JP2020002445A - Method for producing alloy particle dispersion, alloy particle dispersion, and method for producing coated base material - Google Patents
Method for producing alloy particle dispersion, alloy particle dispersion, and method for producing coated base material Download PDFInfo
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本発明は、導電性材料等に有用な合金粒子分散液の製造方法に関する。 The present invention relates to a method for producing an alloy particle dispersion useful for conductive materials and the like.
金属粒子は、触媒材料、半導体材料、導電性材料等として各種用途に用いられている。例えば、導電性材料は、各種電子デバイスの電極、回路、帯電防止用透明被膜、電磁波遮蔽用透明被膜、コンデンサ用電極等に用いられている（非特許文献１参照）。 Metal particles are used in various applications as catalyst materials, semiconductor materials, conductive materials, and the like. For example, conductive materials are used for electrodes, circuits, antistatic transparent films, electromagnetic wave shielding transparent films, capacitor electrodes, and the like of various electronic devices (see Non-Patent Document 1).
このような金属粒子の製造方法として、有機溶剤中で金属塩を還元して金属粒子を製造する方法が提案されている（例えば、特許文献１及び２参照）。しかしながら、この有機溶剤を用いる方法で得られる金属粒子は、導電性が低いという問題がある。 As a method for producing such metal particles, a method for producing metal particles by reducing a metal salt in an organic solvent has been proposed (for example, see Patent Documents 1 and 2). However, the metal particles obtained by the method using the organic solvent have a problem of low conductivity.
そこで、導電性のより高い金属粒子を得るべく、水中で金属粒子分散液を製造することも試みられている。例えば、溶媒に不活性ガスを流通させながら有機安定化剤を使用して、金属粒子にクエン酸被覆層を設け、耐酸化性能を向上させる方法が提案されている（例えば、特許文献３参照）。 In order to obtain metal particles having higher conductivity, production of a metal particle dispersion in water has been attempted. For example, a method has been proposed in which an organic stabilizer is used while flowing an inert gas through a solvent to provide a citric acid coating layer on metal particles to improve oxidation resistance (for example, see Patent Document 3). .
しかしながら、金属粒子の酸化やイオン化を抑制するには不充分であり、安定した金属粒子分散液を得ることが難しい。また、有機物で被覆されているため、導電性が低いという問題がある。 However, it is insufficient to suppress oxidation and ionization of metal particles, and it is difficult to obtain a stable metal particle dispersion. In addition, since it is covered with an organic substance, there is a problem that the conductivity is low.
また、合金粒子を使用することによって、単一種の金属粒子よりも高い耐酸化性能を示す場合があるが、導電性は向上しないという問題がある（例えば、特許文献４参照）。 In addition, the use of alloy particles may exhibit higher oxidation resistance than a single kind of metal particles, but has a problem that the conductivity is not improved (for example, see Patent Document 4).
本発明の課題は、導電性が高く、保存安定性が高い合金粒子分散液を提供することにある。 An object of the present invention is to provide an alloy particle dispersion having high conductivity and high storage stability.
平均気泡径が４０ｎｍ〜１０μｍの微小気泡を含み、かつ有機安定化剤を含まない液中で、複数種の金属塩の還元反応（粒子調製工程）を行う。次いで、この複数種の金属塩を還元して得た合金粒子を洗浄液で洗浄して塩を除去（洗浄工程）することによって、合金粒子の酸化やイオン化を抑制して、合金粒子分散液の保存安定性が飛躍的に向上（長期化）する合金粒子分散液が得られる。 A reduction reaction (particle preparation step) of a plurality of types of metal salts is performed in a liquid containing microbubbles having an average bubble diameter of 40 nm to 10 μm and no organic stabilizer. Next, the alloy particles obtained by reducing the plural kinds of metal salts are washed with a washing liquid to remove salts (washing step), thereby suppressing oxidation and ionization of the alloy particles and storing the alloy particle dispersion. An alloy particle dispersion in which stability is dramatically improved (extended) is obtained.
金属塩の還元反応時において、この微小気泡を含む液を使用することで、有機安定化剤がなくとも合金粒子が凝集せずに、粒子の分散性が高く、保存安定性が高い合金粒子分散液が得られることを見出した。さらに、この液中には有機安定化剤が含まれず、得られた分散液を用いた被膜付基材の合金粒子は有機物で被覆されないため、高い導電性能を示すことを見出した。 During the reduction reaction of the metal salt, by using the liquid containing the microbubbles, the alloy particles do not agglomerate without an organic stabilizer, the dispersibility of the particles is high, and the storage stability of the alloy particles is high. It was found that a liquid was obtained. Furthermore, it has been found that this liquid does not contain an organic stabilizer and that the alloy particles of the coated substrate using the obtained dispersion are not coated with an organic substance, so that they exhibit high conductive performance.
合金粒子の酸化やイオン化が抑制された保存安定性が高い合金粒子分散液を得られる。また、この合金粒子分散液を用いた被膜付基材は、高い導電性能を示す。 An alloy particle dispersion having high storage stability in which oxidation and ionization of the alloy particles are suppressed can be obtained. Further, the coated substrate using the alloy particle dispersion exhibits high conductive performance.
本発明の合金粒子分散液の製造方法は、微小気泡（マイクロナノバブル）を含み、かつ有機安定化剤を含まない液（以下、反応液ということがある）中で複数種の金属塩を還元して合金粒子を調製する粒子調製工程と、粒子調製工程で調製した合金粒子を洗浄液で洗浄する洗浄工程とを有する。
この製造方法は、上記各工程の前後に他の工程を有していてもよい。例えば、洗浄工程の後に、粗大粒子を除去する粗大粒子除去工程を有していてもよい。
The method for producing an alloy particle dispersion liquid of the present invention comprises reducing a plurality of metal salts in a liquid containing microbubbles (micro-nano bubbles) and containing no organic stabilizer (hereinafter, sometimes referred to as a reaction liquid). And a cleaning step of cleaning the alloy particles prepared in the particle preparation step with a cleaning liquid.
This manufacturing method may have other steps before and after each of the above steps. For example, after the washing step, a coarse particle removing step of removing coarse particles may be provided.
本発明に使用する微小気泡を含む液（微小気泡を含むバブリング液を含む）は、従来の不活性ガスによる脱気（脱酸素）処理水よりも溶存酸素濃度が高く、酸化還元電位も高い。このため、微小気泡を含む液の使用は、より酸化されやすい条件となるので、微小気泡を含む液を還元反応系に用いることは一般的には好ましくないと考えられる。また、有機安定化剤については、金属塩や合金粒子に吸着して、分散安定性を高める機能がある。このため、金属塩の還元反応において、有機安定化剤が存在しないと、合金粒子が凝集し、合金粒子分散液の安定性も低下するので、一般的には好ましくないと考えられる。
ところが、意外にも、この微小気泡を含む液を用いて金属塩の還元反応を行うと、有機安定化剤が存在しなくても、金属塩の分散性が高く、製造される合金粒子分散液の合金粒子が高い収率で得られ、合金粒子の分散性や保存安定性が向上することを見出した。また、この合金粒子分散液を使用した塗布液のポットライフも向上することを見出した。さらに、この塗布液を用いて作製した被膜付基材は、高い導電性（低い表面抵抗値）を有することを見出した。この導電性能は、微小気泡存在下、還元反応時に有機安定化剤を使用しない方が高性能であることを見出した。これらの理由は、よく分からないが、反応液中に含まれる微小気泡によって、合金粒子が酸化されずに、合金として存在するための保護作用があるためと推察している。加えて、金属塩の還元反応において、有機安定化剤が存在しないため、有機安定化剤が金属塩や合金粒子に吸着することはない。その結果、得られた合金粒子分散液、それを使用した塗布液および被膜付基材中の合金粒子は、有機安定化剤に由来する有機物で被覆されないため、導電性能が向上していると考えている。
The liquid containing microbubbles (including the bubbling liquid containing microbubbles) used in the present invention has a higher dissolved oxygen concentration and a higher oxidation-reduction potential than conventional degassed (deoxygenated) water treated with an inert gas. For this reason, the use of a liquid containing microbubbles is more likely to be oxidized, and it is generally considered undesirable to use a liquid containing microbubbles in a reduction reaction system. Further, the organic stabilizer has a function of adsorbing to metal salts or alloy particles to enhance the dispersion stability. For this reason, in the reduction reaction of the metal salt, if the organic stabilizer is not present, the alloy particles are aggregated and the stability of the alloy particle dispersion liquid is lowered, so that it is generally considered to be undesirable.
However, surprisingly, when the reduction reaction of the metal salt is performed using the liquid containing the microbubbles, the dispersibility of the metal salt is high even without the presence of an organic stabilizer. It has been found that alloy particles of the formula (1) are obtained in a high yield, and that the dispersibility and storage stability of the alloy particles are improved. It has also been found that the pot life of a coating solution using this alloy particle dispersion is improved. Furthermore, it has been found that a substrate with a film produced using this coating liquid has high conductivity (low surface resistance). It has been found that this conductive performance is higher when no organic stabilizer is used during the reduction reaction in the presence of microbubbles. Although the reason for this is not clear, it is presumed that the microbubbles contained in the reaction solution do not oxidize the alloy particles but have a protective action to exist as an alloy. In addition, since no organic stabilizer is present in the reduction reaction of the metal salt, the organic stabilizer does not adsorb to the metal salt or the alloy particles. As a result, the alloy particles in the obtained alloy particle dispersion, the coating solution using the same, and the base material with a coating are not covered with the organic substance derived from the organic stabilizer, and thus the conductive performance is considered to be improved. ing.
また、上述の複数種の金属塩の還元反応（粒子調製工程）での液と、これら金属塩を還元して得た合金粒子の洗浄（洗浄工程）での洗浄液の両方で微小気泡を含む液を使用することで、より高い収率で合金粒子が得られ、合金粒子分散液の保存安定性が向上し、この合金粒子分散液を使用した塗布液のポットライフがさらに向上することを見出した。 In addition, a liquid containing microbubbles is used in both the liquid in the above-described reduction reaction of the plurality of metal salts (particle preparation step) and the cleaning liquid in the cleaning of the alloy particles obtained by reducing these metal salts (cleaning step). By using, the alloy particles are obtained in a higher yield, the storage stability of the alloy particle dispersion is improved, and the pot life of the coating liquid using the alloy particle dispersion is further improved. .
さらに、この合金粒子分散液は、その金属種にもよるが、単一種の金属粒子分散液よりも高い保存安定性を有することを見出した。 Furthermore, it has been found that this alloy particle dispersion has higher storage stability than a single type of metal particle dispersion, depending on the type of metal.
加えて、この合金粒子を用いて形成した被膜は、その金属種にもよるが、単一種の金属粒子を用いて形成した被膜よりも、長期間にわたり導電性の低下を抑えられることを見出した。 In addition, it has been found that, depending on the metal species, the coating formed using the alloy particles can suppress the decrease in conductivity over a longer period than the coating formed using a single type of metal particles. .
このことは、金属粒子を単一種の金属粒子ではなく合金粒子とすることで、単体の金属粒子にはない性能を発現することを示すものである。さらに、例えば、貴金属粒子を使用している場合と比べて、貴金属と比較的安価な卑金属との合金粒子を使用する場合は、その金属種によっては単一種の金属粒子分散液よりも保存安定性が向上し、被膜の導電性の低下を長期間にわたり抑えられる。
また、使用する金属の種類や割合にもよるが、貴金属と卑金属、あるいは卑金属同士の合金粒子の方が貴金属粒子よりも製造コストが抑えられるメリットもある。
以下に、合金粒子分散液の製造方法について説明する。
This indicates that by using metal particles not as a single kind of metal particles but as alloy particles, performances not exhibited by a single metal particle are exhibited. Furthermore, for example, when alloy particles of a noble metal and a relatively inexpensive base metal are used, compared to the case where noble metal particles are used, the storage stability of some metal species is higher than that of a single metal particle dispersion. And the decrease in the conductivity of the coating film can be suppressed for a long period of time.
Further, although it depends on the type and proportion of the metal used, there is also an advantage that the production cost of the noble metal and the base metal, or the alloy particles of the base metals is lower than that of the noble metal particles.
Hereinafter, a method for producing the alloy particle dispersion will be described.
［合金粒子分散液の製造方法］
〈粒子調製工程〉
反応液中で、還元剤と複数種の金属塩とを混合して合金粒子を調製する。反応液としては、有機安定化剤を含まず、後述する微小気泡を含む液を用いるのであれば、有機溶媒であっても、水であってもよい。ただし、水の場合に、効果がより発揮される。
反応液中に酸素等の酸化性ガスが存在すると、合金や金属が酸化するおそれがある。このため、反応液及び反応液が接する空間において、酸化性ガスを可能な限り減じることが望ましい。本工程は、酸化性ガスの混入を抑制するため、Ｎ２ガスや希ガス等の不活性ガスによりパージした状態で行うことが好ましい。
ここで、酸化性ガスとしては、酸素、オゾン、炭酸ガス、一酸化窒素、一酸化二窒素、二酸化窒素、フッ素、塩素、二酸化塩素、三フッ化窒素、三フッ化塩素、四塩化珪素、二フッ化酸素、ペルクロリルフルオリド等が例示される。
[Method for producing alloy particle dispersion]
<Particle preparation step>
In the reaction liquid, a reducing agent and a plurality of metal salts are mixed to prepare alloy particles. As the reaction solution, an organic solvent or water may be used as long as a solution containing microbubbles described below without using an organic stabilizer is used. However, in the case of water, the effect is more exhibited.
If an oxidizing gas such as oxygen is present in the reaction solution, the alloy or metal may be oxidized. For this reason, it is desirable to reduce the amount of oxidizing gas as much as possible in the reaction solution and the space in contact with the reaction solution. This step is preferably performed in a state of being purged with an inert gas such as N 2 gas or a rare gas in order to suppress mixing of an oxidizing gas.
Here, as the oxidizing gas, oxygen, ozone, carbon dioxide, nitrogen monoxide, nitrous oxide, nitrogen dioxide, fluorine, chlorine, chlorine dioxide, nitrogen trifluoride, chlorine trifluoride, silicon tetrachloride, Oxygen fluoride, perchloryl fluoride and the like are exemplified.
還元反応において、もし反応液中に有機安定化剤が存在すると、金属塩に有機安定化剤が吸着されるため、金属塩の分散性が向上し、金属塩の還元もスムーズに行われる。また、有機安定化剤は、金属塩が還元されて得られた合金粒子に吸着して、合金粒子分散液の分散性安定性が向上する。このため、この合金粒子分散液を使用した塗布液のポットライフも向上する。ところが、合金粒子表面が有機物に被覆されるため、この合金粒子を使用した被膜の導電性は、有機安定化剤を使用していないものに比べて低下するおそれがある。
この有機安定化剤は、ゼラチン、ポリビニルアルコール、ポリビニルピロリドン、酢酸ビニル、ポリアクリル酸、カルボン酸化合物等が例示される。
In the reduction reaction, if an organic stabilizer is present in the reaction solution, the organic stabilizer is adsorbed on the metal salt, so that the dispersibility of the metal salt is improved and the reduction of the metal salt is performed smoothly. Further, the organic stabilizer is adsorbed on the alloy particles obtained by reducing the metal salt, and the dispersibility of the alloy particle dispersion is improved. Therefore, the pot life of the coating liquid using the alloy particle dispersion is also improved. However, since the surface of the alloy particles is coated with an organic substance, the conductivity of a film using the alloy particles may be lower than that of a film using no organic stabilizer.
Examples of the organic stabilizer include gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, vinyl acetate, polyacrylic acid, and carboxylic acid compounds.
本工程の反応液は、酸化還元電位（ＯＲＰ）が、−５０ｍＶ以下が好ましく、−１００ｍＶ以下がより好ましい。また、ｐＨが、２．５〜１０．５が好ましく、２．７〜１０．０がより好ましい。この酸化還元電位及びｐＨの範囲内で複数種の金属塩の還元を行うことにより、合金粒子の生成がスムーズに行われる。また、反応温度としては、１０〜８０℃が好ましい。 The reaction solution in this step preferably has an oxidation-reduction potential (ORP) of -50 mV or less, more preferably -100 mV or less. Further, the pH is preferably from 2.5 to 10.5, and more preferably from 2.7 to 10.0. By performing reduction of a plurality of types of metal salts within the ranges of the oxidation-reduction potential and the pH, generation of alloy particles is performed smoothly. Moreover, as reaction temperature, 10-80 degreeC is preferable.
《微小気泡》
微小気泡は、好ましくは平均気泡径が４０ｎｍ〜１０μｍの微小気泡（マイクロナノバブル）である。かかる微小気泡は、気泡径が４０〜１００ｎｍ（０．１μｍ）のいわゆるナノバブル、及び気泡径が０．１〜１０μｍのいわゆるマイクロバブルの少なくとも一方を含むものであり、両者を含むものが好ましい。微小気泡の平均気泡径の上限は、５００ｎｍが好ましく、３５０ｎｍがより好ましく、２００ｎｍがさらに好ましい。また、微小気泡の平均気泡径の下限は、５０ｎｍが好ましく、６０ｎｍがより好ましく、６５ｎｍがさらに好ましい。
《Micro bubbles》
The microbubbles are preferably microbubbles (micro-nano bubbles) having an average bubble diameter of 40 nm to 10 μm. Such microbubbles include at least one of a so-called nanobubble having a bubble diameter of 40 to 100 nm (0.1 μm) and a so-called microbubble having a bubble diameter of 0.1 to 10 μm, and preferably include both. The upper limit of the average bubble diameter of the microbubbles is preferably 500 nm, more preferably 350 nm, and still more preferably 200 nm. The lower limit of the average bubble diameter of the microbubbles is preferably 50 nm, more preferably 60 nm, and even more preferably 65 nm.
微小気泡の含有量は、本発明の効果を有効に発揮すべく、１．０×１０６個／ｍＬ以上が好ましく、１．０×１０７個／ｍＬ以上がより好ましく、１．０×１０８個／ｍＬ以上がさらに好ましい。その上限は特に制限はないが、１．０×１０１１個／ｍＬが好ましく、５．０×１０１０個／ｍＬがより好ましく、１．０×１０１０個／ｍＬがさらに好ましい。 The content of the microbubbles is preferably 1.0 × 10 6 / mL or more, more preferably 1.0 × 10 7 / mL or more, and 1.0 × 10 6 / mL in order to effectively exert the effects of the present invention. More preferably, the number is 8 / mL or more. The upper limit is not particularly limited, but is preferably 1.0 × 10 11 / mL, more preferably 5.0 × 10 10 / mL, and still more preferably 1.0 × 10 10 / mL.
微小気泡の平均気泡径及び気泡個数は、液中の気泡のブラウン運動移動速度を、ナノ粒子トラッキング解析法（ＮＴＡ）で解析して求められる。例えば、Ｍａｌｖｅｒｎ社製「ナノサイト ＮＳ３００」を用いて測定できる。 The average bubble diameter and the number of bubbles of the microbubbles can be obtained by analyzing the Brownian movement speed of the bubbles in the liquid by a nanoparticle tracking analysis method (NTA). For example, it can be measured using "Nanosite NS300" manufactured by Malvern.
微小気泡を形成する気体は、非酸化性ガスが好ましい。具体的には、窒素、水素、及び希ガスの少なくとも１種が好ましい。 The gas forming the microbubbles is preferably a non-oxidizing gas. Specifically, at least one of nitrogen, hydrogen, and a rare gas is preferable.
《金属塩》
合金粒子の原料となる金属塩は、周期表の４族、５族、６族、８族、９族、１０族、１１族、１３族、１４族及び１５族から選ばれる複数種の金属の塩が用いられる。これらの金属塩は予め混合して用いてもよい。塩の種類としては、例えば、塩化物塩、硝酸塩、硫酸塩、有機酸塩等が挙げられる。
《Metal salt》
The metal salt used as the raw material of the alloy particles is a metal salt of a plurality of metals selected from Groups 4, 5, 6, 8, 9, 9, 10, 11, 13, 14 and 15 of the periodic table. Salt is used. These metal salts may be mixed in advance and used. Examples of the type of salt include chloride, nitrate, sulfate, and organic acid salt.
好ましい金属元素は、４族ではＴｉ、５族ではＴａ、６族ではＷ、８族ではＲｕ、９族ではＣｏ、Ｒｈ、１０族ではＮｉ、Ｐｄ、Ｐｔ、１１族ではＣｕ、Ａｇ、Ａｕ、１３族ではＡｌ、Ｉｎ、１４族ではＳｎ、１５族ではＳｂが例示される。この製造方法は、ＡｕやＡｇ以外の酸化されやすい金属にも適用可能である。 Preferred metal elements are Ti for Group 4, Ti for Group 5, Ta for Group 6, Ru for Group 8, Co, Rh for Group 9, Ni, Pd, Pt for Group 10, Cu, Ag, Au for Group 11, and so on. Group 13 is exemplified by Al and In, group 14 is exemplified by Sn, and group 15 is exemplified by Sb. This manufacturing method is also applicable to easily oxidizable metals other than Au and Ag.
合金粒子を形成する金属元素の割合は任意に設定できる。その方法は特に限定されないが、例えば、合金粒子の原料となる金属塩を所望する合金の金属比となるように液中で混合して、還元することが好ましい。 The ratio of the metal element forming the alloy particles can be set arbitrarily. The method is not particularly limited, but, for example, it is preferable to mix and reduce a metal salt as a raw material of the alloy particles in a liquid so as to have a desired metal ratio of the alloy.
《還元剤》
粒子調製工程における還元反応は、通常、還元剤を用いる。
還元剤は、例えば、硫酸第一鉄、ＮａＢＨ４、ヒドラジン、水素、アルコール、次亜リン酸ナトリウム、ＬｉＢＨ４、ＬｉＡｌＨ４、ジボランが挙げられる。
《Reducing agent》
The reduction reaction in the particle preparation step usually uses a reducing agent.
Examples of the reducing agent include ferrous sulfate, NaBH 4 , hydrazine, hydrogen, alcohol, sodium hypophosphite, LiBH 4 , LiAlH 4 , and diborane.
還元剤の使用量は、金属塩の還元性によっても異なるが、合金粒子を構成する各金属種の金属塩１モルに対し、０．５〜１０モルが好ましく、１〜５モルがより好ましい。ここで、還元剤が合金粒子を構成する各金属種の金属塩１モルに対し０．５モル未満の場合は、還元が不充分となり、所望の合金粒子が得られない場合がある。逆に、還元剤が合金粒子を構成する各金属種の金属塩１モルに対し１０モルを超えると、必要以上に粒子径の大きな合金粒子が生成する場合がある。 The amount of the reducing agent used depends on the reducibility of the metal salt, but is preferably 0.5 to 10 mol, more preferably 1 to 5 mol, per 1 mol of the metal salt of each metal species constituting the alloy particles. Here, when the reducing agent is less than 0.5 mol with respect to 1 mol of the metal salt of each metal species constituting the alloy particles, the reduction becomes insufficient and desired alloy particles may not be obtained. Conversely, if the reducing agent exceeds 10 moles with respect to 1 mole of the metal salt of each metal species constituting the alloy particles, alloy particles having a particle size larger than necessary may be generated.
《ｐＨ調整剤》
粒子調製工程の反応液は、上記のように、ｐＨが２．５〜１０．５になるように、ｐＨ調整剤を用いて調整しても良い。ｐＨ調整剤は、鉱酸、有機酸が適している。
ここで、有機酸を使用する場合、その分子量が大きいものは、合金粒子への有機物被覆のおそれがあるため、炭素数が１〜３の低分子量のものが好ましい。その使用量は、金属塩１モルに対して０．５モル未満が好ましい。
<< pH adjuster >>
As described above, the reaction solution in the particle preparation step may be adjusted using a pH adjuster such that the pH is 2.5 to 10.5. As the pH adjuster, mineral acids and organic acids are suitable.
Here, when an organic acid is used, the one having a large molecular weight may have a low molecular weight of 1 to 3 carbon atoms because the alloy particles may be coated with an organic substance. The use amount is preferably less than 0.5 mol per 1 mol of the metal salt.
〈洗浄工程〉
洗浄工程では、粒子調製工程で調製した合金粒子を洗浄液で洗浄する。ここで、脱塩が行われる。この塩とは、複数種の金属塩の還元処理によって生じた合金粒子以外の物質であり、反応液中にイオンとして存在する。具体的には、ナトリウム、鉄等の金属イオンや、ホウ素イオン、塩化物イオン、硝酸イオン、硫酸イオン、有機酸イオン等が例示される。この洗浄工程では、カルボン酸化合物等の金属イオンと錯体を形成する有機安定化剤を使用しても構わない。それは、例えば、還元剤として硫酸第一鉄のような金属を含む還元剤を使用した場合、この還元剤の金属イオンと有機安定化剤とが錯体を形成して、効率よく還元剤を除去できるためである。
<Cleaning process>
In the washing step, the alloy particles prepared in the particle preparation step are washed with a washing liquid. Here, desalination is performed. This salt is a substance other than alloy particles generated by the reduction treatment of a plurality of types of metal salts, and exists as an ion in the reaction solution. Specific examples include metal ions such as sodium and iron, boron ions, chloride ions, nitrate ions, sulfate ions, and organic acid ions. In this washing step, an organic stabilizer which forms a complex with a metal ion such as a carboxylic acid compound may be used. For example, when a reducing agent containing a metal such as ferrous sulfate is used as a reducing agent, a metal ion of the reducing agent and an organic stabilizer form a complex, and the reducing agent can be efficiently removed. That's why.
洗浄液は、水やアルコールが適しており、その他の成分を含んでいてもよい。この洗浄液は、予め不活性ガスをバブリングして酸素を除去したバブリング液及び微小気泡を含有した液の少なくとも一方を用いることが好ましい。特に、微小気泡を含む液を用いることが好ましい。微小気泡を含む液の詳細は、上記粒子調製工程で用いた微小気泡を含む液（反応液）と同様である。また、洗浄後に製造された合金粒子分散液も微小気泡を含むことが好ましい。 The cleaning liquid is suitably water or alcohol, and may contain other components. As this cleaning liquid, it is preferable to use at least one of a bubbling liquid from which oxygen has been removed by bubbling an inert gas in advance and a liquid containing microbubbles. In particular, it is preferable to use a liquid containing microbubbles. The details of the liquid containing microbubbles are the same as the liquid containing microbubbles (reaction liquid) used in the particle preparation step. Further, it is preferable that the alloy particle dispersion produced after the washing also contains microbubbles.
微小気泡を含む洗浄液で合金粒子を洗浄することにより、合金粒子のイオン化や酸化を防止して、合金粒子分散液の保存安定性及びこの合金粒子分散液を使用した塗布液のポットライフを飛躍的に向上できる。また、製造される合金粒子の分散性が向上し、最終的な分散液中の塩や有機安定化剤に由来する有機物の量を低減できる。したがって、被膜にした際、合金粒子同士がより直接的に接触し、粒子境界の抵抗が小さくなり、結果として、高い導電性を有する被膜を形成できる。 By washing the alloy particles with a cleaning solution containing microbubbles, ionization and oxidation of the alloy particles are prevented, and the storage stability of the alloy particle dispersion and the pot life of the coating liquid using this alloy particle dispersion are dramatically improved. Can be improved. Further, the dispersibility of the produced alloy particles is improved, and the amount of salts and organic substances derived from the organic stabilizer in the final dispersion can be reduced. Therefore, when a film is formed, the alloy particles come into direct contact with each other, and the resistance at the particle boundary is reduced. As a result, a film having high conductivity can be formed.
洗浄方法は、限外ろ過膜法やデカンテーション法が例示される。洗浄によって、硝酸イオン、硫酸イオン等の不純分を除去することができる。さらに、イオン交換樹脂を用いて精製することが好ましい。 Examples of the washing method include an ultrafiltration membrane method and a decantation method. By washing, impurities such as nitrate ions and sulfate ions can be removed. Further, it is preferable to purify using an ion exchange resin.
微小気泡を含む液を用いると、十分に不純分を除去でき、後のイオン交換樹脂による処理の簡略化（樹脂量の低減）も図れるため、効率的に合金粒子を製造できる。また、洗浄回数を減らすことも可能であり、これによっても効率的に合金粒子を製造できる。このような洗浄工程の簡略化により、合金粒子のロスが少なくなり、収率を向上できる。さらに、洗浄工程の簡略化によって、合金粒子の酸化の誘発が抑制されるので、この合金粒子を用いて形成した被膜は導電性が高くなる。 When a liquid containing microbubbles is used, impurities can be sufficiently removed, and subsequent treatment with an ion exchange resin can be simplified (resin amount can be reduced), so that alloy particles can be efficiently produced. Further, it is possible to reduce the number of times of cleaning, and thereby, it is possible to efficiently produce alloy particles. Such simplification of the cleaning step reduces the loss of alloy particles and improves the yield. Furthermore, the induction of oxidation of the alloy particles is suppressed by the simplification of the cleaning process, so that the film formed using the alloy particles has high conductivity.
〈粗大粒子除去工程〉
洗浄工程の後、遠心分離等により、粗大粒子を除去することが好ましい。
<Coarse particle removal process>
After the washing step, it is preferable to remove coarse particles by centrifugation or the like.
また、本発明は、上述の製造方法により調製された合金粒子分散液に関する。以下に、これについて説明をする。
［合金粒子分散液］
本発明の合金粒子分散液は、微小気泡を含む液中に合金粒子が分散していることを特徴とする。微小気泡を含む液の詳細は、上記粒子調製工程で用いた微小気泡を含む液（反応液）と同様である。また、合金粒子としては、周期表の４族、５族、６族、８族、９族、１０族、１１族、１３族、１４族、１５族から選ばれる金属の合金粒子が挙げられる。合金粒子は、複数種を混合して用いてもよい。この合金粒子分散液は、上記の製造方法により製造できる。
分散媒は、水や有機溶媒が適している。ここで、有機溶媒は、特に種類を選ばないが、塗布液としての加工のしやすさや被膜付基材の製造のしやすさからアルコール類が好ましく、メタノールやエタノールがより好ましい。
The present invention also relates to an alloy particle dispersion prepared by the above-described production method. Hereinafter, this will be described.
[Alloy particle dispersion]
The alloy particle dispersion of the present invention is characterized in that alloy particles are dispersed in a liquid containing microbubbles. The details of the liquid containing microbubbles are the same as the liquid containing microbubbles (reaction liquid) used in the particle preparation step. In addition, examples of the alloy particles include alloy particles of a metal selected from Group 4, Group 5, Group 6, Group 8, Group 9, Group 10, Group 11, Group 13, Group 14, and Group 15 of the periodic table. The alloy particles may be used as a mixture of a plurality of types. This alloy particle dispersion can be produced by the above production method.
Water and organic solvents are suitable as the dispersion medium. Here, the kind of the organic solvent is not particularly limited, but alcohols are preferable, and methanol and ethanol are more preferable, because of easiness of processing as a coating liquid and easiness of production of a substrate with a film.
金属粒子分散液の保存安定性は、不活性ガスでバブリングした溶媒のみを使用して製造された場合、その金属種にもよるが、通常、１年程度である。これに対し、本発明の合金粒子分散液の保存安定性は多くの場合１年を超える。これは、単に気泡が存在する場合の作用とは異なり、微小気泡と合金粒子との間で何らかの作用が働いているためと考えられる。 The storage stability of the metal particle dispersion is usually about one year, depending on the type of metal when manufactured using only a solvent bubbled with an inert gas. In contrast, the storage stability of the alloy particle dispersion of the present invention often exceeds one year. This is considered to be due to the fact that some action is acting between the microbubbles and the alloy particles, which is different from the action when only bubbles are present.
合金の種類は、前述の周期表の同じ族同士の金属種を組み合わせでも構わないし、違う族同士の金属種を組み合わせでも構わない。例えば、Ａｇ−Ｃｕ、Ａｇ−Ｐｄ、Ａｇ−Ａｕ、Ａｇ−Ｐｔ、Ｃｕ−Ｐｄ、Ｃｕ−Ｓｎ、Ｃｕ−Ｔｉ、Ｎｉ−Ｃｕ、Ａｇ−Ｃｕ−Ｐｄ、Ｃｕ−Ｓｎ−Ｎｉ、Ｎｉ−Ｃｕ−Ｓｉ、Ｒｕ−Ｐｔ等が例示される。
中でも、Ａｇ−Ｐｄ、Ｃｕ−Ｐｄ、Ｎｉ−Ｃｕといった合金粒子は酸化やイオン化を受けにくい。その結果、合金粒子との電気的な相互作用があると推定される微小気泡粒子との安定化効果もあり、保存安定性の高い分散液を得やすい。
The type of alloy may be a combination of metal species of the same group in the above-mentioned periodic table, or a combination of metal species of different groups. For example, Ag-Cu, Ag-Pd, Ag-Au, Ag-Pt, Cu-Pd, Cu-Sn, Cu-Ti, Ni-Cu, Ag-Cu-Pd, Cu-Sn-Ni, Ni-Cu- Si, Ru-Pt and the like are exemplified.
Among them, alloy particles such as Ag-Pd, Cu-Pd, and Ni-Cu are hardly oxidized or ionized. As a result, there is also a stabilizing effect with microbubble particles that are presumed to have an electrical interaction with the alloy particles, and it is easy to obtain a dispersion having high storage stability.
また、合金粒子の金属比は、合金粒子を構成する金属種の合計量に対して、最も割合の低い金属種が質量基準で０．５質量％以上が好ましく、１．０質量％以上がより好ましく、１０質量％以上がさらに好ましい。最も割合の低い金属種の割合が０．５質量％未満であると、合金粒子とした場合に単一種の金属粒子よりも高い保存安定性を示すものであっても、その効果を充分に示さないおそれがある。なお、割合の低い金属種は、通常、高価な貴金属であり、コストと効果の両面を考慮して、その金属比を決定することが好ましい。 Further, the metal ratio of the alloy particles is preferably 0.5% by mass or more, and more preferably 1.0% by mass or less, based on the mass of the metal species having the lowest ratio based on the total amount of metal species constituting the alloy particles. It is preferably at least 10% by mass. When the ratio of the lowest metal species is less than 0.5% by mass, even if the alloy particles show higher storage stability than a single metal particle, the effect is sufficiently exhibited. May not be. The metal species having a low ratio is usually an expensive noble metal, and it is preferable to determine the metal ratio in consideration of both cost and effect.
なお、現状の技術では、合金粒子と微小気泡が共存している分散液のまま、微小気泡の平均気泡径や気泡個数を測定することは困難である。このため、合金粒子を限外濾過膜で取り除き、この濾液に含まれる微小気泡を測定することにより、微小気泡の平均気泡径及び気泡個数を求める。すなわち、本発明の平均気泡径及び気泡個数は、分画分子量４０００の限外濾過膜を通過した濾液を測定したものをいう。 In the current technology, it is difficult to measure the average bubble diameter and the number of bubbles of the microbubbles in the state of the dispersion in which the alloy particles and the microbubbles coexist. Therefore, the alloy particles are removed with an ultrafiltration membrane, and the microbubbles contained in the filtrate are measured to determine the average bubble diameter and the number of microbubbles. That is, the average bubble diameter and the number of bubbles in the present invention refer to the values obtained by measuring the filtrate passed through an ultrafiltration membrane having a molecular weight cutoff of 4000.
合金粒子分散液の酸化還元電位（ＯＲＰ）は、０〜３００ｍＶが好ましく、１００〜２５０ｍＶがより好ましい。ここで、ＯＲＰが０ｍＶ未満の場合は、還元場にあるため合金粒子の分散性が不安定になる場合がある。逆に、ＯＲＰが３００ｍＶを超える場合は、合金粒子が酸化される場合がある。
また、ｐＨは、通常、４．０〜７．０であり、４．５〜６．５が好ましい。ここで、ｐＨが４．０未満の場合は、イオンの状態で存在し、合金粒子が得られない場合がある。逆に、ｐＨが７．０を超える場合は、塩濃度が高いため、合金粒子が凝集する場合がある。
The redox potential (ORP) of the alloy particle dispersion is preferably from 0 to 300 mV, more preferably from 100 to 250 mV. Here, if the ORP is less than 0 mV, the dispersibility of the alloy particles may be unstable due to the presence of the reducing field. Conversely, if the ORP exceeds 300 mV, the alloy particles may be oxidized.
Further, the pH is usually 4.0 to 7.0, and preferably 4.5 to 6.5. Here, when the pH is less than 4.0, it may exist in an ionic state, and alloy particles may not be obtained. Conversely, if the pH exceeds 7.0, the salt concentration is high, and the alloy particles may aggregate.
合金粒子分散液の電気伝導度は、１０〜５００μＳ／ｃｍが好ましく、５０〜３００μＳ／ｃｍがより好ましい。ここで、電気伝導度が１０μＳ／ｃｍ未満の場合は、分散剤が少なく保存安定性が低下する（寿命が短い）場合がある。逆に、電気伝導度が５００μＳ／ｃｍを超える場合は、塩濃度が高くなるため、保存安定性が低下する場合がある。また、導電膜を形成しても導電性が悪化する場合がある。 The electric conductivity of the alloy particle dispersion is preferably from 10 to 500 μS / cm, more preferably from 50 to 300 μS / cm. Here, when the electric conductivity is less than 10 μS / cm, the amount of the dispersant is small, and the storage stability may be reduced (the life may be short). Conversely, when the electric conductivity exceeds 500 μS / cm, the salt concentration becomes high, so that the storage stability may decrease. Further, even when a conductive film is formed, the conductivity may be deteriorated.
合金粒子分散液の不純分の各々の含有量は、合金粒子に対して、１００ｐｐｍ以下が好ましく、８０ｐｐｍ以下がより好ましく、５０ｐｐｍ以下がさらに好ましい。ここで、１００ｐｐｍを超えると、塩濃度が高くなるため、保存安定性が低下する場合がある。また、導電膜を形成しても導電性が悪化する場合がある。合金粒子分散液の不純分は、合金粒子と分散媒および有機安定化剤以外の物質である。これは、金属塩の還元処理によって生じた合金粒子以外の物質で、反応液中にイオンとして存在する。具体的には、ナトリウムや鉄等の金属イオンやホウ素イオン、塩化物イオン、硝酸イオン、硫酸イオン等が例示される。特に、ナトリウムと鉄の金属イオンは、導電性から見て、ナトリウムが１０ｐｐｍ以下、鉄が５０ｐｐｍ以下の両方を満足することが好ましい。 The content of each of the impurities in the alloy particle dispersion is preferably 100 ppm or less, more preferably 80 ppm or less, even more preferably 50 ppm or less, based on the alloy particles. Here, when the concentration exceeds 100 ppm, the salt concentration becomes high, so that the storage stability may decrease. Further, even when a conductive film is formed, the conductivity may be deteriorated. The impurities in the alloy particle dispersion are substances other than the alloy particles, the dispersion medium and the organic stabilizer. This is a substance other than the alloy particles generated by the reduction treatment of the metal salt, and exists as ions in the reaction solution. Specific examples include metal ions such as sodium and iron, boron ions, chloride ions, nitrate ions, and sulfate ions. In particular, from the viewpoint of conductivity, sodium and iron metal ions preferably satisfy both sodium of 10 ppm or less and iron of 50 ppm or less.
また、合金粒子分散液に含まれる合金粒子の炭素含有量は、合金粒子に対して０．１質量％以下が好ましく、０．０５質量％以下がより好ましい。
この合金粒子に含有される炭素は、金属塩、還元剤、ｐＨ調整剤、洗浄液、溶媒等の有機化合物に由来する。これには、合金粒子分散液の製造のために、意図的に添加されたものの他、原料等に不可避的に存在するものも含まれる。特に、合金粒子分散液に、前述の有機安定化剤が含まれていると、合金粒子表面が有機物で被覆されるため、被膜にした場合、導電性が低下するおそれがある。このような有機物に由来する炭素含有量は、後述のように、Ｃ（カーボン）量を分析することで求めることができる。
The carbon content of the alloy particles contained in the alloy particle dispersion is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, based on the alloy particles.
The carbon contained in the alloy particles is derived from organic compounds such as a metal salt, a reducing agent, a pH adjuster, a cleaning solution, and a solvent. This includes not only those intentionally added for the production of the alloy particle dispersion but also those inevitably present in the raw materials and the like. In particular, when the above-mentioned organic stabilizer is contained in the alloy particle dispersion liquid, the surface of the alloy particles is coated with an organic substance. The carbon content derived from such an organic substance can be determined by analyzing the C (carbon) content, as described later.
この合金粒子分散液に含まれる合金粒子の平均粒子径は、３〜２００ｎｍが好ましく、５〜７０ｎｍがより好ましい。平均粒子径が３〜２００ｎｍであれば、透明性の高い導電性被膜を得ることができる。
合金粒子の平均粒子径は、電子顕微鏡写真を撮影し、任意の５００個の粒子について、粒子径を測定し、その平均値として得る。
The average particle size of the alloy particles contained in the alloy particle dispersion is preferably from 3 to 200 nm, more preferably from 5 to 70 nm. When the average particle diameter is 3 to 200 nm, a highly transparent conductive film can be obtained.
The average particle diameter of the alloy particles is obtained by taking an electron micrograph, measuring the particle diameter of arbitrary 500 particles, and obtaining the average value.
本発明の合金粒子分散液は、合金粒子の酸化やイオン化を抑制できる。したがって、水系においても、従来実現できなかった長期の保存安定性が実現できる。また、この合金粒子分散液を使用した塗布液でも従来実現できなかった長期のポットライフが実現できる。さらに、この合金粒子分散液は、酸化物粒子の含有量が非常に少なく、導電性の高い被膜の製造が可能である。ここで、合金粒子分散液中の金属酸化物は、Ｘ線回折で確認することができる。この金属酸化物はＸ線回折で検出されないことが好ましい。その含有量は、粒子に対して、５００ｐｐｍ以下が好ましく、２００ｐｐｍ以下がより好ましく、１００ｐｐｍ以下がさらに好ましい。もし、金属酸化物の含有量が５００ｐｐｍを超えると、分散液の保存安定性が低下し、粒子が凝集して析出するおそれがある。また、合金粒子がイオン化してしまうと、液中で粒子として存在せず、これを塗布液として使用しても所望の被膜は得られない。 The alloy particle dispersion of the present invention can suppress oxidation and ionization of alloy particles. Therefore, even in an aqueous system, long-term storage stability that could not be realized conventionally can be realized. In addition, a long-term pot life that could not be realized conventionally can be realized even with a coating solution using the alloy particle dispersion liquid. Furthermore, this alloy particle dispersion has a very low content of oxide particles, and can produce a highly conductive coating film. Here, the metal oxide in the alloy particle dispersion can be confirmed by X-ray diffraction. This metal oxide is preferably not detected by X-ray diffraction. The content is preferably 500 ppm or less, more preferably 200 ppm or less, and still more preferably 100 ppm or less, based on the particles. If the content of the metal oxide exceeds 500 ppm, the storage stability of the dispersion is reduced, and the particles may aggregate and precipitate. Further, when the alloy particles are ionized, they do not exist as particles in the liquid, and a desired coating cannot be obtained even if the alloy particles are used as a coating liquid.
また、本発明は、上述の合金粒子分散液を用いた塗布液を基材上に塗布することを特徴とする被膜付基材の製造方法に関する。以下に、これらについて説明をする。
［塗布液の製造方法］
本発明の合金粒子分散液に含まれる合金粒子を用いて被膜形成用塗布液が製造できる。被膜形成用塗布液には、従来公知の各種添加剤を添加することができる。
The present invention also relates to a method for producing a substrate with a coating, characterized by applying a coating solution using the above-mentioned alloy particle dispersion to a substrate. Hereinafter, these will be described.
[Production method of coating liquid]
A coating liquid for forming a film can be produced using the alloy particles contained in the alloy particle dispersion of the present invention. Various conventionally known additives can be added to the coating solution for forming a film.
［被膜付基材の製造方法］
被膜付基材の製造は、この塗布液を基材上に塗布した後、乾燥し、必要に応じて焼成を行う。
[Manufacturing method of coated substrate]
In the production of a substrate with a film, after applying this coating solution on the substrate, the substrate is dried and, if necessary, baked.
基材は、ガラス、プラスチック、セラミック、金属等からなるフィルム状、シート状等の基材が例示される。塗布液の塗布方法は、ディッピング法、スピナー法、スプレー法、ロールコーター法、フレキソ印刷法等が例示される。被膜の膜厚は、３０〜３００ｎｍ程度が好ましく、５０〜２００ｎｍ程度がより好ましい。 Examples of the substrate include film, sheet, and other substrates made of glass, plastic, ceramic, metal, and the like. Examples of the application method of the application liquid include a dipping method, a spinner method, a spray method, a roll coater method, and a flexographic printing method. The thickness of the coating is preferably about 30 to 300 nm, more preferably about 50 to 200 nm.
乾燥温度は、例えば常温〜９０℃程度の温度である。焼成温度は、例えば１２０〜９００℃程度であり、１５０〜３５０℃程度であってもよい。本発明の分散液に含まれる合金粒子は有機安定化剤等の有機物の付着が、合金粒子に対して炭素含有量が０．１質量％以下と、少ないため、例えば４００℃以上といった高温で焼成して有機物を除去する必要がない。これにより、高温焼成による合金粒子の凝集、融着を防止できるとともに、得られる被膜のへーズの劣化を抑制できる。 The drying temperature is, for example, a temperature from normal temperature to about 90 ° C. The firing temperature is, for example, about 120 to 900 ° C, and may be about 150 to 350 ° C. The alloy particles contained in the dispersion of the present invention have a small carbon content of 0.1% by mass or less with respect to the alloy particles due to the adhesion of an organic substance such as an organic stabilizer. There is no need to remove organic matter. Thereby, aggregation and fusion of the alloy particles due to high-temperature firing can be prevented, and deterioration of the haze of the obtained coating film can be suppressed.
次に、実施例および比較例を挙げて本発明の合金粒子分散液の製造方法について説明するが、本発明はこれら実施例によって何ら限定されるものではない。 Next, the method for producing the alloy particle dispersion of the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.
［実施例１］
〈粒子調製工程〉
旋回流方式のバブル発生装置（株式会社Ｌｉｇａｒｉｃ製 ＨＹＫ−２０−ＳＤ）で超純水とＮ２を接触させて、Ｎ２マイクロナノバブル水（平均気泡径７０ｎｍ、気泡個数２．４億個／ｍＬ、ｐＨ５．７９、電気伝導度１．１７μＳ／ｃｍ、ＤＯ１．７０ｐｐｍ、ＯＲＰ３３０ｍＶ）を準備した。
Ｎ２マイクロナノバブル水６００ｇに硫酸第一鉄７水和物（還元剤）１８０ｇを溶解し、溶液Ａ１を調製した。
[Example 1]
<Particle preparation step>
In bubble generator of the swirling flow type (Ligaric manufactured HYK-20-SD Corporation) contacting the ultra pure water and N 2, N 2 micronanobubble water (average cell diameter 70 nm, the bubbles number 240 million cells / mL , PH 5.79, electric conductivity 1.17 μS / cm, DO 1.70 ppm, and ORP 330 mV).
N 2 micro-nano water 600g ferrous sulfate heptahydrate (reducing agent) was dissolved 180 g, the solution A1 was prepared.
Ｎ２マイクロナノバブル水６００ｇに硝酸銅（ＩＩ）３水和物３８ｇと硝酸パラジウム（ＩＩ）２水和物２５ｇを溶解し、溶液Ｂ１を調製した。その後、溶液Ｂ１に溶液Ａ１を添加し、１０時間攪拌して得られた分散液から合金粒子を遠心分離機により分離回収した。 N 2 micro-nano water 600g was dissolved copper nitrate (II) 3 hydrate 38g and palladium nitrate (II) 2-hydrate 25 g, the solution B1 was prepared. Thereafter, the solution A1 was added to the solution B1, and the alloy particles were separated and collected from the dispersion obtained by stirring for 10 hours using a centrifuge.
〈洗浄工程〉
粒子調製工程と同様にして、Ｎ２マイクロナノバブル水を準備した。
Ｎ２マイクロナノバブル水２００ｇに、上記分離回収した合金粒子を浸漬して洗浄（脱塩）した後、再度遠心分離により分離回収した。
<Cleaning process>
In analogy to the particle preparation step, it was prepared N 2 micro-nano water.
The N 2 micronanobubble water 200 g, washed by immersing the separated recovered alloy particles (demineralized) were separated and recovered again by centrifugation.
〈合金粒子分散液の調製〉
ＩＣＰ分析で上記分離回収した合金粒子の金属濃度を定量し、Ｎ２マイクロナノバブル水を用いて金属換算で濃度が２．５質量％の合金粒子水分散液を調製した。その後、両性イオン交換樹脂１０ｇを用いて脱イオンを行い、金属換算で濃度が２．５質量％の黒茶色の合金粒子分散液Ｐ１を得た。
<Preparation of alloy particle dispersion>
To quantify the metal concentration of the separated and recovered alloy particles by ICP analysis, the concentration was prepared alloy particle aqueous dispersion of 2.5% by mass in terms of a metal with a N 2 micro-nano water. Thereafter, deionization was performed using 10 g of the amphoteric ion exchange resin to obtain a black-brown alloy particle dispersion P1 having a concentration of 2.5% by mass in terms of metal.
［微小気泡の平均気泡径と気泡個数］
合金粒子分散液Ｐ１中の微小気泡については、この合金粒子分散液を限外濾過膜（旭化成製ＳＥＰ−１０１３分画分子量４０００）で濾過して合金粒子を取り除き、濾液中の微小気泡の平均気泡径と気泡個数を測定した。微小気泡の平均気泡径及び気泡個数は、液中の気泡のブラウン運動移動速度を、ナノ粒子トラッキング解析法を用いて測定した。具体的には、測定試料（溶液Ａ１、溶液Ｂ１又は合金粒子分散液Ｐ１の濾液）約２０ｍＬを吸引させながら測定機器（Ｍａｌｖｅｒｎ社製「ナノサイト ＮＳ３００」）に注入し、ナノ粒子トラッキング解析法にて測定した。なお、マイクロナノバブル水は、濾過処理をせずに、そのまま上記方法で測定した。
[Average bubble diameter and number of bubbles]
Regarding the microbubbles in the alloy particle dispersion liquid P1, this alloy particle dispersion liquid was filtered through an ultrafiltration membrane (SEP-1013 manufactured by Asahi Kasei Corporation, molecular weight cut off 4000) to remove alloy particles, and the average bubbles of microbubbles in the filtrate were removed. The diameter and the number of bubbles were measured. The average bubble diameter and the number of bubbles of the microbubbles were measured by measuring the Brownian movement speed of bubbles in the liquid by using a nanoparticle tracking analysis method. Specifically, about 20 mL of a measurement sample (solution A1, solution B1 or a filtrate of alloy particle dispersion P1) is sucked and injected into a measurement device (“Nanosite NS300” manufactured by Malvern) while aspirating. Measured. The micro-nano bubble water was measured by the above method without filtering.
粒子調製工程で還元後の溶液の物性（ｐＨ、ＯＲＰ）、最終的に得られた合金粒子分散液の物性（ｐＨ、ＯＲＰ、合金粒子の収率、微小気泡の平均気泡径と気泡個数、合金の一次粒子の平均粒子径、合金の二次粒子の平均粒子径、合金粒子の含有量（金属濃度）、Ｃ（カーボン）量、不純分（Ｎａ、Ｆｅ、Ｎａ、Ｂ、ＳＯ４、ＮＯ３）含有量）を表１に示した。また、合金粒子分散液中の合金および金属酸化物の有無、合金粒子分散液の保存安定性を表２に示した（以下の実施例、比較例も同様）。 Physical properties (pH, ORP) of the solution after reduction in the particle preparation process, physical properties (pH, ORP, yield of alloy particles, average particle size and number of microbubbles, alloy alloy dispersion liquid finally obtained) Average particle diameter of primary particles, average particle diameter of secondary particles of alloy, content of alloy particles (metal concentration), C (carbon) amount, impurity (Na, Fe, Na, B, SO 4 , NO 3) ) Content) are shown in Table 1. Table 2 shows the presence or absence of the alloy and the metal oxide in the alloy particle dispersion, and the storage stability of the alloy particle dispersion (the same applies to the following Examples and Comparative Examples).
［電気伝導度］
電気伝導度は、交流２電極法によって測定した。具体的には、ｐＨメーター（堀場製作所製Ｆ−７４ 、電極型番３５５１−１０Ｄ）を導電率測定モードにて、測定する液に電極を浸漬させて求めた。なお、バブリング水、マイクロナノバブル水、合金粒子分散液の各液温は２５℃に調整した。
[Electric conductivity]
The electric conductivity was measured by an AC two-electrode method. Specifically, a pH meter (F-74, manufactured by Horiba, electrode model number 3551-10D) was obtained by immersing the electrode in the liquid to be measured in the conductivity measurement mode. In addition, each liquid temperature of bubbling water, micro nano bubble water, and alloy particle dispersion liquid was adjusted to 25 degreeC.
［酸化還元電位（ＯＲＰ）］
酸化還元電位（Ｏｘｉｄａｔｉｏｎ Ｒｅｄｕｃｔｉｏｎ Ｐｏｔｅｎｔｉａｌ）は、ｐＨメーター（堀場製作所製Ｆ−７４、電極型番９３００−１０Ｄ）の設定をＯＲＰ測定モードにて、電極を測定する液に電極を浸漬させて求めた。なお、バブリング水、マイクロナノバブル水、合金粒子分散液の各液温は２５℃に調整した。
[Oxidation-reduction potential (ORP)]
The oxidation-reduction potential (Oxidation Reduction Potential) was determined by immersing the electrode in a liquid for measuring the electrode in an ORP measurement mode by setting a pH meter (F-74 manufactured by Horiba, electrode model number 9300-10D). In addition, each liquid temperature of bubbling water, micro nano bubble water, and alloy particle dispersion liquid was adjusted to 25 degreeC.
［溶存酸素濃度 （ＤＯ）］
溶存酸素（Ｄｉｓｓｏｌｖｅｄ Ｏｘｙｇｅｎ）濃度は、隔膜式ガルバニ電池法によって測定した。具体的には、ｐＨメーター（堀場製作所製ＯＭ−５１ 、電極型番９５２０−１０Ｄ）を導電率測定モードにて、測定する液に電極を浸漬させて大気圧下で求めた。なお、バブリング水、マイクロナノバブル水、合金粒子分散液の各液温は２５℃に調整した。
[Dissolved oxygen concentration (DO)]
The dissolved oxygen (Dissolved Oxygen) concentration was measured by a diaphragm galvanic cell method. Specifically, a pH meter (OM-51, manufactured by Horiba, electrode model No. 9520-10D) was measured at atmospheric pressure by immersing the electrode in the liquid to be measured in the conductivity measurement mode. In addition, each liquid temperature of bubbling water, micro nano bubble water, and alloy particle dispersion liquid was adjusted to 25 degreeC.
［粒子の収率］
合金粒子の収率は、合金粒子分散液中の金属量をＩＣＰで測定した合金分散液中の金属濃度から算出し、これを仕込みの金属塩から計算される理論上の金属量で割ったものに１００を乗じて求めた。
[Particle yield]
The yield of alloy particles is calculated by calculating the amount of metal in the alloy particle dispersion from the metal concentration in the alloy dispersion measured by ICP, and dividing this by the theoretical amount of metal calculated from the metal salt used. Multiplied by 100.
［一次粒子の平均粒子径］
合金粒子の平均粒子径は、画像解析法により測定した。具体的には、透過型電子顕微鏡（株式会社日立製作所製、Ｈ−８００）により、合金粒子分散液を電子顕微鏡用銅セルのコロジオン膜上で乾燥して、倍率２５万倍で写真撮影して得られる写真投影図における、任意の５００個の粒子について、その粒子径を測定し、その平均値を合金粒子の平均粒子径とした。
[Average primary particle diameter]
The average particle size of the alloy particles was measured by an image analysis method. Specifically, the alloy particle dispersion was dried on a collodion film of a copper cell for an electron microscope using a transmission electron microscope (H-800, manufactured by Hitachi, Ltd.) and photographed at a magnification of 250,000 times. The particle diameters of arbitrary 500 particles in the obtained photograph projection were measured, and the average value was defined as the average particle diameter of the alloy particles.
［二次粒子の平均粒子径］
合金粒子分散液をそのままセルに入れ、マイクロトラック法にて測定し、その平均値（Ｄ５０）を合金粒子の平均粒子径とした。
[Average particle diameter of secondary particles]
The alloy particle dispersion was placed in the cell as it was, and measured by a microtrack method, and the average value (D50) was defined as the average particle size of the alloy particles.
［ＩＣＰ分析］
各元素の質量分析は、誘導結合プラズマ分光分析装置にて化学分析を行った。具体的には、合金粒子分散液を濃硝酸に溶解して、水で濃度１０〜１００質量ｐｐｍに調整した溶液を島津製作所（株）製 ＳＥＱＵＥＮＴＩＡＬ ＰＬＡＳＭＡ ＳＰＥＣＴＲＯＭＥＴＥＲ（ＩＣＰＳ−８１００）にて分析した。
[ICP analysis]
For mass analysis of each element, chemical analysis was performed using an inductively coupled plasma spectrometer. Specifically, the alloy particle dispersion was dissolved in concentrated nitric acid, and the solution adjusted to a concentration of 10 to 100 mass ppm with water was analyzed by SEQUENTIAL PLASMA SPECTROMETER (ICPS-8100) manufactured by Shimadzu Corporation.
［Ｃ（カーボン）量測定］
合金粒子中の炭素含有量は、合金粒子分散液を１００℃で乾燥させ、炭素硫黄分析装置（ＨＯＲＩＢＡ製 ＥＭＩＡ−３２０Ｖ）を用いて測定した。
[C (carbon) amount measurement]
The carbon content in the alloy particles was measured by drying the alloy particle dispersion at 100 ° C. and using a carbon-sulfur analyzer (HORIBA EMIA-320V).
［イオンクロマト分析］
合金粒子分散液を、超純水を用いて１００倍希釈して、イオン交換クロマトグラフ（東ソー製 ＴＳＫｇｅｌ ＳｕｐｅｒＱ−５ＰＷ）を用いて、ＳＯ４、ＮＯ３の濃度を測定した。
[Ion chromatographic analysis]
The alloy particle dispersion was diluted 100-fold with ultrapure water, and the concentrations of SO 4 and NO 3 were measured using an ion exchange chromatograph (TSKgel SuperQ-5PW manufactured by Tosoh Corporation).
［Ｘ線回折による合金及び金属酸化物の有無の確認］
合金粒子分散液を溶液のまま、Ｘ線回折による解析を行い、合金及び金属酸化物の存在の有無を確認した。試料のＸ線回折による定性分析は、ＲＩＧＡＫＵ（株）製Ｘ−ＲＡＹ ＤＩＦＦＲＡＣＴ ＭＥＴＥＲ（ＳｍａｒｔＬａｂ）にて行った。具体的には、試料をセルに入れ装置にセットし、管電圧４５．０ｋＶ、管電流２００．０ｍＡ、対陰極Ｃｕ、測定範囲：開始角度〜終了角度（２θ）５．０００°〜７０．０００°、スキャンスピード５．０００°／ｍｉｎにて測定した。
合金のピークが観察され、かつ金属単体のピークが観察されない場合、合金が存在すると判断する。
合金の存在が確認された場合 ：○
合金の存在が確認されなかった場合 ：×
金属酸化物のピークが観察されなかった場合：○
金属酸化物のピークが観察された場合 ：×
[Confirmation of presence of alloy and metal oxide by X-ray diffraction]
X-ray diffraction analysis was performed on the alloy particle dispersion in the form of the solution to confirm the presence or absence of the alloy and the metal oxide. The qualitative analysis of the sample by X-ray diffraction was performed using X-RAY DIFFRACT METER (SmartLab) manufactured by RIGAKU. Specifically, the sample was put in the cell and set in the apparatus, and the tube voltage was 45.0 kV, the tube current was 200.0 mA, the cathode was Cu, and the measurement range was from start angle to end angle (2θ) 5.000 ° to 70.000. ° and a scan speed of 5.000 ° / min.
When an alloy peak is observed and a metal simple substance peak is not observed, it is determined that an alloy is present.
When the presence of alloy is confirmed: ○
When the presence of the alloy was not confirmed: ×
When no metal oxide peak was observed: ○
When a metal oxide peak is observed: ×
［保存安定性］
２５℃で保管した合金粒子分散液のＸ線回折（ＸＲＤ）による合金粒子の酸化の有無および導電性の変化を確認した。
[Storage stability]
X-ray diffraction (XRD) of the alloy particle dispersion stored at 25 ° C. confirmed the presence or absence of oxidation of the alloy particles and the change in conductivity.
〈塗布液および被膜付基材の作製〉
得られた合金粒子分散液Ｐ１をエタノールで０．５質量％に希釈し、塗布液を作製した。これをスピンコート法でガラスに塗布し、ついで窒素雰囲気下で、２００℃で３０分間焼成し、被膜付基材を作製した。この被膜付基材の導電性をローレスタ（三菱化学製 ＮＳＣＰプローブ）で測定した。また、被膜の一部をカッターナイフで剥離させ段差をつくり、レーザー顕微鏡でこの段差を測定し、これを膜厚とした。これらの結果を表２に示した（以下の実施例、比較例も同様）。
<Preparation of coating liquid and substrate with film>
The obtained alloy particle dispersion liquid P1 was diluted to 0.5% by mass with ethanol to prepare a coating liquid. This was applied to glass by spin coating, and then baked at 200 ° C. for 30 minutes in a nitrogen atmosphere to produce a coated substrate. The conductivity of this coated substrate was measured with a Loresta (NSCP probe manufactured by Mitsubishi Chemical Corporation). In addition, a part of the coating was peeled off with a cutter knife to form a step, and the step was measured with a laser microscope to determine the film thickness. The results are shown in Table 2 (the same applies to the following Examples and Comparative Examples).
［実施例２］
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
実施例１の洗浄工程で、Ｎ２マイクロナノバブル水の代わりに、Ｎ２マイクロナノバブル水を用いて調製した濃度２０質量％のクエン酸３ナトリウム水溶液２００ｇを使用した以外は、実施例１と同様にして、黒茶色の合金粒子分散液Ｐ２を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液Ｐ２を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
[Example 2]
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
In the step of washing Example 1, in place of N 2 micro-nano water, except for using a concentration of 20% by mass of trisodium citrate aqueous solution 200g prepared with N 2 micro-nano water, in the same manner as in Example 1 Thus, a black-brown alloy particle dispersion P2 was obtained.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion P2 was used instead of the alloy particle dispersion P1.
［実施例３］
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
超純水（ｐＨ（２５℃、以下同じ）６．３２、電気伝導度０．０５μＳ／ｃｍ、溶存酸素量（ＤＯ）６．１７ｐｐｍ、酸化還元電位（ＯＲＰ）３５０ｍＶ）をＮ２にてバブリングを１時間行い、溶存酸素を除去したＮ２バブリング水（ｐＨ６．６、電気伝導度０．６μＳ／ｃｍ、ＤＯ０．６ｐｐｍ、ＯＲＰ２６０ｍＶ）を準備した。
実施例１の洗浄工程で、Ｎ２マイクロナノバブル水の代わりに、Ｎ２バブリング水を使用した以外は実施例１と同様にして、黒茶色の合金粒子分散液Ｐ３を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液Ｐ３を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
[Example 3]
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
Bubble ultrapure water (pH (25 ° C., the same applies hereinafter) 6.32, electric conductivity 0.05 μS / cm, dissolved oxygen (DO) 6.17 ppm, redox potential (ORP) 350 mV) with N 2 . for 1 hour, the dissolved oxygen N 2 bubbling water was removed (pH 6.6, electric conductivity 0.6μS / cm, DO0.6ppm, ORP260mV) was prepared.
In the step of washing Example 1, in place of N 2 micro-nano water, except using N 2 bubbling water in the same manner as in Example 1 to obtain an alloy particle dispersion P3 black brown.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion P3 was used instead of the alloy particle dispersion P1.
［実施例４］
〈粒子調製工程〉
実施例１の溶液Ａ１と同様にして、溶液Ａ４を調製した。
次に、Ｎ２マイクロナノバブル水６００ｇに硝酸銅（ＩＩ）３水和物６０．８ｇと硝酸パラジウム（ＩＩ）２水和物１０ｇを溶解し、溶液Ｂ４を調製した。その後、溶液Ｂ４に溶液Ａ４を添加し、１０時間攪拌して得られた分散液から合金粒子を遠心分離機により分離回収した。
[Example 4]
<Particle preparation step>
A solution A4 was prepared in the same manner as in the solution A1 of Example 1.
Then dissolved copper nitrate (II) 3 hydrate 60.8g and palladium nitrate (II) 2-hydrate 10g in N 2 micronanobubble water 600 g, the solution B4 was prepared. Thereafter, the solution A4 was added to the solution B4, and the alloy particles were separated and collected by a centrifugal separator from the dispersion obtained by stirring for 10 hours.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄工程以降、実施例１と同様にして、黒茶色の合金粒子分散液Ｐ４を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液Ｐ４を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
After the washing step, a black-brown alloy particle dispersion P4 was obtained in the same manner as in Example 1.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion P4 was used instead of the alloy particle dispersion P1.
［実施例５］
〈粒子調製工程〉
実施例１の溶液Ａ１と同様にして、溶液Ａ５を調製した。
次に、Ｎ２マイクロナノバブル水６００ｇに硝酸銅（ＩＩ）３水和物７５ｇと硝酸パラジウム（ＩＩ）２水和物０．５ｇを溶解し、溶液Ｂ５を調製した。その後、溶液Ｂ５に溶液Ａ５を添加し、１０時間攪拌して得られた分散液から、合金粒子を遠心分離機により分離回収した。
[Example 5]
<Particle preparation step>
A solution A5 was prepared in the same manner as in the solution A1 of Example 1.
Then dissolved copper nitrate (II) 3 hydrate 75g and palladium nitrate (II) 2 dihydrate 0.5g of N 2 micro-nano water 600 g, the solution B5 was prepared. Thereafter, the solution A5 was added to the solution B5, and the alloy particles were separated and recovered from the dispersion obtained by stirring for 10 hours using a centrifuge.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄工程以降、実施例１と同様にして、黒茶色の合金粒子分散液Ｐ５を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液Ｐ５を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
After the washing step, a black-brown alloy particle dispersion P5 was obtained in the same manner as in Example 1.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion P5 was used instead of the alloy particle dispersion P1.
［実施例６］
〈粒子調製工程〉
Ｎ２マイクロナノバブル水５００ｇに硫酸第一鉄７水和物１００ｇを溶解し、溶液Ａ６を調製した。
次に、Ｎ２マイクロナノバブル水３００ｇに硝酸銀（Ｉ）２８．５ｇと硝酸パラジウム（ＩＩ）２水和物４５．３ｇを溶解し、溶液Ｂ６を調製した。その後、溶液Ｂ６に溶液Ａ６を添加し、１０時間攪拌して得られた分散液から、合金粒子を遠心分離機により分離回収した。
[Example 6]
<Particle preparation step>
Dissolving ferrous heptahydrate 100g sulfate N 2 micronanobubble water 500 g, the solution A6 was prepared.
Then dissolved N 2 micro-nano water 300g silver nitrate (I) 28.5 g palladium nitrate (II) 2-hydrate 45.3 g, the solution B6 was prepared. Then, the solution A6 was added to the solution B6, and the alloy particles were separated and collected by a centrifugal separator from the dispersion obtained by stirring for 10 hours.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄工程以降、実施例１と同様にして、黒茶色の合金粒子分散液Ｐ６を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液Ｐ６を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
After the washing step, a black-brown alloy particle dispersion P6 was obtained in the same manner as in Example 1.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion P6 was used instead of the alloy particle dispersion P1.
［実施例７］
〈粒子調製工程〉
実施例６と同様にして、合金粒子を調製し、これを遠心分離機により分離回収した。
[Example 7]
<Particle preparation step>
In the same manner as in Example 6, alloy particles were prepared, and separated and collected by a centrifuge.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
実施例１の洗浄工程で、Ｎ２マイクロナノバブル水の代わりに、Ｎ２バブリング水を使用した以外は実施例１と同様にして、黒茶色の合金粒子分散液Ｐ７を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液Ｐ７を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
In the step of washing Example 1, in place of N 2 micro-nano water, except using N 2 bubbling water in the same manner as in Example 1 to obtain an alloy particle dispersion P7 black brown.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion P7 was used instead of the alloy particle dispersion P1.
［実施例８］
〈粒子調製工程〉
実施例６の溶液Ａ６と同様に、溶液Ａ８を調製した。
次に、Ｎ２マイクロナノバブル水３００ｇに硝酸銀（Ｉ）５１．３ｇと硝酸パラジウム（ＩＩ）２水和物９．１ｇを溶解し、溶液Ｂ８を調製した。その後、溶液Ｂ８に溶液Ａ８を添加し、１０時間攪拌して得られた分散液から、合金粒子を遠心分離機により分離回収した。
Example 8
<Particle preparation step>
A solution A8 was prepared in the same manner as the solution A6 of Example 6.
Then dissolved N 2 micro-nano water 300g silver nitrate (I) 51.3 g palladium nitrate (II) 2 hydrate 9.1 g, the solution B8 was prepared. After that, the solution A8 was added to the solution B8, and alloy particles were separated and collected by a centrifuge from the dispersion obtained by stirring for 10 hours.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄以降、実施例１と同様にして、黒茶色の合金粒子分散液Ｐ７を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液Ｐ８を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
After the washing, in the same manner as in Example 1, a black-brown alloy particle dispersion P7 was obtained.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion P8 was used instead of the alloy particle dispersion P1.
［実施例９］
〈粒子調製工程〉
Ｎ２マイクロナノバブル水４５０ｇに硝酸ニッケル六水和物（Ｎｉ（ＮＯ３）２６Ｈ２Ｏ）（関東化学（株）製）５０ｇと、硝酸銅（ＩＩ）３水和物１０ｇを溶解し、溶液Ａ９を調製した。
[Example 9]
<Particle preparation step>
N 2 micro-nano water 450g nickel nitrate hexahydrate was dissolved and (Ni (NO 3) 2 6H 2 O) ( manufactured by Kanto Chemical (Co.)) 50 g, copper nitrate (II) 3 hydrate 10 g, solution A9 was prepared.
Ｎ２マイクロナノバブル水１０００ｇに水素化ホウ素ナトリウム（還元剤）５０ｇを溶解し、溶液Ｂ９を調製した。溶液Ａ９を撹拌しながら、溶液Ｂ９を添加し、１時間攪拌した。このとき、液が緑色から黒色に変化した。得られた分散液から合金粒子を遠心分離機により分離回収した。 N 2 sodium borohydride micronanobubble water 1000 g (reducing agent) was dissolved 50 g, the solution B9 was prepared. While stirring solution A9, solution B9 was added and stirred for 1 hour. At this time, the liquid changed from green to black. The alloy particles were separated and collected from the obtained dispersion by a centrifuge.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄工程以降、実施例１と同様にして、黒色の合金粒子分散液Ｐ９を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液Ｐ９を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
After the washing step, a black alloy particle dispersion P9 was obtained in the same manner as in Example 1.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion P9 was used instead of the alloy particle dispersion P1.
［比較例１］
〈粒子調製工程〉
実施例３の洗浄工程に記載の方法と同様にして、Ｎ２バブリング水を準備した。
Ｎ２バブリング水９３０ｇにクエン酸３ナトリウム２水和物（有機安定化剤）４００ｇを溶解し、溶液（ＲＳ１−１）を調製した。
Ｎ２バブリング水６００ｇに硫酸第一鉄７水和物（還元剤）１８０ｇを溶解し、溶液（ＲＳ１−２）を調製した。
溶液（ＲＳ１−１）と溶液（ＲＳ１−２）とを混合して３０分間攪拌し、溶液ＲＡ１を調製した。
[Comparative Example 1]
<Particle preparation step>
N 2 bubbling water was prepared in the same manner as in the method described in the washing step of Example 3.
400 g of trisodium citrate dihydrate (organic stabilizer) was dissolved in 930 g of N 2 bubbling water to prepare a solution (RS1-1).
N 2 bubbling water 600g ferrous sulfate heptahydrate (reducing agent) was dissolved 180 g, the solution (RS1-2) was prepared.
The solution (RS1-1) and the solution (RS1-2) were mixed and stirred for 30 minutes to prepare a solution RA1.
Ｎ２バブリング水６００ｇに硝酸銅（ＩＩ）３水和物３８ｇと硝酸パラジウム（ＩＩ）２水和物２５ｇを溶解し、溶液ＲＢ１を調製した。その後、溶液ＲＢ１に溶液ＲＡ１を添加し、１０時間攪拌して得られた分散液から、合金粒子を遠心分離機により分離回収した。 Dissolving copper nitrate (II) 3 hydrate 38g and palladium nitrate (II) 2-hydrate 25g of N 2 bubbling water 600 g, a solution RB1 was prepared. Thereafter, the solution RA1 was added to the solution RB1, and the alloy particles were separated and recovered from the dispersion obtained by stirring for 10 hours using a centrifuge.
〈洗浄工程〉
Ｎ２バブリング水を用いて調製した濃度２０質量％のクエン酸３ナトリウム水溶液２００ｇに、上記分離回収した合金粒子を浸漬して洗浄（脱塩）した後、再度遠心分離により分離回収した。
<Cleaning process>
N in concentration of 20 mass% trisodium citrate aqueous solution 200g prepared with 2 bubbling water, washed by immersing the separated recovered alloy particles (demineralized) were separated and recovered again by centrifugation.
〈金属粒子分散液の調製、塗布液および被膜付基材の作製〉
Ｎ２マイクロナノバブル水の代わりにＮ２バブリング水を使用した以外は、実施例１と同様にして、黒茶色の金属粒子分散液ＲＰ１を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液ＲＰ１を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of metal particle dispersion, preparation of coating liquid and coated substrate>
Except using N 2 bubbling water instead of N 2 micro-nano water, in the same manner as in Example 1 to obtain a metal particle dispersion RP1 black brown.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion liquid RP1 was used instead of the alloy particle dispersion liquid P1.
［比較例２］
〈粒子調製工程〉
Ｎ２マイクロナノバブル水の代わりにＮ２バブリング水を使用した以外は、実施例１と同様にして得られた分散液から、合金粒子を遠心分離機により分離回収した。
[Comparative Example 2]
<Particle preparation step>
Except using N 2 bubbling water instead of N 2 micro-nano water from the dispersion obtained in the same manner as in Example 1, and the alloy particles were separated and recovered by a centrifuge.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄工程以降、比較例１と同様にして、黒色の合金粒子分散液ＲＰ２を得た。しかしながら、この分散液はすぐに沈殿を生じ、塗布液および被膜付基材の作製は出来なかった。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
After the washing step, a black alloy particle dispersion RP2 was obtained in the same manner as in Comparative Example 1. However, this dispersion immediately precipitated, and a coating solution and a substrate with a film could not be produced.
［比較例３］
〈粒子調製工程〉
Ｎ２バブリング水の代わりにＮ２マイクロナノバブル水を使用した以外は、比較例１と同様にして、合金粒子を調製し、これを遠心分離機により分離回収した。
[Comparative Example 3]
<Particle preparation step>
Except using N 2 micro-nano water instead of N 2 bubbling water, in the same manner as in Comparative Example 1, the alloy particles were prepared, which were separated and collected by centrifuge.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄工程以降、実施例１と同様にして、黒茶色の合金粒子分散液ＲＰ３を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液ＲＰ３を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
After the washing step, a black-brown alloy particle dispersion RP3 was obtained in the same manner as in Example 1.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion RP3 was used instead of the alloy particle dispersion P1.
［比較例４］
〈粒子調製工程および洗浄工程〉
Ｎ２バブリング水の代わりにＮ２マイクロナノバブル水を使用した以外は、比較例１と同様にした。
[Comparative Example 4]
<Particle preparation step and washing step>
Except for using N 2 micro-nano water instead of N 2 bubbling water, in the same manner as in Comparative Example 1.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
実施例１と同様にして、黒茶色の合金粒子分散液ＲＰ４を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液ＲＰ４を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
In the same manner as in Example 1, a black-brown alloy particle dispersion RP4 was obtained.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion RP4 was used instead of the alloy particle dispersion P1.
［比較例５］
〈粒子調製工程〉
比較例２と同様に行った。
[Comparative Example 5]
<Particle preparation step>
Performed in the same manner as in Comparative Example 2.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄工程以降、実施例１と同様にして、黒茶色の合金粒子分散液ＲＰ５を得た。しかしながら、この分散液はすぐに沈殿を生じ、塗布液および被膜付基材の作製は出来なかった。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
After the washing step, a black-brown alloy particle dispersion RP5 was obtained in the same manner as in Example 1. However, this dispersion immediately precipitated, and a coating solution and a substrate with a film could not be produced.
［比較例６］
〈粒子調製工程および洗浄工程〉
比較例１の溶液ＲＡ１と同様にして、溶液ＲＡ６を調製した。
次に、Ｎ２バブリング水６００ｇに硝酸銅（ＩＩ）３水和物６０．８ｇと硝酸パラジウム（ＩＩ）２水和物１０ｇを溶解し、溶液ＲＢ６を調製した。その後、溶液ＲＢ６に溶液ＲＡ６を添加し、１０時間攪拌して得られた分散液から合金粒子を遠心分離機により分離回収した。
次いで、比較例１の洗浄工程と同様にした。
[Comparative Example 6]
<Particle preparation step and washing step>
A solution RA6 was prepared in the same manner as in the solution RA1 of Comparative Example 1.
Next, 60.8 g of copper (II) nitrate trihydrate and 10 g of palladium (II) nitrate dihydrate were dissolved in 600 g of N 2 bubbling water to prepare a solution RB6. Thereafter, the solution RA6 was added to the solution RB6, and the alloy particles were separated and recovered from the dispersion obtained by stirring for 10 hours using a centrifuge.
Next, the same procedure as in the cleaning step of Comparative Example 1 was performed.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
実施例１と同様にして、黒茶色の合金粒子分散液ＲＰ６を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液ＲＰ６を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
In the same manner as in Example 1, a black-brown alloy particle dispersion RP6 was obtained.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion liquid RP6 was used instead of the alloy particle dispersion liquid P1.
［比較例７］
〈粒子調製工程および洗浄工程〉
比較例１の溶液ＲＡ１と同様にして、溶液ＲＡ７を調製した。
次に、Ｎ２バブリング水６００ｇに硝酸銅（ＩＩ）３水和物７５ｇと硝酸パラジウム（ＩＩ）２水和物０．５ｇを溶解し、溶液ＲＢ７を調製した。その後、溶液ＲＢ７に溶液ＲＡ７を添加し、１０時間攪拌して得られた分散液から合金粒子を遠心分離機により分離回収した。
次いで、比較例１の洗浄工程と同様にした。
[Comparative Example 7]
<Particle preparation step and washing step>
A solution RA7 was prepared in the same manner as the solution RA1 of Comparative Example 1.
Next, 75 g of copper (II) nitrate trihydrate and 0.5 g of palladium (II) nitrate dihydrate were dissolved in 600 g of N 2 bubbling water to prepare a solution RB7. Thereafter, the solution RA7 was added to the solution RB7, and the alloy particles were separated and recovered from the dispersion obtained by stirring for 10 hours using a centrifuge.
Next, the same procedure as in the cleaning step of Comparative Example 1 was performed.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
実施例１と同様にして、黒茶色の合金粒子分散液ＲＰ７を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液ＲＰ７を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
In the same manner as in Example 1, a black-brown alloy particle dispersion RP7 was obtained.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion RP7 was used instead of the alloy particle dispersion P1.
［比較例８］
〈粒子調製工程〉
Ｎ２バブリング水９３０ｇにクエン酸３ナトリウム２水和物４００ｇを溶解し、溶液（ＲＳ８−１）を調製した。
Ｎ２バブリング水５００ｇに硫酸第一鉄７水和物１００ｇを溶解し、溶液（ＲＳ８−２）を調製した。
溶液（ＲＳ８−１）と溶液（ＲＳ８−２）とを混合して３０分間攪拌し、溶液ＲＡ８を調製した。
[Comparative Example 8]
<Particle preparation step>
Dissolving trisodium citrate dihydrate 400g to N 2 bubbling water 930 g, the solution (RS8-1) was prepared.
Dissolving ferrous heptahydrate 100g sulfate N 2 bubbling water 500 g, the solution (RS8-2) was prepared.
The solution (RS8-1) and the solution (RS8-2) were mixed and stirred for 30 minutes to prepare a solution RA8.
Ｎ２バブリング水３００ｇに硝酸銀（Ｉ）２８．５ｇと硝酸パラジウム（ＩＩ）２水和物４５．３ｇを溶解し、溶液ＲＢ８を調製した。その後、溶液ＲＢ８に溶液ＲＡ８を添加し、１０時間攪拌して得られた分散液から、合金粒子を遠心分離機により分離回収した。 N 2 bubbling water 300g was dissolved silver nitrate (I) 28.5 g palladium nitrate (II) 2-hydrate 45.3 g, the solution RB8 was prepared. Thereafter, the solution RA8 was added to the solution RB8, and the alloy particles were separated and recovered from the dispersion obtained by stirring for 10 hours using a centrifuge.
〈洗浄工程〉
Ｎ２バブリング水を用いて調製した濃度３０質量％のクエン酸３ナトリウム水溶液２００ｇに、上記分離回収した合金粒子を浸漬して洗浄（脱塩）した後、遠心分離により分離回収した。次いで、同様にＮ２バブリング水を用いて調製した濃度２０質量％のクエン酸３ナトリウム水溶液２００ｇに、上記分離回収した合金粒子を浸漬して洗浄（脱塩）した後、再度遠心分離により分離回収した。
<Cleaning process>
The N 2 bubbling water concentration of 30% by mass of trisodium citrate aqueous solution 200g prepared using, washed by immersing the separated recovered alloy particles (demineralized) was separated and recovered by centrifugation. Next, the separated and recovered alloy particles are immersed and washed (desalted) in 200 g of a 20% by mass aqueous solution of trisodium citrate similarly prepared using N 2 bubbling water, and then separated and recovered by centrifugation again. did.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
実施例１と同様にして、黒茶色の合金粒子分散液ＲＰ８を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液ＲＰ８を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
In the same manner as in Example 1, a black-brown alloy particle dispersion RP8 was obtained.
A coating liquid and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion liquid RP8 was used instead of the alloy particle dispersion liquid P1.
［比較例９］
〈粒子調製工程〉
Ｎ２マイクロナノバブル水９３０ｇにクエン酸３ナトリウム２水和物４００ｇを溶解し、溶液（ＲＳ９−１）を調製した。
Ｎ２マイクロナノバブル水５００ｇに硫酸第一鉄７水和物１００ｇを溶解し、溶液（ＲＳ９−２）を調製した。
溶液（ＲＳ９−１）と溶液（ＲＳ９−２）とを混合して３０分間攪拌し、溶液ＲＡ９を調製した。
[Comparative Example 9]
<Particle preparation step>
N 2 was dissolved in micro-nano water 930g of trisodium citrate dihydrate 400 g, the solution (RS9-1) was prepared.
Dissolving ferrous heptahydrate 100g sulfate N 2 micronanobubble water 500 g, the solution (RS9-2) was prepared.
The solution (RS9-1) and the solution (RS9-2) were mixed and stirred for 30 minutes to prepare a solution RA9.
Ｎ２マイクロナノバブル水３００ｇに硝酸銀（Ｉ）２８．５ｇと硝酸パラジウム（ＩＩ）２水和物４５．３ｇを溶解し、溶液ＲＢ９を調製した。その後、溶液ＲＢ９に溶液ＲＡ９を添加し、１０時間攪拌して得られた分散液から、合金粒子を遠心分離機により分離回収した。 N 2 was dissolved silver nitrate (I) 28.5 g palladium nitrate (II) 2 dihydrate 45.3g micro-nano bubbles water 300 g, a solution RB9 was prepared. Thereafter, the solution RA9 was added to the solution RB9, and the alloy particles were separated and collected by a centrifugal separator from the dispersion obtained by stirring for 10 hours.
〈洗浄工程〉
Ｎ２バブリング水の代わりにＮ２マイクロナノバブル水を使用した以外は、比較例８の洗浄工程と同様にした。
<Cleaning process>
Except using N 2 micro-nano water instead of N 2 bubbling water were the same as the cleaning process of Comparative Example 8.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
実施例１と同様にして、金属換算で濃度が２．５質量％の黒茶色の合金粒子分散液ＲＰ９を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液ＲＰ９を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
In the same manner as in Example 1, a black-brown alloy particle dispersion RP9 having a concentration of 2.5% by mass in terms of metal was obtained.
A coating liquid and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion liquid RP9 was used instead of the alloy particle dispersion liquid P1.
［比較例１０］
〈粒子調製工程および洗浄工程〉
Ｎ２バブリング水９３０ｇにクエン酸３ナトリウム２水和物４００ｇを溶解し、溶液（ＲＳ１０−１）を調製した。
Ｎ２バブリング水５００ｇに硫酸第一鉄７水和物１００ｇを溶解し、溶液（ＲＳ１０−２）を調製した。
溶液（ＲＳ１０−１）と溶液（ＲＳ１０−２）とを混合して３０分間攪拌し、溶液ＲＡ１０を調製した。
[Comparative Example 10]
<Particle preparation step and washing step>
Dissolving trisodium citrate dihydrate 400g to N 2 bubbling water 930 g, the solution (RS10-1) was prepared.
Dissolving ferrous heptahydrate 100g sulfate N 2 bubbling water 500 g, the solution (RS10-2) was prepared.
The solution (RS10-1) and the solution (RS10-2) were mixed and stirred for 30 minutes to prepare a solution RA10.
Ｎ２バブリング水３００ｇに硝酸銀（Ｉ）５１．３ｇと硝酸パラジウム（ＩＩ）２水和物９．１ｇを溶解し、溶液ＲＢ１０を調製した。その後、溶液ＲＢ１０に溶液ＲＡ１０を添加し、１０時間攪拌して得られた分散液から、合金粒子を遠心分離機により分離回収した。
次いで、比較例８の洗浄工程と同様にした。
N 2 bubbling water 300g was dissolved silver nitrate (I) 51.3 g palladium nitrate (II) 2 hydrate 9.1 g, the solution RB10 was prepared. Thereafter, the solution RA10 was added to the solution RB10, and the alloy particles were separated and recovered from the dispersion obtained by stirring for 10 hours using a centrifuge.
Next, the same procedure as in the cleaning step of Comparative Example 8 was performed.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
実施例１と同様にして、黒茶色の合金粒子分散液ＲＰ１０を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液ＲＰ１０を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
In the same manner as in Example 1, a black-brown alloy particle dispersion RP10 was obtained.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion liquid RP10 was used instead of the alloy particle dispersion liquid P1.
［比較例１１］
〈粒子調製工程および洗浄工程〉
Ｎ２バブリング水４５０ｇに硝酸ニッケル六水和物（Ｎｉ（ＮＯ３）２６Ｈ２Ｏ）（関東化学（株）製）５０ｇと、硝酸銅（ＩＩ）３水和物１０ｇと、クエン酸水和物（有機安定化剤）（キシダ化学（株）製）０．５ｇを溶解し、溶液ＲＡ１１を調製した。
[Comparative Example 11]
<Particle preparation step and washing step>
And N nickel nitrate hexahydrate in 2 bubbling water 450g (Ni (NO 3) 2 6H 2 O) ( manufactured by Kanto Chemical (Co.)) 50 g, and copper nitrate (II) 3 hydrate 10 g, citric acid sum 0.5 g of a product (organic stabilizer) (manufactured by Kishida Chemical Co., Ltd.) was dissolved to prepare a solution RA11.
Ｎ２バブリング水１０００ｇに水素化ホウ素ナトリウム（還元剤）５０ｇを溶解し、溶液ＲＢ１１を調製した。溶液ＲＡ１１を撹拌しながら、溶液ＲＢ１１を添加し、１時間攪拌した。このとき、液が緑色から黒色に変化した。得られた分散液から合金粒子を遠心分離機により分離回収した。
次いで、比較例１の洗浄工程と同様にした。
N sodium borohydride in 2 bubbling water 1000 g (reducing agent) was dissolved 50 g, the solution RB11 was prepared. While stirring the solution RA11, the solution RB11 was added and stirred for 1 hour. At this time, the liquid changed from green to black. The alloy particles were separated and collected from the obtained dispersion by a centrifuge.
Next, the same procedure as in the cleaning step of Comparative Example 1 was performed.
〈合金粒子分散液の調製、塗布液および被膜付基材の作製〉
実施例１と同様にして、黒茶色の合金粒子分散液ＲＰ１１を得た。
合金粒子分散液Ｐ１の代わりに合金粒子分散液ＲＰ１１を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of alloy particle dispersion, preparation of coating liquid and substrate with film>
In the same manner as in Example 1, a black-brown alloy particle dispersion RP11 was obtained.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the alloy particle dispersion RP11 was used instead of the alloy particle dispersion P1.
［比較例１２］
〈粒子調製工程〉
比較例１の溶液ＲＡ１と同様にして、溶液ＲＡ１２を調製した。
[Comparative Example 12]
<Particle preparation step>
A solution RA12 was prepared in the same manner as in the solution RA1 of Comparative Example 1.
Ｎ２バブリング水６００ｇに硝酸銅（ＩＩ）３水和物７６ｇを溶解し、溶液ＲＢ１２を調製した。その後、溶液ＲＢ１２に溶液ＲＡ１２を添加し、１０時間攪拌して得られた分散液から、金属粒子を遠心分離機により分離回収した。 Dissolving copper nitrate (II) 3 hydrate 76g to N 2 bubbling water 600 g, a solution RB12 was prepared. Thereafter, the solution RA12 was added to the solution RB12, and the metal particles were separated and recovered from the dispersion obtained by stirring for 10 hours using a centrifuge.
〈金属粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄工程以降、比較例１と同様にして、黒茶色の金属粒子分散液ＲＰ１２を得た。
合金粒子分散液Ｐ１の代わりに金属粒子分散液ＲＰ１２を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of metal particle dispersion, preparation of coating liquid and coated substrate>
After the washing step, a black-brown metal particle dispersion RP12 was obtained in the same manner as in Comparative Example 1.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the metal particle dispersion RP12 was used instead of the alloy particle dispersion P1.
［比較例１３］
〈粒子調製工程〉
Ｎ２バブリング水の代わりにＮ２マイクロナノバブル水を使用する以外は、比較例１２と同様にして、粒子調製を行った。
[Comparative Example 13]
<Particle preparation step>
Except using N 2 micro-nano water instead of N 2 bubbling water, in the same manner as in Comparative Example 12 were subjected to particle preparation.
〈金属粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄工程以降、実施例１と同様にして、黒茶色の金属粒子分散液ＲＰ１３を得た。
合金粒子分散液Ｐ１の代わりに金属粒子分散液ＲＰ１３を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of metal particle dispersion, preparation of coating liquid and coated substrate>
After the washing step, a black-brown metal particle dispersion RP13 was obtained in the same manner as in Example 1.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the metal particle dispersion RP13 was used instead of the alloy particle dispersion P1.
［比較例１４］
〈粒子調製工程〉
Ｎ２マイクロナノバブル水９３０ｇにクエン酸３ナトリウム２水和物４００ｇを溶解し、溶液（ＲＳ１４−１）を調製した。
Ｎ２マイクロナノバブル水５００ｇに硫酸第一鉄７水和物１００ｇを溶解し、溶液（ＲＳ１４−２）を調製した。
溶液（ＲＳ１４−１）と溶液（ＲＳ１４−２）とを混合して３０分間攪拌し、溶液ＲＡ１４を調製した。
[Comparative Example 14]
<Particle preparation step>
N 2 was dissolved in micro-nano water 930g of trisodium citrate dihydrate 400 g, the solution (RS14-1) was prepared.
Dissolving ferrous heptahydrate 100g sulfate N 2 micronanobubble water 500 g, the solution (RS14-2) was prepared.
The solution (RS14-1) and the solution (RS14-2) were mixed and stirred for 30 minutes to prepare a solution RA14.
Ｎ２マイクロナノバブル水３００ｇに硝酸銀（Ｉ）５７ｇを溶解し、溶液ＲＢ１４を調製した。その後、溶液ＲＢ１４に溶液ＲＡ１４を添加し、１０時間攪拌して得られた分散液から、金属粒子を遠心分離機により分離回収した。 It was dissolved silver nitrate (I) 57 g of N 2 micro-nano water 300 g, a solution RB14 was prepared. Thereafter, the solution RA14 was added to the solution RB14, and the metal particles were separated and collected by a centrifugal separator from the dispersion obtained by stirring for 10 hours.
〈洗浄工程〉
Ｎ２バブリング水の代わりにＮ２マイクロナノバブル水を使用した以外は、比較例８の洗浄工程と同様にした。
<Cleaning process>
Except using N 2 micro-nano water instead of N 2 bubbling water were the same as the cleaning process of Comparative Example 8.
〈金属粒子分散液の調製、塗布液および被膜付基材の作製〉
実施例１と同様にして、黒茶色の金属粒子分散液ＲＰ１４を得た。
合金粒子分散液Ｐ１の代わりに金属粒子分散液ＲＰ１４を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of metal particle dispersion, preparation of coating liquid and coated substrate>
In the same manner as in Example 1, a black-brown metal particle dispersion RP14 was obtained.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the metal particle dispersion RP14 was used instead of the alloy particle dispersion P1.
［比較例１５］
〈粒子調製工程〉
Ｎ２マイクロナノバブル水４５０ｇに硝酸ニッケル六水和物（Ｎｉ（ＮＯ３）２６Ｈ２Ｏ）（関東化学（株）製）５０ｇと、クエン酸水和物（有機安定化剤）（キシダ化学（株）製）０．５ｇを溶解し、溶液ＲＡ１５を調製した。
[Comparative Example 15]
<Particle preparation step>
N 2 and nickel nitrate hexahydrate (Ni (NO 3) 2 6H 2 O) ( manufactured by Kanto Chemical (Co.)) 50 g in micro-nano bubbles water 450 g, citric acid hydrate (organic stabilizer) (Kishida Chemical ( 0.5 g was dissolved to prepare a solution RA15.
Ｎ２マイクロナノバブル水１０００ｇに水素化ホウ素ナトリウム（還元剤）５０ｇを溶解し、溶液ＲＢ１５を調製した。溶液ＲＡ１５を撹拌しながら、溶液ＲＢ１５を添加し、１時間攪拌した。このとき、液が緑色から黒色に変化した。得られた分散液から金属粒子を遠心分離機により分離回収した。 N 2 sodium borohydride micronanobubble water 1000 g (reducing agent) was dissolved 50 g, the solution RB15 was prepared. While stirring the solution RA15, the solution RB15 was added and stirred for 1 hour. At this time, the liquid changed from green to black. Metal particles were separated and collected from the obtained dispersion by a centrifuge.
〈金属粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄工程以降、実施例１と同様にして、黒色の金属粒子分散液ＲＰ１５を得た。
合金粒子分散液Ｐ１の代わりに金属粒子分散液ＲＰ１）を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of metal particle dispersion, preparation of coating liquid and coated substrate>
After the washing step, a black metal particle dispersion RP15 was obtained in the same manner as in Example 1.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1 except that the metal particle dispersion RP1) was used instead of the alloy particle dispersion P1.
［比較例１６］
〈粒子調製工程〉
Ｎ２マイクロナノバブル水９３０ｇにクエン酸３ナトリウム２水和物（有機安定化剤）４００ｇを溶解し、溶液（ＲＳ１６−１）を調製した。
Ｎ２マイクロナノバブル水６００ｇに硫酸第一鉄７水和物（還元剤）１８０ｇを溶解し、溶液（ＲＳ１６−２）を調製した。
溶液（ＲＳ１６−１）と溶液（ＲＳ１６−２）とを混合して３０分間攪拌し、溶液ＲＡ１６を調製した。
[Comparative Example 16]
<Particle preparation step>
N 2 trisodium citrate dihydrate in micronanobubble water 930 g (organic stabilizer) were dissolved 400 g, the solution (RS16-1) was prepared.
N 2 micro-nano water 600g ferrous sulfate heptahydrate (reducing agent) was dissolved 180 g, the solution (RS16-2) was prepared.
The solution (RS16-1) and the solution (RS16-2) were mixed and stirred for 30 minutes to prepare a solution RA16.
Ｎ２マイクロナノバブル水６００ｇに硝酸パラジウム（ＩＩ）２水和物９．１ｇを溶解し、溶液ＲＢ１６を調製した。その後、溶液ＲＢ１６に溶液ＲＡ１６を添加し、１０時間攪拌して得られた分散液から、金属粒子を遠心分離機により分離回収した。 Dissolving palladium nitrate (II) 2 dihydrate 9.1g of N 2 micro-nano water 600 g, a solution RB16 was prepared. Thereafter, the solution RA16 was added to the solution RB16, and the metal particles were separated and collected by a centrifugal separator from the dispersion obtained by stirring for 10 hours.
〈金属粒子分散液の調製、塗布液および被膜付基材の作製〉
洗浄工程以降、実施例１と同様にして、黒茶色の金属粒子分散液ＲＰ１６を得た。
合金粒子分散液Ｐ１の代わりに金属粒子分散液ＲＰ１６を用いた以外は、実施例１と同様にして、塗布液および被膜付基材を作製し、評価した。
<Preparation of metal particle dispersion, preparation of coating liquid and coated substrate>
After the washing step, a black-brown metal particle dispersion RP16 was obtained in the same manner as in Example 1.
A coating solution and a substrate with a film were prepared and evaluated in the same manner as in Example 1, except that the metal particle dispersion RP16 was used instead of the alloy particle dispersion P1.
本発明の合金粒子分散液は、導電性被膜の形成等に用いることができることから、産業上有用である。
The alloy particle dispersion of the present invention is industrially useful because it can be used for forming a conductive film and the like.
Claims (5)
前記合金粒子を洗浄する工程と、
を有し、
平均気泡径が４０ｎｍ〜１０μｍの微小気泡が、前記液に含まれることを特徴とする合金粒子分散液の製造方法。 A step of preparing a metal alloy particle by reducing the metal salt in a liquid containing no organic stabilizer,
Washing the alloy particles,
Has,
A method for producing an alloy particle dispersion, wherein microbubbles having an average bubble diameter of 40 nm to 10 µm are contained in the liquid.
基材上に前記塗布液を塗布して、被膜を形成する工程と、
を有することを特徴とする被膜付基材の製造方法。 Using an alloy particle dispersion prepared by the method according to any one of claims 1 to 3, a step of producing a coating solution containing alloy particles,
A step of applying the coating solution on a substrate to form a coating,
A method for producing a coated substrate, comprising:
An alloy particle dispersion, wherein alloy particles are dispersed in a liquid containing microbubbles having an average cell diameter of 40 nm to 10 μm, and the carbon content of the alloy particles is 0.1% by mass or less.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0135044B2 (en) * | 1986-05-30 | 1989-07-24 | Mitsui Mining & Smelting Co | |
| JP2017206750A (en) * | 2016-05-20 | 2017-11-24 | Ｈａｃｋ Ｊａｐａｎ ホールディングス株式会社 | Method for producing metal nanoparticle |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0135044B2 (en) * | 1986-05-30 | 1989-07-24 | Mitsui Mining & Smelting Co | |
| JP2017206750A (en) * | 2016-05-20 | 2017-11-24 | Ｈａｃｋ Ｊａｐａｎ ホールディングス株式会社 | Method for producing metal nanoparticle |
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