JP6039844B1 - Plating decoration, writing instrument, and method of manufacturing plating decoration - Google Patents

Abstract

An object of the present invention is to provide a plated decorative article that has an aesthetic appearance as if it was inlaid, and has an elegant and dull inlaid decoration that is not present in conventional plated decorations, or a glittering and luxurious decoration. SOLUTION: The pattern layer 20 is composed of a silver layer forming a black layer 40 and a noble metal layer forming a noble metal color layer 60, and one of the silver layer 40 and the noble metal layer 60 forms a lower layer, and the other is the other. The noble metal layer 60 is composed of gold and platinum thin films adjacent to each other, and has a silver sulfide thin film on the surface of the silver layer 20, and the silver sulfide thin film is a black layer 20 forming jet black. Plating ornaments 1 A plated ornament 1 in which the film thickness of the noble metal layer 60 is 2 to 10 μm. [Selection] Figure 1

Description

  The present invention relates to a plated ornament, a writing instrument decorated by plating, and a method for producing a plated ornament. In more detail, with a black and noble metal color weaving pattern, mass-produced plating ornaments, writing instruments, and these plated ornaments that are decorated with elegance and a dignified inlay, or glittering and luxuriously decorated. It is related with the manufacturing method which can be performed. Furthermore, the present invention relates to a plated ornament, a writing instrument, and a manufacturing method capable of mass-producing these plated ornaments, as if they are undulating on the groundwork, as if they have an aesthetic appearance like inlay work.

  As a traditional ornament, an inlay work is known in which a pattern made of gold and silver is decorated with a lacquer coating that forms a glossy black base. The inlay has an elegant and subtle aesthetic due to the contrast between jet black and gold and silver patterns, and has attracted many people for many years.

  In the process of inlaying, first, fine grooves forming a texture pattern are engraved on the surface of the base material using a special chisel. Next, a line or plate of pure gold or the like that is thinly drawn and embedded is embedded in the groove, and a pattern is drawn. Then, after the surface is coated with lacquer and baked, sharpening is repeated and the surface is smoothed so that there are no fine steps on the surface. Finally, the whole is reground and finish engraved.

  Each process of inlaying, for example, the texture patterning process, which is said to be the most important work in inlaying, is engraved with fine grooves that are indistinguishable with the naked eye, etc. It takes time and effort. Therefore, the problem is that it is not suitable for mass production. Furthermore, since the inlay work is sharpened so as to eliminate fine steps on the surface, the surface of the decorative article becomes smooth, and there is a problem that it is not possible to decorate a rough base.

  Therefore, the inventor of the present invention, as well as the case where the base is flat, even if the base is a curved surface or a surface with undulations on the base, it is as if it is a refined and elegant appearance such as inlay work. An object of the present invention is to provide a product and a decoration method by plating that can mass-produce the product.

  As a conventional decoration technique by plating, first, as a first aspect for enhancing the beauty of a plated decorative article, there is an old-fashioned plating technique. Patent Document 1 and Patent Document 2 disclose a technique for polishing a black plating layer, which is the outermost layer, to make it appear as if it was an antique art work, and to give a decorative product a high-class feeling by plating. Has been.

  In Patent Document 1, there is a technique for a jewelry having a mottled pattern composed of three colors of silver, gold, and black, with a white tone by base plating, a gold tone by precious metal plating, and a black tone by black chrome plating or the like. It is disclosed. According to the technique described in Patent Document 1, a base layer of white silver color is plated on a base material with nickel or the like, and a noble metal layer of gold color is plated so as to be a thin film of about 1 to 5 μm from above. .

  Then, the upper gold layer is buffed in a random direction to form a mottled pattern with fine irregularities. Further, a black chrome layer is plated from above the noble metal plating layer, and the surface thereof is buffed in a random direction to form a mottled pattern with fine irregularities.

  According to the technique described in Patent Document 1, since the mottled pattern of the gold layer and the black layer is formed by buffing, the boundary of each color tone becomes cloudy and becomes unclear, and gold plating or the like is partially peeled off. Only the antique decoration such as Taka could be expressed, the vividness of the light reflection was lost, and it was not possible to express the elegant and gorgeous beauty like inlaywork.

  Patent Document 2 was decorated with two color tones, a portion in which white tone is used as a base surface and a black tone is applied, and a portion in which gold color tone is used as a base surface and a black tone is applied. Techniques for processing decorative parts are disclosed. According to the technique described in Patent Document 2, first, the entire surface of the substrate having white tone is plated with gold color, and the surface layer plated with gold color is partially masked and masked. The gold-colored plating other than the part is peeled off to form a two-color surface layer of white tone and gold tone. Next, by plating a black chrome layer on the two-color surface layer and partially polishing a part of the black chrome layer, it is possible to obtain a smoldering decoration based on two colors of white and gold. It is said that.

  According to the technique described in Patent Document 2, both gold and white are dull tones, and the reflection of light is not vivid, and an elegant and dignified aesthetic like inlaying is expressed. I couldn't.

  Patent Document 3 and Patent Document 4 disclose a technique of blackening a part of the surface of the plated ornament as a second aspect for improving the appearance of the plated ornament. The technique of Patent Document 3 discloses a technique of a method for imparting a black pattern to a part of a writing instrument outer cylinder having a noble metal plating layer.

  According to the technique described in Patent Document 3, the surface of a writing instrument outer cylinder made of copper or the like is plated with a noble metal such as gold plating, and the noble metal plating layer is partially deleted by diamond cutting or engraving. The base material is exposed so as to form a surface, and the exposed copper surface is dipped in an aqueous solution such as potassium sulfide so as to be blackened.

  The groove surface forming the black part is formed by partially removing the noble metal plating layer by diamond cutting or engraving to expose the base material, so that thin linear grooves can be freely formed It was difficult to do. And because it is not possible to express a thin line-shaped free-form black decoration, the decoration is monotonous and lacks change, and it is a durable decoration that is difficult to peel off, and it has an elegant and dignified aesthetic like inlay work. I couldn't get the ornaments to present.

  Patent Document 4 discloses a technique for decorating medals by metal vapor deposition, regardless of the electroplating technique. According to the technique described in Patent Document 4, a base material made of a material such as silver is press-molded to give a pattern, and the entire surface of the base material is sulfidized to blacken, and then applied to a portion other than the pattern. Masking is performed, and a noble metal such as gold is plated only on the pattern portion by vapor deposition.

  According to the technique described in Patent Document 4, the entire base material is sulfurized to form a black base, and gold is vapor-deposited only on the pattern portion. Because it is by vapor deposition, a gold film can be formed even on a non-conductive silver sulfide film, but the gold film thickness by vapor deposition is thinner than that by electroplating. There has been a problem that the gold-plated portion on the black base may appear dark due to the influence of the black of the base.

  On the other hand, when the base material after sulfidation is adjusted in advance so that it becomes grayish white by buffing, the portion to be masked later is also shaved by buffing, so the black color becomes brighter. There was a possibility of losing. Even with this technology, it is not possible to express a thin line-shaped free-form black decoration, the reflection of light disappears, the elegance and graceful aesthetics such as inlay work, and the highly durable decoration that prevents plating from peeling off I couldn't get the goods.

  As a third mode for enhancing the appearance of plated ornaments, a three-dimensional pattern is given to ornaments by masking parts of the ornaments, plating parts other than the masking, and then removing the masking. The technique to do is disclosed by patent document 5 and patent document 6.

  Patent Document 5 discloses a technique in which a pattern is formed by a plurality of metal plating layers and decorated by plating. According to the technique described in Patent Document 5, patterning is performed on the surface of a decorative article by masking, a fine rough surface is formed by acid treatment or the like on an unpatterned portion, and the rough surface portion is electroplated. It is said that the handle will be raised. However, even with this technology, it is only possible to arrange multiple colors of metal plating layers on the surface of a flat base material and to distinguish colors, and like inlaywork, a pattern made of gold and silver etc. with a glossy black background as a background Could not be decorated.

  Patent Document 6 discloses a technique of a partial plating method that can increase the adhesion of decorative plating. According to the technique of Patent Document 6, masking is performed on only a part of the shining silver plating base to form a pattern, and the entire part is immersed in an etching solution, and only the part that is not masked is masked. It is going to be activated. Thereafter, decorative plating of a copper layer having a convex portion on the activated portion and a gold layer thereon is performed. Then, the masking is removed to make a decorative body made of silver and gold.

  This technique also improves the adhesion of the plating layer, but the decorative plating only shines in the noble metal color, as if the gold and silver pattern floats in the black base like inlay work. It was not possible to provide an elegant and elegant ornament, or a glittering and luxurious ornament.

Patent Document 1: JP-A-2-145760 Patent Document 2: JP-A-6-306675 Patent Document 3: JP-A-54-107439 Patent Document 4: JP-A-9-310166 Patent Document 5: Special Japanese Patent Laid-Open No. 57-63690 Patent Document 6: Japanese Patent Laid-Open No. 2003-183877

  The inventor of the present application, as a result of earnest efforts to develop a decorative product by plating that exhibits an aesthetics like an inlay with a black background of jet black, as a result of an inlay with black and a noble metal color such as gold or white This led to the development of technology for forming decorations by plating. The problem to be solved by the present invention is a plating ornament, a writing instrument, and these plating ornaments, which are not like the conventional plating ornaments, but have an elegant and dignified decoration such as an inlay work, or a glittering and luxurious decoration. It is providing the manufacturing method which can mass-produce.

  The first invention of the present invention is a plating ornamental article having a pattern layer comprising a silver layer forming a black layer and a noble metal layer forming a noble metal color layer, of the silver layer and the noble metal layer. One of them forms a lower layer, the other forms an upper layer, the noble metal layer is made of at least one thin film of gold and platinum, and has a silver sulfide thin film on the surface of the silver layer, and the silver sulfide thin film Is a black layer forming jet black, and the pattern formed by the pattern layer is a spotted pattern. Since the two plating layers are copper plating layers having excellent ductility on the base material side, irregularities such as pinholes on the surface of the base material are smoothed. Since the outer layer side is a nickel plating layer, it is suitable as a base for the gold plating layer.

  The pattern layer may be planar or curved. A curved surface is an object that has a curved surface at the edge, such as an automobile emblem, in addition to an object that is entirely curved, such as an outer cylinder of a writing instrument shaft such as a fountain pen or pole pen. May be. In the pattern layer, the lower layer refers to a plating layer on the side close to the substrate.

  The noble metal layer may be a thin film made of only a gold layer or a thin film made of only platinum. Further, the gold layer and the platinum layer may be adjacent to each other, or the gold layer and the platinum layer may be disposed in a state of being separated in a stepping stone shape. The pattern layer may be a geometric pattern, a concrete pattern, or an abstract pattern such as an intricate spotted pattern. Here, the gold layer is not limited to pure gold, and may be a gold alloy, or may be an alloy including the platinum layer and the silver layer.

  In the pattern layer, when the silver layer forms a lower layer, the silver layer is plated on the base material in advance, masking is performed so as to form a pattern on the surface of the silver layer, and the noble metal layer is plated on the portion without masking. Then, after removing the masking, the silver layer may be sulfided to form a black thin film of silver sulfide. The masking agent may be a known resist ink or the like.

  On the other hand, when the noble metal layer is a lower layer, the noble metal layer is plated on the base material in advance, masked so as to form a pattern on the surface of the noble metal layer, and a pattern is formed on the silver layer thin film. The layer may be sulfurized to form a black layer. When the silver layer is an upper layer, the masking may be removed before the sulfiding treatment, or the masking may be removed after the sulfiding treatment.

  According to the first invention, since the pattern layer is formed without being polished by a buff or a brush, the black layer exhibits a blackish jet black, and the jet black that makes the gold and platinum colors stand out as if it were an inlaid black There is an advantageous effect that a black layer can be obtained. Furthermore, since the pattern layer is not polished, the boundary between the noble metal layer and the black layer becomes clear, and it is possible to obtain a plated decorative article that is difficult to peel off and has high durability. In addition, it is possible to express the beautiful appearance of gold and platinum patterns in a black background, as if it were an elegant and dignified plating ornament such as an inlaywork, or a plating ornament with a glittering and luxurious decoration. Can be obtained. It goes without saying that if the clear lacquer is applied on the pattern layer, the blackish black layer is prevented from being deteriorated and the durability of the pattern layer is improved.

  A second invention of the present invention is a plated ornament, and has a pattern layer comprising a silver layer forming a black layer and a noble metal layer forming a noble metal color layer, and the silver layer and the noble metal layer One of them forms a lower layer, the other forms an upper layer, and the noble metal layer has a thin film made of gold and platinum adjacent to each other, and has a silver sulfide thin film on the surface of the silver layer, and the silver sulfide thin film Is a black layer that forms jet black.

  In order to obtain a pattern layer in which the thin film of the gold layer and the thin film of the platinum layer are adjacent to each other, one thin film is plated first, and a part of the thin film formed earlier is masked to form a pattern. Next, the other thin film may be formed in a portion that is not masked, and then the masking is removed. The pattern formed on the thin film may be a geometric pattern, a concrete pattern, or an abstract pattern such as an intricate spot pattern.

  According to the second invention, it is possible to obtain a plated ornament provided with a pattern layer in which two precious metal colors composed of adjacent gold and platinum colors and black are woven. Thereby, the range of aesthetics that can be expressed by the plated ornaments is widened, and it is possible to obtain a plated ornament that exhibits a more elegant and dignified aesthetic.

  According to a third aspect of the present invention, there is provided a plated ornament according to the first or second aspect, wherein the noble metal layer has a thickness of 2 μm or more and 10 μm or less. If a thin film is formed by electroplating so that the film thickness is 2 μm or more, even if it is a noble metal layer such as a gold layer or a platinum layer that is easily affected by the underlying color when the film thickness is thin, It becomes difficult to be affected by the color. Further, since the film thickness is 10 μm or less, there are advantageous effects that the plating bath time is short, the amount of noble metal used is reduced, and mass production is easy. Thereby, it is possible to obtain a plated decorative article in which both the noble metal color and the black color shine vividly.

  According to a fourth aspect of the present invention, there is provided a plated decorative article according to the first to third aspects, wherein the pattern layer is provided with a undulating base layer.

  Due to the undulations in the foundation layer, an inlaid pattern is formed on the undulating foundation. The place where the undulating base layer is formed is not limited to the case where it is formed below the lower layer, and may be formed between the upper layer and the lower layer, both of which are provided with the base layer. May be.

  When the base layer is formed on the substrate side of the lower layer, both the upper layer and the lower layer are provided so as to follow the undulations. Can be used as a decorative item. In the case where the underlayer is formed between the upper layer and the lower layer, the upper layer is emphasized by undulations, and a decorative product that exhibits a more elegant and dignified beauty can be obtained.

  When the base layer is provided on both the base material side of the lower layer and between the upper layer and the lower layer, the surface of the upper layer and the surface of the lower layer are approximately the same height, and the noble metal layer The boundary with the black layer becomes clearer. In addition to the undulations in the base, the boundary between the noble metal layer and the black layer is clear, so that any pattern on the black layer and the noble metal layer can be made into a plating ornament that has a more elegant and aesthetic appearance. . As a result, it is possible to express decoration such as inlay work on an unprecedented undulating base, and to obtain an advantageous effect that it is possible to obtain a plated decorative article that is more elegant and has a dignified beauty.

  According to a fifth aspect of the present invention, there is provided a plated ornament according to any one of the first to fourth aspects, wherein the plated ornament is a writing instrument, and the pattern is formed on an outer cylinder of the writing instrument. Yes. Here, the outer cylinder of the writing instrument refers to an outer cylinder used for a writing instrument such as a fountain pen and a ballpoint pen. Thereby, even if it is a thin cylinder like writing instrument outer cylinders, such as a fountain pen and a ball-point pen, there exists an advantageous effect that it can be decorated like an inlay work.

  A sixth invention of the present invention is a method for producing a plated decorative article, wherein a part of the silver layer is masked on a base material plated with a silver layer, and the part of the silver layer that is not masked is masked. Including a base step for plating an underlying layer that forms relief, and a noble metal layer plating step for forming at least one thin film of gold and platinum on the base layer, wherein the noble metal layer plating step is performed on the base layer. The first step includes a first step of forming at least one of a gold layer and a platinum layer, a second step of peeling off the masking, and a third step of blackening the silver layer of the masked portion. Forming the thin film by electroplating, and the third step is to sulfidize the silver layer after removing the masking to form a vivid black layer, and at least one color of gold and platinum and vivid Black There has been characterized by causing decorated in different colors so as to form a pattern.

  The foundation process includes a masking process for masking a part of the silver layer and a process for plating the foundation layer on a portion that is not masked. Each process may be performed by a known plating process. In the masking step, masking may be performed using a sprayer or a brush so that a pattern is formed. The pattern may be a geometric pattern, a concrete pattern, or an abstract pattern such as an intricate spotted pattern, and is not limited. The underlying layer may be formed so as to be undulated by copper plating or the like.

  The noble metal layer plating step includes a gold or platinum plating step, a step of removing masking by the masking step, and a sulfuration treatment step. Since the gold or platinum thin film is formed by electroplating to a film thickness of 2 μm or more and 10 μm or less, the film thickness is hardly affected by the color of the base or the color of the substrate. In the sulfiding treatment step, sulfur and the silver layer may be reacted to form black silver sulfide. For example, the surface of the silver layer becomes vivid black by immersing the plated ornament in an aqueous solution containing sulfur, and jet black. The concentration of sulfur is not limited, and may be a concentration according to the temperature of the heated aqueous solution.

  By plating the base layer between the silver layer and the noble metal layer, undulations are formed by the base layer and the silver layer. Then, by plating the noble metal layer on the base layer, it is possible to obtain a plated ornament in which gold and white are three-dimensionally decorated against a black layer made of silver sulfide.

  Further, the base process and the noble metal layer plating process do not include a buffing or brushing process in any process. Thereby, a black layer can be made into vivid black like the jet black base in inlay work. Furthermore, the boundary line between the black layer and the gold layer or the platinum layer is also clearly expressed, and a decorative product having an aesthetic appearance such as an inlaying work in which the gold color and the platinum color stand out on the black base can be obtained.

  Since a polishing step using a buff or a brush is not included, even if a fine pattern is formed by plating, there is an advantageous effect that the plating is hardly peeled off. In addition, since the sulfurating treatment is performed after the step of plating the gold plating, it is not necessary to previously adjust the base color of the gold plating layer by the polishing treatment. As a result, it is easy to mass-produce plated ornaments that are elegant and have an elegant appearance such as inlaywork.

  A seventh invention of the present invention is a method for manufacturing a plated ornament, wherein a noble metal made of at least one of gold and platinum is formed on a base material in which a silver layer is plated on the entire underlying layer that forms the relief. Including a layer plating step, wherein the noble metal layer plating step forms a first step of masking a part of the silver layer, and forms at least one of a gold layer or a platinum layer in a portion of the silver layer that is not masked A second step of peeling off the masking, and a fourth step of blackening the silver layer. The second step is to form the thin film by electroplating, and the fourth step is masking. The silver layer that has been subjected to sulfidation is treated with sulfur to form a vivid black layer, and at least one color of gold and platinum and the vivid black are colored and decorated so as to form a pattern. No .

  In the second step, when any of the thin films of gold and platinum is provided, either one of the thin films is formed first, masking is performed so as to form a pattern thereon, and the other of the portions other than the masked portion is masked. A thin film may be formed to remove the masking. The removal of the masking in the third step may be the removal of the masking in the first step and the masking in the second step at the same time.

  The size of the undulations of the underlayer is not limited, and may be fine undulations or large undulations. By forming the base layer closer to the base material than the silver layer, the black layer and the noble metal layer are decorated along the undulation of the base layer. Thereby, it becomes easy to mass-produce an unprecedented plating ornamental product that exhibits an elegant and dignified aesthetic like an inlay work on a rough base.

  An eighth invention of the present invention is a method for producing a plated decorative article, wherein a noble metal made of at least one of gold and platinum is formed on a base material in which a silver layer is plated on the entire underlying layer that makes ups and downs. The noble metal layer plating step includes a first step of masking a part of the silver layer, a second step of bathing a non-masked portion of the silver layer in a nitric acid bath, and a nitric acid bath. A third step of forming a second underlayer on the silver layer, a fourth step of forming at least one of a gold layer and a platinum layer on the second underlayer, and a fifth step of removing the masking. And a sixth step of blackening the silver layer, the fourth step is to form the thin film by electroplating, and the sixth step is to sulfidize the portion of the silver layer that has been masked. A bright black layer, of gold and platinum It is characterized in that is decorated in different colors so as to form a single color, a vivid black and the pattern even without.

  Since the underlayer is formed on the substrate side with respect to the silver layer, the entire underlayer is rich in undulations. The second underlayer is formed in a portion where the silver layer is slightly thinned by a nitric acid bath in the second step, and the surface of the noble metal layer formed on the second underlayer and the silver layer are sulfided to black The surface of the layer becomes a surface having substantially the same height, and the boundary between the noble metal layer and the black layer becomes clearer. In addition to the undulations on the ground, the boundary between the noble metal layer and the black layer becomes clearer, so that it is possible to obtain a plated decorative article that exhibits a more elegant and dignified beauty.

-According to 1st invention, while the boundary of a noble metal layer and a black layer becomes clear, it can be set as the plating decoration product with high durability that plating is hard to peel off. In addition, it is possible to express the beautiful appearance of gold and platinum patterns in a black background, as if it were an elegant and dignified plating ornament such as an inlaywork, or a plating ornament with a glittering and luxurious decoration. Can be obtained.
-According to 2nd invention, the width | variety of the beauty | look which can be expressed with a plating ornament expands, and it can obtain the plating ornament which exhibits a more refined and dull beauty.
-According to the third invention, it is possible to obtain a plated ornament in which both the noble metal color and the black color shine vividly.
-According to the 4th invention, the advantageous effect that the decoration like an inlay work can be expressed on the ground with an unprecedented undulation, and the plating decoration which exhibits a refined and dignified beauty can be obtained. Play.

-According to 5th invention, even if it is a thin cylinder like writing instrument outer cylinders, such as a fountain pen and a ball-point pen, there exists an advantageous effect that it can be decorated like an inlay work.
-According to 6th invention, a black layer can be made into vivid black like the jet black base in inlay work. Furthermore, the boundary line between the black layer and the gold layer or the platinum layer is also clearly expressed, and a decorative product having an aesthetic appearance such as an inlaying work in which the gold color and the platinum color stand out on the black base can be obtained. In addition, it is easy to mass-produce plated ornaments that are elegant and have a delicate aesthetic, such as inlay work.
-According to 7th invention, it becomes easy to mass-produce an unprecedented plating ornamental article which exhibits refined and deep beauty like an inlay work on a rough foundation.
-According to 8th invention, it can be set as the metal-plating ornament which shows a more refined and dignified aesthetics, when the foundation | substrate has undulations and the boundary of a noble metal layer and a black layer becomes clearer.

The perspective view of a writing instrument (Example 1). Explanatory drawing explaining a plating process (Example 1). Explanatory drawing explaining a plating process (Example 1). A photograph of a writing instrument with a spotted pattern (Example 1). Explanatory drawing explaining a plating process (Example 2). Explanatory drawing explaining a plating process (Example 2).

  A pattern layer consisting of a silver layer forming a black layer and a noble metal layer forming a noble metal color layer is formed on the decorative article by electroplating, so that at least one color of gold and platinum and black forming a jet black By making it color-coded, we realized a plated ornament that looks as beautiful as an inlay. Hereinafter, an embodiment in which the plated ornament is a writing instrument shaft will be described.

  In Example 1, the writing tool shaft 1 having a cylindrical body provided with a pattern layer in which the underlying layer is provided with undulations and the upper gold layer is emphasized, and the manufacturing method thereof are shown in FIGS. Will be described with reference to FIG. FIG. 1 shows a perspective view of the writing instrument 1. 1A shows a perspective view of the writing instrument shaft, and FIG. 1B shows a partially enlarged view thereof. Each of FIGS. 2 to 3 shows a process chart for explaining a plating process of the writing instrument 1. FIG. 4 is a photograph of a writing instrument manufactured by the process shown in Example 1.

  First, the writing instrument shaft 1 will be described with reference to FIG. The writing instrument shaft 1 is provided with a pattern layer 20 including a black layer 40 forming a jet black and a gold layer 60 along the entire curved surface. The patterned layer 20 is a silver layer whose lower layer is a black layer 40 and a thin layer of a gold layer 60 whose upper layer is a noble metal layer. In addition, an underlying layer that makes ups and downs is provided between the black layer 40 and the gold layer 60, the black layer 40 forms a flat part of the ups and downs, and the gold layer 60 forms a protruding part of the ups and downs. The shape of the pattern layer 20 is a spotted pattern.

  Next, the manufacturing process of this spot pattern will be described with reference to FIGS. Each drawing of FIG. 2 shows a base process for forming the base layer by electroplating. First, FIG. 2 (A) shows the process of electroplating the silver layer 30 on the base material 10 of the writing instrument shaft made of brass or the like, and FIG. 2 (B) shows a part of the silver layer in a patchy shape. A masking process for masking is shown, and FIG. 2C shows a nitric acid bath process for roughening the surface of the silver layer of the portion 31 that is not masked. FIG. 2D shows a process of plating the copper layer 50 that forms the foundation layer so that the silver layer of the portion 32 slightly thinned by the nitric acid bath is undulated.

  Each drawing of FIG. 3 shows a noble metal layer plating step for forming a gold thin film. FIG. 3 (E) shows a sulfuric acid bath process in which the oxide film generated on the surface of the copper layer 50 forming the underlayer is removed and the surface of the copper layer is activated. FIG. 3 (F) shows the sulfuric acid bath. A step of plating the gold layer 60 on the copper layer thus formed is shown, and FIG. 3G shows a step of peeling the masking 90. FIG. 3H shows a step of sulfiding the silver layer of the portion 33 that has been masked.

(Base process)
First, the base process will be described with reference to FIGS.
(Silver plating process)
A silver layer 30 is plated on the surface of the base material 10 made of brass or the like by electroplating (FIG. 2A). The silver layer has a thickness of 10 to 20 μm, and the silver plating solution contains 37 to 75 g of silver bromide, 150 to 170 g of potassium bromide, and 5 to 60 g of potassium carbonate per liter. The temperature is 18-20 ° C. Current density need only be a 0.5~1A / dm ^2.
(Masking process)
Next, masking 90 is performed on a part of the surface of the silver layer 30 so as to form an intricate spotted pattern (see FIG. 2B). The masking 90 that forms the spotted pattern may be formed by attaching fine splashes with a sprayer or hanging a paint, or a masking agent may be applied with a brush. Of course, the sprayer and the brush may be combined and masked. The masked portion is the black layer 40, and the base layer of the noble metal layer is formed in the unmasked portion (see FIG. 1B). The masking agent is a resist ink that is not peeled off when pickling with sulfuric acid or the like and is easily peeled off by an organic solvent such as thinner.

(Nitric acid bath process)
Next, a portion 31 of the surface of the silver layer 30 that is not masked is bathed in nitric acid. Then, the silver layer 30 is slightly dissolved, the surface is roughened, and the film thickness is slightly reduced (see FIG. 2C). The concentration of the nitric acid solution is, for example, diluted by adding water to a nitric acid stock solution containing 67.5% nitric acid component by weight, so that the nitric acid stock solution: water has a volume ratio of 2: 1. Anything can be used. After the nitric acid bath, it is washed with water so that the nitric acid component is washed away. Thereby, the plating adhesion between the silver layer and the underlayer formed on the silver layer is increased, and even if a fine pattern such as an intricate spot pattern is formed, the plating is difficult to peel off.

(Underlayer forming process)
Then, the surface of the silver layer 30 is slightly roughened by a nitric acid bath, and a base layer is plated on the portion 32 where the film pressure is thinned so as to make undulations (see FIG. 2D). The underlayer is a copper layer 50, and the thickness of the copper layer 50 is 30 to 80 μm. The copper plating solution contains 180 to 250 g of copper sulfate per liter, 45 to 60 g of a sulfuric acid stock solution containing 98% by weight of the sulfuric acid component, and the bath temperature is 20 to 35 ° C. Current density is 2~6A / dm ^2. The material of the underlayer is not limited to copper, and nickel or the like may be used. Further, the film thickness of the underlayer, plating conditions, and the like are not limited and may be adjusted as appropriate.

(Sulfuric acid bath process)
Next, the writing instrument shaft body 1 is bathed in a sulfuric acid bath to activate the surface of the undulating copper layer 50 (see FIG. 3E). Thereby, the oxide film which generate | occur | produced on the surface of the copper layer 50 is removed, and the adhesiveness of the copper layer 50 and the gold layer mentioned later is made high. The concentration of the sulfuric acid solution is, for example, diluted by adding water to a sulfuric acid stock solution containing 98% by weight of the sulfuric acid component so that the sulfuric acid stock solution: water has a volume ratio of 10:90. If it is. After the sulfuric acid bath, it is washed with water so that the sulfuric acid component is washed away.

(Precious metal layer plating process)
Next, the noble metal layer plating step will be described with reference to FIG. 3 (F) to FIG. 3 (H).
(Gold plating process)
A gold layer 60 is plated by electroplating on the copper layer 50 activated by the sulfuric acid bath (see FIG. 3F). Since the gold layer 60 is formed on the undulating copper layer 50, the gold layer 60 shines vividly at a position slightly higher than the silver layer 30 to be the black layer 40, and the shine of the noble metal is more emphasized. Pattern layer 20 (see FIG. 1B). The film thickness of the gold layer 60 is 2 to 3 μm, and the gold plating solution may contain 2 to 6 g of potassium gold cyanide per liter, and the bath temperature may be 30 to 40 ° C. Current density is 0.5~2A / dm ^2. The material of the gold layer may be pure gold or a gold alloy such as gold cobalt.

(Masking peeling process)
The mask stripper is a thinner of a general commercially available lacquer diluent, and may be a liquid in which an alcohol such as toluene, methyl alcohol or isobutyl alcohol, or an acetate such as methyl acetate is mixed. By this masking peeling, only the masking 90 is dissolved and removed (see FIG. 3G). As a result, the silver layer 30 of the portion 33 that has been masked is exposed.

(Sulfurization process)
In the sulfuration treatment step, the writing instrument shaft 1 is immersed in an aqueous solution containing sulfur, and the silver layer of the portion 33 that has been masked reacts with sulfur to form a thin film of silver sulfide. (See FIG. 3H). Here, the temperature of the aqueous solution in which the writing instrument shaft 1 is immersed is set to 65 ° C. to 75 ° C. Thereby, the silver layer 30 which makes the lower layer of the pattern layer 20 is made into the vivid black layer 40 (refer FIG.1 (B) figure). The component of the aqueous solution containing sulfur is, for example, as long as the component per kg is an aqueous solution containing about 200 g of sulfur and about 70 g of quicklime, and a few drops are mixed with 1 liter of water. The concentration may be adjusted as appropriate according to the heating conditions.

(Protective coating process)
Use a colorless water-soluble clear lacquer that does not contain pigment in the protective coating. What is necessary is just to melt | dissolve resin in highly volatile solvents, such as naphtha, xylene, toluene, and acetone. By setting the coating thickness to a thin film having a thickness of 2 to 6 μm, the solvent is volatilized and dried to obtain a hard protective film, and durability that does not change the jet black and the noble metal color is obtained.

  As described above, neither the base process nor the noble metal layer plating process includes a polishing process using a buff or a brush. Further, the pattern layer 20 is formed by a thick noble metal layer by electroplating. Therefore, the black layer 40 can be made bright black, and can be a decorative product having a beautiful appearance in which the boundary line between the gold layer 60 and the black layer 40 is clearly defined (see FIGS. 1 and 4). ).

  It was possible to make a writing instrument shaft with a beautiful black-colored gold pattern on a bright black base. Since the gold layer 60 is plated on an uneven spot pattern, the angle of the reflected light changes depending on the viewing angle, and the beauty changes variously. As a result, it was possible to obtain a plated decorative article that was as elegant as an inlaywork and had a delicate aesthetic appearance (see FIG. 4). Of course, by changing the pattern, it is possible to make a plated ornament with a gorgeous and luxurious decoration.

  In Example 2, referring to each of FIGS. 5 and 6 showing partially enlarged cross-sectional views, the surface of the noble metal layer and the surface obtained by sulfiding the silver layer into a black layer are substantially the same height. The writing instrument shaft 2 as the surface and the manufacturing method thereof will be described. In the writing instrument 2, the lower layer of the pattern layer 21 is a silver layer 70 and the upper layer is a gold layer 60. Further, a copper layer 80 is provided under the silver layer 70 so that the underlayer is undulated. The silver of the portion 72 in which the surface is slightly roughened by a nitric acid bath and the film pressure is reduced so that the surface of the noble metal layer and the surface of the black layer 40 obtained by sulfiding the silver layer are approximately the same height. A copper layer as a second underlayer 82 is provided on the layer 70 (see FIG. 6K).

  FIG. 5A to FIG. 5E show a base process for forming a base layer that forms relief by electroplating. FIG. 5 (A) shows a first masking process in which the first masking 91 is applied to the base material 10 of the writing instrument shaft body made of brass or the like, and FIG. 5 (B) shows the first masking 91 not applied. FIG. 5 (C) shows a second masking step for plating the copper layer 80 and then applying the second masking 92 to the portion. (D) The figure shows the process of plating the underlayer 81 which makes a second layer on the second masking 92, and FIG. 5 (E) shows the peeling process for peeling the first and second masking. ing.

  FIG. 6F shows a process of forming the silver layer 70 on the entire writing instrument shaft 2 by electroplating. 6G to 6K show the noble metal layer plating step. FIG. 6G shows a third masking process in which a third masking 93 is applied to a part of the surface of the silver layer 70, and FIG. 6H shows the silver in the portion 71 where the third masking is not performed. The process of immersing layer 70 in a nitric acid bath is shown. FIG. 6 (I) shows the step of forming the second underlayer 82 in the portion 72 where the silver layer has been slightly thinned by a nitric acid bath, and FIG. 6 (J) shows the top of the second underlayer. FIG. 6 (K) shows a step of sulfiding the silver layer of the portion 73 that has been subjected to the third masking.

(Base process)
First, the base process will be described with reference to FIGS.
(First masking process)
A first masking 91 is applied to the base material 10 of the writing instrument shaft 2 made of brass or the like so as to form an intricate spotted pattern (see FIG. 5A). Since the masking agent and the masking method are the same as those in Example 1, the description thereof is omitted here.
(Underlayer forming process)
By electroplating, a base layer is plated so as to form undulations on the portion where the first masking 91 is not performed (see FIG. 5B). The underlayer is a copper layer 80, and the bath conditions such as the thickness and the component / concentration of the copper plating solution may be the same as those in the first embodiment.

(Second masking process)
The second masking 92 is performed on the copper layer 80 and the first masking layer without peeling off the first masking 91 (see FIG. 5C). As a result, the second masking 92 is applied to a part of the copper layer 80. Regarding the second masking 92, the masking agent and the masking method are the same as those in the first embodiment, and thus the description thereof is omitted here.
(Multilayer underlayer forming process)
In a state in which a part of the copper layer is masked by the second masking, the part not subjected to the second masking is plated by electroplating, and a part of the copper layer is used as a base layer 81 forming a multilayer ( (See FIG. 5D). By forming a part of the base layer as a multiple layer, the entire base becomes more undulating, and the angle of the reflected light is more varied depending on the viewing angle, and the aesthetics are variously changed.

(Masking peeling process)
The first masking 91 and the second masking 92 may be peeled in the same manner as in the first embodiment (see FIG. 5E). Since it is the same as that of Example 1, description is abbreviate | omitted here. Although an example in which the first masking and the second masking are peeled off at the same time has been described, it goes without saying that each masking may be peeled off separately.

A base layer 81 forming a multilayer is formed on a part of the copper layer 80, and then a silver layer 70 forming a black layer is plated.
(Sulfuric acid bath process)
First, a sulfuric acid bath is applied so as to activate the surface of the base material after removing the masking and the surface of the undulated copper layer forming a multilayer. The sulfuric acid bath may be the same as in Example 1. The concentration of sulfuric acid and the like are the same as in Example 1, and the description is omitted here.
(Silver plating process)
A silver layer 70 is formed by electroplating on the entire surface of the base material 10 after removing the masking and the underlying layer 81 forming a multilayer (see FIG. 6F). The silver plating step may be performed in the same manner as in Example 1. The thickness of the silver layer 70 and the bath conditions such as the silver plating solution are the same as in Example 1, and the description thereof is omitted here.

(Precious metal layer plating process)
Next, the noble metal plating layer process will be described with reference to FIGS. 6 (G) to 6 (K).
(Third masking process)
A third masking 93 is performed on a part of the surface of the silver layer so as to form a pattern (see FIG. 6G). Since the masking agent and the masking method are the same as those in Example 1, the description thereof is omitted here. Similarly to the first masking 91 and the second masking 92, the third masking 93 may be drawn with a sprayer or a brush. In the first to third masking, if a pattern is drawn using different sprayers or brushes, a richer expression pattern can be drawn. The form of the pattern is not limited, and may be a geometric pattern, a concrete pattern, or an abstract pattern such as an intricate spotted pattern.
(Nitric acid bath process)
Of the surface of the silver layer 70, a portion 71 not subjected to the third masking is bathed in nitric acid. The silver layer is slightly dissolved, the surface is roughened, and the film thickness is slightly reduced (FIG. 6H). The nitric acid bath may be the same as in Example 1. The concentration of nitric acid and the like are the same as in Example 1, and a description thereof is omitted here.

(Second base layer forming step)
A second underlayer 82 is formed by electroplating in a portion 72 of the silver layer that has been thinned by a nitric acid bath (see FIG. 6I). The thickness of the second underlayer 82 is adjusted so that the surface height of adjacent silver layers and the surface height of a gold layer described later are substantially the same height. The second underlayer 82 may be a copper layer as in the formation of the underlayer of Example 1, but the material of the underlayer is not limited to this, and nickel or the like may be used. The bath conditions such as the components and concentration of the copper plating solution may be the same as those in Example 1, and the description thereof is omitted here.
(Gold plating process)
A gold layer 60 that forms the upper layer of the pattern layer is formed on the second base layer 82 by electroplating (see FIG. 6J). Thereby, the height of the surface of an adjacent gold layer and silver layer becomes substantially the same, and each boundary becomes clearer. The bath conditions such as the composition and concentration of the gold plating solution may be the same as those in the first embodiment, and the description is omitted here.

(Masking peeling process)
The third masking 93 is peeled off and the silver layer 70 is exposed (see FIG. 6 (K)). The third masking 93 may be peeled off as in the first embodiment. The mask stripper and the like may be the same as those in Example 1, and the description thereof is omitted here.
(Sulfurization process)
The surface of the silver layer 70 is brightly black by performing the sulfidation process, and the surface height of the black layer 40 adjacent to the writing instrument shaft 2 and the gold layer 60 is substantially the same. Layer 21 is formed. The sulfidation process may be the same as that in Example 1, and the description is omitted here.
(Protective coating process)
For the protective coating, the same paint as in Example 1 may be used. The details of the protective coating may be the same as those in the first embodiment, and the description is omitted here.

  By forming a part of the copper layer 80 that forms the underlayer as a multi-layer, the entire underlayer becomes more undulating, and the angle of the reflected light is more varied depending on the viewing angle, and the aesthetics are diverse. The shaft body of the writing instrument that changes to As a result, it was possible to obtain a plated ornament that had a more elegant and dignified aesthetic as if it was inlaying.

(Other)
In Example 1, the example in which the gold layer is the upper layer and the blackened silver layer is the lower layer has been described, but it is needless to say that the gold layer may be the lower layer and the silver layer may be the upper layer. is there.
In Example 1, the base layer is a single layer, and in Example 2, the base layer is stacked in two layers, but the number of base layers is not limited. By superimposing the number of base layers, the reflection of light becomes rich and it is possible to express a gorgeous and gorgeous beauty.
In the above embodiment, the example of the writing instrument in which the undulation is formed on the base is shown. However, it is needless to say that the base is not required to have the undulation, and the plated ornament is not limited to the writing instrument.
In the above embodiment, the precious metal layer is described as a single gold film for easy understanding. However, the gold film may be replaced with a platinum film, and the gold film and the platinum film are adjacent to each other. Needless to say, it may be a noble metal layer having a pattern.
The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The technical scope of the present invention is shown not by the above description but by the scope of the claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of the claims.

1, 2, ... writing instrument shaft,
10 ... base material,
20, 21 ... pattern layer,
30 ... Silver layer, 31 ... Unmasked part,
32: Portion slightly diluted with nitric acid bath, 33: Portion masked,
40 ... black layer, 50 ... copper layer, 60 ... gold layer,
70 ... silver layer, 71 ... part where the third masking is not performed,
72: a portion slightly diluted with a nitric acid bath, 73 ... a portion where the third masking was performed,
80 ... a copper layer, 81 ... an underlayer forming a multilayer, 82 ... a second underlayer,
90 ... masking, 91 ... first masking, 92 ... second masking, 93 ... third masking

Claims (8)

Plating ornaments,
Having a pattern layer composed of a silver layer forming a black layer and a noble metal layer forming a noble metal color layer;
One of the silver layer and the noble metal layer is a lower layer, the other is an upper layer,
The noble metal layer is made of at least one thin film of gold and platinum, has a silver sulfide thin film on the surface of the silver layer, and the silver sulfide thin film is a black layer forming jet black,
The pattern formed by the pattern layer has a spotted pattern,
Plating decoration characterized by that. Plating ornaments,
Having a pattern layer composed of a silver layer forming a black layer and a noble metal layer forming a noble metal color layer;
One of the silver layer and the noble metal layer is a lower layer, the other is an upper layer,
The noble metal layer is composed of gold and platinum adjacent to each other, has a silver sulfide thin film on the surface of the silver layer, and the silver sulfide thin film is a black layer forming jet black.
Plating decoration characterized by that. The noble metal layer has a thickness of 2 μm or more and 10 μm or less,
The plated decorative article according to claim 1 or 2, characterized by the above. The base of the pattern layer is provided with a base layer that makes ups and downs,
The plated decorative article according to any one of claims 1 to 3, wherein The plated ornament is a writing instrument, and the pattern layer is formed on the outer cylinder of the writing instrument.
The plated decorative article according to any one of claims 1 to 4, wherein: A method for manufacturing a plating ornament,
An underlayer step of masking a part of the silver layer on a base material plated with a silver layer and plating an underlayer that undulates the unmasked portion of the silver layer; and a gold layer on the underlayer And a noble metal layer plating step for forming at least one thin film of platinum,
The precious metal layer plating step includes a first step of forming at least one of a gold layer and a platinum layer on the underlayer, a second step of peeling the masking, and blackening the silver layer of the masked portion. Comprising a third step,
The first step is to form the thin film by electroplating,
In the third step, the silver layer after the masking is peeled is sulfurized to form a vivid black layer, and is color-coded so that at least one color of gold and platinum and vivid black form a pattern. Decorate,
A method for producing a plated decorative article. A method for manufacturing a plating ornament,
Including a noble metal layer plating step for forming a thin film of at least one of gold and platinum on a base material in which a silver layer is plated on the entire underlying layer forming the undulations,
The noble metal layer plating step includes a first step of masking a part of the silver layer, a second step of forming at least one of a gold layer or a platinum layer on a portion of the silver layer that is not masked, It consists of a third step for peeling off the masking and a fourth step for blackening the silver layer,
In the second step, the thin film is formed by electroplating,
In the fourth step, the masked portion of the silver layer is sulfurized to form a bright black layer, and is color-coded so that at least one color of gold and platinum and a bright black form a pattern. Decorate,
A method for producing a plated decorative article. A method for manufacturing a plating ornament,
Including a noble metal layer plating step for forming a thin film of at least one of gold and platinum on a base material in which a silver layer is plated on the entire underlying layer forming the undulations,
The noble metal layer plating step includes a first step of masking a part of the silver layer, a second step of bathing a non-masked portion of the silver layer in a nitric acid bath, and a second step on the silver layer bathed in the nitric acid bath. A third step of forming a second underlayer, a fourth step of forming at least one of a gold layer and a platinum layer on the second underlayer, a fifth step of peeling off the masking, and the silver layer And the sixth step of blackening
In the fourth step, the thin film is formed by electroplating,
In the sixth step, the portion of the silver layer that has been masked is sulfidized to form a vivid black layer, and is color-coded so that at least one color of gold and platinum and vivid black form a pattern. Decorate,
A method for producing a plated decorative article.

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