JP7014414B2 - Plating fiber and electric wire - Google Patents
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Description
本発明は、繊維の上にめっき膜を備えためっき繊維と、めっき繊維を使用した電線に関するものである。 The present invention relates to a plated fiber having a plated film on the fiber and an electric wire using the plated fiber.
従来より、繊維の上に金属めっき膜を形成しためっき繊維を、電磁シールド布、静電気防止布、導電性布、遮光性布等に用いることが知られている。 Conventionally, it has been known that a plated fiber having a metal plating film formed on the fiber is used for an electromagnetic shield cloth, an antistatic cloth, a conductive cloth, a light-shielding cloth and the like.
また、近年では、電線としての銅線を、繊維の上に銅めっき膜を形成しためっき繊維に置き換えることにより、電線の軽量化・低コスト化を図ることが検討されている（特許文献１，２）。 Further, in recent years, it has been studied to reduce the weight and cost of electric wires by replacing copper wires as electric wires with plated fibers having a copper plating film formed on the fibers (Patent Documents 1 and 1). 2).
しかし、銅めっき膜は酸化しやすく摩耗しやすいため、めっき繊維が変色や抵抗値増加等の経時劣化を起こしやすい。 However, since the copper plating film is easily oxidized and easily worn, the plated fibers are liable to deteriorate with time such as discoloration and increase in resistance value.
そこで、銅めっき膜の上に接して錫めっき膜を形成したものも検討されている（特許文献３）。錫は、銅よりイオン化傾向が高いので銅より酸化されやすいが、銅とは異なり酸化膜が変色しにくく白色のままである。また、錫は銅の犠牲陽極として働くため、銅の酸化、抵抗値の上昇を遅らせる働きがある。よって、めっき繊維の上記経時劣化を防止することを期待できる。さらに、錫めっき膜はハンダ付け性が良いという利点もある。 Therefore, a tin-plated film formed in contact with the copper-plated film has also been studied (Patent Document 3). Since tin has a higher ionization tendency than copper, it is more easily oxidized than copper, but unlike copper, the oxide film is less likely to discolor and remains white. In addition, since tin acts as a sacrificial anode of copper, it has the function of delaying the oxidation of copper and the increase in resistance value. Therefore, it can be expected to prevent the deterioration of the plated fiber over time. Further, the tin-plated film has an advantage that it has good solderability.
しかしながら、本発明者の検討によると、銅めっき膜の上に接して錫めっき膜を形成したものを、塩水噴霧試験してみると、１サイクル後の観察で赤黒く変色していて、抵抗値も測定できないほどに増加しており、上記の期待どおりにはいかないことが分かった。これは、銅めっき膜の銅が錫めっき膜へ拡散することによるものと考えられる。 However, according to the study of the present inventor, when a tin-plated film was formed in contact with the copper-plated film and subjected to a salt spray test, the color changed to red-black in the observation after one cycle, and the resistance value was also high. It was found that the increase was unmeasurable and did not meet the above expectations. It is considered that this is because the copper in the copper plating film diffuses into the tin plating film.
そこで、本発明の目的は、非金属繊維の上に銅めっき膜を備えためっき繊維とそれを使用した電線の変色や抵抗値増加等の経時劣化を防止することにある。 Therefore, an object of the present invention is to prevent deterioration over time such as discoloration and increase in resistance value of a plated fiber having a copper plating film on a non-metal fiber and an electric wire using the plated fiber.
本願において、「…の上に」とは、…の上に接して又は他の膜を介してという意味である。
本願において、「ニッケル系めっき膜」とは、ニッケルめっき膜、ニッケル合金めっき膜又はニッケル複合めっき膜の意味である。
In the present application, "on top of ..." means in contact with ... or through another membrane.
In the present application, the "nickel-based plating film" means a nickel plating film, a nickel alloy plating film, or a nickel composite plating film.
（１）参考発明のめっき繊維は、非金属繊維と、非金属繊維の上に形成された銅めっき膜と、銅めっき膜の上に形成されたニッケル系めっき膜とを含むことを特徴とする。 (1) The plating fiber of the reference invention is characterized by including a non-metal fiber, a copper plating film formed on the non-metal fiber, and a nickel-based plating film formed on the copper plating film. ..
［作用］
ニッケル系めっき膜は、銅めっき膜の銅の拡散するのを抑止する。また、ニッケル系めっき膜は、銅めっき膜を酸化・摩耗から保護するとともに、ニッケル系めっき膜自体が銅めっき膜よりも酸化・摩耗しにくい。これらにより、めっき繊維の変色、抵抗値増加、摩耗等の経時劣化を防止することができる。
[Action]
The nickel-based plating film suppresses the diffusion of copper in the copper plating film. Further, the nickel-based plating film protects the copper plating film from oxidation and wear, and the nickel-based plating film itself is less likely to be oxidized and worn than the copper plating film. As a result, it is possible to prevent deterioration over time such as discoloration of the plated fiber, increase in resistance value, and wear.
（２）本発明のめっき繊維は、非金属繊維と、非金属繊維の上に形成された銅めっき膜と、銅めっき膜の上に形成されたニッケル系めっき膜と、ニッケル系めっき膜の上に形成された錫めっき膜とを含むめっき繊維であって、
前記錫めっき膜は、めっき繊維のめっき層として最外層であり、
前記ニッケル系めっき膜は、前記銅めっき膜の銅が前記錫めっき膜へ拡散するのを抑止するためのものであって、膜厚が０．１μｍ以上であり、
めっき繊維は、ＪＩＳ Ｚ２３７１に準拠した塩水噴霧試験３サイクル後の観察で変色が無く、該塩水噴霧試験前に対して抵抗値増加が無いことを特徴とする。
(2) The plating fiber of the present invention is a non-metal fiber, a copper plating film formed on the non-metal fiber, a nickel-based plating film formed on the copper plating film, and a nickel-based plating film. A plating fiber containing a tin-plated film formed on the surface of the plating fiber.
The tin-plated film is the outermost layer as a plating layer for plating fibers.
The nickel-based plating film is for suppressing the copper of the copper plating film from diffusing into the tin plating film, and has a film thickness of 0.1 μm or more.
The plated fiber is characterized in that there is no discoloration in the observation after 3 cycles of the salt spray test according to JIS Z2371, and there is no increase in resistance value as compared with that before the salt spray test .
［作用］
ニッケル系めっき膜は、銅めっき膜の銅が錫めっき膜へ拡散するのを抑止する。また、錫めっき膜は、銅めっき膜と錫めっき膜の間に挟むことによって、銅の錫への拡散を抑えることができるため、めっき繊維は変色や抵抗値増加等の経時劣化を起こしにくい。
[Action]
The nickel-based plating film suppresses the diffusion of copper in the copper plating film into the tin plating film. Further, since the tin-plated film can suppress the diffusion of copper into tin by sandwiching it between the copper-plated film and the tin-plated film, the plated fiber is less likely to cause deterioration over time such as discoloration and increase in resistance value.
（３）本発明の電線は、上記（２）のめっき繊維を使用して構成したことを特徴とする。 (3) The electric wire of the present invention is characterized in that it is constructed by using the plated fiber of (2) above .
本発明によれば、非金属繊維の上に銅めっき膜を備えためっき繊維とそれを使用した電線の変色や抵抗値増加等の経時劣化を防止することができる。 According to the present invention, it is possible to prevent deterioration over time such as discoloration and increase in resistance value of a plated fiber having a copper plating film on a non-metal fiber and an electric wire using the plated fiber.
＜１＞非金属繊維
非金属繊維としては、特に限定されないが、次の（ａ）（ｂ）（ｃ）を例示できる。
（ａ）有機繊維
・合成繊維：ポリエステル繊維（ポリエチレンテレフタレート（ＰＥＴ）繊維、ポリブチレンテレフタレート（ＰＢＴ）繊維等）、ポリオレフィン系繊維（ポリエチレン（ＰＥ）繊維、ポリプロピレン（ＰＰ）繊維等）、ビニロン繊維、レーヨン繊維、ナイロン繊維、ポリカ―ボネート繊維、ポリアセタ―ル繊維、アクリル繊維、ポリアミド系繊維、アラミド繊維等。
・天然繊維：綿、麻、絹、竹等。
（ｂ）無機繊維
ガラス繊維、鉱物繊維、セラミック繊維、シリカ繊維等。
（ｃ）電線として用いるめっき繊維の繊維には、高抗張力であるパラ系アラミド繊維、ＰＢＯ（poly(p-phenylenebenzobisoxazole)）繊維、ポリアリレート繊維、超高分子量ポリエチレン繊維等が好ましい。また、抗張力が１５ｃＮ／ｄｔｅｘ以上の繊維が好ましいが、抗張力が例えば６～８ｃＮ／ｄｔｅｘと低い繊維でも繊度が１００ｄｔｅｘ以上と太い繊維を使うことによって対応することができる。
非金属繊維は、モノフィラメントでも、マルチフィラメント（複数本のフィラメントの束）でもよい。１本のフィラメントの直径は、特に限定されず、１０～２００μｍを例示できる。マルチフィラメントの場合、１本のフィラメントの直径は１０～２５μｍが好ましい。
<1> Non-metal fiber The non-metal fiber is not particularly limited, but the following (a), (b) and (c) can be exemplified.
(A) Organic fiber / synthetic fiber: polyester fiber (polyethylene terephthalate (PET) fiber, polybutylene terephthalate (PBT) fiber, etc.), polyolefin fiber (polyethylene (PE) fiber, polypropylene (PP) fiber, etc.), vinylon fiber, Rayon fiber, nylon fiber, polycarbonate fiber, polyacetal fiber, acrylic fiber, polyamide fiber, aramid fiber, etc.
-Natural fibers: cotton, linen, silk, bamboo, etc.
(B) Inorganic fiber Glass fiber, mineral fiber, ceramic fiber, silica fiber, etc.
(C) As the fibers of the plated fibers used as electric wires, para-aramid fibers having high tensile strength, PBO (poly (p-phenylenebenzobisoxazole)) fibers, polyarylate fibers, ultra-high molecular weight polyethylene fibers and the like are preferable. Further, fibers having a tensile strength of 15 cN / dtex or more are preferable, but fibers having a low tensile strength of, for example, 6 to 8 cN / dtex can be dealt with by using thick fibers having a fineness of 100 dtex or more.
The non-metal fiber may be a monofilament or a multifilament (a bundle of a plurality of filaments). The diameter of one filament is not particularly limited, and can be exemplified by 10 to 200 μm. In the case of multifilament, the diameter of one filament is preferably 10 to 25 μm.
＜２＞前処理
非金属繊維は、めっき処理前に、めっき付着性向上等を目的とする前処理を行うことが好ましい。前処理としては、特に限定されないが、次の（ａ）（ｂ）を例示できる。
（ａ）湿式前処理
アルカリエッチング→中和→表面調整→触媒付与→活性化、の順で行うことができる。
表面調整は、例えば、カチオン界面活性剤液に浸漬して行うことができる。
触媒付与は、例えば、錫－パラジウムコロイドに浸漬して行うことができる。
活性化は、例えば、酸またはアルカリ液に浸漬してコロイドの塩化第一錫を溶解する工程である。
（ｂ）乾式前処理
超臨界核付け→熱処理（還元）、の順で行うことができる。
超臨界核付けは、高温・高圧で超臨界状態になるパラジウム錯体をチャンバーにいれ、超臨界状態でパラジウムを繊維に付着させることで行うことができる。
<2> Pretreatment For non-metal fibers, it is preferable to perform a pretreatment for the purpose of improving plating adhesion and the like before the plating treatment. The pretreatment is not particularly limited, but the following (a) and (b) can be exemplified.
(A) Wet pretreatment Alkaline etching → neutralization → surface adjustment → catalyst application → activation can be performed in this order.
The surface adjustment can be performed, for example, by immersing in a cationic surfactant solution.
The catalyst application can be carried out, for example, by immersing in a tin-palladium colloid.
Activation is, for example, the step of immersing in an acid or alkaline solution to dissolve the colloidal stannous chloride.
(B) Dry pretreatment Supercritical nucleation → heat treatment (reduction) can be performed in this order.
Supercritical nucleation can be performed by placing a palladium complex that is in a supercritical state at high temperature and high pressure in a chamber and adhering palladium to the fiber in the supercritical state.
＜３＞導通性付与膜
次に行う電気めっきのために、前処理後の非金属繊維繊維の表面に接して金属の導通性付与膜を形成することが好ましい。
導通性付与膜の膜厚は、特に限定されないが、０．１～１μｍが好ましい。
導通性付与膜は、例えば、銅等の無電解めっきにより形成することができる。
<3> Conductivity-imparting film For the next electroplating, it is preferable to form a metal continuity-imparting film in contact with the surface of the non-metal fiber after the pretreatment.
The film thickness of the conductivity-imparting film is not particularly limited, but is preferably 0.1 to 1 μm.
The continuity-imparting film can be formed by, for example, electroless plating of copper or the like.
＜４＞銅めっき膜
銅めっき膜の膜厚は、特に限定されないが、めっき繊維の主たる導電膜であるから、他のめっき膜よりも厚いことが好ましく、例えば０．５～４μｍが好ましく、１～３．５μｍがより好ましい。
また、本発明のめっき繊維を複数本使用して電線を構成する場合、電線としての抵抗値を０．２～２０Ω／ｍとすることが好ましい。
銅めっき膜は、電気めっき等により形成することができる。
<4> Copper plating film The thickness of the copper plating film is not particularly limited, but is preferably thicker than other plating films because it is the main conductive film of the plating fiber, for example, 0.5 to 4 μm is preferable. It is more preferably ~ 3.5 μm.
Further, when a wire is formed by using a plurality of plated fibers of the present invention, it is preferable that the resistance value of the wire is 0.2 to 20 Ω / m.
The copper plating film can be formed by electroplating or the like.
＜５＞ニッケル系めっき膜
ニッケル系めっき膜は、前述のとおりニッケルめっき膜、ニッケル合金めっき膜又はニッケル複合めっき膜である。ニッケル合金めっき膜のニッケル合金としては、特に限定されないが、ニッケル－リン合金、ニッケル－ボロン合金、ニッケル－クロム合金、ニッケル－コバルト合金、ニッケル－亜鉛合金等を例示できる。
ニッケル系めっき膜の膜厚は、特に限定されないが、０．１～１μｍが好ましい。０．１μｍ以上あれば銅の拡散を抑えることができ、１μｍ以上ではめっき繊維独特のしなやかさが無くなり、生産コストも高くなる。
ニッケル系めっき膜は、無電解めっき、電気めっき等により形成することができる。
<5> Nickel-based plating film The nickel-based plating film is a nickel plating film, a nickel alloy plating film, or a nickel composite plating film as described above. The nickel alloy of the nickel alloy plating film is not particularly limited, and examples thereof include a nickel-phosphorus alloy, a nickel-boron alloy, a nickel-chromium alloy, a nickel-cobalt alloy, and a nickel-zinc alloy.
The film thickness of the nickel-based plating film is not particularly limited, but is preferably 0.1 to 1 μm. If it is 0.1 μm or more, the diffusion of copper can be suppressed, and if it is 1 μm or more, the suppleness peculiar to the plated fiber is lost and the production cost is high.
The nickel-based plating film can be formed by electroless plating, electroplating, or the like.
＜６＞錫めっき膜
錫めっき膜の膜厚は、特に限定されないが、０．１～１μｍが好ましい。
錫めっき膜は、無電解めっき、電気めっき等により形成することができる。
<6> Tin-plated film The thickness of the tin-plated film is not particularly limited, but is preferably 0.1 to 1 μm.
The tin plating film can be formed by electroless plating, electroplating, or the like.
＜７＞変色防止剤
めっき繊維は、最外層の錫めっき膜の上に接して変色防止剤を塗布形成することが好ましい。変色防止剤としては、特に限定されないが、チオエーテル系、チオール系、Ｎｉ系有機化合物系、ベンゾトリアゾール系、イミダゾール系、オキサゾール系、テトラザインデン系、ピリミジン系、チアジアゾール系等を例示できる。
<7> Discoloration inhibitor The plated fiber is preferably formed by applying a discoloration inhibitor in contact with the tin plating film of the outermost layer. The discoloration inhibitor is not particularly limited, and examples thereof include thioether-based, thiol-based, Ni-based organic compound-based, benzotriazole-based, imidazole-based, oxazole-based, tetrazyneden-based, pyrimidine-based, thiadiazole-based, and the like.
＜８＞めっき繊維の用途
本発明のめっき繊維の用途は、特に限定されないが、電線が好適であり、さらに布（織布、編物、不織布等）に加工して電磁シールド布、静電気防止布、導電性布、遮光性布にも使用することができる。
<8> Use of plated fiber The use of the plated fiber of the present invention is not particularly limited, but an electric wire is suitable, and the cloth (woven cloth, knitted fabric, non-woven fabric, etc.) is further processed into an electromagnetic shield cloth, an antistatic cloth, and the like. It can also be used for conductive cloth and light-shielding cloth.
次に、本発明の実施例について図面を参照して説明する。なお、実施例の各部の構造、材料、形状及び寸法は例示であり、発明の趣旨から逸脱しない範囲で適宜変更できる。 Next, examples of the present invention will be described with reference to the drawings. The structure, material, shape and dimensions of each part of the embodiment are examples and can be appropriately changed without departing from the spirit of the invention.
次の表１（○印は各例が備える要素）に示す、実施例１～５及び比較例１のめっき繊維を作製した（但し、実施例５は参考例である。）。実施例１～５はニッケル系めっき膜の種類が互いに相違し、実施例５は錫めっき膜がない点で他の実施例と相違する。比較例は、ニッケル系めっき膜がない点で実施例と相違する。 The plated fibers of Examples 1 to 5 and Comparative Example 1 shown in Table 1 below (marked with ◯ are elements included in each example) were prepared (however, Example 5 is a reference example) . Examples 1 to 5 are different from each other in the types of nickel-based plating films, and Example 5 is different from other examples in that there is no tin plating film. The comparative example differs from the example in that there is no nickel-based plating film.
ここで、各要素の仕様及び形成方法について詳述する。
＜１＞非金属繊維
全例で、非金属繊維には、図２に示すように、繊度が例えば４４０ｄｔｅｘ－２６７ｆ（フィラメントが２６７本集まって１束（４４０ｄｔｅｘ）となる）であるパラ系アラミド繊維を使用した。図１はその１束のうちの一本のフィラメント（直径は１２μｍ）とその上に形成されためっき膜等の断面の１／４部分を示している。
Here, the specifications and forming method of each element will be described in detail.
<1> Non-metal fibers In all cases, the non-metal fibers include para-aramid fibers having a fineness of, for example, 440 dtex-267f (267 filaments are gathered to form one bundle (440 dtex)). It was used. FIG. 1 shows one filament (diameter: 12 μm) in one bundle and a quarter portion of a cross section of a plating film or the like formed on the filament.
＜２＞前処理
全例で、パラ系アラミド繊維を湿式前処理法で前処理した。湿式前処理法は、前述したアルカリエッチング→酸中和→表面調整→触媒付与→活性化の順に、前述した材料にて行った。図１及び表１に示すように、膜厚約５０ｎｍの触媒（パラジウム核）が非金属繊維の上に接して付着した。
<2> Pretreatment In all cases, para-aramid fibers were pretreated by a wet pretreatment method. The wet pretreatment method was carried out using the above-mentioned materials in the order of alkali etching → acid neutralization → surface preparation → catalyst application → activation described above. As shown in FIGS. 1 and 1, a catalyst (palladium nucleus) having a film thickness of about 50 nm was in contact with and adhered to the non-metal fiber.
＜３＞導電性付与膜
全例で、パラ系アラミド繊維に導通性（次の銅めっき膜の電気めっきで必要）を付与するために、触媒の上に接して膜厚０．３μｍの導通性付与膜を、無電解銅めっきにより形成した。使用しためっき液は、次の組成の水溶液である。ＥＤＴＡ－４Ｎａはエチレンジアミン四酢酸・四ナトリウムである。
硫酸銅 １５ｇ／Ｌ
ホルマリン ３ｇ／Ｌ
ＥＤＴＡ－４Ｎａ ３５ｇ／Ｌ
水酸化ナトリウム ５ｇ／Ｌ
安定剤 少量
潤滑剤 少量
<3> Conductivity-imparting film In all cases, in order to impart conductivity (necessary for electroplating of the next copper plating film) to para-aramid fibers, the film is in contact with the catalyst and has a film thickness of 0.3 μm. The imparting film was formed by electroless copper plating. The plating solution used is an aqueous solution having the following composition. EDTA-4Na is ethylenediaminetetraacetic acid / tetrasodium.
Copper sulphate 15g / L
Formalin 3g / L
EDTA-4Na 35g / L
Sodium hydroxide 5g / L
Stabilizer Small amount Lubricant Small amount
＜４＞銅めっき膜
全例で、めっき繊維の主たる導電膜として、導通性付与膜の上に接して膜厚３．０μｍの銅めっき膜を、電気めっきにより形成した。使用しためっき液は、次の組成の水溶液である。
硫酸銅 ２００ｇ／Ｌ
硫酸 ５０ｇ／Ｌ
<4> Copper plating film In all cases, as the main conductive film of the plating fiber, a copper plating film having a film thickness of 3.0 μm was formed by electroplating on the continuity-imparting film. The plating solution used is an aqueous solution having the following composition.
Copper sulfate 200g / L
Sulfuric acid 50g / L
＜５＞ニッケル系めっき膜
（ａ）ニッケルめっき膜（電気）
実施例１では、銅めっき膜の上に接して膜厚０．５μｍのニッケルめっき膜を、電気めっきにより形成した。使用しためっき液は、次の組成の水溶液である。
硫酸ニッケル ２４０ｇ／Ｌ
塩化ニッケル ４５ｇ／Ｌ
ホウ酸 ３０ｇ／Ｌ
<5> Nickel-based plating film (a) Nickel plating film (electricity)
In Example 1, a nickel plating film having a film thickness of 0.5 μm was formed by electroplating in contact with the copper plating film. The plating solution used is an aqueous solution having the following composition.
Nickel sulfate 240g / L
Nickel chloride 45g / L
Boric acid 30g / L
（ｂ）ニッケル－リン合金めっき膜（無電解）
実施例２では、銅めっき膜の上に接して膜厚０．３μｍのニッケル－リンめっき膜を、無電解めっきにより形成した。使用しためっき液は、奥野製薬工業株式会社の商品名「トップニコロンＰ－１３」である。
(B) Nickel-phosphorus alloy plating film (electroless)
In Example 2, a nickel-phosphorus plating film having a film thickness of 0.3 μm was formed by electroless plating in contact with the copper plating film. The plating solution used was the trade name "Top Nicolon P-13" of Okuno Pharmaceutical Industry Co., Ltd.
（ｃ）ニッケル－リン合金めっき膜（電気）
実施例３及び５では、銅めっき膜の上に接して膜厚０．４μｍのニッケル－リンめっき膜を、電気めっきにより形成した。使用しためっき液は、次の組成の水溶液である。
硫酸ニッケル ２５０ｇ／Ｌ
次亜リン酸ナトリウム ４０ｇ／Ｌ
クエン酸 １５ｇ／Ｌ
(C) Nickel-phosphorus alloy plating film (electricity)
In Examples 3 and 5, a nickel-phosphorus plating film having a film thickness of 0.4 μm was formed by electroplating on the copper plating film. The plating solution used is an aqueous solution having the following composition.
Nickel sulfate 250g / L
Sodium hypophosphite 40 g / L
Citric acid 15g / L
（ｄ）ニッケル－ボロン合金めっき膜（無電解）
実施例４では、銅めっき膜の上に接して膜厚０．３μｍのニッケル－ボロンめっき膜を、無電解めっきにより形成した。使用しためっき液は、奥野製薬工業株式会社の商品名「トップケミアロイ６６」である。
(D) Nickel-boron alloy plating film (electroless)
In Example 4, a nickel-boron plating film having a film thickness of 0.3 μm was formed by electroless plating in contact with the copper plating film. The plating solution used was the trade name "Top Chemi Alloy 66" of Okuno Pharmaceutical Industry Co., Ltd.
＜６＞錫めっき膜
実施例１～４ではニッケル系めっき膜の上に接して、また、比較例１では銅めっき膜の上に接して、膜厚０．５μｍの錫めっき膜を、電気めっきにより形成した。使用しためっき液は、次の組成の水溶液である。
硫酸第一錫 ３０ｇ／Ｌ
硫酸 １０５ｍｌｇ／Ｌ
光沢剤 適量
<6> Tin-plated film In Examples 1 to 4, the tin-plated film having a thickness of 0.5 μm was electroplated in contact with the nickel-based plating film and in Comparative Example 1 on the copper-plated film. Formed by. The plating solution used is an aqueous solution having the following composition.
Stannous sulfate 30 g / L
Sulfuric acid 105mlg / L
Appropriate amount of brightener
＜７＞変色防止剤
実施例１～４及び比較例１では錫めっき膜の上に接して、また、実施例５ではニッケル系めっき膜の上に接して、変色防止剤を塗布形成した。使用した変色防止剤は、奥野製薬工業社製「トップ防錆剤Ｙ」である。
<7> Anti-tarnish agent In Examples 1 to 4 and Comparative Example 1, the anti-tarnish agent was applied and formed in contact with the tin-plated film and in Example 5 on the nickel-based plating film. The discoloration inhibitor used was "Top Rust Inhibitor Y" manufactured by Okuno Pharmaceutical Industry Co., Ltd.
以上のように作製した実施例１～５及び比較例１のめっき繊維について、ＪＩＳ Ｚ２３７１に準拠して塩水噴霧試験を行った。各めっき繊維を、温度が３５℃に維持されている試験槽に入れ、濃度５％の塩水を噴霧し、試験１サイクル終了ごとに表面を観察し、抵抗値を測定した。 The plated fibers of Examples 1 to 5 and Comparative Example 1 prepared as described above were subjected to a salt spray test in accordance with JIS Z2371. Each plated fiber was placed in a test tank whose temperature was maintained at 35 ° C., salt water having a concentration of 5% was sprayed, the surface was observed after each test cycle, and the resistance value was measured.
その結果、比較例１のめっき繊維は、試験１サイクル後の観察で赤黒く変色していて、抵抗値は測定できないほど増加していた。
これに対して、実施例１～５のめっき繊維は、試験３サイクル後の観察で変色はほとんど無く、抵抗値は塩水噴霧テスト前の１～１．５Ω／ｍから増加がみられなかった。これは、銅めっき膜の上にニッケル系めっき膜を形成したことで、銅の拡散が抑えられたことによるものと考えられる。
As a result, the plated fiber of Comparative Example 1 was discolored red and black in the observation after one cycle of the test, and the resistance value increased beyond measurement.
On the other hand, the plated fibers of Examples 1 to 5 showed almost no discoloration in the observation after 3 cycles of the test, and the resistance value did not increase from 1 to 1.5 Ω / m before the salt spray test. It is considered that this is because the diffusion of copper was suppressed by forming the nickel-based plating film on the copper plating film.
実施例１～５のめっき繊維は、図２に示す１束で抵抗値が０．２～２０Ω／ｍの範囲内にあるので、電線として特に好適に使用することができる。 Since the plated fibers of Examples 1 to 5 have a resistance value in the range of 0.2 to 20 Ω / m in one bundle shown in FIG. 2, they can be particularly preferably used as an electric wire.
なお、本発明は前記実施例に限定されるものではなく、発明の趣旨から逸脱しない範囲で適宜変更して具体化することができる。 The present invention is not limited to the above embodiment, and can be appropriately modified and embodied without departing from the spirit of the invention.
Claims (6)
前記錫めっき膜は、めっき繊維のめっき層として最外層であり、
前記ニッケル系めっき膜は、前記銅めっき膜の銅が前記錫めっき膜へ拡散するのを抑止するためのものであって、膜厚が０．１μｍ以上であり、
めっき繊維は、ＪＩＳ Ｚ２３７１に準拠した塩水噴霧試験３サイクル後の観察で変色が無く、該塩水噴霧試験前に対して抵抗値増加が無いことを特徴とするめっき繊維。 It includes a non-metal fiber, a copper plating film formed on the non-metal fiber, a nickel-based plating film formed on the copper plating film, and a tin plating film formed on the nickel-based plating film. It is a plated fiber
The tin-plated film is the outermost layer as a plating layer for plating fibers.
The nickel-based plating film is for suppressing the copper of the copper plating film from diffusing into the tin plating film, and has a film thickness of 0.1 μm or more.
The plated fiber is a plated fiber according to JIS Z2371, which is characterized by no discoloration in observation after 3 cycles of the salt spray test and no increase in resistance value as compared with that before the salt spray test .
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| JP2005310827A (en) | 2004-04-16 | 2005-11-04 | Seiren Co Ltd | Protective material for aperture of electronic apparatus housing |
| JP2012087434A (en) | 2010-10-20 | 2012-05-10 | Toyota Boshoku Corp | Heat generating yarn and woven or knitted fabric using the same |
| JP2012216526A (en) | 2011-03-30 | 2012-11-08 | Furukawa Electric Co Ltd:The | Metal-coated carbon fiber wire |
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