JPH11311395A - Vacuum heat insulator, heat insulating box body, heat insulating panel, and manufacture of vacuum heat insulator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the recycle property of a vacuum heat insulator, and reduce the weight thereof by filling the powder carrying at least the oxidation inhibitor in a part of the powder formed by crashing the organic resin composition as a core material of a vacuum heat insulator in an inner bag material having a ventilating property. SOLUTION: The powder 4 of the crashed organic resin composition powder and the oxidation inhibitor 5 are mixed and agitated so as to manufacturing the powder 4 carrying the oxidation inhibitor 5. The predetermined a quantity of this powder 4 is filled in an inner bag material 3 having a ventilating property so as to manufacture a core material 2 for vacuum heat insulator 1. After performing the heating to the core material 2, the core material 2 is inserted with the gas adsorbent 6 into an outer material 7 made of the gas barrier type laminated film. Thereafter, evacuation is performed in a vacuum chamber provided with a thermal fusion device, and an end of the outer material 7 is sealed by thermal fusion so as to form a vacuum heat insulator 1. As an organic resin composition, the hard urethane foam as a foaming body of the urethane resin composition is especially desirable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vacuum heat insulator which can be used as a heat insulating material for a refrigerator or a building, and a heat insulating panel.

[0002]

2. Description of the Related Art In recent years, resource saving and energy saving for home electric appliances have been unavoidable important issues, and recycling of waste and improving the performance of heat insulating materials are also indispensable for refrigerators.

[0003] Also, with respect to buildings, due to the recent increase in high airtightness and high heat insulation of houses, hard urethane foams having better heat insulation performance have begun to be used from glass wool, which is currently the mainstream heat insulating material.

As described above, urgent demands of refrigerators and buildings include energy saving, and improvement of heat insulation performance is an important issue.

One means for solving such a problem is a vacuum heat insulator. For example, a vacuum insulator using an inorganic powder is described in Japanese Patent Application Laid-Open No. 57-173689. The content is as follows.
A vacuum heat insulator is obtained by filling the powder having a size of not more than μm, sealing the inside after reducing the pressure.

The effect is 13 to 133, which can be easily industrialized.
Since it can be manufactured at a vacuum of Pascal and the powder to be filled is fine, the pressure dependency of the heat insulating performance is small and excellent heat insulating performance is exhibited. Such a vacuum heat insulator generally has heat insulation performance three times or more that of rigid urethane foam.

[0007]

However, in a vacuum heat insulator in which a synthetic silica which is an inorganic powder is applied to a core material as disclosed in Japanese Patent Application Laid-Open No. 57-173689, it is inevitable to increase the density of the core material, There is a problem that the weight increases.

When disposing of a refrigerator or a heat insulating panel using a vacuum heat insulator, the vacuum heat insulator breaks during the volume reduction process due to a crash or the like, and the filled silica particles are scattered to deteriorate the working environment. cause.

Further, when the urethane foam and the vacuum heat insulator have a multi-layer structure, the composite is composed of an organic resin composition and an inorganic composition, so that the recyclability deteriorates.

In view of the above problems, the present invention fills a gas-permeable inner bag material with at least a powder carrying an antioxidant as a core material of a vacuum heat insulator on a part of a powder obtained by pulverizing an organic resin composition. Therefore, the present invention aims to improve the weight reduction and the recyclability of the vacuum heat insulator, which have been problems when the conventional inorganic powder is used as the core material.

Further, in order to cope with global environmental protection and waste problems, which will become more and more important in the future, it is possible to recycle urethane foam used particularly as a heat insulating material for refrigerators, and to use a vacuum heat insulating material. It is an object of the present invention to provide a novel vacuum heat insulator capable of improving the heat insulation performance over time.

[0012]

Means for Solving the Problems In order to solve the above-mentioned problems, a vacuum heat insulator of the present invention is obtained by pulverizing an organic resin composition into a gas-permeable inner bag material inside a gas barrier laminate film exterior material. It comprises a core material in which at least a part of the powder is filled with a powder carrying at least an antioxidant, and a gas adsorbent, and the interior of the exterior material is evacuated and evacuated.

Accordingly, the powder comprising the organic resin composition constituting the core material is a powder obtained by pulverizing waste materials such as refrigerator waste materials, waste building materials, and production loss materials in the production of resin products.
These are lighter in weight and easier to handle than inorganic materials such as conventional synthetic silica.

Further, the pulverization can be achieved easily and at low cost, and the core material of the vacuum heat insulator can be manufactured at low cost.

Further, since an antioxidant is carried on the powder obtained by pulverizing the organic resin composition, deterioration and decomposition of the resin due to radicals generated in the pulverization and heat treatment steps are suppressed, and vacuum insulation is performed. The thermal insulation performance of the body over time is also improved.

Further, in the vacuum heat insulator of the present invention, an organic resin composition containing at least a urethane resin composition foam is crushed into an air-permeable inner bag material inside an exterior material made of a gas barrier laminate film. It comprises a core material in which at least a part of the powder is filled with a powder carrying at least an antioxidant, and a gas adsorbent, and the interior of the exterior material is evacuated and evacuated.

Therefore, the powder obtained by pulverizing the foam of the urethane resin composition constituting the core material is a waste urethane material recovered from a used refrigerator, a urethane board for building materials, and a factory production loss material when urethane foam products are manufactured. It can be easily applied to waste materials such as. In addition, the pulverization can be achieved easily and at low cost, and the core material of the vacuum heat insulator can be manufactured at low cost.

Further, since the crushed urethane foam powder has a needle-like structure and is bulky, it is possible to maintain a low density even if it is a fine powder.

Further, since an antioxidant is carried on the powder obtained by pulverizing the waste urethane foam, deterioration and decomposition of the resin caused by radicals generated in the pulverization and heat treatment processes are suppressed, and the vacuum heat insulating material is reduced. Thermal insulation performance over time is also improved.

In the vacuum heat insulator of the present invention, the melting point of the antioxidant carried on the powder as the core material is 200 ° C. or more.

Therefore, even when the core material is subjected to heat degassing at a high temperature, the antioxidant is stably supported on the urethane resin powder without melting, so that the organic resin composition containing the urethane resin can be used. Degradation and decomposition due to oxidation and thermal oxidation can be suppressed stably.

Further, since the antioxidant having a high melting point is applied, the antioxidant does not melt during the heat treatment of the core material, and the powder constituting the core material does not condense.

Further, in the vacuum heat insulator of the present invention, the specific surface area of the antioxidant carried on the powder as the core material is the specific ratio of the powder obtained by pulverizing the foam of the urethane resin composition. The powder is at least 5 times larger than the surface area.

Therefore, even if it is not compatible with the urethane resin,
The effect of the antioxidant can be sufficiently exerted easily only by mixing and stirring.

Further, the vacuum heat insulator of the present invention is an antioxidant in which an organic resin composition is supported on pulverized powder,
The supported amount is 0.1% by weight or more and 5% by weight or less of the core material.

Therefore, the effect of the antioxidant can be sufficiently exhibited without adversely affecting the heat insulating performance of the vacuum heat insulator.

Further, the method for producing a vacuum heat insulator according to the present invention comprises:
The powder obtained by pulverizing the organic resin composition and the antioxidant are mixed and stirred, and the antioxidant is supported on the powder composed of the organic resin composition. After filling the core material and performing heat treatment on the core material at 120 ° C. to 180 ° C., it is inserted together with a gas adsorbent into an exterior material made of a gas barrier laminate film, and the inside is decompressed and vacuumed to 133 Pascal or less. In this case, the end of the exterior material is sealed by heat fusion.

Therefore, it is possible to easily produce a powder made of an organic resin composition carrying an antioxidant as a core material, and a core material of a vacuum insulator filled with the powder.

Further, in the heat treatment step for the purpose of dehydrating and degassing the core material, and also in the production steps of the vacuum heat insulating material such as the vacuum evacuation step, it can be easily produced by general-purpose equipment.

Further, since the antioxidant is applied even at the conventional heat treatment temperature at which the powder of the organic resin composition used as the core material causes thermal oxidative decomposition, heat treatment can be performed without any problem. Also, gas components that have been strongly dissolved in the urethane resin that could not be treated can be easily removed.

Further, the heat insulation box of the present invention has a vacuum heat insulator inside a box composed of an inner box and an outer box, and a space other than the vacuum heat insulator is foam-filled with a urethane resin composition. In a heat-insulated box, the vacuum heat-insulating body is formed by a vacuum.
It is a vacuum insulator described.

Therefore, a heat insulating box having excellent heat insulating performance over a long period of time can be obtained. Further, the weight of the heat insulating box is reduced.

Further, the heat insulating panel of the present invention comprises a structure having a concave structure made of an organic resin composition, a vacuum heat insulator disposed in a concave portion of the structure, and a surface covering an open surface of the concave portion of the structure. In a heat insulation panel constituted by a material, the vacuum heat insulator is the vacuum heat insulator according to claim 1 or 2.

Therefore, a heat insulating panel having excellent heat insulating performance over a long period of time can be obtained. Further, the weight of the heat insulating panel is reduced.

The heat insulating panel of the present invention comprises a urethane resin composition, a plurality of vacuum heat insulators, and a face material provided outside the vacuum heat insulator, and at least one plane of the vacuum heat insulator is provided. In a heat insulating panel covered with a urethane resin composition, the vacuum heat insulator is the vacuum heat insulator according to claim 1 or 2.

Accordingly, a heat insulating panel having excellent heat insulating performance over a long period of time can be obtained. Further, the weight of the heat insulating panel is reduced.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION The vacuum heat insulator according to the present invention is characterized in that at least a part of a powder obtained by pulverizing an organic resin composition into a gas-permeable inner bag material is oxidized inside an exterior material made of a gas barrier laminate film. It contains a core material filled with a powder carrying an inhibitor and a gas adsorbent, and the interior of the exterior material is evacuated to a reduced pressure.

Therefore, even if the organic resin composition constituting the core material is a refrigerator waste material, a waste building material, and a waste material such as a production loss material in the production of a resin product, the organic resin composition is collected, separated, and pulverized. The process can be easily applied. Also, pulverization can be achieved easily and at low cost by a general-purpose pulverizer.

The pulverizer can be applied to a general-purpose device such as a cutter mill or a hammer mill without any problem. However, a pulverization type pulverizer which can easily adjust the particle size of the powder is particularly excellent.

On the other hand, as the organic resin composition, most organic resin compositions such as urethane, phenol, polystyrene, polypropylene, polyethylene resin and the like can be applied irrespective of thermosetting resin or thermoplastic resin. Resin compositions with low conductivity are suitable. Among them, the powder obtained by pulverizing hard urethane foam, which is a foam of the urethane resin composition, is particularly bulky powder, resin thermal conductivity,
It is more suitable as a core material of a vacuum heat insulator in terms of aging characteristics such as gas generated from resin.

Therefore, the application of urethane waste materials recovered from used refrigerators, waste materials such as urethane boards and urethane panels of waste construction materials for buildings, and waste materials produced at the factory when manufacturing rigid urethane foam products can be applied. It is also suitable from the viewpoint of resource saving and recycling.

Further, the crushed rigid urethane foam powder has a needle-like structure and is a bulky powder, so that the core material can be reduced in density and the vacuum heat insulator can be reduced in weight.

Further, since an antioxidant is carried on the powder obtained by pulverizing the organic resin composition, radicals generated mechanochemically in the pulverization step and radicals generated in the heat treatment step of the core material. Generation of low molecular weight products and gas components due to degradation and decomposition of resin caused by radicals and peroxides caused by oxygen and peroxides and oxygen in the vacuum insulator over time, and vacuum insulation The heat insulation performance of the body over time is improved.

Incidentally, the antioxidant is a general-purpose antioxidant usually added to the organic resin composition and used to suppress the deterioration of the organic resin composition with time.
It refers to a radical chain inhibitor that supplements the generated radicals and inhibits the progress of the radical chain reaction, and a peroxide decomposer that decomposes the generated peroxide without generating radicals.

The radical chain inhibitor may be phenol, monophenol, bisphenol, high molecular phenol, amine or the like, and the peroxide decomposer may be sulfur, phosphorus or the like. Can be applied. They are,
Although they can be used alone or as a mixture, it is particularly effective to use a radical chain inhibitor and a peroxide decomposer in combination.

Specifically, bis (2.6-di-t-butyl-4-methylphenyl) pentaerythol-di-phosphite (mp 234 ° C.), 1.3.5-tris (3.5 -Di-t-butyl-4-hydroxybenzyl)
-S-Triazine-2.4.6- (1H.3H.5H)
Trione (melting point 221 ° C), 1.3.5-trimethyl-
2.4.6 Tris (3.5-di-t-butyl-4-hydroxybenzyl) benzene (melting point: 244 ° C.) can be used.

The powder composed of the organic resin composition thus prepared and the above-mentioned antioxidant are mixed and stirred, and the antioxidant is carried on the powder composed of the organic resin composition to constitute the core material. Make a body.

At this time, since the specific surface area of the antioxidant is limited, dispersion and support of the organic resin composition in the powder can be easily achieved.

At this time, in addition to the antioxidant, a flame retardant or the like can be applied as necessary. Thereafter, the powder is filled into a gas-permeable inner bag material to prepare a core material of a vacuum heat insulator.

After the core material is subjected to a heat treatment at 120 ° C. to 180 ° C., it is inserted together with a gas adsorbent into an exterior material made of a gas barrier laminate film. The vacuum heat insulator is manufactured by sealing the end of the exterior material by attaching.

It is to be noted that the heat treatment step for dehydrating and degassing the core material, as well as all the steps for manufacturing the vacuum heat insulator such as the vacuum evacuation step, can be easily made with general-purpose equipment.

With such an embodiment, the weight reduction and the recyclability, which are problems when the conventional inorganic powder is used as the core material, are intended to be improved.

Further, in order to protect the global environment and deal with the problem of waste, it is possible to recycle urethane foam used particularly as a heat insulating material for refrigerators, and it is also possible to improve the temporal insulation performance of a vacuum heat insulator. A new vacuum insulator can be provided.

[0054]

Embodiments of the present invention will be described below with reference to the drawings.

(Embodiment 1) FIG. 1 is a schematic view of a cross section of a vacuum heat insulator according to one embodiment of the present invention.
Reference numeral 2 denotes a core material, 3 denotes an inner bag material, 4 denotes a powder obtained by pulverizing an organic resin composition, 5 denotes an antioxidant, and shows how the powder is carried by the powder 4. Reference numeral 6 denotes a gas adsorbent, and reference numeral 7 denotes an exterior material made of a gas barrier laminate film.

The inner bag material 3 is made by forming a non-woven fabric made of polyethylene terephthalate into a bag by heat fusion.

The powder 4 is obtained by pulverizing hard urethane foam collected, separated and fractionated from a used refrigerator to an average particle size of 150 to 200 μm using a general-purpose pulverizer. The average particle size of the urethane pulverized product is a laser diffraction type particle size distribution analyzer SALD-30 manufactured by Shimadzu Corporation.
It was measured by 00J.

The antioxidant 5 is a phosphorus-based antioxidant that is a peroxide decomposer, and is a bis (2.
6-di-t-butyl-4-methylphenyl) pentaeristol-di-phosphite and a hindered phenol-based antioxidant which is a radical chain inhibitor, having a melting point of 24
1.3.5-trimethyl-2.4.6-tris (3.5-di-t-butyl-4-hydroxybenzyl) at 4 ° C.
Benzene and benzene were mixed one by one and applied. The antioxidant 5 was adjusted by a ball mill so that the specific surface area became 10 m ² / g or more.

As the gas adsorbent, synthetic zeolite 5A was used.
Was applied. The exterior material has polyethylene terephthalate (12 μm) as a surface protective layer on one side, aluminum foil (6 μm) as an intermediate layer, and high-density polyethylene (50 μm) as a heat-sealing layer.
m), the other side of which is a laminated film in which polyethylene terephthalate (12 μm) is laminated on the surface protective layer, aluminum-deposited ethylene / vinyl alcohol copolymer (15 μm) is laminated on the intermediate layer, and high-density polyethylene (50 μm) is laminated on the heat-sealing layer. Is used.

In addition to the above-mentioned constitution, biaxially stretched nylon or the like having excellent piercing strength, bending strength and the like can be applied to the surface protective layer. In addition, polypropylene, polyacrylonitrile, low-density polyethylene, and the like, which are excellent in heat-sealing properties, can be applied to the heat-sealing layer.

Further, depending on the application state of the vacuum heat insulator, polyethylene terephthalate (12 μm) is applied to the surface protective layer on both sides of the exterior material, aluminum foil (6 μm) is applied to the intermediate layer, and high-density polyethylene (50 μm) is applied to the heat sealing layer. In some cases, an exterior material is suitable.

Next, a method of manufacturing this vacuum heat insulator will be described. A powder made of the hard urethane foam powder pulverized and produced by the above method and a mixture of the antioxidant corresponding to 3% by weight of the core material are mixed and stirred to prepare a powder carrying the antioxidant.

Thereafter, a predetermined amount of the powder is filled in a gas-permeable inner bag material to prepare a core material of a vacuum heat insulator.

At this time, in order to improve the fluidity of the powder, 3 wt% of the core material is added with synthetic silica powder generally known as a fluidizing agent.

The core material was subjected to a heat treatment at 180 ° C. for 1 hour, then inserted together with a gas adsorbent into an exterior material made of a gas barrier laminate film, and evacuated in a vacuum chamber equipped with a heat fusion device. Then, a vacuum heat insulator was produced by sealing the end of the exterior material by heat fusion.

At this time, the exhaust pressure was reduced so that the internal pressure of the vacuum heat insulator became 13 Pascal or less.

The density of the vacuum heat insulator in the vacuum heat insulator thus manufactured was reduced by 20% or more as compared with the vacuum heat insulator using the synthetic silica powder as the core material. Therefore, it is possible to improve the handleability and transport efficiency of the vacuum insulator itself and reduce the weight of the product to be applied.

The thermal conductivity of the vacuum heat insulator was measured using AUTO-A manufactured by Eiko Seiki Co., Ltd. and compared with the case where the antioxidant was supported on the powder and the case where the antioxidant was not supported. As a result, the rate of increase of the thermal conductivity is improved by 50% by applying the antioxidant at aging conditions and 40 ° C. for 6 months.

The reason why the thermal conductivity is improved as described above is that when an antioxidant is supported on the powder, the thermal oxidation of the urethane resin, which is the main component of the powder, occurs in the step of heating and degassing the core material. It is considered that this is suppressed and a hydroperoxide group is hardly generated in the urethane molecule. As a result, after the vacuum insulator is formed, the decomposition reaction due to the radicals caused by the alkoxy groups and the hydroxyl groups generated by the decomposition of the hydroperoxide groups is suppressed, and the decomposition of water, carbon monoxide, carbon dioxide, and other low molecular weights is suppressed. It is considered that a product is hardly generated.

In addition, since the organic resin composition is pulverized and applied, radicals generated mechanochemically at the time of pulverization are also supplemented. Think it will be suppressed.

Therefore, it is effective to use, among the antioxidants, one having both the action of inhibiting the radical chain and the action of decomposing the peroxide, or one having the above action.

When an antioxidant is used, the amount of the gas adsorbent can be greatly reduced.
In addition, since it is not necessary to consider the decomposition reaction of the unstable resin caused by radicals, the specification of the gas adsorbent can be easily determined, and the long-term reliability of the heat insulation performance of the vacuum heat insulator can be easily guaranteed.

However, even when an antioxidant is applied, a small amount of gas components entering from the outside of the vacuum heat insulator can be considered. Therefore, it is necessary to add a small amount of a gas adsorbent to remove the gas components.

When an antioxidant having a low melting point is used, the antioxidant is melted in the heating and degassing process of the core material, and the powder constituting the core material is condensed, thereby deteriorating the properties of the core material. Connect. Furthermore, the effect of improving the thermal conductivity was reduced, possibly because the dispersion of the antioxidant in the powder was not uniform and the antioxidant effect was reduced.

When the specific surface area of the antioxidant is less than 5 times the specific surface area of the powder obtained by pulverizing the organic resin composition, the dispersion of the antioxidant in the powder also becomes non-uniform. Presumably, the effect of improving the thermal conductivity was reduced, probably because the antioxidant effect was reduced.

Further, with respect to the loading amount of the antioxidant, the effect of improving the thermal conductivity was most efficiently obtained when the amount of the antioxidant was 0.1% by weight or more and 5% by weight or less.

It is most efficient to apply the antioxidant at the melting point, the specific surface area, and the amount of addition, and the antioxidant is also high in heat insulation performance over time. There is no problem even if it is applied in the form of a powder. When a low melting point antioxidant is used, the powder can be condensed and solidified.

On the other hand, most organic resin compositions such as urethane, phenol, polystyrene, polypropylene, polyethylene resin and the like, regardless of thermosetting resin or thermoplastic resin, can be used as the organic resin composition constituting the core material. Although it is possible, a resin composition having a low resin thermal conductivity is suitable. Among them, a powder obtained by grinding hard urethane foam, which is a foam of the urethane resin composition, was most effective as the core material of the vacuum heat insulator.

When a powder obtained by crushing hard urethane foam is used, urethane waste collected from used refrigerators, urethane board waste for buildings, and loss of materials produced at the factory for manufacturing rigid urethane foam products, etc.
Since various waste materials and industrial wastes can be applied, they are also suitable from the viewpoint of global environmental protection and resource saving and recycling.

Further, the rigid urethane foam was prepared with an average particle size of 1
Urethane powder pulverized to a particle size of about 50 to 200 μm has a needle-like structure, and has a small bulk density and is a bulky powder, so that the core material can have a low density. Achieved.

(Embodiment 2) FIG. 2 is a sectional view of a heat insulating box according to an embodiment of the present invention.
The vacuum heat insulator 1 is disposed in advance in a box body including an inner box 9 formed by vacuum-molding an ABS resin and an outer box 10 formed by press-forming an iron plate via a flange 11, and a space other than the vacuum heat insulator is provided. Is foam-filled with a rigid urethane foam 12.

The vacuum heat insulator 1 is equivalent to that shown in the first embodiment. Therefore, with the above configuration, excellent heat insulating performance can be maintained over time. Also,
The weight of the heat-insulating box is reduced as compared with the case where a vacuum heat-insulating material having an inorganic powder as a core material is applied. Furthermore, the recyclability of the heat insulating box is greatly improved.

Further, as core materials, urethane waste materials recovered from used refrigerators and urethane board waste materials for buildings,
Since various types of waste materials, such as loss of materials produced at the factory when manufacturing rigid urethane foam products, and powders obtained by crushing hard urethane foam that has become industrial waste are applied, from the viewpoint of global environmental protection and resource saving recycling. An excellent heat insulation box can be provided.

Further, such a heat-insulating box has extremely high heat-insulating performance, and is more effective when applied as a housing of a general refrigerator or freezer and a door thereof.

(Embodiment 3) FIG. 3 is a sectional view of a heat insulating panel according to an embodiment of the present invention.

Reference numeral 13 denotes a heat insulating panel, 1 denotes a vacuum heat insulator, 14 denotes a structure having a concave structure formed by foaming styrene resin, and 15 denotes a face material formed by injection molding of an ABS resin. They are made in combination as possible.

The vacuum heat insulator 1 is equivalent to that shown in the first embodiment. Therefore, with the above configuration, excellent heat insulating properties can be maintained over time. Also,
The weight of the heat insulating panel is reduced as compared with the case where a vacuum heat insulator using inorganic powder as a core material is applied. Furthermore, the recyclability of the heat insulating panel is greatly improved.

Further, as core materials, urethane waste materials recovered from used refrigerators and urethane board waste materials for buildings,
Since various types of waste materials, such as loss of materials produced at the factory when manufacturing rigid urethane foam products, and powders obtained by crushing hard urethane foam that has become industrial waste are applied, from the viewpoint of global environmental protection and resource saving recycling. Excellent insulation panels can be provided.

Further, such a heat insulating panel has extremely high heat insulating performance, and is used in various applications such as a general refrigerator, a panel for a barrier separating a refrigerator compartment and a freezer compartment, and a door panel of a refrigerator. Applicable as

Further, since the vacuum heat insulator is not adhered and fixed to the structure of the heat insulating panel, the serviceability in the case where the vacuum heat insulator breaks or the like is good.

(Embodiment 4) FIG. 4 is a sectional view of a heat insulating panel according to an embodiment of the present invention.

Reference numeral 16 denotes a heat insulating panel, and 1 denotes a plurality of vacuum heat insulators. Reference numeral 17 denotes a urethane resin composition, and reference numeral 18 denotes a face material made of polyethylene-coated paper laminated with aluminum foil.

As shown in FIG. 4, at least one plane of the vacuum heat insulator is covered with a urethane resin composition by foam filling, and the outside of the vacuum heat insulator or the urethane resin composition is a face material. It is a heat insulation panel covered with.

The vacuum heat insulator 1 is equivalent to that shown in the first embodiment. Further, in the present embodiment, a plurality of heat insulating panels are arranged on a plane, but there is no problem even if a plurality of heat insulating panels are arranged in a stack, and the size and the number of vacuum heat insulators to be arranged are arbitrarily determined. Can be set.

Therefore, with the above configuration, excellent heat insulating properties can be maintained over time. In addition, since the weight of the heat insulating panel is reduced as compared with the case where a vacuum heat insulator having an inorganic powder as a core material is applied, handleability is improved.
Furthermore, the recyclability of the heat insulating panel is greatly improved.

Further, since the vacuum heat insulator is covered with the face material and the urethane resin composition, no external impact is directly applied to the vacuum heat insulator.

Further, in the core material, urethane waste materials recovered from used refrigerators and urethane board waste materials for buildings,
Since various types of waste materials, such as loss of materials produced at the factory when manufacturing rigid urethane foam products, and powders obtained by crushing hard urethane foam that has become industrial waste are applied, from the viewpoint of global environmental protection and resource saving recycling. Excellent insulation panels can be provided.

Further, such a heat insulating panel has extremely high heat insulating performance, and is generally used for a building.
It can be applied as a heat insulating panel in various uses such as structural materials for buildings.

The material of the face material is not particularly limited, and any of an organic material and an inorganic material may be used. However, considering the flame retardancy of the entire panel, a flame-retardant surface such as a gypsum board is used. Desirably, it is a material.

Further, it is desirable to use a material having a gas barrier property for preventing moisture penetration into the foamed heat insulating material, gas diffusion from inside the foamed heat insulating material bubbles, and permeation and invasion of air. When the property is low, it is more desirable to use a material such as a metal foil in combination.

The urethane resin composition is preferably a flame-retardant urethane resin composition, such as a benzylic ether-type phenol polyol, an organic phosphorus-containing flame-retardant polyol, or an isocyanurate ring-containing polymer polyol. It is preferable to use a urethane resin composition foamed by applying a water-soluble polyol component, or an isocyanurate foam foamed by increasing an isocyanate index.

It is desirable to apply a flame retardant to the urethane resin composition. Examples of the flame retardant include organic, inorganic, and non-halogen flame retardants that do not generate toxic combustion gas, regardless of reaction type or addition type. Desirably, it is a compound.
More preferably, a compound obtained by complexing an organic phosphoric acid compound with an ammonium polyphosphate compound, melamine, or a derivative thereof is particularly effective.

Although not shown in this embodiment, the heat insulation panel may be provided with a frame, a vertical member, or a horizontal member depending on the application.

[0104]

As described above, the vacuum heat insulator of the present invention can be used as a part of the powder obtained by pulverizing the organic resin composition into a gas-permeable inner bag material inside the exterior material made of a gas barrier laminate film. It contains a core material filled with at least a powder carrying an antioxidant and a gas adsorbent, and the interior of the exterior material is evacuated to a reduced pressure.

Therefore, the powder of the organic resin composition constituting the core material is a powder obtained by pulverizing waste materials such as refrigerator waste materials, waste building materials, and production loss materials in the production of resin products. Lighter weight than inorganic substances such as silica,
easy to handle. In addition, the pulverization can be achieved easily and at low cost, and the core material of the vacuum heat insulator can be manufactured at low cost.

Further, since an antioxidant is carried on the powder obtained by pulverizing the organic resin composition, deterioration and decomposition of the resin caused by radicals generated during the pulverization and heat treatment are suppressed, and the vacuum insulator The heat insulation performance over time is also improved.

Further, in the vacuum heat insulator of the present invention, an organic resin composition containing at least a urethane resin composition foam is crushed into an air-permeable inner bag material inside an exterior material made of a gas barrier laminate film. It comprises a core material in which at least a part of the powder is filled with a powder carrying at least an antioxidant, and a gas adsorbent, and the interior of the exterior material is evacuated and evacuated.

Therefore, the powder obtained by pulverizing the foam of the urethane resin composition constituting the core material is a waste of urethane recovered from used refrigerators, a waste of urethane boards for building materials, and a factory production loss in the production of urethane foam products. Even waste materials such as materials can be easily applied. In addition, the pulverization can be achieved easily and at low cost, and the core material of the vacuum heat insulator can be manufactured at low cost.

Further, the crushed urethane foam powder has a needle-like structure and is bulky, so that it is possible to maintain a low density even if it is a fine powder.

Further, since an antioxidant is carried on the powder obtained by pulverizing the waste urethane foam, deterioration and decomposition of the resin caused by radicals generated in the pulverization and heat treatment processes are suppressed, and the vacuum heat insulator is reduced. Thermal insulation performance over time is also improved.

In the vacuum heat insulator of the present invention, the melting point of the antioxidant carried on the powder as the core material is 200 ° C. or higher.

Therefore, even when the core material is subjected to heat degassing at a high temperature, the antioxidant is stably supported on the urethane resin powder without melting, so that the urethane resin is oxidized and thermally oxidized. Deterioration and decomposition can be suppressed stably.

Further, since the antioxidant having a high melting point is applied, the antioxidant does not melt during the heat treatment of the core material, and the powder constituting the core material does not condense.

Further, in the vacuum heat insulator of the present invention, the specific surface area of the antioxidant carried on the powder as the core material is the same as that of the powder obtained by pulverizing the foam of the urethane resin composition. The powder is at least 5 times larger than the surface area.

Therefore, even if it is not compatible with the urethane resin,
The effect of the antioxidant can be sufficiently exerted easily only by mixing and stirring.

Further, the vacuum heat insulator of the present invention is an antioxidant in which an organic resin composition is supported on pulverized powder.
The supported amount is 0.1% by weight or more and 5% by weight or less of the core material.

Therefore, the effect of the antioxidant can be sufficiently exhibited without adversely affecting the heat insulating performance of the vacuum heat insulator.

The method for producing a vacuum heat insulator of the present invention
The powder obtained by pulverizing the organic resin composition and the antioxidant are mixed and stirred, and the antioxidant is supported on the powder composed of the organic resin composition. After filling the core material and performing heat treatment on the core material at 120 ° C. to 180 ° C., it is inserted together with a gas adsorbent into an exterior material made of a gas barrier laminate film, and the inside is decompressed and vacuumed to 133 Pascal or less. In this case, the end of the exterior material is sealed by heat fusion.

Therefore, it is possible to easily produce a powder made of an organic resin composition carrying an antioxidant as a core material, and a core material of a vacuum insulator filled with the powder.

Further, it can be easily manufactured with general-purpose equipment in the heating process for the purpose of dehydrating and degassing the core material, and also in the vacuum insulating material manufacturing process such as vacuum evacuation.

Further, since the antioxidant is applied even at the conventional heat treatment temperature at which the powder of the organic resin composition used as the core material causes thermal oxidative decomposition, heat treatment can be performed without any problem. Also, gas components that have been strongly dissolved in the urethane resin that could not be treated can be easily removed.

Further, the heat insulating box of the present invention has a vacuum heat insulator inside a box composed of an inner box and an outer box, and a space other than the vacuum heat insulator is foam-filled with a urethane resin composition. In a heat-insulated box, the vacuum heat-insulating body is formed by a vacuum.
It is a vacuum insulator described.

Accordingly, a heat insulating box having excellent heat insulating performance over a long period of time can be obtained. Further, the weight of the heat insulating box is reduced.

Further, the heat insulating panel of the present invention has a structure having a concave structure made of an organic resin composition, a vacuum heat insulator disposed in a concave portion of the structure, and a surface covering an open surface of the concave portion of the structure. In a heat insulation panel constituted by a material, the vacuum heat insulator is the vacuum heat insulator according to claim 1 or 2.

Therefore, a heat insulating panel having excellent heat insulating performance over a long period of time can be obtained. Further, the weight of the heat insulating panel is reduced.

The heat insulation panel of the present invention comprises a urethane resin composition, a plurality of vacuum heat insulators, and a face material provided outside the vacuum heat insulator, and at least one plane of the vacuum heat insulator is provided. In a heat insulating panel covered with a urethane resin composition, the vacuum heat insulator is the vacuum heat insulator according to claim 1 or 2.

Accordingly, a heat insulating panel having excellent heat insulating performance over a long period of time can be obtained. Further, the weight of the heat insulating panel is reduced.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a cross section of a vacuum insulator according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view of a heat insulating box according to one embodiment of the present invention.

FIG. 3 is a cross-sectional view of a heat insulating panel according to an embodiment of the present invention.

FIG. 4 is a sectional view of a heat insulating panel according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Vacuum heat insulator 2 Core material 3 Inner bag material 4 Powder 5 Antioxidant 6 Gas adsorbent 7 Exterior material 8 Heat insulation box 9 Inner box 10 Outer box 11 Flange 12 Rigid urethane foam 13, 16 Heat insulation panel 14 Organic resin composition Object 15,18 face material 17 urethane resin composition

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI E04B 1/80 E04B 1/80 D (72) Inventor Tsukasa Tsushima 4-5-2-5 Takaida Hondori, Higashi-Osaka-shi, Osaka Matsushita Refrigerator Inside (72) Inventor Chie Hayashi 4-5-2-5 Takaida Hondori, Higashiosaka-shi, Osaka Matsushita Refrigeration Co., Ltd.

Claims (9)

[Claims] 1. An outer package made of a gas barrier laminate film is filled with a powder in which at least an antioxidant is carried on a part of a powder obtained by pulverizing an organic resin composition into a breathable inner bag material. A vacuum heat insulator comprising: a core material formed as described above; and a gas adsorbent, wherein the interior of the exterior material is evacuated to a reduced pressure. 2. At least a part of a powder obtained by pulverizing an organic resin composition containing a foam of a urethane resin composition into an inner bag material having air permeability inside an exterior material made of a gas barrier laminate film is oxidized to at least a part of the powder. A vacuum heat insulator comprising a core material filled with a powder carrying an inhibitor and a gas adsorbent, wherein the interior of the exterior material is evacuated to a reduced pressure. 3. At least a part of a powder obtained by pulverizing an organic resin composition containing a foam of a urethane resin composition into an inner bag material having air permeability inside an exterior material made of a gas barrier laminate film is at least oxidized. In a vacuum insulator comprising a core material filled with a powder carrying an antioxidant and a gas adsorbent, and the interior of the exterior material is evacuated to a reduced pressure, the melting point of the antioxidant is 200 ° C or more. A vacuum insulator comprising: 4. At least a part of a powder obtained by pulverizing an organic resin composition containing a foam of a urethane resin composition into an inner bag material having air permeability inside an exterior material made of a gas barrier laminate film is at least oxidized. In a vacuum insulating body including a core material filled with a powder carrying an antioxidant and a gas adsorbent, and the inside of the exterior material is evacuated to a reduced pressure, the specific surface area of the antioxidant is an organic resin composition. A vacuum heat insulator characterized in that the powder is at least five times as large as the specific surface area of the powder obtained by grinding the material. 5. At least a part of a powder obtained by pulverizing an organic resin composition containing a foam of a urethane resin composition into an inner bag material having air permeability inside an exterior material made of a gas barrier laminate film is at least oxidized. In a vacuum insulator including a core material filled with a powder loaded with an antioxidant and a gas adsorbent, and the interior of the exterior material is evacuated to a reduced pressure, the amount of the antioxidant carried is the core material. A vacuum insulator having a content of 0.1% by weight or more and 5% by weight or less. 6. A powder obtained by pulverizing and molding an organic resin composition and an antioxidant are mixed and stirred, and the antioxidant is carried on a powder comprising the organic resin composition. The core material is filled in the inner bag material having the core material,
After performing the heat treatment at 80 ° C, together with the gas adsorbent,
Insert into the gas barrier laminate film exterior material,
A method for manufacturing a vacuum heat insulator, comprising reducing the pressure of the interior to 133 Pascal or less and then sealing the end of the exterior material by heat fusion. 7. A heat insulating box body having a vacuum heat insulator inside a box constituted by an inner box and an outer box, wherein a space other than the vacuum heat insulator is foam-filled with a urethane resin composition. A heat insulating box, wherein the vacuum heat insulator is the vacuum heat insulator according to claim 1. 8. A heat insulator comprising a structure having a concave structure made of an organic resin composition, a vacuum heat insulator disposed in a concave portion of the structure, and a surface material covering an open surface of the concave portion of the structure. 3. A heat insulating panel, wherein the vacuum heat insulator is the vacuum heat insulator according to claim 1 or 2. 9. A urethane resin composition, a plurality of vacuum heat insulators, and a face material provided outside the vacuum heat insulator, wherein at least one plane of the vacuum heat insulator is covered with the urethane resin composition. A heat insulation panel, wherein the vacuum heat insulator is the vacuum heat insulator according to claim 1 or 2.