JP6201494B2 - Gas barrier laminate and vacuum insulation exterior material - Google Patents

Description

  The present invention relates to a gas barrier laminate comprising two gas barrier films bonded together with an isocyanate adhesive. This gas barrier laminate can be used as an exterior material for a vacuum heat insulating material by further laminating a heat seal layer or the like.

  Vacuum insulation material wraps the core material with the exterior material, seals the surrounding exterior material with the vacuum around the core material, and seals it, thereby making the thermal conductivity of the gas close to zero as much as possible. It is a heat insulating material with improved performance.

  The exterior material is required to have a gas barrier property in order to maintain the internal vacuum. However, since the conventional vacuum heat insulating material uses aluminum foil as a gas barrier film, the heat insulating effect of the vacuum heat insulating material is reduced by heat conduction that travels through the vacuum heat insulating material, that is, a so-called heat bridge phenomenon.

  Therefore, in order to solve the heat bridge phenomenon, there is a vacuum heat insulating material using an exterior material in which the gas barrier film is not a metal foil but a gas barrier film (deposited film) having a deposited film (for example, Patent Document 1). ~ 2). According to Patent Document 2, it is desirable to laminate a plurality of vapor deposition films in order to improve the gas barrier properties, and it is desirable to arrange a plurality of vapor deposition films so that the vapor deposition surfaces face each other when laminating. It is described. Lamination is possible, for example, by dry lamination.

JP 2006-21429 A JP 2010-138956 A

  A typical example of the adhesive used for dry lamination is an isocyanate adhesive. Therefore, when a plurality of vapor-deposited films are bonded together using an isocyanate-based adhesive, a slight amount of carbon dioxide gas is generated due to the curing reaction of the isocyanate group of this adhesive. And there existed a problem that this carbon dioxide gas might remain between two vapor deposition films, and may produce a bubble.

  Therefore, an object of the present invention is to provide a laminate that does not generate bubbles due to an isocyanate-based adhesive when two gas barrier films are bonded together with an isocyanate-based adhesive.

  By the way, the present inventor uses one of the two gas barrier films as a film in which an inorganic thin film is formed on a specific vapor deposition substrate, and the vapor deposition substrate is the isocyanate-based adhesive. It has been found that bubbles caused by the isocyanate-based adhesive do not occur when arranged so as to come into contact with each other.

  Although the mechanism of action is not clear, it can be assumed that the generated carbon dioxide gas is absorbed by the specific vapor deposition base material, or is discharged to the outside through the specific vapor deposition base material from its end face.

Therefore, the invention according to claim 1 is a gas barrier laminate comprising two gas barrier films bonded together with an isocyanate-based adhesive.
Of two of the gas barrier film, a first gas barrier film one, when the other was a second gas barrier film, the first deposition substrate the first gas barrier film is made of polyethylene terephthalate film A first inorganic thin film made of a metal oxide is formed thereon, the first vapor deposition substrate is disposed so as to contact the isocyanate-based adhesive , and the second A gas barrier film is obtained by forming a second inorganic thin film made of an aluminum thin film on a second vapor deposition substrate made of an ethylene-vinyl alcohol copolymer film, and the isocyanate of the first gas barrier film. A surface protective layer made of a biaxially stretched nylon film is laminated on the side not in contact with the adhesive, and the second gas barrier film On the side not in contact with the isocyanate-based adhesive Lum heat seal layer is a gas barrier laminate, characterized in that it is laminated.

Next, claims 2 and 3 are inventions in which the respective materials are specified on the premise of the invention of claim 1 .

The invention described in Claim 2 is a gas barrier laminate according to claim 1, wherein the inorganic thin film of the first gas barrier film is a thin film of alumina.

The invention described in Claim 3 is a gas barrier laminate according to claim 1, wherein the inorganic thin film of the first gas barrier film is a thin film of silicon oxide.

  The second gas barrier film is composed of alumina as the inorganic thin film of the first gas barrier film for reasons such as high gas barrier properties, high bending resistance, and no deterioration in gas barrier properties even when bent. However, what formed the thin film of aluminum on the vapor deposition base material which consists of an ethylene-vinyl alcohol copolymer film is excellent.

Next, the invention of claim 4, relates to a vacuum insulation material for exterior materials used as part of a gas barrier laminate according to any one of claims 1 to 3 according to claim 1 to 3 It is the exterior material for vacuum heat insulating materials which contains the gas-barrier laminated body in any one in the layer structure.

That is, by laminating a heat seal layer or the like on the inner surface side of the gas barrier laminate according to any one of claims 1 to 3 , it can be used as a vacuum heat insulating material exterior material. In addition to laminating a heat seal layer on the inner surface side of the gas barrier laminate, a surface protective layer is laminated on the outer surface side, or an intermediate reinforcing layer is laminated between the gas barrier laminate and the heat seal layer. And it is good also as an exterior material for vacuum heat insulating materials.

  As described above, according to the present invention, when two gas barrier films are bonded together with an isocyanate-based adhesive, it is possible to prevent bubbles caused by the isocyanate-based adhesive.

The principal part sectional drawing of the exterior material for vacuum heat insulating materials which concerns on this invention. Sectional drawing of the vacuum heat insulating material using the exterior material for vacuum heat insulating materials which concerns on this invention. Sectional drawing for demonstrating the bending part of the vacuum heat insulating material using the exterior material for vacuum heat insulating materials which concerns on this invention. The top view of the vacuum heat insulating material using the exterior material for vacuum heat insulating materials which concerns on this invention. Sectional drawing of the principal part of the exterior material for vacuum heat insulating materials which concerns on the comparative example 1. FIG. The principal part sectional drawing of the exterior material for vacuum heat insulating materials which concerns on the comparative example 2. FIG. The principal part sectional drawing of the exterior material for vacuum heat insulating materials which concerns on the comparative example 3. FIG.

  The present invention will be described with reference to an exterior material for a vacuum heat insulating material using the gas barrier laminate of the present invention. FIG. 1 is a cross-sectional view illustrating an example of the vacuum heat insulating material exterior material 1.

  The gas barrier laminate of the present invention comprises two gas barrier films and an isocyanate adhesive as essential components. In order to distinguish between the two gas barrier films, one of them is called a first gas barrier film and the other is called a second gas barrier film, which will be described below. When the exterior material 1 for a vacuum heat insulating material is prepared using the gas barrier laminate of the present invention, generally, the first gas barrier film is positioned on the outer side and the second gas barrier film is positioned on the inner surface side. Is.

  Then, the first gas barrier film and the second gas barrier film are bonded to each other with an isocyanate adhesive interposed therebetween, and the isocyanate adhesive is reacted and cured to obtain the gas barrier laminate of the present invention. it can. For convenience of explanation, an adhesive layer obtained by reaction curing of an isocyanate adhesive is hereinafter referred to as a “urethane adhesive layer”.

  And the exterior material 1 for vacuum heat insulating materials can be obtained by laminating | stacking a heat seal layer on the inner surface side of the gas-barrier laminated body obtained in this way, ie, a 2nd gas-barrier film. In addition to the heat seal layer, a surface protective layer or an intermediate reinforcing layer may be laminated to form the vacuum heat insulating material exterior material 1.

  In FIG. 1, a first gas barrier film 20 and a second gas barrier film 30 are bonded together via a urethane-based adhesive layer ad2, and a heat seal layer 40 is provided on the inner surface side, and a surface protective layer 10 is provided on the outer surface side. The exterior material 1 for vacuum heat insulating materials obtained by laminating | stacking is shown. The heat seal layer 40 and the surface protective layer 10 can be bonded together via urethane adhesive layers ad3 and ad1. For this reason, the vacuum heat insulating exterior material 1 shown in FIG. 1 has a surface protective layer 10, a urethane-based adhesive layer ad1, a first gas barrier film 20, a urethane-based adhesive layer ad2, 2 gas barrier film 30, urethane adhesive layer ad 3, and heat seal layer 40.

In the present invention, the first gas barrier film 20 needs to be configured by forming the inorganic thin film 22 on the vapor deposition substrate 21. In addition, in order to distinguish from the case where the 2nd gas barrier film 30 is comprised by forming the inorganic thin film 32 on the vapor deposition base material 31, the vapor deposition base material 21 of the 1st gas barrier film 20 is "1st. The inorganic thin film 22 formed on the first vapor deposition substrate is called “first inorganic thin film” 22. On the other hand, the vapor deposition substrate 31 of the second gas barrier film 30 is referred to as a “second vapor deposition substrate” 31, and the inorganic thin film 32 formed on the second vapor deposition substrate 31 is referred to as the “second vapor deposition substrate 31”. It is called “inorganic thin film” 32.

  And the 1st vapor deposition base material 21 needs to be arrange | positioned so that the urethane type adhesive bond layer ad2 may be contacted.

  If the first deposition base material 21 is not in contact with the urethane-based adhesive layer ad2 and the first inorganic thin film 22 is disposed in contact with the urethane-based adhesive layer ad2, a comparison described later is performed. As in Example 1, bubbles may be generated in the urethane-based adhesive layer ad2 due to reaction hardening of the urethane-based adhesive layer ad2.

  Moreover, the 1st vapor deposition base material 21 needs to be comprised with the plastic film of a specific material. When a plastic film of a material other than this is in contact with the urethane-based adhesive layer ad2, bubbles are generated in the urethane-based adhesive layer ad2 due to reaction hardening of the urethane-based adhesive layer ad2. There is.

  A plastic film suitable for the first vapor deposition substrate 21 is a plastic film having a melting point of 150 ° C. or higher. Moreover, a polyethylene terephthalate film can also be used as the first vapor deposition substrate 21. As can be seen from Example 1 to be described later, a polyethylene terephthalate film having a melting point of 150 ° C. or higher is used as the first vapor deposition substrate 21, and the polyethylene terephthalate film is disposed so as to be in contact with the urethane-based adhesive layer ad2. In such a case, no bubbles are generated due to reaction hardening of the urethane-based adhesive layer ad2.

  As the first inorganic thin film 22, a metal or metal oxide thin film can be used. As the metal thin film, an aluminum thin film, a cobalt thin film, a nickel thin film, a zinc thin film, a copper thin film, a silver thin film, or a thin film of these alloys can be used. As the metal oxide thin film, an alumina thin film or a silicon oxide thin film can be used. An alumina thin film is desirable. In addition, a diamond-like carbon thin film can be used as the first inorganic thin film 22. The 1st inorganic thin film 22 can be formed on the 1st vapor deposition base material 21 by vapor phase growth methods, such as a vacuum evaporation method, sputtering method, CVD method, for example. Further, prior to the formation of the first inorganic thin film 22, the surface of the first vapor deposition substrate 21 may be chemically or physically treated.

  Next, as the second gas barrier film 30, a vapor deposition film configured by forming the second inorganic thin film 32 on the second vapor deposition substrate 31 can be used. In addition, a metal foil can also be used. Examples of the metal foil include aluminum foil, stainless steel foil, and iron foil. Moreover, you may use the laminated body comprised by laminating | stacking another film on these metal foils.

  When using the vapor deposition film comprised by forming the 2nd inorganic thin film 32 on the 2nd vapor deposition base material 31 as the 2nd gas barrier film 30, as the 2nd vapor deposition base material 31, polyethylene terephthalate is used. A film, an ethylene-vinyl alcohol copolymer film, a polyethylene naphthalate film, a polyamide film, a polyimide film, a polyvinyl chloride film, or the like can be used. As the second inorganic thin film 32, a metal thin film, a metal oxide thin film, or a diamond-like carbon thin film can be used in the same manner as the first inorganic thin film 22. Further, the second inorganic thin film 32 can be formed by a vapor phase growth method such as a vacuum deposition method, a sputtering method, a CVD method or the like, similarly to the first inorganic thin film 22.

  In addition, what used the ethylene-vinyl alcohol copolymer film as the 2nd vapor deposition base material 31 as the 2nd gas-barrier film 30, and formed the aluminum thin film on this ethylene-vinyl alcohol copolymer film. It can be preferably used. In this case, the gas barrier property of the obtained gas barrier laminate is excellent, and its bending resistance is also excellent.For this reason, when manufacturing the vacuum heat insulating material described later, the vacuum heat insulating material is laterally outward. Even if the protruding fins (heat-sealed part and vacuum contact part) are bent, the gas barrier property does not deteriorate.

  Note that, as described above, the first inorganic thin film 22 is made of alumina and the second gas barrier because of its high gas barrier property, high bending resistance, and no deterioration in gas barrier property even when bent. It is desirable to use a conductive film 30 in which an aluminum thin film 32 is formed on a vapor deposition base 31 made of an ethylene-vinyl alcohol copolymer film.

  Next, as the isocyanate-based adhesive used for the urethane-based adhesive layer ad2, a well-known two-component curable urethane-based adhesive for dry lamination can be used.

  As the heat seal layer 40, a low density polyethylene resin, a linear low density polyethylene resin, a polypropylene resin, a polyacrylonitrile resin, a polyethylene terephthalate resin, a nylon resin, or the like can be used. A co-extruded film that is co-extruded with other resins can also be used. For example, it is a co-extruded film having a two-layer structure in which low-density polyethylene and an ethylene-vinyl alcohol copolymer are co-extruded to form a film. A co-extruded film having a three-layer structure in which low-density polyethylene, ethylene-vinyl alcohol copolymer, and polyamide are co-extruded to form a film can also be used.

  Next, the surface protective layer 10 improves the resistance of the exterior material for a vacuum heat insulating material against external piercing or the like. As the surface protective layer 10, it is desirable to use a material excellent in mechanical properties, physical properties, chemical properties, and other various properties. For example, it is excellent in mechanical strength, heat resistance, moisture resistance, pinhole resistance, puncture resistance and the like.

  As such a surface protective layer 10, a nylon film, a polyethylene terephthalate film, a polypropylene film, or the like can be used. Either an unstretched film or a stretched film may be used, but a biaxially stretched film is preferred from the viewpoint of mechanical strength and heat resistance.

  What is preferable as the surface protective layer 10 is a biaxially stretched nylon film. By using a biaxially stretched nylon film as the surface protective layer 10, the puncture resistance is improved and the toughness of the exterior material is increased. A laminated film obtained by laminating a polypropylene film and a stretched nylon film may be used as the surface protective layer 10. Also in this case, the puncture resistance is improved and the toughness of the vacuum heat insulating exterior material 1 can be increased. The thickness may be 9-50 μm.

  Further, the intermediate reinforcing layer is located between the second gas barrier film 30 and the heat seal layer 40 and is pierced from the outside instead of the surface protective layer 10 or in addition to the surface protective layer 10. This improves the resistance to mechanical strength and mechanical strength. As the intermediate reinforcing layer, the same film as the surface protective layer 10 can be used.

In addition, the lamination of the second gas barrier film 30 and the heat seal layer 40, the lamination of the first gas barrier film 20 and the surface protective layer 10, and the lamination of the second gas barrier film 30 and the intermediate reinforcing layer are: Both are possible by dry lamination using a urethane-based adhesive. In FIG. 1, ad1 and ad3 both indicate urethane adhesive layers.

  Using this vacuum heat insulating material exterior material 1, a vacuum heat insulating material can be manufactured by the following method.

  First, two rectangular vacuum heat insulating material exterior materials 1 are heat-sealed with the heat seal layer 40 faced, three sides are heat-sealed in a bag shape, the core material 3 is inserted therein, and vacuuming is performed. At this time, a vacuum contact portion 5 where the exterior materials 1 are in close contact with each other is formed around the core material 3. And the heat sealing | fusion part 4 is provided in the outer periphery of the vacuum contact | adherence part 5 by heat-sealing the exterior materials 1 with the periphery (refer FIG. 2).

  As the core material 3, inorganic fibers such as glass fibers and organic fibers such as polystyrene fibers can be used. Moreover, what hardened powder and made into a board and a foamed resin can also be used. Moreover, you may use powder, such as foaming pearlite.

  By the way, as can be seen from FIG. 2, both the vacuum contact portion 5 and the heat fusion portion 4 have a shape protruding outward from the side portion of the vacuum heat insulating material. Therefore, as shown in the cross-sectional view of FIG. 3, the close contact portion 5 and the heat fusion portion 4 are bent to the outside air side so as not to come to the cold insulation or heat insulation side. A portion where the close contact portion 5 and the heat fusion portion 4 are bent is stopped with a tape 6 as shown in FIG. Thus, a vacuum heat insulating material can be manufactured.

  Hereinafter, the present invention will be described with reference to examples and comparative examples.

(Example)
A vapor deposition film in which an alumina thin film 22 was formed on a vapor deposition substrate 21 made of a polyethylene terephthalate film (thickness: 12 μm) having a melting point of 255 ° C. was prepared as the first gas barrier film 20. Moreover, the vapor deposition film which formed the thin film 32 of aluminum on the vapor deposition base material 31 which consists of an ethylene-vinyl alcohol copolymer film (15 micrometers in thickness) as the 2nd gas barrier film 30 was prepared. And it arrange | positions so that the vapor deposition base material 21 of the 1st gas barrier film 20 and the aluminum thin film 32 of the 2nd gas barrier film 30 may face each other, and it dry-laminates with a commercially available two-component curable urethane type adhesive. A gas barrier laminate was produced.

  Next, the stretched nylon film (thickness 15 μm) was dry laminated on the alumina thin film 22 of the gas barrier laminate as the surface protective layer 10. As the adhesive, a commercially available two-component curable urethane adhesive was used.

  Then, a linear low density polyethylene film (thickness: 15 μm) was dry laminated on the ethylene-vinyl alcohol copolymer film 31 of the gas barrier laminate as the heat seal layer 40. As the adhesive, a commercially available two-component curable urethane adhesive was used.

  The vacuum insulation material 1 thus obtained has the layer structure shown in the sectional view of FIG. That is, in order from the outer surface side, a surface protective layer (stretched nylon film) 10, a urethane adhesive layer ad1, a first inorganic thin film (alumina thin film) 22, a first vapor deposition base material (polyethylene terephthalate film) 21, urethane Adhesive layer ad2, second inorganic thin film (aluminum thin film) 32, second deposition base material (ethylene-vinyl alcohol copolymer film) 31, urethane adhesive layer ad3, heat seal layer (linear low (Density polyethylene film) 40.

(Comparative Example 1)
The comparative example 1 arrange | positions the front and back of the 1st gas barrier film 20 reversely. Others were the same as in the example. That is, the difference between the example and the comparative example 1 is that the gas barrier laminate of the example is arranged so that the first vapor deposition base material (polyethylene terephthalate film) 21 is in contact with the urethane-based adhesive layer ad2. On the other hand, the gas barrier laminate of Comparative Example 1 is arranged such that the first inorganic thin film (alumina thin film) 22 is in contact with the urethane-based adhesive layer ad2.

  Therefore, the vacuum insulating material exterior material 1 of Comparative Example 1 has the layer configuration shown in the cross-sectional view of FIG. That is, in order from the outer surface side, a surface protective layer (stretched nylon film) 10, a urethane-based adhesive layer ad1, a first vapor deposition substrate (polyethylene terephthalate film) 21, a first inorganic thin film (alumina thin film) 22, urethane Adhesive layer ad2, second inorganic thin film (aluminum thin film) 32, second deposition base material (ethylene-vinyl alcohol copolymer film) 31, urethane adhesive layer ad3, heat seal layer (linear low (Density polyethylene film) 40.

(Comparative Example 2)
The exterior material of Comparative Example 2 is the same as that of Comparative Example 1 except for the surface protective layer (stretched nylon film) 10, and instead of the nylon film between the first gas barrier film 20 and the second gas barrier film 30. (Thickness 15 μm) 50 is interposed.

  In this exterior material, the first gas barrier film 20 and the nylon film (thickness 15 μm) 50 are bonded by a urethane-based adhesive layer ad4. The urethane-based adhesive layer ad4 is a first inorganic thin film ( It is in contact with the alumina thin film) 22 and the nylon film 50 and is not in contact with the first vapor deposition substrate (polyethylene terephthalate film) 21. Further, the nylon film 50 and the second gas barrier film 30 are also bonded by the urethane-based adhesive layer ad5. The urethane-based adhesive layer ad5 is composed of the second inorganic thin film (aluminum thin film) 32 and the nylon film 50. In contact with.

  The layer structure of the exterior material according to Comparative Example 2 is shown in FIG. That is, from the outer surface side, in order, a first vapor deposition base material (polyethylene terephthalate film) 21, a first inorganic thin film (alumina thin film) 22, a urethane adhesive layer ad4, a nylon film 50, a urethane adhesive layer ad5, The second inorganic thin film (aluminum thin film) 32, the second vapor deposition substrate (ethylene-vinyl alcohol copolymer film) 31, the urethane adhesive layer ad3, and the heat seal layer (linear low density polyethylene film) 40 It is a layer structure.

(Comparative Example 3)
The packaging material of Comparative Example 3 uses a vapor deposition film 30 ′ similar to the second gas barrier film 30 in place of the first gas barrier film 20 in Comparative Example 1. That is, this vapor deposition film 30 'is obtained by forming an aluminum thin film 32' on a vapor deposition substrate 31 'made of an ethylene-vinyl alcohol copolymer film (thickness 15 .mu.m). Is arranged so that the urethane adhesive layer ad2 contacts.

  The layer structure of the exterior material of Comparative Example 3 is shown in FIG. That is, in order from the outer surface side, the surface protective layer (stretched nylon film) 10, the urethane adhesive layer ad1, the ethylene-vinyl alcohol copolymer film 31 ′, the aluminum thin film 32 ′, the urethane adhesive layer ad2, the second. Layer structure of inorganic thin film (aluminum thin film) 32, second vapor deposition base material (ethylene-vinyl alcohol copolymer film) 31, urethane adhesive layer ad3, and heat seal layer (linear low density polyethylene film) 40 It is.

(Evaluation and discussion)
About the exterior material of an Example and Comparative Examples 1-3, it was observed whether the bubble was produced in the adhesive bond layer. Observation was made by visual observation.

  As a result, in Comparative Example 1 in which the first inorganic thin film (alumina thin film) 22 and the second inorganic thin film (aluminum thin film) 32 are bonded to each other with the urethane-based adhesive layer ad2, slight bubbles are formed in the urethane-based adhesive layer ad2. It was confirmed that this occurred. Comparison in which an aluminum thin film 32 ′ is used in place of the first inorganic thin film (alumina thin film) 22 and this aluminum thin film 32 ′ and the second inorganic thin film (aluminum thin film) 32 are bonded with a urethane-based adhesive layer ad2. The same was true for Example 3. In these examples, the urethane-based adhesive layer ad2 is sandwiched between inorganic thin films, and the carbon dioxide gas generated from the urethane-based adhesive layer ad2 is not released, so this carbon dioxide gas remains to form bubbles. I can guess it.

  On the other hand, in the example in which the first vapor deposition substrate (polyethylene terephthalate film) 21 and the second inorganic thin film (aluminum thin film) 32 were bonded with the urethane-based adhesive layer ad2, the generation of bubbles was not recognized. The difference between this example and Comparative Example 1 is that the front and back of the first gas barrier film 20 are arranged opposite to each other, and therefore, the vapor deposition substrate made of a polyethylene terephthalate film having a urethane adhesive layer ad2 having a melting point of 255 ° C. When the gas is in contact with the gas 21, it can be assumed that the generated carbon dioxide gas is absorbed by the vapor deposition base material 21 or passes through the vapor deposition base material 21 and is discharged to the outside.

  In addition, the exterior of the comparative example 2 laminated | stacked in order of the 1st inorganic thin film (alumina thin film) 22, the urethane type adhesive layer ad4, the nylon film 50, the urethane type adhesive layer ad5, and the 2nd inorganic thin film (aluminum thin film) 32. In the material, it was observed that bubbles were generated in both the urethane-based adhesive layer ad4 and the urethane-based adhesive layer ad5. Moreover, the amount of bubbles was larger than that in Comparative Example 1. From this result, it can be seen that a thermoplastic resin layer of a specific material needs to be in contact with the urethane adhesive layer in order to prevent bubbles in the urethane adhesive layer.

  In Comparative Example 2, the reason why a larger amount of bubbles was generated than in Comparative Example 1 is not clear, but since nylon film 50 is a material having high water absorption and high gas barrier properties, It can be presumed that a large amount of carbon dioxide gas is generated by the reaction between the isocyanate group and the isocyanate group, and this large amount of carbon dioxide gas cannot be permeated through the nylon film and remains.

1: Exterior material 2: Vacuum heat insulating material 3: Core material 4: Thermal fusion part 5: Adhering part 6: Tape 10: Surface protective layer 20: First gas barrier film 21: First vapor deposition base material 22: First 1 Inorganic thin film 30: 2nd gas barrier film 31: 2nd vapor deposition base material 32: 2nd inorganic thin film 30 ': Gas barrier film 31': Ethylene-vinyl alcohol copolymer film 32 ': Aluminum thin film 40 : Heat seal layer 50: Nylon film ad1 to ad5: Urethane adhesive layer

Claims (4)

In a gas barrier laminate comprising two gas barrier films laminated with an isocyanate-based adhesive,
Of two of the gas barrier film, a first gas barrier film one, when the other was a second gas barrier film, the first deposition substrate the first gas barrier film is made of polyethylene terephthalate film A first inorganic thin film made of a metal oxide is formed thereon, the first vapor deposition substrate is disposed so as to contact the isocyanate-based adhesive , and the second A gas barrier film is obtained by forming a second inorganic thin film made of an aluminum thin film on a second vapor deposition substrate made of an ethylene-vinyl alcohol copolymer film, and the isocyanate of the first gas barrier film. A surface protective layer made of a biaxially stretched nylon film is laminated on the side not in contact with the adhesive, and the second gas barrier film Gas barrier laminate on the side not in contact with the isocyanate-based adhesive Lum heat seal layer is characterized in that it is laminated. Gas barrier laminate according to claim 1, wherein the inorganic thin film of the first gas barrier film is characterized in that it is a thin film of alumina. Gas barrier laminate according to claim 1, wherein the inorganic thin film of the first gas barrier film is characterized in that it is a thin film of silicon oxide. The exterior material for vacuum heat insulating materials which contains the gas-barrier laminated body in any one of Claims 1-3 in the layer structure.

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