JPS5881966A - Exterior parts for portable watch - Google Patents

Abstract

PURPOSE:To provide exterior parts for a portable watch not thoroughly losing characteristics of a TiN film and having appearance entirely equal to gold plating, obtained by forming four layers comprising a TiN layer, an Ni layer, a gold plating layer and a gold-Ni-In layer on the surface of exterior parts. CONSTITUTION:After a vacuum chamber 1 is evacuated through an evacuation port 2, an Ar gas is introduced into a chamber 1 from an introducing port 3 to hold internal pressure to 2X10<-4>torr and voltage of 30-60V is applied to an ionizing electrode 6 from a power source A. In addition, voltage of -400- 1,200V is applied to a base plate 5 comprising a stainless steel watch case arranged in the chamber 1 from a power source K and, after the introducing port 3 is changed over to N2 to hold the internal pressure to 6X10<-4>torr, the evaporation source 4 and an evaporation power source B are operated to carry out ion plating at a production speed of 10-50Angstrom /sec to form a TiN film with a thickness of 0.1-6mum. In the next step, this TiN film is immersed in an acidic bath containing nickel sulfate to form a Ni film by electroless plating and the plated base plate is immersed in an electrolyte containing gold cyanide to apply substitution type electroplating and finishing electroplating of gold is further carried out to obtain the titled exterior parts having a gold-Ni-In strike layer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the improvement of decorative exterior parts, especially gold-colored exterior parts. This invention relates to an exterior part for a mobile watch, characterized in that a 1M layer is formed by electrolytic plating, and a gold-nickel-indium layer is formed by electrolytic plating as a finishing layer of metal by substitution type electroless plating. .

Exterior parts for wristwatches have traditionally had a strong decorative element, and the outer parts of the exterior parts have a strong decorative element. The value difference between the products is easily influenced (also, because people are always using mobile phones,
There is a growing demand for the quality of exterior parts to withstand long-term mobile use. Therefore, exterior parts for mobile watches must have excellent appearance quality such as gloss and color, and materials must have excellent corrosion resistance and abrasion resistance. has been done. Among these exterior parts, gold-plated exterior parts are most widely used and valued due to their decorative value, but due to the recent rise in the price of gold, the cost of gilding has become very high, and the hardness has also increased. II
Since the v150 level is so low, the quality of the appearance deteriorates even after long-term use, and there are two problems.

In recent years, the hard, abrasion-resistant, gold-colored titanium nitride film formed by ion blating technology has been attracting attention as a new surface treatment technology that can be used as a surface treatment film for exterior parts and can replace gold plating. By using titanium, which is less expensive than gold plating, it is expected that manufacturing costs, especially material costs, will be significantly reduced. The above-mentioned ion plating technology and UB 10''1-1 (1) In a low-pressure gas atmosphere evacuated to a vertical vacuum, the substrate is placed opposite to the cathode and the evaporation source is opposed to the anode, and when a voltage of several KV is applied between them, glow discharge occurs. is generated, and the gas is ionized and becomes a plasma.In this case, the object to be treated is placed at the @ pole, the coating material is placed at the anode, and the anode is heated.The coating material evaporates and the gas ions of the plasma Since the mean free path of the evaporated metal ions is short, they repeatedly collide with each other and deposit on the fractured workpiece.
It also precipitates in the pores, and the kinetic energy of the evaporated material is very high (therefore, a dense film is obtained and the adhesion is good. This is one of the reasons for the improved adhesion, as substances are constantly sputtered into the ionized gas.Furthermore, since the coating material is evaporated and supplied, a large amount can be supplied, resulting in a faster deposition rate. It is possible to form a thick coating in a short period of time.In addition, the film obtained by the ion blating method has many advantages over the conventional vapor phase coating.

The titanium nitride film is formed by the reactive ion blasting method in which a gas containing M is introduced into the plasma described above to form a compound of 1% Nl and evaporated metal of T. Generally, it is hard and has excellent wear resistance, and the color m111 is golden yellow. For this reason, in recent years, gold plating has been replaced by gold plating, which has been put into practical use as exterior parts for watches.However, especially for watch exteriors, whose value tends to be influenced by appearance, although it is golden in color, it is not completely gold in color. It is hard to argue with a new technology that has limited commercial value and can completely replace gold plating.

The present invention is for exterior parts! One-sided treatment coating, titanium nitride, nickel, gold plating, and gold-nickel-indium were used to remove the conventional technology and remove the hammer, without losing any of the characteristics of titanium nitride pancreas. It has now become possible to provide an exterior part for a watch having the appearance of the following.The present invention will be described in detail below with reference to Examples.

The figure shows an example of an ion brating device for providing the exterior part for a timepiece according to the present invention. Ion blasting i*f shown in Figure 1: In practical terms, vacuum chamber 1 is connected to exhaust system 2.
After exhausting the gas, make a gas introduction system 3 and introduce argon gas to maintain the vacuum chamber 1 t 2 XIOtorr, apply an ionization electrode 6 to the same power supply voltage of +60"I E5, and then remove it from the stainless steel watch case. -40 to the substrate 5
After applying a voltage of 0 to 1200 V with the power supply, switch the gas introduction system valve to nitrogen and add 6
rrK maintenance [7, evaporation $4. Activate the same power supply B and
Reactive ion brating between 205+ and 0.1μ to 6μ thickness with ~50A/860 generating station nW = 20
00 titanium nitride was formed. As a result, a watch case with a bright golden color was obtained. Further, the titanium nitride coating was activated by immersing it in hydrofluoric acid 154 sulfuric acid for 35+ minutes, followed by 30 f/J of nickel sulfate and 20 f/Z of sodium hypophosphite.

Sodium acetate 14 t/A, sodium citrate added 4, ammonium chloride 5 f/J, lactic acid 0.5 f/7
Electroless plating was performed by immersing the blade in a 40° C. composition bath for about 300 OA to form H41fjjt-. Furthermore, gold potassium cyanide 2 f/J, [ammonium chloride 75
1μ, sodium oxalate 50 f/Z, and sodium phosphite 10 fμ in a 90° composition solution &C for 1 minute.A layer was formed on 24 of 500X. Furthermore, as a finishing touch, potassium gold cyanide 1
(l f/J, citric acid 901/J, nickel cyanide 0.5 f/l, insium cyanide 15f) in a 45°C composition bath. A strike layer of Tsukeru-indium was formed. As a result, the watch case became gold in appearance and withstood the corrosion resistance test of immersion in artificial sweat and artificial seawater for 24 hours, and also passed the thermal shock test of rapid cooling from ℃ to room temperature and 900℃ of corrosion resistance. Even in the bending test, the adhesion between the electroless plated titanium nitride film and the nickel layer and the nickel layer was good and no peeling occurred.Furthermore, the wear resistance test showed that the adhesion between the electroless plated titanium nitride film and the nickel layer and the metal was good, and no peeling occurred. Gold-nickel-indium layer #: t3000
3 times due to wear due to the titanium nitride coating as the base layer.
Even after 10,000 wears, the base material was not completely exposed and the appearance of the worn area was the golden color of the titanium nitride film with no problems at all.

By using the above-mentioned invention, the exterior parts of watches can be plated with the conventional expensive metal plating.

It has become possible to use a gold-plated case with excellent corrosion resistance and wear resistance at a low cost, and a new technology has been realized to replace the conventional general gold-plated case.

[Brief explanation of drawings]

FIG. 1 is a simple sectional view of an ion blating device for providing the exterior parts of the present invention. 1.-Vacuum chamber 2..Exhaust system 4..Evaporation source 5e Kenki @ (watch case) Applicant: Hoei Kosha Co., Ltd.! lPi prisoner

Claims (1)

[Claims] ■ The ion blating method uses titanium nitride as the base layer, M(layer) as the intermediate layer, and a gold plating layer on top of it.
A portable exterior component characterized by forming a gold-nickel-indium layer as a finishing layer. ■ Claim 1, characterized in that the IT layer as an intermediate layer is formed by electroless plating, the primary metal is formed by substitution type electroless plating, and the gold-nickel-indium layer as a finishing layer is formed by electroplating. Exterior parts for portable watches as described in section. ■ Titanium nitride as a base layer of 0.1 μ to 6 μ, intermediate layer of Mttd', 1 to o, s μ, and K14l
Claim 1, characterized in that the thickness of the gold-nickel-indium finishing layer is 0.1 to 0.5μ, and the finishing layer of gold-nickel-indium t-0.1 to 0.5ts is formed. Exterior parts for mobile watches.