WO2018062047A1 - Matériau d'emballage externe pour matériau d'isolation sous vide, matériau d'isolation sous vide, et article pourvu d'un matériau d'isolation sous vide - Google Patents

Matériau d'emballage externe pour matériau d'isolation sous vide, matériau d'isolation sous vide, et article pourvu d'un matériau d'isolation sous vide Download PDF

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Publication number
WO2018062047A1
WO2018062047A1 PCT/JP2017/034357 JP2017034357W WO2018062047A1 WO 2018062047 A1 WO2018062047 A1 WO 2018062047A1 JP 2017034357 W JP2017034357 W JP 2017034357W WO 2018062047 A1 WO2018062047 A1 WO 2018062047A1
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Prior art keywords
gas barrier
film
outer packaging
barrier layer
packaging material
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PCT/JP2017/034357
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English (en)
Japanese (ja)
Inventor
琢 棟田
将博 今井
結香 立川
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大日本印刷株式会社
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Publication of WO2018062047A1 publication Critical patent/WO2018062047A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/06—Arrangements using an air layer or vacuum
    • F16L59/065—Arrangements using an air layer or vacuum using vacuum

Definitions

  • the present disclosure relates to an outer packaging material for a vacuum heat insulating material that can form a vacuum heat insulating material, a vacuum heat insulating material, and an article with a vacuum heat insulating material.
  • the vacuum heat insulating material has a core material and an outer packaging material in which the core material is enclosed.
  • the inside of the bag body constituted by the outer packaging material is held in a vacuum state in which the core material is disposed and the pressure is lower than the atmospheric pressure. Since heat convection inside the bag is suppressed, the vacuum heat insulating material can exhibit good heat insulating performance.
  • the outer packaging material constituting the vacuum heat insulating material has a gas barrier property for suppressing the passage of gas and heat welding for forming a bag body. Sex is required. Therefore, the outer packaging material for a vacuum heat insulating material generally has a gas barrier film and a heat-weldable film (for example, Patent Documents 1 to 3).
  • Patent Documents 1 to 3 disclose that the outer packaging material may be bent when the vacuum heat insulating material is manufactured or used. Even if the outer packaging material for a vacuum heat insulating material is bent, it is desirable that defects such as minute cracks are less likely to occur. Even if vacuum insulation materials with minute defects in the outer packaging material show the same level of insulation performance as the one without them in the initial state, the deterioration of the insulation performance is larger during use. It is to become.
  • This disclosure mainly aims to provide an outer packaging material for a vacuum heat insulating material and the like capable of forming a vacuum heat insulating material capable of maintaining good heat insulating performance.
  • the present disclosure is an outer packaging material for a vacuum heat insulating material having a heat-weldable film, a first gas barrier film, and a second gas barrier film in this order, and the first gas barrier
  • the film has a first resin base material and a first gas barrier layer
  • the second gas barrier film has a second resin base material and a second gas barrier layer
  • the first gas barrier film and the first gas barrier layer The two-gas barrier film is arranged so that the first gas barrier layer and the second gas barrier layer face each other, and for each film constituting the outer packaging material for vacuum heat insulating material, the indentation elastic modulus and thickness of each film are When the product is the indentation elastic index of each film, the pressing for each film positioned on the second gas barrier layer side with respect to the first gas barrier layer.
  • the outer packaging material for a vacuum heat insulating material in which the difference between the sum of the elastic indices and the sum of the indentation elastic indices of the respective films located on the first gas barrier layer side with respect to the second gas barrier layer is 50 GPa ⁇ ⁇ m or less I will provide a.
  • the present disclosure is a vacuum heat insulating material having a core material and an outer packaging material for a vacuum heat insulating material in which the core material is enclosed, and the outer packaging material for the vacuum heat insulating material is the outer packaging material for a vacuum insulating material described above.
  • a vacuum insulation material is provided.
  • the present disclosure provides an article having a heat insulating region and an article with a vacuum heat insulating material including a vacuum heat insulating material, wherein the vacuum heat insulating material is the above-described vacuum heat insulating material.
  • an outer packaging material for a vacuum heat insulating material capable of forming a vacuum heat insulating material capable of maintaining good heat insulating performance.
  • the present disclosure relates to an outer packaging material for a vacuum heat insulating material, a vacuum heat insulating material using the same, and an article with a vacuum heat insulating material.
  • the outer packaging material for vacuum heat insulating material, the vacuum heat insulating material, and the article with the vacuum heat insulating material of the present disclosure will be described.
  • the “wrapping material for vacuum heat insulating material” may be abbreviated as “wrapping material”.
  • the first gas barrier film and the second gas barrier film are collectively referred to as a “gas barrier film”, the first resin base material and the second resin base material are collectively referred to as a “resin base material”, and the first gas barrier layer and the second gas barrier layer are collectively illustrated.
  • the heat-weldable film side which is the inner side of the vacuum heat insulating material is “the inner side of the outer packaging material” and the outer side of the vacuum heat insulating material is the heat-weldable film.
  • the side far from the position may be described as “the outside of the outer packaging material”.
  • the outer packaging material for vacuum heat insulating material of the present disclosure is an outer packaging material for a vacuum heat insulating material having a heat-weldable film, a first gas barrier film, and a second gas barrier film in this order, and the first gas barrier film is The first resin base material and the first gas barrier layer, the second gas barrier film has the second resin base material and the second gas barrier layer, and the first gas barrier film and the second gas barrier film are: The first gas barrier layer and the second gas barrier layer are arranged so as to face each other, and for each film constituting the outer packaging material for vacuum heat insulating material, the product of the indentation elastic modulus and the thickness of each film is expressed as the indentation elastic index of each film.
  • the difference between the sum of the indentation elastic index for each film located on the side is, is not more than 50 GPa ⁇ [mu] m.
  • FIG. 1 is a schematic cross-sectional view illustrating an example of the outer packaging material of the present disclosure.
  • the outer packaging material 10 of the present disclosure includes a thermally weldable film 1, a first gas barrier film 2, and a second gas barrier film 3 in this order.
  • the first gas barrier film 2 has a first resin base material 4 and a first gas barrier layer 5
  • the second gas barrier film 3 has a second resin base material 6 and a second gas barrier layer 7.
  • the first gas barrier film 2 and the second gas barrier film 3 are arranged so that the first gas barrier layer 5 and the second gas barrier layer 7 face each other.
  • FIG. 2 is a schematic cross-sectional view showing an example of a vacuum heat insulating material using the outer packaging material of the present disclosure.
  • the vacuum heat insulating material 20 includes a core material 11 and an outer packaging material 10 in which the core material 11 is enclosed.
  • the outer packaging material 10 is formed into a bag by joining the inner sides of the outer packaging material 10 at the end 12.
  • a core material 11 is disposed inside the bag body constituted by the outer packaging material 10 and is maintained in a vacuum state in which the pressure is lower than the atmospheric pressure.
  • FIG. 3 is an explanatory view showing an example of the usage state of the vacuum heat insulating material, and is a cross-sectional view showing an example in which two vacuum heat insulating materials are used side by side.
  • the end portion 12 in the two vacuum heat insulating materials 20, the end portion 12 is bent to form a bent portion 13.
  • the area ratio occupied by the end portions 12 having low heat insulating performance when the two vacuum heat insulating materials 20 are viewed in plan is small.
  • tensile / compressive stress is applied to the bent portion 13.
  • tensile / compressive stress is also applied to the bent portion 14 that is the base portion of the end portion 12 on the core material 11 side, the corner portion 15 of the outer packaging material 10 that covers the corner portion of the core material 11, and the like. Therefore, in the bent portion 13, the bent portion 14, and the corner portion 15, minute defects such as minute cracks and minute pinholes are likely to occur in the outer packaging material 10.
  • the outer packaging material of the present disclosure is the second gas barrier film rather than the first gas barrier film when the product of the indentation elastic modulus and the thickness of each film is the indentation elastic index of each film.
  • a gas barrier film that is a laminate of a gas barrier layer composed of an extremely thin film such as a metal vapor deposition film and a resin base material is used. is there. Since the thickness of the gas barrier layer of the laminate as described above is significantly thinner than a conventionally used aluminum foil or the like, minute defects are likely to occur even with a small stress. Therefore, the present inventors have conducted intensive studies on the arrangement of the gas barrier layer in the outer packaging material and the relationship with each film used together with the outer packaging material in order to suppress the occurrence of minute defects in the gas barrier layer.
  • a plurality of gas barrier films may be used for one outer packaging material.
  • the gas barrier layers of the two gas barrier films are arranged in the same direction or face each other (the resin bases face each other).
  • the thickness and indentation elastic modulus of each film so that the two gas barrier layers are positioned in the vicinity of the neutral plane described above It is presumed that the occurrence of minute defects can be suppressed more effectively and efficiently by adjusting.
  • the outer packaging material of the present disclosure includes a heat-weldable film, a first gas barrier film, and a second gas barrier film.
  • Characteristics of outer packaging material for vacuum heat insulating material (1) Difference in indentation elastic index The outer packaging material of the present disclosure is obtained by calculating the product of the indentation elastic modulus and the thickness of each film, and the indentation elasticity of each film.
  • the sum of the indentation elastic index for each film located on the second gas barrier layer side with respect to the first gas barrier layer and the indentation for each film located on the first gas barrier layer side with respect to the second gas barrier layer is 50 GPa ⁇ ⁇ m or less, preferably 40 GPa ⁇ ⁇ m or less, more preferably 20 GPa ⁇ ⁇ m or less, more preferably 10 GPa ⁇ ⁇ m. The following is more preferable.
  • the lower limit of the difference in indentation elastic index is preferably 0 GPa ⁇ ⁇ m, but may be 0.5 GPa ⁇ ⁇ m, 1 GPa ⁇ ⁇ m, or 3 GPa ⁇ ⁇ m, for example. It may be 5 GPa ⁇ ⁇ m or 7.5 GPa ⁇ ⁇ m. Therefore, the difference of the indentation elastic index can be set in a range of any combination of the upper limit and the lower limit described above, for example, a range of 0 GPa ⁇ ⁇ m to 50 GPa ⁇ ⁇ m, and a range of 0 GPa ⁇ ⁇ m to 40 GPa ⁇ ⁇ m.
  • the difference in the indentation elastic index exceeds the above range, a minute defect may easily occur in the outer packaging material.
  • the difference in the indentation elastic index is preferably as small as possible. Such “difference in indentation elasticity index” will be described in detail below.
  • the indentation elastic modulus and thickness of any one film constituting the outer packaging material are measured and multiplied by these values is the “indentation elastic index” for the film.
  • the indentation elastic index is calculated for each film constituting the outer packaging material. For example, in the case of an outer packaging material in which a heat-weldable film, a first gas barrier film, and a second gas barrier film are laminated as illustrated in FIG. 1, these heat-weldable films, The indentation elasticity index is calculated for each of the first gas barrier film and the second gas barrier film.
  • Each gas barrier film has a resin base material and a gas barrier layer, but the gas barrier layer is thin and has a small influence on the indentation elastic index of the laminate, and is negligible. Therefore, the indentation elastic index of the resin base material is regarded as the indentation elastic index of the gas barrier film.
  • the “difference in indentation elastic index” includes “the sum of indentation elastic indices for each film (outer film) positioned on the second gas barrier layer side with respect to the first gas barrier layer” and “the first indentation over the second gas barrier layer”. It can be determined by calculating the difference from the “sum of indentation elastic indices for each film (inner film) located on the gas barrier layer side”.
  • the indentation elastic index for the adhesive layer is equal to the “sum of the indentation elastic index” of the inner or outer film described above.
  • the adhesive generally used for the outer packaging material for vacuum heat insulating materials can be used.
  • the outer packaging material 10 includes the heat-weldable film 1, the first gas barrier film 2, the second gas barrier film 3, and the protective film 8 in this order.
  • the sum of the indentation elastic index of the second gas barrier film 3 and the indentation elastic index of the protective film 8 located on the second gas barrier layer 7 side of the first gas barrier layer 5 is the indentation elastic index of the outer film
  • the sum of the indentation elastic index of the first gas barrier film 2 and the indentation elastic index of the heat-weldable film 1 located on the first gas barrier layer 5 side of the second gas barrier layer 7 is the indentation elastic index of the inner film.
  • the indentation elastic modulus of the heat-weldable film, the first gas barrier film, the second gas barrier film, and the protective film is E1, E2, E3, and E8, and the thicknesses of these films are T1, T2, T3, and T8.
  • the difference in the indentation elastic index of the outer packaging material 10 illustrated in FIG. 4 is a difference between (E1 ⁇ T1 + E2 ⁇ T2) and (E3 ⁇ T3 + E8 ⁇ T8).
  • FIG. 4 is a schematic cross-sectional view showing another example of the outer packaging material of the present disclosure, and reference numerals not described in FIG. 4 are the same as those in FIG.
  • the indentation elastic modulus is measured according to ISO 14577, with a Vickers indenter (a square pyramid diamond indenter with a face angle of 136 °) in an environment of about 23 ° C and about 60% RH on the sample cross section or surface.
  • a method of measuring indentation elastic modulus using an ultra-micro load hardness tester is used. The measurement is performed at an indentation speed of 0.1 ⁇ m / second, an indentation depth of 2 ⁇ m, a holding time of 5 seconds, and an extraction speed of 0.1 ⁇ m / second.
  • the micro hardness tester is preferably Picodenter HM500 (Fischer Instruments).
  • the average of the measured values is taken as the value of the indentation elastic modulus of the condition.
  • the outer periphery of the sample is fixed by fixing with a cured resin adhesive, the fixed sample is cut in the thickness direction with a diamond knife, and the exposed cross section of the sample is measured.
  • the surface of the sample is fixed to a flat glass plate having a thickness of 1.1 mm with a cured resin adhesive, and the surface of the sample is measured.
  • the thickness of each film when calculating the indentation elasticity index can be measured by measuring the cut section with an optical microscope. The same applies to the thickness in the following description.
  • the tensile elastic modulus of the outer packaging material is not particularly limited as long as the difference in the indentation elastic modulus of the outer packaging material can be within the above-described range.
  • it can be 1.0 GPa or more.
  • the tensile modulus of the outer packaging material is preferably 1.5 GPa or more, more preferably 2.0 GPa or more, more preferably 2.5 GPa or more, and 2.8 GPa or more. Particularly preferred. It is because generation
  • the upper limit of the tensile modulus of the outer packaging material is not particularly limited, and can be, for example, 5.0 GPa or less, and preferably 3.5 GPa or less. If the tensile modulus of the outer packaging material is too high, it is necessary to apply a strong stress when the outer packaging material is bent.If the outer packaging material has a weak portion, the stress concentrates on the portion and is very small. This is because defects may easily occur. Therefore, the tensile elastic modulus of the outer packaging material can be set within the range of any combination of the upper limit and the lower limit described above in consideration of these points, specifically, 1.5 GPa or more and 5.0 GPa or less.
  • Range 1.5 GPa to 3.5 GPa range, 2.0 GPa to 5.0 GPa range, 2.0 GPa to 3.5 GPa range, 2.3 GPa to 5.0 GPa range, 2.3 GPa or more
  • the tensile modulus was measured in accordance with JIS K7161-1: 2014 (Plastics-Determination of tensile properties-Part 1: General rules), and the outer packaging material was cut into a rectangle with a width of 15 mm, and a sample was collected.
  • JIS K7161-1: 2014 Plastics-Determination of tensile properties-Part 1: General rules
  • a method is used in which the tensile elastic modulus is measured under the conditions that the distance between chucks is 100 mm, the tensile speed is 100 mm / min, and the reserve force is used.
  • the measurement environment is 23 ° C. and humidity 55%.
  • the length of the sample is determined within a range in which a gripping tool is attached so that the length of the sample coincides with the axis of the testing machine and the gripping portion does not shift during measurement, and is, for example, about 120 mm.
  • the tensile tester is preferably Instron 5565 (Instron Japan).
  • the reserve force is, for example, the stress as ⁇ 0 and the elastic modulus as Et (if the appropriate elastic modulus or stress for the reserve force is unknown, test in advance to obtain the predicted value of the elastic modulus or stress. ( Et / 10000) ⁇ ⁇ 0 ⁇ (E t / 3000).
  • At least five samples are measured, and the average of the measured values is taken as the value of the tensile modulus of the condition.
  • the value of a tensile elasticity modulus may change with directions in an outer packaging material surface, use of an in-plane average value is preferable.
  • the average of the values of the eight conditions obtained by changing the condition in the in-plane direction of the outer packaging material by approximately 22.5 degrees can be regarded as the in-plane average value.
  • the tensile modulus of the outer packaging material is measured for the entire outer packaging material. Therefore, when the outer packaging material includes a film other than a heat-weldable film or a gas barrier film, the outer packaging material is measured in a state including those films. For example, when each film is laminated
  • the outer packaging material of this indication has the 1st gas barrier film and the 2nd gas barrier film.
  • the first gas barrier film has a first resin base material and a first gas barrier layer
  • the second gas barrier film has a second resin base material and a second gas barrier layer.
  • the first gas barrier film and the second gas barrier film are arranged so that the first gas barrier layer and the second gas barrier layer face each other.
  • the first gas barrier film and the second gas barrier film may each be a gas barrier film having the same configuration, or may be a gas barrier film having a different configuration, such as a different gas barrier layer or resin substrate. May be.
  • the first gas barrier film and the second gas barrier film in the present disclosure may have the following configurations, respectively.
  • Gas barrier layer A gas barrier layer is arrange
  • the gas barrier layer In the first gas barrier film or the second gas barrier film, when the gas barrier layer is disposed only on one surface side of the resin base material, the gas barrier layer is disposed so as to face the second gas barrier film or the first gas barrier film side. Is done.
  • the gas barrier layer when the gas barrier layer is arrange
  • the gas barrier layer thus formed is the first gas barrier layer or the second gas barrier layer.
  • Such a gas barrier layer is not particularly limited as long as a desired gas barrier property can be exhibited, and examples thereof include a metal thin film such as a metal vapor deposition film and an inorganic compound film that is a vapor deposition film of an inorganic compound.
  • the metal which forms a metal thin film should just be a metal which can exhibit desired barrier performance, for example, aluminum, stainless steel, titanium, nickel, iron, copper etc. are mentioned.
  • the inorganic compound that forms the inorganic compound film may be any material that can exhibit a desired gas barrier property, such as inorganic oxide, inorganic oxynitride, inorganic nitride, inorganic oxide carbide, inorganic oxycarbonitride, and the like.
  • examples thereof include one or more inorganic compounds selected from silicon zinc oxide and the like.
  • the said inorganic compound may be used independently, and the said material may be mixed and used for arbitrary ratios.
  • the gas barrier layer is preferably a metal thin film, and particularly preferably an aluminum thin film. This is because the effect of the present disclosure that the generation of cracks can be suppressed can be more effectively exhibited.
  • the thickness of the gas barrier layer is not particularly limited as long as a desired gas barrier property can be exhibited. Depending on the type of the gas barrier layer, for example, the thickness is in the range of 5 nm or more and 500 nm or less. In particular, it is preferably in the range of 10 nm or more and 300 nm or less, and particularly preferably in the range of 20 nm or more and 100 nm or less. If the thickness of the gas barrier layer is less than the above range, film formation may be insufficient and the desired gas barrier property may not be exhibited. If the thickness exceeds the above range, cracks are likely to occur and flexibility is reduced. This is because when the gas barrier layer is a metal thin film, a heat bridge may occur in the vacuum heat insulating material formed using the outer packaging material of the present disclosure.
  • the gas barrier layer may be a single layer, or two or more layers may be laminated so that the total thickness is within the above range.
  • gas barrier layers having the same composition may be combined, or gas barrier layers having different compositions may be combined.
  • the gas barrier layer may be subjected to surface treatment such as corona discharge treatment from the viewpoint of improving gas barrier properties and adhesion to other films.
  • a conventionally known method can be used depending on the type of the gas barrier layer.
  • the gas barrier layer is a metal thin film
  • a method of forming a film on a resin substrate using a dry film forming method such as a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method, specifically For example, a vacuum deposition method or the like can be used.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • a vacuum deposition method or the like can be used.
  • the method of sticking a resin base material and a gas barrier layer through an adhesive bond layer etc. using a ready-made metal thin film, the resin base material and the metal thin film heated previously is mentioned.
  • the inorganic compound film can be formed on the resin substrate using, for example, a dry film forming method such as a PVD method or a CVD method.
  • a dry film forming method such as a PVD method or a CVD method.
  • a specific method for forming the gas barrier layer by the PVD method and the CVD method for example, a method disclosed in JP 2011-5835 A can be used.
  • the resin base material is not particularly limited as long as it can support the gas barrier layer.
  • a resin film or a resin sheet is preferably used.
  • the resin film may be unstretched or may be uniaxially or biaxially stretched.
  • the resin used for the resin substrate is not particularly limited, and examples thereof include polyolefins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene.
  • polyolefins such as polyethylene and polypropylene
  • polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate
  • cyclic polyolefin resins such as polyethylene terephthalate (PET) and polyethylene naphthalate
  • polystyrene resins such as polystyrene resins
  • acrylonitrile-styrene acrylonitrile-styrene.
  • Polyvinyl alcohol such as copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), (meth) acrylic resin, polycarbonate resin, polyvinyl alcohol (PVA) and ethylene-vinyl alcohol copolymer (EVOH)
  • Various resins such as resins, saponified ethylene-vinyl ester copolymers, polyamide resins such as nylon, polyurethane resins, polyacetal resins, and cellulose resins can be used.
  • the resin base material may contain various plastic compounding agents and additives.
  • the additive include a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and a modifying resin.
  • the resin substrate may be subjected to a surface treatment. This is because the adhesion to the gas barrier layer can be improved.
  • the surface treatment include oxidation treatment, roughening treatment (roughening treatment), easy adhesion coating treatment and the like disclosed in Japanese Patent Application Laid-Open No. 2014-180837.
  • the thickness of the resin base material is not particularly limited as long as the indentation elastic index difference in the outer packaging material described above can be set to a desired value.
  • the thickness of the resin base material is in the range of 6 ⁇ m or more and 200 ⁇ m or less. Especially, it can be in the range of 9 ⁇ m or more and 100 ⁇ m or less.
  • the indentation elastic modulus of the resin base material is not particularly limited as long as the indentation elastic index difference in the outer packaging material can be set to a desired value, but is preferably 1.0 GPa or more, , 1.5 GPa or more and 4.0 GPa or less is preferable, and 2.0 GPa or more and 3.0 GPa or less is particularly preferable.
  • the resin base material can more effectively protect the gas barrier layer disposed in the vicinity, and the generation of minute defects is further suppressed. Because it can.
  • the oxygen permeability is preferably 0.5 cc / (m 2 ⁇ day ⁇ atm) or less, and in particular, 0.1 cc / (m 2 ⁇ day ⁇ atm).
  • the water vapor permeability is preferably 0.2 g / (m 2 ⁇ day) or less, and more preferably 0.1 g / (m 2 ⁇ day) or less.
  • the oxygen permeability is measured according to JIS K7126-2A: 2006 (Plastics-Film and Sheet-Gas Permeability Test Method-Part 2: Isobaric Method, Appendix A: Oxygen Gas Permeability by Electrolytic Sensor Method.
  • JIS K7126-2A 2006 (Plastics-Film and Sheet-Gas Permeability Test Method-Part 2: Isobaric Method, Appendix A: Oxygen Gas Permeability by Electrolytic Sensor Method.
  • the outer side of the outer packaging material (the side where the gas barrier film of the heat-weldable film is disposed) is oxygen using an oxygen permeability measuring device.
  • a measurement method is used under the condition of a permeation area of 50 cm 2 in contact with the gas.
  • the oxygen permeability measuring device is preferably OXTRAN (OXTRAN 2/21 10X, manufactured by MOCON, a US company).
  • the test gas is purged with at least 99.5% dry oxygen at a carrier gas flow rate of 10 cc / min for 60 minutes or more, and then the test gas is flowed.
  • the measurement was started after 12 hours were secured as the time from the start of flowing the test gas until the equilibrium state was reached. In one condition, at least three samples are measured, and the average of the measured values is taken as the oxygen permeability value for that condition.
  • the water vapor transmission rate is measured in accordance with JIS K7129-B: 2008 (Plastics-Films and Sheets-Method for determining water vapor transmission rate (instrument measurement method), Appendix B: Infrared sensor method).
  • the outer side of the outer packaging material (the side where the gas barrier film of the heat-weldable film is disposed) is on the high humidity side (water vapor supply)
  • the measurement method is used under the condition of a transmission area of 50 cm 2 .
  • the water vapor transmission rate measuring device is preferably Permatran (PERMATRAN-3 / 33G +, manufactured by MOCON, an American company).
  • NIST film # 3 is used as a standard test piece. Under one condition, at least three samples are measured, and the average of the measured values is taken as the value of the water vapor permeability of the condition.
  • Heat-weldable film in the present disclosure is a part in contact with a core material when a vacuum heat insulating material is formed using the outer packaging material. Moreover, it is a site
  • thermoplastic resin As a film material that can be thermally welded, a thermoplastic resin is preferable because it can be melted and fused by heating.
  • polyethylene such as linear short-chain branched polyethylene (LLDPE) or unstretched polypropylene ( CPP), polyolefin resins such as biaxially oriented polypropylene (OPP), polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyvinyl acetate resins, polyvinyl chloride Resin, (meth) acrylic resin, polyurethane resin and the like.
  • LLDPE linear short-chain branched polyethylene
  • CPP unstretched polypropylene
  • OPP biaxially oriented polypropylene
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PBT polybutylene terephthalate
  • polyvinyl acetate resins polyvinyl chlor
  • linear short-chain branched polyethylene, unstretched polypropylene, or polybutylene terephthalate is preferable, and polybutylene terephthalate is particularly preferable. This is because when the vacuum heat insulating material is formed, generation of minute defects can be further suppressed at the end portion where the outer packaging materials are bonded together.
  • the heat-weldable film may contain other materials such as an anti-blocking agent, a lubricant, a flame retardant, and an organic filler in addition to the above-described resin.
  • the melting temperature of the heat-weldable film is preferably, for example, in the range of 80 ° C. or higher and 300 ° C. or lower, and more preferably in the range of 100 ° C. or higher and 250 ° C. or lower.
  • the melting temperature (Tm) is measured in accordance with JIS K7121: 2012 (plastic transition temperature measuring method), using a differential scanning calorimetry (DSC) apparatus to measure the DSC curve to obtain the melting temperature. . About 10 mg of sample was collected, placed in an aluminum container, and attached to the apparatus. The DSC curve was measured by increasing the temperature from a starting temperature of 20 ° C. to 250 ° C. at a heating rate of 10 ° C./min, holding at 250 ° C. for 10 minutes, and decreasing the temperature from 250 ° C. to 20 ° C. at a cooling rate of 10 ° C./min. Do it. The melting temperature is determined from the DSC curve at the time of temperature increase.
  • the DSC device is preferably DSC204 (manufactured by NETZSCH).
  • the indentation elastic modulus of the heat-weldable film is not particularly limited as long as the indentation elastic index difference in the outer packaging material described above can be set to a desired value, but is 0.5 GPa or more. In particular, it is preferably in the range of 0.8 GPa or more and 3.0 GPa or less, and particularly preferably in the range of 1.0 GPa or more and 2.5 GPa or less.
  • the indentation elastic modulus of the heat-weldable film is within the above-described range, when a vacuum heat insulating material is formed, generation of minute defects can be further suppressed at the end portion where the outer packaging materials are bonded together. Because. Moreover, it is because generation
  • the thickness of the heat-weldable film is not particularly limited as long as the difference in the indentation elastic index in the outer packaging material described above can be set to a desired value.
  • the thickness is in the range of 20 ⁇ m or more and 100 ⁇ m or less.
  • the inside is preferable, and the range of 25 ⁇ m or more and 90 ⁇ m or less is particularly preferable, and the range of 30 ⁇ m or more and 80 ⁇ m or less is particularly preferable. If the thickness of the heat-weldable film is larger than the above range, the gas barrier property of the outer packaging material may be lowered. If the thickness is smaller than the above range, a desired adhesive force may not be obtained. .
  • the outer packaging material of the present disclosure includes at least a heat-weldable film, a first gas barrier film, and a second gas barrier film, but may have other arbitrary configurations.
  • the outer packaging material of this indication may have a protective film other than the heat-weldable film and gas barrier film mentioned above. It is because each film used together as an outer packaging material, such as a heat-weldable film and a gas barrier film, can be protected from damage and deterioration by having the protective film as a protective film.
  • the protective film can be distinguished from the above-described gas barrier film in that a layer having gas barrier properties is not disposed on either side of the protective film.
  • the arrangement position of the protective film in the outer packaging material is not particularly limited, but the protective film is preferably arranged on the side opposite to the thermally weldable film of the first gas barrier film and the second gas barrier film, It is more preferable that a protective film is disposed at a position to be the outermost layer (outermost layer) when forming the material.
  • the protective film may be any film using a resin having a higher melting point than a heat-weldable film, and may be in the form of a sheet or film.
  • a protective film for example, a sheet or film of a nylon resin, a polyester resin, a polyamide resin, a polypropylene resin, or the like can be given.
  • the protective film may be a single layer, or may be a multilayer formed by laminating layers made of the same material or layers made of different materials.
  • the protective film may be subjected to a surface treatment such as a corona discharge treatment from the viewpoint of improving the adhesion with other layers.
  • the thickness of the protective film is not particularly limited as long as it can make the difference in the indentation elastic index in the outer packaging material described above a desired value and can protect the heat-weldable film and the gas barrier film. Although it is not a thing, generally it can be in the range of 5 micrometers or more and 80 micrometers or less.
  • the indentation elastic modulus of the protective film is not particularly limited as long as the difference in the indentation elastic index in the outer packaging material described above can be a desired value, but is preferably 1.0 GPa or more, Especially, it is preferable that it exists in the range of 1.5 GPa or more and 4.0 GPa or less, and it is especially preferable that it exists in the range of 2.0 GPa or more and 3.0 GPa or less. If the indentation elastic modulus of the protective film is less than the above range, there is a possibility that the films used together as the outer packaging material cannot be sufficiently protected from damage and deterioration. On the other hand, when the indentation elastic modulus of the protective film exceeds the above range, it may be difficult to adjust the difference in the indentation elastic index as the outer packaging material within a desired range.
  • the outer packaging material of this indication may have the further gas barrier film other than the 1st gas barrier film and the 2nd gas barrier film which were mentioned above.
  • the gas barrier film located on the thermally weldable film side of the two gas barrier films facing each other is the first gas barrier film and can be thermally welded.
  • the gas barrier film located on the side away from the film is the second gas barrier film, and the layer configuration is designed so that the difference in indentation elastic modulus is within the above range for each of the inner and outer gas barrier layers facing each other. can do.
  • the layer configuration can be designed.
  • the further gas barrier film may be arranged inside the first gas barrier film and the second gas barrier film, may be arranged outside, or may be arranged both inside and outside.
  • Such a further gas barrier film can be the same as that described in “2. Gas barrier film” described above, and thus the description thereof is omitted here.
  • the oxygen permeability after the bending test is preferably 1.2 cc / (m 2 ⁇ day ⁇ atm) or less, and in particular, 0.8 cc / ( m 2 ⁇ day ⁇ atm) or less. Since the gas barrier property of the outer packaging material is within the above-described range, it is possible to maintain a high degree of vacuum inside the vacuum heat insulating material even when the outer packaging material is bent when forming the vacuum heat insulating material using the outer packaging material. This is because good heat insulation performance can be maintained for a long time.
  • the bending test is a test in which a rectangular sample having a width of 210 mm and a length of 297 mm (A4 size) is subjected to refraction treatment three times with a gelbo flex tester in accordance with ASTM F392.
  • the model name BE1006 (manufactured by Tester Sangyo Co., Ltd.) is preferable for the gelboflex tester.
  • the thickness of the outer packaging material is not particularly limited as long as the difference in the indentation elastic index in the outer packaging material described above can be set to a desired value.
  • the thickness is in the range of 30 ⁇ m or more and 200 ⁇ m or less. In particular, it is preferably in the range of 50 ⁇ m or more and 150 ⁇ m or less.
  • the method of laminating the outer packaging material is not particularly limited as long as an outer packaging material having a desired configuration can be obtained, and a known method can be used.
  • a dry lamination method in which each film formed in advance is bonded using an adhesive, and each material of a gas barrier film that has been melted by heat is extruded and bonded using a T-die, etc.
  • the method etc. which bond the film which can be heat-welded through an adhesive agent are mentioned.
  • the vacuum heat insulating material of the present disclosure is a vacuum heat insulating material including a core material and a vacuum heat insulating material outer packaging material in which the core material is enclosed, and the vacuum heat insulating material outer material is the above-described vacuum heat insulating material outer package. It is a material.
  • the vacuum heat insulating material of the present disclosure can be the same as that illustrated in FIG. According to this indication, it can be set as the vacuum heat insulating material which can maintain heat insulation performance for a long period of time because the outer packaging material for vacuum heat insulating materials is the above-mentioned outer packaging material for vacuum heat insulating materials.
  • the vacuum heat insulating material of the present disclosure has a vacuum heat insulating material outer packaging material and a core material.
  • the vacuum heat insulating material of the present disclosure will be described for each configuration.
  • Outer packaging material for vacuum heat insulating material The outer packaging material for vacuum heat insulating material of the present disclosure encloses a core material.
  • the outer packaging material is the above-described outer packaging material.
  • Such an outer packaging material can be the same as the content described in the section “A.
  • the term “encapsulated” refers to sealing inside a bag formed using an outer packaging material.
  • the core material in the present disclosure is encapsulated by an outer packaging material.
  • the core material is preferably one having low thermal conductivity.
  • the core material is preferably a porous material having a porosity of 50% or more, particularly 90% or more.
  • the powder may be either inorganic or organic, and for example, dry silica, wet silica, agglomerated silica powder, conductive powder, calcium carbonate powder, perlite, clay, talc and the like can be used.
  • dry silica, wet silica, agglomerated silica powder, conductive powder, calcium carbonate powder, perlite, clay, talc and the like can be used.
  • a mixture of dry silica and conductive powder is advantageous when used in a temperature range in which an increase in internal pressure occurs because deterioration in heat insulation performance associated with an increase in internal pressure of the vacuum heat insulating material is small.
  • the infrared absorptivity of the core material can be reduced.
  • examples of the foam include urethane foam, styrene foam, phenol foam, and the like. Among these, a foam that forms open cells is preferable.
  • the fiber body may be inorganic fiber or organic fiber, but it is preferable to use inorganic fiber from the viewpoint of heat insulation performance.
  • inorganic fibers include glass fibers such as glass wool and glass fibers, alumina fibers, silica alumina fibers, silica fibers, ceramic fibers, and rock wool. These inorganic fibers are preferable in that they have low thermal conductivity and are easier to handle than powders.
  • the core material may be the above-described material alone or a composite material in which two or more materials are mixed.
  • the vacuum heat insulating material of the present disclosure is such that the inside sealed with the outer packaging material is sealed under reduced pressure to be in a vacuum state.
  • the degree of vacuum inside the vacuum heat insulating material is preferably 5 Pa or less.
  • the heat conductivity of a vacuum heat insulating material is low, for example, it is preferable that the heat conductivity (initial heat conductivity) in 25 degreeC of a vacuum heat insulating material is 15 mW / (m * K) or less. It is preferably 10 mW / (m ⁇ K) or less, and particularly preferably 5 mW / (m ⁇ K) or less. This is because by setting the thermal conductivity of the vacuum heat insulating material within the above-mentioned range, the vacuum heat insulating material becomes difficult to conduct heat to the outside, so that a high heat insulating effect can be achieved.
  • Measurement of thermal conductivity is based on JIS A1412-2: 1999 (Measurement method of thermal resistance and thermal conductivity of thermal insulation materials-Part 2: Heat flow meter method (HFM method)).
  • the test takes 15 minutes or more to complete the test, standard plate type EPS, hot surface temperature 30 ° C, cold surface temperature 10 ° C, sample average temperature 20 ° C, and both main surfaces of the sample are A method is used that is arranged so as to face in the vertical direction and is measured by a heat flow meter method.
  • the thermal conductivity measuring device is preferably Auto Lambda HC-074 (manufactured by Eiko Seiki Co., Ltd.).
  • the sample size is, for example, 29 ⁇ 0.5 cm wide and 30 ⁇ 0.5 cm long. Under one condition, at least three samples are measured, and the average of the measured values is taken as the thermal conductivity value of the condition.
  • the vacuum heat insulating material preferably has a high gas barrier property. This is because it is possible to prevent a decrease in the degree of vacuum due to intrusion of moisture, oxygen, and the like from the outside.
  • the gas barrier property of the vacuum heat insulating material is the same as the oxygen permeability and water vapor permeability described in the above-mentioned sections of “A. Outer packaging material for vacuum heat insulating material, 2. Gas barrier film, (3) Gas barrier film”. The description here is omitted.
  • Manufacturing method As a manufacturing method of the vacuum heat insulating material of this indication, a general method can be used. For example, two laminates that can form the above-described outer packaging material and cut into a quadrilateral are prepared. The respective heat-weldable films face each other, and the outer edges of the three sides of the two laminates are heat-welded to obtain a bag having one side open. After putting the core material through the opening of the bag, air is sucked from the opening of the bag. In the state where the inside of the bag body is depressurized, the remaining outer edge portion is heated. Thereby, a vacuum heat insulating material in which the core material is enclosed by the outer packaging material is obtained.
  • the vacuum heat insulating material of the present disclosure has low thermal conductivity and is excellent in heat insulating properties and durability even at high temperatures. Therefore, the vacuum heat insulating material can be used in a part that has a heat source and generates heat, or a part that becomes high temperature when heated from the outside.
  • the article with a vacuum heat insulating material of the present disclosure is an article having a heat insulating region and an article with a vacuum heat insulating material including the vacuum heat insulating material, and the vacuum heat insulating material is the above-described vacuum heat insulating material.
  • the heat insulating region is a region that is thermally insulated by a vacuum heat insulating material, for example, a region that is kept warm or cold, a region that surrounds a heat source or a cooling source, or a region that is isolated from a heat source or a cooling source. These areas may be spaces or objects.
  • electric devices such as refrigerators, freezers, heat insulators, and coolers, heat insulation containers, cold insulation containers, transport containers, containers, containers for storage containers, vehicles, aircraft, ships and other vehicles, houses, warehouses, etc. Buildings, etc.
  • vacuum heat insulating material in the present disclosure is the same as the content described in the above-mentioned section “B. Vacuum heat insulating material”, description thereof is omitted here.
  • the article with a vacuum heat insulating material of the present disclosure include a device having a heat source part or a heat retaining part inside the main body or inside, and a device with a vacuum heat insulating material provided with a vacuum heat insulating material.
  • the “heat source section” refers to a portion that generates heat in the apparatus main body or inside the apparatus when the apparatus itself is driven, such as a power source or a motor.
  • the “insulated part” refers to a part that does not have a heat source part in the apparatus body or inside, but the apparatus receives heat from an external heat source and becomes high temperature.
  • the vacuum heat insulating material is the above-described vacuum heat insulating material and can maintain heat insulating performance for a long period of time
  • heat from the heat source part is insulated by the vacuum heat insulating material.
  • the temperature of the entire device can be prevented from becoming high, and in the device having the heat retaining portion, the temperature state of the heat retaining portion can be maintained by the vacuum heat insulating material.
  • it can be set as the apparatus which has the high energy saving characteristic which suppressed power consumption.
  • the device in the present disclosure has a main body or a heat source section or a heat retaining section inside the main body.
  • equipment in the present disclosure include natural refrigerant heat pump water heaters, refrigerators, vending machines, rice cookers, pots, microwave ovens, commercial ovens, IH cooking heaters, electrical appliances such as OA equipment, automobiles, residential walls, and transportation. Container etc. are mentioned.
  • an apparatus uses the above-mentioned vacuum heat insulating material of this indication for a natural refrigerant heat pump water heater, a commercial oven, a microwave oven, and a car.
  • the vacuum heat insulating material may be directly attached to the heat source portion or the heat retaining portion of the device, and the vacuum heat insulating material is provided between the heat retaining portion and the heat source portion or the external heat source. It may be mounted so as to be sandwiched.
  • Example 1 An outer packaging material having a configuration of a first film / second film / third film / fourth film was produced from the inner side (core side) when the vacuum heat insulating material was formed.
  • a biaxially stretched nylon film (ON15) having a thickness of 15 ⁇ m was used as each of the first film and the fourth film.
  • a gas barrier film (VM-PET12) having a gas barrier layer of aluminum deposited on a biaxially stretched polyethylene terephthalate film having a thickness of 12 ⁇ m and a thickness of about 40 nm was used.
  • the second film and the third film were arranged so that the respective gas barrier layers face each other.
  • thermosetting composition (A) was applied to the protective film and then dried to evaporate the solvent, thereby forming an adhesive layer on one surface of the protective film.
  • the protective film and the gas barrier film were bonded from each other by pressing the adhesive layer of the protective film and the gas barrier film from both sides.
  • the gas barrier film was bonded to the intermediate film after forming the adhesive layer on the gas barrier film, and the film capable of being thermally welded was bonded to the intermediate film after forming the adhesive layer on the intermediate film.
  • the outer packaging material was completed by performing the aging process for 3 days in the room (humidity is uncontrolled) of the laminated body of each film joined by the adhesive at a temperature of about 40 degrees.
  • the heat-weldable film was joined last.
  • a gas barrier film having a metal foil as described above, an adhesive layer is formed on the film located on the outside with a vacuum heat insulating material, and then the adhesive layer and the inside on the film located on the outside. The film located in the position was bonded together.
  • two or more gas barrier films having a gas barrier layer and a resin base material were used, the gas barrier layers of the gas barrier film were joined together, and then joined in the order of the film located outside and the film located inside.
  • An outer packaging material was obtained in the same manner as in Example 1, except that a biaxially stretched nylon film (ON25) having a thickness of 25 ⁇ m was used as each of the first film and the fourth film.
  • Example 3 An outer packaging material was obtained in the same manner as in Example 1 except that a biaxially stretched nylon film (ON25) having a thickness of 25 ⁇ m was used as the first film.
  • Example 4 An outer packaging material was obtained in the same manner as in Example 1 except that a biaxially stretched nylon film (ON35) having a thickness of 35 ⁇ m was used as the first film.
  • a biaxially stretched nylon film (ON35) having a thickness of 35 ⁇ m was used as the first film.
  • Example 5 Example 1 except that a 25 ⁇ m thick stretched polybutylene terephthalate film (PBT25) was used as the first film and a 25 ⁇ m thick biaxially stretched polyethylene terephthalate film (PET25) was used as the fourth film. Thus, an outer packaging material was obtained.
  • PBT25 polybutylene terephthalate film
  • PET25 biaxially stretched polyethylene terephthalate film
  • Example 6 An outer packaging material was obtained in the same manner as in Example 1 except that a biaxially stretched nylon film (ON35) having a thickness of 35 ⁇ m was used as each of the first film and the fourth film.
  • a biaxially stretched nylon film ON35 having a thickness of 35 ⁇ m was used as each of the first film and the fourth film.
  • Example 7 An outer packaging material was obtained in the same manner as in Example 6 except that a biaxially stretched nylon film (ON25) having a thickness of 25 ⁇ m was used as the fourth film.
  • Example 8 An outer packaging material was obtained in the same manner as in Example 7 except that a stretched polybutylene terephthalate film (PBT25) having a thickness of 25 ⁇ m was used as the first film.
  • PBT25 stretched polybutylene terephthalate film
  • Example 9 An outer packaging material was obtained in the same manner as in Example 7 except that an unstretched polypropylene film (CPP30) having a thickness of 30 ⁇ m was used as the first film.
  • CPP30 unstretched polypropylene film
  • Example 10 An outer packaging material was obtained in the same manner as in Example 7 except that an unstretched polypropylene film (CPP50) having a thickness of 50 ⁇ m was used as the first film.
  • CPP50 unstretched polypropylene film
  • Example 11 An outer packaging material was obtained in the same manner as in Example 1 except that an unstretched polypropylene film (CPP30) having a thickness of 30 ⁇ m was used as each of the first film and the fourth film.
  • CPP30 unstretched polypropylene film
  • Example 12 An outer packaging material was obtained in the same manner as in Example 1 except that an unstretched polypropylene film (CPP50) having a thickness of 50 ⁇ m was used as each of the first film and the fourth film.
  • CPP50 unstretched polypropylene film
  • Example 1 An outer packaging material was obtained in the same manner as in Example 5 except that a biaxially stretched polyethylene terephthalate film (PET50) having a thickness of 50 ⁇ m was used as the fourth film.
  • PET50 polyethylene terephthalate film
  • Examples 1 to 10 in which the tensile elastic modulus of the outer packaging material is 2.0 GPa or more are bent more than Examples 11 to 12 in which the tensile elastic modulus of the outer packaging material is less than 2.0 GPa.
  • the oxygen permeability after the test was low, and the durability of the gas barrier property was high.
  • a vacuum heat insulating material that can maintain better heat insulating performance can be manufactured from the outer packing material in which the difference in the indentation elastic index of the outer packing material is 50 GPa ⁇ ⁇ m or less and the tensile elastic modulus of the outer packing material is 2.0 GPa or more.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Thermal Insulation (AREA)

Abstract

Ce matériau d'emballage externe destiné à un matériau d'isolation sous vide comprend un film pouvant être soudé thermiquement, un premier film barrière contre les gaz, et un second film barrière contre les gaz, dans cet ordre. Le premier film barrière contre les gaz comprend un premier matériau de base en résine, et une première couche barrière contre les gaz. Le second film barrière contre les gaz comprend un second matériau de base en résine, et une seconde couche barrière contre les gaz. Le premier film barrière contre les gaz et le second film barrière contre les gaz sont agencés de sorte que la première couche barrière contre les gaz et la seconde couche barrière contre les gaz se font face l'une à l'autre. Si le produit de l'épaisseur et du module élastique d'indentation de chacun des films formant le matériau d'emballage externe destiné au matériau d'isolation sous vide est défini comme étant l'indice élastique d'indentation de chacun des films, la différence entre la somme des indices élastiques d'indentation de chacun des films positionnés davantage vers le côté de la seconde couche barrière contre les gaz que la première couche barrière contre les gaz, et la somme des indices élastiques d'indentation de chacun des films positionnés davantage vers le côté de la première couche barrière contre les gaz que la seconde couche barrière contre les gaz est inférieure ou égale à 50 GPa∙µm.
PCT/JP2017/034357 2016-09-30 2017-09-22 Matériau d'emballage externe pour matériau d'isolation sous vide, matériau d'isolation sous vide, et article pourvu d'un matériau d'isolation sous vide WO2018062047A1 (fr)

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JP7247495B2 (ja) * 2018-09-12 2023-03-29 大日本印刷株式会社 蓄電デバイス用外装材、蓄電デバイス用外装材の製造方法、および蓄電デバイス

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JP2004011709A (ja) * 2002-06-05 2004-01-15 Matsushita Refrig Co Ltd 真空断熱材及び真空断熱材の製造方法
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JP2010107823A (ja) * 2008-10-31 2010-05-13 Dainippon Printing Co Ltd ハードコートフィルム
JP2014020473A (ja) * 2012-07-19 2014-02-03 Mitsubishi Electric Corp 真空断熱材およびその製造方法、並びに保温体
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JP2002225170A (ja) * 2001-01-30 2002-08-14 Matsushita Electric Ind Co Ltd 気体遮蔽性フィルム、その製造方法およびそれを用いた真空断熱体
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JP2005132004A (ja) * 2003-10-31 2005-05-26 Toppan Printing Co Ltd 断熱パネル用バリア性外装材料及び断熱パネル
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