TW201817914A - Electroless nickel plating method - Google Patents

Electroless nickel plating method Download PDF

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Publication number
TW201817914A
TW201817914A TW106116113A TW106116113A TW201817914A TW 201817914 A TW201817914 A TW 201817914A TW 106116113 A TW106116113 A TW 106116113A TW 106116113 A TW106116113 A TW 106116113A TW 201817914 A TW201817914 A TW 201817914A
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substrate
plated
composite
nickel plating
group
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TW106116113A
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Chinese (zh)
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深澤憲正
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迪愛生股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites

Abstract

The present invention provides an electroless nickel plating method for forming a nickel film on a substrate (S) to be plated by immersing the substrate (S) to be plated, on which a composite (C) of metal particles (M) such as silver particles and a polymer (P) with anionic groups, polyalkylene imine, etc. has been attached, in an electroless nickel plating solution containing a water-soluble nickel salt, a reducing agent and a complexing agent. In the electroless nickel plating method, the reducing agent is hypophosphoric acid or a salt thereof, and when immersing the substrate (S) to be plated in the electroless plating solution, at least one kind of solid metal selected from a group consisting of nickel, iron and cobalt is included in the plating solution. Said plating method provides an adequate amount of adsorbed catalyst and is able to form a good electroless nickel plating film on a useful substrate to be plated such as resin, glass or ceramic without a complicated two-stage process.

Description

無電鎳鍍覆方法    Electroless nickel plating method   

本發明係關於可在樹脂、玻璃、陶瓷、金屬等的各種基材表面形成鎳金屬的被膜之無電鎳鍍覆方法。 The present invention relates to an electroless nickel plating method capable of forming a coating of nickel metal on the surface of various substrates such as resin, glass, ceramics, and metals.

鎳鍍覆，由於顯示銀色的漂亮色調，因此被用於裝飾用途，又，由於具有適度的硬度而耐蝕性優異，因此以提升各種材料的耐久性為目的而被使用。又，在組裝領域上，廣泛使用以提升焊接性、接合性、或改善耐蝕性、耐熱性為目的之鎳鍍覆。特別是無電鎳鍍覆即使在非導電性的基材表面也可形成鎳膜，因此被視為重要的基材表面處理法。 Nickel plating is used for decorative purposes because it displays a beautiful silver hue, and because it has moderate hardness and excellent corrosion resistance, it is used for the purpose of improving the durability of various materials. In the field of assembly, nickel plating is widely used for the purpose of improving weldability, bonding properties, or improving corrosion resistance and heat resistance. In particular, electroless nickel plating can form a nickel film even on the surface of a non-conductive substrate, and is therefore regarded as an important substrate surface treatment method.

在無電鎳鍍覆中，通常對於還原劑的氧化反應，必須使基材表面成為觸媒活性的表面，以往為了此目的而使用昂貴的鈀觸媒。作為使鈀觸媒附著於被鍍覆基材的方法，主要使用以下兩個方法。 In electroless nickel plating, it is generally necessary to make the surface of the substrate a catalytically active surface for the oxidation reaction of the reducing agent. Conventionally, an expensive palladium catalyst has been used for this purpose. As a method for attaching a palladium catalyst to a substrate to be plated, the following two methods are mainly used.

(1)將被鍍覆物浸漬於敏化劑溶液(氯化鈀的鹽酸溶液)後，在被鍍覆物上將鈀鹽還原而得到鈀膠體附著體的方法(敏化劑-活化劑法)。 (1) A method of immersing an object to be plated in a sensitizer solution (a solution of palladium chloride in hydrochloric acid) and reducing a palladium salt on the object to obtain a palladium colloid (sensitizer-activator method ).

(2)浸漬於錫-鈀混合膠體溶液，使膠體附著於被鍍覆物後，浸漬於包含硫酸等的酸性溶液之加速劑 溶液中，使過剩的錫離子溶解而表現觸媒活性的方法(觸媒-加速劑法)。 (2) A method of immersing in a tin-palladium mixed colloid solution to adhere the colloid to the object to be plated, and then immersing it in an accelerator solution containing an acidic solution such as sulfuric acid to dissolve excess tin ions to exhibit catalytic activity ( Catalyst-accelerator method).

即，一般為首先使觸媒金屬化合物附著於被鍍覆物表面，接著轉換為表現觸媒效果之還原金屬微粒子的方法，但這些方法需要經過兩個階段(賦予與活化)的步驟，為非常繁雜的方法，除此之外，因步驟數增加而有所謂製程成本變大的缺點。 That is, it is generally a method of first attaching a catalytic metal compound to the surface of a plated object, and then converting it to a reduced metal particle that exhibits a catalytic effect. However, these methods require two steps (giving and activating). In addition to the complicated method, there is a disadvantage that the so-called process cost increases due to an increase in the number of steps.

相對於此，長久以來亦開發不需要還原操作而將預先調製的金屬奈米粒子(或金屬膠體)賦予至被鍍覆物而用作鍍覆觸媒的方法，除了鈀膠體之外，亦有提案使用銀膠體或銀奈米粒子、銅奈米粒子這樣的經濟性金屬種的方法(例如，參照專利文獻1~4及非專利文獻1、2)。 In contrast, for a long time, there has been developed a method for imparting metal nano particles (or metal colloids) prepared in advance to a plated object without using a reduction operation as a plating catalyst. In addition to palladium colloids, A method using economical metal species such as silver colloid, silver nano particles, and copper nano particles is proposed (for example, refer to Patent Documents 1 to 4 and Non-Patent Documents 1 and 2).

然而，在使用這些金屬膠體的情況下，由於觸媒浴的穩定性低、無法得到對被鍍覆基材之充分的觸媒附著量等的理由，難以利用作為可利用於工業上的實用性觸媒，現狀為主要使用如前述的經過繁雜的兩階段步驟之鍍覆手法，仍要求有所改善。 However, when these metal colloids are used, it is difficult to use them as industrial practicability due to reasons such as the low stability of the catalyst bath, the inability to obtain a sufficient catalyst adhesion amount to the substrate to be plated, and the like. Catalysts, the current situation is that the plating method, which mainly uses the complicated two-stage steps described above, still requires improvement.

為了解決這樣的問題，有提案藉由簡便的浸漬操作，而對被鍍覆基材的賦予性優異且顯示觸媒活性之穩定性優異的無電鍍覆用觸媒(例如，參照專利文獻5)。又，有揭示藉由塗布法將無電鍍覆用觸媒的金屬粒子賦予至基材上的技術(例如，參照專利文獻6)。 In order to solve such a problem, there is a proposal for an electroless plating catalyst that is excellent in imparting properties to a plated substrate and exhibits stability of catalyst activity by a simple dipping operation (for example, refer to Patent Document 5). . In addition, there is a technique for applying metal particles of a catalyst for electroless plating to a substrate by a coating method (for example, refer to Patent Document 6).

在這些技術中，其特徵為使用特定的高分子與金屬奈米粒子的複合體來作為穩定且對被鍍覆基材 給予充分的吸附量之無電鍍覆用觸媒，雖可得到良好的結果，但在選擇便宜且價格變動少的銀或銅作為金屬奈米粒子的金屬的情況下，仍留有欲使無電鎳鍍覆的活性進一步提升這樣的改良點。 These technologies are characterized by using a composite of a specific polymer and metal nano-particles as a catalyst for electroless plating which is stable and gives a sufficient adsorption amount to a substrate to be plated, although good results can be obtained However, in the case where silver or copper, which is cheap and has little price fluctuation, is selected as the metal of the metal nanoparticle, there is still an improvement point to further improve the activity of electroless nickel plating.

對於以銀為觸媒而進行無電鎳鍍覆，有揭示使用硼系化合物的二甲胺硼烷作為還原劑的技術(例如，參照非專利文獻4及5)。藉由使用硼系化合物，可使無電鎳鍍覆的活性提升，但在此情況下，鎳鍍覆膜成為含有硼的鎳-硼合金，有成為特性與將次磷酸還原的情況相異的鍍覆膜、製程成本變高等的課題，將次磷酸鹽用於還原劑的情況下之活性提升成為課題。 For electroless nickel plating using silver as a catalyst, there has been disclosed a technique using a dimethylamine borane of a boron compound as a reducing agent (for example, see Non-Patent Documents 4 and 5). By using a boron-based compound, the activity of electroless nickel plating can be improved, but in this case, the nickel plating film becomes a nickel-boron alloy containing boron, and has a plating property different from that in the case of reducing hypophosphorous acid. The problems such as coating and process cost increase, and the improvement of the activity in the case of using hypophosphite as a reducing agent has become a problem.

先前技術文獻Prior art literature 專利文獻Patent literature

專利文獻1 日本特開昭61-227175號公報 Patent Document 1 Japanese Patent Laid-Open No. 61-227175

專利文獻2 日本特開昭62-207877號公報 Patent Document 2 Japanese Patent Laid-Open No. 62-207877

專利文獻3 日本特開昭64-68478號公報 Patent Document 3 Japanese Unexamined Patent Publication No. 64-68478

專利文獻4 日本特開平10-229280號公報 Patent Document 4 Japanese Patent Application Laid-Open No. 10-229280

專利文獻5 日本特開2015-25198號公報 Patent Document 5 Japanese Patent Laid-Open No. 2015-25198

專利文獻6 WO2014/045972號公報 Patent Document 6 WO2014 / 045972

非專利文獻Non-patent literature

非專利文獻1 A.Vaskelis等人，Electrochim. Acta 2005, 50, 4586. Non-Patent Document 1 A. Vaskelis et al., Electrochim. Acta 2005, 50, 4586.

非專利文獻2 Ohno等人，J. Electrochem. Soc. 1985, 132, 2323. Non-Patent Document 2 Ohno et al., J. Electrochem. Soc. 1985, 132, 2323.

非專利文獻3 高橋等人，表面技術2007, 58(12), 841. Non-Patent Document 3 Takahashi et al. Surface Technology 2007, 58 (12), 841.

非專利文獻4 Yiang Lu等人，Applied Surf. Sci. 2012, 258, 4782. Non-Patent Document 4 Yiang Lu et al., Applied Surf. Sci. 2012, 258, 4782.

非專利文獻5 Yiang Lu等人，Surface & Coatings Tech. 2012, 206, 3639. Non-Patent Document 5 Yiang Lu et al., Surface & Coatings Tech. 2012, 206, 3639.

有鑑於如上述的技術背景，本發明所欲解決的課題係提供下述的方法：不經過複雜的兩階段步驟而給予充分的觸媒吸附量，以便宜的銀、銅的粒子為觸媒，使用次磷酸鹽作為還原劑，對樹脂、玻璃、陶瓷等之有用的被鍍覆基材，效率佳地形成良好的無電鎳鍍覆膜。 In view of the technical background as described above, the problem to be solved by the present invention is to provide a method for providing a sufficient catalyst adsorption amount without going through a complicated two-step process, and using cheap silver and copper particles as a catalyst, Using hypophosphite as a reducing agent, it is effective to form a good electroless nickel plating film on a substrate to be plated which is useful for resin, glass, ceramics, and the like.

本發明人等，為了解決上述課題而反覆銳意研究的結果，關於特徵為將附著有「包含銀粒子、銅粒子中任一種、或銀與銅的混合粒子的金屬粒子」與「特定的高分子」之複合體的被鍍覆基材，浸漬於含有水溶性鎳鹽、還原劑、及錯合劑的無電鎳鍍覆液，而在被鍍覆基材(S)上形成鎳的膜的無電鎳鍍覆方法，發現藉由使前述無電鎳鍍覆液中存在從鎳、鐵、鈷所選出的一種固體金屬而提升次磷酸還原系中無電鎳鍍覆的析出性，進而完成本發明。 As a result of intensive research to solve the above-mentioned problems, the inventors of the present invention are characterized in that "metal particles containing any one of silver particles, copper particles, or mixed particles of silver and copper" and "specific polymers The electroplated base material of the composite body is impregnated with an electroless nickel plating solution containing a water-soluble nickel salt, a reducing agent, and a complexing agent, and electroless nickel that forms a film of nickel on the plated base material (S). The plating method found that the presence of a solid metal selected from nickel, iron, and cobalt in the electroless nickel plating solution improves the precipitation of electroless nickel plating in the hypophosphorous acid reduction system, and completed the present invention.

即，本發明提供一種無電鎳鍍覆方法，其係將附著有複合體(C)的被鍍覆基材(S)浸漬於含有水溶性鎳鹽、還原劑、與錯合劑的無電鎳鍍覆液，而在被鍍覆基材(S)上形成鎳的膜之無電鎳鍍覆方法，其中該複合體(C)為金屬粒子(M)與高分子(P)之複合體，該金屬粒子(M)包含銀粒子、銅粒子、或銀與銅的混合粒子，其特徵為：前述高分子(P)為化合物(P1)或化合物(P2)，該化合物(P1)為含有(甲基)丙烯酸系單體的單體混合物(I)的聚合物，該(甲基)丙烯酸系單體具有從包含羧基、磷酸基、亞磷酸基、磺酸基、亞磺酸基及次磺酸基的群組所選出的一種以上的陰離子性官能基，該化合物(P2)為分子內具有聚伸乙基亞胺嵌段、聚伸丙基亞胺嵌段、聚烯丙胺嵌段中的任一種以上的化合物；前述還原劑為次磷酸或其鹽；在將前述被鍍覆基材(S)浸漬於前述無電鍍覆液之際，使該鍍覆液中存在從包含鎳、鐵及鈷的群組所選出的一種以上的固體金屬。 That is, the present invention provides an electroless nickel plating method in which a substrate to be plated (S) to which a composite (C) is adhered is immersed in an electroless nickel plating containing a water-soluble nickel salt, a reducing agent, and a complexing agent. Electroless nickel plating method for forming a film of nickel on a substrate (S) to be plated, wherein the composite (C) is a composite of metal particles (M) and a polymer (P), and the metal particles (M) silver particles, copper particles, or mixed particles of silver and copper, characterized in that the polymer (P) is a compound (P1) or a compound (P2), and the compound (P1) contains (methyl) A polymer of a monomer mixture (I) of an acrylic monomer having a group including a carboxyl group, a phosphate group, a phosphite group, a sulfonate group, a sulfinate group, and a sulfinate group. One or more anionic functional groups selected by the group, and the compound (P2) has any one or more of a poly (ethyleneimine) block, a poly (propyleneimine) block, and a polyallylamine block in the molecule The compound; the reducing agent is hypophosphorous acid or a salt thereof; and when the substrate to be plated (S) is immersed in the electroless plating solution, the plating solution is There is more than one solid metal from the group comprising nickel, iron and cobalt is selected.

本發明的無電鎳鍍覆方法，係使用附著有「包含銀粒子、銅粒子中任一種、或銀與銅的混合粒子的金屬粒子(M)」與「高分子(P)」之複合體的基材作為被鍍覆基材(S)。藉由使用這樣的特定構造的高分子(P)與金屬粒子(M)的複合體(C)，可將金屬粒子(M)穩定且均勻地賦予至基材上，因此可藉由簡便的方法在被鍍覆基材(S)上均勻地形成無電鎳鍍覆被膜。 The electroless nickel plating method of the present invention is a method in which a composite of "metal particles (M) containing any of silver particles, copper particles, or mixed particles of silver and copper" and "polymer (P)" is used. The base material was used as a base material to be plated (S). By using the composite (C) of the polymer (P) and the metal particles (M) having such a specific structure, the metal particles (M) can be stably and uniformly applied to the substrate, and therefore, a simple method can be used. An electroless nickel plating film was uniformly formed on the plated substrate (S).

又，藉由在從鎳、鐵、鈷所選出的一種固體金屬存在下進行無電鎳鍍覆，而鍍覆析出性提升，可效率佳地實施鍍覆處理。 In addition, by performing electroless nickel plating in the presence of a solid metal selected from nickel, iron, and cobalt, the plating precipitation is improved, and the plating treatment can be performed efficiently.

再者，在本發明的無電鎳鍍覆方法中，藉由使用比鈀便宜且價格變動風險小的金屬之銀、銅中任一種、或銀與銅的混合金屬粒子(M)，可期待更高的經濟性，又，可由以往所使用的無電鎳鍍覆步驟減少步驟數量，因此製程成本也可大幅減低。 Furthermore, in the electroless nickel plating method of the present invention, by using any one of silver, copper, or a mixed metal particle (M) of silver and copper, which is a metal that is cheaper than palladium and has a low risk of price fluctuation, it is expected that High economy, and the number of steps can be reduced by the conventional electroless nickel plating step, so the process cost can also be greatly reduced.

用以實施發明的形態A form for implementing the invention [金屬粒子(M)與高分子(P)的複合體(C)]     [Compound (C) of metal particles (M) and polymer (P)]     [金屬粒子(M)]     [Metal particles (M)]    

作為本發明中使用的金屬粒子(M)，可適合使用銀、銅，可單獨使用這些金屬種，也可使銀、銅混合存在，又，也可為銀與銅的合金。在銀與銅混合存在的情況下，銀與銅的粒子可各自個別地存在，也可以銀芯-銅殼、或銅芯-銀殼的形態存在。 As the metal particles (M) used in the present invention, silver and copper can be suitably used. These metal species can be used alone, silver and copper can be mixed, and an alloy of silver and copper can also be used. When silver and copper are mixed, the silver and copper particles may exist individually, and may exist in the form of a silver core-copper shell or a copper core-silver shell.

[與金屬粒子(M)形成複合體的高分子(P)]     [Polymer (P) forming a complex with metal particles (M)]    

在本發明中，與金屬粒子(M)形成複合體的高分子(P)係具有下述特徵的化合物：抑制金屬粒子(M) 的凝集、熔合，確保複合體(C)在水性媒體中的分散穩定性，同時具有利用起因於構造中的官能基的電荷、反應性而提高對各種基材的吸附及接著性的功能。 In the present invention, the polymer (P) that forms a complex with the metal particles (M) is a compound having the following characteristics: inhibits the aggregation and fusion of the metal particles (M), and ensures the complex (C) in the aqueous medium Dispersion stability has the function of improving the adsorption and adhesion to various substrates by utilizing the charge and reactivity of functional groups in the structure.

高分子(P1)：本發明中使用的與金屬粒子(M)形成複合體(C)的高分子(P)之一形態(P1)為將單體混合物(I)進行聚合而成的化合物，該單體混合物(I)含有具有從包含羧基、磷酸基、亞磷酸基、磺酸基、亞磺酸基及次磺酸基的群組所選出的一種以上的陰離子性官能基的(甲基)丙烯酸系單體，即具有丙烯醯基或甲基丙烯醯基的聚合性單體。 Polymer (P1): One form (P1) of the polymer (P) that forms the complex (C) with the metal particles (M) used in the present invention is a compound obtained by polymerizing the monomer mixture (I), This monomer mixture (I) contains a (methyl group) having one or more anionic functional groups selected from the group consisting of a carboxyl group, a phosphate group, a phosphite group, a sulfonic acid group, a sulfinic acid group, and a sulfinic acid group. ) Acrylic monomer, that is, a polymerizable monomer having an acrylfluorene group or a methacrylfluorene group.

前述羧基、磷酸基、亞磷酸基、磺酸基、亞磺酸基、次磺酸基，具有透過雜原子所具有的未共用電子對而吸附於前述金屬粒子(M)的功能，同時對金屬粒子(M)表面賦予負電荷，因此可藉由粒子間的電荷排斥來防止膠體粒子的凝集，可使高分子(P1)與金屬粒子(M)的複合體(C)穩定地分散於水系溶媒中。 The carboxyl group, phosphate group, phosphite group, sulfonate group, sulfinate group, and sulfenyl group have the function of adsorbing the metal particles (M) through the unshared electron pair possessed by the hetero atom, and simultaneously The surface of the particle (M) is given a negative charge, so the agglomeration of colloidal particles can be prevented by the charge repulsion between the particles, and the complex (C) of the polymer (P1) and the metal particles (M) can be stably dispersed in the aqueous solvent in.

作為將前述陰離子性官能基導入本發明中使用的高分子(P1)的方法，只要為使將具有這些官能基的(甲基)丙烯酸系單體作為必要成分的單體混合物(I)進行聚合的方法即可，特佳為使包含(甲基)丙烯酸系單體的單體混合物進行聚合。 As a method for introducing the anionic functional group into the polymer (P1) used in the present invention, it is sufficient to polymerize a monomer mixture (I) using (meth) acrylic monomers having these functional groups as an essential component. The method is sufficient, and it is particularly preferable to polymerize a monomer mixture containing a (meth) acrylic monomer.

例如，導入有羧基的化合物(X)可藉由(甲基)丙烯酸的均聚合、或使其與其他(甲基)丙烯酸系單體的混合物以各種方法進行共聚合而容易地得到。同樣地，導入有磷酸基、亞磷酸基的高分子(P1)可藉由將具 有磷酸基的(甲基)丙烯酸系單體作為必要成分，使其進行均聚合、或者調製其與其他單體的混合物並使該混合物共聚合而容易地得到。再者，將磺酸基、亞磺酸基、次磺酸基導入高分子(P1)的情況也相同，只要將含有具有磺酸基的(甲基)丙烯酸系單體的單體類進行聚合即可。 For example, the compound (X) having a carboxyl group introduced can be easily obtained by homopolymerizing (meth) acrylic acid or copolymerizing a mixture with other (meth) acrylic monomers by various methods. Similarly, in the polymer (P1) into which a phosphate group and a phosphite group have been introduced, a (meth) acrylic monomer having a phosphate group can be used as an essential component to homopolymerize it, or prepare it with other monomers. It is easily obtained by copolymerizing the mixture. The same applies to the case where the sulfonic acid group, sulfinic acid group, and sulfinic acid group are introduced into the polymer (P1), as long as the monomers containing a (meth) acrylic monomer having a sulfonic acid group are polymerized. Just fine.

與金屬粒子(M)形成複合體(C)的高分子(P1)可為均聚物也可為共聚物，特別是，也可為具有複數種前述的陰離子性官能基的共聚物。共聚合形式沒有特別的限定，無規或嵌段中的任一者均可較佳地使用。又，也可將具有不同的陰離子性官能基的兩種類以上的高分子(P1)混合使用。 The polymer (P1) forming a complex (C) with the metal particles (M) may be a homopolymer or a copolymer, and in particular, may be a copolymer having a plurality of the aforementioned anionic functional groups. The copolymerization form is not particularly limited, and either a random or a block can be preferably used. Further, two or more types of polymers (P1) having different anionic functional groups may be used in combination.

作為前述高分子(P1)中之前述特定的陰離子性官能基的導入量，沒有特別的限定，從對金屬(M)之粒子的吸附與製成分散體時的穩定性的觀點來看，較佳為一分子中包含三個以上。 The introduction amount of the specific anionic functional group in the polymer (P1) is not particularly limited. From the viewpoints of adsorption of particles of the metal (M) and stability when the dispersion is made, Preferably, there are more than three in one molecule.

作為高分子(P1)的質量平均分子量，沒有特別的限定，如前所述，從作為與金屬(M)的粒子之複合體(C)的無電鍍覆觸媒的效果(對基板的吸附、製成分散液時的分散穩定性等)的觀點來看，較佳為3,000~20,000，更佳為4,000~8,000。 The mass average molecular weight of the polymer (P1) is not particularly limited. As described above, the effect of the electroless plating catalyst as a composite (C) with particles of the metal (M) (adhesion to the substrate, From the viewpoint of dispersion stability when preparing a dispersion, etc.), it is preferably 3,000 to 20,000, and more preferably 4,000 to 8,000.

又，若在前述高分子(P1)分子中併入藉由在媒體中以適當的體積擴展而表現分散穩定化的聚乙二醇鏈、聚伸烷基鏈等，則在表現由電荷所帶來的斥力的同時，可利用由立體排斥效果所帶來的膠體保護作用，因而較佳。 In addition, if the polymer (P1) molecule incorporates a polyethylene glycol chain, a polyalkylene chain, or the like that exhibits dispersion and stabilization by expanding in the medium with an appropriate volume, it is expressed by the charge At the same time, the colloidal protection effect brought by the three-dimensional repulsion effect can be used at the same time, so it is better.

作為此之例，可藉由使前述單體混合物(I)含有具有聚乙二醇鏈的(甲基)丙烯酸系單體，並與前述的(甲基)丙烯酸、具有磷酸基的(甲基)丙烯酸、具有磺酸基的(甲基)丙烯酸等進行共聚合而容易地得到。 As such an example, the monomer mixture (I) may contain a (meth) acrylic monomer having a polyethylene glycol chain, and be combined with the (meth) acrylic acid and (meth) ) Acrylic acid, (meth) acrylic acid having a sulfonic acid group, and the like are easily obtained by copolymerization.

特別是使用具有乙二醇的平均單元數為20以上的聚乙二醇鏈之(甲基)丙烯酸系單體進行聚合而成的化合物之具有陰離子性官能基的高分子(P1)，其將貴金屬，特別是銀、銅的奈米粒子穩定化的能力高，成為合適的保護劑，為較佳者。這樣的具有陰離子性官能基與聚乙二醇鏈的化合物之合成等，可藉由參照例如日本專利第4697356號公報、日本特開2010-209421號公報等而容易地得到。 In particular, the polymer (P1) having an anionic functional group is a compound obtained by polymerizing a (meth) acrylic monomer having a polyethylene glycol chain having an average number of ethylene glycol units of 20 or more. Nanoparticles of noble metals, especially silver and copper, have a high ability to stabilize and are suitable protective agents, and are preferred. The synthesis of a compound having such an anionic functional group and a polyethylene glycol chain can be easily obtained by referring to, for example, Japanese Patent No. 4697356, Japanese Patent Laid-Open No. 2010-209421, and the like.

作為前述的具有乙二醇的平均單元數為20以上的聚乙二醇鏈之(甲基)丙烯酸系單體的質量平均分子量，較佳為1,000~2,000。若質量平均分子量在此範圍內，則與金屬(M)的粒子之複合體(C)的水分散性變得更良好。對於質量平均分子量超過2,000者，現狀而言由於市售品少，因此變得難以取得便宜的原料。 The mass average molecular weight of the (meth) acrylic monomer having a polyethylene glycol chain having an average number of ethylene glycol units of 20 or more is preferably 1,000 to 2,000. When the mass average molecular weight is within this range, the water dispersibility of the composite (C) with the particles of the metal (M) becomes better. If the mass average molecular weight exceeds 2,000, there are few commercially available products, and it is difficult to obtain cheap raw materials.

例如，可藉由以任意的聚合起始劑(例如，油溶性偶氮聚合起始劑「V-59」)使市售的2-甲基丙烯醯氧基磷酸酯(例如，共榮社化學製「Light Ester P-1M」)、與市售的具有聚乙二醇鏈的甲基丙烯酸酯單體(例如，日油製「Blemmer PME-1000」)進行共聚合而得到。 For example, a commercially available 2-methacryloxyphosphate (for example, Kyoeisha Chemical Co., Ltd.) can be used with any polymerization initiator (for example, an oil-soluble azo polymerization initiator "V-59"). "Light Ester P-1M", and copolymerized with a commercially available methacrylate monomer having a polyethylene glycol chain (for example, "Blemmer PME-1000" manufactured by Nippon Oil).

此時，若使具有磷酸基的(甲基)丙烯酸酯單體的質量分率相對於單體混合物(I)小於40質量%，則 抑制與金屬(M)的粒子的保護無關之具有聚乙二醇鏈的(甲基)丙烯酸系單體的均聚物等之副產物的產生，由所得到的高分子(P1)所帶來的分散穩定性提升。 At this time, if the mass fraction of the (meth) acrylic acid ester monomer having a phosphoric acid group is less than 40% by mass relative to the monomer mixture (I), it is possible to suppress polyethylene having no relation to the protection of particles of the metal (M) The production of by-products such as homopolymers of diol chain (meth) acrylic monomers improves dispersion stability due to the obtained polymer (P1).

前述單體混合物(I)可包含除了具有陰離子性基的(甲基)丙烯酸系單體、具有聚乙二醇鏈的(甲基)丙烯酸系單體以外的第3聚合性單體。此時，為了保證良好的水分散性，第3聚合性單體為疏水性單體的情況之質量分率係相對於具有聚乙二醇鏈的(甲基)丙烯酸系單體較佳為20質量%以下，更佳為10質量%以下。第3聚合性單體並非疏水性單體的情況則不限於此範圍。 The monomer mixture (I) may include a third polymerizable monomer other than the (meth) acrylic monomer having an anionic group and the (meth) acrylic monomer having a polyethylene glycol chain. In this case, in order to ensure good water dispersibility, the mass fraction when the third polymerizable monomer is a hydrophobic monomer is preferably 20 relative to the (meth) acrylic monomer having a polyethylene glycol chain. Mass% or less, more preferably 10 mass% or less. When the third polymerizable monomer is not a hydrophobic monomer, it is not limited to this range.

如前所述，高分子(P1)的質量平均分子量較佳為在3,000~20,000的範圍內，但在併用具有聚乙二醇鏈的(甲基)丙烯酸系單體的情況下，藉由聚合反應所得到的高分子(P1)變得具有分子量分布。由於質量平均分子量越小，越不包含源自具有聚乙二醇鏈的(甲基)丙烯酸系單體的構造，因此對於將與金屬粒子(M)的複合體(C)分散於水性媒體的情況之分散穩定性沒有貢獻，因此，從此觀點來看，高分子(P1)的質量平均分子量變得更佳為4,000以上。相反地，從若質量平均分子量變大，則容易引起與金屬粒子(M)的複合體(C)的粗大化，觸媒液體中變得容易產生沉澱的觀點來看，高分子(P1)的質量平均分子量更佳為8,000以下。 As described above, the mass average molecular weight of the polymer (P1) is preferably in the range of 3,000 to 20,000. However, when a (meth) acrylic monomer having a polyethylene glycol chain is used in combination, the polymer is polymerized by polymerization. The polymer (P1) obtained by the reaction has a molecular weight distribution. The smaller the mass-average molecular weight, the less the structure derived from the (meth) acrylic monomer having a polyethylene glycol chain. Therefore, it is important to disperse the composite (C) with the metal particles (M) in an aqueous medium. In this case, the dispersion stability does not contribute. Therefore, from this viewpoint, the mass average molecular weight of the polymer (P1) is more preferably 4,000 or more. On the contrary, if the mass average molecular weight becomes large, coarsening of the complex (C) with the metal particles (M) tends to occur, and the precipitation of the catalyst liquid tends to occur. The mass average molecular weight is more preferably 8,000 or less.

為了將前述高分子(P1)的質量平均分子量調整在上述的範圍內，可使用周知文獻，例如日本特開2010-209421號公報等中記載的鏈轉移劑，也可不使用鏈轉移劑而藉由聚合條件進行控制。 In order to adjust the mass average molecular weight of the polymer (P1) within the above-mentioned range, a chain transfer agent described in a well-known document such as Japanese Patent Application Laid-Open No. 2010-209421 may be used, or the chain transfer agent may be used without using a chain transfer agent. The polymerization conditions are controlled.

高分子(P2)：本發明中使用的與金屬粒子(M)形成複合體(C)的高分子(P)之另一形態(P2)為分子內具有聚伸乙基亞胺嵌段、聚伸丙基亞胺嵌段、聚烯丙胺嵌段中的任一者以上的化合物，此等當中，從取得的容易性的觀點來看，可特別適合使用具有聚伸乙基亞胺嵌段的化合物。 Polymer (P2): Another form (P2) of the polymer (P) that forms a complex (C) with the metal particles (M) used in the present invention is a polyethylenimine block in a molecule, a polymer Among the compounds of any one or more of the propyleneimine block and the polyallylamine block, among these, from the standpoint of easiness of obtaining, it is particularly suitable to use a compound having a polyethylenimine block. Compound.

形成前述複合體(C)的高分子(P2)當中，若具有聚伸乙基亞胺嵌段的化合物進一步具有聚乙二醇嵌段，則可提高與前述金屬粒子(M)的複合體(C)之在溶媒中的分散穩定性，可特別適合使用。 Among the polymers (P2) forming the composite (C), if the compound having a polyethyleneimine block further has a polyethylene glycol block, the composite (with the metal particles (M) can be improved ( C) The dispersion stability in a solvent is particularly suitable for use.

前述具有聚伸乙基亞胺嵌段與聚乙二醇嵌段的化合物(高分子(P2))，例如，可藉由將市售的聚乙二醇的末端羥基衍生為活性基，使其與市售的聚伸乙基亞胺進行化學鍵結而得到，可特別適合使用數量平均分子量為500~5,000的聚乙二醇鍵結於數量平均分子量為500~50,000的聚伸乙基亞胺中的胺基而成的化合物。本發明中使用的化合物(P2)具有聚伸乙基亞胺嵌段與聚乙二醇嵌段，也可進一步導入其他構造。 The compound (Polymer (P2)) having a polyethyleneimine block and a polyethylene glycol block, for example, can be obtained by deriving a terminal hydroxyl group of a commercially available polyethylene glycol as an active group, It is obtained by chemically bonding with commercially available polyethylenimine, and it is particularly suitable to use polyethylene glycol having a number average molecular weight of 500 to 5,000 to bond to polyethylenimine having a number average molecular weight of 500 to 50,000. Amino compounds. The compound (P2) used in the present invention has a polyethyleneimine block and a polyethylene glycol block, and other structures may be introduced.

[金屬粒子(M)與高分子(P)的複合體(C)]     [Compound (C) of metal particles (M) and polymer (P)]    

本發明中使用的金屬粒子(M)與有機保護劑(P)的複合體(C)係指「銀、銅、銀與銅的合金、銀芯-銅殼、或銅芯-銀殼的粒子」與「前述高分子(P)」之複合體，在本發明的無電鎳鍍覆方法中，使用使此複合體(C)附著在各種基材上者作為被鍍覆基材(S)。 The composite (C) of the metal particles (M) and the organic protective agent (P) used in the present invention refers to "silver, copper, an alloy of silver and copper, silver core-copper shell, or copper core-silver shell particles In the electroless nickel plating method of the present invention, the composite of "" and "the aforementioned polymer (P)" uses the composite (C) adhered to various substrates as the substrate to be plated (S).

金屬粒子(M)與高分子(P)的複合化，可在前述高分子(P)存在下製造金屬粒子(M)而進行複合化，也可在製造金屬粒子(M)後，添加高分子(P)而進行複合化。例如，可將使用低真空氣體中的蒸發法等之氣相法製造的金屬粒子(M)在溶媒中與高分子(P)進行複合化，也可在液相中、在高分子(P)存在下，將金屬化合物還原而合成金屬粒子(M)，使其複合化。氣相、液相法皆可因應需要，適宜地藉由溶媒交換、溶媒添加來變更複合化時的分散溶媒與塗布時的分散溶媒的溶劑組成。氣相、液相法當中，從複合體(C)的分散液的穩定性、製造步驟的簡便性來看，可特別適合使用液相法。 The composite of the metal particles (M) and the polymer (P) may be performed by producing the metal particles (M) in the presence of the polymer (P), or may be added after the production of the metal particles (M). (P). For example, the metal particles (M) produced by a gas phase method such as the evaporation method in a low vacuum gas can be compounded with a polymer (P) in a solvent, or in a liquid phase or a polymer (P). In the presence of this, a metal compound is reduced to synthesize metal particles (M) and complex them. Both the gas-phase and liquid-phase methods can appropriately change the solvent composition of the dispersing solvent at the time of compounding and the dispersing solvent at the time of coating by solvent exchange or solvent addition. Among the gas-phase and liquid-phase methods, the liquid-phase method can be particularly suitably used from the viewpoint of the stability of the dispersion of the composite (C) and the simplicity of the production steps.

作為使金屬粒子(M)分散的溶媒，若為可使金屬粒子(M)穩定地分散，在使金屬粒子(M)分散的狀態下對實施無電鎳鍍覆的目的之基材的潤濕性良好，且可在該基材上形成液膜的溶媒，則沒有特別的限制，可使用各種溶媒，可為水、水與水溶性的有機溶媒的混合溶媒、不含水的有機溶媒中的任一者，在將後述的被鍍覆基材(S)的製造作為鍍覆步驟的一連串步驟而實施的情況下，較佳為使用水系溶媒，即水、或水與水溶性的有機溶媒的混合溶媒。 As a solvent for dispersing the metal particles (M), if the metal particles (M) are stably dispersed, the wettability of the substrate for the purpose of performing electroless nickel plating in a state where the metal particles (M) are dispersed Good, and a solvent capable of forming a liquid film on the substrate is not particularly limited. Various solvents can be used, and any of water, a mixed solvent of water and a water-soluble organic solvent, or a non-aqueous organic solvent can be used. In the case where the production of a substrate to be plated (S) described later is carried out as a series of plating steps, it is preferable to use an aqueous solvent, that is, water or a mixed solvent of water and a water-soluble organic solvent. .

作為使前述複合體(C)分散之可與水混合的水溶性的溶媒，例如，可舉出：甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、三級丁醇等醇類、丙酮、2-丁酮等酮類、乙二醇、甘油等多元醇或其他酯類、乙二醇單乙基醚、乙二醇二甲基醚、二乙二醇單丁基醚、二 乙二醇二甲基醚、丙二醇甲基醚乙酸酯、丁基二乙二醇乙酸酯等二醇醚類，可將這些溶媒單獨使用或混合複數種使用。 Examples of the water-miscible solvent in which the complex (C) is dispersed include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol. Other alcohols, ketones such as acetone, 2-butanone, polyols such as ethylene glycol, glycerol, or other esters, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monobutyl Glycol ethers, such as ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, and butyl diethylene glycol acetate, may be used alone or in combination.

又，作為使前述複合體(C)分散的前述有機溶媒，可舉出前述的可與水混合的水溶性的溶媒，例如，甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、三級丁醇等醇類、丙酮、2-丁酮等酮類、乙二醇、甘油等多元醇或其他酯類、乙二醇單乙基醚、乙二醇二甲基醚、二乙二醇單丁基醚、二乙二醇二甲基醚、丙二醇甲基醚乙酸酯、丁基二乙二醇乙酸酯等二醇醚類，只要不混合水而將這些溶媒單獨使用或混合複數種使用即可。在此情況下，有因吸濕等而稍微含有水的情形，但並非有意與水混合，因此，在本發明中係作為不含水的有機溶媒來操作。 Examples of the organic solvent in which the complex (C) is dispersed include the water-soluble solvents that can be mixed with water, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isopropyl alcohol. Alcohols such as butanol and tertiary butanol, ketones such as acetone, 2-butanone, polyhydric alcohols such as ethylene glycol, glycerol or other esters, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, Glycol ethers such as diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, and butyl diethylene glycol acetate, as long as these solvents are not mixed with water, Use or mix multiple types. In this case, water may be contained slightly due to moisture absorption or the like, but it is not intentionally mixed with water. Therefore, in the present invention, it is handled as a non-aqueous organic solvent.

作為液相法中的金屬粒子(M)與高分子(P)的複合體(C)的製造法，使前述高分子(P)溶解或分散於水性媒體後，對其添加金屬化合物，例如硝酸銀、乙酸銅等，因應需要併用錯合劑而製成均勻的分散體後、或者與錯合劑同時，藉由混合還原劑，可將這些金屬化合物還原，在被還原的金屬成為奈米尺寸粒子(具有奈米等級的大小的微粒子)的同時，得到與前述高分子(P)複合而成的金屬粒子(M)的複合體(C)的水系分散體。 As a method for producing a composite (C) of metal particles (M) and a polymer (P) in a liquid phase method, after dissolving or dispersing the polymer (P) in an aqueous medium, a metal compound such as silver nitrate is added thereto. And copper acetate, etc., can be made into a homogeneous dispersion by using a complexing agent in combination with the complexing agent, or at the same time as the complexing agent, by mixing a reducing agent, these metal compounds can be reduced, and the reduced metal becomes nano-sized particles (with Nano-sized particles), and an aqueous dispersion of a composite (C) of metal particles (M), which is compounded with the polymer (P).

液相法中，作為可用於製造複合體(C)的分散液的情況的金屬化合物，例如，在金屬種為銀的情況下，可使用硝酸銀、氧化銀、乙酸銀、氯化銀、硫化銀 等，在製成水溶液而操作的情況下，在溶解度方面上，較佳為硝酸銀，在金屬種為銅的情況下，除了Cu(OAc)2、Cu(NO3)2、CuCl2、Cu(HCOO)2、Cu(CH3COO)2、Cu(CH3CH2COO)2、CuCO3、CuSO4、C5H7CuO2以外，也可同樣地使用將羧酸鹽加熱所得到的鹼性鹽，例如Cu(OAc)2‧CuO。 In the liquid phase method, as the metal compound that can be used in the production of a dispersion of the composite (C), for example, when the metal species is silver, silver nitrate, silver oxide, silver acetate, silver chloride, and silver sulfide can be used For example, when operating as an aqueous solution, silver nitrate is preferred in terms of solubility. When the metal species is copper, in addition to Cu (OAc) 2 , Cu (NO 3 ) 2 , CuCl 2 , Cu ( HCOO) 2 , Cu (CH 3 COO) 2 , Cu (CH 3 CH 2 COO) 2 , CuCO 3 , CuSO 4 , C 5 H 7 CuO 2 can be used in the same manner as the base obtained by heating the carboxylate Alkaline salts, such as Cu (OAc) 2 ‧CuO.

在本發明的無電鎳鍍覆方法中，使用藉由這樣的方法所得到的附著有包含金屬粒子(M)的複合體(C)的被鍍覆基材(S)，但在製造此被鍍覆基材(S)之際，可直接使用前述的複合體(C)的水系分散體，或者，也可使用將剩餘的錯合劑、還原劑、或用作原料的金屬化合物中所含的相對離子等，經過將超過濾法或沉澱法、離心分離、減壓蒸餾、減壓乾燥等各種精製法單獨或組合兩種以上而進行的精製步驟者；將其進一步變更濃度(不揮發成分)或水系媒體而重新調製成分散體者等。在以電子電路形成等組裝用途為目的而使用的情況下，較佳為使用經過前述的精製步驟的水系媒體。 In the electroless nickel plating method of the present invention, a substrate to be plated (S) to which a composite (C) containing metal particles (M) is adhered is used, but the plated substrate is produced here. In the case of coating the substrate (S), the above-mentioned aqueous dispersion of the composite (C) may be used as it is, or a relative compound contained in the remaining complexing agent, reducing agent, or metal compound used as a raw material may be used. Ions, etc., are subjected to a purification step in which various purification methods such as ultrafiltration or precipitation, centrifugal separation, vacuum distillation, and vacuum drying are used alone or in combination of two or more types; the concentration (non-volatile content) or Those who reconstitute the dispersion in aqueous media. When it is used for the purpose of assembly, such as formation of an electronic circuit, it is preferable to use the aqueous medium which went through the said purification process.

前述金屬粒子(M)與高分子(P)的複合體(C)係以前述高分子(P)、與平均粒徑較佳在0.5~100nm範圍內的金屬粒子(M)為成分者。 The composite (C) of the metal particles (M) and the polymer (P) is composed of the polymer (P) and metal particles (M) having an average particle diameter preferably in a range of 0.5 to 100 nm.

在本發明中，金屬粒子(M)可藉由透射型電子顯微鏡照片估計其大小，其100個的平均值在0.5~100nm範圍內者，例如，高分子(P1)與金屬粒子(M)的複合體(C)可藉由按照前述的日本專利第4697356號公報、日本特開2010-209421號公報等的方法而容易地得 到。又，有機保護劑(P2)與金屬(M)的粒子的複合體(C)可使用日本特開2008-037884號公報、日本特開2008-037949號公報、日本特開2008-03818號公報、日本特開2010-007124號公報中記載的方法來製造。 In the present invention, the size of the metal particles (M) can be estimated from a transmission electron microscope photograph, and the average value of 100 of them is in the range of 0.5 to 100 nm. For example, the polymer (P1) and the metal particles (M) The composite (C) can be easily obtained by a method according to the aforementioned Japanese Patent No. 4697356, Japanese Patent Laid-Open No. 2010-209421, and the like. As the composite (C) of the organic protective agent (P2) and the particles of the metal (M), Japanese Patent Application Laid-Open No. 2008-037884, Japanese Patent Application Laid-Open No. 2008-037949, Japanese Patent Application Laid-Open No. 2008-03818 can be used, It is manufactured by the method described in Japanese Patent Application Laid-Open No. 2010-007124.

前述金屬粒子(M)的粒徑可根據金屬化合物的種類、成為膠體保護劑的前述高分子(P)的分子量、或化學構造、其使用比例、錯合劑或還原劑的種類或其用量、還原反應時的溫度等而容易地控制，對於此等，只要參照前述專利文獻等中的實施例即可。 The particle diameter of the metal particles (M) can be determined according to the type of the metal compound, the molecular weight of the polymer (P) serving as a colloid protective agent, or the chemical structure, the proportion of its use, the type of the complexing agent or the reducing agent, the amount of the reducing agent, and the reduction. The temperature and the like at the time of the reaction can be easily controlled. For these, it is sufficient to refer to the examples in the aforementioned patent documents and the like.

作為前述高分子(P)與金屬粒子(M)的複合體(C)中的前述高分子(P)的含有比率，從使複合體(C)在水性媒體中穩定地分散的觀點來看，在複合體中較佳為1~30質量%，為1~20質量%則適合在之後的無電鎳鍍覆步驟中形成均勻且穩定的鍍覆金屬膜。即，在複合體(C)中，較佳為金屬粒子(M)佔其質量的大部分者。 As a content ratio of the polymer (P) in the composite (C) of the polymer (P) and the metal particles (M), from the viewpoint of stably dispersing the composite (C) in an aqueous medium, The composite is preferably 1 to 30% by mass, and 1 to 20% by mass is suitable for forming a uniform and stable plated metal film in a subsequent electroless nickel plating step. That is, in the composite (C), it is preferable that the metal particles (M) account for most of its mass.

[被鍍覆基材(S)]     [Substrate to be plated (S)]    

本發明中使用的被鍍覆基材(S)係使前述「包含銀粒子、銅粒子中任一種、或銀與銅的混合粒子的金屬粒子(M)」與「高分子(P)」之複合體附著於其表面的基材，作為基材種類，可適合使用導電性基材、非導電性基材中任一者，只要因應目的而適宜選擇即可，又，也可為導電性部與非導電性部混合存在的基材。又，可使前述複合體(C)附著於基材表面整面，也可使其部分選擇性地附著。再者，在導電性部與非導電性部混合存在的基材中，可僅附著在導電性部，或者，也可僅附著在非導電性部。 The substrate to be plated (S) used in the present invention is one of the aforementioned "metal particles (M) containing any one of silver particles, copper particles, or mixed particles of silver and copper" and "polymer (P)" The substrate on which the composite is adhered to the surface may be any one of a conductive substrate and a non-conductive substrate as the substrate type, and may be selected as appropriate depending on the purpose, or may be a conductive portion. A substrate mixed with a non-conductive portion. Moreover, the said composite (C) can be made to adhere to the whole surface of a base material surface, and can also be made to adhere selectively to a part. Furthermore, the base material in which the conductive portion and the non-conductive portion are mixed may be attached only to the conductive portion, or may be attached only to the non-conductive portion.

作為附著有前述複合體(C)的導電性基材，例如，可使用包含銅、銀、金、鉑的基材。又，作為非導電性基材，係將樹脂、玻璃、陶瓷、金屬氧化物、紙、合成或天然纖維等材質中的一種或使其組合而成者，作為其形狀，可為板狀、薄膜狀、布狀、纖維狀、管狀、柱狀、球狀等中的任一者。 As the conductive substrate to which the composite (C) is adhered, for example, a substrate containing copper, silver, gold, and platinum can be used. In addition, as the non-conductive substrate, one of a combination of materials such as resin, glass, ceramics, metal oxides, paper, synthetic, or natural fibers, or a combination thereof may be used. The shape may be a plate shape or a film. Any one of a shape, a cloth shape, a fibrous shape, a tubular shape, a columnar shape, a spherical shape, and the like.

本發明的被鍍覆基材(S)，係前述的附著有前述複合體(C)的基材，係使前述「包含銀粒子、銅粒子中任一種、或銀與銅的混合粒子的金屬粒子(M)的粒子」與「高分子(P)」之複合體(C)附著於其表面的基材，作為使前述複合體(C)附著於基材上的方法，沒有特別的限制，可因應目的而使用周知慣用的方法。例如，可適合使用：將前述複合體(C)的分散液印刷或塗布在基材上，使複合體(C)附著在基材上的方法；使基材浸漬於前述複合體(C)的分散液而使複合體(C)吸附的方法。 The substrate (S) to be plated according to the present invention is the substrate to which the composite (C) is attached, and is a metal containing any one of silver particles, copper particles, or mixed particles of silver and copper. There is no particular limitation on the method of attaching the composite (C) to the substrate as a substrate on which the composite (C) of the particles (M) and "polymer (P)" adheres to the surface, Well-known methods can be used depending on the purpose. For example, a method of printing or coating the dispersion of the composite (C) on a substrate and attaching the composite (C) to the substrate can be suitably used; the substrate is immersed in the composite (C). A method for dispersing a liquid to adsorb the composite (C).

在本發明中，作為將前述複合體(C)的分散液印刷或塗布在基材上的方法，沒有特別的限制，只要根據使用的基材的形狀、尺寸、剛柔程度等而適宜選擇周知慣用的各種印刷.塗敷方法即可，具體而言，可舉出：凹版法、平版法、凹版平版(gravure offset)法、凸版法、凸版反轉法、柔版法、網版法、微觸(micro-contact)法、反轉法、氣動刮刀塗布機法、刮刀塗布機法、氣刀塗布機法、擠壓式塗布機法、含浸塗布機法、轉印輥塗布機法、接觸式塗布機(kiss coater)法、澆鑄塗布機法、噴霧塗布機法、噴墨法、模具(die)法、旋轉塗布機法、棒塗布機法等。 In the present invention, the method for printing or coating the dispersion of the composite (C) on a substrate is not particularly limited, as long as it is appropriately selected according to the shape, size, degree of rigidity, and flexibility of the substrate used Various conventional printing and coating methods may be used. Specific examples include a gravure method, a lithography method, a gravure offset method, a letterpress method, a letterpress inversion method, a flexographic method, a screen method, and a micro printing method. Micro-contact method, reversal method, pneumatic blade coater method, blade coater method, air knife coater method, extrusion coater method, immersion coater method, transfer roll coater method, contact type A coater method, a cast coater method, a spray coater method, an inkjet method, a die method, a spin coater method, a rod coater method, and the like.

在將前述複合體(C)分散液印刷或塗布在基材上，使前述複合體(C)附著在基材上，而製造本發明的被鍍覆基材(S)的情況下，將前述複合體(C)的分散液塗布在基材後，基材可藉由清洗操作來除去基材上的剩餘的複合體(C)，也可直接使用。又，可將塗布膜暫時乾燥，也可不經過乾燥步驟而直接作為被鍍覆基材(S)，用於無電鎳鍍覆。 When the composite (C) dispersion is printed or coated on a substrate, and the composite (C) is adhered to the substrate to produce the plated substrate (S) of the present invention, the foregoing is coated. After the dispersion of the composite (C) is applied to the substrate, the substrate can be cleaned to remove the remaining composite (C) from the substrate, or it can be used directly. In addition, the coating film may be temporarily dried, or may be directly used as a substrate to be plated (S) without being subjected to a drying step for electroless nickel plating.

在經過塗布膜的乾燥而形成被鍍覆基材(S)的情況下，塗布膜的乾燥可在室溫下進行，也可進行加熱乾燥。又，在乾燥時，可進行送風，也可不特意進行送風。對於送風，可輸送熱風，也可僅在室溫下進行送風。又，乾燥可在大氣中進行，也可在氮、氬等置換氣體環境或氣流下進行，亦可在真空下進行。又，也可在小於***下限濃度的氫氣環境下進行。 When the coated substrate (S) is formed by drying the coating film, the coating film may be dried at room temperature or may be dried by heating. In addition, the air may be blown during drying, or may be unintentionally blown. For the air supply, hot air can be delivered or air supply can be performed only at room temperature. In addition, drying may be performed in the air, or may be performed under a substitution gas environment such as nitrogen or argon, or under a gas flow, or may be performed under vacuum. It can also be carried out in a hydrogen environment with a concentration lower than the lower explosive limit.

塗布膜的乾燥，在基材形狀為單片的薄膜、薄片、板的情況下，除了在塗敷場所的自然乾燥以外，也可在送風、定溫乾燥器等的乾燥器內進行。又，在基材形狀為軌製薄片(rolled sheet)的情況下，可接著前述印刷.塗布步驟，在所設置的非加熱或加熱空間內使軌製薄片連續地移動，藉此進行乾燥。 In the case of a single-layer film, sheet, or board, the coating film may be dried in a dryer such as a blower or a constant-temperature dryer, in addition to natural drying at a coating place. When the shape of the base material is a rolled sheet, the printing or coating step may be followed, and the rail-shaped sheet may be continuously moved in a non-heated or heated space to be installed, thereby drying.

在本發明中，製造附著有前述複合體(C)的被鍍覆基材(S)的步驟，可在與無電鎳鍍覆步驟不同的步驟中預先準備，也可作為無電鎳鍍覆步驟的一連串步驟而實施。 In the present invention, the step of manufacturing the plated substrate (S) to which the aforementioned composite (C) is attached may be prepared in advance in a step different from the electroless nickel plating step, or may be used as a step in the electroless nickel plating step. A series of steps.

在作為無電鎳鍍覆步驟的一連串步驟而實施的情況下，前述複合體(C)可藉由使基材浸漬於複合體(C)的分散液的操作，而使複合體(C)附著在作為目的之基材上。 When implemented as a series of steps in the electroless nickel plating step, the composite (C) can be adhered to the composite (C) by the operation of immersing the substrate in the dispersion of the composite (C). As the target substrate.

在藉由浸漬來使複合體(C)附著在基材表面的情況下，以提升前述複合體(C)的附著量並使其穩定化為目的，可預先將陰離子性或陽離子性的化合物賦予至作為目的之基材表面。在本發明的無電鎳鍍覆方法中，藉由進行這樣的前處理，而可藉由利用前述複合體(C)之高分子(P)所具有的電荷之靜電相互作用，在作為目的之基材上達成均勻且穩定的複合體(C)的附著。 When the composite (C) is adhered to the surface of the substrate by immersion, an anionic or cationic compound may be provided in advance for the purpose of increasing and stabilizing the adhesion amount of the composite (C). To the surface of the substrate for the purpose. In the electroless nickel plating method of the present invention, by performing such a pretreatment, the electrostatic interaction using the electric charge possessed by the polymer (P) of the composite (C) can be used as a basis for the purpose. A uniform and stable adhesion of the composite (C) to the material is achieved.

使用陰離子性或陽離子性化合物中的任一者，只要根據形成複合體(C)的高分子(P)的種類選擇即可，在使用前述高分子(P1)的情況下，由於其構造中具有陰離子性官能基，因此基材表面較佳為具有正電荷，較佳為使用陽離子性化合物進行處理。 The use of either an anionic or cationic compound may be selected according to the type of the polymer (P) forming the complex (C). When the polymer (P1) is used, it has a structure An anionic functional group, so the surface of the substrate preferably has a positive charge, and is preferably treated with a cationic compound.

作為用於此目的之陽離子性化合物，可使用各種陽離子性界面活性劑、或具有陽離子性的官能基(胺基、銨鹽)的化合物，作為前述陽離子性的化合物，例如，可適合使用：作為單烷基胺鹽(乙酸鹽)等高級烷基單胺鹽、N-烷基丙二胺二油酸鹽等烷基二胺鹽、烷基三甲基銨鹽(氯化物)等四級銨鹽等(烷基中的碳數為6~32，較佳為8~24左右)所市售的陽離子性界面活性劑；聚伸乙基亞胺、聚烯丙胺、聚烯丙胺鹽(鹽酸、硫酸)、聚烯丙胺鹽二烯丙胺鹽共聚物、聚苯胺等陽離子性聚合 物(就質量平均分子量而言為1,000~100,000左右，較佳為5000~20,000)。 As the cationic compound used for this purpose, various cationic surfactants or compounds having a cationic functional group (amine group, ammonium salt) can be used. As the aforementioned cationic compound, for example, it can be suitably used as: Higher alkyl monoamine salts such as monoalkylamine salts (acetate), alkyldiamine salts such as N-alkylpropanediamine dioleate, and quaternary ammonium salts such as alkyltrimethylammonium salt (chloride) Commercially available cationic surfactants (carbon number in the alkyl group is 6 to 32, preferably about 8 to 24); polyethylenimine, polyallylamine, polyallylamine salt (hydrochloric acid, Cationic polymers such as sulfuric acid), polyallylamine salt diallylamine salt copolymer, and polyaniline (about 1,000 to 100,000 in terms of mass average molecular weight, preferably 5,000 to 20,000).

這些陽離子性化合物，可在0.01~50g/L的範圍內溶解或分散於水性媒體中，更佳為0.1~20g/L。在使用難以在此範圍內均勻地溶解或分散的化合物的情況下，可併用與水相溶的有機溶劑。 These cationic compounds can be dissolved or dispersed in an aqueous medium in a range of 0.01 to 50 g / L, and more preferably 0.1 to 20 g / L. When a compound which is difficult to dissolve or disperse uniformly within this range is used, an organic solvent compatible with water can be used in combination.

在前述陽離子性化合物的水性溶液或水系分散液中，可使用硼酸、磷酸、氯化銨、氨、碳酸、乙酸等作為pH緩衝劑。pH緩衝劑的用量較佳為1~50g/L，更佳為1~20g/L。 In the aqueous solution or dispersion of the cationic compound, boric acid, phosphoric acid, ammonium chloride, ammonia, carbonic acid, acetic acid, or the like can be used as a pH buffer. The amount of the pH buffering agent is preferably 1 to 50 g / L, and more preferably 1 to 20 g / L.

作為以陽離子性化合物處理基材表面的方法，沒有特別的限定，可將基材浸漬於陽離子性化合物的水性溶液或水系分散液，也可將陽離子性化合物的水性溶液或水系分散液塗布於基材表面，但以浸漬的方法進行處理的方法簡便而較佳。特別是，以浸漬進行的方法可在無電鎳鍍覆的一連串的步驟中，作為所謂的調節劑(conditioner)處理的形式而實施。對於其條件，沒有特別的限定，但通常將陽離子性化合物的水性溶液或水系分散液的溫度設為10~80℃左右，較佳為設為20~50℃，藉由於其中浸漬基材來實施。對於浸漬時間，較佳為1~20分鐘左右，更佳為在2~10分鐘的範圍內。 The method for treating the surface of the substrate with a cationic compound is not particularly limited, and the substrate may be immersed in an aqueous solution or an aqueous dispersion of the cationic compound, or an aqueous solution or an aqueous dispersion of the cationic compound may be applied to the substrate. Material surface, but the method of treating by the dipping method is simple and preferable. In particular, the method by dipping can be implemented as a so-called conditioner process in a series of steps of electroless nickel plating. The conditions are not particularly limited, but the temperature of an aqueous solution or dispersion of a cationic compound is generally set to about 10 to 80 ° C, preferably 20 to 50 ° C, and the temperature is controlled by impregnating the substrate therein. . The immersion time is preferably about 1 to 20 minutes, and more preferably in the range of 2 to 10 minutes.

在使用前述高分子(P2)作為形成複合體(C)的高分子(P)的情況下，由於在其構造中具有陽離子性官能基，因此基材表面較佳為具有負電荷。通常，由於許多基材表面具有負電荷，因此在使使用高分子(P2)所形 成的複合體(C)附著的情況下，可僅藉由使基材浸漬於前述複合體(C)的分散液，而形成附著有複合體(C)的被鍍覆基材(S)，但為了使複合體(C)更均勻且穩定地附著，可使用暫時以陽離子性化合物處理基材表面，進一步使用陰離子性化合物進行處理的方法。 When the aforementioned polymer (P2) is used as the polymer (P) forming the complex (C), since the structure has a cationic functional group, the surface of the substrate preferably has a negative charge. Generally, since many substrates have a negative charge on the surface, when the composite (C) formed using the polymer (P2) is adhered, the substrate (D) can be dispersed only by immersing the substrate in the composite (C). Liquid to form the plated substrate (S) to which the composite (C) is adhered, but in order to make the composite (C) adhere more uniformly and stably, the surface of the substrate may be temporarily treated with a cationic compound, and further used Method for treating anionic compounds.

作為用於此目的之陰離子性化合物，可使用市售的陰離子性界面活性劑、或者具有陰離子性的官能基(各種酸基等)的化合物。 As the anionic compound used for this purpose, a commercially available anionic surfactant or a compound having an anionic functional group (such as various acid groups) can be used.

作為前述陰離子性的界面活性劑，例如，可使用各種作為磺酸型、磷酸酯型、烷基硫酸鹽型、烷基醚硫酸鹽型、磺基琥珀酸型界面活性劑所市售者。又，作為具有陰離子性的官能基的化合物，例如，可適合使用聚丙烯酸、聚丙烯酸鹽(鈉、銨)、聚丙烯酸馬來酸共聚物、聚丙烯酸烷酯共聚物(就重量平均分子量而言為1,000~100,000左右，較佳為5000~20,000)等。 As the anionic surfactant, various commercially available surfactants such as sulfonic acid type, phosphate type, alkyl sulfate type, alkyl ether sulfate type, and sulfosuccinic acid type surfactant can be used. In addition, as the compound having an anionic functional group, for example, polyacrylic acid, polyacrylate (sodium, ammonium), polyacrylic acid maleic copolymer, and polyalkyl acrylate copolymer (in terms of weight average molecular weight) can be suitably used. It is about 1,000 to 100,000, preferably 5000 to 20,000).

上述的陰離子性的化合物，通常製成水性溶液或水系分散液，較佳為調整在0.01~50g/L的範圍內，更佳為0.1~20g/L。在使用難以在此範圍內均勻地溶解或分散的化合物的情況下，可併用與水相溶的有機溶劑。 The aforementioned anionic compound is usually prepared as an aqueous solution or an aqueous dispersion, and it is preferably adjusted in a range of 0.01 to 50 g / L, and more preferably 0.1 to 20 g / L. When a compound which is difficult to dissolve or disperse uniformly within this range is used, an organic solvent compatible with water can be used in combination.

在上述的陰離子化合物的水性溶液或水系分散液中，可使用硼酸、磷酸、氯化銨、氨、碳酸、乙酸等作為pH緩衝劑。pH緩衝劑的用量較佳為1~50g/L，更佳為1~20g/L。 In the above-mentioned aqueous solution or dispersion of the anionic compound, boric acid, phosphoric acid, ammonium chloride, ammonia, carbonic acid, acetic acid, or the like can be used as a pH buffer. The amount of the pH buffering agent is preferably 1 to 50 g / L, and more preferably 1 to 20 g / L.

在對基材表面賦予負電荷的情況下，將已進行使用前述陽離子性化合物的水性溶液或水系分散液的處理的基材，浸漬於前述陰離子性化合物的水性溶液或水系分散體而進行處理的方法最為簡便。對於其條件，沒有特別的限定，通常將陰離子性化合物的水性溶液或水系分散液的溫度設為10~80℃左右，較佳為設為20~50℃，於其中浸漬使用陽離子性化合物處理完畢的基材。對於浸漬時間，較佳為1~20分鐘左右，更佳為在2~10分鐘的範圍內。 When a negative charge is applied to the surface of the substrate, the substrate treated with the aqueous solution or the aqueous dispersion of the cationic compound is immersed in the aqueous solution or the aqueous dispersion of the anionic compound and treated. The method is the easiest. The conditions are not particularly limited. Generally, the temperature of the aqueous solution or dispersion of the anionic compound is set to about 10 to 80 ° C, preferably 20 to 50 ° C, and the treatment with the cationic compound after immersion is completed there. Substrate. The immersion time is preferably about 1 to 20 minutes, and more preferably in the range of 2 to 10 minutes.

如此操作，使前述複合體(C)附著於表面而用作本發明的被鍍覆基材(S)的基材，係使用水性溶液或水系分散液，使複合體(C)附著於表面，因此顯示被水潤濕的傾向，即理想的是基材表面的水接觸角為75°以下。又，即使為包含難以被水潤濕的材質者，只要為可將其施加表面處理，例如，電漿照射、電暈照射、紫外線照射、臭氧處理、蝕刻等而對表面賦予親水性者，則也可適合使用。 In this way, the composite (C) is adhered to the surface to be used as the substrate of the plated substrate (S) of the present invention, and the composite (C) is adhered to the surface using an aqueous solution or an aqueous dispersion. Therefore, it shows the tendency to be wet with water, that is, it is desirable that the water contact angle on the surface of the substrate is 75 ° or less. In addition, even if it contains a material that is difficult to wet with water, as long as it can be subjected to surface treatment, such as plasma irradiation, corona irradiation, ultraviolet irradiation, ozone treatment, etching, etc., to impart hydrophilicity to the surface, Also suitable for use.

用作本發明的被鍍覆基材(S)的基材，可在附著前述複合體(C)之前，先進行各種表面粗化處理。作為表面粗化處理的方法，例如，可舉出：鉻酸蝕刻、過錳酸蝕刻等的化學處理、或噴砂處理等的機械性處理。又，用作本發明的被鍍覆基材(S)的基材，也可在附著前述複合體(C)之前，先對基材表面進行底漆(primer)處理。表面粗化、底漆處理可各自單獨進行，也可併用。表面粗化、底漆處理，除了提升被鍍覆基材(S)與鍍覆膜 的接著性以外，也可以提升前述複合體(C)對被鍍覆基材(S)的附著性為目的而實施。 The substrate used as the substrate (S) to be plated according to the present invention may be subjected to various surface roughening treatments before the composite (C) is adhered. Examples of the method for the surface roughening treatment include chemical treatments such as chromic acid etching and permanganic acid etching, and mechanical treatments such as sandblasting. In addition, the substrate used as the substrate (S) to be plated in the present invention may be subjected to a primer treatment on the surface of the substrate before the composite (C) is adhered. The surface roughening and primer treatment may be performed independently or in combination. Surface roughening and primer treatment can not only improve the adhesion between the plated substrate (S) and the plated film, but also improve the adhesion of the composite (C) to the plated substrate (S). While implementing.

在本發明中，作為為了製造被鍍覆基材(S)而使用的前述金屬粒子(M)與高分子(P)的複合體(C)之分散液的含有濃度，在藉由在基材上塗布該分散液來製造被鍍覆基材(S)的情況下，較佳為在該分散液中，含有0.5質量%以上的前述複合體(C)。即，若過度稀薄，則複合體(C)的分布變得過度稀疏，有難以在被鍍覆基材(S)上形成均勻的無電鎳鍍覆膜的情形。另一方面，若過度濃厚，則塗布在基材上的複合體(C)會進行積層，若積層膜變得過厚，則有不能充分發揮作為顯示強接著性的鍍覆膜之基礎的功能的情形。從這樣的觀點來看，作為用於藉由在基材上塗布複合體(C)來製造被鍍覆基材(S)的前述複合體(C)之分散液中的金屬微粒子的含有濃度，較佳為0.5~35質量%，再者，從塗敷性及成本的觀點來看，較佳為1~20質量%。 In the present invention, the content concentration of the dispersion liquid of the complex (C) of the metal particles (M) and the polymer (P) used for producing the plated substrate (S) is determined by When the dispersion liquid is applied on the substrate to be plated (S), it is preferable that the dispersion (C) contains the above-mentioned composite (C) in an amount of 0.5% by mass or more. That is, if it is excessively thin, the distribution of the composite (C) becomes excessively sparse, and it may be difficult to form a uniform electroless nickel plating film on the substrate (S) to be plated. On the other hand, if it is excessively thick, the composite (C) coated on the substrate is laminated, and if the laminated film becomes too thick, it may fail to fully function as a basis for a plating film exhibiting strong adhesion. Situation. From such a viewpoint, as the content concentration of the metal fine particles in the dispersion liquid of the aforementioned composite (C) for producing the plated substrate (S) by coating the composite (C) on the substrate, It is preferably 0.5 to 35% by mass, and more preferably 1 to 20% by mass from the viewpoint of coatability and cost.

在本發明中，在藉由將基材浸漬於前述複合體(C)的分散液的方法來製造被鍍覆基材(S)的情況下，作為前述複合體(C)之水性媒體中的分散濃度，從確保對基材的吸附量且得到均勻的無電鎳鍍覆膜的觀點來看，較佳為濃度(不揮發成分濃度)在0.05~5g/L的範圍內，若加上穩定的鍍覆析出性與經濟性，則更佳為將其濃度調整在0.1~2g/L的範圍內，特佳為調整在0.2~2g/L的範圍內。 In the present invention, when a substrate to be plated (S) is produced by a method of immersing a substrate in a dispersion liquid of the composite (C), it is used as an aqueous medium in the composite (C). The dispersion concentration is preferably from a viewpoint of ensuring an adsorption amount to the substrate and obtaining a uniform electroless nickel plating film (concentration of non-volatile components) within a range of 0.05 to 5 g / L. For plating precipitation and economy, it is more preferable to adjust the concentration in the range of 0.1 to 2 g / L, and particularly preferable to adjust it in the range of 0.2 to 2 g / L.

對於在基材表面上賦予前述複合體(C)之際的浸漬條件，也沒有特別的限定，通常只要將複合體(C)的水性分散體的溫度設為5~70℃，較佳為設為10~60℃左右，如前述方式操作，於其中浸漬以陰離子性或陽離子性的化合物處理過的基板即可。 There are also no particular restrictions on the immersion conditions when the composite (C) is provided on the surface of the substrate. Generally, the temperature of the aqueous dispersion of the composite (C) is preferably 5 to 70 ° C. The temperature is about 10 to 60 ° C. As described above, a substrate treated with an anionic or cationic compound may be immersed therein.

對於將基材浸漬於複合體(C)的分散液的時間，沒有特別的限制，只要因應目的而適宜決定即可，浸漬時間在30分鐘左右則複合體(C)的吸附量隨著浸漬時間的增加而增加，但即使進行其以上之長時間的浸漬，複合體(C)的吸附量也幾乎不增加，因此從製程成本削減的觀點來看，較佳為將浸漬時間設為30分鐘以內，通常可藉由2~15分鐘左右的浸漬時間而得到作為目的之被鍍覆基材(S)。 There is no particular limitation on the time for immersing the substrate in the dispersion of the composite (C), as long as it is appropriately determined in accordance with the purpose, and the amount of adsorption of the composite (C) with the immersion time is about 30 minutes. Increases, but the amount of adsorption of the composite (C) hardly increases even if the impregnation is performed for a long period of time or longer. From the viewpoint of reducing process costs, the impregnation time is preferably set to within 30 minutes. In general, the target substrate (S) to be plated can be obtained by an immersion time of about 2 to 15 minutes.

在將基材浸漬於複合體(C)的分散液而製造本發明的被鍍覆基材(S)的情況下，浸漬於複合體(C)的分散液而使複合體(C)吸附於表面的基材，可在從分散液取出後，進行清洗操作，將未充分吸附在表面的剩餘的複合體(C)除去。作為清洗操作，係作為通常的無電鎳鍍覆的一步驟，將被鍍覆基材(S)浸漬於水槽進行流水清洗，簡便而較佳。 When the base material (S) of the present invention is produced by immersing the base material in the dispersion liquid of the composite body (C), the dispersion body is immersed in the dispersion liquid of the composite body (C) to adsorb the composite body (C) to The substrate on the surface can be removed from the dispersion and then subjected to a cleaning operation to remove the remaining composite (C) which is not sufficiently adsorbed on the surface. As a cleaning operation, as a step of ordinary electroless nickel plating, the plated substrate (S) is immersed in a water tank for flowing water cleaning, which is simple and preferable.

在本發明的被鍍覆基材(S)中，前述複合體(C)可藉由前述的印刷法‧塗布法、或浸漬法來使其附著於基材表面整面，但也可使其部分選擇性地附著。作為使複合體(C)部分選擇性地附著的方法，沒有特別的限制，可使用周知慣用的各種方法，例如，只要藉由前述 的有版、無版的各種印刷法而形成複合體(C)之任意的附著圖案即可。又，可在基材上形成光阻(resist)，藉由光微影法，而僅使需要的圖案部露出，在使複合體(C)附著後，除去光阻部，形成複合體(C)的附著圖案。 In the substrate (S) to be plated according to the present invention, the composite (C) may be adhered to the entire surface of the substrate by the printing method, coating method, or dipping method described above, but it may be adhered to the entire surface of the substrate. Partially selective attachment. The method of selectively attaching the composite (C) portion is not particularly limited, and various known and commonly used methods can be used. For example, as long as the composite (C) is formed by the aforementioned various printing methods with and without a plate, ). In addition, a resist can be formed on the substrate, and only a necessary pattern portion is exposed by a photolithography method. After the composite body (C) is adhered, the photoresist portion is removed to form a composite body (C). ) 'S attachment pattern.

在本發明的被鍍覆基材(S)中，賦予在基材上的整面或部分之前述複合體(C)可為導電性膜或導電性圖案，也可形成非導電性層膜或非導電性圖案。 In the substrate (S) to be plated according to the present invention, the aforementioned composite (C) provided on the entire surface or part of the substrate may be a conductive film or a conductive pattern, or may form a non-conductive layer film or Non-conductive pattern.

[無電鎳鍍覆液]     [Electroless nickel plating solution]    

本發明中使用的無電鎳鍍覆液係含有水溶性鎳鹽、還原劑、及錯合劑者，可適合使用文獻中所記載的周知慣用的組成、市售的無電鎳鍍覆液。 The electroless nickel plating solution to be used in the present invention contains a water-soluble nickel salt, a reducing agent, and a complexing agent, and a commercially available electroless nickel plating solution with a well-known and commonly used composition described in the literature can be suitably used.

作為本發明中用於無電鎳鍍覆液的水溶性鎳鹽，只要為可得到既定濃度的水溶液者則沒有特別的限制，例如，可舉出：硫酸鎳、氯化鎳、胺磺酸鎳(nickel aminosulfonate)、次磷酸鎳等。從溶解性的觀點來看，特別可適合使用硫酸鎳。這些水溶性鎳鹽可單獨使用，或混合兩種以上使用，鍍覆液中的摻合量較佳為0.5~50g/L，更佳為5~40g/L。 The water-soluble nickel salt used in the electroless nickel plating solution in the present invention is not particularly limited as long as an aqueous solution having a predetermined concentration can be obtained, and examples thereof include nickel sulfate, nickel chloride, and nickel sulfamate ( nickel aminosulfonate), nickel hypophosphite and the like. From the viewpoint of solubility, nickel sulfate is particularly suitably used. These water-soluble nickel salts can be used singly or in combination of two or more. The blending amount in the plating solution is preferably 0.5 to 50 g / L, and more preferably 5 to 40 g / L.

作為本發明中用於無電鍍覆液的還原劑，使用次磷酸或次磷酸鹽。作為次磷酸鹽，例如，可舉出：次磷酸的鈉鹽、鉀鹽、銨鹽等。還原劑之無電鍍覆液中的摻合量較佳為0.01~100g/L左右，更佳為0.1~50g/L。 As the reducing agent used in the electroless plating solution in the present invention, hypophosphorous acid or hypophosphite is used. Examples of the hypophosphite include sodium, potassium, and ammonium salts of hypophosphorous acid. The blending amount of the reducing agent in the electroless plating solution is preferably about 0.01 to 100 g / L, and more preferably 0.1 to 50 g / L.

在本發明的無電鎳鍍覆方法中，在無電鎳鍍覆液中，進一步存在從鎳、鐵、鈷所選出的一種固體金屬。藉由在無電鎳鍍覆液中進一步存在這些固體金 屬，而形成為被鍍覆基材(S)狀的無電鎳鍍覆膜的析出性提升，可效率佳地形成更均勻的鎳膜。此外，用作前述固體金屬的鎳、鐵、或鈷，可為各自的單體金屬，也可為以各自的金屬為主要成分的合金。 In the electroless nickel plating method of the present invention, a solid metal selected from nickel, iron, and cobalt further exists in the electroless nickel plating solution. The presence of these solid metals in the electroless nickel plating solution further improves the precipitation of the electroless nickel plating film formed in the form of the plated substrate (S), and can form a more uniform nickel film with high efficiency. The nickel, iron, or cobalt used as the solid metal may be a single metal or an alloy containing each metal as a main component.

在前述固體金屬之中，從可使無電鎳鍍覆有效率地進行來看，較佳為鎳金屬。前述鎳金屬，除了單體的鎳以外，也可為鎳合金，可適合使用鎳-磷合金、鎳-硼合金等。又，可為在各種基材上鍍覆有鎳或鎳合金者。這些固體金屬可使用一種，也可併用兩種以上。 Among the foregoing solid metals, nickel metal is preferred in terms of enabling efficient electroless nickel plating. The nickel metal may be a nickel alloy other than nickel alone, and a nickel-phosphorus alloy, a nickel-boron alloy, or the like may be suitably used. In addition, it is possible to plate nickel or nickel alloy on various substrates. These solid metals may be used singly or in combination of two or more kinds.

又，前述固體金屬，有因其表面的有機物所造成的污染、氧化等而本發明的鍍覆方法之活性降低的情況，因此較佳為藉由周知的清洗方法而清洗前述固體金屬的表面。作為清洗方法，例如，可舉出：鍍覆製程中所使用的藉由清潔劑(cleaner)的清洗、藉由酸或鹼的清洗。這些清洗方法可使用一種，也可併用兩種以上。 In addition, the solid metal may reduce the activity of the plating method of the present invention due to contamination, oxidation, or the like caused by organic substances on the surface. Therefore, it is preferable to clean the surface of the solid metal by a known cleaning method. Examples of the cleaning method include cleaning with a cleaner used in a plating process, and cleaning with an acid or an alkali. These cleaning methods may be used singly or in combination of two or more.

前述固體金屬的形態，沒有特別的限制，例如，除了粒子狀、球狀、板狀、薄膜狀、棒狀、塊狀、纖維狀以外，亦可為成形物等的任一形態。又，作為前述固體金屬，可使用在無電鍍覆液中固定被鍍覆基材的支撐體或固定具中具有鎳金屬或鎳合金者，例如，經鎳鍍覆的夾具等。再者，前述固體金屬可在不與被鍍覆基材接觸的狀態下，僅存在於無電鍍覆液中。例如，若前述固體金屬為棒狀、塊狀者，則可以沉到無電鍍覆浴的容器底部的態樣使用，若前述固體金屬為微粒子狀者，則可以分散在無電鍍覆液中的態樣使用。 The form of the solid metal is not particularly limited. For example, the form of the solid metal may be any form other than particles, spheres, plates, films, rods, blocks, and fibers. In addition, as the solid metal, a support having a base material to be plated in an electroless plating solution or a fixture having nickel metal or a nickel alloy, such as a nickel-plated jig, can be used. In addition, the solid metal may exist only in the electroless plating solution without being in contact with the substrate to be plated. For example, if the solid metal is rod-shaped or lumpy, it can be used by sinking to the bottom of the container of the electroless plating bath. If the solid metal is fine, it can be dispersed in the electroless plating solution. Kind of use.

此外，在使用固定被鍍覆基材的支撐體或固定具作為前述固體金屬的情況下，若為在無電鍍覆液中前述固體金屬與被鍍覆基材直接接觸的狀態，則前述固體金屬與被鍍覆基材有因析出的鎳鍍覆膜而固著的情形。若前述固體金屬與被鍍覆基材固著，則也有在無電鍍覆處理後從支撐體或固定具卸除被鍍覆基材之際，對鍍覆膜造成損傷的情形，因此前述固體金屬較佳為使其在不與被鍍覆基材直接接觸的非接觸狀態下存在。例如，在使用支撐體或固定具作為前述固體金屬的情況下，可使用以前述固體金屬不與被鍍覆基材直接接觸的方式，將非金屬的間隔物設置在前述固體金屬(支撐體或固定具)與被鍍覆基材之間等的方法。 In addition, in the case where a support or a fixture that fixes the plated substrate is used as the solid metal, the solid metal is in a state where the solid metal is in direct contact with the plated substrate in an electroless plating solution. It may be fixed to the plated substrate by the deposited nickel plating film. If the solid metal is fixed to the plated substrate, the plated film may be damaged when the plated substrate is removed from the support or fixture after the electroless plating treatment. Therefore, the solid metal Preferably, it exists in the non-contact state which does not directly contact a to-be-plated base material. For example, when a support or a fixture is used as the solid metal, a non-metal spacer may be provided on the solid metal (support or Between fixtures) and the substrate to be plated.

藉由進一步使前述的固體金屬存在於無電鎳鍍覆液中，在被鍍覆基材(S)上所形成的無電鎳鍍覆膜的析出性提升，達成更加均勻的鎳膜形成的機制尚不明確，但推測為以下兩個機制。在本發明的無電鎳鍍覆方法中，可認為主要為以下兩個機制中任一者或兩者起作用，而無電鎳鍍覆被鍍覆基材(S)上之鎳鍍覆的析出性提升。 By further allowing the aforementioned solid metal to be present in the electroless nickel plating solution, the precipitation property of the electroless nickel plating film formed on the substrate (S) to be plated is improved, and a mechanism for achieving a more uniform nickel film formation remains. It is not clear, but it is speculated as the following two mechanisms. In the electroless nickel plating method of the present invention, it can be considered that either or both of the following mechanisms work, and the precipitation of nickel plating on the electroless nickel plating substrate (S) Promotion.

推定機制(1)：還原劑的氧化反應在存在於鍍覆液中的前述固體金屬表面進行，藉由此氧化反應而形成原子狀氫。生成的原子狀氫的一部分進行鍵結而成為氫氣，在水中擴散，使鍍覆液成為還原氣體環境，藉此使鎳鍍覆的析出性提升。又，一部分溶解、擴散於水中，到達被鍍覆基材(S)表面的前述複合體(C)附近，透過金屬粒子(M)進行與鎳離子的電子授受，使鎳析出。 Presumed mechanism (1): The oxidation reaction of the reducing agent proceeds on the surface of the solid metal existing in the plating solution, and atomic hydrogen is formed by the oxidation reaction. Part of the generated atomic hydrogen is bonded to become hydrogen gas, which is diffused in water to make the plating solution into a reducing gas environment, thereby improving the precipitation of nickel plating. In addition, a part is dissolved and diffused in water, reaches the vicinity of the composite body (C) on the surface of the substrate to be plated (S), and transmits and receives electrons with nickel ions through the metal particles (M) to precipitate nickel.

推定機制(2)：鎳鹽在存在於鍍覆液中的前述固體金屬表面被還原，生成微小的鎳粒子，此微小的鎳粒子在液中浮游、擴散，到達被鍍覆基材(S)表面的前述複合體(C)附近。該微小鎳粒子係作為還原劑的氧化觸媒而作用，此時，透過附著在被鍍覆基材(S)上的複合體(C)之金屬粒子(M)，表現與鎳鹽的電子授受路徑，使被鍍覆基材(S)上的鎳膜析出性提升。 Presumed mechanism (2): The nickel salt is reduced on the surface of the aforementioned solid metal existing in the plating solution to generate minute nickel particles. The minute nickel particles float and diffuse in the liquid and reach the substrate to be plated (S). Near the aforementioned complex (C) on the surface. The minute nickel particles act as an oxidation catalyst for the reducing agent. At this time, the metal particles (M) of the composite (C) adhered to the substrate (S) to be plated express electron transfer with the nickel salt. The path improves the precipitation of the nickel film on the plated substrate (S).

在本發明中使用的無電鎳鍍覆液中，作為錯合劑，可利用周知慣用的無電鎳鍍覆液中所使用的各種錯合劑，具體而言，可適合使用：蘋果酸、檸檬酸、乳酸、琥珀酸、己二酸等、與其鈉鹽的羧酸類；甘胺酸、丙胺酸、亞胺基二乙酸、精胺酸、天冬胺酸、麩胺酸等、其鈉鹽的胺基酸鹽類。錯合劑可單獨使用一種，或混合兩種以上使用，錯合劑的摻合量較佳為設為1~100g/L左右，更佳為設為5~50g/L。 In the electroless nickel plating solution used in the present invention, as the complexing agent, various complexing agents used in well-known and commonly used electroless nickel plating solutions can be used. Specifically, it can be suitably used: malic acid, citric acid, lactic acid. , Succinic acid, adipic acid, etc., and carboxylic acids of its sodium salt; glycine, alanine, iminodiacetic acid, spermine, aspartic acid, glutamic acid, etc., amino acids of their sodium salts Salt. The complexing agent may be used singly or in combination of two or more kinds. The blending amount of the complexing agent is preferably about 1 to 100 g / L, and more preferably 5 to 50 g / L.

在本發明中使用的無電鎳鍍覆液中，除了錯合劑以外，也可使用適宜的pH緩衝劑。作為pH緩衝劑，例如，可使用乙酸等的脂肪族單羧酸類、琥珀酸等的二羧酸類、苯二甲酸等的芳香族二羧酸類等，其摻合量較佳為設為3~25g/L，更佳為設為7~20g/L。 In the electroless nickel plating solution used in the present invention, a suitable pH buffering agent may be used in addition to the complexing agent. As the pH buffering agent, for example, aliphatic monocarboxylic acids such as acetic acid, dicarboxylic acids such as succinic acid, and aromatic dicarboxylic acids such as phthalic acid can be used. The blending amount thereof is preferably 3 to 25 g. / L, more preferably 7 to 20 g / L.

本發明中使用的無電鎳鍍覆液可進一步因應需要，將硝酸鉛、乙酸鉛等的鉛鹽、硝酸鉍、乙酸鉍等的鉍鹽、硫代二乙酸(thiodiglycolic acid)等的硫化合物等添加單獨一種或兩種以上作為穩定劑。穩定劑的添加量較佳為0.01~100mg/L左右。 The electroless nickel plating solution used in the present invention can further add lead salts such as lead nitrate and lead acetate, bismuth salts such as bismuth nitrate and bismuth acetate, sulfur compounds such as thiodiglycolic acid, etc., as needed. One kind or two or more kinds are used as stabilizers. The addition amount of the stabilizer is preferably about 0.01 to 100 mg / L.

本發明的無電鎳鍍覆方法，鍍覆浴溫度只要設定在40~98℃(較佳為50~95℃)的範圍內即可，鍍覆浴的pH可調整在4~10的範圍內。 In the electroless nickel plating method of the present invention, the temperature of the plating bath may be set in a range of 40 to 98 ° C (preferably 50 to 95 ° C), and the pH of the plating bath may be adjusted in a range of 4 to 10.

本發明中使用的無電鎳鍍覆液，只要因應消耗量而適宜添加各成分，則可長時間使用。各成分的添加，只要按照通常的方法進行即可，可單獨添加各成分，也可添加將複數成分混合者。 The electroless nickel plating solution used in the present invention can be used for a long time as long as each component is appropriately added in accordance with the consumption amount. The addition of each component may be performed according to a usual method, and each component may be added alone or a mixture of plural components may be added.

對於使用本發明的無電鎳鍍覆方法進行鍍覆處理，只要將前述被鍍覆基材(S)浸漬於設定為既定溫度的無電鎳鍍覆液中即可。此時，可因應需要進行鍍覆液的攪拌、被鍍覆物的搖動。 The plating treatment using the electroless nickel plating method of the present invention may be performed by immersing the substrate to be plated (S) in an electroless nickel plating solution set to a predetermined temperature. In this case, stirring of the plating solution and shaking of the object to be plated may be performed as necessary.

在本發明的無電鎳鍍覆方法中，被鍍覆基材(S)可在浸漬於無電鎳鍍覆液中之前，因應需要進行電漿照射、電暈照射、紫外線照射、臭氧處理、蝕刻等的使親水性提升的表面處理。 In the electroless nickel plating method of the present invention, the substrate to be plated (S) may be subjected to plasma irradiation, corona irradiation, ultraviolet irradiation, ozone treatment, etching, etc., as necessary, before being immersed in the electroless nickel plating solution. Surface treatment that improves hydrophilicity.

又，在本發明的無電鎳鍍覆方法中，前述被鍍覆基材(S)可在浸漬於無電鎳鍍覆液中之前，因應需要進行脫脂處理、藉由酸或鹼的表面清洗。 Moreover, in the electroless nickel plating method of the present invention, the substrate to be plated (S) may be degreased as required before being immersed in the electroless nickel plating solution, and the surface may be cleaned by acid or alkali.

[實施例]     [Example]    

以下，藉由實施例詳細地說明本發明。 Hereinafter, the present invention will be described in detail by examples.

本發明中使用的機器類如下。 The types of machines used in the present invention are as follows.

1H-NMR：日本電子股份有限公司製，AL300，300Hz 1 H-NMR: manufactured by Japan Electronics Co., Ltd., AL300, 300Hz

TEM觀察：日本電子股份有限公司製，JEM-2200FS TEM observation: made by Japan Electronics Co., Ltd., JEM-2200FS

TGA測定：SII NanoTechnology股份有限公司製，TG/DTA6300 TGA measurement: SII NanoTechnology Co., Ltd., TG / DTA6300

動態光散射粒徑測定裝置：大塚電子股份有限公司製，FPAR-1000 Dynamic light scattering particle size measurement device: manufactured by Otsuka Electronics Co., Ltd., FPAR-1000

又，本發明中使用的複合體及其水性分散體係基於日本特開2010-209421號公報、日本專利4697356號公報，以下述的方式進行。 The composite used in the present invention and its aqueous dispersion system were performed in the following manner based on Japanese Patent Application Laid-Open No. 2010-209421 and Japanese Patent No. 4697356.

[合成例1：銀奈米粒子與具有磷酸基的高分子之複合體的合成]     [Synthesis Example 1: Synthesis of composite of silver nanoparticle and polymer having phosphate group]     [具有磷酸基的高分子(P1)的合成]     [Synthesis of Polymer (P1) with Phosphate Group]    

在氮氣環境下，於反應容器中加入乙醇210g與2-丁酮174g，一邊攪拌一邊加熱至75℃。耗費3.5小時對其滴加使Light Ester P-1M(共榮社化學股份有限公司製)120g、Blenmer PME-1000(日油股份有限公司製)450g、Blenmer PME-100(日油股份有限公司製)30g溶解於乙醇90g與2-丁酮90g的混合溶液，耗費4.5小時同時滴加使聚合起始劑「V-59」3g、鏈轉移劑(3-巰基丙酸甲酯)18g溶解於2-丁酮30g者。從反應開始起21小時後停止加熱，空氣冷卻至室溫後，添加蒸餾水300g。以旋轉蒸發器將溶劑進行減壓蒸餾除去，補充蒸餾水100g，再次進行減壓蒸餾除去，以聚丙烯篩網將殘液進行過濾，得到具有磷酸基作為陰離子性官能基的化合物(P1)的水溶液(950g，不揮發成分62.6質量%，酸價99)。該樹脂(化合物(P1))之藉由凝膠滲透層析所測定的質量平均分子量為7,000左右。 Under a nitrogen environment, 210 g of ethanol and 174 g of 2-butanone were added to the reaction vessel, and heated to 75 ° C. while stirring. Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.) 120g, Blenmer PME-1000 (manufactured by Nippon Oil Co., Ltd.) 450g, and Blenmer PME-100 (manufactured by Nippon Oil Co., Ltd.) were added dropwise over 3.5 hours. ) 30g was dissolved in a mixed solution of 90g of ethanol and 90g of 2-butanone, and 4.5g was added simultaneously to dissolve 3g of the polymerization initiator "V-59" and 18g of a chain transfer agent (methyl 3-mercaptopropionate) in 2 -30 g of methyl ethyl ketone. After 21 hours from the start of the reaction, heating was stopped, and after air cooling to room temperature, 300 g of distilled water was added. The solvent was distilled off under reduced pressure using a rotary evaporator, and 100 g of distilled water was replenished. The solvent was distilled off under reduced pressure again, and the residual liquid was filtered through a polypropylene mesh to obtain an aqueous solution of a compound (P1) having a phosphate group as an anionic functional group. (950 g, 62.6% by mass of non-volatile content, and acid value of 99). The mass average molecular weight of this resin (compound (P1)) measured by gel permeation chromatography was about 7,000.

將所得到的生成物的1H-NMR的測定結果顯示於下。 The measurement results of 1 H-NMR of the obtained product are shown below.

1H-NMR(CD3OD)測定結果：δ(ppm)：3.85~4.45(bs),3.45~3.75(bs),3.20~3.40,2.65~2.95(bs),2.40~2.65(bs),1.75~2.35(bs),0.75~1.50(m) 1 H-NMR (CD 3 OD) measurement results: δ (ppm): 3.85 ~ 4.45 (bs), 3.45 ~ 3.75 (bs), 3.20 ~ 3.40, 2.65 ~ 2.95 (bs), 2.40 ~ 2.65 (bs), 1.75 ~ 2.35 (bs), 0.75 ~ 1.50 (m)

[化合物(P1)與銀奈米粒子之複合體(C1)的水性分散體的合成]     [Synthesis of Aqueous Dispersion of Compound (C1) of Compound (P1) and Silver Nanoparticles]    

於反應容器中加入使前述所得到的化合物(P1)的水溶液15.5g溶解於2-二甲基胺基乙醇155g(1.75mol)、65質量%硝酸170g(1.75mol)、蒸餾水195g的混合物者，進一步添加使150g的硝酸銀溶解於150g的蒸餾水者，最後添加2-二甲基胺基乙醇172.5g(1.95mol)。將反應容器浸於油浴中，在內溫50℃下加熱4小時，得到茶黑色的分散體。 A mixture of 15.5 g of the aqueous solution of the compound (P1) obtained above which was dissolved in 155 g (1.75 mol) of 2-dimethylaminoethanol, 170 g (1.75 mol) of 65% by mass nitric acid, and 195 g of distilled water was added to a reaction vessel, Further, 150 g of silver nitrate dissolved in 150 g of distilled water was added, and finally 172.5 g (1.95 mol) of 2-dimethylaminoethanol was added. The reaction vessel was immersed in an oil bath and heated at an internal temperature of 50 ° C. for 4 hours to obtain a tea-black dispersion.

將在上述所得到的反應結束後的分散體，使用中空纖維型UF膜模組(Daicen Membrane-Systems股份有限公司製，膜面積0.13m2)進行超過濾精製。濾液的導電度最初為20mS/cm以上，在其達到10μS/cm以下時結束超過濾。接著，為了從此殘渣成分除去粗大粒子而以孔徑0.45μm的薄膜過濾器進行抽氣過濾，以濾液的形式得到與銀奈米粒子之複合體的水性分散體(A-1)(1,029g，不揮發成分9.9質量%，產率97%)。此時的過濾物(粗大粒子)為135mg(以原料的銀換算為0.14質量%)。 The dispersion obtained after the completion of the reaction described above was purified by ultrafiltration using a hollow fiber-type UF membrane module (manufactured by Daicen Membrane-Systems, Inc., membrane area: 0.13 m 2 ). The conductivity of the filtrate was initially 20 mS / cm or more, and the ultrafiltration was terminated when it reached 10 μS / cm or less. Next, in order to remove coarse particles from this residue component, suction filtration was performed with a membrane filter having a pore diameter of 0.45 μm, and an aqueous dispersion (A-1) (1,029 g, without Volatile components (9.9% by mass, yield 97%). The filtered matter (coarse particles) at this time was 135 mg (0.14% by mass based on the silver of the raw material).

將所得到的分散體(A-1)進行取樣，若製成10倍稀釋液則成為黃褐色的液體，若測定其可見吸收光譜，則可於400nm處觀察到電漿子吸收光譜的波峰，因此確認銀奈米粒子的生成。又，由TEM觀察確認球形的銀奈米粒子(平均粒徑6.8nm)。使用TG-DTA，測定固體中的銀含有率，結果顯示93.5質量%，由此可估計複合體中的化合物(P1)的含量為6.5質量%。 The obtained dispersion (A-1) was sampled, and when it was made into a 10-fold dilution, it became a yellow-brown liquid. If the visible absorption spectrum was measured, the peak of the plasma absorption spectrum was observed at 400 nm. Therefore, generation of silver nanoparticle was confirmed. Moreover, spherical silver nanoparticle (average particle diameter: 6.8 nm) was confirmed by TEM observation. The silver content in the solid was measured using TG-DTA. As a result, it was 93.5% by mass. From this, it was estimated that the content of the compound (P1) in the complex was 6.5% by mass.

[合成例2：銀奈米粒子、與具有聚伸乙基亞胺嵌段及聚乙二醇嵌段的高分子的複合體(P2)的合成]     [Synthesis Example 2: Synthesis of silver nano particles and a complex (P2) with a polymer having a polyethyleneimine block and a polyethylene glycol block]     [具有聚伸乙基亞胺(PEI)嵌段及聚乙二醇(PEG)嵌段的高分子的合成]     [Synthesis of polymers with polyethyleneimine (PEI) block and polyethylene glycol (PEG) block]     [甲苯磺醯化聚乙二醇的合成]     [Synthesis of toluenesulfonated polyethylene glycol]    

分別調製在氯仿150ml中混合單末端甲氧基化聚乙二醇(以下，PEGM)[數量平均分子量(Mn)5000](Aldrich公司製)150g[30mmol]與吡啶24g(300mmol)而成的溶液、及將甲苯磺醯氯29g(150mmol)與氯仿30ml均勻混合而成的溶液。 A solution of 150 g [30 mmol] of mono-terminal methoxylated polyethylene glycol (hereinafter, PEGM) [number average molecular weight (Mn) 5000] (manufactured by Aldrich) and 24 g (300 mmol) of pyridine was prepared in 150 ml of chloroform, respectively. And a solution in which 29 g (150 mmol) of tosylsulfonium chloride and 30 ml of chloroform were uniformly mixed.

在20℃下一邊攪拌PEGM與吡啶的混合溶液，一邊對其滴加甲苯磺醯氯的甲苯溶液。滴加結束後，使其在40℃下反應2小時。反應結束後，加入氯仿150ml進行稀釋，以5質量% HCl水溶液250ml(340mmol)清洗後，以飽和食鹽水與水進行清洗。以硫酸鈉將所得到的氯仿溶液進行乾燥後，以蒸發器將溶媒蒸餾除去，進一 步進行乾燥。產率為100%。藉由1H-NMR光譜進行各波峰的釐定(2.4ppm：甲苯磺醯基中的甲基，3.3ppm：PEGM末端的甲基，3.6ppm：PEG的EG鏈，7.3~7.8ppm：甲苯磺醯基中的苯環)，確認為甲苯磺醯化聚乙二醇。 While stirring the mixed solution of PEGM and pyridine at 20 ° C, a toluene solution of tosylsulfonium chloride was added dropwise thereto. After completion of the dropwise addition, the mixture was allowed to react at 40 ° C for 2 hours. After the reaction was completed, 150 ml of chloroform was added to dilute, and then washed with 250 ml (340 mmol) of a 5% by mass HCl aqueous solution, and then washed with saturated saline and water. After the obtained chloroform solution was dried with sodium sulfate, the solvent was distilled off with an evaporator, and further dried. The yield is 100%. Determination of each peak by 1H-NMR spectrum (2.4 ppm: methyl in tosylsulfonyl, 3.3 ppm: methyl at terminal PEGM, 3.6 ppm: EG chain of PEG, 7.3 to 7.8 ppm: tosylsulfonyl Benzene ring), confirmed to be tosylate polyethylene glycol.

[具有聚伸乙基亞胺嵌段-聚乙二醇嵌段的高分子的合成]     [Synthesis of polymer with polyethyleneimine block-polyethylene glycol block]    

將在上述所得到的甲苯磺醯化聚乙二醇23.2g(4.5mmol)、與支鏈狀聚伸乙基亞胺(日本觸媒股份有限公司製，Epomin SP200)15.0g(1.5mmol)溶解在二甲基乙醯胺(以下，DMA)180ml後，加入碳酸鉀0.12g，在氮氣環境下，以100℃使其反應6小時。反應結束後，除去固體殘渣，加入乙酸乙酯150ml與己烷450ml的混合溶媒，得到沉澱物。將該沉澱物溶解在氯仿100ml中，再次加入乙酸乙酯150ml與己烷450ml的混合溶媒，使其再沉澱。將其過濾，在減壓下進行乾燥。藉由1H-NMR光譜進行各波峰的釐定(2.3~2.7ppm：支鏈PEI的伸乙基，3.3ppm：PEG末端的甲基，3.6ppm：PEG的EG鏈)，確認為具有PEG-支鏈PEI構造的化合物(P2)。產率為99%。 23.2 g (4.5 mmol) of the toluenesulfonated polyethylene glycol obtained above was dissolved with 15.0 g (1.5 mmol) of a branched polyethylenimine (Epomin SP200, manufactured by Nippon Catalysts Co., Ltd.). After 180 ml of dimethylacetamide (hereinafter, DMA), 0.12 g of potassium carbonate was added, and the mixture was reacted at 100 ° C. for 6 hours under a nitrogen atmosphere. After completion of the reaction, the solid residue was removed, and a mixed solvent of 150 ml of ethyl acetate and 450 ml of hexane was added to obtain a precipitate. This precipitate was dissolved in 100 ml of chloroform, and a mixed solvent of 150 ml of ethyl acetate and 450 ml of hexane was added again to reprecipitate. This was filtered and dried under reduced pressure. Determination of each peak by 1H-NMR spectrum (2.3 to 2.7 ppm: extended ethyl group of branched PEI, 3.3 ppm: methyl group at PEG end, 3.6 ppm: EG chain of PEG), and confirmed to have PEG-branched chain Compound (P2) constructed by PEI. The yield was 99%.

[銀奈米粒子、與具有聚伸乙基亞胺嵌段及聚乙二醇嵌段的高分子之複合體(C2)合成]     [Synthesis of silver nano particles and a polymer (C2) with a polyethyleneimine block and a polyethylene glycol block]    

在包含上述所得到的化合物(P2)0.592g的水溶液138.8g中加入氧化銀10.0g，在25℃下攪拌30分鐘。然後，一邊攪拌一邊緩慢加入二甲基乙醇胺46.0g，結果反應溶液變為黑紅色，雖稍微發熱但保持該 狀態不特別處理，在25℃下攪拌30分鐘。之後，一邊攪拌一邊緩慢加入10質量%抗壞血酸水溶液15.2g。一邊保持該溫度一邊再繼續攪拌20小時，得到黑紅色的分散體。 10.0 g of silver oxide was added to 138.8 g of an aqueous solution containing 0.592 g of the compound (P2) obtained above, and the mixture was stirred at 25 ° C. for 30 minutes. Then, 46.0 g of dimethylethanolamine was slowly added while stirring. As a result, the reaction solution turned black-red. Although slightly heated, the state was maintained without special treatment, and the mixture was stirred at 25 ° C for 30 minutes. Thereafter, while stirring, 15.2 g of a 10% by mass aqueous solution of ascorbic acid was slowly added. While maintaining the temperature, stirring was continued for another 20 hours to obtain a black-red dispersion.

在上述所得到的反應結束後的分散液中添加異丙醇200ml與己烷200ml的混合溶劑，攪拌2分鐘後，以3000rpm進行5分鐘離心濃縮。將上澄液除去後，在沉澱物中添加異丙醇50ml與己烷50ml的混合溶劑，攪拌2分鐘後，以3000rpm進行5分鐘離心濃縮。將上澄液除去後，在沉澱物中再添加水20g，攪拌2分鐘，在減壓下將有機溶劑除去，得到銀粒子的水性分散體(B-1)。 A mixed solvent of 200 ml of isopropyl alcohol and 200 ml of hexane was added to the dispersion liquid obtained after the reaction was completed, and the mixture was stirred for 2 minutes and then concentrated by centrifugation at 3000 rpm for 5 minutes. After removing the supernatant, a mixed solvent of 50 ml of isopropanol and 50 ml of hexane was added to the precipitate, and after stirring for 2 minutes, centrifugation was performed at 3000 rpm for 5 minutes and concentrated. After the supernatant liquid was removed, 20 g of water was further added to the precipitate, and the mixture was stirred for 2 minutes. The organic solvent was removed under reduced pressure to obtain an aqueous dispersion of silver particles (B-1).

將所得到的分散體(B-1)進行取樣，藉由10倍稀釋液的可見吸收光譜測定，於400nm處觀察到電漿子吸收光譜的波峰，確認銀奈米粒子的生成。又，由TEM觀察確認球形的銀奈米粒子(平均粒徑17.5nm)。使用TG-DTA，測定固體中的銀含有率，結果顯示97.2質量%。由此可估計藉由本合成法所得到的分散體中的不揮發成分中的化合物(P1-1)含量為2.8質量%。 The obtained dispersion (B-1) was sampled, and by measuring the visible absorption spectrum of a 10-fold dilution, a peak of the plasmonic absorption spectrum was observed at 400 nm, and the generation of silver nanoparticles was confirmed. Moreover, spherical silver nano particles (average particle diameter: 17.5 nm) were confirmed by TEM observation. When TG-DTA was used to measure the silver content in the solid, it was 97.2% by mass. From this, it can be estimated that the content of the compound (P1-1) in the nonvolatile matter in the dispersion obtained by this synthesis method is 2.8% by mass.

(被鍍覆基材(S)的製作)     (Production of plated substrate (S))     (被鍍覆基材(S1)的製作)     (Production of the plated substrate (S1))    

將合成例(1)所示的銀奈米粒子與高分子(P1)之複合體(C1)的水性分散體(A-1)調整為10質量%。將玻璃環氧基板(日光化成製，2.5cm×1cm，1mm厚)浸漬 於聚伸乙基亞胺10000(純正化學製)的1質量%水溶液2分鐘，取出並進行水洗。接著浸漬於調整為10質量%的銀奈米粒子複合體(C1)的水性分散體(A-1)5分鐘，取出並使其乾燥，得到被鍍覆基材(S1)。 The aqueous dispersion (A-1) of the composite (C1) of the silver nanoparticle and the polymer (P1) shown in Synthesis Example (1) was adjusted to 10% by mass. A glass epoxy substrate (manufactured by Nikko Kasei Co., Ltd., 2.5 cm x 1 cm, 1 mm thick) was immersed in a 1% by mass aqueous solution of polyethyleneimine 10000 (manufactured by Pure Chemicals) for 2 minutes, and was taken out and washed with water. Next, it was immersed in the aqueous dispersion (A-1) of the silver nanoparticle composite (C1) adjusted to 10% by mass for 5 minutes, taken out and dried to obtain a plated substrate (S1).

(被鍍覆基材(S2)的製作)     (Production of the plated substrate (S2))    

在合成例2所示的銀奈米粒子與高分子(P2)之複合體(C2)的水性分散體(B-1)中添加乙醇，製成銀濃度5質量%、水/乙醇(7/3(w/w))的銀粒子分散液，添加相對於液量為0.05質量%的KF-351A(Shin-Etsu Silicone公司製)。使用0號的K101棒(濕膜厚4μm)，以K-control coater(K101，RK Print Coat Instruments公司製)的速度刻度6的條件，將此分散液塗布(棒塗布)在玻璃環氧基板(日光化成製，5cm×10cm，1mm厚)上，在120℃下進行燒製5分鐘，藉此得到被鍍覆基材(S2)。 Ethanol was added to the aqueous dispersion (B-1) of the composite (C2) of the silver nanoparticle and the polymer (P2) shown in Synthesis Example 2 to obtain a silver concentration of 5% by mass and water / ethanol (7 / 3 (w / w)) was added to the silver particle dispersion liquid, and KF-351A (manufactured by Shin-Etsu Silicone) was added in an amount of 0.05% by mass based on the liquid amount. This dispersion was coated (rod coated) on a glass epoxy substrate (K-control coater (K101, manufactured by RK Print Coat Instruments) with a speed scale of 6 using a No. 0 K101 rod (wet film thickness of 4 μm). It was manufactured by Nikko Kasei Co., Ltd. (5 cm × 10 cm, 1 mm thick) and fired at 120 ° C. for 5 minutes to obtain a plated substrate (S2).

(被鍍覆基材(S3、S4)的製作)     (Production of plated substrates (S3, S4))    

除了使用聚醯亞胺薄膜(Kapton EN150-C，38μm厚，Toray-Dupont製)取代前述玻璃環氧基板以外，與被鍍覆基材(S2)的製作同樣地操作，在聚醯亞胺薄膜上塗布(棒塗布)銀奈米粒子與高分子(P2)之複合體(C2)的分散液，得到被鍍覆基材(S3)。進一步藉由在120℃下進行燒製5分鐘，得到被鍍覆基材(S4)。 A polyimide film (Kapton EN150-C, 38 μm thick, manufactured by Toray-Dupont) was used in place of the glass epoxy substrate in the same manner as in the production of the plated substrate (S2). A dispersion liquid of a composite (C2) of silver nanoparticle and polymer (P2) was applied (rod coated) to obtain a plated substrate (S3). Furthermore, it baked at 120 degreeC for 5 minutes, and obtained the to-be-plated base material (S4).

(被鍍覆基材(S5、S6)的製作)     (Production of plated substrates (S5, S6))    

除了將前述銀粒子分散液的銀濃度從5質量%改變為10質量%以外，與被鍍覆基材(S3、4)的製作同樣地操作，在聚醯亞胺薄膜上塗布(棒塗布)銀奈米粒 子與高分子(P2)之複合體(C2)的分散液，得到被鍍覆基材(S5)。進一步藉由在120℃下進行燒製5分鐘，得到被鍍覆基材(S6)。以測試機確認被鍍覆基材的銀粒子塗敷表面，結果確認被鍍覆基材(S5)不導電，但被鍍覆基材(S6)導電。 Except that the silver concentration of the silver particle dispersion liquid was changed from 5% by mass to 10% by mass, the same procedure as in the preparation of the plated substrate (S3, 4) was performed, and the polyimide film was applied (rod coating). A dispersion of a composite (C2) of silver nanoparticle and polymer (P2) to obtain a plated substrate (S5). Furthermore, it baked at 120 degreeC for 5 minutes, and obtained the to-be-plated base material (S6). It was confirmed with a testing machine that the coated surface of the silver particles of the plated substrate was conductive, and as a result, it was confirmed that the plated substrate (S5) was non-conductive, but the plated substrate (S6) was conductive.

(無電鎳鍍覆步驟)     (Electroless nickel plating step)    

將上述經賦予銀粒子-高分子複合體(C)的被鍍覆基材(S)作為試驗片，使用下表的組成的無電鎳鍍覆液，進行無電鎳鍍覆。 Electroless nickel plating was performed using the above-mentioned plated base material (S) provided with the silver particle-polymer composite (C) as a test piece, and using the electroless nickel plating solution having the composition shown in the following table.

(實施例1)     (Example 1)    

將被鍍覆基材(S1)的端部以Plus股份有限公司製銀色長尾夾(鎳鍍覆)夾住，浸漬於前述鎳鍍覆液。隨著來自該夾具的氣泡產生，氣泡也而在被鍍覆基材(S1)表面產生，在基材(S1)的表面形成鎳鍍覆膜。 The end portion of the substrate to be plated (S1) was sandwiched by a silver long tail clip (nickel plating) made by Plus Co., Ltd., and immersed in the aforementioned nickel plating solution. With the generation of air bubbles from the jig, air bubbles are generated on the surface of the substrate (S1) to be plated, and a nickel plating film is formed on the surface of the substrate (S1).

(實施例2~6)     (Examples 2 to 6)    

除了使用被鍍覆基材(S2)~(S6)取代在實施例1使用的鍍覆基材(S1)以外，與實施例1同樣地進行。在使用任一被鍍覆基材的情況下，皆隨著來自夾具的氣泡產生，氣泡也而在被鍍覆基材的表面產生，在被鍍覆基材(S2)~(S6)的表面形成鎳鍍覆膜。 It carried out similarly to Example 1 except having used the to-be-plated base material (S2)-(S6) instead of the plating base material (S1) used in Example 1. In the case of using any plated substrate, bubbles are generated along with the bubbles from the jig, and bubbles are also generated on the surface of the plated substrate, and on the surface of the plated substrate (S2) to (S6) A nickel plating film is formed.

(實施例7)     (Example 7)    

在被鍍覆基材(S1)的端部，貼附日東電工股份有限公司製印刷基板用遮蔽膠帶(masking tape)的ELEP遮蔽膠帶N-300，從該膠帶之上，以Plus股份有限公司製銀色長尾夾(鎳鍍覆)夾住，藉此作成試驗片與夾具不直接接觸的狀態。接著，與實施例1同樣地操作，浸漬於前述鎳鍍覆液，結果隨著來自夾具的氣泡產生，而氣泡也在被鍍覆基材(S1)的表面產生，在基材(S1)表面形成鎳鍍覆膜。 On the end of the plated substrate (S1), an ELEP masking tape N-300, which is a masking tape for printed circuit boards made by Nitto Denko Corporation, is attached, and from this tape, it is manufactured by Plus Co., Ltd. The silver long tail clip (nickel plating) is clamped, thereby making the test piece not in direct contact with the jig. Next, the same operation as in Example 1 was carried out, and the nickel plating solution was immersed. As a result, air bubbles were generated from the jig, and air bubbles were also generated on the surface of the substrate (S1) to be plated. A nickel plating film is formed.

(實施例8~12)     (Examples 8 to 12)    

除了使用被鍍覆基材(S2)~(S6)取代在實施例7使用的鍍覆基材(S1)以外，與實施例7同樣地進行。在使用任一被鍍覆基材的情況下，皆隨著來自夾具的氣泡產生，而氣泡也在被鍍覆基材的表面產生，在被鍍覆基材(S2)~(S6)的表面形成鎳鍍覆膜。 Except having used the to-be-plated base material (S2)-(S6) instead of the plating base material (S1) used in Example 7, it carried out similarly to Example 7. In the case of using any substrate to be plated, bubbles are generated along with bubbles from the jig, and bubbles are also generated on the surface of the plated substrate, and on the surfaces of the plated substrates (S2) to (S6) A nickel plating film is formed.

(實施例13)     (Example 13)    

除了將1mm厚的聚乙烯板放置在被鍍覆基材的端部來取代在實施例7使用的遮蔽膠帶後，以Plus股份有限公司製銀色長尾夾(鎳鍍覆)夾住而作成試驗片與夾具不直接接觸的狀態以外，與實施例7同樣地進行，結果隨著來自夾具的氣泡產生，而氣泡也在被鍍覆基材(S1)表面產生，在被鍍覆基材(S1)的表面形成鎳鍍覆膜。 A test piece was prepared by placing a 1-mm-thick polyethylene plate on the end of the plated substrate in place of the masking tape used in Example 7 and sandwiching it with a silver long clip (nickel plating) made by Plus Co., Ltd. Except for the state where it is not in direct contact with the jig, it was carried out in the same manner as in Example 7. As a result, air bubbles were generated from the jig, and air bubbles were also generated on the surface of the substrate to be plated (S1). A nickel-plated film is formed on the surface.

(實施例14~18)     (Examples 14 to 18)    

除了使用被鍍覆基材(S2)~(S6)取代在實施例13使用的鍍覆基材(S1)以外，與實施例13同樣地進行。在使用任一被鍍覆基材的情況下，皆隨著來自夾具的氣泡產生，而氣泡也在被鍍覆基材的表面產生，在被鍍覆基材(S2)~(S6)的表面形成鎳鍍覆膜。 It carried out similarly to Example 13 except having used the to-be-plated base material (S2)-(S6) instead of the plating base material (S1) used in Example 13. In the case of using any substrate to be plated, bubbles are generated along with bubbles from the jig, and bubbles are also generated on the surface of the plated substrate, and on the surfaces of the plated substrates (S2) to (S6) A nickel plating film is formed.

(實施例19)     (Example 19)    

使Plus股份有限公司製銀色長尾夾(鎳鍍覆)浸漬於無電鎳鍍覆液中，在未與該夾具接觸的狀態下使被鍍覆基材(S1)浸漬於無電鎳鍍覆液中，結果氣泡在被鍍覆基材(S1)的表面產生，在被鍍覆基材(S1)的表面形成無電鎳鍍覆膜。 A silver long tail clip (nickel plating) made by Plus Co., Ltd. is immersed in an electroless nickel plating solution, and the substrate to be plated (S1) is immersed in an electroless nickel plating solution without being in contact with the jig. As a result, air bubbles were generated on the surface of the substrate (S1) to be plated, and an electroless nickel plating film was formed on the surface of the substrate (S1).

(實施例20~24)     (Examples 20 to 24)    

除了使用在上述所得到的被鍍覆基材(S2)~(S6)取代在實施例19使用的鍍覆基材(S1)以外，與實施例19同樣地進行。在使用任一被鍍覆基材的情況下，皆隨著來自夾具的氣泡產生，而氣泡也在被鍍覆基材的表面產生，在被鍍覆基材(S2)~(S6)的表面形成鎳鍍覆膜。 Except having used the plated base material (S2)-(S6) obtained above mentioned instead of the plated base material (S1) used in Example 19, it carried out similarly to Example 19. In the case of using any substrate to be plated, bubbles are generated along with bubbles from the jig, and bubbles are also generated on the surface of the plated substrate, and on the surfaces of the plated substrates (S2) to (S6) A nickel plating film is formed.

(實施例25)     (Example 25)    

與被鍍覆基材(S3)的製作同樣地操作，在聚醯亞胺薄膜上塗布銀奈米粒子與高分子(P2)之複合體(C2)的分散液。此時，薄膜表面的一部分係以未塗布該分散液的狀態殘留，製作具有被賦予前述複合體(C2)的部分、與未賦予前述複合體(C2)的部分之被鍍覆基材(S7)。 In the same manner as in the production of the plated substrate (S3), a dispersion liquid of a composite (C2) of silver nanoparticle and polymer (P2) was coated on a polyimide film. At this time, a part of the surface of the film remained in a state where the dispersion liquid was not applied, and a plated substrate (S7) having a portion to which the composite (C2) was provided and a portion to which the composite (C2) was not provided was prepared. ).

與實施例19同樣地，於已浸漬Plus股份有限公司製銀色長尾夾(鎳鍍覆)的無電鎳鍍覆液中，將此被鍍覆基材(S7)在未與該夾具接觸的狀態下浸漬於無電鎳鍍覆液中，結果氣泡僅在被鍍覆基材(S7)表面之被賦予前述複合體(C2)的表面產生，形成鎳鍍覆膜，在未賦予前述複合體(C2)的部分則未形成鎳鍍覆膜。 In the same manner as in Example 19, the plated base material (S7) was immersed in an electroless nickel plating solution which had been impregnated with a silver long tail clip (nickel plating) made by Plus Co., Ltd. without being in contact with the jig. When immersed in the electroless nickel plating solution, air bubbles were generated only on the surface of the substrate (S7) to which the aforementioned composite (C2) was provided, forming a nickel plating film, and the aforementioned composite (C2) was not provided. The nickel plating film was not formed on the part.

(比較例1)     (Comparative example 1)    

除了沒有以夾具固定以外，與實施例1同樣地操作，將被鍍覆基材(S1)浸漬於前述無電鎳鍍覆液，結果即使浸漬後經過5分鐘，氣泡也未在被鍍覆基材(S1)的表面產生，未形成鎳鍍覆膜。 Except that it was not fixed with a jig, the same operation as in Example 1 was performed, and the substrate to be plated (S1) was immersed in the aforementioned electroless nickel plating solution. As a result, even if 5 minutes elapsed after the immersion, bubbles did not enter the plated substrate The surface of (S1) was generated, and no nickel plating film was formed.

(比較例2~6)     (Comparative Examples 2 to 6)    

除了使用被鍍覆基材(S2)~(S6)取代在比較例1使用的鍍覆基材(S1)以外，與比較例1同樣地進行。在使用任一被鍍覆基材的情況下，即使浸漬後經過5分鐘，氣泡皆未在被鍍覆基材(S1)的表面產生，未形成鎳鍍覆膜。 Except having used the to-be-plated base material (S2)-(S6) instead of the plating base material (S1) used by the comparative example 1, it carried out similarly to the comparative example 1. In the case of using any of the plated substrates, even if 5 minutes elapsed after the immersion, no bubbles were generated on the surface of the plated substrate (S1), and a nickel plating film was not formed.

(比較例7)     (Comparative Example 7)    

除了使用僅有未賦予銀奈米粒子與高分子(P1)之複合體(C1)的玻璃環氧基板(日光化成製，2.5cm×1cm，1mm厚)的基材取代前述被鍍覆基材(S1)以外，與實施例1同樣地進行，結果即使浸漬於無電鎳鍍覆液後經過1小時，也未形成無電鎳鍍覆膜。 Instead of using a glass epoxy substrate (manufactured by Nikko Kasei Co., Ltd., 2.5 cm × 1 cm, 1 mm thick) without a silver nanoparticle and a polymer (P1) complex (C1), a substrate was used instead of the substrate to be plated. Except (S1), it carried out similarly to Example 1, and as a result, even if 1 hour passed after immersion in the electroless nickel plating liquid, the electroless nickel plating film was not formed.

Claims (2)

一種無電鎳鍍覆方法，其係將附著有複合體(C)的被鍍覆基材(S)浸漬於含有水溶性鎳鹽、還原劑、與錯合劑的無電鎳鍍覆液，而在被鍍覆基材(S)上形成鎳的膜之無電鎳鍍覆方法，其中該複合體(C)為金屬粒子(M)與高分子(P)之複合體，該金屬粒子(M)包含銀粒子、銅粒子、或銀與銅的混合粒子，其特徵為：該高分子(P)為化合物(P1)或化合物(P2)，該化合物(P1)為含有(甲基)丙烯酸系單體的單體混合物(I)的聚合物，該(甲基)丙烯酸系單體具有從包含羧基、磷酸基、亞磷酸基、磺酸基、亞磺酸基及次磺酸基的群組所選出的一種以上的陰離子性官能基，該化合物(P2)為分子內具有聚伸乙基亞胺嵌段、聚伸丙基亞胺嵌段、聚烯丙胺嵌段中的任一種以上的化合物；該還原劑為次磷酸或其鹽；在將該被鍍覆基材(S)浸漬於該無電鍍覆液之際，使該鍍覆液中存在從包含鎳、鐵及鈷的群組所選出的一種以上的固體金屬。     An electroless nickel plating method, wherein a substrate to be plated (S) to which a composite (C) is attached is immersed in an electroless nickel plating liquid containing a water-soluble nickel salt, a reducing agent, and a complexing agent, and Electroless nickel plating method for forming a nickel film on a plating substrate (S), wherein the composite (C) is a composite of metal particles (M) and a polymer (P), and the metal particles (M) include silver Particles, copper particles, or mixed particles of silver and copper, characterized in that the polymer (P) is a compound (P1) or a compound (P2), and the compound (P1) is a (meth) acrylic monomer A polymer of a monomer mixture (I), the (meth) acrylic monomer having a group selected from the group consisting of a carboxyl group, a phosphate group, a phosphite group, a sulfonic group, a sulfinate group, and a sulfinate group. One or more anionic functional groups, and the compound (P2) is a compound having any one or more of a polyethylenimine block, a polypropylenimine block, and a polyallylamine block in the molecule; the reduction The agent is hypophosphorous acid or a salt thereof; when the substrate to be plated (S) is immersed in the electroless plating solution, the plating solution contains nickel, iron, and cobalt. The selected group of one or more of solid metal.     如請求項1的無電鎳鍍覆方法，其中該固體金屬係從包含鎳、鎳與磷的合金、及鎳與硼的合金之群組所選出的至少一種。     The electroless nickel plating method according to claim 1, wherein the solid metal is at least one selected from the group consisting of nickel, an alloy of nickel and phosphorus, and an alloy of nickel and boron.    
TW106116113A 2016-05-17 2017-05-16 Electroless nickel plating method TW201817914A (en)

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