JP2010196120A - Method for manufacturing metal fine particle, metal fine particle dispersion and sintered compact - Google Patents
Method for manufacturing metal fine particle, metal fine particle dispersion and sintered compact Download PDFInfo
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Abstract
【課題】硫黄、窒素を含有せず、さらに金属微粒子を極性溶媒に安定に分散可能な金属微粒子の製造方法、金属微粒子分散液ならびに焼結体を提供する。
【解決手段】下記式（I）：
（式中、X1は(CH2)nOHを示し（n＝0〜3）、mは1〜5の整数を示す。）で表されるジアゾニウム塩と、金化合物とを、還元剤の存在下に極性溶媒中で反応させて、下記式（II）：
で表される共有結合および配位結合から選ばれるいずれかの相互作用を有する金属微粒子を得る。
【選択図】なしDisclosed are a method for producing metal fine particles that do not contain sulfur and nitrogen and that can stably disperse metal fine particles in a polar solvent, a metal fine particle dispersion, and a sintered body.
The following formula (I):
(Wherein X 1 represents (CH 2 ) n OH (n = 0 to 3), and m represents an integer of 1 to 5)) and a gold compound, Reaction in a polar solvent in the presence of the following formula (II):
Metal fine particles having any interaction selected from a covalent bond and a coordinate bond represented by
[Selection figure] None
Description
本発明は、金属微粒子の製造方法、金属微粒子分散液ならびに焼結体に関するものである。 The present invention relates to a method for producing metal fine particles, a metal fine particle dispersion, and a sintered body.
従来、金属微粒子分散液を得る方法として、物理的方法、気相法や液相法等の化学的方法等が知られている。液相法では、チオール、アミン、アルコール、カルボン酸、PVA等の高分子等を保護剤に用いて金属微粒子を得る方法、長鎖アルキル基を有するジアゾニウム塩を原料に用いて金属微粒子を得る方法（非特許文献１参照）、2,4,6-トリクロロベンゼンジアゾニウムクロライド等を分散剤に用いて吸着もしくは塩構造を有する金属微粒子を得る方法（特許文献１参照）が知られている。 Conventionally, as a method for obtaining a metal fine particle dispersion, a physical method, a chemical method such as a gas phase method or a liquid phase method, and the like are known. In the liquid phase method, a method of obtaining metal fine particles using a polymer such as thiol, amine, alcohol, carboxylic acid, PVA or the like as a protective agent, a method of obtaining metal fine particles using a diazonium salt having a long chain alkyl group as a raw material (See Non-Patent Document 1), a method of obtaining metal fine particles having an adsorption or salt structure using 2,4,6-trichlorobenzenediazonium chloride or the like as a dispersant is known (see Patent Document 1).
しかしながら、物理的方法では一般に均一な粒径の金属微粒子を大量に合成するのは難しく、気相法では一般にコストが高くなる。また、従来の液相法に用いられる保護剤、換言すれば配位子は孤立電子対を持つ基を有しており、この基が金属と配位結合し、錯体を形成する。配位する基としてはチオール基、アミノ基、ヒドロキシル基、カルボキシル基、フォスフィノ基等があり、その配位原子は硫黄、窒素、酸素、リンであるが、チオールを保護剤に用いた方法では銀微粒子の焼結時にAg2SやSOxが発生し、アミンを用いた方法では焼結時にNOxが発生する。アルコールやカルボン酸を保護剤に用いた方法では、得られる金属微粒子分散液の安定性においてさらに改善の余地がある。PVA等の高分子を保護剤に用いた方法では、有機含有量が多く、また単分子膜とすることができない。長鎖アルキル基を有するジアゾニウム塩を原料に用いた方法では、微粒子製造時に溶剤を用いることを必須とし、水に分散しない。 However, in general, it is difficult to synthesize a large amount of metal fine particles having a uniform particle diameter by a physical method, and the cost is generally high in a gas phase method. In addition, the protective agent used in the conventional liquid phase method, in other words, the ligand has a group having a lone pair, and this group coordinates with the metal to form a complex. Coordinating groups include thiol groups, amino groups, hydroxyl groups, carboxyl groups, and phosphino groups. Coordinating atoms are sulfur, nitrogen, oxygen, and phosphorus. Ag 2 S and SO x are generated during the sintering of the fine particles, and NO x is generated during the sintering in the method using the amine. In the method using alcohol or carboxylic acid as a protective agent, there is room for further improvement in the stability of the resulting metal fine particle dispersion. In a method using a polymer such as PVA as a protective agent, the organic content is large and a monomolecular film cannot be obtained. In the method using a diazonium salt having a long-chain alkyl group as a raw material, it is essential to use a solvent during the production of fine particles, and it is not dispersed in water.
そして特許文献１に記載の金属微粒子を得る方法では、還元剤により金属塩のみを還元して、還元された金属と光感受性分散剤とが吸着もしくは塩として相互作用する構造の金属微粒子を含有するパターン形成用の金属微粒子分散液を得ているが、この金属微粒子分散液は光感受性分散剤が感光すると吸着能力を失い金属微粒子から光感受性分散剤が遊離し、分散状態が解除される。また、感光性が高いため自然光下でも分散剤が解離する虞があり、金属微粒子の安定性に問題がある。さらに、金属微粒子分散液を焼結体の原料として用いる場合の焼結時発生ガスに対する配慮がなされていない。例えば2,4,6-トリクロロベンゼンジアゾニウムクロライドを光感受性分散剤として用いた場合では、グルコースにより塩化金酸のみが還元され、還元析出した金微粒子表面は2,4,6-トリクロロベンゼンジアゾニウムクロライドが吸着もしくは塩を形成し保護されるため分散状態となるが、この保護金属微粒子にはCl原子およびN原子が含有しているため、焼結時に塩素系ガスおよびNOxが発生する虞がある。 In the method for obtaining metal fine particles described in Patent Document 1, only metal salts are reduced by a reducing agent, and the metal fine particles having a structure in which the reduced metal and the photosensitive dispersant adsorb or interact as a salt are contained. A metal fine particle dispersion for pattern formation has been obtained. When the photosensitive fine particle dispersion is exposed to light, the metal fine particle dispersion loses its adsorption ability, and the photosensitive fine particle is released from the metal fine particles, and the dispersed state is released. Further, since the photosensitivity is high, the dispersant may be dissociated even under natural light, and there is a problem in the stability of the metal fine particles. Furthermore, no consideration is given to the gas generated during sintering when the metal fine particle dispersion is used as a raw material of the sintered body. For example, when 2,4,6-trichlorobenzenediazonium chloride is used as a photosensitive dispersion agent, only chloroauric acid is reduced by glucose, and 2,4,6-trichlorobenzenediazonium chloride is deposited on the surface of the gold fine particles deposited by reduction. Although it is in a dispersed state because it is adsorbed or formed to form a salt and protected, the protective metal fine particles contain Cl atoms and N atoms, so that there is a possibility that chlorine gas and NO x are generated during sintering.
本発明は、以上の通りの事情に鑑みてなされたものであり、硫黄、窒素を含有せず、さらに金属微粒子を極性溶媒に安定に分散可能な金属微粒子の製造方法、金属微粒子分散液ならびに焼結体を提供することを課題としている。 The present invention has been made in view of the circumstances as described above, and does not contain sulfur and nitrogen, and further, a method for producing metal fine particles capable of stably dispersing metal fine particles in a polar solvent, a metal fine particle dispersion, and a sintering method. The challenge is to provide a body.
本発明は、上記の課題を解決するために、以下のことを特徴としている。 The present invention is characterized by the following in order to solve the above problems.
第１：下記式（I）： First: Formula (I) below:
（式中、X1は(CH2)nOHを示し（n＝0〜3）、mは1〜5の整数を示す。）で表されるジアゾニウム塩と、金化合物とを、還元剤の存在下に極性溶媒中で反応させて、下記式（II）： (Wherein X 1 represents (CH 2 ) n OH (n = 0 to 3), and m represents an integer of 1 to 5)) and a gold compound, Reaction in a polar solvent in the presence of the following formula (II):
（式中、X2は(CH2)nOHまたはその塩、あるいは対応するアルコキシドイオンを示し（n＝0〜3）、mは1〜5の整数を示す。Mは金を示す。）で表される共有結合および配位結合から選ばれるいずれかの相互作用を有する金属微粒子を得ることを特徴とする金属微粒子の製造方法。 (Wherein X 2 represents (CH 2 ) n OH or a salt thereof, or a corresponding alkoxide ion (n = 0 to 3), m represents an integer of 1 to 5, and M represents gold). A method for producing metal fine particles, comprising obtaining metal fine particles having any interaction selected from a covalent bond and a coordinate bond represented.
第２：下記式（II）： Second: Formula (II) below:
（式中、X2は(CH2)nOHまたはその塩、あるいは対応するアルコキシドイオンを示し（n＝0〜3）、mは1〜5の整数を示す。Mは金を示す。）で表される共有結合および配位結合から選ばれるいずれかの相互作用を有する金属微粒子が極性溶媒に分散されていることを特徴とする金属微粒子分散液。 (Wherein, X 2 is (CH 2) n OH or a salt thereof, or show a corresponding alkoxide ion, (n = 0~3), m is .M represents an integer of 1 to 5 show the gold.) In A metal fine particle dispersion, wherein metal fine particles having any interaction selected from a covalent bond and a coordinate bond represented are dispersed in a polar solvent.
第３：上記第２の金属微粒子分散液を基材に塗布し焼結してなることを特徴とする焼結体。 Third: A sintered body obtained by applying the second metal fine particle dispersion to a base material and sintering it.
上記第１の発明の金属微粒子の製造方法によれば、硫黄、窒素を含有せず、さらに金属微粒子を極性溶媒に安定に分散可能なコスト、環境面に優れた金属微粒子を得ることができる。 According to the method for producing metal fine particles of the first invention, it is possible to obtain metal fine particles that do not contain sulfur and nitrogen, and that can stably disperse the metal fine particles in a polar solvent and are excellent in terms of cost and environment.
上記第２の発明の金属微粒子分散液によれば、硫黄、窒素を含有せず、さらに金属微粒子を極性溶媒に安定に分散可能である。 According to the metal fine particle dispersion of the second aspect of the invention, sulfur and nitrogen are not contained, and the metal fine particles can be stably dispersed in the polar solvent.
上記第３の発明の焼結体によれば、上記第２の発明の金属微粒子分散液を用いているので、焼結時にNOx、SOx等の酸性ガス、ハロゲン系ガスを発生せず、各種の用途に応用できる良好な焼結体を得ることができる。 According to the sintered body of the third aspect of the invention, since the metal fine particle dispersion of the second aspect of the invention is used, an acid gas such as NO x and SO x and a halogen-based gas are not generated during the sintering, A good sintered body applicable to various uses can be obtained.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明に用いられる式（I）で表されるジアゾニウム塩は、例えば、テトラフルオロほう酸水溶液に、対応するアミノフェニルアルコールを添加、攪拌し、亜硝酸ナトリウム水溶液を滴下し熟成した後、ろ別、溶剤洗浄、再結晶等の精製を行うことにより得ることができる。 The diazonium salt represented by the formula (I) used in the present invention is, for example, added to the tetrafluoroboric acid aqueous solution, stirred, and aged by dropwise addition of an aqueous sodium nitrite solution, followed by filtration, It can be obtained by performing purification such as solvent washing and recrystallization.
本発明では、ジアゾニウム塩として、水酸基を有する式（I）の官能基X1を導入したものを用いたことを特徴としているが、これは経済性、極性溶剤への溶解性、合成の簡便性、および安定性を考慮したものである。しかも、このような官能基X1を有する構造の式（I）で表されるジアゾニウム塩は、非常に安定であり、例えば、遮光、５℃以下、不活性ガス雰囲気下等で酸素、水を除外した環境にて保存した場合、1ヶ月以上の保存が可能である。さらに製造時の仕込み時等においては、空気雰囲気下での取り扱いも可能である。 In the present invention, the diazonium salt is characterized by using a hydroxyl group-containing functional group X 1 of formula (I), which is economical, soluble in a polar solvent, and easy to synthesize. , And stability. Moreover, the diazonium salt represented by the formula (I) having the structure having such a functional group X 1 is very stable. For example, oxygen and water are shielded from light at 5 ° C. or less in an inert gas atmosphere. When stored in an excluded environment, it can be stored for more than a month. Furthermore, it can be handled in an air atmosphere at the time of manufacturing.
本発明において、式（I）で表されるジアゾニウム塩と反応させる金化合物としては、金塩、金錯体等を用いることができ、極性溶媒に溶解できるものであれば特に限定されない。例えば、テトラクロロ金（III）酸（H(AuCl4)）、テトラクロロ金（III）酸ナトリウム（Na(AuCl4)）、ジエチルアミン金（III）三塩化物（(C2H5)2NH(AuCl3)）、ジシアノ金（I）酸カリウム（KAu(CN)2）、シアン化金（I）（AuCN）等を用いることができる。中でも、テトラクロロ金（III）酸が好ましい。 In the present invention, the gold compound to be reacted with the diazonium salt represented by the formula (I) is not particularly limited as long as it can be a gold salt, a gold complex or the like and can be dissolved in a polar solvent. For example, tetrachloroauric (III) acid (H (AuCl 4)), tetrachloroaurate (III) sodium (Na (AuCl 4)), diethylamine gold (III) trichloride ((C 2 H 5) 2 NH (AuCl 3 )), potassium dicyanogold (I) acid (KAu (CN) 2 ), gold cyanide (I) (AuCN), and the like can be used. Of these, tetrachloroauric (III) acid is preferred.
本発明では、式（I）で表されるジアゾニウム塩と、金化合物とを、還元剤の存在下に極性溶媒中で反応させて、式（II）で表される共有結合および配位結合から選ばれるいずれかの相互作用（式（II）中の点線で示される（アルキル）アルコキシフェニル基と、金Mとの相互作用）を有する金属微粒子を合成する。反応は、100℃未満、好ましくは30℃以下の温度で行うことができる。 In the present invention, a diazonium salt represented by the formula (I) and a gold compound are reacted in a polar solvent in the presence of a reducing agent to form a covalent bond and a coordination bond represented by the formula (II). Metal fine particles having any one of the selected interactions (interaction between the (alkyl) alkoxyphenyl group indicated by the dotted line in the formula (II) and gold M) are synthesized. The reaction can be carried out at a temperature below 100 ° C, preferably below 30 ° C.
より具体的には、例えば、式（I）で表されるジアゾニウム塩、および金化合物を極性溶媒に溶解、攪拌する。次いで還元剤を滴下し、これにより金化合物と式（I）で表されるジアゾニウム塩とを同時に還元し、熟成を行うことにより、式（II）で表される、フェニル基と金属とが直接に相互作用する金属微粒子が合成される。その後、必要に応じて水洗、溶剤洗浄、遠心分離、ろ過、電気透析等で精製を行い、窒素化合物、ハロゲン化合物等を除去し、式（II）で表される金属微粒子を得る。 More specifically, for example, a diazonium salt represented by the formula (I) and a gold compound are dissolved in a polar solvent and stirred. Subsequently, a reducing agent is dropped, whereby the gold compound and the diazonium salt represented by the formula (I) are simultaneously reduced and ripened to directly form the phenyl group and the metal represented by the formula (II). Metal fine particles that interact with each other are synthesized. Then, if necessary, purification is performed by washing with water, solvent washing, centrifugation, filtration, electrodialysis and the like to remove nitrogen compounds, halogen compounds, etc., and obtain metal fine particles represented by the formula (II).
なお、式（II）においてX2は(CH2)nOHまたはその塩、あるいは対応するアルコキシドイオンを示し、塩としてはナトリウム塩、カリウム塩等のアルカリ金属塩、アミン塩等が挙げられる。なお、金属微粒子は、X2として(CH2)nOHとその塩との両方が混在するものであってもよい。また、金属微粒子がX2としてアルコキシドイオンを有する場合としては、金属微粒子が分散液の状態である場合が挙げられる。 In the formula (II), X 2 represents (CH 2 ) n OH or a salt thereof, or a corresponding alkoxide ion. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, amine salts and the like. The metal fine particles may be a mixture of (CH 2 ) n OH and a salt thereof as X 2 . Further, the case where the metal fine particles have an alkoxide ion as X 2 includes a case where the metal fine particles are in a dispersion state.
反応溶媒、分散溶媒として用いる極性溶媒としては、水、THF（テトラヒドロフラン）、メタノール、エタノール、1-プロパノール、2-プロパノール等のアルコールが挙げられる。中でも、水、メタノールが好ましい。還元剤は、ジアゾニウム塩と、金化合物（金塩、金錯体）とを同時に効率よく還元できるものを選択する必要がある。例えば、水素化ホウ素ナトリウム（NaBH4）、シアノ水素化ホウ素ナトリウム（NaBH3CN）、水素化トリエチルホウ素リチウム（LiBH(C2H5)3）、水素化ホウ素リチウム（LiBH4）、水素化ホウ素カリウム（KBH4）、水素化ホウ素テトラブチルアンモニウム（(CH3(CH2)3)4NBH4）、水素化ホウ素テトラメチルアンモニウム（(CH3)4NBH4）等の水素化ホウ素塩系還元剤、ジボラン（B2H6）、アンモニアボラン（NH3-BH3）、トリメチルアンモニアボラン（(CH3)3N-BH3）等のボラン系還元剤を用いることができるが、中でも水素化ホウ素ナトリウムが好ましく用いられる。 Examples of the polar solvent used as the reaction solvent and the dispersion solvent include water, alcohols such as THF (tetrahydrofuran), methanol, ethanol, 1-propanol, and 2-propanol. Of these, water and methanol are preferable. It is necessary to select a reducing agent that can efficiently reduce a diazonium salt and a gold compound (gold salt, gold complex) simultaneously. For example, sodium borohydride (NaBH 4 ), sodium cyanoborohydride (NaBH 3 CN), lithium triethylborohydride (LiBH (C 2 H 5 ) 3 ), lithium borohydride (LiBH 4 ), borohydride Boron hydride salt reduction such as potassium (KBH 4 ), borohydride tetrabutylammonium borohydride ((CH 3 (CH 2 ) 3 ) 4 NBH 4 ), borohydride tetramethyl ammonium ((CH 3 ) 4 NBH 4 ) Borane reducing agents such as diborane (B 2 H 6 ), ammonia borane (NH 3 -BH 3 ), trimethylammonia borane ((CH 3 ) 3 N-BH 3 ) can be used. Sodium boron is preferably used.
本発明によれば、金微粒子の製造時の反応溶媒、また分散溶媒として極性溶媒を用いることができる。特に反応溶媒、分散溶媒として水を用いることができることから環境、コスト面において優れている。また、金微粒子は、硫黄、窒素を含有せず、焼結時のSOx、NOx発生を抑制できる。さらに、金微粒子の分散状態を長期間安定に維持することができる。 According to the present invention, a polar solvent can be used as a reaction solvent and a dispersion solvent in the production of gold fine particles. In particular, since water can be used as a reaction solvent and a dispersion solvent, it is excellent in terms of environment and cost. Further, the gold fine particles do not contain sulfur and nitrogen, and can suppress generation of SO x and NO x during sintering. Furthermore, the dispersion state of the gold fine particles can be maintained stably for a long period of time.
本発明の金属微粒子分散液は、例えば、導電性薄膜、導電性細線、電極、プリント配線等への導電性材料、電顕用染色材料、生体センシング材料等の用途に好適に用いることができる。特に、この金属微粒子分散液を金属基板等の基材に塗布して焼結し、焼結体として導電性材料に関わる各種の分野において用いることができる。 The metal fine particle dispersion of the present invention can be suitably used for applications such as conductive thin films, conductive thin wires, electrodes, conductive materials for printed wiring, dyeing materials for electron microscopes, biological sensing materials, and the like. In particular, the metal fine particle dispersion can be applied to a base material such as a metal substrate and sintered, and can be used as a sintered body in various fields related to conductive materials.
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらの実施例に何ら限定されるものではない。
＜参考例１＞
下記式で表される化合物１を合成した。
EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples at all.
<Reference Example 1>
Compound 1 represented by the following formula was synthesized.
42%テトラフルオロほう酸水溶液（16.98g、0.081mol）に、2-アミノベンジルアルコール（5.00g、0.041mol）を添加、攪拌した。40%亜硝酸ナトリウム水溶液（7.00g、0.041mol）を10〜15℃下、30分で滴下し、10分間熟成した後、ろ別、溶剤洗浄、再結晶を行うことにより、薄赤色粉末を得た。
赤外線吸収スペクトル 2278cm-1：N≡N+伸縮振動、3329cm-1：Ｏ−Ｈ伸縮振動、768cm-1：C−H面外変角振動
＜参考例２＞
下記式で表される化合物２を合成した。
2-Aminobenzyl alcohol (5.00 g, 0.041 mol) was added to a 42% tetrafluoroboric acid aqueous solution (16.98 g, 0.081 mol) and stirred. A 40% sodium nitrite aqueous solution (7.00 g, 0.041 mol) was added dropwise at 10-15 ° C. in 30 minutes, and after aging for 10 minutes, a light red powder was obtained by filtration, solvent washing, and recrystallization. It was.
Infrared absorption spectrum 2278cm -1: N≡N + stretching vibration, 3329cm -1: O-H stretching vibration, 768cm -1: C-H out-of-plane deformation vibration <Reference Example 2>
Compound 2 represented by the following formula was synthesized.
42%テトラフルオロほう酸水溶液（16.98g、0.081mol）に、3-アミノベンジルアルコール（5.00g、0.041mol）を添加、攪拌した。40%亜硝酸ナトリウム水溶液（7.00g、0.041mol）を10〜15℃下、30分で滴下し、10分間熟成した後、ろ別、溶剤洗浄、再結晶等の精製を行うことにより、薄赤色粉末を得た。
赤外線吸収スペクトル 2274cm-1：N≡N+伸縮振動、3377cm-1：Ｏ−Ｈ伸縮振動、797cm-1：C−H面外変角振動
＜参考例３＞
下記式で表される化合物３を合成した。
To a 42% tetrafluoroboric acid aqueous solution (16.98 g, 0.081 mol), 3-aminobenzyl alcohol (5.00 g, 0.041 mol) was added and stirred. A 40% sodium nitrite aqueous solution (7.00 g, 0.041 mol) was added dropwise at 10 to 15 ° C. in 30 minutes, and after aging for 10 minutes, purification by filtration, solvent washing, recrystallization, etc. A powder was obtained.
Infrared absorption spectrum 2274cm -1: N≡N + stretching vibration, 3377cm -1: O-H stretching vibration, 797cm -1: C-H out-of-plane deformation vibration <Reference Example 3>
Compound 3 represented by the following formula was synthesized.
42%テトラフルオロほう酸水溶液（15.24g、0.073mol）に、4-アミノフェネチルアルコール（5.01g、0.037mol）を添加、攪拌した。40%亜硝酸ナトリウム水溶液（6.28g、0.037mol）を10〜15℃下、30分で滴下し、10分間熟成した後、ろ別、溶剤洗浄、再結晶等の精製を行うことにより、赤色粉末を得た。
赤外線吸収スペクトル 2262cm-1：N≡N+伸縮振動、3431cm-1：Ｏ−Ｈ伸縮振動、824cm-1：C−H面外変角振動
＜実施例１＞
テトラクロロ金（III）酸（0.1030g、0.2501mmol）をイオン交換水（25g）に溶解させ、N2を15分間フローし、脱気した。N2雰囲気下、化合物１（0.0555g、0.2501mmol）を加え、1分間攪拌させた後、イオン交換水7.5gで溶解させた水素化ホウ素ナトリウム（0.0095g、0.2511mmol）を室温下、2時間で滴下した。滴下後、2時間熟成し、黒紫色分散液が得られた。得られた分散液を遠心分離、水洗等で精製し、金含有量29.67ppmの黒紫色分散液が得られた。
紫外−可視吸収スペクトル 560nm
＜実施例２＞
テトラクロロ金（III）酸（0.1997g、0.4849mmol）をイオン交換水（45g）に溶解させ、N2を15分間フローし、脱気した。N2雰囲気下、化合物２（0.1076g、0.4848mmol）を加え、1分間攪拌させた後、イオン交換水15gで溶解させた水素化ホウ素ナトリウム（0.0183g、0.4837mmol）を室温下、2時間で滴下した。滴下後、2時間熟成し、青紫色分散液が得られた。得られた分散液を遠心分離、水洗等で精製し、金含有量785ppmの黒紫色分散液が得られた。
紫外−可視吸収スペクトル 578nm
＜実施例３＞
テトラクロロ金（III）酸（0.1545g、0.3751mmol）をイオン交換水（37.5g）に溶解させ、N2を15分間フローし、脱気した。N2雰囲気下、化合物３（0.0885g、0.3750mmol）を加え、1分間攪拌させた後、イオン交換水11.3gで溶解させた水素化ホウ素ナトリウム（0.0142g、0.3753mmol）を室温下、2時間で滴下した。滴下後、2時間熟成し、黒紫色分散液が得られた。得られた分散液を遠心分離、水洗等で精製し、金含有量704ppmの黒紫色分散液が得られた。
紫外−可視吸収スペクトル 583nm
なお、実施例１〜３の金微粒子について赤外線吸収スペクトルを測定した結果、ジアゾニウム基由来の吸収ピークが消失し、3645cm-1、3210cm-1付近にO−H伸縮振動、770〜860 cm-1の範囲に芳香環のC−H面外変角振動が認められた。
4-Aminophenethyl alcohol (5.01 g, 0.037 mol) was added to a 42% tetrafluoroboric acid aqueous solution (15.24 g, 0.073 mol) and stirred. A 40% sodium nitrite aqueous solution (6.28 g, 0.037 mol) was added dropwise at 10 to 15 ° C. in 30 minutes, aged for 10 minutes, and then purified by filtration, solvent washing, recrystallization, etc. Got.
Infrared absorption spectrum 2262cm -1: N≡N + stretching vibration, 3431cm -1: O-H stretching vibration, 824cm -1: C-H out-of-plane deformation vibration <Example 1>
Tetrachloroauric (III) acid (0.1030 g, 0.2501 mmol) was dissolved in ion-exchanged water (25 g), and N 2 was flowed for 15 minutes to deaerate. Under N 2 atmosphere, Compound 1 (0.0555g, 0.2501mmol) was added and allowed to stir for 1 minute, sodium borohydride dissolved in deionized water 7.5g (0.0095g, 0.2511mmol) at room temperature for 2 hours It was dripped at. After dropping, the mixture was aged for 2 hours to obtain a black purple dispersion. The obtained dispersion was purified by centrifugation, washing with water, etc., and a black purple dispersion having a gold content of 29.67 ppm was obtained.
UV-Vis absorption spectrum 560nm
<Example 2>
Tetrachloroauric (III) acid (0.1997 g, 0.4849 mmol) was dissolved in ion-exchanged water (45 g), and N 2 was allowed to flow for 15 minutes for degassing. Under N 2 atmosphere, compound 2 (0.1076 g, 0.4848 mmol) was added and stirred for 1 minute, and then sodium borohydride (0.0183 g, 0.4837 mmol) dissolved in 15 g of ion-exchanged water was added at room temperature for 2 hours. It was dripped. After the dropwise addition, the mixture was aged for 2 hours to obtain a blue-violet dispersion. The resulting dispersion was purified by centrifugation, washing with water, etc., and a black purple dispersion having a gold content of 785 ppm was obtained.
UV-Vis absorption spectrum 578nm
<Example 3>
Tetrachloroauric (III) acid (0.1545 g, 0.3751 mmol) was dissolved in ion-exchanged water (37.5 g), and N 2 was allowed to flow for 15 minutes for degassing. Under N 2 atmosphere, compound 3 (0.0885 g, 0.3750 mmol) was added and stirred for 1 minute, and then sodium borohydride (0.0142 g, 0.3753 mmol) dissolved in 11.3 g of ion-exchanged water was added at room temperature for 2 hours. It was dripped at. After dropping, the mixture was aged for 2 hours to obtain a black purple dispersion. The obtained dispersion was purified by centrifugation, washing with water, etc., and a black purple dispersion having a gold content of 704 ppm was obtained.
UV-Vis absorption spectrum 583nm
As a result of measuring the infrared absorption spectrum of the gold particles of Examples 1 to 3, disappeared absorption peak derived from diazonium groups, 3645cm -1, O-H stretching vibration in the vicinity of 3210cm -1, 770~860 cm -1 A C-H out-of-plane bending vibration of the aromatic ring was observed in the range.
また、実施例１〜３の金微粒子は、１ヶ月以上、室温、自然光下にて安定に分散状態を維持した。
＜実施例４＞
実施例３で得られた分散液を4％に濃縮し、アルミナ基板に塗布した。空気雰囲気下、150℃または200℃で1時間焼結した結果、金属光沢のある膜が得られ、導電性が確認された。
Moreover, the gold fine particles of Examples 1 to 3 stably maintained a dispersed state at room temperature and natural light for one month or longer.
<Example 4>
The dispersion obtained in Example 3 was concentrated to 4% and applied to an alumina substrate. As a result of sintering at 150 ° C. or 200 ° C. for 1 hour in an air atmosphere, a metallic glossy film was obtained, and conductivity was confirmed.
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| JP2012117173A (en) * | 2010-12-01 | 2012-06-21 | Miyoshi Oil & Fat Co Ltd | Metal particulate carrier material |
| RU2584288C2 (en) * | 2014-07-09 | 2016-05-20 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Synthesis of zero-valence transition metal nanoparticles with surface covalently modified with organic functional groups |
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