JP6414965B2 - Porous layer manufacturing method, interpenetrating layer manufacturing method, metal and resin bonding method - Google Patents

Description

The present invention relates to a method for manufacturing a multi-porous layer, a method for manufacturing a interpenetration layer, to a bonding method of a metal and a resin.

  For example, in various fields including transportation equipment such as automobiles and airplanes, multi-materialization is progressing in which excellent materials are arranged at appropriate places. In particular, by using a carbon fiber reinforced plastic (CFRP), a significant weight reduction can be achieved. For example, there is a movement in which CFRP is used for a cabin portion in an automobile and CFRP is used for a fan blade portion of a jet engine in an aircraft. In any case, a strong bond between a metal and a resin is indispensable.

  As a method for joining a metal and a resin, there is a method in which an open pore type porous layer is provided on the surface of the metal and the resin is infiltrated into voids (pores) of the porous layer. In this method, the resin penetrates into the void portion so that the plant takes root, thereby forming an interpenetrating layer, and the metal and the resin are joined through the interpenetrating layer (see, for example, Non-Patent Documents 1 to 3).

Materials Letters 59 (2005) 2178−2182 Journal of Materials Processing Technology 212 (2012) 1061-1069 Proceedings of the 124th Spring Conference of the Japan Institute of Light Metals (April 18, 2013)

  FIG. 18 shows a tensile test in the axial direction (arrows D1 and D2 directions) of a sample prepared by preparing a porous layer on an Al (aluminum) substrate and infiltrating an epoxy resin into the void of the porous layer. The results are shown. It was confirmed that the bonding strength of the sample having a resin volume fraction of 70% of the interpenetrating layer was about 50% of the bonding strength of the epoxy resin. At this time, the rupture occurred at the boundary between the epoxy resin and the interpenetrating layer (the intrusion portion of the epoxy resin into the interpenetrating layer), and Al and the epoxy resin are on the fracture surface (observation position A) on the interpenetrating layer side. As observed, Al was not observed on the fracture surface (observation position B) on the side where the epoxy resin entered, and only the epoxy resin was observed. When the fracture state is schematically shown, it is as shown in FIG. In the fracture surface of the epoxy resin and the interpenetrating layer, it was confirmed that peeling occurred at the portion where the epoxy resin was in contact with Al, and fracture occurred at the portion where the epoxy resin entered the interpenetrating layer. It was.

  FIG. 20 shows the result of imaging a sample with X-ray CT, creating a three-dimensional model, and calculating the stress distribution generated inside the sample by finite element analysis (FEM). In the calculation results, it was confirmed that high stress was generated near the darkest portion (hatched portion indicated by arrow P in the schematic diagram), that is, near the boundary between the epoxy resin and the interpenetrating layer. From these FIG. 18 to FIG. 20, it was confirmed that high stress was locally generated in a portion near the boundary with the interpenetrating layer inside the epoxy resin, and that portion was the starting point of fracture.

By the way, it is clear that the higher the joint strength, the higher the quality, and there is a demand for increasing the joint strength.
The present invention has been made in view of the above, the object is achieved by a method for manufacturing a multi-porous layer high bonding strength capable of forming an interpenetration layer may be implemented between resin interpenetration layer It is in providing the manufacturing method of this, and the joining method of a metal and resin.

The porous layer of the present disclosure is a porous layer that is interposed between a metal and a resin and has a void that allows the resin to permeate, and has a relatively low porosity on the side in contact with the metal. It is characterized by having a relatively high porosity on the intrusion side.
The method for producing a porous layer according to claim 1 , wherein the raw material powder containing a metal powder and a spacer powder is pressurized and heated under conditions of pressure and temperature at which the spacer powder is not crushed or decomposed. , And thereafter the spacer powder is removed to form a void, so that the porosity on the side in contact with the metal is relatively low and the porosity on the side in which the resin enters is relatively high A porous layer is prepared.

In the structure in which the resin penetrates into the voids (pores) of the porous layer to form an interpenetrating layer, and the metal and the resin are joined through the interpenetrating layer, the description is given in [Problems to be solved by the invention] As described above, it has been confirmed that the portion close to the boundary with the interpenetrating layer inside the resin is the starting point of the fracture. In this regard, according to the porous layer of the present disclosure, the porosity is relatively low on the side in contact with the metal, and the porosity is relatively high on the side into which the resin enters, so that it is fabricated on the metal. When the resin penetrates into the voids of the porous layer, the resin volume fraction is relatively low on the side in contact with the metal, and the resin volume fraction is relatively high on the side in which the resin is infiltrated. . That is, at the boundary between the resin and the interpenetrating layer, the resin area ratio (contact area ratio) relative to the entire boundary surface of the surface where the resin is in contact with the metal is relatively small, and conversely, the resin enters the interpenetrating layer. The resin area ratio (penetration area ratio) with respect to the entire boundary surface of the existing surface becomes relatively large, and the amount of the resin that has entered the interpenetrating layer at the boundary increases. Since the breakage between the resin and the interpenetrating layer shown in FIG. 19 occurs near the boundary between the resin and the interpenetrating layer inside the resin, the resin becomes an interpenetrating layer at the boundary between the resin and the interpenetrating layer in this way. Since the resin area ratio of the surface to be infiltrated becomes relatively large, the stress generated in the resin is reduced. As a result, breakage hardly occurs at the boundary between the resin and the interpenetrating layer, and the bonding strength between the resin and the interpenetrating layer can be increased.

According to the method for producing a porous layer according to claim 1 , as with the porous layer of the present disclosure , the resin with respect to the entire boundary surface of the surface where the resin is in contact with the metal at the boundary between the resin and the interpenetrating layer. The contact area ratio, which is the area ratio, becomes relatively small, and conversely, the infiltration area ratio, which is the resin area ratio with respect to the entire boundary surface of the surface where the resin intrudes into the interpenetrating layer, becomes relatively large and The amount of resin that penetrates into the permeation layer increases. As a result, breakage hardly occurs at the boundary between the resin and the interpenetrating layer, and the bonding strength between the resin and the interpenetrating layer can be increased.

The figure which shows one Embodiment of this invention and shows the aspect which produces the porous layer single-piece | unit The figure which shows the aspect which produces the conjugate | zygote of Ti substrate and a porous layer Diagram showing the procedure for preparing a sample Diagram showing the transition to sample preparation The figure which shows the aspect of sintering of Ti powder The figure which shows the SEM image of Ti powder, Al powder, NaCl powder The figure which shows the external appearance image of a sample, and the SEM image of a cross section Diagram showing model (A) is a diagram showing a model, (b) is a diagram showing a calculation result, and (c) is a schematic diagram. (A) is a diagram showing a model, (b) is a diagram showing a calculation result, and (c) is a schematic diagram. (A) is a diagram showing a model, (b) is a diagram showing a calculation result, and (c) is a schematic diagram. (A) is a diagram showing a model, (b) is a diagram showing a calculation result, and (c) is a schematic diagram. (A) is a figure which shows the whole X-ray CT image, (b) is a figure which shows the image which extracted only Al, (c) is a figure which shows the image which extracted only the epoxy resin Diagram showing the distribution of Al and epoxy resin in the horizontal section for the slope volume fraction model (A) shows the entire X-ray CT image of the constant volume fraction model, and (b) and (c) show the stress distribution in the Al portion of the vertical section. (A) is a diagram showing an entire X-ray CT image, and (b) and (c) are diagrams showing a stress distribution in an Al portion of a vertical section, showing a stress distribution in a vertical section. Diagram showing the transition until a sample with an inclined volume fraction is made SEM image showing fracture surface Diagram showing the broken state Diagram showing the stress distribution generated inside the sample

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings. First, a method for producing a porous layer will be described. In this embodiment, Ti having excellent characteristics for weight reduction is used as a metal, Al having a melting point lower than that of Ti is used as an auxiliary for sintering Ti, and NaCl powder having a melting point higher than that of Al is used as a spacer powder. The case where a porous layer is produced using will be described. The melting point of Ti is about 1668 ° C., the melting point of Al is about 660 ° C., and the melting point of NaCl is about 800 ° C. NaCl has the property of dissolving in still water. The porous layer is produced by producing only the porous layer (producing a porous layer alone) or producing the porous layer on the Ti substrate (on the metal surface) (Ti substrate and porous). In some cases, a joined body with a porous layer is produced. Hereinafter, the porous layer alone and the joined body are collectively referred to as a sample.

  In this embodiment, the apparatus 1 shown in FIG.1 and FIG.2 is used as a means to pressurize and heat raw material powder (mixed powder of Ti powder, Al powder, and NaCl powder). The apparatus 1 includes a cylindrical mold (graphite mold) 2, an upper member 3, and a lower member 4, and the upper member 3 and the lower member 4 extend the hollow portion 2 a of the mold 2 in the axial direction. It is movable. A sample is produced from the raw material powder using the apparatus 1 under the following conditions and the procedure shown in FIG.

-Particle size of Ti powder: <45 μm, <150 μm
-Particle size of Al powder: <45 μm
-Particle size of NaCl powder: 330-430 μm
-Atomic composition ratio of Ti powder and Al powder: Ti-0, 20, 50 at% Al
-Volume fraction of NaCl powder (ratio of NaCl powder to the whole raw material powder): 0-70 vol%
・ Pressure: 1.8MPa, 10MPa
・ Raising rate: 1 ℃ / sec
・ Set temperature: 500-650 ° C
-Holding time (holding time at set temperature): 0h, 1h
The set temperature is measured by providing a thermocouple in the vicinity of the portion where the raw material powder is filled in the mold 2.

Procedure 1: Ti powder and Al powder are mixed at a predetermined atomic composition ratio, and NaCl powder is added to the Ti-Al mixed powder at a predetermined volume fraction to produce a raw material powder.
Procedure 2: In the case of producing a single porous layer, the raw material powder is filled in the hollow portion 2 a of the mold 2 with the lower member 4 mounted on the mold 2. In the case of producing a joined body, first, the Ti substrate is filled in the hollow portion 2a of the mold 2, and then the raw material powder is filled in the hollow portion 2a of the mold 2. The size of the Ti substrate is, for example, 20 mm in diameter and 5 mm in height.

  Procedure 3: The upper member 3 is mounted on the mold 2 from above, pressurized at a predetermined pressure, and heated to a predetermined set temperature at a predetermined temperature increase rate. At this time, since the set temperature (500-650 ° C.) is heated to a temperature close to the melting point of Al (about 660 ° C.), as shown in FIGS. 4 and 5, the Al powder diffuses into the gap between the Ti powders, The following reaction proceeds between the diffused Al powder and Ti powder.

Ti (S) + 3Al (S) → TiAl ₃ (S)
The TiAl ₃ (compound) thus produced functions as a binder for bonding Ti powders together. That is, by adding Al powder, TiAl ₃ is generated, and the generated TiAl ₃ bonds the Ti powder to form voids (pores). At this time, Al powder that does not diffuse may remain depending on the set temperature. Further, since the set temperature is suppressed to a temperature sufficiently lower than the melting point (about 800 ° C.) of the NaCl powder, the NaCl powder is not decomposed while the bonding between the Ti powders proceeds. That is, a Ti-Al alloy in which voids are formed by sintering of Ti powder by bonding of Ti powders via TiAl ₃ and NaCl powder is dispersed (preserving the original shape) is produced.

Procedure 4: Hold for a predetermined holding time at the set temperature.
Procedure 5: After cooling the Ti—Al alloy to room temperature, it is released from the mold 2 and left in a container (beaker) 5 into which still water is poured, and the Ti—Al alloy is washed with still water. At this time, since the NaCl powder is dissolved and removed in the still water, voids (pores) are also formed at locations where the NaCl powder was scattered, as shown in FIG.
Procedure 6: Take out the Ti—Al alloy from which the NaCl powder has been removed from the container 5.
By performing such procedures 1 to 6, it is possible to produce a sample in which voids formed by sintering of Ti powder and voids formed by removing NaCl powder are formed.

FIG. 6 shows raw materials, (a) Ti powder with particle size <45 μm, (b) Al powder with particle size <45 μm, (c) SEM (Scanning Electron Microscope) with NaCl powder with particle size 330-430 μm. ) Show the image.
FIG. 7 shows the particle size of Ti powder: <45 μm, the particle size of Al powder: <45 μm, the particle size of NaCl powder: 330-430 μm, the atomic composition ratio of Ti powder to Al powder: Ti-50 at% Al, NaCl A sample prepared by performing steps 1 to 6 under the conditions of powder volume fraction: 70 vol%, pressure: 1.8 MPa, temperature rising rate: 1 ° C./sec, set temperature: 600 ° C., holding time: 0 h (A) shows the appearance image which imaged the external appearance, (b) shows the SEM image which imaged the structure | tissue of the cross section (vertical cross section). In the sample manufactured under the above conditions, it was confirmed that TiAl ₃ was generated by EDX (Energy Dispersive X-ray Spectroscopy) analysis of the cross section. In FIG. 7B, the circled number “1” is a void formed by removing NaCl powder. That is, since the added NaCl powder has a particle size of about several hundred μm, it was confirmed that a void of about several hundred μm was formed by removing the NaCl powder. In FIG. 7C, the circled number “2” is a void formed by sintering of Ti powder. Although not as large as the gap formed by removing the NaCl powder, it was confirmed that a gap of several to several tens of μm was formed by sintering the Ti powder. Thus, by adding Al powder having a lower melting point than Ti powder, it is possible to achieve both high porosity and sufficient sinterability. The porosity is a value obtained by dividing the sum of the volume of the void portion communicating with the outside and the volume of the void portion enclosed inside by the total volume (apparent volume), and the mass and volume of the sample. It is calculated using

  Next, the bonding strength in a structure in which a resin is infiltrated into the void portion of the porous layer produced by the above-described procedure to produce an interpenetrating layer and the metal and the resin are joined through the interpenetrating layer will be considered. In a structure in which a metal and a resin are joined via an interpenetrating layer, as described in [Problems to be Solved by the Invention], a portion close to the boundary with the interpenetrating layer inside the resin is the starting point of fracture. Has been confirmed. In this regard, as shown in FIG. 8, three types of models in which the structure of the interpenetrating layer was simplified were created, and the influence of the structure of the interpenetrating layer on the stress inside the resin was calculated by finite element analysis. The model of the constant volume fraction shown in FIG. 8A is a model in which the resin volume fraction of the interpenetrating layer is constant (does not change) from the side in contact with the metal toward the side in which the resin enters. The slope volume fraction model shown in FIG. 8B is a model in which the resin volume fraction of the interpenetrating layer increases linearly from the side in contact with the metal toward the side into which the resin enters. The model of the reverse gradient volume fraction shown in FIG. 8C is a model in which the resin volume fraction of the interpenetrating layer linearly decreases from the side in contact with the metal toward the side in which the resin enters.

FIG. 9 to FIG. 12 show the results of calculating the stress distribution generated in the resin by finite element analysis (FEM) for these models. In FIGS. 8 to 12, only the resin is shown and the metal is not shown. In FIGS. 9 and 12, the darkest shaded portion in the calculation results (the hatched portion indicated by the arrow P in the schematic diagram) is the portion where the stress is maximized, and as the distance from the portion where the stress is maximized is increased. The stress is decreasing. In this case, the maximum value of stress is about 1.3 × 10 ⁴ Pa (N / m ² ), for example.

  FIG. 9 shows the calculation results when the resin diameter (thickness) in the interpenetrating layer is changed for the constant volume fraction model. The resin volume fraction increases as the resin diameter in the interpenetrating layer increases. The stress generated in the resin depends on the resin diameter in the interpenetrating layer, and the locally generated stress decreases as the resin diameter in the interpenetrating layer increases (the resin volume fraction increases). Was confirmed. However, the greater the resin diameter in the interpenetrating layer, the greater the stress generated inside the metal, and there is a risk of breakage at the boundary with the metal. I can't.

  FIG. 10 shows a calculation result when the resin thickness (height) in the interpenetrating layer is changed for the constant volume fraction model. It was confirmed that the stress generated in the resin was constant without depending on the resin thickness in the interpenetrating layer. However, if the resin thickness in the interpenetrating layer is thin, peeling occurs on the side surface of the portion into which the resin penetrates, and the resin may be pulled out, so a certain thickness is required.

  FIG. 11 shows the calculation result of the model of the gradient volume fraction. In the slope volume fraction model, it was confirmed that, compared with the constant volume fraction model, the stress generated in the resin was reduced, that is, the joint strength was improved. The bonding strength is improved for the following reason. In the slope volume fraction model, the resin volume fraction increases as it approaches the boundary with the resin in the interpenetrating layer in a state where the resin is infiltrated into the gap. Therefore, at the boundary between the resin and the interpenetrating layer, the resin area ratio (contact area ratio) relative to the entire boundary surface of the surface where the resin is in contact with the metal is relatively small, and conversely the surface where the resin enters the interpenetrating layer. By relatively increasing the resin area ratio (penetration area ratio) with respect to the entire boundary surface, the amount of resin that enters the interpenetrating layer at the boundary increases. As a result, due to the same effect as the constant volume fraction model shown in FIG. 9 (the effect that the locally generated stress decreases as the resin diameter in the interpenetrating layer increases) The stress generated in the portion near the boundary is reduced (reduced to the same level as the stress generated in the resin base material). In addition, in the constant volume fraction model shown in FIG. 9, the stress generated in the metal increases as the resin diameter in the interpenetrating layer increases, but in the gradient volume fraction model, the side in contact with the metal increases. However, since the resin diameter is small, the stress generated in the metal does not increase, and there is no possibility that fracture occurs at the boundary between the metal and the interpenetrating layer.

  On the other hand, FIG. 12 shows the calculation result of the model of the reverse gradient volume fraction. Compared with the constant volume fraction model, the reverse slope volume fraction model has increased stress generated inside the resin, that is, very high stress is locally generated inside the resin. confirmed.

  FIG. 13 shows the production of a porous layer on the Al (aluminum) substrate in which the porosity from the Al substrate side to the side into which the epoxy resin enters linearly changes from 40% to 60%. The X-ray CT image of the sample produced by making it osmose | permeate the space | gap part of a layer is shown. In such a gradient volume fraction model, as shown in FIG. 14, in the horizontal section on the Al substrate side, the Al distribution is 60% and the epoxy resin distribution is 40%. In the horizontal cross section, the Al distribution is 40% and the epoxy resin distribution is 60%, and the volume fraction of the epoxy resin increases from the Al substrate side toward the side where the epoxy resin enters (inclined). ing).

  FIG. 15 shows the stress distribution in the Al portion of the vertical section for the constant volume fraction model, and FIG. 16 shows the stress distribution in the Al portion of the vertical section for the tilt volume fraction model. In FIGS. 15 and 16, the dark and shaded portions (hatched portions indicated by arrows P in the schematic diagrams) show high stress, and the slope volume fraction model has an interpenetrating layer as compared with the constant volume fraction model. It was confirmed that the stress generated in the Al portion was significantly reduced.

  FIG. 17 shows an example of a procedure for actually manufacturing a porous layer having an inclined volume fraction that is expected to have such a high bonding strength. As described above with reference to FIGS. 1 to 3, in the method of filling the raw material powder into the hollow portion 2 a of the mold 2 and pressurizing and heating, the volume fraction of the NaCl powder with respect to the whole raw material powder is divided into a plurality of stages. Thus, the porosity can be inclined. That is, for example, first, a raw material powder having a volume fraction of NaCl powder of 50% is filled in the hollow portion 2a of the mold 2, and then the volume fraction of NaCl powder is sequentially increased to 60%, 70%, and 80%. Thus, it becomes possible to produce a porous layer having an inclined porosity, and it is possible to produce an interpenetrating layer having an inclined volume fraction by infiltrating the resin. However, when the volume fraction of the NaCl powder exceeds 90%, the Ti powders are not bonded to each other. Therefore, the volume fraction of the NaCl powder is desirably set to 90% at the maximum. As a method of dividing the volume fraction of NaCl powder in a plurality of stages, the number and particle diameter of NaCl powder to be filled may be changed. That is, for example, when filling NaCl powder with a constant particle size, the number of NaCl powders to be filled may be increased stepwise, and when filling the NaCl powder with a constant number, NaCl to be filled is filled. What is necessary is just to increase the particle size of a powder in steps. Of course, both the number of NaCl powders to be filled and the particle size may be adjusted. In addition, the porosity can be increased linearly as the number of steps for dividing the volume fraction of NaCl powder is increased, and the change in porosity in the porous layer can be made linear. The change in the resin volume fraction in the permeation layer can be made linear.

  As described above, according to the present embodiment, in the structure in which the resin penetrates into the void portion of the porous layer to form the interpenetrating layer, and the metal and the resin are joined via the interpenetrating layer, The porous layer was configured such that the porosity on the side in contact with the metal was relatively low and the porosity on the side where the resin entered was relatively high. As a result, at the boundary between the resin and the interpenetrating layer, the resin area ratio (contact area ratio) relative to the entire boundary surface of the surface where the resin is in contact with the metal is relatively small, and conversely, the resin enters the interpenetrating layer The resin area ratio (penetration area ratio) with respect to the entire boundary surface of the surface that is in operation is relatively large, and the amount of resin that has entered the interpenetrating layer at the boundary increases. As described above, since the resin area ratio of the surface where the resin enters the interpenetrating layer at the boundary between the resin and the interpenetrating layer is relatively increased, the stress generated in the resin is reduced. As a result, breakage hardly occurs at the boundary between the resin and the interpenetrating layer, and the bonding strength between the resin and the interpenetrating layer can be increased.

  In this case, since the metal volume fraction is larger on the side in contact with the metal than on the side in which the resin enters, the bonding strength between the metal and the interpenetrating layer does not decrease. That is, if the porosity is increased as a whole from the side in contact with the metal to the side into which the resin enters, high stress is generated at the boundary between the metal and the interpenetrating layer, and the bonding strength between the metal and the interpenetrating layer is increased. Although there is a possibility of causing a decrease, by inclining so as to increase the porosity from the side in contact with the metal to the side into which the resin enters, while maintaining the bonding strength between the metal and the interpenetrating layer to some extent, Bonding strength between the resin and the interpenetrating layer can be increased.

The present invention is not limited to the above-described embodiment, and can be modified or expanded as follows.
In the present embodiment, Ti having a relatively small specific gravity (specific gravity is about 4.54 g / cm ³ ) is exemplified as a metal used as a substrate. However, if the demand for weight reduction is small, the specific gravity is larger than Ti, for example, Cu (copper, Melting point is about 1085 ° C., specific gravity is about 8.96 g / cm ³ ), Ni (nickel, melting point is about 1455 ° C., specific gravity is about 8.902 g / cm ³ ), Fe (iron, melting point is about 1538 ° C., specific gravity is about Another metal such as about 7.874 g / cm ³ ), W (tungsten, melting point is about 3422 ° C., specific gravity is about 19.3 g / cm ³ ) may be used. Al is exemplified as a metal used as an auxiliary agent for sintering Ti, but Mg (melting point is about 650 ° C.) and Pb (melting point is about 327.degree. C.) if the melting point is lower than that of NaCl powder as a spacer powder. Another metal such as 5 ° C.) may be used.

  In the present embodiment, the case where NaCl powder is used as the spacer powder is exemplified, but the melting point is higher than that of the metal used as an auxiliary agent, it does not melt at the time of sintering, and can be removed by a method such as washing with water, volatilization or combustion. Any material may be used as the spacer powder as long as the conditions are satisfied. For example, KCl (potassium chloride) powder may be used. Moreover, although the method of dissolving NaCl powder in still water was illustrated, it may be removed by any method such as burning.

  In the present embodiment, the case has been described in which the porosity always increases from the side in contact with the metal toward the side where the resin enters (there is no area to decrease), but the porosity does not always increase (decreases). (There may be an area to do). For example, when the raw material powder is filled in the hollow portion 2a of the mold 2, the volume fraction of the NaCl powder may be in the order of 50%, 60%, 50%, 70%, and 80%.

  In the present embodiment, the volume fraction of the NaCl powder is divided into a plurality of stages, and the procedure for producing the interpenetrating layer having the gradient volume fraction is exemplified. However, the pressure for heating the raw material powder and the temperature for heating are adjusted (discrimination). In this case, an interpenetrating layer having an inclined volume fraction may be produced. That is, the volume fraction of NaCl powder is kept constant, and on the side in contact with the metal, the heating temperature is relatively high to promote densification of the powder, so that the porosity is relatively low and the resin penetrates. On the other hand, the porosity may be made relatively high by lowering the heating temperature to suppress densification of the powder.

Claims (11)

  The raw material powder containing the metal powder and the spacer powder is pressurized and heated under conditions of pressure and temperature at which the spacer powder is not crushed or decomposed to sinter the metal powder, and then the spacer powder is removed. A porous layer characterized by producing a porous layer by a method of forming a void portion so that the porosity on the side in contact with the metal is relatively low and the porosity on the side into which the resin enters is relatively high Method for making the layer. The method for producing a porous layer according to claim 1 ,
On the side in contact with the metal, the volume fraction of the spacer powder relative to the entire raw material powder is relatively low, and on the side where the resin permeates, the volume fraction of the spacer powder relative to the entire raw material powder is relatively increased to burn the metal powder. A method for producing a porous layer, characterized in that the porous layer is produced by bonding. The method for producing a porous layer according to claim 1 ,
At least one of the pressure to press the raw material powder and the heating temperature is relatively high on the side in contact with the metal, and at least one of the pressure to press the raw material powder and the heating temperature is relatively high on the side where the resin enters. A method for producing a porous layer, characterized in that the metal powder is sintered at a low temperature to produce a porous layer. In the manufacturing method of the porous layer as described in any one of Claim 1 to 3 ,
A method for producing a porous layer, comprising producing a porous layer so that the porosity is constantly increased from a side in contact with a metal toward a side into which a resin enters. In the manufacturing method of the porous layer as described in any one of Claim 1 to 4 ,
A method for producing a porous layer, wherein the spacer powder is produced using a powder that dissolves in still water.   On a metal substrate, a raw material powder containing a metal powder and a spacer powder is pressed and heated under pressure and temperature conditions that prevent the spacer powder from being crushed or decomposed, and then the metal powder is sintered. By removing the spacer powder to prepare a porous layer, the resin volume fraction on the side in contact with the metal is relatively low due to the method of allowing the resin to penetrate into the voids of the porous layer, and the resin penetrates. A method for producing an interpenetrating layer, comprising producing an interpenetrating layer so that the resin volume fraction on the side of the inner side is relatively high. The method for producing an interpenetrating layer according to claim 6 ,
On the side in contact with the metal, the volume fraction of the spacer powder relative to the entire raw material powder is relatively low, and on the side where the resin penetrates, the volume fraction of the spacer powder relative to the entire raw material powder is relatively high. A method for producing an interpenetrating layer, which comprises sintering an interpenetrating layer to produce an interpenetrating layer. The method for producing an interpenetrating layer according to claim 6 ,
At least one of the pressure to press the raw material powder and the heating temperature is relatively high on the side in contact with the metal, and at least one of the pressure to press the raw material powder and the heating temperature on the side where the resin enters A method for producing an interpenetrating layer, wherein the metal powder is sintered with a relatively low value to produce an interpenetrating layer. In the method for producing an interpenetrating layer according to any one of claims 6 to 8 ,
A method for producing an interpenetrating layer, characterized in that the interpenetrating layer is produced so that the resin volume fraction is constantly increased from the side in contact with the metal toward the side in which the resin has entered. In the method for producing an interpenetrating layer according to any one of claims 6 to 9 ,
A method for producing an interpenetrating layer, wherein the spacer powder is produced using a powder that dissolves in still water. A method for producing an interpenetrating layer according to any one of claims 6 to 10 ,
A method of joining a metal and a resin, wherein the metal and the resin are joined through the interpenetrating layer.