JP2003082491A - Fine electroforming die, and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fine electroforming die which can be used in an excellent manner without degradation for a long time because very fine metal products can be manufactured by using an electroforming method with excellent reproducibility of the dimension and the shape and with good accuracy, and the manufactured metal products can be easily peeled, and an efficiency manufacturing method of the fine electroforming die. SOLUTION: In the very fine electroforming die, 1 the protrusion D1 of a tip surface 11a of a very small electrode part 11 having the flat shape corresponding to the shape of the metal product manufactured by electroforming from the surface 12a of an insulating layer 12 constituting the surface of the die is set to be in a range of 0.1 to 2 μm. In the manufacturing method of the die 1, a resin composition with a flowability forming a basis of an insulating layer is fed to the surface of the base body with the very small electrode part disposed thereon, and the resin composition is applied spread to the surface of the base while filling the resin composition in a filling space between small electrodes by moving a blade in an abutted manner on a tip surface part of the fine electrode part, and the resin composition is hardened.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention forms a fine shape corresponding to the shape of the above-mentioned tip surface by forming a thin metal film on the tip surface of a fine electrode portion having a predetermined fine shape by electroforming and then peeling it off. The present invention relates to a fine electroforming die for producing a metal product and a method for producing the die.

[0002]

2. Description of the Related Art The electroforming method has the advantages that it can be processed with ultra-precision, that it can be integrated with a base material to produce a metal product, and that it can be copied accurately. For example, copper foil for printed wiring boards and electric razors can be used. It is applied to various metal products such as blades, precision screens, clock faces, and compact disc molds. Particularly, as typified by the miniaturization of internal parts accompanying the miniaturization of electronic devices in recent years, there is an increasing demand for fine electroforming, particularly the dimensions of which are in the micron order.

In electroforming, there are a case where a metal thin film is plated on a mold to manufacture a metal product integrated with the mold, and a case where the plated metal thin film is peeled from the mold to obtain a metal product. . At present, it is common to manufacture the former metal product integrated with the mold, but it is expected that demand for the latter metal product will increase in the future.
However, when manufacturing the latter metal products,
There is a problem that peeling from the mold is not easy. The cause is that a so-called anchor effect occurs between the surface of the mold and the metal thin film. And, if the peeling is not easy as described above, since the metal product has a microstructure, it is likely to be deformed or damaged by the stress at the time of peeling, which causes a problem that the yield of the metal product is significantly reduced. . Moreover, if the mold is forcibly peeled off with a strong force, the mold is also subjected to an excessive force, so that the mold deteriorates quickly.

Therefore, the inventor has studied to facilitate release from the mold by applying a reverse polarity voltage to the metal thin film and subjecting it to anodic electrolysis. However, since anodic electrolysis increases corrosion of the metal of the mold, repeating this process causes a problem of promoting deterioration of the mold. The object of the present invention is to produce a particularly fine metal product by electroforming with high reproducibility of dimensions and shape and with high precision, and since the produced metal product can be easily peeled off, deterioration occurs over a long period of time. It is an object of the present invention to provide a fine electroforming mold that can be used satisfactorily without use, and an efficient manufacturing method of the fine electroforming mold.

[0005]

According to a first aspect of the present invention, the tip surface of a microelectrode portion having a tip surface having a planar shape corresponding to the shape of a metal product to be manufactured is A fine electroforming mold, which is arranged so as to be exposed on the surface of an insulating layer that constitutes the surface of the mold, wherein the tip end surface of the microelectrode portion is projected from the surface of the insulating layer in the range of 0.1 to 2 μm. This is a fine electroforming mold characterized by the above.

According to the structure of claim 1, the protrusion amount of the surface shell of the insulating layer on the tip surface of the microelectrode portion is 2 μm as described above.
Since the thickness is m or less, it is possible to prevent a strong anchoring effect from being formed between the thin film which is a metal product and is formed on the tip surface of the microelectrode portion. On the other hand, when the amount of protrusion of the tip surface of the microelectrode portion is set to a range exceeding 2 μm, the metal thin film grows at the edge portion so as to wrap around from the tip surface of the microelectrode portion to the side surface, and thus the anchor effect. Is promoted and peeling becomes difficult.

On the other hand, when the amount of protrusion of the tip surface of the microelectrode portion is less than 0.1 μm, the stress for peeling the metal thin film cannot be concentratedly applied to the metal thin film. After all, peeling becomes difficult. Furthermore, when the tip surface of the microelectrode part is recessed from the surface of the insulating layer,
As a result of the metal thin film growing so as to fit into the holes of the insulating layer formed by the depression, the anchor effect is also promoted and the peeling becomes difficult.

On the other hand, when the tip surface of the microelectrode portion is projected in the range of 0.1 to 2 μm from the surface of the insulating layer as described above, promotion of the anchor effect due to these phenomena can be prevented. At the same time, since the stress for peeling can be concentratedly applied to the metal thin film, the metal thin film can be easily peeled as a metal product with a weaker force than before. Therefore, it is possible to suppress the deformation and damage of the metal product due to the stress at the time of peeling more than ever, and it is also possible to suppress the deterioration of the mold.

Therefore, when anodic electrolysis is performed alternately with electroforming or after electroforming, the electric field strength and / or frequency thereof can be made smaller than before, and the mold is not deteriorated by anodic electrolysis. It can be suppressed. Therefore, according to the configuration of claim 1, particularly fine metal products can be manufactured by electroforming with high reproducibility of dimensions and shapes with high precision, and the manufactured metal products can be easily peeled off, and thus, over a long period of time. Therefore, it becomes possible to provide a fine electroforming mold that can be favorably used without causing deterioration.

The invention according to claim 11 is a method for producing the fine electroforming die according to claim 1, wherein a base having a fine electrode portion arranged on the surface is prepared, and the fine electrode portion of the base is prepared. The resin composition having a fluidity that is a base of the insulating layer is supplied to the surface on which the blade is made to contact the blade of the metal or resin while contacting the tip surface of the fine electrode portion with the blade. It is characterized by comprising a step of forming an insulating layer by solidifying or curing the resin composition after applying the resin composition to the surface of the substrate while filling the gaps of the microelectrode parts by relative movement and spreading the resin composition. It is a method for manufacturing a fine electroforming mold.

The fine electroforming die according to claim 1 may be manufactured by various conventionally known manufacturing methods to which a technique for manufacturing a printed wiring board using a photolithography method is applied. . However, for example, in a manufacturing method involving polishing or etching, the tip surface of the microelectrode portion and the surface of the insulating layer, which are made of different materials of metal and resin, which are different in processability (polishing rate, etching rate, etc.), are used. In addition, since a step is likely to occur due to the difference in ease of processing and it is not easy to perform uniform processing especially with the polishing method, the amount of protrusion of the tip end surface of the minute electrode portion should be distributed over the entire surface of the mold. It is not easy to set the thickness within the range of 0.1 to 2 μm.

On the other hand, in the manufacturing method of the eleventh aspect of the present invention, since the processing steps such as polishing and etching are not included, the protrusion of the tip end surface of the microelectrode portion is simpler and more efficient than the conventional method. The amount is 0.1 to 2 over the entire surface of the mold.
It becomes possible to manufacture the fine electroforming die according to the first aspect of the invention while maintaining it within the range of μm.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below. (Fine Electroforming Mold) The fine electroforming mold is configured such that the above-mentioned tip surface of the microelectrode portion having the tip surface having a planar shape corresponding to the shape of the metal product to be manufactured constitutes the above-mentioned tip surface. The insulating layer is exposed on the surface of the insulating layer.

For example, in the case of producing a flat metal powder having a predetermined shape, such as a circular planar shape, as a metal product, as shown in FIGS. A large number of columnar microelectrode portions 11 each having a tip surface 11a corresponding to a planar shape are formed integrally with a conductive substrate 10 provided on the back surface side of an insulating layer 12 forming the front surface of the mold 1. Then, the microelectrode portion 11 is penetrated through the insulating layer 12 and the tip surface 11a thereof is exposed on the surface 12a of the insulating layer 12, whereby the fine electroforming mold 1 is configured. The fine electroforming die 1 having such a structure is efficient because a large number of metal powders corresponding to the number of the fine electrode portions 11 can be produced by one electroforming.

In the present invention, the tip surface 11 of the microelectrode portion 11 is
a of the protrusion D ₁ from the surface 12a of the insulating layer 12 is 0.
It must be 1 to 2 μm. Due to this limitation, the metal thin film formed by electroforming as described above can be easily separated from the tip surface 11a of the microelectrode portion 11. The material forming each part of the fine electroforming mold 1 is not particularly limited, but it is preferable that at least the tip surface 11a of the microelectrode part 11 is formed of SUS316 series stainless steel. Since SUS316 series stainless steel has excellent corrosion resistance, it is highly resistant to plating solutions and the like. Therefore, the durability of the mold is improved, especially when it is applied to a method for manufacturing a metal product that promotes peeling of a metal thin film by anodic electrolysis.

Considering how long the mold can be used when the tip surface of the microelectrode portion 11 is gradually eroded due to corrosion or the like, the microelectrode portion 11 is not limited to the tip surface 11a. It is preferable that the whole is made of SUS316 series stainless steel. Furthermore, the microelectrode portion 11 and the conductive substrate 10 are connected to each other by SUS3
Most preferably, they are integrally formed of 16 series stainless steel. Among them, as the SUS316 series stainless steel, SUS316L, which is particularly excellent in corrosion resistance, can be most preferably used.

A release layer for facilitating the peeling of the metal thin film may be provided on the tip surface 11a of the microelectrode portion 11. As the release layer, for example, a passivation film formed when a metal is rolled or heat-treated can be used, and if necessary, a passivation film is chemically or electrochemically formed to release the release film. It may be a layer. Examples of the latter include a thiazole-based compound coating in which a forming agent for electroforming is commercially available. The insulating layer 12 can be formed of various insulating materials. However, the insulating layer 12
In consideration of easiness of forming, etc., it is preferable to form the insulating layer 12 by a composition of various resins that are thermoplastic or curable, particularly in a solventless system or in a state containing a very small amount of solvent. It is more preferable to use a curable resin composition that exhibits fluidity (including a curable resin and a curing agent thereof). Since the curable resin composition has a small volume shrinkage rate when cured to form the insulating layer 12,
The protrusion amount D ₁ of the tip surface 11a of the microelectrode portion 11 is set to 0.1
It is easy to set the thickness in the range of 2 μm, and the corrosion resistance after curing is good. Epoxy resin is particularly preferable as the curable resin.

The composition of a curable resin such as an epoxy resin further reduces the volumetric shrinkage rate when the resin is cured to form the insulating layer 12, and the temperature change of the insulating layer 12 after the formation is changed. In order to reduce the expansion / shrinkage rate due to, and to maintain the protrusion amount D ₁ of the tip end surface 11a of the microelectrode portion 11 in the range of 0.1 to 2 μm when the fine electroforming mold is used, an insulating filler is used. Is preferably blended. The insulating layer 12 containing the filler is also excellent in abrasion resistance against friction applied when peeling the metal thin film.

As the filler, inorganic fillers such as alumina, silica and glass are preferable. The filler is preferably spherical. The spherical filler has an advantage of functioning to suppress an increase in viscosity of the composition and maintaining good fluidity when compounded in a curable resin composition, and having an advantage that it can be highly filled. The average particle size of the filler is 0.5 μm or less in consideration of forming a uniform insulating layer 12 having excellent smoothness of the surface 12a and having no cavities or the like corresponding to the fine shape of the fine electrode portion 11. Is preferable, and it is more preferable that the thickness is about 0.05 to 0.2 μm. Note that the average particle diameter of the filler is the average value of the maximum diameters of the individual fillers when the filler is not spherical.

The compounding ratio of the filler in the epoxy resin composition is preferably 1 to 30% by weight based on the total amount of the composition. If the blending ratio of the filler is less than 1% by weight, the effect described above due to the blending of the filler may not be sufficiently obtained. On the other hand, when the compounding ratio of the filler exceeds 30% by weight, the fluidity and the followability of the composition before curing are deteriorated, the surface 12a is excellent in smoothness, and the insulating layer 12 is uniform without voids. May not be formed. Further, the cured insulating layer 12 may become brittle and its durability may be reduced. In addition, it is more preferable that the blending ratio of the filler be 5 to 20% by weight, even within the above range.

A silane coupling agent is preferably added to the epoxy resin composition. According to the study by the inventor, the main causes of deterioration of the fine electroforming die 1 are (a) corrosion of the microelectrode portion 11, (b) abrasion of the surface of the insulating layer 12, and (c) microelectrode portion. 11 and the base 10, and the insulating layer 1
The occurrence of peeling at the interface with No. 2 due to a decrease in adhesion is mentioned.

Of these, (a) can be solved by forming the fine electrode portion 11 from SUS316 series stainless steel as described above. Further, (b) can be solved by forming the insulating layer 12 with a curable resin such as an epoxy resin and blending an insulating filler. Therefore, in order to solve (c) further, a silane coupling agent is added to the composition of the epoxy resin, and the fine electrode portion 11 and the base 10 are mixed.
And to improve the adhesion to the insulating layer 12.

When the step of forming a metal thin film on the tip end surface 11a of the microelectrode portion 11 and then peeling it off is repeated, the difference in the expansion / contraction rate between the microelectrode portion 11 or the base 10 and the insulating layer 12 or the metal thin film is removed. Due to the stress applied to the fine electroforming mold 1 during peeling, peeling is likely to occur at the interface between the fine electrode portion 11 and the substrate 10 and the insulating layer 12 due to the decrease in adhesion. Then, when the microelectrode portion 11 and the insulating layer 12 are peeled off, the metal thin film grows in a state of entering the peeled gap to generate a strong anchor effect. Therefore, in order to recover the metal thin film, a stronger force is applied. It is necessary to forcibly peel off or carry out anodic electrolysis for a long time. Further, as a result of the growth of the metal thin film that has entered the gap, the gap is further widened, or the peeling progresses to the interface between the base 10 and the insulating layer 12, so that the insulating layer 12 is likely to drop off and the like. The casting mold 1 deteriorates.

On the other hand, if a silane coupling agent is added to the epoxy resin composition to improve the adhesion between the microelectrode portion 11 and the substrate 10 and the insulating layer 12, the occurrence of peeling can be prevented. Therefore, deterioration of the fine electroforming mold 1 can be suppressed, and the fine electroforming mold 1 can be favorably used for a longer period of time than before without deterioration. The compounding ratio of the silane coupling agent in the epoxy resin composition is preferably 1 to 20% by weight based on the total amount of the composition. If the blending ratio of the silane coupling agent is less than 1% by weight, the effect of improving the adhesiveness due to the blending of the silane coupling agent may not be sufficiently obtained. On the contrary, the compounding ratio of the silane coupling agent is 2
If it exceeds 0% by weight, the insulating layer 12 having predetermined heat resistance, corrosion resistance, abrasion resistance, and durability may not be formed even when the composition is cured. In addition, the compounding ratio of the silane coupling agent is particularly 2 to within the above range.
More preferably, it is 10% by weight.

As a method of using the silane coupling agent, it is common to insert a layer of the silane coupling agent at the interface where adhesion is desired to be imparted. For example, in the case of the fine electroforming mold 1 shown in the figure, the insulating layer 1 of the fine electrode portion 11 or the base body 10 is
It is conceivable that a silane coupling agent is applied to the surface in contact with 2 to form a layer, and then the composition of the epoxy resin is poured to form the insulating layer 12. However, in the fine electroforming die 1, the fine electrode portion 11 formed extremely finely.
Since the thickness of the silane coupling agent layer is larger than that of the insulating layer 12 and the insulating layer 12, the ratio of the silane coupling agent layer in the insulating layer 12 may increase and the strength of the insulating layer 12 may decrease. . Therefore, it is preferable that the silane coupling agent is blended in the composition of the epoxy resin forming the insulating layer 12 as described above.

In order to improve the adhesion between the microelectrode portion 11 and the base 10 and the insulating layer 12,
The microelectrode portion 11 is at least on the surface in contact with the insulating layer 12.
It is also preferable to provide a metal thin film layer having a higher OH group concentration. With such a configuration, the microelectrode portion 11 or the base 10 and the insulating layer 12 can be more firmly adhered to each other by the reaction between the OH group and the epoxy group in the epoxy resin in particular. Moreover, since the metal thin film is integrated with the microelectrode portion 11 and the base body 10, there is no fear of lowering the strength of the insulating layer 12 unlike the silane coupling agent layer.

A Ti layer is preferably used as the metal thin film layer. In addition, the microelectrode portion 11 and the substrate 1 of this Ti layer
In order to improve the adhesion with 0 and prevent peeling, it is preferable to provide a Cr layer between these members and the Ti layer. These layers can be formed by, for example, a sputtering method. The thickness of the metal thin film layer such as the Ti layer is preferably 0.01 to 1.0 μm. If the thickness is less than 0.01 μm, the effect of improving the adhesiveness may not be sufficiently obtained, while if it exceeds 1.0 μm, the residual stress may be large and the layer may be broken or peeled. There is.

If the above-described compounding of the epoxy resin composition with the silane coupling agent and the above-mentioned formation of the metal thin film layer are used together, the fine electrode portion 11 is formed.
The adhesiveness between the substrate 10 and the insulating layer 12 can be further improved. (Manufacturing Method of Fine Electroforming Mold) The fine electroforming mold 1 is manufactured by using, for example, a photolithography method,
It can be manufactured by various methods such as (1) to (3) to which the technology for manufacturing a printed wiring board is applied.

(1) At least a metal plate having a thickness corresponding to the thickness of the base 10 plus the height of the microelectrode 11 is etched to etch the base 10 and the microelectrode 11 shown in FIG.
And (4) are integrally formed, the voids between the microelectrode portions 11 are filled with the above-mentioned resin composition without any gap, and the surface 12a thereof is formed.
And the tip surfaces 11a of the fine electrode portions 11 are polished to be flush with each other to form the insulating layer 12. (2) The pre-formed insulating layer 12 is etched to form a large number of through holes corresponding to the outer shapes of the large number of microelectrode portions 11, ... Then, the substrate 10 is formed on the back surface side of the insulating layer 12 by electroforming or the like. After forming and forming a large number of minute electrode portions 11 ... By filling the through holes with metal without any gaps, the tip surfaces 11a of the minute electrode portions 11 ... And the surface 12a of the insulating layer 12 are made the same surface. To be polished.

(3) A laminated body in which the substrate 10 is laminated on the back surface side of the insulating layer 12 is prepared, and the insulating layer 12 of the laminated body is prepared.
Are etched to form a large number of through holes corresponding to the outer shapes of a large number of minute electrode parts 11 ... Reaching the base body 10, and then the through holes are filled with metal by electroforming or the like without any gaps to form a large number of minute electrode parts. After forming 11 ..., the microelectrode portions 11 ...
.. and the surface 12a of the insulating layer 12 are polished to be flush with each other.

However, it is preferable to manufacture a fine electroforming mold by the manufacturing method of the present invention described below, which does not include a step such as polishing as described above. For example, in Figure 1,
When manufacturing a fine electroforming mold for metal powder production,
First, as shown in FIG. 2 (a), a large number of microelectrode parts 1 are formed on the surface.
A substrate 10 on which 1 is integrally formed is prepared. The substrate 10 is at least the substrate 1 as in the case of the manufacturing method (1).
It is manufactured by, for example, etching a metal plate (preferably a SUS316-based stainless steel plate) having a thickness of 0 plus the height of the microelectrode portion 11. Further, on the surface thereof, the above-mentioned metal thin film layer is formed, if necessary.

Then, a resin composition R having fluidity for forming the insulating layer 12, such as one containing the above-mentioned epoxy resin and filler, and optionally a silane coupling agent, is applied to the base 10. , To the surface on which the microelectrode portion 11 is arranged. Next, as shown in FIGS. 2 (b) to (c),
The metal or resin blade B is attached to the tip surface 1 of the microelectrode portion 11.
The blade B and the substrate 10 are moved relative to each other as shown by the white arrow in the drawing while being in contact with 1a, so that the resin composition R is applied to the surface of the substrate 10 while filling the gaps of the minute electrode portions 11. Expand.

Then, the resin in the resin composition R is dried and solidified,
Alternatively, when it is cured, the fine electroforming mold 1 shown in FIG. 1 is manufactured. In the above-described manufacturing method, the resin composition R is moved to the tip surface 11 by moving the blade B having the adjusted blade edge while contacting the tip surface 11a of the microelectrode portion 11.
It is possible to fill the gaps between the minute electrode portions 11 so that they are substantially flush with a.

Therefore, no steps such as polishing are required,
As described above, the fine electroforming mold 1 in which the protrusion amount D ₁ of the tip end surface 11a of the fine electrode portion 11 is in the range of 0.1 to 2 μm is simpler and more efficient than the conventional one. It becomes possible to manufacture. (Manufacture of Metal Product) In order to manufacture metal powder as a metal product using the above-mentioned fine electroforming die 1, first, referring to FIG.
As shown in (1), the electrocasting power source is connected to the cathode 21 and immersed in a plating solution (not shown) to perform electrocasting using the microelectrode portions 11 as cathodes.

Then, as shown in FIG. 3 (b), the plating metal is selectively deposited on the tip surface 11a of each of the minute electrode portions 11, and a large number of minute metal thin films 30 corresponding to the shape of the tip surface are formed. Is formed. Next, when the minute metal thin film 30 thus formed is scraped off and peeled off from the tip surfaces 11a of the respective microelectrode portions 11 as shown in FIG. 3C, the tip surfaces 11a of the respective microelectrode portions 11 are separated. A large number of metal powders 3 having a fine shape corresponding to the shape are manufactured.

In electroforming, the film thickness of the metal thin film 30 can be strictly controlled by adjusting the conditions such as energization time and current density, so that the thickness of the metal powder 3 to be manufactured can be made uniform with high accuracy. it can. Moreover, the fine electroforming mold 1 of the present invention
When the metal thin film 30 is used, it is possible to easily rub the metal thin film 30 with a slight force such as rubbing it with a rubber roller.
It can be peeled off from the front end surface 11a of the. Therefore, the metal thin film 3
0 can prevent deformation or damage due to stress at the time of peeling as much as possible, and the yield of the metal powder 3 as a metal product can be improved more than ever. It is also possible to prevent damage to the die 1 and make it last longer than before.

In the electroforming, it is preferable to carry out anodic electrolysis for a certain period of time after the metal thin film 30 is formed by electroforming, or for a short time alternately with the growth of the metal thin film 30 by electroforming. By this processing, the microelectrode portion 11
It is possible to dissolve and remove the protrusions or the like at the edge portions of the thin film, which are the basis for producing the anchor effect between the tip surface 11a and the metal thin film 30, and to reduce the adhesive force between the two.
It is possible to more easily peel the metal thin film 30 from the tip end surface 11a of the microelectrode portion 11.

The structure of the fine electroforming mold of the present invention is as follows.
It is not limited to the mold for producing the metal powder described in the above figures. For manufacturing various products that can be manufactured by electroforming, such as a mesh-shaped metal thin film formed with a large number of through holes each having a predetermined plane shape, which is preferably used for a battery electrode plate or the like. The structure of the present invention can be applied to a mold.

[0039]

EXAMPLES The present invention will be described below based on Examples and Comparative Examples. Example 1 Stainless steel 200 mm long × 300 mm wide (SUS31
6L) One side of the steel sheet was etched using a photolithography method, and the surface had a diameter of 30 μm and a height of 7 μm.
A base body having a large number of m-shaped columnar microelectrode portions integrally formed was obtained.

Next, while the substrate was suctioned and fixed on a stainless steel table having a surface accuracy of ± 2 μm, a resin composition (each of which was composed of the following components) was provided on one side of the surface on which the fine electrode portion was arranged. Viscosity 400P) Approximately 2 ml was fed. (Component) (Parts by weight) Special modified epoxy resin 68 Special amine curing agent 22 Spherical alumina filler 10 (Average particle size 0.1 μm) Next, a stainless steel blade with a blade width of 12 mm is attached to the tip surface of the microelectrode portion. By moving the blade with respect to the substrate while making contact with the substrate, the operation of coating the resin composition on the surface of the substrate while filling the gaps of the microelectrode parts and spreading it over the entire surface of the substrate. It was

Then, the epoxy resin in the resin composition was cured to form an insulating layer filling the spaces between the fine electrode portions, and a fine electroforming mold was manufactured. The amount of protrusion D ₁ of the tip surface of the microelectrode portion from the surface of the insulating layer in the above-mentioned fine electroforming mold was measured at a plurality of locations on the substrate, and was 0.1 to 2 μm at any location. It was within the range, and the average value was 0.6 μm. Next, the above-mentioned fine electroforming die and a nickel plating solution (pH =
Using 3) and, nickel was electroformed under the condition of a liquid temperature of 60 ° C. during air bubbling. A nickel plate was used for the anode.

(Component) (Concentration) Nickel Sulfate Hexahydrate 200 g / L Nickel Chloride Hexahydrate 40 g / L Boric Acid 30 g / L Saccharin 4 g / L 20 at 10 A / dm ²
After the nickel thin film was grown by applying an electric current for 0 seconds, the mold was used as an anode, and an electric current was applied for 10 seconds at a direct current of 10 A / dm ² for anodic electrolysis.

Then, the nickel thin film formed on the tip surface of the microelectrode portion by electroforming was scraped off by rubbing with a rubber roller to produce nickel powder. The obtained nickel powder was magnified 1000 times using a scanning electron microscope.
Upon observing at double magnification, it was confirmed that all of the powders were disc-shaped powders having a diameter of 30 μm and a thickness of 5 μm without any defects. No nickel thin film remained on the surface of the mold.

Further, even if the same electroforming and peeling operations as described above are repeated 50 times using the same mold, no change is observed in the state of the nickel powder which is a metal product.
No nickel thin film remained on the mold surface, and no damage was found on the mold. Comparative Example 1 On the same substrate used in Example 1, this was also done in Example 1.
After thickly applying the same resin composition as used in 1 above and curing it, it was attempted to expose the surface of the microelectrode portion by polishing the surface with a No. 2000 abrasive paper. However, it is difficult to evenly expose the tip surface of the microelectrode part over the entire surface of the base, and the tip surface is not exposed at all due to insufficient polishing of the insulating layer, or conversely, excessive polishing causes protrusion. Amount D ₁
Occurs where the thickness exceeds 2 μm.

Then, the portion where the polishing was insufficient was further polished, and the electroforming was performed under the same conditions as in Example 1 with the tip surfaces of all the fine electrode portions exposed, and then formed. When the nickel thin film was rubbed with a rubber roller, it could be peeled off clearly when the protrusion D ₁ was 2 μm or less.
_A large number of nickel thin films that could not be peeled off cleanly occurred in the area where ₁ exceeded 2 μm. In addition, the protrusion amount D ₁ is 0.1
When the thickness was less than μm, the rubber roller slipped up, and many nickel thin films that could not be peeled off cleanly were generated.

Then, the remaining nickel thin film was scraped against a blade of a cutter and then observed with an electron microscope. As a result, it was confirmed that most of the nickel thin films had defects and deformations. Moreover, when the nickel thin film was forcibly scraped off, it was confirmed that the surface of the mold was scratched. Example 2 The same substrate used in Example 1 was used, and the surface accuracy was ± 2 μm.
About 2 ml of a resin composition (viscosity 400P) comprising each of the following components was supplied to one side of the surface on which the microelectrode portion was arranged while being sucked and fixed on a stainless steel table of m.

(Component) (Parts by Weight) Special Modified Epoxy Resin 58 Special Amine Hardener 22 Spherical Alumina Filler 10 (Average Particle Size 0.1 μm) Silane Coupling Agent 10 Next, a stainless steel blade having a blade width of 12 mm is used. While the blade is brought into contact with the tip end surface of the microelectrode portion, the blade is moved with respect to the base body, so that the resin composition can be applied to the surface of the base body while filling the gap between the microelectrode portions. , Over the entire surface of the substrate.

Then, by curing the epoxy resin in the resin composition, an insulating layer filling the space between the fine electrode portions was formed to manufacture a fine electroforming mold. The amount of protrusion D ₁ of the tip surface of the microelectrode portion from the surface of the insulating layer in the above-mentioned fine electroforming mold was measured at a plurality of locations on the substrate, and was 0.1 to 2 μm at any location. It was within the range, and the average value was 0.6 μm. Next, using this fine electroforming mold, electroforming was performed under the same conditions as in Example 1, and then the formed nickel thin film was scraped by rubbing with a rubber roller to produce nickel powder.

When the obtained nickel powder was observed with a scanning electron microscope at a magnification of 1000 times, it was confirmed that none of the powders was a disk-like powder having a diameter of 30 μm and a thickness of 5 μm. No nickel thin film remained on the surface of the mold. Further, when the same electroforming and peeling operations as described above were repeated using the same mold, peeling occurred at the interface between the fine electrode portion and the insulating layer after 50 times in Example 1 above. However, in Example 2, even when the above operation was repeated 100 times, no change was observed in the state of the nickel powder, which was a metal product, and no nickel thin film remained on the surface of the mold, and the amount was very small. No damage to the mold such as peeling at the interface between the electrode part and the insulating layer was confirmed.

Example 3 A Cr layer having a thickness of 10 nm and a Ti layer having a thickness of 0.1 μm were formed by sputtering on the entire surface of the same substrate as used in Example 1 on the side where the fine electrode portion was formed. The layers were laminated in this order. Next, with this substrate being sucked and fixed on a stainless steel table having a surface accuracy of ± 2 μm, the same resin composition as that used in Example 2 Viscosity 400P) Approximately 2 ml was fed.

Next, the stainless steel blade having a blade width of 12 mm is brought into contact with the tip surface of the fine electrode portion, and the blade is moved with respect to the substrate, whereby the above resin composition is applied to the fine electrode portion. The operation of coating and spreading the surface of the substrate while filling the gap was performed over the entire surface of the substrate. Then, by curing the epoxy resin in the resin composition, an insulating layer filling the space between the fine electrode portions was formed to manufacture a fine electroforming mold.

The amount D ₁ of protrusion of the tip surface of the fine electrode portion from the surface of the insulating layer in the above-mentioned fine electroforming mold was measured at a plurality of locations on the substrate, and was 0.1 at any location. It was within a range of ˜2 μm, and the average value was 0.6 μm. Next, using this fine electroforming mold, electroforming was performed under the same conditions as in Example 1, and then the formed nickel thin film was scraped by rubbing with a rubber roller to produce nickel powder.

When the obtained nickel powder was observed with a scanning electron microscope at a magnification of 1000 times, it was confirmed that none of the powders had a defect and had a disk-like powder with a diameter of 30 μm and a thickness of 5 μm. No nickel thin film remained on the surface of the mold. Furthermore, when the same electroforming and peeling operations as described above were repeated using the same mold, even if the above operation was repeated 500 times,
No change was seen in the state of nickel powder, which is a metal product, and no nickel thin film remained on the mold surface.
Moreover, such as peeling at the interface between the microelectrode and the insulating layer,
No damage to the mold was confirmed.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of an embodiment of a fine electroforming mold of the present invention.

2 (a) to 2 (c) are cross-sectional views showing steps of manufacturing the fine electroforming die of the example of FIG. 1 by a manufacturing method of the present invention.

3 (a) to 3 (c) are cross-sectional views showing a process of producing a metal powder as a metal product by using the fine electroforming die of the example of FIG. 1, respectively.

[Explanation of Codes] 1 Micro Electroforming Mold 11 Micro Electrode Part 11a Tip Surface 12 Insulating Layer 12a Surface D ₁ Projection Amount

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Akihisa Hosoe             1-3-3 Shimaya, Konohana-ku, Osaka Sumitomo Electric             Ki Industry Co., Ltd. Osaka Works (72) Inventor Isao Okuyama             1-3-3 Shimaya, Konohana-ku, Osaka Sumitomo Electric             Ki Industry Co., Ltd. Osaka Works (72) Inventor Masaharu Okamoto             1-3-3 Shimaya, Konohana-ku, Osaka Sumitomo Electric             Ki Industry Co., Ltd. Osaka Works F term (reference) 4K029 AA02 AA29 BA07 BA17 BB02                       BC02 BD03 CA05

Claims (11)

[Claims] 1. A microelectrode portion having a tip surface having a plane shape corresponding to the shape of a metal product to be manufactured, the tip surface being arranged so as to be exposed on the surface of an insulating layer constituting the surface of a mold. A fine electroforming mold, characterized in that the tip end surface of the microelectrode portion is projected from the surface of the insulating layer within a range of 0.1 to 2 μm. 2. The SUS is formed on at least the tip surface of the microelectrode portion.
The micro electroforming mold according to claim 1, which is formed of 316 series stainless steel. 3. The fine electroforming mold according to claim 1, wherein the insulating layer is formed of an epoxy resin composition containing an insulating filler. 4. The fine electroforming mold according to claim 3, wherein the average particle diameter of the filler is 0.5 μm or less. 5. The fine electroforming mold according to claim 3, wherein the blending ratio of the filler is 1 to 30% by weight based on the total amount of the composition. 6. The fine electroforming mold according to claim 3, wherein the filler is spherical. 7. The mold for fine electroforming according to claim 3, wherein a silane coupling agent is added to the epoxy resin composition. 8. The micro electroforming mold according to claim 3, wherein a thin film layer of a metal having an OH group concentration higher than that of the fine electrode portion is provided on at least a surface of the fine electrode portion which is in contact with the insulating layer. 9. The fine electroforming mold according to claim 8, wherein the thin film layer is a Ti layer. 10. The fine electroforming die according to claim 9, wherein a Cr layer is provided between the fine electrode portion and the Ti layer. 11. A method for producing a fine electroforming die according to claim 1, wherein a base having a fine electrode portion arranged on the surface thereof is prepared, and a surface of the base having the fine electrode portion arranged thereon is By supplying a resin composition having fluidity that is a base of the insulating layer, and bringing the blade made of metal or resin into contact with the tip surface of the microelectrode portion, the blade and the base body are relatively moved,
A micro electroforming mold characterized by including a step of coating and spreading the resin composition on the surface of the substrate while filling the gaps between the microelectrode parts, and then solidifying or curing the resin composition to form an insulating layer. Manufacturing method.