JP6922322B2 - Watch parts and watches - Google Patents

Description

The present invention relates to timepiece parts and timepieces.

Watches are required to function as practical products and to have excellent aesthetics (aesthetic appearance) as ornaments.

For this reason, precious metal materials having an excellent texture are used for watch parts such as cases and bands (see, for example, Patent Document 1).

However, precious metal materials are generally expensive, have low hardness, and are easily scratched (inferior in abrasion resistance).

Further, in the past, it has been difficult to obtain a high-class appearance with a calm impression because the brightness is not too high while having an appropriate glossiness.

Japanese Patent No. 2990917

An object of the present invention is to have excellent aesthetics (particularly, to have a high-class appearance with a calm impression without being too bright while having an appropriate luster), excellent corrosion resistance, and abrasion resistance. It is an object of the present invention to provide a timepiece component having excellent wear resistance, and to provide a timepiece provided with the timepiece part.

Such an object is achieved by the following invention.
The watch component of the present invention includes a base material and
It is provided with a first coating material composed of a material containing Co as a main component, Cr in a content of 26% by mass or more and 30% by mass or less, and Mo in a content of 5% by mass or more and 7% by mass or less.
A film having a thickness of 1.0 μm having a composition of Co: 62.8% by mass, Cr: 28.2% by mass, Mo: 6.0% by mass, C: 1.5% by mass, Ar: 1.5% by mass. The average signal intensity of oxygen in the first coating film measured by SIMS is 160 count / sec or more and 300 count / sec or less.

As a result, it has excellent aesthetics (particularly, it has an appropriate luster, but the brightness is not too high and gives a high-class appearance with a calm impression), and it has excellent corrosion resistance, as well as abrasion resistance and abrasion resistance. It is also possible to provide excellent watch parts.

The timepiece component of the present invention, the surface on the side where the first coating is visually recognized, ^{L *} in the chromaticity diagram of the the ^L * ^a * ^{b *} display defined in JIS Z 8729 is 70.0 or more 78. It is preferably 4 or less.

As a result, the glossiness of the timepiece component can be made more suitable, and a more luxurious appearance can be obtained.

In the watch component of the present invention, the base material is preferably made of a material containing at least one of stainless steel and Ti.

As a result, the durability of the timepiece parts can be made more excellent. Further, when the thickness of the first coating film is relatively thin, the appearance of the watch component as a whole can be adversely affected, and the aesthetic appearance of the watch component as a whole is more reliably improved. can do.

In the timepiece component of the present invention, it is preferable that at least one base layer made of a material containing Ti is provided between the base material and the first coating film.

As a result, the durability of the timepiece parts can be made more excellent. In addition, it is possible to finely adjust the color of the timepiece parts as a whole, and it is possible to make the aesthetics of the timepiece parts more surely excellent.

In the timepiece component of the present invention, it is preferable that a second coating film made of a material containing at least one of TiC and TiCN is provided between the base material and the first coating film.

As a result, the hardness of the watch parts can be made higher, and the dent resistance (difficulty of making dents) of the watch parts can be made more excellent. Durability can be made better. Further, the color tone can be preferably adjusted (particularly, the glossiness can be adjusted).

In the timepiece component of the present invention, a second coating film made of a material containing at least one of TiC and TiCN is provided between the base material and the first coating film.
It is preferable that the base layer is provided on both side surfaces of the second coating film.

As a result, the durability of the timepiece parts can be further improved. In addition, it is possible to finely adjust the color of the timepiece parts as a whole, and it is possible to make the aesthetics of the timepiece parts more surely excellent.

In the timepiece component of the present invention, it is preferable that the second coating film has a portion whose composition changes in an inclined manner in the thickness direction.

As a result, for example, the effect of providing a second coating such as improvement of dent resistance, abrasion resistance, abrasion resistance, etc. of watch parts, color tone adjustment (particularly, glossiness adjustment), etc. It is possible to improve the durability of the timepiece parts while obtaining the above.

In the timepiece component of the present invention, it is preferable that the second coating film has a region in which the sum of the contents of C and N decreases toward the surface side of the second coating film.

As a result, for example, the effect of providing a second coating such as improvement of dent resistance, abrasion resistance, abrasion resistance, etc. of watch parts, color tone adjustment (particularly, glossiness adjustment), etc. It is possible to further improve the durability of the timepiece parts while obtaining the above.

In the timepiece component of the present invention, it is preferable that the second coating film has the regions on both side surfaces of the second coating film.
As a result, the durability of the timepiece parts can be made particularly excellent.

In the timepiece component of the present invention, the thickness of the second coating film is preferably 0.05 μm or more and 4.0 μm or less.

As a result, the hardness of the watch parts can be further increased, the dent resistance (difficulty of dents) of the watch parts, etc. can be further improved, and the durability of the watch parts can be further improved. It can be excellent. In addition, it is possible to more preferably adjust the delicate color of the entire timepiece component.

The watch component of the present invention is preferably a case or band.
Since these parts (watch parts) have a great influence on the appearance of the entire watch, the aesthetics of the watch as a whole can be improved by applying the present invention to these parts. be able to. In addition, these parts are usually exposed to the outside when a watch is used, and are easily in contact with the skin. Among various parts, they have particularly excellent abrasion resistance and abrasion resistance. , It is particularly strongly required to have excellent allergic resistance (difficulty of causing allergic reaction). Therefore, by applying the present invention to these parts, the effects of the present invention as described above are more prominently exhibited.

The timepiece of the present invention is characterized by comprising the parts for the timepiece of the present invention.
As a result, it has excellent aesthetics (particularly, it has an appropriate luster, but the brightness is not too high and gives a high-class appearance with a calm impression), and it has excellent corrosion resistance, as well as abrasion resistance and abrasion resistance. It is possible to provide a watch having excellent watch parts.

It is sectional drawing which shows typically 1st Embodiment of the timepiece component of this invention. It is sectional drawing which shows typically the 2nd Embodiment of the timepiece component of this invention. It is sectional drawing which shows typically the 3rd Embodiment of the timepiece component of this invention. It is sectional drawing which shows typically the 4th Embodiment of the timepiece component of this invention. It is sectional drawing which shows typically 5th Embodiment of the timepiece component of this invention. It is a partial cross-sectional view schematically showing a preferable embodiment of the timepiece (wrist watch) of this invention.

Hereinafter, preferred embodiments will be described in detail with reference to the accompanying drawings.
《Watch parts》
First, the timepiece component of the present invention will be described.

[First Embodiment]
FIG. 1 is a cross-sectional view schematically showing a first embodiment of a timepiece component of the present invention. Hereinafter, the case where the upper side in FIG. 1 is the viewpoint side of the observer will be mainly described (the same applies to FIGS. 2 to 5 described later).

The watch component 10 is composed of a base material 1 and a material containing Co as a main component, Cr in a content of 26% by mass or more and 30% by mass or less, and Mo in a content of 5% by mass or more and 7% by mass or less. It also has a first coating film 2.

Then, a thickness of 1.0 μm having a composition of Co: 62.8% by mass, Cr: 28.2% by mass, Mo: 6.0% by mass, C: 1.5% by mass, Ar: 1.5% by mass. The average signal intensity of oxygen in the first coating film 2 measured by SIMS (secondary ion mass spectrometry) is 160 count / sec or more and 300 count / sec or less.

With such a configuration, it has excellent aesthetics (particularly, it has a high-class appearance with a calm impression without being too bright while having an appropriate luster), and has excellent corrosion resistance and abrasion resistance. It is possible to provide a timepiece component 10 having excellent wear resistance. In particular, the above-mentioned excellent appearance can be obtained without using a precious metal as a main material. Further, even when a base material 1 made of various materials is used, the aesthetics and the like of the timepiece component 10 as a whole can be excellent, and the base material 1 can be widely selected. Further, the constituent material of the first coating film 2 as described above is a material that does not easily cause the problem of allergies. Further, even when the thickness of the first coating film 2 is relatively thin, excellent aesthetics can be obtained, so that the manufacturing cost of the timepiece part 10 can be suppressed, and the productivity of the timepiece part 10 can be suppressed. Can be made excellent.

In particular, since the average signal intensity of oxygen in the first coating film 2 measured by SIMS is within the above range, the impression is calm without the brightness being too high while having an appropriate glossiness. The appearance of the watch has a high-class appearance, and the aesthetics of the watch component 10 are particularly excellent.

Further, when the average signal intensity of oxygen in the first coating film 2 measured by SIMS is within the above range, the average signal intensity of oxygen is too small (the average signal intensity is less than 160 count / sec). Compared to (especially when it is 150 count / sec or less), the first coating film 2 has excellent chemical stability like a passivation film, and the watch component 10 has a stable appearance for a long period of time. Obtainable.

On the other hand, if the above conditions are not satisfied, the above excellent effects cannot be obtained.

For example, if the Cr content in the first coating film 2 is less than the lower limit, the corrosion resistance, abrasion resistance, and abrasion resistance become insufficient.

Further, when the Cr content in the first coating film 2 exceeds the upper limit value, the aesthetics are deteriorated and a high-quality glossiness cannot be obtained.

Further, if the Mo content in the first coating film 2 is less than the lower limit value, the abrasion resistance and the abrasion resistance become insufficient.

Further, when the Mo content in the first coating film 2 exceeds the upper limit value, the aesthetics are deteriorated and a high-quality glossiness cannot be obtained.

Further, when a coating made of a noble metal material such as Pt is used as the first coating 2 instead of a coating made of an alloy containing Co, Cr and Mo, the abrasion resistance and abrasion resistance are remarkably high. It will be low.

Further, if the average signal intensity of oxygen in the first coating film 2 measured by SIMS is too small, the aesthetics of the timepiece component 10 are not inferior, but the brightness becomes too high. It gives a gorgeous impression, and it is not possible to obtain a high-class appearance with a calm impression. In addition, the chemical stability of the constituent material of the first coating film 2 is lowered, and it becomes difficult for the timepiece component 10 to obtain a stable appearance for a long period of time.

Further, if the average signal intensity of oxygen in the first coating film 2 measured by SIMS is too large, the brightness becomes insufficient, a sufficient glossiness cannot be obtained, and the aesthetic appearance of the watch component 10 deteriorates. do.

The average signal intensity of oxygen in the first coating film 2 measured using SIMS is an index showing how much the oxygen content in the first coating film 2 is higher than the oxygen content of the above standard. Is. It can be said that the larger this value is, the higher the oxygen content is.

Since the reference film (reference sample) as described above has a specific composition, the average signal intensity of oxygen in the first film 2 is evaluated based on the reference sample. The oxygen content in the first coating film 2 can be quantitatively evaluated.

The reference sample may have the above composition and thickness, but using a magnetron sputtering device, Ar gas flow rate: 100 ccm, atmospheric pressure: 0.3 Pa, power: 5 kW, bias voltage: -80 V. , Substrate temperature: It is preferable that it is manufactured under the condition of 160 ° C. As a result, the reliability of the oxygen content in the reference sample can be increased, and even if the reference sample is prepared in a different device, at a different time, and in a different place, the variation in the oxygen content between them can be extremely reduced. can. The reliability of numerical values can be further improved.

The reference sample has a thickness of 1 having a composition of Co: 62.8% by mass, Cr: 28.2% by mass, Mo: 6.0% by mass, C: 1.5% by mass, and Ar: 1.5% by mass. It is a film of 0.0 μm. The composition of the reference sample can be suitably controlled by adjusting the composition of the target of sputtering. In addition to these components, the reference sample may contain impurities (other components) such as components that are inevitably mixed. The content of other components in the quasi-sample (the sum of these when a plurality of elements are contained as other components) is sufficiently low, but specifically, it is preferably 2000 ppm or less, preferably 1000 ppm or less. Is more preferable, and 500 ppm or less is further preferable.

The reference sample was manufactured using a magnetron sputtering device under the conditions of Ar gas flow rate: 100 ccm, atmospheric pressure: 0.3 Pa, power: 5 kW, bias voltage: -80 V, and substrate temperature: 160 ° C. However, the flow rate of the gas containing oxygen atoms during the production (sputtering) of the reference sample is preferably 5 ccm or less, and the partial pressure of the gas containing oxygen atoms in the atmosphere is ^10-5 Pa or less. Is preferable.

The chamber size of the magnetron sputtering apparatus is not particularly limited, but it is preferable that the inner diameter is 1000 mm or more and 1500 mm or less and the height is 750 mm or more and 1500 mm or less.

Examples of the magnetron sputtering apparatus that can be used for producing the reference sample include AS14G manufactured by ProChina.

The reference sample is preferably manufactured using the same apparatus used for forming the first coating film 2 constituting the timepiece component 10 according to the present invention.
This improves the reliability of the numerical value of the average signal intensity of oxygen for the first coating 2.

For example, by post-treatment after the formation of the first film 2 (for example, oxidation treatment, reduction treatment, etc.), adjustment of atmospheric conditions at the time of formation of the first film 2, and the like, the average signal of oxygen as described above is obtained. The first coating film 2 that satisfies the strength condition can be preferably formed.

≪Base material≫
The base material 1 has a function as a support for supporting the first coating film 2 and the like.
The base material 1 may be made of any material, and the constituent materials of the base material 1 include, for example, Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Zr, and the like. Metallic materials such as Nb, Mo, In, Sn, Hf, Ta, W, Bi, Mg and alloys containing at least one of these; oxide-based ceramics such as alumina, zirconia and titania, and water such as hydroxyapatite. Oxide-based ceramics, nitride-based ceramics such as silicon nitride, carbide-based ceramics such as silicon carbide, halide-based ceramics such as fluorite, carbonate-based ceramics, various ceramic materials such as phosphate-based ceramics; sapphire glass, Glass materials such as soda glass, crystalline glass, quartz glass, lead glass, potassium glass, borosilicate glass, and non-alkali glass; plastic materials such as various thermoplastic resins and various curable resins can be mentioned.

Among these, the base material 1 is preferably a metal material, and in particular, it is preferably made of a material containing at least one of stainless steel and Ti.

As a result, the base material 1 having high strength and high corrosion resistance can be obtained, and the adhesion to the first coating film 2 and the like can be made more excellent, and the durability of the timepiece component 10 can be made more excellent. Can be. Further, when the thickness of the first coating film 2 is relatively thin, the appearance of the watch component 10 as a whole can be suitably affected, and the aesthetic appearance of the watch component 10 as a whole is more reliably improved. It can be a clock. Further, even when the thickness of the first coating film 2 is relatively thin, sufficiently excellent aesthetics can be obtained, which is advantageous from the viewpoint of suppressing the production cost of the timepiece component 10.

As Ti, any of pure Ti and Ti alloy (α alloy, α-β alloy, β alloy) may be used.
As the stainless steel, any of ferrite type, austenitic type, martensitic type, austenitic / ferrite type and the like can be used.
Here, among the ferritic stainless steels, SUS444 used in the embodiment described later is a high-purity ferritic stainless steel having an extremely low C, an extremely low N, and 18Cr-2Mo, and is particularly resistant to pitting corrosion and crevice corrosion. Since it has excellent properties and stress corrosion cracking resistance, it can be suitably used.

The content of stainless steel and Ti in the base material 1 is preferably 95% by mass or more, and more preferably 99% by mass or more.
As a result, the above-mentioned effect is more prominently exhibited.

The base material 1 preferably has a sufficiently low content of noble metal elements (Au, Ag, Pt, Pd, Rh, Ir, Ru, Os), and the content of the noble metal elements in the base material 1 (plurality). When a species of noble metal element is contained, the total content of these elements) is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and 0.1% by mass or less. Is even more preferable.

As a result, the effect of obtaining an excellent appearance without using a precious metal as a main material is more remarkable.

The base material 1 may have a uniform composition at each site, or may have sites having different compositions. For example, the base material 1 has a base and at least one film that covers the base and has a composition different from that of the base, or a functionally graded material whose composition changes in a gradient (for example, a composition in the thickness direction). May be made of a functionally graded material (such as a functionally graded material).

The shape and size of the base material 1 are not particularly limited, and are usually determined based on the shape and size of the timepiece component 10.

The base material 1 may have, for example, a surface subjected to surface treatment such as mirror surface treatment (polishing processing), roughening treatment (roughening processing), streak processing, and satin finish processing. Further, the base material 1 may be provided with an uneven pattern such as letters, numbers, symbols, and patterns.

As a result, for example, the glossiness of the surface of the timepiece component 10 can be varied, and the aesthetics of the timepiece part 10 can be further improved. Further, since the various films (for example, the first film 2) described in detail later are generally relatively thin, the base material 1 is surface-treated as compared with the case where the film is surface-treated. In this case, the processing is easy and the occurrence rate of defective products can be reduced.

In particular, by performing mirror surface processing (polishing processing), the surface state of the base material 1 can be made smoother, whereby the surface of the timepiece component 10 (the surface 22 of the first coating film 2) can be made smoother. The state can be made smoother.

Further, by performing the roughening treatment (roughening processing), the surface condition of the base material 1 can be appropriately roughened, whereby the surface of the watch component 10 (first coating film 2) can be more reliably roughened. The surface 22) of the above can satisfy the condition of the surface area increase rate as described in detail later. Further, the adhesion between the base material 1 and the first coating film 2 and the like can be made more excellent, and the durability of the timepiece component 10 can be made more excellent.

In particular, by performing the mirror surface processing (polishing process) and the roughening process (roughening process) in combination, the surface of the watch component 10 (the surface 22 of the first coating film 2) will be described in detail later. It is possible to satisfy the condition of the surface area increase rate as described above.

When the mirror surface processing (polishing process) and the roughening process (roughening process) are performed in combination, it is preferable to perform the roughening process (roughening process) after the mirror surface processing (polishing process).

The mirror surface processing can be performed using, for example, a well-known polishing method, and for example, buff polishing, barrel polishing, other mechanical polishing, or the like can be adopted.

Examples of the roughening treatment include a plasma etching treatment and a blasting treatment.

≪First film≫
The first coating film 2 is composed of a material containing Co as a main component, Cr in a content of 26% by mass or more and 30% by mass or less, and Mo in a content of 5% by mass or more and 7% by mass or less. ..

The first coating film 2 made of such a material exhibits a high-class luster with a calm impression even if it does not contain a precious metal, and is excellent in aesthetics. It is also excellent in corrosion resistance, abrasion resistance, wear resistance and the like.

The first coating film 2 contains Co as a main component, and the content of Co in the first coating film 2 is preferably 55% by mass or more and 69% by mass or less, and 62% by mass or more and 68 by mass. It is more preferably 63% by mass or less, and further preferably 63% by mass or more and 67% by mass or less.

As a result, aesthetics and abrasion resistance / wear resistance can be achieved at a higher level.

The content of Cr in the first coating film 2 may be 26% by mass or more and 30% by mass or less, but preferably 26.2% by mass or more and 29.8% by mass or less, and 26.4% by mass or less. It is more preferably 29.6% by mass or less, and further preferably 26.6% by mass or more and 29.4% by mass or less.

As a result, it is possible to make the corrosion resistance, the abrasion resistance, and the wear resistance particularly excellent while making the aesthetics more excellent.

The content of Mo in the first coating film 2 may be 5% by mass or more and 7% by mass or less, but preferably 5.2% by mass or more and 6.8% by mass or less, and 5.3% by mass or less. It is more preferably 6.7% by mass or less, and further preferably 5.4% by mass or more and 6.6% by mass or less.

As a result, aesthetics and abrasion resistance / wear resistance can be achieved at a higher level.

The first coating film 2 may contain components other than the above. Examples of such a component include Si, Mn, N, Fe, C, Ni, Ti, Al, Ag, Pt, Pd, Rh, Ir and the like.

However, the content of components other than Co, Cr and Mo in the first coating film 2 (the sum of these contents when a plurality of types of components are contained) is preferably 3.0% by mass or less. , 2.0% by mass or less, more preferably 1.5% by mass or less.

In particular, the content of noble metal elements (Au, Ag, Pt, Pd, Rh, Ir, Ru, Os) in the first coating film 2 (the sum of these contents when a plurality of kinds of noble metal elements are contained) is determined. It is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less.

As a result, the effect of obtaining an excellent appearance without using a precious metal as a main material is more remarkable.

The first coating film 2 may have a uniform composition at each site, or may have sites having different compositions. For example, the first coating film 2 is composed of a laminated body in which a plurality of layers are laminated or a functionally graded material whose composition changes in an inclined manner (for example, a functionally graded material whose composition changes in an inclined manner in the thickness direction). It may be a product or the like. As a result, for example, it is possible to obtain the effect of providing the first coating film 2 as described above, and to improve the adhesion between the first coating film 2 and the base material 1 or the like, which is suitable for watches. The durability of the component 10 can be made more excellent.

When the reference sample is used, the average signal intensity of oxygen in the first coating film 2 measured by SIMS may be 160 count / sec or more and 300 count / sec or less, but 170 count / sec or more and 290 count / sec or more. It is preferably sec or less, more preferably 180 count / sec or more and 285 count / sec or less, and further preferably 190 count / sec or more and 280 count / sec or less.
As a result, the aesthetics of the timepiece component 10 become more excellent.

The surface 22 of the first coating film 2 (the second surface 22 opposite to the first surface 21 facing the base material 1) is not particularly limited, but the surface 22 is measured by an atomic force microscope. When the measurement is performed, the surface area increase rate with respect to the flat surface is preferably 1.5% or more and 5.0% or less, and 1.6% or more and 4.5% or less. More preferably, it is 1.7% or more and 4.0% or less.
As a result, the timepiece component 10 has a more calm and more luxurious appearance, and is more aesthetically pleasing. In addition, the timepiece component 10 is less likely to be scratched, and even if it is scratched, the scratches are less noticeable, and deterioration of aesthetics can be suppressed.

The surface area increase rate of the surface 22 of the first coating film 2 is determined by measurement using an atomic force microscope with reference to the area (projected area) of the surface (flat surface) assuming that there is no unevenness. The ratio (specific surface area) to the actual surface area of the sample (the area of the surface on which minute nanometer-order irregularities are formed) is obtained, and the increase is expressed as a percentage. In other words, when the actual surface area is A [μm ² ] and the projected area to be measured when the sample surface is completely flat is B [μm ² ], the surface area increase rate C [%] is defined as follows. Will be done.
C = [(A / B) -1] x 100

The measurement using an atomic force microscope can be performed, for example, on a region of 5 μm square on the sample surface.

Further, the measurement field of view may be changed to measure at a plurality of points (for example, 5 points), and the surface area increase rate may be obtained based on the average value.

Examples of the atomic force microscope include "Nanoscope IIIa" manufactured by Digital Instruments.

For example, by adjusting various manufacturing conditions of the timepiece component 10, it is possible to satisfy the above-mentioned surface area increase rate condition. More specifically, for example, the film forming conditions of the first coating film 2, the surface processing after the formation of the first coating film 2 (for example, polishing processing, roughening processing, etc.), and the formation of the first coating film 2. The condition of the surface area increase rate can be adjusted by adjusting the surface condition of the base material (base material 1 or the like) in front of the film.

The thickness of the first coating film 2 is preferably 0.02 μm or more and 2.0 μm or less, more preferably 0.04 μm or more and 1.8 μm or less, and 0.07 μm or more and 1.6 μm or less. Is even more preferable.

As a result, it is possible to improve the glossiness, aesthetics, abrasion resistance, wear resistance, etc. of the watch component 10 as a whole while suppressing the production cost of the watch component 10. Further, it is possible to more effectively prevent the first coating film 2 from being unintentionally peeled off, and to improve the durability of the timepiece component 10.

The method for forming the first coating film 2 is not particularly limited, and for example, spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating and the like, electrolytic plating, dip plating, electroless plating and the like. Wet plating methods, chemical vapor deposition methods such as thermal CVD, plasma CVD, laser CVD, vacuum deposition, sputtering, ion plating, dry plating methods such as laser ablation (vapor deposition method), spraying, etc. However, a dry plating method (vapor deposition method) is preferable.

By applying the dry plating method (gas phase film formation method) as the method for forming the first film 2, the film has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 1 and the like. The first film 2 can be reliably formed. As a result, the aesthetics and durability of the timepiece component 10 can be made particularly excellent.

Further, by applying the dry plating method (gas phase film formation method) as the method for forming the first film 2, even if the first film 2 to be formed is relatively thin, the film thickness is unwilling. The variation can be made sufficiently small. Therefore, it is also advantageous in improving the reliability of the timepiece component 10.

When the first coating film 2 is formed by sputtering, the flow rate of the gas containing oxygen atoms during sputtering is preferably 1 ccm or more and 50 ccm or less, and more preferably 2 ccm or more and 30 ccm or less.

Thereby, the average signal intensity of oxygen in the first coating film 2 measured by SIMS can be easily and surely adjusted by the one satisfying the above-mentioned conditions.

When the first coating film 2 is formed by sputtering, the Ar gas flow rate during sputtering is preferably 50 ccm or more and 150 ccm or less, and more preferably 80 ccm or more and 120 ccm or less.

Thereby, the average signal intensity of oxygen in the first coating film 2 measured by SIMS can be easily and surely adjusted by the one satisfying the above-mentioned conditions. Further, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the first coating film 2 is formed by sputtering, the atmospheric pressure during sputtering is preferably 0.1 Pa or more and 2.5 Pa or less, and more preferably 0.2 Pa or more and 1.0 Pa or less.

Thereby, the average signal intensity of oxygen in the first coating film 2 measured by SIMS can be easily and surely adjusted by the one satisfying the above-mentioned conditions. Further, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the first coating film 2 is formed by sputtering, the power of the sputtering apparatus at the time of sputtering is preferably 0.1 kW or more and 1.8 kW or less, and more preferably 0.3 kW or more and 1.4 kW or less.

Thereby, the average signal intensity of oxygen in the first coating film 2 measured by SIMS can be easily and surely adjusted by the one satisfying the above-mentioned conditions. Further, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the first coating film 2 is formed by sputtering, the bias voltage during sputtering is preferably −150V or more and −30V or less, and more preferably −120V or more and −50V or less.

Thereby, the average signal intensity of oxygen in the first coating film 2 measured by SIMS can be easily and surely adjusted by the one satisfying the above-mentioned conditions. Further, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the first coating film 2 is formed by sputtering, the temperature of the base material 1 during sputtering is preferably 100 ° C. or higher and 210 ° C. or lower, and more preferably 120 ° C. or higher and 190 ° C. or lower.

Thereby, the average signal intensity of oxygen in the first coating film 2 measured by SIMS can be easily and surely adjusted by the one satisfying the above-mentioned conditions. Further, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

The first coating film 2 formed by the above method may be subjected to, for example, an oxidation treatment or a reduction treatment.

Thereby, the average signal intensity of oxygen in the first coating film 2 measured by SIMS can be easily and surely adjusted by the one satisfying the above-mentioned conditions.

The oxidation treatment can be performed, for example, by exposure to an oxidizing gas such as oxygen gas or ozone gas (particularly, exposure to an oxidizing gas under heated conditions).

The reduction treatment can be carried out, for example, by exposure to a reducing gas such as hydrogen gas (particularly, exposure to a reducing gas under heated conditions).

Further, the first coating film 2 may have a surface surface treatment such as a mirror surface treatment (polishing process) or a rough surface processing (roughening process).

Thereby, the surface of the timepiece component 10 (the surface 22 of the first coating film 2) can more reliably satisfy the condition of the surface area increase rate as described above.

In particular, by performing the mirror surface processing (polishing process) and the roughening process (roughening process) in combination, the surface of the watch component 10 (the surface 22 of the first coating film 2) is more reliably described above. The condition of the surface area increase rate can be satisfied.

When the mirror surface processing (polishing process) and the roughening process (roughening process) are performed in combination, it is preferable to perform the roughening process (roughening process) after the mirror surface processing (polishing process). As a result, the above-mentioned effect can be obtained more reliably.

The surface 22 of the first coating 2 (the surface on the side where the first coating 2 is visible, that is, the surface on the viewpoint side of the observer when the timepiece component 10 is used) is L defined by JIS Z 8729. ^{* A *} b ^{* The L *} in the chromaticity diagram displayed is preferably 70.0 or more and 78.4 or less, more preferably 72.0 or more and 78.3 or less, and 74.0 or more and 78. It is more preferably 2 or less.

As a result, the glossiness of the timepiece component 10 becomes more suitable, and the aesthetics of the timepiece part 10 becomes more excellent.

In ^{the measurement of L *} , a light source of D65 defined by JIS Z 8720 can be used as the light source. Further, the viewing angle at the time of measuring ^{L * can be 2 °.}

Further, the surface 22 of the first coating film 2 (the surface on the side where the first coating film 2 is visually recognized, that is, the surface on the viewpoint side of the observer when the timepiece component 10 is used) is defined by JIS Z 8729. L ^* a ^* b ^{* The a *} in the chromaticity diagram displayed is preferably -2.0 or more and 3.0 or less, more preferably -1.5 or more and 2.5 or less, and -1. It is more preferably 0.0 or more and 2.0 or less.

Further, the surface 22 of the first coating film 2 (the surface on the side where the first coating film 2 is visually recognized, that is, the surface on the viewpoint side of the observer when the clock component 10 is used) is defined by JIS Z 8729. that ^L * ^a * ^{b *} is ^{b *} in chromaticity diagram of display, preferably at -1.0 to 10.0, more preferably at 0.0 to 9.0, 1.0 It is more preferably 8.0 or less.

By satisfying such conditions, the aesthetics of the timepiece component 10 become particularly excellent.

^{In the measurement of a *} and b ^* , a light source of D65 defined by JIS Z 8720 can be used. Further, the viewing angle at the time of measuring ^{a *} and b ^{* can be set to 2 °.}

The watch component 10 may be any component that constitutes the watch, but it is preferably a component that can be visually recognized from the outside when the watch is used. Specifically, the windshield, the case, and the case. Bezel, back cover, band (including band piece, band clasp, buckle, buckle, band / bangle attachment / detachment mechanism, etc.), dial, watch hands, rotor, crown (for example, screw lock type crown), Buttons, dial rings, parting plates and the like can be mentioned, and among them, a case or a band is preferable.

Since these parts (watch parts) have a great influence on the appearance of the entire watch, the aesthetics of the watch as a whole can be improved by applying the present invention to these parts. be able to. In addition, these parts are usually exposed to the outside when a watch is used, and are easily in contact with the skin. Among various parts, they have particularly excellent abrasion resistance and abrasion resistance. , It is particularly strongly required to have excellent allergic resistance (difficulty of causing allergic reaction). Therefore, by applying the present invention to these parts, the effects of the present invention as described above are more prominently exhibited.

[Second Embodiment]
Next, the timepiece parts of the second embodiment will be described.
FIG. 2 is a cross-sectional view schematically showing a second embodiment of the timepiece component of the present invention. In the following description, the differences from the above-described embodiment will be mainly described, and the description of the same items will be omitted.

In the timepiece component 10 of the present embodiment, on the surface of the base material 1, the base layer (first base layer) 3 made of a material containing Ti and Co are the main components, and Cr is 26% by mass or more. The first coating film 2 composed of a material containing 30% by mass or less and Mo in a content of 5% by mass or more and 7% by mass or less is laminated in this order. In other words, in the timepiece component 10 of the present embodiment, a base layer 3 made of a material containing Ti is provided between the base material 1 and the first coating film 2.

As a result, the adhesion between the base material 1 and the first coating film 2 can be made more excellent, and the impact applied to the timepiece component 10 can be alleviated, so that the durability of the timepiece part 10 can be improved. It can be better. Further, the surface of the base material 1 can be smoothed, and the color of the watch component 10 as a whole can be finely adjusted, so that the aesthetic appearance of the watch component 10 is more reliably improved. Can be.

The base layer 3 may contain a component other than Ti.
However, the content of the components other than Ti in the base layer 3 is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and 0.5% by mass or less. Is even more preferable.

In particular, the content of noble metal elements (Au, Ag, Pt, Pd, Rh, Ir, Ru, Os) in the base layer 3 (when a plurality of kinds of noble metal elements are contained, the total of these contents) is 1. It is preferably 0% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less.

The thickness of the base layer 3 is preferably 0.01 μm or more and 1.0 μm or less, more preferably 0.02 μm or more and 0.5 μm or less, and further preferably 0.03 μm or more and 0.3 μm or less. preferable.

As a result, the adhesion between the base material 1 and the first coating film 2 and the function of shock mitigation can be further improved, and the durability of the timepiece component 10 can be further improved. , The productivity of the timepiece component 10 can be made more excellent, and the production cost of the timepiece part 10 can be suppressed more effectively. Further, for example, even when surface treatment such as polishing and roughening of the base material 1 is omitted or simplified, the surface area increase rate of the surface 22 of the first coating film 2 is set to a value within the above range. It can be easily adjusted.

The method for forming the base layer 3 is not particularly limited, and for example, coating such as spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, electrolytic plating, dip plating, and wet plating such as electroless plating. Examples thereof include chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD, dry plating (vapor deposition) such as vacuum vapor deposition, sputtering, ion plating, and laser ablation, and spraying. , Dry plating method (vapor deposition method) is preferable.

By applying the dry plating method (gas phase film formation method) as the method for forming the base layer 3, the base layer has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the base material 1 and the like. 3 can be reliably formed. As a result, the aesthetics and durability of the timepiece component 10 can be made particularly excellent.

Further, by applying the dry plating method (gas phase film formation method) as the method for forming the base layer 3, even if the base layer 3 to be formed is relatively thin, the undesired variation in the film thickness is sufficient. Can be small. Therefore, it is also advantageous in improving the reliability of the timepiece component 10.

When the base layer 3 is formed by sputtering, the Ar gas flow rate during sputtering is preferably 50 ccm or more and 150 ccm or less, and more preferably 80 ccm or more and 120 ccm or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the base layer 3 is formed by sputtering, the atmospheric pressure during sputtering is preferably 0.1 Pa or more and 2.5 Pa or less, and more preferably 0.2 Pa or more and 1.0 Pa or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the base layer 3 is formed by sputtering, the power of the sputtering apparatus at the time of sputtering is preferably 0.1 kW or more and 1.8 kW or less, and more preferably 0.3 kW or more and 1.4 kW or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the base layer 3 is formed by sputtering, the bias voltage during sputtering is preferably −150V or more and −30V or less, and more preferably −120V or more and −50V or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the base layer 3 is formed by sputtering, the temperature of the base material 1 during sputtering is preferably 100 ° C. or higher and 210 ° C. or lower, and more preferably 120 ° C. or higher and 190 ° C. or lower.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

The surface of the base layer 3 may be surface-treated, for example, by mirroring (polishing) or roughening (roughening).

As a result, the surface of the timepiece component 10 (the surface 22 of the first coating film 2) can satisfy the condition of the surface area increase rate as described above.

In particular, by performing the mirror surface processing (polishing process) and the roughening process (roughening process) in combination, the surface of the watch component 10 (the surface 22 of the first coating film 2) is more reliably described above. The condition of the surface area increase rate can be satisfied.

When the mirror surface processing (polishing process) and the roughening process (roughening process) are performed in combination, it is preferable to perform the roughening process (roughening process) after the mirror surface processing (polishing process). As a result, the above-mentioned effect can be obtained more reliably.

[Third Embodiment]
Next, the timepiece parts of the third embodiment will be described.
FIG. 3 is a cross-sectional view schematically showing a third embodiment of the timepiece component of the present invention. In the following description, the differences from the above-described embodiment will be mainly described, and the description of the same items will be omitted.

In the timepiece component 10 of the present embodiment, the surface of the base material 1 is made of a material containing at least one of a base layer (first base layer) 3, TiC, and TiCN made of a material containing Ti. The first film composed of the coating film 4 of No. 2 and a material containing Co as a main component, Cr in a content of 26% by mass or more and 30% by mass or less, and Mo in a content of 5% by mass or more and 7% by mass or less. The coating film 2 is laminated in this order. In other words, the same as the above-described second embodiment, except that a second coating film 4 made of a material containing at least one of TiC and TiCN is provided between the base material 1 and the first coating film 2. The same is true.

As a result, the hardness of the timepiece component 10 can be made higher, the dent resistance (difficulty of denting) of the timepiece part 10 can be made more excellent, and the stress can be made. Can be relaxed more effectively, and the durability of the timepiece component 10 can be made more excellent. Further, the color tone can be preferably adjusted (particularly, the glossiness can be adjusted).

The second coating film 4 may contain components other than TiC and TiCN.
However, the content of the components other than TiC and TiCN in the second coating film 4 is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and 0.5% by mass. The following is more preferable.

In particular, the content of noble metal elements (Au, Ag, Pt, Pd, Rh, Ir, Ru, Os) in the second coating film 4 (the sum of these contents when a plurality of kinds of noble metal elements are contained) is determined. It is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less.

The second coating film 4 may have a uniform composition at each site, or may have sites having different compositions. For example, the second coating film 4 may be a laminated body or the like in which a plurality of layers are laminated.

In particular, the second coating film 4 preferably has a portion whose composition changes in a gradient in the thickness direction.

As a result, for example, a second coating film 4 for improving the dent resistance, abrasion resistance, abrasion resistance, etc. of the watch component 10 and adjusting the color (particularly, adjusting the glossiness) is provided. It is possible to improve the adhesion between the second coating film 4 and the portion adjacent to the second coating film 4 (underlying layer 3 and the first coating film 2 in the illustrated configuration) while obtaining the effect of the above. In addition, the destruction of the second coating film 4 (intra-layer peeling, etc.) can be prevented more effectively, and the durability of the timepiece component 10 can be made more excellent.

The second coating film 4 preferably has a region in which the sum of the contents of C and N decreases toward the surface 42 side of the second coating film 4.

As a result, for example, a second coating film 4 for improving the dent resistance, abrasion resistance, abrasion resistance, etc. of the watch component 10 and adjusting the color (particularly, adjusting the glossiness) is provided. The adhesion between the second coating film 4 and the portion adjacent to the second coating film 4 (underlying layer 3 and the first coating film 2 in the illustrated configuration) can be further improved. In addition, it is possible to more effectively prevent the second coating film 4 from being destroyed (peeling in the layer, etc.), and the durability of the timepiece component 10 can be further improved.

The second coating film 4 may have a region in which the sum of the contents of C and N decreases from the central portion in the thickness direction of the second coating film 4 toward one surface side. It is preferable that the second coating film 4 has a region on both sides from the central portion in the thickness direction in which the sum of the contents of C and N decreases, respectively.

As a result, the adhesion between the second coating 4 and the portions provided on both sides of the second coating 4 (in the illustrated configuration, the base layer 3 and the first coating 2) is particularly excellent. This makes it possible to make the durability of the timepiece component 10 particularly excellent.

The content of C and N in the second coating 4 at the portion where the sum of the contents of C and N is maximum (for example, near the central portion in the thickness direction of the second coating 4) is X1 [mass%]. , The content of C and N at the site where the sum of the contents of C and N is minimized in the second coating film 4 (for example, the surface 42 or the surface opposite to the surface 42) was set to X2 [mass%]. When, it is preferable to satisfy the relationship of 1 ≦ X1-X2 ≦ 20, more preferably to satisfy the relationship of 2 ≦ X1-X2 ≦ 15, and further to satisfy the relationship of 3 ≦ X1-X2 ≦ 12. preferable.
As a result, the above-mentioned effect is more prominently exhibited.

The thickness of the second coating film 4 is preferably 0.05 μm or more and 4.0 μm or less, more preferably 0.1 μm or more and 2.0 μm or less, and 0.2 μm or more and 1.5 μm or less. Is even more preferable.

As a result, the hardness of the watch component 10 can be further increased, the dent resistance (difficulty of denting) of the watch component 10 and the like can be further improved, and the durability of the watch component 10 can be improved. The properties can be further improved, the productivity of the watch component 10 can be further improved, and the production cost of the watch component 10 can be suppressed more effectively. In addition, it is possible to more preferably adjust the delicate color of the timepiece component 10 as a whole.

Further, since the base layer 3 is provided, the adhesion between the base material 1 and the second coating film 4 is more excellent, and the durability of the timepiece component 10 is particularly excellent. There is.

The method for forming the second coating film 4 is not particularly limited, and for example, spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating and the like, electrolytic plating, dip plating, electroless plating and the like. Wet plating methods, chemical vapor deposition methods such as thermal CVD, plasma CVD, laser CVD, vacuum deposition, sputtering, ion plating, dry plating methods such as laser ablation (vapor deposition method), spraying, etc. However, a dry plating method (vapor deposition method) is preferable.

By applying the dry plating method (gas phase film formation method) as the method for forming the second coating film 4, the film has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the underlying layer 3 and the like. The second coating film 4 can be reliably formed. As a result, the aesthetics and durability of the timepiece component 10 can be made particularly excellent.

Further, by applying the dry plating method (gas phase film formation method) as the method for forming the second film 4, even if the second film 4 to be formed is relatively thin, the film thickness is unwilling. The variation can be made sufficiently small. Therefore, it is also advantageous in improving the reliability of the timepiece component 10.

When the second coating film 4 is formed by sputtering, the Ar gas flow rate during sputtering is preferably 50 ccm or more and 150 ccm or less, and more preferably 80 ccm or more and 120 ccm or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the second coating film 4 is formed by sputtering, the C ₂ H ₂ gas flow rate during sputtering is preferably 10 ccm or more and 50 ccm or less, and more preferably 15 ccm or more and 30 ccm or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the second coating film 4 is formed by sputtering, the atmospheric pressure during sputtering is preferably 0.1 Pa or more and 2.5 Pa or less, and more preferably 0.2 Pa or more and 1.0 Pa or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the second coating 4 is formed by sputtering, the power of the sputtering apparatus at the time of sputtering is preferably 2.0 kW or more and 6 kW or less, and more preferably 2.5 kW or more and 5.8 kW or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the second coating 4 is formed by sputtering, the bias voltage during sputtering is preferably −150V or more and −30V or less, and more preferably −120V or more and −50V or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the second coating film 4 is formed by sputtering, the temperature of the base material 1 during sputtering is preferably 100 ° C. or higher and 210 ° C. or lower, and more preferably 120 ° C. or higher and 190 ° C. or lower.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

The surface of the second coating film 4 may be, for example, surface-treated such as a mirror surface treatment (polishing process) or a roughening process (roughening process).

Thereby, the surface of the timepiece component 10 (the surface 22 of the first coating film 2) can more reliably satisfy the condition of the surface area increase rate as described above.

In particular, by performing the mirror surface processing (polishing process) and the roughening process (roughening process) in combination, the surface of the watch component 10 (the surface 22 of the first coating film 2) is more reliably described above. The condition of the surface area increase rate can be satisfied.

When the mirror surface processing (polishing process) and the roughening process (roughening process) are performed in combination, it is preferable to perform the roughening process (roughening process) after the mirror surface processing (polishing process). As a result, the above-mentioned effect can be obtained more reliably.

The second coating film 4 as described above can be applied to the first embodiment and exhibits the same effect.

[Fourth Embodiment]
Next, the timepiece parts of the fourth embodiment will be described.
FIG. 4 is a cross-sectional view schematically showing a fourth embodiment of the timepiece component of the present invention. In the following description, the differences from the above-described embodiment will be mainly described, and the description of the same matters will be omitted.

In the clock component 10 of the present embodiment, the surface of the base material 1 is made of a material containing at least one of a base layer (first base layer) 3, TiC, and TiCN made of a material containing Ti. The coating material 4 of 2 and the base layer (second base layer) 5 composed of a material containing Ti, and Co as a main component, Cr content of 26% by mass or more and 30% by mass or less, Mo content of 5% by mass. The first coating film 2 made of a material containing% or more and 7% by mass or less is laminated in this order. In other words, in the present embodiment, a second coating film 4 made of a material containing at least one of TiC and TiCN is provided between the base material 1 and the first coating film 2, and the second coating film 4 is provided. Underlayers 3 and 5 are provided on both sides of the above.

As a result, not only the adhesion between the base material 1 and the second coating film 4 but also the adhesion between the second coating film 4 and the first coating film 2 can be made excellent, and the timepiece component The impact applied to the watch 10 can be more effectively mitigated, and the durability of the timepiece component 10 can be further improved. Further, the surface of the second coating film 4 can be smoothed, and the color of the watch component 10 as a whole can be finely adjusted, so that the aesthetic appearance of the watch component 10 is more reliably improved. It can be a clock.

The base layer 5 may contain components other than Ti.
However, the content of the components other than Ti in the base layer 5 is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and 0.5% by mass or less. Is even more preferable.

In particular, the content of noble metal elements (Au, Ag, Pt, Pd, Rh, Ir, Ru, Os) in the base layer 5 (when a plurality of kinds of noble metal elements are contained, the total of these contents) is 1. It is preferably 0% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less.

The thickness of the base layer 5 is preferably 0.01 μm or more and 1.0 μm or less, more preferably 0.02 μm or more and 0.5 μm or less, and further preferably 0.03 μm or more and 0.3 μm or less. preferable.

As a result, the adhesion between the second coating 4 and the first coating 2 and the shock absorbing function can be further improved, and the durability of the timepiece component 10 can be further improved. At the same time, the productivity of the timepiece component 10 can be made more excellent, and the production cost of the timepiece part 10 can be suppressed more effectively. Further, it is possible to more preferably smooth the surface of the second coating film 4 and finely adjust the color of the watch component 10 as a whole.

The method for forming the base layer 5 is not particularly limited, and for example, coating such as spin coating, dipping, brush coating, spray coating, electrostatic coating, electrodeposition coating, electrolytic plating, dip plating, and wet plating such as electroless plating. Examples thereof include chemical vapor deposition (CVD) such as thermal CVD, plasma CVD, and laser CVD, dry plating (vapor deposition) such as vacuum vapor deposition, sputtering, ion plating, and laser ablation, and spraying. , Dry plating method (vapor deposition method) is preferable.

By applying the dry plating method (gas phase film formation method) as the method for forming the base layer 5, the film has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the second film 4 and the like. The base layer 5 can be reliably formed. As a result, the aesthetics and durability of the timepiece component 10 can be made particularly excellent.

Further, by applying the dry plating method (gas phase film formation method) as the method for forming the base layer 5, even if the base layer 5 to be formed is relatively thin, the undesired variation in the film thickness is sufficient. Can be small. Therefore, it is also advantageous in improving the reliability of the timepiece component 10.

When the base layer 5 is formed by sputtering, the Ar gas flow rate during sputtering is preferably 50 ccm or more and 150 ccm or less, and more preferably 80 ccm or more and 120 ccm or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the base layer 5 is formed by sputtering, the atmospheric pressure during sputtering is preferably 0.1 Pa or more and 2.5 Pa or less, and more preferably 0.2 Pa or more and 1.0 Pa or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the base layer 5 is formed by sputtering, the power of the sputtering apparatus at the time of sputtering is preferably 0.1 kW or more and 1.8 kW or less, and more preferably 0.3 kW or more and 1.4 kW or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the base layer 5 is formed by sputtering, the bias voltage during sputtering is preferably −150V or more and −30V or less, and more preferably −120V or more and −50V or less.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

When the base layer 5 is formed by sputtering, the temperature of the base material 1 during sputtering is preferably 100 ° C. or higher and 210 ° C. or lower, and more preferably 120 ° C. or higher and 190 ° C. or lower.

Thereby, even when the post-treatment such as the polishing treatment is omitted or simplified, the first coating film 2 satisfying the above-mentioned condition of the surface area increase rate can be more preferably formed.

The surface of the base layer 3 may be surface-treated, for example, by mirroring (polishing) or roughening (roughening).

Thereby, the surface of the timepiece component 10 (the surface 22 of the first coating film 2) can more reliably satisfy the condition of the surface area increase rate as described above.

[Fifth Embodiment]
Next, the timepiece parts of the fifth embodiment will be described.
FIG. 5 is a cross-sectional view schematically showing a fifth embodiment of the timepiece component of the present invention. In the following description, the differences from the above-described embodiment will be mainly described, and the description of the same matters will be omitted.

In the clock component 10 of the present embodiment, the surface of the base material 1 is made of a material containing at least one of a base layer (first base layer) 3, TiC, and TiCN made of a material containing Ti. 2 film 4, base layer (second base layer) 5 composed of material containing Ti, Co as the main component, Cr content of 26% by mass or more and 30% by mass or less, Mo content of 5% by mass or more The first coating film 2 made of a material containing 7% by mass or less and the coat layer 6 made of a material containing a fluorine-containing organosilicon compound are laminated in this order. In other words, it is the same as the above-described fourth embodiment except that the coat layer 6 made of a material containing a fluorine-containing organosilicon compound is provided on the outer surface side of the first coating film 2.

As a result, it is possible to more effectively prevent deterioration of aesthetics due to adhesion of dirt. Further, even when dirt is attached, the dirt can be removed more easily. Therefore, it is possible to more preferably maintain excellent aesthetics under various environments for a long period of time. Further, by having the coat layer 6 made of a material containing a fluorine-containing organosilicon compound, not only antifouling property but also touch feeling, waterproof property and the like are improved. Further, since the fluorine-containing organosilicon compound has a small influence on the appearance of the watch component 10 as a whole, the aesthetics of the watch component 10 can be more reliably improved.

Specific examples of the fluorine-containing organic silicon compound include CF ₃ (CF ₂ ) ₂ C ₂ H ₄ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₄ C ₂ H ₄ Si (OCH ₃ ) ₃ , CF ₃ ( CF ₂ ) ₆ C ₂ H ₄ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₈ C ₂ H ₄ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₁₀ C ₂ H ₄ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₁₂ C ₂ H ₄ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₁₄ C ₂ H ₄ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₁₆ C ₂ H ₄ Si ( OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₁₈ C ₂ H ₄ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₆ C ₂ H ₄ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₈ C ₂ H ₄ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₆ C ₂ H ₄ SiCl ₃ , CF ₃ (CF ₂ ) ₈ C ₂ H ₄ SiCl ₃ , CF ₃ (CF ₂ ) ₆ C ₃ H ₆ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₈ C ₃ H ₆ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₆ C ₃ H ₆ Si (OC ₂ H ₅ ) ₃ , CF ₃ ( CF ₂ ) ₈ C ₃ H ₆ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₆ C ₃ H ₆ SiCl ₃ , CF ₃ (CF ₂ ) ₈ C ₃ H ₆ SiCl ₃ , CF ₃ (CF ₂₎ ) ₆ C ₄ H ₈ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₈ C ₄ H ₈ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₆ C ₄ H ₈ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₈ C ₄ H ₈ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₆ C ₂ H ₄ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₈ C ₂ H ₄ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₆ C ₂ H ₄ Si (CH ₃ ) Cl ₂ , CF ₃ (CF ₂ ) ₈ C ₂ H ₄ Si (CH ₃ ) Cl ₂ , CF ₃ (CF ₂ ) ₆ C ₂ H ₄ Si (C ₂ H ₅ ) (OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₈ C ₂ H ₄ Si (C ₂ H ₅ ) (OC ₂ H ₅ ) _{2 and the} like can be mentioned.

Further, as the fluorine-containing organosilicon compound, a compound containing an amino group can also be preferably used.

Examples of the fluorine-containing organosilicon compound containing an amino group include C ₉ F ₁₉ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₉ F ₁₉ CONH (CH ₂ ) ₃ SiCl ₃ , C ₉ F. ₁₉ CONH (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , C ₉ F ₁₉ CONH (CH ₂ ) NH (CH ₂ ) Si (OC ₂ H ₅ ) ₃ , C ₉ F ₁₉ CONH (CH ₂ ) ₅ CONH (CH 2) CH ₂ ) Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₅ CONH (CH ₂ ) Si (OC ₂ H ₅ ) ₃ , C ₃ F ₇ O (CF (CF ₃ ) CF _{2 O) 2 -CF (CF 3} ) -CONH (CH 2) Si (OC 2 H 5) 3, C 3 F 7 O (CF (CF 3) CF 2 O) m '-CF (CF 3) -CONH (CH ₂ ) Si (OCH ₃ ) ₃ [Here, m'is an integer of 1 or more] and the like.

As the fluorine-containing organic silicon compound, for _{example, R f '(CH 2)} 2 SiCl 3, R f' (CH 2) 2 Si (CH 3) Cl 2, (R f 'CH 2 CH 2) 2 SiCl _{2, R f '(CH 2} ) 2 Si (OCH 3) 3, R f' CONH (CH 2) 3 Si (OC 2 H 5) 3, R f 'CONH (CH 2) 2 NH (CH 2) 3 _{Si (OC 2 H 5) 3} , R f 'SO 2 N (CH 3) (CH 2) 2 CONH (CH 2) 3 Si (OC 2 H 5) 3, R f' (CH 2) 2 OCO (CH _{2) 2 S (CH 2)} 3 Si (OCH 3) 3, R f '(CH 2) 2 OCONH (CH 2) 2 Si (OC 2 H 5) 3, R f' COO-Cy (OH) - ( CH ₂ ) ₂ Si (OCH ₃ ) ₃ , R _f '(CH ₂ ) ₂ NH (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , and R _f '(CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH) ₂ ) ₂ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ or the like may be used. In each of the above formulas, Cy is a cyclohexane residue and R _f'is a polyfluoroalkyl group having 4 or more and 16 or less carbon atoms.

As the fluorine-containing organosilicon compound constituting the coat layer 6, a compound represented by the following formula (1) or the following formula (2) is particularly preferable.

In formula (1), R _f ¹ represents a perfluoroalkyl group. X represents bromine, iodine or hydrogen. Y represents a hydrogen or lower alkyl group and Z represents a fluorine or trifluoromethyl group. R ¹ represents a hydrolyzable group and R ² represents a hydrogen or an inert monovalent hydrocarbon group. a, b, c, d, e are 0 or an integer of 1 or more, and a + b + c + d + e is at least 1 or more, and the existence order of each repeating unit enclosed by a, b, c, d, e is in the formula. Not limited to. f is 0, 1 or 2. g is 1, 2 or 3. h is an integer greater than or equal to 1.

In formula (2), R _f ² is a divalent group containing a unit represented by the formula: "-(C _k F _2k ) O-" and having a linear perfluoropolyalkylene ether structure without branching. Is shown. _{In addition, k} in the formula: "-(C k F _2k ) O-" is an integer of 1 or more and 6 or less. R ³ is a monovalent hydrocarbon group having 1 or more carbon atoms and 8 or less carbon atoms, and W represents a hydrolyzable group or a halogen atom. p is 0, 1 or 2, and n is an integer of 1 or more and 5 or less. m and r are 2 or 3.

The thickness of the coat layer 6 is preferably 0.01 μm or more and 1.0 μm or less, more preferably 0.02 μm or more and 0.5 μm or less, and further preferably 0.03 μm or more and 0.3 μm or less. preferable.

The coat layer 6 as described above can be applied to any of the first to fourth embodiments, and exhibits the same effect.

"clock"
Next, the clock of the present invention will be described.

FIG. 6 is a partial cross-sectional view schematically showing a preferred embodiment of the watch (wrist watch) of the present invention.
The wristwatch (clock) W10 of the present embodiment includes a body (case) W22, a back cover W23, a bezel (edge) W24, and a glass plate (windshield) W25. Further, a movement (for example, one with a dial and hands) (not shown) is housed in the case W22.

A winding stem pipe W26 is fitted and fixed to the body W22, and a shaft portion W271 of a crown W27 is rotatably inserted into the winding stem pipe W26.

The body W22 and the bezel W24 are fixed by the plastic packing W28, and the bezel W24 and the glass plate W25 are fixed by the plastic packing W29.

Further, the back cover W23 is fitted (or screwed) to the body W22, and a ring-shaped rubber packing (back cover packing) W40 is inserted into the joint portion (seal portion) W50 in a compressed state. Has been done. With this configuration, the seal portion W50 is liquid-tightly sealed, and a waterproof function can be obtained.

A groove W272 is formed on the outer periphery of the shaft portion W271 of the crown W27, and a ring-shaped rubber packing (crown packing) W30 is fitted in the groove W272. The rubber packing W30 is in close contact with the inner peripheral surface of the winding pipe W26, and is compressed between the inner peripheral surface and the inner surface of the groove W272. With this configuration, the space between the crown W27 and the winding pipe W26 is hermetically sealed to obtain a waterproof function. When the crown W27 is rotated, the rubber packing W30 rotates together with the shaft portion W271 and slides in the circumferential direction while being in close contact with the inner peripheral surface of the winding stem pipe W26.

The wristwatch W10 as a timepiece of the present invention has at least one of its components composed of the timepiece parts of the present invention as described above. In other words, the timepiece of the present invention is provided with the timepiece parts of the present invention.

As a result, it has excellent aesthetics (particularly, it has an appropriate luster, but the brightness is not too high and gives a high-class appearance with a calm impression), and it has excellent corrosion resistance, as well as abrasion resistance and abrasion resistance. It is possible to provide a timepiece W10 provided with excellent parts for a timepiece.

Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto.

For example, in the timepiece parts and the timepiece of the present invention, the configuration of each part can be replaced with an arbitrary configuration that exhibits the same function, or an arbitrary configuration can be added.
For example, the timepiece component may include a base layer made of a material other than Ti, a coat layer made of a material other than the fluorine-containing organosilicon compound, and the like.

Further, in the above-described embodiment, as the form of the timepiece component having the base layer, the configuration having one or two base layers has been described, but the timepiece part includes three or more base layers. It may be. Further, in the above-described embodiment, as the form of the timepiece component having the second coating film, the configuration having one layer of the second coating film has been described, but the timepiece component has two or more layers of the second coating film. It may be provided with.
Further, the timepiece component may include a plurality of sets of the base layer and the second coating film.

Further, in the above-described embodiment, the case where the observer's viewpoint when using the watch component is the surface side on which the first coating film is provided of the watch component has been mainly described, but the base material is transparent. The observer's viewpoint may be on the opposite side when the material is made of a material having a property. In other words, the first coating film may be visible through the base material. In such a case, it is preferable that the surface of the first coating film on the observer side facing the base material satisfies the above-mentioned surface area increase rate condition.

Next, specific examples of the present invention will be described. The sputtering described below was performed using AS14G (inner diameter: 1250 mm, height: 1000 mm) manufactured by ProChina as a magnetron sputtering apparatus.

[1] Manufacture of watch parts (Example 1)
First, a pure Ti base material having a shape corresponding to the wristwatch case was prepared.
Next, the surface of the base material (the surface on the side where the first film is formed) was buffed, and then plasma etching was performed. When the surface was measured by an atomic force microscope, the surface area increase rate with respect to the flat surface was 2.0%.

Next, the substrate subjected to this surface treatment (buffing and plasma etching treatment) was washed. As the washing of the base material, first, alkaline electrolytic degreasing was carried out for 30 seconds, then neutralization was carried out for 10 seconds, water washing was carried out for 10 seconds, and pure water washing was carried out for 10 seconds.

Next, by performing sputtering, a first film having a thickness of 0.5 μm made of a CoCrMo alloy was formed on the surface of the base material. The Ar gas flow rate at the time of forming the first film is 100 ccm, the flow rate of the gas containing oxygen atoms (O ₂ gas) is 10 c cm, the atmospheric pressure is 0.3 Pa, and the gas containing oxygen atoms (O ₂ gas) in the atmosphere. The partial pressure was set to 0.03 Pa, the power was set to 1 kW, the bias voltage was set to −80 V, and the substrate temperature was set to 160 ° C.
As a result, a wristwatch case as a watch part was obtained.

Using the same magnettron sputtering device (manufactured by ProChina, AS14G) used for manufacturing the above clock parts, Ar gas flow rate: 100 cm, gas flow rate containing oxygen atoms: 0 cm cm, atmospheric pressure: 0.3 Pa. , Co: 62.8% by mass, Cr: 28.2% by mass under the conditions of partial pressure of gas containing oxygen atoms in the atmosphere: 0Pa, power: 5kW, bias voltage: -80V, substrate temperature: 160 ° C. , Mo: 6.0% by mass, C: 1.5% by mass, Ar: 1.5% by mass, and a film having a thickness of 1.0 μm was produced as a reference sample. The content of components other than Co, Cr, Mo, C and Ar in the obtained reference sample was 500 ppm or less. When the film was used as a reference sample, the average signal intensity of oxygen in the first film measured using SIMS was 270 count / sec.

Further, the surface area of the surface (second surface) of the first coating film had a surface area increase rate of 2.5% with respect to the flat surface when measured by an atomic force microscope.

The measurement using the atomic force microscope was performed for five 5 μm square regions with different measurement fields of view on the sample surface, the surface area increase rate was obtained for each region, and the surface area increase rate was used as the average value of these regions. The surface area increase rate of the surface was used. As the atomic force microscope, "Nanoscope IIIa" manufactured by Digital Instruments was used. The same applies to each of the following Examples and Comparative Examples.

(Example 2)
As the base material, a ferrite-based stainless steel that has not been surface-processed (polishing, roughening, etc.) made of SUS444 (measurement by an interatomic force microscope on the surface on the side where the first coating is formed). _{A gas containing oxygen atoms (O 2} gas) with an Ar gas flow rate of 100 ccm at the time of forming the first coating film, using a gas having a surface area increase rate of 2.5% with respect to a flat surface). ) Flow rate is 10 cm, atmospheric pressure is 0.3 Pa, _{partial pressure of gas containing oxygen atoms (O 2} gas) in the atmosphere is 0.03 Pa, power is 1 kW, bias voltage is -80 V, and substrate temperature is 160 ° C. A clock component (wristcase case) was manufactured in the same manner as in Example 1 above, except that the surface of the formed first film was buffed and plasma-etched in this order.

(Example 3)
First, a pure Ti base material having a shape corresponding to the wristwatch case was prepared.
Next, the surface of the base material (the base layer, the surface on the side where the first film is formed) was buffed, and then plasma etching was performed. When the surface was measured by an atomic force microscope, the surface area increase rate with respect to the flat surface was 2.0%.

Next, the substrate subjected to this surface treatment (buffing and plasma etching treatment) was washed. As the washing of the base material, first, alkaline electrolytic degreasing was carried out for 30 seconds, then neutralization was carried out for 10 seconds, water washing was carried out for 10 seconds, and pure water washing was carried out for 10 seconds.

Next, by performing sputtering, a base layer (first base layer) having a thickness of 0.1 μm composed of Ti was formed on the surface of the base material. The Ar gas flow rate at the time of forming the base layer was set to 100 ccm, the atmospheric pressure was set to 0.3 Pa, the power was set to 1 kW, the bias voltage was set to −80 V, and the base material temperature was set to 160 ° C.

Subsequently, by sputtering, a first film having a thickness of 0.5 μm composed of a CoCrMo alloy was formed on the surface of the base layer. The Ar gas flow rate at the time of forming the first film is 100 ccm, the flow rate of the gas containing oxygen atoms (O ₂ gas) is 10 c cm, the atmospheric pressure is 0.3 Pa, and the gas containing oxygen atoms (O ₂ gas) in the atmosphere. The partial pressure was set to 0.03 Pa, the power was set to 1 kW, the bias voltage was set to −80 V, and the substrate temperature was set to 160 ° C.
As a result, a wristwatch case as a watch part was obtained.

(Example 4)
When the base material is made of SUS444 without surface processing (polishing, roughening, etc.) (underlying layer, the surface on the side where the first coating is formed) is measured by an interatomic force microscope. , The rate of increase in surface area with respect to the flat surface is 2.5%), the Ar gas flow rate at the time of forming the first coating is 100 cm, and the flow rate of gas _{containing oxygen atoms (O 2 gas) is set.} It is formed with 10 ccm, atmospheric pressure of 0.3 Pa, _{partial pressure of gas (O 2} gas) containing oxygen atoms in the atmosphere of 0.03 Pa, power of 1 kW, bias voltage of -80 V, and substrate temperature of 160 ° C. A watch part (wristwatch case) was manufactured in the same manner as in Example 3 except that the surface of the first coating film was buffed and plasma-etched in this order.

(Example 5)
First, a pure Ti base material having a shape corresponding to the wristwatch case was prepared.
Next, the surface of the base material (the base layer, the second coating, and the surface on the side where the first coating is formed) was buffed, and then plasma etching was performed. When the surface was measured by an atomic force microscope, the surface area increase rate with respect to the flat surface was 2.0%.

Next, the substrate subjected to this surface treatment (buffing and plasma etching treatment) was washed. As the washing of the base material, first, alkaline electrolytic degreasing was carried out for 30 seconds, then neutralization was carried out for 10 seconds, water washing was carried out for 10 seconds, and pure water washing was carried out for 10 seconds.

Next, by performing sputtering, a base layer having a thickness of 0.1 μm composed of Ti was formed on the surface of the base material. The Ar gas flow rate at the time of forming the base layer was set to 100 ccm, the atmospheric pressure was set to 0.3 Pa, the power was set to 1 kW, the bias voltage was set to −80 V, and the base material temperature was set to 160 ° C.

Subsequently, by sputtering, a second film having a thickness of 0.35 μm composed of TiC was formed on the surface of the base layer. The Ar gas flow rate at the time of forming the second film was set to 100 ccm, the C ₂ H ₂ gas flow rate was set to 22 ccm, the atmospheric pressure was set to 0.3 Pa, the power was set to 5 kW, the bias voltage was set to −80 V, and the substrate temperature was set to 160 ° C.

Subsequently, by sputtering, a first film having a thickness of 0.5 μm composed of a CoCrMo alloy was formed on the surface of the base layer. The Ar gas flow rate at the time of forming the first film is 100 ccm, the flow rate of the gas containing oxygen atoms (O ₂ gas) is 10 c cm, the atmospheric pressure is 0.3 Pa, and the gas containing oxygen atoms (O ₂ gas) in the atmosphere. The partial pressure was set to 0.03 Pa, the power was set to 1 kW, the bias voltage was set to −80 V, and the substrate temperature was set to 160 ° C.
As a result, a wristwatch case as a watch part was obtained.

(Example 6)
Measured by an interatomic force microscope on the surface on the side where the base layer, the second coating, and the first coating are formed, which is made of SUS444 without surface processing (polishing, roughening, etc.) as the base material. The composition of the CoCrMo alloy used as the target at the time of forming the first coating film was changed by using the one in which the rate of increase in surface area with respect to the flat surface was 2.5%). The Ar gas flow rate at the time of forming the film is 100 ccm, the flow rate of the gas containing oxygen atoms (O ₂ gas) is 10 cm cm, the atmospheric pressure is 0.3 Pa, and the partial pressure of the gas _{containing oxygen atoms (O 2 gas) in the atmosphere is divided.} The above steps were carried out except that the surface of the first coating film formed was 0.03 Pa, the power was 1 kW, the bias voltage was -80 V, the substrate temperature was 160 ° C., and the surface of the first coating film was buffed and plasma-etched in this order. A watch part (watch case) was manufactured in the same manner as in Example 5.

(Example 7)
First, a pure Ti base material having a shape corresponding to the wristwatch case was prepared.
Next, the surface of the base material (the first base layer, the second coating, the second base layer, the surface on the side where the first coating is formed) is buffed, and then plasma etching treatment is performed. provided. When the surface was measured by an atomic force microscope, the surface area increase rate with respect to the flat surface was 2.0%.

Next, the substrate subjected to this surface treatment (buffing and plasma etching treatment) was washed. As the washing of the base material, first, alkaline electrolytic degreasing was carried out for 30 seconds, then neutralization was carried out for 10 seconds, water washing was carried out for 10 seconds, and pure water washing was carried out for 10 seconds.

Next, by performing sputtering, a first base layer having a thickness of 0.1 μm composed of Ti was formed on the surface of the base material. The Ar gas flow rate at the time of forming the first base layer was set to 100 ccm, the atmospheric pressure was set to 0.3 Pa, the power was set to 1 kW, the bias voltage was set to −80 V, and the base material temperature was set to 160 ° C.

Subsequently, by sputtering, a second film having a thickness of 0.50 μm composed of TiC was formed on the surface of the first base layer. The Ar gas flow rate at the time of forming the second coating film was set to 100 ccm, the atmospheric pressure was set to 0.3 Pa, the power was set to 5 kW, the bias voltage was set to −80 V, and the substrate temperature was set to 160 ° C. Further, at this time, _{the flow rate of the C 2} H ₂ gas is increased from 10 ccm to 20 ccm, and then _{the flow rate of the C 2} H ₂ gas is decreased from 20 ccm to 10 c cm, whereby the second coating film is formed at the center of the thickness. It was formed as a functionally graded material in which the sum of the contents of C and N was large in the vicinity and the value of the sum of the contents of C and N gradually decreased toward both surfaces.

Subsequently, by sputtering, a second base layer having a thickness of 0.05 μm composed of Ti was formed on the surface of the second coating film. The Ar gas flow rate at the time of forming the second base layer was set to 100 ccm, the atmospheric pressure was set to 0.3 Pa, the power was set to 1 kW, the bias voltage was set to −80 V, and the base material temperature was set to 160 ° C.

Subsequently, by sputtering, a first film having a thickness of 0.5 μm composed of a CoCrMo alloy was formed on the surface of the second base layer. The Ar gas flow rate at the time of forming the first film is 100 ccm, the flow rate of the gas containing oxygen atoms (O ₂ gas) is 10 c cm, the atmospheric pressure is 0.3 Pa, and the gas containing oxygen atoms (O ₂ gas) in the atmosphere. The partial pressure is set to 0.03 Pa, the substrate temperature is set to 160 ° C., the power is changed over time from 0.3 kW to 1 kW, and the bias voltage is changed over time from -40 V to -80 V. As a result, the first coating film was formed as an inclined material whose composition and film quality changed in an inclined manner in the thickness direction.
As a result, a wristwatch case as a watch part was obtained.

(Example 8)
A base material made of SUS444 that has not been surface-processed (polishing, roughening, etc.) (first base layer, second coating, second base layer, side on which the first coating is formed). When the surface of the gas is measured with an interatomic force microscope, the rate of increase in surface area with respect to the flat surface is 2.5%), and the film formation time of each film (each layer) is changed. The Ar gas flow rate at the time of forming the first coating film is 100 ccm, the flow rate of the gas containing oxygen atoms (O ₂ gas) is 10 cm cm, the atmospheric pressure is 0.3 Pa, and the gas containing oxygen atoms in the atmosphere (O ₂ gas). The partial pressure is 0.03 Pa, the power is 1 kW, the bias voltage is -80 V, the substrate temperature is 160 ° C., and the surface of the formed first coating film is buffed and plasma-etched in this order. , A watch part (wristcase case) was manufactured in the same manner as in Example 7 except that the configuration was as shown in Table 1.

(Example 9)
First, a pure Ti base material having a shape corresponding to the wristwatch case was prepared.
Next, the surface of the base material (the surface on the side where the first base layer, the second coating, the second base layer, the first coating, and the coat layer are formed) is buffed, and then plasma is applied. It was etched. When the surface was measured by an atomic force microscope, the surface area increase rate with respect to the flat surface was 2.0%.

Next, the substrate subjected to this surface treatment (buffing and plasma etching treatment) was washed. As the washing of the base material, first, alkaline electrolytic degreasing was carried out for 30 seconds, then neutralization was carried out for 10 seconds, water washing was carried out for 10 seconds, and pure water washing was carried out for 10 seconds.

Next, by performing sputtering, a first base layer having a thickness of 0.1 μm composed of Ti was formed on the surface of the base material. The Ar gas flow rate at the time of forming the first base layer was set to 100 ccm, the atmospheric pressure was set to 0.3 Pa, the power was set to 1 kW, the bias voltage was set to −80 V, and the base material temperature was set to 160 ° C.

Subsequently, by sputtering, a second film having a thickness of 0.35 μm composed of TiC was formed on the surface of the first base layer. The Ar gas flow rate at the time of forming the second film was set to 100 ccm, the C ₂ H ₂ gas flow rate was set to 22 ccm, the atmospheric pressure was set to 0.3 Pa, the power was set to 5 kW, the bias voltage was set to −80 V, and the substrate temperature was set to 160 ° C.

Subsequently, by sputtering, a second base layer having a thickness of 0.05 μm composed of Ti was formed on the surface of the second coating film. The Ar gas flow rate at the time of forming the second base layer was set to 100 ccm, the atmospheric pressure was set to 0.3 Pa, the power was set to 1 kW, the bias voltage was set to −80 V, and the base material temperature was set to 160 ° C.

Subsequently, by sputtering, a first film having a thickness of 0.5 μm composed of a CoCrMo alloy was formed on the surface of the second base layer. The Ar gas flow rate at the time of forming the first film is 100 ccm, the flow rate of the gas containing oxygen atoms (O ₂ gas) is 10 c cm, the atmospheric pressure is 0.3 Pa, and the gas containing oxygen atoms (O ₂ gas) in the atmosphere. The partial pressure was set to 0.03 Pa, the power was set to 1 kW, the bias voltage was set to −80 V, and the substrate temperature was set to 160 ° C.

Next, as described below, a coat layer having a thickness of 0.03 μm composed of a fluorine-containing organosilicon compound was formed on the surface of the first coating film to obtain a wristwatch case as a watch component.

That is, first, a fluorine-containing organosilicon compound (manufactured by Shin-Etsu Chemical Co., Ltd., KY-130 (3)) is diluted with a fluorine-based solvent (manufactured by Shin-Etsu Chemical Co., Ltd., FR thinner) so that the solid content becomes 3% by mass. A container (cylindrical copper container with an open upper part, inner diameter 16 mm x inner height) filled with 0.5 g of steel wool (manufactured by Nippon Steel Wool Co., Ltd., # 0, wire diameter 0.025 mm) in advance. 6 mm) was filled with 1.0 g and dried at 120 ° C. for 1 hour. Next, this copper container is placed in a vacuum evaporator together with a first base layer, a second coating, a second base layer, and a base material on which the first coating is formed, and the inside of the device is set to 0. After the pressure was set to 0.01 Pa, the fluorine-containing organosilicon compound was evaporated from the copper container so as to have a film formation rate (vaporization rate) of 0.6 Å / s. A molybdenum resistance heating boat was used as the heating source.

(Example 10)
A base material made of SUS444 that has not been surface-processed (polishing, roughening, etc.) (first base layer, second coating, second base layer, first coating, coat layer is formed. Ar gas at the time of forming the first coating film using the one with a surface area increase rate of 2.5% with respect to the flat surface when measured by an interatomic force microscope on the surface on the side to be subjected to. The flow rate is 100 ccm, the flow rate of the gas containing oxygen atoms (O ₂ gas) is 10 cm cm, the atmospheric pressure is 0.3 Pa, _{the partial pressure of the gas containing oxygen atoms (O 2} gas) in the atmosphere is 0.03 Pa, and the power is 1 kW. , The bias voltage was -80 V, the substrate temperature was 160 ° C., and the surface of the formed first coating film was buffed and plasma-etched in this order. Manufactured parts for watches (cases for watches).

(Comparative Example 1)
A watch component (wristwatch case) was manufactured in the same manner as in Example 1 above, except that a film made of Pt was formed instead of the first film made of CoCrMo alloy.

(Comparative Examples 2 to 5)
A watch component (wristwatch case) was manufactured in the same manner as in Example 1 except that the composition of the CoCrMo alloy used as the target when forming the first film was changed.

(Comparative Example 6)
The Ar gas flow rate at the time of forming the first film is 100 ccm, the flow rate of the gas containing oxygen atoms is 0 ccm, the atmospheric pressure is 0.3 Pa, the partial pressure of the gas containing oxygen atoms in the atmosphere is 0 Pa, the power is 9 kW, and the bias. A watch component (watch case) was manufactured in the same manner as in Example 1 except that the voltage was −120 V and the substrate temperature was 200 ° C.

(Comparative Example 7)
The Ar gas flow rate at the time of forming the first film is 100 ccm, the flow rate of the gas containing oxygen atoms is 0 ccm, the atmospheric pressure is 0.3 Pa, the partial pressure of the gas containing oxygen atoms in the atmosphere is 0 Pa, the power is 9 kW, and the bias. A watch component (watch case) was manufactured in the same manner as in Example 5 except that the voltage was −120 V and the substrate temperature was 200 ° C.

(Comparative Example 8)
The Ar gas flow rate at the time of forming the first film is 100 ccm, the flow rate of the gas containing oxygen atoms (O ₂ gas) is 50 c cm, the atmospheric pressure is 0.4 Pa, and the gas containing oxygen atoms (O ₂ gas) in the atmosphere. Oxygen gas, which is an oxidizing gas heated to 200 ° C., with respect to the first coating formed by sputtering, with a partial pressure of 0.15 Pa, a power of 1 kW, a bias voltage of -70 V, and a substrate temperature of 150 ° C. A watch part (watch case) was manufactured in the same manner as in Example 1 except that it was exposed to (pressure: 10 Pa) for 1 minute.

(Comparative Example 9)
The Ar gas flow rate at the time of forming the first film is 100 ccm, the flow rate of the gas containing oxygen atoms (O ₂ gas) is 50 c cm, the atmospheric pressure is 0.4 Pa, and the gas containing oxygen atoms (O ₂ gas) in the atmosphere. Oxygen gas, which is an oxidizing gas heated to 200 ° C., with respect to the first coating formed by sputtering, with a partial pressure of 0.15 Pa, a power of 1 kW, a bias voltage of -70 V, and a substrate temperature of 150 ° C. A watch component (watch case) was manufactured in the same manner as in Example 5 except that it was exposed to (pressure: 10 Pa) for 1 minute.

Table 1 summarizes the configurations of the timepiece parts of each example and each comparative example. In Comparative Example 1, the conditions of the film made of Pt are shown in the column of the first film. Further, the content of the components other than those shown in Table 1 in the first coating film (the sum of the contents of the plurality of components) was 0.1% by mass or less in each of the Examples and the Comparative Examples. there were. In addition, the content of the components shown in the table for each part constituting the timepiece component was 99.9% by mass or more.

[2] Evaluation [2-1] Visual evaluation of appearance Each watch component manufactured in each of the above Examples and Comparative Examples was visually observed and evaluated according to the following criteria.

A: It has an extremely excellent appearance with a high-class feeling of calm impression without being too bright while having an appropriate luster.
B: While having an appropriate luster, it exhibits a very excellent appearance with a high-class feeling of a calm impression without being too bright.
C: While having an appropriate luster, it exhibits a high-class appearance with a calm impression without being too bright.
D: The appearance is slightly inferior due to insufficient glossiness or too high brightness.
E: The glossiness is low, or the brightness is extremely high, and the appearance is inferior.

[2-2] Appearance evaluation by spectrophotometer [2-2-1] Evaluation of L ^* For the clock parts manufactured in each of the above Examples and Comparative Examples, a spectrophotometer (manufactured by Konica Minolta Co., Ltd., Measurements were performed using CM-5) and evaluated according to the following criteria.

A: In the chromaticity diagram of the ^{L *} a ^* b ^* display specified in JIS Z 8729 ^{, L *} is in the range of 74.0 or more and 78.2 or less.
B: In the chromaticity diagram of the ^{L *} a ^* b ^* display specified by JIS Z 8729 ^{, L *} is within the range of 72.0 or more and 78.3 or less (however, the range of A is excluded).
C: In the chromaticity diagram of ^{L *} a ^* b ^* indication specified by JIS Z 8729 ^{, L *} is within the range of 70.0 or more and 78.4 or less (however, the range of A and B is excluded).
D: In the chromaticity diagram of the ^{L *} a ^* b ^* display defined by JIS Z 8729 ^{, L *} is within the range of 68.0 or more and 80 or less (however, the range of A, B and C is excluded).
E: In the chromaticity diagram of the ^{L *} a ^* b ^* display defined by JIS Z 8729 ^{, L *} is a value outside the range of 68.0 or more and 80 or less.

As the light source of the spectrocolorimeter, a D65 specified by JIS Z 8720 was used, and the measurement was performed at a viewing angle of 2 °.

[2-2-2] ^{Evaluation of a *} and b ^* Measurement using a spectrocolorimeter (CM-5, manufactured by Konica Minolta) was performed on the clock parts manufactured in each of the above Examples and Comparative Examples. The results were evaluated according to the following criteria.

A: In the chromaticity diagram of ^{L *} a ^* b ^* display specified in JIS Z 8729 ^{, a *} is -1.0 or more and 2.0 or less and b ^* is 1.0 or more and 8.0 or less. Inside.
B: In the chromaticity diagram of ^{L *} a ^* b ^* display specified by JIS Z 8729 ^{, a *} is -1.5 or more and 2.5 or less and b ^* is 0.0 or more and 9.0 or less. (However, the range of A is excluded).
C: In the chromaticity diagram of ^{L *} a ^* b ^* display specified by JIS Z 8729 ^{, a *} is -2.0 or more and 3.0 or less and b ^* is -1.0 or more and 10.0 or less. Within range (but excluding ranges A and B).
D: In the chromaticity diagram of ^{L *} a ^* b ^* display specified by JIS Z 8729 ^{, a *} is -3.0 or more and 4.0 or less and b ^* is -2.0 or more and 11.0 or less. Within range (excluding ranges A, B and C).
E: In the chromaticity diagram of ^{L *} a ^* b ^* display specified by JIS Z 8729 ^{, a *} is -3.0 or more and 4.0 or less and b ^* is -2.0 or more and 11.0 or less. It is out of range.

As the light source of the spectrocolorimeter, a D65 specified by JIS Z 8720 was used, and the measurement was performed at a viewing angle of 2 °.

[2-3] Corrosion resistance evaluation Artificial sweat was placed in a desiccator and left at 45 ° C. for 12 hours. Then, each watch component was put in a desiccator and left at 45 ° C. At this time, each watch part was arranged so as not to be immersed in artificial sweat. After 120 hours, each watch component is taken out of the desiccator, the color tone of the watch component is measured using a spectrophotometer (CM-5 manufactured by Konica Minolta), and the color difference before and after the aeration test is performed. It was calculated and evaluated according to the following criteria.

A: The color difference ΔE is less than 3.
B: The color difference ΔE is 3 or more and less than 4.
C: The color difference ΔE is 4 or more and less than 5.
D: The color difference ΔE is 5 or more and less than 6.
E: The color difference ΔE is 6 or more.

As the light source of the spectrocolorimeter, a D65 specified by JIS Z 8720 was used, and the measurement was performed at a viewing angle of 2 °.

[2-4] Scratch resistance / abrasion resistance evaluation The scratch resistance / abrasion resistance is evaluated by conducting the following tests on each watch part manufactured in each of the above Examples and Comparative Examples. bottom.

Using a Suga test machine (NUS-ISO-1 manufactured by Suga Test Instruments Co., Ltd.), the surface of each watch component is worn by a total of 300 DS (double stroke) under the condition of load: 200 gf, and then each watch component. The appearance of the above was visually observed, and these appearances were evaluated according to the following criteria. The above test was carried out using a wrapping film (aluminum oxide, particle size: 30 μm) manufactured by Sumitomo 3M Ltd.

A: No scratches are found on the surface.
B: Almost no scratches are observed on the surface.
C: Slight scratches are observed on the surface.
D: Scratches are noticeably observed on the surface. Alternatively, peeling of the coating film (first coating film, coat layer, etc.) is observed.

[2-5] Evaluation of dent resistance The dent resistance was evaluated by conducting the following tests on each watch component manufactured in each of the above Examples and Comparative Examples.

A stainless steel ball (diameter 1 cm) is dropped from a height of 100 cm toward a specific part of each watch part, and the size of the dent on the surface of the watch part (diameter of the dent mark) is measured. The results were evaluated according to the following criteria.

A: The diameter of the dent mark is less than 0.5 mm, or the dent mark is not required.
B: The diameter of the dent mark is 0.5 mm or more and less than 1.0 mm.
C: The diameter of the dent mark is 1.0 mm or more and less than 1.5 mm.
D: The diameter of the dent mark is 1.5 mm or more.
These results are summarized in Table 2.

As is clear from Table 2, excellent results were obtained in the present invention. Moreover, when a patch test based on the ICDRG standard by the International Dermatology Society was conducted, no allergic reaction was confirmed in the watch component of the present invention. In addition, when an elution test with artificial sweat based on JCWA-T003 and EN1811 was performed, elution of components in which an allergic reaction was a problem was not confirmed. On the other hand, in the comparative example, satisfactory results were not obtained. Further, the watch parts of Examples 9 and 10 having a coat layer made of a material containing a fluorine-containing organosilicon compound were particularly excellent in antifouling property, touch feeling and the like.

A watch component (band) was manufactured in the same manner as in each of the above Examples and Comparative Examples except that the shape of the base material was changed to a band, and the same evaluation as described above was performed. As a result, the same result as described above was performed. was gotten.

Further, a timepiece component was manufactured in the same manner as in Examples 5 to 10 except that the second coating film was formed of TiCN instead of TiC, and the same evaluation as described above was performed. , The same result as described above was obtained.

In addition, a wristwatch as shown in FIG. 6 was assembled using the clock parts manufactured in each of the above Examples and Comparative Examples. When the same evaluation as above was performed on these watches, the same results as above were obtained.

10 ... Clock parts, 1 ... Base material, 2 ... First coating, 21 ... First surface, 22 ... Second surface (surface), 3 ... Underlayer (first underlayer), 4 ... First 2 coating, 42 ... surface, 5 ... base layer (second base layer), 6 ... coat layer, W10 ... watch (watch), W22 ... body (case), W23 ... back cover, W24 ... bezel (edge) , W25 ... Glass plate (windshield), W26 ... Winding pipe, W27 ... Crown, W271 ... Shaft, W272 ... Groove, W28 ... Plastic packing, W29 ... Plastic packing, W30 ... Rubber packing (crown packing), W40 ... Rubber packing (back cover packing), W50 ... Joint (seal)

Claims (12)

With the base material
It is provided with a first coating material composed of a material containing Co as a main component, Cr in a content of 26% by mass or more and 30% by mass or less, and Mo in a content of 5% by mass or more and 7% by mass or less.
A film having a thickness of 1.0 μm having a composition of Co: 62.8% by mass, Cr: 28.2% by mass, Mo: 6.0% by mass, C: 1.5% by mass, Ar: 1.5% by mass. The clock component, wherein the average signal intensity of oxygen in the first coating film measured by SIMS is 160 count / sec or more and 300 count / sec or less. Surface where the first coating is visually recognized, to claim 1 ^{L *} is 70.0 or more 78.4 or less in the chromaticity diagram of ^{the L} * ^a * ^{b *} as defined in JIS Z 8729 Described watch parts. The watch component according to claim 1 or 2, wherein the base material is made of a material containing at least one of stainless steel and Ti. The timepiece component according to any one of claims 1 to 3, wherein at least one base layer made of a material containing Ti is provided between the base material and the first coating film. The timepiece according to any one of claims 1 to 4, wherein a second coating made of a material containing at least one of TiC and TiCN is provided between the base material and the first coating. Parts for. A second coating made of a material containing at least one of TiC and TiCN is provided between the base material and the first coating.
The timepiece component according to claim 4, wherein the base layer is provided on both side surfaces of the second coating film. The timepiece component according to claim 5 or 6, wherein the second coating film has a portion whose composition changes obliquely in the thickness direction. The timepiece according to any one of claims 5 to 7, wherein the second coating film has a region in which the sum of the contents of C and N decreases toward the surface side of the second coating film. parts. The timepiece component according to claim 8, wherein the second coating has the regions on both sides of the second coating. The timepiece component according to any one of claims 5 to 9, wherein the thickness of the second coating film is 0.05 μm or more and 4.0 μm or less. The watch component according to any one of claims 1 to 10 , wherein the watch component is a case or a band. A timepiece comprising the timepiece component according to any one of claims 1 to 11.

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