JP2006283088A - Golden ornament and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ornament having excellent wear resistance and scratch resistance and having a golden film layer which is not peeled even when the film thickness is made extremely thin. <P>SOLUTION: The golden ornament comprises a base material, a Ti film deposited on the surface of the base material under the inert gas atmosphere other than nitrogen while the rate of content of Ti atoms is fixed in the film thickness direction, a TiN inclined film deposited on the Ti film while the rate of content of N atoms has the gradient in the film thickness direction, a TiN film deposited on the TiN inclined film while the rate of content of Ti atoms and N atoms is fixed in the film thickness direction, an Au-TiN mixed inclined film deposited on the TiN film while the rate of content of Au atoms has the gradient in the film thickness direction, and an Au-TiN mixed film deposited on the Au-TiN mixed inclined film while the rate of content of Au atoms, Ti atoms and N atoms is fixed in the film thickness direction. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a golden decorative article having excellent scratch resistance and peel resistance and a method for producing the same.

  Exterior parts such as watches and accessories are required to have a color tone as a decorative element and wear resistance as a functional element at the same time. Gold is most suitable for this requirement, and has been conventionally used by processing a raw material as it is or by forming a gold plating coating layer on another metal. However, when corrosion resistance is not required, the purpose has been achieved even in a multilayer of 1 micron or less in the sense of showing a gold color. Since it was required, the gold plating required a film thickness of at least 10 microns or more.

  However, since gold is a very expensive metal, there is a limit to use it for exterior parts having sufficient corrosion resistance and wear resistance. Further, since the hardness of gold is about 350 Hv, there is a problem that it is inferior in scratch resistance and easily damaged by carrying a wristwatch or jewelry. For this reason, it has been desired to develop a gold-colored coating layer that is cheaper and exhibits a sufficient function.

  Therefore, a coating layer made of titanium nitride and gold or a gold alloy has been proposed by dry plating techniques such as ion plating and sputtering (see, for example, Patent Documents 1 to 3), and has excellent corrosion resistance and wear resistance. However, a thin and inexpensive golden coating has been formed.

However, although the coating layer made of titanium nitride and gold or gold alloy has improved adhesion to the underlying metal layer made of titanium, titanium nitride or the like compared to the conventional gold plating coating layer, the adhesion There was still room for improvement. In particular, when the coating layer made of titanium nitride and gold or a gold alloy is made extremely thin, there is a problem that it easily peels off.
JP-A-54-2942 JP 58-104176 A JP-A-60-67654

  The present invention is intended to solve the problems associated with the prior art as described above, and has a golden coating layer that is excellent in wear resistance and scratch resistance and does not peel even if the film thickness is extremely thin. The object is to provide a decorative article and a method for manufacturing the same.

In the method for producing a golden ornament according to the present invention, titanium is evaporated on the surface of a base material in an inert gas atmosphere other than nitrogen in a dry plating apparatus so that the amount of evaporation per unit time is constant. Forming a Ti coating;
Next, while evaporating titanium in the dry plating apparatus so that the evaporation amount per unit time is constant, nitrogen gas in the dry plating apparatus is increased so that the nitrogen amount in the dry plating apparatus increases with time. To form a TiN gradient coating film having a N atom content gradient in the film thickness direction on the Ti coating film,
Next, while evaporating titanium in the dry plating apparatus so that the evaporation amount per unit time is constant, the nitrogen amount in the dry plating apparatus is kept constant, and TiN is deposited on the TiN gradient coating. Forming a film,
Next, the evaporation amount of gold per unit time while evaporating titanium in the dry plating apparatus so that the evaporation amount per unit time is constant and keeping the nitrogen amount in the dry plating apparatus constant. As a result, gold or gold and other metals are evaporated so as to increase with time, and an Au—TiN mixed gradient film having a gradient in the film thickness direction of the content of Au atoms is formed on the TiN film. ,
Next, while keeping the amount of nitrogen in the dry plating apparatus constant, the evaporation amount per unit time of titanium and gold or titanium, gold, and other metals is constant in the dry plating apparatus. Evaporating to form an Au—TiN mixed coating film on the Au—TiN mixed gradient coating.

  When forming the Au-TiN mixed gradient coating, the Au atom content in the Au-TiN mixed gradient coating is increased per unit time so as to increase in the film thickness direction at a rate of 2 to 10 atomic% / 0.001 μm. It is preferable to increase the evaporation amount of gold over time, and it is also preferable to supply nitrogen gas in a dry plating apparatus that is 2.5 times the nitrogen gas supply amount at the time of TiN film formation.

When forming the Au—TiN mixed film, it is preferable to supply nitrogen gas in a dry plating apparatus that is at least 2.5 times the amount of nitrogen gas supplied when the TiN film is formed.
When forming the TiN gradient coating, the amount of nitrogen in the dry plating apparatus is adjusted so that the N atom content in the TiN gradient coating increases in the film thickness direction at a rate of 4 to 12 atomic% / 0.1 μm. Increasing with time is preferred.

  The golden ornament according to the present invention includes a base material, a Ti coating formed on the surface of the base material in an inert gas atmosphere other than nitrogen and having a constant Ti atom content in the film thickness direction, and the Ti coating. The TiN gradient coating formed on the coating has a gradient in the film thickness direction of N atoms, and the content of Ti atoms and N atoms formed on the TiN gradient coating is constant in the film thickness. A certain TiN film, an Au-TiN mixed gradient film formed on the TiN film and having an Au atom content gradient in the film thickness direction, and an Au atom formed on the Au-TiN mixed gradient film And an Au—TiN mixed film in which the content of Ti atoms and N atoms is constant in the film thickness direction.

  In the Au—TiN mixed gradient coating, it is preferable that the content of Au atoms increases in the film thickness direction from the TiN coating to the Au—TiN mixed coating, and the content of Au atoms is 2 to 10 atomic% / 0.00%. It is preferable to increase at a rate of 001 μm.

  In the TiN gradient coating, it is preferable that the content of N atoms increases in the film thickness direction from the Ti coating to the TiN coating, and the content of N atoms increases at a rate of 4 to 12 atomic% / 0.1 μm. It is preferable.

  The golden ornament according to the present invention has a Ti film thickness of 0.1 to 0.5 μm, a total film thickness of the TiN gradient film and the TiN film is 0.5 to 2.0 μm, and the total The ratio of the film thickness of the TiN gradient coating film to the film thickness is in the range of 10 to 60%, and the total film thickness of the Au—TiN mixed gradient coating film and the Au—TiN mixed coating film is 0.005 to 0.1 μm. And the ratio of the thickness of the Au—TiN mixed gradient coating to the total thickness is preferably in the range of 10 to 90%.

In the golden decorative article according to the present invention, each coating layer has excellent adhesion to each other, and the outermost Au-TiN mixed coating has high surface hardness and excellent corrosion resistance, abrasion resistance and scratch resistance. In particular, since the Au-TiN mixed gradient coating exhibits excellent adhesion to both the Au-TiN mixed coating and the TiN coating, even if the Au-TiN mixed gradient coating is extremely thin, the surface of the golden decorative article No wear, frictional flaws, or peeling of the coating occurs. For this reason, the usage-amount of gold | metal | money can be reduced and a golden ornament can be obtained cheaply.

  Moreover, according to the manufacturing method of the golden ornament which concerns on this invention, such a golden ornament can be manufactured.

Hereinafter, the golden decorative article and the manufacturing method thereof according to the present invention will be described in detail.
The golden ornament according to the present invention forms a Ti film on the surface of a substrate by a dry plating method, forms a TiN gradient film on the Ti film, forms a TiN film on the TiN gradient film, It can be manufactured by forming an Au-TiN mixed gradient coating on the TiN coating and forming an Au-TiN mixed coating on the Au-TiN mixed gradient coating.

  Examples of the dry plating method used in the present invention include a vacuum deposition method, a sputtering method, and an ion plating method. Of these, the ion plating method is preferably used.

Hereinafter, a method for forming each film will be described in detail.
(1) Formation of Ti film First, the base material is placed in a dry plating apparatus, and after evacuating the dry plating apparatus, an inert gas other than nitrogen is introduced. Next, a titanium film is formed on the surface of the substrate by dry plating so that the amount of titanium evaporated per unit time is constant in this inert gas atmosphere, that is, the titanium is constantly evaporated. At this time, the evaporation amount of titanium per unit time is set so that the film formation rate of the Ti film is preferably 0.005 to 0.05 μm / min, more preferably 0.01 to 0.03 μm / min. It is desirable.

  At this time, after evacuating the inside of the dry plating apparatus to usually 5 to 0.1 mPa, preferably 1 to 0.1 mPa, an inert gas other than nitrogen is usually 0.01 to 1.0 Pa, preferably 0.1 to 0. Introduced up to 5 Pa. Examples of the inert gas other than nitrogen include argon, helium, and neon. It is preferable to lower the exhaust pressure in the dry plating apparatus as much as possible. Thereby, the remaining amount of inevitable components (nitrogen, oxygen, carbon) inside the apparatus can be sufficiently reduced to obtain a high purity Ti coating. .

  Examples of the material of the base material include stainless steel, titanium, titanium alloy, copper, copper alloy, tungsten carbide, ceramics, and the like. Such a substrate is preferably cleaned and degreased with an organic solvent or the like before placing the substrate in a dry plating apparatus.

  In the Ti film formed in this way, the content of Ti atoms is substantially constant in the film thickness direction. In this Ti film, an inevitable component consisting of at least one of nitrogen, oxygen, and carbon is preferably 0.5 to 20 atomic%, more preferably 0.5 to 12 atomic%, and particularly preferably 0.5. It may be contained at ˜5 atomic%. At this time, the content rate of Ti atom becomes like this. Preferably it is 80-99.5 atomic%, More preferably, it is 88-99.5 atomic%, More preferably, it is 95-99.5 atomic%.

In the Ti coating, the total content of Ti atoms and inevitable components is 100 atomic%.
(2) Formation of TiN Inclined Film Following (1) above, nitrogen gas is introduced into the dry plating apparatus while titanium is constantly evaporated to keep the Ti atom amount in the dry plating apparatus constant. By the introduction of this nitrogen gas, the amount of nitrogen in the dry plating apparatus, that is, the amount of N atoms increases with time. A film containing Ti and N is formed on the Ti film by a dry plating method in a state where the N atomic weight is increasing with time. The film thus formed has a gradient in the film thickness direction of the content of N atoms and Ti atoms (hereinafter, this film is referred to as “TiN gradient film”).

  At this time, the nitrogen content in the dry plating apparatus is such that the content of N atoms in the formed TiN gradient coating is preferably 4 to 12 atomic% / 0.1 μm, preferably 6 to 10 atomic% / 0.1 μm, More preferably, it is desirable to increase with time so as to increase in the film thickness direction at a rate of 7-9 atomic% / 0.1 μm.

  For example, when a mixed gas of nitrogen gas and an inert gas such as argon is used as the introduced gas, the amount of nitrogen in the dry plating apparatus is increased over time by increasing the ratio of the nitrogen gas in the mixed gas over time. Can be increased. Nitrogen gas introduction conditions are appropriately set depending on the dry plating apparatus, plating conditions, and the like so that the TiN gradient coating film having the above-described content rate gradient is formed. For example, the flow rate ratio of nitrogen gas to inert gas (nitrogen gas / inert gas) is started from 0, preferably in the range of 1.5 to 3.0, more preferably 1.8 to 2.5. To the range, preferably in 10-60 minutes, more preferably in 20-40 minutes.

  The amount of evaporation of titanium per unit time may be set so that the TiN gradient coating film formation rate is preferably 0.005 to 0.05 μm / min, more preferably 0.01 to 0.03 μm / min. desirable. For example, it is desirable to evaporate titanium under the same conditions as the amount of titanium evaporation per unit time when the Ti film is formed.

  The N atom content in the thus formed TiN gradient coating increases from the Ti coating to the TiN coating in the film thickness direction, and the Ti atom content increases from the Ti coating to the TiN coating in the film thickness direction. Is preferably reduced. Specifically, the N atom content is preferably increased from the Ti film to the TiN film in the film thickness direction at a rate within the above range. The Ti atom content is preferably 4 to 12 atom% / 0.1 μm, preferably 6 to 10 atom% / 0.1 μm, more preferably 7 to 9 atom% / 0.1 μm. It is desirable to decrease with respect to the film thickness direction from TiN to TiN film.

The TiN gradient coating in which N atoms and Ti atoms increase or decrease at the above-described ratio is excellent in adhesion to both the Ti coating and the TiN coating.
The TiN gradient coating has an inevitable component consisting of at least one of oxygen and carbon, preferably 0.5 to 20 atomic%, more preferably 0.5 to 12 atomic%, and particularly preferably 0.5 to It may be contained at 5 atomic%.

In the TiN gradient coating, the total content of Ti atoms, N atoms and inevitable components is 100 atomic%.
(3) Formation of TiN film Following (2) above, nitrogen gas is constantly supplied into the dry plating apparatus to keep the amount of nitrogen in the dry plating apparatus constant, Titanium is steadily evaporated so that the Ti atomic weight is constant, and a TiN film is formed on the TiN gradient film by a dry plating method.

  At this time, the amount of nitrogen in the dry plating apparatus is such that the content of N atoms in the formed TiN film is preferably 10 to 60 atom%, more preferably 20 to 50 atom%, and particularly preferably 30 to 45 atom%. So that it is constant. At this time, the amount of nitrogen gas supplied into the dry plating apparatus is appropriately set depending on the dry plating apparatus, plating conditions, etc. so that the amount of nitrogen in the dry plating apparatus is kept constant.

  For example, when a mixed gas of nitrogen gas and an inert gas such as argon is used as the introduction gas, the flow rate ratio of nitrogen gas to inert gas (nitrogen gas / inert gas) is preferably 1.5-3. It is desirable to keep it constant within a range of 0.0, more preferably 1.8 to 2.5.

  The amount of titanium evaporation per unit time is desirably set so that the deposition rate of the TiN film is preferably 0.005 to 0.05 μm / min, more preferably 0.01 to 0.03 μm / min. . For example, it is desirable to evaporate titanium under the same conditions as the amount of titanium evaporation per unit time when the Ti film is formed.

  In the TiN film thus formed, the content of Ti atoms and N atoms is substantially constant in the film thickness direction. The N atom content is in the above range, and the Ti atom content is preferably 30 to 80 atom%, more preferably 40 to 70 atom%, and particularly preferably 45 to 60 atom%.

  In addition, the TiN film has an inevitable component consisting of at least one of oxygen and carbon, preferably 0.5 to 20 atomic%, more preferably 0.5 to 12 atomic%, and particularly preferably 0.5. It may be contained at ˜5 atomic%.

In the TiN coating, the total content of Ti atoms, N atoms and inevitable components is 100 atomic%.
(4) Formation of Au-TiN mixed gradient coating Following the above (3), this dry process is carried out while constantly supplying nitrogen gas into the dry plating apparatus and keeping the amount of nitrogen in the dry plating apparatus constant. Titanium is constantly evaporated so that the amount of Ti atoms in the plating apparatus is constant. At this time, the nitrogen gas is preferably 2.5 times or more, more preferably 2.8 times or more the amount of nitrogen gas supplied into the dry plating apparatus when the TiN film is formed. It is desirable to supply. By increasing and maintaining the nitrogen gas supply amount as described above, a decorative product exhibiting a more golden hue can be obtained.

  The amount of evaporation of titanium per unit time is set so that the deposition rate of the Au—TiN mixed gradient coating is preferably 0.005 to 0.05 μm / min, more preferably 0.01 to 0.03 μm / min. It is desirable to do. For example, it is desirable to evaporate titanium under the same conditions as the amount of titanium evaporation per unit time when the Ti film is formed.

  While maintaining the above state, gold or gold and other metals are evaporated so that the amount of gold evaporation per unit time increases over time, and Au atoms or Au atoms and other metals are evaporated in this dry plating apparatus. Introduce metal atoms. Next, a film containing Ti, N, Au, and, if necessary, another metal is formed on the TiN film by a dry plating method while increasing the evaporation amount of gold per unit time with time. By increasing the amount of gold evaporation per unit time over time as described above, the deposition amount of gold per unit time increases with time, and a gradient film in which the gold content increases in the film growth direction is obtained. Can be formed. In the film formed in this way, the content of Ti atoms, N atoms, Au atoms and other metal atoms has a gradient in the film thickness direction (hereinafter this film is referred to as “Au—TiN mixed gradient film”). .

  At this time, the evaporation amount of gold per unit time is preferably 2 to 10 atomic% / 0.001 μm, more preferably 4 to 9 atomic% in terms of the content of Au atoms in the formed Au—TiN mixed gradient coating. It is desirable to increase it with time so that it increases in the film thickness direction at a ratio of /0.001 μm, particularly preferably 6 to 8 atomic% / 0.001 μm.

For example, when converted into a case where an Au—TiN mixed gradient film is formed at a film formation rate of 0.02 μm / min, the content of Au atoms in all atoms deposited per unit time is preferably 0 per second. It is desirable to evaporate gold so that it increases at a rate of .6 to 3.4 atom%, more preferably 1.3 to 3.0 atom%, and particularly preferably 2.0 to 2.7 atom%.

  In the Au-TiN mixed gradient coating thus formed, the content of Au atoms increases in the film thickness direction from the TiN coating to the Au-TiN mixed coating, and the content of Ti atoms and N atoms is TiN. It is preferable to decrease in the film thickness direction from the coating to the Au—TiN mixed coating. Specifically, it is desirable that the content of Au atoms is increased in the film thickness direction from the TiN coating to the Au—TiN mixed coating at a rate within the above range. The Ti atom content is preferably 1-10 atomic% / 0.001 μm, more preferably 2-8 atomic% / 0.001 μm, and particularly preferably 3-5 atomic% / 0.001 μm. It is desirable to decrease in the film thickness direction from the coating to the Au—TiN mixed coating. Further, the content of N atoms is preferably 1-10 atomic% / 0.001 μm, more preferably 2-8 atomic% / 0.001 μm, particularly preferably 4-6 atomic% / 0.001 μm. It is desirable to decrease in the film thickness direction from the coating to the Au—TiN mixed coating.

  The Au—TiN mixed gradient coating in which Au atoms, Ti atoms, and N atoms increase or decrease at the above-described ratio has excellent adhesion to both the TiN coating and the Au—TiN mixed coating.

  When this Au-TiN mixed gradient coating contains another metal atom, it is preferable that the Au atom and the other metal atom form a gold alloy. Examples of other metal atoms include germanium, silicon, silver, copper, palladium, nickel, iron, platinum, niobium, and chromium. The content of other metal atoms is preferably 1 to 20 atomic%, more preferably 3 to 15 atomic%, and particularly preferably 5 to 10 atomic%.

  The Au—TiN mixed gradient coating preferably contains at least one of oxygen and carbon, preferably 0.5 to 20 atomic%, more preferably 0.5 to 12 atomic%, and particularly preferably. It may be contained at 0.5 to 5 atomic%.

In the Au—TiN mixed gradient coating, the total content of Ti atoms, Au atoms, N atoms and unavoidable components is 100 atomic%.
(5) Formation of Au—TiN mixed film Following the above (4), this dry plating is performed while constantly supplying nitrogen gas into the dry plating apparatus to keep the amount of nitrogen in the dry plating apparatus constant. Titanium and gold or titanium, gold and other metals are steadily evaporated so that the Ti atomic weight and Au atomic weight in the apparatus are constant, and Au—TiN mixed gradient coating is formed on the Au—TiN mixed gradient coating by dry plating. A TiN mixed film is formed.

  At this time, the amount of nitrogen in the dry plating apparatus is preferably 5 to 50 atom%, more preferably 15 to 40 atom%, and particularly preferably 20 to 20% by atom content in the Au—TiN mixed film to be formed. It is kept constant so as to be 30 atomic%. At this time, the nitrogen gas is preferably 2.5 times or more, more preferably 2 times the amount of nitrogen gas supplied into the dry plating apparatus when the TiN film is formed, as in the formation of the Au-TiN mixed gradient film. It is desirable to supply more than 8 times the amount of nitrogen gas into the dry plating apparatus. By increasing and maintaining the nitrogen gas supply amount as described above, a decorative product exhibiting a more golden hue can be obtained. The amount of nitrogen gas supplied into the dry plating apparatus is appropriately set according to the dry plating apparatus, plating conditions, etc., as in the case of forming the TiN film, so that the nitrogen amount in the dry plating apparatus is kept constant. .

The evaporation amount of titanium per unit time is preferably set to a film formation speed of the Au—TiN mixed film.
It is desirable to set it to be 005 to 0.05 μm / min, more preferably 0.01 to 0.03 μm / min. For example, it is desirable to evaporate titanium under the same conditions as the amount of titanium evaporation per unit time when the Ti film is formed.

  The amount of gold evaporation per unit time is preferably 10 to 60 atomic%, more preferably 20 to 55 atomic%, and particularly preferably 25 to 45 atoms in terms of the Au atom content in the Au—TiN mixed film to be formed. % To keep constant.

  In the Au—TiN mixed film thus formed, the content of Au atoms, Ti atoms, and N atoms is substantially constant in the film thickness direction. The content of Au atoms and N atoms is in the above range, and the content of Ti atoms is preferably 10 to 60 atomic%, more preferably 20 to 50 atomic%, and particularly preferably 30 to 45 atomic%.

  When this Au-TiN mixed film contains another metal atom, it is preferable that the Au atom and the other metal atom form a gold alloy. Examples of other metal atoms include germanium, silicon, silver, copper, palladium, nickel, iron, platinum, niobium, and chromium. The content of other metal atoms is preferably 1 to 20 atomic%, more preferably 3 to 15 atomic%, and particularly preferably 5 to 10 atomic%.

  In addition, the Au—TiN mixed film has an inevitable component composed of at least one of oxygen and carbon, preferably 0.5 to 20 atomic%, more preferably 0.5 to 12 atomic%, particularly preferably. It may be contained at 0.5 to 5 atomic%.

In the Au—TiN mixed film, the total content of Ti atoms, Au atoms, N atoms and inevitable components is 100 atomic%.
The golden ornament according to the present invention can be manufactured by the above manufacturing method. This golden decorative article is excellent in adhesion because the Au—TiN mixed coating and the TiN coating are laminated via the Au—TiN mixed gradient coating. Thereby, an Au-TiN mixed film can be made extremely thin. Moreover, since the Au—TiN mixed coating can be made extremely thin, it is possible to increase the thickness of the TiN coating and to improve the strength as a laminated film.

  The preferable range of the film thickness of each film of this golden decorative article is shown below. The thickness of the Ti coating is preferably 0.1 to 0.5 μm, more preferably 0.2 to 0.5 μm, and particularly preferably 0.3 to 0.5 μm.

  The total film thickness of the TiN gradient coating and the TiN coating is preferably 0.5 to 2.0 μm, more preferably 0.7 to 1.8 μm, and particularly preferably 1.0 to 1.5 μm. The ratio of the thickness of the TiN gradient coating to the total thickness of the TiN gradient coating and the TiN coating is preferably 10 to 60%, more preferably 20 to 55%, and particularly preferably 30 to 50%. If the film thickness ratio of the TiN gradient coating exceeds the upper limit, the TiN film ratio may decrease and the film strength may decrease.

  The total film thickness of the Au—TiN mixed gradient coating and the Au—TiN mixed coating is preferably 0.005 to 0.1 μm, more preferably 0.005 to 0.05 μm, and particularly preferably 0.01 to 0.02 μm. The ratio of the thickness of the Au-TiN mixed gradient coating to the total thickness of the Au-TiN mixed gradient coating and the Au-TiN mixed coating is preferably 10 to 90%, more preferably 20 to 70%, particularly Preferably it is 30 to 50%. When the ratio of the film thickness of the Au—TiN mixed gradient coating is within the above range, the golden ornament exhibits a golden hue.

When the film thickness of each layer is in the above range, delamination of each layer does not occur, and a golden decorative article having excellent adhesion can be obtained.
Such a golden decorative article has a high coating hardness of the outermost layer. For example, the Vickers hardness measured and converted under the condition of a load of 50 μN with a nanoindenter is preferably 500 to 800 Hv, more preferably 600 to 700 Hv. . The hardness of the outermost layer of the conventional golden ornament is about 370 Hv.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In addition, the corrosion resistance test and the abrasion test in the examples were performed according to the following methods.

(1) Corrosion resistance test The corrosion resistance test was performed according to JIS H8502 (CASS test). The test time was 96 hours, and the corrosion resistance evaluation of the test surface was accepted when the rating number was 9.8 or more according to the rating number standard chart.
(2) Abrasion test As shown in FIG. 1, the test piece mounting base 4 is opened by the test piece presser plate 2 and the test piece presser screw 3 with the test piece 1 having the coating formed facing downward. Fixed to the part. Next, abrasive paper (not shown) was attached to the wear wheel 5. An upward load that presses the abrasive paper against the test piece 1 was applied to the wear wheel 5 by a balance mechanism (not shown).

  Thereafter, the specimen mounting base 4 is reciprocated by a mechanism that converts the rotational movement of the motor (not shown) into a reciprocating movement, and the wear wheel 5 is moved in the direction of the arrow by an angle of 0.9 ° for each reciprocation of the specimen mounting base 4. Rotated. By this rotation, the test piece 1 always comes into contact with a new area of the abrasive paper affixed to the wear ring 5 that is not worn. The number of reciprocations of the test specimen mounting base 4 can be automatically set, and the wear tester automatically stops at the set number of times.

Further, as the abrasive paper to be affixed to the wear ring 5, a wrapping film (# 1200 having Al ₂ O ₃ particles having a particle diameter of 12 μm on the film surface) is used, and the contact load between the abrasive paper and the test piece 1 is 500 g. The wear test was performed with a wear tester (NUS-ISO-2, manufactured by Suga Test Instruments Co., Ltd.) under the condition that the number of reciprocating motions of the test specimen mounting base 4 was 100 times.

A mirror-finished wristwatch case obtained by machining stainless steel (SUS316L) was washed and degreased with an organic solvent, and this substrate was mounted in an ion plating apparatus.
Next, after evacuating the inside of the apparatus to 1.3 mPa, argon gas was introduced to 0.13 Pa. In this argon atmosphere, plasma was generated by a plasma gun provided inside the apparatus, and then titanium was constantly evaporated for 10 minutes to form a Ti film having a thickness of 0.2 μm on the surface of the watch base material. It was.

Subsequently, the introduced gas was switched from an argon gas to a mixed gas of nitrogen and argon while evaporating titanium under the same conditions as when the Ti film was formed. At this time, with the gas flow rate kept constant at 300 sccm, the flow rate ratio (N ₂ / Ar) of nitrogen gas and argon gas was increased from 0 to 2.0 over 35 minutes. As a result, a TiN gradient coating having a thickness of 0.6 μm was formed on the Ti coating.

  Next, under the same conditions as when the Ti film was formed, the evaporation of titanium and the supply of a mixed gas of nitrogen and argon were continuously continued to form a 0.6 μm thick TiN film on the TiN gradient film. I let you.

Subsequently, while constantly evaporating titanium under the same conditions as those for forming the TiN film and supplying a mixed gas of nitrogen and argon having a flow rate ratio (N ₂ / Ar) of 5.8 at a flow rate of 680 sccm, Was evaporated to form a 0.005 μm thick Au—TiN mixed gradient coating on the TiN coating. At this time, the evaporation amount of gold per unit time was increased with time so that the content of Au atoms with respect to the deposition amount of all atoms per unit time increased by 2.67 atom% per second. Specifically, this Au—TiN mixed gradient coating was formed at a film formation rate of 0.02 μm / min for 15 seconds. At this time, the Au content in the Au—TiN mixed gradient coating was 8 atomic% in the film growth direction. The amount of evaporation of gold was increased with time so as to increase at a rate of /0.001 μm.

  Next, under the same conditions as the end of the Au-TiN mixed gradient coating formation, the titanium and gold evaporation and the supply of the mixed gas of nitrogen and argon are continuously continued to form the Au-TiN mixed gradient coating on the Au-TiN mixed gradient coating. An Au—TiN mixed film having a thickness of 0.01 μm was formed.

The obtained wristwatch case had a uniform gold color tone.
When the corrosion resistance test was conducted on the obtained wristwatch case, the rating number was 9.9. Further, when the abrasion test was carried out, no abrasion was observed on the surface and no abrasion scratch was observed. Further, no peeling of the Au—TiN mixed film was observed.

  As a result of analyzing the composition of the obtained wristwatch case with an X-ray photoelectron analyzer (ESCA), the Au—TiN mixed film is 40 atomic% gold, 38 atomic% titanium, 20 atomic% nitrogen, 1 atomic% oxygen, carbon. It was composed of 1 atom%. The TiN film was composed of 54 atom% titanium, 45 atom% nitrogen, 0.5 atom% oxygen, and 0.5 atom% carbon. Furthermore, in the Au-TiN mixed gradient coating, the content of Au atoms increases at a rate of 8 atomic% / 0.001 μm, and the content of Ti atoms decreases at a rate of 3.2 atomic% / 0.001 μm, The N atom content decreased at a rate of 5 atomic% / 0.001 μm. In the TiN gradient coating film, the N atom content increased at a rate of 7.5 atomic% / 0.1 μm, and the Ti atom content decreased at a rate of 7.7 atomic% / 0.1 μm. The change in composition in the film thickness direction from the Au—TiN mixed coating to the TiN coating of this watch case is shown in FIG.

  The present invention includes, for example, a watch case, a watch band, a watch crown, a watch exterior part such as a watch back cover, a belt buckle, a ring, a necklace, a bracelet, an earring, a pendant, a brooch, a cufflink, a necktie, a badge, It can be applied to medals, eyeglass frames, camera bodies, door knobs, and the like.

FIG. 1 is a schematic plan view of a wear tester for explaining a wear test method. FIG. 2 is a graph showing the result of composition analysis in the film thickness direction of the film of the watch case manufactured in the example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Test piece 2 ... Test piece holding plate 3 ... Test piece holding screw 4 ... Test piece mounting base 5 ... Wear wheel

Claims (11)

On the surface of the base material, a titanium film is formed by evaporating titanium in an inert gas atmosphere other than nitrogen in a dry plating apparatus so that the amount of evaporation per unit time is constant,
Next, while evaporating titanium in the dry plating apparatus so that the evaporation amount per unit time is constant, nitrogen gas in the dry plating apparatus is increased so that the nitrogen amount in the dry plating apparatus increases with time. To form a TiN gradient coating film having a N atom content gradient in the film thickness direction on the Ti coating film,
Next, while evaporating titanium in the dry plating apparatus so that the evaporation amount per unit time is constant, the nitrogen amount in the dry plating apparatus is kept constant, and TiN is deposited on the TiN gradient coating. Forming a film,
Next, the evaporation amount of gold per unit time while evaporating titanium in the dry plating apparatus so that the evaporation amount per unit time is constant and keeping the nitrogen amount in the dry plating apparatus constant. As a result, gold or gold and other metals are evaporated so as to increase with time, and an Au—TiN mixed gradient film having a gradient in the film thickness direction of the content of Au atoms is formed on the TiN film. ,
Next, while keeping the amount of nitrogen in the dry plating apparatus constant, the evaporation amount per unit time of titanium and gold or titanium, gold and other metals in the dry plating apparatus is constant. A method for producing a golden ornament, characterized by evaporating to form an Au-TiN mixed coating film on the Au-TiN mixed gradient coating.   When forming the Au-TiN mixed gradient coating, the Au atom content in the Au-TiN mixed gradient coating is increased per unit time so as to increase in the film thickness direction at a rate of 2 to 10 atomic% / 0.001 μm. The method for producing a golden ornament according to claim 1, wherein the amount of evaporation of gold is increased over time.   3. The nitrogen gas of 2.5 times or more of the nitrogen gas supply amount at the time of TiN film formation is supplied into the dry plating apparatus when forming the Au-TiN mixed gradient film. The manufacturing method of the golden ornament of description.   2. The gold color according to claim 1, wherein when the Au—TiN mixed film is formed, nitrogen gas is supplied into the dry plating apparatus at least 2.5 times the amount of nitrogen gas supplied when the TiN film is formed. A method for manufacturing ornaments.   When forming the TiN gradient coating, the amount of nitrogen in the dry plating apparatus is adjusted so that the N atom content in the TiN gradient coating increases in the film thickness direction at a rate of 4 to 12 atomic% / 0.1 μm. The method for producing a golden ornament according to claim 1, wherein the method increases over time.   A base material, a Ti film formed in an inert gas atmosphere other than nitrogen on the surface of the base material, with a Ti atom content constant in the film thickness direction, and an N atom formed on the Ti film TiN gradient coating having a gradient in the film thickness direction, TiN coating formed on the TiN gradient coating with a constant content of Ti atoms and N atoms in the film thickness direction, and on the TiN coating An Au—TiN mixed gradient coating having an Au atom content gradient in the film thickness direction, and an Au atom, Ti atom, and N atom content formed on the Au—TiN mixed gradient coating A golden decorative article having an Au—TiN mixed film in which the thickness is constant in the film thickness direction.   The gold decorative article according to claim 6, wherein the Au-TiN mixed gradient coating increases the content of Au atoms in the film thickness direction from the TiN coating to the Au-TiN mixed coating. In the Au—TiN mixed gradient coating, the content of Au atoms is 2 to 10 atomic% / 0.001.
The golden decorative article according to claim 7, wherein the golden decorative article increases at a rate of μm.   The golden decorative article according to claim 6, wherein in the TiN gradient coating film, the content of N atoms increases in the film thickness direction from the Ti coating film to the TiN coating film.   The golden decorative article according to claim 9, wherein in the TiN gradient coating film, the content of N atoms increases at a rate of 4 to 12 atomic% / 0.1 μm. The film thickness of the Ti coating is 0.1 to 0.5 μm,
The total thickness of the TiN gradient coating and the TiN coating is 0.5 to 2.0 μm, and the ratio of the thickness of the TiN gradient coating to the total thickness is in the range of 10 to 60%.
The total thickness of the Au—TiN mixed gradient coating and the Au—TiN mixed coating is 0.005 to 0.1 μm, and the ratio of the thickness of the Au—TiN mixed gradient coating to the total thickness is 10 The golden ornament according to any one of claims 6 to 10, which is in a range of -90%.

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