WO2012008372A1 - Matrice à isolation thermique et son procédé de production - Google Patents

Matrice à isolation thermique et son procédé de production Download PDF

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Publication number
WO2012008372A1
WO2012008372A1 PCT/JP2011/065668 JP2011065668W WO2012008372A1 WO 2012008372 A1 WO2012008372 A1 WO 2012008372A1 JP 2011065668 W JP2011065668 W JP 2011065668W WO 2012008372 A1 WO2012008372 A1 WO 2012008372A1
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WIPO (PCT)
Prior art keywords
film
heat insulating
metal
mold
heat insulation
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PCT/JP2011/065668
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English (en)
Japanese (ja)
Inventor
鳥井　秀雄
真也 小島
鈴木　孝芳
Original Assignee
神戸セラミックス株式会社
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Priority to JP2011552653A priority Critical patent/JP4966437B2/ja
Publication of WO2012008372A1 publication Critical patent/WO2012008372A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/02—Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/02—Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means
    • B29C2033/023—Thermal insulation of moulds or mould parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/26—Moulds
    • B29C45/263—Moulds with mould wall parts provided with fine grooves or impressions, e.g. for record discs
    • B29C45/2632—Stampers; Mountings thereof
    • B29C2045/2634—Stampers; Mountings thereof mounting layers between stamper and mould or on the rear surface of the stamper
    • B29C2045/2636—Stampers; Mountings thereof mounting layers between stamper and mould or on the rear surface of the stamper insulating layers

Definitions

  • the present invention relates to a heat insulating mold used for resin molding of, for example, optical elements and precision parts, and a manufacturing method thereof.
  • Various resin molded products are manufactured by, for example, a resin injection molding method in which a molten resin is injected into a molding space formed between a fixed die, which is a molding die, and a movable die.
  • injection molding which is a typical molding method for resin molding
  • the heat of the molten resin quickly moves to the mold and comes into contact with the mold.
  • the surface of the molten resin is rapidly cooled and solidified, and proceeds to the inside to complete the molding.
  • the temperature of the charged resin is not lowered so that the viscosity of the resin suitable for molding is maintained until the mold molding surface can be sufficiently transferred to the charged resin. Is to do.
  • the other is that once the predetermined shape can be transferred, the heat held by the molten resin in the mold is immediately released through the mold and the temperature of the resin is lowered to cause solidification.
  • After improving the transferability by heating the entire mold before injection molding it is possible to immediately cool the entire mold and solidify the transferred resin to release the mold, It is necessary to add a large-scale heating / cooling facility for the entire mold to the resin molding apparatus, which is not appropriate in terms of cost and energy.
  • the thermal spraying method melts or softens the coating material by heating with plasma, etc., accelerates and sprays at a high speed into fine particles, collides with the surface of the object to be coated, solidifies and deposits the flattened particles, It is a coating technology that forms a film.
  • a ceramic material having low thermal conductivity and high mechanical strength, particularly a film formed by spraying zirconia, as a heat insulating film of a conventional mold for example, Patent Document 2).
  • FIG. 24 the conventional heat insulation metal mold
  • a heat insulating mold 101 is composed of a mold base material 102, a heat insulating film (heat insulating layer) 105, and a metal film layer 108 having a precision processed surface 107a.
  • the heat insulating film 105 is characterized in that it is a heat insulating film made of a sprayed film of a ceramic material such as zirconia.
  • the sprayed film on which the ceramic fine particles are sprayed on the surface of the mold base material is The thickness of the sprayed film tends to be different at the outer peripheral portion. Therefore, by forming a metal plating film on the surface of the sprayed coating that is considerably thicker than usual, and machining the thick plated film precisely, the surface that has changed due to the formation of the sprayed coating is corrected by processing, and as a heat insulating mold Used.
  • the heat insulating property varies depending on the location of the surface of the molding surface.
  • the following method has been proposed to make the heat insulation of the mold more uniform.
  • a sprayed film that is thicker than the target thickness is formed in the sprayed film forming process, and then this is subjected to machining such as grinding and cutting.
  • machining such as grinding and cutting.
  • the added machining process is a process for precisely processing a sprayed film having high hardness, it involves difficulty and labor. Further, in the sprayed film, internal stress distortion may occur in the sprayed film in the sprayed film forming stage or the subsequent processing stage. When such an internal stress distortion occurs, cracks and the like are generated in the sprayed film, resulting in a fatal defect such as peeling of the sprayed film, which greatly impedes the molding process.
  • the thermal spraying method is a method of forming a film by spraying a high-velocity high-velocity fluid with a high degree of molten fine particles onto the surface to be formed. It is increasingly difficult to coat with a large thickness.
  • the main object of the present invention is to provide a mold having a heat insulating layer that does not require post-processing, has a uniform thickness compared to the prior art, and has excellent adhesion to the mold. It is in.
  • this invention relates to the following heat insulation metal mold
  • a metal mold having a heat insulating layer between a metal mold base material and a metal film constituting a molding surface, wherein the heat insulating layer is a porous structure in which ferrite crystal particles are formed in a three-dimensional network.
  • a heat insulating mold characterized by comprising a solid body.
  • the ferrite has the following general formula A x Fe 3-x O 4 (where A represents at least one metal element that can be substituted for the Fe site constituting the spinel-type iron oxide crystal, and x is 0 ⁇ x ⁇ 1 Meet) Item 2.
  • the heat-insulating mold according to Item 1 which is a compound having a spinel-type crystal structure represented by: 3.
  • Item 3. The heat insulating mold according to Item 2, wherein A is at least one of Ca, Zn, Mn, Al, Cr, Li, and Mg. 4).
  • Item 2. The heat insulating mold according to Item 1, wherein the heat insulating layer has a porosity of 5 to 75%. 5.
  • Item 2. The heat insulating mold according to Item 1, wherein the heat insulating layer has a Vickers hardness of Hv130 to Hv560. 7.
  • a heat insulating layer is generated by reacting 1) the surface of a metal mold base or 2) the surface of a metallic layer previously formed on the surface of the mold base with an aqueous solution or water dispersion containing a metal component.
  • Item 2. The heat insulation mold according to Item 1, wherein the heat insulation mold is prepared. 8).
  • Item 2. The heat insulating mold according to Item 1, wherein the metal film includes at least 1) a seed layer including a plating catalyst formed on the heat insulating layer, and 2) a metal plating film formed on the seed layer. 9.
  • the heat insulating mold according to Item 1 which is used for molding a composition containing a resin component. 10.
  • Production method. 11. Item 11. The method according to Item 10, comprising: 1) a step of forming a seed layer containing a catalyst on the heat insulating layer; and 2) a step of forming a metal plating film on the seed layer as the metal film forming step. . 12 Item 12.
  • the reaction is 1) the surface of the metal mold base material or 2) the surface of the metal layer previously formed on the mold base material is in contact with the treatment liquid obtained by mixing the metal salt, alkali and water.
  • Item 11 The method according to Item 10, comprising a heat treatment at a temperature of 85 ° C or higher.
  • the heat treatment is performed in an environment of a saturated water vapor pressure of 100 to 200 ° C or higher.
  • Item 11 The method according to Item 10, wherein the reaction is performed in the presence of a reducing agent.
  • the present invention it is possible to provide a mold having a heat-insulating layer that does not require post-processing, has a uniform thickness compared to the prior art, and has excellent adhesion to the mold. Thereby, especially when resin molding is performed, a complicated molding surface can be accurately transferred, and a precise molding can be freely produced.
  • the heat insulating layer can be formed by a wet reaction (particularly hydrothermal synthesis reaction) using the material that is the base of the heat insulating layer as a starting material.
  • a heat insulating layer having a relatively uniform thickness can be formed along the surface shape of a metal mold or the like as a base.
  • the heat insulation layer is formed integrally with the metal mold etc. by the hydrothermal synthesis reaction, the risk of dropping, peeling, etc. due to cracks, internal stress, etc., as in the conventional sprayed film is greatly reduced. As a result, it is possible to further increase the production efficiency of the resin molded body.
  • the heat retention and cooling properties of the fine region of the mold forming surface through which the molten resin flows can be improved. It can be finely controlled. As a result, resin molding of a molded product having a more complicated uneven shape can be expected. In this case, it is required that the material for forming the heat insulating layer can be easily processed, but the heat insulating film of the present invention is excellent in machinability, so that it is necessary to partially control the heat dissipation of the mold surface during resin molding.
  • a resin to be injected at the time of molding by cutting only a necessary portion with respect to the heat insulating film formed to have a uniform thickness on the entire surface of the heat insulating mold surface of the present invention It becomes possible to control the heat flow or cooling of the glass more precisely.
  • Such a mold of the present invention is particularly suitable for the production of a resin molded body. Therefore, it is useful for manufacturing optical materials (lenses, prism sheets, light guide plates, optical disks such as CD / DVD disks, and other recording media), for example.
  • FIG. It is an X-ray-diffraction pattern figure of the heat insulation film
  • FIG. It is a figure which shows the heat insulation evaluation result at the time of temperature rising of the sample for heat insulation evaluation provided with the heat insulation film
  • the heat-insulating mold of the present invention (the mold according to the present invention) is a mold having a heat-insulating layer between a metal mold base material and a metal film constituting the molding surface, It is characterized by comprising a porous body in which ferrite crystal particles are formed in a three-dimensional network.
  • the mold of the present invention has a basic structure of a) metal mold base material / heat insulating layer / metal film or b) metal mold base material / metallic layer / heat insulating layer / metal film.
  • other layers may be included as necessary.
  • the configuration of each layer will be described.
  • metal includes not only a metal simple substance but also an alloy and an intermetallic compound.
  • Metal mold base metal The metal mold base material only needs to be made of metal, and may be the same material as that used in known or commercially available molds. Examples thereof include metals such as iron, aluminum, and copper (metal simple substance), alloys such as carbon steel, stainless steel, copper alloy, and titanium alloy. Further, the metal mold base material may be either a melted material or a sintered body.
  • an iron-based metal as a metal mold base material because of the advantage that a ferrite layer as a heat insulating layer can be formed directly on the surface of the iron-based metal. That is, it is preferable to use at least one iron-based metal of metallic iron and iron alloy. It does not specifically limit as an iron alloy, For example, carbon steel, stainless steel (SUS), chromium molybdenum steel etc. can be used suitably.
  • the molding surface side of the metal mold base material may be either a flat surface or a curved surface, and may be a reversing mold of a fine shape to be imparted to the final molded body. It can comprise suitably according to the shape of the molded object to perform. For example, in particular, when the mold requires a deep recess (groove), an inverted mold having a shape to be transferred to the molding surface in advance or a similar shape (concave) is formed on the molding surface side of the metal mold base material. May be.
  • Metal film should just be comprised from the metal, and may be the same as the material employ
  • metals such as iron, nickel, copper, and chromium, alloys such as nickel phosphorus alloys, nickel boron, nickel tungsten phosphorus alloys, nickel copper phosphorus alloys, and the like.
  • the metal film may be composed of a single layer or multiple layers.
  • the metal film in order to further improve the adhesion (bondability) between the heat insulating layer and the metal film, the metal film has a two-layer structure of a first metal film and a second metal film, and between the heat insulating layer and the second metal film.
  • a first metal film may be interposed as an adhesive layer (underlayer). More specifically, a configuration including 1) a seed layer including a plating catalyst formed on the heat insulating layer and 2) a metal plating film formed on the seed layer can be employed.
  • a layer made of a metal that can be a catalyst during plating of the upper metal plating film is adopted, and the metal plating film is formed while using it as a catalyst.
  • a film can be formed.
  • a finely processed metal film having a finely processed surface as a layer constituting the molding surface can be formed on the second metal film as the third metal film.
  • the formation method of the metal film is not particularly limited, and can be appropriately selected from known methods according to the metal species to be employed, the composition of the underlying layer, and the like.
  • plating methods such as electrolytic plating and electroless plating (liquid phase growth method); chemical vapor deposition methods such as thermal CVD, MOCVD, and RF plasma CVD; sputtering methods, ion plating methods, MBE methods, and vacuum deposition methods
  • Various known thin film forming methods such as physical vapor deposition methods such as the above can be appropriately employed in combination of one or more.
  • each layer can be formed by the following method. It can. For example, 1) A seed layer (first metal film) containing a plating catalyst (metal catalyst) formed by a sputtering method is formed on the heat insulation layer, and metal plating is performed on the seed layer by a plating method using the catalyst. A film (second metal film) can be suitably formed.
  • first metal film as the adhesive layer (underlying layer) and the second metal film formed thereon are formed as described above
  • each layer can be formed by the following method. it can. For example, 1) A seed layer (first metal film) containing a plating catalyst (metal catalyst) formed by a sputtering method is formed on the heat insulation layer, and metal plating is performed on the seed layer by a plating method using the catalyst.
  • a film (second metal film) can be suitably formed.
  • a micromachined metal film can be formed by the plating method on the metal plating film which is the said 2nd metal film.
  • the thickness of the metal film in the mold of the present invention (total thickness of each layer in the case of a multilayer structure) is not particularly limited, but is usually about 20 to 300 ⁇ m, and preferably 50 to 150 ⁇ m. What is necessary is just to set the thickness of each layer in the case of a multilayer structure suitably according to the number of layers, the material of each layer, etc.
  • the heat insulating layer (also referred to as “heat insulating film”) in the mold of the present invention is formed between a metal mold base material and a metal film constituting the molding surface. As a result, it is possible to effectively suppress or prevent the phenomenon in which the heat of the molten molding material is rapidly taken away by the metal mold base material.
  • the heat insulating layer is composed of a porous body in which ferrite crystal particles are formed in a three-dimensional network.
  • a material of the heat insulating layer by adopting ferrite among metal oxides, it is possible to obtain higher heat insulating properties and to exhibit high adhesion to the metal mold or metallic layer which is the base. Can do.
  • the structure of the porous body is formed by connecting ferrite crystal particles in a three-dimensional network.
  • a porous body is formed from a three-dimensional network structure in which a plurality of polyhedral crystal grains that are not rounded and have one or more corners are connected.
  • communication holes are formed in the porous body.
  • the ferrite crystal particles may be twins or may be a series of crystals.
  • the ferrite crystal particles constituting the porous structure preferably have a spinel crystal structure.
  • the ferrite has the following general formula A x Fe 3-x O 4 (where A represents at least one metal element that can be substituted for the Fe site constituting the spinel-type iron oxide crystal, and x represents 0 It is preferable that the compound has a spinel type crystal structure represented by ⁇ x ⁇ 1.
  • x 0 ⁇ x ⁇ 1
  • the case of x 0, that is, the case of iron ferrite (that is, spinel-type iron oxide Fe 3 O 4 ) is included, and a part of the Fe site is replaced with other parts.
  • the composition may be substituted with a metal element.
  • A is not limited as long as it is at least one metal element that can be substituted for the Fe site constituting the spinel-type iron oxide crystal, but Ca, Zn, Mn, Al, Cr, Li, and Mg are not particularly limited. It is desirable to be at least one of these. Therefore, in the present invention, a composition in which the A component is at least one of Ca, Zn, Mn, Al, Cr, Li, and Mg may be used.
  • Such a composition itself may be any known one, for example, Ca 0.5 Fe 2.5 O 4 , ZnFe 2 O 4 , MnFe 2 O 4 , AlFe 2 O 4 , CrFe 2 O 4 , Li can be mentioned 0.5 Fe 2.5 O 4, MgFe least one such 2 O 4.
  • the thermal expansion coefficient of the heat insulation layer is not particularly limited, but the metal mold is used under severe conditions where the temperature rises and falls severely, so the thermal expansion coefficient of the heat insulation layer is the same as that of the metal mold. A closer value is desirable in terms of durability. Therefore, the thermal expansion coefficient of the heat insulating layer is preferably in the range of 90 to 110% of the thermal expansion coefficient of the metal mold used particularly at a high molding temperature of 200 ° C. or higher.
  • the porosity of the heat insulating layer is not limited, it is usually preferably in the range of about 5 to 75%, particularly 40 to 60% from the viewpoint that higher heat insulating performance can be achieved.
  • the porosity can be controlled by synthesis conditions such as synthesis temperature and raw material concentration.
  • the measuring method of the porosity in the present invention is based on the method shown in the examples described later.
  • the hardness of the heat insulating layer can be appropriately set according to the type of material to be molded, etc., but in general, the Vickers hardness (average value) is preferably Hv 130 to Hv 560, particularly preferably Hv 200 to Hv 400.
  • the metal oxide is preferably conductive.
  • molding surface can be formed on a heat insulation layer with an electroplating method. This makes it possible to form the plating base layer relatively easily.
  • the conductivity of the oxide constituting the heat insulating layer is not particularly limited, but usually the conductivity at 25 ° C. may be 40 S / m or more.
  • the content of the metal oxide in the heat insulating layer is preferably as high as possible from the viewpoint of the heat insulating property and adhesion, but usually 90% by weight or more is preferable in the heat insulating layer, and particularly 98% by weight or more. More preferred.
  • the thickness of the heat insulating layer may be appropriately set according to the type of molding material to be used, desired heat insulating properties, etc., but can generally be set within a range of 15 ⁇ m or more. In particular, it is preferably 15 to 1000 ⁇ m, more preferably 30 to 150 ⁇ m. By setting the thickness of the heat insulating layer within the above range, it is possible to more effectively trace the base mold shape (base material surface) with a uniform film thickness.
  • the heat-insulating layer of the present invention comprises: 1) the surface of a metal mold base material or 2) the surface of the metal layer previously formed on the surface of the mold base material containing an aqueous solution or water dispersion (hereinafter “ What is also produced by reacting with a "treatment solution”) (wet reaction, particularly hydrothermal synthesis reaction) can be suitably used.
  • a treatment solution aqueous solution or water dispersion
  • wet reaction particularly hydrothermal synthesis reaction
  • the reaction with the treatment liquid can also be carried out under conditions such as a known wet reaction (hydrothermal synthesis reaction). Preferably, 2. According to the method described in 1.
  • the heat insulating layer in the mold of the present invention may be formed directly on the surface of the metal mold base material, but a metallic layer (heat insulating film base layer) is interposed as the base layer of the heat insulating layer. May be. In this case, it is desirable that the metallic layer be formed between the surface of the metal mold base material and the heat insulating layer in contact with both.
  • the composition of the metallic layer is not particularly limited as long as it is composed of metal, and the metal exemplified in the above metal film can be used.
  • the metallic layer may be composed of a single layer or may be composed of multiple layers.
  • 1) a metal layer composed of a seed layer and a metal plating film, and 2) a metal layer composed of one or more layers of the metal plating film can be adopted as the metal layer.
  • the thin film formation method exemplified in the formation of the metal film can be appropriately employed depending on the configuration of the metal layer and the like.
  • 1) a method including a step of forming a seed layer on the surface of a metal mold base material by sputtering and a step of forming a metal plating film on the seed layer by a plating method, and 2) of a metal mold base material A method including a step of forming a metal plating film on the surface by a plating method can be employed.
  • the thickness of the metallic layer may be appropriately set according to the type of metallic element constituting the metallic layer, the thickness of the heat insulating layer, etc., but it is usually within a range of about 1 to 5 ⁇ m.
  • die of this invention is not restrict
  • resin components especially synthetic resins
  • Other components may also be included in the composition as necessary.
  • heat insulating mold of the present invention can be used in the same manner as known or commercially available molds. Moreover, the molding conditions and the like when molding using a mold can be carried out according to a known method.
  • the mold of the present invention can be used as a part or all of the molding space of the mold.
  • the mold of the present invention can be adopted as at least one of the fixed mold and the movable mold.
  • FIG. 25 shows a schematic diagram of a process example in which the mold of the present invention is used as a movable mold in a mold composed of a fixed mold and a movable mold.
  • a mold composed of a fixed mold 301 and a movable mold 401 is used as the molding apparatus.
  • the resin R is injected and introduced into the space (molding space) between the fixed mold and the movable mold in a molten state, the resin R is cooled while maintaining the pressure as shown in the figure.
  • the movable mold 401 is lowered, the mold is opened, the mold is released, and then a desired molding resin is recovered.
  • the mold of the present invention is adopted as the movable mold 401, and a predetermined shape is given to the molding surface of the mold of the present invention.
  • the heat insulating layer of the mold of the present invention even when the molten resin is injected and introduced into the molding space of the mold, the unevenness imparted to the molding surface without the heat of the molten resin being rapidly taken away by the mold Alternatively, as a result of the molten resin all over the groove, the shape is faithfully transferred to the resin side. Thereby, a molded product in which a fine shape is accurately reproduced can be obtained.
  • die can be suitably manufactured especially with the following method. That is, a method of manufacturing a mold having a heat insulating layer between a metal mold base material and a metal film constituting a molding surface, and as a step of forming the heat insulating layer, 1) a metal mold base material Or 2) a step of generating a metal oxide by reacting the surface of a metallic layer previously formed on the surface of the mold base material with an aqueous solution or aqueous dispersion (treatment liquid) containing a metal component.
  • the method of including can be employ
  • an aqueous solution or a water dispersion containing a metal component can be suitably used.
  • a metal component a component that can form a ferrite crystal may be adopted, and at least one of Fe, Ca, Zn, Mn, Al, Cr, Li, and Mg is particularly desirable.
  • a compound serving as a supply source of a metal component can be used.
  • a metal salt, a metal oxide, a metal hydroxide, or the like can be used.
  • any of water-soluble (water-soluble) or poorly water-soluble metal compounds can be used, but in the present invention, a water-soluble metal compound can be more suitably used.
  • the concentration of the metal component in the treatment liquid can be appropriately set according to the type of metal component to be used, reaction conditions, etc., but it is usually preferably 0.03 to 0.35 g / mL.
  • the reaction can be carried out according to a known wet reaction method, and for example, any of a method of immersing in a processing solution, a method of applying a processing solution by spraying, or the like can be employed.
  • the hydrothermal synthesis reaction condition itself may be a known method, but it is particularly preferable to carry out the following method. That is, as the hydrothermal synthesis reaction, 1) a metal mold base material surface or 2) a metal layer surface previously formed on the mold base material is a treatment liquid in which a metal salt, alkali and water are mixed. It is preferable to employ a method including a step of heat-treating in an environment of a saturated water vapor pressure of 100 to 200 ° C. or higher while in contact with
  • a treatment liquid obtained by mixing a metal salt, an alkali and water it is preferable to use a treatment liquid obtained by mixing a metal salt, an alkali and water.
  • the mixing method is not particularly limited, and the blending order is not limited.
  • an inorganic acid salt and an organic acid salt can be used.
  • the inorganic acid salt for example, sulfate, carbonate, chloride and the like can be used.
  • acetate, an oxalate, etc. can be used as organic acid salt.
  • alkali is not particularly limited, and for example, at least one of sodium hydroxide, potassium hydroxide, ammonia and the like can be used.
  • the treatment liquid may be a metal salt or alkali dissolved in water or a partly dissolved solution. Moreover, the thing (suspension (water dispersion)) disperse
  • the content of the metal salt in the treatment liquid is generally preferably 0.03 to 0.35 g / mL, although it depends on the type of metal salt used.
  • the alkali is generally 0.05 to 0.18 g / mL, although it depends on the type of alkali used.
  • the reaction with the treatment liquid can also be carried out in the presence of a reducing agent.
  • a reducing agent By using a reducing agent, it is possible to form a more excellent heat insulating film by suppressing or preventing the production of trivalent iron ions in the reaction system. Therefore, the reducing agent is not limited as long as it can suppress or prevent the production of trivalent iron ions, and can be appropriately selected from known reducing agents. For example, compounds known as antioxidants such as ascorbic acid and hydroquinones can be suitably used.
  • the treatment liquid is brought into contact with 1) the surface of a metal mold base material or 2) the surface of a metal layer previously formed on the mold base material. That is, the treatment liquid is applied to the region where the heat insulating layer is to be formed.
  • the method of providing is not particularly limited, and can be performed according to a known method such as dipping or coating. As a usage amount of the treatment liquid, it is preferable to give a sufficient amount for forming a predetermined heat insulating layer. Therefore, in this invention, the method of immersing the site
  • the conditions for reacting with the treatment liquid are not particularly limited as long as ferrite can be generated.
  • the temperature and pressure conditions are preferably heat treatment in an environment of a saturated water vapor pressure of 100 to 200 ° C. (particularly 110 to 200 ° C.) or higher.
  • a predetermined heat insulation layer can be suitably formed by heat-treating under such temperature and pressure.
  • Such temperature and pressure conditions can be set using a known device such as an autoclave device (sealed system).
  • reaction time for hydrothermal synthesis reaction can be appropriately adjusted according to the desired thickness of the heat insulating layer. That is, the reaction may be continued until the heat insulating film having the preferred thickness is formed. In order to obtain a heat insulating film having a uniform thickness with a desired thickness, the reaction is usually performed for 2 to 12 hours in the case of hydrothermal synthesis reaction. What is necessary is just to form by the method of repeating reaction within the range several times.
  • an iron-based metal as the metal base material or the metallic layer.
  • a ferrite layer as a heat insulating layer can be suitably formed.
  • ferrite can be generated from iron through the following steps 1) to 2). 1) Fe 2+ + OH ⁇ ⁇ Fe (OH) 2 , 2) Fe (OH) 2 ⁇ Fe 3 O 4
  • hydrothermal synthesis reaction or normal wet reaction
  • a process of forming a heat insulation film on the metal mold base material by a hydrothermal synthesis reaction (wet reaction), sputtering on the surface of the heat insulation film A method including a step of forming a seed layer by a method and a step of forming a metal film layer by contact with the seed layer by a plating method.
  • a method comprising a step of forming a base adhesion film of a metal film layer by contact with an upper surface of the film by an electroplating method or a sputtering method, and a step of forming a metal film layer by a plating method in contact
  • Example 1 In FIG. 26, sectional drawing of the layer structure of the heat insulation metal mold
  • the heat insulating mold 1001 is a mold used for molding a resin part having a precise finely processed shape. This uses pure copper having high thermal conductivity as the material of the mold base material, and has the following layer structure. That is, an iron sulfate plating bath is formed on the surface of a mold base material 1002 having a height of 15.0 mm and a diameter of 20.0 mm from a bottom surface having a collar portion (diameter: 25.0 mm) having a height of 2.5 mm.
  • the heat insulating film base layer 1003 made of an iron film having a film thickness of 3 ⁇ m is disposed, and a heat insulating film 1004 made of iron ferrite (that is, spinel iron oxide) having a thickness of 50 ⁇ m is further formed thereon, and a palladium catalyst is formed thereon.
  • a seed layer 1005 made of a fine particle film is disposed, and a metal film layer 1008 is formed thereon.
  • the metal film layer 1008 is made of a plating base film 1006 (thickness 1 ⁇ m) made of nickel and a microfabricated metal film 1007 (average thickness 6 ⁇ m) made of an amorphous nickel-phosphorus alloy film formed thereon. It is configured.
  • On the molding surface side of the microfabricated metal film 1007 is a precision machined surface 1007a in which a micropattern for press molding of a molded part having a maximum depth of 3 ⁇ m is formed by machining.
  • an oxide material that is a metal oxide (spinel type iron oxide) with low thermal conductivity and has pores as a heat insulating layer it is possible to perform good resin molding with a fine pattern. Become. In other words, as seen in the prior art, the heat of the hot molten resin that is molded on the molding surface of the metal mold escapes through the mold substrate, so that the resin is more than necessary during molding. It is possible to effectively avoid a resin molding defect caused by a temperature drop.
  • FIG. 27 the example of a manufacturing process of the heat insulation metal mold
  • a heat insulating film base layer 1003 made of an iron film having a thickness of 3 ⁇ m was formed on the surface of the mold base 1002 on the molding surface side using an iron sulfate plating bath (FIG. 27 (1)).
  • a heat insulating film 1004 made of spinel iron oxide having a thickness of 50 ⁇ m was formed on this surface (FIG. 27 (2)).
  • the heat insulating film 1004 was formed as follows.
  • an aqueous solution in which 41.7 g of ferrous sulfate (FeSO 4 ⁇ 7H 2 O) was dissolved in 60 ml of water produced by distillation in nitrogen gas was mixed with 60 ml of a 21.6 g aqueous solution of sodium hydroxide (NaOH).
  • NaOH sodium hydroxide
  • the suspension was placed in a stainless steel autoclave reaction vessel having an internal volume of 200 ml, and the mold base material on which the heat insulating base layer 1003 was formed was immersed therein and held using a jig.
  • the mold base material 1002 was previously masked with a sealing tape made of ethylene tetrafluoride except for the molding surface on which the heat insulating base layer 1003 was formed.
  • the above operation was performed in a nitrogen gas atmosphere.
  • the autoclave reaction vessel was heated from the outside to react at 150 ° C. for 10 hours. After the reaction, the mold base material was taken out together with the jig, and washed sufficiently with water in order to separate from the powder compound of the reaction residue produced at the same time.
  • the autoclave reaction vessel was also washed with water in order to remove the reaction residue produced in the same manner, and again the same amount of suspension was prepared as above, and the mold base material was attached together with the jig. For 10 hours to form a heat insulating film 1004 having a thickness of 50 ⁇ m.
  • a seed layer 1005 was formed (FIG. 27 (3)).
  • a plating base film 1006 made of a nickel film having a thickness of 1 ⁇ m was coated by an electroless nickel plating method.
  • a metal film layer 1008 is formed by forming a microfabricated metal film 1007 made of a nickel phosphorus alloy plating film for precision processing having a thickness of 6 ⁇ m by an electroless nickel plating method, and heat-treated at 200 ° C. for 3 hours (FIG. 27 (4)). Thereafter, a precision machining surface 1007a was formed using a precision cutting machine to obtain a heat insulating mold 1001 for a fine machining die (FIG. 27 (5)).
  • the example of the method by a plating method was described in the present Example as a formation method of the heat insulation film
  • membrane is described.
  • a metal film made of a metal element that forms the heat insulating film may be provided immediately below.
  • the method for forming the metal film is not limited to the plating method described in this embodiment.
  • this iron film may be formed directly on the surface of the mold base material by a sputtering method.
  • the heat insulating film of the present invention is different from the mold using the conventional zirconia sprayed film as the heat insulating film, and does not require post-processing such as precision grinding, and the molding surface of the metal mold.
  • the desired thickness can be formed directly on the side.
  • a rectangular substrate (size: 50 mm length, 20 mm width) of the same material (pure copper) as the mold base material 1002 is separately provided. A thickness of 2.0 mm) was prepared, and a heat insulating film was formed using this substrate. The obtained sample was used as the heat insulation film A, and the material was evaluated in detail. A method for producing the heat insulating film A will be described below. First, a similar heat insulating film foundation layer was formed on the surface of the substrate in the same manner as in the step of manufacturing the heat insulating mold 1001 (FIG. 27).
  • the film thus formed on the substrate was a black film.
  • the X-ray diffraction pattern is shown in FIG. Further, FIG. 41 shows a scanning electron microscope image of the surface after the heat insulating film A is formed.
  • the film structure has a three-dimensional network structure with sharp corners and continuous crystal grains of different sizes. Furthermore, if you observe closely, it is a film in which the crystal grains that appear to be twin crystals are continuously grown in three dimensions, and it is a porous film that has numerous pores inside the film. I understand that.
  • Ferrite ceramics a type of iron-based oxide, is a material that is easy to machine into complex shapes, such as cutting, and is a material that is finely processed and used as the core material of magnetic heads. is there.
  • the heat insulating film of the present invention is an iron ferrite material having the same spinel crystal structure as the above ferrite ceramic material, and is a material that is relatively easy to machine. Therefore, for the heat insulating film A formed in this example, when the surface is polished gradually from the surface, when the film sample is observed with a scanning electron microscope, not only the pores opened on the film surface in the heat insulating film, It was found that there were many closed pores. Therefore, after forming the heat insulation film A, the porosity is determined by a simple method of forming a smooth surface by surface polishing and measuring the existence ratio of pores to the entire smooth surface including pores formed by polishing. It was measured.
  • a sample having a smooth polished surface necessary for measuring the porosity was prepared as follows. Using the 1000th polishing sheet, the surface of the heat insulating film A was roughly polished from the film surface to a depth of about 30 to 50 ⁇ m. Next, this rough polished surface was hand-polished using a No. 4000 wrapping film sheet made of an aluminum oxide fine powder abrasive to prepare a sample having a polished surface for measuring porosity.
  • the smooth polished surface is observed with a scanning electron microscope (SEM), and the degree of surface roughness looks average over the entire sample.
  • SEM scanning electron microscope
  • the length is 150 ⁇ m and the width is 150 ⁇ m.
  • the unevenness shape in the depth direction of the square region was measured.
  • the magnification of the laser microscope at this time was 2000 times.
  • an image of the cross section of the straight portion of the upper lateral side (length: 150 ⁇ m) of this square region is cut out, and the uneven profile is measured with a laser microscope in the obtained uneven profile depth profile (FIG. 40B).
  • the ratio of the sum of the horizontal distances of the concave portions having a depth of 5 ⁇ m from the surface to the total distance of 150 ⁇ m (FIG. 40C) is obtained, and the percentage is the ratio of the pores existing on the measurement line, that is, the porosity. Pa 1 was set.
  • FIG. 29 shows a scanning electron microscope image of the polished surface of the heat insulation film A whose porosity was measured in this way.
  • the Vickers hardness of the heat insulation film A was measured using a Vickers hardness meter.
  • the Vickers hardness meter used was equipped with a regular quadrangular pyramid diamond indenter, and the hardness was measured under a test load of 50 g.
  • membrane sample used for the measurement of a porosity was measured so that it might be hard to be influenced by the hardness of the base material which is the foundation
  • Each of the cross sections of the heat insulating film was polished by the same method as in the porosity measurement, and the smooth cross section was used as the surface for Vickers measurement.
  • FIG. 1 A polished cross section of the heat insulation film A is shown in FIG.
  • the heat insulating film A synthesized under exactly the same reaction conditions as the heat insulating film 1004 had a Vickers hardness of a maximum value Hv407, a minimum value Hv190, and an average value Hv257.
  • a heat insulation film sample B having a porosity different from that of the heat insulation film sample A was tried by selecting a synthesis condition different from the hydrothermal synthesis condition of the heat insulation film sample A having a porosity of 55%.
  • Formation of the heat insulation film B was performed as follows. That is, an aqueous solution obtained by dissolving 10.4 g of ferrous sulfate (FeSO 4 .7H 2 O) in 60 ml of water produced by distillation in nitrogen gas, and an aqueous solution similar to the alkaline aqueous solution used for the synthesis of the heat insulating film A A suspension was prepared by mixing 60 ml of an aqueous solution of 21.6 g of sodium hydroxide (NaOH).
  • the same reaction vessel as the synthesis of the heat insulating film A was used, and a sample base material in which a heat insulating base layer (iron film similar to the heat insulating base layer 1003 of the heat insulating mold 1001) was formed was prepared. It was immersed and held using a jig. The above operation was performed in a nitrogen gas atmosphere. This autoclave reaction vessel was heated from the outside to react at 140 ° C. for 12 hours. After the reaction, the sample substrate was taken out together with the jig, and washed sufficiently with water in order to separate from the powder compound of the reaction residue at the same time.
  • a heat insulating base layer iron film similar to the heat insulating base layer 1003 of the heat insulating mold 1001
  • the heat insulating film B thus obtained was also a black film.
  • membrane it carried out similarly to the heat insulation film
  • the surface of the heat insulating film B after the film formation is observed in a scanning electron microscope (SEM), as in the case of the heat insulating film A, the crystal grains that look like twin crystals with sharp corners are continuously three-dimensionally.
  • the film was a grown film, and the film was a porous film having innumerable pores inside the film.
  • FIG. 31 shows a scanning electron microscope image of the polished surface of the heat insulation film B whose porosity was measured.
  • FIG. 32 shows a schematic cross-sectional configuration diagram of a measurement sample 1011A in which the heat insulation film A is arranged.
  • the measurement sample 1011B is the same as the configuration shown in FIG. 32 except that the material of the heat insulating film is the heat insulating film B.
  • the measurement sample 1011A was produced as follows.
  • a round bar made of the same material as the mold base material 1002 used in the heat insulating mold 1001 of the present embodiment having a diameter of 10.0 mm and a length of 44.0 mm is prepared, and a diameter of 3.5 mm is provided at the center of one end face thereof.
  • a thermocouple mounting hole 1012a having a depth of 22.0 mm was formed, and a metal rod 1012 was produced.
  • a manufacturing method similar to the method shown in FIG. 27 is made of an iron film having a thickness of 3 ⁇ m from the bottom of the end face at a position opposite to the end face with the thermocouple mounting hole 1012 a to a position of 30.0 mm.
  • a heat insulating film base layer 1013 was formed, and a heat insulating film 1014 made of the heat insulating film A of the present invention having a thickness of 50 ⁇ m was formed thereon. Subsequently, resin masking is performed from the end face with the thermoelectric mounting hole 1012a thereon, and a seed layer 1015 made of an ultrathin palladium catalyst fine particle film is formed from the bottom of the end face to a position of 23.0 mm by a sputtering method.
  • a plating base film 1016 (thickness 1 ⁇ m) made of nickel is formed thereon by electroless nickel plating, and further, a plating metal made of an amorphous nickel phosphorus alloy film 6 ⁇ m thick by electroless nickel plating thereon A film 1017 was formed, and a metal film layer 1018 composed of a plating base film 1016 and a plating metal film 1017 was formed.
  • Measurement sample 1011B is a measurement sample produced by forming a heat insulating film made of heat insulating film B in place of heat insulating film 1014 made of heat insulating film A in measurement sample 1011A shown in FIG.
  • a comparative sample 1211 having no thermal insulation film was also produced.
  • the structure of this comparative sample is shown in FIG.
  • a base material 1212 processed in the same shape and with the same material as that of the base material 1012 was prepared. Resin masking was applied to the end face side having the thermocouple mounting hole 1212a, leaving a position of 23.0 mm from the bottom of the end face. Thereafter, a 1 ⁇ m-thick plating base film 1216 made of a nickel plating film is formed by a wood strike bath, and an amorphous nickel phosphorus alloy film having a thickness of 6 ⁇ m is formed thereon by electroless nickel plating in the same manner as described above. A plated metal film 1217 was formed, and a metal film layer 1218 was formed. In this way, a measurement sample 1211 was produced.
  • the three types of measurement samples 1011A, 1011B, and 1211 thus produced were simultaneously evaluated for heat insulation properties as follows.
  • FIG. 34 shows a schematic cross-sectional view of the thermal insulation evaluation device 21 used in this example.
  • This apparatus is made of a rigid foamed polystyrene resin holding a constant temperature water tank 22 for high temperature water, a constant temperature water tank 23 for cold water, and three measurement samples 1011A, 1011B, and 1211, both of which are made of a transparent glass beaker.
  • the heat insulating plate 1024 has a size (square, size 20 cm) that can cover the top surface of the thermostatic water tank and can be used as a lid, and is 5 mm thick.
  • An electric heater 25 is disposed below the constant temperature water tank 22 for high-temperature water, and has a structure that can be heated.
  • a constant temperature water tank 23 for cold water is placed on a table 26 so as to have the same height.
  • the heat insulating plate 1024 three through-holes with a diameter of 10.0 mm are formed at equal intervals, and the measurement sample is such that 20 mm from the end surface of the measurement sample exits from the heat insulating plate 1024 at the portion where each metal film layer is formed. 1011A, 1011B, and 1211 are arranged.
  • Each measurement sample has thermocouples 18, 118, 218 attached to thermocouple attachment holes provided on the other end face, and is connected to each temperature indicator 19, 119, 219 for each measurement. It is the structure which can display the temperature of the base material of the metal round bar which comprises a sample.
  • the upper part connected to the thermocouple is completely hidden from the upper side of the heat insulating plate 24. Further, they were covered with heat insulating covers 27, 28, 29 made of styrene foam resin having exactly the same shape.
  • High temperature water and cold water were used in the two constant temperature water tanks 22 and 23 so that the 15 mm portions were immersed from the lower end surfaces of the three types of measurement samples 1011A, 1011B, and 1211 attached to the heat insulating plate 24, respectively. .
  • the constant-temperature water tank 22 for high-temperature water was adjusted using an electric heater 25 so that the water temperature was constant, and the constant-temperature water tank 23 for cold water was used while maintaining a constant water temperature by replacing the cold water.
  • the heat insulating property evaluation of the heat insulating film of the present invention is performed using three measurement samples 1011A, 1011B, and 1211 that are kept at room temperature in high-temperature water maintained at 95 ° C. in the constant temperature water tank 22 of the heat insulating evaluation device 21.
  • the heat insulation effect at the time of temperature rise was investigated by immersing at the same time with attaching to the heat insulation board 1024, and measuring the speed of the temperature rise. Subsequently, the measurement samples 1011A, 1011B, and 1211 that have risen in temperature are directly attached to the heat insulating plate 24 while being immersed in water kept at 32 ° C. in the constant temperature water bath 23, and the rate of temperature drop is measured by measuring the rate of temperature drop.
  • the heat insulation effect was investigated.
  • the thermal insulation film of the present invention is provided in comparison with the measurement sample 1211 having no thermal insulation film with respect to the time change of the temperature rise when immersed in the constant temperature water bath 22 kept at 95 ° C. from room temperature.
  • the measurement results of the measurement sample 1011A (porosity 55%) and 1011B (porosity 40%) the time change of the temperature rise and the time change of the temperature difference between the two measurement samples are shown.
  • FIG. 36 shows the measurement result of the time change of the temperature drop when the measurement samples 1011A, 1011B, and 1211 once heated are immersed in a constant temperature water bath maintained at 32 ° C. at the same time.
  • the heat insulating film of the present invention has an effect of making it difficult to transfer heat to the base material against an external temperature change. Further, it can be seen that the heat insulation effect becomes higher as the measurement sample is provided with a heat insulating film having a higher porosity.
  • Example 2 In FIG. 1, sectional drawing which shows the laminated structure of the heat insulation metal mold
  • the heat insulating mold 1 is a stainless steel mold used for molding a resin part having a precise finely processed shape, and has the following layer structure. That is, a 3 ⁇ m thick iron is formed on the surface of a mold base 2 having a height of 15.0 mm and a diameter of 20.0 mm from a bottom surface having a brim shape (diameter 25.0 mm) having a height of 2.5 mm.
  • a heat insulating film base layer 3 made of a film is formed, a heat insulating film 4 made of iron ferrite (that is, spinel iron oxide) having a thickness of 150 ⁇ m is formed thereon, and a seed layer 5 made of a catalyst fine particle film of palladium is formed thereon.
  • the metal film layer 8 is formed thereon.
  • the metal film layer 8 is composed of a plating base film 6 (thickness 2 ⁇ m) made of nickel and a microfabricated metal film 7 (average thickness 60 ⁇ m) made of an amorphous nickel-phosphorus alloy film formed thereon. Has been.
  • the molding surface side of the microfabricated metal film 7 is a precision machined surface 7a on which a micropattern for press molding of a molded part is formed by machining.
  • Example 2 Production of the heat insulating mold of this example was performed in the same manner as in Example 1. An example of the manufacturing process is shown in FIG. A heat insulating film base layer 3 made of an iron film having a thickness of 3 ⁇ m was formed on the surface of the mold base 2 on the molding surface side using an iron sulfate plating bath. Subsequently, a heat insulating film 4 made of spinel iron oxide having a thickness of 150 ⁇ m was formed on the surface. The heat insulating film 4 was formed as follows.
  • aqueous solution in which 41.7 g of ferrous sulfate (FeSO 4 ⁇ 7H 2 O) is dissolved in 60 ml of water produced by distillation in nitrogen gas is mixed with 60 ml of a 21.6 g sodium hydroxide (NaOH) aqueous solution.
  • a suspension was prepared as a treatment liquid.
  • the suspension was placed in a stainless steel autoclave reaction vessel having an internal volume of 200 ml, and the mold base material on which the heat insulating base layer 3 was formed was immersed therein and held using a jig. This mold base material was masked in advance with a tetrafluoroethylene sealing tape except for the molding surface on which the heat insulating base layer 3 was formed.
  • the above operation was performed in a nitrogen gas atmosphere.
  • the autoclave reaction vessel was heated from the outside to react at 150 ° C. for 10 hours. After the reaction, the mold base material was taken out together with the jig and washed sufficiently with water in order to separate from the powder compound produced at the same time. Similarly, the autoclave reaction vessel was washed with water to remove the generated powder, and again the same amount of suspension was prepared as above, and the mold base material was attached together with the jig. For 10 hours. By repeating this operation six times in total, a heat insulating film 4 made of spinel iron oxide having a film thickness of 150 ⁇ m was formed.
  • the mold on which the laminated film is formed is washed with water and sufficiently dried, and then a direct-current sputtering apparatus equipped with a palladium target is used to form a palladium fine particle film on the surface of the heat insulating film 4.
  • a seed layer 5 was formed.
  • a plating base film 6 made of a nickel film having a thickness of 2 ⁇ m was coated by an electroless nickel plating method.
  • a metal film layer 8 was formed by forming a microfabricated metal film 7 made of a nickel phosphorus alloy plating film for precision processing having a thickness of 150 ⁇ m by an electroless nickel plating method, and then heat-treated at 200 ° C. for 3 hours.
  • the heat-insulating mold 1 for a microfabrication mold was obtained by forming the precision-machined surface 7a using a precision cutting machine.
  • a square plate (size: 18.0 mm square with a thickness of 2 with the same material as the mold base material 2) is separately provided. 0.0 mm), and in the step of manufacturing the heat insulating mold 1 described above, a similar heat insulating film base layer was formed. Thereafter, in the step of forming the heat insulating film 4 of the heat insulating mold 1, the square plate sample is put in the same autoclave reaction vessel together with the heat insulating mold 1, and simultaneously with the heat insulating film 4, A heat insulating film was formed. For the film formed on the square plate, the same material evaluation as in Example 1 was performed.
  • thermocouple mounting hole 12a having a depth of 5 mm and a depth of 22.0 mm was formed.
  • a concave and convex groove having a pitch of 125 ⁇ m and a depth of 15 ⁇ m was formed on the entire side surface of the round bar to prepare a metal round bar base 12.
  • a metal round bar base 12 Using this base material 12, an iron film having a thickness from the bottom of the end surface at a position opposite to the end surface with the thermocouple mounting hole 12 a to a position of 30.0 mm by the same manufacturing method as the heat insulating mold of this example
  • membrane underlayer 13 which consists of was formed, and the heat insulation film
  • the resin masking is performed from the end face with the thermocouple mounting hole 12a thereon, and the seed layer 15 made of an ultrathin palladium catalyst fine particle film is formed by a sputtering method from the bottom of the end face to a position of 23.0 mm,
  • a plating base film 16 (thickness 2 ⁇ m) made of nickel is formed by electroless nickel plating, and further on the amorphous nickel phosphorus alloy film having a thickness of 18 ⁇ m by electroless nickel plating.
  • a plated metal film 17 was formed, and a metal film layer 18 composed of the plating base film 16 and the plated metal film 17 was formed.
  • One comparative sample is a measurement sample 111 provided with a conventional heat insulating film using a zirconia sprayed film as a heat insulating film, and its configuration is shown in FIG.
  • the measurement sample 111 was produced as follows. Prepare the base material 112 processed into the same shape and the same material as the base material 12 of the measurement sample 11 above, from the bottom of the end surface at the position opposite to the end surface with the thermocouple mounting hole 112a, to a position of 30.0 mm, High temperature zirconia fine particles were uniformly sprayed so as to have an average thickness of about 250 ⁇ m by a thermal spraying method to form a zirconia sprayed film.
  • the thermally sprayed film was precisely ground to reduce the thickness to 150 ⁇ m, and a heat insulating film 114 made of a zirconia sprayed film was formed. Then, resin masking was performed from the end surface having the thermoelectric mounting hole 112a on the top, leaving a position of 23.0 mm from the bottom of the end surface.
  • a palladium catalyst seed layer 115 was formed by a pretreatment step of degreasing and pickling, an immersion treatment in a hydrochloric acid acidic stannous chloride solution, and an immersion treatment in a palladium chloride solution.
  • a plating base film 116 (thickness 2 ⁇ m) made of nickel is formed thereon, and a plating metal film 117 made of an amorphous nickel phosphorus alloy film having a thickness of 18 ⁇ m is formed thereon by electroless nickel plating, A metal film layer 118 was formed. In this way, a measurement sample 111 was produced.
  • the other comparative sample is a measurement sample 211 having no heat insulation film.
  • the configuration is shown in FIG.
  • a 2 ⁇ m-thick plating base film 216 made of a nickel plating film is formed in a wood strike bath, and a plating made of an amorphous nickel phosphorus alloy film having a thickness of 18 ⁇ m is formed thereon by electroless nickel plating in the same manner as described above.
  • a metal film 217 was formed, and a metal film layer 218 was formed. In this way, a measurement sample 211 was produced.
  • the three types of measurement samples 11, 111 and 211 prepared as described above were simultaneously evaluated for heat insulation properties as follows.
  • Evaluation of heat insulation is performed by three measurement samples 11, 111, and 211 which are kept at a constant temperature by being kept at room temperature in high-temperature water kept at 90 ° C. in a constant temperature water tank 22 of the heat insulation evaluation device 21 shown in FIG. was attached to the heat insulating plate 24 at the same time, and the heat insulation effect at the time of temperature rise was examined by measuring the rate of temperature rise. Subsequently, the measurement samples 11, 111, and 211 that have risen in temperature are attached to the heat insulating plate 24 as they are, and are simultaneously immersed in cold water kept at 20 ° C. in the constant temperature water bath 23, and the rate of temperature drop is measured. The heat insulation effect of was investigated.
  • the thermal insulation film of the present invention is provided in comparison with the measurement sample 211 that does not have the thermal insulation film regarding the time change of the temperature rise when immersed in the constant temperature water tank 22 that is kept at 90 ° C. from room temperature.
  • the time change of the temperature rise and the time change of the temperature difference between the two measurement samples are shown.
  • maintained the measurement samples 11 and 211 once temperature-rise at 20 degreeC simultaneously is shown.
  • the heat insulating film of the present invention has a clear effect of making it difficult to transfer heat to the base material against an external temperature change. Moreover, it turns out that the heat insulation effect is substantially equivalent to the heat insulation film which consists of a conventional zirconia sprayed film.
  • the heat insulating mold 31 is a mold used for resin molding of an optical element having a precise finely processed surface, and has the following layer structure. That is, a steel with a height of 15.0 mm having a cylindrical shape with a diameter of 10.0 mm processed into an approximate molded shape of the optical element and a collar-shaped portion with a diameter of 14.0 mm and a height of 2.0 mm at the bottom.
  • a heat insulating layer 34 made of spinel iron oxide and having a thickness of 105 ⁇ m is disposed on the molding surface side of the mold base material 32 made of a material.
  • An adhesion layer 35 made of an iron film having a thickness of 3 ⁇ m is disposed on the surface, and a metal film layer 38 is disposed on the upper surface.
  • the metal film layer 38 is composed of a nickel plating base film 36 having a thickness of 2 ⁇ m, and a microfabricated metal film 37 made of an amorphous nickel phosphorus alloy film having a thickness of 100 ⁇ m thereon.
  • the surface of the microfabricated metal film 37 is a molding transfer surface at the time of resin molding, and is a precision machined surface 37a that is micromachined to the shape of the molding object.
  • FIG. 13 shows the steps in the method for manufacturing a heat insulating mold of this example.
  • a heat insulating film 34 made of spinel-type iron oxide having a thickness of 105 ⁇ m is formed on the molding surface of a die base material 32 obtained by machining a rod made of steel containing iron as a main component, and the same autoclave reaction as that of the second embodiment.
  • the same hydrothermal reaction was repeated four times to form (FIG. 13 (1)).
  • die base material masked the surface other than the molding surface of the metal mold
  • adherence layer 35 which consists of an iron plating film
  • a plating base film 36 made of a nickel film having a thickness of 2 ⁇ m was coated by an electroless nickel plating method.
  • a microfabricated metal film 37 made of a nickel phosphorus alloy plating film for precision machining having a thickness of 150 ⁇ m is formed by electroless nickel plating to produce a metal film layer 38, and heat-treated at 200 ° C. for 3 hours (FIG. 13). (3)).
  • the surface of the microfabricated metal film 37 is machined using a precision cutting machine to form a precision machined surface 38 in the shape of a molding, and a heat insulating mold used for resin molding of optical elements. 31 was produced (FIG. 13 (4)).
  • membrane of a present Example is a metal oxide which has electroconductivity, in the electroplating method to the fine ceramic heat insulation film
  • a measurement sample 41 for thermal insulation evaluation comprising the same material and the same configuration including the thermal insulation film of the present invention was produced.
  • a schematic cross-sectional view thereof is shown in FIG.
  • the measurement sample 41 was produced as follows. First, a round bar made of the same material as the mold base material 32 of this embodiment having a diameter of 5.5 mm and a length of 52.0 mm is prepared, and from the one end, a thermocouple for measuring the temperature of the base material is embedded. A thermocouple mounting through hole 42a having a diameter of 2.0 mm was formed on the cylindrical side surface at a position of 0 mm at right angles to the axial direction, and the base material 42 was produced.
  • this base material 42 Thereafter, from one end of this base material 42, it is masked in advance with a tetrafluoroethylene seal tape, and in the same manner as the method of forming the heat insulating film 34 in FIG. 13, the other end is 22.0 mm from the bottom of the end face.
  • a heat insulating film 44 having a thickness of 105 ⁇ m was formed.
  • the portion up to a position of 20.0 mm from the bottom of the end face is left, the remaining portion is masked with a resin sealing material, and the adhesion layer 45 made of an iron plating film is formed in the same manner as the formation method of the adhesion layer 35 in the heat insulating mold 31.
  • a measurement sample 41 was produced by coating the film.
  • a measurement sample 241 having no heat insulation film was produced as follows. A schematic cross-sectional view thereof is shown in FIG. A base material 242 processed in the same shape and with the same material as the base material 42 was prepared, and resin masking was applied to the end face side where the thermocouple mounting hole 242a is provided, leaving a position of 20.0 mm from the bottom of the end face. .
  • a 2 ⁇ m-thickness plating base film 246 made of a nickel plating film is formed by electroless nickel plating, and an amorphous nickel phosphorus alloy film having a thickness of 28 ⁇ m is formed thereon by electroless nickel plating in the same manner as described above.
  • a plated metal film 247 was formed. In this way, a measurement sample 241 was produced.
  • the measurement samples 41 and 241 produced in this manner were the same as those used in Example 1, except that the heat insulating plate 24 was changed to provide a through hole having a diameter of 6.0 mm so as to hold the measurement samples 41 and 241.
  • the heat insulation property was evaluated in the same manner as in Example 1.
  • thermal insulation evaluation was performed so that the 15-mm part from the lower end surface of the measurement samples 41 and 241 attached to the heat insulation film 24 was immersed in the high temperature water and cold water which were stored in the thermostat.
  • FIG. 16 shows that the thermal insulation film of the present invention is provided in comparison with the measurement sample 241 that does not have the thermal insulation film with respect to the time change of the temperature rise when immersed in a constant temperature water bath maintained at 95 ° C. from room temperature.
  • the measurement result of the measurement sample 41 is shown.
  • FIG. 17 shows the measurement results of the time change of the temperature drop when the measurement samples 41 and 241 that have once increased in temperature are immersed in a constant temperature water bath that is maintained at different temperatures and at 18 ° C. at the same time.
  • the heat insulating film of the present invention clearly shows the effect of making it difficult to transfer heat to the substrate with respect to an external temperature change. I understand.
  • a measurement sample 341 having a heat insulation film thickness of 15 ⁇ m and a measurement sample 441 having a heat insulation film thickness of 30 ⁇ m are prepared, and three samples of the measurement sample 241 having no heat insulation film are prepared. Evaluation was carried out in the same manner as in the measurement of heat insulation. However, the heat insulation was evaluated so that the 19 mm portions from the lower end faces of the three measurement samples 241, 341, and 441 were immersed in high-temperature water and cold water stored in a thermostatic bath.
  • the thermal insulation film of the present invention is provided in comparison with the measurement sample 241 that does not have the thermal insulation film with respect to the time change of the temperature rise when immersed in a constant temperature water bath maintained at 95 ° C. from room temperature.
  • the measurement results of the measurement samples 341 and 441 are shown.
  • FIG. 19 shows the measurement results of the time change of the temperature drop when the measurement samples 241, 341 and 441 whose temperature has once increased are immersed in a constant temperature water bath maintained at 27 ° C. at different temperatures at the same time.
  • Example 4 As shown in Example 1, by selecting the reaction conditions for hydrothermal synthesis, it is possible to form heat insulating films having various porosities that greatly affect the heat insulating performance.
  • three types of heat insulating films C, D, and E having different porosities were produced by variously changing hydrothermal synthesis conditions.
  • hydrothermal synthesis all raw material solutions were prepared using water distilled in nitrogen gas.
  • the heat insulating film C was formed as follows.
  • a suspension was prepared by mixing an aqueous solution in which 38.3 g of ferrous sulfate (FeSO 4 .7H 2 O) was dissolved in 60 ml of water and 60 ml of an aqueous solution of 29.7 g of sodium hydroxide (NaOH).
  • the suspension is put into an autoclave reaction vessel having the same shape as that used in Example 1, the substrate is held and immersed using a jig, the reaction vessel is sealed, and heated at 100 ° C. Held. After 45 hours, the pressure inside the reaction vessel had risen to 0.20 MPa.
  • membrane C formed in this way it is the same as the material evaluation of the heat insulation film
  • membrane A of Example 1, and a chemical composition is measured using a fluorescent X-ray apparatus, an X-ray diffractometer, a laser microscope, a Vickers hardness meter, etc. The crystal structure, porosity and Vickers hardness were examined respectively. As a result, it was confirmed that the heat insulating film C was spinel type iron oxide having a lattice constant a 0 8.40 ⁇ . The porosity was 5%, and it was found that the Vickers hardness was the maximum value Hv314, the minimum value Hv230, and the average value HV278.
  • membrane D is as follows. First, an aqueous solution in which 41.7 g of ferrous sulfate (FeSO 4 ⁇ 7H 2 O) is dissolved in 60 ml of water produced by distillation in nitrogen gas, and 60 ml of an aqueous solution of 26.0 g of sodium hydroxide (NaOH) are mixed. To prepare a suspension. This suspension was placed in a reaction vessel having the same shape as that used for forming the heat insulation film C, and reacted at 110 ° C. for 40 hours in the same manner as in the case of the heat insulation film C.
  • FeSO 4 ⁇ 7H 2 O ferrous sulfate
  • NaOH sodium hydroxide
  • the film-formed substrate is taken out, washed thoroughly with water, the substrate is immersed in a new raw material suspension in a reaction vessel, the vessel is sealed, and the same reaction is performed at 110 ° C. for 40 hours. It was. By repeating this operation four times in total, a heat insulating film D having a film thickness of 150 ⁇ m was formed.
  • the minimum value was Hv303 and the average value was Hv448.
  • membrane E is as follows. First, an aqueous solution in which 41.7 g of ferrous sulfate (FeSO 4 ⁇ 7H 2 O) is dissolved in 60 ml of water produced by distillation in nitrogen gas is mixed with 60 ml of a 21.6 g sodium hydroxide (NaOH) aqueous solution. To prepare a suspension. This suspension was put in a reaction vessel having the same shape as that used for forming the heat insulation film C, and reacted at 145 ° C. for 90 minutes in the same manner as in the case of the heat insulation film C.
  • FeSO 4 ⁇ 7H 2 O ferrous sulfate
  • NaOH sodium hydroxide
  • the film-formed substrate is taken out, washed thoroughly with water, again immersed in a new raw material suspension in the reaction vessel, the vessel is sealed, and reacted at 145 ° C. for 90 minutes. It was. By repeating this operation 14 times in total, a heat insulating film E having a film thickness of 150 ⁇ m was formed.
  • the heat insulating film E having a large porosity of 75% cannot measure a Vickers hardness because a smooth polished surface having a size capable of forming an indentation by pressing a Vickers indenter cannot be obtained. could not.
  • FIG. 37 shows scanning microscope images of the polished surfaces of the heat insulating films C, D, and E having different porosities.
  • the surfaces after the formation of the heat insulation films C, D, and E are films in which crystal grains that look like twin crystals with sharp corners are continuously grown in three dimensions.
  • the film is a porous film having innumerable pores inside the film.
  • a zirconia sintered body or a zirconia sprayed film which is a conventional heat-insulating oxide material, has a high Vickers hardness Hv of 1200 and is a difficult-to-work material.
  • the heat insulating film material of the present invention has a low hardness regardless of the size of the porosity, and is a material that can be finely processed, such as precision cutting and precision grinding, relatively easily like conventional ferrite ceramics. I understand.
  • Example 5 Whether or not substituted ferrites of various compositions can be formed into a film shape on a substrate by hydrothermal synthesis reaction by substituting some of the iron ions forming spinel iron oxide Fe 3 O 4 with various metal ions It was investigated. These ferrites have almost no difference in thermal conductivity depending on the type of substitution ions, but other material properties such as thermal expansion coefficient can be changed. The film formation is important.
  • the substitution ferrite film was synthesized as follows.
  • the base substrate used for film formation for the purpose of confirming whether a desired ferrite film can be formed by a hydrothermal reaction similar to the method shown in Example 1 was used for the material evaluation of the heat insulating film of Example 1.
  • a treatment liquid 60 ml of an aqueous solution in which 19.9 g of ferrous chloride (FeCl 2 .4H 2 O) and 7.4 g of calcium chloride (CaCl 2 .2H 2 O) are dissolved in water and 21.6 g of hydroxylated water are used.
  • a suspension was prepared by mixing 60 ml of an aqueous sodium (NaOH) solution. The suspension is put into a stainless steel autoclave reaction vessel having an internal volume of 200 ml similar to that used in Example 1, and the base substrate for evaluation is immersed therein, and a jig is used. Held. After reacting at 150 ° C.
  • the base material was taken out together with the jig, and washed sufficiently with water in order to separate it from the produced powder compound.
  • the autoclave reaction vessel was washed with water in order to remove the generated powder, and again the same amount of suspension was prepared as above, and the mold base material was attached together with the jig, and the same reaction was performed. Repeated times.
  • membrane formed on the base material was a black film
  • Example 42 shows a scanning electron microscope image of the surface of this film after the film formation. Similar to the heat insulation film A shown in Example 1, the crystal grains that appear to be twin crystals with sharp corners are continuously grown in three dimensions, and there are innumerable pores inside the film. It can be seen that the film has a porous structure.
  • FIG. 39 shows a scanning microscope image of the film surface after polishing. As a result, the porosity was 20%.
  • the Vickers hardness had a maximum value of Hv339 and a minimum value of Hv130, and the average value thereof was Hv220.
  • a suspension was prepared by mixing 60 ml of an aqueous sodium (NaOH) solution.
  • the suspension is placed in a stainless steel autoclave reaction vessel having an internal volume of 200 ml used in the synthesis of the calcium ferrite, and the substrate for evaluation is immersed therein and held using a jig. did.
  • the substrate was taken out together with the jig, and washed sufficiently with water to separate from the produced powder compound at the same time.
  • the inside was washed with water to remove the generated powder, the same amount of suspension was prepared again, the mold base material was attached together with the jig, and the same reaction was repeated. Repeated times.
  • SEM scanning electron microscope
  • Example 6 the schematic perspective view of the layer structure of the heat insulation metal mold
  • the heat insulating mold 51 is a mold used for resin molding having a precise finely machined surface, and has a rectangular shape with a minor axis of 6.00 mm and a major axis of 9.00 mm and a height of 20.00 mm. And has the following laminated structure.
  • the mold base material 52 is made of a steel material having the same composition as that of the third embodiment. On the surface of the mold base 52 on the rectangular molding surface side, a concave groove pattern finely processed into a cross-sectional shape with the dimensions shown in FIG. 21 is formed at the center of the minor axis of the molding surface side surface.
  • a heat insulating layer 54 made of spinel iron oxide and having a thickness of 50 ⁇ m is disposed so as to cover the surface of the finely processed surface.
  • An adhesion layer 55 made of an iron film having a thickness of 3 ⁇ m is disposed on the surface.
  • a metal film layer 58 is formed on the surface, and a microfabricated metal film made of nickel plating film 56 having a thickness of 2 ⁇ m and an amorphous nickel phosphorus alloy film having a film thickness of 65 ⁇ m formed thereon. 57.
  • the surface of the microfabricated metal film 57 is a molding transfer surface at the time of resin molding, and is a precision machined surface 57a that is micromachined to the same dimensions as in FIG.
  • the manufacturing method of the heat insulating mold in the present example was performed through the same steps as in Example 3 except that the formation conditions of the heat insulating film 54 were different. That is, a heat insulating film 54 made of spinel iron oxide having a thickness of 50 ⁇ m is formed on a mold base material 52 on which a microfabricated pattern is formed using the same autoclave reaction vessel as the same raw material in the same operation as in Example 1. A 7 hour hydrothermal reaction at 155 ° C. was repeated twice. Further, a finely processed metal film 57 of nickel phosphorus alloy plating alloy having a thickness of 100 ⁇ m was formed on the plating base film 56 covered with the adhesion layer formed in the same manner as in Example 2.
  • this finely machined metal film 57 is machined to the same dimensions as those shown in FIG. 21 using a precision cutting machine to form a precision machined surface 57a, and four sides are precisely ground. It processed and produced the heat insulation metal mold
  • FIG. 21 is a precision cutting machine to form a precision machined surface 57a, and four sides are precisely ground. It processed and produced the heat insulation metal mold
  • the cross section of the laminated film including the heat insulating film could be observed on the ground side.
  • the thickness of the heat insulation film of the present invention was observed using a scanning microscope.
  • the coverage and adhesion of the mold base material 52, the heat insulating film 53, and the heat insulating film 53 and the metal laminated film on the heat insulating film 53 are both good. It was observed that there were no cracks or gaps between the layers. Subsequently, the thickness measurement of the heat insulating film is performed on the processing pattern cross-sectional view of the mold base material shown in FIG.
  • A, A ′, B, B ′, C, C ′, E, E ′, F, F ′ It performed about 10 parts shown by.
  • five points A, B, C, D, and E are five points of the mold base material 52 on one side surface of the short axis side of the rectangular shaped surface of the heat insulating mold 51
  • a ′, B ′, C ′, D ′, and E ′ are five points of the mold base material 52 on the other short-axis side surface.
  • Their positions are the dimensions shown in FIG.
  • the thicknesses of the heat insulating films present immediately above the locations indicated by the above symbols are A: 50 ⁇ m, A ′: 50 ⁇ m, B: 50 ⁇ m, B ′: 50 ⁇ m, C: 51 ⁇ m, C ′: 51 ⁇ m, E: They were 50 ⁇ m, E ′: 50 ⁇ m, F: 50 ⁇ m, and F ′: 50 ⁇ m. From the above results, it can be seen that the formed heat insulating film 54 can be coated with good adhesion in a substantially uniform film state on the concave groove pattern formed in the mold base material 52.
  • the method for producing a heat insulating film of the present invention in order to form a heat insulating film by a chemical reaction called a hydrothermal synthesis reaction, it is performed evenly and slowly with respect to the mold surface in contact with the treatment liquid of the raw material for the hydrothermal synthesis reaction. A film can be grown. For this reason, it is possible to form a heat insulating film with good rounding even on a mold base material molding surface having a complicated shape subjected to deep groove processing or the like. Furthermore, according to the present invention, a thin film thickness is possible, no post-machining is required, and a heat insulating film can be formed efficiently.
  • Example 7 A heat insulating mold made of a non-ferrous metal mold base material was produced.
  • the heat insulation mold 201 is a mold composed of a non-ferrous metal mold base material and a heat insulation film used for molding a resin part having a precise micro-fabrication shape composed of deep grooves. Become. That is, it is made of a titanium alloy that has low thermal conductivity and does not lose its strength even at high temperatures, and has a height from the bottom surface having a brim-shaped portion (diameter 25.0 mm) having a diameter of 20.0 mm ⁇ height of 2.5 mm.
  • a base layer 203a made of a nickel plating film having a thickness of 2 ⁇ m is formed on the surface of a mold base material 202 having a thickness of 10.0 mm, and a heat insulating film base layer 203 made of an iron film having a thickness of 3 ⁇ m is formed thereon.
  • a heat insulating film 204 made of zinc ferrite which is a kind of ferrite material having a thickness of 200 ⁇ m is formed, a seed layer 205 made of a catalyst fine particle film of palladium is disposed thereon, and a metal film layer 208 is formed thereon. Yes.
  • the metal film layer 208 is composed of a plating base film 206 (thickness 2 ⁇ m) made of nickel and a microfabricated metal film 207 (average thickness 78 ⁇ m) made of an amorphous nickel phosphorus alloy film formed thereon. Has been.
  • the molding surface side of the microfabricated metal film 207 is a precision machined surface 207a on which a micropattern for press molding of a molded part is formed by machining.
  • a molding surface subjected to microfabrication of deep and fine grooves can be obtained.
  • a deep fine pattern can be formed even in resin molding using a mold having a mold.
  • the heat of the high temperature resin molded on the molding surface of the mold escapes through the mold base and the resin causes an excessive temperature drop during molding, preventing the resin molding Occurs.
  • the present invention as a result of effectively avoiding such a situation, a fine pattern can be more reliably formed.
  • the above-described heat insulation mold 201 was produced as follows.
  • a base film 203a having a thickness of 2 ⁇ m made of a nickel plating film is formed by a wood strike bath on the surface of the mold base material 202 made by machining a titanium alloy that is a non-ferrous metal, and the surface thereof.
  • a heat insulating film base layer 203 made of an iron film having a thickness of 3 ⁇ m was formed using an iron sulfate plating bath.
  • a heat insulating film 204 made of a zinc ferrite film having a thickness of 200 ⁇ m was formed on the surface as follows.
  • This mold base material was masked in advance with a tetrafluoroethylene sealing tape except for the molding surface on which the heat insulating base layer 203 was formed.
  • the above operation was performed in a nitrogen gas atmosphere.
  • the autoclave reaction vessel was externally heated to react at 180 ° C. for 6 hours. After the reaction, the mold base material was taken out together with the jig and washed sufficiently with water in order to separate from the powder compound produced at the same time. Similarly, the autoclave reaction vessel was washed with water in order to remove the generated powder, and again the same amount of suspension was prepared as above, and the mold base material was attached together with the jig, and similarly 180 ° C. For 6 hours. By repeating this operation eight times in total, a heat insulating film 204 made of a zinc ferrite film having a thickness of 200 ⁇ m was formed.
  • a seed layer 205 was formed.
  • a plating base film 206 made of a nickel film having a thickness of 2 ⁇ m was coated by an electroless nickel plating method.
  • a metal film layer 208 was formed by forming a microfabricated metal film 207 made of a nickel phosphorus alloy plating film for precision processing having a thickness of 100 ⁇ m by an electroless nickel plating method.
  • the metal film layer 208 was heat-treated at 200 ° C. for 3 hours. Then, the precision processing surface 207a was formed using the precision cutting machine, and the heat insulation metal mold
  • a square plate (size 20.0 mm square and thickness 2 made of the same titanium alloy as the mold base material 202) is separately provided.
  • a base film having a thickness of 2 ⁇ m made of the same nickel plating film is formed, and a heat insulation film made of an iron plating film having a thickness of 3 ⁇ m is further formed on the surface thereof. An underlayer was formed.
  • the square plate sample is put in the same autoclave reaction container together with the heat insulating mold 201, and simultaneously with the heat insulating film 204, A heat insulating film was formed.
  • membrane formed on the said square plate as a result of investigating a composition using the fluorescent X ray apparatus, it has confirmed that it was a compound which consists of a composition of iron and zinc.
  • a zinc ferrite film having the same composition as described above can be formed.
  • a heat insulating film having the same thickness as described above can be formed by appropriately changing the conditions of hydrothermal synthesis, the number of treatments, and the like as necessary.
  • the base of the heat insulating film is a metal film made of a metal element that forms the heat insulating film immediately below the heat insulating film.
  • the present invention is not limited to the above laminated film.
  • an iron film formed directly on the surface of a mold base material by a sputtering method may be used.
  • the process of forming the seed layer on the surface of the heat insulating film was described by sputtering, but apart from this method, the iron film was directly formed by using the same sputtering method and using the target of metallic iron.
  • the same heat insulation mold can be manufactured by the method of doing.
  • this iron film is also omitted, and a nickel target is used instead of the nickel plating film as a plating base film of a microfabricated metal film made of a nickel phosphorus alloy plating film for precision processing.
  • a nickel film formed by a sputtering method may be used.
  • Example 8 A sectional view of the heat insulating mold in Example 8 is shown in FIG.
  • the heat insulating mold 2001 is a mold used for molding a resin part having a precise mirror surface shape.
  • pure copper having high thermal conductivity is used as a material for the mold base material, and the following lamination is performed. It is configured in the form of a structure.
  • a heat insulating film base layer 2003 made of an iron film having a thickness of 3 ⁇ m is disposed, and further a heat insulating film 2004 made of iron ferrite (ie, spinel iron oxide) having a thickness of 50 ⁇ m is formed thereon, and a palladium catalyst fine particle film is formed thereon.
  • a seed layer 2005 is disposed, and a metal film layer 2008 is formed thereon.
  • the metal film layer 2008 is composed of a plating base film 2006 (thickness 1 ⁇ m) made of nickel and a microfabricated metal film 2007 (thickness 6 ⁇ m) made of an amorphous nickel-phosphorus alloy film formed thereon. ing.
  • the molding surface side of the microfabricated metal film 2007 is a precision machined surface 2007a on which a mirror surface is formed by machining. That is, the configuration is similar to the stacked configuration shown in FIG. 26 of Example 1, except that the precision processing surface is a mirror surface.
  • the above-described precision processed surface is prepared by forming a finely processed metal film with an average thickness of 10 ⁇ m in advance and then machining it into a mirror surface to a thickness of 6 ⁇ m.
  • the manufacturing method is different from the formation method by hydrothermal synthesis of the heat insulating film 1004 of the first embodiment under an atmospheric pressure of 100 ° C. or less. It is characterized in that it is made by combining with.
  • an oxide material composed of a metal oxide (spinel type iron oxide) having a low thermal conductivity and having pores as a heat insulating layer resin molding with good specularity becomes possible. That is, the heat of the high-temperature molten resin molded by the mirror surface of the metal mold escapes through the mold base, and the resin molding occurs due to the temperature dropping more than necessary during molding. Defects can be avoided.
  • FIG. 44 the manufacturing process of the heat insulation metal mold
  • a heat insulating film base layer 2003 made of an iron film having a thickness of 3 ⁇ m was formed on the surface of the mold base 2002 on the molding surface side using an iron sulfate plating bath (FIG. 44 (1)).
  • a heat insulating film 2004 made of spinel iron oxide having a thickness of 50 ⁇ m was formed on this surface (FIG. 44 (2)).
  • the heat insulating film 2004 was formed in the air as follows.
  • an aqueous solution in which 41.7 g of ferrous sulfate (FeSO 4 ⁇ 7H 2 O) was dissolved in 60 ml of water was prepared, and 21.6 g of sodium hydroxide was further added to this aqueous solution.
  • a suspension 2021 was prepared by mixing 60 ml of a strong alkaline aqueous solution prepared by dissolving (NaOH). The water used here was water distilled in nitrogen gas.
  • a heat insulating film 2004 was formed using this suspension 2021. For the film formation at that time, a heat insulating film forming apparatus 2022 shown in FIG. 45 was used.
  • a glass Aleen cooler 2023 is attached to the upper part, and further comprises a reaction vessel 2024 made of stainless alloy having an internal volume of 300 ml so that nitrogen gas can flow inside.
  • the above suspension 2021 was placed in the reaction container 2024, and the mold base material 2002 on which the heat insulating base layer 2003 was formed was immersed therein and held using a jig 2025.
  • This mold base material was masked in advance with a tetrafluoroethylene sealing tape except for the molding surface on which the heat insulating base layer 2003 was formed.
  • the reaction vessel 2024 was placed in an oil bath 2026 heated and maintained at 98 ° C. and heated to react for 120 hours. During the reaction time, nitrogen gas was kept flowing into the reaction vessel 2024. After the reaction, the mold base material was taken out together with the jig and thoroughly washed with water.
  • the mold on which the heat insulating film 1004 having a film thickness of 50 ⁇ m is formed is washed with water and sufficiently dried, and then a palladium fine particle film is formed on the surface of the heat insulating film 2004 using a DC sputtering apparatus with a palladium target attached.
  • a seed layer 2005 was formed (FIG. 44 (3)).
  • a plating base film 2006 made of a nickel film having a thickness of 1 ⁇ m was coated by an electroless nickel plating method.
  • a metal film layer 2008 was formed by forming a micro-processed metal film 2007 made of a nickel phosphorus alloy plating film for precision processing having a thickness of 10 ⁇ m by an electroless nickel plating method, and heat-treated at 200 ° C. for 3 hours (FIG. 44 (4)). Thereafter, using the precision cutting machine, the finely processed metal film 2007 was ground to a thickness of 6 ⁇ m to form a precise mirror surface 1007a, thereby obtaining a heat insulating mold for a finely processed die (FIG. 44 (5)). ).
  • the example of the method by a plating method was described in the present Example as a formation method of the heat insulation film
  • the formation method of the film base layer 2003 is not limited to the plating method described in this embodiment.
  • this iron film may be formed directly on the surface of the mold base material by a sputtering method.
  • a rectangular substrate size: 50 mm length, 20 mm width
  • the same material pure copper
  • a thickness of 2.0 mm was prepared, a heat insulating film was formed using this substrate, and the material was evaluated in detail as this heat insulating film F.
  • the production of the heat insulating film F will be described below.
  • a similar heat insulating film foundation layer was formed on the surface of the substrate in the same manner as in the step of manufacturing the heat insulating mold 2001 (FIG. 44 (1)).
  • a suspension having the same composition as the suspension 2021 described above was used, and the reaction vessel shown in FIG. The above reaction was repeated a total of 3 times (a total of 360 hours) to produce a heat insulating film F having a film thickness of about 150 ⁇ m.
  • a film having a thicker film than that used for the mold was produced in the same manner as in Example 1, in addition to the composition and crystal structure necessary to specify the material of the heat insulating film, the porosity and Vickers hardness. This is because the same sample is evaluated simultaneously.
  • the X-ray diffraction pattern is shown in FIG. FIG. 47 shows a scanning electron microscope image of the surface after the heat insulating film F is formed. Similar to the heat insulation film A of Example 1, it can be seen that the film structure has a three-dimensional network structure with sharp corners and connected crystal grains having different sizes. Furthermore, when closely observed, the crystal grains that appear to be twin crystals are continuously three-dimensionally grown, and there are innumerable pores consisting of gaps formed by the network structure inside the film. It was confirmed that the film had a porous structure.
  • FIG. 48 shows a scanning electron microscope image of the polished surface of the heat insulating film F in which the porosity was measured. From this example, it was confirmed that the film produced at 100 ° C. or lower under atmospheric pressure was also a porous ferrite film, similar to the films obtained by hydrothermal synthesis in Examples 1 to 7.
  • Example 9 When the iron ferrite (Fe 3 O 4 ) film is formed by the wet synthesis reaction of the present invention, 1) Fe 2+ + OH ⁇ ⁇ Fe (OH) 2 and 2) Fe (OH) 2 ⁇ Fe 3 O 4 That is, 1) Ferrous hydroxide (Fe (OH) 2 ) is produced from divalent iron ions in an alkaline atmosphere. 2) As the hydrolysis reaction proceeds, this ferrous hydroxide changes to an iron ferrite (Fe 3 O 4 ) film, Through these two reactions, ferrite is generated from iron ions.
  • Example 9 a sample film was prepared in the same manner as the heat insulating film F except for the raw material suspension used for the synthesis of the heat insulating film F of Example 8, and the other steps. That is, in the preparation of the raw material suspension, instead of water distilled in a nitrogen atmosphere used in the synthesis of the heat insulating membrane F, water in which ascorbic acid, which is a kind of reducing agent, is dissolved in ion exchange water is used as water. Using.
  • an aqueous solution in which 41.7 g of ferrous sulfate (FeSO 4 .7H 2 O) was dissolved in 60 ml of ion-exchanged water was prepared, and further 24 mg of ascorbic acid as a reducing agent was added and dissolved in this aqueous solution. Furthermore, 60 ml of a strong alkaline aqueous solution prepared by dissolving 21.6 g of sodium hydroxide (NaOH) in ion exchange water was mixed with the above aqueous solution to prepare a raw material suspension.
  • FeSO 4 .7H 2 O ferrous sulfate
  • 60 ml of a strong alkaline aqueous solution prepared by dissolving 21.6 g of sodium hydroxide (NaOH) in ion exchange water was mixed with the above aqueous solution to prepare a raw material suspension.
  • the material was evaluated in exactly the same manner as the heat insulating film F for the purpose of confirming whether a film of a desired material was formed. Similar to Example 1, in addition to the composition and crystal structure necessary for specifying the material of the heat insulating film, the porosity and Vickers hardness were also evaluated.
  • the X-ray diffraction pattern is shown in FIG. FIG. 50 shows a film scanning electron microscope image of the surface after the heat insulation film G is formed. Similar to the heat insulation film A of Example 1, crystal grains having different sizes are connected to form a film structure grown in a three-dimensional network structure, and a gap portion in which the network structure is formed inside It can be seen that there are innumerable pores consisting of.
  • FIG. 51 shows a scanning electron microscope image of the polished surface of the heat insulating film G in which the porosity was measured. From this example, it can be seen that even when ion-exchanged water in which a reducing agent is dissolved is used for the synthesis of the heat insulating film, a porous ferrite film can be produced in the same manner as the films obtained by hydrothermal synthesis in Examples 1 to 8. .
  • the X-ray diffraction pattern is shown in FIG.
  • a scanning electron microscope image of the film surface after the film formation is shown in FIG. It can be seen that the heat-insulating film G and the porous film have the same shape but different in particle size.
  • the heat insulating film obtained by synthesis under atmospheric pressure of 100 ° C. or less was described.
  • the raw material suspension of the heat insulating film obtained by hydrothermal synthesis shown in Examples 1 to 7 was used.
  • water used for the synthesis of the heat insulating film in place of the water distilled in the nitrogen atmosphere, water obtained by adding a reducing agent to ion-exchanged water can be used in the same manner as in this example. It can be seen that a heat insulating film made of ferrite can be synthesized.
  • Divalent iron ions (Fe 2+ ions) in an aqueous solution of an iron salt are immediately produced in an iron hydroxide suspension produced until a strong alkaline aqueous solution is added or a strong alkaline aqueous solution is added.
  • Any reducing reagent having an effect of preventing oxidation to trivalent iron ions (Fe 3+ ions) may be used.
  • water-soluble hydroquinone compounds of various derivatives of hydroquinone may be used as the reducing agent.
  • FIG. 56 shows a schematic cross-sectional configuration diagram of the measurement sample 2011 on which the heat insulating film G is arranged.
  • the measurement sample 2011I has the same configuration as that shown in FIG. 56 except that the material of the heat insulating film is the heat insulating film I having a film thickness of 25 ⁇ m.
  • the measurement sample 2011G was produced as follows. First, a round bar made of the same material as the mold base material 2002 used for the heat insulating mold 2001 having the diameter of 10.0 mm and the length of 44.0 mm in the configuration of the eighth embodiment is prepared, and the diameter is formed at the center of one end face thereof. A thermocouple mounting hole 2012a having a depth of 3.5 mm and a depth of 22.0 mm was formed to produce a metal round bar base material 2012. Using this base material 2012, from the iron film having a thickness of 3 ⁇ m from the bottom of the end face at the position opposite to the end face with the thermocouple mounting hole 2012a to the position of 23.0 mm, by the same manufacturing method as shown in FIG.
  • a heat insulating film base layer 2013 is formed, and a heat insulating film 2014 made of the heat insulating film G of the present invention having a thickness of 50 ⁇ m is formed thereon by the same method as that for forming the heat insulating film G described above.
  • a seed layer 2015 made of an ultrathin palladium catalyst fine particle film is formed by sputtering from the end face with the thermoelectric attachment hole 2012a thereon to the position of 23.0 mm from the bottom face of the end face by sputtering.
  • a plating base film 2016 (thickness 1 ⁇ m) made of nickel is formed by an electroless nickel plating method, and further on the amorphous nickel phosphorus alloy film having a thickness of 6 ⁇ m by an electroless nickel plating method.
  • a plated metal film 2017 was formed, and a metal film layer 2018 composed of a plating base film 2016 and a plated metal film 2017 was formed.
  • the measurement sample 2011I is the measurement sample 2011 shown in FIG. 56, in which a heat insulating film made of a heat insulating film I having a film thickness of 25 ⁇ m is formed instead of the heat insulating film 2014 made of the heat insulating film G having a film thickness of 50 ⁇ m. It is a sample.
  • the comparative sample 1211 (FIG. 33) used in Example 1 was used as a comparative sample having a structure having no heat insulating film. Evaluation of heat insulation was performed as follows using the heat insulation evaluation apparatus 21 (FIG. 34) used in Example 1. First, the heat insulating property of the heat insulating film G was measured using the measurement sample 2011G and the comparative sample 1211.
  • the thermal insulation evaluation of the thermal insulation film G of the present invention was performed at the same time with the two measurement samples 2011G and 1211 kept in the constant temperature water tank 22 shown in FIG.
  • the thermal insulation effect at the time of temperature rise was investigated by measuring the rate of temperature rise.
  • both measurement samples 2011F and 1211 whose temperature rose were attached to the heat insulation plate 24, and were immersed in the low-temperature water of the constant temperature water bath 23 at the same time, and the heat insulation effect at the time of temperature reduction was investigated by measuring the rate of temperature drop. .
  • both measurement samples 2011G and 1211 are compared with the measurement sample 1211 having no heat insulation film with respect to the time change of the temperature rise when immersed in the constant temperature water bath 22 kept at 90 ° C. from room temperature.
  • a measurement result of the measurement sample 2011G provided with the heat insulating film of the present invention a time change in temperature rise and a time change in temperature difference between the two measurement samples are shown.
  • FIG. 58 shows the measurement result of the time change of the temperature drop when both the measurement samples 2011G and 1211 whose temperature has been once increased are immersed in a constant temperature water bath kept at 28 ° C. at the same time.
  • FIG. 59 shows the time change of the temperature rise when the measurement sample 2011I and the comparison sample 1211 are immersed in the constant temperature water bath 22 kept at 92 ° C. from room temperature, compared with the measurement sample 1211 having no heat insulation film.
  • FIGS. 57 to 60 shows the measurement results of the time change of the temperature drop when both the measurement samples 2011I and 1211 whose temperature has been increased are immersed in a constant temperature water bath maintained at 22 ° C. at the same time.
  • the two types of heat insulating films of the present invention have an effect of making it difficult to transfer heat to the substrate with respect to an external temperature change.
  • Example 10 As shown in Example 5, in the case of a heat insulating film by a hydrothermal synthesis method, by replacing some of iron ions forming spinel iron oxide Fe 3 O 4 with various metal ions, substituted ferrites having various compositions Can be produced in the form of a film on the substrate. In the same manner as in Example 5, in the synthesis under the atmospheric pressure of 100 ° C. or less, which is the synthesis condition of the heat insulating film described in Examples 8 and 9, can substituted ferrites of various compositions be formed in a film shape on the substrate? I examined whether.
  • the base substrate used for film formation for the purpose of confirming whether a desired ferrite film can be formed by the reaction under atmospheric pressure similar to the method shown in Example 8 is the material evaluation of the heat insulating film of Example 8.
  • the same material (pure copper) and the same shape as the substrate used for the substrate (size: 50 mm long, 20 mm wide, 2.0 mm thick), and the same heat insulating film underlayer (3 ⁇ m thick iron plating film) Is formed.
  • ferrous sulfate FeSO 4 ⁇ 7H 2 O
  • aluminum sulfate AlSO 4 ⁇ 16H 2 O
  • 48 mg of ascorbic acid are dissolved in ion-exchanged water in 60 ml of water.
  • a suspension was prepared by mixing 60 ml of the prepared aqueous solution and 60 ml of a strong alkaline aqueous solution prepared by dissolving 21.6 g of sodium hydroxide (NaOH) in ion-exchanged water.
  • the above-described suspension is put into a stainless steel reaction vessel 2024 having an internal volume of 300 ml using a heat insulating film forming apparatus 2022 shown in FIG. 45, and a heat insulating base layer is formed therein.
  • the substrate was immersed and held using a jig 2025.
  • the reaction was carried out at 98 ° C. for 40 hours.
  • the substrate was taken out together with the jig and thoroughly washed with water.
  • a film having a thickness of 47 ⁇ m was formed on the substrate.
  • This film was subjected to composition analysis using a fluorescent X-ray apparatus. As a result, it was confirmed to be a compound of iron and aluminum.
  • the crystal structure was examined using X-ray diffraction.
  • the X-ray diffraction pattern is shown in FIG.
  • observation of the raw surface of this film with a scanning electron microscope revealed that this film was a porous film.
  • a film having a thickness of 6 ⁇ m was formed on the substrate.
  • the X-ray diffraction pattern is shown in FIG. Although this film was a thin film, it was found from observation of the unprocessed surface with a scanning electron microscope that the film was a porous film.
  • a film having a thickness of 11 ⁇ m was formed on the substrate.
  • the X-ray diffraction pattern is shown in FIG. This membrane was also a porous membrane.
  • a film having a thickness of 18 ⁇ m was formed on the substrate.
  • the X-ray diffraction pattern is shown in FIG. This membrane was also a porous membrane.
  • a film having a thickness of 20 ⁇ m was formed on the substrate.
  • the X-ray diffraction pattern is shown in FIG. This membrane was also a porous membrane.
  • a film having a thickness of 21 ⁇ m was formed on the substrate.
  • the X-ray diffraction pattern is shown in FIG. This membrane was also a porous membrane.
  • the mold of the present invention with a predetermined heat insulation layer has excellent mold base forming surface coverage and can be directly formed while adjusting the film thickness without post-processing. Therefore, it is useful as a heat insulating mold for resin molding having a complicated shape such as an optical element or a molded product having a fine pattern shape. It can also be applied to uses such as a mold for nanoimprinting.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

L'invention concerne une matrice comprenant une couche d'isolation thermique qui ne nécessite pas de traitement ultérieur, offre un degré d'uniformité supérieur en termes d'épaisseur et présente une propriété d'adhérence supérieure à la matrice. L'invention concerne une matrice à isolation thermique et son procédé de production, la matrice présentant une couche d'isolation thermique entre une base de matrice métallique et un film métallique configurant une surface de moulage, et la couche d'isolation thermique étant constituée d'un corps poreux dans lequel des particules cristallines de ferrite sont reliées sous la forme d'une structure maillée tridimensionnelle.
PCT/JP2011/065668 2010-07-12 2011-07-08 Matrice à isolation thermique et son procédé de production WO2012008372A1 (fr)

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TWI468238B (zh) * 2012-08-22 2015-01-11 China Steel Corp 鑄模及其熱處理方法
WO2016147428A1 (fr) * 2015-03-14 2016-09-22 神戸セラミックス株式会社 Élément de moteur à combustion interne et son procédé de production
JP6118446B1 (ja) * 2016-09-13 2017-04-19 神戸セラミックス株式会社 内燃機関構成部品及びその製造方法
TWI622491B (zh) * 2016-12-16 2018-05-01 財團法人金屬工業研究發展中心 Hot stamping forming low heat transfer heating mold and hot stamping part forming method

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JPS6315990B2 (fr) * 1982-12-15 1988-04-07 Masanori Abe
JPH09300357A (ja) * 1996-05-17 1997-11-25 Asahi Eng Co Ltd 金型加熱装置
JP2001162648A (ja) * 1999-12-13 2001-06-19 Idemitsu Petrochem Co Ltd 表皮一体軽量樹脂成形品の成形方法および成形品
JP2002096335A (ja) * 2000-09-25 2002-04-02 Minolta Co Ltd 光学素子成形用金型及び光学素子成形方法
JP2004175112A (ja) * 2002-11-13 2004-06-24 Maxell Hi Tec Ltd 成型用金型及びその製造方法
JP2006044247A (ja) * 2004-06-29 2006-02-16 Konica Minolta Opto Inc 射出成形用金型及び射出成形方法
WO2007020769A1 (fr) * 2005-08-18 2007-02-22 Konica Minolta Opto, Inc. Moule de métal servant à former un dispositif optique et son procédé de production

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DE3529329A1 (de) * 1985-08-16 1987-02-26 Kochs Adler Ag Vorrichtung an einer naehmaschine zum aufbringen einer zugspannung in einem dem naehprozess zuzufuehrenden material
EP2591912A1 (fr) * 2006-02-20 2013-05-15 Daicel Chemical Industries, Ltd. Ensemble multicouche et matériau composite le comprenant

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Publication number Priority date Publication date Assignee Title
JPS6315990B2 (fr) * 1982-12-15 1988-04-07 Masanori Abe
JPH09300357A (ja) * 1996-05-17 1997-11-25 Asahi Eng Co Ltd 金型加熱装置
JP2001162648A (ja) * 1999-12-13 2001-06-19 Idemitsu Petrochem Co Ltd 表皮一体軽量樹脂成形品の成形方法および成形品
JP2002096335A (ja) * 2000-09-25 2002-04-02 Minolta Co Ltd 光学素子成形用金型及び光学素子成形方法
JP2004175112A (ja) * 2002-11-13 2004-06-24 Maxell Hi Tec Ltd 成型用金型及びその製造方法
JP2006044247A (ja) * 2004-06-29 2006-02-16 Konica Minolta Opto Inc 射出成形用金型及び射出成形方法
WO2007020769A1 (fr) * 2005-08-18 2007-02-22 Konica Minolta Opto, Inc. Moule de métal servant à former un dispositif optique et son procédé de production

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JP4966437B2 (ja) 2012-07-04
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TWI477381B (zh) 2015-03-21

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