JPH0551957U - Nickel allergic prevention ornaments - Google Patents

Abstract

(57) [Summary] [Purpose] To prevent nickel allergy from nickel-containing ornaments. [Structure] Pd for nickel-containing decorative base material
0.5-5μm on white finish plating layer of Sn series or Sn series
Formed with a thickness of. A base plating layer containing nickel and components of the finish plating layer may be previously formed on the base material.
The value of free nickel is suppressed below the legal limit. The base plating layer improves the adhesion to the base material and more effectively reduces the amount of free nickel.

Description

[Detailed description of the device]

[0001]

[Industrial application]

 The present invention relates to a white-colored decorative article composed of a base material mainly containing nickel or a base material having a nickel-containing plating formed thereon, and in particular, a nickel-based decorative article effective for preventing skin allergy caused when such a decorative article is used. Regarding white ornaments.

[0002]

[Prior Art]

 Decorative items such as eyeglass frames that have a white appearance have been obtained mainly by forming materials such as nickel-chromium alloy, nickel silver, monel, etc., or a base plating and finish plating made of various nickel alloys on these materials. ..

[0003]

[Issues to be solved by the device]

 However, since these white ornaments contain nickel of several% to several tens of percent, nickel is released during use and causes so-called nickel allergy when directly contacting the skin as in the case of eyeglass frames. There is a risk.

Although this nickel allergy is currently regarded as a problem in various countries, legal regulations are applied to metal products made of a nickel-containing alloy or a material coated with a nickel-containing substance, especially in the EC sphere. In some cases, administrative measures have been taken to prohibit the sale of substances that produce more than a certain amount of free nickel.

However, in the present situation of white ornaments, apart from the case of using a high-grade material such as titanium, the material such as an eyeglass frame or its plating layer almost always contains nickel. For white color ornaments, nickel alternatives are not easily found in terms of color and cost.

[0006]

[Means for Solving the Problems]

 The above-mentioned problems of the prior art can be solved by a nickel-alergic prevention decorative article in which a white finish plating layer made of Pd and a Pd-based alloy or Sn alloy is formed in a thickness of 0.5 to 5 μm on a nickel-containing substrate.

[0007]

[Action]

 In the present invention, a white finish plating layer made of Pd and a Pd-based alloy or Sn alloy is applied to the nickel-containing base material, and the appearance is the same as that of the conventional nickel-containing base material or such base material. It has a white color that is almost equivalent to that of the plated nickel alloy. Also, since nickel contained in the substrate is prevented from being released to the surface by the finish plating layer, nickel allergy is not induced even when these ornaments are used in direct contact with the skin. ..

[0008] Currently, EC regulates the regulated value of free nickel according to the legal regulations applied to nickel products to 0.5 mg / cm ² / week, and the analysis method shows a specific color reaction to nickel. Dimethylglyoxime is used as a reagent.

That is, the surface of the test article is rubbed for 30 seconds with a constant motion by a gauze in which two drops of a 1% ethanol solution of dimethylclyoxime and a 10% aqueous solution of ammonium hydroxide are dropped, and a light rose to a bright color is obtained. If there is a reddish color up to the thier color, it is considered that 0.5 mg / cm ² / week or more of free nickel is present.

In the plating layer of nickel silver, nickel silver, nickel alloy, SUS-304, nickel as white plating, Pd-Ni alloy (Ni> 15%), which is currently used as a base material for white ornaments, In each case, the free nickel exceeds the regulation value.

In the present invention, since such a nickel-containing base material is coated with the nickel-free finish plating layer such as the Pd-based or Au—Sn-based material, the release of nickel from the base material is effectively prevented. To be done.

FIG. 1 is an explanatory view showing a state in which a finish plating layer is formed on a nickel-containing base material of a decorative article according to the present invention through an undercoat plating layer (described later), and FIG. 2 is glasses to which the present invention is applied. It is a perspective view which shows the principal part of a frame.

In FIG. 1, when the thickness of the finish plating layer II formed on the base material 1 containing nickel is 0.5 μm or less, the plating layer is easily worn during the above test, and the nickel is sufficiently prevented from being released to the surface. Can not. When the thickness of the finish plating layer is about 0.5 μm on average, no substantial color development is observed even after repeating the above color development test for 3 cycles (30 seconds × 3).

In the case of plating ornaments such as spectacle frames, the amount of electrodeposition varies greatly depending on the shape of each part, and usually the amount of electrodeposition at the bent part (lower part in contact with skin) 1 of the frame shown in FIG. Is the average representative value. However, the difference between the thin part of the plating layer and the thick part in the figure (for example, parts 2 and 3 in Fig. 2) may be about twice, so in actual products it is the original purpose of finish plating. In addition to improving wear resistance and corrosion resistance, it is considered necessary to make the finish plating layer II thicker so that the value of the free nickel is sufficiently smaller than the standard value. The average lower limit of the thickness of the finish plating layer II was set to 0.5 μ.

On the other hand, although it depends on the nickel content in the substrate I, when the thickness of the plating layer becomes about 2.0 μ, the release of nickel from the substrate I almost disappears, and even if it exceeds 5.0 μ, it is simply increased. This results in increased plating costs. Furthermore, in finish plating of Pd-based alloys, defects such as cracks are more likely to occur as the thickness increases, and as described above, the amount of electrodeposition changes significantly depending on the shape of each part. Therefore, the underlying nickel base material may be exposed from the defective portion. Therefore, the upper limit of the thickness of the finish plating layer II is set to 5.0μ on average.

The material of the finish plating layer II does not contain nickel, the appearance of the plating is white which is equivalent to that of nickel plating, it has abrasion resistance, and it is well compatible with the base material I. However, Pd-based alloys such as Pd and Au-Pd, and Sn-based alloys such as Au-Sn are suitable.

In the present invention, the base plating layer III may be formed in advance on the base material I in order to smooth the surface of scratches, roughness, pinholes and the like. In this case, the base plating layer III is preferably plated with Pd-Ni alloy containing nickel to a thickness of 1 μm or more. The Pd and Ni components in the base plating layer III are well compatible with Pd of the finish plating layer II and Ni of the base material I, and thus improve the adhesion between the base material I and the finish plating layer II.

Unlike the conventional undercoating, the undercoating layer III has a thickness (1 μm or more) sufficient to repair and smooth scratches and pinholes on the substrate I, unlike the conventional undercoating. The sex and the like are given for the purpose of preventing nickel release. The nickel content of the base plating layer III is preferably smaller than the nickel content of the substrate I, and is usually in the range of 20-40% with a limit of about 40%.

Example 1 2-10 g of Pd (as metal) per liter of plating bath for a material of an eyeglass frame made of nickel-chromium alloy (Ni 80-95%, Cr 5-15%, other Ag, Mg, etc.) Using a bath composition containing 5 to 15 g of Ni (metal equivalent), 50 to 100 g of conductive salt, and 1 to 10 cc of organic additive, pH 7.5 to 8.5, liquid temperature 20 to 40 ° C., time 10 minutes, current density, 0.5 Undercoating of Pd-Ni alloy was formed to a thickness of about 2 μm under the plating condition of ˜1.5 A / dm ² .

Next, with respect to the spectacle frame with the undercoat, 5-25 g of Pd (metal conversion), 50-100 g of conductive salt, 10-20 g of ammonium hydroxide and organic luster for 1 liter of bath liquid. Using a bath containing 2-10 cc of the agent, a Pd finish plate was prepared under the plating conditions of pH 12-13, liquid temperature 25-40 ° C, time 15 minutes, and current density 0.5-1.5 A / cm ^2. It was formed to a thickness of 2 μm.

The appearance of the obtained spectacle frame was white and exhibited a color tone almost equal to that of a normal product plated with Ni or Pd—Ni.

This spectacle frame showed that in the color development test with dimethylglyoxime, no color developed at all even after repeating the regular coloration test for 3 cycles, and the free value of nickel was below the standard value.

Example 2 A meganeframe composed of nickel-chromium alloy (Ni 80-95%, Cr 5-15%, other Ag, Mg, etc.) and nickel silver (Cu 60-70%, Ni 15-20%, balance Zn) On the other hand, for one liter of the bath liquid, 5-25 g of Pd (metal conversion), 50-150 g of conductive salt, 10-20 g of ammonium hydroxide and 2-10 cc of organic brightener were used. A Pd finish plating was formed to a thickness of 2 μm under the plating conditions of a liquid temperature of 25-40 ° C., a time of 15 minutes, and a current density of 0.5-1.5 A / cm ² .

The spectacle frame obtained had a white appearance and exhibited a color tone almost equivalent to that of a normal product plated with Ni or Pd—Ni.

This spectacle frame showed that in the color development test with dimethylglyoxime, no color developed at all even after repeating the prescribed color development test for 3 cycles, and the release value of nickel was below the standard value.

Reference Example A spectacle frame made of pure titanium (having a titanium content of 99.9% or more) was subjected to a final plating of 2 μm in thickness under the same conditions using the same Pd plating bath composition as the final plating of Examples 1 and 2. Layers were formed. The obtained spectacle frame had a white appearance similar to that of each example.

[0027]

EFFECTS OF THE INVENTION According to the present invention, it is possible to prevent release of nickel from a base material containing nickel or formed with a nickel-containing plating to prevent nickel allergy in use.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a cross section of a decorative article of the present invention.

FIG. 2 is a perspective view of a main part of an eyeglass frame to which the present invention is applied.

[Explanation of symbols]

 I Base material II Finish plating layer III Base plating layer

Claims (2)

[Scope of utility model registration request] 1. A white finish plating layer made of a Pd-based alloy or a Sn-based alloy based on a nickel-containing base material on average 0.5-.
Nickel allergic prevention ornaments formed with a thickness of 5 μm. 2. The nickel-allergic preventing decorative article according to claim 1, wherein a Pd—Ni based undercoat having a Nitzle content of 40% or less is previously formed on the nickel-containing base material.