JP3073148B2 - Decorative material - Google Patents

Abstract

PURPOSE: To produce a decorative member of the color of white, gold, black or the like causing no Ni allergies by coating the surface of a base material with a copper-base metal plated substrate, a tin-copper-Pd alloy plated layer having a specified compsn. and a finish plated layer composed of Pd, Rh and Rt in succession respectively by specified thickness. CONSTITUTION: The surface of a base material 1 constituted by brass is applied with a substrate 2 of copper or a copper alloy of >=1μm thickness. This surface is applied with a tin-copper-Pd alloy plated layer 3 of >=0.2μm thickness contg., as essential components, by weight, 10 to 20% Sn, 10 to 80% Cu and 50% Pd. This surface is applied with a finish plated layer 4 of 0.2 to 0.5μm thickness composed of one or more kinds among Pd, Ph and Pt. Or, the layer 4 is formed of a gold or gold alloy plated layer contg. no Ni with 0.02 to 5μm thickness, or the layer 3 is applied with a TiN layer of 0.1 to 10μm thickness and the layer 4 is formed of a gold or gold alloy plated layer contg. no Ni with 0.005 to 0.5μm thickness. or the layere 3 is applied with a Ti layer of 0.2 to 1.0μm thickness and the layer 4 is formed of a TiNCO layer or the like with 0.5 to 2.0μm thickness.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative member, and more particularly, to a white decorative member, a golden decorative member, a black decorative member, or a multicolor decorative member having a combination of these colors, in which a wearer does not cause Ni allergy. Regarding members.

[0002]

2. Description of the Related Art Wristwatch case parts, back lids, bands, and other watch external parts and eyeglass frames, necklaces,
Jewelry such as bracelets, earrings, rings, and earrings are all decorative members worn in direct contact with the skin, and most of them have a color tone such as white gloss, golden gloss, and black gloss.

When these decorative members are manufactured industrially, usually, a wet plating method or a dry plating method is applied. For example, in the case of a watch case having white gloss, a Ni plating layer having a thickness of about 2 to 3 μm is formed as a base layer on the surface of a base made of brass, nickel silver, or the like, and then the N
A Pd—Ni alloy plating layer having a thickness of about 2 to 3 μm is formed as a finishing layer on the i plating layer,
Usually, it is manufactured by flash plating Rh, Pt, or the like on the Ni alloy plating layer.

[0004] In the case of a decorative member having a golden luster, a thickness of 2-3 μm is generally applied to the surface of a base material such as brass or nickel silver.
After forming a Ni plating layer having a thickness of about
A Pd-Ni alloy plating layer having a thickness of about 3 [mu] m is formed, and an Au plating layer having a thickness of about 1 to 2 [mu] m or an Au-Ni alloy plating layer having a thickness of, for example, 22 carats is formed thereon. In the case of a golden decorative member, Ni
After the plating layer and the Pd-Ni alloy plating layer are formed in this order by a wet plating method, a thickness of 0.1 to 10 μm is formed on the Pd-Ni alloy plating layer by a dry plating method such as a sputtering method or an evaporation method. About TiN layer and Au or A
A structure in which a layer of a u-Ni alloy is formed in this order has also been proposed.

In the case of a decorative member having a black luster, a Ni plating layer having a thickness of about 2 to 3 μm or a Cu—Ni—C
After forming an r-alloy plating layer, a thickness of 0.5 to 3
A black Ni plating layer or black Cr plating layer of about μm is formed. Furthermore, in the black decorative member, after the above-mentioned Ni plating layer or Cu-Ni-Cr alloy plating layer is formed on the surface of the base material by a wet plating method, an ion plating method or a sputtering method is applied thereon. There has been proposed a method in which a TaC layer having a thickness of about 0.1 to 2 μm is formed by a PVD method.

However, since the above-mentioned conventional white decorative member, golden decorative member and black decorative member all contain Ni, this Ni is free Ni by body sweat or the like.
, Which may cause skin irritation and the like due to contact with the skin. In order to suppress the occurrence of such Ni allergy, recently, white decorative members, golden decorative members, and black decorative members that do not use Ni have been proposed.

For example, in the case of a white decorative member, a Cu plating layer or Sn 30 to 35% by weight is formed on the surface of a base material such as brass.
A Sn-Cu alloy plating layer containing 2 μm or more is formed thereon, and a Pd plating layer having a thickness of about 0.1 to 5 μm is further formed thereon as a finishing layer, or further formed on the Pd plating layer. What formed the flash plating layer of Rh or Pt is known.

In the case of a gold decorative member, a Cu plating layer or the above-mentioned Sn-C
After forming a Cu alloy plating layer such as a u alloy, a Pd plating layer is formed thereon, and then an Au plating layer or an Au alloy containing no Ni such as an Au-Fe alloy is formed on the Pd plating layer. What formed the plating layer is known.

[0009] Further, a TiN layer having a thickness of about 0.1 to 10 μm and a layer of Au alone or a layer of an Au alloy containing no Ni are formed in this order on the Pd plating layer by a dry plating method. Decorative members are also known. And
There is also known a black decorative member containing no Ni component by directly forming the above-described TaC layer on the above-mentioned Pd plating layer by a dry plating method.

[0010]

The decorative member described above is
Neither contains Ni components, so Ni
Does not cause allergies. However, since these decorative members use the expensive noble metal Pd to form the plating layer, the manufacturing cost is extremely high.

Therefore, in order to reduce the relative content of Pd in the plating layer and reduce the overall manufacturing cost, efforts have been made to apply a Pd alloy plating layer instead of the Pd plating layer. . As such a Pd alloy plating layer, for example, a plating layer made of a Sn—Cu—Pd alloy is known. However, this Sn-Cu
-In the case of a Pd alloy plating layer, the content of Pd is 50 to 9
This is considerably as large as about 9% by weight, which is insufficient in terms of reduction in manufacturing cost.

[0012] From these facts, the present inventors consider that Pd
A study on a Sn—Cu—Pd alloy plating layer with a small content was conducted, and Sn: 10 to 20% by weight, Cu: 10 to 8
Sn-Cu composed of 0% by weight and Pd: 10 to 50% by weight
-We have developed a Pd ternary alloy plating method and a plating bath used therefor, and have already filed an application as Japanese Patent Application No. 5-80844.

The Sn—Su—Pd alloy plating layer proposed here has a lower density than a pure Pd plating layer. For example, when compared as a plating layer having the same thickness,
Since the content of Pd is reduced by about 60%, the manufacturing cost is reduced. Further, the plating layer has good corrosion resistance and excellent mirror gloss. The present invention relates to this Sn-C
Utilizing the above-mentioned excellent properties of the u-Pd alloy plating layer, a white decorative member, a golden decorative member, or a black decorative member which does not cause Ni allergy and is inexpensive in production cost, and a combination thereof. An object is to provide a multicolor decorative member.

[0014]

In order to achieve the above object, the present invention relates to a base material; a base material which covers the surface of the base material and which is made of a Cu plating layer or a Cu alloy plating layer and has a thickness of 1 μm or more. Plating layer; covers the surface of the base plating layer, Sn: 10 to 20% by weight, Cu: 10 to 80%
Wt%, Pd: a Sn—Cu—Pd alloy plating layer having a thickness of 0.2 μm or more containing 10 to 50% by weight as an essential component; and coating the Sn—Cu—Pd alloy plating layer with P
a decorative plating layer of at least one member selected from the group consisting of d, Rh, and Pt and having a thickness of 0.2 to 5 μm;

A base material; which covers the surface of the base material;
1μm thick consisting of u plating layer or Cu alloy plating layer
Above base plating layer; thickness covering the surface of the base plating layer and essentially containing Sn: 10 to 20% by weight, Cu: 10 to 80% by weight, and Pd: 10 to 50% by weight.
An Au—Sn—Cu—Pd alloy plating layer having a thickness of 0.2 μm or more;
A gold-plated decorative component (hereinafter referred to as a first gold-colored decorative member) comprising: a plating layer or a plating layer having a thickness of 0.2 to 5 μm, which is made of a Ni alloy-containing Au alloy plating layer; TiN having a thickness of 0.1 to 10 μm and covering the surface of the Sn—Cu—Pd alloy plating layer
And a layer of Au alone or Ni
And a finish layer having a thickness of 0.05 to 0.5 [mu] m made of an Au alloy containing no gold (hereinafter, referred to as a second golden decorative member).

Further, a base material;
1μm thick consisting of u plating layer or Cu alloy plating layer
Above base plating layer; thickness covering the surface of the base plating layer and essentially containing Sn: 10 to 20% by weight, Cu: 10 to 80% by weight, and Pd: 10 to 50% by weight.
A Sn—Cu—Pd alloy plating layer having a thickness of 0.2 μm or more;
Thickness 0.2 covering the surface of the n-Cu-Pd alloy plating layer
A Ti layer of about 1.0 μm;
a 0.5-2.0 μm-thick finishing layer of iNCO;

Further, a substrate; which covers the surface of the substrate,
1μm thick consisting of u plating layer or Cu alloy plating layer
Above base plating layer; thickness covering the surface of the base plating layer and essentially containing Sn: 10 to 20% by weight, Cu: 10 to 80% by weight, and Pd: 10 to 50% by weight.
A Sn—Cu—Pd alloy plating layer having a thickness of 0.2 μm or more;
The surface of the n-Cu-Pd alloy plating layer is covered, and Pd, R
h, Pt, Au, Au alloy, TiNCO, a finishing layer having a thickness of 0.2 to 5.0 μm; and covering a part of the surface of the finishing layer, A partial finish layer of different shades of different materials.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a white decorative member A of the present invention will be described with reference to FIG. In FIG. 1, a substrate 1 is made of brass, and the surface of the substrate 1 has a Cu plating layer or a Cu plating layer.
Base plating layer 2 having a thickness of 1 μm or more made of an alloy plating layer
It is covered with. The base plating layer 2 is formed by a wet plating method, and the surface of the base material 1 and a Sn—Cu—Pd
It has the function of ensuring the adhesion to the alloy plating layer and preventing the plating coating from peeling off, and also improves the glossiness of the base material by the leveling property of Cu.

The substrate 1 is not limited to brass, but may be, for example, copper, copper alloy (tan copper, phosphor bronze), zinc,
A zinc alloy (Zn-Al alloy, Zn-Al-Cu alloy) or the like may be used. The thickness of the base plating layer 2 is 1 μm
When the thickness becomes thinner, a brittle intermetallic compound is generated between the substrate 1 (brass) during wet plating, and the adhesion between the base plating layer 2 and the surface of the substrate 1 is reduced. However, even if the thickness is too large, not only is it meaningless as a base plating layer, but also the accumulation of plating distortion becomes large and causes a peeling phenomenon. The preferred thickness of the base plating layer 2 is 1 to 5 μm.

When the base plating layer 2 is formed of a Cu alloy, the Cu alloy may be, for example, a Cu—Sn alloy,
Cu-Sn-Zn alloy, Cu-Sn-Pb alloy, Cu-
Examples thereof include Sn—Cd alloys. Of these, Sn: 20 to 40% by weight, Zn: 1 to 10% by weight.
Is preferable, and the balance is Cu.

When the base material is made of brass, the base plating layer 2 formed of such a Cu alloy may be combined with a Zn component in the base material 1 or a Sn component in a Sn—Cu—Pd alloy plating layer described later. Since the affinity becomes good, the substrate 1 and the Sn-Cu-
Good adhesion with the Pd alloy plating layer can be ensured. In this case, if the content of Sn is less than 20% by weight, the corrosion resistance is deteriorated, and if it is more than 40% by weight, the strain is increased and it is easy to peel off from the surface of the substrate. Further, when the content of Zn in the Cu alloy is less than 1% by weight, the function of alleviating the difference between the deposition potentials of Cu and Sn during plating is weakened, which is favorable during low-current operation and high-current operation. Luster is difficult to appear. Also, Zn
Is more than 10% by weight, the corrosion resistance is reduced, and the amount of Cu deposited in the plating layer is increased, so that the whole becomes yellowish, which is inconvenient.

Such an alloy composition can be easily realized by adjusting the composition of a plating bath used in wet plating. Next, an Sn—Cu—Pd alloy plating layer 3 is formed on the surface of the base plating layer 2 by a wet plating method. The Sn—Cu—Pd alloy plating layer 3 is formed by a method described in Japanese Patent Application No. 5-80844, and the composition thereof is Sn: 10 to 20.
%, Cu: 10 to 80% by weight, and Pd: 10 to 50% by weight as essential components.

In the above-mentioned Sn—Cu—Pd alloy plating layer, when the Sn content is less than 10% by weight, the surface gloss is deteriorated, the corrosion resistance is reduced, and the Sn content is 20% by weight. Since the surface gloss becomes worse as the amount increases, the Sn content is set in the above range. It is preferably from 13 to 19% by weight, particularly preferably from 16 to 18% by weight.

Further, in the case of a plating layer having a Cu content of less than 10% by weight, the surface gloss deteriorates, and if it exceeds 80% by weight, the surface gloss deteriorates and the corrosion resistance of the plating layer deteriorates. The Cu content is set in the above range. It is preferably from 35 to 65% by weight, particularly preferably from 43 to 45% by weight. Further, in the case of a plating layer having a Pd content of less than 10% by weight, the surface gloss is poor, and if it is more than 50% by weight, the surface gloss is also poor and the corrosion resistance is poor, and the production cost is increased. Therefore, the Pd content is set in the above range. It is preferably from 25 to 45% by weight, particularly preferably from 37 to 40% by weight.

In particular, when the composition of the Sn—Cu—Pd alloy plating layer is 16 to 18% by weight of Sn, 43 to 45% by weight of Cu, and 37 to 40% by weight of Pd, the plating layer The production cost is low due to the low content of expensive Pd, the surface gloss is excellent, the corrosion resistance is good, and the effect of increasing the adhesion between the above-mentioned base plating layer 2 and the finish plating layer described below is obtained. It is preferable because it is extremely excellent and has good heat resistance.

The thickness of the Sn—Cu—Pd alloy plating layer 3 is set to 0.2 μm or more. This thickness is 0.2 μm
This is because if the thickness is made thinner, a poorly formed portion occurs at the time of plating, and the corrosion resistance at that portion decreases. The preferred thickness is from 0.2 to 10 μm. Finally, S
By covering the surface of the n-Cu-Pd alloy plating layer 3, P
One, two or more finish plating layers 4 of d, Rh, and Pt are formed by a wet plating method, and the white decorative member A of the present invention is formed.
Is manufactured.

The thickness of the finish plating layer 4 is 0.2 to 5 μm.
m. If this thickness is thinner than 0.2 μm,
Difficulty in white gloss color tone as a decorative member.
Even if the thickness is larger than m, the improvement in color tone reaches saturation, and only expensive precious metals are consumed, which leads to an increase in manufacturing cost. The thickness of the finish plating layer 4 is preferably 0.2 to 3 μm in terms of securing economically favorable white gloss color tone.

By making the thickness of the Sn—Cu—Pd alloy plating layer 3 relatively thick, 4 to 5 μm, the thickness of the finish plating layer 4 can be reduced, thereby improving the surface quality. It is possible to develop a color tone with a white luster, which is economically advantageous. In this white decorative member A, since neither the base material 1 nor each plating layer contains Ni, even if it comes into contact with body sweat or the like, no free Ni is eluted, and Ni allergy is not caused. Absent. The Sn—Cu—Pd alloy plating layer 3 has a white luster as a whole and has good corrosion resistance. For example, even if the uppermost finishing plating layer 4 is damaged, the surface of the decorative member A is kept for a long time. White glossiness.

Further, since the hardness (Hv) of the Sn—Cu—Pd alloy plating layer 3 is as high as about 250 to 350, even if the finish plating layer 4 may be damaged, for example, it may cause damage to the base layer. The situation where the material 1 is damaged can be effectively prevented. Next, the first golden decorative member B of the present invention will be described with reference to FIG.

This gold decorative member B is shown in FIG. 1 except that the uppermost finish plating layer 5 is a gold luster plating layer composed of an Au plating layer or an Au alloy plating layer containing no Ni. It is the same as the layer structure of the white decorative member A. The above-mentioned finish plating layer 5 is formed by a wet plating method, and its thickness is set to 0.2 to 5 μm.

When the thickness is smaller than 0.2 μm, the white color tone of the Sn—Cu—Pd alloy plating layer 3 located as the lower layer appears, and it is difficult to achieve the golden gloss color tone as the golden decorative member. And even if thicker than 5 μm
This is because the color tone of the golden luster does not change and only expensive Au is consumed, leading to an increase in manufacturing cost. When the finish plating layer 5 is formed of an Au alloy, the Au alloy may be, for example, an Au—Fe alloy, an Au—Pd alloy, or an Au alloy.
u-Pt alloy, Au-Sn alloy, Au-Ag alloy, Au
-In alloy, Au-Cu alloy, Au-Pd-Fe alloy,
Au which does not contain Ni like Au-In-Fe alloy
Alloys are used.

In the case of this gold decorative member, as shown in FIG. 3, a Pd plating layer 6 is interposed between the Sn—Cu—Pd alloy plating layer 3 and the finish plating layer 5 by a wet plating method. The structure B ′ may be used. This layer structure B ′ is preferable because the adhesion between the Sn—Cu—Pd alloy plating layer 3 and the finish plating layer 5 is improved as compared with the layer structure of FIG.

At this time, if the thickness of the Pd plating layer 6 is too large, the production cost is increased. If the thickness is too small, the above-mentioned effect of improving the adhesion is not effectively exhibited. It is preferable to be within the range. Next, the second gold decorative member C will be described with reference to FIG. In this golden decorative member C, the golden finish plating layer 5 in the golden decorative member B shown in FIG. 2 is composed of a TiN layer 7 formed by a dry plating method and a finishing layer 8 made of Au alone or an Au alloy containing no Ni. Except for the layer structure laminated in this order, the layer structure is the same as that of the golden decorative member B.

First, the TiN layer 7 has a golden luster and has good abrasion resistance. Even when the finishing layer 8 formed on the TiN layer 7 is worn away and no longer shows the golden luster. The TiN layer plays a role of securing the function as a golden decorative member for a long period of time by expressing golden luster. Further, even if the thickness of the finishing layer 8 made of Au or an Au alloy is greatly reduced, the gold decorative property of the surface of the obtained member is ensured, so that the manufacturing cost can be reduced.

The thickness of the TiN layer 7 is set to 0.1 to 10 μm. If the thickness is less than 0.1 μm, sufficient abrasion resistance cannot be maintained, and the white luster of the underlying Sn—Cu—Pd alloy plating layer 3 will be exposed in a short period of time. If the thickness is more than 10 μm, TiN
Fogging occurs in the layer 7 itself, which impairs its appearance and increases the production cost. The preferred thickness is 0.2 to 0.3 μm.

The thickness of the finishing layer 8 formed on the TiN layer 7 is set to 0.05 to 0.5 μm. This thickness is 0.0
If the thickness is less than 5 μm, the covering power is insufficient and the TiN layer 7 serving as an underlayer is exposed, and even if the thickness is more than 0.5 μm, the color tone of the golden luster does not change and the expensive A
it only consumes u. The preferred thickness of the finishing layer 8 is
0.2 to 0.3 μm.

Both the TiN layer 7 and the finishing layer 8 are formed by a known dry plating method. Examples of the dry plating method applied at this time include a sputtering method, an ion plating method, and a vacuum evaporation method. In the case of the gold decorative member C, Ni is not contained in any of the constituent materials, so that free Ni does not elute at all even when it comes into contact with body sweat, etc., and the wearer may not cause Ni allergy. Absent.

Further, even if the soft finishing layer 8 wears out and loses its golden luster during wearing, the underlying TiN layer 7 having excellent wear resistance exhibits golden luster over a long period of time. Can be. Furthermore, even if the finishing layer 8 and the TiN layer 7 are damaged and body sweat or the like intrudes into them, the Sn—Cu—Pd alloy plating layer 3 located thereunder has excellent corrosion resistance, so that it is decorative. The corrosion resistance of the member is ensured for a long time.

In the case of this golden decorative member, as shown in FIG. 5, a Pd plating layer 6 is interposed between the Sn—Cu—Pd alloy plating layer 3 and the TiN layer 7 by a wet plating method. It may be C '. In the case of this layer structure C ′, Sn
This is preferable because the adhesion between the Cu—Pd alloy plating layer 3 and the TiN layer 7 is improved as compared with the case of the layer structure of FIG.

At this time, if the thickness of the Pd plating layer 6 is too large, the production cost is increased. If the thickness is too small, the above-mentioned effect of improving the adhesion is not effectively exerted, so that the thickness is 0.2 to 1 μm. It is preferably within the range. Next, the black decorative member D of the present invention will be described with reference to FIG. The black decorative member D is a layer made of TiNCO in which the uppermost finishing layer 10 is formed by dry plating, and the same between the finishing layer 10 and the Sn—Cu—Pd alloy plating layer 3 by dry plating. Except that the formed Ti layer 9 is interposed, the layer structure is the same as that of the white decorative member A shown in FIG.

First, the finishing layer 10 has a black gloss. And the hardness (Hv) is 1000-1500, it is extremely excellent in abrasion resistance, and keeps the function as a black decorative member for a long time. The Ti layer 9 formed under the finishing layer 10 is formed of Sn-Cu-P
It functions to firmly adhere the d alloy plating layer 3 to the finishing layer 10. By interposing this Ti layer 9,
In the case of the black decorative member D, the black finishing layer 10 is made of Sn-C
The problem of peeling off from the u-Pd alloy plating layer 3 does not occur at all.

Even when the Ti layer 9 is not interposed, that is, even when the finishing layer 10 is formed directly on the Sn—Cu—Pd alloy plating layer 3, the black decorative member D can be used. However, as long as the user carries the mobile phone in a normal state, the problem that the finishing layer 10 peels off does not occur. The thickness of the finishing layer 10 is set to 0.5 to 2.0 μm. If this thickness is made smaller than 0.5 μm, the T
Due to the influence of the color tone of the i-layer 9 and the Sn—Cu—Pd alloy plating layer 3 (all of which are white), it becomes difficult to obtain beautiful black gloss. When the thickness is more than 2.0 μm, the finishing layer 1
0, the strain accumulation at the time of forming 0 increases,
Cracks and the like may occur, and the workability at the time of forming the layer is deteriorated. The preferred thickness is between 0.8 and 1.5 μm.

The thickness of the Ti layer 9 formed under the finishing layer 10 is set to 0.2 to 1.0 μm. Set this thickness to 0.
When the thickness is smaller than 2 μm, the finish layer 10 and the Sn—Cu—
The tendency to decrease the adhesion between the Pd alloy plating layer 3 appears, and even if the thickness is more than 1.0 μm, not only the effect of improving the adhesion does not change but also the workability at the time of forming the layer is deteriorated. . The preferred thickness is 0.4 to 0.8 μm.

Both the finishing layer 10 and the Ti layer 9 are formed by a dry plating method. The dry plating method applied at this time includes, for example, an ion plating method, a sputtering method, and a vacuum deposition method. In particular, it is preferable to apply the method disclosed in JP-A-63-161158 for forming the finishing layer 10 having black gloss.

In the above description, the surface is white gloss,
The present invention relates to a decorative member having a golden gloss or a black gloss. In the present invention, by combining these, a multicolor decorative member having at least two glossy colors combined on the surface can be manufactured. That is, Pd, R is formed on the Sn-Cu-Pd alloy plating layer.
h, Pt (all white) layers, Au, Au alloy (all gold) layers, or TiNCO (black) layers are formed as finishing layers, and then a part of the surface of the finishing layers To form a layer having a color tone different from that of the finish layer, thereby forming a surface in which the color tone of the finish layer and a color tone different from the color tone are mixed.

[0046] For example, based on FIG. 7, of the multi-color decorative member of the present invention, the surface will be described decorative member E ₁ having a 2-color white glossy and golden gloss. This decorative member E ₁
A part of the surface of the finish plating layer 4 of the platinum decorative member A shown in FIG. 1 is covered to form a pattern 5a of an Au plating layer or an Au alloy plating layer.

[0047] When manufacturing the decorative member E _1, first, by coating a white decorative member entire final plating layer 4 of A shown in FIG. 1, to form a plating layer 5 of Au or Au alloy ( (FIG. 8). Next, a mask pattern as shown in FIG. 9 is formed on a portion to be left of the surface of the plating layer 5 by a printing method such as screen printing, pad printing, offset printing, a brush coating method, or a photoengraving method. 11 is formed. Thereafter, the member shown in FIG.
The plating layer 5 other than the portion covered with the mask pattern 11 is dissolved and removed by dipping in a u-strip solution.
Thus, as shown in FIG. 10, the mask pattern 1 in a predetermined pattern is formed on the plating layer 4 having white luster.
The portion of the plating layer 5 covered with 1 is left.

Thereafter, the mask pattern 11 is peeled and removed.
Thus, the white and gold two-color decorative member E shown in FIG.₁But
can get. FIG. 11 shows another two-color decorative member E._TwoShowing the cross section
FIG. This decorative member E_TwoIn the case of, black shown in FIG.
On the finishing layer 10 of the color decoration member D, the decoration member described above
E ₁The pattern of the gold plating layer in the same way as
5a are formed. Therefore, this decorative member E_Two
Is black with a gold pattern formed on a black glossy surface
It is a two-color gold decorative member.

[0049]

【Example】

Example 1 A white decorative member was manufactured by forming the layer structure A shown in FIG. 1 on the surface of a watch case made of brass as follows. (1) Formation of base plating layer 2 Composition of plating bath: Na ₂ SnO ₃ .3H ₂ O 60 g /
Liter CuCN 20 g / liter K ₂ SO ₃ H 10 g / liter KCN (free) 30 g / liter KOH 60 g / liter Zn (CN) ₂ 5 g / liter Plating conditions: bath temperature 50 ° C., current density 2.4 A / dm ² , pH 1
2.5, deposition rate 0.33 μm / min, time 10 minutes.

The surface of the watch case 1 has a thickness of about 3 μm C
The u-Sn-Zn alloy plating layer 2 was formed. (2) Formation of Sn—Cu—Pd alloy plating layer Next, an Sn—Cu—Pd alloy plating layer 3 was formed on the Cu—Sn—Zn alloy plating layer 2 under the following conditions.

Plating bath: Na ₂ SnO ₃ .3H ₂ O 6
0 g / liter (Sn equivalent 26.7 g / l) CuCN 20 g / l (Cu equivalent 14.2 g / l) K ₂ SO ₃ H 10 g / l KCN (free) 30 g / l KOH 60 g / l K ₂ Pd ( _{CN) 4 · 3H 2 O 30g} / l (Pd equivalent amount 9.3 g / l) plating conditions: bath temperature 50-55 ° C., a current density of 2.0A / dm ^2,
Current efficiency 47.8%, pH 12.5-13, deposition rate 0.33
μm / min, time 9 minutes.

A plating layer having a thickness of about 3 μm, a hardness (Hv) of about 300, and a density of 9.6 g / cm ³ was formed. When the composition of this plating layer was simply quantified with a scanning electron microscope and an X-ray microanalyzer, it was a ternary alloy of Sn: 17.12% by weight, Cu: 44.22% by weight, and Pd: 38.66% by weight. . (3) Formation of Finish Plating Layer 4 The plating layer 4 was formed on the Sn—Cu—Pd alloy plating layer 3 under the following conditions.

Plating bath: "PARABRITE-SSS" (trade name) manufactured by Japan Pure Chemical Co., Ltd. Plating conditions: bath temperature 55 ° C., current density 1.5 A / dm ² , pH 7.
6, deposition rate 0.33 μm / min, time 6 minutes. The Pd plating layer 4 having a thickness of about 2 μm and having white luster was formed. The white watch case thus obtained was subjected to 9.9 g / l of sodium chloride, 0.8 g / l of sodium sulfide, 7.1 g / l of urea, 0.19 ml / l of aqueous ammonia, 0.2 g / l of saccharose. , Lactic acid (50%) in 0.8 ml / liter artificial sweat (temperature 40 ° C.) for 24 hours.

No surface discoloration occurred and good corrosion resistance was exhibited. The white watch case was left at a temperature of 200 ° C. for 5 hours and subjected to a heating test. Peeling of the plating was not observed at all. Example 2 A gold decorative member having a layer structure B shown in FIG. 2 was produced on the surface of a watch case made of brass as follows. Example 1 was applied to a base plating layer 2 and a Sn—Cu—Pd alloy plating layer 3.
It was formed in the same manner as described above.

Then, Au 10 g / liter, Pt 0.3
g / L, 100 g / L of citric acid, 50 g / L of sodium citrate, a plating bath having a pH of 4.0, a bath temperature of 40 ° C., and a current density of 1.0 A / dm ^2.
By performing wet plating for 5 minutes, an Au-Pt alloy plating layer 5 having a thickness of 3.6 μm was formed on the Sn-Cu-Pd alloy plating layer 3.

The obtained decorative member exhibited substantially the same corrosion resistance and heat resistance as those of Example 1. Example 3 A gold decorative member having a layer structure B ′ shown in FIG. 3 was manufactured on the surface of a watch case made of brass as follows.

First, the base plating layer 2 was formed under the same conditions as in Example 1, and the thickness of the base plating layer 2 was changed to 2.0 under the same conditions as in Example 1 except that the plating time was 7.5 minutes. 5 μm S
Example 1 except that an n-Cu-Pd alloy plating layer 3 was formed, and further that the plating time was 1 minute.
A Pd plating layer 6 having a thickness of 0.5 μm is formed under the same conditions as when the finish plating layer is formed, and finally, the Pd plating layer 6 is formed.
Then, an Au—Pt alloy plating layer 5 was formed under the same conditions as in Example 2.

The obtained decorative member exhibited substantially the same corrosion resistance and heat resistance as those in Example 1. Example 4 Underplating layer 2 and Sn—Cu—Pd alloy plating layer 3 were sequentially formed on the surface of a watch case made of brass under the same conditions as in Example 1 and then over Sn—Cu—Pd alloy plating layer 3. Then, a TiN layer 7 and a finishing layer 8 were formed under the following conditions to form a golden decorative member having a layer structure C shown in FIG.

The member on which the Sn—Cu—Pd alloy plating layer 3 is formed is set in an ion plating apparatus,
After the inside of the apparatus was evacuated, Ar gas was introduced to reduce the degree of vacuum in the apparatus to 1.0 × 10 ⁻³ Torr. The thermoelectron filament and the plasma electrode provided in the apparatus were activated to generate Ar plasma, and the surface of the Sn—Cu—Pd alloy plating layer 3 was washed with ion bombard for 10 minutes.

Next, N ₂ gas was introduced into the apparatus to maintain the degree of vacuum in the apparatus at 2.0 × 10 ⁻³ Torr, and Ti was evaporated for 10 minutes while generating plasma with the plasma gun of the apparatus. A thickness of 0,0 on the Sn-Cu-Pd alloy plating layer 3.
A 5 μm TiN layer 7 was formed. After stopping the evaporation of Ti and the introduction of N ₂ gas, Au-F containing 6% by weight of Fe is used.
e alloy is evaporated to a thickness of 0.3 μm on the TiN layer 7.
The Au-Fe alloy plating layer 8 of m m was formed.

The obtained watch case has a uniform designated gold tone satisfying 1N-14 colors of the Swiss gold plating color standard, and the color tone measured by the color difference meter is L ^* 80, a ^* 1.0, b
^* It was 15.0. Further, a corrosion resistance test for 24 hours was performed using the same artificial sweat as in Example 1. No corrosion or discoloration was observed.

Further, the watch case was wiped with a gauze impregnated with a dimethylglyoxime alcohol solution to remove Ni
A reaction detection test was performed. There was no red coloration and no free Ni was detected. Example 5 In Example 4, the thickness of the Sn—Cu—Pd alloy plating layer 3 was set to 2.5 μm in the same manner as in Example 3, and on top of that, the thickness was 0.5 μm under the same conditions as in Example 3. After the Pd plating layer 6 is formed, the Pd
On the plating layer 6, a TiN layer 7 having a thickness of 0.5 μm,
A 3 μm Au—Fe alloy plating layer 8 was formed to obtain a watch case having a layer structure C ′ shown in FIG.

This watch case was subjected to a 48-hour corrosion resistance test using the same artificial sweat as in Example 1. No corrosion or discoloration was observed. Example 6 Under the same conditions as in Example 1, the base plating layer 2 and the Sn—Cu—Pd alloy plating layer 3 were sequentially formed on the surface of the watch case made of brass, and then the Sn—Cu—Pd alloy plating layer 3 Then, a Ti layer 9 and a TiNCO finishing layer 1 under the following conditions
0 was formed to produce a black decorative member D having a layer structure shown in FIG.

The member on which the Sn—Cu—Pd alloy plating layer 3 is formed is set in a bell jar of an ion plating apparatus, and after evacuating the bell jar, introducing Ar gas to reduce the degree of vacuum in the bell jar to 5 ×. 10 ^-4 to 1 × 10
^-2 Torr. Activating a thermoelectron filament and a plasma electrode provided in the apparatus to generate Ar plasma,
The surface of the Sn—Cu—Pd alloy plating layer 3 was washed with ion bombard for about 10 minutes.

Next, the degree of vacuum in the bell jar was set to 3 × 10
An electron beam generated by a plasma gun of the apparatus was irradiated to metal Ti as an evaporation source at ^-4 to 1 × 10 ^-2 Torr. T that occurred
i-vapor and Ar gas are ionized in the plasma, and a negative potential of 50 to 200 V is applied to the member to accelerate the Sn-Cu
A Ti layer 9 having a thickness of 0.5 μm was formed on the Pd alloy plating layer 3.

Then, O ₂ : 0.1 to 5.0% by volume and C
O: A mixed gas of N ₂ gas and Ar gas containing 0.1 to 3.0% by volume is introduced into the bell jar, and supply / exhaust control is performed to maintain the degree of vacuum in the bell jar at 5 × 10 ⁻³ Torr. did. Next, the electron beam generated by the plasma gun is irradiated on the metal Ti to generate Ti vapor, the metal Ti is used as an anode, the member is used as a cathode, and a DC voltage of 50 V is applied between the two to apply a 5 A ion current. For about 30 minutes.

On the Ti layer 9, a Ti layer having a thickness of about 1 μm
A black finish layer 10 of NCO was formed. The obtained black decorative member D had a glossy black color tone on the surface, and exhibited the same corrosion resistance and heat resistance as the white decorative member of Example 1. Further, even when a bending test at 90 ° was performed, no peeling of the black finish layer on the surface was observed, and the film had excellent adhesion to the substrate.

Example 7 Under the same conditions as in Example 1, a base plating layer 2 and an Sn—Cu—Pd alloy plating layer 3 were sequentially formed on the surface of a watch case made of brass, and then a Sn—Cu—Pd alloy plating layer was formed. 3 and a finish plating layer 4 made of Rh as described below.
Forming a was further produced a decorative member E ₁ of the layer structure shown in FIG. 7 to form a partial final plating layer 5 made of Au-Pt alloy thereon.

First, on the surface of the member on which the Sn—Cu—Pd alloy plating layer 3 is formed, the following conditions are applied: composition of plating bath: Rh 2 g / liter, H ₂ SO ₄ 38
Wet plating was performed at a rate of milliliter / liter, a bath temperature of 40 ° C., and a current density of 1 A / dm ² to form a 1.5 μm-thick Rh finish plating layer 4. The finish plating layer 4 had a deep white luster, a hardness of 850 Hv, and was excellent in abrasion resistance.

On this finish plating layer 4, a 2.5 μm thick Au—Pt alloy plating layer 5 was formed under the same conditions as in Example 2.
Was formed (FIG. 8). Then, a mask ink composed of an epoxy resin is screen-printed on a portion of the surface of the Au-Pt alloy plating layer 5 which is to be left to form a pattern mask 11 as shown in FIG. It was immersed in an Au strip solution to remove the Au-Pt alloy plating layer at locations not covered by the pattern mask 11.

Then, the pattern mask was peeled off by immersion in a peeling solution comprising a mixture of a chlorinated hydrocarbon solvent, alcohols, a nonionic surfactant and paraffin wax. The resulting decorative member E _1, the pattern 5a partial final plating layer of gold tones in a part of the final plating layer 4 on the surface of the white color tone having a deep are drawn, exerts a decorative effect rich in design I was Also, this decorative member E ₁
Showed the same corrosion resistance and heat resistance as the white decorative member of Example 1.

[0072] Incidentally, in this decorative member E _1, when it is desired to increase the area of the partial finishing plating layer of gold color tone, after forming the final plating layer 4 of the white color tone, a pattern mask portion to leave a white color It is preferable to form a partially finished plating layer 5 having a golden tone on the remaining portion after the formation, and finally, it is preferable to peel and remove the pattern mask. Example 8 Under the same conditions as in Example 6, a base plating layer 2, a Sn—Cu—Pd alloy plating layer 3, a Ti layer 9, and a finishing layer 10 made of TiNCO were sequentially formed on the surface of a watch case made of brass. After manufacturing the black decorative member D shown in FIG. 6,
A pattern 5a of a gold-tone partial finish plating layer made of an Au-Pt alloy was formed on the black finishing layer 10 of the black decorative member D in the same manner as in Example 7, and the decorative member E ₂ shown in FIG. Was manufactured.

In the obtained decorative member E ₂ , a pattern of a partially finished plating layer of a gold color tone is drawn on a part of the surface of the finishing layer 10 of a glossy black color tone. Was showing. Further, the decorative member E ₂ is substantially similar corrosion and black decorative member of Example 6, the heat resistance, exhibited adhesiveness. This decorative member E ₂
In the case where it is desired to increase the area of the gold-tone partial finish plating layer, after forming the black-tone finish plating layer 10, a pattern mask is formed on a portion where the black tone is to be left, and the gold-tone finish plating layer is formed on the remaining portion. It is preferable that the partially finished plating layer 5 is formed, and finally, the pattern mask is peeled off.

The decorative member E ₂ can also be manufactured as follows. That is, first, a golden decorative member B having a layer structure as shown in FIG. 2 is manufactured, a finishing layer made of TiNCO is formed on the surface of the finishing plating layer 5, and the surface of a portion of the finishing layer which is desired to be left is patterned. After covering with a mask, Ti
Form a partial finish layer of NCO. Next, the whole is immersed in a 10 to 15% sodium hydroxide solution for a predetermined time to remove and remove other TiNCO except for the TiNCO under the pattern mask, and finally, chlorinated hydrocarbon solvent, alcohols and the like. The pattern mask may be selectively stripped and removed by dipping in a stripping solution composed of a mixture of a nonionic surfactant and paraffin wax.

[0075]

As is apparent from the above description, claim 1
The white decorative member does not elute free Ni because none of the constituent materials contain Ni. The interlayer adhesion of each plating layer is good, the peeling phenomenon does not occur even by a heating test, and the corrosion resistance is excellent due to the function of the Sn—Cu—Pd alloy plating layer.

The gold decorative member of the second and third aspects does not elute free nickel because the constituent material does not contain Ni. Since the black decorative member according to the fourth aspect does not contain Ni, free nickel does not elute at all, and the outermost black finish layer made of TiNCO has extremely high hardness and excellent wear resistance. Moreover, by the function of the Ti layer, Sn-C
It is firmly adhered to the u-Pd alloy plating layer, and can exhibit a black decoration effect over a long period of time.

The surface of the multicolor decorative member according to claim 5 is white-white.
It has a color tone of gold, white-black, black-gold, etc., and exhibits a decorative effect rich in design. Further, in the golden decorative member according to the third and ninth aspects, since all the constituent materials do not contain Ni, the elution of free Ni does not occur, and the uppermost golden layer formed by the dry plating method and the Sn- Cu-
Golden TiN with excellent wear resistance between Pd alloy plating layers
Since the layer is formed by the dry plating method, the overall wear resistance is improved, and the gold decorative member has a long service life.

In the decorative member according to the eighth and tenth aspects, the Pd plating layer formed by the wet plating method is interposed between the Sn—Cu—Pd alloy plating layer and the white finish plating layer or the gold finish plating layer. The interlayer adhesion of the plating layer is further improved. INDUSTRIAL APPLICABILITY The decorative member of the present invention is very useful as a decorative member that eliminates the occurrence of Ni allergy, is white, gold, black, and a combination of these colors.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a layer structure of a white decorative member A of the present invention.

FIG. 2 is a cross-sectional view showing a layer structure of a gold decorative member B of the present invention.

FIG. 3 is a sectional view showing a layer structure of another golden decorative member B ′ of the present invention.

FIG. 4 is a cross-sectional view showing a layer structure of another golden decorative member C of the present invention.

FIG. 5 is a sectional view showing a layer structure of still another golden decorative member C ′ of the present invention.

FIG. 6 is a sectional view showing a layer structure of a black decorative member D of the present invention.

7 is a sectional view showing a layer structure of a multicolor decorative member E ₁ of the present invention.

FIG. 8 shows a case where Au or Au is applied to the surface of the white decorative member A in FIG.
It is sectional drawing which shows the state in which the plating layer which consists of an alloy was formed.

9 is a cross-sectional view showing a state where a pattern mask is formed on the plating layer of FIG.

FIG. 10 is a cross-sectional view showing a state where a plating layer other than a portion where a pattern mask is formed is removed in FIG. 9;

11 is a sectional view showing another layer structure of a multicolor decorative member E ₂ of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Base material (brass) 2 Base plating layer (Cu or Cu alloy) 3 Sn-Cu-Pd alloy plating layer 4 Finish plating layer (Pd, Rh, Pt) 5 Finish plating layer (Au or Au alloy) 6 Pd plating layer 7 TiN layer by dry plating 8 Finished layer of Au or Au alloy by dry plating 9 Ti layer by dry plating 10 Finished layer of TiNCO by dry plating 11 Pattern mask

Continuation of front page (56) References JP-A-2-38556 (JP, A) JP-A-4-83897 (JP, A) JP-A-7-11477 (JP, A) Patent 3029948 (JP, B2) Patent 2921200 (JP, B2) Patent 2921001 (JP, B2) Patent 2921004 (JP, B2) Patent 2925441 (JP, B2) Patent 2630344 (JP, B2) Japanese Patent Publication 2-10876 (JP, B2) (58) Field (Int.Cl. ⁷ , DB name) C25D 3/00-7/12

Claims (12)

(57) [Claims] 1. a substrate; a base plating layer covering the surface of the base material and comprising a Cu plating layer or a Cu alloy plating layer and having a thickness of 1 μm or more;
n: 10 to 20% by weight, Cu: 10 to 80% by weight, P
d: thickness 0.2 μ containing 10 to 50% by weight as essential
m or more of Sn-Cu-Pd alloy plating layer; and Pd, Rh,
Thickness of at least one selected from the group of Pt 0.2
A white decorative member comprising: a finish plating layer having a thickness of about 5 µm. 2. a substrate; a base plating layer having a thickness of 1 μm or more comprising a Cu plating layer or a Cu alloy plating layer, which covers the surface of the base material;
n: 10 to 20% by weight, Cu: 10 to 80% by weight, P
d: thickness 0.2 μ containing 10 to 50% by weight as essential
m or more of a Sn—Cu—Pd alloy plating layer; and a thickness formed of an Au plating layer or an Au alloy plating layer containing no Ni and covering the Sn—Cu—Pd alloy plating layer.
0.2 to 5 μm of a finish plating layer. 3. a substrate; an undercoat layer having a thickness of 1 μm or more comprising a Cu plating layer or a Cu alloy plating layer, which covers the surface of the substrate;
n: 10 to 20% by weight, Cu: 10 to 80% by weight, P
d: thickness 0.2 μ containing 10 to 50% by weight as essential
m or more of Sn—Cu—Pd alloy plating layer;
Thickness 0.1 to 10 covering the surface of the u-Pd alloy plating layer
μm TiN layer; and covering the TiN layer with Au
A thickness of 0.05 consisting of simple substance or Au alloy not containing Ni
A gold decorative member comprising: a finish layer of about 0.5 μm; 4. a base material; a base plating layer having a thickness of 1 μm or more, comprising a Cu plating layer or a Cu alloy plating layer, covering the surface of the base material;
n: 10 to 20% by weight, Cu: 10 to 80% by weight, P
d: thickness 0.2 μ containing 10 to 50% by weight as essential
m or more of Sn—Cu—Pd alloy plating layer;
Thickness that covers the surface of the u-Pd alloy plating layer 0.2 to 1.0
.mu.m of a Ti layer; and
A decorative layer made of O having a thickness of 0.5 to 2.0 μm; 5. A base material; a base plating layer having a thickness of 1 μm or more comprising a Cu plating layer or a Cu alloy plating layer and covering the surface of the base material;
n: 10 to 20% by weight, Cu: 10 to 80% by weight, P
d: thickness 0.2 μ containing 10 to 50% by weight as essential
m or more of Sn—Cu—Pd alloy plating layer;
The surface of the u-Pd alloy plating layer is covered, and Pd, Rh, P
a finishing layer of any one of t, Au, Au alloy, and TiNCO having a thickness of 0.2 to 5.0 μm; and covering a part of the surface of the finishing layer, which is different from the constituent material of the finishing layer A multicolor decorative member, comprising: a partially finished layer of a material having a different color tone; 6. The Cu alloy plating layer comprises a Cu—Sn alloy, a Cu—Sn—Zn alloy, a Cu—Sn—Pb alloy,
2. The method according to claim 1, wherein the alloy comprises one of a u-Sn-Cd alloy.
2, 3, 4 or 5 decorative members. 7. The method according to claim 7, wherein the Cu alloy plating layer has a Sn: 20 to
7. The decorative member according to claim 6, wherein 40% by weight, Zn: 1 to 10% by weight, and the balance is an alloy of Cu. 8. The gold decorative member according to claim 2, wherein a Pd plating layer is interposed between said Sn—Cu—Pd alloy plating layer and said finish plating layer. 9. The gold decorative member according to claim 3, wherein said TiN layer and said finishing layer are both formed by a dry plating method. 10. The gold decorative member according to claim 3, wherein a Pd plating layer is interposed between the Sn—Cu—Pd alloy plating layer and the TiN layer. 11. The gold decorative member according to claim 8, wherein said Pd plating layer is formed by a wet plating method. 12. The black decorative member according to claim 4, wherein both the Ti layer and the finishing layer are formed by a dry plating method.