JP4983967B2 - Foamed resin composite structure and method for producing the same - Google Patents

Description

  The present invention relates to a foamed resin composite structure using a base material made of foamed resin and a method for producing the same.

  In the previous application, the inventors of the present application proposed a method for producing a foamed resin composite structure in which a resin aqueous emulsion or the like is permeated into the communicating holes of the foamed resin base material using a differential pressure generator (Patent Document 1). ).

JP 2010-89267 A

  The inventors of the present application then tested the combustibility of the foamed resin composite structure produced by the above-described production method. This test was performed according to the method for measuring flammability defined in JIS A 9511. In addition, a base material made of a foamed resin having an oxygen index (oxygen index defined in JIS K 7201; the same shall apply hereinafter) greater than 21 is used. A large one was used.

As a result, when the filling rate of the filling material with respect to the base material exceeds a specified filling rate, the flammability requirement (required as one of the characteristics of the Class A bead method polystyrene foam heat insulating material in the provisions of JIS A 9511) ) Was found to be unable to satisfy.
That is, if the base material made of foamed resin having an oxygen index greater than 21 is filled with a filling material having an oxygen index greater than 21 at a specific filling rate or more, the property of flame retardancy of the foamed resin composite structure may be impaired. I understood.

  Accordingly, the present invention provides a foamed resin composite structure which is formed by filling the voids and communication holes of a foamed resin base material having an oxygen index greater than 21 with a filler material having an oxygen index greater than 21, and hardly impairing flame retardancy. It aims to be realized. In the following, the determination of flame retardancy was performed based on the flammability requirement defined as one of the characteristics of the Class A bead method polystyrene foam heat insulating material in the provisions of JIS A 9511.

In order to achieve the above object, according to the present invention described in claims 1 to 6, a closed cell structure is formed by fusing adjacent foam beads (1c) to each other. A void is formed between the foam beads, and there is a communication hole (1d) communicating from one surface (1a) to the other surface (1b) by communicating the air gap, and The foamed resin composite structure (5) is formed by filling the voids and communication holes of the base material (1) having an oxygen index greater than 21 with the filling material (4), and the base material is formed of a beaded polystyrene foam. The filling material is mainly composed of an organic substance, has an oxygen index greater than 21, and has a filling rate with respect to the voids and communication holes of the base material of 0.1 to 0.1 depending on the type of the filling material. 4.5 vol% range And characterized in that determined from.
In the following, the bead method polystyrene foam refers to a bead method polystyrene foam that matches the characteristics of the type A bead method polystyrene foam heat insulating material specified in JIS A 9511. The typical oxygen index is 26.
Here, the base material formed by the bead method polystyrene foam is a foamed resin molded body itself according to the shape of the mold, which is formed by filling the mold with foam beads and heating and foaming the mold, or the foam It is a foamed resin molded body produced by fusing a resin molded body with a heated nichrome wire or the like.

In the invention described in claim 2, in the foaming resin composite structure according to claim 1 (5), wherein the organic based material and characterized der Rukoto content of 85% or more as a main component Ri der vinylidene chloride To do.

In the invention according to claim 3 , in the foamed resin composite structure (5) according to claim 2 , the filling rate of the base material with respect to the voids and the communication holes is determined from a range of 1.0 to 4.5 vol%. It is characterized by being made.

In the invention according to claim 4 , in the foamed resin composite structure (5) according to claim 3 , the filling rate of the base material with respect to the voids and communication holes is determined from a range of 1.0 to 2.5 vol%. It is characterized by being made.

According to a fifth aspect of the present invention, in the foamed resin composite structure (5) according to any one of the first to fourth aspects, the filling material (4) comprises an organic flame retardant as a main component. It is what was added.

According to a sixth aspect of the present invention, in the method for producing a foamed resin composite structure according to any one of the first to fifth aspects, the filling material is disposed on one surface of the base material. A first step, and a second step of generating a differential pressure between one surface of the base material and the other surface and filling the filling material disposed on the one surface into the gap and the communication hole of the base material; And a third step of generating a differential pressure between one surface of the base material and the other surface and passing gas from the one surface through the communication hole of the base material.

  In addition, the code | symbol in each above-mentioned parenthesis shows the correspondence with embodiment mentioned later.

(Effect of the invention according to claims 1 to 6 )
According to the present inventors' experiments, filling the voids and the communication hole of the preform oxygen index oxygen index filling material larger organic substances mainly composed than 21 is formed by the size rather bead polystyrene foam than 21 It was found that the foamed resin composite structure can be made difficult to impair the flame retardancy by determining the filling rate of the filling material from the range of 0.1 to 4.5 vol% according to the type of the filling material. .

(Effect of the invention according to claim 2 )
Greater vinylidene chloride than oxygen index 21 a filling material that will be contained content of 85% or more as a main component 0. The foamed resin composite structure filled at a filling rate determined from the range of 1 to 4.5 vol% is also unlikely to lose flame retardancy. In particular, if the filling rate is determined from the range of 0.1 to 2.5 vol%, the flame retardancy of the foamed resin composite structure is less likely to be impaired.

(Effect of the invention according to claim 3 )
In particular, as in the invention according to claim 2 , when filling the filling material whose oxygen index is larger than 21 and the resin is the main component, the lower limit value of the filling rate is increased from 0.1 to 1.0 vol%. Even if the filling rate is determined from the range of 0.0 to 4.5 vol%, the flame retardancy of the foamed resin composite structure is unlikely to be impaired.

(Effect of the invention according to claim 4 )
In particular, in the invention according to claim 3 , if the upper limit value of the filling rate is lowered from 4.5 to 2.5 vol% and the filling rate is determined from the range of 1.0 to 2.5 vol%, the foamed resin composite structure The flame retardancy of is less likely to be impaired.

(Effect of the invention according to claim 5 )
In the case of filling a filling material in which an organic substance is added with a main component flame retardant, if the filling rate is determined according to the characteristics according to any one of claims 1 to 4 , the foamed resin composite The flame retardancy of the structure is difficult to be impaired.

(Effect of the invention according to claim 6 )
After filling the filling material into the gap and communication hole of the base material, gas is passed from one side of the base material to the communication hole of the base material, so the filled filling material can be discharged from the base material. The filling rate of the material can be adjusted. Further, filling unevenness can be reduced and the filling can be stabilized.

It is explanatory drawing of the base material 1, (a) is a perspective view of the base material 1, (b) is an enlarged view of the area | region D shown to (a). It is the further enlarged view of the area | region D shown in FIG.1 (b), (a) is an enlarged view which shows the state in which the filling material is not filled with the space | gap, (b) shows the state with which the filling material was filled with the space | gap. It is an enlarged view. 2A and 2B are schematic views of communication holes formed in the base material shown in FIG. 1, in which FIG. 1A is a schematic view showing a state where a filling material is filled in the communication holes, and FIG. It is a schematic diagram which shows the state formed in the surface. It is a longitudinal cross-sectional view which shows the state by which the base material and the filling material were set to the apparatus. It is the graph which summarized the result of Experiments 1-4. 10 is a chart summarizing the results of Experiment 5. It is a chart which shows the detail of the filling material used in each experiment.

An embodiment of a foamed resin composite structure according to the present invention will be described with reference to the drawings.
[Base material structure]
The structure of the base material for producing the foamed resin composite structure will be described.
FIG. 1 is an explanatory diagram of the base material 1, (a) is a perspective view of the base material 1, and (b) is an enlarged view of a region D shown in (a). 2A and 2B are further enlarged views of the region D shown in FIG. 1B. FIG. 2A is an enlarged view showing a state where the filling material is not filled in the gap, and FIG. 2B is a drawing showing the filling material filled in the gap. It is an enlarged view which shows the state. FIG. 3 is a schematic diagram of the communication holes formed in the base material shown in FIG. 1, (a) is a schematic diagram showing a state in which the filling material is filled in the communication holes, and (b) is a film of the filling material. It is a schematic diagram which shows the state formed in one surface of a base material.

  As shown in FIG. 1 (b), the base material 1 is formed of a beaded polystyrene foam (hereinafter abbreviated as EPS (Expanded Polystyrene)) and is composed of a large number of foam beads 1c fused together. ing. Adjacent foam beads 1c are fused together to form a closed cell structure, and a gap 1d is formed between the foam beads 1c.

  Further, some of the gaps 1d are in communication with each other. As a result, as shown in FIG. 3, the base material 1 has a large number of communication holes 1e communicating from one surface 1a to the other surface 1b. Yes. The communication hole 1e 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 or between the side surface and the side surface.

[Experiment]
As shown in FIG. 2 (b), the inventors of the present application fill the gap 1d formed in the base material 1 with the filling material 4, and also fill the communication hole 1e with the filling material 4 as shown in FIG. The foamed resin composite structure 5 was manufactured by filling, and an experiment was conducted to determine the relationship between the filling rate of the filler material 4 and the flame retardancy of the foamed resin composite structure 5. FIG. 4 is a longitudinal sectional view showing a state in which the base material 1 and the filling material 4 are set in the filling device. FIG. 5 is a chart summarizing the results of Experiments 1 to 4, and FIG. 6 is a chart summarizing the results of Experiment 5. FIG. 7 is a chart showing details of the filling material used in each experiment.

(Manufacturing equipment)
A filling device used for filling the gap 1d and the communication hole 1e of the base material 1 with the filling material 4 in this experiment will be described with reference to the drawings.

  The filling device 10 includes a container 2 for housing the base material 1 and the filling material 4 and a decompression device 3 for generating a differential pressure between one surface 1a and the other surface 1b of the base material 1. Prepare. 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 for accommodating the base material 1 and the filling material 4, and the lower space 2c is formed in the 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.

(experimental method)
In the following experiments, the above-described filling device 10 was used. Further, as the base material 1, an EPS base material having a size of 150 × 25 × 10 (mm) and a porosity of 3% was used. And the test piece (foamed resin composite structure) was manufactured by filling the base material 1 with the filling material by the following steps.

  The base material 1 is placed on the partition 2a of the manufacturing apparatus 10, and the filling material 4 is placed on the surface of the base material 1 (first step). Next, the decompression device (vacuum pump) 3 is operated to generate a differential pressure between the front surface and the back surface of the base material 1 to fill the gap 1d and the communication hole 1e of the base material 1 (second step). ). Next, even after the filling material 4 disappears from the surface of the base material 1, the decompression device 3 is operated to suck air from the surface of the base material 1, thereby controlling the filling rate of the filling material 4 with respect to the base material 1 and filling. Unevenness is reduced to stabilize the filling (third step). Moreover, the filling rate with respect to the base material 1 of the filling material 4 was adjusted by adjusting the amount of water mixed with the filling material 4.

The filling rate of the filling material 4 with respect to the gap 1d and the communication hole 1e of the base material 1 is that the weight (g) of the filling material 4 filled in the base material 1 is A, the specific gravity of the filling material 4 is B, and The volume was calculated using the formula of filling rate (vol%) = (A / B) / (0.03 × C), where C is the volume. Further, the flammability test for the test piece filled with the filling material 4 by the filling device 10 was performed according to the flammability test method defined in JIS-A-9511. In addition, the flammability test was performed five times for each filling rate. That is, the flammability test was performed using a total of five test pieces for one filling rate.

  And flame retardance was evaluated based on the number of the test pieces which did not satisfy the acceptance criteria prescribed | regulated to JIS. The acceptance criteria specified in JIS are the result of tests conducted according to the rules of JIS-A-9511. As a result, flame disappears within 3 seconds, there is no residue, and combustion does not exceed the combustion limit indicator line. is there. And among the five test pieces, the case where the number of test pieces that did not satisfy the acceptance criteria is 3 to 5 is evaluated as “x” because there is no flame retardancy, and the case of 1 to 2 is flame retardant. It was evaluated as “Δ” because the property was not easily impaired (flame retardance was slightly inferior), and “◯” was evaluated as 0 when the flame resistance was not impaired (has flame retardancy).

<Experiment 1. When filled with flame retardant organic material>
(Experiment 1-1)
A test piece was manufactured by filling the base material 1 with a flame retardant organic material, and the flame retardance of the test piece was evaluated. As a flame retardant organic material, Saran latex L131A manufactured by Asahi Kasei Chemicals Corporation (Saran latex is a registered trademark of Asahi Kasei Chemicals Corporation) was used.

  Saran latex L131A is an aqueous emulsion mainly composed of vinylidene chloride (PVDC (Poly Vinylidene Chloride)), has an oxygen index greater than 21, and is generally used mainly as a flame retardant binder. Saran latex L131A has a solid content of 55%, a specific gravity of 1.65, a viscosity of 10 mPa · s, a surface tension of 35 MN / m, and a minimum film formation temperature of 12 to 18 ° C.

  As a result of the experiment, as shown in No. 5 of FIG. 5, the evaluation result in the range where the filling rate of Saran latex L131A (described in the table as flame retardant organic (H-PVDC)) is 0.1 to 2.5 vol%. Were all ◯, and the evaluation results in the range where the filling rate was more than 2.5 vol% and 4.5 vol% or less were all Δ.

From this experimental result, if the filling rate of Saran latex L131A with respect to the space | gap 1d of the base material 1 and the communicating hole 1e is determined from the range of 0.1-4.5 vol%, a foamed resin composite structure with which flame retardance is hard to be impaired It was found that 5 could be produced.
Moreover, if the upper limit of a filling rate is reduced from 4.5 vol% to 2.5 vol% and a filling rate is determined from the range of 0.1 to 2.5 vol%, a foamed resin composite structure that does not impair flame retardancy It was found that 5 could be produced.

(Experiment 1-2)
Next, the above experiment was performed using Saran latex L106C manufactured by Asahi Kasei Chemicals Corporation as a flame-retardant organic material to be filled in the base material 1. Saran latex L106C is an aqueous emulsion mainly composed of vinylidene chloride (PVDC), has an oxygen index greater than 21, and is generally used mainly as a flame retardant binder. Saran latex L106C has a solid content of 55%, a specific gravity of 1.55, a viscosity of 12 mPa · s, a surface tension of 43 MN / m, and a minimum film formation temperature of 0 to 5 ° C.

  As a result of the experiment, as shown in No. 4 of FIG. 5, the evaluation results in the range where the filling rate of Saran latex L106C (described as flame retardant organic (L-PVDC) in the table) is 0.1 or more and less than 1.0 vol%. Are all ◯, and the evaluation results in the range where the filling rate is 1.0 or more and less than 2.5 vol% are all Δ.

From this experimental result, if the filling rate of Saran latex L106C with respect to the gap 1d and the communication hole 1e of the base material 1 is determined from the range of 0.1 or more and less than 2.5 vol%, the foamed resin composite structure in which flame retardancy is hardly impaired It has been found that the body 5 can be manufactured.
Moreover, if the upper limit of a filling rate is lowered from 2.5 vol% to 1.0 vol% and determined from the range of 0.1 or more and less than 1.0 vol%, the foamed resin composite structure 5 that does not impair flame retardancy is obtained. It turns out that it can be manufactured.

(Experiment 1-3)
Next, the above-described experiment was performed using a test piece filled with a flame-retardant organic material added with a combustible organic material. The above-mentioned Saran Latex L131A was used as the flame retardant organic material, and Acronal YJ2720D (ACRONAL is a registered trademark of BSF Societas Europea) manufactured by BASF Japan Ltd. was used as the flammable organic material. Acronal YJ2720D is an acrylic styrene aqueous emulsion (AS resin) of a one-component room temperature crosslinkable compound, having an oxygen index of 21 or less, a resin solid content of 48% by weight, a specific gravity of 1.0, and a film forming temperature of 6 ° C. is there.

  Moreover, what set the weight ratio of acronal YJ2720D with respect to Saran latex L131A to 5/95, 1/9, and 1/4, respectively was created, and the same experiment was conducted about each.

As a result of the experiment, as shown in No. 8 of FIG. 5, a test piece having a weight ratio of acronal YJ2720D (denoted as flammable organic / flame retardant organic (AS / H-PVDC) in the table) to Saran latex L131A is 5/95. The evaluation results in the range where the filling rate is 0.1 to 0.5 vol% are all ◯, and the evaluation results in the range where the filling rate is more than 0.5 and less than 2.0 vol% are all Δ. .
Moreover, as shown in No. 7 of FIG. 5, the test piece having a weight ratio of 1/9 of acronal YJ2720D (described as flammable organic / flame retardant organic (AS / H-PVDC) in the table) with respect to Saran latex L131A is The evaluation results in the range where the filling rate was 0.1 to 0.5 vol% were all ◯, and the evaluation results in the range where the filling rate was more than 0.5 and less than 1.5 vol% were all Δ.

  Furthermore, as shown in No. 9 of FIG. 5, the test piece having a weight ratio of 1/4 of Acronal YJ2720D (described as “flammable organic / flame retardant organic (AS / H-PVDC)” in the table) has a filling rate of 0. The evaluation results in the range of 0.1 or more and less than 0.5 vol% were all ◯, and the evaluation results in the range where the filling rate was 0.5 or more and less than 1.5 vol% were all Δ.

From these experimental results, the filling rate of the base material 1 of the substance obtained by adding acronal YJ2720D to Saran latex L131A at a weight ratio of 5/95 to 1/4 is 0.1 or more and 0.1. It was found that if it was determined from the range of less than 5 vol%, the foamed resin composite structure 5 in which the flame retardance is hardly impaired can be produced.
Moreover, in order to raise a filling rate, without impairing a flame retardance, it turned out that the addition amount of acronal YJ2720D which is a combustible organic type material should just be decreased.

<Experiment 2. When filled with flame retardant inorganic material>
(Experiment 2-1)
Next, the above-described experiment was performed using a test piece filled with a flame-retardant inorganic material. H-42M manufactured by Showa Denko KK was used as a flame retardant inorganic material. H-42M is aluminum hydroxide and has an oxygen index greater than 21, and is generally used mainly as a flame retardant binder. Moreover, the dispersion liquid which disperse | distributed H-42M in water was created, the base material 1 was filled with it, and the test piece was created.

  As a result of the experiment, as shown in No. 2 of FIG. 5, the evaluation result when the filling rate of H-42M (described as “flame-retardant inorganic substance (aluminum hydroxide)” in the table) is 0.1 vol is ○, and the filling rate is The evaluation results in the range exceeding 0.1 and less than 1.5 vol% were all Δ.

From this experimental result, if the filling rate of the aluminum hydroxide base material 1 with respect to the gap 1d and the communication hole 1e is determined from the range of 0.1 to less than 1.5 vol%, the foamed resin composite structure in which flame retardancy is hardly impaired It has been found that the body 5 can be manufactured.
Further, it was found that if the filling rate is determined to be 0.1 vol%, the foamed resin composite structure 5 that does not impair the flame retardancy can be produced.

(Experiment 2-2)
Next, Softon 1500 manufactured by Shiroishi Calcium Co., Ltd. was used as a flame retardant inorganic material. Softon 1500 is calcium carbonate and has an oxygen index greater than 21. Moreover, the dispersion liquid which disperse | distributed Softon 1500 in water was created, it filled with the base material 1, and the test piece was created.

  As a result of the experiment, as shown in No. 1 in FIG. 5, the evaluation result when the filling rate of Softon 1500 (described as inorganic (calcium carbonate) in the table) is 0.1 vol is ○, and the filling rate is 0. The evaluation results in the range of more than 1 and less than 1.0 vol% were all Δ.

From this experimental result, if the filling rate of the softon 1500 with respect to the gap 1d and the communication hole 1e of the base material 1 is determined from the range of 0.1 or more and less than 1.0 vol%, the foamed resin composite structure in which flame retardancy is hardly impaired. It was found that 5 could be produced.
Moreover, it turned out that the foamed resin composite structure 5 which does not impair a flame retardance can be manufactured by determining said filling rate to 0.1 vol%.

<Experiment 3. When filled with a flame retardant organic material plus a flame retardant inorganic material>
Next, the above-described experiment was performed using a test piece filled with a flame retardant organic material added with a flame retardant inorganic material. The aforementioned Saran latex L131A was used as the flame retardant organic material, and the aforementioned Softon 1500 was used as the flame retardant inorganic material. The ratio of resin solids to solids of this mixture is 80%.

  As a result of the experiment, as shown in No. 10 of FIG. 5, the evaluation results when the filling rate is 0.1 to 1.5 vol% are all ◯, and the filling rate exceeds 1.5 and is less than 2.0 vol%. The evaluation results in the range were all Δ.

From this experimental result, the filling rate with respect to the void 1d and the communication hole 1e of the base material 1 of Soften 1500 added to Saran latex L131A (described in the table as flame retardant organic / inorganic (H-PVDC / charcoal)) is 0. It was found that if it was determined from the range of 0.1 to 2.0 vol%, the foamed resin composite structure 5 in which the flame retardancy is hardly impaired can be produced.
Moreover, if the upper limit of a filling rate is reduced from 2.0 vol% to 1.5 vol% and a filling rate is determined from the range of 0.1 to 1.5 vol%, a foamed resin composite structure that does not impair flame retardancy It was found that 5 could be produced.

<Experiment 4. When flame retardant is added>
(Experiment 4-1)
Next, the above-described experiment was performed using a test piece filled with a combustible organic material added with a flame retardant. The aforementioned acronal YJ2720D was used as the flammable organic material, and nonnene SM-18 manufactured by Maruhishi Oil Chemical Co., Ltd. was used as the flame retardant (nonnene is a registered trademark of Maruhishi Oil Chemical Co., Ltd.). Nonene SM-18 is an organic dispersion, and its components are a halogen / polyvalent metal oxide system, and the oxygen index is greater than 21. Moreover, the weight ratio of nonene SM-18 to acronal YJ2720D is 30%.

  As a result of the experiment, as shown in No. 1 of FIG. 6, the evaluation results when the filling rate is 0.1 to 0.5 vol are all ◯, and the filling rate is more than 0.5 and less than 3.0 vol%. The evaluation results in were all Δ.

  From this experimental result, although the nonnene SM-18 was added to the acronal YJ2720D at a weight ratio of 30%, the filling rate with respect to the gap 1d and the communication hole 1e of the base material 1 was in the range of 0.1 or more and less than 3.0 vol%. From this, it was found that the foamed resin composite structure 5 in which the flame retardancy is hardly impaired can be produced.

Moreover, if the upper limit of said filling rate is reduced from 3.0 vol% to 0.5 vol%, and a filling rate is determined from the range of 0.1-0.5 vol%, a foamed resin composite that does not impair flame retardancy It turned out that the structure 5 can be manufactured.
Further, as can be seen in comparison with No. 3 in FIG. 5 (Experiment 4-1), the addition of nonene SM-18, which is a flame retardant organic material, to acronal YJ2720D, which is a flammable organic material. Thereby, the filling rate of the combustible organic substance can be increased while ensuring the flame retardancy of the foamed resin composite structure 5.

(Experiment 4-2)
Next, the above-described experiment was performed using a polyvinyl acetate methanol solution as the flammable organic material and the above-described nonene SM-18 as the flame retardant. The oxygen index of the polyvinyl acetate methanol solution is 21 or less. The weight ratio of nonene SM-18 to the polyvinyl acetate methanol solution is 30%.

  As a result of the experiment, as shown in No. 3 of FIG. 6, the evaluation results when the filling rate is 0.1 to 0.5 vol% are all ◯, and the filling rate exceeds 0.5 and is less than 3.0 vol%. The evaluation results in the range were all Δ.

From the results of this experiment, the mother of nonene SM-18 added at a weight ratio of 30% to the polyvinyl acetate methanol solution (described in the table as polyvinyl acetate methanol solution / flame retardant (vinyl acetate / SM-18)). It was found that if the filling rate of the material 1 with respect to the gap 1d and the communication hole 1e is determined from a range of 0.1 or more and less than 3.0 vol%, the foamed resin composite structure 5 in which flame retardancy is hardly impaired can be produced.
Moreover, if the upper limit of a filling rate is reduced from 3.0 vol% to 0.5 vol%, and a filling rate is determined from the range of less than 0.1-0.5 vol%, a foamed resin composite structure that does not impair flame retardancy It has been found that the body 5 can be manufactured.

<Experiment 5. When a flame retardant is added to a flame retardant organic material>
(Experiment 5-1)
Next, the above-described experiment was performed using a test piece filled with a flame retardant organic material added with a flame retardant. Halogenated epoxy resin was used as the flame retardant organic material, and antimony trioxide was used as the flame retardant. Antimony trioxide is an inorganic substance. The oxygen index of the halogenated epoxy resin is greater than 21. The weight ratio of antimony trioxide to halogenated epoxy resin is 3%.

  As a result of the experiment, as shown in No. 4 of FIG. 6, the evaluation results when the filling rate is 0.1 or more and less than 1.0 vol% are all ◯, and the filling rate is 1.0 or more and less than 2.0 vol%. The evaluation results in the range were all Δ.

From this experimental result, the voids of the base material 1 of antimony trioxide added at a weight ratio of 3% to the halogenated epoxy resin (described in the table as halogenated epoxy resin / flame retardant (YL7726 / antimony trioxide)) It was found that if the filling rate with respect to 1d and the communication hole 1e is determined from the range of 0.1 or more and less than 2.0 vol%, the foamed resin composite structure 5 in which flame retardancy is hardly impaired can be produced.
Further, if the upper limit value of the filling rate is lowered from 2.0 vol% to 1.0 vol% and the filling rate is determined from the range of 0.1 or more and less than 1.0 vol%, the foamed resin composite structure that does not impair the flame retardancy It has been found that the body 5 can be manufactured.

(Experiment 5-2)
Next, the above-mentioned Saran latex L131A was used as the flame retardant organic material, and Nonen BC-52EM manufactured by Maruhishi Oil Chemical Co., Ltd. was used as the flame retardant. Nonene BC-52EM is an organic emulsion, the component of which is a phosphorus / halogen compound, and the oxygen index is greater than 21. The weight ratio of nonene BC-52EM to Saran latex L131A is 30%.

  As a result of the experiment, as shown in No. 2 of FIG. 6, the evaluation results when the filling rate is 0.1 or more and less than 2.5 vol% are all ◯, and the filling rate is in the range of 2.5 to 4.5 vol%. The evaluation results in were all Δ.

  From this experimental result, it is shown that the base material 1 of non-bene BC-52EM added to Saran latex L131A at a weight ratio of 30% (described as a flame retardant organic / flame retardant (H-PVDC / BC-52EM) in the table). It was found that if the filling rate with respect to the gap 1d and the communication hole 1e is determined from the range of 0.1 to 4.5 vol%, the foamed resin composite structure 5 in which flame retardancy is hardly impaired can be manufactured.

Further, if the upper limit value of the filling rate is lowered from 4.5 vol% to 2.5 vol% and the filling rate is determined from the range of 0.1 or more and less than 2.5 vol%, the foamed resin composite structure that does not impair the flame retardancy It has been found that the body 5 can be manufactured.
Furthermore, as can be seen from comparison with No. 5 (Experiment 1-1) in FIG. 5, when the base material 1 is filled with only Saran latex L131A, which is a flame retardant organic material, and an organic flame retardant The flame retardancy hardly changes when non-Nenen BC-52EM is added.

<Summary>
When the experimental results of Experiments 1 to 5 described above are summarized, it has been clarified that the following effects can be obtained by carrying out the method for manufacturing a foamed resin composite structure according to this embodiment.

(1) In the case where the foamed resin composite structure 5 is manufactured by filling the void 1d and the communication hole 1e of the base material 1 having an oxygen index greater than 21 with the filler material having an oxygen index greater than 21 from the experiments 1 to 5 described above. Can increase the flame retardancy of the foamed resin composite structure 5 as its filling rate is lower.

(2) Moreover, if the filling rate is determined from the range of 0.1 to 4.5 vol% according to the type of the filling material to be filled, the foamed resin composite structure 5 in which the flame retardancy is hardly impaired can be produced. it can.

(3) As the filling material, a filling material mainly composed of an organic substance can be selected, and as the organic substance, a resin can be selected.

(4) In particular, when selecting a filling material mainly composed of a resin, the lower limit value of the filling rate is increased from 0.1 to 1.0 vol%, and the filling rate is within a range of 1.0 to 4.5 vol%. Even if determined, it is possible to produce a foamed resin composite structure in which flame retardancy is hardly impaired.

(5) In particular, in the case of selecting a filling material mainly composed of a resin, the upper limit value of the filling rate is lowered from 4.5 to 2.5 vol%, and the filling rate is changed from a range of 1.0 to 2.5 vol%. If determined, it is possible to produce a foamed resin composite structure in which the flame retardancy is hardly further impaired.

(6) As the filling material, a filling material mainly composed of an inorganic substance can also be selected. In this case, the filling rate is determined from the range of 0.1 to 1.5 vol% according to the type. Thus, it is possible to produce a foamed resin composite structure in which flame retardancy is hardly impaired.

(7) Moreover, the filling material which added the flame retardant to the main component can also be selected, and also in this case, if a filling rate is determined from the range of 0.1 to 4.5 vol% according to the kind, it is difficult. A foamed resin composite structure in which the flammability is hardly impaired can be produced.

(8) Also, in the case of filling a filling material in which an organic substance is added with a main component flame retardant, if the filling rate is determined from the range of 0.1 to 4.5 vol% according to the type, the flame retardant It is possible to produce a foamed resin composite structure that is not easily damaged.

(9) In addition, when filling a filling material containing a flame retardant whose main component is an inorganic substance, if the filling rate is determined from the range of 0.1 to 1.5 vol% according to the type, the flame retardant It is possible to produce a foamed resin composite structure that is not easily damaged.

[Other Embodiments]
(1) When the filling material 4 is filled from one surface of the base material 1, the filling material 4 can remain on the one surface. For example, as shown in FIG. 3B, when the fluid resin 4 is filled from one surface 1a of the base material 1, the resin 4 is left on the one surface 1a, and the remaining resin 4 is If dried, one surface can be covered with the resin film 4a. According to this manufacturing method, the foamed resin composite structure 5 having a waterproof effect on the surface covered with the resin film 4a can be manufactured.

(2) In the above-described embodiment, the base material 1 is filled with the filling material 4 by generating a differential pressure between the one surface 1a and the other surface 1b of the base material 1 using the decompression device 3. A pressurizing device that pressurizes the filling material 4 disposed on one surface 1a of the material 1 can also be used in combination. For example, a lid is disposed in the upper space 2 b of the filling device 10 shown in FIG. 4, and air is sent out and pressurized into a space formed between the lid and the filling material 4. According to this method, since the differential pressure between the one surface 1a and the other surface 1b of the base material 1 can be increased efficiently, the filling speed of the filling material 4 with respect to the base material 1 can be increased. The production efficiency of the foamed resin composite structure 5 can be increased. An air pump or the like can be used for air delivery.

(3) The region of the base material 1 that is not desired to be filled with the filling material 4 may be previously masked with a film or the like. According to this method, it is possible to fill the desired region of the base material 1 with the filling material 4.

(4) In the case of using the filling material 4 in which evaporation of the evaporation component is promoted by heating, the base material 1 filled with the filling material 4 can be heated to promote drying, and the manufacturing time can be shortened.

(5) By filling the base material 1 with the filling material 4 containing a functional substance, the foamed resin composite structure 5 having a function exhibited by the filled functional substance can be manufactured. For example, by filling the base material 1 with a fluid resin containing a drug, the foamed resin composite structure 5 having the effect of the filled drug can be manufactured.

  For example, if the base material 1 is filled with a fluid resin in which a biological repellent is dispersed, a foamed resin composite structure 5 having a biological repellent effect can be produced. Further, since the resin in which the biological repellent is dispersed is filled not only in the gap 1d of the base material 1 but also in the communication hole 1e, the biological repellent takes time from the resin filled in the communication hole 1e. Since it evaporates, the biological repellent effect can be maintained over a long period of time.

  For example, if the above-mentioned foamed resin composite structure 5 having a biological repellent effect is used as a heat insulating material for a building, insect pests such as termites, cockroaches, and ticks are eliminated, and further, antifungal and antibacterial properties are imparted. be able to. 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 the biological repellent can be filled up to the inside of the base material 1, the biological repellent effect can be maintained even when the surface of the foamed resin composite structure 5 is peeled off or chipped.

  Also, a bioresin is contained in microcapsules, and a foamed resin composite structure 5 having a biorepellent effect is produced by infiltrating the base material 1 with a filler 4 in which a powder composed of a large number of microcapsules is dispersed. You can also For example, as a shell (wall material) constituting an outer shell of a microcapsule, a shell having a property of cracking when an outside air temperature exceeds a predetermined temperature is used, and a biological repellent is included in the shell as a core (core material). . Then, by infiltrating the base material 1 with the filler 4 in which the microcapsules are dispersed as a powder, if the outside air temperature exceeds a predetermined temperature, the microcapsules in the communication holes crack and the boric acid component is introduced into the outside air. Can be released.

  In addition, a shell that decomposes naturally over time can also be used. The “microcapsule” refers to a minute container having a diameter between nanometers and millimeters. Microcapsules include sealed and porous types.

(6) Moreover, the foaming resin composite structure 5 which has electroconductivity can be manufactured by filling the base material 1 with the filling material 4 in which electroconductive powder is dispersed. Gold, silver, copper, nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium, osmium, aluminum, zinc, tin, lead and other metal powders, and alloys of these metals Powdered metal oxide such as tin oxide, conductive carbon allotrope such as carbon powder, but coated with conductive metal on the surface of particles such as glass, carbon, mica and plastic Things can be used.
In addition, since copper powder has a biological repellent effect, if the copper powder is infiltrated into the base material 1, the foamed resin composite structure 5 having the biological repellent effect can be manufactured.

(7) Filling material 4 in which magnetic powder is dispersed is filled in base material 1, and foamed resin composite structure 5 having magnetism can be manufactured. As the magnetic powder, powders such as ferrite, cobalt ferrite magnetic material, metal magnetic material, CrO ₂ , γ-Fe ₂ O ₃ , Fe ₄ N, and Ba ferrite can be used.

(8) As the filling material 4, a solvent type or dispersion type resin composed of at least one of acrylic, synthetic rubber, vinyl acetate, ethylene, vinyl chloride, vinylidene chloride, epoxy, and urethane is used. be able to. For example, acrylic solvent-type or dispersion-type resins include butyl acrylate-methyl methacrylate-acrylic acid copolymer, ethyl acrylate-styrene-acrylamide copolymer, 2-ethylhexyl acrylate-methacrylic acid-acrylic acid copolymer. A polymer or the like can be used. In addition, when using the said filling material whose oxygen index is 21 or less, a flame retardant is mix | blended as needed and the oxygen index of a filling material is made larger than 21.

  As the synthetic rubber solvent type or dispersion type resin, styrene-butadiene latex, styrene-acrylonitrile-butadiene latex, polybutadiene latex, or the like can be used. In addition, vinyl acetate, solvent-type or dispersion-type resins include polyvinyl acetate, vinyl acetate-ethyl acrylate copolymer, vinyl acetate-methyl methacrylate copolymer, vinyl acetate-veova copolymer, polyvinyl Alcohol or the like can be used. Also, polyethylene emulsion, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-acrylic acid copolymer, ethylene-acrylonitrile-vinyl acetate copolymer, etc. should be used as ethylene-based solvent-type or dispersion-type resins. Can do. In addition, when using these resin, a flame retardant is mix | blended as needed and the oxygen index of a filling material is made larger than 21.

  In addition, epoxy, butyl acrylate-glycidyl methacrylate-acrylamide copolymer, or the like can be used as an epoxy-based solvent-type or dispersion-type resin. In addition, polyurethane, urethane-modified acrylic acid-methacrylic acid copolymer, or the like can be used as the urethane-based solvent-type or dispersion-type resin. In addition, when using these resin, a flame retardant is mix | blended as needed and the oxygen index of a filling material is made larger than 21.

  Furthermore, various resin aqueous emulsions obtained by dispersing each of the above resins in water 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. In addition, when using these resin aqueous emulsions, a flame retardant is mix | blended as needed and the oxygen index of a filling material is made larger than 21.

(9) The filling material 4 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 5 can be changed.

(10) The foamed resin material for forming the base material 1 is not particularly limited as long as it is foamed at a specific foaming temperature, but it is impregnated with a thermoplastic substance as a main material and gas or liquid as a foaming agent. Or those containing a thermally decomposable foaming agent are preferably used, but those containing both may also be used. The thermoplastic substance may be cross-linked.

As a material in which a thermoplastic material is a main material and gas or liquid is impregnated as a foaming agent, in addition to polystyrene foamable beads, which are the foamed resin raw materials of the bead method polystyrene foam used in the above-mentioned experiment, polyethylene foamable beads, Polypropylene expandable beads or the like may be used, or may be impregnated with hydrocarbons such as butane, pentane and 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 foam material is selected because the foamed material can be foamed neatly.

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.
Even when the base material 1 is formed from the above-mentioned raw materials, the oxygen index of the base material 1 needs to be greater than 21.

  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 expanded beads is preferably 0.3 to 5 mm. Here, the size of the expanded beads is the average diameter when the expanded beads are substantially spherical. Further, in the case of a flat or strand-like material, the size of the expanded bead refers to the size having the smallest width, and hereinafter the expanded bead size is assumed to follow this example. The foam beads with a size of 0.3 to 5 mm are preferably used because of the ease of manufacturing the foam beads, the surface area of the foam beads, and the softening unevenness due to the heat transfer delay. It is a result. It is possible to use beads smaller than 0.3 mm, but in this case, the total surface area of the beads increases, so the area of the interface where the final foamed beads contact increases, forming a thin-film rigid cell wall. Much more material to do. Therefore, although the compressive strength is increased, the effect of reducing the weight is reduced.

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

  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. .

(11) <Reference experiment. When filled with flammable organic substances>
(Experiment A)
The above-described experiment was performed using a test piece filled with a combustible organic material. The aforementioned acronal YJ2720D was used as the combustible organic material.

  As a result of the experiment, as shown in No. 3 in FIG. 5, the evaluation result when the filling rate of acronal 2720D (described as “flammable organic (AS resin)” in the table) is 0.1 vol is “◯”, and the filling rate is 0.1. The evaluation results in the range of more than and less than 1.0 vol% were all Δ.

From this experimental result, the foamed resin composite structure in which the flame retardancy is hardly impaired if the filling rate of the acronal YJ2720D with respect to the gap 1d and the communication hole 1e of the base material 1 is determined in the range of 0.1 to less than 1.0 vol%. It was found that 5 could be produced.
Further, it was found that if the filling rate is determined to be 0.1 vol%, the foamed resin composite structure 5 that does not impair the flame retardancy can be produced.

(Experiment B)
Next, the above-mentioned experiment was performed using a test piece filled with Cellosol 524 manufactured by Chukyo Yushi Co., Ltd. as a combustible organic material. Cerozole 524 is a wax emulsion called carnauba wax, having an oxygen index of 21 or less and a specific gravity of 0.9.

  As a result of the experiment, as shown in No. 6 of FIG. 5, the evaluation result when the filling rate of cellosol 524 (described as flammable organic (wax (carnauba)) in the table) is 0.1 or more and less than 0.5 vol% is ○. In addition, the evaluation results in the range where the filling rate is more than 0.5 and less than 1.0 vol% were Δ.

From this experimental result, if the filling rate is determined from the range of 0.1 or more and less than 1.0 vol% to the void 1d and the communication hole 1e of the base material 1 of the cellosol 524, the foamed resin composite structure in which flame retardancy is not easily impaired. It was found that 5 could be produced.
Further, it was found that if the filling rate is determined to be 0.1 vol%, the foamed resin composite structure 5 that does not impair the flame retardancy can be produced.

  From the experiments A and B described above, when filling a filling material having an oxygen index of 21 or less, that is, a flammable filling material, if the filling rate is determined from a range of 0.1 or more and less than 1.0 vol%, It has been found that it is possible to produce a foamed resin composite structure in which flame retardancy is hardly impaired.

1 ·· Base material, 1a ·· One side, 1b ·· Other side, 1c ·· Foamed beads, 1d ·· Void,
1e ··· communication hole 2 ·· container 2d · · decompression chamber 3 · · decompression device,
4 .... Filling material, 4a ... Film, 5. Foamed resin composite structure, 10. Filling device.

Claims (6)

Adjacent foam beads are fused together to form a closed cell structure, voids are formed between the foam beads, and the air gap communicates to communicate from one surface to the other. A foamed resin composite structure in which the above-mentioned communication holes exist and the voids and communication holes of the base material having an oxygen index greater than 21 are filled with a filler material,
The base material is formed of a polystyrene bead method,
The filling material is mainly composed of an organic substance, has an oxygen index greater than 21, and has a filling rate of 0.1 to 4.5 vol% depending on the type of the filling material. A foamed resin composite structure characterized by being determined from the above range. The organic material is a foamed resin composite structure according to claim 1, characterized in der Rukoto content of 85% or more as a main component Ri vinylidene chloride der.   The foamed resin composite structure according to claim 2, wherein the filling rate is determined from a range of 1.0 to 4.5 vol%.   4. The foamed resin composite structure according to claim 3, wherein the filling rate is determined from a range of 1.0 to 2.5 vol%.   The foamed resin composite structure according to any one of claims 1 to 4, wherein the filling material is obtained by adding an organic flame retardant as a main component. A method for producing a foamed resin composite structure according to any one of claims 1 to 5,
A first step of disposing the filling material on one surface of the base material;
A second step of generating a differential pressure between one surface of the base material and the other surface to fill the voids and communication holes of the base material with the filling material disposed on the one surface;
A third step of generating a differential pressure between one surface of the base material and the other surface to pass gas from the one surface to the communication hole of the base material;
A method for producing a foamed resin composite structure, comprising:

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