JPH11118956A - Parts for decoration and its manufacturing method, decoration, electronic equipment, and clock - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide parts for decoration with superior discoloration resistance, corrosion resistance, or the like and decoration electronic equipment and a clock with the parts. SOLUTION: In an exterior finish part 1 for a clock, at least a surface is constituted of a metal material containing 1B family element and a thiol coating 2 consisting of a thiol compound is formed on the surface of the metal material. The thiol coating 2 is preferably formed by the thiol compound containing fluorine. The thiol coating is dipped in the solution of the thiol compound for forming.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative part, a decorative article provided with the same, an electronic device, a watch, and a method of manufacturing a decorative part.

[0002]

2. Description of the Related Art A coating layer made of gold or a gold-based alloy or the like formed by plating on the surface of a watch exterior component is affected by oxygen, sulfur oxides, nitrogen oxides, etc. existing in the air or ultraviolet rays. Compared to immediately after forming the coating layer,
There is a problem that the color tone of the surface changes over time. In addition, gold is optimal for giving a luxury in color tone and has good adaptability to the skin, but has a drawback that dirt due to fingerprints or the like easily adheres.

In order to prevent such discoloration and dirt,
It has been practiced to coat SiO ₂ , Al ₂ O _3, or the like on a coating layer of gold or a gold-based alloy by CVD or PVD.

However, since CVD and PVD are very expensive and the coating is dry, the thickness of the coating film is inadequate when, for example, it has a complex shape with many irregularities such as a watch exterior part. The interference color causes unevenness such as stripes and the like, which has the disadvantage of impairing the appearance of the surface.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a decorative part which has excellent resistance to discoloration and discoloration and stain resistance, can maintain the appearance and gloss of a coating layer, and a decoration provided with the same. It is an object of the present invention to provide a method of manufacturing an article, an electronic device, a timepiece, and an ornamental part that can easily and inexpensively produce such an ornamental part.

[0006]

This and other objects are achieved by the present invention which is defined below as (1) to (17).

(1) A decorative part having at least a surface made of a metal material containing a Group 1B element, wherein a thiol film made of a thiol compound is formed on the surface of the metal material. Parts for decorations.

(2) A decorative component having at least a surface made of at least one metal material selected from the group consisting of Au, Au-based alloy, Ag, Ag-based alloy, Cu, and Cu-based alloy. And a thiol film made of a thiol compound is formed on the surface of the metal material.

(3) The decorative component according to the above (1) or (2), wherein the thiol compound is a fluorine-containing thiol compound.

(4) The decorative part according to the above (3), wherein the fluorine-containing thiol compound is represented by the following general formula (I).

R-SH (I) (R represents a hydrocarbon having 1 to 25 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom.) (5) The above R represents at least 1 The decorative article component according to the above (4), which is a hydrocarbon to which two fluorine atoms are bonded.

(6) The decorative part according to the above (4) or (5), wherein the fluorine-containing thiol compound is represented by the following general formula (II).

C _n F _{2n + 1} -SH (II) (n is 1 ≦
(7) The fluorine-containing thiol compound according to the above (4) or (5), wherein the fluorine-containing thiol compound is represented by the following general formula (III).

C _m F _{2m + 1} -C _q H _2q -SH (III) (m is 1 ≦ m ≦ 24, q is 1 ≦ q ≦ 24, 1 ≦ m + q ≦
(8) An ornamental part according to any one of the above (1) to (7), wherein the ornamental part is a watch exterior part.

(9) A decorative article comprising the decorative part according to any one of the above (1) to (8).

(10) An electronic device comprising the decorative component according to any one of (1) to (8).

(11) A timepiece comprising the timepiece exterior part according to (8).

(12) A method for manufacturing a decorative part, the surface of which is made of a metal material containing at least a Group 1B element, wherein a thiol film is formed on the surface of the metal material. A method for producing a component for decorative articles, characterized by being formed by immersion in a solution of (1).

(13) The surface is made of at least one metal material selected from the group consisting of Au, an Au-based alloy, Ag, an Ag-based alloy, Cu, and a Cu-based alloy. A method for manufacturing a decorative part, wherein a thiol film is formed, wherein the thiol film is formed by dipping in a solution of the thiol compound.

(14) The method for producing a decorative part according to the above (12) or (13), wherein the thiol compound is a fluorine-containing thiol compound.

(15) The method for producing a decorative part according to any one of the above (12) to (14), wherein the concentration of the thiol compound solution is 0.5 to 10 mM.

(16) The method for producing a decorative part according to any one of the above (12) to (15), wherein the immersion time is 5 to 80 minutes.

(17) The temperature of the solution of the thiol compound at the time of immersion is 5 to 50 ° C.
6) The method for producing a decorative part according to any one of the above.

[0024]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a decorative part according to the present invention.

FIG. 1 is a partial cross-sectional view of a watch exterior part 1 showing an example of a decorative part according to the present invention.

As shown in FIG. 1, a watch exterior part 1 of the present invention comprises a base 4 constituting the part, a base layer 3 composed of at least one layer on the base 4, and a base layer 3 formed on the base layer 3. Au-
And a coating layer 7 made of an Fe-based alloy. The thiol film 2 is formed on the surface of the coating layer 7.

The constituent material of the base 4 is a base material for forming the timepiece exterior part 1, and is appropriately selected from the viewpoint of durability against external influences, workability, and the like.

For example, when the watch exterior component 1 is, for example, a wristwatch, it is selected from the viewpoints of corrosion resistance, strength, workability such as cutting and polishing, and manufacturing cost. For example, stainless steel, brass, nickel silver Copper alloys such as titanium, gold,
Metal materials such as precious metals such as silver and platinum or alloys containing these precious metals, ceramic materials such as Al ₂ O ₃ , SiO ₂ and ZrO ₂ ceramics, ABS resin (acrylonitrile butadiene styrene), FRP
A resin material such as (fiber reinforced plastic) is used.
These metal materials, ceramic materials, and resin materials are not limited to those constituting the entire part, but may be those constituting a part of the part in combination with other materials.

The method for producing the base 4 is not particularly limited, and examples thereof include press working, cutting work, forging work, casting work, powder metallurgy sintering, metal powder injection molding (MIM), lost wax method and the like.

The surface of the substrate 4 is preferably subjected to surface finishing, and if necessary, surface finishing such as mirror polishing, streaking, honing, marking, etc. may be mentioned. May be applied to the surface finish.

On the substrate 4, an underlayer 3 composed of at least one layer is provided for various purposes. By providing the underlayer 3, corrosion resistance can be ensured. For example, if there is a pinhole on the surface of the substrate 4, it plays a role in preventing water and gas from entering into the substrate 4, and thereby preventing the substrate 4 from being rusted and cracked. Furthermore, the base 4 has burr,
When there is a defect such as rough skin, a coating layer 7 described later becomes thin at a burr portion, and the corrosion resistance may be insufficient. Therefore, it is provided for the purpose of covering such a defect on the surface of the substrate 4.

Further, by providing a layer having good adhesion to the coating layer 7 on the outermost surface of the underlayer 3, the adhesion between the underlayer 3 and the coating layer 7 can be improved.

The watch exterior part 1 of the present embodiment comprises a base layer 3
Is composed of a layer 5 made of Cu and a layer 6 made of a Cu—Sn alloy from the side closer to the substrate 4. The thickness of each of the layers 5 and 6 is not particularly limited.
The thickness is preferably about 5 μm, and the thickness of the layer 6 is preferably about 0.5 to 5 μm. With such a thickness, it is possible to more easily and reliably ensure the corrosion resistance as described above.

The thickness of the underlayer 3 is not particularly limited, but is preferably about 0.55 to 10 μm in total. If the underlayer 3 is too thin, it may be difficult to ensure corrosion resistance. If it is too thick, cracks may occur in the underlayer 3 itself, and eventually the corrosion resistance may not be ensured.

The thickness of each layer constituting the underlayer 3 may be any thickness as long as it is within the range of the above total film thickness, and the film forming method is not particularly limited.
Any method such as a normal wet plating method, a vapor deposition method, a dry plating method such as sputtering and ion plating, an immersion method, and a coating method may be used.

The configuration of the underlayer 3 is an example, and the layer configuration, the purpose of the formation, the method of formation, and the like of the underlayer may be any.

On the underlayer 3, a coating layer 7 containing a metal containing 1B element is provided. Thereby, the corrosion resistance and discoloration resistance quality of the timepiece exterior component 1 are improved. The element 1B is not particularly limited, and may be gold, a gold-based alloy, silver, a silver-based alloy,
It is preferable to be made of at least one metal material selected from the group consisting of copper and copper-based alloys. This can give a more upscale appearance.

In particular, by providing the coating layer 7 made of gold or a gold-based alloy, a golden color tone can be given.
You can get luxury. Also, by combining with the silver or silver-based alloy, or copper or copper-based alloy,
By the combination of silver and gold, the coating layer 7 can have a higher quality texture and color tone than a single color tone, and the aesthetic feeling can be increased.

Here, the gold-based alloy is, for example, about 5
It means an alloy mainly containing gold that contains 0 wt% or more. Elements that can form the coating layer 7 together with gold include, for example, Cu, Ag, Zn, Pd, Fe, In, Ti, C
o, Sn, Ni and the like. By adding such an element to gold, it is possible to change the color tone of red gold, pink gold, and the like from red to reddish from the original tone of gold which is called yellow gold.

Similarly, a silver-based alloy means an alloy mainly containing silver, containing about 50% by weight or more of silver. Examples of elements that can form the coating layer 7 together with silver include, for example, A
u, Cu, Zn, Pd, Fe, In, Ti, Co, S
n, Ni and the like. Further, the copper-based alloy means an alloy mainly containing copper, which contains about 50% by weight or more of copper. Elements that can form the coating layer 7 together with copper include
For example, Au, Ag, Zn, Pd, Fe, In, Ti,
Co, Sn, Ni, and the like.

It is preferable that such a coating layer 7 is formed by plating. This makes it possible to form a film having excellent adhesion, abrasion resistance and the like. In addition, the covering layer 7 can be provided regardless of the shape and size of the watch exterior component 1, and the thickness of the layer can be easily adjusted.

The plating method that can be used to form the coating layer 7 in the present invention is not particularly limited. For example, a wet plating method such as electrolytic plating or electroless plating, or a dry plating method such as vapor deposition, sputtering, or ion plating. And the like.

The thickness of the coating layer 7 is preferably 0.5 to 10 μm. If the thickness of the coating layer 7 is too thin, it may be difficult to improve the corrosion resistance and the like. On the other hand, if the thickness is too thick, the crack resistance may decrease, and the production cost will increase. .

On the surface of the coating layer 7, a thiol film 2 made of a thiol compound is formed. Thereby, the discoloration resistance and discoloration resistance and the stain resistance are improved.

The thiol compound is not particularly limited.
Any compound having at least one SH group, which is a main functional group, directly bonded to a carbon atom may be used.

Among such thiol compounds, for example, those represented by the following general formula (I) are preferable.

R-SH (I) (R represents a hydrocarbon having 1 to 25 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom.) In the above general formula (I), R is Particularly preferred is a hydrocarbon group having at least one fluorine atom bonded to a terminal carbon. As a result, the discoloration and discoloration resistance and stain resistance of the metal material surface are further improved.

As shown in FIG. 2 (a), the fluorine-containing compound has a fluorine-containing alkyl group at the head and a mercapto group at the tail. Such a fluorine-containing thiol compound is considered to form an S-Au bond between an S atom in the molecule and a gold atom on the surface of the metal material, for example, as shown in FIGS. . The adsorption energy between S-Au is approximately equivalent to the covalent energy (about 40 to 45 kcal / mol), and forms a very stable and dense monomolecular film. Therefore, since it functions as a protective layer that blocks air, water, oil, and the like and protects the surface of the metal material, it exhibits effects such as resistance to discoloration and discoloration and resistance to contamination.

Further, since the film is a monomolecular film, it is very thin (for example, about 2 nm), and even when such a film is formed, the appearance such as color tone and gloss of the metal material surface does not change.

Furthermore, by using an organic compound such as a thiol compound represented by a fluorine-containing thiol compound, the metal of the substance to be adsorbed is utilized by utilizing self-organization developed from the stereochemical structure of each molecule. It is also possible to create excellent functions such as specific recognition of atoms and molecules.

In this embodiment, in particular, gold (A
u) is described assuming a metal material containing silver (A).
g), a self-assembled film (thiol film) of a fluorine-containing thiol compound is similarly formed on copper (Cu).

The above-mentioned fluorine-containing thiol compound includes
Those represented by the following general formula (II) or those represented by the following general formula (III) are particularly preferred, and they may be used alone or in combination of two or more.

C _n F _{2n + 1} −SH (II) (n represents an integer of 1 ≦ n ≦ 25) C _m F _{2m + 1} −C _q H _2q −SH (III) ( m is 1 ≦ m ≦ 24, q is 1 ≦ q ≦ 24, 1 ≦ m + q ≦
By using such a fluorine-containing thiol compound, a stable thiol film can be more easily formed on the surface of the metal material.

The thiol compound is not limited to a compound having one SH group in one molecule, and may be, for example, a compound having two or more SH groups as shown in the general formula (IV). Alternatively, it can be used in combination with the above thiol compound. In the formula (IV), R ₃ is not particularly limited, and examples thereof include those shown in (1) to (4).

[0055]

Embedded image

The method of forming the thiol film 2 is not particularly limited, but it is preferable to immerse the thiol film 2 in a fluorine-containing thiol compound solution for a certain period of time (FIGS. 2A and 2B).

As a result, the fluorine-containing thiol compound in the solution is spontaneously chemically adsorbed on the metal surface containing gold or the like (FIG. 2C) to form a monomolecular film close to a two-dimensional crystal structure. (FIG. 2D). The molecular film obtained by the spontaneous chemisorption is converted into a self-assembled film, or a self-assembled film or a self-assembled film.
y).

More specifically, for example, a fluorine-containing thiol compound is dissolved in an ethanol solution, and a metal material surface made of gold or the like as shown in FIG. Then, the fluorine-containing thiol compound spontaneously assembles with the S atom directed to the gold atom (FIG. 3C).
Then, an extremely thin (eg, about 2 nm), dense and stable thiol film 2 is formed on the surface of the metal material in a two-dimensional manner (FIG. 2D).

At this time, the concentration of the solution of the fluorine-containing thiol compound is preferably 0.5 to 10 mM. When the content is within this range, the fluorine-containing thiol molecules can be regularly adsorbed on the metal surface, and a monomolecular film can be easily formed.

The time of immersion in the fluorine-containing thiol compound solution for forming a thiol film is not particularly limited, but is preferably 5 to 80 minutes, particularly preferably 10 to 60 minutes. Thereby, the fluorine-based thiol molecules can be regularly adsorbed on the metal surface, and a monomolecular film can be easily formed.

The temperature of the solution of the fluorine-containing thiol compound during immersion is preferably 5 to 50 ° C., and is preferably 25 to 50 ° C.
40 ° C. is more preferred. If the temperature is lower than 5 ° C., a longer immersion time is required, and the production efficiency may be deteriorated. On the other hand, if the temperature is higher than 50 ° C., the decomposition of the fluorine-containing thiol compound proceeds or the evaporation amount of the solvent increases significantly, Since replenishment is frequently required, workability may be deteriorated.

FIG. 4 shows the decorative article according to the present invention.
The watch 1A (watch) shown in FIG. As shown in the figure, a wristwatch 1A of the present invention has a
2, back cover 23, bezel (edge) 24, glass plate 25
And A movement (not shown) (for example, one with a dial and a needle) is stored in the case 22.

A winding stem pipe 26 is fitted into and fixed to the body 22.
1 is rotatably inserted.

The body 22, the back cover 23, the bezel 24, and the winding stem pipe 26 are each made of the above-described metal material. The body 22 and the bezel 24 are fixed by a plastic packing 28, and the bezel 24 and the glass plate 25 are fixed by a plastic packing 29.

The back cover 23 is fitted (or screwed) to the body 22, and these joints (seal portions) 50 are joined.
, A ring-shaped rubber packing (back cover packing) 40 is inserted in a compressed state. With this configuration, the sealing portion 5
0 is sealed in a liquid-tight manner to obtain a waterproof function.

A groove 272 is formed in the outer periphery of the shaft 271, of the crown 27, and a ring-shaped rubber packing (crown packing) 30 is fitted in the groove 272. The rubber packing 30 is in close contact with the inner peripheral surface of the winding stem pipe 26 and is compressed between the inner peripheral surface and the inner surface of the groove 272. With this configuration, the space between the crown 27 and the winding stem pipe 26 is liquid-tightly sealed, and a waterproof function is obtained. In addition, crown 2
7 is rotated, the rubber packing 30 is moved to the shaft portion 271.
, And slides in the circumferential direction while closely contacting the inner peripheral surface of the winding stem pipe 26.

The wristwatch 1A of the present invention has a bezel 24, a torso 2
2. A component provided with at least one of the aforementioned thiol films 2 among watch exterior components such as a crown 27 and a back cover 23.

Although the decorative component 1 of the present invention has been described with reference to the illustrated embodiments, the present invention is not limited to these embodiments. For example, the decorative article component 1 is not limited to the one provided with the coating layer 7. For example, the base 4 itself is made of gold, a gold-based alloy (solid gold), or the like, and the thiol film 2 is directly formed on the surface of the base 4. May be formed.

The underlayer 3 may have a structure in which at least one intermediate layer formed by various strike plating is provided in order to improve the adhesion between different kinds of layers.

Although the decorative component 1 of the present invention has been described with reference to the illustrated embodiments, the present invention is not limited to these embodiments. The ornaments provided with the ornamental parts 1 are not limited to watches, but also include clocks such as table clocks, mobile watches, down clocks, rings, necklaces, bracelets, earrings, earrings, eyeglass frames, lighters, tie pins, cuffs. Buttons and other various accessories may be used.

Also, electronic devices provided with the decorative component 1 of the present invention and used so as to at least partially exhibit a decorative effect are also covered by the present invention. Examples of such electronic devices include electronic watches, mobile phones, pagers, calculators, personal computers, word processors, printers, copiers, electronic toys, various measuring devices, liquid crystal display devices (LCD), and the like.

[0072]

Next, specific examples of the present invention will be described.

1. Production of Decorative Parts (Example 1) Decorative parts (watch exterior parts) were produced as follows.

Formation of Parts First, a body 22 for a wristwatch was formed by casting using brass (Bs). The material surface of this part was mirror-finished.

Formation of Underlayer 3 Next, the underlayer 3 composed of the layer 5 and the layer 6 was formed on the surface of the material (substrate). The thicknesses of the layers 5 and 6 and the forming method are as follows. The layers 5 and 6 are arranged from the side closer to the base of the body 22.

[0076] Formation of coating layer 7 A coating layer 7 made of an Au-based alloy was provided on the underlayer 3 by electrolytic plating.

The plating conditions and the properties of the coating layer 7 are as follows.

Au plating solution: Au—Fe—In alloy plating solution Plating solution temperature: 40 ° C. Plating solution pH: 3.5 Current density: 1.0 [A / dm ² ] Plating time: 40 [min] Coating layer 7 Formation of thiol film 2 C ₁₈ F ₃₇ SH as a fluorine-containing thiol compound is dissolved in ethyl alcohol to prepare a 1 mM solution. Next, the watch exterior component provided with the coating layer 7 in this solution was heated at 25 ° C.
For 10 minutes.

The timepiece exterior part was taken out, the surface was washed with ethyl alcohol, and dried at room temperature to produce the timepiece exterior part 1 of the present invention.

Example 2 A watch exterior part 1 was produced in the same manner as in Example 1 except that the thiol film 2 was formed under the following conditions.

Formation of Thiol Film As a fluorine-containing thiol compound, C ₁₀ F ₂₁ -C ₁₁ H ₂₂ S
H is dissolved in ethyl alcohol to prepare a 1 mM solution. Next, the watch exterior component provided with the coating layer 7 was immersed in this solution at 40 ° C. for 60 minutes.

The timepiece exterior part was taken out, the surface was washed with ethyl alcohol, and then dried at room temperature to produce the timepiece exterior part 1 of the present invention.

Example 3 A watch exterior part 1 was produced in the same manner as in Example 1 except that the coating layer 7 was formed under the following conditions.

Formation of Coating Layer 7 A coating layer 7 made of an Au-based alloy was provided on the underlayer 3 by electrolytic plating.

The plating conditions and the properties of the coating layer 7 are as follows.

Au plating solution: Au—Ag—Cu alloy plating solution Plating solution temperature: 60 ° C. Plating solution pH: 10 to 11 Current density: 2 [A / dm ² ] Plating time: 30 [min] Thickness of coating layer 7 (Example 4) Except that the coating layer 7 was provided by Ag plating.
, And in the same manner as in Example 1, a watch exterior component 1 was produced.

Formation of Coating Layer 7 A coating layer 7 made of an Ag-based alloy was provided on the underlayer 3 by electrolytic plating.

The plating conditions and the properties of the coating layer 7 are as follows.

Ag plating solution: Ag plating solution (coating composition Ag 99.9%
Plating solution temperature: 30 ° C. Plating solution pH: 9 to 10 Current density: 1 [A / dm ² ] Plating time: 6 [min] Thickness of coating layer 7: 2 μm (Example 5) Fluorine was used as a coating material. A watch exterior part 1 was produced in the same manner as in Example 1 except that a thiol compound C ₁₈ H ₃₇ SH not containing was used.

Comparative Example 1 A watch exterior part was produced in the same manner as in Example 1 except that no thiol film was formed.

Comparative Example 2 A watch external part was produced in the same manner as in Example 3 except that no thiol film was formed.

Comparative Example 3 A watch exterior part was produced in the same manner as in Example 4 except that no thiol film was formed.

2. Performance Evaluation The performance of the watch exterior parts produced in Examples 1 to 5 and Comparative Examples 1 to 3 was evaluated as follows.

Discoloration / fading test Each of the watch exterior parts produced in Examples 1 to 5 and Comparative Examples 1 to 3 was subjected to an accelerated light resistance test using an ultraviolet carbon arc lamp type light resistance tester according to JIS B 7751 for 250. Time went.

Before and after the test, the color difference (ΔE ^* ab) on the surface of each watch exterior component was measured. The smaller the value of ΔE ^* ab, the better the resistance to discoloration and fading, that is, the smaller the degree of discoloration.

The results are shown in Table 1.

[0097]

[Table 1]

Stain Resistance a. Fingerprint adhesion test Press the thumb with a load of 200 to 300 gf on the surface of each of the watch exterior parts produced in Examples 1 to 5 and Comparative examples 1 to 3 and hold for 1 to 2 seconds, then release the thumb and remove the fingerprint on the surface. The degree of adhesion of dirt was visually evaluated.

The evaluation was performed as follows.

A: No fingerprint attached at all O: Slight adhesion of fingerprint observed X: Fingerprint remarkably adhered The results are shown in Table 1.

B. Water repellency test A drop of pure water and a drop of ink made of the following material were placed on the surface of each watch exterior component produced in Examples 1 to 5 and Comparative Examples 1 to 3, and the static contact angle was set to room temperature. Measured in As a contact angle measuring device, CA-D manufactured by Kyowa Interface Science Co., Ltd. was used.

The ink used was "Cardridge MJIC7 Black Ink for Mach Jet Printer" (manufactured by Seiko Epson Corporation).

Table 1 shows the results.

From the above results, all of the timepiece exterior parts manufactured in the examples exhibited excellent resistance to discoloration and discoloration and stain resistance. On the other hand, the timepiece exterior parts of the comparative examples were all inferior in discoloration and fading resistance. Furthermore, fingerprints easily adhered to the surface and the contact angle was small, so that they were particularly poor in stain resistance.

[0105]

As described above, according to the decorative component and the method of manufacturing the same according to the present invention, since a dense thiol film is formed on the coating layer, Au, Ag,
A coating layer containing a Group 1B element such as Cu is used to form O, S, N in air.
Excellent discoloration resistance is obtained without discoloration due to the effects of the above.

Further, it is also rich in water repellency, so that even if water, ink or the like adheres, dirt does not permeate. Furthermore, fingerprints are less likely to adhere to the surface, a beautiful metallic color and luster can be maintained forever, and the quality value of ornaments and the like can be further enhanced.

[Brief description of the drawings]

FIG. 1 is a partial sectional view showing an example of a decorative component according to the present invention.

FIG. 2 is a schematic diagram illustrating a bonding state between a fluorine-based thiol molecule and a gold surface.

FIG. 3 is a schematic diagram illustrating a bonding state between a sulfur atom and a gold atom.

FIG. 4 is a partial cross-sectional view showing an embodiment of a portable timepiece (wristwatch) provided with a decorative article component of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Ornament parts (exterior parts for watches) 1A Watch (watch) 2 Thiol film 3 Underlayer 4 Base 5 Cu layer 6 Cu-Sn layer 7 Coating layer 22 Body 23 Back cover 24 Bezel 25 Glass plate 26 Winding pipe 27 Crown 271 Shaft 272 Groove 28 Plastic packing 29 Plastic packing 30 Rubber packing 40 Back cover packing 50 Seal part

Claims (17)

[Claims] 1. A decorative part having at least a surface made of a metal material containing a Group 1B element, wherein a thiol film made of a thiol compound is formed on the surface of the metal material. Goods parts. 2. At least the surface is made of Au, an Au-based alloy, A
g, an Ag-based alloy, Cu, a decorative component comprising at least one metal material selected from the group consisting of Cu-based alloys, wherein a thiol film made of a thiol compound is formed on the surface of the metal material. A decorative article part characterized by being formed. 3. The decorative component according to claim 1, wherein the thiol compound is a fluorine-containing thiol compound. 4. The decorative part according to claim 3, wherein the fluorine-containing thiol compound is represented by the following general formula (I). R-SH (I) (R represents a hydrocarbon having 1 to 25 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom) 5. The decorative component according to claim 4, wherein R is a hydrocarbon having at least one fluorine atom bonded to a terminal carbon. 6. The decorative part according to claim 4, wherein the fluorine-containing thiol compound is represented by the following general formula (II). C _n F _{2n + 1} -SH (II) (n represents an integer of 1 ≦ n ≦ 25) 7. The decorative component according to claim 4, wherein the fluorine-containing thiol compound is represented by the following general formula (III). _{C m F 2m + 1 -C q} H 2q -SH ··· (III) (m is 1 ≦ m ≦ 24, q is 1 ≦ q ≦ 24,1 ≦ m + q ≦
Represents an integer satisfying 25) 8. The decorative part according to claim 1, wherein said decorative part is a watch exterior part. 9. A decorative article comprising the decorative article part according to claim 1. 10. An electronic device, comprising the decorative component according to claim 1. 11. A timepiece comprising the timepiece exterior part according to claim 8. 12. A method for manufacturing a decorative part, wherein a surface is made of a metal material containing at least a Group 1B element and a thiol film is formed on the surface of the metal material, wherein the thiol film is formed of the thiol compound. A method for producing a decorative part, characterized by being formed by immersion in a solution. 13. A surface having at least Au, an Au-based alloy,
A method for producing a decorative part, comprising a metal material of at least one selected from the group consisting of Ag, an Ag-based alloy, Cu, and a Cu-based alloy, wherein a thiol film is formed on the surface of the metal material. The thiol film is formed by immersing the thiol film in a solution of the thiol compound. 14. The method for producing a decorative part according to claim 12, wherein the thiol compound is a fluorine-containing thiol compound. 15. The method according to claim 12, wherein the concentration of the thiol compound solution is 0.5 to 10 mM. 16. The method according to claim 12, wherein said immersion time is 5 to 80 minutes. 17. The method according to claim 12, wherein the temperature of the thiol compound solution during the immersion is 5 to 50 ° C.