JPS61231162A - Gold-colored outer ornament parts - Google Patents

Abstract

PURPOSE:To obtain gold-colored outer ornament parts having a superior color tone and excelling in resistance to corrosion and wear by forming a TiN film with good adhesion on a base material, forming a highly corrosion resistant conductive film on it and then forming a wet plating film of gold or gold alloy. CONSTITUTION:The primary layer consisting of a component mainly composed of alpha-phase on the equilibrium diagram of Ti and N, the secondary layer mainly composed of a mixture of >=2 kinds among alpha-, epsilon-, and delta-phases and the third layer mainly composed of delta-phase are formed on the base material with satisfactory adhesion, on which the fourth layer consisting of mixed cermet layer mainly composed of delta-phase, pure metal or its alloy and nitride of the metal and the fifth layer mainly composed of the pure metal or its alloy having the same composition that is mentioned above are formed to a prescrobed thickness or below, respectively. Then the sixth layer of wet plating film mainly composed of gold or gold alloy is formed on the above. In this way, the gold-colored outer ornament parts having a gold-colored coating layer formed on a part or the whole thereof can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a gold-colored exterior component with excellent corrosion resistance and abrasion resistance.

[Conventional technology]

As a means of improving abrasion resistance and scratch resistance while maintaining the color tone, appearance, and corrosion resistance of conventional gold or gold alloy plated exterior parts for mobile watches, ordinary gold plated Or a method of applying hard plating with excellent hardness and wear resistance under finish plating with gold alloy, or Japanese Patent Publication No. 59-26664, US Pat. No. 4,252,862, Japanese Patent Publication No. 58-153776, or US Pat.
A method has been proposed in which a hard golden metal nitride or metal carbide is formed by ion plating etc. under the final plating with gold or gold alloy, or a method is coated with a mixed film of these. ing.

[Problems to be Solved by the Invention] Among the above-mentioned conventional techniques, methods based only on a combination of wet plating have limitations in hardness, abrasion resistance, and scratch resistance. In addition, in the technology of combining metal nitrides or metal carbides with gold or gold alloys, ■ Problems with poor adhesion between nitrides or carbides and gold or gold alloys. Or the problem of total recovery yield and cine quality due to gold alloy formation. ■ There is a problem of color tone control acid when forming gold or gold alloy by PVD method.

[Object of the present invention]

Therefore, the object of the present invention is to form a TiN coating with excellent abrasion resistance and corrosion resistance on the base under the final surface coating of gold or gold alloy, and to form a TiN coating with good adhesion and corrosion resistance on the base. A highly conductive film is formed below a certain thickness, and a conventional wet plating film of gold or gold alloy can be formed on this film, and the appearance, color tone, and overall recovery yield are better than that of conventional gold or gold alloy plating. This means that it can be maintained to the same level or better than the exhibited items.

In addition, even after a part of the gold or gold alloy layer has worn off after being put into practical use, the hard base layer can prevent further wear, thereby minimizing the appearance defects caused by color unevenness in this part. This is what we do.

[Means for solving problems]

The golden exterior part of the present invention has α on the equilibrium state diagram of Ti and N.
The first layer consists mainly of phase, α phase, ε phase, and δ phase.
A second layer mainly composed of a mixture of two or more phases selected from among the phases, a third layer mainly composed of a δ phase, and a δ phase and a pure metal or an alloy thereof and a metal nitride thereof. A golden coating layer on the surface consists of a fourth layer consisting of a mixed cermet layer, a fifth layer consisting mainly of pure metal or its alloy with the same composition as above, and a sixth layer consisting mainly of gold or gold alloy. It is characterized by being formed in part or in whole.

The golden exterior part of the present invention can be applied to any decorative member, such as a case member of a mobile watch, a band, a lighter case,
Effective for eyeglass frames, tie clips, rings, etc.
The base material is not limited to stainless steel, Ni-based alloy, Co-based alloy, brass, copper-based alloy such as nickel silver, zinc alloy, aluminum alloy, ceramics, heat-resistant plastic, etc.

Incidentally, the α phase, ε phase, δ phase, etc. referred to in the present invention are generally known, but in particular, they are described in the document McGRAW-BOOKCoMPANY.
Published by “HANSEN CoNSTITUTION of BINARYA”
Please refer to page 990 of ``LLOYS''.

For example, 6 near the upper limit of the ion plating treatment temperature.
At 00°C, the white α phase contains up to about 5% N by weight.
It is known that the white ε phase contains up to about 9 H of N, and the δ phase contains about 12 H or more of N, and that this δ phase exhibits a golden color. In addition, at the boundary between each phase, α + ε phase, ε + δ phase, and α + δ phase at higher temperatures.
It is known that there are also α+β phase and β phase.

In quant plating of Ti in N2 gas,
As the ratio of the amount of inflowing N2 gas to the amount of Ti evaporation increases from a state close to 0, it will change from α phase → ε phase → δ phase, and due to changes in conditions such as bias voltage and heating temperature, α phase will change. →There is also a possibility of a change in the δ phase.

Further, the features of the present invention will be explained in detail along the typical manufacturing steps (see the conceptual diagram of film formation in Figure 1, below (
( ) corresponds to the symbol in Fig. 1) [Function] ■ Regarding the base hard coating by ion plating, the present invention is directed to the formation of a TiN-based golden coating similar to that of JP-A-50-159057. Layer (1) is formed in an inert gas or in an inert gas slightly mixed with N2 gas (B
In step 1), Ti is evaporated by ion plating (C
I) A Ti film is formed, and the second layer (2) is disclosed in Japanese Patent Publication No. 53-19325° US Pat. No. 3,900,592. Tokuko Showa 5
6-21068° Japanese Patent Publication No. 56-62961. Jitsuko 59
-58442 or US Pat. No. 4,226,082, but instead of gradually increasing the N concentration, the inflow amount of the inert gas (B1) is reduced B2)T
The N concentration in the film is maintained constant at a constant inflow of 20 to 80% of the amount of N2 gas required for iN- formation (B
6) Make things the first characteristic.

This is because the color tone of the second layer (2) does not gradually change,
The purpose is to improve workability during processing, eliminate factors that cause quality variations, and facilitate color tone control. In the case of ion plating with the above gas amount atmosphere, α and ε
, at least two of the three phases of δ are formed. Furthermore, in the present invention, when forming the third layer (3), Ar gas is stopped (BS) and N
2 gas B6) to obtain a gold-colored titanium nitride layer consisting mainly of δ1.

■ Regarding gold or gold alloy coatings, the present invention is characterized in that it is possible to form gold or gold alloy coatings by wet plating, which has been well proven in the market in terms of total recovery yield, color tone, specular gloss, and corrosion resistance. The important feature is good adhesion of the conductive metal coating in this case.

From the viewpoint of emphasizing appearance quality, this conductive film must have a pure metal or pure metal alloy layer with as little contamination or exposure of defective conductors as possible, and this film must be a third base layer (3).
), as well as high corrosion resistance and good wet plating properties.

Regarding ensuring adhesion in forming a pure metal layer on a TiN film, for example, US Pat.
-153776, a method and apparatus based on the idea of ion plating + sputtering have been proposed.

In the present invention, first, in the final step of forming the third layer (3), a pure metal or an alloy thereof is used as the fourth layer (4).
Within the same batch and in the same atmosphere (in N2 gas (B6), only the gas flow rate is increased or decreased according to the evaporation amount), the amount of evaporation of Ti is also slightly reduced from an evaporation source different from Ti (3) Ti
After a certain period of time, the pure metal or its alloy is continuously evaporated (C2), and the evaporation of Ti is stopped (C5), and four layers (4) are formed, and then the pure metal or its alloy is evaporated. Increase the amount slightly (C6). At the same time or at a slightly earlier timing, the atmospheric gas (B2) is switched from a reactive gas to an inert gas (3311).

A pure metal or alloy thereof layer as the fifth layer (15) is obtained after the complete substitution with the inert gas (3312) and until the evaporation of the pure metal or its alloy is stopped (C7).

In this coating structure, the third layer (3) and the fourth layer (4) are T
The common presence of i and N provides good adhesion. The fourth layer and the fifth layer have strong adhesion due to the presence of a metal or an alloy thereof in common and the greatly improved conductivity caused by this.

The sixth layer is formed by using the fifth layer as a base and applying a normal wet plating process to, for example, A11-Ni-In based layer 24.
Au-Ni system, Au-(:u-pd system, Au-Cu system.

Wet plating can be performed with all gold or gold alloys that have been conventionally used for exterior parts of portable watches, such as Au-Cu-Cd, and all gold or gold alloys that may be developed in the future. In addition, in the case of products and grades where restrictions such as gold recovery rate, color tone, appearance, etc. can be ignored, methods other than wet methods such as sputtering, vapor deposition ion plating, etc. can be used to form the gold or gold alloy layer. . Also in this case, the fifth layer has the same effect on improving the adhesion of the sixth layer. As long as the sixth layer is a gold or gold alloy layer, it may be multilayered by a combination of wet plating and surface treatment other than wet plating.

For the purpose of improving adhesion, heat treatment at a temperature below the recrystallization temperature of the paste material after the formation of the seventh layer film is also highly effective.

A little more explanation is as follows.

■ Regarding the pure metal layer or its alloy layer in the coating and related coatings, the fifth layer aims to improve the adhesion, specular gloss, and corrosion resistance of the sixth layer, but the metal composition must be able to withstand these requirements. are pure Pd, pure C09pd-C,O alloy, p
A d-Ni alloy or a Co-Ni alloy is optimal. These alloys are all solid solution combinations, but alloys containing Ni have poor corrosion resistance, so the amount of Ni in Pd-Ni is limited to 90 and the amount of Ni in Co-Ni is limited to 80. shall be. The composition of the Pd-C0 alloy is not limited because it is a solid solution and has good corrosion resistance in any composition.

Furthermore, regarding the pure metal or alloy part other than Ti, N, and metal nitride in the fourth layer, it is possible to follow the composition ratio of the fifth layer.
It is advantageous in manufacturing. However, a combination in which the fourth and fifth layers have different metal or alloy ratios may be used.

■Restrictions on film thickness The purpose of the fourth layer is to ensure adhesion between the third and fifth layers, but if it is less than about 30λ, its effect will be small, and if it exceeds about 200OA, there will be a large difference in color tone from the third layer. becomes.

The purpose of the fifth layer is to improve the adhesion of the sixth layer.

Hardness is not high because the coating is ion plated in an inert gas. Therefore, there is no practical problem even if the current is applied up to about 500 OA. However, if the current is about 30 A or less, color unevenness, fogging, or poor adhesion is likely to occur during subsequent wet plating.

■ Regarding the metal component ratio of the cermet part, the Ti of the fourth layer
Pure metal components or alloy components other than pNt metal nitride have a favorable effect on the adhesion, especially in the fifth layer and beyond, but the weight ratio is 3.
If it is less than 50 cm, there is little effect on adhesion, and if it is more than 50 cm, it will not exhibit the golden color of TiN, causing problems after being used in practical use.

The present invention will be described in detail below with reference to Examples.

[Example-1] 250 portable watch cases were manufactured from SUS 304 material, and 200 of them were placed in an ion plating device after organic cleaning. Bombarded at a bias voltage of 450 V in an Ar gas atmosphere of 5 x 10" Torr, and evaporated by Ti with an electron beam of 500 A at a bias voltage of 30 V in an Ar gas atmosphere of 5 x 10" Torr. was formed (first layer formation). While continuing to evaporate the 5 minute diameter Ti from the start of formation, part of the Ar gas was replaced with N2 gas in the same vacuum range, held at a N2 gas flow rate of 55 cc/min for 3 minutes (second layer formation), and then N2 The gas flow rate was set to 110 cc/min, the flow of Ar gas was stopped, and the process was performed for 3 minutes (third layer formation). Furthermore, in the same atmosphere, Pd was heated at 180A from a resistance heating source.
The electron beam on the Ti side was set to 28 OA, and after holding for 1 minute (fourth layer formation), the Ti evaporation source was shuttered.
The electron beam was set to 0 to stop the evaporation of Ti, and the Pd was
Evaporate with A and at the same time stop the N2 gas inflow and switch to argon gas.5. Ox10 Torr, 1.5m
A pd film was formed as 1n (fifth layer formation). For 50 of these, PdNII″f!: Hess, Au
- After flushing, a coating of 1.9μ was applied to Au-Ni-In-based 22.5 by wet plating. In addition, another 50 pieces were similarly coated with a coating of 2.1 μm on Au-Cu-PD type No. 21 by wet plating.

Another 50 pieces were subjected to sputtering using a 4% Ni--Au alloy as a target to obtain a film of 2.1 μm, followed by heat treatment at 500° C. for 2 hours in a water atmosphere. The remaining 50 Pd products were left as they were. Furthermore, of the 50 cases that were not ion plated, 25 of them were wet-plated with a 2μ Au-Ni-In alloy, and the remaining 25 were the same wet-plated products with a thickness of 4μ.

For these six types of samples, artificial sweat, artificial seawater,
Abrasion resistance test, bending test, corrosion resistance test after abrasion resistance test,
As a result of conducting bending adhesion tests after the corrosion test, the product of the present invention showed much better results than the product with stainless steel paste and only wet plating, and at the same time, the product with only Pd film did not discolor due to artificial sweat. However, other characteristics showed good quality.

[Example-2] A sample 500 plate of SUS 304 plate 4011x 4011x 5H was used as the substrate, and the fourth layer of Example-1.

The metals forming the fifth layer are pure Pd and pure Co.

Pd-50chi Co alloy, pd-70chi Ni alloy.

Co-6Q-Ni alloy and pure Ni were used as evaporation sources, and 50 ions of each were ion-plated under the same conditions as in Example-1. In addition, all parts are wet plated with Au.
-Ni-In coating of 1 μm was applied, and 25 pieces of each were subjected to an artificial sweat test, a corrosion resistance test at 40°C, and a nitric acid steam test at 25°C. As a result, pd-Ni and co-Ni
In some cases, corrosion and discoloration occurred in some parts of the fifth layer, and in all pure Ni-based cases, corrosion and discoloration occurred in the fifth layer.

As a result of analyzing the fifth layer of pd-Ni and Co-Ni samples with corrosion or discoloration,
It became clear that the discolored or corroded parts of the sample were rich in Ni content. In particular, parts of the sample that have poor repulsion with respect to the evaporation source are Co, or N with respect to Pd.
It has become clear that the limit for corrosion resistance is 80% Ni for Co and 90% for Pd.

In addition, the remaining 25 samples were subjected to an abrasion resistance test, a folding test, and a corrosion resistance test after the abrasion resistance test.

After conducting the corrosion resistance test, the bending adhesion test etc. resulted in pure PD.
, pure Co, and Pd-Co-based samples showed good results in all tests, and some of the pd-Ni-based, Co-Ni-based, and pure Ni-based samples showed good corrosion resistance and
It did not perform well in the bending adhesion test after the corrosion resistance test.
Only other tests showed good results. The defects in this case were almost the same as the results of the artificial sweat and nitric acid steam tests.

[Example-5] As shown in Fig. 2, 80. .

Prepare 100 sheets of x40m x 3mt a), bend it by half the length in the longitudinal direction at an elevation angle of 10° (this bent part is designated as A) (b), and bend it under the same conditions as Example 1. The first to fifth layers are subjected to ion plating treatment from the direction of F (C), after the ion plate ink treatment, the folded part of the sample is returned to its original position (d), and then wet plating is applied to the Au- Ni-In plating of 4μ was applied (el. These 100 samples were bent in a direction perpendicular to the above-mentioned folded part (refer to the folded part B)), and a film adhesion test was conducted. . As a result, the coating mainly peeled off from the inner portion of the bent portion A. This peeled part becomes part QC in FIG. In addition, in Figure 2, which includes this part, the range of E indicated by ) is gold-plated (e).
Capri occurred at the end of the process. There is almost no metal Pd detected on the base side of the peeled part, and a mixture of Pd and Ti or no Ti is detected on the peeled coating side, so it cannot be concluded that the peeling is between the third and fifth layers. ,
TEM-XM the coating thickness along the direction shown in the second diagram.
As a result of measurement and analysis using the ultra-thin section method A, it was found that poor adhesion occurred in the range below the estimated value of approximately 30A, and the cost was low. In addition, as a result of a similar investigation of wet plating capri occurrence areas, it was found that capri occurred in areas where the thickness of the fifth layer was less than the estimated value of approximately 60A, and it was clear that the gloss of the wet plating film was impaired. became.

[Example-4] The same sample as Example-2 was ion-plated in the same process as Example-1, but only the fourth layer molding time was extended,
As a result of sampling as it is, the thickness of the fourth layer is approximately 200 mm.
It was found that at 0A or higher, the coating became brownish and the specular gloss decreased.

[Example-5] 120 proprietary type cases were manufactured using SUS 504 material, and the same coating as in Example-1 was formed, and the thickness of the fifth layer at the thickest part of the tip was 4900λ. , 520
Balance with the aim of 0A and 5500A, 2 each
We made 0 prototypes. This is wet plated with Au-Cu-C.
d When a 2μ plating was formed and an abrasion resistance test was conducted on the heel part using cowhide, all samples aimed at 5200A or more showed that the raceway surface was white from the tip and was easily visible, and Similar results were obtained in the practical mobile test.

The thickness of the fifth layer of the sample aimed at 5200A is approximately 5.
It was 10OA.

[Example-6] At the time of forming the fourth layer, the evaporation amount of Ti and Pd and the balance of N2 gas and acetylene gas were varied.
When the amount of Pd exceeded 50 inches by weight, the color of the film was not white and it was hard with Hv1200, which was a problem in practical use. In addition, when it was 3% or less, poor adhesion occurred frequently between the fourth and fifth layers.

〔Effect of the invention〕

As described above, according to the present invention, a TiN coating that is easy to manufacture, inexpensive, and has excellent wear resistance and corrosion resistance is formed under the final surface coating of gold or gold alloy with good adhesion to the base. A conductive film with good adhesion, high corrosion resistance, and no contamination of metal nitrides with high hardness is formed to a certain thickness or less, and a conventional wet plating film of gold or gold alloy is formed on this film. We were able to maintain the appearance, color tone, and overall recovery yield at or above the same level as conventional gold or gold alloy plated products. Even when the sixth gold (alloy) layer and the fifth Met layer are worn away, the fourth layer of titanium nitride layer exhibiting a golden color appears, so the golden color is not impaired in appearance.

Further, even after a portion of the gold or gold alloy thickness has worn off after being put into practical use, the underlying hard layer can prevent further wear.

[Brief explanation of drawings]

FIG. 1 is a conceptual diagram of film formation from the first layer to the sixth layer due to changes in evaporated substances, evaporation amounts, inflow gases, and inflow amounts during ion plating in the present invention. 1... First layer (mainly α phase) 2... Second layer (mainly a mixture of two or more of α phase, ε phase, and σ phase) 3... Second layer 3 layers (mainly α phase) 4...Fourth layer (mainly δ phase, metal, metal nitride)
5...Fifth layer (mainly metal) M...Base material Figure 2 is a conceptual diagram of the process of adhesion test in Example-3. A...First diffraction bending part B...Second bending part C...Coating peeling part D...Coating thickness measurement part E...・・・Exceeding the capri occurrence range on gold plated surface

Claims (9)

[Claims] (1) The first layer consists mainly of the α phase on the Ti and N equilibrium phase diagram, and the mixture of two or more phases selected from the α phase, ε phase, and δ phase. a second layer, a third layer mainly composed of δ phase, a fourth layer consisting of a mixed cermet layer mainly composed of δ phase and pure metal or its alloy and metal nitride, and pure metal with the same composition as above. A gold-colored exterior component characterized in that a gold-colored coating layer is formed on a part or the entire surface, consisting of a fifth layer mainly composed of gold or an alloy thereof, and a sixth layer mainly composed of gold or a gold alloy. . (2) The golden exterior component according to claim 1, wherein at least the first layer to the fifth layer are formed by an ion plating method within the same batch. (3) The gold color according to claim 1, wherein the pure metal or its alloy portion of the fourth layer and the fifth layer are mainly pure PD or a Pd-Ni alloy containing up to 90% Ti by weight. Exterior parts. (4) The pure metal or its alloy part in the fourth layer and the pure C in the sixth layer
Claim 1 in which O or Pd-Co alloy is the main component
Golden exterior parts listed in section. (5) The golden exterior component according to claim 1, wherein the fourth layer of pure metal or its alloy portion and the fifth layer are mainly composed of a Ni--Co alloy containing up to 80% Ni by weight. (6) The golden exterior component according to claim 1, wherein the fourth layer contains a pure metal or an alloy thereof in a weight ratio of 3% to 50%. (7) The golden exterior component according to claim 1, wherein the thickness of the fourth layer is in the range of about 30 Å or more and about 2000 Å or less. (8) The golden exterior component according to claim 1, wherein the thickness of the fifth layer is in the range of about 30 Å or more and about 5000 Å or less. (9) The sixth layer is Au-Ni-In alloy, Au-Ni alloy, Au-Cu-Pd alloy, Au-Cu-Cd alloy, A
The golden exterior component according to claim 1, which is a layer formed by wet plating of a u-Cu alloy or an Au-Cu-Ag alloy.