JP2012147014A - Composition for forming electrode of solar cell and formation method of the electrode, and solar cell using electrode obtained by the formation method - Google Patents

Composition for forming electrode of solar cell and formation method of the electrode, and solar cell using electrode obtained by the formation method Download PDF

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JP2012147014A
JP2012147014A JP2012083491A JP2012083491A JP2012147014A JP 2012147014 A JP2012147014 A JP 2012147014A JP 2012083491 A JP2012083491 A JP 2012083491A JP 2012083491 A JP2012083491 A JP 2012083491A JP 2012147014 A JP2012147014 A JP 2012147014A
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JP5435063B2 (en
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Toshiharu Hayashi
年治 林
Yoshiaki Takada
佳明 高田
Kazuhiko Yamazaki
和彦 山崎
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Mitsubishi Materials Corp
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Abstract

PROBLEM TO BE SOLVED: To obtain an electrode capable of maintaining high conductivity and high reflectance even after use for a long period of time and thus having excellent aging stability, which is formed by using a composition for forming an electrode of a solar cell of the present invention.SOLUTION: The composition for forming an electrode of a solar cell is configured by dispersing, in a dispersion medium, a metal nanoparticle chemically modified with a protective agent comprising 75 wt.% or more of a silver nanoparticle and having a carbon skeleton with an organic molecular main chain having a carbon number of 1 to 3. This metal nanoparticle contains a number average of 70% or more of a metal nanoparticle having a primary particle diameter within the range of 10 to 50 nm. The dispersion medium contains 1 wt.% or more of water and 2 wt.% or more of alcohols; the content of the metal nanoparticle is 2.5 to 95.0 wt.% based on 100 wt.% of the composition comprising the metal nanoparticle and the dispersion medium; and the protective agent contains a hydroxyl group and/or a carbonyl group.

Description

本発明は、太陽電池の電極を形成するための組成物と、この組成物を用いて電極を形成する方法並びにこの形成方法により得られた電極を用いた太陽電池に関するものである。   The present invention relates to a composition for forming an electrode of a solar cell, a method for forming an electrode using the composition, and a solar cell using an electrode obtained by the formation method.

従来、この種の電極の形成方法として、０．０３μｍ以下の粒径の金属超微粒子を１００〜２００程度の低分子量の有機溶媒に分散させた溶液を光電変換半導体層に塗布・焼成することにより下層電極層を形成し、金属超微粒子の含有重量濃度が下層電極層の形成に用いた溶液と同じか或いは下層電極層の形成に用いた溶液より高い濃度の溶液を光電変換半導体層に塗布・焼成することにより上層電極層を形成する太陽電池の金属電極形成方法が開示されている（例えば、特許文献１参照。）。この金属電極形成方法では、金属超微粒子を分散させかつ粘度を１００００ｃｐｓ程度に調整した溶液をスクリーン印刷法等により光電変換半導体層に塗布した後に、１００〜２５０℃、好ましくは２５０℃の温度に３０分以上保持して焼成することにより、金属電極（下層電極層又は上層電極層）を形成する。
このように構成された太陽電池の金属電極形成方法では、金属超微粒子を有機溶媒に分散させた溶液を光電変換半導体層に塗布した後に、１００〜２５０℃の低温で焼結することにより、高真空プロセスを用いずに、高い反射率及び導電率を有しかつ大きな面積の金属電極を得られるようになっている。 Conventionally, as a method for forming this type of electrode, a solution obtained by dispersing ultrafine metal particles having a particle size of 0.03 μm or less in an organic solvent having a low molecular weight of about 100 to 200 is applied to a photoelectric conversion semiconductor layer and fired. Form a lower electrode layer, and apply a solution with a concentration of ultrafine metal particles equal to or higher than the solution used for forming the lower electrode layer to the photoelectric conversion semiconductor layer. A method for forming a metal electrode of a solar cell that forms an upper electrode layer by firing is disclosed (for example, see Patent Document 1). In this metal electrode forming method, a solution in which ultrafine metal particles are dispersed and the viscosity is adjusted to about 10,000 cps is applied to the photoelectric conversion semiconductor layer by a screen printing method or the like, and then the temperature is set to 100 to 250 ° C., preferably 250 ° C. A metal electrode (lower electrode layer or upper electrode layer) is formed by holding and baking for at least a minute.
In the method for forming a metal electrode of a solar cell configured in this way, after applying a solution in which metal ultrafine particles are dispersed in an organic solvent to a photoelectric conversion semiconductor layer, sintering is performed at a low temperature of 100 to 250 ° C. Without using a vacuum process, a metal electrode having a high reflectance and conductivity and a large area can be obtained.

特許第３２８７７５４号（請求項１、段落［００２４］、段落［００３５］）Japanese Patent No. 3287754 (claim 1, paragraph [0024], paragraph [0035])

上記従来の特許文献１に示された太陽電池の金属電極形成方法では、焼成後の金属電極中の金属超微粒子を安定化させるために、所定の導電性を確保しながら金属超微粒子を１００〜２００程度の低分子量の有機物で保護する必要がある。一方、有機溶媒に分散させた金属超微粒子を低温で焼結化させるために、この金属超微粒子のサイズを小さくすると、金属超微粒子の比表面積が増大し、上記有機物の占める割合が大きくなる。このため、上記従来の特許文献１に示された太陽電池の金属電極形成方法では、有機溶媒に分散させた金属超微粒子の低温焼結化は、上記有機物を熱により脱離、或いは分解（分離・燃焼）させなければ実現できず、特に有機溶媒に分散させた金属超微粒子を２２０℃以下で焼成して得られた金属電極について耐候性試験を行うと、具体的には、温度を１００℃に保ちかつ湿度を５０％に保った恒温恒湿槽に金属電極を１０００時間収容すると、上記有機物が変質又は劣化して、導電性及び反射率が低下してしまう問題点があった。
本発明の目的は、長年使用しても高導電率及び高反射率を維持することができ、経年安定性に優れた電極を得ることができる、太陽電池の電極形成用組成物及びその製造方法を提供することにある。
本発明の別の目的は、１３０〜４００℃という低温の焼成プロセスにより、長年使用しても高導電率及び高反射率を維持することができ、経年安定性に優れた電極を得ることができる、太陽電池の電極の形成方法及び該形成方法により得られた電極を用いた太陽電池を提供することにある。 In the conventional method for forming a metal electrode of a solar cell shown in Patent Document 1, in order to stabilize the metal ultrafine particles in the fired metal electrode, the metal ultrafine particles are added in an amount of 100 to 100 while ensuring predetermined conductivity. It is necessary to protect with an organic substance having a low molecular weight of about 200. On the other hand, if the size of the metal ultrafine particles is reduced in order to sinter the metal ultrafine particles dispersed in the organic solvent at a low temperature, the specific surface area of the metal ultrafine particles increases and the proportion of the organic matter increases. For this reason, in the conventional metal electrode forming method for solar cells shown in Patent Document 1, low-temperature sintering of metal ultrafine particles dispersed in an organic solvent is performed by desorbing or decomposing (separating) the organic matter by heat. If the weather resistance test is performed on a metal electrode obtained by firing metal ultrafine particles dispersed in an organic solvent at 220 ° C. or lower, specifically, the temperature is set to 100 ° C. When the metal electrode is housed in a constant temperature and humidity chamber maintained at 50% and humidity of 50% for 1000 hours, the organic matter is altered or deteriorated, resulting in a decrease in conductivity and reflectance.
An object of the present invention is to provide a composition for forming an electrode for a solar cell and a method for producing the same , which can maintain high conductivity and high reflectivity even when used for many years, and can obtain an electrode having excellent aging stability. Is to provide.
Another object of the present invention is that a high-conductivity and high reflectivity can be maintained even when used for many years by a low-temperature baking process of 130 to 400 ° C., and an electrode having excellent aging stability can be obtained. An object of the present invention is to provide a method for forming an electrode of a solar cell and a solar cell using an electrode obtained by the method.

請求項１に係る発明は、金属ナノ粒子が分散媒に分散した太陽電池の電極形成用組成物であって、金属ナノ粒子が７５重量％以上の銀ナノ粒子を含有し、金属ナノ粒子は炭素骨格が炭素数１〜３の有機分子主鎖の保護剤で化学修飾され、金属ナノ粒子が一次粒径１０〜５０ｎｍの範囲内の金属ナノ粒子を数平均で７０％以上含有し、分散媒が１重量％以上の水と２重量％以上のアルコール類とを含有し、金属ナノ粒子の含有量が金属ナノ粒子及び分散媒からなる組成物１００重量％に対して２．５〜９５．０重量％であり、保護剤が水酸基(-OH)又はカルボニル基(-C=O)のいずれか一方又は双方を含有することを特徴とする。
この請求項１に記載された組成物では、一次粒径１０〜５０ｎｍとサイズの比較的大きな金属ナノ粒子を多く含むため、金属ナノ粒子の比表面積が減少し、保護剤の占める割合が小さくなるため、この組成物を用いて太陽電池の電極を形成すると、上記保護剤中の有機分子が焼成時の熱により脱離し又は分解し、或いは離脱しかつ分解することにより、実質的に有機物を含有しない銀を主成分とする電極が得られる。 The invention according to claim 1 is a composition for forming an electrode of a solar cell in which metal nanoparticles are dispersed in a dispersion medium, the metal nanoparticles containing 75% by weight or more of silver nanoparticles, and the metal nanoparticles are carbon. backbone is chemically modified with a protecting agent of the organic molecular main chain of 1 to 3 carbon atoms, metal nano-particles are contained a number average of 70% or more of the metal nanoparticles in the range of primary particle size 10 to 50 nm, dispersion medium 2.5 to 95.0 weight with respect to 100 weight% of composition which contains 1 weight% or more of water and 2 weight% or more of alcohol, and content of metal nanoparticles consists of metal nanoparticles and a dispersion medium. And the protective agent contains one or both of a hydroxyl group (—OH) and a carbonyl group (—C═O) .
In the composition described in claim 1, since it contains a large amount of metal nanoparticles having a primary particle size of 10 to 50 nm and a relatively large size, the specific surface area of the metal nanoparticles is reduced and the proportion of the protective agent is reduced. Therefore, when an electrode of a solar cell is formed using this composition, the organic molecules in the protective agent are desorbed or decomposed by the heat at the time of baking, or are separated and decomposed to substantially contain organic matter. An electrode mainly composed of silver is obtained.

請求項２に係る発明は、請求項１に係る発明であって、金属ナノ粒子が前記銀ナノ粒子以外に更にＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ及びＭｎからなる群より選ばれた１種又は２種以上の混合組成又は合金組成からなる金属ナノ粒子を２重量％以上かつ２５重量％未満含有する。The invention according to claim 2 is the invention according to claim 1, wherein the metal nanoparticles are further Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr in addition to the silver nanoparticles. And metal nanoparticles composed of one or two or more mixed compositions or alloy compositions selected from the group consisting of Mn and 2 wt% or more and less than 25 wt%.

請求項３に係る発明は、請求項１に係る発明であって、アルコール類がメタノール、エタノール、プロパノール、ブタノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、イソボニルヘキサノール、グリセロール及びエリトリトールからなる群より選ばれた１種又は２種以上である。The invention according to claim 3 is the invention according to claim 1, wherein the alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, isobornyl hexanol, glycerol and erythritol. 1 type or 2 types or more.

請求項４に係る発明は、硝酸銀を水に溶解して第１金属塩水溶液を調製する工程と、濃度１０〜４０％のクエン酸ナトリウム、りんご酸ナトリウム又はグリコール酸ナトリウムの水溶液に不活性ガスの気流中で粒状又は粉状の硫酸第一鉄を加えて溶解させて還元剤水溶液を調製する工程と、前記不活性ガス気流中で前記還元剤水溶液を撹拌しながら、前記還元剤水溶液の量の１／１０以下の割合で反応温度が３０〜６０℃に保持されるように室温の前記第１金属塩水溶液を前記還元剤水溶液に滴下して混合する工程と、前記混合液の撹拌を更に１０〜３００分間続けて銀コロイドからなる第１分散液を調製する工程と、前記第１分散液を室温で放置することにより沈降した銀ナノ粒子の凝集物をデカンテーション又は遠心分離法により分離する工程と、前記第１分散液から分離した固形分に水を加えて第１分散体の前駆体を得る工程と、前記第１分散体の前駆体を限外ろ過により脱塩処理する工程と、前記脱塩処理した第１分散体の前駆体をアルコール類で置換洗浄して銀の含有量を２．５〜５０重量％に調整する工程と、前記アルコール類で置換洗浄した第１分散体の前駆体を遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより全ての銀粒子１００％に対する一次粒径１０〜５０ｎｍの範囲内の銀ナノ粒子を数平均で７０％以上含有する第１分散体からなる太陽電池の電極形成用組成物を得る工程とを含むことを特徴とする請求項１に記載された太陽電池の電極形成用組成物を製造する方法である。According to a fourth aspect of the present invention, there is provided a step of preparing a first metal salt aqueous solution by dissolving silver nitrate in water, and an inert gas in an aqueous solution of sodium citrate, sodium malate or sodium glycolate having a concentration of 10 to 40%. The step of preparing a reducing agent aqueous solution by adding granular or powdered ferrous sulfate in an air stream and dissolving it, and stirring the reducing agent aqueous solution in the inert gas stream, the amount of the reducing agent aqueous solution The step of dropping the first metal salt aqueous solution at room temperature into the reducing agent aqueous solution and mixing so that the reaction temperature is maintained at 30 to 60 ° C. at a ratio of 1/10 or less, and stirring of the mixed solution is further performed by 10 A step of preparing a first dispersion composed of colloidal silver for ˜300 minutes, and agglomeration of silver nanoparticles precipitated by leaving the first dispersion at room temperature is separated by decantation or centrifugation A step of adding water to the solid content separated from the first dispersion to obtain a precursor of the first dispersion, a step of desalting the precursor of the first dispersion by ultrafiltration, A step of substituting and washing the precursor of the first dispersion subjected to the desalting treatment with an alcohol to adjust the silver content to 2.5 to 50% by weight; and a step of substituting and washing the first dispersion with the alcohol. By using a centrifuge as a precursor and adjusting the centrifugal force of the centrifuge to separate coarse particles, silver nanoparticles in the range of primary particle size of 10 to 50 nm with respect to 100% of all silver particles are averaged. A method for producing a composition for forming an electrode for a solar cell according to claim 1, comprising obtaining a composition for electrode formation for a solar cell comprising a first dispersion containing 70% or more. is there.

請求項５に係る発明は、塩化金酸、塩化白金酸、硝酸パラジウム、三塩化ルテニウム、塩化ニッケル、硝酸第一銅、二塩化錫、硝酸インジウム、塩化亜鉛、硫酸鉄、硫酸クロム又は硫酸マンガンを水に溶解して第２金属塩水溶液を調製する工程と、濃度１０〜４０％のクエン酸ナトリウム、りんご酸ナトリウム又はグリコール酸ナトリウムの水溶液に不活性ガスの気流中で粒状又は粉状の硫酸第一鉄を加えて溶解させて還元剤水溶液を調製する工程と、前記不活性ガス気流中で前記還元剤水溶液を撹拌しながら、前記還元剤水溶液の量の１／１０以下の割合で反応温度が３０〜６０℃に保持されるように室温の前記第２金属塩水溶液を前記還元剤水溶液に滴下して混合する工程と、前記混合液の撹拌を更に１０〜３００分間続けてＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ又はＭｎの金属コロイドからなる第２分散液を調製する工程と、前記第２分散液を室温で放置することにより沈降したＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ又はＭｎの金属ナノ粒子の凝集物をデカンテーション又は遠心分離法により分離する工程と、前記第２分散液から分離した固形分に水を加えて第２分散体の前駆体を得る工程と、前記第２分散体の前駆体を限外ろ過により脱塩処理する工程と、前記脱塩処理した前記第２分散体の前駆体をアルコール類で置換洗浄してＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ又はＭｎの含有量を２．５〜５０重量％に調整する工程と、前記アルコール類で置換洗浄した第２分散体の前駆体を遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより全てのＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ又はＭｎの金属ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの範囲内のＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ又はＭｎの金属ナノ粒子を数平均で７０％以上含有する第２分散体を得る工程と、請求項４に記載された７５重量％以上の前記第１分散体と２重量％以上かつ２５重量％未満の前記第２分散体とを前記第１及び第２分散体の合計含有量が１００重量％となるように混合することにより太陽電池の電極形成用組成物を得る工程とを含むことを特徴とする請求項２に記載された太陽電池の電極形成用組成物を製造する方法である。The invention according to claim 5 includes chloroauric acid, chloroplatinic acid, palladium nitrate, ruthenium trichloride, nickel chloride, cuprous nitrate, tin dichloride, indium nitrate, zinc chloride, iron sulfate, chromium sulfate or manganese sulfate. A step of preparing an aqueous solution of the second metal salt by dissolving in water; and an aqueous solution of sodium citrate, sodium malate, or sodium glycolate having a concentration of 10 to 40% in the form of granular or powdered sulfuric acid in an inert gas stream A step of preparing a reducing agent aqueous solution by adding and dissolving ferrous iron, while stirring the reducing agent aqueous solution in the inert gas stream, the reaction temperature is 1/10 or less of the amount of the reducing agent aqueous solution. A step of dropping and mixing the second metal salt aqueous solution at room temperature to the reducing agent aqueous solution so as to be maintained at 30 to 60 ° C., and stirring the mixed solution for another 10 to 300 minutes, Au, Pt A step of preparing a second dispersion composed of a metal colloid of Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr, or Mn; and Au precipitated by leaving the second dispersion at room temperature. A step of separating agglomerates of metal nanoparticles of Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr or Mn by decantation or centrifugation, and a solid separated from the second dispersion A step of adding water to the mixture to obtain a precursor of the second dispersion, a step of desalting the precursor of the second dispersion by ultrafiltration, and a precursor of the desalted second dispersion Replacing the body with alcohols and adjusting the content of Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr or Mn to 2.5 to 50% by weight; and Dispersion-dispersed second dispersion with alcohols All the Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr or the like by separating the coarse particles by adjusting the centrifugal force of the centrifuge using a centrifuge The number average of metal nanoparticles of Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr, or Mn within a range of primary particle size of 10 to 50 nm with respect to 100% of Mn metal nanoparticles is 70. % Of the second dispersion containing 75% by weight or more, and 75% by weight or more of the first dispersion described in claim 4 and 2% by weight or more and less than 25% by weight of the second dispersion. And a step of obtaining a composition for forming an electrode of a solar cell by mixing so that the total content of the first and second dispersions is 100% by weight. It is a method for producing a composition for electrode formation .

請求項６に係る発明は、請求項１ないし３いずれか１項に記載の電極形成用組成物を基材上に湿式塗工法で塗工して太陽電池用電極を形成する方法である。The invention according to claim 6 is a method of forming an electrode for a solar cell by applying the electrode forming composition according to any one of claims 1 to 3 on a substrate by a wet coating method.

請求項７に係る発明は、請求項１ないし３いずれか１項に記載の電極形成用組成物を基材上に湿式塗工法で塗工して焼成後の厚さが０．１〜２．０μｍの範囲内となるように成膜する工程と、上面に成膜された基材を１３０〜４００℃で焼成する工程とを含む太陽電池の電極の形成方法である。
この請求項７に記載された太陽電池の電極の形成方法では、１３０〜４００℃という低温での焼成により、金属ナノ粒子の表面を保護していた保護剤中の有機分子が脱離し又は分解し、或いは離脱しかつ分解することにより、実質的に有機物を含有しない銀を主成分とする電極が得られる。 In the invention according to claim 7, the electrode-forming composition according to any one of claims 1 to 3 is coated on a substrate by a wet coating method, and the thickness after firing is 0.1 to 2. This is a method for forming an electrode of a solar cell, which includes a step of forming a film so as to be in the range of 0 μm and a step of baking the base material formed on the upper surface at 130 to 400 ° C.
In the method for forming an electrode of a solar cell described in claim 7, organic molecules in the protective agent that protected the surface of the metal nanoparticles were desorbed or decomposed by firing at a low temperature of 130 to 400 ° C. Alternatively, by separating and decomposing, an electrode containing silver as a main component and containing substantially no organic substance can be obtained.

請求項８に係る発明は、請求項６又は７に係る発明であって、基材がシリコン、ガラス、透明導電材料を含むセラミックス、高分子材料又は金属からなる基板のいずれか、或いは前記シリコン、前記ガラス、前記透明導電材料を含むセラミックス、前記高分子材料及び前記金属からなる群より選ばれた２種以上の積層体である。The invention according to claim 8 is the invention according to claim 6 or 7, wherein the substrate is made of silicon, glass, ceramics containing a transparent conductive material, a polymer material or a substrate made of metal, or the silicon, Two or more types of laminates selected from the group consisting of the glass, ceramics including the transparent conductive material, the polymer material, and the metal.

請求項９に係る発明は、請求項６又は７に係る発明であって、基材が太陽電池素子又は透明電極付き太陽電池素子のいずれかである。The invention according to claim 9 is the invention according to claim 6 or 7, wherein the substrate is either a solar cell element or a solar cell element with a transparent electrode.

請求項１０に係る発明は、請求項６又は７に係る発明であって、湿式塗工法がスプレーコーティング法、ディスペンサコーティング法、スピンコーティング法、ナイフコーティング法、スリットコーティング法、インクジェットコーティング法、スクリーン印刷法、オフセット印刷法又はダイコーティング法のいずれかである。The invention according to claim 10 is the invention according to claim 6 or 7, wherein the wet coating method is spray coating method, dispenser coating method, spin coating method, knife coating method, slit coating method, ink jet coating method, screen printing. Method, offset printing method or die coating method.

請求項１１に係る発明は、請求項６ないし１０いずれか１項に記載の電極の形成方法により形成した電極を用いたことを特徴とする太陽電池である。The invention according to claim 11 is a solar cell using the electrode formed by the method for forming an electrode according to any one of claims 6 to 10.

以上述べたように、本発明によれば、分散媒に分散された金属ナノ粒子が７５重量％以上の銀ナノ粒子を含有し、炭素骨格が炭素数１〜３の有機分子主鎖の保護剤で金属ナノ粒子を化学修飾し、更に金属ナノ粒子が一次粒径１０〜５０ｎｍの範囲内の金属ナノ粒子を数平均で７０％以上含有するので、この組成物中の金属ナノ粒子の比表面積が比較的減少し、保護剤の占める割合が小さくなる。この結果、この組成物を用いて太陽電池の電極を形成すると、上記保護剤中の有機分子が焼成時の熱により脱離し又は分解し、或いは離脱しかつ分解することにより、実質的に有機物を含有しない銀を主成分とする電極が得られる。従って、上記電極の形成された太陽電池を長年使用しても、有機物が変質又は劣化するということがなく、導電率及び反射率が高い状態に維持されるので、経年安定性に優れた電極を得ることができる。
また上記電極形成用組成物を基材上に湿式塗工法で塗工して焼成後の厚さが０．１〜２．０μｍの範囲内となるように成膜し、この上面に成膜された基材を１３０〜４００℃で焼成すれば、金属ナノ粒子の表面を保護していた保護剤中の有機分子が脱離し又は分解し、或いは離脱しかつ分解することにより、実質的に有機物を含有しない銀を主成分とする電極が得られる。この結果、上記と同様に、電極の形成された太陽電池を長年使用しても、導電率及び反射率が高い状態に維持されるので、経年安定性に優れた電極を得ることができる。 As described above, according to the present invention, the metal nanoparticles dispersed in the dispersion medium contain 75% by weight or more of silver nanoparticles, and the protective agent for the organic molecular main chain having a carbon skeleton of 1 to 3 carbon atoms. The metal nanoparticles are chemically modified with a metal nanoparticle containing 70% or more of the average number of metal nanoparticles having a primary particle size of 10 to 50 nm. Therefore, the specific surface area of the metal nanoparticles in this composition is Reducing relatively, the proportion of protective agent becomes smaller. As a result, when an electrode of a solar cell is formed using this composition, the organic molecules in the protective agent are desorbed or decomposed by the heat at the time of firing, or desorbed and decomposed, thereby substantially reducing the organic matter. An electrode composed mainly of silver not containing is obtained. Therefore, even if the solar cell on which the electrode is formed is used for many years, the organic matter is not deteriorated or deteriorated, and the electrical conductivity and the reflectance are maintained in a high state. Can be obtained.
In addition, the electrode forming composition is applied onto a substrate by a wet coating method, and a film is formed so that the thickness after firing is within a range of 0.1 to 2.0 μm, and the film is formed on this upper surface. If the base material is baked at 130 to 400 ° C., the organic molecules in the protective agent that protected the surface of the metal nanoparticles are detached or decomposed, or separated and decomposed, so that the organic matter is substantially removed. An electrode composed mainly of silver not containing is obtained. As a result, similarly to the above, even if the solar cell on which the electrode is formed is used for many years, the conductivity and the reflectance are maintained at a high level, so that an electrode having excellent aging stability can be obtained.

次に本発明を実施するための最良の形態を説明する。
本発明の組成物は、金属ナノ粒子が分散媒に分散した太陽電池の電極形成用組成物である。上記金属ナノ粒子は７５重量％以上、好ましくは８０重量％以上の銀ナノ粒子を含有する。また金属ナノ粒子は炭素骨格が炭素数１〜３の有機分子主鎖の保護剤で化学修飾される。更に金属ナノ粒子は一次粒径１０〜５０ｎｍの範囲内の金属ナノ粒子を数平均で７０％以上、好ましくは７５％以上含有する。ここで、銀ナノ粒子の含有量を全ての金属ナノ粒子１００重量％に対して７５重量％以上の範囲に限定したのは、７５重量％未満ではこの組成物を用いて形成された太陽電池の電極の反射率が低下してしまうからである。また金属ナノ粒子を化学修飾する保護剤の有機分子主鎖の炭素骨格の炭素数を１〜３の範囲に限定したのは、炭素数が４以上であると焼成時の熱により保護剤が脱離或いは分解（分離・燃焼）し難く、上記電極内に有機残渣が多く残り、変質又は劣化して電極の導電性及び反射率が低下してしまうからである。また一次粒径１０〜５０ｎｍの範囲内の金属ナノ粒子の含有量を、数平均で全ての金属ナノ粒子１００％に対して７０％以上の範囲に限定したのは、７０％未満では金属ナノ粒子の比表面積が増大して有機物の占める割合が大きくなり、焼成時の熱により脱離或いは分解（分離・燃焼）し易い有機分子であっても、この有機分子の占める割合が多いため、電極内に有機残渣が多く残り、この残渣が変質又は劣化して電極の導電性及び反射率が低下したり、或いは金属ナノ粒子の粒度分布が広くなり電極の密度が低下し易くなって、電極の導電性及び反射率が低下してしまうからである。更に上記金属ナノ粒子の一次粒径を１０〜５０ｎｍの範囲内に限定したのは、統計的手法より一次粒径が１０〜５０ｎｍの範囲内にある金属ナノ粒子が経時安定性（経年安定性）と相関しているからである。 Next, the best mode for carrying out the present invention will be described.
The composition of the present invention is a composition for forming an electrode of a solar cell in which metal nanoparticles are dispersed in a dispersion medium. The metal nanoparticles contain 75% by weight or more, preferably 80% by weight or more of silver nanoparticles. The metal nanoparticles are chemically modified with a protective agent having an organic molecular main chain having a carbon skeleton of 1 to 3 carbon atoms. Further, the metal nanoparticles contain 70% or more, preferably 75% or more of metal nanoparticles having a primary particle size in the range of 10 to 50 nm in terms of number average. Here, the content of silver nanoparticles was limited to a range of 75% by weight or more with respect to 100% by weight of all metal nanoparticles, and less than 75% by weight of solar cells formed using this composition. This is because the reflectance of the electrode is lowered. Moreover, the carbon number of the carbon skeleton of the organic molecular main chain of the protective agent for chemically modifying the metal nanoparticles was limited to the range of 1 to 3 because the protective agent was removed by the heat during firing if the carbon number was 4 or more. This is because separation or decomposition (separation / combustion) is difficult, and a large amount of organic residue remains in the electrode, resulting in alteration or deterioration, resulting in a decrease in the conductivity and reflectance of the electrode. The content of the metal nanoparticles in the range of primary particle diameter of 10 to 50 nm, was limited to a range of 70% or more relative to 100% all the metal nanoparticles by the number average, metal nano in less than 7 0% The specific surface area of the particles increases and the proportion of organic matter increases, and even if the organic molecule is easily desorbed or decomposed (separated or burned) by the heat during firing, the proportion of this organic molecule is large. A large amount of organic residue remains inside, and the residue is altered or deteriorated to reduce the conductivity and reflectance of the electrode, or the particle size distribution of the metal nanoparticles is widened and the density of the electrode is likely to be reduced. This is because conductivity and reflectivity are reduced. Furthermore, the primary particle size of the metal nanoparticles was limited to the range of 10 to 50 nm because the metal nanoparticles having a primary particle size within the range of 10 to 50 nm are stable over time (statistical stability). It is because it correlates.

一方、銀ナノ粒子を含む金属ナノ粒子の含有量は、金属ナノ粒子及び分散媒からなる組成物１００重量％に対して２．５〜９５．０重量％、好ましくは３．５〜９０．０重量％含有する。また分散媒は、全ての分散媒１００重量％に対して、１重量％以上、好ましくは２重量％以上の水と、２重量％以上、好ましくは３重量％以上のアルコール類とを含有する。例えば、分散媒が水及びアルコール類のみからなる場合、水を２重量％含有するときはアルコール類を９８重量％含有し、アルコール類を２重量％含有するときは水を９８重量％含有する。更に保護剤、即ち金属ナノ粒子表面に化学修飾している保護分子は、水酸基（−ＯＨ）又はカルボニル基（−Ｃ＝Ｏ）のいずれか一方又は双方を含有する。ここで、銀ナノ粒子を含む金属ナノ粒子の含有量を金属ナノ粒子及び分散媒からなる組成物１００重量％に対して２．５〜９５．０重量％の範囲に限定したのは、２．５重量％未満では特に焼成後の電極の特性には影響はないけれども、必要な厚さの電極を得ることが難しく、９５．０重量％を越えると組成物の湿式塗工時にインク或いはペーストとしての必要な流動性を失ってしまうからである。また水の含有量を全ての分散媒１００重量％に対して１重量％以上の範囲に限定したのは、１重量％未満では、組成物を湿式塗工法により塗工して得られた膜を低温で焼結し難く、また焼成後の電極の導電性と反射率が低下してしまい、アルコール類の含有量を全ての分散媒１００重量％に対して２重量％以上の範囲に限定したのは、２重量％未満では、上記と同様に組成物を湿式塗工法により塗工して得られた膜を低温で焼結し難く、また焼成後の電極の導電性と反射率が低下してしまうからである。なお、水酸基（−ＯＨ）が銀ナノ粒子等の金属ナノ粒子を化学修飾する保護剤に含有されると、組成物の分散安定性に優れ、塗膜の低温焼結にも効果的な作用があり、カルボニル基（−Ｃ＝Ｏ）が銀ナノ粒子等の金属ナノ粒子を化学修飾する保護剤に含有されると、上記と同様に組成物の分散安定性に優れ、塗膜の低温焼結にも効果的な作用がある。   On the other hand, the content of the metal nanoparticles including silver nanoparticles is 2.5 to 95.0% by weight, preferably 3.5 to 90.0% with respect to 100% by weight of the composition comprising the metal nanoparticles and the dispersion medium. Contains by weight. The dispersion medium contains 1% by weight or more, preferably 2% by weight or more of water, and 2% by weight or more, preferably 3% by weight or more of alcohols with respect to 100% by weight of all the dispersion media. For example, when the dispersion medium is composed of only water and alcohols, it contains 98% by weight of alcohol when it contains 2% by weight of water and 98% by weight of water when it contains 2% by weight of alcohol. Further, the protective agent, that is, the protective molecule chemically modified on the surface of the metal nanoparticle contains either one or both of a hydroxyl group (—OH) and a carbonyl group (—C═O). Here, the content of the metal nanoparticles including silver nanoparticles was limited to the range of 2.5 to 95.0% by weight with respect to 100% by weight of the composition composed of the metal nanoparticles and the dispersion medium. If it is less than 5% by weight, the properties of the electrode after firing are not particularly affected, but it is difficult to obtain an electrode having a required thickness. If it exceeds 95.0% by weight, it is used as an ink or paste when wet-coating the composition. This is because the necessary liquidity is lost. Further, the content of water is limited to a range of 1% by weight or more with respect to 100% by weight of all the dispersion media. When the content is less than 1% by weight, a film obtained by applying the composition by a wet coating method is used. It was difficult to sinter at low temperature, and the conductivity and reflectance of the electrode after firing were lowered, and the content of alcohols was limited to a range of 2% by weight or more with respect to 100% by weight of all dispersion media. If it is less than 2% by weight, it is difficult to sinter the film obtained by applying the composition by the wet coating method at a low temperature as described above, and the conductivity and reflectance of the electrode after firing are reduced. Because it ends up. In addition, when a hydroxyl group (—OH) is contained in a protective agent that chemically modifies metal nanoparticles such as silver nanoparticles, the composition has excellent dispersion stability and has an effective effect on low-temperature sintering of the coating film. Yes, when a carbonyl group (—C═O) is contained in a protective agent that chemically modifies metal nanoparticles such as silver nanoparticles, the composition has excellent dispersion stability as described above, and the coating film is sintered at low temperature. Also has an effective action.

一方、銀ナノ粒子以外の金属ナノ粒子は、Ａｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｃｒ、Ｆｅ及びＭｎからなる群より選ばれた１種又は２種以上の混合組成又は合金組成からなる金属ナノ粒子であり、この銀ナノ粒子以外の金属ナノ粒子は全ての金属ナノ粒子１００重量％に対して０．０２重量％以上かつ２５重量％未満、好ましくは０．０３重量％〜２０重量％含有する。また上記アルコール類は、メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、グリセロール、イソボニルヘキサノール及びエリトリトールからなる群より選ばれた１種又は２種以上であることが好ましい。ここで、銀ナノ粒子以外の金属ナノ粒子の含有量を全ての金属ナノ粒子１００重量％に対して０．０２重量％以上かつ２５重量％未満の範囲に限定したのは、０．０２重量％未満では特に大きな問題はないけれども、０．０２〜２５重量％の範囲内においては、耐候性試験（温度１００℃かつ湿度５０％の恒温恒湿槽に１０００時間保持する試験）後の電極の導電性及び反射率が耐候性試験前より悪化しないという特徴があり、２５重量％以上では焼成直後の電極の導電性及び反射率が低下し、しかも耐候性試験後の電極が耐候性試験前の電極より導電性及び反射率が低下してしまうからである。   On the other hand, the metal nanoparticles other than silver nanoparticles are one or a mixture of two or more selected from the group consisting of Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Cr, Fe and Mn. Metal nanoparticles having a composition or an alloy composition. The metal nanoparticles other than silver nanoparticles are 0.02% by weight or more and less than 25% by weight, preferably 0.03% with respect to 100% by weight of all metal nanoparticles. Contains from 20% to 20% by weight. The alcohols are preferably one or more selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, isobornyl hexanol and erythritol. Here, the content of the metal nanoparticles other than the silver nanoparticles is limited to 0.02% by weight or more and less than 25% by weight with respect to 100% by weight of all the metal nanoparticles. However, in the range of 0.02 to 25% by weight, the conductivity of the electrode after a weather resistance test (a test held in a constant temperature and humidity chamber at a temperature of 100 ° C. and a humidity of 50% for 1000 hours). And 25% by weight or more, the conductivity and reflectance of the electrode immediately after firing are reduced, and the electrode after the weathering test is the electrode before the weathering test. This is because the conductivity and reflectance are further reduced.

このように構成された太陽電池の電極形成用組成物の製造方法を説明する。
(a) 銀ナノ粒子を化学修飾する保護剤の有機分子主鎖の炭素骨格の炭素数を３とする場合
先ず硝酸銀を脱イオン水等の水に溶解して第１金属塩水溶液を調製する。一方、クエン酸ナトリウムを脱イオン水等の水に溶解させて得られた濃度１０〜４０％のクエン酸ナトリウム水溶液に、窒素ガス等の不活性ガスの気流中で粒状又は粉状の硫酸第一鉄を直接加えて溶解させ、クエン酸イオンと第一鉄イオンを３：２のモル比で含有する還元剤水溶液を調製する。次に上記不活性ガス気流中で上記還元剤水溶液を撹拌しながら、この還元剤水溶液に上記第１金属塩水溶液を滴下して混合する。ここで、第１金属塩水溶液の添加量は還元剤水溶液の量の１／１０以下になるように、各溶液の濃度を調整することで、室温の第１金属塩水溶液を滴下しても反応温度が３０〜６０℃に保持されるようにする。また上記両水溶液の混合比は、第１金属塩水溶液中の金属イオンの総原子価数に対する、還元剤水溶液中のクエン酸イオンと第一鉄イオンのモル比がいずれも３倍モルとなるようにする。第１金属塩水溶液の滴下が終了した後、混合液の撹拌を更に１０〜３００分間続けて金属コロイドからなる第１分散液を調製する。この分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションや遠心分離法等により分離した後、この分離物に脱イオン水等の水を加えて第１分散体の前駆体とし、限外ろ過により脱塩処理し、更に引き続いて第１分散体の前駆体をアルコール類で置換洗浄して、金属（銀）の含有量を２．５〜５０重量％にする。その後、第１分散体の前駆体を遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、金属ナノ粒子が一次粒径１０〜５０ｎｍの範囲内の金属ナノ粒子を数平均で７０％以上含有するように調製する、即ち数平均で全ての金属ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの範囲内の金属ナノ粒子の占める割合が７０％以上になるように調整する。なお、金属ナノ粒子と記載したが、この(a)の場合では、数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの範囲内の銀ナノ粒子の占める割合が７０％以上になるように調整している。 The manufacturing method of the composition for electrode formation of the solar cell comprised in this way is demonstrated.
(a) When the carbon number of the carbon skeleton of the organic molecular main chain of the protective agent for chemically modifying the silver nanoparticles is set to 3 First, silver nitrate is dissolved in water such as deionized water to prepare a first metal salt aqueous solution. On the other hand, the aqueous solution of sodium citrate having a concentration of 10 to 40% obtained by dissolving sodium citrate in deionized water or the like is mixed with granular or powdered sulfuric acid in a stream of inert gas such as nitrogen gas. Iron is directly added and dissolved to prepare an aqueous reducing agent solution containing citrate ions and ferrous ions in a molar ratio of 3: 2. Next, the first metal salt aqueous solution is dropped into and mixed with the reducing agent aqueous solution while stirring the reducing agent aqueous solution in the inert gas stream. Here, by adjusting the concentration of each solution so that the amount of the first metal salt aqueous solution added is 1/10 or less of the amount of the reducing agent aqueous solution, the reaction can be performed even when the first metal salt aqueous solution at room temperature is dropped. temperature he to is held at 30 to 60 ° C.. The mixing ratio of the two aqueous solutions is such that the molar ratio of the citrate ion and the ferrous ion in the reducing agent aqueous solution is 3 times as much as the total valence of the metal ions in the first metal salt aqueous solution. To. After the dropping of the first metal salt aqueous solution is completed, stirring of the mixed solution is further continued for 10 to 300 minutes to prepare a first dispersion composed of metal colloid. The dispersion is allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles are separated by decantation, centrifugation, or the like, and then water such as deionized water is added to the separated material to form a precursor of the first dispersion. And desalting by ultrafiltration, followed by substitution washing of the precursor of the first dispersion with alcohols to make the metal (silver) content 2.5 to 50% by weight. Thereafter, the precursor of the first dispersion is adjusted using a centrifuge to adjust the centrifugal force of the centrifuge to separate the coarse particles, whereby the metal nanoparticles having a primary particle size in the range of 10 to 50 nm are obtained. The particles are prepared so as to contain 70% or more of the number average, that is, the ratio of the metal nanoparticles within the range of the primary particle size of 10 to 50 nm with respect to 100% of all the metal nanoparticles is 70% or more. Adjust to. Although described as metal nanoparticles, in the case of (a), the proportion of silver nanoparticles in the range of the primary particle size of 10 to 50 nm with respect to 100% of all silver nanoparticles is 70% or more. It is adjusted so that

数平均の測定方法は、先ず、得られた金属ナノ粒子をＴＥＭ（Transmission Electron Microscope、透過型電子顕微鏡）により約５０万倍程度の倍率で撮影する。次いで、得られた画像から金属ナノ粒子２００個について一次粒径を測定し、この測定結果をもとに粒径分布を作成する。次に、作成した粒径分布から、一次粒径１０〜５０ｎｍの範囲内の金属ナノ粒子が全金属ナノ粒子で占める個数割合を求める。   In the number average measurement method, first, the obtained metal nanoparticles are photographed with a TEM (Transmission Electron Microscope) at a magnification of about 500,000 times. Next, a primary particle size is measured for 200 metal nanoparticles from the obtained image, and a particle size distribution is created based on the measurement result. Next, from the created particle size distribution, the ratio of the number of metal nanoparticles within the range of the primary particle size of 10 to 50 nm occupied by all metal nanoparticles is determined.

これにより銀ナノ粒子を化学修飾する保護剤の有機分子主鎖の炭素骨格の炭素数が３である第１分散体（太陽電池の電極形成用組成物）が得られる。なお、この分散体１００重量％に対する最終的な金属含有量（銀含有量）は２．５〜９５重量％とするとともに、溶媒の水及びアルコール類をそれぞれ１％以上及び２％以上にそれぞれ調整する。 Thereby, the 1st dispersion | distribution (composition for electrode formation of a solar cell) whose carbon number of the carbon skeleton of the organic molecular principal chain of the protective agent which chemically modifies silver nanoparticles is 3 is obtained. The final metal content (silver content) with respect to 100% by weight of the dispersion is 2.5 to 95% by weight, and the solvent water and alcohol are adjusted to 1% or more and 2% or more, respectively. To do.

(b) 銀ナノ粒子を化学修飾する保護剤の有機分子主鎖の炭素骨格の炭素数を２とする場合
還元剤水溶液を調製するときに用いたクエン酸ナトリウムをりんご酸ナトリウムに替えること以外は上記(a)と同様にして第１分散体を調製する。これにより銀ナノ粒子を化学修飾する有機分子主鎖の炭素骨格の炭素数が２である分散体（太陽電池の電極形成用組成物）が得られる。
(c) 銀ナノ粒子を化学修飾する保護剤の有機分子主鎖の炭素骨格の炭素数を１とする場合
還元剤水溶液を調製するときに用いたクエン酸ナトリウムをグリコール酸ナトリウムに替えること以外は上記(a)と同様にして第１分散体を調製する。これにより銀ナノ粒子を化学修飾する有機分子主鎖の炭素骨格の炭素数が１である第１分散体（太陽電池の電極形成用組成物）が得られる。
(d) 銀ナノ粒子以外の金属ナノ粒子を化学修飾する保護剤の有機分子主鎖の炭素骨格の炭素数を３とする場合
銀ナノ粒子以外の金属ナノ粒子を構成する金属としては、Ａｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ又はＭｎが挙げられる。第１金属塩水溶液を調製するときに用いた硝酸銀を、塩化金酸、塩化白金酸、硝酸パラジウム、三塩化ルテニウム、塩化ニッケル、硝酸第一銅、二塩化錫、硝酸インジウム、塩化亜鉛、硫酸鉄、硫酸クロム又は硫酸マンガンに替えること以外は上記(a)と同様にして第２分散体を調製する。これにより銀ナノ粒子以外の金属ナノ粒子を化学修飾する保護剤の有機分子主鎖の炭素骨格の炭素数が３である第２分散体（太陽電池の電極形成用組成物）が得られる。
なお、銀ナノ粒子以外の金属ナノ粒子を化学修飾する保護剤の有機分子主鎖の炭素骨格の炭素数を１や２とする場合、第１金属塩水溶液を調製するときに用いた硝酸銀を、上記種類の金属塩に替えること以外は上記(b)や上記(c)と同様にして第２分散体を調製する。これにより、銀ナノ粒子以外の金属ナノ粒子を化学修飾する保護剤の有機分子主鎖の炭素骨格の炭素数が１や２である第２分散体（太陽電池の電極形成用組成物）が得られる。 (b) When the carbon number of the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the silver nanoparticles is 2, except that the sodium citrate used when preparing the reducing agent aqueous solution is replaced with sodium malate A first dispersion is prepared in the same manner as (a) above. As a result, a dispersion (a composition for forming an electrode for a solar cell) in which the carbon skeleton of the organic molecular main chain that chemically modifies the silver nanoparticles has 2 carbon atoms is obtained.
(c) When the carbon number of the carbon skeleton of the organic molecular main chain of the protective agent for chemically modifying the silver nanoparticles is 1, except that sodium citrate used when preparing the reducing agent aqueous solution is replaced with sodium glycolate A first dispersion is prepared in the same manner as (a) above. Thereby, the 1st dispersion | distribution (composition for electrode formation of a solar cell) whose carbon number of the carbon skeleton of the organic molecular principal chain which chemically modifies silver nanoparticles is 1 is obtained.
(d) When the number of carbon atoms in the carbon skeleton of the organic molecular main chain of the protective agent for chemically modifying metal nanoparticles other than silver nanoparticles is 3, the metal constituting the metal nanoparticles other than silver nanoparticles is Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr, or Mn may be mentioned. The silver nitrate used in preparing the first metal salt aqueous solution was chloroauric acid, chloroplatinic acid, palladium nitrate, ruthenium trichloride, nickel chloride, cuprous nitrate, tin dichloride, indium nitrate, zinc chloride, iron sulfate. The second dispersion is prepared in the same manner as in the above (a) except that it is replaced with chromium sulfate or manganese sulfate. Thereby, the 2nd dispersion (composition for electrode formation of a solar cell) whose carbon number of the carbon skeleton of the organic molecular principal chain of the protective agent which chemically modifies metal nanoparticles other than silver nanoparticles is 3 is obtained.
In addition, when the carbon number of the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the metal nanoparticles other than the silver nanoparticles is 1 or 2, the silver nitrate used when preparing the first metal salt aqueous solution, A second dispersion is prepared in the same manner as in the above (b) and (c) except that the above metal salt is used. Thereby, the 2nd dispersion | distribution (composition for electrode formation of a solar cell) whose carbon number of the carbon skeleton of the organic molecular principal chain of the protective agent which chemically modifies metal nanoparticles other than a silver nanoparticle is 1 or 2 is obtained. It is done.

金属ナノ粒子として、銀ナノ粒子とともに、銀ナノ粒子以外の金属ナノ粒子を含有させる場合には、７５重量％以上の第１分散体と２５重量％未満の第２分散体とを第１及び第２分散体の合計含有量が１００重量％となるように混合する。なお、第１分散体は、上記(a)の方法で製造した銀ナノ粒子を含む分散体に留まらず、上記(b)の方法で製造した銀ナノ粒子を含む分散体や上記(c)の方法で製造した銀ナノ粒子を含む分散体を使用しても良い。 As the metal nanoparticles, with silver nanoparticles, in the case of containing the metal nanoparticles other than silver nanoparticles, 7 5 first dispersion wt% or more and a second dispersion of less than 25% by weight the first and Mixing is performed so that the total content of the second dispersion is 100% by weight. The first dispersion is not limited to the dispersion containing the silver nanoparticles produced by the method (a), but the dispersion containing the silver nanoparticles produced by the method (b) or the above (c). You may use the dispersion containing the silver nanoparticle manufactured by the method.

このように製造された分散体（太陽電池の電極形成用組成物）を用いて電極を形成する方法を説明する。
先ず太陽電池の電極形成用組成物である上記第１分散体又は第１分散体と第２分散体の混合物（以下、単に「分散体」という。）を基材上に湿式塗工法で塗工する。この湿式塗工法での塗工は、焼成後の厚さが０．１〜２．０μｍ、好ましくは０．３〜１．５μｍの範囲内となるように成膜する。上記基材は、シリコン、ガラス、透明導電材料を含むセラミックス、高分子材料又は金属からなる基板のいずれか、或いはシリコン、ガラス、透明導電材料を含むセラミックス、高分子材料及び金属からなる群より選ばれた２種以上の積層体であることができる。また基材は太陽電池素子又は透明電極付き太陽電池素子のいずれかであることが好ましい。透明電極としては、インジウム錫酸化物（Indium Tin Oxide：ＩＴＯ）、アンチモンドープ酸化錫（Antimony Tin Oxide：ＡＴＯ）、ネサ（酸化錫ＳｎＯ2）、ＩＺＯ（Indium Zic Oxide）、ＡＺＯ（アルミドープＺｎＯ）等などが挙げられる。上記分散体は太陽電池素子の光電変換半導体層の表面や、透明電極付き太陽電池素子の透明電極の表面に塗布される。更に上記湿式塗工法は、スプレーコーティング法、ディスペンサコーティング法、スピンコーティング法、ナイフコーティング法、スリットコーティング法、インクジェットコーティング法、スクリーン印刷法、オフセット印刷法又はダイコーティング法のいずれかであることが特に好ましいが、これに限られるものではなく、あらゆる方法を利用できる。スプレーコーティング法は分散体を圧縮エアにより霧状にして基材に塗布したり、或いは分散体自体を加圧し霧状にして基材に塗布する方法であり、ディスペンサコーティング法は例えば分散体を注射器に入れこの注射器のピストンを押すことにより注射器先端の微細ノズルから分散体を吐出させて基材に塗布する方法である。スピンコーティング法は分散体を回転している基材上に滴下し、この滴下した分散体をその遠心力により基材周縁に拡げる方法であり、ナイフコーティング法はナイフの先端と所定の隙間をあけた基材を水平方向に移動可能に設け、このナイフより上流側の基材上に分散体を供給して基材を下流側に向って水平移動させる方法である。スリットコーティング法は分散体を狭いスリットから流出させて基材上に塗布する方法であり、インクジェットコーティング法は市販のインクジェットプリンタのインクカートリッジに分散体を充填し、基材上にインクジェット印刷する方法である。スクリーン印刷法は、パターン指示材として紗を用い、その上に作られた版画像を通して分散体を基材に転移させる方法である。オフセット印刷法は、版に付けた分散体を直接基材に付着させず、版から一度ゴムシートに転写させ、ゴムシートから改めて基材に転移させる、インクの撥水性を利用した印刷方法である。ダイコーティング法は、ダイ内に供給された分散体をマニホールドで分配させてスリットより薄膜上に押し出し、走行する基材の表面を塗工する方法である。ダイコーティング法には、スロットコート方式やスライドコート方式、カーテンコート方式がある。 A method for forming an electrode using the dispersion (a composition for forming an electrode of a solar cell) thus manufactured will be described.
First, the first dispersion or the mixture of the first dispersion and the second dispersion (hereinafter simply referred to as “dispersion”) , which is a composition for forming an electrode for a solar cell, is applied onto a substrate by a wet coating method. To do. Coating by this wet coating method is performed so that the thickness after firing is in the range of 0.1 to 2.0 μm, preferably 0.3 to 1.5 μm. The substrate is selected from the group consisting of silicon, glass, ceramics containing a transparent conductive material, a polymer material or a metal substrate, or silicon, glass, ceramics containing a transparent conductive material, a polymer material and a metal. It can be a laminate of two or more types. Moreover, it is preferable that a base material is either a solar cell element or a solar cell element with a transparent electrode. Transparent electrodes include indium tin oxide (ITO), antimony-doped tin oxide (ATO), nesa (tin oxide SnO 2 ), IZO (Indium Zic Oxide), and AZO (aluminum-doped ZnO). Etc. The said dispersion is apply | coated to the surface of the photoelectric conversion semiconductor layer of a solar cell element, or the surface of the transparent electrode of a solar cell element with a transparent electrode. Further, the wet coating method is particularly a spray coating method, a dispenser coating method, a spin coating method, a knife coating method, a slit coating method, an ink jet coating method, a screen printing method, an offset printing method or a die coating method. Although it is preferable, the present invention is not limited to this, and any method can be used. The spray coating method is a method in which the dispersion is atomized by compressed air and applied to the substrate, or the dispersion itself is pressurized and atomized to apply to the substrate. The dispenser coating method is, for example, a method in which the dispersion is injected into a syringe. The dispersion is discharged from the fine nozzle at the tip of the syringe and applied to the substrate by pushing the piston of the syringe. The spin coating method is a method in which a dispersion is dropped onto a rotating substrate, and the dropped dispersion is spread to the periphery of the substrate by its centrifugal force. The knife coating method leaves a predetermined gap from the tip of the knife. In this method, the substrate is provided so as to be movable in the horizontal direction, the dispersion is supplied onto the substrate upstream of the knife, and the substrate is moved horizontally toward the downstream side. The slit coating method is a method in which a dispersion is discharged from a narrow slit and applied onto a substrate, and the inkjet coating method is a method in which a dispersion is filled in an ink cartridge of a commercially available inkjet printer and ink jet printing is performed on the substrate. is there. The screen printing method is a method in which wrinkles are used as a pattern indicating material and a dispersion is transferred to a substrate through a plate image formed thereon. The offset printing method is a printing method utilizing the water repellency of ink, in which the dispersion attached to the plate is not directly attached to the substrate, but is transferred from the plate to a rubber sheet and then transferred from the rubber sheet to the substrate again. . The die coating method is a method in which a dispersion supplied in a die is distributed by a manifold and extruded onto a thin film from a slit to coat the surface of a traveling substrate. The die coating method includes a slot coat method, a slide coat method, and a curtain coat method.

次に上面に成膜された基材を大気中で１３０〜４００℃、好ましくは１４０〜２００℃の温度に、１０分間〜１時間、好ましくは１５〜４０分間保持して焼成する。ここで、基材上に形成された分散体の膜厚を、焼成後の厚さが０．１〜２．０μｍの範囲内となるように限定したのは、０．１μｍ未満では太陽電池に必要な電極の表面抵抗値が不十分となり、２．０μｍを越えると特性上の不具合はないけれども、材料の使用量が必要以上に多くなって材料が無駄になるからである。また基材上に形成された分散体の膜の焼成温度を１３０〜４００℃の範囲に限定したのは、１３０℃未満では金属ナノ粒子同士の焼結が不十分になるとともに保護剤の焼成時の熱により脱離或いは分解（分離・燃焼）し難いため、焼成後の電極内に有機残渣が多く残り、この残渣が変質又は劣化して導電性及び反射率が低下してしまい、４００℃を越えると低温プロセスという生産上のメリットを生かせない、即ち製造コストが増大し生産性が低下してしまうからである。更に基材上に形成された分散体の膜の焼成時間を１０分間〜１時間の範囲に限定したのは、１０分間未満では金属ナノ粒子同士の焼結が不十分になるとともに保護剤の焼成時の熱により脱離或いは分解（分離・燃焼）し難いため、焼成後の電極内に有機残渣が多く残り、この残渣が変質又は劣化して電極の導電性及び反射率が低下してしまい、１時間を越えると特性には影響しないけれども、必要以上に製造コストが増大して生産性が低下してしまうからである。   Next, the base material formed on the upper surface is fired in the air at a temperature of 130 to 400 ° C., preferably 140 to 200 ° C., for 10 minutes to 1 hour, preferably 15 to 40 minutes. Here, the film thickness of the dispersion formed on the substrate was limited so that the thickness after firing was in the range of 0.1 to 2.0 μm. This is because the necessary surface resistance value of the electrode becomes insufficient, and if it exceeds 2.0 μm, there is no problem in characteristics, but the amount of material used is increased more than necessary and the material is wasted. In addition, the firing temperature of the dispersion film formed on the base material was limited to the range of 130 to 400 ° C. When the temperature was lower than 130 ° C., the sintering between the metal nanoparticles became insufficient and the protective agent was fired. It is difficult to desorb or decompose (separate / combust) due to the heat of heat, so that a lot of organic residue remains in the electrode after firing, and this residue is altered or deteriorated, resulting in a decrease in conductivity and reflectance. This is because the production advantage of the low-temperature process cannot be utilized, that is, the manufacturing cost increases and the productivity decreases. Furthermore, the firing time of the dispersion film formed on the base material was limited to the range of 10 minutes to 1 hour because the sintering of the metal nanoparticles became insufficient and the firing of the protective agent in less than 10 minutes. Due to the difficulty of desorption or decomposition (separation / combustion) due to the heat of the time, a lot of organic residue remains in the electrode after firing, the residue is altered or deteriorated, and the conductivity and reflectivity of the electrode decrease, This is because, if the time exceeds 1 hour, the characteristics are not affected, but the manufacturing cost is increased more than necessary and the productivity is lowered.

上記太陽電池の電極形成用組成物では、一次粒径１０〜５０ｎｍとサイズの比較的大きい金属ナノ粒子を多く含むため、金属ナノ粒子の比表面積が減少し、保護剤の占める割合が小さくなる。この結果、上記組成物を用いて太陽電池の電極を形成すると、上記保護剤中の有機分子が焼成時の熱により脱離し又は分解し、或いは離脱しかつ分解することにより、実質的に有機物を含有しない銀を主成分とする電極が得られる。従って、上記電極の形成された太陽電池を長年使用しても、有機物が変質又は劣化するということがなく、電極の導電率及び反射率が高い状態に維持されるので、経年安定性に優れた電極を得ることができる。具体的には、上記電極を、温度を１００℃に保ちかつ湿度を５０％に保った恒温恒湿槽に１０００時間収容した後であっても、波長７５０〜１５００ｎｍの電磁波、即ち可視光領域から赤外線領域までの電磁波を８０％以上電極により反射できるとともに、電極の導電性、即ち電極の体積抵抗率を２×１０-5Ω・ｃｍ（２０×１０-6Ω・ｃｍ）未満と極めて低い値に維持できる。このようにして形成された電極を用いた太陽電池は、長年使用しても高導電率及び高反射率を維持することができ、経年安定性に優れる。 Since the composition for forming an electrode of the solar cell contains a large amount of metal nanoparticles having a primary particle size of 10 to 50 nm and a relatively large size, the specific surface area of the metal nanoparticles is reduced and the proportion of the protective agent is reduced. As a result, when an electrode of a solar cell is formed using the composition, the organic molecules in the protective agent are desorbed or decomposed by the heat at the time of firing, or desorbed and decomposed, thereby substantially reducing the organic matter. An electrode composed mainly of silver not containing is obtained. Therefore, even if the solar cell on which the electrode is formed is used for many years, the organic matter is not deteriorated or deteriorated, and the conductivity and reflectivity of the electrode are maintained in a high state, so that the aging stability is excellent. An electrode can be obtained. Specifically, even after the electrode is accommodated for 1000 hours in a constant temperature and humidity chamber maintained at a temperature of 100 ° C. and a humidity of 50%, the electromagnetic wave having a wavelength of 750 to 1500 nm, that is, from the visible light region. Electromagnetic waves up to the infrared region can be reflected by 80% or more by the electrode, and the conductivity of the electrode, that is, the volume resistivity of the electrode is extremely low, less than 2 × 10 −5 Ω · cm (20 × 10 −6 Ω · cm). Can be maintained. The solar cell using the electrode formed in this way can maintain high conductivity and high reflectance even when used for many years, and is excellent in aging stability.

次に本発明の実施例を比較例とともに詳しく説明する。
＜実施例１＞
先ず硝酸銀を脱イオン水に溶解して金属塩水溶液を調製した。一方、クエン酸ナトリウムを脱イオン水に溶解させて得られた濃度２６％のクエン酸ナトリウム水溶液に、温度３５℃の窒素ガス気流中で粒状の硫酸第一鉄を直接加えて溶解させ、クエン酸イオンと第一鉄イオンを３：２のモル比で含有する還元剤水溶液を調製した。次に上記窒素ガス気流を温度３５℃に保った状態で、マグネチックスターラーの撹拌子を１００ｒｐｍの回転速度で回転させて上記還元剤水溶液を撹拌しながら、この還元剤水溶液に上記金属塩水溶液を滴下して混合した。ここで、金属塩水溶液の添加量は還元剤水溶液の量の１／１０以下になるように、各溶液の濃度を調整することで、室温の金属塩水溶液を滴下しても反応温度が４０℃に保持されるようにした。また上記両水溶液の混合比は、金属塩水溶液中の金属イオンの総原子価数に対する、還元剤水溶液中のクエン酸イオンと第一鉄イオンのモル比がいずれも３倍モルとなるようにした。金属塩水溶液の滴下が終了した後、混合液の撹拌を更に１５分間続けて金属コロイドからなる分散液を得た。この分散液のｐＨは５．５であり、分散液中の金属粒子の化学量論的生成量は５ｇ／リットルであった。この得られた分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションにより分離した。この分離物に脱イオン水を加えて分散体とし、限外ろ過により脱塩処理した後、更に引き続いてメタノールで置換洗浄して、金属（銀）の含有量を５０重量％にした。その後、遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７１％含有するように調製した、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの範囲内の銀ナノ粒子の占める割合が７１％になるように調整した。この分散体を実施例１とした。なお、分散体１００重量％に対する最終的な金属（銀）、水、メタノール及び溶媒Ａの混合割合を５０．０重量％、２．５重量％、５．０重量％及び４２．５重量％にそれぞれ調整した。ここで、溶媒Ａとは、アセトンとイソプロピルグリコールとを重量比で１：１の割合で混合した混合液である。また分散体中の銀ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。なお、硫酸第一鉄中の鉄はメタノールによる置換洗浄時等に除去された。 Next, examples of the present invention will be described in detail together with comparative examples.
<Example 1>
First, silver nitrate was dissolved in deionized water to prepare an aqueous metal salt solution. On the other hand, granular ferrous sulfate was directly added and dissolved in a 26% concentration sodium citrate aqueous solution obtained by dissolving sodium citrate in deionized water in a nitrogen gas stream at a temperature of 35 ° C. A reducing agent aqueous solution containing ions and ferrous ions in a molar ratio of 3: 2 was prepared. Next, with the nitrogen gas stream maintained at a temperature of 35 ° C., the magnetic salt stirrer is rotated at a rotational speed of 100 rpm to stir the reducing agent aqueous solution, and the metal salt aqueous solution is added to the reducing agent aqueous solution. Dropped and mixed. Here, by adjusting the concentration of each solution so that the amount of the metal salt aqueous solution added is 1/10 or less of the amount of the reducing agent aqueous solution, the reaction temperature is 40 ° C. even when the metal salt aqueous solution at room temperature is dropped. To be retained. The mixing ratio of the two aqueous solutions was such that the molar ratio of the citrate ion and ferrous ion in the reducing agent aqueous solution to the total valence of the metal ions in the metal salt aqueous solution was 3 times as much as each other. . After the dropping of the aqueous metal salt solution was completed, the mixture was further stirred for 15 minutes to obtain a dispersion composed of metal colloid. The pH of this dispersion was 5.5, and the stoichiometric amount of metal particles in the dispersion was 5 g / liter. The obtained dispersion was allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles were separated by decantation. Deionized water was added to the separated product to form a dispersion, which was desalted by ultrafiltration, and then further washed by displacement with methanol to make the metal (silver) content 50% by weight. Thereafter, the centrifugal force of the centrifuge is adjusted using a centrifuge to separate coarse particles so that the silver nanoparticles contain 71% of silver nanoparticles with a primary particle size of 10 to 50 nm in number average. Adjustment was made so that the proportion of silver nanoparticles in the range of primary particle diameter of 10 to 50 nm with respect to 100% of all prepared silver nanoparticles was 71%. This dispersion was designated as Example 1. The final mixing ratio of metal (silver), water, methanol and solvent A with respect to 100% by weight of the dispersion is 50.0% by weight, 2.5% by weight, 5.0% by weight and 42.5% by weight. Each was adjusted. Here, the solvent A is a mixed solution in which acetone and isopropyl glycol are mixed at a weight ratio of 1: 1. The silver nanoparticles in the dispersion were chemically modified with a protective agent for an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O). In addition, iron in ferrous sulfate was removed at the time of displacement washing with methanol.

＜実施例２＞
実施例１と同様にして得られた分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションにより分離した。この分離物に脱イオン水を加えて分散体とし、限外ろ過により脱塩処理した後、更に引き続いてエタノールで置換洗浄して、金属の含有量を５０重量％にした。その後、遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように調製した、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように調整した。この分散体を実施例２とした。なお、分散体１００重量％に対する最終的な金属（銀）、水、エタノール及び溶媒Ａの混合割合を５０．０重量％、４．０重量％、５．０重量％及び４１．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例３＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７３％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７３％になるように遠心分離機により調整した。この分散体を実施例３とした。なお、分散体１００重量％に対する最終的な金属（銀）、水、エタノール及び溶媒Ｂの混合割合を５０．０重量％、１．０重量％、５．０重量％及び４４．０重量％にそれぞれ調整した。ここで、溶媒Ｂとは、シクロヘキサンとメチルエチルケトンとを重量比で１：１になるように混合した混合液である。また分散体中の銀ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例４＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７５％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７５％になるように、遠心分離機により調整した。この分散体を実施例４とした。なお、分散体１００重量％に対する最終的な金属（銀）、水及びエタノールの混合割合を５０．０重量％、４８．０重量％及び２．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 2>
The dispersion obtained in the same manner as in Example 1 was allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles were separated by decantation. Deionized water was added to this separated product to form a dispersion, which was desalted by ultrafiltration, and then further washed by displacement with ethanol to make the metal content 50% by weight. Thereafter, the centrifugal force of this centrifuge is adjusted using a centrifuge to separate coarse particles so that the silver nanoparticles contain 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average. Adjustment was made so that the proportion of silver nanoparticles having a primary particle size of 10 to 50 nm with respect to 100% of all prepared silver nanoparticles was 72%. This dispersion was designated as Example 2. The final mixing ratio of metal (silver), water, ethanol and solvent A with respect to 100% by weight of the dispersion was 50.0% by weight, 4.0% by weight, 5.0% by weight and 41.0% by weight. Each was adjusted. The silver nanoparticles in the dispersion were chemically modified with a protective agent for an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).
<Example 3>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 73% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. It adjusted with the centrifuge so that the ratio for which the silver nanoparticle with a primary particle diameter of 10-50 nm with respect to 100% of particles might be 73%. This dispersion was designated as Example 3. The final mixing ratio of metal (silver), water, ethanol and solvent B to 100% by weight of the dispersion is 50.0% by weight, 1.0% by weight, 5.0% by weight and 44.0% by weight. Each was adjusted. Here, the solvent B is a mixed solution in which cyclohexane and methyl ethyl ketone are mixed at a weight ratio of 1: 1. The silver nanoparticles in the dispersion were chemically modified with a protective agent for an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).
<Example 4>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was used so that the silver nanoparticles contained 75% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. It adjusted with the centrifuge so that the ratio for which silver nanoparticles with a primary particle diameter of 10-50 nm accounted for 100% of particles might be 75%. This dispersion was designated as Example 4. The final mixing ratio of metal (silver), water and ethanol to 100% by weight of the dispersion was adjusted to 50.0% by weight, 48.0% by weight and 2.0% by weight, respectively. The silver nanoparticles in the dispersion were chemically modified with a protective agent for an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).

＜実施例５＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７５％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７５％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を塩化金酸に替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、金ナノ粒子が一次粒径１０〜５０ｎｍの金ナノ粒子を数平均で７５％含有するように、即ち数平均で全ての金ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの金ナノ粒子の占める割合が７５％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体９５重量％と第２分散体５重量％とを混合した。この分散体を実施例５とした。なお、分散体１００重量％に対する最終的な金属（銀及び金の合計）、水及びエタノールの混合割合を５０．０重量％、３．５重量％及び４６．５重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及び金ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及び金ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例６＞
実施例２と同様にして銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７１％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７１％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を塩化白金酸に替え、実施例２と同様にして白金ナノ粒子が一次粒径１０〜５０ｎｍの白金ナノ粒子を数平均で７５％含有するように、即ち数平均で全ての白金ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの白金ナノ粒子の占める割合が７５％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体９５重量％と第２分散体５重量％とを混合した。この分散体を実施例６とした。なお、分散体１００重量％に対する最終的な金属（銀及び白金の合計）、水、エタノール及び溶媒Ａの混合割合を５０．０重量％、３．５重量％、２．５重量％及び４４．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及び白金ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及び白金ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 5>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was used so that the silver nanoparticles contained 75% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 75%. On the other hand, the silver nitrate of Example 2 was replaced with chloroauric acid, and the dispersion which was substituted and washed with ethanol in the same manner as in Example 2 was used. The gold nanoparticles with a primary particle diameter of 10 to 50 nm were 75 in average number. The second dispersion is adjusted by a centrifuge so that the proportion of gold nanoparticles having a primary particle size of 10 to 50 nm is 75% with respect to 100% of all gold nanoparticles in terms of number average. Got. Next, 95% by weight of the first dispersion and 5% by weight of the second dispersion were mixed. This dispersion was designated as Example 5. The mixing ratio of final metal (total of silver and gold), water, and ethanol to 100% by weight of the dispersion was adjusted to 50.0% by weight, 3.5% by weight, and 46.5% by weight, respectively. The silver nanoparticles and gold nanoparticles in the dispersion were chemically modified with an organic molecular main chain protecting agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and gold nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).
<Example 6>
In the same manner as in Example 2, the silver nanoparticles contain 71% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, the primary particle size of 10 to 50 nm with respect to 100% of all silver nanoparticles in number average. The first dispersion was obtained by adjusting with a centrifuge so that the silver nanoparticle occupies 71%. On the other hand, the silver nitrate of Example 2 was replaced with chloroplatinic acid, and the platinum nanoparticles contained 75% of the average number of platinum nanoparticles having a primary particle size of 10 to 50 nm as in Example 2, that is, the number average. A second dispersion was obtained by adjusting with a centrifuge so that the ratio of platinum nanoparticles having a primary particle size of 10 to 50 nm to 75% of all platinum nanoparticles was 75%. Next, 95% by weight of the first dispersion and 5% by weight of the second dispersion were mixed. This dispersion was designated as Example 6. The mixing ratio of the final metal (total of silver and platinum), water, ethanol and solvent A with respect to 100% by weight of the dispersion was 50.0% by weight, 3.5% by weight, 2.5% by weight and 44.%. It adjusted to 0 weight%, respectively. The silver nanoparticles and platinum nanoparticles in the dispersion were chemically modified with an organic molecular main chain protecting agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and platinum nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).

＜実施例７＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を硝酸パラジウムに替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、パラジウムナノ粒子が一次粒径１０〜５０ｎｍのパラジウムナノ粒子を数平均で７２％含有するように、即ち数平均で全てのパラジウムナノ粒子１００％に対する一次粒径１０〜５０ｎｍのパラジウムナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体７７重量％と第２分散体２３重量％とを混合した。この分散体を実施例７とした。なお、分散体１００重量％に対する最終的な金属（銀及びパラジウムの合計）、水、エタノール及び溶媒Ａの混合割合を５０．０重量％、１．５重量％、２．５重量％及び４６．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及びパラジウムナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及びパラジウムナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例８＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を三塩化ルテニウムに替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、ルテニウムナノ粒子が一次粒径１０〜５０ｎｍのルテニウムナノ粒子を数平均で７２％含有するように、即ち数平均で全てのルテニウムナノ粒子１００％に対する一次粒径１０〜５０ｎｍのルテニウムナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第２分散体を得た。次に上記第１分散体７６重量％と上記第２分散体２４重量％とを混合した。この分散体を実施例８とした。なお、分散体１００重量％に対する最終的な金属（銀及びルテニウムの合計）、水、エタノール及び溶媒Ａの混合割合を７５．０重量％、１．５重量％、２．０重量％及び２１．５重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及びルテニウムナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及びルテニウムナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 7>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 72%. On the other hand, the silver nitrate of Example 2 was replaced with palladium nitrate, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was used. The number of palladium nanoparticles having a primary particle diameter of 10 to 50 nm was 72% on average. The second dispersion is adjusted by a centrifuge so that the proportion of palladium nanoparticles having a primary particle diameter of 10 to 50 nm to 72% is contained in the number average of 100% of all palladium nanoparticles. Obtained. Next, 77% by weight of the first dispersion and 23% by weight of the second dispersion were mixed. This dispersion was designated as Example 7. The mixing ratio of final metal (total of silver and palladium), water, ethanol and solvent A with respect to 100% by weight of the dispersion was 50.0% by weight, 1.5% by weight, 2.5% by weight and 46.%. It adjusted to 0 weight%, respectively. The silver nanoparticles and palladium nanoparticles in the dispersion were each chemically modified with a protective agent having an organic molecular main chain having a carbon skeleton of 3 carbon skeletons. Furthermore, the protective agent chemically modifying silver nanoparticles and palladium nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).
<Example 8>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 72%. On the other hand, the silver nitrate of Example 2 was replaced with ruthenium trichloride, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was used. The ruthenium nanoparticles with ruthenium nanoparticles having a primary particle size of 10 to 50 nm had a number average of 72 The second dispersion is adjusted by a centrifuge so that the proportion of ruthenium nanoparticles having a primary particle size of 10 to 50 nm is 72% with respect to 100% of all ruthenium nanoparticles in terms of number average. Got. Next, 76% by weight of the first dispersion and 24% by weight of the second dispersion were mixed. This dispersion was designated as Example 8. In addition, the final metal (total of silver and ruthenium), water, ethanol and solvent A are mixed at a ratio of 75.0 wt%, 1.5 wt%, 2.0 wt% and 21.100 wt% with respect to 100 wt% of the dispersion. Each was adjusted to 5% by weight. The silver nanoparticles and ruthenium nanoparticles in the dispersion were each chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and ruthenium nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).

＜実施例９＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７３％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７３％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を塩化ニッケルに替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、ニッケルナノ粒子が一次粒径１０〜５０ｎｍのニッケルナノ粒子を数平均で７３％含有するように、即ち数平均で全てのニッケルナノ粒子１００％に対する一次粒径１０〜５０ｎｍのニッケルナノ粒子の占める割合が７３％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体７６重量％と第２分散体２４重量％とを混合した。この分散体を実施例９とした。なお、分散体１００重量％に対する最終的な金属（銀及びニッケルの合計）、水、エタノール及び溶媒Ａの混合割合を７５．０重量％、２．２重量％、２．０重量％及び２０．８重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子及びニッケルナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例１０＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を硝酸第一銅に替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、銅ナノ粒子が一次粒径１０〜５０ｎｍの銅ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての銅ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銅ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体７６重量％と第２分散体２４重量％とを混合した。この分散体を実施例１０とした。なお、分散体１００重量％に対する最終的な金属（銀及び銅の合計）、水、エタノール及び溶媒Ｂの混合割合を７５．０重量％、４．０重量％、５．０重量％及び１６．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及び銅ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及び銅ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 9>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 73% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the ratio of silver nanoparticles having a primary particle diameter of 10 to 50 nm to 100% of the particles was 73%. On the other hand, the silver nitrate of Example 2 was replaced with nickel chloride, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was used. The number of nickel nanoparticles having a primary particle diameter of 10 to 50 nm was 73% on average. The second dispersion is adjusted by a centrifuge so that the proportion of nickel nanoparticles having a primary particle size of 10 to 50 nm is 73% with respect to 100% of all nickel nanoparticles in terms of number average. Obtained. Next, 76% by weight of the first dispersion and 24% by weight of the second dispersion were mixed. This dispersion was designated as Example 9. In addition, the final metal (total of silver and nickel), water, ethanol, and solvent A are mixed at a ratio of 75.0 wt%, 2.2 wt%, 2.0 wt%, and 20 wt% with respect to 100 wt% of the dispersion. Each was adjusted to 8% by weight. The silver nanoparticles in the dispersion were chemically modified with a protective agent for an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and nickel nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).
<Example 10>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 72%. On the other hand, the silver nitrate of Example 2 was replaced with cuprous nitrate, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was compared with the number average of copper nanoparticles having a primary particle size of 10 to 50 nm. The second dispersion is adjusted by a centrifuge so that it contains 72%, that is, the ratio of the copper nanoparticles having a primary particle diameter of 10 to 50 nm to 72% in terms of the number average of 100% of all copper nanoparticles. Got the body. Next, 76% by weight of the first dispersion and 24% by weight of the second dispersion were mixed. This dispersion was designated as Example 10. In addition, the final metal (total of silver and copper), water, ethanol, and solvent B with respect to 100 wt% of the dispersion were mixed at 75.0 wt%, 4.0 wt%, 5.0 wt%, and 16. It adjusted to 0 weight%, respectively. The silver nanoparticles and copper nanoparticles in the dispersion were each chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and copper nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).

＜実施例１１＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を二塩化錫に替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、錫ナノ粒子が一次粒径１０〜５０ｎｍの錫ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての錫ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの錫ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体７６重量％と第２分散体２４重量％とを混合した。この分散体を実施例１１とした。なお、分散体１００重量％に対する最終的な金属（銀及び錫の合計）、水、エタノール及び溶媒Ｂの混合割合を７５．０重量％、４．０重量％、５．０重量％及び１６．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及び錫ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及び錫ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例１２＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を硝酸インジウムに替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、インジウムナノ粒子が一次粒径１０〜５０ｎｍのインジウムナノ粒子を数平均で７２％含有するように、即ち数平均で全てのインジウムナノ粒子１００％に対する一次粒径１０〜５０ｎｍのインジウムナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体８０重量％と第２分散体２０重量％とを混合した。この分散体を実施例１２とした。なお、分散体１００重量％に対する最終的な金属（銀及びインジウムの合計）、水、エタノール及び溶媒Ｃの混合割合を７５．０重量％、５．０重量％、５．０重量％及び１５．０重量％にそれぞれ調整した。ここで、溶媒Ｃとは、トルエンとヘキサンとを重量比で１：１になるように混合した混合液である。また分散体中の銀ナノ粒子及びインジウムナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及びインジウムナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 11>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 72%. On the other hand, the silver nitrate of Example 2 was replaced with tin dichloride, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was used. The number of tin nanoparticles having a primary particle size of 10 to 50 nm was 72 on average. The second dispersion is adjusted by a centrifuge so that the proportion of tin nanoparticles having a primary particle size of 10 to 50 nm is 72% with respect to 100% of all tin nanoparticles. Got. Next, 76% by weight of the first dispersion and 24% by weight of the second dispersion were mixed. This dispersion was designated as Example 11. The final metal (total of silver and tin), water, ethanol, and solvent B with respect to 100% by weight of the dispersion were mixed at 75.0% by weight, 4.0% by weight, 5.0% by weight and 16.% by weight. It adjusted to 0 weight%, respectively. The silver nanoparticles and tin nanoparticles in the dispersion were each chemically modified with an organic molecular main chain protecting agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles and tin nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).
<Example 12>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 72%. On the other hand, the silver nitrate of Example 2 was replaced with indium nitrate, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was obtained by using 72% indium nanoparticles whose indium nanoparticles had a primary particle size of 10 to 50 nm. The second dispersion is adjusted by a centrifuge so that the proportion of indium nanoparticles having a primary particle size of 10 to 50 nm is 72% so as to contain, that is, the number average of 100% of all indium nanoparticles. Obtained. Next, 80% by weight of the first dispersion and 20% by weight of the second dispersion were mixed. This dispersion was designated as Example 12. In addition, the final metal (total of silver and indium), water, ethanol, and solvent C with respect to 100% by weight of the dispersion were mixed at 75.0%, 5.0%, 5.0%, and 15. It adjusted to 0 weight%, respectively. Here, the solvent C is a mixed solution in which toluene and hexane are mixed at a weight ratio of 1: 1. The silver nanoparticles and indium nanoparticles in the dispersion were each chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and indium nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).

＜実施例１３＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７４％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７４％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を塩化亜鉛に替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、亜鉛ナノ粒子が一次粒径１０〜５０ｎｍの亜鉛ナノ粒子を数平均で７４％含有するように、即ち数平均で全ての亜鉛ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの亜鉛ナノ粒子の占める割合が７４％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体８０重量％と第２分散体２０重量％とを混合した。この分散体を実施例１３とした。なお、分散体１００重量％に対する最終的な金属（銀及び亜鉛の合計）、水及びエタノールの混合割合を７５．０重量％、１０．０重量％及び１５．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及び亜鉛ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及び亜鉛ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例１４＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７５％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７５％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を硫酸クロムに替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、クロムナノ粒子が一次粒径１０〜５０ｎｍのクロムナノ粒子を数平均で７５％含有するように、即ち数平均で全てのクロムナノ粒子１００％に対する一次粒径１０〜５０ｎｍのクロムナノ粒子の占める割合が７５％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体９５重量％と第２分散体５重量％とを混合した。この分散体を実施例１４とした。なお、分散体１００重量％に対する最終的な金属（銀及びクロムの合計）、水及びエタノールの混合割合を７５．０重量％、５．０重量％及び２０．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及びクロムナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及びクロムナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 13>
In the same manner as in Example 2, the dispersion washed with ethanol was washed so that the silver nanoparticles contained 74% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 74%. On the other hand, the silver nitrate of Example 2 was replaced with zinc chloride, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was used. The number of zinc nanoparticles having a primary particle diameter of 10 to 50 nm was 74% on average. The second dispersion is adjusted by a centrifuge so that the ratio of the zinc nanoparticles having a primary particle size of 10 to 50 nm to 74% is contained on the average, that is, the average number of all zinc nanoparticles is 100%. Obtained. Next, 80% by weight of the first dispersion and 20% by weight of the second dispersion were mixed. This dispersion was designated as Example 13. The mixing ratio of final metal (total of silver and zinc), water and ethanol to 100% by weight of the dispersion was adjusted to 75.0% by weight, 10.0% by weight and 15.0% by weight, respectively. The silver nanoparticles and zinc nanoparticles in the dispersion were chemically modified with an organic molecular main chain protecting agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and zinc nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).
<Example 14>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was used so that the silver nanoparticles contained 75% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 75%. On the other hand, the silver nitrate of Example 2 was replaced with chromium sulfate, and the dispersion substituted and washed with ethanol in the same manner as in Example 2 contains 75% of chromium nanoparticles with a primary particle size of 10 to 50 nm in terms of number average. In other words, the second dispersion was obtained by adjusting with a centrifuge so that the ratio of the chromium nanoparticles having a primary particle size of 10 to 50 nm to the chromium particles of 100% in terms of number average was 75%. Next, 95% by weight of the first dispersion and 5% by weight of the second dispersion were mixed. This dispersion was designated as Example 14. The mixing ratio of final metal (total of silver and chromium), water, and ethanol with respect to 100% by weight of the dispersion was adjusted to 75.0% by weight, 5.0% by weight, and 20.0% by weight, respectively. The silver nanoparticles and chromium nanoparticles in the dispersion were each chemically modified with a protective agent having an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and chromium nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).

＜実施例１５＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を硫酸マンガンに替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、マンガンナノ粒子が一次粒径１０〜５０ｎｍのマンガンナノ粒子を数平均で７２％含有するように、即ち数平均で全てのマンガンナノ粒子１００％に対する一次粒径１０〜５０ｎｍのマンガンナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体９５重量％と第２分散体５重量％とを混合した。この分散体を実施例１５とした。なお、分散体１００重量％に対する最終的な金属（銀及びマンガンの合計）、水及びエタノールの混合割合を７５．０重量％、３．０重量％及び２２．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及びマンガンナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及びマンガンナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例１６＞
実施例１と同様にして得られた分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションにより分離した。この分離物に脱イオン水を加えて分散体とし、限外ろ過により脱塩処理した後、更に引き続いてエチレングリコール及びエタノールで置換洗浄して、金属の含有量を５０重量％にした。その後、遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７１％含有するように調製した、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７１％になるように調整した。この分散体を実施例１６とした。なお、分散体１００％に対する最終的な金属（銀）、水、エチレングリコール及びエタノールの混合割合を３５．０重量％、２．０重量％、１．０重量％及び５３．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有しなかった。 <Example 15>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 72%. On the other hand, the silver nitrate of Example 2 was replaced with manganese sulfate, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was used. The manganese nanoparticles with manganese nanoparticles having a primary particle size of 10 to 50 nm had a number average of 72%. The second dispersion is adjusted by a centrifuge so that the proportion of manganese nanoparticles having a primary particle size of 10 to 50 nm is 72% so that it is contained, that is, the number average of 100% of all manganese nanoparticles. Obtained. Next, 95% by weight of the first dispersion and 5% by weight of the second dispersion were mixed. This dispersion was designated as Example 15. The mixing ratio of final metal (total of silver and manganese), water, and ethanol to 100% by weight of the dispersion was adjusted to 75.0% by weight, 3.0% by weight, and 22.0% by weight, respectively. The silver nanoparticles and manganese nanoparticles in the dispersion were each chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and manganese nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).
<Example 16>
The dispersion obtained in the same manner as in Example 1 was allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles were separated by decantation. Deionized water was added to the separated product to form a dispersion, which was desalted by ultrafiltration, and then further subjected to substitution washing with ethylene glycol and ethanol to make the metal content 50% by weight. Thereafter, the centrifugal force of the centrifuge is adjusted using a centrifuge to separate coarse particles so that the silver nanoparticles contain 71% of silver nanoparticles with a primary particle size of 10 to 50 nm in number average. The proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of all prepared silver nanoparticles was adjusted to 71%. This dispersion was designated as Example 16. The final mixing ratio of metal (silver), water, ethylene glycol and ethanol with respect to 100% of the dispersion was 35.0 wt%, 2.0 wt%, 1.0 wt% and 53.0 wt%, respectively. It was adjusted. The silver nanoparticles in the dispersion were chemically modified with a protective agent for an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles did not contain a hydroxyl group (—OH) and a carbonyl group (—C═O).

＜実施例１７＞
実施例１と同様にして得られた分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションにより分離した。この分離物に脱イオン水を加えて分散体とし、限外ろ過により脱塩処理した後、更に引き続いてブタノールで置換洗浄して、金属の含有量を５０重量％にした。その後、遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７３％含有するように調製した、即ち数平均で全ての銀ナノ粒子１００重量％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７３％になるように調整した。この分散体を実施例１７とした。なお、分散体１００％に対する最終的な金属（銀）、水、ブタノール及び溶媒Ａの混合割合を３５．０重量％、１．５重量％、５０．０重量％及び１３．５重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有したけれども、カルボニル基（−Ｃ＝Ｏ）を含有しなかった。
＜実施例１８＞
実施例１と同様にして得られた分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションにより分離した。この分離物に脱イオン水を加えて分散体とし、限外ろ過により脱塩処理した後、更に引き続いてプロピレングリコール及びエタノールで置換洗浄して、金属の含有量を５０重量％にした。その後、遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように調製した、即ち数平均で全ての銀ナノ粒子１００重量％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように調整した。この分散体を実施例１８とした。なお、分散体１００％に対する最終的な金属（銀）、水、プロピレングリコール及びエタノールの混合割合を３５．０重量％、２．０重量％、１．０重量％及び６２．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有したけれども、カルボニル基（−Ｃ＝Ｏ）を含有しなかった。 <Example 17>
The dispersion obtained in the same manner as in Example 1 was allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles were separated by decantation. Deionized water was added to this separated product to form a dispersion, which was desalted by ultrafiltration, and then further subjected to displacement washing with butanol to make the metal content 50% by weight. Thereafter, the centrifugal force of the centrifuge is adjusted using a centrifuge to separate coarse particles so that the silver nanoparticles contain 73% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average. The ratio of the prepared silver nanoparticles having a primary particle diameter of 10 to 50 nm to the weight average of 100% by weight of all silver nanoparticles was adjusted to 73%. This dispersion was designated as Example 17. The final mixing ratio of metal (silver), water, butanol and solvent A to 100% of the dispersion was 35.0% by weight, 1.5% by weight, 50.0% by weight and 13.5% by weight, respectively. It was adjusted. The silver nanoparticles in the dispersion were chemically modified with a protective agent for an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles contained a hydroxyl group (—OH) but no carbonyl group (—C═O).
<Example 18>
The dispersion obtained in the same manner as in Example 1 was allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles were separated by decantation. Deionized water was added to this separated product to form a dispersion, which was desalted by ultrafiltration, and then further subjected to displacement washing with propylene glycol and ethanol to make the metal content 50% by weight. Thereafter, the centrifugal force of this centrifuge is adjusted using a centrifuge to separate coarse particles so that the silver nanoparticles contain 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average. The ratio of the prepared silver nanoparticles having a primary particle diameter of 10 to 50 nm to 100% by weight of all silver nanoparticles was adjusted to 72%. This dispersion was designated as Example 18. The final mixing ratio of metal (silver), water, propylene glycol and ethanol to 100% of the dispersion was 35.0% by weight, 2.0% by weight, 1.0% by weight and 62.0% by weight, respectively. It was adjusted. The silver nanoparticles in the dispersion were chemically modified with a protective agent for an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles contained a hydroxyl group (—OH) but no carbonyl group (—C═O).

＜実施例１９＞
還元剤水溶液の調製時にクエン酸ナトリウムに替えてりんご酸ナトリウムを用いたこと以外は実施例１と同様にして得られた分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションにより分離した。この分離物に脱イオン水を加えて分散体とし、限外ろ過により脱塩処理した後、更に引き続いてジエチレングリコール及びエタノールで置換洗浄して、金属の含有量を５０重量％にした。その後、遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように調製した、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように調整した。この分散体を実施例１９とした。なお、分散体１００重量％に対する最終的な金属（銀）、水、ジエチレングリコール及びエタノールの混合割合を３５．０重量％、５．０重量％、１．０重量％及び５９．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数２の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例２０＞
還元剤水溶液の調製時にクエン酸ナトリウムに替えてりんご酸ナトリウムを用いたこと以外は実施例１と同様にして得られた分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションにより分離した。この分離物に脱イオン水を加えて分散体とし、限外ろ過により脱塩処理した後、更に引き続いてグリコール及びエタノールで置換洗浄して、金属の含有量を５０重量％にした。その後、遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように調製した、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように調整した。この分散体を実施例２０とした。なお、分散体１００重量％に対する最終的な金属（銀）、水、グリセロール及びエタノールの混合割合を３５．０重量％、３５．０重量％、１．０重量％及び２９．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数２の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 19>
The dispersion obtained in the same manner as in Example 1 except that sodium malate was used in place of sodium citrate when preparing the reducing agent aqueous solution was allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles were decanted. Separated by. Deionized water was added to this separated product to form a dispersion, which was desalted by ultrafiltration, and then further subjected to displacement washing with diethylene glycol and ethanol to make the metal content 50% by weight. Thereafter, the centrifugal force of this centrifuge is adjusted using a centrifuge to separate coarse particles so that the silver nanoparticles contain 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average. Adjustment was made so that the proportion of silver nanoparticles having a primary particle size of 10 to 50 nm with respect to 100% of all prepared silver nanoparticles was 72%. This dispersion was designated as Example 19. The final mixing ratio of metal (silver), water, diethylene glycol and ethanol to 100% by weight of the dispersion was 35.0% by weight, 5.0% by weight, 1.0% by weight and 59.0% by weight, respectively. It was adjusted. The silver nanoparticles in the dispersion were chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 2 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).
<Example 20>
The dispersion obtained in the same manner as in Example 1 except that sodium malate was used in place of sodium citrate when preparing the reducing agent aqueous solution was allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles were decanted. Separated by. Deionized water was added to this separated product to form a dispersion, which was desalted by ultrafiltration, and then further subjected to substitution washing with glycol and ethanol to make the metal content 50% by weight. Thereafter, the centrifugal force of this centrifuge is adjusted using a centrifuge to separate coarse particles so that the silver nanoparticles contain 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average. Adjustment was made so that the proportion of silver nanoparticles having a primary particle size of 10 to 50 nm with respect to 100% of all prepared silver nanoparticles was 72%. This dispersion was designated as Example 20. Note that the final mixing ratio of metal (silver), water, glycerol and ethanol to 100% by weight of the dispersion was 35.0% by weight, 35.0% by weight, 1.0% by weight and 29.0% by weight, respectively. It was adjusted. The silver nanoparticles in the dispersion were chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 2 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).

＜実施例２１＞
還元剤水溶液の調製時にクエン酸ナトリウムに替えてグリコール酸ナトリウムを用いたこと以外は実施例１と同様にして得られた分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションにより分離した。この分離物に脱イオン水を加えて分散体とし、限外ろ過により脱塩処理した後、更に引き続いてジエチレングリコール及びエタノールで置換洗浄して、金属の含有量を５０重量％にした。その後、遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７３％含有するように調製した、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７３％になるように調整した。この分散体を実施例２１とした。なお、分散体１００重量％に対する最終的な金属（銀）、水及びエタノールの混合割合を３５．０重量％、１０．０重量％及び５５．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数１の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）を含有しなかったけれども、カルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例２２＞
還元剤水溶液の調製時に実施例１と同様にして得られた分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションにより分離した。この分離物に脱イオン水を加えて分散体とし、限外ろ過により脱塩処理した後、更に引き続いてエリトリトール及びエタノールで置換洗浄して、金属の含有量を５０重量％にした。その後、遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７３％含有するように調製した、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７３％になるように調整した。この分散体を実施例２２とした。なお、分散体１００重量％に対する最終的な金属（銀）、水、エリトリトール、エタノール及び溶媒Ｂの混合割合を３５．０重量％、５．０重量％、１．０重量％、２４．０重量％及び３５．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数２の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 21>
The dispersion obtained in the same manner as in Example 1 except that sodium glycolate was used instead of sodium citrate when preparing the reducing agent aqueous solution was allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles were decanted. Separated by. Deionized water was added to this separated product to form a dispersion, which was desalted by ultrafiltration, and then further subjected to displacement washing with diethylene glycol and ethanol to make the metal content 50% by weight. Thereafter, the centrifugal force of the centrifuge is adjusted using a centrifuge to separate coarse particles so that the silver nanoparticles contain 73% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average. The proportion of silver nanoparticles having a primary particle size of 10 to 50 nm with respect to 100% of all prepared silver nanoparticles was adjusted to 73%. This dispersion was designated as Example 21. The final mixing ratio of metal (silver), water and ethanol with respect to 100% by weight of the dispersion was adjusted to 35.0% by weight, 10.0% by weight and 55.0% by weight, respectively. The silver nanoparticles in the dispersion were chemically modified with a protective agent for the organic molecular main chain having a carbon skeleton of 1 carbon. Furthermore, the protective agent chemically modifying the silver nanoparticles did not contain a hydroxyl group (—OH) but contained a carbonyl group (—C═O).
<Example 22>
The dispersion obtained in the same manner as in Example 1 during the preparation of the reducing agent aqueous solution was allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles were separated by decantation. Deionized water was added to the separated product to form a dispersion, which was desalted by ultrafiltration, and then further washed by substitution with erythritol and ethanol to make the metal content 50% by weight. Thereafter, the centrifugal force of the centrifuge is adjusted using a centrifuge to separate coarse particles so that the silver nanoparticles contain 73% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average. The proportion of silver nanoparticles having a primary particle size of 10 to 50 nm with respect to 100% of all prepared silver nanoparticles was adjusted to 73%. This dispersion was designated as Example 22. The final mixing ratio of metal (silver), water, erythritol, ethanol and solvent B with respect to 100% by weight of the dispersion was 35.0% by weight, 5.0% by weight, 1.0% by weight and 24.0% by weight. % And 35.0% by weight, respectively. The silver nanoparticles in the dispersion were chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 2 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).

＜実施例２３＞
還元剤水溶液の調製時にクエン酸ナトリウムに替えてりんご酸ナトリウムを用いたこと以外は実施例１と同様にして得られた分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションにより分離した。この分離物に脱イオン水を加えて分散体とし、限外ろ過により脱塩処理した後、更に引き続いてイソボニルヘキサノール及びエタノールで置換洗浄して、金属の含有量を５０重量％にした。その後、遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７５％含有するように調整した、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７５％になるように調整した。この分散体を実施例２３とした。なお、分散体１００重量％に対する最終的な金属（銀）、水、イソボニルヘキサノール及びエタノールの混合割合を３５．０重量％、１．０重量％、１．０重量％及び６３．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数２の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例２４＞
還元剤水溶液の調製時にクエン酸ナトリウムに替えてりんご酸ナトリウムを用いたこと以外は実施例１と同様にして得られた分散液を室温で放置し、沈降した金属ナノ粒子の凝集物をデカンテーションにより分離した。この分離物に脱イオン水を加えて分散体とし、限外ろ過により脱塩処理した後、更に引き続いてメタノールで置換洗浄して、金属の含有量を５０重量％にした。その後、遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７５％含有するように調製した、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７５％になるように調整した。この分散体を実施例２４とした。なお、分散体１００重量％に対する最終的な金属（銀）、水及びメタノールの混合割合を３５．０重量％、３０．０重量％及び３５．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数２の有機分子主鎖の保護剤で化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 23>
The dispersion obtained in the same manner as in Example 1 except that sodium malate was used in place of sodium citrate when preparing the reducing agent aqueous solution was allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles were decanted. Separated by. Deionized water was added to the separated product to form a dispersion, which was desalted by ultrafiltration, and then further subjected to displacement washing with isobornyl hexanol and ethanol to make the metal content 50% by weight. Thereafter, the centrifugal force of the centrifuge is adjusted using a centrifuge to separate coarse particles so that the silver nanoparticles contain 75% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average. It adjusted so that the ratio for which the silver nanoparticle with a primary particle diameter of 10-50 nm might occupy 75% with respect to 100% of all the silver nanoparticles on the number average. This dispersion was designated as Example 23. The final mixing ratio of metal (silver), water, isobornyl hexanol and ethanol with respect to 100% by weight of the dispersion was 35.0% by weight, 1.0% by weight, 1.0% by weight and 63.0% by weight. Respectively. The silver nanoparticles in the dispersion were chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 2 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).
<Example 24>
The dispersion obtained in the same manner as in Example 1 except that sodium malate was used in place of sodium citrate when preparing the reducing agent aqueous solution was allowed to stand at room temperature, and the aggregates of the precipitated metal nanoparticles were decanted. Separated by. Deionized water was added to this separated product to form a dispersion, which was desalted by ultrafiltration, and then further subjected to displacement washing with methanol to make the metal content 50% by weight. Thereafter, the centrifugal force of the centrifuge is adjusted using a centrifuge to separate coarse particles so that the silver nanoparticles contain 75% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average. The ratio of the prepared silver nanoparticles having a primary particle diameter of 10 to 50 nm to 75% of all silver nanoparticles was adjusted to 75%. This dispersion was designated as Example 24. The final mixing ratio of metal (silver), water and methanol with respect to 100% by weight of the dispersion was adjusted to 35.0% by weight, 30.0% by weight and 35.0% by weight, respectively. The silver nanoparticles in the dispersion were chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 2 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).

＜実施例２５＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７１％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７１％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を塩化ニッケルに替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、ニッケルナノ粒子が一次粒径１０〜５０ｎｍのニッケルナノ粒子を数平均で７１％含有するように、即ち数平均で全てのニッケルナノ粒子１００％に対する一次粒径１０〜５０ｎｍのニッケルナノ粒子の占める割合が７１％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体９８重量％と第２分散体２重量％とを混合した。この分散体を実施例２５とした。なお、分散体１００重量％に対する最終的な金属（銀及びニッケルの合計）、水及びエタノールの混合割合を３５．０重量％、５．０重量％及び６０．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及びニッケルナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及びニッケルナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例２６＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７１％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７１％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を硝酸第一銅に替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、銅ナノ粒子が一次粒径１０〜５０ｎｍの銅ナノ粒子を数平均で７１％含有するように、即ち数平均で全ての銅ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銅ナノ粒子の占める割合が７１％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体９８重量％と第２分散体２重量％とを混合した。この分散体を実施例２６とした。なお、分散体１００重量％に対する最終的な金属（銀及び銅の合計）、水及びエタノールの混合割合を３５．０重量％、５．０重量％及び６０．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及び銅ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及び銅ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 25>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 71% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the ratio of silver nanoparticles having a primary particle diameter of 10 to 50 nm to 100% of the particles was 71%. On the other hand, the silver nitrate of Example 2 was replaced with nickel chloride, and the dispersion which was substituted and washed with ethanol in the same manner as in Example 2 was used, and the number average of nickel nanoparticles having a primary particle diameter of 10 to 50 nm was 71%. The second dispersion is adjusted by a centrifuge so that the proportion of nickel nanoparticles having a primary particle size of 10 to 50 nm is 71% with respect to 100% of all nickel nanoparticles in terms of number average. Obtained. Next, 98% by weight of the first dispersion and 2% by weight of the second dispersion were mixed. This dispersion was designated as Example 25. The mixing ratio of final metal (total of silver and nickel), water and ethanol with respect to 100% by weight of the dispersion was adjusted to 35.0% by weight, 5.0% by weight and 60.0% by weight, respectively. The silver nanoparticles and nickel nanoparticles in the dispersion were chemically modified with an organic molecular main chain protecting agent having a carbon skeleton of 3 carbon atoms, respectively. Furthermore, the protective agent chemically modifying silver nanoparticles and nickel nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).
<Example 26>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 71% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the ratio of silver nanoparticles having a primary particle diameter of 10 to 50 nm to 100% of the particles was 71%. On the other hand, the silver nitrate of Example 2 was replaced with cuprous nitrate, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was compared with the number average of copper nanoparticles having a primary particle size of 10 to 50 nm. The second dispersion is adjusted by a centrifuge so that the content is 71%, that is, the ratio of the copper nanoparticles having a primary particle size of 10 to 50 nm to the copper particles of 100% is 71%. Got the body. Next, 98% by weight of the first dispersion and 2% by weight of the second dispersion were mixed. This dispersion was designated as Example 26. The mixing ratio of final metal (total of silver and copper), water and ethanol with respect to 100% by weight of the dispersion was adjusted to 35.0% by weight, 5.0% by weight and 60.0% by weight, respectively. The silver nanoparticles and copper nanoparticles in the dispersion were each chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and copper nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).

＜実施例２７＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を二塩化錫に替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、錫ナノ粒子が一次粒径１０〜５０ｎｍの錫ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての錫ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの錫ナノ粒子の占める割合が７２重量％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体９８重量％と第２分散体２重量％とを混合した。この分散体を実施例２７とした。なお、分散体１００重量％に対する最終的な金属（銀及び錫の合計）、水及びエタノールの混合割合を３５．０重量％、２．０重量％及び６３．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及び錫ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及び錫ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例２８＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を塩化亜鉛に替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、亜鉛ナノ粒子が一次粒径１０〜５０ｎｍの亜鉛ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての亜鉛ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの亜鉛ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体９８重量％と第２分散体２重量％とを混合した。この分散体を実施例２８とした。なお、分散体１００重量％に対する最終的な金属（銀及び亜鉛の合計）、水及びメタノールの混合割合を３５．０重量％、２．０重量％及び６３．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及び亜鉛ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及び亜鉛ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 27>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 72%. On the other hand, the silver nitrate of Example 2 was replaced with tin dichloride, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was used. The number of tin nanoparticles having a primary particle size of 10 to 50 nm was 72 on average. The second dispersion is adjusted by a centrifuge so that the ratio of the tin nanoparticles having a primary particle diameter of 10 to 50 nm to 72% by weight with respect to 100% of all tin nanoparticles is 72% by weight. Got the body. Next, 98% by weight of the first dispersion and 2% by weight of the second dispersion were mixed. This dispersion was designated as Example 27. The mixing ratio of final metal (total of silver and tin), water and ethanol to 100% by weight of the dispersion was adjusted to 35.0% by weight, 2.0% by weight and 63.0% by weight, respectively. The silver nanoparticles and tin nanoparticles in the dispersion were each chemically modified with an organic molecular main chain protecting agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and tin nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).
<Example 28>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 72%. On the other hand, the silver nitrate of Example 2 was replaced with zinc chloride, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was used. The number of zinc nanoparticles having a primary particle diameter of 10 to 50 nm was 72% on average. The second dispersion is adjusted by a centrifuge so that the ratio of the zinc nanoparticles having a primary particle diameter of 10 to 50 nm to 72% is contained in the average number average of 100% of all zinc nanoparticles. Obtained. Next, 98% by weight of the first dispersion and 2% by weight of the second dispersion were mixed. This dispersion was designated as Example 28. The mixing ratio of final metal (total of silver and zinc), water and methanol to 100% by weight of the dispersion was adjusted to 35.0% by weight, 2.0% by weight and 63.0% by weight, respectively. The silver nanoparticles and zinc nanoparticles in the dispersion were chemically modified with an organic molecular main chain protecting agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and zinc nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).

＜実施例２９＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を硫酸クロムに替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、クロムナノ粒子が一次粒径１０〜５０ｎｍのクロムナノ粒子を数平均で７２％含有するように、即ち数平均で全てのクロムナノ粒子１００％に対する一次粒径１０〜５０ｎｍのクロムナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体９９重量％と第２分散体１重量％とを混合した。この分散体を実施例２９とした。なお、分散体１００重量％に対する最終的な金属（銀及びクロムの合計）、水及びエタノールの混合割合を３５．０重量％、２．０重量％及び６３．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及びクロムナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及びクロムナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。
＜実施例３０＞
実施例２と同様にしてエタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で７２％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第１分散体を得た。一方、実施例２の硝酸銀を硫酸マンガンに替え、実施例２と同様にしてエタノールで置換洗浄された分散体を、マンガンナノ粒子が一次粒径１０〜５０ｎｍのマンガンナノ粒子を数平均で７２％含有するように、即ち数平均で全てのマンガンナノ粒子１００％に対する一次粒径１０〜５０ｎｍのマンガンナノ粒子の占める割合が７２％になるように、遠心分離機により調整して第２分散体を得た。次に第１分散体９９重量％と第２分散体１重量％とを混合した。この分散体を実施例３０とした。なお、分散体１００重量％に対する最終的な金属（銀及びマンガンの合計）、水及びエタノールの混合割合を３５．０重量％、２．０重量％及び６３．０重量％にそれぞれ調整した。また分散体中の銀ナノ粒子及びマンガンナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子及びマンガンナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 29>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 72%. On the other hand, the silver nitrate of Example 2 was replaced with chromium sulfate, and the dispersion which was substituted and washed with ethanol in the same manner as in Example 2 contained 72% of chromium nanoparticles having a primary particle size of 10 to 50 nm in terms of number average. In other words, the second dispersion was obtained by adjusting with a centrifuge so that the ratio of the chromium nanoparticles having a primary particle size of 10 to 50 nm to the chromium particles having a number average of 100% was 72%. Next, 99% by weight of the first dispersion and 1% by weight of the second dispersion were mixed. This dispersion was determined as Example 29. The mixing ratio of final metal (total of silver and chromium), water and ethanol to 100% by weight of the dispersion was adjusted to 35.0% by weight, 2.0% by weight and 63.0% by weight, respectively. The silver nanoparticles and chromium nanoparticles in the dispersion were each chemically modified with a protective agent having an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and chromium nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).
<Example 30>
The dispersion substituted and washed with ethanol in the same manner as in Example 2 was prepared so that the silver nanoparticles contained 72% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A first dispersion was obtained by adjusting with a centrifuge so that the proportion of silver nanoparticles having a primary particle diameter of 10 to 50 nm with respect to 100% of the particles was 72%. On the other hand, the silver nitrate of Example 2 was replaced with manganese sulfate, and the dispersion subjected to substitution washing with ethanol in the same manner as in Example 2 was used. The manganese nanoparticles with manganese nanoparticles having a primary particle size of 10 to 50 nm had a number average of 72%. The second dispersion is adjusted by a centrifuge so that the proportion of manganese nanoparticles having a primary particle size of 10 to 50 nm is 72% so that it is contained, that is, the number average of 100% of all manganese nanoparticles. Obtained. Next, 99% by weight of the first dispersion and 1% by weight of the second dispersion were mixed. This dispersion was designated as Example 30. The mixing ratio of final metal (total of silver and manganese), water and ethanol to 100% by weight of the dispersion was adjusted to 35.0% by weight, 2.0% by weight and 63.0% by weight, respectively. The silver nanoparticles and manganese nanoparticles in the dispersion were each chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying silver nanoparticles and manganese nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).

＜実施例３１＞
実施例１と同様にしてメタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で１００％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が１００％になるように、遠心分離機により調整して分散体を得た。この分散体を実施例３１とした。なお、分散体１００重量％に対する最終的な金属（銀）、水及びメタノールの混合割合を３．５重量％、１．０重量％及び９５．５重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 31>
In the same manner as in Example 1, the dispersion washed with methanol was washed so that the silver nanoparticles contained 100% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A dispersion was obtained by adjusting with a centrifuge so that the ratio of the silver nanoparticles having a primary particle diameter of 10 to 50 nm to 100% of the particles was 100%. This dispersion was designated as Example 31. The final mixing ratio of metal (silver), water and methanol to 100% by weight of the dispersion was adjusted to 3.5% by weight, 1.0% by weight and 95.5% by weight, respectively. The silver nanoparticles in the dispersion were each chemically modified with a protective agent for an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).

＜実施例３２＞
実施例１と同様にしてメタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で１００％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が１００％になるように、遠心分離機により調整して分散体を得た。この分散体を実施例３２とした。なお、分散体１００重量％に対する最終的な金属（銀）、水及びメタノールの混合割合を９０．０重量％、９．８重量％及び０．２重量％にそれぞれ調整した。また分散体中の銀ナノ粒子は炭素骨格が炭素数３の有機分子主鎖の保護剤でそれぞれ化学修飾された。更に銀ナノ粒子を化学修飾している保護剤は水酸基（−ＯＨ）及びカルボニル基（−Ｃ＝Ｏ）を含有した。 <Example 32>
In the same manner as in Example 1, the dispersion washed with methanol was washed so that the silver nanoparticles contained 100% of silver nanoparticles having a primary particle size of 10 to 50 nm in number average, that is, all silver nanoparticles in number average. A dispersion was obtained by adjusting with a centrifuge so that the ratio of the silver nanoparticles having a primary particle diameter of 10 to 50 nm to 100% of the particles was 100%. This dispersion was designated as Example 32. The final mixing ratio of metal (silver), water and methanol with respect to 100% by weight of the dispersion was adjusted to 90.0% by weight, 9.8% by weight and 0.2% by weight, respectively. The silver nanoparticles in the dispersion were each chemically modified with a protective agent for an organic molecular main chain having a carbon skeleton of 3 carbon atoms. Furthermore, the protective agent chemically modifying the silver nanoparticles contained a hydroxyl group (—OH) and a carbonyl group (—C═O).

＜比較例１＞
メタノールで置換洗浄された分散体を、銀ナノ粒子が一次粒径１０〜５０ｎｍの銀ナノ粒子を数平均で６８％含有するように、即ち数平均で全ての銀ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合が６８％になるように、遠心分離機により調整した。また分散体１００重量％に対する最終的な金属（銀）、水及びメタノールの混合割合を５０．０重量％、２．５重量％及び４７．５重量％にそれぞれ調整した。上記以外は実施例１と同様にして分散体を調製した。この分散体を比較例１とした。
＜比較例２＞
還元剤水溶液の調製時にクエン酸ナトリウムに替えてメバロン酸ナトリウムを用い、分散体１００重量％に対する最終的な金属（銀）、水及びエタノールの混合割合を５０．０重量％、４．０重量％及び４６．０重量％にそれぞれ調整したこと以外は実施例２と同様にして分散体を調製した。この分散体を比較例２とした。なお、分散体中の銀ナノ粒子は炭素骨格が炭素数４の有機分子主鎖の保護剤で化学修飾された。
＜比較例３＞
分散体１００重量％に対する最終的な金属（銀）、水、エタノール及び溶媒Ａの混合割合を５０．０重量％、０．７重量％、３０．０重量％及び１９．３重量％にそれぞれ調整したこと以外は、実施例３と同様にして分散体を調製した。この分散体を比較例３とした。
＜比較例４＞
分散体１００重量％に対する最終的な金属（銀）、水、エタノール及び溶媒Ｂの混合割合を５０．０重量％、４０．０重量％、１．０重量％及び９．０重量％にそれぞれ調整したこと以外は、実施例４と同様にして分散体を調製した。この分散体を比較例４とした。
＜比較例５＞
プロパノールで置換洗浄し、第１分散体７３重量％と第２分散体２７重量％とを混合し、更に分散体１００重量％に対する最終的な金属（銀及び金）、水、プロパノール及び溶媒Ｃの混合割合を５０．０重量％、３．５重量％、３０．０重量％及び１６．５重量％にそれぞれ調整したこと以外は、実施例５と同様にして分散体を調製した。この分散体を比較例５とした。 <Comparative Example 1>
Dispersion-washed dispersion with methanol is such that the silver nanoparticles contain 68% of silver nanoparticles with a primary particle size of 10-50 nm on average, that is, the primary particle size with respect to 100% of all silver nanoparticles on average. It adjusted with the centrifuge so that the ratio for which 10-50 nm silver nanoparticles occupied might be 68%. Further, the final mixing ratio of metal (silver), water and methanol with respect to 100% by weight of the dispersion was adjusted to 50.0% by weight, 2.5% by weight and 47.5% by weight, respectively. A dispersion was prepared in the same manner as in Example 1 except for the above. This dispersion was designated as Comparative Example 1.
<Comparative example 2>
When preparing the reducing agent aqueous solution, sodium mevalonate was used instead of sodium citrate, and the final mixing ratio of metal (silver), water and ethanol with respect to 100% by weight of the dispersion was 50.0% by weight, 4.0% by weight. And a dispersion was prepared in the same manner as in Example 2 except that the amount was adjusted to 46.0% by weight. This dispersion was designated as Comparative Example 2. The silver nanoparticles in the dispersion were chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 4 carbon atoms.
<Comparative Example 3>
The final metal (silver), water, ethanol and solvent A mixing ratio with respect to 100% by weight of the dispersion was adjusted to 50.0%, 0.7%, 30.0% and 19.3% by weight, respectively. A dispersion was prepared in the same manner as in Example 3 except that. This dispersion was designated as Comparative Example 3.
<Comparative example 4>
Adjust the final metal (silver), water, ethanol and solvent B mixing ratios to 50.0 wt%, 40.0 wt%, 1.0 wt% and 9.0 wt% with respect to 100 wt% of the dispersion, respectively. A dispersion was prepared in the same manner as in Example 4 except that. This dispersion was designated as Comparative Example 4.
<Comparative Example 5>
Substitution washing with propanol, mixing 73% by weight of the first dispersion and 27% by weight of the second dispersion and further adding the final metals (silver and gold), water, propanol and solvent C to 100% by weight of the dispersion. A dispersion was prepared in the same manner as in Example 5 except that the mixing ratio was adjusted to 50.0 wt%, 3.5 wt%, 30.0 wt% and 16.5 wt%, respectively. This dispersion was designated as Comparative Example 5.

＜比較例６＞
第１分散体７４重量％と第２分散体２６重量％とを混合し、分散体１００重量％に対する最終的な金属（銀及び白金）、水及びエタノールの混合割合を７５．０重量％、３．５重量％及び２１．５重量％にそれぞれ調整したこと以外は、実施例６と同様にして分散体を調製した。この分散体を比較例６とした。
＜比較例７＞
第１分散体７３重量％と第２分散体２７重量％とを混合し、分散体１００重量％に対する最終的な金属（銀及びパラジウム）、水及びエタノールの混合割合を７５．０重量％、２．２重量％及び２２．８重量％にそれぞれ調整したこと以外は、実施例７と同様にして分散体を調製した。この分散体を比較例７とした。
＜比較例８＞
第１分散体７４重量％と第２分散体２６重量％とを混合し、分散体１００重量％に対する最終的な金属（銀及びルテニウム）、エタノール及び溶媒Ａの混合割合を７５．０重量％、１５．０重量％及び１０．０重量％にそれぞれ調整したこと以外は、実施例８と同様にして分散体を調製した。この分散体を比較例８とした。
＜比較例９＞
第１分散体７４重量％と第２分散体２６重量％とを混合し、分散体１００重量％に対する最終的な金属（銀及びニッケル）、水、エタノール及び溶媒Ｂの混合割合を７５．０重量％、２．２重量％、１２．８重量％及び１０．０重量％にそれぞれ調整したこと以外は、実施例９と同様にして分散体を調製した。この分散体を比較例９とした。
＜比較例１０＞
第１分散体７２重量％と第２分散体２８重量％とを混合し、分散体１００重量％に対する最終的な金属（銀及び銅）、水、エタノール及び溶媒Ｃの混合割合を７５．０重量％、４．０重量％、１１．０重量％及び１０．０重量％にそれぞれ調整したこと以外は、実施例１０と同様にして分散体を調製した。この分散体を比較例１０とした。 <Comparative Example 6>
74% by weight of the first dispersion and 26% by weight of the second dispersion were mixed, and the final metal (silver and platinum), water and ethanol mixing ratio was 75.0% by weight, 3% with respect to 100% by weight of the dispersion. A dispersion was prepared in the same manner as in Example 6 except that the amount was adjusted to 5% by weight and 21.5% by weight, respectively. This dispersion was designated as Comparative Example 6.
<Comparative Example 7>
73 wt% of the first dispersion and 27 wt% of the second dispersion were mixed, and the final mixing ratio of metal (silver and palladium), water and ethanol with respect to 100 wt% of the dispersion was 75.0 wt%, 2 A dispersion was prepared in the same manner as in Example 7, except that the amount was adjusted to 2% by weight and 22.8% by weight, respectively. This dispersion was designated as Comparative Example 7.
<Comparative Example 8>
74 wt% of the first dispersion and 26 wt% of the second dispersion were mixed, and the final metal (silver and ruthenium), ethanol and solvent A mixing ratio with respect to 100 wt% of the dispersion was 75.0 wt%, A dispersion was prepared in the same manner as in Example 8, except that the amount was adjusted to 15.0% by weight and 10.0% by weight, respectively. This dispersion was designated as Comparative Example 8.
<Comparative Example 9>
74 wt% of the first dispersion and 26 wt% of the second dispersion were mixed, and the final mixing ratio of metal (silver and nickel), water, ethanol and solvent B with respect to 100 wt% of the dispersion was 75.0 wt%. A dispersion was prepared in the same manner as in Example 9, except that the content was adjusted to%, 2.2% by weight, 12.8% by weight, and 10.0% by weight, respectively. This dispersion was designated as Comparative Example 9.
<Comparative Example 10>
72 wt% of the first dispersion and 28 wt% of the second dispersion were mixed, and the final mixing ratio of metal (silver and copper), water, ethanol and solvent C with respect to 100 wt% of the dispersion was 75.0 wt%. %, 4.0 wt%, 11.0 wt%, and 10.0 wt%, respectively, except that the dispersion was prepared in the same manner as in Example 10. This dispersion was designated as Comparative Example 10.

＜比較例１１＞
第１分散体７３重量％と第２分散体２７重量％とを混合し、分散体１００重量％に対する最終的な金属（銀及び錫）、水及びメタノールの混合割合を３５．０重量％、４．０重量％及び６１．０重量％にそれぞれ調整したこと以外は、実施例１１と同様にして分散体を調製した。この分散体を比較例１１とした。
＜比較例１２＞
第１分散体７４重量％と第２分散体２６重量％とを混合し、分散体１００重量％に対する最終的な金属（銀及びインジウム）、水及びエタノールの混合割合を３５．０重量％、３０．０重量％及び３５．０重量％にそれぞれ調整したこと以外は、実施例１２と同様にして分散体を調製した。この分散体を比較例１２とした。
＜比較例１３＞
第１分散体７４重量％と第２分散体２６重量％とを混合し、分散体１００重量％に対する最終的な金属（銀及び亜鉛）、水、エタノール及び溶媒Ａの混合割合を３５．０重量％、１０．０重量％、２０．０重量％及び３５．０重量％にそれぞれ調整したこと以外は、実施例１３と同様にして分散体を調製した。この分散体を比較例１３とした。
＜比較例１４＞
第１分散体７３重量％と第２分散体２７重量％とを混合し、分散体１００重量％に対する最終的な金属（銀及びクロム）、水、エタノール及び溶媒Ｂの混合割合を３５．０重量％、５．０重量％、２０．０重量％及び４０．０重量％にそれぞれ調整したこと以外は、実施例１４と同様にして分散体を調製した。この分散体を比較例１４とした。
＜比較例１５＞
第１分散体７４重量％と第２分散体２６重量％とを混合し、分散体１００重量％に対する最終的な金属（銀及びマンガン）、水、エタノール及び溶媒Ｃの混合割合を３５．０重量％、３．０重量％、２０．０重量％及び４２．０重量％にそれぞれ調整したこと以外は、実施例１５と同様にして分散体を調製した。この分散体を比較例１５とした。 <Comparative Example 11>
73 wt% of the first dispersion and 27 wt% of the second dispersion were mixed, and the final mixing ratio of metal (silver and tin), water and methanol with respect to 100 wt% of the dispersion was 35.0 wt%, A dispersion was prepared in the same manner as in Example 11 except that the content was adjusted to 0.0% by weight and 61.0% by weight, respectively. This dispersion was designated as Comparative Example 11.
<Comparative Example 12>
74 wt% of the first dispersion and 26 wt% of the second dispersion were mixed, and the final metal (silver and indium), water and ethanol mixing ratio with respect to 100 wt% of the dispersion was 35.0 wt%, 30 A dispersion was prepared in the same manner as in Example 12 except that the content was adjusted to 0.0% by weight and 35.0% by weight, respectively. This dispersion was designated as Comparative Example 12.
<Comparative Example 13>
74 wt% of the first dispersion and 26 wt% of the second dispersion were mixed, and the final mixing ratio of metal (silver and zinc), water, ethanol and solvent A to 35.0 wt% with respect to 100 wt% of the dispersion %, 10.0 wt%, 20.0 wt%, and 35.0 wt%, respectively, except that the dispersion was prepared in the same manner as in Example 13. This dispersion was designated as Comparative Example 13.
<Comparative example 14>
73 wt% of the first dispersion and 27 wt% of the second dispersion were mixed, and the final mixing ratio of metal (silver and chromium), water, ethanol and solvent B with respect to 100 wt% of the dispersion was 35.0 wt%. A dispersion was prepared in the same manner as in Example 14 except that the content was adjusted to%, 5.0% by weight, 20.0% by weight, and 40.0% by weight, respectively. This dispersion was designated as Comparative Example 14.
<Comparative Example 15>
74 wt% of the first dispersion and 26 wt% of the second dispersion are mixed, and the final mixing ratio of metal (silver and manganese), water, ethanol and solvent C to 35.0 wt% with respect to 100 wt% of the dispersion A dispersion was prepared in the same manner as in Example 15 except that the content was adjusted to%, 3.0% by weight, 20.0% by weight, and 42.0% by weight, respectively. This dispersion was designated as Comparative Example 15.

＜比較試験１及び評価＞
実施例１〜３２及び比較例１〜１５の分散体を基材上に、焼成後の厚さが次の表３及び表４に示される膜厚となるように塗布した後に、次の表３及び表４に示される温度で焼成することにより、基材上に電極を形成した。基材としては、ＩＴＯ膜付き太陽電池、ＩＴＯ膜なし太陽電池、シリコン基板、ガラス板、ポリイミド板、ＰＥＴフィルム又はＩＴＯ膜付きガラス板を用いた。これらの電極を形成した基材について、耐候性試験を行う前に、各基材に形成された電極の反射率及び導電性を測定するとともに、耐候性試験を行った後に、各基材に形成された電極の反射率及び導電性を測定した。その結果を、表３及び表４に示す。
なお、耐候性試験は、電極の形成された基材を、温度を１００℃に保ち湿度を５０％に保った恒温恒湿槽に１０００時間収容することにより行った。
また、反射率は、波長７５０〜１５００ｎｍの電磁波（赤外線及び可視光線）を電極に照射し、反射した電磁波を紫外可視分光光度計（Ｖ−５７０：日本分光社製）を用いて測定し、全照射量に対する反射量の割合（％）を算出して求めた。
また、金属ナノ粒子の一次粒径は、ＦＥ−ＴＥＭ（電界放出型透過電子顕微鏡：日本電子社製）を用いて計測し、一次粒径１０〜５０ｎｍの銀ナノ粒子の占める割合は、上記ＦＥ−ＴＥＭを用いて撮影した金属ナノ粒子の一次粒径の写真から画像処理により粒子径の数を計測して評価した。
また導電性は、四端子法により測定し算出した体積抵抗率（Ω・ｃｍ）として求めた。具体的には、電極の体積抵抗率は、先ず焼成後の電極の厚さをＳＥＭ（電子顕微鏡Ｓ８００：日立製作所社製）を用いて電極断面から電極の厚さを直接計測し、次に四端子法による比抵抗測定器（ロレスタ：三菱化学社製）を用い、この測定器に上記実測した電極の厚さを入力して測定した。
更に水酸基（−ＯＨ）、カルボニル基（−Ｃ＝Ｏ）の有無は、ＸＰＳ（Quantum 2000：PHI社製のＸ線光電子分光分析装置）、ＴＯＦ−ＳＩＭＳ（TOF-SIMS IV：ION-TOF社製の飛行時間型二次イオン質量分析装置）、ＦＴＩＲ（NEXUS 670：Nicolet社製のフーリエ変換赤外分光光度計）及びＴＰＤ−ＭＳ（5973N：Agilent社製の昇温熱脱離・質量分析装置）を用いた機器分析を併用して存在を確認した。 <Comparative test 1 and evaluation>
After coating the dispersions of Examples 1 to 32 and Comparative Examples 1 to 15 on the base material so that the thickness after firing would be the film thicknesses shown in the following Table 3 and Table 4, the following Table 3 And the electrode was formed on the base material by baking at the temperature shown in Table 4. As the substrate, a solar cell with an ITO film, a solar cell without an ITO film, a silicon substrate, a glass plate, a polyimide plate, a PET film, or a glass plate with an ITO film was used. Before performing the weather resistance test on the base material on which these electrodes are formed, the reflectance and conductivity of the electrode formed on each base material are measured, and after the weather resistance test is performed, each electrode is formed on each base material. The reflectivity and conductivity of the prepared electrodes were measured. The results are shown in Tables 3 and 4.
In addition, the weather resistance test was performed by accommodating the substrate on which the electrode was formed in a constant temperature and humidity chamber having a temperature of 100 ° C. and a humidity of 50% for 1000 hours.
The reflectance was measured by irradiating an electrode with electromagnetic waves (infrared rays and visible rays) having a wavelength of 750 to 1500 nm, and measuring the reflected electromagnetic waves using an ultraviolet-visible spectrophotometer (V-570: manufactured by JASCO Corporation). The ratio (%) of the reflection amount with respect to the irradiation amount was calculated and obtained.
The primary particle size of the metal nanoparticles is measured using FE-TEM (field emission transmission electron microscope: manufactured by JEOL Ltd.), and the proportion of silver nanoparticles having a primary particle size of 10 to 50 nm is determined by the above FE. -From the photograph of the primary particle diameter of the metal nanoparticles photographed using TEM, the number of particle diameters was measured and evaluated.
The conductivity was determined as a volume resistivity (Ω · cm) measured and calculated by the four probe method. Specifically, the volume resistivity of the electrode is determined by first measuring the thickness of the electrode after firing directly from the electrode cross section using an SEM (Electron Microscope S800: manufactured by Hitachi, Ltd.), Using a specific resistance measuring instrument (Loresta: manufactured by Mitsubishi Chemical Corporation) by the terminal method, the measured thickness of the electrode was input to this measuring instrument.
Furthermore, the presence or absence of a hydroxyl group (—OH) and a carbonyl group (—C═O) is determined by XPS (Quantum 2000: X-ray photoelectron spectrometer manufactured by PHI), TOF-SIMS (TOF-SIMS IV: manufactured by ION-TOF). Time-of-flight secondary ion mass spectrometer), FTIR (NEXUS 670: Fourier transform infrared spectrophotometer manufactured by Nicolet) and TPD-MS (5973N: temperature-programmed thermal desorption / mass spectrometer manufactured by Agilent) Presence was confirmed using the instrumental analysis used together.

一方、表１及び表２に、実施例１〜３２及び比較例１〜１５の分散体における一次粒径１０〜５０ｎｍの金属ナノ粒子の占める割合と、有機分子主鎖の炭素数と、水酸基（−ＯＨ）の有無と、カルボニル基（−Ｃ＝Ｏ）の有無と、分散体（組成物）の種類及び混合割合と、異種金属（銀以外の金属）の種類及び含有率（銀と銀以外の金属の合計を１００重量％としたときの異種金属の含有率）とを示した。また表３及び表４には、反射率、導電性（体積抵抗率）及び耐候性とともに、基材の種類、膜厚及び焼成温度を示した。更に表３及び表４の耐候性の欄において、『良好』とは、反射率が８０％以上でありかつ体積抵抗率が２０×１０-6Ω・ｃｍ未満であった場合を示し、『不良』とは反射率が８０％未満でありかつ体積抵抗率が２０×１０-6Ω・ｃｍ未満であるか、又は反射率が８０％以上でありかつ体積抵抗率が２０×１０-6Ω・ｃｍを越えるか、或いは反射率が８０％未満でありかつ体積抵抗率が２０×１０-6Ω・ｃｍを越えた場合を示す。
なお、表１及び表２のアルコール類の欄において、『ＭＥ』はメタノールを示し、『ＥＴ』はエタノールを示し、『ＥＧ』はエチレングリコールを示し、『ＢＵ』はブタノールを示し、『ＰＧ』はプロピレングリコールを示し、『ＤＥＧ』はジエチレングリコールを示し、『ＧＬ』はグリセロースを示し、『ＥＲ』はエリトリトールを示し、『ＩＨ』はイソボニルヘキサノールを示し、『ＰＲ』はプロパノールを示す。
また、表１及び表２の他の溶媒の欄において、『Ａ』はアセトンとイソプロピルグリコールとを重量比で１：１に混合した混合液を示し、『Ｂ』はシクロヘキサンとメチルエチルケトンとを重量比で１：１に混合した混合液を示し、『Ｃ』はトルエンとヘキサンとを重量比で１：１に混合した混合液を示す。 On the other hand, in Tables 1 and 2, the ratio of the metal nanoparticles having a primary particle size of 10 to 50 nm in the dispersions of Examples 1 to 32 and Comparative Examples 1 to 15, the number of carbon atoms in the organic molecular main chain, and the hydroxyl group ( -OH), presence / absence of carbonyl group (-C = O), type and mixing ratio of dispersion (composition), type and content of different metals (metals other than silver) (except silver and silver) The content of dissimilar metals when the total amount of metals is 100% by weight). Tables 3 and 4 show the substrate type, film thickness, and firing temperature, as well as reflectance, conductivity (volume resistivity), and weather resistance. Furthermore, in the weather resistance column of Tables 3 and 4, “good” indicates a case where the reflectance is 80% or more and the volume resistivity is less than 20 × 10 −6 Ω · cm. or "a less than 80% reflectivity and the volume resistivity is less than 20 × 10 -6 Ω · cm, or reflectance is not less than 80% and a volume resistivity of 20 × 10 -6 Ω · It shows a case where it exceeds cm, or the reflectance is less than 80% and the volume resistivity exceeds 20 × 10 −6 Ω · cm.
In the column of alcohols in Tables 1 and 2, “ME” indicates methanol, “ET” indicates ethanol, “EG” indicates ethylene glycol, “BU” indicates butanol, and “PG”. Represents propylene glycol, “DEG” represents diethylene glycol, “GL” represents glycerose, “ER” represents erythritol, “IH” represents isobornyl hexanol, and “PR” represents propanol.
In the column of other solvents in Tables 1 and 2, “A” indicates a mixed solution of acetone and isopropyl glycol mixed at a weight ratio of 1: 1, and “B” indicates a weight ratio of cyclohexane and methyl ethyl ketone. Indicates a mixed solution of 1: 1 mixed, and “C” indicates a mixed solution of toluene and hexane mixed at a weight ratio of 1: 1.

Figure 2012147014
Figure 2012147014

Figure 2012147014
Figure 2012147014

Figure 2012147014
Figure 2012147014

Figure 2012147014
表３及び表４から明らかなように、比較例１及び３では、焼成直後、即ち耐候性試験前の電極の反射率は８０％以上でありかつ体積抵抗率は２０×１０-6Ω・ｃｍ未満であり、初期特性は十分に満足するものであったけれども、耐候性試験を行った後は、電極の反射率及び体積抵抗率が低下（経年劣化）して不良となった。その他の比較例では、耐候性試験前の電極の反射率又は体積抵抗率のいずれか一方又は両方において不十分であり、耐候性試験後の電極の反射率及び体積抵抗率も不良となった。これらに対し、実施例では、耐候性試験前及び耐候性試験後のいずれであっても、電極の反射率が８０％以上でありかつ体積抵抗率が２０×１０-6Ω・ｃｍ未満であり、耐候性試験前の初期特性も耐候性も十分に満足するものとなった。
Figure 2012147014
 As is apparent from Tables 3 and 4, in Comparative Examples 1 and 3, the reflectivity of the electrode immediately after firing, that is, before the weather resistance test, is 80% or more and the volume resistivity is 20 × 10 −6 Ω · cm. Although the initial characteristics were sufficiently satisfactory, after the weather resistance test, the reflectivity and volume resistivity of the electrode decreased (deteriorated over time), resulting in failure. In other comparative examples, either or both of the reflectance and volume resistivity of the electrode before the weather resistance test were insufficient, and the reflectance and volume resistivity of the electrode after the weather resistance test were also poor. On the other hand, in the examples, the reflectance of the electrode is 80% or more and the volume resistivity is less than 20 × 10 −6 Ω · cm, both before and after the weather resistance test. The initial characteristics and weather resistance before the weather resistance test were sufficiently satisfied.

Claims (11)

金属ナノ粒子が分散媒に分散した太陽電池の電極形成用組成物であって、
前記金属ナノ粒子が７５重量％以上の銀ナノ粒子を含有し、
前記金属ナノ粒子は炭素骨格が炭素数１〜３の有機分子主鎖の保護剤で化学修飾され、
前記金属ナノ粒子が一次粒径１０〜５０ｎｍの範囲内の金属ナノ粒子を数平均で７０％以上含有し、
前記分散媒が１重量％以上の水と２重量％以上のアルコール類とを含有し、
前記金属ナノ粒子の含有量が金属ナノ粒子及び分散媒からなる組成物１００重量％に対して２．５〜９５．０重量％であり、
前記保護剤が水酸基(-OH)又はカルボニル基(-C=O)のいずれか一方又は双方を含有する
ことを特徴とする太陽電池の電極形成用組成物。 A composition for forming an electrode of a solar cell in which metal nanoparticles are dispersed in a dispersion medium,
The metal nanoparticles contain 75% by weight or more of silver nanoparticles,
The metal nanoparticles are chemically modified with an organic molecular main chain protective agent having a carbon skeleton of 1 to 3 carbon atoms,
The metal nanoparticles contain 70% or more of average number of metal nanoparticles having a primary particle size of 10 to 50 nm ,
The dispersion medium contains 1% by weight or more of water and 2% by weight or more of alcohols,
The content of the metal nanoparticles is 2.5 to 95.0% by weight with respect to 100% by weight of the composition comprising the metal nanoparticles and the dispersion medium,
A composition for forming an electrode of a solar cell, wherein the protective agent contains one or both of a hydroxyl group (—OH) and a carbonyl group (—C═O) . 金属ナノ粒子が銀ナノ粒子以外に更にＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ及びＭｎからなる群より選ばれた１種又は２種以上の混合組成又は合金組成からなる金属ナノ粒子を２重量％以上かつ２５重量％未満含有する請求項１記載の太陽電池の電極形成用組成物。 In addition to silver nanoparticles, the metal nanoparticles may be one or more mixed compositions selected from the group consisting of Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr and Mn, or The composition for forming an electrode of a solar cell according to claim 1, wherein the composition contains metal nanoparticles having an alloy composition of 2 wt% or more and less than 25 wt%. アルコール類がメタノール、エタノール、プロパノール、ブタノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、イソボニルヘキサノール、グリセロール及びエリトリトールからなる群より選ばれた１種又は２種以上である請求項１記載の太陽電池の電極形成用組成物。 Methanol alcohol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, isobornyl hexanol, glycerol and one or more in which electrodes of a solar cell according to claim 1 selected from the group consisting of erythritol Forming composition. 硝酸銀を水に溶解して第１金属塩水溶液を調製する工程と、Preparing a first metal salt aqueous solution by dissolving silver nitrate in water;
濃度１０〜４０％のクエン酸ナトリウム、りんご酸ナトリウム又はグリコール酸ナトリウムの水溶液に不活性ガスの気流中で粒状又は粉状の硫酸第一鉄を加えて溶解させて還元剤水溶液を調製する工程と、A step of preparing an aqueous reducing agent solution by adding granular or powdered ferrous sulfate in an inert gas stream to an aqueous solution of sodium citrate, sodium malate or sodium glycolate having a concentration of 10 to 40%; ,
前記不活性ガス気流中で前記還元剤水溶液を撹拌しながら、前記還元剤水溶液の量の１／１０以下の割合で反応温度が３０〜６０℃に保持されるように室温の前記第１金属塩水溶液を前記還元剤水溶液に滴下して混合する工程と、While stirring the reducing agent aqueous solution in the inert gas stream, the first metal salt at room temperature so that the reaction temperature is maintained at 30 to 60 ° C. at a rate of 1/10 or less of the amount of the reducing agent aqueous solution. Dropping and mixing an aqueous solution into the reducing agent aqueous solution;
前記混合液の撹拌を更に１０〜３００分間続けて銀コロイドからなる第１分散液を調製する工程と、Continuing the stirring of the mixed solution for another 10 to 300 minutes to prepare a first dispersion composed of silver colloid;
前記第１分散液を室温で放置することにより沈降した銀ナノ粒子の凝集物をデカンテーション又は遠心分離法により分離する工程と、Separating the aggregate of silver nanoparticles precipitated by allowing the first dispersion to stand at room temperature by decantation or centrifugation; and
前記第１分散液から分離した固形分に水を加えて第１分散体の前駆体を得る工程と、Adding water to the solid content separated from the first dispersion to obtain a precursor of the first dispersion;
前記第１分散体の前駆体を限外ろ過により脱塩処理する工程と、Desalting the precursor of the first dispersion by ultrafiltration;
前記脱塩処理した第１分散体の前駆体をアルコール類で置換洗浄して銀の含有量を２．５〜５０重量％に調整する工程と、A step of substituting and washing the precursor of the desalted first dispersion with alcohols to adjust the silver content to 2.5 to 50% by weight;
前記アルコール類で置換洗浄した第１分散体の前駆体を遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより全ての銀粒子１００％に対する一次粒径１０〜５０ｎｍの範囲内の銀ナノ粒子を数平均で７０％以上含有する第１分散体からなる太陽電池の電極形成用組成物を得る工程とA primary particle size of 10 to 100% of all silver particles is obtained by separating the coarse particles by adjusting the centrifugal force of the centrifuge using the centrifuge and the precursor of the first dispersion subjected to substitution washing with the alcohols. A step of obtaining a composition for forming an electrode of a solar cell comprising a first dispersion containing silver nanoparticles within a range of 50 nm in a number average of 70% or more;
を含むことを特徴とする請求項１に記載された太陽電池の電極形成用組成物を製造する方法。The method of manufacturing the composition for electrode formation of the solar cell described in Claim 1 characterized by the above-mentioned. 塩化金酸、塩化白金酸、硝酸パラジウム、三塩化ルテニウム、塩化ニッケル、硝酸第一銅、二塩化錫、硝酸インジウム、塩化亜鉛、硫酸鉄、硫酸クロム又は硫酸マンガンを水に溶解して第２金属塩水溶液を調製する工程と、Second metal by dissolving chloroauric acid, chloroplatinic acid, palladium nitrate, ruthenium trichloride, nickel chloride, cuprous nitrate, tin dichloride, indium nitrate, zinc chloride, iron sulfate, chromium sulfate or manganese sulfate in water Preparing an aqueous salt solution;
濃度１０〜４０％のクエン酸ナトリウム、りんご酸ナトリウム又はグリコール酸ナトリウムの水溶液に不活性ガスの気流中で粒状又は粉状の硫酸第一鉄を加えて溶解させて還元剤水溶液を調製する工程と、A step of preparing an aqueous reducing agent solution by adding granular or powdered ferrous sulfate in an inert gas stream to an aqueous solution of sodium citrate, sodium malate or sodium glycolate having a concentration of 10 to 40%; ,
前記不活性ガス気流中で前記還元剤水溶液を撹拌しながら、前記還元剤水溶液の量の１／１０以下の割合で反応温度が３０〜６０℃に保持されるように室温の前記第２金属塩水溶液を前記還元剤水溶液に滴下して混合する工程と、While stirring the reducing agent aqueous solution in the inert gas stream, the second metal salt at room temperature so that the reaction temperature is maintained at 30 to 60 ° C. at a ratio of 1/10 or less of the amount of the reducing agent aqueous solution. Dropping and mixing an aqueous solution into the reducing agent aqueous solution;
前記混合液の撹拌を更に１０〜３００分間続けてＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ又はＭｎの金属コロイドからなる第２分散液を調製する工程と、Stirring the mixture for another 10 to 300 minutes to prepare a second dispersion composed of a metal colloid of Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr or Mn; ,
前記第２分散液を室温で放置することにより沈降したＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ又はＭｎの金属ナノ粒子の凝集物をデカンテーション又は遠心分離法により分離する工程と、Decantation or centrifugation of aggregates of Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr, or Mn metal nanoparticles precipitated by allowing the second dispersion to stand at room temperature Separating by the method,
前記第２分散液から分離した固形分に水を加えて第２分散体の前駆体を得る工程と、Adding water to the solid content separated from the second dispersion to obtain a precursor of the second dispersion;
前記第２分散体の前駆体を限外ろ過により脱塩処理する工程と、Desalting the precursor of the second dispersion by ultrafiltration;
前記脱塩処理した前記第２分散体の前駆体をアルコール類で置換洗浄してＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ又はＭｎの含有量を２．５〜５０重量％に調整する工程と、The precursor of the second dispersion subjected to the desalting treatment is substituted and washed with alcohols so that the content of Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr, or Mn is 2. Adjusting to 5 to 50% by weight;
前記アルコール類で置換洗浄した第２分散体の前駆体を遠心分離機を用いこの遠心分離機の遠心力を調整して粗粒子を分離することにより全てのＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ又はＭｎの金属ナノ粒子１００％に対する一次粒径１０〜５０ｎｍの範囲内のＡｕ、Ｐｔ、Ｐｄ、Ｒｕ、Ｎｉ、Ｃｕ、Ｓｎ、Ｉｎ、Ｚｎ、Ｆｅ、Ｃｒ又はＭｎの金属ナノ粒子を数平均で７０％以上含有する第２分散体を得る工程と、The precursor of the second dispersion that has been subjected to substitution washing with the alcohols is separated by using a centrifuge to adjust the centrifugal force of the centrifuge to separate coarse particles, thereby making all Au, Pt, Pd, Ru, Ni, Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, in a primary particle size range of 10 to 50 nm with respect to 100% of Cu, Sn, In, Zn, Fe, Cr, or Mn metal nanoparticles. Obtaining a second dispersion containing 70% or more of Cr or Mn metal nanoparticles in number average;
請求項４に記載された７５重量％以上の前記第１分散体と２重量％以上かつ２５重量％未満の前記第２分散体とを前記第１及び第２分散体の合計含有量が１００重量％となるように混合することにより太陽電池の電極形成用組成物を得る工程とA total content of the first and second dispersions of 100% by weight of the first dispersion of 75% by weight or more and the second dispersion of 2% by weight or more and less than 25% by weight according to claim 4. % To obtain a composition for forming an electrode of a solar cell by mixing so as to be
を含むことを特徴とする請求項２に記載された太陽電池の電極形成用組成物を製造する方法。The method of manufacturing the composition for electrode formation of the solar cell described in Claim 2 characterized by the above-mentioned. 請求項１ないし３いずれか１項に記載の電極形成用組成物を基材上に湿式塗工法で塗工して太陽電池用電極を形成する方法。 A method for forming a solar cell electrode by applying the electrode-forming composition according to any one of claims 1 to 3 on a substrate by a wet coating method. 請求項１ないし３いずれか１項に記載の電極形成用組成物を基材上に湿式塗工法で塗工して焼成後の厚さが０．１〜２．０μｍの範囲内となるように成膜する工程と、
前記上面に成膜された基材を１３０〜４００℃で焼成する工程と
を含む太陽電池の電極の形成方法。 The electrode-forming composition according to any one of claims 1 to 3 is applied on a substrate by a wet coating method so that the thickness after firing is within a range of 0.1 to 2.0 µm. Forming a film;
And baking the substrate formed on the upper surface at 130 to 400 ° C. 基材がシリコン、ガラス、透明導電材料を含むセラミックス、高分子材料又は金属からなる基板のいずれか、或いは前記シリコン、前記ガラス、前記透明導電材料を含むセラミックス、前記高分子材料及び前記金属からなる群より選ばれた２種以上の積層体である請求項６又は７記載の太陽電池の電極の形成方法。 The substrate is made of silicon, glass, ceramics containing a transparent conductive material, a substrate made of a polymer material or a metal, or made of the silicon, the glass, a ceramic containing the transparent conductive material, the polymer material or the metal. The method for forming an electrode of a solar cell according to claim 6 or 7, which is a laminate of two or more selected from the group. 基材が太陽電池素子又は透明電極付き太陽電池素子のいずれかである請求項６又は７記載の太陽電池の電極の形成方法。 The method for forming an electrode of a solar cell according to claim 6 or 7 , wherein the substrate is either a solar cell element or a solar cell element with a transparent electrode. 湿式塗工法がスプレーコーティング法、ディスペンサコーティング法、スピンコーティング法、ナイフコーティング法、スリットコーティング法、インクジェットコーティング法、スクリーン印刷法、オフセット印刷法又はダイコーティング法のいずれかである請求項６又は７記載の太陽電池の電極の形成方法。 Wet coating method is a spray coating method, dispenser coating method, spin coating method, knife coating method, a slit coating method, inkjet coating method, screen printing method, according to claim 6 or 7, wherein either the offset printing method or die coating method Of forming solar cell electrode. 請求項６ないし１０いずれか１項に記載の電極の形成方法により形成した電極を用いたことを特徴とする太陽電池。 A solar cell using an electrode formed by the method for forming an electrode according to any one of claims 6 to 10 .
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