Patent Application
20180217560
The present invention relates to a timepiece component and a timepiece.
A timepiece is required to have a function as a practical item, and is also required to have an aesthetic property (aesthetic appearance) as an ornamental item.
Therefore, a noble metal material having an excellent texture is used in a timepiece component such as a dial or a case (see, for example, JP-A-2009-69078 (Patent Document 1)).
However, a noble metal material is generally expensive, and also in relation to reserves or the like, there has been a demand to avoid excess use of a noble metal material.
An advantage of some aspects of the invention is to provide a timepiece component having an excellent appearance even without using a noble metal as a main material, and also to provide a timepiece including the timepiece component.
The advantage can be achieved by the following configurations.
A timepiece component according to an aspect of the invention includes a metallic luster portion which is constituted by a first material containing a nitride or a carbide of Ti, a nitride or a carbide of Cr, or a metal material, and exhibits a metallic luster, a toning film which covers at least a part of the metallic luster portion, is constituted by a stacked body including a plurality of layers constituted by a material containing a metal oxide, and has a function of adjusting a color tone, and a functional film which is provided on a surface on the opposite side to a surface facing the metallic luster portion of the toning film, and imparts a specific function.
According to this configuration, a timepiece component having an excellent appearance can be provided even without using a noble metal as a main material.
In the timepiece component according to the aspect of the invention, it is preferred that the functional film has a function of improving an antifouling property.
According to this configuration, a decrease in the aesthetic property due to adhesion of dirt can be more effectively prevented. Further, even if dirt adheres thereto, the dirt can be more easily removed. Therefore, an excellent aesthetic property can be more favorably maintained in various environments for a longer period of time. Further, the timepiece component also has an excellent touch.
In the timepiece component according to the aspect of the invention, it is preferred that the functional film is constituted by a material containing a fluorine-containing organosilicon compound.
According to this configuration, a decrease in the aesthetic property due to adhesion of dirt can be still more effectively prevented. Further, even if dirt adheres thereto, the dirt can be still more easily removed. Therefore, an excellent aesthetic property can be still more favorably maintained in various environments for a still longer period of time. Further, when the functional film is constituted by a material containing a fluorine-containing organosilicon compound, not only an antifouling property and a touch, but also a waterproof property, scratch resistance, and the like are improved. Further, adhesion of the functional film to the toning film or the like can be further enhanced, and thus, the durability of the timepiece component or a timepiece including the timepiece component can be further enhanced. Further, the fluorine-containing organosilicon compound little affects the appearance of the timepiece component as a whole, and therefore, the aesthetic property of the timepiece component can be more reliably enhanced.
In the timepiece component according to the aspect of the invention, it is preferred that the functional film has a function of improving an antibacterial property.
A timepiece (particularly, a portable timepiece such as a wristwatch or a pocket watch) is often used in contact with the skin, and is often used outside where the timepiece frequently comes into contact with various types of bacteria. Therefore, the timepiece component preferably has a high antibacterial property, and when the functional film has a function of improving an antibacterial property, such a demand can be favorably satisfied.
In the timepiece component according to the aspect of the invention, it is preferred that the functional film has a function of improving a hardness.
According to this configuration, scratch resistance (less susceptible to scratches), dent resistance (less susceptible to dents), etc. can be enhanced, and thus, the durability of the timepiece component or a timepiece as a whole including the timepiece component can be further enhanced.
In the timepiece component according to the aspect of the invention, it is preferred that the functional film is constituted by a material containing one of silicon nitride and aluminum nitride.
According to this configuration, while suppressing the production cost of the timepiece component, the aesthetic property of the timepiece component is further enhanced, and also the scratch resistance, dent resistance, etc. of the timepiece component can be further enhanced, and thus, the durability of the timepiece component or a timepiece as a whole including the timepiece component can be still further enhanced. Further, the productivity of the timepiece component can be further enhanced. In addition, silicon nitride and aluminum nitride have a transmission property as well as having excellent characteristics as described above, and therefore little affect the appearance of an underlying layer, and thus can more reliably enhance the aesthetic property of the timepiece component.
In the timepiece component according to the aspect of the invention, it is preferred that the metallic luster portion is a substrate constituted by the first material.
According to this configuration, the structure of the timepiece component can be further simplified, and the productivity of the timepiece component can be further enhanced.
In the timepiece component according to the aspect of the invention, it is preferred that the metallic luster portion is a coating film provided on a substrate constituted by a material containing substantially no nitride or carbide of Ti, nitride or carbide of Cr, or metal material.
According to this configuration, the range of choices for the constituent material or the like of the substrate is expanded, and therefore, the range of choices for the molding method for the timepiece component, the range of choices for the placement site of the timepiece component in a timepiece, etc. can be further expanded. Further, the amount of a metal material used in the timepiece component as a whole can be further decreased.
In the timepiece component according to the aspect of the invention, it is preferred that the toning film includes a layer constituted by a material containing at least one member selected from the group consisting of Ta2O5, SiO2, TiO2, Al2O3, ZrO2, Nb2O5, and HfO2.
According to this configuration, the aesthetic property of the timepiece component can be further enhanced, and also the range of the color tone which can be expressed by the timepiece component as a whole can be further expanded. Further, these compounds are materials having particularly high chemical stability among various types of metal oxides, and therefore can further enhance the stability of the appearance and the durability of the timepiece component as a whole.
In the timepiece component according to the aspect of the invention, it is preferred that the toning film has a thickness of 100 nm or more and 2000 nm or less.
According to this configuration, the aesthetic property of the timepiece component can be further enhanced, and the range of the color which can be expressed (color reproducible range) can be further expanded, and also unintended peel-off or the like of the toning film can be more effectively prevented, and therefore, the durability and reliability of the timepiece component can be further enhanced, and also the productivity of the timepiece component can be further enhanced.
In the timepiece component according to the aspect of the invention, it is preferred that each layer constituting the toning film has a thickness of 10 nm or more and 300 nm or less.
According to this configuration, the aesthetic property of the timepiece component can be further enhanced, and the color reproducible range can be further expanded, and also unintended peel-off or the like of the toning film can be more effectively prevented, and therefore, the durability and reliability of the timepiece component can be further enhanced.
In the timepiece component according to the aspect of the invention, it is preferred that the metallic luster portion is constituted by a material containing Ti, Cr, or Al.
According to this configuration, the timepiece component as a whole can favorably exhibit a bluish luxurious metallic luster.
In the timepiece component according to the aspect of the invention, it is preferred that the timepiece component is a crystal, a case, or a band.
These components (timepiece components) greatly affect the appearance of a timepiece as a whole, and therefore, by applying the invention to these components, the aesthetic property of the timepiece as a whole can be further enhanced. Further, these components (timepiece components) are components which are generally exposed to the outside in the timepiece. Such components are particularly strongly required to have a function to be exhibited by including the functional film as described above. Therefore, by applying the invention to these components, the effect of the invention is more remarkably exhibited.
A timepiece according to an aspect of the invention includes the timepiece component according to the aspect of the invention.
According to this configuration, a timepiece having an excellent appearance can be provided even without using a noble metal as a main material.
The invention will be described with reference to the accompanying drawings, wherein like numbers reference like elements.
Hereinafter, preferred embodiments will be described in detail with reference to the accompanying drawings.
First, a timepiece component according to the invention will be described.
A timepiece component 10 includes a metallic luster portion 1 which is constituted by a first material containing a nitride or a carbide of Ti, a nitride or a carbide of Cr, or a metal material, and exhibits a metallic luster, a toning film 5 which covers at least a part of the metallic luster portion 1, is constituted by a stacked body including a plurality of layers (metal oxide layers 51) constituted by a material containing a metal oxide, and has a function of adjusting a color tone of the timepiece component 10 as a whole, and a functional film 6 which is provided on a surface on the opposite side to a surface facing the metallic luster portion 1 of the toning film 5, and imparts a specific function.
The “nitride” as used herein refers to a metal compound containing nitrogen (N) and includes a carbonitride and the like. Further, the “carbide” as used herein refers to a metal compound containing carbon (C) and includes a carbonitride and the like.
The metallic luster portion 1 is a portion which exhibits a metallic luster.
The toning film 5 has a function of adjusting a color tone of the timepiece component 10 as a whole while making use of the metallic luster of the metallic luster portion 1.
The view point of an observer is on the upper side in
According to such a configuration, the timepiece component 10 which has an excellent appearance (an appearance exhibiting a metallic luster), particularly a luxurious appearance can be provided even without using a noble metal as a main material. Further, even if a noble metal is used, the amount of the noble metal to be used can be suppressed. More specifically, for example, a luxurious appearance as being exhibited by a noble metal material can be obtained even if the timepiece component contains substantially no noble metal. Further, a noble metal generally has a characteristic that it is susceptible to scratches or the like, however, according to the configuration as described above, the scratch resistance, etc. of the timepiece component 10 as a whole can be enhanced. In particular, in the timepiece component 10, both excellent appearance and excellent scratch resistance can be achieved. Further, various color tones such as a metallic look with a bluish luster and a metallic look with a reddish luster, which are hardly expressed only by a metal material, can be expressed, and an appearance with a color tone which cannot be obtained when only a metal material (particularly, a noble metal material) is merely used can be obtained. That is, the range of the color which can be expressed (color reproducible range) can be further expanded. Further, even if the metallic luster portion 1 is constituted by a metal material (for example, a metal material or the like, which has relatively low chemical stability, and with which a reaction such as oxidation easily proceeds), by covering the metallic luster portion 1 with the toning film 5 constituted by an oxide having excellent chemical stability, the stability of the appearance and the durability of the timepiece component 10 as a whole are improved.
Further, by including the functional film 6, a specific function can be imparted to the timepiece component 10. According to this, for example, a function such as an antifouling property, an antibacterial property, a hardness, scratch resistance, or dent resistance of the timepiece component 10 as a whole or a timepiece as a whole to which the timepiece component 10 is applied can be improved.
In particular, in the timepiece component 10 according to this embodiment, the metallic luster portion 1 is a substrate 2 constituted by the first material. In other words, the timepiece component 10 according to this embodiment includes the substrate 2 which functions as the metallic luster portion 1 and the toning film 5.
According to this, the structure of the timepiece component 10 can be further simplified, and the productivity of the timepiece component 10 can be further enhanced.
In this embodiment, the substrate 2 (metallic luster portion 1) is constituted by a first material containing a nitride or a carbide of Ti, a nitride or a carbide of Cr, or a metal material.
The metal material constituting the metallic luster portion 1 is preferably a metal which is less noble than a noble metal, and includes, for example, Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, In, Sn, Hf, Ta, W, Bi, and Mg, and alloys containing at least one member thereof. It should be noted that this does not preclude the inclusion of a small amount of a noble metal.
In particular, when the metallic luster portion 1 is constituted by a material containing Ti, Cr, or Al, the timepiece component 10 as a whole can favorably exhibit a bluish luxurious metallic luster.
Further, when the metallic luster portion 1 is constituted by a nitride of Ti or Cr, the timepiece component 10 as a whole can favorably exhibit a luxurious gold appearance (an appearance similar to Au as a simple substance).
Further, when the metallic luster portion 1 is constituted by a carbide of Ti, the timepiece component 10 as a whole can favorably exhibit a luxurious blackish appearance. In particular, the timepiece component 10 as a whole can exhibit a blackish red or blackish blue appearance or the like which is particularly difficult to express in the related art.
When the metallic luster portion 1 is constituted by a material containing a carbonitride of Ti, for example, a color tone similar to pink gold can be favorably expressed.
It is preferred that the metallic luster portion 1 has a sufficiently low content of a noble metal element (Au, Ag, Pt, Pd, Rh, Ir, Ru, or Os), and the content of a noble metal element (when a plurality of types of noble metal elements are contained, the sum of the contents of these elements) in the metallic luster portion 1 is preferably 1.0 mass % or less, more preferably 0.5 mass % or less, further more preferably 0.1 mass % or less.
According to this, the effect of obtaining an excellent appearance of the invention is more remarkably exhibited even without using a noble metal as a main material.
The metallic luster portion 1 may contain a component other than the nitride and the carbide of Ti, the nitride and the carbide of Cr, and the metal material as long as it has a metallic luster. However, the content of the component other than the above-mentioned materials (the nitride and the carbide of Ti, the nitride and the carbide of Cr, and the metal material) in the metallic luster portion 1 is preferably 5 mass % or less, more preferably 1 mass % or less.
The substrate 2 may have a uniform composition in the respective portions, or may have a portion having a different composition.
The metallic luster portion 1 has a thickness of preferably 30 nm or more, more preferably 40 nm or more, further more preferably 50 nm or more.
According to this, the luster and aesthetic property of the timepiece component 10 as a whole can be further enhanced.
The shape and size of the substrate 2 are not particularly limited, and are generally determined based on the shape and size of the timepiece component 10. Further, in the substrate 2, an engraved pattern of letters, numbers, symbols, a design, or the like may be provided.
The substrate 2 may be subjected to, for example, surface processing such as mirror finish, streaked finish, or sand blast finish on the surface.
According to this, it is possible to impart variations to the lustrous texture of the surface of the timepiece component 10, and thus, the aesthetic property of the timepiece component 10 can be further improved. The mirror finish can be performed using, for example, a known polishing method, and for example, buff (fabric) polishing, barrel polishing, another mechanical polishing, or the like can be adopted.
In the timepiece component 10 produced using the substrate 2 subjected to such surface processing, glare or the like is suppressed as compared with those obtained by directly performing surface processing for the respective types of films to be described in detail later, and therefore, the aesthetic property is particularly enhanced. Further, the respective types of films to be described in detail later are generally relatively thin, and when surface processing is directly performed for the films, a defect such as chipping or peeling off is likely to occur in the films when performing the surface processing, and the production yield of the timepiece component 10 is significantly decreased in some cases. However, by performing surface processing for the substrate 2, the occurrence of such a problem can be effectively prevented, and also the film thickness is relatively thin, and therefore, deterioration of the aesthetic property due to the surface processing does not occur. Further, the surface processing for the substrate 2 can be easily performed under mild conditions as compared with the surface processing for the respective types of films to be described in detail later.
The toning film 5 is constituted by a multilayer film of a metal oxide. In other words, the toning film 5 is a stacked body including a plurality of metal oxide layers 51.
The toning film 5 (metal oxide layer 51) may be any as long as it is constituted by an oxide of a metal material, but preferably includes layers (metal oxide layers 51) constituted by a material containing at least one member selected from the group consisting of Ta2O5, SiO2, TiO2, Al2O3, ZrO2, Nb2O5, and HfO2, more preferably includes layers constituted by mutually different materials selected from the group as the plurality of metal oxide layers 51.
According to this, the aesthetic property of the timepiece component 10 can be further enhanced, and also the range of the color tone which can be expressed by the timepiece component 10 as a whole can be further expanded. Further, these compounds are materials having particularly high chemical stability among various types of metal oxides, and therefore can further enhance the stability of the appearance and the durability of the timepiece component 10 as a whole.
Above all, Al2O3 and HfO2 are materials having a particularly high hardness, and therefore can provide not only chemical durability, but also excellent durability to mechanical force.
The toning film 5 (metal oxide layer 51) may be any as long as it is mainly constituted by a metal oxide, and may contain a component other than the metal oxide. However, the content of the component other than the metal oxide in the toning film 5 (metal oxide layer 51) is preferably 5 mass % or less, more preferably 1 mass % or less.
Further, the toning film 5 may have a layer which is not shown in the drawing other than the metal oxide layer 51, for example, as an intermediate layer provided between the metal oxide layers 51.
The thickness of the toning film 5 is preferably 100 nm or more and 2000 nm or less, more preferably 150 nm or more and 1000 nm or less, further more preferably 200 nm or more and 800 nm or less.
According to this, the aesthetic property of the timepiece component 10 can be further enhanced, and the color reproducible range can be further expanded, and also unintended peel-off or the like of the toning film 5 can be more effectively prevented, and therefore, the durability and reliability of the timepiece component 10 can be further enhanced, and also the productivity of the timepiece component 10 can be further enhanced.
The thickness of each layer (each metal oxide layer 51) constituting the toning film 5 is preferably 10 nm or more and 300 nm or less, more preferably 15 nm or more and 200 nm or less, further more preferably 25 nm or more and 150 nm or less.
According to this, the aesthetic property of the timepiece component 10 can be further enhanced, and the color reproducible range can be further expanded, and also unintended peel-off or the like of the toning film 5 can be more effectively prevented, and therefore, the durability and reliability of the timepiece component 10 can be further enhanced.
The number of metal oxide layers 51 constituting the toning film 5 is preferably 2 or more, more preferably 3 or more.
According to this, the aesthetic property of the timepiece component 10 can be further enhanced, and the color reproducible range can be further expanded, and also unintended peel-off or the like of the toning film 5 can be more effectively prevented, and therefore, the durability and reliability of the timepiece component 10 can be further enhanced.
The forming method for the toning film 5 is not particularly limited, and includes, for example, a coating method such as spin coating, dipping, coating with a brush, spray coating, electrostatic coating, and electrodeposition coating, a wet plating method such as electrolytic plating, immersion plating, and electroless plating, a chemical vapor deposition (CVD) method such as thermal CVD, plasma CVD, and laser CVD, a dry plating method (gas phase deposition method) such as vacuum vapor deposition, sputtering, ion plating, and laser ablation, and thermal spraying, but is preferably a dry plating method (gas phase deposition method).
By applying a dry plating method (gas phase deposition method) as the forming method for the toning film 5, the toning film 5 which has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2 or the like can be reliably formed. As a result, the aesthetic appearance and durability of the timepiece component 10 can be particularly enhanced.
Further, by applying a dry plating method (gas phase deposition method) as the forming method for the toning film 5, even if the respective metal oxide layers 51 constituting the toning film 5 to be formed are relatively thin, the variation in the film thickness can be sufficiently reduced. Therefore, this is also advantageous to the improvement of the reliability of the timepiece component 10.
Further, by applying a dry plating method (gas phase deposition method) as the forming method for the toning film 5, the content of oxygen in the respective portions (respective metal oxide layers 51) in the toning film 5 can be more reliably controlled.
Among the dry plating methods (gas phase deposition methods) as described above, ion plating is particularly preferred.
By applying ion plating as the forming method for the toning film 5, the effect as described above becomes more remarkable. That is, by applying ion plating as the forming method for the toning film 5, the toning film 5 which has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2 or the like can be more reliably formed. As a result, the aesthetic appearance and durability of the timepiece component 10 to be obtained finally can be further enhanced.
Further, by applying ion plating as the forming method for the toning film 5, even if the respective metal oxide layers 51 constituting the toning film 5 to be formed are relatively thin, the variation in the film thickness can be particularly reduced.
Further, by applying ion plating as the forming method for the toning film 5, the content of oxygen in the respective portions (respective metal oxide layers 51) in the toning film 5 can be more reliably controlled.
Further, when the toning film 5 is formed by a dry plating method, for example, by setting a plurality of targets, the respective metal oxide layers 51 constituting the toning film 5 can be formed successively in the same device without taking out the substrate 2 from the device.
According to this, the adhesion between the respective layers constituting the toning film 5 can be particularly enhanced, and also the productivity of the timepiece component 10 is improved.
The functional film 6 which imparts a specific function is provided on a surface on the opposite side to a surface facing the metallic luster portion 1 of the toning film 5.
For example, the functional film 6 is preferably a film (antifouling film) having a function of improving an antifouling property.
According to this, a decrease in the aesthetic property due to adhesion of dirt can be more effectively prevented. Further, even if dirt adheres thereto, the dirt can be more easily removed. Therefore, an excellent aesthetic property can be more favorably maintained in various environments for a longer period of time. Further, the timepiece component 10 also has an excellent touch.
Examples of the functional film 6 having an antifouling property include films constituted by a material containing a fluorine-based compound, however, above all, a film constituted by a material containing a fluorine-containing organosilicon compound is preferred.
According to this, a decrease in the aesthetic property due to adhesion of dirt can be still more effectively prevented. Further, even if dirt adheres thereto, the dirt can be still more easily removed. Therefore, an excellent aesthetic property can be still more favorably maintained in various environments for a still longer period of time. Further, when the functional film 6 is constituted by a material containing a fluorine-containing organosilicon compound, not only an antifouling property and a touch, but also a waterproof property, scratch resistance, and the like are improved. Further, adhesion of the functional film 6 to the toning film 5 or the like can be further enhanced, and thus, the durability of the timepiece component 10 or a timepiece including the timepiece component 10 can be further enhanced. Further, the fluorine-containing organosilicon compound little affects the appearance of the timepiece component 10 as a whole, and therefore, the aesthetic property of the timepiece component 10 can be more reliably enhanced.
Specific examples of the fluorine-containing organosilicon compound include CF3(CF2)2C2H4Si(OCH3)3, CF3(CF2)4C2H4Si(OCH3)3, CF3(CF2)6C2H4Si(OCH3)3, CF3(CF2)8C2H4Si(OCH3)3, CF3(CF2)10C2H4Si(OCH3)3, CF3(CF2)12C2H4Si(OCH3)3, CF3(CF2)14C2H4Si(OCH3)3, CF3(CF2)16C2H4Si(OCH3)3, CF3(CF2)18C2H4Si(OCH3)3, CF3(CF2)6C2H4Si(OC2H5)3, CF3(CF2)8C2H4Si(OC2H5)3, CF3(CF2)6C2H4SiCl3, CF3(CF2)8C2H4SiCl3, CF3(CF2)6C3H6Si(OCH3)3, CF3(CF2)8C3H6Si(OCH3)3, CF3(CF2)6C3H6Si(OC2H5)3, CF3(CF2)8C3H6Si(OC2H5)3, CF3(CF2)6C3H6SiCl3, CF3(CF2)8C3H6SiCl3, CF3(CF2)6C4H8Si(OCH3)3, CF3(CF2)8C4H8Si(OCH3)3, CF3(CF2)6C4H8Si(OC2H5)3, CF3(CF2)8C4H8Si(OC2H5)3, CF3(CF2)6C2H4Si(CH3)(OCH3)2, CF3(CF2)8C2H4Si(CH3)(OCH3)2, CF3(CF2)6C2H4Si(CH3)Cl2, CF3(CF2)8C2H4Si(CH3)Cl2, CF3(CF2)6C2H4Si(C2H5)(OC2H5)2, and CF3(CF2)8C2H4Si(C2H5)(OC2H5)2.
Further, as the fluorine-containing organosilicon compound, a fluorine-containing organosilicon compound containing an amino group can also be preferably used.
Examples of the fluorine-containing organosilicon compound containing an amino group include C9F19CONH(CH2)3Si(OC2H5)3, C9F19CONH(CH2)3SiCl3, C9F19CONH(CH2)3Si(CH3)Cl2, C9F19CONH(CH2)NH(CH2)Si(OC2H5)3, C9F19CONH(CH2)5CONH(CH2)Si(OC2H5)3, C8F17SO2NH(CH2)5CONH(CH2)Si(OC2H5)3, C3F7O(CF(CF3)CF2O)2—CF(CF3)—CONH(CH2)Si(OC2H5)3, and C3F7O(CF(CF3)CF2O)m′—CF(CF3)—CONH(CH2)Si(OCH3)3 [wherein m′ is an integer of 1 or more].
Further, as the fluorine-containing organosilicon compound, for example, Rf′(CH2)2SiCl3, Rf′(CH2)2Si(CH3)Cl2, (Rf′CH2CH2)2SiCl2, Rf′(CH2)2Si(OCH3)3, Rf′CONH(CH2)3Si(OC2H5)3, Rf′CONH(CH2)2NH(CH2)3Si(OC2H5)3, Rf′SO2N(CH3)(CH2)2CONH(CH2)3Si(OC2H5)3, Rf′(CH2)2OCO(CH2)2S(CH2)3Si(OCH3)3, Rf′(CH2)2OCONH(CH2)2Si(OC2H5)3, Rf′COO—Cy(OH)—(CH2)2Si(OCH3)3, Rf′(CH2)2NH(CH2)2Si(OCH3)3, Rf′(CH2)2NH(CH2)2NH(CH2)2Si(OCH2CH2OCH3)3, or the like may be used. In the above respective formulae, Cy is a cyclohexane residue, and Rf′ is a polyfluoroalkyl group having 4 or more and 16 or less carbon atoms.
As the fluorine-containing organosilicon compound constituting the functional film 6, particularly, a compound represented by the following formula (1) or the following formula (2) is preferred.
In the formula (1), Rf1 represents a perfluoroalkyl group; X represents bromine, iodine, or hydrogen; Y represents hydrogen or a lower alkyl group, and Z represents fluorine or a trifluoromethyl group; R1 represents a hydrolyzable group, and R2 represents hydrogen or an inert monovalent hydrocarbon group; a, b, c, d, and e are each 0 or an integer of 1 or more, and a+b+c+d+e is at least 1 or more, and the existing order of the repeating units in parentheses represented by a, b, c, d, and e is not limited to the order shown in the formula; f is 0, 1, or 2; g is 1, 2, or 3; and h is an integer of 1 or more.
In the formula (2), Rf2 represents a divalent group having a linear perfluoropolyalkylene ether structure which includes a unit represented by the formula: —(CkF2k)O—, and has no branch, wherein k in the formula: —(CkF2k)O— is an integer of 1 or more and 6 or less; R3 is a monovalent hydrocarbon group having 1 to 8 carbon atoms; W denotes a hydrolyzable group or a halogen atom; p is 0, 1, or 2; n is an integer of 1 or more and 5 or less; and m and r are each 2 or 3.
Further, the functional film 6 may be a film (antibacterial film) having a function of improving an antibacterial property.
A timepiece (particularly, a portable timepiece such as a wristwatch or a pocket watch) is often used in contact with the skin, and is often used outside where the timepiece frequently comes into contact with various types of bacteria. Therefore, the timepiece component 10 preferably has a high antibacterial property, and when the functional film 6 has a function of improving an antibacterial property, such a demand can be favorably satisfied.
Examples of the constituent material of the functional film 6 having a function of improving an antibacterial property include photocatalysts such as TiO2, imidazole derivatives such as 2-(4-thiazolyl)benzimidazole, N-haloalkylthio-based compounds such as dichlofluanid, phenyl ether derivatives such as 10,10′-oxybisphenoxarsine, quaternary ammonium salts such as cetyl dimethyl ethyl ammonium bromide, sulfone derivatives such as 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, amides, triazine derivatives, triazole derivatives, methylol group-containing compounds, active halogen-containing compounds, activated N—S bond-containing compounds, isothiazolone-based compounds, organoiodine-based compounds, benzisothiazolone-based compounds, pyrithione-based compounds, and natural product-derived antibacterial agents such as hinokitiol, chitin, chitosan, a Japanese horseradish extract, and a moso bamboo extract.
According to this, the antibacterial property of the timepiece component 10 can be further enhanced, and also the adhesion of the functional film 6 to the toning film 5 or the like can be further enhanced, and thus, the durability of the timepiece component 10 or a timepiece including the timepiece component 10 can be further enhanced.
Further, the functional film 6 may be a film (hard film) having a function of improving a hardness.
According to this, scratch resistance (less susceptible to scratches), dent resistance (less susceptible to dents), etc. can be enhanced, and thus, the durability of the timepiece component 10 or a timepiece as a whole including the timepiece component 10 can be further enhanced.
Examples of the constituent material of the functional film 6 having a function of improving a hardness include carbon-based materials such as DLC, diamond, and a carbon nanotube, metal nitrides such as chromium nitride, silicon nitride, and aluminum nitride, metal carbides such as chromium carbide, silicon carbide, aluminum carbide, and titanium carbide, metal fluorides such as chromium fluoride, silicon fluoride, aluminum fluoride, and titanium fluoride, and metal sulfides such as chromium sulfide, silicon sulfide, aluminum sulfide, and titanium sulfide, however, the functional film 6 having a function of improving a hardness is preferably constituted by a material containing one of silicon nitride and aluminum nitride.
According to this, while suppressing the production cost of the timepiece component 10, the aesthetic property of the timepiece component 10 is further enhanced, and also the scratch resistance, dent resistance, etc. of the timepiece component 10 can be further enhanced, and thus, the durability of the timepiece component 10 or a timepiece as a whole including the timepiece component 10 can be still further enhanced. Further, the productivity of the timepiece component 10 can be further enhanced. Further, silicon nitride and aluminum nitride have a transmission property as well as having excellent characteristics as described above, and therefore little affect the appearance of an underlying layer, and thus can more reliably enhance the aesthetic property of the timepiece component 10.
The functional film 6 may have a uniform composition in the respective portions, or may have a portion having a different composition. For example, the functional film 6 may be a stacked body including a plurality of layers, or may be constituted by a gradient material in which the composition changes in a gradient manner in the thickness direction.
The functional film 6 is not limited to those having a function as described above.
The content of the above-mentioned component in the functional film 6 (when a plurality of components are contained, the sum of the contents of these components) is preferably 90 mass % or more, more preferably 95 mass % or more, further more preferably 99 mass % or more.
According to this, the effect as described above is more remarkably exhibited.
The thickness of the functional film 6 is preferably 2 nm or more and 1000 nm or less, more preferably 3 nm or more and 500 nm or less, further more preferably 4 nm or more and 300 nm or less.
According to this, the effect of providing the functional film 6 as described above can be more remarkably exhibited while effectively preventing unintended peel-off or the like of the functional film 6.
The forming method for the functional film 6 is not particularly limited, and includes, for example, a coating method such as spin coating, dipping, coating with a brush, spray coating, electrostatic coating, and electrodeposition coating, a wet plating method such as electrolytic plating, immersion plating, and electroless plating, a chemical vapor deposition (CVD) method such as thermal CVD, plasma CVD, and laser CVD, a dry plating method (gas phase deposition method) such as vacuum vapor deposition, sputtering, ion plating, and laser ablation, and thermal spraying, but is preferably a dry plating method (gas phase deposition method).
By applying a dry plating method (gas phase deposition method) as the forming method for the functional film 6, the functional film 6 which has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the toning film 5 or the like can be reliably formed.
Further, by applying a dry plating method (gas phase deposition method) as the forming method for the functional film 6, even if the functional film 6 to be formed is relatively thin, the variation in the film thickness can be sufficiently reduced.
Further, by applying a dry plating method (gas phase deposition method) as the forming method for the functional film 6, an unintended variation in the composition in the respective portions in the functional film 6 can be more effectively suppressed.
Among the dry plating methods (gas phase deposition methods) as described above, ion plating is particularly preferred.
By applying ion plating as the forming method for the functional film 6, the effect as described above becomes more remarkable. That is, by applying ion plating as the forming method for the functional film 6, the functional film 6 which has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the toning film 5 or the like can be more reliably formed.
Further, by applying ion plating as the forming method for the functional film 6, even if the functional film 6 to be formed is relatively thin, the variation in the film thickness can be particularly reduced.
Further, by applying ion plating as the forming method for the functional film 6, an unintended variation in the composition in the respective portions in the functional film 6 can be more effectively suppressed.
Further, the functional film 6 is preferably formed by the same film forming method as the toning film 5. For example, in a case where the toning film 5 is formed by ion plating, the functional film 6 is preferably also formed by ion plating.
According to this, for example, by changing a target, an atmospheric gas (reaction gas), etc., the toning film 5 and the functional film 6 can be formed successively in the same device without taking out the substrate 2 from the device. According to this, the adhesion between the toning film 5 and the functional film 6 can be particularly enhanced, and also the productivity of the timepiece component 10 is improved.
Next, a timepiece component according to a second embodiment will be described.
In a timepiece component 10 according to this embodiment, a substrate 2 which is constituted by a material containing substantially no nitride or carbide of Ti, nitride or carbide of Cr, or metal material, a coating film 3 which is constituted by a first material and covers the substrate 2, a toning film 5 which covers the coating film 3, and a functional film 6 which covers the toning film 5 are stacked in this order. In other words, in the timepiece component 10 according to this embodiment, a metallic luster portion 1 is the coating film 3 provided on the substrate 2 which is constituted by a material containing substantially no nitride or carbide of Ti, nitride or carbide of Cr, or metal material.
According to this, by providing the coating film 3 serving as the metallic luster portion 1 as a portion different from the substrate 2, the range of choices for the constituent material or the like of the substrate 2 is expanded. For example, a glass, a ceramic, a plastic material, or the like can also be favorably used as the constituent material of the substrate 2, and the range of choices for the molding method for the timepiece component 10, the range of choices for the placement site of the timepiece component 10 in a timepiece, etc. can be further expanded. Further, the amount of a metal material used in the timepiece component 10 as a whole can be further decreased. Accordingly, this can contribute to, for example, the weight reduction of the timepiece component 10. Further, the radio wave transmission property of the timepiece component 10 can be enhanced, and for example, the timepiece component 10 can be favorably applied to a radio-controlled timepiece or the like. Further, by using a substrate constituted by a material having a light transmission property as the substrate 2 and also making the thickness of the coating film 3 relatively thin, a sufficient light transmission property can be ensured while allowing the timepiece component 10 as a whole to exhibit excellent luster and aesthetic property. As a result, the timepiece component 10 can be favorably applied to, for example, a component required to have a light transmission property such as a crystal or a see-through back cover.
In this embodiment, examples of the constituent material of the substrate 2 include glass materials such as sapphire glass, soda-lime glass, crystalline glass, quartz glass, lead glass, potassium glass, borosilicate glass, and alkali-free glass, ceramic materials such as alumina and titania, and plastic materials such as various types of thermoplastic resins and various types of curable resins.
In this embodiment, the substrate 2 may be any as long as it contains substantially no nitride or carbide of Ti, nitride or carbide of Cr, or metal material, but may contain a nitride or a carbide of Ti, a nitride or a carbide of Cr, or a metal material as, for example, a filler, an inevitable component, or the like if the amount is small. For example, the substrate 2 may contain a nitride and a carbide of Ti, a nitride and a carbide of Cr, and a metal material in such an amount that the sum of the contents of these materials is 5 mass % or less. In such a case, the effect as described above is sufficiently obtained.
In this embodiment, the coating film 3 functions as the metallic luster portion 1.
The constituent material of the coating film 3 is the same as that cited for the substrate 2 (metallic luster portion 1) in the above-mentioned embodiment. That is, in this embodiment, the coating film 3 is constituted by the first material.
The thickness of the coating film 3 is preferably 30 nm or more and 5000 nm or less, more preferably 40 nm or more and 3000 nm or less, further more preferably 50 nm or more and 500 nm or less.
According to this, the luster and aesthetic property of the timepiece component 10 as a whole can be further enhanced, and also unintended peel-off or the like of the coating film 3 can be more effectively prevented, and therefore, the durability of the timepiece component 10 can be further enhanced, and also the productivity of the timepiece component 10 can be further enhanced.
The coating film 3 may have a uniform composition in the respective portions, or may have a portion having a different composition. For example, the coating film 3 may be constituted by a gradient material in which the composition changes in a gradient manner (for example, a gradient material or the like in which the composition changes in a gradient manner in the thickness direction) or the like.
The forming method for the coating film 3 is not particularly limited, and includes, for example, a coating method such as spin coating, dipping, coating with a brush, spray coating, electrostatic coating, and electrodeposition coating, a wet plating method such as electrolytic plating, immersion plating, and electroless plating, a chemical vapor deposition (CVD) method such as thermal CVD, plasma CVD, and laser CVD, a dry plating method (gas phase deposition method) such as vacuum vapor deposition, sputtering, ion plating, and laser ablation, and thermal spraying, but is preferably a dry plating method (gas phase deposition method).
By applying a dry plating method (gas phase deposition method) as the forming method for the coating film 3, the coating film 3 which has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2 or the like can be reliably formed. As a result, the aesthetic appearance and durability of the timepiece component 10 can be particularly enhanced.
Further, by applying a dry plating method (gas phase deposition method) as the forming method for the coating film 3, even if the coating film 3 to be formed is relatively thin, the variation in the film thickness can be sufficiently reduced. Therefore, this is also advantageous to the improvement of the reliability of the timepiece component 10.
Among the dry plating methods (gas phase deposition methods) as described above, ion plating is particularly preferred.
By applying ion plating as the forming method for the coating film 3, the effect as described above becomes more remarkable. That is, by applying ion plating as the forming method for the coating film 3, the coating film 3 which has a uniform film thickness, is homogeneous, and has particularly excellent adhesion to the substrate 2 or the like can be more reliably formed. As a result, the aesthetic appearance and durability of the timepiece component 10 to be obtained finally can be further enhanced.
Further, by applying ion plating as the forming method for the coating film 3, even if the coating film 3 to be formed is relatively thin, the variation in the film thickness can be particularly reduced.
Next, a timepiece component according to a third embodiment will be described.
In a timepiece component 10 according to this embodiment, a substrate 2 has a light transmission property, and a functional film 6, the substrate 2, a toning film 5, and a coating film 3 (metallic luster portion 1) are stacked in this order.
In this manner, the placement of the respective members constituting the timepiece component 10 may be different from that described above.
Further, as in this embodiment, by stacking the functional film 6, the substrate 2, the toning film 5, and the coating film 3 (metallic luster portion 1) in this order, an observer can be allowed to visually recognize the toning film 5 and the coating film 3 (metallic luster portion 1) through the functional film 6 and the substrate 2, each having a predetermined thickness and a light transmission property, and therefore, a sense of depth can be imparted to the appearance of the timepiece component 10.
The substrate 2 and the functional film 6 may be any as long as these members each have a light transmission property, however, the visible light transmittance (for example, the light transmittance at a wavelength of 550 nm) of each of the substrate 2 and the functional film 6 is preferably 80% or more, more preferably 85% or more, further more preferably 90% or more.
According to this, the effect of placement of the respective members as described above is more remarkably exhibited, and the aesthetic property of the timepiece component 10 can be further enhanced.
Next, a timepiece component according to a fourth embodiment will be described.
In a timepiece component 10 according to this embodiment, a substrate 2 (a first region 11 of a metallic luster portion 1) which is constituted by a first material, a coating film 3 (a second region 12 of the metallic luster portion 1) which is constituted by a first material, a toning film 5 which covers the coating film 3, and a functional film 6 are stacked in this order, and the substrate 2 and the coating film 3 are constituted by mutually different materials. In other words, in this embodiment, the metallic luster portion 1 includes the first region 11 and the second region 12 which is provided in the form of a layer overlapping with the first region 11 on a side closer to the toning film 5 than the first region 11, and the second region 12 is constituted by a material different from that of the first region 11.
According to this, subtle color adjustment can be performed, and the color reproducible range of the timepiece component 10 as a whole can be further expanded, and thus, the aesthetic property of the timepiece component 10 can be further enhanced. In addition, the aesthetic property of the timepiece component 10 can be enhanced while further suppressing the amount of a metal used therein as a whole.
The thickness of the first region 11 is preferably 20 nm or more, more preferably 25 nm or more, further more preferably 30 nm or more.
According to this, the luster and aesthetic property of the timepiece component 10 as a whole can be further enhanced.
The thickness of the second region 12 is preferably 30 nm or less, more preferably 20 nm or less, further more preferably 10 nm or less.
According to this, the aesthetic property of the timepiece component 10 can be further enhanced, and also unintended peel-off or the like of the second region 12 can be more effectively prevented, and therefore, the durability and reliability of the timepiece component 10 can be further enhanced, and also the productivity of the timepiece component 10 can be further enhanced.
The first region 11 and the second region 12 may be any as long as these regions are constituted by the first materials, respectively, and the combination of the materials is not particularly limited, and the first region 11 and the second region 12 may have the same composition or may have different compositions, however, it is preferred that the first region 11 is constituted by TiN, and the second region 12 is constituted by a metal material containing Ti, Cr, Al, or Fe.
According to this, a particularly highly luxurious gold color can be expressed.
Next, a timepiece component according to a fifth embodiment will be described.
In a timepiece component 10 according to this embodiment, a substrate 2 which is constituted by a material other than the first material, a coating film 3 (metallic luster portion 1) which is constituted by the first material, atoning film 5 which covers the coating film 3 (metallic luster portion 1), and a functional film 6 which covers the toning film 5 are stacked in this order, and the metallic luster portion 1 includes a first region 11 and a second region 12 which is provided in the form of a layer overlapping with the first region 11 on a side closer to the toning film 5 than the first region 11, and the second region 12 is constituted by a material different from that of the first region 11. That is, the timepiece component 10 of this embodiment is the same as that of the above-mentioned fourth embodiment except that the substrate 2 does not constitute the metallic luster portion 1, and also the coating film 3 serving as the metallic luster portion 1 includes the first region 11 (first layer) and the second region 12 (second layer).
By providing the first region 11 in the form of a layer, the range of choices for the constituent material or the like of the substrate 2 and the first region 11 is expanded, and for example, even a material which is difficult to cast or the like can be favorably used. Further, the amount of a metal material used in the timepiece component 10 as a whole can be further decreased.
The thickness of the first region 11 is preferably 20 nm or more and 1500 nm or less, more preferably 25 nm or more and 1000 nm or less, further more preferably 30 nm or more and 500 nm or less.
According to this, the luster and aesthetic property of the timepiece component 10 as a whole can be further enhanced, and also unintended peel-off or the like of the first region 11 can be more effectively prevented, and therefore, the durability of the timepiece component 10 can be further enhanced, and also the productivity of the timepiece component 10 can be further enhanced.
Next, a timepiece component according to a sixth embodiment will be described.
In a timepiece component 10 according to this embodiment, a substrate 2 has a light transmission property, and a functional film 6, the substrate 2, a toning film 5, and a coating film 3 (metallic luster portion 1) which includes a second region 12 and a first region 11 are stacked in this order. That is, the timepiece component 10 according to this embodiment is the same as that of the fifth embodiment except that the placement of the constituent members is different. Further, the timepiece component 10 of this embodiment is the same as that of the above-mentioned third embodiment except that the coating film 3 (metallic luster portion 1) is different.
The timepiece component 10 may be any as long as it is a component constituting a timepiece, but is preferably a component which can be visually recognized from the outside when using the timepiece, and specific examples thereof include a crystal, a case, a bezel, a back cover, a band (including a band block, a band clasp, a buckle, a band/bangle attachment/detachment mechanism, etc.), a dial, timepiece hands, a rotor, a crown (for example, a screw-lock crown, etc.), a button, a dial ring, and a parting plate, and above all, the timepiece component 10 is preferably a crystal, a case, or a band.
These components (timepiece components) greatly affect the appearance of a timepiece as a whole, and therefore, by applying the invention to these components, the aesthetic property of the timepiece as a whole can be further enhanced. Further, these components (timepiece components) are components which are generally exposed to the outside in the timepiece. Such components are particularly strongly required to have a function to be exhibited by including the functional film as described above. Therefore, by applying the invention to these components, the effect of the invention as described above is more remarkably exhibited.
Next, a timepiece according to the invention will be described.
A wristwatch (timepiece) W10 according to this embodiment includes a barrel (case) W22, a back cover W23, a bezel (frame) W24, and a glass plate (crystal) W25. Further, in the case W22, a movement (for example, a movement with a dial and hands) not shown in the drawing is housed.
In the barrel W22, a winding stem pipe W26 is fitted and fixed, and in this winding stem pipe W26, a shaft W271 of a crown W27 is rotatably inserted.
The barrel W22 and the bezel W24 are fixed to each other with a plastic packing W28, and the bezel W24 and the glass plate W25 are fixed to each other with a plastic packing W29.
In the barrel W22, the back cover W23 is fitted (or threadedly engaged), and in a joint portion (seal portion) W50 of these members, a ring-shaped rubber packing (back cover packing) W40 is inserted in a compressed state. According to this configuration, the seal portion W50 is liquid-tightly sealed, whereby a water-proof function is obtained.
A groove W272 is formed on the outer periphery in the middle of the shaft W271 of the crown W27, and in this groove W272, a ring-shaped rubber packing (crown packing) W30 is fitted. The rubber packing W30 is in close contact with the inner peripheral surface of the winding stem pipe W26 and compressed between the inner peripheral surface and the inner surface of the groove W272. According to this configuration, liquid-tight sealing is provided between the crown W27 and the winding stem pipe W26, so that a water-proof function is obtained. When the crown W27 is rotated, the rubber packing W30 rotates along with the shaft W271 and slides in the circumferential direction while being in close contact with the inner peripheral surface of the winding stem pipe W26.
In the wristwatch W10 as the timepiece according to the invention, at least one of the constituent components is constituted by the timepiece component according to the invention as described above. In other words, the timepiece according to the invention includes the timepiece component according to the invention.
Accordingly, the wristwatch W10 having an excellent appearance (an appearance exhibiting a metallic luster) can be provided even without using a noble metal as a main material.
Hereinabove, preferred embodiments of the invention have been described, however, the invention is not limited thereto.
For example, in the timepiece component and the timepiece according to the invention, the configuration of each portion can be replaced with an arbitrary configuration exhibiting a similar function, and also an arbitrary configuration can be added.
For example, at least one intermediate layer may be provided between the metallic luster portion and the toning film or between the substrate and the coating film.
Further, in the above-mentioned embodiments, a case where the functional film constitutes an outer surface of the timepiece member has been representatively described, however, the functional film may be disposed, for example, between the metallic luster portion and the toning film or may be provided between the substrate having a light transmission property and the toning film.
Further, in the above-mentioned fourth, fifth, and sixth embodiments, the metallic luster portion has been described as a portion which includes the first region and the second region, however, the metallic luster portion may further include a third region which is different from the first region and the second region.
Further, in the above-mentioned embodiments, the configuration in which the toning film is provided on one surface side of the metallic luster portion has been representatively described, however, the toning film may be provided on the surfaces on both sides of the metallic luster portion.
Further, in the above-mentioned embodiments, the configuration in which the functional film is provided on one surface side of the metallic luster portion has been representatively described, however, the functional film may be provided on the surfaces on both sides of the metallic luster portion.
Next, specific examples of the invention will be described.
First, a substrate having the shape of a wristwatch case was fabricated by casting using stainless steel (SUS304), and thereafter, a necessary portion was cut and polished.
Subsequently, this substrate was washed. In the washing of the substrate, first, alkaline electrolytic degreasing was performed for 30 seconds, and thereafter, neutralization for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds were performed.
Subsequently, a toning film constituted by a multilayer film of a metal oxide was formed on an outer surface (a portion to be exposed to the outside when forming a timepiece) of a case (timepiece component) to be obtained finally of the surfaces of the substrate by performing ion plating in a state where the substrate was partially covered with a mask.
The toning film was formed as a film in which a TiO2 layer (thickness: 47 nm), a SiO2 layer (thickness: 110 nm), a TiO2 layer (thickness: 66 nm), a SiO2 layer (thickness: 45 nm), a TiO2 layer (thickness: 20 nm), a SiO2 layer (thickness: 108 nm), a TiO2 layer (thickness: 78 nm), and a SiO2 layer (thickness: 33 nm) were stacked in this order from the substrate side.
Subsequently, a functional film (hard film) having a thickness of 32 nm constituted by SiN was formed on the surface of the toning film by ion plating, and thereafter, the mask was removed, whereby a wristwatch case as a timepiece component was obtained.
First, an inorganic glass substrate having the shape of a wristwatch case was prepared.
Subsequently, this substrate was washed. In the washing of the substrate, first, alkaline immersion degreasing was performed for 30 seconds, and thereafter, neutralization for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds were performed.
Subsequently, a coating film (metallic luster portion) having a thickness of 160 nm constituted by TiN was formed on an outer surface (a portion to be exposed to the outside when forming a timepiece) of a case (timepiece component) to be obtained finally of the surfaces of the substrate by performing ion plating in a state where the substrate was partially covered with a mask.
Subsequently, a toning film constituted by a multilayer film of a metal oxide was formed on the surface of the coating film (metallic luster portion) by ion plating.
The toning film was formed as a film in which a SiO2 layer (thickness: 66 nm), a Ta2O5 layer (thickness: 74 nm), a SiO2 layer (thickness: 120 nm), a Ta2O5 layer (thickness: 71 nm), and a SiO2 layer (thickness: 47 nm) were stacked in this order from the coating film (metallic luster portion) side.
Subsequently, a functional film (antifouling film) having a thickness of 5 nm constituted by a fluorine-containing organosilicon compound was formed on the surface of the toning film as described below, and thereafter, the mask was removed, whereby a wristwatch case as a timepiece component was obtained.
That is, first, 1.0 g of a dilution prepared by diluting a fluorine-containing organosilicon compound (KY-130(3), manufactured by Shin-Etsu Chemical Co., Ltd.) with a fluorine-based solvent (FR thinner, manufactured by Shin-Etsu Chemical Co., Ltd.) to a solid content of 3 mass % was placed in a vessel (an open-top cylindrical copper vessel, inner diameter: 16 mm, inner height: 6 mm) previously filled with 0.5 g of steel wool (#0, wire diameter: 0.025 mm, manufactured by Nihon Steel Wool Co., Ltd.), and dried at 120° C. for 1 hour. Subsequently, this copper vessel was placed in a vacuum evaporator along with the substrate having the coating film (metallic luster portion) and the toning film formed thereon, and the pressure in the evaporator was set to 0.01 Pa. Thereafter, the fluorine-containing organosilicon compound was evaporated from the copper vessel so that the film formation rate (vapor deposition rate) was 0.6 Å/s. As a heating source, a molybdenum resistance heating boat was used.
A timepiece component (case) was produced in the same manner as in the above-mentioned Example 2 except that the configuration of the coating film (metallic luster portion), the toning film, and the functional film was changed as shown in Table 1 by adjusting the film forming conditions when forming the coating film (metallic luster portion), the film forming conditions when forming the toning film, and the film forming conditions when forming the functional film.
First, a substrate (a first region of a metallic luster portion) having the shape of a wristwatch case was fabricated by casting using stainless steel (SUS304), and thereafter, a necessary portion was cut and polished.
Subsequently, this substrate was washed. In the washing of the substrate, first, alkaline electrolytic degreasing was performed for 30 seconds, and thereafter, neutralization for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds were performed.
Subsequently, a coating film (a second region of a metallic luster portion) having a thickness of 160 nm constituted by TiN was formed on an outer surface (a portion to be exposed to the outside when forming a timepiece) of a case (timepiece component) to be obtained finally of the surfaces of the substrate by performing ion plating in a state where the substrate was partially covered with a mask.
Subsequently, a toning film constituted by a multilayer film of a metal oxide was formed on the surface of the coating film by ion plating.
The toning film was formed as a film in which a SiO2 layer (thickness: 82 nm), a Ta2O5 layer (thickness: 63 nm), and a SiO2 layer (thickness: 91 nm) were stacked in this order from the coating film side.
Subsequently, a functional film (hard film) having a thickness of 110 nm constituted by SiN was formed on the surface of the toning film by ion plating, and thereafter, the mask was removed, whereby a wristwatch case as a timepiece component was obtained.
A timepiece component (wristwatch case) was produced in the same manner as in the above-mentioned Example 4 except that the configuration of the toning film and the functional film was changed as shown in Table 1 by adjusting the film forming conditions when forming the toning film and the film forming conditions when forming the functional film.
First, an inorganic glass substrate having the shape of a wristwatch case was prepared.
Subsequently, this substrate was washed. In the washing of the substrate, first, alkaline immersion degreasing was performed for 30 seconds, and thereafter, neutralization for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds were performed.
Subsequently, a coating film (metallic luster portion) as a stacked body in which a first region (first layer) and a second region (second layer) were stacked in this order was formed on an outer surface (a portion to be exposed to the outside when forming a timepiece) of a case (timepiece component) to be obtained finally of the surfaces of the substrate by performing ion plating in a state where the substrate was partially covered with a mask.
The first region (first layer) was constituted by TiN and had a thickness of 100 nm. The second region (second layer) was constituted by Al and had a thickness of 5 nm.
Subsequently, a toning film constituted by a multilayer film of a metal oxide was formed on the surface of the coating film (metallic luster portion) by ion plating.
The toning film was formed as a film in which a SiO2 layer (thickness: 109 nm), a Ta2O5 layer (thickness: 65 nm), and a SiO2 layer (thickness: 42 nm) were stacked in this order from the coating film (metallic luster portion) side.
Subsequently, a functional film (antifouling film) having a thickness of 5 nm constituted by a fluorine-containing organosilicon compound was formed on the surface of the toning film as described below, and thereafter, the mask was removed, whereby a wristwatch case as a timepiece component was obtained.
That is, first, 1.0 g of a dilution prepared by diluting a fluorine-containing organosilicon compound (KY-130(3), manufactured by Shin-Etsu Chemical Co., Ltd.) with a fluorine-based solvent (FR thinner, manufactured by Shin-Etsu Chemical Co., Ltd.) to a solid content of 3 mass % was placed in a vessel (an open-top cylindrical copper vessel, inner diameter: 16 mm, inner height: 6 mm) previously filled with 0.5 g of steel wool (#0, wire diameter: 0.025 mm, manufactured by Nihon Steel Wool Co., Ltd.), and dried at 120° C. for 1 hour. Subsequently, this copper vessel was placed in a vacuum evaporator along with the substrate having the coating film (metallic luster portion) and the toning film formed thereon, and the pressure in the evaporator was set to 0.01 Pa. Thereafter, the fluorine-containing organosilicon compound was evaporated from the copper vessel so that the film formation rate (vapor deposition rate) was 0.6 Å/s. As a heating source, a molybdenum resistance heating boat was used.
First, a substrate (a first region of a metallic luster portion) having the shape of a wristwatch case was fabricated by casting using stainless steel (SUS304), and thereafter, a necessary portion was cut and polished.
Subsequently, this substrate was washed. In the washing of the substrate, first, alkaline electrolytic degreasing was performed for 30 seconds, and thereafter, neutralization for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds were performed.
Subsequently, a coating film (a second region of a metallic luster portion) having a thickness of 160 nm constituted by TiN was formed on an outer surface (a portion to be exposed to the outside when forming a timepiece) of a case (timepiece component) to be obtained finally of the surfaces of the substrate by performing ion plating in a state where the substrate was partially covered with a mask.
Subsequently, a toning film constituted by a multilayer film of a metal oxide was formed on the surface of the coating film by ion plating.
The toning film was formed as a film in which a SiO2 layer (thickness: 70 nm), a Nb2O5 layer (thickness: 60 nm), a SiO2 layer (thickness: 130 nm), and a Nb2O5 layer (thickness: 42 nm) were stacked in this order from the coating film side.
Subsequently, a functional film (hard film) having a thickness of 45 nm constituted by SiN was formed on the surface of the toning film by ion plating, and thereafter, the mask was removed, whereby a wristwatch case as a timepiece component was obtained.
First, a substrate (a first region of a metallic luster portion) having the shape of a wristwatch case was fabricated by casting using stainless steel (SUS304), and thereafter, a necessary portion was cut and polished.
Subsequently, this substrate was washed. In the washing of the substrate, first, alkaline electrolytic degreasing was performed for 30 seconds, and thereafter, neutralization for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds were performed.
Subsequently, a coating film (a second region of a metallic luster portion) having a thickness of 160 nm constituted by TiN was formed on an outer surface (a portion to be exposed to the outside when forming a timepiece) of a case (timepiece component) to be obtained finally of the surfaces of the substrate by performing ion plating in a state where the substrate was partially covered with a mask.
Subsequently, a toning film constituted by a multilayer film of a metal oxide was formed on the surface of the coating film by ion plating.
The toning film was formed as a film in which a SiO2 layer (thickness: 65 nm), a ZrO2 layer (thickness: 67 nm), a SiO2 layer (thickness: 130 nm), a ZrO2 layer (thickness: 78 nm), a SiO2 layer (thickness: 130 nm), a ZrO2 layer (thickness: 94 nm), and a SiO2 layer (thickness: 60 nm) were stacked in this order from the coating film side.
Subsequently, a functional film (antifouling film) having a thickness of 5 nm constituted by a fluorine-containing organosilicon compound was formed on the surface of the toning film as described below, and thereafter, the mask was removed, whereby a wristwatch case as a timepiece component was obtained.
That is, first, 1.0 g of a dilution prepared by diluting a fluorine-containing organosilicon compound (KY-130(3), manufactured by Shin-Etsu Chemical Co., Ltd.) with a fluorine-based solvent (FR thinner, manufactured by Shin-Etsu Chemical Co., Ltd.) to a solid content of 3 mass % was placed in a vessel (an open-top cylindrical copper vessel, inner diameter: 16 mm, inner height: 6 mm) previously filled with 0.5 g of steel wool (#0, wire diameter: 0.025 mm, manufactured by Nihon Steel Wool Co., Ltd.), and dried at 120° C. for 1 hour. Subsequently, this copper vessel was placed in a vacuum evaporator along with the substrate having the coating film (metallic luster portion) and the toning film formed thereon, and the pressure in the evaporator was set to 0.01 Pa. Thereafter, the fluorine-containing organosilicon compound was evaporated from the copper vessel so that the film formation rate (vapor deposition rate) was 0.6 Å/s. As a heating source, a molybdenum resistance heating boat was used.
A timepiece component (wristwatch case) was produced in the same manner as in the above-mentioned Example 9 except that the configuration was changed as shown in Table 1 by adjusting the film forming conditions for the coating film (the second region of the metallic luster portion), the film forming conditions for the toning film, and the film forming conditions for the functional film.
A timepiece component (wristwatch case) was produced in the same manner as in the above-mentioned Example 9 except that the configuration was changed as shown in Table 1 by adjusting the film forming conditions for the coating film (the second region of the metallic luster portion), the film forming conditions for the toning film, and the film forming conditions for the functional film.
First, a polycarbonate substrate having the shape of a dial was prepared.
Subsequently, this substrate was washed. In the washing of the substrate, first, alkaline immersion degreasing was performed for 30 seconds, and thereafter, neutralization for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds were performed.
Subsequently, a toning film constituted by a multilayer film of a metal oxide was formed on one surface of the substrate by ion plating.
The toning film was formed as a film in which a SiO2 layer (thickness: 212 nm), an Al2O3 layer (thickness: 70 nm), a SiO2 layer (thickness: 235 nm), an Al2O3 layer (thickness: 78 nm), a SiO2 layer (thickness: 88 nm), a TiO2 layer (thickness: 35 nm), a SiO2 layer (thickness: 31 nm), a TiO2 layer (thickness: 62 nm), a SiO2 layer (thickness: 105 nm), and a TiO2 layer (thickness: 50 nm) were stacked in this order from the substrate side.
Subsequently, a coating film (metallic luster portion) having a thickness of 90 nm constituted by CrC was formed on the surface of the toning film by ion plating.
Thereafter, a HfO2 layer (thickness: 12 nm) and a SiO2 layer (thickness: 28 nm) were stacked in this order by ion plating on the other surface of the substrate (on a surface on the opposite side to the surface having the toning film and the coating film (metallic luster portion) formed thereon), and further, a functional film having a thickness of 120 nm constituted by SiN was formed on the surface of the SiO2 layer (thickness: 28 nm) by subsequently performed ion plating.
Subsequently, a SiO2 layer (thickness: 84 nm) was formed on the surface of the functional film by ion plating.
By doing this, a dial as a timepiece component was obtained.
First, a polycarbonate substrate having the shape of a dial was prepared.
Subsequently, this substrate was washed. In the washing of the substrate, first, alkaline immersion degreasing was performed for 30 seconds, and thereafter, neutralization for 10 seconds, washing with water for 10 seconds, and washing with pure water for 10 seconds were performed.
Subsequently, a toning film constituted by a multilayer film of a metal oxide was formed on one surface of the substrate by ion plating.
The toning film was formed as a film in which a HfO2 layer (thickness: 87 nm), a SiO2 layer (thickness: 125 nm), a TiO2 layer (thickness: 71 nm), and a SiO2 layer (thickness: 64 nm) were stacked in this order from the substrate side.
Subsequently, a coating film (metallic luster portion) having a thickness of 160 nm constituted by TiN was formed on the surface of the toning film by ion plating.
Thereafter, a SiO2 layer (thickness: 10 nm) was formed by ion plating on the other surface of the substrate (on a surface on the opposite side to the surface having the toning film and the coating film (metallic luster portion) formed thereon.
Subsequently, a functional film (antifouling film) having a thickness of 5 nm constituted by a fluorine-containing organosilicon compound was formed on the surface of the SiO2 layer (thickness: 10 nm) as described below, whereby a dial as a timepiece component was obtained.
That is, first, 1.0 g of a dilution prepared by diluting a fluorine-containing organosilicon compound (KY-130(3), manufactured by Shin-Etsu Chemical Co., Ltd.) with a fluorine-based solvent (FR thinner, manufactured by Shin-Etsu Chemical Co., Ltd.) to a solid content of 3 mass % was placed in a vessel (an open-top cylindrical copper vessel, inner diameter: 16 mm, inner height: 6 mm) previously filled with 0.5 g of steel wool (#0, wire diameter: 0.025 mm, manufactured by Nihon Steel Wool Co., Ltd.), and dried at 120° C. for 1 hour. Subsequently, this copper vessel was placed in a vacuum evaporator along with the substrate having the above-mentioned respective layers provided thereon, and the pressure in the evaporator was set to 0.01 Pa. Thereafter, the fluorine-containing organosilicon compound was evaporated from the copper vessel so that the film formation rate (vapor deposition rate) was 0.6 Å/s. As a heating source, a molybdenum resistance heating boat was used.
A timepiece component (dial) was produced in the same manner as in the above-mentioned Example 14 except that the configuration was changed as shown in Table 1 by adjusting the film forming conditions for the toning film and the coating film (metallic luster portion).
A timepiece component (wristwatch case) was produced in the same manner as in the above-mentioned Example 4 except that the configuration of the coating film (the second region of the metallic luster portion), the toning film, and the functional film was changed as shown in Table 1 by adjusting the film forming conditions when forming the coating film (the second region of the metallic luster portion), the film forming conditions when forming the toning film, and the film forming conditions when forming the functional film.
A timepiece component (wristwatch case) was produced in the same manner as in the above-mentioned Example 1 except that the toning film was not formed.
A timepiece component (wristwatch case) was produced in the same manner as in the above-mentioned Comparative Example 1 except that the functional film was not formed.
A member having the shape of a wristwatch case made of Au was fabricated by casting, and thereafter, a necessary portion was cut and polished, whereby a wristwatch case (timepiece component) was obtained. That is, the timepiece component of this Comparative Example was constituted by a pure gold material.
The configurations of the timepiece components of the respective Examples and the respective Comparative Examples are shown together in Table 1. The thickness of each portion excluding the substrate is shown in parentheses. Further, in the table, the inorganic glass is denoted by “G” and SUS304 is denoted by “SUS”. Further, with respect to each portion constituting the timepiece component, the content of the component shown in the table was all 99.9 mass % or more in all cases.
Further, with respect to those including a layer constituted by TiC among the respective Examples, the content of C (carbon) in the layer was within the range of 50 mass % or more and 60 mass % or less in all cases.
Further, with respect to those including a layer constituted by TiN among the respective Examples, the content of N (nitrogen) in the layer was within the range of 50 mass % or more and 60 mass % or less in all cases.
Further, with respect to those including a layer constituted by TiCN among the respective Examples, the content of C (carbon) in the layer was within the range of 5 mass % or more and 15 mass % or less, and the content of N (nitrogen) in the layer was within the range of 1 mass % or more and 5 mass % or less in all cases.
The respective timepiece components produced in the above-mentioned respective Examples and respective Comparative Examples were observed by visual inspection.
As a result, the timepiece components of the above-mentioned respective Examples all exhibited a very luxurious and excellent appearance. In particular, the timepiece components of Examples 2, 4, 5, 6, 7, 8, 9, 11, 12, 14, and 15 exhibited a luxurious gold color in the same manner as the timepiece component of Comparative Example 3, and in Examples 1, 3, and 13, an excellent appearance exhibiting a luxurious bluish luster was obtained. Further, in the timepiece component of Example 10 in which the metallic luster portion is constituted by a carbonitride of Ti, a luxurious appearance similar to pink gold was obtained. Further, in the timepiece component of Example 16 in which the metallic luster portion is constituted by a carbide of Ti, an excellent appearance exhibiting a luxurious bluish black color was obtained.
Further, in the respective Examples, a function corresponding to the functional film included in each timepiece component was effectively exhibited.
That is, the timepiece components of Examples 1, 3, 4, 8, 13, and 16 including the functional film (hard film) constituted by SiN or AlN had particularly excellent scratch resistance (less susceptible to scratches), dent resistance (less susceptible to dents), etc. and particularly excellent durability. Further, in the timepiece components of Examples, 2, 5, 7, 9, 10, 14, and 15 including the functional film (antifouling film) constituted by the fluorine-containing organosilicon compound, a decrease in the aesthetic property due to adhesion of dirt was prevented, and even if dirt adhered thereto, the dirt could be more easily removed, and thus, the touch, waterproof property, scratch resistance, etc. were also excellent, the adhesion of the functional film to the toning film was excellent, and the durability of the timepiece components was excellent. Further, the timepiece components of Examples 5, 11, and 12 including the functional film (antibacterial film) constituted by a photocatalyst layer of TiO2, and the timepiece component of Example 6 including the functional film (antibacterial film) constituted by 2-(4-thiazolyl)benzimidazole had an excellent antibacterial property. Further, when a standard light source D50 was used, the timepiece component of Example 1 had an L* value of 36.8, an a* value of 42.1, and a b* value of −90.1, the timepiece component of Example 2 had an L* value of 84.7, an a* value of 13.2, and a b* value of 49.3, the timepiece component of Example 3 had an L* value of 42.2, an a* value of 38.0, and a b* value of −87.3, the timepiece component of Example 4 had an L* value of 85.4, an a* value of 14.2, and a b* value of 40.2, the timepiece component of Example 5 had an L* value of 87.5, an a* value of 10.1, and a b* value of 41.4, the timepiece component of Example 6 had an L* value of 87.5, an a* value of 10.1, and a b* value of 41.4, the timepiece component of Example 7 had an L* value of 87.6, an a* value of 3.5, and a b* value of 41.1, the timepiece component of Example 8 had an L* value of 88.5, an a* value of 10.6, and a b* value of 41.4, the timepiece component of Example 9 had an L* value of 83.8, an a* value of 9.3, and a b* value of 42.2, the timepiece component of Example 10 had an L* value of 84.9, an a* value of 11.6, and a b* value of 22.6, the timepiece component of Example 11 had an L* value of 89.3, an a* value of 8.6, and a b* value of 36.6, the timepiece component of Example 12 had an L* value of 89.5, an a* value of 9.4, and a b* value of 38.5, the timepiece component of Example 13 had an L* value of 38.0, an a* value of 40.4, and a b* value of −86.5, the timepiece component of Example 14 had an L* value of 85.4, an a* value of 8.6, and a b* value of 42.8, the timepiece component of Example 15 had an L* value of 88.0, an a* value of 10.6, and a b* value of 36.9, and the timepiece component of Example 16 had an L* value of 38.7, an a* value of 2.8, and a b* value of −39.7.
On the other hand, in Comparative Example 1, only a poor luxurious appearance was obtained. Further, in Comparative Example 2, not only a poor luxurious appearance was only obtained, but also, the functions (high hardness, scratch resistance, dent resistance, antifouling property, antibacterial property, etc.) of the timepiece components of the respective Examples were not exhibited. In Comparative Example 3, although an excellent appearance was exhibited, a large amount of a noble metal was required for the production of the timepiece component.
The timepiece components of the respective Examples and Comparative Example 1 were observed from the surface on the side on which the functional film was provided.
When timepiece components (bands) were produced in the same manner as in the above-mentioned respective Examples and respective Comparative Examples except that the shape of the substrate was changed to the shape of a band, and evaluation was performed in the same manner as described above, the same results as described above were obtained.
Further, when timepiece components were produced in the same manner as in the above-mentioned Examples 1, 5 to 7, 9, and 10 except that Al, Cr, or Ti was used in place of SUS304 as the material of the metallic luster portion, and evaluation was performed in the same manner as described above, the same results as described above were obtained.
Further, when timepiece components were produced in the same manner as in the above-mentioned Example 8 except that Ti, Cr, or Fe was used in place of Al as the constituent material of the second region, and evaluation was performed in the same manner as described above, the same results as described above were obtained.
Further, wristwatches as shown in
The entire disclosure of Japanese Patent Application Nos. 2017-014557, filed Jan. 30, 2017 and 2017-216500, filed Nov. 9, 2017 are expressly incorporated by reference herein.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017-014557 | Jan 2017 | JP | national |
| 2017-216500 | Nov 2017 | JP | national |
