WO2018016351A1

WO2018016351A1 - Outer packaging member for vacuum heat insulating member, vacuum heat-insulating member, and article provided with vacuum heat-insulating member

Info

Publication number: WO2018016351A1
Application number: PCT/JP2017/024955
Authority: WO
Inventors: 将博今井; 琢棟田; 誠溝尻
Original assignee: 大日本印刷株式会社
Priority date: 2016-07-21
Filing date: 2017-07-07
Publication date: 2018-01-25
Also published as: JP6149997B1; JP2018021662A; JP2018021653A

Abstract

The present invention provides an outer packaging member for a vacuum heat insulating member having a film that can be heat-sealed and a gas barrier film, the outer packaging member for a vacuum heat insulating member characterized in that the modulus of tensile elasticity of the outer packaging member for a vacuum heat insulating member is within the range of 1.0-4.0 GPa inclusive, and the ash content of the outer packaging member for a vacuum heat insulating member is within the range of 1.0-20 mass% inclusive.

Description

Vacuum insulation outer packaging, vacuum insulation, and articles with vacuum insulation

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.

In recent years, the reduction of greenhouse gases has been promoted to prevent global warming, and there is a demand for energy saving in electrical products, vehicles, equipment and buildings. Among these, from the viewpoint of reducing power consumption, the use of vacuum heat insulating materials for electrical products and the like is being promoted. In equipment that has a heat generating part inside the main body, such as electrical products, and equipment that has a heat retaining function using heat from the outside, it is possible to improve the heat insulation performance of the equipment as a whole by providing a vacuum heat insulating material It becomes. For this reason, efforts are being made to reduce the energy of devices such as electrical products by using vacuum heat insulating materials.

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.

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 Document 1 and Patent Document 2).

JP 2006-70923 A JP 2014-62562 A JP 2013-103343 A JP 2002-310385 A JP 2011-143893 A

For example, Patent Document 1 and Patent Document 2 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 the vacuum insulation material with minute defects in the outer packaging material shows the same level of insulation performance as the one without it in the initial state, the insulation performance deteriorates during long-term use. This is because becomes larger.

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.

That is, the present disclosure is an outer packaging material for a vacuum heat insulating material having a heat-weldable film and a gas barrier film, and the tensile elastic modulus of the outer packaging material for the vacuum heat insulating material is 1.0 GPa or more and 4.0 GPa or less. And the ash content of the outer packaging material for vacuum heat insulating material is within the range of 1.0 mass% or more and 20 mass% or less.

In the outer packaging material for vacuum heat insulating material of the present disclosure, the outer packaging material for vacuum heat insulating material may have two or more gas barrier films, or may have three or more gas barrier films.

The outer packaging material for a vacuum heat insulating material of the present disclosure may include the gas barrier film including a resin base material and a gas barrier layer containing an inorganic compound disposed on one or both surfaces of the resin base material. Good. Furthermore, you may have the overcoat layer containing an inorganic compound in the surface side opposite to the said resin base material of the said gas barrier layer.

The outer packaging material for a vacuum heat insulating material of the present disclosure may have a tensile elastic modulus of 2.0 GPa or more.

In the outer packaging material for a vacuum heat insulating material of the present disclosure, the gas barrier film may have a metal foil.

The outer packaging material for a vacuum heat insulating material of the present disclosure may have a tensile elastic modulus of the outer packaging material for a vacuum heat insulating material of 2.0 GPa or less.

In the outer packaging material for vacuum heat insulating material of the present disclosure, the heat-weldable film may contain an inorganic compound. Moreover, the said outer packaging material for vacuum heat insulating materials may have made the protective film containing an inorganic compound in the surface side opposite to the said heat weldable film of the said gas barrier film. Moreover, the said outer packaging material for vacuum heat insulating materials may have the contact bonding layer containing an inorganic compound.

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 above-described outer packaging material for vacuum heat insulating material. Provide vacuum insulation.

The present disclosure provides an article with a heat insulating region and a device 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.

In the present disclosure, it is possible to provide an outer packaging material for a vacuum heat insulating material or the like that can form a vacuum heat insulating material capable of maintaining good heat insulating performance.

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

Hereinafter, 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 in detail.
In the present specification, “external packaging material for vacuum heat insulating material” may be abbreviated as “external packaging material”.
In addition, when a vacuum heat insulating material is formed using an outer packaging material, the heat-weldable film side that 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 a heat-weldable film The side far from the position may be described as “the outside of the outer packaging material”.

A. First, the outer packaging material for vacuum heat insulating material according to the present disclosure will be described.
The outer packaging material of the present disclosure is an outer packaging material for vacuum heat insulating material having a heat-weldable film and a gas barrier film, and the tensile elastic modulus of the outer packaging material for vacuum heat insulating material is 1.0 GPa or more and 4.0 GPa or less. And the ash content of the outer packaging material for a vacuum heat insulating material is in the range of 1.0 mass% or more and 20 mass% or less.

The outer packaging material of the present disclosure will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view illustrating an example of the outer packaging material of the present disclosure. As illustrated in FIG. 1, an outer packaging material 10 of the present disclosure includes a heat-weldable film 1 and a gas barrier film 2, and the outer packaging material 10 has a tensile elastic modulus within a specific range and a specific range. It has the ash content.

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. As illustrated in FIG. 2, 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. In FIG. 2, reference numerals not described indicate the same members as those in FIG. 1, and thus description thereof is omitted here.

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. In FIG. 3, in the two vacuum heat insulating materials 20, the end portion 12 is bent to form a bent portion 13. Compared with the case where the end portions 12 are arranged without being bent, 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. However, tensile / compressive stress is applied to the bent portion 13. Further, 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, minute defects are likely to occur in the outer packaging material 10 at the bent portion 13, the bent portion 14, and the corner portion 15.

Furthermore, when the end portions 12 of the vacuum heat insulating material are present on two adjacent sides of the outer edge of the vacuum heat insulating material, and both of these two sides are bent, the intersection of the two folding lines is bent twice. become. A bent portion that has been bent a plurality of times, such as this intersection point, is subjected to a stronger tensile / compressive stress than a bent portion in the case where the number of times of bending is 1, so that minute defects are more likely to occur.

Since the outer packaging material of the present disclosure has both the tensile elastic modulus of the outer packaging material and the ash content of the outer packaging material within a specific range, defects such as minute cracks and minute pinholes can be obtained even when folded. It is possible to form a vacuum heat insulating material that does not easily occur and can maintain a good heat insulating performance over a relatively long period of time.
Hereinafter, characteristics of the outer packaging material and each configuration of the outer packaging material in the present disclosure will be described.

1. Characteristics of vacuum insulation outer packaging material (1) Tensile elastic modulus of vacuum insulation outer packaging material In the present disclosure, the tensile elastic modulus of the outer packaging material is in the range of 1.0 GPa or more and 4.0 GPa or less. If the tensile elastic modulus of the outer packaging material is less than the range, the outer packaging material may be too soft and the strength as the outer packaging material may be insufficient. If the tensile elastic modulus of the outer packaging material exceeds the range, the outer packaging material is too hard, and there is a possibility that minute cracks and minute pinholes are likely to occur. The tensile elastic modulus of the outer packaging material can be 1.5 GPa or more, and can be 3.5 or less. Further, as will be described later, when a laminate 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 is used as a gas barrier film, The tensile elastic modulus is preferably 2.0 GPa or more. On the other hand, when the metal foil is used as the gas barrier film, the tensile elastic modulus of the outer packaging material is preferably 2.0 GPa or less.

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. Using a tensile tester, 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 σ 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. _put) in the range of (E t / 10000) ≦ σ 0 ≦ (E t / 3000). Under one condition, 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. In addition, since the value of a tensile elasticity modulus may change with directions in an outer packaging material surface, use of a surface 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 elastic modulus is a value measured for one outer packaging material. Therefore, when the outer packaging material includes a film or a layer other than a heat-weldable film or a gas barrier film, it is a value measured in a state including those layers. For example, the film passes through an adhesive layer. In the case of being laminated, it is a value measured in a state including an adhesive. That is, the tensile elastic modulus is measured in a state including all films and layers existing in the outer packaging material. In addition, when the inner side of an outer packaging material is joined and it is a bag body, it is the value measured about the outer packaging material of the part which is not joined.

(2) Ash content of outer packaging material for vacuum heat insulating material In the present disclosure, the ash content of the outer packaging material is in the range of 1.0 mass% or more and 20 mass% or less. In order to maintain the heat insulation performance for a long period of time, it is not sufficient that the tensile elastic modulus of the outer packaging material is within a specific range, and it is important that the ash content of the outer packaging material is also within a specific range. That is, even if the outer packaging material has a similar value of tensile modulus, if the ash content is different, the likelihood of occurrence of minute defects when bent is different.

The tensile elastic modulus of the outer packaging material is a characteristic that correlates with the stress applied to the bent portion when the outer packaging material is bent, and defects are likely to occur when a large stress is applied. And the ash content of an outer packaging material approximates the content rate of the inorganic compound component which occupies for the whole outer packaging material. In general, inorganic compounds are more fragile than organic compounds and are more likely to have defects than organic compounds when subjected to the same stress. In general, inorganic compounds, and inorganic compounds and organic compounds tend to be less bonded to each other than organic compounds. Therefore, the portion where defects are likely to occur when stress is applied to the outer packaging material is the inorganic compound itself, the inorganic compound, or the joint between the inorganic compound and the organic compound, rather than the organic compound. That is, when the content of the inorganic compound component in the entire outer packaging material is large, even if the stress is the same, there are many factors that can cause defects, and it can be said that minute defects are likely to occur when bent. .

Therefore, it may be possible to specify the thickness of each film or layer in which the inorganic compound is used. Examples of the inorganic compound component contained in the outer packaging material include the gas barrier film itself or a gas barrier layer constituting the gas barrier film. However, as will be described later, the gas barrier film and the gas barrier layer are appropriately formed by various methods such as foil, vapor deposition, or coating. Moreover, in vapor deposition and application | coating, the density of the film | membrane obtained, for example according to formation conditions differs, and an organic compound component may be contained in a film | membrane. For this reason, it is difficult to evaluate the ease of occurrence of minute defects when folded only by the thickness of the gas barrier film or gas barrier layer. It is also difficult to determine the content of the inorganic compound component only from the thickness of the gas barrier film or gas barrier layer. Further, as will be described later, an inorganic compound component may be included in a heat-bondable film, an adhesive layer, a protective film, or the like for various purposes, and the influence of the inorganic compound component needs to be considered. However, as with gas barrier films and gas barrier layers, there are various methods for forming these films and layers, their conditions, and raw materials, etc., so that only the thickness of these films causes the generation of minute defects when folded. It is difficult to evaluate the ease.

Therefore, the inventors of the present disclosure pay attention to the ash content of the outer packaging material as a comprehensive index, and verify the ash value and the gas permeability when bent, and the fluctuation of the ash value and the thermal conductivity in the high temperature test. As a result, it was found that there was a good correlation between them, and the outer packaging material of the present disclosure was completed.

The ash content of the outer packaging material is, for example, a case where a plurality of gas barrier films having an inorganic compound are used, a case where the gas barrier film is composed of a layer having a plurality of inorganic compounds, or a heat-weldable film, a protective film, Alternatively, when the inorganic compound is used in a complicated manner as in the case where the inorganic compound is used in a configuration other than the gas barrier film such as an adhesive layer, the advantage as a comprehensive index is great.

The ash content of the outer packaging material can be 1.0% by mass or more, and further 1.5% by mass, 3.0% by mass, or 5.0% by mass or more. Further, the ash content of the outer packaging material can be 20% by mass or less, and further can be 16% by mass or less, 15% by mass or less, and 5.0% by mass or less. For example, the ash content of the outer packaging material can be in the range of 1.0 mass% or more and 16 mass% or less, and can be in the range of 1.0 mass% or more and 15 mass% or less, Furthermore, it can be in the range of 1.0 mass% or more and 5.0 mass% or less. Further, for example, the ash content of the outer packaging material can be in the range of 1.5% by mass to 16% by mass, and can be in the range of 3.0% by mass to 16% by mass. Furthermore, it can be in the range of 5.0 mass% or more and 16 mass% or less.

The ash content is used to examine the ratio of the non-flammable inorganic compound remaining after the outer packaging material is burned out in the mass of the entire outer packaging material. In the present disclosure, the mass of the measurement sample is measured using a thermogravimetric / differential thermal analyzer (TG-DTA) and then heated in an aluminum pan and in an air atmosphere at a heating rate of 10 ° C./min. After the temperature is raised from room temperature to 600 ° C., the measurement sample is incinerated by heating at 600 ° C. for 30 minutes as it is, and the value obtained by expressing the mass after heating with respect to the mass before heating as a percentage is defined as ash. As the thermogravimetric / differential thermal simultaneous analyzer at this time, TG8120 manufactured by Rigaku Corporation can be used.

2. Gas barrier film A gas barrier film is arrange | positioned on the outer side of the film which can be heat-welded, and mainly contributes to the gas barrier property of an outer packaging material. The gas barrier film is not particularly limited as long as a desired gas barrier property can be obtained, and a metal foil may be used as the gas barrier film (first aspect), and the resin base material and one of the resin base materials or You may use the laminated body which has a gas barrier layer containing the inorganic compound arrange | positioned at both surface sides as a gas barrier film (2nd aspect).
Hereinafter, each aspect of the gas barrier film will be described.

(1) 1st aspect The 1st aspect in this indication is an aspect in which the said gas barrier film is metal foil. The metal foil is generally a thin stretch of metal, for example by tapping. Examples of such metal foils include metal foils such as aluminum, nickel, stainless steel, iron, copper, and titanium. Among these, aluminum foils are preferably used. Since the metal foil has good gas barrier properties and excellent bending resistance, it is possible to obtain an outer packaging material having high gas barrier properties by using the metal foil as the gas barrier film, and maintain high gas barrier properties. be able to.

The metal foil may be a single layer or a laminate in which layers made of the same material or layers made of different materials are laminated. The thickness of the metal foil (in the case of a laminate) is not particularly limited as long as the tensile elastic modulus and ash content of the outer packaging material can be within a predetermined range. 9 μm or less is preferable. Further, the lower limit of the thickness is not particularly limited, but can be, for example, 5 μm or more. If the thickness of the metal foil is less than 5 μm, pinholes or the like are likely to occur in the metal foil, and the gas barrier property may be lowered. On the other hand, if the thickness is greater than 9 μm, the ash content of the outer packaging material is within the above range. May be difficult to do. The thickness of the metal foil may be 7 μm or less, or may be 6.5 μm or less.

As the gas barrier property of the metal foil, the oxygen permeability is preferably 0.01 cc / (m ² · day · atm) or less. The water vapor permeability is preferably 0.01 g / (m ² · day) or less. When the oxygen and water vapor permeability of the metal foil is within the above-described range, it is possible to make it difficult for moisture, gas, and the like that have permeated from the outside to penetrate into the inner core material. The oxygen permeability is more preferably 0.005 cc / (m ² · day · atm) or less. The oxygen permeability is measured in accordance with JIS K7126-2A: 2006 (Plastics-Film and Sheet-Gas permeability test method-Part 2: Isobaric method, Appendix A: Test method of oxygen gas permeability by electrolytic sensor 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 gas using an oxygen permeability measuring device. A method of measurement is used under the condition of a transmission area of 50 cm ² so as to be in contact with each other. 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-Film and Sheet-Determination of water vapor transmission rate (instrument measurement method), Appendix B: Infrared sensor method), temperature 40 ° C, humidity Under the condition of 90% RH (Condition 3), using the water vapor transmission rate measuring device, the outer side of the outer packaging material (the side where the gas barrier film of the heat-weldable film is disposed) becomes the high humidity side (the water vapor supply side). Thus, 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 same applies to the methods for measuring oxygen permeability and water vapor permeability in the following description.

When the gas barrier film in the outer packaging material is of the first aspect, it is preferable that a protective film such as a resin film is disposed on the outer side of the gas barrier film (on the opposite side to the film capable of being thermally welded). This is because the gas barrier film can be protected from exposure to water vapor and physical stress. Since such a protective film is the same as that described in “4. Protective film” described later, description thereof is omitted here.

(2) 2nd aspect The gas barrier film of the 2nd aspect in this indication has a resin base material and a gas barrier layer containing an inorganic compound arranged on one or both sides of the resin base material. . In the present disclosure, the gas barrier film is preferably the second embodiment. This is because it is relatively difficult to reduce the thickness of the metal foil while maintaining the gas barrier property, whereas the gas barrier layer can provide the gas barrier property even with a relatively small thickness. Moreover, it is because it is easy to adjust the tensile elastic modulus and ash content of the outer packaging material by laminating a plurality of gas barrier layers or using a plurality of gas barrier films having a gas barrier layer.

The outer packaging material having the gas barrier film of this aspect will be described with reference to the drawings. FIG. 4 is a schematic cross-sectional view illustrating another example of the outer packaging material of the present disclosure. As illustrated in FIG. 4, the outer packaging material 10 having the gas barrier film 2 ′ of this aspect includes the heat-weldable film 1 and the gas barrier film 2 ′ in the same manner as the outer packaging material having the gas barrier film of the first aspect described above. It is what you have. The gas barrier film 2 ′ of this aspect includes a resin base material 3 and a gas barrier layer 4 disposed on one surface side of the resin base material 3.

(A) Gas barrier layer A gas barrier layer is arrange | positioned at the one or both surface side of a resin base material, contains an inorganic compound, and mainly contributes to the gas barrier property of a gas barrier film. The gas barrier layer is not particularly limited as long as it can exhibit a desired gas barrier property. As such a layer having gas barrier properties, for example, a metal layer, a layer mainly containing an inorganic compound, a layer mainly containing a mixed compound of an organic part and an inorganic part, or the like can be used. As a metal layer, what is comprised from metals, such as aluminum, stainless steel, titanium, nickel, iron, copper, or an alloy containing these, can be mentioned. Moreover, as a mixed compound of the organic part and inorganic part of the layer which has the mixed compound of the said organic part and an inorganic part as a main component, the mixed compound of a resin part and an inorganic part is mentioned, for example. For example, as the organic compound constituting the organic part, those described later as the resin of the resin substrate can be used, and as the inorganic compound constituting the inorganic part, the inorganic compound of the layer mainly composed of the inorganic compound is described later. Can be used. Or what shows gas barrier property independently among the things mentioned later as a material of an overcoat layer can be used, specifically, Kuraray Co., Ltd. Clarista CF etc. can be used.

The inorganic compound of the layer mainly composed of an inorganic compound may be any material that can exhibit a desired gas barrier property. For example, the inorganic oxide, inorganic oxynitride, inorganic nitride, inorganic oxide carbide,

inorganic oxycarbonitride

1 or 2 or more inorganic compounds selected from the above and silicon oxide zinc. Specifically, an inorganic compound containing one or more elements selected from silicon, aluminum, magnesium, calcium, potassium, tin, sodium, titanium, boron, yttrium, zirconium, mucerium, and zinc Can do. More specifically, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, silicon zinc alloy oxide, indium alloy oxide, silicon nitride, aluminum nitride, titanium nitride, oxidation Examples thereof include silicon nitride. An inorganic compound may be used independently and may mix and use the above-mentioned material in arbitrary ratios.

The thickness of the gas barrier layer is not particularly limited as long as a desired gas barrier property can be exhibited. Although it depends on the type of the gas barrier layer, for example, it is in the range of 5 nm or more and 800 nm or less. It is preferable. If the thickness of the gas barrier layer is less than the above range, the film formation may be insufficient and the desired gas barrier property may not be exhibited, and the gas barrier layer may deteriorate over time. If the above range is exceeded, cracks are likely to occur and flexibility may be reduced, or if the gas barrier layer contains a metal or an alloy, a heat bridge is formed using the outer packaging material of the present disclosure. This is because there is a risk of occurrence. The thickness of the gas barrier layer is more preferably in the range of 10 nm or more and 700 nm or less.

By combining the resin base material and the gas barrier layer to obtain a desired strength as the whole gas barrier film, damage or the like can be suppressed even with the thin gas barrier layer as described above.

The gas barrier layer may be a single layer or a laminate of two or more. When two or more gas barrier layers are used, gas barrier layers having the same composition may be combined, or gas barrier layers having different compositions may be combined.

As a method for forming the gas barrier layer on one surface side of the resin base material, a conventionally known method can be used according to the type of the gas barrier layer. For example, a method of forming a gas barrier layer 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, a vacuum evaporation method or the like. Can be used. Moreover, the method of sticking a resin base material and a gas barrier layer through an adhesive bond layer etc. using the ready-made gas barrier layer is mentioned.

As the gas barrier properties of the gas barrier layer alone (one layer) is preferably an oxygen permeability of at ^{0.5cc / (m 2 · day ·} atm) or ^{less, 0.1cc / (m 2 · day} · atm) or less It is more preferable that It is more preferable that the water vapor permeability is 0.5g ^/ (m 2 · day) or less is preferably 0.1g ^/ (m 2 · day) or less.

(B) Resin base material The resin base material is not particularly limited as long as it can support the gas barrier layer. For example, a resin film is preferably used. When the resin base material is a resin film, the resin film may be unstretched or 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, polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), and cyclic. Polyolefin, polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), (meth) acryl, polycarbonate, polyvinyl alcohol (PVA) and ethylene-vinyl alcohol copolymer (EVOH) ) And other resins such as polyamide-polyamide, polyurethane, polyacetal, cellulose, etc. It is possible. In the present disclosure, among the above-mentioned resins, polyamide, PET, polypropylene and the like are preferably used, and polyamide and PET are more preferably used from the viewpoints of toughness, oil resistance, chemical resistance, availability, and the like. It is done.

When a plurality of gas barrier films are used for the outer packaging material, the resin base material of the gas barrier film disposed at a position closer to the heat-weldable film includes polyvinyl alcohol such as PVA and EVOH, (meth) acryl, cellulose, and polysaccharide. It is preferable to use a hydrophilic group-containing resin such as a natural polymer such as polyvinyl alcohol resin such as PVA or EVOH, and particularly EVOH. This is because the hydrophilic group-containing resin exhibits a high barrier property against oxygen even at a high temperature, so that the barrier property against oxygen as an outer packaging material can be improved. The “hydrophilic group” refers to an atomic group that forms a weak bond with a water molecule by electrostatic interaction or hydrogen bond, and has an affinity for water, such as a hydroxy group (—OH), An atomic group containing a polar group or a dissociating group such as a carboxy group (—COOH), an amino group (—NH ₂ ), a carbonyl group (> CO), or a sulfo group (—SO ₃ H) shows its properties.

The resin base material may contain various plastic compounding agents and additives. Examples of 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 base material may be subjected to a surface treatment. This is because the adhesion to the gas barrier layer can be improved.

The thickness of the resin substrate is not particularly limited, but is, for example, in the range of 6 μm to 200 μm, more preferably in the range of 9 μm to 100 μm.

(C) Overcoat layer The gas barrier film may have an overcoat layer containing an inorganic compound on the surface of the gas barrier layer opposite to the resin substrate. This is because the gas barrier property of the gas barrier film can be improved. Such an overcoat layer is not particularly limited, and those generally used as an overcoat agent can be used. For example, a mixed compound containing an organic portion and an inorganic portion can be used as the main component of the overcoat layer.

The thickness of the overcoat layer is not particularly limited, but can be, for example, in the range of 50 nm or more and 500 nm or less.

Examples of the mixed compound include various compounds such as an alumina phosphate-based mixed compound such as Clarista CF (registered trademark) manufactured by Kuraray Co., Ltd., and Besera (registered trademark) manufactured by Toppan Printing Co., Ltd. A gas barrier resin composition comprising a zinc acrylate-based mixed compound, a resin and an inorganic layered compound, or a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are the number of carbon atoms) 1 represents an organic group of 1 or more, 8 or less, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) And a sol-gel compound using a raw material liquid obtained by polycondensation by a sol-gel method can be used. Examples of the water-soluble polymer include polyvinyl alcohol resin, ethylene / vinyl alcohol copolymer, acrylic acid resin, natural polymer methyl cellulose, carboxymethyl cellulose, cellulose nanofiber, and polysaccharide. In the present disclosure, it is preferable to use a sol-gel compound for the overcoat layer. This is because the sol-gel compound has a high adhesive strength at the interface and can perform a process during film formation at a relatively low temperature, thereby suppressing deterioration of the resin base material due to heat.

(D) Others The order of the above-described resin base material and gas barrier layer is not particularly limited, and is appropriately set according to the layer configuration of each layer other than the gas barrier film, the number of gas barrier films, etc. used together with the outer packaging material. can do. For example, as illustrated in FIG. 4, when the vacuum heat insulating material is formed using the outer packaging material 10, the gas barrier layer 4 may be disposed so as to be inside the resin base material 3. As illustrated in 5 (a), when the outer packaging material 10 includes the protective film 5, the gas barrier layer 4 may be disposed outside the resin base material 3. Further, when the outer packaging material 10 has two gas barrier films 2 ′, as illustrated in FIG. 5B, even if the gas barrier layers 4 are arranged to face each other, as shown in FIG. As illustrated in FIG. 5, even if both gas barrier layers 4 are disposed so as to be inside the resin base material 3, both gas barrier layers 4 are formed on the resin base as illustrated in FIG. You may arrange | position so that it may become the outer side of the material 3. FIG. Furthermore, as illustrated in FIGS. 5 (e) and 5 (f), when the gas barrier film 2 ′ is disposed in the outermost layer of the vacuum heat insulating material, from the viewpoint of protecting the gas barrier layer 4, the outermost layer The gas barrier layer 4 of the gas barrier film 2 ′ is preferably arranged so as to be inside the resin base material 3. FIG. 5 is a schematic cross-sectional view illustrating another example of the outer packaging material of the present disclosure.

(3) Others The outer packaging material of the present disclosure may include a plurality of gas barrier films as described above. The number of gas barrier films in one outer packaging material is not particularly limited as long as the tensile elastic modulus and ash content of the outer packaging material can be within the above-described ranges. It can be in the range, and in particular, it is preferably in the range of 2 or more and 4 or less, particularly in the range of 2 or more and 3 or less. By increasing the number of gas barrier films to be used, the gas barrier properties of the outer packaging material can be improved. However, if the number of gas barrier films is too large, it becomes difficult to make the ash content of the outer packaging material within the above-mentioned range, and the bent portion This is because it may be difficult to suppress the occurrence of cracks and the like. When the outer packaging material has a plurality of gas barrier films, the configuration of each gas barrier film may be the same or different.

3. Heat-weldable film The heat-weldable film in the present disclosure can be heat-welded, and is a part that comes into contact with a core material when a vacuum heat insulating material is formed using the outer packaging material. Moreover, it is a site | part which forms the heat welding surface which heat-welds the edge part of the outer packaging materials which oppose.

The heat-weldable film material is preferably a thermoplastic resin because it can be melted and fused by heating. For example, polyethylene such as linear short-chain branched polyethylene (LLDPE) or unstretched polypropylene Polyolefins such as (CPP), polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyamides such as polyvinyl acetate, polyvinyl chloride, (meth) acryl, polyurethane, nylon Examples thereof include polyvinyl alcohol such as resin, polyvinyl alcohol (PVA), and ethylene-vinyl alcohol copolymer (EVOH).

In the present disclosure, it is preferable that a resin having a relatively high tensile elastic modulus, such as polypropylene or polybutylene terephthalate (PBT), is used as a film material that can be thermally welded. It is because generation | occurrence | production of a micro defect can be suppressed in the case of heat welding.

The melting point of the heat-weldable film is preferably in the range of 80 ° C. or higher and 300 ° C. or lower, for example. If the melting point of the heat-weldable film is less than the above range, the sealing surface of the outer packaging material may be peeled off under the usage environment of the vacuum heat insulating material formed using the outer packaging material of the present disclosure. Further, if the melting point of the heat-weldable film exceeds the above range, the outer packaging material needs to be heat-welded at a high temperature, so that the gas barrier film and the like used together as the outer packaging material may be deteriorated by heat. The melting point is more preferably in the range of 100 ° C. or more and 250 ° C. or less.

The heat-weldable film may contain other materials such as an anti-blocking agent, a lubricant, a flame retardant, and a filler in addition to the above-described resin. These materials can be composed of inorganic compounds.

The thickness of the heat-weldable film is not particularly limited, and is preferably in the range of 15 μm or more and 100 μm or less, for example. When the thickness of the heat-weldable film is larger than the above range, the gas barrier property of the outer packaging material may be deteriorated. When the thickness is smaller than the above range, a desired adhesive force cannot be obtained. There is. The thickness of the heat-weldable film is more preferably in the range of 25 μm or more and 90 μm or less, and further preferably in the range of 30 μm or more and 80 μm or less.

The tensile elastic modulus of the heat-weldable film is not particularly limited, and is preferably 1.0 GPa or more, for example. The tensile modulus of the heat-weldable film is within the above range, so that the tensile modulus of the outer packaging material can be within the desired range, and the occurrence of cracks in the gas barrier film is suppressed. Because you can. Moreover, it is because generation | occurrence | production of the pinhole by the stab from the core material used for the said vacuum heat insulating material can be suppressed. The tensile modulus of the heat-weldable film is preferably in the range of 1.0 GPa or more and 5.0 GPa or less, and more preferably in the range of 1.0 GPa or more and 3.0 GPa or less.

4). Protective Film The outer packaging material of the present disclosure may have a protective film in addition to the above-described heat-weldable film and gas barrier film. 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 films in that no layer having a gas barrier property is disposed on either side of the protective film. Although the arrangement position in the outer packaging material of the protective film is not particularly limited, it is preferably arranged on the opposite side of the gas barrier film from the thermally weldable film, and when forming a vacuum heat insulating material It is more preferable that a protective film is disposed at a position to be the outermost layer (outermost layer).

As the protective film, it is preferable to use a resin having a higher melting point than the heat-weldable film, and it may be in the form of a sheet or film. As such a protective film, for example, nylon, polyester, polyamide, polypropylene, polyurethane, amino resin, silicone resin, epoxy resin, thermosetting resin such as polyimide (PI), polyvinyl chloride (PVC), polycarbonate (PC) , Polystyrene (PS), polyvinyl alcohol (PVA), ethylene / vinyl acetate copolymer (EVAL), polyacrylonitrile (PAN), cellulose nanofiber (CNF), etc. ), Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), expanded polypropylene (OPP), polyvinyl chloride (PVC) and the like are preferably used.

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, but is generally in the range of 5 μm or more and 80 μm or less.

The protective film may contain other materials such as an anti-blocking agent, a lubricant, a flame retardant, and a filler. These materials can be composed of inorganic compounds. Alternatively, a hard coat layer containing an inorganic compound may be formed.

5. Adhesive Layer The outer packaging material of the present disclosure may be bonded using a known adhesive. The adhesive may contain an inorganic compound such as a silane coupling agent or a metal chelating agent in order to improve the adhesive force.

6). The outer packaging material for vacuum heat insulating material The thickness of the outer packaging material is not particularly limited as long as the tensile elastic modulus and ash content of the outer packaging material can be within the above-described ranges, and for example, 30 μm or more and 200 μm or less. It is preferable that it is in the range of 50 μm or more and 150 μm or less.

The method for producing 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. For example, a method of pasting each film manufactured in advance with an adhesive, a method of sequentially extruding the raw materials of each heat-melted film with a T-die or the like, and the like can be cited.

Outer cover material, the oxygen permeability of ^{0.1cc / (m 2 · day ·} atm) or less, is preferably Among them ^{0.05cc / (m 2 · day ·} atm) or less. Further, the vacuum heat insulating material for outer material water vapor permeability of 0.5g ^/ (m 2 · day) or less, preferably 0.1g ^/ (m 2 · day) or less, particularly 0.05g ^/ (m 2 · day It is preferable that This is because a vacuum heat insulating material having high heat insulating performance can be formed by having the gas barrier property within the above-described range.

B. Next, the vacuum heat insulating material of the present disclosure will be described. The vacuum heat insulating material of the present disclosure is a vacuum heat insulating material having a core material and a vacuum heat insulating material outer packaging material that encloses the core material, and the vacuum heat insulating material outer packaging material described above is the vacuum heat insulating material outer packaging material. It is characterized by being.

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.
Hereinafter, the vacuum heat insulating material of the present disclosure will be described for each configuration.

1. Outer packaging material for vacuum heat insulating material The outer packaging material in 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. Outer packaging material for vacuum heat insulating material”, and the description thereof is omitted here.
The term “encapsulated” refers to sealing inside a bag formed using an outer packaging material.

2. Core Material The core material in the present disclosure is encapsulated with an outer packaging material for a vacuum heat insulating material.
The core material preferably has a low thermal conductivity. The core material is preferably a porous material having a porosity of 50% or more, particularly 90% or more.

As a material constituting the core material, powder, foam, fiber, or the like can be used.
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. Among these, 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. Furthermore, when a substance having a small infrared absorptance such as titanium oxide, aluminum oxide or indium-doped tin oxide is added as a radiation suppressing material to the above-described material, the infrared absorptivity of the core material can be reduced.

Also, 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. Examples of such 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.

3. Vacuum heat insulating material The vacuum heat insulating material of this indication WHEREIN: The inside enclosed with the outer packaging material for vacuum heat insulating materials is pressure-reduced, and is made into the vacuum state. The degree of vacuum inside the vacuum heat insulating material is preferably 5 Pa or less. By setting the degree of vacuum inside the vacuum heat insulating material within the above range, heat conduction due to convection of air remaining inside can be reduced, and excellent heat insulation can be exhibited.

Also, the heat conductivity of the vacuum heat insulating material is preferably low. For example, the heat conductivity (initial heat conductivity) at 25 ° C. of the vacuum heat insulating material is preferably 5 mW / (m · K) or less. This is because, by setting the heat conductivity of the vacuum heat insulating material in the range, the vacuum heat insulating material becomes difficult to conduct heat to the outside, so that a high heat insulating effect can be achieved. The thermal conductivity (initial thermal conductivity) at 25 ° C. of the vacuum heat insulating material is more preferably 4 mW / (m · K) or less, and further preferably 3 mW / (m · K) or less. The thermal conductivity is measured in accordance with JIS A1412-2: 1999 (Measurement method of thermal resistance and thermal conductivity of thermal insulation materials-Part 2: Heat flow meter method (HFM method)). Using the apparatus, the time required for the test to be steady is 15 minutes or more, the standard plate type EPS, the temperature of the hot surface is 30 ° C., the temperature of the cold surface is 10 ° C., and the sample average temperature is 20 ° C. A method in which the surface is arranged in the vertical direction and measured by a heat flow meter method is used. 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.

4). 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.

5. Applications 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.

C. Next, an article with a vacuum heat insulating material of the present disclosure will be described.
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, wherein 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.

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.

Since the 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.

Specific examples of 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.

Here, 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.

According to the present disclosure, since the outer packaging material is the above-described outer packaging material, and the vacuum heat insulating material can maintain the heat insulating performance for a long period of time, in the apparatus having the heat source unit, the heat from the heat source unit is generated by the vacuum heat insulating material. It heat-insulates and prevents that the temperature of the whole apparatus becomes high temperature, On the other hand, in the apparatus which has a heat retaining part, the temperature state of a heat retaining part can be maintained with a vacuum heat insulating material. Thereby, 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. Examples of 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.

As a mode of attaching the vacuum heat insulating material to the device, 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.

Note that the present disclosure is not limited to the above-described embodiment. The above-described embodiment is an exemplification, and any configuration that has substantially the same configuration as the technical idea described in the scope of the claims of the present disclosure and that exhibits the same effect can be used. It is included in the technical scope of the present disclosure.

Hereinafter, the present disclosure will be described more specifically with reference to examples and comparative examples.
[Example 1]
(Preparation of outer packaging material for vacuum insulation)
From the inside of the outer packaging material, an unstretched polypropylene film (CPP50) having a thickness of 50 μm is deposited as a heat-weldable film, and an aluminum film having a thickness of 40 nm is deposited as a first gas barrier film. (PET) film (Al vapor-deposited PET12 (1)), a film (Al vapor-deposited PET12 (1) with OC) on which an overcoat layer (mixture of resin and inorganic layered compound) of about 230 nm is disposed, As a two-gas barrier film, a film (Al-deposited PET 12 (1) with OC) in which an overcoat layer (a mixture of a resin and an inorganic layered compound) of about 230 nm is disposed on the deposited film of Al-deposited PET12 (1), 3 As a gas barrier film, a silica film having a thickness of 10 nm is deposited, and a 15 μm thick nano film is deposited. The outer cover material having a layer structure of the Ron film (SiO ₂ deposited nylon 15) was prepared. A deposited film side of the deposition film side and OC with Al deposition of the second gas barrier film PET 12 (1) of the Al deposition PET 12 (1) with OC is arranged to face the first gas barrier film, SiO ₂ of the third gas barrier film It arrange | positioned so that the silica membrane of vapor deposition nylon 15 might face the inner side. Each film was bonded with an adhesive layer. The adhesive for forming the adhesive layer is composed of a main component mainly composed of polyester polyol (product name: RU-77T manufactured by Rock Paint), and a curing agent containing aliphatic polyisocyanate (product name: manufactured by Rock Paint). -7), and a two-component curable adhesive in which a solvent of ethyl acetate was mixed so that the weight ratio was main agent: curing agent: solvent = 10: 1: 14. An adhesive layer is formed by applying the above-mentioned adhesive on one surface of the film on the outer side so as to have an application amount of 3.5 g / m ^2, and the film on the outer side on which the adhesive layer is formed; The film on the inner side was pressed with an adhesive layer in between.
Table 1 below shows the layer structure of the outer packaging material of each example and comparative example. In Table 1, when forming the vacuum heat insulating material using the outer packaging material, the outer film is described on the left side of the table, and the inner film is described on the right side of the table. Table 2 shows product names of the films used for the outer packaging material. In addition, the last number of each film name represents the thickness (micrometer) of each film.

(Preparation of vacuum insulation)
With respect to the obtained outer packaging materials of Examples 1 to 5 and Comparative Examples 1 to 5, two outer packaging materials were overlapped, and a three-sided quadrilateral was heat-sealed to create a bag body having only one side opened. The glass wool of 300 mm × 300 mm × 30 mm was used as a core material, and after drying treatment, 5 g of calcium oxide was stored in the bag body as a core material and a desiccant, and the inside of the bag body was evacuated. Then, the opening part of the bag body was sealed by heat sealing to obtain a vacuum heat insulating material. The ultimate pressure was 0.05 Pa.

[Example 2]
50 μm-thick linear short-chain branched polyethylene film (LLDPE50) as a film that can be heat-welded from the inner layer structure of the outer packaging material, and a 12 μm-thick ethylene-vinyl alcohol copolymer as the first gas barrier film A film (Al vapor-deposited EVOH12), a PET film (thick-film Al vapor-deposited PET12) having a thickness of 55 nm deposited as a second gas barrier film, and a metal oxide phosphorous as a third gas barrier film. An outer packaging material and a vacuum heat insulating material were obtained in the same manner as in Example 1 except that a PET film having an acid layer (Clarista CF12) was used.

[Example 3]
50 μm thick linear short-chain branched polyethylene film (LLDPE50) as a film that can be heat-welded from the inner layer structure of the outer packaging material, and 15 μm thick ethylene-vinyl alcohol copolymer as the first gas barrier film A film (Al vapor-deposited EVOH15), a 55-nm thick aluminum film deposited as a second gas barrier film, a 12-μm thick PET film (thick-film Al-deposited PET12), and a third gas barrier film, 55-nm thick An outer packaging material and a vacuum heat insulating material were obtained in the same manner as in Example 1 except that a 12 μm thick PET film (thick film Al deposited PET12) on which an aluminum film was deposited was used.

[Example 4]
The layer structure of the outer packaging material was deposited from the inside as a heat-weldable film, a 30 μm thick unstretched polypropylene film (CPP30), and a first gas barrier film, a 30 nm thick silica film was deposited. a PET film (SiO ₂ deposited PET 12 (1)), as the second gas barrier film, a silica film having a thickness of 30nm was deposited, and the thickness of 12 [mu] m PET film (SiO ₂ deposited PET 12 (1)), the third barrier The outer packaging material and the vacuum heat insulating material were obtained in the same manner as in Example 1 except that the film was a 15 μm thick nylon film (SiO ₂ vapor deposited nylon 15) on which a 10 nm thick silica film was deposited. It was.

[Example 5]
Except that the layer structure of the outer packaging material is CPP50, a 6 μm thick aluminum foil (Al6), a 12 μm thick PET film (PET12), and a 25 μm thick nylon film (ON25) from the inside. In the same manner as in Example 1, an outer packaging material and a vacuum heat insulating material were obtained.

[Comparative Example 1]
50 μm-thick linear short-chain branched polyethylene film (LLDPE50) as a film that can be heat-welded from the inner layer structure of the outer packaging material, and a 12 μm-thick ethylene-vinyl alcohol copolymer as the first gas barrier film A film (Al-deposited EVOH12), a 12 μm thick polyethylene terephthalate (PET) film (Al-deposited PET12 (2)) on which an aluminum film of about 40 nm is deposited as a second gas barrier film, and a protective layer of 25 μm in thickness An outer packaging material and a vacuum heat insulating material were obtained in the same manner as in Example 1 except that the nylon film (ON25) was used.

[Comparative Example 2]
As a film that can be thermally welded from the inside, the layer structure of the outer packaging material is an unstretched polypropylene film (CPP40) having a thickness of 40 μm, a first gas barrier film, a second gas barrier film, and a third gas barrier film, each having a thickness of 10 nm. An outer packaging material and a vacuum heat insulating material were obtained in the same manner as in Example 1 except that a PET film having a thickness of 12 μm (SiO ₂ vapor-deposited PET12 (2)) on which a silica film was deposited was obtained.

[Comparative Example 3]
Other than having made the layer structure of the outer packaging material into 80 μm thick unstretched polypropylene film (CPP80), 40 μm thick aluminum foil (Al40), 15 μm thick nylon film (ON15), and PET12 from the inside. Obtained the outer packaging material and the vacuum heat insulating material in the same manner as in Example 1.

[Comparative Example 4]
An outer packaging material and a vacuum heat insulating material were obtained in the same manner as in Example 1 except that the layer structure of the outer packaging material was changed to an unstretched polypropylene film (CPP40) having a thickness of 40 μm, Al40, and ON25 from the inside.

[Comparative Example 5]
Except that the layer structure of the outer packaging material was changed from the inside to an unstretched polypropylene film (CPP25) with a thickness of 25 μm, an aluminum foil (Al25) with a thickness of 25 μm, and a nylon film (ON12) with a thickness of 12 μm. In the same manner as in Example 1, an outer packaging material and a vacuum heat insulating material were obtained.

[Evaluation]
(Measurement of tensile modulus of outer packaging material for vacuum insulation)
With respect to the outer packaging materials obtained in Examples 1 to 5 and Comparative Examples 1 to 5, the tensile modulus was measured by the method described above. The measurement results of the tensile modulus are shown in Table 3 below.

(Measurement of ash content of outer packaging material for vacuum insulation)
The ash content of each outer packaging material obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was measured by the method described above. The measurement results of the tensile modulus are shown in Table 3 below.

(Measurement of gas barrier property of the twice bent part)
About each side of the rectangle of each vacuum heat insulating material obtained in Examples 1 to 5 and Comparative Examples 1 to 5, it is a place where the core material is not disposed (the outer periphery of the core material), and the facing outer packaging materials The opposite outer packaging material was bent in one direction at a place where no heat welding was performed. Then, the bent portion of the vacuum heat insulating material with each side bent is opened, and the outer packaging material including the two-time bent portion subjected to the two-fold bending is cut out from the vacuum heat insulating material, and transmitted through the two-time bent portion of the outer packaging material. Measurements were made for water vapor and oxygen. Oxygen permeability and water vapor permeability were measured by the methods described above. The measurement results are shown in Table 3 below.

(Measurement of thermal conductivity)
With respect to the vacuum heat insulating materials obtained in Examples 1 to 5 and Comparative Examples 1 to 5, the thermal conductivity before and after the heating test was measured. 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 temperature-controlled room having a temperature of 100 ° C. (humidity is not controlled) for 500 hours was measured. The thermal conductivity was measured by the method described above. The measurement results are shown in Table 3 below.

(Summary)
In the vacuum heat insulating materials of Examples 1 to 5 in which the tensile elastic modulus of the outer packaging material is within a specific range and the ash content of the outer packaging material is within the specific range, the thermal conductivity has a time-dependent value of 11.5 mW. It can be seen that the low thermal conductivity is maintained even after being stored at a high temperature. Note that ASTM C1484-09 stipulates that the heat insulating performance is 11.5 mW / mK or less as a vacuum heat insulating material. On the other hand, the thermal conductivity of the vacuum heat insulating materials of Comparative Examples 1 and 2 in which the ash content of the outer packaging material is low has a low initial value but a high temporal value. This is presumed to be due to the deterioration of the gas barrier film as a result of the outer packaging material being exposed to a high temperature and the gas barrier properties as the outer packaging material being lowered. In addition, the heat conductivity of the vacuum heat insulating materials of Comparative Examples 3 to 5 in which the ash content of the outer packaging material is high has a high initial value and a time-dependent value. This is because the ratio of the metal in the outer packaging material is too high and hardens, so that cracks and the like occur in the outer packaging material particularly at the twice bent portion, and the gas barrier property of the outer packaging material is low at the initial stage. I guess that. The occurrence of cracks or the like in the outer packaging material at the twice bent portions of the vacuum heat insulating materials of Comparative Examples 3 to 5 is also inferred from the measurement results of oxygen permeability at the twice bent portions. In addition, although the water vapor permeability in the 2nd bending part of Example 1 is a comparatively high value, since the desiccant is accommodated in the vacuum heat insulating material, if it is permeation | transmission of the water vapor | steam about Example 1. It can be seen from the measurement results (initial value and time-lapse value) of the thermal conductivity that the influence on the thermal conductivity as a vacuum heat insulating material is extremely small.

DESCRIPTION OF SYMBOLS 1 ... Heat-weldable film 2, 2 '... Gas barrier film 3 ... Resin base material 4 ... Gas barrier layer 5 ... Protective film 10 ... Outer packaging material for vacuum heat insulating material 11 ... Core material 20 ... Vacuum heat insulating material

Claims

A vacuum heat insulating outer packaging material having a heat-weldable film and a gas barrier film,
The tensile elastic modulus of the vacuum insulation outer packaging material is in the range of 1.0 GPa or more and 4.0 GPa or less,
The outer packaging material for vacuum heat insulating materials, wherein the ash content of the outer packaging material for vacuum heat insulating materials is in the range of 1.0 mass% or more and 20 mass% or less.
The outer packaging material for vacuum heat insulating materials according to claim 1, wherein the outer packaging material for vacuum heat insulating materials has two or more gas barrier films.
The outer packaging material for vacuum heat insulating material according to claim 2, wherein the outer packaging material for vacuum heat insulating material has three or more gas barrier films.
The said gas barrier film has a resin base material and the gas barrier layer containing the inorganic compound arrange | positioned at the one or both surface side of the said resin base material, The any one of Claim 1 to 3 characterized by the above-mentioned. The outer packaging material for a vacuum heat insulating material according to one item.
The outer packaging material for a vacuum heat insulating material according to claim 4, further comprising an overcoat layer containing an inorganic compound on a surface of the gas barrier layer opposite to the resin base material.
The outer packaging material for vacuum heat insulating materials according to any one of claims 1 to 3, wherein the tensile elastic modulus of the outer packaging material for vacuum heat insulating materials is 2.0 GPa or more.
The outer packaging material for a vacuum heat insulating material according to any one of claims 1 to 3, wherein the gas barrier film has a metal foil.
The outer packaging material for a vacuum heat insulating material according to any one of claims 1 to 3, wherein the tensile elastic modulus of the outer packaging material for a vacuum heat insulating material is 2.0 GPa or less.
The outer packaging material for a vacuum heat insulating material according to any one of claims 1 to 3, wherein the heat-weldable film contains an inorganic compound.
The outer packaging material for a vacuum heat insulating material has a protective film containing an inorganic compound on the surface of the gas barrier film opposite to the heat-weldable film. The outer packaging material for a vacuum heat insulating material according to one item.
The outer packaging material for vacuum heat insulating material according to any one of claims 1 to 3, wherein the outer packaging material for vacuum heat insulating material has an adhesive layer containing an inorganic compound.
A vacuum heat insulating material having a core material and a vacuum heat insulating material encapsulating the core material,
The outer packaging material for vacuum heat insulating material has a heat-weldable film and a gas barrier film,
The tensile elastic modulus of the vacuum insulation outer packaging material is in the range of 1.0 GPa or more and 4.0 GPa or less,
The vacuum heat insulating material whose ash content of the said outer packaging material for vacuum heat insulating materials exists in the range of 1.0 mass% or more and 20 mass% or less with respect to the said outer packaging material for vacuum heat insulating materials.
An article having a thermal insulation region, and an article with a vacuum insulation comprising 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 outer packaging material for vacuum heat insulating material has a heat-weldable film and a gas barrier film,
The tensile elastic modulus of the vacuum insulation outer packaging material is in the range of 1.0 GPa or more and 4.0 GPa or less,
The article with a vacuum heat insulating material, wherein the ash content of the vacuum heat insulating material outer packaging material is in the range of 1.0% by mass to 20% by mass with respect to the vacuum heat insulating material outer packaging material.