JPS605679B2 - Manufacturing method of electroformed products and substrate for electroforming - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a manufacturing method for haze rust products and a base for haze coins, and more specifically, to a metal having a complex shape that has good precision and mass production, and has excellent yield and quality. The present invention relates to a method for industrially providing electronic mirror products at low cost, and a substrate used therein.

Conventionally, a method has been used in which a conductive support is placed in an exposure solution, the surface of the support is coated with mist, the support is then taken out from the exposure solution, and the deposited metal is peeled off from the support. Methods for producing rusted products are well known and are widely used in various fields such as the electronic industry, chemical industry, and watch industry.

In order to obtain a metal electric mirror product with a desired image, the substrate for the crab blind can be formed by forming an electrically insulating film such as a photoresist on the surface of the metal, or by etching the metal to form a recess. , the hole is filled with an electrically insulating material. Alternatively, a metal or other conductive film is deposited on the surface of an electrically insulating material such as glass or plastic using techniques such as electroless coating, vacuum deposition, or sputtering, and this film is partially etched to create the desired image. is used. In addition, methods have been proposed and implemented in which a base made of metal and an electrically insulating material is used as a coin by combining various other methods.

However, these conventional lightning mirror bases have poor durability, and most of them can withstand only one to three uses, and have an extremely short lifespan.

This is often because when the exposed material is peeled off from the substrate, a portion of either the metal or the insulating material, or in some cases both, falls off or is missing from the substrate, making it impossible to maintain the desired image. This is undesirable as it reduces the mass productivity of Russian coin products and unnecessarily increases the number of haze key bases produced. On the other hand, “indium oxide,
Since the conductive film of tin oxide or chromium has conductivity, it is thought that metal can be deposited on the surface thereof by adhesion.

Moreover, even if the deposits are peeled off from these conductive films, the conductive films of indium oxide, tin oxide, or chromium do not easily peel off from the glass, and the adhesion between the glass and these conductive films is extremely poor. It is solid. On the other hand, indium oxide and tin oxide are often used as transparent electrodes in liquid crystal display devices and other devices, and transparency is important, so although they are conductive, they have relatively high electrical resistance, so they cannot be used with normal fin attachment methods. It can be electrodeposited only on a very limited small area, and it is difficult to uniformly electrodeposit it over a relatively wide area.

Furthermore, the lightning speed was slow, and if the voltage was increased to increase the lightning speed, the indium oxide and tin oxide would be partially burned out, causing dielectric breakdown, making it impossible to continue landing.

In addition, even if the electrical lead part is held in place by a clip, the conductive film may burn out even if the voltage is slightly increased, or if a part of the clip is submerged in the hook,
The clip becomes a cathode, while the conductive film near the clip becomes an anode due to the bipolar phenomenon, so the conductive film near the clip dissolves in the electrodeposition bath, resulting in either no conductivity or very high electrical conductivity. This may create resistance and make it impossible to continue Kamejiku. Therefore, for these reasons, it is difficult to obtain a coin product by electrodepositing a metal on a conductive film of indium oxide, tin oxide, or chromium using a conventional method. The present inventor believes that if a substrate having a conductive film of indium oxide or tin oxide on the glass surface can be used for coins, its durability will be unparalleled. As a result of research aimed at eliminating the above drawbacks,
This has led to the present invention.

That is, the present invention provides a method in which a highly conductive substance is provided on the conductive film at the periphery of the glass of the substrate, and conduction is established through the substance to the conductive/suspicious film to form a tortoise bond. This article focuses on the above-mentioned coin base used. The above-mentioned substrate of the present invention can be used to manufacture metal foils, metal cylinders, endless belts, three-dimensional fin coin items, etc. with high precision, which may or may not have a desired image even after being reused tens or hundreds of times. It has the characteristics of being able to

Hereinafter, the above-mentioned present invention will be explained in detail.

FIG. 1 is a perspective view conceptually showing an example of the base for coins of the present invention, in which a glass plate 1 has a conductive film 2 made of indium oxide or tin oxide on its surface, A substance 3 having good conductivity is provided on the conductive film 2 at the periphery of the surface having the conductive film 2. In Figure 1, the case where the glass is plate-shaped is illustrated, so the substance 3
are provided around the four sides of the liquid, but for example, if the glass is cylindrical, they can be provided around the top and/or bottom end of the cylinder.

Note that even when the glass is plate-shaped as shown in FIG. 1, it is not necessary to provide the substance 3 on all four sides as shown in the figure.
It is sufficient that the substance 3 is provided at least in a part of the peripheral area. To provide the above conductive film on the glass surface, vacuum evaporation,
This can be done by conventional means such as sputtering.

If the electrical resistance of this film is less than 5000', it can be energized and normal work can be done, but if it is greater than 5000/', an excessive voltage is required for energization, so it is preferable that the electrical resistance is 5,000'/'. Set it so that it is smaller.

If this film is left on the entire surface of the glass, it is possible to obtain a flat foil-like flea coin product without an image.
By removing a portion of this film by photoetching or other means to form a desired image, it is possible to obtain an electrical money product with a desired pattern. As described above, the electrical resistance of a conductive film made of indium oxide or tin oxide, with or without an image, provided on glass is generally relatively large.

That is, for example, in the case of indium oxide, the thickness of 0.5 peaks is about 1000'□.

For this reason, it is conceivable to make the film thicker in order to lower the resistance value, but doing so would make the film more likely to peel off from the glass, which is not practical. Therefore, in order to improve this drawback, a material with good conductivity is provided on the conductive film around the base. This substance is, for example, gold, silver,
copper, nickel, lead, etc., and its electrical resistance is 300/
It is desirable that it be smaller than the size of a mouth. This material can be provided, for example, by applying a silver paste or by depositing a foil of copper, nickel, etc. with a silver paste or other conductive adhesive. In order to keep the electrical resistance within the above range, for example, when using silver paste, the thickness is 1
Apply approximately 0.01, and in the case of copper foil or nickel foil, apply approximately 50 to 0.01.
It is preferable to use one with a thickness of about 200 mm. Further, in the present invention, it is desirable to make the contact area of the clip for introducing electricity as wide as possible.

Next, a method for manufacturing an open-air casting product according to the present invention will be explained.

The manufacturing method is characterized by electrodeposition by making it conductive to the conductive film through the highly conductive substance of the base for dew coins according to the present invention, and other aspects are carried out in almost the same manner as the conventional method. However, in the present invention, the above-mentioned coin substrate is placed in an electrodeposition solution for an extremely short period of time (for example, 3
By performing lightning deposition at a high voltage (for example, 7V) and then performing electrodeposition under the same conditions as before (4V, 3A'd pillow), more uniform electrodeposition can be achieved. be able to. In order to establish continuity with the conductive film through a substance with good conductivity in the above case, the lead wire can be connected to the above substance by a normal method, but in particular, a clip with a lead wire and a large contact area can be used. It is preferable to use the method of sandwiching the above-mentioned substances from the viewpoint of reliability of connection, repeatability, etc., and is "industrially effective."

Furthermore, in the present invention, the conductive film of indium oxide or tin oxide has extremely good adhesion to glass, whereas the exposed metal has the characteristic that it is very easy to peel off from these conductive films.

Therefore, even if the electrodeposited metal is peeled off from the coin base after exposure,
The conductive films of indium oxide or tin oxide do not peel off from the substrate, and the images formed by these conductive films are maintained with high accuracy, and this favorable state was maintained even after using this substrate many times. It will be done. On the other hand, since glass is used as the non-conductive material in this case, even if the electrodeposited metal is peeled off from the electroformed substrate, no damage will occur. Either embedding an electrically insulating material in metal as in the past, or
With the adhesion method, the insulating material may partially peel off or fall off after just 1 to 3 uses, resulting in defects in kasumei products, decreased accuracy, and
A surprising result can be obtained when compared with the fact that the base for Russian coins has become unusable. In other words, the military base of the present invention can be used repeatedly an extremely large number of times because the image made of the combination of the conductive film of indium oxide or tin oxide and glass is maintained stably without falling off or being damaged. However, it does not cause any abnormality in its performance, has extremely good accuracy, and is extremely durable. Furthermore, glass plates coated with indium oxide or tin oxide can be obtained relatively easily and inexpensively.

When using indium oxide or tin oxide as a conductive film, commercially available ones for transparent electrodes can be used, and for coins, even if the transparency is reduced,
It is also possible to use a glass plate coated with a large amount of indium oxide or tin oxide to improve electrical conductivity. Moreover, such a base with improved conductivity allows the required voltage and military conditions for lightning attachment to be exactly the same as the base for dragon coins that have been used in the past. This has the advantage of reducing defects and improving the quality of coin items.In addition, since it is easy to remove the bonded metal from the conductive film, when using the base for military coins according to the present invention, it is generally recommended to It has a feature that there is no need for the conventional stripping solution immersion treatment (for example, ammonium dichromate solution immersion).In addition, due to the internal stress of the de-deposited metal, some of the electrodeposited metal is removed from the substrate during de-deposition. If the glass surface peels off or warps, if necessary, roughen the surface by sandblasting, hydrofluoric acid treatment, etc. before applying a conductive film. As a result, the adhesion of military uniform metal is slightly increased, and the phenomenon of peeling off from the base during exposure is also eliminated.The base for dew coins in the present invention is not limited to a flat plate-like one,
It goes without saying that dome-shaped, cylindrical, and other three-dimensional substrates can be used, and in these cases, desired three-dimensional electrical money products can be obtained depending on the shape of each substrate.

Furthermore, when using a cylindrical base for electroplating, electrodeposition is carried out while rotating it in a turtle bath, and if one end of the lightning kimono is peeled off and pulled out, a sheet-like dragonfly product with a high-density image can be obtained. can be obtained continuously. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail below based on embodiments and shown in drawings.

Example 1 As shown in FIG. 2, a conductive film 12 of indium oxide with a thickness of 0.3 mounds is applied by vacuum evaporation on one side of a glass plate 11 having two thicknesses, so that the electrical resistance becomes approximately 2000/mm. After that, a photoresist is applied and dried, and then a pattern with the desired image is adhered to it, and then it is exposed and developed. The indium oxide film was etched and removed by soaking it in a mixed solution of and hydrochloric acid.

Thereafter, the photoresist was removed by treatment with a stripping solution of sodium hydroxide, yielding a glass plate 11 having a complex desired image 13 made of indium oxide, as shown in FIG. Next, as shown in FIG. 4, a silver paste 14 was applied to a thickness of about 10 mm on the indium oxide film 13 around the plate and dried to obtain a substrate for electrolytic rusting. Furthermore, one end of this military grade base was held with a clip that would make the contact area as large as possible to reduce the electrical resistance, and it was immersed in a nickel electrodeposition bath to perform dew deposition, as shown in Figure 5. Deposition was terminated when a thickness of nickel electrodeposited metal 15 was obtained.

Next, as shown in FIG. 6, the deposited nickel 15 was peeled off from the base to obtain an electric money product 15, and the peelability of the electric money product 15 from the base was very good. The shape of the hole was sharper than before, and the dimensional accuracy was good.In addition, when plating started, the current density was lowered and plating was performed at IA/d, so the high electrical resistance of indium oxide was also a factor. Well, 10-3 in the early stages of Ryukyu.
At 0 seconds, the electroplating speed at the center of the substrate is slightly slower than at the surrounding area, but after about 3 seconds, it is electrodeposited uniformly over the entire surface, and the plating conditions are all the same as before, voltage is 4V, current density is 3A nod. Therefore, the plating time could be reduced to 10 minutes. After the haze deposited metal was removed, the electronic mirror base was put into the open plating condition again, and after the same plating conditions were applied, the electronic mirror products were collected again. The shape, dimensional accuracy, etc. were always maintained well, and the base for Kasumi coins withstood repeated use over 100 times.

Therefore, with conventional substrates that can be used only one to three times, it is necessary to create a large number of substrates to obtain a desired haze mirror product, which requires a large amount of labor and material costs.
When using the substrate according to the present invention, the number of substrates to be manufactured is a few tenths of that of conventional substrates, and there is no need for the labor of embedding resin in metal, for example, resulting in extremely large savings in labor and material costs. We were able to produce a large number of Russian coin products that were not only simple, but also had significantly improved accuracy, quality, and quality.
It goes without saying that production volume can be doubled by forming a desired image not only on one side but also on both sides of the base for turtle mirrors.Also, if a part of the base is raised into a dome shape in advance, it is possible to create a dome-shaped exposure mold. You can also create items.

Example 2 As shown in FIG. 7, the entire outer circumference of the glass cylinder 16 has a thickness of 1
After a conductive film 7 of tin oxide (electrical resistance of approximately 1000') is applied, a photoresist is applied to the entire outer periphery and dried, and then a pattern having a desired image is adhered along the outer periphery. After that, print and develop the 8th
As shown in the figure, the part 1 where photoresist is not attached
The tin oxide of No. 8 was removed by etching with hydrochloric acid and zinc powder.

Thereafter, the photoresist was removed by treatment with a stripping solution of sodium hydroxide to produce an exposure mirror substrate having a complex desired image 19 made of tin oxide on the outer periphery of the glass cylinder 16.
Furthermore, both ends of this cylindrical coin base are wrapped with a steel plate two inches thick and 50 mm thick, and are brought into close contact to facilitate the conduction of electricity.
A shaft was passed through the cylinder, and while rotating in a copper electrodeposition bath, lightning bonding of steel was carried out at a voltage of 2 V and a current density of 2 A/d for about 4 hours until the thickness was about 0.2 ribs. Lightning bonding was completed. Then, the turtle film is pulled out from the base for lightning coins and separated.
As shown in FIG. 9, a cylindrical copper electric mirror product 21 with a complex image and high precision was obtained. The base for rosen coins from which the Kame-casting products had been peeled off was again deposited in a copper electrodeposition bath to obtain cylindrical Kasumi coin products, but the conductive image formed by the tin oxide remained undamaged. The substrate withstood dozens of uses and exhibited a very long lifespan compared to the 1-3 uses of conventional methods.

In Example 2, a conductive film was applied to the outer periphery of the glass cylinder, but it is also possible to apply a conductive film to the inner periphery of the glass cylinder and collect cylindrical coin products.

Furthermore, by using a cylindrical base, not only cylindrical coin items but also endless products such as endless belts can be manufactured with good mass productivity. Example 3 As shown in FIG. 10, a dew conductive film 23 of indium oxide is applied to the entire outer circumference of the glass cylinder 22 to a thickness of 0.3 mounds, so that the electrical resistance is approximately 20.
00'□, then apply photoresist to the entire outer periphery, dry it, and then apply a pattern with the desired image to the outer periphery, and then apply and develop the area to which the photoresist is not attached. The indium oxide was soaked in a mixed solution of ferric chloride and hydrochloric acid and etched to remove it.

Thereafter, the photoresist was removed by treatment with a stripping solution of sodium hydroxide, and a base for coins having a complex desired image 24 made of an indium oxide film on the outer periphery of the glass cylinder 22 was created. Next, conductive silver paste is applied to the outer periphery of both ends of this cylindrical coin base to a thickness of about 10 r, and after passing the shaft through the cylinder, it is coated with an appropriate thickness in the nickel electrodeposition 25. The sheet-like nickel coin metal foil 26 having the image is taken out from a part of the base and placed on another cylinder 2.
I wound it up to 7. The shape and size accuracy of the image of the sheet metal foil 26 produced in this way is extremely good not only at the initial stage of production, but also after a long sheet is collected by continuing electrodeposition for a considerable period of time. , it was shown that the indium oxide image was maintained with high accuracy, the life of the cylindrical substrate was proved to be extremely long, and a long high-precision coin sheet could be obtained continuously. Furthermore, when using the base for wire twill according to the present invention, since the helmet-coated metal 26 is extremely easy to peel off from the base, the thickness can be reduced to an extremely thin 4 to 5 mm, which was previously possible.
It was also possible to collect metal foil smaller than 100 yen. This applies not only to the case where an image is present as described above, but also to the case where there is no image. In addition, although nickel and copper Kamesen products were described in the example given in (a) above, good quality Kasumikyo products can be mass-produced by using the highly durable substrate of the present invention with any metal that can be scratched. It goes without saying that it can be done.

[Brief explanation of drawings]

FIG. 1 is a perspective view conceptually showing an example of the coin base of the present invention. Figures 2 to 10 are for explaining embodiments of the present invention, and Figures 2 to 6 show the manufacturing process of a plate-shaped dew coin base and the manufacturing process of a dew mirror product using the same. FIG. 7 to FIG. 9 are cross-sectional views conceptually showing the manufacturing process of a cylindrical silk coin base and a coin coin product manufactured using the same, and FIG. FIG. 2 is a cross-sectional view conceptually showing a state in which a long electric money sheet is manufactured using a cylindrical base. 1...
Glass plate, 2... Conductive film made of indium oxide or tin oxide, 3... Substance with good conductivity. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10

Claims (1)

[Claims] 1. Electrodeposition is performed on the surface of the support by placing a conductive support in an electrodeposition solution, and then removing the support from the electrodeposition solution, and then transferring the deposited metal to the support. In a method for manufacturing an electroformed product that is more easily peeled off, the conductive support has a conductive film made of indium oxide or tin oxide on a part or all of at least one surface of the glass, and the conductive support Electroforming is carried out by using an electroforming substrate in which a material with good conductivity is provided in the periphery of the film, and conducting electrically to the conductive film through the material with good conductivity on the electroforming substrate. A method of manufacturing electroformed products characterized by: 2. The method of manufacturing an electroformed product according to claim 1, wherein the substance with good conductivity is gold, silver, copper, lead, or nickel. 3 Having a conductive film made of indium oxide or tin oxide on part or all of at least one surface of the glass, and having good conductivity on the conductive film in the periphery of the surface of the glass having the conductive film. A substrate for electroforming characterized by being provided with a substance. 4. The electroforming substrate according to claim 3, wherein the substance with good conductivity is gold, silver, copper, lead, or nickel. 5. The electroforming substrate according to claim 3 or 4, wherein the glass is plate-shaped. 6. The electroforming substrate according to claim 3 or 4, wherein the glass is cylindrical.