JP6269909B1 - Metal nanoparticle aqueous dispersion - Google Patents
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Images
Abstract
本発明は、金属ナノ粒子（Ｘ）及び有機化合物（Ｙ）の複合体（前記有機化合物（Ｙ）がポリビニルピロリドンである複合体を除く。）と、ポリビニルピロリドン（Ｚ）とを含有する金属ナノ粒子水分散液を提供する。さらには、前記有機化合物（Ｙ）が、カルボキシ基、リン酸基、亜リン酸基、スルホン酸基、スルフィン酸基及びスルフェン酸基からなる群から選ばれる１種以上のアニオン性官能基を有する（メタ）アクリル酸系単量体を含有する単量体混合物の重合物である金属ナノ粒子水分散液を提供する。該金属ナノ粒子水分散液は、貯蔵時や輸送時に起こりうる、加温、又は凍結後に融解するといった熱的負荷が加えられても優れた分散安定性を有し、かつ基材への十分な吸着性、及び、表面活性を有する。The present invention relates to a metal nanoparticle containing a composite of metal nanoparticles (X) and an organic compound (Y) (excluding a composite in which the organic compound (Y) is polyvinylpyrrolidone) and polyvinylpyrrolidone (Z). An aqueous particle dispersion is provided. Furthermore, the organic compound (Y) has one or more anionic functional groups selected from the group consisting of carboxy group, phosphoric acid group, phosphorous acid group, sulfonic acid group, sulfinic acid group and sulfenic acid group. Provided is a metal nanoparticle aqueous dispersion which is a polymer of a monomer mixture containing a (meth) acrylic acid monomer. The metal nanoparticle aqueous dispersion has excellent dispersion stability even when a thermal load such as heating or thawing after freezing, which can occur during storage or transportation, and has sufficient dispersion to the substrate. Adsorbability and surface activity.
Description
本発明は、貯蔵時や輸送時に起こりうる、加温、又は凍結後に融解するといった熱的負荷が加えられても優れた分散安定性を有し、かつ基材への十分な吸着性、及び、表面活性を有する金属ナノ粒子水分散液に関する。 The present invention has excellent dispersion stability even when a thermal load such as heating or thawing after freezing, which can occur during storage or transportation, and has sufficient adsorptivity to a substrate, and The present invention relates to an aqueous dispersion of metal nanoparticles having surface activity.
金属ナノ粒子は、触媒、抗菌、および導電材料等として工業的に使用されている。主な形態は、金属ナノ粒子を分散安定化させたペーストやインク、塗料であり、印刷、塗布、浸漬処理等の方法で、対象基材の任意の場所に金属ナノ粒子を付与することができる。 Metal nanoparticles are industrially used as catalysts, antibacterials, conductive materials and the like. The main forms are pastes, inks and paints in which metal nanoparticles are dispersed and stabilized, and metal nanoparticles can be applied to any location of the target substrate by printing, coating, dipping treatment, etc. .
金属ナノ粒子を分散させる溶媒としては、有機溶媒、水性溶媒の両方が検討されており、金属ナノ粒子を基材上に付与する目的やプロセスによって選択が可能であるが、環境への負荷低減の観点から、水性溶媒を用いることが好ましい。 Both organic solvents and aqueous solvents have been studied as a solvent for dispersing metal nanoparticles, and can be selected depending on the purpose and process of applying metal nanoparticles on a substrate. From the viewpoint, it is preferable to use an aqueous solvent.
このような金属ナノ粒子水性分散液に求められる基本的性質の一つは、長期間の分散安定性である。これは、一般的には、分散液中の分散剤量を増大させることで高めることができるが、余剰の分散剤は金属ナノ粒子の表面活性や、基材に対する吸着性に悪影響を与える傾向があり、材料本来の機能（触媒活性、抗菌活性、導電性等）が損なわれる懸念がある。 One of the basic properties required for such an aqueous dispersion of metal nanoparticles is long-term dispersion stability. This can generally be increased by increasing the amount of dispersant in the dispersion, but the excess dispersant tends to adversely affect the surface activity of the metal nanoparticles and the adsorptivity to the substrate. There is a concern that the original functions (catalytic activity, antibacterial activity, conductivity, etc.) of the material may be impaired.
分散安定性と機能とを両立する技術として、分散剤量を増大させる代わりに、分散性能の高い高分子分散剤を使用する方法が開示されており（例えば、特許文献１参照。）、この発明の金属ナノ粒子の水性分散液は、無電解めっきの触媒として使用しうる、基材への吸着性と、表面活性を有することが開示されている（例えば、特許文献２参照。）。 As a technique for achieving both dispersion stability and function, a method of using a polymer dispersant having high dispersion performance instead of increasing the amount of the dispersant has been disclosed (for example, see Patent Document 1). It has been disclosed that the aqueous dispersion of metal nanoparticles can be used as a catalyst for electroless plating and has an adsorptivity to a substrate and surface activity (see, for example, Patent Document 2).
常温から冷蔵状態の温度範囲においては、このように高性能な分散剤を最小限量用いるという方法によって、長期間の分散安定性と機能との両立が可能である。一方で、製品の貯蔵環境や輸送条件によっては、金属ナノ粒子水性分散液の凍結や温度上昇が想定される。従来の銀ナノ粒子の水性分散液では、このような熱的負荷による不可逆な凝集と、それに伴う性能低下が問題となっている。従って、金属ナノ粒子分散液の品質維持のために、使用条件が限定されると共に、貯蔵や輸送時に温度管理が必要であり、管理コストも問題となっている。 In the temperature range from room temperature to refrigerated state, it is possible to achieve both long-term dispersion stability and function by using such a minimum amount of a high-performance dispersant. On the other hand, depending on the storage environment and transport conditions of the product, freezing of the metal nanoparticle aqueous dispersion and an increase in temperature are assumed. In conventional aqueous dispersions of silver nanoparticles, irreversible aggregation due to such a thermal load and accompanying performance degradation are problematic. Therefore, in order to maintain the quality of the metal nanoparticle dispersion liquid, use conditions are limited, and temperature management is required during storage and transportation, and management costs are also a problem.
本発明が解決しようとする課題は、貯蔵時や輸送時に起こりうる、温度上昇、又は凍結後に融解するといった熱的負荷が加えられても優れた分散安定性を有し、かつ基材への十分な吸着性、及び、表面活性を有する金属ナノ粒子水分散液を提供することである。 The problem to be solved by the present invention is that it has excellent dispersion stability even when a thermal load such as temperature rise or melting after freezing, which may occur during storage or transportation, and is sufficient for the substrate. It is to provide a metal nanoparticle aqueous dispersion having excellent adsorptivity and surface activity.
本発明者等は、上記の課題を解決すべく鋭意研究した結果、金属ナノ粒子水分散液を特定の組成で構成することによって、上記の課題を解決できることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by configuring the metal nanoparticle aqueous dispersion with a specific composition, and have completed the present invention.
すなわち、本発明は、金属ナノ粒子（Ｘ）及び有機化合物（Ｙ）の複合体（前記有機化合物（Ｙ）がポリビニルピロリドンである複合体を除く。）と、ポリビニルピロリドン（Ｚ）とを含有する金属ナノ粒子水分散液であって、前記有機化合物（Ｙ）が、アニオン性官能基を有する有機化合物（Ｙ１）であり、前記有機化合物（Ｙ１）が、カルボキシ基、リン酸基、亜リン酸基、スルホン酸基、スルフィン酸基及びスルフェン酸基からなる群から選ばれる１種以上のアニオン性官能基を有する（メタ）アクリル酸系単量体を含有する単量体混合物（Ｉ）の重合物（Ｙ２）であることを特徴とする金属ナノ粒子水分散液を提供するものである。
That is, the present invention contains a composite of metal nanoparticles (X) and an organic compound (Y) (excluding a composite in which the organic compound (Y) is polyvinyl pyrrolidone) and polyvinyl pyrrolidone (Z). Metal nanoparticle aqueous dispersion, wherein the organic compound (Y) is an organic compound (Y1) having an anionic functional group, and the organic compound (Y1) is a carboxy group, a phosphate group, phosphorous acid Polymerization of monomer mixture (I) containing a (meth) acrylic acid monomer having one or more anionic functional groups selected from the group consisting of a group, a sulfonic acid group, a sulfinic acid group and a sulfenic acid group The present invention provides a metal nanoparticle aqueous dispersion characterized by being a product (Y2) .
本発明の金属ナノ粒子水分散液は、銀ナノ粒子の基材への吸着性、活性を低下させることなく、分散安定性を向上させることができる。このため、工業材料としての有用性を何ら損なうことなく、加温、又は凍結後に融解するといった熱的負荷が加えられても特性劣化（凝集や液外観の悪化）を防止できる。このように、本発明の金属ナノ粒子水分散液は、熱的負荷に対して優れた分散安定性を有しているため、輸送（陸送、海運、空輸）、保管における温度管理コストを低減できる。 The aqueous dispersion of metal nanoparticles of the present invention can improve the dispersion stability without reducing the adsorptivity and activity of the silver nanoparticles to the substrate. For this reason, characteristic deterioration (aggregation and deterioration of liquid appearance) can be prevented even if a thermal load such as heating or melting after freezing is applied without impairing the usefulness as an industrial material. As described above, since the metal nanoparticle aqueous dispersion of the present invention has excellent dispersion stability against thermal load, the temperature management cost in transportation (land transportation, sea transportation, air transportation) and storage can be reduced. .
本発明の金属ナノ粒子水分散液は、金属ナノ粒子（Ｘ）及び有機化合物（Ｙ）の複合体（前記有機化合物（Ｙ）がポリビニルピロリドンである複合体を除く。）と、ポリビニルピロリドン（Ｚ）とを含有するものである。 The aqueous dispersion of metal nanoparticles of the present invention comprises a composite of metal nanoparticles (X) and an organic compound (Y) (excluding a composite in which the organic compound (Y) is polyvinyl pyrrolidone), and polyvinyl pyrrolidone (Z ).
前記金属ナノ粒子（Ｘ）を構成する金属としては、例えば、銀、銅、パラジウムの単体、もしくはこれらの合金等が挙げられる。また、前記金属ナノ粒子（Ｘ）としては、銀コア銅シェル粒子、銅シェル銀コア粒子、銀を一部パラジウムで置換した粒子、銅を一部パラジウムで置換した粒子等も挙げられる。これらの金属又は合金は、１種で用いることも２種以上併用することもできる。これらの金属又は合金は、目的に応じて、適宜選択すればよいが、配線、導電性層を形成する目的で用いる場合には、銀、銅が好ましく、触媒機能の観点からは、銀、銅、パラジウムが好ましい。また、コストの観点からは、銀、銅、これらの合金、一部置換体、又はこれらの混合物が好ましい。 As a metal which comprises the said metal nanoparticle (X), silver, copper, palladium simple substance, or these alloys etc. are mentioned, for example. Examples of the metal nanoparticles (X) include silver core copper shell particles, copper shell silver core particles, particles in which silver is partially substituted with palladium, and particles in which copper is partially substituted with palladium. These metals or alloys can be used alone or in combination of two or more. These metals or alloys may be appropriately selected according to the purpose. However, when used for the purpose of forming a wiring or a conductive layer, silver and copper are preferable. From the viewpoint of the catalytic function, silver, copper Palladium is preferred. From the viewpoint of cost, silver, copper, alloys thereof, partially substituted products, or mixtures thereof are preferable.
前記金属ナノ粒子（Ｘ）の形状は、水性媒体中での分散安定性を阻害しない限り、特に限定はなく、種々の形状のナノ粒子を目的に応じて、適宜選択できる。具体的には、球状、多面体状、板状、棒状、及び、これらの組み合わせた形状の粒子が挙げられる。前記金属ナノ粒子（Ｘ）としては、単一の形状のもの、もしくは複数の形状のものを混合して用いることができる。また、これらの形状の中でも、分散安定性の観点から、球状又は多面体状の粒子が好ましい。 The shape of the metal nanoparticles (X) is not particularly limited as long as the dispersion stability in an aqueous medium is not impaired, and nanoparticles having various shapes can be appropriately selected according to the purpose. Specific examples include spherical, polyhedral, plate-like, rod-like, and combinations of these particles. As said metal nanoparticle (X), the thing of a single shape or a thing of a some shape can be mixed and used. Among these shapes, spherical or polyhedral particles are preferable from the viewpoint of dispersion stability.
前記金属ナノ粒子（Ｘ）を構成する金属は、水性の分散媒中で、長期間安定に均一な分散状態を保つために、金属ナノ粒子（Ｘ）の表面に、分散剤として有機化合物（Ｙ）が吸着した金属ナノ粒子（Ｘ）及び有機化合物（Ｙ）の複合体として用いる。前記有機化合物（Ｙ）は、目的に応じて、適宜選択して用いればよいが、分散安定性の観点から、アニオン性官能基を有する化合物（Ｙ１）が好ましい。なお、前記有機化合物（Ｙ）は、後述するポリビニルピロリドン（Ｚ）以外のものである。 The metal constituting the metal nanoparticle (X) is an organic compound (Y) as a dispersant on the surface of the metal nanoparticle (X) in order to maintain a uniform dispersed state for a long period of time in an aqueous dispersion medium. ) Are adsorbed and used as a composite of the metal nanoparticle (X) and the organic compound (Y). The organic compound (Y) may be appropriately selected and used according to the purpose, but from the viewpoint of dispersion stability, the compound (Y1) having an anionic functional group is preferable. The organic compound (Y) is other than polyvinylpyrrolidone (Z) described later.
前記アニオン性官能基を有する化合物（Ｙ１）は、分子中にアニオン性官能基を１種以上有する化合物である。また、分散安定性を阻害しない限り、分子中にアニオン性官能基の他にカチオン性官能基を有する化合物を用いてもよい。前記アニオン性官能基を有する化合物（Ｙ１）は、１種で用いることも２種以上併用することもできる。 The compound (Y1) having an anionic functional group is a compound having at least one anionic functional group in the molecule. Further, a compound having a cationic functional group in addition to an anionic functional group in the molecule may be used as long as the dispersion stability is not inhibited. The compound (Y1) having an anionic functional group can be used alone or in combination of two or more.
前記、アニオン性官能基を有する化合物（Ｙ１）としては、水性分散媒中での長期分散安定性と、基材上に付与された後の金属ナノ粒子表面の活性保持を両立する観点から、カルボキシ基、リン酸基、亜リン酸基、スルホン酸基、スルフィン酸基及びスルフェン酸基からなる群から選ばれる１種以上のアニオン性官能基を有する（メタ）アクリル酸系単量体を含有する単量体混合物（Ｉ）の重合物（Ｙ２）が、特に好ましい。 As the compound (Y1) having an anionic functional group, from the viewpoint of achieving both long-term dispersion stability in an aqueous dispersion medium and maintaining the activity of the metal nanoparticle surface after being imparted on the substrate, A (meth) acrylic acid monomer having at least one anionic functional group selected from the group consisting of a group, a phosphoric acid group, a phosphorous acid group, a sulfonic acid group, a sulfinic acid group and a sulfenic acid group The polymer (Y2) of the monomer mixture (I) is particularly preferable.
前記重合物（Ｙ２）は、単独重合物であっても、共重合物であってもよい。また、共重合物である場合、ランダム共重合物であっても、ブロック共重合物であってもよい。 The polymer (Y2) may be a homopolymer or a copolymer. Moreover, when it is a copolymer, it may be a random copolymer or a block copolymer.
前記重合物（Ｙ２）は、カルボキシ基、リン酸基、亜リン酸基、スルホン酸基、スルフィン酸基、スルフェン酸基からなる群から選ばれる１種以上のアニオン性官能基を有するため、ヘテロ原子が有する非共有電子対を介して金属ナノ粒子（Ｘ）に吸着する機能を有すると同時に、金属ナノ粒子（Ｘ）表面に負の電荷を付与するので、粒子間の電荷反発によりコロイド粒子の凝集を防ぐことができ、水中で重合物（Ｙ２）及び金属ナノ粒子（Ｘ）の複合体を安定的に分散できる。 Since the polymer (Y2) has one or more anionic functional groups selected from the group consisting of carboxy group, phosphoric acid group, phosphorous acid group, sulfonic acid group, sulfinic acid group and sulfenic acid group, Since it has a function of adsorbing to the metal nanoparticle (X) through the lone pair of atoms, and at the same time, a negative charge is imparted to the surface of the metal nanoparticle (X), the repulsion of the colloidal particles Aggregation can be prevented, and the composite of polymer (Y2) and metal nanoparticles (X) can be stably dispersed in water.
前記重合物（Ｙ２）は、金属ナノ粒子（Ｘ）への吸着と水分散液での分散安定性がより向上できることから、１分子中にアニオン性官能基を３つ以上有するものが好ましい。 The polymer (Y2) preferably has three or more anionic functional groups in one molecule because the adsorption to the metal nanoparticles (X) and the dispersion stability in the aqueous dispersion can be further improved.
また、前記重合物（Ｙ２）の重量平均分子量は、金属ナノ粒子（Ｘ）への吸着と水分散液での分散安定性がより向上できることから、３，０００〜２０，０００の範囲が好ましく、４，０００〜８，０００の範囲がより好ましい。 Further, the weight average molecular weight of the polymer (Y2) is preferably in the range of 3,000 to 20,000, because the adsorption to the metal nanoparticles (X) and the dispersion stability in the aqueous dispersion can be further improved. The range of 4,000 to 8,000 is more preferable.
また、前記重合物（Ｙ２）中に、ポリエチレングリコール鎖等のポリオキシアルキレン鎖を導入すると、電荷による斥力発現と同時に、立体反発効果によるコロイド保護作用を利用することができ、より分散安定性が向上するため好ましい。 In addition, when a polyoxyalkylene chain such as a polyethylene glycol chain is introduced into the polymer (Y2), it is possible to utilize a colloid protective effect due to a steric repulsion effect simultaneously with the expression of repulsive force due to electric charge, and more dispersion stability. It is preferable because it improves.
例えば、前記単量体混合物（Ｉ）にポリエチレングリコール鎖を有する（メタ）アクリル酸系単量体と、前記アニオン性基を有する（メタ）アクリル酸系単量体等とを共重合させることで、ポリエチレングリコール鎖を有する前記重合物（Ｙ２）を容易に得ることができる。 For example, the monomer mixture (I) is copolymerized with a (meth) acrylic acid monomer having a polyethylene glycol chain and a (meth) acrylic acid monomer having an anionic group. The polymer (Y2) having a polyethylene glycol chain can be easily obtained.
特にエチレングリコールの平均ユニット数が２０以上のポリエチレングリコール鎖を有する（メタ）アクリル酸系単量体を用いて重合した前記重合物（Ｙ２）は、貴金属、特に銀、銅のナノ粒子を安定化する能力が高く、好適な保護剤となり好ましい。このようなアニオン性官能基とポリエチレングリコール鎖とを有する重合物の合成は、例えば、特許第４６９７３５６号公報、特開２０１０−２０９４２１号公報等に記載の方法により、容易に行うことができる。 In particular, the polymer (Y2) polymerized using a (meth) acrylic acid monomer having a polyethylene glycol chain with an average unit number of ethylene glycol of 20 or more stabilizes nanoparticles of noble metals, particularly silver and copper. This is preferable because it is a suitable protective agent. Synthesis of such a polymer having an anionic functional group and a polyethylene glycol chain can be easily carried out, for example, by the methods described in Japanese Patent No. 4697356, Japanese Patent Application Laid-Open No. 2010-209421, and the like.
前記のエチレングリコールの平均ユニット数が２０以上のポリエチレングリコール鎖を有する（メタ）アクリル酸系単量体の重量平均分子量としては、１，０００〜２，０００の範囲が好ましい。重量平均分子量がこの範囲であると、金属ナノ粒子（Ｘ）との複合体の水分散性がより良好となる。 The weight average molecular weight of the (meth) acrylic acid monomer having a polyethylene glycol chain having an ethylene glycol average unit number of 20 or more is preferably in the range of 1,000 to 2,000. When the weight average molecular weight is within this range, the water dispersibility of the composite with the metal nanoparticles (X) becomes better.
リン酸基とポリエチレングリコール鎖とを有する重合物（Ｙ２）のより具体的な合成方法としては、例えば、市販されている２−メタクリロイルオキシホスフェート（例えば、共栄社化学株式会社製「ライトエステルＰ−１Ｍ」）と、市販のポリエチレングリコール鎖を有するメタクリル酸エステルモノマー（例えば、日油株式会社製「ブレンマーＰＭＥ−１０００」）を重合開始剤（例えば、油溶性アゾ重合開始剤「Ｖ−５９」）を用いて共重合する方法が挙げられる。 As a more specific synthesis method of the polymer (Y2) having a phosphate group and a polyethylene glycol chain, for example, commercially available 2-methacryloyloxyphosphate (for example, “Light Ester P-1M” manufactured by Kyoeisha Chemical Co., Ltd.). )) And a commercially available methacrylic acid ester monomer having a polyethylene glycol chain (for example, “Blenmer PME-1000” manufactured by NOF Corporation) is used as a polymerization initiator (for example, oil-soluble azo polymerization initiator “V-59”). And a method of copolymerization using these.
この際、リン酸基を有する（メタ）アクリル酸エステルモノマーの比率を、単量体混合物（Ｉ）中の３０質量％未満とすると、金属ナノ粒子（Ｘ）の保護に関与しないポリエチレングリコール鎖を有する（メタ）アクリル酸系単量体の単独重合物等の副生成物の発生を抑制し、得られる重合物（Ｙ２）による分散安定性が向上する。 At this time, if the ratio of the (meth) acrylic acid ester monomer having a phosphate group is less than 30% by mass in the monomer mixture (I), a polyethylene glycol chain that does not participate in the protection of the metal nanoparticles (X) Generation | occurrence | production of by-products, such as a homopolymer of the (meth) acrylic acid-type monomer which has, is suppressed, and the dispersion stability by the polymer (Y2) obtained improves.
前記単量体混合物（Ｉ）は、アニオン性基を有する（メタ）アクリル酸系単量体、ポリエチレングリコール鎖を有する（メタ）アクリル酸系単量体以外の第３の重合性モノマーを含んでいてもよい。この際、第３の重合性モノマーが疎水性モノマーである場合、その使用量は、良好な水分散性を維持できることから、ポリエチレングリコール鎖を有する（メタ）アクリル酸系単量体１００質量部に対して２０質量部以下が好ましく、１０質量部以下がより好ましい。なお、第３の重合性モノマーが疎水性モノマーでない場合はこの範囲に限定されない。 The monomer mixture (I) contains a third polymerizable monomer other than the (meth) acrylic acid monomer having an anionic group and the (meth) acrylic acid monomer having a polyethylene glycol chain. May be. At this time, when the third polymerizable monomer is a hydrophobic monomer, the amount used thereof can maintain good water dispersibility, so that the amount of the (meth) acrylic acid monomer having a polyethylene glycol chain is 100 parts by mass. The amount is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. In addition, when the 3rd polymeric monomer is not a hydrophobic monomer, it is not limited to this range.
前述のように、重合物（Ｙ２）の重量平均分子量は３，０００〜２０，０００の範囲であることが好ましいが、ポリエチレングリコール鎖を有する（メタ）アクリル酸系単量体を併用した場合、重合反応により得られる重合物（Ｙ２）は、分子量分布を有することになる。重量平均分子量の小さいもの程、ポリエチレングリコール鎖を有する（メタ）アクリル酸系単量体由来構造を含まないものであることから、金属ナノ粒子（Ｘ）との複合体を水性媒体に分散する場合の分散安定性には寄与しないことになるので、この観点からは、重合物（Ｙ２）の重量平均分子量は４，０００以上であることがより好ましくなる。逆に重量平均分子量が大きくなると、金属ナノ粒子（Ｘ）との複合体の粗大化が起こりやすく、触媒液中に沈殿を生じやすくなる観点から、重合物（Ｙ２）の重量平均分子量は８，０００以下であることがより好ましい。 As described above, the weight average molecular weight of the polymer (Y2) is preferably in the range of 3,000 to 20,000, but when a (meth) acrylic acid monomer having a polyethylene glycol chain is used in combination, The polymer (Y2) obtained by the polymerization reaction has a molecular weight distribution. When the composite with the metal nanoparticles (X) is dispersed in an aqueous medium, the smaller the weight average molecular weight, the less the structure derived from a (meth) acrylic acid monomer having a polyethylene glycol chain. From this point of view, the weight average molecular weight of the polymer (Y2) is more preferably 4,000 or more. Conversely, when the weight average molecular weight is increased, the complex with the metal nanoparticle (X) is likely to be coarsened, and the weight average molecular weight of the polymer (Y2) is 8, from the viewpoint of easily causing precipitation in the catalyst solution. More preferably, it is 000 or less.
前記重合物（Ｙ２）の重量平均分子量を上記の範囲内に調整するためには、公知文献、例えば、特開２０１０−２０９４２１号公報等に記載の連鎖移動剤を用いてもよく、連鎖移動剤を使用せずに重合条件によって制御してもよい。 In order to adjust the weight average molecular weight of the polymer (Y2) within the above range, a chain transfer agent described in a known document, for example, JP 2010-209421 A may be used. You may control by polymerization conditions, without using.
本発明の金属ナノ粒子水分散液に用いる複合体としては、前記の重合物（Ｙ２）をコロイド保護剤として製造した、銀、銅、パラジウム等の金属ナノ粒子（Ｘ）との複合体を用いることができる。 As a composite used for the aqueous dispersion of metal nanoparticles of the present invention, a composite with metal nanoparticles (X) such as silver, copper, palladium, etc., produced using the polymer (Y2) as a colloid protective agent is used. be able to.
また、本発明の金属ナノ粒子水分散液に用いる複合体の調製方法としては、例えば、前記重合物（Ｙ２）を水性媒体に溶解又は分散させた後、ここに、硝酸銀、酢酸銅、硝酸パラジウム等の金属化合物を添加し、必要に応じて錯化剤を添加し均一な分散体とした後、還元剤を混合することによって、前記金属化合物を還元し、還元された金属がナノサイズ粒子（ナノメートルオーダーの大きさを有する微粒子）となると同時に前記重合物（Ｙ２）と複合した金属ナノ粒子（Ｘ）の水性分散体として得る方法が挙げられる。なお、錯化剤を用いる場合、還元剤と同時に混合してもよい。 Moreover, as a preparation method of the composite used for the metal nanoparticle aqueous dispersion of the present invention, for example, the polymer (Y2) is dissolved or dispersed in an aqueous medium, and then silver nitrate, copper acetate, palladium nitrate is added thereto. After adding a metal compound such as a complexing agent as necessary to obtain a uniform dispersion, the metal compound is reduced by mixing a reducing agent, and the reduced metal is nanosized particles ( And a method of obtaining an aqueous dispersion of metal nanoparticles (X) combined with the polymer (Y2) at the same time. In addition, when using a complexing agent, you may mix simultaneously with a reducing agent.
本発明で用いる金属ナノ粒子（Ｘ）及び前記有機化合物（Ｙ）の複合体は、配線、導電層形成に有利な、低温での融着性、及び、触媒活性の観点から、前記金属ナノ粒子（Ｘ）の平均粒子径が０．５〜１００ｎｍの範囲にあることが好ましい。 The composite of the metal nanoparticles (X) and the organic compound (Y) used in the present invention is advantageous from the viewpoints of fusion property at low temperatures and catalytic activity, which is advantageous for wiring and conductive layer formation. The average particle size of (X) is preferably in the range of 0.5 to 100 nm.
なお、金属ナノ粒子（Ｘ）の平均粒子径は、透過型電子顕微鏡写真によって見積もることが可能で、その１００個の平均値が０．５〜１００ｎｍの範囲であるものは、例えば、前述の特許第４６９７３５６号公報、特開２０１０−２０９４２１号公報等に記載の方法によって容易に得ることができる。このようにして得られる金属ナノ粒子（Ｘ）は、前記重合物（Ｙ２）で保護されて１個ずつが独立して存在し、水性分散媒中に分散させた状態で得ることができる。 The average particle diameter of the metal nanoparticles (X) can be estimated by a transmission electron micrograph, and the average value of 100 particles in the range of 0.5 to 100 nm is, for example, the above-mentioned patent It can be easily obtained by the methods described in Japanese Patent No. 4697356, Japanese Patent Application Laid-Open No. 2010-209421, and the like. The metal nanoparticles (X) obtained in this manner are protected by the polymer (Y2) and are present one by one and can be obtained in a state of being dispersed in an aqueous dispersion medium.
前記金属ナノ粒子（Ｘ）の平均粒子径は、金属化合物の種類、コロイド保護剤となる前記有機化合物（Ｙ）の分子量、化学構造及び使用量、錯化剤や還元剤の種類及び使用量、還元反応時における温度等によって容易に制御可能であり、これらについては、上記の特許文献等に記載の実施例を参照すればよい。 The average particle diameter of the metal nanoparticles (X) is the type of metal compound, the molecular weight of the organic compound (Y) to be a colloid protective agent, the chemical structure and the amount used, the type and amount of complexing agent and reducing agent, The temperature can be easily controlled by the temperature at the time of the reduction reaction. For these, the examples described in the above-mentioned patent documents and the like may be referred to.
また、前記有機化合物（Ｙ）と金属ナノ粒子（Ｘ）との複合体中の前記有機化合物（Ｙ）の含有比率としては、１〜３０質量％の範囲が好ましく、２〜２０質量％の範囲がより好ましい。すなわち、前記複合体は、その質量の大部分を金属ナノ粒子（Ｘ）が占めるものが、配線、導電層形成、各種触媒用途に使用する上で適している。 Moreover, as a content ratio of the said organic compound (Y) in the composite_body | complex of the said organic compound (Y) and metal nanoparticle (X), the range of 1-30 mass% is preferable, and the range of 2-20 mass% Is more preferable. That is, in the composite, the metal nanoparticle (X) occupies most of the mass is suitable for use in wiring, conductive layer formation, and various catalyst applications.
前記金属ナノ粒子（Ｘ）が前記重合物（Ｙ２）で保護された複合体は、水性媒体、即ち水や水と相溶可能な有機溶剤との混合溶剤中において、０．０１〜７０質量％程度の範囲で分散することが可能であり、この分散液中に、さらに前記ポリビニルピロリドン（Ｚ）を共存させることによって、加温、又は凍結後に融解といった熱的負荷が加えられても、前記、金属ナノ粒子（Ｘ）と有機化合物（Ｙ）の複合体は、優れた分散安定性と、基材への高い吸着性、及び表面活性を維持することができる。 The composite in which the metal nanoparticles (X) are protected with the polymer (Y2) is 0.01 to 70% by mass in an aqueous medium, that is, a mixed solvent of water or an organic solvent compatible with water. Even if a thermal load such as heating or thawing after freezing is applied by further coexisting the polyvinylpyrrolidone (Z) in this dispersion, The composite of the metal nanoparticles (X) and the organic compound (Y) can maintain excellent dispersion stability, high adsorptivity to the substrate, and surface activity.
ポリビニルピロリドン（Ｚ）の共存によってこのような効果が現れることについてのメカニズムは定かではないが、金属ナノ粒子（Ｘ）の凝集機構との相関から、次のように推測できる。加温によって、分散液中で金属ナノ粒子（Ｘ）の凝集が起こるのは、温度上昇により有機化合物（Ｙ）が、金属ナノ粒子（Ｘ）表面から脱離する方向に平衡が傾くとともに、粒子のブラウン運動が活発となり、活性表面の露出した金属ナノ粒子（Ｘ）同士の衝突頻度が高まるためと考えられる。一方、凍結によって凝集が起こるのは、金属ナノ粒子分散液が凍結する際、分散液中の水が結晶化して氷となる際、水にとって夾雑物である金属ナノ粒子複合体を排除しながら結晶成長が起こり、金属ナノ粒子複合体が極度に濃縮されるためと考えられる。従って、加温、または凍結による、粒子の不加逆な凝集を抑止するためには、金属ナノ粒子（Ｘ）表面に吸着し、保護する性質を持つ化合物を分散液中に共存させることが有効と考えられる。 Although the mechanism about such an effect appearing by the coexistence of polyvinylpyrrolidone (Z) is not clear, it can be estimated as follows from the correlation with the aggregation mechanism of the metal nanoparticles (X). The aggregation of the metal nanoparticles (X) occurs in the dispersion due to heating. The equilibrium is inclined in the direction in which the organic compound (Y) is desorbed from the surface of the metal nanoparticles (X) as the temperature rises. This is considered to be because the Brownian motion of the metal becomes active and the collision frequency between the metal nanoparticles (X) exposed on the active surface increases. On the other hand, aggregation occurs due to freezing, when the metal nanoparticle dispersion is frozen, and when the water in the dispersion crystallizes to become ice, it is crystallized while eliminating metal nanoparticle complexes that are contaminants for water. It is thought that growth occurs and the metal nanoparticle composite is extremely concentrated. Therefore, in order to suppress irreversible aggregation of particles due to heating or freezing, it is effective to allow a compound having the property of adsorbing and protecting the metal nanoparticles (X) to coexist in the dispersion. it is conceivable that.
金属ナノ粒子複合体が基材に吸着するドライビングフォースとなるのは、主として基材表面の電荷と、金属ナノ粒子複合体の電荷との静電的相互作用である。このため、金属ナノ粒子複合体と同じ符号の電荷を有する添加物を共存させた場合、基材上の吸着点に対して、添加物と金属ナノ粒子複合体とが競合して、金属ナノ粒子複合体の基材への吸着を阻害すると考えられる。逆に、金属ナノ粒子複合体と逆符号の電荷を有する添加物を共存させた場合は、金属ナノ粒子複合体同士の静電的反発力を遮蔽し、金属ナノ粒子複合体の凝集を誘発すると考えられる。従って、分散安定性と基材への高い吸着性を維持するためには、金属ナノ粒子（Ｘ）に吸着し、保護する性質を有する化合物としてノニオン性の化合物を添加物として用いるのが好適と考えられる。 The driving force by which the metal nanoparticle composite is adsorbed to the base material is mainly an electrostatic interaction between the charge on the surface of the base material and the charge of the metal nanoparticle composite. For this reason, when an additive having the same charge as that of the metal nanoparticle composite is allowed to coexist, the additive and the metal nanoparticle composite compete with each other for the adsorption point on the base material. It is thought to inhibit the adsorption of the composite to the substrate. Conversely, when an additive having a charge opposite to that of the metal nanoparticle composite is allowed to coexist, the electrostatic repulsion between the metal nanoparticle composites is shielded, and aggregation of the metal nanoparticle composite is induced. Conceivable. Therefore, in order to maintain the dispersion stability and the high adsorptivity to the base material, it is preferable to use a nonionic compound as an additive as a compound having the property of adsorbing and protecting the metal nanoparticles (X). Conceivable.
また、金属ナノ粒子（Ｘ）に吸着し、保護する性質を有する化合物が、金属ナノ粒子（Ｘ）に強く吸着しているほど、基材付与後に、導電性や触媒活性を発現させるために、金属ナノ粒子（Ｘ）の活性表面を露出させることは、より困難になると考えられる。従って、表面活性維持のためには、金属ナノ粒子（Ｘ）に吸着し、保護する性質を有する化合物として、前記金属ナノ粒子（Ｘ）に対して強い吸着性を有しないものが好適と考えられる。 Moreover, in order to express conductivity and catalytic activity after applying the base material, the more the compound having the property of adsorbing and protecting the metal nanoparticle (X) is strongly adsorbed to the metal nanoparticle (X), It will be more difficult to expose the active surface of the metal nanoparticles (X). Therefore, in order to maintain the surface activity, it is considered suitable as a compound having the property of adsorbing and protecting the metal nanoparticles (X) and having no strong adsorptivity to the metal nanoparticles (X). .
以上のように、金属ナノ粒子（Ｘ）に吸着し、保護する性質を有する化合物としては、前記金属ナノ粒子（Ｘ）に対して、弱すぎず、強すぎない吸着性を有し、水溶性で、ノニオン性であることが、優れた分散安定性と、基材への高い吸着性、及び、金属ナノ粒子（Ｘ）の表面活性を維持するために好適と考えられる。ポリビニルピロリドン（Ｚ）はこの条件に合致する。 As described above, the compound having the property of adsorbing and protecting the metal nanoparticles (X) is not too weak and not too strong for the metal nanoparticles (X), and is water-soluble. Thus, it is considered that nonionic properties are preferable for maintaining excellent dispersion stability, high adsorptivity to the substrate, and surface activity of the metal nanoparticles (X). Polyvinylpyrrolidone (Z) meets this condition.
本発明の金属ナノ粒子水分散液は、前記金属ナノ粒子（Ｘ）と前記有機化合物（Ｙ）との複合体の他に、ポリビニルピロリドン（Ｚ）を必須成分とするが、ポリビニルピロリドンの混合方法としては、特に制限はないが、前記金属ナノ粒子（Ｘ）と前記有機化合物（Ｙ）との複合体の水性分散体にポリビニルピロリドン（Ｚ）を添加する方法が簡便であり、好適である。 The aqueous dispersion of metal nanoparticles of the present invention contains polyvinylpyrrolidone (Z) as an essential component in addition to the composite of the metal nanoparticles (X) and the organic compound (Y). Although there is no restriction | limiting in particular, The method of adding polyvinylpyrrolidone (Z) to the aqueous dispersion of the composite_body | complex of the said metal nanoparticle (X) and the said organic compound (Y) is simple and suitable.
ポリビニルピロリドン（Ｚ）は、前記の調製方法によって得られた有機化合物（Ｙ）と金属ナノ粒子（Ｘ）との複合体の水分散液に添加してもよいし、余剰の錯化剤、還元剤、又は原料として用いた金属化合物に含まれた対イオン等を限外ろ過法、沈殿法、遠心分離、減圧蒸留、減圧乾燥等の各種精製法を単独又は２種以上を組み合わせた精製工程を経たものや、さらに精製工程後に濃度（不揮発分）や水性媒体を変更して新たに分散体として調製し直したものに添加してもよい。電子回路形成など、実装用途の目的で用いる場合には、前記の精製工程を経た水性媒体に添加する方法を用いることが好ましい。 Polyvinyl pyrrolidone (Z) may be added to the aqueous dispersion of the complex of the organic compound (Y) and metal nanoparticles (X) obtained by the above preparation method, or an excess complexing agent, reduced A purification process in which various kinds of purification methods such as ultrafiltration, precipitation, centrifugation, vacuum distillation, and vacuum drying are used alone or in combination of two or more for counter ions contained in the metal compound used as an agent or raw material. You may add to what passed, and what was newly re-prepared as a dispersion by changing a density | concentration (nonvolatile content) and an aqueous medium after a refinement | purification process. When used for the purpose of mounting such as electronic circuit formation, it is preferable to use a method of adding to the aqueous medium that has undergone the purification step.
本発明で用いる前記ポリビニルピロリドン（Ｚ）の重量平均分子量（以下、「Ｍｗ」と略記する。）は、加温、又は凍結後に融解を経た場合でも、より優れた分散安定性、基材への高い吸着性、表面活性を同時に保持した金属ナノ粒子水分散液を提供する観点から、１万〜１００万の範囲が好ましく、３万〜５０万の範囲がより好ましい。なお、前記重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法による測定で得られた値である。 The weight average molecular weight (hereinafter abbreviated as “Mw”) of the polyvinyl pyrrolidone (Z) used in the present invention is superior in dispersion stability, even when it is heated or thawed after freezing. The range of 10,000 to 1,000,000 is preferable and the range of 30,000 to 500,000 is more preferable from the viewpoint of providing an aqueous dispersion of metal nanoparticles having simultaneously maintained high adsorptivity and surface activity. The weight average molecular weight is a value obtained by measurement by gel permeation chromatography (GPC) method.
本発明に用いるポリビニルピロリドンは、公知慣用の方法を用いて合成したものを用いてもよいし、市販品を用いてもよい。市販品としては、例えば、第一工業製薬株式会社製の「ピッツコール Ｋ−３０」（Ｍｗ：４０，０００）、「ピッツコール Ｋ−９０」（Ｍｗ：３６０，０００）等が挙げられる。 As the polyvinylpyrrolidone used in the present invention, one synthesized by a known and commonly used method may be used, or a commercially available product may be used. Examples of commercially available products include “Pittscall K-30” (Mw: 40,000) and “Pitskor K-90” (Mw: 360,000) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
前記ポリビニルピロリドン（Ｚ）の添加量は、加温、又は凍結後に融解を経た場合でも、より優れた分散安定性、基材への高い吸着性、及び、表面活性を同時に満たす観点から、前記金属ナノ粒子（Ｘ）と前記有機化合物（Ｙ）との複合体１００質量部に対して、０．１〜２０質量％の範囲が好ましく、０．５〜１５質量部の範囲がより好ましく、１〜１０質量部の範囲がより好ましく、２〜８の範囲が特に好ましい。 The added amount of the polyvinyl pyrrolidone (Z) is the metal from the viewpoint of simultaneously satisfying excellent dispersion stability, high adsorptivity to the substrate, and surface activity even when heated or thawed after freezing. The range of 0.1-20 mass% is preferable with respect to 100 mass parts of composites of nanoparticles (X) and the organic compound (Y), more preferably 0.5-15 mass parts. The range of 10 parts by mass is more preferable, and the range of 2 to 8 is particularly preferable.
本発明の金属ナノ粒子水分散液をインク、塗工液として、配線、導電層形成用に用いる場合には、水性分散体中の前記複合体の濃度は、０．５〜４０質量％の範囲が好ましく、１〜３０質量％の範囲がより好ましい。 When the metal nanoparticle aqueous dispersion of the present invention is used as an ink or a coating liquid for forming a wiring or a conductive layer, the concentration of the composite in the aqueous dispersion is in the range of 0.5 to 40% by mass. Is preferable, and the range of 1-30 mass% is more preferable.
本発明の金属ナノ粒子水分散液をインク、塗工液として、配線、導電層形成を行う場合、前記金属ナノ粒子（Ｘ）及び有機化合物（Ｙ）の複合体を基材上に付与する方法としては、特に制限は無く、公知慣用の種々の印刷・塗工手法を、使用する基材の形状、サイズ、剛柔の度合いなどによって適宜選択すればよい。具体的には、グラビア法、オフセット法、グラビアオフセット法、凸版法、凸版反転法、フレキソ法、スクリーン法、マイクロコンタクト法、リバース法、エアドクターコーター法、ブレードコーター法、エアナイフコーター法、スクイズコーター法、含浸コーター法、トランスファーロールコーター法、キスコーター法、キャストコーター法、スプレイコーター法、インクジェット法、ダイ法、スピンコーター法、バーコーター法等が挙げられる。 A method of applying a composite of the metal nanoparticles (X) and the organic compound (Y) on a substrate when wiring and conductive layer formation are performed using the metal nanoparticle aqueous dispersion of the present invention as an ink and a coating liquid. There is no particular limitation, and various known and commonly used printing / coating techniques may be appropriately selected depending on the shape, size, degree of flexibility, and the like of the substrate to be used. Specifically, gravure method, offset method, gravure offset method, letterpress method, letterpress inversion method, flexo method, screen method, microcontact method, reverse method, air doctor coater method, blade coater method, air knife coater method, squeeze coater Method, impregnation coater method, transfer roll coater method, kiss coater method, cast coater method, spray coater method, ink jet method, die method, spin coater method, bar coater method and the like.
前記複合体を基材上に印刷、もしくは塗工して、基材上に前記複合体を付与して配線、導電層形成を行う場合、印刷、もしくは塗工した基材を乾燥、焼成することによって、直接、配線、導電層形成を行ってもよいし、さらに無電解、もしくは電解めっき処理を行ってもよい。 When the composite is printed or coated on a substrate and the composite is applied on the substrate to form a wiring or conductive layer, the printed or coated substrate is dried and fired. In this case, the wiring and the conductive layer may be directly formed, or electroless or electrolytic plating may be performed.
また、本発明の金属ナノ粒子水分散液は、浸漬処理による通常のめっき処理工程で用いる無電解めっき用触媒液としても使用可能である。本発明の金属ナノ粒子水分散液を無電解めっき用触媒として用いる場合には、被めっき物への吸着量を確保し、かつ、めっき皮膜の被めっき物との密着性を良好にできることから、金属ナノ粒子水分散液中の前記複合体の濃度は、０．０５〜５ｇ／Ｌの範囲が好ましく、経済性を考慮すると、０．０２〜２ｇ／Ｌの範囲がより好ましい。 Moreover, the metal nanoparticle aqueous dispersion of the present invention can also be used as a catalyst solution for electroless plating used in a normal plating treatment step by immersion treatment. When the metal nanoparticle aqueous dispersion of the present invention is used as a catalyst for electroless plating, the amount of adsorption to the object to be plated can be secured, and the adhesion of the plating film to the object to be plated can be improved. The concentration of the complex in the metal nanoparticle aqueous dispersion is preferably in the range of 0.05 to 5 g / L, and more preferably in the range of 0.02 to 2 g / L in consideration of economy.
上記の方法により、その表面に本発明の金属ナノ粒子水分散液中の前記複合体を付着させた被めっき物は、公知の無電解めっき処理を施すことにより、その表面に金属皮膜を効率良く形成することができる。 By the above method, the object to be plated with the composite in the metal nanoparticle aqueous dispersion of the present invention attached to the surface thereof is subjected to a known electroless plating treatment, whereby a metal film is efficiently applied to the surface. Can be formed.
本発明の金属ナノ粒子水分散液に用いられる水性媒体としては、水単独、水と相溶可能な有機溶剤との混合溶媒が挙げられる。前記有機溶媒としては、複合体の分散安定性を損なわず、被めっき物が不要な損傷を受けないものであれば、特に制限無く選択することができる。前記有機溶媒の具体例としては、メタノール、エタノール、イソプロパノール、アセトン等が挙げられる。これらの有機溶媒は、１種で用いることも２種以上併用することもできる。 Examples of the aqueous medium used in the metal nanoparticle aqueous dispersion of the present invention include water alone and a mixed solvent of water and an organic solvent compatible with water. The organic solvent can be selected without particular limitation as long as it does not impair the dispersion stability of the composite and does not damage the object to be plated. Specific examples of the organic solvent include methanol, ethanol, isopropanol, acetone and the like. These organic solvents can be used alone or in combination of two or more.
前記水性媒体において、前記有機溶媒の混合割合は、前記複合体の分散安定性の観点から、５０質量％以下が好ましく、めっき工程での利便性の観点から、３０質量％以下がより好ましい。 In the aqueous medium, the mixing ratio of the organic solvent is preferably 50% by mass or less from the viewpoint of dispersion stability of the complex, and more preferably 30% by mass or less from the viewpoint of convenience in the plating step.
本発明の金属ナノ粒子水分散液を用いて、前記金属ナノ粒子（Ｘ）及び前記有機化合物（Ｙ）の複合体を付与する基材としては、特に限定されず、例えば、素材としては、ガラス繊維強化エポキシ、エポキシ系絶縁材、ポリイミド、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリカーボネート、液晶ポリマー（ＬＣＰ）、シクロオレフィンポリマー（ＣＯＰ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリフェニレンスルフィド（ＰＰＳ）等の樹脂、ガラス、セラミック、金属酸化物、金属、紙、合成又は天然繊維などの材質を１種又は複数種を組み合わせてなるものであり、その形状としては、板状、フィルム状、布状、繊維状、チューブ状等のいずれであってもよい。 The base material to which the composite of the metal nanoparticles (X) and the organic compound (Y) is applied using the metal nanoparticle aqueous dispersion of the present invention is not particularly limited. Fiber reinforced epoxy, epoxy insulation, polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate, liquid crystal polymer (LCP), cycloolefin polymer (COP), polyetheretherketone (PEEK), polyphenylene sulfide ( PPS) and other materials such as resin, glass, ceramic, metal oxide, metal, paper, synthetic or natural fiber, or a combination of one or more types. Any of cloth shape, fiber shape, tube shape, etc. may be sufficient.
本発明の金属ナノ粒子水分散液は、印刷、塗工、浸漬等の簡便な方法で、基材上に、金属ナノ粒子と有機化合物の複合体を付与することで、配線、導電層等を形成でき、また、無電解めっき用の触媒液として、好適に使用可能である。 The metal nanoparticle aqueous dispersion of the present invention provides a composite of metal nanoparticles and an organic compound on a substrate by a simple method such as printing, coating, or dipping. It can be formed and can be suitably used as a catalyst solution for electroless plating.
以下、実施例により本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail by way of examples.
［試料の分析］
試料の分析は次の装置を用いて実施した。透過型電子顕微鏡（ＴＥＭ）観察は、日本電子株式会社製「ＪＥＭ−１４００」で行った。紫外可視吸光スペクトル測定は、ＴｈｅｒｍｏＦｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ製「Ｎａｎｏｄｒｏｐ ＮＤ−１０００」）で行った。[Sample analysis]
The sample was analyzed using the following apparatus. Observation with a transmission electron microscope (TEM) was performed with “JEM-1400” manufactured by JEOL Ltd. The UV-visible absorption spectrum measurement was performed with ThermoFisher Scientific “Nanodrop ND-1000”).
（合成例１：アニオン性官能基を有する重合物（Ｙ２−１）の合成）
温度計、攪拌機及び還流冷却器を備えた四つ口フラスコに、メチルエチルケトン（以下、「ＭＥＫ」と略記する。）３２質量部及びエタノール３２質量部を仕込んで、窒素気流下で攪拌しながら８０℃に昇温した。次に、ホスホオキシエチルメタクリレート（共栄社化学株式会社製「ライトエステル Ｐ−１Ｍ」）２０質量部、メトキシポリエチレングリコールメタクリレート（日油株式会社製「ブレンマー ＰＭＥ−１０００」、分子量１，０００）８０質量部、３−メルカプトプロピオン酸メチル４．１質量部及びＭＥＫ８０質量部の混合物と、重合開始剤（和光純薬株式会社「Ｖ−６５」、２，２’−アゾビス（２，４−ジメチルバレロニトリル））０．５質量部及びＭＥＫ５質量部の混合物とをそれぞれ２時間かけて滴下した。滴下終了後、４時間ごとに重合開始剤（日油株式会社製「パーブチルＯ」）０．３質量部を２回添加し、８０℃で１２時間攪拌した。得られた樹脂溶液に水を加え転相乳化し、減圧脱溶剤した後、水を加えて濃度を調整することで、不揮発分７６．８質量％の重合物（Ｙ２−１）の水溶液が得られた。この重合物（Ｙ２−１）は、メトキシカルボニルエチルチオ基、リン酸基及びポリエチレングリコール鎖を有するものであり、その重量平均分子量（ゲルパーミエーション・クロマトグラフィーにより測定されたポリスチレン換算値）は４，３００、酸価は９７．５ｍｇＫＯＨ／ｇであった。(Synthesis Example 1: Synthesis of Polymer (Y2-1) Having Anionic Functional Group)
A four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 32 parts by mass of methyl ethyl ketone (hereinafter abbreviated as “MEK”) and 32 parts by mass of ethanol, and stirred at 80 ° C. under a nitrogen stream. The temperature was raised to. Next, 20 parts by mass of phosphooxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. “Light Ester P-1M”), methoxypolyethylene glycol methacrylate (manufactured by NOF Corporation “Blenmer PME-1000”, molecular weight 1,000) 80 parts by mass , A mixture of 4.1 parts by mass of methyl 3-mercaptopropionate and 80 parts by mass of MEK and a polymerization initiator (Wako Pure Chemical Industries, Ltd. “V-65”, 2,2′-azobis (2,4-dimethylvaleronitrile) ) A mixture of 0.5 parts by mass and 5 parts by mass of MEK was added dropwise over 2 hours. After the completion of dropping, 0.3 parts by mass of a polymerization initiator (“Perbutyl O” manufactured by NOF Corporation) was added twice every 4 hours, and the mixture was stirred at 80 ° C. for 12 hours. Water was added to the obtained resin solution for phase inversion emulsification, and after desolvation under reduced pressure, water was added to adjust the concentration to obtain an aqueous solution of a polymer (Y2-1) having a nonvolatile content of 76.8% by mass. It was. This polymer (Y2-1) has a methoxycarbonylethylthio group, a phosphate group, and a polyethylene glycol chain, and its weight average molecular weight (polystyrene conversion value measured by gel permeation chromatography) is 4. 300, and the acid value was 97.5 mgKOH / g.
（調製例１：銀ナノ粒子水分散液の調製）
Ｎ，Ｎ−ジエチルヒドロキシルアミンの８５質量％水溶液４６３ｇ（４．４１ｍｏｌ）、合成例１で得られた重合物（Ｙ２−１）の水溶液３０ｇ（重合物（Ｙ２−１）として２３ｇ）及び水１，２５０ｇを混合し還元剤溶液を調製した。(Preparation Example 1: Preparation of silver nanoparticle aqueous dispersion)
463 g (4.41 mol) of an 85 mass% aqueous solution of N, N-diethylhydroxylamine, 30 g of an aqueous solution of the polymer (Y2-1) obtained in Synthesis Example 1 (23 g as the polymer (Y2-1)) and water 1 , 250 g was mixed to prepare a reducing agent solution.
次に、合成例１で得られた重合物（Ｙ２−１）の水溶液１５ｇ（重合物（Ｙ２−１）として１１．５ｇ）を水３３３ｇに溶解し、これに硝酸銀５００ｇ（２．９４ｍｏｌ）を水８３３ｇに溶解した溶液を加えて、よく攪拌した。この混合物に上記で得られた還元剤溶液を室温（２５℃）で２時間かけて滴下した。得られた反応混合物をメンブレンフィルター（細孔径０．４５マイクロメートル）で濾過し、濾液を中空糸型限外濾過モジュール（ダイセンメンブレンシステムズ社製「ＭＯＬＳＥＰモジュールＦＢ−０２型」、分画分子量１５万）中を循環させ、流出する濾液の量に対応する量の水を随時添加して精製した。濾液の電導度が１００μＳ／ｃｍ以下になったことを確認した後、注水を中止して濃縮した。濃縮物を回収することで、不揮発分３６．７質量％の銀ナノ粒子含有複合体の水分散液が得られた。動的光散乱法による複合体の平均粒子径は３９ｎｍであり、透過型電子顕微鏡（ＴＥＭ）像からは１０〜４０ｎｍと見積もられた。 Next, 15 g of an aqueous solution of polymer (Y2-1) obtained in Synthesis Example 1 (11.5 g as polymer (Y2-1)) was dissolved in 333 g of water, and 500 g (2.94 mol) of silver nitrate was added thereto. A solution dissolved in 833 g of water was added and stirred well. To this mixture, the reducing agent solution obtained above was added dropwise at room temperature (25 ° C.) over 2 hours. The obtained reaction mixture was filtered with a membrane filter (pore diameter 0.45 micrometer), and the filtrate was a hollow fiber type ultrafiltration module ("MOLSEP module FB-02 type" manufactured by Daisen Membrane Systems Co., Ltd., molecular weight cut off 150,000). ) It was circulated through and purified by adding water in an amount corresponding to the amount of filtrate flowing out as needed. After confirming that the electric conductivity of the filtrate was 100 μS / cm or less, water injection was stopped and the filtrate was concentrated. By collecting the concentrate, an aqueous dispersion of a silver nanoparticle-containing composite having a nonvolatile content of 36.7% by mass was obtained. The average particle diameter of the composite by the dynamic light scattering method was 39 nm, and was estimated to be 10 to 40 nm from a transmission electron microscope (TEM) image.
（実施例１）
調製例１で得られた銀ナノ粒子水分散液２７２．５質量部（銀ナノ粒子含有複合体として１００質量部）に、ポリビニルピロリドン（第一工業製薬株式会社製「ピッツコール Ｋ−３０」、Ｍｗ：４０，０００）の２０質量％水溶液２０質量部（ポリビニルピロリドンとして４質量部）を加えた後、均一に撹拌し、銀ナノ粒子含有複合体の濃度が１０質量％になるようにイオン交換水を加え、銀ナノ粒子水分散液（１）を得た。Example 1
To 272.5 parts by mass of the silver nanoparticle aqueous dispersion obtained in Preparation Example 1 (100 parts by mass as a silver nanoparticle-containing complex), polyvinylpyrrolidone (“Pitzkor K-30” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., After adding 20 parts by mass of a 20% by mass aqueous solution (Mw: 40,000) (4 parts by mass as polyvinylpyrrolidone), the mixture is stirred uniformly and ion-exchanged so that the concentration of the silver nanoparticle-containing complex is 10% by mass. Water was added to obtain a silver nanoparticle aqueous dispersion (1).
［銀ナノ粒子水分散液の外観評価］
上記で得られた銀ナノ粒子水分散液（１）の分散安定性の評価指標として、外観を目視で観察し、懸濁の有無を確認した。また、後述する加熱試験、又は凍結−融解試験後の外観評価については、色の変化も併せて確認した。[Appearance evaluation of silver nanoparticle aqueous dispersion]
As an evaluation index of the dispersion stability of the silver nanoparticle aqueous dispersion (1) obtained above, the appearance was visually observed to confirm the presence or absence of suspension. Moreover, the color change was also confirmed about the external appearance evaluation after the heating test mentioned later or a freeze-thaw test.
［基材への吸着性評価とめっき被覆率の測定］
銀ナノ粒子の活性を判断する指標として、基材上に付与した金属ナノ粒子を触媒とした無電解銅めっき処理を行った。[Evaluation of adsorptivity to substrate and measurement of plating coverage]
As an index for judging the activity of silver nanoparticles, an electroless copper plating treatment was performed using metal nanoparticles applied on the substrate as a catalyst.
基材としてスライドガラスを用意し、そのスライドガラスをポリエチレンイミン（株式会社日本触媒製「エポミン ＳＰ−２００」）の２質量％水溶液に１分間浸漬して取り出し、１分間流水洗浄した後、エアーブローで水切りをして、表面処理スライドガラスを得た。 A slide glass is prepared as a base material. The slide glass is immersed in a 2% by weight aqueous solution of polyethyleneimine (“Epomin SP-200” manufactured by Nippon Shokubai Co., Ltd.) for 1 minute, taken out, washed with running water for 1 minute, and then air blown. The surface-treated slide glass was obtained by draining with
次いで、無電解銅めっき浴として、硫酸銅五水和物０．０４ｍｏｌ／Ｌ、ホルムアルデヒド０．０４ｍｏｌ／Ｌ、及びエチレンジアミン四酢酸二ナトリウム０．０８ｍｏｌ／Ｌを含有する水溶液を水酸化ナトリウムによりｐＨを１２．３に調整した溶液を調製し、５５℃に加温したものを準備した。 Next, as an electroless copper plating bath, an aqueous solution containing copper sulfate pentahydrate 0.04 mol / L, formaldehyde 0.04 mol / L, and ethylenediaminetetraacetic acid disodium 0.08 mol / L was adjusted to pH with sodium hydroxide. A solution adjusted to 12.3 was prepared, and a solution heated to 55 ° C. was prepared.
上記で表面処理したスライドガラスを、上記で得られた銀ナノ粒子水分散液（１）を２００倍に希釈したものに２５℃で１０分間浸漬し、スライドガラスの表面に銀ナノ粒子を吸着させた。このとき銀ナノ粒子が着色しているため、スライドガラス表面への銀ナノ粒子の吸着量が多いほど、スライドガラスが黄色く着色した。この着色の程度を目視で観察し、後述する添加剤未添加のもの（比較例１）を標準として、下記のような基準にしたがって基材への吸着性評価を行った。
○：添加剤未添加のものと同等である。
△：添加剤未添加のものより着色が薄い。
×：ほとんど着色せず、無色透明に近い。The slide glass surface-treated above is immersed in a 200-fold diluted silver nanoparticle aqueous dispersion (1) obtained above at 25 ° C. for 10 minutes to adsorb the silver nanoparticles on the surface of the slide glass. It was. Since the silver nanoparticles were colored at this time, the slide glass colored yellow as the amount of silver nanoparticles adsorbed on the slide glass surface increased. The degree of coloring was visually observed, and the adsorptivity to the base material was evaluated according to the following criteria with the additive-free additive (Comparative Example 1) described below as a standard.
○: Equivalent to those without additives.
(Triangle | delta): Coloring is lighter than the thing without an additive.
X: Almost no color and almost colorless and transparent.
次いで、銀ナノ粒子を吸着させたスライドガラスを取り出して１分間水洗を行った後、上記で準備した無電解銅めっき浴に、空気攪拌を行いながら３０分間浸漬した後、取り出して１分間水洗を行い、無電解銅めっきを施した。 Next, after taking out the slide glass on which the silver nanoparticles were adsorbed and washing with water for 1 minute, the glass was immersed in the electroless copper plating bath prepared above for 30 minutes with air stirring, then taken out and washed with water for 1 minute. And electroless copper plating was applied.
無電解銅めっきされたスライドガラスの写真の画像処理によって明度基準で白黒２値化を行い、めっきされている部分の面積からめっき被覆率を算出した。得られためっき被覆率から、銀ナノ粒子複合体の活性を評価した。ここで、触媒活性が充分に高い場合には、基材表面全体にめっきが析出し、活性が低下するとめっきの析出面積が低下する。したがって、スライドガラスの表面全面にめっき被覆されている（めっき被覆率１００％）ものを、銀ナノ粒子複合体の活性が良好であると判断した。 Black and white binarization was performed on the basis of lightness by image processing of a photograph of a slide glass plated with electroless copper, and the plating coverage was calculated from the area of the plated portion. The activity of the silver nanoparticle composite was evaluated from the obtained plating coverage. Here, when the catalytic activity is sufficiently high, plating is deposited on the entire surface of the substrate, and when the activity is reduced, the deposition area of the plating is reduced. Therefore, it was judged that the activity of the silver nanoparticle composite was good when the entire surface of the slide glass was plated (plating coverage: 100%).
［加温試験］
５０ｍＬスクリュー管に、上記で得られた銀ナノ粒子水分散液（１）を入れて密閉した。次いで、これを５０℃の恒温槽で１４日間加温した。加温後に、上記の方法と同様に外観を評価した。また、加温前後の銀ナノ粒子水分散液（１）について、銀ナノ粒子複合体の濃度を５０ｐｐｍに希釈し、紫外可視吸光スペクトルを測定したところ（図１参照）、銀のナノ粒子表面状態と相関するプラズモン吸収スペクトルが観測された。銀ナノ粒子が凝集した場合、表面状態とスペクトル形状が変化するが、加温前後でスペクトル形状が変化しないことから、銀ナノ粒子水分散液（１）中の銀ナノ粒子の分散状態に変化がないことを確認した。[Warming test]
The silver nanoparticle aqueous dispersion (1) obtained above was placed in a 50 mL screw tube and sealed. Next, this was heated in a thermostat at 50 ° C. for 14 days. After heating, the appearance was evaluated in the same manner as described above. Moreover, about the silver nanoparticle aqueous dispersion (1) before and behind heating, when the density | concentration of a silver nanoparticle composite was diluted to 50 ppm and the ultraviolet visible absorption spectrum was measured (refer FIG. 1), the nanoparticle surface state of silver A plasmon absorption spectrum correlating with was observed. When silver nanoparticles are aggregated, the surface state and spectral shape change, but since the spectral shape does not change before and after heating, there is a change in the dispersion state of silver nanoparticles in the silver nanoparticle aqueous dispersion (1). Confirmed that there is no.
次いで、加熱後の銀ナノ粒子水分散液（１）を２００倍に希釈したものを用意し、上記と同様の方法で、めっき被覆率を測定した。 Subsequently, what diluted the silver nanoparticle aqueous dispersion (1) after heating 200 times was prepared, and the plating coverage was measured by the method similar to the above.
［凍結−融解試験］
５０ｍＬスクリュー管に、上記で得られた銀ナノ粒子水分散液（１）を入れて密閉した。次いで、これをドライアイスチップに５分間接触させ凍結させた後、常温で解凍した。この凍結して解凍する操作を１サイクルとして、３サイクル繰り返した。凍結して解凍する操作を３サイクル行った後、上記の方法と同様に外観を評価した。また、凍結前と凍結して解凍する操作を３サイクル行った後の銀ナノ粒子水分散液（１）について、紫外可視吸光スペクトルを測定した（図２参照）。この紫外可視吸光スペクトルの測定結果から、凍結、解凍を繰り返しても、銀ナノ粒子水分散液（１）中の銀ナノ粒子の分散状態に変化がないことを確認した。[Freeze-thaw test]
The silver nanoparticle aqueous dispersion (1) obtained above was placed in a 50 mL screw tube and sealed. Next, this was contacted with a dry ice chip for 5 minutes to freeze, and then thawed at room temperature. This operation of freezing and thawing was defined as one cycle and repeated three times. After three cycles of freezing and thawing, the appearance was evaluated in the same manner as in the above method. Moreover, the ultraviolet-visible absorption spectrum was measured about the silver nanoparticle aqueous dispersion liquid (1) after performing freezing and the operation which freezes and thaws 3 cycles (refer FIG. 2). From the measurement result of the UV-visible absorption spectrum, it was confirmed that the dispersion state of the silver nanoparticles in the silver nanoparticle aqueous dispersion (1) did not change even when freezing and thawing were repeated.
次いで、凍結して解凍する操作を３サイクル行った後の銀ナノ粒子水分散液（１）を２００倍に希釈したものを用意し、上記と同様の方法で、めっき被覆率を測定した。 Subsequently, the silver nanoparticle aqueous dispersion (1) after the operation of freezing and thawing three cycles was prepared by diluting it 200 times, and the plating coverage was measured by the same method as described above.
［総合評価］
上記で行った加熱試験及び凍結−融解試験の結果から、分散安定性及び基材への吸着性を評価し、下記の基準にしたがって総合評価を行った。
○：加熱試験及び凍結−融解試験において、分散安定性及び基材への吸着性に問題が無かった。
×：加熱試験及び凍結−融解試験において、分散安定性及び基材への吸着性のいずれかに問題があった。[Comprehensive evaluation]
From the results of the heating test and the freeze-thaw test performed above, the dispersion stability and the adsorptivity to the substrate were evaluated, and a comprehensive evaluation was performed according to the following criteria.
○: In the heating test and the freeze-thaw test, there was no problem in dispersion stability and adsorptivity to the substrate.
X: There was a problem in either the dispersion stability or the adsorptivity to the substrate in the heating test and the freeze-thaw test.
（実施例２）
実施例１で用いたポリビニルピロリドンの２０質量％水溶液を２０質量部から、１０質量部（ポリビニルピロリドンとして２質量部）に変更した以外は実施例１と同様に操作して、銀ナノ粒子水分散液（２）を得た。また、得られた銀ナノ粒子水分散液（２）について、実施例１と同様に測定及び評価を行った。(Example 2)
Silver nanoparticle water dispersion was carried out in the same manner as in Example 1 except that the 20% by mass aqueous polyvinylpyrrolidone solution used in Example 1 was changed from 20 parts by mass to 10 parts by mass (2 parts by mass as polyvinylpyrrolidone). A liquid (2) was obtained. Further, the obtained silver nanoparticle aqueous dispersion (2) was measured and evaluated in the same manner as in Example 1.
（実施例３）
実施例１で用いたポリビニルピロリドンの２０質量％水溶液を２０質量部から、５０質量部（ポリビニルピロリドンとして１０質量部）に変更した以外は実施例１と同様に操作して、銀ナノ粒子水分散液（３）を得た。また、得られた銀ナノ粒子水分散液（３）について、実施例１と同様に測定及び評価を行った。(Example 3)
Silver nanoparticle water dispersion was carried out in the same manner as in Example 1 except that the 20% by mass aqueous polyvinylpyrrolidone solution used in Example 1 was changed from 20 parts by mass to 50 parts by mass (10 parts by mass as polyvinylpyrrolidone). A liquid (3) was obtained. Further, the obtained silver nanoparticle aqueous dispersion (3) was measured and evaluated in the same manner as in Example 1.
（実施例４）
実施例１で用いたポリビニルピロリドンを、ポリビニルピロリドン（第一工業製薬株式会社製「ピッツコール Ｋ−９０」、Ｍｗ：３６０，０００）に変更し、その水溶液の濃度を１０質量％とした以外は実施例１と同様に操作して、銀ナノ粒子水分散液（４）を得た。また、得られた銀ナノ粒子水分散液（４）について、実施例１と同様に測定及び評価を行った。Example 4
The polyvinyl pyrrolidone used in Example 1 was changed to polyvinyl pyrrolidone (“Pitscol K-90” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Mw: 360,000), and the concentration of the aqueous solution was changed to 10% by mass. The same operation as in Example 1 was carried out to obtain a silver nanoparticle aqueous dispersion (4). Further, the obtained silver nanoparticle aqueous dispersion (4) was measured and evaluated in the same manner as in Example 1.
（比較例１）
調製例１で得られた銀ナノ粒子水分散液にイオン交換水を加え、水分散液中の銀ナノ粒子含有複合体の濃度が１０質量％になるように調製し、銀ナノ粒子水分散液（Ｒ１）を得た。また、得られた銀ナノ粒子水分散液（Ｒ１）について、実施例１と同様に測定及び評価を行った。なお、この銀ナノ粒子水分散液（Ｒ１）を銀ナノ粒子複合体の濃度が５０ｐｐｍになるように希釈し、加熱前の紫外可視吸光スペクトルを測定したところ、ポリビニルピロリドンを添加した実施例１のものと差は無かった。また、加熱後の紫外可視吸光スペクトルを測定したところ、スペクトル形状に変化はなかった（図１参照）。(Comparative Example 1)
Ion-exchanged water is added to the silver nanoparticle aqueous dispersion obtained in Preparation Example 1 so that the concentration of the silver nanoparticle-containing complex in the aqueous dispersion is 10% by mass. (R1) was obtained. Further, the obtained silver nanoparticle aqueous dispersion (R1) was measured and evaluated in the same manner as in Example 1. In addition, when this silver nanoparticle aqueous dispersion (R1) was diluted so that the density | concentration of a silver nanoparticle composite might be set to 50 ppm, and the ultraviolet-visible absorption spectrum before a heating was measured, polyvinylpyrrolidone of Example 1 which added polyvinylpyrrolidone was measured. There was no difference. Moreover, when the ultraviolet visible absorption spectrum after a heating was measured, the spectrum shape did not change (refer FIG. 1).
一方、この銀ナノ粒子水分散液（Ｒ１）を凍結して解凍する操作を１サイクル行ったところ、５０ｐｐｍに希釈したときの液色は黄色から黒緑色に変化した。この黒緑色に変化した液の紫外可視吸光スペクトルを測定したところ、銀ナノ粒子の凝集に基づくプラズモン吸収ピークの強度減少と長波長側の吸収増大が認められ、分散状態が悪化したことを確認した（図２参照）。 On the other hand, when the silver nanoparticle aqueous dispersion (R1) was frozen and thawed for one cycle, the liquid color when diluted to 50 ppm changed from yellow to black-green. When the UV-visible absorption spectrum of the liquid changed to black-green was measured, a decrease in the intensity of the plasmon absorption peak and an increase in absorption on the long wavelength side due to the aggregation of silver nanoparticles were observed, confirming that the dispersion state deteriorated. (See FIG. 2).
（比較例２〜１５）
実施例１で用いたポリビニルピロリドンを、表１に示した添加物及び添加量に変更した以外は実施例１と同様に操作して、銀ナノ粒子水分散液（Ｒ２）〜（Ｒ１５）を調製した。また、得られた銀ナノ粒子水分散液（Ｒ２）〜（Ｒ１５）について、実施例１と同様に分散安定性と活性の測定及び評価を行った。(Comparative Examples 2-15)
Silver nanoparticle aqueous dispersions (R2) to (R15) were prepared in the same manner as in Example 1 except that the polyvinylpyrrolidone used in Example 1 was changed to the additives and addition amounts shown in Table 1. did. Further, the obtained silver nanoparticle aqueous dispersions (R2) to (R15) were subjected to measurement and evaluation of dispersion stability and activity in the same manner as in Example 1.
実施例１〜４及び比較例１〜１５で得られた銀ナノ粒子水分散液（１）〜（４）及び（Ｒ１）〜（Ｒ１５）の添加物とその添加量、及び評価結果を表１に示す。なお、表１中の添加量は、銀ナノ粒子含有複合体（金属ナノ粒子（Ｘ）及び有機化合物（Ｙ）の複合体）１００質量部に対する添加物の量を表す。 Table 1 shows the additives of the silver nanoparticle aqueous dispersions (1) to (4) and (R1) to (R15) obtained in Examples 1 to 4 and Comparative Examples 1 to 15, their addition amounts, and evaluation results. Shown in In addition, the addition amount of Table 1 represents the quantity of the additive with respect to 100 mass parts of silver nanoparticle containing composites (complex of a metal nanoparticle (X) and an organic compound (Y)).
表１中に記載の添加物の詳細は、下記の通りである。
ポリエチレングリコール：重量平均分子量６，０００
ポリビニルアルコール：重合度５００、ケン化度８６〜９０ｍｏｌ％
重合物（Ｙ２−１）：合成例１で得られた重合物をそのまま添加剤として用いた。The details of the additives described in Table 1 are as follows.
Polyethylene glycol: weight average molecular weight 6,000
Polyvinyl alcohol: polymerization degree 500, saponification degree 86-90 mol%
Polymer (Y2-1): The polymer obtained in Synthesis Example 1 was directly used as an additive.
表１中の加熱試験後の外観変化で「有り」となっているものは、銀ナノ粒子の凝集によって、灰色に懸濁したことを示す。また、凍結−融解試験後の外観変化で「有り」となっているものは、銀ナノ粒子の凝集に基づく、プラズモン吸収の変化によって、液色が黄色から黒緑色に変色したことを示す。 A change in appearance after heating test in Table 1 that is “present” indicates that the particles are suspended in gray due to aggregation of silver nanoparticles. Moreover, what is “Yes” in the appearance change after the freeze-thaw test indicates that the liquid color has changed from yellow to black-green due to the change in plasmon absorption based on the aggregation of silver nanoparticles.
表１に示した評価結果から、本発明の金属ナノ粒子分散液である実施例１〜４のものは、加温、又は凍結後に融解する操作を繰り返すといった熱的負荷が加えられても優れた分散安定性を有し、かつ基材への十分な吸着性を有することが確認できた。 From the evaluation results shown in Table 1, the metal nanoparticle dispersions of Examples 1 to 4 according to the present invention were excellent even when a thermal load was applied such as heating or repeated thawing after freezing. It was confirmed that it had dispersion stability and sufficient adsorptivity to the substrate.
一方、添加物を添加しなかったもの（比較例１）及びポリビニルピロリドン以外の添加物を添加したもの（比較例２〜１５）は、加温、又は凍結後に融解する操作を行うことで、分散安定性が低下したり、基材への吸着性が低下したりすることが確認できた。 On the other hand, those in which no additives were added (Comparative Example 1) and those in which additives other than polyvinylpyrrolidone were added (Comparative Examples 2 to 15) were dispersed by performing an operation of heating or thawing after freezing. It was confirmed that the stability was lowered and the adsorptivity to the substrate was lowered.
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| JP2015025198A (en) * | 2013-06-21 | 2015-02-05 | Dic株式会社 | Electroless plating catalyst, metal film using the same and method for manufacturing metal film |
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| JP2008226816A (en) * | 2006-10-11 | 2008-09-25 | Mitsubishi Materials Corp | Electrode forming composition and forming method of electrode using the same |
| JP2010209421A (en) * | 2009-03-11 | 2010-09-24 | Dic Corp | Protective agent for metal nanoparticle, dispersion of metal nanoparticle, and method for producing dispersion of metal nanoparticle |
| WO2011048876A1 (en) * | 2009-10-20 | 2011-04-28 | Dic株式会社 | Metal nanoparticle containing complex, fluid dispersion thereof and production methods for metal nanoparticle containing complex and fluid dispersion thereof |
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