JPH10122477A - Vacuum heat insulating body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress worsening of heat conductivity with the lapse of time by applying a plastic film formed of ethylene-vinyl alcohol copolymer resin with A1 evaporation applied to one side, to a gas barrier layer, and providing the Al evaporated face on the heat welded layer side. SOLUTION: Polyethylene terephthalate resin is used for an outermost layer, and an ethylene-vinyl alcohol copolymer resin with A1 evaporation applied is used for a gas barrier layer 5. An A1 evaporated layer is provided on the heat welded layer 6 side, and high density polyethylene resin is used for the heat welded layer 6. Accordingly, even in the case moisture absorbed in the ethylene-vinyl alcohol copolymer resin is desorbed in an vacuum atmosphere, the permeation of moisture is suppressed by A1 evaporation. This results in preventing worsening of heat conductivity of a vacuum heat insulating body caused by the increase of heat conductivity by gas due to degradation of vacuum generated by the influence of moisture.

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 insulator.

[0002]

2. Description of the Related Art In recent years, from the viewpoint of protection of the global environment, destruction of the ozone layer by CFC11 used as a foaming agent for refrigerator insulation has attracted attention worldwide.

[0003] From such a background, research on a heat insulating material using a novel foaming agent has been conducted.
141b, cyclopentane and the like are being selected as candidates in the non-fluorocarbon system.

[0004] However, all of these new foaming agents have a higher gas thermal conductivity than CFC 11, and the heat insulation performance of the refrigerator is inevitably reduced. On the other hand, energy saving of refrigerators is an unavoidable problem with respect to future energy regulations, and improving the heat insulation performance is a major issue to be achieved.

[0005] As described above, the current refrigerator has the contradictory issues of lowering the heat insulation performance due to the use of CFCs and improving the heat insulation performance to achieve energy saving.

As one means for solving such conflicting problems, a vacuum heat insulator using inorganic powder has been devised, and the contents thereof are described in Japanese Patent Application Laid-Open No. 57-173689.
The content is that a film-shaped plastic container is filled with powder having a single particle diameter of 1 μm or less, and the inside thereof is depressurized and then sealed to obtain a vacuum insulator.

The effect is 0.1 to 1 m, which is easy to industrialize.
It can be manufactured at a vacuum degree of mHg, and since the silica particles are fine powder, it has been found that, when the vacuum degree is the same, the heat insulating performance of the vacuum heat insulator is further improved.

[0008]

The heat insulating principle of a vacuum heat insulator is to eliminate air that conducts heat. However, it is difficult to achieve a high vacuum on an industrial level, and a practically achievable degree of vacuum is 0.1 to 10 mmHg.

Therefore, the desired heat insulation performance must be obtained at this degree of vacuum. There is a mean free path as a physical property that affects the heat insulation performance when heat is conducted through air. The mean free path is the distance that one of the molecules that make up air travels before colliding with another molecule.If the gap formed is larger than the mean free path, the molecules collide with each other within the gap. In addition, heat conduction by air occurs, so that the thermal conductivity of the vacuum heat insulator increases.
Conversely, when the gap is smaller than the mean free path, the heat conduction of the vacuum insulator becomes smaller. This is because there is almost no heat conduction due to the collision of air.

Therefore, if a powder having a fine particle size such as a silica powder is used, the gap becomes small, and heat conduction due to the collision of air is almost eliminated. As a result, the heat insulation performance of the vacuum heat insulator is improved. However, in the conventional configuration, the degree of vacuum is deteriorated due to the generation of water or the like adsorbed on the outer material over time, and the heat conductivity of the vacuum heat insulator is deteriorated because the heat conduction by the gas is increased. was there.

The present invention has been made in view of the above, and has as its object to suppress the deterioration of thermal conductivity over time, which is a problem of a vacuum heat insulator.

[0012]

Means for Solving the Problems In order to solve the above-mentioned problems, a vacuum heat insulator according to the present invention employs a gas barrier layer in which a plastic film made of ethylene-vinyl alcohol copolymer resin is subjected to A1 vapor deposition on one side. And A1
The surface on which the vapor deposition has been performed is provided on the heat welding layer side.

Therefore, even when a hydrophilic material such as an ethylene-vinyl alcohol copolymer resin is used,
It is possible to suppress the deterioration of the thermal conductivity caused by the deterioration of the degree of vacuum due to the desorption of the adsorbed moisture.

Further, the vacuum heat insulator of the present invention has an ethylene-vinyl alcohol copolymer resin having an oxygen adsorbent comprising an unsaturated fatty acid.

Therefore, oxygen entering the vacuum insulator can be adsorbed and removed, and deterioration of the thermal conductivity due to deterioration of the degree of vacuum due to the penetration of oxygen over time can be suppressed.

Further, in the vacuum heat insulator of the present invention, the outermost layer of the jacket material contains a moisture adsorbent. Therefore, hydrogen bonds of the ethylene-vinyl alcohol copolymer resin are broken by the intrusion and permeation of moisture in the atmosphere, so that it is possible to suppress the deterioration of the thermal conductivity due to the decrease in gas barrier properties.

Further, in the vacuum heat insulator of the present invention, an ethylene-vinyl alcohol copolymer resin is coated with a polyvinylidene chloride resin.

Therefore, it is possible to suppress the deterioration of the thermal conductivity due to the decrease in the gas barrier property due to the moisture absorption of the ethylene-vinyl alcohol copolymer resin.

Further, in the vacuum heat insulator of the present invention, the peripheral edge of the heat-welded portion is deposited by SiO2.

Therefore, it is possible to prevent gas from entering from the peripheral edge of the heat welding layer without being affected by the heat bridge, and to suppress deterioration of the thermal conductivity due to deterioration of the degree of vacuum.

The heat insulation panel of the present invention comprises:
A vacuum heat insulator, in which a plastic film made of an ethylene-vinyl alcohol copolymer resin is applied with A1 vapor deposition on one side, and the A1 vapor-deposited surface is provided on the heat welding layer side; Is multi-layered.

Therefore, even when insulation performance is required to be maintained for a very long time, such as in a heat insulation wall of a house, vacuum is generated by desorption of water adsorbed on the ethylene-vinyl alcohol copolymer resin over time. Degree worse,
As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, and the heat conductivity of the entire heat insulating panel does not deteriorate.

For this reason, it is possible to prevent the occurrence of condensation on the heat insulating wall of the house. In addition, the heat insulation panel of the present invention is characterized in that the ethylene-vinyl alcohol copolymer resin used for the barrier layer of the covering material has a multilayer structure of a vacuum heat insulator having an oxygen adsorbent composed of unsaturated fatty acid and urethane foam. I have.

Therefore, the unsaturated fatty acid provided in the barrier layer adsorbs and removes oxygen that has entered the inside of the vacuum heat insulator, so that even when used for a long time, there is little deterioration in thermal conductivity. As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, and the heat conductivity of the entire heat insulating panel does not deteriorate.

For this reason, it is possible to prevent the occurrence of condensation on the heat insulating wall of the house. The heat insulation panel of the present invention has a vacuum insulation body provided with a moisture adsorbent on the outermost layer of the outer cover material and a urethane foam in multiple layers.

Therefore, since the moisture adsorbent provided in the outermost layer adsorbs and removes moisture that enters the inside of the vacuum heat insulator, even when used for a long time, there is little deterioration in thermal conductivity. As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, and the heat conductivity of the entire heat insulating panel does not deteriorate.

For this reason, it is possible to prevent the occurrence of dew condensation, mold generation, aging due to corrosion, etc. on the heat insulating wall of the house.

Further, the heat insulation panel of the present invention has a multilayer structure of a vacuum heat insulator using an ethylene-vinyl alcohol copolymer resin coated with a polyvinylidene chloride resin on a gas barrier layer of a jacket material, and a urethane foam. .

Therefore, it is possible to suppress the deterioration of the thermal conductivity due to the decrease in the gas barrier property due to the moisture absorption of the ethylene-vinyl alcohol copolymer resin. As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, the thermal conductivity of the entire heat insulating panel does not deteriorate, and it is possible to prevent the occurrence of dew condensation, mold generation, and aging due to corrosion on the heat insulating wall of the house.

Further, the heat insulation panel of the present invention comprises a vacuum insulation body in which the peripheral edge of the heat-welded portion of the jacket material is vapor-deposited with SiO 2 and a urethane foam.

Therefore, it is possible to prevent the gas from entering from the peripheral edge of the heat welding layer without being affected by the heat bridge, and to suppress the deterioration of the thermal conductivity due to the deterioration of the degree of vacuum. As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, the thermal conductivity of the entire heat insulating panel does not deteriorate, and it is possible to prevent the occurrence of dew condensation, mold generation, and aging due to corrosion on the heat insulating wall of the house.

In the heat insulating box of the present invention, the gas barrier layer is formed by applying a plastic film made of an ethylene-vinyl alcohol copolymer resin on one side of which A1 vapor deposition is applied, and the surface on which the A1 vapor deposition is applied is heated. This is a heat insulation box in which the vacuum heat insulator provided on the welding layer side is provided in an outer box or an inner box.

Therefore, it is possible to suppress the deterioration of the thermal conductivity caused by the deterioration of the degree of vacuum due to the desorption of the adsorbed moisture, and when applied to a refrigerator, the rapid thermal conductivity of the vacuum heat insulator even when used for a long time. There is no deterioration. As a result, the problem that the operation rate of the compressor becomes excessive due to the rapid thermal conductivity of the vacuum insulator and the reliability of the refrigerator is reduced is solved.

Further, in the heat insulation box of the present invention, the ethylene-vinyl alcohol copolymer resin used for the barrier layer of the outer cover material is a vacuum heat insulator having an oxygen adsorbent composed of unsaturated fatty acid, or an outer case or a vacuum heat insulator. This is a heat insulating box provided in the inner box.

Therefore, the unsaturated fatty acid provided in the barrier layer adsorbs and removes oxygen that enters the inside of the vacuum heat insulator, so that the thermal conductivity does not deteriorate even when used for a long time. As a result, the problem that the thermal conductivity of the vacuum insulator deteriorates, the operating rate of the compressor becomes excessive, and the reliability of the refrigerator decreases is solved.

The heat-insulating box of the present invention is a heat-insulating box in which a vacuum heat insulator provided with a moisture adsorbent in the outermost layer of a jacket material is provided in an outer box or an inner box.

Therefore, the moisture adsorbent provided in the outermost layer adsorbs and removes moisture that enters the inside of the vacuum heat insulator, so that even when used for a long time, there is little deterioration in thermal conductivity. As a result, the problem that the thermal conductivity of the vacuum insulator deteriorates, the operating rate of the compressor becomes excessive, and the reliability of the refrigerator decreases is solved.

The heat insulating box of the present invention is a heat insulating box in which an outer or inner box is provided with a vacuum insulator using an ethylene-vinyl alcohol copolymer resin coated with a polyvinylidene chloride resin for a gas barrier layer of a jacket material. It is a box.

Therefore, it is possible to suppress the deterioration of the thermal conductivity due to the decrease in the gas barrier property due to the moisture absorption of the ethylene-vinyl alcohol copolymer resin. As a result, the thermal conductivity of the vacuum insulator does not deteriorate, the thermal conductivity of the entire heat insulating panel does not deteriorate, and the operation rate of the compressor becomes excessive, and the problem that the reliability of the refrigerator decreases is solved. .

The heat-insulating box of the present invention is a heat-insulating box in which a vacuum heat insulator in which the peripheral edge of the heat-welded portion of the jacket material is vapor-deposited with SiO2 is provided in the outer box or the inner box.

Therefore, it is possible to prevent gas from entering from the peripheral edge of the heat welding layer without being affected by the heat bridge, and to suppress the deterioration of the thermal conductivity caused by the deterioration of the degree of vacuum. As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, and the heat conductivity of the entire heat insulating panel does not deteriorate.

As a result, the problem that the thermal conductivity of the vacuum insulator deteriorates, the operating rate of the compressor becomes excessive, and the reliability of the refrigerator decreases is solved.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention according to claim 1 of the present invention comprises a core material, and a jacket material surrounding the core material, wherein the jacket material is a laminate film having a vapor deposition layer,
Or a laminate film having a vapor deposition layer, and a laminate film having a metal foil, in the form of a bag by heat welding, the laminate film having the vapor deposition layer, a heat welding layer, a gas barrier layer, the outermost layer and Wherein the gas barrier layer is formed on one side of a plastic film made of an ethylene-vinyl alcohol copolymer resin.
This is a vacuum heat insulator that has been subjected to 1 vapor deposition and has a surface on which the A1 vapor deposition has been performed, which is provided on the side of the heat welding layer.

The ethylene-vinyl alcohol copolymer resin has an OH group as a functional group in a side chain due to its molecular structure. For this reason, the polarity is strong, and the bonding force is very large because hydrogen bonds are formed. As a result, there is little vibration between molecules and excellent gas barrier properties are exhibited.

However, since it has an OH group, it has a strong affinity for water and easily adsorbs water. For this reason, when applied as a gas barrier layer to the outer cover material of the vacuum heat insulator, the adsorbed moisture is desorbed into a reduced-pressure atmosphere, thereby deteriorating the degree of vacuum.

Therefore, in order to maintain the degree of vacuum of the vacuum insulator for a long time, it is necessary to overcome the disadvantages of the ethylene-vinyl alcohol copolymer resin.

In view of the above problems, the present invention solves the problem by optimizing the laminate structure when applying an ethylene-vinyl alcohol copolymer resin to the gas barrier layer of the jacket material.

In the present invention, A1 vapor deposition is performed on one side of the ethylene-vinyl alcohol copolymer resin applied to the gas barrier layer, and the outer material provided with the A1 vapor deposition side on the heat welding layer side is vacuum insulated. Apply to the body.

Therefore, even if the adsorbed moisture of the ethylene-vinyl alcohol copolymer resin is desorbed, the permeation of the moisture is suppressed by the A1 vapor deposition provided on the heat welding layer side.

As a result, moisture cannot enter the inside of the vacuum heat insulator, so that the degree of vacuum can be maintained and the deterioration of the thermal conductivity due to this can be suppressed.

The invention according to claim 2 of the present invention provides:
As a gas barrier layer, an ethylene-vinyl alcohol copolymer resin having an unsaturated fatty acid having A1 vapor-deposited on one surface is applied, and the outer material provided with the A1 vapor-deposited surface on the side of the heat welding layer is vacuum-sealed. Applied to thermal insulation.

When the ethylene-vinyl alcohol copolymer resin absorbs moisture, hydrogen bonds are broken and the bonding strength of molecules is reduced. For this reason, the rigidity of the main chain is reduced, so that the gas barrier property is reduced.

In view of this point, the present invention employs an ethylene-vinyl alcohol copolymer resin having an unsaturated fatty acid. Since unsaturated fatty acids have a carboxyl group in the side chain, they have high oxidation reactivity with oxygen and form hydroperoxides. Therefore, an autoxidation reaction occurs, and the oxygen adsorption capacity does not decrease.

Therefore, when using the vacuum insulator for a long time, even if the ethylene-vinyl alcohol copolymer resin absorbs moisture, it is possible to suppress the deterioration of the degree of vacuum,
Deterioration of the thermal conductivity of the vacuum heat insulator can be suppressed.

Further, the invention according to claim 3 of the present invention provides:
For the gas barrier layer, a plastic film made of an ethylene-vinyl alcohol copolymer resin, which has been subjected to A1 deposition on one side, is applied, the A1 deposited surface is provided on the heat welding layer side, and An outer layer containing a moisture adsorbent is applied to a vacuum insulator.

When the vacuum insulator is used for a long time,
The moisture in the atmosphere permeates and reacts with the ethylene-vinyl alcohol copolymer resin provided on the gas barrier layer to deteriorate the gas barrier property.

In the present invention, in consideration of such a problem, a moisture adsorbent is provided in the outermost layer. Therefore, since the moisture adsorbent in the outermost layer invades and permeates over time and absorbs and removes moisture in the atmosphere, the hydrogen bond of the ethylene-vinyl alcohol copolymer resin is broken, and the heat conduction caused by the decrease in gas barrier property is caused. The deterioration of the rate can be suppressed.

According to a fourth aspect of the present invention, as a gas barrier layer, an ethylene-vinyl alcohol copolymer resin coated with vinylidene chloride resin, which has been subjected to A1 vapor deposition on one side, is applied. The covering material provided with the surface on which the heat treatment is performed on the side where heat treatment is performed is applied to the vacuum heat insulator.

The vinylidene chloride resin has a C1 group in a side chain and exhibits hydrophobicity. Also, it shows excellent gas barrier properties against carbon dioxide gas.

By coating the ethylene-vinyl alcohol copolymer resin with the vinylidene chloride resin having such properties, the hydrogen bonds of the ethylene-vinyl alcohol copolymer resin are broken by moisture absorption, and the gas barrier property is reduced. The deterioration of the thermal conductivity due to the above can be suppressed.

Further, as a new performance addition, it is possible to improve the gas barrier property against carbon dioxide gas, and it becomes more reliable in using the vacuum heat insulator for a long time.

Further, the invention according to claim 5 of the present invention provides:
For the gas barrier layer, a plastic film made of an ethylene-vinyl alcohol copolymer resin having one side subjected to A1 vapor deposition is applied, the A1 vapor-deposited surface is provided on the heat welding layer side, and the end of the heat welding layer is provided. A jacket material whose peripheral edge is deposited by SiO2 is applied to the vacuum heat insulator.

Even if a material having excellent gas barrier properties is used for the barrier layer, the gas cannot be permeated from the heat-sealing layer, and when a vacuum heat insulator is used for a long time, the heat conduction by the gas increases. There is a problem.

In view of the above problems, the present invention deposits the peripheral edge of the heat-welded portion with SiO2. Since SiO2 deposition forms very dense groups of particles, it has a gas barrier property equivalent to that of A1 deposition. This makes it possible to suppress gas permeation from the peripheral edge of the heat welding layer, which has been difficult in the past, and to reduce the performance of the vacuum heat insulator even when the vacuum heat insulator is used for a long time. It becomes possible to suppress.

Further, since SiO2 does not form a metal bond, its thermal conductivity is small, and there is no rapid deterioration in thermal conductivity due to heat leak, which is observed when A1 vapor deposition is applied to the periphery of the end of the thermal welding layer.

The invention according to claim 6 of the present invention comprises a core material and a jacket material surrounding the core material, wherein the jacket material is a laminate film having a vapor deposition layer or a vapor deposition layer. Laminate film having, and a laminate film having a metal foil, is formed into a bag shape by heat welding, the laminate film having the vapor deposition layer, a heat welding layer, a gas barrier layer, and an outermost layer,
A vacuum heat insulator, wherein the gas barrier layer is formed by subjecting one side of a plastic film made of an ethylene-vinyl alcohol copolymer resin to A1 vapor deposition, and the surface on which the A1 vapor deposition is performed is provided to the heat welding layer side. And a urethane foam.

In the heat insulating panel having the structure of the present invention, even if the adsorbed moisture of the ethylene-vinyl alcohol copolymer is desorbed, the permeation of the moisture is suppressed by the A1 vapor deposition provided on the heat welding layer side. As a result, moisture cannot enter the inside of the vacuum heat insulator, so that the degree of vacuum can be maintained, and deterioration of thermal conductivity due to this can be suppressed.

Therefore, the thermal conductivity of the vacuum heat insulator does not deteriorate, so that the thermal conductivity of the entire heat insulating panel does not deteriorate. Can be prevented.

Further, the moisture absorption of the heat insulating material, which is an important issue in the heat insulating wall of a house, is higher than that of the conventional glass wool.
Since urethane foam itself has low hygroscopicity and the covering material used for the vacuum heat insulator also has low moisture hygroscopicity, it is possible to solve the problems such as corrosion of columns and generation of mold caused by moisture absorption.

The invention according to claim 7 of the present invention provides
As the gas barrier layer, an ethylene-vinyl alcohol copolymer resin having an unsaturated fatty acid having A1 vapor deposited on one side is used, and a jacket material having the A1 vapor deposited surface provided on the heat welding layer side is used. This is a heat insulation panel in which a vacuum insulation body and a urethane foam are laminated.

Since unsaturated fatty acids have a carboxyl group in the side chain, they have high oxidation reactivity with oxygen and form hydroperoxides. Therefore, an autoxidation reaction occurs, and the oxygen adsorption capacity does not decrease.

As a result, when using the vacuum insulator for a long time, even if the ethylene-vinyl alcohol copolymer resin absorbs moisture, it is possible to suppress the deterioration of the degree of vacuum and to reduce the thermal conductivity of the vacuum insulator. Deterioration can be suppressed.

Therefore, the thermal conductivity of the vacuum heat insulator does not deteriorate, so that the thermal conductivity of the whole heat insulating panel does not deteriorate. Can be prevented.

The invention according to claim 8 of the present invention provides
For the gas barrier layer, a plastic film made of an ethylene-vinyl alcohol copolymer resin, which has been subjected to A1 deposition on one side, is applied, the A1 deposited surface is provided on the heat welding layer side, and This is a heat insulating panel in which a vacuum heat insulator using a jacket material whose outer layer contains a moisture adsorbent and urethane foam are multi-layered.

The heat insulating panel having the structure as in the present invention has a structure in which the water adsorbent in the outermost layer penetrates over time and absorbs and removes moisture in the atmosphere. Collapses, and the deterioration of the thermal conductivity caused by the decrease in gas barrier properties can be suppressed.

Therefore, the heat conductivity of the heat insulating panel does not deteriorate due to the deterioration of the heat conductivity of the vacuum heat insulator, and the dew condensation of the heat insulating wall of the house occurs when the heat insulating panel is used for a long time. Can be prevented.

Further, since the outermost adsorbent adsorbs and removes the moisture in the surrounding atmosphere, it is an important issue in the heat insulation wall of a house.
Problems such as corrosion of pillars and generation of mold caused by moisture absorption can also be solved.

The invention according to claim 9 of the present invention provides
As a gas barrier layer, a jacket material in which an ethylene-vinyl alcohol copolymer resin coated with vinylidene chloride resin coated with A1 on one side is applied, and the surface coated with A1 is provided on the heat-welding layer side. This is a heat insulation panel in which a vacuum heat insulator using the above and a urethane foam are multi-layered.

The vinylidene chloride resin has a C1 group in a side chain and exhibits hydrophobicity. Also, it shows excellent gas barrier properties against carbon dioxide gas.

By coating the ethylene-vinyl alcohol copolymer resin with the vinylidene chloride resin having such properties, it is possible to suppress the deterioration of the thermal conductivity of the vacuum heat insulator due to the moisture absorption chamber.

Therefore, the heat conductivity of the heat insulating panel does not deteriorate due to the deterioration of the heat conductivity of the vacuum heat insulator, and the dew condensation of the heat insulating wall of the house occurs when the heat insulating panel is used for a long time. Can be prevented.

Further, since it is possible to improve the gas barrier property against carbon dioxide gas, it is possible to apply water-foamed urethane to heat insulation of a house, and to provide a heat insulation wall for a house that also addresses the problem of CFCs. .

Further, in the invention according to claim 10 of the present invention, a gas barrier layer obtained by applying A1 vapor deposition to one side of a plastic film made of an ethylene-vinyl alcohol copolymer resin is applied. A heat insulating layer side, and a vacuum heat insulator using a jacket material in which the peripheral edge of the heat welding portion is deposited with SiO2, and a heat insulating panel in which urethane foam is multi-layered.

Since SiO2 vapor deposition forms very dense groups of particles, it has the same gas barrier properties as Al vapor deposition. This makes it possible to suppress gas permeation from the peripheral edge of the heat-welded layer, which has been difficult in the past, and to reduce the performance of the vacuum heat insulator even when the vacuum heat insulator is used for a long time. It becomes possible to suppress.

Further, since SiO2 does not form a metal bond, its thermal conductivity is small, and vacuum insulation which does not cause a rapid deterioration in thermal conductivity due to heat leak, which is observed when A1 vapor deposition is applied to the peripheral edge of the thermal welding layer. You can get the body.

In the heat insulation panel having such a structure in which the vacuum heat insulator and the urethane foam are multi-layered, the heat conductivity of the entire heat insulation panel does not deteriorate due to the deterioration of the heat conductivity of the vacuum heat insulator. It is possible to prevent the occurrence of dew condensation on the heat insulating wall of a house, which occurs when the device is used for a long time.

Further, since there is no influence of the heat leak, the problem that local condensation occurs on the heat insulating wall can be solved.

According to an eleventh aspect of the present invention, there is provided the heat insulating box, wherein the outer box, the inner box, and a space formed by the outer box and the inner box are filled with a foamed heat insulating material. Or, on the inner surface of the inner box, a core material, and a jacket material surrounding the core material, wherein the jacket material is a laminate film having a vapor deposition layer, or a laminate film having a vapor deposition layer, and a metal foil. And a laminated film having a vapor-deposited layer, the laminated film having the vapor-deposited layer is composed of a heat-welded layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is formed of ethylene-vinyl alcohol. A1 vapor-deposited on one side of a plastic film made of a copolymer resin, and
A heat-insulated box provided with a vacuum heat-insulating body provided on the heat-welded layer side with the A1 deposited surface.

In the heat insulating box having the structure of the present invention, even if the adsorbed water of the ethylene-vinyl alcohol copolymer resin is desorbed, the permeation of the water is suppressed by the A1 vapor deposition provided on the heat welding layer side. As a result, moisture cannot enter the inside of the vacuum heat insulator, so that the degree of vacuum can be maintained, and deterioration of thermal conductivity due to this can be suppressed.

Therefore, it is possible to suppress the deterioration of the thermal conductivity caused by the deterioration of the degree of vacuum due to the desorption of the adsorbed moisture. When applied to a refrigerator, the rapid thermal conductivity of the vacuum heat insulator even when used for a long time. There is no deterioration. As a result, the problem that the operating rate of the compressor becomes excessive due to the rapid deterioration of the thermal conductivity of the vacuum insulator and the reliability of the refrigerator is reduced is solved.

Further, the invention according to claim 12 of the present invention provides a vacuum heat insulator having an oxygen adsorbent comprising an unsaturated fatty acid as the ethylene-vinyl alcohol copolymer resin used for the barrier layer of the jacket material. , An insulating box provided in the outer box or the inner box.

Since unsaturated fatty acids have a carboxyl group in the side chain, they have high oxidation reactivity with oxygen and form hydroperoxides. Therefore, an autoxidation reaction occurs, and the oxygen adsorption capacity does not decrease.

As a result, when the vacuum insulator is used for a long time, even if the ethylene-vinyl alcohol copolymer resin absorbs moisture, it is possible to suppress the deterioration of the degree of vacuum and to reduce the thermal conductivity of the vacuum insulator. Deterioration can be suppressed.

Therefore, in the heat insulating box having the structure of the present invention, the problem that the operating rate of the compressor becomes excessive due to the rapid deterioration of the thermal conductivity of the vacuum heat insulator and the reliability of the refrigerator is reduced is solved. You.

Further, according to the invention of claim 13 of the present invention, a gas barrier layer obtained by applying A1 vapor deposition to one side of a plastic film made of an ethylene-vinyl alcohol copolymer resin is applied. A heat insulating layer is provided on the outer or inner box, and a vacuum insulator using an outer covering material containing a moisture adsorbent is provided on the outer or inner box.

In the heat-insulating box of the present invention, since the moisture adsorbent in the outermost layer penetrates over time and adsorbs and removes moisture in the atmosphere, hydrogen bonding of the ethylene-vinyl alcohol copolymer resin is prevented. It is possible to suppress the deterioration of the thermal conductivity due to the collapse and the decrease in the gas barrier property.

As a result, even when used for a long time, the problem that the operation rate of the compressor becomes excessive due to the rapid deterioration of the thermal conductivity of the vacuum insulator and the reliability of the refrigerator is reduced is solved. You.

The invention according to claim 14 of the present invention is characterized in that an ethylene-vinyl alcohol copolymer resin coated with vinylidene chloride resin and having A1 deposited on one side is applied as a gas barrier layer, and This is a heat insulating box in which a vacuum heat insulator using a jacket material provided with the surface on which the A1 vapor deposition has been performed is provided on the heat welding layer side is provided in an outer box or an inner box.

The vinylidene chloride resin has a D1 group in a side chain and is hydrophobic. Also, it shows excellent gas barrier properties against carbon dioxide gas.

By coating the ethylene-vinyl alcohol copolymer resin with the vinylidene chloride resin having such properties, it is possible to suppress the deterioration of the thermal conductivity of the vacuum insulator due to moisture absorption.

Therefore, in the heat-insulating box constructed in accordance with the present invention, even when used for a long time, the operating rate of the compressor becomes excessive due to the rapid deterioration of the thermal conductivity of the vacuum heat insulator, so that the refrigerator is not used. The problem that reliability is reduced is solved.

The invention according to claim 15 of the present invention is characterized in that a gas barrier layer obtained by applying A1 vapor deposition to one side of a plastic film made of an ethylene-vinyl alcohol copolymer resin is applied, and the A1 vapor deposition is applied. A heat insulating layer is provided on the side of the heat welding layer, and an outer or inner box is provided with a vacuum heat insulator using a jacket material whose peripheral edge of the heat welding portion is deposited by SiO2. .

Since SiO2 vapor deposition forms very dense groups of particles, it has the same gas barrier properties as A1 vapor deposition. This makes it possible to suppress gas permeation from the peripheral edge of the heat-welded layer, which has been difficult in the past, and to reduce the performance of the vacuum heat insulator even when the vacuum heat insulator is used for a long time. It becomes possible to suppress.

Further, since SiO2 does not form a metal bond, its thermal conductivity is small, and vacuum insulation which does not cause a rapid deterioration of thermal conductivity due to heat leak, which is observed when A1 vapor deposition is applied to the peripheral edge of the thermal welding layer. You can get the body.

In the heat insulating box of the present invention to which such a vacuum heat insulator is applied, even when used for a long time,
This solves the problem that the operating rate of the compressor becomes excessive due to the rapid deterioration of the thermal conductivity of the vacuum insulator, and the reliability of the refrigerator is reduced.

[0106]

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

(Example 1) FIG. 1 is a cross-sectional view of a vacuum heat insulator, and 1 is a vacuum heat insulator. A core material 2 made of a water-foaming and communicating foam having a cell diameter of 150 μm is heated at 120 ° C.
After drying for an hour, fill the jacket material 3 with a vacuum of 0.1 mmH
The inside was sealed under reduced pressure to obtain g.

The core material 3 is not limited to the water-foaming communication foam, but may be a powdered material such as silica or perlite, or calcium silicate.

FIG. 2 is an enlarged cross-sectional view of the jacket material 3. The outermost layer 4 is made of polyethylene terephthalate resin having a thickness of 12 μm, and the gas barrier layer 5 is formed by A1 evaporation.
μm-thick ethylene-vinyl alcohol copolymer resin, and the A1 vapor-deposited layer is provided on the heat-welding layer 6 side. I have.

As the ethylene-vinyl alcohol copolymer resin, one having an ethylene content of 12 mol% is used, but is not particularly limited, and the ethylene content can be appropriately changed depending on the performance of the vacuum insulator. it can.

The vacuum heat insulator 1 having the above-described structure
In the above, the A1 vapor deposition layer provided on the gas barrier layer 5 is located on the heat welding layer 6 side. Therefore, even when moisture absorbed by the ethylene-vinyl alcohol copolymer resin is desorbed into the vacuum atmosphere, the transmission of moisture is suppressed by the A1 vapor deposition layer.

As a result, the degree of vacuum deteriorates due to the influence of moisture absorbed by the ethylene-vinyl alcohol copolymer resin, and the thermal conductivity of the vacuum insulator deteriorates due to the increase in thermal conductivity due to gas. Is resolved.

Further, since the permeation of water is suppressed by the A1 vapor-deposited layer, the ethylene content of the ethylene-vinyl alcohol copolymer resin can be reduced, and the gas barrier property is improved by increasing the ratio of the polyvinyl alcohol resin. It is possible to further improve.

The resin used for the outermost layer of the jacket material is not limited to polyethylene terephthalate resin, but may be nylon resin, polypropylene resin, polyvinyl chloride, or the like.

The resin used for the heat-sealing layer is not limited to the high-density polyethylene resin, but may be a low-density polyethylene resin, a polyacrylonitrile resin, or a polyacrylonitrile resin. I prefer
High-density polyethylene resin and polyacrylonitrile resin which are excellent in chemical resistance and gas barrier properties are suitable.

(Example 2) FIG. 3 is a detailed sectional view of a jacket material 3, and 7 is an oxygen adsorbent composed of unsaturated fatty acid.
Oleic acid was obtained by filling and kneading 1% by weight with respect to an ethylene-vinyl alcohol copolymer resin.

The carboxyl group on the side chain of oleic acid has a high oxidation reactivity with oxygen and forms a hydroperoxide. Therefore, an autoxidation reaction occurs, and the oxygen adsorption capacity does not decrease.

Therefore, in the vacuum heat insulator having the structure of the present invention, when the vacuum heat insulator is used for a long time, oleic acid is reduced even if the ethylene-vinyl alcohol copolymer resin absorbs moisture and gas barrier property is deteriorated. Since oxygen is selectively adsorbed, deterioration of the degree of vacuum is small, and deterioration of the thermal conductivity of the vacuum insulator can be suppressed.

Similar effects can be obtained by using soybean oil, cottonseed oil or the like as unsaturated fatty acids in addition to oleic acid.

(Example 3) FIG. 4 is a detailed sectional view of a jacket material 3, and 8 is a moisture adsorbent made of synthetic zeolite, which is filled at a weight ratio of 1% to the polyethylene terephthalate resin of the outermost layer 4. , Kneaded.

In the vacuum insulator having such a configuration,
Even when used in a humid atmosphere, the zeolite filled in the outermost layer adsorbs moisture, so the ethylene-vinyl alcohol copolymer resin absorbs moisture and deteriorates gas barrier properties, resulting in poor thermal conductivity of the vacuum insulator. Problem is solved.

The water adsorbent is not limited to synthetic zeolite, but the same effect can be obtained by using silica or alumina powder as the physical adsorbent. In the case of scientific adsorption, lithium hydroxide or barium hydroxide is used. Such powders can also be used.

In consideration of handling properties in actual production, physical adsorption is more suitable because of its lower activity.

In order to further reduce the influence of moisture, the outermost layer of polyethylene terephthalate resin should have A
If one vapor deposition is performed, it is more effective.

(Example 4) FIG. 5 is a detailed sectional view of a jacket material 3 in which the surface of an ethylene-vinyl alcohol copolymer resin is coated with a polyvinylidene chloride resin 9;
The coating thickness is 20 μm.

The polyvinylidene chloride resin 9 has a C1 group in a side chain as a functional group. Therefore, since it is hydrophobic, it has low hygroscopicity. As a result, the problem that the ethylene vinyl alcohol copolymer resin absorbs moisture to deteriorate the gas barrier property and the thermal conductivity of the vacuum heat insulator to be deteriorated is solved.

The polyvinylidene chloride resin has a high degree of crystallinity and a dense molecular structure, and therefore exhibits excellent gas barrier properties against carbon dioxide.

As a result, by using the vacuum insulator having the structure as in the present invention, a vacuum insulator having not only a high gas barrier property against oxygen and nitrogen gas but also an excellent gas barrier property against carbon dioxide gas can be obtained. can get.

(Example 51) FIG. 6 is a detailed cross-sectional view of an outer covering material 3, in which SiO2 vapor deposition 11
Has been given.

[0130] The vacuum heat insulator is sealed by heat sealing with a heat welding layer. At this time, the heat welding layer is thermally degraded. As a result, gas invades from the heat welding layer over time, and the thermal conductivity of the vacuum heat insulator deteriorates due to the deterioration of the degree of vacuum.

However, by applying SiO2 vapor deposition having excellent gas barrier properties to the periphery of the end portion of the heat-welded portion, it is possible to prevent gas from entering the thermally-degraded heat-welded layer.

As described above, by using the vacuum heat insulator having the structure of the present invention, gas invades from the heat welding layer over time, and the thermal conductivity of the vacuum heat insulator is reduced due to the deterioration of the degree of vacuum. The problem of getting worse can be solved.

Further, since the thermal conductivity of SiO2 is very small, there is no heat leak which is a problem when A1 deposition is applied, and a vacuum insulator having excellent reliability without deteriorating the thermal conductivity is provided. It is possible to obtain.

(Embodiment 6) FIG. 7 is a sectional view of a heat insulating panel. A heat insulating panel 12 is composed of a rigid urethane foam 13 and the vacuum heat insulator 1 obtained in the first embodiment.

The heat insulating panel 12 having such a configuration
Since the A1 vapor deposition layer provided on the gas barrier layer of the vacuum heat insulator 1 is located on the heat welding layer side, even when moisture absorbed by the ethylene-vinyl alcohol copolymer resin is desorbed into the vacuum atmosphere, The transmission of moisture is suppressed by the Al deposition layer.

As a result, the degree of vacuum deteriorates due to the influence of moisture absorbed by the ethylene-vinyl alcohol copolymer resin, and the thermal conductivity of the vacuum insulator deteriorates due to the increase in heat conduction by gas. The problem that the thermal conductivity of the whole heat insulation panel becomes bad is solved.

In addition, when applied to a heat insulating wall of a house in a high-temperature and high-humidity environment, there are many problems that the moisture of the outside air diffuses in the urethane foam to generate mold and the like on the indoor wall and rot wood. As will be appreciated, by applying the heat insulating panel of the present invention, the moisture diffused inside the urethane foam is blocked by the vapor deposition layer, so that the above-mentioned problem is solved.

(Embodiment 7) Heat insulation panel 12 according to the present invention
Is composed of the rigid urethane foam 13 and the vacuum heat insulator 1 obtained in Example 2. The vacuum heat insulator 1 applied to the heat insulation panel 12 of the present invention is prepared by filling oleic acid, which is an unsaturated fatty acid, as an oxygen adsorbent 7 with a weight ratio of 1% to an ethylene-vinyl alcohol copolymer resin, and kneading. An outer covering material having a barrier layer obtained as described above is applied.

The carboxyl group on the side chain of oleic acid is highly oxidatively reactive with oxygen and forms a hydroperoxide. Therefore, an autoxidation reaction occurs, and the oxygen adsorption capacity does not decrease.

Therefore, when the vacuum insulator is used for a long time, even if the ethylene-vinyl alcohol copolymer resin absorbs moisture and the gas barrier property is deteriorated, oleic acid selectively adsorbs oxygen, and Can be suppressed from becoming worse,
Deterioration of the thermal conductivity of the vacuum heat insulator can be suppressed.

As described above, the problem that the heat conductivity of the vacuum heat insulator is deteriorated by applying the heat insulation panel having the structure of the present invention and the heat conductivity of the whole heat insulation panel is deteriorated is solved.

As a result, when the heat insulation panel of the present invention is applied as a heat insulation wall for a house, the problem that the heat conductivity of the heat insulation panel deteriorates with time and dew condensation occurs on the wall surface is solved.

(Embodiment 8) Heat insulation panel 12 according to the present invention
Is constituted by the rigid urethane foam 13 and the vacuum heat insulator 1 obtained in Example 3. The vacuum heat insulator 1 applied to the heat insulation panel 12 of the present invention is a vacuum heat insulator having a jacket material filled with a moisture adsorbent 8 composed of 1% by weight of synthetic zeolite with respect to the polyethylene terephthalate resin of the outermost layer 4. 1 is applied.

In the vacuum insulator having such a structure,
Even when used in a humid atmosphere, the zeolite filled in the outermost layer adsorbs moisture, so the ethylene-vinyl alcohol copolymer resin absorbs moisture and deteriorates gas barrier properties, resulting in poor thermal conductivity of the vacuum insulator. Problem is solved.

As a result, the degree of vacuum deteriorates due to the influence of moisture absorbed by the ethylene-vinyl alcohol copolymer resin, and the thermal conductivity of the vacuum insulator deteriorates due to the increase in heat conduction by gas. The problem that the thermal conductivity of the whole heat insulation panel becomes bad is solved.

In addition, when applied to a heat insulating wall of a house in a high-temperature and high-humidity environment, there are many problems that the moisture of the outside air diffuses in the urethane foam to generate mold and the like on the indoor wall and to rot wood. As will be appreciated, by applying the heat insulating panel of the present invention, the water diffused inside the urethane foam is adsorbed and removed by the water adsorbent filled in the outermost layer of the outer cover material, so that the above problem is solved.

(Embodiment 9) Heat insulation panel 12 according to the present invention
Is constituted by the rigid urethane foam 13 and the vacuum heat insulator 1 obtained in Example 4. The vacuum heat insulator 1 applied to the heat insulation panel 12 of the present invention has a jacket material in which the surface of an ethylene-vinyl alcohol copolymer resin is coated with a polyvinylidene chloride resin 9.

The polyvinylidene chloride resin 9 has a C1 group in a side chain as a functional group. Therefore, since it is hydrophobic, it has low hygroscopicity. As a result, the problem that the ethylene-vinyl alcohol copolymer resin absorbs moisture to deteriorate the gas barrier property and the thermal conductivity of the vacuum heat insulator to be deteriorated is solved.

The polyvinylidene chloride resin has a high degree of crystallinity and a dense molecular structure, and thus exhibits excellent gas barrier properties against carbon dioxide.

As a result, a vacuum insulator having not only a high gas barrier property against oxygen and nitrogen gas but also an excellent gas barrier property against carbon dioxide gas is obtained, and even when used for a long time, the degree of vacuum is reduced. It does not deteriorate and the thermal conductivity deteriorates.

In the heat insulation panel of the present invention to which the vacuum heat insulator having such features is applied, when the heat insulation panel is applied to a heat insulation wall of a house in a high-temperature and high-humidity environment, the moisture of the outside air diffuses in the urethane foam and the inside of the room is diffused. Problems such as generation of mold on walls and decay of wood are solved.

(Embodiment 10) Thermal insulation panel 1 according to the present invention
2 is composed of the rigid urethane foam 13 and the vacuum heat insulator 1 obtained in Example 15.

The vacuum heat insulating body 1 applied to the heat insulating panel 12 of the present invention has an SiO 2 vapor
1 is provided.

Since SiO2 vapor deposition is excellent in gas barrier properties and low in thermal conductivity, it is applied to the peripheral edge of the heat-welded portion, so that gas penetration from the heat-welded layer thermally degraded without being affected by heat leak. Can be prevented.

The heat insulation panel of the present invention to which the vacuum heat insulator having such features is applied solves the problem that the heat conductivity of the vacuum heat insulator deteriorates and the heat conductivity of the entire heat insulation panel deteriorates. You.

As a result, when the heat insulation panel of the present invention is applied as a heat insulation wall for a house, the problem that the thermal conductivity of the heat insulation panel deteriorates with time and dew condensation occurs on the wall surface is solved.

(Embodiment 11) FIG. 8 is a sectional view of a heat insulating box. The heat insulating box 14 is composed of an outer box 15, an inner box 16, a rigid urethane foam 13, and the vacuum heat insulator 1 obtained by the first embodiment. The vacuum heat insulator 1 is attached to the inner surface of the outer box 15.

In the vacuum heat insulator 1 applied to the heat insulation box 14 of the present invention, the degree of vacuum deteriorates due to the effect of moisture absorbed by the ethylene-vinyl alcohol copolymer resin applied to the barrier layer of the outer cover material 3, Therefore, the thermal conductivity of the vacuum heat insulator does not deteriorate due to the increase in the thermal conductivity due to the heat.

Therefore, in the refrigerator having the structure of the present invention, even when the refrigerator is used for a long time, the operating rate of the compressor becomes excessive due to the rapid deterioration of the thermal conductivity of the vacuum heat insulator, and the reliability of the refrigerator is reduced. Is solved.

(Embodiment 12) The heat insulating box 14 of the present invention
The outer box 15, the inner box 16, the rigid urethane foam 12, and the vacuum heat insulator 1 obtained in the second embodiment are provided. The vacuum heat insulator 1 is attached to the inner surface of the outer box 15.

The vacuum insulator 1 applied to the heat-insulating box 14 of the present invention is characterized in that oleic acid, which is an unsaturated fatty acid, is used as an oxygen adsorbent 7 in a ratio of 1% by weight to an ethylene-vinyl alcohol copolymer resin. The cover material having a barrier layer obtained by filling and kneading is applied.

The carboxyl group on the side chain of oleic acid has a high oxidation reactivity with oxygen and forms a hydroperoxide. Therefore, an autoxidation reaction occurs, and the oxygen adsorption capacity does not decrease.

Therefore, when the vacuum insulator is used for a long time, even if the ethylene-vinyl alcohol copolymer resin absorbs moisture and deteriorates the gas barrier property, oleic acid selectively adsorbs oxygen and the vacuum Can be suppressed from becoming worse,
Deterioration of the thermal conductivity of the vacuum heat insulator can be suppressed.

In the heat insulating box of the present invention using the vacuum heat insulator having the above-mentioned features, even when the heat insulator is used for a long time, the heat conductivity of the compressor is deteriorated due to the rapid deterioration of the thermal conductivity of the vacuum heat insulator. The problem that the operation rate becomes excessive and the reliability of the refrigerator decreases is solved.

(Embodiment 13) The heat insulating box 14 of the present invention
It is composed of the outer box 15, the inner box 16, the rigid urethane foam 12, and the vacuum heat insulator 1 obtained in the third embodiment, and the vacuum heat insulator 1 is attached to the inner surface of the outer box 15.

The vacuum insulator 1 applied to the heat-insulating box 14 of the present invention comprises a jacket material filled with a moisture adsorbent 8 composed of 1% by weight of synthetic zeolite with respect to the polyethylene terephthalate resin of the outermost layer 4. The vacuum heat insulator 1 is applied.

In the vacuum insulator having such a configuration,
Even when used in a humid atmosphere, the zeolite filled in the outermost layer adsorbs moisture, so the ethylene-vinyl alcohol copolymer resin absorbs moisture and deteriorates gas barrier properties, resulting in poor thermal conductivity of the vacuum insulator. Problem is solved.

As a result, when the vacuum insulator is used for a long time, even if the ethylene-vinyl alcohol copolymer resin absorbs moisture and the gas barrier property is deteriorated, oleic acid selectively adsorbs oxygen and the vacuum Deterioration can be suppressed, and deterioration of the thermal conductivity of the vacuum heat insulator can be suppressed.

(Embodiment 14) The heat insulating box 14 of the present invention
The outer box 15, the inner box 16, the rigid urethane foam 12, and the vacuum insulator 1 obtained in the fourth embodiment are provided. The vacuum insulator 1 is attached to the inner surface of the outer box 15.

The vacuum heat insulator 1 applied to the heat insulation box 14 of the present invention has an outer cover material in which the surface of an ethylene-vinyl alcohol copolymer resin is coated with a polyvinylidene chloride resin 9.

The polyvinylidene chloride resin has a C1 group in a side chain as a functional group, and therefore is hydrophobic, and has a dense molecular structure, and thus exhibits excellent gas barrier properties against carbon dioxide gas.

Therefore, in the heat insulation box of the present invention to which such a vacuum heat insulator is applied, the degree of vacuum of the vacuum heat insulator is deteriorated by carbon dioxide gas or moisture of the rigid urethane foam, the operation rate of the compressor becomes excessive, and the refrigerator operates. The problem that the reliability of the device is reduced is solved.

(Embodiment 15) The heat insulating box 14 of the present invention
The outer box 15, the inner box 16, the rigid urethane foam 12, and the vacuum heat insulator 1 obtained in Example 5 are provided. The vacuum heat insulator 1 is attached to the inner surface of the outer box 15.

The vacuum insulator 1 applied to the heat-insulating box 14 of the present invention has a SiO 2 vapor deposition 11
It has an outer covering material.

Since SiO2 vapor deposition has excellent gas barrier properties and low thermal conductivity, it is applied to the periphery of the end of the heat welded portion, so that gas penetration from the heat welded layer which has been thermally degraded without being affected by heat leak. Can be prevented.

In the heat insulating box of the present invention to which the vacuum heat insulator having such features is applied, the thermal conductivity of the vacuum heat insulator deteriorates, so that the operation rate of the compressor becomes excessive.
The problem that the reliability of the refrigerator is reduced is solved.

[0177]

As described above, the vacuum insulator of the present invention is
As the gas barrier layer, a plastic film made of an ethylene-vinyl alcohol copolymer resin obtained by applying A1 vapor deposition to one side is applied, and the surface subjected to A1 vapor deposition is provided on the heat welding layer side.

Therefore, even when a hydrophilic material such as an ethylene-vinyl alcohol copolymer resin is used,
It is possible to suppress the deterioration of the thermal conductivity caused by the deterioration of the degree of vacuum due to the desorption of the adsorbed moisture.

The vacuum heat insulator of the present invention has an ethylene-vinyl alcohol copolymer resin having an oxygen adsorbent comprising an unsaturated fatty acid.

Therefore, it is possible to adsorb and remove oxygen invading the inside of the vacuum heat insulator, and it is possible to suppress the deterioration of the thermal conductivity caused by the deterioration of the degree of vacuum due to the invasion of oxygen over time.

In the vacuum heat insulator of the present invention, the outermost layer of the jacket material contains a moisture adsorbent. Accordingly, the penetration and permeation of moisture in the atmosphere breaks down the hydrogen bonds of the ethylene-vinyl alcohol copolymer resin, thereby suppressing the deterioration of the thermal conductivity due to the decrease in gas barrier properties.

Further, in the vacuum heat insulator of the present invention, an ethylene-vinyl alcohol copolymer resin is coated with a polyvinylidene chloride resin.

Therefore, it is possible to suppress the deterioration of the thermal conductivity caused by the decrease in gas barrier property due to the moisture absorption of the ethylene-vinyl alcohol copolymer resin.

Further, in the vacuum heat insulator of the present invention, the peripheral edge of the heat-welded portion is deposited by SiO 2.

Therefore, it is possible to prevent gas from entering from the peripheral edge of the heat welding layer without being affected by the heat bridge, and it is possible to suppress the deterioration of the thermal conductivity caused by the deterioration of the degree of vacuum.

[0186] The heat insulating panel of the present invention comprises a gas barrier layer,
A vacuum heat insulator, in which a plastic film made of an ethylene-vinyl alcohol copolymer resin is applied with A1 vapor deposition on one side, and the A1 vapor-deposited surface is provided on the heat welding layer side; Is multi-layered.

Therefore, even when insulation performance is required to be maintained for a very long time, such as in a heat insulation wall of a house, vacuum is generated by the elimination of water adsorbed on the ethylene-vinyl alcohol copolymer resin over time. Degree worse,
As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, and the heat conductivity of the entire heat insulating panel does not deteriorate.

For this reason, it is possible to prevent the occurrence of condensation on the heat insulating wall of the house. In addition, the heat insulation panel of the present invention is characterized in that the ethylene-vinyl alcohol copolymer resin used for the barrier layer of the covering material has a multilayer structure of a vacuum heat insulator having an oxygen adsorbent composed of unsaturated fatty acid and urethane foam. I have.

Therefore, since the unsaturated fatty acid provided in the barrier layer adsorbs and removes oxygen that enters the inside of the vacuum heat insulator, deterioration of the thermal conductivity is small even when used for a long time. As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, and the heat conductivity of the entire heat insulating panel does not deteriorate.

For this reason, it is possible to prevent condensation from forming on the heat insulating wall of the house. The heat insulation panel of the present invention has a vacuum insulation body provided with a moisture adsorbent on the outermost layer of the outer cover material and a urethane foam in multiple layers.

Therefore, the moisture adsorbent provided in the outermost layer adsorbs and removes moisture that enters the inside of the vacuum heat insulator, so that even when used for a long time, there is little deterioration in thermal conductivity. As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, and the heat conductivity of the entire heat insulating panel does not deteriorate.

For this reason, it is possible to prevent the occurrence of dew condensation, mold generation, aging due to corrosion, etc. on the heat insulating wall of the house.

Further, the heat insulating panel of the present invention is composed of a vacuum heat insulator using an ethylene-vinyl alcohol copolymer resin coated with a polyvinylidene chloride resin as a gas barrier layer of a jacket material, and a urethane foam. .

Therefore, it is possible to suppress the deterioration of the thermal conductivity due to the decrease in the gas barrier property due to the adsorption of the ethylene-vinyl alcohol copolymer resin. As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, the thermal conductivity of the entire heat insulating panel does not deteriorate, and it is possible to prevent the occurrence of dew condensation, mold generation, and aging due to corrosion on the heat insulating wall of the house.

Further, the heat insulation panel of the present invention has a multilayer structure of a vacuum heat insulator and a urethane foam in which the peripheral edge of the heat-sealed portion of the jacket material is vapor-deposited with SiO2.

Therefore, it is possible to prevent the gas from entering from the peripheral edge of the heat welding layer without being affected by the heat bridge, and to suppress the deterioration of the thermal conductivity due to the deterioration of the degree of vacuum. As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, the thermal conductivity of the entire heat insulating panel does not deteriorate, and it is possible to prevent the occurrence of dew condensation, mold generation, and aging due to corrosion on the heat insulating wall of the house.

In the heat insulating box of the present invention, the gas barrier layer is formed by applying a plastic film made of an ethylene-vinyl alcohol copolymer resin on one side to which A1 vapor deposition is applied, and the surface on which the A1 vapor deposition is applied is heated. This is a heat insulation box in which the vacuum heat insulator provided on the welding layer side is provided in an outer box or an inner box.

Therefore, it is possible to suppress the deterioration of the thermal conductivity caused by the deterioration of the degree of vacuum caused by the desorption of the adsorbed moisture. When applied to a refrigerator, the rapid thermal conductivity of the vacuum heat insulator can be maintained for a long time. There is no deterioration. As a result, the problem that the operating rate of the compressor becomes excessive due to the rapid deterioration of the thermal conductivity of the vacuum insulator and the reliability of the refrigerator is reduced is solved.

Further, the heat insulating box of the present invention is characterized in that the ethylene-vinyl alcohol copolymer resin used for the barrier layer of the outer cover material is a vacuum heat insulator having an oxygen adsorbent composed of unsaturated fatty acid, or an outer box or a vacuum heat insulator. This is a heat insulating box provided in the inner box.

Therefore, since the unsaturated fatty acid provided in the barrier layer adsorbs and removes oxygen that enters the inside of the vacuum heat insulator, deterioration of the thermal conductivity is small even when used for a long time. As a result, the problem that the thermal conductivity of the vacuum insulator deteriorates, the operating rate of the compressor becomes excessive, and the reliability of the refrigerator decreases is solved.

Further, the heat insulating box of the present invention is a heat insulating box in which a vacuum heat insulator having a moisture adsorbent provided on the outermost layer of a jacket material is provided in an outer box or an inner box.

Therefore, the moisture adsorbent provided in the outermost layer adsorbs and removes water that enters the inside of the vacuum heat insulator, so that the heat conductivity is not deteriorated even when used for a long time. As a result, the problem that the thermal conductivity of the vacuum insulator deteriorates, the operating rate of the compressor becomes excessive, and the reliability of the refrigerator decreases is solved.

The heat insulating box of the present invention is a heat insulating box in which an outer or inner box is provided with a vacuum heat insulator using an ethylene-vinyl alcohol copolymer resin coated with a polyvinylidene chloride resin for a gas barrier layer of a jacket material. It is a box.

Therefore, it is possible to suppress the deterioration of the thermal conductivity due to the decrease in the gas barrier property due to the moisture absorption of the ethylene-vinyl alcohol copolymer resin. As a result, the thermal conductivity of the vacuum insulator does not deteriorate, the thermal conductivity of the entire heat insulating panel does not deteriorate, and the operation rate of the compressor becomes excessive, and the problem that the reliability of the refrigerator decreases is solved. .

Further, the heat insulating box of the present invention is a heat insulating box in which a vacuum heat insulator in which the peripheral edge of the heat-sealed portion of the jacket material is vapor-deposited with SiO2 is provided in the outer box or the inner box.

Therefore, gas intrusion from the peripheral edge of the heat welding layer can be prevented without being affected by the heat bridge, and deterioration of the thermal conductivity due to deterioration of the degree of vacuum can be suppressed. As a result, the thermal conductivity of the vacuum heat insulator does not deteriorate, and the heat conductivity of the entire heat insulating panel does not deteriorate.

As a result, the problem that the thermal conductivity of the vacuum insulator deteriorates, the operating rate of the compressor becomes excessive, and the reliability of the refrigerator decreases is solved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a vacuum insulator according to an embodiment of the present invention.

FIG. 2 is a detailed sectional view of a covering material according to an embodiment of the present invention.

FIG. 3 is a detailed sectional view of a covering material according to an embodiment of the present invention.

FIG. 4 is a detailed sectional view of a jacket material according to an embodiment of the present invention;

FIG. 5 is a detailed sectional view of a covering material according to an embodiment of the present invention.

FIG. 6 is a detailed sectional view of a covering material according to an embodiment of the present invention.

FIG. 7 is a cross-sectional view of a heat insulating panel according to an embodiment of the present invention.

FIG. 8 is a sectional view of a heat insulating box according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Vacuum heat insulator 2 Core material 3 Outer cover material 4 Outermost layer 5 Gas barrier layer 6 Heat welding layer 7 Oxygen adsorbent 8 Moisture adsorbent 9 Polyvinylidene chloride resin 10 Edge periphery of heat welding part 11 SiO2 vapor deposition 12 Heat insulation panel 13 Hard Urethane foam 14 Insulated box 15 Outer box 16 Inner box

Claims (15)

[Claims] 1. A laminate comprising: a core material; and a jacket material surrounding the core material, wherein the jacket material includes laminated films having a vapor deposition layer, or a laminate film having a vapor deposition layer, and a laminate having a metal foil. The film is formed into a bag shape by heat welding, wherein the laminated film having the vapor deposition layer comprises a heat welding layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is formed of ethylene-vinyl alcohol copolymer. A vacuum insulator in which a plastic film made of a united resin is subjected to A1 vapor deposition on one side, and the A1 vapor-deposited surface is provided on the heat-welding layer side. 2. An ethylene-vinyl alcohol copolymer resin having an oxygen adsorbent comprising an unsaturated fatty acid.
The vacuum insulator as described. 3. The vacuum heat insulator according to claim 1, wherein the outermost layer contains a moisture adsorbent. 4. The vacuum heat insulator according to claim 1, wherein the ethylene-vinyl alcohol copolymer resin is covered with a polyvinylidene chloride resin. 5. The vacuum heat insulator according to claim 1, wherein the peripheral edge of the end portion of the heat-welded portion is deposited with SiO2. 6. A laminate comprising a core material and a jacket material surrounding the core material, wherein the jacket material is a laminate film having a vapor deposition layer, or a laminate film having a vapor deposition layer, and a laminate having a metal foil. The film is formed into a bag shape by heat welding, wherein the laminated film having the vapor deposition layer comprises a heat welding layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is formed of ethylene-vinyl alcohol copolymer. A heat insulating panel comprising a vacuum heat insulator in which A1 vapor deposition is applied to one side of a plastic film made of a united resin, and a surface on which the A1 vapor deposition is applied is provided on the heat welding layer side, and urethane foam. . 7. A laminate comprising: a core material; and a jacket material for enclosing the core material, wherein the jacket material is a laminate film having a vapor deposition layer or a laminate film having a vapor deposition layer, and a laminate having a metal foil. The film is formed into a bag shape by heat welding, and the laminated film having the vapor deposition layer is a laminated film including a heat welding layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is formed of ethylene-based. A plastic film made of a vinyl alcohol copolymer resin having one side subjected to A1 vapor deposition, and a surface having the A1 vapor deposited provided on the heat-welding layer side, wherein the ethylene-vinyl alcohol copolymer is provided. A heat insulation panel in which a vacuum heat insulator having an oxygen adsorbent whose polymer resin is composed of unsaturated fatty acid and a urethane foam are laminated. 8. A laminate comprising a core material and a jacket material surrounding the core material, wherein the jacket material is a laminate film having a vapor deposition layer, or a laminate film having a vapor deposition layer, and a laminate having a metal foil. The film is formed into a bag shape by heat welding, and the laminated film having the vapor deposition layer is a laminated film including a heat welding layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is formed of ethylene-based. A plastic film made of a vinyl alcohol copolymer resin is provided with A1 vapor deposition on one side, and the A1 vapor-deposited surface is provided on the heat-welding layer side. A heat insulation panel comprising a vacuum insulation body containing an agent and urethane foam. 9. A laminate comprising a core material and a jacket material surrounding the core material, wherein the jacket material is a laminate film having a vapor deposition layer, or a laminate film having a vapor deposition layer, and a laminate having a metal foil. The film is formed into a bag shape by heat welding, and the laminated film having the vapor deposition layer is a laminated film including a heat welding layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is formed of ethylene-based. A plastic film made of a vinyl alcohol copolymer resin having one side subjected to A1 vapor deposition, and a surface having the A1 vapor deposited provided on the heat-welding layer side, wherein the ethylene-vinyl alcohol copolymer is provided. A heat insulation panel in which a vacuum heat insulator in which a polymer resin is coated with a polyvinylidene chloride resin and a urethane foam are laminated. 10. A laminate comprising a core material and a jacket material surrounding the core material, wherein the jacket material is a laminate film having a vapor deposition layer, or a laminate film having a vapor deposition layer, and a laminate having a metal foil. The film is formed into a bag shape by heat welding, and the laminated film having the vapor deposition layer is a laminated film including a heat welding layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is formed of ethylene-based. A plastic film made of a vinyl alcohol copolymer resin is provided with A1 vapor deposition on one side, and the A1 vapor-deposited surface is provided on the side of the heat-welding layer, and the end of the heat-welded portion is provided. S peripheral part is S
A heat insulation panel in which a vacuum heat insulator on which iO2 is deposited and a urethane foam are multi-layered. 11. A heat insulating box in which a space formed by an outer box, an inner box, and the outer box and the inner box is filled with a foamed heat insulating material, wherein a core material is provided on an inner surface of the outer box or the inner box. And a jacket material for enclosing the core material, wherein the jacket material is formed by laminating laminated films each having a vapor deposition layer, or a laminate film having a vapor deposition layer, and a laminate film having a metal foil by heat welding. The laminated film having the vapor-deposited layer is composed of a heat-sealing layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is formed on one side of a plastic film made of an ethylene-vinyl alcohol copolymer resin. A heat-insulating box provided with a vacuum heat-insulating body provided with A1 vapor deposition on the heat-sealing layer side. 12. An insulating box in which a space formed by an outer box, an inner box, and the outer box and the inner box is filled with a foamed insulating material, wherein a core material is provided on an inner surface of the outer box or the inner box. And a jacket material for enclosing the core material, wherein the jacket material is formed by laminating laminated films each having a vapor deposition layer, or a laminate film having a vapor deposition layer, and a laminate film having a metal foil by heat welding. Wherein the laminated film having the vapor-deposited layer is a laminated film including a heat-sealing layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is formed of an ethylene-vinyl alcohol copolymer resin. A plastic film on which one side is subjected to A1 vapor deposition, and wherein the surface on which the A1 vapor deposition is performed is provided on the side of the heat-welding layer; A heat insulation box provided with a vacuum heat insulator having an oxygen adsorbent in which an alcohol copolymer resin is composed of an unsaturated fatty acid. 13. An insulating box in which a space formed by an outer box, an inner box, and the outer box and the inner box is filled with a foamed heat insulating material, wherein a core material is provided on an inner surface of the outer box or the inner box. And a jacket material for enclosing the core material, wherein the jacket material is formed by laminating laminated films each having a vapor deposition layer, or a laminate film having a vapor deposition layer, and a laminate film having a metal foil by heat welding. The laminated film having the vapor-deposited layer is a laminated film composed of a heat-sealing layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is composed of an ethylene-vinyl alcohol copolymer resin. One side of the plastic film is subjected to A1 vapor deposition, and the surface on which the A1 vapor deposition is performed is provided on the heat-welding layer side. Insulated box provided with vacuum insulator containing agent. 14. A heat insulating box in which a space formed by an outer box, an inner box, and the outer box and the inner box is filled with a foamed heat insulating material, wherein a core material is provided on an inner surface of the outer box or the inner box. And a jacket material for enclosing the core material, wherein the jacket material is formed by laminating laminated films each having a vapor deposition layer, or a laminate film having a vapor deposition layer, and a laminate film having a metal foil by heat welding. Wherein the laminated film having the vapor-deposited layer is a laminated film including a heat-sealing layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is formed of an ethylene-vinyl alcohol copolymer resin. A plastic film on which one side is subjected to A1 vapor deposition, and wherein the surface on which the A1 vapor deposition is performed is provided on the side of the heat-welding layer; A heat insulation box provided with a vacuum heat insulator in which an alcohol copolymer resin is covered with a polyvinylidene chloride resin. 15. A heat insulating box in which a space formed by an outer box, an inner box, and the outer box and the inner box is filled with a foamed heat insulating material, wherein a core material is provided on an inner surface of the outer box or the inner box. And a jacket material for enclosing the core material, wherein the jacket material is formed by laminating laminated films each having a vapor deposition layer, or a laminate film having a vapor deposition layer, and a laminate film having a metal foil by heat welding. The laminated film having the vapor-deposited layer is a laminated film composed of a heat-sealing layer, a gas barrier layer, and an outermost layer, and the gas barrier layer is composed of an ethylene-vinyl alcohol copolymer resin. One side of the plastic film is subjected to A1 vapor deposition, and the surface on which the A1 vapor deposition is performed is provided on the side of the heat-welding layer. A heat-insulating box provided with a vacuum heat-insulating body whose edge is deposited with SiO2.