resin foam aggregate

Abstract

The premise is to reuse even the scraps of phenolic resin foam insulation, by reducing them to a roughly uniform size within a closed space before reusing the phenolic resin foam insulation. [Solution] A resin foam assembly comprising a resealable container and a plurality of resin foams inside the container, wherein 80% or more of the resin foam is phenolic resin foam, and the density of the phenolic resin foam is 20 kg / m³ 3 More than 70kg / m 3 A resin foam assembly that is as follows: the closed-cell ratio of the phenolic resin foam is 85% or more, the brittleness of the phenolic resin foam is 15% or more and 35% or less, and when the total mass of the phenolic resin foam in the container is M1 and the mass of one phenolic resin foam having the same volume as the internal volume of the container is M2, the mass ratio (M1 / M2) is 0.50 or more and 0.95 or less.

Description

[Technical Field]

[0001] This invention relates to a resin foam assembly. [Background technology]

[0002] In recent years, concerns about global warming have made the reduction of greenhouse gases an urgent priority. Among these, high-performance insulation of buildings, i.e., insulation materials, is considered extremely important as one means of reducing greenhouse gases through energy conservation. Among these, phenolic resin foam laminates are known as foamed plastic insulation materials with high insulation performance. Unlike fibrous materials such as glass wool and rock wool, phenolic resin foam laminates achieve low thermal conductivity by encapsulating gases with low thermal conductivity within fine, closed-cell structures. However, they are generally supplied in the form of boards, such as 3x6 boards, measuring 910mm wide and 1820mm long. On the other hand, there are many applications where 3x6 boards cannot be used as is, and cutting and processing are necessary to use the insulation material to fit the required space size.

[0003] On the other hand, because the size of the scraps generated by cutting processes often varies, these scraps are often incinerated because they are difficult to reuse. However, there has been a strong demand for the reuse of these scraps due to concerns about the environmental impact.

[0004] As a technique for using materials as aggregates within a closed space such as a bag, the technique disclosed in Patent Document 1 is known. Specifically, the technique disclosed involves compressing crushed rigid foam resin or the like into a flat shape using a press device or the like via packaging material, then sealing the packaging material and using it as an insulating material.

[0005] Furthermore, Patent Document 2 discloses a building insulation material in which a packaging material filled with foamed plastic granules is bonded to a moisture-proof sheet, and the packaging material is formed from a moisture-permeable sheet. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 11-325386 [Patent Document 2] Japanese Patent Publication No. 2008-231780 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, Patent Document 1 is a technology that is based on the premise of flattening and compressing crushed rigid foam resin, etc., into a flat shape using a press device or the like via packaging material. Therefore, although it is suitable for low-brittle materials such as urethane foam, when it contains a large amount of relatively brittle phenolic resin foam, there is a problem that the thermal conductivity deteriorates because the phenolic resin foam is destroyed by the compressive force.

[0008] On the other hand, Patent Document 2 is characterized by the packaging material being formed from a moisture-permeable sheet, based on the premise of multiple reuse of foamed plastic, particularly rigid polyurethane foam, similar to Patent Document 1. However, since it does not perform the pressurization operation described in Patent Document 1, it was found that it is not possible to sufficiently fill the gaps between the granules of the foamed plastic. As a result, it was difficult to produce a good resin foam aggregate with low thermal conductivity.

[0009] Therefore, the present invention aims to provide a technology that allows for the reuse of irregularly shaped scraps of phenolic resin foam insulation, which are not necessarily of a uniform shape, by reducing them to a roughly uniform size within a closed space, thereby enabling the reuse of the relatively brittle material known as phenolic resin foam insulation, and that takes advantage of the inherently low thermal conductivity of phenolic resin foam. [Means for solving the problem]

[0010] The inventors of the present invention have conducted extensive research to solve the above problems and have developed a technology to reduce gaps and improve thermal insulation performance by reducing the size of the irregularly cut scraps of phenolic resin foam insulation material to a nearly uniform size and then placing them within a closed space, while increasing the filling rate of the phenolic resin foam insulation material scraps within the closed space, that is, increasing the density of the resin foam aggregate. In other words, the present invention is as follows.

[0011] [1] A resin foam assembly comprising a resealable container and a plurality of resin foams within the container, wherein 80% or more by mass of the resin foam is phenolic resin foam, and the density of the phenolic resin foam is 20 kg / m³ 3 More than 70kg / m 3 A resin foam assembly having the following characteristics: the closed-cell ratio of the phenolic resin foam is 85% or more; the brittleness of the phenolic resin foam is 15% or more and 35% or less; and when the total mass of the phenolic resin foam in the container is M1 and the mass of one phenolic resin foam having the same volume as the internal volume of the container is M2, the mass ratio (M1 / M2) is 0.50 or more and 0.95 or less. [2] A resin foam assembly comprising a resealable container and a plurality of resin foams within the container, wherein 80% or more by mass of the resin foam is phenolic resin foam, and the density of the phenolic resin foam is 20 kg / m³ 3 More than 70kg / m 3 A resin foam assembly having the following characteristics: the closed-cell ratio of the phenolic resin foam is 85% or more; the brittleness of the phenolic resin foam is 15% or more and 35% or less; and the filling rate of the plurality of resin foams relative to the volume of the container is 50% or more and 95% or less. [3] A resin foam assembly according to [1] or [2], wherein 50% by mass or more of the phenolic resin foam is substantially rectangular. [4] Among the three sides extending from one corner of the rectangular parallelepiped, when the length of the shortest side is X and the length of the second shortest side is Y, the resin foam aggregate according to [3], where X / Y is 0.5 or less. [5] The resin foam aggregate according to any one of [1] to [4], wherein the thermal conductivity of the resin foam aggregate at 23°C is 0.040 W / (m·K) or less. [6] The resin foam aggregate according to any one of [1] to [5], wherein the phenolic resin foam contains at least one selected from the group consisting of hydrocarbons, hydrofluorocarbons, chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins, and chlorinated hydrocarbons.

Advantages of the Invention

[0012] According to the present invention, on the premise of reusing the end materials of the irregular phenolic resin foam heat insulating material that is not necessarily of a fixed shape, in a closed space, after reducing it to a substantially uniform size, the phenolic resin foam heat insulating material, which is a material with relatively high brittleness, is reused. That is, the original low thermal conductivity of the phenolic resin foam can be utilized.

Brief Description of the Drawings

[0013] [Figure 1] FIG. 1 is a perspective view schematically showing an example of the resin foam aggregate of the present embodiment. [Figure 2] FIG. 2 is a perspective view schematically showing an example of a rectangular parallelepiped-shaped phenolic resin foam. [Figure 3] FIG. 3 is a plan view schematically showing the cardboard frame used in the examples. [Figure 4] FIG. 4 is a side view schematically showing the cardboard frame used in the examples.

Embodiments for Carrying Out the Invention

[0014] The following describes in detail embodiments for carrying out the present invention (hereinafter referred to as "this embodiment"). It should be noted that the present invention is not limited to the following embodiments, and can be implemented in various modifications within the scope of its gist.

[0015] In this embodiment, the density, closed-cell ratio, brittleness, mass ratio (M1 / M2) of the phenolic resin foam (described later), the filling rate of multiple resin foams relative to the volume of the container, the thermal conductivity of the resin foam assembly at a 23°C environment, and the identification of the type of foaming agent in the phenolic resin foam are determined by the method described in the example.

[0016] In this embodiment, phenolic resin foam refers to phenolic resin foam that has been reduced to a substantially uniform size. Furthermore, a resin foam assembly refers to a collection of multiple resin foams, each containing phenolic resin foam, housed in a resealable container.

[0017] (Resin foam aggregate) The resin foam assembly of the first embodiment includes a resealable container, Multiple resin foams inside the container and A resin foam aggregate comprising, 80% by mass or more of the aforementioned resin foam is phenolic resin foam. The density of the phenolic resin foam is 20 kg / m³. 3 More than 70kg / m 3 The following: The closed-cell ratio of the phenolic resin foam is 85% or more. The brittleness of the phenolic resin foam is 15% or more and 35% or less. The resin foam assembly is such that, when M1 is the total mass of the phenolic resin foam inside the container, and M2 is the mass of one phenolic resin foam having the same volume as the internal volume of the container, the mass ratio (M1 / M2) is 0.50 or more and 0.95 or less.

[0018] Figure 1 is a schematic perspective view showing an example of a resin foam assembly according to this embodiment. The resin foam assembly 1 consists of multiple phenolic resin foams 2 inside a container 3. In the example in Figure 1, the container 3 is a bag and is closed.

[0019] • Resin foam The resin foam forming the resin foam aggregate is configured such that 80% or more by mass of the resin foam is phenolic resin foam, which has excellent thermal insulation properties. Other foam materials may be partially mixed in or laminated as phenolic resin foam, but the mass ratio of phenolic resin foam must be considered in order to lower the thermal conductivity. Furthermore, a surface material (face material) may be attached to a part of the phenolic resin foam, and if necessary, a binder, coating agent, etc. may be applied to the outer periphery of the phenolic resin foam. Multiple resin foams may be partially or completely bonded together using adhesives, etc. In addition, the phenolic resin foam may contain additives other than the main component.

[0020] The size of the phenolic resin foam can be set appropriately according to the purpose. In the case of a roughly rectangular prism shape, it is preferable that one side is 5 mm to 100 mm, more preferably 10 mm to 60 mm, even more preferably 10 mm to 50 mm, and most preferably 10 mm to 40 mm. In the case of a roughly rectangular prism, the lengths of the three sides may be different and can be set as appropriate. If one side of the roughly rectangular prism is 5 mm or more, it is possible to easily create the roughly rectangular prism and aggregates. On the other hand, if one side of the roughly rectangular prism is 100 mm or less, it is possible to fill it into a container efficiently, and the aggregates exhibit low thermal conductivity. Note that the size and shape of the phenolic resin foam may vary.

[0021] The number of phenolic resin foams forming the resin foam assembly can be appropriately set according to the purpose while considering the heat insulation space at the usage location. However, if the number is too small, efficient filling of the phenolic resin foam cannot be achieved. Therefore, it is preferably 10 or more in one closed space. Also, a plurality of resin foam assemblies can be combined and used.

[0022] The shape of the phenolic resin foam is not particularly limited and can be any shape. For example, a rectangular parallelepiped (e.g., plate-like, layered, sheet-like, etc.), a polyhedron other than a rectangular parallelepiped (e.g., a regular tetrahedron, a regular octahedron, a regular dodecahedron, a regular icosahedron, etc.), a sphere, a pyramid, a cone, a torus, a hollow cylinder, a solid cylinder (cylinder), an irregular shape, etc. can be mentioned. However, it is preferable that the phenolic resin foam to be used is a substantially rectangular parallelepiped because the filling rate in the closed space increases. More preferably, 50% or more by mass ratio is a substantially rectangular parallelepiped, even more preferably 70% or more is a substantially rectangular parallelepiped, and most preferably 80% or more is a substantially rectangular parallelepiped. When 50% or more is a substantially rectangular parallelepiped, the filling rate in the container increases and a low thermal conductivity is exhibited. The "substantially rectangular parallelepiped" in this embodiment means that the surfaces forming the rectangular parallelepiped are not necessarily flat surfaces, and those with curved surfaces, those with curved connections between surfaces, and those with curved corners are also included.

[0023] The density of the phenolic resin foam in this embodiment is 20 kg / m 3 or more and 70 kg / m 3 or less, preferably 20 kg / m 3 or more and 50 kg / m 3 or less, more preferably 25 kg / m 3 or more and 45 kg / m 3 or less, even more preferably 25 kg / m 3 or more and 40 kg / m 3 or less, most preferably 25 kg / m 3 or more and 35 kg / m 3 or less. When the density of the phenolic resin foam is 20 kg / m 3As described above, the mechanical strength, such as compressive strength, can be ensured when multiple phenolic resin foams are filled and tightly bonded, and damage to the phenolic resin foam can be avoided. On the other hand, the density of the phenolic resin foam is 70 kg / m³. 3 The following conditions result in a single enclosed resin foam assembly that is easy to handle without increasing its weight.

[0024] The closed-cell ratio of the phenolic resin foam in this embodiment is 85% or more, preferably 87% or more, more preferably 89% or more, even more preferably 91% or more, and most preferably 93% or more. A closed-cell ratio of 85% or more in the phenolic resin foam allows for lower initial and long-term thermal conductivity of the phenolic resin foam. This is preferable because it allows for lower initial and long-term thermal conductivity of the resin foam assembly.

[0025] The brittleness of the phenolic resin foam in this embodiment is 15% to 35%, preferably 17% to 33%, more preferably 19% to 31%, even more preferably 19% to 29%, and most preferably 19% to 27%. For the phenolic resin foam to exhibit the required thermal and mechanical properties, the brittleness should be 15% or more, and if the brittleness is 35% or less, the filling rate can be increased without damaging the phenolic resin foam when it is assembled into a resin foam assembly.

[0026] Figure 2 is a schematic perspective view showing an example of a rectangular prism-shaped phenolic resin foam. When the length of the shortest of the three sides of the rectangular prism is X and the length of the shorter of the other two sides is Y, it is preferable that X / Y is 0.5 or less, as this makes it easier to uniformly determine the direction of the shortest side of the rectangular prism, thereby further increasing the filling efficiency of the phenolic resin foam in the closed space. It is more preferable that X / Y be 0.35 or less, even more preferable that X / Y be 0.2 or less, and most preferable that X / Y be 0.1 or less.

[0027] ·container The container that can be closed (hereinafter sometimes simply referred to as "container") is not particularly limited, as long as it can hold multiple phenolic resin foams together. The container may be either permeable or impermeable, but an impermeable container is more preferable because it can suppress the emission of volatile substances such as formaldehyde from the phenolic resin foam. The external dimensions of the container can also be set arbitrarily.

[0028] Furthermore, the shape of the container can be appropriately selected according to the intended use, such as a bag, box, or cylindrical shape. Examples of bag-type containers include two-sided bags, three-sided bags, three-sided bags with zippers, gusseted bags, bottom gusseted bags, stand-up pouches, stand-up zippered bags, four-sided flat-bottom gusseted bags, side-sealed bags, and bottom bags.

[0029] The container only needs to be able to be closed. In the case of a resin foam assembly, the container may be partially open, i.e., not closed, or it may be closed. In one embodiment, the container is closed or sealed. In another embodiment, the container is not closed. In yet another embodiment, the container is closed but not sealed.

[0030] In this embodiment, the term "closed" usually refers to a state in which substances cannot enter or leave the container, or a state in which substances cannot enter or leave the container, even more so than in an unclosed container, and is less airtight than "sealed".

[0031] The method of closing the container is not particularly limited, and known means can be used. For example, if it is a bag-shaped container, the open part may be simply closed by folding it once or twice or more, or the opening of the bag may be tied by hand (for example, with a knot), or the opening of the bag may be tied with string, cable ties or wire, or the opening of the bag may be closed with a zipper, clip, stapler, heat seal or heat bond. For example, if it is a box-shaped container, the container may be closed by closing the lid, and the closed part of the lid may or may not be sealed. The method of sealing is not particularly limited, and examples include tape and adhesive.

[0032] Furthermore, it is preferable to use compression bags or heat shrink bags to enhance exhaust efficiency by utilizing reduced pressure and heat, thereby creating a closed space with higher filling efficiency between phenolic resin foams. However, when reducing pressure, it is preferable to maintain a reduced pressure state within the closed space that does not destroy the phenolic resin foam. More specifically, the pressure within the closed space is 91 kPa or more and 100 kPa or less, preferably 96 kPa or more and 100 kPa or less, and even more preferably 98 kPa or more and 100 kPa or less. If the pressure within the closed space is less than 91 kPa, the phenolic resin foam will be destroyed, and the thermal conductivity of the resin foam assembly at a 23°C environment will increase, so compression operations such as those described in Patent Document 1 should not be performed before or after reducing pressure. Also, in the case of box-shaped or cylindrical shapes, it is preferable to select a highly rigid material such as corrugated cardboard or mold to make it easier to maintain a stable and constant shape. Furthermore, when forming a closed space using, for example, a flexible bag-shaped material, it is also possible to use a highly rigid material such as a box-shaped or cylindrical material on the outside of the closed space to maintain its shape.

[0033] In this embodiment, when the total mass of the phenolic resin foam in the container is M1, and the mass of one phenolic resin foam having the same volume as the internal volume of the closed container is M2, the mass ratio (M1 / M2) is 0.50 or more and 0.95 or less. M1 / M2 is preferably 0.53 or more and 0.92 or less, more preferably 0.56 or more and 0.89 or less, even more preferably 0.59 or more and 0.86 or less, and most preferably 0.62 or more and 0.83 or less. An M1 / M2 of 0.50 or more indicates that the phenolic resin foam is more densely packed, which is preferable because it reduces the thermal conductivity of the resin foam aggregate. Also, if M1 / M2 exceeds 0.95, it becomes necessary to pack the container more densely, which worsens workability. Note that if the container is double-walled, for example, if a bag-shaped container containing phenolic resin foam is placed inside another box-shaped container, the container whose internal volume is considered for determining M2 is the inner container in contact with the phenolic resin foam (the bag-shaped container in the above example).

[0034] In order to exhibit good thermal insulation performance, the thermal conductivity of the resin foam aggregate of this embodiment at a 23°C environment is preferably 0.040 W / (m·K) or less, more preferably 0.038 W / (m·K) or less, even more preferably 0.036 W / (m·K) or less, and most preferably 0.034 W / (m·K) or less.

[0035] For a resin foam assembly to exhibit low thermal conductivity, multiple phenolic resin foams must be tightly packed together without being destroyed. If the phenolic resin foam is destroyed by operations such as compression, the low-thermal-conductivity gas (foaming agent) within the phenolic resin foam's bubbles will escape from the bubble rupture, resulting in a higher thermal conductivity of the resin foam assembly at 23°C, which is undesirable. On the other hand, if gaps occur between the phenolic resin foams, convection of the air in those gaps occurs, accelerating heat transfer and thus increasing the thermal conductivity of the resin foam assembly. To improve the filling efficiency of the phenolic resin foam, it is preferable to set the ratio X / Y of the three sides of a rectangular parallelepiped, where X is the length of the shortest side and Y is the length of the second shortest side, to 0.5 or less. This reduces the gaps between the phenolic resin foams, thus achieving low thermal conductivity in the resin foam assembly.

[0036] To further reduce the thermal conductivity of an aggregate formed from multiple phenolic resin foams at a 23°C environment, it is preferable to include at least one selected from the group consisting of hydrocarbons, hydrofluorocarbons, chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins, and chlorinated hydrocarbons as a blowing agent.

[0037] Preferred hydrocarbons are cyclic or chain-like alkanes, alkenes, and alkynes having 3 to 7 carbon atoms. Specifically, examples include n-butane, isobutane, cyclobutane, n-pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, etc. Among these, pentanes such as n-pentane, isopentane, cyclopentane, and neopentane, and butanes such as n-butane, isobutane, and cyclobutane are preferred.

[0038] Examples of hydrofluorocarbons include hydrofluoropropene, hydrochlorofluoropropene, hydrobromofluoropropene, hydrofluorobutene, hydrochlorofluorobutene, hydrobromofluorobutene, hydrofluoroethane, hydrochlorofluoroethane, and hydrobromofluoroethane.

[0039] Chlorinated hydrofluoroolefins include HCFO-1224yd(Z) (chemical name: (Z)-1-Chloro-2,3,3,3-Tetrafluoropropene), which has particularly low thermal conductivity as a blowing agent, and 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd, for example, the E-isomer (HCFO-1233zd(E)), manufactured by Honeywell Japan Co., Ltd., product name: Solstice® LBA), and 1,1,2-tri- LOLO-3,3,3-trifluoropropene (HCFO-1213xa), 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za), 1-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224zb), 2,3,3-trichloro-3-fluoropropene (HCFO-1231xf), 2,3-dichloro-3,3-difluoropropene (H CFO-1232xf), 2-chloro-1,1,3-trifluoropropene (HCFO-1233xc), 2-chloro-1,3,3-trifluoropropene (HCFO-1233xe), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-1,2,3-trifluoropropene (HCFO-1233yb), 3-chloro-1,1,3-trifluoropropene (HCFO-1233yc), 1-chloro-2,3,3-trifluoro Examples include chloropropene (HCFO-1233yd), 3-chloro-1,2,3-trifluoropropene (HCFO-1233ye), 3-chloro-2,3,3-trifluoropropene (HCFO-1233yf), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb), and 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), and their stereoisomers, i.e., the E-isomer or the Z-isomer, or a mixture thereof, can be used. Furthermore, (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)) can also be mentioned.

[0040] Examples of non-chlorinated hydrofluoroolefins include 1,3,3,3-tetrafluoropropane-1-ene (HFO-1234ze, e.g., the E-isomer (HFO-1234ze(E)), manufactured by Honeywell Japan Co., Ltd., product name: Solstice(trademark)ze), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz, e.g., the Z-isomer (HFO-1336mzz(Z)), manufactured by Chemours K.K., Opteon(trademark) 1100), and 2,3,3,3 Examples include -tetrafluoro-1-propene (HFO-1234yf), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 3,3,3-trifluoropropene (HFO-1243zf), and 1,1,1,4,4,5,5,5-octafluoro-2-pentene (HFO-1438mzz). One or a mixture of these stereoisomers, i.e., the E-isomer or the Z-isomer, is used.

[0041] When using chlorinated hydrofluoroolefins or non-chlorinated hydrofluoroolefins, it is preferable that the content of these blowing agents in the total blowing agent is 30% by mass or more.

[0042] As chlorinated hydrocarbons, linear or branched chlorinated aliphatic hydrocarbons having 2 to 5 carbon atoms are preferably used. The number of bonded chlorine atoms is preferably 1 to 4, and examples include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Of these, propyl chloride and isopropyl chloride, which are chloropropanes, are more preferably used.

[0043] The foaming agents mentioned above may be used individually or in combination of two or more types, and can be selected at will.

[0044] (Resin foam aggregate) The resin foam assembly of the second embodiment includes a resealable container, Multiple resin foams inside the container and A resin foam aggregate comprising, 80% by mass or more of the aforementioned resin foam is phenolic resin foam. The density of the phenolic resin foam is 20 kg / m³. 3 More than 70kg / m 3 The following: The closed-cell ratio of the phenolic resin foam is 85% or more. The brittleness of the phenolic resin foam is 15% or more and 35% or less. The resin foam assembly is characterized in that the filling rate of the plurality of resin foams relative to the internal volume of the container is 50% or more and 95% or less.

[0045] In the resin foam assembly of the second embodiment, the filling rate of the multiple resin foams with respect to the internal volume of the container is 50% to 95%. The filling rate is preferably 53% to 92%, more preferably 54% to 89%, more preferably 56% to 89%, even more preferably 59% to 86%, and most preferably 62% to 83%.

[0046] In the resin foam assembly of the second embodiment, the container and multiple resin foams are the same as those of the resin foam assembly of the first embodiment, except that the filling rate of the "multiple resin foams" relative to the internal volume of the container is 50% or more and 95% or less, regardless of whether there is one type of resin foam or multiple types. In other words, the resin foam assembly of the second embodiment replaces the feature of the resin foam assembly of the first embodiment, which states that "when the total mass of the phenol resin foams in the container is M1, and the mass of one of the phenol resin foams having the same volume as the internal volume of the container is M2, the mass ratio (M1 / M2) is 0.50 or more and 0.95 or less," with the feature that "the filling rate of the multiple resin foams relative to the internal volume of the container is 50% or more and 95% or less." Therefore, in the resin foam assembly of the second embodiment, the container and multiple resin foams are the same as those of the resin foam assembly of the first embodiment. [Examples]

[0047] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0048] <Manufacturing of phenolic resin foam> In the production of phenol resin foam according to Example 1 of Japanese Patent Publication No. 2021-192962, a phenol resin foam (A) with a thickness of 45 mm was obtained in the same manner, except that 0.3% by mass of nitrogen relative to the foaming agent was used as a foaming nucleating agent instead of 4.0 parts by mass of phenol resin foam powder. The density, closed-cell ratio, and brittleness of the phenol resin foam (A) were measured using the method described later, and the density was found to be 29.1 kg / m³. 3 The closed-cell ratio was 93%, and the brittleness was 19%.

[0049] Furthermore, a phenolic resin foam (B) with a thickness of 45 mm was obtained in the same manner as in Example 12 of Publication WO2021 / 157698. The density, closed-cell ratio, and brittleness of the phenolic resin foam (B) were measured using the method described later, and the density was found to be 32.0 kg / m³. 3 The closed-cell ratio was 91%, and the brittleness was 21%.

[0050] <Preparation of multiple phenolic resin foams> Phenolic resin foam (A), (B) and polystyrene foam (manufactured by DuPont Styrofoam Corporation, trade name "Styrofoam® IB", thickness 30 mm, density 25 kg / m³) 3 Regarding the above, multiple specimens were prepared using a vertical cutter. When preparing the specimens, no specific cutting area was defined, and specimens including the surface layer and specimens without the surface layer were mixed together. Test piece A: A roughly rectangular (cube-shaped) test piece made of phenolic resin foam (A) with sides of 25 mm. Test piece B: A roughly rectangular specimen measuring 50mm x 50mm x 5mm, made of phenolic resin foam (A). Test specimen C: A roughly rectangular specimen measuring 25 mm × 25 mm × 12.5 mm, made of phenolic resin foam (A). Test piece D: A roughly rectangular (cube-shaped) test piece made of phenolic resin foam (B) with sides of 25 mm. Test piece E: A roughly rectangular (cube-shaped) test piece made of polystyrene foam, measuring 25 mm.

[0051] <Preparation of molds for thermal conductivity measurement> Prepare 5mm thick cardboard and make 20 pieces each of 45mm x 300mm cardboard A and 45mm x 200mm cardboard B. Stack 10 pieces of cardboard A and secure them together with adhesive tape (approximately 0.05mm thick) to create two 50mm thick, 45mm x 300mm cardboard corner rods A. Using cardboard B, make two 50mm thick, 45mm x 200mm cardboard corner rods B using the same procedure. Place the corner rods A on the floor with a 200mm gap between them, so that the 300mm x 45mm sides are parallel to each other and the 300mm x 50mm side faces downwards. Next, as shown in Figure 3, place corner rods B between the ends of the opposing corner rods A (when viewed from above, the whole thing is a 300mm square with a 200mm square hole in the center. See Figure 3). As shown in Figures 3 and 4, the parts where the square bars meet were secured with adhesive tape (approximately 0.05 mm thick) to prevent any gaps, thereby creating a cardboard frame.

[0052] (Example 1) <Fabrication of resin foam assemblies> Next, a 350mm long sheet was cut from a 280mm wide Wevac vacuum pack roll, and one end of the opening was heat-sealed. The resulting bag was used as a container. The inside of the bag was spread open, 60 specimens of test piece A were prepared, and the specimens A were placed into the bag through the opening and placed in an atmosphere of 23±1℃ and 50±2% humidity. In the procedure for measuring thermal conductivity described later, "after checking and adjusting the condition until the weight change after 24 hours was 0.2 mass% or less," the opening of the bag was heat-sealed to obtain a resin foam assembly. This resin foam assembly was placed in a space (internal volume of 200mm × 200mm × 45mm) made of a cardboard frame. Subsequently, the thermal conductivity was measured, as will be described later. The thermal conductivity of the resin foam aggregate was measured at 23°C and found to be 0.0390 W / (m·K). The M1 / M2 ratio was 0.52, and the filling density was 52%.

[0053] <Thermal conductivity of resin foam aggregate at 23°C> In accordance with JIS A 1412-2:1999, the thermal conductivity in the thickness direction of a resin foam assembly was measured at a temperature of 23°C using the following method. The specific procedure is as follows. When a resin foam assembly is stably installed on a horizontal surface, the height direction (perpendicular to the horizontal installation surface) at which its height is at its lowest is defined as the thickness direction. If the size of the resin foam assembly is such that two sides excluding the thickness direction are between 290 mm and 300 mm square, the thermal conductivity can be measured directly at 23°C. However, if the size is larger than 300 mm square or the surface is not smooth, the resin foam assembly must be cut to 300 mm square perpendicular to the thickness direction. However, to prevent changes in the filling state of the phenolic resin foam forming the resin foam assembly during cutting, it is desirable to cut one side at a time with the cut surface parallel to the horizontal installation surface, and immediately after cutting, all cut surfaces must be quickly fixed to prevent changes in the filling state of the phenolic resin foam. The fixing method is preferably to use tape or to fix the surface as thinly as possible with a surface hardening spray (a hardening accelerator specifically for instant adhesives), but the fixing method is not limited. Similarly, if the top and bottom surfaces in the thickness direction are not smooth, a smooth surface should be created by cutting and then the surface should be fixed. The method of surface fixing is not limited, but it is important that it does not affect the measurement of thermal conductivity at 23°C, and the thickness of the fixed surface should be 5 mm or less. Furthermore, if the surface perpendicular to the thickness direction of the resin foam assembly used to measure thermal conductivity at 23°C is less than 290 mm square, after performing the cutting and surface fixing described above, multiple resin foam assemblies are combined to make the entire resin foam assembly, consisting of multiple assemblies, between 290 mm square and 300 mm square, with the surface perpendicular to the thickness direction of the resin foam assembly being 290 mm square or more, and then the thermal conductivity at 23°C is measured. Place the specimen to be measured in an atmosphere of 23±1°C and 50±2% humidity. Then, monitor and adjust the conditions until the weight change after 24 hours is 0.2% by mass or less. Introduce the conditioned resin foam assembly into a thermal conductivity measuring device, which is also placed in an atmosphere of 23±1°C and 50±2% humidity. If the thermal conductivity measuring device is not located in a room controlled to 23±1°C and 50±2% humidity, as the foam laminate specimen was placed, immediately place the specimen in a polyethylene bag, seal the bag, remove it from the bag within one hour, and immediately measure the thermal conductivity. Thermal conductivity measurements are performed using a single-sample measurement device (Eiko Seiki Co., Ltd., product name "HC-074 / FOX304") with a low-temperature plate at 13°C and a high-temperature plate at 33°C for thermal conductivity at 23°C.

[0054] <Density of phenolic resin foam> The density of the phenolic resin foam was determined using the following procedure. All the resin foam is removed from the resin foam assembly, and the mass M1 of the phenolic resin foam is measured. Next, a water tank is prepared with a volume approximately twice that of the removed phenolic resin foam. The water tank is filled to the top with non-perforated beads with a diameter of approximately 2 mm. Next, all the non-perforated beads in the water tank are removed, and the mass Ma1 of the removed non-perforated beads (hereinafter, the entire set of removed non-perforated beads will be referred to as "non-perforated beads A") is measured. The apparent density ρa (=Ma1 / V0) of non-perforated beads A is calculated from Ma1 and the volume V0 of the water tank. Next, all of the removed phenolic resin foam is placed into the water tank. Furthermore, some of the non-perforated beads A are placed up to the top of the water tank, filling it completely so that all of the phenolic resin foam is in contact with the water tank or the non-perforated beads without any gaps. After that, the mass Ma2 of the non-perforated beads A that did not enter the water tank is measured. The total volume Vp of the phenolic resin foam contained in the container is calculated using the following formula. Vp = V0 - (Ma1 - Ma2) ÷ ρa The density (ρp) of phenolic resin foam is determined by the formula M1 / Vp.

[0055] <Closed-cell ratio of phenolic resin foam> The closed-cell ratio of phenolic resin foam was measured according to ASTM-D-2856 (Method C). Specifically, after removing the surface material from the phenolic resin foam, a cylindrical sample was drilled using a cork borer (one size smaller) selected according to the size of the phenolic resin foam, and the sample volume was measured using an air-comparison hydrometer (Tokyo Science Co., Ltd., Model 1000). The volume of the walls (parts other than bubbles and voids) was calculated from the sample mass and the density of the cured phenolic resin. The apparent volume was also calculated from the external dimensions of the sample. The closed-cell ratio was then calculated by subtracting the wall volume from the sample volume and dividing the result by the apparent volume. Here, the density of the phenolic resin was assumed to be 1.3 kg / L.

[0056] <Brittleness of phenolic resin foam> Twelve cubes with sides of 25 mm were cut out to serve as test specimens. However, if the side length of the phenolic resin foam was less than 25 mm, it was used as a test specimen as is. Twenty-four oak cubes with sides of 19 mm, dried at room temperature, and the twelve test specimens were placed in an oak wooden box with internal dimensions of 191 × 197 × 197 mm that could be sealed to prevent powder from escaping, and rotated at a speed of 60 ± 2 revolutions per minute for 600 ± 3 rotations. After the rotation was complete, the contents of the box were transferred to a mesh with nominal dimensions of 9.5 mm, and small pieces were removed by sieving. The value calculated using the following formula with the weight of the remaining test specimens (Wt2) and the weight of the test specimens before the test (Wt1) was defined as the brittleness (%). Brittleness (%)={(Wt1-Wt2) / Wt1}×100

[0057] <How to determine the mass ratio (M1 / M2)> The mass ratio (M1 / M2) was determined using the following procedure. Prepare a water tank at least three times the volume of the resin foam assembly, fill the tank with water to approximately twice the volume of the resin foam assembly, and record the water level in the tank. Then, submerge the resin foam assembly in the tank while applying pressure from above with a horizontal plate. Check and record the water level in the tank when the resin foam assembly is completely submerged. Convert the difference between the water level before and after submerging the resin foam assembly into volume, and determine the volume of the resin foam assembly V1(m³). 3 First, determine the volume V1. Next, calculate the mass (M2) by multiplying the volume V1 by the density (ρp) of the phenolic resin foam that was determined. Meanwhile, take out only the phenolic foam from the resin foam contained in the container and measure its mass (M1). It can be easily confirmed that it is phenolic foam by visual inspection, but if it is difficult to identify, it can be confirmed by measuring and recording the mass of the phenolic resin foam as appropriate and then performing various fracture analyses. From the obtained M1 and M2, calculate M1 / M2.

[0058] <Filling ratio of multiple resin foams relative to the container volume> The filling ratio of multiple resin foams relative to the container volume was determined using the following procedure. All the resin foam is removed from the resin foam assembly, and a tank is prepared with a volume approximately twice that of the removed resin foam. The tank is then filled to the top with non-perforated beads with a diameter of approximately 2 mm. Next, all the non-perforated beads are removed from the tank, and the mass Mb1 of the removed non-perforated beads (hereinafter, the entire set of removed non-perforated beads will be referred to as "non-perforated beads B") is measured. The apparent density ρb (=Mb1 / V1) of the non-perforated beads is calculated from Mb1 and the volume V1 of the tank. Next, place all of the removed resin foam into the tank. Then, fill the tank completely with a portion of the non-perforated beads B up to the top edge, ensuring that all of the resin foam is in contact with either the tank or the non-perforated beads. After that, measure the mass Mb2 of the non-perforated beads B that did not enter the tank. The total volume Vf of the resin foam contained in the container is calculated using the following formula. Vf = V1 - (Mb1 - Mb2) ÷ ρb The volume V1(m³) of the aforementioned resin foam assembly 3 Using (Vf) and Vf, the filling rate is calculated as (Vf / V1) × 100 = filling rate (%).

[0059] <Identification of foaming agent types in phenolic resin foam> First, the retention times were determined using halogenated hydrocarbons and standard hydrocarbon gases under the following GC / MS measurement conditions. Phenolic resin foam is used as the sample. If a surface material is attached, it is removed from the sample. A total of 0.25 mg of the phenolic resin foam is then cut out and placed in a dedicated container. 10 mL of chloroform and 12 crushed glass beads are added. The sample is homogenized using an IKA ULTRA-TURRAX Tube Drive at 6000 rpm for 7-11 minutes while extracting the components into the chloroform. The extract is then filtered through a 0.45 μm filter and subjected to GC / MS measurement. A standard sample solution of known concentration is prepared by dissolving the target component in chloroform and subjected to GC / MS measurement under the same conditions as the sample. Hydrocarbons, hydrofluorocarbons, chlorinated hydrofluoroolefins, unchlorinated hydrofluoroolefins, and chlorinated hydrocarbons are identified based on their pre-determined retention times and mass spectra.

[0060] <The ratio of the length of the shortest side X to the length of the second shortest side Y of a rectangular prism: X / Y> The width, length, and thickness of each test specimen were measured using a caliper as specified in JIS K 7248 or JIS B 7507. The length of the shortest side was denoted as X, and the length of the second shortest side as Y, and the ratio X / Y was calculated.

[0061] (Example 2) The procedure was carried out in the same manner as in Example 1, except that instead of using 60 specimens of specimen A as in Example 1, 51 specimens of specimen A (82% by mass) and 13 specimens of specimen E (18% by mass) were used. The thermal conductivity of the resin foam assembly at 23°C was 0.0398 W / (m·K), M1 / M2 was 0.53, and the filling rate was 54%.

[0062] (Example 3) The procedure was carried out in the same manner as in Example 1, except that instead of using 60 specimens of specimen A as in Example 1, 38 specimens of specimen A and 48 specimens of specimen B, each representing 50% of the mass, were used. The thermal conductivity of the resin foam assembly at 23°C was 0.0360 W / (m·K), M1 / M2 was 0.66, and the filling rate was 66%.

[0063] (Example 4) The procedure was carried out in the same manner as in Example 1, except that 101 specimens of specimen B were used instead of 60 specimens of specimen A as in Example 1. The thermal conductivity of the resin foam assembly at a 23°C environment was 0.0340 W / (m·K), M1 / M2 was 0.70, and the filling rate was 70%.

[0064] (Example 5) The procedure was carried out in the same manner as in Example 4, except that 52 specimens of specimen D were used instead of 60 specimens of specimen A as in Example 1. The thermal conductivity of the resin foam assembly at a 23°C environment was 0.0359 W / (m·K), M1 / M2 was 0.50, and the filling rate was 50%.

[0065] (Example 6) The procedure was carried out in the same manner as in Example 4, except that the number of specimens B was increased to 113 and the following operations were performed. After placing specimens B in a bag prepared according to the procedure of Example 1, the bag was placed in an atmosphere of 23±1℃ and 50±2% humidity. Subsequently, the change in weight was measured every 24 hours, and the condition was checked and adjusted until the change in weight after 24 hours was 0.2 mass% or less. Then, using the manual suction mode of a Wevac vacuum packing machine (model: V20f), a pressure gauge was attached to a location other than the suction part so that the internal pressure could be checked, and the pressure was reduced to 95kPa. After that, the pressure gauge attachment part was heat-sealed to prevent the internal pressure from changing, the pressure gauge was removed, and the opening of the bag was heat-sealed. The thermal conductivity of the resin foam assembly at a 23℃ environment was 0.0333 W / (m·K), M1 / M2 was 0.79, and the filling rate was 79%.

[0066] (Example 7) The procedure was carried out in the same manner as in Example 1, except that 150 specimens of specimen C were used instead of 60 specimens of specimen A as in Example 1. The thermal conductivity of the resin foam assembly at a 23°C environment was 0.0372 W / (m·K), M1 / M2 was 0.65, and the filling rate was 65%.

[0067] (Example 8) The procedure was carried out in the same manner as in Example 1, except that instead of using 60 specimens of specimen A, 37 specimens of specimen A and 75 specimens of specimen C were used. The thermal conductivity of the resin foam assembly at 23°C was 0.0380 W / (m·K), M1 / M2 was 0.65, and the filling rate was 65%.

[0068] (Comparative Example 1) The procedure was the same as in Example 1, except that the number of specimens A was changed to 51. The thermal conductivity of the resin foam assembly at 23°C was 0.0411 W / (m·K), M1 / M2 was 0.45, and the filling rate was 45%.

[0069] (Comparative Example 2) The procedure was the same as in Example 1, except that the number of specimens A was changed to 46. The thermal conductivity of the resin foam assembly at 23°C was 0.0424 W / (m·K), M1 / M2 was 0.40, and the filling rate was 40%.

[0070] (Comparative Example 3) A 350mm long sheet was cut from a 280mm wide Wevac vacuum pack roll, and the opening on one side was heat-sealed. The inside of the resulting bag was spread open, 81 specimens of test piece A were prepared, and the specimens A were placed into the bag through the opening. The bag was then placed in an atmosphere of 23±1℃ and 50±2% humidity (the thickness of the phenolic resin foam assembly in this state was 68mm). Metal plates were placed above and below, and the thickness was compressed from 68mm to 45mm (compression ratio of 0.66). Subsequently, the samples were placed in an atmosphere of 23±1℃ and 50±2% humidity. The weight change was measured every 24 hours, and the condition was checked and adjusted until the weight change after 24 hours was 0.2% by mass or less. Then, using the manual suction mode of a Wevac vacuum packing machine (model: V20f), a pressure gauge was attached to a location other than the suction area to check the internal pressure. After reducing the pressure to 95kPa, the pressure gauge attachment area was heat-sealed to prevent the internal pressure from changing, and then the opening of the bag was heat-sealed. The thermal conductivity of the resin foam aggregate at a 23℃ environment was 0.0419 W / (m·K), M1 / M2 was 0.70, and the filling rate was 70%.

[0071] (Comparative Example 4) The procedure was the same as in Example 1, except that 97 specimens of specimen E were used instead of 60 specimens of specimen A. The thermal conductivity of the resin foam assembly at 23°C was 0.0460 W / (m·K), M1 / M2 was 0.84, and the filling efficiency was 84%.

[0072] Table 1 shows the evaluation results for phenolic resin foam and resin foam assemblies in Examples 1-8 and Comparative Examples 1-4.

[0073] [Table 1]

[0074] The resin foam assemblies obtained in Examples 1 to 8 exhibit lower thermal conductivity and superior handling compared to the resin foam assemblies obtained in Comparative Examples 1 to 4. [Explanation of Symbols]

[0075] 1. Resin foam aggregate 2 Phenolic resin foam 3 containers 4. The shortest of the three edges extending from one corner of the rectangular prism. 5. The second shortest of the three edges extending from one corner of a rectangular prism. 6 square bar A 7 Square bar B 8 Adhesive tape [Industrial applicability]

[0076] According to the present invention, by utilizing an assembly of multiple phenolic resin foams contained within a closed space, it is possible to effectively reuse scraps from cutting processes and other materials, and to provide high thermal insulation properties to suit the desired construction space.

Claims

1. A container that can be closed, Multiple resin foams inside the container and A resin foam aggregate comprising, 80% or more by mass of the aforementioned resin foam is phenolic resin foam. The density of the phenolic resin foam is 20 kg / m³. ３ More than 70kg / m ３ The following: The closed-cell ratio of the phenolic resin foam is 85% or more. The brittleness of the phenolic resin foam is 15% or more and 35% or less. A resin foam assembly in which, when the total mass of the phenolic resin foam in the container is M1, and the mass of one phenolic resin foam having the same volume as the internal volume of the container is M2, the mass ratio (M1 / M2) is 0.50 or more and 0.95 or less.

2. A container that can be closed, Multiple resin foams inside the container and A resin foam aggregate comprising, 80% or more by mass of the aforementioned resin foam is phenolic resin foam. The density of the phenolic resin foam is 20 kg / m³. ３ More than 70kg / m ３ The following: The closed-cell ratio of the phenolic resin foam is 85% or more. The brittleness of the phenolic resin foam is 15% or more and 35% or less. A resin foam assembly in which the filling rate of the plurality of resin foams relative to the internal volume of the container is 50% or more and 95% or less.

3. The resin foam assembly according to claim 1 or 2, wherein 50% by mass or more of the phenolic resin foam is substantially rectangular.

4. The resin foam assembly according to claim 3, wherein, of the three sides extending from one corner of the substantially rectangular parallelepiped, the length of the shortest side is X and the length of the second shortest side is Y, and X / Y is 0.5 or less.

5. The resin foam assembly according to claim 1 or 2, wherein the thermal conductivity of the resin foam assembly at a 23°C environment is 0.040 W / (m·K) or less.

6. The resin foam assembly according to claim 1 or 2, wherein the phenolic resin foam comprises at least one selected from the group consisting of hydrocarbons, hydrofluorocarbons, chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins, and chlorinated hydrocarbons.

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