Thermal insulation retaining laminate

Abstract

To provide a heat-insulating holding laminate for a vacuum heat-insulating panel outer packaging material, a heat-insulating holding packaging material, and a heat-insulating holding package which adsorb gas generated from a sealant layer itself and a gas from a space in contact with the sealant layer, have a sealant layer having a small amount of gas discharge, suppress rise in an atmospheric pressure in an internal depressurized condition inside a vacuum heat-insulating panel due to degradation with time, and suppress rise of thermal conductivity in a thickness direction of the vacuum heat-insulating panel.SOLUTION: A heat-insulating holding laminate 1 has a gas barrier base material layer 3, and a low gas dischargeable gas adsorption sealant layer 4, in which the low gas dischargeable gas adsorption sealant layer contains a low gas dischargeable resin having heat sealability, a gas adsorbent 6a and a moisture absorbent 6b, and the low gas dischargeable resin has a density of 0.915 g / cm3 or more and 0.935 g / cm3 or less.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a heat insulating laminate for use in packaging materials for vacuum insulation panels, which has a sealant layer that adsorbs gases generated from the sealant layer itself and gases including water (water vapor) from the space in contact with the sealant layer, thereby reducing the amount of gas released. [Background technology]

[0002] A vacuum insulation panel has an internal structure with a core material sealed within an outer packaging material, and the pressure inside the vacuum insulation panel is much lower than atmospheric pressure, maintaining a reduced pressure state close to a vacuum. Since the inside of the vacuum insulation panel is in a reduced pressure state, which suppresses thermal convection, the vacuum insulation panel can exhibit good insulation performance in the thickness direction, and the insulation performance per unit thickness of the vacuum insulation panel is higher than that of general foam insulation materials. Furthermore, since the insulation efficiency is high, the vacuum insulation panel can be made thin while maintaining the desired insulation properties. Therefore, by using a vacuum insulation panel to manufacture an insulated container, it is possible to reduce the weight and space of the insulated container. However, if the vacuum insulation panel is damaged or deteriorates over time, causing the internal air pressure to rise and the reduced pressure state to be lost, the insulation performance of the panel will rapidly decrease. Conventionally, the reason for the increase in internal air pressure due to deterioration over time caused by the outer packaging material has been said to be the intrusion of air as it permeates the outer packaging material. In order to improve the gas barrier properties of the outer packaging material, laminated films having a metal aluminum foil with a thickness of about 6 to 15 μm as a gas barrier layer have been mainly used for the outer packaging material, and laminated films having an additional layer made of a vapor-deposited film or coated film of various inorganic materials have been proposed (Patent Document 1). However, these have been insufficient in terms of maintaining stable insulation properties over the long term. A method has been proposed in which a porous material such as synthetic zeolite is incorporated into the sealant layer of the packaging material to adsorb gas components and thereby maintain the degree of vacuum inside the package (Patent Document 2). However, this method is insufficient in terms of maintaining a stable insulation effect over the long term, due to the limited types of gases that can be adsorbed, the low heat resistance of the resin that constitutes the sealant layer, and the large amount of outgassing. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2008-087176 A [Patent Document 2] JP 2018-189220 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention aims to provide a heat-insulating laminate, heat-insulating packaging material, and heat-insulating packaging body for use as an outer packaging material for vacuum insulation panels, which has a sealant layer that adsorbs gases generated from the sealant layer itself and gases containing water (water vapor) from the space with which the sealant layer is in contact, with a low amount of gas emission, and which suppresses an increase in air pressure in the internal reduced pressure state inside the vacuum insulation panel due to deterioration over time, thereby suppressing an increase in the thermal conductivity of the vacuum insulation panel in the thickness direction. [Means for solving the problem]

[0005] As a result of various investigations, the present inventors have found that the above object can be achieved by a heat insulating laminate that at least emits a small amount of gas and has gas adsorption properties including water (water vapor) adsorption properties. That is, the present invention is characterized in the following points. 1. A heat insulating retaining laminate for a vacuum insulation panel that adsorbs gases generated from the sealant layer itself and from the space in contact with the sealant layer, the gas is one or a combination of two or more selected from the group consisting of hydrocarbons, aldehydes, ketones, carboxylic acids, esters, alcohols, carbon dioxide, and water vapor; The heat insulating support laminate has a gas barrier substrate layer and a low outgassing gas adsorbent sealant layer, The low outgassing gas adsorbing sealant layer contains a low outgassing resin having heat sealability, a gas adsorbent, and a moisture absorbent, The low gas emission resin has a density of 0.915 g / cm 3 More than 0.935g / cm 3 A heat insulating laminate, characterized in that: 2. The content of the low gas-releasing resin in the entire low gas-releasing gas adsorption sealant layer is 70% by mass or more and 99.9% by mass or less; The content of the gas adsorbent in the layer containing the gas adsorbent is 0.1% by mass or more and 30% by mass or less, The content of the moisture absorbent in the layer containing the moisture absorbent is 1% by mass or more and 50% by mass or less. 2. The heat insulating retaining laminate according to 1 above. 3. The heat insulating laminate according to 1 or 2 above, wherein the low gas releasing resin is a polyethylene resin. 4. A heat insulating laminate according to any one of 1 to 3 above, characterized in that the concentration of soluble total organic carbon (TOC) contained in the film made of the low gas releasing resin is 1.5 ppm or more and 250 ppm or less. 5. The heat insulating laminate described in any one of 1 to 4 above, characterized in that the low gas releasing resin is one or a combination of two or more selected from the group consisting of medium density polyethylene, low density polyethylene, and linear low density polyethylene. 6. The heat insulating laminate according to any one of 1 to 5 above, characterized in that the gas adsorbent comprises one or a combination of two or more selected from the group consisting of hydrophobic zeolite, molecular sieve, metal-organic framework (MOF), and activated carbon. 7. The heat insulating laminate according to any one of 1 to 6 above, wherein the moisture absorbent is one or a combination of two or more selected from the group consisting of calcium oxide, magnesium oxide, barium oxide, and hydrophilic zeolite. 8. The low outgassing gas adsorbent sealant layer has an adsorbent layer and a heat seal layer, the adsorption layer is a layer containing the low gas release resin, the gas adsorbent, and the moisture absorbent, the heat seal layer contains the low gas release resin and has heat sealability; At least one outermost layer of the low outgassing gas adsorbent sealant layer is a heat seal layer, The low gas-releasing resin contained in the adsorption layer and the low gas-releasing resin contained in the heat seal layer are the same or different. 8. The heat insulating laminate according to any one of 1 to 7 above. 9. The heat insulating laminate according to the above item 8, wherein the adsorption layer comprises a gas adsorption layer and a moisture absorption layer. 10. The heat insulating laminate according to any one of 1 to 9 above, wherein the low outgassing gas adsorbing sealant layer further contains an antioxidant. 11. The heat insulating laminate according to claim 10, characterized in that the content of the antioxidant in the entire low gas releasing gas adsorbing sealant layer is 0.005 mass % or more and 0.5 mass % or less. 12. The antioxidant is contained in the adsorption layer and / or the heat seal layer, The antioxidant contained in the adsorption layer and the antioxidant contained in the heat seal layer are the same or different. 12. The heat insulating laminate according to any one of 9 to 11 above. 13. The heat insulating retaining laminate according to any one of 1 to 12 above, wherein the low outgassing, gas adsorbing sealant layer is a layer made of a low outgassing, gas adsorbing sealant film. 14. The amount of an organic gas component having a carbon number of 16 released when heated in air at 90°C for 60 minutes is 10 μg / cm per unit volume of the low outgassing gas adsorbing sealant film. 3 More than 1000μg / cm 3 14. The heat insulating laminate according to claim 13, characterized in that: 15. A heat insulating property-retaining packaging material for a vacuum insulation panel, produced using the heat insulating property-retaining laminate according to any one of 1 to 14 above. 16. A vacuum insulation panel produced using the heat insulating packaging material described in 15 above. Effect of the Invention

[0006] According to the present invention, it is possible to obtain a heat insulating laminate, a heat insulating packaging material, and a heat insulating packaging body for use as an outer packaging material for a vacuum insulation panel, which has a sealant layer with a low amount of gas emission that adsorbs gas generated from the sealant layer itself and gas containing water (water vapor) from the space with which the sealant layer is in contact, suppresses an increase in air pressure in the internal reduced pressure state inside the vacuum insulation panel due to deterioration over time, and suppresses an increase in thermal conductivity in the thickness direction of the vacuum insulation panel. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the heat insulating property-retaining laminate or heat insulating property-retaining packaging material of the present invention. [Diagram 2] FIG. 2 is a schematic cross-sectional view showing an example of another embodiment of the layer structure of the heat insulating property retaining laminate or heat insulating property retaining packaging material of the present invention. [Diagram 3] FIG. 2 is a schematic cross-sectional view showing another example of the layer structure of the heat insulating property retaining laminate or heat insulating property retaining packaging material of the present invention. [Figure 4] FIG. 2 is a schematic cross-sectional view showing another example of the layer structure of the heat insulating property retaining laminate or heat insulating property retaining packaging material of the present invention. [Diagram 5] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a heat insulating packaging body (vacuum insulation panel) of the present invention.

[0008] In each drawing, the size and ratio of the components may be changed or exaggerated for ease of understanding. Also, for ease of understanding, parts that are unnecessary for the explanation or repeated reference numerals may be omitted. Although not shown in the drawings, an adhesive layer may be provided between each layer. Furthermore, if necessary, in order to strengthen the adhesive strength (adhesion strength) between each layer, the laminated surfaces of each layer may be subjected in advance to a physical surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, sandblasting treatment, etc., or a chemical surface treatment such as an oxidation treatment using chemicals. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The heat insulating laminate, the heat insulating packaging material, and the heat insulating packaging body of the present invention will be described in more detail below. Specific examples will be given, but the present invention is not limited thereto. In the present invention, the terms film and sheet are used synonymously.

[0010] <Thermal insulation retaining laminate> The heat insulating property-retaining laminate of the present invention is a laminate used as an outer packaging material for a vacuum insulation panel, and has a layer structure including a gas barrier substrate layer and a low outgassing gas adsorbent sealant layer. The low outgassing gas adsorbing sealant layer contains a low outgassing resin, a gas adsorbent, and a moisture absorbent, and the low outgassing resin is preferably a low outgassing resin having heat sealability.

[0011] Although depending on the application, the inside of the vacuum insulation panel is often reduced in pressure to 0.1 to 100 Pa. A vacuum insulation panel packaged with the heat insulation retaining laminate of the present invention maintains its internal reduced pressure state over a long period of time, thereby maintaining its insulation properties in the thickness direction. Regarding the insulation maintenance of the vacuum insulation panel, for example, the increase in thermal conductivity after storage for 1000 hours in an environment of 100° C. is preferably 0 mW / mK or more and 7.0 mW / mK or less, and more preferably 0 mW / mK or more and 6.5 mW / mK or less. It is most preferable that there is no increase in thermal conductivity, and those exceeding the above range are likely to be inferior in practical use over a long period of time.

[0012] In order to maintain a reduced pressure state inside the vacuum insulation panel, it is necessary to suppress the increase in gas molecules inside the vacuum insulation panel. To do this, it is necessary to suppress the amount of gas released from the outer packaging material of the vacuum insulation panel itself, the amount of gas that penetrates through the thickness of the outer packaging material and enters the inside of the vacuum insulation panel, and the amount of gas that penetrates into the inside of the vacuum insulation panel through the interface of the joints created by heat sealing the outer packaging material, etc.

[0013] Of the gas released from the outer packaging material itself into the interior of the vacuum insulation panel, a large amount is released from the sealant layer of the outer packaging material, and a heat seal layer is present at the interface of the joints of the outer packaging material, such as those formed by heat sealing, and a sealant layer is in contact with the internal space of the vacuum insulation panel. Therefore, the sealant layer of the heat insulating laminate of the present invention is a low outgassing gas adsorbing sealant layer, which generates a small amount of gas itself and has excellent heat sealing properties. By adsorbing gases containing water (water vapor) from the space with which the low outgassing gas adsorbing sealant layer is in contact, it adsorbs gases that penetrate into the vacuum insulation panel through the interface of the joint and gases that have permeated the barrier substrate layer, preventing them from reaching the inside of the vacuum insulation panel. It also adsorbs gases containing water (water vapor) present inside the vacuum insulation panel, preventing an increase in air pressure inside the vacuum insulation panel and maintaining a reduced pressure state, thereby maintaining insulation properties.

[0014] The gas release properties of the heat insulating retaining laminate of the present invention are dominated by the gas release properties of the low gas release, gas adsorption sealant layer that constitutes the heat insulating retaining laminate, and can be determined by measuring the gas release properties of the low gas release, gas adsorption sealant film that forms the low gas release, gas adsorption sealant layer. For example, two strips of film obtained by cutting a low outgassing gas adsorption sealant film to 50 mm x 10 mm are placed in a test tube and heated at 90°C for 60 minutes. The air in the test tube is then sampled and the concentrations of organic gas components with each carbon number in the sampled air are measured by gas chromatography, and the amount of organic gas components released by the low outgassing gas adsorption sealant film when heated can be calculated. Among organic gas components, the amount of C16 gas components (organic gas components with 16 carbon atoms) in particular is highly correlated with the thermal conductivity of vacuum insulation panels made using insulation-retaining packaging materials having a sealant layer formed from a low-gas-releasing gas-adsorbing sealant film.

[0015] The amount of C16 gas component released when the low outgassing gas adsorbent sealant film is heated, as determined by the above method, per unit volume of the low outgassing gas adsorbent sealant film is 10 μg / cm 3 More than 1000μg / cm 3 It is preferable that:

[0016] The gas adsorption properties of the heat insulating laminate of the present invention can be measured by cutting the heat insulating laminate to, for example, 10 cm x 10 cm, placing it in a gas sampling bag, filling it with a gas to be adsorbed of known concentration, and leaving it for two days, after which the change in gas concentration can be measured using a detector tube.

[0017] (Gas to be adsorbed) The gas components to be adsorbed in the present invention are mainly gas components originally contained in the heat insulating laminate of the present invention (particularly the low outgassing gas adsorbent sealant layer), gas components consisting of resin decomposition products generated by decomposition of the resin in the heat insulating laminate by heating such as heat sealing or irradiation with UV or EB, and gas components containing water (water vapor) present in the atmosphere. Here, examples of gas components originally contained in the heat insulating laminate include gas components contained in the raw materials constituting the heat insulating laminate (particularly the low outgassing gas adsorption sealant layer), gas components generated due to the thermal history when forming the heat insulating laminate, and gas components generated when the heat insulating laminate is heat sealed.

[0018] Specific examples of gases to be adsorbed include low molecular weight organic substances, carbon dioxide, nitrogen, oxygen, and water (water vapor). Organic matter is a gas component derived from the heat insulating laminate, and the compounds of the gas components often have a carbon number of 1 to 16, and the most common type is hydrocarbons, but other examples include alcohols, aldehydes, ketones, and carboxylic acids.

[0019] Specific examples of hydrocarbon compounds include propane, propene, butane, isobutane, 2-methylbutane, butene, isobutene, 2-methylpentane, 3-ethylpentane, 2,2-dimethylpentane, 3,3-dimethylpentane, hexane, cyclohexane, 2-methylhexane, 3-methylhexane, 2,5-dimethylhexane, heptane, 2-methylheptane, 3-methylheptane, 3-ethylheptane, 2,2,4,6,6-pentamethylheptane, 3-ethyl-3-methylheptane, 3-methylheptene, octane, 2-methyloctane, 4-ethyloctane, nonane, 3-methylnonane, decane, and dodecane.

[0020] Specific examples of alcohol compounds include 2-methyl-2-propanol, 2-methylpropanol, ethanol, and 1-propanol.

[0021] Specific examples of aldehyde compounds include formaldehyde, acetaldehyde, 2-methylpropanal, and 3-methylbutanal.

[0022] Specific examples of ketone compounds include acetone, MEK, MIBK, and 3,3-dimethyl-2-butanone.

[0023] Specific examples of carboxylic acid compounds include acetic acid, isovaleric acid, 2-methylpropanoic acid, and 2,2-dimethylpropanoic acid.

[0024] Specific examples of ester compounds include ethyl acetate, butyl acetate, and the like.

[0025] Carbon dioxide originates from atmospheric components, aldehydes, ketones, carboxylic acids, and alcohols originate from the thermal history of the low outgassing gas adsorbing sealant film or heat insulating retaining laminate and atmospheric components, and esters originate from the adhesive layer.

[0026] <Gas barrier substrate layer> The gas barrier substrate layer in the present invention refers to a substrate layer having gas barrier properties, and may be composed of a single layer such as a gas barrier resin film having both gas barrier properties and substrate properties, or may have a multi-layer structure including a gas barrier layer and a substrate layer. Furthermore, in order to improve adhesion, an adhesive layer may be provided between each layer constituting the gas barrier substrate layer or between each layer and other layers, and a desired surface treatment layer may be provided in advance on the surface of each layer as necessary.

[0027] For example, a corona-treated layer, an ozone-treated layer, a plasma-treated layer, an oxidation-treated layer, or the like can be formed by optionally carrying out pretreatment such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, or the like, glow discharge treatment, or oxidation treatment using chemicals, or the like.

[0028] Alternatively, various coating layers such as a primer coating layer, an undercoating layer, an anchor coating layer, an adhesive layer, and a vapor-deposited anchor coating layer may be optionally formed on the surface of each layer to form a surface treatment layer. For the various coating layers, for example, a resin composition containing a polyester resin, a polyamide resin, a polyurethane resin, an epoxy resin, a phenol resin, a (meth)acrylic resin, a polyvinyl acetate resin, a polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof, a cellulose resin, or the like as the main component of the vehicle can be used. The thickness of the gas barrier substrate layer is preferably 5 μm or more and 100 μm or less, more preferably 7 μm or more and 75 μm or less. If the thickness is less than the above range, the rigidity and / or gas barrier properties may be insufficient, and if the thickness exceeds the above range, the rigidity may be too high, resulting in reduced workability.

[0029] [Base material layer] The substrate layer may be a resin film, a paper material, or the like, and may be composed of a single layer or a multilayer structure including two or more layers having the same or different compositions.

[0030] The thickness of the base layer varies depending on the material, but in the case of a resin film, it is preferably 15 μm or more and 60 μm or less, more preferably 7 μm or more and 45 μm or less. The resin film used for the base layer may be a film of a thermoplastic resin, and it is preferable that the thermoplastic resin has excellent chemical and physical strength, can withstand the conditions for forming a vapor-deposited film of a metal or metal oxide, and can well retain the properties of the vapor-deposited film without impairing the properties.

[0031] Examples of such resins include polyolefin resins such as polyethylene resins and polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), poly(meth)acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyurethane resins, acetal resins, and cellulose resins. In the present invention, the resin is preferably a polyester resin, a polyamide resin, or a polyolefin resin, and in particular, polyethylene terephthalate (PET), nylon, or polypropylene (PP).

[0032] In the present invention, the thermoplastic resin used in the substrate layer can be formed into a film by various film-forming methods. For example, a method of forming a film using one type of resin by a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, or an inflation method, a method of forming a multilayer film by co-extrusion using two or more types of resins, a method of mixing two or more types of resins before film formation and forming a film by the above-mentioned film formation method, etc. Furthermore, a film can be uniaxially or biaxially stretched using a tenter method, a tubular method, etc.

[0033] Alternatively, one or more resins may be coated on another resin film by applying and drying, or a molten resin may be laminated by a T-die method or the like. In the present invention, the resin film is preferably a biaxially oriented PET film, a biaxially oriented nylon film, or a biaxially oriented PP film or sheet.

[0034] In addition, when forming the resin film, various plastic compounding agents and additives can be added to the resin film for the purpose of improving or modifying, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability, oxidation resistance, slipperiness, release properties, flame retardancy, mold resistance, electrical properties, strength, etc. of the film. The amount of these additives can range from a very small amount to several tens of percent and can be added at any amount depending on the purpose. In the above, examples of common additives that can be used include lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, modifying resins, and the like.

[0035] [Gas barrier layer] The gas barrier layer is a layer that, in a vacuum insulation panel produced using the heat insulating laminate of the present invention, prevents gas containing water (water vapor) in the atmosphere from passing through the heat insulating laminate from the outside to the inside of the vacuum insulation panel. The gas barrier layer can be made of one or a combination of two or more selected from the group consisting of a gas barrier resin film, a metal foil, a resin film with a metal or metal oxide vapor-deposited layer, and a gas barrier resin coating film.

[0036] As the gas barrier resin film, for example, a resin film made of a resin such as PET, polybutylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyvinyl alcohol, or an ethylene-vinyl alcohol copolymer is preferable.

[0037] The metal foil is preferably an aluminum foil having a thickness of 3 μm or more and 15 μm or less.

[0038] The resin film with a metal or metal oxide vapor deposition layer is preferably one in which an aluminum vapor deposition film, a silica vapor deposition film, or an aluminum oxide vapor deposition film is formed on at least one surface of the above-mentioned base resin film. Commercially available resin films with an aluminum oxide vapor deposition film include, for example, alumina vapor deposition IB-PET-PIR (thickness 12 μm) and silica vapor deposition IB-ON-UB (thickness 15 μm) manufactured by Dai Nippon Printing Co., Ltd., which are PET films with alumina vapor-deposited on one side by the PVD method.

[0039] As the gas barrier resin coating film, a coating film containing a sol-gel hydrolysis polycondensate formed from a metal alkoxide and a water-soluble polymer is preferred.

[0040] The metal foil for the gas barrier layer, or the resin film with the metal or metal oxide vapor-deposited layer can be bonded to other layers using a dry lamination adhesive. Alternatively, by using a resin film for the base layer as the resin film of the resin film with a metal or metal oxide vapor-deposited layer, lamination onto the base layer can be omitted.

[0041] <Low gas release gas adsorption sealant layer> The low outgassing gas adsorbing sealant layer is a layer containing a low outgassing resin having heat sealing properties and a gas adsorbent, and has heat sealing properties, low outgassing properties, and can adsorb gases including water (water vapor). The low outgassing gas adsorbent sealant layer may have a single layer structure or a multi-layer structure of two or more layers. For example, it may be composed of an adsorption layer containing a low gas-releasing resin, a gas adsorbent, and a moisture absorbent, and a heat seal layer containing a low gas-releasing resin, or it may have a three-layer structure in which an adsorption layer is sandwiched between two heat seal layers. Alternatively, the adsorption layer may be a layer consisting of an adsorption layer containing a low outgassing resin and a gas adsorbent, and a moisture absorption layer containing a low outgassing resin and a moisture absorbent.

[0042] The content of the low gas-releasing resin in the entire low gas-releasing gas adsorption sealant layer is preferably 70% by mass or more and 99.9% by mass or less, more preferably 80% by mass or more and 99.9% by mass or less. If it is less than the above range, the low gas-releasing property of the low gas-releasing gas adsorption sealant may be insufficient, and if it is more than the above range, it is difficult to balance various physical properties and workability, but the low gas-releasing property is not improved much.

[0043] The content of the gas adsorbent in the layer containing the gas adsorbent is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.5% by mass or more and 25% by mass or less. If the content is less than the above range, the gas adsorption effect may be insufficient, and if the content is more than the above range, the film formability may be deteriorated. Here, the layer containing a gas adsorbent refers to the entire low outgassing gas adsorption sealant layer when the low outgassing gas adsorption sealant layer is composed of only one layer, and refers to, for example, the adsorption layer when the low outgassing gas adsorption sealant layer is a multi-layer structure having an adsorption layer and a heat seal layer, etc., and further refers to, for example, the adsorption layer when the adsorption layer is composed of an adsorption layer and a moisture absorption layer.

[0044] The content of the moisture absorbent in the layer containing the moisture absorbent is preferably 1% by mass or more and 50% by mass or less, and more preferably 2% by mass or more and 45% by mass or less. If the content is less than the above range, the moisture absorption effect may be insufficient, and if the content is more than the above range, the film formability may be deteriorated. Here, the layer containing a moisture absorbent refers to the entire low outgassing gas-adsorbing sealant layer when the low outgassing gas-adsorbing sealant layer is composed of only one layer, and refers to, for example, the adsorption layer when the low outgassing gas-adsorbing sealant layer is a multi-layer structure having an adsorption layer and a heat seal layer, etc., and further refers to, for example, the moisture absorbent layer when the adsorption layer is composed of an adsorption layer and a moisture absorption layer.

[0045] When the low outgassing gas adsorption sealant layer has a multi-layer structure having an adsorption layer, a heat seal layer, etc., in order to improve heat sealability and lamination properties, it is preferable that the outermost layer on at least one side of the low outgassing gas adsorption sealant layer is a heat seal layer. Furthermore, the low gas-releasing resin contained in the adsorption layer and the low gas-releasing resin contained in the heat seal layer may be the same or different.

[0046] Inside the vacuum insulation panel, the low outgassing gas adsorption sealant layer is in contact with the space inside the vacuum insulation panel and is present at the joint interface of the heat seal part, so that the thickness of the low outgassing gas adsorption sealant layer can be adjusted to adjust the gas adsorption properties and low outgassing properties. The thickness of the low gas release gas adsorption sealant layer is preferably 25 μm or more and 150 μm or less, more preferably 30 μm or more and 100 μm or less, in order to have a good balance between heat sealability, gas adsorption, and low gas release. If the thickness is thinner than the above range, the heat sealability and / or gas adsorption may be insufficient, and if the thickness is thicker than the above range, the low gas release may be inferior.

[0047] And, the low outgassing, gas adsorbing sealant layer may further contain small amounts of slip agents, antiblocking agents, antioxidants, solvents, and other additives. The low gas release gas adsorption sealant layer of the present invention preferably contains an antioxidant in order to suppress the generation of gas released due to resin deterioration in a high temperature environment. Conversely, it is preferable to limit the use of additives that may increase the amount of gas released at high temperatures.

[0048] [Adsorption layer] The adsorption layer is a layer containing a gas adsorbent and a moisture absorbent, and has high gas adsorption properties, and preferably further contains a low gas release resin as a binder resin in order to maintain low gas release properties. However, other resins and various additives such as antioxidants can be contained within a range that does not significantly impair the gas adsorption properties and low gas release properties. The low outgassing gas adsorbent sealant layer may contain one adsorbent layer or two or more layers having the same or different compositions.

[0049] In order to exhibit good gas adsorption, the thickness of the adsorption layer is preferably 5 μm or more and 80 μm or less, more preferably 7 μm or more and 75 μm or less. If the thickness is thinner than the above range, the gas adsorption may be insufficient, and if the thickness is thicker than the above range, the gas adsorption may not be improved much, and the rigidity of the low gas release gas adsorption sealant layer may become too strong, resulting in a decrease in workability.

[0050] [Gas adsorption layer] A gas adsorbing layer is one in which the adsorbing layer contains a gas adsorbent but does not contain a moisture absorbent.

[0051] [Moisture absorption layer] A moisture absorbing layer is when the adsorption layer contains a moisture absorbent but no gas adsorbent.

[0052] [Heat seal layer] The heat seal layer is a layer containing a low gas releasing resin and has high heat sealability. In order to have high heat sealability, it is preferable that the heat seal layer does not contain a gas adsorbent. In order to achieve both high heat sealability and low gas release, the heat sealable resin contained is preferably a low gas release resin. However, various additives such as gas adsorbents, other resins, and antioxidants may be contained within the range that does not significantly impair the heat sealability and low gas release properties. The low outgassing gas adsorbent sealant layer may contain one heat seal layer or two or more layers having the same or different compositions.

[0053] In order to exhibit good heat sealability, the thickness of the heat seal layer is preferably 3 μm or more and 30 μm or less, more preferably 5 μm or more and 25 μm or less. If the thickness is thinner than the above range, the heat sealability may be insufficient, and if the thickness is thicker than the above range, the heat sealability may not be improved much, and the rigidity of the low gas release gas adsorption sealant layer may become too weak, resulting in a decrease in workability.

[0054] [Low gas emission resin] A low gas release resin is a resin that releases a small amount of gas, and the amount of gas released varies depending on the shape and thermal history of the resin. By incorporating a low outgassing resin with heat sealing properties into a low outgassing gas adsorption sealant layer that contacts the internal space of the vacuum insulation panel, the low outgassing gas adsorption sealant layer is imparted with heat sealing properties, the amount of gas released is reduced, and an increase in air pressure inside the vacuum insulation panel can be suppressed. The amount of gas released from low gas release resins is highly correlated with the concentration of elutable total organic carbon (TOC) contained in the low gas release resins. TOC is the concentration of the total amount of organic matter (organic carbon) in water that can be oxidized, expressed as a carbon concentration. It is used as one of the most representative water quality indicators and is standardized in JIS K0805 (total organic carbon (TOC) automatic measuring device) etc.

[0055] The concentration of soluble total organic carbon (TOC) contained in the film made of the low gas release resin in the present invention is preferably 1.5 ppm or more and 250 ppm or less, and more preferably 5 ppm or more and 200 ppm or less. It is difficult to prepare a film having a concentration lower than the above range, and it is difficult to show a significant difference in practical effect. If it is higher than the above range, the low gas release resin may become insufficient.

[0056] The reason why the concentration of elutable TOC for the low outgassing resin as a single raw material is measured in a film state rather than in the state of raw material pellets, etc., is that when the low outgassing resin is made into a film to form a low outgassing gas adsorption sealant layer, etc., it is subjected to various heat histories, etc., which may increase the amount of eluted TOC.

[0057] The concentration of soluble total organic carbon (TOC) contained in the film made of the above-mentioned low outgassing resin is determined, for example, by filling a pouch made of a film made of the low outgassing resin of the present invention with distilled water as the filling water, allowing the organic carbon to elute, measuring the TOC concentration of the filling water, subtracting the TOC concentration of the filling water before filling as a blank to calculate the increase in TOC concentration, and then calculating the soluble TOC concentration contained in the film made of the low outgassing resin.

[0058] The increase in TOC concentration of the filling water is preferably 0.01 ppm or more and 1.5 ppm or less, more preferably 0.02 ppm or more and 1.45 ppm or less, and even more preferably 0.025 ppm or more and 1.4 ppm or less. It is difficult to prepare something less than the above range, and it is difficult to show a significant difference in practical effect. If it is more than the above range, the low gas release resin may have insufficient low gas release properties. From the viewpoint of both cost and performance, it is preferable that it is in the above range.

[0059] More specifically, although it depends on the application, it is preferable that the temperature of the water during filling is 40°C to 80°C, the temperature during storage is 25°C to 50°C, the storage period is several days to 4 weeks, and the TOC concentration of the water is measured using a total organic carbon meter or HS-GC.

[0060] In the present invention, the elutable TOC concentration contained in the resin film made of low outgassing resin is preferably calculated by filling and sealing a pouch made of a resin film made of low outgassing resin and having an inner dimension of 15 cm x 44 cm with 1000 g of distilled water (distilled water for high performance liquid chromatography, manufactured by Junsei Chemical Co., Ltd.) at 65°C as the filling water, storing the pouch at 35°C for 2 weeks, and then measuring the TOC concentration of the filled water with a TOC-L total organic carbon meter (manufactured by Shimadzu Corporation) as a standard method.

[0061] For example, when a pouch measuring 15 cm x 44 cm x 50 μm in thickness is used and 1,000 g of water is filled, the concentration C of leachable TOC contained in the film made of low gas releasing resin is calculated from the increase in TOC concentration in the filled water as shown below. Filled water (distilled water) weight: W1 = 1000 [g] Density of film made of low gas emission resin: S [g / cm 3 ] Pouch size: 15cm x 44cm x 50μm thick Pouch weight: W2=15×44×50×10 -4 ×2×S=6.6×S[g] Concentration of soluble TOC contained in a film made of low gas emission resin: C [ppm] Increase in TOC concentration in filling water: X [ppm] Then, Total weight of extractable TOC contained in the film made of low gas emission resin = C × W2 [g] This dissolves in W1[g] of water, so X=C×W2 / W1=C×6.6×S×10 -3 [ppm] The TOC concentration C of the elutable TOC contained in the film made of low gas release resin is calculated from the following formula: C = X / (6.6 × S × 10 -3 ) [ppm] For example, the density S of the film made of low gas releasing resin that constitutes the pouch is 0.92 [g / cm 3 ], if the increase in TOC concentration of the filling water is 0.01 [ppm], C = 0.01 / (6.6×0.92×10 -3 )=1.64[ppm] It is calculated as follows:

[0062] The density of low gas emission polyethylene resin is 0.915g / cm 3 More than 0.935g / cm 3 Less than 0.919 g / cm is preferred. 3 More than 0.933g / cm 3 The following is more preferable: A polyethylene resin having a density within the above range tends to be able to reduce the amount of organic gas released.

[0063] The MFR (melt flow rate) of the low gas release polyethylene resin is preferably 0.2 g / 10 min or more and 10 g / 10 min or less, and more preferably 0.5 g / 10 min or more and 7 g / 10 min or less. If the MFR is within the above range, even if it is mixed with other resins or gas adsorbents, it can maintain a good MFR and exhibit good film-forming properties and adhesive properties.

[0064] As the low gas-releasing resin, a polyethylene resin (low gas-releasing polyethylene resin) is preferable because it has excellent heat sealability, resistance to UV or EB irradiation and heating, and resistance to decomposition. Low gas release polyethylene resins originally contain a small amount of gas that can be released, and are resistant to UV or EB irradiation and heating and therefore difficult to decompose, thereby enabling the amount of gas released to be reduced.

[0065] Specific examples of polyethylene species in low gas emission polyethylene-based resins include low gas emission polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylic acid copolymer, ethylene-propylene copolymer, and the like, and mixtures of these resins, but are not limited to these resins.

[0066] Among the above, one or a combination of two or more selected from the group consisting of MDPE, LDPE and LLDPE is preferred. The LLDPE is preferably one or a combination of two or more selected from the group consisting of C4-LLDPE, C6-LLDPE, and C8-LLDPE, and C6-LLDPE is more preferable.

[0067] Here, C4-LLDPE is a linear low-density polyethylene made of a copolymer of ethylene and 1-butene, C6-LLDPE is a linear low-density polyethylene made of a copolymer of ethylene and 1-hexene and / or 4-methyl-1-pentene, and C8-LLDPE is a linear low-density polyethylene made of a copolymer of ethylene and 1-octene. Each of the molecular structures has an ethylene-derived LLDPE main chain with side chains having 4, 6 and 8 carbon atoms derived from 1-butene, 1-hexene and / or 4-methyl-1-pentene and 1-octene, respectively.

[0068] In order to keep the amount of released gas contained in the resin low, for example, it is effective to reduce the amount of unreacted raw materials, low molecular weight products, and by-products, and to remove the polymerization catalyst when producing the resin.Specific examples of such methods include improving the purity of raw materials, precisely controlling conditions such as reaction temperature and pressure, removing unreacted raw materials, low molecular weight products, by-products, and polymerization catalysts by distillation or washing, and preventing oxidation due to exposure to oxygen in the air at high temperatures. Another method is to limit the use of additives that may increase the amount of outgassing when the resin is pelletized or filmed, and to prevent oxidation due to high temperatures. Specific additives include lubricants, antioxidants, antiblocking agents, solvents, etc.

[0069] The hydrophobic zeolite may have any external shape, such as a sphere, a rod, an ellipse, or the like, and may be in any form, such as a powder, a lump, or a granule. From the viewpoints of uniform dispersibility, kneading characteristics, film-forming properties, and the like, when dispersed in a resin, the powder form is preferred.

[0070] In the present invention, the average particle size of the hydrophobic zeolite can be appropriately selected from any average particle size depending on the application, but the average particle size is preferably 0.01 μm or more and 30 μm or less, and more preferably 0.1 μm or more and 20 μm or less. Here, the average particle size is a value measured by a dynamic light scattering method. If the average particle size is smaller than the above range, the hydrophobic zeolite is likely to aggregate and the dispersibility tends to decrease.If the average particle size is larger than the above range, the film-forming property of the layer containing the hydrophobic zeolite tends to be poor, so it tends to be difficult to add a large amount of hydrophobic zeolite, and the surface area is also reduced, so there is a possibility that a sufficient gas adsorption effect cannot be obtained.

[0071] [Gas adsorbent] In the present invention, the gas adsorbent preferably contains one or a combination of two or more selected from the group consisting of hydrophobic zeolite, molecular sieve, MOF, and activated carbon.

[0072] (Hydrophobic Zeolite) In the present invention, the hydrophobic zeolite used as the gas adsorbent preferably has a SiO2 / Al2O3 molar ratio of 30 / 1 to 10000 / 1, more preferably 30 / 1 to 3000 / 1. When the molar ratio is within the above range, the hydrophobicity and the pore size are well balanced, and good gas adsorption properties can be achieved. Hydrophobic zeolite is preferably used because it maintains its gas component adsorption effect even when exposed to temperatures of 230° C. or higher.

[0073] Hydrophobic zeolites are hydrophobic, so they are difficult to adsorb highly polar water molecules, but conversely have a high affinity with organic gases with low polarity, and also have a high affinity with other gas components with low polarity, hydrophobic gases, and lipophilic gases (including solvent-based gases), and are easy to adsorb these. In other words, they have an excellent function of adsorbing gas components that do not have functional groups. Furthermore, when alkali metals and alkaline earth metals such as Ca, Na, and K are present on the zeolite surface, the zeolite surface exhibits basicity and is easy to adsorb acidic gases by neutralization reaction.

[0074] (Molecular sieve) Molecular sieves are a type of hydrophilic zeolite that adsorb highly polar molecules, especially water molecules, into their porous pores. Molecular sieves are designated as 3A, 4A, 5A, or 13X depending on the type of raw zeolite, where the number indicates the approximate pore diameter (angstroms) and the capital letters indicate the type of zeolite, with A representing LTA zeolite and X representing FAU zeolite. 3A is suitable for adsorbing acetonitrile and ethanol, 5A is suitable for adsorbing aromatic compounds, and 13X is suitable for adsorbing large molecules such as long-chain tertiary amines.

[0075] (Metal-organic framework (MOF)) For metal organic frameworks (MOFs), a salt consisting of a metal ion and an organic ligand is preferably used. The metal-organic framework can have a porous structure with a smaller pore size and a larger specific surface area compared to common activated carbon or zeolite. Specific examples of the metal organic framework include aluminum fumarate, zirconium fumarate, copper trimesate, aluminum trimesate, zirconium trimesate, iron trimesate, aluminum terephthalate, zirconium terephthalate, 2-methylimidazole zinc, magnesium formate, zinc benzene-1,3,5-tribenzoate, zinc 2,6-naphthalene-dicarboxylate, aluminum aminobenzene-1,4-dicarboxylate, magnesium 2,5-dioxidobenzene-1,4-dicarboxylate, and magnesium 4,4-dioxidobiphenyl-3,3-dicarboxylate. One or a combination of two or more selected from this group can be used.

[0076] The pore size of the metal organic framework is preferably 0.3 nm or more and 3.0 nm or less, and more preferably 0.3 nm or more and 2.0 nm or less. For example, the pore size of 2-methylimidazole zinc salt is 1.1 nm and 0.6 nm, that of copper trimesate is 0.90 nm or 0.3 nm and 0.5 nm, that of aluminum terephthalate is 0.8 nm and 0.5 nm, that of aluminum fumarate is 1.1 nm and 0.5 nm, that of aluminum trimesate is 0.7 nm and 0.6 nm, that of zirconium trimesate is 0.46 nm, 1.15 nm, and 1.8 nm, that of magnesium formate is 0.3 nm and 0.4 nm, and that of iron trimesate is 2.5 nm and 2.9 nm.

[0077] The specific surface area of ​​the metal-organic framework can be expressed as a BET specific surface area or a Langmuir specific surface area. In the case of the BET specific surface area, 2 / g or more, 4000m 2 / g or less is preferable, and 900m 2 / g or more, 2100m 2 / g or less is more preferable. For Langmuir specific surface area, 500m 2 / g or more, 5000m 2 / g or less is preferable, and 1200m 2 / g or more, 2400m2 / g or less is more preferable.

[0078] For example, the BET specific surface area of ​​2-methylimidazole zinc is 1350 m 2 / g, copper trimesate 1500m 2 / g, aluminum terephthalate is 950m 2 / g, aluminum fumarate is 1000m 2 / g, aluminum trimesate is 1100m 2 / g, zirconium trimesate is 2060m 2 / g, magnesium formate is 400m 2 / g, benzene-1,3,5-tribenzoic acid zinc is 3600m 2 There are ones that are / g. For example, the Langmuir specific surface area of ​​2-methylimidazole zinc is 1800 m 2 / g, copper trimesate 2000m 2 / g, aluminum terephthalate is 1500m 2 / g, aluminum fumarate is 1200m 2 / g, aluminum trimesate 1500m 2 / g, zirconium trimesate 2390m 2 / g, magnesium formate is 500m 2 / g, benzene-1,3,5-tribenzoic acid zinc is 5000m 2 There are ones that are / g.

[0079] The metal organic frameworks described above can absorb gases in amounts corresponding to the molecular size and specific surface area of ​​the pores. For example, 2-methylimidazole zinc salt is excellent in absorbing lower hydrocarbons and carbon dioxide, copper trimesate is excellent in absorbing lower hydrocarbons (especially methane) and carbon dioxide, aluminum terephthalate is excellent in absorbing methane, water vapor, and carbon dioxide, aluminum fumarate and zircon trimesate are excellent in absorbing water vapor, and aluminum trimesate is excellent in absorbing lower hydrocarbons (especially methane) and water vapor.

[0080] In the present invention, among the above metal organic frameworks, it is preferable to use one or a combination of two or more selected from the group consisting of 2-methylimidazole zinc salt, copper trimesate, and aluminum terephthalate.

[0081] (activated carbon) Activated carbon is a porous material that is primarily composed of carbon and also contains oxygen, hydrogen, calcium, etc., and has been chemically or physically processed. Because it is porous, it has a large surface area relative to its volume, and therefore has the ability to adsorb many substances. Since the surface of activated carbon is non-polar, it has a low adsorption power for polar molecules and is more likely to selectively adsorb granular organic matter that is smaller than the pores of activated carbon.

[0082] (Moisture absorbent) In the present invention, the moisture absorbent preferably contains one or a combination of two or more selected from the group consisting of calcium oxide, magnesium oxide, and barium oxide.

[0083] (Improved dispersion by making gas adsorbents into master batches) The gas adsorbent may be directly mixed with other components of the low outgassing gas adsorption sealant layer and melt-kneaded, but it is preferable to increase the dispersibility of the gas adsorbent in the low outgassing gas adsorption sealant layer by mixing the gas adsorbent with a thermoplastic resin at a high concentration and then melt-kneading (melt blending) to prepare a master batch, which is then mixed with other components of the low outgassing gas adsorption sealant layer in a ratio corresponding to the target content and melt-kneaded, a so-called master batch method. By employing the master batch method, even when a gas adsorbent that is prone to aggregation is used, the gas adsorbent can be efficiently and uniformly dispersed in the low outgassing gas adsorbent sealant layer.

[0084] The mass ratio of the gas adsorbent to the thermoplastic resin in the master batch is not particularly limited, but is preferably 3 / 97 or more and 50 / 50 or less, and more preferably 5 / 95 or more and 40 / 60 or less. As a method for kneading the gas adsorbent and the thermoplastic resin, various kneading methods can be applied. The thermoplastic resin used in the masterbatch can be of a type and content within a range that does not significantly adversely affect the heat sealability, film formability, gas adsorption, and low outgassing of the entire low outgassing gas adsorption sealant layer, but it is preferable that the resin has high compatibility with other resins such as heat sealable resins and low outgassing resins contained in the low outgassing gas adsorption sealant layer and has the same degree of heat sealability, and may be the same as or different from these. For example, it may be a low outgassing resin.

[0085] Specific examples of the thermoplastic resin used in the masterbatch include, for example, general-purpose polyethylene, polypropylene, methylpentene polymer, polyolefin resins such as acid-modified polyolefin resins, and mixtures of these resins, but are not limited to these resins, and the type of thermoplastic resin can be selected depending on the purpose.

[0086] The MFR (melt flow rate) of the thermoplastic resin used in the master batch is preferably 0.2 g / 10 min or more and 10 g / 10 min or less. If the MFR is in this range, melt mixing with the gas adsorbent is easy, the gas adsorbent is easily dispersed in the low outgassing gas adsorption sealant layer, and the film formability of the low outgassing gas adsorption sealant layer is easily maintained.

[0087] [Antioxidants] The thermal insulation support laminate preferably further comprises an antioxidant in the low outgassing gas adsorbing sealant layer. The content of the antioxidant in the entire low gas release gas adsorption sealant layer is preferably 0.005 mass% or more and 0.5 mass% or less, and more preferably 0.01 mass% or more and 0.4 mass% or less. If the content is less than the above range, the effect of containing the antioxidant may be insufficient, and if the content is more than the above range, the effect of increasing the antioxidant will not change much, and the heat sealability may tend to deteriorate. The antioxidant may be contained in the adsorption layer and / or the heat seal layer constituting the low outgassing gas adsorption sealant layer, and the antioxidant contained in the adsorption layer and the antioxidant contained in the heat seal layer may be the same or different.

[0088] Specific examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and mixed phenol-based and phosphorus-based antioxidants. It is preferable to use one or a combination of two or more selected from the group consisting of these antioxidants.

[0089] <Adhesive layer> The heat insulating laminate of the present invention can be laminated by providing an adhesive layer between each of the constituent layers and between layers within each layer. Furthermore, before forming the adhesive layer, an anchor coat layer may be formed in advance on the surface of the layer to be adhered in order to improve adhesion.

[0090] The adhesive (adhesive composition) forming the adhesive layer may be of a thermosetting type, an ultraviolet-curing type, an electron beam-curing type, or the like, and may be in any form, such as an aqueous type, a solution type, an emulsion type, a dispersion type, or the like. In addition, the adhesive may be in any form, such as a film / sheet type, a powder type, a solid type, or the like, and the adhesive mechanism may be in any form, such as a chemical reaction type, a solvent volatilization type, a thermal melting type, a thermal pressure type, or the like.

[0091] Examples of such adhesives include polyvinyl acetate adhesives such as polyvinyl acetate and vinyl acetate-ethylene copolymers, polyacrylic acid adhesives made of copolymers of polyacrylic acid and polystyrene, polyester, polyvinyl acetate, etc., cyanoacrylate adhesives, ethylene copolymer adhesives made of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc., cellulose adhesives, polyurethane adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, polyolefin adhesives, amino resin adhesives made of urea resin or melamine resin, etc., phenol resin adhesives, epoxy adhesives, reactive (meth)acrylic adhesives, elastomer adhesives made of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc., silicone adhesives, inorganic adhesives made of alkali metal silicates, low-melting point glass, etc. When a laminate is formed by coextrusion and film formation using an inflation method, among the above, polyolefin-based adhesives are preferred.

[0092] In one embodiment of the present invention, the adhesive layer may be a layer made of any of an adhesive for EC (extrusion coating), an adhesive for dry lamination, an adhesive for non-solvent lamination, and the like. When an EC adhesive is used, although there are no particular limitations, for example, the adhesive is first heated and melted, expanded and stretched in the required width direction using a T-die or the like, extruded into a curtain shape, allowed to flow down onto the layer to be bonded, and then sandwiched between a rubber roll and a cooled metal roll, thereby simultaneously forming an adhesive layer and bonding and laminating to the layer to be bonded.

[0093] In another embodiment, the adhesive layer may be formed by sand lamination. In this case, any resin that can be applied by heating and melting in an extruder can be used for the adhesive layer. Specifically, the resins listed above as thermoplastic resins having heat sealability can be preferably used.

[0094] When using a dry lamination adhesive, the adhesive dispersed or dissolved in a solvent is applied onto one film and dried, and the other film is then laminated on top of it. The adhesive is then cured by aging at 30 to 120°C for several hours to several days to bond and laminate the films.

[0095] When using a non-solvent laminating adhesive, the adhesive itself is applied to the layer to be adhered without being dispersed or dissolved in a solvent, and then dried. The film that will form the other layer is then laminated on top of it, and the adhesive is hardened by aging at 30 to 120°C for several hours to several days before laminating.

[0096] The adhesive for dry lamination or the adhesive for non-solvent lamination can be used by coating, for example, by roll coating, gravure roll coating, kiss coating, etc., and the coating amount is 0.1 to 10 g / m 2 By setting the coating amount within the above range, good adhesion can be obtained.

[0097] (Anchor coat layer) The anchor coat layer can be formed from any anchor coat agent. Examples of anchor coating agents that can be used include organic titanium-based, isocyanate (urethane-based), polyethyleneimine-based, acid-modified polyethylene-based, polybutadiene-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based, and other anchor coating agents.

[0098] [Method of manufacturing the heat insulating laminate] The preparation method described below is an example and is not intended to limit the present invention. The formation and lamination of each layer constituting the heat insulating laminate can be carried out by any method, such as wet lamination, dry lamination, solventless dry lamination, extrusion lamination, T-die coextrusion molding, coextrusion lamination, inflation molding, and the like. The obtained heat insulating laminate can be subjected to secondary processing for the purpose of imparting surface functions such as chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubrication functions, optical functions, thermal functions, and biocompatibility.

[0099] Examples of secondary processing include embossing, painting, adhesives, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromic treatment, physical vapor deposition, chemical vapor deposition, coating, etc.), and the like.

[0100] As an example, the following describes the production of a heat insulating laminate (heat insulating packaging material) having a layer structure of gas barrier substrate layer [substrate layer / adhesive layer / substrate layer / adhesive layer / gas barrier layer] / adhesive layer / low outgassing gas adsorption sealant layer [heat seal layer 1 / adsorption layer / heat seal layer 2].

[0101] (Preparation of low outgassing gas adsorption sealant film) An adsorption layer resin composition for the adsorption layer and a low outgassing resin for the heat seal layer are separately prepared and then subjected to an inflation method to obtain a low outgassing gas adsorption sealant film having the following layer structure. Layer structure: heat seal layer 1 / adsorption layer / heat seal layer 2

[0102] (Preparation of heat insulating laminate) Next, the low outgassing gas adsorption sealant film obtained above for the low outgassing gas adsorption sealant layer, the base film 1 and base film 2 for the base layer, and the aluminum foil for the gas barrier layer were dry laminated in this order via the DL adhesive for the adhesive layer (coating amount: 3.5 g / m 2 , drying temperature: 70° C.) to obtain a heat insulating laminate having the above layer structure.

[0103] (Another embodiment of a method for forming and laminating a low gas-releasing gas-adsorbing sealant layer) The low outgassing gas adsorbent sealant layer may be laminated on another layer such as a gas barrier substrate layer by extrusion coating or co-extrusion. Even in the case of extrusion coating, the layer may be laminated via an adhesive layer as necessary.

[0104] <Insulation-retaining packaging materials> The heat insulating packaging material of the present invention is a packaging material made from the heat insulating laminate of the present invention, and may be the same as the heat insulating laminate, and may further include various functional layers, printed layers, etc., as necessary. The heat insulating packaging material of the present invention can also be subjected to lamination (dry lamination or extrusion lamination), bag making, and other post-treatments. A specific example of the heat insulating property-retaining packaging material of the present invention is a heat insulating property-retaining packaging material for a vacuum insulation panel.

[0105] <Thermal insulation packaging> The heat insulating packaging body of the present invention is a packaging body produced using the heat insulating packaging material of the present invention, and a specific example thereof is a vacuum insulation panel. The vacuum insulation panel can be used to produce a highly insulating container, such as a refrigerator, a freezer, a low-temperature container, a cooler box, a heat-retaining cabinet, a greenhouse, or a heat-retaining box. EXAMPLES

[0106] Details of the raw materials used in the examples are as follows. [Low gas emission resin] Low gas emission resin 1: Urutozex 3520L, manufactured by Prime Polymer Co., Ltd. C6-LLDPE, density 0.931g / cm 3 , MFR 2.1g / 10min. TOC concentration in the extracted water was 0.26ppm, and the elutable TOC concentration in the resin film was 42.3ppm. Low gas emission resin 2: Prime Polymer Co., Ltd., Neozex 3510F. C4-LLDPE, density 0.933g / cm 3, MFR 1.6g / 10min. TOC concentration in the extracted water was 0.32ppm, and the elutable TOC concentration in the resin film was 52.0ppm. Low gas emission resin 3: Urutozex 2021L, manufactured by Prime Polymer Co., Ltd. C6-LLDPE, density 0.919g / cm 3 , MFR 2.0g / 10min. TOC concentration in the extracted water was 0.56ppm, and the elutable TOC concentration in the resin film was 92.3ppm. Low gas emission resin 4: Novatec LC522, manufactured by Japan Polyethylene Co., Ltd. LDPE. Density 0.923g / cm 3 , MFR4g / 10min. TOC concentration in the extracted water was 0.32ppm, and the elutable TOC concentration in the resin film was 52.5ppm.

[0107] [General-purpose polyethylene] General-purpose polyethylene 1: Evolu SP4020 manufactured by Prime Polymer Co., Ltd. C6-LLDPE, density 0.937g / cm 3 , MFR 1.7g / 10min. TOC concentration in the extracted water was 2.85ppm, and the elutable TOC concentration in the resin film was 461ppm. General-purpose polyethylene 2: Prime Polymer Co., Ltd., Evolu SP1520. C6-LLDPE, density 0.913g / cm 3 , MFR 2.0g / 10min. TOC concentration in the extracted water was 3.05ppm, and the elutable TOC concentration in the resin film was 506ppm.

[0108] [Gas adsorbent] Hydrophobic zeolite 1: Mizusawa Chemical Industry Co., Ltd. hydrophobic zeolite, Mizuka Sieves EX-122. SiO2 / AL2O3 molar ratio = 32 / 1, average particle size = 2.5 to 5.5 μm. Hydrophobic zeolite 2: Silton MT400, a hydrophobic zeolite manufactured by Mizusawa Chemical Industry Co., Ltd. SiO2 / AL2O3 molar ratio = 400 / 1, average particle size = 5 to 7 μm. Hydrophobic zeolite 3: Silton MT-2000, a hydrophobic zeolite manufactured by Mizusawa Chemical Industry Co., Ltd. SiO2 / AL2O3 molar ratio = 2000 / 1, average particle size = 0.8 μm.

[0109] [Moisture absorbent] Moisture absorbent 1: Calcium oxide manufactured by Kalfain Co., Ltd. F-1300K, average particle size 4.3μm. Moisture absorbent 2: Magnesium oxide manufactured by Konoshima Chemical Co., Ltd. Starmag PSF-150, average particle size 0.6 μm.

[0110] [Antioxidants] Antioxidant 1: EAG-5, manufactured by Prime Polymer Co., Ltd. Contains a total of 5% by mass of phenol-based antioxidant and phosphorus-based antioxidant. MFR 4.5g / 10min.

[0111] [Film for base layer] Base film 1: Manufactured by Unitika Ltd., emblem ON, thickness 25μm. Base film 2: Toyobo Co., Ltd., Espet T4102, thickness 12 μm. Base film 3: IB-PET-PIR manufactured by Dai Nippon Printing Co., Ltd. Alumina-deposited PET film with a barrier-coat resin layer. Thickness: 12 μm.

[0112] [Metal foil for barrier layer] Aluminum foil 1: Manufactured by Toyo Aluminum Co., Ltd. Thickness: 6 μm.

[0113] [glue] DL Adhesive 1: ADOLOCK RU77T / H7 manufactured by Rock Paint Co., Ltd. Polyester adhesive.

[0114] [Preparation of master batch] The masterbatch used in the low outgassing, gas adsorbing sealant layer was prepared as follows.

[0115] (Preparation of Masterbatch 1) Low gas releasing resin 4 and hydrophobic zeolite 1 were melt blended in the following ratio to obtain master batch 1 (MB1). Low gas emission resin 4 60 parts by mass Hydrophobic zeolite 1 40 parts by weight

[0116] [Adjustment of Masterbatches 2 to 7] According to the formulation in Table 1, the raw materials were melt-blended in the same manner as for Masterbatch 1 to obtain Masterbatches 2 to 7 (MB2 to 7).

[0117] [Table 1]

[0118] [Preparation of Adsorption Layer Resin Composition] The adsorption layer resin composition used in the adsorption layer was prepared as follows.

[0119] (Preparation of Adsorption Layer Resin Composition 1) MB1 and low gas releasing resin 1 were dry blended in the following ratio to obtain an adsorption layer resin composition 1. MB1 4.2 parts by mass Low gas emission resin 1 95.8 parts by mass

[0120] (Preparation of Adsorption Layer Resin Compositions 2 to 9) According to the formulations shown in Table 2, the raw materials were dry-blended in the same manner as for the adsorption layer resin composition 1 to prepare adsorption layer resin compositions 2 to 9.

[0121] [Table 2]

[0122] [Preparation of moisture-absorbing layer resin composition] (Preparation of moisture absorbing layer resin composition 1) MB5 and low gas releasing resin 1 were dry blended in the following ratio to obtain moisture absorbing layer resin composition 1. MB1 58 parts by mass Low gas emission resin 1 42 parts by mass (Preparation of Moisture Absorbing Layer Resin Compositions 2 to 8) According to the formulations shown in Table 3, the raw materials were dry-blended in the same manner as in the case of the moisture absorbent layer resin composition 1 to prepare moisture absorbent layer resin compositions 2 to 8.

[0123] [Table 3]

[0124] (Preparation of Gas-Absorbing / Moisture-Absorbing Layer Resin Composition 1) The adsorption layer resin composition 4 and the moisture absorption layer resin composition 3 obtained above were dry-blended in the following ratio to obtain a gas-adsorbing / moisture absorption layer resin composition 1. Adsorption layer resin composition 4 50 parts by mass Moisture absorption layer resin composition 3 50 parts by mass

[0125] [Preparation of Heat Seal Layer Resin Composition] The following raw materials were dry-blended to obtain a resin composition 1 for a heat seal layer. Low gas emission resin 1 99.68 parts by mass Antioxidant 1 0.32 parts by mass

[0126] <Example 1> [Preparation of low gas-releasing, gas-adsorbing sealant film] Using the adsorption layer resin composition 1, moisture absorption layer resin composition 1, and low gas release resin 1 obtained above, a low gas release gas adsorption sealant film 1 having the following layer structure was obtained by an inflation method. The obtained low outgassing gas adsorbent sealant film 1 was used to evaluate film formability, low outgassing property, and gas adsorption performance. Layer structure of low gas release gas adsorption sealant film 1: Heat seal layer 1 / adsorption layer / moisture absorption layer / heat seal layer 2=low gas release resin 1 (10 μm thick) / adsorption layer resin composition 1 (20 μm thick) / moisture absorption layer resin composition 1 (20 μm thick) / low gas release resin 1 (10 μm thick)

[0127] [Preparation of heat insulating laminate] Next, the gas adsorption sealant film 1 and the base film 1 obtained above, and the base film 2 and the aluminum foil 1 were dry laminated with the DL adhesive 1 (coating amount: 3.5 g / m 2 , drying temperature: 70° C.) to obtain a heat insulation retaining laminate 1 having the following layer structure. Composition of heat insulating laminate 1: Gas barrier base layer (base film 1 / DL adhesive 1 / base film 2 / DL adhesive 1 / aluminum foil 1) / DL adhesive 1 / low gas release gas adsorption sealant film 1 The obtained heat insulation retaining laminate 1 was used to carry out evaluation of heat sealability and heat insulation. The evaluation results are shown in Table 5.

[0128] <Examples 2 to 13 and Comparative Examples 1 to 4> Using the raw materials shown in Tables 4, 6, and 8, low gas release gas adsorption sealant films and heat insulation retaining laminates were produced and evaluated in the same manner as in Example 1. The results are shown in Tables 5, 7, and 9.

[0129] <Evaluation method> [Film forming property] The appearance of the low outgassing gas adsorbent sealant film was observed and evaluated sensorily according to the following criteria: ○: Film formation is possible without wrinkles or bumps. ×: Numerous wrinkles and bumps were generated, making film formation difficult.

[0130] [Gas release amount] The low outgassing gas adsorption sealant film was cut to 50 mm x 10 mm, and two pieces of film were placed in a test tube and heated at 90°C for 60 minutes. The air in the test tube was sampled and the concentration of the organic gas component with carbon number 16 in the sampled air was measured by gas chromatography, and the amount of the organic gas component with carbon number 16 released per unit volume by the low outgassing gas adsorption sealant film was calculated.

[0131] [Gas adsorption] The low gas emission gas adsorption sealant film was cut to 10 x 10 cm and placed in a gas sampling bag (GL Sciences, SMART BAG) together with 600 cc of acetaldehyde gas adjusted to 100 ppm. After leaving it for 2 days, the gas concentration was measured using a detector tube (Gastec, Acetaldehyde No. 92M). In addition, instead of acetaldehyde gas, acetic acid gas adjusted to 30 ppm and ethyl acetate gas adjusted to 400 ppm were used to carry out the evaluation in the same manner as for acetaldehyde gas. The gas concentration measuring detector tubes used for acetic acid gas were "Gastec Co., Ltd., Acetic Acid No. 81" and for ethyl acetate gas were "Gastec Co., Ltd., Ethyl Acetate No. 141L".

[0132] [Heat sealability] The heat insulating laminate was cut into 10 cm x 10 cm pieces, and the low gas release gas adsorption sealant layer surfaces were overlapped. Using a heat seal tester (TP-701-A manufactured by Tester Sangyo Co., Ltd.), an area of ​​1 cm x 10 cm was heat sealed under the following conditions to produce a peel strength test piece in which the ends were not heat sealed or bonded and were divided into two. This test piece was cut into a strip of 15 mm width, and each bifurcated end was attached to a tensile tester to measure the peel strength (N / 15 mm) under the conditions below, and the pass / fail judgment was made according to the pass / fail judgment criteria below. Heat sealing conditions Temperature: 160℃ Pressure: 1kgf / cm 2 Time: 1 second Test conditions Test speed: 300mm / min Load range: 50N Pass / Fail Criteria ○: 30N / 15mm or more, passed. ×: Less than 30N / 15mm, failing.

[0133] [Thermal insulation maintenance] Two pieces of insulating laminate cut into a rectangle measuring 40 cm wide and 50 cm long were prepared, and the low gas-releasing gas adsorption sealant layers of the two insulating laminates were stacked facing each other, and a bag with one side open was obtained by heat-sealing an area of ​​2 cm to 3 cm from the ends of the outer edges of the three sides. From the opening of the bag, a 29cm wide x 30cm long x 3cm thick glass wool (weight 800g / m) is inserted as a core material. 2After placing a binder-free glass wool (product name: White Roll WR800, manufactured by Mag Isover) in the bag, air was sucked out from the opening of the bag. Suction was performed using a vacuum packaging machine (MVR-1000 model, manufactured by Shitara Seisakusho), and when the pressure inside the bag was reduced to 0.05 Pa, an area of ​​5 to 6 cm from the edge of the outer edge of the remaining side was heat sealed. The heat sealing was performed using a heat sealer (Impulse Sealer FA-600-10W, manufactured by Fuji Impulse Co., Ltd.). Furthermore, the entire outer edge was folded and fixed with tape to prepare a simple vacuum insulation panel as a test piece for evaluating insulation maintenance, in which the core material was wrapped in the insulation retaining laminate. The thermal conductivity was measured in the thickness direction of the simple vacuum insulation panel. First, the thermal conductivity was measured immediately after preparation (LMD1), and then the thermal conductivity was measured after storage for 1000 hours in a 100°C environment (LMD2). Then, Δthermal conductivity was calculated using the following formula, and the pass / fail of the insulation maintenance was judged according to the pass / fail judgment criteria below. ΔThermal conductivity = LMD2-LMD1 Pass / Fail Criteria Pass: ΔThermal conductivity is 7.0mW / mK or less. Fail: Δthermal conductivity is greater than 7.0 mW / mK.

[0134] [Leachable TOC concentration] Water was filled into a pouch made of a resin film, which was then sealed and stored at 35° C. for 2 weeks. The TOC concentration of the water was then measured to determine the increase in TOC concentration. Pouch size: inner dimensions 15cm x 44cm x 50μm thick. Filling water: Distilled water for high performance liquid chromatography manufactured by Junsei Chemical Co., Ltd. 65°C 1000g. TOC concentration measuring device: TOC-L total organic carbon meter manufactured by Shimadzu Corporation. Next, the concentration of soluble TOC contained in the resin film was calculated from the increased concentration of TOC in the filling water obtained above using the following formula. C = X × W1 / W2 =X×W1 / (6.6×S) C: Concentration of elutable TOC contained in the resin film [ppm] X: Increased concentration of TOC in the filling water [ppm] W1: Filled water weight = 1000[g] W2: Pouch weight = 15 x 44 x 50 x 10 -4 ×2×S=6.6×S[g] S: Density of resin film [g / cm 3 ]

[0135] [Table 4]

[0136] [Table 5]

[0137] [Table 6]

[0138] [Table 7]

[0139] [Table 8]

[0140] [Table 9]

[0141] <Summary of results> The heat insulating laminates of all the Examples exhibited good film-forming properties, low gas emission properties, and excellent adsorption properties for various gas components, and the heat insulating laminates exhibited good heat sealing properties and heat insulating property maintaining effects. However, the laminates of Comparative Examples 1 and 2, which had an insufficient content of the low gas-releasing resin, released a large amount of gas, and the laminate of Comparative Example 1, which did not contain a gas adsorbent, tended to have a low adsorption effect on various gas components. The laminates of Comparative Examples 1 to 3 showed poor heat insulation maintenance effects. In addition, the laminate of Comparative Example 4, in which the gas adsorbent content in the adsorption layer was too high, had a good gas adsorption effect but was poor in film formability. Furthermore, the heat insulation retention effect could not be evaluated because test pieces could not be prepared. [Explanation of symbols]

[0142] 1. Thermal insulation retaining laminate 2. Thermal insulation packaging materials 3 Gas barrier substrate layer 4. Low outgassing gas adsorption sealant layer 5a Adsorption layer 5b Adsorption layer 5c moisture absorption layer 5f Heat seal layer 6a Gas adsorbents 6b Moisture absorbent 7 Adhesive layer 10. Thermal insulation packaging (vacuum insulation panel) 11 Core material 12 Heat seal joint

Claims

1. A heat insulating retaining laminate for a vacuum insulation panel, which adsorbs gas generated from a sealant layer itself and gas from a space in contact with the sealant layer, the gas is one or a combination of two or more selected from the group consisting of hydrocarbons, aldehydes, ketones, carboxylic acids, esters, alcohols, carbon dioxide, and water vapor; The heat insulating support laminate has a gas barrier substrate layer and a low outgassing gas adsorbent sealant layer, The low outgassing gas adsorbing sealant layer contains a low outgassing resin having heat sealability, a gas adsorbent, and a moisture absorbent, The low gas emission resin is a polyethylene resin having a density of 0.915 g / cm ３ Above, 0.935g / cm ３ is as follows: The concentration of elutable total organic carbon (TOC) contained in the film made of the low gas emission resin is 1.5 ppm or more and 250 ppm or less, The low outgassing gas adsorbent sealant layer is a layer made of a low outgassing gas adsorbent sealant film, The low outgassing gas adsorbing sealant film has a carbon number of 16 organic gas component released when heated in air at 90° C. for 60 minutes, and the amount of the low outgassing gas adsorbing sealant film per unit volume of the low outgassing gas adsorbing sealant film is 10 μg / cm ３ Above, 1000μg / cm ３ is as follows: The gas adsorbent comprises one or a combination of two or more selected from the group consisting of hydrophobic zeolite, molecular sieve, metal-organic framework (MOF), and non-polar activated carbon; The content of the low gas release resin in the entire low gas release gas adsorption sealant layer is 70% by mass or more and 99.9% by mass or less, the content of the gas adsorbent in the layer containing the gas adsorbent is 0.1% by mass or more and 30% by mass or less; The content of the moisture absorbent in the layer containing the moisture absorbent is 1% by mass or more and 50% by mass or less. A heat insulating laminate comprising:

2. The low gas emission resin is selected from medium density polyethylene, low density polyethylene and linear low density polyethylene.

2. The heat insulating laminate according to claim 1, which is made of one or a combination of two or more selected from the group consisting of polyethylene and ethylene.

3. 3. The heat insulating laminate according to claim 1, wherein the moisture absorbent is one or a combination of two or more selected from the group consisting of calcium oxide, magnesium oxide, barium oxide, and hydrophilic zeolite.

4. The low outgassing gas adsorbent sealant layer has an adsorbent layer and a heat seal layer, the adsorption layer is a layer containing the low gas release resin, the gas adsorbent, and the moisture absorbent, the heat seal layer contains the low gas release resin and has heat sealability; At least one outermost layer of the low outgassing gas adsorbent sealant layer is a heat seal layer, The low gas-releasing resin contained in the adsorption layer and the low gas-releasing resin contained in the heat seal layer are the same or different. The heat insulating laminate according to any one of claims 1 to 3.

5. 5. The heat insulating laminate according to claim 4, wherein the adsorption layer comprises a gas adsorption layer and a moisture absorption layer.

6. The heat insulating laminate according to any one of claims 1 to 5, wherein the low outgassing gas adsorbing sealant layer further contains an antioxidant.

7. The heat insulating laminate according to claim 6, wherein the content of the antioxidant is 0.005% by mass or more and 0.5% by mass or less in the entire low outgassing gas adsorption sealant layer.

8. The low outgassing gas adsorbent sealant layer has an adsorbent layer and a heat seal layer, the antioxidant is contained in the adsorption layer and / or the heat seal layer, The antioxidant contained in the adsorption layer and the antioxidant contained in the heat seal layer are the same or different. The heat insulating retaining laminate according to claim 6 or 7.

9. A heat insulating packaging material for a vacuum insulation panel, produced using the heat insulating laminate according to any one of claims 1 to 8.

10. A vacuum insulation panel made using the heat insulating packaging material according to claim 9.

Images