JPH03226556A - Production of ornamental member - Google Patents

Abstract

PURPOSE:To obtain a multicolored ornamental member excellent in adhesive strength, corrosion resistance, and wear resistance by removing the part, other than the part masked with solder resist, from the surface of a Ti type hard film applied to the surface of a metallic material by an ion plating method. CONSTITUTION:Ti is applied by means of ion plating to the whole surface of a material made of metal or alloy or an ornamental member prepared by providing an undercoat layer on the above material, such as a watchcase 1 made of SUS304, and then an N2 gas is introduced as a reactive gas to form a TiN layer. Further, a C2H2 gas is introduced, and finally a hard gold-colored film 2 composed essentially of Ti, N, and C is formed on the above material. Subsequently, a pattern is printed with a solder resist agent by means of screen printing, and this resist agent is dried and then hardened by heating, by which a patterned masking fill 3 is formed. This material is immersed into a mixed solution of hydrochloric acid and nitric acid in the volume ratio of 1:1, by which the film 2 in an unnecessary part is removed by etching. Then, this material is immersed into an organic solvent to undergo the removal of the film 3 by peeling, by which the watchcase having two colors formed by the combination of the material 1 and the film 2 can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing a decorative member, such as an exterior part for a watch, whose appearance is finished in multiple colors.

[Summary of the invention]

In the present invention, a Ti-based hard coating is applied to the entire surface of a metal or alloy material or a decorative member with a base layer provided on the material by ion plating, and the Ti-based hard coating is optionally applied by tacho printing and screen printing. The surface is masked horizontally or character-wise with a solder resist, and the Ti-based hard coating other than the masked areas is peeled off and the masking is removed to form a Ti-based hard coating on a part or the whole. III, J l't having multiple color tones of coating color and moon color or base layer color
('): It is an object of the present invention to provide a method for manufacturing a decorative member having excellent adhesion and abrasion resistance and having high decorative value.

[Conventional technology]

As a manufacturing method for multi-colored products by changing the appearance color tone of the horizontal or letter parts and other surfaces of decorative parts such as 311r1 exterior parts, ■ Wet plating such as gold plating is applied to the entire surface and masking for plating! A method in which after printing with R material, the wet plating other than the masking area is removed ^1 [and then the masking paint is removed.

■Printing on a metal base assembly by pad printing or screen printing, and then forming a film by an ion plating method, as in Publication Special Publication D1, 1986-75660,
A method to make the metal surface multicolored by peeling off the coating on the printed area.

■At the time of publication, as in Publication No. 81-117269, a plating layer of nickel plating, copper plating, or their alloys is formed on the entire surface of the board, and then an organic resist is applied to the important parts of the dry plating, and after hardening by baking, the plating layer is dissolved and removed. , then there are
A method in which the quality resist is dissolved and removed, a dry plating layer is formed, and then the plating layer is dissolved and removed.

- Boat fishing.

[Problem to be solved by the invention]

However, the above-mentioned IF technology has several drawbacks.

In the method of ■, the design point is the pattern, the character part is 4
Because it is treated with formula plating, the coating hardness is Hv200~3
00, and is easily worn and damaged by contact with clothing, daily necessities, and buildings during the practical use period, and the appearance of horizontal lines or letters due to the soft wet plating finish deteriorates significantly due to scratches and abrasion. There are major drawbacks as a product.

In method (2), the temperature of the substrate surface increases during the ion plating process due to the influence of radiant heat due to the melting of the evaporated metal, so the gas inherent in the masking and the decomposed gas of the masking are generated as released gas during the ion plating process. This adversely affects the formation of the ion plating film, causing interference colors, color unevenness, discharge, and poor adhesion of the film. In addition, chipping and overgrowth tended to occur on the outer periphery of the masking, which tended to impair the intended appearance. For this reason, there was a drawback that the yield rate was extremely low, making mass production difficult and increasing costs.

In method (2), over-etching occurs under the resist film when a plating layer such as a nickel plating layer is removed after resist application. In addition, due to the heat generated during dry plating, nickel,
Copper or its alloy thermally diffuses onto the substrate surface, causing discoloration of the substrate surface. In addition, it takes a long time to remove the plating layer such as the nickel plating layer after dry plating, resulting in poor work efficiency.

In the methods of Zaraani■ and ■, the pattern and letters are finished with precious metal plating such as gold plating, first the entire surface is coated with t't#.
L-group plating is applied, then masked in a pattern using masking plating or a printed mask, and a film with a different color tone from the precious metal plating is formed, and the masking part is peeled off and M removed, so even areas where precious metal plating is not visible on the outside can be coated. It has the disadvantage of being plated with precious metals, which is a major factor in increasing costs.

Therefore, the present invention is intended to solve these problems, and its purpose is to form a Ti-based hard coating in a horizontal or letter shape with a coating hardness of HvlOOOO or higher and a metallic feel with high decorative value. By printing with a solder resist that can withstand partial peeling of the Ti-based hard coating, we are able to maintain the appearance of patterns and text, which is a design point, over long periods of use, and by printing with a solder resist that can withstand partial peeling of the Ti-based hard coating, we can create complex patterns and text on the Ti-based hard coating. It is an object of the present invention to provide a method for manufacturing a decorative member having high quality, excellent finish adhesion, corrosion resistance, scratch resistance, and abrasion resistance, and having high decorative value.

[Means to solve the problem]

The method for producing a decorative member of the present invention includes (1) applying a Ti-based hard coating to the entire surface of a metal or alloy material or a decorative member with an underlayer provided on the material by ion plating, and then tacho printing and screen printing. Masking is applied to any surface of the Ti-based hard coating using a solder resist in a horizontal or letter-like manner, and the Ti-based rI! l! By peeling off and removing the hard coating and further applying the masking process, a part or the whole of the Ti-based hard τ1 coating color and base I
It is characterized in that it can be finished in multiple colors with the color of the base layer or the color of the base layer.

(2) It is also assumed that the metal listed in OII or the alloy element I is stainless steel, Ti, a Ti alloy, a copper alloy, or a zinc alloy.

(3) Furthermore, the base layer is Cu, N by wet plating.
It is characterized by nine layers or several types (I41 layer) of Ni, Pd, Ni-gold alloy, Pd base metal, Rh, gold, gold alloy, or Cr-based hard 7'l sleeve 119 made by ion plating.

[Effect]

1. of the present invention. According to Kisuri, the horizontal lines or letters formed on any surface of the decorative float 4, which is a design point as an ornament, are given an N1 finish that is scratch resistant (') and abrasion resistant.1. A Ti-based ion plating film is formed on the product, which allows the original decorative appearance of the product to be maintained without deteriorating the appearance of the patterns and letters, which are the appealing points of the decoration, even with long-term 11% banding. I'm doing it like that.

It is well known that a hard film can be produced by forming a Ti compound film of Ti, C, N, and 0 using an ion plating method. It is also well known that the coating has excellent abrasion resistance and scratch resistance, and has a metallic luster texture. However, although the ion plating film has high hardness, it has the characteristic of becoming brittle because the internal stress increases as the film thickness increases. Therefore, in the present invention, in order to obtain adhesion as a decorative member, the thickness of the single hard coating layer is set to 0. Adhesion is ensured by setting the thickness of the laminated portion to 2 to 1.5 μm, and in the case of lamination, to 3 μm or less. When the thickness of the laminated portion exceeds 3 μm, the adhesion begins to deteriorate due to the influence of the internal stress described above. In particular, peeling between coatings is likely to occur, so for decorative members, the single layer thickness of the hard coating is 0.2 to 1.5% from the viewpoint of adhesion.
A range of .mu.m is preferable, and a range of 0.2 to 0.8 .mu.m is optimal. In addition, the hard coating single layer thickness is 0.2 μm.
Since the thickness is thin, the scratch resistance is 1'F, and the abrasion resistance is 4'F.
If the quality is poor, the predetermined color tone becomes unstable and cannot be ensured, so this can be avoided. (In addition to the ion plating method, similar physical fr
A sputtering method or a chemical evaporation method ((:VD method)) and a plasma chemistry: 5?f method (PCVD) vF, which can be easily applied to the r method, can be easily applied.

Next, the gold/black-gray color of the Ti-based hard coating produced by the ion plating method is produced by using Ti, N, and C elements, which are produced using Ti or a Ti alloy as an evaporation source and nitrogen-based gas and hydrocarbon-based gas as reaction gases. Compounds can be applied. For the black-brown type, a compound of Ti, C, and O elements produced by using Ti or a Ti alloy as a 71 source and using a hydrocarbon gas and an oxygen gas as a 11 gas can be applied. For the blue color, a compound of Ti and C elements produced using Ti or a Ti alloy as an evaporation source and oxygen gas as a reactive gas can be applied. Also Cr-based 1iIJ! For the 141-layer M film, a black-gray compound of Cr and one or more of ClN and O, and a stainless steel compound of Cr, N, and C can be applied.

Next, as a material for the decorative member of the present invention, for example, when using an ion plating method, basically any material may be used as long as it can withstand the temperature during the ion plating process. For example, ceramics, cemented carbide Ni-based alloys, Co-based alloys, stainless steel, copper alloys, zinc, lead alloys, plastics, etc. can be used. Since most of the hard coatings obtained by the ion plating method have relatively pinholes, it is necessary to satisfy the corrosion resistance quality before applying the hard coating.

Substrates such as ceramics, carbide Ni-based alloys, Co-based alloys, and stainless steel have good corrosion resistance, so they basically do not require base plating, but stainless steel with a high free-cutting component such as S (sulfur) Since the substrate has somewhat poor corrosion resistance, it is necessary to use a single layer or a stack of several layers of gold, gold alloy, chromium, palladium, palladium alloy, ruthenium, or rhodium plating layer as an underlayer to ensure the corrosion resistance of the substrate. In addition, when copper alloy, zinc, or zinc alloy is used as a substrate, copper, Ni, or Ni alloy is plated in a single layer or in a laminated manner (wheat, gold, gold alloy, chromium, palladium, palladium alloy, rhodium, ruthenium, etc. are plated). It is necessary to ensure corrosion resistance by using a single layer or multiple layers.

In particular, for copper alloy, zinc, and lead alloy substrates, the above-mentioned subplating is applied before ion plating to prevent the substrate material from being directly exposed to high temperature and high vacuum atmosphere during ion plating. It is possible to prevent the temperature rise inside the substrate material and prevent the occurrence of blisters due to the dezincing phenomenon. Furthermore, when plastic is used for the substrate, it is common to apply Ni to the copper alloy, zinc, and zinc alloy substrates mentioned above by electroless plating prior to the same plating process as plating. .

Since the plastic substrate has a low melting point and is an organic substance, gas is likely to be blown out due to the temperature rise during the ion plating process, resulting in frequent failures in adhesion of the ion plating to the film. "Prevention of poor adhesion" 2.
] Plating becomes essential.

In terms of productivity and functionality, the optimal thickness of the subplating is 2 μm to 10 μm, whether it is a single layer or a laminated layer, but even if the range is expanded to 0.2 μm to 20 μm, the basic product T1 will not change. .

Next, a method for manufacturing the ff1li part shrine of the present invention will be described.

In the present invention, a Ti-based hard coating is first formed by ion plating on the entire surface of a metal or alloy material or a decorative member provided with an appropriate base layer on the material. Since masking with an organic paint is not performed before ion plating, the quality such as adhesion and appearance is good, and a good product rate of almost 100% can be obtained. Next, the pattern and letters are masked using solder resist [.] by tacho printing or screen printing. The use of tacho printing and screen printing is selected depending on the shape of the decorative member to be printed. If the shape is flat, screen printing is used; if the shape is not flat, such as a rounded surface or slope, tacho printing is used6.
In addition, in the case of screen printing, one coat of resist can be applied, so printing only needs to be done once, but in the case of tacho printing, since the resist is thin, it is necessary to repeat the process of coating and drying 2 to 3 times. Generally, a strong acid solution of boiling acid + nitric acid is used to remove Ti-based hard coatings, so if the masking is too weak, there is a risk of being immersed in the peeling N 1lJi.
The thicker the masking, the better. Next, we will discuss masking agents. As mentioned above, Tl-based peeling is 1%! Because the liquid is a strong acid,
A general masking agent such as a masking agent for plating has low acid resistance, and the masking agent dissolves when immersed in the peeling 1111t solution, causing floating and the like, making it impossible to obtain the desired appearance.

In the present invention, as a result of various experiments, it has been found that the above-mentioned problems can be completely alleviated by using a solder resist. Solder resist is generally used as a solder plating resist for circuit boards, but in the present invention, by applying this resist, a high quality Y( It made it possible to peel it off.

After partially peeling off the Ti-based hard coating, the masking agent was removed using Htlig agent, and finally 1! A multi-color appearance of the Ti-based hard coating color formed in a character shape and the base I4 color or the base layer color can be obtained.

〔Example〕

Embodiments of the present invention will be described below based on the drawings.

Example 1 FIG. 1 shows step by step the manufacturing process of a filli member of the present invention, which is finished in a composite color of SUS base color and patterned golden hard material. First, as shown in Figure 1(a), 8033
Argon gas was introduced into the watch case 1 formed by 04 in an ion plating device, the pressure was maintained at 0.02 torr, and ion bombardment was performed for 5 minutes at a negative voltage of 0.5 kV applied to the substrate to remove the surface of the watch case substrate. Cleaned. Next, after exhausting the argon gas and returning the vacuum chamber to lXl0-'torr, pure T1 was heated to 0. After 2μm ion plating and introducing N2 gas as a reactive gas, the TiN layer was 0.2μm thick.
m was formed. Furthermore, C2H2 gas is introduced and N2 gas and C2
H2 gas is introduced at a ratio of 2:1 up to 9X10-'torr, and finally the entire surface of the watch case 1 is coated with Ti, N,
As shown in (b), a 0.5 μm thick golden hard coating 2 containing C as a main component was applied by screen printing using a commercially available solder resist agent (manufactured by Taiyo Ink Manufacturing Al) as shown in (c). A pattern was printed, and after air drying, it was cured for 15 minutes at 120°C in a hot air dryer to form a patterned masked mask. The gold-colored hard coating 2 on the unnecessary portion was etched away by immersing it in a mixed solution of hydrobutic acid and nitric acid at a ratio of 1:1, and then, as shown in (e), it was etched. 1! By immersing it in a solvent and peeling off the masking material III 3, the finished appearance exhibits two colors due to the combination of the 5US304 material 1 and the patterned golden hard coating 2.
One case was formed. The stainless steel watch case made using this method has a coating hardness of Hv12 in the golden pattern.
It was 00.

Quality test is artificial sweat corrosion resistance test (40°C x 90% humidity x 4
8H), artificial seawater corrosion resistance test (40°C x 90% humidity x 4
8H), bending test (180° bending), heat shock test (heating at 300°C for 10 minutes → quenching in water, repeated 5 times), abrasion test (500 g 6<7 weights on cowhide was applied to the watch case) , rubbing the patterned part of one GT case 30,000 times with a 5cm stroke), and a scratch resistance test (dropping 20 times from 1 meter above vinyl tile). It satisfies the properties of hardness, abrasion resistance, and scratch resistance.

Embodiment 2 FIG. 2 is a step-by-step process of manufacturing a decorative member of the present invention, which uses hard coatings of different tones to create a character-like multicolor finish. First, the surface of the decorative wire for a watch rim 1 formed of 3U3304 shown in FIG. Ion plating was performed using C as a reactive gas, and the C shown in (b) was applied to the entire surface.
A gray-black hard coating 4 containing r, O as a main component was coated to a thickness of 1 μm. Next, it was taken out of the ion plating device, and after checking the appearance, color tone, etc., ion bombardment was performed again in the ion plating device in the same manner as in Example 1, and then the entire surface was coated with (C) by ion plating. A 0-order (d
) As shown in Example 1, characters were printed by tacho printing using the same solder resist agent as in Example 1, dried naturally and cured to form a character-shaped masking film 3, and then gold colored as shown in (e). Remove unnecessary parts of the hard coating 2 by etching,
Next, as shown in (f), by peeling off and removing the masking film 3, a decorative rim for a watch is formed which exhibits two colors due to the combination of the gray-black hard film 4 and the letter-shaped golden hard film IllI2 as a completed appearance. I let it happen. The surface hardness of the gray-black hard coating obtained by this method was Hv1500 or more, and the surface hardness of the golden hard coating was Hv1200. Also, Example 1
As a result of the same quality test as above, the material satisfies the corrosion resistance, adhesion, abrasion resistance, and scratch resistance as a decorative rim for a watch.

Embodiment 3 FIG. 3 is a step-by-step process of manufacturing a decorative part of the present invention, which is finished in multiple colors by using a hard coating with letters and patterns and a plating coating on the other side. First, as shown in (b) on the surface of the watch case 5 formed of a brass material on the collar shown in Fig. 3 (a), a nickel plating layer 6 of 3 μm thickness was applied as a base plating layer by a plating method. A palladium alloy plating layer 7 having a thickness of 3 μm was formed. After cleaning the surface of the brass watch case on which the base plating layer was formed in an ion plating device in the same manner as in Example 1, ion plating was applied to the entire surface (c).
As shown in the figure, a gray-black hard coating WA8 containing Ti, N, and C as main components was coated to a thickness of 1 μm.

Next, as shown in (d), letters and patterns were printed by screen printing using the same solder resist agent as in Example 1, and air-dried and hardened to form masked B'A 3 in the form of letters and patterns. After that, as shown in (e), unnecessary parts of the gray-black hard coating 1lSI8 are removed, and then, as shown in (f), the masking film 3 is peeled off.
As a completed appearance, a watch case exhibiting two colors was formed by the combination of the Pd-Ni alloy plating film 7 and the gray-black hard film 8 with letters and patterns. The brass watch case made by this method has a coating hardness of Hv for the gray-black letters and pattern.
The hardness of the Pd-Ni alloy plated coating was Hv400 or higher.Also, as a result of the same quality test as in Example 1, the corrosion resistance, adhesion, and abrasion resistance as a watch case were confirmed. The scratch resistance was sufficiently satisfied.

〔Effect of the invention〕

As described above, according to the present invention, a Ti-based hard coating is applied to the entire surface of a decorative member in which a base layer is provided on a metal or alloy material or a base layer by ion plating, and then by tacho printing and screen printing. Masking any surface of the Ti-based hard coating with a solder resist in a horizontal or letter shape, peeling off and removing the Ti-based hard coating other than the masked area, and further removing the masking to partially or completely cure the Ti-based hard coating. By using a manufacturing method for decorative parts having a multicolor tone of a Ti-based hard coating color and a grain color or base layer color, the coating hardness Hvl
000 or higher, H 41 T with a metallic feel with high decorative value
By forming the l-based hard τ1 coating in a horizontal or letter shape, the appearance of the pattern and letters, which are the design points, is similar to that of the J-period 41! It lasts for a long time, and further Ti-based (stool T1+I
By printing with a solder resist that can withstand partial peeling of the Li film, the Ti-based hard coating can be finished with high quality in complex patterns and letters, and the external color tone of the patterns and letters and other surfaces can be improved. It has become possible to provide a decorative member with very high decorative and functional value in various combinations of multiple colors, such as gold-white, gold-gray-black, and blue-ish color, and a method for manufacturing the same. Applications include not only exterior parts for watches, but also general decorative items such as eyeglass frames, lighter cases, decorative bands, buckles, tie bins, rings, spoons, and forks.

[Brief explanation of drawings]

Figures 1(a) to (e), Figures 2(a) to (f), and Figures 3(a) to (f) each show the structure of the laminated film at each manufacturing stage in the embodiment of the present invention. It is a sectional view of the main part. 1...5US304 2...Golden hard ττ coating (Ti-based) 3...Masking coating 4...Gray-black hard N coating (Cr-based) 5...Brass 6...Ni plating coating 7...・Pd-Ni alloy plating film

Claims (3)

[Claims] (1) A Ti-based hard coating is applied to the entire surface of a metal or alloy material or a decorative member with a base layer provided on the material by ion plating, and then any arbitrary surface of the Ti-based hard coating is applied by tacho printing or screen printing. Masking is applied horizontally or character-wise with solder resist, and the Ti-based hard coating other than the masked areas is peeled off, and the masking is further removed to partially or entirely change the color and material of the Ti-based hard coating. A method for producing a decorative member, characterized in that the decorative member is finished in multiple colors or a base layer color. (2) The metal or alloy material is stainless steel, Ti, Ti
The method for manufacturing a decorative member according to claim 1, wherein the decorative member is made of an alloy, a copper alloy, or a zinc alloy. (3) The base layer is made of Cu, Ni, and Ni by wet plating.
2. The method of manufacturing a decorative member according to claim 1, wherein a single layer or a stack of several types of alloy, Pd, Pd alloy, Rh, gold, gold alloy, or Cr-based hard coating formed by an ion plating method are formed.