JP4973636B2 - Method for producing foamed resin composite structure - Google Patents

Description

  The present invention relates to a method for manufacturing a foamed resin composite structure using a base material made of foamed resin.

  Conventionally, synthetic resins having functions such as conductivity and insect protection have been proposed. For example, a method is known in which a liquid resin composite material in which metal powder is mixed with a thermoplastic resin such as an epoxy resin is injection-molded to produce a conductive resin molded product (Patent Document 1). Further, a method is known in which a liquid resin composite material in which an insecticide is mixed with a thermoplastic resin such as an epoxy resin is injection-molded to produce a conductive resin molded product (Patent Document 2).

JP-A-5-255517 (paragraphs 25-39, Tables 1 and 2) JP-A-6-183904 (paragraphs 15 to 24)

  However, all of the conductive resin molded products manufactured by the conventional methods described above have a problem that they are heavy because they are molded from a thermoplastic resin.

  Therefore, an object of the present invention is to realize a foamed resin composite structure having functions such as conductivity and insect repellent while being lightweight.

In order to achieve the above object, according to the present invention described in claims 1 to 19, the closed cell structure is formed by fusing adjacent foam cells (1c) to each other. The base material (1) having communication holes (1d) communicating from one surface (1a) to the other surface (1b) and the powder (7) are dispersed by communication between the closed cells. And a first flowable material (4) in which a first component for adhering the powder to the inner wall surface of the communication hole is dissolved or dispersed, and the powder is adhered to the inner wall surface of the communication hole. A second flowable material (6) comprising a second component and between the one surface and the other surface such that the pressure on the other surface is lower than the one surface; And a differential pressure generating device (3) for generating a differential pressure in the first flowable material The first step disposed on the one surface and the first step disposed on the one surface by generating a differential pressure between the one surface and the other surface by the differential pressure generating device. A fluid material is infiltrated into the communication hole, and the powder contained in the infiltrated first fluid material is contained in the communication hole by the first component contained in the infiltrated first fluid material. A second step of creating a state of adhering to the wall surface (1e), a third step of arranging the second fluid material on the one surface, and the one surface and the other surface by the differential pressure generator. The second fluid material disposed on the one surface is permeated into the communication hole by generating a differential pressure between the second fluid material and the second fluid material contained in the permeated second fluid material. create a state in which the communication hole the powder is fixed to the inner wall surface of the communication hole is closed by the component The technical means of having a fourth step, is used.
In addition, said fixation means the state which is hard to peel rather than adhesion.

In the invention according to claim 2, Iote the manufacturing method of the foamed resin molded article according to claim 1 (5), the second component, a technique called ing from the same component as the first component Use appropriate means.

  According to a third aspect of the present invention, in the method for producing a foamed resin composite structure (5) according to the first or second aspect, the state made in the second step is that the powder (7) A technical means is used in which the surface is continuously attached from the opening surface opened to the one surface (1a) of the hole (1d) to the inner wall surface (1e) having a predetermined depth (d).

  According to a fourth aspect of the present invention, in the method for producing a foamed resin composite structure (5) according to any one of the first to third aspects, the state created in the second step is the powder (7 ) Continuously attached to the inner wall surface (1e) from the opening surface opened to the one surface (1a) of the communication hole (1d) to the opening surface opened to the other surface (1b). Use technical means that there is.

  According to a fifth aspect of the present invention, in the method for producing a foamed resin composite structure (5) according to any one of the first to fourth aspects, the second step includes the differential pressure generating device (3). ) To generate the differential pressure between the one surface (1a) and the other surface (1b), so that the first fluid material (4) disposed on the one surface is Allowing the powder (7) to continuously penetrate from the inner wall surface (1e) of the communication hole to the one surface by infiltrating from the surface into the communication hole (1d) and remaining on the one surface. In the fourth step, the second fluid material disposed on the one surface is generated by generating a differential pressure between the one surface and the other surface by the differential pressure generating device. (6) is infiltrated into the communication hole and is allowed to remain on the one surface, and the second fluid material It said powder by said second component includes use of technical means that is a step of making a state where the inner wall surface and fixed in succession to the one surface of the communication hole.

  According to a sixth aspect of the present invention, in the method for producing a foamed resin molded article (5) according to any one of the first to fifth aspects, the technical means that the second component is a resin. Use.

  According to a seventh aspect of the present invention, in the method for producing a foamed resin molded article (5) according to any one of the first to fifth aspects, the first and second components are resins. Use appropriate means.

  According to an eighth aspect of the present invention, in the method for producing a foamed resin composite structure (5) according to the sixth or seventh aspect, the fourth step is performed by the differential pressure generating device (3). By generating a differential pressure between the surface (1a) and the other surface (1b), the second fluid material (4) disposed on the one surface is introduced into the communication hole (1d). The powder (7) is fixed to the inner wall surface (1e) of the communication hole by the second component contained in the second fluid material that has permeated and remains on the one surface. At the same time, a technical means is used that is a step of forming a film (6a) on the one surface by the second component.

  According to a ninth aspect of the present invention, in the method for producing a foamed resin composite structure (5) according to any one of the first to eighth aspects, the first and second flowable materials (4, 4) are provided. The technical means that the viscosity of 6) is 2000 mPa · s or less is used.

  According to a tenth aspect of the invention, in the method for producing a foamed resin molded article (5) according to the ninth aspect, the technical means that the first component is at least 1 vol% or more is used.

  According to an eleventh aspect of the present invention, in the method for producing a foamed resin composite structure (5) according to the ninth or tenth aspect, the average diameter of the communication holes (1d) is 10 to 150 μm. Use means.

  According to a twelfth aspect of the present invention, in the method for producing a foamed resin composite structure (5) according to the eleventh aspect, the total volume ratio of the first and second components and the powder is set to the size of the communication hole. A technical means of selecting from 18 to 95 vol% according to the average diameter is used.

  According to a thirteenth aspect of the present invention, in the method for producing a foamed resin composite structure (5) according to any one of the first to twelfth aspects, the powder (7) is a conductive powder and a magnetic powder. Use at least one technical means.

  In the invention described in claim 14, in the method for producing the foamed resin composite structure (5) according to claim 13, a technical means that the conductive powder (7) is a powder made of at least copper is used.

  According to a fifteenth aspect of the present invention, in the method for producing a foamed resin composite structure (5) according to the thirteenth or fourteenth aspect, the technical means that the magnetic powder (7) is a powder made of at least ferrite. Is used.

  In the invention described in claim 16, in the method for producing a foamed resin composite structure (5) according to any one of claims 1 to 15, the powder (7) is a powder comprising at least boric acid. Use technical means that there is.

  The invention according to claim 17 is the method for producing a foamed resin composite structure according to any one of claims 1 to 16, wherein the first fluid material (4) is acrylic, synthetic The technical means of being a solvent-type or dispersion-type resin composed of at least one of rubber, vinyl acetate, ethylene, epoxy, and urethane is used.

  The invention according to claim 18 is the method for producing a foamed resin composite structure (5) according to any one of claims 1 to 17, wherein the second fluid material (6) is acrylic. A technical means is used that is a solvent type or dispersion type resin composed of at least one of a resin, a synthetic rubber, a vinyl acetate, an ethylene, an epoxy, and a urethane.

  According to a nineteenth aspect of the present invention, in the method for producing a foamed resin composite structure (5) according to the seventeenth or eighteenth aspect, the first fluid material (4) is an aqueous resin emulsion. Use technical means.

  According to a twentieth aspect of the present invention, in the method for producing a foamed resin composite structure (5) according to any one of the seventeenth to nineteenth aspects, the second fluid material (6) is a resin. The technical means of being an aqueous emulsion is used.

  The base material according to any one of claims 1 to 20 is a foamed resin molded body having a shape of a mold obtained by filling a mold with a foamed resin raw material such as foam beads and heating and foaming it. This is a foamed resin molded body prepared by fusing the foamed resin molded body itself with a heated nichrome wire or the like.

In addition, the above-mentioned foamed resin molded body includes a foamed resin molded body having a roughened predetermined surface of the foamed resin molded body itself according to the shape of the above-described mold or the above-described melt-cutting. The body is included.
In addition, the code | symbol in said parenthesis shows the correspondence with embodiment mentioned later.

(Effect of the invention according to claims 1 to 20)
Since the powder can be fixed to the inner wall surface of the communication hole formed in the base material made of foamed resin, the function of the powder can be given to the base material.
Therefore, it is possible to realize a foamed resin composite structure that is lightweight and has the function of powder.

  In particular, since the base material is a so-called foamed resin molded product in which a closed cell structure is formed by fusing adjacent foam cells, a large number of communication holes exist on each surface of the base material. For this reason, since the surface infiltrated with the first fluid material has many communication holes in which the powder is fixed to the inner wall surface, the function of the powder is maximized.

For example, if conductive powder or magnetic powder is used as the powder, a foamed resin composite structure having conductivity or magnetism can be realized while being lightweight. This foamed resin composite structure can be used, for example, as an electromagnetic shielding material or an antistatic material.
If boric acid is used as the powder, a foamed resin composite structure having a biological repellent effect while being lightweight can be realized. This foamed resin composite structure can be used, for example, as a building material such as an outer wall heat insulating board having an insecticidal effect. Moreover, if it uses as a float which gives buoyancy to an offshore structure, it can prevent that organisms, such as a shellfish and algae, adhere to a float.

In particular, since the communication hole formed in the base material made of foamed resin can be closed, it is possible to realize a foamed resin composite structure in which powder does not spill from the communication hole. In addition, when the foamed resin composite structure is used for use in contact with water, it is possible to realize a foamed resin composite structure with no risk of water leakage through the communication hole.

For example, if it is used as a water pan (drain pan) such as a refrigerator or an air conditioner, a water pan that is light and does not leak can be realized.
For example, if conductive powder or magnetic powder is used as the powder, the foamed resin composite structure is light and has conductivity or magnetism, and the conductive powder or magnetic powder does not leak from the communication hole. Can be realized. Therefore, there is no possibility that the conductivity or magnetism will decrease due to leakage of the conductive powder or magnetic powder.

Further, when boric acid is used as the powder, it is possible to realize a foamed resin composite structure that is lightweight but has a biological repellent effect and does not cause boric acid to leak from the communication hole. Therefore, there is no possibility that the biological repellent effect is lowered due to leakage of boric acid.
Furthermore, if a foamed resin composite structure in which boric acid is fixed to the inner wall surface of the communication hole is used as an outer wall heat insulating material, an outer wall heat insulating material that does not attract termites and does not leak rainwater can be realized.

(Effect of the invention according to claim 3)
Since it is possible to create a state in which the powder continuously adheres from the opening surface opened to one surface of the communication hole to the inner wall surface of a predetermined depth, the powder adheres only to one surface of the base material The amount of powder contained in the base material can be increased as compared with the product.
Accordingly, it is possible to lengthen the time for which the function of the powder is exhibited. Further, even when one surface of the base material is scratched, the powder is exposed also to the scratched region, so that the function of the powder is not partially lost.

For example, if boric acid is used as the powder, it is possible to realize a foamed resin composite structure that is lightweight and has a long duration of biological repellent effect. In addition, even if scratched, the biological repellent effect is not partially lost.
Further, if conductive powder or magnetic powder is used as the powder, there is no possibility that the conductivity or magnetism will be partially lost even if scratched.

(Effect of the invention according to claim 4)
Since the powder can be made to continuously adhere to the inner wall surface from the opening surface opened to one surface of the communication hole to the opening surface opened to the other surface, the function of the powder is one end of the communication hole. To the other end.
Therefore, it is possible to realize a foamed resin composite structure in which the function of the powder is continuous from one surface to the other surface.

For example, if conductive powder is used as the powder, it is possible to realize a foamed resin composite structure in which the connection between one surface and the other surface is conducted while being lightweight.
If boric acid is used as the powder, a foamed resin composite structure having a biological repellent effect on both one surface and the other surface can be realized while being lightweight.

(Effect of the invention according to claim 5)
Since the powder adheres to the inner wall surface of the communication hole and one surface of the base material, and can create a continuous state from the inner wall surface of the communication hole to one surface of the base material, the function of the powder is From one surface to the inner wall surface of the communication hole.

  In particular, since the powder is also fixed to one surface of the base material, the density of the powder on one surface of the base material can be made higher than that fixed only to the inner wall surface of the communication hole. The effect of powder can be increased.

For example, if a conductive powder is used as the powder, it is possible to realize a foamed resin composite structure having a small electrical resistance on one surface while being lightweight. If conductive powder or magnetic powder is used as the powder, it is possible to realize a foamed resin composite structure having a large electromagnetic shielding effect while being lightweight.
Moreover, if boric acid is used as the powder, it is possible to realize a foamed resin composite structure having a large biological repellent effect in one aspect while being lightweight.

(Effect of the invention according to claim 6)
Since the second component is a resin, the adhesion force of the powder to the inner wall surface of the communication hole and one surface of the base material can be increased. A foamed resin composite structure that is difficult to peel off can be realized.

(Effect of the invention according to claim 7)
Since the first component is a resin, the powder attached to the inner wall surface of the communication hole in the second step is difficult to peel off. That is, there is little possibility that the adhesion position of the powder fluctuates before starting the fourth step.
In addition, since the second component is a resin, the adhesion force of the powder to the inner wall surface of the communication hole and one surface of the base material can be increased. A foamed resin composite structure that hardly peels off from the surface can be realized.

(Effect of the invention according to claim 8)
Since the film is formed on one surface of the base material by the second component, the powder fixed on the one surface can be further prevented from peeling off.
Further, since all the communication holes opened on one surface of the base material can be closed, powder leaking from the communication holes can be eliminated. Furthermore, water leakage can be eliminated.

(Effect of the invention according to claim 9)
Since the viscosity of the first flowable material is 2000 mPa · s or less, the first flowable material can easily penetrate into the communication holes of the base material. Therefore, the powder dispersed in the first flowable material is connected to the communication holes. Easy to reach inside. In addition, since the viscosity of the second fluid material is 2000 mPa · s or less, the second fluid material can easily penetrate into the communication hole of the base material. It is easy to fix with the component of 2.

(Effect of the invention according to claim 10)
When the first component is at least 1 vol% or more, the powder can be attached to the inner wall surface of the communication hole.

(Effect of the invention according to claim 11)
Since the average diameter of the communication holes is 10 to 150 μm, the first and second fluid materials can easily penetrate into the communication holes of the base material.

(Effect of the invention according to claim 12)
By selecting the total volume ratio of the first and second components and the powder from 18 to 95 vol% according to the average diameter of the communicating holes of the base material, the first and second components and the powder Can be penetrated into the communication hole of the base material efficiently and at low cost.

(Effect of the invention according to claim 13)
Since at least one of the conductive powder and the magnetic powder is dispersed in the first fluid material, the foamed resin composite structure can have at least one property of conductivity and magnetism.

(Effect of the invention according to claim 14)
Since the powder made of at least copper is dispersed in the first fluid material, the foamed resin composite structure can have at least conductivity.

(Effect of the invention according to claim 15)
Since the powder consisting of at least ferrite is dispersed in the first fluid material, at least magnetism can be given to the foamed resin composite structure.

(Effect of the invention according to claim 16)
Since the powder made of at least boric acid is dispersed in the first fluid material, the foamed resin composite structure can have at least the property of repelling living organisms.

(Effect of the invention according to claim 17)
Since the first fluid material is a solvent-type or dispersion-type resin composed of at least one of acrylic, synthetic rubber, vinyl acetate, ethylene, epoxy, and urethane, the first fluid material It is easy to adhere the powder dispersed in the inner wall surface of the communication hole using the adhesive force of the resin.

(Effect of the Invention of Claim 18)
The second fluid material is a solvent-type or dispersion-type resin composed of at least one of acrylic, synthetic rubber, vinyl acetate, ethylene, epoxy, and urethane. The adhesion force of the adhering powder can be increased and the powder can be fixed to the inner wall surface of the communication hole.

(Effect of the Invention of Claim 19)
Since the first fluid material is a resin aqueous emulsion, it does not dissolve the base material. Further, the viscosity can be easily adjusted by diluting with water. Furthermore, there is little generation of VOC (Volatile Organic Compounds).

(Effect of the invention according to claim 20)
Since the second fluid material is an aqueous resin emulsion, it does not dissolve the base material. Further, the viscosity can be easily adjusted by diluting with water. Furthermore, the occurrence of VOC is small.

<First Embodiment>
A method for producing a foamed resin composite structure according to an embodiment of the present invention will be described with reference to the drawings.

[Base material structure]
The structure of the base material for manufacturing the foamed resin composite structure will be described with reference to the drawings.
FIG. 1 is an explanatory diagram of a base material, where (a) is a perspective view of the base material, and (b) is an enlarged view of a region D shown in (a). As shown in FIG. 1B, the base material 1 is formed by aggregating a large number of foam cells 1c formed by foaming a foamed resin molding raw material such as foam beads. The respective foam cells 1c are fused to each other by heating.

  Between each foam cell 1c, the space | gap 1d is formed and each space | gap 1d is each independent. That is, the base material 1 is formed in a closed cell structure. However, some of the gaps 1d are in communication with each other, whereby the base material 1 is formed with a large number of communication holes that communicate from one surface 1a to the other surface 1b. The communication hole exists not only between the front surface and the back surface of the base material 1 but also between the front surface and the side surface or between the back surface and the side surface.

[Experiment 1]
The inventors of the present application conducted an experiment to determine the upper limit of the viscosity of the fluid material that can penetrate into the communication hole of the base material 1.

(apparatus)
An apparatus for infiltrating the fluid material into the base material 1 will be described with reference to the drawings. FIG. 2 is a longitudinal sectional view showing a state in which the base material 1 and the flowable material 4 are set in the apparatus.

  The apparatus includes a container 2 and a decompression device 3. The upper surface of the container 2 is opened, and the inside thereof is divided into two upper and lower spaces by a partition 2a. The upper space 2b is formed in a space that accommodates the base material 1 and the flowable material 4, and the lower space 2c is a decompression chamber 2d. Vents 2e that communicate from the upper space 2b to the decompression chamber 2d are formed through the middle partition 2a at a plurality of locations. The decompression chamber 2d communicates with an exhaust port 2f formed through the side wall of the decompression chamber 2d, and the exhaust port 2f is connected to the decompression device 3 through a pipe 3a. In this experiment, a vacuum pump capable of adjusting the pressure in the decompression chamber 2d was used as the decompression device 3.

(Experiment contents)
As the flowable material 4, water having a viscosity of 1 mPa · s and a vinyl acetate solution having a viscosity higher than that of water were used. Also, a plurality of flowable materials having different viscosities were prepared by diluting the vinyl acetate solution. The vinyl acetate solution was diluted with methanol. As the base material 1, a plurality of materials having EPS (Expanded Poly-Styrene: beaded polystyrene foam), different expansion ratios, and different average diameters of communication holes were prepared. Of the prepared base material 1, the smallest average diameter of the communication holes is 12 μm, and the largest is 130 μm. The thickness of each base material 1 is 25 mm. A method for calculating the average diameter of the communication holes will be described later.

  And it experimented with the following procedure. First, the base material 1 is arrange | positioned on the partition 2a of the above-mentioned apparatus. Next, the fluid material 4 is disposed on the base material 1. Next, the decompression device 3 was operated, the decompression chamber 2d was decompressed to −80 kPa, and evacuation was performed. Then, the time required for the fluid material 4 to reach the lower surface through the communication hole of the base material 1 from the start of pressure reduction was measured.

(Experimental result)
FIG. 3 is a chart showing the results of Experiment 1 for a base material having an expansion ratio of 60 times, an average diameter of communication holes of 70 μm, and a porosity (ratio of voids in the base material volume) of 3%. As shown in the figure, in the case of water having a viscosity of 1 mPa · s, it reached the lower surface of the base material 1 instantaneously from the start of pressure reduction. And in the case of the diluted product of the vinyl acetate solution whose viscosity is 500, 1000, 1500 mPa * s, the measurement time was 10 seconds, 30 seconds, and 5 minutes, respectively. In the case of a diluted product of a vinyl acetate solution having a viscosity of 2000 mPa · s, the measurement time was 15 minutes, and the solution slightly reached the lower surface.
In addition, the measurement time at each viscosity tends to be slightly longer as the average diameter of the communication holes is smaller, and slightly shorter as the average diameter of the communication holes is larger, but the average of the communication holes in the range of 12 to 130 μm. The difference in measurement time due to the difference in diameter was small.

(Conclusion)
From the above experimental results, it was found that the upper limit of the viscosity of the flowable material that can penetrate the base material 1 is 2000 mPa · s.
In other words, it was found that in order to close the communication hole of the base material 1, a fluid material containing resin and having a viscosity of 2000 mPa · s or less may be used.

[Experiment 2]
Next, the inventors of the present application conducted an experiment for obtaining the upper limit value of the particle size of the powder that can penetrate into the base material 1. 4 is a chart summarizing the results of Experiment 2, wherein (a) is a chart showing the particle size distribution of copper powder MA-CC, (b) is a chart showing the particle size distribution of copper powder MA-C04J, (c). Is a chart showing the results of Experiment 2. FIG.

(Experiment contents)
In this experiment, a mixture of two types of powders, copper powder MA-CC (hereinafter referred to as copper powder A) and MA-C04J (hereinafter referred to as copper powder B) manufactured by Mitsui Mining & Smelting Co., Ltd. was used. As shown in FIG. 4A, the particle size distribution of the copper powder A is 4.6% for 75 μm or more, 5.8% for 75 to 63 μm, 14.8% for 63 to 45, and 74.8 for 45 μm or less. % (Both wt%). Moreover, as shown in FIG.4 (b), as for the particle size distribution of the copper powder B, 8.4 micrometers or more are 10%, and 8.4 micrometers or less are 90% (all are wt%). In this experiment, water was used as a solvent for dispersing copper powder. And what mixed copper powder A and B was disperse | distributed to water, and the fluid material was created. The base material is made of EPS, the expansion ratio is 60 times, the average diameter of the communication holes is 70 μm, the porosity is 3%, and the thickness is 20 mm.

  And using the same apparatus as Experiment 1, said fluid material was arrange | positioned on the upper surface of the base material 1, evacuation was performed at -80kPa, and the state of the lower surface of the base material 1 was observed. Moreover, after evacuation was completed, the base material 1 was cut longitudinally and the cross section was observed. In addition, a plurality of types of flowable materials having different mass ratios of the copper powders A and B were prepared and the same experiment was performed.

(Experimental result)
As a result, when the volume ratio of the copper powders A and B is 1%: 20%, 5%: 20%, 15%: 20% and 20%: 20% (both wt%), the vacuum is drawn for 15 seconds. Thus, it was observed that the copper powder reached the lower surface of the base material 1. Further, when the base material 1 was cut vertically after drying and the cross section was observed, it was found that the entire base material was impregnated with the copper powders A and B.

Moreover, when copper powder B was not disperse | distributed and only copper powder A was disperse | distributed 10 wt%, only water reached | attained the lower surface of the base material 1, and copper powder A did not reach | attain. When the cross section of the base material 1 was observed, it was found that the copper powder A remained only on the surface of the base material.
Further, when copper powder A is not dispersed and only copper powder B is dispersed by 50%, 40%, 30% and 20% (all wt%), copper powder B is the lower surface of base material 1 in any case. Observed that Moreover, when the cross section of each base material was observed, it turned out that the copper powder B impregnates the whole base material in all.

(Conclusion)
From the above experimental results, the copper powder A alone cannot penetrate the communication hole of the base material 1, but the copper powder B alone allows the copper powder B to penetrate the communication hole of the base material 1. Can do.
That is, a copper material dispersed in water is prepared by preparing a fluid material obtained by dispersing copper powder having a particle size of about 10 μm or less in water, placing the material on the upper surface of the base material 1, and performing vacuuming. Powder can be penetrated into the communication holes of the base material 1.

[Experiment 3]
Next, the inventors of the present application conducted an experiment to determine the amount of resin necessary for the inorganic powder not to flow out of the communication hole of the base material 1. FIG. 5 is a chart summarizing the results of Experiment 3.

(Experiment contents)
In this experiment, the same base material as in Experiment 2 was used. Further, as the fluid material, a material obtained by dispersing the aforementioned copper powder B in Acronal S400 (Acronal is a registered trademark of BASF) manufactured by BASF Japan Ltd. was used. Acronal S400 is an aqueous emulsion of an acrylate-styrene copolymer resin, and the resin content of the stock solution is 60 vol%.

  Further, the acronal S400 is diluted with water, and the ratio of the resin content and the copper powder B is 30: 6, 2.5: 10, 2.5: 6, 1:50 (the unit is vol%). Made the material. Moreover, the copper powder B was disperse | distributed to water, and three types of fluid materials with 40 vol%, 50 vol%, and 60 vol% of copper powder B were prepared with a resin content of 0 vol%. The flowable material having a resin component and the flowable material having no resin component both have a viscosity of 2000 mPa · s or less.

  And using the same apparatus as Experiment 1, said fluid material was arrange | positioned on the upper surface of the base material 1, evacuation was performed at -80kPa, and the state of the lower surface of the base material 1 was observed.

(Experimental result)
As a result, in the case of a fluid material having a resin content of 1 to 30 vol%, as a result of performing evacuation for 30 seconds, only water flowed out from the lower surface of the base material 1 and copper powder B did not flow out. . Further, in the case of a fluid material having a resin content of 0 vol%, evacuation for 15 seconds was performed for all, and as a result, water and copper powder B flowed out from the lower surface of the base material 1.

(Conclusion)
From the above experimental results, if the fluid material in which the copper powder B is dispersed in the acronal S400 containing at least 1 vol% of the resin component is infiltrated into the base material 1, then water is disposed on the upper surface of the base material 1. Even when evacuation is performed, the copper powder B does not flow out from the lower surface of the base material 1.
That is, if a flowable material in which an inorganic powder having a particle size of 10 μm or less is dispersed in an emulsion containing at least 1 vol% of the resin component, the inorganic powder can be impregnated in the base material. Can be prevented from flowing out of the base material.

[Experiment 4]
Next, the inventors of the present application conducted an experiment for determining the amount of resin necessary for preventing the organic powder from flowing out of the communication hole of the base material 1. FIG. 6 is a chart summarizing the results of Experiment 4.

(Experiment contents)
In this experiment, the same base material as in Experiment 3 was used. In addition, a material obtained by dispersing polymethyl methacrylate powder in Acronal S400 was used as the fluid material. Further, Acronal S400 was diluted with water to prepare a flowable material having a resin content and a powder ratio of 30: 6, 2.5: 10, and 1:50 (the unit is vol%). Moreover, the powder was disperse | distributed to water and three types of fluid materials with a resin content of 0 vol% and a powder of 40 vol%, 50 vol%, and 60 vol% were created. The flowable material having a resin component and the flowable material having no resin component both have a viscosity of 2000 mPa · s or less.

  And using the same apparatus as Experiment 3, said fluid material was arrange | positioned on the upper surface of the base material 1, evacuation was performed at -80kPa, and the state of the lower surface of the base material 1 was observed.

(Experimental result)
As a result, in the case of a fluid material having a resin content of 1 to 30 vol%, all were evacuated for 30 seconds. As a result, only water flowed out from the lower surface of the base material 1 and powder did not flow out. Further, in the case of a fluid material having a resin content of 0 vol%, evacuation for 15 seconds was performed for all, and as a result, water and powder flowed out from the lower surface of the base material 1.

(Conclusion)
From the above experimental results, if a flowable material in which a polymethyl methacrylate powder is dispersed in an acronal S400 containing at least 1 vol% of resin is infiltrated into the base material 1, then water is applied to the upper surface of the base material 1. Even if it is arranged and vacuumed, the powder does not flow out from the lower surface of the base material 1.
That is, if a flowable material in which an organic powder having a particle size of 10 μm or less is dispersed in an emulsion containing at least 1 vol% of the resin content, the organic powder can be impregnated in the base material, and the impregnated organic powder Can be prevented from flowing out of the base material.

[Experiment 5]
The inventors of the present application examined the resin content and the volume ratio of the powder necessary to give the base material a water stop effect.

(Experiment contents)
In this experiment, copper powder B was dispersed in a product obtained by diluting acronal S400 with water, and a plurality of types of flowable materials having a resin content and a volume ratio of copper powder of 20 to 76 vol% were used. Further, as the base material, a plurality of types of foamed resin moldings having an average diameter of communication holes of 12 to 130 μm were used. Then, using the same apparatus as in each of the above-described experiments, a fluid material was placed on the base material, evacuated at −80 kPa, and the fluid material was infiltrated into the base material. Then, after drying the base material, using the same apparatus, water was placed on the top surface of the base material, and evacuation was performed at −80 kPa for 6 minutes to observe whether water leaked from the bottom surface of the base material.

(Experimental result)
FIG. 7 is a chart summarizing the results of Experiment 5, and FIG. 8 is a graph of the data of FIG. For example, as shown in FIG. 7, a water-stopping effect can be achieved to the inside by allowing a flowable material having a volume fraction of the resin component and the powder to be at least 50 vol% into a base material having an average diameter of communication holes of 70 μm. It has been found that a foamed resin composite structure having can be produced.
As shown in FIG. 8, as the average diameter of the communication holes of the base material before the fluid material penetrates, the volume fraction of the resin component and the powder necessary for obtaining a water stop effect increases. Of the regions partitioned by the graph, the region above the graph (including the line on the graph) is a region having waterstop, and the region below the graph is a region without waterstop.

Among the areas having water-stopping properties, when the resin content and the volume fraction of the powder become larger than necessary, the viscosity of the fluid material exceeds 2000 mPa · s and does not penetrate into the base material, so the viscosity does not exceed 2000 mPa · s. Thus, it is necessary to select the resin content and the volume ratio of the powder.
That is, according to the average diameter of the 12 to 130 μm communicating holes of the base material, the resin content and the volume ratio of the powder are selected from 20 to 76 vol% so as to enter the region having water blocking properties, and the viscosity is 2000 mPa · s. What is necessary is just to produce a fluid material so that it may become the following.

Further, from the graph shown in FIG. 8, the volume fraction of the resin component and the powder is selected from 18 to 85 vol% so as to enter the region having water-stopping property according to the average diameter of the communication holes of 10 to 150 μm of the base material. In addition, it has been found that the flowable material may be prepared so that the viscosity is 2000 mPa · s or less.
In addition, it is desirable to select a volume fraction that is on the line of the graph in order to minimize the flowable material required to produce a water stop effect and maximize cost effectiveness.

  In addition, when low molecular weight acrylic acid or the like is used in a dispersive manner, the viscosity may be 2000 mPa · s or less even when the volume fraction of the resin and the powder exceeds 95 vol%. In the range of the resin that can be used, the viscosity can be set to 2000 mPa · s or less by selecting the volume ratio from 18 to 95 vol%. Desirably, when the volume ratio is selected from 18 to 85 vol%, the viscosity is easily set to 2000 mPa · s or less.

  FIG. 9 is an explanatory view of a foamed resin composite structure in which a fluid material has permeated, (a) is a perspective view of the foamed resin composite structure, and (b) is an enlarged view of a region indicated by D in (a). is there. As shown in FIG. 2B, the communication holes formed between the foamed cells 1 c are closed by the resin layer 6. Moreover, the resin layer 6 is also formed in the voids in which the communication holes are not formed. This resin layer is formed by drying the fluid material that has penetrated into the gap mainly by capillary action and drying the resin contained in the fluid material. As described above, since the resin layer is formed also in the voids where the communication holes are not formed, the strength of the foamed resin composite structure can be increased.

[Experiment 6]
The inventors of the present application conducted an experiment to examine the relationship between the evacuation time and the penetration depth of the fluid material. FIG. 10 is a chart showing the results of Experiment 6.

(Experiment contents)
The base material used in this experiment is EPS, the expansion ratio is 60 times, the average diameter of the communication holes is 70 μm, the porosity is 3%, and the thickness is 50 mm. Further, as a fluid material, a material obtained by dispersing 10 vol% carbon in acronal S400 having a resin content of 20 vol% was used. In addition, the same apparatus as that used in each experiment described above was used, and the pressure in the decompression chamber 2d was set to −80 kPa. And when 1 minute passed since the pressure of the decompression chamber 2d reached -80 kPa, the base material was cut longitudinally and its cross section was observed, and the depth of the region that was changed to black by carbon was measured. Thereafter, the vacuuming time was changed to 2.5 minutes and 5 minutes, and the same measurement was performed.

(Experimental result)
As shown in FIG. 10, the penetration depths of the flowable material when the vacuuming time was 1 minute, 2.5 minutes, and 5 minutes were 5 mm, 10-20 mm, and 25-30 mm, respectively. That is, the penetration depth of the fluid material increased as the evacuation time increased.

FIG. 11 is a schematic diagram of the communication holes, (a) is a schematic diagram showing a state where the powder has penetrated partway through the communication holes, and (b) is a schematic diagram showing a state where the powder has penetrated to the lower surface of the base material. is there.
The powder particles 7 carried into the communication hole 1d by the fluid material are adhered to each other by the resin component 6 contained in the fluid material, and the inside of the communication hole 1d is closed as an aggregate of the particles 7. Then, it was estimated that the particles 7 sent thereafter were accumulated on the blocked site, and the communication holes 1d were filled with the particles 7 as shown in FIG.
In addition, it was estimated that the longer the time of evacuation, the more the aggregate of the particles 7 moves below the communication hole 1d, and the part blocked by the aggregate also moves downward.

(Conclusion)
It was found that the penetration depth of the flowable material in the base material can be controlled by changing the evacuation time.

[Experiment 7]
The inventors of the present application conducted an experiment to impart conductivity to the fluid material. FIG. 12 is a chart showing the results of Experiment 7.

(Experiment contents)
The flowable material used in this experiment is obtained by dispersing copper powder (MA-C04J) in a vinyl acetate solution (resin content 60 vol%) diluted with methanol. Moreover, four types of fluidity | liquidity materials from which the ratio (vol%) of copper powder and resin differed were created. The viscosity of each flowable material is 2000 mPa · s or less. Then, the prepared fluid material is applied to the upper surface of the base material, the base material is dried to evaporate the evaporation component contained in the fluid material, and a film is formed on the upper surface of the base material by the resin component in which the copper powder is dispersed. Formed. And the electrical resistance of the film | membrane surface formed in the upper surface of the foamed resin composite structure was measured.
Moreover, it attached to one kind of fluid material, said measurement was performed with respect to three same base materials of A, B, and C, and the average value was calculated | required.

(Experimental result)
As shown in FIG. 11, the electrical resistance of the top surface of the foamed resin composite structure is 7.31 × 10 ⁸ Ω to 2.11 × 10 ¹⁰ Ω, and the top surface of the foamed resin composite structure has conductivity. I understood. It was also found that there was no significant difference in the electrical resistance of the film even when the ratio of copper powder and resin was changed.

(Conclusion)
From the above experimental results, by applying a fluid material having a viscosity of 2000 mPa · s or less in which copper powder is dispersed in a diluted vinyl acetate solution to a base material, a foamed resin composite structure having conductivity on the coated surface It was found that can be manufactured. In addition, the fluid material is infiltrated into the base material so that the fluid material remains on the top surface of the base material and dried to form a conductive film on the top surface of the base material. It was considered that a foamed resin composite structure that conducted to the inside of the material could be manufactured. Furthermore, it was considered that a foamed resin composite structure in which the upper and lower surfaces of the base material are conductive can be manufactured by infiltrating the fluid material from the upper surface to the lower surface of the base material.

The foamed resin composite structure having the above conductivity has various uses. For example, it is an application requiring antistatic. For example, it can be used for a plate or a container on which electronic components are placed in a factory for assembling electrical products.
FIG. 13 is an explanatory diagram of a dish on which electronic components are placed. In the dish 10, the conductive film is formed on the upper surface 11 on which the electronic component 20 is placed, and the upper surface 11 is electrically connected to the lower surface 12 through the communication hole. The lower surface 12 is connected to the ground. Thereby, the static electricity charged in the electronic component 20 can be released to the ground through the conductive film.

  In particular, the above-described dish 10 is highly effective when used as a dish on which electronic parts such as an IC chip to be gripped by a robot hand are placed in a line for assembling an electric product by a robot. That is, since the static electricity charged on the electronic component can be released from the conductive film to the ground, there is no possibility that the electronic component is destroyed due to the electrostatic discharge when the robot hand grasps the electronic component.

[Production method]
Next, a method for producing a foamed resin composite structure will be described with reference to the drawings. FIG. 14 is a flowchart showing a process flow. 15A and 15B are schematic views of the communication holes of the base material, where FIG. 15A is a schematic view showing a state where powder is attached to the inner wall surface of the communication holes, and FIG. 15B is a schematic view showing a state where resin has penetrated into the communication holes. FIG.

  First, a base material having a communication hole with a desired average diameter is selected from 10 to 150 μm, and the base material is loaded into the apparatus shown in FIG. 2 (step 1). Next, the first fluid material is disposed on the upper surface of the base material (step 2), the decompression device is operated to perform evacuation, and the first fluid material is permeated into the communication hole of the base material (step). 3). At this time, evacuation is performed so that the first fluid material remains in a film shape on the upper surface of the base material. The first fluid material plays a role of delivering the powder to the inside of the communication hole of the base material. In the first fluid material, powder is dispersed, and a first component for adhering the powder to the inner wall surface of the communication hole is dissolved or dispersed.

  For example, as a first fluid material, a fluid having a viscosity of 2000 mPa · s or less obtained by dispersing an inorganic or organic powder having a particle size of 10 μm or less in an aqueous resin emulsion containing 1 vol% of the resin component as the first component. Uses a functional material. If this fluid material is used, as explained in the experiments 3 and 4, the fluid material is infiltrated into the communication hole of the base material, thereby delivering the powder contained in the fluid material to the inside of the communication hole. It can be adhered to the inner wall surface of the communication hole, and the adhered powder can be prevented from moving or flowing out of the communication hole.

  Moreover, the kind of powder is selected according to the function given to the foamed resin composite structure. For example, when producing a foamed resin composite structure having conductivity, a conductive powder such as copper powder is selected as the powder, and when producing a foamed resin composite structure having magnetism, a magnetic material such as ferrite is used as the powder. Select powder. Moreover, when manufacturing the foamed resin composite structure which has a biological repellent effect, boric acid or copper powder is selected as a powder.

Next, the base material is dried to evaporate evaporation components such as water contained in the first fluid material that has penetrated into the communication holes and the first fluid material that remains on the upper surface of the base material (step 4). This drying may be natural drying or forced drying that promotes drying by blowing warm air.
As shown in FIG. 15A, powder particles 7 are adhered to the upper surface 1a of the base material and the inner wall surface 1e of the communication hole after drying. Since each particle 7 is adhered by the adhesive force of the resin contained in the first fluid material, it is difficult to peel off.

  Next, the dried base material is loaded again into the apparatus, the second fluid material is placed on the top surface of the base material (step 5), the decompression device is operated to perform vacuuming, and the second fluidity The material is infiltrated into the communication hole of the base material (step 6). At this time, evacuation is performed so that the second fluid material remains in a film shape on the upper surface of the base material. The second fluid material plays a role of enhancing the adhesion force of the powder adhering to the inner wall surface of the communication hole of the base material and closing the communication hole to provide water-stopping. The second fluid material includes a second component that adheres the powder to the inner wall surface of the communication hole.

  For example, an aqueous resin emulsion in which a resin as the second component is dispersed is used as the second fluid material. The volume fraction of the resin dispersed in the second fluid material is determined by the resin content of the first fluid material used in the previous step and the powder volume fraction. For example, it is assumed that a base material having an average diameter of communication holes of 70 μm is used, and in step 3, a first fluid material having a resin content of 1 vol% and a powder of 19 vol% is infiltrated into the base material.

Here, as shown in FIG. 7, in the case of a base material having an average diameter of communication holes of 70 μm, a foamed resin composite structure having a water-stopping effect is produced if the volume fraction of the resin component and the powder is at least 50 vol%. can do. Accordingly, an aqueous resin emulsion in which at least 30 (= 50-20) vol% resin is dispersed may be used as the second fluid material. The second fluid material may be powdered or an emulsion (second component) alone.

  That is, the resin and powder contained in the first fluid material and the resin contained in the second fluid material are communicated with the base material so that the sum thereof is at least the volume ratio shown in FIG. What is necessary is just to determine according to the average diameter of a hole.

  In addition, it is only necessary to increase the adhesive force of the powder adhering to the inner wall surface of the communication hole, and when the water stop effect is not required, the resin aqueous emulsion in which less than 30 vol% resin is dispersed is used as the second flow. What is necessary is just to use as a property material.

  Next, the base material is dried to evaporate evaporation components such as water contained in the second fluid material penetrating the communication holes and the second fluid material remaining on the upper surface of the base material (step 7). This drying may be natural drying or forced drying that promotes drying by blowing warm air. Then, the foamed resin composite structure completed by drying is taken out from the apparatus (step 8).

  As shown in FIG. 15 (b), the resin portion 6 contained in the second fluid material has permeated into the communication hole 1 d of the foamed resin composite structure 5, and the communication portion 6 allows the communication hole to pass through the communication hole 1 d. 1d is blocked. Further, since the resin portion 6 covers the powder particles 7, the particles 7 are fixed to the inner wall surface 1 e, and are more difficult to peel off. Further, a resin film 6a is formed on the upper surface 1a by curing the resin component 6.

  Further, since the powder particles 7 are continuously attached from the upper surface 1a to the inner wall surface 1e of the communication hole 1d, the function of the powder is continuously exhibited from the upper surface 1a to the inner wall surface 1e of the communication hole 1d. . Furthermore, since the upper surface 1a is covered with the resin coating 6a, even if there is a communication hole 1d that is not blocked by the resin component 6, the communication hole 1d can be blocked by the resin coating 6a. There is no risk that the water stop effect will be lost.

  The first component contained in the first flowable material and the second component contained in the second flowable material may be the same component or different components, but in order to make the powder reach the inside of the communication hole It is desirable to select a low viscosity material as the first flowable material. Moreover, in order to improve the adhesive force and water-stopping effect of the powder, it is possible to select a resin aqueous emulsion having a resin having high adhesive strength as the second component, such as an epoxy resin aqueous emulsion, as the second fluid material. desirable.

[Calculation method of average diameter of communication holes]
Next, a method for calculating the average diameter of the communication holes formed in the base material will be described.

  First, the ratio of the radius of the pre-foamed beads before foaming and the radius of the void formed surrounded by the pre-foamed beads is obtained. FIG. 16 is a schematic view of a pre-foamed bead. Here, it is assumed that the pre-foamed beads are true spheres. As illustrated, the pre-foamed beads 6 are in contact with each other, and a gap 7 is formed in a region surrounded by the three pre-foamed beads 6. Here, it is assumed that the gap 7 is a capillary tube 8 in contact with the three preliminary foam beads 6. A radius of the pre-foamed beads 6 is A, a radius of the capillary 8 is r, an angle formed by a line L1 connecting the centers of the pre-foamed beads 6 and the capillaries 8 and a line L2 connecting the centers of the pre-foamed beads 6 is θ. Then, since θ = 30 °, the following equation (1) is established.

  cos30 ° = A / (A + r) (1)

  Here, substituting cos30 ° ≈0.866 into equation (1) to obtain r,

  r = 0.155A (2)

  That is, the ratio between the radius r of the capillary 8 and the radius A of the pre-foamed beads 6 was obtained. Here, if it is assumed that the expanded beads are expanded while maintaining a true spherical state, the above formula (2) is calculated by the following equation: It can also be applied to the relationship with the radius. Further, since the radius of the capillary 8 surrounded by the pre-expanded beads 6 is increased by the foaming of the pre-expanded beads 6, the above formula (2) can be applied to the relationship between the capillaries before and after the foaming.

  Next, the average diameter of the communication holes formed in the base material actually manufactured by heating, foaming and fusing the preliminary foam beads 6 is determined.

  It is known that the liquid capillary pressure Fc is given by the following formula (3) (cited by Soichi Muroi, published by Kobunsha Co., Ltd., “Polymer Latex for Beginners”).

  Fc = 12.9γ / C (3)

  Here, γ represents the surface tension (N / m) of the liquid, and C represents the radius (m) of the foamed cell forming the capillary tube.

  FIG. 17 is a chart showing the results of a water leak experiment performed on a base material having a foaming magnification of 15 times, and FIG. 18 shows the results of a water leak experiment performed on a base material having a foaming ratio of 60 times. It is a chart. Both base materials are EPS and the thickness is 20 mm. From FIG. 17, in the base material with a foaming ratio of 15 times, water penetrates at a vacuum pressure of −10 kPa. Further, as shown in FIG. 18, in the base material having a foaming magnification of 60 times, water penetrates at a vacuum pressure of −4 kPa.

First, the average diameter of the communication holes formed in the base material having a foaming ratio of 15 is obtained. Since water permeates at -10 kPa (water leakage occurs), the capillary pressure per 1 cm ^{2 of the} base material is 0.1 kPa. Further, the surface tension of water is set to 70 mN / m. Substituting Fc = 0.1 kPa and γ = 70 mN / m into the above equation (3),

0.1 = (12.9 × 70) / (C × 10 ² ) (4)

  When C is obtained from the above equation (4), C = 90.3 μm. Substituting C = 90.3 μm into the above equation (2),

  r = 0.155 × 90.3 μm≈14 μm (5)

  It becomes. Therefore, the average diameter of the communication holes is r × 2 = 14 μm × 2 = 28 μm.

Next, when the average diameter of the communication holes formed in the base material having a foaming ratio of 60 times is obtained, the capillary pressure per 1 cm ^{2 of the} base material is 0. 04 kPa. Further, the surface tension of water is set to 70 mN / m. Substituting Fc = 0.01 kPa and γ = 70 mN / m into the above equation (3),

0.04 = (12.9 × 70) / (C × 10 ² ) (6)

  When C is obtained from the above equation (6), C = 225.75 μm. Then, if C = 225.75 μm is substituted into the above equation (2),

  r = 0.155 × 225.75 μm≈35 μm (7)

  It becomes. Therefore, the average diameter of the communication holes is r × 2 = 35 μm × 2 = 70 μm.

(Effect of embodiment)
(1) If the manufacturing method of the foamed resin composite structure according to the above-described embodiment is performed, the powder can be fixed to the inner wall surface of the communication hole formed in the base material made of foamed resin. The function it has can be given to the base material.
Therefore, it is possible to realize a foamed resin composite structure that is lightweight and has the function of powder.

(2) In particular, since the base material is a so-called foamed resin molded product in which a closed cell structure is formed by fusing adjacent foam cells, a large number of communication holes exist on each surface of the base material. For this reason, since the surface infiltrated with the first fluid material has many communication holes in which the powder is fixed to the inner wall surface, the function of the powder is maximized.

(3) Moreover, since the communicating hole formed in the base material made of foamed resin can be closed, it is possible to realize a foamed resin composite structure in which powder does not spill from the communicating hole. In addition, when the foamed resin composite structure is used for use in contact with water, it is possible to realize a foamed resin composite structure with no risk of water leakage through the communication hole.
For example, if the foamed resin composite structure of the above embodiment is used as a water tray such as a refrigerator or an air conditioner, it is possible to realize a water tray that is lightweight but does not cause water leakage.

(4) Furthermore, since it is possible to create a state in which the powder is continuously attached from the opening surface opened on one surface of the communication hole to the inner wall surface of a predetermined depth, the powder is only on one surface of the base material. Compared with what has adhered, the quantity of the powder contained in the base material can be increased.
Accordingly, it is possible to lengthen the time for which the function of the powder is exhibited. Further, even when one surface of the base material is scratched, the powder is exposed also to the scratched region, so that the function of the powder is not partially lost.
For example, even when the water pan is damaged during transportation of the water pan, or when a tool such as a screwdriver is dropped and cracked or depressed during installation of the water pan, There is no risk of water leaking.

(5) Furthermore, even if the fusion between the foam cells is incomplete and a gap is formed in the base material, the resin component penetrates into the gap, resulting in incomplete fusion. Water leakage can be eliminated.

(6) If an aqueous emulsion in which a curable resin such as an epoxy resin aqueous emulsion is dispersed is infiltrated into the base material, the curable resin that has penetrated into the communicating holes is cured, so that a high-strength foamed resin composite structure is obtained. Can be manufactured.

(7) Since the powder can be made to adhere continuously to the inner wall surface from the opening surface opened to one surface of the communication hole to the opening surface opened to the other surface, the function of the powder is communicated It can be made continuous from one end of the hole to the other end.
Therefore, it is possible to realize a foamed resin composite structure in which the function of the powder is continuous from one surface to the other surface.

(8) Since powder can adhere to the inner wall surface of the communication hole and one surface of the base material and can create a continuous state from the inner wall surface of the communication hole to one surface of the base material, the function of the powder Can be continued from one surface of the base material to the inner wall surface of the communication hole.
In particular, since the powder is also fixed to one surface of the base material, the density of the powder on one surface of the base material can be made higher than that fixed only to the inner wall surface of the communication hole. The effect of powder can be increased.

(9) By selecting the resin as the first component contained in the first fluid material, the powder that has permeated the communication hole can be adhered to the inner wall surface of the communication hole and prevented from moving.

(10) Since the resin can be selected as the second component contained in the second fluid material, the adhesion force of the powder to the inner wall surface of the communication hole and one surface of the base material can be increased. Therefore, it is possible to realize a foamed resin composite structure that does not easily peel off from the inner wall surface of the communication hole or one surface of the base material.

(11) Since a resin is selected as the second component contained in the second fluid material and a resin film is formed on one surface of the base material by the resin, the powder fixed on the one surface is further increased. It can be made difficult to peel off.

(12) Since all the communication holes opened on one surface of the base material can be closed, powder leaking from the communication holes can be eliminated. Furthermore, water leakage can be eliminated.

(13) Since the viscosity of the first flowable material is 2000 mPa · s or less, the first flowable material can easily penetrate into the communication holes of the base material, and thus the powder dispersed in the first flowable material Can easily reach the inside of the communication hole. In addition, since the viscosity of the second fluid material is 2000 mPa · s or less, the second fluid material can easily penetrate into the communication hole of the base material. It is easy to fix with the component of 2.

(14) If the first component contained in the first fluid material is at least 1 vol% or more, the powder can be adhered to the inner wall surface of the communication hole.

(15) Since the average diameter of the communication holes is 10 to 150 μm, the first and second fluid materials can easily penetrate into the communication holes of the base material.

(16) By selecting the total volume ratio of the first and second components and the powder from 18 to 95 vol% according to the average diameter of the communication holes of the base material, the first and second components And powder can be penetrated into the communicating holes of the base material efficiently and at low cost.

(17) A foamed resin composite structure having electrical conductivity can be produced by allowing the first fluid material in which the copper powder is dispersed to permeate the base material.

(18) By selecting a resin aqueous emulsion as the first and second fluid materials, the base material is not dissolved. Further, the viscosity can be easily adjusted by diluting with water. Furthermore, the occurrence of VOC is small.

[Other Embodiments]
(1) A pressurizing device that pressurizes the upper surface of the fluid material disposed on the upper surface of the base material can be used in combination. For example, a lid is disposed in the upper space 2b of the apparatus shown in FIG. 2, and the space formed between the lid and the flowable material is pressurized by sending air with an air pump. According to this method, since the differential pressure between one surface of the base material 1 and the other surface can be increased efficiently, the permeation speed of the flowable material into the base material 1 can be increased. The production efficiency of the resin composite structure can be increased.

(2) It is possible to mask a region of the base material that is not desired to be infiltrated with the fluid material with a film or the like. According to this method, the fluid material can be infiltrated into a desired region of the base material.

(3) Gold, silver, copper, nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium, osmium, aluminum, zinc, tin, lead, etc. powdered as conductive powder, these metals Metal powders such as tin oxides, metal oxides such as tin oxide powders, and conductive carbon allotropes such as carbon powders, but conductive metals on the surface of particles such as glass, carbon, mica, and plastics. Those coated with can be used.

(4) Magnetic powder made of ferrite can be used in place of the conductive powder. According to this, a magnetic foamed resin composite structure can be manufactured. Also be in place of ferrite, cobalt ferrite-based magnetic material, metal _{magnetic, CrO 2, γ-Fe 2} O 3, Fe 4 N, also possible to use a powder such as Ba ferrite. Furthermore, by using a mixture of conductive powder and magnetic powder, a foamed resin composite structure having conductivity and magnetism can be produced.

(5) A fluid material in which a powder made of boric acid is dispersed can be allowed to penetrate into the base material. According to this, it is possible to manufacture a foamed resin composite structure having at least the property of avoiding living things. For example, if the foamed resin composite structure is used as a heat insulating material for a building, insects such as termites and cockroaches can be removed or killed. Moreover, if the foamed resin composite structure is used for a float of an offshore structure, shellfish such as barnacles can be prevented from adhering to the float. In addition, since boric acid can penetrate into the base material, even if the surface of the heat insulating material or float is peeled off or chipped, the biological repellent effect can be maintained. In addition, since copper powder also has a biological repellent effect, when a foamed resin composite structure in which copper powder is infiltrated into a base material is applied to a heat insulating material or a float, the same effect as boric acid can be obtained. Can do.

(6) Further, boric acid or copper powder can be accommodated in microcapsules, and a fluid material in which a powder in which a large number of microcapsules are collected is dispersed can be allowed to penetrate into the base material. For example, as a shell (wall material) constituting the outer shell of the microcapsule, a shell having a property of cracking when the outside air temperature exceeds a predetermined temperature is used, and boric acid is included in the shell as a core (core material). Then, by allowing the flowable material in which the microcapsules are dispersed as a powder to permeate the base material, if the outside air temperature exceeds a predetermined temperature, the microcapsules in the communication holes crack and release boric acid components into the outside air. can do. For example, if the foamed resin composite structure is used as a heat insulating material for a building, insects such as termites and cockroaches can be removed or killed.

(7) It is also possible to use a shell that decomposes naturally over time. The “microcapsule” refers to a minute container having a diameter between nanometers and millimeters. Microcapsules include sealed and porous types.

(8) Use of calcium carbonate, talc, clay, magnesium oxide, zinc oxide, carbon black, silicon dioxide, titanium oxide, glass powder, hollow glass balloon, diatomaceous earth, kaolin, perlite, fluorite, bentonite, etc. as the powder it can.

(9) As the fluid material, a solvent-type or dispersion-type resin composed of at least one of acrylic, synthetic rubber, vinyl acetate, and ethylene can be used. For example, an aqueous resin emulsion such as an epoxy resin aqueous emulsion, an ethylene-acrylic acid copolymer resin aqueous emulsion, a modified aliphatic polyamine resin aqueous emulsion, and a biodegradable resin aqueous emulsion can be used.

An epoxy resin can also be used as the second fluid material. Here, the epoxy resin refers to an epoxy resin obtained by mixing a reactive diluent and a curing agent. Moreover, the thing which mixed the solvent with the epoxy resin and the thing which is not mixed are said.
Examples of the epoxy resin include bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, and alicyclic type. Epoxy resin, heterocyclic epoxy resin, glycidyl ester epoxy resin, glycidyl ether epoxy resin, glycidyl amine epoxy resin, urethane modified epoxy resin, rubber modified epoxy resin, epoxidized elastomer, epoxidized stearate ester, epoxidized Soybean oil, epoxy-modified polysiloxane, flexible epoxy resin, epoxidized (meth) acrylic oligomer, reactive diluent having an epoxy group, and the like can be used.

  Examples of the epoxy resin curing agent include maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl hymic anhydride, methyl CD acid anhydride, methyl nadic acid anhydride, pyromellitic anhydride. , Acid anhydride-based curing agents such as heptic anhydride, dodecenyl succinic anhydride, polyazeline succinic anhydride; ethyleneamines, diethylaminopropylamine, dimethylaminopropylamine, N-aminoethylpiperazine, trimethylhexamethylenediamine, aliphatic Aliphatic amine curing agents such as amine modifications; aromatic amine curing agents such as m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, metaxylylenediamine, aromatic amine modifications; and other curing agents, Isophorondia Emissions, dicyandiamide, piperidine, polyamide resins, phenolic resins, polythiol resins, mercaptan compounds, boron trifluoride amine complex, can be used imidazole compounds.

  Further, as curing accelerators for epoxy resins, tertiary amines, triphenylphosphine, stannous octoate, boron trifluoride complex, benzyldimethylamine, DBU, 2,4,6-tris (dimethylaminomethyl) ) Phenol, isocyanates, sulfonium salts, iodonium salts, diazonium salts, hydrazide compounds, nylon salt compounds, organometallic compounds and the like may be further used.

(10) The fluid material can also be colored. As the colorant, a general pigment or dye can be used. Examples of the pigment include those used as coloring materials and fillers, such as titanium oxide, calcium carbonate, dolomite, cinnamon sand, iron oxide, carbon black, cyanine pigment, and quinacrine pigment. Examples of the dye include azo dyes, anthraquinone dyes, indigoid dyes, and stilbene dyes.

Furthermore, metal powders such as aluminum flakes, nickel powder, gold powder, silver powder, copper powder, and titanium oxide may be used as the colorant.
By coloring the epoxy resin with these colorants, the color and pattern of the foamed resin composite structure can be changed.

(11) The foamed resin raw material for forming the base material 1 is not particularly limited as long as it is foamed at a specific foaming temperature, but is impregnated with a thermoplastic material as a main material and gas or liquid as a foaming agent. Although the thing made to use or the thing containing a thermally decomposable foaming agent is used suitably, what contains both may be used. The thermoplastic substance may be cross-linked.

Commercially available polystyrene foam beads, polyethylene foam beads, polypropylene foam beads, etc. may be used as the thermoplastic resin as the main material and gas or liquid impregnated as a foaming agent, butane, pentane, It may be impregnated with hydrocarbon such as chlorofluorocarbon, water, CO ₂ and N ₂ . Moreover, as a thing containing a thermally decomposable foaming agent, you may use suitably preparing from the thermally decomposable foaming agent and thermoplastic material which are shown below. In this thermally decomposable foaming agent and thermoplastic material, the decomposition temperature of the foaming agent is preferably higher than the plasticizing temperature of the thermoplastic material, and the decomposition temperature of the foaming agent and the plasticizing temperature of the thermoplastic material are almost equal. It is further preferable that the foamed material can be foamed neatly.

  The main material of the foam material is not particularly limited as long as it is a substance that is softened by heating, and a group of synthetic plastic materials known as thermoplastic resins are preferably used. For example, poly (styrene); olefin-based resins such as poly (ethylene) and poly (propylene); poly (vinylidene chloride), poly (vinyl chloride), ethylene-tetrafluoroethylene copolymer, poly (vinylidene fushiide), Poly (vinyl fluoride), poly (chlorotrifluoroethylene), fluorinated ethylene propylene copolymer, poly (tetrafluoroethylene), chlorinated poly (vinyl chloride), chlorinated poly (ethylene), chlorinated poly ( Halogenated resins such as propylene); polyamides such as nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon MXD6, nylon 46, N-methoxymethylated poly (amide), aminopoly (acrylamide); Styrene-isoprene-styrene block copolymer, Tylene-butadiene-styrene block copolymer, styrene- (ethylene-butylene) -styrene block copolymer, polypropylene-EPDM, polyethylene-EPDM, isobutylene-oleic anhydride copolymer, acrylonitrile-acrylate-styrene copolymer Acrylonitrile-ethylene-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-vinyl chloride-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, Copolymers such as ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer; ionomer, ketone resin, poly (acrylic acid), poly (acrylic acid ester), poly (Methacrylic acid ester), poly (vinyl propionate), poly (acetal), poly (amidoimide), poly (arylate), thermoplastic poly (imide), poly (ether imide), poly (ether ethertone), poly ( Ethylene terephthalate), polycarbonate, poly (vinyl acetate), poly (sulfone), poly (ethersulfone), poly (aminosulfone), poly (paramethylstyrene), poly (allylamine), poly (vinyl alcohol), poly (vinyl ether) ), Poly (vinyl butyral), poly (phenylene oxide), poly (phenylene sulfide), poly (butadiene), poly (butylene terephthalate), poly (methyl pentene), poly (methyl methacrylate), liquid crystal polymer, poly (urethane) Etc. It is possible. A polylactic acid resin can also be used. In addition, a modified product or a crosslinked product of the above polymer may be used as appropriate, or a copolymer obtained by combining these may be used. Furthermore, these thermoplastic resins may be used independently and may use 2 or more types together.

The thermally decomposable foaming agent to be kneaded with the foamed resin raw material is not particularly limited as long as it is a commonly used thermal decomposable foaming agent, and is selected according to the plasticizing temperature of the main material of the foamed resin raw material. It is.
Examples of such thermally decomposable blowing agents include azo compounds such as azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), azocyclohexylnitrile, diazoaminobenzene, azodicarbonamide ester; Nitroso compounds such as methylenetetramine (DPT); p-toluenesulfonyl hydrazide (TSH), benzenesulfonyl hydrazide (BSH), p, p′-oxybisbenzenesulfonyl hydrazide, diphenylsulfone-3,3′-disulfonyl hydrazide, etc. Sulfonyl hydrazide compounds; azide compounds such as 4,4′-diphenyldisulfonyl azide, p-toluenesulfoazide; p-toluenesulfo semicarbazide, trihydrazinotriazine, sodium hydrogen carbonate, ammonium carbonate, ammonium nitrite, etc. it can Furthermore, these thermally decomposable foaming agents may be used alone or in combination of two or more.

  In addition to these foaming agents, various additives may be added to the foamed resin raw material for the purpose of improving molding characteristics. Additives include metal soaps such as zinc stearate and calcium stearate, and inorganic salts such as zinc zinc nitrate.

  The foaming aid varies depending on the type of resin, foaming agent, and aid used, but it is usually preferred to add at a ratio of about 0.1 to 2.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin. This is because the effect is small when the addition amount is 0.1 parts by weight or less, and the effect tends to be saturated when the addition amount is 2.0 parts by weight or more.

  The size of the expandable beads is preferably 0.3 to 5 mm. Here, the size of the expandable beads is the average diameter when the expandable beads are substantially spherical. Further, in the case of flat or strand-shaped ones, the size of the expandable bead refers to the smallest width, and hereinafter, the size of the expandable bead is assumed to follow this example. The reason why foamed beads with a size of 0.3 mm to 5 mm are suitably used is that the foamable beads are easy to manufacture, the surface area of the foamable beads, and softening unevenness due to heat transfer delay is less likely to occur. This is the result of the trade-off. It is possible to use beads smaller than 0.3 mm, but in this case, the total surface area of the beads increases, so that the area of the interface where the final foam cell contacts increases, forming a thin-walled rigid cell wall. Much more material to do. Therefore, although the compressive strength is increased, the effect of reducing the weight is reduced.

If a mechanism for generating heat from the inside of the expandable beads is used in combination, expandable beads having a diameter larger than 5 mm can also be used. As a mechanism for causing heat generation from the inside of the expandable bead, for example, electromagnetic induction in a high frequency electromagnetic field environment by mixing metal powder into the expandable bead can be used.
In order to obtain a foamed resin composite structure having a homogeneous foamed cell structure, it is desirable that the sizes of the expandable beads are substantially uniform. However, they do not have to be strictly aligned. In addition, since the foamed cell membrane can have a specific three-dimensional structure by intentionally distributing the size of the expandable beads, different sizes of expandable beads may be used in combination.

  Further, the foamed material may be a material in which a foamed material such as pre-foamed beads or a foamed product is impregnated with gas under high pressure. Further, it may be a foamed chip-shaped or straw-shaped material or a crushed foam, and the base material 1 may be formed by condensing the material and heat-sealing it in a mold. .

It is explanatory drawing of a base material, (a) is a perspective view of a base material, (b) is an enlarged view of the area | region D shown to (a). It is a longitudinal cross-sectional view of the state in which the base material 1 and the flowable material 4 are set in the apparatus. It is a graph which shows the result of the experiment 1 with respect to the base material whose expansion ratio is 60 times, the average diameter of a communicating hole is 70 micrometers, and the porosity is 3%. It is the table | surface which put together the result of Experiment 2, (a) is a chart which shows the particle size distribution of copper powder MA-CC, (b) is a chart which shows the particle size distribution of copper powder MA-C04J, (c) is the chart of experiment 2. It is a chart which shows a result. 6 is a chart summarizing the results of Experiment 3. 6 is a chart summarizing the results of Experiment 4. 10 is a chart summarizing the results of Experiment 5. 8 is a graph of the data of FIG. It is explanatory drawing of the foamed resin composite structure which the fluid material osmose | permeated, (a) is a perspective view of a foamed resin composite structure, (b) is an enlarged view of the area | region shown by D in (a). 10 is a chart showing the results of Experiment 6. It is a schematic diagram of a communicating hole, (a) is a schematic diagram which shows the state which the powder osmose | permeated to the middle of the communicating hole, (b) is a schematic diagram which shows the state which the powder osmose | permeated to the lower surface of the base material. 10 is a chart showing the results of Experiment 7. It is explanatory drawing of the tray which mounts an electronic component. It is a flowchart which shows the flow of a process. It is a schematic diagram of the communicating hole of a base material, (a) is a schematic diagram which shows the state which the powder adhered to the inner wall face of a communicating hole, (b) is a schematic diagram which shows the state which resin penetrate | infiltrated into the communicating hole. It is a schematic diagram of a pre-foaming bead. It is a graph which shows the result of the water leak experiment performed with respect to the base material of 15 times of foaming magnifications. It is a graph which shows the result of the water leak experiment performed with respect to the base material of 60 times of expansion ratios.

Explanation of symbols

1 .. Base material, 1a .. Upper surface (one surface), 1b .. Lower surface (other surface), 1c .. Foamed cell,
1d ··· Communication hole, 2 ·· Container, 2d · · Pressure reducing chamber, 2e · · Ventilation port · · · Pressure reducing device,
4 .... Flowable material, 5 .... Foamed resin composite structure, 6 .... Resin layer.

Claims (20)

A closed cell structure is formed by fusing adjacent foam cells, and a base material having a communication hole communicating from one surface to the other by communicating between the closed cells, and
A first fluid material in which a powder is dispersed, and a first component for adhering the powder to the inner wall surface of the communication hole is dissolved or dispersed;
A second fluid material containing a second component for adhering the powder to the inner wall surface of the communication hole;
Preparing a differential pressure generating device that generates a differential pressure between the one surface and the other surface so that the pressure on the other surface is lower than the one surface;
A first step of disposing the first flowable material on the one surface;
By generating a differential pressure between the one surface and the other surface by the differential pressure generator, the first fluid material disposed on the one surface is allowed to permeate the communication hole, A second step of creating a state in which the powder contained in the infiltrated first fluid material adheres to the inner wall surface of the communication hole by the first component contained in the infiltrated first fluid material;
A third step of disposing the second flowable material on the one surface;
By generating a differential pressure between the one surface and the other surface by the differential pressure generating device, the second fluid material disposed on the one surface is infiltrated into the communication hole, A fourth step of creating a state in which the powder is fixed to the inner wall surface of the communication hole by the second component contained in the infiltrated second fluid material, and the communication hole is closed ;
A method for producing a foamed resin composite structure, comprising: The second component, the manufacturing method of the foamed resin molded article according to claim 1, characterized in Rukoto such from the same ingredients as the first component. The state created in the second step is:
The foam according to claim 1 or 2, wherein the powder is in a state of being continuously attached from an opening surface opened on the one surface of the communication hole to an inner wall surface having a predetermined depth. A method for producing a resin composite structure. The state created in the second step is:
2. The powder according to claim 1, wherein the powder is continuously attached to an inner wall surface from an opening surface opened on the one surface of the communication hole to an opening surface opened on the other surface. Item 4. The method for producing a foamed resin composite structure according to any one of Items 3 to 4. The second step includes
By generating a differential pressure between the one surface and the other surface by the differential pressure generating device, the first flowable material disposed on the one surface can be transferred from the one surface to the communication hole. And making the powder adhere to the one surface continuously from the inner wall surface of the communication hole.
The fourth step includes
By generating a differential pressure between the one surface and the other surface by the differential pressure generating device, the second fluid material disposed on the one surface penetrates the communication hole and It is a step of making a state in which the powder remains on one surface and is continuously fixed to the one surface from the inner wall surface of the communication hole by the second component contained in the second fluid material. The method for producing a foamed resin composite structure according to any one of claims 1 to 4, wherein:   The method for producing a foamed resin molded product according to any one of claims 1 to 5, wherein the second component is a resin.   The method for producing a foamed resin molded article according to any one of claims 1 to 5, wherein the first and second components are resins. The fourth step includes
By causing the differential pressure generating device to generate a differential pressure between the one surface and the other surface, the second fluid material disposed on the one surface is infiltrated into the communication hole. The second component contained in the permeated second fluid material that remains on the one surface creates a state in which the powder is fixed to the inner wall surface of the communication hole, and the second component causes the one The method for producing a foamed resin composite structure according to claim 6 or 7, wherein a film is formed on the surface.   The method for producing a foamed resin composite structure according to any one of claims 1 to 8, wherein the first and second flowable materials each have a viscosity of 2000 mPa · s or less.   The method for producing a foamed resin molded product according to claim 9, wherein the first component is at least 1 vol% or more.   The method for producing a foamed resin composite structure according to claim 9 or 10, wherein an average diameter of the communication holes is 10 to 150 µm.   12. The foamed resin according to claim 11, wherein a total volume ratio of the first and second components and the powder is selected from 18 to 95 vol% according to an average diameter of the communication holes. A method for producing a composite structure.   The method for producing a foamed resin composite structure according to any one of claims 1 to 12, wherein the powder is at least one of a conductive powder and a magnetic powder.   The method for producing a foamed resin composite structure according to claim 13, wherein the conductive powder is a powder made of at least copper.   The method for producing a foamed resin composite structure according to claim 13 or 14, wherein the magnetic powder is a powder comprising at least ferrite.   The method for producing a foamed resin composite structure according to any one of claims 1 to 15, wherein the powder is a powder comprising at least boric acid.   The first fluid material is a solvent-type or dispersion-type resin composed of at least one of acrylic, synthetic rubber, vinyl acetate, ethylene, epoxy, and urethane. The method for producing a foamed resin composite structure according to any one of claims 1 to 16.   The second fluid material is a solvent-type or dispersion-type resin composed of at least one of acrylic, synthetic rubber, vinyl acetate, ethylene, epoxy, and urethane. The method for producing a foamed resin composite structure according to any one of claims 1 to 17.   The method for producing a foamed resin composite structure according to claim 17 or 18, wherein the first fluid material is an aqueous resin emulsion.   The method for producing a foamed resin composite structure according to any one of claims 17 to 19, wherein the second fluid material is an aqueous resin emulsion.

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