JP3262782B2 - Substrate for forming electroformed product, electroformed product with substrate, and method for producing electroformed product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electroforming method (electroforming).
More specifically, the present invention relates to an electroformed product and a method for producing the same, and a substrate for forming an electroformed product useful for producing such an electroformed product and a method for producing the same. The invention also relates to an electroformed sheet and a decorative product provided with such an electroformed product. The substrate for forming an electroformed product of the present invention can be manufactured easily and with high yield and high accuracy.In addition, when this substrate is used, a fine electroformed product excellent in design and decorativeness can be precisely formed. It can be manufactured with good yield. The substrate for forming an electroformed product of the present invention can be advantageously used particularly for producing roses on a dial of a wristwatch and other decorative products.

[0002]

2. Description of the Related Art Conventionally, rose letters (HM) on a dial of a wristwatch have been known.
(Also referred to as R) has often been used to make electroforming. For example, Japanese Patent Application Laid-Open No. 62-187
No. 099 discloses a decorative character,
Alternatively, a 30-100 μm metal electroforming (nickel electroforming) is performed on the electroformed master substrate on which the decorative pattern is patterned, and the electroformed metal layer on which the pattern is formed is adhered to the temporary holding adhesive tape while the electroformed substrate is adhered. A method for producing a decorative pattern transfer tape, characterized in that a pressure-sensitive adhesive type adhesive, or an ultraviolet-curable, heat-curable combined type adhesive is applied to the surface side of the electroformed metal layer after peeling off. Is disclosed. When the decorative pattern transfer tape thus prepared is used, as described in Example 2 with reference to FIG. 2 attached to the official gazette, the dial of the wristwatch is electroformed with an adhesive. While pressing the metal layer with the urethane rubber pad, the lower part of the dial is heated to transfer the electroformed metal layer to the dial. After the transfer is completed, the temporary holding adhesive tape is peeled from the electroformed metal layer of the dial. However, in the case of this method, when the electroformed metal layer is composed of fine characters or the like, the adhesion area between the electroformed metal layer and the adhesive tape is too small. There is a problem that it cannot be peeled off.

A method developed to solve the above-mentioned problems and the like is a method for forming an electrodeposited image disclosed in Japanese Patent Application Laid-Open No. 7-331479. In this publication, a conductive coating is formed on the surface of a metal plate, an electrodeposition image is formed on the surface of the conductive coating, and the pressure-sensitive adhesive layer of a support substrate provided with a pressure-sensitive adhesive layer is formed. The electrodeposited image is peeled and transferred from a metal plate together with the conductive film, the conductive film is peeled from the electrodeposited image, a fixing adhesive layer is formed on an exposed surface of the electrodeposited image, and the support base material is formed. A method for forming an electrodeposited image, comprising attaching the electrodeposited image to the surface of an adherend via the fixing adhesive layer while peeling the electrodeposited image from the substrate. In this method of forming an electrodeposited image, as shown in FIG.
An electrodeposition image peeling step of peeling only the conductive film 53 from the supporting substrate 55 with the electrodeposition image 54 after peeling from the metal plate 52 while sandwiching the conductive film 53 and the conductive film 53 is adopted. The support substrate 55 has a pressure-sensitive adhesive layer 56 on the surface. Each time the electrodeposition image 54 is used, the electrodeposition image 54 can be peeled off from the supporting substrate 55 and attached to the surface of an adherend (not shown) via a fixing adhesive layer. Note that the electrodeposited image peeling step described with reference to FIG.
4 involves the complicated work of peeling off the metal plate 52 together with the conductive film 53, but this work is required to prevent the scattering of the electrodeposited image, the deformation of the electrodeposited image and the metal plate, and the repetition of the metal plate. Necessary for use etc.

[0004]

As described above, in the method of forming an electrodeposited image (electroformed product) disclosed in Japanese Patent Application Laid-Open No. 7-331479, the electrodeposited image is formed on a metal plate together with a conductive film. And a work of peeling only the conductive film from the support substrate with the electrodeposited image is required. If such a complicated and complicated peeling step is repeated twice, it is difficult to manufacture a fine electroformed product with high precision, with good yield, and at low cost.

[0005] Further, in the conventional electroformed products, including those described in the above-mentioned publications, when the electroformed products are peeled from the metal plate and transferred to the supporting substrate, they are transferred without displacement. There was a problem that it was difficult. Furthermore, since the electroformed product has a high internal stress, it may peel off from the metal plate during electroforming,
There was also a problem of warping and deformation. The present invention is directed to overcoming the problems of the prior art as described above. That is, an object of the present invention is to manufacture various electroformed products including, for example, roses on a dial of a wristwatch with high accuracy and high yield without repeating a complicated and complicated peeling step. It is an object of the present invention to provide an improved substrate for forming an electroformed product and a method of manufacturing the same.

Another object of the present invention is to provide a fine electroformed product excellent in design and decoration, and a method for producing such an electroformed product with high accuracy and high yield by a simplified process. To provide. Another object of the present invention is to provide an electroformed product sheet which can easily handle the excellent electroformed product according to the present invention.

A further object of the present invention is to provide a decorative product having excellent design and decorativeness using the excellent electroformed product according to the present invention. The above and other objects of the present invention can be easily understood from the following detailed description.

[0008]

SUMMARY OF THE INVENTION The present invention comprises, on one surface thereof, a metal plate and an electrodeposition film formed on the surface thereof, wherein an electroformed product is formed on the electrodeposition film in a releasable manner. Substrate, wherein the metal plate has a degree of flexibility that can be deformed when the electroformed product is peeled off, and the electrodeposition film covers the entire surface of the metal plate. And all side surfaces and at least the peripheral portion of the back surface of the metal plate is covered, the ease of peeling from the underlying metal plate, the peripheral region of the metal plate and the central region inside the peripheral region near the peripheral region. And a substrate for forming an electroformed product.

According to another aspect of the present invention, there is provided a substrate comprising a metal plate and an electrodeposition film formed on the surface of the metal plate, and capable of forming an electroformed product on the electrodeposition film in a peelable manner. In manufacturing, when peeling the electroformed product from the substrate, prepare a metal plate having a degree of flexibility that can deform itself, and the entire surface and all side surfaces of the metal plate and the metal plate An electrodeposition film is formed on at least a peripheral portion of the back surface of the metal plate. At this time, the electrodeposition film covering the entire surface of the metal plate is easily peeled from the underlying metal plate. A method for manufacturing a substrate for forming an electroformed product, characterized in that processing is performed so that the vicinity region is different from the central region inside the periphery vicinity region.

In another aspect of the present invention, an electroformed product and a substrate supporting the electroformed product in a releasable manner.
A substrate with electroformed article comprising said substrate is composed of a metal plate and formed electrodeposition film on the surface thereof, the metal plate is allowed a degree deformable when peeling the electroformed article It has flexibility, and the electrodeposition film covers the entire surface and all side surfaces of the metal plate and at least the peripheral portion of the back surface of the metal plate, and is easily peeled from the base metal plate. However, there is provided an electroformed product with a substrate , characterized in that a region near the periphery of the metal plate is different from a central region inside the region near the periphery.

Further, the present invention has a Te yet another aspect <br/> smell, in manufacturing the electroformed product, the metal plate that
Prepare a substrate consisting of an electrodeposition film formed on the surface,
At this time, the substrate, to prepare a metal plate having a degree of flexibility that can be deformed when peeling the electroformed product from the substrate,
Then , an electrodeposition film is formed on the entire surface and all side surfaces of the metal plate and at least a peripheral portion of the back surface of the metal plate. At this time, a metal plate as a base of the electrodeposition film covering the entire surface of the metal plate The metal plate is manufactured by processing so that the area near the periphery of the metal plate and the central area inside the area near the periphery of the metal plate are different from each other. Forming an electroformed product by performing electroforming using a selected electroformed metal while covering an area other than the electroformed product forming area with a masking element, Manufacturing method.

In another aspect, the present invention provides, in another aspect, an electroformed product which is peeled off from a substrate and has a fixed layer on a back surface, and is laminated on the back surface of the electroformed product. An electroformed product comprising: a release liner that can be separated from the electroformed product when the electroformed product is applied to an adherend; and an application tape laminated on a surface of the electroformed product. On the sheet.

Still further, the present invention relates to an electroformed product having, on another side thereof, the present invention, wherein the electroformed product is peeled off from a substrate and has a fixed layer on the back surface, and the electroformed product has the fixed layer formed on the back surface. A decorative article comprising an adherend bonded and held through the cover. [Operation] In the case of the conventional electroformed product, as described above, there are problems in the warpage due to the internal stress and the color tone of the decorative plating applied to the surface of the electroformed product. For example, in the case of bright nickel (Ni) electroforming, a first brightener and a second brightener are separately added to the electroforming bath, or a one-pack type brightener (also a first brightener). And a second brightener). Here, the first brightener has an action of giving a compressive stress to the precipitated Ni, while the second brightener gives a tensile stress.
Regarding the cathode surface, the adsorption of the brightener decreases in the portion where the current density is high, but the adsorption of the first brightener particularly increases in the portion where the current density is low. Therefore, the residual concentration ratio of the first and second brighteners and the current distribution (depending on the shape of the pattern and the density)
In some cases, a large compressive stress is applied to the deposited Ni in the important pattern portion to cause a warp in the electroformed product. As a result, the electroformed product cannot be transferred well to the adherend during use, Even if the image could be transferred, it was sometimes peeled or deformed later.

Further, when decorative plating is applied to the surface of an electroformed product after the completion of electroforming, plating with a thin film thickness, such as decorative gold or white plating, tends to receive the color of the underlying metal. . In particular, in the case of a Ni underlayer (electroformed product), since a reddish color peculiar to the Ni undercoat appears, the decorative plating tends to have a dark color tone. In order to solve this, decorative plating is formed thick, an intermediate plating layer is added,
It was necessary to make very laborious adjustments, such as changing the alloy ratio.

On the other hand, when bright Ni electroforming is performed in the present invention, about 0.5 to 12% of the total metal amount of cobalt (Co) is added to the Ni bath to obtain the deposited Ni.
Becomes an alloy containing 1 to 20% of Co. At a current density (approximately ^{2 to} 5 A / dm ² ), which is a practical range, the Co content increases as the current density decreases. Further, as the Co content increases, the tensile stress increases, so that it works to cancel the compressive stress caused by the first brightener. Since the crystal grains of the Ni-Co alloy are finer than those of Ni alone, the total amount of the brightener can be reduced, the stress derived from the brightener is reduced, and the problems of poor transfer and peeling are solved. be able to. Further, since the color of the Ni—Co alloy is whiter than that of Ni alone, the problem that the tint of the decorative plating is adversely affected by the Ni color can also be solved. Such an operation and effect unique to the present invention will be apparent from the following description.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below with reference to the accompanying drawings. In addition,
It is to be understood that this invention is not limited by the particular embodiments described below. FIG. 2 is a cross-sectional view showing an example of the substrate for forming an electroformed product according to the present invention. The substrate 1 includes a metal plate 2 and an electrodeposition film 3 formed on the surface of the metal plate 2, though the substrate 1 may have additional elements as required. Although not shown, an electroformed product can be formed on the electrodeposition film 3 in an arbitrary pattern.

In the substrate for forming an electroformed product of the present invention, the metal plate constituting the skeleton is deformed when the electroformed product is peeled off so that the electroformed product formed on the surface thereof can be easily peeled off. It has as much flexibility as possible. Here, “flexibility to the extent that it can be deformed” cannot be specified in particular by numerical values, but usually causes the metal plate to be easily bent when both ends of the metal plate are moved up and down by hand. Refers to the degree of flexibility that can be achieved.
The flexibility of the metal plate is one of the requirements for separating the electroformed product from the base metal plate in the present invention while the electrodeposition film remains on the metal plate. As the metal plate, various metal plates, for example, a stainless steel plate, a copper plate, a copper alloy plate (such as a brass plate), an aluminum plate, an aluminum alloy plate, and the like can be used. These metal plates are usually used alone, but may be used in a laminate or other forms if necessary. Further, it is preferable that the surface of such a metal plate is usually chemically pretreated by a common technique. Suitable chemical pretreatments include, for example, a degreasing treatment for removing oils and fats adhering to the surface of the metal plate, an activation treatment for removing adhering oxides and the like, and a release treatment after both these treatments. Can be mentioned. The release treatment is performed on the entire metal plate 2, but is preferably performed on the remaining portion of the metal plate 2 excluding the side surface 2 </ b> C,
More preferably, the side surface 2C of the metal plate 2 and the front and back surfaces 2A and 2A
B is applied to the remaining portion excluding the vicinity of the side surface 2C in B.

It is preferable that the electrodeposition film 3 on the surface of the metal plate 2 is not formed so as to cover the entire surface uniformly, but is selectively formed at a specific portion. The selective formation of such an electrodeposition film is also necessary in order to enable the electroformed product to be easily peeled off from the substrate without a defect or the like due to a synergistic effect with the flexibility of the metal plate described above. . As shown in FIG. 2, the electrodeposition film 3 covers the entire surface 2 </ b> A of the metal plate 2 and the entire side surface 2 </ b> C (the wood edge and the edge of the wood) and at least the peripheral portion of the back surface 2 </ b> B of the metal plate. Preferably, it is formed. As a result, the electrodeposition film 3 covering the entire surface 2A of the metal plate 2 is easily peeled from the underlying metal plate 2 in a region near the periphery of the metal plate 2, that is, the peripheral portion of the metal plate 2 and the periphery thereof. The difference is different between the small area inside and the central area (the area indicated by arrow X in the figure) inside the peripheral area. Describing the easiness of peeling of the electrodeposition film 3 from the metal plate 2, it is usually preferable that the easiness of peeling in the region near the peripheral edge of the metal plate 2 is smaller than that in the central region of the metal plate 2. Due to such easiness of peeling, in other words, the distribution of the adhesive force, as will be described in detail below, when the metal plate 2 is deformed, the metal plate 2 is formed in the central region of the metal plate earlier than in the peripheral region of the metal plate. As a result of the electrodeposition film peeling off from the surface of the metal plate and appropriate deformation of the electrodeposition product, efficient separation of the electrodeposition product can be achieved.

FIG. 3 is a perspective view showing an example of an electroformed product according to the present invention, and FIG. 4 is a sectional view taken along line IV-IV of FIG. In the illustrated example, an electroformed product (here, an electroformed number “7”) 4 is adhered to the surface of the substrate 1. The substrate 1 includes the metal plate 2 and the electrodeposition film 3, as described above with reference to FIG. The illustrated metal plate 1 is made of a rectangular metal plate, and has a front surface 2A, a back surface 2B, and a side surface 2A.
C, and the entire front surface 2A and side surface 2C and the periphery of the rear surface 2B are covered with the electrodeposition film 3.

The electroformed product of the present invention can be manufactured from any electroformed metal by using an electroforming method generally used conventionally. Electroformed metals useful for forming electroformed products are:
Although not limited to those listed below, for example, copper (Cu), gold (Au), silver (Ag), cobalt (Co), nickel (Ni), and the like, preferably
Fe, Co, Ni, and alloys thereof, for example, Ni-
Co, Ni-Sn, Ni-Au, Au-Ag and the like. According to the findings of the present inventor, from the viewpoint of preventing peeling, warping, deformation, and the like, and improving the appearance quality, in particular, pure nickel, a cobalt alloy or a nickel alloy, such as a nickel-cobalt alloy, is advantageously used as an electroformed metal. Can be used. In addition, such an electroformed metal usually has inevitable impurities such as C, N, Fe, Cu, and M in its composition.
Contains trace amounts of n, Si, etc.

Examples of cobalt alloys and nickel alloys useful as electroformed metals are as follows. (1) A nickel-cobalt alloy containing 0.1 to 20% by weight of cobalt, with the balance being nickel and unavoidable impurities. (2) A nickel-gold alloy containing 1 to 25% by weight of nickel, with the balance being gold and unavoidable impurities.

(3) A nickel alloy containing 80 to 99.99% by weight of nickel and the balance being inevitable impurities. The thickness of the electroformed product of the present invention is usually determined in relation to the thickness of an electrodeposition film existing as a base, as described above. Although the thickness of the electroformed product can be widely changed depending on the manufacturing conditions and use of the electroformed product,
Usually, it is in the range of about 15 to 80 μm, preferably in the range of about 40 to 60 μm. A thickness of around 50 μm is most advantageous. If the thickness of the electroformed product is less than about 15 μm,
There is a possibility that peeling from the underlying electrodeposited film cannot be performed smoothly or deformation of the electroformed product may be caused. Conversely, if the thickness exceeds about 80 μm, it will only cause disadvantages such as prolonging the electroforming time, and it is unnecessary to adopt such a large thickness.

The electroformed product can have any characteristic planar shape, three-dimensional pattern (cross-sectional shape) and dimensions as long as it does not cause inconvenience such as complicating the manufacturing process. Although a typical cross-sectional shape is a protrusion having a uniform height as shown in FIG. 4, it may have a concave or convex portion, a combination of concave and convex portions, or other cross-sectional shapes as necessary. It may be.

In the electroformed product of the present invention, the surface of the electroformed product may be subjected to finish plating or the like in order to improve the appearance quality. In particular, it is preferable to apply finish plating and other surface treatments, such as anodic oxidation, to the surface of the electroformed product having the three-dimensional pattern. For example, the finish plating can be formed by plating a metal such as gold, silver, platinum, palladium, rhodium, chromium, tin, or a mixture or alloy of the metals using a conventional technique. Further, this finish plating is usually formed in a single layer, but may have a multilayer structure as required. Further, the surface of the electroformed product may be coated according to a conventional method, in combination with the finish plating or alone. The type and method of coating are not limited.

Further, in order to protect the surface of the electroformed product and further enhance the appearance quality, a protective film may be further coated on the electroformed product. Suitable protective films include, for example, a transparent clear layer. Such a clear layer,
For example, it can be easily formed by thinly coating a transparent polyester resin. The clear layer is usually transparent, but may be lightly colored if necessary.

Since the electroformed product of the present invention is fine and has excellent appearance quality and accuracy, it can be advantageously used as a decorative product by applying it to the surface of various adherends in various fields. Can be. For example, this electroformed product can be advantageously used as a display means of a precision instrument.
Examples of applications include rose letters on a clock face (minute scale, regular scale, etc.), nameplates for cameras and home appliances, logo letters, model numbers, scales for speedometers, and the like. Further, the electroformed product of the present invention can also be used as a substitute for a nameplate or a sticker of a vehicle (automobile, motorcycle, scooter, etc.).

[0027] In another aspect, the present invention resides in an electroformed sheet using the electroformed product of the present invention. That is, the electroformed product sheet of the present invention is the electroformed product of the present invention (one that has been peeled off from the substrate and further provided with a fixing layer on the back surface).
And a release liner that is laminated on the back surface of the electroformed product and that can be separated from the electroformed product when the electroformed product is applied to an adherend, and at least an application tape laminated on the surface of the electroformed product. It is characterized by having. The electroformed product sheet of the present invention can have various laminated structures within the above-described range.
This will be described with reference to FIG.

The electroformed product sheet 10 is made of the electroformed product 4 of the present invention.
Is sandwiched between a release liner 8 and an application tape (holding sheet) 7. Electroformed product 4
Although not shown, a fixing layer (for example, an adhesive layer) is provided on the back surface. In the figure, a release liner 8, which is schematically shown in a shape different from the actual shape for simplicity of description, is laminated on a fixing layer provided on the back surface of the electroformed product 4, and Can be peeled from the electroformed product when applied to an adherend (not shown). As the release liner 8, a commercially available release paper, release sheet, or the like can be used. In addition, the application tape 7 is for protecting the electroformed product 4 while preventing it from falling off or being damaged, and can be formed from various materials as long as it has a predetermined holding force. It is advantageous to form the application tape from a transparent plastic film, for example, a polyester film, a polypropylene film, etc., from the advantage that the contents of the design of the electroformed product can be confirmed as it is. On one side of the application tape, a fixing layer (for example, an adhesive layer) is provided to hold the electroformed product.

The electroformed sheet of the present invention can be provided in various forms based on the layer structure as shown in FIG. In particular, it is preferable that a plurality of electroformed products are arranged at substantially equal intervals. Further, it is preferable that such an electroformed product sheet is further provided with a positioning means for applying the electroformed product at a position where the operation of applying the electroformed product to the adherend is not obstructed. As a suitable alignment means, for example, a register mark which is often used in the field of printing and the like can be cited. The alignment means can be formed simultaneously by, for example, electroforming when forming an electroformed product.

The substrate for forming an electroformed product, the electroformed product, the electroformed product sheet, and the decorative product of the present invention can be manufactured by using various techniques commonly used in respective technical fields. Although not limited to those described below, the substrate for forming an electroformed product can be advantageously manufactured by, for example, the following steps. (1) Preparation of a metal plate having a predetermined flexibility; (2) Covering of a predetermined region of the metal plate with an electrodeposition film.

An electroformed product can be advantageously manufactured by sequentially performing the following steps using the substrate manufactured as described above. (3) applying a masking element to the surface of the electrodeposited film on the substrate; (4) forming an electroformed product on the exposed surface of the electrodeposited film;
(5) removal of the masking element, (6) application of the application tape, (7) separation of the electroformed product from the substrate.

The electroformed product manufactured as described above can be used as the decorative product of the present invention by applying a fixing layer to the back surface and then applying and fixing it to the surface of the adherend. On the other hand, when a fixing layer is applied to the back surface of the electroformed product after being separated from the substrate, and the fixing layer is further protected by a release liner, the electrodeposited product sheet of the present invention can be formed.

The above-described method for manufacturing a substrate or the like can be implemented through various steps using a conventional technique. A typical manufacturing method is described with reference to FIGS. I will explain. Although the illustrated manufacturing method shows a typical example of the present invention, it goes without saying that various changes and improvements can be made within the scope of the present invention.

First, in order to manufacture a substrate for forming an electroformed product,
As shown in FIG. 5A, a metal plate 2 having flexibility is prepared. As described above, a copper plate, a stainless steel plate, a brass plate, an aluminum plate, and the like are useful as the metal plate used here. The weight and thickness of such a metal plate can be arbitrarily changed, but it is preferable that the metal plate be as light as possible in consideration of handleability. Also,
The thickness of the metal plate must be thin enough to bend the metal plate when the electroformed product is peeled from the electrodeposition film on the substrate surface. Is preferred. Before forming an electrodeposition film on the surface of the metal plate, it is necessary to perform a pretreatment such as a degreasing process, an activation process for removing oxides and the like on the surface, a washing process, and a mold release process. preferable. The release treatment can be performed, for example, by immersing the pretreated metal plate in an aqueous solution of potassium dichromate. The release treatment is performed on the entire metal plate, but preferably, on the entire metal plate except for the side surface, and more preferably, on the metal plate except for the peripheral portion adjacent to the side surface of the side surface and the front and back surfaces. It can be applied to the whole.

After the completion of the predetermined pretreatment, two metal plates 2 are formed to selectively form an electrodeposition film on the surface of the metal plate.
As shown in the figure, the jigs are fixed back to back with the back surfaces 2B leaving a slight gap therebetween. When such a superposed metal plate is immersed in a plating bath and subjected to plating under predetermined conditions, the central region of the rear surface portion of the metal plate does not allow a sufficient amount of plating solution to enter that portion. This is because no electrodeposition film is formed.

Next, as shown in step (B) of FIG.
After a predetermined pretreatment, an electrodeposition film 3 is formed on the surface of the metal plate 2 after the superposition. The electrodeposition film 3 can be advantageously formed by plating from a metal such as nickel, tin, cobalt, copper, iron or an alloy thereof, for example. The electrodeposition film 3 is usually applied to the surface of the metal plate 2 in a state of a thin film of fine metal / alloy particles. The thickness of the electrodeposited film 3 can be changed in a wide range depending on the composition of the electrodeposited film, the relationship with the underlying substrate, and the like.
~ 50 μm, more preferably about 20 ~
It is in the range of 30 μm. The thickness of the electrodeposited film, if specified in relation to the thickness of the electroformed product thereon,
The thickness is preferably set to 60 to 90% of the thickness of the electroformed product, and more preferably 80 to 90%.

In order to easily and effectively perform the work of peeling the electroformed product from the electrodeposited film on the substrate,
As shown in the figure, it is preferable that the metal plate is formed only on the front surface, the side surface, and at least the peripheral portion of the back surface. this is,
As described below, by performing plating in a state where two metal plates are overlapped as shown in the drawing, it is possible to carry out efficiently.

The formation of the electrodeposited film can be carried out using a conventional plating method and plating bath. Since the electrodeposition film preferably has a smooth surface in order to facilitate the stripping operation of the electroformed product in a later step, the plating bath may include, for example, a first electrode such as sulfinic acid or sulfonic acid. It is preferable to add a second brightener such as a brightener or butynediol. Further, a pit preventing agent (wetting agent) may be added.

In order for the electrodeposition film to be easily peeled off from the metal plate surface in the central region inside the peripheral region of the metal plate, the amount ratio of the first brightener and the second brightener is set as follows: It is preferable to increase the amount of the first brightener from 18 to 30: 1 to 5 to 15: 1 in the ordinary plating bath. In the electrodeposited film obtained by using the plating bath having such a composition, the electrodeposition stress indicated by the electrodeposition is a strong compressive force. That is, the electrodeposition film is attached to the surface of the metal plate in a state where a compressive force acts on the electrodeposition film. Furthermore, in order to prevent the electrodeposition film from being easily peeled off in the vicinity of the peripheral edge of the metal plate, a rough surface may be obtained by applying an abrasive such as sandpaper to the side surface or the vicinity of the metal plate. ,
It is effective to form pores penetrating both the front and back surfaces near the side surfaces.

The plating bath which can be advantageously used for forming the electrodeposition film is a bath having the following composition, although not limited to the following. (1) Watt bath Nickel sulfate 240-300 g / l Nickel chloride 30-50 g / l Boric acid 30-45 g / l Brightener (2) Watt bath Nickel sulfate 240-300 g / l Nickel chloride 30-50 g / l Boric acid 30- 45 g / l Pit inhibitor proper amount In the step (C) in FIG. 5, after the formation of the electroformed film, the two metal plates are separated, and the metal plate 2 having the electrodeposition film 3 in a predetermined pattern, that is, 1 shows a state in which a substrate 1 for forming an electroformed product of the present invention is obtained. The details of the electroformed product forming substrate 1 are as described above with reference to FIG.

After preparing the substrate for forming an electroformed product as described above, an electroformed product is formed on the surface thereof. First, as shown in step (D) of FIG. 5, the entire surface of the substrate 1 is entirely covered with a patternable masking element. Subsequently, an opening of a predetermined pattern is provided, and an electroformed product is formed in the opening. As the masking element,
Various materials can be used as long as it has resistance to electroforming and can be patterned, but a resist material is particularly preferable. Usable resist materials include, for example, a photoresist sensitive to ultraviolet light (UV), an electron beam resist sensitive to electron beam (EB), and the like. Further, instead of such a resist material, a resist ink, a plating resist, a resist film (dry film resist), or the like may be used. here,
In particular, a description will be given with reference to an example in which a photoresist is used as a masking element.

As shown in step (D) of FIG. 5, a photoresist 6 is applied to the entire surface of the substrate 1 at a predetermined thickness (usually using spin coating or the like), dried, and then dried.
As shown in step (E), the electroformed product forming region 6A of the photoresist 6 is removed. This step can be advantageously performed using photolithography technology. That is, after the photoresist 6 is applied, it is exposed to a predetermined pattern, and further, patterning, ie, dissolving and removing unnecessary portions with a developing solution is performed to form the opening 6A corresponding to the pattern of the electroformed product. can do. The pattern exposure step is performed using a positive or negative photomask depending on the type of photoresist used. The exposure source is an ultraviolet ray, an electron beam, a laser beam, or the like.

Subsequently, as shown in step (F) of FIG. 6, the opening 6A formed in the previous step is filled with an electroformed metal, and the electroformed product 4 is formed in a predetermined pattern. Opening 6A
It is preferable that the electroformed film 3 exposed by the above process be subjected to a release treatment that is weaker than the release treatment performed on the metal plate 2. Electroformed product 4
Can be advantageously formed from an electroformed metal such as a nickel alloy or a cobalt alloy using a conventional electroforming method in the same manner as in the case of forming the above-mentioned electrodeposition film. According to the findings of the present inventors, the present invention is not intended to limit the present invention, but particularly good results can be obtained when an electroforming bath having the following specific composition is used. (1) Sulfate bath Nickel sulfate 266-278 g / l Cobalt sulfate 2-15 g / l Nickel chloride 30-45 g / l Boric acid 30-45 g / l Brightener (2) Sulfate bath Nickel sulfate 240-300 g / l Chloride Nickel 30-45 g / l Boric acid 30-45 g / l Brightener Suitable amount (3) Sulfamate bath Nickel sulfamate 430-443 g / l Cobalt sulfamate 2.5-20 g / l Nickel chloride 0-30 g / l Boric acid 30- 45g / l Brightener proper amount (4) Matte sulfamate bath Nickel sulfamate 300-600g / l Nickel chloride 0-30g / l Boric acid 30-45g / l Pit inhibitor proper amount (5) Matte sulfamate bath sulfamine Nickel acid 300-600 g / l Nickel bromide 1-30 g / l Boric acid 30 In the practice of the present invention, if necessary, a plating bath having the same composition as that used for forming the above-mentioned electrodeposited film may be used. May be formed. Further, although it is also used in the above-mentioned electroforming bath, a non-smoothing brightener (non-level brightener), a cobalt salt for reducing the size of precipitated crystal grains, and others May be included in the bath.

After an electroformed product having a required thickness is formed by the electroforming process, the photoresist used as the masking element is dissolved and removed. Usually, a metal plate is immersed in a solvent to dissolve the photoresist, then washed with water and dried. As shown in the step (G) of FIG. 6, an electrodeposit 4 held by the substrate 1 composed of the metal plate 2 and the electrodeposition film 3 coated thereon is obtained.

The formation of the electroformed product will be further described.
In the present invention, when copper, brass, aluminum, or the like is used for the metal plate, an electrodeposition film of a fine-grained metal such as nickel, chromium, or an alloy of tin and cobalt is strongly adhered to the surface of the metal to form a metal. When used as a plate, the metal plate and the electrodeposition film can be easily separated. Further, in such an embodiment, the electrodeposition film can be formed on the entire front and back surfaces of the substrate, so that instead of forming an electroformed product on the surface of the substrate as shown in FIG. An electroformed product can also be formed on the back surface.

After forming the electroformed product as described above, although not shown, it is preferable that the surface of the electroformed product is subjected to a surface treatment such as finish plating or painting. For example,
The plating process can be advantageously performed usually by plating various metals such as gold, silver, and platinum or alloys thereof with a thin film. Of course, other surface treatments such as anodic oxidation may be performed instead of this plating treatment. Such a surface treatment may be performed, if necessary, at a stage before removing the photoresist used as the masking element.

Subsequently, the decorative product 20 of the present invention or the electroformed sheet 10 (described above) shown in FIG. 8 is formed according to the method shown in FIG. First, as shown in step (H) of FIG. 7, an application tape 7 is attached to the surface of the electroformed product 4 held by the substrate 1. The application tape 7 used here is transparent and has an adhesive layer (not shown) on one side. The application tape 7 is, for example, a polyester film, a polypropylene film, or the like.
In the electroformed product of the present invention, other types of application tapes may be used if necessary, but it is advantageous to use a general single-sided adhesive film as it is as the application tape.

Next, as shown in step (I) of FIG.
Application tape 7 from electrodeposition film 3 on substrate 1
It is peeled off with the electroformed product 4 still attached thereto. According to the present invention, this operation is advantageous by deforming the substrate 1 by, for example, bending the substrate 1 with a hand or a jig so that the metal plate 2 becomes convex and the electrodeposition film 3 becomes concave. Can be implemented. A slight gap G is generated between the metal plate 2 and the electrodeposition film 3 thereon, and the electrodeposition film 3 is slightly peeled off from the metal plate 2 on the surface (center region) excluding the region near the peripheral edge of the substrate 1. . Also in this case, the electrodeposition film 3 is still firmly bonded to the metal plate 2 in the region near the periphery of the substrate 1. In such a state, the application tape 7 can be peeled off from the electrodeposition film 3 on the substrate 1 in the direction of the arrow lightly and without causing deformation, damage, displacement or the like of the electroformed product 4. Of course, the electrodeposition film 3 is completely removed from the metal plate 2 and the electroformed product 4
At the same time, the inconvenience of shifting to the application tape 7 side does not occur.

The above-mentioned desirable effects can be obtained because, in the case of the electroformed product of the present invention, the substrate used has a configuration unique to the present invention. That is, although the electrodeposition film is coated around the substrate, this electrodeposition film is formed so as to cover the surface of the substrate, the entire side surface, and at least the peripheral portion of the back surface, and The electrodeposition film covering the whole is formed so as not to be easily peeled off from the surface of the substrate in the region near the periphery of the substrate, while the electrodeposition film is formed in the central region of the substrate (a part other than the region near the periphery). Is formed so as to be easily peeled off from the surface of the substrate, and as described above, so that a slight gap is generated between the metal plate of the substrate and the electrodeposited film thereon. In other words, the electrodeposition film is formed on the substrate in such a manner that a compressive force acts on the electrodeposition film.

In addition to the compressive force of the electrodeposited film, the peeling force between the electrodeposited film and the electroformed product is also important. That is, when the electroformed product is separated from the electrodeposited film of the substrate by pulling the application tape, the thick electroformed product remains almost flat, but the thin electrodeposited film of the part peeled off from the substrate is Since it has flexibility, it is deformed so as to facilitate peeling of the electroformed product, in other words, so that a so-called peeling force easily acts between the electrodeposition film and the electroformed product. . As a result, the electroformed product is smoothly separated from the electrodeposited film on the substrate,
Can be migrated to application tape. Of course, the pressure-sensitive adhesive layer applied to the application tape needs to have a sufficient adhesive strength to meet the requirement.

Step (J) of FIG. 7 shows a state after the application tape 7 has been peeled off from the electrodeposition film on the substrate while the electroformed product 4 is still attached thereto. After obtaining an application tape with an electroformed product as described above, a fixing layer is applied to the back surface of the electroformed product, and the upper surface is further protected by a release liner. An electroformed sheet 10 can be obtained. Here, an example in which an adhesive layer is used as the fixing layer will be described. The application of the pressure-sensitive adhesive layer can be performed efficiently and accurately by, for example, screen-printing the pressure-sensitive adhesive. The pressure-sensitive adhesive that can be used here is a conventional pressure-sensitive adhesive having an appropriate viscosity for screen printing, such as an acrylic pressure-sensitive adhesive. The release liner is preferably replaced with a commercially available release paper with a pressure-sensitive adhesive layer or the like in order to increase work efficiency.

Since the electroformed product sheet has the electroformed product firmly fixed to the application tape, even if the sheet is bent, the electroformed product does not deform, displace, or peel off. A large number of electroformed sheets can be stored and transported in a stacked state. Also, since the release liner can be used immediately just by pulling it apart with a light force, the handleability is very good.

On the other hand, using the application tape 7 with the electroformed product 4 obtained in the step (J) of FIG.
The decorative product 20 of the present invention as shown in FIG. The decorative product 20 can be manufactured by, for example, applying a thin acrylic adhesive 22 on the back surface of the electroformed product 4 and then attaching and fixing the acrylic adhesive 22 to a predetermined portion of the adherend 21. The application tape 7 can be removed after the decoration product 20 is completed. The illustrated decorative product 20
In this case, although the adherend 21 is a plate for easy understanding, the electroformed product 4 of the present invention can be advantageously applied to any type of adherend as well.

[0054]

The following examples serve to further illustrate the invention. The following example is an example,
It goes without saying that the present invention can be applied to various electroformed products, methods for producing the same, and articles using those electroformed products. Example 1 A dial with a wristwatch character (KHR) is manufactured by the following procedure. (1) Preparation of substrate A copper plate having a length of 300 mm, a length of 300 mm, and a thickness of 0.4 mm was immersed in a 5% aqueous solution of caustic soda to obtain a current density of 3 to 5 A /
Cathodic electrolysis is performed at dm ² for 1 to 3 minutes to degrease the copper plate surface. After washing with water, the degreased copper plate is immersed in 5% diluted sulfuric acid at room temperature for 1 minute to perform an activation treatment, and then washed again with water. Next, the activated copper plate is immersed in a 0.5% aqueous potassium dichromate solution at room temperature for 2 minutes and washed with water. (2) Formation of Electrodeposited Film After completion of the release treatment as described above, an electrodeposited film made of nickel is formed on the surface of the copper plate as follows.

A jig is fixed with two copper plates back to back with their back surfaces slightly spaced. Electroplating is performed by dipping in a bright plating bath (Watts bath) having the following composition. Composition of plating bath Nickel sulfate 280 g / l Nickel chloride 40 g / l Boric acid 40 g / l Brightener (first and second) Suitable amount Plating condition temperature 55 ° C. ± 5 ° C. pH 4.0 ± 0.5 Current density 3 A / dm ² Time Approximately 45 minutes After the electrolytic plating, the two copper plates are separated, each copper plate is immersed in acid, washed with water and dried.

As a result of the electrolytic plating, a nickel film having a uniform film thickness of about 25 μm is formed on the surface and the side surface of the copper plate directly in contact with the plating bath. On the back surface where the copper plates face each other, a nickel film is formed only on the periphery (width of about 5 cm). This is because the plating solution could not enter the gap between the two copper plates because the copper plates overlapped. (3) Preparation of electroformed mold A negative dry film resist having a thickness of 50 μm (trade name “FOTEC H-N65 manufactured by Hitachi Chemical Co., Ltd.)
0 ”), and a roll temperature of 100 ° C. is applied between the pair of rolls.
Then, it is guided at a feed speed of 1 m / min and laminated.

Next, a positive photomask corresponding to the pattern of the electroformed product is brought into close contact with the copper plate with the dry film resist in a vacuum frame, and is exposed with a mercury lamp (wavelength 365 nm). The exposure amount is 70 mJ / cm ² and the exposure time is 60 seconds. After leaving the exposed dry film resist for 15 minutes, it is developed with a 1% anhydrous sodium carbonate aqueous solution by a pressure shower. The development temperature is about 30 ° C. After the development is completed, the film is washed with water and dried by air blow. A copper plate (electroformed master) having a dry film resist having an opening in a region where an electroformed product is to be formed is obtained.

In order to perform electroforming, a lead wire is connected to the obtained electroformed master, and an adhesive tape for plating masking is attached to the side and back surfaces of the electroformed mother. (4) Formation of Electroformed Article The electroformed mold prepared in the previous step is immersed in a 5% dilute sulfuric acid aqueous solution for 1 minute, activated, and washed with water. Next, for mold release treatment, the electroformed mold is immersed in a 0.5% aqueous potassium dichromate solution at room temperature for 2 minutes and washed with water. Instead of such a release treatment, a method such as anodic oxidation in an aqueous alkaline solution may be used.

After the release process is completed as described above,
An electroformed product made of nickel is formed on the surface of the electroformed mold as follows. The electroforming mold is immersed in an electroforming bath (bright sulfate bath) having the following composition, and electroforming is performed under the following conditions. Composition of electroforming bath Nickel sulfate 275 g / l Cobalt sulfate 5 g / l Nickel chloride 40 g / l Boric acid 40 g / l Brightener Appropriate amount Electroforming condition temperature 55 ° C. ± 5 ° C. pH 3.5 ± 0.5 Current density 3 A / dm ² Time Approximately 1.5 hours In the obtained electroformed product, the following method is used to keep the alloy composition constant.

1. The anode is a separate anode of Ni and Co, a separate power supply is connected to each anode, and the alloy ratio is controlled by controlling the current flowing through the anode. 2. The anode is a separate anode of Ni and Co, and the power supply is common. The current of the Co anode is controlled by a variable resistor. 3. Only the Ni anode is used, and the alloy ratio is controlled by the Co content in the electroforming bath. Periodically analyze the composition of the electroforming bath and determine
When the o-content is reduced by consumption, it is replenished by adding Co salts. For example, at a current density of 3 A / dm ² , the proportion of Co ⁺⁺ of all metals in the electroforming bath is 2%, 4%, 4%, 8%, 12%, and 20% of the proportion of Co in the deposited metal .

After the completion of the electroforming, the lead wire connected to the electroforming mold and the adhesive tape covering the same are removed, washed with water and dried. The thickness of the obtained electroformed product is about 50 μm, as with the dry film resist used for masking.
m. (5) Finish Plating After forming an electroformed product as described above, the electroformed
It is immersed in a 2% aqueous solution of caustic soda at ℃, and the dry film resist is peeled off while brush-washing.

After immersion in acid and washing with water, the surface of the electroformed mold is subjected to finish gold plating. The plating bath is “Lumine gold plating” (trade name) manufactured by Victoria. The conditions of the finish plating are as follows. Temperature 40 ° C. pH 4.0 Current density 1 A / dm ² hours Approximately 40 seconds In place of the above-described gold plating, plating of gold alloy, silver, silver alloy, tin alloy, or the like may be performed. (6) Separation of electroformed product Application tape (in this example,
Using a film masking tape manufactured by Teraoka Seisakusho Co., Ltd.) and firmly fixed to the surface of the electroformed product. Next, the electroformed matrix is deformed while being bent upward by hand at both ends. At the center of the electroformed mold, the electrodeposition film is separated from the copper plate. Under such a condition, the application tape is peeled from the surface of the electroformed mold. The peel angle of the application tape is approximately 90 ° with respect to the surface of the electroformed mold. The electroformed product is transferred from the surface of the electroformed mold to the adhesive surface of the application tape without any problem. (7) Production of electroformed product sheet Back side of electroformed product (surface without application tape)
With an acrylic resin-based pressure-sensitive adhesive (trade name “Olivine BPS4891S” manufactured by Toyo Ink Mfg.). Coat thinly and heat in an oven to cause a crosslinking reaction. The cross-linking reaction is carried out by air drying at room temperature for 1 hour and then leaving at 40 ° C. for 8 hours or more.
When the pressure-sensitive adhesive layer of the application tape is made of a UV-reactive pressure-sensitive adhesive, the adhesive force of the pressure-sensitive adhesive is reduced by irradiating ultraviolet rays. After the pressure-sensitive adhesive layer is dried, release paper (trade name “Separator KP-8B” manufactured by Nitto Denko) is laminated on the surface thereof. An electroformed product sheet in which the electroformed product is sandwiched between application tape and release paper and fixed is obtained. (8) Manufacture of the dial While releasing the release paper from the electroformed product sheet, the electroformed product sheet is affixed to the surface of the separately prepared blue-coated dial while aligning the electroformed product sheet. For registration, registration marks for positioning are formed in advance at corners of the electroformed product sheet. A dial is obtained in which the KHR is accurately affixed at a predetermined position. Example 2 A dial with a KHR of a wristwatch is manufactured according to the method described in Example 1 above. In this example, the electroformed product is formed using the following electroforming bath. Composition of electroforming bath Nickel sulfamate 445 g / l Cobalt sulfamate 5 g / l Nickel chloride 10 g / l Boric acid 30 g / l Brightener Appropriate amount Electroforming conditions Temperature 55 ° C. ± 5 ° C. pH 3.5 ± 0.5 Current density 2. 5 A / dm ² hours About 6.5 hours In this example, the same satisfactory results as in Example 1 are obtained. [Preferred Embodiments] The present invention has been described in detail with reference to the embodiments and examples. Finally, for further understanding of the present invention, preferred embodiments of the present invention are summarized as follows.

[Embodiment 1] A substrate comprising a metal plate and an electrodeposition film formed on the surface thereof, on which the electroformed product can be peelably formed on the electrodeposition film, wherein the metal plate But,
The electroformed product has a degree of flexibility that can be deformed when peeled off, and the electrodeposition film covers the entire surface and all side surfaces of the metal plate and at least the peripheral portion of the back surface of the metal plate. It is characterized in that it is configured to cover and be easily peeled from the underlying metal plate in a region near the periphery of the metal plate and a central region inside the region near the periphery of the metal plate. For forming an electroformed product.

[Embodiment 2] The embodiment 1 is characterized in that the electrodeposited film is more easily peeled from the metal plate in the central region than in the region near the peripheral edge of the metal plate. Substrate for forming electroformed products. [Aspect 3] Aspect 1 or 2, wherein when the metal plate is deformed, the electrodeposition film can be separated from the surface of the metal plate in the central region earlier than in the region near the peripheral edge of the metal plate. 3. The substrate for forming an electroformed product according to item 2.

[Embodiment 4] The electroforming method according to any one of Embodiments 1 to 3, wherein the electrodeposition film is formed on the surface of the metal plate in a state where a compressive force acts on the electrodeposition film. Product forming substrate. [Embodiment 5] The substrate for forming an electroformed product according to any one of Embodiments 1 to 4, wherein the electrodeposition film is made of nickel, tin, cobalt, copper, iron or an alloy thereof.

[Embodiment 6] The thickness of the electrodeposited film is 10 to
The substrate for forming an electroformed product according to any one of aspects 1 to 5, wherein the substrate has a thickness of 50 µm. [Embodiment 7] The electroformed product according to any one of Embodiments 1 to 6, wherein the metal plate is made of a stainless steel plate, a copper plate, a copper alloy plate, an aluminum plate, an aluminum alloy plate or a laminate thereof. Forming substrate.

[Embodiment 8] In manufacturing a substrate comprising a metal plate and an electrodeposited film formed on the surface thereof and capable of forming an electroformed product on the electrodeposited film in a releasable manner, Prepare a metal plate having a degree of flexibility that can be deformed when the casting is peeled from the substrate, and at least on the entire peripheral surface and all side surfaces of the metal plate and at least the peripheral portion of the back surface of the metal plate. An electrodeposition film is formed, and at that time, the electrodeposition film covering the entire surface of the metal plate is more easily peeled from the underlying metal plate, and the peripheral region of the metal plate and the peripheral region thereof A substrate different from the inner central region.

[Embodiment 9] The metal plate is coated with an electrodeposition film such that the electrodeposited film is larger in the central region than in the region near the peripheral edge of the metal plate. 9. The method for manufacturing a substrate for forming an electroformed product according to aspect 8. [Aspect 10] Aspect 8 or 9, wherein a stainless steel plate, a copper plate, a copper alloy plate, an aluminum plate, an aluminum alloy plate, or a laminate thereof is used as the metal plate.
4. The method for producing a substrate for forming an electroformed product according to claim 1.

[Embodiment 11] Any one of Embodiments 8 to 10, wherein the electrodeposited film is formed after the surface of the metal plate is subjected to electrolytic degreasing treatment, activation treatment and release treatment.
The method for producing a substrate for forming an electroformed product according to the above item. [Aspect 12] The substrate for forming an electroformed product according to any one of Aspects 8 to 11, wherein the electrodeposition film is formed by plating from nickel, tin, cobalt, copper, iron or an alloy thereof. Production method.

[Embodiment 13] In any one of Embodiments 8 to 12, wherein the metal plate is immersed in a plating bath (1) or (2) having the following composition to form the electrodeposited film. (1) Watt bath Nickel sulfate 240-300 g / l Nickel chloride 30-50 g / l Boric acid 30-45 g / l Brightener (2) Watt bath Nickel sulfate 240-300 g / L Nickel chloride 30-50 g / l Boric acid 30-45 g / l Pit inhibitor Suitable amount.

[Embodiment 14] The electrodeposition film is formed by immersing two metal plates in a plating bath with the back surfaces of the metal plates facing each other with a slight gap therebetween. The method for producing a substrate for forming an electroformed product according to any one of aspects 8 to 13. [Aspect 15] An electroformed product formed releasably on a substrate, wherein the substrate comprises a metal plate and an electrodeposition film formed on a surface of the metal plate, and the metal plate is formed of the electroformed product. The electrodeposited film has a degree of flexibility that can be deformed when peeled off, and the electrodeposition film covers the entire surface and all side surfaces of the metal plate and at least the peripheral portion of the back surface of the metal plate. Electroforming is characterized in that the metal sheet is easily peeled off from the metal plate in a region near the periphery of the metal plate and a central region inside the region near the periphery. Goods.

[Embodiment 16] The ease with which the electrodeposition film is peeled from the metal plate is greater in the central region than in the region near the periphery of the metal plate. The electrodeposition film is separated in the central region before the peripheral region of the metal plate is separated from the metal plate, so that the subsequent operation of separating the electroformed product from the substrate can be easily performed. Item 15. The electroformed product according to item 15.

[Embodiment 17] The embodiment 15 or 16 is characterized in that the work of peeling the electroformed product from the substrate is performed by attaching an application tape to the electroformed product holding surface of the substrate and then peeling the application tape. Electroformed product as described. [Aspect 18] The electroformed product according to any one of Aspects 15 to 17, wherein the film thickness of the electrodeposited film is in a range of 10 to 50 µm.

[Embodiment 19] The electroformed product is formed by performing electroforming in a state where a region other than the electroformed product forming region on the electrodeposited film is covered with a masking element. The electroformed product according to any one of aspects 15 to 18, wherein [Aspect 20] The electroformed product according to any one of Aspects 15 to 19, wherein the thickness of the electroformed product is in a range of 15 to 80 µm.

[Embodiment 21] The embodiment 1 is characterized in that the metal plate is made of a stainless steel plate, a copper plate, a copper alloy plate, an aluminum plate, an aluminum alloy plate or a laminate thereof.
21. The electroformed product according to any one of 5 to 20. [Aspect 22] Aspects 15 to 21, wherein the electroformed product is formed of at least one type of electroformed metal selected from the group consisting of copper, gold, silver, cobalt, nickel and alloys thereof. The electroformed product according to any one of the above. [Aspect 23] An aspect 2 characterized in that the electroformed metal is a nickel-cobalt alloy, contains 1 to 20% by weight of cobalt, and the balance is nickel and unavoidable impurities.
2. The electroformed product according to 2.

[Aspect 24] The electroforming according to aspect 22, wherein the electroformed metal is nickel or an alloy thereof, contains 80 to 99.99% by weight of nickel, and the remainder is inevitable impurities. Goods. [Aspect 25] Finish plating and / or painting of at least one metal material selected from the group consisting of gold, silver, platinum, palladium, rhodium, chromium and tin and alloys thereof on the surface of the electroformed product 25. The electroformed product according to any one of aspects 15 to 24, wherein the electroformed product is provided.

[Aspect 26] The electroformed product according to any one of Aspects 15 to 25, wherein the electroformed product is peeled off from the substrate and used as a rose character or the like on a clock face of a timepiece. [Aspect 27] In manufacturing an electroformed product formed to be peelable on a substrate, a metal plate having a degree of flexibility that can be deformed when the electroformed product is peeled from the substrate is prepared. Forming an electrodeposition film on the entire surface and all side surfaces of the metal plate and at least a peripheral portion of the back surface of the metal plate, wherein the base metal plate of the electrodeposition film covering the entire surface of the metal plate; The metal plate is processed so that the peeling from the peripheral region is different between the peripheral region of the metal plate and the central region inside the peripheral region, and the surface of the electrodeposited film is electroformed. A method for producing an electroformed product, comprising forming an electroformed product by performing electroforming using a selected electroformed metal in a state where a region other than a formation region is covered with a masking element.

[Aspect 28] The method for producing an electroformed product according to Aspect 27, wherein a resist material is used as the masking element. [Aspect 29] A solution of a resist material or a resist ink is applied to the surface of the electrodeposited film to form a resist film or a resist film is applied, and then, if necessary, the resist film or the resist film The method for producing an electroformed product according to aspect 28, wherein a region other than the electroformed product formation region of the electrodeposited film is covered with a resist material by patterning.

[Embodiment 30] The electroformed metal is copper, gold,
30. The method for producing an electroformed product according to any one of aspects 27 to 29, wherein the electroformed product is at least one type of electroformed metal selected from the group consisting of silver, cobalt, nickel, and an alloy thereof. [Embodiment 31] An embodiment 3 wherein the electroformed metal is a nickel-cobalt alloy, contains 1 to 20% by weight of cobalt, and the balance is nickel and unavoidable impurities.
0. The method for producing an electroformed product according to item 0.

[Aspect 32] The electroforming according to aspect 30, wherein the electroformed metal is nickel or an alloy thereof, contains 80 to 99.99% by weight of nickel, and the remainder is inevitable impurities. Product manufacturing method. [Aspect 33] The electroforming step is performed by bathing (1) having the following composition.
-(5): (1) Sulfate bath Nickel sulfate 266-278 g / l Cobalt sulfate 2-15 g / l Nickel chloride 30-45 g / l Boric acid 30-45 g / l Brightener Appropriate amount (2) Sulfate bath Nickel sulfate 240 -300 g / l Nickel chloride 30-45 g / l Boric acid 30-45 g / l Brightener (3) sulfamate bath nickel sulfamate 430-443 g / l cobalt sulfamate 2.5-20 g / l nickel chloride 0-30 g / L boric acid 30-45g / l brightener proper amount (4) matte sulfamate bath nickel sulfamate 300-600g / l nickel chloride 0-30g / l boric acid 30-45g / l pit inhibitor proper amount (5) matte Sulfamate bath Nickel sulfamate 300-600 g / l Nickel bromide 1-30 g / Boric 30~45g / l method of manufacturing electroformed article according to any one of embodiments 27-32, wherein the performed using a member selected from the group consisting of a pit preventing agent qs.

[Embodiment 34] Embodiments 27 to 33 characterized in that the electroformed product is formed thicker than the electrodeposited film.
The method for producing an electroformed product according to any one of the above. [Aspect 35] The method for producing an electroformed product according to any one of Aspects 27 to 34, wherein the thickness of the electroformed product is in a range of 15 to 80 μm. [Aspect 36] The method for producing an electroformed product according to Aspect 35, wherein the thickness of the electrodeposited film is in a range of 10 to 50 µm.

[Embodiment 37] On the surface of the electroformed product, gold,
Aspects 27 to 27 further comprising a step of applying a finish plating and / or coating of at least one metal material selected from the group consisting of silver, platinum, palladium, rhodium, chromium and tin and alloys thereof. 36. The method for producing an electroformed product according to any one of 36. [Aspect 38] Any of Aspects 27 to 37, further comprising a step of attaching an application tape to the electroformed product holding surface of the substrate and then peeling the application tape to separate the electroformed product from the substrate. 2. The method for producing an electroformed product according to claim 1.

[Embodiment 39] The method for producing an electroformed product according to the embodiment 38, further comprising a step of forming a fixed layer on the back surface of the electroformed product after the electroformed product is separated from the substrate. . [Aspect 40] The method for producing an electroformed product according to Aspect 39, further comprising a step of laminating a release liner on the fixed layer side of the electroformed product.

[Embodiment 41] The electroformed product according to any one of Aspects 15 to 26, wherein the electroformed product is peeled off from the substrate and has a fixed layer on the back surface, the electroformed product being laminated on the back surface of the electroformed product. An electroformed product sheet comprising: a release liner that can be separated from the electroformed product when the product is applied to an adherend; and an application tape laminated on a surface of the electroformed product.

[Embodiment 42] The electroformed product according to any one of Embodiments 15 to 26, wherein the electroformed product is separated from the substrate and has a fixed layer on the back surface, and the electroformed product is bonded via the fixed layer, A decorative product comprising an adherend being held.

[0086]

As described above, according to the present invention, an electroformed product (KHR) such as a rose character formed on a substrate is provided.
Can be quickly transferred to the application tape, and at that time, the occurrence of defective products (peeling, breakage, etc.) during production due to misalignment can be greatly reduced,
The yield can be improved. Furthermore, according to the present invention, since the production process can be shortened and the operation can be simplified as compared with the conventional electroformed product, mass productivity can be greatly improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically illustrating a conventional method of forming an electrodeposited image.

FIG. 2 is a cross-sectional view illustrating an example of the substrate for forming an electroformed product of the present invention.

FIG. 3 is a perspective view showing an example of an electroformed product of the present invention.

4 is a cross-sectional view of the electroformed product of FIG. 3 taken along line IV-IV.

FIG. 5 is a cross-sectional view sequentially showing a manufacturing process (first half) of the electroformed product of the present invention.

FIG. 6 is a cross-sectional view showing the manufacturing process (second half) of the electroformed product of the present invention in order.

FIG. 7 is a cross-sectional view showing the manufacturing process of the decorative product of the present invention in order.

FIG. 8 is a sectional view showing an example of an electroformed product sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate for forming electroformed products 2 ... Metal plate 3 ... Electrodeposited film 4 ... Electroformed product 6 ... Resist material 7 ... Application tape 8 ... Release liner 10 ... Electroformed product sheet 20 ... Decorative product 21 ... Substrate 22 … Adhesive layer

Claims (14)

(57) [Claims] 1. A substrate comprising a metal plate and an electrodeposition film formed on a surface thereof, wherein the metal plate is capable of forming an electroformed product on the electrodeposition film in a releasable manner. The electrodeposited film has flexibility enough to be deformable when the electroformed product is peeled off, and the electrodeposition film covers at least a peripheral portion of the entire surface and all side surfaces of the metal plate and the back surface of the metal plate. It is characterized in that it is configured to cover and be easily peeled from the underlying metal plate in a region near the periphery of the metal plate and a central region inside the region near the periphery of the metal plate. For forming an electroformed product. 2. The substrate according to claim 1, wherein the electrodeposition film is made of nickel, tin, cobalt, copper, iron or an alloy thereof. 3. A method for manufacturing a substrate comprising a metal plate and an electrodeposited film formed on a surface thereof and capable of forming an electroformed product on the electrodeposited film in a releasable manner. Prepare a metal plate having such a degree of flexibility that it can be deformed when peeled off from the substrate, and electrodeposit the entire surface and all side surfaces of the metal plate and at least the peripheral portion of the back surface of the metal plate. A film is formed, and at this time, the electrodeposited film covering the entire surface of the metal plate is easily peeled from the underlying metal plate, and the region near the periphery of the metal plate and the region closer to the periphery of the metal plate. A method for producing a substrate for forming an electroformed product, wherein the substrate is processed so as to be different from a central region of the substrate. 4. An electroformed product, and the electroformed product is detachably supported.
An electroformed product with a substrate , comprising: a metal substrate and an electrodeposition film formed on a surface of the electroformed product, wherein the metal plate is deformable when the electroformed product is peeled off. The electrodeposited film covers the entire surface and all side surfaces of the metal plate and at least the peripheral portion of the back surface of the metal plate, and is separated from the base metal plate. The electroformed product with a substrate is characterized in that the ease with which the metal plate is formed is different between a region near the periphery of the metal plate and a central region inside the region near the periphery. 5. The electroformed product is made of at least one type of electroformed metal selected from the group consisting of copper, gold, silver, cobalt, nickel and alloys thereof. An electroformed product with a substrate according to the item. 6. The electrode with a substrate according to claim 5, wherein the electroformed metal is nickel or an alloy thereof, contains 80 to 99.99% by weight of nickel, and the remainder is inevitable impurities. Castings. 7. A finish plating of at least one metal material selected from the group consisting of gold, silver, platinum, palladium, rhodium, chromium and tin and alloys thereof on the surface of the electroformed product, and / or The base according to any one of claims 4 to 6, wherein the base is coated.
Electroformed product with plate . In producing the 8. electroforms, a substrate made of a metal plate and formed electrodeposition film on the surface thereof
Preparing, at this time, preparing a metal plate having such flexibility that the substrate can be deformed when the electroformed product is peeled off from the substrate, and the entire surface and the entire surface of the metal plate An electrodeposition film is formed on at least a peripheral portion of the side surface and the back surface of the metal plate. At this time, the electrodeposition film covering the entire surface of the metal plate is easily peeled from the underlying metal plate by the metal. The plate is manufactured by processing so as to be different in the peripheral region and the central region inside the peripheral region, and on the surface of the electrodeposition film, a region other than the electroformed product forming region is formed. Forming an electroformed product by performing electroforming using a selected electroformed metal in a state where the electroformed product is covered with the masking element. 9. A surface of the electrodeposition film, a solution or resist ink resist material is applied whether or resist film to form a resist film was coated, patterning the resist film or the resist film followed Teso 9. The method of manufacturing an electroformed product according to claim 8, wherein the masking element is prepared by coating a region other than the electroformed product forming region of the electrodeposition film with a resist material. 10. The electroformed metal according to claim 8, wherein the electroformed metal is at least one type of electroformed metal selected from the group consisting of copper, gold, silver, cobalt, nickel and alloys thereof. The method for producing the electroformed product described in the above. 11. The electroforming step is performed by baths (1) to (5) having the following composition: (1) Sulfate bath Nickel sulfate 266 to 278 g / l Cobalt sulfate 2 to 15 g / l Nickel chloride 30 to 45 g / l boric acid 30-45 g / l brightener proper amount (2) sulfate bath nickel sulfate 240-300 g / l nickel chloride 30-45 g / l boric acid 30-45 g / l brightener proper amount (3) sulfamate bath nickel sulfamate 430 ４４443 g / l cobalt sulfamate 2.5-20 g / l nickel chloride 0-30 g / l boric acid 30-45 g / l brightener suitable amount (4) matte sulfamate bath nickel sulfamate 300-600 g / l nickel chloride 0 -30 g / l boric acid 30-45 g / l pit inhibitor proper amount (5) matte sulfamate bath sulfamate nit Kel 300 to 600 g / l Nickel bromide 1 to 30 g / l Boric acid 30 to 45 g / l Pit inhibitor An appropriate amount selected from the group consisting of: 2. The method for producing an electroformed product according to claim 1. 12. The surface of the electroformed product, wherein gold, silver, platinum,
12. The method according to claim 8, further comprising a step of applying a finish plating and / or coating of at least one metal material selected from the group consisting of palladium, rhodium, chromium, tin and alloys thereof. Or 1
The method for producing an electroformed product according to the above item. 13. An electroformed product provided with a substrate as described above.
After manufacturing, an application tape is attached to the electroformed product holding surface of the substrate, and the application tape is pulled.
Ri by, electroforms method according to any one of claims 8 to 12, wherein the this <br/> detaching the substrate electrodeposition film from electroformed article. 14. An application with an electroformed product as described above.
After producing the application tape, manufacturing method of electroforming article according to claim 13, wherein the benzalkonium to form a fixing layer on the back surface of the electroformed article.