粒子分散溶液、微粒子の製造方法、及び微粒子分散溶液の製造方法を提供することを目的とする。 The present invention has been made in order to solve the above-described problems, and has high dispersibility in a dispersion and can be fired at a low temperature, a fine particle dispersion in which the fine particles are dispersed, and fine particles It is an object of the present invention to provide a method for producing a fine particle dispersion solution.
発明者は上述した従来の問題点について鋭意研究を重ねた。その結果、低分子ビニルピロリドンに被覆された微粒子は、低温での焼結性を向上させることが判明した。 The inventor conducted extensive research on the above-described conventional problems. As a result, it was found that fine particles coated with low molecular weight vinyl pyrrolidone improve the sinterability at low temperature.
また、分子ビニルピロリドンに被覆された微粒子を、有機溶媒の中に分散させることにより、粒子分散性の高い微粒子分散溶液が得られることが判明した。この発明は、上述した研究成果によってなされたものである。 It was also found that a fine particle dispersion having high particle dispersibility can be obtained by dispersing fine particles coated with molecular vinylpyrrolidone in an organic solvent. The present invention has been made based on the research results described above.
本発明の第１の態様にかかる微粒子は、ナノサイズの微粒子であって、低分子量ビニルプロリドンに被覆されていることを特徴とする。 The fine particles according to the first aspect of the present invention are nano-sized fine particles, and are characterized by being coated with a low molecular weight vinylprolidone.
これにより、還元剤を用いることなく、不活性ガス雰囲気中１９０℃以上の温度で、熱処理することにより、微粒子自体が表面に露出して粒子同士が直接接合している焼成体を生成することができる。また、この微粒子を分散液中に分散することにより、粒子分散性の高い微粒子分散溶液を生成することができる。 Thereby, by using a heat treatment at a temperature of 190 ° C. or higher in an inert gas atmosphere without using a reducing agent, a fired body in which the fine particles themselves are exposed on the surface and the particles are directly bonded can be generated. it can. Further, by dispersing the fine particles in the dispersion, a fine particle dispersion having high particle dispersibility can be produced.
本発明の第２の態様にかかる微粒子は、本発明の第１の態様にかかる微粒子における前記低分子量ビニルプロリドンが、ポリビニルプロリドンにハロゲン化水素を反応させることによって得られたものであることを特徴とする。 The fine particles according to the second aspect of the present invention are obtained by reacting the hydrogen halide with polyvinyl prolidone in the low molecular weight vinylprolidone in the fine particles according to the first aspect of the present invention. It is characterized by.
これにより、還元剤を用いることなく、不活性ガス雰囲気中１９０℃以上の温度で、熱処理することにより、微粒子自体が表面に露出して粒子同士が直接接合している焼成体を生成することができる。また、この微粒子を分散液中に分散することにより、粒子分散性の高い微粒子分散溶液を生成することができる。 Thereby, by using a heat treatment at a temperature of 190 ° C. or higher in an inert gas atmosphere without using a reducing agent, a fired body in which the fine particles themselves are exposed on the surface and the particles are directly bonded can be generated. it can. Further, by dispersing the fine particles in the dispersion, a fine particle dispersion having high particle dispersibility can be produced.
本発明の第３の態様にかかる微粒子は、本発明の第１または２の態様にかかる微粒子における前記微粒子が、金属または前記金属の酸化物であることを特徴とする。 The fine particles according to the third aspect of the present invention are characterized in that the fine particles in the fine particles according to the first or second aspect of the present invention are a metal or an oxide of the metal.
これにより、還元剤を用いることなく、不活性ガス雰囲気中１９０℃以上の温度で、熱処理することにより、導電性の金属焼成体を生成することができる。ここで、更に、微粒子は、半導体等であっても良い。 Thereby, an electroconductive metal fired body can be produced | generated by heat-processing at the temperature of 190 degreeC or more in inert gas atmosphere, without using a reducing agent. Here, the fine particles may be a semiconductor or the like.
本発明の第４の態様にかかる微粒子は、本発明の第３の態様にかかる微粒子における前記金属が、銅、ニッケル、コバルト、鉄、亜鉛、スズ、及び銀の中から選択された１種類、または、２種類以上からなる合金であることを特徴とする。 The fine particles according to the fourth aspect of the present invention are one kind in which the metal in the fine particles according to the third aspect of the present invention is selected from copper, nickel, cobalt, iron, zinc, tin, and silver, Or it is an alloy which consists of two or more types, It is characterized by the above-mentioned.
本発明の第５の態様にかかる微粒子は、本発明の第１乃至４のいずれか１つの態様にかかる微粒子における前記微粒子が、粒径が１ｎｍ以上でかつ５００ｎｍ以下であることを特徴とする。 The fine particles according to the fifth aspect of the present invention are characterized in that the fine particles according to any one of the first to fourth aspects of the present invention have a particle size of 1 nm or more and 500 nm or less.
本発明の第１の態様にかかる微粒子分散溶液は、本発明の第１乃至５のいずれか１つの態様にかかる微粒子を、分子中に１つ以上のヒドロキシル基を有する有機化合物を含む有機溶媒に分散させることを特徴とする。 The fine particle dispersion solution according to the first aspect of the present invention is obtained by adding the fine particle according to any one of the first to fifth aspects of the present invention to an organic solvent containing an organic compound having one or more hydroxyl groups in the molecule. It is characterized by being dispersed.
これより、更に、粒子分散性を向上させることが可能となる。 As a result, the particle dispersibility can be further improved.
本発明の第１の態様にかかる微粒子の製造方法は、ナノサイズの微粒子の製造方法であって、ポリビニルプロリドンで被覆された微粒子を分散させた水溶液の中に、ハロゲン化水素を添加混合する工程を備えていることを特徴とする。 The method for producing fine particles according to the first aspect of the present invention is a method for producing nano-sized fine particles, in which hydrogen halide is added and mixed in an aqueous solution in which fine particles coated with polyvinylprolidone are dispersed. It has the process, It is characterized by the above-mentioned.
これにより、還元剤を用いることなく、不活性ガス雰囲気中１９０℃以上の温度で、熱処理することにより、微粒子自体が表面に露出して粒子同士が直接接合している焼成体を生成することができる。また、この微粒子を分散液中に分散することにより、粒子分散性の高い微粒子分散溶液を生成することができる。 Thereby, by using a heat treatment at a temperature of 190 ° C. or higher in an inert gas atmosphere without using a reducing agent, a fired body in which the fine particles themselves are exposed on the surface and the particles are directly bonded can be generated. it can. Further, by dispersing the fine particles in the dispersion, a fine particle dispersion having high particle dispersibility can be produced.
本発明の第１の態様にかかる微粒子分散溶液の製造方法は、本発明の第１乃至５のいずれか１つの態様にかかる微粒子を、水または有機溶媒の中に分散させる工程を備えていることを特徴とする微粒子分散溶液の製造方法。 The method for producing a fine particle dispersion according to the first aspect of the present invention includes a step of dispersing the fine particles according to any one of the first to fifth aspects of the present invention in water or an organic solvent. A method for producing a fine particle dispersion.
これにより、還元剤を用いることなく、不活性ガス雰囲気中１９０℃以上の温度で、熱処理することにより、微粒子自体が表面に露出して粒子同士が直接接合している焼成体を生成することができる。また、粒子分散性の高い微粒子分散溶液を生成することができる。ここで、有機溶媒は、極性を有することが好ましい。 Thereby, by using a heat treatment at a temperature of 190 ° C. or higher in an inert gas atmosphere without using a reducing agent, a fired body in which the fine particles themselves are exposed on the surface and the particles are directly bonded can be generated. it can. In addition, a fine particle dispersion solution with high particle dispersibility can be produced. Here, the organic solvent preferably has polarity.
本発明の第２の態様にかかる微粒子分散溶液の製造方法は、本発明の第１の態様にかかる微粒子分散溶液の製造方法における前記有機溶媒が、分子中に１つ以上のヒドロキシル基を有する有機化合物を含むことを特徴とする。
これにより、更に、粒子分散性の高い微粒子分散溶液を生成することができる。
In the method for producing a fine particle dispersion solution according to the second aspect of the present invention, the organic solvent in the method for producing the fine particle dispersion solution according to the first aspect of the present invention is an organic compound having one or more hydroxyl groups in the molecule. It is characterized by including a compound.
Thereby, a fine particle dispersion solution with high particle dispersibility can be generated.
本発明によれば、低分子ビニルピロリドンで被覆された微粒子を、還元剤を用いることなく、不活性ガス雰囲気中１９０℃以上の温度で、熱処理することにより、微粒子自体が表面に露出して粒子同士が直接接合している焼成体を生成することが出来る。またこのとき微粒子として金属微粒子を用いた場合、導電性の金属焼成体を生成することができる。 According to the present invention, fine particles coated with a low molecular weight vinyl pyrrolidone are heat-treated at a temperature of 190 ° C. or higher in an inert gas atmosphere without using a reducing agent, whereby the fine particles themselves are exposed on the surface. A fired body in which the members are directly joined can be produced. At this time, when metal fine particles are used as the fine particles, a conductive metal fired body can be produced.
また、特に、分子ビニルピロリドンに被覆された金属微粒子を、極性を有する有機溶媒の中に分散させることにより、分散性の優れた金属微粒子分散溶液を得ることができる。 In particular, a metal fine particle dispersion having excellent dispersibility can be obtained by dispersing metal fine particles coated with molecular vinyl pyrrolidone in a polar organic solvent.
この発明の一実施態様を、図面を参照しながら説明する。なお、以下に説明する実施態様は説明のためのものであり、本発明の範囲を制限するものではない。従って、当業者であればこれらの各要素もしくは全要素をこれと均等なもので置換した実施態様を採用することが可能であるが、これらの実施態様も本発明の範囲に含まれる。 An embodiment of the present invention will be described with reference to the drawings. In addition, the embodiment described below is for explanation, and does not limit the scope of the present invention. Accordingly, those skilled in the art can employ embodiments in which each or all of these elements are replaced by equivalents thereof, and these embodiments are also included in the scope of the present invention.
まず、本発明を適用可能な金属微粒子及び金属微粒子分散溶液の製造方法を説明する。図１は、本発明を適用可能な金属微粒子及び金属微粒子分散溶液の製造方法の概念図である。ここでは、有機物保護被膜に被膜された微粒子を生成し、生成した微粒子を有機溶媒に分散して微粒子分散溶液を生成する。 First, a method for producing metal fine particles and a metal fine particle dispersion solution to which the present invention can be applied will be described. FIG. 1 is a conceptual diagram of a method for producing metal fine particles and a metal fine particle dispersion solution to which the present invention can be applied. Here, fine particles coated with an organic protective film are generated, and the generated fine particles are dispersed in an organic solvent to generate a fine particle dispersion solution.
図１に示すように、まず、不活性ガス（窒素ガス等）の雰囲気で、金属微粒子の原料である金属イオン原料１０と、還元剤１１と、還元制御剤１２とを、溶媒である蒸留水１３に混合した水溶液の中で液相還元させて、ポリビニルプロリドン（ＰＶＰ：Ｋ１２、分子量約３５００）で被覆された金属微粒子が分散した金属微粒子分散溶液１４を生成する（図中（１）参照）。 As shown in FIG. 1, first, in an atmosphere of an inert gas (nitrogen gas or the like), a metal ion raw material 10, which is a raw material of metal fine particles, a reducing agent 11, and a reduction control agent 12, are distilled water as a solvent. 13 is subjected to liquid phase reduction in an aqueous solution mixed with 13 to produce a metal fine particle dispersion solution 14 in which metal fine particles coated with polyvinylprolidone (PVP: K12, molecular weight of about 3500) are dispersed (see (1) in the figure). ).
次に、金属微粒子分散溶液１４にハロゲン化水素１５を添加して、粒子成分１６を凝集沈殿した反応液１７を生成する（図中（２）参照）。次に、反応液１７を遠心分離器で、低分子ビニルプロリドンで被覆された金属微粒子１８を分離回収する（図中（３）参照）。ここで、分離回収した金属微粒子１８は、水洗浄とアルコール洗浄を行う。アルコール洗浄は、特に、より分子量の大きいアルコールを使用して洗浄する。 Next, hydrogen halide 15 is added to the metal fine particle dispersion solution 14 to produce a reaction liquid 17 in which the particle component 16 is agglomerated and precipitated (see (2) in the figure). Next, the reaction solution 17 is separated and recovered from the metal fine particles 18 coated with the low-molecular vinylprolidone using a centrifuge (see (3) in the figure). Here, the separated and recovered metal fine particles 18 are washed with water and alcohol. In the alcohol cleaning, particularly, alcohol having a higher molecular weight is used for cleaning.
得られた金属微粒子１８を水または有機溶媒に再分散させることで、分散性の優れた金属微粒子分散溶液２０（図中（４）参照）を得ることができる。ここで、再分散させる再分散溶媒１９として、極性を有する有機溶媒、特に、ヒドロキシル基を１つ以上有した有機化合物からなる有機溶媒が好ましい。 By redispersing the obtained metal fine particles 18 in water or an organic solvent, a metal fine particle dispersion solution 20 (see (4) in the figure) having excellent dispersibility can be obtained. Here, as the redispersion solvent 19 to be redispersed, an organic solvent having polarity, particularly an organic solvent composed of an organic compound having one or more hydroxyl groups is preferable.
次に、本発明の好適ないくつかの実施例を説明する。 Next, several preferred embodiments of the present invention will be described.
本発明の金属微粒子および金属微粒子分散溶液の作成方法として、１−ビニル−２−プロリドンに被覆された銅ナノ粒子およびその分散溶液の作成方法の一例を示す。なお本発明は必ずしもこの方法に限定されるものではない。 As a method for producing the metal fine particles and the metal fine particle dispersion of the present invention, an example of a method for producing copper nanoparticles coated with 1-vinyl-2-prolidone and a dispersion thereof will be shown. The present invention is not necessarily limited to this method.
まず、銅ナノ粒子の原料として酢酸銅０．２ｇを蒸留水１０ｍｌに溶解させた酢酸銅水溶液１０ｍｌと、金属イオン還元剤として５．０ｍｏｌ／ｌとなるように水素化ホウ素ナトリウムと蒸留水とを混合した水素化ホウ素ナトリウム水溶液１００ｍｌと、を作成した。その後、上記水素化ホウ素ナトリウム水溶液に、１−ビニル−２−プロリドン０．５ｇを添加して、攪拌溶解させた後、窒素ガス雰囲気中で、上記酢酸銅水溶液１０ｍｌを滴下した。この混合液を約６０分間よく攪拌しながら反応させた結果、１−ビニル−２−プロリドンで被覆された銅ナノ粒子分散水溶液が得られた。更に、得られた銅ナノ粒子分散水溶液を遠心分離器に入れ、粒子成分を沈殿回収した。 First, 10 ml of a copper acetate aqueous solution in which 0.2 g of copper acetate was dissolved in 10 ml of distilled water as a raw material for copper nanoparticles, and sodium borohydride and distilled water so as to be 5.0 mol / l as a metal ion reducing agent. 100 ml of a mixed aqueous sodium borohydride solution was prepared. Thereafter, 0.5 g of 1-vinyl-2-prolidone was added to the sodium borohydride aqueous solution and dissolved by stirring, and 10 ml of the copper acetate aqueous solution was added dropwise in a nitrogen gas atmosphere. As a result of reacting this mixed liquid with sufficient stirring for about 60 minutes, an aqueous copper nanoparticle dispersion solution coated with 1-vinyl-2-prolidone was obtained. Further, the obtained copper nanoparticle-dispersed aqueous solution was put into a centrifuge, and the particle components were collected by precipitation.
その後、試験管に得られた粒子と適量の蒸留水とを入れ、超音波ホモジナイザーを用いてよく攪拌した後、遠心分離器で粒子成分を回収する水洗浄を３回、続いて、同じく試験管中で、得られた粒子と適量のブタノールとを入れ、超音波ホモジナイザーを用いてよく攪拌した後、遠心分離器で粒子成分を回収するアルコール洗浄を３回行った。更に、得られた粒子成分を最終分散溶媒の一例として、１，２エタンジオール１０ｍｌに入れ、その後、超音波ホモジナイザーを用いてよく攪拌することで、本発明の１−ビニル−２−プロリドンに被覆された銅ナノ粒子分散溶液が得られた。 Then, after putting the obtained particles and an appropriate amount of distilled water into a test tube, stirring well with an ultrasonic homogenizer, washing with water to collect the particle components with a centrifuge three times, followed by the same test tube Inside, the obtained particles and an appropriate amount of butanol were added, and after thoroughly stirring using an ultrasonic homogenizer, alcohol washing for recovering the particle components with a centrifuge was performed three times. Furthermore, as an example of the final dispersion solvent, the obtained particle component is put in 10 ml of 1,2 ethanediol, and then thoroughly stirred using an ultrasonic homogenizer to coat the 1-vinyl-2-prolidone of the present invention. A copper nanoparticle dispersion solution was obtained.
得られた１−ビニル−２−プロリドンで被覆された銅ナノ粒子分散溶液をガラス基板上に塗布し、不活性（アルゴン）雰囲気中、１５０℃、１８０℃、１９０℃、２００℃、２５０℃、及び３００℃において、それぞれ１時間熱処理を行った。得られた焼成膜について、デジタルマルチメータを用いて、それぞれ直流４端子法にて、その電気抵抗値を測定した。図２は、１−ビニル−２−プロリドンで被覆された銅ナノ粒子分散溶液の熱処理後の電気抵抗値の測定結果を示した図である。この結果より、１−ビニル−２−プロリドンで被覆された銅ナノ粒子分散溶液は、不活性雰囲気中、１９０℃以上の熱処理で、良好な導電性を持つ金属膜となることが確認された。 The obtained 1-vinyl-2-prolidone-coated copper nanoparticle dispersion solution was applied onto a glass substrate, and was 150 ° C., 180 ° C., 190 ° C., 200 ° C., 250 ° C. in an inert (argon) atmosphere. And 300 ° C. for 1 hour, respectively. About the obtained fired film, the electric resistance value was measured by the direct current | flow 4-terminal method using the digital multimeter, respectively. FIG. 2 is a diagram showing the measurement results of the electrical resistance value after heat treatment of the copper nanoparticle dispersion solution coated with 1-vinyl-2-prolidone. From this result, it was confirmed that the copper nanoparticle dispersion solution coated with 1-vinyl-2-prolidone becomes a metal film having good conductivity by heat treatment at 190 ° C. or higher in an inert atmosphere.
本発明の金属微粒子および金属微粒子分散溶液の作成方法として、分子量が１０００以下のポリビニルプロリドンに被覆された銅ナノ粒子およびその分散溶液の作成方法の一例を示す。なお本発明は必ずしもこの方法に限定されるものではない。 As a method for producing the metal fine particles and metal fine particle dispersion solution of the present invention, an example of copper nanoparticles coated with polyvinylprolidone having a molecular weight of 1000 or less and a method for producing the dispersion solution will be shown. The present invention is not necessarily limited to this method.
まず、銅ナノ粒子の原料として酢酸銅０．２ｇを蒸留水１０ｍｌに溶解させた酢酸銅水溶液１０ｍｌと、金属イオン還元剤として５．０ｍｏｌ／ｌとなるように水素化ホウ素ナトリウムと蒸留水とを混合した水素化ホウ素ナトリウム水溶液１００ｍｌと、を作成した。その後、上記水素化ホウ素ナトリウム水溶液に、ポリビニルプロリドン（ＰＶＰ：Ｋ１２、分子量約３５００）０．５ｇを添加して、攪拌溶解させた後、窒素ガス雰囲気中で、上記酢酸銅水溶液１０ｍｌを滴下した。この混合液を約６０分間よく攪拌しながら反応させた結果、ポリビニルプロリドンで被覆された銅ナノ粒子分散水溶液が得られた。次に、上記方法で得られたポリビニルプロリドンで被覆された銅ナノ粒子分散水溶液１００ｍｌに、ポリビニルピロリドンの分解剤としてクロロホルムを５ｍｌ添加してよく攪拌した。数分間攪拌した後、反応液を遠心分離器に入れ、粒子成分を沈殿回収した。得られた粒子に被覆している低分子ビニルプロリドンの分子量を、サイズ排除クロマトグラフィーを用いて測定したところ、約８００であった。 First, 10 ml of a copper acetate aqueous solution in which 0.2 g of copper acetate was dissolved in 10 ml of distilled water as a raw material for copper nanoparticles, and sodium borohydride and distilled water so as to be 5.0 mol / l as a metal ion reducing agent. 100 ml of a mixed aqueous sodium borohydride solution was prepared. Thereafter, 0.5 g of polyvinylprolidone (PVP: K12, molecular weight of about 3500) was added to the sodium borohydride aqueous solution and dissolved by stirring, and then 10 ml of the copper acetate aqueous solution was added dropwise in a nitrogen gas atmosphere. . As a result of reacting this mixed solution with sufficient stirring for about 60 minutes, an aqueous copper nanoparticle dispersion solution coated with polyvinylprolidone was obtained. Next, 5 ml of chloroform as a polyvinylpyrrolidone decomposing agent was added to 100 ml of the copper nanoparticle-dispersed aqueous solution coated with polyvinylprolidone obtained by the above method and stirred well. After stirring for several minutes, the reaction solution was put into a centrifuge and the particulate component was collected by precipitation. When the molecular weight of the low molecular weight vinylprolidone coated on the obtained particles was measured using size exclusion chromatography, it was about 800.
その後、試験管に得られた粒子と適量の蒸留水とを入れ、超音波ホモジナイザーを用いてよく攪拌した後、遠心分離器で粒子成分を回収する水洗浄を３回、続いて、同じく試験管中で、得られた粒子と適量のブタノールとを入れ、超音波ホモジナイザーを用いてよく攪拌した後、遠心分離器で粒子成分を回収するアルコール洗浄を３回行った。更に、得られた粒子成分を最終分散溶媒の一例として、１，２エタンジオール１０ｍｌに入れ、その後、超音波ホモジナイザーを用いてよく攪拌することで、本発明の低分子ビニルプロリドンに被覆された銅ナノ粒子分散溶液が得られた。尚、得られた粒子に被覆している低分子ビニルプロリドンの分子量を、サイズ排除クロマトグラフィーを用いて測定したところ、約８００であった。 Then, after putting the obtained particles and an appropriate amount of distilled water into a test tube, stirring well with an ultrasonic homogenizer, washing with water to collect the particle components with a centrifuge three times, followed by the same test tube Inside, the obtained particles and an appropriate amount of butanol were added, and after thoroughly stirring using an ultrasonic homogenizer, alcohol washing for recovering the particle components with a centrifuge was performed three times. Furthermore, the obtained particle component was placed in 10 ml of 1,2 ethanediol as an example of a final dispersion solvent, and then thoroughly stirred using an ultrasonic homogenizer, so that the low molecular weight vinyl prolidone of the present invention was coated. A copper nanoparticle dispersion solution was obtained. The molecular weight of the low molecular weight vinylprolidone coated on the obtained particles was measured using size exclusion chromatography and found to be about 800.
得られた低分子ビニルプロリドンで被覆された銅ナノ粒子分散溶液をガラス基板上に塗布し、不活性（アルゴン）雰囲気中、１５０℃、１８０℃、１９０℃、２００℃、２５０℃、及び３００℃において、それぞれ１時間熱処理を行った。得られた焼成膜について、デジタルマルチメータを用いて、それぞれ直流４端子法にて、その電気抵抗値を測定した。図３は、分子量が約８００の低分子ビニルプロリドンで被覆された銅ナノ粒子分散溶液の熱処理後の電気抵抗値の測定結果を示した図である。この結果より、低分子ビニルプロリドンで被覆された銅ナノ粒子分散溶液は、不活性雰囲気中、１９０℃以上の熱処理で、良好な導電性を持つ金属膜となることが確認された。 The obtained copper nanoparticle dispersion solution coated with low molecular weight vinylprolidone was applied onto a glass substrate, and was 150 ° C, 180 ° C, 190 ° C, 200 ° C, 250 ° C, and 300 ° C in an inert (argon) atmosphere. Heat treatment was performed at 1 ° C. for 1 hour. About the obtained fired film, the electric resistance value was measured by the direct current | flow 4-terminal method using the digital multimeter, respectively. FIG. 3 is a diagram showing the measurement results of the electrical resistance value after heat treatment of a copper nanoparticle dispersion solution coated with a low molecular weight vinylprolidone having a molecular weight of about 800. From this result, it was confirmed that the copper nanoparticle dispersion solution coated with the low-molecular vinylprolidone becomes a metal film having good conductivity by heat treatment at 190 ° C. or higher in an inert atmosphere.
得られた銅ナノ粒子分散溶液の分散性についても調べるため、動的光散乱型粒度分布測定装置（ゼータサイザーナノシリーズ）を用いて、分散溶液中での銅ナノ粒子凝集体の粒度分布の測定を行った。その結果、実施例１に記載の１−ビニル−２−プロリドンで被覆された銅ナノ粒子分散溶液、実施例２に記載の低分子ビニルプロリドンに被覆された銅ナノ粒子分散溶液中での微粒子凝集体の平均サイズは、それぞれ２４０ｎｍ、１６０ｎｍであった。比較のため、実施例１の銅ナノ粒子分散溶液の製法において、１−ビニル−２−プロリドンを添加せずに作成した、有機物被覆がない銅ナノ粒子分散溶液についても、同様の粒度分布測定を行ったところ、その平均凝集サイズは１２００ｎｍであった。これにより、本発明の微粒子分散溶液の良好な液中分散性が確認された。 In order to investigate the dispersibility of the obtained copper nanoparticle dispersion, the particle size distribution of copper nanoparticle aggregates in the dispersion is measured using a dynamic light scattering particle size distribution analyzer (Zetasizer Nano Series). Went. As a result, the copper nanoparticle dispersion solution coated with 1-vinyl-2-prolidone described in Example 1 and the fine particles in the copper nanoparticle dispersion solution coated with the low-molecular vinylprolidone described in Example 2 The average size of the aggregates was 240 nm and 160 nm, respectively. For comparison, in the method for producing a copper nanoparticle dispersion solution of Example 1, the same particle size distribution measurement was performed for a copper nanoparticle dispersion solution without an organic substance coating prepared without adding 1-vinyl-2-prolidone. As a result, the average aggregate size was 1200 nm. Thereby, good dispersibility in the liquid of the fine particle dispersion of the present invention was confirmed.
本発明の比較例としてとして、分子量が３５００のポリビニルプロリドンに被覆された銅ナノ粒子およびその分散溶液を次のように作成した。 As a comparative example of the present invention, copper nanoparticles coated with polyvinylprolidone having a molecular weight of 3500 and a dispersion thereof were prepared as follows.
まず、銅ナノ粒子の原料として酢酸銅０．２ｇを蒸留水１０ｍｌに溶解させた酢酸銅水溶液１０ｍｌと、金属イオン還元剤として５．０ｍｏｌ／ｌとなるように水素化ホウ素ナトリウムと蒸留水とを混合した水素化ホウ素ナトリウム水溶液１００ｍｌと、を作成した。その後、上記水素化ホウ素ナトリウム水溶液に、ポリビニルプロリドン（ＰＶＰ：Ｋ１２、分子量約３５００）０．５ｇを添加して、攪拌溶解させた後、窒素ガス雰囲気中で、上記酢酸銅水溶液１０ｍｌを滴下した。この混合液を約６０分間よく攪拌しながら反応させた結果、ポリビニルプロリドンで被覆された銅ナノ粒子分散水溶液が得られた。これを数日間放置した後、生成した凝集沈殿物を、遠心分離器を用いて沈殿回収した。 First, 10 ml of a copper acetate aqueous solution in which 0.2 g of copper acetate was dissolved in 10 ml of distilled water as a raw material for copper nanoparticles, and sodium borohydride and distilled water so as to be 5.0 mol / l as a metal ion reducing agent. 100 ml of a mixed aqueous sodium borohydride solution was prepared. Thereafter, 0.5 g of polyvinylprolidone (PVP: K12, molecular weight of about 3500) was added to the sodium borohydride aqueous solution and dissolved by stirring, and then 10 ml of the copper acetate aqueous solution was added dropwise in a nitrogen gas atmosphere. . As a result of reacting this mixed solution with sufficient stirring for about 60 minutes, an aqueous copper nanoparticle dispersion solution coated with polyvinylprolidone was obtained. After leaving this for several days, the produced aggregated precipitate was collected by precipitation using a centrifuge.
その後、試験管に得られた粒子と適量の蒸留水とを入れ、超音波ホモジナイザーを用いてよく攪拌した後、遠心分離器で粒子成分を回収する水洗浄を３回、続いて、同じく試験管中で、得られた粒子と適量のブタノールとを入れ、超音波ホモジナイザーを用いてよく攪拌した後、遠心分離器で粒子成分を回収するアルコール洗浄を３回行った。更に、得られた粒子成分を１，２エタンジオール１０ｍｌに入れ、更に、再び、ポリビニルプロリドン（ＰＶＰ：Ｋ１２、分子量約３５００）０．１ｇを添加してから、その後、超音波ホモジナイザーを用いてよく攪拌することで、比較例である分子量３５００のポリビニルプロリドンに被覆された銅ナノ粒子分散溶液が得られた。 Then, after putting the obtained particles and an appropriate amount of distilled water into a test tube, stirring well with an ultrasonic homogenizer, washing with water to collect the particle components with a centrifuge three times, followed by the same test tube Inside, the obtained particles and an appropriate amount of butanol were added, and after thoroughly stirring using an ultrasonic homogenizer, alcohol washing for recovering the particle components with a centrifuge was performed three times. Further, the obtained particle component was put into 10 ml of 1,2 ethanediol, and 0.1 g of polyvinylprolidone (PVP: K12, molecular weight of about 3500) was added again, and thereafter using an ultrasonic homogenizer. By thoroughly stirring, a copper nanoparticle dispersion solution coated with polyvinylprolidone having a molecular weight of 3500, which is a comparative example, was obtained.
得られた分子量３５００のポリビニルプロリドンに被覆された銅ナノ粒子分散溶液をガラス基板上に塗布し、不活性（アルゴン）雰囲気中、１５０℃、１８０℃、１９０℃、２００℃、２５０℃、及び３００℃において、それぞれ１時間熱処理を行った。得られた焼成膜について、デジタルマルチメータを用いて、それぞれ直流４端子法にて、その電気抵抗値を測定した。図４は、分子量３５００のポリビニルプロリドンで被覆された銅ナノ粒子分散溶液の熱処理後の電気抵抗値の測定結果を示した図である。この結果より、分子量３５００のポリビニルプロリドンに被覆された銅ナノ粒子分散溶液は、不活性雰囲気中、３００℃以下の熱処理で、良好な導電性を持つ金属膜にはならないことが確認された。 The obtained dispersion solution of copper nanoparticles coated with polyvinylprolidone having a molecular weight of 3500 was coated on a glass substrate, and was 150 ° C., 180 ° C., 190 ° C., 200 ° C., 250 ° C. in an inert (argon) atmosphere, and Heat treatment was performed at 300 ° C. for 1 hour. About the obtained fired film, the electric resistance value was measured by the direct current | flow 4-terminal method using the digital multimeter, respectively. FIG. 4 is a view showing a measurement result of an electrical resistance value after heat treatment of a copper nanoparticle dispersion solution coated with polyvinylprolidone having a molecular weight of 3500. From this result, it was confirmed that the copper nanoparticle dispersion solution coated with polyvinylprolidone having a molecular weight of 3500 does not become a metal film having good conductivity by heat treatment at 300 ° C. or lower in an inert atmosphere.
１０ 金属イオン原料
１１ 還元剤
１２ 還元制御剤
１３ 蒸留水
１４ 金属微粒子分散溶液
１５ ハロゲン化水素
１６ 粒子成分
１７ 反応液
１８ 金属微粒子
１９ 再分散溶媒
２０ 金属微粒子分散溶液
DESCRIPTION OF SYMBOLS 10 Metal ion raw material 11 Reducing agent 12 Reduction control agent 13 Distilled water 14 Metal particulate dispersion solution 15 Hydrogen halide 16 Particle component 17 Reaction liquid 18 Metal particulate 19 Redispersion solvent 20 Metal particulate dispersion solution
Claims (9)
低分子量ビニルプロリドンに被覆されていることを特徴とする微粒子。 Nano-sized particles,
Fine particles characterized by being coated with low molecular weight vinylprolidone.
ポリビニルプロリドンで被覆された微粒子を分散させた水溶液の中に、ハロゲン化水素を添加混合する工程を備えていることを特徴とする微粒子の製造方法。 A method for producing nano-sized fine particles,
A method for producing fine particles, comprising a step of adding and mixing hydrogen halide into an aqueous solution in which fine particles coated with polyvinylprolidone are dispersed.
The method for producing a metal fine particle dispersion solution according to claim 8, wherein the organic solvent contains an organic compound having one or more hydroxyl groups in a molecule.
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| US8226863B2 (en) | 2009-01-26 | 2012-07-24 | Empire Technology Development Llc | Method for producing three-dimensional product having nanoporous surface |
| JP2014156627A (en) * | 2013-02-15 | 2014-08-28 | Furukawa Electric Co Ltd:The | Method of producing copper fine particle, and copper fine particle dispersion solution |
| JP2014156626A (en) * | 2013-02-15 | 2014-08-28 | Furukawa Electric Co Ltd:The | Copper fine particle dispersion solution, manufacturing method of sintered conductor, and manufacturing method of conductor connection member |
| JP2016011448A (en) * | 2014-06-30 | 2016-01-21 | 古河電気工業株式会社 | Fine particle, method for producing fine particle, and fine particle dispersion solution |
| JP2017002364A (en) * | 2015-06-11 | 2017-01-05 | 古河電気工業株式会社 | Dispersion solution of surface-coated metal particulate, and methods of producing sintered electrical conductor and electrically conductive connection member, including steps of applying and sintering the dispersion solution |
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| JP2005213626A (en) * | 2004-01-30 | 2005-08-11 | Sumitomo Osaka Cement Co Ltd | Method for manufacturing metal element-containing nanoparticle powder |
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| WO2010084613A1 (en) | 2009-01-26 | 2010-07-29 | アイランド ジャイアント デベロップメント エルエルピー | Method of producing cell culture scaffold |
| US8226863B2 (en) | 2009-01-26 | 2012-07-24 | Empire Technology Development Llc | Method for producing three-dimensional product having nanoporous surface |
| JP2014156627A (en) * | 2013-02-15 | 2014-08-28 | Furukawa Electric Co Ltd:The | Method of producing copper fine particle, and copper fine particle dispersion solution |
| JP2014156626A (en) * | 2013-02-15 | 2014-08-28 | Furukawa Electric Co Ltd:The | Copper fine particle dispersion solution, manufacturing method of sintered conductor, and manufacturing method of conductor connection member |
| JP2016011448A (en) * | 2014-06-30 | 2016-01-21 | 古河電気工業株式会社 | Fine particle, method for producing fine particle, and fine particle dispersion solution |
| JP2017002364A (en) * | 2015-06-11 | 2017-01-05 | 古河電気工業株式会社 | Dispersion solution of surface-coated metal particulate, and methods of producing sintered electrical conductor and electrically conductive connection member, including steps of applying and sintering the dispersion solution |
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