CN108707882B - Bronze golden tooth color zipper and manufacturing method thereof - Google Patents

Bronze golden tooth color zipper and manufacturing method thereof Download PDF

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CN108707882B
CN108707882B CN201810557897.6A CN201810557897A CN108707882B CN 108707882 B CN108707882 B CN 108707882B CN 201810557897 A CN201810557897 A CN 201810557897A CN 108707882 B CN108707882 B CN 108707882B
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bronze
zipper
water
aqueous solution
cupronickel
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CN108707882A (en
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姚耀华
张江南
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Zhejiang Weixing Industrial Development Co Ltd
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Zhejiang Weixing Industrial Development Co Ltd
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    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Dental Preparations (AREA)

Abstract

The invention provides a bronze golden tooth color zipper and a manufacturing method thereof, wherein the method comprises the following steps: soaking the zipper to be colored in the bronze aqueous solution for 1-3 min, cleaning, soaking in the cupronickel aqueous solution for 3-60 s, cleaning again, and performing passivation treatment to obtain a bronze golden tooth colored zipper; the bronze water solution comprises the following components in percentage by mass: 0.8-1% of selenium dioxide, 4-5% of sodium persulfate, 3-4% of copper nitrate, 2-3% of sulfuric acid, 2-3% of nitric acid, 6-7.5% of phosphoric acid, 0.6-0.8% of soda ash and the balance of water; the cupronickel aqueous solution consists of the following components: 2-4% of stannous chloride, 5-12% of thiourea, 1-2% of hydrochloric acid, 0.4-1% of fatty alcohol-polyoxyethylene ether emulsifier, 0.5-14% of auxiliary agent and the balance of water. The method endows the bronze gold tooth color zipper with unique visual sense, improves the grade of the zipper, makes up for the defect between light gold and bronze, and meets the requirement of customers on diversity.

Description

Bronze golden tooth color zipper and manufacturing method thereof
Technical Field
The invention belongs to the technical field of surface coloring of metal materials, and particularly relates to a bronze golden tooth color zipper and a manufacturing method thereof.
Background
The zipper can be divided into nylon, plastic steel and metal zipper according to the color of the zipper teeth. With the diversification of clothes, as an important component of the clothes, the tooth color of the zipper is more and more colorful in combination with the current fashion trend. Various tooth colors mainly comprising metal product zippers are more and more, the zipper production cost (coloring) is more and more diversified, and along with the diversified tooth color requirements of customers, the tooth color between light golden color and bronze color is favored by the customers.
Light golden and bronze zippers are common in the market; however, the teeth of the light golden zipper are brighter, and the production cost is higher; the bronze zipper teeth are darker and are a defect for high-end customers, special customers and factory production cost.
Disclosure of Invention
In view of the above, the present invention provides a bronze gold-tooth zipper and a manufacturing method thereof, which can manufacture a bronze gold-tooth zipper and satisfy usability.
The invention provides a manufacturing method of a bronze golden tooth color zipper, which comprises the following steps:
soaking the zipper to be colored in the bronze aqueous solution for 1-3 min, cleaning, soaking in the cupronickel aqueous solution for 3-60 s, cleaning again, and performing passivation treatment to obtain a bronze golden tooth colored zipper;
the bronze aqueous solution comprises the following components in parts by mass:
0.8-1% of selenium dioxide, 4-5% of sodium persulfate, 3-4% of copper nitrate, 2-3% of sulfuric acid, 2-3% of nitric acid, 6-7.5% of phosphoric acid, 0.6-0.8% of soda ash and the balance of water;
the cupronickel aqueous solution comprises the following components in parts by mass:
2-4% of stannous chloride, 5-12% of thiourea, 1-2% of hydrochloric acid, 0.4-1% of fatty alcohol-polyoxyethylene ether emulsifier, 0.5-14% of auxiliary agent and the balance of water.
Preferably, the soaking temperature in the bronze water solution is 20-30 ℃.
Preferably, the soaking temperature in the cupronickel water solution is 20-30 ℃.
Preferably, the time of the passivation treatment is 50-70 s.
Preferably, the auxiliary agent is selected from one or more of malic acid, disodium edetate, citric acid and sodium hypophosphite.
Preferably, the cupronickel aqueous solution consists of the following components in percentage by mass:
2-4% of stannous chloride, 5-12% of thiourea, 1-2% of hydrochloric acid, 0.4-1% of fatty alcohol-polyoxyethylene ether emulsifier, 0.4-1% of malic acid, 0.4-1% of disodium ethylene diamine tetraacetate, 1-2% of citric acid, 0.5-10% of sodium hypophosphite and the balance of water.
Preferably, both the immersion in the aqueous bronze solution and the immersion in the aqueous cupronickel solution are performed under tumbling conditions.
The invention provides a bronze golden tooth color zipper which is prepared by the manufacturing method of the technical scheme.
The invention provides a manufacturing method of a bronze golden tooth color zipper, which comprises the following steps: soaking the zipper to be colored in the bronze aqueous solution for 1-3 min, cleaning, soaking in the cupronickel aqueous solution for 3-60 s, cleaning again, and performing passivation treatment to obtain a bronze golden tooth colored zipper; said green isThe copper aqueous solution comprises the following components in parts by mass: 0.8-1% of selenium dioxide, 4-5% of sodium persulfate, 3-4% of copper nitrate, 2-3% of sulfuric acid, 2-3% of nitric acid, 6-7.5% of phosphoric acid, 0.6-0.8% of soda ash and the balance of water; the cupronickel aqueous solution comprises the following components in parts by mass: 2-4% of stannous chloride, 5-12% of thiourea, 1-2% of hydrochloric acid, 0.4-1% of fatty alcohol-polyoxyethylene ether emulsifier, 0.5-14% of auxiliary agent and the balance of water. According to the invention, the bronze water solution and the cupronickel water solution with specific formulas are adopted to soak the surface of the zipper under a specific process, so that the zipper is endowed with unique visual sensation, the grade of the zipper is improved, the defect between light gold and bronze is partially compensated, the bronze golden tooth color zipper is obtained, and the requirement of customers on diversity is met. In addition, the paint is resistant to water washing and salt spray; does not contain chromium ions and chloride ions, and accords with the environmental protection concept. The experimental results show that: visually observing, wherein the zipper is bronze and golden tooth color; no color change after 5 times of water washing; 5% salt spray test for 24h has no color change; cr (chromium) component6+And APEOS were not detected.
Drawings
FIG. 1 is a photograph showing the appearance of a slide fastener produced in example 1 of the present invention.
Detailed Description
The invention provides a manufacturing method of a bronze golden tooth color zipper, which comprises the following steps:
soaking the zipper to be colored in the bronze aqueous solution for 1-3 min, cleaning, soaking in the cupronickel aqueous solution for 3-60 s, cleaning again, and performing passivation treatment to obtain a bronze golden tooth colored zipper;
the bronze aqueous solution comprises the following components in parts by mass:
0.8-1% of selenium dioxide, 4-5% of sodium persulfate, 3-4% of copper nitrate, 2-3% of sulfuric acid, 2-3% of nitric acid, 6-7.5% of phosphoric acid, 0.6-0.8% of soda ash and the balance of water;
the cupronickel aqueous solution comprises the following components in parts by mass:
2-4% of stannous chloride, 5-12% of thiourea, 1-2% of hydrochloric acid, 0.4-1% of fatty alcohol-polyoxyethylene ether emulsifier, 0.5-14% of auxiliary agent and the balance of water.
According to the invention, the bronze water solution and the cupronickel water solution with specific formulas are adopted to soak the surface of the zipper under a specific process, so that the zipper is endowed with unique visual sensation, the grade of the zipper is improved, the defect between light gold and bronze is partially compensated, the bronze golden tooth color zipper is obtained, and the requirement of customers on diversity is met. In addition, the paint is resistant to water washing and salt spray; does not contain chromium ions and chloride ions, and accords with the environmental protection concept.
The zipper to be colored is soaked in bronze aqueous solution for 1-3 min, washed, soaked in cupronickel aqueous solution for 3-60 s, washed again and passivated to obtain the bronze golden tooth colored zipper.
In the invention, the bronze aqueous solution consists of the following components in parts by mass:
0.8-1% of selenium dioxide, 4-5% of sodium persulfate, 3-4% of copper nitrate, 2-3% of sulfuric acid, 2-3% of nitric acid, 6-7.5% of phosphoric acid, 0.6-0.8% of soda ash and the balance of water.
The raw material of the bronze aqueous solution comprises 0.8-1.0% of selenium dioxide; preferably comprising selenium dioxide 0.8%, 0.9% or 1.0%.
The raw material of the bronze aqueous solution comprises 4-5% of sodium persulfate; preferably 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9% or 5.0% sodium persulfate.
The bronze aqueous solution comprises 3-4% of copper nitrate as a raw material; preferably, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, or 1.0% copper nitrate is included.
The bronze aqueous solution comprises 2-3% of sulfuric acid as a raw material; preferably 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9% or 3.0% is included.
The bronze water solution comprises 2-3% of nitric acid as a raw material; preferably, nitric acid is included at 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9% or 3.0%.
The bronze water solution comprises 6-7.5% of phosphoric acid, preferably 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3%, 7.4% or 7.5% of phosphoric acid.
The bronze aqueous solution comprises 0.6-0.8% of sodium carbonate; preferably, soda ash is included at 0.60%, 0.61%, 0.62%, 0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.70%, 0.71%, 0.72%, 0.73%, 0.74%, 0.75%, 0.76%, 0.77%, 0.78%, 0.79% or 0.80%.
The raw material of the bronze aqueous solution includes the balance water. Deionized water is preferred for the present invention.
The method comprises the steps of soaking a zipper to be colored in a bronze aqueous solution for 1-3 min, preferably 10-120 s, more preferably 60-90 s; in the embodiment of the invention, the time for soaking the zipper to be colored in the bronze water solution is 60s, 80s or 90 s.
The immersion of the zipper to be colored in the bronze aqueous solution is preferably carried out under the condition of overturning.
Cleaning the bronze after soaking in the bronze aqueous solution; the invention preferably adopts water for cleaning; the cleaning temperature is preferably 20-30 ℃.
And soaking in a cupronickel water solution for 3-60 s after cleaning. In the invention, the cupronickel aqueous solution comprises the following components in parts by mass:
2-4% of stannous chloride, 5-12% of thiourea, 1-2% of hydrochloric acid, 0.4-1% of fatty alcohol-polyoxyethylene ether emulsifier, 0.5-14% of auxiliary agent and the balance of water.
The cupronickel aqueous solution comprises 2-4% of stannous chloride; preferably including stannous chloride 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9% or 4.0%.
The cupronickel aqueous solution comprises 5-12% of thiourea; preferably, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 11.0%, or 12.0% thiourea is included.
The cupronickel aqueous solution comprises 1-2% of hydrochloric acid; preferably, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% or 2.0% hydrochloric acid is included.
The cupronickel water solution comprises 0.4-1% of fatty alcohol-polyoxyethylene ether emulsifier; preferably, the environmentally friendly emulsifier is included at 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1.0%.
The cupronickel aqueous solution comprises 0.5-14% of an auxiliary agent; the auxiliary agent preferably comprises one or more of malic acid, disodium ethylene diamine tetraacetate, citric acid and sodium hypochlorite. The malic acid preferably accounts for 0.4-1.0% of the mass of the cupronickel aqueous solution. The disodium ethylene diamine tetraacetate preferably accounts for 0.4-1.0% of the mass of the cupronickel aqueous solution. The citric acid preferably accounts for 1.0-2.0% of the mass of the cupronickel aqueous solution. The optimal weight of the sodium sulfoxylate accounts for 0.5-10.0% of the weight of the cupronickel solution.
The aqueous cupronickel solution includes the balance water.
Soaking in a cupronickel water solution for 3-60 s; preferably 3 to 30 seconds, and more preferably 3 to 15 seconds. The immersion in the cupronickel solution is preferably carried out under tumbling conditions.
And after soaking in the cupronickel water solution, cleaning again. The invention preferably adopts water to wash again; the temperature for the secondary cleaning is preferably 20-30 ℃.
And cleaning again and then passivating to obtain the bronze golden tooth color zipper. The time of the passivation treatment is preferably 50-70 s.
According to the invention, after the passivation treatment is finished, the cleaning and spin-drying are preferably carried out, so that the bronze gold tooth color zipper is obtained. The bronze tooth color is between light gold and bronze.
The manufacturing method provided by the invention is suitable for zippers made of all metal materials.
The invention provides a bronze golden tooth color zipper which is prepared by the manufacturing method of the technical scheme.
For further illustration of the present invention, the following will describe in detail a bronze gold tooth color zipper and its manufacturing method with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
450g of selenium dioxide, 2500g of sodium persulfate, 2000g of copper nitrate, 1480g of sulfuric acid, 1420g of nitric acid, 3750g of phosphoric acid and 400g of soda ash are mixed, 38kg of water is added to obtain a bronze aqueous solution, the zipper is soaked in the mixed water and turned over for 1 minute, and then the zipper is taken out and washed in water at the temperature of 22 ℃. After the cleaning is finished, soaking in the following components: 2000g of stannous chloride, 6000 g of thiourea, 700 ml of hydrochloric acid with the mass fraction of 38%, 200g of malic acid, 200g of fatty alcohol-polyoxyethylene ether emulsifier, 200g of disodium ethylenediamine tetraacetic acid, 500g of citric acid and 800 g of sodium hypophosphite, 50kg of water is added and mixed together to be uniformly stirred to form a cupronickel water solution, the mixture is soaked and turned over for 10 seconds, then the mixture is washed by water again, and the passivation is carried out for 1 minute after the mixture is washed again; and finally, washing and drying to obtain the zipper.
The invention photographs the zipper prepared in example 1, as shown in fig. 1; FIG. 1 is a photograph showing the appearance of a slide fastener produced in example 1 of the present invention; it can be seen from figure 1 that the appearance is between bronze and light gold, i.e. bronze-gold tooth.
The zippers prepared in the examples 1 to 3 were subjected to water washing resistance, salt fog resistance and Cr resistance6+And APEOS, results are shown in table 1:
TABLE 1 Performance test results of zippers prepared in inventive examples 1-3
Figure BDA0001681860900000051
Figure BDA0001681860900000061
Example 2
400g of selenium dioxide was mixed with 2250g of sodium persulfate, 1500g of copper nitrate, 1000g of sulfuric acid, 1200g of nitric acid, 3100g of phosphoric acid and 300g of soda ash, water was added to obtain 50kg of bronze aqueous solution, the slide fastener was immersed in the mixed water and turned over for 80 seconds, and then taken out and washed in 20 ℃ water. After the cleaning is finished, soaking in the following components: 1000g of stannous chloride, 4750 g of thiourea, 860 ml of hydrochloric acid with the mass fraction of 38%, 350g of malic acid, 350g of fatty alcohol-polyoxyethylene ether emulsifier, 350g of disodium ethylenediamine tetraacetic acid, 750g of citric acid and 2500g of sodium hypophosphite, 50kg of water is added and mixed together to be uniformly stirred to form a cupronickel aqueous solution, the mixture is soaked and turned over for 10 seconds, then the mixture is washed by water again, and passivation is carried out for 50 seconds after the mixture is washed again; and finally, washing and drying to obtain the zipper.
The appearance of the zipper prepared in the example 2 of the invention is consistent with that of the zipper prepared in the figure 1, and the color of the appearance is between bronze color and light golden color, namely bronze tooth color.
The zippers prepared in the examples 1 to 3 were subjected to water washing resistance, salt fog resistance and Cr resistance6+And APEOS, results are shown in table 1.
Example 3
500g of selenium dioxide, 2000g of sodium persulfate, 1750g of copper nitrate, 1250g of sulfuric acid, 1000g of nitric acid, 3450g of phosphoric acid and 350g of soda ash are mixed, water is added to obtain 50kg of bronze aqueous solution, the zipper is soaked in the mixed water and turned over for 90s, and then the zipper is taken out and washed in water at 25 ℃. After the cleaning is finished, soaking in the following components: 1500g of stannous chloride, 2550 g of thiourea, 450 ml of hydrochloric acid with the mass fraction of 38%, 500g of malic acid, 500g of fatty alcohol-polyoxyethylene ether emulsifier, 500g of disodium ethylenediamine tetraacetic acid, 1000g of citric acid and 4500 g of sodium hypophosphite, 50kg of the mixture is added with water and then uniformly mixed together to form a cupronickel aqueous solution, the mixture is soaked and turned over for 10 seconds, then the mixture is washed by water again, and passivation is carried out for 70 seconds after the mixture is washed again; and finally, washing and drying to obtain the zipper.
The appearance of the zipper prepared in the example 3 of the invention is consistent with that of the zipper prepared in the figure 1, and the color of the appearance is between bronze color and light golden color, namely bronze tooth color.
The zippers prepared in the examples 1 to 3 were subjected to water washing resistance, salt fog resistance and Cr resistance6+And APEOS, results are shown in table 1.
Comparative example 1
600g of selenium dioxide, 1500g of sodium persulfate, 2000g of copper nitrate, 2000g of sulfuric acid, 1500g of nitric acid, 4000g of phosphoric acid and 300g of soda ash are mixed, water is added to obtain 50kg of bronze aqueous solution, and the zipper is soaked in the mixed water and turned over for about 2 minutes, and then cleaned. After the cleaning is finished, soaking in the following components: 1500g of stannous chloride, 5000 g of thiourea, 800 ml of hydrochloric acid with the mass fraction of 38%, 200g of malic acid, 100g of environment-friendly emulsifier, 200g of disodium ethylenediamine tetraacetic acid, 1500g of citric acid and 900 g of sodium hypophosphite, 50kg of water is added, and the mixture is uniformly mixed together and stirred to form a mixed solution, and the mixed solution is soaked and overturned for 10 seconds. Then cleaning, and passivating for 1 minute after cleaning; and (4) spin-drying after cleaning, wherein the obtained zipper cannot meet the bronze color requirement, and the zipper is scrapped.
From the above embodiment, the invention provides a manufacturing method of a bronze gold tooth color zipper, comprising the following steps: soaking the zipper to be colored in the bronze aqueous solution for 1-3 min, cleaning, soaking in the cupronickel aqueous solution for 3-60 s, cleaning again, and performing passivation treatment to obtain a bronze golden tooth colored zipper; the bronze aqueous solution comprises the following components in parts by mass: 0.8-1% of selenium dioxide, 4-5% of sodium persulfate, 3-4% of copper nitrate, 2-3% of sulfuric acid, 2-3% of nitric acid, 6-7.5% of phosphoric acid, 0.6-0.8% of soda ash and the balance of water; the cupronickel aqueous solution comprises the following components in parts by mass: 2-4% of stannous chloride, 5-12% of thiourea, 1-2% of hydrochloric acid, 0.5-1% of fatty alcohol-polyoxyethylene ether emulsifier, 0.5-14% of auxiliary agent and the balance of water. According to the invention, the bronze water solution and the cupronickel water solution with specific formulas are adopted to soak the surface of the zipper under a specific process, so that the zipper is endowed with unique visual sensation, the grade of the zipper is improved, the defect between light gold and bronze is partially compensated, the bronze golden tooth color zipper is obtained, and the requirement of customers on diversity is met. In addition, the paint is resistant to water washing and salt spray; does not contain chromium ions and chloride ions, and accords with the environmental protection concept. The experimental results show that: visually observing, wherein the zipper is bronze and golden tooth color; no color change after 5 times of water washing; 5% salt spray test for 24h has no color change; cr (chromium) component6+And APEOS were not detected.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (4)

1. A manufacturing method of a bronze gold tooth color zipper comprises the following steps:
soaking the zipper to be colored in the bronze aqueous solution for 1-3 min, cleaning, soaking in the cupronickel aqueous solution for 3-60 s, cleaning again, and performing passivation treatment to obtain a bronze golden tooth colored zipper;
the bronze aqueous solution comprises the following components in parts by mass:
0.8-1% of selenium dioxide, 4-5% of sodium persulfate, 3-4% of copper nitrate, 2-3% of sulfuric acid, 2-3% of nitric acid, 6-7.5% of phosphoric acid, 0.6-0.8% of soda ash and the balance of water;
the cupronickel aqueous solution comprises the following components in parts by mass:
2-4% of stannous chloride, 5-12% of thiourea, 1-2% of hydrochloric acid, 0.4-1% of fatty alcohol-polyoxyethylene ether emulsifier, 0.5-14% of auxiliary agent and the balance of water;
the soaking temperature in the bronze water solution is 20-30 ℃;
the soaking temperature in the cupronickel water solution is 20-30 ℃;
the time of the passivation treatment is 50-70 s;
the auxiliary agent is selected from one or more of malic acid, disodium ethylene diamine tetraacetate, citric acid and sodium hypophosphite.
2. The manufacturing method according to claim 1, wherein the cupronickel aqueous solution consists of the following components in mass fraction:
2-4% of stannous chloride, 5-12% of thiourea, 1-2% of hydrochloric acid, 0.4-1% of fatty alcohol-polyoxyethylene ether emulsifier, 0.4-1% of malic acid, 0.4-1% of disodium ethylene diamine tetraacetate, 1-2% of citric acid, 0.5-10% of sodium hypophosphite and the balance of water.
3. The method of claim 1, wherein the immersion in the aqueous bronze solution and the immersion in the aqueous cupronickel solution are performed under tumbling conditions.
4. A bronze gold tooth color zipper produced by the production method according to any one of claims 1 to 3.
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