WO2004024987A1 - Procede de traitement destine a reduire l'elution de plomb dans un alliage de cuivre contenant du plomb et elements d'adduction d'eau fabriques en alliage de cuivre contenant du plomb - Google Patents

Procede de traitement destine a reduire l'elution de plomb dans un alliage de cuivre contenant du plomb et elements d'adduction d'eau fabriques en alliage de cuivre contenant du plomb Download PDF

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Publication number
WO2004024987A1
WO2004024987A1 PCT/JP2003/011093 JP0311093W WO2004024987A1 WO 2004024987 A1 WO2004024987 A1 WO 2004024987A1 JP 0311093 W JP0311093 W JP 0311093W WO 2004024987 A1 WO2004024987 A1 WO 2004024987A1
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WO
WIPO (PCT)
Prior art keywords
lead
copper alloy
containing copper
solution
phosphoric acid
Prior art date
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PCT/JP2003/011093
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English (en)
Japanese (ja)
Inventor
Masashi Kawamoto
Mikio Orita
Akira Goto
Mitsuo Imamoto
Original Assignee
Toto Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Toto Ltd. filed Critical Toto Ltd.
Priority to JP2004535893A priority Critical patent/JPWO2004024987A1/ja
Priority to AU2003257600A priority patent/AU2003257600A1/en
Publication of WO2004024987A1 publication Critical patent/WO2004024987A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the present invention relates to a lead elution reduction treatment method for reducing the elution of lead from a lead-containing copper alloy, and to a lead-containing copper alloy water supply device with reduced lead elution.
  • Water supply equipment includes faucet fittings, water meter meters, water heater components, hot water flush toilet seat components, water heaters, water heaters, water coolers, ice makers, Joda water heaters, hot water boilers, vending machines, Includes all equipment that connects to the water supply pipe, such as rutap, low tank, valve, flush valve, heat exchanger, fittings, water supply and hot water supply header, pipe, sink, wash basin, toilet bowl, bathtub, and housing equipment unit.
  • water supply appliances such as faucet fittings are generally made or forged of copper or a copper alloy material such as bronze or brass, and are shaped by cutting, polishing, etc., and nickel-chrome plating, painting, It is manufactured through various surface treatments such as ion plating and the final product assembly process.
  • lead is added to the above-mentioned copper alloys in order to improve workability such as machinability, so that a small amount of lead is eluted into drinking water. In recent years, there has been a concern that this may have a negative effect on water quality.
  • Patent No. 318,765 focused on the form of lead and its physical properties, and immersed a lead-containing copper alloy in an alkaline etching solution, chromic acid solution, and chromate solution. An invention that significantly reduces the elution of glycerol was announced. '' Among the lead elution reduction methods described in Patent No. 3 182 7 65, among the chromate treatment methods, a lead-containing copper alloy may be immersed in a solution containing both chromic acid and phosphoric acid at the same time. It was announced that lead elution was most effective.
  • the appearance of the copper alloy part after immersion has a whitish discolored appearance, which may reduce the commercial value. This is probably because a colored film is formed on the surface of the copper alloy by the link chromatization treatment comprising chromic acid and phosphoric acid.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a method for reducing lead elution of a lead-containing copper alloy which does not reduce its commercial value due to discoloration of appearance, and a lead-containing copper alloy water supply.
  • the equipment is provided. Disclosure of the invention
  • Claim 1 is characterized in that a lead-containing copper alloy is immersed in an acidic solution containing a phosphoric acid compound without containing chromic acid in the solution to remove lead on the surface. This is a method for reducing lead elution of a lead-containing copper alloy.
  • claim 2 is characterized in that a lead-containing copper alloy is immersed in an acidic solution containing a phosphoric acid compound and sodium chloride without containing chromic acid in the solution. This is a method for reducing lead elution of a copper alloy.
  • claim 3 is that a lead-containing copper alloy is immersed in an alkaline etching solution to remove lead on the surface, and then the solution is free of chromic acid and contains a phosphoric acid compound. This is a method for reducing lead elution of a lead-containing copper alloy, characterized by being immersed in a solution.
  • the lead on the surface of the copper alloy can be almost selectively removed by immersion in an etching solution having an alkaline force.
  • an acid solution immersion process that does not contain chromic acid but contains a phosphoric acid compound in the solution in the subsequent process Combined with the effect of reducing lead elution, a more sufficient effect on reducing lead elution is recognized.
  • only a small amount of etching effect and a minute phosphoric acid film are formed by the acidic phosphoric acid compound. .
  • the scope of claim 4 is to immerse the lead-containing copper alloy in an alkaline etching solution to remove lead on the surface, and then contain a phosphoric acid compound and sodium chloride containing no chromic acid in the solution.
  • a method for reducing lead elution of a lead-containing copper alloy characterized by immersing the lead-containing copper alloy in an acidic solution containing.
  • the scope of claim 5 is characterized in that mainly the outer surface is subjected to a plating treatment, and the lead which is not plated is mainly removed from the inner surface. 3.
  • the portion of the outer surface that has been plated is subjected to a dissolution or etching reaction in the above-described immersion step using an alkaline etching solution or the immersion step using an acid solution containing a phosphoric acid compound without containing chromic acid in the solution. Since no discoloration occurs, 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 because only a slight etching effect of the acidic phosphoric acid compound and a minute phosphoric acid film are formed.
  • the scope of claim 6 is characterized in that, mainly, the plating on the outer surface is a plating in which chrome is applied after nickel plating. This is a method for reducing lead elution of a copper alloy.
  • Water-supply fixtures made of lead-containing copper alloys are often chrome-plated after nickel plating in order to impart decorativeness, corrosion resistance, abrasion resistance, etc. to the outer surface. This is the plating used.
  • the immersion step using the alkaline etching solution described above, or the acidic step including a phosphoric acid compound is performed. Since no dissolution reaction or etching reaction occurs in the immersion step with the solution, discoloration does not occur, and a lead elution reduction effect can be achieved mainly only on the inner surface where the lead-containing copper alloy is exposed without being plated.
  • the inner 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.
  • claim 7 is a lead-containing copper alloy water supply according to claims 1 to 6, characterized in that the tap is immersed in an acidic solution containing a phosphoric acid compound. Equipment.
  • FIG. 1 is a view showing a faucet made of bronze ceramic used in an embodiment of the present invention.
  • FIG. 2 (a) is an enlarged photograph of the surface of a lead-containing copper alloy water supply device before 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.
  • 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.
  • the progress of the reaction is improved, thereby achieving an etching effect and a fine phosphoric acid film. May increase, and a stable appearance may be secured.
  • the activator include sodium chloride, sodium sulfate, sodium fluoride, sodium nitrate, and the like. The addition amount is about 0.1 to 10 g / L, and may be used alone or in combination.
  • Phosphoric acid compounds include potassium phosphate, sodium phosphate, calcium phosphate, ammonium phosphate, zinc phosphate, etc., and the amount of addition is about 0.1 to 50 g ZL.Single or several kinds may be added. .
  • Add an inorganic acid such as phosphoric acid, nitric acid, sulfuric acid, or hydrofluoric acid to make the solution containing these components acidic.
  • the addition amount is about 0.1 to 50 g ZL, and it may be added alone or in several kinds.
  • 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, more preferably 1 or less.
  • a metal compound such as zinc, iron, copper, manganese, and nickel may be appropriately added. Incidentally, chemical conversion treatment solutions of phosphates are widely marketed, and these may be used.
  • the processing temperature is from room temperature to about 70 ° C
  • the processing time is between several seconds and several minutes, and it is appropriately determined according to the shape and size of the object to be processed. In the case of parts with complicated shapes, care should be taken not to create pockets of air when immersing in the solution, and the workpiece may be rocked to increase the processing efficiency. After the treatment, it is desirable to wash quickly, and then wash with hot water and dry with hot air in order to eliminate the bad appearance due to the remaining water droplets and water film.
  • the lead on the lead-containing copper alloy surface can be selectively dissolved and removed by immersion in an alkaline etching solution.
  • good Since lead is an amphoteric metal and does not form an alloy in the copper alloy and exists as a simple substance of lead, the base of the copper alloy hardly reacts with the alkali etching solution, and only the lead compound can be selectively dissolved and removed. Therefore, the load in the immersion step of an acidic solution containing a phosphoric acid compound without containing chromic acid in the solution can be reduced.
  • the degreasing process which removes dirt such as oil components attached to the lead-containing copper alloy in the previous process, is an extremely efficient process.
  • the main component of the alkaline etching solution is an alkaline solution in which one or several of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, sodium tripolyphosphate, sodium metasilicate, sodium orthosilicate, etc. are dissolved. .
  • the concentration is generally several g ZL to several 10 g ZL, and is appropriately determined depending on the combination of components used.
  • the processing temperature is about 60 to 90 ° C., and the processing time is between several minutes to several ten minutes, which is appropriately determined according to the shape and size of the object to be processed. In the case of parts with complicated shapes, be careful not to create air pockets when immersing in the solution, and the workpiece may be swung to increase the processing efficiency. After the treatment, it is good to wash immediately and proceed to the next step.
  • a surfactant may be added for the purpose of lowering the surface tension of the solution.
  • an anionic surfactant or a nonionic surfactant is often used, and these may be used alone or in combination.
  • anionic surfactants include sodium higher fatty acids, sulfated oils, sodium higher alcohol sulfates, sodium alkylbenzene sulfate, sodium higher alkyl ether sulfates, and sodium alpha-refine sulfate.
  • nonionic surfactants include alkyl polyoxyethylene ether, alkyl phenyl polyoxyethylene ether, fatty acid ethylene oxide adduct, and polypropylene glycol ethylene oxide adduct (pull nick).
  • the amount of addition is generally from several g / L to several 10 g ZL.
  • a chelating agent can be added to the alkaline etching solution to prevent lead from becoming a hydroxide and re-adhering, and to promote the dissolution of lead.
  • the chelating agent for example, a compound which easily forms a complex with lead, such as EDTA, ethylenediamine, triethanolamine, thiourea, Rossier salt and tartaric acid, is desirable.
  • the amount of addition is generally several g / L to several 10 g / L.
  • oxidizing agent to Al force Li of etching solution
  • lead is oxidized two step reaction which dissolves in alkaline occurs once through lead oxide (P b 0 2). This reaction is quicker than the one-step reaction in which lead dissolves in the aluminum alloy, thereby accelerating lead removal, increasing removal efficiency and reducing processing time.
  • the oxidizing agent include sodium metanitrobenzenesulfonate, sodium paranitrobenzoate, and the like.
  • Use inorganic compounds such as organic oxidizing compounds, hypochlorite, bleaching powder, hydrogen peroxide, potassium permanganate, persulfate and perchlorate.
  • the amount of addition is generally several g ZL to several 10 g ZL.
  • Water faucet fittings and other water supply appliances are sometimes plated for the purpose of external aesthetics, corrosion resistance, abrasion resistance, and the like.
  • chrome plating after nickel plating using the electroplating method is the most common in terms of quality and cost.
  • gold plating, silver plating, rhodium plating, platinum plating, copper plating, tin plating, tin-cobalt alloy plating, and tin-nickel alloy plating are examples of silver plating, rhodium plating, platinum plating, copper plating, tin plating, tin-cobalt alloy plating, and tin-nickel alloy plating.
  • Dry plating methods include vacuum deposition, ion plating, sputtering, and CVD methods, including titanium nitride, titanium carbide, zirconium nitride, chromium nitride, silicon carbide, diamond, alumina, and titanium carbonitride.
  • plating is hardly applied to the inner surface of lead-containing copper alloy water supply equipment such as faucet fittings, so the copper alloy base is exposed in that part. It is.
  • the lead-containing copper alloy is immersed in the above-mentioned aluminum-based etching solution or an acidic solution containing a phosphoric acid compound without containing chromic acid in the solution, so that any plated portion is not formed. It does not change and effectively removes lead from the exposed copper alloy.
  • FIGS. 2 (a) and 2 (b) and FIGS. 3 (a) and 3 (b) are enlarged photographs of the surface before and after the treatment and enlarged photographs of the cross section. If you compare these photos, after processing It can be seen that lead is eluted from 5 to 6 m from the surface.
  • Table 1 summarizes the processing conditions, appearance conditions, and lead elution amount.
  • the alkaline etching conditions were the same, using a solution of sodium hydroxide 50 g / L + sodium paranitrobenzoate lg / L, at 80 ° C and 10 minutes.
  • the appearance was rated as X, which was severely discolored and had a serious problem on the product, as V was a level with discoloration and had a problem on the product, and as a level was a level with little discoloration and no problem on the product.
  • the appearance condition is X for a level that is severely discolored and has a serious problem on the product, X indicates a level that has discoloration and a problem on the product, A indicates a level that has little discoloration and has no problem on the product, The level with no was judged as ⁇ .
  • the concentration of eluted lead was prayed.
  • Table 2 summarizes the processing conditions, appearance conditions, and lead elution amount.
  • the conditions of the alkaline etching were unified at 60 ° C. for 5 minutes using a solution of 50 g / L of sodium hydroxide + lg / L of sodium paranitrobenzoate.
  • the appearance condition is X, which is severely discolored and has a major problem on the product, X is the level with discoloration and there is a problem on the product, and the level is that there is almost no discoloration and there is no problem on the product C determined as ⁇
  • the present invention has the following effects by the above configuration. That is, acidic phosphoric acid compound Since only a slight etching effect and a minute phosphoric acid film are formed by the product, there is no significant discoloration and the commercial value does not decrease.
  • an appropriate amount of sodium chloride as an activator to an acidic solution containing a phosphoric acid compound without containing chromic acid in the solution of the present invention, the progress of the reaction is improved, and the etching effect and fine phosphoric acid are reduced. The formation of a film increases, a stable appearance can be secured, and the effect of reducing lead elution is sufficiently effective.
  • the lead on the surface of the copper alloy can be almost selectively removed by immersion in an alkaline etching solution, the lead leaching effect is reduced in conjunction with the lead leaching effect of the acid solution containing a phosphoric acid compound in the subsequent process. Is more effective. In addition, even after these steps, the lead-containing copper alloy does not undergo significant discoloration and does not decrease its commercial value.
  • a dissolution reaction or an etching reaction occurs in the immersion step using the above alkaline etching liquid or the immersion step using an acidic solution containing a phosphoric acid compound without containing chromic acid in the solution. Since no discoloration occurs, the effect of reducing lead elution can be achieved mainly only on the inner surface where the lead-containing copper alloy is exposed without being plated. Of course, its inner surface does not undergo significant discoloration either.
  • water faucet fittings such as faucet fittings are made of nickel-chrome and then chrome-plated in order to provide decorativeness, corrosion resistance, abrasion resistance, etc. on the outer surface.
  • This plating has been widely used in the past.
  • no discoloration reaction or etching reaction occurs in the immersion step using the alkaline etching solution described above or in the immersion step using 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, its inner surface does not undergo significant discoloration.
  • the plating process is performed before the immersion step using the acidic solution containing the phosphoric acid compound, but may be performed after the immersion step.
  • the method for reducing lead elution of a 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.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un procédé de traitement destiné à réduire l'élution du plomb dans un alliage de cuivre contenant du plomb, caractérisé en ce qu'il consiste à immerger l'alliage de cuivre contenant du plomb dans une solution acide sans acide chromique et contenant de l'acide phosphorique ou un de ses dérivés, et à éliminer le plomb dans la partie de surface de l'alliage. L'invention concerne aussi des éléments d'adduction d'eau fabriqués à partir d'alliage de cuivre contenant du plomb et traités par ce procédé. Les éléments traités par ce procédé montrent une réduction effective satisfaisante de l'élution du plomb, ne se décolorent pas de façon importante, ce qui n'entraîne pas de réduction de la valeur commerciale due à la décoloration, seul s'étant produit un faible décapage dû à l'utilisation d'acide phosphorique ou de ses dérivés avec formation d'une couche mince de phosphate. On peut ajouter, en outre, du chlorure de sodium, l'alliage de cuivre contenant du plomb pouvant être immergé à l'avance dans un liquide alcalin de décapage afin d'éliminer le plomb en surface, la surface extérieure de l'alliage pouvant être recouvert par placage électrolytique d'un métal tel que le nickel-chrome.
PCT/JP2003/011093 2002-08-30 2003-08-29 Procede de traitement destine a reduire l'elution de plomb dans un alliage de cuivre contenant du plomb et elements d'adduction d'eau fabriques en alliage de cuivre contenant du plomb WO2004024987A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2004535893A JPWO2004024987A1 (ja) 2002-08-30 2003-08-29 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
AU2003257600A AU2003257600A1 (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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JP2002256207 2002-08-30
JP2002-256207 2002-08-30

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WO2004024987A1 true WO2004024987A1 (fr) 2004-03-25

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CN (1) CN1678768A (fr)
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Cited By (7)

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EP1548155A1 (fr) * 2002-09-09 2005-06-29 Kitz Corporation Procede pour empecher l'elution du plomb et/ou du nickel d'un materiau de tuyauterie en alliage de cuivre, par exemple d'une vanne ou d'un raccord de tuyau, et materiau de tuyauterie en alliage de cuivre, et fluide utilise pour le nettoyage de ce materiau de tuyauterie
WO2006035695A1 (fr) * 2004-09-28 2006-04-06 Hayakawa Valve Production Co., Ltd. Procédé de traitement de surface exempt de chrome hexavalent et matériau métallique à base de cuivre contenant du plomb exempt de chrome hexavalent
EP1722010A1 (fr) * 2004-03-05 2006-11-15 Kitz Corporation Procede pour empecher le lessivage par nickelage partir d'un quipement en alliage de cu ivre au contact d'un liquide , agent formateur d'un film de protection pour la prevention du lessivage par nickelage et produit nettoyant pour la prevention
JP2011012342A (ja) * 2009-06-01 2011-01-20 Inax Corp 鉛含有銅合金製水道用器具の製造方法及び処理方法
KR101782697B1 (ko) * 2015-12-11 2017-09-28 엄영호 중금속 오염방지층을 갖는 수도계량기 및 그 제조방법
JP2018092880A (ja) * 2016-07-05 2018-06-14 日本特殊陶業株式会社 セラミックヒータ
US11252790B2 (en) 2016-07-05 2022-02-15 Ngk Spark Plug Co., Ltd. Ceramic heater

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CN103143890A (zh) * 2013-03-04 2013-06-12 阮伟光 低铅铜合金卫浴器具的制造方法
JP6599475B2 (ja) * 2015-11-11 2019-10-30 Ｙｋｋ株式会社 ファスナーストリンガー及びその製造方法、並びにスライドファスナー
CN106086894B (zh) * 2016-06-23 2018-06-19 台州德尊洁具厂(普通合伙) 一种水龙头主体除铅工艺及水龙头主体的加工工艺

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EP1038990A1 (fr) * 1997-12-03 2000-09-27 Toto Ltd. Procede attenuant l'elution du plomb des alliages de cuivre contenant du plomb, et accessoires de distribution d'eau de ville faits en alliage de cuivre contenant du plomb

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JPS6324074A (ja) * 1986-07-17 1988-02-01 Nippon Denso Co Ltd 銅系金属の化成処理浴組成物
EP1038990A1 (fr) * 1997-12-03 2000-09-27 Toto Ltd. Procede attenuant l'elution du plomb des alliages de cuivre contenant du plomb, et accessoires de distribution d'eau de ville faits en alliage de cuivre contenant du plomb

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1548155A4 (fr) * 2002-09-09 2005-11-23 Kitz Corp Procede pour empecher l'elution du plomb et/ou du nickel d'un materiau de tuyauterie en alliage de cuivre, par exemple d'une vanne ou d'un raccord de tuyau, et materiau de tuyauterie en alliage de cuivre, et fluide utilise pour le nettoyage de ce materiau de tuyauterie
EP1548155A1 (fr) * 2002-09-09 2005-06-29 Kitz Corporation Procede pour empecher l'elution du plomb et/ou du nickel d'un materiau de tuyauterie en alliage de cuivre, par exemple d'une vanne ou d'un raccord de tuyau, et materiau de tuyauterie en alliage de cuivre, et fluide utilise pour le nettoyage de ce materiau de tuyauterie
US8182879B2 (en) 2004-03-05 2012-05-22 Kitz Corporation Method for preventing elution of nickel from water-contact instrument of copper alloy by formation of a protective film
EP1722010A1 (fr) * 2004-03-05 2006-11-15 Kitz Corporation Procede pour empecher le lessivage par nickelage partir d'un quipement en alliage de cu ivre au contact d'un liquide , agent formateur d'un film de protection pour la prevention du lessivage par nickelage et produit nettoyant pour la prevention
JPWO2005085500A1 (ja) * 2004-03-05 2008-04-24 株式会社キッツ 銅合金製接液器材のニッケル溶出防止方法及びニッケル溶出防止用保護膜形成剤並びにニッケル溶出防止用洗浄剤
EP1722010A4 (fr) * 2004-03-05 2010-02-24 Kitz Corp Procede pour empecher le lessivage par nickelage a partir d'un equipement en alliage de cuivre au contact d'un liquide , agent formateur d'un film de protection pour la prevention du lessivage par nickelage et produit nettoyant pour la prevention
WO2006035695A1 (fr) * 2004-09-28 2006-04-06 Hayakawa Valve Production Co., Ltd. Procédé de traitement de surface exempt de chrome hexavalent et matériau métallique à base de cuivre contenant du plomb exempt de chrome hexavalent
JP2011012342A (ja) * 2009-06-01 2011-01-20 Inax Corp 鉛含有銅合金製水道用器具の製造方法及び処理方法
KR101782697B1 (ko) * 2015-12-11 2017-09-28 엄영호 중금속 오염방지층을 갖는 수도계량기 및 그 제조방법
JP2018092880A (ja) * 2016-07-05 2018-06-14 日本特殊陶業株式会社 セラミックヒータ
KR20190025670A (ko) * 2016-07-05 2019-03-11 니혼도꾸슈도교 가부시키가이샤 세라믹 히터
KR102229299B1 (ko) * 2016-07-05 2021-03-17 니혼도꾸슈도교 가부시키가이샤 세라믹 히터
US11252790B2 (en) 2016-07-05 2022-02-15 Ngk Spark Plug Co., Ltd. Ceramic heater

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