JP6681722B2 - Mold for molding, method for manufacturing mold for molding, and method for recycling mold for molding - Google Patents

Description

  The present invention relates to a molding die provided with a release film, a method for manufacturing the molding die, and a method for recycling the molding die.

  Conventionally, when a molded product such as glass is manufactured using a mold having fine irregularities formed on its surface or a mold requiring high surface accuracy, the molding mold and the molded product such as glass are separated from each other. It is a problem that a molded product is defective due to insufficient moldability. Therefore, in the molding die, a mold release film is generally formed on the molding surface thereof for the purpose of improving excellent mold releasability and repetition durability of molding.

  Here, since a mold used for press molding of an optical glass material is required to have high heat resistance and high strength, a cemented carbide mainly containing tungsten carbide (WC), tantalum carbide (TaC) is usually used. ), Titanium carbide (TiC), chrome carbide (CrC) and alumina (Al2O3) as main components, chrome (Cr), molybdenum (Mo), nickel (Ni), cobalt (Co), tungsten (W), Materials such as titanium (Ti), stainless steel (SUS), and silicon carbide (SiC) are used. For the release film, platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh), osmium ( Os) and noble metals such as ruthenium (Ru), or rhenium (Re), tungsten (W) and Transition metals such as barrel (Ta) is used (e.g., see Patent Document 1).

JP, 2009-73707, A

  However, in the case of a mold used for molding glass or the like, since the heating temperature is as high as 500 ° C. or higher, the life of the release film is several tens to several hundreds of shots, and there is a problem that durability is low. When the mold release film deteriorates due to repeated molding, the deteriorated mold release film is generally removed and regenerated.

  In the case of glass molding, since the molding temperature is as high as 500 ° C. or higher, a noble metal-based metal is often used as the mold release film. When regenerating a mold using a noble metal-based release film, it is common to physically remove the release film by polishing / grinding using a diamond grindstone or the like. At that time, not only the release film but also the die base material was ground, and there was a problem of damaging the die. When the mold release film is regenerated without repairing the scratched mold, the surface accuracy of the mold cannot be maintained. Therefore, there has been a problem that an additional process for dimensioning the mold is required to regenerate the release film. In addition, since the weight of the die is significantly changed by polishing / grinding and additional machining of the die, the heat capacity of the die is changed, and it is necessary to readjust the molding conditions of the molded product.

  The present invention has been made to solve the above problems, and a molding die in which the mold release film of the die is easily regenerated, a method for manufacturing the molding die, and a molding die. The aim is to get a way of playing.

The molding die according to the present invention is a mold base material, a protective film formed on the mold base material in a state of covering the molding surface of the mold base material, and formed on the protective film, A release film made of a material having a higher chemical reactivity than the die base material and the protective film, and a release film formed on the release film and made of a material having a lower chemical reactivity than the release film , The protective film is formed on the mold base material in a state of covering a region over the molding surface of the mold base material, and the release film covers a region over the molding surface of the mold base material. Formed on the protective film in the state of, the release film is formed on the release film in a state of covering a region beyond the molding surface of the mold base material, the peripheral portion of the protective film, It is exposed all around .

  According to the present invention, since the release film made of a material having high chemical reactivity is formed on the lower surface of the release film, the release film can be removed at the same time by dissolving and removing the release film. Therefore, it is not necessary to remove the release film by polishing and grinding, and damage to the die base material can be reduced. Further, since the protective film is formed between the mold base material and the release film, contact between the release liquid that dissolves and removes the release film and the mold base material is avoided, and the mold base material is removed by the release liquid. The occurrence of damage at the interface with the protective film is suppressed. This eliminates the need for additional work for dimensioning the die base material, which was required when the mold release film was regenerated by polishing and grinding, and the cost of regenerating the mold release film can be greatly reduced. Further, since the surface accuracy and heat capacity of the mold do not change before and after the release film is peeled off, the change in the molding conditions of the molded product by the mold before and after the regeneration is small, and the molding conditions of the molded product can be stabilized. .

It is sectional drawing which shows the metal mold | die base material in the metal mold | die for molding which concerns on Embodiment 1 of this invention. It is sectional drawing which shows the state which applied the resist to the metal mold | die base material in the metal mold | die which concerns on Embodiment 1 of this invention. FIG. 3 is a cross-sectional view showing a state in which a protective film, a release film, and a release film are formed on the mold base material in the molding die according to Embodiment 1 of the present invention. It is an A section enlarged view of FIG. FIG. 3 is a cross-sectional view showing the molding die according to Embodiment 1 of the present invention. It is sectional drawing which shows the state which apply | coated the 1st resist to the metal mold | die base material in the metal mold | die which concerns on Embodiment 3 of this invention. It is sectional drawing which shows the state which formed the protective film in the metal mold | die base material in the metal mold | die for molding which concerns on Embodiment 3 of this invention. It is sectional drawing which shows the state which apply | coated the 2nd resist to the metal mold | die base material in which the protective film was formed in the metal mold | die which concerns on Embodiment 3 of this invention. It is sectional drawing which shows the state which formed the protective film, the peeling film, and the mold release film in the metal mold | die base material in the metal mold | die which concerns on Embodiment 3 of this invention. It is sectional drawing which shows the metal mold | die which concerns on Embodiment 3 of this invention.

  Hereinafter, the molding die of the present invention and the method for manufacturing the same will be described. The same or corresponding members and portions in each drawing will be denoted by the same reference numerals.

Embodiment 1.
1 is a sectional view showing a mold base material in a molding die according to Embodiment 1 of the present invention, and FIG. 2 shows a resist on the mold base material in a molding die according to Embodiment 1 of the present invention. 4 is a cross-sectional view showing the applied state, FIG. 3 is a cross-sectional view showing a state in which a protective film, a release film and a release film are formed on the mold base material in the molding die according to Embodiment 1 of the present invention, FIG. 3 is an enlarged view of part A in FIG. 3, and FIG. 5 is a cross-sectional view showing a molding die according to Embodiment 1 of the present invention.

  In FIG. 5, the molding die 1 includes a mold base material 2, a protective film 3 formed on the molding surface 2 a of the mold base material 2, and a release film 4 formed on the surface of the protective film 3. And a release film 5 formed on the surface of the release film 4.

  Since the mold base material 2 is required to have high heat resistance and high strength, it is formed of, for example, a cemented carbide containing tungsten carbide (WC) as a main component and another light metal element as a binder. Other light metal elements contained in the mold base material 2 include, for example, cobalt (Co), nickel (Ni), and chromium (Cr), and are added to increase the strength of the mold base material 2. It

The protective film 3 protects the mold base material 2 so as not to damage the mold base material 2 when the release film 5 is chemically removed, and protects the mold base material 2 and the release film 4. In order to improve the adhesion, it is formed so as to cover at least the molding surface 2a of the mold base material 2. The release film 4 is formed between the protective film 3 and the release film 5, and when the release film 5 deteriorates due to repeated molding, the release film 5 is selectively dissolved to simultaneously remove the release film 5. With function. The release film 4 is composed of a single layer or multiple layers, and each layer has a higher chemical reactivity than the mold base material 2, the protective film 3, and the release film 5, for example, nickel (Ni) or nickel. - phosphorus (Ni-P), gold (Au), chromium (Cr), is formed by a single material selected from chromium oxide _(Cr 2 _{O 3).}

  As described above, the material of the peeling film 4 can be selected from a plurality of metal species and the compounds thereof, so that the range of materials that can be used for peeling the mold releasing film 5 is widened. The thickness of the release film 4 is, for example, 0.05 to 0.50 μm, and the average surface roughness Ra of the release film 4 is, for example, 40 nm or less. The average surface roughness Ra is set to about 40 nm or less as a guide, but if the average surface roughness Ra exceeds 40 nm, the surface accuracy required for the molded product may not be maintained.

Since the release film 5 is in direct contact with the molding material, particularly in glass molding, a material that is hard to oxidize at the softening temperature of the glass material and is chemically stable, such as platinum (Pt), palladium (Pd), It is formed of one metal selected from iridium (Ir), rhodium (Rh), and ruthenium (Ru), or an alloy combining a plurality of metals. The film thickness of the release film 5 is, for example, 0.05 to 2 μm, and the average surface roughness Ra of the release film 5 is, for example, 40 nm or less. The release film 5 should not contain the same metal element as the element forming the release film 4. Further, the release film 5 needs to ensure good adhesion to the release film 4. As the adhesion, a strength of 0.05 kN / m or more is required. The release film 4 and the release film 5 may contain a metal element having a good compatibility with respect to bonding.
In this way, the material of the release film 5 can be selected from a plurality of metal species, so that the range of molding materials that can be used for the molded product can be widened.

  Next, a method for manufacturing the molding die 1 configured as described above will be described.

First, as shown in FIG. 1, a mold base material 2 processed into a desired shape is prepared.
Next, as shown in FIG. 2, a resist 21 is applied to the side surface 2b of the die base material 2.
Next, as shown in FIG. 3, a protective film 3 is formed on the molding surface 2 a of the mold base material 2, a release film 4 is formed on the protective film 3, and a release film 5 is formed on the release film 4. To do. Then, the resist 21 is removed and the molding die 1 shown in FIG. 5 is manufactured. Here, the protective film 3 can be formed by a dry film forming technique such as sputtering or vacuum evaporation. The release film 4 and the release film 5 can be formed by a dry film forming technique such as sputtering or vacuum deposition, or a wet film forming technique by electroplating or electroless plating.

  Hereinafter, a specific method for forming the protective film 3 and the peeling film 4 will be described.

  First, the mold base material 2 processed into a desired shape is degreased to remove surface contaminants such as organic contaminants from the tungsten carbide (WC) surface of the mold base material 2. Then, the degreased mold base material 2 is subjected to etching treatment to remove surface contaminants such as inorganic foreign matters and oxide film from the surface of the mold base material 2 to expose the active metal surface. Then, tungsten (W) is formed on the surface of the die base material 2 by a sputtering method in a film thickness range of 0.05 to 0.50 μm. If the thickness of the protective film 3 is less than 0.05 μm, the protective film 3 may be too thin, and the mold base material 2 may be damaged when the peeling film 4 is peeled off. Further, when the thickness of the protective film 3 exceeds 0.5 μm, the adhesion between the mold base material 2 and the protective film 3 is reduced, and film peeling may occur.

  Next, the protective film 3 is formed, and the mold base material 2 is subjected to an acid etching treatment to remove surface contaminants such as inorganic foreign matters and oxide film from the tungsten (W) surface of the protective film 3. Therefore, the active metal surface of tungsten (W) of the protective film 3 is exposed, and the liquid wettability is secured. As a result, the adhesion between the plating film formed in the subsequent plating step and the protective film of tungsten (W) is secured. The peeling film 4 also functions as a binder layer that secures close contact between the release film 5 and the tungsten (W) of the protective film 3.

  When a nickel-phosphorus film is formed as the peeling film 4, first, a strike nickel plating film is formed on the tungsten (W) of the protective film 3 that has been subjected to the acid etching treatment. As the strike nickel plating solution, a conventionally used wood bath or a commercially available plating solution can be used. As the liquid composition of the wood bath, for example, a plating solution in which 37 wt% hydrochloric acid is 120 mL / L, nickel chloride hexahydrate is 240 g / L, and pure water is added to adjust to 1 L can be used. Immersion of the die base material 2 on which the protective film 3 is formed in a strike nickel plating solution, plating conditions such as energization time and solution temperature are appropriately selected so that a strike nickel plating film having a desired film thickness can be obtained. Can be set. For example, by setting the liquid temperature to 25 ° C., the current density to 10 A / dm 2, and the plating time to 10 seconds, a strike nickel plating film of about 0.2 μm can be obtained.

  Then, electroless nickel plating is performed to form a nickel-phosphorus plated film 41 on the strike nickel plated film. As the electroless nickel plating solution, a conventionally known plating solution for electroless nickel plating in which the phosphorus concentration of the nickel plating film is low phosphorus (less than 5 wt%) and medium phosphorus (less than 5 wt% to 10 wt%) can be used. . For example, containing 2 wt% nickel sulfate as a metal salt, 2 wt% sodium hypophosphite as a reducing agent, 10 wt% citric acid, malic acid, succinic acid, etc. as a complexing agent, and using sulfuric acid or sodium hydroxide. A plating solution having a pH adjusted to 4.5 can be used. Unless otherwise specified, wt% in the present invention means a value with respect to the entire prepared solution.

  As for the plating conditions such as the immersion of the mold base material 2 on which the protective film 3 and the strike nickel plating film are formed in the electroless nickel plating solution, the energizing time and the solution temperature, the nickel-phosphorus plating film 41 having a desired film thickness is used. It can be set as appropriate so that it can be obtained. For example, when the liquid temperature is 80 ° C. and the plating time is 5 minutes, the nickel-phosphorus plated film 41 having a thickness of about 1 μm can be obtained.

  Then, the electroless gold plating film 42 is formed as the final layer of the peeling film 4. As the electroless gold plating solution, a commercially available gold cyanide plating solution or gold sulfite plating solution which has been conventionally used can be used. For example, as the cyan plating solution, a plating solution containing potassium gold cyanide as a metal salt, ethylenediaminetetraacetic acid as a complexing agent, citric acid, etc., and a pH adjusting agent, etc. can be used. As the gold sulfite-based plating solution, a plating solution containing sodium gold sulfite as a metal salt and sodium sulfite or ethylenediamine as a complexing agent can be used. The plating conditions such as immersion time and solution temperature of the mold base material 2 on which the protective film 3, the strike nickel plating film and the nickel-phosphorus plating film 41 are formed are electroless with a desired film thickness. It can be appropriately set so that the gold plating film 42 can be obtained. For example, when a cyan-based substitution type electroless gold plating solution is used, a solution temperature of 90 ° C. and a plating time of 10 minutes can provide an electroless gold plating film 42 of about 0.05 μm.

  As a result, in FIG. 4, a two-layer structure including the nickel-phosphorus plating film 41 and the electroless gold plating film 42 is formed. However, in reality, the strike nickel plating film, the nickel-phosphorus plating film 41, and the electroless gold plating are used. The peeling film 4 having a three-layer structure including the plating film 42 is formed on the protective film 3.

  Then, electroplating is performed to select from platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh), and ruthenium (Ru) on the electroless gold plating film 42 which is the peeling film 4. The release film 5 made of one metal or an alloy of a plurality of metals is formed.

  The electroplating solution has a platinum (Pt) plating solution having a platinum concentration of 15 to 25 g / L and a pH adjusted to 11 to 14, and the palladium plating solution has a palladium concentration of 1 to 5 g / L and a pH of A liquid adjusted to 8 to 10, an iridium plating liquid having an iridium concentration of 10 to 20 g / L and a pH adjusted to 2 to 5, and a rhodium plating liquid having a rhodium concentration of 1 to 10 g / L and a pH of As the solution adjusted to 0 to 3 and the ruthenium plating solution, a solution adjusted to a ruthenium concentration of 1 to 5 g / L and a pH of 0 to 3 can be used. As for the plating conditions such as the immersion of the mold base material 2 on which the protective film 3 and the peeling film 4 are formed in the electroplating solution, the energizing time and the solution temperature, the electroplating film as the release film 5 having a desired film thickness is selected. It can be set as appropriate so that it can be obtained.

  For example, with a platinum plating solution, a platinum plating film of about 1 μm can be formed by setting the solution temperature to 90 ° C., the cathode current density to 2 to 3 A / dm 2, and the plating time to 3 minutes. With the palladium plating solution, a solution temperature of 55 ° C., a cathode current density of 0.5 to 1 A / dm 2, and a plating time of 4 minutes can form a palladium plating film of about 1 μm. With the iridium plating solution, an iridium plating film of about 1 μm can be formed by setting the solution temperature to 85 ° C., the cathode current density to 0.2 to 0.5 A / dm 2, and the plating time to 15 minutes. With a rhodium plating solution, a solution temperature of 50 ° C., a cathode current density of 0.5 to 2.0 A / dm 2, and a plating time of 5 minutes can form a rhodium plating film of about 1 μm. With the ruthenium plating solution, a solution temperature of 65 ° C., a cathode current density of 0.5 to 2.0 A / dm 2, and a plating time of 10 minutes can provide a ruthenium plated film of about 1 μm.

  In addition, depending on the electroplating, the distribution may vary widely, and a desired alloy composition may not be obtained. In such a case, the desired release film 5 may be formed using a vacuum vapor deposition device or a sputtering device. When the film is formed by these dry film forming techniques, the film thickness distribution is smaller than that of the wet film forming technique, and the film thickness can be accurately determined. Is effective for.

  Next, a method of remanufacturing the molding die 1 thus manufactured will be described.

  First, concentrated hydrochloric acid is used as a stripping solution for the release film 5. By dipping the used molding die 1 in concentrated hydrochloric acid, the nickel-phosphorus plating film 41 of the release film 4 is dissolved and the release film 5 is released. Tungsten (W) of the protective film 3 does not react with concentrated hydrochloric acid. The immersion of the molding die 1 in concentrated hydrochloric acid can be appropriately set depending on the size of the die and the film thickness of the nickel-phosphorus plated film 41 of the release film 4. Further, dilute nitric acid can be used instead of concentrated nitric acid by adjusting the immersion time and the liquid temperature. Then, the molding die 1 from which the release film 4 and the release film 5 have been removed, that is, the mold base material 2 on which the protective film 3 has been formed, is taken out from concentrated hydrochloric acid and washed with water at room temperature for about 1 minute to obtain concentrated nitric acid. To remove.

  Then, a resist 21 is applied to the side surface 2b of the die base material 2. After that, in the same manner as the method described in the manufacturing method of the molding die 1, a strike nickel plating film is formed on the protective film 3, a nickel-phosphorus plating film 41 is formed on the strike nickel plating film, and a nickel-plating film is formed. An electroless nickel plating film 42 is formed on the phosphorus plating film 41. Next, the release film 5 is formed on the electroless nickel plated film 42, the resist 21 is removed, and the molding die 1 on which the release film 4 and the release film 5 are formed is regenerated.

  The molding die 1 according to the first embodiment includes a die base material 2, a protective film 3 made of tungsten (W) on the die base material 2, and nickel (Ni) and gold (on the protective film 3). Au) a pure metal or a compound thereof, and a peeling film 4 formed of platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh) and ruthenium (Ru) on the peeling film 4. The release film 5 is made of one metal or an alloy in which a plurality of metals are combined.

Therefore, since the release film 4 having high chemical reactivity is formed on the mold base material 2 side of the release film 5 which has poor chemical reactivity and is difficult to be physically removed by polishing or grinding, The release film 5 can be removed at the same time by dissolving and removing the release film 4 during reproduction. As a result, it is not necessary to physically remove the release film 5 by polishing / grinding using a diamond grindstone or the like, and the mold can be easily regenerated. Furthermore, since there is no damage to the die base material 2 due to polishing / grinding, no additional work is required to maintain the surface accuracy of the die after recycling. Furthermore, the heat capacity of the mold does not fluctuate due to the large fluctuation of the mold weight due to the additional machining, and the readjustment of the molding condition of the molded product becomes unnecessary.
Further, since the protective film 3 is formed on the mold base material 2, it is possible to suppress damage to the mold base material 2 due to the peeling liquid when the mold release film 5 is chemically removed, and at the same time, to prevent the mold base material from being damaged. The adhesion between 2 and the release film 4 is improved.

Embodiment 2.
In the first embodiment, the peeling film 4 made of a single metal of nickel (Ni) or gold (Au) or a compound thereof is used, but in the second embodiment, chromium or chromium oxide (Cr2O3) is used. The peeling film 4 made of is used.
Note that the other configurations are similar to those of the molding die 1 of the first embodiment.

  Next, a method of manufacturing the molding die 1 according to the second embodiment will be described.

  First, similarly to the method of manufacturing the molding die 1 according to the first embodiment, the die base material 2 is prepared, and the tungsten (W) protective film 3 is formed on the die base material 2 using the sputtering device. To be done.

Then, the peeling film 4 is formed by using a dry film forming technique such as sputtering or vacuum evaporation. When forming a chromium film as the peeling film 4, an electron beam vapor deposition apparatus is used. First, the mold base material 2 having the protective film 3 formed therein is put into an electron beam evaporation apparatus. At the same time, the release film material is put into the electron beam vapor deposition apparatus to be in a vacuum state. When the release film 4 is chromium (Cr), chromium (Cr) is used as the release film material, and when the release film 4 is chromium oxide (Cr ₂ O ₃ ), the release film material is chromium oxide (Cr ₂ O ₃ ). Is charged into the electron beam evaporation apparatus. Then, after reaching a predetermined degree of vacuum, energy is applied to the peeling film material by an electron beam to heat the peeling film material. As a result, the vapor pressure rises, film formation is started, and the peeling film 4 is formed on the protective film 3. The peeling film 4 thus formed also functions as a binder layer that secures the adhesion between the release film 5 and the tungsten (W) of the protective film 3.

When chromium (Cr) is selected for the peeling film 4, a chromium film having a film thickness of 0.05 to 0.50 μm is formed at a film forming rate of 0.2 to 2.0 nm / sec and peeling is performed. The film 4 is used. When chromium oxide (Cr ₂ O ₃ ) is selected for the peeling film 4, a chromium oxide layer having a thickness of 0.05 to 0.50 μm is formed at a film forming rate of 0.2 to 2.0 nm / sec. Then, the peeling film 4 is formed.

  Then, the release film 5 is formed on the release film 4 by electroplating in the same manner as in the method of manufacturing the molding die 1 according to the first embodiment. In addition, depending on the electroplating, the distribution may vary widely, and a desired alloy composition may not be obtained. In that case, a desired release film 5 may be obtained by a vacuum vapor deposition device or a sputtering device. When the film is formed by these dry film forming techniques, the film thickness distribution is smaller than that of the wet film forming technique, and the film thickness can be accurately determined. Is effective for.

Next, a method for recycling the molding die 1 according to the second embodiment will be described.
When a chromium film is used as the release film 5, diluted hydrochloric acid or diluted sulfuric acid is used as a stripping solution for the chromium film. By dipping the used molding die 1 in diluted hydrochloric acid or diluted sulfuric acid, the chromium film of the release film 4 is dissolved and the release film 5 is released. Tungsten (W) of the protective film 3 does not react with dilute hydrochloric acid. The immersion time of the molding die 1 in dilute hydrochloric acid can be appropriately set depending on the size of the die and the thickness of the chromium film of the release film 4. Further, since dilute sulfuric acid slightly damages tungsten (W) of the protective film 3, it can be used by adjusting the immersion time and the liquid temperature. Next, the molding die 1 from which the release film 4 and the release film 5 are peeled off, that is, the mold base material 2 on which the protective film 3 is formed is taken out from diluted hydrochloric acid or diluted sulfuric acid, and washed with water at room temperature for about 1 minute, Remove dilute hydrochloric acid or dilute sulfuric acid. Instead of the method of stripping a chromium film using dilute hydrochloric acid or dilute sulfuric acid, a method of stripping a chromium film by anodic electrolysis using an aqueous solution of sodium hydroxide may be used.

  When a chromium oxide film is used as the stripping film 4, sodium bromate is used as the stripping solution for the chromium oxide film. By dipping the used molding die 1 in sodium bromate, the chromium oxide film of the release film 4 is dissolved and the release film 5 is released. Tungsten (W) in the protective film does not react with sodium bromate. The immersion time of the molding die 1 in alkali bromate can be appropriately set depending on the size of the die and the thickness of the chromium oxide film as the release film 4. Then, the molding die 1 from which the release film 4 and the release film 5 are peeled off, that is, the mold base material 2 on which the protective film 3 is formed is taken out from sodium bromate and washed with water for about 1 minute at room temperature to remove bromine Remove sodium acidate.

  Next, the release film 5 is peeled off, and the mold base material 2 on which the protective film 3 is formed is inserted into the electron beam vapor deposition apparatus, and the peeling film 4 made of chromium or chromium oxide is formed on the protective film 3. Further, the release film 5 is formed on the release film 4 by using a wet film forming technique or a dry film forming technique, and the molding die 1 on which the release film 4 and the release film 5 are formed is regenerated.

  The molding die 1 according to the second embodiment includes a die base material 2, a protective film 3 made of tungsten (W) on the die base material 2, and chromium (Cr) or chromium oxide on the protective film 3. A release film 4 made of (Cr), and one metal or a plurality of metals selected from platinum (Pt), palladium (Pd), iridium (Ir), rhodium (Rh), and ruthenium (Ru) on the release film 4. And a release film 5 made of an alloy in which

Therefore, in the second embodiment, the peeling film 4 having high chemical reactivity is formed on the lower surface of the mold releasing film 5 which is poor in chemical reactivity and is difficult to physically remove by polishing or grinding, on the side of the mold base material 2. Therefore, the releasing film 5 can be removed at the same time by dissolving and removing the releasing film 4 when the mold is regenerated. Therefore, also in the second embodiment, the same effect as in the first embodiment can be obtained.
According to the second embodiment, chromium or a chromium compound is used as the peeling film 4. Since chromium (Cr) is the same Group 6 element as tungsten (W), it has good compatibility with tungsten (W) in view of the crystal structure and the coefficient of linear expansion. That is, the adhesion between the protective film 3 and the peeling film 4 is increased, and the occurrence of poor adhesion when using the mold can be suppressed.

Embodiment 3.
FIG. 6 is a sectional view showing a state in which a first resist is applied to a mold base material in a molding die according to Embodiment 3 of the present invention, and FIG. 7 is a molding die according to Embodiment 3 of the present invention. FIG. 8 is a cross-sectional view showing a state in which a protective film is formed on the mold base material in FIG. 8; 9 is a sectional view showing a state in which a protective film, a release film and a release film are formed on the die base material in the molding die according to Embodiment 3 of the present invention, and FIG. It is sectional drawing which shows the metal mold | die which concerns on Embodiment 3 of invention.

  In FIG. 10, a molding die 10 includes a die base material 2, a protective film 11 formed so as to cover the molding surface 2 a and the side surface 2 b of the die base material 2, and a surface of the protective film 11. The release film 12 is formed so as to cover the protective film 11 except for the peripheral portion, and the release film 13 is formed so as to cover the entire surface of the release film 12. The peeling film 12 is formed of any one of nickel-phosphorus, gold, chromium, and chromium oxide used in the first and second embodiments. Protective film 11 and release film 13 are made of the same material as protective film 3 and release film 5 in the first and second embodiments. The release film 12 and the release film 13 have a structure that covers the entire molding surface 2a of the mold base material 2 and a part of the side surface 2b, and the peripheral edge of the protective film 11 is exposed over the entire circumference. .

  Next, a method of manufacturing the molding die 10 according to the third embodiment will be described.

First, the die base material 2 processed into a desired shape is prepared. Next, as shown in FIG. 6, the first resist 22 is applied to the mold base material 2 so that the molding surface 2a and the side surface 2b are exposed.
Next, as shown in FIG. 7, the protective film 3 is formed on the die base material 2 by a dry film forming technique such as sputtering or vacuum deposition. Then, the first resist 22 is removed, and as shown in FIG. 8, the second resist 23 is applied to the mold base material 2 so as to cover the peripheral portion of the protective film 11 over the entire circumference. Then, as shown in FIG. 9, the release film 4 and the release film 5 are protected by a dry film forming technique such as sputtering or vacuum deposition, or a wet film forming technique by electroplating. Form on 11. Further, the second resist 23 is removed, and the molding die 10 shown in FIG. 10 is manufactured.
The specific method of forming the protective film 11 and the peeling film 12 is the same as in the first and second embodiments.

The molding die 10 according to the third embodiment includes a die base material 2, a protective film 11 made of tungsten (W) on the die base material 2, and nickel-phosphorus (Ni-P) on the protective film 11. , Gold (Au), chromium (Cr), or chromium oxide (Cr ₂ O ₃ ), a peeling film 12, and platinum (Pt), palladium (Pd), iridium (Ir) on the peeling film 12. , A release film 13 made of one metal selected from rhodium (Rh) and ruthenium (Ru) or an alloy combining a plurality of metals.

  Therefore, in the third embodiment, the release film 12 having a high chemical reactivity is formed on the mold base material 2 side of the release film 13 which has a low chemical reactivity and is difficult to be physically removed by polishing or grinding. Therefore, the mold release film 13 can be removed at the same time by dissolving and removing the release film 12 when the mold is regenerated. Therefore, also in the third embodiment, the same effect as in the first embodiment can be obtained.

  In the first and second embodiments, the protective film 3, the peeling film 4, and the release film 5 cover the molding surface 2a of the mold base material 2 with their side surfaces flush with each other. 2b is exposed. Therefore, at the time of peeling the peeling film 3, the peeling liquid may come into contact with the side surface 2b of the mold base material 2 depending on the immersion state of the mold base material 2 in the peeling liquid, and the interface between the mold base material 2 and the protective film 11 may be removed. There was a risk of damage. When the interface between the die base material 2 and the protective film 11 is damaged, it is necessary to perform additional dimensioning of the die.

  In the third embodiment, the protective film 11 is formed so as to cover the molding surface 2a and the side surface 2b of the mold base material 2, and the release film 12 and the release film 13 expose only the peripheral portion of the protective film 11. Since it is formed so as to prevent the release liquid from coming into contact with the side surface 2b of the mold base material 2 at the time of peeling the release film 12, the release liquid is removed from the mold base material 2 and the protective film 11. Does not damage the interface. Therefore, it is not necessary to perform dimensioning by additional machining of the mold due to damage to the mold base material 2, and therefore the reclaiming work of the release film 13 becomes easy.

  Hereinafter, examples and comparative examples of the present invention will be described in detail. The present invention is not limited to these embodiments. The specifications of Examples and Comparative Examples are shown in Table 1, and the results of the peeling test of Examples and Comparative Examples are shown in Table 2.

Examples 1, 2.
The first and second embodiments are based on the first embodiment.
Specifically, as shown in FIG. 2, the resist is formed on the side surface 2b of the die base material 2 so that the forming surface 2a of the die base material 2 made of tungsten carbide having a film forming surface of φ30 mm is exposed. 21 was applied. Then, degreasing treatment was carried out using a degreasing agent ELC-400 (manufactured by World Metal Co., Ltd.) to remove organic substances. Then, the mold base material 2 was immersed in pure water, left for 1 minute and then taken out.

  Then, using HS-55 (manufactured by World Metal Co., Ltd.), the mold base material 2 is subjected to an acid electrolytic etching treatment, and further by using HC-55 (manufactured by World Metal Co., Ltd.), the mold base material 2 is used. 2 was subjected to etching treatment to remove surface contaminants such as inorganic foreign matters and oxide film. Then, the mold base material 2 was immersed in pure water, left for 1 minute and then taken out.

  Next, using a sputtering apparatus, tungsten was formed into a film having a thickness of 0.1 μm on the surface of the die base material 2. As a result, the protective film 3 made of tungsten was formed on the surface of the die base material 2.

  Then, the die base material 2 on which tungsten is formed is subjected to an acid etching treatment, and a strike nickel plating film having a thickness of 0.1 μm is formed on the surface of the tungsten by using a plating solution of NI-STK (manufactured by World Metal Co., Ltd.). It was formed into a film. Then, an electroless Ni-P plating film having a thickness of 0.5 μm was formed on the surface of the strike nickel plating film by using Top Nicolon BL (produced by Okuno Chemical Industries Co., Ltd.) as a plating solution. Further, an electroless Au plating film having a thickness of 0.05 μm was formed on the surface of the electroless Ni—P plating film using a plating solution of Flash Gold 2000 (manufactured by Okuno Chemical Industries Co., Ltd.). As a result, the peeling film 4 having a three-layer structure including the strike nickel plating film, the electroless Ni—P plating film, and the electroless Au plating film was formed on the surface of the protective film 3.

  Then, a platinum plating film having a thickness of 500 nm was formed on the surface of the peeling film 4 using a plating solution of Platinate 100 (manufactured by EEJA Co., Ltd.). As a result, the release film 5 made of the platinum plating film was formed on the surface of the release film 4. Then, the resist 21 was peeled off and removed, and the molding die 1 shown in FIG. 5 was produced.

  Then, a peeling test of the release film 5 of the molding die 1 was performed. In Example 1, the molding die 1 was immersed in concentrated hydrochloric acid and left at room temperature for 5 minutes. Further, in Example 2, the molding die 1 was immersed in dilute nitric acid and left at room temperature for 5 minutes.

Examples 3-5.
Examples 3 to 5 are based on the second embodiment.
In Examples 3 to 5, using the tungsten carbide mold base material 2 having a film-forming surface of φ30 mm, the resist 21 was applied, degreasing treatment, and acid electrolytic etching treatment were performed in the same manner as in Examples 1 and 2. , And etching treatment were performed, and then a protective film 3 of tungsten was formed on the surface of the die base material 2 using a sputtering device.

  Then, in Examples 3 and 4, chromium was deposited to a thickness of 0.5 μm on the surface of tungsten using a vacuum vapor deposition apparatus. In Example 5, a vacuum vapor deposition apparatus was used to deposit chromium oxide on the surface of tungsten to a thickness of 0.5 μm. As a result, the peeling film 4 made of chromium or chromium oxide was formed on the surface of the protective film 3.

  Then, a platinum plating film having a thickness of 500 nm was formed on the surface of the peeling film 4 using a plating solution of Platinate 100 (manufactured by EEJA Co., Ltd.). As a result, the release film 5 made of the platinum plating film was formed on the surface of the release film 4. Then, the resist 21 was peeled off and removed, and the molding die 1 shown in FIG. 5 was produced.

  Then, a peeling test of the release film 5 of the molding die 1 was performed. In Example 3, the molding die 1 was immersed in concentrated hydrochloric acid and left at room temperature for 5 minutes. Further, in Example 4, the molding die 1 was immersed in dilute sulfuric acid and left at room temperature for 5 minutes. Further, in Example 5, the molding die 1 was immersed in alkali bromate and left at room temperature for 5 minutes.

Examples 6, 7.
Examples 6 and 7 are based on the third embodiment.
As shown in FIG. 6, the first resist 22 is applied to the mold base material 2 so that the molding surface 2a and the side surface 2b of the tungsten carbide mold base material 2 having a film forming surface of φ30 mm are exposed. To do. Then, degreasing treatment was carried out using a degreasing agent ELC-400 (manufactured by World Metal Co., Ltd.) to remove organic substances. Then, the mold base material 2 was immersed in pure water, left for 1 minute and then taken out.

  Then, using HS-55 (manufactured by World Metal Co., Ltd.), the mold base material 2 is subjected to an acid electrolytic etching treatment, and further by using HC-55 (manufactured by World Metal Co., Ltd.), the mold base material 2 is used. 2 was subjected to etching treatment to remove surface contaminants such as inorganic foreign matters and oxide film. Then, the mold base material 2 was immersed in pure water, left for 1 minute and then taken out.

  Next, using a sputtering apparatus, tungsten was formed into a film having a thickness of 0.1 μm on the surface of the die base material 2. As a result, the protective film 11 made of tungsten was formed on the surface of the die base material 2. Then, the first resist 22 was removed, and as shown in FIG. 8, the second resist 23 was applied to the mold base material 2 so as to cover the peripheral portion of the protective film 11.

  Then, the die base material 2 on which tungsten is formed is subjected to an acid etching treatment, and a strike nickel plating film having a thickness of 0.1 μm is formed on the surface of the tungsten by using a plating solution of NI-STK (manufactured by World Metal Co., Ltd.). It was formed into a film. Then, an electroless Ni-P plating film having a thickness of 0.5 μm was formed on the surface of the strike nickel plating film by using Top Nicolon BL (produced by Okuno Chemical Industries Co., Ltd.) as a plating solution. Further, an electroless Au plating film having a thickness of 0.05 μm was formed on the surface of the electroless Ni—P plating film using a plating solution of Flash Gold 2000 (manufactured by Okuno Chemical Industries Co., Ltd.). Thereby, the peeling film 12 having a three-layer structure including the strike nickel plating film, the electroless Ni—P plating film, and the electroless Au plating film was formed on the surface of the protective film 11.

  Then, a platinum plating film having a thickness of 500 nm was formed on the surface of the peeling film 12 using a plating solution of Platinate 100 (manufactured by EEJA Co., Ltd.). As a result, the release film 13 made of the platinum plating film was formed on the surface of the release film 12. After that, the second resist 23 was peeled and removed, and the molding die 10 shown in FIG. 10 was produced.

  Then, a peeling test of the release film 13 of the molding die 10 was performed. In Example 6, the molding die 10 was immersed in concentrated hydrochloric acid and left at room temperature for 5 minutes. Further, in Example 7, the molding die 10 was immersed in dilute nitric acid and left at room temperature for 5 minutes.

Examples 8-10.
Examples 8 to 10 are based on the third embodiment.
In Examples 8 to 10, the mold base material 2 made of tungsten carbide having a film-forming surface of φ30 mm was used, and the first resist 22 was applied, degreasing treatment, and acid electrolysis were performed as in Examples 6 and 7. After performing the etching process and the etching process, a tungsten protective film 11 was formed on the surface of the die base material 2 by using a sputtering apparatus. Then, the first resist 22 was removed, and as shown in FIG. 8, the second resist 23 was applied to the mold base material 2 so as to cover the peripheral portion of the protective film 11.

  Then, in Examples 8 and 9, chromium was deposited to a thickness of 0.5 μm on the surface of tungsten using a vacuum vapor deposition apparatus. In Example 10, a vacuum vapor deposition apparatus was used to deposit chromium oxide on the surface of tungsten to a thickness of 0.5 μm. As a result, the peeling film 12 made of chromium or chromium oxide was formed on the surface of the protective film 11.

  Then, a platinum plating film having a thickness of 500 nm was formed on the surface of the peeling film 12 using a plating solution of Platinate 100 (manufactured by EEJA Co., Ltd.). As a result, the release film 13 made of the platinum plating film was formed on the surface of the release film 12. After that, the second resist 23 was peeled and removed, and the molding die 10 shown in FIG. 10 was produced.

  Then, a peeling test of the release film 13 of the molding die 10 was performed. In Example 8, the molding die 10 was immersed in concentrated hydrochloric acid and left at room temperature for 5 minutes. Further, in Example 9, the molding die 10 was immersed in dilute sulfuric acid and left at room temperature for 5 minutes. Further, in Example 10, the molding die 10 was immersed in alkali bromate and left at room temperature for 5 minutes.

Comparative Examples 1 to 4.
In Comparative Examples 1 to 4, the same mold base material 2 as in Examples 1 to 10 was used, and similarly to Examples 1 to 5, the mold base 2 was exposed so that the molding surface 2a of the mold base material 2 was exposed. A resist 21 was applied to the side surface 2b of the base material 2. Then, similarly to Examples 1 to 10, the mold base material 2 was subjected to degreasing treatment, acid electrolytic etching treatment, and etching treatment. Then, similarly to Examples 1 to 10, the release film 5 made of a platinum plating film was formed on the surface of the molding surface 2a of the mold base material 2. After that, the resist 21 was peeled and removed, and the molding dies of Comparative Examples 1 to 4 were produced. In the molding dies of Comparative Examples 1 to 4, the protective film and the peeling film are omitted.

  Then, a peeling test of the release film 5 of the molding die was carried out. In Comparative Example 1, the molding die was immersed in concentrated hydrochloric acid and left at room temperature for 5 minutes. Further, in Comparative Example 2, the molding die was immersed in dilute sulfuric acid and left at room temperature for 5 minutes. In Comparative Example 3, the molding die was dipped in dilute hydrochloric acid and left at room temperature for 5 minutes. In Comparative Example 4, the molding die was dipped in dilute sulfuric acid and left at room temperature for 5 minutes.

  Table 2 shows the results of the peeling test of the release film 5. In the peeling test, after the peeling test, the peeled state of the release film and the damaged state of the die base material were investigated. Regarding the peeling state of the release film, visually inspect the mold base material after peeling, and check that the release film is completely peeled off (the outermost surface on the mold side is only the protective film of tungsten). The state in which a part of the film remained or the release film completely remained was defined as x. In addition, regarding the damaged state of the mold base material, the mold base material after peeling is inspected visually and with an optical microscope, and if there is no peeling at the interface between the mold base material and the protective film, a small amount is peeled. (The peeled area is within 1/10 of the contact area between the protective film and the mold base material), and the peeling is observed (the peeled area is 1/10 of the contact area between the protective film and the mold base material). Is exceeded.

As is clear from the evaluation results shown in Table 2, in Comparative Examples 1 to 4 in which the protective film and the release film were not formed on the mold base material, the release film could not be released, and the mold base material by the release liquid was used. Damage was seen.
However, in contrast to this, in the present invention, as shown in Examples 1 to 10 in which the protective film and the release film are formed on the mold base material, the release film can be removed by the chemical treatment, and the gold can be removed by the release liquid. The mold base material was not damaged. Thus, the clear effect of the present invention could be confirmed.

  1, 10 Mold for molding, 2 Mold base material, 3 11, Protective film, 4, 12 Release film, 5, 13 Release film, 21 Resist, 22 First resist, 23 Second resist.

Claims (6)

A mold base material, a protective film formed on the mold base material in a state of covering the molding surface of the mold base material, and a protective film formed on the protective film, the mold base material and the protective film A release film made of a material having a high chemical reactivity, and a release film formed on the release film and made of a material having a lower chemical reactivity than the release film ,
The protective film is formed on the mold base material in a state of covering a region exceeding the molding surface of the mold base material,
The release film is formed on the protective film in a state of covering a region exceeding the molding surface of the mold base material,
The release film is formed on the release film in a state of covering a region exceeding the molding surface of the mold base material,
A molding die in which a peripheral portion of the protective film is exposed over the entire circumference .   The molding die according to claim 1, wherein the protective film is made of tungsten.   The molding die according to claim 1 or 2, wherein the release film has a single-layer structure or a multi-layer structure, and each layer is made of one selected from nickel, nickel-phosphorus, gold, chromium, and chromium oxide. The molding die according to claim 1 or 2 , wherein the release film is made of one metal selected from platinum, palladium, iridium, rhodium, and ruthenium or an alloy in which a plurality of metals are combined. A mold base material, a protective film formed on the mold base material in a state of covering the molding surface of the mold base material, a release film formed on the protective film, and formed on the release film A method for manufacturing a molding die including:
A step of applying a first resist on the surface of the mold base material so that a region beyond the molding surface of the mold base material is exposed;
A protective film forming step of forming the protective film on the surface of the mold base material coated with the first resist by using a dry film forming technique;
A step of removing the first resist and applying a second resist to the mold base material so that the protective film is exposed except for the peripheral portion thereof;
A peeling film forming step of forming a peeling film on the die base material coated with the second resist by using a wet film forming technique or a dry film forming technique;
A release film forming step of forming a release film on the mold base material on which the release film is formed by using a wet film forming technique or a dry film forming technique;
A step of removing the second resist,
A method for manufacturing a molding die including: A mold base material, a protective film formed on the mold base material in a state of covering the molding surface of the mold base material, a release film formed on the protective film, and formed on the release film The release film is formed on the mold base material in a state of covering the region beyond the molding surface of the mold base material, and the release film is the mold base material. Is formed on the protective film in a state of covering a region beyond the molding surface of the material and exposing at least the peripheral portion of the protective film over the entire circumference, and the release film is the molding of the mold base material. A method of regenerating a molding die formed on the release film in a state of covering a region exceeding a surface ,
A mold release film removing step of removing the mold release film by immersing the molding die in a mold release liquid to dissolve and remove the mold release film.
A step of applying a resist to the mold base material so that the protective film is exposed except for the peripheral portion;
A peeling film re-forming step of reforming a peeling film using a wet film forming technique or a dry film forming technique on the mold base material coated with the resist ;
A release film re-forming step of re-forming a release film on the mold base material on which the release film is formed using a wet film forming technique or a dry film forming technique,
A step of removing the resist,
And a method for regenerating a molding die.

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