Colored rigid decorative member

Patent metadata

Field	Value
Publication number	US-9464355-B2
Application number	US-201314385165-A
Country	US
Kind code	B2
Filing date	Feb 28, 2013
Priority date	Mar 19, 2012
Publication date	Oct 11, 2016
Grant date	Oct 11, 2016

Abstract

Provided is a colored rigid decorative member in which scratch resistance is improved, and deterioration of appearance quality due to a flaw, abrasion, or the like is suppressed, and which has various color variations with a high quality feel. An alloy adhesion layer having a high adhesion effect, an alloy gradient adhesion layer of which the content of a reactant gas is increased in a gradient manner, an abrasion-resistant layer having high hardness, an alloy recolored gradient layer of which the content of a reactant gas is decreased in a gradient manner, and a colored decorative layer having high decorativeness and color variations on the outermost layer are formed on a base using a film with an alloy of a metal having the high effect of adhering to a metal and high brightness (metal having poor corrosion resistance; Mo, W), a metal having high film hardness and high corrosion resistance (metal having poor adhesion; Nb, Ta), and a metal improving corrosion resistance performance (Cr, Ti, Hf, Zr).

First claim

The invention claimed is:

1. A colored rigid decorative member comprising:
a base;
an adhesion layer, stacked on the base, comprising a lower oxide layer of an alloy in which a metal M1 and a metal M2, and, in addition, selectively a metal M3 are combined;
an inclined adhesion layer, stacked on the adhesion layer, comprising a reaction compound of an alloy in which a metal M4 and a metal M5, and, in addition, selectively a metal M6 are combined and of a non-metallic element selected from one or two or more of nitrogen, carbon, and oxygen;
an abrasion-resistant layer, stacked on the inclined adhesion layer, comprising a reaction compound of an alloy in which a metal M7 and a metal M8, and, in addition, selectively a metal M9 are combined and of a non-metallic element selected from one or two or more of nitrogen, carbon, and oxygen; a recolored inclined layer, stacked on the abrasion-resistant layer, comprising a reaction compound of an alloy in which a metal M10 and a metal M11, and, in addition, selectively a metal M12 are combined and of a non-metallic element selected from one or two or more of nitrogen, carbon, and oxygen; and
a colored decorative layer stacked on the recolored inclined layer, wherein
each of the metals M1, M4, M7, and M10 is selected from one or two of Mo and W;
each of the metals M2, M5, M8, and M11 is selected from one or two of Nb and Ta;
the metals M3, M6, M9, and M12 are selected from one or two or more of Cr, Ti, Hf, and Zr;
the content of a non-metallic element in a reaction compound included in the inclined adhesion layer is increased in an inclining manner in a thickness direction with departing from a substrate; and
the content of a non-metallic element in a reaction compound included in the recolored inclined layer is decreased in an inclining manner in a thickness direction with departing from the substrate.

2. The colored rigid decorative member according to claim 1 , wherein
the colored decorative layer is a white noble metal film of Pt, Pd, or Rh; and
an intermetallic compound of a metal in the recolored inclined layer and the white noble metal is formed in a boundary between the colored decorative layer and the recolored inclined layer.

3. The colored rigid decorative member according to claim 1 , wherein the colored decorative layer is a colored rigid film comprising a nitride, a carbide, a carbonitride, or a nitroxide of Ti, Zr, or Hf.

4. The colored rigid decorative member according to claim 1 , wherein the colored decorative layer is a DLC (diamond-like carbon) rigid film.

5. The colored rigid decorative member according to claim 1 , wherein the colored decorative layer is a dielectric layer obtained by forming a single- or multi-layered dielectric film.

6. The colored rigid decorative member according to claim 4 , wherein a single- or multi-layered adhesion layer comprising Si or Ti is formed between the recolored inclined layer and the colored decorative layer.

7. The colored rigid decorative member according to claim 1 , wherein the decorative film comprises a two-tone structure.

8. A method for producing a colored rigid decorative member, comprising:
a step of forming, on a base, an adhesion layer comprising a lower oxide layer of an alloy in which a metal M1 and a metal M2, and, in addition, selectively a metal M3 are combined;
a step of forming, on the adhesion layer, an inclined adhesion layer comprising a reaction compound of an alloy in which a metal M4 and a metal M5, and, in addition, selectively a metal M6 are combined and of a non-metallic element selected from one or two or more of nitrogen, carbon, and oxygen so that the content of a non-metallic element in a reaction mixture included in the inclined adhesion layer is increased in an inclining manner in a thickness direction with departing from a substrate;
a step of forming, on the inclined adhesion layer, an abrasion-resistant layer comprising a reaction compound of an alloy in which a metal M7 and a metal M8, and, in addition, selectively a metal M9 are combined and of a non-metallic element selected from one or two or more of nitrogen, carbon, and oxygen;
a step of forming, on the abrasion-resistant layer, a recolored inclined layer comprising a reaction compound of an alloy in which a metal M10 and a metal M11, and, in addition, a metal M12 are combined and of a non-metallic element selected from one or two or more of nitrogen, carbon, and oxygen so that the content of a non-metallic element in a reaction compound included in the recolored inclined layer is decreased in an inclining manner in a thickness direction with departing from the substrate; and
a step of stacking a colored decorative layer on the recolored inclined layer, wherein
each of the metals M1, M4, M7, and M10 is selected from one or two of Mo and W;
each of the metals M2, M5, M8, and M11 is selected from one or two of Nb and Ta; and
each of the metals M3, M6, M9, and M12 is selected from one or two or more of Cr, Ti, and Hf.

9. The method for producing a colored rigid decorative member according to claim 8 , wherein at least one of the adhesion layer, the inclined adhesion layer, the abrasion-resistant layer, the recolored inclined layer, and the colored decorative layer is formed by a reactive sputtering method.

10. The method for producing a colored rigid decorative member according to claim 9 , wherein
the inclined adhesion layer is formed by chronologically increasing or decreasing the amount of reactant gas containing the non-metallic element in a reactive sputtering method in the step of forming the inclined adhesion layer; and
the recolored inclined layer is formed by chronologically increasing or decreasing the amount of reactant gas containing the non-metallic element in a reactive sputtering method in the step of forming the recolored inclined layer.

11. The method for producing a colored rigid decorative member according to claim 8 , further comprising a step of applying a mask to a portion of the colored decorative layer and peeling a non-masked portion of the colored decorative layer with an acid or an alkali, to thereby allow the colored decorative layer to comprise a two-tone structure.

Assignees

• Citizen Holdings Co Ltd
• Citizen Watch Co Ltd

Inventors

• Takazaki Koutarou

Classifications

• Y10T428/30

  Self-sustaining carbon mass or layer with impregnant or other layer · CPC title

• C23C14/0084

  Producing gradient compositions · CPC title

• C23C14/06

  characterised by the coating material ({C23C14/0021} , C23C14/04 take precedence) · CPC title

• C23C28/345

  with at least one oxide layer · CPC title

• C23C14/083

  of refractory metals or yttrium · CPC title