JP4436093B2 - Ultrafine metal particles and method for producing the same - Google Patents
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Description
本発明は、金属超微粒子及びその製造方法に関する。 The present invention relates to ultrafine metal particles and a method for producing the same.
金属ペーストは、電子回路、電極等の導電膜の形成に用いられている。これらの導電膜は、金属ペーストをセラミックス、ガラス等の非導電性基板上に塗布し、塗膜を焼成・硬化することにより形成されている。近年、電子材料の多様化、需要増大等に伴って、金属ペーストの用途も急速に拡大しつつあるが、その一つとして金属粉末と樹脂成分とを混練して製造される金属導電膜形成用厚膜ペーストが知られている。 Metal paste is used to form conductive films such as electronic circuits and electrodes. These conductive films are formed by applying a metal paste onto a nonconductive substrate such as ceramics or glass, and baking and curing the coating film. In recent years, with the diversification of electronic materials and increasing demand, the use of metal pastes is rapidly expanding. One of them is for forming metal conductive films produced by kneading metal powder and resin components. Thick film pastes are known.
しかしながら、従来における金属導電膜形成用厚膜ペーストでは、次のような問題がある。 However, the conventional thick paste for forming a metal conductive film has the following problems.
第一に、金属粉末の粒子サイズが数ミクロンと大きいため、焼成温度が必然的に高くなり、最低でも５００〜６００℃という高温で焼成しなければ所定の導電膜を形成することが困難である。また、このように焼成温度が高いことから、耐熱性の低いプラスチック等の基材に適用することも困難である。 First, since the particle size of the metal powder is as large as several microns, the firing temperature is inevitably high, and it is difficult to form a predetermined conductive film unless it is fired at a high temperature of at least 500 to 600 ° C. . In addition, since the firing temperature is high as described above, it is difficult to apply to a base material such as plastic having low heat resistance.
第二に、上記のように金属粉末の粒子サイズが大きいことから、形成される導電膜にもピンホールが発生しやすい。このため、ピンホールのない緻密な導電膜を得るためには、厚膜ペーストを塗布し、焼成するという一連の工程を何回も繰り返す必要がある。 Secondly, since the particle size of the metal powder is large as described above, pinholes are easily generated in the formed conductive film. For this reason, in order to obtain a dense conductive film without pinholes, it is necessary to repeat a series of steps of applying a thick film paste and baking it many times.
第三に、上記厚膜ペーストは、少なくとも金属粉末の調製、樹脂成分の調製及び両者の混練という工程が必要であり、その製造工程も効率的なものとは言えない。 Thirdly, the thick film paste requires at least the steps of preparation of metal powder, preparation of resin components, and kneading of both, and the production process is not efficient.
従って、本発明は、特に、金属膜の形成をより確実かつ容易に実現できる材料を提供することを主な目的とする。 Therefore, the main object of the present invention is to provide a material that can realize the formation of the metal film more reliably and easily.
本発明者は、かかる従来技術の問題点を解決するために鋭意研究を重ねた結果、特定の金属錯体化合物を用いる場合には上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the problems of the prior art, the present inventor has found that the above object can be achieved when a specific metal complex compound is used, and has completed the present invention.
すなわち、本発明は、下記の金属超微粒子及びその製造方法に係るものである。 That is, the present invention relates to the following metal ultrafine particles and a method for producing the same.
１．一般式［Ｒ １ Ｒ ２ Ｒ ３ Ｒ ４ Ｎ］ ｘ ［Ｍ ｙ （Ａ） ｚ ］（但し、Ｒ １ 〜Ｒ ４ は、同一又は別異の炭化水素基であって置換基を有していても良いもの、Ｍは遷移金属、Ａは有機硫黄系配位子、ｘは０よりも大きい整数、ｙは０よりも大きい整数、ｚは０よりも大きい整数を示す。）で表わされる４級アンモニウム塩型金属錯体化合物を出発原料とし、当該化合物の有機硫黄系配位子の還元的脱離反応から中心金属を還元する製造方法により得られる金属超微粒子であって、
中心部とその周囲の保護層から構成され、中心部が金属成分からなり、保護層が有機成分からなり、有機成分として当該４級アンモニウム塩［Ｒ １ Ｒ ２ Ｒ ３ Ｒ ４ Ｎ］の熱分解により生じるアルキル基の一部又は全部を含むことを特徴とする金属超微粒子。
２．金属超微粒子とともにジスルフィドを生成させる上記項１に記載の金属超微粒子。
３．有機硫黄系配位子がチオレート配位子（ＳＲ’）又はチオアセチレン配位子（ＳＣ≡ＣＲ’）（いずれについても、Ｒ’は炭化水素基であって置換基を有していても良いものを示す。）である上記項１又は２に記載の金属超微粒子。
４．Ｍが、Ａｕ、Ｐｔ、Ｃｕ、Ｎｉ又はＰｄである上記項１〜３のいずれかに記載の金属超微粒子。
５．金属成分の含有量が８０重量％以上である上記項１〜４のいずれかに記載の金属超微粒子。
６．上記項１〜５のいずれかに記載の金属超微粒子を含む金属膜成形用材料。
1. [R 1 R 2 R 3 R 4 N] x [M y (A) z ] (wherein R 1 to R 4 are the same or different hydrocarbon groups and have a substituent) M is a transition metal, A is an organic sulfur-based ligand, x is an integer greater than 0, y is an integer greater than 0, and z is an integer greater than 0). Ultrafine metal particles obtained by a production method in which an ammonium salt-type metal complex compound is used as a starting material and a central metal is reduced from a reductive elimination reaction of the organic sulfur ligand of the compound,
It consists of a central part and a protective layer around it, the central part is made of a metal component, the protective layer is made of an organic component, and the heat of the quaternary ammonium salt [R 1 R 2 R 3 R 4 N] as the organic component A metal ultrafine particle comprising part or all of an alkyl group generated by decomposition .
2. 2. The ultrafine metal particles according to
3. The organic sulfur ligand is a thiolate ligand (SR ′) or a thioacetylene ligand (SC≡CR ′) (in any case, R ′ is a hydrocarbon group and may have a substituent. 3. The ultrafine metal particles according to
4). Item 4. The ultrafine metal particles according to any one of
5. Item 5. The ultrafine metal particles according to any one of
6). Item 6. A metal film forming material comprising the metal ultrafine particles according to any one of
本発明の製造方法によれば、ナノオーダーの粒径をもつ金属超微粒子を効率的かつ確実に製造することができる。 According to the production method of the present invention, ultrafine metal particles having a nano-order particle size can be produced efficiently and reliably.
本発明の金属超微粒子は、中心部が金属成分からなり、保護層が有機成分からなるという特異な構造を有しているので、凝集が起こりにくく、ナノオーダーの粒径を安定して維持することができる。 The ultrafine metal particles of the present invention have a unique structure in which the central portion is composed of a metal component and the protective layer is composed of an organic component, so that aggregation is unlikely to occur and the nano-order particle size is stably maintained. be able to.
これにより、従来技術のような問題点のない金属膜を効率的かつ確実に形成することができる。特に、金属超微粒子を金属膜形成用に用いる場合は、その焼成温度が４００℃以下という低温で金属膜を形成することができ、コスト面のみならず、幅広い種類の基材に適用できるという点でも有利である。 As a result, a metal film free from problems as in the prior art can be formed efficiently and reliably. In particular, when metal ultrafine particles are used for forming a metal film, the metal film can be formed at a low temperature of 400 ° C. or lower, and it can be applied not only to the cost but also to a wide variety of substrates. But it is advantageous.
本発明の製造方法は、一般式［Ｒ1Ｒ2Ｒ3Ｒ4Ｎ］x［Ｍy（Ａ）z］（但し、Ｒ1〜Ｒ4は、同一又は別異の炭化水素基であって置換基を有していても良いもの、Ｍは遷移金属、Ａは有機硫黄系配位子、ｘは０よりも大きい整数、ｙは０よりも大きい整数、ｚは０よりも大きい整数を示す。）で表わされる４級アンモニウム塩型金属錯体化合物を出発原料とし、当該化合物の有機硫黄系配位子の還元的脱離反応から中心金属を還元することを特徴とする。 Production method of the present invention have the general formula [R 1 R 2 R 3 R 4 N] x [M y (A) z] ( where, R 1 to R 4 are the same or different, hydrocarbon radicals What may have a substituent, M is a transition metal, A is an organic sulfur-based ligand, x is an integer greater than 0, y is an integer greater than 0, and z is an integer greater than 0 )) As a starting material, and the central metal is reduced from the reductive elimination reaction of the organosulfur ligand of the compound.
本発明の製造方法の出発原料（以下「前駆体」ともいう）である４級アンモニウム塩型金属錯体化合物は、一般式［Ｒ1Ｒ2Ｒ3Ｒ4Ｎ］x［Ｍy（Ａ）z］で表わされる。この一般式を有するものであれば、公知の製法で得られるもの又は市販品を用いることもできる。例えば、上記化合物が一般式［Ｒ4Ｎ］［Ａｕ（ＳＲ’）2］（Ｒはアルキル基、Ｒ’はアルキル基を示す。以下の１）及び２）においても同じ。）で示される４級アンモニウム塩型金属錯体化合物を製造する場合は次のような工程１）〜２）（溶媒中での反応）によって製造することができる。 The starting material (hereinafter referred to as "precursor") quaternary ammonium salt type metal complex compound which is a production method of the present invention have the general formula [R 1 R 2 R 3 R 4 N] x [M y (A) z ]. If it has this general formula, what is obtained by a well-known manufacturing method or a commercial item can also be used. For example, the above compound is the same in the general formula [R 4 N] [Au (SR ′) 2 ] (R represents an alkyl group, R ′ represents an alkyl group. The following 1) and 2). In the case of producing a quaternary ammonium salt type metal complex compound represented by (), it can be produced by the following steps 1) to 2) (reaction in a solvent).
１）ＨＡｕＣｌ4＋Ｒ4ＮＣｌ→［Ｒ4Ｎ］［ＡｕＣｌ4］＋ＨＣｌ
２）［Ｒ4Ｎ］［ＡｕＣｌ4］＋４Ｒ’ＳＮａ→［Ｒ4Ｎ］［Ａｕ（ＳＲ’）2］
＋Ｒ’Ｓ−ＳＲ’＋４ＮａＣｌ
すなわち、塩化金酸等の金属塩の溶液に炭化水素基を有する４級アンモニウム塩を反応させ、得られた生成物をナトリウムメチラートの存在下でチオール化合物を反応させることによって所定の４級アンモニウム塩型金属錯体化合物を得ることができる。従って、この場合は、４級アンモニウム塩型金属錯体化合物におけるＲ1〜Ｒ4は、上記の４級アンモニウム塩を適宜選択することによって決定することができる。また、中心金属に配位する配位子は、上記チオール化合物の種類によって決定することができる。溶媒は、用いる原料の種類等に応じて公知の溶媒から適宜採択すれば良い。
1) HAuCl 4 + R 4 NCl → [R 4 N] [AuCl 4 ] + HCl
2) [R 4 N] [AuCl 4 ] + 4R′SNa → [R 4 N] [Au (SR ′) 2 ]
+ R'S-SR '+ 4NaCl
That is, a solution of a metal salt such as chloroauric acid is reacted with a quaternary ammonium salt having a hydrocarbon group, and the resulting product is reacted with a thiol compound in the presence of sodium methylate to give a predetermined quaternary ammonium salt. A salt-type metal complex compound can be obtained. Therefore, in this case, R 1 to R 4 in the quaternary ammonium salt type metal complex compound can be determined by appropriately selecting the quaternary ammonium salt. Moreover, the ligand coordinated to the central metal can be determined by the type of the thiol compound. The solvent may be appropriately selected from known solvents according to the type of raw material used.
本発明における４級アンモニウム塩型金属錯体化合物のＲ1〜Ｒ4は、同一又は別異の炭化水素基であって置換基を有していても良いものを適用できる。炭化水素基としては特に限定的ではないが、通常は炭素数１〜２０のアルキル基であって置換基を有していても良いものことが好ましい。具体的には、［Ｒ1Ｒ2Ｒ3Ｒ4Ｎ］部として［Ｃ12Ｈ25（ＣＨ3）3Ｎ］、［Ｃ14Ｈ29（ＣＨ3）3Ｎ］、［（Ｃ18Ｈ37）2（ＣＨ3）2Ｎ］、［Ｃ6Ｈ13（ＣＨ3）3Ｎ］等の直鎖アルキル基をもつものが例示される。 In the present invention, R 1 to R 4 of the quaternary ammonium salt type metal complex compound may be the same or different hydrocarbon groups which may have a substituent. Although it does not specifically limit as a hydrocarbon group, Usually, it is a C1-C20 alkyl group and the thing which may have a substituent is preferable. Specifically, [C 12 H 25 (CH 3 ) 3 N], [C 14 H 29 (CH 3 ) 3 N], [(C 18 H 37 ) as the [R 1 R 2 R 3 R 4 N] part. Examples thereof include those having a linear alkyl group such as 2 (CH 3 ) 2 N] and [C 6 H 13 (CH 3 ) 3 N].
上記炭化水素基が置換基を有する場合、その置換基の種類も制限されない。例えば、メチル基、エチル基、ＯＨ基、ニトロ基、ハロゲン基（Ｃｌ、Ｂｒ等）、メトキシ基、エトキシ基等が挙げられる。 When the hydrocarbon group has a substituent, the type of the substituent is not limited. Examples thereof include a methyl group, an ethyl group, an OH group, a nitro group, a halogen group (Cl, Br, etc.), a methoxy group, and an ethoxy group.
上記Ｍは遷移金属であり、上記４級アンモニウム塩型金属錯体化合物の中心金属を構成する。遷移金属としては、例えばＡｕ、Ｐｔ、Ｃｕ、Ｎｉ、Ｐｄ、Ｃｏ、Ｆｅ、Ｔｉ、Ｃｒ、Ｍｎ、Ｚｒ等が挙げられる。本発明では、特にＡｕ、Ｐｔ、Ｃｕ、Ｎｉ又はＰｄが好ましい。 M is a transition metal and constitutes the central metal of the quaternary ammonium salt type metal complex compound. Examples of the transition metal include Au, Pt, Cu, Ni, Pd, Co, Fe, Ti, Cr, Mn, and Zr. In the present invention, Au, Pt, Cu, Ni or Pd is particularly preferable.
Ａは有機硫黄系配位子を示す。硫黄原子を含む配位子であれば、その化学構造は特に限定されず、また単座配位子、二座配位子等のいずれであっても良い。 A represents an organic sulfur-based ligand. As long as it is a ligand containing a sulfur atom, its chemical structure is not particularly limited, and may be any of a monodentate ligand, a bidentate ligand, and the like.
特に、本発明の有機硫黄系配位子としては、チオレート配位子（ＳＲ’）又はチオアセチレン配位子（ＳＣ≡ＣＲ’）（いずれについても、Ｒ’は炭化水素基であって置換基を有していても良いものを示す。）であることが好ましい。上記Ｒ’は、特に炭素数１〜２０のアルキル基であって置換基を有していても良いものことが好ましい。置換基を有する場合、その置換基の種類も制限されず、前記と同様のものを適用できる。有機硫黄系配位子は、のいずれであっても良く、中心金属の種類等により適宜選択すれば良い。 In particular, the organic sulfur-based ligand of the present invention includes a thiolate ligand (SR ′) or a thioacetylene ligand (SC≡CR ′) (in which R ′ is a hydrocarbon group and a substituent It is preferable that it may have. R ′ is particularly preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent. When it has a substituent, the kind of the substituent is not limited, and the same one as described above can be applied. The organic sulfur-based ligand may be any of them, and may be appropriately selected depending on the type of the central metal.
チオレート配位子としては、Ｒ’部としてＣnＨ2n+1（ｎ＝１〜２０）で示されるものが好ましく、例えばＣ12Ｈ25、Ｃ6Ｈ13、Ｃ13Ｈ37等の直鎖アルキル基が適用できる。チオアセチレン配位子のＲ’部としては、例えばＣnＨ2n+1（ｎ＝１〜８）で示されるものが例示される。 As the thiolate ligand, those represented by C n H 2n + 1 (n = 1 to 20) as the R ′ portion are preferable. For example, linear chains such as C 12 H 25 , C 6 H 13 , and C 13 H 37 are used. Alkyl groups can be applied. Examples of the R ′ portion of the thioacetylene ligand include those represented by C n H 2n + 1 (n = 1 to 8).
置換基を有するチオアセチレン配位子は、Ｃ≡ＣＲ’部としてプロピン、２−プロピン−１−オール、１−ブチン−３−オール、３−メチル−１−ブチン−３−オール、３，３−ジメチル−１−ブチン、１−ペンチン、１−ペンチン−３−オール、４−ペンチン−１−オール、４−ペンチン−２−オール、４−メチル−１−ペンチン、３−メチル−１−ペンチン−３−オール、５−ヘキシン−１−オール、５−メチル−１−ヘキシン−３−オール、３，５−ジメチル−１−ヘキシン−３−オール、１−ヘプチン、１−ヘプチン−３−オール、５−ヘプチン−３−オール、３，６−ジメチル−１−ヘプチン−３−オール、３，６−ジメチル−１−ヘプチン−３−オール、１−オクチン、１−オクチン−３−オール等が例示される。 The substituted thioacetylene ligand includes propyne, 2-propyn-1-ol, 1-butyn-3-ol, 3-methyl-1-butyn-3-ol, 3, 3 as C≡CR ′ moiety. -Dimethyl-1-butyne, 1-pentyne, 1-pentyne-3-ol, 4-pentyn-1-ol, 4-pentyn-2-ol, 4-methyl-1-pentyne, 3-methyl-1-pentyne -3-ol, 5-hexyn-1-ol, 5-methyl-1-hexyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptin, 1-heptin-3-ol 5-heptin-3-ol, 3,6-dimethyl-1-heptin-3-ol, 3,6-dimethyl-1-heptin-3-ol, 1-octyne, 1-octin-3-ol, and the like Illustrated.
また、例えば水酸基を有する環状炭化水素を含むチオアセチレン配位子も適用できる。このような配位子ＳＣ≡ＣＲ’は、Ｃ≡ＣＲ’部として１−エチニル−１−シクロプロパノール、１−エチニル−１−シクロブタノール、１−エチニル−１−シクロペンタノール、１−エチニル−１−シクロヘキサノール、１−プロピン−３−シクロプロパノール、１−プロピン−３−シクロブタノール、１−プロピン−３−シクロペンタノール、１−ブチン−４−シクロブタノール、１−ペンチン−５−シクロプロパノール等が例示される。 Further, for example, a thioacetylene ligand containing a cyclic hydrocarbon having a hydroxyl group can also be applied. Such ligand SC≡CR ′ has 1-ethynyl-1-cyclopropanol, 1-ethynyl-1-cyclobutanol, 1-ethynyl-1-cyclopentanol, 1-ethynyl- as C≡CR ′ moiety. 1-cyclohexanol, 1-propyne-3-cyclopropanol, 1-propyne-3-cyclobutanol, 1-propyne-3-cyclopentanol, 1-butyne-4-cyclobutanol, 1-pentyne-5-cyclopropanol Etc. are exemplified.
上記ｘは０よりも大きい整数、ｙは０よりも大きい整数、ｚは０よりも大きい整数をそれぞれ示し、中心金属の種類、有機硫黄系配位子の種類等により適宜決定される。例えば、４級アンモニウム塩型金属錯体化合物の有機硫黄系配位子がチオレート配位子（ＳＲ’）又はチオアセチレン配位子（ＳＣ≡ＣＲ’）である場合において、中心金属ＭがＡｕのときはｘ＝２、ｙ＝１及びｚ＝２、ＭがＡｇのときはｘ＝１、ｙ＝１及びｚ＝２、ＭがＰｔのときはｘ＝２、ｙ＝１及びｚ＝４、ＭがＣｕのときはｘ＝１、ｙ＝１及びｚ＝２（又はｘ＝２、ｙ＝１及びｚ＝３）、ＭがＰｄのときはｘ＝２、ｙ＝１及びｚ＝４、ＭがＮｉのときはｘ＝２、ｙ＝１及びｚ＝４等とすれば良い。 The above x is an integer greater than 0, y is an integer greater than 0, and z is an integer greater than 0, and is appropriately determined depending on the type of the central metal, the type of the organic sulfur-based ligand, and the like. For example, when the organic sulfur-based ligand of the quaternary ammonium salt metal complex compound is a thiolate ligand (SR ′) or a thioacetylene ligand (SC≡CR ′), the central metal M is Au. X = 2, y = 1 and z = 2, when M is Ag, x = 1, y = 1 and z = 2, when M is Pt, x = 2, y = 1 and z = 4, M When Cu is Cu, x = 1, y = 1 and z = 2 (or x = 2, y = 1 and z = 3), and when M is Pd, x = 2, y = 1 and z = 4, M When Ni is Ni, x = 2, y = 1, z = 4, etc. may be set.
本発明の製造方法では、上記のような４級アンモニウム塩型金属錯体化合物を出発原料として用い、この化合物の有機硫黄系配位子の還元的脱離反応から中心金属を還元する。 In the production method of the present invention, the quaternary ammonium salt type metal complex compound as described above is used as a starting material, and the central metal is reduced from the reductive elimination reaction of the organic sulfur ligand of this compound.
例えば、出発原料として［Ｒ4Ｎ］［Ａｕ（ＳＣ12Ｈ25）2］（Ｒはアルキル基）を用いる場合の反応は、下記のように進行する。
［Ｒ4Ｎ］［Ａｕ（ＳＣ12Ｈ25）2］→Ａｕ（−Ｒ）＋Ｒ3Ｎ＋（ＳＣ12Ｈ25）2
すなわち、チオレート配位子が還元的脱離を起こし、ジスルフィドを生成するとともに金を生成するが、同時に起こる４級アンモニウム塩の分解（熱分解）により生じるアルキル基の一部又は全部が金のまわりに保護層を形成し、平均粒径が１０数ナノメータの金超微粒子（Ａｕ（−Ｒ））となる。
For example, the reaction when [R 4 N] [Au (SC 12 H 25 ) 2 ] (R is an alkyl group) is used as a starting material proceeds as follows.
[R 4 N] [Au (SC 12 H 25 ) 2 ] → Au (−R) + R 3 N + (SC 12 H 25 ) 2
That is, the thiolate ligand undergoes reductive elimination to produce disulfide and gold, but part or all of the alkyl group generated by the simultaneous decomposition (thermal decomposition) of the quaternary ammonium salt is around the gold. A protective layer is formed on the substrate, and ultrafine gold particles (Au (-R)) having an average particle size of a few tens of nanometers are obtained.
本発明の製造方法においては、上記のような還元的脱離反応が起こる限り、いずれの操作方法によって上記出発原料を処理しても良いが、通常は出発原料の熱処理によって実施することができる。 In the production method of the present invention, as long as the reductive elimination reaction as described above occurs, the starting material may be treated by any operating method, but it can be usually carried out by heat treatment of the starting material.
熱処理における条件は、かかる反応が生ずる限り特にその条件に制限はなく、出発原料の種類、最終製品の用途・使用目的等に応じて適宜設定すれば良い。特に、金属超微粒子の金属成分の含有量が８０重量％以上となるように熱処理するのが好ましい。上記含有量の上限は特に限定されないが、通常は９５重量％程度（炭化水素基成分が５重量％以上）となるようにすれば良い。換言すれば、金属成分の含有量が８０〜９５重量％程度となるように熱処理すれば良い。 Conditions for the heat treatment are not particularly limited as long as such a reaction occurs, and may be set as appropriate according to the type of the starting material, the use and purpose of use of the final product, and the like. In particular, heat treatment is preferably performed so that the content of the metal component in the ultrafine metal particles is 80% by weight or more. The upper limit of the content is not particularly limited, but it may be usually about 95% by weight (hydrocarbon group component is 5% by weight or more). In other words, heat treatment may be performed so that the content of the metal component is about 80 to 95% by weight.
従って、加熱温度、加熱時間、加熱雰囲気等も、出発原料の種類、所望の粒径・金属成分含有量、最終製品の用途等との関係で設定すれば良い。例えば、出発材料として［Ｃ12Ｈ25Ｎ（ＣＨ3）3］［Ａｕ（ＳＣ12Ｈ25）2］を用いる場合は、窒素ガス等の不活性ガス雰囲気中１６０℃で７時間程度加熱すれば、粒径３０〜４０ｎｍの粒子が多く分布する金超微粒子（金含有量９０重量％以上）を得ることができる。 Accordingly, the heating temperature, heating time, heating atmosphere, etc. may be set in relation to the type of starting material, desired particle size / metal component content, use of the final product, and the like. For example, when [C 12 H 25 N (CH 3 ) 3 ] [Au (SC 12 H 25 ) 2 ] is used as a starting material, it can be heated at 160 ° C. for about 7 hours in an inert gas atmosphere such as nitrogen gas. In addition, ultrafine gold particles (gold content of 90% by weight or more) in which many particles having a particle size of 30 to 40 nm are distributed can be obtained.
還元的脱離反応が完了した後、生成した金属超微粒子は、一般には副生したジスルフィドとともに存在する。生成したジスルフィドは通常は液状であり、その中に沈殿するようなかたちで金属超微粒子が生成する。この場合は、濾過、遠心分離等の通常の固液分離方法に従って金属超微粒子を回収し、必要に応じて水、溶剤等で洗浄すれば良い。さらに、必要に応じて金属超微粒子を自然乾燥又は強制乾燥させても良い。 After the reductive elimination reaction is completed, the produced ultrafine metal particles are generally present with by-produced disulfides. The produced disulfide is usually in a liquid state, and ultrafine metal particles are produced in such a manner that it precipitates therein. In this case, the ultrafine metal particles may be collected according to a normal solid-liquid separation method such as filtration or centrifugation, and washed with water, a solvent or the like as necessary. Further, the ultrafine metal particles may be naturally dried or forcedly dried as necessary.
本発明の金属超微粒子は、中心部とその周囲の保護層から構成される金属超微粒子であって、中心部が金属成分からなり、保護層が有機成分からなることを特徴とする。 The ultrafine metal particles of the present invention are ultrafine metal particles composed of a central portion and a protective layer around the central portion, wherein the central portion is composed of a metal component, and the protective layer is composed of an organic component.
金属超微粒子の保護層を構成する有機成分は、本発明の製造方法により製造される場合には、通常は出発原料の対カチオンてある４級アンモニウム塩に由来の炭化水素基成分を含有する。但し、有機硫黄系配位子の由来する成分が含まれていても差し支えない。本発明では、特に、炭素数１〜２０アルキル基成分が含まれていることが好ましい。 When the organic component constituting the protective layer of metal ultrafine particles is produced by the production method of the present invention, it usually contains a hydrocarbon group component derived from a quaternary ammonium salt as a counter cation of the starting material. However, a component derived from an organic sulfur-based ligand may be included. In this invention, it is preferable that a C1-C20 alkyl group component is contained especially.
本発明の金属超微粒子の金属成分としては特に限定されず、通常は遷移金属（好ましくはＡｕ、Ｐｔ、Ｃｕ、Ｎｉ又はＰｄ）のいずれかを適用できる。本発明の製造方法により製造される場合には、出発原料として用いる４級アンモニウム塩型金属錯体化合物の中心金属に由来する金属成分が存在する。 The metal component of the ultrafine metal particles of the present invention is not particularly limited, and usually any of transition metals (preferably Au, Pt, Cu, Ni or Pd) can be applied. When manufactured by the manufacturing method of this invention, the metal component derived from the central metal of the quaternary ammonium salt type metal complex compound used as a starting material exists.
金属成分の含有量は、最終製品の用途、出発原料の種類等により適宜変更できるが、通常は８０重量％以上（好ましくは８０〜９５重量％、より好ましくは８０〜９０重量％）とすれば良い。 The content of the metal component can be appropriately changed depending on the use of the final product, the kind of the starting material, etc., but is usually 80% by weight or more (preferably 80 to 95% by weight, more preferably 80 to 90% by weight) good.
本発明の金属超微粒子の平均粒径は特に限定されず、通常は１００ｎｍ以下（数１０〜数ｎｍ）の範囲内で最終製品の用途・使用目的等に応じて適宜設定できる。特に、本発明では、平均粒径５０ｎｍ以下の金属超微粒子を製造することもできる。金属超微粒子の形態も特に限定されず、球状、多角形状、フレーク状、柱状等のいずれであっても良いが、通常は球状又はそれに近い形状であることが好ましい。 The average particle diameter of the ultrafine metal particles of the present invention is not particularly limited, and can be appropriately set within the range of 100 nm or less (several tens to several nm), depending on the use / purpose of use of the final product. In particular, in the present invention, ultrafine metal particles having an average particle size of 50 nm or less can also be produced. The form of the ultrafine metal particles is not particularly limited, and may be any of a spherical shape, a polygonal shape, a flake shape, a columnar shape, and the like, but usually a spherical shape or a shape close thereto is preferable.
本発明の金属超微粒子は、例えば本発明の上記製造方法によってより効率良くかつ確実に製造することができる。すなわち、本発明の金属超微粒子は、上記製造方法によって製造されるものであることが特に好ましい。 The ultrafine metal particles of the present invention can be produced more efficiently and reliably by, for example, the production method of the present invention. That is, it is particularly preferable that the ultrafine metal particles of the present invention are produced by the above production method.
本発明の金属超微粒子は、金属膜形成用、装飾用、触媒用等のあらゆる分野での利用が可能である。特に、金属膜成形用材料（具体的には、電子回路、電極等の電子材料用、その他装飾用）として最適である。その使用形態は特に限定的でないが、本発明の金属超微粒子はそのままでも用いることができ、また必要に応じて溶剤に分散させて用いることもできる。また、本発明の効果を妨げない範囲内で、樹脂成分、溶剤等と混練してペースト化することも可能である。上記材料中における金属超微粒子の含有量は、用いる金属超微粒子の種類、最終製品の用途等に応じて適宜決定すれば良い。 The ultrafine metal particles of the present invention can be used in various fields such as metal film formation, decoration, and catalyst. In particular, it is optimal as a metal film forming material (specifically, for electronic materials such as electronic circuits and electrodes, and for other decorations). The form of use is not particularly limited, but the ultrafine metal particles of the present invention can be used as they are, and can be used by dispersing in a solvent as required. Moreover, it is also possible to knead with a resin component, a solvent, etc. within the range which does not prevent the effect of this invention. What is necessary is just to determine suitably content of the metal ultrafine particle in the said material according to the kind of metal ultrafine particle to be used, the use of a final product, etc.
このように、本発明の金属膜成形用材料は本発明の金属超微粒子を含むものである。この材料は、実質的にあらゆる基材に適用できる。例えば、プラスチック、セラミックス、ガラス、紙類、金属等に適用可能である。特に、本発明材料は、比較的低温で金属膜を形成することができるので、耐熱性の低いプラスチック等に好適である。基材に適用する際には、公知の電子回路、電極等の形成方法に従って塗布、乾燥、焼成等を行えば良く、これによって所望の金属膜を得ることができる。 Thus, the metal film forming material of the present invention contains the ultrafine metal particles of the present invention. This material can be applied to virtually any substrate. For example, it can be applied to plastics, ceramics, glass, papers, metals, and the like. In particular, the material of the present invention can form a metal film at a relatively low temperature, and therefore is suitable for plastics having low heat resistance. When applied to a substrate, it may be applied, dried, fired, etc. according to a known method for forming electronic circuits, electrodes and the like, whereby a desired metal film can be obtained.
以下に実施例を示し、本発明の特徴をより一層明確にする。本発明は、これら実施例の範囲に限定されるものではない。 Examples are given below to further clarify the features of the present invention. The present invention is not limited to the scope of these examples.
製造例１
前駆体として［Ｃ14Ｈ29Ｎ（ＣＨ3）3］［Ａｕ（ＳＣ12Ｈ25）2］の合成を行った。
Production Example 1
[C 14 H 29 N (CH 3 ) 3 ] [Au (SC 12 H 25 ) 2 ] was synthesized as a precursor.
塩化金酸ＨＡｕＣｌ4・４Ｈ2Ｏ（３．９４ｇ、９．５６ｍｍｏｌ）のメタノール溶液（３０ｃｍ3）に、ミリスチルトリメチルアンモニウムブロミド［Ｃ14Ｈ29Ｎ（ＣＨ3）3］Ｂｒ（３．２２ｇ、９．５７ｍｍｏｌ）のメタノール溶液（３０ｃｍ3）を滴下により加え、３時間攪拌した。その後、メタノールを減圧下で除き、濃縮し、蒸留水（３０ｃｍ3）を加えた後、桐山ロートでろ過し、蒸留水（３０ｃｍ3）、続いてメタノール（１５ｃｍ3）で洗浄し、減圧下で乾燥させて［Ｃ12Ｈ25Ｎ（ＣＨ3）3］「ＡｕＣｌ4」を得た。これにメタノール（４０ｃｍ3）を加えて懸濁液とし、１−ドデカンチオールＣ12Ｈ25ＳＨ（７．７４ｇ、３８．２ｍｍｏｌ）とナトリウムメチラートＣＨ3ＯＮａ（２．０７ｇ、３８．２ｍｍｏｌ）を含むメタノール溶液（３０ｃｍ3）を室温で滴下しながら加えて反応させた。１３時間の攪拌後、生じた黄白色の沈殿を桐山ロートでろ別し、蒸留水で２回（３０ｃｍ3×２）、続いてメタノールで２回（３０ｃｍ3×２）、さらにジエチルエーテルで３回（３０ｃｍ3×３）洗浄し、減圧下で乾燥させ、下記の物性をもつ標記前駆体を得た。 To a methanol solution (30 cm 3 ) of chloroauric acid HAuCl 4 .4H 2 O (3.94 g, 9.56 mmol) was added myristyltrimethylammonium bromide [C 14 H 29 N (CH 3 ) 3 ] Br (3.22 g, 9 .57 mmol) in methanol (30 cm 3 ) was added dropwise and stirred for 3 hours. Thereafter, the methanol was removed under reduced pressure, concentrated, distilled water (30 cm 3 ) was added, filtered through a Kiriyama funnel, washed with distilled water (30 cm 3 ), and then methanol (15 cm 3 ). It was dried to obtain [C 12 H 25 N (CH 3 ) 3 ] “AuCl 4 ”. Methanol (40 cm 3 ) was added to form a suspension, and 1-dodecanethiol C 12 H 25 SH (7.74 g, 38.2 mmol) and sodium methylate CH 3 ONa (2.07 g, 38.2 mmol) were added. The methanol solution containing (30 cm 3 ) was added dropwise at room temperature to react. After stirring for 13 hours, the resulting yellowish white precipitate was filtered off with a Kiriyama funnel, twice with distilled water (30 cm 3 × 2), then twice with methanol (30 cm 3 × 2) and three times with diethyl ether. It was washed (30 cm 3 × 3) and dried under reduced pressure to obtain the title precursor having the following physical properties.
［Ｃ14Ｈ29Ｎ（ＣＨ3）3］［Ａｕ（ＳＣ12Ｈ25）2］
収量：７．１９ｇ
収率：８７．９％
融点：９７．５〜９９．５℃
Ｃ41Ｈ88ＮＳ2Ａｕ：計算値Ｃ，５７．５１％；Ｈ，１０．３６％；Ｎ，１．６４％、実測値Ｃ，５７．４９％；Ｈ，９．９５％；Ｎ，１．９１％
1Ｈ−ＮＭＲ：δ＝０．８８（ｔ，９Ｈ，ＣＨ 3ＣＨ2）、１．２４〜１．２６（ｍ，５２Ｈ，ＣＨ3ＣＨ 2ＣＨ 2ＣＨ2）、１．３９〜１．３２（ｍ、６Ｈ，ＮＣＨ2ＣＨ2ＣＨ 2ＣＨ2，ＳＣＨ2ＣＨ2ＣＨ 2ＣＨ2）、１．６６（ｐ，４Ｈ，ＳＣＨ2ＣＨ 2ＣＨ2）、１．７８（ｐ，２Ｈ，ＮＣＨ2ＣＨ 2ＣＨ2）、２．７６（ｔ，４Ｈ，ＳＣＨ 2ＣＨ2）、３．４０（ｓ，９Ｈ，ＮＣＨ 3）、３．５４〜３．６２（ｍ，２Ｈ，ＮＣＨ 2ＣＨ2）（なお、ＮＭＲスペクトル測定は、重クロロホルム（ＣＤＣｌ3）を溶媒とし、内部基準としてテトラメチルシランを用いた。以下同じ。）
製造例２
前駆体［Ｃ12Ｈ25Ｎ（ＣＨ3）3］［Ａｕ（ＳＣ12Ｈ25）2］の合成は、実施例１と同様にして［Ｃ12Ｈ25Ｎ（ＣＨ3）3］［ＡｕＣｌ4］のメタノール懸濁液を調製し、これに１−ドデカンチオールとナトリウムメチラートを含むメタノール溶液を反応させて合成した。
［Ｃ12Ｈ25Ｎ（ＣＨ3）3］［Ａｕ（ＳＣ12Ｈ25）2］
収量：７．１９ｇ
収率：９０．８％
融点：９６．４〜９８．２℃
Ｃ39Ｈ84ＮＳ2Ａｕ：計算値Ｃ，５６．５６％；Ｈ，１０．２２％；Ｎ，１．６９％、実測値Ｃ，５５．０１％；Ｈ，９．９２％；Ｎ，１．９１％
1Ｈ−ＮＭＲ：δ＝０．８８（ｔ，９Ｈ，ＣＨ 3ＣＨ2）、１．２４〜１．２７（ｍ，４８Ｈ，ＣＨ3ＣＨ 2ＣＨ 2ＣＨ2）、１．３２〜１．３９（ｍ、６Ｈ，ＮＣＨ2ＣＨ2ＣＨ 2ＣＨ2，ＳＣＨ2ＣＨ2ＣＨ 2ＣＨ2）、１．６７（ｐ，４Ｈ，ＳＣＨ2ＣＨ 2ＣＨ2）、１．７９（ｐ，２Ｈ，ＮＣＨ2ＣＨ 2ＣＨ2）、２．７６（ｔ，４Ｈ，ＳＣＨ 2ＣＨ2）、３．４１（ｓ，９Ｈ，ＮＣＨ 3）、３．５３〜３．６０（ｍ，２Ｈ，ＮＣＨ 2ＣＨ2）
製造例３
前駆体［（Ｃ18Ｈ37）2Ｎ（ＣＨ3）2］［Ａｕ（ＳＣ12Ｈ25）2］の合成は、実施例１と同様にして［（Ｃ18Ｈ37）2Ｎ（ＣＨ3）2］［ＡｕＣｌ4］のメタノール懸濁液を調製し、これに１−ドデカンオールとナトリウムメチラートを含むメタノール溶液を反応させて合成した。
[C 14 H 29 N (CH 3 ) 3 ] [Au (SC 12 H 25 ) 2 ]
Yield: 7.19g
Yield: 87.9%
Melting point: 97.5-99.5 ° C
C 41 H 88 NS 2 Au: Calculated value C, 57.51%; H, 10.36%; N, 1.64%, measured value C, 57.49%; H, 9.95%; N, 1 .91%
1 H-NMR: δ = 0.88 (t, 9H,
Production Example 2
The precursor [C 12 H 25 N (CH 3 ) 3 ] [Au (SC 12 H 25 ) 2 ] was synthesized in the same manner as in Example 1 [C 12 H 25 N (CH 3 ) 3 ] [AuCl 4 ]. A methanol suspension was prepared and reacted with a methanol solution containing 1-dodecanethiol and sodium methylate.
[C 12 H 25 N (CH 3) 3] [Au (SC 12 H 25) 2]
Yield: 7.19g
Yield: 90.8%
Melting point: 96.4-98.2 ° C
C 39 H 84 NS 2 Au: Calculated value C, 56.56%; H, 10.22%; N, 1.69%, measured value C, 55.01%; H, 9.92%; N, 1 .91%
1 H-NMR: δ = 0.88 (t, 9H,
Production Example 3
The precursor [(C 18 H 37 ) 2 N (CH 3 ) 2 ] [Au (SC 12 H 25 ) 2 ] was synthesized in the same manner as in Example 1 [(C 18 H 37 ) 2 N (CH 3 2 ) [AuCl 4 ] methanol suspension was prepared, and this was synthesized by reacting methanol solution containing 1-dodecanol and sodium methylate.
［（Ｃ18Ｈ37）2Ｎ（ＣＨ3）3］［Ａｕ（ＳＣ12Ｈ25）2］
収量：８．８０
収率：７４．２％
融点：８６．０〜９１．０℃
Ｃ62Ｈ130ＮＳ2Ａｕ：計算値Ｃ，６４．７１％；Ｈ，１１．３９％；Ｎ，１．２２％、実測値Ｃ，６３．２２％；Ｈ，１１．２３％；Ｎ，１．５３％
1Ｈ−ＮＭＲ：δ＝０．８８（ｔ，１２Ｈ，ＣＨ 3ＣＨ2）、１．２４〜１．３５（ｍ，８８Ｈ，ＣＨ3ＣＨ 2ＣＨ 2ＣＨ2）、１．３５〜１．３８（ｍ、８Ｈ，ＮＣＨ2ＣＨ2ＣＨ 2ＣＨ2，ＳＣＨ2ＣＨ2ＣＨ 2ＣＨ2）、１．６４〜１．７５（ｍ，８Ｈ，ＮＣＨ2ＣＨ 2ＣＨ2，ＳＣＨ2ＣＨ 2ＣＨ2）、２．７６（ｔ，４Ｈ，ＳＣＨ 2ＣＨ2）、３．３２（ｓ，６Ｈ，ＮＣＨ 3）、３．４５〜３．５２（ｍ，４Ｈ，ＮＣＨ 2ＣＨ2）
実施例１
製造例１で得られた前駆体［Ｃ14Ｈ29Ｎ（ＣＨ3）3］［Ａｕ（ＳＣ12Ｈ25）2］の還元的脱離反応による金超微粒子の製造を行った。
[(C 18 H 37 ) 2 N (CH 3 ) 3 ] [Au (SC 12 H 25 ) 2 ]
Yield: 8.80
Yield: 74.2%
Melting point: 86.0-91.0 ° C
C 62 H 130 NS 2 Au: calculated value C, 64.71%; H, 11.39%; N, 1.22%, measured value C, 63.22%; H, 11.23%; N, 1 .53%
1 H-NMR: δ = 0.88 (t, 12H,
Example 1
Gold ultrafine particles were produced by the reductive elimination reaction of the precursor [C 14 H 29 N (CH 3 ) 3 ] [Au (SC 12 H 25 ) 2 ] obtained in Production Example 1.
［Ｃ14Ｈ29Ｎ（ＣＨ3）3］［Ａｕ（ＳＣ12Ｈ25）2］（７．７４ｇ、９．０４ｍｍｏｌ）をパイレックス製三ツ口フラスコにとり、油浴により１３０℃まで加熱して完全に融解させた後、１６０℃まで徐々に加熱した。その後、１６０℃で９時間反応を持続させた後、放冷した。生成した褐色の粉末を液状のジスルフィド（ＳＣ12Ｈ25）2を分離し、エタノールで２回（３０ｃｍ3×２）で洗浄し、桐山ロートでろ別し、減圧下で乾燥させ、褐色の金超微粒子を得た。得られた金超微粒子の透過型電子顕微鏡（ＴＥＭ）により観察し、その観察結果に基づいて粒度分布を求めた。得られた金超微粒子の粒度分布を図１に示す。 [C 14 H 29 N (CH 3 ) 3 ] [Au (SC 12 H 25 ) 2 ] (7.74 g, 9.04 mmol) is placed in a Pyrex three-necked flask and heated to 130 ° C. in an oil bath to completely melt. And then gradually heated to 160 ° C. Thereafter, the reaction was continued at 160 ° C. for 9 hours and then allowed to cool. The resulting brown powder was separated from liquid disulfide (SC 12 H 25 ) 2 , washed twice with ethanol (30 cm 3 × 2), filtered through a Kiriyama funnel, dried under reduced pressure, Fine particles were obtained. The obtained gold ultrafine particles were observed with a transmission electron microscope (TEM), and the particle size distribution was determined based on the observation results. The particle size distribution of the obtained ultrafine gold particles is shown in FIG.
図１に示すように、４級アンモニウム塩型金属錯体化合物を熱処理（熱分解）することによって、粒径３０〜４０ｎｍの中心分布をもつ金属超微粒子が得られることがわかる。 As shown in FIG. 1, it is understood that ultrafine metal particles having a center distribution with a particle size of 30 to 40 nm can be obtained by heat treatment (thermal decomposition) of the quaternary ammonium salt type metal complex compound.
実施例２
加熱温度１８０℃及び１８０℃での保持時間９時間としたほかは、製造例１で得られた前駆体を用いて実施例１と同様にして金超微粒子の製造を行った。得られた金超微粒子の粒度分布を実施例１と同様にして求めた。その結果を図１に示す。図１の結果からも明らかなように、本発明では、加熱温度及び加熱時間により金属超微粒子の粒径を制御できることもわかる。
Example 2
Ultrafine gold particles were produced in the same manner as in Example 1 using the precursor obtained in Production Example 1 except that the heating temperature was 180 ° C. and the holding time was 9 hours at 180 ° C. The particle size distribution of the obtained ultrafine gold particles was determined in the same manner as in Example 1. The result is shown in FIG. As is clear from the results of FIG. 1, it can be seen that in the present invention, the particle size of the ultrafine metal particles can be controlled by the heating temperature and the heating time.
図２には、実施例２で得られた金超微粒子を透過型電子顕微鏡により観察した結果（ＴＥＭ像）を示す。図２によれば、約５０ｎｍ以下の粒径をもつほぼ球状の金超微粒子が生成していることがわかる。 In FIG. 2, the result (TEM image) which observed the gold | metal | money ultrafine particle obtained in Example 2 with the transmission electron microscope is shown. According to FIG. 2, it can be seen that substantially spherical ultrafine gold particles having a particle size of about 50 nm or less are generated.
実施例３
製造例２で得られた前駆体［Ｃ12Ｈ25Ｎ（ＣＨ3）3］［Ａｕ（ＳＣ12Ｈ25）2］を用い、加熱温度１６０℃及び１６０℃での保持時間７時間としたほかは、実施例１と同様にして金超微粒子の製造を行った。得られた金超微粒子の粒度分布を実施例１と同様にして求めた。その結果を図１に示す。
Example 3
Using the precursor [C 12 H 25 N (CH 3 ) 3 ] [Au (SC 12 H 25 ) 2 ] obtained in Production Example 2, the heating temperature was 160 ° C. and the holding time at 160 ° C. was 7 hours. Produced gold ultrafine particles in the same manner as in Example 1. The particle size distribution of the obtained ultrafine gold particles was determined in the same manner as in Example 1. The result is shown in FIG.
実施例４
製造例３で得られた前駆体［（Ｃ18Ｈ37）2Ｎ（ＣＨ3）2］［Ａｕ（ＳＣ12Ｈ25）2］を用い、加熱温度１７０℃及び１７０℃での保持時間６時間としたほかは、実施例１と同様にして金超微粒子の製造を行った。得られた金超微粒子の粒度分布を実施例１と同様にして求めた。その結果を図１に示す。
Example 4
Using the precursor [(C 18 H 37 ) 2 N (CH 3 ) 2 ] [Au (SC 12 H 25 ) 2 ] obtained in Production Example 3, holding temperatures at 170 ° C. and 170 ° C. for 6 hours Other than the above, ultrafine gold particles were produced in the same manner as in Example 1. The particle size distribution of the obtained ultrafine gold particles was determined in the same manner as in Example 1. The result is shown in FIG.
また、図３には、実施例４で得られた金超微粒子の粉末Ｘ線回折分析を行った結果を示す。 FIG. 3 shows the result of powder X-ray diffraction analysis of the ultrafine gold particles obtained in Example 4.
実施例５
加熱温度を１９０℃及び１９０℃での保持時間６時間としたほかは、製造例３で得られた前駆体を用いて実施例４と同様にして金超微粒子の製造を行った。得られた金超微粒子の粒度分布を実施例１と同様にして求めた。その結果を図１に示す。
Example 5
Gold ultrafine particles were produced in the same manner as in Example 4 using the precursor obtained in Production Example 3, except that the heating temperature was 190 ° C. and the holding time at 190 ° C. was 6 hours. The particle size distribution of the obtained ultrafine gold particles was determined in the same manner as in Example 1. The result is shown in FIG.
Claims (6)
中心部とその周囲の保護層から構成され、中心部が金属成分からなり、保護層が有機成分からなり、有機成分として当該４級アンモニウム塩［Ｒ １ Ｒ ２ Ｒ ３ Ｒ ４ Ｎ］の熱分解により生じるアルキル基の一部又は全部を含むことを特徴とする金属超微粒子。 [R 1 R 2 R 3 R 4 N] x [M y (A) z ] (wherein R 1 to R 4 are the same or different hydrocarbon groups and have a substituent) M is a transition metal, A is an organic sulfur-based ligand, x is an integer greater than 0, y is an integer greater than 0, and z is an integer greater than 0). Ultrafine metal particles obtained by a production method in which an ammonium salt-type metal complex compound is used as a starting material and a central metal is reduced from a reductive elimination reaction of the organic sulfur ligand of the compound,
It consists of a central part and a protective layer around it, the central part is made of a metal component, the protective layer is made of an organic component, and the heat of the quaternary ammonium salt [R 1 R 2 R 3 R 4 N] as the organic component A metal ultrafine particle comprising part or all of an alkyl group generated by decomposition .
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