JP2018189163A - Outer packing material for vacuum heat insulation material, vacuum heat insulation material, and article with vacuum heat insulation material - Google Patents

Abstract

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 for a long time even in a high temperature environment. A gas barrier film having at least a heat-weldable film and a gas barrier film, the gas barrier film being disposed on one side or both sides of the resin base material, and containing an inorganic substance. When the storage elastic modulus is measured at a frequency of 10 Hz by a tensile method using a dynamic viscoelasticity measuring device, the outer packaging material 10 for a vacuum heat insulating material having a ash content within a predetermined range is 0. An outer packaging material for a vacuum heat insulating material, wherein a ratio of a storage elastic modulus value at 100 ° C to a value of the above storage elastic modulus at ° C is within a predetermined range. [Selection] Figure 1

Description

  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, vacuum heat insulating materials have been used for the purpose of energy saving of articles. The vacuum heat insulating material is a member in which the core material is arranged in the bag body of the outer packaging material, and the bag body is held in a vacuum state in which the pressure is lower than the atmospheric pressure, and the internal heat convection is suppressed. Can exhibit excellent heat insulation performance. In addition, the said outer packaging material used for a vacuum heat insulating material is called and called the outer packaging material for vacuum heat insulating materials, or just an outer packaging material.

  The outer packaging material for vacuum heat insulating material is bonded to the end when wrapping the core material, gas barrier performance to suppress the permeation of gas such as oxygen and water vapor in order to keep the vacuum state inside the vacuum heat insulating material for a long time. Therefore, physical properties such as heat welding properties for sealing and sealing the core material are required. In order to satisfy these physical properties, the outer packaging material generally employs a configuration including a gas barrier layer and a heat-weldable film as members (Patent Documents 1 to 4). Examples of the gas barrier layer include a metal foil having a thickness of several μm to several tens of μm, a gas barrier film having a thickness of several nm to several hundred nm on one surface of the resin base material, and the gas barrier film containing an inorganic substance. A film is used.

  Among the gas barrier layers, the gas barrier film, in particular, can exhibit high gas barrier performance even if it is thin, and heat bridges are unlikely to occur. Further, since the gas barrier film has better flexibility than the metal foil, defects are less likely to occur when forming the vacuum heat insulating material, and the gas barrier performance is less likely to deteriorate due to the occurrence of defects. For this reason, in the vacuum insulation outer packaging material, a gas barrier film can be suitably used as the gas barrier layer.

JP 2003-262296 A JP 2013-103343 A JP 2006-70923 A JP 2014-62562 A

  An outer packaging material for a vacuum heat insulating material using a gas barrier film having a gas barrier film containing an inorganic substance can be thin and have high gas barrier performance and excellent flexibility. And it is thought that the vacuum heat insulating material formed using such an outer packaging material for vacuum heat insulating materials can maintain the heat insulating performance for a long period of time due to the high gas barrier performance of the outer packaging material.

  However, even when the present inventors use such a gas barrier film having a high gas barrier performance and an outer packaging material for a vacuum heat insulating material, the vacuum heat insulating material formed using the same is in an initial state at room temperature. Despite being able to show high thermal insulation performance, it is known that thermal insulation performance may deteriorate over time in high temperature environments, making it difficult to maintain thermal insulation performance for a long period of time. Got.

  The main object of the present disclosure is to provide an outer packaging material for a vacuum heat insulating material and the like capable of producing a vacuum heat insulating material capable of maintaining good heat insulating performance for a long time even in a high temperature environment.

  The present disclosure includes at least a heat-weldable film and a gas barrier film, and the gas barrier film is disposed on one side or both sides of the resin base material and includes a gas barrier film containing an inorganic substance. An outer packaging material for a vacuum heat insulating material having an ash content of 1.0% by mass or more and 5.0% by mass or less, and a storage elastic modulus was measured at a frequency of 10 Hz by a tensile method using a dynamic viscoelasticity measuring apparatus. When the ratio of the value of the storage elastic modulus at 100 ° C to the value of the storage elastic modulus at 0 ° C is 20% or more, an outer packaging material for a vacuum heat insulating material is provided.

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

  The present disclosure also provides an article with a heat insulating region and an article with a vacuum heat insulating material including a vacuum heat insulating material, wherein the vacuum heat insulating material is the above-described vacuum heat insulating material.

  According to 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 for a long period of time even in a high temperature environment. Moreover, according to this indication, the vacuum heat insulating material which can maintain favorable heat insulation performance for a long period of time also in high temperature environment, and articles | goods with a vacuum heat insulating material using the same 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 the schematic perspective view and sectional drawing which show an example of the vacuum heat insulating material of this indication. It is explanatory drawing explaining the collection method of a measurement sample. It is a schematic sectional drawing which shows the other example of the outer packaging material for vacuum heat insulating materials of this indication.

  The present disclosure includes an outer packaging material for a vacuum heat insulating material, a vacuum heat insulating material, and an article with a vacuum heat insulating material in embodiments. Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. 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, etc. of each part as compared with the embodiment, but are merely examples, and the interpretation of the present disclosure may be interpreted. It is not limited. 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. Further, for convenience of explanation, the description may be made using the terms “upper” or “lower”, but the vertical direction may be reversed.

  Further, in this specification, when a certain configuration such as a certain member or a certain region is “above (or below)” another configuration such as another member or another region, there is no particular limitation. As long as this is not just above (or directly below) other configurations, but also above (or below) other configurations, i.e. Including the case where the above-mentioned components are included.

A. The outer packaging material for vacuum heat insulating material The outer packaging material for vacuum heat insulating material of the present disclosure includes at least a heat-weldable film and a gas barrier film, and the gas barrier film includes a resin base and one side of the resin base or An outer packaging material for a vacuum heat insulating material, which is disposed on both surfaces and includes a gas barrier film containing an inorganic substance, and has an ash content within a predetermined range, and is stored at a frequency of 10 Hz by a tensile method using a dynamic viscoelasticity measuring device. The ratio of the value of the storage elastic modulus at 100 ° C. to the value of the storage elastic modulus at 0 ° C. when the elastic modulus is measured is a predetermined value or more.

In the present disclosure, a value of a storage elastic modulus measured at a frequency of 10 Hz by a tensile method using a dynamic viscoelasticity measuring device may be referred to as a tensile storage elastic modulus value. Moreover, the tensile storage elastic modulus value at 0 ° C. may be expressed as “E ′ ₀ ”, and the tensile storage elastic modulus value at 100 ° C. may be expressed as “E ′ ₁₀₀ ”.
In addition, in the present disclosure, “gas barrier performance” means a function of preventing permeation of a gas such as oxygen and / or water vapor unless otherwise specified.

  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, the outer packaging material 10 of the present disclosure includes at least a heat-weldable film 1 and a gas barrier film 2, and the gas barrier film 2 includes a resin base material 3 and a resin base material 3. The gas barrier film 4 is disposed on one side or both sides (in FIG. 1, one side of the resin base material 3 on the heat-weldable film side) and includes an inorganic substance. The outer packaging material 10 of the present disclosure has an ash content within a predetermined range, and a ratio of a tensile storage elastic modulus value at 100 ° C. to a tensile storage elastic modulus value at 0 ° C. is a predetermined value or more.

  2A and 2B are a schematic perspective view and an XX line sectional view showing an example of a vacuum heat insulating material using the outer packaging material of the present disclosure. The vacuum heat insulating material 20 includes a core material 11 and an outer packaging material 10 in which the core material 11 is enclosed. The outer packaging material 10 is formed into a bag by joining the film sides of the outer packaging material 10 that can be heat-welded at the end 12. A core material 11 is arranged in 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. 2 that are not described are the same members as those in FIG. 1 and are not described here.

  According to the outer packaging material of the present disclosure, the ratio of the tensile storage elastic modulus value at 100 ° C. to the ash content and the tensile storage elastic modulus value at 0 ° C. is within a predetermined range, which is good for a long time in a high temperature environment. It is possible to obtain a vacuum heat insulating material capable of maintaining a good heat insulating performance.

  Specifically, the outer packaging material of the present disclosure can include an inorganic substance in an amount sufficient to exhibit a desired gas barrier performance for a long period of time when the ash content is within a predetermined range. For this reason, the vacuum heat insulating material using the outer packaging material of the present disclosure can maintain low thermal conductivity for a long period of time. Moreover, in the vacuum heat insulating material using the outer packaging material of the present disclosure, an increase in thermal conductivity due to an inorganic substance contained in the outer packaging material such as a heat bridge can be suppressed. Thereby, the vacuum heat insulating material using the outer packaging material of this indication can maintain favorable heat insulation performance for a long period of time.

  In the outer packaging material of the present disclosure, the ratio of the tensile storage elastic modulus value at 100 ° C. to the tensile storage elastic modulus value at 0 ° C. is within a predetermined range, and the amount of change in the tensile storage elastic modulus value due to temperature change Therefore, expansion or contraction due to heat can be suppressed. Thereby, the outer packaging material of this indication can show favorable dimensional stability for a long time in a high temperature environment. At this time, the resin base material of the gas barrier film and the other resin layers constituting the outer packaging material also reduce the dimensional deformation due to heat, and the shear stress generated by thermal expansion and contraction also decreases. For this reason, the said shear stress which a gas barrier film receives can be made small, and it can suppress that a defect generate | occur | produces in a gas barrier film. As a result, the outer packaging material of the present disclosure can exhibit good gas barrier performance for a long period of time in a high temperature environment. The reason why the gas barrier film is defective due to dimensional deformation of the resin base material will be described in detail later.

  Furthermore, the resin base material and the other resin layers may exhibit gas barrier performance, particularly oxygen barrier performance, depending on the type of the resin, but the performance decreases when softened and deformed by heat. May end up. Since the amount of change in the value of the tensile storage modulus due to temperature change is small, the outer packaging material of the present disclosure can suppress dimensional deformation of the resin base material and other resin layers. Thereby, the said resin base material and said other resin layer can exhibit gas barrier performance for a long period of time also in a high temperature environment, and can contribute to maintenance of the long-term gas barrier performance of an outer packaging material.

  Since the outer packaging material of the present disclosure has the above-described effects, the vacuum heat insulating material using the outer packaging material of the present disclosure can maintain good thermal insulation performance for a long time even in a high temperature environment.

The outer packaging material of the present disclosure includes at least a heat-weldable film and a gas barrier film as constituent members.
Hereinafter, the characteristics and configuration of the outer packaging material of the present disclosure will be described.

1. Characteristics of outer packaging material for vacuum heat insulating material The outer packaging material of the present disclosure has an ash content within a predetermined range, and a ratio of a tensile storage elastic modulus value at 100 ° C to a tensile storage elastic modulus value at 0 ° C is predetermined. It is characterized by having two characteristics of being within the range at the same time. Hereinafter, each characteristic will be described.

(1) Characteristics 1
The outer packaging material of the present disclosure is characterized in that the ash content is within a predetermined range. Here, the ash content of the outer packaging material refers to the ratio of the non-combustible component remaining after the outer packaging material burns out in the mass of the entire outer packaging material, and the above ratio approximates the content of inorganic matter in the entire outer packaging material. Here, the inorganic substance refers to an inorganic compound such as a metal (including an alloy), a compound of a metal element, and a compound of a non-metal element.

  The gas barrier performance of the outer packaging material is exhibited by a layer (inorganic material layer) containing an inorganic material such as a gas barrier film in a large proportion. For this reason, the gas barrier performance of an outer packaging material can be prescribed | regulated by the content rate of the inorganic substance which occupies for the whole outer packaging material. Here, as a method for adjusting the content of the inorganic substance, for example, a method of specifying the thickness of the inorganic layer is conceivable. However, for example, the gas barrier film has a different film density depending on the formation conditions, and since the inorganic layer may contain an organic compound, the inorganic content in the entire outer packaging material is simply determined as the inorganic layer. It is difficult to specify only by the thickness of the film.

  The present inventors focused on the ash content of the outer packaging material as a comprehensive index, and as a result of examining the fluctuation of the ash content and the thermal conductivity in the high temperature test, they found that there was a good correlation between them. The ash content of the outer packaging material has a great advantage as a comprehensive index when the inorganic material is used in a complicated manner. That is, the outer packaging material of the present disclosure can contain an inorganic substance in an amount sufficient to exhibit a desired gas barrier performance for a long period of time when the ash content is within a predetermined range. As a result, the vacuum heat insulating material using the outer packaging material of the present disclosure can maintain a low thermal conductivity for a long period of time, and in the vacuum heat insulating material, the heat bridging due to the outer packaging material containing an excessive amount of inorganic substances. Occurrence can be suppressed.

  The outer packaging material of this indication should just be in the range whose ash content is 1.0 mass% or more and 5.0 mass% or less. Specifically, the ash content may be 1.0% by mass or more, preferably 1.1% by mass or more, and more preferably 1.2% by mass or more. Moreover, the said ash content should just be 5.0 mass% or less, it is preferable that it is 4.9 mass% or less, and it is more preferable that it is 4.8 mass% or less.

  The theoretical value of the ash can be calculated from the configuration of the outer packaging material, the specific gravity and thickness of each layer in the outer packaging material, the number of layers of inorganic substances such as a gas barrier film and an overcoat layer, and the like. Specifically, the weight per unit area of each layer in the outer packaging material is calculated from the specific gravity and thickness, and the total weight of the layers mainly composed of inorganic substances is divided by the total weight of the entire outer packaging material. Can do. Here, each layer in the outer packaging material means each layer when one member constituting the outer packaging material is composed of two or more layers, such as a gas barrier film having a resin base material and a gas barrier film. . Examples of the layer containing an inorganic substance as a main component include a gas barrier film and an overcoat layer.

The upper limit of the ash content is, for example, the following three gas barrier films A, one gas barrier film B below, and the following heat-weldable film having a gas barrier film and an overcoat layer on the gas barrier film B side surface, In this order, the layers between the gas barrier films A, the layers between the gas barrier film A and the gas barrier film B located on the most heat-weldable film side, and the layers between the gas barrier film B and the heat-weldable film are respectively adhesive layers. It can be defined from an outer packaging material having a configuration of bonding at a thickness of 3 μm and a specific gravity of about 1.0 g / cm ³ .
The gas barrier film A has an Al—O—P bond (wherein Al represents an aluminum atom and O represents an oxygen atom) on one side of a polyethylene terephthalate (PET) film (thickness 12 μm, specific gravity 1.38 g / cm ³ ). And P represents a phosphorus atom) and has a gas barrier film A (thickness: 500 nm, specific gravity: 2.566 g / cm ³ ). The gas barrier film B, PET film (thickness 12 [mu] m, a specific gravity of 1.38 g / cm ³⁾ on one side of a gas barrier layer B (thickness 65 nm, a specific gravity of 2.7 g / cm ³⁾ is a vapor-deposited aluminum film, further the The inorganic layered compound-containing overcoat layer A (thickness 200 nm, specific gravity 2.60 g / cm ³ ) is assumed to be provided on the gas barrier film B. The heat-weldable film is a CPP film (thickness 25 μm, specific gravity 0.9 g / cm ³ ), and the heat-weldable film is a gas barrier film C (thickness 40 nm) that is an aluminum vapor deposition film on the surface on the gas barrier film B side. has a specific gravity of 2.7 g / cm ^3), further the gas barrier layer C on an inorganic laminar compound-containing overcoat layer B (thickness 200 nm, and having a specific gravity of 2.60g / cm ^3). The inorganic layered compound-containing overcoat layer means an overcoat layer formed of a gas barrier resin composition containing a resin and an inorganic layered compound, which will be described later.
As for the ash content of the outer packaging material having the above-described configuration, a theoretical value of about 4.88% by mass can be obtained from the following formula (1).

(In Formula (1), W ₁ is the mass of the gas barrier film A, W ₂ is the mass of the gas barrier film B, W ₃ is the mass of the gas barrier film C, W ₄ is the mass of the inorganic layered compound-containing overcoat layer B, W _5. Is the mass of the heat-weldable film, W ₆ is the mass of the adhesive layer, W ₇ is the mass of the gas barrier film A of the gas barrier film A, W ₈ is the mass of the gas barrier film B of the gas barrier film B, and W ₉ is the mass of the gas barrier film B. The mass per unit area (1 cm ² ) of each layer is calculated as the product of the thickness (cm) and the specific gravity (g / cm ³ ).

  If the ash content is less than the above-mentioned range, the content of the inorganic matter in the entire outer packaging material is too small, so if good initial gas barrier performance cannot be obtained, even if the initial barrier performance is good, long-term It may not be maintained. Moreover, since the occupation rate of the gas barrier film with respect to the entire outer packaging material is also low, it is suggested that the gas barrier film does not have a sufficient thickness to exhibit the desired gas barrier performance. When the outer packaging material uses a plurality of gas barrier films, the thickness per gas barrier film is expected to be further reduced. For this reason, it is expected that the gas barrier film is likely to transmit gas and that defects such as cracks are likely to occur. As a result, when the outer packaging material of the present disclosure is used as a vacuum heat insulating material, the internal vacuum state may be impaired in a short time, and the heat insulating performance may not be maintained for a long time due to an increase in thermal conductivity. On the other hand, when the ash content is larger than the above-described range, the content of the inorganic matter in the entire outer packaging material is increased, so that heat bridge is generated in the vacuum heat insulating material using the outer packaging material and the thermal conductivity is increased. There is a case.

  In the present disclosure, the ash content is measured using a thermogravimetric / differential thermal analyzer (TG-DTA), and after measuring the mass of the measurement sample, the heating rate is 10 ° C./min in an aluminum pan and in an air atmosphere. After heating from room temperature to 600 ° C., the sample is ashed by heating at 600 ° C. for 30 minutes as it is, and the mass after heating with respect to the mass before heating is expressed as a percentage. As the thermogravimetric / differential thermal simultaneous analyzer, for example, TG8120 manufactured by Rigaku Corporation can be used.

(2) Characteristic 2
The outer packaging material of the present disclosure includes the storage elastic modulus at 100 ° C. with respect to the value of the storage elastic modulus at 0 ° C. when the storage elastic modulus is measured at a frequency of 10 Hz by a tensile method using a dynamic viscoelasticity measuring device. Is a ratio of 20% or more. The above ratio is preferably 25% or more. Moreover, although the said ratio is so preferable that it is large, it is preferable that it is 50% or less. This is because the use of a member that does not easily cause dimensional changes results in high cost for the outer packaging material. Moreover, in the outer packaging material of the present disclosure having a gas barrier film, it is difficult to increase the ratio to 50% or more by using a resin base material widely used for the outer packaging material. Even if it is possible to set the above ratio to 50% or more, in order to satisfy the above ratio, it is necessary to include a large amount of an inorganic substance having a small change in storage elastic modulus due to temperature, resulting in excessive ash content. In some cases, a heat bridge may occur in the vacuum heat insulating material using the outer packaging material.

  In the vacuum heat insulating material used in a high temperature environment, the outer packaging material is exposed to heat in a state where the end portions are joined, so that expansion or contraction occurs to change the dimensions. In the case of a gas barrier film having a resin base material and a gas barrier film that is disposed on one or both sides of the resin base material and contains an inorganic substance, the resin base material and the gas barrier film have greatly different degrees of expansion or contraction due to heat. The resin base material tends to expand or contract more easily. For this reason, in a gas barrier film having a resin base material and a gas barrier film, when the resin base material contracts due to heat, the gas barrier film is likely to be subjected to compressive stress from the resin base material, while the resin base material is subject to heat. When is expanded, the gas barrier film is easily subjected to tensile stress from the resin base material. It is presumed that the gas barrier film is subject to shear stress due to these thermal expansions and contractions, so that defects such as minute cracks are likely to occur.

  In addition, the outer packaging material usually has, in addition to the gas barrier film, a film such as a heat-weldable film and a protective film as other constituent members, and since these other constituent members also contain a resin, they are heated. Expansion or contraction is expected to occur. Since the gas barrier film of the gas barrier film adjacent to the other constituent member receives shear stress due to thermal expansion and contraction of the other constituent member, it is assumed that defects are more likely to occur.

  Here, as an index for obtaining the degree of dimensional change due to heat, the amount of change in the value of the tensile storage modulus due to temperature change can be used. Usually, when the amount of change in the value of the tensile storage modulus due to the temperature change of the entire laminate is large, the laminate tends to expand or contract due to heat, and the dimensional stability tends to decrease. In addition, if even one of the layers constituting the laminate has a large amount of change in the value of the tensile storage modulus due to temperature change, the amount of change in the value of the tensile storage modulus due to a temperature change of the entire laminate is also increased. There is a tendency. This is also true for the outer packaging material of the present disclosure. If even one of the members constituting the outer packaging material has a large expansion or contraction due to heat, the amount of change in the value of the tensile storage elastic modulus of the entire outer packaging material increases. The dimensions change greatly. And when the amount of change in the value of the tensile storage modulus increases, the shear stress that the gas barrier film receives increases, so that defects tend to occur.

  Thus, in order for the vacuum heat insulating material to maintain the heat insulating performance in a high temperature environment for a long time, it is not sufficient to specify the ash content of the outer packaging material, and further, the tensile storage elastic modulus due to the temperature change of the outer packaging material. It is also important to reduce the amount of change in value. That is, even if the packaging material has the same ash content, if the amount of change in the tensile storage modulus due to temperature changes is different, the degree of dimensional change and the occurrence of defects due to shear stress are likely to occur in a high-temperature environment. Therefore, it is assumed that the dimensions cannot be maintained under a high temperature environment and the occurrence of defects cannot be sufficiently suppressed. Therefore, in the present disclosure, in addition to the above-described ash, the above problem has been solved by reducing the amount of change in the value of the storage elastic modulus due to temperature change.

Here, the amount of change in the value of the storage elastic modulus due to temperature change is small that the tensile storage elastic modulus value (E ′ ₀ ) at 0 ° C. and the tensile storage elastic modulus value at 100 ° C. (E ′ ₁₀₀ ) of the outer packaging material. ), That is, the ratio of the tensile storage modulus value (E ′ ₁₀₀ ) at 100 ° C. to the tensile storage modulus value (E ′ ₀ ) at 0 ° C. of the outer packaging material is large. . The oxygen barrier performance of the outer packaging material can be confirmed mainly in the temperature range from 0 ° C. to 100 ° C. When the amount of change in the value of the tensile storage elastic modulus is large in the above temperature range, the oxygen barrier performance of the outer packaging material decreases. It becomes easy to do. Further, in the above case, defects are likely to occur in the inorganic layer formed on one side or both sides of the resin base material in the temperature range, so that the outer packaging material deteriorates not only the oxygen barrier performance but also the water vapor barrier performance.

  According to the outer packaging material of the present disclosure, the ratio of the value of the tensile storage elastic modulus at 100 ° C. to the value of the tensile storage elastic modulus at 0 ° C. is within a predetermined range. The amount of change is small and expansion or contraction due to heat can be suppressed. For this reason, the outer packaging material of the present disclosure can exhibit good dimensional stability even in a high-temperature environment, and can reduce the shear stress that the gas barrier film receives due to the heat shrinkage of the resin base material and other components. . Thereby, generation | occurrence | production of a defect in a gas barrier film | membrane can be suppressed, and a gas barrier film | membrane can exhibit favorable gas barrier performance for a long period of time in a high temperature environment.

  In addition, the resin base material constituting the gas barrier film and the other resin layers constituting the outer packaging material of the present disclosure may have gas barrier performance, particularly oxygen barrier performance, depending on the type of the resin, When the resin is softened, it is presumed that the gas barrier performance of the resin base material and the other resin layer is lowered, and as a result, the gas barrier performance of the entire outer packaging material is lowered. On the other hand, in the outer packaging material of the present disclosure, the ratio of the value of the tensile storage elastic modulus at 100 ° C. to the value of the tensile storage elastic modulus at 0 ° C. is within a predetermined range, and the value of the storage elastic modulus due to temperature change. That is, the resin base material and the other resin layers constituting the outer packaging material of the present disclosure are not easily softened by heat and have high dimensional stability. For this reason, also in the said resin base material and said other resin layer, favorable gas barrier performance can be maintained for a long period of time in a high temperature environment.

The outer packaging material of the present disclosure preferably has a tensile storage modulus value (E ′ ₀ ) at 0 ° C. in the range of 1000 MP to 5000 MP, and particularly preferably in the range of 1500 MP to 4500 MP. .

  The tensile storage modulus value of the outer packaging material at each temperature of 0 ° C. and 100 ° C. is in accordance with JIS K7244-4: 1999 (Plastics—Test method of dynamic mechanical properties, Part 4: Tensile vibration—Non-resonance method) Then, it can be measured by the following method. First, a measurement sample is collected from the outer packaging material by a method to be described later, and both ends of the measurement sample are attached to the chuck (distance between chucks: 20 mm) of the dynamic viscoelasticity measurement apparatus so that the tensile direction is the longitudinal direction of the measurement sample. Applying a tensile load (static load 150 mg), tensile storage elasticity from 0 ° C to 200 ° C at a constant frequency of 10 Hz and a heating rate of 5 ° C / min by the tensile method (sine wave strain, tensile mode, strain: automatic strain) Measure the rate. The measured values at 0 ° C. and 100 ° C. at this time are the tensile storage modulus value of the measurement sample at 0 ° C. and the tensile storage modulus value of the measurement sample at 100 ° C., respectively. Each temperature defining the tensile storage modulus value of the measurement sample can be allowed within a range of ± 1.0 ° C. As the dynamic viscoelasticity measuring device, for example, Rheogel-E4000 manufactured by UBM can be used. Specific measurement conditions in the above method are shown below.

(Measurement conditions for tensile storage modulus)
・ Measurement sample: 40 mm × 5 mm rectangle ・ Distance between chucks (measurement sample length between chucks): 20 mm
・ Measurement mode: Tensile method (sine wave strain tension mode)
・ Raising rate: 5 ° C / min
・ Frequency: 10Hz
・ Measurement temperature range: 0 ℃ ～ 200 ℃
・ Static load: 150mg
・ Distortion amount: Automatic distortion

The ratio of the tensile storage modulus value (E ′ ₁₀₀ ) at 100 ° C. to the tensile storage modulus value (E ′ ₀ ) at ₀ ° C. can be a value obtained from the following formula.
Ratio of tensile storage modulus value (E ′ ₁₀₀ ) at 100 ° C. to tensile storage modulus value (E ′ ₀ ) at ₀ ° C. = (E ′ ₁₀₀ / E ′ ₀ ) × 100 (%)

  A measurement sample used for measurement of the tensile storage modulus can be collected by the method shown in FIG. As shown in FIG. 3, first, a test piece Q having a desired size is cut out from the outer packaging material 10. The number N of test pieces Q sampled from the outer packaging material may be at least N ≧ 1, and preferably N ≧ 3. Next, in the plane of each test piece Q, a reference point P and a reference axis L extending in one arbitrary direction X in the plane from the reference point P as a starting point are set. The measurement sample S is collected so that the one direction X of the axis L is the longitudinal direction of the measurement sample. The measurement sample S has the dimensions described in the tensile storage modulus measurement conditions. The sampling position of the measurement sample S on the reference axis L can be, for example, a position where the center of the rectangle passes through the reference axis L. Subsequently, the reference axis L is rotated by 22.5 ° around the reference point P as a rotation center, and the measurement sample S is similarly collected at each rotation position. As a result, for one test piece Q, 16 measurement samples S are collected radially around the reference point P in the plane. The measurement samples are all rectangular with the above dimensions.

The number of the test pieces cut out from the outer packaging material is preferably at least 1 or more, and more preferably 3 or more. When the number of test pieces is 2 or more, the tensile storage elastic modulus of the outer packaging material is the average of 16 points of the tensile storage elastic modulus of the measurement sample as the tensile storage elastic modulus per test piece, which is further expressed as the number of test pieces. It can be an averaged value.
In the present disclosure, the storage modulus value at each temperature of the outer packaging material may be the value of a total of 16 measurement samples when the number of test pieces N = 1, but the total number when the number of test pieces N = 3. The average value of 48 measurement samples is preferable. The same applies to the ratio of the tensile storage modulus value (E ′ ₁₀₀ ) at 100 ° C. to the tensile storage modulus value (E ′ ₀ ) at 0 ° C. of the outer packaging material.

(3) Others The outer packaging material of the present disclosure preferably has an oxygen permeability of 0.1 cc / (m ² · day · atm) or less, particularly 0.05 cc / (m ² · day · atm) or less. Further, the outer packaging material of the present disclosure has a water vapor permeability of 0.5 g / (m ² · day) or less, particularly 0.1 g / (m ² · day) or less, particularly 0.05 g / (m ² · day). The following is preferable. This is because a vacuum heat insulating material having high heat insulating performance can be formed by having the gas barrier performance within the above-described range.

Oxygen permeability is measured according to JIS K7126-2: 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) For reference, the state of the carrier gas and the test gas can be measured using an oxygen gas permeability measuring device under conditions of a temperature of 100 ° C. and a humidity of 0% RH. As an oxygen gas permeability measuring device, for example, OXTRAN manufactured by MOCON, USA can be used. The measurement is carried out by mounting in the apparatus such that the surface located on the gas barrier film side is in contact with oxygen gas with respect to the film that can be heat-welded in the thickness direction of the outer packaging material among the surfaces of the outer packaging material. It is performed under the condition of about 50 cm ² (transmission region: circular shape with a diameter of 8 cm). The said measurement is performed in the following procedures. First, the carrier gas is purged by supplying the carrier gas at a flow rate of 10 cc / min for 60 minutes or more. As the carrier gas, nitrogen gas containing about 5% hydrogen can be used. After purging, the test gas is allowed to flow through the apparatus, and after 12 hours have been secured as the time from the start of flowing until reaching the equilibrium state, the measurement is started under the above conditions. The test gas uses at least 99.5% dry oxygen. 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 oxygen permeability described in this specification can be measured using the same method as described above.

In addition, the water vapor permeability can be measured using a water vapor permeability measuring device in accordance with ISO 15106-5: 2015 (differential pressure method) under conditions of a temperature of 40 ° C. and a relative humidity difference of 90% RH. it can. As the water vapor transmission rate measuring device, for example, DELTAPERRM manufactured by Technolox, UK can be used. The measurement is carried out so that the surface located on the gas barrier film side of the surface of the outer packaging material on the gas barrier film side is the high humidity side (water vapor supply side) with respect to the film that can be thermally welded in the thickness direction of the outer packaging material. It is mounted between the upper chamber and the lower chamber, and the transmission area is 50.24 cm ² (transmission area: circular shape with a diameter of 8 cm), and the above conditions are used. At least three samples are measured under one condition, and the average of these measured values is taken as the value of water vapor transmission rate under that condition. The water vapor permeability described in the present specification can be measured using a method similar to the above-described method.

2. Configuration of outer packaging material The outer packaging material of the present disclosure includes at least a heat-weldable film and a gas barrier film.

(1) Gas barrier film The gas barrier film in this indication has a resin base material and the gas barrier film which is arranged on the single side or both sides of the resin base material and contains an inorganic substance. The said gas barrier film is arrange | positioned at the one surface side of the film which can be heat-welded, and mainly contributes to the gas barrier performance of an outer packaging material.

(A) Gas barrier film | membrane The said gas barrier film | membrane is a film | membrane which is arrange | positioned at the single side | surface or both surfaces of the resin base material, and contains an inorganic substance. The gas barrier film mainly contributes to the gas barrier performance of the gas barrier film. Examples of inorganic substances include metals (including alloys) and inorganic compounds. Examples of the gas barrier film containing an inorganic substance include a metal film, an inorganic compound film containing an inorganic compound as a main component, an organic-inorganic composite film, and an M—O—P bond (where M represents a metal atom and O represents an oxygen atom) And P represents a phosphorus atom), a film containing a reaction product of a polycarboxylic acid polymer and a polyvalent metal compound, and the like.

  As a metal which comprises a metal film, metals, such as aluminum, stainless steel, titanium, nickel, iron, copper, or an alloy containing these can be mentioned, for example.

Examples of the inorganic compound constituting the inorganic compound film include oxides of metal elements or non-metal elements such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, titanium, boron, yttrium, zirconium, mucerium, and zinc, Examples thereof include oxynitrides, nitrides, oxycarbides, oxycarbonitrides, and the like. Specifically, silicon oxide such as SiO ₂ , aluminum oxide such as Al ₂ O ₃ , magnesium oxide, titanium oxide, tin oxide, silicon zinc alloy oxide, indium alloy oxide, silicon nitride, Examples thereof include aluminum nitride, titanium nitride, silicon oxynitride, and silicon oxide zinc. An inorganic compound may be used independently and may mix and use the above-mentioned material in arbitrary ratios.

  Examples of the organic / inorganic composite film include a film containing a mixed compound having an organic part and an inorganic part. As resin which comprises an organic part, resin illustrated as a constituent material of the resin base material mentioned later is mentioned, for example. As an inorganic substance which comprises an inorganic part, the inorganic substance illustrated with the metal film and the inorganic compound film | membrane is mentioned, for example. Such a mixed compound is not particularly limited as long as the desired gas barrier performance can be exhibited. For example, a mixed compound containing a metal element, an oxygen element, and a hydrophilic group-containing resin, a resin, and an inorganic layered compound described later can be used. Examples thereof include a gas barrier resin composition.

  As a film having an M—O—P bond (wherein M represents a metal atom, O represents an oxygen atom, and P represents a phosphorus atom), for example, a reaction product of a metal oxide and a phosphorus compound is used. It can be set as the film | membrane containing. Examples of the metal oxide include oxides of metals having a valence of 2 or more. Specifically, metals of Group 2 of the periodic table such as magnesium and calcium; Group 12 of the periodic table of zinc and the like. Examples include metals of Group 13 of the periodic table such as aluminum; metals of Group 14 of the periodic table such as silicon; and oxides of metals such as transition metals such as titanium and zirconium. Among these, aluminum oxide (alumina) is preferable. Examples of the phosphorus compound include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. Of these, phosphoric acid is preferred. Specific reaction products of metal oxides and phosphorus compounds can be the same as the reaction products disclosed in, for example, Japanese Patent Application Laid-Open No. 2011-226644.

The presence of the M-O-P bond appears in the infrared absorption spectrum (measured wave number range; 800 cm ⁻¹ or more and 1400 cm ⁻¹ or less), and the maximum infrared absorption peak is in the range of 1080 cm ⁻¹ or more and 1130 cm ⁻¹ or less. This can be confirmed. The method of measuring the infrared absorption spectrum is not particularly limited, for example, a measurement method by total reflection measurement method (ATR method), a method of scraping a sample from the gas barrier film of the outer packaging material, and measuring the infrared absorption spectrum by the KBr method, A method of measuring the collected sample by micro infrared spectroscopy can be used.

  A film containing a reaction product of a polycarboxylic acid polymer and a polyvalent metal compound has a cross-linking bond due to polyvalent metal ions between carboxyl groups of the polycarboxylic acid polymer. The reaction product is a polyvalent metal salt of a polycarboxylic acid polymer. Examples of the polyvalent metal salt of the polycarboxylic acid polymer include zinc acrylate. A film containing a reaction product of a polycarboxylic acid polymer and a polyvalent metal compound includes, for example, a carboxylic acid resin film such as polyacrylic acid, and a coating film in which fine particles of a polyvalent metal compound such as zinc oxide are dispersed. Can be formed by reaction.

  Examples of the gas barrier film having a gas barrier film containing a reaction product of a metal oxide and a phosphorus compound include Kuraray Co., Ltd. manufactured by Kuraray Co., Ltd. Examples of the gas barrier film having a gas barrier film containing a reaction product of a polycarboxylic acid polymer and a polyvalent metal compound include Besela (registered trademark) manufactured by Toppan Printing Co., Ltd.

  The gas barrier film may be a coating film by coating or the like, or may be a vapor deposition film. Among these, a deposited film is preferable from the viewpoint of high adhesion to a resin base material and high gas barrier performance. One gas barrier film may be a single film formed by single vapor deposition, or may be a multilayer film formed by multiple vapor deposition. When one gas barrier film is a multilayer film, films having the same composition may be combined or films having different compositions may be combined. When one gas barrier film is a multilayer film, the entire multilayer film is one gas barrier film.

The thickness per one of the gas barrier films is not particularly limited as long as the desired gas barrier performance can be exhibited, and can be appropriately set according to the type and configuration of the gas barrier film, for example, 5 nm to 200 nm. In particular, it is preferably in the range of 10 nm to 100 nm. When one gas barrier film is a multilayer film, the thickness per gas barrier film refers to the thickness of the entire multilayer film constituting one gas barrier film.
If the thickness of the gas barrier film is less than the above range, film formation may be insufficient and desired gas barrier performance may not be exhibited. In addition, the strength may not be ensured, and deterioration with time may occur. On the other hand, if the thickness of the gas barrier film exceeds the above range, defects may easily occur when subjected to mechanical stress such as bending, or flexibility may be reduced. Moreover, the content rate of the inorganic substance which occupies for the whole outer packaging material becomes excessive, and it may become easy to produce a heat bridge in a vacuum heat insulating material.

  The method for forming the gas barrier film may be any method that can form a film with a desired thickness on one or both sides of the resin base material, and a conventionally known method according to the type of the gas barrier film, such as a coating method, a vapor deposition method, or a pressure bonding method. Can be used.

(B) Resin base material The resin base material is not particularly limited as long as it can support the gas barrier film. For example, a resin film or a resin sheet 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. For example, a polyolefin resin such as polyethylene or polypropylene; a polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polybutylene terephthalate (PBT); a cyclic polyolefin Resin; Polystyrene resin; Acrylonitrile-styrene copolymer (AS resin); Acrylonitrile-butadiene-styrene copolymer (ABS resin); Poly (meth) acrylic resin; Polycarbonate resin; Polyvinyl alcohol (PVA) resin, Ethylene-vinyl alcohol Polyvinyl alcohol resins such as copolymer (EVOH) resins; various polyamide resins such as nylon; polyimide resins; polyurethane resins; acetal resins; various resins such as cellulose resins It can be used.

When a plurality of gas barrier films are used for the outer packaging material, it is preferable to use a hydrophilic group-containing resin for the resin base material of the gas barrier film disposed at a position closer to the heat-weldable film. This is because the hydrophilic group-containing resin exhibits good barrier performance against oxygen even at a high temperature, and thus can improve the oxygen barrier performance as an outer packaging material. 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. Examples of the hydrophilic group-containing resin include natural polymers such as PVA resin, (meth) acrylic resin, cellulose resin, and polysaccharide.

  In the outer packaging material of the present disclosure, it is preferable that at least the resin base material does not contain an ethylene-vinyl alcohol copolymer resin (EVOH resin). Since EVOH resin has high oxygen barrier performance and large thermal shrinkage, when the vacuum heat insulating material using the outer packaging material of the present disclosure is used in a high temperature environment, the gas barrier film is sheared by thermal expansion and contraction of the resin base material. Defects such as cracks are likely to occur due to stress, and the gas barrier performance that the EVOH resin base material originally can exhibit due to heat shrinkage, in particular, oxygen barrier performance cannot be exhibited. As a result, the entire outer packaging material in a high temperature environment The gas barrier performance may be reduced.

  Further, in the EVOH resin layer on which aluminum is vapor-deposited, there is a case where “heat shrinkage wrinkles” and “sagging” occur because the EVOH resin thermally shrinks during the aluminum vapor deposition process. In addition, as a problem due to this, in the laminating process when making the outer packaging material, “thermal shrinkage wrinkles” leave wrinkle marks and “sagging” becomes wrinkles, both of which have poor appearance and poor oxygen gas barrier performance, etc. Poor quality may occur. For the above reasons, it is more preferable to use a resin base material that does not contain an EVOH resin.

  The above-mentioned resin base material does not contain an EVOH resin not only when the resin base material contains no EVOH resin but also the content of the EVOH resin in the resin base material described above in the outer packaging material of the present disclosure. This includes cases where the amount does not impair the characteristics. Specifically, the EVOH resin content in the resin base material is 50% by mass or less, preferably 25% by mass or less, and particularly preferably 0% by mass. When the resin base material has a multilayer structure, the EVOH resin content in the resin base material can be the EVOH resin content relative to the total amount of one resin base material. The presence and content of the EVOH resin in the resin substrate can be specified using, for example, infrared absorption (FT-IR) analysis, X-ray photoelectron analyzer (XPS), or the like. In addition, it can prescribe similarly to the above that layers and members other than the resin base material do not contain EVOH resin.

  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 film can be improved.

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

(C) Overcoat layer The gas barrier film may further have an overcoat layer on the surface of the gas barrier film opposite to the resin substrate. It is because the gas barrier performance of the gas barrier film can be further improved by having the overcoat layer on the gas barrier film.

  The material which comprises an overcoat layer is not specifically limited, The material generally used as a barrier coat agent or an overcoat agent can be used. Examples of the material include a gas barrier resin composition containing a resin and an inorganic layered compound, a sol-gel compound, a reaction product of a metal oxide and a phosphorus compound described in the above section “(a) Gas barrier film”, poly Examples include reaction products of carboxylic acid polymers and polyvalent metal compounds.

  The inorganic layered compound contained in the gas barrier resin composition refers to an inorganic compound in which unit crystal layers overlap to form one layered particle. Examples of the inorganic layered compound include clay minerals such as smectite, kaolin, mica, hydrotalcite, and chlorite. Examples of the resin contained in the gas barrier resin composition include polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN), polysaccharides, and polyacrylic. Examples thereof include acids and esters thereof.

  The overcoat layer formed of the gas barrier resin composition is prepared by, for example, applying an aqueous solution of the gas barrier resin composition in which the resin and the inorganic stratiform compound are dissolved and dispersed in a solvent onto the gas barrier film of the gas barrier film and drying. Can be formed. In preparing the aqueous solution of the gas barrier resin composition, the inorganic layered compound may be swollen and cleaved in a dispersion medium such as water in advance if necessary. The overcoat layer formed from the gas barrier resin composition may be referred to as an inorganic layered compound-containing overcoat layer.

The overcoat layer containing the sol-gel compound is, for example, a general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, 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.) It can be formed from a raw material liquid containing a hydrophilic group-containing resin and further obtained by polycondensation by a sol-gel method. Examples of the metal atom M of the alkoxide represented by the above general formula include silicon, zirconium, titanium, aluminum and the like. Of these, silicon is preferred. The silicon alkoxide is preferably tetraethyl orthosilicate (TEOS). In addition, examples of the hydrophilic group-containing resin include resins containing a hydrophilic group. Specifically, polyvinyl alcohol resins, ethylene / vinyl alcohol copolymers, acrylic resins, natural polymer methyl cellulose, carboxymethyl cellulose, Examples thereof include cellulose nanofibers and polysaccharides. Of these, polyvinyl alcohol resins are preferred.

  The sol-gel compound can be a mixed compound containing a metal element, an oxygen element, and a hydrophilic group-containing resin, and includes a carbon atom (C) in the hydrophilic group-containing resin and a metal atom (M) in the metal alkoxide. There can be a C—O—M bond through oxygen (O) in between. Among these, the sol-gel compound is preferably a polycondensate of tetraethyl orthosilicate (TEOS) and a polyvinyl alcohol resin. The polycondensate of tetraethyl orthosilicate (TEOS) and polyvinyl alcohol resin can be the same as that disclosed in, for example, Japanese Patent No. 5568897.

  Especially, it is preferable that an overcoat layer is formed with a sol-gel compound. This is because the sol-gel compound has a high adhesive strength at the interface and can perform the treatment during film formation at a relatively low temperature, thereby suppressing thermal deterioration of the resin base material and the like.

  Although the thickness of an overcoat layer is not specifically limited, For example, it can be in the range of 50 nm or more and 500 nm or less.

(D) Others The gas barrier film only needs to have a gas barrier film disposed on at least one surface of the resin base material, and the gas barrier film may be disposed on both surfaces of the resin base material.

3. Heat-weldable film The heat-weldable film in the present disclosure is a film that can be welded by heating. The heat-weldable film is in contact with the core material when forming the vacuum heat insulating material using the outer packaging material of the present disclosure, and when the core material is sealed, the end portions of the outer packaging materials facing each other are sealed. It is a member to join.

For the heat-weldable film, a material that can be melted and fused by heating is used. As such a material, a thermoplastic resin is preferably used. Examples of the thermoplastic resin include polyolefin resins, polyester resins, polyvinyl acetate resins, polyvinyl chloride resins, poly (meth) acrylic resins, urethane resins, polyvinyl alcohol resins, and ethylene-vinyl alcohol copolymers. (EVOH) resin, polyphenylene sulfide (PPS) resin, tetrafluoroethylene (C ₂ F ₄ ) / ethylene (C ₂ H ₄ ) copolymer (ETFE) resin, and the like.

The heat-weldable film is preferably a film mainly composed of the above-described thermoplastic resin. Specifically, polyethylene resin films such as polyethylene such as linear short chain branched polyethylene (LLDPE) and high density polyethylene (HDPE) and unstretched polypropylene (CPP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN). ), Polyester resin films such as polybutylene terephthalate (PBT), polyvinyl acetate resin films, polyvinyl chloride resin films, poly (meth) acrylic resin films, urethane resin films, polyvinyl alcohol resin films, ethylene- vinyl alcohol copolymer (EVOH) resin films, polyphenylene sulfide (PPS) resin film, tetrafluoroethylene (C ₂ F ₄₎ · ethylene (C ₂ H ₄₎ a copolymer (ETFE) resin film is ani It is. A main component means the component which occupies 50 mass% or more in the film in which heat welding is possible.

  The heat-weldable film can be appropriately selected from the above resin films according to the melting point to be set. For example, a resin film mainly composed of a low melting point resin such as a linear short chain branched polyethylene (LLDPE) has high versatility, and the melting point of a heat-weldable film can be set low, so that the temperature is relatively low. Can be suitably used from the viewpoint that heat welding is possible. In addition, for resin films mainly composed of a resin having a melting point of 145 ° C. or higher, such as PP resin, EVOH resin, PET resin, PBT resin, ETFE resin, PPS resin, etc., the melting point of the heat-weldable film is set to 145 ° C. or higher. The film can be suitably used from the viewpoint of being able to prevent thermal deterioration of the heat-weldable film and obtaining a vacuum heat insulating material that can withstand use in a higher temperature environment.

  The heat-weldable film preferably does not contain EVOH resin. This is because the EVOH resin has a large shrinkage due to heat, so that the dimensional stability of the outer packaging material is impaired, the gas barrier film is likely to be defective, and the gas barrier performance of the entire outer packaging material is deteriorated. The details of “not including EVOH resin” are as described above.

  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.

  The melting point of the heat-weldable film is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 145 ° C. or higher, although it depends on the material. The melting point is preferably 300 ° C. or lower, more preferably 290 ° C. or lower, more preferably 280 ° C. or lower. By setting the melting point of the thermally weldable film within the above range, it is possible to suppress peeling of the sealing surface of the outer packaging material under the usage environment of the vacuum heat insulating material manufactured using the outer packaging material of the present disclosure. Can withstand use in high temperature environments. Moreover, when manufacturing a vacuum heat insulating material using the outer packaging material of this indication, the heat deterioration of the gas barrier film or the film which can be heat-welded can be suppressed by the heating for sealing. Furthermore, the heat-weldable film can be made difficult to expand or contract even when used in a high temperature environment for a long period of time by increasing the melting point.

  The melting point of the heat-weldable film in the outer packaging material of the present disclosure can be measured by the following method using a differential scanning calorimeter (DSC). First, a heat-weldable film is peeled off from the outer packaging material to obtain a measurement sample of about 10 mg. This measurement sample was put in an aluminum cell, and the temperature was raised from 20 ° C. to 300 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere using a differential scanning calorimeter (DSC204, manufactured by NETZSCH). Hold for 10 minutes. Furthermore, after cooling to 20 ° C. at a temperature lowering rate of 10 ° C./min and holding at that temperature for 10 minutes, the temperature is raised again to 300 ° C. at a temperature rising rate of 10 ° C./min (second temperature increase). The intersection of the tangent at the melting point observed at the second temperature rise and the baseline of the DSC curve on the lower temperature side than the melting point can be the melting point of the heat-weldable film.

  The thickness of the heat-weldable film is not particularly limited, but can be, for example, in the range of 15 μm to 100 μm, preferably in the range of 25 μm to 90 μm, and more preferably in the range of 30 μm to 80 μm. . By making the thickness of the heat-weldable film within the above range, it is possible to suppress a decrease in gas barrier performance of the outer packaging material, and to produce a desired adhesive force when joining the outer packaging materials in the production of the vacuum heat insulating material. Can be obtained.

4). Protective film The outer packaging material of this indication may have a protective film. It is because the constituent member of the outer packaging material of the present disclosure other than the protective film can be protected from damage and deterioration by having the protective film. The protective film can be distinguished from the above-described gas barrier film in that no gas barrier film is disposed on either side of the protective film. Although the arrangement position of the protective film in the outer packaging material of the present disclosure is not particularly limited, the gas barrier film is preferably arranged on the side opposite to the thermally weldable film, and when forming a vacuum heat insulating material. More preferably, the outermost layer (outermost layer) is disposed at a position.

  The material constituting the protective film and a resin having a higher melting point than the heat-weldable film are preferable. For example, nylon resin, polyester resin, polyamide resin, polypropylene resin, polyurethane resin, amino resin, silicone resin, epoxy resin, polyimide ( PI) resin, polyvinyl chloride (PVC) resin, polycarbonate (PC) resin, polystyrene (PS) resin, polyvinyl alcohol (PVA), ethylene-vinyl acetate copolymer (EVAL), polyacrylonitrile (PAN) resin, cellulose nano A fiber (CNF) etc. are mentioned. The said protective film can be made into the resin film which has at least 1 sort (s) selected from the resin group mentioned above as a main component. A main component means the component which occupies 50 mass% or more in a protective film.

  Among these, as the protective film, stretched nylon (ONY) film, polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polybutylene terephthalate (PBT) film, stretched polypropylene (OPP) film, polyvinyl chloride (PVC) ) A film or the like is preferably used.

  The protective film preferably does not contain EVOH resin. Since EVOH resin has a large shrinkage due to heat, there is a risk that the dimensional stability of the outer packaging material is impaired, the gas barrier film is likely to be defective due to the thermal shrinkage of the protective film, and the gas barrier performance of the entire outer packaging material is deteriorated. Because there is. The detailed reason and details of “not including EVOH resin” are as described above.

  The protective film may contain other materials such as an antiblocking agent, a lubricant, a flame retardant, and a filler.

  The protective film may be a single layer or may have a laminated structure in which a plurality of layers made of the same material or layers made of different materials are laminated. Although the thickness of a protective film is not specifically limited, Generally it can be in the range of 5 micrometers or more and 80 micrometers or less.

  The protective film can exhibit high gas barrier performance by itself depending on the constituent material. In addition, the said protective film can also have an overcoat layer on one side. The overcoat layer can be the same as the overcoat layer described in the section “2. Gas barrier film” described above. When the said protective film has an overcoat layer on one side, it is preferable to arrange | position so that the surface by the side of the overcoat layer of the said protective film may become the film side which can be heat-welded.

5. Arbitrary Configuration In the outer packaging material of the present disclosure, each member constituting the outer packaging material may be bonded using a known adhesive. In order to improve the adhesive force, the adhesive may contain a silane coupling agent, a metal chelating agent, and the like. In addition, it is preferable that the arbitrary member which comprises the outer packaging material of this indication does not contain EVOH resin.

6). External packaging material for vacuum heat insulating material In the external packaging material of the present disclosure, when the gas barrier film has a resin base material and a gas barrier film disposed on one side of the resin base material, as shown in FIG. The gas barrier film 4 and the resin base material 3 may be provided in this order from the heat-weldable film 1 side. As shown in FIG. 4A, the gas-barrier film 2 is heat-weldable from the film 1 side. You may have the base material 3 and the gas barrier film | membrane 4 in this order. In addition, the outer packaging material 10 of this indication shown to Fig.4 (a) has the structure by which the protective film 5 was further arrange | positioned on the surface on the opposite side to the film 1 of the gas barrier film 2 which can be heat-welded.

  Especially, it is preferable that the outer packaging material of this indication has the resin base material and the gas barrier film in this order from the film side in which the gas barrier film which contact | connects one side of the film in which heat welding is possible is heat-weldable. When the heat-weldable film and the resin base material are in contact with each other, shear stress generated by thermal expansion and contraction of the heat-weldable film can be buffered by the resin base material, and the occurrence of defects in the gas barrier film is suppressed. Because it can.

  In addition, the outer packaging material of the present disclosure may include a plurality of gas barrier films as long as the two characteristics described above can be provided. The number of gas barrier films can be appropriately set in accordance with the specifications of the gas barrier film and the gas barrier performance per gas barrier film within a range in which two characteristics can be provided. For example, if the gas barrier film in the outer packaging material of the present disclosure is a case where the gas barrier film is disposed on one side of the resin base material, the number of the gas barrier films included in the outer packaging material of the present disclosure is one or more. Well, preferably 3 or more, more preferably 4 or more. The number of gas barrier films can be 6 or less, preferably 5 or less, more preferably 4 or less. This is because if the number of gas barrier films is too large, the outer packaging material becomes hard, and the possibility that the gas barrier film breaks at the corners of the core material during the production of the vacuum heat insulating material increases. In addition, when it is difficult to keep the ash content of the outer packaging material within a predetermined range, or even when the ash content of the outer packaging material is within the predetermined range, the thickness per one of the gas barrier film is reduced, and a defect occurs. It may be easier. When the outer packaging material has a plurality of gas barrier films, the gas barrier films may be the same or different.

As an arrangement | positioning aspect of a some gas barrier film, the following aspects are mentioned, for example.
FIGS. 4B to 4D show a case where the outer packaging material of the present disclosure has two gas barrier films, and the outer packaging material 10 of the present disclosure includes a heat-weldable film 1 and a heat-weldable film. The first gas barrier film 2a disposed on one surface of the first gas barrier film, the second gas barrier film 2b disposed on the surface opposite to the heat-weldable film 1 of the first gas barrier film 2a, and the second gas barrier film 2b The example of the structure which has the protective film 5 arrange | positioned on the surface on the opposite side to the 1st gas barrier film 2a is shown.
In the above case, as shown in FIG. 4 (b), the arrangement of the two gas barrier films is such that the first gas barrier film 2a is bonded to the resin base material 3 and the gas barrier film 4 from the thermally weldable film 1 side. The second gas barrier film 2b can have the gas barrier film 4 and the resin base material 3 in this order from the thermally weldable film 1 side. Further, as shown in FIG. 4C, the first gas barrier film 2a has the gas barrier film 4 and the resin base material 3 in this order from the heat-weldable film 1 side, and the second gas barrier film 2b is heated. You may have the gas barrier film | membrane 4 and the resin base material 3 in this order from the film 1 side which can be welded. Furthermore, as shown in FIG. 4D, the first gas barrier film 2a has the resin base material 3 and the gas barrier film 4 in this order from the heat-weldable film 1 side, and the second gas barrier film 2b You may have the resin base material 3 and the gas barrier film | membrane 4 in this order from the film 1 side which can be welded.

FIGS. 4E and 4F show the case where the outer packaging material of the present disclosure has three gas barrier films, and the outer packaging material 10 of the present disclosure can be thermally welded to the film 1 that can be thermally welded. A first gas barrier film 2a disposed on one surface of the transparent film 1, a second gas barrier film 2b disposed on a surface opposite to the thermally weldable film 1 of the first gas barrier film 2a, and a second gas barrier The example of the structure which has the 3rd gas bar film 3c arrange | positioned at the surface on the opposite side to the 1st gas barrier film 2a of the film 2b is shown.
In the above case, as the arrangement of the three gas barrier films, as shown in FIG. 4 (e), the first gas barrier film 2a is bonded to the resin base material 3 and the gas barrier film 4 from the thermally weldable film 1 side. The second gas barrier film 2b has the gas barrier film 4 and the resin base material 3 in this order from the thermally weldable film 1 side, and the third gas barrier film 2c has the gas barrier from the thermally weldable film 1 side. The film 4 and the resin base material 3 can be provided in this order. Further, as another example of the above arrangement mode, as shown in FIG. 4 (f), the first gas barrier film 2a has the gas barrier film 4 and the resin base material 3 in this order from the thermally weldable film 1 side. The second gas barrier film 2b has the gas barrier film 4 and the resin base material 3 in this order from the thermally weldable film 1 side, and the third gas barrier film 2c has the gas barrier film 4 from the thermally weldable film 1 side. And the resin base material 3 can be provided in this order.

  When the outer packaging material of the present disclosure has a plurality of gas barrier films, the first gas barrier film on the most thermally weldable film side has a resin base material and a gas barrier film in this order from the thermally weldable film side, It is preferable that the 2nd gas barrier film arrange | positioned on the surface on the opposite side to the said heat weldable film of a 1st gas barrier film has a gas barrier film | membrane and the resin base material in this order from the film weldable film side. By disposing the two gas barrier films closest to the heat weldable film so that the gas barrier films are in contact with each other, deterioration of the gas barrier film due to mechanical stress from the outside can be suppressed. . Further, since the resin base material is not interposed between the two gas barrier films, it is possible to suppress the occurrence of defects in the gas barrier film due to the shear stress due to the thermal expansion and contraction of the resin base material.

  The outer packaging material of the present disclosure may include a gas barrier film as a gas barrier layer and may not include a metal foil. However, the outer packaging material may include the gas barrier film and have the above-described two characteristics. In addition to the gas barrier film, a metal foil can be further included.

  The thickness of the outer packaging material of the present disclosure is not particularly limited as long as it has the above-described characteristics, and can be, for example, in the range of 30 μm to 200 μm, preferably in the range of 50 μm to 150 μm.

  The manufacturing method of the outer packaging material of the present disclosure is not particularly limited, for example, a method in which each film manufactured in advance is bonded with an adhesive, a raw material of each heat-melted film is sequentially extruded with a T die or the like, and a laminate is formed. A known method such as a obtaining method can be used.

  The outer packaging material of this indication is used for a vacuum heat insulating material. The outer packaging material of the present disclosure is a film in which one of two surfaces facing each other in the thickness (lamination) direction can be heat-welded. In a vacuum heat insulating material, usually, a pair of outer packaging materials are arranged to face each other via a core material such that the heat-weldable film side surface is on the core material side.

B. Vacuum heat insulating material The vacuum heat insulating material of this indication is a vacuum heat insulating material which has a core material and the outer packaging material for vacuum heat insulating materials which encloses the said core material, Comprising: The said outer packaging material for vacuum heat insulating materials mentioned above "A. This is the same as that described in the section “Vacuum insulation material for vacuum heat insulating material”.

FIG. 2 described above shows an example of the vacuum heat insulating material of the present disclosure.
According to the present disclosure, the outer packaging material of the vacuum heat insulating material is composed of the outer packaging material for vacuum heat insulating material described in the above-mentioned section of “A. Insulation performance can be maintained.
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 is a member that encloses a core material, and is the same as the outer packaging material described in the above-mentioned section “A. Outer packaging material for vacuum heat insulating material”. Description is omitted. The term “encapsulated” refers to sealing inside a bag formed using an outer packaging material.

2. Core Material A core material in the present disclosure is a member that is enclosed by an outer packaging material for a vacuum heat insulating material. The core material preferably has a low thermal conductivity. The core material can be 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 the decrease 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.

  As the foam, urethane foam, styrene foam, phenol foam and the like can be used. Among them, a foam that forms open cells is preferable.

  The fiber body may be an inorganic fiber or an organic fiber, but it is preferable to use an 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.

  As the core material, the above-described materials may be used alone, or a composite material in which two or more materials are mixed may be used.

3. Vacuum heat insulating material As for the vacuum heat insulating material of this indication, a core material is enclosed with the inside of an outer packaging material, and the above-mentioned inside is decompressed and it is in a vacuum state. The degree of vacuum inside the vacuum heat insulating material is preferably 5 Pa or less, for example. This is because heat conduction by convection of air remaining inside can be lowered, and excellent heat insulation can be exhibited.

  The heat conductivity of the vacuum heat insulating material is preferably as low as possible. For example, the heat conductivity (initial heat conductivity) is preferably 5 mW / (m · K) or less. This is because the vacuum heat insulating material is difficult to conduct heat to the outside, and a high heat insulating effect can be achieved. Among these, the initial thermal conductivity is more preferably 4 mW / (m · K) or less, and further preferably 3 mW / (m · K) or less.

  The thermal conductivity conforms to JIS A1412-2: 1999 (Method for measuring thermal resistance and thermal conductivity of thermal insulation material-Part 2: Heat flow meter method (HFM method)), and uses a thermal conductivity measuring device. It can be a value measured by a heat flow meter method. As the thermal conductivity measuring device, for example, a thermal conductivity measuring device Auto Lambda HC-074 (manufactured by Eihiro Seiki) can be used. The measurement is performed under the following conditions so that both main surfaces of the measurement sample are directed in the vertical direction. Before measuring the thermal conductivity, it is preferable to measure in advance using a heat flow meter or the like whether the temperature of the measurement sample is equal to the measurement environment temperature. 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.

(Measurement conditions for thermal conductivity)
・ Measurement sample: width 29cm ± 0.5cm, length 30cm ± 0.5cm
・ Time required for steady state of test: 15 minutes or more ・ Type of standard plate: EPS
・ Hot surface temperature: 30 ℃
・ Cold surface temperature: 10 ℃
-Average temperature of measurement sample: 20 ° C

4). Others A general method can be used for the manufacturing method of the vacuum heat insulating material of the present disclosure. For example, two outer packaging materials are prepared, each heat-weldable film is faced and overlapped, and the outer edges of three sides are heat-welded to obtain a bag body having one side open. After putting the core material into the bag body from the opening, the vacuum heat insulating material can be obtained by sucking air from the opening and sealing the opening in a state where the inside of the bag body is decompressed.

  The vacuum heat insulating material of the present disclosure 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 is an article having a heat insulating region and an article with a vacuum heat insulating material provided with a vacuum heat insulating material, wherein the vacuum heat insulating material includes a core material and a core material. The vacuum insulation material outer packaging material is the one described in the above-mentioned section "A. Vacuum insulation material packaging material".

  According to the present disclosure, the vacuum heat insulating material used for the article is configured by the outer packaging material described in the section “A. Vacuum heat insulating material outer packaging material”, and the vacuum heat insulating material is highly insulated for a long time even in a high temperature environment. Since the performance can be exhibited, the article can exhibit energy saving properties for a long time.

  The vacuum heat insulating material and the outer packaging material used therefor in the present disclosure have been described in detail in the above-mentioned sections “B. Vacuum heat insulating material” and “A. Vacuum heat insulating material outer packaging material”, and thus the description thereof is omitted here. .

The article in the present disclosure has a thermally insulating region. Here, 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. It is. These areas may be spaces or objects.
Examples of the above-mentioned articles include, for example, electric devices such as refrigerators, freezers, heat insulators, and coolers, heat insulation containers, cold insulation containers, transport containers, containers, containers such as storage containers, vehicles such as vehicles, airplanes, and ships, houses, warehouses, etc. Building materials such as building materials, wall materials and floor materials.

  Hereinafter, the present disclosure will be described more specifically with reference to examples and comparative examples.

The abbreviations of the films used in the production of the vacuum insulation outer packaging material are as follows. Details of each film are shown in Table 1.
Al-deposited PET12: Polyethylene terephthalate (PET) film (thickness 12 μm) with an aluminum (Al) film (thickness 55 nm) deposited on one side
-Al vapor-deposited PET12 with OC layer (A): Overcoat (abbreviated as OC) obtained by coating an Al film of Al-deposited PET12 with an aqueous solution of a gas barrier resin composition containing an inorganic layered compound and a resin. The same shall apply hereinafter.) Film with layer (A) and thick film Al-deposited PET12: Polyethylene terephthalate (PET) film (thickness 12 μm) with an aluminum (Al) film (thickness 65 nm) deposited on one side
Thick film Al vapor-deposited PET12 with OC layer (A): Overcoat of about 200 nm obtained by coating an aqueous solution of a gas barrier resin composition containing an inorganic layered compound and a resin on the Al film of the thick film Al vapor-deposited PET12 OC) layer (A) arranged film / OC layer (B) thick film Al vapor-deposited PET12: on the Al film of thick film Al vapor-deposited PET12, an alkoxide containing silicon and a water-soluble high film containing a polyvinyl alcohol-based resin A film in which an overcoat (OC) layer (B) of about 200 nm is obtained by polycondensation with molecules by a sol-gel method. Al vapor deposition EVOH12: Aluminum (Al) film (thickness 40 nm) was vapor-deposited on one side. Ethylene-vinyl alcohol copolymer (EVOH) film (thickness 12 μm)
-Al vapor deposition EVOH15: An ethylene-vinyl alcohol copolymer (EVOH) film (thickness 15 μm) in which an aluminum (Al) film (thickness 55 nm) is vapor-deposited on one side
· SiO ₂ deposition ON15: silicon dioxide (SiO ₂₎ film nylon (thickness 10 nm) was deposited on one side (ON) film (thickness 15 [mu] m)
SiO ₂ vapor-deposited PET12: PET film (thickness 12 μm) with a silicon dioxide (SiO ₂ ) film (thickness 10 nm) deposited on one side
Al ₂ O ₃ vapor-deposited PET12 (A): PET film (thickness 12 μm) with an aluminum oxide (Al ₂ O ₃ ) film (thickness 10 nm) deposited on one side
Al ₂ O ₃ vapor-deposited PET12 (B): PET film (thickness 12 μm) with an aluminum oxide (Al ₂ O ₃ ) film (thickness 10 nm) deposited on one side
· OC layer (B) with _Al 2 _{O 3} deposited _{PET12 (B): Al 2 O} 3 in _{the Al} 2 _{O 3} film on the deposition PET 12 (B), and alkoxides containing silicon, water-soluble high containing a polyvinyl alcohol resin PET film with an Al—O—P bond-containing layer provided with an overcoat (OC) layer (B) of about 200 nm obtained by polycondensation of molecules with a sol-gel method: Aluminum oxide and phosphoric acid on one surface Polyethylene terephthalate (PET) film (thickness 12 μm) having a gas barrier film containing the reaction product of (Al-OP bond containing layer)
・ ON25: Nylon film (thickness 25μm)
PET12: PET film (thickness 12 μm)
PET30: PET film (thickness 30 μm)
CPP50: unstretched polypropylene film (thickness 50 μm)
・ PBT25: PBT film (thickness 25 μm)
EVOH30: ethylene-vinyl alcohol copolymer film (thickness 30 μm)
LLDPE50: linear short chain branched polyethylene film (thickness 50 μm)
LLDPE30: linear short chain branched polyethylene film (thickness 30 μm)

(Formation method of overcoat layer (B))
The overcoat layer (B) in the thick film Al vapor-deposited PET12 with OC layer (B) and Al ₂ O ₃ vapor-deposited PET12 (B) with OC layer (B) was formed by the following method. First, liquid A (mixed solution composed of polyvinyl alcohol (PVA), isopropyl alcohol and ion-exchanged water) prepared according to the composition shown in Table 2, and liquid B (tetraethyl orthosilicate (TEOS)) prepared in advance according to the composition shown in Table 2 were used. Then, a hydrolyzed solution comprising isopropyl alcohol, hydrochloric acid and ion-exchanged water) was added and stirred, and a colorless and transparent barrier coating composition was obtained by a sol-gel method. Then, on the Al film of the thick Al deposition PET 12, or in _{the Al} 2 _{O 3} film on the _Al 2 _{O 3} deposited PET 12 (B), the barrier coating film composition prepared by the method described above by a gravure coating method Coating is performed, and then heat treatment is performed at 120 ° C., 140 ° C., and 150 ° C. for 20 seconds each to form a barrier coating film, and aging is performed at 55 ° C. for 1 week, and a PVA-TEOS-based overcoat (OC) layer (B ) Was formed.

[Example 1]
(Preparation of outer packaging material for vacuum insulation)
And CPP50 as heat-weldable film, and Al deposited PET12 with OC layer (A) as the first gas barrier film, the OC layer (A) with Al deposited PET12 as the second gas barrier film, SiO ₂ deposited as a third gas barrier film ON15 And were laminated in this order to obtain an outer packaging material. The first gas barrier film and the second gas barrier film are arranged so that the Al film side of the first gas barrier film faces the Al film side of the second gas barrier film, and the SiO ₂ film can be thermally welded to the third gas barrier film. Arranged to face the film side.
Each film was bonded with an adhesive layer. The adhesive for forming the adhesive layer is composed mainly of a polyester polyol as a main component (product name: RU-77T manufactured by Rock Paint) and a curing agent containing an aliphatic polyisocyanate (product name: manufactured by Rock Paint). -7), and a solvent of ethyl acetate was used, and a two-component curable adhesive in which the weight ratio was main agent: curing agent: solvent = 10: 1: 14 was used. 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.

(Preparation of vacuum insulation)
Two outer packaging materials (dimensions: 360 mm × 450 mm) obtained in Example 1 were prepared, two sheets were stacked so that the heat-weldable films face each other, and the three sides of the quadrilateral were heat-sealed, and only one side. A bag with an opening was created. 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]
And EVOH30 as heat-weldable film, and Al deposited PET12 with OC layer (A) as the first gas barrier film, the OC layer (A) with Al deposited PET12 as the second gas barrier film, SiO ₂ deposited as a third gas barrier film ON15 The outer packaging material was obtained in the same manner as in Example 1. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. The arrangement of each film was the same as in Example 1.

[Example 3]
PBT25 as the heat-weldable film, Al-deposited PET12 with OC layer (A) as the first gas barrier film, Al-deposited PET12 with OC layer (A) as the second gas barrier film, and OC layer (A The outer packaging material was obtained in the same manner as in Example 1 using Al vapor-deposited PET12. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. The arrangement of each film was the same as in Example 1.

[Example 4]
PET 30 as heat weldable film, Al vapor-deposited PET12 with OC layer (A) as first gas barrier film, Al vapor-deposited PET12 with OC layer (A) as second gas barrier film, and SiO ₂ vapor-deposited ON15 as third gas barrier film The outer packaging material was obtained in the same manner as in Example 1. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. The arrangement of each film was the same as in Example 1.

[Example 5]
And LLDPE50 as heat-weldable film, and Al deposition EVOH15 as the first gas barrier film, the Al deposited PET12 with OC layer (A) as the second gas barrier film, the SiO ₂ deposition ON15, was used as the third gas barrier film, carried An outer packaging material was obtained in the same manner as in Example 1. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. The arrangement of each film was the same as in Example 1.

[Example 6]
Using LLDPE50 as the heat-weldable film, using thick film Al deposited PET12 as the first gas barrier film, using thick film Al deposited PET12 as the second gas barrier film, and using thick film Al deposited PET12 as the third gas barrier film An outer packaging material was obtained in the same manner as in Example 1. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. The arrangement of each film was the same as in Example 1.

[Example 7]
LLDPE30 is used as the heat-weldable film, thick film Al-deposited PET12 with OC layer (A) is used as the first gas barrier film, and PET12 with Al—O—P bond-containing layer is used as the second gas barrier film. An outer packaging material was obtained in the same manner as in Example 1 using PET12 with an Al—O—P bond-containing layer as the film and SiO ₂ vapor deposition ON15 as the fourth gas barrier film. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. The first gas barrier film is arranged so that the thick film Al film with an OC layer faces the second gas barrier film side with respect to the PET film, and the second gas barrier film has an Al—O—P bond-containing layer with respect to the PET film. The third gas barrier film is arranged so that the Al-OP bond containing layer faces the second gas barrier film side with respect to the PET film, and the fourth gas barrier film is arranged so as to face the first gas barrier film side. The SiO ₂ film was disposed so as to face the third gas barrier film side with respect to the ON film.

[Example 8]
LLDPE30 is used as the heat-weldable film, thick film Al-deposited PET12 with OC layer (A) is used as the first gas barrier film, and PET12 with Al—O—P bond-containing layer is used as the second gas barrier film. Using PET12 with an Al—O—P bond-containing layer as the film and PET12 with an Al—O—P bond-containing layer as the fourth gas barrier film, an outer packaging material was obtained in the same manner as in Example 1. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. The first gas barrier film is arranged so that the thick film Al film with an OC layer faces the second gas barrier film side with respect to the PET film, and the second gas barrier film has an Al—O—P bond-containing layer with respect to the PET film. And arranged to face the first gas barrier film side. The third gas barrier film is arranged such that the Al—O—P bond-containing layer faces the second gas barrier film with respect to the PET film, and the fourth gas barrier film has the Al—O—P bond-containing layer made of PET. It arrange | positioned so that it might face the 3rd gas barrier film side with respect to a film.

[Example 9]
LLDPE30 is used as a heat-weldable film, Al-deposited PET12 with an OC layer (A) is used as a first gas barrier film, PET12 with an Al—O—P bond-containing layer is used as a second gas barrier film, and a third gas barrier film is used. An outer packaging material was obtained in the same manner as in Example 1 using PET 12 with an Al—O—P bond-containing layer and using PET 12 with an Al—O—P bond-containing layer as the fourth gas barrier film. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. The first gas barrier film is arranged so that the Al film with an OC layer faces the second gas barrier film side with respect to the PET film, and the second gas barrier film has an Al—O—P bond-containing layer with respect to the PET film. 1 Arranged to face the gas barrier film side. The third gas barrier film is arranged such that the Al—O—P bond-containing layer faces the second gas barrier film with respect to the PET film, and the fourth gas barrier film has the Al—O—P bond-containing layer made of PET. It arrange | positioned so that it might face the 3rd gas barrier film side with respect to a film.

[Example 10]
LLDPE30 is used as the heat-weldable film, thick film Al-deposited PET12 with OC layer (A) is used as the first gas barrier film, thick film Al-deposited PET12 with OC layer (A) is used as the second gas barrier film, and third film An outer packaging material was obtained in the same manner as in Example 1 using Al ₂ O ₃ vapor-deposited PET12 (A) as the gas barrier film and PET 12 with an Al—O—P bond-containing layer as the fourth gas barrier film. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. The first gas barrier film is arranged so that the thick film Al film with OC layer faces the second gas barrier film side with respect to the PET film, and the second gas barrier film has the thick film Al film with OC layer with respect to the PET film. It arrange | positioned so that it might face the 1st gas barrier film side. The third gas barrier film is arranged so that the Al ₂ O ₃ film faces the second gas barrier film side with respect to the PET film, and the fourth gas barrier film has an Al—O—P bond-containing layer with respect to the PET film. And arranged to face the third gas barrier film side.

[Comparative Example 1]
Using LLDPE50 as a heat-weldable film, Al-deposited EVOH12 as a first gas barrier film, Al-deposited PET12 as a second gas barrier film, and ON25 as a protective film, an outer packaging material was obtained in the same manner as in Example 1. . The first gas barrier film and the second gas barrier film were disposed so that the Al film side of the first gas barrier film and the Al film side of the second gas barrier film face each other. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1.

[Comparative Example 2]
And CPP50 as heat-weldable film, a SiO ₂ deposition PET 12, the SiO ₂ deposition PET 12 as the second gas barrier film, the SiO ₂ deposition PET 12 as the third gas barrier film, was used as the first gas barrier film, as in Example 1 Thus, an outer packaging material was obtained. The first gas barrier film and the second gas barrier film, a SiO ₂ film side of the first gas barrier film and the SiO ₂ film of the second gas barrier film was positioned to face. Further, the third gas barrier film was disposed so as to face the film side on which the SiO ₂ film can be thermally welded. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1.

[Comparative Example 3]
And CPP50 as heat-weldable film, and Al deposition EVOH15 as the first gas barrier film, the SiO ₂ deposition PET12 as the second gas barrier film, the SiO ₂ deposition ON15, was used as the third gas barrier film, in the same manner as in Example 1 The outer packaging material was obtained. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. The arrangement of each film was the same as in Comparative Example 2.

[Comparative Example 4]
Example 1 using LLDPE50 as the heat-weldable film, thick film Al-deposited PET12 with OC layer (B) as the first gas barrier film, PET12 as the first protective film, and ON25 as the second protective film An outer packaging material was obtained in the same manner. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. In addition, the 1st gas barrier film was arrange | positioned so that Al film | membrane with OC layer might face the 1st protective film side with respect to PET film.

[Comparative Example 5]
And LLDPE50 as heat-weldable film, and Al deposition EVOH12 as the first gas barrier film, the OC layer (B) with _Al 2 _{O 3} deposited PET 12 (B) as the second gas barrier film, ON25 and as a first protective film, the The outer packaging material was obtained in the same manner as in Example 1. Moreover, the vacuum heat insulating material was obtained by the same method as Example 1. The first gas barrier film is arranged so that the Al film faces the second gas barrier side with respect to the EVOH film, and the second gas barrier film is such that the Al ₂ O ₃ film with an OC layer is on the first gas barrier film side with respect to the PET film. Arranged to face.

  Table 3 shows the configuration of the outer packaging material of each example and comparative example. “/” In Table 3 indicates a lamination interface of each member constituting the outer packaging material via an adhesive layer.

[Evaluation]
1. Ratio of tensile storage modulus value at 100 ° C. to tensile storage modulus value at 0 ° C. of the outer packaging material for vacuum heat insulating material 0 ° C. of each outer packaging material obtained in Examples 1-10 and Comparative Examples 1-5 The ratio of the tensile storage elastic modulus value at 100 ° C. to the tensile storage elastic modulus value in was calculated according to the conditions and method described in the above section “A. Outer packaging material for vacuum heat insulating material”. The number N of test specimens sampled from each outer packaging material was N = 3, and a 16-point measurement sample was collected from each test specimen by the method described in the section “A. Outer packaging material for vacuum heat insulating material”. The tensile storage modulus value at each temperature of 0 ° C. and 100 ° C. of the outer packaging material is calculated by calculating the average of 16 points of the tensile storage modulus value at each temperature of 0 ° C. and 100 ° C. for each test piece. The value was averaged by a number (N = 3). The details of the measurement method of the tensile storage modulus at each temperature of 0 ° C. and 100 ° C. of the measurement sample are as described in the above section “A. Outer packaging material for vacuum heat insulating material”. The results are shown in Table 4.

2. Measurement of ash content of outer packaging material for vacuum heat insulating material For each outer packaging material obtained in Examples 1 to 10 and Comparative Examples 1 to 5, ash content was determined by the method described in the above section "A. Outer packaging material for vacuum heat insulating material". It was measured. The results are shown in Table 4 below.

3. Deterioration amount of oxygen permeability of outer packaging material for vacuum heat insulating material before and after high-temperature storage The oxygen permeability of each outer packaging material obtained in Examples 1 to 10 and Comparative Examples 1 to 5 was determined in accordance with “A. Vacuum insulating material”. Measured according to the conditions and methods described in the section “Outer packaging material”, and set as “initial value”. Moreover, after each vacuum heat insulating material obtained in Examples 1-10 and Comparative Examples 1-5 was stored in a thermostatic chamber (temperature 100 ° C., humidity-free atmosphere) for 500 hours, each vacuum heat insulating material was thermally welded. The outer packaging material of the uncut portion was cut out, and the oxygen permeability of the outer packaging material of the cut-out portion was measured by the conditions and methods described in the above section “A. Outer packaging material for vacuum heat insulating material”.
For each outer packaging material, the difference in oxygen permeability before and after high-temperature storage was calculated and used as the amount of deterioration with time. The results are shown in Table 4.

4). Vapor permeability and oxygen permeability after bending treatment About each of the outer packaging materials obtained in Examples 1 to 10 and Comparative Examples 1 to 5, rectangular test pieces (width of 210 mm × length of 297 mm (A4 size)) (number of test pieces) N = 1) were collected respectively. In accordance with ASTM F392, each test piece was bent three times using a gelbo flex tester (manufactured by Tester Sangyo Co., Ltd., model name: BE1006). With respect to each test piece after the third bending treatment, the water vapor transmission rate and the oxygen transmission rate were measured by the method and conditions described in the above section “A. Outer packaging material for vacuum heat insulating material”. The results are shown in Table 4.

5. Measurement of thermal conductivity About each vacuum heat insulating material obtained in Examples 1 to 10 and Comparative Examples 1 to 5, the thermal conductivity was measured by the method and conditions described in the above section "B. Vacuum heat insulating material". “Initial value”. For each vacuum insulation, the thermal conductivity after storage for 500 hours in a temperature-controlled room (temperature 100 ° C., humidity-free atmosphere) was measured by the same method and conditions as the initial value, and “after 500 hours storage” Value ”. Furthermore, the value obtained by dividing the value after storage for 500 hours by the initial value was defined as the amount of change. The results are shown in Table 4 below.

[Discussion]
In Examples 1 to 10, the ash content (characteristic 1) of the outer packaging material is within a predetermined range, and the ratio of the tensile storage elastic modulus value at 100 ° C. to the tensile storage elastic modulus value at 0 ° C. (characteristic 2) is It was within the prescribed range. The vacuum heat insulating materials of Examples 1 to 10 were shown to retain high heat insulating performance for a long period of time because the amount of deterioration with time of oxygen permeability was small and the amount of change in thermal conductivity was small before and after high temperature storage. . In particular, when Examples 1 to 10 are compared with Comparative Examples 1, 2, 4, and 5 in which the characteristic 1 does not reach the lower limit, the amount of change in thermal conductivity is increased by setting the ash content of the outer packaging material to 1% by mass or more. Was confirmed to be small. On the other hand, when Examples 1 to 10 and Comparative Example 3 in which the characteristic 2 was not achieved were provided, it was confirmed that the deterioration of the oxygen permeability with time before and after high-temperature storage was small by having the characteristic 2.

  Among the examples, Examples 3 and 6 suggest that the value of the characteristic 2 is higher and the dimensional stability is higher than the other examples. This is because, in the outer packaging materials of Examples 3 and 6, the PET film, which is the resin base material of the third gas barrier film, is the outermost outer packaging material, so it is compared with other examples in which the nylon film is the outermost layer. Thus, it is assumed that the deterioration is small even when exposed to a high temperature environment.

  Further, even in the case of using a gas barrier film having an overcoat layer from Comparative Examples 4 and 5, if both the characteristic 1 and the characteristic 2 are not within the predetermined range in the entire outer packaging material, It was shown that high heat insulation performance cannot be maintained.

  From Table 4, since there is no correlation between the amount of deterioration of oxygen permeability with time before and after storage at high temperature and the amount of deterioration of oxygen permeability with time before and after the bending treatment test, shear due to thermal expansion and contraction of the outer packaging material It was suggested that there is no correlation between the decrease in gas barrier performance due to stress and the decrease in gas barrier performance due to external mechanical stress.

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

Claims (5)

Having at least a heat-weldable film and a gas barrier film,
The gas barrier film is an outer packaging material for a vacuum heat insulating material having a resin base material and a gas barrier film that is disposed on one or both surfaces of the resin base material and contains an inorganic substance,
The storage elastic modulus at 0 ° C. when the ash content is 1.0% by mass or more and 5.0% by mass or less and the storage elastic modulus is measured at a frequency of 10 Hz by a tensile method using a dynamic viscoelasticity measuring device. The outer packaging material for a vacuum heat insulating material, wherein the ratio of the value of the storage elastic modulus at 100 ° C. to the value of 20% is 20% or more. The gas barrier film has the gas barrier film on one side of the resin substrate;
The outer packaging material for vacuum heat insulating materials according to claim 1, wherein the outer packaging material for vacuum heat insulating materials has three or more gas barrier films.   The outer packaging material for a vacuum heat insulating material according to claim 1 or 2, wherein at least the resin base material does not contain an ethylene-vinyl alcohol copolymer resin. A vacuum heat insulating material having a core material and a vacuum heat insulating material encapsulating the core material,
The vacuum heat insulating material, wherein the vacuum heat insulating material outer packaging material is the vacuum heat insulating material outer packaging material according to any one of claims 1 to 3. 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 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 3.