JP7014663B2 - Method for manufacturing alloy particle dispersion - Google Patents
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本発明は、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 liquid.
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 for various purposes as catalyst materials, semiconductor materials, conductive materials and the like. For example, the conductive material is used for electrodes, circuits, antistatic transparent coatings, electromagnetic wave shielding transparent coatings, 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 (see, for example, Patent Documents 1 and 2). However, the metal particles obtained by the method using this organic solvent have a problem of low conductivity.
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３参照）。 Further, by using the alloy particles, the oxidation resistance performance may be higher than that of the single type metal particles, but there is a problem that the conductivity is not improved (see, for example, Patent Document 3).
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が、金属粒子の酸化やイオン化が生じやすく、安定した金属粒子分散液を得ることが難しい。 Therefore, in order to obtain metal particles with higher conductivity, it has been attempted to produce a metal particle dispersion in water, but it is possible to obtain a stable metal particle dispersion because the metal particles are easily oxidized and ionized. difficult.
本発明の課題は、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 storage stability.
微小気泡を含む液中で複数種の金属塩を還元することにより、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）することを見いだした。
微小気泡を含む液は、従来用いられていたＮ２バブリング水等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ため、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。ところが、意外にも、この微小気泡を含む液を用いて複数種の金属塩を還元することにより、製造される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向上することを見いだした。
It was found that by reducing multiple types of metal salts in a liquid containing fine bubbles, oxidation and ionization of alloy particles are suppressed, and the storage stability of the alloy particle dispersion is dramatically improved (prolonged). rice field.
The liquid containing microbubbles has a higher dissolved oxygen concentration and a higher redox potential than the conventionally used degassed (deoxidized) treated water with an inert gas such as N2 bubbling water, and is therefore used in the reduction reaction system. This is generally considered unfavorable. However, surprisingly, by reducing a plurality of kinds of metal salts using the liquid containing the fine bubbles, the storage stability of the produced alloy particle dispersion is improved, and the coating using this alloy particle dispersion is used. We have found that the pot life of the liquid is improved.
さらに、微小気泡を含む液を用いて複数種の金属塩を還元して製造した合金粒子分散液は、その金属種によっては単一種の金属粒子分散液よりも高い保存安定性を有し、この合金粒子分散液を使用した塗布液のポットライフも向上することを見いだした。 Further, the alloy particle dispersion produced by reducing a plurality of kinds of metal salts using a liquid containing fine bubbles has higher storage stability than the single type metal particle dispersion depending on the metal species. It was found that the pot life of the coating liquid using the alloy particle dispersion liquid is also improved.
加えて、この合金粒子を用いて形成した被膜は、その金属種によっては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いだした。 In addition, it has been found that the film formed by using the alloy particles can suppress the decrease in conductivity for a long period of time as compared with the film formed by using a single type of metal particles depending on the metal species.
このことは、金属の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。例えば、貴金属と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卑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、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。
This indicates that by using alloy particles instead of a single type of metal particles, the metal particles exhibit performance not found in a single metal particle. For example, when alloy particles of a noble metal and a base metal are used, storage stability is improved as compared with a single type base metal particle dispersion liquid depending on the metal type, and deterioration of the conductivity of the coating film can be suppressed for a long period of time.
Further, although it depends on the type and ratio of the metal used, the alloy particles have an advantage that the manufacturing cost can be suppressed as compared with the noble metal particles.
すなわち、本発明は、微小気泡を含む液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、この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含むことを特徴とする合金粒子分散液の製造方法に関する。また、この製造方法により調製された合金粒子を含む被膜形成用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。 That is, the present invention comprises a particle preparation step of reducing a plurality of types of metal salts in a liquid containing microbubbles to prepare alloy particles, and a cleaning step of cleaning the alloy particles prepared in this particle preparation step with a cleaning liquid. The present invention relates to a method for producing an alloy particle dispersion liquid, which comprises the same. The present invention also relates to a method for producing a coated base material, which comprises applying a coating liquid for forming a film containing alloy particles prepared by this production method onto the base material.
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ることができる。 It is possible to obtain an alloy particle dispersion liquid having high storage stability in which oxidation and ionization of alloy particles are suppressed.
本発明の合金粒子分散液の製造方法は、微小気泡を含む液（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含む。この製造方法は、上記各工程の前後に他の工程を含んでもよい。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含んでもよい。 The method for producing an alloy particle dispersion liquid of the present invention includes a particle preparation step of reducing a plurality of types of metal salts in a liquid containing microbubbles (hereinafter, may be referred to as a reaction liquid) to prepare alloy particles, and particle preparation. It includes a cleaning step of cleaning the alloy particles prepared in the step with a cleaning liquid. This manufacturing method may include other steps before and after each of the above steps. For example, the cleaning step may be followed by a coarse particle removing step of removing the coarse particles.
粒子調製工程において微小気泡を含む液を用いることにより、分散液に含まれる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を向上できる。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を長期化できる。
この製造方法では、高い収率で合金粒子が得られる。さらに、この合金粒子を用いた被膜は、高い導電性を有する。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、複数種の金属塩から合金への還元反応が促進されること、及び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ことによるものと推察している。
By using a liquid containing fine bubbles in the particle preparation step, it is possible to suppress the oxidation and ionization of the alloy particles contained in the dispersion liquid and improve the storage stability of the alloy particle dispersion liquid. In addition, the pot life of the coating liquid using this alloy particle dispersion liquid can be extended.
With this production method, alloy particles can be obtained in high yield. Further, the coating film using the alloy particles has high conductivity. The reasons for these are not clear, but the microbubbles contained in the reaction solution promote the reduction reaction from multiple metal salts to the alloy, and the alloy particles exist as an alloy without being oxidized. It is presumed that this is due to the protective effect.
［合金粒子分散液の製造方法］
〈粒子調製工程〉
粒子調製工程は、上記のように、微小気泡を含む液中で複数種の金属塩を還元して合金粒子を調製する。微小気泡を含む液としては、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。ただし、本製造法では、不活性ガスでの反応液のバブリングは、必ずしも行う必要はない。
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。
[Manufacturing method of alloy particle dispersion]
<Particle preparation process>
In the particle preparation step, as described above, alloy particles are prepared by reducing a plurality of kinds of metal salts in a liquid containing fine bubbles. The liquid containing fine bubbles may be an organic solvent or water. However, it is more effective in the case of water. If an oxidizing gas such as oxygen is present in the reaction solution, the alloy may be oxidized. Therefore, it is desirable to reduce the oxidizing gas as much as possible in the space in contact with the reaction solution and the reaction solution. This step is preferably performed in a state of being purged with an inert gas such as N2 gas or a rare gas in order to suppress the mixing of oxidizing gas. However, in this production method, it is not always necessary to bubbling the reaction solution with the inert gas.
Here, as the oxidizing gas, oxygen, ozone, carbon dioxide gas, nitric oxide, nitric oxide dinitrogen, nitrogen dioxide, fluorine, chlorine, chlorine dioxide, nitrogen trifluoride, chlorine trifluoride, silicon tetrachloride, difluoride. Examples thereof include oxygen fluoride and perchlorylfluoride.
本工程の反応液は、酸化還元電位が、－５０ｍＶ以下が好ましく、－１００ｍＶ以下がより好ましい。また、ｐＨが、４．０～１１．０が好ましく、４．５～７．０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 of −50 mV or less, more preferably −100 mV or less. The pH is preferably 4.0 to 11.0, more preferably 4.5 to 7.0. By reducing a plurality of types of metal salts within the range of the redox potential and pH, alloy particles are smoothly produced. The reaction temperature is preferably 10 to 80 ° C.
《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んでいるものであり、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 so-called nanobubbles having a bubble diameter of 40 to 100 nm (0.1 μm) and so-called microbubbles having a bubble diameter of 0.1 to 10 μm, and those containing both are preferable. .. The upper limit of the average bubble diameter of the fine bubbles is preferably 500 nm, more preferably 350 nm, and even more preferably 200 nm. The lower limit of the average bubble diameter of the fine bubbles is preferably 50 nm, more preferably 60 nm, and even more preferably 65 nm.
微小気泡の含有量は、１．０×１０３個／ｍＬ以上が好ましく、１．０×１０５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 microbubbles is preferably 1.0 × 10 3 cells / mL or more, more preferably 1.0 × 10 5 cells / mL or more, and even more preferably 1.0 × 10 8 cells / mL or more. The upper limit is not particularly limited, but 1.0 × 10 11 pieces / mL is preferable, 5.0 × 10 10 pieces / mL is more preferable, and 1.0 × 10 10 pieces / mL is further preferable.
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 fine bubbles are obtained by analyzing the Brownian motion moving speed of the bubbles in the liquid by the 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 fine bubbles 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。また、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 that is the raw material of the alloy particles is a metal salt of multiple kinds selected from the 4th group, 5th group, 6th group, 8th group, 9th group, 10th group, 11th group, 13th group, 14th group and 15th group in the periodic table. Salt is used. Further, these metal salts may be mixed and used in advance. Examples of the type of salt include chloride salt, nitrate, sulfate, organic acid salt and the like.
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。とりわけ、ＡｕやＡｇ以外の酸化されやすい金属であっても、酸化を抑制して、高い収率で合金粒子が得られる。 Preferred metal elements are Ti in Group 4, Ta in Group 5, W in Group 6, Ru in Group 8, Co, Rh in Group 9, Ni, Pd, Pt in Group 10, and Cu, Ag, Au in Group 11. Examples are Al and In in the 13th group, Sn in the 14th group, and Sb in the 15th group. In particular, even with easily oxidizable metals other than Au and Ag, alloy particles can be obtained in high yield by suppressing oxidation.
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。その割合の調整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の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 metal elements forming alloy particles can be set arbitrarily. The method for adjusting the ratio is not particularly limited, but for example, it is preferable to mix a metal salt as a raw material for the alloy particles in a liquid so as to have a metal ratio of a desired alloy and reduce the ratio.
〈還元剤〉
粒子調製工程の還元反応は、通常、還元剤を用いて行われる。
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、クエン酸３ナトリウム、酒石酸、次亜リン酸ナトリウム、ギ酸、ＬｉＢＨ４、ＬｉＡｌＨ４、ジボランが挙げられる。中でも、クエン酸３ナトリウム、酒石酸、ギ酸が好ましい。これらは、還元剤と安定剤の両方の機能を有している。このため、不純分を除去する際の工程が軽減されるとともに安定性も向上する。
<Reducing agent>
The reduction reaction in the particle preparation step is usually carried out using a reducing agent.
Examples of the reducing agent include ferrous sulfate, NaBH 4 , hydrazine, hydrogen, alcohol, trisodium citrate, tartrate acid, sodium hypophosphite, formic acid, LiBH 4 , LiAlH 4 , and diboran. Of these, trisodium citrate, tartaric acid, and formic acid are preferable. They have both reducing and stabilizing functions. Therefore, the process for removing the impure component is reduced and the stability is improved.
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 varies depending on the reducing property of the metal salt, but is preferably 0.5 to 10 mol, more preferably 1 to 5 mol, with respect to 1 mol of the metal salt of each metal species constituting the alloy particles. Here, if the reducing agent is less than 0.5 mol with respect to 1 mol of the metal salt, the reduction may be insufficient and the desired alloy particles may not be obtained. On the contrary, if the reducing agent exceeds 10 mol with respect to 1 mol of the metal salt, alloy particles having a larger particle diameter than necessary may be produced.
《有機安定化剤》
粒子調製工程では、有機安定化剤を用いることが好ましい。有機安定化剤の添加により、金属塩に有機安定化剤が吸着され、金属塩の分散性が向上し、金属塩の還元をよりスムーズに行える。また、生成した合金粒子が分散媒中に安定的に分散される。
《Organic stabilizer》
In the particle preparation step, it is preferable to use an organic stabilizer. By adding the organic stabilizer, the organic stabilizer is adsorbed on the metal salt, the dispersibility of the metal salt is improved, and the reduction of the metal salt can be performed more smoothly. Further, the generated alloy particles are stably dispersed in the dispersion medium.
有機安定化剤は、金属塩や合金粒子に吸着して分散安定性を高められるものであればよい。例えば、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適している。中でも、金属塩や合金粒子の表面との相互作用が大きなカルボキシル基を有するカルボン酸化合物が好ましく、多価カルボン酸化合物が特に好ましい。 The organic stabilizer may be any as long as it can be adsorbed on metal salts or alloy particles to enhance dispersion stability. For example, gelatin, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate, polyacrylic acid, carboxylic acid compounds and the like are suitable. Among them, a carboxylic acid compound having a carboxyl group having a large interaction with the surface of a metal salt or alloy particles is preferable, and a polyvalent carboxylic acid compound is particularly preferable.
カルボン酸化合物は、例えば、アンス酸、ヒドロキシアントラセンカルボン酸、ヒドロキシナフトエ酸、没食子酸、クレソチン酸、パラヒドロキシ安息香酸、オルト－アセチルサリチル酸、リンゴ酸、マンデル酸、グルコン酸、クエン酸、酒石酸、乳酸、ベンゼンカルボン酸、ギ酸、酢酸、ブタン酸、プロピオン酸、ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ドデカン酸、テトラデカン酸、ペンタデカン酸、ヘキサデカン酸、９－ヘキサデセン酸、ヘプタデカン酸、オクタデカン酸、グリコール酸、Ｌ－アスコルビン酸、フマル酸、マレイン酸、アジピン酸や、これらの塩が挙げられる。これらは、１種で用いてもよく、２種以上混合して用いてもよい。中でも、クエン酸又はその塩が好ましく、金属塩や合金粒子の表面との相互作用が大きいことから、クエン酸３ナトリウムが特に好ましい。 The carboxylic acid compounds include, for example, anthic acid, hydroxyanthracene carboxylic acid, hydroxynaphthoic acid, galvanic acid, cresotic acid, parahydroxybenzoic acid, ortho-acetylsalicylic acid, malic acid, mandelic acid, gluconic acid, citric acid, tartaric acid, lactic acid. , Benzenecarboxylic acid, formic acid, acetic acid, butanoic acid, propionic acid, pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, 9-hexadecenoic acid, Examples thereof include heptadecanoic acid, octadecanoic acid, glycolic acid, L-ascorbic acid, fumaric acid, maleic acid, adipic acid and salts thereof. These may be used alone or in admixture of two or more. Of these, citric acid or a salt thereof is preferable, and trisodium citric acid is particularly preferable because it has a large interaction with the surface of metal salts and alloy particles.
有機安定化剤の使用量は、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、有機安定化剤が金属塩１モルに対し０．５モル未満の場合は、有機安定化剤の金属塩への吸着量が少なすぎて、金属塩の分散性が不充分となり、金属塩の還元や合金粒子の分散性が不充分となるおそれがある。逆に、有機安定化剤が金属塩１モルに対し１０モルを超えると、特に金属塩の分散性や還元性および合金粒子の分散性が向上するわけではなく、後の洗浄工程での有機安定化剤の除去処理や排水処理に余計な労力を要す場合がある。 The amount of the organic stabilizer used is preferably 0.5 to 10 mol, more preferably 1 to 5 mol, with respect to 1 mol of the metal salt of each metal species constituting the alloy particles. Here, when the amount of the organic stabilizer is less than 0.5 mol with respect to 1 mol of the metal salt, the amount of the organic stabilizer adsorbed on the metal salt is too small, and the dispersibility of the metal salt becomes insufficient, resulting in insufficient metal dispersibility. There is a risk that the reduction of salts and the dispersibility of alloy particles will be insufficient. On the contrary, when the amount of the organic stabilizer exceeds 10 mol per 1 mol of the metal salt, the dispersibility and reducibility of the metal salt and the dispersibility of the alloy particles are not particularly improved, and the organic stability in the subsequent cleaning step is not improved. Extra labor may be required for the removal treatment of the agent and the wastewater treatment.
《ｐＨ調整剤》
粒子調製工程の反応液のｐＨが４．０～１１．０になるように、ｐＨ調整剤を用いることができる。ｐＨ調整剤は、鉱酸、有機酸が適している。中でもＣ１～Ｃ３の炭素数をもつ有機酸が好ましい。なお、上記有機安定化剤が、ｐＨ調整剤の機能を兼ねてもよい。
<< pH adjuster >>
A pH adjuster can be used so that the pH of the reaction solution in the particle preparation step is 4.0 to 11.0. A mineral acid or an organic acid is suitable as the pH adjuster. Of these, organic acids having C 1 to C 3 carbon atoms are preferable. The organic stabilizer may also function as a pH adjuster.
〈洗浄工程〉
洗浄工程は、粒子調製工程で調製した合金粒子を洗浄液で洗浄する。本工程で、脱塩が行われ、また、有機安定化剤の除去が行われる。ここで、塩とは、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。
<Washing process>
In the cleaning step, the alloy particles prepared in the particle preparation step are washed with a cleaning liquid. In this step, desalting is performed and the organic stabilizer is removed. Here, the salt 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 thereof include metal ions such as sodium and iron, boron ions, chloride ions, nitrate ions, sulfate ions, and organic acid ions.
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。また、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く、微小気泡を含む液（微小気泡を含むバブリング液を含む）を用いることが特に好ましい。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 suitable for water or alcohol, and may contain other components. Further, 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 fine bubbles, and a liquid containing fine bubbles (including a bubbling liquid containing fine bubbles). ) Is particularly preferable. The details of the liquid containing fine bubbles are the same as the liquid containing fine bubbles (reaction liquid) used in the particle preparation step. Further, it is preferable that the alloy particle dispersion liquid produced after cleaning also contains fine bubbles.
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有機安定化剤の量を低減できる。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 cleaning the alloy particles with a cleaning liquid containing fine bubbles, ionization and oxidation of the alloy particles are prevented, and the storage stability of the alloy particle dispersion liquid and the pot life of the coating liquid using this alloy particle dispersion liquid are dramatically improved. Can be improved. In addition, the dispersibility of the produced alloy particles is improved, and the amount of the organic stabilizer in the final dispersion can be reduced. Therefore, when the film is formed, the alloy particles come into direct contact with each other, the resistance at the particle boundary is reduced, and as a result, a film having high conductivity can be formed.
洗浄方法は、デカンテーションによる方法や、限外膜やセラミック膜を使用した洗浄方法が例示される。デカンテーションによる方法は、例えば、上記粒子調製工程にて調製した合金粒子分散液から合金粒子を回収し、かかる回収した合金粒子を洗浄液中に浸漬して洗浄（脱塩）を行う。この洗浄液は、高濃度の有機安定化剤を含むものが好ましい。これにより、合金粒子を適度に凝集させると共に、上澄み液に、硝酸イオン、硫酸イオン等の不純分を溶出させて、この不純分を除去できる。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。なお、洗浄工程で用いる有機安定化剤は、粒子調製工程で用いるものと同一であってもよいし、異なっていてもよい。 Examples of the cleaning method include a decantation method and a cleaning method using an ultrafiltration membrane or a ceramic membrane. In the decantation method, for example, alloy particles are recovered from the alloy particle dispersion liquid prepared in the particle preparation step, and the recovered alloy particles are immersed in the cleaning liquid for cleaning (desalting). This cleaning liquid preferably contains a high concentration of an organic stabilizer. As a result, the alloy particles can be appropriately aggregated, and the impurities such as nitrate ions and sulfate ions can be eluted into the supernatant liquid to remove the impurities. Further, it is preferable to purify using an ion exchange resin. The organic stabilizer used in the cleaning step may be the same as that used in the particle preparation step, or may be different.
本発明では、有機安定化剤の濃度が比較的低い洗浄液を用いた場合でも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）を図れるため、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となり、これによっても効率的に合金粒子を製造できる。洗浄工程の簡略化により、合金粒子のロスが少なくなり、収率が向上する。さらに、洗浄工程の簡略化により、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。 In the present invention, the impure component can be sufficiently removed even when a cleaning liquid having a relatively low concentration of the organic stabilizer can be used, and the subsequent treatment with an ion exchange resin can be simplified (reduction of the amount of resin), which is efficient. Can produce alloy particles. In addition, it is possible to reduce the number of cleanings, which also makes it possible to efficiently produce alloy particles. By simplifying the cleaning process, the loss of alloy particles is reduced and the yield is improved. Further, since the induction of oxidation of the alloy particles is suppressed by the simplification of the cleaning step, the coating film formed by 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 the coarse particles by centrifugation or the like.
［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。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い。中でも、メタノールやエタノールが好ましい。
[Alloy particle dispersion]
The alloy particle dispersion liquid of the present invention is characterized in that alloy particles are dispersed in a liquid containing fine bubbles. The details of the liquid containing fine bubbles are the same as the liquid containing fine bubbles (reaction liquid) used in the particle preparation step. This alloy particle dispersion can be produced by the above-mentioned production method.
Water or an organic solvent is suitable as the dispersion medium. Here, the organic solvent is not particularly limited in type, but alcohols are preferable because of the ease of processing as a coating liquid and the ease of producing a coated substrate. Of these, methanol and ethanol are preferable.
合金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と考えられる。 The storage stability of the alloy particle dispersion is usually about one year when it is produced using only a solvent bubbled with an inert gas, although it depends on the metal species. On the other hand, the storage stability of the alloy particle dispersion of the present invention often exceeds one year. It is considered that this is different from the action when bubbles are simply present, and some action is working between the fine bubbles and the alloy particles.
合金粒子の種類は、上記金属塩の金属として例示したものを組み合わせることができる。これは、周期表の同じ族同士の金属種の組み合わせでもよいし、異なる族の金属種の組み合わせでもよい。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等が挙げられる。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く、有機安定化剤との親和性も高い。したがって、これらの合金粒子は、有機安定化剤及び微小気泡の安定化作用により、より保存安定性の高い分散液が得られやすい。 As the type of alloy particles, those exemplified as the metal of the above metal salt can be combined. This may be a combination of metal species of the same group in the 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- Examples thereof include Si and Ru-Pt. Among them, alloy particles such as Ag-Pd, Cu-Pd, and Ni-Cu are less susceptible to oxidation and ionization, and have a high affinity with organic stabilizers. Therefore, with these alloy particles, it is easy to obtain a dispersion liquid having higher storage stability due to the action of the organic stabilizer and the stabilizing action of microbubbles.
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 based on the mass of the metal species having the lowest ratio with respect to the total amount of the metal species constituting the alloy particles, and more preferably 1.0% by mass or more. It is preferable, and 10% by mass or more is more preferable. When the proportion of the metal species having the lowest proportion is less than 0.5% by mass, the effect is sufficiently shown even if the alloy particles exhibit higher storage stability than the metal particles of a single species. There is no risk. 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。 With the current technology, it is difficult to measure the average bubble diameter and the number of bubbles of the fine bubbles in the dispersion liquid in which the alloy particles and the fine bubbles coexist. Therefore, the alloy particles are removed with an ultrafiltration membrane, and the fine bubbles contained in this filtrate are measured to obtain the average bubble diameter and the number of fine bubbles. That is, the average bubble diameter and the number of bubbles of the present invention refer to those obtained by measuring a filtrate that has passed through an ultrafiltration membrane having a molecular weight cut-off 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 0 to 300 mV, more preferably 100 to 250 mV. Here, when the ORP is less than 0 mV, the dispersibility of the alloy particles may become unstable because it is in the reducing field. On the contrary, when the ORP exceeds 300 mV, the alloy particles may be oxidized.
The pH is usually 4.0 to 7.0, preferably 4.5 to 6.5. Here, when the pH is less than 4.0, it exists in an ionic state, and alloy particles may not be obtained. On the contrary, when the pH exceeds 7.0, the alloy particles may aggregate due to the high salt concentration.
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 electrical conductivity of the alloy particle dispersion is preferably 10 to 500 μS / cm, more preferably 50 to 300 μS / cm. Here, when the electric conductivity is less than 10 μS / cm, the amount of the dispersant may be small and the storage stability may be lowered (the life may be short). On the contrary, when the electric conductivity exceeds 500 μS / cm, the salt concentration becomes high, so that the storage stability may decrease. Further, even if a conductive film is formed, the conductivity may deteriorate.
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、分散媒、有機安定化剤、及び各種添加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。 The content of each of the impure components of the alloy particle dispersion is preferably 100 ppm or less, more preferably 80 ppm or less, still more preferably 50 ppm or less, based on the alloy particles. Here, if it exceeds 100 ppm, the salt concentration becomes high, so that the storage stability may decrease. Further, even if a conductive film is formed, the conductivity may deteriorate. The impure content of the alloy particle dispersion is a substance other than the alloy particles, the dispersion medium, the organic stabilizer, and various additives. This is a substance other than the alloy particles produced by the reduction treatment of the metal salt, and exists as ions in the reaction solution. Specifically, metal ions such as sodium and iron, boron ions, chloride ions, nitrate ions, sulfate ions and the like are exemplified.
また、合金粒子分散液中の有機安定化剤量は、合金粒子に対して、０．１～５質量％が好ましく、０．２～３質量％がより好ましい。ここで、有機安定化剤が合金粒子に対して０．１質量％未満の場合は、有機安定化剤の合金粒子への吸着量が少なすぎて、合金粒子の分散性が不充分となるおそれがある。逆に、有機安定化剤が合金粒子に対して５質量％を超えると、洗浄が不充分であり、合金粒子の分散性が向上せず、むしろ粒子同士が凝集するおそれがある。この合金粒子分散液に含まれる有機安定化剤の含有量は、有機安定化剤に由来するＣ（カーボン）量を分析することで求めることができる。 The amount of the organic stabilizer in the alloy particle dispersion is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, based on the alloy particles. Here, when the amount of the organic stabilizer is less than 0.1% by mass with respect to the alloy particles, the amount of the organic stabilizer adsorbed on the alloy particles is too small, and the dispersibility of the alloy particles may be insufficient. There is. On the contrary, if the amount of the organic stabilizer exceeds 5% by mass with respect to the alloy particles, the cleaning is insufficient, the dispersibility of the alloy particles is not improved, and the particles may rather aggregate with each other. The content of the organic stabilizer contained in this alloy particle dispersion can be determined by analyzing the amount of C (carbon) derived from the organic stabilizer.
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が得られる。
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 this alloy particle dispersion is preferably 3 to 200 nm, more preferably 5 to 70 nm. When the average particle size is 3 to 200 nm, a highly transparent conductive film can be obtained.
The average particle size of the alloy particles is obtained by taking an electron micrograph, measuring the particle size of any 500 particles, and obtaining the average value thereof.
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ような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、本発明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、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 liquid 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 in the past can be realized. In addition, a long-term pot life that could not be realized in the past can be realized even with a coating liquid using this alloy particle dispersion liquid. Further, the alloy particle dispersion liquid of the present invention has a very low content of oxide particles and can produce a highly conductive film. Here, it is preferable that the metal oxide is not detected by X-ray diffraction. The content thereof is preferably 500 ppm or less, more preferably 200 ppm or less, still more preferably 100 ppm or less with respect to the particles. If the content of the metal oxide exceeds 500 ppm, the storage stability of the dispersion is lowered, and the particles may aggregate and precipitate. Further, when the alloy particles are ionized, they do not exist as particles in the liquid, and even if they are used as a coating liquid, a desired film cannot be obtained.
［被膜形成用塗布液］
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。
[Coating liquid for film formation]
A coating liquid for forming a film can be produced using the alloy particles contained in the alloy particle dispersion liquid of the present invention. Various conventionally known additives can be added to the coating liquid for film formation.
被膜付基材の製造は、この被膜形成用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。 In the production of a coated base material, the coating liquid for forming a coating is applied onto the base material, dried, and fired if necessary.
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挙げられる。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 base material include film-like and sheet-like base materials made of glass, plastic, ceramic, metal and the like. Examples of the coating method of the coating liquid include a dipping method, a spinner method, a spray method, a roll coater method, a flexographic printing method and the like. The film thickness of the film 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金属粒子は有機安定化剤等の有機物の付着が少ないため、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、高温焼成による金属粒子の凝集、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 of about room temperature to 90 ° C. The firing temperature is, for example, about 120 to 900 ° C., and may be about 150 to 350 ° C. Since the metal particles contained in the dispersion liquid of the present invention have little adhesion of organic substances such as an organic stabilizer, it is not necessary to bake them at a high temperature such as 400 ° C. or higher to remove the organic substances. As a result, it is possible to prevent aggregation and fusion of metal particles due to high-temperature firing, and it is possible to suppress deterioration of the haze of the obtained film.
［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（２５℃、以下同じ）、電気伝導度１．１７μＳ／ｃｍ、溶存酸素濃度（ＤＯ）１．７０ｐｐｍ、酸化還元電位（ＯＲＰ）３３０ｍＶ）を準備した。
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（Ｓ１－１）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（Ｓ１－２）を調製した。
溶液（Ｓ１－１）と溶液（Ｓ１－２）とを混合して３０分間攪拌し、溶液Ａ１を調製した。
[Example 1]
<Particle preparation process>
N 2 micro - nano bubble water (average bubble diameter 70 nm, number of bubbles 240 million cells / mL) is brought into contact with ultrapure water using a swirling flow type bubble generator (HYK-20-SD manufactured by Ligaric Co., Ltd.). , PH 5.79 (25 ° C., the same applies hereinafter), electrical conductivity 1.17 μS / cm, dissolved oxygen concentration (DO) 1.70 ppm, redox potential (ORP) 330 mV).
400 g of trisodium citrate dihydrate (organic stabilizer) was dissolved in 930 g of N 2 micro-nano bubble water to prepare a solution (S1-1).
180 g of ferrous sulfate heptahydrate (reducing agent) was dissolved in 600 g of N2 micro-nanobubble water to prepare a solution (S1-2).
The solution (S1-1) and the solution (S1-2) were mixed and stirred for 30 minutes to prepare a solution A1.
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。 A solution B1 was prepared by dissolving 38 g of copper (II) nitrate trihydrate and 25 g of palladium (II) nitrate dihydrate in 600 g of N2 micro-nanobubble water. Then, the solution A1 was added to the solution B1 and stirred for 10 hours, and the alloy particles were separated and recovered from the obtained dispersion by a centrifuge.
〈洗浄工程〉
超純水（ｐＨ６．３２、電気伝導度０．０５μＳ／ｃｍ、ＤＯ６．１７ｐｐｍ、ＯＲＰ３５０ｍＶ）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。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。
<Washing process>
Ultrapure water (pH 6.32, electrical conductivity 0.05 μS / cm, DO 6.17 ppm, ORP350 mV) was bubbling with N 2 for 1 hour to remove dissolved oxygen, and N 2 bubbling water (pH 6.6, electrical conductivity). Degree 0.6 μS / cm, DO 0.6 ppm, ORP 260 mV) was prepared. The alloy particles separated and recovered were immersed in 200 g of a trisodium citrate aqueous solution having a concentration of 20% by mass prepared using N2 bubbling water, washed (demineralized), and then separated and recovered by centrifugation again.
ＩＣＰ分析で金属濃度を定量し、Ｎ２バブリング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（Ｐ－１）を得た。 The metal concentration was quantified by ICP analysis, and an alloy particle aqueous dispersion having a metal-equivalent concentration of 2.5% by mass was prepared using N2 bubbling water. Then, deionization was performed using 10 g of an amphoteric ion exchange resin to obtain a black-brown alloy particle dispersion (P-1) having a metal-equivalent concentration of 2.5% by mass.
［微小気泡の平均気泡径と気泡個数］
合金粒子分散液（Ｐ－１）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（Ｐ－１）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 microbubbles]
For the fine particles in the alloy particle dispersion (P-1), the alloy particle dispersion is filtered through an ultrafiltration membrane (SEP-1013 fractional molecular weight 4000 manufactured by Asahi Kasei) to remove the alloy particles, and the fine particles in the filtrate are removed. The average bubble diameter and the number of bubbles were measured. The average bubble diameter and the number of bubbles of the fine bubbles were measured by measuring the Brownian motion moving speed of the bubbles in the liquid by using the nanoparticle tracking analysis method. Specifically, about 20 mL of the measurement sample (solution A1, solution B1 or the filtrate of the alloy particle dispersion (P-1)) is injected into the measuring instrument (“Nanosite NS300” manufactured by Malvern) while sucking the nanoparticles. It was measured by the tracking analysis method. The micro-nano bubble water was measured by the above method as it was without filtration treatment.
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（微小気泡の平均気泡径と気泡個数、ｐＨ、ＯＲＰ、合金粒子の含有量及び収率、一次粒子の平均粒子径、二次粒子の平均粒子径、金属酸化物の有無、不純分（Ｆｅ，Ｎａ，Ｂ，ＳＯ４，ＮＯ３）含有量、Ｃ（カーボン）量、保存安定性）を表１に示した（以下の実施例、比較例も同様）。 Physical properties of the solution after reduction in the particle preparation step (pH, ORP), physical properties of the finally obtained alloy particle dispersion (average bubble diameter and number of microbubbles, pH, ORP, content and yield of alloy particles) Rate, average particle size of primary particles, average particle size of secondary particles, presence / absence of metal oxide, impure content (Fe, Na, B, SO 4 , NO 3 ), C (carbon) amount, storage stability ) Is shown in Table 1 (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。
[Electrical conductivity]
The electrical conductivity was measured by the AC two-electrode method. Specifically, a pH meter (F-74 manufactured by HORIBA, Ltd., electrode model number 3551-10D) was obtained by immersing the electrode in the liquid to be measured in the conductivity measurement mode. The temperatures of the bubbling water, the micro-nano bubble water, and the alloy particle dispersion were adjusted to 25 ° C.
［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。
[Redox potential (ORP)]
The redox potential (Oxidation Reduction Potential) was determined by immersing the electrode in a liquid for measuring the electrode in the ORP measurement mode for setting the pH meter (F-74 manufactured by Horiba Seisakusho, electrode model number 9300-10D). The temperatures of the bubbling water, the micro-nano bubble water, and the alloy particle dispersion were adjusted to 25 ° C.
［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)]
Dissolved Oxygen concentration was measured by the septal galvanic cell method. Specifically, a pH meter (OM-51 manufactured by HORIBA, Ltd., electrode model number 9520-10D) was obtained by immersing the electrode in the liquid to be measured in the conductivity measurement mode under atmospheric pressure. The temperatures of the bubbling water, the micro-nano bubble water, and the alloy particle dispersion were adjusted to 25 ° C.
［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で測定した金属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 metal dispersion measured by ICP, and dividing this by the theoretical amount of metal calculated from the charged metal salt. Was 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 particle size of primary particles]
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 by a transmission electron microscope (H-800 manufactured by Hitachi, Ltd.), and photographed at a magnification of 250,000 times. The particle size of any 500 particles in the obtained photographic projection was measured, and the average value was taken as the average particle size 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）を金属粒子の平均粒子径とした。
[Average particle size of secondary particles]
The alloy particle dispersion was placed in the cell as it was, measured by the microtrack method, and the average value (D50) was taken as the average particle diameter of the metal particles.
［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 the presence or absence of alloys and metal oxides by X-ray diffraction]
The presence or absence of the alloy and the metal oxide was confirmed by performing an analysis by X-ray diffraction with the alloy particle dispersion liquid as a solution. The qualitative analysis of the sample by X-ray diffraction was performed by X-RAY DIFFRACT METER (SmartLab) manufactured by RIGAKU Co., Ltd. Specifically, the sample is placed in a cell, set in a device, tube voltage 45.0 kV, tube current 200.0 mA, anti-cathode Cu, measurement range: start angle to end angle (2θ) 5.000 ° to 70.000. The measurement was performed at ° and a scan speed of 5.000 ° / min.
If the peak of the alloy is observed and the peak of the metal alone is not observed, it is judged that the alloy is present.
When the presence of alloy is confirmed: ○
If the presence of alloy is not confirmed: ×
If no metal oxide peak is observed: ○
When a peak of metal oxide is observed: ×
［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]
Mass spectrometry of each element was performed by chemical analysis using an inductively coupled plasma spectrophotometer. Specifically, a solution prepared by dissolving an alloy particle dispersion in concentrated nitric acid and adjusting the concentration to 10 to 100 mass ppm with water was analyzed by SEQUENTIAL PLASMA SPECTROMETER (ICPS-8100) manufactured by Shimadzu Corporation.
［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、Ｃｌ、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 , Cl, and NO 3 were measured using an ion exchange chromatograph (TSKgel SuperQ-5PW manufactured by Tosoh).
［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。
[Measurement of C (carbon) amount]
The carbon content in the alloy particles was measured by drying the alloy particle dispersion at 100 ° C. and using a carbon sulfur analyzer (EMIA-320V manufactured by HORIBA).
［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]
It was confirmed whether or not the alloy particles were oxidized by X-ray diffraction (XRD) of the alloy particle dispersion stored at 25 ° C. and the change in conductivity.
〈被膜形成用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（Ｐ－１）をエタノールで０．５質量％に希釈し、被膜形成用塗布液を作製した。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－１に示した（以下の実施例、比較例も同様）。
<Preparation of coating liquid for film formation and substrate with film>
The obtained alloy particle dispersion liquid (P-1) was diluted with ethanol to 0.5% by mass to prepare a coating liquid for film formation. This was applied to glass by a spin coating method, and then fired at 200 ° C. for 30 minutes in a nitrogen atmosphere to prepare a coated substrate. The conductivity of this coated substrate was measured with a low resta (NSP probe manufactured by Mitsubishi Chemical Corporation). In addition, a part of the coating film was peeled off with a cutter knife to create a step, and this step was measured with a laser microscope, and this was used as the film thickness. These results are shown in Table 1 (the same applies to the following examples and comparative examples).
［実施例２］
〈粒子調製工程〉
実施例１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９３０ｇにクエン酸３ナトリウム２水和物４００ｇを溶解し、溶液（Ｓ２－１）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１８０ｇを溶解し、溶液（Ｓ２－２）を調製した。
溶液（Ｓ２－１）と溶液（Ｓ２－２）とを混合して３０分間攪拌し、溶液Ａ２を調製した。
[Example 2]
<Particle preparation process>
N2 micro-nano bubble water was prepared in the same manner as in Example 1.
400 g of trisodium citrate dihydrate was dissolved in 930 g of N2 micro-nanobubble water to prepare a solution (S2-1).
180 g of ferrous sulfate heptahydrate was dissolved in 600 g of N2 micro-nano bubble water to prepare a solution (S2-2).
The solution (S2-1) and the solution (S2-2) were mixed and stirred for 30 minutes to prepare a solution A2.
Ｎ２マイクロナノバブル水６００ｇに硝酸銅（ＩＩ）３水和物６１ｇと硝酸パラジウム（II）２水和物１０ｇを溶解し、溶液Ｂ２を調製した。その後、溶液Ｂ２に溶液Ａ２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。 A solution B2 was prepared by dissolving 61 g of copper (II) nitrate trihydrate and 10 g of palladium (II) nitrate dihydrate in 600 g of N2 micro-nanobubble water. Then, the solution A2 was added to the solution B2, and the alloy particles were separated and recovered from the dispersion obtained by stirring for 10 hours by a centrifuge.
〈洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。以降、実施例１と同様にして、黒茶色の合金粒子分散液（Ｐ－２）を得た。
<Washing process>
N2 bubbling water was prepared in the same manner as in Example 1. After that, a black-brown alloy particle dispersion liquid (P-2) was obtained in the same manner as in Example 1.
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（Ｐ－２）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (P-2) was used.
［実施例３］
〈粒子調製工程〉
実施例１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９３０ｇにクエン酸３ナトリウム２水和物４００ｇを溶解し、溶液（Ｓ３－１）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１８０ｇを溶解し、溶液（Ｓ３－２）を調製した。
溶液（Ｓ３－１）と溶液（Ｓ３－２）とを混合して３０分間攪拌し、溶液Ａ３を調製した。
[Example 3]
<Particle preparation process>
N2 micro-nano bubble water was prepared in the same manner as in Example 1.
400 g of trisodium citrate dihydrate was dissolved in 930 g of N2 micro-nano bubble water to prepare a solution (S3-1).
180 g of ferrous sulfate heptahydrate was dissolved in 600 g of N2 micro-nano bubble water to prepare a solution (S3-2).
The solution (S3-1) and the solution (S3-2) were mixed and stirred for 30 minutes to prepare a solution A3.
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Ｂ３を調製した。その後、溶液Ｂ３に溶液Ａ３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。 Solution B3 was prepared by dissolving 75 g of copper (II) nitrate trihydrate and 0.5 g of palladium (II) nitrate dihydrate in 600 g of N2 micro-nanobubble water. Then, the solution A3 was added to the solution B3, and the alloy particles were separated and recovered from the dispersion obtained by stirring for 10 hours by a centrifuge.
〈洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。以降、実施例１と同様にして、黒茶色の合金粒子分散液（Ｐ－３）を得た。
<Washing process>
N2 bubbling water was prepared in the same manner as in Example 1. After that, a black-brown alloy particle dispersion liquid (P-3) was obtained in the same manner as in Example 1.
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（Ｐ－３）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (P-3) was used.
［実施例４］
〈粒子調製工程〉
実施例１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９３０ｇにクエン酸３ナトリウム２水和物４００ｇを溶解し、溶液（Ｓ４－１）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（Ｓ４－２）を調製した。
溶液（Ｓ４－１）と溶液（Ｓ４－２）とを混合して３０分間攪拌し、溶液Ａ４を調製した。
[Example 4]
<Particle preparation process>
N2 micro-nano bubble water was prepared in the same manner as in Example 1.
400 g of trisodium citrate dihydrate was dissolved in 930 g of N 2 micro-nano bubble water to prepare a solution (S4-1).
A solution (S4-2) was prepared by dissolving 100 g of ferrous sulfate heptahydrate in 500 g of N 2 micro-nano bubble water.
The solution (S4-1) and the solution (S4-2) were mixed and stirred for 30 minutes to prepare a solution A4.
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、金属粒子を遠心分離機により分離回収した。 Solution B4 was prepared by dissolving 28.5 g of silver nitrate (I) and 45.3 g of palladium (II) nitrate dihydrate in 300 g of N2 micro-nano bubble water. Then, the solution A4 was added to the solution B4, and the metal particles were separated and recovered from the dispersion obtained by stirring for 10 hours by a centrifuge.
〈洗浄工程〉
実施例１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、上記分離回収した金属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。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、上記分離回収した金属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。
<Washing process>
N2 bubbling water was prepared in the same manner as in Example 1. The metal particles separated and recovered were immersed in 200 g of a trisodium citrate aqueous solution having a concentration of 30% by mass prepared using N2 bubbling water, washed (demineralized), and then separated and recovered by centrifugation. Similarly, the metal particles separated and recovered were immersed in 200 g of a trisodium citrate aqueous solution having a concentration of 20% by mass prepared using N2 bubbling water, washed (demineralized), and then separated and recovered by centrifugation again. ..
ＩＣＰ分析で金属濃度を定量し、Ｎ２バブリング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（Ｐ－４）を得た。 The metal concentration was quantified by ICP analysis, and an alloy particle aqueous dispersion having a metal-equivalent concentration of 2.5% by mass was prepared using N2 bubbling water. Then, deionization was performed using 10 g of an amphoteric ion exchange resin to obtain a black-brown alloy particle dispersion (P-4) having a concentration of 2.5% by mass in terms of metal.
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（Ｐ－４）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (P-4) was used.
［実施例５］
〈粒子調製工程〉
実施例１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９３０ｇにクエン酸３ナトリウム２水和物４００ｇを溶解し、溶液（Ｓ５－１）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（Ｓ５－２）を調製した。
溶液（Ｓ５－１）と溶液（Ｓ５－２）とを混合して３０分間攪拌し、溶液Ａ５を調製した。
[Example 5]
<Particle preparation process>
N2 micro-nano bubble water was prepared in the same manner as in Example 1.
400 g of trisodium citrate dihydrate was dissolved in 930 g of N 2 micro-nano bubble water to prepare a solution (S5-1).
A solution (S5-2) was prepared by dissolving 100 g of ferrous sulfate heptahydrate in 500 g of N2 micro-nanobubble water.
The solution (S5-1) and the solution (S5-2) were mixed and stirred for 30 minutes to prepare a solution A5.
Ｎ２マイクロナノバブル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、金属粒子を遠心分離機により分離回収した。 Solution B5 was prepared by dissolving 51.3 g of silver nitrate (I) and 9.1 g of palladium (II) dihydrate in 300 g of N 2 micro-nano bubbles. Then, the solution A5 was added to the solution B5, and the metal particles were separated and recovered from the dispersion obtained by stirring for 10 hours by a centrifuge.
〈洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。以降、実施例４と同様にして、黒茶色の合金粒子分散液（Ｐ－５）を得た。
<Washing process>
N2 bubbling water was prepared in the same manner as in Example 1. After that, a black-brown alloy particle dispersion liquid (P-5) was obtained in the same manner as in Example 4.
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（Ｐ－５）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (P-5) was used.
［実施例６］
〈粒子調製工程〉
実施例１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９３０ｇにクエン酸３ナトリウム２水和物４００ｇを溶解し、溶液（Ｓ６－１）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（Ｓ６－２）を調製した。
溶液（Ｓ６－１）と溶液（Ｓ６－２）とを混合して３０分間攪拌し、溶液Ａ６を調製した。
[Example 6]
<Particle preparation process>
N2 micro-nano bubble water was prepared in the same manner as in Example 1.
400 g of trisodium citrate dihydrate was dissolved in 930 g of N 2 micro-nano bubble water to prepare a solution (S6-1).
A solution (S6-2) was prepared by dissolving 100 g of ferrous sulfate heptahydrate in 500 g of N2 micro-nanobubble water.
The solution (S6-1) and the solution (S6-2) were mixed and stirred for 30 minutes to prepare a solution A6.
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、金属粒子を遠心分離機により分離回収した。 Solution B6 was prepared by dissolving 51.3 g of silver nitrate (I) and 9.1 g of palladium (II) dihydrate in 300 g of N 2 micro-nano bubble water. Then, the solution A6 was added to the solution B6, and the metal particles were separated and recovered from the dispersion obtained by stirring for 10 hours by a centrifuge.
〈洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。以降、実施例１と同様にして、黒茶色の合金粒子分散液（Ｐ－６）を得た。
<Washing process>
N2 bubbling water was prepared in the same manner as in Example 1. After that, a black-brown alloy particle dispersion liquid (P-6) was obtained in the same manner as in Example 1.
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（Ｐ－６）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (P-6) was used.
［実施例７］
〈粒子調製工程〉
実施例１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Ａ７を調製した。
[Example 7]
<Particle preparation process>
N2 micro-nano bubble water was prepared in the same manner as in Example 1.
Nickel nitrate hexahydrate (Ni (NO 3 ) 26H 2 O ) (manufactured by Kanto Chemical Co., Ltd.) 50 g, copper (II) nitrate trihydrate 10 g, and citrate water in 450 g of N 2 micro-nano bubble water. 0.5 g of a Japanese product (organic stabilizer) (manufactured by Kishida Chemical Co., Ltd.) was dissolved to prepare a solution A7.
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Ｂ７を調製した。溶液Ａ７を撹拌しながら、溶液Ｂ７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。 50 g of sodium borohydride (reducing agent) was dissolved in 1000 g of N 2 micro-nano bubble water to prepare a solution B7. While stirring the solution A7, the solution B7 was added and stirred for 1 hour. At this time, the liquid changed from green to black. Metal particles were separated and recovered from the obtained dispersion by a centrifuge.
〈洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。以降、実施例１と同様にして、黒茶色の合金粒子分散液（Ｐ－７）を得た。
<Washing process>
N2 bubbling water was prepared in the same manner as in Example 1. After that, a black-brown alloy particle dispersion liquid (P-7) was obtained in the same manner as in Example 1.
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（Ｐ－７）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (P-7) was used.
［実施例８］
〈粒子調製工程〉
実施例１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９３０ｇにクエン酸３ナトリウム２水和物４００ｇを溶解し、溶液（Ｓ８－１）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１８０ｇを溶解し、溶液（Ｓ８－２）を調製した。
溶液（Ｓ８－１）と溶液（Ｓ８－２）とを混合して３０分間攪拌し、溶液Ａ８を調製した。
[Example 8]
<Particle preparation process>
N2 micro-nano bubble water was prepared in the same manner as in Example 1.
400 g of trisodium citrate dihydrate was dissolved in 930 g of N 2 micro-nano bubble water to prepare a solution (S8-1).
180 g of ferrous sulfate heptahydrate was dissolved in 600 g of N2 micro-nano bubble water to prepare a solution (S8-2).
The solution (S8-1) and the solution (S8-2) were mixed and stirred for 30 minutes to prepare a solution A8.
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１２５ｇ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、金属粒子を遠心分離機により分離回収した。 A solution B8 was prepared by dissolving 38 g of copper (II) nitrate trihydrate and 125 g of palladium (II) nitrate dihydrate in 600 g of N2 micro-nanobubble water. Then, the solution A8 was added to the solution B8, and the metal particles were separated and recovered from the dispersion obtained by stirring for 10 hours by a centrifuge.
〈洗浄工程〉
実施例１の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。以降、Ｎ２バブリング水の代わりに、このＮ２マイクロナノバブル水を使用する以外は、実施例１と同様にして、黒茶色の合金粒子分散液（Ｐ－８）を得た。
<Washing process>
N2 micro-nano bubble water was prepared in the same manner as in the particle preparation step of Example 1. Hereinafter, a black-brown alloy particle dispersion liquid (P-8) was obtained in the same manner as in Example 1 except that this N 2 micro-nano bubble water was used instead of the N 2 bubbling water.
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（Ｐ－８）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (P-8) was used.
［比較例１］
〈粒子調製工程〉
実施例１の洗浄工程と同様にして、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 process>
N2 bubbling water was prepared in the same manner as in the washing step of Example 1. 400 g of trisodium citrate dihydrate (organic stabilizer) was dissolved in 930 g of N2 bubbling water to prepare a solution (RS1-1).
180 g of ferrous sulfate heptahydrate (reducing agent) was dissolved in 600 g of N2 bubbling water to prepare a solution (RS1-2).
The solution (RS1-1) and the solution (RS1-2) were mixed and stirred for 30 minutes to prepare solution RA1.
Ｎ２バブリング水６００ｇに硝酸銅（ＩＩ）３水和物７６ｇ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、金属粒子を遠心分離機により分離回収した。 76 g of copper (II) nitrate trihydrate was dissolved in 600 g of N2 bubbling water to prepare a solution RB1. Then, the solution RA1 was added to the solution RB1 and stirred for 10 hours, and the metal particles were separated and recovered from the obtained dispersion by a centrifuge.
〈洗浄工程〉
実施例１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、上記分離回収した金属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。
<Washing process>
N2 bubbling water was prepared in the same manner as in Example 1. The metal particles separated and recovered were immersed in 200 g of a trisodium citrate aqueous solution having a concentration of 20% by mass prepared using N2 bubbling water, washed (demineralized), and then separated and recovered by centrifugation again.
ＩＣＰ分析で金属濃度を定量し、Ｎ２バブリング水を用いて金属換算で濃度が２．５質量％の金属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％の黒茶色の金属粒子分散液（ＲＰ－１）を得た。 The metal concentration was quantified by ICP analysis, and a metal particle aqueous dispersion having a metal equivalent concentration of 2.5% by mass was prepared using N2 bubbling water. Then, deionization was performed using 10 g of an amphoteric ion exchange resin to obtain a black-brown metal particle dispersion (RP-1) having a concentration of 2.5% by mass in terms of metal.
〈被膜形成用塗布液および被膜付基材の作製〉
金属粒子分散液（ＲＰ－１）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for film formation and a substrate with a coating were prepared and evaluated in the same manner as in Example 1 except that the metal particle dispersion liquid (RP-1) was used.
［比較例２］
〈粒子調製工程〉
実施例１の洗浄工程と同様にして、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４００ｇを溶解し、溶液（ＲＳ２－１）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（ＲＳ２－２）を調製した。
溶液（ＲＳ２－１）と溶液（ＲＳ２－２）とを混合して３０分間攪拌し、溶液ＲＡ２を調製した。
[Comparative Example 2]
<Particle preparation process>
N2 bubbling water was prepared in the same manner as in the washing step of Example 1.
400 g of trisodium citrate dihydrate was dissolved in 930 g of N2 bubbling water to prepare a solution (RS2-1).
A solution (RS2-2) was prepared by dissolving 100 g of ferrous sulfate heptahydrate in 500 g of N2 bubbling water.
The solution (RS2-1) and the solution (RS2-2) were mixed and stirred for 30 minutes to prepare solution RA2.
Ｎ２バブリング水３００ｇに硝酸銀（Ｉ）５７ｇを溶解し、溶液ＲＢ２を調製した。その後、溶液ＲＢ２に溶液ＲＡ２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。 57 g of silver nitrate (I) was dissolved in 300 g of N2 bubbling water to prepare a solution RB2. Then, the solution RA2 was added to the solution RB2, and the metal particles were separated and recovered from the dispersion obtained by stirring for 10 hours by a centrifuge.
〈洗浄工程〉
実施例１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、上記分離回収した金属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。同様に、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に、上記分離回収した金属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。
<Washing process>
N2 bubbling water was prepared in the same manner as in Example 1. The metal particles separated and recovered were immersed in 200 g of a trisodium citrate aqueous solution having a concentration of 30% by mass prepared using N2 bubbling water, washed (demineralized), and then separated and recovered by centrifugation. Similarly, the metal particles separated and recovered are immersed in 200 g of a trisodium citrate aqueous solution having a concentration of 20% by mass prepared using N 2 micro-nano bubble water, washed (demineralized), and then separated and recovered by centrifugation again. did.
ＩＣＰ分析で金属濃度を定量し、Ｎ２バブリング水を用いて金属換算で濃度が２．５質量％の金属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％の黒茶色の金属粒子分散液（ＲＰ－２）を得た。 The metal concentration was quantified by ICP analysis, and a metal particle aqueous dispersion having a metal equivalent concentration of 2.5% by mass was prepared using N2 bubbling water. Then, deionization was performed using 10 g of an amphoteric ion exchange resin to obtain a black-brown metal particle dispersion (RP-2) having a concentration of 2.5% by mass in terms of metal.
〈被膜形成用塗布液および被膜付基材の作製〉
金属粒子分散液（ＲＰ－２）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for film formation and a substrate with a coating were prepared and evaluated in the same manner as in Example 1 except that the metal particle dispersion liquid (RP-2) was used.
［比較例３］
〈粒子調製工程〉
実施例１の洗浄工程と同様にして、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ＲＡ３を調製した。
[Comparative Example 3]
<Particle preparation process>
N2 bubbling water was prepared in the same manner as in the washing step of Example 1.
Nickel nitrate hexahydrate (Ni (NO 3 ) 26H 2 O ) (manufactured by Kanto Chemical Co., Ltd.) 50 g and citric acid hydrate (organic stabilizer) (Kishida Chemical Co., Ltd.) in 450 g of N 2 bubbling water. )) 0.5 g was dissolved to prepare a solution RA3.
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ＲＢ３を調製した。溶液ＲＡ３を撹拌しながら、溶液ＲＢ６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。 Sodium borohydride (reducing agent) 50 g was dissolved in 1000 g of N2 bubbling water to prepare a solution RB3. While stirring the solution RA3, the solution RB6 was added and stirred for 1 hour. At this time, the liquid changed from green to black. Metal particles were separated and recovered from the obtained dispersion by a centrifuge.
〈洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。以降、実施例１と同様にして、黒色の金属粒子分散液（ＲＰ－４）を得た。
<Washing process>
N2 bubbling water was prepared in the same manner as in Example 1. After that, a black metal particle dispersion (RP-4) was obtained in the same manner as in Example 1.
〈被膜形成用塗布液および被膜付基材の作製〉
金属粒子分散液（ＲＰ－３）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for film formation and a substrate with a coating were prepared and evaluated in the same manner as in Example 1 except that the metal particle dispersion liquid (RP-3) was used.
［比較例４］
〈粒子調製工程〉
実施例１の洗浄工程と同様にして、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（ＲＳ４－１）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（ＲＳ４－２）を調製した。
溶液（ＲＳ４－１）と溶液（ＲＳ４－２）とを混合して３０分間攪拌し、溶液ＲＡ４を調製した。
[Comparative Example 4]
<Particle preparation process>
N2 bubbling water was prepared in the same manner as in the washing step of Example 1. 400 g of trisodium citrate dihydrate (organic stabilizer) was dissolved in 930 g of N2 bubbling water to prepare a solution (RS4-1).
180 g of ferrous sulfate heptahydrate (reducing agent) was dissolved in 600 g of N2 bubbling water to prepare a solution (RS4-2).
The solution (RS4-1) and the solution (RS4-2) were mixed and stirred for 30 minutes to prepare solution RA4.
Ｎ２バブリング水６００ｇに硝酸パラジウム（II）２水和物９．１ｇを溶解し、溶液ＲＢ４を調製した。その後、溶液ＲＢ４に溶液ＲＡ４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。 9.1 g of palladium (II) nitrate dihydrate was dissolved in 600 g of N2 bubbling water to prepare a solution RB4. Then, the solution RA4 was added to the solution RB4, and the metal particles were separated and recovered from the dispersion obtained by stirring for 10 hours by a centrifuge.
〈洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。以降、実施例１と同様にして、黒茶色の金属粒子分散液（ＲＰ－４）を得た。
<Washing process>
N2 bubbling water was prepared in the same manner as in Example 1. After that, a black-brown metal particle dispersion (RP-4) was obtained in the same manner as in Example 1.
〈被膜形成用塗布液および被膜付基材の作製〉
金属粒子分散液（ＲＰ－４）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for film formation and a substrate with a coating were prepared and evaluated in the same manner as in Example 1 except that the metal particle dispersion liquid (RP-4) was used.
［比較例５］
〈粒子調製および洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。このＮ２バブリング水を溶液Ａ１及び溶液Ｂ１の調製、洗浄、並びに合金粒子分散液の分散媒に使用する以外は、実施例１と同様にして、黒茶色の合金粒子分散液（ＲＰ－５）を得た。
[Comparative Example 5]
<Particle preparation and cleaning process>
N2 bubbling water was prepared in the same manner as in Example 1. The black-brown alloy particle dispersion (RP-5) is the same as in Example 1 except that the N 2 bubbling water is used as a dispersion medium for the preparation and washing of the solution A1 and the solution B1 and the alloy particle dispersion. Got
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（ＲＰ－５）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (RP-5) was used.
［比較例６］
〈粒子調製および洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。このＮ２バブリング水を溶液Ａ２及び溶液Ｂ２の調製、洗浄、並びに合金粒子分散液の分散媒に使用する以外は、実施例２と同様にして、黒茶色の合金粒子分散液（ＲＰ－６）を得た。
[Comparative Example 6]
<Particle preparation and cleaning process>
N2 bubbling water was prepared in the same manner as in Example 1. The black-brown alloy particle dispersion (RP-6) is the same as in Example 2 except that the N 2 bubbling water is used as a dispersion medium for the preparation and washing of the solution A2 and the solution B2, and the alloy particle dispersion. Got
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（ＲＰ－６）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (RP-6) was used.
［比較例７］
〈粒子調製および洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。このＮ２バブリング水を溶液Ａ３及び溶液Ｂ３の調製、洗浄、並びに合金粒子分散液の分散媒に使用する以外は、実施例３と同様にして、黒茶色の合金粒子分散液（ＲＰ－７）を得た。
[Comparative Example 7]
<Particle preparation and cleaning process>
N2 bubbling water was prepared in the same manner as in Example 1. The black-brown alloy particle dispersion (RP-7) is the same as in Example 3 except that the N 2 bubbling water is used as a dispersion medium for the preparation and washing of the solution A3 and the solution B3, and the alloy particle dispersion. Got
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（ＲＰ－７）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (RP-7) was used.
［比較例８］
〈粒子調製および洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。このＮ２バブリング水を溶液Ａ４及び溶液Ｂ４の調製、洗浄、並びに合金粒子分散液の分散媒に使用する以外は、実施例４と同様にして、黒茶色の合金粒子分散液（ＲＰ－８）を得た。
[Comparative Example 8]
<Particle preparation and cleaning process>
N2 bubbling water was prepared in the same manner as in Example 1. The black-brown alloy particle dispersion (RP-8) is the same as in Example 4 except that the N 2 bubbling water is used as a dispersion medium for the preparation and washing of the solution A4 and the solution B4, and the alloy particle dispersion. Got
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（ＲＰ－８）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (RP-8) was used.
［比較例９］
〈粒子調製および洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。このＮ２バブリング水を溶液Ａ５及び溶液Ｂ５の調製、洗浄、並びに合金粒子分散液の分散媒に使用する以外は、実施例５と同様にして、黒茶色の合金粒子分散液（ＲＰ－９）を得た。
[Comparative Example 9]
<Particle preparation and cleaning process>
N2 bubbling water was prepared in the same manner as in Example 1. The black-brown alloy particle dispersion (RP-9) is the same as in Example 5, except that the N 2 bubbling water is used as a dispersion medium for the preparation and washing of the solution A5 and the solution B5, and the alloy particle dispersion. Got
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（ＲＰ－９）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (RP-9) was used.
［比較例１０］
〈粒子調製および洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。このＮ２バブリング水を溶液Ａ６及び溶液Ｂ６の調製、洗浄、並びに合金粒子分散液の分散媒に使用する以外は、実施例６と同様にして、黒茶色の合金粒子分散液（ＲＰ－１０）を得た。
[Comparative Example 10]
<Particle preparation and cleaning process>
N2 bubbling water was prepared in the same manner as in Example 1. The black-brown alloy particle dispersion (RP-10) is the same as in Example 6 except that the N 2 bubbling water is used as a dispersion medium for the preparation and washing of the solution A6 and the solution B6, and the alloy particle dispersion. Got
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（ＲＰ－１０）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (RP-10) was used.
［比較例１１］
〈粒子調製および洗浄工程〉
実施例１と同様にして、Ｎ２バブリング水を準備した。このＮ２バブリング水を溶液Ａ７及び溶液Ｂ７の調製、洗浄、並びに合金粒子分散液の分散媒に使用する以外は、実施例７と同様にして、黒色の合金粒子分散液（ＲＰ－１１）を得た。
[Comparative Example 11]
<Particle preparation and cleaning process>
N2 bubbling water was prepared in the same manner as in Example 1. A black alloy particle dispersion (RP-11) was prepared in the same manner as in Example 7 except that the N 2 bubbling water was used as a dispersion medium for the preparation and washing of the solution A7 and the solution B7, and the alloy particle dispersion. Obtained.
〈被膜形成用塗布液および被膜付基材の作製〉
合金粒子分散液（ＲＰ－１１）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for forming a film 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 (RP-11) was used.
［比較例１２］
〈粒子調製および洗浄工程〉
ＣｕＣｌ２粉末、溶媒として水、分散剤としてＣＴＡＢ、銅ナノ粒子の酸化を抑制する保護剤としてクエン酸を用いた。容積１００ｍｌのビーカーに水を入れ、水中に窒素を流し、攪拌した状態で、１．０×１０－２Ｍの塩化銅、０．０３６４ｇのＣＴＡＢ、１．５×１０－３Ｍのクエン酸を水に混合した後、還元剤として０．４Ｍのヒドラジンを加えて銅ナノ粒子の作製を行った。このとき加えた試薬と水は全体で２０ｍｌとなるように水の量を調整した。３時間室温で攪拌した後、得られた粒子に遠心洗浄を３回行った後、純水を用いて金属換算で濃度が２．５質量％の金属粒子分散液（ＲＰ－１２）水分散液を調製した。
[Comparative Example 12]
<Particle preparation and cleaning process>
CuCl 2 powder, water as a solvent, CTAB as a dispersant, and citric acid as a protective agent for suppressing the oxidation of copper nanoparticles were used. Put water in a beaker with a volume of 100 ml, pour nitrogen into the water, and in a state of stirring, add 1.0 × 10 −2 M copper chloride, 0.0364 g of CTAB, and 1.5 × 10 -3 M of citric acid. After mixing with water, 0.4 M hydrazine was added as a reducing agent to prepare copper nanoparticles. The amount of water was adjusted so that the total amount of the reagent and water added at this time was 20 ml. After stirring at room temperature for 3 hours, the obtained particles were centrifugally washed three times, and then a metal particle dispersion (RP-12) aqueous dispersion having a metal equivalent concentration of 2.5% by mass using pure water was used. Was prepared.
〈被膜形成用塗布液および被膜付基材の作製〉
金属粒子分散液（ＲＰ－１２）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for film formation and a substrate with a coating were prepared and evaluated in the same manner as in Example 1 except that the metal particle dispersion liquid (RP-12) was used.
［比較例１３］
〈粒子調製および洗浄工程〉
硫酸銅０．１モル、次亜リン酸ナトリウム０．４モル、ＰＶＰ１モル及びエチレングリコール５００ｍｌをビーカーで混合して４０℃に昇温した後、撹拌機を用いて溶解させて混合溶液を製造した。製造した混合溶液をマイクロ波オーブンに投入して３分間マイクロ波を照射した。還元反応により黒褐色の反応物が得られたらマイクロ波の照射を止め、前記混合溶液に予め冷却した蒸留水５００ｍｌを投入して急冷した。遠心分離により黒褐色の銅ナノ粒子を回収し、アセトンと蒸留水とを用いて３回洗浄した後、エチレングリコールを用いて金属換算で濃度が２．５質量％の金属粒子エチレングリコール分散液（ＲＰ－１３）を調製した。
[Comparative Example 13]
<Particle preparation and cleaning process>
0.1 mol of copper sulfate, 0.4 mol of sodium hypophosphite, 1 mol of PVP and 500 ml of ethylene glycol were mixed in a beaker, heated to 40 ° C., and then dissolved using a stirrer to prepare a mixed solution. .. The prepared mixed solution was put into a microwave oven and irradiated with microwaves for 3 minutes. When a dark brown reaction product was obtained by the reduction reaction, microwave irradiation was stopped, and 500 ml of pre-cooled distilled water was added to the mixed solution for rapid cooling. Black-brown copper nanoparticles are recovered by centrifugation, washed three times with acetone and distilled water, and then metal particles ethylene glycol dispersion (RP) having a metal-equivalent concentration of 2.5% by mass using ethylene glycol. -13) was prepared.
〈被膜形成用塗布液および被膜付基材の作製〉
金属粒子分散液（ＲＰ－１３）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for film formation and a substrate with a coating were prepared and evaluated in the same manner as in Example 1 except that the metal particle dispersion liquid (RP-13) was used.
［参考例１］
〈粒子調製および洗浄工程〉
実施例１の粒子調製工程と同様にして、Ｎ２マイクロバブル水を準備した。このＮ２マイクロバブル水を、Ｎ２バブリング水の代わりに、粒子調製工程に使用する以外は、比較例１と同様にして、黒茶色の金属粒子分散液（ＳＰ－１）を得た。
[Reference Example 1]
<Particle preparation and cleaning process>
N2 microbubble water was prepared in the same manner as in the particle preparation step of Example 1. A black-brown metal particle dispersion (SP-1) was obtained in the same manner as in Comparative Example 1 except that the N 2 microbubble water was used in the particle preparation step instead of the N 2 bubbling water.
〈被膜形成用塗布液および被膜付基材の作製〉
金属粒子分散液（ＳＰ－１）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for film formation and a substrate with a coating were prepared and evaluated in the same manner as in Example 1 except that the metal particle dispersion liquid (SP-1) was used.
［参考例２］
〈粒子調製および洗浄工程〉
実施例１の粒子調製工程と同様にして、Ｎ２マイクロバブル水を準備した。このＮ２マイクロバブル水を、Ｎ２バブリング水の代わりに、粒子調製工程に使用する以外は、比較例２と同様にして、黒茶色の金属粒子分散液（ＳＰ－２）を得た。
[Reference Example 2]
<Particle preparation and cleaning process>
N2 microbubble water was prepared in the same manner as in the particle preparation step of Example 1. A black-brown metal particle dispersion (SP-2) was obtained in the same manner as in Comparative Example 2 except that the N 2 microbubble water was used in the particle preparation step instead of the N 2 bubbling water.
〈被膜形成用塗布液および被膜付基材の作製〉
金属粒子分散液（ＳＰ－２）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for film formation and a substrate with a coating were prepared and evaluated in the same manner as in Example 1 except that the metal particle dispersion liquid (SP-2) was used.
［参考例３］
〈粒子調製および洗浄工程〉
実施例１の粒子調製工程と同様にして、Ｎ２マイクロバブル水を準備した。このＮ２マイクロバブル水を、Ｎ２バブリング水の代わりに、粒子調製工程に使用する以外は、比較例３と同様にして、黒茶色の金属粒子分散液（ＳＰ－３）を得た。
[Reference Example 3]
<Particle preparation and cleaning process>
N2 microbubble water was prepared in the same manner as in the particle preparation step of Example 1. A black-brown metal particle dispersion (SP-3) was obtained in the same manner as in Comparative Example 3 except that the N 2 microbubble water was used in the particle preparation step instead of the N 2 bubbling water.
〈被膜形成用塗布液および被膜付基材の作製〉
金属粒子分散液（ＳＰ－３）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for film formation and a substrate with a coating were prepared and evaluated in the same manner as in Example 1 except that the metal particle dispersion liquid (SP-3) was used.
［参考例４］
〈粒子調製および洗浄工程〉
実施例１の粒子調製工程と同様にして、Ｎ２マイクロバブル水を準備した。このＮ２マイクロバブル水を、Ｎ２バブリング水の代わりに、粒子調製工程に使用する以外は、比較例４と同様にして、黒茶色の金属粒子分散液（ＳＰ－４）を得た。
[Reference example 4]
<Particle preparation and cleaning process>
N2 microbubble water was prepared in the same manner as in the particle preparation step of Example 1. A black-brown metal particle dispersion (SP-4) was obtained in the same manner as in Comparative Example 4 except that the N 2 microbubble water was used in the particle preparation step instead of the N 2 bubbling water.
〈被膜形成用塗布液および被膜付基材の作製〉
金属粒子分散液（ＳＰ－４）を用いた以外は実施例１と同様にして、被膜形成用塗布液および被膜付基材を作製し、評価した。
<Preparation of coating liquid for film formation and substrate with film>
A coating liquid for film formation and a substrate with a coating were prepared and evaluated in the same manner as in Example 1 except that the metal particle dispersion liquid (SP-4) was used.
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。 Since the alloy particle dispersion liquid of the present invention can be used for forming a conductive film or the like, it is industrially useful.
Claims (5)
前記合金粒子を洗浄液で洗浄する洗浄工程と、
を含むことを特徴とする合金粒子分散液の製造方法。 A particle preparation step of reducing a plurality of metal salts in a liquid containing microbubbles composed of a non-oxidizing gas having an average bubble diameter of 40 to 500 nm and an organic stabilizer to prepare alloy particles.
A cleaning step of cleaning the alloy particles with a cleaning liquid, and
A method for producing an alloy particle dispersion liquid, which comprises.
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| JP2000090737A (en) | 1998-09-16 | 2000-03-31 | Mitsubishi Materials Corp | Conductive membrane and coating liquid for forming conductive membrane |
| US20070131056A1 (en) | 2005-07-08 | 2007-06-14 | Halalay Ion C | Preparing nanosize platinum-titanium alloys |
| CN101161379A (en) | 2007-11-22 | 2008-04-16 | 同济大学 | A method for preparing Co-Ni-Cu architecture amorphous alloy monodispersity nanometer particle |
| JP2008221121A (en) | 2007-03-12 | 2008-09-25 | National Institute Of Advanced Industrial & Technology | Cavitation reaction acceleration method and method of producing metallic nanoparticle using the same |
| JP2019178386A (en) | 2018-03-30 | 2019-10-17 | 日揮触媒化成株式会社 | Alloy particle dispersion liquid and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000090737A (en) | 1998-09-16 | 2000-03-31 | Mitsubishi Materials Corp | Conductive membrane and coating liquid for forming conductive membrane |
| US20070131056A1 (en) | 2005-07-08 | 2007-06-14 | Halalay Ion C | Preparing nanosize platinum-titanium alloys |
| JP2008221121A (en) | 2007-03-12 | 2008-09-25 | National Institute Of Advanced Industrial & Technology | Cavitation reaction acceleration method and method of producing metallic nanoparticle using the same |
| CN101161379A (en) | 2007-11-22 | 2008-04-16 | 同济大学 | A method for preparing Co-Ni-Cu architecture amorphous alloy monodispersity nanometer particle |
| JP2019178386A (en) | 2018-03-30 | 2019-10-17 | 日揮触媒化成株式会社 | Alloy particle dispersion liquid and method for producing the same |
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