KR20160117286A - Molding die and low-adhesion material - Google Patents

Abstract

Provided is a molding die used when molding molded articles, the molding die comprising a substrate (10) which is made of a metallic material, and a ceramic layer (20) which is provided on the substrate (10), includes yttrium oxide, nitrogen and cations of an element of Group 4A, and comes into contact with a molded article. Preferably, the molding die can further comprise a middle layer (30) interposed between the substrate (10) and the ceramic layer (20). The middle layer (30) has a greater hardness than the substrate (10) and has a portion which has a greater toughness than the ceramic layer (20). The molding die, after the molding surface thereof is cleaned, continues to be used for molding molded articles. The molding die of the present invention has excellent release, low adhesion, and anti-fouling properties.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a molding die and a low-

TECHNICAL FIELD [0001] The present invention relates to a molding die (molding die) used for molding a molded article and a low-adhesion material.

Patent Literature 1 (Japanese Patent Laid-Open Publication No. 2011-79261) discloses a forming die in which a release layer 4 is formed on a surface 8 of a base material 5 made of ceramics.

Japanese Patent Laid-Open Publication No. 11-79261

The release layer 4 described in Patent Document 1 is said to be excellent in releasing property, low adhesion property and antifouling property. On the other hand, in Patent Document 1, a substrate made of ceramics is used. In such a case, it is difficult to machine the substrate, and there is a problem in that handling of the substrate is difficult (easy to cause cracking or aggravation). In the present application, the phrase " antifouling property " means both properties that prevent the adhesion of contamination and properties that allow the contamination to be easily dropped (removed). It is considered that a material exhibiting low adhesion to a substance has antifouling property to the substance. Based on this, in the present application, both the phrase "antifouling property" and the phrase "low adhesion property" are appropriately used.

The present invention has been made in view of the above-described problems. It is a first object of the present invention to provide a molding frame that is excellent in releasability and low adhesion property and is less prone to cracking and fatigue. A second object of the present invention is to provide a low-adhesion material which is excellent in low-adhesion property and is less prone to cracking or bending.

A molding die according to the present invention is a molding die used for molding a molded product. The molding die is provided with a base made of metal, ceramics which is provided on the base material and contains cations of yttrium oxide, nitrogen and 4A group elements, And is used for molding a molded article after the mold surface is cleaned.

The molding die according to the present invention is characterized by further comprising an adhesive layer interposed between the base material and the ceramic layer in the above-described molding die.

A molding die according to the present invention is a molding die used for molding a molded product. The molding die includes a metal base, a ceramics layer containing a yttrium oxide, a nitrogen and a cation of the 4A group element and in contact with the molded product, And an intermediate layer interposed between the mold and the mold, and is used for molding the molded article after the mold surface is cleaned.

The molding die according to the present invention is characterized by further comprising an adhesive layer interposed between the substrate and the intermediate layer in the above-described molding die.

The molding die according to the present invention is characterized by further comprising an adhesive layer interposed between the intermediate layer and the ceramics layer in the above-described molding die.

The molding die according to the present invention is characterized in that, in the molding die described above, the intermediate layer is formed as a single layer.

The molding die according to the present invention is characterized in that, in the molding die described above, the intermediate layer is formed in a plurality of layers.

The molding die according to the present invention is characterized in that in the above molding die, the intermediate layer is formed in a plurality of layers, and the adhesive layer is interposed between at least two intermediate layers in the plurality of intermediate layers.

The molding die according to the present invention is characterized in that, in the above molding die, the adhesive layer is formed as a single layer.

The molding die according to the present invention is characterized in that, in the above molding die, the adhesive layer is formed in a plurality of layers.

The molding die according to the present invention is characterized in that in the molding die described above, the intermediate layer has a portion having higher hardness than the base material and higher toughness than the ceramic layer.

The molding die according to the present invention is characterized in that in the above-described molding die, the intermediate layer has a hardness higher than that of the base material at least on the surface portion on the ceramic layer side.

The molding die according to the present invention is characterized in that in the above molding die, the intermediate layer includes a buffer layer whose hardness changes so as to have a high hardness from the base side to the ceramics layer side.

The molding die according to the present invention is characterized in that in the molding die described above, the intermediate layer includes a buffer layer continuously changing the hardness by changing the composition of the intermediate layer.

The molding die according to the present invention is characterized in that in the molding die described above, the intermediate layer is made of an MA-based (M is titanium, chromium, nickel, zirconium, aluminum or silicon and A is nitrogen, A nitride, a carbide, and an oxide.

The molding die according to the present invention is characterized in that in the molding die described above, the adhesive layer is made of a single metal or a mixture thereof of titanium, chromium, nickel, zirconium, yttrium, aluminum, And a portion made of an oxide containing a plurality of oxides.

The low-adhesion material according to the present invention is a low-adhesion material having low adhesion to a resin used for molding a molded article. The low-adhesion material is composed of a metal base material and a layer made of a material selected from the group consisting of yttrium oxide, And a ceramic layer contacting the resin.

The low-adhesion material according to the present invention is characterized by further comprising an adhesive layer interposed between the substrate and the ceramic layer in the above-mentioned low-adhesion material.

The low-adhesion material according to the present invention is a low-adhesion material having low adhesion to a resin used for molding a molded article, which comprises a metal base and a cation of yttrium oxide, nitrogen and a group 4A element, And an intermediate layer interposed between the substrate and the ceramic layer.

The low-adhesion material according to the present invention is characterized by further comprising an adhesive layer interposed between the substrate and the intermediate layer in the above-mentioned low-adhesion material.

The low-adhesion material according to the present invention is characterized by further comprising an adhesive layer interposed between the intermediate layer and the ceramic layer in the above-mentioned low-adhesion material.

The low-adhesion material according to the present invention is characterized in that, in the above-mentioned low-adhesion material, the intermediate layer is formed as a single layer.

The low-adhesion material according to the present invention is characterized in that, in the above-mentioned low-adhesion material, the intermediate layer is formed of a plurality of layers.

The low-adhesion material according to the present invention is characterized in that in the low-adhesion material described above, the intermediate layer is formed of a plurality of layers, and the adhesive layer is interposed between at least two intermediate layers in the plurality of intermediate layers.

The low-adhesion material according to the present invention is characterized in that, in the above-mentioned low-adhesion material, the adhesive layer is formed as a single layer.

The low-adhesion material according to the present invention is characterized in that, in the above-mentioned low-adhesion material, the adhesive layer is formed of a plurality of layers.

The low-adhesion material according to the present invention is characterized in that, in the above-mentioned low-adhesion material, the intermediate layer has a hardness higher than that of the substrate and higher toughness than the ceramic layer.

The low-adhesion material according to the present invention is characterized in that in the above-described low-adhesion material, the intermediate layer has a hardness higher than that of the substrate at least on the surface portion on the ceramic layer side.

The low-adhesion material according to the present invention is characterized in that, in the above-mentioned low-adhesion material, the intermediate layer includes a buffer layer whose hardness changes so as to have a high hardness from the substrate side to the ceramics layer side.

The low-adhesion material according to the present invention is characterized in that, in the above-mentioned low-adhesion material, the intermediate layer includes a buffer layer continuously changing the hardness by changing the composition of the intermediate layer.

The low-adhesion material according to the present invention is a low-adhesion material as described above, wherein the intermediate layer is an MA-based material (M is titanium, chromium, nickel, zirconium, aluminum, or silicon and A is nitrogen, , A nitride, a carbide, and an oxide.

The low-adhesion material according to the present invention is a low-adhesion material in which the adhesive layer is made of a metal single or a mixture of titanium, chromium, nickel, zirconium, yttrium, aluminum or silicon, And a plurality of oxide-containing portions.

In the present specification, "hardness" means "dynamic microhardness tester" (model number: DUH-211S) manufactured by Shimadzu Corporation, and measurement conditions are "indenter: triangular indenter (Berkovich type, Quot ;, and a load holding time: 15 seconds "), a depth of penetration from the surface of 0.1 [micro] m, a loading speed of 80 (0.8758 mN / sec) and a load holding time of 15 seconds.

According to the present invention, it is possible to provide a molding frame which is excellent in releasability and low-adhesion property and which is less prone to cracking and fatigue, a low-adhesion material which is excellent in low-adhesion property and which is less prone to cracking or bending .

These and other objects, features, aspects and advantages of the present invention will become apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a section of a mold according to one embodiment of the present invention. Fig.
2 is a view showing a section of a mold according to another embodiment of the present invention.
3 is a sectional view showing an example of the structure of the intermediate layer in more detail;
4 is a cross-sectional view showing another example of the structure of the intermediate layer in more detail;
5 is a cross-sectional view showing another example of the structure of the intermediate layer in more detail;
6 is a view showing an experimental result of evaluating the moldability of a mold according to one embodiment of the present invention and a mold of a comparative example.
7 is a photograph showing a bottom surface of the molding die after a predetermined number of molding operations are performed using the molding die according to one embodiment of the present invention.
8 is a photograph showing the bottom surface of the molding die after a predetermined number of molding operations are performed using the molding die according to the comparative example.
Figs. 9A and 9B are views showing a case where a predetermined number of molding operations are performed using the bottom surface of the molding die after a predetermined number of molding operations have been performed using the molding die according to one embodiment of the present invention, and a molding die according to a comparative example And the bottom surface of the molding die after that, respectively.
Figs. 10A and 10B show the results of an experiment in which four types of resins were used to evaluate the adhesive force, and Fig. 10B shows the results of experiments, And the results of evaluating the relationship between the number of continuous adhesion and the adhesive force using the same resin.

Hereinafter, embodiments of the present invention will be described. In addition, the same or equivalent portions are denoted by the same reference numerals, and the description thereof may not be repeated.

In addition, in the embodiments described below, the scope of the present invention is not necessarily limited to the number, amount, and the like, unless specifically stated otherwise. In the following embodiments, each component is not necessarily essential to the present invention except for the case where there is a substrate in particular.

First, an embodiment of the present invention will be outlined.

One embodiment of the present invention is a mold for molding a molded article, which comprises a metal base, and a cation provided on the base, the yttrium oxide, the nitrogen and the cations of the 4A group element, And a ceramic layer which is in contact with the ceramic layer. An adhesive layer may be provided between the substrate and the ceramic layer.

In addition, one embodiment of the present invention is a molding die used for molding a molded article, which comprises a metal base, a ceramic layer containing a yttrium oxide, a nitrogen and a cation of a 4A group element and in contact with the molded article And an intermediate layer interposed between the substrate and the ceramics layer. An adhesive layer may be interposed between the substrate and the intermediate layer. Further, an adhesive layer may be interposed between the intermediate layer and the ceramics layer.

When the intermediate layer is formed of a plurality of layers, an adhesive layer may be interposed between at least two intermediate layers in the plurality of intermediate layers.

The adhesive layer may be a single layer or a plurality of layers.

Further, in the above-described mold, the intermediate layer has a hardness higher than that of the base material and a toughness higher than that of the ceramics layer. In addition, the intermediate layer has a hardness higher than that of the substrate at least on the surface portion on the ceramic layer side.

In the molding die, the intermediate layer may include a buffer layer. For example, the buffer layer is configured to change its hardness so as to have a high hardness from the substrate side toward the ceramics layer side.

Further, in the above-described mold, the intermediate layer may include an adhesive layer.

Further, a plurality of buffer layers can be provided, and a single layer or a plurality of adhesive layers can be interposed between at least two buffer layers.

In addition, the adhesive layer may function as a buffer layer.

Further, for example, it may be difficult to bond the intermediate layer (buffer layer) and the ceramics layer with a single-layer adhesive layer. In this case, the intermediate layer (buffer layer) and the ceramics layer may be step-wise bonded with a multi-layered adhesive layer (for example, in the case of three layers, the first adhesive layer, the second adhesive layer and the third adhesive layer from the ceramic layer side) 5).

That is, the first adhesive layer in contact with the ceramics layer is made of a material that is easy to adhere to the ceramic layer and the other adhesive layer (corresponding to the third adhesive layer) in contact with the intermediate layer (buffer layer) . That is, the adhesive layer can be formed into a multi-layered structure as required.

When the multilayer adhesive layer has three layers, the first adhesive layer and the third adhesive layer may be bonded to each other with a second adhesive layer formed of a material that is easily adhered to the first and third adhesive layers.

Generally speaking, the intermediate layer is substantially a buffer layer, and the intermediate layer (buffer layer) can be bonded to another layer through an adhesive layer (external addition of the adhesive layer to the intermediate layer).

Further, as shown in the example shown in the drawing, the intermediate layer may be composed of a buffer layer and an adhesive layer, and the intermediate layer is an intermediate layer including the adhesive layer (inner portion of the adhesive layer in the intermediate layer).

Therefore, in the intermediate layer according to the present invention, the adhesive layer can be externally or internally added to the buffer layer, which is a substantial intermediate layer.

The intermediate layer according to the present invention may be only a buffer layer or only an adhesive layer.

In addition, the buffer layer may have an adhesive action, and the adhesive layer may have a buffer action.

The buffering action by the above-mentioned intermediate layer (buffer layer or adhesive layer) is also mentioned. The ceramic layer is a thin layer and has a hardness harder and a low toughness with respect to the metal base. An intermediate layer is provided as a layer for buffering the difference in hardness and toughness between the two.

Hereinafter, the present invention will be described in more detail with reference to the drawings.

1 is a view showing a section of a mold according to the present embodiment. As shown in Fig. 1, the mold frame according to the present embodiment is used for molding a resin molded article and the like. The mold frame 10 includes a metal base 10, And a ceramic layer (20).

The metal base 10 may be made of a ferrous material (for example, stainless steel, carbon steel, alloy steel, alloy tool steel, high speed steel, free hard steel, etc.) Or the like). As a result, the metal base 10 can be made excellent in workability and less prone to cracking or bending.

Ceramics layer 20 includes yttria, nitrogen, and cations of Group 4A elements. Thereby, a molding frame excellent in releasability and low adhesion property is provided. The metal base 10 and the ceramics layer 20 may be joined to each other through an adhesive layer (not shown).

The metal base 10 can be formed by a conventional metal working method such as cutting or electric discharge machining. The ceramic layer can be formed by, for example, physical vapor deposition (PVD) such as sputtering or ion plating.

In the example of Fig. 1, the thickness of the ceramics layer 20 is about 0.1 mu m to 5 mu m. The thickness of the adhesive layer between the metal substrate 10 and the ceramic layer 20 is about 0.01 mu m to 1 mu m.

Fig. 2 is a view showing a section of a mold according to another embodiment. Fig. 2, the forming mold further includes an intermediate layer 30 interposed between the base material 10 and the ceramic layer 20. [0050] The intermediate layer 30 has a portion higher in hardness than the metal base 10 and higher in toughness than the ceramic layer 20. As a result, it is possible to prevent the ceramic layer 20 from being cracked or peeling off from the metal base 10.

In the example of Fig. 2, the thickness of the intermediate layer 30 is about 0.2 to 5 m. The thickness of the ceramics layer 20 is about 0.1 m to 5 m in the same manner as in the example of Fig.

Next, the structure of the intermediate layer 30 will be described in more detail with reference to Figs. 3 to 5. Fig. In the example of Fig. 3, the intermediate layer 30 has the buffer layers 31A and 31B and the adhesive layers 32A and 32B. In the example of Fig. 4, the intermediate layer 30 includes the buffer layer 31 and the adhesive layers 32A and 32B In the example of Fig. 5, the intermediate layer 30 has buffer layers 31A and 31B and adhesive layers 32A to 32D.

That is, the buffer layer may be composed of a plurality of layers as shown in Figs. 3 and 5, or a single layer as shown in Fig. As shown in Figs. 3 and 4, the adhesive layer may be composed of a single layer on both sides of the buffer layer. Alternatively, as shown in Fig. 5, the adhesive layer may be composed of a plurality of layers on one side of the buffer layer and a single layer on the other side , Or it may be composed of a plurality of layers on both sides of the buffer layer.

In the intermediate layer 30 shown in Fig. 5, a single layer or a plurality of adhesive layers may be provided between the buffer layer 31A and the buffer layer 31B, which are substantially intermediate layers. Further, in the case where an adhesive layer with another layer is provided in the buffer layer (substantial intermediate layer), the intermediate layer includes an adhesive layer.

4, the buffer layer 31 and the metal base 10 can be directly bonded. 4, the buffer layer 31 and the ceramic layer 20 can be directly bonded.

Both the buffer layer and the adhesive layer can be formed by physical vapor deposition (PVD) such as sputtering or ion plating.

It is preferable that the buffer layer changes its hardness so as to have a high hardness from the side of the metal base 10 having a low hardness to the side of the ceramic layer 20 having a high hardness. 3 and 5, the hardness of the buffer layer 31A on the side of the metal base 10 is set to be larger than the hardness of the buffer layer 31B on the side of the ceramic layer 20 in the case of the buffer layers 31A and 31B of the laminated structure, By making the hardness lower than the hardness, the hardness can be changed stepwise. In the case of the single-layer structure buffer layer 31 as shown in Fig. 4, the hardness is changed continuously by changing the composition in the thickness direction of the buffer layer (for example, by decreasing the nitrogen concentration in the vicinity of the metal substrate 10) Can be changed.

The buffer layer is composed of, for example, nitride, carbide, or oxide of an MA system (M is titanium, chromium, nickel, zirconium, aluminum, or silicon and A is nitrogen, carbon, or oxygen).

The adhesive layer is composed of, for example, a single metal or a mixture thereof of titanium, chromium, nickel, zirconium, yttrium, aluminum, or silicon, or an oxide of the metal alone or an oxide containing a plurality of the metals.

The material constituting the buffer layer and the material constituting the adhesive layer can be appropriately selected and combined. The thickness (total) of the buffer layer is about 0.2 탆 to 5 탆.

Next, the improvement in releasability according to the embodiment of the present invention will be described with reference to FIG. Fig. 6 is a graph showing the relationship between the molding die according to one embodiment of the present invention and a molding die (hard metal chromium-plated metal substrate) according to a comparative example in a predetermined number of times, And the results are shown in FIG. The resin used in the experiment is a thermosetting resin (specifically, an epoxy resin), including an experiment to be described later.

Referring to Fig. 6, the forming mold according to the embodiment of the present invention has a reduced releasing force as compared with the forming mold according to the comparative example, and the forming mold is excellent in releasability by the ceramics layer 20 .

Next, the improvement of the low adhesion property according to the embodiment of the present invention will be described with reference to FIGS. 7 and 8. FIG. Figs. 7 and 8 are diagrams for explaining a case where the molding operation is performed a predetermined number of times (Fig. 7: 1000 times, Fig. 8: 300 times) using the molding die according to the embodiment of the present invention and the molding die according to the comparative example Is a photograph showing the bottom surface of the molding die after the molding.

7 and 8, in the mold (FIG. 7) according to the embodiment of the present invention, even after performing the molding operation for 1000 times, no noticeable contamination is recognized, (Fig. 8), adhesion of the resin is recognized in part A after 300 molding operations, and flash deposition is recognized in part B. Also, discoloration is recognized throughout the cavity bottom surface. From the above results, it can be seen that the ceramics layer 20 provides a molding frame excellent in low adhesion.

As described above, according to the molding die of the present embodiment, by using the ceramics layer 20, a molding frame excellent in releasability and low adhesion can be obtained. In addition, by using the metal base 10, It is possible to inhibit or prevent overloading. The intermediate layer 30 improves the bonding structure between the metal base 10 and the ceramic layer 20 and can prevent cracking of the ceramic layer 20 and peeling from the metal base 10. [

Further, the above-described mold can be used for injection molding, transfer molding, compression molding, for example.

In the case of transfer molding (or compression molding), the semiconductor chip mounted on the substrate is sealed (or compression molded) in a package (molded product) corresponding to the shape of the cavity in the cavity provided with the ceramic layer .

The low-adhesion material according to the present invention is used for each of the above-described molds. The low-adhesion material according to the present invention is used in the following molds in addition to the molds described so far. The first mold is a punching type (a type of a molding machine) used by attaching to a tableting machine. The second mold is a molding mold for heating and pressing a prepreg used for producing a carbon fiber-reinforced plastic or the like, or a mold such as a rod (mandrel).

With reference to Figs. 9A and 9B, reduction of adhesion of contamination by a low-adhesion material (developed material) according to an embodiment of the present invention will be described. As a comparative example, a molding frame made of a material (conventional material) coated with hard chromium on a metal base material (steel base material) was used. The molding operation was carried out for each 250 times using the mold made of the developed material and the mold made of the conventional material.

As a result of the experiment, the state of the mold surface after molding shown in Fig. 9B can be obtained as compared with the initial state of the mold surface shown in Fig. 9A. As shown in the photograph on the left side of Fig. 9B, in the developed material, adhesion of faint resin contamination is observed in the lower right portion. Other than that, adhesion of resin contamination is not shown. As shown in the photograph on the right side of Fig. 9B, adhesion of black resin (extra resin) is reliably shown in the upper right portion in the conventional material. Metallic luster is shown in the portion that continues to the left below from the attached excess resin. This metallic luster may be a sign that the surface layer is peeled off when the attached extra resin peels off. In the remaining part, adhesion of resin contamination is uniformly seen. It is presumed from the color hue shown in the photograph that the resin contamination of the remaining portion has an equal or strong adhesion degree as compared with the resin contamination which appears dimly on the lower right portion in the developed material. From the above, it can be understood that the low-adhesion material according to the embodiment of the present invention has a low adhesion property to the thermosetting resin.

With reference to Figs. 10A and 10B, the reduction of adhesion of contamination by the low-adhesion material (developed material) according to the embodiment of the present invention will be described. As a comparative example, a mold made of a conventional material was used. As shown in Fig. 10A, the adhesive force between the developed material and the resin is reduced to 28 to 50% of the adhesive strength between the conventional material and the resin, for all four kinds of resins. As shown in Fig. 10B, the adhesive force between the developed material and the resin is reduced to 28% of the adhesive strength between the conventional material and the resin, for the first time after cleaning the surface of the material.

These results indicate that the molded article can be molded without cleaning the surface (mold surface) of the mold with the low-adhesion material, so-called tampering. The term tame molding means molding performed using a special resin (a resin different from a resin used for molding a molded product) for the purpose of adhering a release agent to a mold surface. Therefore, since the molded product can be molded after the mold surface is cleaned, the efficiency of the molding process is improved. Depending on the compatibility between the low-adhesion material and the resin, shaping may be performed.

As the resin used for molding, thermosetting resins typified by the above-mentioned epoxy resins can be mentioned. The mold and the low-adhesion material according to the present invention can also be applied to a thermoplastic resin.

The subject to which the low-adhesion material according to the present invention is applied is not limited to a molding frame used for molding a molded article. The low-adhesion material according to the present invention can be applied to a molding frame, a component, a fixture, a tool, etc. used in a step of producing a resin used for molding a molded article, a step of molding a molded article, The material can be applied to parts used for kneading resin, for example, parts used for kneading, tableting, tableting, tools and the like. The low-adhesion material according to the present invention can be used as a prepreg A jig, a tool, or the like for increasing or shaping or cutting the heated prepreg, which is used when producing an intermediate product of the present invention. Further, the low-adhesion material according to the present invention can be applied to injection molding parts such as nozzles, screws and the like.

DESCRIPTION OF THE PREFERRED EMBODIMENTS [0028] The embodiments of the present invention will now be described, but it should be understood that the embodiments disclosed herein are illustrative and non-restrictive in all respects. It is intended that the scope of the invention be indicated by the appended claims and that all changes which come within the meaning and range of equivalency of the claims are intended to be embraced therein.

10: metal substrate
20: Ceramic layer
30: middle layer
31, 31A, 31B: buffer layer
32A, 32B, 32C and 32D:

Claims (32)

As a molding die used for molding a molded article,
A metal substrate,
A ceramic layer provided on the substrate and including a cation of yttrium oxide, nitrogen, and a Group 4A element, the ceramic layer being in contact with the molded product,
Wherein the mold is used for molding the molded article after the mold surface is cleaned. The method according to claim 1,
Further comprising an adhesive layer interposed between the substrate and the ceramic layer. As a molding die used for molding a molded article,
A metal substrate,
A ceramic layer including a yttrium oxide, a nitrogen and a cation of a Group 4A element,
And an intermediate layer interposed between the substrate and the ceramics layer,
Wherein the mold is used for molding the molded article after the mold surface is cleaned. The method of claim 3,
Further comprising an adhesive layer interposed between the substrate and the intermediate layer. The method of claim 3,
Further comprising an adhesive layer interposed between the intermediate layer and the ceramics layer. The method of claim 3,
Wherein the intermediate layer is formed as a single layer. The method of claim 3,
Wherein the intermediate layer is formed in a plurality of layers. The method of claim 3,
Wherein the intermediate layer is formed in a plurality of layers, and an adhesive layer is interposed between at least two intermediate layers in the plurality of intermediate layers. The method according to any one of claims 2, 4, 5, and 8,
Wherein the adhesive layer is formed as a single layer. The method according to any one of claims 2, 4, 5, and 8,
Wherein the adhesive layer is formed in a plurality of layers. The method of claim 3,
Wherein the intermediate layer has a portion higher in hardness than the substrate and higher in toughness than the ceramic layer. The method of claim 3,
Wherein the intermediate layer has a hardness higher than that of the substrate at least on a surface portion of the ceramics layer side. The method of claim 3,
Wherein the intermediate layer includes a buffer layer whose hardness changes so as to have a high hardness toward the ceramic layer side from the substrate side. The method of claim 3,
Wherein the intermediate layer comprises a buffer layer continuously changing the hardness by changing the composition of the intermediate layer. The method of claim 3,
Characterized in that said intermediate layer comprises a portion composed of nitride, carbide and oxide of MA series (M is titanium, chromium, nickel, zirconium, aluminum or silicon and A is nitrogen, carbon or oxygen) . The method according to any one of claims 2, 4, 5, and 8,
Wherein the adhesive layer comprises a metal single layer or a mixture thereof of titanium, chromium, nickel, zirconium, yttrium, aluminum or silicon, or a portion composed of an oxide of the metal single crystal or an oxide containing a plurality of the metal single crystals Molding frame. As a low-adhesion material having low adhesion to a resin used for molding a molded article,
A metal substrate,
And a ceramic layer provided on the substrate and including a cation of yttrium oxide, nitrogen, and a group 4A element, and contacting the resin. 18. The method of claim 17,
Further comprising an adhesive layer interposed between the substrate and the ceramic layer. As a low-adhesion material having low adhesion to a resin used for molding a molded article,
A metal substrate,
A ceramic layer containing a yttrium oxide, a nitrogen and a cation of a Group 4A element and in contact with the resin,
And an intermediate layer interposed between the substrate and the ceramics layer. 20. The method of claim 19,
Further comprising an adhesive layer interposed between the substrate and the intermediate layer. 20. The method of claim 19,
Further comprising an adhesive layer interposed between the intermediate layer and the ceramics layer. 20. The method of claim 19,
Wherein the intermediate layer is formed as a single layer. 20. The method of claim 19,
Wherein the intermediate layer is formed in a plurality of layers. 20. The method of claim 19,
Wherein the intermediate layer is formed in a plurality of layers, and an adhesive layer is interposed between at least two intermediate layers in the plurality of intermediate layers. The method according to any one of claims 18, 20, 21, and 24,
Wherein the adhesive layer is formed as a single layer. The method according to any one of claims 18, 20, 21, and 24,
Wherein the adhesive layer is formed in a plurality of layers. 20. The method of claim 19,
Wherein the intermediate layer has a hardness higher than that of the substrate and a higher toughness than the ceramic layer. 20. The method of claim 19,
Wherein the intermediate layer has a hardness higher than that of the substrate at least on the surface portion of the ceramics layer side. 20. The method of claim 19,
Wherein the intermediate layer comprises a buffer layer whose hardness changes so as to have a high hardness toward the ceramics layer side from the substrate side. 20. The method of claim 19,
Wherein the intermediate layer comprises a buffer layer continuously changing the hardness by changing the composition of the intermediate layer. 20. The method of claim 19,
Characterized in that said intermediate layer comprises a portion composed of nitride, carbide and oxide of MA series (M is titanium, chromium, nickel, zirconium, aluminum or silicon and A is nitrogen, carbon or oxygen) As the low adhesion material. The method according to any one of claims 18, 20, 21, and 24,
Wherein the adhesive layer includes a metal single layer or a mixture thereof of titanium, chromium, nickel, zirconium, yttrium, aluminum, silicon, or a portion composed of an oxide of the metal single crystal or an oxide containing a plurality of the metal single crystals Low adhesion material.

Images