JP2009085255A - Vacuum heat insulating material and apparatus using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vacuum heat insulating material capable of restraining deterioration with time of a heat insulating characteristic, and an apparatus with the same. <P>SOLUTION: The vacuum heat insulating material is provided with an inorganic fiber core material, a getter agent, and a jacket material covering the core material and the getter agent, and the jacket material is provided with a welded layer sealing a peripheral end of the jacket material, and a gas barrier layer, and an inside of the jacket material is decompressed. The vacuum heat insulating material is characterized in that a hydrophobic laminar clay material and a polymer material are used in a member of the gas barrier layer. This vacuum heat insulating material can be applicable to not only a refrigerator or a freezer, but also a high temperature and high humidity member such as a water heater, an electric water heater, a heat-retaining bathtub, or an inverter module. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a vacuum heat insulating material that blocks heat influence, and more particularly to a vacuum heat insulating material that can be used under high temperature and high humidity conditions and a device using the same.

  From the viewpoint of global warming, energy reduction such as power consumption is desired for various products including home appliances. Up to now, vacuum heat insulating materials with reduced thermal conductivity have been developed and are often used in refrigerators and freezers. For example, if the negative capacity in the refrigerator is constant, the power consumption of the refrigerator can be reduced by improving the heat insulation performance of the heat insulating material related to the efficiency of the cooling compressor and the amount of heat leakage. The structure of the vacuum heat insulating material is such that a core material serving as a core material and a getter agent that adsorbs an outgas is put in a jacket material, and the inside is evacuated and decompressed. The vacuum heat insulating material has a much higher thermal conductivity than a heat insulating material such as urethane foam. Many of the vacuum insulation materials currently used are manufactured by a laminate method in which an organic film is bonded to a gas barrier layer with an adhesive.

  Furthermore, in recent years, it has been desired to apply a vacuum heat insulating material to the periphery of high-temperature, high-humidity members such as water heaters, electric water heaters, heat insulation bathtubs, inverter modules, solar heat collectors and the like. Development of a vacuum heat insulating material in which an inorganic compound is introduced into the gas barrier layer of the jacket material is being carried out for use under high temperature and high humidity conditions.

  Japanese Unexamined Patent Publication No. 2006-29686 (Patent Document 1) uses a jacket material made of a multilayer resin film using a reinforcing layer in which an ethylene-vinyl alcohol copolymer and an inorganic material are hybrid-mixed together with an aluminum foil or the like. Is disclosed. Japanese Patent Laying-Open No. 2006-77799 (Patent Document 2) discloses the use of a jacket material in which a sealant layer made of polyethylene or the like is used together with an aluminum foil or the like. In JP-A-1999-257573 (Patent Document 3), as a getter agent, a resin molded article containing iron powder, pellets or sheet-like iron powder, synthetic zeolite, zirconium alloy or barium-lithium alloy may be used in combination. It is disclosed. Moreover, as a gas barrier layer other than the aluminum foil, Japanese Patent Application Laid-Open No. 1999-182781 (Patent Document 4) discloses a vacuum heat insulating material using a gas barrier layer made of a resin and an inorganic layered compound.

JP 2006-29686 A JP 2006-77799 A JP 1999-257573 A JP 1999-182781

  Vacuum insulation materials used in the vicinity of high-temperature components such as water heaters, electric water heaters, thermal insulation baths, inverter modules, solar heat collectors, etc. require a jacket material that can withstand high temperatures and high humidity for a long time. The aluminum foil used in Patent Documents 1 to 3 can maintain a high degree of vacuum over a long period of time and is excellent as a gas barrier layer, but has a problem of high thermal conductivity. On the other hand, if aluminum is used as a thin foil in order to reduce the thermal conductivity, the thinner the aluminum, the more pinholes exist, and the gas barrier property is lowered. As an alternative to the aluminum foil, aluminum vapor deposition exists. However, since moisture and gas permeability are higher than those of the aluminum foil, the thermal conductivity is greatly deteriorated over time as compared with the vacuum heat insulating material made of the aluminum foil.

  Moreover, the vacuum heat insulating material using the gas barrier layer which consists of resin and an inorganic layered compound described in patent document 4 is calculated | required in the further heat insulation performance improvement.

  Therefore, a feature of the present invention is to provide a vacuum heat insulating material having a jacket material that exhibits a high heat insulating effect for a long time without using aluminum. Another object of the present invention is to provide equipment such as a water heater, an electric water heater, a hot tub, an inverter module, and a solar heat collecting device that uses the vacuum heat insulating material to reduce energy consumption.

  The vacuum heat insulating material of the present invention that solves the above problems includes a core material of inorganic fibers, a getter agent for adsorbing moisture and atmospheric components and maintaining an internal vacuum, and a jacket material that covers the core material and the getter agent A vacuum heat insulating material in which the inside of the jacket material is decompressed, and the jacket material has a gas barrier layer having low moisture and gas permeability. The present invention is characterized in that a hydrophobic inorganic layered compound, particularly a mixture of a layered clay material and a polymer material is used as the gas barrier layer.

  The inorganic layered compound is preferably an inorganic layered clayey material in which unit crystal layers are stacked on each other to have a layered structure, particularly a smectite clay composed of a three-layered crystal.

  Moreover, it is desirable to use a hydrophobic polymer material as the polymer material.

  According to the said structure, the vacuum heat insulating material which has high heat insulation performance can be provided. In addition, it is possible to provide equipment such as a water heater, an electric water heater, a hot tub, an inverter module, and a solar heat collector that can reduce energy consumption for a long period of time.

  Hereinafter, the present invention will be further described using specific examples. The vacuum heat insulating material is used in equipment such as a refrigerator, and cuts off the heat effect of the equipment and the outside air or the heat generating part in the equipment, thereby reducing the energy consumption and power consumption of the product. The inventors of the present application have obtained a vacuum heat insulating material having high heat insulating performance by dispersing a hydrophobic inorganic layered compound in a polymer material such as a resin in order to improve the heat insulating effect.

  Hot water heaters, electric water heaters, hot water baths, inverter modules, solar heat collectors, etc. that generate and maintain high temperatures need to be kept warm under high temperature and high humidity conditions. For this reason, a vacuum heat insulating material used for keeping the temperature of the equipment, for example, a water heater, an electric water heater, etc., may boil the water, so that it must be able to withstand use at a temperature of 110 ° C. or higher. Further, as the high humidity condition, a condition of 80% or more at 60 ° C. is assumed. Under high temperature and high humidity conditions, the air pressure inside the vacuum insulation rises and the thermal conductivity tends to increase. Even under such conditions, a vacuum heat insulating material that has a heat insulating effect over a long period of time and maintains the effect of reducing the energy consumption of the device is very useful. The inventors of the present application have studied a jacket material in combination with a hydrophobic polymer material in order to achieve both a reduction in gas entry and a reduction in water vapor transmission rate. According to the said structure, the coating | coated material excellent in long-term gas-barrier property can be provided also in high temperature and high humidity conditions, and the apparatus excellent in long-term reliability can be provided.

  Hereinafter, an example of a vacuum heat insulating material, a device in which the vacuum heat insulating material is inserted, and a manufacturing method thereof will be described with reference to the drawings.

  FIG. 1 shows a structure of a conventional vacuum heat insulating material example. FIG. 1A is a schematic cross-sectional view of the whole, and FIG. 1B is an enlarged view including the welded portion of FIG. The outer cover material of the vacuum heat insulating material has a welding layer that hermetically seals the peripheral portion, a gas barrier layer, and an overcoat layer for avoiding external impact and the like. The gas barrier layer is an aluminum foil or an aluminum vapor deposition layer. The core of the vacuum heat insulating material is an inorganic fiber such as glass wool that does not contain a binder. The getter agent is covered with a jacket material together with a core material, and the inside is reduced in pressure and sealed with a welding layer.

  In FIG. 2, the structure of the vacuum heat insulating material of a present Example is shown. 2A is a schematic cross-sectional view of the whole, and FIG. 2B is an enlarged view including the welded portion of FIG. 2A. The jacket material of the present embodiment is also composed of a welding layer, a gas barrier layer, and an overcoat layer as in the conventional case. As shown in the figure, the vacuum heat insulating material of the present example includes a core material of inorganic fibers, a getter agent, and a jacket material covering the core material and the getter agent, and the inside of the jacket material is decompressed. . The jacket material has a welded layer and a gas barrier layer that blocks gas, liquid, etc., and the jacket material is tightly sealed at the peripheral edge of the core material by the welded layer. As the gas barrier layer, a layer containing a hydrophobic inorganic layered compound and a polymer material is used.

  Inorganic layered compounds include clay minerals, graphite, phosphate compounds, chalcogenides, and the like. Since the inorganic stratiform compound has a flat shape with a large diameter-thickness ratio (aspect ratio), mixing into the gas barrier layer can prevent moisture and gas from entering. The layered clayey material is an inorganic substance and has crystallinity, and has little gas molecule permeation in the thickness direction. Moreover, since it is flat shape, it is easy to pile up in the thickness direction. By laminating the layered clayey material in the thickness direction, it is assumed that the layered clayey material must be bypassed for the permeation of gas molecules, and the gas barrier property is exhibited by the curved path effect. According to said structure, it is excellent in long-term gas-barrier property, without using an aluminum layer. However, if the amount of the layered clayey material is too large, cracks may easily occur.

  The inorganic layered compound is preferably hydrophobic. If hydrophilic clay is used, moisture remaining in the film may enter the heat insulating material, and water vapor in the outside air may pass through after film formation, increasing the thermal conductivity, and under high temperature and high humidity. Causes further deterioration of thermal conductivity. Examples of the layered clayey material having hydrophobicity include montmorillonite, saponite, mica, or a mixture, and montmorillonite is particularly preferable. Montmorillonite has a flat shape with a major axis of 1 μm to 10 μm and a thickness of about 1 nm to 100 nm, and a film can be easily formed by flatness and surface charge.

  The clay-like material usually has a hydrophilic property because it has a hydroxyl group on its surface and an inorganic cation between layers. Water may remain in the hydrophilic inorganic layered compound. A hydrophilic clayey material can be dispersed in water and mixed with a water-soluble polymer to easily form a film. However, when such a hydrophilic substance is used as a gas barrier film, moisture can be introduced into the film. May penetrate and diffuse, increasing the internal gas and lowering the thermal conductivity. Further, under conditions of high temperature and humidity, water vapor is more easily transmitted, and it is difficult to exhibit sufficient gas barrier performance.

  Therefore, in the present invention, it was studied to use a hydrophobic layered clayey material as a gas barrier layer without using a conventional combination of a hydrophilic layered clayey material and a water-soluble polymer. Furthermore, a hydrophobic layered clayey material was combined with a hydrophobic polymer material. As a result, it has been found that it has a sufficient gas barrier property and can suppress deterioration of thermal conductivity with time even in a high temperature and humidity state. The feature of the present invention is that a hydrophobic layered clayey material is mixed in a polymer material. Even in the case of a hydrophilic clay-like material, the clay-like material can be made hydrophobic and mixed with the polymer material by substituting the organic cation for the inorganic cation present between the layers.

The polymer material is preferably hydrophobic for long-term use under high temperature and high humidity. If a resin that dissolves in water, such as polyvinyl alcohol, is used for the gas barrier layer, the internal gas increases due to the permeation of moisture (moisture residue) and water vapor remaining in the polyvinyl alcohol, particularly at high temperatures, and the thermal conductivity increases. This is because it may decrease. The water vapor permeability is preferably 100 cc / m ² · day (thickness 25 μm, 60 ° C./80% Rh) or less. For example, polymethyl methacrylate, polyacrylonitrile, polyacryl-styrene, polyacrylonitrile-butadiene, polyamide, and polyimide can be used, and any of these or a mixture thereof is preferable. By using a combination of a hydrophobic inorganic layered compound and a hydrophobic polymer material, it becomes a vacuum heat insulating material suitable for long-term use.

  By using a hydrophobic polymer material and a hydrophobic layered clay material, water vapor permeation can be suppressed even under high temperature (110 ° C.) and high humidity (60 ° C. and 80%) conditions, and the thermal conductivity is deteriorated over time. A small and highly durable vacuum heat insulating material can be provided. Moreover, since it is not necessary to use an aluminum foil having a large heat bridge as the gas barrier layer member of the jacket material, the heat bridge can be further reduced and the heat insulation performance can be improved.

  As the jacket material, other layers may be appropriately combined. According to the inorganic layered compound layer, the heat insulating effect can be improved even when aluminum foil or the like is not used, but the aluminum foil is particularly effective for maintaining a high degree of vacuum for a long period of time. When combined with the compound layer, durability for a longer period can be obtained. Examples of conventional gas barrier layers include those obtained by laminating an aluminum foil, an aluminum vapor deposition film, an ethylene-vinyl alcohol copolymer resin film, a polyester film, and the like. Further, a nylon film is attached as an overcoat layer, and a polyethylene film or a polypropylene film is used as a cover material for the weld layer. Any of the gas barrier layers having such a configuration may be replaced with the inorganic layered compound layer, or an inorganic layered compound layer may be added.

  Usually, since aluminum has a large thermal conductivity, a thin aluminum foil (about 6 μm) is used when aluminum is used. In addition, the thinner the aluminum foil, the more pinholes exist and the lower the gas barrier property, so the resin layer (ethylene-vinyl alcohol copolymer resin film, polyester film, polyester film, nylon film, polyvinyl alcohol, polyacrylonitrile, ethylene-vinyl) Alcohol copolymers, polyvinylidene chloride, polysaccharides, polyacrylic acid and esters thereof are laminated in several layers to supplement the pinholes in the aluminum foil. Resins such as polyvinyl alcohol (PVA), polyethylene vinyl alcohol (EVOH), and polyvinylidene chloride (PVDC) are preferable because of their high gas barrier properties. In the case of using a water-soluble resin (polyvinyl alcohol or the like), the thermal conductivity may be deteriorated due to the remaining moisture, and thus arrangement and combination are required. In addition, when the barrier property at a high temperature and high humidity is drastically reduced in a high hydrogen bond resin such as polyvinyl alcohol (PVA) or polyethylene vinyl alcohol (EVOH) that exhibits a barrier property by a hydrogen bond by a hydroxyl group Also pay attention to the conditions used. Further, since polyvinylidene chloride (PVDC) is a chlorine compound, there is a problem that dioxins are generated during incineration, and it is necessary to suppress its use as much as possible. Moreover, you may use the hybrid mixed material which mixed the inorganic material with such a resin layer. Examples of the inorganic compound to be mixed include montmorillonite, mica, hectorite, and saponite.

  As a core material (core material) of the vacuum heat insulating material, an inorganic fiber (glass wool or the like) having no binding material is preferable. In addition, the glass wool core material is preferably short fibers that are needled with glass wool having a fiber diameter of several μm or less. It is particularly preferable to use glass wool having an average fiber diameter of 3 to 5 μm. In addition, as a core material, a core material of powder or resin foam (perlite, silica, precipitated silica powder, glass wool, rock wool, foamed material of continuous foamed resin) is used. However, when inorganic powder, rock wool, continuous foamed resin, or the like is used, the thermal conductivity tends to be high (usually 5 mW / m · K or more). Since pearlite has a large heat conduction in the solid itself, the fine volume of the powder requires less space volume for heat insulation. This is because there are cases where there are few cases.

  As the getter agent, it is preferable to use a hydrophobic synthetic zeolite such as molecular sieve. Other examples include iron powder, synthetic zeolite, zirconium alloy, and barium-lithium alloy.

  In particular, the vacuum heat insulating material is used as a heat insulating member in a heat insulating box having a heat retaining portion and a heat insulating member for maintaining the temperature state of the heat retaining portion. When the vacuum heat insulating material of the present embodiment is used, the gas barrier property of the jacket material is improved, so that a heat insulating box having a low thermal conductivity can be obtained. It is effective for refrigerators and freezers with low temperature insulation parts, but is particularly effective for equipment such as water heaters, electric water heaters, insulation tubs, inverter modules, and solar heat collectors with high temperature insulation parts. . These devices are energy-saving devices with little heat transfer and low power consumption.

〔Example〕
In order to improve the gas barrier property, the present inventors selected a hydrophobic layered clayey material as an inorganic layered compound to be mixed in the gas barrier layer. A layered clayey material such as hydrophobic montmorillonite can be obtained by substituting an organic cation for an inorganic cation present between layers of a hydrophilic clayey material. The hydrophilic inorganic cation contained in montmorillonite or the like can be exchanged with an organic cation, and when substituted with an organic cation by an ion exchange reaction, the montmorillonite or the like becomes hydrophobic. The hydrophobic lamellar clay material can also be dispersed in the polymer.

  Specific examples of the layered clay material include products such as Kunipia D of Kunimine Industries, Lucentite SAN, Lucentite STN, and Lucentite SPN of Co-op Chemical.

  Hydrophilization of the lamellar clay material is performed by ion exchange of exchangeable inorganic ions such as sodium and magnesium of the lamellar clay with organic ions, and as a result, an organized lamellar clay material is generated. For ion exchange, organic onium ions can be used, for example, ammonium ion, pyridinium ion, sulfonium ion, and phosphonium ion. In particular, organic ammonium ions are easy to use. For example, organic ammonium ions and ions using quaternary ammonium salts such as alkylamine hydrochlorides and tetraalkylammonium salts obtained by cationizing organic amines such as dodecylamine, tetradecylamine, hexadecylamine and octadecylamine with hydrochloric acid. It is possible to exchange and organicize the layered clayey material. In that case, it is desirable to use an organic ammonium ion equivalent to the cation exchange amount of the layered clayey material.

  As the solvent for ion exchange, a protic solvent such as water or alcohol can be used due to the dispersibility of the layered clayey material. In the ion exchange method, the layered clayey material is sufficiently solvated with water, alcohol or the like, and then organic ammonium ions are added and further stirred to replace inorganic ions with organic ammonium ions between the layers of the layered clayey material. Thereafter, the ion-exchanged hydrophobic lamellar clay material is thoroughly washed, filtered and dried before use. The hydrophobic organically modified layered clayey material thus obtained is considered to have an insertion structure in which organic ammonium ions are inserted between the silicate layers, which are the main components, and are adsorbed on the silicate surface by ionic interaction. It is done. This structure makes it easier to attract the polymer material between the layers. The insertion structure can quantitate the interlayer spacing by wide-angle or small-angle X-ray scattering analysis.

  Moreover, as a result of analyzing the hydrophobic lamellar clay material produced using the tetraalkylammonium salt with a Fourier transform infrared spectrometer, a peak due to the tetraalkylammonium bentonite was observed. Therefore, it can be seen that the tetraalkylammonium salt is chemically bonded to the layered clayey material. Furthermore, when a gas generated by heating a hydrophobic layered clayey material prepared using a tetraalkylammonium salt was analyzed by gas chromatography, a tertiary amine which was a decomposition product of the tetraalkylammonium salt was detected. This also indicates that it is chemically bonded to the layered clay material.

  Solvents for dispersing and mixing the polymer material and the hydrophobic lamellar clay material include, for example, toluene, xylene, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, hexane, methanol, ethanol, isopropanol, ethyl acetate, dimethyl Formamide, dimethyl sulfoxide, methyl cellosolve, etc. can be used.

The polymer material to be mixed is preferably a hydrophobic material instead of the conventionally used hydrophilic polymer. In addition, a polymer material having a low water vapor permeability is preferable. That is, a 20 μm-thick polymer film having a moisture permeability of 100 cc / m ² · day (40 ° C., 90% RH) or less under high humidity conditions is preferable. Specific examples of the hydrophobic polymer material include polymethyl methacrylate, polyacrylonitrile, polyacryl-styrene, polyacrylonitrile-butadiene, polyamide, polyimide, and the like. Although the thickness of a gas barrier layer is not specifically limited, 10 nm-50 micrometers are suitable. When the gas barrier layer is 10 nm or less, the gas barrier property may be lowered unless attention is paid to the adjustment and handling of the thickness. Moreover, even if the gas barrier layer is thicker than 50 μm, the effect of improving the gas barrier property cannot be obtained, and cracks are more likely to occur.

  The gas barrier layer of the jacket material can be manufactured by coating and drying on the surface of the support. As the coating method, a roll coating method, a direct gravure method, a dip coating method, a doctor knife method, a die coating method, a blade method, a bar coating method, a spray method, a dipping method, a brush coating method and the like can be used. As a drying method, drying using hot air, dry air, infrared rays, microwaves, or the like can be arbitrarily used. Although there is no restriction | limiting in particular in drying temperature, Preferably it is 50-120 degreeC. The gas barrier layer may be a laminate composed of a plurality of layers.

  A welded layer or other film can be laminated on the gas barrier layer to improve heat sealability, moisture resistance, and puncture strength. As a film to be laminated, a thermoplastic resin film, an aluminum vapor deposition film, silica, an inorganic vapor deposition film, or the like can be used. As a method of laminating the thermoplastic film, there is a dry laminating method in which an adhesive layer is provided on the gas barrier layer and a thermoplastic resin film is laminated, and a melt extrusion lamination in which a thermoplastic resin is melt-extruded on the gas barrier layer to provide a thermoplastic resin layer. Examples thereof include a thermocompression bonding method in which a gas barrier layer and a thermoplastic resin are pressure-bonded by a hot roll.

  An overcoat layer serving as a support can be provided on the jacket material, and the shape can be appropriately selected from a synthetic resin film, a sheet, and a molded body. Specific examples of synthetic resins include polyethylene, polypropylene, cycloaliphatic polyolefin resin, polyethylene terephthalate, polyethylene naphthalate ester resin, nylon 6, nylon 66 polyamide resin, polylactic acid, polycaprolactone biodegradable resin, Examples of the resin include polymethyl methacrylate acrylic resin and polyacrylonitrile.

  Among these resins, polyethylene, polypropylene, polyethylene terephthalate, nylon 66 films and sheets are preferably used. The film may be a non-stretched film, a uniaxially stretched film or a biaxially stretched film. When the gas barrier layer is laminated on the support of these synthetic resins, the gas barrier layer may be laminated directly on the support, or may be laminated after treating the surface of the synthetic resin in order to improve adhesion. The synthetic resin surface treatment method includes corona discharge treatment, plasma discharge treatment, electron beam treatment, ultraviolet treatment, acid treatment, and the like.

  The inorganic fiber core material is preferably glass wool. The average fiber diameter of glass wool is preferably 3 to 5 μm. Glass wool varies greatly in thermal conductivity and cost depending on the average fiber diameter. With a fiber diameter in this range, 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. Moreover, the thing which does not contain a binder and the binder which produces outgas is preferable. This is to avoid deterioration of thermal conductivity.

  A getter agent contributes to the reduction of thermal conductivity by drying and removing moisture and gas components. In particular, a hydrophobic synthetic zeolite such as a molecular sieve which is difficult to adsorb moisture from the outside again after drying before the decompression step is preferable. As appropriate, silica gel, calcium oxide, synthetic zeolite, activated carbon and the like can be mixed and used.

  The vacuum heat insulating material of the present invention is suitable for a water heater, an electric water heater, a hot tub, etc. in which the use of the vacuum heat insulating material is in a high temperature and high humidity environment, but also for a heat insulating material used in a low temperature state such as a refrigerator. Can be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the measuring method of the water vapor permeability and the presence / absence of cracks performed in this example is as follows.

<Water vapor permeability>
The measurement was carried out with a GTR-100 manufactured by GTR Tech under humidified conditions (40 ° C., 90% RH) by a differential pressure type gas chromatography method according to JIS K 7126.

<Presence of cracks>
A coating film made of layered clayey material and polymer material is applied to a support film in which aluminum vapor deposition is formed on a polypropylene film, which is a welded layer of the jacket material, and then dried. The presence or absence of cracks was measured with a type mandrel bending tester.

  Table 1 shows the core materials used in the vacuum heat insulating materials of the examples and comparative examples, the gas barrier layer (layered clay material, polymer material) of the jacket material, water vapor permeability, crack presence, initial thermal conductivity, time The thermal conductivity after deterioration is shown. The material composition of the weld layer, gas barrier layer, and overcoat layer, the method for producing the vacuum heat insulating material, and the method for evaluating the thermal conductivity used in the present invention will be described in detail in each example.

  This example is an example of a gas barrier layer using hydrophobic montmorillonite and polymethyl methacrylate. Hydrophobic montmorillonite (Kunimine Kogyo Co., Ltd .; Kunipia D) is used as the layered clay material, polymethyl methacrylate is used as the hydrophobic polymer material, and the ratio of the polymer material to the layered clay material is 4: 1 (toluene solvent). , Nonvolatile content 3%) and dispersed to prepare a gas barrier solution (MA coating solution).

  A welding layer was formed as the first layer of the jacket material. The weld layer was a polypropylene film having a thickness of 50 μm. Aluminum vapor deposition was formed thereon to form a support film. The MA coating solution was applied on the aluminum vapor deposition layer by a roll coating method to form a gas barrier layer. The thickness of the gas barrier layer was about 10 μm. On the gas barrier layer, a stretched polypropylene film having a thickness of 12 μm and deposited with aluminum as an overcoat layer was laminated to prepare a jacket material.

  After heat-sealing the three sides of the jacketed aluminum material with a heat sealer, glass wool with an average fiber diameter of 3 μm (size: 250 mm x 250 mm x 100 mm) and a hydrophobic getter agent are inserted into the vacuum chamber. It was installed and evacuated with a rotary pump for 10 minutes and with a diffusion pump for 10 minutes until the pressure in the chamber reached 1.3 Pa. Thereafter, the end portion was sealed with a heat seal to obtain a vacuum heat insulating material.

  The thickness of the vacuum heat insulating material thus obtained was about 10 mm. When the thermal conductivity was measured using AUTO-Λ manufactured by Eihiro Seiki Co., Ltd., the initial thermal conductivity was 2.2 mW / m · K at 20 ° C. When a deterioration test was performed at 70 ° C. for one month, the thermal conductivity after the deterioration test was 2.8 mW / m · K. As described above, the vacuum heat insulating material of the present invention hardly deteriorated with time even when an aluminum-coated outer covering material was used. From this result, it was found that the vacuum heat insulating material of this example can maintain the thermal conductivity, and the heat bridge involved in the amount of heat leakage is small.

(Refrigerator example using the vacuum heat insulating material of Example 1)
The vacuum heat insulating material of Example 1 was inserted into the heat insulating part in the refrigerator box and used. This example is an example used around the refrigerator interior space. In FIG. 3, the cross-sectional schematic diagram of the refrigerator of a present Example is shown. Compared to the case where no vacuum heat insulating material is provided, the power consumption of the refrigerator is reduced by about 5%. Moreover, the heat insulation effect can be maintained for a long time. Furthermore, by using the vacuum heat insulating material, the heat insulating layer can be made thinner than the conventional heat insulating material, and the space in the cabinet can be widened with respect to the device volume. As is apparent from the drawing, it can be suitably used particularly around the refrigerator around the refrigerator, but it is also possible to cover the entire surface by forming a bent shape. Further, by filling the gap of the vacuum heat insulating material with a conventionally used heat insulating material (polyurethane or the like), higher heat insulating performance can be exhibited.

  This example is an example of a gas barrier layer using hydrophobic montmorillonite and polyacrylonitrile. Hydrophobic montmorillonite (Coop Chemical Co., Ltd .; Lucentite SAN) is used as the layered clay material, and polyacrylonitrile is used as the hydrophobic polymer material, and the mixture ratio is 3: 1 (toluene solvent, nonvolatile content 4%). A gas barrier solution (MB coating solution) was prepared by dispersing.

  Similar to Example 1, a welded layer was formed as the first layer of the jacket layer. The weld layer was a polypropylene film having a thickness of 50 μm, and an aluminum vapor deposition film was formed thereon to form a support film. The MB coating solution was applied on the aluminum vapor deposition layer by a roll coating method to form a gas barrier layer of about 10 μm. A 12 μm stretched polypropylene film deposited with aluminum was laminated as an overcoat layer on the gas barrier layer to prepare a jacket material.

  After heat-sealing the three sides of the jacket material with a heat sealer, glass wool with an average fiber diameter of 3 μm (size: 250 mm × 250 mm × 100 mm) and a hydrophobic getter agent are inserted into the vacuum chamber of the vacuum packaging machine. It was installed and evacuated with a rotary pump for 10 minutes and with a diffusion pump for 10 minutes until the pressure in the chamber reached 1.3 Pa. Thereafter, the end portion was sealed with a heat seal to obtain a vacuum heat insulating material.

  The thickness of the vacuum heat insulating material thus obtained was about 10 mm. When the thermal conductivity was measured using AUTO-Λ manufactured by Eihiro Seiki Co., Ltd. as in Example 1, the initial thermal conductivity was 2.5 mW / m · K at 20 ° C. When a deterioration test was performed at 110 ° C. for one month, the thermal conductivity after the deterioration test was 3.2 mW / m · K. As described above, the vacuum heat insulating material of the present invention hardly deteriorated with time even when an aluminum-coated outer covering material was used. From this result, it can be seen that the vacuum heat insulating material of this example has little deterioration in thermal conductivity with time even in a high temperature environment, can maintain the thermal conductivity, and has a small heat bridge related to the amount of heat leakage. It was.

(Example of a water heater using the vacuum heat insulating material of Example 2)
The vacuum heat insulating material of Example 2 was used around the hot water storage tank of the water heater. FIG. 4 shows a schematic cross-sectional view of the water heater of this embodiment. Since the periphery of the water heater becomes high temperature (100 ° C. or higher), conventionally, a vacuum heat insulating material could not be laid. When the vacuum heat insulating material of Example 2 was used, the power consumption of the water heater was reduced by about 3% compared to the case where no vacuum heat insulating material was provided. Furthermore, since the heat insulating layer can be made thinner than the conventional heat insulating material by using the vacuum heat insulating material of the present embodiment, the capacity of the hot water storage tank can be increased with respect to the apparatus volume. Moreover, the heat insulation effect of the vacuum heat insulating material of a present Example can be maintained for a long period of time.

  This example is an example of a gas barrier layer using hydrophobic montmorillonite and polyacryl-styrene. Hydrophobic montmorillonite (Coop Chemical Co., Ltd .; Lucentite STN) is used as the layered clay material, and polyacryl-styrene is used as the hydrophobic polymer material, with a mixing ratio of 2: 1 (xylene solvent, nonvolatile content 3%). A gas barrier solution (MC coating solution) was prepared by mixing and dispersing.

  As the covering material, unstretched polypropylene having a thickness of 40 μm was used as the first layer, and an aluminum vapor deposition layer was formed thereon. Moreover, the aluminum vapor deposition layer was formed on the 25 micrometer-thick biaxially-stretched polypropylene film as a 2nd layer. The first layer and the second layer were laminated by dry lamination. Then, MC coating liquid was apply | coated by the roll coating method on the biaxially stretched polypropylene film surface, and the gas barrier layer of about 10 micrometers was formed. This gas barrier layer also serves as an overcoat layer. A vacuum heat insulating material was manufactured using the jacket material thus manufactured.

  After heat-sealing the three sides of the jacket material with a heat sealer, glass wool with an average fiber diameter of 5 μm (size: 250 mm × 250 mm × 120 mm) and a hydrophobic getter agent are inserted into the vacuum chamber of the vacuum packaging machine. It was installed and evacuated with a rotary pump for 10 minutes and with a diffusion pump for 10 minutes until the pressure in the chamber reached 1.3 Pa. Thereafter, the end portion was sealed with a heat seal to obtain a vacuum heat insulating material.

  The thickness of the vacuum heat insulating material thus obtained was about 12 mm. When the thermal conductivity was measured using AUTO-Λ manufactured by Eihiro Seiki Co., Ltd. as in Example 1, the initial thermal conductivity was 2.9 mW / m · K at 20 ° C. When a deterioration test was performed at 110 ° C. for one month, the thermal conductivity after the deterioration test was 3.6 mW / m · K. As described above, the vacuum heat insulating material of the present invention hardly deteriorated with time even when an aluminum-coated outer covering material was used. From this result, it can be seen that the vacuum heat insulating material of this example has little deterioration in thermal conductivity with time even in a high temperature environment, can maintain the thermal conductivity, and has a small heat bridge related to the amount of heat leakage. It was.

(Example of electric water heater using vacuum heat insulating material Example 3)
The vacuum heat insulating material of Example 3 was used in the interior space of an electric water heater, particularly around a hot water storage tank. In FIG. 5, the cross-sectional schematic diagram of the electric water heater of a present Example is shown. Since the peripheral part of the electric water heater is also hot, conventionally, a vacuum heat insulating material could not be laid. When the vacuum heat insulating material of Example 3 was used, the power consumption was reduced by about 3% compared to the case where no vacuum heat insulating material was provided. By using the vacuum heat insulating material of the present embodiment, the heat insulating layer can be made thinner than the conventional heat insulating material, so that the capacity of the hot water storage tank can be increased with respect to the device volume. Moreover, the heat insulation effect of the vacuum heat insulating material of a present Example can be maintained for a long period of time.

  This example is an example of a gas barrier layer using hydrophobic montmorillonite and polyacrylonitrile-butadiene. Hydrophobic montmorillonite (Kunimine Kogyo Co., Ltd .; Kunipia D) is used as the layered clay material, and polyacrylonitrile-butadiene is used as the hydrophobic polymer material, blended in a 2: 1 blending ratio (toluene solvent, non-volatile content 3%). -Dispersed to prepare a gas barrier solution (MD coating solution).

  Similar to Example 1, a welded layer was formed as the first layer of the jacket layer. The weld layer was a polypropylene film having a thickness of 50 μm, and an aluminum vapor deposition film was formed thereon to form a support film. An MD coating solution was applied on the aluminum vapor deposition layer by a roll coating method to form a gas barrier layer of about 10 μm. A 12 μm stretched polypropylene film deposited with aluminum was laminated as an overcoat layer on the gas barrier layer to prepare a jacket material.

  After heat-sealing the three sides of the jacket material with a heat sealer, glass wool with an average fiber diameter of 3 μm (size: 250 mm × 250 mm × 100 mm) and a hydrophobic getter agent are inserted into the vacuum chamber of the vacuum packaging machine. It was installed and evacuated with a rotary pump for 10 minutes and with a diffusion pump for 10 minutes until the pressure in the chamber reached 1.3 Pa. Thereafter, the end portion was sealed with a heat seal to obtain a vacuum heat insulating material.

  The thickness of the vacuum heat insulating material thus obtained was about 10 mm. When the thermal conductivity was measured using AUTO-Λ manufactured by Eihiro Seiki Co., Ltd. as in Example 1, the initial thermal conductivity was 2.5 mW / m · K at 20 ° C. When a deterioration test was conducted for one month under high humidity conditions of 60 ° C. and 80%, the thermal conductivity after the deterioration test was 3.2 mW / m · K. As described above, the vacuum heat insulating material of the present invention was less deteriorated with time under high humidity conditions even when an aluminum-coated outer covering material was used. As a result, the vacuum heat insulating material of the present example has little deterioration in thermal conductivity over time even in a high humidity environment, can maintain the thermal conductivity, and the heat bridge involved in the amount of heat leakage is also small. understood.

(Example of a warm tub using the vacuum heat insulating material of Example 4)
The vacuum heat insulating material of Example 4 was inserted around the tub and used as a heat insulation tub. FIG. 6 shows a cross-sectional view of the heat insulation bathtub of this embodiment. The peripheral part of the heat insulation bathtub is hot, and conventionally, a vacuum heat insulating material could not be laid. When the vacuum heat insulating material of Example 4 was used, the power consumption was reduced by about 4% compared to the case where no vacuum heat insulating material was provided. By using the vacuum heat insulating material of the present embodiment, the heat insulating layer can be made thinner than the conventional heat insulating material, so that the bathroom and the bathtub can be widened. Moreover, the heat insulation effect of the vacuum heat insulating material of a present Example can be maintained for a long time.

  This example is an example of a gas barrier layer using hydrophobic montmorillonite and polyamide. Hydrophobic montmorillonite (Coop Chemical Co., Ltd .; Lucentite SEN) is used as the layered clay material, and polyamide is used as the hydrophobic polymer material. Formulated at a 1: 1 mixing ratio (dimethylformamide solvent, nonvolatile content 5%) A gas barrier solution (ME coating solution) was prepared by dispersing.

  Similar to Example 1, a welded layer was formed as the first layer of the jacket layer. The weld layer was a polypropylene film having a thickness of 50 μm, and an aluminum vapor deposition film was formed thereon to form a support film. An ME coating solution was applied on the aluminum vapor deposition layer by a roll coating method to form a gas barrier layer of about 10 μm. A 12 μm stretched polypropylene film deposited with aluminum was laminated as an overcoat layer on the gas barrier layer to prepare a jacket material.

  After heat-sealing the three sides of the jacket material with a heat sealer, glass wool with an average fiber diameter of 4 μm (size: 250 mm × 250 mm × 80 mm) and a hydrophobic getter agent are inserted into the vacuum chamber of the vacuum packaging machine. It was installed and evacuated with a rotary pump for 10 minutes and with a diffusion pump for 10 minutes until the pressure in the chamber reached 1.3 Pa. Thereafter, the end portion was sealed with a heat seal to obtain a vacuum heat insulating material.

  The thickness of the vacuum heat insulating material thus obtained was about 8 mm. When the thermal conductivity was measured using AUTO-Λ manufactured by Eihiro Seiki Co., Ltd. as in Example 1, the initial thermal conductivity was 2.9 mW / m · K at 20 ° C. When a deterioration test was performed at 110 ° C. for one month, the thermal conductivity after the deterioration test was 3.6 mW / m · K. As described above, the vacuum heat insulating material of the present invention hardly deteriorated with time even when an aluminum-coated outer covering material was used. From this result, it can be seen that the vacuum heat insulating material of this example has little deterioration in thermal conductivity with time even in a high temperature environment, can maintain the thermal conductivity, and has a small heat bridge related to the amount of heat leakage. It was.

  This example is an example of a gas barrier layer using hydrophobic montmorillonite and polyimide. Hydrophobic montmorillonite (Coop Chemical Co., Ltd .; Lucentite SPN) is used as the layered clay material, and polyimide is used as the hydrophobic polymer material, and is blended at a 1: 1 mixing ratio (dimethylformamide solvent, non-volatile content 6%). A gas barrier solution (MF coating solution) was prepared by dispersing.

  Similar to Example 1, a welded layer was formed as the first layer of the jacket layer. The weld layer was a polypropylene film having a thickness of 50 μm, and an aluminum vapor deposition film was formed thereon to form a support film. An MF coating solution was applied on the aluminum vapor deposition layer by a roll coating method to form a gas barrier layer of about 10 μm. A 12 μm stretched polypropylene film deposited with aluminum was laminated as an overcoat layer on the gas barrier layer to prepare a jacket material.

  After heat-sealing the three sides of the jacket material with a heat sealer, glass wool with an average fiber diameter of 3 μm (size: 250 mm x 250 mm x 100 mm and a hydrophobic getter agent is inserted and installed in the vacuum chamber of the vacuum packaging machine. Then, it was evacuated with a rotary pump for 10 minutes and with a diffusion pump for 10 minutes until the pressure in the chamber reached 1.3 Pa. The rear end portion was sealed with a heat seal to obtain a vacuum heat insulating material.

  The thickness of the vacuum heat insulating material thus obtained was about 10 mm. When the thermal conductivity was measured using AUTO-Λ manufactured by Eihiro Seiki Co., Ltd. as in Example 1, the initial thermal conductivity was 2.8 mW / m · K at 20 ° C. When a one month deterioration test was performed at 60 ° C. and 80% high humidity, the thermal conductivity after the deterioration test was 3.5 mW / m · K. As described above, the vacuum heat insulating material of the present invention had little deterioration with time under high humidity conditions even when an aluminum-coated outer covering material was used. As a result, the vacuum heat insulating material of the present example has little deterioration in thermal conductivity over time even in a high humidity environment, can maintain the thermal conductivity, and the heat bridge involved in the amount of heat leakage is also small. understood.

  As a gas barrier layer of the present invention, hydrophobic montmorillonite (Kunimine Industry Co., Ltd .; Kunipia D) is used as a lamellar clay material, and polycarbonate is used as a hydrophobic polymer material in a mixing ratio of 4: 1 (toluene solvent, nonvolatile content 3%). A dispersed gas barrier solution (MG coating solution) was prepared. Then, the support film which formed aluminum vapor deposition on the 50-micrometer-thick polypropylene film was used as a welding layer for the 1st layer of the jacket material. Thereafter, a gas barrier layer of about 10 μm is formed by roll coating with the MG coating solution of the second layer on the aluminum vapor deposition on the first layer, and further, a 12 μm stretched polypropylene deposited with aluminum as an overcoat on the third layer. The film was laminated to produce a jacket material.

  After vacuum welding the three sides of the above-mentioned jacket material deposited with aluminum with a heat sealer, after inserting glass wool with an average fiber diameter of 3 μm (size: 250 mm × 250 mm × 100 mm) and a hydrophobic getter agent, It was installed in a vacuum chamber and evacuated with a rotary pump of the vacuum packaging machine for 10 minutes and with a diffusion pump for 10 minutes until the pressure in the chamber became 1.3 Pa. Then, the edge part was sealed by heat sealing.

The thermal conductivity of the vacuum heat insulating material (thickness: about 10 mm) thus obtained was measured. The initial thermal conductivity was 2.2 mW / m · K under the condition of 20 ° C. using AUTO-Λ manufactured by Eihiro Seiki Co., Ltd., and the heat insulation performance was excellent. When a deterioration test was performed at 70 ° C. for one month, the thermal conductivity after the deterioration test was 8.0 mW / m · K. Therefore, when a hydrophobic resin having a high water vapor permeability (100 g / m ² · day or more) is used, it is suitable to use under normal conditions in order to suppress the deterioration of thermal conductivity over time.

[Comparative Example 1]
Comparative Example 1 is an example of a gas barrier layer using hydrophilic montmorillonite and water-soluble polyvinyl alcohol. Uses hydrophilic montmorillonite (Kunimine Kogyo Co., Ltd .; Kunipia F) as a layered clay material, and water-soluble polyvinyl alcohol as a polymer material, and is blended at a 1: 1 blending ratio (toluene solvent, nonvolatile content 3%). A gas barrier solution (MH coating solution) was prepared by dispersing.

  Similar to Example 1, a welded layer was formed as the first layer of the jacket layer. The weld layer was a polypropylene film having a thickness of 50 μm, and an aluminum vapor deposition film was formed thereon to form a support film. An MH coating solution was applied on the aluminum vapor deposition layer by a roll coating method to form a gas barrier layer of about 15 μm.

  However, the adhesion between the support film and the gas barrier layer was low, causing peeling and cracking. A 12 μm stretched polypropylene film was laminated as an overcoat layer on the gas barrier layer to prepare a jacket material.

  After heat-sealing the three sides of the jacket material with a heat sealer, glass wool with an average fiber diameter of 6 μm (size: 250 mm × 250 mm × 100 mm) and a synthetic zeolite getter agent are inserted into the vacuum chamber of the vacuum packaging machine. It was installed and evacuated with a rotary pump for 10 minutes and with a diffusion pump for 10 minutes until the pressure in the chamber reached 1.3 Pa. Thereafter, the end portion was sealed with a heat seal to obtain a vacuum heat insulating material.

  The thickness of the vacuum heat insulating material thus obtained was about 10 mm. When the thermal conductivity was measured using AUTO-Λ manufactured by Eihiro Seiki Co., Ltd. as in Example 1, the initial thermal conductivity was high at 4.2 mW / m · K at 20 ° C. When a deterioration test was conducted at 70 ° C. for one month, the heat conductivity after the deterioration test was 9.6 mW / m · K. From this, when the hydrophilic montmorillonite and the polyvinyl alcohol which is a water-soluble polymer material were used, the heat insulation performance was lower than when the hydrophobic viscosity material was used. In addition, cracks were generated and the thermal conductivity was greatly deteriorated with time. Moreover, it turned out that heat bridge also becomes large and deterioration of thermal conductivity cannot be suppressed. The reason why the initial thermal conductivity was increased is that the average fiber diameter of glass wool was increased to 6 μm.

[Comparative Example 2]
This comparative example is an example of a gas barrier layer using hydrophilic montmorillonite and methylcellulose as a water-soluble polymer. As in Comparative Example 1, a hydrophilic layered clay material montmorillonite (Kunimine Industry Co., Ltd .; Kunipia F) is used as the layered clay material, and water-soluble methylcellulose is used as the polymer material. A gas barrier solution (MI coating solution) in which a molecular material was dispersed at a mixing ratio of 2: 1 (toluene solvent, nonvolatile content 3%) was prepared.

  A welding layer was formed as the first layer of the jacket material. The weld layer was a polypropylene film having a thickness of 50 μm. Aluminum vapor deposition was formed thereon to form a support film. An MI coating solution was applied on the aluminum vapor deposition layer by a roll coating method to form a gas barrier layer. The thickness of the gas barrier layer was about 10 μm. However, the adhesion between the support film and the gas barrier layer was low, and the gas barrier layer peeled off and cracks occurred. The stretched polypropylene film having a thickness of 12 μm and deposited with aluminum as the third overcoat layer was laminated as it was to prepare a jacket material.

  After heat-sealing the three sides of the jacketed aluminum material with a heat sealer, glass wool with an average fiber diameter of 4 μm (size: 250 mm x 250 mm x 80 mm) and a synthetic zeolite getter agent are inserted into the vacuum chamber. It was installed and evacuated with a rotary pump for 10 minutes and with a diffusion pump for 10 minutes until the pressure in the chamber reached 1.3 Pa. Thereafter, the end portion was sealed with a heat seal to obtain a vacuum heat insulating material.

  The thickness of the vacuum heat insulating material thus obtained was about 8 mm. When the thermal conductivity was measured using AUTO-Λ manufactured by Eihiro Seiki Co., Ltd., the initial thermal conductivity was 4.0 mW / m · K at 20 ° C. When a deterioration test was conducted at 110 ° C. for one month, the thermal conductivity after the deterioration test was 14.5 mW / m · K. From this, when hydrophilic montmorillonite is used as a layered clay material and water-soluble methylcellulose is used as a polymer material, cracks occur in the gas barrier layer and the vacuum heat insulating material is placed in a high temperature environment. The deterioration of thermal conductivity could not be suppressed.

[Comparative Example 3]
This comparative example is an example of a gas barrier layer using hydrophilic montmorillonite and polyvinyl alcohol. Hydrophilic montmorillonite (Kunimine Kogyo Co., Ltd .; Kunipia F) is used as the layered clay material, and water-soluble polyvinyl alcohol is used as the polymer material. The ratio of the polymer material to the layered clay material is 1: 2. , Nonvolatile content 4%), and dispersed to prepare a gas barrier solution (MJ coating solution).

  A welding layer was formed as the first layer of the jacket material. The weld layer was a polypropylene film having a thickness of 50 μm. A gas barrier layer of about 15 μm was formed on the second layer MJ coating solution by roll coating. The adhesion between the polypropylene film and the gas barrier layer was low, and the gas barrier layer was peeled off. In addition, cracks in the gas barrier layer occurred. The stretched polypropylene film having a thickness of 12 μm and deposited with aluminum as the third overcoat layer was laminated as it was to prepare a jacket material.

  Three sides of the jacket material are heat welded with a heat sealer, glass wool with an average fiber diameter of 5 μm (size: 250 mm × 250 mm × 100 mm) and a getter agent of synthetic zeolite are inserted and placed in a vacuum chamber. The pressure was evacuated with a rotary pump for 10 minutes and with a diffusion pump for 10 minutes until the pressure reached 1.3 Pa. Thereafter, the end portion was sealed with a heat seal to obtain a vacuum heat insulating material.

  The thickness of the vacuum heat insulating material thus obtained was about 10 mm. When the thermal conductivity was measured using AUTO-Λ manufactured by Eihiro Seiki Co., Ltd., the initial thermal conductivity was 4.3 mW / m · K at 20 ° C. When a deterioration test was conducted for one month at a temperature of 60 ° C. and a humidity of 80%, the thermal conductivity after the deterioration test was 12.5 mW / m · K. As described above, the vacuum heat insulating material of the present invention hardly deteriorated with time even when an aluminum-coated outer covering material was used. From this result, it was found that the vacuum heat insulating material of this example can maintain the thermal conductivity, and the heat bridge involved in the amount of heat leakage is small. Therefore, when hydrophilic montmorillonite and water-soluble polyvinyl alcohol are used, cracks occur in the gas barrier layer, and if the vacuum insulation is placed in a high temperature / high humidity environment, the thermal conductivity is degraded. Could not be suppressed.

  By using a hydrophobic lamellar clay material and a hydrophobic polymer material for the gas barrier layer of the vacuum insulation material, cracks do not occur and water vapor permeability is excellent. Therefore, it is possible to produce a vacuum heat insulating material that has little deterioration with time in thermal conductivity and can withstand high temperatures and high humidity. In addition, by applying this vacuum heat insulating material to a water heater, an electric water heater, a hot tub, or the like, the amount of power consumption can be reduced, and energy saving equipment can be provided.

The cross-sectional schematic diagram of this invention vacuum heat insulating material. The cross-sectional schematic diagram of the conventional vacuum heat insulating material. The refrigerator provided with the vacuum heat insulating material of this invention. The water heater provided with the vacuum heat insulating material of this invention. The electric water heater provided with the vacuum heat insulating material of this invention. The heat insulation bathtub provided with this invention vacuum heat insulating material.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conventional vacuum heat insulating material 2 Conventional covering material 3 Glass wool 4 Getter agent 5 Welding layer 6 Gas barrier layer (aluminum vapor deposition resin film)
7 Gas barrier layer (aluminum foil)
8 Overcoat layer 9 Invention vacuum heat insulating material 10 Invention jacket material 11 Gas barrier layer (layered clay mineral layer)
12 Rigid urethane foam 13 Box 14 Refrigerator box 15 Hot water storage tank 16 Relief valve 17 Earth leakage breaker 18 Relief valve operation valve 19 Drainage operation valve 20 Drainage pipe 21 Main plug 22 Water supply pipe 23 Water stoppage valve 24 Hot water supply pipe 25 Hot water storage tank unit 26 Heat pump unit 27 bathtub

Claims (9)

It consists of a core material of inorganic fiber, a getter agent, and a jacket material covering the core material and the getter agent, and is a vacuum heat insulating material in which the inside of the jacket material is decompressed,
The jacket material includes a weld layer for hermetically sealing a peripheral portion, a gas barrier layer for reducing moisture and gas permeability, and the gas barrier layer includes a layered clayey material having hydrophobicity and a polymer A vacuum heat insulating material characterized by containing a material.   2. The vacuum heat insulating material according to claim 1, wherein the polymer material is hydrophobic. 2. The vacuum heat insulating material according to claim 1, wherein the polymer material has a water vapor permeability of 100 cc / m ² · day or less.   2. The vacuum heat insulating material according to claim 1, wherein the polymer material contains one or more of polymethyl methacrylate, polyacrylonitrile, polyacryl-styrene, polyacrylonitrile-butadiene, polyamide, polyimide. Vacuum insulation material characterized by   2. The vacuum heat insulating material according to claim 1, wherein the layered clayey material contains one or more of montmorillonite, saponite, mica.   2. The vacuum heat insulating material according to claim 1, wherein the core material is glass wool having an average fiber diameter of 3 to 5 [mu] m.   The vacuum heat insulating material according to claim 1, wherein the getter agent is a hydrophobic synthetic zeolite. A heat insulation box having a heat insulation part and a heat insulation member that maintains the temperature state of the heat insulation part,
The heat insulating member is a vacuum heat insulating material, and the vacuum heat insulating material is the vacuum heat insulating material according to any one of claims 1 to 7.   The refrigerator provided with the vacuum heat insulating material as described in any one of Claim 1 thru | or 7.

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