JP2008156720A - Method for producing silver nanoparticle - Google Patents
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本発明は、銀ナノ粒子の製造方法に関する。本発明にしたがい製造される銀ナノ粒子は、例えば導電性インクの原料として特に好適に用いられる。 The present invention relates to a method for producing silver nanoparticles. Silver nanoparticles produced according to the present invention are particularly preferably used as a raw material for conductive ink, for example.
本出願人は先に、硝酸銀溶液にＥＤＴＡ塩を加え、銀とＥＤＴＡの錯体スラリーを調製し、このスラリーにホルマリン等の還元剤を加え緩やかに還元反応を起こさせることで微粒銀粉を得る方法を提案した（特許文献１参照）。この方法により得られる微粒銀粉は低凝集性のものである。 The present applicant firstly added a EDTA salt to a silver nitrate solution, prepared a complex slurry of silver and EDTA, and added a reducing agent such as formalin to this slurry to cause a slow reduction reaction to obtain a fine silver powder. Proposed (see Patent Document 1). The fine silver powder obtained by this method has low agglomeration.
特許文献１に記載の方法とは別に、銀微粒子の製造方法として、高分子化合物、還元剤、及び銀塩を溶解してなる溶液を、２５℃以上、６０℃以下の温度にて撹拌する方法が提案されている（特許文献２参照）。この製造方法においては、高分子化合物としてポリエチレンイミン等が用いられ、還元剤としてアスコルビン酸、アスコルビン酸アルカリ金属塩、ゲンチシン酸、ハイドロキノン、アミノフェノール類、ジハイドロキシナフタレン、アミドール、メトール、フェニドン、没食子酸、プロトカテク酸、ピロガロール、アミノナフタレンが用いられる。この製造方法で得られる銀粒子は板状のものである。 In addition to the method described in Patent Document 1, as a method for producing silver fine particles, a method in which a solution obtained by dissolving a polymer compound, a reducing agent, and a silver salt is stirred at a temperature of 25 ° C. or higher and 60 ° C. or lower. Has been proposed (see Patent Document 2). In this production method, polyethyleneimine or the like is used as the polymer compound, and ascorbic acid, alkali metal ascorbate, gentisic acid, hydroquinone, aminophenols, dihydroxynaphthalene, amidol, methol, phenidone, gallic acid as the reducing agent. , Protocatechuic acid, pyrogallol, and aminonaphthalene are used. Silver particles obtained by this production method are plate-shaped.
本発明の目的は、前述した従来技術の製造方法で得られる銀微粒子よりも更に性能が向上した銀微粒子を製造し得る方法を提供することにある。 An object of the present invention is to provide a method capable of producing silver fine particles having further improved performance as compared with the silver fine particles obtained by the above-described conventional production method.
本発明は、エチレンジアミン四酢酸塩及びポリエチレンイミンの存在下に、銀イオンをホルマリンで還元することを特徴とする銀ナノ粒子の製造方法を提供するものである。 The present invention provides a method for producing silver nanoparticles, wherein silver ions are reduced with formalin in the presence of ethylenediaminetetraacetate and polyethyleneimine.
本発明によれば、粒径がそろった球状の銀ナノ粒子を容易に製造することができる。 According to the present invention, spherical silver nanoparticles having a uniform particle diameter can be easily produced.
以下本発明を、その好ましい実施形態に基づき説明する。本発明の製造方法では、主に水溶液中の銀塩を還元して銀ナノ粒子を製造する。反応は、エチレンジアミン四酢酸塩（以下、ＥＤＴＡ塩ともいう）及びポリエチレンイミン（以下、ＰＥＩともいう）の存在下に行う。 Hereinafter, the present invention will be described based on preferred embodiments thereof. In the production method of the present invention, silver nanoparticles are produced mainly by reducing a silver salt in an aqueous solution. The reaction is carried out in the presence of ethylenediaminetetraacetate (hereinafter also referred to as EDTA salt) and polyethyleneimine (hereinafter also referred to as PEI).
ＥＤＴＡ塩としては水溶性塩を用いることができる。例えばそのナトリウム塩などを用いることができる。ポリエチレンイミンとしては、重量平均分子量が４００〜１０００００、特に１０００〜１００００のものを用いることが、銀ナノ粒子の粒径を均一化し得ると共に、分散性を良好にし得る点から好ましい。 A water-soluble salt can be used as the EDTA salt. For example, a sodium salt thereof can be used. As the polyethyleneimine, it is preferable to use those having a weight average molecular weight of 400 to 100,000, particularly 1,000 to 10,000, from the viewpoint that the particle diameter of the silver nanoparticles can be made uniform and the dispersibility can be improved.
反応液中における銀イオンの濃度は、０．０１〜８重量％、特に０．５〜３重量％であることが、得られる銀ナノ粒子の分散性を良好にすることと、工業的生産性を両立できる点から好ましい。なお反応液は銀塩水溶液が好適で、銀イオン源としては水溶性の銀塩を特に制限なく用いることができる。例えば硝酸銀、酢酸銀、硫酸銀、過塩素酸銀、亜硝酸銀などが挙げられる。特に好ましくは硝酸銀が用いられる。 The concentration of silver ions in the reaction solution is 0.01 to 8% by weight, particularly 0.5 to 3% by weight, to improve the dispersibility of the resulting silver nanoparticles and to improve industrial productivity. It is preferable from the viewpoint that both can be achieved. The reaction solution is preferably an aqueous silver salt solution, and a water-soluble silver salt can be used without particular limitation as the silver ion source. Examples thereof include silver nitrate, silver acetate, silver sulfate, silver perchlorate, and silver nitrite. Particularly preferably, silver nitrate is used.
ＥＤＴＡ塩及びＰＥＩの量は、銀イオンとの使用量の関係で決定される。ＥＤＴＡ塩に関しては、反応液中に含まれる銀イオンに対して１００〜５００重量％、特に１５０〜３００重量％用いられることが、銀ナノ粒子の粒径を小さくし得ると共に、分散性を良好にし得る点から好ましい。同様の理由により、ＰＥＩに関しては、反応液中に含まれる銀イオンに対して１０〜２００重量％、特に２０〜１００重量％用いられることが好ましい。 The amount of EDTA salt and PEI is determined in relation to the amount used with silver ions. With respect to the EDTA salt, the use of 100 to 500% by weight, particularly 150 to 300% by weight, based on the silver ions contained in the reaction solution can reduce the particle size of the silver nanoparticles and improve the dispersibility. It is preferable from the point of obtaining. For the same reason, PEI is preferably used in an amount of 10 to 200% by weight, particularly 20 to 100% by weight, based on silver ions contained in the reaction solution.
本製造方法においては、ＥＤＴＡ塩及びＰＥＩの存在下に、銀イオンを還元剤としてのホルマリンで還元する。反応温度は、４０〜８０℃、特に５０〜７０℃であることが、還元速度を適度に速くしつつ、粒子の凝集を防止し得る点から好ましい。反応時間は、０．５〜３時間、特に１〜２時間であることが好ましい。 In this production method, silver ions are reduced with formalin as a reducing agent in the presence of EDTA salt and PEI. The reaction temperature is preferably 40 to 80 ° C., particularly 50 to 70 ° C., from the viewpoint that aggregation of particles can be prevented while appropriately increasing the reduction rate. The reaction time is preferably 0.5 to 3 hours, particularly 1 to 2 hours.
還元剤であるホルマリンは水に希釈した状態で反応液に添加される。添加は一括添加でもよく、逐次添加でもよい。ホルマリンの希釈液の濃度は、１〜３７重量％、特に３０〜３７重量％であることが、銀ナノ粒子を工業的に効率よく生産し得る点から好ましい。ホルマリンの添加量は、銀イオンの量との関係で決定される。詳細には、反応液中に含まれる銀イオンに対して、ホルマリンを４０〜１００重量％、特に５０〜６０重量％添加することが好ましい。 Formalin as a reducing agent is added to the reaction solution in a state diluted with water. The addition may be batch addition or sequential addition. The concentration of the diluted formalin solution is preferably 1 to 37% by weight, more preferably 30 to 37% by weight, from the viewpoint of efficiently producing silver nanoparticles industrially. The amount of formalin added is determined in relation to the amount of silver ions. In detail, it is preferable to add 40-100 weight%, especially 50-60 weight% of formalin with respect to the silver ion contained in a reaction liquid.
ホルマリンの添加によって銀イオンの還元が生じる。この場合、反応液中において、銀イオンはＥＤＴＡ塩と錯体を形成しているので、銀イオンの還元によって生成する銀ナノ粒子は球状のものとなる。また、ホルマリンは比較的還元性の低い還元剤なので、銀イオンの還元が急速には進行しないので、微粒の銀粒子が生成する。更に、反応系にＰＥＩが共存していることによって、銀イオンは粒径のそろった銀ナノ粒子に還元される。 Addition of formalin causes reduction of silver ions. In this case, since silver ions form a complex with the EDTA salt in the reaction solution, the silver nanoparticles generated by the reduction of silver ions are spherical. Further, since formalin is a reducing agent having a relatively low reducing property, the reduction of silver ions does not proceed rapidly, so that fine silver particles are generated. Furthermore, the presence of PEI in the reaction system reduces silver ions to silver nanoparticles having a uniform particle size.
粒径が一層そろった銀ナノ粒子を首尾良く生成させる観点から、反応液中には、上述したＰＥＩに加えてポリビニルピロリドンも存在させ、ＰＥＩ及びポリビニルピロリドンの共存下に銀イオンを還元することが好ましい。ポリビニルピロリドンの添加量は、銀イオンの量との関係で決定される。詳細には、反応液中に含まれる銀イオンに対して、ポリビニルピロリドンを１０〜１００重量％、特に３０〜７０重量％添加することが好ましい。 From the viewpoint of successfully producing silver nanoparticles having a more uniform particle size, polyvinyl pyrrolidone may also be present in the reaction solution in addition to the PEI described above, and silver ions can be reduced in the presence of PEI and polyvinyl pyrrolidone. preferable. The amount of polyvinyl pyrrolidone added is determined in relation to the amount of silver ions. Specifically, it is preferable to add 10 to 100% by weight, particularly 30 to 70% by weight of polyvinylpyrrolidone with respect to silver ions contained in the reaction solution.
ポリビニルピロリドンとしては、重量平均分子量が１００００〜５０００００、特に３００００〜１０００００のものを用いることが、反応液の粘度上昇に起因する銀ナノ粒子の沈降性の悪化を防ぎ、良好な分散性を維持し得る点から好ましい。 Polyvinylpyrrolidone having a weight average molecular weight of 10,000 to 500,000, particularly 30,000 to 100,000, prevents deterioration of the settling property of silver nanoparticles due to an increase in viscosity of the reaction solution, and maintains good dispersibility. It is preferable from the point of obtaining.
上述の操作によって銀イオンが還元されて銀ナノ粒子が生成したスラリーを、静置又は遠心分離して銀ナノ粒子を沈降させる。この場合、沈降を促進させる観点から、生成した銀ナノ粒子を疎水化処理に付することが好ましい。銀ナノ粒子はその微粒のゆえに、通常の状態では沈降に長時間を要する。これに対して銀ナノ粒子を疎水化処理することで、沈降時間の短縮化が図られる。 The slurry in which silver ions are generated by the reduction of silver ions by the above operation is allowed to stand or be centrifuged to precipitate the silver nanoparticles. In this case, it is preferable to subject the produced silver nanoparticles to a hydrophobization treatment from the viewpoint of promoting sedimentation. Since silver nanoparticles are fine, they usually take a long time to settle. On the other hand, the settling time can be shortened by hydrophobizing the silver nanoparticles.
銀ナノ粒子の疎水化処理には、スラリー中に疎水化剤を添加すればよい。疎水化剤としては、銀ナノ粒子の表面と親和性が良好であり且つ疎水基を有する化合物が用いられる。そのような化合物としては、例えばオレイルアミン、トリオクチルアミン、オクチルアミン等の炭化水素基を有するアミン、オレイン酸、ステアリン酸、デカン酸等の脂肪酸などが挙げられる。これらの疎水化剤のうち、オレイルアミンを用いることが、銀ナノ粒子の分散性を維持したまま、これを凝集沈殿させ得る点から好ましい。 In order to hydrophobize the silver nanoparticles, a hydrophobizing agent may be added to the slurry. As the hydrophobizing agent, a compound having a good affinity with the surface of the silver nanoparticles and having a hydrophobic group is used. Examples of such compounds include amines having a hydrocarbon group such as oleylamine, trioctylamine and octylamine, and fatty acids such as oleic acid, stearic acid and decanoic acid. Among these hydrophobizing agents, it is preferable to use oleylamine because it can be coagulated and precipitated while maintaining the dispersibility of the silver nanoparticles.
疎水化剤によって銀ナノ粒子を疎水化するときには、疎水化剤の相溶化剤をスラリー中に共存させることが好ましい。相溶化剤の作用によって、疎水化剤が銀ナノ粒子の表面に結合しやすくなり、疎水化を一層首尾良く行い得るからである。相溶化剤としては、エタノール等の低級アルコール（炭素数１〜４）、アセトン等のケトン類、酢酸エチル等のエステル類などが挙げられる。相溶化剤の添加量は、疎水化剤に対して１００〜１００００重量％、特に５００〜２０００重量％であることが好ましい。 When the silver nanoparticles are hydrophobized with a hydrophobizing agent, it is preferable that a compatibilizer for the hydrophobizing agent coexists in the slurry. This is because the action of the compatibilizing agent makes it easier for the hydrophobizing agent to bind to the surface of the silver nanoparticles, and the hydrophobization can be performed more successfully. Examples of the compatibilizer include lower alcohols (1 to 4 carbon atoms) such as ethanol, ketones such as acetone, esters such as ethyl acetate, and the like. The addition amount of the compatibilizer is preferably 100 to 10,000% by weight, particularly 500 to 2000% by weight, based on the hydrophobizing agent.
疎水化剤によって疎水化されて沈降した銀ナノ粒子は、例えばデカンテーションによってその上澄み液が廃棄される。その後、必要に応じて溶媒置換や濃縮を行う。更に銀ナノ粒子に所定の成分を配合することで、例えば導電性インクや導電性ペーストが得られる。 The silver nanoparticles that have been hydrophobized by the hydrophobizing agent and precipitated are discarded, for example, by decantation. Then, solvent substitution and concentration are performed as necessary. Furthermore, for example, a conductive ink or a conductive paste can be obtained by blending predetermined components into the silver nanoparticles.
銀イオンが還元されて銀ナノ粒子が生成したスラリーに、銀よりもイオン化傾向の大きな他の金属を、固体の形態、水溶性塩の形態又はイオンの形態で添加することもできる。この操作によってスラリー（水性スラリー）中における銀ナノ粒子の分散性を良好にすることができる。この理由は次のとおりである。水性スラリー中に存在する銀ナノ粒子は、その一部が銀イオンとして水中に溶解し、溶解した銀イオンが再び析出する。この再析出によって銀ナノ粒子の凝集が起こり、スラリーの保存中における銀ナノ粒子の分散性が低下する傾向にある。これに対して、銀ナノ粒子の水性スラリー中に、銀よりもイオン化傾向の大きな他の金属を、固体の形態、水溶性塩の形態又はイオンの形態で添加することで、スラリー中に該他の金属の固体及び／又はイオンが共存することになり、それによって銀ナノ粒子の溶解が抑制され、ひいては銀イオンの再析出が抑制される。その結果、スラリーの保存中における銀ナノ粒子の分散性を高めることが可能になる。前記の他の金属は、固体の形態、水溶性塩の形態又はイオンの形態の少なくとも一種の形態で、スラリー中に添加することができる。これらの形態の少なくとも二種の組み合わせを用いてもよい。 Other metals having a higher ionization tendency than silver may be added to the slurry in which silver ions are generated by reducing silver ions in the form of a solid, a water-soluble salt, or an ion. By this operation, the dispersibility of the silver nanoparticles in the slurry (aqueous slurry) can be improved. The reason for this is as follows. A part of the silver nanoparticles present in the aqueous slurry is dissolved in water as silver ions, and the dissolved silver ions are precipitated again. This reprecipitation causes aggregation of silver nanoparticles, and the dispersibility of the silver nanoparticles during storage of the slurry tends to decrease. On the other hand, by adding another metal having a higher ionization tendency than silver in an aqueous slurry of silver nanoparticles in the form of a solid, a water-soluble salt, or an ion, the other metal is added to the slurry. The metal solids and / or ions coexist, whereby the dissolution of the silver nanoparticles is suppressed, and thus the reprecipitation of the silver ions is suppressed. As a result, it is possible to improve the dispersibility of the silver nanoparticles during storage of the slurry. The other metal may be added to the slurry in at least one of a solid form, a water-soluble salt form or an ionic form. A combination of at least two of these forms may be used.
銀よりもイオン化傾向の大きな他の金属としては、例えばニッケル、銅、鉄、スズ、亜鉛などが挙げられる。これらのうちニッケルや銅を用いることが特に好ましい。銀よりもイオン化傾向の大きな他の金属を、固体の形態でスラリー中に配合する場合には、バルク状の形態や、粒子の形態で配合することができる。粒子の形態でスラリー中に配合する場合には、該粒子はナノ粒子でもよく、或いはナノ粒子よりも粒径の大きなものであってもよい。該粒子の粒径は例えば１〜１０００μｍ程度とすることができる。銀ナノ粒子との分離のしやすさを考慮すると、粒子の形態で用いるよりも、水溶性塩の形態及び／又はイオンの形態で用いることが好ましい。 Examples of other metals having a greater ionization tendency than silver include nickel, copper, iron, tin, and zinc. Of these, nickel and copper are particularly preferred. When other metals having a higher ionization tendency than silver are blended in the slurry in a solid form, they can be blended in a bulk form or a particle form. When blended in the slurry in the form of particles, the particles may be nanoparticles or may have a larger particle size than the nanoparticles. The particle size of the particles can be, for example, about 1 to 1000 μm. Considering the ease of separation from silver nanoparticles, it is preferable to use in the form of a water-soluble salt and / or ions rather than in the form of particles.
銀よりもイオン化傾向の大きな他の金属の配合量は、それが固体の形態であるか、水溶性塩の形態であるか、イオンの形態であるかを問わず、銀１当量に対して０．０１〜１０当量、特に０．５〜２当量であることが、スラリー中での銀の溶解を効果的に防止する観点から好ましい。前記の他の金属として銅を用いる場合には、銀１当量に対して銅１当量とは、銀１モルに対して銅を０．５モル用いることをいう。 The compounding amount of other metals having a higher ionization tendency than silver is 0 with respect to 1 equivalent of silver regardless of whether it is in the form of a solid, a water-soluble salt, or an ion. 0.01 to 10 equivalents, particularly 0.5 to 2 equivalents are preferable from the viewpoint of effectively preventing dissolution of silver in the slurry. When copper is used as the other metal, 1 equivalent of copper per 1 equivalent of silver means that 0.5 mole of copper is used per 1 mole of silver.
銀よりもイオン化傾向の大きな他の金属を銀ナノ粒子と分離するためには、例えば該金属を水溶性塩の形態及び／又はイオンの形態で用いる場合には、他の金属のイオンの濃度が所定の値以下となるまで、純水を用いてデカンテーションを繰り返せばよい。該金属を固体の形態で用いる場合には、製造する銀ナノ粒子の１００倍以上の粒径を有する大きな粒子又はインゴットを用い、フィルトレーション等によって分離除去すればよい。 In order to separate other metal having a higher ionization tendency than silver from silver nanoparticles, for example, when the metal is used in the form of a water-soluble salt and / or ion, the concentration of ions of the other metal is What is necessary is just to repeat a decantation using a pure water until it becomes below a predetermined value. When the metal is used in the form of a solid, it may be separated and removed by filtration or the like using large particles or ingots having a particle size 100 times or more that of the silver nanoparticles to be produced.
本発明においては、銀イオンが還元されて銀ナノ粒子が生成したスラリー中の銀ナノ粒子に対して、先に述べた疎水化処理を施し、その後に該スラリーに、銀よりもイオン化傾向の大きな他の金属を、固体の形態、水溶性塩の形態又はイオンの形態で添加することができる。或いは、銀イオンが還元されて銀ナノ粒子が生成したスラリーに、銀よりもイオン化傾向の大きな金属を、固体の形態、水溶性塩の形態又はイオンの形態で添加し、その後に、銀ナノ粒子に対して疎水化処理を施してもよい。 In the present invention, the silver nanoparticles in the slurry in which the silver ions are reduced to form silver nanoparticles are subjected to the hydrophobic treatment described above, and then the slurry has a higher ionization tendency than silver. Other metals can be added in solid form, water-soluble salt form or ionic form. Alternatively, a metal having a higher ionization tendency than silver is added in a solid form, a water-soluble salt form or an ionic form to a slurry in which silver ions are generated by reducing silver ions, and then silver nanoparticles are added. Hydrophobization treatment may be performed on the.
このようにして得られた銀ナノ粒子は、その一次粒子の平均粒径が好ましくは５〜１００ｎｍ、更に好ましくは１０〜５０ｎｍという微粒のものになる。一次粒子の平均粒径は、透過型電子顕微鏡（ＴＥＭ）によって撮影された粒子の写真を用い、個々の粒子のうち最も長い部分の長さを測定し、その平均値を算出することで求められる。 The silver nanoparticles thus obtained have fine particles with an average primary particle diameter of preferably 5 to 100 nm, more preferably 10 to 50 nm. The average particle size of the primary particles can be obtained by measuring the length of the longest part of each particle using a photograph of the particles taken with a transmission electron microscope (TEM) and calculating the average value. .
以上の操作によって得られた銀ナノ粒子は、例えば導電性インクや導電性ペーストの原料として好適に用いられる。かかるインクやペーストを用いてプラズマディスプレイパネルやチップ部品、ガラスセラミックパッケージ、セラミックフィルタ等の電子機器の配線回路や電極等を形成することができる。微細な回路や電極を形成するためには、銀粒子が微粒であることや凝集性が低いことが要求されるところ、本発明にしたがい製造された銀ナノ粒子は上述のとおり粒径のそろった微粒のものであり、また凝集性が低いので、前記の要求にまさに合致したものとなる。 The silver nanoparticles obtained by the above operation are suitably used as a raw material for conductive ink or conductive paste, for example. Wiring circuits and electrodes of electronic devices such as plasma display panels, chip parts, glass ceramic packages, and ceramic filters can be formed using such inks and pastes. In order to form fine circuits and electrodes, it is required that the silver particles are fine or have low agglomeration properties. The silver nanoparticles produced according to the present invention have the same particle size as described above. Since it is fine and has low cohesiveness, it exactly meets the above requirements.
以下、実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲はかかる実施例に制限されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples.
〔実施例１〕
１リットルのビーカー中に、硝酸銀１０．０ｇ、ＥＤＴＡ４Ｎａ塩１５．０ｇ、重量平均分子量１８００のＰＥＩ３．０ｇ及び純水３００ｍｌを投入し十分に撹拌した。液温を５０℃に保った状態下に、３７重量％のホルマリン水溶液１００．０ｇを一括投入し銀イオンの還元反応を行った。反応は、液温を５０℃に保ち１．５時間行った。このようにして、銀ナノ粒子のスラリーを得た。ＴＥＭによる銀ナノ粒子の一次粒子の平均粒径は２８ｎｍであった。
[Example 1]
In a 1 liter beaker, 10.0 g of silver nitrate, 15.0 g of EDTA4Na salt, 3.0 g of PEI having a weight average molecular weight of 1800 and 300 ml of pure water were added and sufficiently stirred. While maintaining the liquid temperature at 50 ° C., 100.0 g of a 37 wt% formalin aqueous solution was added all at once to carry out a silver ion reduction reaction. The reaction was carried out for 1.5 hours while maintaining the liquid temperature at 50 ° C. In this way, a slurry of silver nanoparticles was obtained. The average particle diameter of primary particles of silver nanoparticles by TEM was 28 nm.
銀ナノ粒子のスラリーに、硝酸銅三水和物（Ｃｕ（ＮＯ3）2・３Ｈ2Ｏ）１０．９ｇを純水１００ｍｌに溶解した水溶液を添加して１分間撹拌した。スラリーの温度は５０℃に維持した。なお、銅は銀よりもイオン化傾向の大きな金属である。 An aqueous solution in which 10.9 g of copper nitrate trihydrate (Cu (NO 3 ) 2 .3H 2 O) was dissolved in 100 ml of pure water was added to the silver nanoparticle slurry and stirred for 1 minute. The temperature of the slurry was maintained at 50 ° C. Copper is a metal that has a higher ionization tendency than silver.
次いで、エタノール１００ｍｌにオレイルアミン０．３ｇを溶解させた溶液をスラリーに添加して３０分間撹拌を行い、銀ナノ粒子の疎水化処理を行った。スラリーの温度は５０℃に維持した。 Next, a solution in which 0.3 g of oleylamine was dissolved in 100 ml of ethanol was added to the slurry and stirred for 30 minutes to hydrophobize the silver nanoparticles. The temperature of the slurry was maintained at 50 ° C.
最後に、純水でスラリーのデカンテーションを繰り返し行い、スラリー中の銅イオンを除去した。このようにして得られた銀ナノ粒子のＴＥＭ像を図１に示す。図１に示す結果から明らかなように、銀ナノ粒子の粒径は非常に均一であることが判る。また銀ナノ粒子に凝集がほとんど観察されないことも判る。ＴＥＭ観察とは別に、銀ナノ粒子についてレーザー回折散乱式粒度分布測定を行ったところ、Ｄ10＝０．１９２μｍ、Ｄ50＝０．２５６μｍ、Ｄ90＝０．３５７μｍとなり、粒度分布がシャープであることが判った。この結果から、ＴＥＭ観察の結果が裏付けられた。粒度分布の測定に際しては、前分散として濃度１重量％のヘキサメタリン酸ナトリウム水溶液中で５分間超音波分散を行った。 Finally, the decantation of the slurry was repeated with pure water to remove copper ions in the slurry. A TEM image of the silver nanoparticles thus obtained is shown in FIG. As is clear from the results shown in FIG. 1, it can be seen that the silver nanoparticles have a very uniform particle size. It can also be seen that almost no aggregation is observed in the silver nanoparticles. Apart from the TEM observation, was subjected to laser diffraction scattering particle size distribution measurement for silver nanoparticles, D 10 = 0.192μm, D 50 = 0.256μm, D 90 = 0.357μm , and the particle size distribution is sharp I found out. From this result, the result of TEM observation was supported. When measuring the particle size distribution, ultrasonic dispersion was performed for 5 minutes in an aqueous sodium hexametaphosphate solution having a concentration of 1% by weight as pre-dispersion.
〔実施例２〕
実施例１において、硝酸銅の添加及び疎水化処理を行わなかった以外は実施例１と同様にして銀ナノ粒子を得た。ＴＥＭによる銀ナノ粒子の一次粒子の平均粒径は３６ｎｍであった。得られた銀ナノ粒子のＴＥＭ像を図２に示す。ＴＥＭ観察とは別に、銀ナノ粒子について実施例１と同様にレーザー回折散乱式粒度分布測定を行ったところ、Ｄ10＝１．２８４μｍ、Ｄ50＝５．５９７μｍ、Ｄ90＝１３．６８μｍとなった。
[Example 2]
In Example 1, silver nanoparticles were obtained in the same manner as in Example 1 except that copper nitrate was not added and the hydrophobic treatment was not performed. The average particle diameter of primary particles of the silver nanoparticles by TEM was 36 nm. A TEM image of the obtained silver nanoparticles is shown in FIG. Apart from the TEM observation, the laser diffraction scattering type particle size distribution measurement was performed on the silver nanoparticles in the same manner as in Example 1. As a result, D 10 = 1.284 μm, D 50 = 5.597 μm, and D 90 = 13.68 μm. It was.
〔実施例３〕
実施例１における疎水化処理において、更にポリビニルピロリドン（重量平均分子量３５０００）を３．０ｇ添加する以外は実施例１と同様にして銀ナノ粒子を得た。ＴＥＭによる銀ナノ粒子の一次粒子の平均粒径は２５ｎｍであった。また、銀ナノ粒子について実施例１と同様にレーザー回折散乱式粒度分布測定を行ったところ、Ｄ10＝０．１７８μｍ、Ｄ50＝０．２３０μｍ、Ｄ90＝０．２９７μｍとなった。
Example 3
In the hydrophobization treatment in Example 1, silver nanoparticles were obtained in the same manner as in Example 1 except that 3.0 g of polyvinyl pyrrolidone (weight average molecular weight 35000) was further added. The average particle diameter of primary particles of silver nanoparticles by TEM was 25 nm. When it was laser diffraction scattering particle size distribution measurement in the same manner as in Example 1 Silver nanoparticles became D 10 = 0.178μm, D 50 = 0.230μm, and D 90 = 0.297μm.
〔比較例１〕
特開２００５−１０５３７６号公報（上述の特許文献２）の実施例１に準拠し、以下の手順で銀粒子を調製した。水１００重量部に、重量平均分子量１８００のＰＥＩを０．３重量部溶解させ、得られた水溶液に硝酸銀を０．０２４重量部添加して溶解させた。液温を６０℃に保持し、還元剤としてアルコルビン酸を０．０３重量部添加し、２時間撹拌させながら反応を完遂させた。ＴＥＭによる銀粒子の一次粒子の平均粒径は１２０ｎｍであった。粒子の形状は不定形状であった。また、銀粒子について実施例１と同様にレーザー回折散乱式粒度分布測定を行ったところ、Ｄ10＝０．３５８μｍ、Ｄ50＝０．７１１μｍ、Ｄ90＝１．３０６μｍとなった。
[Comparative Example 1]
Based on Example 1 of Unexamined-Japanese-Patent No. 2005-105376 (above-mentioned patent document 2), the silver particle was prepared in the following procedures. In 100 parts by weight of water, 0.3 part by weight of PEI having a weight average molecular weight of 1800 was dissolved, and 0.024 part by weight of silver nitrate was added and dissolved in the obtained aqueous solution. The liquid temperature was kept at 60 ° C., 0.03 part by weight of ascorbic acid was added as a reducing agent, and the reaction was completed while stirring for 2 hours. The average particle diameter of primary particles of silver particles by TEM was 120 nm. The shape of the particles was indefinite. Moreover, when laser diffraction scattering type particle size distribution measurement was performed on silver particles in the same manner as in Example 1, D 10 = 0.358 μm, D 50 = 0.711 μm, and D 90 = 1.306 μm.
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