JP2002249887A - Surface treatment method for ornament, and the ornament - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ornament which has an excellent aesthetic appearance, and a surface treatment method for the ornament. SOLUTION: The surface treatment method contains stages (3a, 3b) where a first substrate 41 is formed at least on a part of the surface of a base material 2; a stage (3c) where a second substrate 42 is formed thereon; a stage (3d) where a third substrate 43 is formed thereon; and a stage (3e) where a covering layer 3 consisting of a stainless steel is formed at least on a part of the third substrate 43 by a dry plating method. The second substrate 42 is a buffer layer relaxing the potential difference between the first substrate 41 and the third substrate 43. The average thickness of the covering layer 3 is preferably 0.5 to 2.5 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative article surface treatment method and a decorative article.

[0002]

2. Description of the Related Art Decorative articles such as watch exterior parts are required to have an excellent aesthetic appearance.

Conventionally, in order to achieve such an object,
For example, a silver-white metal material has been used as a constituent material of a decorative article.

[0004] Examples of the metal material used for such a purpose include Pd, Rd, Pt and the like. However, these constituent materials are all precious metals, and have a problem that the production cost of decorative articles is increased.

[0005] In addition to the above-mentioned noble metals, Ti, Cr and the like can be mentioned as materials having a silvery white color. However, these metal materials had a lower reflectance than the above-mentioned noble metals and were inferior in luxury. For this reason, the obtained decorative article may not have a satisfactory aesthetic appearance.

When the decorative article has a structure in which the outer surface of the substrate is coated with a coating layer made of the above-mentioned material, the adhesion between the substrate and the coating layer and the corrosion resistance of the decorative article are reduced. Sometimes it was not enough.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a decorative article having an aesthetic appearance having a silver luster and a surface treatment method capable of providing the decorative article. .

[0008]

This and other objects are achieved by the present invention which is defined below as (1) to (24).

(1) At least a part of the surface of the substrate is
A surface treatment method for decorative articles, comprising a step of forming a coating layer made of stainless steel by a dry plating method.

(2) The surface treatment method for a decorative article according to the above (1), wherein the coating layer is formed by ion plating.

(3) The surface treatment method for a decorative article according to the above (1) or (2), wherein the substrate is made of Cu, Zn, Ni or an alloy containing at least one of them. .

(4) The surface treatment method for decorative articles according to any one of the above (1) to (3), wherein the base material is produced by casting or metal powder injection molding.

(5) At least a part of the surface of the substrate,
A decorative article comprising: a step of forming at least one underlayer; and a step of forming a coating layer made of stainless steel on at least a part of the surface of the underlayer by a dry plating method. Surface treatment method.

(6) The surface treatment method for a decorative article according to the above (5), wherein the coating layer is formed by ion plating.

(7) A step of forming at least one underlayer on at least a part of the surface of the base material made of a metal material, and forming at least a part of the surface of the underlayer by ion plating. Forming a coating layer made of stainless steel.

(8) The decorative article according to any one of the above (5) to (7), wherein the substrate is made of Cu, Zn, Ni or an alloy containing at least one of them. Surface treatment method.

(9) The surface treatment method for decorative articles according to any one of the above (5) to (8), wherein the base material is produced by casting or metal powder injection molding.

(10) At least one of the underlayers
The surface treatment method for decorative articles according to any one of the above (5) to (9), wherein the layer is a buffer layer for relaxing a potential difference between one surface side and the other surface side.

(11) forming at least one underlayer on at least a part of the surface of the substrate made of a non-metallic material;
Forming a coating layer made of stainless steel by ion plating.

(12) The underlayer is made of Cu, Co, P
d, Au, Ag, In, Sn, Ni, Ti, Zn, C
(5) to (1), which are composed of r, Al, Fe or an alloy containing at least one of them.
The surface treatment method of a decorative article according to any one of 1).

(13) The surface treatment method for a decorative article according to any one of the above (5) to (11), wherein the underlayer is made of a metal compound.

(14) In the decorative article, the base layer may be formed by two
The surface treatment method for decorative articles according to any one of the above (5) to (13), which has at least one layer.

(15) The adjacent base layer is made of a material containing a common element.
The surface treatment method for a decorative article according to 4).

(16) The decorative article surface treatment method according to the above (15), wherein the common element is Cu.

(17) A decorative article comprising a step of forming a coating layer made of stainless steel on at least a part of the surface of a substrate made of a nonmetallic material by ion plating. Surface treatment method.

(18) The average thickness of the coating layer is 0.5.
The surface treatment method for decorative articles according to any one of the above (1) to (17), which has a thickness of 1 to 5.0 μm.

(19) The substrate according to the above (1) to (18), wherein at least a part of the surface of the substrate has been subjected to a surface treatment selected from mirror finishing, streaking, and satin finishing. A surface treatment method for a decorative article according to any one of the above.

(20) The decorative article according to any one of (1) to (19), wherein at least a part of the surface of the base material is subjected to a cleaning treatment before the step of coating the coating layer. Surface treatment method.

(21) The surface treatment method for a decorative article according to the above (20), wherein the cleaning treatment is a bombardment treatment.

(22) After the step of forming the coating layer, a step of forming a masking film on a part of the surface of the coating layer, and the masking film is coated with a release agent. The surface treatment method for a decorative article according to any one of the above (1) to (21), comprising a step of removing the coating layer in a portion that does not exist and a step of removing the masking film.

(23) The surface treatment method for decorative articles according to the above (22), wherein the average thickness of the masking film is 100 to 2000 μm.

(24) A decorative article manufactured by using the surface treatment method for a decorative article according to any one of the above (1) to (23).

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of a surface treatment method and a decorative article according to the present invention will be described below with reference to the accompanying drawings.

FIG. 1 is a sectional view showing a first embodiment of the surface treatment method of the present invention. As shown in FIG. 1, the surface treatment method of the present embodiment includes a step (1b) of forming a coating layer 3 made of stainless steel on at least a part (1a) of the surface of the substrate 2 by dry plating. ).

[Substrate] The substrate 2 may be composed of any material, may be composed of a metal material, or may be composed of a non-metal material. .

When the substrate 2 is made of a metal material, it is possible to provide a decorative article 1A having particularly excellent strength characteristics.

When the substrate 2 is made of a metal material, even when the surface roughness of the substrate 2 is relatively large,
The surface roughness of the obtained decorative article 1A can be reduced by the leveling effect when forming the coating layer 3 described later. For example, even if machining such as cutting and polishing on the surface of the base material 2 is omitted, mirror finishing can be performed, or the base material 2 is formed by the MIM method, Even in the case of a matte surface, it can be easily made a mirror surface. Thereby, it is possible to obtain a decorative article having excellent gloss.

When the base material 2 is made of a non-metallic material, it is possible to provide a decorative article 1A which is relatively lightweight, easy to carry and has a heavy appearance.

When the substrate 2 is made of a non-metallic material, it can be relatively easily formed into a desired shape. For this reason, in the case of stainless steel, it is possible to provide the decorative article 1A having a shape that is difficult to mold.

When the substrate 2 is made of a nonmetallic material, an effect of shielding electromagnetic noise can be obtained.

Examples of the metal material constituting the base material 2 include Fe, Cu, Zn, Ni, Mg, Cr, Mn, M
o, Nb, Al, V, Zr, Sn, Au, Pd, Pt,
Examples include various metals such as Ag and alloys containing at least one of these metals. Among them, particularly, Cu, Zn,
Various metals such as Ni or an alloy containing at least one of them is preferable. When the base material 2 is composed of the above-described material, the adhesion between the base material 2 and the coating layer 3 described below is particularly excellent, and the workability of the base material 2 is improved. The degree of freedom in forming the material 2 is further increased.

The non-metallic material forming the substrate 2 includes, for example, plastics, ceramics, stones, and wood.

Examples of the plastic include various thermoplastic resins and various thermosetting resins, for example, polyethylene, polypropylene, ethylene-propylene copolymer,
Polyolefins such as ethylene-vinyl acetate copolymer (EVA), cyclic polyolefins, modified polyolefins, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamides (eg, nylon 6, nylon 46, nylon 6)
6, nylon 610, nylon 612, nylon 11,
Nylon 12, Nylon 6-12, Nylon 6-6
6), polyimide, polyamide imide, polycarbonate (PC), poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene Copolymer (AS resin), butadiene-styrene copolymer, polyoxymethylene, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly Polyester such as cyclohexane terephthalate (PCT), polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyfe Rene oxide, modified polyphenylene oxide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluororesins, styrene, polyolefin, polyvinyl chloride System, polyurethane system, polyester system, polyamide system,
Various thermoplastic elastomers such as polybutadiene, trans polyisoprene, fluoro rubber, and chlorinated polyethylene, epoxy resin, phenol resin, urea resin,
Melamine resin, unsaturated polyester, silicone resin,
Examples thereof include polyurethane and the like, or copolymers, blends, and polymer alloys mainly containing these, and one or more of these can be used in combination (for example, as a laminate of two or more layers). .

When the substrate 2 is made of the above-mentioned plastic, the decorative article 1A having a relatively light weight, easy to carry, and having a heavy appearance can be obtained.

When the substrate 2 is made of the above-mentioned plastic, it can be relatively easily formed into a desired shape. For this reason, in the case of stainless steel, it is possible to provide the decorative article 1A having a shape that is difficult to mold.

When the substrate 2 is made of the above-mentioned plastic, an effect of shielding electromagnetic noise can be obtained.

As ceramics, for example, Al
₂ O ₃ , SiO ₂ , TiO ₂ , Ti ₂ O ₃ , ZrO ₂ , Y
Oxide ceramics such as ₂ O ₃ , barium titanate, strontium titanate, etc., AlN, Si ₃ N ₄ , SiN, T
iN, BN, ZrN, HfN, VN, TaN, NbN,
CrN, nitride ceramics such as Cr ₂ N, _{graphite, SiC, ZrC, Al 4 C} 3, CaC 2, WC, T
Examples include carbide ceramics such as iC, HfC, VC, TaC, and NbC, boride ceramics such as ZrB ₂ and MoB, and composite ceramics in which two or more of these are arbitrarily combined.

When the substrate 2 is made of the above-mentioned ceramics, a decorative article 1A having high strength and high hardness can be obtained.

The method for producing the substrate 2 is not particularly limited.
When the base material 2 is made of a metal material, examples of the manufacturing method include press working, cutting work, forging work, casting work, powder metallurgy sintering, metal powder injection molding (MIM), lost wax method, and the like. Among them, casting or metal powder injection molding (MIM) is particularly preferable.
Casting and metal powder injection molding (MIM) are particularly excellent in workability. Therefore, when these methods are used, the substrate 2 having a complicated shape can be obtained relatively easily.

[0050] Metal powder injection molding (MIM) is usually performed as follows. First, a material containing a metal powder and an organic binder is mixed and kneaded to obtain a kneaded material.

Next, a molded article is formed by injection molding the kneaded material. Thereafter, the molded body is subjected to a degreasing treatment (a binder removal treatment) to obtain a degreased body. This degreasing treatment is usually performed by heating under reduced pressure conditions.

Furthermore, a sintered body is obtained by sintering the obtained degreased body. This sintering process is usually performed by heating at a higher temperature than the degreasing process.

In the present invention, the sintered body obtained as described above can be used as a substrate.

When the substrate 2 is made of the above-mentioned plastic, examples of the production method include compression molding, extrusion molding, injection molding, and optical molding.

For the surface of the substrate 2, for example,
It is preferable that a surface treatment such as mirror finishing, streaking, satin finish or the like is performed. Thereby, the obtained decorative article 1A
It is possible to give a variation to the glossiness of the surface of the present invention, and it is possible to further improve the decorativeness of the obtained decorative article 1A.

Further, for the purpose of improving the adhesion between the base material 2 and the coating layer 3 and the like, the base material 2 may be subjected to a pretreatment before forming the coating layer 3 described later. Examples of the pretreatment include a blast treatment, a cleaning treatment such as an alkali cleaning, an acid cleaning, a water cleaning, an organic solvent cleaning, a bombardment treatment and the like, and an etching treatment. Among these, the purification treatment is particularly preferable. By subjecting the surface of the substrate 2 to a cleaning treatment, the adhesion between the substrate 2 and the coating layer 3 becomes particularly excellent. Among the cleaning treatments, the bombardment treatment is advantageous in that the substrate 2 can be easily applied even if the substrate 2 is made of the above-described plastic.

[Formation of coating layer] A coating layer 3 made of stainless steel is formed on the surface of the substrate 2 (1b).

In the present specification, “stainless steel” refers to an Fe—Cr alloy or an Fe—Cr—Ni alloy. Examples of the Fe—Cr—Ni-based alloy include SUS304, SUS303, SUS316, and SU.
S316L, SUS316J1, SUS316J1L, and the like. As the Fe—Cr alloy, for example, SU
S405, SUS430, SUS434, SUS44
4, SUS429, SUS430F and the like.

The coating layer 3 is formed by a dry plating method (gas phase film forming method).
Is formed. By forming the coating layer 3 using a dry plating method, the coating layer 3 having excellent adhesion to the substrate 2 can be obtained. As a result, the obtained decorative article 1A is
It will be excellent in durability. In addition, by forming the coating layer 3 using a dry plating method, the coating layer 3 has excellent corrosion resistance and wear resistance.

As the dry plating method, for example, thermal CV
D, chemical vapor deposition (CVD) such as plasma CVD, laser CVD, etc., vacuum vapor deposition, sputtering, ion plating, ion implantation, and the like. Among them, ion plating is particularly preferable.

By using ion plating as a dry plating method, it is possible to relatively easily obtain a coating layer 3 that is uniform and has particularly excellent adhesion to the substrate 2.
As a result, the durability of the obtained decorative article 1A is further improved. Further, by using ion plating, the corrosion resistance and wear resistance of the coating layer 3 are also particularly excellent.

The ion plating is preferably performed, for example, under the following conditions. The ionization voltage at the time of ion plating is preferably, for example, 20 to 600 V, and more preferably 40 to 300 V.

When the ionization voltage is in the above range, the coating layer 3 having excellent adhesion to the substrate 2 can be formed. Further, the coating layer 4 to be formed has a small variation in the film thickness in each part, has a small internal stress, and hardly causes cracks.

The ionization current at the time of ion plating is preferably, for example, 20 to 100 A.
More preferably, it is 40 to 70A.

When the ionization current is within the above range, the coating layer 3 having excellent adhesion to the substrate 2 can be formed. Further, the coating layer 4 to be formed has a small variation in the film thickness in each part, has a small internal stress, and hardly causes cracks.

The average thickness of the coating layer 3 formed by the dry plating method is not particularly limited.
It is preferably 5.0 μm, more preferably 0.5 to 2.5 μm.

If the average thickness of the coating layer 3 is less than the lower limit, pinholes are likely to occur in the coating layer 3 and the aesthetic appearance of the obtained decorative article 1A may be deteriorated.

On the other hand, when the average thickness of the coating layer 3 exceeds the upper limit, the thickness of each portion of the coating layer 3 tends to vary widely. In addition, the internal stress of the coating layer 3 is increased, and as a result, the adhesion between the coating layer 3 and the base material 2 is reduced, and cracks are easily generated.

The composition of each part of the coating layer 3 is as follows:
It may or may not be constant. For example, the coating layer 3 may be a material (gradient material) whose composition changes sequentially along the thickness direction.

Further, in the configuration shown in the drawing, the coating layer 3
Is formed on the entire surface of the substrate 2, but may be formed on at least a part of the surface of the base material 2. The decorative article 1A is obtained by the surface treatment method described above.

The decorative article 1A may be any article having a decorative property. Examples of the decorative article 1A include interior decorations, exterior supplies, jewelry, watch cases, watch bands, dials, watch hands, and the like. Watch exterior parts, movement base plates, gears, train wheel holders, rotating weights and other clock interior parts, glasses, tie pins, cufflinks, rings, necklaces, bracelets, brooches, pendants, earrings, earrings, earrings, earrings, earrings, earrings, earrings, piercings, etc. Or its case,
Sports equipment such as golf clubs, nameplates, panels, prizes,
In addition, various equipment parts including a housing and the like, various containers, and the like are included. Of these, watch exterior parts are particularly preferred. Watch exterior parts are required to have a beautiful appearance as a decorative product, and to have durability, corrosion resistance, abrasion resistance, and the like as practical products. According to the surface treatment method of the present invention, these requirements are satisfied. Can all be satisfied.

Next, a description will be given of a surface treatment method and a decorative article according to a second embodiment of the present invention. FIG. 2 is a sectional view showing a second embodiment of the surface treatment method of the present invention.

Hereinafter, the surface treatment method of the second embodiment and the decorative article of the second embodiment manufactured by using the method will be described, focusing on the differences from the first embodiment. The description is omitted.

As shown in FIG. 2, according to the surface treatment method of the present embodiment, a step (2b) of forming an underlayer 40 on at least a part (2a) of the surface of the base material 2 is performed. (2c) of forming the coating layer 3 made of stainless steel by dry plating.

That is, it is the same as the above-described first embodiment except that the underlayer 40 is formed on at least a part of the surface of the base material 2 before the formation of the coating layer 3.

Hereinafter, the underlayer 40 will be described in detail. [Underlayer] The underlayer 40 functions as, for example, a buffer layer that reduces a potential difference between the base material 2 and the coating layer 3. This makes it possible to more effectively prevent the occurrence of corrosion due to the potential difference between the base material 2 and the coating layer 3 (contact corrosion of dissimilar metals).

The underlayer 40 has, for example, a function of improving the adhesion between the base material 2 and the coating layer 3 and a function of repairing holes, scratches and the like of the base material 2 by leveling. It may be something.

As a method for forming the underlayer 40, for example,
Wet plating methods such as electrolytic plating, immersion plating, and electroless plating; chemical vapor deposition methods (CVD) such as thermal CVD, plasma CVD, and laser CVD; dry plating methods such as vacuum deposition, sputtering, and ion plating; thermal spraying; and metal foil. And the like, among which the wet plating method or the dry plating method is particularly preferred.

By using a wet plating method or a dry plating method as a method for forming the underlayer 40, the formed underlayer 40 has particularly excellent adhesion to the substrate 2. As a result, the obtained decorative article 1B has particularly excellent long-term durability.

The underlayer 40 is formed by subjecting the surface of the base material 2 to a chemical treatment such as an oxidation treatment, a nitridation treatment, a chromate treatment, a carbonization treatment, an acid immersion treatment, an acid electrolytic treatment, an alkali immersion treatment, and an alkaline electrolytic treatment. It may be a film formed by application, particularly a passivation film.

The standard potential of the underlayer 40 is preferably a value between the standard potential of the base material 2 and the standard potential of the coating layer 3. That is, the standard potential of the base layer 40 is
And a material having a value between the standard potential of the constituent material and the standard potential of the constituent material of the coating layer 3. This makes it possible to more effectively prevent the occurrence of corrosion due to the potential difference between the base material 2 and the coating layer 3 (contact corrosion of dissimilar metals).

As a constituent material of the underlayer 40, for example,
Ni, Cu, Au, Pd, Sn, Zn, Ag, In, C
o, Ti, Fe, Al, Cr, Ir, and other metal materials, alloys containing at least one of the metal materials, and metal compounds of at least one of the metal materials (for example,
Metal oxide, metal nitride, metal carbide, etc.), or a combination of two or more of these.

The constituent material of the underlayer 40 preferably contains at least one of the material forming the base material 1 and the material forming the coating layer 3. Thereby, the adhesiveness with the base material 1 and the coating layer 3 is further improved.

The average thickness of the underlayer 40 is not particularly limited, but is preferably, for example, 0.1 to 20.0 μm, and more preferably 0.5 to 10.0 μm.

If the average thickness of the underlayer 40 is less than the lower limit, the effect of the underlayer 40 may not be sufficiently exhibited.

On the other hand, when the average thickness of the underlayer 40 exceeds the upper limit, the thickness of each portion of the underlayer 40 tends to vary widely. In addition, the internal stress of the underlayer 40 increases, and cracks easily occur.

As described above, by forming the base layer 40 on the surface of the base material 2, the adhesion between the base material 2 and the coating layer 3 and the corrosion resistance of the decorative article 1B are further improved. As a result, the decorative article 1B is particularly excellent in durability.

The underlayer 40 is formed on the entire surface of the substrate 2 in the configuration shown in the drawing, but may be formed on at least a part of the surface of the substrate 2.

The composition of each part of the underlayer 40 may or may not be constant. For example, the underlayer 40 may be a material (gradient material) whose composition changes sequentially along the thickness direction.

The underlayer 40 is not limited to a layer functioning as a buffer layer. For example, the underlayer 40 may have a function of preventing corrosion from occurring during storage (before the step of forming the coating layer 3) or the like.

Next, a third embodiment of the surface treatment method and the decorative article of the present invention will be described. FIG. 3 is a sectional view showing a third embodiment of the surface treatment method of the present invention.

Hereinafter, the surface treatment method of the third embodiment and the decorative article of the third embodiment manufactured using the method will be described, focusing on the differences from the first and second embodiments. The description of the above item is omitted.

As shown in FIG. 3, according to the surface treatment method of the present embodiment, at least a part (3a) of the surface of the substrate 2 is provided with an underlayer (first underlayer 41, (3b, 3 base layer 42, third base layer 43)
c, 3d) and at least a part of the surface of the underlayer,
(3e) forming a coating layer 3 made of stainless steel by dry plating.

That is, prior to the formation of the coating layer 3, the first underlayer 41 and the second
This is the same as the above-described first embodiment except that the underlayer 42 and the third underlayer 43 are stacked in this order.

Hereinafter, the first underlayer 41 and the second underlayer 4
The second and third underlayers 43 will be described in order.

[First Underlayer] A first underlayer 41 is formed on the surface of the substrate 2.

The first underlayer 41 has, for example, a function of improving the adhesion between the substrate 2 and the second underlayer 42, and a function of improving the
It has the function of repairing holes, scratches, etc. by leveling.

Examples of the method of forming the first underlayer 41 include wet plating methods such as electrolytic plating, immersion plating, and electroless plating, thermal CVD, plasma CVD, and laser CVD.
Chemical vapor deposition (CVD), vacuum deposition, sputtering, dry plating such as ion plating, thermal spraying, bonding of metal foil, chemical treatment on the surface of the substrate 2 (for example,
Oxidation treatment, nitridation treatment) and the like. Among them, a wet plating method or a dry plating method is particularly preferable.

By using a wet plating method or a dry plating method as a method for forming the first underlayer 41, the first underlayer 41 formed has excellent adhesion to the substrate 2. Become. As a result, the long-term durability of the obtained decorative article 1C is particularly excellent.

As the constituent material of the first underlayer 41, for example, Cu, Sn, Ni, Zn, Fe, In, Co, A
l, a metal alloy containing at least one of the above metal materials, a metal compound of at least one of the above metal materials (for example, metal oxide, metal nitride, metal carbide, etc.), or A combination of at least two or more species may be used.

It is preferable that the constituent material of the first underlayer 41 contains at least one of the material of the base material 1 and the material of the second underlayer 42. Thereby, the adhesion between the base material 1 and the second underlayer 42 is further improved.

The average thickness of the first underlayer 41 is not particularly limited, but is preferably, for example, 0.1 to 20.0 μm, and more preferably 0.5 to 10.0 μm.

If the average thickness of the first underlayer 41 is less than the lower limit, the effect of the first underlayer 41 may not be sufficiently exhibited.

On the other hand, when the average thickness of the first underlayer 41 exceeds the upper limit value, the thickness of each portion of the first underlayer 41 tends to vary widely. Further, the internal stress of the first underlayer 41 is increased, and cracks are easily generated.

In the structure shown, the first underlayer 41
Is formed on the entire surface of the substrate 2, but may be formed on at least a part of the surface of the substrate 2.

The composition of each part of the first underlayer 41 may or may not be constant. For example, the first underlayer 41 may be a material (gradient material) whose composition changes sequentially along the thickness direction.

[Second Underlayer] Next, the first underlayer 41
A second underlayer 42 is formed on the surface of the substrate.

The second underlayer 42 functions, for example, as a buffer layer for reducing a potential difference between one surface (the first underlayer 41) and the other surface (the third underlayer 43). . Thereby, one surface side of the underlayer 42 (the first underlayer 4
It is possible to more effectively prevent corrosion (dissimilar metal contact corrosion) due to a potential difference between 1) and the other surface side (third underlayer 43).

As a method for forming the second underlayer 42, for example, wet plating methods such as electrolytic plating, immersion plating, and electroless plating, thermal CVD, plasma CVD, and laser CVD
Chemical vapor deposition (CVD), vacuum deposition, sputtering, dry plating such as ion plating, thermal spraying, bonding of metal foil, chemical treatment on the surface of the first underlayer 41 (eg, oxidation treatment, nitridation treatment) And the like. Of these, a wet plating method or a dry plating method is particularly preferable.

By using a wet plating method or a dry plating method as a method for forming the second underlayer 42, the second underlayer 42 formed is particularly excellent in adhesion to the first underlayer 41. It will be. As a result, the long-term durability of the obtained decorative article 1C is particularly excellent.

The standard potential of the second underlayer 42 is preferably a value between the standard potential of the first underlayer 41 and the standard potential of the third underlayer 43. That is, the second underlayer 42 is a material whose standard potential is a value between the standard potential of the constituent material of the first underlayer 41 and the standard potential of the constituent material of the third underlayer 43. Preferably, it is constructed. Thereby, the occurrence of corrosion (dissimilar metal contact corrosion) due to the potential difference between one surface side (first underlayer 41) and the other surface side (third underlayer 43) of second underlayer 42 is improved. This can be effectively prevented.

As the constituent material of the second underlayer 42, for example, Cu, Sn, Zn, Fe, In, Ag, Au, P
d, a metal material such as Ti or Cr, an alloy containing at least one of the metal materials, a metal compound (for example, a metal oxide, a metal nitride, and a metal carbide) of at least one of the metal materials; Alternatively, a combination of two or more of these may be used.

The constituent material of the second base layer 42 may be the material of the first base layer 41 or the third base layer 43.
It is preferable to include at least one of the materials constituting In other words, it is preferable that two adjacent underlayers are made of a material containing a common element. Thereby, the adhesion to the adjacent base layers (the first base layer 41 and the third base layer 43) is further improved. In particular, when the common element is Cu, the adhesion with the adjacent underlayer becomes particularly excellent.

The average thickness of the second underlayer 42 is not particularly limited, but is preferably, for example, 0.1 to 20.0 μm, and more preferably 0.5 to 10.0 μm.

If the average thickness of the second underlayer 42 is less than the lower limit, the effect of the second underlayer 42 may not be sufficiently exhibited.

On the other hand, if the average thickness of the second underlayer 42 exceeds the above upper limit, the thickness of each portion of the second underlayer 42 tends to vary widely. In addition, the internal stress of the second underlayer 42 increases, and cracks easily occur.

In the structure shown, the second underlayer 42
Is formed on the entire surface of the first underlayer 41, but the first
What is necessary is just to be formed on at least a part of the surface of the underlayer 41 of FIG.

The composition of each part of the second underlayer 42 may be constant or not constant. For example, the second underlayer 42 may be a material (graded material) whose composition changes sequentially along the thickness direction.

[Third Underlayer] Further, the second underlayer 4
On the surface of No. 2, a third underlayer 43 is formed.

The third underlayer 43 has, for example, a function of improving the adhesion between the second underlayer 42 and the coating layer 3 and a corrosion during storage (before the step of forming the coating layer 3). And the like to prevent the occurrence of

As a method of forming the third underlayer 43, for example, wet plating methods such as electrolytic plating, immersion plating, and electroless plating, thermal CVD, plasma CVD, and laser CVD
Chemical vapor deposition (CVD), vacuum deposition, sputtering, dry plating such as ion plating, thermal spraying, bonding of metal foil, chemical treatment on the surface of the second underlayer 42 (eg, oxidation treatment, nitridation treatment) And the like. Among them, the wet plating method or the dry plating method is particularly preferable.

By using a wet plating method or a dry plating method as a method for forming the third underlayer 43, the third underlayer 43 formed is particularly excellent in adhesion to the second underlayer 42. It will be. As a result, the long-term durability of the obtained decorative article 1C is particularly excellent.

The constituent material of the third underlayer 43 is, for example, Ni, Au, Pd, Ag, Fe, In, Ti, C
metal materials such as r, Sn, Cu, Pt, Rh, and Ru; alloys containing at least one of the metal materials; and metal compounds of at least one of the metal materials (for example,
Metal oxide, metal nitride, metal carbide, etc.), or a combination of two or more of these.

It is preferable that the constituent material of the third underlayer 43 contains at least one of the material forming the second underlayer 42 and the material forming the coating layer 3. Thereby, the adhesion between the second underlayer 42 and the coating layer 3 is further improved.

The average thickness of the third underlayer 43 is not particularly limited, but is preferably, for example, 0.1 to 20.0 μm, and more preferably 1.0 to 3.0 μm.

If the average thickness of the third underlayer 43 is less than the lower limit, the effect of the third underlayer 43 may not be sufficiently exhibited.

On the other hand, when the average thickness of the third underlayer 43 exceeds the upper limit, the thickness of each portion of the third underlayer 43 tends to vary widely. Further, the internal stress of the third underlayer 43 increases, and cracks are easily generated.

In the structure shown, the third underlayer 43
Is formed on the entire surface of the second underlayer 42,
What is necessary is just to be formed on at least a part of the surface of the underlayer 42 of FIG.

The composition of each part of the third underlayer 43 may be constant or not constant. For example, the third underlayer 43 may be a material (gradient material) whose composition changes sequentially along the thickness direction.

As described above, the first underlayer 41, the second underlayer 42, and the third underlayer 4
3 are laminated in this order, the adhesion between the base material 2 and the coating layer 3 and the corrosion resistance of the decorative article 1C are further improved. As a result, the decorative article 1C is particularly excellent in durability.

The first underlayer 41 and the second underlayer 4
The second and third underlayers 43 are not limited to those having the functions described above, but may have other effects.

Next, a surface treatment method and a decorative article according to a fourth embodiment of the present invention will be described. FIG. 4 is a sectional view showing a fourth embodiment of the surface treatment method of the present invention.

Hereinafter, the surface treatment method of the fourth embodiment and the decorative article of the fourth embodiment manufactured by using the method will be described, focusing on differences from the first, second and third embodiments. The description of the same items is omitted.

As shown in FIG. 4, according to the surface treatment method of the present embodiment, an underlayer (a first underlayer 41, a second underlayer 42, A step (4b, 4c, 4d) of forming a third underlayer 43) and a step of forming a coating layer 3 made of stainless steel on at least a part of the surface of the underlayer by dry plating. 4e) and a masking film 5 on a part of the surface of the coating layer 3.
(4f), a step (4g) of using a release agent to remove the coating layer 3 at a portion where the masking film 5 is not covered, and a step (4f) of removing the masking film 5
h).

That is, after forming the coating layer 3, a step (4f) of forming a masking coating 5 on a part of the surface of the coating layer 3
And a step (4g) of using a release agent to remove the coating layer 3 at a portion where the masking film 5 is not covered, and a step (4h) of removing the masking film 5
This is the same as the third embodiment described above.

[Coating of Masking Film] After the formation of the coating layer 3, a part of the surface of the coating layer 3 is coated with the masking film 5 (4f). This masking film 5 is used in a step of removing the coating layer 3 described later to cover the coating layer 3
It functions as a mask for protecting.

The masking film 5 may be any as long as it has a function of protecting the coating layer 3 at the site where the coating layer 3 is covered in the step of removing the coating layer 3.
In a step of removing the masking film 5 described later, it is preferable that the masking film 5 can be easily removed.

Examples of the material constituting such a masking film 5 include resin materials such as acrylic resin, polyimide resin, polysulfone resin, epoxy resin and fluorine resin, Au, Ni, Pd, Cu, Ag and the like. , Ti, Cr
And the like.

The method of forming the masking film 5 is not particularly limited, and includes, for example, dipping, brushing, spray coating,
Coating such as electrostatic coating and electrodeposition coating, wet plating such as electrolytic plating, immersion plating, and electroless plating; chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD;
Examples include a dry plating method such as vacuum deposition, sputtering, and ion plating, and thermal spraying.

The average thickness of the masking film 5 is not particularly limited, but is preferably, for example, 100 to 2000 μm, and more preferably 500 to 1000 μm.

When the average thickness of the masking film 5 is less than the lower limit, pinholes tend to be easily formed in the masking film 5. For this reason, in the step of removing the coating layer 3 described below, a part of the coating layer 3 where the masking coating 5 is coated may be dissolved or peeled off, and the aesthetic appearance of the obtained decorative article 1D may be reduced. There is.

On the other hand, when the average thickness of the masking film 5 exceeds the upper limit, the variation in the film thickness in each part of the masking film 5 tends to increase. Further, the internal stress of the masking film 5 is increased, and as a result, the adhesion between the masking film 5 and the coating layer 3 is reduced, and cracks are easily generated.

The masking film 5 is preferably transparent. This makes it possible to visually check the state of adhesion to the coating layer 3 from the outside.

The masking film 5 is provided on the surface of the coating layer 3.
The invention is not limited to those directly formed into a desired shape. For example, a masking film 5 having a desired pattern may be formed by coating the constituent material of the masking film 5 on almost the entire surface of the coating layer 3 and then removing a part thereof.

As a method of removing a part of the masking film 5 covering almost the entire surface of the coating layer 3, for example, a method of irradiating a laser beam to the masking film 5 at a portion to be removed can be mentioned. Examples of the laser used at this time include a gas laser such as a Ne—He laser, an Ar laser, and a CO ₂ laser, a ruby laser, a semiconductor laser, a YAG laser, a glass laser, and a YVO ₄ laser.

[Removal of Coating Layer] Next, the masking coating 5
Of the coating layer 3 not covered with (4)
g).

The removal of the coating layer 3 is performed using a release agent which can remove the coating layer 3 and does not substantially dissolve or peel off the masking film 5.

The release agent used for removing the coating layer 3 is not particularly limited as long as it can remove the coating layer 3 and does not substantially dissolve or peel off the masking film 5. , And a fluid such as a gas, and among them, a liquid is particularly preferable. This makes it possible to easily and reliably remove the coating layer 3.

Examples of the release agent include nitric acid, sulfuric acid,
Ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, etc.
Inorganic solvents, methyl ethyl ketone (MEK),
, Diethyl ketone, methyl isobutyl tetone (MIB
K), methyl isopropyl ketone (MIPK), cyclo
Ketone solvents such as hexanone, methanol, ethanol
, Isopropanol, ethylene glycol, diethyl
Alcohol (DEG), alcohols such as glycerin
Solvent, diethyl ether, diisopropyl ether,
1,2-dimethoxyethane (DME), 1,4-diox
Sun, tetrahydrofuran (THF), tetrahydropi
Orchid (THP), anisole, diethylene glycol di
Ether solvents such as methyl ether (diglyme), methyl
Lucerosolve, ethyl cellosolve, phenyl cellosolve
, Hexane, pentane, hepta
Aliphatic solvents such as toluene and cyclohexane, toluene
Aromatic solvents such as benzene, xylene, benzene, etc.
Lysine, pyrazine, furan, pyrrole, thiophene, etc.
Aromatic heterocyclic compound solvent, N, N-dimethylforma
Amide (DMF), N, N-dimethylacetamide (DM
Amide solvents such as A), dichloromethane, chloroform
Solution of halogen compounds such as 1,2-dichloroethane
Medium, esters such as ethyl acetate, methyl acetate and ethyl formate
System solvent, dimethyl sulfoxide (DMSO), sulfora
Solvents such as sulfur compounds, acetonitrile, propioni
Nitrile solvents such as tolyl, formic acid, acetic acid, trichlorovinegar
Organic solvents such as acid, trifluoroacetic acid and hydrofluoric acid
One or two or more selected from organic solvents
Stuff and these, nitric acid, sulfuric acid, hydrogen chloride, fluorinated water
Acidic substances such as sulfuric acid and phosphoric acid, sodium hydroxide, potassium hydroxide
Lithium, lithium hydroxide, calcium hydroxide,
Alkaline substances such as gnesium and ammonia, overmanga
Potassium phosphate (KMnO)₄), Manganese dioxide (MnO)
₂), Potassium dichromate (K ₂Cr₂O₇), Ozo
Acid, concentrated sulfuric acid, nitric acid, salad powder, hydrogen peroxide, quinones, etc.
Oxidizing agent, sodium thiosulfate (Na₂S₂O₃), Sulfuric acid
Mixing reducing agents such as hydrogen fluoride, hydrogen peroxide and hydroquinones
And the like.

The method of removing the coating layer 3 includes, for example, a method of spraying a release agent, a method of dipping in a liquid release agent (dipping), and a method of electrolyzing in a state of being dipped in a liquid release agent. Among them, a method of dipping in a liquid release agent is particularly preferable. This makes it possible to more easily and reliably remove the coating layer 3.

When the coating layer 3 is removed by dipping in a liquid release agent, the temperature of the release agent is not particularly limited, but is preferably, for example, 15 to 100 ° C., and 30 to 80 ° C. More preferably, 40-60
C. is more preferred.

When the temperature of the release agent is lower than the lower limit,
Depending on the thickness of the coating layer 3 and the like, the time required for sufficiently removing the coating layer 3 in a portion not covered with the masking coating 5 becomes longer, and the productivity of the decorative article 1D may decrease.

On the other hand, when the temperature of the release agent exceeds the above upper limit, the amount of the release agent volatilized increases depending on the vapor pressure, boiling point, etc. of the release agent, and the amount of the release agent required for removing the coating layer 3 becomes small. Shows a tendency to increase.

The time of immersion in the release agent is not particularly limited, but is preferably, for example, 5 to 120 minutes, more preferably 20 to 60 minutes.

If the immersion time in the release agent is less than the above lower limit, the coating layer 3 at a portion where the masking film 5 is not coated may be sufficiently removed depending on the thickness of the coating layer 3 and the temperature of the release agent. Can be difficult to do.

On the other hand, when the immersion time in the release agent exceeds the above upper limit, the productivity of the decorative article 1D is reduced.

[Removal of Masking Film] Thereafter, by removing the masking film 5, the decorative article 1D is obtained.

The masking film 5 may be removed by any method. However, the masking film 5 can be removed, and the substrate 2 and the coating layer 3 are not substantially damaged. It is preferable to use a masking film removing agent.

By using such a masking film removing agent, the masking film 5 can be easily and reliably removed.

The masking film remover used for removing the masking film 5 is not particularly limited, but is preferably a fluid such as a liquid or a gas, and particularly preferably a liquid. This makes it possible to more easily and reliably remove the masking film 5.

As the masking film remover, for example,
Inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, etc., methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl tetone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone Ketone solvents such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG), alcohol solvents such as glycerin, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DM
E), 1,4-dioxane, tetrahydrofuran (TH
F), ether solvents such as tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and phenyl cellosolve; and aliphatic hydrocarbons such as hexane, pentane, heptane, and cyclohexane. Solvents, aromatic hydrocarbon solvents such as toluene, xylene and benzene, aromatic heterocyclic compound solvents such as pyridine, pyrazine, furan, pyrrole and thiophene;
Amide solvents such as N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMA); halogen compound solvents such as dichloromethane, chloroform and 1,2-dichloroethane; and esters such as ethyl acetate, methyl acetate and ethyl formate. System solvent, dimethyl sulfoxide (DM
SO), one or more selected from sulfur compound solvents such as sulfolane, nitrile solvents such as acetonitrile and propionitrile, and organic solvents such as organic acid solvents such as formic acid, acetic acid, trichloroacetic acid and trifluoroacetic acid. Mixtures of two or more, and acid substances such as nitric acid, sulfuric acid, hydrogen chloride, hydrogen fluoride, and phosphoric acid, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, Alkaline substances such as ammonia, potassium permanganate (KMnO ₄ ), manganese dioxide (MnO ₂ ), potassium dichromate (K ₂ Cr)
₂ O ₇ ), oxidizing agents such as ozone, concentrated sulfuric acid, nitric acid, salad powder, hydrogen peroxide and quinones, sodium thiosulfate (Na ₂
S ₂ O ₃ ), a mixture of reducing agents such as hydrogen sulfide, hydrogen peroxide, and hydroquinones.

The method of removing the masking film 5 includes, for example, a method of spraying a masking film removing agent, a method of dipping in a liquid state masking film removing agent, and a method of electrolyzing in a state of being immersed in a liquid state masking film removing agent. Although a method etc. are mentioned, a method of immersing in a liquid state masking film removing agent is particularly preferable. This makes it possible to more easily and reliably remove the masking film 5.

When the masking film 5 is removed by dipping in a liquid state masking film removing agent, the temperature of the masking film removing agent is not particularly limited, but is preferably, for example, 15 to 100 ° C. 30-50
C. is more preferred.

When the temperature of the masking film removing agent is lower than the lower limit, depending on the thickness of the masking film 5, etc.
The time required for sufficiently removing the masking film 5 becomes longer, and the productivity of the decorative article 1D may decrease.

On the other hand, if the temperature of the masking film remover exceeds the above upper limit, the volatilization amount of the masking film remover increases depending on the vapor pressure, boiling point, etc. of the masking film remover, and it is necessary to remove the masking film 5. It tends to increase the amount of the masking film removing agent.

The immersion time in the masking film removing agent is not particularly limited, but is preferably, for example, 5 to 60 minutes, more preferably 5 to 30 minutes.

If the immersion time in the masking film removing agent is less than the above lower limit, the masking film 5 may vary depending on the thickness of the masking film 5 and the temperature of the masking film removing agent.
May be difficult to remove sufficiently.

On the other hand, if the immersion time in the masking film removing agent exceeds the above upper limit, the productivity of the decorative article 1D decreases.

As described above, removing a part of the coating layer 3 makes it easier to pattern the coating layer 3 into a predetermined shape.

Further, by removing a part of the coating layer 3, for example, a pattern of concavo-convex is formed between a portion where the coating layer 3 remains and a portion where the coating layer 3 is removed, and a difference in color is obtained. Becomes remarkable. As a result, the aesthetic appearance of the decorative article 1D is further improved.

Although the preferred embodiments of the surface treatment method and the decorative article according to the present invention have been described above, the present invention is not limited to these.

For example, in the above-described second embodiment, one underlayer is formed, and in the third embodiment, three underlayers (a first underlayer, a second underlayer, The third underlying layer is formed, but the underlying layer to be formed is 2
It may be a layer or four or more layers. In this case, it is preferable that at least one of the underlayers has an action of reducing a potential difference between one surface side and the other side.

Further, even when the number of the underlying layers is two or four or more, as described above, the two adjacent underlying layers are made of a material containing a common element. preferable. Thereby, the adhesion between the adjacent base layers is further improved. Further, when the common element is Cu, the adhesion between the adjacent underlayers is particularly excellent.

Further, at least a part of the surface of the decorative article is provided with corrosion resistance, weather resistance, water resistance, oil resistance, abrasion resistance, discoloration resistance, etc., and is rustproof, stainproof, antifogging, and scratchproof. A protective layer or the like for improving the effects such as the above may be formed.

In the fourth embodiment, a part of the coating layer 3 is removed using a release agent. However, together with the coating layer 3, the underlying layer (the first underlying layer and the second At least a part of the ground layer and the third underlayer may be removed.

[0176]

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

[0177] 1. Manufacture of Decorative Articles (Example 1) Decorative articles (watch cases) were manufactured by performing the following surface treatments.

First, compression molding was performed using ABS resin (acrylonitrile-butadiene-styrene resin).
A base material having the shape of a watch case was prepared, and then necessary portions were cut and polished.

Next, the substrate was washed. First, alkali electrolytic degreasing was performed for 30 seconds, and then alkali immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, water was washed for 10 seconds, and pure water was washed for 10 seconds.

A coating layer composed of stainless steel was formed on the surface of the substrate thus cleaned.

The coating layer was formed by ion plating as described below. First, the base material is mounted in the ion plating apparatus, and then, while preheating the inside of the apparatus, the inside of the ion plating apparatus is 2 × 10 ^−5.
The gas was exhausted (reduced pressure) to Torr.

Further, the inside of the ion plating apparatus
The mixture was evacuated (reduced pressure) to × 10 ⁻⁶ Torr, and bombarding was performed for 5 minutes at an argon gas flow rate of 470 ml / min.

Subsequently, the pressure of the atmosphere gas (argon gas) in the ion plating apparatus was set to 6 × 10 ⁻⁴ To
After rr, a decorative product was obtained by forming a coating layer made of stainless steel under the conditions of ionization voltage: 40 V and ionization current: 40 A using SUS444 as a target.

The average thickness of the formed coating layer is as follows:
It was 1.0 μm. The thickness of the coating layer is JIS H5
821 was measured by a microscope cross section test method.

Further, the substrate and the obtained decorative article have a surface roughness R defined by JIS B 0601.
_{The max} was measured.

The surface roughness R _max of the cut and polished portion of the substrate was 1.6 μm. After the formation of the coating layer, the surface roughness R _max of the corresponding portion is formed.
Was 0.3 μm (mirror surface).

The surface roughness R _max of the portion of the base material not subjected to cutting or polishing was 4.5 μm (pear-skinned). After the formation of the coating layer, the surface roughness R _max of the corresponding portion was 0.9 μm (semi-specular surface).

As described above, it can be seen that the surface was smoothed by forming the coating layer by ion plating.

(Example 2) Metal powder injection molding (MIM)
A decorative article (wristwatch case) was manufactured in the same manner as in Example 1 except that the base material made of Ti was used.

[0190] The substrate made of Ti was produced as follows. First, a Ti powder having an average particle size of 52 μm manufactured by a gas atomizing method was prepared.

The Ti powder: 75 vol%, polyethylene: 8 vol%, polypropylene: 7 vol%,
A material consisting of paraffin wax: 10 vol% was kneaded. A kneader was used for kneading the materials. The material temperature during kneading was 60 ° C.

Next, the obtained kneaded material was pulverized and classified to obtain pellets having an average particle diameter of 3 mm. Using the pellets, metal powder injection molding (MIM) was performed by an injection molding machine to produce a molded article having a watch case shape. At this time, the compact was molded in consideration of shrinkage during binder removal treatment and sintering. The molding conditions at the time of injection molding are: mold temperature 40 ° C., injection pressure 80 kgf / cm ² , injection time 20
Seconds and the cooling time was 40 seconds.

Next, the molded body was subjected to a debinding treatment using a degreasing furnace to obtain a degreased body. This binder removal treatment was performed in an argon gas atmosphere of 1 × 10 ⁻³ Torr at 80 ° C. for 1 hour, and then heated to 400 ° C. at a rate of 10 ° C./hour. The weight of the sample at the time of the heat treatment was measured, and the point in time at which the weight loss disappeared was regarded as the end point of the debinding.

Next, the degreased body thus obtained was sintered using a sintering furnace to obtain a base material. This sintering was performed by performing a heat treatment at 900 to 1100 ° C. for 6 hours in an argon gas atmosphere of 1 × 10 ⁻⁵ to 1 × 10 ⁻⁶ Torr.

Further, regarding the base material and the obtained decorative article, the surface roughness R specified in JIS B 0601 was used.
_{The max} was measured.

The surface roughness R _max of the cut and polished portion of the substrate was 1.2 μm. After the formation of the coating layer, the surface roughness R _max of the corresponding portion is formed.
Was 0.25 μm (mirror surface).

The surface roughness R _max of the portion of the substrate that was not subjected to cutting or polishing was 6.0 μm (pear cloth). After the formation of the coating layer, the surface roughness R _max of the corresponding portion was 1.1 μm (semi-specular surface).

As described above, it can be seen that the surface was smoothed by forming the coating layer by ion plating.

Example 3 A decorative article (wristwatch dial) was manufactured by performing the following surface treatment.

First, a base material having the shape of a wristwatch dial was prepared by powder metallurgy sintering using alumina (Al ₂ O ₃ ) powder, and then necessary portions were cut and polished.

Next, the substrate was washed. First, alkali electrolytic degreasing was performed for 30 seconds, and then alkali immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, water was washed for 10 seconds, and pure water was washed for 10 seconds.

[0202] A coating layer composed of stainless steel was formed on the surface of the base material thus washed.

The formation of the coating layer was performed by ion plating as described below. First, the base material is mounted in the ion plating apparatus, and then, while preheating the inside of the apparatus, the inside of the ion plating apparatus is 2 × 10 ^−5.
The gas was exhausted (reduced pressure) to Torr.

Furthermore, the inside of the ion plating apparatus
The mixture was evacuated (reduced pressure) to × 10 ⁻⁶ Torr, and bombarding was performed for 5 minutes at an argon gas flow rate of 470 ml / min.

Subsequently, the pressure of the atmosphere gas (argon gas) in the ion plating apparatus was set to 6 × 10 ⁻⁴ To
After rr, a decorative product was obtained by forming a coating layer made of stainless steel under the conditions of ionization voltage: 40 V and ionization current: 40 A using SUS444 as a target.

Incidentally, the average thickness of the formed coating layer is as follows:
It was 1.0 μm. The thickness of the coating layer is JIS H5
821 was measured by a microscope cross section test method.

Example 4 A decorative article (wristwatch hand) was manufactured by performing the following surface treatment.

First, a Cu—Zn alloy (alloy composition: Cu
(60wt% -Zn40wt%)
A base material having the shape of a wristwatch needle was prepared, and after that, necessary portions were cut and then mirror-finished by diamond cutting.

Next, the substrate was washed. As for the cleaning of the substrate, first, alkali immersion degreasing is performed for 30 seconds, then neutralization is performed for 10 seconds, water cleaning is performed for 10 seconds, and pure water cleaning is performed for 10 seconds.
Seconds.

Next, a base layer made of Ni was formed on the mirror-finished surface of the base material.

The underlayer was formed by wet plating under the conditions of a bath temperature: 60 ° C., a current density: 3 A / dm ² , and a time: 10 minutes. The average thickness of the underlayer thus formed was 5 μm.

Next, the substrate on which the underlayer was laminated was washed. As this cleaning, first, alkaline electrolytic degreasing is performed for 30 minutes.
Second, and then alkali immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, water was washed for 10 seconds, and pure water was washed for 10 seconds.

After washing, a coating layer made of stainless steel was formed on the surface of the underlayer.

The coating layer was formed by ion plating as described below. First, the base material is mounted in the ion plating apparatus, and then, while preheating the inside of the apparatus, the inside of the ion plating apparatus is 2 × 10 ^−5.
The gas was exhausted (reduced pressure) to Torr.

Furthermore, the inside of the ion plating apparatus
The mixture was evacuated (reduced pressure) to × 10 ⁻⁶ Torr, and a bombardment treatment was performed at an argon gas flow rate of 470 ml / min for 5 minutes.

Subsequently, the pressure of the atmosphere gas (argon gas) in the ion plating apparatus was set to 6 × 10 ⁻⁴ To
After setting to rr, a decorative article was obtained by forming a coating layer made of stainless steel under the conditions of ionization voltage: 40 V and ionization current: 40 A using SUS316L as a target.

The average thickness of the formed coating layer is as follows:
It was 2.5 μm. The thicknesses of the underlayer and the coating layer were measured by a microscope cross-sectional test method according to JIS H 5821.

(Example 5) A decorative article (watch case) was manufactured by performing the following surface treatment.

First, an aluminum base material having the shape of a wristwatch case was prepared by casting, and then necessary portions were cut and polished.

Next, emery # 18
A line processing was performed by zero polishing. Next, aluminum oxide (Al ₂ O ₃ ) is applied to the surface of the substrate subjected to the streak processing.
Was formed.

The underlayer was formed by anodic oxidation under the conditions of a bath temperature of 30 ° C., a current density of 2 A / dm ² and a time of 60 minutes. The average thickness of the underlayer thus formed was 20 μm.

Next, the underlayer was washed. As cleaning of the underlayer, first, alkali immersion degreasing is performed for 30 seconds.
Thereafter, neutralization was performed for 10 seconds, water was washed for 10 seconds, and pure water was washed for 10 seconds.

A coating layer made of stainless steel was formed on the surface of the underlayer washed as described above.

The coating layer was formed by ion plating as described below. First, the base material on which the underlayer is formed is mounted in an ion plating apparatus,
Thereafter, the inside of the ion plating apparatus was evacuated (reduced pressure) to 2 × 10 ⁻⁵ Torr while preheating the inside of the apparatus.

Furthermore, the inside of the ion plating apparatus
Evacuation (reduced pressure) was performed to × 10 ⁻⁶ Torr, and bombardment treatment was performed at an argon gas flow rate of 470 ml / min for 5 minutes.

Subsequently, the pressure of the atmosphere gas (argon gas) in the ion plating apparatus was set to 6 × 10 ⁻⁴ To
After rr, a decorative product was obtained by forming a coating layer made of stainless steel under the conditions of ionization voltage: 40 V and ionization current: 40 A using SUS444 as a target. The average thickness of the formed coating layer was 1.0 μm.

The thickness of the underlayer and the coating layer is JIS H5
821 was measured by a microscope cross section test method.

(Example 6) A decorative article (wristwatch dial) was manufactured by performing the following surface treatment.

First, a Cu—Zn alloy (alloy composition: Cu
(60wt% -Zn40wt%)
Produce a substrate having the shape of a watch dial, and then
Necessary parts were cut and polished.

Next, the substrate was washed. First, alkali electrolytic degreasing was performed for 30 seconds, and then alkali immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, water was washed for 10 seconds, and pure water was washed for 10 seconds.

[0231] A first underlayer made of Cu was formed on the surface of the cleaned base material.

The first underlayer is formed by wet plating using a bath temperature of 60 ° C., a current density of 3 A / dm ² and a time of 1 hour.
The test was performed under the condition of 0 minutes. The average thickness of the first underlayer thus formed was 5 μm.

Thereafter, the surface of the first underlayer is coated with Cu-S
A second underlayer composed of an n-based alloy was formed.

The second underlayer is formed by wet plating at a bath temperature of 60 ° C., a current density of 3 A / dm ² , and a time of 2 hours.
Minutes. The average thickness of the second underlayer thus formed was 3 μm.

Further, the surface of the second underlayer was Ni-S
n-based alloy (alloy composition: Ni80wt% -Sn20wt)
%) Was formed.

The third underlayer is formed by wet plating at a bath temperature of 60 ° C., a current density of 3 A / dm ² , and a time of 1 hour.
The test was performed under the condition of 0 minutes. The average thickness of the third underlayer formed in this manner was 3 μm.

Next, the substrate on which the first to third underlayers were laminated was washed. As this cleaning, first, alkaline electrolytic degreasing is performed for 30 seconds, and then alkali immersion degreasing is performed for 30 seconds.
Seconds. Thereafter, neutralization was performed for 10 seconds, water was washed for 10 seconds, and pure water was washed for 10 seconds.

After the cleaning, a coating layer made of stainless steel was formed on the surface of the third underlayer.

The coating layer was formed by ion plating as described below. First, the base material is mounted in the ion plating apparatus, and then, while preheating the inside of the apparatus, the inside of the ion plating apparatus is 2 × 10 ^−5.
The gas was exhausted (reduced pressure) to Torr.

Furthermore, the inside of the ion plating apparatus
The mixture was evacuated (reduced pressure) to × 10 ⁻⁶ Torr, and a bombardment treatment was performed at an argon gas flow rate of 470 ml / min for 5 minutes.

Subsequently, the pressure of the atmosphere gas (argon gas) in the ion plating apparatus was set to 6 × 10 ⁻⁴ To
After setting to rr, a decorative article was obtained by forming a coating layer made of stainless steel under the conditions of ionization voltage: 40 V and ionization current: 40 A using SUS316L as a target.

Incidentally, the average thickness of the formed coating layer is as follows:
It was 2.5 μm. The thicknesses of the first underlayer, the second underlayer, the third underlayer, and the coating layer are determined according to JIS H
The measurement was carried out according to a microscope sectional test method of No. 5821.

Example 7 A decorative article (wristwatch dial) was manufactured by performing the following surface treatment.

First, a base material having the shape of a dial for a wristwatch was prepared by injection molding using polycarbonate (PC), and then necessary portions were cut and polished.

Next, the substrate was washed. First, alkali electrolytic degreasing was performed for 30 seconds, and then alkali immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, water was washed for 10 seconds, and pure water was washed for 10 seconds.

The surface of the substrate thus cleaned was subjected to a bombardment treatment at a reduced pressure of 2 × 10 ⁻⁶ Torr at a flow rate of argon gas of 470 ml / min for 5 minutes.

Next, a first underlayer made of Ni was formed on the surface of the substrate on which the bombardment treatment was performed.

The first underlayer was formed by electroless wet plating under the conditions of a bath temperature of 60 ° C., a current density of 3 A / dm ² and a time of 5 minutes. The average thickness of the first underlayer thus formed was 0.5 μm.

Then, a second underlayer made of Cu was formed on the surface of the first underlayer. The second underlayer is formed by electrolytic plating using a bath temperature of 60 ° C. and a current density of 3 A.
/ Dm ² , time: 15 minutes. The average thickness of the second underlayer thus formed is 15 μm
Met.

Next, a third underlayer made of Ni was formed on the surface of the second underlayer. The third underlayer is formed by wet plating at a bath temperature of 60 ° C. and a current density of 3 A.
/ Dm ² , time: 10 minutes. The average thickness of the third underlayer thus formed is 10 μm.
m.

Next, the base material on which the first underlayer, the second underlayer, and the third underlayer were laminated was washed. As this cleaning, first, alkali immersion degreasing is performed for 30 seconds, then neutralization is performed for 10 seconds, water cleaning is performed for 10 seconds, and pure water cleaning is performed for 10 seconds.
Seconds.

After the washing, a coating layer made of stainless steel was formed on the surface of the third underlayer.

The formation of the coating layer was performed by ion plating as described below. First, the base material is mounted in the ion plating apparatus, and then, while preheating the inside of the apparatus, the inside of the ion plating apparatus is 2 × 10 ^−5.
The gas was exhausted (reduced pressure) to Torr.

Furthermore, the inside of the ion plating apparatus
Evacuation (reduced pressure) was performed to × 10 ⁻⁶ Torr, and bombardment treatment was performed at an argon gas flow rate of 470 ml / min for 5 minutes.

Subsequently, the pressure of the atmosphere gas (argon gas) in the ion plating apparatus was set to 6 × 10 ⁻⁴ To
After setting to rr, a decorative article was obtained by forming a coating layer made of stainless steel under the conditions of ionization voltage: 40 V and ionization current: 40 A using SUS316L as a target.

Incidentally, the average thickness of the formed coating layer is as follows:
It was 2.5 μm. The thicknesses of the first underlayer, the second underlayer, the third underlayer, and the coating layer are determined according to JIS H
The measurement was carried out according to a microscope sectional test method of No. 5821.

Example 8 A decorative article (wristwatch case) was manufactured by performing the following surface treatment.

First, a base material having the shape of a wristwatch case was prepared by casting using Zn, and then necessary portions were cut and polished.

Next, the surface of the substrate was subjected to satin finish. For satin finish, 2 kg /
It was performed by spraying at a pressure of cm ² .

Next, the base material subjected to satin finish was washed.
First, alkali electrolytic degreasing was performed for 30 seconds, and then alkali immersion degreasing was performed for 30 seconds.
Thereafter, neutralization was performed for 10 seconds, water was washed for 10 seconds, and pure water was washed for 10 seconds. A first underlayer composed of Cu was formed on the surface of the base material thus cleaned.

The first underlayer is formed by wet plating at a bath temperature of 60 ° C., a current density of 3 A / dm ² and a time of 2 hours.
The test was performed under the condition of 0 minutes. The average thickness of the first underlayer formed in this manner was 20 μm.

Thereafter, the surface of the first underlayer is coated with Cu-S
A second underlayer composed of an n-based alloy was formed.

The second underlayer is formed by wet plating at a bath temperature of 60 ° C., a current density of 3 A / dm ² , and a time of 3 hours.
Minutes. The average thickness of the second underlayer thus formed was 3 μm.

Next, the substrate on which the first underlayer and the second underlayer were laminated was washed. As this cleaning, first, alkali immersion degreasing was performed for 30 seconds, and then neutralization was performed for 10 seconds, water cleaning was performed for 10 seconds, and pure water cleaning was performed for 10 seconds.

After the cleaning, a coating layer made of stainless steel was formed on the surface of the third underlayer.

The coating layer was formed by ion plating as described below. First, the base material is mounted in the ion plating apparatus, and then, while preheating the inside of the apparatus, the inside of the ion plating apparatus is 2 × 10 ^−5.
The gas was exhausted (reduced pressure) to Torr.

Furthermore, the inside of the ion plating apparatus
Evacuation (reduced pressure) was performed to × 10 ⁻⁶ Torr, and bombardment treatment was performed at an argon gas flow rate of 470 ml / min for 5 minutes.

Subsequently, the pressure of the atmosphere gas (argon gas) in the ion plating apparatus was set to 6 × 10 ⁻⁴ To
After setting to rr, a decorative article was obtained by forming a coating layer made of stainless steel under the conditions of ionization voltage: 40 V and ionization current: 40 A using SUS316L as a target. The average thickness of the formed coating layer was 2.5 μm.

The thicknesses of the first underlayer, the second underlayer, and the coating layer were measured by a microscope cross section test method according to JIS H 5821.

Example 9 A decorative article was manufactured in the same manner as in Example 4 except that a part of the coating layer formed on the surface of the third underlayer was removed as follows. .

First, a masking film was formed in a predetermined shape on a part of the surface of the coating layer. The masking film is formed by brush-coating a rubber-based resin to partially cover the surface of the coating layer.
This was done by drying for minutes. The average thickness of the masking film thus formed was 500 μm.

Next, using a release agent, the coating layer was removed from the area where the masking film was not coated.

The removal of the coating layer was performed by dipping in a release agent. At this time, hydrochloric acid was used as a release agent.
In this step, the temperature of the release agent and the immersion time in the release agent were 70 ° C. and 30 minutes, respectively.

Thereafter, the masking film was removed by immersion in a masking film removing agent comprising a halogen compound solvent and a ketone solvent. The temperature of the masking film removing agent and the immersion time in the masking film removing agent in this step were 30 ° C. and 30 minutes, respectively.

(Comparative Example) A decorative article (watch case) was manufactured by performing the following surface treatment.

First, a Cu—Zn alloy (alloy composition: Cu
(60wt% -Zn40wt%)
Produce a substrate having the shape of a watch dial, and then
Necessary parts were cut and polished.

Next, the substrate was washed. First, alkali electrolytic degreasing was performed for 30 seconds, and then alkali immersion degreasing was performed for 30 seconds. Thereafter, neutralization was performed for 10 seconds, water was washed for 10 seconds, and pure water was washed for 10 seconds.

A coating layer composed of Cr was formed on the surface of the cleaned base material.

The coating layer had a bath temperature of 50 ° C. and a current density of 3 A.
/ Dm ² , time: 5 minutes. The average thickness of the formed coating layer is
It was 2.5 μm. The thickness of the coating layer is JIS H5
821 was measured by a microscope cross section test method. Table 1 shows the conditions of the surface treatment method of each example and comparative example.

[0280]

[Table 1]

[0281] 2. Evaluation of Appearance of Decorative Article Each ornament manufactured in Examples 1 to 9 and Comparative Example was visually observed and observed with a microscope, and the appearance was evaluated according to the following four-grade criteria. ：: Excellent appearance (high whiteness and glossiness). ：: Good appearance (medium whiteness and glossiness). Δ: Appearance slightly poor (whiteness, glossiness slightly small, or surface roughness). X: Poor appearance (whiteness, low gloss, or remarkable surface roughness).

[0282] 3. Evaluation of Adhesion of Coating Layer For each of the decorative articles manufactured in Examples 1 to 9 and Comparative Example, the coating was performed when the sample was heated at 150 ° C. for 10 minutes and quenched with normal-temperature water according to JIS H 8166. The peeling and swelling of the layer were evaluated according to the following four criteria. A: No peeling or swelling of the coating layer. ：: Almost no peeling or swelling of the coating layer. Δ: Some peeling and swelling of the coating layer. X: A thing with severe peeling and swelling of the coating layer.

[0283] 4. Evaluation of Corrosion Resistance of Decorative Articles Each of the decorative articles manufactured in Examples 1 to 9 and Comparative Example was evaluated for corrosion resistance by performing a salt solution immersion test as described below.

Each piece of ornament, once fully soaked in saline, was placed on gauze or cotton wool soaked in saline in a closed container, and about half the height of the ornament was soaked in saline. . In this state, it was left for 72 hours at 40 ° C. and 100% humidity, and the appearance of the decorative article was visually observed. The concentration of the saline used in this test was 50 g / liter.

The corrosion resistance of each decorative article was evaluated according to the following four criteria. A: No swelling of the coating layer, no corrosion on the surface. ：: Swelling of the coating layer is slightly observed. Δ: Swelling of the coating layer is clearly observed. ×: Corrosion on the surface is observed. Table 2 shows the results.

[0286]

[Table 2]

As is clear from Table 2, all the decorative articles produced by using the surface treatment method of the present invention had an excellent aesthetic appearance and excellent adhesion of the coating layer.
The decorative article manufactured by using the surface treatment method of the present invention also had excellent corrosion resistance. In addition, the decorative article having the base layer functioning as the buffer layer had particularly excellent corrosion resistance. In addition, the decorative article (Example 3) obtained by using a mirror-finished substrate as the base material was particularly high in glossiness and excellent in aesthetic appearance as a decorative article.

On the other hand, the decorative article manufactured by the surface treatment method of the comparative example was inferior in aesthetic appearance and inferior in adhesion of the coating layer. Also, the corrosion resistance was poor.

[0289]

As described above, according to the surface treatment method of the present invention, it is possible to easily and quickly manufacture a decorative article having an excellent aesthetic appearance.

In addition, a decorative article having excellent adhesion of the coating layer and excellent corrosion resistance and durability can be obtained.

Further, by selecting the constituent material of the base material, it is possible to easily manufacture a decorative article having a complicated shape, and to achieve a reduction in the weight of the decorative article and a reduction in manufacturing cost. be able to.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a first embodiment of a surface treatment method of the present invention.

FIG. 2 is a sectional view showing a second embodiment of the surface treatment method of the present invention.

FIG. 3 is a sectional view showing a third embodiment of the surface treatment method of the present invention.

FIG. 4 is a sectional view showing a fourth embodiment of the surface treatment method of the present invention.

[Explanation of symbols]

 1A, 1B, 1C, 1D Decorative article 2 Base material 3 Coating layer 40 Underlayer 41 First underlayer 42 Second underlayer 43 Third underlayer 5 Masking film

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C23C 28/00 C23C 28/00 C EF term (reference) 4K018 AA03 AA06 AA07 AA40 BA02 BA03 BA04 BA20 CA29 DA32 FA23 KA25 4K029 AA02 AA04 AA11 BA26 BB02 BB03 BD06 CA03 EA01 FA01 FA04 FA05 4K044 AA04 AA06 AA13 AA16 BA02 BA06 BA10 BB01 BB03 BB04 BC09 CA07 CA13 CA15 CA16 CA17 CA18 CA64

Claims (24)

[Claims] 1. A surface treatment method for decorative articles, comprising a step of forming a coating layer made of stainless steel on at least a part of the surface of a substrate by a dry plating method. 2. The surface treatment method for decorative articles according to claim 1, wherein the coating layer is formed by ion plating. 3. The decorative article surface treatment method according to claim 1, wherein the base material is made of Cu, Zn, Ni, or an alloy containing at least one of them. 4. The surface treatment method for decorative articles according to claim 1, wherein said base material is produced by casting or metal powder injection molding. 5. A step of forming at least one underlayer on at least a part of the surface of a base material; and a coating made of stainless steel on at least a part of the surface of the underlayer by dry plating. And a step of forming a layer. 6. The surface treatment method for a decorative article according to claim 5, wherein the coating layer is formed by ion plating. 7. A step of forming at least one underlayer on at least a part of the surface of a base material made of a metal material; Forming a coating layer made of steel. 8. The decorative article surface treatment method according to claim 5, wherein the base material is made of Cu, Zn, Ni, or an alloy containing at least one of them. 9. The surface treatment method for decorative articles according to claim 5, wherein said base material is produced by casting or metal powder injection molding. 10. At least one of the underlayers comprises:
The surface treatment method for decorative articles according to any one of claims 5 to 9, wherein the buffer layer is a buffer layer for reducing a potential difference between the one surface side and the other surface side. 11. A step of forming at least one underlayer on at least a part of the surface of a substrate made of a nonmetallic material, and at least part of the surface of the underlayer is subjected to ion plating. Forming a coating layer made of stainless steel. 12. The method according to claim 12, wherein the underlayer is made of Cu, Co, Pd, A
u, Ag, In, Sn, Ni, Ti, Zn, Cr, A
The decorative article surface treatment method according to any one of claims 5 to 11, comprising l, Fe or an alloy containing at least one of these. 13. The surface treatment method for decorative articles according to claim 5, wherein said underlayer is made of a metal compound. 14. The surface treatment method for a decorative article according to claim 5, wherein the decorative article has two or more base layers. 15. The surface treatment method for a decorative article according to claim 14, wherein the adjacent base layers are made of a material containing an element common to each other. 16. The surface treatment method for a decorative article according to claim 15, wherein the common element is Cu. 17. A surface of a decorative article, comprising a step of forming a coating layer made of stainless steel on at least a part of the surface of a substrate made of a nonmetallic material by ion plating. Processing method. 18. The coating layer has an average thickness of 0.1 to 0.1.
The surface treatment method for decorative articles according to any one of claims 1 to 17, wherein the thickness is 5.0 µm. 19. The substrate according to claim 1, wherein at least a part of a surface of the substrate has been subjected to a surface treatment selected from a mirror surface treatment, a line processing, and a satin finish. Surface treatment method of decorative products. 20. The surface treatment method for decorative articles according to claim 1, wherein at least a part of the surface of the base material is subjected to a cleaning treatment before the step of coating the coating layer. 21. The method according to claim 20, wherein the cleaning process is a bombardment process. 22. After the step of forming the coating layer, a step of forming a masking film on a part of the surface of the coating layer, and the masking film is not coated using a release agent. 2. The method according to claim 1, further comprising: a step of removing the coating layer at a site;
22. The surface treatment method for a decorative article according to any one of the above items. 23. An average thickness of the masking film is 1
The surface treatment method for decorative articles according to claim 22, wherein the thickness is from 00 to 2000 µm. 24. A decorative article manufactured by using the decorative article surface treatment method according to claim 1. Description: