JP2002348699A - Plated film and coated article therewith - Google Patents
Plated film and coated article therewithInfo
- Publication number
- JP2002348699A JP2002348699A JP2001213073A JP2001213073A JP2002348699A JP 2002348699 A JP2002348699 A JP 2002348699A JP 2001213073 A JP2001213073 A JP 2001213073A JP 2001213073 A JP2001213073 A JP 2001213073A JP 2002348699 A JP2002348699 A JP 2002348699A
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- Prior art keywords
- nickel
- plating
- plating film
- electrolytic
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐食性及び耐熱性
に優れた複合メッキ皮膜及びそれを用いたメッキ被覆物
に関する。より詳細には、優れた撥水性、非粘着性及び
摺動性を有する複合メッキ皮膜（耐食性複合メッキ皮
膜）及びそれを施したメッキ被覆物に関する。The present invention relates to a composite plating film having excellent corrosion resistance and heat resistance, and a plating coating using the same. More specifically, the present invention relates to a composite plating film (corrosion-resistant composite plating film) having excellent water repellency, non-adhesiveness, and slidability, and a plating coating provided with the same.
【０００２】[0002]
【従来の技術】ニッケル等の金属メッキ皮膜中にフッ素
化合物の微粒子が取り込まれた複合メッキ皮膜は、例え
ば、金属メッキ液中にフッ素化合物の微粒子を分散させ
てメッキを行うことにより得られる。このような複合メ
ッキ皮膜は、摺動性、耐衝撃性、耐傷つき性、撥水性、
非粘着性、防汚性、耐摩耗性などの特性に優れるため、
種々の用途に使用されている。例えば、特開平７−２３
８６２号公報には、金属−フッ素化合物複合メッキ皮膜
を調理器具部材に施した調理器具が開示されている。ま
た、特開平１１−３４１４２号公報には、金属−フッ素
化合物複合メッキ皮膜を樹脂押出機ダイプレートに施し
た例が開示されている。2. Description of the Related Art A composite plating film in which fine particles of a fluorine compound are incorporated in a metal plating film of nickel or the like can be obtained, for example, by dispersing fine particles of a fluorine compound in a metal plating solution and performing plating. Such a composite plating film has slidability, impact resistance, scratch resistance, water repellency,
Because it has excellent properties such as non-adhesiveness, antifouling property and abrasion resistance,
It is used for various applications. For example, JP-A-7-23
No. 862 discloses a cooking utensil in which a metal-fluorine compound composite plating film is applied to a cooking utensil member. Japanese Patent Application Laid-Open No. H11-34142 discloses an example in which a metal-fluorine compound composite plating film is applied to a resin extruder die plate.
【０００３】一般に、このような複合メッキ皮膜の金属
マトリックスとしては、ニッケル、銅、亜鉛などが使用
されている。しかし、これらの金属では、耐食性や耐熱
性が不十分である。例えば、金属マトリックスとしてニ
ッケルを使用した場合、一部の薬品（無機酸、有機酸
等）により腐食が発生したり、イオウを含有するゴム等
の樹脂との接触により、ニッケルの硫化物が生じ、メッ
キ皮膜が変色して脆くなる。さらに、５００℃程度の高
温にさらされると、ニッケルメッキ皮膜表面のフッ素化
合物の一部が分解するとともに、皮膜が青色に変色す
る。特に調理器具などでは、空だきといったユーザーの
誤った使用方法などにより５００℃程度の高温にさらさ
れる場合も多い。Generally, nickel, copper, zinc and the like are used as a metal matrix of such a composite plating film. However, these metals have insufficient corrosion resistance and heat resistance. For example, when nickel is used as a metal matrix, corrosion occurs due to some chemicals (inorganic acid, organic acid, etc.), and sulfide of nickel is generated by contact with a resin such as rubber containing sulfur, The plating film discolors and becomes brittle. Further, when exposed to a high temperature of about 500 ° C., part of the fluorine compound on the surface of the nickel plating film is decomposed, and the film turns blue. Particularly, cooking utensils and the like are often exposed to a high temperature of about 500 ° C. due to a user's erroneous usage such as emptying.
【０００４】さらに、このニッケル−フッ素樹脂複合メ
ッキの外観は、灰色であり、光沢がない。光沢を出すた
めに、メッキ後、表面をバフ研磨することも可能である
が、研磨には熟練した技術が必要であるため、コスト高
となる。また、形成した複合メッキ皮膜を数ミクロンの
厚さで削ることとなるため、不経済であるとともに、削
りすぎによりメッキ皮膜が薄膜化し、耐食性を損なう虞
がある。Further, the appearance of the nickel-fluorine resin composite plating is gray and has no luster. It is also possible to buff the surface after plating in order to make the surface glossy, but the polishing requires a skilled technique, which increases the cost. In addition, since the formed composite plating film is shaved to a thickness of several microns, it is uneconomical, and too much shaving may make the plating film thinner, which may impair corrosion resistance.
【０００５】一方、ニッケル−スズ合金は、ローズピン
クの色彩を有し、耐食性に優れているため、その合金メ
ッキは、一部の装飾用途や耐食性を必要とする用途など
で用いられている。しかし、前記ニッケル−スズ合金メ
ッキは内部応力が高いため、１０μｍ以上の膜厚を得る
ことが困難である。また、合金メッキであるため、陽極
にカーボン板などの不溶性陽極を用いて、ニッケル塩や
スズ塩などをその都度補給する必要があり、メッキ液の
管理が複雑であるという問題がある。[0005] On the other hand, nickel-tin alloys have a rose pink color and are excellent in corrosion resistance. Therefore, the alloy plating is used for some decorative applications and applications requiring corrosion resistance. However, since the nickel-tin alloy plating has a high internal stress, it is difficult to obtain a film thickness of 10 μm or more. In addition, since it is an alloy plating, it is necessary to use an insoluble anode such as a carbon plate as the anode to supply a nickel salt or a tin salt each time, and there is a problem that the management of the plating solution is complicated.
【０００６】[0006]
【発明が解決しようとする課題】従って、本発明の目的
は、耐食性及び耐熱性が改善された複合メッキ皮膜及び
その製造方法、並びに前記メッキ皮膜を施したメッキ被
覆物を提供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a composite plating film having improved corrosion resistance and heat resistance, a method for producing the same, and a plating coating provided with the plating film.
【０００７】本発明の他の目的は、耐食性及び耐熱性に
優れるとともに、加熱下で非粘着性又は摺動性に優れる
複合メッキ皮膜及びその製造方法、並びに前記メッキ皮
膜を施したメッキ被覆物を提供することにある。Another object of the present invention is to provide a composite plating film which is excellent in corrosion resistance and heat resistance and which is non-adhesive or slidable under heating, a method for producing the same, and a plated coating provided with the plating film. To provide.
【０００８】本発明のさらに他の目的は、メッキ液の管
理が簡単であり、耐傷付き性（耐摩耗性、基材との密着
性）に優れたメッキ皮膜を製造する方法を提供すること
にある。Still another object of the present invention is to provide a method for producing a plating film which is easy to manage a plating solution and has excellent scratch resistance (abrasion resistance and adhesion to a substrate). is there.
【０００９】本発明の別の目的は、膜厚を厚くしても、
割れ、剥がれなどを防止できる耐食性複合メッキ皮膜及
びその製造方法、並びに前記メッキ皮膜を施したメッキ
被覆物を提供することにある。[0009] Another object of the present invention is to provide a semiconductor device,
An object of the present invention is to provide a corrosion-resistant composite plating film capable of preventing cracking, peeling, and the like, a method for producing the same, and a plating coating provided with the plating film.
【００１０】[0010]
【課題を解決するための手段】本発明者は、前記課題を
達成するために鋭意検討した結果、フッ素化合物の微粒
子を含有するニッケル系複合メッキ皮膜を、ニッケルと
融点が４２０℃以下の第２の金属との合金で形成する
と、複合メッキ皮膜の耐食性、耐熱性、摺動性、非粘着
性などを改善できることを見いだし、本発明を完成し
た。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that a nickel-based composite plating film containing fine particles of a fluorine compound has a second melting point of 420 ° C. or less. It has been found that the formation of an alloy with the above-mentioned metal can improve the corrosion resistance, heat resistance, slidability, non-adhesiveness and the like of the composite plating film, and completed the present invention.
【００１１】すなわち、本発明のメッキ皮膜は、フッ素
化合物の微粒子を含有するニッケル系複合メッキ皮膜で
あって、この複合メッキ皮膜は、ニッケル（又はニッケ
ル系マトリックス金属）と融点が４２０℃以下の第２の
金属との合金で構成されている。但し、第２の金属がス
ズである場合、スズは、通常、表面から深さ方向に拡散
し、かつニッケル−スズ合金を形成している。That is, the plating film of the present invention is a nickel-based composite plating film containing fine particles of a fluorine compound, and the composite plating film has a melting point of 420 ° C. or less with nickel (or a nickel-based matrix metal). It is composed of an alloy with the second metal. However, when the second metal is tin, tin usually diffuses from the surface in the depth direction and forms a nickel-tin alloy.
【００１２】本発明には、フッ素化合物の微粒子を含有
するニッケル系複合メッキ皮膜であって、融点が４２０
℃以下の第２の金属が表面から深さ方向に拡散している
メッキ皮膜も含まれる。すなわち、ニッケル（又はニッ
ケル系マトリックス金属）に、前記第２の金属が表面か
ら深さ方向に拡散しているメッキ皮膜も含まれる。According to the present invention, there is provided a nickel-based composite plating film containing fine particles of a fluorine compound, the melting point of which is 420.
It also includes a plating film in which the second metal at a temperature of not more than ° C is diffused in the depth direction from the surface. That is, nickel (or a nickel-based matrix metal) includes a plating film in which the second metal is diffused from the surface in the depth direction.
【００１３】前記第２の金属は、少なくとも第２の金属
で構成された金属単体又は合金であってもよい。第２の
金属は、亜鉛、カドミウム、水銀、ガリウム、インジウ
ム、タリウム、スズ、鉛などであってもよい。なお、第
２の金属がスズである場合、第２の金属としてのスズは
表面から深さ方向に拡散し、かつニッケル−スズ合金を
形成していてもよい。第２の金属の融点は２０〜４２０
℃程度であってもよい。フッ素化合物の微粒子は、メッ
キ皮膜の表面に露出していてもよい。前記ニッケル系複
合メッキ皮膜は、前記第２の金属の拡散層とニッケル系
メッキ層とで構成されていてもよい。前記ニッケル系複
合メッキ皮膜において、第２の金属の拡散層とニッケル
系メッキ層との厚みの比は、前者／後者＝１／９９〜９
９／１程度であってもよい。前記微粒子は、フッ素樹
脂、フッ化黒鉛、フッ化ピッチなどのフッ素化合物で構
成できる。[0013] The second metal may be a simple metal or an alloy composed of at least the second metal. The second metal may be zinc, cadmium, mercury, gallium, indium, thallium, tin, lead, and the like. When the second metal is tin, tin as the second metal may diffuse from the surface in the depth direction and form a nickel-tin alloy. The melting point of the second metal is 20 to 420
It may be about ° C. The fine particles of the fluorine compound may be exposed on the surface of the plating film. The nickel-based composite plating film may include a diffusion layer of the second metal and a nickel-based plating layer. In the nickel-based composite plating film, the ratio of the thickness of the second metal diffusion layer to the thickness of the nickel-based plating layer is the former / the latter = 1/99 to 9
It may be about 9/1. The fine particles can be composed of a fluorine compound such as a fluororesin, fluorinated graphite, and fluorinated pitch.
【００１４】本発明には、基材上に前記メッキ皮膜が形
成されたメッキ被覆物も含まれる。メッキ被覆物は、加
熱下で非粘着性又は易摺動性を有する。前記メッキ被覆
物は、調理器具、調理器具用部材、成型用金型、摺動部
材、軸受け部材、航空機用部材などとして使用できる。[0014] The present invention also includes a plating coating formed by forming the plating film on a substrate. The plating coating has a non-adhesive or slidable property under heating. The plated coating can be used as a cooking utensil, a cooking utensil member, a molding die, a sliding member, a bearing member, an aircraft member, and the like.
【００１５】本発明には、基材上にフッ素化合物の微粒
子を含有するニッケル系複合メッキ皮膜を形成するメッ
キ皮膜の製造方法であって、前記複合メッキ皮膜をニッ
ケルと融点が４２０℃以下の第２の金属との合金で構成
するメッキ皮膜の製造方法も含まれる。The present invention provides a method for producing a plating film for forming a nickel-based composite plating film containing fine particles of a fluorine compound on a substrate, wherein the composite plating film has a melting point of 420 ° C. or less. The present invention also includes a method for producing a plating film composed of an alloy with the second metal.
【００１６】また、本発明には、フッ素化合物の微粒子
を含有するニッケル系複合メッキ皮膜の上に、少なくと
も融点が４２０℃以下の第２の金属で構成された皮膜を
形成し、加熱処理して、前記ニッケル系複合メッキ皮膜
中（少なくとも表面）に前記第２の金属を溶融拡散させ
るメッキ皮膜の製造方法も含まれる。前記第２の金属で
構成された皮膜は、フッ素化合物の微粒子が表面に露出
可能な厚みで形成してもよい。Further, according to the present invention, a film composed of a second metal having a melting point of at most 420 ° C. is formed on a nickel-based composite plating film containing fine particles of a fluorine compound, followed by heat treatment. The present invention also includes a method for producing a plating film in which the second metal is melted and diffused in the nickel-based composite plating film (at least on the surface). The film made of the second metal may be formed with a thickness that allows fine particles of the fluorine compound to be exposed on the surface.
【００１７】なお、本明細書中、「複合メッキ皮膜」と
は、フッ素化合物の微粒子を含有する金属メッキ皮膜を
意味する。また、複合メッキ皮膜の少なくとも表面にニ
ッケルと第２の金属との合金層が形成されたメッキ皮膜
を「耐食性複合メッキ皮膜」という場合がある。In the present specification, the term "composite plating film" means a metal plating film containing fine particles of a fluorine compound. Further, a plating film in which an alloy layer of nickel and a second metal is formed on at least the surface of the composite plating film may be referred to as a “corrosion-resistant composite plating film”.
【００１８】「非粘着性に優れる」とは、調理器具部材
においては、調理とともに飛散する油や食品の汚れが付
着しにくく、また、付着した場合でも容易にふき取るこ
とができ、手入れ性に優れていることをいう。また、成
型用金型においては、成型した樹脂などが付着せずに容
易に金型から剥離することをいう。アイロンなどの摺動
部材においては、アイロン掛けで使用する糊がアイロン
に付着するのを防止できることをいう。"Excellent in non-adhesiveness" means that cooking utensil members are less likely to adhere to oil or food stains that scatter during cooking, and even if adhered, can be easily wiped off and have excellent careability. I mean. Also, in a molding die, it means that the molded resin or the like is easily separated from the die without adhering thereto. In a sliding member such as an iron, it means that glue used for ironing can be prevented from adhering to the iron.
【００１９】「摺動性に優れる」とは、静摩擦係数と動
摩擦係数が低く、例えば、アイロンなどの摺動部材にお
いては、アイロン掛け作業でアイロンが滑りやすいこと
をいう。また、車輌や航空機のエンジンのピストンやシ
リンダー、車輪の軸受けなどの摺動部材においては、摩
擦が少なく滑りやすい、すなわち、前記摺動部材の摩耗
が防止されたり、エンジンの効率が向上することをい
う。"Excellent in slidability" means that the coefficient of static friction and the coefficient of kinetic friction are low, and, for example, in a sliding member such as an iron, the iron is liable to slip during ironing work. In addition, sliding members such as pistons and cylinders of vehicle and aircraft engines and bearings of wheels have low friction and are easy to slip, that is, wear of the sliding members is prevented or engine efficiency is improved. Say.
【００２０】[0020]
【発明の実施の形態】本発明のメッキ皮膜は、少なくと
もフッ素化合物の微粒子を含有し、かつニッケルと融点
が４２０℃以下の第２の金属との合金層で構成されてい
る。前記ニッケルと第２の金属との合金層は、均一な合
金層であってもよく、第２の金属がニッケルに拡散して
いてもよい。このような合金層では、下記式で表される
ニッケルと第２の金属との合金が形成されている。BEST MODE FOR CARRYING OUT THE INVENTION The plating film of the present invention contains at least fine particles of a fluorine compound, and is composed of an alloy layer of nickel and a second metal having a melting point of 420 ° C. or lower. The alloy layer of nickel and the second metal may be a uniform alloy layer, or the second metal may be diffused into nickel. In such an alloy layer, an alloy of nickel and the second metal represented by the following formula is formed.
【００２１】ＮｉＭx（式中、Ｍは第２の金属を示し、
ｘは０．１〜２である）前記Ｍは一種の第２の金属であ
ってもよく、複数の第２の金属であってもよい。ｘは好
ましくは０．２〜１．５程度である。例えば、第２の金
属がスズの場合、合金層では、ニッケル−スズ合金、例
えば、Ｎｉ3Ｓｎ、Ｎｉ3Ｓｎ2、Ｎｉ3Ｓｎ4などが形成
されている。NiM x (where M represents a second metal,
(x is 0.1 to 2) The M may be a kind of a second metal or a plurality of second metals. x is preferably about 0.2 to 1.5. For example, if the second metal is tin, the alloy layer, a nickel - tin alloy, for example, Ni 3 Sn, like Ni 3 Sn 2, Ni 3 Sn 4 is formed.
【００２２】本発明のメッキ皮膜において、フッ素化合
物の微粒子は、メッキ皮膜の表面に露出しているのが好
ましい。In the plating film of the present invention, the fluorine compound fine particles are preferably exposed on the surface of the plating film.
【００２３】本発明では、ニッケルと第２の金属との合
金層において、第２の金属がニッケルに拡散しているの
が有利である。好ましいメッキ皮膜は、少なくとも表面
が、フッ素化合物の微粒子を分散して含有する第２の金
属の拡散層（ニッケルと第２の金属との合金層）で構成
されている。In the present invention, in the alloy layer of nickel and the second metal, it is advantageous that the second metal is diffused into the nickel. A preferable plating film has at least a surface formed of a diffusion layer of a second metal (an alloy layer of nickel and the second metal) containing fine particles of a fluorine compound dispersed therein.
【００２４】以下、添付図面を参照しつつ、本発明のメ
ッキ皮膜をより詳細に説明する。Hereinafter, the plating film of the present invention will be described in more detail with reference to the accompanying drawings.
【００２５】図１は、本発明の複合メッキ皮膜の一例を
示す概略断面図である。この例では、基材１上に、複合
メッキ皮膜２が形成されており、この複合メッキ皮膜２
は、マトリックス金属３中にフッ素化合物の微粒子４が
分散した構造を有している。すなわち、フッ素化合物の
微粒子４が分散した複合メッキ皮膜は、表面側の第２の
金属の拡散層５と基材側のニッケル系メッキ層６とで構
成されている。前記フッ素化合物の微粒子４の一部はメ
ッキ皮膜２の表面に露出している。前記第２の金属の拡
散層５は、ニッケル系マトリックス金属３中に第２の金
属が表面から深さ方向に拡散したニッケルと第２の金属
との合金で構成されている。FIG. 1 is a schematic sectional view showing an example of the composite plating film of the present invention. In this example, a composite plating film 2 is formed on a substrate 1, and the composite plating film 2
Has a structure in which fine particles 4 of a fluorine compound are dispersed in a matrix metal 3. That is, the composite plating film in which the fine particles 4 of the fluorine compound are dispersed is composed of the diffusion layer 5 of the second metal on the surface side and the nickel-based plating layer 6 on the base material side. Part of the fluorine compound fine particles 4 is exposed on the surface of the plating film 2. The second metal diffusion layer 5 is made of an alloy of nickel and the second metal in which the second metal diffuses in the nickel matrix metal 3 from the surface in the depth direction.
【００２６】このようなメッキ皮膜は、少なくとも表面
が、フッ素化合物の微粒子を分散して含有する第２の金
属の拡散層（ニッケルと第２の金属との合金層）で構成
されているため、外観特性（装飾性、光沢など）、耐食
性、耐熱性、撥水性、強度［耐衝撃性、耐傷つき性（耐
摩耗性、基材との密着性など）など］、摺動性に優れる
とともに、樹脂などに対する非粘着性にも優れている。Since at least the surface of such a plating film is constituted by a diffusion layer of a second metal (an alloy layer of nickel and the second metal) containing dispersed fine particles of a fluorine compound, It has excellent appearance characteristics (decorative properties, glossiness, etc.), corrosion resistance, heat resistance, water repellency, strength [impact resistance, scratch resistance (abrasion resistance, adhesion to base material, etc.)], and slidability. It is also excellent in non-adhesion to resin and the like.
【００２７】メッキ皮膜は、前記第２の金属の拡散層を
少なくとも含んでいればよく、全体が、第２の金属の拡
散層であってもよい。このような第２の金属の拡散層に
おいて、第２の金属の割合は、合金中、例えば、５〜８
０重量％、好ましくは１０〜７０重量％、さらに好まし
くは１５〜６５重量％程度である。It is sufficient that the plating film includes at least the diffusion layer of the second metal, and the whole may be a diffusion layer of the second metal. In such a second metal diffusion layer, the ratio of the second metal is, for example, 5 to 8 in the alloy.
It is about 0% by weight, preferably about 10 to 70% by weight, and more preferably about 15 to 65% by weight.
【００２８】複合メッキ皮膜は、通常、第２の金属の拡
散層とニッケル系メッキ層とで構成されており、両者の
厚みの比は、第２の金属の拡散層／ニッケル系メッキ層
＝１／９９〜９９／１、好ましくは１０／９０〜６０／
４０、さらに好ましくは２０／８０〜４０／６０程度で
ある。The composite plating film is usually composed of a diffusion layer of the second metal and a nickel-based plating layer, and the thickness ratio between the two is such that the diffusion layer of the second metal / the nickel-based plating layer = 1. / 99-99 / 1, preferably 10 / 90-60 /
40, more preferably about 20/80 to 40/60.
【００２９】基材としては、用途に応じてメッキ可能な
種々の基材が使用でき、例えば、金属基材［銅、鉄（一
般鋼など）、アルミニウムなどの金属製基材；ステンレ
ス鋼、アルミニウム合金などの合金製基材など］、プラ
スチック基材［ポリオレフィン（ポリプロピレンな
ど）、ポリカーボネート、ポリスチレン、ＡＢＳ樹脂な
どの各種樹脂で構成された基材など］、非金属基材［炭
素材、木材、石材、ガラス、タイル、セラミックスなど
で構成された基材など］などが使用できる。好ましい基
材は金属基材である。特に、調理器具、調理器具用部
材、成型用金型、摺動部材用基材、航空機用部材（エン
ジン基材、降着装置用構成部品基材など）が好ましい。As the substrate, various substrates that can be plated depending on the intended use can be used. For example, metal substrates [metal substrates such as copper, iron (such as general steel), aluminum, etc .; stainless steel, aluminum Base materials made of alloys such as alloys), plastic base materials [base materials composed of various resins such as polyolefin (polypropylene), polycarbonate, polystyrene, ABS resin, etc.], non-metal base materials [carbon materials, wood, stone materials , A substrate made of glass, tile, ceramics, etc.]. Preferred substrates are metal substrates. In particular, cooking utensils, members for cooking utensils, molding dies, base materials for sliding members, and members for aircraft (engine base materials, component base materials for landing gears, etc.) are preferable.
【００３０】調理器具又は調理器具用部材に適した基材
としては、安価で高強度の基材、例えば、一般鋼、ステ
ンレス鋼、アルミニウム、アルミニウム合金などが挙げ
られる。成型用金型の基材としては、一般鋼、合金鋼
（Ｍｎ、Ｃｒ、Ｍｏ、Ｎｉ、Ａｌなどを含む合金鋼な
ど）、ステンレス鋼などが挙げられる。特に安価かつ高
強度であるため一般鋼が好ましい。摺動部材の基材とし
ては、銅、ステンレス鋼、一般鋼、アルミニウム、アル
ミニウム合金などが挙げられ、この中でも、アルミニウ
ム又はアルミニウム合金が、軽量及び安価であるため好
ましい。航空機用部材（特に、エンジン基材、降着装置
の構成部品の基材）としては、一般鋼、ステンレス鋼、
アルミニウム、アルミニウム合金などが挙げられ、この
中でも、アルミニウム又はアルミニウム合金が、軽量及
び安価であるため好ましい。これらの基材の形状及び厚
さは、特に制限されず、用途又は目的に応じて選択でき
る。Suitable base materials for cooking utensils or cooking utensil members include inexpensive and high-strength base materials such as general steel, stainless steel, aluminum and aluminum alloys. Examples of the base material of the molding die include general steel, alloy steel (such as alloy steel containing Mn, Cr, Mo, Ni, and Al), and stainless steel. In particular, general steel is preferable because of its low cost and high strength. Examples of the base material of the sliding member include copper, stainless steel, general steel, aluminum, and aluminum alloy. Among them, aluminum or aluminum alloy is preferable because it is lightweight and inexpensive. Aircraft components (especially engine base materials, base materials for landing gear components) include general steel, stainless steel,
Aluminum and an aluminum alloy are mentioned, and among them, aluminum or an aluminum alloy is preferable because it is lightweight and inexpensive. The shape and thickness of these substrates are not particularly limited and can be selected according to the application or purpose.
【００３１】ニッケル系複合メッキ皮膜を構成するマト
リックス金属としては、メッキ皮膜に用いられる慣用の
ニッケル系金属、例えば、ニッケル単独、ニッケルを主
成分とするニッケル合金（Ｎｉ基合金）などが使用でき
る。ニッケル合金を構成する金属及び非金属としては、
例えば、クロム、モリブデン、タングステンなどの周期
表第６Ａ族金属；マンガン、テクネチウム、レニウムな
どの周期表第７Ａ族金属；鉄、ルテニウム、オスミウ
ム、コバルト、ロジウム、イリジウム、パラジウム、白
金などの周期表第８族金属；銅、銀、金、水銀などの周
期表第１Ｂ族金属；亜鉛、カドミウムなどの周期表第２
Ｂ族金属；ガリウム、インジウム、タリウムなどの周期
表第３Ｂ族金属；スズ、鉛などの周期表第４Ｂ族金属；
ホウ素、周期表第５Ｂ族元素（リン、アンチモン、ビス
マスなど）、周期表第６Ｂ族元素（セレン、テルル、ポ
ロニウムなど）などの非金属が挙げられる。これらの金
属及び非金属は、１種で又は２種以上組み合わせて使用
できる。なお、ニッケル合金を構成する金属は、通常、
後述の第２の金属と異種の金属が用いられる。As the matrix metal constituting the nickel-based composite plating film, a conventional nickel-based metal used for the plating film, for example, nickel alone or a nickel alloy containing nickel as a main component (Ni-based alloy) can be used. The metals and non-metals that make up the nickel alloy include:
For example, periodic table group 6A metals such as chromium, molybdenum, and tungsten; periodic table group 7A metals such as manganese, technetium, and rhenium; Group 8 metal; Periodic table 1 such as copper, silver, gold, and mercury Group 1B; Periodic table 2 such as zinc and cadmium
Group B metal; Group 3B metal of the periodic table such as gallium, indium, and thallium; Group 4B metal of the periodic table such as tin and lead;
Non-metals such as boron, Group 5B elements of the periodic table (such as phosphorus, antimony, and bismuth) and Group 6B elements of the periodic table (such as selenium, tellurium, and polonium) are included. These metals and nonmetals can be used alone or in combination of two or more. The metal that constitutes the nickel alloy is usually
A metal different from a second metal described later is used.
【００３２】このようなニッケル合金としては、例え
ば、ニッケル−コバルト、ニッケル−鉄、ニッケル−パ
ラジウム、ニッケル−マンガン、ニッケル−レニウム、
ニッケル−クロム、ニッケル−モリブデン、ニッケル−
タングステン、ニッケル−銅、ニッケル−金、ニッケル
−亜鉛、ニッケル−スズ、ニッケル−カドミウム、ニッ
ケル−リン、ニッケル−ホウ素などの２元素合金の他、
ニッケル−コバルト−リン、ニッケル−鉄−リンなどの
３元素合金が挙げられる。Examples of such nickel alloys include nickel-cobalt, nickel-iron, nickel-palladium, nickel-manganese, nickel-rhenium,
Nickel-chromium, nickel-molybdenum, nickel-
In addition to two-element alloys such as tungsten, nickel-copper, nickel-gold, nickel-zinc, nickel-tin, nickel-cadmium, nickel-phosphorus, nickel-boron,
Three-element alloys such as nickel-cobalt-phosphorus and nickel-iron-phosphorus are exemplified.
【００３３】好ましいマトリックス金属は、ニッケル単
独、ニッケルとコバルト及び／又はリンとの合金（ニッ
ケル−コバルト合金、ニッケル−リン合金、ニッケル−
コバルト−リン合金など）である。Preferred matrix metals are nickel alone, alloys of nickel and cobalt and / or phosphorus (nickel-cobalt alloys, nickel-phosphorus alloys, nickel-
Cobalt-phosphorus alloy).
【００３４】第２の金属は、融点が４２０℃以下である
限り、特に制限されず、マトリックスを構成するニッケ
ルと合金化可能であってもよく、また、合金化しなくて
もよい。第２の金属としては、例えば、亜鉛、カドミウ
ムなどの周期表第２Ｂ族金属、水銀などの周期表第１Ｂ
族金属、ガリウム、インジウム、タリウムなどの周期表
第３Ｂ族金属、スズ、鉛などの周期表第４Ｂ族金属など
が挙げられる。中でも、亜鉛、カドミウムなどの周期表
第２Ｂ族金属、インジウムなどの周期表第３Ｂ族金属、
スズ、鉛などの周期表第４Ｂ族金属が好ましい。前記第
２の金属は、単独で又は二種以上組み合わせて使用でき
る。The second metal is not particularly limited as long as it has a melting point of 420 ° C. or less, and may be alloyable with nickel constituting the matrix or may not be alloyed. As the second metal, for example, a metal belonging to Group 2B of the periodic table such as zinc or cadmium, or a metal belonging to Group 1B of the periodic table such as mercury can be used.
Group 3B metals of the periodic table, such as group metals, gallium, indium, and thallium; and Group 4B metals of the periodic table, such as tin and lead. Among them, a metal of Group 2B of the periodic table such as zinc and cadmium, a metal of Group 3B of the periodic table such as indium,
Group 4B metals of the periodic table such as tin and lead are preferred. The second metal can be used alone or in combination of two or more.
【００３５】前記第２の金属の融点は、好ましくは２０
〜４２０℃、さらに好ましくは１００〜４２０℃程度で
ある。このような比較的低融点の金属を用いることによ
り、特に、第２の金属の拡散によりメッキ層を形成する
場合に、ニッケル系マトリックス金属中に効率よく第２
の金属を拡散できる。The melting point of the second metal is preferably 20
To 420 ° C, more preferably about 100 to 420 ° C. By using such a metal having a relatively low melting point, particularly when the plating layer is formed by diffusion of the second metal, the second metal can be efficiently contained in the nickel-based matrix metal.
Metal can be diffused.
【００３６】第２の金属は、少なくとも第２の金属で構
成された金属単体又は合金であってもよい。前記合金に
は、複数の第２の金属で構成された合金、及び少なくと
も一種の第２の金属と前記マトリックス金属の項で例示
の非金属（ホウ素、リン、アンチモン、ビスマス、セレ
ン、テルル、ポロニウムなど）とで構成された合金など
が含まれる。The second metal may be a simple metal or an alloy composed of at least the second metal. Examples of the alloy include alloys composed of a plurality of second metals, and nonmetals (boron, phosphorus, antimony, bismuth, selenium, tellurium, and polonium) exemplified in the section of at least one second metal and the matrix metal. And the like).
【００３７】前記第２の金属は、用途に応じて適宜選択
でき、例えば、調理器具や調理器具用部材では、毒性の
ない亜鉛、スズ、亜鉛−スズ合金などを用いるのが好ま
しい。また、軸受け部材などの摺動部材では、インジウ
ム、鉛−スズ合金、鉛−スズ−アンチモン合金などが、
さらに航空機用部材では、カドミウム、カドミウム−ス
ズ合金などがそれぞれ好ましい。The second metal can be appropriately selected according to the application. For example, in a cooking utensil or a cooking utensil member, it is preferable to use non-toxic zinc, tin, zinc-tin alloy or the like. In addition, in sliding members such as bearing members, indium, lead-tin alloy, lead-tin-antimony alloy, etc.
Cadmium, cadmium-tin alloy, and the like are each preferable for aircraft members.
【００３８】前記ニッケル系複合メッキ皮膜に含有され
るフッ素化合物の微粒子としては、複合メッキに使用さ
れる慣用のフッ素化合物（フッ素樹脂、フッ化黒鉛、フ
ッ化ピッチなど）の微粒子が使用できる。なお、本願明
細書中、これらのフッ素樹脂、フッ化黒鉛及びフッ化ピ
ッチをフッ素化合物と総称する。As the fine particles of the fluorine compound contained in the nickel-based composite plating film, fine particles of a conventional fluorine compound (fluorine resin, graphite fluoride, pitch fluoride, etc.) used in the composite plating can be used. In the specification of the present application, these fluororesin, fluorinated graphite and fluorinated pitch are collectively referred to as a fluorine compound.
【００３９】前記フッ素樹脂としては、特に限定され
ず、慣用のフッ素樹脂、例えば、フッ素含有単量体の単
独又は共重合体、例えば、ポリテトラフルオロエチレン
（ＰＴＦＥ）、テトラフルオロエチレン−パーフルオロ
アルキルビニルエーテル共重合体（ＰＦＡ）、テトラフ
ルオロエチレン−ヘキサフルオロプロピレン共重合体
（ＦＥＰ）、ポリクロロトリフルオロエチレン（ＰＣＴ
ＦＥ）、テトラフルオロエチレン−エチレン共重合体
（ＥＴＦＥ）などが挙げられる。好ましいフッ素樹脂
は、ＰＴＦＥ及びＰＦＡなどである。これらのフッ素樹
脂は、自己潤滑性、摺動性（低摩擦性）、撥水性、撥油
性、非粘着性などに優れている。The fluororesin is not particularly limited, and a conventional fluororesin, for example, a homo- or copolymer of a fluorine-containing monomer, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl Vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polychlorotrifluoroethylene (PCT)
FE), tetrafluoroethylene-ethylene copolymer (ETFE) and the like. Preferred fluororesins are PTFE and PFA. These fluororesins are excellent in self-lubricating properties, sliding properties (low friction properties), water repellency, oil repellency, non-adhesiveness, and the like.
【００４０】前記フッ化ピッチは、組成式ＣＦx（式
中、ｘは０．５＜ｘ＜１．８である）で表される組成を
有する化合物である。フッ化ピッチでは、通常、共有結
合により、各炭素原子に１〜３個程度のフッ素が強固に
結合している。このようなフッ化ピッチは、フッ化黒鉛
に類似した層状構造を有し、褐色乃至黄白色、黄白色乃
至白色などの色調を呈し、自己潤滑性、耐水性、耐薬品
性、撥水性、撥油性、非粘着性などに優れ、空気中でも
非常に安定な化合物である。フッ化ピッチの原料及び製
造方法などは、特に制限されず、例えば、ピッチを常温
付近でフッ素ガスと直接反応させることにより工業的に
得られるフッ化ピッチなどを用いてもよい。フッ化ピッ
チの製造方法及び構造の詳細については、例えば、特開
昭６２−２７５１９０号公報などを参照できる。また、
フッ化ピッチと染料又は顔料とを反応させることによっ
て得られる着色フッ化ピッチも使用できる。着色フッ化
ピッチの製造方法及び構造の詳細については、例えば、
特開平９−１１８８８５号公報や特開平９−２６３６４
３号公報などを参照できる。The fluorinated pitch is a compound having a composition represented by a composition formula CF x (where x is 0.5 <x <1.8). In the fluorinated pitch, usually about 1 to 3 fluorine atoms are firmly bonded to each carbon atom by a covalent bond. Such a fluorinated pitch has a layered structure similar to fluorinated graphite, exhibits a color tone such as brown to yellowish white, yellowish white to white, etc., and has self-lubricating properties, water resistance, chemical resistance, water repellency, and water repellency. It is a compound that is excellent in oiliness and non-adhesiveness, and is very stable in air. The raw material and manufacturing method of the pitch fluoride are not particularly limited, and for example, pitch fluoride industrially obtained by directly reacting the pitch with fluorine gas at around normal temperature may be used. For details of the production method and structure of the pitch fluoride, for example, JP-A-62-275190 can be referred to. Also,
Colored fluorinated pitch obtained by reacting fluorinated pitch with a dye or pigment can also be used. For details of the production method and structure of the colored fluorinated pitch, for example,
JP-A-9-118885 and JP-A-9-26364
No. 3 publication can be referred to.
【００４１】前記フッ素化合物は、単独で又は２種以上
組み合わせて使用できる。２種以上のフッ素化合物を組
み合わせて使用する場合、例えば、ＰＴＦＥとＰＦＡと
の組み合わせ、ＰＴＦＥとＦＥＰとの組み合わせ、ＰＦ
ＡとＦＥＰとの組み合わせ、ＰＦＡとフッ化黒鉛との組
み合わせ、ＰＦＡとフッ化ピッチとの組み合わせなどが
挙げられる。２種以上のフッ素化合物を併用する場合で
あっても、各フッ素化合物の割合は特に限定されず、任
意に選択することができる。The above-mentioned fluorine compounds can be used alone or in combination of two or more. When two or more fluorine compounds are used in combination, for example, a combination of PTFE and PFA, a combination of PTFE and FEP, PF
A combination of A and FEP, a combination of PFA and fluorinated graphite, a combination of PFA and fluorinated pitch, and the like can be given. Even when two or more fluorine compounds are used in combination, the ratio of each fluorine compound is not particularly limited and can be arbitrarily selected.
【００４２】前記フッ素化合物の微粒子は、微粒子の一
部がメッキ皮膜の表面に露出しているのが好ましい。一
方、微粒子の露出部分が増大しすぎると、摩擦によりメ
ッキ皮膜表面から微粒子が脱落する虞がある。そのた
め、ニッケル系複合メッキ皮膜の厚みに応じてフッ素化
合物の微粒子の平均粒径を選択するのが望ましい。It is preferable that a part of the fine particles of the fluorine compound is exposed on the surface of the plating film. On the other hand, if the exposed portion of the fine particles is too large, the fine particles may fall off the plating film surface due to friction. Therefore, it is desirable to select the average particle size of the fine particles of the fluorine compound according to the thickness of the nickel-based composite plating film.
【００４３】複合メッキ皮膜全体の厚さは、フッ素化合
物微粒子の粒径、基材の材質、形状及びマトリックス金
属の種類などに応じて、例えば、１〜１０００μｍ程度
の広い範囲から選択でき、好ましくは２〜１００μｍ、
より好ましくは５〜５０μｍ程度である。The thickness of the composite plating film as a whole can be selected from a wide range of, for example, about 1 to 1000 μm, depending on the particle diameter of the fluorine compound fine particles, the material and shape of the base material, and the type of the matrix metal. 2-100 μm,
More preferably, it is about 5 to 50 μm.
【００４４】また、フッ素化合物微粒子の平均粒径は、
例えば、０．０１〜１０μｍ、好ましくは０．０５〜５
μｍ、さらに好ましくは０．１〜２μｍ程度である。前
記平均粒径が複合メッキ皮膜全体の膜厚よりも大きい場
合には、摩擦によりメッキ皮膜表面から微粒子がより脱
落しやすいので、メッキ皮膜の膜厚よりも小さい微粒子
を使用することが望ましい。なお、複合メッキ液及び複
合メッキ皮膜中で、フッ素化合物微粒子を均一に分散さ
せるため、３０μｍ以上の粗大粒子を含まないのが望ま
しい。The average particle size of the fluorine compound fine particles is as follows:
For example, 0.01 to 10 μm, preferably 0.05 to 5
μm, and more preferably about 0.1 to 2 μm. When the average particle size is larger than the entire thickness of the composite plating film, fine particles are more likely to fall off the surface of the plating film due to friction. Therefore, it is desirable to use fine particles smaller than the thickness of the plating film. In order to uniformly disperse the fine particles of the fluorine compound in the composite plating solution and the composite plating film, it is preferable that coarse particles of 30 μm or more are not included.
【００４５】一般に、金属と共析物とからなる複合メッ
キ皮膜では、共析物の体積分率（共析率）が大きくなる
ほど、メッキ層と基材との密着性は低下する。本発明に
おいても、メッキ皮膜と基材との密着性を考慮すると、
複合メッキ皮膜中の共析物（フッ素化合物微粒子）の体
積分率は、６０％が限度である。一方、フッ素化合物微
粒子の体積分率が低すぎる場合には、撥水性、非粘着
性、摺動性の改善が十分に行なわれない。従って、本発
明においては、複合メッキ皮膜中のフッ素化合物微粒子
の体積分率は、第２の金属を含有しない状態で、皮膜全
体の１０〜６０％（例えば、１５〜６０％）程度、好ま
しくは１０〜５０％（例えば、２０〜４０％）程度、さ
らに好ましくは２５〜４０％程度である。In general, in a composite plating film composed of a metal and an eutectoid, the adhesion between the plating layer and the substrate decreases as the volume fraction (eutectoid) of the eutectoid increases. Also in the present invention, considering the adhesion between the plating film and the substrate,
The volume fraction of eutectoids (fluorine compound fine particles) in the composite plating film is limited to 60%. On the other hand, when the volume fraction of the fluorine compound fine particles is too low, the water repellency, the non-adhesiveness, and the slidability are not sufficiently improved. Therefore, in the present invention, the volume fraction of the fine particles of the fluorine compound in the composite plating film is about 10 to 60% (for example, 15 to 60%) of the whole film in a state where the second metal is not contained, preferably. It is about 10 to 50% (for example, 20 to 40%), and more preferably about 25 to 40%.
【００４６】本発明のメッキ皮膜は、基材上に、フッ素
化合物の微粒子を含有するニッケルと第２の金属との合
金で構成された複合メッキ皮膜を形成することにより製
造できる。このような複合メッキ皮膜は、慣用のニッケ
ルと第２の金属との合金メッキ液にフッ素化合物の微粒
子を添加した複合メッキ液を用いて基材をメッキ処理す
ることにより形成してもよく、フッ素化合物の微粒子を
含有するニッケル系複合メッキ皮膜に第２の金属を拡散
させることにより形成してもよい。The plating film of the present invention can be produced by forming a composite plating film composed of an alloy of nickel containing fine particles of a fluorine compound and a second metal on a base material. Such a composite plating film may be formed by plating a base material using a composite plating solution obtained by adding fine particles of a fluorine compound to a conventional alloy plating solution of nickel and a second metal. It may be formed by diffusing a second metal into a nickel-based composite plating film containing compound fine particles.
【００４７】特に、第２の金属の拡散によりニッケルと
第２の金属との合金層を形成するのが好ましく、例え
ば、フッ素化合物の微粒子を含有するニッケル系複合メ
ッキ皮膜を形成し、このニッケル系複合メッキ皮膜の上
に、さらに、少なくとも第２の金属で構成された皮膜を
形成し、加熱処理して、前記ニッケル系複合メッキ皮膜
中に第２の金属を拡散溶融させることにより形成しても
よい。In particular, it is preferable to form an alloy layer of nickel and the second metal by diffusion of the second metal. For example, a nickel-based composite plating film containing fine particles of a fluorine compound is formed. On the composite plating film, a film composed of at least a second metal is further formed, and heat treatment is performed to form the nickel-based composite plating film by diffusing and melting the second metal. Good.
【００４８】なお、複合メッキ皮膜は、必ずしも基材上
に直接形成する必要はなく、基材上に慣用のエッチング
処理を施したり、下地メッキ層（例えば、ニッケルメッ
キ、銅メッキなど）を形成した後、複合メッキ皮膜を形
成してもよい。It should be noted that the composite plating film does not necessarily need to be formed directly on the substrate, but may be formed by subjecting the substrate to a conventional etching treatment or forming a base plating layer (eg, nickel plating, copper plating, etc.). Thereafter, a composite plating film may be formed.
【００４９】ニッケル系複合メッキ皮膜は、少なくとも
ニッケルを含む金属塩（硫酸ニッケル、塩化ニッケル、
スルファミン酸ニッケルなど）を用いたメッキ浴を用い
て形成でき、電解メッキ法及び無電解メッキ法のいずれ
によって形成してもよい。The nickel-based composite plating film is made of a metal salt containing at least nickel (nickel sulfate, nickel chloride,
It can be formed using a plating bath using nickel sulfamate or the like, and may be formed by any of an electrolytic plating method and an electroless plating method.
【００５０】電解メッキ法としては、ワット浴、スルフ
ァミン酸ニッケル浴、全塩化ニッケル浴（全塩化物
浴）、硫酸塩−塩化物浴、全硫酸塩浴などを用いる無光
沢ニッケルメッキ法；光沢剤を用いる光沢ニッケルメッ
キ法（有機光沢ニッケルメッキ、ニッケル−コバルト合
金光沢ニッケルメッキなど）；黒色ニッケル浴、ストラ
イクニッケル浴、ホウフッ化ニッケル浴などを用いるメ
ッキ法などが挙げられる。As the electrolytic plating method, a matte nickel plating method using a Watts bath, a nickel sulfamate bath, a total nickel chloride bath (a total chloride bath), a sulfate-chloride bath, a total sulfate bath, etc .; A bright nickel plating method (organic bright nickel plating, nickel-cobalt alloy bright nickel plating, etc.); a plating method using a black nickel bath, a strike nickel bath, a nickel borofluoride bath, and the like.
【００５１】前記無電解メッキ法としては、酸性浴、中
性浴、水酸化アルカリ浴、アンモニアアルカリ浴などを
用いる無電解メッキ法などが挙げられる。無電解メッキ
においては、還元剤に次亜リン酸ナトリウムやジメチル
アミンボランなどを用いてメッキすることにより、マト
リックス金属とともに、リンやホウ素を共析させ、合金
としてもよい。Examples of the electroless plating method include an electroless plating method using an acidic bath, a neutral bath, an alkali hydroxide bath, an ammonia alkali bath and the like. In the electroless plating, phosphorous or boron may be co-deposited with the matrix metal by plating using sodium hypophosphite, dimethylamine borane, or the like as a reducing agent to form an alloy.
【００５２】好ましいメッキ方法は、ワット浴、スルフ
ァミン酸ニッケル浴（全スルファミン酸浴、塩化物含有
スルファミン酸浴、高速度スルファミン酸ニッケル浴な
ど）を用いた電解メッキ法、及び無電解メッキ法などで
ある。Preferred plating methods include an electrolytic plating method using a Watts bath, a nickel sulfamate bath (such as a total sulfamate bath, a chloride-containing sulfamate bath, and a high-speed nickel sulfamate bath), and an electroless plating method. is there.
【００５３】複合メッキ液中のフッ素化合物微粒子の濃
度は、例えば、２００ｇ／Ｌ以下（例えば、０．１〜２
００ｇ／Ｌ程度）、好ましくは１〜１５０ｇ／Ｌ、さら
に好ましくは５〜１００ｇ／Ｌ（例えば、１０〜１００
ｇ／Ｌ程度）、特に５〜８０ｇ／Ｌ（例えば、２０〜８
０ｇ／Ｌ）程度である。The concentration of the fine particles of the fluorine compound in the composite plating solution is, for example, 200 g / L or less (for example, 0.1 to 2 g / L).
00 g / L), preferably 1 to 150 g / L, more preferably 5 to 100 g / L (for example, 10 to 100 g / L).
g / L), especially 5 to 80 g / L (for example, 20 to 8 g / L).
0 g / L).
【００５４】このようなフッ素化合物の微粒子を含む複
合メッキ皮膜は、フッ素化合物の微粒子（ＤＴＦＥ微粒
子など）を、マトリックス金属を構成する金属の塩（メ
ッキ金属塩）を含む水溶液中に分散させ、基材上にマト
リックス金属とともにフッ素化合物の微粒子を共析させ
ることにより形成でき、非金属であるフッ素化合物の固
有の性質とマトリックスである金属の性質とを併せ持っ
ている。このような複合メッキ皮膜は、例えば、特開昭
４９−２７４４３号公報や特開平４−３２９８９７号公
報などのメッキ方法などにより形成できる。The composite plating film containing the fine particles of the fluorine compound is prepared by dispersing the fine particles of the fluorine compound (such as DTFE fine particles) in an aqueous solution containing a salt of a metal constituting the matrix metal (a plating metal salt). It can be formed by co-depositing fine particles of a fluorine compound together with a matrix metal on a material, and has both the inherent properties of a non-metallic fluorine compound and the properties of a metal as a matrix. Such a composite plating film can be formed by, for example, a plating method described in JP-A-49-27443 or JP-A-4-329897.
【００５５】本発明のメッキ皮膜は、慣用のメッキ用添
加剤、例えば、光沢剤［一次光沢剤（サッカリン、１，
５−ナフタレンジスルホン酸ナトリウム、１，３，６−
ナフタレントリスルホン酸ナトリウム、パラトルエンス
ルホンアミドなど）、二次光沢剤（クマリン、２−ブテ
ン−１，４−ジオール、エチレンシアンヒドリン、プロ
パルギルアルコール、ホルムアルデヒド、チオ尿素、キ
ノリン、ピリジン、アリルスルホン酸ナトリウムなど）
など］、メッキ皮膜着色のための着色剤（顔料、染料な
ど）などを含んでいてもよい。The plating film of the present invention may be prepared by adding a conventional plating additive such as a brightener [a primary brightener (saccharin, 1,
Sodium 5-naphthalenedisulfonic acid, 1,3,6-
Sodium naphthalene trisulfonate, p-toluenesulfonamide, etc.), secondary brighteners (coumarin, 2-butene-1,4-diol, ethylene cyanohydrin, propargyl alcohol, formaldehyde, thiourea, quinoline, pyridine, allyl sulfonic acid) Sodium, etc.)
Etc.), and a coloring agent (a pigment, a dye, etc.) for coloring the plating film may be included.
【００５６】複合メッキ皮膜を形成させるための複合メ
ッキ液では、撥水性が非常に高いフッ素化合物の微粒子
をメッキ液中に均一に分散させるとともに、前記微粒子
の表面を完全に濡れた状態にする必要があるため、界面
活性剤を用いるのが好ましい。このような界面活性剤と
しては、例えば、水溶性のカチオン系界面活性剤、非イ
オン系界面活性剤、及びメッキ液のｐＨ値においてカチ
オン性を示す両性界面活性剤などが使用できる。前記カ
チオン系界面活性剤としては、第４級アンモニウム塩、
第２及び第３級アミン類などが挙げられ、非イオン系界
面活性剤としては、ポリオキシエチレン系、ポリエチレ
ンイミン系及びエステル系の界面活性剤などが挙げら
れ、両性界面活性剤としては、カルボン酸系及びスルホ
ン酸系の界面活性剤などが挙げられる。特に、フッ素化
合物微粒子の濡れ性を高めるため、分子中にＣ−Ｆ結合
を有するフッ素系界面活性剤、例えば、ＣＦ3−（Ｃ
Ｆ2）n−、ＣＦ3−（ＣＨ2）n−、ＣＦ3−（ＣＦ2）n−
（ＣＨ2）m−などのフッ化炭素基を有する界面活性剤な
どを用いるのが好ましい。In a composite plating solution for forming a composite plating film, it is necessary to uniformly disperse fluorine compound fine particles having extremely high water repellency in the plating solution and to make the surface of the fine particles completely wet. Therefore, it is preferable to use a surfactant. As such a surfactant, for example, a water-soluble cationic surfactant, a nonionic surfactant, and an amphoteric surfactant showing cationicity at a pH value of a plating solution can be used. As the cationic surfactant, a quaternary ammonium salt,
Secondary and tertiary amines, etc., and nonionic surfactants include polyoxyethylene, polyethyleneimine and ester surfactants, and amphoteric surfactants include carboxyl groups. Acid-based and sulfonic acid-based surfactants and the like can be mentioned. In particular, in order to enhance the wettability of the fluorine compound fine particles, a fluorine-based surfactant having a CF bond in the molecule, for example, CF 3- (C
F 2) n -, CF 3 - (CH 2) n -, CF 3 - (CF 2) n -
(CH 2) m - to use a surfactant having a fluorocarbon group of such preferred.
【００５７】メッキ液中への界面活性剤の添加量は、フ
ッ素化合物１ｇに対して、通常、１〜５００ｍｇ程度の
範囲から選択でき、好ましくは１〜３００ｍｇ、さらに
好ましくは１〜１００ｍｇ（例えば、１０〜５０ｍｇ）
程度である。The amount of the surfactant to be added to the plating solution can be generally selected from the range of about 1 to 500 mg, preferably 1 to 300 mg, more preferably 1 to 100 mg (for example, 1 g of the fluorine compound). 10-50mg)
It is about.
【００５８】本発明においては、上記の複合メッキ液に
一次光沢剤、二次光沢剤、メッキ皮膜着色のための顔料
などの公知の添加剤をさらに配合することができる。In the present invention, known additives such as a primary brightener, a secondary brightener, and a pigment for coloring a plating film can be further added to the composite plating solution.
【００５９】フッ素化合物の微粒子を均一に分散させる
ためには、複合メッキ液を撹拌しつつメッキ操作を行な
うことが好ましい。撹拌方法は特に限定されず、慣用の
機械的撹拌手段、例えば、スクリュー撹拌、マグネチッ
クスターラーによる撹拌などの方法を採用できる。In order to uniformly disperse the fine particles of the fluorine compound, it is preferable to perform the plating operation while stirring the composite plating solution. The stirring method is not particularly limited, and a conventional mechanical stirring means, for example, a method of screw stirring, a method of stirring with a magnetic stirrer or the like can be adopted.
【００６０】ニッケル系複合メッキの条件は、基材の材
質、使用する複合メッキ液の種類などに応じて、適宜設
定でき、一般に、通常の複合メッキ法において採用され
ているのと同様の液温、ｐＨ値、電流密度などから選択
すればよい。例えば、無電解メッキの場合、メッキ液の
組成に応じて、ｐＨは、酸性又は中性メッキ浴で４〜
７、塩基性メッキ浴で８．５〜１２．５程度から選択で
き、温度は４０〜９０℃程度の範囲から選択できる。ま
た、例えば、塩化物含有スルファミン酸ニッケル浴を用
いる電解メッキでは、ｐＨは３．５〜４．５程度、温度
は２５〜７０℃程度、電流密度は２〜１４Ａ／ｄｍ2程
度の範囲からそれぞれ選択できる。The conditions of the nickel-based composite plating can be appropriately set according to the material of the base material, the type of the composite plating solution to be used, and the like. In general, the same solution temperature as that used in the ordinary composite plating method is used. , PH value, current density and the like. For example, in the case of electroless plating, depending on the composition of the plating solution, the pH is 4 to 4 in an acidic or neutral plating bath.
7. The basic plating bath can be selected from about 8.5 to 12.5, and the temperature can be selected from the range of about 40 to 90 ° C. Further, for example, in electrolytic plating using a chloride-containing nickel sulfamate bath, the pH is about 3.5 to 4.5, the temperature is about 25 to 70 ° C., and the current density is about 2 to 14 A / dm 2. You can choose.
【００６１】ニッケル系複合メッキ皮膜の厚みは、特に
制限されず、例えば、１〜１０００μｍ、好ましくは２
〜１００μｍ、さらに好ましくは５〜５０μｍ程度であ
る。The thickness of the nickel-based composite plating film is not particularly limited, and is, for example, 1 to 1000 μm, preferably 2 to 1000 μm.
１００100 μm, more preferably about 5-50 μm.
【００６２】第２の金属の拡散方法は、特に制限され
ず、例えば、複合メッキ皮膜上に少なくとも第２の金属
で構成された皮膜を形成し、加熱することなどにより、
前記複合メッキ皮膜中に第２の金属を溶融拡散できる。
第２の金属の拡散によりニッケルと第２の金属との合金
を形成するので、フッ素化合物の微粒子が含まれた複合
メッキであってもメッキ液の管理が簡単である。特に、
第２の金属としてスズを用いる場合には内部応力が大き
くなる傾向にある。そのため、このようにスズの溶融拡
散によりニッケル−スズ合金を形成すると、ニッケル−
スズ合金でありながらも内部応力を低減でき、皮膜の膜
厚を厚くしても（例えば、１０μｍ以上）、割れや剥が
れ等のない良好なメッキ皮膜を維持できる。The method of diffusing the second metal is not particularly limited. For example, by forming a film composed of at least the second metal on the composite plating film and heating it,
The second metal can be melt-diffused in the composite plating film.
Since the alloy of nickel and the second metal is formed by diffusion of the second metal, it is easy to manage the plating solution even in the case of composite plating containing fine particles of a fluorine compound. In particular,
When tin is used as the second metal, the internal stress tends to increase. Therefore, when a nickel-tin alloy is formed by melting and diffusing tin in this manner, nickel-tin alloy is formed.
Even though it is a tin alloy, the internal stress can be reduced, and even if the film thickness is large (for example, 10 μm or more), a good plating film without cracking or peeling can be maintained.
【００６３】第２の金属の皮膜は、メッキにより形成し
てもよく、また、金属溶射、真空蒸着、スパッタリン
グ、イオンプレーティングなどの手法により形成しても
よい。前記メッキは、複合メッキの金属表面に第２の金
属を析出させる慣用のメッキ法、例えば、電解メッキ
（酸性メッキ浴、アルカリ性メッキ浴、中性メッキ浴な
どを用いた電解メッキ法など）、無電解メッキ、溶融メ
ッキなどにより行うことができ、特に電解メッキが好ま
しい。例えば、電解亜鉛メッキ法としては、酸性亜鉛メ
ッキ浴（硫酸亜鉛浴、塩化亜鉛浴など）、アルカリ性亜
鉛メッキ浴（シアン化亜鉛浴、ジンケート浴など）など
を用いた電解メッキ法が挙げられる。また、電解カドミ
ウムメッキとしては、酸性メッキ浴（硫酸浴、ホウフッ
化浴など）、アルカリ性メッキ浴（シアン化浴、アミン
浴など）などを用いた電解メッキ法が挙げられる。The second metal film may be formed by plating, or may be formed by a technique such as metal spraying, vacuum evaporation, sputtering, or ion plating. The plating is carried out by a conventional plating method for depositing a second metal on the metal surface of the composite plating, such as electrolytic plating (electrolytic plating using an acidic plating bath, an alkaline plating bath, a neutral plating bath, etc.), It can be performed by electrolytic plating, hot-dip plating, or the like, and electrolytic plating is particularly preferable. For example, examples of the electrolytic zinc plating method include an electrolytic plating method using an acidic zinc plating bath (a zinc sulfate bath, a zinc chloride bath, etc.), an alkaline zinc plating bath (a zinc cyanide bath, a zincate bath, etc.). Examples of the electrolytic cadmium plating include an electrolytic plating method using an acidic plating bath (sulfuric acid bath, borofluoride bath, etc.), an alkaline plating bath (cyanide bath, amine bath, etc.).
【００６４】また、メッキ条件も使用するメッキ液の種
類に応じて適宜決定すればよく、通常のメッキの場合と
同様の液温、ｐＨ、電流密度などが採用できる。The plating conditions may be appropriately determined according to the type of the plating solution to be used, and the same liquid temperature, pH, current density and the like as in the case of ordinary plating can be adopted.
【００６５】ここで、前記複合メッキ皮膜上に形成する
第２の金属のメッキ皮膜の厚みは、複合メッキ皮膜に分
散しているフッ素化合物の微粒子の粒径に応じて、例え
ば、０．０１〜２μｍ（例えば、０．１〜１．５μ
ｍ）、好ましくは０．１〜１μｍである。第２の金属の
皮膜の厚みが０．０１μｍより小さいと、皮膜の均一性
がなく、熱処理した場合にニッケルと第２の金属との合
金が十分に形成されない虞がある。また、第２の金属の
皮膜の厚みが２μｍを越えると第２の金属の皮膜を形成
する前のフッ素化合物の微粒子を含有する複合メッキ皮
膜において、表面に露出しているフッ素化合物の微粒子
が、第２の金属の皮膜で埋もれてしまい、フッ素化合物
微粒子の持つ自己潤滑性、低摩擦性、撥水性、撥油性、
非粘着性などの性質が十分に発揮できなくなる。従っ
て、フッ素化合物微粒子が表面に露出可能な厚みで第２
の金属の皮膜を形成するのが好ましい。Here, the thickness of the second metal plating film formed on the composite plating film is, for example, from 0.01 to 0.01 depending on the particle diameter of the fluorine compound fine particles dispersed in the composite plating film. 2 μm (for example, 0.1 to 1.5 μm
m), preferably from 0.1 to 1 μm. When the thickness of the second metal film is less than 0.01 μm, the film is not uniform, and there is a possibility that an alloy of nickel and the second metal may not be sufficiently formed upon heat treatment. Further, when the thickness of the second metal film exceeds 2 μm, in the composite plating film containing fine particles of the fluorine compound before forming the second metal film, the fine particles of the fluorine compound exposed on the surface are: Being buried in the second metal film, the self-lubricating property, low friction property, water repellency, oil repellency,
Properties such as non-adhesion cannot be sufficiently exhibited. Therefore, the second thickness is such that the fluorine compound fine particles can be exposed on the surface.
It is preferable to form a metal film of
【００６６】第２の金属をニッケル系複合メッキ皮膜中
に熱拡散させる熱処理温度は、第２の金属の融点に応じ
て適宜選択でき、例えば、２００〜４５０℃（例えば、
２００〜４２０℃）程度、好ましくは２００〜４００℃
（例えば、２５０〜４００℃）程度、さらに好ましくは
２５０〜３８０℃（例えば、２５０〜３５０℃）程度で
ある。また、熱処理時間は、特に限定されず、例えば、
５分〜２時間程度の範囲から選択でき、通常、１０〜６
０分（例えば、２０〜４０分）程度である。前記熱処理
温度が２００℃未満である場合には、十分な処理効果を
得るために処理時間を長くする必要があり、一方、熱処
理温度が高すぎると、フッ素化合物が分解する虞があ
る。加熱処理により、第２の金属がニッケル系複合メッ
キ皮膜の少なくとも表面に拡散して耐食性の高いニッケ
ルと第２の金属との合金が形成される。The heat treatment temperature at which the second metal is thermally diffused into the nickel-based composite plating film can be appropriately selected according to the melting point of the second metal, and is, for example, 200 to 450 ° C. (for example,
200-420 ° C.), preferably 200-400 ° C.
(For example, about 250 to 400 ° C.), and more preferably about 250 to 380 ° C. (for example, about 250 to 350 ° C.). The heat treatment time is not particularly limited, for example,
It can be selected from a range of about 5 minutes to 2 hours, usually 10 to 6
It is about 0 minutes (for example, 20 to 40 minutes). When the heat treatment temperature is lower than 200 ° C., it is necessary to lengthen the treatment time in order to obtain a sufficient treatment effect. On the other hand, when the heat treatment temperature is too high, the fluorine compound may be decomposed. By the heat treatment, the second metal diffuses into at least the surface of the nickel-based composite plating film to form an alloy of nickel and the second metal having high corrosion resistance.
【００６７】このような加熱処理により、第２の金属を
拡散させ、フッ素化合物微粒子を含有するニッケルと第
２の金属との合金を形成すると、耐食性複合メッキ皮膜
の撥水・撥油性や基材に対する密着性も著しく改善され
る。これは、耐食性複合メッキ皮膜自体の熱的改質、界
面活性剤の除去(熱分解、蒸発、昇華など)による濡れ性
の低下などによるものと推測される。When the second metal is diffused by such a heat treatment to form an alloy of nickel containing the fluorine compound fine particles and the second metal, the water and oil repellency of the corrosion-resistant composite plating film and the substrate Adhesion to the substrate is also remarkably improved. This is presumed to be due to thermal reforming of the corrosion-resistant composite plating film itself, and a decrease in wettability due to removal of a surfactant (eg, thermal decomposition, evaporation, sublimation, etc.).
【００６８】ニッケルと第２の金属との合金の耐食性を
さらに高めるとともに、外観を美しくするため、クロメ
ート処理を行ってもよい。クロメート処理は、通常、最
終仕上げとして行う場合が多い。クロメート処理は、慣
用のクロメート処理液［例えば、第２の金属の種類に応
じたクロメート液（例えば、スズメッキ用、亜鉛メッキ
用、カドミウムメッキ用など）の光沢クロメート液、有
色クロメート液、緑色クロメート液、黒色クロメート液
など］を用いて、慣用の方法により行うことができる。
例えば、フッ素化合物微粒子を含有するニッケルと第２
の金属（例えば、スズ、亜鉛、カドミウムなど）との複
合メッキ皮膜を施した被覆物を、前記のようなクロメー
ト処理液に浸漬し（例えば、数秒乃至数十秒間程度浸漬
し）、必要により水洗、乾燥などを行うことによりクロ
メート処理した被覆物を得てもよい。前記クロメート処
理液は市販品であってもよい。In order to further enhance the corrosion resistance of the alloy of nickel and the second metal and to make the appearance beautiful, a chromate treatment may be performed. Usually, the chromate treatment is often performed as a final finish. The chromate treatment is performed by using a conventional chromate treatment liquid [for example, a chromate liquid corresponding to the type of the second metal (for example, tin plating, zinc plating, cadmium plating, etc.), a gloss chromate liquid, a colored chromate liquid, and a green chromate liquid. , A black chromate solution, etc.] using a conventional method.
For example, nickel containing fluorine compound fine particles and the second
The coated material provided with the composite plating film with the metal (for example, tin, zinc, cadmium, etc.) is immersed in the chromate treatment solution as described above (for example, immersed for several seconds to several tens of seconds) and, if necessary, washed with water. , Drying or the like to obtain a chromate-treated coating. The chromate treatment liquid may be a commercially available product.
【００６９】このようにして得られたメッキ皮膜は、フ
ッ素化合物に基づく撥水性、撥油性、摺動性、非粘着
性、耐薬品性及び耐磨耗性、マトリックス金属に基づく
高硬度、高強度、高熱伝導度及び耐熱性などの特性を損
なうことなく、さらに第２の金属の拡散処理を行って表
面をニッケルと第２の金属との合金系としているため、
耐薬品性、耐熱性、耐腐食性及び装飾性を大きく改善で
きる。また、加熱処理により、撥水性、撥油性及び非粘
着性などの特性は著しく改善される。従って、このよう
なメッキ皮膜は、種々の基材の表面に形成して、基材に
前記のような特性（特に、耐食性、耐熱性、非粘着性、
摺動性など）を付与するのに有用であり、前記メッキ皮
膜を施したメッキ被覆物は、特に、加熱下で非粘着性及
び／又は易摺動性を示すため、調理器具（コンロ、レン
ジ用部材など）、調理器具用部材（フライパン、焼き
網、炊飯器内釜、鍋など）、成型用金型、摺動部材（ア
イロン底板のかけ面などのアイロン用部材など）、軸受
け部材、航空機用部材（エンジン部材、降着装置の構成
部材、制御機器部材、操縦機器部材など）などとして有
用である。The plating film thus obtained has a water repellency, an oil repellency, a sliding property, a non-adhesive property, a chemical resistance and an abrasion resistance based on a fluorine compound, a high hardness and a high strength based on a matrix metal. Since the surface of the alloy is made of nickel and the second metal by further diffusing the second metal without deteriorating properties such as high thermal conductivity and heat resistance,
Chemical resistance, heat resistance, corrosion resistance and decorativeness can be greatly improved. Further, the properties such as water repellency, oil repellency and non-adhesion are remarkably improved by the heat treatment. Therefore, such a plating film is formed on the surface of various base materials, and the base material has the above-mentioned properties (in particular, corrosion resistance, heat resistance, non-adhesion,
It is useful for imparting slidability and the like, and the plated coating provided with the plating film is particularly non-adhesive and / or easily slidable under heating. Components, cooking utensils (frying pans, grills, rice cookers, pots, etc.), molding dies, sliding members (ironing members, such as the bottom surface of an iron bottom plate), bearing members, aircraft It is useful as a member for use (engine member, component member of landing gear, control device member, steering device member, etc.).
【００７０】[0070]
【発明の効果】本発明では、メッキ皮膜を、フッ素化合
物微粒子を含むニッケルと特定の融点を有する第２の金
属との合金で構成するので、メッキ皮膜の耐食性及び耐
熱性を改善できる。また、本発明のメッキ皮膜は、耐傷
付き性（耐摩耗性、基材との密着性）にも優れている。
さらに、ニッケルと第２の金属との合金を、前記第２の
金属の拡散により構成すると、メッキ液の管理が簡単で
ある。前記第２の金属としてスズを用いると、膜厚を厚
くしても、割れ、剥がれなどを防止でき、加熱下であっ
ても非粘着性又は摺動性に優れる。According to the present invention, the plating film is composed of an alloy of nickel containing fluorine compound fine particles and a second metal having a specific melting point, so that the corrosion resistance and heat resistance of the plating film can be improved. Further, the plating film of the present invention is also excellent in scratch resistance (wear resistance, adhesion to a substrate).
Further, when the alloy of nickel and the second metal is formed by diffusion of the second metal, the management of the plating solution is easy. When tin is used as the second metal, cracking and peeling can be prevented even if the film thickness is increased, and excellent non-adhesiveness or slidability is obtained even under heating.
【００７１】[0071]
【実施例】以下に、実施例に基づいて本発明をより詳細
に説明するが、本発明はこれらの実施例によって限定さ
れるものではない。The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.
【００７２】なお、実施例及び比較例で用いた基材を以
下に示す。The substrates used in Examples and Comparative Examples are shown below.
【００７３】基材Ａ：板状試験片（縦５０ｍｍ×横５０
ｍｍ×厚さ０．５ｍｍ、材質ＳＵＳ４３０） 基材Ｂ：板状試験片（縦５０ｍｍ×横５０ｍｍ×厚さ３
ｍｍ、材質ＳＳ４００） 基材Ｃ：直径５ｍｍの棒材で構成された外枠と、直径３
ｍｍの棒材で形成された網部とを有する幅１８５ｍｍ×
奥行き２５５ｍｍの焼き網（材質ＳＰＣＣ） 基材Ｄ：テーブルコンロのグリル皿（開口部：縦２７６
ｍｍ×横１９０ｍｍ、深さ２０ｍｍ、厚さ０．５ｍｍ、
材質ＳＰＣＣ） 上記基材を用いて、実施例及び比較例で得られたメッキ
皮膜の物性及び特性を次のように評価した。Substrate A: Plate-shaped test piece (50 mm long × 50 mm wide)
mm × thickness 0.5 mm, material SUS430) Substrate B: plate-shaped test piece (50 mm long × 50 mm wide × thickness 3)
mm, material SS400) Substrate C: Outer frame made of 5 mm diameter rod, and 3 mm diameter
185 mm width with a net formed of a bar material of mm
255 mm deep grid (material SPCC) Base material D: Grill for table stove (opening: 276 vertical)
mm × 190 mm wide, 20 mm deep, 0.5 mm thick,
Material SPCC) Using the above substrate, the physical properties and characteristics of the plating films obtained in Examples and Comparative Examples were evaluated as follows.
【００７４】（１）フッ素化合物の共析率測定 フッ素化合物の微粒子を含む複合メッキ皮膜を形成した
基材Ａを、硝酸水溶液（硝酸：水（容量比）＝１：１）
に浸漬して、メッキ皮膜を溶解し、この溶解液をメンブ
ランフィルター（平均孔径＝０．１μｍ）を用いて濾過
した。次いで、このメンブランフィルターを乾燥機に入
れ、１００℃で２０分間乾燥した後、１時間デシケータ
ー中で冷却して重量を測り、フッ素化合物微粒子の共析
率を算出した。(1) Measurement of eutectoid rate of fluorine compound A substrate A on which a composite plating film containing fine particles of a fluorine compound was formed was treated with an aqueous nitric acid solution (nitric acid: water (volume ratio) = 1: 1).
To dissolve the plating film, and the solution was filtered using a membrane filter (average pore size = 0.1 μm). Next, the membrane filter was placed in a drier, dried at 100 ° C. for 20 minutes, cooled in a desiccator for 1 hour, weighed, and the eutectoid rate of the fluorine compound fine particles was calculated.
【００７５】（２）撥水性 メッキ皮膜を形成した基材Ｂについて、ＦＡＣＥ接触角
測定器（協和界面科学（株）製、「ＣＡ−Ａ型」）を用
いて、液滴法により、水の接触角を測定し、撥水性の指
標とした。(2) Water repellency The base material B on which the plating film was formed was treated with a FACE contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., “CA-A type”) by a droplet method to obtain water. The contact angle was measured and used as an index of water repellency.
【００７６】（３）密着性 メッキ皮膜を形成した基材Ｂに１ｃｍ2あたり１００個
の碁盤目を入れ、下記の各条件下に放置した後常温に戻
し、セロファン粘着テープにより、ＪＩＳ Ｋ５４００
に準拠して圧着剥離試験（密着力試験）を行った。(3) Adhesiveness 100 grids per 1 cm 2 were placed on the base material B on which the plating film was formed, left under the following conditions, and then returned to room temperature, and then adhered to JIS K5400 using a cellophane adhesive tape.
A pressure-bonding peel test (adhesion test) was performed in accordance with.
【００７７】（ａ）２５０℃で２時間放置 （ｂ）−１０℃で２時間放置 （ｃ）（２００℃で１時間放置した後、−１０℃で１時
間放置）×１０サイクル なお、メッキ皮膜の密着性は、１ｃｍ2あたり剥離した
碁盤目の数により、下記の基準で評価した。(A) Leave at 250 ° C. for 2 hours (b) Leave at −10 ° C. for 2 hours (c) (Leave at 200 ° C. for 1 hour and then at −10 ° C. for 1 hour) × 10 cycles Was evaluated according to the following criteria by the number of grids peeled per cm 2 .
【００７８】 ○：全く剥離せず △：剥離した碁盤目の数が１００個中５０個未満であっ
た ×：剥離した碁盤目の数が１００個中５０個以上であっ
た （４）耐衝撃変形性試験（ＪＩＳ Ｋ５４００） ＪＩＳ Ｋ５４００に準拠して、メッキ皮膜を形成した
基材Ｂ上に、２０℃でデュポン式により５００ｍｍの高
さから５００ｇのおもりを落とし、変形させた部分の皮
膜の損傷を観察し、下記の基準により目視で評価した。：: No peeling at all Δ: Number of peeled grids was less than 50 out of 100 ×: Number of peeled grids was 50 or more out of 100 (4) Impact resistance Deformability test (JIS K5400) In accordance with JIS K5400, a 500 g weight was dropped from a height of 500 mm at a temperature of 20 ° C. on a base material B on which a plating film was formed by a DuPont method, and the damaged portion of the film was deformed. Was observed and evaluated visually by the following criteria.
【００７９】 ○：損傷なし ×：損傷あり （５）耐薬品性試験 メッキ皮膜を形成した基材Ｂ上に１ｃｍ2あたり１００
個の碁盤目を形成し、下記の薬品又は材料に９６時間浸
漬した。４時間毎に試験片を取り出して、水洗いし、変
色及び剥がれの有無を肉眼で確認すると共に、９６時間
浸漬後にセロファン粘着テープにより、圧着剥離試験を
行い、メッキ皮膜の耐薬品性を評価した。：: No damage ×: Damaged (5) Chemical resistance test 100 per cm 2 on base material B on which plating film was formed
Each grid was formed and immersed in the following chemicals or materials for 96 hours. Every 4 hours, the test piece was taken out, washed with water, visually checked for discoloration and peeling, and immersed for 96 hours, and then subjected to a pressure peel test with a cellophane adhesive tape to evaluate the chemical resistance of the plating film.
【００８０】（ａ）ラッカーシンナー （ｂ）界面活性剤（登録商標「ファミリーフレッシ
ュ」，花王（株）製） （ｃ）カレー（登録商標「ククレカレー辛口」，ハウス
食品（株）製） （ｄ）こいくち醤油（キッコーマン（株）製） （ｅ）台所用漂白剤（登録商標「キッチンハイター」，
花王（株）製）１５容量％水溶液 （ｆ）台所用漂白剤（登録商標「キッチンハイター」，
花王（株）製）５０容量％水溶液 （ｇ）台所用漂白剤（登録商標「キッチンハイター」，
花王（株）製） （ｈ）４容量％酢酸水溶液 （ｉ）１０容量％塩酸水溶液 （ｊ）１０容量％硫酸水溶液 （ｋ）１０容量％硝酸水溶液 なお、耐薬品性は、下記の基準で評価した。(A) Lacquer thinner (b) Surfactant (registered trademark "Family Fresh", manufactured by Kao Corporation) (c) Curry (registered trademark "Kukure Curry Dry", manufactured by House Foods Co., Ltd.) (d) Koikuchi soy sauce (made by Kikkoman Corporation) (e) Bleaching agent for kitchen (registered trademark “Kitchen Highter”,
(F) Kao Corporation 15% by volume aqueous solution (f) Kitchen bleach (registered trademark "Kitchen Highter")
Kao Corporation 50% by volume aqueous solution (g) Kitchen bleach (registered trademark "Kitchen Highter")
(H) 4% aqueous acetic acid solution (i) 10% aqueous hydrochloric acid solution (j) 10% aqueous sulfuric acid solution (k) 10% aqueous nitric acid solution Chemical resistance is evaluated according to the following criteria. did.
【００８１】 ○：変色及び剥離のいずれもなし ×：少なくとも一部の薬品又は材料について変色及び／
又は剥離が生じる （６）５００℃耐熱試験 メッキ皮膜を形成した基材Ｂを、電気炉中（５００℃）
で２０分間加熱した後、自然冷却させ、メッキ皮膜の変
色を目視にて観察した。なお、メッキ皮膜の耐熱性は、
下記の基準で評価した。：: Neither discoloration nor peeling ×: Discoloration and / or at least a part of chemicals or materials
(6) 500 ° C. heat resistance test The base material B on which the plating film is formed is placed in an electric furnace (500 ° C.)
And then allowed to cool naturally, and the discoloration of the plating film was visually observed. The heat resistance of the plating film is
Evaluation was made according to the following criteria.
【００８２】 ○：変色なし ×：青色に変色した （７）摺動試験 メッキ皮膜を形成した基材Ｂについて、表面性測定機
（新東科学（株）製、ＨＥＩＤＯＮ−１４Ｄ型）を用い
てメッキ表面における静摩擦係数及び動摩擦係数を測定
した。：: no discoloration ×: discolored to blue (7) Sliding test The substrate B on which the plating film was formed was measured using a surface property measuring device (HEIDON-14D, manufactured by Shinto Kagaku Co., Ltd.). The coefficient of static friction and the coefficient of dynamic friction on the plating surface were measured.
【００８３】（８）耐摩耗試験 （ａ）ラビングテスター（太平理化（株）製）の可動ス
テージにメッキ皮膜を形成した基材Ｂを固定し、上から
２．４５Ｎの重力を加えた状態で羊毛フェルトを摺動さ
せた。１回の摺動距離は１００ｍｍであった。１０万回
摺動させた後に羊毛フェルトの汚れの有無を目視にて確
認した。(8) Abrasion Resistance Test (a) The base material B on which the plating film was formed was fixed to a movable stage of a rubbing tester (manufactured by Taihei Rika Co., Ltd.), and a gravity of 2.45 N was applied from above. The wool felt was slid. One sliding distance was 100 mm. After sliding 100,000 times, the wool felt was visually checked for stains.
【００８４】 ○：汚れなし ×：汚れあり （ｂ）上記（ａ）の試験前後のメッキ皮膜の膜厚を、蛍
光Ｘ線分析（（株）リガク製、Ｗａｆｅｒ−Ｘ３００）
を用いて測定し、膜厚の減少度合いにより摩耗性を下記
の基準で評価した。：: No dirt X: Dirt (b) The thickness of the plating film before and after the test (a) was measured by X-ray fluorescence analysis (Wafer-X300, manufactured by Rigaku Corporation).
The abrasion was evaluated according to the following criteria based on the degree of decrease in film thickness.
【００８５】 ○：膜厚の減少が１μｍ未満である ×：膜厚の減少が１μｍ以上である （９）成型用金型としての非粘着性試験 メッキ皮膜を形成した基材Ｂ２枚に、板状のスチレンブ
タジエンゴム（ＳＢゴム、５０ｍｍ×５０ｍｍ×３ｍ
ｍ）を挟み込み、９．８×１０4Ｐａの圧力をかけて１
８０℃で１０分間保持した。その後、ＳＢゴムの剥がれ
具合とメッキ皮膜の変色の有無を目視にて観察し、非粘
着性を下記の基準で評価した。：: decrease in film thickness is less than 1 μm ×: decrease in film thickness is 1 μm or more (9) Non-adhesion test as a molding die A plate was formed on two base materials B on which a plating film was formed. Styrene butadiene rubber (SB rubber, 50 mm x 50 mm x 3 m
m) and apply a pressure of 9.8 × 10 4 Pa
It was kept at 80 ° C. for 10 minutes. Thereafter, the degree of peeling of the SB rubber and the presence or absence of discoloration of the plating film were visually observed, and the non-adhesion was evaluated according to the following criteria.
【００８６】 ○：メッキ皮膜に変色はなく、ＳＢゴムも容易に剥離し
た △：メッキ皮膜に変色はないが、ＳＢゴムの一部が付着
してとれなかった ×：メッキ皮膜が黒色に変色し、ＳＢゴムの一部が付着
してとれなかった （１０）焦げ付き試験 メッキ皮膜を形成した基材Ｄに、下記の食品及び調味材
料（ａ）又は（ｂ）２ｍｌを滴下し、２５０℃で３０分
間加熱して焦げ付かせた後、冷却し、指先で炭化物を軽
く圧迫して、炭化物の剥離の難易により、焦げ付き性を
下記の基準で評価した。 （ａ）カレー（登録商標「ククレカレー辛口」，ハウス
食品（株）製） （ｂ）醤油＋砂糖＋卵（重量比１：１：１） ○：炭化物が容易に剥離する ×：炭化物が剥離しない （１１）魚焼き試験 それぞれにメッキ皮膜を形成した基材Ｃ（焼き網）及び
基材Ｄ（グリル皿）をテーブルコンロ（大阪ガス（株）
製１０−６６６型）のグリルにセットし、基材Ｃにサン
マ（体長２５ｃｍ）を置いて両面焼きで５分間加熱を行
った。加熱後、グリルより焼き魚を置いたままの基材Ｃ
を取り出し、焼き魚を凧糸で２カ所固定してテンション
ゲージを付けて吊り上げ、焼き魚が基材Ｃより離れた時
点での指示値を測定した。基材Ｃより剥がした焼き魚の
重さを測定し、テンションゲージ指示値より焼き魚の重
さを差し引いた値を焼き魚の身離れ荷重とした。この試
験を連続５回行って平均値を求めた。：: No discoloration of the plating film, and the SB rubber was easily peeled off. Δ: No discoloration of the plating film, but a part of the SB rubber was not removed, and ×: The plating film discolored to black. (10) Burning test 2 ml of the following food and seasoning material (a) or (b) was dropped on the base material D on which the plating film was formed, and 30 ° C. at 250 ° C. After heating for a minute for scorching, the mixture was cooled and lightly pressed against the carbide with a fingertip. The scoring property was evaluated according to the following criteria due to the difficulty of peeling the carbide. (A) Curry (registered trademark "Kukure Curry Dry", manufactured by House Foods Co., Ltd.) (b) Soy sauce + sugar + egg (weight ratio 1: 1: 1) ○: Carbide easily peels ×: Carbide does not peel (11) Fish roasting test A substrate stove (Osaka Gas Co., Ltd.) was prepared by plating the base material C (grate net) and the base material D (grill dish) each having a plating film formed thereon.
10-666 type grill), a saury (25 cm in length) was placed on the substrate C, and heating was performed for 5 minutes by baking on both sides. After heating, substrate C with grilled fish on grill
The grilled fish was fixed at two places with a kite string, lifted with a tension gauge, and the indicated value when the grilled fish was separated from the substrate C was measured. The weight of the grilled fish peeled from the base material C was measured, and the value obtained by subtracting the weight of the grilled fish from the indicated value of the tension gauge was taken as the separation load of the grilled fish. This test was performed five times in succession, and the average value was determined.
【００８７】また、５回試験後、基材Ｄをティッシュペ
ーパーにてふき取った場合の油汚れの取れ易さと、メッ
キ皮膜の変色の有無とを下記の基準で評価した。After the test was performed five times, the ease of removing oil stains when the substrate D was wiped off with tissue paper and the presence or absence of discoloration of the plating film were evaluated according to the following criteria.
【００８８】（油汚れの取れ易さ） ○：油汚れが容易にとれる ×：油汚れが取れにくい （メッキ皮膜の変色） ○：変色なし ×：皮膜の一部が黒色に変色した 実施例１ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。(Easy removal of oil stains) ：: Oil stains are easily removed ×: Oil stains are not easily removed (discoloration of plating film) ：: No discoloration ×: Part of film is discolored to black Example 1 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【００８９】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−ＰＴＦＥ複合メッキ液の調製 電解ニッケルメッキ液（組成：スルファミン酸ニッケル
３６０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ
／Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子
径０．２μｍ、ダイキン工業（株）製、ルブロンＬ−
２）５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面
活性剤としての第４級パーフルオロアンモニウム塩［Ｃ
8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録
商標「メガファックＦ１５０」，大日本インキ化学
（株）製］を３０．０ｍｇ添加して、電解ニッケル−Ｐ
ＴＦＥ複合メッキ液を調製した。 （３）電解スズメッキ液の調製 下記の組成を有するスズメッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-PTFE composite plating solution Electrolytic nickel plating solution (composition: nickel sulfamate 360 g / L, nickel chloride 45 g / L, boric acid 30 g)
/ L) PTFE fine particles (average particle diameter 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-
2) 50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C
8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3 · Cl -, R "Megafac F150", Dainippon Ink and Chemicals Co., Ltd.] was added 30.0mg of electrolytic nickel - P
A TFE composite plating solution was prepared. (3) Preparation of electrolytic tin plating solution A tin plating solution having the following composition was prepared.
【００９０】 硫酸スズ ４３ｇ／Ｌ グルコン酸ナトリウム １３１ｇ／Ｌ ｐ−メトキシベンズアルデヒド ０．１ｇ／Ｌ ポリエチレングリコール７５００ １ｇ／Ｌ ３７％ホルマリン ０．６ｍｌ／Ｌ （４）メッキ法 前記各基材（被メッキ材料）をアルカリ脱脂液で脱脂し
た後、それぞれを負極とし、前記（１）の組成のニッケ
ルストライクメッキ液を含むメッキ槽を用いて、液温２
５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッケルス
トライクメッキ処理を２分間行った。Tin sulfate 43 g / L Sodium gluconate 131 g / L p-methoxybenzaldehyde 0.1 g / L Polyethylene glycol 7500 1 g / L 37% formalin 0.6 ml / L (4) Plating method ) Was degreased with an alkaline degreasing solution, each was used as a negative electrode, and the solution temperature was adjusted to 2 using a plating tank containing the nickel strike plating solution having the composition (1).
Under a condition of 5 ° C. and a current density of 10 A / dm 2 , nickel strike plating was performed for 2 minutes.
【００９１】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−ＰＴＦＥ複合メッキ液を
含むメッキ槽中、液温５０℃、ｐＨ４．２、電流密度２
Ａ／ｄｍ2の条件で、スクリュー撹拌しつつ、膜厚が１
０μｍとなるまで電解メッキを行って、電解ニッケル−
ＰＴＦＥ複合メッキ皮膜を形成した。この時点で共析率
測定用試験片を使用し、ＰＴＦＥの共析率（容量％）を
求めたところ、３０容量％であった。Next, using the obtained coating material, in a plating bath containing the electrolytic nickel-PTFE composite plating solution having the composition (2), a solution temperature of 50 ° C., a pH of 4.2, and a current density of 2 were used.
Under the condition of A / dm 2 , the film thickness is 1
Electroplating is performed until the thickness becomes 0 μm.
A PTFE composite plating film was formed. At this point, the eutectoid rate (volume%) of PTFE was determined using a test piece for eutectoid rate measurement, and was 30 vol%.
【００９２】さらに、前記複合メッキを施した被覆物を
負極として、前記（３）の組成を有する電解スズメッキ
液を含むメッキ槽中、液温３５℃、ｐＨ６．０及び電流
密度２Ａ／ｄｍ2の条件で、膜厚が０．５μｍとなるま
で電解メッキを行って、スズメッキ皮膜を形成した。メ
ッキ終了後、水洗し、１００℃で５分間乾燥させた。Further, the composite-plated coating was used as a negative electrode in a plating bath containing an electrolytic tin plating solution having the composition of (3) above at a solution temperature of 35 ° C., a pH of 6.0 and a current density of 2 A / dm 2 . Under the conditions, electrolytic plating was performed until the film thickness became 0.5 μm to form a tin plating film. After the plating was completed, the plate was washed with water and dried at 100 ° C. for 5 minutes.
【００９３】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上にスズメッキ皮膜を施したメッキ被覆物を、
熱風循環式乾燥炉中で、３５０℃で３０分間加熱した
後、常温で１時間室内放置した。このメッキ被覆物の表
面をＸ線回折装置（理学電機（株）、ＲＩＮＴ２５０
０）を用いて分析したところ、Ｎｉ3Ｓｎ2の組成のニッ
ケル−スズ合金が生成しているのがわかった。ＥＰＭＡ
分析装置（日本電子（株）製ＪＸＡ−８９００ＲＬ）を
用いて被覆物表面を分析したところ、被覆物表面のニッ
ケル−スズ合金の組成は、ニッケル：６４重量％及びス
ズ：３６重量％であった。A plating coating obtained by applying a tin plating film on the obtained electrolytic nickel-PTFE composite plating film was
After heating at 350 ° C. for 30 minutes in a hot air circulating drying oven, it was left indoors at room temperature for 1 hour. An X-ray diffractometer (Rigaku Corporation, RINT250)
As a result of analysis using (0), it was found that a nickel-tin alloy having a composition of Ni 3 Sn 2 was formed. EPMA
When the surface of the coating was analyzed using an analyzer (JXA-8900RL manufactured by JEOL Ltd.), the composition of the nickel-tin alloy on the surface of the coating was 64% by weight of nickel and 36% by weight of tin. .
【００９４】また、前記ＥＰＭＡ分析装置を用いて、断
面深さ方向のスズの分析を行ったところ、スズの拡散層
の厚みは３μｍであった。この耐食性複合メッキ皮膜が
施された被覆物を用いて共析率以外の前記（２）〜（１
１）の試験を行った。Further, when the tin was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the tin diffusion layer was 3 μm. Using the coating provided with the corrosion-resistant composite plating film, the above (2) to (1) except for the eutectoid ratio were used.
The test of 1) was performed.
【００９５】実施例２ 実施例１の電解スズメッキの膜厚を０．２μｍとした以
外は、実施例１と同様にして、基材にニッケルストライ
クメッキ、電解ニッケル−ＰＴＦＥメッキ皮膜及び電解
スズメッキ皮膜を順次形成した。Example 2 A nickel strike plating, an electrolytic nickel-PTFE plating film and an electrolytic tin plating film were applied to a substrate in the same manner as in Example 1 except that the film thickness of the electrolytic tin plating of Example 1 was changed to 0.2 μm. Formed sequentially.
【００９６】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上にスズメッキ皮膜を施したメッキ被覆物を、
熱風循環式乾燥炉中で、３５０℃で３０分間加熱した
後、常温で１時間室内放置した。このメッキ被覆物の表
面をＸ線回折装置（理学電機（株）、ＲＩＮＴ２５０
０）を用いて分析したところ、Ｎｉ3ＳｎおよびＮｉ3Ｓ
ｎ 2の２種類の組成のニッケル−スズ合金が生成してい
ることが分かった。また、メッキ被覆物の表面をＥＰＭ
Ａ分析装置（日本電子（株）製ＪＸＡ−８９００ＲＬ）
を用いて分析したところ、ニッケル：８３重量％及びス
ズ：１７重量％のニッケル−スズ合金が形成されてい
た。また、前記ＥＰＭＡ分析装置を用いて、断面深さ方
向のスズの分析を行ったところ、スズの拡散層の厚みは
３μｍであった。この耐食性複合メッキ皮膜が施された
被覆物を用いて実施例１と同様の試験評価を行った。The resulting electrolytic nickel-PTFE composite
Plating coating with tin plating on top
Heated at 350 ° C. for 30 minutes in a hot-air circulation drying oven
Then, it was left indoors at room temperature for 1 hour. Table of this plated coating
X-ray diffractometer (Rigaku Denki Co., Ltd., RINT250)
0), it was found that NiThreeSn and NiThreeS
n TwoNickel-tin alloys of the two types
I found out. In addition, the surface of the plating coating is
A analyzer (JXA-8900RL manufactured by JEOL Ltd.)
When analyzed by using, nickel: 83% by weight and
: 17% by weight of a nickel-tin alloy is formed
Was. In addition, using the EPMA analyzer,
The analysis of the direction of tin showed that the thickness of the tin diffusion layer was
It was 3 μm. This corrosion resistant composite plating film was applied
The same test evaluation as in Example 1 was performed using the coating.
【００９７】実施例３ 実施例１の電解スズメッキの膜厚を１．２μｍとした以
外は、実施例１と同様にして、基材にニッケルストライ
クメッキ、電解ニッケル−ＰＴＦＥメッキ皮膜及び電解
スズメッキ皮膜を順次形成した。Example 3 A nickel strike plating, an electrolytic nickel-PTFE plating film and an electrolytic tin plating film were applied to a substrate in the same manner as in Example 1 except that the film thickness of the electrolytic tin plating of Example 1 was changed to 1.2 μm. Formed sequentially.
【００９８】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上にスズメッキ皮膜を施したメッキ被覆物を、
熱風循環式乾燥炉中で、３５０℃で３０分間加熱した
後、常温で１時間室内放置した。このメッキ被覆物の表
面をＸ線回折装置（理学電機（株）、ＲＩＮＴ２５０
０）を用いて分析したところ、Ｎｉ3Ｓｎ2、及びＮｉ3
Ｓｎ4の２種類の組成のニッケル−スズ合金が生成して
いることが分かった。また、メッキ被覆物の表面をＥＰ
ＭＡ分析装置（日本電子（株）製ＪＸＡ−８９００Ｒ
Ｌ）を用いて分析したところ、ニッケル：４１重量％及
びスズ：５９重量％のニッケル−スズ合金が形成されて
いた。また、前記ＥＰＭＡ分析装置を用いて、断面深さ
方向のスズの分析を行ったところ、スズの拡散層の厚み
は３μｍであった。この耐食性複合メッキ皮膜が施され
た被覆物を用いて実施例１と同様の試験評価を行った。A plating coating obtained by applying a tin plating film on the obtained electrolytic nickel-PTFE composite plating film was
After heating at 350 ° C. for 30 minutes in a hot air circulating drying oven, it was left indoors at room temperature for 1 hour. An X-ray diffractometer (Rigaku Corporation, RINT250)
0), Ni 3 Sn 2 and Ni 3
It was found that nickel-tin alloys of two compositions of Sn 4 were formed. In addition, the surface of the plating coating is EP
MA analyzer (JXA-8900R manufactured by JEOL Ltd.)
As a result of analysis using L), a nickel-tin alloy of 41% by weight of nickel and 59% by weight of tin was formed. When tin was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the tin diffusion layer was 3 μm. The same test evaluation as in Example 1 was performed using the coating provided with the corrosion-resistant composite plating film.
【００９９】実施例４ 実施例１の電解ニッケル−ＰＴＦＥ複合メッキ液におい
て、ＰＴＦＥ微粒子の代わりにＦＥＰ微粒子（平均粒子
径１μｍ、ダイキン工業（株）製）を電解ニッケルメッ
キ液１リットルに対して５０ｇ添加した以外は、実施例
１と同様にして、被メッキ材料にニッケルストライクメ
ッキ、電解ニッケル−ＦＥＰ複合メッキ皮膜及び電解ス
ズメッキ皮膜を順次形成した。Example 4 In the electrolytic nickel-PTFE composite plating solution of Example 1, 50 g of FEP fine particles (average particle diameter: 1 μm, manufactured by Daikin Industries, Ltd.) were used in place of 1 μl of the electrolytic nickel plating solution instead of the PTFE fine particles. Except for the addition, a nickel strike plating, an electrolytic nickel-FEP composite plating film and an electrolytic tin plating film were sequentially formed on the material to be plated in the same manner as in Example 1.
【０１００】得られた電解ニッケル−ＦＥＰ複合メッキ
皮膜の上に電解スズメッキ皮膜を施したメッキ被覆物
を、熱風循環式乾燥炉中で、３００℃で３０分間加熱し
た後、常温で１時間室内放置した。また、メッキ被覆物
の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−
８９００ＲＬ）を用いて分析したところ、ニッケル：６
４重量％及びスズ：３６重量％のニッケル−スズ合金が
形成されていた。また、前記ＥＰＭＡ分析装置を用い
て、断面深さ方向のスズの分析を行ったところ、スズの
拡散層の厚みは３μｍであった。この耐食性複合被メッ
キ材料を用いて実施例１と同様の試験評価を行った。The plated coating obtained by applying an electrolytic tin plating film on the obtained electrolytic nickel-FEP composite plating film was heated at 300 ° C. for 30 minutes in a hot air circulating drying oven, and then left indoors at room temperature for 1 hour. did. In addition, the surface of the plating coating was measured with an EPMA analyzer (JXA-JEOL).
8900 RL), it was found that nickel: 6
4% by weight and 36% by weight of tin: a nickel-tin alloy was formed. When tin was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the tin diffusion layer was 3 μm. Using this corrosion-resistant composite plating material, the same test and evaluation as in Example 1 were performed.
【０１０１】なお、ＦＥＰ共析率（容量％）は、ニッケ
ルストライクメッキ及び電解ニッケル−ＦＥＰ複合メッ
キ皮膜を形成した後、評価した。ＦＥＰ共析率は３０容
量％であった。The FEP eutectoid rate (% by volume) was evaluated after forming nickel strike plating and electrolytic nickel-FEP composite plating film. The FEP eutectoid rate was 30% by volume.
【０１０２】実施例５ 実施例１の電解ニッケル−ＰＴＦＥ複合メッキ液におい
て、ＰＴＦＥ微粒子の代わりにＰＦＡ微粒子（平均粒子
径０．５μｍ、ダイキン工業（株）製）を電解ニッケル
メッキ液１リットルに対して５０ｇ添加した以外は、実
施例１と同様にして、基材にニッケルストライクメッ
キ、電解ニッケル−ＰＦＡ複合メッキ皮膜及び電解スズ
メッキ皮膜を順次形成した。Example 5 In the electrolytic nickel-PTFE composite plating solution of Example 1, PFA fine particles (average particle diameter: 0.5 μm, manufactured by Daikin Industries, Ltd.) were used instead of PTFE fine particles per liter of electrolytic nickel plating solution. A nickel strike plating, an electrolytic nickel-PFA composite plating film and an electrolytic tin plating film were sequentially formed on the substrate in the same manner as in Example 1 except that 50 g was added.
【０１０３】得られた電解ニッケル−ＰＦＡ複合メッキ
皮膜の上に電解スズメッキ皮膜を施したメッキ被覆物
を、熱風循環式乾燥炉中で、３５０℃で３０分間加熱し
た後、常温で１時間室内放置した。また、メッキ被覆物
の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−
８９００ＲＬ）を用いて分析したところ、ニッケル：６
４重量％及びスズ：３６重量％のニッケル−スズ合金が
形成されていた。また、前記ＥＰＭＡ分析装置を用い
て、断面深さ方向のスズの分析を行ったところ、スズの
拡散層の厚みは３μｍであった。この耐食性複合被メッ
キ材料を用いて実施例１と同様の試験評価を行った。The plated coating obtained by applying an electrolytic tin plating film on the obtained electrolytic nickel-PFA composite plating film was heated at 350 ° C. for 30 minutes in a circulating hot air drying oven, and then left indoors at room temperature for 1 hour. did. In addition, the surface of the plating coating was measured with an EPMA analyzer (JXA-JEOL).
8900 RL), it was found that nickel: 6
4% by weight and 36% by weight of tin: a nickel-tin alloy was formed. When tin was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the tin diffusion layer was 3 μm. Using this corrosion-resistant composite plating material, the same test and evaluation as in Example 1 were performed.
【０１０４】なお、ＰＦＡ共析率（容量％）は、ニッケ
ルストライクメッキ及び電解ニッケル−ＰＦＡ複合メッ
キ皮膜を形成した後、評価した。ＰＦＡ共析率は３０容
量％であった。The PFA eutectoid ratio (% by volume) was evaluated after nickel strike plating and electrolytic nickel-PFA composite plating film formation. The PFA eutectoid rate was 30% by volume.
【０１０５】実施例６ 実施例１の電解ニッケル−ＰＴＦＥ複合メッキ液におい
て、ＰＴＦＥ微粒子の代わりにＰＣＴＦＥ微粒子（平均
粒子径２μｍ、ダイキン工業（株）製）を電解ニッケル
メッキ液１リットルに対して５０ｇ添加した以外は、実
施例１と同様にして、基材にニッケルストライクメッ
キ、電解ニッケル−ＰＣＴＦＥ複合メッキ皮膜及び電解
スズメッキ皮膜を順次形成した。Example 6 In the electrolytic nickel-PTFE composite plating solution of Example 1, PCTF fine particles (average particle diameter: 2 μm, manufactured by Daikin Industries, Ltd.) were used in place of PTFE fine particles in an amount of 50 g per liter of the electrolytic nickel plating solution. Except for the addition, a nickel strike plating, an electrolytic nickel-PCTFE composite plating film and an electrolytic tin plating film were sequentially formed on the substrate in the same manner as in Example 1.
【０１０６】得られた電解ニッケル−ＰＣＴＦＥ複合メ
ッキ皮膜の上に電解スズメッキ皮膜を施したメッキ被覆
物を、熱風循環式乾燥炉中で、２５０℃で３０分間加熱
した後、常温で１時間室内放置した。また、メッキ被覆
物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ
−８９００ＲＬ）を用いて分析したところ、ニッケル：
６４重量％及びスズ：３６重量％のニッケル−スズ合金
が形成されていた。また、前記ＥＰＭＡ分析装置を用い
て、断面深さ方向のスズの分析を行ったところ、スズの
拡散層の厚みは３μｍであった。この耐食性複合被メッ
キ材料を用いて実施例１と同様の試験評価を行った。The plated coating obtained by applying an electrolytic tin plating film on the obtained electrolytic nickel-PCTFE composite plating film was heated at 250 ° C. for 30 minutes in a circulating hot air drying oven, and then left indoors at room temperature for 1 hour. did. In addition, the surface of the plating coating was measured using an EPMA analyzer (JXA manufactured by JEOL Ltd.).
-8900 RL), the nickel:
A nickel-tin alloy of 64% by weight and 36% by weight of tin was formed. When tin was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the tin diffusion layer was 3 μm. Using this corrosion-resistant composite plating material, the same test and evaluation as in Example 1 were performed.
【０１０７】なお、ＰＣＴＦＥ共析率（容量％）は、ニ
ッケルストライクメッキ及び電解ニッケル−ＰＣＴＦＥ
複合メッキ皮膜を形成した後、評価した。ＰＣＴＦＥ共
析率は３０容量％であった。The PCTFE eutectoid rate (% by volume) was determined by nickel strike plating and electrolytic nickel-PCTFE.
After forming the composite plating film, evaluation was made. The PCTFE eutectoid rate was 30% by volume.
【０１０８】実施例７ 実施例１の電解ニッケル−ＰＴＦＥ複合メッキ液におい
て、ＰＴＦＥ微粒子の代わりにＥＴＦＥ微粒子（平均粒
子径２μｍ、ダイキン工業（株）製）を電解ニッケルメ
ッキ液１リットルに対して５０ｇ添加した以外は、実施
例１と同様にして、被メッキ材料にニッケルストライク
メッキ、電解ニッケル−ＥＴＦＥ複合メッキ皮膜及び電
解スズメッキ皮膜を順次形成した。Example 7 In the electrolytic nickel-PTFE composite plating solution of Example 1, 50 g of ETFE fine particles (average particle diameter: 2 μm, manufactured by Daikin Industries, Ltd.) was used in place of 1 g of the electrolytic nickel plating solution instead of PTFE fine particles. Except for the addition, a nickel strike plating, an electrolytic nickel-ETFE composite plating film and an electrolytic tin plating film were sequentially formed on the material to be plated in the same manner as in Example 1.
【０１０９】得られた電解ニッケル−ＥＴＦＥ複合メッ
キ皮膜の上に電解スズメッキ皮膜を施したメッキ被覆物
を、熱風循環式乾燥炉中で、２５０℃で３０分間加熱し
た後、常温で１時間室内放置した。このメッキ被覆物の
表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−８
９００ＲＬ）を用いて分析したところ、ニッケル：６４
重量％及びスズ：３６重量％のニッケル−スズ合金が形
成されていた。また、前記ＥＰＭＡ分析装置を用いて、
断面深さ方向のスズの分析を行ったところ、スズの拡散
層の厚みは３μｍであった。この耐食性複合被メッキ材
料を用いて実施例１と同様の試験評価を行った。[0109] The plated coating obtained by applying an electrolytic tin plating film on the obtained electrolytic nickel-ETFE composite plating film was heated at 250 ° C for 30 minutes in a hot-air circulation drying furnace, and then left indoors at room temperature for 1 hour. did. The surface of the plated coating was measured with an EPMA analyzer (JXA-8 manufactured by JEOL Ltd.).
900 RL), nickel: 64
% By weight and tin: 36% by weight of a nickel-tin alloy was formed. Further, using the EPMA analyzer,
When tin was analyzed in the cross-sectional depth direction, the thickness of the tin diffusion layer was 3 μm. Using this corrosion-resistant composite plating material, the same test and evaluation as in Example 1 were performed.
【０１１０】なお、ＥＴＦＥ共析率（容量％）は、ニッ
ケルストライクメッキ及び電解ニッケル−ＥＴＦＥ複合
メッキ皮膜を形成した後、評価した。ＥＴＦＥ共析率は
３０容量％であった。The ETFE eutectoid ratio (% by volume) was evaluated after nickel strike plating and electrolytic nickel-ETFE composite plating film were formed. The ETFE eutectoid rate was 30% by volume.
【０１１１】実施例８ 実施例１の電解ニッケル−ＰＴＦＥ複合メッキ液におい
て、ＰＴＦＥ微粒子の代わりにフッ化黒鉛微粒子（平均
粒子径１μｍ、旭硝子（株）製）を電解ニッケルメッキ
液１リットルに対して５０ｇ添加した以外は、実施例１
と同様にして、被メッキ材料にニッケルストライクメッ
キ、電解ニッケル−フッ化黒鉛複合メッキ皮膜及び電解
スズメッキ皮膜を順次形成した。Example 8 In the electrolytic nickel-PTFE composite plating solution of Example 1, fluorinated graphite fine particles (average particle size: 1 μm, manufactured by Asahi Glass Co., Ltd.) were used instead of PTFE fine particles per liter of electrolytic nickel plating solution. Example 1 except that 50 g was added.
In the same manner as in the above, a nickel strike plating, an electrolytic nickel-fluorinated graphite composite plating film and an electrolytic tin plating film were sequentially formed on the material to be plated.
【０１１２】得られた電解ニッケル−フッ化黒鉛複合メ
ッキ皮膜の上に電解スズメッキ皮膜を施したメッキ被覆
物を、熱風循環式乾燥炉中で、３５０℃で３０分間加熱
した後、常温で１時間室内放置した。このメッキ被覆物
の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−
８９００ＲＬ）を用いて分析したところ、ニッケル：６
４重量％及びスズ：３６重量％のニッケル−スズ合金が
形成されていた。また、前記ＥＰＭＡ分析装置を用い
て、断面深さ方向のスズの分析を行ったところ、スズの
拡散層の厚みは３μｍであった。この耐食性複合被メッ
キ材料を用いて実施例１と同様の試験評価を行った。[0112] The plated coating obtained by applying an electrolytic tin plating film on the obtained electrolytic nickel-fluorinated graphite composite plating film was heated at 350 ° C for 30 minutes in a hot-air circulation drying furnace, and then at room temperature for 1 hour. Left indoors. The surface of the plating coating was measured using an EPMA analyzer (JXA-
8900 RL), it was found that nickel: 6
4% by weight and 36% by weight of tin: a nickel-tin alloy was formed. When tin was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the tin diffusion layer was 3 μm. Using this corrosion-resistant composite plating material, the same test and evaluation as in Example 1 were performed.
【０１１３】なお、フッ化黒鉛共析率（容量％）は、ニ
ッケルストライクメッキ及び電解ニッケル−フッ化黒鉛
複合メッキ皮膜を形成した後、評価した。フッ化黒鉛共
析率は３０容量％であった。The graphite eutectoid rate (volume%) was evaluated after nickel strike plating and formation of an electrolytic nickel-fluorinated graphite composite plating film. The fluorinated graphite eutectoid ratio was 30% by volume.
【０１１４】実施例９ 実施例１の電解ニッケル−ＰＴＦＥ複合メッキ液におい
て、ＰＴＦＥ微粒子の代わりにフッ化ピッチ（平均粒子
径１μｍ、大阪ガス（株）製）を電解ニッケルメッキ液
１リットルに対して５０ｇ添加した以外は、実施例１と
同様にして、被メッキ材料にニッケルストライクメッ
キ、電解ニッケル−フッ化ピッチ複合メッキ皮膜及び電
解スズメッキ皮膜を順次形成した。Example 9 In the electrolytic nickel-PTFE composite plating solution of Example 1, pitch fluoride (average particle diameter: 1 μm, manufactured by Osaka Gas Co., Ltd.) was used instead of PTFE fine particles per liter of electrolytic nickel plating solution. Except for adding 50 g, a nickel strike plating, an electrolytic nickel-fluoride pitch composite plating film and an electrolytic tin plating film were sequentially formed on the material to be plated in the same manner as in Example 1.
【０１１５】得られた電解ニッケル−フッ化ピッチ複合
メッキ皮膜の上に電解スズメッキ皮膜を有する被メッキ
材料を、熱風循環式乾燥炉中で、３００℃で３０分間加
熱した後、常温で１時間室内放置した。このメッキ被覆
物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ
−８９００ＲＬ）を用いて分析したところ、ニッケル：
６４重量％及びスズ：３６重量％のニッケル−スズ合金
が形成されていた。また、前記ＥＰＭＡ分析装置を用い
て、断面深さ方向のスズの分析を行ったところ、スズの
拡散層の厚みは３μｍであった。この耐食性複合被メッ
キ材料を用いて実施例１と同様の試験評価を行った。A material to be plated having an electrolytic tin plating film on the obtained electrolytic nickel-fluoride pitch composite plating film was heated at 300 ° C. for 30 minutes in a hot-air circulating drying oven, and then indoors at room temperature for 1 hour. I left it. The surface of this plated coating is measured using an EPMA analyzer (JXA manufactured by JEOL Ltd.).
-8900 RL), the nickel:
A nickel-tin alloy of 64% by weight and 36% by weight of tin was formed. When tin was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the tin diffusion layer was 3 μm. Using this corrosion-resistant composite plating material, the same test and evaluation as in Example 1 were performed.
【０１１６】なお、フッ化ピッチ共析率（容量％）は、
ニッケルストライクメッキ及び電解ニッケル−フッ化ピ
ッチ複合メッキ皮膜を形成した後、評価した。フッ化ピ
ッチ共析率は３０容量％であった。The pitch fluoride eutectoid ratio (% by volume)
After forming a nickel strike plating and an electrolytic nickel-fluoride pitch composite plating film, evaluation was made. The pitch fluoride eutectoid ratio was 30% by volume.
【０１１７】実施例１０ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 10 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０１１８】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−コバルト−ＰＴＦＥ複合メッキ液
の調製 電解ニッケル−コバルト合金メッキ液（組成：スルファ
ミン酸ニッケル３６０ｇ／Ｌ、スルファミン酸コバルト
１０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ／
Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子径
０．２μｍ、ダイキン工業（株）製、ルブロンＬ−２）
５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面活性
剤としての第４級パーフルオロアンモニウム塩［Ｃ8Ｆ
17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録商
標「メガファックＦ１５０」，大日本インキ化学（株）
製］を３０．０ｍｇ添加して、電解ニッケル−コバルト
−ＰＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-cobalt-PTFE composite plating solution Electrolytic nickel-cobalt alloy plating solution (composition: nickel sulfamate 360 g / L, cobalt sulfamate 10 g / L, Nickel chloride 45g / L, boric acid 30g /
L) PTFE fine particles (average particle diameter 0.2 μm, Lubron L-2, manufactured by Daikin Industries, Ltd.) per 1 liter
50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C 8 F
17 SO 2 NH (CH 2 ) 3 N + (CH 3 ) 3 .Cl − , registered trademark “MegaFac F150”, Dainippon Ink and Chemicals, Inc.
Was added to prepare an electrolytic nickel-cobalt-PTFE composite plating solution.
【０１１９】（３）電解スズメッキ液の調製 実施例１と同様に電解スズメッキ液を調製した。(3) Preparation of Electrolytic Tin Plating Solution An electrolytic tin plating solution was prepared in the same manner as in Example 1.
【０１２０】（４）メッキ法 前記各基材（被メッキ材料）をアルカリ脱脂液で脱脂し
た後、それぞれを負極とし、上記（１）の組成のニッケ
ルストライクメッキ液を含むメッキ槽を用いて、液温２
５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッケルス
トライクメッキ処理を２分間行った。(4) Plating Method After degreased each of the base materials (materials to be plated) with an alkaline degreasing solution, each was used as a negative electrode, and a plating tank containing a nickel strike plating solution having the composition (1) was used. Liquid temperature 2
Under a condition of 5 ° C. and a current density of 10 A / dm 2 , nickel strike plating was performed for 2 minutes.
【０１２１】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−コバルト−ＰＴＦＥ複合
メッキ液を含むメッキ槽中、液温５０℃、ｐＨ４．２、
電流密度２Ａ／ｄｍ2の条件で、スクリュー撹拌しつ
つ、膜厚が１０μｍとなるまで電解メッキを行って、電
解ニッケル−コバルト−ＰＴＦＥ複合メッキ皮膜を形成
させた。この時点で共析率測定用試験片を使用し、ＰＴ
ＦＥの共析率（容量％）を求めたところ、３０容量％で
あった。Next, using the obtained coating material, in a plating tank containing the electrolytic nickel-cobalt-PTFE composite plating solution having the composition of the above (2), a solution temperature of 50 ° C. and a pH of 4.2
Under a condition of a current density of 2 A / dm 2 , electrolytic plating was performed until the film thickness became 10 μm while stirring with a screw to form an electrolytic nickel-cobalt-PTFE composite plating film. At this point, the test piece for eutectoid ratio measurement was
When the eutectoid rate (volume%) of FE was determined, it was 30 vol%.
【０１２２】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解スズメッキ液
を含むメッキ槽を用いて、液温３５℃、ｐＨ６．０及び
電流密度２Ａ／ｄｍ2の条件で、膜厚が０．５μｍとな
るまで電解メッキを行って、スズメッキ皮膜を形成させ
た。メッキ終了後、水洗し、１００℃で、５分間乾燥さ
せた。Further, using the composite-plated coating as a negative electrode and a plating bath containing an electrolytic tin plating solution having the composition of (3) above, a solution temperature of 35 ° C., a pH of 6.0 and a current density of 2 A / dm 2 Under the conditions of 2, the electrolytic plating was performed until the film thickness became 0.5 μm to form a tin plating film. After plating was completed, it was washed with water and dried at 100 ° C. for 5 minutes.
【０１２３】得られた電解ニッケル−コバルト−ＰＴＦ
Ｅ複合メッキ皮膜の上にスズメッキ皮膜を施したメッキ
被覆物を、熱風循環式乾燥炉中で、３５０℃で３０分間
加熱した後、常温で１時間室内放置した。このメッキ被
覆物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸ
Ａ−８９００ＲＬ）を用いて分析したところ、ニッケ
ル：５１重量％、コバルト：１３重量％及びスズ：３６
重量％のニッケル−コバルト−スズ合金が形成されてい
た。また、前記ＥＰＭＡ分析装置を用いて、断面深さ方
向のスズの分析を行ったところ、スズの拡散層の厚みは
３μｍであった。The obtained electrolytic nickel-cobalt-PTF
The plated coating obtained by applying a tin plating film on the E composite plating film was heated at 350 ° C. for 30 minutes in a hot-air circulation drying oven, and then left indoors at room temperature for 1 hour. The surface of the plated coating is measured with an EPMA analyzer (JX manufactured by JEOL Ltd.).
A-8900RL), it was found that nickel: 51% by weight, cobalt: 13% by weight, and tin: 36% by weight.
By weight, a nickel-cobalt-tin alloy was formed. When tin was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the tin diffusion layer was 3 μm.
【０１２４】この耐食性複合メッキ皮膜が施された被覆
物を用いて共析率以外の上記（２）〜（１１）の試験を
行った。Using the coating provided with the corrosion-resistant composite plating film, the above tests (2) to (11) other than the eutectoid ratio were performed.
【０１２５】実施例１１ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 11 (1) Preparation of nickel strike plating solution A nickel strike plating solution having the following composition was prepared.
【０１２６】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）無電解ニッケル／リンメッキ液の調製 下記の組成を有する無電解ニッケル／リンメッキ液を調
製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electroless nickel / phosphorus plating solution An electroless nickel / phosphorus plating solution having the following composition was prepared.
【０１２７】 硫酸ニッケル ２０ｇ／Ｌ 次亜リン酸ナトリウム ２５ｇ／Ｌ 乳酸 ２０ｇ／Ｌ プロピオン酸 ３ｇ／Ｌ （３）無電解ニッケル／リン−ＰＴＦＥ複合メッキ液の
調製 上記組成を有する無電解ニッケル／リンメッキ液１リッ
トルに対して、ＰＴＦＥ微粒子（平均粒子径０．２μ
ｍ、ダイキン工業（株）製、ルブロンＬ−２）１０ｇを
添加し、このＰＴＦＥ１ｇに対して、界面活性剤として
の第４級パーフルオロアンモニウム塩［Ｃ8Ｆ17ＳＯ2Ｎ
Ｈ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録商標「メガフ
ァックＦ１５０」，大日本インキ化学（株）製］を３
０．０ｍｇ添加して、無電解ニッケル／リン−ＰＴＦＥ
複合メッキ液を調製した。Nickel sulfate 20 g / L Sodium hypophosphite 25 g / L Lactic acid 20 g / L Propionic acid 3 g / L (3) Preparation of electroless nickel / phosphorus-PTFE composite plating solution Electroless nickel / phosphorus plating solution having the above composition PTFE fine particles (average particle size 0.2μ
m, Lubron L-2, manufactured by Daikin Industries, Ltd.), and 10 g of the PTFE was added to 1 g of the PTFE to form a quaternary perfluoroammonium salt [C 8 F 17 SO 2 N] as a surfactant.
H (CH 2 ) 3 N + (CH 3 ) 3 .Cl − , registered trademark “MegaFac F150”, manufactured by Dainippon Ink and Chemicals, Inc.]
0.0mg added, electroless nickel / phosphorus-PTFE
A composite plating solution was prepared.
【０１２８】（４）電解スズメッキ液の調製 実施例１と同様に電解スズメッキ液を調製した。(4) Preparation of Electrolytic Tin Plating Solution An electrolytic tin plating solution was prepared in the same manner as in Example 1.
【０１２９】（５）メッキ法 前記各基材（被メッキ材料）をアルカリ脱脂液で脱脂し
た後、それぞれを負極とし、前記（１）の組成のニッケ
ルストライクメッキ液を含むメッキ槽を用いて、液温２
５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッケルス
トライクメッキ処理を２分間行った。(5) Plating method After each of the base materials (materials to be plated) was degreased with an alkali degreasing solution, each was used as a negative electrode, and a plating tank containing a nickel strike plating solution having the composition (1) was used. Liquid temperature 2
Under a condition of 5 ° C. and a current density of 10 A / dm 2 , nickel strike plating was performed for 2 minutes.
【０１３０】次いで、得られた被覆物を用いて、前記
（２）の組成の無電解ニッケル／リンメッキ液を含むメ
ッキ槽を用いて、液温９０℃、ｐＨ４．６の条件下に、
スクリュー撹拌しつつ、膜厚が３μｍとなるまで無電解
メッキを行って、無電解下地ニッケル／リンメッキ皮膜
を形成させた。Next, using the obtained coating, a plating bath containing an electroless nickel / phosphorous plating solution having the composition of the above (2) was used under the conditions of a liquid temperature of 90 ° C. and a pH of 4.6.
While stirring with a screw, electroless plating was performed until the film thickness became 3 μm, thereby forming an electroless base nickel / phosphorus plating film.
【０１３１】さらに、この無電解下地ニッケル／リンメ
ッキ皮膜が施された被覆物を、前記（３）の組成の無電
解ニッケル／リン−ＰＴＦＥ複合メッキ液を含む複合メ
ッキ槽を用いて、液温９０℃、ｐＨ５．１の条件で、ス
クリュー撹拌しつつ、膜厚が７μｍとなるまで無電解メ
ッキを行って、無電解ニッケル／リン−ＰＴＦＥ複合メ
ッキ皮膜を形成させた。Further, the coating having the electroless base nickel / phosphorous plating film formed thereon was treated with a composite plating bath containing the electroless nickel / phosphorus-PTFE composite plating solution of the composition (3) above at a solution temperature of 90%. Electroless plating was performed under conditions of a temperature of 5 ° C. and a pH of 5.1 until the film thickness became 7 μm while stirring with a screw to form an electroless nickel / phosphorus-PTFE composite plating film.
【０１３２】この時点でＰＴＦＥ共析率（容量％）を求
めたところ、３０容量％であった。At this point, the PTFE eutectoid rate (volume%) was determined to be 30 vol%.
【０１３３】得られた無電解ニッケル／リン−ＰＴＦＥ
複合メッキ皮膜が施された被覆物をを水洗した後、負極
として前記（４）の電解スズメッキ液を含むメッキ槽
中、液温３５℃、ｐＨ６．０及び電流密度２Ａ／ｄｍ2
の条件で、膜厚が０．５μｍとなるまで電解メッキを行
って、電解スズメッキ皮膜を形成させた。メッキ終了
後、得られた被覆物を水洗し、１００℃で、５分間乾燥
させた。The obtained electroless nickel / phosphorus-PTFE
After washing the coated body with the composite plating film with water, in a plating tank containing the electrolytic tin plating solution of the above (4) as a negative electrode, the solution temperature is 35 ° C., the pH is 6.0, and the current density is 2 A / dm 2.
Under the conditions described above, electrolytic plating was performed until the film thickness became 0.5 μm to form an electrolytic tin plating film. After the plating was completed, the obtained coating was washed with water and dried at 100 ° C. for 5 minutes.
【０１３４】得られた無電解ニッケル／リン−ＰＴＦＥ
複合メッキ皮膜の上にスズメッキ皮膜を施した被覆物
を、熱風循環式乾燥炉中で、３５０℃で３０分間加熱し
た後、常温で１時間室内放置した。このメッキ被覆物の
表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−８
９００ＲＬ）を用いて分析したところ、ニッケル：５９
重量％、リン：５重量％、及びズ：３６重量％のニッケ
ル−スズ−リン合金が形成されていた。また、前記ＥＰ
ＭＡ分析装置を用いて、断面深さ方向のスズの分析を行
ったところ、スズの拡散層の厚みは３μｍであった。The obtained electroless nickel / phosphorus-PTFE
The coated product obtained by applying the tin plating film on the composite plating film was heated at 350 ° C. for 30 minutes in a hot-air circulation drying oven, and then left at room temperature for 1 hour at room temperature. The surface of the plated coating was measured with an EPMA analyzer (JXA-8 manufactured by JEOL Ltd.).
900 RL), nickel: 59
By weight, a nickel-tin-phosphorus alloy of 5% by weight of phosphorus, and 36% by weight of phosphorus was formed. The EP
When tin was analyzed in the cross-section depth direction using an MA analyzer, the thickness of the tin diffusion layer was 3 μm.
【０１３５】この耐食性複合メッキ皮膜が施された被覆
物を用いて共析率以外の上記（２）〜（１１）の試験を
行った。Using the coating provided with the corrosion-resistant composite plating film, the above tests (2) to (11) other than the eutectoid ratio were performed.
【０１３６】比較例１ スズメッキを行わない以外は、実施例１と同様に操作及
び評価を行った。なお、共析率の測定は、熱風循環式乾
燥炉中での加熱の前に行った。Comparative Example 1 The operation and evaluation were performed in the same manner as in Example 1 except that tin plating was not performed. The eutectoid ratio was measured before heating in a hot air circulation type drying furnace.
【０１３７】実施例１と同様の基材に、実施例１と同様
にして脱脂、ニッケルストライクメッキ、電解ニッケル
−ＰＴＦＥ複合メッキ皮膜を形成させた。このあと、ス
ズメッキを行うことなく、電解ニッケル−ＰＴＦＥ複合
メッキ皮膜が施された被覆物を、熱風循環式乾燥炉中
で、３５０℃で３０分間加熱した後、次いで常温で１時
間室内放置した。得られたメッキ被覆物を用いて実施例
１と同様の試験評価を行った。On the same substrate as in Example 1, degreasing, nickel strike plating, and electrolytic nickel-PTFE composite plating film were formed in the same manner as in Example 1. Thereafter, the coating on which the electrolytic nickel-PTFE composite plating film was applied was heated at 350 ° C. for 30 minutes in a hot-air circulation drying oven without tin plating, and then left indoors at room temperature for 1 hour. The same test and evaluation as in Example 1 were performed using the obtained plated coating.
【０１３８】なお、ＰＴＦＥ共析率（容量％）は、上記
加熱処理の前に評価した。ＰＴＦＥ共析率は３０容量％
であった。The PTFE eutectoid rate (% by volume) was evaluated before the above heat treatment. PTFE eutectoid rate is 30% by volume
Met.
【０１３９】比較例２ （１）ニッケルストライクメッキ液の調製 実施例１と同様のニッケルストライクメッキ液を調製し
た。Comparative Example 2 (1) Preparation of Nickel Strike Plating Solution The same nickel strike plating solution as in Example 1 was prepared.
【０１４０】（２）電解ニッケルメッキ液の調製 下記の組成を有する電解ニッケルメッキ液を調製した。(2) Preparation of Electrolytic Nickel Plating Solution An electrolytic nickel plating solution having the following composition was prepared.
【０１４１】 スルファミン酸ニッケル ３６０ｇ／Ｌ 塩化ニッケル ４５ｇ／Ｌ ホウ酸 ３０ｇ／Ｌ （３）電解スズメッキ液の調製 実施例１と同様に電解スズメッキ液を調製した。Nickel sulfamate 360 g / L Nickel chloride 45 g / L Boric acid 30 g / L (3) Preparation of electrolytic tin plating solution In the same manner as in Example 1, an electrolytic tin plating solution was prepared.
【０１４２】（４）メッキ法 実施例１と同様の基材をアルカリ脱脂液で脱脂した後、
負極とし、上記（１）の組成のニッケルストライクメッ
キ液を含むメッキ槽を用いて、液温２５℃、電流密度１
０Ａ／ｄｍ2の条件下で、ニッケルストライクメッキ処
理を２分間行った。(4) Plating method After the same substrate as in Example 1 was degreased with an alkaline degreasing solution,
Using a negative electrode as a negative electrode and a plating bath containing a nickel strike plating solution having the composition (1), a liquid temperature of 25 ° C. and a current density of 1 were used.
Under a condition of 0 A / dm 2 , nickel strike plating was performed for 2 minutes.
【０１４３】次いで、得られた被覆物を負極とし、上記
（２）の組成の電解ニッケルメッキ液を含むメッキ槽を
用いて、液温５０℃、ｐＨ４．２及び電流密度４Ａ／ｄ
ｍ2の条件で、スクリュー撹拌しつつ、膜厚が１０μｍ
となるまで電解ニッケルメッキを行った。Next, the obtained coating material was used as a negative electrode, and using a plating tank containing an electrolytic nickel plating solution having the composition (2), a solution temperature of 50 ° C., a pH of 4.2 and a current density of 4 A / d
Under the conditions of m 2 , the film thickness is 10 μm while stirring with a screw.
Electrolytic nickel plating was performed until
【０１４４】更に、得られた被覆物を水洗した後、負極
とし、上記（３）の組成を有する電解スズメッキ液を含
むメッキ槽を用いて、液温３５℃、ｐＨ６．０及び電流
密度２Ａ／ｄｍ2の条件下に、膜厚が０．５μｍとなる
まで電解メッキを行って、スズメッキ皮膜を形成させ
た。メッキ終了後、水洗して１００℃、５分間乾燥させ
た。さらに熱風循環式乾燥炉中で、３５０℃で３０分間
加熱した後、次いで常温で１時間室内放置した。このメ
ッキ被覆物の表面をＥＰＭＡ分析装置（日本電子（株）
製ＪＸＡ−８９００ＲＬ）を用いて分析したところ、ニ
ッケル：６４重量％及びスズ：３６重量％のニッケル−
スズ合金が形成されていた。また、前記ＥＰＭＡ分析装
置を用いて、断面深さ方向のスズの分析を行ったとこ
ろ、スズの拡散層の厚みは３μｍであった。得られたメ
ッキ被覆物を用いて実施例１と同様の試験評価を行っ
た。Further, after the obtained coating was washed with water, it was used as a negative electrode, and a plating bath containing an electrolytic tin plating solution having the composition of the above (3) was used. The solution temperature was 35 ° C., the pH was 6.0, and the current density was 2 A / A. Electroplating was performed under the condition of dm 2 until the film thickness became 0.5 μm to form a tin plating film. After the plating was completed, it was washed with water and dried at 100 ° C. for 5 minutes. Further, after heating at 350 ° C. for 30 minutes in a hot-air circulation drying oven, the resultant was left indoors at room temperature for 1 hour. The surface of this plated coating is analyzed with an EPMA analyzer (JEOL Ltd.)
The product was analyzed using JXA-8900RL manufactured by Nissan Co., Ltd. to find that nickel: 64 wt% and tin: 36 wt%
Tin alloy had been formed. When tin was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the tin diffusion layer was 3 μm. The same test and evaluation as in Example 1 were performed using the obtained plated coating.
【０１４５】実施例及び比較例のメッキ被覆物につい
て、前記物性及び特性の評価を行った。結果を表１及び
表２に示す。The physical properties and characteristics of the plated coatings of the examples and comparative examples were evaluated. The results are shown in Tables 1 and 2.
【０１４６】[0146]
【表１】 [Table 1]
【０１４７】[0147]
【表２】 [Table 2]
【０１４８】表１及び２から明らかなように、実施例の
メッキ皮膜は、撥水性、基材との密着性、耐衝撃変形
性、耐薬品性、耐熱性、非粘着性のいずれにも優れてお
り、摺動性も高い。また、魚を焼いた後でも、焼き網か
らの魚の身離れ性が良好で、焼き網における魚の皮の残
存もわずかであるとともに、グリル皿の変色もない。さ
らに、カレーや卵などを高温で焦げ付かせても、生じた
炭化物は指先で軽く圧迫するだけで、容易に剥離した。As is clear from Tables 1 and 2, the plating films of Examples are excellent in water repellency, adhesion to a substrate, impact deformation resistance, chemical resistance, heat resistance, and non-adhesiveness. And high slidability. Also, even after grilling the fish, the fish are easily detached from the grill, the fish skin remains little in the grill, and there is no discoloration of the grill plate. Furthermore, even when curries and eggs were scorched at a high temperature, the resulting carbides were easily peeled off by lightly pressing with a fingertip.
【０１４９】これに対して、スズを含まない比較例１で
は、撥水性、密着性、耐衝撃変形性、摺動性などは高い
ものの、耐薬品性、耐熱性及び非粘着性が低く、魚焼き
試験においてもグリル皿が変色した。特に、耐薬品性に
おいては、台所用漂白剤の５０容量％水溶液に対して茶
褐色錆状物が生じ、１００個中１０個の碁盤目が剥離す
るとともに、４容量％の酢酸水溶液に対して黒色錆状物
が生じ、１００個中１０個の碁盤目が剥離した。また、
非粘着性試験では、ＳＢゴムが付着するとともに、メッ
キ皮膜も黒色に変色した。On the other hand, in Comparative Example 1 containing no tin, although water repellency, adhesion, impact deformation resistance, slidability, etc. were high, chemical resistance, heat resistance and non-adhesion were low, and fish The grill plate also discolored in the baking test. In particular, in terms of chemical resistance, a brown rust-like substance is generated in a 50% by volume aqueous solution of a kitchen bleach, 10 grids out of 100 are peeled off, and a 4% by volume aqueous solution of acetic acid is black. A rust-like substance was formed, and ten grids out of 100 were peeled off. Also,
In the non-adhesion test, the SB rubber adhered and the plating film turned black.
【０１５０】フッ素化合物微粒子を含まない比較例２で
は、密着性、耐衝撃変形性、耐薬品性、耐熱性、耐摩耗
性などは高いものの、撥水性、摺動性が低い。また、焦
げ付き試験や魚焼き試験などにおいて、炭化物や魚の剥
離性が特に低く、油汚れも取れ難かった。さらに非粘着
性試験においてはＳＢゴムが付着した。In Comparative Example 2 containing no fluorine compound fine particles, adhesion, impact deformation resistance, chemical resistance, heat resistance, abrasion resistance, etc. are high, but water repellency and slidability are low. Further, in the scorching test, the grilled fish test, etc., the releasability of carbides and fish was particularly low, and it was difficult to remove oil stains. Further, in the non-adhesion test, SB rubber adhered.
【０１５１】実施例１２ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 12 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０１５２】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−亜鉛−ＰＴＦＥ複合メッキ液の調
製 電解ニッケル−亜鉛合金メッキ液（組成：ニッケル１８
ｇ／Ｌ、亜鉛２０ｇ／Ｌ、ピロリン酸カリウム２４５ｇ
／Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子
径０．２μｍ、ダイキン工業（株）製、ルブロンＬ−
２）５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面
活性剤としての第４級パーフルオロアンモニウム塩［Ｃ
8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録
商標「メガファックＦ１５０」，大日本インキ化学
（株）製］を３０．０ｍｇ添加して、電解ニッケル−亜
鉛−ＰＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-zinc-PTFE composite plating solution Electrolytic nickel-zinc alloy plating solution (composition: nickel 18
g / L, zinc 20g / L, potassium pyrophosphate 245g
/ L) PTFE fine particles (average particle diameter 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-
2) 50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C
8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3 · Cl -, R "Megafac F150", Dainippon Ink and Chemicals Co., Ltd.] was added 30.0mg of electrolytic nickel - A zinc-PTFE composite plating solution was prepared.
【０１５３】（３）メッキ法 前記各基材（被メッキ材料）をアルカリ脱脂液で脱脂し
た後、それぞれを負極とし、前記（１）の組成のニッケ
ルストライクメッキ液を含むメッキ槽を用いて、液温２
５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッケルス
トライクメッキ処理を２分間行った。(3) Plating method Each of the base materials (materials to be plated) was degreased with an alkali degreasing solution, each was then used as a negative electrode, and a plating tank containing a nickel strike plating solution having the composition (1) was used. Liquid temperature 2
Under a condition of 5 ° C. and a current density of 10 A / dm 2 , nickel strike plating was performed for 2 minutes.
【０１５４】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−亜鉛−ＰＴＦＥ複合メッ
キ液を含むメッキ槽中、液温６０℃、ｐＨ９．０、電流
密度２Ａ／ｄｍ2の条件で、スクリュー撹拌しつつ、膜
厚が１０μｍとなるまで電解メッキを行って、電解ニッ
ケル−亜鉛−ＰＴＦＥ複合メッキ皮膜を形成させた。メ
ッキ終了後、水洗し、１００℃で５分間乾燥させた。こ
の時点で共析率測定用試験片を使用し、ＰＴＦＥの共析
率（容量％）を求めたところ、３０容量％であった。ま
た、メッキ被覆物の表面をＥＰＭＡ分析装置（日本電子
（株）製ＪＸＡ−８９００ＲＬ）を用いて分析したとこ
ろ、ニッケル：２５重量％及び亜鉛：７５重量％のニッ
ケル−亜鉛合金が形成されていた。Next, using the obtained coating material, in a plating bath containing the electrolytic nickel-zinc-PTFE composite plating solution having the composition (2), a solution temperature of 60 ° C., a pH of 9.0, and a current density of 2 A / dm. Under the conditions of 2, the electrolytic plating was performed with a screw stirring until the film thickness became 10 μm, thereby forming an electrolytic nickel-zinc-PTFE composite plating film. After the plating was completed, the plate was washed with water and dried at 100 ° C. for 5 minutes. At this point, the eutectoid rate (volume%) of PTFE was determined using a test piece for eutectoid rate measurement, and was 30 vol%. When the surface of the plated material was analyzed using an EPMA analyzer (JXA-8900RL, manufactured by JEOL Ltd.), a nickel-zinc alloy of 25% by weight of nickel and 75% by weight of zinc was formed. .
【０１５５】得られた電解ニッケル−亜鉛−ＰＴＦＥ複
合メッキ皮膜を施したメッキ被覆物を、熱風循環式乾燥
炉中、３５０℃で３０分間加熱した後、常温で１時間、
室内放置した。この耐食性複合メッキ皮膜が施された被
覆物を用いて共析率以外の前記（２）〜（１１）の試験
を行った。[0155] The resulting coated nickel-zinc-PTFE composite plating film was heated at 350 ° C for 30 minutes in a hot air circulating drying oven, and then at room temperature for 1 hour.
Left indoors. Using the coating provided with the corrosion-resistant composite plating film, tests (2) to (11) other than the eutectoid ratio were performed.
【０１５６】実施例１３ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 13 (1) Preparation of nickel strike plating solution A nickel strike plating solution having the following composition was prepared.
【０１５７】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−ＰＴＦＥ複合メッキ液の調製 電解ニッケルメッキ液（組成：スルファミン酸ニッケル
３６０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ
／Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子
径０．２μｍ、ダイキン工業（株）製、ルブロンＬ−
２）５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面
活性剤としての第４級パーフルオロアンモニウム塩［Ｃ
8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録
商標「メガファックＦ１５０」，大日本インキ化学
（株）製］を３０．０ｍｇ添加して、電解ニッケル−Ｐ
ＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-PTFE composite plating solution Electrolytic nickel plating solution (composition: nickel sulfamate 360 g / L, nickel chloride 45 g / L, boric acid 30 g)
/ L) PTFE fine particles (average particle diameter 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-
2) 50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C
8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3 · Cl -, R "Megafac F150", Dainippon Ink and Chemicals Co., Ltd.] was added 30.0mg of electrolytic nickel - P
A TFE composite plating solution was prepared.
【０１５８】（３）電解亜鉛メッキ液の調製 下記の組成を有する電解亜鉛メッキ液を調製した。(3) Preparation of electrolytic zinc plating solution An electrolytic zinc plating solution having the following composition was prepared.
【０１５９】 酸化亜鉛 １７ｇ／Ｌ 水酸化ナトリウム １４０ｇ／Ｌ ３７％ホルマリン ２０ｍＬ／Ｌ （４）メッキ法 前記各基材（被メッキ材料）をアルカリ脱脂液で脱脂し
た後、それぞれを負極とし、前記（１）の組成のニッケ
ルストライクメッキ液を含むメッキ槽を用いて、液温２
５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッケルス
トライクメッキ処理を２分間行った。Zinc oxide 17 g / L sodium hydroxide 140 g / L 37% formalin 20 mL / L (4) Plating method Each of the above-mentioned base materials (material to be plated) was degreased with an alkaline degreasing solution, and then each was made a negative electrode, Using a plating bath containing a nickel strike plating solution having the composition of 1), a solution temperature of 2
Under a condition of 5 ° C. and a current density of 10 A / dm 2 , nickel strike plating was performed for 2 minutes.
【０１６０】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−ＰＴＦＥ複合メッキ液を
含むメッキ槽中、液温５０℃、ｐＨ４．２、電流密度２
Ａ／ｄｍ2の条件で、スクリュー撹拌しつつ、膜厚が１
０μｍとなるまで電解メッキを行って、電解ニッケル−
ＰＴＦＥ複合メッキ皮膜を形成させた。この時点で共析
率測定用試験片を使用し、ＰＴＦＥの共析率（容量％）
を求めたところ、３０容量％であった。Next, using the obtained coating material, in a plating tank containing the electrolytic nickel-PTFE composite plating solution having the composition (2), a solution temperature of 50 ° C., a pH of 4.2, and a current density of 2 were used.
Under the condition of A / dm 2 , the film thickness is 1
Electroplating is performed until the thickness becomes 0 μm.
A PTFE composite plating film was formed. At this point, the eutectoid rate of PTFE (volume%) was measured using a test piece for eutectoid rate measurement.
Was 30% by volume.
【０１６１】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解亜鉛メッキ液
を含むメッキ槽を用いて、液温３０℃、電流密度３Ａ／
ｄｍ 2の条件で、膜厚が０．５μｍとなるまで電解メッ
キを行って、亜鉛メッキ皮膜を形成させた。メッキ終了
後、水洗し、１００℃で、５分間乾燥させた。[0161] Further, the coating material subjected to the composite plating is
As an electrode, an electrolytic galvanizing solution having the composition of (3) above
Using a plating tank containing
dm TwoUnder the conditions described above, until the film thickness becomes 0.5 μm.
The plating was performed to form a galvanized film. Finish plating
Thereafter, it was washed with water and dried at 100 ° C. for 5 minutes.
【０１６２】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上に亜鉛メッキ皮膜を施したメッキ被覆物を、
熱風循環式乾燥炉中で、４００℃で１５分間加熱した
後、常温で１時間室内放置した。このメッキ被覆物の表
面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−８９
００ＲＬ）を用いて分析したところ、ニッケル：６０重
量％及び亜鉛：４０重量％のニッケル−亜鉛合金が形成
されていた。また、前記ＥＰＭＡ分析装置を用いて、断
面深さ方向の亜鉛の分析を行ったところ、亜鉛の拡散層
の厚みは３μｍであった。この耐食性複合メッキ皮膜が
施された被覆物を用いて共析率以外の前記（２）〜（１
１）の試験を行った。A plated coating obtained by applying a zinc plating film on the obtained electrolytic nickel-PTFE composite plating film was
After heating at 400 ° C. for 15 minutes in a hot air circulating drying oven, it was left indoors at room temperature for 1 hour. The surface of the plated coating was measured with an EPMA analyzer (JXA-89 manufactured by JEOL Ltd.).
(00RL), it was found that a nickel-zinc alloy of 60% by weight of nickel and 40% by weight of zinc was formed. When zinc was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the zinc diffusion layer was 3 μm. Using the coating provided with the corrosion-resistant composite plating film, the above (2) to (1) except for the eutectoid ratio were used.
The test of 1) was performed.
【０１６３】実施例１４ 実施例１３の電解亜鉛メッキの膜厚を０．２μｍとした
以外は、実施例１３と同様にして、基材にニッケルスト
ライクメッキ、電解ニッケル−ＰＴＦＥメッキ皮膜及び
電解亜鉛メッキ皮膜を形成した。Example 14 A nickel strike plating, an electrolytic nickel-PTFE plating film and an electrolytic zinc plating were applied to the substrate in the same manner as in Example 13 except that the film thickness of the electrolytic zinc plating in Example 13 was changed to 0.2 μm. A film was formed.
【０１６４】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上に亜鉛メッキ皮膜を施したメッキ被覆物を、
熱風循環式乾燥炉中で、４００℃で１５分間加熱した
後、常温で１時間室内放置した。また、メッキ被覆物の
表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−８
９００ＲＬ）を用いて分析したところ、ニッケル：８０
重量％及び亜鉛：２０重量％のニッケル−亜鉛合金が形
成されていた。また、前記ＥＰＭＡ分析装置を用いて、
断面深さ方向の亜鉛の分析を行ったところ、亜鉛の拡散
層の厚みは３μｍであった。[0164] A plating coating obtained by applying a zinc plating film on the obtained electrolytic nickel-PTFE composite plating film was prepared as follows:
After heating at 400 ° C. for 15 minutes in a hot air circulating drying oven, it was left indoors at room temperature for 1 hour. In addition, the surface of the plating coating was measured with an EPMA analyzer (JXA-8 manufactured by JEOL Ltd.).
900 RL), the nickel: 80
% By weight and zinc: 20% by weight of a nickel-zinc alloy was formed. Further, using the EPMA analyzer,
Analysis of zinc in the cross-sectional depth direction revealed that the thickness of the zinc diffusion layer was 3 μm.
【０１６５】この耐食性複合メッキ皮膜が施された被覆
物を用いて共析率以外の上記（２）〜（１１）の試験を
行った。Using the coating provided with the corrosion-resistant composite plating film, the above tests (2) to (11) other than the eutectoid ratio were performed.
【０１６６】実施例１５ 実施例１３の電解亜鉛メッキの膜厚を１．２μｍとした
以外は、実施例１３と同様にして、基材にニッケルスト
ライクメッキ、電解ニッケル−ＰＴＦＥメッキ皮膜及び
電解亜鉛メッキ皮膜を形成した。Example 15 A nickel strike plating, an electrolytic nickel-PTFE plating film and an electrolytic zinc plating were applied to a substrate in the same manner as in Example 13 except that the film thickness of the electrolytic zinc plating of Example 13 was changed to 1.2 μm. A film was formed.
【０１６７】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上に亜鉛メッキ皮膜を施したメッキ被覆物を、
熱風循環式乾燥炉中で、４００℃で１５分間加熱した
後、常温で１時間室内放置した。また、メッキ被覆物の
表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−８
９００ＲＬ）を用いて分析したところ、ニッケル：４０
重量％及び亜鉛：６０重量％のニッケル−亜鉛合金が形
成されていた。また、前記ＥＰＭＡ分析装置を用いて、
断面深さ方向の亜鉛の分析を行ったところ、亜鉛の拡散
層の厚みは３μｍであった。A plated coating obtained by applying a zinc plating film on the obtained electrolytic nickel-PTFE composite plating film was
After heating at 400 ° C. for 15 minutes in a hot air circulating drying oven, it was left indoors at room temperature for 1 hour. In addition, the surface of the plating coating was measured with an EPMA analyzer (JXA-8 manufactured by JEOL Ltd.).
900 RL), the nickel: 40
% By weight and zinc: 60% by weight of a nickel-zinc alloy was formed. Further, using the EPMA analyzer,
Analysis of zinc in the cross-sectional depth direction revealed that the thickness of the zinc diffusion layer was 3 μm.
【０１６８】この耐食性複合メッキ皮膜が施された被覆
物を用いて共析率以外の上記（２）〜（１１）の試験を
行った。Using the coating provided with the corrosion-resistant composite plating film, the above tests (2) to (11) other than the eutectoid ratio were performed.
【０１６９】実施例１６ 実施例１３の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにＦＥＰ微粒子（平均粒
子径１μｍ、ダイキン工業（株）製）を電解ニッケルメ
ッキ液１リットルに対して５０ｇ添加した以外は、実施
例１３と同様にして、被メッキ材料にニッケルストライ
クメッキ、電解ニッケル−ＦＥＰ複合メッキ皮膜及び電
解亜鉛メッキ皮膜を順次形成させた。Example 16 In the electrolytic nickel-PTFE composite plating solution of Example 13, 50 g of FEP fine particles (average particle diameter: 1 μm, manufactured by Daikin Industries, Ltd.) were used in place of 1 g of the electrolytic nickel plating solution instead of the PTFE fine particles. Except for the addition, a nickel strike plating, an electrolytic nickel-FEP composite plating film, and an electrolytic zinc plating film were sequentially formed on the material to be plated in the same manner as in Example 13.
【０１７０】得られた電解ニッケル−ＦＥＰ複合メッキ
皮膜の上に電解亜鉛メッキ皮膜を施したメッキ被覆物
を、熱風循環式乾燥炉中で、３５０℃で１５分間加熱し
た後、常温で１時間室内放置した。また、メッキ表面を
ＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−８９００
ＲＬ）を用いて分析したところ、ニッケル：５０重量
％、亜鉛：５０重量％のニッケル−亜鉛合金が形成され
ていた。また、前記ＥＰＭＡ分析装置を用いて、断面深
さ方向の亜鉛の分析を行ったところ、亜鉛の拡散層の厚
みは２．５μｍであった。この耐食性複合被メッキ材料
を用いて実施例１３と同様の試験評価を行った。[0170] The plated coating obtained by applying an electrolytic zinc plating film on the obtained electrolytic nickel-FEP composite plating film was heated at 350 ° C for 15 minutes in a hot air circulation type drying furnace, and then indoors at room temperature for 1 hour. I left it. In addition, the plating surface was measured with an EPMA analyzer (JXA-8900 manufactured by JEOL Ltd.).
RL), a nickel-zinc alloy of 50% by weight of nickel and 50% by weight of zinc was formed. Further, when zinc was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the zinc diffusion layer was 2.5 μm. The same test evaluation as in Example 13 was performed using this corrosion-resistant composite plating material.
【０１７１】なお、ＦＥＰ共析率（容量％）は、ニッケ
ルストライクメッキ及び電解ニッケル−ＦＥＰ複合メッ
キ皮膜を形成した後、評価した。ＦＥＰ共析率は３０容
量％であった。The FEP eutectoid rate (volume%) was evaluated after nickel strike plating and electrolytic nickel-FEP composite plating film formation. The FEP eutectoid rate was 30% by volume.
【０１７２】実施例１７ 実施例１３の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにＰＦＡ微粒子（平均粒
子径０．５μｍ、ダイキン工業（株）製）を電解ニッケ
ルメッキ液１リットルに対して５０ｇ添加した以外は、
実施例１３と同様にして、基材にニッケルストライクメ
ッキ、電解ニッケル−ＰＦＡ複合メッキ皮膜及び電解亜
鉛メッキ皮膜を順次形成させた。Example 17 In the electrolytic nickel-PTFE composite plating solution of Example 13, PFA fine particles (average particle size: 0.5 μm, manufactured by Daikin Industries, Ltd.) were used instead of PTFE fine particles per liter of electrolytic nickel plating solution. Except that 50g was added.
In the same manner as in Example 13, a nickel strike plating, an electrolytic nickel-PFA composite plating film, and an electrolytic zinc plating film were sequentially formed on the substrate.
【０１７３】得られた電解ニッケル−ＰＦＡ複合メッキ
皮膜の上に電解亜鉛メッキ皮膜を施したメッキ被覆物
を、熱風循環式乾燥炉中で、４００℃で１５分間加熱し
た後、常温で１時間室内放置した。また、メッキ被覆物
の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−
８９００ＲＬ）を用いて分析したところ、ニッケル：６
０重量％及び亜鉛：４０重量％のニッケル−亜鉛合金が
形成されていた。また、前記ＥＰＭＡ分析装置を用い
て、断面深さ方向の亜鉛の分析を行ったところ、亜鉛の
拡散層の厚みは３μｍであった。この耐食性複合被メッ
キ材料を用いて実施例１３と同様の試験評価を行った。[0173] The plated product obtained by applying an electrolytic zinc plating film on the obtained electrolytic nickel-PFA composite plating film was heated at 400 ° C for 15 minutes in a hot air circulation type drying furnace, and then indoors at room temperature for 1 hour. I left it. In addition, the surface of the plating coating was measured with an EPMA analyzer (JXA-JEOL).
8900 RL), it was found that nickel: 6
0% by weight and zinc: 40% by weight of a nickel-zinc alloy was formed. When zinc was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the zinc diffusion layer was 3 μm. The same test evaluation as in Example 13 was performed using this corrosion-resistant composite plating material.
【０１７４】なお、ＰＦＡ共析率（容量％）は、ニッケ
ルストライクメッキ及び電解ニッケル−ＰＦＡ複合メッ
キ皮膜を形成した後、評価した。ＰＦＡ共析率は３０容
量％であった。Incidentally, the PFA eutectoid rate (volume%) was evaluated after nickel strike plating and electrolytic nickel-PFA composite plating film were formed. The PFA eutectoid rate was 30% by volume.
【０１７５】実施例１８ 実施例１３の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにＰＣＴＦＥ微粒子（平
均粒子径２μｍ、ダイキン工業（株）製）を電解ニッケ
ルメッキ液１リットルに対して５０ｇ添加した以外は、
実施例１３と同様にして、基材にニッケルストライクメ
ッキ、電解ニッケル−ＰＣＴＦＥ複合メッキ皮膜及び電
解亜鉛メッキ皮膜を順次形成させた。Example 18 In the electrolytic nickel-PTFE composite plating solution of Example 13, 50 g of PCTFE fine particles (average particle size: 2 μm, manufactured by Daikin Industries, Ltd.) were used in place of 1 g of the electrolytic nickel plating solution instead of PTFE fine particles. Except for the addition,
In the same manner as in Example 13, a nickel strike plating, an electrolytic nickel-PCTFE composite plating film, and an electrolytic zinc plating film were sequentially formed on the substrate.
【０１７６】得られた電解ニッケル−ＰＣＴＦＥ複合メ
ッキ皮膜の上に電解亜鉛メッキ皮膜を施したメッキ被覆
物を、熱風循環式乾燥炉中で、３００℃で１５分間加熱
した後、常温で１時間室内放置した。また、メッキ表面
をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−８９０
０ＲＬ）を用いて分析したところ、ニッケル：４０重量
％及び亜鉛：６０重量％のニッケル−亜鉛合金が形成さ
れていた。また、前記ＥＰＭＡ分析装置を用いて、断面
深さ方向の亜鉛の分析を行ったところ、亜鉛の拡散層の
厚みは２μｍであった。この耐食性複合被メッキ材料を
用いて実施例１３と同様の試験評価を行った。The plated coating obtained by applying an electrolytic zinc plating film on the obtained electrolytic nickel-PCTFE composite plating film was heated at 300 ° C. for 15 minutes in a circulating hot air drying oven, and then indoors at room temperature for 1 hour. I left it. Further, the plating surface was measured with an EPMA analyzer (JXA-890 manufactured by JEOL Ltd.).
0RL), it was found that a nickel-zinc alloy of 40% by weight of nickel and 60% by weight of zinc was formed. Further, when the zinc was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the zinc diffusion layer was 2 μm. The same test evaluation as in Example 13 was performed using this corrosion-resistant composite plating material.
【０１７７】なお、ＰＣＴＦＥ共析率（容量％）は、ニ
ッケルストライクメッキ及び電解ニッケル−ＰＣＴＦＥ
複合メッキ皮膜を形成した後、評価した。ＰＣＴＦＥ共
析率は３０容量％であった。The PCTFE eutectoid rate (% by volume) was determined by nickel strike plating and electrolytic nickel-PCTFE.
After forming the composite plating film, evaluation was made. The PCTFE eutectoid rate was 30% by volume.
【０１７８】実施例１９ 実施例１３の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにＥＴＦＥ微粒子（平均
粒子径２μｍ、ダイキン工業（株）製）を電解ニッケル
メッキ液１リットルに対して５０ｇ添加した以外は、実
施例１３と同様にして、被メッキ材料にニッケルストラ
イクメッキ、電解ニッケル−ＥＴＦＥ複合メッキ皮膜及
び電解亜鉛メッキ皮膜を順次形成させた。Example 19 In the electrolytic nickel-PTFE composite plating solution of Example 13, 50 g of ETFE fine particles (average particle diameter: 2 μm, manufactured by Daikin Industries, Ltd.) was used in place of 1 g of the electrolytic nickel plating solution instead of the PTFE fine particles. Except for the addition, a nickel strike plating, an electrolytic nickel-ETFE composite plating film and an electrolytic zinc plating film were sequentially formed on the material to be plated in the same manner as in Example 13.
【０１７９】得られた電解ニッケル−ＥＴＦＥ複合メッ
キ皮膜の上に電解亜鉛メッキ皮膜を施したメッキ被覆物
を、熱風循環式乾燥炉中で、３００℃で１５分間加熱し
た後、常温で１時間室内放置した。このメッキ被覆物の
表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−８
９００ＲＬ）を用いて分析したところ、ニッケル：４０
重量％及び亜鉛：６０重量％のニッケル−亜鉛合金が形
成されていた。また、前記ＥＰＭＡ分析装置を用いて、
断面深さ方向の亜鉛の分析を行ったところ、亜鉛の拡散
層の厚みは２μｍであった。この耐食性複合被メッキ材
料を用いて実施例１３と同様の試験評価を行った。[0179] The plated coating obtained by applying an electrolytic zinc plating film on the obtained electrolytic nickel-ETFE composite plating film was heated at 300 ° C for 15 minutes in a hot air circulating drying oven, and then indoors at room temperature for 1 hour. I left it. The surface of the plated coating was measured with an EPMA analyzer (JXA-8 manufactured by JEOL Ltd.).
900 RL), the nickel: 40
% By weight and zinc: 60% by weight of a nickel-zinc alloy was formed. Further, using the EPMA analyzer,
When zinc was analyzed in the cross-sectional depth direction, the thickness of the zinc diffusion layer was 2 μm. The same test evaluation as in Example 13 was performed using this corrosion-resistant composite plating material.
【０１８０】なお、ＥＴＦＥ共析率（容量％）は、ニッ
ケルストライクメッキ及び電解ニッケル−ＥＴＦＥ複合
メッキ皮膜を形成した後、評価した。ＥＴＦＥ共析率は
３０容量％であった。The ETFE eutectoid rate (% by volume) was evaluated after nickel strike plating and electrolytic nickel-ETFE composite plating film were formed. The ETFE eutectoid rate was 30% by volume.
【０１８１】実施例２０ 実施例１３の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにフッ化黒鉛微粒子（平
均粒子径１μｍ、旭硝子（株）製）を電解ニッケルメッ
キ液１リットルに対して５０ｇ添加した以外は、実施例
１３と同様にして、被メッキ材料にニッケルストライク
メッキ、電解ニッケル−フッ化黒鉛複合メッキ皮膜及び
電解亜鉛メッキ皮膜を順次形成させた。Example 20 In the electrolytic nickel-PTFE composite plating solution of Example 13, fluorinated graphite fine particles (average particle diameter: 1 μm, manufactured by Asahi Glass Co., Ltd.) were used instead of PTFE fine particles per liter of electrolytic nickel plating solution. Except that 50 g was added, a nickel strike plating, an electrolytic nickel-fluorinated graphite composite plating film, and an electrolytic zinc plating film were sequentially formed on the material to be plated in the same manner as in Example 13.
【０１８２】得られた電解ニッケル−フッ化黒鉛複合メ
ッキ皮膜の上に電解亜鉛メッキ皮膜を施したメッキ被覆
物を、熱風循環式乾燥炉中で、４００℃で１５分間加熱
した後、常温で１時間室内放置した。このメッキ被覆物
の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−
８９００ＲＬ）を用いて分析したところ、ニッケル：６
０重量％、及び亜鉛：４０重量％のニッケル−亜鉛合金
が形成されていた。また、前記ＥＰＭＡ分析装置を用い
て、断面深さ方向の亜鉛の分析を行ったところ、亜鉛の
拡散層の厚みは３μｍであった。この耐食性複合被メッ
キ材料を用いて実施例１３と同様の試験評価を行った。[0182] The plating coating obtained by applying an electrolytic zinc plating film on the obtained electrolytic nickel-fluorinated graphite composite plating film was heated at 400 ° C for 15 minutes in a hot-air circulating drying furnace, and then heated at room temperature for 1 minute. Left indoors for hours. The surface of the plating coating was measured using an EPMA analyzer (JXA-
8900 RL), it was found that nickel: 6
A nickel-zinc alloy of 0% by weight and 40% by weight of zinc was formed. When zinc was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the zinc diffusion layer was 3 μm. The same test evaluation as in Example 13 was performed using this corrosion-resistant composite plating material.
【０１８３】なお、フッ化黒鉛共析率（容量％）は、ニ
ッケルストライクメッキ及び電解ニッケル−フッ化黒鉛
複合メッキ皮膜を形成した後、評価した。フッ化黒鉛共
析率は３０容量％であった。The graphite eutectoid rate (volume%) was evaluated after nickel strike plating and electrolytic nickel-fluorinated graphite composite plating film formation. The fluorinated graphite eutectoid ratio was 30% by volume.
【０１８４】実施例２１ 実施例１３の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにフッ化ピッチ（平均粒
子径１μｍ、大阪ガス（株）製）を電解ニッケルメッキ
液１リットルに対して５０ｇ添加した以外は、実施例１
３と同様にして、被メッキ材料にニッケルストライクメ
ッキ、電解ニッケル−フッ化ピッチ複合メッキ皮膜及び
電解亜鉛メッキ皮膜を順次形成させた。Example 21 In the electrolytic nickel-PTFE composite plating solution of Example 13, pitch fluoride (average particle diameter: 1 μm, manufactured by Osaka Gas Co., Ltd.) was used instead of PTFE fine particles per liter of electrolytic nickel plating solution. Example 1 except that 50 g was added.
In the same manner as in No. 3, a nickel strike plating, an electrolytic nickel-fluoride pitch composite plating film and an electrolytic zinc plating film were sequentially formed on the material to be plated.
【０１８５】得られた電解ニッケル−フッ化ピッチ複合
メッキ皮膜の上に電解亜鉛メッキ皮膜を有する被メッキ
材料を、熱風循環式乾燥炉中で、３５０℃で１５分間加
熱した後、常温で１時間室内放置した。このメッキ被覆
物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ
−８９００ＲＬ）を用いて分析したところ、ニッケル：
５０重量％及び亜鉛：５０重量％のニッケル−亜鉛合金
が形成されていた。また、前記ＥＰＭＡ分析装置を用い
て、断面深さ方向の亜鉛の分析を行ったところ、亜鉛の
拡散層の厚みは２．５μｍであった。この耐食性複合被
メッキ材料を用いて実施例１３と同様の試験評価を行っ
た。A material to be plated having an electrolytic zinc plating film on the obtained electrolytic nickel-fluoride pitch composite plating film was heated at 350 ° C. for 15 minutes in a hot air circulating drying oven, and then at room temperature for 1 hour. Left indoors. The surface of this plated coating is measured using an EPMA analyzer (JXA manufactured by JEOL Ltd.).
-8900 RL), the nickel:
50% by weight and zinc: 50% by weight of a nickel-zinc alloy was formed. Further, when zinc was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the zinc diffusion layer was 2.5 μm. The same test evaluation as in Example 13 was performed using this corrosion-resistant composite plating material.
【０１８６】なお、フッ化ピッチ共析率（容量％）は、
ニッケルストライクメッキ及び電解ニッケル−フッ化ピ
ッチ複合メッキ皮膜を形成した後、評価した。フッ化ピ
ッチ共析率は３０容量％であった。The pitch fluoride eutectoid rate (% by volume)
After forming a nickel strike plating and an electrolytic nickel-fluoride pitch composite plating film, evaluation was made. The pitch fluoride eutectoid ratio was 30% by volume.
【０１８７】実施例２２ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 22 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０１８８】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−コバルト−ＰＴＦＥ複合メッキ液
の調製 電解ニッケル−コバルト合金メッキ液（組成：スルファ
ミン酸ニッケル３６０ｇ／Ｌ、スルファミン酸コバルト
１０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ／
Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子径
０．２μｍ、ダイキン工業（株）製、ルブロンＬ−２）
５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面活性
剤としての第４級パーフルオロアンモニウム塩［Ｃ8Ｆ
17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録商
標「メガファックＦ１５０」，大日本インキ化学（株）
製］を３０．０ｍｇ添加して、電解ニッケル−コバルト
−ＰＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-cobalt-PTFE composite plating solution Electrolytic nickel-cobalt alloy plating solution (composition: nickel sulfamate 360 g / L, cobalt sulfamate 10 g / L, Nickel chloride 45g / L, boric acid 30g /
L) PTFE fine particles (average particle diameter 0.2 μm, Lubron L-2, manufactured by Daikin Industries, Ltd.) per 1 liter
50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C 8 F
17 SO 2 NH (CH 2 ) 3 N + (CH 3 ) 3 .Cl − , registered trademark “MegaFac F150”, Dainippon Ink and Chemicals, Inc.
Was added to prepare an electrolytic nickel-cobalt-PTFE composite plating solution.
【０１８９】（３）電解亜鉛メッキ液の調製 下記の組成を有する電解亜鉛メッキ液を調製した。(3) Preparation of electrolytic zinc plating solution An electrolytic zinc plating solution having the following composition was prepared.
【０１９０】 酸化亜鉛 １７ｇ／Ｌ 水酸化ナトリウム １４０ｇ／Ｌ ３７％ホルマリン ２０ｍＬ／Ｌ （４）メッキ法 前記各基材（被メッキ材料）をアルカリ脱脂液で脱脂し
た後、それぞれを負極とし、上記（１）の組成のニッケ
ルストライクメッキ液を含むメッキ槽を用いて、液温２
５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッケルス
トライクメッキ処理を２分間行った。Zinc oxide 17 g / L Sodium hydroxide 140 g / L 37% formalin 20 mL / L (4) Plating method Each of the above-mentioned base materials (material to be plated) was degreased with an alkaline degreasing solution, and each was made a negative electrode, Using a plating bath containing a nickel strike plating solution having the composition of 1), a solution temperature of 2
Under a condition of 5 ° C. and a current density of 10 A / dm 2 , nickel strike plating was performed for 2 minutes.
【０１９１】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−コバルト−ＰＴＦＥ複合
メッキ液を含むメッキ槽中、液温５０℃、ｐＨ４．２、
電流密度２Ａ／ｄｍ2の条件で、スクリュー撹拌しつ
つ、膜厚が１０μｍとなるまで電解メッキを行って、電
解ニッケル−コバルト−ＰＴＦＥ複合メッキ皮膜を形成
させた。この時点で共析率測定用試験片を使用し、ＰＴ
ＦＥの共析率（容量％）を求めたところ、３０容量％で
あった。Next, using the obtained coating material, in a plating tank containing the electrolytic nickel-cobalt-PTFE composite plating solution having the composition (2), a solution temperature of 50 ° C. and a pH of 4.2
Under a condition of a current density of 2 A / dm 2 , electrolytic plating was performed until the film thickness became 10 μm while stirring with a screw to form an electrolytic nickel-cobalt-PTFE composite plating film. At this point, the test piece for eutectoid ratio measurement was
When the eutectoid rate (volume%) of FE was determined, it was 30 vol%.
【０１９２】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解亜鉛メッキ液
を含むメッキ槽を用いて、液温３０℃、電流密度３Ａ／
ｄｍ 2の条件で、膜厚が０．５μｍとなるまで電解メッ
キを行って、亜鉛メッキ皮膜を形成させた。メッキ終了
後、水洗し、１００℃で、５分間乾燥させた。Further, the coating material subjected to the composite plating is negatively charged.
As an electrode, an electrolytic galvanizing solution having the composition of (3) above
Using a plating tank containing
dm TwoUnder the conditions described above, until the film thickness becomes 0.5 μm.
The plating was performed to form a galvanized film. Finish plating
Thereafter, it was washed with water and dried at 100 ° C. for 5 minutes.
【０１９３】得られた電解ニッケル−コバルト−ＰＴＦ
Ｅ複合メッキ皮膜の上に亜鉛メッキ皮膜を施したメッキ
被覆物を、熱風循環式乾燥炉中で、４００℃で１５分間
加熱した後、常温で１時間室内放置した。このメッキ被
覆物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸ
Ａ−８９００ＲＬ）を用いて分析したところ、ニッケ
ル：４８重量％、コバルト：１２重量％及び亜鉛：４０
重量％のニッケル−コバルト−亜鉛合金が形成されてい
た。また、前記ＥＰＭＡ分析装置を用いて、断面深さ方
向の亜鉛の分析を行ったところ、亜鉛の拡散層の厚みは
３μｍであった。Obtained electrolytic nickel-cobalt-PTF
The plated coating obtained by applying a zinc plating coating on the E composite plating coating was heated at 400 ° C. for 15 minutes in a hot-air circulation drying oven, and then left indoors at room temperature for 1 hour. The surface of the plated coating is measured with an EPMA analyzer (JX manufactured by JEOL Ltd.).
A-8900RL), it was found that nickel: 48% by weight, cobalt: 12% by weight, and zinc: 40% by weight.
By weight, a nickel-cobalt-zinc alloy was formed. When zinc was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the zinc diffusion layer was 3 μm.
【０１９４】この耐食性複合メッキ皮膜が施された被覆
物を用いて共析率以外の上記（２）〜（１１）の試験を
行った。Using the coating provided with the corrosion-resistant composite plating film, the above tests (2) to (11) other than the eutectoid ratio were performed.
【０１９５】実施例２３ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 23 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０１９６】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）無電解ニッケル／リンメッキ液の調製 下記の組成を有する無電解ニッケル／リンメッキ液を調
製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electroless nickel / phosphorus plating solution An electroless nickel / phosphorus plating solution having the following composition was prepared.
【０１９７】 硫酸ニッケル ２０ｇ／Ｌ 次亜リン酸ナトリウム ２５ｇ／Ｌ 乳酸 ２０ｇ／Ｌ プロピオン酸 ３ｇ／Ｌ （３）無電解ニッケル／リン−ＰＴＦＥ複合メッキ液の
調製 上記組成を有する無電解ニッケル／リンメッキ液１リッ
トルに対して、ＰＴＦＥ微粒子（平均粒子径０．２μ
ｍ、ダイキン工業（株）製、ルブロンＬ−２）１０ｇを
添加し、このＰＴＦＥ１ｇに対して、界面活性剤として
の第４級パーフルオロアンモニウム塩［Ｃ8Ｆ17ＳＯ2Ｎ
Ｈ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録商標「メガフ
ァックＦ１５０」，大日本インキ化学（株）製］を３
０．０ｍｇ添加して、無電解ニッケル／リン−ＰＴＦＥ
複合メッキ液を調製した。Nickel sulfate 20 g / L Sodium hypophosphite 25 g / L Lactic acid 20 g / L Propionic acid 3 g / L (3) Preparation of electroless nickel / phosphorus-PTFE composite plating solution Electroless nickel / phosphorus plating solution having the above composition PTFE fine particles (average particle size 0.2μ
m, Lubron L-2, manufactured by Daikin Industries, Ltd.), and 10 g of the PTFE was added to 1 g of the PTFE to form a quaternary perfluoroammonium salt [C 8 F 17 SO 2 N] as a surfactant.
H (CH 2 ) 3 N + (CH 3 ) 3 .Cl − , registered trademark “MegaFac F150”, manufactured by Dainippon Ink and Chemicals, Inc.]
0.0mg added, electroless nickel / phosphorus-PTFE
A composite plating solution was prepared.
【０１９８】（４）電解亜鉛メッキ液の調製 下記の組成を有する電解亜鉛メッキ液を調製した。(4) Preparation of electrolytic zinc plating solution An electrolytic zinc plating solution having the following composition was prepared.
【０１９９】 酸化亜鉛 １７ｇ／Ｌ 水酸化ナトリウム １４０ｇ／Ｌ ３７％ホルマリン ２０ｍＬ／Ｌ （５）メッキ法 前記各基材（被メッキ材料）をアルカリ脱脂液で脱脂し
た後、それぞれを負極とし、前記（１）の組成のニッケ
ルストライクメッキ液を含むメッキ槽を用いて、液温２
５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッケルス
トライクメッキ処理を２分間行った。Zinc oxide 17 g / L Sodium hydroxide 140 g / L 37% formalin 20 mL / L (5) Plating method Each of the above-mentioned base materials (material to be plated) was degreased with an alkali degreasing solution, and then each was made a negative electrode, Using a plating bath containing a nickel strike plating solution having the composition of 1), a solution temperature of 2
Under a condition of 5 ° C. and a current density of 10 A / dm 2 , nickel strike plating was performed for 2 minutes.
【０２００】ついで、得られた被覆物を用い手、前記
（２）の組成の無電解ニッケル／リンメッキ液を含むメ
ッキ槽を用いて、液温９０℃、ｐＨ４．６の条件下に、
スクリュー撹拌しつつ、膜厚が３μｍとなるまで無電解
メッキを行って、無電解下地ニッケル／リンメッキ皮膜
を形成させた。Next, using the obtained coating material, a plating bath containing an electroless nickel / phosphorous plating solution having the composition of (2) above was used, under the conditions of a liquid temperature of 90 ° C. and a pH of 4.6.
While stirring with a screw, electroless plating was performed until the film thickness became 3 μm, thereby forming an electroless base nickel / phosphorus plating film.
【０２０１】無電解下地ニッケル／リンメッキ皮膜が施
された被覆物を、前記（３）の組成の無電解ニッケル／
リン−ＰＴＦＥ複合メッキ液を含む複合メッキ槽を用い
て、液温９０℃、ｐＨ５．１の条件で、スクリュー撹拌
しつつ、膜厚が７μｍとなるまで無電解メッキを行っ
て、無電解ニッケル／リン−ＰＴＦＥ複合メッキ皮膜を
形成させた。The coating provided with the electroless base nickel / phosphorus plating film was treated with the electroless nickel / phosphorous
Using a composite plating tank containing a phosphorus-PTFE composite plating solution, electroless plating was performed under a condition of a liquid temperature of 90 ° C. and a pH of 5.1 until the film thickness became 7 μm while stirring with a screw. A phosphorus-PTFE composite plating film was formed.
【０２０２】この時点でＰＴＦＥ共析率（容量％）を求
めたところ、３０容量％であった。At this time, the PTFE eutectoid ratio (volume%) was determined to be 30 vol%.
【０２０３】得られた無電解ニッケル／リン−ＰＴＦＥ
複合メッキ皮膜が施された被覆物を水洗した後、負極と
して前記（４）の電解亜鉛メッキ液を含むメッキ槽中、
液温３０℃、電流密度３Ａ／ｄｍ2の条件で、膜厚が
０．５μｍとなるまで電解メッキを行って、電解亜鉛メ
ッキ皮膜を形成させた。メッキ終了後、得られた被覆物
を水洗し、１００℃で、５分間乾燥させた。The obtained electroless nickel / phosphorus-PTFE
After washing the coated material provided with the composite plating film with water, in a plating tank containing the electrolytic zinc plating solution of the above (4) as a negative electrode,
Electroplating was performed under the conditions of a liquid temperature of 30 ° C. and a current density of 3 A / dm 2 until the film thickness became 0.5 μm, thereby forming an electrolytic zinc plating film. After the plating was completed, the obtained coating was washed with water and dried at 100 ° C. for 5 minutes.
【０２０４】得られた無電解ニッケル／リン−ＰＴＦＥ
複合メッキ皮膜の上に亜鉛メッキ皮膜を施した被覆物
を、熱風循環式乾燥炉中で、４００℃で１５分間加熱し
た後、常温で１時間室内放置した。このメッキ被覆物の
表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−８
９００ＲＬ）を用いて分析したところ、ニッケル：５５
重量％、リン：５重量％及び亜鉛：４０重量％のニッケ
ル−亜鉛−リン合金が形成されていた。また、前記ＥＰ
ＭＡ分析装置を用いて、断面深さ方向の亜鉛の分析を行
ったところ、亜鉛の拡散層の厚みは３μｍであった。The obtained electroless nickel / phosphorus-PTFE
The coated product obtained by applying a zinc plating film on the composite plating film was heated at 400 ° C. for 15 minutes in a hot-air circulation drying oven, and then left indoors at room temperature for 1 hour. The surface of the plated coating was measured with an EPMA analyzer (JXA-8 manufactured by JEOL Ltd.).
900 RL), the nickel: 55
A nickel-zinc-phosphorus alloy of 5% by weight, phosphorus: 5% by weight and zinc: 40% by weight was formed. The EP
When zinc was analyzed in the cross-sectional depth direction using an MA analyzer, the thickness of the zinc diffusion layer was 3 μm.
【０２０５】この耐食性複合メッキ皮膜が施された被覆
物を用いて共析率以外の上記（２）〜（１１）の試験を
行った。Using the coating provided with the corrosion-resistant composite plating film, the above tests (2) to (11) except for the eutectoid ratio were performed.
【０２０６】比較例３ （１）ニッケルストライクメッキ液の調製 実施例１３と同様のニッケルストライクメッキ液を調製
した。Comparative Example 3 (1) Preparation of Nickel Strike Plating Solution The same nickel strike plating solution as in Example 13 was prepared.
【０２０７】（２）電解ニッケルメッキ液の調製 下記の組成を有するメッキ液を調製した。(2) Preparation of electrolytic nickel plating solution A plating solution having the following composition was prepared.
【０２０８】 スルファミン酸ニッケル ３６０ｇ／Ｌ 塩化ニッケル ４５ｇ／Ｌ ホウ酸 ３０ｇ／Ｌ （３）電解亜鉛メッキ液の調製 実施例１３と同様に電解亜鉛メッキ液を調製した。Nickel sulfamate 360 g / L Nickel chloride 45 g / L Boric acid 30 g / L (3) Preparation of electrolytic zinc plating solution An electrolytic zinc plating solution was prepared in the same manner as in Example 13.
【０２０９】（４）メッキ法 実施例１３と同様の基材をアルカリ脱脂液で脱脂した
後、負極とし、上記（１）の組成のニッケルストライク
メッキ液を含むメッキ槽を用いて、液温２５℃、電流密
度１０Ａ／ｄｍ2の条件で、ニッケルストライクメッキ
処理を２分間行った。(4) Plating method After the same substrate as in Example 13 was degreased with an alkaline degreasing solution, a negative electrode was prepared using a plating tank containing the nickel strike plating solution having the composition (1), and a solution temperature of 25%. Nickel strike plating was performed for 2 minutes at a temperature of 10 ° C. and a current density of 10 A / dm 2 .
【０２１０】次いで、得られた被覆物を負極とし、上記
（２）の組成の電解ニッケルメッキ液を含むメッキ槽を
用いて、液温５０℃、ｐＨ４．２、電流密度４Ａ／ｄｍ
2の条件で、スクリュー撹拌しつつ、膜厚が１０μｍと
なるまで電解ニッケルメッキを行った。Next, the obtained coating material was used as a negative electrode, and using a plating bath containing an electrolytic nickel plating solution having the composition of the above (2), a liquid temperature of 50 ° C., a pH of 4.2, and a current density of 4 A / dm.
Under the conditions of 2, the electrolytic nickel plating was performed while stirring with a screw until the film thickness became 10 μm.
【０２１１】更に、得られた被覆物を水洗した後、負極
とし、上記（３）の組成を有する電解亜鉛メッキ液を含
むメッキ槽を用いて、液温３０℃、電流密度３Ａ／ｄｍ
2の条件で、膜厚が０．５μｍとなるまで電解メッキを
行って、亜鉛メッキ皮膜を形成させた。メッキ終了後、
水洗して１００℃、５分間乾燥させた。さらに熱風循環
式乾燥炉中で、４００℃で１５分間加熱した後、次いで
常温で１時間室内放置した。このメッキ被覆物の表面を
ＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−８９００
ＲＬ）を用いて分析したところ、ニッケル：６０重量％
及び亜鉛：４０重量％のニッケル−亜鉛合金が形成され
ていた。得られたメッキ被覆物を用いて実施例１３と同
様の試験評価を行った。Further, after the obtained coating was washed with water, it was used as a negative electrode, using a plating tank containing an electrolytic zinc plating solution having the composition of (3) above, at a liquid temperature of 30 ° C. and a current density of 3 A / dm.
Under the conditions of 2 , electrolytic plating was performed until the film thickness became 0.5 μm to form a galvanized film. After plating,
It was washed with water and dried at 100 ° C. for 5 minutes. Furthermore, after heating at 400 ° C. for 15 minutes in a hot-air circulation type drying furnace, it was then left indoors at room temperature for 1 hour. The surface of the plated coating is coated with an EPMA analyzer (JXA-8900 manufactured by JEOL Ltd.).
RL), nickel: 60% by weight
And zinc: 40% by weight of a nickel-zinc alloy was formed. The same test and evaluation as in Example 13 were performed using the obtained plated coating.
【０２１２】実施例及び比較例のメッキ被覆物につい
て、前記物性及び特性の評価を行った結果を表３及び表
４に示す。Tables 3 and 4 show the results of the evaluation of the physical properties and characteristics of the plated coatings of the examples and comparative examples.
【０２１３】[0213]
【表３】 [Table 3]
【０２１４】[0214]
【表４】 [Table 4]
【０２１５】表３及び表４から明らかなように、本発明
による耐食性（フッ素化合物共析）複合メッキ皮膜は、
極めて優れた撥水性、非粘着性、密着性、耐衝撃変形
性、耐薬品性、耐磨耗性、摺動性、耐熱性、装飾性等を
備えている。As is clear from Tables 3 and 4, the corrosion-resistant (fluorine compound eutectoid) composite plating film according to the present invention was
It has extremely excellent water repellency, non-adhesion, adhesion, impact deformation resistance, chemical resistance, abrasion resistance, slidability, heat resistance, decorativeness, etc.
【０２１６】実施例２４ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 24 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０２１７】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−カドミウム−ＰＴＦＥ複合メッキ
液の調製 電解ニッケル−カドミウム合金メッキ液（組成：硫酸ニ
ッケル７９ｇ／Ｌ、硫酸カドミウム１０ｇ／Ｌ、硫酸ナ
トリウム２０ｇ／Ｌ、デキストリン０．５ｇ／Ｌ）１リ
ットルに対して、ＰＴＦＥ微粒子（平均粒子径０．２μ
ｍ、ダイキン工業（株）製、ルブロンＬ−２）５０ｇを
添加し、このＰＴＦＥ１ｇに対して、界面活性剤として
の第４級パーフルオロアンモニウム塩［Ｃ8Ｆ17ＳＯ2Ｎ
Ｈ（ＣＨ 2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録商標「メガフ
ァックＦ１５０」，大日本インキ化学（株）製］を３
０．０ｍｇ添加して、電解ニッケル−カドミウム−ＰＴ
ＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Electrolytic nickel-cadmium-PTFE composite plating
Preparation of solution Electrolytic nickel-cadmium alloy plating solution (composition: sulfuric acid
79g / L, cadmium sulfate 10g / L, sodium sulfate
Thorium 20 g / L, dextrin 0.5 g / L) 1 l
PTFE fine particles (average particle size 0.2μ
m, 50 g of Lubron L-2) manufactured by Daikin Industries, Ltd.
As a surfactant for 1 g of this PTFE
Quaternary perfluoroammonium salt [C8F17SOTwoN
H (CH Two)ThreeN+(CHThree)Three・ Cl-, Registered trademark "Megafu
ACK F150 ", manufactured by Dainippon Ink and Chemicals, Inc.]
0.0mg added, electrolytic nickel-cadmium-PT
An FE composite plating solution was prepared.
【０２１８】（３）メッキ法 前記基材Ａ及びＢ（被メッキ材料）をアルカリ脱脂液で
脱脂した後、それぞれを負極とし、前記（１）の組成の
ニッケルストライクメッキ液を含むメッキ槽を用いて、
液温２５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッ
ケルストライクメッキ処理を２分間行った。(3) Plating Method After the base materials A and B (material to be plated) were degreased with an alkali degreasing solution, each was used as a negative electrode, and a plating tank containing a nickel strike plating solution having the composition (1) was used. hand,
Nickel strike plating was performed for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 .
【０２１９】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−カドミウム−ＰＴＦＥ複
合メッキ液を含むメッキ槽中、液温５０℃、ｐＨ５．
０、電流密度４Ａ／ｄｍ2の条件で、スクリュー撹拌し
つつ、膜厚が１０μｍとなるまで電解メッキを行って、
電解ニッケル−カドミウム−ＰＴＦＥ複合メッキ皮膜を
形成させた。メッキ終了後、水洗し、１００℃で５分間
乾燥させた。この時点で共析率測定用試験片を使用し、
ＰＴＦＥの共析率（容量％）を求めたところ、３０容量
％であった。また、メッキ被覆物の表面をＥＰＭＡ分析
装置（日本電子（株）製ＪＸＡ−８９００ＲＬ）を用い
て分析したところ、ニッケル：７５重量％及びカドミウ
ム：３５重量％のニッケル−カドミウム合金が形成され
ていた。Next, using the obtained coating, in a plating tank containing an electrolytic nickel-cadmium-PTFE composite plating solution having the composition of the above (2), a solution temperature of 50 ° C. and a pH of 5.
0, electrolytic plating was performed under a condition of a current density of 4 A / dm 2 while stirring the screw until the film thickness became 10 μm.
An electrolytic nickel-cadmium-PTFE composite plating film was formed. After the plating was completed, the plate was washed with water and dried at 100 ° C. for 5 minutes. At this point, use a test piece for eutectoid rate measurement,
The eutectoid rate (volume%) of PTFE was determined to be 30 vol%. When the surface of the plated coating was analyzed using an EPMA analyzer (JXA-8900RL, manufactured by JEOL Ltd.), a nickel-cadmium alloy of nickel: 75% by weight and cadmium: 35% by weight was formed. .
【０２２０】得られた電解ニッケル−カドミウム−ＰＴ
ＦＥ複合メッキ皮膜を施したメッキ被覆物を、熱風循環
式乾燥炉中、３５０℃で３０分間加熱した後、常温で１
時間、室内放置した。この耐食性複合メッキ皮膜が施さ
れた被覆物を用いて前記（２）〜（９）の試験を行っ
た。The obtained electrolytic nickel-cadmium-PT
The FE composite plating film is heated at 350 ° C. for 30 minutes in a hot air circulating drying oven, and then heated at room temperature for 1 minute.
Left indoors for hours. The tests (2) to (9) were performed using the coating provided with the corrosion-resistant composite plating film.
【０２２１】実施例２５ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 25 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０２２２】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−ＰＴＦＥ複合メッキ液の調製 電解ニッケルメッキ液（組成：スルファミン酸ニッケル
３６０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ
／Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子
径０．２μｍ、ダイキン工業（株）製、ルブロンＬ−
２）５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面
活性剤としての第４級パーフルオロアンモニウム塩［Ｃ
8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録
商標「メガファックＦ１５０」，大日本インキ化学
（株）製］を３０．０ｍｇ添加して、電解ニッケル−Ｐ
ＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-PTFE composite plating solution Electrolytic nickel plating solution (composition: nickel sulfamate 360 g / L, nickel chloride 45 g / L, boric acid 30 g)
/ L) PTFE fine particles (average particle diameter 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-
2) 50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C
8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3 · Cl -, R "Megafac F150", Dainippon Ink and Chemicals Co., Ltd.] was added 30.0mg of electrolytic nickel - P
A TFE composite plating solution was prepared.
【０２２３】（３）電解カドミウムメッキ液の調製 下記の組成を有する電解カドミウムメッキ液を調製し
た。(3) Preparation of Electrolytic Cadmium Plating Solution An electrolytic cadmium plating solution having the following composition was prepared.
【０２２４】 ホウフッ化カドミウム ２４２ｇ／Ｌ 金属カドミウム ９５ｇ／Ｌ ホウフッ化アンモニウム ６０ｇ／Ｌ ホウ酸 ２７ｇ／Ｌ 甘草エキス １ｇ／Ｌ （４）メッキ法 前記基材Ａ及びＢ（被メッキ材料）をアルカリ脱脂液で
脱脂した後、それぞれを負極とし、前記（１）の組成の
ニッケルストライクメッキ液を含むメッキ槽を用いて、
液温２５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッ
ケルストライクメッキ処理を２分間行った。Cadmium borofluoride 242 g / L Metal cadmium 95 g / L Ammonium borofluoride 60 g / L Boric acid 27 g / L Licorice extract 1 g / L After degreasing by using each as a negative electrode, using a plating tank containing a nickel strike plating solution having the composition of the above (1),
Nickel strike plating was performed for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 .
【０２２５】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−ＰＴＦＥ複合メッキ液を
含むメッキ槽中、液温５０℃、ｐＨ４．２、電流密度２
Ａ／ｄｍ2の条件で、スクリュー撹拌しつつ、膜厚が１
０μｍとなるまで電解メッキを行って、電解ニッケル−
ＰＴＦＥ複合メッキ皮膜を形成させた。この時点で共析
率測定用試験片を使用し、ＰＴＦＥの共析率（容量％）
を求めたところ、３０容量％であった。Next, using the obtained coating material, in a plating tank containing the electrolytic nickel-PTFE composite plating solution having the composition of the above (2), a solution temperature of 50 ° C., a pH of 4.2, and a current density of 2
Under the condition of A / dm 2 , the film thickness is 1
Electroplating is performed until the thickness becomes 0 μm.
A PTFE composite plating film was formed. At this point, the eutectoid rate of PTFE (volume%) was measured using a test piece for eutectoid rate measurement.
Was 30% by volume.
【０２２６】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解カドミウムメ
ッキ液を含むメッキ槽を用いて、ｐＨ３．５、液温３０
℃、電流密度４Ａ／ｄｍ2の条件で、膜厚が０．５μｍ
となるまで電解メッキを行って、カドミウムメッキ皮膜
を形成させた。メッキ終了後、水洗し、１００℃で、５
分間乾燥させた。Further, using the composite-plated coating as a negative electrode, a plating bath containing an electrolytic cadmium plating solution having the composition of the above (3) was used at a pH of 3.5 and a liquid temperature of 30.
Under the condition of 4 ° C. and a current density of 4 A / dm 2 ,
The cadmium plating film was formed by performing electroplating until the thickness became. After plating, rinse with water and
Dried for minutes.
【０２２７】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上にカドミウムメッキ皮膜を施したメッキ被覆
物を、熱風循環式乾燥炉中で、３５０℃で３０分間加熱
した後、常温で１時間室内放置した。このメッキ被覆物
の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−
８９００ＲＬ）を用いて分析したところ、ニッケル：６
０重量％及びカドミウム：４０重量％のニッケル−カド
ミウム合金が形成されていた。また、前記ＥＰＭＡ分析
装置を用いて、断面深さ方向のカドミウムの分析を行っ
たところ、カドミウムの拡散層の厚みは３μｍであっ
た。この耐食性複合メッキ皮膜が施された被覆物を用い
て前記（２）〜（９）の試験を行った。[0227] The plated coating obtained by applying a cadmium plating film on the obtained electrolytic nickel-PTFE composite plating film was heated at 350 ° C for 30 minutes in a hot-air circulation drying furnace, and then left indoors at room temperature for 1 hour. did. The surface of the plating coating was measured using an EPMA analyzer (JXA-
8900 RL), it was found that nickel: 6
A nickel-cadmium alloy of 0% by weight and 40% by weight of cadmium was formed. When cadmium was analyzed in the sectional depth direction using the EPMA analyzer, the thickness of the cadmium diffusion layer was 3 μm. The tests (2) to (9) were performed using the coating provided with the corrosion-resistant composite plating film.
【０２２８】実施例２６ 実施例２５の電解カドミウムメッキの膜厚を０．２μｍ
とした以外は、実施例２５と同様にして、基材にニッケ
ルストライクメッキ、電解ニッケル−ＰＴＦＥメッキ皮
膜及び電解カドミウムメッキ皮膜を形成した。Example 26 The thickness of the electrolytic cadmium plating film of Example 25 was 0.2 μm.
A nickel strike plating, an electrolytic nickel-PTFE plating film, and an electrolytic cadmium plating film were formed on the substrate in the same manner as in Example 25 except that the above conditions were adopted.
【０２２９】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上にカドミウムメッキ皮膜を施したメッキ被覆
物を、熱風循環式乾燥炉中で、３５０℃で３０分間加熱
した後、常温で１時間室内放置した。また、メッキ被覆
物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ
−８９００ＲＬ）を用いて分析したところ、ニッケル：
８０重量％及びカドミウム：２０重量％のニッケル−カ
ドミウム合金が形成されていた。また、前記ＥＰＭＡ分
析装置を用いて、断面深さ方向のカドミウムの分析を行
ったところ、カドミウムの拡散層の厚みは３μｍであっ
た。The plated coating obtained by applying a cadmium plating film on the obtained electrolytic nickel-PTFE composite plating film was heated at 350 ° C. for 30 minutes in a hot air circulation type drying furnace, and then left indoors at room temperature for 1 hour. did. In addition, the surface of the plating coating was measured using an EPMA analyzer (JXA manufactured by JEOL Ltd.).
-8900 RL), the nickel:
A nickel-cadmium alloy of 80% by weight and 20% by weight of cadmium was formed. When cadmium was analyzed in the sectional depth direction using the EPMA analyzer, the thickness of the cadmium diffusion layer was 3 μm.
【０２３０】この耐食性複合メッキ皮膜が施された被覆
物を用いて前記（２）〜（９）の試験を行った。The tests (2) to (9) were performed using the coating provided with the corrosion-resistant composite plating film.
【０２３１】実施例２７ 実施例２５の電解カドミウムメッキの膜厚を１．２μｍ
とした以外は、実施例２５と同様にして、基材にニッケ
ルストライクメッキ、電解ニッケル−ＰＴＦＥメッキ皮
膜及び電解カドミウムメッキ皮膜を形成した。Example 27 The film thickness of the electrolytic cadmium plating of Example 25 was 1.2 μm.
A nickel strike plating, an electrolytic nickel-PTFE plating film, and an electrolytic cadmium plating film were formed on the substrate in the same manner as in Example 25 except that the above conditions were adopted.
【０２３２】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上にカドミウムメッキ皮膜を施したメッキ被覆
物を、熱風循環式乾燥炉中で、３５０℃で３０分間加熱
した後、常温で１時間室内放置した。また、メッキ被覆
物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ
−８９００ＲＬ）を用いて分析したところ、ニッケル：
４０重量％及びカドミウム：６０重量％のニッケル−カ
ドミウム合金が形成されていた。また、前記ＥＰＭＡ分
析装置を用いて、断面深さ方向のカドミウムの分析を行
ったところ、カドミウムの拡散層の厚みは３μｍであっ
た。[0232] The plated coating obtained by applying a cadmium plating film on the obtained electrolytic nickel-PTFE composite plating film was heated at 350 ° C for 30 minutes in a hot-air circulating drying oven, and then left indoors at room temperature for 1 hour. did. In addition, the surface of the plating coating was measured using an EPMA analyzer (JXA manufactured by JEOL Ltd.).
-8900 RL), the nickel:
A nickel-cadmium alloy of 40% by weight and 60% by weight of cadmium was formed. When cadmium was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the cadmium diffusion layer was 3 μm.
【０２３３】この耐食性複合メッキ皮膜が施された被覆
物を用いて前記（２）〜（９）の試験を行った。The tests (2) to (9) were carried out using the coating provided with the corrosion-resistant composite plating film.
【０２３４】実施例２８ 実施例２５の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにＦＥＰ微粒子（平均粒
子径１μｍ、ダイキン工業（株）製）を電解ニッケルメ
ッキ液１リットルに対して５０ｇ添加した以外は、実施
例２５と同様にして、被メッキ材料にニッケルストライ
クメッキ、電解ニッケル−ＦＥＰ複合メッキ皮膜及び電
解カドミウムメッキ皮膜を順次形成させた。Example 28 In the electrolytic nickel-PTFE composite plating solution of Example 25, FEP fine particles (average particle diameter: 1 μm, manufactured by Daikin Industries, Ltd.) were used in place of PTFE fine particles at 50 g per liter of electrolytic nickel plating solution. Except for the addition, a nickel strike plating, an electrolytic nickel-FEP composite plating film and an electrolytic cadmium plating film were sequentially formed on the material to be plated in the same manner as in Example 25.
【０２３５】得られた電解ニッケル−ＦＥＰ複合メッキ
皮膜の上に電解カドミウムメッキ皮膜を施したメッキ被
覆物を、熱風循環式乾燥炉中で、３２０℃で３０分間加
熱した後、常温で１時間室内放置した。また、メッキ被
覆物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸ
Ａ−８９００ＲＬ）を用いて分析したところ、ニッケ
ル：５０重量％及びカドミウム：５０重量％のニッケル
−カドミウム合金が形成されていた。また、前記ＥＰＭ
Ａ分析装置を用いて、断面深さ方向のカドミウムの分析
を行ったところ、カドミウムの拡散層の厚みは２．５μ
ｍであった。この耐食性複合被メッキ材料を用いて実施
例２５と同様の試験評価を行った。The plated coating obtained by applying an electrolytic cadmium plating film on the obtained electrolytic nickel-FEP composite plating film was heated at 320 ° C. for 30 minutes in a hot-air circulation drying furnace, and then indoors at room temperature for 1 hour. I left it. In addition, the surface of the plating coating is measured with an EPMA analyzer (JX JX
A-8900RL), a nickel-cadmium alloy of 50% by weight of nickel and 50% by weight of cadmium was formed. In addition, the EPM
When the cadmium was analyzed in the cross-sectional depth direction using the A analyzer, the thickness of the cadmium diffusion layer was 2.5 μm.
m. The same test and evaluation as in Example 25 were performed using this corrosion-resistant composite plating material.
【０２３６】なお、ＦＥＰ共析率（容量％）は、ニッケ
ルストライクメッキ及び電解ニッケル−ＦＥＰ複合メッ
キ皮膜を形成した後、評価した。ＦＥＰ共析率は３０容
量％であった。The FEP eutectoid rate (% by volume) was evaluated after nickel strike plating and electrolytic nickel-FEP composite plating film formation. The FEP eutectoid rate was 30% by volume.
【０２３７】実施例２９ 実施例２５の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにＰＦＡ微粒子（平均粒
子径０．５μｍ、ダイキン工業（株）製）を電解ニッケ
ルメッキ液１リットルに対して５０ｇ添加した以外は、
実施例２５と同様にして、基材にニッケルストライクメ
ッキ、電解ニッケル−ＰＦＡ複合メッキ皮膜及び電解カ
ドミウムメッキ皮膜を順次形成させた。Example 29 In the electrolytic nickel-PTFE composite plating solution of Example 25, PFA fine particles (average particle diameter: 0.5 μm, manufactured by Daikin Industries, Ltd.) were used instead of PTFE fine particles per liter of the electrolytic nickel plating solution. Except that 50g was added.
In the same manner as in Example 25, a nickel strike plating, an electrolytic nickel-PFA composite plating film, and an electrolytic cadmium plating film were sequentially formed on the substrate.
【０２３８】得られた電解ニッケル−ＰＦＡ複合メッキ
皮膜の上に電解カドミウムメッキ皮膜を施したメッキ被
覆物を、熱風循環式乾燥炉中で、３５０℃で３０分間加
熱した後、常温で１時間室内放置した。また、メッキ被
覆物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸ
Ａ−８９００ＲＬ）を用いて分析したところ、ニッケ
ル：６０重量％及びカドミウム：４０重量％のニッケル
−カドミウム合金が形成されていた。また、前記ＥＰＭ
Ａ分析装置を用いて、断面深さ方向のカドミウムの分析
を行ったところ、カドミウムの拡散層の厚みは３μｍで
あった。この耐食性複合被メッキ材料を用いて実施例２
５と同様の試験評価を行った。The resulting plated nickel-PFA composite plating film coated with an electrolytic cadmium plating film was heated at 350 ° C. for 30 minutes in a circulating hot air drying oven and then room temperature at room temperature for one hour. I left it. In addition, the surface of the plating coating was measured using an EPMA analyzer (JX JX).
A-8900RL), a nickel-cadmium alloy of 60% by weight of nickel and 40% by weight of cadmium was formed. In addition, the EPM
When cadmium was analyzed in the cross-sectional depth direction using an A analyzer, the thickness of the cadmium diffusion layer was 3 μm. Example 2 using this corrosion resistant composite plating material
The same test evaluation as in Example 5 was performed.
【０２３９】なお、ＰＦＡ共析率（容量％）は、ニッケ
ルストライクメッキ及び電解ニッケル−ＰＦＡ複合メッ
キ皮膜を形成した後、評価した。ＰＦＡ共析率は３０容
量％であった。The PFA eutectoid rate (% by volume) was evaluated after nickel strike plating and electrolytic nickel-PFA composite plating film were formed. The PFA eutectoid rate was 30% by volume.
【０２４０】実施例３０ 実施例２５の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにＰＣＴＦＥ微粒子（平
均粒子径２μｍ、ダイキン工業（株）製）を電解ニッケ
ルメッキ液１リットルに対して５０ｇ添加した以外は、
実施例２５と同様にして、基材にニッケルストライクメ
ッキ、電解ニッケル−ＰＣＴＦＥ複合メッキ皮膜及び電
解カドミウムメッキ皮膜を順次形成させた。Example 30 In the electrolytic nickel-PTFE composite plating solution of Example 25, 50 g of PCTF fine particles (average particle size: 2 μm, manufactured by Daikin Industries, Ltd.) were used in place of 1 g of the electrolytic nickel plating solution instead of PTFE fine particles. Except for the addition,
In the same manner as in Example 25, a nickel strike plating, an electrolytic nickel-PCTFE composite plating film, and an electrolytic cadmium plating film were sequentially formed on the substrate.
【０２４１】得られた電解ニッケル−ＰＣＴＦＥ複合メ
ッキ皮膜の上に電解カドミウムメッキ皮膜を施したメッ
キ被覆物を、熱風循環式乾燥炉中で、３００℃で３０分
間加熱した後、常温で１時間室内放置した。また、メッ
キ被覆物の表面をＥＰＭＡ分析装置（日本電子（株）製
ＪＸＡ−８９００ＲＬ）を用いて分析したところ、ニッ
ケル：４０重量％及びカドミウム：６０重量％のニッケ
ル−カドミウム合金が形成されていた。また、前記ＥＰ
ＭＡ分析装置を用いて、断面深さ方向のカドミウムの分
析を行ったところ、カドミウムの拡散層の厚みは２μｍ
であった。この耐食性複合被メッキ材料を用いて実施例
２５と同様の試験評価を行った。[0241] The plated product obtained by applying an electrolytic cadmium plating film on the obtained electrolytic nickel-PCTFE composite plating film was heated at 300 ° C for 30 minutes in a hot air circulation type drying furnace, and then indoors at room temperature for 1 hour. I left it. When the surface of the plating coating was analyzed using an EPMA analyzer (JXA-8900RL, manufactured by JEOL Ltd.), a nickel-cadmium alloy of nickel: 40% by weight and cadmium: 60% by weight was formed. . The EP
Cadmium was analyzed in the cross-sectional depth direction using an MA analyzer, and the thickness of the cadmium diffusion layer was 2 μm.
Met. The same test and evaluation as in Example 25 were performed using this corrosion-resistant composite plating material.
【０２４２】なお、ＰＣＴＦＥ共析率（容量％）は、ニ
ッケルストライクメッキ及び電解ニッケル−ＰＣＴＦＥ
複合メッキ皮膜を形成した後、評価した。ＰＣＴＦＥ共
析率は３０容量％であった。The PCTFE eutectoid ratio (% by volume) was determined by nickel strike plating and electrolytic nickel-PCTFE.
After forming the composite plating film, evaluation was made. The PCTFE eutectoid rate was 30% by volume.
【０２４３】実施例３１ 実施例２５の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにＥＴＦＥ微粒子（平均
粒子径２μｍ、ダイキン工業（株）製）を電解ニッケル
メッキ液１リットルに対して５０ｇ添加した以外は、実
施例２５と同様にして、被メッキ材料にニッケルストラ
イクメッキ、電解ニッケル−ＥＴＦＥ複合メッキ皮膜及
び電解カドミウムメッキ皮膜を順次形成させた。Example 31 In the electrolytic nickel-PTFE composite plating solution of Example 25, ETFE fine particles (average particle diameter: 2 μm, manufactured by Daikin Industries, Ltd.) were used in place of PTFE fine particles in an amount of 50 g per liter of the electrolytic nickel plating solution. Except for the addition, a nickel strike plating, an electrolytic nickel-ETFE composite plating film and an electrolytic cadmium plating film were sequentially formed on the material to be plated in the same manner as in Example 25.
【０２４４】得られた電解ニッケル−ＥＴＦＥ複合メッ
キ皮膜の上に電解カドミウムメッキ皮膜を施したメッキ
被覆物を、熱風循環式乾燥炉中で、３００℃で３０分間
加熱した後、常温で１時間室内放置した。このメッキ被
覆物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸ
Ａ−８９００ＲＬ）を用いて分析したところ、ニッケ
ル：４０重量％及びカドミウム：６０重量％のニッケル
−カドミウム合金が形成されていた。また、前記ＥＰＭ
Ａ分析装置を用いて、断面深さ方向のカドミウムの分析
を行ったところ、カドミウムの拡散層の厚みは２μｍで
あった。この耐食性複合被メッキ材料を用いて実施例２
５と同様の試験評価を行った。The resulting plated nickel-ETFE composite plating film coated with an electrolytic cadmium plating film was heated at 300 ° C. for 30 minutes in a circulating hot air drying oven and then room temperature at room temperature for 1 hour. I left it. The surface of the plated coating is measured with an EPMA analyzer (JX manufactured by JEOL Ltd.).
A-8900RL), a nickel-cadmium alloy of 40% by weight of nickel and 60% by weight of cadmium was formed. In addition, the EPM
When cadmium was analyzed in the cross-sectional depth direction using the A analyzer, the thickness of the cadmium diffusion layer was 2 μm. Example 2 using this corrosion resistant composite plating material
The same test evaluation as in Example 5 was performed.
【０２４５】なお、ＥＴＦＥ共析率（容量％）は、ニッ
ケルストライクメッキ及び電解ニッケル−ＥＴＦＥ複合
メッキ皮膜を形成した後、評価した。ＥＴＦＥ共析率は
３０容量％であった。The ETFE eutectoid ratio (volume%) was evaluated after nickel strike plating and electrolytic nickel-ETFE composite plating film were formed. The ETFE eutectoid rate was 30% by volume.
【０２４６】実施例３２ 実施例２５の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにフッ化黒鉛微粒子（平
均粒子径１μｍ、旭硝子（株）製）を電解ニッケルメッ
キ液１リットルに対して５０ｇ添加した以外は、実施例
２５と同様にして、被メッキ材料にニッケルストライク
メッキ、電解ニッケル−フッ化黒鉛複合メッキ皮膜及び
電解カドミウムメッキ皮膜を順次形成させた。Example 32 In the electrolytic nickel-PTFE composite plating solution of Example 25, graphite fluoride fine particles (average particle diameter: 1 μm, manufactured by Asahi Glass Co., Ltd.) were used instead of PTFE fine particles per liter of electrolytic nickel plating solution. A nickel strike plating, an electrolytic nickel-fluorinated graphite composite plating film, and an electrolytic cadmium plating film were sequentially formed on the material to be plated in the same manner as in Example 25 except that 50 g was added.
【０２４７】得られた電解ニッケル−フッ化黒鉛複合メ
ッキ皮膜の上に電解カドミウムメッキ皮膜を施したメッ
キ被覆物を、熱風循環式乾燥炉中で、３５０℃で３０分
間加熱した後、常温で１時間室内放置した。このメッキ
被覆物の表面をＥＰＭＡ分析装置（日本電子（株）製Ｊ
ＸＡ−８９００ＲＬ）を用いて分析したところ、ニッケ
ル：６０重量％及びカドミウム：４０重量％のニッケル
−カドミウム合金が形成されていた。また、前記ＥＰＭ
Ａ分析装置を用いて、断面深さ方向のカドミウムの分析
を行ったところ、カドミウムの拡散層の厚みは３μｍで
あった。この耐食性複合被メッキ材料を用いて実施例２
５と同様の試験評価を行った。[0247] The plated product obtained by applying an electrolytic cadmium plating film on the obtained electrolytic nickel-fluorinated graphite composite plating film was heated at 350 ° C for 30 minutes in a hot-air circulating drying oven, and then heated at room temperature for 1 minute. Left indoors for hours. The surface of the plated coating is measured with an EPMA analyzer (JEOL Ltd. J
XA-8900RL), a nickel-cadmium alloy of 60% by weight of nickel and 40% by weight of cadmium was formed. In addition, the EPM
When cadmium was analyzed in the cross-sectional depth direction using an A analyzer, the thickness of the cadmium diffusion layer was 3 μm. Example 2 using this corrosion resistant composite plating material
The same test evaluation as in Example 5 was performed.
【０２４８】なお、フッ化黒鉛共析率（容量％）は、ニ
ッケルストライクメッキ及び電解ニッケル−フッ化黒鉛
複合メッキ皮膜を形成した後、評価した。フッ化黒鉛共
析率は３０容量％であった。The graphite eutectoid ratio (volume%) was evaluated after nickel strike plating and electrolytic nickel-fluorinated graphite composite plating film formation. The fluorinated graphite eutectoid ratio was 30% by volume.
【０２４９】実施例３３ 実施例２５の電解ニッケル−ＰＴＦＥ複合メッキ液にお
いて、ＰＴＦＥ微粒子の代わりにフッ化ピッチ（平均粒
子径１μｍ、大阪ガス（株）製）を電解ニッケルメッキ
液１リットルに対して５０ｇ添加した以外は、実施例２
５と同様にして、被メッキ材料にニッケルストライクメ
ッキ、電解ニッケル−フッ化ピッチ複合メッキ皮膜及び
電解カドミウムメッキ皮膜を順次形成させた。Example 33 In the electrolytic nickel-PTFE composite plating solution of Example 25, pitch fluoride (average particle diameter: 1 μm, manufactured by Osaka Gas Co., Ltd.) was used instead of PTFE fine particles per liter of the electrolytic nickel plating solution. Example 2 except that 50 g was added.
In the same manner as in No. 5, a nickel strike plating, an electrolytic nickel-fluoride pitch composite plating film, and an electrolytic cadmium plating film were sequentially formed on the material to be plated.
【０２５０】得られた電解ニッケル−フッ化ピッチ複合
メッキ皮膜の上に電解カドミウムメッキ皮膜を有する被
メッキ材料を、熱風循環式乾燥炉中で、３２０℃で３０
分間加熱した後、常温で１時間室内放置した。このメッ
キ被覆物の表面をＥＰＭＡ分析装置（日本電子（株）製
ＪＸＡ−８９００ＲＬ）を用いて分析したところ、ニッ
ケル：５０重量％及びカドミウム：５０重量％のニッケ
ル−カドミウム合金が形成されていた。また、前記ＥＰ
ＭＡ分析装置を用いて、断面深さ方向のカドミウムの分
析を行ったところ、カドミウムの拡散層の厚みは２．５
μｍであった。この耐食性複合被メッキ材料を用いて実
施例２５と同様の試験評価を行った。The material to be plated having an electrolytic cadmium plating film on the obtained electrolytic nickel-fluoride pitch composite plating film was placed in a hot-air circulation drying oven at 320 ° C. for 30 minutes.
After heating for minutes, it was left indoors at room temperature for 1 hour. When the surface of the plated coating was analyzed using an EPMA analyzer (JXA-8900RL, manufactured by JEOL Ltd.), a nickel-cadmium alloy of 50% by weight of nickel and 50% by weight of cadmium was formed. The EP
Cadmium was analyzed in the cross-sectional depth direction using an MA analyzer, and the thickness of the cadmium diffusion layer was 2.5
μm. The same test and evaluation as in Example 25 were performed using this corrosion-resistant composite plating material.
【０２５１】なお、フッ化ピッチ共析率（容量％）は、
ニッケルストライクメッキ及び電解ニッケル−フッ化ピ
ッチ複合メッキ皮膜を形成した後、評価した。フッ化ピ
ッチ共析率は３０容量％であった。The pitch fluoride eutectoid rate (% by volume)
After forming a nickel strike plating and an electrolytic nickel-fluoride pitch composite plating film, evaluation was made. The pitch fluoride eutectoid ratio was 30% by volume.
【０２５２】実施例３４ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 34 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０２５３】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−コバルト−ＰＴＦＥ複合メッキ液
の調製 電解ニッケル−コバルト合金メッキ液（組成：スルファ
ミン酸ニッケル３６０ｇ／Ｌ、スルファミン酸コバルト
１０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ／
Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子径
０．２μｍ、ダイキン工業（株）製、ルブロンＬ−２）
５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面活性
剤としての第４級パーフルオロアンモニウム塩［Ｃ8Ｆ
17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録商
標「メガファックＦ１５０」，大日本インキ化学（株）
製］を３０．０ｍｇ添加して、電解ニッケル−コバルト
−ＰＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-cobalt-PTFE composite plating solution Electrolytic nickel-cobalt alloy plating solution (composition: nickel sulfamate 360 g / L, cobalt sulfamate 10 g / L, Nickel chloride 45g / L, boric acid 30g /
L) PTFE fine particles (average particle diameter 0.2 μm, Lubron L-2, manufactured by Daikin Industries, Ltd.) per 1 liter
50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C 8 F
17 SO 2 NH (CH 2 ) 3 N + (CH 3 ) 3 .Cl − , registered trademark “MegaFac F150”, Dainippon Ink and Chemicals, Inc.
Was added to prepare an electrolytic nickel-cobalt-PTFE composite plating solution.
【０２５４】（３）電解カドミウムメッキ液の調製 下記の組成を有する電解カドミウムメッキ液を調製し
た。(3) Preparation of Electrolytic Cadmium Plating Solution An electrolytic cadmium plating solution having the following composition was prepared.
【０２５５】 ホウフッ化カドミウム ２４２ｇ／Ｌ 金属カドミウム ９５ｇ／Ｌ ホウフッ化アンモニウム ６０ｇ／Ｌ ホウ酸 ２７ｇ／Ｌ 甘草エキス １ｇ／Ｌ （４）メッキ法 前記基材Ａ及びＢ（被メッキ材料）をアルカリ脱脂液で
脱脂した後、それぞれを負極とし、上記（１）の組成の
ニッケルストライクメッキ液を含むメッキ槽を用いて、
液温２５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッ
ケルストライクメッキ処理を２分間行った。Cadmium borofluoride 242 g / L Metal cadmium 95 g / L Ammonium borofluoride 60 g / L Boric acid 27 g / L Licorice extract 1 g / L (4) Plating method The bases A and B (material to be plated) are alkali-degreased. After degreased by using each as a negative electrode, using a plating tank containing a nickel strike plating solution having the composition of the above (1),
Nickel strike plating was performed for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 .
【０２５６】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−コバルト−ＰＴＦＥ複合
メッキ液を含むメッキ槽中、液温５０℃、ｐＨ４．２、
電流密度２Ａ／ｄｍ2の条件で、スクリュー撹拌しつ
つ、膜厚が１０μｍとなるまで電解メッキを行って、電
解ニッケル−コバルト−ＰＴＦＥ複合メッキ皮膜を形成
させた。この時点で共析率測定用試験片を使用し、ＰＴ
ＦＥの共析率（容量％）を求めたところ、３０容量％で
あった。Next, using the obtained coating material, in a plating tank containing an electrolytic nickel-cobalt-PTFE composite plating solution having the composition of the above (2), a solution temperature of 50 ° C. and a pH of 4.2
Under a condition of a current density of 2 A / dm 2 , electrolytic plating was performed until the film thickness became 10 μm while stirring with a screw to form an electrolytic nickel-cobalt-PTFE composite plating film. At this point, the test piece for eutectoid ratio measurement was
When the eutectoid rate (volume%) of FE was determined, it was 30 vol%.
【０２５７】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解カドミウムメ
ッキ液を含むメッキ槽を用いて、液温３０℃、電流密度
３Ａ／ｄｍ2の条件で、膜厚が０．５μｍとなるまで電
解メッキを行って、カドミウムメッキ皮膜を形成させ
た。メッキ終了後、水洗し、１００℃で、５分間乾燥さ
せた。Further, using the coating subjected to the composite plating as a negative electrode and a plating bath containing an electrolytic cadmium plating solution having the composition of (3) above, at a liquid temperature of 30 ° C. and a current density of 3 A / dm 2 . Then, electrolytic plating was performed until the film thickness became 0.5 μm to form a cadmium plating film. After plating was completed, it was washed with water and dried at 100 ° C. for 5 minutes.
【０２５８】得られた電解ニッケル−コバルト−ＰＴＦ
Ｅ複合メッキ皮膜の上にカドミウムメッキ皮膜を施した
メッキ被覆物を、熱風循環式乾燥炉中で、３５０℃で３
０分間加熱した後、常温で１時間室内放置した。このメ
ッキ被覆物の表面をＥＰＭＡ分析装置（日本電子（株）
製ＪＸＡ−８９００ＲＬ）を用いて分析したところ、ニ
ッケル：４８重量％、コバルト：１２重量％及びカドミ
ウム：４０重量％のニッケル−コバルト−カドミウム合
金が形成されていた。また、前記ＥＰＭＡ分析装置を用
いて、断面深さ方向のカドミウムの分析を行ったとこ
ろ、カドミウムの拡散層の厚みは３μｍであった。The obtained electrolytic nickel-cobalt-PTF
E The plating coating obtained by applying a cadmium plating film on the composite plating film was heated at 350 ° C. for 3 hours in a hot-air circulation type drying furnace.
After heating for 0 minutes, it was left indoors at room temperature for 1 hour. The surface of this plated coating is analyzed with an EPMA analyzer (JEOL Ltd.)
As a result of analysis using a JXA-8900RL manufactured by Nissan Co., a nickel-cobalt-cadmium alloy of nickel: 48% by weight, cobalt: 12% by weight, and cadmium: 40% by weight was formed. When cadmium was analyzed in the sectional depth direction using the EPMA analyzer, the thickness of the cadmium diffusion layer was 3 μm.
【０２５９】この耐食性複合メッキ皮膜が施された被覆
物を用いて前記（２）〜（９）の試験を行った。The tests (2) to (9) were performed using the coating provided with the corrosion-resistant composite plating film.
【０２６０】実施例３５ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 35 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０２６１】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）無電解ニッケル／リンメッキ液の調製 下記の組成を有する無電解ニッケル／リンメッキ液を調
製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electroless nickel / phosphorus plating solution An electroless nickel / phosphorus plating solution having the following composition was prepared.
【０２６２】 硫酸ニッケル ２０ｇ／Ｌ 次亜リン酸ナトリウム ２５ｇ／Ｌ 乳酸 ２０ｇ／Ｌ プロピオン酸 ３ｇ／Ｌ （３）無電解ニッケル／リン−ＰＴＦＥ複合メッキ液の
調製 上記組成を有する無電解ニッケル／リンメッキ液１リッ
トルに対して、ＰＴＦＥ微粒子（平均粒子径０．２μ
ｍ、ダイキン工業（株）製、ルブロンＬ−２）１０ｇを
添加し、このＰＴＦＥ１ｇに対して、界面活性剤として
の第４級パーフルオロアンモニウム塩［Ｃ8Ｆ17ＳＯ2Ｎ
Ｈ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録商標「メガフ
ァックＦ１５０」，大日本インキ化学（株）製］を３
０．０ｍｇ添加して、無電解ニッケル／リン−ＰＴＦＥ
複合メッキ液を調製した。Nickel sulfate 20 g / L Sodium hypophosphite 25 g / L Lactic acid 20 g / L Propionic acid 3 g / L (3) Preparation of electroless nickel / phosphorus-PTFE composite plating solution Electroless nickel / phosphorus plating solution having the above composition PTFE fine particles (average particle size 0.2μ
m, Lubron L-2, manufactured by Daikin Industries, Ltd.), and 10 g of the PTFE was added to 1 g of the PTFE to form a quaternary perfluoroammonium salt [C 8 F 17 SO 2 N] as a surfactant.
H (CH 2 ) 3 N + (CH 3 ) 3 .Cl − , registered trademark “MegaFac F150”, manufactured by Dainippon Ink and Chemicals, Inc.]
0.0mg added, electroless nickel / phosphorus-PTFE
A composite plating solution was prepared.
【０２６３】（４）電解カドミウムメッキ液の調製 下記の組成を有する電解カドミウムメッキ液を調製し
た。(4) Preparation of Electrolytic Cadmium Plating Solution An electrolytic cadmium plating solution having the following composition was prepared.
【０２６４】 ホウフッ化カドミウム ２４２ｇ／Ｌ 金属カドミウム ９５ｇ／Ｌ ホウフッ化アンモニウム ６０ｇ／Ｌ ホウ酸 ２７ｇ／Ｌ 甘草エキス １ｇ／Ｌ （５）メッキ法 前記基材Ａ及びＢ（被メッキ材料）をアルカリ脱脂液で
脱脂した後、それぞれを負極とし、前記（１）の組成の
ニッケルストライクメッキ液を含むメッキ槽を用いて、
液温２５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッ
ケルストライクメッキ処理を２分間行った。Cadmium borofluoride 242 g / L Metal cadmium 95 g / L Ammonium borofluoride 60 g / L Boric acid 27 g / L Licorice extract 1 g / L After degreasing by using each as a negative electrode, using a plating tank containing a nickel strike plating solution having the composition of the above (1),
Nickel strike plating was performed for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 .
【０２６５】ついで、得られた被覆物を用いて、前記
（２）の組成の無電解ニッケル／リンメッキ液を含むメ
ッキ槽を用いて、液温９０℃、ｐＨ４．６の条件下に、
スクリュー撹拌しつつ、膜厚が３μｍとなるまで無電解
メッキを行って、無電解下地ニッケル／リンメッキ皮膜
を形成させた。Then, using the obtained coating, a plating bath containing an electroless nickel / phosphorous plating solution having the composition of the above (2) was used under the conditions of a liquid temperature of 90 ° C. and a pH of 4.6.
While stirring with a screw, electroless plating was performed until the film thickness became 3 μm, thereby forming an electroless base nickel / phosphorus plating film.
【０２６６】無電解下地ニッケル／リンメッキ皮膜が施
された被覆物を、前記（３）の組成の無電解ニッケル／
リン−ＰＴＦＥ複合メッキ液を含む複合メッキ槽を用い
て、液温９０℃、ｐＨ５．１の条件で、スクリュー撹拌
しつつ、膜厚が７μｍとなるまで無電解メッキを行っ
て、無電解ニッケル／リン−ＰＴＦＥ複合メッキ皮膜を
形成させた。The coating provided with the electroless base nickel / phosphorus plating film was treated with the electroless nickel /
Using a composite plating tank containing a phosphorus-PTFE composite plating solution, electroless plating was performed under a condition of a liquid temperature of 90 ° C. and a pH of 5.1 until the film thickness became 7 μm while stirring with a screw. A phosphorus-PTFE composite plating film was formed.
【０２６７】この時点でＰＴＦＥ共析率（容量％）を求
めたところ、３０容量％であった。At this time, the PTFE eutectoid ratio (volume%) was determined to be 30 vol%.
【０２６８】得られた無電解ニッケル／リン−ＰＴＦＥ
複合メッキ皮膜が施された被覆物をを水洗した後、負極
として前記（４）の電解カドミウムメッキ液を含むメッ
キ槽中、液温３０℃、電流密度３Ａ／ｄｍ2の条件で、
膜厚が０．５μｍとなるまで電解メッキを行って、電解
カドミウムメッキ皮膜を形成させた。メッキ終了後、得
られた被覆物を水洗し、１００℃で、５分間乾燥させ
た。The obtained electroless nickel / phosphorus-PTFE
After washing the coated material provided with the composite plating film with water, in a plating tank containing the electrolytic cadmium plating solution of the above (4) as a negative electrode, at a solution temperature of 30 ° C. and a current density of 3 A / dm 2 ,
Electrolytic plating was performed until the film thickness became 0.5 μm to form an electrolytic cadmium plating film. After the plating was completed, the obtained coating was washed with water and dried at 100 ° C. for 5 minutes.
【０２６９】得られた無電解ニッケル／リン−ＰＴＦＥ
複合メッキ皮膜の上にカドミウムメッキ皮膜を施したメ
ッキ被覆物を、熱風循環式乾燥炉中で、３５０℃で３０
分間加熱した後、常温で１時間室内放置した。このメッ
キ被覆物の表面をＥＰＭＡ分析装置（日本電子（株）製
ＪＸＡ−８９００ＲＬ）を用いて分析したところ、ニッ
ケル：５５重量％、リン：５重量％及びカドミウム：４
０重量％のニッケル−カドミウム−リン合金が形成され
ていた。また、前記ＥＰＭＡ分析装置を用いて、断面深
さ方向のカドミウムの分析を行ったところ、カドミウム
の拡散層の厚みは３μｍであった。The obtained electroless nickel / phosphorus-PTFE
The plated coating obtained by applying the cadmium plating film on the composite plating film is heated at 350 ° C. for 30 seconds in a hot air circulation type drying furnace.
After heating for minutes, it was left indoors at room temperature for 1 hour. When the surface of the plated coating was analyzed using an EPMA analyzer (JXA-8900RL manufactured by JEOL Ltd.), nickel: 55% by weight, phosphorus: 5% by weight, and cadmium: 4%
0% by weight of a nickel-cadmium-phosphorus alloy was formed. When cadmium was analyzed in the sectional depth direction using the EPMA analyzer, the thickness of the cadmium diffusion layer was 3 μm.
【０２７０】この耐食性複合メッキ皮膜が施された被覆
物を用いて前記（２）〜（９）の試験を行った。The tests (2) to (9) were carried out using the coating provided with the corrosion-resistant composite plating film.
【０２７１】比較例４ （１）ニッケルストライクメッキ液の調製 実施例２５と同様のニッケルストライクメッキ液を調製
した。Comparative Example 4 (1) Preparation of Nickel Strike Plating Solution The same nickel strike plating solution as in Example 25 was prepared.
【０２７２】（２）電解ニッケルメッキ液の調製 下記の組成を有するメッキ液を調製した。(2) Preparation of Electrolytic Nickel Plating Solution A plating solution having the following composition was prepared.
【０２７３】 スルファミン酸ニッケル ３６０ｇ／Ｌ 塩化ニッケル ４５ｇ／Ｌ ホウ酸 ３０ｇ／Ｌ （３）電解カドミウムメッキ液の調製 実施例２５と同様に電解カドミウムメッキ液を調製し
た。Nickel sulfamate 360 g / L Nickel chloride 45 g / L Boric acid 30 g / L (3) Preparation of electrolytic cadmium plating solution An electrolytic cadmium plating solution was prepared in the same manner as in Example 25.
【０２７４】（４）メッキ法 実施例２５と同様の基材をアルカリ脱脂液で脱脂した
後、負極とし、上記（１）の組成のニッケルストライク
メッキ液を含むメッキ槽を用いて、液温２５℃、電流密
度１０Ａ／ｄｍ2の条件で、ニッケルストライクメッキ
処理を２分間行った。(4) Plating Method After the same substrate as in Example 25 was degreased with an alkaline degreasing solution, a negative electrode was prepared using a plating tank containing the nickel strike plating solution having the composition of (1) above and a plating temperature of 25%. Nickel strike plating was performed for 2 minutes at a temperature of 10 ° C. and a current density of 10 A / dm 2 .
【０２７５】次いで、得られた被覆物を負極とし、上記
（２）の組成の電解ニッケルメッキ液を含むメッキ槽を
用いて、液温５０℃、ｐＨ４．２、電流密度４Ａ／ｄｍ
2の条件で、スクリュー撹拌しつつ、膜厚が１０μｍと
なるまで電解ニッケルメッキを行った。Next, the obtained coating material was used as a negative electrode, and using a plating bath containing an electrolytic nickel plating solution having the composition of the above (2), a liquid temperature of 50 ° C., a pH of 4.2, and a current density of 4 A / dm.
Under the conditions of 2, the electrolytic nickel plating was performed while stirring with a screw until the film thickness became 10 μm.
【０２７６】更に、得られた被覆物を水洗した後、負極
とし、上記（３）の組成を有する電解カドミウムメッキ
液を含むメッキ槽を用いて、液温３０℃、電流密度３Ａ
／ｄｍ2の条件で、膜厚が０．５μｍとなるまで電解メ
ッキを行って、カドミウムメッキ皮膜を形成させた。メ
ッキ終了後、水洗して１００℃、５分間乾燥させた。さ
らに熱風循環式乾燥炉中で、３５０℃で３０分間加熱し
た後、次いで常温で１時間室内放置した。このメッキ被
覆物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸ
Ａ−８９００ＲＬ）を用いて分析したところ、ニッケ
ル：６０重量％及びカドミウム：４０重量％のニッケル
−カドミウム合金が形成されていた。得られたメッキ被
覆物を用いて実施例２５と同様の試験評価を行った。Further, after the obtained coating was washed with water, it was used as a negative electrode and a plating bath containing an electrolytic cadmium plating solution having the above-mentioned composition (3) was used at a liquid temperature of 30 ° C. and a current density of 3 A.
Under the condition of / dm 2 , electrolytic plating was performed until the film thickness became 0.5 μm to form a cadmium plating film. After the plating was completed, it was washed with water and dried at 100 ° C. for 5 minutes. Further, after heating at 350 ° C. for 30 minutes in a hot-air circulation drying oven, the resultant was left indoors at room temperature for 1 hour. The surface of the plated coating is measured with an EPMA analyzer (JX manufactured by JEOL Ltd.).
A-8900RL), a nickel-cadmium alloy of 60% by weight of nickel and 40% by weight of cadmium was formed. The same test evaluation as in Example 25 was performed using the obtained plated coating.
【０２７７】実施例及び比較例のメッキ被覆物につい
て、前記物性及び特性の評価を行った結果を表５及び表
６に示す。Tables 5 and 6 show the results of the evaluation of the physical properties and characteristics of the plated coatings of the examples and comparative examples.
【０２７８】[0278]
【表５】 [Table 5]
【０２７９】[0279]
【表６】 [Table 6]
【０２８０】表５及び表６から明らかなように、本発明
による耐食性（フッ素化合物共析）複合メッキ皮膜は、
極めて優れた撥水性、非粘着性、密着性、耐衝撃変形
性、耐薬品性、耐磨耗性、摺動性、耐熱性、装飾性等を
備えている。As is clear from Tables 5 and 6, the corrosion-resistant (fluorine compound eutectoid) composite plating film according to the present invention
It has extremely excellent water repellency, non-adhesion, adhesion, impact deformation resistance, chemical resistance, abrasion resistance, slidability, heat resistance, decorativeness, etc.
【０２８１】実施例３６ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 36 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０２８２】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−ＰＴＦＥ複合メッキ液の調製 電解ニッケルメッキ液（組成：スルファミン酸ニッケル
３６０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ
／Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子
径０．２μｍ、ダイキン工業（株）製、ルブロンＬ−
２）５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面
活性剤としての第４級パーフルオロアンモニウム塩［Ｃ
8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録
商標「メガファックＦ１５０」，大日本インキ化学
（株）製］を３０．０ｍｇ添加して、電解ニッケル−Ｐ
ＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-PTFE composite plating solution Electrolytic nickel plating solution (composition: nickel sulfamate 360 g / L, nickel chloride 45 g / L, boric acid 30 g)
/ L) PTFE fine particles (average particle diameter 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-
2) 50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C
8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3 · Cl -, R "Megafac F150", Dainippon Ink and Chemicals Co., Ltd.] was added 30.0mg of electrolytic nickel - P
A TFE composite plating solution was prepared.
【０２８３】（３）電解インジウムメッキ液の調製 下記の組成を有する電解インジウムメッキ液を調製し
た。(3) Preparation of Electrolytic Indium Plating Solution An electrolytic indium plating solution having the following composition was prepared.
【０２８４】 硫酸インジウム ２０ｇ／Ｌ 硫酸ナトリウム １０ｇ／Ｌ （４）メッキ法 前記基材Ａ及びＢ（被メッキ材料）をアルカリ脱脂液で
脱脂した後、それぞれを負極とし、前記（１）の組成の
ニッケルストライクメッキ液を含むメッキ槽を用いて、
液温２５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッ
ケルストライクメッキ処理を２分間行った。Indium sulfate 20 g / L Sodium sulfate 10 g / L (4) Plating method After the base materials A and B (material to be plated) were degreased with an alkaline degreasing solution, each was used as a negative electrode, Using a plating tank containing a nickel strike plating solution,
Nickel strike plating was performed for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 .
【０２８５】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−ＰＴＦＥ複合メッキ液を
含むメッキ槽中、液温５０℃、ｐＨ４．２、電流密度２
Ａ／ｄｍ2の条件で、スクリュー撹拌しつつ、膜厚が１
０μｍとなるまで電解メッキを行って、電解ニッケル−
ＰＴＦＥ複合メッキ皮膜を形成させた。この時点で共析
率測定用試験片を使用し、ＰＴＦＥの共析率（容量％）
を求めたところ、３０容量％であった。Next, using the obtained coating material, in a plating bath containing the electrolytic nickel-PTFE composite plating solution having the composition of the above (2), a solution temperature of 50 ° C., a pH of 4.2, and a current density of 2
Under the condition of A / dm 2 , the film thickness is 1
Electroplating is performed until the thickness becomes 0 μm.
A PTFE composite plating film was formed. At this point, the eutectoid rate of PTFE (volume%) was measured using a test piece for eutectoid rate measurement.
Was 30% by volume.
【０２８６】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解インジウムメ
ッキ液を含むメッキ槽を用いて、ｐＨ２．４、液温２５
℃、電流密度３Ａ／ｄｍ2の条件で、膜厚が０．５μｍ
となるまで電解メッキを行って、インジウムメッキ皮膜
を形成させた。メッキ終了後、水洗し、１００℃で、５
分間乾燥させた。Further, using the coating subjected to the composite plating as a negative electrode, a plating bath containing an electrolytic indium plating solution having the composition of (3) above was used, and the pH was 2.4 and the solution temperature was 25.
Under the conditions of ° C and a current density of 3 A / dm 2 , the film thickness is 0.5 μm.
The indium plating film was formed by performing electroplating until the thickness became. After plating, rinse with water and
Dried for minutes.
【０２８７】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上にインジウムメッキ皮膜を施したメッキ被覆
物を、熱風循環式乾燥炉中で、３５０℃で３０分間加熱
した後、常温で１時間室内放置した。このメッキ被覆物
の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−
８９００ＲＬ）を用いて分析したところ、ニッケル：６
０重量％及びインジウム：４０重量％のニッケル−イン
ジウム合金が形成されていた。また、前記ＥＰＭＡ分析
装置を用いて、断面深さ方向のインジウムの分析を行っ
たところ、インジウムの拡散層の厚みは３μｍであっ
た。この耐食性複合メッキ皮膜が施された被覆物を用い
て前記（２）〜（９）の試験を行った。The plated coating obtained by applying an indium plating film on the obtained electrolytic nickel-PTFE composite plating film was heated at 350 ° C. for 30 minutes in a hot-air circulation drying furnace, and then left indoors at room temperature for 1 hour. did. The surface of the plating coating was measured using an EPMA analyzer (JXA-
8900 RL), it was found that nickel: 6
A nickel-indium alloy of 0% by weight and 40% by weight of indium was formed. In addition, when indium was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the indium diffusion layer was 3 μm. The tests (2) to (9) were performed using the coating provided with the corrosion-resistant composite plating film.
【０２８８】実施例３７ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 37 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０２８９】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−ＰＴＦＥ複合メッキ液の調製 電解ニッケルメッキ液（組成：スルファミン酸ニッケル
３６０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ
／Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子
径０．２μｍ、ダイキン工業（株）製、ルブロンＬ−
２）５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面
活性剤としての第４級パーフルオロアンモニウム塩［Ｃ
8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録
商標「メガファックＦ１５０」，大日本インキ化学
（株）製］を３０．０ｍｇ添加して、電解ニッケル−Ｐ
ＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-PTFE composite plating solution Electrolytic nickel plating solution (composition: nickel sulfamate 360 g / L, nickel chloride 45 g / L, boric acid 30 g)
/ L) PTFE fine particles (average particle diameter 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-
2) 50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C
8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3 · Cl -, R "Megafac F150", Dainippon Ink and Chemicals Co., Ltd.] was added 30.0mg of electrolytic nickel - P
A TFE composite plating solution was prepared.
【０２９０】（３）電解鉛メッキ液の調製 下記の組成を有する電解鉛メッキ液を調製した。(3) Preparation of Electrolytic Lead Plating Solution An electrolytic lead plating solution having the following composition was prepared.
【０２９１】 ホウフッ化鉛 ４００ｇ／Ｌ ホウフッ酸 ３０ｇ／Ｌ ホウ酸 ３０ｇ／Ｌ ゼラチン ０．５ｇ／Ｌ （４）メッキ法 前記基材Ａ及びＢ（被メッキ材料）をアルカリ脱脂液で
脱脂した後、それぞれを負極とし、前記（１）の組成の
ニッケルストライクメッキ液を含むメッキ槽を用いて、
液温２５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッ
ケルストライクメッキ処理を２分間行った。Lead borofluoride 400 g / L Borofluoric acid 30 g / L Boric acid 30 g / L Gelatin 0.5 g / L (4) Plating method After degreased the base materials A and B (material to be plated) with an alkaline degreaser, Using each as a negative electrode and a plating tank containing a nickel strike plating solution of the composition of the above (1),
Nickel strike plating was performed for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 .
【０２９２】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−ＰＴＦＥ複合メッキ液を
含むメッキ槽中、液温５０℃、ｐＨ４．２、電流密度２
Ａ／ｄｍ2の条件で、スクリュー撹拌しつつ、膜厚が１
０μｍとなるまで電解メッキを行って、電解ニッケル−
ＰＴＦＥ複合メッキ皮膜を形成させた。この時点で共析
率測定用試験片を使用し、ＰＴＦＥの共析率（容量％）
を求めたところ、３０容量％であった。Next, using the obtained coating material, in a plating bath containing the electrolytic nickel-PTFE composite plating solution having the composition of the above (2), a liquid temperature of 50 ° C., a pH of 4.2, and a current density of 2
Under the condition of A / dm 2 , the film thickness is 1
Electroplating is performed until the thickness becomes 0 μm.
A PTFE composite plating film was formed. At this point, the eutectoid rate of PTFE (volume%) was measured using a test piece for eutectoid rate measurement.
Was 30% by volume.
【０２９３】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解鉛メッキ液を
含むメッキ槽を用いて、液温３０℃、電流密度４Ａ／ｄ
ｍ2の条件で、膜厚が０．５μｍとなるまで電解メッキ
を行って、鉛メッキ皮膜を形成させた。メッキ終了後、
水洗し、１００℃で、５分間乾燥させた。Further, using the composite-plated coating as a negative electrode, a plating bath containing an electrolytic lead plating solution having the composition of (3) above was used at a liquid temperature of 30 ° C. and a current density of 4 A / d.
Under a condition of m 2 , electrolytic plating was performed until the film thickness became 0.5 μm to form a lead plating film. After plating,
It was washed with water and dried at 100 ° C. for 5 minutes.
【０２９４】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上に鉛メッキ皮膜を施したメッキ被覆物を、熱
風循環式乾燥炉中で、３５０℃で３０分間加熱した後、
常温で１時間室内放置した。このメッキ被覆物の表面を
ＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ−８９００
ＲＬ）を用いて分析したところ、ニッケル：６０重量％
及び鉛：４０重量％のニッケル−鉛合金が形成されてい
た。また、前記ＥＰＭＡ分析装置を用いて、断面深さ方
向の鉛の分析を行ったところ、鉛の拡散層の厚みは３μ
ｍであった。この耐食性複合メッキ皮膜が施された被覆
物を用いて前記（２）〜（９）の試験を行った。[0294] The plated coating obtained by applying a lead plating film on the obtained electrolytic nickel-PTFE composite plating film was heated at 350 ° C for 30 minutes in a hot-air circulating drying oven.
It was left indoors at room temperature for 1 hour. The surface of the plated coating is coated with an EPMA analyzer (JXA-8900 manufactured by JEOL Ltd.).
RL), nickel: 60% by weight
And lead: 40% by weight of a nickel-lead alloy was formed. When the lead was analyzed in the cross-sectional depth direction using the EPMA analyzer, the thickness of the lead diffusion layer was 3 μm.
m. The tests (2) to (9) were performed using the coating provided with the corrosion-resistant composite plating film.
【０２９５】実施例３８ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 38 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０２９６】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−ＰＴＦＥ複合メッキ液の調製 電解ニッケルメッキ液（組成：スルファミン酸ニッケル
３６０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ
／Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子
径０．２μｍ、ダイキン工業（株）製、ルブロンＬ−
２）５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面
活性剤としての第４級パーフルオロアンモニウム塩［Ｃ
8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録
商標「メガファックＦ１５０」，大日本インキ化学
（株）製］を３０．０ｍｇ添加して、電解ニッケル−Ｐ
ＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-PTFE composite plating solution Electrolytic nickel plating solution (composition: nickel sulfamate 360 g / L, nickel chloride 45 g / L, boric acid 30 g)
/ L) PTFE fine particles (average particle diameter 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-
2) 50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C
8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3 · Cl -, R "Megafac F150", Dainippon Ink and Chemicals Co., Ltd.] was added 30.0mg of electrolytic nickel - P
A TFE composite plating solution was prepared.
【０２９７】（３）電解スズ−亜鉛合金メッキ液の調製 下記の組成を有する電解スズ−亜鉛合金メッキ液を調製
した。(3) Preparation of electrolytic tin-zinc alloy plating solution An electrolytic tin-zinc alloy plating solution having the following composition was prepared.
【０２９８】 金属スズ ２０ｇ／Ｌ 金属亜鉛 ８ｇ／Ｌ プロピオン酸 ７５ｇ／Ｌ 硫酸ナトリウム ８０ｇ／Ｌ （４）メッキ法 前記各基材（被メッキ材料）をアルカリ脱脂液で脱脂し
た後、それぞれを負極とし、前記（１）の組成のニッケ
ルストライクメッキ液を含むメッキ槽を用いて、液温２
５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッケルス
トライクメッキ処理を２分間行った。Metal tin 20 g / L Metal zinc 8 g / L Propionic acid 75 g / L Sodium sulfate 80 g / L (4) Plating method Each of the base materials (material to be plated) was degreased with an alkaline degreaser, and each was used as a negative electrode. Using a plating tank containing a nickel strike plating solution having the composition (1),
Under a condition of 5 ° C. and a current density of 10 A / dm 2 , nickel strike plating was performed for 2 minutes.
【０２９９】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−ＰＴＦＥ複合メッキ液を
含むメッキ槽中、液温５０℃、ｐＨ４．２、電流密度２
Ａ／ｄｍ2の条件で、スクリュー撹拌しつつ、膜厚が１
０μｍとなるまで電解メッキを行って、電解ニッケル−
ＰＴＦＥ複合メッキ皮膜を形成させた。この時点で共析
率測定用試験片を使用し、ＰＴＦＥの共析率（容量％）
を求めたところ、３０容量％であった。Then, using the obtained coating material, in a plating tank containing the electrolytic nickel-PTFE composite plating solution having the composition of the above (2), a solution temperature of 50 ° C., a pH of 4.2, and a current density of 2
Under the condition of A / dm 2 , the film thickness is 1
Electroplating is performed until the thickness becomes 0 μm.
A PTFE composite plating film was formed. At this point, the eutectoid rate of PTFE (volume%) was measured using a test piece for eutectoid rate measurement.
Was 30% by volume.
【０３００】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解スズ−鉛合金
メッキ液を含むメッキ槽を用いて、液温２５℃、電流密
度２Ａ／ｄｍ2の条件で、膜厚が０．５μｍとなるまで
電解メッキを行って、スズ−鉛合金メッキ皮膜を形成さ
せた。メッキ終了後、水洗し、１００℃で、５分間乾燥
させた。Further, using the composite-plated coating as a negative electrode and a plating bath containing an electrolytic tin-lead alloy plating solution having the composition of (3) above, a solution temperature of 25 ° C. and a current density of 2 A / dm 2 Under the conditions of 2 , electrolytic plating was performed until the film thickness became 0.5 μm to form a tin-lead alloy plating film. After plating was completed, it was washed with water and dried at 100 ° C. for 5 minutes.
【０３０１】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上にスズ−鉛合金メッキ皮膜を施したメッキ被
覆物を、熱風循環式乾燥炉中で、３５０℃で３０分間加
熱した後、常温で１時間室内放置した。このメッキ被覆
物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ
−８９００ＲＬ）を用いて分析したところ、ニッケル：
６０重量％、スズ：２４重量％及び鉛：１６重量のニッ
ケル−スズ−鉛合金が形成されていた。また、前記ＥＰ
ＭＡ分析装置を用いて、断面深さ方向のスズ及び鉛の分
析を行ったところ、スズ及び鉛の拡散層の厚みは３μｍ
であった。この耐食性複合メッキ皮膜が施された被覆物
を用いて前記（２）〜（１１）の試験を行った。[0301] The plated coating obtained by applying a tin-lead alloy plating film on the obtained electrolytic nickel-PTFE composite plating film was heated at 350 ° C for 30 minutes in a hot-air circulation drying furnace, and then heated at room temperature for 1 minute. Left indoors for hours. The surface of this plated coating is measured using an EPMA analyzer (JXA manufactured by JEOL Ltd.).
-8900 RL), the nickel:
A nickel-tin-lead alloy of 60% by weight, 24% by weight of tin and 16% by weight of lead was formed. The EP
Analysis of tin and lead in the cross-sectional depth direction using an MA analyzer revealed that the thickness of the tin and lead diffusion layer was 3 μm.
Met. The tests (2) to (11) were performed using the coating provided with the corrosion-resistant composite plating film.
【０３０２】実施例３９ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 39 (1) Preparation of nickel strike plating solution A nickel strike plating solution having the following composition was prepared.
【０３０３】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−ＰＴＦＥ複合メッキ液の調製 電解ニッケルメッキ液（組成：スルファミン酸ニッケル
３６０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ
／Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子
径０．２μｍ、ダイキン工業（株）製、ルブロンＬ−
２）５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面
活性剤としての第４級パーフルオロアンモニウム塩［Ｃ
8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録
商標「メガファックＦ１５０」，大日本インキ化学
（株）製］を３０．０ｍｇ添加して、電解ニッケル−Ｐ
ＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-PTFE composite plating solution Electrolytic nickel plating solution (composition: nickel sulfamate 360 g / L, nickel chloride 45 g / L, boric acid 30 g)
/ L) PTFE fine particles (average particle diameter 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-
2) 50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C
8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3 · Cl -, R "Megafac F150", Dainippon Ink and Chemicals Co., Ltd.] was added 30.0mg of electrolytic nickel - P
A TFE composite plating solution was prepared.
【０３０４】（３）電解スズ−鉛合金メッキ液の調製 下記の組成を有する電解スズ−鉛合金メッキ液を調製し
た。(3) Preparation of electrolytic tin-lead alloy plating solution An electrolytic tin-lead alloy plating solution having the following composition was prepared.
【０３０５】 ホウフッ化第一スズ １３０ｇ／Ｌ ホウフッ化鉛 ５０ｇ／Ｌ ホウフッ酸 １２５ｇ／Ｌ ホウ酸 ２５ｇ／Ｌ ペプトン ５ｇ／Ｌ （４）メッキ法 前記基材Ａ及びＢ（被メッキ材料）をアルカリ脱脂液で
脱脂した後、それぞれを負極とし、前記（１）の組成の
ニッケルストライクメッキ液を含むメッキ槽を用いて、
液温２５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッ
ケルストライクメッキ処理を２分間行った。Stannous borofluoride 130 g / L Lead borofluoride 50 g / L Borofluoric acid 125 g / L Boric acid 25 g / L Peptone 5 g / L (4) Plating method The base materials A and B (material to be plated) are alkali-degreased. After degreased with a solution, each was used as a negative electrode, and using a plating tank containing a nickel strike plating solution having the composition of the above (1),
Nickel strike plating was performed for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 .
【０３０６】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−ＰＴＦＥ複合メッキ液を
含むメッキ槽中、液温５０℃、ｐＨ４．２、電流密度２
Ａ／ｄｍ2の条件で、スクリュー撹拌しつつ、膜厚が１
０μｍとなるまで電解メッキを行って、電解ニッケル−
ＰＴＦＥ複合メッキ皮膜を形成させた。この時点で共析
率測定用試験片を使用し、ＰＴＦＥの共析率（容量％）
を求めたところ、３０容量％であった。Next, using the obtained coating material, in a plating tank containing the electrolytic nickel-PTFE composite plating solution having the composition (2), a solution temperature of 50 ° C., a pH of 4.2, and a current density of 2 were used.
Under the condition of A / dm 2 , the film thickness is 1
Electroplating is performed until the thickness becomes 0 μm.
A PTFE composite plating film was formed. At this point, the eutectoid rate of PTFE (volume%) was measured using a test piece for eutectoid rate measurement.
Was 30% by volume.
【０３０７】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解スズ−鉛合金
メッキ液を含むメッキ槽を用いて、液温２５℃、電流密
度２Ａ／ｄｍ2の条件で、膜厚が０．５μｍとなるまで
電解メッキを行って、スズ−鉛合金メッキ皮膜を形成さ
せた。メッキ終了後、水洗し、１００℃で、５分間乾燥
させた。Further, using the composite-plated coating as a negative electrode, a plating bath containing an electrolytic tin-lead alloy plating solution having the composition of (3) above was used at a liquid temperature of 25 ° C. and a current density of 2 A / dm 2. Under the conditions of 2 , electrolytic plating was performed until the film thickness became 0.5 μm to form a tin-lead alloy plating film. After plating was completed, it was washed with water and dried at 100 ° C. for 5 minutes.
【０３０８】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上にスズ−鉛合金メッキ皮膜を施したメッキ被
覆物を、熱風循環式乾燥炉中で、３５０℃で３０分間加
熱した後、常温で１時間室内放置した。このメッキ被覆
物の表面をＥＰＭＡ分析装置（日本電子（株）製ＪＸＡ
−８９００ＲＬ）を用いて分析したところ、ニッケル：
６０重量％、スズ：２４重量％及び鉛：１６重量のニッ
ケル−スズ−鉛合金が形成されていた。また、前記ＥＰ
ＭＡ分析装置を用いて、断面深さ方向のスズ及び鉛の分
析を行ったところ、スズ及び鉛の拡散層の厚みは３μｍ
であった。この耐食性複合メッキ皮膜が施された被覆物
を用いて前記（２）〜（９）の試験を行った。[0308] A plating coating obtained by applying a tin-lead alloy plating coating on the obtained electrolytic nickel-PTFE composite plating coating was heated at 350 ° C for 30 minutes in a hot air circulating drying oven, and then heated at room temperature for 1 minute. Left indoors for hours. The surface of this plated coating is measured using an EPMA analyzer (JXA manufactured by JEOL Ltd.).
-8900 RL), the nickel:
A nickel-tin-lead alloy of 60% by weight, 24% by weight of tin and 16% by weight of lead was formed. The EP
Analysis of tin and lead in the cross-sectional depth direction using an MA analyzer revealed that the thickness of the tin and lead diffusion layer was 3 μm.
Met. The tests (2) to (9) were performed using the coating provided with the corrosion-resistant composite plating film.
【０３０９】実施例４０ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 40 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０３１０】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−ＰＴＦＥ複合メッキ液の調製 電解ニッケルメッキ液（組成：スルファミン酸ニッケル
３６０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ
／Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子
径０．２μｍ、ダイキン工業（株）製、ルブロンＬ−
２）５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面
活性剤としての第４級パーフルオロアンモニウム塩［Ｃ
8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録
商標「メガファックＦ１５０」，大日本インキ化学
（株）製］を３０．０ｍｇ添加して、電解ニッケル−Ｐ
ＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-PTFE composite plating solution Electrolytic nickel plating solution (composition: nickel sulfamate 360 g / L, nickel chloride 45 g / L, boric acid 30 g)
/ L) PTFE fine particles (average particle diameter 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-
2) 50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C
8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3 · Cl -, R "Megafac F150", Dainippon Ink and Chemicals Co., Ltd.] was added 30.0mg of electrolytic nickel - P
A TFE composite plating solution was prepared.
【０３１１】（３）電解カドミウム−スズメッキ液の調
製 下記の組成を有する電解カドミウム−スズメッキ液を調
製した。(3) Preparation of electrolytic cadmium-tin plating solution An electrolytic cadmium-tin plating solution having the following composition was prepared.
【０３１２】 ホウフッ化カドミウム １２０ｇ／Ｌ ホウフッ化スズ ３０ｇ／Ｌ ホウ酸 ２０ｇ／Ｌ ホウフッ化アンモニウム ５０ｇ／Ｌ ホウフッ酸 ２５ｇ／Ｌ ｐ−フェノールスルホン酸ナトリウム ２ｇ／Ｌ ゼラチン ２０ｇ／Ｌ （４）メッキ法 前記基材Ａ及びＢ（被メッキ材料）をアルカリ脱脂液で
脱脂した後、それぞれを負極とし、前記（１）の組成の
ニッケルストライクメッキ液を含むメッキ槽を用いて、
液温２５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッ
ケルストライクメッキ処理を２分間行った。Cadmium borofluoride 120 g / L tin borofluoride 30 g / L boric acid 20 g / L ammonium borofluoride 50 g / L borofluoric acid 25 g / L sodium p-phenolsulfonate 2 g / L gelatin 20 g / L (4) Plating method After degreasing the base materials A and B (material to be plated) with an alkaline degreasing solution, each was used as a negative electrode, and using a plating tank containing a nickel strike plating solution having the composition of (1) above,
Nickel strike plating was performed for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 .
【０３１３】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−ＰＴＦＥ複合メッキ液を
含むメッキ槽中、液温５０℃、ｐＨ４．２、電流密度２
Ａ／ｄｍ2の条件で、スクリュー撹拌しつつ、膜厚が１
０μｍとなるまで電解メッキを行って、電解ニッケル−
ＰＴＦＥ複合メッキ皮膜を形成させた。この時点で共析
率測定用試験片を使用し、ＰＴＦＥの共析率（容量％）
を求めたところ、３０容量％であった。Next, using the obtained coating material, in a plating tank containing the electrolytic nickel-PTFE composite plating solution having the composition (2), a solution temperature of 50 ° C., a pH of 4.2 and a current density of 2 were prepared.
Under the condition of A / dm 2 , the film thickness is 1
Electroplating is performed until the thickness becomes 0 μm.
A PTFE composite plating film was formed. At this point, the eutectoid rate of PTFE (volume%) was measured using a test piece for eutectoid rate measurement.
Was 30% by volume.
【０３１４】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解カドミウム−
スズ合金メッキ液を含むメッキ槽を用いて、ｐＨ３．
０、液温２５℃、電流密度３Ａ／ｄｍ2の条件で、膜厚
が０．５μｍとなるまで電解メッキを行って、カドミウ
ム−スズ合金メッキ皮膜を形成させた。メッキ終了後、
水洗し、１００℃で、５分間乾燥させた。Further, using the composite-plated coating as a negative electrode, an electrolytic cadmium alloy having the composition of (3) above was used.
Using a plating bath containing a tin alloy plating solution, a pH of 3.
Under a condition of 0, a liquid temperature of 25 ° C., and a current density of 3 A / dm 2 , electrolytic plating was performed until the film thickness became 0.5 μm to form a cadmium-tin alloy plating film. After plating,
It was washed with water and dried at 100 ° C. for 5 minutes.
【０３１５】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上にカドミウム−スズ合金メッキ皮膜を施した
メッキ被覆物を、熱風循環式乾燥炉中で、３５０℃で３
０分間加熱した後、常温で１時間室内放置した。このメ
ッキ被覆物の表面をＥＰＭＡ分析装置（日本電子（株）
製ＪＸＡ−８９００ＲＬ）を用いて分析したところ、ニ
ッケル：６０重量％、カドミウム：２８重量％及びス
ズ：１２重量％のニッケル−カドミウム−スズ合金が形
成されていた。また、前記ＥＰＭＡ分析装置を用いて、
断面深さ方向のカドミウム及びスズの分析を行ったとこ
ろ、カドミウム及びスズの拡散層の厚みは３μｍであっ
た。この耐食性複合メッキ皮膜が施された被覆物を用い
て前記（２）〜（９）の試験を行った。[0315] The plated coating obtained by applying a cadmium-tin alloy plating film on the obtained electrolytic nickel-PTFE composite plating film was dried at 350 ° C in a hot-air circulating drying furnace.
After heating for 0 minutes, it was left indoors at room temperature for 1 hour. The surface of this plated coating is analyzed with an EPMA analyzer (JEOL Ltd.)
As a result of analysis using a JXA-8900RL manufactured by Nissan Co., a nickel-cadmium-tin alloy of 60% by weight of nickel, 28% by weight of cadmium and 12% by weight of tin was formed. Further, using the EPMA analyzer,
When cadmium and tin were analyzed in the cross-sectional depth direction, the thickness of the cadmium and tin diffusion layer was 3 μm. The tests (2) to (9) were performed using the coating provided with the corrosion-resistant composite plating film.
【０３１６】実施例４１ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 41 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０３１７】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−ＰＴＦＥ複合メッキ液の調製 電解ニッケルメッキ液（組成：スルファミン酸ニッケル
３６０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ
／Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子
径０．２μｍ、ダイキン工業（株）製、ルブロンＬ−
２）５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面
活性剤としての第４級パーフルオロアンモニウム塩［Ｃ
8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録
商標「メガファックＦ１５０」，大日本インキ化学
（株）製］を３０．０ｍｇ添加して、電解ニッケル−Ｐ
ＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-PTFE composite plating solution Electrolytic nickel plating solution (composition: nickel sulfamate 360 g / L, nickel chloride 45 g / L, boric acid 30 g)
/ L) PTFE fine particles (average particle diameter 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-
2) 50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C
8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3 · Cl -, R "Megafac F150", Dainippon Ink and Chemicals Co., Ltd.] was added 30.0mg of electrolytic nickel - P
A TFE composite plating solution was prepared.
【０３１８】（３）電解鉛−スズ−亜鉛合金メッキ液の
調製 下記の組成を有する電解鉛−スズ−亜鉛メッキ液を調製
した。(3) Preparation of electrolytic lead-tin-zinc alloy plating solution An electrolytic lead-tin-zinc plating solution having the following composition was prepared.
【０３１９】 ホウフッ化鉛 ４０ｇ／Ｌ ホウフッ化スズ １５ｇ／Ｌ ホウフッ化亜鉛 ２ｇ／Ｌ にかわ １ｇ／Ｌ （４）メッキ法 前記基材Ａ及びＢ（被メッキ材料）をアルカリ脱脂液で
脱脂した後、それぞれを負極とし、前記（１）の組成の
ニッケルストライクメッキ液を含むメッキ槽を用いて、
液温２５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッ
ケルストライクメッキ処理を２分間行った。Lead borofluoride 40 g / L tin borofluoride 15 g / L zinc borofluoride 2 g / L glue 1 g / L (4) Plating method After the base materials A and B (material to be plated) were degreased with an alkaline degreaser, Using each as a negative electrode and a plating tank containing a nickel strike plating solution of the composition of the above (1),
Nickel strike plating was performed for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 .
【０３２０】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−ＰＴＦＥ複合メッキ液を
含むメッキ槽中、液温５０℃、ｐＨ４．２、電流密度２
Ａ／ｄｍ2の条件で、スクリュー撹拌しつつ、膜厚が１
０μｍとなるまで電解メッキを行って、電解ニッケル−
ＰＴＦＥ複合メッキ皮膜を形成させた。この時点で共析
率測定用試験片を使用し、ＰＴＦＥの共析率（容量％）
を求めたところ、３０容量％であった。Next, using the obtained coating material, in a plating tank containing the electrolytic nickel-PTFE composite plating solution having the composition of the above (2), a liquid temperature of 50 ° C., a pH of 4.2, and a current density of 2
Under the condition of A / dm 2 , the film thickness is 1
Electroplating is performed until the thickness becomes 0 μm.
A PTFE composite plating film was formed. At this point, the eutectoid rate of PTFE (volume%) was measured using a test piece for eutectoid rate measurement.
Was 30% by volume.
【０３２１】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解鉛−スズ−亜
鉛合金メッキ液を含むメッキ槽を用いて、液温２０℃、
電流密度１Ａ／ｄｍ2の条件で、膜厚が０．５μｍとな
るまで電解メッキを行って、鉛−スズ−亜鉛合金メッキ
皮膜を形成させた。メッキ終了後、水洗し、１００℃
で、５分間乾燥させた。Further, using the composite-plated coating as a negative electrode, a plating bath containing an electrolytic lead-tin-zinc alloy plating solution having the composition of the above (3) was used.
Electroplating was performed at a current density of 1 A / dm 2 until the film thickness reached 0.5 μm, to form a lead-tin-zinc alloy plating film. After plating, wash with water and 100 ℃
And dried for 5 minutes.
【０３２２】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上に鉛−亜鉛−スズ合金メッキ皮膜を施したメ
ッキ被覆物を、熱風循環式乾燥炉中で、３５０℃で３０
分間加熱した後、常温で１時間室内放置した。このメッ
キ被覆物の表面をＥＰＭＡ分析装置（日本電子（株）製
ＪＸＡ−８９００ＲＬ）を用いて分析したところ、ニッ
ケル：６０重量％、鉛：３５重量％、スズ：４重量％及
び亜鉛：１重量％のニッケル−鉛−スズ−亜鉛合金が形
成されていた。また、前記ＥＰＭＡ分析装置を用いて、
断面深さ方向の鉛、スズ及び亜鉛の分析を行ったとこ
ろ、鉛、亜鉛及びスズの拡散層の厚みは３μｍであっ
た。この耐食性複合メッキ皮膜が施された被覆物を用い
て前記（２）〜（９）の試験を行った。[0322] The plated coating obtained by applying a lead-zinc-tin alloy plating film on the obtained electrolytic nickel-PTFE composite plating film was dried at 350 ° C for 30 minutes in a hot-air circulation drying oven.
After heating for minutes, it was left indoors at room temperature for 1 hour. When the surface of the plated coating was analyzed using an EPMA analyzer (JXA-8900RL manufactured by JEOL Ltd.), nickel: 60% by weight, lead: 35% by weight, tin: 4% by weight, and zinc: 1% by weight. % Nickel-lead-tin-zinc alloy was formed. Further, using the EPMA analyzer,
Analysis of lead, tin and zinc in the cross-section depth direction revealed that the thickness of the lead, zinc and tin diffusion layer was 3 μm. The tests (2) to (9) were performed using the coating provided with the corrosion-resistant composite plating film.
【０３２３】実施例４２ （１）ニッケルストライクメッキ液の調製 下記の組成を有するニッケルストライクメッキ液を調製
した。Example 42 (1) Preparation of Nickel Strike Plating Solution A nickel strike plating solution having the following composition was prepared.
【０３２４】 塩化ニッケル ２４５ｇ／Ｌ 塩酸 １２０ｇ／Ｌ （２）電解ニッケル−ＰＴＦＥ複合メッキ液の調製 電解ニッケルメッキ液（組成：スルファミン酸ニッケル
３６０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸３０ｇ
／Ｌ）１リットルに対して、ＰＴＦＥ微粒子（平均粒子
径０．２μｍ、ダイキン工業（株）製、ルブロンＬ−
２）５０ｇを添加し、このＰＴＦＥ１ｇに対して、界面
活性剤としての第４級パーフルオロアンモニウム塩［Ｃ
8Ｆ17ＳＯ2ＮＨ（ＣＨ2）3Ｎ+（ＣＨ3）3・Ｃｌ-，登録
商標「メガファックＦ１５０」，大日本インキ化学
（株）製］を３０．０ｍｇ添加して、電解ニッケル−Ｐ
ＴＦＥ複合メッキ液を調製した。Nickel chloride 245 g / L Hydrochloric acid 120 g / L (2) Preparation of electrolytic nickel-PTFE composite plating solution Electrolytic nickel plating solution (composition: nickel sulfamate 360 g / L, nickel chloride 45 g / L, boric acid 30 g)
/ L) PTFE fine particles (average particle diameter 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-
2) 50 g was added, and 1 g of this PTFE was added to a quaternary perfluoroammonium salt [C
8 F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3 · Cl -, R "Megafac F150", Dainippon Ink and Chemicals Co., Ltd.] was added 30.0mg of electrolytic nickel - P
A TFE composite plating solution was prepared.
【０３２５】（３）電解鉛−スズ−アンチモン合金メッ
キ液の調製 下記の組成を有する電解鉛−スズ−アンチモンメッキ液
を調製した。(3) Preparation of electrolytic lead-tin-antimony alloy plating solution An electrolytic lead-tin-antimony plating solution having the following composition was prepared.
【０３２６】 ホウフッ化鉛 １００ｇ／Ｌ ホウフッ化スズ ３０ｇ／Ｌ ホウフッ化アンチモン ６ｇ／Ｌ ホウフッ酸 ８０ｇ／Ｌ ハイドロキノン ０．５ｇ／Ｌ ペプトン １５ｇ／Ｌ （４）メッキ法 前記基材Ａ及びＢ（被メッキ材料）をアルカリ脱脂液で
脱脂した後、それぞれを負極とし、前記（１）の組成の
ニッケルストライクメッキ液を含むメッキ槽を用いて、
液温２５℃、電流密度１０Ａ／ｄｍ2の条件下で、ニッ
ケルストライクメッキ処理を２分間行った。Lead borofluoride 100 g / L tin borofluoride 30 g / L antimony borofluoride 6 g / L borofluoric acid 80 g / L hydroquinone 0.5 g / L peptone 15 g / L (4) Plating method The substrates A and B (plated) Material) was degreased with an alkali degreasing solution, each was used as a negative electrode, and using a plating tank containing a nickel strike plating solution having the composition of (1) above,
Nickel strike plating was performed for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 .
【０３２７】ついで、得られた被覆物を用いて、前記
（２）の組成の電解ニッケル−ＰＴＦＥ複合メッキ液を
含むメッキ槽中、液温５０℃、ｐＨ４．２、電流密度２
Ａ／ｄｍ2の条件で、スクリュー撹拌しつつ、膜厚が１
０μｍとなるまで電解メッキを行って、電解ニッケル−
ＰＴＦＥ複合メッキ皮膜を形成させた。この時点で共析
率測定用試験片を使用し、ＰＴＦＥの共析率（容量％）
を求めたところ、３０容量％であった。Next, using the obtained coating material, in a plating tank containing the electrolytic nickel-PTFE composite plating solution having the composition of the above (2), a liquid temperature of 50 ° C., a pH of 4.2, and a current density of 2
Under the condition of A / dm 2 , the film thickness is 1
Electroplating is performed until the thickness becomes 0 μm.
A PTFE composite plating film was formed. At this point, the eutectoid rate of PTFE (volume%) was measured using a test piece for eutectoid rate measurement.
Was 30% by volume.
【０３２８】更に、前記複合メッキを施した被覆物を負
極として、前記（３）の組成を有する電解鉛−スズ−ア
ンチモン合金メッキ液を含むメッキ槽を用いて、液温２
０℃、電流密度４Ａ／ｄｍ2の条件で、膜厚が０．５μ
ｍとなるまで電解メッキを行って、鉛−スズ−アンチモ
ン合金メッキ皮膜を形成させた。メッキ終了後、水洗
し、１００℃で、５分間乾燥させた。Further, using the coated material subjected to the composite plating as a negative electrode, a plating bath containing an electrolytic lead-tin-antimony alloy plating solution having the composition of the above (3) was used, and a solution temperature of 2% was used.
Under the conditions of 0 ° C. and a current density of 4 A / dm 2 , the film thickness is 0.5 μm.
m, to form a lead-tin-antimony alloy plating film. After plating was completed, it was washed with water and dried at 100 ° C. for 5 minutes.
【０３２９】得られた電解ニッケル−ＰＴＦＥ複合メッ
キ皮膜の上に鉛−亜鉛−アンチモン合金メッキ皮膜を施
したメッキ被覆物を、熱風循環式乾燥炉中で、３５０℃
で３０分間加熱した後、常温で１時間室内放置した。こ
のメッキ被覆物の表面をＥＰＭＡ分析装置（日本電子
（株）製ＪＸＡ−８９００ＲＬ）を用いて分析したとこ
ろ、ニッケル：６０重量％、鉛：３２重量％、スズ：５
重量％及びアンチモン：３重量％のニッケル−鉛−スズ
−アンチモン合金が形成されていた。また、前記ＥＰＭ
Ａ分析装置を用いて、断面深さ方向の鉛、スズ及びアン
チモンの分析を行ったところ、鉛、スズ及びアンチモン
の拡散層の厚みは３μｍであった。この耐食性複合メッ
キ皮膜が施された被覆物を用いて前記（２）〜（９）の
試験を行った。The plated nickel-PTFE composite coating on which the lead-zinc-antimony alloy plating was applied was heated at 350 ° C. in a hot-air circulation drying oven.
And then left indoors at room temperature for 1 hour. When the surface of the plated coating was analyzed using an EPMA analyzer (JXA-8900RL, manufactured by JEOL Ltd.), nickel: 60% by weight, lead: 32% by weight, tin: 5
% By weight and antimony: 3% by weight of a nickel-lead-tin-antimony alloy was formed. In addition, the EPM
Analysis of lead, tin, and antimony in the cross-section depth direction using an A analyzer showed that the thickness of the diffusion layer of lead, tin, and antimony was 3 μm. The tests (2) to (9) were performed using the coating provided with the corrosion-resistant composite plating film.
【０３３０】実施例のメッキ被覆物について、前記物性
及び特性の評価を行った結果を表７及び表８に示す。Tables 7 and 8 show the results of the evaluation of the physical properties and characteristics of the plated coatings of the examples.
【０３３１】[0331]
【表７】 [Table 7]
【０３３２】[0332]
【表８】 [Table 8]
【０３３３】表から明らかなように、本発明による耐食
性（フッ素化合物共析）複合メッキ皮膜は、極めて優れ
た撥水性、非粘着性、密着性、耐衝撃変形性、耐薬品
性、耐摩耗性、摺動性、耐熱性、装飾性等を備えてい
る。As is clear from the table, the corrosion-resistant (fluoride compound eutectoid) composite plating film of the present invention has extremely excellent water repellency, non-adhesion, adhesion, impact deformation resistance, chemical resistance, and abrasion resistance. Slidability, heat resistance, decorativeness, etc.
【図１】図１は本発明のメッキ皮膜を説明するための概
略断面図である。FIG. 1 is a schematic cross-sectional view for explaining a plating film of the present invention.
１…基材 ２…耐食性複合メッキ皮膜 ３…ニッケル系マトリックス金属 ４…フッ素化合物微粒子 ５…第２の金属の拡散層 ６…ニッケル系メッキ層 DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Corrosion-resistant composite plating film 3 ... Nickel-based matrix metal 4 ... Fluorine compound fine particles 5 ... Diffusion layer of 2nd metal 6 ... Nickel-based plating layer
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２５Ｄ 7/00 Ｃ２５Ｄ 7/00 Ｃ Ｆ Ｍ 7/10 7/10 Ｆ１６Ｃ 33/12 Ｆ１６Ｃ 33/12 Ｚ Ｆターム(参考） 3J011 CA05 QA03 SB05 SB15 SB20 SC04 SC05 4K022 AA02 AA48 AA50 BA14 BA16 BA32 BA34 BA36 BA37 DA01 EA01 EA04 4K024 AA01 AA03 AA05 AA06 AA07 AA08 AA14 AA19 AA22 AB02 AB12 AB17 BB04 BB05 BB07 BB17 DA09 GA03 GA16 Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) C25D 7/00 C25D 7/00 C F M 7/10 7/10 F16C 33/12 F16C 33/12 Z F term (reference 3J011 CA05 QA03 SB05 SB15 SB20 SC04 SC05 4K022 AA02 AA48 AA50 BA14 BA16 BA32 BA34 BA36 BA37 DA01 EA01 EA04 4K024 AA01 AA03 AA05 AA06 AA07 AA08 AA14 AA19 AA22 AB02 AB12 AB17 BB04 BB05 BB05 BB05 GA03
Claims (17)
ル系複合メッキ皮膜であって、この複合メッキ皮膜が、
ニッケルと融点が４２０℃以下の第２の金属との合金で
構成されているメッキ皮膜。1. A nickel-based composite plating film containing fine particles of a fluorine compound, wherein the composite plating film comprises:
A plating film made of an alloy of nickel and a second metal having a melting point of 420 ° C. or less.
ル系複合メッキ皮膜であって、融点が４２０℃以下の第
２の金属が表面から深さ方向に拡散しているメッキ皮
膜。2. A nickel-based composite plating film containing fine particles of a fluorine compound, wherein a second metal having a melting point of 420 ° C. or less is diffused from a surface in a depth direction.
構成された金属単体又は合金である請求項１又は２記載
のメッキ皮膜。3. The plating film according to claim 1, wherein the second metal is a single metal or an alloy composed of at least the second metal.
銀、ガリウム、インジウム、タリウム、スズ、及び鉛か
ら選択された少なくとも一種である請求項３記載のメッ
キ皮膜。4. The plating film according to claim 3, wherein the second metal is at least one selected from zinc, cadmium, mercury, gallium, indium, thallium, tin, and lead.
方向に拡散し、かつニッケル−スズ合金を形成している
請求項１記載のメッキ皮膜。5. The plating film according to claim 1, wherein tin as the second metal diffuses in the depth direction from the surface and forms a nickel-tin alloy.
る請求項１又は２記載のメッキ皮膜。6. The plating film according to claim 1, wherein the melting point of the second metal is 20 to 420 ° C.
いる請求項１又は２記載のメッキ皮膜。7. The plating film according to claim 1, wherein fine particles of a fluorine compound are exposed on the surface.
属の拡散層とニッケル系メッキ層とで構成されており、
表面にフッ素化合物の微粒子が露出している請求項２記
載のメッキ皮膜。8. A nickel-based composite plating film comprising a diffusion layer of a second metal and a nickel-based plating layer,
3. The plating film according to claim 2, wherein fine particles of a fluorine compound are exposed on the surface.
２の金属の拡散層とニッケル系メッキ層との厚みの比
が、前者／後者＝１／９９〜９９／１である請求項８記
載のメッキ皮膜。9. The plating according to claim 8, wherein in the nickel-based composite plating film, the ratio of the thickness of the diffusion layer of the second metal to the thickness of the nickel-based plating layer is the former / the latter = 1/99 to 99/1. Film.
びフッ化ピッチから選択された少なくとも一種のフッ素
化合物で構成されている請求項１又は２記載のメッキ皮
膜。10. The plating film according to claim 1, wherein the fine particles are composed of at least one fluorine compound selected from a fluororesin, fluorinated graphite and fluorinated pitch.
チレン、テトラフルオロエチレン−ヘキサフルオロプロ
ピレン共重合体、テトラフルオロエチレン−パーフルオ
ロアルキルビニルエーテル共重合体、ポリクロロトリフ
ルオロエチレン及びテトラフルオロエチレン−エチレン
共重合体から選択された少なくとも一種である請求項１
０記載のメッキ皮膜。11. The fluororesin is polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, polychlorotrifluoroethylene and tetrafluoroethylene-ethylene copolymer. 2. The at least one member selected from the union.
0 plating film.
ッキ皮膜が形成されているメッキ被覆物。12. A plated coating having a plating film according to claim 1 formed on a surface of a substrate.
請求項１２記載のメッキ被覆物。13. The plated coating according to claim 12, which exhibits non-adhesiveness or slidability under heating.
型、摺動部材、軸受け部材及び航空機用部材から選択さ
れた少なくとも一種である請求項１２記載のメッキ被覆
物。14. The plated coating according to claim 12, which is at least one selected from a cooking utensil, a cooking utensil member, a molding die, a sliding member, a bearing member and an aircraft member.
するニッケル系複合メッキ皮膜を形成するメッキ皮膜の
製造方法であって、前記複合メッキ皮膜をニッケルと融
点が４２０℃以下の第２の金属との合金で構成するメッ
キ皮膜の製造方法。15. A method for producing a plating film for forming a nickel-based composite plating film containing fine particles of a fluorine compound on a substrate, wherein the composite plating film is formed of nickel and a second metal having a melting point of 420 ° C. or less. Production method of plating film composed of alloy with
ケル系複合メッキ皮膜の上に、少なくとも融点が４２０
℃以下の第２の金属で構成された皮膜を形成し、加熱処
理して、前記ニッケル系複合メッキ皮膜中に前記第２の
金属を溶融拡散させるメッキ皮膜の製造方法。16. At least a melting point of 420 on a nickel-based composite plating film containing fine particles of a fluorine compound.
A method for producing a plating film in which a film composed of a second metal at a temperature of not more than ° C is formed and heat-treated to melt-diffuse the second metal into the nickel-based composite plating film.
の金属で構成された皮膜を形成する請求項１６記載の製
造方法。17. The second layer having a thickness such that the fine particles can be exposed on the surface.
The method according to claim 16, wherein a film composed of the metal is formed.
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| JP2001213073A JP4681161B2 (en) | 2000-07-14 | 2001-07-13 | Plating film and plating coating using the same |
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| JP2000214549 | 2000-07-14 | ||
| JP2001023450 | 2001-01-31 | ||
| JP2001-23450 | 2001-03-23 | ||
| JP2001-85205 | 2001-03-23 | ||
| JP2001085205 | 2001-03-23 | ||
| JP2000-214549 | 2001-03-23 | ||
| JP2001213073A JP4681161B2 (en) | 2000-07-14 | 2001-07-13 | Plating film and plating coating using the same |
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| JP4681161B2 JP4681161B2 (en) | 2011-05-11 |
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