TW201210789A - Heat insulation metal mold and method of manufacturing the same - Google Patents

Abstract

The present invention provides a metal mold that requires no post-processing and has a heat insulation layer having better uniformity in its thickness compared to the prior art and exhibiting excellent bonding property to the mold. The present invention relates to a heat insulation metal mold comprising a heat insulation layer between a base metal material of the metal mold and a metal film constituting a molding surface, characterized in that the heat insulation layer is formed of a porous material in which ferrite crystal particles are linked to form a three dimensional network, and to a method of producing the same.

Description

201210789 VI. Description of the Invention: C Technical Field of Invention: 1 Field of the Invention The present invention relates to a heat insulating mold for resin molding of optical components, precision parts, and the like, and a method of manufacturing the same. I. Prior Art 3 Background of the Invention Various resin molded articles are produced by a resin injection molding method in which molten resin is injected into a molding space formed between a fixed mold and a movable mold of a molding die. In the case of injection molding of a representative molding method for resin molding, once the molten resin is injected into the molding space of the mold, the heat of the molten resin is rapidly moved to the mold immediately, and at the same time, the melting of the contact mold is "resin" The surface is rapidly cooled and solidified, and the operation proceeds to the inside, and the molding is completed. In recent years, more complicated or subtle shapes have been demanded for resin molded articles. Therefore, in the case of resin molding, it is necessary to process a three-dimensional finely processed pattern of a mold forming surface having a complicated or fine shape, and it is necessary to faithfully transfer the finely processed pattern to the resin molded article. However, in the mold of the fine groove processing, when the molten resin reaches the inside (deep) of the groove at the time of injection molding, the solidification of the surface of the molten resin starts, and the mold surface is not properly transferred, and the molding is performed. The end of the situation. In order to achieve a proper transfer, a method of improving the molding conditions, a method of increasing the injection pressure of the molten resin, and a method of increasing the injection speed, etc., are considered, but there is a limit in improving the transferability. 201210789 Therefore, the two points shown below are strongly requested. That is, one of the points is in the mold "the period during which the mold forming surface can be sufficiently transferred to the resin to be injected" is to maintain the viscosity of the resin suitable for molding, so that the temperature of the input resin does not decrease. Another point is that once the predetermined shape can be transferred, the heat retained by the molten resin in the mold is immediately discharged through the mold, and the temperature of the resin is lowered to cause solidification. For the above-mentioned technical means, it is also considered that before the injection molding, the entire mold is heated to improve the transferability, and then the entire mold is quenched immediately, and the transferred resin is solidified and then released, but the resin is required. The forming device is attached to the heating and cooling device of the entire mold, which is not suitable from the cost side and the energy side. Therefore, the method for controlling the temperature of the mold to reduce the temperature during the molding of the resin is to provide a heat insulating layer composed of various materials having a thermal conductivity lower than that of the mold material in the vicinity of the forming surface of the mold (for example, Patent Document 1). In view of the fact that the resin molded article of the optical element which is particularly required to have high precision is formed at the time of molding, a material having a high mechanical strength and a high-precision heat insulating layer thickness are required in the heat-sensitive layer of the mold. Therefore, it has been proposed to use a material having a high mechanical strength, instead of forming it into a plate shape to be attached to a mold, and directly forming a film on a mold base material. The most suitable method for film formation is the riding method. The coating technology is based on the heating of the electric material, so that the coating material is melted or softened to make it into a microparticle shape and accelerate. The film is ejected at a high speed, and the surface of the object to be coated is struck to cause the particles to be crushed into flat particles to condense @, _, thereby forming a film. In this technique, a ceramic-based material having a low thermal conductivity and high mechanical strength, in particular, a film formed by oxidation is formed as a heat-insulating film of a conventional mold (see, for example, Patent Document 2). A conventional heat insulating mold described in Patent Document 2 is shown in Fig. 24. In Fig. 24, the heat insulating mold 101 is composed of a mold base material 102, a heat insulating film (heat insulating layer) 1〇5, and a metal coating layer 108 having a precision machined surface 10a. In particular, the heat-insulating film 1 〇 5 is a heat-insulating film composed of a spray film of a ceramic composition such as an oxide bond. PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1 Japanese Patent No. 3382281 Patent Document 2 Japanese Patent No. 4135304 [Abstract] Summary of Invention The object of the invention is to provide heat insulation by a spray film as in the prior art. The film is not easy to form a sentence thickness, and further improvement is required. Generally, in the heat-insulating mold, the transfer of the fine mold can be carried out, so the heat-insulating properties of the forming surface of the mold should be as uniform as possible. Therefore, the thickness of the insulation layer needs to be uniform. In this case, a resin is used to form a heat-insulating film for applying a mold having a shape that is more precise than that of a conventional method: the film is easy to be used as an example, and when it is a small mold base material, it is flat- When the surface of the mold base material forms a heat insulating mold, the surface of the mold base material is sprayed with the particles and the growth of the smear film is the same as the thickness W of the outer peripheral portion. Therefore, the surface of the (10) surface is precisely machined by adding a normal thickness of the ore metal, and the surface which is changed by the formation of the film is used as a heat insulating mold 201210789. However, at this time, since the thickness of the heat insulating film of the central portion of the forming surface is different from that of the outer portion, it is strictly speaking that the heat insulating property is deviated due to the difference in the surface of the surface of the forming surface. On the other hand, in order to make the heat insulation of the mold more uniform, the following method has been proposed. For example, in the case of a mold having a flat surface having a high degree of flatness, the step of forming a sprayed film employs a step of forming a spray film having a thickness larger than a target thickness, and then grinding the same. By machining such as cutting, the thickness of the spray film formed on the surface of the mold base material is processed into a uniform shape, whereby the heat insulating property of the mold forming surface during molding can be uniformized, and accuracy can be further improved. High resin molding. Since the increased mechanical processing step is a step of processing the high-hardness spray film, the difficulty and labor accompany it. Further, there is a case where the melt film is subjected to a p-stress in the spray film at the processing stage of the tenth or later stage of the spray film. When such an internal stress strain occurs, a serious defect such as a crack or the like is generated in the refining, which causes a peeling of the spray film, and a large gap is formed in the forming step. When the weaner molding die is a mold having a deep recessed portion, it is necessary to form a heat-insulating film similar to the thickness of the molding surface in the molding surface side of the mold base material located on the heat insulating portion. However, as described above, the high-intensity flying high-speed fluid of the molten fine particles is sprayed on the surface of the broken surface and the film is formed by the filming method, so that the surface of the processed object having the concave portion as described above is uniform. The thickness of the film becomes more and more difficult. The formation of the field heat-insulating film relies on the conventional technique of the spray method to be used for the warfare type. When the mold is formed by the spray, the film formed by the spray cannot be directly used in 201210789, and it needs to be precision-- The thickness C is a high-density glare film post-processing, especially for the formation of a film having a complicated deep recessed portion. The positive microparticles are stacked and shaped _-. Both are: Even if the film can form the film to form the concave portion, the molten film is not easy to open the V-thickness of the mold, so the above-mentioned mechanical post-processing is required '·the other t-face' is processed after the steps are indispensable The risk of stress and strain applied to the glare film is such that when the strain is applied, cracks, peeling, and the like of the glare film are caused. Therefore, the main object of the present invention is to provide a mold which does not require post-processing and has a heat-insulating layer which is higher in uniformity in thickness than conventional techniques and which is excellent in adhesion to a mold. Means for Solving the Problems The present inventors have made efforts to continuously study the results of the prior art, and found that the above object can be achieved by using a metal oxide formed by a hydrothermal synthesis reaction as a heat insulating layer. The present invention has been completed. That is, the present invention relates to the following heat insulating mold and a method of manufacturing the same. L is a heat insulating mold which is provided with a heat insulating layer between a metal mold base material and a metal film constituting a molding surface, wherein the heat insulating layer is formed by connecting crystal particles of the fat granules into a three-dimensional mesh shape. The formed porous body is composed. 2. The insulating mold of the first aspect, wherein the fertilizer system has a spinel crystal structure represented by the following general formula.

AxFe3_x04 (where 'A' indicates at least one of the metal elements which can be formed in the Fe position of the crystallized iron oxide 7 201210789, and χ meets OSx<1 〇) ° 3. As in the thermal mold of item 2, The lanthanide is at least one of Ca, Ζη, Μη, CrCr, Li, and Mg. 4. The insulation mold of item 1, wherein the thermal insulation layer has a porosity of 5 to 75%. 5. The insulation mold of item 1, wherein the thickness of the insulation layer is 15/zm or more. 6. The insulation mold of item 1, wherein the insulation layer has a Vickers hardness of Hvl30~Hv560. 7. The heat insulating mold according to item 1, wherein the heat insulating layer is made of 1) a surface of a metal mold base material or 2) a surface of a metal layer previously formed on a surface of the mold base material, and a metal component The aqueous solution or the aqueous dispersion reacts to form a generator. 8. The heat insulating mold according to Item 1, wherein the metal film comprises at least: 1) a seed layer formed on the heat insulating layer and containing a plating catalyst; and 2) formed in the seed layer Metallized film on it. 9. The heat insulating mold according to item 1, which is used for forming a composition containing a resin component. 10. A method for producing a heat insulating mold, which is a mold having a heat insulating layer between a metal mold base material and a metal film constituting a forming surface, the step of forming the heat insulating layer comprising the steps of: 1) The surface of the metal mold base material or 2) the surface of the metal layer previously formed on the surface of the mold base material reacts with the aqueous solution or the aqueous dispersion containing the metal component, thereby forming a metal oxide. 11. The method of manufacturing the heat insulating mold according to Item 10, wherein the step of forming the metal film 201210789 comprises the steps of: 1) forming a seed layer containing a catalyst on the heat insulating layer; and 2) The step of forming a mineral metal film on the § hai seed layer. 12. The method of producing an insulating mold according to item 11, wherein the seed layer is formed by a sputtering method or a plating method. 13. The method of manufacturing the heat insulating mold according to Item 1, wherein the foregoing reaction comprises the steps of: 1) the surface of the metal mold base material or 2) the surface of the metal layer previously formed on the mold base material has been In the state in which the mixed metal salt and the treatment liquid obtained by the test are in contact with each other, the heat treatment is performed at a temperature of 85 ° C or more. 12. The manufacturing method of the heat insulating mold according to item 13 is in the range of 1 〇〇 2 Hey. Heat treatment in a saturated water vapor pressure or higher. A method of producing a heat insulating mold according to item 10, which is carried out in the presence of a reducing agent. Advantageous Effects of Invention According to the present invention, it is possible to provide a mold which does not require post-processing and has a heat-insulating layer which is higher in uniformity in thickness than conventional techniques and which is excellent in adhesion to a mold. Thereby, in particular, when the resin is molded, a complicated molding surface can be transferred with good precision, and a precise molded body can be produced freely. In particular, in the mold of the present invention, it can be used as a base material of the heat insulating layer as a starting material to form a heat insulating layer by a wet reaction (particularly, a money synthesis reaction). At this time, a relatively uniform thickness of the barrier layer can be formed along the surface shape of the metal mold or the like which is the base. According to the drawing (reproduction) mode and the shape of the surface of the base material which can be more faithfully printed, the molded body having the structure of the Japanese Patent No. 201210789 can be manufactured freely. In other words, when the (four) melt resin is used as the molding material, the (four)' can effectively maintain the (four) melt state, and the secret grease can pass through the fine groove portion of the molding surface without dead angle, and as a result, the surface shape of the molding surface can be faithfully reproduced ( Concave shape). In addition, due to the hydrothermal synthesis reaction, the heat-insulating layer and the metal mold are reduced, and the cracks such as the conventional spray film, the peeling of the bow, the peeling, and the like can be greatly reduced. Risk, as a result, can further improve the manufacturing efficiency of resin formation. Further, when the resin is formed, it is heat-insulated, and if the thickness of each of the fine heat-insulating layers is intentionally changed, the melting can be finely controlled. The heat retention and cooling properties of the fine areas of the mold forming surface. The resin molding of a molded article having a more complicated uneven shape is expected. At this time, it is required that the material forming the heat insulating layer can be easily reinforced, and since the heat insulating film of the present invention is excellent in mechanical reinforcement, it is necessary to perform heat control of the surface of the mold during the molding of the resin (4). The heat-insulating film which forms a uniform thickness on the entire surface of the reducer only cuts the necessary portion and changes the film thickness, thereby making it possible to perform the heat flow or cooling of the resin more precisely. control. Such a mold of the present invention is particularly suitable for the production of a resin molded body. Therefore, it is also useful for the manufacture of optical materials (lenses, cymbals, light guides, CDs, discs, etc., other recording media). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a heat insulating mold according to a second embodiment of the present invention. Fig. 2 (1) to (5) show the manufacture of the heat insulating mold of the magic embodiment of the present invention 10 201210789 • A diagram of the steps. Fig. 3 is a view showing an X-ray diffraction pattern of the heat insulating film of the second embodiment of the present invention. Fig. 4 is a schematic cross-sectional view showing a sample for heat insulation evaluation of the heat insulating film of the second embodiment of the present invention. Fig. 5 is a schematic cross-sectional view showing a sample for heat insulation evaluation of a conventional heat insulating film. Fig. 6 is a schematic cross-sectional view of a comparative sample which does not have thermal insulation evaluation of a heat insulating film. Fig. 7 is a schematic configuration diagram of a measuring device for evaluating the heat insulating property of the heat insulating film of the present invention. Fig. 8 is a view showing the results of evaluation of the heat insulating properties at the time of temperature rise of the heat-insulating sample of the heat-insulating film of the second embodiment of the present invention. Fig. 9 is a view showing the results of heat insulation evaluation at the time of temperature drop of the sample for heat insulation evaluation of the heat insulating film of the second embodiment of the present invention. Fig. 10 is a view showing the results of heat insulation evaluation at the time of temperature rise of a sample for heat insulation evaluation of a conventional heat insulating film. Fig. 11 is a view showing the results of heat insulation evaluation at the time of cooling of the sample for heat insulation evaluation of the conventional heat insulating film. Fig. 12 is a schematic cross-sectional view showing a heat insulating mold of a third embodiment of the present invention. Fig. 13 (1) to (4) are views showing the steps of producing the heat insulating mold of the third embodiment of the present invention. Fig. 14 is a schematic cross-sectional view showing a sample for heat insulation evaluation of the same structure as the heat insulating mold of the third embodiment of the present invention. 201210789 Fig. 15 is a schematic cross-sectional view of a comparative sample for thermal insulation evaluation without a heat insulating film. Fig. 16 is a view showing the results of heat insulation evaluation at the time of temperature rise of the sample for heat insulation evaluation of the heat insulating film of the third embodiment of the present invention. Fig. 17 is a view showing the results of evaluation of the heat insulating properties at the time of temperature lowering of the sample for heat insulation evaluation of the heat insulating film of the third embodiment of the present invention. Fig. 18 is a view showing the results of heat insulation evaluation at the time of temperature rise of the sample for heat insulation evaluation of the heat insulating film of the third embodiment of the present invention. Fig. 19 is a view showing the results of heat insulation evaluation at the time of temperature drop of the sample for heat insulation evaluation of the heat insulating film of the third embodiment of the present invention. Fig. 20 is a schematic perspective view showing a heat insulating mold of a sixth embodiment of the present invention. Figure 21 is a cross-sectional view showing the processing pattern of the mold base material of the sixth embodiment of the present invention. Fig. 22 is a view showing an X-ray diffraction pattern of a heat insulating film containing zinc in the fifth embodiment of the present invention. Figure 23 is a schematic cross-sectional view showing a heat insulating mold of a seventh embodiment of the present invention. Figure 24 is a schematic cross-sectional view of a conventional heat insulating mold. Fig. 25 is a view showing an example of a procedure for molding a molten resin using the mold of the present invention. Figure 26 is a schematic cross-sectional view showing a heat insulating mold according to a first embodiment of the present invention. Fig. 27 (1) to (5) are views showing the steps of producing the heat insulating mold according to the first embodiment of the present invention. Fig. 28 is a view showing an X-ray diffraction pattern of the heat insulating film A of the first embodiment of the present invention. 12 201210789 Fig. 29 is a view showing a broom type electron microscope image of the polishing surface of the heat insulating film A of the first embodiment of the present invention. Fig. 30 is a view showing a polishing section of the heat insulating film A of the first embodiment of the present invention. Fig. 31 is a view showing a scanning electron microscope image of the polishing surface of the heat insulating film B of the first embodiment of the present invention. Fig. 32 is a schematic cross-sectional view showing a sample for heat insulation evaluation of the same structure as the heat insulating mold of the first embodiment of the present invention. Fig. 3 is a schematic cross-sectional view of a comparative sample for thermal insulation evaluation without a heat insulating film. Fig. 34 is a schematic structural view of a measuring device for evaluating the heat insulating property of the heat insulating film of the present invention. Fig. 35 is a view showing the results of heat insulation evaluation at the time of temperature rise of the sample for heat insulation evaluation of the heat insulating film of the first embodiment of the present invention. Fig. 36 is a view showing the results of heat insulation evaluation at the time of temperature drop of the sample for heat insulation evaluation of the heat insulating film of the first embodiment of the present invention. Fig. 37 is a view showing a scanning electron microscope image of the polishing surface of the heat insulating films C, D, and E of the fourth embodiment of the present invention. Fig. 38 is a view showing an X-ray diffraction pattern of a heat-insulating film containing calcium in the fifth embodiment of the present invention. Fig. 39 is a view showing a scanning electron microscope image of a polishing surface of a heat-insulating film containing calcium in the fifth embodiment of the present invention. Fig. 40 is a view showing a method of measuring the porosity of the heat insulating layer of the present invention. 13 201210789 Fig. 41 is a view showing a scanning electron microscope image of the surface of the heat insulating film A of the first embodiment of the present invention. Fig. 4 is a view showing a scanning electron microscope image of the surface of the heat-insulating film containing calcium in the fifth embodiment of the present invention. Figure 43 is a schematic cross-sectional view showing a heat insulating mold of an eighth embodiment of the present invention. Fig. 44 (1) to (5) are views showing the steps of producing the heat insulating mold of the eighth embodiment of the present invention. Fig. 45 is a schematic view showing a reaction vessel used in the eighth embodiment of the present invention. Fig. 46 is a view showing an X-ray diffraction pattern of the heat insulating film of the eighth embodiment of the present invention. Fig. 47 is a view showing a scanning electron microscope image of the surface of the heat insulating film of the eighth embodiment of the present invention. Fig. 4 is a view showing a scanning cat electron microscope image of the polishing surface of the heat insulating film of the eighth embodiment of the present invention. Fig. 49 is an X-ray diffraction pattern diagram of the heat insulating film G of the ninth embodiment of the present invention. Fig. 50 is a view showing a scanning electron microscope image of the surface of the heat insulating film G of the ninth embodiment of the present invention. Fig. 51 is a view showing a scanning electron microscope image of the polishing surface of the heat insulating film G of the ninth embodiment of the present invention. Fig. 5 is a view showing an X-ray diffraction pattern of the heat-insulating film of the ninth embodiment of the present invention. Fig. 53 is a view showing the scanning of the surface of the insulating film of the ninth embodiment of the present invention. Fig. 54 is a view showing an X-ray diffraction pattern of the heat insulating film I of the ninth embodiment of the present invention. Fig. 55 is a view showing a scanning electron microscope image of the surface of the heat insulating film I of the ninth embodiment of the present invention. Fig. 56 is a schematic cross-sectional view showing a sample for heat insulation evaluation in which the heat insulating film G is disposed. Fig. 57 is a view showing the results of heat insulation evaluation at the time of temperature rise of the sample for heat insulation evaluation of the heat insulating film G of the ninth embodiment of the present invention. Fig. 58 is a view showing the results of heat insulation evaluation at the time of temperature drop of the sample for heat insulation evaluation of the heat insulating film G of the ninth embodiment of the present invention. Fig. 59 is a view showing the results of heat insulation evaluation at the time of temperature rise of the sample for evaluation of the heat insulating film 1 of the heat insulating film 1 of the ninth embodiment of the present invention. Fig. 60 is a view showing the results of heat insulation evaluation at the time of temperature drop of the sample for heat insulation evaluation of the heat insulating film 1 of the ninth embodiment of the present invention. Fig. 61 is a view showing an X-ray diffraction pattern of a heat-insulating film having a different composition according to a tenth embodiment of the present invention. I: Embodiment 3: Embodiment for carrying out the invention 1. Insulation mold The mold for insulation of the present invention (the mold of the present invention) is a mold having a heat insulation layer between a metal mold base material and a metal film constituting a molding surface. The heat insulating layer is composed of a porous body formed by connecting crystal particles of a fat body to a three-dimensional network. 15 201210789 In the mold of the present invention, as described above, it is a basic constructor having a) a metal mold base material/heat insulation layer/metal film or b) a metal mold base material/metal layer/heat insulation layer/metal film. It can also include other layers as needed. Hereinafter, the structure of each layer will be described. Further, in the present specification, the term "metal" means not only a metal monomer but also an alloy or an intermetallic compound, unless otherwise specified. Metal mold base material The metal mold base material may be made of metal, and may be the same material as that of a mold which is well known or commercially available. For example, metals such as iron, aluminum, and copper (metal monomers), carbon steel, stainless steel, copper alloys, and alloys such as titanium alloys can be exemplified. Further, the metal mold base material may be either a melted material or a sintered body. In particular, in the present invention, it is preferable to use an iron-based metal as a metal mold base material in the advantage that the fertilizer-granular layer which can be directly formed as a heat-insulating layer on the surface of the iron-based metal. That is, it is preferable to use at least one type of iron-based metal of metallic iron and iron alloy. The iron alloy is not particularly limited, and carbon steel, stainless steel (SUS), chrome molybdenum steel or the like is suitably used. Further, the forming surface side of the metal mold base material may be formed into any shape of a flat surface or a curved surface, or may be an inverted shape in which the fine shape of the final molded body is to be applied, or may be a shape of the molded body according to the purpose. Suitable for constitution. For example, in particular, when the mold requires a deep recessed portion (groove portion), an inverted type or a similar shape (recessed portion) to be transferred to the shape of the forming surface may be formed in advance on the molding surface side of the metal mold base material. Metal film The metal film may be made of a metal, and may be the same material as that of a molding surface of a mold which is well known or sold in the market. For example, metals such as iron, nickel, copper, and chromium, alloys such as nickel magnetic a total turbid phosphorus, gold nickel boron, nickel tungsten phosphorus alloy, and nickel copper phosphorus alloy may be exemplified. Further, the structure of the metal film may be a single layer or a plurality of layers. For example, in order to further improve the adhesion (bonding property) between the heat insulating layer and the metal film, the metal film is a two-layer structure of the first metal film and the second metal film, and the metal film is separated. The case where the thermal layer and the second metal film are used as the adhesion layer (base layer). More specifically, a structure comprising a seed layer formed on the heat insulating layer and containing a plating catalyst, and 2) a metal plating film formed on the seed layer may be employed. That is, the seed layer is a layer made of a metal which can form a catalyst for plating a metal plating film as an upper layer, and is used as a catalyst to form a metal plating film, which is suitable for forming a metal on the heat insulating layer. Membrane. At this time, a stable metal film can be effectively formed regardless of the material constituting the heat insulating layer. Further, in the above-described second metal film, a finely processed metal film which is subjected to fine processing as a layer constituting the molding surface on the surface of the second metal film may be formed as the third metal film. The method for forming the metal film is not particularly limited, and can be appropriately selected from the known methods, such as the metal species to be used, the composition of the layer as the substrate, and the like. For example, electroplating, electroless plating, etc. (liquid phase deposition); thermal CVD, MOCVD, RF plasma CVD, etc.; chemical vapor deposition; sputtering, ion plating, hydrazine, vacuum evaporation One or two or more types of thin film forming methods, such as a physical vapor deposition method such as a plating method, are suitably employed. When the metal film is formed in a multilayer structure, the method of forming each layer may be different, and it may be suitably combined from the film forming method described. For example, when the first metal film as the adhesive layer (base layer) and the second metal film formed thereon are formed as described above, the layers can be formed by the following method, for example, 1) The insulating layer is formed by a sputtering method, and a seed layer (first metal film) of a beer medium (metal catalyst) is forged and coated with the catalyst to form a crystal layer. It is suitable for forming a metal plating film (second metal film). Pushing _ ' '' step, more finely processed metal film as the third metal film

It is possible to form a finely processed M-long film on the metal-plated film of the second metal film. By adopting such a structure, the joint strength between the heat insulating layer and the metal bead can be further improved. The thickness of the metal coating film in the mold of the present invention (in the case of a multilayer structure, the total thickness of each layer) is not particularly limited, but is usually about 20 to 300 / zm, and particularly preferably 5 to 15 inches. The thickness of each layer in the multilayer structure may be appropriately set in accordance with the number of layers, the material of each layer, and the like. Insulating layer The heat insulating layer (also referred to as "heat insulating film") of the mold of the present invention is formed between a metal, a base material, and a metal film constituting a forming surface. Thereby, it is possible to effectively suppress or prevent the phenomenon that the molten molding material has a rapid and rapid take-up of the metal mold base material. In the present invention, the heat insulating layer is composed of a porous body formed by connecting crystal particles of the fat granules into a three-dimensional network. The material of the heat insulating material is also particularly made of a metal granule, whereby a higher heat insulating property can be obtained, and the high adhesion of the metal mold or the metal layer to the base thereof can be exerted. . The structure of the porous body is formed by connecting the crystal particles of the granules into a three-dimensional mesh 201210789. For example, as shown in Fig. 42, a plurality of crystal particles having a polyhedral shape having one or two or more corner portions which are not circular are connected to each other to form a porous body from a three-dimensional network structure. Further, as shown in Fig. 42, it is preferable that a continuous hole is formed in the porous body. The crystal particles of the fat granules may be double crystals or may be a plurality of crystal linkers. Further, it is preferable that the crystal particles constituting the porous structure of the porous structure have a spinel crystal structure. In the present invention, it is preferable that the fertilizer granule has at least one of the following general formulas AxFe3_x04 (wherein A represents a metal which can be substituted with the Fe site constituting the crystal of the spinel type iron oxide, and X satisfies 〇Sx <l.). A compound represented by a spinel crystal structure. Since the aforementioned X system is 0$χ<1, it may include not only x = 0, that is, an iron-based fertilizer body (i.e., spinel-type iron oxide Fe304), but also a part of the Fe site. The composition of other metal element substitutions. As described above, the above-mentioned A is not limited to at least one metal element which can be substituted with the Fe site constituting the crystal of the spinel-type iron oxide, and particularly, Ca, Ζη, Μη, Al, Cr, Li, and Mg are used. At least one of them is preferred. Therefore, in the present invention, at least one of the components A, Ca, Ζη, Μη, A, Cr, Li, and Mg may be used. Such a composition itself is well known, for example, Ca〇.5Fe2.5〇4, ZnFe2〇4, MnFe2〇4, AlFe2〇4, CrFe2〇4, Lio.5Fe2.5O4, At least one of MgFe2〇4 or the like is taken as an example. The thermal expansion coefficient of the heat insulating layer is not particularly limited, and since the metal mold is used under conditions in which the temperature rise and fall are too large and severe, the thermal expansion coefficient of the heat insulating layer is closer to the value of the thermal expansion rate of the metal mold. The better the durability. Therefore, the thermal expansion coefficient of the heat insulating layer is particularly high for gold used at a temperature of 200 ° C or higher; 201210789 South forming temperature; and when the metal is > 1 mold, it is preferably within a range of 90 to 110% of the thermal expansion rate of the extinguishing device. The porosity of the heat insulating layer is not limited, and from the viewpoint of achieving higher heat insulating performance, it is usually about 5 to 75%, and particularly preferably 4 to 15 inches. The porosity can be controlled particularly by synthesis conditions such as synthesis temperature and raw material concentration. The method of mosquitoes of the porosity in the present invention is a method according to the examples described later. Further, the hardness of the heat insulating layer may be appropriately set depending on the type of the material to be formed, and the Vickers hardness (average value) is preferably Hvl30 to Hv560, particularly preferably Hv200 to Hv400. Further, in the present invention, the metal oxide preferably has electrical conductivity. When a thermally conductive layer having conductivity is formed, a base plating layer for forming a finely processed metal coating layer on which a forming surface is formed is formed on the heat insulating layer by electroplating. Thereby, the base plating layer can be formed relatively easily. In this case, the conductivity of the oxide constituting the heat insulating layer is not particularly limited, and the conductivity at 25 ° C is usually 40 S/m or more. The content of the metal oxide in the heat insulating layer is preferably from a viewpoint of heat insulating properties and adhesion, and is preferably 90% by weight or more in the heat insulating layer, and 98% by weight. The above is especially good. Further, the thickness of the heat insulating layer may be appropriately set depending on the type of the molding material to be used, the heat insulating property expected, and the like, and it is generally set within a range of 15 # m or more. In particular, it is preferably 15 to 1 〇〇〇//m. Further, it is preferably 30 to 150 μm. By setting the thickness of the heat insulating layer within the above range, the mold shape (substrate surface) as the base can be more effectively drawn with a uniform film thickness. 20 201210789 The heat insulating layer of the present invention may be suitably used by using the surface of the 1) metal mold base material or 2) the surface of the metal layer previously formed on the surface of the mold base material and the aqueous solution or water dispersion containing the metal component. The body (hereinafter also referred to as "treatment liquid".) The reaction (wet reaction, especially hydrothermal synthesis reaction) is produced. In this way, it is possible to maintain the standard heat insulating properties equivalent to the heat insulating layer of the conventional article, and to exhibit excellent film thickness uniformity, such as adhesion, and as a result, it is possible to accurately reproduce (depice) the substrate as a base. The effect of the mold shape (concave shape). The reaction with the treatment liquid can also be carried out under the conditions of a well-known wet reaction (hydrothermal synthesis reaction). Preferably, it may be carried out according to the method described in the following 2. Metallic layer The heat insulating layer of the mold of the present invention may be directly formed on the surface of the metal mold base material, or the metal layer (heat insulating film base layer) may be used as a base layer of the heat insulating layer. In this case, the metal layer is preferably formed by contacting both the surface of the metal mold base material and the heat insulating layer. Further, the composition of the metal layer is not particularly limited as long as it is composed of a metal, and a metal exemplified in the metal film can be used. In the present invention, it is particularly preferable to contain a metal element constituting a composition of the heat insulating layer. g卩, since the heat insulating layer of the present invention can be suitably formed by a hydrothermal synthesis reaction, the surface of the metal layer as a substrate can be dissolved, and the surface layer is formed on the surface of the metal layer to form a heat insulating layer. The core, and using this as a core, forms a homogeneous and tightly sealed insulation layer. Therefore, when the heat insulating film is formed into a ferrite layer of iron oxide, it is preferable to have a metal layer containing metal iron (particularly, a metal iron structure layer). 21 201210789 In the present invention, the metal layer may be composed of a single layer or a plurality of layers. For example, the metal layer may be 1) a metal layer composed of a seed layer and a metal plating film, 2) a metal layer composed of one or more metal plating films, or the like. Therefore, the formation of the metal material may be carried out in accordance with the structure of the metal layer, etc., and the film formation method exemplified in the formation of the metal beryllium is suitably employed. For example, a method comprising the steps of: forming a surface of a metal mold base material into a layer of aa of a metal mold base material and forming a metal plating film by a plating method on the seed layer; 2) A method of forming a metal plating film by a plating method on the surface of a metal mold base material. The thickness of the metal layer may be appropriately determined according to the type of the metal element constituting the metal layer, the thickness of the heat insulating layer, and the like, and is usually in the range of about 1 to 5 " m. Molding material The material (molding material) for which the heat insulating mold of the present invention is applied is not limited, and is particularly suitable for a wire containing a component of a component (a resin containing a resin component as a main component). It is also suitable for resin molding. Resin component (special; I: synthetic resin) can be polyethylene, polypropylene, polystyrene, polyethylene, polydecyl decyl acid, polyamine, polycarbonate, ABS resin A thermoplastic resin such as ruthenic acid oxalic acid or polytetraethylene is also preferable as a polycyclic ring. Other ingredients may also be included in the above composition as needed. Use of Insulating Mold The insulating mold of the present invention can be used in the same manner as the well-known or commercially available molds 22 201210789. Further, the molding conditions and the like at the time of molding using a mold can be carried out according to a well-known method. When molding using the mold of the present invention, the mold of the present invention can be used as part or all of the molding space constituting the mold. For example, at least one of the fixed mold and the movable mold can be formed by injection molding by forming a molding space formed by fixing the mold and the movable mold into two molds. Further, only part or all of the commercially available mold (forming apparatus) may be replaced with the mold of the present invention. The molding of the mold of the present invention may also be carried out. Fig. 25 is a view showing an example of a step of forming a mold using the mold of the present invention as a movable mold in a mold composed of a fixed mold and a movable mold. In Fig. 25, the molding apparatus can use a mold composed of a fixed mold 3〇1 and a movable mold 401. After the resin r is injected in a molten state and introduced into a space (forming space) between the fixed mold and the movable mold, the resin ruler is cooled while maintaining the pressure as shown in the drawing. Thereafter, the movable mold 4〇1 is lowered, and the mold is released after the mold is released. At this time, the movable mold 401 employs the mold of the present invention, and the forming surface of the mold of the present invention is preliminarily J-shaped. Then, with the heat insulating layer of the mold of the present invention, even when the molten resin is injected and introduced into the forming space of the mold, the heat of the molten resin is not rushed to the mold, and the molten resin can be applied without any dead angle. The unevenness or the groove portion of the molding surface is obtained, and as a result, the shape can be faithfully transferred to the resin side. Thereby, a molded article in which a fine shape is accurately reproduced can be obtained. 2. Method of Manufacturing Insulating Mold The mold of the present invention can be particularly suitably produced by the following method. That is, it is suitable to employ 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 the step of forming the heat insulation layer has the following steps.丨) The surface of the metal mold base material or 2) The surface of the metal layer previously formed on the surface of the mold base material reacts with an aqueous solution or a water dispersion (treatment liquid) containing a metal component to form a metal oxide. The above treatment liquid may be suitably used in the form of an aqueous solution containing a metal component or a moisture dispersion. The metal component may be a component which can constitute a fat granule structure, and particularly preferably Fe, Ca, Zn, Mn, A, Cr, and at least one of them. The preparation of the aqueous solution or the aqueous dispersion described above can be carried out using a compound as a supply source of the metal component. For example, a metal salt, a metal oxide, a metal argon oxide or the like can be used. All of these may be water-soluble (water-soluble) or water-insoluble metal compounds, and in the present invention, it is particularly preferable to use a water-soluble metal compound. Further, the concentration of the metal component in the treatment liquid can be appropriately set depending on the type of the metal component to be used, the reaction conditions, etc., and is usually preferably 〇·〇3 to 3535 g/mL. The above reaction can also be carried out according to a well-known wet reaction method. For example, any one of a method of immersing in a treatment liquid, a method of coating a treatment liquid by spraying, or the like can be employed. In particular, in the present invention, it is preferable to use a treatment liquid to perform a hydrothermal synthesis reaction. The conditions of the hydrothermal synthesis reaction are themselves well known in the art, and in particular, the following methods are preferred. That is, the hydrothermal synthesis reaction preferably employs a method comprising: coating the surface of the metal base material of the metal mold or 2) the surface of the metal layer previously formed on the mold base material thereof with a mixed metal salt, an alkali and The treatment liquid formed by the contact of water is in contact with the state at 100 to 200. (: The step of heat treatment in an environment of saturated steam or more. 24 201210789 In the hydrothermal synthesis reaction described above, it is preferred to use a mixed metal salt, a base, and water in the hydrothermal synthesis reaction. The mixing method is not particularly limited, and the mixing method is not particularly limited. The order of the metal salt may be at least one of a mineral acid salt and an organic acid salt. The inorganic acid salt may be a sulfate, a carbonate, a chloride, etc. Further, the organic acid salt may be an acetate or an oxalate. Further, the 'base is not particularly limited, and at least one of sodium hydroxide, potassium hydroxide, ammonia, etc. may be used. The treatment liquid may be a metal salt or an alkali dissolved in water, or a part of it may be dissolved. Metal salt or alkali is insoluble and dispersible (suspension (water dispersion)). At this time, the content of the treatment liquid towel of the gold material can also be (4) the metal salt used, etc., - the average skin 3~G.35g The /mL is preferably also 〇〇5 to 〇18 g/mL depending on the type of the base to be used, etc. Further, in the present invention, the reaction with the treatment liquid may be carried out in the presence of a reducing agent. Use of reducing agent to inhibit or even prevent 3 in the reaction system The formation of iron ions can form an excellent heat-insulating film more reliably. Therefore, the reducing agent is not limited as long as it can suppress or prevent the formation of trivalent iron ions, and the reducing agent can be appropriately selected. For example, it may be suitably used as a compound known as an ascorbic acid, hydroquinone or the like as an antioxidant. In the present invention, it is preferred that the treatment liquid contains a reducing agent (particularly, a reducing agent is dissolved in the treatment liquid). In the present invention, the treatment liquid is brought into contact with the surface of the base material of the mold base or 2) the surface of the metal layer previously formed on the mold base material. #, Give the treatment liquid to form the barrier. The method of giving is not particularly (four), can be carried out according to the method known in the paint. The use of the treatment liquid "/, to give '^ is sufficient to form a predetermined amount of insulation layer. Therefore, in the present invention, it is suitable for the method of immersing the portion where the heat insulating layer is to be formed in the treatment liquid. The conditions for the liquid reaction are as long as the conditions for the formation of the fertilizer granules, tni. The hydrothermal combination of the special funds should be used as the reaction with the treatment liquid = the temperature and pressure conditions are at (10) ~ · · c (especially ιι〇 ~·.c) = ° water money (four) in the environment under the heat of the temperature, pressure heat treatment, cup / such degree, pressure strip Du Yi, in the formation of pre-heat insulation layer. This warm, 3 again疋 It can be carried out using a well-known device such as an autoclave device (closed system). The whitening and the time of reaction with the treatment liquid (the reaction of the hydrothermal synthesis reaction can be carried out according to the thick material of the hot layer. That is, the reaction may be continued until the heat-insulating film of the thickness of the moon is described, and the heat-sensitive film of the uniform thickness is obtained for the desired thickness, and the hydrothermal synthesis reaction may be carried out. Usually, the method of forming a plurality of times in the range of 2 to 12 hours is formed. In the manufacturing method of the present invention, since it is preferable to form the heat insulating layer of the fat body material described in the above L, it is preferable to use (4) (10) and metal as the metal. Base metal or metal (4). By reacting the surface of the aged metal with the job (especially The thermal synthesis reaction can be adapted to form a fertilizer granule layer as a heat insulating layer. For example, when iron-based fertilizer granules are formed (the foregoing χ=〇), the hydrothermal artificial reaction according to the present invention can be Stages 1) to 2), producing fertilizer granules from iron. Q l) Fe2+ + 0H, Fe(0H)2, 2) Fe(〇H)2-Fe304 The embodiment of the manufacturing method of the present invention according to its layer structure There are various variations 26 201210789, and these are all included in the present invention. For example, in the case of a hydrothermal synthesis reaction (or a usual wet reaction), there are the following methods, etc., which are all included in the present invention. In the manufacturing method, the following method 1) has a step of forming a heat insulating film on the upper layer of a metal mold base material by a hydrothermal synthesis reaction (wet reaction), and forming a seed crystal by sputtering on the surface of the heat insulating film. a step of forming a metal film layer by a plating method on the step of contacting the seed layer; 2) a step of forming a base layer of the heat insulating film on the upper layer of the metal mold base material by a plating method or a sputtering method, Hydrothermal synthesis reaction (wet reaction) step of forming a heat insulation film on the surface of the base layer of the heat insulation film, a step of forming a seed layer on the surface of the heat insulating film, and a step of contacting the seed layer to form a metal film layer by plating; 3) having a metal mold by plating or sputtering a step of forming a base layer of the heat insulating film on the upper layer of the material, a step of forming a heat insulating film on the base layer of the heat insulating film by a water 'thermal synthesis reaction (wet reaction), contacting the upper surface of the heat insulating film by electroplating or sputtering The step of forming a base adhesion film of the metal coating layer and the step of contacting the upper surface of the base film of the metal coating layer to form a metal coating layer by a plating method. EXAMPLES Hereinafter, the present invention will be described, and the present invention will be more specifically described. However, the scope of the present invention is not limited to the embodiment. The first embodiment shows a sectional view of the layer structure of the heat insulating mold of the present embodiment in Fig. 26. The heat insulating mold 1001 is used for a fine micromachined shape. A mold for forming a resin part. This uses pure copper having high thermal conductivity as a material for the mold base material and has the layer structure shown below. That is, on the surface of the mold base material 1002 described below, an iron sulfate plating bath is used, and a heat insulating film base layer 1〇〇3 formed of an iron film having a thickness of 3 μm is disposed on the surface of the mold base material 1002, and the mold base material has a twist of 2.5 mm. The hat-like part (diameter 25.0mm), and the height from the bottom surface is 15.0mm 'diameter 2〇.〇mm, further, the iron-based fertilizer with a thickness of 50/im is formed on the base layer of the thermal insulation film. A heat insulating film 1004 composed of granules (i.e., spinel type iron oxide) is then provided with a seed layer 1005 composed of a catalyst film of palladium, and a metal film layer 1 is formed thereon. 8. The metal film layer 1008 is a finely processed metal film 1007 composed of a base plating film made of nickel (thickness 1 #m) and an amorphous nickel-phosphorus alloy film further formed thereon (average thickness 6/zm) ) constitutes. The forming surface side of the finely machined metal film 1007 is formed as a precision machined surface 1?7a which is formed by machining a fine pattern for press forming of a molded part having a maximum depth of 3" m. According to the above structure, by using a metal oxide (spinel-type iron oxide) having a low thermal conductivity and an oxide material having pores as a heat insulating layer, good resin molding having a fine pattern can be performed. In other words, as seen in the prior art, the heat of the molten resin of the high temperature formed on the forming surface of the metal mold passes through the mold base material, and as a result, it is possible to effectively prevent the temperature of the resin from being lowered to more than necessary during the molding. The formation is not good. Fig. 27 shows an example of a manufacturing procedure of the heat insulating mold 1〇〇1 of the present invention. On the surface of the molding surface side of the mold base material 1G G 2 , an iron sulfate bond bath was used to form a heat insulating film base layer 1〇〇3 (Fig. 27) composed of an iron film having a thickness of 3/zm. Then, a heat-insulating film 1_ (Fig. 27 (2)) composed of spinel-treated iron is formed on the surface. The heat insulating film surface was formed as follows. That is, '6Qml of water prepared by steaming in a nitrogen atmosphere is dissolved in 41 7g of sulfuric acid 28 201210789; g of sodium argon oxide (NaOH) is dissolved in water to put the above suspension into an aqueous solution of internal iron (?68〇4.7112〇) It was mixed with 60 ml of 21.6 liquid to prepare a suspension. 2 (4) Steel high-pressure system should be allowed to contain, the mold base material of the insulating base layer 1003 is immersed in it, and the heart is given to (4). Mode

Row. The high pressure dad reaction vessel was heated from the outside to react for 10 hours. After the reaction, the mold base material was taken out together with the jig, and it was sufficiently washed with water to separate it from the powder compound of the reaction residue formed at the same time. The high-pressure dad reaction vessel is also used to remove the generated reaction residue, and the inner water is washed again and mixed with the same amount of the above suspension, and then the mold base material is installed together with the jig, and similarly, the reaction is carried out at 150 ° C. After 10 hours, a heat-insulating film 1〇〇4 having a film thickness of 50#m was formed. In this manner, the mold in which the heat insulating film 1〇〇4 is formed is washed with water and sufficiently dried, and a palladium particle film is formed on the surface of the heat insulating film 1004 by using a DC sputtering device to which a palladium target is attached. The seed layer 1005 is formed (Fig. 27 (3)). Then, the base plating film 1〇〇6 composed of a nickel film having a thickness of 1/zm is coated by an electroless nickel plating method. Further, a fine-worked metal film 1007 composed of a nickel-phosphorus alloy film for precision machining having a thickness of 6 #m is formed by electroless nickel plating, thereby forming a metal film layer 1008, and heat-treating at 200 ° C for 3 hours ( 27 (4)). Then, using a precision cutting machine to form a precision machined surface l〇〇7a, a heat insulating mold 1001 for a micromachining mold was obtained (Fig. 27 (5)). Further, 'the method of forming the insulating film base layer 1003 from the iron film formed on the surface of the mold base material 1002. In the present embodiment, an example of the method by the keying method is described. The substrate may be a metal film composed of a metal element forming the heat-insulating film directly under the heat-insulating film. Moreover, the method of forming the metal film is not limited to those described in the plating method of the present embodiment. For example, the iron film may be directly formed on the surface of the mold base material by sputtering. According to the above steps, the heat-insulating film of the present invention is different from the mold in which the conventional zirconia spray film is used for the heat-insulating film. It is not required to be subjected to post-processing such as precision grinding, and can be directly formed on the forming surface side of the metal mold. The thickness of the period. In the heat-insulating film 1004, in order to confirm whether or not a film of the desired material is formed, a rectangular substrate (size: length 50 mm, width 20 mm, thickness 2.0 mm) of the same material (pure copper) as the mold base material 1002 is prepared, and the substrate is used. , a thermal insulation film is formed. The obtained sample was used as the heat insulating film A, and the material was evaluated in detail. The method of producing the heat insulating film A will be described below. First, in the same manner as the step of producing the above-described heat insulating mold 1001 (Fig. 27), the same heat insulating film underlayer is formed on the surface of the substrate. Thereafter, similarly to the heat insulating film 1004 of the heat insulating mold 1〇〇1, the same autoclave reaction vessel was used in the same composition in which the same composition was prepared, and the same hydrothermal synthesis conditions were used. The reaction was repeated at 150 ° C for 5 times for 1 hour (repeated 6 times in total), and a heat-insulating film A having a film thickness of 15 inches was prepared. Here, the reason why the film thickness is formed to be larger than the film is to evaluate the porosity and Vickers hardness which are described later in the same sample in addition to the composition and crystal structure required for the material defining the film. . The film-based black film formed on the substrate was thus carried out. About the film, 30 201210789 The composition was investigated using a fluorescent x-ray device. As a result, it is known that the metal ion is composed of only a compound composed of iron. Further, the crystal structure was investigated by ray diffraction analysis. As a result, it was found that the crystal lattice constant % = 8 4 of the spinel-type iron oxide (= iron fertilizer granule), and FqOc, that is, the heat-insulating film 1 〇〇 4 was confirmed to be spinel-type iron oxide. The ray diffraction pattern is shown in Fig. 28. Further, in Fig. 41, a scanning electron microscopic image of the surface after the formation of the film of the heat insulating film a is shown. It is understood that the film structure is formed such that the film structure is sharp and the crystal particles having different sizes are connected, and the three-dimensional mesh structure is formed. Further, as a result of further observation, it was found that a crystal film in which the crystal grains of the twin crystal day and day were continuously grown into a three-dimensional film and a porous film having a structure in which numerous pores exist inside the film were formed. A granular granule ceramic material which is a type of oxide containing iron as a material which is machined into a complicated shape such as a free-cutting process, and is a material which is used as a core material of a magnetic head by fine processing. The heat insulating film of the present invention is an iron-based fertilizer granular material having the same spinel crystal structure as the above-mentioned fat-granular ceramic material, and is a material which is easy to be machined. Therefore, when the heat-insulating film A formed in the present embodiment is gradually polished from the surface and observed by a scanning electron microscope, it is understood that the heat-insulating film is present on the film surface. Open pores, there are also many closed pores. Therefore, in forming the heat insulating film, a smooth surface is formed by surface grinding, and the porosity is measured by a simple method of measuring the ratio of the concave portion of the pore to the entire smooth surface including the pores formed by the polishing. First, with a smooth polished surface required for porosity measurement 31 201210789

The sample was produced as follows. Using the polishing sheet No. 1000, the surface of the heat insulating film A was roughly ground from the surface of the film to a depth of about 30 to 5 〇 β m . Next, using a 4th honed polished sheet composed of a polishing material of alumina fine powder, the coarsely polished surface was hand-polished to prepare a sample having a polishing surface for measuring porosity. Next, regarding the heat insulating film A, the measurement area of the porosity is extracted, and the smooth polished surface is observed by a scanning electron microscope (SEM), and the degree of surface roughness is extracted from the entire surface of the sample. The whole sample appears to be flat on one side of the square 〇15. For each of the square areas extracted by SEM observation, as shown in the fourth section (shown in the figure, using the method of measuring the non-contact surface roughness using a laser microscope), the length is 150 "m, width 150/zm. The measurement of the unevenness in the depth direction of the square region is performed. The magnification of the corrected laser beam is 2 times. Then, the upper lateral side of the square region is cut (the image of the cross section of the straight portion of the length is obtained in the obtained cross section) In the depth profile of the uneven shape (Fig. 40(b)), the sum of the distances in the horizontal direction from the surface to the depth of the concave portion is determined, and the ratio of the total distance of the unevenness measured by the laser microscope is obtained (Fig. 40 (4)) Let the percentage of the pores present on the measurement line, that is, the porosity pa丨. Similarly, the length 150_ every 25_, in parallel with the upper side of the above square area, 'pull out the two ends of the joint 6 straight lines, the porosity corresponding to each straight portion is obtained from the cross-section of the cross-section of the straight portions, and the respective porosity μ~ρ&7 obtained from the seven straight portions The value of the sum average 'as the above square Porosity h of the shape region. 32 201210789 For the heat-insulating film A, the porosity Pa, Pb, Pc, and Pd of the square region of one of the above four sides of 150 μm are obtained, and the heat-insulating film is calculated from the sum of the average values. The porosity P of A. Further, regarding the porosity, the measurement error in the sampling of the measurement region is considered, and it is displayed as a value of P per 5% as the value of the porosity P of the thermal insulation film A. The porosity of the heat-insulating film A was 55%. The scanning electron microscope image of the polishing surface of the heat-insulating film A in which the porosity was measured was measured in Fig. 29. Further, the heat insulation was measured using a Vickers hardness tester. Vickers hardness of film A. The Vickers hardness tester used has a regular quadrangular diamond indenter and the hardness is measured under the condition of a test load of 5 〇g. The sample for the thermal insulation film used for the measurement is not susceptible to heat insulation. The influence of the hardness of the substrate of the film substrate is determined by measuring the film cross section of each of the heat insulating film samples for the measurement of the porosity. The method of grinding the heat insulating film is the same as the method of measuring the respective porosity, and the smoothing is performed. The cross section is used as a surface for Vickers measurement. Fig. 30 is a view showing the polishing cross section of the heat insulating film a. There are many abrasive smooth surface areas which can be pressed into the size of the diamond indenter for evaluation, and the Vickers hardness can be measured by pressing the Vickers indenter. The measurement was carried out by measuring any 12 of the regions formed by the smooth surface in the surface of the polishing cross section shown in Fig. 30. As a result, it was synthesized under the same reaction conditions as the thermal barrier film. The heat-insulating film A has a Vickers hardness maximum value of Hv407, a minimum value of Hvl9〇, and an average value of Hv257. _ Next, the heat of the heat-insulating film sample a with the above-mentioned porosity of 55% is selected. The synthesis conditions 'the production of the heat insulating film sample B having a porosity different from that of the heat insulating sample A was attempted. 33 201210789 The formation of the thermal barrier film B is carried out as follows. That is, 60 ml of water prepared by distillation in nitrogen gas was dissolved in an aqueous solution of 10 g of ferrous sulfate (FeS04 · 7H20) and 21.6 g of hydrogen in the same aqueous solution as the aqueous solution for the synthesis of the heat insulating film A. A 60 ml portion of a sodium oxide (NaOH) aqueous solution was mixed to prepare a suspension. The suspension as the starting material 'using the same reaction vessel as the synthesis of the heat insulating film A' will form an insulating base layer (the same iron film as the heat insulating base layer 1003 of the heat insulating mold 1). The sample substrate was dipped therein and held using a jig. Further, the above work was carried out in a nitrogen atmosphere. This high pressure helium reaction vessel was heated from the outside and reacted at 140 ° C for 12 hours. After the reaction, the sample substrate is taken out together with the jig, and at the same time, it is separated from the powder compound of the reaction residue, and sufficiently washed with water. The autoclave reaction vessel was similarly washed with water to remove the reaction residue, and then re-blended with the same amount of suspension as above. The mold base material was again mounted together with the jig, and reacted at 140 ° C for 12 hours in the same manner. By repeating this operation a total of 8 times, a heat insulating film B having a film thickness of 15 〇vm was formed. The heat insulating film B thus obtained is also a black film. With respect to this film, the composition, crystal structure, and porosity were investigated in the same manner as the heat insulating film A. As a result, the heat insulating film B was also the same spinel type iron oxide Fe3〇4 having the same lattice constant a 〇 = 8.40 A as that of the heat insulating film a. Further, the surface after the formation of the film of the heat-insulating film was observed from a scanning electron microscope (SEM), and as in the case of the heat-insulating film A, a sharp angle was formed, and the crystal grains of the twin crystal were continuously observed. It grows into a three-dimensional film' and forms a porous film in which numerous pores are present inside the film. In the same manner as the heat insulating film A, the porosity and the Vickers hardness of the heat insulating film B were measured, and the porosity was 40%, the Vickers hardness maximum was Hv435, the minimum 34 201210789 was Hv239, and the average value was Hv298. Fig. 31 shows a scanning electron microscope image of the polished surface of the thermal barrier film B in which the porosity was measured. Evaluation of the heat insulating properties The heat insulating properties of the two types of the heat insulating film A and the heat insulating film b were evaluated in the same layer structure as the heat insulating mold of the present invention. The measurement samples 1011A and 1011B for heat insulation evaluation including the heat insulating material a or B and having the same material and the same structure were produced. Fig. 32 is a schematic cross-sectional view showing a sample 1011A in which the heat insulating film a is disposed. The measurement sample 1〇11B differs only in the case where the material of the heat insulating film is the heat insulating film B, and the other is the same structure as the structure shown in Fig. 32. The measurement sample 1011A was produced as follows. First, a round bar having a diameter of 10.0 mm and a length of 44.0 mm and having the same material as that of the mold base material 1002 used for the heat insulating mold of the present embodiment was prepared, and a diameter of 3.5 mm and a depth of 22_0 mm were formed at the center of one end surface thereof. The thermocouple is mounted with a hole 1012a to form a substrate 1012 of a metal round bar. Using this substrate 1012, in the same manufacturing method as that shown in Fig. 27, a thickness of 3//m is formed from the bottom of the end face at a position opposite to the end face having the thermocouple mounting hole 1012a to a position of 30.0 mm. The heat insulating film base layer 1013 composed of an iron film is then formed thereon with a heat insulating film 1014 composed of the heat insulating film A of the present invention having a thickness of 50 μm. Next, a resin mask is applied from the end surface of the thermoelectric mounting hole 1012a, and a seed layer 1015 composed of a very thin palladium catalyst particle film is formed by sputtering from the bottom of the end surface to a position of 23.0 mm. The base mineral film 1 〇 16 (thickness l " m) composed of nickel is formed by electroless plating, and further, an amorphous nickel-phosphorus alloy film having a thickness of 6 " m is formed thereon by electroless nickel plating. The ore metal film 1〇17' is formed to form a metal film layer 1018 composed of a base mineral film 1016 and a mineral metal 35 201210789 film 1017. The measurement sample 1011B is a measurement sample prepared by forming a heat-insulating film made of heat-insulating film instead of the heat-insulating film 1014 formed of the heat-insulating film A in the measurement sample 1〇1 JA shown in FIG. . In order to compare the evaluation of the heat insulation, it was also produced without a thermal insulation film. < Comparative sample 1211. The structure of this comparative sample is shown in Fig. 33. It is prepared to be processed into the same shape of the substrate 1212 in the same material as the above substrate 1012, and is retained from the bottom of the end face to 23. At a position of 0 mm, resin shielding was performed on the end face side of the thermocouple mounting hole 1212a. Thereafter, a wood strike plating bath is formed by wood to form a base 1 film 1216 made of a nickel-plated film, and then formed by a thickness-free amorphous nickel-phosphorus alloy film by electroless plating. The metal film 1217 is plated to form a metal film layer 1218. In this manner, a measurement sample 1211 was produced. The three kinds of measurement samples 10UA, 1011B, and 1211 produced in this manner were evaluated as follows, and the heat insulating properties were evaluated. Fig. 34 is a schematic cross-sectional view showing the heat insulating property evaluation device 21 used in the present embodiment. This apparatus is made of a rigid foamed styrene resin of the same size, which is composed of a transparent glass beaker, and is made of a rigid foamed water tank 23, a cold water constant temperature water tank 23, and three measurement samples 1011A, 1011B, and 1211. The upper surface of each of the thermostatic chambers can be formed into a size of a cover (square, size 20 cm) and a heat-insulating plate 1〇24 having a thickness of 5 mm. The electrothermal heater 25 is disposed below the constant temperature water tank 22 for high temperature water, and is formed into a heatable structure. Next to this, the cold water temperature control water tank 23 is mounted on the table 26 at the same height. The diameter of the heat insulating plate 1024 is 10. Three of 〇mm are inserted through 36 201210789 holes, and the measurement samples 1011A, l〇UB, and 1211 are disposed so that the metal bead layer is formed, and the end face of the sample is measured to 2 mm & Exposed to the lower part. In each of the measurement samples, thermocouples 18, 118, and 218 are attached to the I-couple female hole provided at the other end surface, and these are connected to the respective temperature display meters 19, 119, and 219, and are formed to be displayable. The structure of the temperature of the substrate of the metal round bar of the sample was measured. In addition, in order to reduce the influence of the outside air temperature on the temperature measurement result, each measurement sample is 1〇11, 1〇nB, 12丨1, and the upper part connected to the thermocouple is completely shielded from the heat shield. The upper side is exposed to the outside, and is covered with a foamed styrene resin insulating cover 27, 28' 29 of exactly the same shape. The two constant-temperature water tanks 22 and 23 are placed in high-temperature water and cold water to be immersed in the portion from the lower end surface of the three kinds of measurement samples 1011A, 1011B, and 1211 mounted on the heat insulating plate 24 to 15 mm. During the measurement, the high-temperature water constant temperature water tank 22 uses the electric heater 25 to adjust the water temperature to a constant temperature, and the cold water is replaced with cold water by the constant temperature water tank 23, and is kept at a constant water temperature. In the heat insulation evaluation of the heat-insulating film of the present invention, the three measurement samples 1011A, 1011B, and 1211 which are kept at a constant temperature are placed in the heat insulating plate 1024 and simultaneously immersed in the heat insulating property evaluation device 21 The constant temperature water tank 22 was kept at a high temperature of 95 ° C, and the temperature rise rate was measured. Thus, the heat insulating effect at the time of temperature rise was examined for 5 weeks. Next, the measurement samples 1011A, 1011B, and 1211 whose temperature has risen are directly immersed in the water of 32 ° C while being immersed in the constant temperature water tank 23 while being mounted on the heat insulation board 24, and the speed at which the temperature is lowered is measured. Therefore, the insulation effect at the time of cooling was investigated. Fig. 35 is a graph showing the time variation of the temperature change and the temperature difference between the two measurement samples of 37 201210789, as the temperature rise from the room temperature while being immersed in the constant temperature water tank 22 maintained at 95 °C. The measurement time of the measurement sample 1011A (porosity: 55%) and ioiib (porosity: 40%) of the heat insulating film of the present invention was compared with the measurement sample 1211 which does not have a heat insulation film. In Fig. 36, the measurement samples 1〇11A, 1011B, and 1211 whose temperature has risen are simultaneously immersed and kept at 32. (The measurement result of the time change of the temperature drop in the constant temperature water tank. It is also clear from the results of Fig. 35 and Fig. 36 that the heat insulating film of the present invention has a temperature change to the outside, and it is difficult to transfer heat to the base. Further, it is also known that the measurement sample of the heat insulating film having a larger porosity has a heat insulating effect. The second embodiment shows the cross section of the laminated structure of the heat insulating mold of the present embodiment in the first embodiment. The heat insulating mold 1 is a stainless steel mold for forming a resin material having a fine fine (four) shape, and is composed of the following layer structure. That is, a film is formed on the surface of the mold base material 2 described below. The base layer of the heat-insulating film formed by the thick iron film 3' The aforementioned mold base material has a cap shape of a height of 2.5 mm (diameter 25. 0 drying), and the height from the bottom is 15 〇, the diameter is ugly, and then form a thick buckle on the base layer of the thermal insulation film - the iron-based fertilizer granules (ie, spinel-type iron oxide The spacer film 4 is formed, and the seed layer 5 composed of the mosquito catalyst fine particle film is placed thereon, and then the metal film layer 8 is placed upright. This metal film layer 8 is composed of (4) a finely processed metal film 7 (average thickness of one m) composed of an amorphous nickel-phosphorus alloy film formed by a thickness of 2 (four) and a step formed thereon. This fine processing 38 201210789 The forming surface side of the metal film 7 is formed as a precision machined surface 7a in which a fine pattern for press forming of a molded part is machined. The manufacture of the heat insulating mold of this embodiment was carried out in the same manner as in the first embodiment. An example of the manufacturing steps is shown in Fig. 2. On the surface of the molding surface side of the mold base material 2, an iron sulfate plating bath was used to form a heat insulating film base layer 3 composed of an iron film having a thickness of 3/m. Then, a heat insulating film 4 made of spinel type iron oxide having a thickness is formed on the surface. The heat insulating film 4 is formed as follows. First, 60 ml of water produced by distillation in nitrogen was dissolved in 41. 7g of ferrous sulfate (FeS〇4. 7H2〇) aqueous solution and 21. 6 g of a sodium hydroxide (Na〇H) aqueous solution was mixed in 60 ml to prepare a suspension as a treatment liquid. The suspension was placed in a 200 ml stainless steel autoclave reaction vessel, and the mold base material on which the heat insulating base layer 3 was formed was impregnated therein and held by a jig. The mold base material was previously shielded with a sealing tape made of tetrafluoroethylene to form a molding surface of the heat insulating base layer 3. Further, the above work was carried out in a nitrogen atmosphere. The high pressure dad reaction vessel was heated from the outside to 150. 〇Reaction for 10 hours. After the reaction, the mold base material was taken out together with the jig, and separated from the powder compound formed at the same time, and sufficiently washed with water. The high-pressure dad reaction vessel is also similarly taken to remove the powder (the powder is formed, and the internal water is washed, and the same amount of the suspension is replaced again, and then the mold base material is installed together with the missing piece, the same as '150° C was reacted for 10 hours, and this operation was repeated for a total of 6 times to form a heat-insulating film 4 made of spinel-type iron oxide having a film thickness of 15 Å #m. Thus, the mold having the laminated film was washed with water. After it is sufficiently dried, a palladium particle film is formed on the surface of the heat insulating film 4 by using a DC sputtering device equipped with a palladium target material, whereby the seed layer 5 is formed. Next, the electroless nickel is applied at the time of no electricity 39 201210789 And coating a base coating film composed of a nickel film having a thickness of 2/m, and forming a finely processed metal film 7 composed of a recording film alloy film of a precision processing thickness of 15 〇em by electroless nickel plating method, whereby After the metal coating layer 8 was produced, heat treatment was performed at 200 ° C for 3 hours. Then, the precision machined surface 7a was formed by a precision cutting machine to obtain a heat insulating mold 1 for a fine processing die. 'Do you want to end up? The film of the desired material is additionally prepared as a square plate of the same material as the base material 2 of the mold (size.  18. 0mm square, thickness 2. 0 mm), in the step of producing the above-mentioned heat insulating mold, the same 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 sample of the square plate is also placed in the same autoclave reaction container together with the heat insulating mold 1, and the square plate sample is also separated. The hot film 4 simultaneously forms a heat insulating film. The same material evaluation as in the first example was carried out on the film formed on the square plate. The results of the analysis of the composition of the Yingguang X-ray device are combined with. As a result of analysis of the X-ray diffraction pattern (Fig. 3) obtained by X-ray diffraction, it was confirmed that the heat insulating film 4 has the same lattice constant as that of the heat insulating film 1004 shown in the first embodiment. =8. 4 The tip of the monk is a spar-type iron oxide Fe3〇4. Further, the heat insulating film 4 has a porosity of 55%, a Vickers hardness Hv maximum of 410, a minimum value of 180, and an average value of 265. The evaluation of the heat insulating property is to evaluate the heat insulating performance of the heat insulating mold of the structure of the present invention, and the heat insulating film of the present invention is prepared, and the heat insulating property evaluation sample 11 composed of the same material and the same structure is produced. . A schematic cross-sectional structural view is shown in Fig. 4. This measurement sample 11 was produced as follows. First, prepare the diameter 40 201210789 9. 5mm, length 45_0mm, and the same material as the mold base material 2 used for the insulating mold 1 of the structure of the present embodiment, the diameter of the round bar is formed at the center of one end face thereof. 5mm ‘depth 22. A 0 mm thermocouple mounting hole 12a. Further, in order to make the heat insulating film formed on the upper surface excellent in adhesion, a concave and convex groove having a pitch of 125 β m and a depth of 15 μm was formed on the entire surface of the round bar, and the substrate 12 of the metal round bar was produced. . The substrate 12 is used in the same manner as the heat insulating mold of the present embodiment, from the bottom end of the end surface opposite to the end surface having the thermocouple mounting hole 12a to 30. At a position of 0 mm, a heat insulating film base layer 13 composed of a thick iron film was formed, and then a heat insulating film 14 made of the spinel type iron oxide of the present invention having a thickness of 150 / / m was formed thereon. Then, resin shielding is performed on the end surface of the thermoelectric mounting hole 12a, and the seed layer 15 composed of the extremely thin palladium catalyst fine particle film is formed by sputtering from the bottom of the end surface to the position of the 23 claws. A base plating film 16 (thickness 2/zm) composed of nickel is formed thereon by electroless nickel plating. Further, an amorphous nickel-phosphorus alloy film having a thickness of 18 #m is formed by electroless nickel plating. The metal film 17 is plated to form a metal film layer a composed of the base mineral film 16 and the metal film π. For the evaluation of the heat insulating properties, comparative samples of two different structures as shown in Figs. 5 and 6 were also produced. One of the comparative samples has a measurement sample 111 of a conventional heat-insulating film using a ruthenium oxide spray film as a heat-insulating film, and its structure is shown in Fig. 5. The measurement sample m was produced as follows. It is prepared to process the substrate 112 having the same shape in the same material as the substrate of the measurement sample u described above, from the bottom end of the end surface opposite to the end surface having the thermocouple mounting hole 112a to 3 〇〇 Position 'spraying the high-temperature oxidized frequency particles homogeneously into a flat 41 201210789 The average thickness is about 2 5 0, for example, and ^, γ,.  / became a spray film. This refining film is precisely ground to form a thin film to a thickness of 15 G/m, and an oxidized film = a thermal film U4. Thereafter, resin shielding is performed from the end face of the end face to the end face side of the (4) even mounting hole 112a. The treatment step before the release of the month y U and the impregnation treatment of the stannous chloride solution in the test and the subsequent impregnation treatment of the methylene chloride domain form a seed layer of 115 ° on which the seed layer is formed. The underlying plating film 116 (thickness: 2 μm) is formed thereon, and a metal film layer 117 composed of an amorphous age gold film of a thickness core (7) is formed thereon by an electroless magnetic bonding method to form a metal film layer 118. In this manner, a measurement sample ln was produced. Another comparative sample was a measurement sample 211 having no heat insulating film at all. The structure is shown in Fig. 6. It is prepared to process the substrate 212 of the same shape in the same material as the above substrate 12 or 112, from the bottom of the end face to 23. At a position of 0 mm, resin shielding was performed on the end face side of the thermocouple mounting hole 212a. Thereafter, the plating bath was struck with wood to form a base plating film 216 having a thickness of 2/zm composed of a nickel-plated film, and then an amorphous nickel phosphorus having a thickness of 18 vm was formed thereon by electroless nickel plating in the same manner as described above. The alloy film constitutes the money metal film 217, and the metal film layer 218 is formed. In this manner, a measurement sample 211 was produced. The three types of measurement samples 11, 111, and 211 produced as described above were evaluated as follows, and the heat insulating properties were evaluated. The evaluation of the heat insulating property was evaluated in the same manner using the same apparatus as the heat insulating property evaluation device shown in Fig. 34 used in the first embodiment. Here, instead of the measurement samples 1011A, 1011B, and 1211 of the first embodiment, the measurement samples 11'111 and 211 of the present embodiment are placed in a heat insulating property evaluation device and measured. In addition, the heat insulation plate holding the three measurement samples is provided with a diameter of 9. The heat insulating plate 24 of the three through holes of 5 mm replaces the heat insulating plate 1024 used in Fig. 34. The state at the time of evaluation of this measurement is shown in Fig. 7. In the evaluation of the heat insulating property, the three measurement samples 11, 111, and 211 which are placed at room temperature and held at a constant temperature are simultaneously immersed in the heat insulating property evaluation device 21 shown in FIG. The thermostatic water tank 22 was kept at 90 C of warm water, and the temperature rise rate was measured, thereby investigating the heat insulating effect at the time of temperature rise. Then, the measurement samples u, m, and 211 whose temperature has risen are directly immersed in the cold water maintained at 20 ° C in the constant temperature water tank 23 while being attached to the heat insulating plate 24, and the temperature is lowered. In this way, the insulation effect during cooling is investigated. Fig. 8 is a graph showing the time variation of the temperature change between the temperature rise and the temperature difference between the two measurement samples as a time change with respect to the temperature rise when immersed in the constant temperature water tank 22 maintained at 9 °C from room temperature. The measurement result of the measurement sample nail of the heat insulation film of the present invention is provided in comparison with the measurement sample 211 which does not have a heat insulation film. Fig. 9 shows the measurement results of the time when the temperature of the measurement samples u and 2, which have been raised in temperature, are simultaneously immersed in the temperature drop of 2 (TC strange temperature water tank). Similarly, the conventional heat insulation is provided. The measurement sample lu is shown in the first and fourth figures in the same manner as the measurement sample of the thermal insulation film of the present invention described above. The results from Fig. 8 to Fig. 11 are also clear. It is understood that the effect of the temperature of the outer surface of the heat insulating film of the present invention on the substrate is clearly '.', 43 201210789 It is also known that the heat insulating effect is almost the same as that of the conventional heat-insulating film. For example, a cross-sectional view of the laminated structure of the heat insulating mold of the present embodiment is shown in Fig. 12. The heat insulating mold 31 is used for a resin molded mold of an optical element having a fine micromachined surface. In other words, a heat insulating layer 34 made of spinel-type iron oxide having a film thickness of 105/zm is disposed on the surface of the mold base material 32 described below, and the mold base material is processed into a substantially formed shape of an optical element. The size of the cylinder is 1〇〇mm in diameter And a lower portion having a diameter of 14. 0mmx height 2. 〇mm's hat shape part, by height 15. 0mm steel material constructor. An adhesion layer 35 made of an iron film having a thickness of 3/zm is disposed on the surface of the heat insulating layer, and a metal film layer 38 is placed thereon. The metal film layer 38 is composed of a nickel base plating film 36 made of a thickness of 2 μm and a finely processed metal film 3 made of an amorphous nickel-phosphorus alloy film having a thickness of 1 m. Further, the surface of the finely processed metal film 37 is a formed transfer surface at the time of resin molding, and is formed into a precision machined surface 37a which is finely processed into a shape of a molded object. Fig. 13 shows the steps of the method of manufacturing the heat insulating mold of the present embodiment. First, the same raw material and the same autoclave reaction vessel as in the second embodiment were used, and the same hydrothermal reaction was repeated four times, and the bar stock made of the steel mainly composed of iron was mechanically processed. The molding surface of 32 is formed of a heat-insulating film 34 made of spinel-type iron oxide having a thickness of 105 # m (Fig. 13 (1)). Further, the mold base material is preliminarily shielded from the molding surface of the mold base material 32 by a sealing tape made of tetrafluoroethylene. 44 201210789 In this way, after the mold in which the heat insulating film 34 is formed is washed with water, an adhesion layer 35 made of an iron-plated film is formed by an electroplating method using an organic acid iron plating bath of #-like acid (Fig. 13 (2) ). Next, a base plating film 36 made of a nickel film having a thickness of 2//01 was coated by an electroless nickel plating method. Further, the metal film layer 38 is formed by the electroless nickel plating method, and the metal film layer 38 is formed by a precision processing alloy plating film having a thickness of 15 〇em, and is heat treated at 20 (TC for 3 hours). (3)). Thereafter, the surface of the finely processed metal film 37 is machined to form a precision machined surface of the shape of the formed object by using a fine cutting machine, thereby producing a resin for the optical element. The formed heat insulating mold 31 (Fig. 13 (4)). Thus, it is understood that since the spinel type iron oxide constituting the heat insulating film of the present embodiment is a conductive metal oxide, it can be a known manufacturing step. It is regarded as the secret method of reading the precision ceramics (4) and directly forms a metal film. The evaluation of the heat insulation property is to evaluate the heat insulation performance of the above-mentioned heat insulation mold, and the heat insulation film containing the present invention is produced from the same material and the same The thermal conductivity evaluation 4 of the structural configuration is shown in Fig. 14. A schematic cross-sectional view is shown in Fig. 14. This measurement sample 41 is produced as follows. First, 'preparation diameter, length 5: in: and: implementation Example mold base material 32 phase The round bar of #f, the thermocouple measured by ==, in the turn-~ becomes 』==, the thermocouple of the right-handed thermocouple is mounted with a through-hole shape, and the axial direction forms a right angle, and the substrate 42 is fabricated. One end is pre-shielded with a four-air-binder sealing tape, similar to the method of forming the IS film: 45 201210789 thermal insulation film 34, at the bottom end of the end face from the other end 22. A heat-insulating film 44 having a thickness of 1〇5//111 is formed at 0〇1111. Next, keep the bottom of the end face to 20. At the position of 0 mm, the remaining portion is shielded by the resin sealing material. In the same manner as the method of forming the adhesion layer 35 of the heat insulating mold 31, the adhesion layer 45 composed of a mineral iron film is formed, and further, no electric key is used. The ruthenium method was coated with a base film 46 made of a nickel film having a thickness of 2, and a metal film 47' made of a nickel-phosphorus alloy ruthenium for precision machining having a thickness of 28/zm by an electroless nickel plating method. Sample 41. The measurement sample 241 having no heat-insulating film was produced as follows, and was used as a comparative sample for evaluation of the heat insulating property of the measurement sample 41 having the heat-insulating film of the present invention. A schematic cross-sectional view is shown in Fig. 15. The substrate 242 having the same shape as that of the above-mentioned substrate 42 is prepared, and is retained from the bottom of the end face to 20. At a position of 0 mm, resin shielding was performed on the end face side of the thermocouple mounting hole 242a. Then, a base plating film 246 having a thickness of 2 made of a nickel-plated film is formed by electroless nickel plating, and then an amorphous nickel-phosphorus alloy film having a thickness of 28 "ιη is formed by electroless plating in the same manner as above. A metallized film 247 is formed. In this manner, the measurement sample 241 was produced. The measurement samples 41 and 241 produced in this manner were changed to have a diameter of 6. In addition to the measurement samples 41 and 241, the device having the same configuration as that of the heat insulation evaluation device 2 used in the first embodiment is used for the simultaneous heat insulation in the same manner as in the first embodiment. Evaluation of sex. In addition, the heat insulating properties were evaluated by immersing the measurement samples 41 and 241 attached to the heat insulating film 24 from the lower end surface to a portion of 15 mm in the high-temperature water and cold water stored in the constant temperature bath. 46 201210789 Figure 16 shows the time change of temperature rise from room temperature while immersed in a constant temperature water bath maintained at 95 ° C. Compared with the measurement sample 241 without a heat shield film, the heat insulation of the present invention is provided. The measurement result of the measurement sample 41 of the film. In Fig. 17, it is shown that the measurement samples 41, 241 whose temperature has risen are directly at different temperatures, and then immersed at 18 at the same time. The measurement result of the time change of the temperature drop in the warm water tank. As is clear from the results of Figs. 16 and 17, it is understood that the effect of the heat-insulating film of the present invention on the external temperature change is not easy to transfer heat to the substrate as in the results of the third embodiment. Further, in the same manner as the above-described measurement sample, the measurement sample 341 having a thickness of 15 / zm and a measurement sample 441 having a thickness of 3 m in thermal insulation film were prepared, similarly to the above-described heat insulation measurement. Three samples of the measurement sample 241 not having the heat insulating film were evaluated. However, the heat insulation properties were evaluated by immersing the portions of the three test specimens 241, 341 '441 from the lower end surface to 19 mm in the high temperature water and cold water stored in the constant temperature bath. In Fig. 18, the time change of the temperature rise from the room temperature while being immersed in the water bath maintained at 95° is shown, and the present invention is provided in comparison with the measurement sample 2 41 without the heat insulating film. The measurement result of the measurement sample 3 4 4 4 4 i of the heat insulating film. Fig. 19 shows the time change of the temperature drop when the measurement samples 24, 341 and 441 whose temperature has risen are directly at different temperatures, and then simultaneously immersed in a warm water bath maintained at 27 °C. As is clear from the results of the first and third figures, it is understood that the heat-insulating film of the present invention has a film thickness of 15 " m as compared with the results of the third embodiment, and it is difficult to transfer heat to external temperature changes. The effect on the substrate is still clear. 47 201210789 Fourth Embodiment As shown in the first embodiment, by selecting the reaction conditions for hydrothermal synthesis, it is possible to form a heat-insulating film having different porosity which greatly affects the heat insulating performance. In the present embodiment, three types of heat insulating red, D, and E having different porosity were produced by various changes in hydrothermal synthesis conditions. Further, in the hydrothermal synthesis, all of the raw material solutions were prepared by using water saturated with nitrogen. The base substrate used for the formation of the heat-insulating film is assumed to be an iron mold, and three rectangular substrates made of iron are prepared (size: length 5 mm, width 2 mm, thickness 2. 0 mm) ' Each of the heat insulating films is formed on the surface of the substrates. The heat insulating film C is formed as follows. Will dissolve in water 6〇ml 38. 3g of ferrous sulfate (FeS〇4 · 7H2〇) aqueous solution and 29. 7 g of a sodium hydroxide (NaOH) aqueous solution was mixed at 6 〇mi to prepare a suspension. The suspension was placed in a high-pressure dad reaction vessel of the same shape as that of the user of the first embodiment, and a dislocation was used, the base substrate was held, and the reaction vessel was sealed, and the reaction vessel was sealed. maintain. After 45 hours, the pressure inside the reaction vessel rose to 0. 2〇MPa. Thereafter, the heating is stopped, the pressure valve is opened, the internal pressure is released, and the reaction vessel is opened, and the sample substrate is taken out together with the jig while being separated from the reaction residue, and sufficiently washed with water. Thereafter, the reaction vessel was similarly removed to remove the reaction residue, and the inside was washed with water, and the same amount of the above suspension was again taken, and the substrate after washing with water was used in the same manner as in the holder. (: Reaction for 45 hours. By repeating this operation, '6 persons' formed a heat-insulating film C having a film thickness of 146/zm. The heat-insulating film C formed in this manner, and the heat-insulating film A of the first embodiment In the same manner, the chemical composition, the crystal structure, the porosity, and the Vickers hardness were investigated using a fluorescent X-ray apparatus, an X-ray diffraction apparatus 48, 201210789, a laser microscope, a Vickers hardness tester, and the like. It can be confirmed that the thermal insulation film c is a lattice crane number a〇=8. 4〇A of spinel-type iron oxide Fe3〇4 〇, it is known that its porosity is 5% ′′, the maximum Vickers hardness is Hv314, the minimum value is 23〇, and the average value is HV278. The method of forming the heat insulating film D is as follows. First, it will be steamed in nitrogen and 60ml of water is dissolved. 7g of ferrous sulfate (FeS〇4.  7h2〇) aqueous solution and 26. A suspension of 0 g of a sodium hydroxide (NaOH) aqueous solution of 6 〇 ml was prepared to prepare a suspension. This suspension was placed in a reaction container having the same shape as that used for the heat insulating crucible C, and reacted with U (rc for 40 hours) in the same manner as in the case of the thermal barrier film C. After the reaction, the substrate on which the film was formed was taken out. The water is thoroughly washed, and the substrate is immersed in a new raw material suspension in a reaction vessel, and the container is sealed to the same size. (: 40 hours of reaction is carried out. This operation is repeated 4 times in total) The film thickness 150 of the thermal insulation film D. The thermal insulation film D is evaluated by the material's result, from the lattice constant a 〇-8. 40A of spinel-type iron oxide fqO4, the porosity, the maximum Vickers hardness is Hv560, the minimum value is Hv303, and the average value is Hv448. The method of forming the heat insulating film E is as follows. First, 60 ml of water prepared by steaming in nitrogen is dissolved in 41. 7g of ferrous sulfate (Fes〇4.  7 〇) aqueous solution and 21. 6 g of a sodium hydroxide (NaOH) aqueous solution was mixed at 6 〇 ml to prepare a suspension. This suspension was placed in a reaction container having the same shape as that for forming the heat insulating film c, and was similar to 145 in the case of the heat insulating film c. 〇 Reaction for 9 minutes. After the reaction, the substrate on which the film was formed was taken out, sufficiently washed with water, and the substrate was immersed in a new raw material suspension in a container of Reaction No. 20121010789, and the container was sealed and reacted at 145 ° C for 90 minutes. This operation was repeated 14 times in total to form a heat-insulating film E having a film thickness of 150 #m. In this way, a black heat-insulating film E was obtained, and as a result of evaluating the material, the heat-insulating film E was made by a lattice constant aQ=8. 4〇A of spinel-type iron oxide Fe304, the porosity of which is 75%. However, the heat-insulating film E having a porosity of up to 75% in porosity cannot be obtained by pressing a Vickers indenter to form a smooth polished surface having a size of a depression of the indentation, so that the Vickers hardness cannot be measured. Fig. 37 shows a scanning microscope image of the polished surfaces of the heat insulating films C, D, and E having different porosity. Further, the surface of the heat-insulating film C, D, and E is formed in the same manner as the heat-insulating film A, and is formed into a film in which a crystal grain of a sharp-angled twin crystal is continuously grown into a three-dimensional film, and is formed in the film. There are numerous porous membranes with numerous pores inside the membrane. It is known that the oxidized error-sintered body or the sprayed film of the conventional heat insulating oxide material has a Vickers hardness Hv of as high as 1200 and is a difficult-to-process material. On the other hand, it is understood that the material of the heat insulating film of the present invention is a material which is low in hardness regardless of the porosity and which can be easily subjected to fine cutting such as precision cutting and precision grinding as in the conventional precision ceramics. The fifth embodiment has examined whether a part of the iron ions forming the spinel-type iron oxide Fe304 is replaced with various metal ions, and whether the replacement fertilizer bodies of various compositions can be hydrothermally synthesized on the substrate. Membrane. These fertilizers and granules have almost no difference in thermal conductivity due to the type of ion exchange, but they can be used as a replacement for the heat-insulating film of the mold due to the change of other material properties such as thermal expansion rate. Forming is important. The formation of the replacement fertilizer granule film of various compositions is carried out in the preparation of the raw material solution, and water which is distilled in nitrogen gas is used. First, the film formation of the lanthanum granules containing calcium ions as replacement ions as the fertilizer granules was attempted. The synthesis of the above-mentioned replacement fertilizer granule film was carried out as follows. In order to confirm whether the desired fat granule film can be formed by the same hydrothermal reaction as the method shown in the first embodiment, the base substrate for bismuth formation and the material evaluation for the thermal insulation film of the first embodiment are used. The same material (pure copper) rectangular opening > substrate (size: length 50mx width 20mmx thickness 2. 0 mm), and the same heat-insulating film base layer (thickness iron film of 3 cm thickness) was formed. It will dissolve in water. 9g of gasified ferrous iron (FeCl2 · 4H20) and 7. 4g of vaporized calcium (CaCl2.  2) 0) aqueous solution 60ml and 21. 6 g of a sodium hydroxide (NaOH) aqueous solution was mixed at 6 ml, and a suspension was prepared as a treatment liquid. The suspension was placed in a stainless steel autoclave reaction vessel having the same internal volume as that of the user of the first embodiment, and the base substrate for evaluation was impregnated therein and held by a jig. . After l5 (rc reaction for 2 hours, the substrate is taken out together with the jig 'is separated from the powder compound formed at the same time' and fully washed with water. The high pressure dad reaction container is also used to remove the raw powder, and will Internal water washing 're-mixing and the same amount of the same as above. Then the mold base material is installed together with the ware, and the same reaction is repeated. The film formed on the substrate is a black film, and the thickness of the film is l〇 4/zm. For this film, using a fluorescent X-ray device, the composition of the composition of eight = jin, which is known as the compound of iron and calcium 'chemical composition (Mo I 51 I) 201210789 iron: feed = 85: 15. The crystal structure was investigated using a xenon ray diffraction device. The \ray diffraction pattern was shown in Fig. 38. As a result, it was confirmed that the display lattice constant a0=8. 4〇A “The composition of the crystal structure of the spar crystal structure. That is, it was confirmed that the obtained film was about granules %45^々4. Further, a scanning electron microscope image of the surface after the film formation of the film was not shown in Fig. 42. In the same manner as the heat-insulating film 8 shown in the first embodiment, it is known that a crystal grain having a sharp-angled twin crystal is continuously grown into a three-dimensional film, and a porous structure having a structure in which numerous pores are present in the film is formed. membrane. Further, in the same manner as in the method shown in Fig. 1, the surface of the film and the cross section of the film were each polished to prepare a measurement surface, and the porosity and Vickers hardness were measured. Fig. 39 shows a scanning microscope image of the surface of the film after grinding. As a result, the porosity was 20%. Further, the maximum Vickers hardness is Hv339, and the minimum value is Ην130, and the average value of these is Ην220. Next, the possibility of film formation of the granules containing the zinc ions as the replacement ions as the fat granules was reviewed. However, here, the evaluation material used a square plate of the same material as the mold base material 32 (steel material) used in the third embodiment (size 18. 0mm square, thickness 2. 0mm). The people are as follows. It will dissolve in water 60ml. 7g of ferrous sulfate (FeS04. 7H20) and 7. An aqueous solution of 2 g of zinc sulfate (ZnS04 · 7H20) was mixed with 60 ml of a 21 - 6 g aqueous solution of sodium hydroxide (NaOH) to prepare a suspension as a treatment liquid. The suspension was placed in a stainless steel autoclave reaction vessel containing 200 ml of the content of the above-mentioned calcium-based fertilizer granules, and the above-mentioned evaluation base substrate was impregnated therein and held by a jig. After reacting at 180 C for 4 hours, the substrate was taken out together with the refreshing device, and separated from the powder compound formed at the same time as 2012 201278, and sufficiently washed with water. The high pressure* reaction vessel is also subjected to the raw red powder for s, (4) (iv) water washing, and the same amount of the above suspension is re-fitted, and then the mold base material is attached to the jig-(four), and the same reaction is repeated four times. The film formed on the square plate was subjected to analysis using a fluorescent xenon ray device. As a result, a compound which is iron and a word was confirmed. However, since the base material of the base material is a steel material, when the composition of the MX ray is analyzed, the composition of the base material (iron) is also added as a composition analysis value, so that the correct composition of the fat granule film is difficult. Only a qualitative analysis of whether or not the replacement metal ion is contained in the composition of the fat body is performed. Further, the crystal structure was examined by X-ray diffraction analysis. The X-ray diffraction pattern is shown in Fig. 22. As a result, it was confirmed that only the lattice constant a 〇 = 8. 49A is composed of a compound of a spinel structure. That is, it was confirmed that the obtained film was a zinc-based fertilizer granule. In the same manner as the production and review of the zinc-based fertilizer and granules described above, the film formation of the fertilizer granules in the case of replacement with the sputum (Μη) ions was examined. Only the following points are different, and the above-mentioned point system will dissolve in water 60ml. 7g of ferrous sulfate (FeS04. 7Η2〇) and 6. 0g of manganese sulfate (MnS〇4 · 5Η20) aqueous solution and 21. 6 g of a sodium hydroxide (NaOH) aqueous solution was mixed at 6 ml, and a suspension was prepared and used as a treatment liquid. The other steps were carried out in exactly the same manner as in the film formation of the above-mentioned rhyolite. The composition of the film formed on the square plate placed in the autoclave reaction vessel was analyzed using a fluorescent X-ray apparatus. As a result, a compound of iron and manganese was confirmed. Further, the crystal structure was investigated by x-ray diffraction analysis. As a result, it can be understood that the obtained film is only composed of a lattice constant ac)=8. A compound of 43A in a spinel crystal structure. That is, it was confirmed that the obtained film was a manganese-based 53 201210789 fat granule. Next, the film formation of the fertilizer granules when the replacement ions were magnesium (Mg) ions was examined. Only the following points are different, the above point will dissolve 34 7g of ferrous sulfate (FeS04. 7H20) and 6. 2g of magnesium sulfate (MgS〇4.  7η2〇) aqueous solution and 21. 6 g of a sodium hydroxide (NaOH) aqueous solution was mixed at 6 〇 ml, and a suspension was prepared and used as a treatment liquid. The other steps were carried out in the same manner as in the film-forming property review of the zinc-based fertilizer granules. Dad responded to the film on the square plate in the barn and analyzed the composition using a fluorescent X-ray device. As a result, a compound which is iron and magnesium was confirmed. Further, the crystal structure was investigated by X-ray diffraction analysis. As a result, it was confirmed that the obtained film was only composed of a lattice constant a0=8. A compound of a spinel crystal structure of 4〇A. That is, it was confirmed that the obtained film was a magnesium-based fertilizer granule. In order to investigate the film formation under the conditions of different reaction temperatures, the suspension prepared in the same manner as above was placed in a high pressure dad container, and a film formation test was conducted at 1 HTC for 4 hours. As a result, as in the above, it was confirmed that the synthesizable lattice constant a 〇 = 8. 4 〇 A spinel type Crystal structure of magnesium granules. Furthermore, the film formation of the granules when the replacement ions are aluminum (A1) ions was reviewed. The above suspension is only used as a treatment liquid, and the suspension is dissolved in 60 ml of water. 7g of ferrous sulfate (FeS04 · 7H2〇) and 7. 9g of aluminum sulfate (AiS〇4.  The aqueous solution of 16H2〇) was mixed with 6 6 g of a sodium hydroxide (NaOH) aqueous solution of 6 〇mi, and the other steps were carried out in the same manner as in the film-forming property evaluation of the zinc-based fertilizer. The composition analysis was carried out using a fluorescent xenon ray device on a film formed on a square plate placed in a high pressure dad reaction container. As a result, a compound which is iron and aluminum was confirmed. In addition, the crystal structure was investigated by 射线 54 201210789 ray diffraction analysis. As a result, it was confirmed that the obtained film was composed only of the compound having a spinel type crystal structure having a lattice constant aQ = 8 - 35A. That is, it was confirmed that the obtained film was an aluminum-based fertilizer granule. In other words, the film formation of the granules when the replacement ions are chromium (Cr) ions is examined. The suspension is only dissolved in 60 ml of water, using only the following suspension as the treatment liquid. 7g of ferrous sulfate (FeSCV 7H20) and 5. 6g of chromium sulfate (CrS〇4. 3H2〇) aqueous solution and 21. 6 g of a sodium oxynitride (NaOH) aqueous solution was mixed and prepared, and the other steps were carried out in the same manner as in the film formation test of the zinc-based fertilizer granules. The composition of the film formed on the square plate placed in the autoclave reaction vessel was analyzed using a fluorescent X-ray apparatus. As a result, it was confirmed that it was a compound of iron and chromium. Further, the crystal structure was investigated by X-ray diffraction analysis. As a result, it was confirmed that the obtained film was only confirmed by the lattice constant a 〇 = 8. A compound of a spinel crystal structure of 38A. That is, it was confirmed that the obtained film was a chromium-based fertilizer granule. In other words, the film formation of the granules when the replacement ions are lithium (Li) ions is examined. The suspension is only dissolved in 60 ml of water, using only the following suspension as the treatment liquid. 7g of ferrous sulfate (FeS04. 7H20) and 3. 2g of chromium sulfate (LiS04.  H20) aqueous solution and 21. 6 g of a sodium hydroxide (NaOH) aqueous solution was mixed and prepared, and the other steps were carried out in the same manner as in the case of the zinc-based fertilizer granule film-forming property evaluation. The film formed on a square plate placed in a high-pressure dad reaction vessel was analyzed by X-ray diffraction to investigate the crystal structure. As a result, it was confirmed that the obtained film was only composed of a lattice constant a 〇 = 8. 39A is a compound of a spinel crystal structure. Further, the obtained film was dissolved in hydrochloric acid. The composition analysis was carried out by ICP emission spectrometry. As a result, it was found that 55 201210789 is a compound of iron and lithium, that is, the film obtained was confirmed to be a lithium-based fertilizer. In addition, as a result of observing the surface of the film by using a scanning electron microscope (SEM), various films of the above-mentioned zinc-to-lithium were obtained, and all the films were formed to have sharp-angled twin crystals as described above. The crystal grains continuously grow into a three-dimensional film 'and are formed into porous crucibles having numerous pores inside the film. From the above results, it has been found that various fertilizer granules substituted with various metal ions can be efficiently formed on the substrate by the hydrothermal synthesis method similar to the formation of the spinel-type iron oxide heat-insulating film. (Sixth embodiment) Fig. 20 is a schematic perspective view showing the layer structure of the heat insulating mold of the present embodiment. The heat insulating mold 51 is used for a resin-molded mold having a fine micro-machined surface, and has a rectangular shaft. 00mm, long axis 9. The height of the 00mm rectangular forming surface is 20. The columnar shape of 00 mm has the following laminated structure. First, the mold base material 52 is composed of a steel material having the same composition as that of the third embodiment. On the surface of the rectangular molding surface side of the mold base material 52, the groove pattern which is finely machined into the cross-sectional shape of the size shown in Fig. 21 is formed in parallel with the long axis at the position of the center of the short axis of the side surface of the forming surface. . A heat insulating layer 54 made of vaporized iron having a film thickness of 50/m is disposed 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 thereof. Further, a metal film layer 58 is formed on the surface thereof, and the metal layer is made of a base film 56 made of nickel and having a film thickness of 6 Å, and an amorphous nickel formed thereon having a film thickness of 65/m. A finely processed metal film 57 composed of a phosphorus alloy film is formed. Further, the surface of the finely-machined metal film 57 is formed on the surface of the resin, and the formed transfer surface is formed into a finely-machined surface 57a having the same size as that of Fig. 21. The manufacturing method of the heat insulating mold of the present embodiment is carried out in the same manner as in the third embodiment except that the conditions for forming the heat insulating film 54 are different. That is, 'the same raw material and the same high-pressure dad reaction vessel are used to carry out the hydrothermal reaction for 7 hours in a stepwise manner, and the thickness of the mold base material 52 formed with the finely processed pattern is formed. A heat insulating rib composed of spinel type iron oxide. Further, a finely-worked metal film 57 of a nickel-phosphorus alloy plating alloy having a thickness of just 0.5 is formed on the plating base film 56 coated with the adhesion layer formed in the same manner as in the embodiment. Further, the surface of the finely processed metal film 57 is machined into the same size as that shown in Fig. 21 by using a precision cutting machine to form a precision machined surface 57a, and the four sides are precisely ground. After the cutting, the heat insulating mold 51 was produced. Evaluation of the coating property of the heat-insulating film The heat-insulating mold 51 thus obtained was observed on the side of the grounded surface of the heat-insulating mold 51 to observe the cross-section of the laminated film including the heat-insulating film. The thickness of the heat insulation of the present invention was observed using a scanning microscope. The coverage and adhesion of the observation tool set 52 and the heat insulating film 53 and the heat insulating film 53 and the metal laminated film of the ± portion (the fourth layer, the base film 56, and the read metal film 57) are all worthy. No cracks or phase _. Next, for the pattern shown in the figure, the processing figure is at 1G as shown by A, a, b, b, c, c, e, e:, f, f. In part, the thickness of the thermal barrier film was measured. Here, A, B, CD, and E5 are the rectangular forming faces of the heat insulating mold 5, which are short 57, 201210789, 5 points of the mold base material 52 on the side of the shaft side, A, B, ρ, L, D ', E'Jij 5 points of the mold base material 52 on the other short-axis side. The thickness of the β m that exists in the small size of the figure shown in Figure 21 is eight: 5〇/^, eight, 50 hearts,隔热5〇 directly above the insulation film C: 51 //m, C,: 51 "m, E: 50# m, E,.  • Sichuan with m, F: 5〇 F’: 50y m. From the above results, we can see that the shape,  The heat-insulating film can be formed to be almost uniform/receptively formed on the groove pattern of the mold base material 52. Mx is well-densified according to the manufacturing method of the heat-insulating film of the present invention, because the chemical reaction of the ruthenium is synthesized by hydrothermal synthesis, so that the surface of the mold of the treatment liquid can be hydrothermally synthesized to make the film uniform and Slow "', the fork grows again. Therefore, even in a mold base material which is subjected to a deep groove processing or the like, the heat insulating film can be sufficiently wound. Further, according to the present invention, even if the film thickness is small, it is not necessary to mechanically add a film to efficiently form a heat insulating film. Seventh Embodiment A heat insulating mold composed of a non-ferrous metal mold base material was produced. In the 23rd ϋ, the layer structure of the separator is displayed. The heat-insulating mold 2 01 is used for forming a resin-made part having a precise fine-machining shape composed of a deep groove, and is made of a non-ferrous metal mold base material and The mold composed of the heat-insulating crucible is composed of the following layer structure. That is, a base layer 2〇3a composed of a nickel plating film having a thickness of 2#m is formed on the surface of the mold base material 2〇2 described below, and the mold base material is low in thermal conductivity and does not lose strength at high temperatures. Made of titanium alloy 'has a diameter of 20. Ommx height 2. The 5mm cap is part of the shape of Zhan (straight 58 201210789 diameter 25. 0mm), the height from the bottom is l〇. In the case of 〇mm, a heat-insulating film base layer 203 formed of an iron film having a thickness of 3"m is formed, and a heat-insulating film composed of a zinc-based fertilizer body having a thickness of 200# m and a kind of a fertilizer-granular material is formed thereon. The film 204 is further provided with a seed layer 205' composed of a palladium catalyst particle film on which a metal film layer 208 is formed. The metal coating layer 208 is composed of a base plating film 206 made of nickel (thickness 2/m) and a finely processed metal film 207 composed of an amorphous nickel-phosphorus alloy film further formed thereon (average thickness 7 8 // m ) constitutes. The molding surface side of the finely-machined metal film 2 〇 7 is formed as a precision processing surface 207a which is mechanically formed to form a fine pattern for press forming of a molded component. According to the above configuration, a ferrite film having a low thermal conductivity and a titanium alloy mold base material having a low thermal conductivity are used as a heat insulating film, and a molding surface having a fine processing in which a deep and fine groove is applied is used. The resin of the mold is formed to form a deep fine pattern. In the prior art, the heat of the high-temperature resin formed on the molding surface of the mold is discharged through the mold substrate, and the resin causes an excessive temperature drop during the molding, and as a result, a state in which the resin is formed is hindered. On the other hand, in the present invention, such a situation can be effectively avoided, and as a result, a fine pattern can be formed more surely. The heat insulating mold 201 is produced as follows. The base film 203a having a thickness of a nickel-plated film is formed on the surface of the molding surface side of the mold base material 2〇2 which is produced by machining a titanium alloy of a non-ferrous metal, and further, The surface was made of an iron sulfate plating bath to form a heat-insulating film base layer 2〇3 composed of an iron film having a thickness of 3 μm. Next, a heat-insulating film 2?4 composed of a zinc-based fertilizer-granular film having a thickness of 200//m was formed on the surface as follows: 59 201210789. That is, 60 ml of water prepared by distillation in nitrogen gas is dissolved. 7g of ferrous sulfate (FeS04·7H20) and 7. 2g of zinc sulfate (ZnS04 · 7H2 〇) aqueous solution and 21. 6 g of a 60 ml aqueous solution of sodium hydroxide (NaOH) was mixed, and a suspension was prepared as a treatment liquid. The suspension was placed in a stainless steel autoclave reaction vessel having a volume of 200 ml, and the mold base material on which the heat insulating base layer 203 was formed was immersed therein, and held by a jig. The mold base material is preliminarily shielded from a molding surface of the heat insulating base layer 203 by a sealing tape made of tetrafluoroethylene. Further, the above work was carried out in a nitrogen atmosphere. The high pressure dad reaction vessel was heated from the outside and reacted at 18 ° C for 6 hours. After the reaction, the mold base material was taken out together with the jig, and separated from the powder compound formed at the same time, and sufficiently washed with water. The autoclave reaction vessel is also similarly used to remove the formed powder, and the internal water is washed, and the same amount of the suspension as above is blended again. Then the mold base material is installed together with the jig, and similarly, the reaction is carried out at 180 ° C. 6 hours. By repeating this operation a total of eight times, a heat-insulating film 204 composed of a zinc-based fertilizer granular film having a film thickness of 200 μm was formed. After the mold having the heat-insulating film formed in this manner is washed with water and sufficiently dried, a micro-particle film is formed on the surface of the heat-insulating film 204 by using a DC sputtering device to which a palladium target is attached, thereby forming a seed crystal. Layer 205. Next, the base plating film 206 made of a nickel film of a thickness is coated with an electroless nickel forging method. A finely processed metal film 207 composed of a nickel-phosphorus plating film for precision processing having a thickness of 1 μm is formed by electroless magnetic recording. Thereby, the metal film layer 208 was produced. Next, the metal coating layer 208 was heat-treated at 2 °C for 3 hours. Thereafter, a precision machined surface 207a' was formed using a precision cutting machine to obtain a heat-insulating mold 2〇1 for a micro-machining die. 201210789 In addition, regarding the heat-insulating film 204, in order to confirm whether or not a film of the desired material is formed, a positive plate made of a titanium alloy that is smothered with the mold base material is prepared (size: 20. 0 drying square, thickness 2. 0mm), in the step of fabricating the above-mentioned heat insulating mold 2〇1, a base film having a thickness of 2"m composed of the same plating film is formed, and a step is formed on the surface thereof to form a cast iron film having a thickness of 3_ Two insulation film base layer. Then, in the step of forming the heat insulating film of the heat insulating mold 2G1, the sample of the square plate is placed in the same autoclave reaction container together with the heat insulating mold 2〇1, simultaneously with the heat insulating film 2〇4. Also, a heat insulating film is formed on the square plate sample. The film formed on the square plate was examined by a fluorescent X-ray apparatus, and as a result, it was confirmed that the film was composed of a composition of iron and zinc. Further, the X-ray diffraction was used to investigate the crystal structure. As a result, it is known that the lattice constant a 〇 = 8. A compound of the spinel crystal structure of 49A. That is, it can be confirmed that the heat insulating film 204 is a zinc-based fertilizer body. Here, even if the temperature of the hydrothermal synthesis reaction of the heat-insulating film composed of the zinc-based fertilizer film is 200 ° C, a zinc-based fertilizer granular film having the same composition as described above can be formed. When the thickness of the film is different, the temperature of the hydrothermal synthesis, the number of times of treatment, and the like can be appropriately changed as needed, whereby a heat insulating film having the same thickness as described above can be formed. Further, the metal layer which is formed on the surface of the mold base material 202 as the base of the heat insulating mold is described in the present embodiment as a laminate of the base layer 203a which is a nickel plating film and the base layer 203 of the heat insulation film which is an iron plating film. In the case of the film, the substrate of the heat insulating film may be a metal film formed of a metal element directly under the heat insulating film, and the method of forming the metal film is not limited to the laminated film of the present embodiment. For example, it may be an iron film formed directly on the surface of the mold base material 201210789 by sputtering. In the present embodiment, the step of forming a seed layer on the surface of the heat-insulating film by sputtering is described. In addition to this method, the method of directly forming the film is also carried out by using the same method. The same hot mold can be manufactured. In addition, the iron film may be omitted as needed, so that the material used for the material: the material directly formed by the _ method is replaced by a finely-added X-metal substrate _ which is composed of a precision-adhesive alloy plating film. Recording film. Eighth Embodiment Example A sectional view of the heat insulating mold of the eighth embodiment is shown in Fig. 43. The heat-insulating mold 2001 is used for a mold for forming a resin component having a (four) dense mirror shape. Here, the material of the mold base material is made of pure copper having high thermal conductivity, and is formed in the form of a laminated structure shown below. . On the surface of the mold base material 2002 described below, a heat-insulating film base layer 2003 composed of an iron-iron plating bath having a thickness of 3/m was disposed on the surface of the mold base material 2002, and the mold base material had a height of 2. Part of the shape of the 5mm cap layer (diameter 25. 0mm), and the height from the bottom is 15. 0mm, diameter 2〇. Further, in the case of 〇0101, a heat-insulating film 2004' composed of an iron-based fertilizer body (i.e., spinel-type iron oxide) having a thickness of 5 〇em is further formed on the base layer of the heat-insulating film, and palladium is further disposed thereon. The seed layer 2005 formed of the catalyst microparticle film has a metal film layer 2008 formed thereon. This metal film layer 2008 is composed of a base plating film 2006 made of nickel (thickness 1/zm) and a finely processed metal film 2007 (thickness 6/zm) composed of an amorphous nickel-phosphorus alloy film further formed thereon. The forming surface side of the finely machined metal film 2007 is formed as a precision machined surface 2007a which is machined to have a mirror surface. That is, in a structure similar to the laminated structure shown in Fig. 26 of the first embodiment, 62 201210789 is a mirror-finished surface of a precision machined surface. This mold is produced by previously forming a finely machined metal film at an average thickness of 1 Å//m, and then machining it into a mirror surface to a thickness of 6 μm to produce the above-mentioned precision machined surface. Further, the method for producing the heat-insulating film 2004 comprising the spinel-type iron oxide of the eighth embodiment is different from the method for forming the water-heat synthesis of the heat-insulating film 10〇4 of the first embodiment. It is made by synthesizing at the atmospheric pressure of loot: below. Thus, by using an oxide material having a low thermal conductivity (metal oxide (spinel type iron oxide)) and having a pore as an insulating layer, it is possible to form a resin having excellent mirror properties. In other words, the heat of the high-temperature molten resin formed by the mirror surface of the metal mold is discharged through the mold base material, and the resin molding failure caused by the temperature drop of the resin during the molding is required to be more than necessary. Fig. 44 shows a manufacturing process of the heat insulating mold 2001 of the present invention. On the surface of the forming surface side of the mold base material 2002, an iron sulfate plating bath was used to form a heat insulating film base layer 2003 composed of an iron film having a thickness of 3/i m (Fig. 44 (1)). Then, a heat-insulating film 2004 made of spinel-type iron oxide having a thickness of 50 μm was formed on the surface (Fig. 44 (2)). The formation of this heat insulating film 2004 is formed in the atmosphere as follows. That is, first, it is prepared to dissolve in water 60ml. 7 g of an aqueous solution of ferrous sulfate (FeS04 · 7H20), further, the aqueous solution is mixed and dissolved in water different from the water. 60 ml of a strong alkali aqueous solution prepared by using 6 g of sodium hydroxide (NaOH) was used to prepare a suspension 2021. Further, the water used here uses water distilled in nitrogen. Next, using this suspension 2021, a heat insulating film 2004 is formed. At this time, the film formation using the heat insulating film forming apparatus 2022 shown in Fig. 45 was carried out. The glass bulb condenser 2023 is attached to the upper portion, and the nitrogen gas is further flowed to the inner portion of the inner stainless steel 63 201210789 alloy reaction vessel 2024. The above suspension 2021 was placed in the reaction vessel 2024, and the mold base material 2002 on which the heat insulating base layer 2003 was formed was impregnated therein and held by a jig 2025. The mold base material was previously shielded with a sealing tape made of a vinyl fluoride to form a molding surface of the heat insulating base layer 2003. The reaction vessel 2024 was heated by heating in an oil bath 2026 maintained at 98 ° C for 120 hours. Further, nitrogen gas was continuously supplied to the inside of the reaction vessel 2024 during the reaction time. After the reaction, the mold base material was taken out together with the jig and thoroughly washed with water. In this manner, 'the mold having the heat-insulating film 1004 having a film thickness of 50/zm is washed with water and sufficiently dried, and then a palladium particle film is formed on the surface of the heat-insulating film 2004 by using a DC sputtering device to which a palladium shoe material is attached. Thereby, the seed layer 2005 is formed (Fig. 44 (3)). Next, a base mineral film 2006 composed of a nickel film having a thickness of 1 "m was coated by electroless nickel plating. Further, a finely processed metal film 2007 composed of a nickel-phosphorus alloy plating film for precision machining having a thickness of 10 μm was formed by electroless nickel plating, whereby a metal coating layer 2008 was produced and heat-treated at 200 ° C for 3 hours (Fig. 44) (4)). Thereafter, the finely-machined metal film 2007 is ground to a thickness of 6/m using a precision cutting machine to form a precise mirror surface l〇〇7a, and a heat-insulating mold for a micro-machining mold is obtained (Fig. 44 (5) ). Further, in the present embodiment, the method of forming the heat insulating film base layer 2003 composed of the iron film formed on the surface of the mold base material 2002 is described in the present embodiment, but the method is the same as in the first embodiment. The method of forming the heat insulating film underlayer 2003 is not limited to the plating method described in the present embodiment. For example, it is also possible to form the iron film directly on the surface of the mold base material by sputtering. In the heat-insulating film 2004, in order to confirm whether or not a film of the desired material is formed, a rectangular substrate of the same material (pure copper) as the mold base material 2002 is prepared (size: length 50 mm, width 20 mm, thickness 2. 0 mm) Using this substrate, a heat insulating film was formed, and this sample was used as the heat insulating film F, and the material was evaluated in detail. The production of the heat insulating film F will be described below. First, in the same manner as in the step of producing the above-described heat insulating mold 2001 (Fig. 44 (1)), the same heat insulating film underlayer is formed on the surface of the substrate. Thereafter, in the same manner as the heat insulating film 2004 of the heat insulating mold 2001, a suspension having the same composition as that of the above suspension 2021 was used, and the reaction container shown in Fig. 45 was used, and the reaction was repeated at 98 ° C under the same synthesis conditions. A 120-hour reaction was carried out 3 times (360 hours in total), and a heat-insulating film F having a film thickness of about 150 / / m was produced. Here, in the same manner as in the first embodiment, in order to define the composition and crystal structure required for the material of the heat insulating film, the pores of the same sample are simultaneously evaluated for pores. Rate and Vickers hardness. The heat-insulating film F formed on the substrate in this manner is black, and from the analysis of the composition of the fluorescent X-ray device using the film, it is known that the metal ion is composed of only a compound composed of iron, and further, X-ray diffraction is performed. Can be identified as a lattice constant aQ=8. 39A. That is, it was confirmed that the heat insulation film F is a spinel type iron oxide, that is, Fe304. The X-ray diffraction pattern is shown in Fig. 46. Fig. 47 shows a scanning electron microscope image of the surface after the formation of the film of the heat insulating film F. In the same manner as the heat insulating film A of the first embodiment, it is known that the crystal particles having sharp corners and different sizes are connected to each other and exhibit a three-dimensional network structure. Further, more closely, it was confirmed that the junction formed into a twin crystal can be seen. 201210789 The crystal grains are continuously grown into a three-dimensional film and formed into a plurality of pores formed by the gap portion formed by the above-mentioned mesh structure inside the film. A porous membrane of the structure. Further, in the same manner as in the first embodiment, the porosity and Vickers hardness of the heat insulating mF were measured. As a result, it was found that the porosity of the heat insulating film F was 65%. Further, the maximum Vickers hardness is Hv370', and the minimum value is Hvl80', and the average value is Hv24〇. Fig. 48 shows a scanning cat electron microscope image of the polished surface of the thermal barrier film F in which the porosity described above was measured. From the present example, it can be confirmed that it is 1 under atmospheric pressure. (The film produced below was also a porous fat granule film similarly to the film formed by the hydrothermal synthesis of the first to seventh examples. The ninth example produced the iron-based fertilizer granule (FqO4) film By the wet synthesis reaction of the present invention, 'the following two reactions are used to generate fertilizer granules from iron ions, the two reaction systems are 1) Fe2+ + OH_-Fe(OH)2, and 2) Fe(OH 2—Fe304, ie, 1) from ferrous iron ions, in the alkaline environment, ferrous hydroxide (Fe(OH)2), 2) hydrolysis reaction, from which ferrous iron changes to iron-based fertilizer (Fe3〇4) film. In the first to eighth embodiments, all of the heat insulating films of the present invention were produced by using water distilled in a nitrogen atmosphere as water for dissolving the raw materials. The reason for this is that the reaction of the above 1) is carried out smoothly to obtain an intermediate product in the case of synthesizing a granular film of a fertilizer, and the purity and homogenization of ferrous hydroxide (Fe(〇H) 2 ). That is, in order to prevent the following, when the oxygen in the atmosphere is dissolved in water which will be a ferrous salt of a raw material (for example, ferrous sulfate), the raw material can be dissolved in the water at a price of 2 One part of the iron ion (Fe2 + ion) is due to the dissolved oxygen present in 66 201210789, and the change to the trivalent iron ion & = mass doping is present in the aqueous solution of the iron raw material. In other words, when the trivalent iron ion stock is originally composed of only the valence of the divalent argon, and the amount of the ternary iron ion is always present, the reproducibility of the formation of the granule film of the present invention is biased. possibility. However, it is desirable to synthesize a mass-produced heat-insulating film for use in the use of easily-treated ion-exchanged water instead of water for distillation in an atmosphere where attention is required. > Regardless of whether or not the water used for the synthesis of the heat-insulating film can be used in the case of the hexahydrate, the water to which the reducing agent is added is substituted for the water distilled in the nitrogen atmosphere, and the heat-insulating film F of the eighth embodiment is used. For the same substrate, the production of the sample film was attempted. In the ninth embodiment, only the raw material suspension * used for the synthesis of the heat insulating film F of the eighth embodiment was used, and the other steps were carried out in the same manner as the heat insulating film, and a sample film was produced. gP, in the preparation of the raw material suspension, the water is used in the ion-exchanged water to dissolve the ascorbic acid water which is one of the reducing agents, and the water distilled in the nitrogen atmosphere for the synthesis of the heat-insulating film F. First, prepare 60ml of ion-exchanged water to dissolve 4l. 7g of ferrous sulfate (FeS04. The aqueous solution of 7H20) was further advanced, and 24 mg of ascorbic acid as a reducing agent was added to the aqueous solution to dissolve. Step-by-step, mixing in the above aqueous solution will be 21. A raw material suspension was prepared by dissolving 6 g of argon oxide sodium (NaOH) in a strong alkali aqueous solution prepared by dissolving in ion-exchanged water. This raw material suspension was used, and the heat insulating film forming apparatus 2022 (Fig. 45) used for the formation of the heat insulating film F of the eighth embodiment was used, and the reaction was repeated for 115 hours under the same synthesis conditions of 98 °C. A total of three times, a film G having a film thickness of about 150 was produced. 67 201210789 For the heat-insulating film G, in order to confirm whether or not a film of the desired material was formed, the material was evaluated in the same manner as the heat-insulating film F. In the same manner as in the first embodiment, in addition to the composition and crystal structure required for the material defining the heat insulating film, the porosity and Vickers hardness were also evaluated. The heat-insulating film G formed on the substrate in this manner was analyzed by composition analysis using a fluorescent X-ray device and X-ray diffraction, and it was confirmed that the lattice constant a 〇 = 8. 39A of spinel type iron oxide Fe3〇4. Figure X shows the X-ray diffraction pattern. Fig. 50 shows a film scanning electron microscope image of the surface after the formation of the heat insulating film G. In the same manner as the heat insulating film A of the first embodiment, it is understood that a film structure in which crystal particles having different sizes are connected and a three-dimensional mesh structure is formed, and a gap portion formed by the mesh structure is formed inside. Countless stomata. Further, in the same manner as in the first embodiment, the porosity and Vickers hardness of the heat insulating film G were measured. As a result, the porosity of the heat insulating film G was 65%. Further, the maximum Vickers hardness is Hv380, the minimum value is Hvl80, and the average value is Hv240. Fig. 51 shows a scanning electron microscope image of the polished surface of the thermal barrier film G in which the above porosity was measured. According to the present embodiment, even if the ion-exchanged water in which the reducing agent is dissolved is used for the synthesis of the heat-insulating film, the porous fertilizer can be produced in the same manner as the film formed by the hydrothermal synthesis of the first to eighth embodiments. Body membrane. Next, in the production of the raw material suspension for the synthesis of the above-mentioned heat insulating film G, only hydroquinone (24 mg) which is added as another type of reducing agent is used instead of ascorbic acid (24 mg) as a reducing agent, and other heat insulation is used. The formation of the membrane was the same as the synthesis conditions, and the reaction was carried out at a98 ° C for 88 hours, and the synthesis of the heat-insulating fine was attempted. As a result, a film having a thickness of 13 is formed on the substrate. This film is the same as the heat insulation 201210789 'amplitude analysis using the fluorescent x-ray device and x-ray diffraction. It can be seen that the lattice constant a 〇 = 8. The spinel-type iron oxide of 38A shows the 乂-ray diffraction pattern in Fig. 52. Fig. 53 shows a scanning electron microscope image of the county surface after the formation of the film. It is understood that the size of the particles is different from that of the heat insulating film +G, but is a porous film of the same form. Further, the production of the heat-insulating film I was attempted by selecting a combination of the temperature conditions of the above-mentioned heat-insulating film G at a low temperature. The synthesis of the heat-insulating film I was carried out in the following manner except that the synthesis temperature was 88 CU, and the synthesis conditions and the synthesis were the same as those of the synthesis of the heat-insulating film g, and the reaction time was set to 212 hours to form a film. In the heat insulating period thus obtained, the thickness was 25, and the composition and the crystal structure were examined in the same manner as the heat insulating film G. As a result, it was found that the heat-insulating film 1 was a spinel-type iron oxide having a lattice constant a 〇 U7A, that is, Fe3 〇 4 showed an X-ray diffraction pattern in Fig. 54. Further, in Fig. 55, the film shape «the silk φ is called the t submicroscope image. It is known from the state that a porous membrane is formed. Here, in the present embodiment, the heat insulating film which can be synthesized under the atmospheric pressure of the loot is described, and it is understood that the raw material suspension of the heat insulating film obtained by the hydrothermal synthesis of the seventh embodiment (4) In the production, even if water is added to the ion-exchange water (4) paste instead of the water vaporized in the nitrogen gas-zone towel as the water for the synthesis of the heat-insulating film, it can be synthesized by the same method as in the present embodiment. A heat-insulating film composed of a fat granule. In addition, in the method of synthesizing a heat-insulating film, an example of a method of using anti-bad acid or hydrogen brewing as a starting material is described, and the prefecture agent is not limited to those described in the present embodiment, and It has the effect of preventing the description of τ. The reductive reagent of 201210789 can be any, and the case is the divalent doping Y m woven ion in the aqueous solution of the ferrous salt (for example, sulfur S ferrous) 2+ ion) is added to the strong alkali water > in the night or by adding a strong aqueous alkali solution to form an iron hydroxide suspension to immediately oxidize 'to form a trivalent iron ion 卬 3 + ion). For example, it is also possible to use the K/grain gas-based compound of various derivatives of hydroquinone as the evaluation of the reduction heat insulation property to evaluate the same layer structure of the heat insulating mold of the present invention, and evaluate the insulation age of the upper station. And the heat-insulating film! The measurement sample 2〇11G and 2()11I for the evaluation of the barrier properties including the hot film G or the heat-insulating ship of the present invention, which are composed of the same material and the same structure. In the first measurement, the surface of the hot filmed sample should be arranged. Take sample 2, the heat-insulating film (4) is different from the point of heat insulation of Lin 25 heart, and the other structure is exactly the same as that shown in Figure 56. The measurement sample 20UG was produced as follows. First, prepare straight l〇_〇mm, length 44. The round bar of the same material as that of the mold base material 2002 used for the heat insulating mold 2〇〇1 of the eighth embodiment has a diameter of 3. 5mm, depth 22. The thermocouple of the crucible was mounted with a hole 2〇12a, and a substrate 2〇丨2 of a metal round bar was fabricated. Using the substrate 2〇12, in the same manner as the method shown in Fig. 42, the thickness is formed from the bottom of the end surface at a position opposite to the end face having the thermocouple mounting hole 2012a to 23 〇 mm. The base layer 2 〇 13 of the heat-insulating film formed of the iron film is formed thereon to form a partition of the heat-insulating film G of the present invention having a thickness of 5 μm in the same manner as the formation of the heat-insulating film G. Hot film 2014. Then, the resin is shielded from the end surface of the electric mounting hole 2012a with heat 70 201210789, and then the forging method is used from the bottom of the end surface to 23. At a position of 0 mm, a seed layer 2015 composed of a very thin catalyst particle film is formed, and then a base coating layer 2016 made of nickel (thickness l//m) is formed thereon by electroless key recording, further On the other hand, a metal plating film 2017 made of an amorphous nickel-phosphorus alloy film having a thickness of 6 mm is formed by an electroless nickel plating method to form a metal coating layer 2018 composed of a base plating film 2016 and a metal plating film 2017. In the measurement sample 2011 shown in Fig. 56, the measurement sample 20111 is formed of a heat-insulating film 2014 composed of a heat-insulating film G having a film thickness of 5 Å/zm, and is formed of a heat-insulating film I having a film thickness of 25 μm. A measurement sample prepared by a heat insulating film. For the evaluation of the heat insulating property, the comparative sample 1211 (Fig. 33) used in the first embodiment was used as a comparative sample having a structure having no heat insulating film at all. The evaluation of the heat insulating property was carried out by using the heat insulating property evaluation device 21 (Fig. 34) used in the first embodiment. First, the heat insulating properties of the heat insulating film G were measured using the measurement sample 2011G and the comparative sample 1211'. In the heat insulating property evaluation of the heat insulating film G of the present invention, two measurement samples 2〇11G and 1211 which are kept at room temperature and held at a constant temperature are directly attached to the heat insulating plate 1024 while being immersed in the state shown in FIG. The high-temperature water of the constant temperature water tank 22 was measured, and the temperature rise rate was measured, and the heat insulation effect at the time of temperature rise was investigated. Then, the measurement samples 2〇111: and 1211 whose temperature has risen are directly immersed in the low-temperature water of the constant temperature water tank 23 while being mounted on the heat insulating plate 24, and the temperature is lowered, thereby investigating Insulation effect when cooling down. In Fig. 57, the time change of the temperature rise and the time difference of the temperature difference of each of the two measurement samples 71 201210789 are shown as the temperature of the two measurement samples 2011G and 1211 simultaneously immersed in the constant temperature of 9 〇c. When the temperature of the water tank 22 rises, the measurement result of the measurement sample 2〇11G of the heat insulating film of the present invention is compared with the measurement sample 1211 which does not have a heat insulation film. Fig. 58 shows the measurement results of the time change of the temperature drop when the two measurement samples 2011G and 1211 whose temperature has risen are simultaneously immersed in a constant temperature water bath maintained at 28 °C. Similarly, the thermal insulation properties of the thermal barrier film I of the present invention were also evaluated using the measurement sample 20111 and the comparative sample 1211. In Fig. 59, the time change of the temperature rise and the time difference of the temperature difference between the two measurement samples are shown as the simultaneous immersion of the two measurement samples 20111 and 1211 from the room temperature in the warm water tank 22 maintained at 92 C. The time change of the temperature rise time is compared with the measurement sample 1211 of the heat insulation film, and the measurement result of the measurement sample 20111 of the heat insulation film of this invention is provided. Fig. 60 shows the measurement results of the time change of the temperature drop when the two samples 201II and 1211 were simultaneously immersed in a constant temperature water bath maintained at 22 °C. As is apparent from the results of Figs. 57 to 60, the heat insulation of the second type of the present invention clearly has a temperature change to the outside and is not easy to transfer heat to the substrate. In the tenth embodiment, as shown in the fifth embodiment, when the heat insulating film is formed by hydrothermal synthesis, a part of the iron ions forming the spinel type iron oxide Fe3〇4 is replaced with various metal ions. The replacement fertilizer granules of various compositions were formed into a film on the substrate. In the same manner as in the fifth embodiment, it was examined in the case of the human body 72 201210789 which is described in the eighth and ninth embodiments as the thermal insulation film synthesis conditions under the atmospheric pressure of 100 ° C or lower, whether or not the various components can be formed on the substrate. The replacement fertilizer body is made into a braid shape. First, a film formation of an aluminum-based fertilizer granule containing aluminum ions as a replacement ion as a fertilizer granule was attempted. The synthesis review was carried out as follows. In order to confirm whether the desired fat or granular film can be formed by the reaction at atmospheric pressure similar to the method shown in the eighth embodiment, the base substrate for film formation and the material for the thermal insulation film of the eighth embodiment are used. The same material (pure copper) and the same shape of the substrate (size: length 50 mm, width 20 mm, thickness 2. 0 mm), and the same heat insulating film base layer (iron plating film having a thickness of 3 #m) was formed. Will be in the water 60ml will be 34. 7g of ferrous sulfate (FeS04. 7H20), 7. 9g of sulfuric acid (AISO4.  16H2〇) and ascorbic acid 48mg dissolved in ion exchange water in an aqueous solution of 6〇ml and will 21. 6 g of a strong alkali aqueous solution prepared by dissolving 6 g of sodium hydroxide (NaOH) in ion-exchanged water was mixed, and a suspension was prepared as a treatment liquid. In the film formation system of the substrate, the heat insulating film forming apparatus 2022 shown in Fig. 45 is used, and the suspension is placed in a stainless steel alloy reaction container 2024 having an internal volume of 300 ml, and the substrate on which the heat insulating base layer is formed is immersed. It is held therein and clamped using a clamp 2025. The reaction was carried out at 98 ° C for 40 hours. After the reaction, the substrate was taken out together with the jig and washed thoroughly with water. After the completion of the reaction, a film having a thickness of 47 #m was formed on the substrate. For this film, composition analysis was carried out using a fluorescent X-ray device. As a result, a compound which is iron and aluminum was confirmed. Further, the crystal structure was examined using X-ray diffraction. The X-ray diffraction pattern is shown in Fig. 61(a). As a result of the analysis, it was confirmed that the obtained film was only composed of a lattice constant a 〇 = 8. A compound of a 35A spinel crystal structure. That is, it was confirmed that the obtained film was an aluminum-based fertilizer granule. Further, from the observation of the unprocessed surface of the film by a scanning electron microscope, the film was found to be a porous film. 73 201210789 Then, the film formation of the granules in the case of replacing the ions with chromium (〇) ions was reviewed. The point of using only the following suspension as the treatment liquid was different, and the other steps were carried out in exactly the same manner as in the film formation review of the aluminum described above. The hydrazine reacted for 4 hours to form a film, and the suspension was dissolved in water 60 with 34 7 g of ferrous sulfate (FeS04. 7H20), 5. 6g of chromium sulfate (CrS04. 3H20) and ascorbic acid A 48 mg aqueous solution was mixed with 60 ml of a strong aqueous solution prepared by dissolving 21 6 g of sodium hydroxide (NaOH) in ion-exchanged water. The film was opened on the substrate to form a film having a thickness of 6 m. In the same manner as in the above-mentioned time, the composition analysis and X-ray diffraction analysis of the fluorescent X-ray device were used, and the chemical composition was iron and chromium. The lattice constant a〇=8. The oxide of the spinel crystal structure of 39A, that is, the chromium-based fertilizer granule. The xenon ray diffraction pattern is shown in Fig. 61(b). Further, although the film was a film, it was found that the film was a porous film from the observation of a scanning electron microscope from the unprocessed surface. The film formation of the granules when the replacement ions were magnesium (Mg) ions was examined. The point of using only the following suspension as the treatment liquid was different, and the other steps were carried out in the same manner as in the film formation review described above. The hydrazine reacted for 4 hours to form a membrane, and the suspension was dissolved in 60 ml of water. 7g of ferrous sulfate (FeS04. 7H20), 6. 2 g of magnesium sulfate (MgS04 · 7H2 〇) and 48 mg of ascorbic acid were mixed with 60 ml of a strong alkali aqueous solution prepared by dissolving 2 to 6 g of sodium hydroxide (Na〇H) in ion exchange water. A film having a thickness of 11 is formed on the substrate. This film was analyzed in the same manner as described above by composition analysis and X-ray diffraction of a fluorescent X-ray device, and it was found that the chemical composition was iron and town, and the lattice constant a 〇 = 8. The oxide of the spinel-type crystal structure of 36A, that is, the magnesium-based fertilizer granule. Figure 61(c) shows the 乂 ray diffraction pattern 74 201210789 shape. Moreover, this film is also a porous film. The film formation of the granules when the replacement ions were violent (Μη) ions was examined. The procedure of using only the following suspension as the treatment liquid was different, and the other steps were carried out in exactly the same manner as in the film formation review described above, and the film was formed by reacting at 98 ° C for 4 hours, and the suspension was dissolved in 60 ml of water. 7g of ferrous sulfate (FeS04. 7H20), 6. 0g of manganese sulfate (MnS〇4.  5h2〇) and ascorbic acid 48mg of aqueous solution 60ml and will 21. 6 g of sodium hydroxide (Na〇H) was dissolved in ion exchange water to prepare 60 ml of a strong aqueous alkali solution, and the mixture was produced. A film having a thickness of 18 μm was formed on the substrate. As a result of analyzing the material in the same manner as described above, it was confirmed that the chemical composition of iron and manganese was composed only of a compound having a spinel crystal structure having a lattice constant a 〇 = 8 43 A. Namely, it was confirmed that the obtained film was an I Meng granule. The X-ray diffraction pattern is shown in Fig. 61(d). Further, this film is also a porous film. The film formation of the granules when the replacement ions were zinc (Zn) ions was examined. The point of using only the following suspension as the treatment liquid was different, and the other steps were carried out in exactly the same manner as in the above film formation review, to 98. (: The reaction is formed into a film for 40 hours. The suspension is dissolved in 60 ml of water. 7g of ferrous sulfate (FeS04. 7H20), 7. 2g of zinc sulfate (ZnS〇4.  60 ml of an aqueous solution of 7 h 2 〇) and ascorbic acid 48 mg and 60 ml of a strong alkali aqueous solution prepared by dissolving 21·6 g of sodium hydroxide (NaOH) in ion-exchanged water, and the makers formed a fullness of 20 " m on the substrate. membrane. As a result of analyzing the material in the same manner as described above, it was found that the chemical composition was iron and the lattice constant aQ=8. The oxide of the spinel-type crystal structure of 45A, that is, the zinc-based fertilizer granule. The X-ray diffraction pattern is shown in Figure 61 (e). Moreover, this film is also a porous film. 75 201210789 A review was made on the formation of fat and granules when the replacement ions were calcium ions. The procedure of using only the following suspension as the treatment liquid was different, and the other steps were carried out in the same manner as in the film formation review described above, and the film was formed by reacting at 98 ° C for 40 hours, and the suspension was dissolved in ion-exchanged water. 9g of gasified ferrous iron (FeCl2. 4H20) '7. 60 g of an aqueous solution of 4 g of calcium chloride (CaCl 2 , 2H20) and ascorbic acid (48 mg) was mixed with 60 ml of a strong alkali aqueous solution prepared by dissolving 21 to 6 g of sodium hydroxide (NaOH) in ion exchange water. A film having a thickness of 21 μm was formed on the substrate. With respect to the film, the result of analyzing the material in the same manner as described above is that the chemical composition is iron and calcium, and the oxide of the spinel crystal structure having a lattice constant % = 8.36 Å, that is, the calcium-based fertilizer granule. In the 61st (the figure shows the X-ray diffraction pattern. The film is also porous.) From the above, various films substituted with various metal ions are the same as in the fifth embodiment, at 1 〇〇t. In the following synthesis at atmospheric pressure, the film can be formed into a film. INDUSTRIAL APPLICABILITY The mold of the present invention having a predetermined heat insulating layer not only has excellent heat insulating properties, but also has excellent formation properties of a molding surface of a mold base material. It can be formed directly by adjusting the film thickness without post-processing. Therefore, it is useful as a heat-insulating film formed of a resin having a complicated shape such as an optical element or a molded body having a fine pattern shape. Use of a molding die for a stamper, etc.: BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a heat insulating mold according to a second embodiment of the present invention. Fig. 2 (1) to (5) show a second embodiment of the present invention. Fig. 3 is a diagram showing an X-ray diffraction pattern of a heat insulating film according to a second embodiment of the present invention. Fig. 4 is a heat insulating film having a second embodiment of the present invention. Summary of the sample for thermal insulation evaluation Fig. 5 is a schematic cross-sectional view of a sample for thermal insulation evaluation of a conventional heat insulating film. Fig. 6 is a schematic cross-sectional view of a comparative sample without thermal insulation evaluation of a heat insulating film. A schematic configuration diagram of a measuring device for evaluating the heat insulating property of the heat insulating film of the present invention. Fig. 8 is a view showing heat insulating at the time of temperature rise of the sample for heat insulating evaluation of the heat insulating film of the second embodiment of the present invention. Fig. 9 is a view showing the results of heat insulation evaluation when the sample for heat insulation evaluation of the heat insulating film of the second embodiment of the present invention is cooled. Fig. 10 shows a conventional partition. FIG. 11 is a view showing the results of heat insulation evaluation at the time of temperature drop of the sample for heat insulation evaluation of the conventional heat insulating film. Fig. 12 is a schematic cross-sectional view showing a heat insulating mold according to a third embodiment of the present invention. Fig. 13 (1) to (4) are views showing a manufacturing step of the heat insulating mold according to the third embodiment of the present invention. The figure is a schematic view of a sample for heat insulation evaluation of the same structure as the heat insulating mold of the third embodiment of the present invention. Fig. 15 is a schematic view of a comparative sample for thermal insulation evaluation without a heat insulating film 77 201210789. Fig. 16 is a view showing a sample for thermal insulation evaluation of a heat insulating film according to a third embodiment of the present invention. Fig. 17 is a view showing the results of heat insulation evaluation at the time of temperature drop of the sample for heat insulation evaluation of the heat insulating film of the third embodiment of the present invention. Fig. 19 is a view showing the results of heat insulation evaluation at the time of temperature rise of the sample for heat insulation evaluation of the heat insulating film of the third embodiment of the present invention. Fig. 19 is a view showing heat insulation of the heat insulating film of the third embodiment of the present invention. Fig. 20 is a schematic perspective view of a heat insulating mold according to a sixth embodiment of the present invention. Fig. 21 is a view showing the processing of a mold base material according to a sixth embodiment of the present invention. The cross-sectional dimension of the graph. Fig. 22 is a view showing an X-ray diffraction pattern of a heat insulating film containing zinc in the fifth embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing a heat insulating mold of a seventh embodiment of the present invention. Figure 24 is a schematic cross-sectional view of a conventional heat insulating mold. Fig. 25 is a view showing an example of a procedure for molding a molten resin using the mold of the present invention. Figure 26 is a schematic cross-sectional view showing a heat insulating mold according to a first embodiment of the present invention. Fig. 27 (1) to (5) are views showing the steps of producing the heat insulating mold according to the first embodiment of the present invention. Fig. 28 is a view showing an X-ray diffraction pattern of the heat insulating film A of the first embodiment of the present invention. Fig. 29 is a view showing a scanning electron microscope image of the polishing surface 78 201210789 of the heat insulating film A of the first embodiment of the present invention. Fig. 30 is a view showing a polishing section of the heat insulating film A of the first embodiment of the present invention. Fig. 31 is a view showing a scanning electron microscope image of the polishing surface of the heat insulating film B of the first embodiment of the present invention. Fig. 32 is a schematic cross-sectional view showing a sample for heat insulation evaluation of the same structure as the heat insulating mold of the first embodiment of the present invention. Fig. 33 is a schematic cross-sectional view showing a comparative sample for heat insulation evaluation without a heat insulating film. Fig. 34 is a schematic configuration diagram of a measuring device for evaluating the heat insulating property of the heat insulating film of the present invention. Fig. 35 is a view showing the results of heat insulation evaluation at the time of temperature rise of the sample for heat insulation evaluation of the heat insulating film of the first embodiment of the present invention. Fig. 36 is a view showing the results of heat insulation evaluation at the time of temperature drop of the sample for heat insulation evaluation of the heat insulating film of the first embodiment of the present invention. Fig. 37 is a view showing a scanning electron microscope image of the polishing surface of the heat insulating films C, D, and E of the fourth embodiment of the present invention. Fig. 38 is a view showing an X-ray diffraction pattern of a heat-insulating film containing calcium in the fifth embodiment of the present invention. Fig. 39 is a view showing a scanning electron microscope image of a polishing surface of a heat-insulating film containing calcium in the fifth embodiment of the present invention. Fig. 40 is a view showing a method of measuring the porosity of the heat insulating layer of the present invention. Fig. 41 is a view showing the scanning of the surface of the heat insulating film A of the first embodiment of the present invention. Fig. 42 is a view showing a scanning electron microscope image of the surface of a heat-insulating film containing calcium in the fifth embodiment of the present invention. Fig. 4 is a schematic cross-sectional view showing the heat insulating mold of the eighth embodiment of the present invention. Fig. 44 (1) to (5) are views showing the steps of producing the heat insulating mold of the eighth embodiment of the present invention. Fig. 45 is a schematic view showing a reaction vessel used in the eighth embodiment of the present invention. Fig. 4 is a view showing an X-ray diffraction pattern of the heat insulating film of the eighth embodiment of the present invention. Fig. 47 is a view showing a scanning electron microscope image of the surface of the heat insulating film of the eighth embodiment of the present invention. Fig. 48 is a view showing a scanning electron microscope image of the polishing surface of the heat insulating film of the eighth embodiment of the present invention. Fig. 49 is an X-ray diffraction pattern diagram of the heat insulating film G of the ninth embodiment of the present invention. Fig. 50 is a view showing a scanning electron microscope image of the surface of the heat insulating film G of the ninth embodiment of the present invention. Fig. 51 is a view showing a scanning electron microscope image of the polishing surface of the heat insulating film G of the ninth embodiment of the present invention. Fig. 5 is a view showing an X-ray diffraction pattern of the heat-insulating film of the ninth embodiment of the present invention. Fig. 5 is a view showing a scanning electron microscope image of the surface of the heat-insulating film of the ninth embodiment of the present invention. 80 201210789 Fig. 54 is a view showing an X-ray diffraction pattern of the heat insulating film I of the ninth embodiment of the present invention. Fig. 55 is a view showing a scanning electron microscope image of the surface of the heat insulating film I of the ninth embodiment of the present invention. Fig. 56 is a schematic cross-sectional view showing a sample for heat insulation evaluation in which the heat insulating film G is disposed. Fig. 57 is a view showing the results of heat insulation evaluation at the time of temperature rise of the sample for heat insulation evaluation of the heat insulating film G of the ninth embodiment of the present invention. Fig. 58 is a view showing the results of heat insulation evaluation at the time of temperature drop of the sample for heat insulation evaluation of the heat insulating film G of the ninth embodiment of the present invention. Fig. 5 is a view showing the results of heat insulation evaluation at the time of temperature rise of the sample for heat insulation evaluation of the heat insulating film 1 of the ninth embodiment of the present invention. Fig. 60 is a view showing the results of heat insulation evaluation at the time of temperature drop of the sample for heat insulation evaluation of the heat insulating film 1 of the ninth embodiment of the present invention. Fig. 61 is a view showing an X-ray diffraction pattern of a heat-insulating film having a different composition according to a tenth embodiment of the present invention. [Main component symbol description] 1,31,51,101,201,10 (H, 2001. . . Insulation mold 2,32,52,102,202,1002,1012,2002,2012. . . Mold base material 3,13,203,1003,1013,2003,2013. . . . Thermal insulation film base layer 4,14,34,44,54,104,114,204,1004,2004,2014. . .  Thermal insulation film (insulation layer) 5,15,55,115,205,1005,2005,2015·. · Seed layer 6 , 16 , 36 , 46 , 56 , 116 , 206 , 216 , 246 , 1006 , 1016 , 2006 , 81 201210789 2016. . . Substrate coating 7,37,47,57,207,247,1007,2007...finely machined metal film 7a, 37a, 57a, 107a, 207a, 1007a, 2007a. . . Precision machined surface 8,18 ’ 38 ’, 58,108,118,208,218,1008,1018,2008,2018. . .  Metal film layer 1 Bu 41, 111, 21 Bu 24 Bu 34 Bu 44 Bu 1011A, 1011B, 1211 ‘2011G, 20111... Measurement sample 12, 42, 112 ' 212 ' 242, 1012 ’ 1212, 2012. . . Substrate 12a, 42a, 112a, 212a, 1012a, 1212a, 2012a. . . Thermocouple mounting holes 17,117,217,1017...metallized film 18,118,218. . . Thermocouple 21. .  . Insulation evaluation device 22. .  . Constant temperature water tank for high temperature water 23. .  . Constant temperature water tank for cold water 24. .  . Insulation board 25. .  . Electric heater 26. "台27,28,29. . . Insulation cover 35. .  . Adhesive layer 203a. . . Base layer 301. .  . Fixed mold 401··. Movable mold 2021. .  . Suspension 2022. .  . Thermal film forming device 82 201210789 2023. .  . Tube condenser 2024. .  . Reaction vessel 2025. .  . Fixture 2026. .  . Oil tank A-E. . . 5 points of the mold base material 52 on one side of the short-axis side of the rectangular forming surface of the heat insulating mold 51 A'-E'. . . 5 points of the mold base material 52 of the other short-axis side surface R...resin 83

Claims (1)

201210789 VII. Patent application scope: 1. A kind of heat insulation mold is a kind of heat insulation layer between a metal mold base material and a metal film which constitutes a rising surface, and is characterized by: 'The aforementioned heat insulation layer is made of fat grain The crystal particles of the body are connected to a porous body formed by the shape of an eye. 2_Insulation mold according to item 1 of the patent application, wherein the fertilizer system has a spinel crystal structure compound represented by the following general formula: AxFehCV, wherein A represents a crystal which can form a spinel type iron oxide The Fe position is changed to at least one of the metal elements, and X satisfies 〇<=3⁄4 X < 1 ° ) ° 3_ as in the thermal insulation mold of claim 2, wherein the aforementioned a system is Ca, Ζη, Μη, A is at least one of Cr, Li, and Mg. 4. For the insulation mold of the first application of the patent scope, the porosity of the insulation layer is 5 to 75%. 5. For the insulation mold of the first application of the patent scope, the thickness of the insulation layer is 15 e m or more. 6. For the insulation mold of claim 1, the Vickers hardness of the insulation layer is Hvl30~Hv560. 7. The heat insulating mold according to claim 1, wherein the heat insulating layer is made by 1) a surface of a metal mold base material or 2) a surface of a metal layer previously formed on a surface of the mold base material, and An aqueous solution containing a metal component or an aqueous dispersion is reacted to form a generator. 8. The heat insulating mold according to claim 1, wherein the metal film comprises at least a layer of a layer formed on the heat insulating layer and containing a plating catalyst 84 201210789 and 2) formed in the sea A metal film on the seed layer. 9. An insulating mold according to claim 1 of the patent application, which is used for forming a composition containing a tree component. 3. A method for producing a heat insulating mold, which is a mold having a heat insulating layer between a metal mold base material and a metal film constituting a forming surface, the step of forming the heat insulating layer comprising the steps of: }The surface of the metal mold base material, or 2) pre-opened on the surface of the metal layer on the surface of the mold base material, reacting with an aqueous solution or aqueous dispersion containing a metal component to form a metal oxide . U. The method for manufacturing an insulated mold according to claim 10, wherein the step of forming the metal film comprises the steps of: 丄 forming a seed layer containing a catalyst on the heat insulating layer; and 2 a step of forming a metallized film on the seed layer. 12. The method for producing an insulating mold according to the above-mentioned patent scope, wherein the formation of the seed layer is carried out by sputtering or plating. η.If you apply for the full-scale 1G slave partition_The manufacturing method of the above-mentioned reaction includes the bamboo material: the surface of the metal material is 2) or the surface of the metal layer previously formed on the mold base material has been In the state where the mixed metal salt and the treatment liquid formed by the test are in contact with each other, (4) heat treatment is performed at a temperature of 5 t or more. 14·If you apply for the manufacturing method of special-purpose _ shape insulation mold, it is processed in the environment of 100~2〇 (Tc saturated water vapor pressure. If you apply for special _U) The manufacturing process is carried out in the presence of a reducing agent. 85 15.