JP2018059536A - Outer packing material for vacuum heat insulation material, vacuum heat insulation material, and article with vacuum heat insulation material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an outer packing material for a vacuum heat insulation material by which the vacuum heat insulation material capable of maintaining a good heat insulation performance can be manufactured, and a vacuum heat insulation material or an article with a vacuum heat insulation material capable of maintaining the good heat insulation performance.SOLUTION: A thermally weldable film 1, and a gas barrier film 2 are sequentially arranged in an outer packing material 10 for a vacuum heat insulation material. Thickness of the outer packing material of the vacuum heat insulation material is 90 μm or less, and a sticking strength of a side of the thermally weldable film of the outer packing material for the vacuum heat insulation material is 15N or more.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to an outer packaging material for a vacuum heat insulating material, a vacuum heat insulating material, and an article with a vacuum heat insulating material capable of producing a vacuum heat insulating material capable of maintaining heat insulating performance for a long period of time.

  A vacuum heat insulating material has a core material and the outer packaging material in which the core material was 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. In order to keep the inside of the vacuum heat insulating material in a vacuum state, the outer packaging material constituting the vacuum heat insulating material requires a gas barrier property for suppressing the passage of gas and a heat welding property for forming a bag body. Is done. Therefore, the outer packaging material for a vacuum heat insulating material is generally composed of a gas barrier film and a heat-weldable film (for example, Patent Documents 1 to 3).

JP 2006-70923 A JP 2008-106532 A JP 2013-103343 A

  For example, 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 when the outer packaging material for the vacuum heat insulating material is bent, it is desirable that defects such as minute cracks and minute pinholes hardly 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.

  Moreover, since a vacuum heat insulating material may be used with a heat retention apparatus, a heat retention container, etc., it is desirable that a heat insulation performance does not fall easily even if it is used in a high temperature environment.

  The present disclosure provides an outer packaging material for a vacuum heat insulating material capable of producing a vacuum heat insulating material capable of maintaining good heat insulating performance, and provides a vacuum heat insulating material and an article with a vacuum heat insulating material capable of maintaining good heat insulating performance. Is an issue.

  In order to solve the above-described problems, the present disclosure provides a vacuum heat insulating material packaging material in which a heat-weldable film and a gas barrier film are arranged in this order, and the thickness of the vacuum heat insulating material packaging material is Provided is an outer packaging material for vacuum heat insulating material, which is 90 μm or less and has a puncture strength of 15 N or more from the heat-weldable film side of the outer packaging material for vacuum heat insulating material.

  The present disclosure is a vacuum heat insulating material having a core material and an outer packaging material for vacuum heat insulating material in which the core material is enclosed, and the outer packaging material for vacuum heat insulating material is the outer packaging material for vacuum heat insulating material described above. Provide vacuum insulation.

  The present disclosure is an article with a vacuum heat insulating material including an article having a heat insulating region and a vacuum heat insulating material, wherein the vacuum heat insulating material is a core material, and an outer packaging material for a vacuum heat insulating material in which the core material is enclosed. There is provided an article with a vacuum heat insulating material, wherein the outer packaging material for a vacuum heat insulating material is the above-described outer packaging material for a vacuum heat insulating material.

  In the present disclosure, it is possible to provide an outer packaging material for a vacuum heat insulating material capable of producing a vacuum heat insulating material capable of maintaining good heat insulating performance. Moreover, the vacuum heat insulating material which can maintain favorable heat insulation performance, and articles | goods with a vacuum heat insulating material can be provided.

It is a schematic sectional drawing which shows an example of the outer packaging material for vacuum heat insulating materials of this indication. It is a schematic sectional drawing which shows an example of the vacuum heat insulating material of this indication. It is explanatory drawing which shows the use condition of the vacuum heat insulating material of this indication. It is explanatory drawing explaining the bending state in a bending part. It is a schematic sectional drawing which shows the other example of the outer packaging material for vacuum heat insulating materials of this indication.

  Embodiments of the present disclosure will be described below with reference to the drawings and the like. However, the present disclosure can be implemented in many different modes and should not be construed as being limited to the description of the embodiments exemplified below. Further, in order to clarify the description, the drawings may be schematically represented with respect to the width, thickness, shape, and the like of each part as compared to the actual form, but are merely examples and limit the interpretation of the present disclosure. Not what you want. In addition, in the present specification and each drawing, elements similar to those described above with reference to the previous drawings are denoted by the same reference numerals, and detailed description may be omitted as appropriate.

  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. In the following description, “the outer packaging material for vacuum heat insulating material” may be abbreviated as “the outer packaging material”. In the outer packaging material, when the vacuum heat insulating material is manufactured, a position close to the inside of the vacuum heat insulating material may be referred to as “the inner side of the outer packaging material”, and a far position may be referred to as “the outer side of the outer packing material”.

A. External packaging material for vacuum heat insulating material An external packaging material for vacuum heat insulating material of the present disclosure is an external packaging material in which a heat-weldable film and a gas barrier film are arranged in this order, and the thickness of the external packaging material is 90 μm or less. The piercing strength from the film side where the material can be thermally welded is 15 N or more.

  FIG. 1 is a schematic cross-sectional view illustrating an example of an outer packaging material for a vacuum heat insulating material according to the present disclosure. In the outer packaging material 10 for vacuum heat insulating material of FIG. 1, the heat-weldable film 1, the gas barrier film 2, and the protective film 3 are arranged in this order using an adhesive 4, and the thickness of the outer packaging material is 90 μm or less. Yes, the puncture strength of the outer packaging material from the heat-weldable film side is 15 N or more.

  FIG. 2 is a schematic cross-sectional view illustrating an example of a vacuum heat insulating material manufactured using the outer packaging material of the present disclosure. The vacuum heat insulating material 20 in FIG. 2 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. Bending that is a portion where the outer packaging material 10 is bent at the base portion of the end portion 12 of the outer packaging material 10 on the core material 11 side or the corner portion of the outer packaging material 10 where the outer packaging material 10 covers the corner of the core material 11. Part 13 exists. Since the bending portion 13 is subjected to tensile stress and / or compressive stress, minute defects are likely to occur.

  FIG. 3 is an explanatory diagram illustrating a usage state of a vacuum heat insulating material manufactured using the outer packaging material of the present disclosure. In the use state of FIG. 3, the plurality of vacuum heat insulating materials 20 are arranged side by side, and the end portion 12 is bent to reduce the area occupied by the end portion 12 having low heat insulating performance. The end portion 12 has a bent portion 13 in which minute defects are likely to occur.

  Even if the outer packaging material of the present disclosure has a bent portion such as the bent portion 13, defects such as minute cracks and minute pinholes are unlikely to occur in the gas barrier film. A heat insulating material can be obtained.

  The outer packaging material of the present disclosure can suppress the occurrence of minute cracks particularly in the folded portion of the outer packaging material by setting the thickness of the outer packaging material to 90 μm or less. The reason can be inferred as follows.

In general, when a thin one is compared with a thick one, a larger force is required to bend the thick one. That is, in general, the length of the sides in those with a rectangular cross-section is b and h, a is section modulus Z is an indication of bending difficulty is expressed by Z = bh ^2/6. Here, h is a side in the same direction as the direction of the bending load, and b is a side perpendicular to h. When considering the section modulus Z of the bent portion of the outer packaging material described above, the thickness of the outer packaging material corresponds to h in the above formula from the direction in which the outer packaging material is bent. At this time, since the difficulty of bending the outer packaging material is proportional to the square of the thickness of the outer packaging material, it can be seen that a greater force is required to bend the thick outer packaging material.

  It is considered that a minute crack of the gas barrier film is generated when a strong stress is applied to a portion where the strength of the gas barrier film is lowered due to the presence of a minute dent or a minute foreign material, for example. When the thickness of the outer packaging material exceeds a predetermined value, the outer packaging material cannot be bent unless a strong stress is applied, and a crack is easily generated in the gas barrier film due to the strong stress. On the other hand, when the thickness of the outer packaging material is equal to or less than a predetermined value, the outer packaging material can be bent with a small stress, so that the stress applied to the gas barrier film is small and cracks are not easily generated. In addition, when the thickness of the outer packaging material is equal to or less than a predetermined value, stress is dispersed at a plurality of locations and bending occurs at many locations. The number of the bent portions formed in is increased as compared with that having a large thickness. As shown in FIG. 4, when the number of bent portions 13a in the bent portion 13 is large (FIG. 4 (b)) as compared to the case where the bent portions 13a in the bent portion 13 are small (FIG. 4 (a)), respectively. Since the bending angle α at the bent portion 13a becomes smaller, the stress applied to the gas barrier film at each bent portion becomes smaller and the generation of cracks is suppressed.

  Furthermore, the outer packaging material of the present disclosure has a thermal insulation performance even when used in a high temperature environment by setting the thickness of the outer packaging material to 90 μm or less and the piercing strength from the thermally weldable film side to 15 N or more. It is possible to obtain a vacuum heat insulating material that is difficult to decrease.

  As described above, since the generation of minute cracks is suppressed in the outer packaging material having a thickness of 90 μm or less for the vacuum insulation material, the vacuum insulation material using the outer packaging material is used in a low temperature environment or a room temperature environment. It can be inferred that good thermal insulation performance is maintained as long as it is used. However, even with such a vacuum heat insulating material, when a predetermined heating test is performed, the thermal conductivity after the heating test may be significantly higher than before the heating test. In particular, the outer packaging material having a relatively small thickness may not be able to obtain a good result in the heating test, although the above-mentioned bending test shows a good result. This disclosure shows the correlation between the degree of deterioration of thermal conductivity by the heating test (difference between the thermal conductivity after the heating test and the thermal conductivity before the heating test) and the piercing strength from the film side on which the outer packaging material can be thermally welded It was completed with a focus on sex. The reason can be inferred as follows.

  It is considered that a minute pinhole in the gas barrier film is generated when, for example, a sharp object such as a foreign material mixed from a core material or a work environment is pierced into the gas barrier film. When the thickness of the outer packaging material is reduced, the resistance of the outer packaging material to piercing is reduced, and, for example, the outer packaging material is constituted by the outer packaging material at the corner portion of the outer packaging material that covers the corner of the core material. As a result, the core material or foreign matter inside the bag body pierces the outer packaging material and minute pinholes are likely to occur. Such pinholes are generated even in a low temperature environment or a room temperature environment. However, in a high temperature environment, the outer packaging material is softened due to the influence of temperature, so that the pinhole is more likely to be generated. Therefore, by setting the puncture strength from the film side on which the outer packaging material can be heat-welded to a certain value or more, resistance to puncture is obtained, so that the generation of pinholes is suppressed even in a high temperature environment.

(1) Characteristics of the outer packaging material for vacuum heat insulating material The thickness of the outer packaging material is 90 μm or less. Generation of minute pinholes at the folded portion of the outer packaging material can be suppressed. The thickness of the outer packaging material may be, for example, 80 μm or less, and the lower limit is not particularly limited, but may be, for example, 30 μm or more, and may be 50 μm or more.

  The puncture strength of the outer packaging material is 15 N or more from the film side that can be heat-welded. Even in a high temperature environment, the generation of minute pinholes at the folded portion of the outer packaging material can be suppressed. The piercing strength of the outer packaging material may be 16N or more, and the upper limit is not particularly limited, but can be, for example, 100N or less, or 50N or less.

  In this disclosure, the puncture strength is measured in accordance with JIS Z1707: 1997 (general rules for plastic film for food packaging), and a semi-circular needle having a diameter of 1.0 mm and a tip shape radius of 0.5 mm with respect to a fixed outer packaging material. Is used to measure the maximum stress until the needle penetrates the outer packaging material at a speed of 50 mm / min from the top to the bottom along the direction perpendicular to the surface. be able to. Using Tensilon universal testing machine RTC-1250A (A & D), the measuring device is arranged with a needle for piercing test (manufactured by Takachiho Seiki Co., Ltd.) on the upper jig, and on the lower jig. It is preferable to measure by placing an outer packaging material fixing base having a hole in the center. Under one condition, at least five samples are measured, and the average of these measured values is taken as the value of the piercing strength for that condition.

  The puncture strength of the outer packaging material can be adjusted by the type and thickness of the heat-weldable film. A film having a high indentation elastic modulus has a high puncture strength. The indentation elastic modulus of the film varies depending on the materials and blending ratios of the main component and the subcomponent, or manufacturing conditions such as film forming. Therefore, in order to increase the puncture strength of the outer packaging material from the thermally weldable film side to a certain value or more, it is conceivable to relatively increase the indentation elastic modulus of the thermally weldable film.

  The piercing strength of the outer packaging material may be adjusted by placing an intermediate film between the heat-weldable film and the gas barrier film. Normally, heat-weldable film and gas barrier film are different, so the piercing strength from the heat-weldable film side and the piercing strength from the gas barrier film side (protective film side when a protective film is placed) It becomes a different value. By setting the puncture strength from the heat-weldable film side to the above value, it is possible to suppress the generation of minute pinholes due to the core material and foreign matters inside the bag body constituted by the outer packaging material.

  The piercing strength of the outer packaging material can be improved by arranging a protective film on the opposite side of the gas barrier film from the heat-weldable film. The protective film can prevent the pinhole generated from the inside from penetrating to the outside of the outer packaging material.

(2) Heat-weldable film The heat-weldable film is arranged inside the outer packaging material than the gas barrier film, and is usually arranged most inside the outer packaging material in many cases. When the vacuum heat insulating material is manufactured, the heat-weldable films are heat-welded so that the outer packaging materials are joined.

  For example, a thermoplastic resin or a heat-meltable resin can be used as the main material of the heat-weldable film because it can be melted and fused by heating. Specifically, polyolefin resins such as cyclopolyolefin, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), polyvinyl acetate resins, polyvinyl chloride resins, Poly (meth) acrylic resins, urethane resins, polyamide resins such as nylon, polyvinyl alcohols such as polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), and the like. Since good adhesive force can be obtained, a polyolefin resin of cyclopolyolefin and a polyester resin of polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate can be used. Moreover, an unstretched film can be used as the heat-weldable film.

  The heat-weldable film may contain other materials such as an antiblocking agent, a lubricant, a flame retardant, and a filler in addition to the above-described resin.

  Although the melting temperature of the heat-weldable film is not particularly limited, in order to increase the heat-weldability, for example, it can be 80 ° C. or higher, may be 100 ° C. or higher, and can be 300 ° C. or lower. It may be 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 and obtaining 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 thickness of the heat-weldable film is not particularly limited, but can be set to, for example, 20 μm or more, 25 μm or more, 30 μm or more, or 100 μm or less in order to improve heat weldability. 90 μm or less, or 80 μm or less.

  The indentation elastic modulus of the heat-weldable film is not particularly limited, but can be 1.0 GPa or more. The puncture strength of the outer packaging material can be improved, and the generation of minute pinholes at the folded portion of the outer packaging material can be suppressed. In order to further suppress the generation of minute pinholes, the indentation elastic modulus of the heat-weldable film may be 1.5 GPa or more, or 1.7 GPa or more. Further, the indentation elastic modulus of the heat-weldable film may be 10 GPa or less, or 5 GPa or less. Usually, the heat-weldable film is disposed on the innermost side of the outer packaging material, and therefore the inner surface of the outer packaging material corresponds to the surface of the heat-weldable film. Therefore, the indentation elastic modulus of the heat-weldable film is obtained by measuring the inner surface of the outer packaging material or the cross section of the outer packaging material.

  The indentation elastic modulus is measured according to ISO 14577. A Vickers indenter (a square pyramid diamond indenter with a face angle of 136 °) is attached to the cross section or surface of the sample in an environment of about 23 ° C. and about 60% RH. 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 μm / second, an indentation depth of 2 μm, a holding time of 5 seconds, and an extraction speed of 0.1 μm / second. The micro hardness tester is preferably Picodenter HM500 (Fischer Instruments). In one condition, at least five samples are measured, and the average of the measured values is taken as the value of the indentation elastic modulus of the condition. When measuring the cross section of the sample, 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. When measuring the surface of the sample, the surface of the sample not to be measured 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.

(3) Gas barrier film The gas barrier film is arranged outside the outer packaging material than the heat-weldable film, and suppresses gas from entering the inside of the vacuum heat insulating material as a barrier for gases such as oxygen and water vapor. .

  Examples of the gas barrier film include a gas barrier film having a metal foil, and a gas barrier film having a resin base material and a gas barrier layer containing an inorganic compound disposed on one or both sides of the resin base material.

  The metal foil used in the gas barrier film having a metal foil is generally a thin metal stretched. The metal foil can be manufactured by rolling, for example. Examples of the metal foil include aluminum, nickel, stainless steel, iron, copper, titanium, and the like. The metal foil has good gas barrier properties and is excellent in bending resistance and stab resistance. Furthermore, aluminum foil is easy to process and inexpensive. The gas barrier film having a metal foil may be composed only of the metal foil, may be composed of a plurality of metal foils, or other layers may be laminated on the metal foil.

  The thickness of the gas barrier film having a metal foil is not particularly limited, but can be, for example, 9 μm or less, 7 μm or less, for example, 4 μm or more, and 5 μm or more.

The oxygen permeability of the gas barrier film having a metal foil is not particularly limited, but can be 0.1 cc / (m ² · day · atm) or less, or 0.01 cc / (m ² · day · atm) or less. Good. It can suppress that gas, such as oxygen, penetrate | invades into the inner side from the outer side of a vacuum heat insulating material, and the vacuum degree inside a vacuum heat insulating material falls.

In this disclosure, the oxygen permeability is measured according to JIS K7126-2A: 2006 (Plastics-Films and Sheets-Gas Permeability Test Method-Part 2: Isobaric Method, Appendix A: Oxygen Gas Permeability by Electrolytic Sensor Method. In accordance with the test method) under the conditions of a temperature of 23 ° C. and a humidity of 60% RH, 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 permeability of the gas barrier film having a metal foil is not particularly limited, but can be 0.1 g / (m ² · day) or less, or 0.01 g / (m ² · day) or less. It can suppress that gas, such as water vapor | steam, penetrate | invades into the inner side from the outer side of a vacuum heat insulating material, and the vacuum degree inside a vacuum heat insulating material falls.

In the present disclosure, the water vapor transmission rate is measured according to JIS K7129-B: 2008 (plastic-film and sheet-method for determining water vapor transmission rate (instrument measurement method), Appendix B: infrared sensor method). Under the conditions of 40 ° C. and humidity 90% RH (Condition 3), using the water vapor permeability measuring device, 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.

  The gas barrier layer of a gas barrier film having a resin substrate and a gas barrier layer is generally obtained by laminating an inorganic compound layer on a resin substrate. The layer of the inorganic compound can be manufactured, for example, by vapor deposition or coating. Examples of the inorganic compound include aluminum, aluminum oxide (alumina), silicon oxide (silica), and the like. Examples of the main component of the resin base material include polyolefin resins such as polyethylene, polypropylene, and cycloolefin, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), and nylon. Polyvinyl alcohol such as polyamide resin such as polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), and the like. Since the gas barrier film which has a resin base material and a gas barrier layer can make the thickness of a gas barrier layer comparatively thin, it can suppress the heat insulation fall by a heat bridge effect. The gas barrier film having a resin base material and a gas barrier layer may have a plurality of gas barrier layers, and other layers other than the gas barrier layer may be laminated.

The thickness of the gas barrier layer of the gas barrier film having the resin substrate and the gas barrier layer is not particularly limited, but may be, for example, 5 nm or more, may be 10 nm or more, and may be, for example, 1000 nm or less, It may be 700 nm or less.
The thickness of the resin base material of the gas barrier film having the resin base material and the gas barrier layer is not particularly limited, but can be, for example, 6 μm or more, 9 μm or more, and, for example, 200 μm or less, It may be 100 μm or less.

The oxygen permeability of the gas barrier film having the resin substrate and the gas barrier layer is not particularly limited, but can be 1.0 cc / (m ² · day · atm) or less, and 0.6 cc / (m ² · day · atm) or less, or 0.1 cc / (m ² · day · atm) or less. It can suppress that gas, such as oxygen, penetrate | invades into the inner side from the outer side of a vacuum heat insulating material, and the vacuum degree inside a vacuum heat insulating material falls.

Water vapor permeability of the gas barrier film having a resin base material and the gas barrier layer is not particularly ^{limited, 1.0g / (m 2 · day} ) can be ^{below, 0.6g / (m 2 · day} ) at less It may be 0.1 g / (m ² · day) or less. It can suppress that gas, such as water vapor | steam, penetrate | invades into the inner side from the outer side of a vacuum heat insulating material, and the vacuum degree inside a vacuum heat insulating material falls.

  The method for forming the gas barrier layer on the resin substrate is not particularly limited, and a known method can be used. For example, a physical vapor deposition (PVD) method such as a vacuum deposition method, a dry film forming method such as a chemical vapor deposition (CVD) method, a wet film forming method such as a coating method, a gas barrier layer from a resin substrate from another substrate. Examples thereof include a transfer method for transferring to a material.

(4) Protective film The outer packaging material may have a protective film. The protective film is disposed on the opposite side of the gas barrier film from the heat-weldable film and protects the outside of the gas barrier film. Note that the protective film can be distinguished from the gas barrier film in that no layer having gas barrier properties is disposed on any surface.

  Examples of the main component material of the protective film include polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), and polyamide resins such as nylon.

  The thickness of the protective film is not particularly limited, but can be, for example, 5 μm or more, 10 μm or more, 200 μm or less, or 100 μm or less.

  The indentation elastic modulus of the protective film is not particularly limited, but can be, for example, 1.0 GPa or more, 1.5 GPa or more, 1.7 Pa or more, and, for example, 10 GPa or less. It may be 5 GPa or less. The puncture strength of the outer packaging material can be improved, and the generation of minute pinholes at the folded portion of the outer packaging material can be suppressed. In addition, by adjusting to the range of the indentation elastic modulus of the heat-weldable film, the balance between stresses on the outer side and the inner side of the outer packaging material applied to the folded portion of the outer packaging material can be adjusted, and the generation of minute cracks can be suppressed. When the outer packaging material has a plurality of protective films, at least the protective film disposed on the innermost side of the outer packaging material can be within the above range.

(5) Intermediate film The outer packaging material may have an intermediate film. The intermediate film is disposed between the gas barrier film and the heat-weldable film, and protects the inside of the gas barrier film. The intermediate film can be distinguished from the gas barrier film in that no layer having gas barrier properties is disposed on either side.

  FIG. 5 is a schematic cross-sectional view illustrating another example of the outer packaging material for a vacuum heat insulating material according to the present disclosure. In the outer packaging material 10 for a vacuum heat insulating material in FIG. 5, an intermediate film 5 is disposed between the heat-weldable film 1 and the gas barrier film 2.

  Examples of the main component material of the intermediate film include polyolefin resins such as polyethylene, polypropylene, and cycloolefin, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), and nylon. Polyamide alcohol, polyvinyl alcohol (PVA), polyvinyl alcohol such as ethylene-vinyl alcohol copolymer (EVOH), and the like.

  The thickness of the intermediate film is not particularly limited, but can be, for example, 5 μm or more, 10 μm or more, 200 μm or less, or 100 μm or less.

(6) Outer packaging material for vacuum heat insulating material The outer packaging material has at least one heat-weldable film and at least one gas barrier film. You may have other films, such as an at least 1 protective film and an at least 1 intermediate film.

  The outer packaging material may be arranged such that the films constituting the outer packaging material are in direct contact by thermal welding or the like, and may be arranged with an adhesive layer interposed therebetween. Examples of the adhesive include a polyester-based adhesive, a polyurethane-based adhesive, and an acrylic adhesive.

The gas barrier property of the outer packaging material varies depending on the type of the gas barrier film used and is not particularly limited. However, when a gas barrier film having a metal foil is used, the oxygen permeability after the bending test is 0.10 cc / (m ² · day · atm) or less. Thereby, a vacuum heat insulating material capable of maintaining good heat insulating performance is obtained. Moreover, when the gas barrier film which has a resin base material and a gas barrier layer is used, the oxygen permeability after a bending test can be 1.0 cc / (m < ² > * day * atm) or less. Thereby, a vacuum heat insulating material capable of maintaining good heat insulating performance is obtained.

  In the present disclosure, the bending test is a test in which a rectangular sample having a width of 210 mm × a length of 297 mm (A4 size) is subjected to three refraction treatments 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 manufacturing method of an outer packaging material is not specifically limited, A well-known method can be used. For example, a method of pasting each film manufactured in advance with an adhesive, a method of sequentially extruding the raw material of each heat-melted film with a T-die, etc., and the like can be mentioned.

B. Vacuum heat insulating material The vacuum heat insulating material of the present disclosure has a core material and an outer packaging material for vacuum heat insulating material in which the core material is enclosed, and the outer packaging material for vacuum heat insulating material is the above-described outer packaging material for vacuum heat insulating material. It is a vacuum insulation material. The vacuum heat insulating material of this indication can maintain favorable heat insulation performance.

The above-mentioned thing can be used for the outer packaging material for vacuum heat insulating materials.
A core material is used in order to ensure the space hold | maintained in a vacuum state inside a vacuum heat insulating material. For example, powder, a porous body, a fiber body, or the like can be used as the main component material of the core material. Since these have low heat conductivity, heat conduction by the core material can be suppressed. Specific examples include fumed silica, porous urethane foam, glass wool, and glass fiber.

  The inside of the vacuum heat insulating material is maintained in a vacuum state. The degree of vacuum inside is not particularly limited, but can be, for example, 5 Pa or less.

  The thermal conductivity of the vacuum heat insulating material is not particularly limited, but can be, for example, 15 mW / (m · K) or less, or 10 mW / (m · K) or less, or 5 mW / (m · K) or less. Good.

  In this disclosure, the thermal conductivity is measured in accordance with JIS A1412-2: 1999 (Measurement method of thermal resistance and thermal conductivity of thermal insulation material-Part 2: Heat flow meter method (HFM method)). Using the rate measuring device, both the sample under the conditions of 15 minutes or more required for steady state of the test, standard plate type EPS, high temperature surface temperature 30 ° C, low temperature surface temperature 10 ° C, sample average temperature 20 ° C A method of measuring by a heat flow meter method is used so that the main surface of the substrate is oriented in the vertical direction. 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 degree of deterioration of the vacuum insulation material after the heating test (the difference between the thermal conductivity after the heating test and the thermal conductivity before the heating test) is not particularly limited, but may be 1.5 mW / (m · K) or less. 1.0 mW / (m · K) or less, or 0.5 or less. Thereby, good heat insulation performance can be maintained even in high temperature environments and high temperature applications. In the present disclosure, the heating test is a test in which storage is performed for 500 hours in a 90 ° C. environment (humidity is not controlled).

  The manufacturing method of a vacuum heat insulating material is not specifically limited, A well-known method can be used. For example, two outer packaging materials cut into a quadrilateral shape are prepared. The heat-weldable films of the two outer packaging materials are overlapped face to face, and the outer edges of the three sides 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 thermally welded. 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 can be used for an article that requires thermal insulation.

C. Article with vacuum heat insulating material Article with vacuum heat insulating material of the present disclosure includes an article having a heat insulating region, and a vacuum heat insulating material, the vacuum heat insulating material being a core material, and an outer packaging material for vacuum heat insulating material in which the core material is enclosed And the outer packaging material for vacuum heat insulating material is the above-described outer packaging material for vacuum heat insulating material. The article with the vacuum heat insulating material of the present disclosure can maintain good heat insulating performance.

As the vacuum heat insulating material, those described above in the section “B. Vacuum heat insulating material” can be used.
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.

  As articles, for example, 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.

  The present disclosure will be described more specifically with reference to the following examples.

The following films were prepared.
(1) AL6: Aluminum foil having a thickness of 6 μm (hereinafter sometimes referred to as “AL foil”) (product name: BESPA8021 manufactured by UACJ).
(2) AL40: aluminum foil having a thickness of 40 μm (hereinafter sometimes referred to as “AL foil”) (product name: BESPA8021 manufactured by UACJ).
(3) VM-PET12: a resin having a 12-μm-thick biaxially stretched polyethylene terephthalate film having a vapor-deposited aluminum layer (hereinafter sometimes referred to as “AL vapor-deposited layer”) having a thickness of about 40 nm. A gas barrier film having a base material and a gas barrier layer (manufactured by Toray Film Processing Co., Ltd .: product name: VM-PET1510).
(4) COP30: a cyclopolyolefin film having a thickness of 30 μm and an indentation elastic modulus of 2.3 GPa (Kozeki ME-1 manufactured by Kurashiki Boseki Co., Ltd.).
(5) CPET30: an unstretched polyethylene terephthalate film having a thickness of 30 μm and an indentation elastic modulus of 2.3 GPa obtained by extrusion-molding polyethylene terephthalate (product name: SI-173 manufactured by Toyobo Co., Ltd.) by the T-die method.
(6) PBT25: a stretched polybutylene terephthalate film (product name: CTG25 manufactured by Unitika Ltd.) having a thickness of 25 μm and an indentation elastic modulus of 2.1 GPa.
(7) LLDPE50: unstretched linear short-chain branched polyethylene film (product name: TUX-HCE, manufactured by Mitsui Chemicals, Inc.) having a thickness of 50 μm and an indentation elastic modulus of 0.6 GPa.
(8) CPP80: an unstretched polypropylene film having a thickness of 80 μm and an indentation elastic modulus of 0.9 GPa (product name: RXC-22 manufactured by Mitsui Chemicals, Inc.).
(9) LLDPE30: unstretched linear short-chain branched polyethylene film (product name: TUX-HCE, manufactured by Mitsui Chemicals, Inc.) having a thickness of 30 μm and an indentation elastic modulus of 0.6 GPa.
(10) ON25: Biaxially stretched nylon film (product name: Emblem ONBC manufactured by Unitika Ltd.) having a thickness of 25 μm and an indentation elastic modulus of 1.8 GPa.
(11) PET16: Biaxially stretched polyethylene terephthalate film having a thickness of 16 μm and an indentation elastic modulus of 2.5 GPa (product name: Emblet PTMB, manufactured by Unitika).
(12) PET12: a biaxially stretched polyethylene terephthalate film (product name: Emblet PTMB, manufactured by Unitika Ltd.) having a thickness of 12 μm and an indentation elastic modulus of 2.5 GPa.
(13) ON15: Biaxially stretched nylon film (product name: Emblem ONBC manufactured by Unitika Ltd.) having a thickness of 15 μm and an indentation elastic modulus of 1.8 GPa.

[Example 1]
An outer packaging material was produced in which ON25 as a protective film, AL6 as a gas barrier film, and COP30 as a heat-weldable film were arranged in this order.

Each film was joined by an adhesive having a thickness of about 4 μm (weight per unit area in the outer packaging material was 3.5 g / m ² ). Adhesive is based on polyester polyol as a main component (product name: ADDLOCK RU-77T, manufactured by Rock Paint), and curing agent containing aliphatic polyisocyanate (product name: LOCK BOND J H-7, manufactured by Rock Paint). And a thermosetting composition (A) in which the solvent of ethyl acetate was mixed so that the weight blending ratio was main agent: curing agent: solvent = 10: 1: 14 was used after thermosetting. The main agent, curing agent, and solvent were stored separately before use and mixed immediately before use.

  In preparation of the outer packaging material, first, the 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. Next, 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. In the same procedure, 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. Finally, the outer packaging material was completed by performing the aging process for 3 days in the room (humidity is uncontrolled) which set the laminated body of each film joined by the adhesive to a temperature of about 40 ° C.

  In any of the examples and comparative examples, the heat-weldable film was joined last. For example, when a gas barrier film having a metal foil is used, 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. On the other hand, when 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.

[Example 2]
The outer packaging material was produced in the same procedure as in Example 1 except that the protective film was ON25, the gas barrier film was AL6, and the heat-weldable film was CPET30 arranged in this order.

[Example 3]
An outer packaging material was produced in the same procedure as in Example 1 except that PET16 as a protective film, AL6 as a gas barrier film, and PBT25 as a heat-weldable film were arranged in this order.

[Example 4]
PET1 as the first protective film, ON25 as the second protective film, AL6 as the gas barrier film, PBT25 as the heat-weldable film is the outer packaging material arranged in this order, in the same procedure as in Example 1, An outer packaging material was prepared.

[Comparative Example 1]
An outer packaging material was produced in the same procedure as in Example 1, except that the protective film was ON15, the gas barrier film was AL6, and the heat-weldable film was LLDPE50 arranged in this order.

[Comparative Example 2]
PET1 as the first protective film, ON15 as the second protective film, AL40 as the gas barrier film, except that the outer packaging material in which CPP80 is arranged in this order as the heat-weldable film is the same procedure as in Example 1, An outer packaging material was prepared.

[Example 5]
Except that VM-PET12 was used as the first gas barrier film, VM-PET12 was used as the second gas barrier film, VM-PET12 was used as the third gas barrier film, and PBT25 was used as the heat-weldable film in this order. An outer packaging material was produced in the same procedure as in Example 1. Note that the VM-PET12 of the first gas barrier film and the VM-PET12 of the second gas barrier film are the AL vapor-deposited layer of the first gas barrier film so that the respective resin bases are arranged outside and the AL vapor-deposited layer is arranged inside. And the resin base material of the second gas barrier layer were bonded with an adhesive. Further, the VM-PET12 of the second gas barrier film and the VM-PET12 of the third gas barrier film are two AL vapor deposition layers between the resin base material of one VM-PET12 and the resin base material of the other VM-PET12. The AL vapor-deposited layers were joined with an adhesive so that the

[Comparative Example 3]
Example 15 except that ON15 is used as the protective film, VM-PET12 is used as the first gas barrier film, VM-PET12 is used as the second gas barrier film, and LLDPE30 is used as the heat-weldable film in this order. The outer packaging material was produced by the procedure described above. The VM-PET12 of the first gas barrier film and the VM-PET12 of the second gas barrier film are two AL vapor deposition layers between the resin base material of one VM-PET12 and the resin base material of the other VM-PET12. The AL vapor-deposited layers were joined with an adhesive so that the

  The following evaluation was performed about the outer packaging material obtained by the Example and the comparative example.

(1) Thickness and piercing strength of outer packaging material The thickness and piercing strength of the outer packaging materials obtained in Examples and Comparative Examples were measured by the above-described methods. The results are shown in Table 1 below.

(2) Water Vapor Permeability and Oxygen Permeability after Bending Test For the outer packaging materials obtained in Examples and Comparative Examples, after performing the bending test by the above method, the water vapor transmission rate and oxygen transmission rate are determined by the above method. It was measured. The results are shown in Table 1 below.

(4) Thermal conductivity before and after the heating test For the outer packaging materials obtained in the examples and comparative examples, the thermal conductivity before and after the heating test is performed by the following method is measured by the above method, and the degree of deterioration of the thermal conductivity. Was calculated. The results are shown in Table 1 below.

Two outer packaging materials cut into a rectangle having a width of 40 cm and a length of 50 cm are prepared. The heat-weldable films of the two outer packaging materials are overlapped face to face, and the outer edges of the three sides are heat-welded to obtain a bag having one side open. The thermal welding is performed using a thermal welding machine (impulse sealer FA-600-10W, manufactured by Fuji Impulse). The optimal conditions for temperature and time during thermal welding differ depending on the layer structure of the outer packaging material and the type and thickness of the heat-meltable film.Therefore, the thermal welding conditions such as cross-sectional observation of the welded surface and measurement of the welding strength should be used. Predetermined by general considerations to determine. The outer edge to be thermally welded is in the range of 2 cm to 3 cm from the end of the outer packaging material. Glass wool having a width of 29 cm, a length of 30 cm, and a thickness of 3 cm was inserted as a core material from the opening of the bag body (glass wool of a binder having a basis weight of 800 g / m ² , product name: White Roll WR800, manufactured by Mag Izobale). Then, air is sucked from the opening of the bag. Suction is performed using a vacuum packaging machine (MVR-1000, manufactured by Shigaraki Seisakusho Co., Ltd.), and the remaining outer edge is thermally welded in a state where the pressure inside the bag is reduced to 0.05 Pa. The thermal welding is performed under the same conditions as described above using the thermal welding machine. The outer edge to be thermally welded is in the range of 5 cm to 6 cm from the end of the outer packaging material. Furthermore, the outer edge of the entire outer periphery was folded and fixed with tape. Thereby, a vacuum heat insulating material in which the core material is enclosed by the outer packaging material is obtained.

First, the heat conductivity of the vacuum heat insulating material manufactured by the said procedure was measured as heat conductivity before a heating test. Next, as the thermal conductivity after the heating test, the thermal conductivity of the vacuum heat insulating material after being placed in a thermostatic chamber (humidity is not controlled) at a temperature of 90 ° C. for 500 hours was measured. The difference between the thermal conductivity after the heating test and the thermal conductivity before the heating test was defined as the degree of deterioration.
[Evaluation results]

  From Table 1, in Examples 1-5 whose thickness of an outer packaging material is 90 micrometers or less, the water vapor permeability and oxygen permeability after a bending test were low, and durability of gas barrier property was high. On the other hand, in Comparative Example 2 in which the thickness of the outer packaging material exceeded 90 μm, the water vapor permeability and oxygen permeability after the bending test were high, and the durability of the gas barrier property was low. The outer packaging material having low water vapor permeability and oxygen permeability after the bending test can produce a vacuum heat insulating material capable of maintaining good heat insulating performance.

  Moreover, from Table 1, in Examples 1-5 in which the piercing strength of the outer packaging material is 15 N or more, the degree of deterioration of thermal conductivity by the heat resistance test was small, and the heat resistance of the heat insulation performance was high. On the other hand, in Comparative Examples 1 and 3 in which the piercing strength of the outer packaging material was less than 15 N, the degree of deterioration of the thermal conductivity by the heat resistance test was large and the heat resistance of the heat insulation performance was low. The outer packaging material having a low degree of deterioration by the heat resistance test can be manufactured as a vacuum heat insulating material capable of maintaining good heat insulating performance.

  Further, when a gas barrier film having a resin base material and a gas barrier layer is used, in Comparative Example 3 in which the piercing strength of the outer packaging material is less than 15 N, the thermal conductivity of the vacuum heat insulating material before the heating test was low. It was significantly higher after the heating test. It can be seen that setting the piercing strength of the outer packaging material to 15 N or more is useful in the case of an outer packaging material using a gas barrier film having a resin base material and a gas barrier layer.

DESCRIPTION OF SYMBOLS 1 ... Film which can be heat-welded 2 ... Gas barrier film 3 ... Protective film 4 ... Adhesive 5 ... Intermediate film 10 ... Outer packaging material for vacuum heat insulating material 11 ... Core material 20 ... Vacuum heat insulating material

Claims (8)

A heat-weldable film and a gas barrier film are vacuum insulation outer packaging materials arranged in this order,
The outer packaging material for vacuum heat insulating material has a thickness of 90 μm or less,
A vacuum insulation material outer packaging material, wherein the vacuum insulation material outer packaging material has a puncture strength of 15 N or more from the heat-weldable film side.   The outer packaging material for vacuum insulation according to claim 1, wherein the heat-weldable film has an indentation elastic modulus of 1.0 GPa or more.   The outer packaging material for vacuum insulation according to claim 2, wherein the gas barrier film has a protective film on the side opposite to the thermally weldable film, and the protective film has an indentation elastic modulus of 1.0 GPa or more.   The outer packaging material for vacuum insulation according to any one of claims 1 to 3, further comprising an intermediate film between the heat-weldable film and the gas barrier film.   The outer packaging material for vacuum insulation according to any one of claims 1 to 4, wherein the gas barrier film has a metal foil.   The said gas barrier film has a gas barrier layer containing the inorganic compound arrange | positioned at the one or both surface side of the resin base material and the said resin base material in any one of Claim 1-5. Outer packaging material for vacuum insulation. A vacuum heat insulating material having a core material and a vacuum heat insulating material encapsulating the core material,
A vacuum heat insulating material, wherein the vacuum heat insulating material is a vacuum heat insulating material according to any one of claims 1 to 6. An article with a vacuum insulation comprising an article having a thermal insulation region and a vacuum insulation,
The vacuum heat insulating material has a core material and an outer packaging material for a vacuum heat insulating material in which the core material is enclosed,
The article with a vacuum heat insulating material, wherein the outer packaging material for a vacuum heat insulating material is the outer packaging material for a vacuum heat insulating material according to any one of claims 1 to 6.