JPWO2004024987A1 - Lead elution reduction processing method for lead-containing copper alloy and lead-containing copper alloy water supply device - Google Patents
Lead elution reduction processing method for lead-containing copper alloy and lead-containing copper alloy water supply device Download PDFInfo
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Abstract
鉛含有銅合金を溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液に浸漬し、表面の鉛を除去することを特徴とする鉛含有銅合金の鉛溶出低減処理方法及び鉛含有銅合金製水道用器具であるため、酸性のリン酸化合物による若干のエッチング効果と微小なリン酸皮膜が形成されるのみであるので大きな変色を伴うことなく、商品価値も低下しない。また、塩化ナトリウムを添加してもよく、鉛溶出低減についても十分効果がある。前工程として、鉛含有銅合金をアルカリ性のエッチング液に浸漬して表面の鉛を除去してもよい。これらの鉛含有銅合金は外部表面が、ニッケルクロムめっきをはじめとするめっきが施されていても問題はない。A lead elution reduction method for a lead-containing copper alloy and a lead-containing copper alloy, wherein the lead-containing copper alloy is immersed in an acidic solution containing no chromic acid in the solution and containing a phosphoric acid compound to remove lead on the surface. Since it is a device for waterworks, only a slight etching effect and a fine phosphoric acid film are formed by an acidic phosphoric acid compound, so that there is no significant discoloration and the commercial value is not lowered. Further, sodium chloride may be added, which is sufficiently effective for reducing lead elution. As a pre-process, the lead-containing copper alloy may be immersed in an alkaline etching solution to remove the lead on the surface. There is no problem even if these lead-containing copper alloys are plated on the outer surface such as nickel chrome plating.
Description
本発明は、鉛含有銅合金から鉛が溶出するのを低減させるための鉛溶出低減処理方法及び鉛の溶出を低減させた鉛含有銅合金製水道用器具に関する。
水道用器具とは、水栓金具、水道メーター、給湯機部材、温水洗浄便座部材、湯沸器、温水器、冷水器、製氷機、浄水器、温水ボイラー、自動販売機、ボールタップ、ロータンク、バルブ、フラッシュバルブ、熱交換器、継手、給水及び給湯ヘッダー、管、流し台、洗面台、便器、浴槽、住宅設備ユニットなどで、給水管につながる器具を全て含む。The present invention relates to a lead elution reduction treatment method for reducing lead elution from a lead-containing copper alloy and a lead-containing copper alloy water supply device that reduces elution of lead.
Water supply appliances include faucet fittings, water meters, water heater parts, warm water toilet seat members, water heaters, water heaters, water coolers, ice makers, water purifiers, hot water boilers, vending machines, ball taps, low tanks, valves Includes all appliances connected to water pipes, such as flush valves, heat exchangers, fittings, water and hot water headers, pipes, sinks, wash basins, toilets, bathtubs, and housing equipment units.
従来から、水道用器具例えば水栓金具は、一般的に銅や、青銅・黄銅等の銅合金材料を鋳造または鍛造し、切削加工、研磨加工等で形状を整え、ニッケルクロムめっき、塗装、イオンプレーティングなどの各種表面処理を施し、最終の製品組み立て工程を経て製造されている。上記銅合金には、切削性等の加工性を向上させるために、素材に鉛を添加されている場合が多いため、その鉛が飲料水中に微量ながら溶出し、その水を長期間飲用すると人体に悪影響を与えるおそれがあることが近年懸念されている。
筆者らは特許第３１８２７６５号において、鉛の存在形態とその物性に着目し、鉛含有銅合金をアルカリ性のエッチング液、クロム酸溶液、クロメート液に浸漬処理することで、鉛の溶出を大幅に低減するという発明を発表した。
特許第３１８２７６５号に記載されている鉛溶出低減方法の内、クロメート処理方法の中ではクロム酸とリン酸を両方同時に含む溶液に鉛含有銅合金を浸漬する場合が鉛溶出低減について最も効果があることを発表した。しかし、このクロメート液に鉛含有銅合金を浸漬する場合、浸漬後の銅合金部分の外観が白っぽくくすんだ変色外観となり、商品価値として低下する場合があった。これはクロム酸とリン酸からなるリンクロメート処理により、銅合金表面に有色の被膜が形成されるためと考えられる。
本発明は、上記課題を解決するためになされたもので、本発明の目的は、外観の変色により商品価値が低下しない鉛含有銅合金の鉛溶出低減処理方法及び鉛含有銅合金製水道用器具を提供するものである。Conventionally, water appliances such as faucet fittings have been generally cast or forged from copper, copper alloy materials such as bronze and brass, and shaped by cutting, polishing, etc., nickel chrome plating, painting, ion Various surface treatments, such as plating, are applied and manufactured through the final product assembly process. In order to improve the workability such as machinability, the copper alloy often has lead added to the material, so that the lead elutes in a small amount in the drinking water, and the human body when drinking the water for a long time In recent years, there is a concern that it may adversely affect
In Japanese Patent No. 3182765, the authors pay attention to the presence of lead and its physical properties, and immerse the lead-containing copper alloy in an alkaline etching solution, chromic acid solution, or chromate solution to significantly reduce lead elution. Announced an invention to do.
Of the lead elution reduction methods described in Japanese Patent No. 3182765, in the chromate treatment method, the case where the lead-containing copper alloy is immersed in a solution containing both chromic acid and phosphoric acid is most effective in reducing lead elution. Announced. However, when a lead-containing copper alloy is immersed in this chromate solution, the appearance of the copper alloy part after immersion becomes a whitish and fading discoloration appearance, which may reduce the commercial value. This is presumably because a colored film is formed on the surface of the copper alloy by the link romate treatment comprising chromic acid and phosphoric acid.
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a lead elution reduction treatment method for lead-containing copper alloys and a lead-containing copper alloy water supply device whose product value does not deteriorate due to discoloration of the appearance. Is to provide.
上記目的を達成するために請求の範囲第１項は、鉛含有銅合金を、溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液に浸漬し、表面の鉛を除去することを特徴とする鉛含有銅合金の鉛溶出低減処理方法である。
よって、酸性のリン酸化合物による若干のエッチング効果と微少なリン酸皮膜が形成されるのみであるので大きな変色を伴うことなく、商品価値も低下しない。また、鉛溶出低減についても十分効果がある。
上記目的を達成するために請求の範囲第２項は、鉛含有銅合金を、溶液中にクロム酸を含まずリン酸化合物と塩化ナトリウムを含む酸性溶液に浸漬することを特徴とする鉛含有銅合金の鉛溶出低減処理方法である。
よって、酸性のリン酸化合物に塩化ナトリウムを適量補充することにより、反応の進行を向上させエッチング効果とリン酸皮膜が増し安定した外観が確保できる。商品価値も低下しない。また、鉛溶質低減についても十分効果がある。
上記目的を達成するために請求の範囲第３項は、鉛含有銅合金をアルカリ性のエッチング液に浸漬して表面の鉛を除去し、次いで溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液に浸漬することを特徴とする鉛含有銅合金の鉛溶出低減処理方法である。
よって、まずアルカリ性のエッチング液に浸漬することで銅合金表面の鉛をほぼ選択的に除去できるため、後工程の溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液浸漬工程の鉛溶出低減効果と相まって、鉛溶出低減についてより十分な効果が認められる。また、これらの工程後でも酸性のリン酸化合物による若干のエッチング効果と微少なリン酸皮膜が形成されるのみであるので鉛含有銅合金は大きな変色を伴うことがなく、商品価値も低下しない。
上記目的を達成するために請求の範囲第４項は、鉛含有銅合金をアルカリ性のエッチング液に浸漬して表面の鉛を除去し、次いで溶液中にクロム酸を含まずリン酸化合物と塩化ナトリウムを含む酸性溶液に浸漬することを特徴とする鉛含有銅合金の鉛溶出低減処理方法である。
よって、まずアルカリ性のエッチング液に浸漬することで銅合金表面の鉛をほぼ選択的に除去できるため、後工程の溶液中にクロム酸を含まずリン酸化合物と塩化ナトリウムを含む酸性溶液浸漬工程の鉛溶出低減効果と相まって、鉛溶出低減についてより十分な効果が認められる。これらの工程後でも酸性のリン酸化合物に塩化ナトリウムを適量補充することにより、反応の進行を向上させエッチング効果とリン酸皮膜が増し安定した外観が確保できる。商品価値も低下しない。また、鉛溶質低減についても十分効果がある。
上記目的を達成するために請求の範囲第５項は、主として外部表面はめっき処理され、めっき処理されていない主として内部表面の鉛を除去することを特徴とする請求の範囲第１項及び第３項記載の鉛含有銅合金の鉛溶出低減処理方法である。
よって、外部表面のめっき処理されている部分は、上記のアルカリ性のエッチング液による浸漬工程や、溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液による浸漬工程で溶解反応やエッチング反応が起こらないため変色が発生せず、めっき処理されていなくて鉛含有銅合金が露出している主として内部表面のみに鉛溶出低減効果が達成できる。もちろん、その内部表面も、酸性のリン酸化合物による若干のエッチング効果と微少なリン酸皮膜が形成されるのみであるので大きな変色を伴うことがない。
上記目的を達成するために請求の範囲第６項は、主として外部表面のめっきは、ニッケルめっき後クロムめっきを施しためっきであることを特徴とする請求の範囲第３項記載の鉛含有銅合金の鉛溶出低減処理方法である。
水栓金具をはじめとする鉛含有銅合金の水道用器具は、外部表面に装飾性、耐食性、耐摩耗性等を付与するためにニッケルめっき後クロムめっきを施した場合が多く、従来から広く使用されているめっきである。このめっきの場合、上記のアルカリ性のエッチング液による浸漬工程や、リン酸化合物を含む酸性溶液による浸漬工程で溶解反応やエッチング反応が起こらないため変色が発生せず、めっき処理されていなくて鉛含有銅合金が露出している主として内部表面のみに鉛溶出低減効果が達成できる。もちろん、その内部表面も、酸性のリン酸化合物による若干のエッチング効果と微少なリン酸皮膜が形成されるのみであるので、大きな変色を伴うことがない。
上記目的を達成するために請求の範囲第７項は、リン酸化合物を含む酸性溶液に浸漬することを特徴とする請求の範囲第１項乃至第６項記載の鉛含有銅合金製水道用器具である。
よって、酸性のリン酸化合物による若干のエッチング効果と微少なリン酸皮膜が形成されるのみであるので、鉛含有銅合金表面の大きな変色を伴うことなく、鉛溶出低減についても十分効果があるため、商品価値が低下しない水道用器具を提供することが出来る。In order to achieve the above object, the first aspect of the present invention is characterized in that the lead-containing copper alloy is immersed in an acidic solution containing a phosphoric acid compound not containing chromic acid in the solution to remove lead on the surface. It is a lead elution reduction processing method of the lead containing copper alloy.
Therefore, since only a slight etching effect and a small phosphoric acid film are formed by the acidic phosphoric acid compound, the product value is not lowered without significant discoloration. Moreover, it is sufficiently effective in reducing lead elution.
In order to achieve the above object, the second aspect of the present invention provides a lead-containing copper alloy characterized by immersing a lead-containing copper alloy in an acidic solution that does not contain chromic acid and contains a phosphoric acid compound and sodium chloride. It is a lead elution reduction processing method of an alloy.
Therefore, by adding an appropriate amount of sodium chloride to the acidic phosphoric acid compound, the progress of the reaction is improved, the etching effect and the phosphoric acid film are increased, and a stable appearance can be secured. Product value will not decline. Moreover, it is sufficiently effective in reducing lead solutes.
In order to achieve the above object, the third aspect of the present invention is to remove the lead from the surface by immersing the lead-containing copper alloy in an alkaline etching solution, and then to add an acid containing a phosphate compound without containing chromic acid in the solution. A lead elution reduction treatment method for a lead-containing copper alloy, wherein the lead-containing copper alloy is immersed in a solution.
Therefore, since the lead on the copper alloy surface can be almost selectively removed by first dipping in an alkaline etchant, lead elution is reduced in the acid solution dipping process that does not contain chromic acid and contains a phosphoric acid compound in the subsequent process solution. Combined with the effect, a more sufficient effect for reducing lead elution is recognized. Further, even after these steps, only a slight etching effect and a slight phosphoric acid film are formed by the acidic phosphoric acid compound, so that the lead-containing copper alloy is not accompanied by a large discoloration and the commercial value is not lowered.
In order to achieve the above object, the fourth aspect of the present invention is to remove lead from the surface by immersing a lead-containing copper alloy in an alkaline etching solution, and then to remove the chromic acid in the solution and the phosphoric acid compound and sodium chloride. A lead elution reduction treatment method for a lead-containing copper alloy, wherein the lead-containing copper alloy is immersed in an acidic solution.
Therefore, since the lead on the surface of the copper alloy can be almost selectively removed by immersing in an alkaline etching solution, the acidic solution immersing step including the phosphoric acid compound and sodium chloride is not included in the solution in the subsequent step. Combined with the lead elution reduction effect, a more sufficient effect is observed for lead elution reduction. Even after these steps, by adding an appropriate amount of sodium chloride to the acidic phosphoric acid compound, the progress of the reaction is improved, the etching effect and the phosphoric acid film are increased, and a stable appearance can be secured. Product value will not decline. Moreover, it is sufficiently effective in reducing lead solutes.
In order to achieve the above object, the fifth aspect of the present invention is characterized in that the outer surface is mainly plated, and lead that is not plated is mainly removed from the inner surface. It is a lead elution reduction processing method of the lead containing copper alloy of description.
Therefore, the part subjected to the plating treatment on the outer surface undergoes a dissolution reaction or an etching reaction in the immersion process using the alkaline etching solution described above or the immersion process using an acidic solution containing a phosphoric acid compound that does not include chromic acid in the solution. Therefore, discoloration does not occur, and the lead elution reduction effect can be achieved mainly only on the inner surface where the lead-containing copper alloy is exposed without being plated. Of course, the internal surface is not accompanied by a large discoloration because only a slight etching effect by the acidic phosphoric acid compound and a slight phosphoric acid film are formed.
In order to achieve the above object, claim 6 is the lead-containing copper alloy according to claim 3, characterized in that the plating of the outer surface is mainly plating after nickel plating and chromium plating. It is a lead elution reduction processing method.
Lead-containing copper alloy water supply equipment, such as faucet fittings, has been widely used in the past because it has been nickel-plated and chrome-plated to provide decoration, corrosion resistance, wear resistance, etc. on the external surface. Plating. In the case of this plating, since no dissolution reaction or etching reaction occurs in the immersion process with the above alkaline etching solution or the immersion process with an acidic solution containing a phosphoric acid compound, discoloration does not occur, the plating treatment is not performed, and lead is contained. Lead elution reduction effect can be achieved mainly on the inner surface where the copper alloy is exposed. Of course, the internal surface is not accompanied by a large discoloration because only a slight etching effect and a slight phosphoric acid film are formed by the acidic phosphoric acid compound.
In order to achieve the above object, Claim 7 is immersed in an acidic solution containing a phosphoric acid compound, and the lead-containing copper alloy water supply device according to any one of Claims 1 to 6 It is.
Therefore, since only a slight etching effect and a slight phosphoric acid film are formed by the acidic phosphoric acid compound, there is a sufficient effect in reducing lead elution without accompanying a large discoloration of the lead-containing copper alloy surface. It is possible to provide a water supply device whose commercial value does not decrease.
（図１） 第１図は、本発明の実施例で使用した青銅鋳物製水栓金具を示す図である。
（図２） 第２図は、（ａ）は本発明に係る鉛含有銅合金の鉛溶出低減処理前の鉛含有銅合金製水道用器具の表面の拡大写真、（ｂ）はその断面写真である。
（図３） 第３図は、（ａ）は本発明に係る鉛含有銅合金の鉛溶出低減処理後の鉛含有銅合金製水道用器具の表面の拡大写真、（ｂ）はその断面写真である。(FIG. 1) FIG. 1 is a figure which shows the faucet metal fittings made from a bronze casting used in the Example of this invention.
(FIG. 2) FIG. 2 is an enlarged photograph of the surface of a lead-containing copper alloy water supply device before lead elution reduction treatment of the lead-containing copper alloy according to the present invention, and (b) is a cross-sectional photograph thereof. is there.
(FIG. 3) FIG. 3 (a) is an enlarged photograph of the surface of a lead-containing copper alloy water supply device after the lead elution reduction treatment of the lead-containing copper alloy according to the present invention, and (b) is a cross-sectional photograph thereof. is there.
本発明である溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液への浸漬により、鉛含有銅合金表面の若干のエッチング効果と微少なリン酸皮膜が形成されるため、鉛溶出低減に大きな低減効果があるだけでなく、外観上の大きな変色は伴わない。これは、クロムとリンの混合被膜が僅かに有色であるのに対しリン酸の単独被膜は無色であることに起因している。
本発明である溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液へ活性剤である塩化ナトリウムを適量補充する事により、反応の進行を向上させエッチング効果と微小なリン酸皮膜の形成が増し、安定した外観を確保してもよい。
活性剤では、塩化ナトリウム、硫酸ナトリウム、フッ化ナトリウム、硝酸ナトリウムなどがあり、添加量は０．１〜１０ｇ／Ｌ程度で、単独または数種添加する場合がある。
リン酸化合物は、リン酸カリウム、リン酸ナトリウム、リン酸カルシウム、リン酸アンモニウム、リン酸亜鉛などがあり、添加量は０．１〜５０ｇ／Ｌ程度で、単独または数種添加する場合がある。これらを添加した溶液を酸性にするため、リン酸、硝酸、硫酸、フッ酸等の無機酸を添加する。添加量は０．１〜５０ｇ／Ｌ程度で、単独または数種添加する場合がある。また、酢酸、シュウ酸、クエン酸、ぎ酸、酪酸、プロピオン酸等の有機酸を添加しても良い。溶液のｐＨは２以下が良く、１以下がより好ましい。添加剤としては、亜鉛、鉄、銅、マンガン、ニッケル等の金属化合物を適宜添加してもよい。尚、リン酸塩の化成処理液が広く市販されており、これらをしても良い。
処理温度は常温〜７０℃程度、処理時間は数秒〜数分の間で、被処理物の形状や大きさによって、適宜決定する。複雑形状の部品の場合、溶液に浸漬する際に、エアーポケットが出来ないように注意し、また、処理の効率を上げるために被処理物を揺動しても良い。処理後は、水滴残りや水膜残りなどによる外観不良をなくすために、速やかに水洗し、湯洗乾燥や熱風乾燥をするのが望ましい。
溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液への浸漬の前に、アルカリ性のエッチング液に浸漬することで鉛含有銅合金表面の鉛を選択的に溶解除去してもよい。鉛は両性金属であり、銅合金中で合金を形成せず鉛単体として存在するため、アルカリエッチング液により銅合金母体はほとんど反応せず、鉛化合物のみを選択的に溶解除去できる。よって、溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液の浸漬工程での負荷を軽減できる。また、鉛含有銅合金に前工程で付着した油成分などの汚れを除去する脱脂工程としても作用するため、非常に効率的な工程である。
アルカリ性のエッチング液の主成分は、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、リン酸ナトリウム、トリポリリン酸ナトリウム、メタケイ酸ナトリウム、オルソケイ酸ナトリウムなどのうち、単独または数種を溶解したアルカリ性溶液である。濃度は、数ｇ／Ｌ〜数１０ｇ／Ｌが一般的であり使用する成分の組み合わせにより適宜判断する。処理温度は６０〜９０℃程度、処理時間は数分〜数１０分の間で、被処理物の形状や大きさによって、適宜決定する。複雑形状の部品の場合、溶液に浸漬する際に、エアーポケットが出来ないように注意し、また、処理の効率を上げるために被処理物を揺動しても良い。処理後は、速やかに水洗して、次工程に進むのがよい。
アルカリ性のエッチング液の浸透、湿潤性を改善するために、液の表面張力を低下させる目的で界面活性剤を添加しても良い。界面活性剤としては、アニオン界面活性剤あるいはノニオン界面活性剤を用いることが多く、これらを単独又は併用する。アニオン界面活性剤としては、高級脂肪酸ナトリウム、硫酸化油、高級アルコール硫酸エステルナトリウム、アルキルベンゼン硫酸ナトリウム、高級アルキルエーテル硫酸エステルナトリウム、α−オレフィン硫酸ナトリウムがある。また、ノニオン界面活性剤としては、アルキルポリオキシエチレンエーテル、アルキルフェニルポリオキシエチレンエーテル、脂肪酸エチレンオキサイド付加物、ポリプロピレングリコールエチレンオキサイド付加物（プルロニック）がある。添加量は、数ｇ／Ｌ〜数１０ｇ／Ｌが一般的である。
また、アルカリ性のエッチング液には、鉛が水酸化物となって再付着するのを防ぐとともに、鉛の溶解を促進するために、キレート剤を添加することができる。キレート剤としては、例えば、ＥＤＴＡ、エチレンジアミン、トリエタノールアミン、チオ尿素、ロッシェル塩、酒石酸等の鉛と錯体を形成しやすい化合物が望ましい。添加量は、数ｇ／Ｌ〜数１０ｇ／Ｌが一般的である。
アルカリ性のエッチング液に酸化剤を添加すると、鉛が酸化され一旦酸化鉛（ＰｂＯ２）を経てアルカリに溶解する２段階反応が起こる。この反応は、鉛がアルカリに溶解する１段階反応よりも速やかであるため、結果として鉛除去を促進し、除去効率アップ、処理時間の短縮が図れる。酸化剤としては例えば、メタニトロベンゼンスルホン酸ナトリウム、パラニトロ安息香酸ナトリウム等の有機酸化性化合物、次亜塩素酸塩、さらし粉、過酸化水素、過マンガン酸カリウム、過硫酸塩、過塩素酸塩等の無機化合物を用いる。添加量は、数ｇ／Ｌ〜数１０ｇ／Ｌが一般的である。
水栓金具をはじめとする水道用器具は、外面の美観、耐食性、耐摩耗性等の目的でめっきを施す場合があるが、その製造方法は、一般に公知のめっき前処理後、公知技術である電気めっき、化学めっき、置換めっきまたは乾式めっきを行うため特に限定されるものではない。これらの中では、電気めっき法で、ニッケルめっき後クロムめっきを施す場合が品質、コストの点で最も一般的である。それ以外にも金めっき、銀めっき、ロジウムめっき、白金めっき、銅めっき、スズめっき、スズコバルト合金めっき、スズニッケル合金めっきなどがある。乾式めっき方法としては、真空蒸着、イオンプレーティング、スパッタリング、ＣＶＤ法などがあり、窒化チタン、炭化チタン、窒化ジルコニウム、窒化クロム、炭化ケイ素、ダイヤモンド、アルミナ、炭窒化チタンなどがある。
これらのめっきは、水栓金具をはじめとする鉛含有銅合金製水道用器具の内部表面には、ほとんどめっきがつかないことが多いため、その部分は銅合金素地が露出している状態である。本発明では、この鉛含有銅合金を、上記、アルカリ性のエッチング液や、溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液に浸漬することで、めっきがついている部分は何ら変化を起こさず、銅合金が露出している部分の鉛を効果的に除去する。By dipping in an acidic solution that does not contain chromic acid and contains a phosphoric acid compound in the solution of the present invention, a slight phosphoric acid film is formed on the lead-containing copper alloy surface, thus reducing lead elution Not only has a great reduction effect, it does not involve a large discoloration in appearance. This is because the mixed film of chromium and phosphorus is slightly colored, whereas the single film of phosphoric acid is colorless.
By adding an appropriate amount of sodium chloride as an activator to an acidic solution that does not contain chromic acid and contains a phosphoric acid compound in the solution of the present invention, the progress of the reaction is improved, and the etching effect and the formation of a fine phosphate film can be achieved. The stable appearance may be ensured.
Examples of the activator include sodium chloride, sodium sulfate, sodium fluoride, sodium nitrate and the like, and the addition amount is about 0.1 to 10 g / L, and may be added alone or in several kinds.
Phosphoric acid compounds include potassium phosphate, sodium phosphate, calcium phosphate, ammonium phosphate, zinc phosphate, and the like. The addition amount is about 0.1 to 50 g / L, and may be added alone or in several kinds. An inorganic acid such as phosphoric acid, nitric acid, sulfuric acid, or hydrofluoric acid is added to make the solution to which these are added acidic. The addition amount is about 0.1 to 50 g / L, and may be added alone or in several kinds. In addition, organic acids such as acetic acid, oxalic acid, citric acid, formic acid, butyric acid, and propionic acid may be added. The pH of the solution is preferably 2 or less, and more preferably 1 or less. As additives, metal compounds such as zinc, iron, copper, manganese, nickel, etc. may be added as appropriate. In addition, the chemical conversion treatment liquid of a phosphate is widely marketed, and these may be performed.
The treatment temperature is from room temperature to about 70 ° C., the treatment time is from several seconds to several minutes, and is appropriately determined depending on the shape and size of the workpiece. In the case of a part having a complicated shape, care should be taken not to form an air pocket when immersed in the solution, and the workpiece may be swung to increase the efficiency of processing. After the treatment, it is desirable to quickly wash with hot water, dry with hot water, or dry with hot air in order to eliminate appearance defects due to residual water droplets or water film.
Before immersing in an acidic solution that does not contain chromic acid and contains a phosphoric acid compound, the lead on the lead-containing copper alloy surface may be selectively dissolved and removed by immersing in an alkaline etching solution. Since lead is an amphoteric metal and does not form an alloy in the copper alloy and exists as lead alone, the copper alloy matrix hardly reacts with the alkali etching solution, and only the lead compound can be selectively dissolved and removed. Therefore, the load in the immersion process of the acidic solution which does not contain chromic acid in a solution but contains a phosphoric acid compound can be reduced. Moreover, since it acts also as a degreasing process which removes stain | pollution | contamination, such as an oil component adhering to a lead containing copper alloy at a previous process, it is a very efficient process.
The main component of the alkaline etching solution is an alkaline solution in which sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, sodium tripolyphosphate, sodium metasilicate, sodium orthosilicate or the like is dissolved alone or in several kinds. . The concentration is generally several g / L to several tens g / L, and is appropriately determined depending on the combination of components used. The treatment temperature is about 60 to 90 ° C., the treatment time is several minutes to several tens of minutes, and is appropriately determined depending on the shape and size of the workpiece. In the case of a part having a complicated shape, care should be taken not to form an air pocket when immersed in the solution, and the workpiece may be swung to increase the efficiency of processing. After the treatment, it is preferable to immediately wash with water and proceed to the next step.
In order to improve the penetration and wettability of the alkaline etching solution, a surfactant may be added for the purpose of reducing the surface tension of the solution. As the surfactant, an anionic surfactant or a nonionic surfactant is often used, and these are used alone or in combination. Examples of the anionic surfactant include higher fatty acid sodium, sulfated oil, higher alcohol sulfate sodium, alkylbenzene sodium sulfate, higher alkyl ether sulfate sodium, and α-olefin sodium sulfate. Nonionic surfactants include alkyl polyoxyethylene ether, alkylphenyl polyoxyethylene ether, fatty acid ethylene oxide adduct, and polypropylene glycol ethylene oxide adduct (pluronic). The addition amount is generally several g / L to several tens g / L.
Further, a chelating agent can be added to the alkaline etching solution in order to prevent lead from adhering again as a hydroxide and to promote dissolution of lead. As the chelating agent, for example, a compound that easily forms a complex with lead such as EDTA, ethylenediamine, triethanolamine, thiourea, Rochelle salt, and tartaric acid is desirable. The addition amount is generally several g / L to several tens g / L.
When an oxidizing agent is added to an alkaline etching solution, lead is oxidized, and a two-step reaction occurs in which it is dissolved in alkali through lead oxide (PbO 2 ). Since this reaction is quicker than the one-step reaction in which lead is dissolved in alkali, lead removal can be promoted, the removal efficiency can be increased, and the treatment time can be shortened. Examples of the oxidizing agent include organic oxidizing compounds such as sodium metanitrobenzenesulfonate and sodium paranitrobenzoate, hypochlorite, bleaching powder, hydrogen peroxide, potassium permanganate, persulfate, perchlorate and the like. Inorganic compounds are used. The addition amount is generally several g / L to several tens g / L.
Water faucets such as faucet fittings may be plated for the purpose of aesthetic appearance, corrosion resistance, wear resistance, etc., but the manufacturing method is generally known after a known plating pretreatment. The electroplating, chemical plating, displacement plating or dry plating is not particularly limited. Of these, electroplating is the most common in terms of quality and cost when chromium plating is applied after nickel plating. In addition, there are gold plating, silver plating, rhodium plating, platinum plating, copper plating, tin plating, tin cobalt alloy plating, tin nickel alloy plating, and the like. Examples of dry plating methods include vacuum deposition, ion plating, sputtering, and CVD, and include titanium nitride, titanium carbide, zirconium nitride, chromium nitride, silicon carbide, diamond, alumina, and titanium carbonitride.
Since these platings often have almost no plating on the inner surface of lead-containing copper alloy water supply equipment such as faucet fittings, the copper alloy substrate is exposed at that part. . In the present invention, by immersing this lead-containing copper alloy in the above-mentioned alkaline etching solution or an acidic solution containing a phosphoric acid compound not containing chromic acid in the solution, the portion with plating is changed. First, the lead where the copper alloy is exposed is effectively removed.
本発明を実施例により具体的に以下に説明するが、本発明はこれにより限定されるものではなく、本発明の技術的思想の範囲内で多くの改変をなしえることはもちろんである。
以下に示す条件で、第１図に記載した青銅鋳物製水栓金具を使用し各種処理条件で鉛除去処理をおこない、外観の状態と鉛溶出低減効果を評価した（実験１）。
処理工程は、アルカリエッチングのあと、酸性溶液での処理の順で行った。第２図（ａ）（ｂ）および第３図（ａ）（ｂ）は、処理前と処理後の表面の拡大写真、及び断面の拡大写真である。これらの写真を比較すると、処理後には表面から５〜６μｍの部分から鉛が溶出していることが分る。
外観は目視で、鉛溶出低減効果はＪＩＳ−Ｓ−３２００−７（２０００年）「水道用器具−浸出性能試験方法」にしたがって、溶出した鉛濃度を分析した。処理条件、外観の状態及び鉛溶出量を表１にまとめた。尚、アルカリエッチングの条件は、水酸化ナトリウム５０ｇ／Ｌ＋パラニトロ安息香酸ナトリウム１ｇ／Ｌの液を使用し、８０℃、１０分の条件で統一した。
外観の状態は、変色が激しく商品上大きく問題があるレベルを×、変色があり商品上問題があるレベルを△、変色がほとんどなく商品上問題がないレベルを○として判定した。
次に、塩化ナトリウムを添加した状態での鉛除去処理をおこない、外観の状態と鉛溶出低減効果を評価した（実験２）。処理工程は、アルカリエッチングのあと、酸性溶液での処理の順で行った。外観評価方法及び鉛溶出低減効果はＪＩＳ−Ｓ−３２００−７（２０００年）「水道用器具−浸出性能試験方法」にしたがって、溶出した鉛濃度を分析した。処理条件は、外観の状態及び鉛溶出量を表２にまとめた。尚、アルカリエッチングの条件は、水酸化ナトリウム５０ｇ／Ｌ＋パラニトロ安息香酸ナトリウム１ｇ／Ｌの液を使用し、６０℃、５分の条件で統一した。
外観の状態は、変色が激しく商品上大きく問題があるレベルを×、変色があり商品上問題があるレベルを△、変色がほとんどなく商品上問題のないレベルを○、変色せず商品上問題がないレベルを◎として判定した。
次に、ニッケルめっき後クロムめっきを施した第１図の青銅鋳物製水栓金具について、各種処理条件で鉛除去処理をおこない、外観の状態と鉛溶出低減効果を評価した（実験３）。処理工程は、アルカリエッチングのあと、酸性溶液での処理の順で行った。外観評価方法及び鉛溶出量の評価方法も実験１と同じ方法で行い、外観は目視で、鉛溶出低減効果はＪＩＳ−Ｓ−３２００−７（２０００年）「水道用器具−浸出性能試験方法」にしたがって、溶出した鉛濃度を分析した。処理条件、外観の状態及び鉛溶出量を表２にまとめた。尚、アルカリエッチングの条件は、水酸化ナトリウム５０ｇ／Ｌ＋パラニトロ安息香酸ナトリウム１ｇ／Ｌの液を使用し、６０℃、５分の条件で統一した。
外観の状態は、変色が激しく商品上大きく問題があるレベルを×、変色があり商品上問題があるレベルを△、変色がほとんどなく商品上問題がないレベルを○として判定した。
本発明は上記構成により次の効果を発揮する。すなわち、酸性のリン酸化合物による若干のエッチング効果と微少なリン酸皮膜が形成されるのみであるので大きな変色を伴うことなく、商品価値も低下しない。また、本発明である溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液へ活性剤である塩化ナトリウムを適量補充する事により、反応の進行を向上させエッチング効果と微小なリン酸皮膜の形成が増し、安定した外観を確保出来き鉛溶出低減についても十分効果がある。また、まずアルカリ性のエッチング液に浸漬することで銅合金表面の鉛をほぼ選択的に除去できるため、後工程のリン酸化合物を含む酸性溶液浸漬工程の鉛溶出低減効果と相まって、鉛溶出低減についてより十分な効果が認められる。また、これらの工程後でも鉛含有銅合金は大きな変色を伴うことがなく、商品価値も低下しない。
外部表面のめっき処理されている部分は、上記のアルカリ性のエッチング液による浸漬工程や、溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液による浸漬工程で溶解反応やエッチング反応が起こらないため変色が発生せず、めっき処理されていなくて鉛含有銅合金が露出している主として内部表面のみに鉛溶出低減効果が達成できる。もちろん、その内部表面も大きな変色を伴うことがない。
水栓金具をはじめとする鉛含有同語金の水道用器具は、外部表面に装飾性、耐食性、耐摩耗性等を付与するためにニッケルクロムめっき後クロムめっきを施した場合が多く、従来から広く使用されているめっきである。このめっきの場合、上記のアルカリ性のエッチング液による浸漬工程や、溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液による浸漬工程で溶解反応やエッチング反応が起こらないため変色が発生せず、めっき処理されていなくて鉛含有銅合金が露出している主として内部表面のみに鉛溶出低減効果が達成できる。もちろん、その内部表面も大きな変色を伴うことがない。
本実施例においてはメッキ処理を、リン酸化合物を含む酸性溶液による浸漬工程前に行ったが浸漬工程後に行ってもよい。The present invention will be specifically described below with reference to examples. However, the present invention is not limited thereto, and it goes without saying that many modifications can be made within the scope of the technical idea of the present invention.
Under the conditions shown below, the bronze cast faucet shown in FIG. 1 was used to perform lead removal treatment under various treatment conditions, and the appearance and lead elution reduction effect were evaluated (Experiment 1).
The treatment process was performed in the order of treatment with an acidic solution after alkali etching. 2 (a) and 2 (b) and 3 (a) and 3 (b) are an enlarged photograph of the surface before and after the treatment, and an enlarged photograph of the cross section. When these photographs are compared, it can be seen that lead is eluted from a portion of 5 to 6 μm from the surface after the treatment.
The appearance was visually observed, and the lead elution reduction effect was analyzed in accordance with JIS-S-3200-7 (2000) "Equipment for water supply-leaching performance test method". Table 1 summarizes the processing conditions, appearance and lead elution amount. In addition, the conditions of alkali etching used the liquid of sodium hydroxide 50g / L + sodium paranitrobenzoate 1g / L, and unified them on the conditions of 80 degreeC and 10 minutes.
Appearance state was determined as “X” for a level where there was a severe color change and a large problem on the product, “Δ” for a level where there was a color change and a problem on the product, and “◯” a level where there was almost no color change and no problem on the product.
Next, the lead removal process in the state which added sodium chloride was performed, and the appearance state and the lead elution reduction effect were evaluated (Experiment 2). The treatment process was performed in the order of treatment with an acidic solution after alkali etching. The appearance evaluation method and the lead elution reduction effect were analyzed in accordance with JIS-S-3200-7 (2000) "Equipment for water supply-leaching performance test method". The processing conditions are summarized in Table 2 for the appearance and lead elution amount. In addition, the conditions of alkali etching used the liquid of sodium hydroxide 50g / L + sodium paranitrobenzoate 1g / L, and unified them on 60 degreeC and the conditions for 5 minutes.
Appearance state is x for a product that has severe discoloration and has a significant problem on the product, △ for a product that has discoloration and has a problem on the product, ◯ for a level that has almost no discoloration and no problem on the product, and has no problem on the product without discoloration No level was judged as ◎.
Next, the bronze cast faucet of FIG. 1 that was plated with nickel after chrome plating was subjected to lead removal treatment under various treatment conditions to evaluate the appearance and lead elution reduction effect (Experiment 3). The treatment process was performed in the order of treatment with an acidic solution after alkali etching. The appearance evaluation method and the lead elution amount evaluation method were also performed in the same manner as in Experiment 1. The appearance was visually observed, and the lead elution reduction effect was JIS-S-3200-7 (2000) "Water supply equipment-Leaching performance test method" The dissolved lead concentration was analyzed. Table 2 summarizes the processing conditions, appearance, and lead elution. In addition, the conditions of alkali etching used the liquid of sodium hydroxide 50g / L + sodium paranitrobenzoate 1g / L, and unified them on 60 degreeC and the conditions for 5 minutes.
Appearance state was determined as “X” for a level where there was a severe color change and a large problem on the product, “Δ” for a level where there was a color change and a problem on the product, and “◯” a level where there was almost no color change and no problem on the product.
The present invention exhibits the following effects by the above configuration. That is, since only a slight etching effect and a slight phosphoric acid film are formed by the acidic phosphoric acid compound, there is no significant discoloration and the commercial value is not lowered. Further, by adding an appropriate amount of sodium chloride as an activator to an acidic solution that does not contain chromic acid and contains a phosphoric acid compound in the solution according to the present invention, the progress of the reaction is improved, and the etching effect and the minute phosphate film are formed. The formation increases, a stable appearance can be secured, and there is a sufficient effect in reducing lead elution. In addition, since the lead on the surface of the copper alloy can be almost selectively removed by immersing in an alkaline etching solution, the reduction of lead leaching is coupled with the effect of reducing lead leaching in an acidic solution dipping process including a phosphoric acid compound in the subsequent process. A more sufficient effect is recognized. Moreover, even after these steps, the lead-containing copper alloy does not cause a large discoloration, and the commercial value does not decrease.
Because the plating process on the outer surface does not cause dissolution reaction or etching reaction in the immersion process with the above alkaline etching solution or the immersion process with an acidic solution containing a phosphoric acid compound without containing chromic acid in the solution. Discoloration does not occur, and the lead elution reduction effect can be achieved mainly only on the inner surface where the lead-containing copper alloy is exposed without being plated. Of course, the inner surface is not accompanied by a large discoloration.
Plumbing fixtures such as faucet fittings have been treated with chrome plating after nickel chrome plating in order to impart decorativeness, corrosion resistance, wear resistance, etc. to the external surface. It is a widely used plating. In the case of this plating, no discoloration occurs because no dissolution reaction or etching reaction occurs in the immersion step with the above alkaline etching solution or the immersion step with an acidic solution containing a phosphoric acid compound without containing chromic acid in the solution, The lead elution reduction effect can be achieved mainly only on the inner surface where the lead-containing copper alloy is exposed without being plated. Of course, the inner surface is not accompanied by a large discoloration.
In this embodiment, the plating process is performed before the dipping process with the acidic solution containing the phosphoric acid compound, but may be performed after the dipping process.
本発明に係る鉛含有銅合金の鉛溶出低減処理方法及び鉛含有銅合金製水道用器具は、給水管につながる各種器具に利用することができる。 The lead elution reduction processing method of lead-containing copper alloy and the lead-containing copper alloy water supply device according to the present invention can be used for various devices connected to a water supply pipe.
【特許請求の範囲】
【請求項１】 鉛含有銅合金を、酸化剤を含むアルカリ性のエッチング液に浸潰して、次いで溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液に浸漬することを特徴とする鉛含有銅合金の鉛溶出低減処理方法。
【請求項２】 鉛含有銅合金を、酸化剤を含むアルカリ性のエッチング液に侵漬して、次いで溶液中にクロム酸を含まずリン酸化合物と塩化ナトリウムを含む酸性溶液に浸漬することを特徴とする鉛含有銅合金の鉛溶出低減処理方法。
【請求項３】 鉛含有銅合金の外部表面にめっき処理を施した後、酸化剤を含むアルカリ性のエッチング液に浸漬して、次いで溶液中にクロム酸を含まずリン酸化合物を含む酸性溶液に浸漬することを特徴とすることを特徴とする鉛含有銅合金の鉛溶出低減処理方法。
【請求項４】 前記外部表面のめっきは、ニッケルめっき後にクロムめっきを施しためっきであることを特徴とする請求項３に記載の鉛含有銅合金の鉛溶出低減処理方法。
【請求項５】 請求項１から請求項４のいずれか１つに記載の鉛含有銅合金の鉛溶出低減処理方法により処理されたことを特徴とする鉛含有銅合金製水道用器具。
[Claims]
Claim1] Lead-containing copper alloyContains oxidizerA method for reducing lead elution of a lead-containing copper alloy, wherein the lead-containing copper alloy is immersed in an alkaline etching solution and then immersed in an acidic solution containing no chromic acid and containing a phosphoric acid compound.
Claim2] Lead-containing copper alloyContains oxidizerSoak in an alkaline etchant,NextA lead elution reduction treatment method for a lead-containing copper alloy, wherein the lead-containing copper alloy is immersed in an acidic solution that does not contain chromic acid and contains a phosphoric acid compound and sodium chloride.
[Claim 3] Of lead-containing copper alloysExternal surfaceInPlatedAfter, containing oxidizerA method for reducing lead elution of a lead-containing copper alloy, wherein the lead-containing copper alloy is immersed in an alkaline etching solution and then immersed in an acidic solution that does not contain chromic acid and contains a phosphoric acid compound.
[Claim 4] Of the external surfacePlating is characterized by plating with nickel plating followed by chromium platingClaim 3The lead elution reduction processing method of the lead containing copper alloy of description.
Claim5] It processed by the lead elution reduction processing method of the lead containing copper alloy as described in any one of Claims 1-4.Equipment for water supply made of lead-containing copper alloy.
Claims (7)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2002256207 | 2002-08-30 | ||
| JP2002256207 | 2002-08-30 | ||
| PCT/JP2003/011093 WO2004024987A1 (en) | 2002-08-30 | 2003-08-29 | Method of treatment for reducing elution of lead from lead containing copper alloy and waterwork utensils made from lead containing copper alloy |
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| JPWO2004024987A1 true JPWO2004024987A1 (en) | 2006-01-12 |
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| JP (1) | JPWO2004024987A1 (en) |
| CN (1) | CN1678768A (en) |
| AU (1) | AU2003257600A1 (en) |
| WO (1) | WO2004024987A1 (en) |
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| JP4197269B2 (en) * | 2002-09-09 | 2008-12-17 | 株式会社キッツ | Nickel elution prevention method for copper alloy piping equipment such as valves and fittings and its copper alloy piping equipment |
| CN1930324B (en) * | 2004-03-05 | 2012-02-08 | 株式会社开滋 | Method of preventing nickel leaching from copper alloy made liquid-contact equipment item, protective film forming agent for nickel leaching prevention and cleaner for nickel leaching prevention |
| WO2006035695A1 (en) * | 2004-09-28 | 2006-04-06 | Hayakawa Valve Production Co., Ltd. | Hexavalent chromium-free surface treating method and hexavalent chromium-free lead-containing copper-base metal material |
| JP5473781B2 (en) * | 2009-06-01 | 2014-04-16 | 株式会社Ｌｉｘｉｌ | Manufacturing method and processing method for lead-containing copper alloy water supply equipment |
| CN103143890A (en) * | 2013-03-04 | 2013-06-12 | 阮伟光 | Manufacturing method for low lead copper alloy bath utensil |
| EP3375317B1 (en) * | 2015-11-11 | 2021-06-30 | YKK Corporation | Fastener stringer, method for manufacturing same, and slide fastener |
| KR101782697B1 (en) * | 2015-12-11 | 2017-09-28 | 엄영호 | Water meter and method for manufacturing |
| CN106086894B (en) * | 2016-06-23 | 2018-06-19 | 台州德尊洁具厂(普通合伙) | A kind of processing technology of tap main body deleading technique and tap main body |
| JP6679511B2 (en) * | 2016-07-05 | 2020-04-15 | 日本特殊陶業株式会社 | Ceramic heater |
| EP3484240B1 (en) | 2016-07-05 | 2022-05-04 | Ngk Spark Plug Co., Ltd. | Ceramic heater |
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| JPS6324074A (en) * | 1986-07-17 | 1988-02-01 | Nippon Denso Co Ltd | Chemical conversion treatment bath composition for copper alloy |
| WO1999028536A1 (en) * | 1997-12-03 | 1999-06-10 | Toto Ltd. | Method of reducing elution of lead in lead-containing copper alloy, and city water service fittings made of lead-containing copper alloy |
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2003
- 2003-08-29 WO PCT/JP2003/011093 patent/WO2004024987A1/en active Application Filing
- 2003-08-29 CN CN 03820699 patent/CN1678768A/en active Pending
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| WO2004024987A1 (en) | 2004-03-25 |
| CN1678768A (en) | 2005-10-05 |
| AU2003257600A1 (en) | 2004-04-30 |
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