JP2008045580A - Vacuum heat insulating panel and equipment equipped therewith - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high performance vacuum heat insulating panel adaptable in a high temperature environment, having higher sticking-in and tearing-off resistance and lower cost while suppressing the aging deterioration of a heat conducting property. <P>SOLUTION: In the vacuum heat insulating panel, glass wool having an average fiber diameter of 3-5 μm and containing no bonding agent, and a getter agent are covered with a facing material formed of metal foil, an organic high polymer (polyimide, polyamideimide, polyimidesiloxane, or polyamide) superior in oxygen permeability is used for welding the facing material, and its inside is depressurized and sealed. A welded layer has a welded portion only formed in a framed shape to suppress the generation of outgas while maintaining adhering strength. The vacuum heat insulating panel is placed in equipment having at least a 150°C heated portion where heat insulation is required. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a vacuum heat insulation panel that blocks heat influence, and more particularly, to a vacuum heat insulation panel used for a high temperature heating element, a manufacturing method thereof, and an apparatus using the same.

  In recent years, from the viewpoint of global warming, energy reduction such as power consumption is desired for various products including home appliances. For example, if the amount of power consumed by the refrigerator is constant, the energy consumed can be reduced by improving the efficiency of the cooling compressor and the heat insulating performance of the heat insulating material related to the amount of heat leakage.

  Until now, high-performance vacuum insulation panels with reduced thermal conductivity have been developed and used in many refrigerators and freezers. In particular, the vacuum heat insulation panel has an excellent thermal conductivity compared to a heat insulating material such as urethane foam. The structure of the vacuum heat insulation panel is such that a core material serving as a core material and a getter agent that adsorbs outgas is put in a jacket material, and the inside is decompressed. The jacket material currently used is produced by a laminating method in which a general-purpose inexpensive organic film is used and the gas barrier layer is adhered to the entire surface with an adhesive. As the gas barrier layer, an aluminum thin foil, aluminum vapor deposition, Eval film, polyester film, etc. are bonded together, and a nylon film is pasted on the protective layer. A polyethylene film or a polypropylene film is used for the welding layer.

  The application of vacuum insulation panels to the periphery of high-temperature components such as microwave ovens, heating cookers, thermostats, photocopiers, laser printers, cars, etc. is desired, and the development of heat-resistant vacuum insulation materials is required. .

In order to improve heat resistance, it is necessary to increase the heat resistance of the jacket material. As a commercially available high-temperature coating material, there is a laminate film for retort foods and using a propylene homopolymer (CPP) as a heat-welded layer. Japanese Patent Application Laid-Open No. 2004-332929 (Patent Document 1), in which the heat resistance temperature of the jacket material using the CPP layer for heat welding is about 120 ° C., is a laminate jacket material having a heat welding layer, a gas barrier layer, and a protective layer. The vacuum heat insulating material provided is described, and it is described that a film having a high melting point is used as the heat welding layer.

  JP-A-2005-1114013 (Patent Document 2) describes that an outermost layer of a heat insulating material is provided with a flame-retardant self-extinguishing film.

  Japanese Patent Laying-Open No. 2005-114014 (Patent Document 3) describes that an adhesive layer is made of an acrylic, polyester, epoxy, or silicone adhesive.

  Japanese Patent Application Laid-Open No. 2001-141179 (Patent Document 4) describes a vacuum heat insulating material using a metal for a gas barrier layer.

JP 2004-332929 A JP 2005-1114013 A JP 2005-111401 A JP 2001-141179 A

  For example, a heat insulating panel used for a microwave oven, a cooking heater or the like needs to have a heat resistance of at least 150 ° C. or more. However, conventionally, a vacuum heat insulating material having high heat resistance and low cost has not been provided.

  The vacuum heat insulation panels described in Patent Documents 1 to 4 are configured to be laminated with a heat resistant film, and outgas is generated in a high temperature environment, so that the heat conductivity of the vacuum heat insulation panel is increased. In addition, since the heat-resistant film is very expensive, the cost of the jacket material is high and becomes a problem.

  Moreover, there exists a method of welding metals, such as an aluminum laminate thin foil, as a jacket material for high temperature. However, it is difficult to make the current size such as 200 × 1500 mm, for example. The reason is that the metal foil of the jacket material becomes thick and the thermal conductivity becomes high, or there are problems that the jacket material is large and it is difficult to keep parallel during welding.

  Moreover, although the heat-bonding layer of the fluorine-based film having a melting point of 200 ° C. or higher is excellent in heat resistance and flame retardancy, it is non-adhesive (contact angle is 100 to 115 degrees and cannot be bonded as a sealant), so If it is used for the heat-welded layer, the adhesive strength is lowered and the heat insulation effect may not be maintained.

  Therefore, an object of the present invention is to provide a vacuum heat insulating panel that is inexpensive and has a high heat insulating effect.

  The feature of the invention that solves the problem of the present application is that a pair of metal foils, an adhesive layer formed or arranged in a shape having one or a plurality of openings between the metal foils, and arranged over the openings. The vacuum panel has an inorganic fiber core material that does not contain a binder and a getter agent that adsorbs a gas component, and the core material and the getter agent are covered with the metal foil and sealed under reduced pressure.

  The said welding layer is formed in frame shape in the peripheral part of the metal foil which welds. The thickness of the vacuum heat insulation panel can be reduced and the cost can be reduced as compared with the case of attaching to the conventional front surface. It is also possible to form a vacuum heat insulating panel in which a frame-like welded layer having a plurality of openings is formed in one metal foil, and a core material or the like is disposed on each of the layers, and the inside is divided into a plurality of sections.

  An organic polymer having a low oxygen permeability is used for the weld layer. In particular, the organic polymer is preferably at least one of polyimide, polyamideimide, polyimidesiloxane, and polyamide resin. In addition, when forming a welding layer using a varnish, it is preferable that the organic-polymerization reaction is completed in the stage of a varnish.

  The core material is preferably glass wool having an average fiber diameter of 3 to 5 μm. This is because the thermal conductivity increases as the fiber diameter increases, and the handling becomes inconvenient when the fiber diameter is small. The core material does not include a binder such as a binder. This is to prevent outgassing from the binder and increase the thermal conductivity.

  The metal foil is preferably an aluminum alloy foil or a stainless steel foil. Compared with frequently used aluminum foil, the thermal conductivity can be lowered. The thickness of the stainless steel foil is preferably 20 to 100 μm, or the aluminum alloy foil is preferably 15 to 30 μm. According to the present invention, it is possible to use a metal foil that is slightly thicker than before.

  Laminate films are often used in combination with aluminum foil, and there is no problem even if the laminate processing is applied to the present invention, but it is not essential. By eliminating the laminate film, it is possible to reduce the manufacturing process and cost.

  According to the above configuration, it is possible to provide a vacuum heat insulating panel that can be used under high temperature conditions, has high heat insulating properties, and is inexpensive.

  Furthermore, energy consumption can be reduced by adopting the heat insulating panel of the present invention in products having various high temperature parts. In particular, the amount of power consumption can be reduced by blocking the thermal effect of a high-temperature heat generating portion of at least about 150 ° C. inside the device such as a thermostatic bath, a microwave oven, an IH cooking heater, or the inside of the device.

  The structure and production of the vacuum heat insulation panel of the present invention and a device in which the vacuum heat insulation panel is inserted will be described with reference to the drawings. Fig.1 (a) shows the structure of the conventional vacuum heat insulation panel, FIG.1 (b) shows the cross-sectional schematic diagram of a jacket material and a welding part. This is a vacuum heat insulation panel having a configuration in which an inorganic fiber core material 2 and a getter agent 3 are sealed under reduced pressure by a jacket material 4 and a weld portion 5 in a vacuum heat insulation panel 1. Fig.2 (a) shows the structure of the vacuum heat insulation panel of this invention, FIG.2 (b) shows the cross-sectional schematic diagram of a jacket material and a welding part. The vacuum heat insulating panel 6 is a vacuum heat insulating panel having a configuration in which the core material 2 and the getter agent 3 of an inorganic fiber material not containing a binder are sealed under reduced pressure by a jacket material 7 and a welded portion 8. FIG. 2C shows a perspective view of a weld layer forming portion in which the weld portion 8 is formed in a frame shape on the metal foil 9.

As a welding layer, it is comprised in frame shape, thickness is about 10-30 mm, and thickness is about 10-10 mm.
It is preferably about 50 μm. Between the welding layer and the jacket material, a layer for other purposes such as a layer for improving adhesion and a layer for improving the strength of the jacket material may be provided in advance. According to the above configuration, a high-priced heat-resistant film is not laminated on the entire surface as in the conventional method of manufacturing a jacket material, and the price is reduced. Moreover, since the adhesive strength is excellent and generation of outgas is suppressed, heat resistance is improved.

  This is a vacuum heat insulation panel in which a core material of inorganic fiber not containing a binder and a getter agent are covered with a jacket material made of a thin metal foil, and the inside is decompressed and sealed. In particular, a frame-like organic polymer is used as a welding layer at the peripheral edge of the jacket material. Various gas permeation can be prevented by using an organic polymer having excellent oxygen permeability only for the seal layer. Moreover, outgas can be suppressed and deterioration with time can be suppressed. Further cost reduction can be achieved.

An organic polymer having a low oxygen permeability is used for the weld layer. The oxygen permeability is preferably 500 cc / m ² · day or less. Here, the oxygen permeability is a permeation index such as H ₂ O, CO ₂ , O ₂ gas. As the welding layer, it is preferable to use at least one of polyimide, polyamideimide, polyimidesiloxane, and polyamide resin. Since these resins are thermosetting resins, they do not have a softening temperature and are suitable for use at high temperatures. In particular, the glass transition temperature is preferably 160 to 230 ° C. By using an organic polymer such as polyimide having a relatively low glass transition temperature, thermocompression bonding becomes easy even at a low temperature of about 200 ° C.

  According to such a configuration, a vacuum heat-insulating panel having little heat deterioration and high heat resistance can be obtained. In addition, the adhesive strength is strong.

  Here, polyimide, polyamideimide, polyimidesiloxane, and polyamide are solvent-soluble and can be made into a varnish. As the solvent, N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, sulfolane, anisole, tetrahydrofuran, dioxane, butyllactone and the like are used.

  A varnish such as polyimide can be directly synthesized by adding raw materials, for example, a diamine component and an acid component in an approximately equimolar amount to a solvent.

  A description will be given below by taking a polyimide resin as an example. Generally, polyimide is synthesized by reacting a diamine component and an acid component. When the polyimide resin is reacted at around room temperature, a polyimide precursor varnish is obtained, and when reacted at around 180 ° C., a polyimide varnish can be synthesized.

  When polyimide resin is usually used, for example, when polyimide is used for flexible printed wiring board of copper foil laminated substrate, semiconductor passivation, etc., polyimide precursor type polyimide is applied and at a high temperature of 250 ° C. or higher after coating film formation. It can be heated and dehydrated.

  However, a polyimide varnish is more preferable than a polyimide precursor as a vacuum sealing material sealing layer used in the present application. This is because when the polyimide precursor varnish is used for the heat-welded layer of the jacket material, water outgassing occurs due to dehydration ring closure during imidization, and the amount of getter agent needs to be increased. Also, when thermocompression sealing is performed at a temperature of about 200 ° C., the adhesive strength is inferior to that of a direct polyimide varnish.

  The resin such as polyimide used in the present invention is preferably a varnish that can synthesize a varnish (reaction solution) directly from the raw material in one stage, complete imidization at the varnish stage, and has excellent storage stability.

Examples of diamine components for polyimide synthesis include 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 3,3'-diaminodiphenyl. Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] sulfone, 1, 7-diaminoheptane, 1,6-diaminohexane, 4,4'-methylenebis (2-methylcyclohexaneamine), isophthalic acid dihydrazide, sebacic acid dihydrazide, succinic acid dihydrazide, bis (3-aminopropyl) tetramethyldisiloxane, 1,1,3,3-tetramethyl- , 1,3-bis (4-aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (4-aminoethyl) can be mentioned disiloxane like.

  Examples of the acid component for the synthesis of polyimide include bicyclo (2,2,2) oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3,3 ', 4,4'- Biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride , Isophthalic acid chloride, stearic acid chloride and the like.

  The weld layer preferably has an adhesive strength at 150 ° C. of 10 N / 15 mm or more. This is because the adhesive strength of the seal welded portion is excellent even in a high temperature environment, and the thermal conductivity is hardly deteriorated with time. The durability of the vacuum insulation panel is improved. The adhesive strength was confirmed by a 90 ° peeling force evaluated using Tensilon after forming a coating film of an organic polymer on a stainless steel foil or an aluminum alloy foil.

  The inorganic fiber material is preferably glass wool. Thermal conductivity and cost vary greatly depending on the average fiber diameter of glass wool. Glass wool having a large average fiber diameter is preferable because of its low cost. Moreover, the thickness of the core material can be easily obtained and handled easily. Further, glass wool having a small average fiber diameter is preferable because the fibers are less likely to be arranged in the same direction and the contact thermal resistance is large, so that the thermal conductivity is low.

  In the present invention, the inorganic fibers are particularly preferably those having an average fiber diameter of 3 to 5 μm. With this fiber diameter, the heat flow path becomes zigzag, and the thermal resistance can be increased and the thermal conductivity can be lowered other than the contact resistance.

  The inorganic fiber material preferably does not contain a binder. The reason why outgas is generated from the binder is that it is necessary to increase the amount of getter agent in order to maintain the thermal conductivity.

  As described above, it is necessary to seal the getter agent that adsorbs the internal gas and keeps the thermal conductivity low together with the core material. This is to increase the reliability of the vacuum insulation panel. Getter agent may be dosorbite, hydrotalcite, metal hydroxide gas adsorbent, etc., or molecular sieves, silica gel, calcium oxide, zeolite, activated carbon, potassium hydroxide, sodium hydroxide, lithium hydroxide as required. It is preferable to use a water adsorbent or the like such as a mixture or a mixture thereof.

  The metal foil can be used even a metal foil that is slightly thicker than before. As a result, it is possible to increase the strength against piercing and tearing and reduce the cost. In particular, either stainless steel foil or aluminum alloy foil is preferable. In addition to thermal conductivity, the thickness of the stainless steel foil is preferably 20 to 100 μm and the thickness of the aluminum alloy foil is preferably 15 to 30 μm from the viewpoints of strength and handleability.

  In addition, you may use together iron, nickel, tin, titanium, carbon steel etc. which are metals with little heat amount which flows in along metal foil. Moreover, you may use together metal vapor deposition, such as aluminum, cobalt, nickel, and zinc.

  The method for producing the weld layer is not particularly limited, and can be appropriately performed by applying a solution coating film, a film, or an impregnated body such as a nonwoven fabric.

  The solution coating film is manufactured by screen printing, roll coater or the like. The film is obtained by casting a varnish on a glass substrate, drying at 90 ° C., and then peeling off the coating film. An impregnated body such as a nonwoven fabric is used as a prepreg or the like by impregnating a reinforcing material composed of reinforcing fibers with a solution. The reinforcing material can be in the form of a sheet, non-woven fabric, or fiber. In particular, the use of glass fiber is preferable because of its low thermal conductivity.

  The welding and sealing of the weld layer is performed by thermocompression bonding. There is no restriction | limiting in particular in the means of thermocompression bonding, What is necessary is just to fix a welding layer. For example, a hot press, a hot roll, etc. are raised. In particular, when a vacuum pressing method is employed, heating and pressurization can be performed in a reduced pressure state, and a jacket material having no defects can be produced.

  The vacuum heat insulation panel of the present invention can be appropriately used for a part requiring heat insulation, such as home appliances and building materials. In particular, it can be suitably used for an oven, a range, a cooking heater, a water heater, or the like that needs to keep a high temperature part, and a thing that needs to separate a high temperature part and a low temperature part.

  Examples of home appliances include refrigerators and air conditioner outdoor units, and building materials include wall materials, bathroom surroundings, other vehicles such as automobiles and railroads, medical inspection equipment, and thermostatic containers. The present invention is not limited to a product having a high-temperature heat generating portion of 150 ° C. or higher, and is preferable because it has excellent durability and heat insulation even when used at 150 ° C. or lower.

  The maximum temperature is preferably about 220 ° C. or lower. This is because deterioration or alteration of the organic polymer weld layer is promoted, and adhesion may not be maintained.

  FIG. 3 is a schematic cross-sectional view of a thermostatic chamber into which the vacuum heat insulating panel 6 of the present invention is inserted. It is the example used around the door 10 of the thermostat, and the space 12 in the store | warehouse | chamber.

  FIG. 4 shows a schematic cross-sectional view of the microwave oven. This is an example in which the vacuum heat insulation panel 6 of the present invention is inserted inside the door 14 and the interior space 13 of the microwave oven.

  FIG. 5 shows a schematic cross-sectional view of the IH cooking heater. The vacuum heat insulation panel 6 of the present invention is inserted into the periphery of the grill of the IH cooking heater.

〔Example〕
With respect to the polyimide, polyamideimide, polyimidesiloxane, and polyamide used in the present invention, the synthesis method, the production of a vacuum heat insulating panel, the evaluation of thermal conductivity, the equipment using the same, and the like will be described in detail below. Table 1 shows the core material, jacket material, welded layer, oxygen permeability, glass transition temperature, adhesive strength, initial thermal conductivity, and thermal conductivity after aging used for the vacuum insulation panel. In addition, this invention is not restrict | limited at all by these Examples.

  In the examples, oxygen permeability, adhesive strength, and glass transition temperature were measured by the following methods.

The oxygen permeable varnish was cast on a glass substrate, dried at 90 ° C., peeled off, and further heat-treated at 230 ° C. to obtain a film. The obtained film was cut to have a width and length of 100 mm, and using an oxygen permeability measuring device (manufactured by MOCON, model OX-TRAN 2/21) under the conditions of a temperature of 25 ° C., dry, and 24 hours. Oxygen permeability was measured.

Adhesive strength A sample film with a width of 15 mm is placed on a stainless steel foil, set in a hot press, the press is closed, and a pressure of about 0.3 to 1.0 kgf / cm ² is applied at 200 ° C. for 5 to 30 ° C. The 90 ° peel force was measured using a test sample obtained by partial pressurization and then cooling. The measurement was performed in accordance with JIS C6481, and Tensilon MPW-300S manufactured by Orientec was used as a testing machine.

Glass transition temperature Using a thermomechanical analyzer TMA manufactured by Seiko Denshi Kogyo Co., Ltd., while applying a load using a cylindrical quartz probe to a test-produced film, within a range from room temperature to 300 ° C. at a temperature rising rate of 10 ° C./min. It was measured.

Example 1 is an example of a vacuum heat insulation panel using polyimide having a glass transition temperature of 176 ° C. and an oxygen permeability of 390 cc / m ² · day as a weld layer.

(Synthesis of polyimide welding material 1)
A reaction vessel having a separable flask equipped with a stirrer and a cooling pipe equipped with a trap with a silicon cock was constructed. In this reaction vessel, the raw material bicyclo (2,2,2) oct-7-ene- 9.9 g of 2,3,5,6-tetracarboxylic dianhydride, 12.0 g of 3,4'-diaminodiphenyl ether, 200 g of N-methyl-2-pyrrolidone and 30 g of toluene were placed in a nitrogen gas atmosphere at room temperature. After stirring for 10 minutes, the contents of the reaction vessel were heated to 180 ° C., and the number of revolutions of the stirrer was set to 180 rpm and reacted for 1 hour. Thereafter, the reaction solution was air-cooled, and further, 14.7 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 16.1 g of 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. 1,7-diaminoheptane (10.4 g), N-methyl-2-pyrrolidone (160 g) and toluene (30 g) were added, and the mixture was stirred again for 2 hours while the temperature was raised to 180 ° C. During this time, the rotational speed of the stirrer was 180 rpm, and water produced was excluded from the silicon cock to synthesize polyimide varnish.

  Furthermore, when improving and using the purity of a varnish, the obtained reaction liquid (varnish) is inject | poured into excess methanol, and resin powder is precipitated by stirring with a mixer. The powder is washed with methanol, dried at room temperature, dried under reduced pressure at about 150 ° C., redissolved in N-methyl-2-pyrrolidone and used to obtain a high-purity polyimide varnish.

The weight average molecular weight (Mw) of the varnish was measured using a TSK gel GMH-M type gel column and UV-8020 type detector manufactured by Tosoh Corporation. As a result, the weight average molecular weight was 42,000, and the resin content was 23.2% by weight. Met. Moreover, as a result of producing a film of about 25 μm and measuring physical properties, it had an oxygen permeability of 390 cc / m ² · day, a glass transition temperature of 176 ° C., and an adhesive strength at a temperature of 150 ° C. of 13.8 N / 15 mm.

(Creation of vacuum heat insulation panel Example 1 using polyimide welding material 1)
The synthesized polyimide welding material 1 was used for the sealing layer of the jacket material, and a vacuum heat insulation panel example 1 was created.

The polyimide varnish synthesized as described above was applied to the periphery of the stainless foil having a thickness of about 30 μm in a frame shape at a thickness of about 30 μm using a screen printer. The coating film was semi-solidified at about 70-90 ° C, a pair of stainless foils were installed in a hot press machine, and sealed at three sides by applying a temperature of about 200 ° C and a pressure of 0.83 kg / cm ² A substrate was prepared.

  As the core material of the vacuum heat insulating panel, glass wool having an average fiber diameter of 3 μm was used after aging treatment at 180 ° C. for 1 hour. The semi-solidified bag-shaped outer jacket material was filled with glass wool as a core material and a gas adsorption getter agent (Molecular Sieves 13X / activated carbon).

  Polyimide was applied to the final sealing portion and evacuated with a rotary pump of the vacuum packaging machine for 10 minutes and with a diffusion pump for 10 minutes until the internal pressure of the vacuum heat insulation panel reached 1.3 Pa. Then, the edge part was sealed by heat sealing.

  The thermal conductivity of the vacuum insulation panel example 1 (thickness: about 8 mm) thus obtained was measured. The initial thermal conductivity was 4.1 mW / m · K under conditions of AUTO-Λ and 10 ° C. manufactured by Eihiro Seiki Co., Ltd. When a deterioration test was conducted at 160 ° C. for one month, the thermal conductivity after the deterioration test was 5.2 mW / m · K. As described above, the vacuum heat insulating panel of the present invention was able to maintain the thermal conductivity without being deteriorated with time even in a high temperature environment.

  Furthermore, since polyimide is a thermosetting resin and does not have a softening point even at a high temperature, the adhesiveness can be maintained up to a high temperature of about 70 to 80 ° C. from the glass transition temperature. Therefore, it is expected that the vacuum heat insulation panel Example 1 can withstand use at about 240 to 260 ° C.

(An example of a thermostatic chamber using the vacuum insulation panel Example 1)
Since the periphery of the thermostatic chamber used at high temperatures and the back of the door are hot, conventional vacuum insulation panels could not be installed. The above vacuum insulation panel Example 1 was used by being inserted into the periphery of the thermostat and the back of the door.

  Compared to the case where no vacuum insulation panel is provided, the power consumption is reduced by about 5%. Moreover, the heat insulation effect could be maintained for a long time. Furthermore, by using the vacuum heat insulation panel, the heat insulation layer can be made thinner than the conventional heat insulation panel, and the space in the cabinet can be widened with respect to the apparatus volume.

Example 2 is an example of a vacuum heat insulation panel using polyimide having a glass transition temperature of 226 ° C. and an oxygen permeability of 420 cc / m ² · day as a weld layer.

(Synthesis of polyimide welding material 2)
A reaction vessel having a separable flask equipped with a stirrer and a cooling pipe equipped with a trap with a silicon cock was constructed. In this reaction vessel, the raw material bicyclo (2,2,2) oct-7-ene- 9.9 g of 2,3,5,6-tetracarboxylic dianhydride, 12.0 g of 3,4'-diaminodiphenyl ether, 200 g of N-methyl-2-pyrrolidone and 30 g of toluene were placed in a nitrogen gas atmosphere at room temperature. After stirring for 10 minutes, the contents of the reaction vessel were heated to 180 ° C., and the number of revolutions of the stirrer was set to 180 rpm and reacted for 1 hour. Thereafter, the reaction solution was air-cooled, and further, 14.7 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 16.1 g of 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. 4,4'-methylenebis (2-methylcyclohexaneamine) 19.1 g, N-methyl-2-pyrrolidone 160 g and toluene 30 g were added, and the mixture was stirred for 1.5 hours with the temperature raised to 180 ° C. went. During this time, the rotational speed of the stirrer was 180 rpm, and water produced was excluded from the silicon cock to synthesize polyimide varnish.

The weight average molecular weight of the varnish was 62000, and the resin content was 20% by weight. As a result of producing a film of about 25 μm and measuring physical properties, the glass transition temperature was 226 ° C. and the adhesive strength was 15.1 N / 15 mm at an oxygen permeability of 420 cc / m ² · day and a temperature of 150 ° C.

(Creation of vacuum heat insulation panel example 2 using polyimide welding material 2)
A vacuum heat insulation panel example 2 was prepared in the same manner as the vacuum heat insulation panel example 1 except that the synthesized polyimide welding material 2 was used for the sealing layer of the jacket material and glass wool having an average fiber diameter of 3.5 μm was used as the core material. .

  The heat conductivity of the vacuum insulation panel example 2 (thickness: about 8 mm) obtained in this way is the same measurement as that of the insulation panel example 1, with an initial thermal conductivity of 4.1 mW / m · The thermal conductivity after a deterioration test for 1 month at K, 200 ° C. was 5.9 mW / m · K. As described above, the vacuum heat insulating panel of the present invention was able to maintain the thermal conductivity without being deteriorated with time even in a high temperature environment.

  Similarly to Example 1, since the adhesiveness can be maintained up to a high temperature of about 70 to 80 ° C. from the glass transition temperature, it is expected that Example 2 of the vacuum heat insulation panel can withstand use at about 280 ° C.

(Example of microwave oven using vacuum insulation panel 2)
The above-mentioned vacuum heat insulation panel example 2 was inserted into the peripheral part of the microwave oven and the back of the door to see the effect. As with the thermostatic chamber, the microwave oven was hot and could not lay a conventional vacuum insulation panel.

  Compared to the case where no vacuum heat insulation panel is provided, the power consumption is reduced by about 3%. Moreover, the heat insulation effect could be maintained for a long time. Furthermore, by using the vacuum heat insulation panel, the heat insulation layer can be made thinner than the conventional heat insulation panel, and the space in the cabinet can be widened with respect to the apparatus volume.

Example 3 is an example of a vacuum thermal insulation panel using polyimide having a glass transition temperature of 161 ° C. and an oxygen transmission rate of 390 cc / m ² · day as a weld layer.

(Synthesis of polyimide welding material 3)
A reaction vessel is constructed by attaching a cooling tube equipped with a trap with a silicon cock to a separable flask equipped with a stirrer, and the bicyclo (2,2,2) oct-7-ene as a raw material is contained in this reaction vessel. 9.9 g of -2,3,5,6-tetracarboxylic dianhydride, 3,
4 g of 4'-diaminodiphenyl ether, 5.2 g of 1,7-diaminoheptane, 200 g of N-methyl-2-pyrrolidone and 30 g of toluene were added and stirred at room temperature in a nitrogen gas atmosphere for 10 minutes. The temperature was raised to 180 ° C., and the number of revolutions of the stirrer was set to 180 rpm to react for 1 hour. Thereafter, the reaction solution was air-cooled, and further, 14.7 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 16.1 g of 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. 1,7-diaminoheptane (10.4 g), N-methyl-2-pyrrolidone (160 g) and toluene (30 g) were added, and the mixture was stirred at a temperature of 180 ° C. for 2.0 hours. During this time, the rotational speed of the stirrer was 180 rpm, and water produced was excluded from the silicon cock to synthesize a polyimide varnish.

The weight average molecular weight of the varnish was 25000, and the resin content was 20% by weight. As a result of producing a film of about 25 μm and measuring physical properties, the glass transition temperature was 161 ° C. and the adhesive strength at a temperature of 150 ° C. was 12.5 N / 15 mm with an oxygen permeability of 390 cc / m ² · day.

(Creation of vacuum heat insulation panel Example 3 using polyimide welding material 3)
A vacuum heat insulation panel example 3 was prepared in the same manner as the vacuum heat insulation panel example 1 except that the synthesized polyimide welding material 2 was used for the sealing layer of the jacket material and glass wool having an average fiber diameter of 4.5 μm was used as the core material. .

  The heat conductivity of the vacuum heat insulation panel example 3 (thickness: about 8 mm) obtained in this way is the same measurement as that of the heat insulation panel example 1, and the initial heat conductivity is 4.3 mW / m · The initial thermal conductivity was 5.5 mW / m · K after a deterioration test at K, 150 ° C. for one month. As described above, the vacuum heat insulating panel of the present invention was able to maintain the thermal conductivity without being deteriorated with time even in a high temperature environment.

  Similarly to Example 1, since the adhesiveness can be maintained up to a high temperature of about 70 to 80 ° C. from the glass transition temperature, it is expected that the vacuum heat insulation panel Example 3 can withstand use at about 230 to 240 ° C.

(Example of cooking heater using vacuum insulation panel 3)
The above-described vacuum heat insulation panel example 3 was used in the periphery of the grill of the IH cooking heater to see the effect. As with the thermostat, the cooking heater could not be laid with a conventional vacuum insulation panel at high temperatures.

  The thermal influence on the control circuit could be eliminated by insulating the grill wall. Furthermore, compared with the case where a vacuum heat insulation panel is not provided, the power consumption was reduced by about 5%. Moreover, the heat insulation effect could be maintained for a long time.

  From the above example, it is considered that the same effect can be obtained even when applied to a product that needs to insulate a high-temperature part and a part that requires a low temperature, such as a control circuit, similarly.

Example 4 is an example of a vacuum heat insulating panel using a polyamideimide having a glass transition temperature of 170 ° C. and an oxygen permeability of 450 cc / m ² · day as a weld layer.

(Synthesis of polyamideimide welding material 4)
A reaction vessel having a separable flask equipped with a stirrer and a cooling pipe equipped with a trap with a silicon cock was constructed. In this reaction vessel, the raw material bicyclo (2,2,2) oct-7-ene- 9.9 g of 2,3,5,6-tetracarboxylic dianhydride, 4 g of 3,4'-diaminodiphenyl ether, 200 g of N-methyl-2-pyrrolidone and 30 g of toluene are added, and at room temperature in a nitrogen gas atmosphere for 10 minutes. After stirring, the contents in the reaction vessel were heated to 180 ° C., and the number of revolutions of the stirrer was set to 180 rpm and reacted for 1 hour. Thereafter, the reaction solution is air-cooled, and further, 14.7 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,
3 ', 4,4'-benzophenonetetracarboxylic dianhydride 16.1 g, isophthalic acid dihydrazide 15.5 g, N-methyl-2-pyrrolidone 160 g and toluene 30 g were added and the temperature was raised to 180 ° C again. The stirring reaction was performed for 2.5 hours. During this time, the rotational speed of the stirrer was 180 rpm, and water produced was excluded from the silicon cock to synthesize polyamideimide varnish.

The weight average molecular weight of the varnish was 45000, and the resin content was 23.4% by weight. Moreover, as a result of producing a film of about 25 μm and measuring physical properties, it had an oxygen permeability of 450 cc / m ² · day, a glass transition temperature of 170 ° C., and an adhesive strength at a temperature of 150 ° C. of 12.8 N / 15 mm.

(Creation of vacuum heat insulation panel Example 4 using polyamideimide welding material 4)
A vacuum heat insulation panel example 4 was prepared in the same manner as the vacuum heat insulation panel example 1 except that the synthesized polyamideimide welding material 4 was used for the sealing layer of the jacket material.

  The heat conductivity of the vacuum heat insulation panel example 4 (thickness: about 5 mm) obtained in this way is the same measurement as that of the heat insulation panel example 1, and the initial heat conductivity is 4.2 mW / m · The thermal conductivity after a deterioration test for one month at K, 160 ° C. was 5.3 mW / m · K. As described above, the vacuum heat insulating panel of the present invention was able to maintain the thermal conductivity without being deteriorated with time even in a high temperature environment.

  Similarly to Example 1, the polyamide-imide resin is also a thermosetting resin, and the adhesiveness can be maintained up to a high temperature of about 70 to 80 ° C. from the glass transition temperature, so that the vacuum heat insulating panel Example 4 is about 230 to 250 ° C. It is expected to withstand use in

Example 5 is an example of a vacuum heat insulation panel using polyimide siloxane having a glass transition temperature of 165 ° C. and an oxygen permeability of 400 cc / m ² · day as a weld layer.

(Synthesis of polyimide siloxane welding material 5)
A reaction vessel having a separable flask equipped with a stirrer and a cooling pipe equipped with a trap with a silicon cock was constructed. In this reaction vessel, the raw material bicyclo (2,2,2) oct-7-ene- 9.9 g of 2,3,5,6-tetracarboxylic dianhydride, 4 g of 3,4'-diaminodiphenyl ether, 200 g of N-methyl-2-pyrrolidone and 30 g of toluene are added, and at room temperature in a nitrogen gas atmosphere for 10 minutes. After stirring, the contents in the reaction vessel were heated to 180 ° C., and the number of revolutions of the stirrer was set to 180 rpm and reacted for 1 hour. Thereafter, the reaction solution is air-cooled, and further, 14.7 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,
Add 16.1 g of 3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 19.8 g of bis (3-aminopropyl) tetramethyldisiloxane, 160 g of N-methyl-2-pyrrolidone and 30 g of toluene, and again add 180 The reaction was stirred for 3.5 hours while the temperature was raised to ° C. During this time, the rotational speed of the stirrer was 180 rpm, and water produced was excluded from the silicon cock to synthesize polyimidesiloxane varnish.

The weight average molecular weight of the varnish was 21000, and the resin content was 21.3% by weight. Moreover, as a result of producing a film of about 25 μm and measuring physical properties, the glass transition temperature was 165 ° C. and the adhesive strength was 12.9 N / 15 mm at an oxygen permeability of 400 cc / m ² · day.

(Creation of vacuum insulation panel Example 5 using polyimide siloxane welding material 5)
A vacuum heat insulation panel example 5 was prepared in the same manner as the vacuum heat insulation panel example 1 except that the synthesized polyimidesiloxane welding material 5 was used for the sealing layer of the jacket material and the varnish was applied to a thickness of about 40 μm.

  The heat conductivity of the vacuum heat insulation panel 5 (thickness: about 10 mm) obtained in this way was measured in the same manner as in heat insulation panel example 1, and the initial heat conductivity was 4.1 mW / m · K at 10 ° C. The thermal conductivity after aging test for 1 month at 150 ° C. was 5.3 mW / m · K. As described above, the vacuum heat insulating panel of the present invention was able to maintain the thermal conductivity without being deteriorated with time even in a high temperature environment.

  Similarly to Example 1, the polyimidesiloxane resin is also a thermosetting resin, and the adhesiveness can be maintained up to a high temperature of about 70 to 80 ° C. from the glass transition temperature, so that the vacuum heat insulating panel Example 5 is about 230 to 250 ° C. It is expected to withstand use in

Example 6 is an example of a vacuum heat insulation panel using polyamide having a glass transition temperature of 161 ° C. and an oxygen transmission rate of 490 cc / m ² · day as a weld layer.

(Synthesis of polyamide welding material 6)
In a separable flask equipped with a stirrer, 8.1 g of isophthalic acid chloride, 12.0 g of 3,4'-diaminodiphenyl ether, and 200 g of N-methyl-2-pyrrolidone were put in a nitrogen gas atmosphere at room temperature or lower. Then, the number of revolutions of the stirrer was set to 180 rpm and the reaction was performed for 1 hour. Thereafter, 20.3 g of isophthalic acid chloride, 19.1 g of 4,4′-methylenebis (2-methylcyclohexaneamine) and 160 g of N-methyl-2-pyrrolidone were added while cooling the reaction solution with air, and the reaction was stirred for about 3 hours. To synthesize a polyamide varnish. The obtained reaction liquid (varnish) was poured into excess methanol and stirred with a mixer to precipitate resin powder. This powder was washed with methanol, dried at room temperature, dried under reduced pressure at about 150 ° C., and redissolved in N-methyl-2-pyrrolidone to obtain a polyamide varnish.

The weight average molecular weight (Mw) of the varnish was 32000, and the resin content was 20.2% by weight. Moreover, as a result of producing a film of about 25 μm and measuring physical properties, the oxygen permeability was 490.
The glass transition temperature was 161 ° C. and the adhesive strength at a temperature of 150 ° C. was 13.2 N / 15 mm at cc / m ² · day.

(Creation of vacuum heat insulation panel Example 6 using polyamide welding material 6)
The synthesized polyamide welding material 6 was used for the sealing layer of the jacket material, and the vacuum insulation panel example 6 was created in the same manner as the vacuum insulation panel example 1 for the outside. The size of the core material is 500mm x 300mm x
It was 10 mm.

  The heat conductivity of the vacuum heat insulation panel example 6 (thickness: about 8 mm) obtained in this way is the same measurement as that of the heat insulation panel example 1, and the initial heat conductivity is 4.2 mW / m · The thermal conductivity after deterioration test for 1 month at K, 150 ° C. was 5.1 mW / m · K.

  As described above, the vacuum heat insulating panel of the present invention was able to maintain the thermal conductivity without being deteriorated with time even in a high temperature environment.

  Example 7 is an example of a vacuum heat insulating panel in which the polyimide welding material of Example 2 is impregnated into glass fiber and an aluminum alloy foil is used as a covering material.

A glass fiber was impregnated with the varnish of the polyimide welding material 1 shown in Example 1 and dried at about 90 ° C. to prepare a semi-solidified prepreg. The prepreg is installed in a frame shape on an aluminum alloy foil having a thickness of about 15 μm, the same type of aluminum alloy foil is placed on the prepreg, and a hot press machine is applied at a temperature of about 200 ° C. and a pressure of 0.83 kg / cm ^2. Was used to produce a jacket material that was hermetically sealed on three sides.

  As the core material, glass wool having an average fiber diameter of 3 μm was used after aging treatment at 180 ° C. for 1 hour. The jacket material is filled with a core material and a gas adsorbing getter agent (molecular sieve 13X / activated carbon), the prepreg is installed in the final sealing part, 10 minutes by the rotary pump of the vacuum packaging machine, 10 by the diffusion pump The vacuum insulation panel was evacuated until the internal pressure of the vacuum insulation panel reached 1.3 Pa, and the ends were sealed with heat seal.

  The heat conductivity of the vacuum heat insulation panel example 7 (thickness: about 8 mm) thus obtained is the same measurement as that of the heat insulation panel example 1, and the initial heat conductivity is 4.2 mW / m · The thermal conductivity after aging test for 1 month at K, 200 ° C. was 5.4 mW / m · K. As described above, the vacuum heat insulating panel of the present invention was able to maintain the thermal conductivity without being deteriorated with time even in a high temperature environment.

  A vacuum heat insulating panel example 8 similar to that of the example 1 was produced using a glass wool material having an average fiber diameter of 6 μm as a core material.

  The heat conductivity of the vacuum heat insulation panel example 8 (thickness: about 8 mm) obtained in this way is the same measurement as that of the heat insulation panel example 1, and the initial heat conductivity is 6.2 mW / m · The thermal conductivity after a deterioration test for one month at K, 160 ° C. was 9.8 mW / m · K.

  As described above, the vacuum heat insulating panel of the present invention was able to maintain the thermal conductivity without being deteriorated with time even in a high temperature environment. However, when the glass wool average fiber diameter was 6 μm, the initial value of thermal conductivity was increased.

Example 9 is an example of a vacuum heat insulation panel using a polyimide having a glass transition temperature of 152 ° C. and an oxygen permeability of 390 cc / m ² · day as a weld layer.

(Synthesis of polyimide welding material 9)
A reaction vessel is constructed by attaching a cooling tube equipped with a trap with a silicon cock to a separable flask equipped with a stirrer, and the bicyclo (2,2,2) oct-7-ene as a raw material is contained in this reaction vessel. 9.9 g of -2,3,5,6-tetracarboxylic dianhydride, 3,
After 4 g of 4'-diaminodiphenyl ether, 6.5 g of 1,7-diaminoheptane, 200 g of N-methyl-2-pyrrolidone and 30 g of toluene were stirred at room temperature in a nitrogen gas atmosphere for 10 minutes, the contents of the reaction vessel were The temperature was raised to 180 ° C., and the number of revolutions of the stirrer was set to 180 rpm to react for 1 hour. Thereafter, the reaction solution was air-cooled, and further, 14.7 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 16.1 g of 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. 1,7-diaminoheptane (10.4 g), N-methyl-2-pyrrolidone (160 g) and toluene (30 g) were added, and the mixture was stirred at a temperature of 180 ° C. for 2.0 hours. During this time, the rotational speed of the stirrer was 180 rpm, and water produced was excluded from the silicon cock to synthesize a polyimide varnish.

The weight average molecular weight of the varnish was 180000, and the resin content was 20% by weight. Moreover, as a result of producing a film of about 25 μm and measuring physical properties, the oxygen permeability was 390 cc / m ^2.
In day, the glass transition temperature was 152 ° C., and the adhesive strength at a temperature of 150 ° C. was 8.5 N / 15 mm.

(Creation of vacuum heat insulation panel Example 9 using polyimide welding material 9)
A vacuum heat insulation panel example 9 was prepared in the same manner as the vacuum heat insulation panel example 1 except that the synthesized polyimide welding material 8 was used for the sealing layer of the jacket material.

  The heat conductivity of the vacuum heat insulation panel example 9 (thickness: about 8 mm) obtained in this way is the same measurement as that of the heat insulation panel example 1, and the initial heat conductivity is 5.2 mW / m · K, thermal conductivity after 1 month deterioration test at 200 ° C. was 18.5 mW / m · K.

  Therefore, although the thickness is suppressed as compared with the conventional product and the effect of heat insulation at a normal temperature is exhibited, the glass transition temperature of the resin used for the welding layer is 160 ° C. or lower, and the adhesive strength at a temperature of 150 ° C. is 10 N. / 15 mm or less, it was found that, under high temperature conditions, the adhesive strength was reduced by heating and the vacuum heat insulating panel was broken, preventing deterioration of thermal conductivity over a long period of time. Therefore, it is necessary to limit the use of such a heat insulation panel to, for example, products up to a temperature of 130 ° C. and products used in a short period of time.

  In addition, the thermal conductivity at the time of the start of use (before deterioration) of the conventionally used polyurethane resin is about 18 to 22 mW / m · K.

Example 10 is an example of a vacuum heat insulating panel using an epoxy resin having a glass transition temperature of 140 ° C., an oxygen permeability of 220 cc / m ² · day, and an adhesive strength of 6.5 N / 15 mm at 150 ° C. as a weld layer.

  A vacuum heat insulation panel example 10 was prepared in the same manner as the vacuum heat insulation panel example 1 except that the above epoxy resin welding material was used for the sealing layer of the jacket material.

  The heat conductivity of the obtained vacuum heat insulation panel example 10 (thickness: about 8 mm) is the same measurement as that of the heat insulation panel example 1, and the initial heat conductivity is 6.5 mW / m · K under the condition of 10 ° C., 160 ° C. The thermal conductivity after 1 month deterioration test was 18.4 mW / m · K.

  Although this has the effect of reducing the thickness compared to conventional products, the use of epoxy resin for the weld layer results in low adhesion to the stainless steel foil, and the heat insulation of the vacuum insulation panel is destroyed by heating under high temperature conditions. It was found that the rate deterioration could not be suppressed.

Example 11 has a glass transition temperature of −10 ° C. and an oxygen permeability of 8100 cc / m ² · as a weld layer.
It is an example of the vacuum heat insulation panel using the polypropylene homopolymer of day.

  A vacuum heat insulation panel example 11 was prepared in the same manner as the vacuum heat insulation panel example 1 except that the above polypropylene homopolymer was used for the sealing layer of the jacket material.

  The heat conductivity of the obtained vacuum heat insulation panel example 11 (thickness: about 8 mm) was the same measurement as that of the heat insulation panel example 1, and the initial heat conductivity was 4.9 mW / m · K at 10 ° C. . However, when a deterioration test was performed at 160 ° C. for one month, the welded portion was destroyed and the thermal conductivity could not be measured. Therefore, although there is an effect that the thickness can be suppressed as compared with the conventional product, the vacuum heat insulating panel cannot be used at a temperature higher than the glass transition temperature of the welded layer resin.

(A) Structural drawing of conventional vacuum heat insulation panel, (b) Cross-sectional schematic diagram of jacket material and welded portion of conventional vacuum heat insulation panel. (A) Structural drawing of this invention vacuum heat insulation panel, (b) The cross-sectional schematic diagram of the jacket material and welding part of this invention vacuum heat insulation panel, (c) The perspective view of this invention welded layer formation part. The cross-sectional schematic diagram of the thermostat which inserted this invention vacuum heat insulation panel. The cross-sectional schematic diagram of the microwave oven which inserted this invention vacuum heat insulation panel. The cross-sectional schematic diagram of the IH cooking heater which inserted this invention vacuum heat insulation panel.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Conventional vacuum heat insulation panel, 2 ... Core material, 3 ... Getter agent, 4, 7 ... Cover material, 4-1 ... Polyethylene terephthalate film, 4-2 ... Nylon film, 4-3 ... Aluminum foil, 5, 8 DESCRIPTION OF SYMBOLS ... Welding part, 6 ... Vacuum insulation panel of this invention, 9 ... Metal foil, 10 ... Constant temperature bath door, 11 ... Partition plate, 12 ... Space in a constant temperature chamber, 13 ... Space in a microwave oven, 14 ... Microwave oven door, DESCRIPTION OF SYMBOLS 15 ... Top plate, 16 ... Induction heater, 17 ... Grill door, 18 ... Grill glass, 19 ... Grill handle, 20 ... Control circuit.

Claims (12)

An inorganic fiber core material, a getter agent, and a metal foil outer sheath material covering the core material and the getter agent, and having a welding layer for hermetically sealing a peripheral edge of the outer sheath material, A vacuum insulation panel with reduced pressure inside the material,
The vacuum heat insulating panel, wherein the welding layer is formed or arranged in a shape having one or a plurality of openings. 2. The vacuum heat insulating panel according to claim 1, wherein the welding layer contains an organic polymer, and the oxygen permeability at a thickness of 25 μm is 500 cc / m ² · day or less. Vacuum insulation panel.   2. The vacuum heat insulation panel according to claim 1, wherein the welding layer contains at least one of a polyimide resin, a polyamideimide resin, a polyimidesiloxane resin, and a polyamide resin. A vacuum insulation panel according to claim 3,
The glass heat insulation temperature of the said resin is 160-230 degreeC, The vacuum heat insulation panel characterized by the above-mentioned.   2. The vacuum heat insulation panel according to claim 1, wherein the welding layer has an adhesive strength with a jacket material at 150 ° C. of 10 N / 15 mm or more. A vacuum insulation panel according to claim 1,
The vacuum heat insulation panel, wherein the metal foil is a stainless steel foil or an aluminum alloy foil. A vacuum insulation panel according to claim 1,
The vacuum insulation panel according to claim 1, wherein the core material is glass wool having an average fiber diameter of 3 to 5 µm. A vacuum insulation panel according to claim 1,
The vacuum heat insulating panel according to claim 1, wherein the welding layer is at least one of a coating film, a film or a nonwoven fabric impregnated body coated with a solution. A heat insulating box having a heat retaining part heated by a heating means and a heat insulating member for maintaining the temperature state of the heat retaining part,
The heat insulating member includes an inorganic fiber core material, a getter agent, a metal foil outer sheath material covering the core material and the getter agent, and a frame shape that is hermetically sealed with a peripheral edge of the outer envelope material. A heat insulation box having a layer and being a vacuum heat insulation panel in which the inside of the jacket material is decompressed.   The heat insulation box according to claim 9, wherein the welding layer contains at least one of a polyimide resin, a polyamideimide resin, a polyimidesiloxane resin, and a polyamide resin.   10. The heat insulation box according to claim 9, wherein the welding layer is made of at least one of a coating film, a film, or a nonwoven fabric impregnated body applied with a solution.   It is the heat insulation box body described in Claim 9, Comprising: The highest temperature of the said to-be-insulated part is 150-220 degreeC, The heat insulation box body characterized by the above-mentioned.

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