KR100804502B1 - Surface Treating and Multi-layer Composite Plating Methods for Preventing Metal Allergy and Multi-layer Composite Plating Structures Thereof - Google Patents

Abstract

        The present invention relates to a metal allergy prevention surface treatment multilayer composite plating method and a multilayer composite plating structure according to the present invention, and according to the present invention, a resin material of a mechanical component, an electronic component, a mechanical electronic component, a portable communication and electronic device, or a portable personal ornament. Or a base plated layer forming step of forming a copper plated layer on at least a portion of the substrate surface of a metal material, in particular magnesium or magnesium alloy; A surface treatment comprising forming a metal allergy prevention layer as an intermediate plating layer forming a copper-tin alloy plating layer or a copper-tin-zinc alloy plating layer on the base plating layer; Provided is a multi-layered composite plating method for forming a noble metal or chromium plating layer on the intermediate plating layer, and a surface-treated multi-layered composite plating structure according to the present invention. Effectively prevent or prevent metal allergies that cause skin side effects such as rashes, papules and itching caused by skin contact with metals used in plating for portable communications and electronic devices, or portable personal ornaments, in particular nickel or cobalt. There is a number.

  Metal Allergy, Plating, Precious Metals, Chrome, Copper-Tin Alloy, Copper-Tin-Zinc Alloy, Substitute Nickel, Nickel-Free

Description

        Surface Treating and Multi-layer Composite Plating Methods for Preventing Metal Allergy and Multi-layer Composite Plating Structures Thereof}

        1 is an exemplary cross-sectional view showing a multilayer composite plating structure according to a first embodiment of the present invention to which a surface treatment multilayer composite plating method according to the present invention is applied.

2 is an exemplary cross-sectional view showing a multilayer composite plating structure according to a second embodiment of the present invention to which a multilayer composite surface treatment plating method according to the present invention is applied.

3 is an exemplary cross-sectional view showing a multilayer composite plating structure according to a third embodiment of the present invention to which a surface treatment multilayer composite plating method according to the present invention is applied.

4 is an exemplary cross-sectional view showing a multilayer composite plating structure according to a fourth embodiment of the present invention to which a surface treatment multilayer composite plating method according to the present invention is applied.

5 is an exemplary cross-sectional view showing a multilayer composite plating structure according to a fifth embodiment of the present invention to which a surface treatment multilayer composite plating method according to the present invention is applied.

6 is an exemplary cross-sectional view showing a multilayer composite plating structure according to a sixth embodiment of the present invention to which a surface treatment multilayer composite plating method according to the present invention is applied.

-Explanation of symbols for the main parts in the drawings-

        1,1a, 1b, 1c, 1d, 1e: Surface treatment multilayer composite plating layer structure according to the present invention

        2: substrate 3: copper plating layer

        4: copper-tin plated layer 4a: copper-tin-zinc plated layer

        5: electrochemical surface treatment plating layer 6,6a: precious metal layer

        7: chrome layer

        The present invention relates to a metal allergy prevention surface treatment multilayer composite plating method and a multilayer composite plating structure according to the present invention, and more particularly, plating of mechanical components, electronic components, mechanical electronic components, portable communication and electronic devices, or portable personal ornaments. Substrate surface treatment multilayer composite plating method for effectively preventing metal allergy causing skin side effects such as rash, papule and itching caused by skin contact with metal, especially nickel or cobalt component It relates to a multilayer composite plating structure thus produced.

        In general, an allergy is a phenomenon in which a living body that is in contact with a specific foreign heterogeneous substance exhibits a changed response to the substance unlike that until then, and the living body recognizes the heterogeneous substance as an antigen and is specific for this antigen. The immune response is produced to produce antibodies and lymphocytes that specifically react with each other. When the antigen is re-contacted, various immune responses are generated. This immune response or immune response is one of the important defense mechanisms for the self-preservation of the living body, which usually protects the living body, but sometimes this defense mechanism adversely affects the living body and causes disorders. This is defined as the systemic or localized disorder of the body caused by the immune response as an allergy.

        On the other hand, metals used in the plating of mechanical parts, electronic parts, mechanical and electronic parts, portable communication and electronic devices, or portable personal ornaments, particularly metal components such as nickel, cobalt, or mercury, may come into contact with the skin to cause rashes, papules, It is known to cause allergic contact dermatitis, such as itching. Particularly problematic here is nickel, which causes a variety of allergic contact dermatitis symptoms, but the general symptom is itching, causing a rash, thickening of the skin and a tendency to pigmentation after inflammation. Instead of itching for a few days topically, the system develops rashes and skin peels, and in more severe cases, internal organs.

        The above metal allergy phenomenon is not only a health problem due to skin side effects, but also a variety of accessories or personal items to be limited to the choice of causing inconvenience to many people, such a metal allergy once once avoided the metal, Medical treatment can relieve symptoms, but ultimate cure is not possible.

        This metal allergy phenomenon is a delayed-type reactive T cell differentiated from liver cells in bone marrow as a cellular delayed immune response caused by the action of the T cell system by antibodies in contact with a specific metal component (sensitization). T lymphocytes).

        In recent years, as the final surface treatment metals of mechanical parts, electronic parts, or mechanical and electronic parts of various industrial fields, and decorative or personal items, gold, silver, precious metal materials including copper, nickel, tin, zinc, chromium, lead, etc. Platinum, rutinium and the like are widely used. In addition, in order to manufacture a functional industrial part suitable for the use environment, various methods of multi-layer plating or alloy plating of simple metals having excellent characteristics have been used.

        Recently, however, as the surface plated portable personal products, which are component combinations of various materials, have rapidly increased, the contact frequency and the possibility of contact with nickel or cobalt, which are particularly problematic as metal allergen metals, have also increased rapidly. Although allergic contact dermatitis is a serious problem, nickel has beautiful luster and corrosion resistance when plating, and is not only the most widely used among various decorative platings, but also added to various special steels, and as a material for telecommunication equipment. Widely used, it is also used as a magnetic material and heat transfer material as an alloy, the non-ferrous alloy is used as a structural material of machinery, and also widely used as a coin, and cobalt has a high oxidation resistance and Excellent corrosion resistance ceramics As it is widely used for coloring pigments such as glass, plating raw materials, etc., the use of these metals is still increasing, and an effective way to overcome the metal allergy problem caused by these metals is currently considered to be a long way. have.

In order to solve the problems described above, some measures have been proposed to prevent or alleviate metal allergic contact dermatitis while maintaining all functions and characteristics of the product in direct contact with the skin. In addition, since the surface of the precious metal plated surface is relatively very thick, there is a disadvantage that a considerable amount of cost-up cannot be avoided.

        Therefore, the first object of the present invention is a metal allergy, in particular nickel or cobalt component metals widely used in plating of mechanical parts, electronic parts, mechanical and electronic parts, portable communication parts or portable personal ornaments used in various industries It is to provide a multi-layer composite plating method for surface treatment of a resin material, or a metal material, especially magnesium or magnesium alloy material as an alternative plating to effectively prevent the.

        The second object of the present invention is to provide a method for coating a multilayer surface coating of a base material of a resin material or a metal material, in particular magnesium or magnesium alloy material, in which a decrease in productivity and cost-up problems are not serious problems in addition to the first object described above. will be.

        A third object of the present invention is to provide a surface treatment multilayer composite plating (layer) structure (body) for metal allergy prevention prepared according to the first and second objects described above.

        According to one preferred aspect of the present invention for smoothly achieving the first and second objects of the present invention described above, a mechanical component, an electronic component, a mechanical electronic component, a portable communication and electronic device, or a portable personal ornament Forming an electrochemical plating layer on a substrate surface of a resin material or a metal material, in particular magnesium or magnesium alloy material; A base plating layer forming step of forming a copper plating layer on at least a part of the surface of the electrochemical plating layer; An intermediate plating layer forming step of forming a copper-tin alloy plating layer or a copper-tin-zinc alloy plating layer on the base plating layer; Provided is a surface treatment multilayer composite plating method including a metal allergy prevention layer forming step of forming a noble metal or chromium plating layer on the intermediate plating layer.

        According to one preferred aspect of the present invention for smoothly achieving the third object of the present invention, a resin material of a mechanical part, an electronic part, a mechanical electronic part, a portable communication and electronic device, or a portable personal ornament, Or an electrochemical plating layer on the substrate surface of a metal material, in particular magnesium or magnesium alloy material; A base plated layer as a copper plated layer formed on at least part of said electrochemical plated layer; A copper-tin alloy plating layer or a copper-tin-zinc alloy plating layer as an intermediate plating layer formed on the base plating layer described above; A surface treatment multilayer composite plating structure composed of a noble metal or a chromium plating layer as the metal allergy prevention layer formed on the intermediate plating layer is provided.

delete

        Hereinafter, the present invention will be described in more detail.

        In the metal allergy prevention surface treatment multilayer composite plating method of the present invention, an electrochemical plating layer is formed on a resin material such as plastics, or a metal material, in particular magnesium or magnesium alloy material, and then on the electrochemical plating layer. A copper plating layer was pre-formed as a plating layer, and then a copper-tin alloy or copper-tin-zinc alloy layer as an intermediate plating layer instead of nickel and nickel alloys or cobalt and cobalt alloys as the main cause of metal allergy on the upper surface of the copper plating layer. And then form a noble metal plating layer, a chromium plating layer, or a multilayer plating layer of noble metal and chromium on the surface thereof as a metal allergy prevention plating layer.

        More specifically, the metal allergy prevention surface treatment multilayer composite plating method according to the present invention will be described.

        (A) Providing resin or metal materials, especially magnesium or magnesium alloy substrates of mechanical parts, electronic parts, mechanical and electronic parts, portable communications and electronics, or portable personal ornaments whose surfaces are electrolytically degreased or etched. Making;

        (B) a pretreatment step of forming an electrochemical plating layer on the surface of the substrate to form a uniform substrate plating layer without erosion by having a uniform current distribution to improve adhesion and uniformity of the substrate plating layer to be described later;

        (C) a base for forming a copper plating layer, a noble metal plating layer, or an alloy layer thereof as a base plating layer for imparting specular glossiness and smoothness to at least part of the surface of the electrochemical plating layer and imparting uniform metal properties to various base materials. Plating layer forming step;

        (D) an intermediate plating layer forming step of forming a copper-tin alloy plating layer or a copper-tin-zinc alloy plating layer on the underlying plating layer to impart wear resistance, acid resistance, and corrosion resistance and to have a stronger surface hardness than the above-described underlying plating layer;

        (E) forming a metal allergy prevention layer as a surface layer for forming a noble metal and / or a chromium plating layer on the intermediate plating layer to impart various colors and gloss on the intermediate plating layer, and at the same time to impart the possibility of preventing metal allergy. do.

        Further, optionally, the method may further include a step of performing laser processing, sand blasting, or other mechanical processing following the base plating layer and / or the intermediate plating layer in steps (C) and / or (D).

        As a noble metal which can be used for the said noble metal plating layer, gold, silver, palladium, iridium, rutin, rhodium, platinum, etc. are mentioned.

        In addition, a copper plating layer, a noble metal plating layer, or an alloy layer thereof may be used as the base plating layer formed in the above step (C), but the preferred one in the present invention may be a copper plating layer in terms of cost, between the base and the intermediate plating layer. Mechanical, physical and chemical buffering properties.

        The intermediate plating layer formed in the above step (D) imparts basic functionality and decorative properties to the base, and in particular, serves to significantly reduce allergic contact dermatitis caused by metal allergy.

        In addition, the noble metal or chromium constituting the metal allergy prevention layer as the surface layer formed in the above (E) is to give a fine metallic gloss or high gloss, respectively.

        Next, the present invention will be described in more detail with reference to the accompanying drawings.

        1 to 6 show multilayer composite plating structures 1, 1a, 1b, 1c, 1d, and 1e according to the first to sixth embodiments of the present invention to which the surface treatment multilayer composite plating method according to the present invention is applied, respectively. An example cross section.

        As shown in Figs. 1 to 6, an electrochemical surface treatment plating layer 5 is formed as a selective plating layer on a base material 2 of a resin material or a metal material, in particular magnesium or magnesium alloy material, and the electrochemical surface treatment plating layer described above. A copper plating layer 3 (which may be a noble metal plating layer, a copper alloy plating layer, or a noble metal alloy plating layer) on (5), and then on the surface thereof, a copper-tin alloy plating layer (4) or a copper-tin-zinc alloy The plating layer 4a is formed, and on the surface thereof, either the precious metal plating layer 6 or 6a or the chrome plating layer 7 is formed as a final surface layer, or as shown in FIGS. 2 and 5, the precious metal plating layer 6a. ) And the chromium plating layer 7 may be sequentially laminated. Of course, after the chrome plating layer 7 is formed, the noble metal plating layer 6a may be formed thereon again, and after the noble metal plating layer 6a is formed, the chrome plating layer 7 may be formed by the final surface treatment. . The chromium plating layer 7 is particularly suitable as the surface treatment of electronic components having high gloss and excellent physical properties.

        In the surface treatment method according to the present invention, the thickness of the copper plating layer 3 as the underlying plating layer is generally in the range of 1 to 150 µm, preferably 3 to 60 µm, and is formed on the upper surface of the underlying plating layer 3. The thickness of the copper-tin alloy plating layer 4 or the copper-tin-zinc alloy plating layer 4a as the intermediate plating layer is generally in the range of 0.5 to 30 µm, preferably 1 to 10 µm, and is formed on the upper surface of the intermediate plating layer. The noble metal plating layers 6 and 6a are in the range of 0.05 to 5.0 탆, preferably 0.1 to 3.0 탆 in the case of the top surface layer as in the case of Figs. 1 and 4, and the chromium plating layer of the top surface as shown in Figs. In the case of the direct layer of (7), it is 0.005-3.0 micrometers which is thinner thickness, Preferably it is the range of 0.01-1.0 micrometer. On the other hand, the thickness of the chromium plating layer 7 is generally 0.05 to 3.0 µm, preferably 0.1 to 3.0 µm, and more preferably 0.1 to 1.0 µm.

        On the other hand, as shown in Figures 1 to 3, the electrochemical surface treatment is performed to form a uniform base plating layer (3) without erosion on the base 2, the electrochemical surface treatment plating layer (5) The thickness of is generally in the range of 0.005 to 5.0 m, preferably in the range of 0.01 to 1.0 m, more preferably in the range of 0.01 to 0.3 m.

In the copper-tin alloy plating layer or the copper-tin-zinc alloy plating layer according to the present invention, the component ratio of the alloy is copper: tin = 30 to 80% by weight: 70 to 20% by weight, and copper: tin: zinc = 40 to 89 weight%: 10-50 weight%: 1-10 weight%, and the current density for formation of the intermediate | middle plating layers 4 and 4a which concerns on this invention is the range of 0.5-3 A / dm <^2> .

        In addition, the precious metal plating layers 6 and 6a may use at least one metal selected from the group consisting of gold, silver, palladium, iridium, rutin, rhodium and platinum, and the content of the precious metal is 80 to 99.9% by weight. Can be. In addition, the content of the chromium plating layer 7 formed as the final surface treatment layer on the noble metal plating layer 6a in FIGS. 2 and 5 may be 80 to 99.9% by weight.

According to the present invention, the copper plating layer 3 imparts mirror gloss and smoothness, and imparts the same and homogeneous properties to various materials used as the substrate of the part. In addition, the copper-tin alloy plating layer 4 or the copper-tin-zinc alloy plating layer 4a formed on the upper surface of the copper plating layer 3 is a metal plating layer having physical and mechanical properties superior to the copper plating layer 3, and is abrasion resistance and acid resistance. , Imparting corrosion resistance, exhibiting a firm surface hardness, and also having excellent properties as a base layer for the noble metal plating layers 6 and 6a and / or the chromium plating layer 7 formed thereon.

        In the example shown in Figs. 2 and 5, the noble metal plating layer 6a is mechanically, physically and chemically buffered at the interface between the lower intermediate plating layers 4 and 4a and the chromium plating layer 7 on the upper surface of the noble metal plating layer 6a. The noble metal plating layer 6 or chromium plating layer 7, which is used as the final surface plating layer, has various colors and functions, and is particularly suitable for decorative surface treatment of portable parts, machine parts, and home appliances.

        The surface treatment multilayer composite plating method according to the present invention can prevent or prevent allergic contact dermatitis caused by skin allergy caused by nickel and nickel alloys, cobalt and cobalt alloys.

        On the other hand, according to the present invention, the properties of the copper-tin plated layer is greatly different depending on the alloy ratio. For example, when the copper content is high, the color of gold is high, the hardness and abrasion resistance are increased, but the corrosion resistance is inferior, and the temperature is high. The same phenomenon occurs even with a high current density. Conversely, low copper content results in inferior hardness and wear resistance, resulting in a haze-like plating. Therefore, the metal ratio of the alloy is as described above: copper: tin = 30 to 80% by weight: 70 to 20% by weight, copper: tin: zinc = 40 to 89% by weight: 10 to 50% by weight: 1 to 10% by weight. It may be desirable.

        Table 1 shows the results of evaluating the physical properties of the intermediate plating layer and the conventional nickel alloy plating layer in the surface-treated multilayer composite plating alloy according to the present invention.

TABLE 1

Nickel Alloy Copper-tin alloy Copper-tin-zinc alloy Alloy ratio 90-99.9 30 to 80: 70 to 20 40 to 89: 10 to 50: 1 to 10 Density (g / cm 3) 8.4 ~ 9.1 7.8 ~ 8.9 7.2 ~ 8.9 color White, light gray (glossy) White, light ivory White Longitude (MVH) 350-550 400-600 350-550 Corrosion Resistance (S.S.T 72hr) Good good Good Plating thickness (㎛) 8 5 5

        Specific examples of the pretreatment and various plating treatment conditions and methods in the surface treatment multilayer composite plating alloy according to the present invention are illustrated below, but the present invention is not limited thereto, and those skilled in the art according to various parameters such as necessity and use Of course, appropriate changes are possible therefrom within the scope of the present invention.

-Degreasing-

Caustic soda 10-150 g / L, or 20-100 g / L compound containing phosphate and surfactant.

Acid activation consisting of room temperature ~ 60 ° C, deposition degreasing or electrolytic degreasing at 3 ~ 10V and sulfuric acid 30 ~ 150g / L + additive 2 seconds ~ 2 minutes or hydrochloric acid 30 ~ 150g / L + additive

-Polishing-

Mixed acid containing 10 ~ 100g / L nitric acid, 5 ~ 100g / L sulfuric acid, 30 ~ 80g / L hydrofluoric acid, solution deposition time including other corrosion inhibitors, stabilizers, surfactants 1sec ~ 60sec, room temperature

Etching

Immersion time 10 ~ 120 sec, 25 ~ 50 degree in solution containing 10 ~ 50g / L of loxel salt and 30 ~ 100g / L of blue soda

Caustic soda 10-50g / L, ammonium bifluoride 10-50g / L, solution containing 5-40g / L oxalic acid, 1-5 minutes deposition, working temperature 40-70 degrees

-Tonghua Copper Plating-

TABLE 2

Temperature Voltage Energization time pH CuCN + NaCN (KCN) + NaOH (KOH) + Additive 40-60 2 ~ 10V 10 to 30 seconds or 3 to 10 minutes 11-13.5

-Acid Copper Plating-

TABLE 3

Temperature Voltage Energization time pH CuSO ₄ (150 ~ 240g / L) + H ₂ SO ₄ (30 ~ 80g / L) + Cl (20 ~ 200ppm) + Additive 15-35 2-5V 10-50 minutes 2 or less

Sn-Cu alloy plating (binary alloy plating) or Sn-Cu-Zn alloy plating (ternary alloy plating)

TABLE 4

Temperature Voltage Energization time pH CuCN (5 ~ 15g / L) + K ₂ [Sn (OH) ₆ ] (5 ~ 40g / L) + Caustic Soda (2 ~ 50g / L) + Caustic (10 ~ 150g / L) + Additive 40-65 1 ~ 6V 3-30 minutes 12 or more

TABLE 5

Temperature Voltage Energization time pH CuCN (5 ~ 15g / L) + K ₂ [Sn (OH) ₆ ] (5 ~ 40g / L) + Cyanated Zinc (1 ~ 20g / L) + Caustic Soda (2 ~ 50g / L) + Caustic (10 ~ 150 g / L) + additive 40-65 1 ~ 6V 3-30 minutes 12 or more

-Precious Metal Plating-

TABLE 6

Temperature Voltage Energization time Solutions containing Ag, Au, Pt, Pd, Ru, Rh, Ir, etc. 10-60 1 ~ 6V 3 ~ 10 minutes

-Chrome Plating-

TABLE 7

Temperature Voltage Energization time Salts and additives containing Cr 10-60 3 ~ 8V 1-8 minutes

Sn-Cu-Zn Alloy Plating

TABLE 8

Temperature Voltage Energization time pH Cu salt (5-15 g / L) + tin salt (5-40 g / L) + Zn (1-8 g / L) additive 40-65 1 ~ 6V 3-30 minutes 12 or more

Laser processing

Applicable after plating binary and tertiary alloys for each material.

-Electrochemical Surface Treatment Plating Layer-

When the base is magnesium or an alloy thereof, it means a substitution treatment of metal ions such as zinc known in the art, and when the base is a resin material, it means surface activation treatment known in the art.

One of these electrochemical surface treatment platings, metal ion substitution, in particular zinc substitution, is a precoat for electroplating to have a uniform surface current distribution for subsequent electroplating, in particular copper plating, using ZnSO ₄ based solutions. For example, it may be performed using, for example, Japan DeepSol Corporation, model name 20000EA or 20000EA, and the other activation treatment may be performed using various active treatment liquids based on Na ₄ P ₂ O ₇ . .

Plating Process

TABLE 9

In case of aluminum, magnesium, zinc, plastic, iron, etc.

Iron and iron alloy Aluminum and aluminum alloy Zinc and zinc alloy Magnesium and magnesium alloy Resin such as plastic Copper and Copper Alloy fair Degreasing Degreasing Degreasing Degreasing Degreasing Degreasing Pickling etching grinding etching etching Pickling Electrolytic degreasing (Zinc) Substitution Pickling (Zinc) Substitution Chinese copper Copper plating (nickel) copper copper catalyst Binary or ternary alloys Binary or ternary alloys copper Binary or ternary alloys Binary or ternary alloys Activation (Precious metals) (Precious metals) Binary or ternary alloys (Precious metals) (Precious metals) (Nickel) Cr plating Cr plating (Precious metals) Cr plating Cr plating copper Cr plating Binary or ternary alloys (Precious metals) Cr plating

        Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, which are intended to illustrate the present invention but are not intended to limit the present invention.

Example 1

        After degreasing and etching on a plate-shaped zinc alloy substrate having a size of 20x20x0.2 cm, subjected to electrolytic degreasing, the copper plating was carried out under the compositions and conditions as shown in Table 2, and then plated copper lactate under the compositions and conditions as shown in Table 3. After the copper plating layer was formed to have a thickness of 30 μm, the copper-tin alloy plating layer was formed to have a thickness of 3 μm under the composition and conditions as shown in Table 4, and the chrome plated layer was 0.5 μm under the conditions as shown in Table 6 again. A composite multilayer plating structure formed to a thickness was formed.

Example 2

        An electrochemical surface treatment plating layer was formed to a thickness of 0.2 μm at 65 to 75 ° C. using a Japan DeepSol Corporation model name 20000EA on a 20 × 20 × 0.2 cm sized magnesium alloy substrate subjected to electrolytic degreasing and surface etching, and then shown in Table 2. The copper plating layer was formed under the composition and the conditions as described above, and copper lactate was formed under the composition and the conditions as shown in Table 3 to form a copper plating layer having a thickness of 30 μm, and then the copper under the composition and the conditions as shown in the Table 4 below. A composite multilayer in which a tin alloy plating layer was formed in a thickness of 3 µm, and the palladium plating layer was formed in a thickness of 0.2 µm under the conditions shown in Table 6, and then the chromium plating layer was formed in a thickness of 0.5 µm under the conditions as shown in Table 7. The plating structure was formed.

Example 3

The activation treatment on the base acrylic resin substrate of size 20x20x0.2cm which was electrolytic degreasing was performed by forming an electrochemical surface treatment plating layer having a thickness of 1 μm using Na ₄ P ₂ O ₇ + CH ₃ COONa-based active treatment solution. , Copper plating layer was carried out under the compositions and conditions as shown in Table 2 and copper lactate plating under the compositions and conditions as shown in Table 3 to form a copper plating layer having a thickness of 30 μm, and then as shown in Table 5 A copper-tin alloy plating layer was formed to have a thickness of 3 µm under the composition and conditions, and a composite multilayer plating structure in which the chromium plating layer was formed to a thickness of 0.5 µm under the conditions as shown in Table 7 was formed.

Example 4

        The copper plating layer was formed by electrolytic degreasing on a flat iron substrate having a size of 20x20x0.2 cm under the composition and conditions as shown in Table 2 and copper lactate plating under the composition and conditions as shown in Table 3. After the thickness was formed to 50 mu m, the copper-tin-zinc alloy plated layer was formed to have a thickness of 3 mu m under the composition and conditions as shown in Table 8, and the gold plated layer was further formed to a thickness of 0.2 mu m under the conditions as shown in Table 6. A composite multilayer plating structure was formed.

Example 5

        Copper plating on electrolytic degreasing and surface etched zinc alloy bases with dimensions 20x20x0.2 cm was carried out under compositions and conditions as shown in Table 2 and copper lactate plating under compositions and conditions as shown in Table 3 After the plated layer was formed to a thickness of 40 μm, a copper-tin-zinc alloy plated layer was formed to have a thickness of 5 μm under the compositions and conditions as shown in Table 8, and the palladium plated layer was then to a thickness of 0.2 μm under the conditions shown in Table 6. After the formation, the composite multilayer plating structure in which the chromium plating layer was formed to a thickness of 0.7 mu m under the conditions as shown in Table 7 was formed.

Example 6

        The copper plating layer was formed to a thickness of 10 탆 by performing copper plating on the plated copper substrate having a size of 20x20x0.2cm and electrolytic degreasing under the composition and conditions as shown in Table 3, and then the composition and conditions as shown in Table 8 A copper-tin-zinc alloy plating layer was formed under 5 mu m thick, and then a composite multilayer plating structure was formed in which a chromium plating layer was formed with a thickness of 0.5 mu m under the conditions as shown in Table 7.

Test Example-Metal Allergy Test

A patch test was performed to determine whether the plating antigen (1 cm x 2 cm x 0.5 mm specimen) prepared according to Examples 1 to 6 was the causative antigen of metal allergic contact dermatitis. This test was judged by attaching and fixing the lower plate of the arm on the lint of the bandage for patch inspection and fixing it after 4 hours.

        Thirty adult men and women who were positive nickel contact allergy were performed and the skin condition was visually read and the results are shown in Table 10.

TABLE 10

 product Judgment result  Stimulus A B C D Example 1 30 26 3 One 0.16 Example 2 30 22 6 One 0.33 Example 3 30 26 2 2 0.19 Example 4 30 27 3 One 0.10 Example 5 30 24 4 2 0.25 Example 6 30 22 6 One 0.33

* Judgment Table

A: No erythema or unusual symptoms

B: Slightly redder than the surroundings

C: noticeably redder than the surroundings

D: Severe reddening and swelling

[Equation 1]

               (Number B1) + (Number C2) + (Number D3)

Stimulus = --------------------------------

            (Number B1) + (Number C2) + (Number D3) + A Number

        As can be seen from the irritation test result of the metal allergy, the surface treatment multilayer composite plating structure according to Examples 1 to 6 of the present invention, which does not contain nickel or cobalt and has a metal allergy prevention surface layer, is nickel allergy. It was found that even those who exhibited almost no allergic to metals.

        As described above, the multilayer composite plating structure (sieve) according to the metal allergy prevention surface treatment multilayer composite plating method of the present invention is a mechanical component, an electronic component used in various industrial fields instead of nickel or cobalt plating, which is a metal allergen causing metal component. It can be widely applied to plating of mechanical, electronic parts, or portable personal ornaments, and is effective in preventing and preventing metal allergic contact dermatitis, and is also effective in reducing productivity and cost-up problems.

Claims (9)

        Metal allergy prevention surface treatment multilayer composite plating method comprising the following steps: (A) Electrochemical surface treatment on the surface of the resin material of mechanical parts, electronic parts, mechanical and electronic parts, portable communication and electronic devices, or portable personal ornaments, or of the substrate of magnesium or magnesium alloy, to a thickness of 0.01 to 1.0. A pretreatment step of forming an electrochemical plating layer of μm; (B) a base plating layer forming step of forming a plating layer of copper, a noble metal, or an alloy thereof on at least part of the surface of the electrochemical plating layer; (C) forming an intermediate plating layer as a metal allergy prevention layer of a copper-tin alloy plating layer or a copper-tin-zinc alloy plating layer on said base plating layer; And (D) forming a noble metal or chromium plating layer on the intermediate plating layer. delete         The surface treatment multilayer composite plating method of claim 1, further comprising performing a laser processing, sand blasting, or a mechanical surface processing step immediately after the base plating layer forming step or the intermediate plating layer forming step.         The surface treatment multilayer composite according to claim 1, wherein the precious metal plating layer is a plating layer formed of at least one precious metal selected from the group consisting of gold, silver, palladium, iridium, rutin, rhodium and platinum. Plating method.         The thickness of the base plating layer is 3 to 60 µm, the thickness of the copper-tin alloy plating layer or the copper-tin-zinc alloy plating layer as the intermediate plating layer is 1 to 10 µm, and the thickness of the noble metal plating layer or the chromium plating layer is 0.1 to 1. Surface treatment multilayer composite plating method for metal allergy prevention of 3.0㎛.         The method of claim 5, wherein both the precious metal plating layer and the chromium plating layer are included, the thickness of the precious metal plating layer is 0.01-1.0 탆, and the thickness of the chromium plating layer is 0.1-1.0 탆.         The alloy ratio of claim 1, wherein the alloy ratio is copper: tin = 30 to 80% by weight: 70 to 20% by weight when the intermediate plating layer is a copper-tin alloy plating layer, and the alloy ratio is copper to a copper-tin-zinc alloy plating layer. : Tin: Zinc = 40-89 weight%: 10-50 weight%: 1-10 weight% The surface treatment multilayer composite plating method for metal allergy prevention. delete         A metal allergy prevention surface treatment multilayer composite plating structure manufactured by the metal allergy prevention surface treatment multilayer composite plating method according to any one of the preceding claims.

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