JPWO2018180837A1 - Manufacturing method of water supply device and water supply device - Google Patents

Manufacturing method of water supply device and water supply device Download PDF

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JPWO2018180837A1
JPWO2018180837A1 JP2019509634A JP2019509634A JPWO2018180837A1 JP WO2018180837 A1 JPWO2018180837 A1 JP WO2018180837A1 JP 2019509634 A JP2019509634 A JP 2019509634A JP 2019509634 A JP2019509634 A JP 2019509634A JP WO2018180837 A1 JPWO2018180837 A1 JP WO2018180837A1
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JP6758794B2 (en
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継志 伊藤
武 西川
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Lixil Corp
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/14—Etching locally
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
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Abstract

クロムめっきに覆われていないニッケルめっきを簡易に除去できる水道用器具の製造方法、及び水道用器具を提供する。本発明では、基体の表面にニッケルめっき又はニッケル合金めっきと、さらにその上にクロムめっきとを施した、銅合金からなる基体を、電解液に浸漬した状態で所定の電位を印加し、水道用器具内部の内通水路のクロムめっきに覆われていないニッケルめっき又はニッケル合金めっきを除去する。電解液は、ワット浴であることが好ましい。また、所定の電位が−０．３Ｖ〜−０．０５Ｖ（ｖｓ ＳＣＥ）であることが好ましい。Provided is a method for manufacturing a water supply device that can easily remove nickel plating that is not covered with chromium plating, and a water supply device. In the present invention, a predetermined potential is applied in a state in which a base made of a copper alloy, which is nickel-plated or nickel-alloy plated on the surface of the base and further chrome-plated thereon, is immersed in an electrolytic solution, Remove any nickel plating or nickel alloy plating that is not covered with chromium plating in the internal water passages inside the appliance. The electrolyte is preferably a watt bath. The predetermined potential is preferably −0.3 V to −0.05 V (vs SCE).

Description

本開示は、水道用器具の製造方法、及び水道用器具に関する。   The present disclosure relates to a method for manufacturing a water supply device and a water supply device.

近年、水道水中のニッケルの規制強化（水質基準化）の可能性が高まっており、水道用器具からのニッケル浸出を抑制する技術が開発されている。例えば、下記特許文献１には、水栓金具等の水道用器具からのニッケル浸出の一つの原因と、それを解決する提案が示されている。すなわち、水道用器具のめっきは器具の外面に施されるが、一部内部にもめっきが回り込んで析出してしまう。通常、ニッケルめっき（ｎｉｃｋｅｌ ｐｌａｔｉｎｇ）を施した後、その上にクロムめっき（ｃｈｒｏｍｉｕｍ ｐｌａｔｉｎｇ）が施されるが、ニッケルめっきの方がクロムめっきより多く通水路等の内面についてまわる傾向が見られる。その結果、ニッケルめっき表面が内部を流れる給水と接触し、ニッケルが浸出してしまう原因となる。このニッケル浸出を防ぐために、クロムめっきに覆われていないニッケルめっきを除去する処理工程が必要となっている。
具体的には、まず、ニッケルめっき、及びクロムめっきが施された水道用器具の基体を用意する。そして、この基体を、無水クロム酸と、硫酸と、場合により過酸化水素とを少なくとも含んでなる第１の処理液に浸漬して、水道用器具内部の内通水路のクロムめっきに覆われていないニッケルめっきを除去する。次いで、基材を、無水クロム酸と、リン酸、硝酸、又はその混合物とを含んでなる第２の処理液に浸漬して、基材表面を安定化する。In recent years, the possibility of strengthening regulations (standardization of water quality) of nickel in tap water has increased, and a technique for suppressing nickel leaching from water supply equipment has been developed. For example, the following Patent Document 1 shows one cause of nickel leaching from a water supply device such as a faucet fitting and a proposal for solving it. That is, the plating of the water supply device is applied to the outer surface of the device, but the plating also circulates and deposits partially inside. Usually, after nickel plating is applied, chromium plating is applied thereon. However, nickel plating is more likely to circulate on the inner surface of a water passage or the like than chromium plating. As a result, the nickel-plated surface comes into contact with the water supply flowing inside, causing nickel to leach out. In order to prevent this nickel leaching, a treatment process for removing nickel plating not covered with chromium plating is required.
Specifically, first, a base for a water supply device having nickel plating and chromium plating is prepared. Then, this substrate is immersed in a first treatment liquid containing at least chromic anhydride, sulfuric acid, and, in some cases, hydrogen peroxide, and is covered with chrome plating in an internal water passage inside the water supply device. Remove no nickel plating. Next, the substrate is immersed in a second treatment solution containing chromic anhydride and phosphoric acid, nitric acid, or a mixture thereof to stabilize the substrate surface.

特開２０１６−１９１０９６号公報Japanese Patent Laid-Open No. 2006-191096

この技術では、クロムめっき及び基材の銅合金を全く溶解せずに、ニッケルめっきだけを選択的に溶解することは非常に難しく、表面のクロムめっきの外観が腐食により変化したり、金具内部の銅合金が腐食するなどの問題点があった。
本発明は、上記実情に鑑みてなされたものであり、クロムめっきに覆われていないニッケルめっきを簡易に除去できる水道用器具の製造方法、及び外観が良好な水道用器具を提供することを目的とする。With this technology, it is very difficult to selectively dissolve only the nickel plating without dissolving the chromium plating and the copper alloy of the base material at all, and the appearance of the surface chromium plating changes due to corrosion, There were problems such as corrosion of copper alloys.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for manufacturing a water supply device that can easily remove nickel plating that is not covered with chrome plating, and a water supply device that has a good appearance. And

本発明者らは、鋭意研究を重ねた結果、新規な水道用器具の製造方法を開発した。
そして、この方法によれば、クロムめっきに覆われていないニッケルめっきを簡易に除去できるということを見いだした。さらに、この方法によれば、外観が良好な新規な水道用器具が提供されることを見いだした。この成果に基づいて、次の発明を提供する。As a result of intensive studies, the present inventors have developed a novel method for manufacturing a water supply device.
And according to this method, it discovered that nickel plating which is not covered with chromium plating can be removed easily. Furthermore, according to this method, it discovered that the novel water supply apparatus with a favorable external appearance was provided. Based on this result, the following invention is provided.

〔１〕水道用器具の製造方法であって、
その表面にニッケルめっき又はニッケル合金めっき（ｎｉｃｋｅｌ ａｌｌｏｙ ｐｌａｔｉｎｇ）と、さらにその上にクロムめっきとを施した、銅合金からなる基体を、電解液に浸漬した状態で所定の電位を印加し、前記クロムめっきに覆われていない前記ニッケルめっき又は前記ニッケル合金めっきを除去して水道用器具にすることを特徴とする水道用器具の製造方法。[1] A method of manufacturing a water supply device,
A predetermined potential is applied in a state in which a base made of a copper alloy having nickel plating or nickel alloy plating on its surface and further chromium plating on the surface is immersed in an electrolytic solution. A method for producing a water supply device, wherein the nickel plating or the nickel alloy plating not covered with plating is removed to form a water supply device.

〔２〕前記電解液がニッケル塩を含有することを特徴とする〔１〕に記載の水道用器具の製造方法。   [2] The method for manufacturing a water supply device according to [1], wherein the electrolytic solution contains a nickel salt.

〔３〕前記電解液は、前記ニッケルめっき又は前記ニッケル合金めっきを形成する際に用いためっき浴と同一の塩を含有することを特徴とする〔１〕又は〔２〕に記載の水道用器具の製造方法。   [3] The water supply apparatus according to [1] or [2], wherein the electrolytic solution contains the same salt as the plating bath used when the nickel plating or the nickel alloy plating is formed. Manufacturing method.

〔４〕前記電解液は、ワット浴（ｗａｔｔ ｂａｔｈ）であることを特徴とする〔１〕〜〔３〕のいずれか１項に記載の水道用器具の製造方法。   [4] The method for manufacturing a water supply device according to any one of [1] to [3], wherein the electrolytic solution is a Watt bath.

〔５〕前記所定の電位が−０．３Ｖ〜−０．０５Ｖ（ｖｓ ＳＣＥ）であることを特徴とする〔４〕に記載の水道用器具の製造方法。   [5] The method for manufacturing a water supply device according to [4], wherein the predetermined potential is −0.3 V to −0.05 V (vs SCE).

〔６〕銅合金からなる基体の内部に内通水路が備えられた水道用器具であって、
外面には、ニッケルめっき又はニッケル合金めっきが施され、さらにその上にクロムめっきが施され、
前記内通水路は、全面に亘って銅合金が露出しており、
前記クロムめっきは、クロムめっき本来の金属光沢を有することを特徴とする水道用器具。
なお、ここでいう「クロムめっき本来の金属光沢」とは、クロムの有する銀白色を意味する。クロムめっき本来の金属光沢を有するか否かは、目視や、各種光学的な測定機器により判断できる。[6] A water supply device provided with an internal water passage inside a base made of a copper alloy,
On the outer surface, nickel plating or nickel alloy plating is applied, and further chromium plating is applied thereon,
The inner water passage has a copper alloy exposed over the entire surface,
The chrome plating has a metallic luster inherent to chrome plating, and is a water supply device.
In addition, "the original metallic luster of chromium plating" here means the silver white that chromium has. Whether or not it has the original metallic luster of chrome plating can be determined by visual observation or various optical measuring instruments.

本発明の水道用器具の製造方法によれば、クロムめっきに覆われていないニッケルめっきを簡易に除去できる。
電解液がニッケル塩を含有する場合には、効率的にニッケルめっきを除去できる。
電解液は、ニッケルめっき又はニッケル合金めっきを形成する際に用いためっき浴と同一の塩を含有することが好ましい。この場合には、ニッケルめっきの除去のために、特別な塩を用意する必要がなくなるのでコスト的に有利である。
電解液に、ワット浴を用いることが好ましい。ワット浴は、一般的なニッケルめっき浴であるため、コスト的に有利である。
電解液に、ワット浴を用いた場合に、所定の電位が−０．３Ｖ〜−０．０５Ｖ（ｖｓ ＳＣＥ）であることが好ましい。この範囲内であると、銅合金からなる基体及びクロムめっきを溶解させることなく、選択的に、不要なニッケルめっきのみを除去できる。
本発明の水道用器具は、内通水路の全面に亘って銅合金が露出しているから、ニッケル浸出のおそれはない。さらに、水道用器具は、外面のクロムめっきがクロムめっき本来の金属光沢を有するから、外観が良好である。According to the method for manufacturing a water supply device of the present invention, nickel plating not covered with chromium plating can be easily removed.
When the electrolytic solution contains a nickel salt, nickel plating can be efficiently removed.
The electrolytic solution preferably contains the same salt as the plating bath used when forming nickel plating or nickel alloy plating. In this case, it is not necessary to prepare a special salt for removing nickel plating, which is advantageous in terms of cost.
It is preferable to use a Watt bath as the electrolyte. Since the Watt bath is a general nickel plating bath, it is advantageous in terms of cost.
When a watt bath is used as the electrolytic solution, the predetermined potential is preferably −0.3 V to −0.05 V (vs SCE). Within this range, only unnecessary nickel plating can be selectively removed without dissolving the base made of copper alloy and chromium plating.
In the water supply device of the present invention, since the copper alloy is exposed over the entire surface of the internal water passage, there is no fear of nickel leaching. Furthermore, since the outer surface chrome plating has the original metallic luster of the chrome plating, the appearance of the water supply device is good.

本発明について、本発明による典型的な実施形態の非限定的な例を挙げ、言及された複数の図面を参照しつつ以下の詳細な記述にて更に説明する。
水道用器具の断面図である。 試験装置を示す説明図である。 分極曲線を示すグラフである。 試験に用いた水栓金具の外観写真である。 試験に用いた水栓金具の内部状況を示す写真である。 試験後の水栓金具の外観写真である。 試験後の水栓金具の内部状況を示す写真である。 試験前の水栓金具の端面からの距離と、元素の検出比率の関係を示すグラフである。 試験後の水栓金具の端面からの距離と、元素の検出比率の関係を示すグラフである。 The invention will be further described in the following detailed description, given by way of non-limiting example of exemplary embodiments according to the invention, with reference to the mentioned drawings.
It is sectional drawing of the appliance for water supply. It is explanatory drawing which shows a test apparatus. It is a graph which shows a polarization curve. It is an external appearance photograph of the faucet metal fitting used for the test. It is a photograph which shows the internal condition of the faucet metal fitting used for the test. It is an external appearance photograph of the faucet metal fitting after a test. It is a photograph which shows the internal condition of the faucet metal fitting after a test. It is a graph which shows the relationship between the distance from the end surface of the faucet metal fitting before a test, and the detection ratio of an element. It is a graph which shows the relationship between the distance from the end surface of the faucet metal fitting after a test, and the detection ratio of an element.

以下、本発明を詳しく説明する。
Ａ．水道用器具の製造方法
本発明の製造方法では、基体の表面にニッケルめっき又はニッケル合金めっきと、さらにその上にクロムめっきとを施した、銅合金からなる基体を、電解液に浸漬した状態で所定の電位を印加し、クロムめっきに覆われていないニッケルめっき又はニッケル合金めっきを除去する。The present invention will be described in detail below.
A. In the manufacturing method of the present invention, a base made of a copper alloy, which is nickel-plated or nickel-alloy plated on the surface of the base and further chrome-plated thereon, is immersed in an electrolytic solution. A predetermined potential is applied to remove nickel plating or nickel alloy plating not covered with chromium plating.

１．水道用器具
水道用器具とは、水道水を供給するために用いる器具を意味する。例えば、飲料用の水を供給するための蛇口、バルブ等の水栓金具、継手、給水管等が挙げられる。なお、水道用器具は、使用される位置及び機能により、例えば末端給水用具、給水管、配管の途中に設置される給水用具等に分類される。水道用器具は、一般的には、水を通す内通水路と、水と接しない外面を備えている。本発明は、特に、水栓金具に好ましく用いられる。1. Water supply equipment The water supply equipment means the equipment used to supply tap water. For example, faucets for supplying drinking water, faucet fittings such as valves, joints, water supply pipes and the like can be mentioned. In addition, the water supply apparatus is classified into, for example, a terminal water supply tool, a water supply pipe, a water supply tool installed in the middle of the piping, and the like depending on the position and function used. In general, a water supply device includes an inner water passage that allows water to pass therethrough and an outer surface that does not contact water. The present invention is particularly preferably used for a faucet fitting.

２．基体
本発明における基体は、銅合金であれば特に限定されず、種々の銅合金を幅広く用いることができる。銅合金としては、例えば、黄銅、青銅を好ましく用いることができる。基体の製造方法は特に限定されない。基体は、一般的には、銅合金を鋳造又は鍛造し、切削加工、研磨加工等で形状を整えて製造される。
基体には、ニッケル又はニッケル合金のめっきが施され、さらにその上にクロムめっきが施されている。2. Substrate The substrate in the present invention is not particularly limited as long as it is a copper alloy, and various copper alloys can be widely used. For example, brass or bronze can be preferably used as the copper alloy. The method for manufacturing the substrate is not particularly limited. The base is generally manufactured by casting or forging a copper alloy and adjusting the shape by cutting, polishing, or the like.
The substrate is plated with nickel or a nickel alloy, and further chrome plated.

図１に水道用器具の断面図を示す。水道用器具Ａは、外面にニッケルめっき又はニッケル合金めっき３と、さらにその上にクロムめっき５とが少なくとも施されている。水道用器具を製造する際に、外面に施されるめっきの一部が、その内部の内通水路にも回り込んで析出してしまう。この様子が図１に示されている。基材１の外面には、ニッケル又はニッケル合金めっき３と、その上にクロムめっき５が施され２層のめっきがなされている。内通水路の端部では、めっきの一部が回り込んで析出する。その際、ニッケル又はニッケル合金めっき３の方が、クロムめっき５よりもより内部に回り込む傾向がある。よって、図１に示されるように、符号７で示す部分では、クロムめっき５がなく、ニッケルめっき又はニッケル合金めっき３が露出した状態となる。よって、この部分のニッケルめっき又はニッケル合金めっき３が水と接触し、ニッケルが水に浸出するものと推測される。
本発明では、クロムめっき５に覆われずに、露出した状態のニッケルめっき又はニッケル合金めっき３を除去する。すなわち、クロムめっき５に覆われていないニッケルめっき又はニッケル合金めっき３を除去する。FIG. 1 shows a cross-sectional view of a water supply device. The water supply device A has at least nickel plating or nickel alloy plating 3 on the outer surface and further chromium plating 5 thereon. When manufacturing a water supply device, a part of the plating applied to the outer surface goes around the inner water passage and precipitates. This is shown in FIG. On the outer surface of the base material 1, nickel or nickel alloy plating 3 and chromium plating 5 thereon are applied to form two layers of plating. A part of the plating wraps around and precipitates at the end of the inner water passage. At that time, the nickel or nickel alloy plating 3 tends to go inside more than the chromium plating 5. Therefore, as shown in FIG. 1, in the portion indicated by reference numeral 7, there is no chromium plating 5 and nickel plating or nickel alloy plating 3 is exposed. Therefore, it is presumed that the nickel plating or nickel alloy plating 3 in this portion comes into contact with water, and nickel is leached into water.
In the present invention, the exposed nickel plating or nickel alloy plating 3 is removed without being covered with the chromium plating 5. That is, the nickel plating or nickel alloy plating 3 that is not covered with the chromium plating 5 is removed.

３．ニッケルめっき、ニッケル合金めっき
ニッケルめっき、ニッケル合金めっきには、公知のめっきを採用することできる。ニッケル合金めっきの組成は特に限定されない。ニッケル合金めっきは、例えば、コバルト、スズ、鉄及びリンからなる群から選択される少なくとも一つと、ニッケルとの合金からなるめっきである。より好ましい態様によれば、ニッケル合金めっきはニッケルコバルト合金めっきとすることができる。
例えば、ニッケル合金めっきがニッケルコバルト合金めっき（ｎｉｃｋｅｌ−ｃｏｂａｌｔ ａｌｌｏｙ ｐｌａｔｉｎｇ）である場合、ニッケル：コバルト比が、重量で３５：６５〜９５：５の範囲にあることが好ましい。
また、ニッケル合金めっきがニッケルスズめっき（ｎｉｃｋｅｌ ｔｉｎ ｐｌａｔｉｎｇ）である場合、ニッケル：スズ比が重量で６５：３５〜３５：６５の範囲にあることが好ましい。ニッケル合金めっきがニッケル鉄めっき（ｎｉｃｋｅｌ−ｉｒｏｎ ｐｌａｔｉｎｇ）である場合、ニッケル：鉄比が重量で７０：３０〜９７：３の範囲にあることが好ましく、またニッケル合金めっきがニッケルリンめっき（ｎｉｃｋｅｌ−ｐｈｏｓｐｈｏｒｕｓ ｐｌａｔｉｎｇ）である場合、ニッケル：リン比が重量で８０：２０〜９７：３の範囲にあることが好ましい。3. Nickel plating and nickel alloy plating Known plating can be employed for nickel plating and nickel alloy plating. The composition of the nickel alloy plating is not particularly limited. The nickel alloy plating is, for example, plating made of an alloy of nickel and at least one selected from the group consisting of cobalt, tin, iron, and phosphorus. According to a more preferred embodiment, the nickel alloy plating can be nickel cobalt alloy plating.
For example, when the nickel alloy plating is nickel-cobalt alloy plating, the nickel: cobalt ratio is preferably in the range of 35:65 to 95: 5 by weight.
When the nickel alloy plating is nickel tin plating, the nickel: tin ratio is preferably in the range of 65:35 to 35:65 by weight. When the nickel alloy plating is nickel-iron plating, the nickel: iron ratio is preferably in the range of 70:30 to 97: 3 by weight, and the nickel alloy plating is nickel phosphorus plating (nickel- (phosphorus plating), the nickel: phosphorus ratio is preferably in the range of 80:20 to 97: 3 by weight.

基体へ、ニッケルめっき又はニッケル合金めっきを施す方法は、特に限定されず、公知の方法を採用することができる。
ニッケルめっき又はニッケル合金めっきは電気めっきにより施されることがコストの観点から好ましい。めっき浴としては、ニッケルめっき又はニッケル合金めっきのめっき浴として公知のものを用いることができる。The method for applying nickel plating or nickel alloy plating to the substrate is not particularly limited, and a known method can be employed.
The nickel plating or nickel alloy plating is preferably performed by electroplating from the viewpoint of cost. As the plating bath, a known plating bath for nickel plating or nickel alloy plating can be used.

ニッケルめっき又はニッケル合金めっきのめっき浴は、特に限定されないが、例えば、ワット浴、スルファミン酸浴（ｓｕｌｆａｍｉｃ ａｃｉｄ ｂａｔｈ）が挙げられる。
ワット浴として、例えば、硫酸ニッケル・６水和物を１００ｇ／Ｌ〜４００ｇ／Ｌ、塩化ニッケル・６水和物を０ｇ／Ｌ〜６０ｇ／Ｌ、ホウ酸を１５〜６０ｇ／Ｌ含有する浴を挙げることができる。例えば、硫酸ニッケル・６水和物の濃度は、濃い方が電流が流れやすくニッケルを溶解し易い。塩化ニッケル・６水和物の濃度は、薄い方がクロムめっきにダメージを与え難い。また、ホウ酸の濃度は、濃い方が水素イオンが多く、電流が流れ易い。
スルファミン酸浴として、例えば、スルファミン酸ニッケル・４水和物を１００ｇ／Ｌ〜６００ｇ／Ｌ、塩化ニッケル・６水和物を１ｇ／Ｌ〜６ｇ／Ｌ、ホウ酸を１５〜６０ｇ／Ｌ含有する浴を挙げることができる。The plating bath for nickel plating or nickel alloy plating is not particularly limited, and examples thereof include a watt bath and a sulfamic acid bath.
As a watt bath, for example, a bath containing 100 g / L to 400 g / L of nickel sulfate hexahydrate, 0 g / L to 60 g / L of nickel chloride hexahydrate, and 15 to 60 g / L of boric acid. Can be mentioned. For example, when the concentration of nickel sulfate hexahydrate is higher, current flows more easily and nickel is more easily dissolved. The thinner the concentration of nickel chloride hexahydrate, the less the chromium plating is damaged. Further, the concentration of boric acid is higher when there are more hydrogen ions, and the current flows more easily.
The sulfamic acid bath contains, for example, 100 g / L to 600 g / L of nickel sulfamate tetrahydrate, 1 g / L to 6 g / L of nickel chloride hexahydrate, and 15 to 60 g / L of boric acid. A bath can be mentioned.

４．クロムめっき
本発明による水道用器具は、ニッケルめっき又はニッケル合金めっきの上に、さらにクロムめっきが施されている。クロムめっきは、めっき業界において公知のクロムめっきであれば特に限定されない。4). Chromium plating The water supply apparatus according to the present invention is further plated with chromium on nickel plating or nickel alloy plating. The chromium plating is not particularly limited as long as it is a known chromium plating in the plating industry.

５．電解液
電解液としは、特に限定されないが、ニッケル塩を含有することが好ましい。ニッケル塩は、特に限定されない。ニッケル塩としては、例えば、硫酸ニッケル、塩化ニッケル、スルファミン酸ニッケル、酢酸ニッケル等が挙げられる。これらは単独で又は２種以上を組み合わせて用いることができる。
電解液は、ニッケルめっき又はニッケル合金めっきを形成する際に用いたニッケルめっき浴と同一の塩を含有することが好ましい。特に、電解液は、ニッケルめっき又はニッケル合金めっきを形成する際に用いためっき浴と同一組成であることが好ましい。ニッケルめっきの除去のために、特別な電解液を用意する必要がなくなるのでコスト的に有利だからである。例えば、ニッケルめっき又はニッケル合金めっきのめっき浴として、ワット浴を用いた場合には、電解液もワット浴と同一組成であることが好ましい。また、例えば、ニッケルめっき又はニッケル合金めっきのめっき浴として、スルファミン酸浴を用いた場合には、電解液もスルファミン酸浴と同一組成であることが好ましい。5). Electrolytic Solution The electrolytic solution is not particularly limited, but preferably contains a nickel salt. The nickel salt is not particularly limited. Examples of the nickel salt include nickel sulfate, nickel chloride, nickel sulfamate, and nickel acetate. These can be used alone or in combination of two or more.
The electrolytic solution preferably contains the same salt as the nickel plating bath used when forming nickel plating or nickel alloy plating. In particular, the electrolytic solution preferably has the same composition as the plating bath used when forming nickel plating or nickel alloy plating. This is because there is no need to prepare a special electrolyte for removing nickel plating, which is advantageous in terms of cost. For example, when a watt bath is used as a plating bath for nickel plating or nickel alloy plating, the electrolytic solution preferably has the same composition as the watt bath. For example, when a sulfamic acid bath is used as a plating bath for nickel plating or nickel alloy plating, the electrolyte solution preferably has the same composition as the sulfamic acid bath.

電解液の具体的な組成としては、例えば、硫酸ニッケル・６水和物を好ましくは１００ｇ／Ｌ〜４００ｇ／Ｌ、より好ましくは２５０ｇ／Ｌ〜３５０ｇ／Ｌ、特に好ましくは３００ｇ／Ｌ〜３５０ｇ／Ｌ含有し、塩化ニッケル・６水和物を好ましくは０ｇ／Ｌ〜６０ｇ／Ｌ、より好ましくは０ｇ／Ｌ〜１５ｇ／Ｌ、特に好ましくは含有しない電解液を挙げることができる。また、電解液は、必要に応じて、Ｈイオンを供給するためのホウ酸（Ｈ３ＢＯ３）等の酸、錯化剤、界面活性剤等の有機添加物を含むことができる。酸を含む場合には、酸を好ましくは１５ｇ／Ｌ〜６０ｇ／Ｌ、より好ましくは３０ｇ／Ｌ〜５０ｇ／Ｌ、特に好ましくは４５ｇ／Ｌ〜５０ｇ／Ｌ含有する。この組成の範囲内であれば、クロムめっきに覆われていないニッケルめっき又はニッケル合金めっきを適切に除去できる。As a specific composition of the electrolytic solution, for example, nickel sulfate hexahydrate is preferably 100 g / L to 400 g / L, more preferably 250 g / L to 350 g / L, and particularly preferably 300 g / L to 350 g / L. An electrolytic solution containing L and preferably containing 0 to 60 g / L, more preferably 0 to 15 g / L, particularly preferably nickel chloride hexahydrate. Further, the electrolyte may contain optionally, acids such as boric acid for supplying H ions (H 3 BO 3), a complexing agent, an organic additive such as a surfactant. When an acid is included, the acid is preferably contained in an amount of 15 g / L to 60 g / L, more preferably 30 g / L to 50 g / L, and particularly preferably 45 g / L to 50 g / L. If it is in the range of this composition, nickel plating or nickel alloy plating which is not covered with chromium plating can be removed appropriately.

６．電位
本発明では、電解液に浸漬した状態で印加する所定の電位は、特に限定されないが、好ましくは、ニッケルめっき又はニッケル合金めっきを選択的に溶解する電位である。すなわち、ニッケルめっき又はニッケル合金めっきは溶解するが、銅合金からなる基体を溶解せず、クロムめっきも溶解しない電位が好ましい。ニッケルめっき又はニッケル合金めっきを選択的に溶解する電位とすれば、クロムめっきに覆われていないニッケルめっき又はニッケル合金めっきのみを除去できるからである。
所定の電位は、好ましくは、−０．３Ｖ〜−０．０５Ｖ（ｖｓ ＳＣＥ）であり、特に好ましくは、−０．１０Ｖ〜−０．０６Ｖ（ｖｓ ＳＣＥ）である。
なお、基体に印加する電位を調整するために、ポテンショスタットを用い、参照電極として飽和カロメル電極（ＳＣＥ）を採用することができる。6). Potential In the present invention, the predetermined potential applied in a state immersed in the electrolytic solution is not particularly limited, but is preferably a potential that selectively dissolves nickel plating or nickel alloy plating. That is, a potential at which nickel plating or nickel alloy plating dissolves but does not dissolve a copper alloy substrate and does not dissolve chromium plating is preferable. This is because if nickel plating or nickel alloy plating is set to a potential that selectively dissolves, only nickel plating or nickel alloy plating not covered with chromium plating can be removed.
The predetermined potential is preferably −0.3 V to −0.05 V (vs SCE), and particularly preferably −0.10 V to −0.06 V (vs SCE).
In order to adjust the potential applied to the substrate, a potentiostat can be used, and a saturated calomel electrode (SCE) can be employed as a reference electrode.

７．電解温度、及び電解時間
電解温度は特に限定されない。電解温度（電解液の温度）は、好ましくは、４０℃〜９０℃であり、より好ましくは、５０℃〜６０℃であり、特に好ましくは、５４℃〜５６℃である。この温度の範囲内であれば、クロムめっきに覆われていないニッケルめっき又はニッケル合金めっきを適切に除去できる。例えば、温度が高い方が反応速度が大きくニッケルめっきを溶解し易い。また、温度が高過ぎると、ニッケルめっき液が蒸発し易くニッケルの濃度が制御し難くなる。
電解時間は、特に限定されないが、クロムめっきに覆われていないニッケルめっき又はニッケル合金めっきの厚みに応じて適宜調整される。電解時間は、好ましくは、１０秒〜１００００秒であり、より好ましくは、７８０秒〜２４００秒であり、特に好ましくは、１８００秒〜１９２０秒である。この電解時間の範囲内であれば、クロムめっきに覆われていないニッケルめっき又はニッケル合金めっきを適切に除去できる。7). Electrolysis temperature and electrolysis time The electrolysis temperature is not particularly limited. The electrolysis temperature (temperature of the electrolytic solution) is preferably 40 ° C to 90 ° C, more preferably 50 ° C to 60 ° C, and particularly preferably 54 ° C to 56 ° C. Within this temperature range, nickel plating or nickel alloy plating not covered with chromium plating can be appropriately removed. For example, the higher the temperature, the higher the reaction rate and the easier the nickel plating is dissolved. On the other hand, if the temperature is too high, the nickel plating solution is likely to evaporate and the nickel concentration is difficult to control.
The electrolysis time is not particularly limited, but is appropriately adjusted according to the thickness of nickel plating or nickel alloy plating not covered with chromium plating. The electrolysis time is preferably 10 seconds to 10,000 seconds, more preferably 780 seconds to 2400 seconds, and particularly preferably 1800 seconds to 1920 seconds. If it is within the range of this electrolysis time, the nickel plating or nickel alloy plating which is not covered with chromium plating can be removed appropriately.

８．本実施形態の水道用器具の製造方法の効果
本実施形態の水道用器具の製造方法によれば、クロムめっきに覆われていないニッケルめっきを簡易に除去できる。8). Advantageous Effects of Manufacturing Method for Water Supply Apparatus According to this Embodiment According to the manufacturing method for a water supply apparatus according to this embodiment, nickel plating that is not covered with chromium plating can be easily removed.

Ｂ．水道用器具
１．本発明の水道用器具は、銅合金からなる基体の内部に内通水路が備えられた水道用器具である。その外面には、ニッケルめっき又はニッケル合金めっきが施され、さらにその上にクロムめっきが施されている。内通水路は、全面に亘って銅合金が露出している。上述のクロムめっきは、クロムめっき本来の金属光沢を有する。
「基体」「ニッケルめっき」「ニッケル合金めっき」「クロムめっき」については、「Ａ．水道用器具の製造方法」の欄での記載をそのまま適用できる。B. Water supply equipment 1. The water supply apparatus of the present invention is a water supply apparatus in which an internal water passage is provided inside a base made of a copper alloy. On the outer surface, nickel plating or nickel alloy plating is applied, and further chromium plating is applied thereon. In the inner water passage, the copper alloy is exposed over the entire surface. The chrome plating described above has the original metallic luster of chrome plating.
With respect to “substrate”, “nickel plating”, “nickel alloy plating”, and “chrome plating”, the description in the column “A.

２．本実施形態の水道用器具の効果
従来の、内通水路にニッケルめっきが存在しない水道用器具は、次のようにして製造されていた。すなわち、内通水路に付着したニッケルめっきの除去に際し、例えば〔１〕無水クロム酸、硫酸等を含む第１の処理液、及び〔２〕無水クロム酸、リン酸、硝酸等を含む第２の処理液を用いていた。そのため、従来の水道用器具では、これらの処理液によって外面のクロムめっきの外観劣化が生じていた。
これに対して、本実施形態の水道用器具では、外面のクロムめっきは、クロムめっき本来の金属光沢を有するから、外観が良好である。
また、本実施形態の水道用器具では、内通水路は、全面に亘って銅合金が露出しているから、ニッケル浸出のおそれはない。2. Effect of water supply device of this embodiment A conventional water supply device in which nickel plating does not exist in the internal water passage has been manufactured as follows. That is, when removing the nickel plating adhering to the internal water passage, for example, [1] a first treatment liquid containing chromic anhydride, sulfuric acid and the like; and [2] a second treatment containing chromic anhydride, phosphoric acid, nitric acid and the like. A processing solution was used. Therefore, in the conventional water supply apparatus, the appearance deterioration of the outer surface chromium plating has occurred due to these treatment liquids.
On the other hand, in the water supply apparatus of the present embodiment, the outer chrome plating has a good metallic appearance because it has the original metallic luster of chrome plating.
Moreover, in the water supply apparatus of this embodiment, since the copper alloy is exposed over the entire surface of the internal water passage, there is no fear of nickel leaching.

以下、実施例により更に具体的に説明する。   Hereinafter, the present invention will be described more specifically with reference to examples.

１．電解液中での分極曲線の測定
（１）試験装置
図２の装置を用いて、光沢ニッケルめっき、基材（青銅）、クロムめっきについて、分極曲線を測定した。図２において、符号１１は対極（Ｐｔ）を示し、符号１３は試料電極（青銅、ニッケルめっき膜、クロムめっき膜）を示し、符号１５は塩橋を示し、符号１７は参照電極（ＳＣＥ電極）を示す。また、符号１９はウォーターバスを示す。なお、図中に示したポテンショスタット（ｐｏｔｅｎｔｉｏｓｔａｔ）は、試料電極と参照電極の間の電位を正確に設定し、そのとき試料電極と対極の間に流れる電流を正確に測定することができる装置である。
使用した電解液の組成を次に示す。
（電解液組成）
ＮｉＳＯ４・６Ｈ２Ｏ ２５０ｇ／Ｌ
ＮｉＣｌ２・６Ｈ２Ｏ ５５ｇ／Ｌ
Ｈ３ＢＯ３ ４５ｇ／Ｌ
有機添加剤 適量
（２）分極曲線
図３の測定によって得られた分極曲線を示す。この図から、−０．３Ｖ〜−０．０５Ｖ（ｖｓ ＳＣＥ）では、ニッケル（Ｎｉ）めっきだけ溶解できると分かった。なお、この範囲よりも大きい電位であると、青銅も溶解し、更に電位を大きくすると酸素が発生することが分かった。
このように、−０．３Ｖ〜−０．０５Ｖ（ｖｓ ＳＣＥ）の電位では、水道用器具の基体である青銅、及びクロムめっきは溶解せず、ニッケルめっきのみが溶解する領域が存在する。従って、この電位の範囲では、クロムめっきに覆われていないニッケルめっき（又はニッケル合金めっき）だけを選択的に溶解することが可能であることが分かった。1. Measurement of Polarization Curve in Electrolyte (1) Test Apparatus Polarization curves were measured for bright nickel plating, base material (bronze), and chromium plating using the apparatus shown in FIG. In FIG. 2, reference numeral 11 indicates a counter electrode (Pt), reference numeral 13 indicates a sample electrode (bronze, nickel plating film, chrome plating film), reference numeral 15 indicates a salt bridge, and reference numeral 17 indicates a reference electrode (SCE electrode). Indicates. Reference numeral 19 denotes a water bath. The potentiostat shown in the figure is an apparatus that can accurately set the potential between the sample electrode and the reference electrode, and can accurately measure the current flowing between the sample electrode and the counter electrode at that time. is there.
The composition of the electrolytic solution used is shown below.
(Electrolytic solution composition)
NiSO 4 · 6H 2 O 250g / L
NiCl 2 · 6H 2 O 55g / L
H 3 BO 3 45 g / L
Organic additive suitable amount (2) Polarization curve The polarization curve obtained by the measurement of FIG. 3 is shown. From this figure, it has been found that only nickel (Ni) plating can be dissolved at -0.3 V to -0.05 V (vs SCE). It was found that bronze was dissolved when the potential was higher than this range, and oxygen was generated when the potential was further increased.
Thus, at a potential of −0.3 V to −0.05 V (vs SCE), bronze and chromium plating, which are bases for water supply equipment, are not dissolved, and there is a region where only nickel plating is dissolved. Therefore, it has been found that in this potential range, only nickel plating (or nickel alloy plating) that is not covered with chromium plating can be selectively dissolved.

２．水栓金具を用いた試験
（１）試験方法
図４に示す水栓金具を用いて試験した。この水栓金具の切断後の内部状況を図５に示す。なお、図４の水栓金具には、ワット浴を用いてニッケルめっきを施し、さらにニッケルめっきの上から公知の方法でクロムめっきを施してある。
この水栓金具を電解液に浸漬し、この状態で電位を印加して電解した。電解の条件を以下に示す。

（設定電位）
−０．０６Ｖ（ｖｓ ＳＣＥ）

（電解液組成）
ＮｉＳＯ４・６Ｈ２Ｏ ２５０ｇ／Ｌ
ＮｉＣｌ２・６Ｈ２Ｏ ５５ｇ／Ｌ
Ｈ３ＢＯ３ ４５ｇ／Ｌ
有機添加剤 適量

（電解時間）
１９２０ｓｅｃ2. Test using faucet fitting (1) Test method Tested using the faucet fitting shown in FIG. FIG. 5 shows the internal situation after cutting the faucet fitting. Note that the faucet fitting of FIG. 4 is nickel-plated using a Watt bath, and further chromium-plated by a known method from above the nickel plating.
This faucet fitting was immersed in an electrolytic solution, and an electric potential was applied in this state to perform electrolysis. The electrolysis conditions are shown below.

(Set potential)
-0.06V (vs SCE)

(Electrolytic solution composition)
NiSO 4 · 6H 2 O 250g / L
NiCl 2 · 6H 2 O 55g / L
H 3 BO 3 45 g / L
Organic additive

(Electrolysis time)
1920sec

（２）試験結果
図６に、試験後の水栓金具を示す。これより、表面のクロムめっきに腐食が見られず、試験前の図４の外観とほとんど変化していないことが分かった。また、この水栓金具の切断後の内部状況を図７に示す。この写真からは若干見にくいが、クロムめっきに覆われていないニッケルめっきが試験後（電解後）に溶解していることが目視により確認された。
この点について更に詳細に検討するために、エネルギー分析装置を用いて、所定の部位における元素の比率を測定した。
図８に、試験前の水栓金具の端面からの距離（図５参照）と、元素の検出比率の関係を示す。この図８から、端面に近い部分ではクロムめっきに覆われていないニッケルめっきの存在が確認された。
図９に、試験後の水栓金具の端面からの距離（図７参照）と、元素の検出比率の関係を示す。この図９から、端面に近い部分ではクロムめっきに覆われていないニッケルめっきが溶解して、その大部分は除去されていることが確認された。(2) Test results FIG. 6 shows the faucet fitting after the test. From this, it was found that the surface chrome plating was not corroded, and hardly changed from the appearance of FIG. 4 before the test. Moreover, the internal condition after cutting | disconnection of this faucet metal fitting is shown in FIG. Although slightly difficult to see from this photograph, it was visually confirmed that nickel plating not covered with chromium plating was dissolved after the test (after electrolysis).
In order to examine this point in more detail, the ratio of elements at a predetermined site was measured using an energy analyzer.
FIG. 8 shows the relationship between the distance from the end face of the faucet fitting before the test (see FIG. 5) and the element detection ratio. From FIG. 8, the presence of nickel plating not covered with chromium plating was confirmed in a portion near the end face.
FIG. 9 shows the relationship between the distance from the end face of the faucet fitting after the test (see FIG. 7) and the element detection ratio. From FIG. 9, it was confirmed that the nickel plating not covered with the chromium plating was dissolved in the portion close to the end face, and most of the nickel plating was removed.

３．実施例の効果
本実施例の水道用器具の製造方法によれば、クロムめっきに覆われていないニッケルめっきを簡易に除去できる。
また、本実施例では、電解液は、ニッケルめっきに用いるワット浴と同一組成のものを用いているため、特別な電解液を用意する必要がなく、コスト的に有利である。
本実施例の水道用器具は、外面のクロムめっきがクロムめっき本来の金属光沢を有するから、外観が良好である。
また、本実施例の水道用器具は、内通水路の全面に亘って銅合金が露出しているから、ニッケル浸出のおそれはない。3. Effect of Example According to the method for manufacturing a water supply device of this example, nickel plating not covered with chromium plating can be easily removed.
In this embodiment, since the electrolytic solution having the same composition as the watt bath used for nickel plating is used, it is not necessary to prepare a special electrolytic solution, which is advantageous in terms of cost.
The water supply device of this example has a good appearance because the outer surface chrome plating has the original metallic luster of chrome plating.
Moreover, since the copper alloy is exposed over the entire surface of the internal water passage, the water supply device of this embodiment has no fear of nickel leaching.

本発明は上記で詳述した実施形態に限定されず、本発明の請求項に示した範囲で様々な変形又は変更が可能である。   The present invention is not limited to the embodiments described in detail above, and various modifications or changes can be made within the scope of the claims of the present invention.

本発明の水道用器具の製造方法は、クロムめっきに覆われていないニッケルめっきを簡易に除去でき、水道水中のニッケルの規制強化に対応することができる。
本発明の水道用器具は、外面のクロムめっきがクロムめっき本来の金属光沢を有するから、外観が良好である。
本発明の水道用器具は、内通水路の全面に亘って銅合金が露出しているから、水道水中のニッケルの規制強化に対応することができる。The method for manufacturing a water supply device of the present invention can easily remove nickel plating that is not covered with chromium plating, and can cope with the stricter regulation of nickel in tap water.
The water supply apparatus of the present invention has a good appearance because the outer chrome plating has the original metallic luster of the chrome plating.
Since the copper alloy is exposed over the entire surface of the internal water passage, the water supply device of the present invention can cope with the stricter regulation of nickel in tap water.

１…基材
３…ニッケルめっき又はニッケル合金めっき
５…クロムめっき
Ａ…水道用器具DESCRIPTION OF SYMBOLS 1 ... Base material 3 ... Nickel plating or nickel alloy plating 5 ... Chrome plating A ... Water supply equipment

Claims (6)

水道用器具の製造方法であって、
その表面にニッケルめっき又はニッケル合金めっきと、さらにその上にクロムめっきとを施した、銅合金からなる基体を、電解液に浸漬した状態で所定の電位を印加し、前記クロムめっきに覆われていない前記ニッケルめっき又は前記ニッケル合金めっきを除去して水道用器具にすることを特徴とする水道用器具の製造方法。A method of manufacturing a water supply device,
A predetermined potential is applied in a state in which a base made of a copper alloy having nickel plating or nickel alloy plating on its surface and further chromium plating thereon is immersed in an electrolytic solution, and is covered with the chromium plating. A method for manufacturing a water supply device, wherein the nickel plating or the nickel alloy plating is removed to form a water supply device. 前記電解液がニッケル塩を含有することを特徴とする請求項１に記載の水道用器具の製造方法。   The method for manufacturing a water supply device according to claim 1, wherein the electrolytic solution contains a nickel salt. 前記電解液は、前記ニッケルめっき又は前記ニッケル合金めっきを形成する際に用いためっき浴と同一の塩を含有することを特徴とする請求項１又は２に記載の水道用器具の製造方法。   The method for manufacturing a water supply device according to claim 1 or 2, wherein the electrolytic solution contains the same salt as the plating bath used when the nickel plating or the nickel alloy plating is formed. 前記電解液は、ワット浴であることを特徴とする請求項１〜３のいずれか１項に記載の水道用器具の製造方法。   The said electrolyte solution is a watt bath, The manufacturing method of the water supply device of any one of Claims 1-3 characterized by the above-mentioned. 前記所定の電位が−０．３Ｖ〜−０．０５Ｖ（ｖｓ ＳＣＥ）であることを特徴とする請求項４に記載の水道用器具の製造方法。   The said predetermined electric potential is -0.3V--0.05V (vs SCE), The manufacturing method of the water supply device of Claim 4 characterized by the above-mentioned. 銅合金からなる基体の内部に内通水路が備えられた水道用器具であって、
外面には、ニッケルめっき又はニッケル合金めっきが施され、さらにその上にクロムめっきが施され、
前記内通水路は、全面に亘って銅合金が露出しており、
前記クロムめっきは、クロムめっき本来の金属光沢を有することを特徴とする水道用器具。A water supply device provided with an internal water passage inside a base made of a copper alloy,
On the outer surface, nickel plating or nickel alloy plating is applied, and further chromium plating is applied thereon,
The inner water passage has a copper alloy exposed over the entire surface,
The chrome plating has a metallic luster inherent to chrome plating, and is a water supply device.
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