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WO2002036856A1 - Procede d'enlevement du plomb d'article cylindrique plaque en alliage de cuivre contenant du plomb et article metallique pour prise d'eau, procede pour empecher la dissolution du plomb d'un article en alliage de cuivre contenant du plomb et article metallique pour prise d'eau - Google Patents

Procede d'enlevement du plomb d'article cylindrique plaque en alliage de cuivre contenant du plomb et article metallique pour prise d'eau, procede pour empecher la dissolution du plomb d'un article en alliage de cuivre contenant du plomb et article metallique pour prise d'eau

Info

Publication number
WO2002036856A1
WO2002036856A1 PCT/JP2001/009488 JP0109488W WO0236856A1 WO 2002036856 A1 WO2002036856 A1 WO 2002036856A1 JP 0109488 W JP0109488 W JP 0109488W WO 0236856 A1 WO0236856 A1 WO 0236856A1
Authority
WO
WIPO (PCT)
Prior art keywords
lead
copper alloy
peripheral surface
containing copper
work
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2001/009488
Other languages
English (en)
Japanese (ja)
Inventor
Takeshi Mizutani
Takeshi Nishikawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Inax Corp
Original Assignee
Inax Corp
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.)
Filing date
Publication date
Application filed by Inax Corp filed Critical Inax Corp
Priority to AU2001296025A priority Critical patent/AU2001296025A1/en
Priority to JP2002539591A priority patent/JP3866198B2/ja
Publication of WO2002036856A1 publication Critical patent/WO2002036856A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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

Definitions

  • the present invention relates to a method for removing lead from a lead-containing copper alloy plated product having a cylindrical portion, a metal fitting, a method for preventing lead leaching of a lead-containing copper alloy product, and a faucet fitting.
  • the first invention relates to a method for removing lead from a plated product made of a lead-containing copper alloy having a cylindrical portion and a faucet fitting.
  • the second invention relates to a method for preventing lead leaching of a lead-containing copper alloy product and a faucet fitting.
  • the method for preventing lead leaching of lead-containing copper alloy products of the second invention is suitable for use in the manufacturing method of faucet fittings.
  • copper alloys such as bronze and brass are used for faucet fittings and water supply appliances such as water pipes from the viewpoint of corrosion resistance. Copper alloys are used.
  • the lead-containing copper alloy constituting the faucet fitting is first cut and then cut to form a work for the faucet fitting having a cylindrical portion through which water passes.
  • the work is provided with a nickel-chrome plating layer by the nickel-chrome plating method mainly from the viewpoint of decorativeness, and is used as a faucet fitting.
  • a general nickel-chromium plating method includes a pretreatment step S1 in which pretreatment is performed in such a short time, and a nickel plating on the outer peripheral surface of the workpiece after the pretreatment step S1.
  • a plating step S2 for applying a chrome plating layer is provided.
  • the pretreatment step S1 has a degreasing step S11 for immersing the work in an alkaline solution to degrease the entire surface of the work.
  • the alkaline liquid used here is usually an alkaline aqueous solution in which sodium hydroxide or the like is dissolved in water. If the work is immersed in this liquid, degreasing is performed according to the pH of the liquid. Note that lead is also removed by etching according to the pH of the alkaline solution.
  • the pre-treatment step S 1 includes, in addition to the degreasing step S 11, a cathodic electrolysis step S 12 for further degreasing the entire surface of the work using the work as a cathode in an alkaline solution, and cleaning the work with an acid solution Acid activation step S13 to activate the entire surface of the workpiece by Washing step performed.
  • the plating step S 2 includes a nickel plating step S 21 in which a nickel plating layer is applied to the outer peripheral surface of the work after the pre-treatment step S 1 using a nickel plating bath, and a nickel plating step using a chrome plating bath.
  • the method may include a chrome plating step S22 for applying a chrome plating layer to the outer peripheral surface of the work after the step S21, and a water washing step provided between these steps.
  • the faucet fitting thus obtained is used by passing water through the tubular part. Disclosure of the invention
  • the first invention has been made in view of the above-mentioned conventional circumstances, and is intended to reduce the amount of lead eluted from the inner peripheral surface of the cylindrical portion into water, to provide an excellent aesthetic appearance, and to be inexpensive to manufacture.
  • the problem to be solved is to provide a lead removal method that can provide You.
  • the first invention has a problem to be solved to provide a faucet fitting that reduces the amount of lead eluted into water, has an excellent appearance, and can be manufactured at low cost.
  • the lead removal method for a lead-containing copper alloy plated product having a cylindrical portion comprises a plating step of forming a plating layer on an outer peripheral surface of a lead-containing copper alloy work having a cylindrical portion through which water passes.
  • the plated product is subjected to a lead removal step of removing lead from the peripheral surface of the cylindrical portion.
  • the lead removal step is performed after the plating step, the outer peripheral surface of the work is protected by the plating layer so that lead is not removed, and lead is removed only from the inner peripheral surface of the work without the plating layer. Will be removed. For this reason, the outer peripheral surface of the workpiece does not have irregularities and the plating layer is not damaged, so that the outer peripheral surface of the plated product has excellent surface properties. For this reason, the plated product has an excellent appearance.
  • the faucet of the first invention as a plated product can be obtained.
  • the faucet fitting includes a base material portion made of a lead-containing copper alloy having a cylindrical portion through which water passes, and a base material portion formed integrally with the base material portion on an outer peripheral surface side of the cylindrical portion, and a lead concentration of the base material portion is reduced.
  • a lead-containing layer that is substantially equal to the material portion, a puck layer formed on the outer peripheral surface side of the lead-containing layer, and an integral part of the base material portion on the inner peripheral surface side of the tubular portion, and the concentration of lead is reduced. It is characterized by comprising a lower, lower opening, and containing layer than the base material.
  • the concentration of lead contained in the low-lead-containing layer on the inner peripheral surface side of the cylindrical portion is low, even when water passes through the inner peripheral surface, lead is eluted into the water. hard. Therefore, when a person drinks water supplied from the faucet, it is possible to eliminate concerns about harm to human health. Also, if the water is discharged into rivers and sewage, the impact on the environment can be reduced.
  • a lead-containing layer is present on the outer peripheral surface side of the cylindrical portion with a lead concentration substantially equal to that of the base material portion, and the lead-containing layer is attached to the outer peripheral surface side of the lead-containing layer. Since the layer was formed, there was no unevenness in the lead-containing layer, and the appearance of the faucet was excellent. Furthermore, in the water faucet fitting of the first invention, it is not necessary to increase the thickness of the plating layer, so that it can be manufactured at low cost.
  • the lead removal method of the first invention preferably includes a passivation step of passivating the inner peripheral surface of the cylindrical portion after the lead removal step.
  • a passivation step of passivating the inner peripheral surface of the cylindrical portion after the lead removal step since the inner peripheral surface is passivated by the passivation step, the amount of lead eluted from the low lead content layer can be further reduced.
  • the lead removing step can be performed by immersing the lead in the inner peripheral surface of the cylindrical portion in an etchant capable of etching lead.
  • an etchant capable of etching lead.
  • the etchant causes a chemical reaction with the lead on the inner peripheral surface, and the lead can be dissolved and removed.
  • an acidic solution or an alkaline solution as the etching solution. Copper reacts with acids, whereas lead, which is an amphoteric metal, reacts with both acids and alkalis. Therefore, it is preferable to use an alkaline solution as an etching solution.
  • an active solution refers to a liquid having a pH in the range of 12 to 14.
  • an active alkali solution is mainly an aqueous solution of sodium carbonate, sodium hydroxide, sodium phosphate, sodium metasilicate, sodium tripolyphosphate, sodium orcayte, hydroxylated water, or the like.
  • Such an etching solution preferably contains a surfactant. If the etching liquid contains a surfactant, the surface tension of the etching liquid can be reduced, so that the permeability and wettability of the etching liquid to the inner peripheral surface of the cylindrical portion can be improved. Therefore, a chemical reaction occurs between the lead contained in the inner peripheral surface and the etching solution.
  • an ionic surfactant and a nonionic surfactant can be used.
  • anionic surfactant for example, sodium higher fatty acid, sulfated oil, sodium higher alcohol sulfate, sodium alkyl benzene sulfate, sodium higher alkyl ether sulfate, sodium sodium olefin sulfate, and the like can be used.
  • non-one surfactant include alkyl polyoxyethylene ether and alkyl phenyl polyoxyethylene ester. Monoter, fatty acid ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, and the like can be used.
  • a chelating agent in the etching solution. Since the chelating agent causes a chemical reaction with lead to form a water-soluble complex, it is possible to easily remove lead contained in the inner peripheral surface of the cylindrical portion.
  • chelating agent for example, ethylenediamine, thiourea, tartaric acid, Rossiel salt, EDTA, triethanolamine and the like can be used.
  • etching solution it is preferable to include an oxidizing agent in the etching solution. That is, if it is attempted to remove lead contained in the inner peripheral surface of the cylindrical portion only with an etching solution that is an active alkaline solution, lead will be dissolved by the following chemical reaction.
  • the oxidizing agent firstly undergoes a chemical reaction with lead as shown in the following Chemical Formula 2 to form lead oxide.
  • the lead oxide is dissolved in the etching solution, which is an active solution, and undergoes a chemical reaction shown in the following chemical formula 3, thereby forming a lead acid salt.
  • the oxidizing agent contained in the etching solution which is an active alkaline solution, is more likely to be present on the inner peripheral surface of the cylindrical portion. The removal of the contained lead can be facilitated.
  • oxidizing agent for example, sodium metabenzene benzenesulfonate, sodium paranitrobenzoate, hypochlorite, bleaching powder, hydrogen peroxide, potassium permanganate, persulfate, perchlorate, etc. are used. can do.
  • the plating step includes a chromium plating step using a chromium plating bath containing chromic acid
  • the passivation step includes immersing the coat in a chromate solution containing chromic acid. It is preferable to have a processing step.
  • chromic acid in the chromium plating bath causes a chemical reaction between chromic acid and lead as shown in the following Chemical Formula 4 to form lead chromate.
  • Lead chromate is passive because of its poor solubility. Therefore, lead does not elute from the outer peripheral surface of the work.
  • the chromate in the chromite solution causes the chemical reaction of the chromate and lead with the above chemical formula 4 to form lead chromate.
  • the lead slightly contained in the inner peripheral surface of the cylindrical portion of the work does not elute.
  • excellent workability is exhibited because chromic acid is used in both.
  • Such click port formate process with chromate film by the chemical reaction of the following Chemical Formula 5 to Chemical Formula 7 to the inner peripheral surface of the cylindrical portion (xC r 2 0 3 'yC r 0 3' zH 2 0) is formed.
  • a chromate film is formed on the inner peripheral surface of the low lead content layer, so that lead remaining on the inner peripheral surface of the cylindrical portion is passivated by the chromate film and melted. It becomes difficult to put out.
  • chromate solution for example, a solution containing sulfuric acid or the like in addition to chromic acid can be employed. Further, those obtained by adding chromate, oxalic acid, acetic acid, hydrofluoric acid, nitric acid and the like to these can also be employed. Further, the chromating agent used for zinc plating or the like may be a chromate solution.
  • the chromium plating bath used in the first invention preferably contains a fluoride. This is because the lead chromate formed in the chrome plating bath may be dissolved by the fluoride.
  • the chromate solution used in the first invention preferably contains phosphoric acid. This is because chromic acid and phosphoric acid are thought to effectively promote the chemical reaction of dissolving lead and the chemical reaction of forming a chromate film. Therefore, lead contained in the inner peripheral surface of the cylindrical portion can be effectively dissolved, and a chromate film can be effectively formed on the inner peripheral surface.
  • ammonium phosphate, phosphate ester, potassium phosphate, calcium phosphate, iron phosphate, tri-n-butyl phosphate, tricresinole phosphate, triphenyl phosphate, sodium triphosphate, sodium phosphate Employs ammonium hydrogen phosphate, potassium dihydrogen phosphate, magnesium phosphate, magnesium ammonium phosphate, lithium phosphate, phospholipid, phosphor bronze, phosphorous stannate, phosphotungstate, phosphomolybdate, phosphomolybdate, etc. It is considered possible.
  • the low lead content layer does not contain lead. If lead is not contained in the low-tin-containing layer, lead does not elute into water passing through the inner peripheral surface, and lead on the inner side rarely elutes through the low-lead-containing layer. ⁇ Second invention ⁇
  • the second invention has been made in view of the above-mentioned conventional circumstances, and prevents lead leaching of a lead-containing copper alloy product that can easily reduce the amount of lead leached into water from the lead-containing copper alloy product. Providing a method is an issue to be solved. In addition, the second invention has a problem to be solved particularly to provide a faucet fitting which can reduce the amount of lead leached into water and can be easily manufactured.
  • the present inventors have conducted trial and error research to solve the above-mentioned problems, and if a work made of a lead-containing copper alloy is immersed in a treatment solution such as a phosphoric acid aqueous solution, a phosphorus-containing film is formed on the surface of the work. As a result, they discovered that the above problem could be solved and completed the second invention.
  • a work made of a lead-containing copper alloy and a treatment liquid in which phosphoric acid or a phosphate is mainly added to water are prepared.
  • the film formed in the film forming step prevents lead leaching.
  • the coating may, for example, when using a treatment liquid composed mainly of the first zinc phosphate (Z n (H 2 P 0 4) 2) and phosphoric acid (H 3 P 0 4), as follows It is considered to be generated.
  • lead may be dissolved in the treatment liquid by phosphoric acid to generate lead ions.
  • part of the zinc monophosphate is dissociated in the treatment liquid.
  • a treatment liquid obtained by adding phosphoric acid or phosphate mainly to water is used, and the phosphoric acid or phosphate is used for forming a chromium plating layer.
  • chromium plating bath containing chromic acid composed of hexavalent chromium or chromate solution containing chromic acid for passivation it is possible to dispose of the cleaning liquid and the waste liquid only by neutralizing and diluting the cleaning liquid and the waste liquid after the contact with the processing liquid. Therefore, the management of the cleaning liquid and the like becomes simpler than the disposal of a chromate solution containing chromic acid as disclosed in JP-A-2000-96269-JP-A-2000-96270.
  • a phosphorus pentoxide (P 2 0 5) is hydrated to varying degrees of arising a series of acid (P 2 O 5 ⁇ nH 2 O).
  • P 2 O 5 ⁇ nH 2 O For example, orthophosphoric acid (H 3 P0 4 (0. 5 P 2 0 5 - 1. 5 H 2 O)), metaphosphate (HP_ ⁇ 3 (0. 5 P 2 O s - 0. 5 H 2 0)) And so on.
  • the phosphate according to the second invention includes zinc phosphate, manganese phosphate, Iron phosphate, zinc phosphate and calcium phosphate can be used.
  • sodium phosphate NaH 2 P_ ⁇ 4, Na 2 HPO 4, etc.
  • phosphoric acid Al Miniumu A l (H 2 P0 4 ) 3 , etc.
  • ammonium phosphate - ⁇ beam NH 4 H 2 P0 4 or the like ) And so on.
  • the concentration of phosphoric acid or phosphate in the treatment liquid in the second invention is preferably 0.01 to 10.0% by mass. According to the experimental results of the inventors, it was found that when the concentration of phosphoric acid or phosphate was 0.01 to 10.0% by mass, a film containing phosphorus was easily formed on the surface of the work.
  • the lead leaching prevention method of the second invention it is preferable to perform a lead removal step of removing lead from the surface of the work before the film formation step.
  • a lead removal step of removing lead from the surface of the work before the film formation step it is preferable to perform a lead removal step of removing lead from the surface of the work before the film formation step.
  • the lead removal step can be performed by immersing lead in an etching solution capable of being etched. This is because the etchant causes a chemical reaction with lead on the surface of the work, and can dissolve and remove the lead.
  • an acidic solution or an alkaline solution as the etching solution.
  • copper reacts with an acid
  • lead which is an amphoteric metal
  • an active solution is an alkaline solution having a pH in the range of 12 to 14. According to the active alkaline solution having a pH in this range, the active alkaline solution causes a chemical reaction with lead on the surface, so that the lead is easily dissolved and removed.
  • Such an active alkali solution is mainly an aqueous solution of sodium carbonate, sodium hydroxide, sodium phosphate, sodium metasilicate, sodium tripolyphosphate, sodium oleate, potassium hydroxide, or the like.
  • Such an etching solution preferably contains a surfactant. If the etching liquid contains a surfactant, the surface tension of the etching liquid can be reduced, so that the permeability and wettability of the etching liquid to the surface can be improved. Therefore, a chemical reaction occurs between the lead contained in the surface and the etching solution.
  • a surfactant an anionic surfactant / nonionic surfactant can be used.
  • anionic surfactant for example, sodium higher fatty acid, sulfated oil, sodium higher alcohol sulfate, sodium alkyl benzene sulfate, sodium higher alkyl ether sulfate, sodium sodium olefin sulfate and the like can be used.
  • nonionic surfactants include, for example, anolequinole polyoxyethylene ether, anole kiln phenylene polyoxyethylene ether, fatty acid ethylene oxide adduct, and polypropylene glycol ethylene oxide adduct. Can be adopted.
  • a chelating agent in the etching solution. Since the chelating agent chemically reacts with lead to form a water-soluble complex, it is possible to easily remove lead contained on the surface.
  • chelating agent for example, ethylenediamine, thiourea, tartaric acid, Rossiel salt, EDTA, triethanolamine and the like can be used.
  • etching solution it is preferable to include an oxidizing agent in the etching solution.
  • an oxidizing agent in the etching solution.
  • the oxidizing agent firstly undergoes a chemical reaction with lead as shown in the following Chemical Formula 15 to form lead oxide.
  • the lead oxide dissolves in the etching solution, which is an active alkali solution, and undergoes a chemical reaction shown in the following Chemical Formula 16 to form a lead oxide salt.
  • oxidizing agent for example, sodium metabenzene benzenesulfonate, sodium para-benzoate, hypochlorite, bleaching powder, hydrogen peroxide, potassium permanganate, persulfate, perchlorate, etc. are used. can do.
  • the lead leaching prevention method of the second invention has a particularly advantageous effect when the workpiece is plated with a nickel-chromium plating layer on the outer peripheral surface and a lead removal step is performed on the plating product. That is, the lead removal step is performed in a state where the outer peripheral surface of the plated workpiece is protected by the nickel-chromium plating layer. For this reason, the work is not affected at all on the outer peripheral surface, and lead is removed only from the inner peripheral surface without the nickel-chromium plating layer. For this reason, no irregularities occur on the outer peripheral surface of the work, and the nickel 'chrome plating layer is not impaired, so that the outer peripheral surface of the plated product has excellent surface properties. For this reason, the product has an excellent appearance.
  • the faucet fitting of the second invention comprises a base material portion made of a lead-containing copper alloy having a cylindrical portion through which water passes, and at least an inner peripheral surface side of the cylindrical portion formed integrally with the base material portion. And a film containing phosphorus.
  • a treatment liquid to which phosphoric acid or a phosphate is mainly added is used as the treatment liquid, so that the management of the cleaning liquid and the like can be simplified, and the production cost can be reduced.
  • the faucet fitting of the second invention is integrated with the base material on the outer peripheral surface side of the cylindrical portion, and the lead concentration is reduced.
  • a lead-containing layer that is approximately equal to the base material, a nickel-chromium plating layer formed on the outer peripheral surface of the lead-containing layer, and a lead concentration that is integrated with the base material on the inner peripheral surface of the cylindrical portion. May have a low lead content layer lower than the base material portion, and the film may be formed on the surface of the low lead content layer. Accordingly, a low-lead-containing layer having a low lead concentration can be formed on the inner peripheral surface side of the cylindrical portion, so that it is possible to further prevent leaching of lead from the work.
  • FIG. 1 is a process chart of a plating method according to Example 1 of the first invention.
  • FIG. 2 is a cross-sectional view of the faucet obtained by the mounting method according to the first embodiment of the first invention.
  • FIG. 3 is a process chart of a plating method according to Example 2 of the first invention.
  • FIG. 4 is a process chart of a plating method according to Example 3 of the first invention.
  • FIG. 5 is a process chart of a plating method according to Example 4 of the first invention.
  • FIG. 6 is a cross-sectional view of the faucet obtained by the mounting method of Example 4 of the first invention.
  • FIG. 7 is a perspective view of the faucet fitting of the first invention.
  • FIG. 8 is a process chart of a method for preventing lead leaching according to Example 1 of the second invention.
  • FIG. 9 is a cross-sectional view of a faucet obtained by the lead leaching prevention method of Example 1 of the second invention.
  • FIG. 10 is a process diagram of a lead leaching prevention method according to Embodiment 2 of the second invention.
  • FIG. 11 is a cross-sectional view of a water faucet obtained by the lead leaching prevention method of Example 2 of the second invention.
  • FIG. 12 is a perspective view of the faucet fitting.
  • FIG. 13 is a process diagram of a nickel-chromium plating method according to a conventional technique.
  • the lead removal method is embodied as a part of the nickel / chrome plating method.
  • this plating method as shown in Fig. 7, first, a peak 50a for a faucet metal obtained by cutting a forged lead-containing copper alloy of JISCAC 406 (six kinds of bronze) is obtained. prepare. This work 50a has a cylindrical portion 10 (see Fig. 2) through which water passes. Then, as shown in FIG. 1, a pre-treatment step S1 for pre-treating the work 50a, and after this pre-treatment step S1, a nickel-chrome plating layer is applied to the outer peripheral surface of the work 50a. A process S2 and a lead removal process S3 for removing lead of the work 50a after the attachment process S2 are sequentially performed.
  • the pretreatment step S 1 is provided between the degreasing step S 11, the cathodic electrolysis step S 12, and the acid activation step S 13, similarly to the general method shown in FIG. 13. Washing process (not shown).
  • the degreasing step S11 the work 50a is immersed in an alkaline solution of pH 11 for 5 minutes to degrease the entire surface of the work 50a.
  • This alkaline solution is an aqueous solution containing sodium hydroxide, a few gZl, and a surfactant, a chelating agent, and an oxidizing agent, and its temperature is 40 ° C.
  • the entire surface of the work 50a is further degreased by using the work 50a as a cathode in the same alkaline solution.
  • the acid activation step S13 the work 50a is washed with a sulfuric acid aqueous solution at pH 2 at room temperature to activate the entire surface of the work 50a. Note that, between these steps S11 to S13, the work 50a is washed with water as a washing step (not shown).
  • the plating step S2 also has a nickel plating step S21 and a chrome plating step S22, as in the general plating method shown in FIG.
  • a nickel plating layer is applied to the outer peripheral surface of the work 50a using a nickel plating bath.
  • a chromium plating layer is applied to the outer peripheral surface of the work 50a after the nickel plating step S21 using a chromium plating bath.
  • the chromium plating bath contains 5 to 10 g / 1 sodium sodium fluoride as a fluoride.
  • chrome plating step S22 chromic acid in the chromium plating bath causes a chemical reaction between the chromic acid and lead, and lead contained in the inner peripheral surface of the cylindrical portion 10 is removed. At this time, it is formed in a chrome plating bath. It is believed that the lead chromate dissolved is dissolved by the fluoride. Note that between these steps S21 and S22, the work 50a is washed as a washing step (not shown).
  • a lead removing step S3 is provided.
  • the workpiece 50a after the plating step S2 is immersed in a pH4 etching solution as an active alkaline solution for 10 minutes.
  • This etching solution is an aqueous solution containing 50 g Zl of sodium hydroxide, and its temperature is 50 ° C.
  • the etchant causes a chemical reaction with the lead on the inner peripheral surface of the cylindrical portion 10, and dissolves and removes the lead.
  • the etching solution is an active alkali solution, copper of the lead-containing copper alloy does not react, but only lead reacts.
  • the work 50a is also washed with water as a washing step (not shown) before and after the lead removing step S3.
  • the faucet fitting 50 of Example 1 shown in FIG. 7 is obtained as a plated product by the plating method of Example 1.
  • the faucet fitting 50 includes a base material 30 made of a lead-containing copper alloy having a tubular portion 10 through which water passes, and a base material on the outer peripheral surface side of the tubular portion 10.
  • Part 30 and a tin-containing layer 30 a having a lead concentration substantially equal to that of the base material part 30, and a nickel-chrome plating layer 20 formed on the outer peripheral surface side of the lead-containing layer 30 a
  • a low-lead-containing layer 30 b that is integrated with the base material 30 on the inner peripheral surface side of the cylindrical portion 10 and has a lower lead concentration than the base material 30.
  • This faucet fitting 50 is used by passing water W through the cylindrical portion 10.
  • the plating method of Comparative Example 1 is a general nickel-chromium plating method shown in FIG. 13, and is different from the plating method of Example 1 in that a lead removal step S 3 is performed after the plating step S 2. That is not. Other conditions are the same as in Example 1.
  • the plating method of Comparative Example 2 is the same as the general method of plating with nickel and chromium shown in FIG. 13 except that in a degreasing step S11, the substrate is simply immersed in a high pH alkaline solution. Yes, as in Comparative Example 1, the lead removal step S3 was not performed after the plating step S2.
  • the alkaline solution used in the degreasing step S11 contained 50 g, l of sodium hydroxide, 2 g / 1 of sodium alkylbenzene sulfonate as a surfactant, and 2 g / 1 of EDTA as a chelating agent.
  • Example 1 and Comparative Examples 1 and 2 were dissolved in water passing through the cylindrical part 10 by JISS 3200-7 (1997) "Test method for leaching performance of water supply equipment".
  • the lead concentration (ppb) was measured, and the surface properties of the nickel-chromium plating layer 20 were visually checked. Table 1 shows the results.
  • the faucet fitting 50 of Comparative Example 1 has good surface properties of the nickel chromium plating layer 20, but does not perform the lead removal step S3 after the plating step S2 in the plating method. It can be seen that the concentration of eluted lead is high.
  • the concentration of the eluted lead is extremely low, and the surface of the nickel / chrome plating layer 20 is formed. It can be seen that the properties are also good. This is the plating method of Example 1.
  • the outer peripheral surface of the work 50a is nickel.
  • the lead is not removed because the lead is not removed by the chrome plating layer 20 and the nickel-chrome plating layer This is because lead is removed only from the inner peripheral surface of the workpiece 50a without 20. Therefore, the outer peripheral surface of the work piece 50a has no unevenness, and the nickel-chrome plating layer 20 is not damaged, so that the outer peripheral surface of the faucet fitting 50 has excellent surface properties. It has an excellent aesthetic.
  • the amount of lead eluting into the water from the inner peripheral surface of the cylindrical portion 10 is reduced, and an excellent aesthetic appearance is produced, and an inexpensive faucet fitting 50 is manufactured. We can see that we can do it.
  • Example 2 According to the plating method of Example 2, as shown in FIG. 3, the lead removal process S was performed for the common faucet 50 as a stock obtained by the chrome plating process shown in FIG. Have done three. Other conditions are the same as in Example 1.
  • the faucet fitting 50 of the stock which has been in compliance with the standard for elution of lead in the past can be replaced with the same faucet fitting 50 of the first working example. Therefore, this plating method can meet the new lead elution standards with almost no special design changes in the factory. For this reason, there is an effect that the production cost does not increase to meet the standards.
  • the lead removing step S3 is performed again on the faucet fitting 50 obtained in the first embodiment.
  • Other conditions were the same as in Example 1. The same is true.
  • a chromate treatment step S4 as a passivation step is performed after the lead removal step S3.
  • the workpiece 50a after the lead removal step S3 is immersed in a chromate solution for one minute.
  • This chromate solution is an aqueous solution containing 20 to 100 g Zl of chromic anhydride and 10 g Zl of phosphoric acid, and its temperature is room temperature.
  • Other configurations are the same as in the first embodiment.
  • chromic acid in the chromate solution causes a chemical reaction between the chromic acid and lead, and lead contained in the inner peripheral surface of the cylindrical portion 10 is further removed. At this time, it is considered that chromic acid and phosphoric acid effectively promote the chemical reaction of dissolving lead and the chemical reaction of forming chromate film 40 (see FIG. 6).
  • chromic acid and phosphoric acid effectively promote the chemical reaction of dissolving lead and the chemical reaction of forming chromate film 40 (see FIG. 6).
  • excellent workability is exhibited since both use chromic acid.
  • the faucet fitting 50 of Example 4 obtained in this manner has a base material portion 30 made of a lead-containing copper alloy having a tubular portion 10 through which water passes, and a tubular portion 10.
  • the lead-containing layer 30a is formed integrally with the base material portion 30 on the outer peripheral surface side and has a lead concentration substantially equal to that of the base material portion 30, and nickel formed on the outer peripheral surface side of the lead-containing layer 30a
  • Low chromium-plated layer 20 and low-lead-containing layer 30 b that are integrated with base metal part 30 on the inner peripheral surface side of cylindrical part 10 and have a lower lead concentration than base metal part 30
  • Example 1 In the lead leaching prevention method of Example 1, first, two types of lead-containing copper alloys of the following materials 1 and 2 are prepared.
  • Material 1 is bronze consisting of 5% by mass of lead, 85% by mass of copper, 5% by mass of zinc, and 5% by mass of tin.
  • Material 2 is brass composed of 2% by mass of lead, 63% by mass of copper, and 35% by mass of zinc.
  • each work 50a for faucet fittings is obtained by cutting these lead-containing copper alloy ingots.
  • the work 50a has a cylindrical portion 10 through which water passes as shown in FIG.
  • a plating step S2 to be applied and a film forming step S3 for forming a phosphorus-containing film on the surface of each work 50a after the plating step S2 are sequentially performed.
  • the pretreatment step S 1 is provided between the degreasing step S 11, the cathodic electrolysis step S 12, and the acid activation step S 13, similarly to the general plating method shown in FIG. Washing step (not shown).
  • each work 50a is immersed in an alkaline solution of pH 11 for 5 minutes to degrease the entire surface of each work 50a.
  • This alkaline solution is an aqueous solution containing sodium hydroxide, a few gZl, and a surfactant, a chelating agent, and an oxidizing agent, and its temperature is 40 ° C.
  • each work 50a is further degreased by using each work 50a as a cathode in the same alkaline solution.
  • each work 50a is washed with a sulfuric acid aqueous solution of pH: 2 at room temperature to activate the entire surface of each work 50a.
  • each work 50a is washed with water as a washing step (not shown).
  • the plating step S2 is the same as the general plating method shown in FIG. It has a nickel plating step S21 and a chrome plating step S22.
  • a nickel plating layer is applied to the outer peripheral surface of each work 50a using a nickel plating bath.
  • a chrome plating layer is applied to the outer peripheral surface of each workpiece 50a after the nickel plating step S21 using a chromium plating bath.
  • the chrome plating bath contains sodium fluoride of 5 to 10 g / 1 as a fluoride.
  • chrome plating step S22 chromic acid in the chromium plating bath causes a chemical reaction between chromic acid and lead, and lead contained in the inner peripheral surface of the cylindrical portion 10 is removed. At this time, it is considered that lead chromate formed in the chromium plating bath is dissolved by the fluoride.
  • each work 50a is washed with water as a washing step (not shown).
  • a film forming step S3 is provided.
  • the workpiece 50a after the plating step S2 is immersed in the processing liquid for 10 minutes.
  • the treatment liquid, phosphoric acid (H 3 P 0 4) is zero. 9 mass% aqueous solution, the temperature is 5 0 ° C.
  • the treatment liquid reacts with copper and / or lead on the inner peripheral surface of the cylindrical portion 10 to form a phosphorus-containing film 40 on the inner peripheral surface of the cylindrical portion 10.
  • each work 50a is also washed as a washing step (not shown).
  • each faucet fitting 50 shown in FIG. 12 is obtained as a plated product.
  • each of the faucet fittings 50 has a base member 30 made of a lead-containing copper alloy having a tubular portion 10 through which water passes, and a base member 30 on the outer peripheral surface side of the tubular portion 10.
  • a lead-containing layer 30a which is formed integrally with the material part 30 and has a concentration of approximately equal to that of the base material part 30, and a nickel-chrome plating layer 20 formed on the outer peripheral surface side of the lead-containing layer 30a
  • the lead-containing layer 30b and the lead-containing layer 30b are formed integrally with the base material 30 on the inner peripheral side of the cylindrical portion 10 and have a lead concentration substantially equal to that of the base material 30.
  • a film 40 containing phosphorus formed on the inner peripheral surface side.
  • Each faucet fitting 50 is used by passing water W through the cylindrical portion 10. '
  • each work 50a for the faucet fitting shown in FIG. 12 was formed from the two types of lead-containing copper alloys of Materials 1 and 2. Get.
  • each workpiece 50a is located between the plating step S2 and the film forming step S3.
  • a lead removal step S4 for removing lead is provided and the processing time of the film formation step S3 is different.
  • each workpiece 50a after the plating step S2 is immersed in an etching solution of pH 4 as an active solution for 3 minutes.
  • the etching solution is an aqueous solution of sodium hydroxide 5 wt 0/0, the temperature is 5 0 ° C.
  • the etching liquid causes a chemical reaction with the lead on the inner peripheral surface of the cylindrical portion 10, and dissolves and removes the lead.
  • the etching solution is an active alkaline solution, copper of the lead-containing copper alloy does not react, but only lead reacts.
  • each work 50a is washed with water as a washing step (not shown).
  • the workpiece 50a after the lead removing step S4 is immersed in the treatment liquid for 3 minutes.
  • Other conditions are the same as in Example 1.
  • each of the faucet fittings 50 shown in FIGS. 12A and 12B are obtained as plated products by the lead leaching prevention method of the second embodiment, similarly to the first embodiment.
  • each of the faucet fittings 50 includes a base member 30 made of a lead-containing copper alloy having a tubular portion 10 through which water passes, and an outer peripheral surface side of the tubular portion 10.
  • the lead-containing layer 30a has a lead concentration approximately equal to that of the base material 30 and a nickel-chromium plating formed on the outer peripheral side of the lead-containing layer 30a
  • Layer 20 and low-lead-containing layer 30 c that are integrated with base material 30 on the inner peripheral surface side of cylindrical portion 10 and have a lower lead concentration than base material 30, and low-lead-containing layer
  • each work 50a for faucet fittings shown in FIG. 12 was formed from two types of lead-containing copper alloys of materials 1 and 2, respectively. Get.
  • Comparative Example 1 the general nickel-chrome plating method shown in Fig. 13 was used. Only a nickel-chromium plating layer is applied, and no lead leaching prevention method is used. Other conditions are the same as in Example 1.
  • the respective workpieces 50a for the faucet fittings shown in FIG. 12 are obtained from the two types of lead-containing copper alloys of Materials 1 and 2. .
  • the lead leaching prevention method of Comparative Example 2 is different from the lead leaching prevention method of Example 2 shown in FIG. 10 in that the film forming step S3 is not provided. Further, in the lead removal step S4, each work 50a is also immersed in an etching solution having a pH of 14 as an active alkaline solution for 10 minutes, which is different from the second embodiment. Other conditions are the same as in the second embodiment.
  • the faucet fitting 50 of Comparative Example 2 performed the film forming step S3 after the plating step S2.
  • the concentration of the leached lead in the material 2 is low because the lead removal step S4 is performed.
  • the concentration of leached lead does not decrease much.
  • the faucet fitting 50 of Example 1 performs the film forming step S3 after the plating step S2, and thus shows that the concentration of leached lead is low in both the materials 1 and 2. .
  • Example 1 it can be seen that it is preferable to immerse each work 50a in the treatment liquid for a relatively long time in order to reduce the concentration of leached lead to some extent.
  • Example 2 since the faucet fitting 50 of Example 2 performs the lead removing step S4 and the film forming step S3 after the plating step S2, it can be seen that the concentration of leached lead is extremely low. Further, in Example 2, since the film forming step S3 is performed, it is sufficient to immerse each work 50a in the etching solution for 3 minutes in the lead removing step S4. That is, in Example 2, although both the lead removal step S4 and the film formation step S3 were performed, the total time required for these steps was 6 minutes. Since the required time is shorter than the required time of 10 minutes, it can be seen that Example 2 is excellent in workability.
  • the low concentration of lead leached in the faucet fittings 50 of Examples 1 and 2 is due to the phosphorus-containing skin formed on the inner peripheral surface of the cylindrical portion 10 in the film forming step S3. This is presumably because the film 40 can prevent the leaching of lead.
  • a treatment liquid obtained by mainly adding phosphoric acid or a phosphate to water is used.
  • the inner peripheral surface of the cylindrical portion 10 It can be seen that the amount of lead leached from the steel into the water is reduced, and an inexpensive faucet fitting 50 can be manufactured.
  • the phosphorus-containing film 40 formed on the inner peripheral surface of the cylindrical portion 10 can prevent the leaching of lead, the inner peripheral surface of Lead is hard to leach into the water. For this reason, it can be seen that when a person drinks the water supplied from the faucet fitting 50, concerns about harm to human health can be eliminated. It also shows that if the water is discharged into rivers and sewage, the impact on the environment can be reduced.
  • a plurality of works 50a for faucet fittings shown in FIG. 12 are obtained from the lead-containing copper alloy of material 3 shown below, as in Example 1.
  • Material 3 lead 5 wt%, 85 wt% copper, zinc 5 mass 0/0, a bronze consisting of tin 5 wt%.
  • these workpieces 50a were processed in the order of the pretreatment step S1, the plating step S2, the lead removal step S4, and the film formation step S3, as in Example 2.
  • the faucet fittings 50 of Samples 1 to 6 are obtained as a plated product.
  • the concentration (ppb) of lead leached into water passing through the inside of the cylindrical portion 10 was measured by the above-mentioned "Test method for leaching performance of water supply equipment".
  • processing conditions such as a phosphoric acid concentration (mass%), a processing solution temperature (° C.), and a processing time (second) are different.
  • Other conditions are the same as in Example 2.
  • Table 3 shows the results with the treatment conditions for the faucet fitting 50 of Sample 1 as standard.
  • Table 3 shows the following. From the data of the water ⁇ tool 5 0 sample 1-3, the concentration of phosphoric acid (H 3 P 0 4) 0 about 9% by weight is desired, 0 0 1 ⁇ :... LO 0 mass% between In this case, the concentration of leached lead does not change much, and a sufficient effect can be obtained.
  • the higher the temperature of the treatment liquid the better. It is clear that a sufficient effect can be obtained. Therefore, it can be seen that the method of the present invention can exert a sufficient effect even in winter or the like.
  • the amount of lead eluted from the inner peripheral surface of the cylindrical portion into the water is reduced, and an excellent appearance can be achieved, and an inexpensive plated product can be manufactured.
  • the amount of lead leached into water from a lead-containing copper alloy product can be easily reduced. For this reason, this method for preventing lead leaching can prevent the leaching of lead and reduce the manufacturing cost. Further, the faucet fitting of the second invention can reduce the amount of lead leached into water and can be easily manufactured.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Domestic Plumbing Installations (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • ing And Chemical Polishing (AREA)
  • Chemically Coating (AREA)

Abstract

L'invention concerne un procédé d'enlèvement du plomb d'un article plaqué en alliage de cuivre contenant du plomb, qui se décompose en une étape (S1) de pré-traitement consistant à soumettre à un pré-traitement une pièce à travailler (50a) en alliage de cuivre contenant du plomb et présentant une partie cylindrique (10) ; en une étape de placage (S2) consistant à plaquer la surface extérieure de ladite pièce à travailler (50a) par l'application d'une couche de nickel-chrome (20), après l'étape de pré-traitement ; et en une étape (S3) d'enlèvement du plomb, consistant à enlever le plomb de la surface intérieure de la partie cylindrique (10), après l'étape de placage (S2). Le procédé de l'invention peut être utilisé pour la production à faible coût d'un article plaqué en alliage de cuivre contenant du plomb, à faible taux de dissolution dans l'eau du plomb de la surface intérieure de sa partie cylindrique et présentant un aspect excellent.
PCT/JP2001/009488 2000-10-31 2001-10-29 Procede d'enlevement du plomb d'article cylindrique plaque en alliage de cuivre contenant du plomb et article metallique pour prise d'eau, procede pour empecher la dissolution du plomb d'un article en alliage de cuivre contenant du plomb et article metallique pour prise d'eau Ceased WO2002036856A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2001296025A AU2001296025A1 (en) 2000-10-31 2001-10-29 Method for removing lead from plated cylindrical article made of lead-containingcopper alloy and metal fitting for hydrant, and method for preventing leaching of lead from article made of lead-containing copper alloy and metal fitting for hydrant
JP2002539591A JP3866198B2 (ja) 2000-10-31 2001-10-29 筒状部をもつ鉛含有銅合金製のめっき製品の鉛除去方法及び水栓金具並びに鉛含有銅合金製品の鉛浸出防止方法及び水栓金具

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JP2000-332190 2000-10-31
JP2000332190 2000-10-31
JP2001-32006 2001-02-08
JP2001032006 2001-02-08

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CN (1) CN1274881C (fr)
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Cited By (6)

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WO2004081257A1 (fr) * 2003-03-14 2004-09-23 Inax Corporation Procede de fabrication d'un ustensile pour systeme d'eau potable, fait d'un alliage de cuivre contenant du plomb, ustensile moule et sans plomb pour systeme d'eau potable, et ustensile pour systeme d'eau potable
WO2005001160A1 (fr) * 2003-06-30 2005-01-06 Inax Corporation Procede de fabrication d'un systeme a eau a partir d'un alliage de cuivre contenant du plomb
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
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
JP2016191096A (ja) * 2015-03-31 2016-11-10 Toto株式会社 鉛およびニッケル溶出が抑制された水道用器具の製造方法
EP3842596A4 (fr) * 2018-09-27 2022-01-19 Toto Ltd. Accessoire de robinet

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CN101003899B (zh) * 2007-01-17 2010-05-19 泉州中宇卫浴科技实业有限公司 铅黄铜及铜合金表面除铅工艺
JP5473781B2 (ja) * 2009-06-01 2014-04-16 株式会社Ｌｉｘｉｌ 鉛含有銅合金製水道用器具の製造方法及び処理方法
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
CN108085684B (zh) * 2017-11-23 2019-10-08 中国科学院近代物理研究所 用于去除铜表面铌镀层的化学退镀液和退镀方法
JP6808180B2 (ja) * 2018-09-27 2021-01-06 Toto株式会社 衛生設備部材
CN112981408A (zh) * 2021-02-04 2021-06-18 九牧厨卫股份有限公司 一种除铅剂及铅黄铜部件的表层除铅工艺

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JP2000096270A (ja) * 1999-08-06 2000-04-04 Toto Ltd 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
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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JPH1072683A (ja) * 1996-08-30 1998-03-17 Toto Ltd 鉛含有銅合金製の水栓金具の鉛溶出防止処理方法
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
JP2000096269A (ja) * 1999-08-06 2000-04-04 Toto Ltd 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
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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
CN100374624C (zh) * 2002-09-09 2008-03-12 株式会社开滋 防止从铜合金制管路器件中洗脱铅和镍的方法及该洗脱后的管路器件
WO2004081257A1 (fr) * 2003-03-14 2004-09-23 Inax Corporation Procede de fabrication d'un ustensile pour systeme d'eau potable, fait d'un alliage de cuivre contenant du plomb, ustensile moule et sans plomb pour systeme d'eau potable, et ustensile pour systeme d'eau potable
CN100441744C (zh) * 2003-03-14 2008-12-10 株式会社伊奈 含铅铜合金制水道用器具的制造方法、水道用器具的铸造脱铅品
WO2005001160A1 (fr) * 2003-06-30 2005-01-06 Inax Corporation Procede de fabrication d'un systeme a eau a partir d'un alliage de cuivre contenant du plomb
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
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
JP2016191096A (ja) * 2015-03-31 2016-11-10 Toto株式会社 鉛およびニッケル溶出が抑制された水道用器具の製造方法
EP3842596A4 (fr) * 2018-09-27 2022-01-19 Toto Ltd. Accessoire de robinet
US11795671B2 (en) 2018-09-27 2023-10-24 Toto Ltd. Faucet fitting

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AU2001296025A1 (en) 2002-05-15
CN1473209A (zh) 2004-02-04
JP3866198B2 (ja) 2007-01-10
JPWO2002036856A1 (ja) 2004-03-11

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