JP7345138B2 - Insulating structures equipped with vacuum insulation materials, home appliances, housing walls, and transportation equipment using the same - Google Patents

Description

The present disclosure relates to a heat insulating structure including a vacuum heat insulating material, and home appliances, house walls, transportation equipment, etc. using the heat insulating structure.

The vacuum heat insulating material has a structure in which a core material is sealed inside an outer covering material in a vacuum sealed state (substantially in a vacuum state). The outer covering material has gas barrier properties in order to maintain a substantially vacuum state inside. Conventionally, as one method for improving gas barrier properties, it has been proposed to incorporate layered clay minerals into the gas barrier layer of the outer covering material.

For example, Patent Document 1 discloses a structure in which an outer covering material of a vacuum insulation material has a welding layer and a gas barrier layer, and this gas barrier layer contains a layered clay material (layered clay mineral) and a polymer material. Disclosed. As described above, if the outer covering material has a gas barrier layer containing a layered clay mineral, it is possible to effectively suppress the permeation and infiltration of gas from the outer surface of the vacuum heat insulating material toward the inside.

However, since common layered clay minerals are hydrophilic, gas barrier layers containing layered clay minerals have reduced gas barrier properties in a humid environment. Therefore, in Patent Document 1, in order to achieve gas barrier properties for a long period of time even under high temperature and high humidity conditions, hydrophobic materials are used as the layered clay material (layered clay mineral) and the polymer material. ing. Such hydrophobic layered clay materials are not common. For example, in the example of Patent Document 1, hydrophobicity is imparted to the layered clay material by ion-exchanging inorganic cations contained in montmorillonite etc. with organic cations.

JP2009-085255A

The present disclosure provides a heat insulating structure including a vacuum heat insulating material that can be satisfactorily used even in a humid environment.

A heat insulating structure according to the present disclosure is a panel-shaped heat insulating structure including a vacuum heat insulating material and a foam heat insulating material. The vacuum heat insulating material includes a jacket material having gas barrier properties, a core material sealed inside the jacket material, and a gas adsorbent sealed inside the jacket material together with the core material. The inside of the outer covering material is under a reduced pressure state, and the outer covering material includes a gas barrier layer containing at least a layered clay mineral as a filler. The gas adsorbent has at least moisture adsorption properties. The foam insulation covers at least a portion of the outer surface of the vacuum insulation.

According to such a configuration, the vacuum insulation material constituting the heat insulation structure includes an outer sheathing material having a gas barrier layer, and the foam insulation material is provided so as to cover at least a portion of this outer sheathing material. . A gas adsorbent having moisture adsorption properties is sealed inside the vacuum heat insulating material. Since the foamed heat insulating material has low hygroscopicity and exhibits good water resistance, it is possible to suppress the infiltration of moisture from the outside of the outer covering material. Further, the gas adsorbent has moisture adsorption properties. Therefore, it is possible to adsorb moisture that has penetrated into the interior through the outer covering material whose gas barrier properties have deteriorated due to moisture absorption. Thereby, even if the heat insulating structure is used in a humid environment, deterioration in gas barrier properties due to moisture absorption can be effectively suppressed. As a result, it is possible to realize a heat insulating structure that can maintain good heat insulation performance not only in a standard humidity environment but also in a humid environment.

In addition to the above-described heat insulating structure, the present disclosure also includes home appliances, residential walls, transportation equipment, and the like that are provided with the heat insulating structure having the configuration of the present disclosure.

According to the present disclosure, it is possible to provide a heat insulating structure including a vacuum heat insulating material that can be satisfactorily used even in a humid environment.

FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a heat insulating structure according to an embodiment of the present disclosure. FIG. 2A is a schematic partial cross-sectional view showing an example of the configuration of an outer covering material included in the heat insulating structure shown in FIG. 1. FIG. FIG. 2B is a schematic partial cross-sectional view showing an example of the configuration of an outer covering material included in the heat insulating structure shown in FIG. 1. FIG. FIG. 2C is a schematic partial cross-sectional view showing an example of the configuration of an outer covering material included in the heat insulating structure shown in FIG. 1. FIG. FIG. 3 is a schematic cross-sectional view showing another example of the structure of the heat insulating structure shown in FIG.

(Findings that formed the basis of this disclosure)
In recent years, demand for vacuum insulation materials is expected to increase as energy conservation is expected to progress, even in hot and humid regions year-round. Furthermore, as global warming progresses, humidity may increase in some regions.

Here, it is assumed that the gas barrier properties of the outer covering material of the vacuum insulation material are derived from a layered clay material. Then, when such a vacuum insulation material is used in a humid environment, the gas barrier properties are reduced due to the water content of the layered clay mineral, as described above, and the insulation effect of the vacuum insulation material is reduced.

Therefore, in order to cope with a humid environment such as a hot and humid region, it is possible to use a hydrophobic layered clay mineral to suppress the deterioration of gas barrier properties, as disclosed in Patent Document 1. However, such hydrophobic layered clay minerals require special processing compared to general layered clay minerals, which increases the cost of the vacuum insulation material.

The present disclosure has been made in view of such problems.

(An example of an aspect of the present disclosure)
A heat insulating structure according to the present disclosure is in the form of a panel including a vacuum heat insulating material and a foam heat insulating material. The vacuum heat insulating material includes a jacket material having gas barrier properties, a core material sealed inside the jacket material, and a gas adsorbent sealed inside the jacket material together with the core material. The interior of the outer covering material is under reduced pressure, and the outer covering material includes a gas barrier layer containing at least a layered clay mineral as a filler. The gas adsorbent has at least moisture adsorption properties. The foam insulation covers at least a portion of the outer surface of the vacuum insulation.

According to such a configuration, the vacuum heat insulating material constituting the heat insulating structure includes an outer covering material having a gas barrier layer, and the foamed heat insulating material is provided so as to cover at least a portion of this outer covering material. There is. Furthermore, a gas adsorbent having moisture adsorption properties is sealed inside the vacuum heat insulating material.

Since the foamed heat insulating material has low hygroscopicity and exhibits good water resistance, it is possible to suppress the infiltration of moisture from the outside of the outer covering material. The gas adsorbent has moisture adsorption properties. Therefore, it is possible to adsorb moisture that has penetrated through the outer covering material whose gas barrier properties have deteriorated due to moisture absorption by the layered clay mineral and has entered the interior. Thereby, even if the heat insulating structure is used in a humid environment, deterioration in gas barrier properties due to moisture absorption can be effectively suppressed. As a result, it is possible to realize a heat insulating structure that can maintain good heat insulation performance not only in a standard humidity environment but also in a humid environment.

The foam insulation material may be a rigid urethane foam.

If the foam insulation material is made of rigid urethane foam, even if moisture infiltrates the foam insulation material, the moisture will be chemically captured by the reaction between the isocyanate groups remaining in the rigid urethane foam and the moisture. . Thereby, it is possible to reduce the possibility that moisture will reach the outer cover material of the vacuum insulation material covered with the foam insulation material. Therefore, moisture absorption of the gas barrier layer can be effectively suppressed. As a result, the deterioration of the gas barrier properties of the outer covering material is also suppressed, and it becomes possible to maintain good heat insulation performance of the vacuum heat insulating material and the heat insulating panel including the same.

The rigid urethane foam is produced by combining a polyol component and an isocyanate component such that the equivalent ratio of the isocyanate group (-NCO) of the isocyanate component to the hydroxyl group (-OH) of the polyol component is within the range of 0.70 or more and 1.10 or less. They may be mixed and reacted.

The mixing ratio of the polyol component and the isocyanate component is set within a predetermined range based on the equivalent ratio of isocyanate groups to hydroxyl groups. This allows a sufficient amount of isocyanate groups to remain in the resulting rigid urethane foam within a range that does not impede heat insulation performance. Therefore, the moisture trapping effect of the isocyanate group can be effectively realized, so that deterioration of the gas barrier properties of the outer covering material can be effectively suppressed.

The thickness of the foam insulation material may be 1 mm or more.

If the thickness of the foam insulation material is at least 1 mm or more, even in a humid environment, it is possible to effectively prevent moisture such as water vapor from reaching the covering material of the vacuum insulation material. .

The gas adsorbent may contain ZSM-5 type zeolite which has been subjected to copper ion exchange.

According to such a configuration, the copper ion exchange ZSM-5 type zeolite has excellent adsorption ability for nitrogen, oxygen, and moisture. Therefore, for example, during the manufacture of vacuum insulation materials, air components that could not be exhausted by vacuum pumps, trace amounts of gas that are generated inside the vacuum insulation material over time, and It is possible to adsorb and remove air components, moisture, etc. that permeate and infiltrate. As a result, the vacuum insulation material can achieve excellent insulation performance for a long period of time.

Copper ion exchange ZSM-5 type zeolite also has excellent adsorption capacity for carbon dioxide. Therefore, when the foam insulation material is rigid urethane foam, the gas adsorbent and foam insulation material can not only trap moisture well, but also prevent by-product carbon dioxide from permeating through the outer covering material. , can be adsorbed well. As a result, the insulation performance of the vacuum insulation material and the insulation panel equipped with the same can be maintained favorably.

The present disclosure also includes home appliances, residential walls, transportation equipment, and the like, which are provided with the heat insulating structure having the above-described configuration.

Hereinafter, typical embodiments of the present disclosure will be described with reference to the drawings. In the following description, the same or corresponding elements are denoted by the same reference numerals throughout all the figures, and redundant description thereof will be omitted.

[Insulating structure]
First, the heat insulating structure according to the present disclosure will be specifically described with reference to FIG. 1, using a heat insulating panel as a typical example thereof.

FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a heat insulating structure according to an embodiment of the present disclosure.

As shown in FIG. 1, a heat insulating panel 10 according to the present embodiment includes a vacuum heat insulating material 20 and a foam heat insulating material 13. Foamed heat insulating material 13 covers at least a portion of the outer surface of vacuum insulating material 20 .

In the configuration shown in FIG. 1, the foam insulation material 13 covers the entire outer surface of the vacuum insulation material 20. Further, the foamed heat insulating material 13 is filled between the front surface material 11 and the back surface material 12 of the heat insulation panel 10. Therefore, the heat insulating panel 10 according to the present embodiment includes a front material 11 and a back material 12 in addition to the vacuum heat insulating material 20 and the foamed heat insulating material 13.

The specific configurations of the front surface material 11 and the back surface material 12 are not limited to specific ones, and those known in the field of heat insulation panels 10 can be suitably used. As the surface material 11, a plate made of wood, plaster, resin, metal, or the like can be used. Specifically, for example, wood plates include those made of plywood, and metal plates include, for example, galvanized steel plates, but are particularly limited to these. Not done.

Further, as the back material 12, a film or foil of paper, resin, metal, etc. can be used. Specifically, for example, examples of paper films include kraft paper and calcium carbonate paper, and examples of metal foil include aluminum foil, but the invention is not particularly limited to these.

The specific structure of the foamed heat insulating material 13 is not particularly limited, and those known in the field of heat insulating panels 10 can be suitably used. Specifically, examples include rigid urethane foam (PUF), polyethylene foam (PEF), bead process polystyrene foam (EPS), extrusion process polystyrene foam (XPS), and phenol foam (PF). , but not particularly limited to these. Among these, rigid urethane foam is preferably used for the reasons described below.

There are no particular limitations on the specific thicknesses of the front material 11, the back material 12, and the foamed heat insulating material 13. These thicknesses can be set as appropriate depending on the use of the heat insulating panel 10 and the like. However, the thickness of the foamed heat insulating material 13 is preferably 1 mm or more. This is because the foamed heat insulating material 13 covers at least a portion of the outer surface of the vacuum heat insulating material 20. Note that the specific configuration of the foam heat insulating material 13 will be described later.

The vacuum insulation material 20 included in the heat insulation panel 10 includes a core material 21, an outer covering material (outer packaging material) 22, and a gas adsorbent 23. is sealed in a vacuum sealed state (substantially vacuum state). Further, a gas adsorbent 23 is sealed inside the outer covering material 22 together with the core material 21 .

The core material 21 is not limited to a specific material as long as it has heat insulating properties. Specifically, known materials such as fiber materials and foam materials can be mentioned. For example, in this embodiment, inorganic fiber is used as the core material 21. The inorganic fibers may be any fibers made of inorganic materials, and specific examples include glass fibers, ceramic fibers, slag wool fibers, and rock wool fibers. Since the core material 21 may be formed into a plate shape, it may contain a known binder material, powder, etc. in addition to these inorganic fibers. These materials contribute to improving the physical properties of the core material 21, such as its strength, uniformity, and rigidity.

In addition to inorganic fibers, thermosetting foam can be mentioned as a material that can be used as the core material 21. The thermosetting foam may be formed by foaming a thermosetting resin or a resin composition containing the thermosetting resin (thermosetting resin composition) by a known method. Specific examples of the thermosetting resin include, but are not limited to, epoxy resins, phenol resins, unsaturated polyester resins, urea resins, melamine resins, polyimides, and polyurethanes.

Further, the foaming method is not particularly limited, and may be foamed using a known foaming agent and under known conditions. In addition, other than inorganic fibers and thermosetting foams, materials that can be used as the core material 21 include known organic fibers (fibers made of organic materials), but the specific types thereof are Not limited.

The outer covering material 22 is a bag-shaped member having gas barrier properties, and in this embodiment, it is formed into a bag-like shape by, for example, placing two laminated sheets facing each other and sealing the periphery thereof. The surrounding sealed portion is configured as a sealed portion 24 in which the core material 21 does not exist inside and the laminated sheets are in contact with each other. The sealing portion 24 has a fin shape extending from the main body of the vacuum heat insulating material 20 toward the outer periphery.

Here, the gas barrier properties in the present disclosure generally mean gas permeability of 10 ⁴ [cm ³ /m ² ·day · atm] or less, preferably 10 ³ [cm ³ /m ² ·day · atm]. *atm] or less, more preferably 10 ² [cm ³ /m ² ·day · atm] or less.

Although the specific structure of the outer cover material 22 is not particularly limited, it has a gas barrier layer that exhibits the above-mentioned gas barrier properties. This gas barrier layer contains at least layered clay mineral as a filler. In the example shown in FIG. 1, the outer covering material 22 has a three-layer structure of an outer surface protective layer 221, a clay mineral gas barrier layer 222, and a thermal adhesive layer 223, but the specific structure of the outer covering material 22 is as follows. Not limited. Further, details of the outer cover material 22 will be described later.

The gas adsorbent 23 is sealed inside the jacket material 22 together with the core material 21 . The gas adsorbent 23 adsorbs and removes gas components remaining inside the jacket material 22, that is, inside the vacuum insulation structure, and gas components that permeate from the outside over time. Furthermore, the gas adsorbent 23 has at least moisture adsorption properties. In other words, the adsorption properties of the gas adsorbent 23 include not only gas adsorption properties but also moisture adsorption properties. The water adsorption property of the gas adsorbent 23 is basically the property of adsorbing water vapor, and can be considered as a part of the gas adsorption property. The specific type of gas adsorbent 23 is not particularly limited, and known materials such as silica gel, activated alumina, activated carbon, metal adsorbent, and zeolite can be suitably used. Among these materials, only one type may be used as the gas adsorbent 23, or two or more types may be appropriately combined and used as the gas adsorbent 23.

In the present disclosure, as the gas adsorbent 23, ZSM-5 type zeolite is preferable, metal ion exchanged ZSM-5 type zeolite is more preferable, copper ion exchanged ZSM-5 type zeolite (copper ion exchanged ZSM -5 type zeolite) is particularly preferred.

The copper ion-exchanged ZSM-5 type zeolite has good gas adsorption properties and water adsorption properties, as will be described later. Further, the usage form of the gas adsorbent 23 is not particularly limited, and examples thereof include powder, a powder package, a powder compact, and the like. If the gas adsorbent 23 is a copper ion exchange ZSM-5 type zeolite, a molded body obtained by molding powder into a predetermined shape can be used.

When the copper ion-exchanged ZSM-5 type zeolite is used as a powder, the specific composition of the powder is not particularly limited, and it can be used as long as it has a general particle size, for example, within the range of several μm to several tens of μm. good. Further, the copper ion exchange ZSM-5 type zeolite may be one in which powder is enclosed in a bag. The specific structure of the bag used at this time is not particularly limited, and when a powdered gas adsorbent is used, a publicly known bag can be suitably used. Further, the copper ion-exchanged ZSM-5 type zeolite may be a molded body formed by molding powder into a predetermined shape, but the shape and molding method of the molded body are not particularly limited, and known methods are preferably used. It can be used for. The molded body may contain a known binder component in addition to the copper ion exchange ZSM-5 type zeolite.

The specific manufacturing method of the vacuum heat insulating material 20 is not particularly limited, and known manufacturing methods can be suitably used. Specifically, for example, as described above, the outer sheathing material 22 is formed into a bag shape, and the core material 21, gas adsorbent 23, etc. are inserted into the bag, and the core material 21, gas adsorbent 23, etc. are inserted into the bag, and the outer covering material 22 is placed in a reduced pressure environment (substantially vacuum state). , a manufacturing method that hermetically seals the bag-shaped outer covering material 22 can be mentioned. As described above, the method for configuring the outer covering material 22 in a bag shape is to prepare two laminated films that will become the outer covering material 22, and with the respective heat-sealing layers 223 facing each other, An example is a method of thermally welding the parts, but the method is not particularly limited thereto.

The heat insulating panel 10 may include members other than the front material 11, the back material 12, the foamed heat insulating material 13, and the vacuum heat insulating material 20. Moreover, the specific manufacturing method of the heat insulation panel 10 is not particularly limited. For example, using a known jig or the like, the vacuum heat insulating material 20 is placed between the front material 11 and the back material 12, and a layer of foamed heat insulating material 13 is formed between the front material 11 and the back material 12. A space may be formed and the foamed heat insulating material 13 may be filled in this space.

[Example of composition of outer covering material]
Next, a specific example of the configuration of the outer cover material 22 included in the vacuum heat insulating material 20 will be described.

2A to 2C are schematic partial cross-sectional views each showing an example of the configuration of an outer cover material included in the heat insulating structure shown in FIG. 1.

As shown in FIGS. 2A to 2C, examples of the outer covering material 22 include outer covering materials 22A to 22C made of laminated sheets having a multilayer structure.

As described above, the outer covering materials 22A to 22B include the clay mineral gas barrier layer 222 containing at least clay mineral as a filler, and also include the thermal adhesive layer 223. This is because, as described above, the outer covering material 22 shown in FIG. 1 is configured in the form of a sealed bag around two laminated sheets.

For example, the outer cover material 22A shown in FIG. 2A is a three-layer laminated sheet including an outer surface protective layer 221, a clay mineral gas barrier layer 222, and a heat sealing layer 223. Clay mineral gas barrier layer 222 is sandwiched between outer surface protective layer 221 and heat sealing layer 223. The outer surface protective layer 221 becomes the outer surface of the vacuum heat insulating material 20 , and the heat sealing layer 223 becomes the inner surface of the vacuum heat insulating material 20 .

Further, the outer cover material 22B shown in FIG. 2B is a 4-layer laminated sheet including an outer surface protection layer 221, a metal gas barrier layer 224, a clay mineral gas barrier layer 222, and a thermal adhesive layer 223. Two gas barrier layers, a metal gas barrier layer 224 and a clay mineral gas barrier layer 222, are sandwiched between the outer surface protective layer 221 and the thermal adhesive layer 223. Therefore, the outer cover material 22B is laminated in this order from the outside to the inside: the outer surface protection layer 221, the metal gas barrier layer 224, the clay mineral gas barrier layer 222, and the heat sealing layer 223. Although not shown, three or more gas barrier layers may be sandwiched between the outer surface protective layer 221 and the heat sealing layer 223.

Further, the outer covering material 22 included in the vacuum heat insulating material 20 includes an outer surface protective layer 221 and a thermal adhesive layer, like the outer covering material 22A shown in FIG. 2A and the outer covering material 22B shown in FIG. 2B. The present invention is not limited to a laminated sheet having one or more gas barrier layers between 223 and 223. For example, if the periphery of two laminated sheets is sealed to form a bag-like structure, it is sufficient that the structure includes the thermal adhesive layer 223 and has gas barrier properties.

For example, the outer covering material 22C shown in FIG. 2C is a laminated sheet with a two-layer structure, in which the outer side is a gas barrier layer and the inner side is a heat sealing layer 223. The outer gas barrier layer is an "outer surface protection/gas barrier layer 225" which also serves as the outer surface protection layer 221. This outer surface protection/gas barrier layer 225 may contain layered clay mineral as a filler. Furthermore, although not shown, a single gas barrier layer may be configured as the outer covering material 22 by serving as the outer surface protective layer 221 and the heat sealing layer 223. In this case, it is sufficient that the single gas barrier layer contains a layered clay mineral as a filler.

The outer surface protection layer 221 is a layer for protecting the outer surface (surface) of the vacuum heat insulating material 20. The specific material thereof is not particularly limited, but typically any resin having a certain degree of durability may be used. Specific resins include, for example, polyethylene terephthalate (PET), nylon (polyamide, PA), polycarbonate (PC), polyimide (PI), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), and polysulfone (PSF). and ultra-high molecular weight polyethylene (U-PE, UHPE or UHMWPE), but are not particularly limited thereto.

These resins may be used alone, or two or more resins may be used in a suitable combination as a polymer alloy. The polymer alloy may contain resins other than resins suitable for the outer surface protective layer 221. Furthermore, the outer surface protective layer 221 may contain components (such as various additives) other than the resin described above. That is, the outer surface protective layer 221 may be composed of only the above-mentioned resin, but may also be composed of a resin composition containing other components.

In the outer covering material 22A and the outer covering material 22B shown in FIGS. 2A and 2B, respectively, the outer surface protective layer 221 is configured as a single layer (single layer) resin film, but a plurality of resin films are laminated. may be configured. The thickness of the outer surface protective layer 221 is not particularly limited, as long as it has a thickness that can protect the outer surface of the outer cover material 22 (as well as the vacuum heat insulating material 20).

The clay mineral gas barrier layer 222, the metal gas barrier layer 224, and the outer surface protection/gas barrier layer 225 are layers for preventing outside air from penetrating into the inside of the vacuum heat insulating material 20. Among these, the clay mineral gas barrier layer 222 and the outer surface protection/gas barrier layer 225 contain at least a layered clay mineral as a filler, and the layered clay mineral exhibits gas barrier properties. Note that the clay mineral gas barrier layer 222 and the outer surface protection/gas barrier layer 225 may contain fillers other than the layered clay mineral.

Specific layered clay minerals include, for example, 1:1 layered clay minerals such as lizardite, amethyst, kaolinite, dickite, halloysite, talc, and pyrophyllite; saponite, hectorite, montmorillonite, beidellite, and octahedral vermiculite. , 2:1 layer of dioctahedral vermiculite, phlogopite, biotite, lepidolite, illite, muscovite, paragonite, clintonite, margarite, clinochlore, chamosite, nimite, donbasite, cookite and sudoite. types; misfits such as antigorite, greenalite, and caryopyrite; examples thereof include, but are not particularly limited to (clintnite can be classified not only as 2:1 layer type but also as misfits). These layered clay minerals may be used alone or in an appropriate combination of two or more types.

Furthermore, the layered clay mineral is not necessarily limited to naturally occurring minerals, but may also be synthetic or modified artificial minerals such as synthetic hectorite and modified bentonite. Therefore, in the present disclosure, the filler contained in the clay mineral gas barrier layer 222 and the outer surface protection/gas barrier layer 225 may be a layered silicate, regardless of whether it is a natural product or an artificial product.

When such a layered clay mineral is contained in the clay mineral gas barrier layer 222 and the outer surface protection/gas barrier layer 225, the layered clay mineral is oriented along the direction in which the layers extend (usually in the horizontal direction). As a result, even if gas attempts to pass through the clay mineral gas barrier layer 222 and the outer surface protection/gas barrier layer 225, the layered clay mineral oriented in the direction in which the layers spread prevents the gas from passing through. As a result, the clay mineral gas barrier layer 222 and the outer surface protection/gas barrier layer 225 can realize good gas barrier properties.

Note that the specific structure of the layered clay mineral, such as the particle size of the layered clay mineral and the aspect ratio of the layered clay mineral, is not particularly limited, and the thickness of the clay mineral gas barrier layer 222 and the outer surface protection/gas barrier layer 225 may vary. It can be set as appropriate depending on various conditions such as. Generally, the aspect ratio of the layered clay mineral is within the range of 10 to 3,000, and the preferable aspect ratio is 20 to 2,000.

The metal gas barrier layer 224 may be any gas barrier layer made of at least a metal, and specifically includes metal foil such as aluminum foil, copper foil, and stainless steel foil; metal vapor deposition in which metal is vapor-deposited on a base film. film; etc. This metal-deposited film may have a vapor-deposited layer in which a metal is vapor-deposited on a resin film serving as a base film, or a film in which the surface of this metal-deposited film is further subjected to a known coating treatment. (Coating metallized film). Examples of the metal to be vapor-deposited include aluminum, copper, and alloys thereof, but are not particularly limited.

Further, although not shown, instead of the metal gas barrier layer 224, an inorganic vapor-deposited film in which an inorganic compound other than metal is vapor-deposited onto a base film may be used. The specific structure of the inorganic vapor-deposited film is not particularly limited, and basically, a vapor-deposited layer in which an inorganic compound is vapor-deposited may be formed on a base film, similarly to the metal-deposited film. Examples of the inorganic compound to be vapor-deposited include oxides such as alumina and silica, but are not particularly limited.

Therefore, the outer cover material 22 only needs to include at least the clay mineral gas barrier layer 222 as a gas barrier layer, but may also be made of known metal foils, metal vapor deposited films, inorganic vapor deposited films, and other materials that do not contain layered clay minerals. The gas barrier layer may include a layer selected from the gas barrier layers of the composition.

Known resins can be used as base materials for the clay mineral gas barrier layer 222, the metal gas barrier layer 224, the outer surface protection/gas barrier layer 225, and other gas barrier layers. Specific resins include polyethylene terephthalate (PET) and ethylene-vinyl alcohol copolymer (EVOH), but are not particularly limited. Moreover, a resin composition containing components other than resin may be used as the base material.

When the gas barrier layer is a vapor-deposited film, a metal or the like may be vapor-deposited on the surface of the resin (resin composition) film that is the base material. When the gas barrier layer contains a layered clay mineral as a filler, the filler may be dispersed in a resin or a resin composition that is a base material, and then formed into a film by a known method.

The thermal adhesive layer 223 may be any layer (adhesive layer) for bonding the laminated sheets facing each other, but it may also function as a layer for protecting the inner surface of the vacuum heat insulating material 20 (inner surface protective layer). preferable.

The material used for the thermal adhesive layer 223 is not particularly limited as long as it has thermal adhesive properties that can be melted and bonded by heating, but typically various thermoplastic resins (thermal adhesive Resin) may be used. Specific resins include, for example, high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-high molecular weight polyethylene (U-PE, UHPE, or UHMWPE), and polypropylene (PP). ), ethylene-vinyl acetate copolymer (EVA), and nylon (polyamide, PE), but are not limited thereto. Among these, thermoplastic resins (polyethylenes, polypropylene, EVA, etc.) having a melting point of 250° C. or lower are more preferred.

These resins may be used alone, or may be used as a polymer alloy in which two or more types are appropriately combined. The polymer alloy may contain resins other than resins suitable for the heat-sealing layer 223. Furthermore, the thermal adhesive layer 223 may contain components (such as various additives) other than the above-mentioned resin. In other words, the heat-sealing layer 223 may be made of only the above-mentioned resin, or may be made of a resin composition containing other components.

Although not shown in the drawings, the heat sealing layer 223 in the outer covering materials 22A to 22C may contain a filler. Similar to the clay mineral gas barrier layer 222 and the outer surface protection/gas barrier layer 225, this filler may be a layered clay mineral or may be any other known filler. By containing the layered clay mineral, the thermal adhesive layer 223 can also function as a gas barrier layer. Further, by containing other known fillers, various functions can be imparted to the heat-sealing layer 223. Further, although not shown, the outer surface protective layer 221 may contain a filler.

Here, the thickness of each layer constituting the outer covering material 22 is not particularly limited. For example, the thickness of the clay mineral gas barrier layer 222 and the outer surface protection/gas barrier layer 225 may be within a range that can exhibit gas barrier properties depending on the material and the like. In particular, if the clay mineral gas barrier layer 222 and the outer surface protection/gas barrier layer 225 contain layered clay minerals as fillers, various conditions such as the particle size, aspect ratio, and amount of addition of the layered clay minerals should be taken into consideration. , just set the thickness.

The outer surface protective layer 221 may have a thickness that is sufficient to protect the outer surface of the outer covering material 22, that is, the outer surface of the vacuum heat insulating material 20, although it depends on the material. Further, the thermal adhesive layer 223 only needs to have a thickness that can exhibit sufficient adhesion when the outer sheathing materials 22 are bonded together, and desirably is used as an inner surface protective layer of the outer sheathing material 22. It is sufficient that the thickness is within a range that protects the inner surface.

As described above, the vacuum heat insulating material 20 is configured by enclosing the gas adsorbent 23 together with the core material 21 inside the jacket material 22 . As described above, copper ion exchange ZSM-5 type zeolite is preferably used as the gas adsorbent 23.

Copper ion exchange ZSM-5 type zeolite has excellent adsorption ability for nitrogen and oxygen, which are air components, as well as moisture. Therefore, if the gas adsorbent is made of copper ion-exchanged ZSM-5 type zeolite, the air components that could not be exhausted by the vacuum pump during the manufacture of the vacuum insulation material 20 will accumulate over time inside the vacuum insulation material 20. It is possible to adsorb and remove a small amount of generated gas, as well as air components and moisture that permeate from the outside to the inside of the vacuum insulation material 20 over time. As a result, the vacuum heat insulating material 20 can achieve excellent heat insulation performance for a long period of time.

Here, the gas barrier property of the clay mineral gas barrier layer 222 is due to the fact that the layered clay minerals are oriented along the spreading direction of the layer, so in the thickness direction of the layer, many layered clay minerals overlap to prevent gas (gas). elongates and complicates the permeation path of In other words, in the clay mineral gas barrier layer 222, the layered clay mineral creates a labyrinth-like gas permeation path (maze effect) in the thickness direction, thereby making it possible to exhibit gas barrier properties.

On the other hand, in the clay mineral gas barrier layer 222, when the layered clay minerals that overlap in the thickness direction absorb moisture, water vapor easily permeates and infiltrates into the vacuum insulation material 20, and other gases also permeate and infiltrate. It becomes easier. As a result, the gas barrier properties of the clay mineral gas barrier layer 222 deteriorate.

In contrast, in the present disclosure, a gas adsorbent 23 having moisture adsorption properties, such as copper ion exchange ZSM-5 type zeolite, is sealed inside the vacuum heat insulating material 20. Therefore, the water vapor remaining or permeating the clay mineral gas barrier layer 222 can be adsorbed (moisture absorbed). Thereby, a substantially vacuum state inside the vacuum heat insulating material 20 can be favorably maintained, and a decrease in the gas barrier properties of the clay mineral gas barrier layer 222 can also be suppressed.

[Foam insulation material]
In the present disclosure, foam insulation material 13 covers at least a portion of the outer surface of vacuum insulation material 20 . Since layered clay minerals are hydrophilic, if a humid environment continues for a long period of time, layered clay minerals will contain water. If the layered clay mineral contains water, the gas barrier properties of the clay mineral gas barrier layer 222, that is, the gas barrier properties of the outer sheathing material 22 of the vacuum heat insulating material 20 will deteriorate.

In contrast, in the present disclosure, as described above, at least a portion of the outer surface of the vacuum heat insulating material 20 is covered with the foam heat insulating material 13. In general, the foamed heat insulating material 13 has lower hygroscopicity than fiber-based heat insulating materials, and its insulation performance is less likely to deteriorate due to moisture absorption. Furthermore, the foamed heat insulating material 13 can have lower hygroscopicity and achieve better water resistance as the foaming rate is relatively lower. Therefore, by covering the outer surface of the vacuum heat insulating material 20, that is, the outside of the jacket material 22, with the foamed heat insulating material 13, it is possible to effectively suppress the clay mineral gas barrier layer 222 from absorbing moisture and deteriorating its gas barrier properties. I can do it.

Furthermore, as described above, the gas adsorbent 23 adsorbs moisture inside the outer cover material 22 (that is, inside the vacuum heat insulating material 20). As a result, due to the synergistic effect of the action of the foamed heat insulating material 13 on the outside of the outer covering material 22 and the action of the gas adsorbent 23 on the inside of the outer covering material 22, vacuum insulation is achieved by reducing the gas barrier properties of the clay mineral gas barrier layer 222. A decrease in the adiabatic resistance of the material 20 can be effectively suppressed.

As the foamed heat insulating material 13, as mentioned above, rigid urethane foam is preferably used. The rigid urethane foam may be one obtained by mixing a polyol component and an isocyanate component and foaming the mixture while performing a condensation polymerization reaction. The hydroxyl group (-OH) of the polyol component and the isocyanate group of the isocyanate component form a urethane bond (-NH-CO-O-) (urethanization reaction). Along with this reaction, a rigid urethane foam is obtained by foaming with a known foaming agent.

As the polyol component for forming the rigid urethane foam, known polyol compounds can be selected and used depending on the conditions required for the foamed heat insulating material 13. Typical examples include polyether polyols, polyester polyols, polyhydric alcohols, and hydroxyl group-containing diene polymers.

More specifically, examples of polyether polyols include compounds obtained by adding cyclic ethers or alkylene oxides to polyhydric alcohols, saccharides, alkanolamines, polyamines, polyhydric phenols, and other initiators. It will be done. As the polyhydric alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc. can be used. As the saccharide, sucrose, dextrose, sorbitol, etc. can be used, and as the alkanolamine, diethanolamine, triethanolamine, etc. can be used. As the polyamine, ethylenediamine, toluenediamine, diaminodiphenylmethane, polymethylene polyphenylamine, etc. can be used, and as the polyhydric phenol, bisphenol A, bisphenol S, phenol resin-based initial condensates, etc. can be used. Examples of the polyester polyols include polyhydric alcohol-polycarboxylic acid condensation polyols, cyclic ester ring-opening polymer polyols, and aromatic polyester polyols. These compounds may be used alone or in an appropriate combination of two or more.

Further, as the isocyanate component for forming the rigid urethane foam, a known isocyanate compound can be selected and used depending on the conditions required for the foamed heat insulating material 13. Representative examples include aromatic, alicyclic and aliphatic polyisocyanates having two or more isocyanate groups, and modified polyisocyanates obtained by modifying these polyisocyanates.

More specifically, isocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dimethylphenylene diisocyanate, dibenzyl diisocyanate, anthracene diisocyanate, and dimethyldiphenyl diisocyanate. Prepolymer-type modified products, isocyanurate-modified products, and urea-modified products of these can be mentioned, but are not particularly limited. The positions of substituents in these compounds are not particularly limited. These compounds and modified products may be used alone, or two or more types may be used in an appropriate combination.

A known catalyst can be used for the condensation polymerization reaction of the polyol component and the isocyanate component. Specifically, amine catalysts such as dimethylethanolamine, triethylenediamine, dimethylcyclohexylamine, 1,2-dimethylimidazole, pentamethyldiethylenetriamine, and bis(2-dimethylaminoethyl)ether; lead octylate, dibutyl Metal compound catalysts such as tin dilaurate; isocyanurate catalysts such as tris(dimethylaminopropyl)hexahydro-S-triazine, potassium acetate, and potassium octylate; and the like, but are not particularly limited. These catalysts may be used alone or in combination of two or more.

Further, the foaming agent may be any substance that can be vaporized and foamed by the reaction heat generated by the chemical reaction of the polyisocyanate component and the polyol component. Specifically, examples thereof include lower hydrocarbons having 6 or less carbon atoms, hydrofluorocarbons (HFC), and the like. Among these, pentanes such as n-pentane, i-pentane (2-methylbutane) and c-pentane (cyclopentane) are preferably used, but are not particularly limited.

As described above, the rigid urethane foam is formed by the urethanization reaction between the hydroxyl groups of the polyol component and the isocyanate groups of the isocyanate component. When water reacts with an isocyanate group instead of a polyol component, two molecules of the isocyanate component (OCN-R-NCO: R is any organic group) and two molecules of water (H ₂ O) react. , a urea bond (-R-NHCONH-R-NHCONH-) is formed, and two molecules of carbon dioxide are generated (CO ₂ ) (ureation reaction). Unreacted isocyanate groups may remain in the rigid urethane foam.

If the foamed heat insulating material 13 is made of rigid urethane foam, even if moisture such as water vapor enters the foamed heat insulating material 13, the moisture will be chemically captured by reacting with the remaining isocyanate groups. Thereby, it is possible to reduce the possibility that moisture will reach the outer cover material 22 of the vacuum heat insulating material 20 covered with the foamed heat insulating material 13. Therefore, moisture absorption of the clay mineral gas barrier layer 222 included in the outer covering material 22 can be effectively suppressed. As a result, the deterioration of the gas barrier properties of the outer cover material 22 is also suppressed, and it becomes possible to maintain good heat insulation performance of the vacuum heat insulating material 20 and the heat insulating panel 10 including the same.

In the present disclosure, as described above, the rigid urethane foam may be one obtained by mixing and reacting a polyol component and an isocyanate component, and the mixing reaction ratio of the polyol component and isocyanate component is not particularly limited. As a typical example, the polyol component and the isocyanate component are mixed such that the equivalent ratio of the isocyanate group (-NCO) of the isocyanate component to the hydroxyl group (-OH) of the polyol component is within a range of 0.70 or more and 1.10 or less. Examples include those obtained by mixing and reacting so that Alternatively, they may be mixed and reacted so that the equivalent ratio of isocyanate groups to hydroxyl groups is within the range of 0.65 or more and 1.10 or less.

As mentioned above, if the mixing ratio of the polyol component and the isocyanate component is set within the range of the equivalent ratio of isocyanate groups to hydroxyl groups, the resulting rigid urethane foam has a sufficient amount of amount of isocyanate groups can remain. Thereby, it is possible to satisfactorily realize the moisture trapping effect by the isocyanate group, so that deterioration in the gas barrier properties of the outer cover material 22 can be effectively suppressed.

The thickness of the foamed heat insulating material 13 may be 1 mm or more, as described above, regardless of its type. If the thickness is at least 1 mm or more, even in a humid environment, moisture such as water vapor can be effectively prevented from reaching the coated vacuum heat insulating material 20 (sheathing material 22). Here, if the foamed heat insulating material 13 is a rigid urethane foam, its preferred thickness may be 2 mm or more, and more preferably 3 mm or more.

As mentioned above, rigid urethane foam is formed by mixing and reacting two components, a polyol component and an isocyanate component. Further, when manufacturing the heat insulating panel 10, a mixture of these two components is spread and reacted in the space where the foamed heat insulating material 13 is formed. Therefore, although it depends on the specific configuration of the insulation panel 10, if the thickness of the foam insulation material 13 is 2 mm or more or 3 mm or more, even if the layer shape of the foam insulation material 13 is complicated, these two components can be well distributed throughout the reaction.

By the way, as mentioned above, if isocyanate groups remain in the rigid urethane foam, a ureation reaction occurs between water and the isocyanate groups, but as mentioned above, in this ureation reaction, carbon dioxide (CO ₂ ) is a by-product. live. Therefore, although the foamed heat insulating material 13 formed of rigid urethane foam can chemically capture moisture due to the remaining isocyanate groups, carbon dioxide is produced as a by-product and remains in the foamed heat insulating material 13 . Therefore, there is a possibility that carbon dioxide may permeate the outer sheathing material 22 and enter the inside of the vacuum heat insulating material 20 .

In the present disclosure, copper ion exchange ZSM-5 type zeolite is particularly preferably used as the gas adsorbent 23 sealed inside the vacuum heat insulating material 20. As mentioned above, this copper ion exchange ZSM-5 type zeolite has an excellent adsorption capacity for nitrogen, oxygen, and moisture, and also has an excellent adsorption capacity for carbon dioxide. In particular, at low partial pressures, copper ion-exchanged ZSM-5 type zeolites exhibit better carbon dioxide adsorption capacity. For example, at an equilibrium pressure of 20 Pa (one of the guidelines for the internal pressure of the vacuum insulation material 20), copper ion-exchanged ZSM-5 type zeolite has a carbon dioxide concentration of 1. It exhibits an adsorption capacity of about 5 times that of nitrogen and about 10 times that of air.

In the present disclosure, the foamed heat insulating material 13 is a rigid urethane foam, and the gas adsorbent 23 included in the vacuum heat insulating material 20 contains copper ion exchange ZSM-5 type zeolite. As a result, not only can moisture be captured well by the foamed heat insulating material 13, but even if by-product carbon dioxide permeates through the jacket material 22, it can be well adsorbed by the gas adsorbent 23. As a result, the insulation performance of the vacuum insulation material 20 and the insulation panel 10 including the same can be maintained favorably.

In this way, the heat insulating panel 10, which is a heat insulating structure according to the present disclosure, includes the foam heat insulating material 13 and the vacuum heat insulating material 20. Vacuum insulation 20 includes an outer covering 22 having a clay mineral gas barrier layer 222 . The foamed heat insulating material 13 is provided so as to cover at least a portion of the outer covering material 22 . A gas adsorbent 23 having moisture adsorption properties is sealed inside the vacuum heat insulating material 20 .

Since the foamed heat insulating material 13 has low hygroscopicity and exhibits good water resistance, it is possible to suppress moisture from entering the outer cover material 22 from outside. The gas adsorbent 23 has not only gas adsorption properties but also moisture adsorption properties. Therefore, it is possible to adsorb moisture that has penetrated into the interior of the outer covering material whose gas barrier properties have been degraded due to moisture absorption by the layered clay mineral. Thereby, even if the heat insulating structure is used in a humid environment, it is possible to effectively suppress a decrease in gas barrier properties due to moisture absorption of the layered clay mineral. As a result, it is possible to realize a heat insulating structure that can maintain good heat insulation performance not only in a standard humidity environment but also in a humid environment.

Note that in the heat insulating panel 10 having the configuration shown in FIG. 1, the foamed heat insulating material 13 covers all the outer surfaces of the vacuum heat insulating material 20, but the present disclosure is not limited thereto.

FIG. 3 is a schematic cross-sectional view showing another example of the structure of the heat insulating structure shown in FIG.

For example, like the heat insulating panel 10 having the configuration shown in FIG. The structure may be such that the surface and all side surfaces are covered with the foamed heat insulating material 13. Although not shown, a columnar frame member or the like is arranged so as to contact at least a part of the peripheral surface of the vacuum heat insulating material 20 (at this time, the fin-shaped sealing portion 24 may be bent). The outer surface other than the frame material may be covered with the foamed heat insulating material 13.

By configuring at least a portion of the vacuum heat insulating material 20 to be covered by the foamed heat insulating material 13, the effect of the present disclosure of suppressing the influence of moisture and carbon dioxide can be achieved.

Further, such a heat insulating panel 10 can be suitably used for various heat insulating purposes. An example of a typical heat insulation application is home appliances. Specific types of home appliances are not particularly limited, but examples include refrigerators, water heaters, rice cookers, and jar pots.

Moreover, as an example of other heat insulation applications, residential walls can be mentioned. An example of yet another insulation application is transportation equipment. Although the specific type of transportation equipment is not particularly limited, examples thereof include ships such as tankers, automobiles, and aircraft. In particular, the heat insulating panel 10 can be used well not only in a standard humidity environment but also in a humid environment such as a hot and humid region. Therefore, it can be suitably used for residential walls, home appliances, and transportation equipment that are expected to be used in humid environments.

Note that the present disclosure is not limited to the description of the embodiments described above, and various changes can be made within the scope of the claims, and the disclosure may be made in different embodiments and multiple modified examples. Embodiments obtained by appropriately combining the technical means described above are also included in the technical scope of the present disclosure.

INDUSTRIAL APPLICABILITY The present disclosure can be suitably used not only in the field of heat insulating structures equipped with vacuum heat insulating materials, but also widely and suitably in the fields of home appliances, residential walls, transportation equipment, etc. using this heat insulating structure. possible and useful.

10 Insulation panel (insulation structure)
11 Surface material 12 Back material 13 Foam insulation material 20 Vacuum insulation material 21 Core material 22, 22A, 22B, 22C Outer covering material (outer packaging material)
23 Gas adsorbent 24 Sealing part 221 Outer surface protection layer 222 Clay mineral gas barrier layer 223 Heat fusion layer 224 Metallic gas barrier layer 225 Outer protection and gas barrier layer

Claims (6)

A panel-shaped insulation structure comprising a vacuum insulation material and a foam insulation material,
The vacuum insulation material is
An outer covering material having gas barrier properties,
a core material sealed inside the outer covering material;
a gas adsorbent sealed inside the outer covering material together with the core material,
The interior of the outer covering material is in a reduced pressure state,
The outer covering material includes a gas barrier layer containing at least a hydrophilic layered clay mineral as a filler,
The gas adsorbent has at least moisture adsorption property,
The foam insulation material covers at least a portion of the outer surface of the vacuum insulation material ,
The foam insulation material is a rigid urethane foam in which unreacted isocyanate groups remain,
The rigid urethane foam includes a polyol component and an isocyanate component, and the equivalent ratio of the isocyanate group (-NCO) of the isocyanate component to the hydroxyl group (-OH) of the polyol component is in the range of 0.70 or more and 1.10 or less. It is a product that is mixed and reacted so that the
Insulated structure. The thickness of the foam insulation material is 1 mm or more,
The insulation structure according to claim 1 . The heat insulating structure according to claim 1 or 2, wherein the gas adsorbent contains copper ion-exchanged ZSM-5 type zeolite. A home appliance comprising the heat insulating structure according to any one of claims 1 to 3 . A residential wall comprising the heat insulating structure according to any one of claims 1 to 3 . A transportation device comprising the heat insulating structure according to any one of claims 1 to 3 .

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