JP2019027444A - External packaging material for vacuum heat insulation material, vacuum heat insulation material and article with vacuum heat insulation material - Google Patents

Abstract

To provide an external packaging material for a vacuum heat insulation material that is hardly damaged by contact with a core material when forming a vacuum heat insulation material, and to provide a vacuum heat insulation material using the same and an article with a vacuum heat insulation material.SOLUTION: An external packaging material 10 for a vacuum heat insulation material includes at least a thermally weldable film 1 and a gas barrier layer 2. The thermally weldable film 1 is a polypropylene film. In the external packaging material 10, a surface on an opposite side to the gas barrier layer 2 of the thermally weldable film 1 has a kinetic friction coefficient of 0.5 or less and an indentation elastic modulus of 1.0 GPa or more.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to an outer packaging material for a vacuum heat insulating material used for forming 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 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 forms a bag body by joining gas barrier properties to suppress the permeation of gas such as oxygen and water vapor, and end parts in order to maintain the vacuum state inside the vacuum heat insulating material for a long period of time. Further, physical properties such as heat-welding property for sealing and sealing the core material are required. In order to satisfy these physical properties, a laminate including a gas barrier layer and a heat-weldable film as constituent members is generally used as the outer packaging material (Patent Documents 1 to 4).

  A polyethylene (PE) film is mainly used as a heat-weldable film for the outer packaging material because it is easy to heat-seal. However, since the PE film has low heat resistance and is likely to be thermally deteriorated, the outer packaging material in which the heat-weldable film is a PE film is not suitable for forming a vacuum heat insulating material intended for long-term use in a high-temperature environment. On the other hand, a polypropylene (PP) film has higher heat resistance than polyethylene and is relatively easy to heat weld. For this reason, the outer packaging material in which the heat-weldable film is a PP film can be suitably used for forming a vacuum heat insulating material assuming long-term use in a high-temperature environment.

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

  By the way, as illustrated in FIGS. 4A to 4D, the core material 11 is inserted into the bag formed by joining the end portions 12 of the two outer packaging materials 10, and the inside is decompressed A. When the rear opening is sealed to form the vacuum heat insulating material 20, the thermally weldable film and the core material come into contact and rub, the core material is pierced into the thermally weldable film and a pinhole is generated. It may be damaged by such as. When the outer packaging material that constitutes the vacuum heat insulating material is damaged, gas enters from the damaged portion, and the vacuum state inside the vacuum heat insulating material is impaired. Therefore, it is difficult for the vacuum heat insulating material to exhibit the heat insulating performance for a long time.

  The present disclosure mainly provides an outer packaging material for a vacuum heat insulating material that is not easily damaged by contact with a core material when forming a vacuum heat insulating material, a vacuum heat insulating material using the same, and an article with a vacuum heat insulating material. Objective.

  The present disclosure is an outer packaging material for a vacuum heat insulating material having at least a heat-weldable film and a gas barrier layer, wherein the heat-weldable film is a polypropylene film, and the gas barrier layer of the heat-weldable film is Provided is an outer packaging material for a vacuum heat insulating material, in which the dynamic friction coefficient of the opposite surface is 0.5 or less and the indentation elastic modulus is 1.0 GPa or more.

  Moreover, this indication is a vacuum heat insulating material which has a core material and the outer packaging material with which the said core material was enclosed, Comprising: The said outer packaging material provides the vacuum heat insulating material which is the outer packaging material for vacuum heat insulating materials mentioned above. .

  Further, the present disclosure is an article having a heat insulating region and an article with a vacuum heat insulating material including a vacuum heat insulating material, the vacuum heat insulating material having a core material and an outer packaging material in which the core material is enclosed. And the articles | goods with a vacuum heat insulating material whose said outer packaging material is the outer packaging material for vacuum heat insulating materials mentioned above are provided.

  According to this indication, when forming a vacuum heat insulating material, the envelope material for vacuum heat insulating materials which cannot be easily damaged by contact with a core material can be provided.

It is a schematic sectional drawing which shows an example of the outer packaging material for vacuum heat insulating materials of this indication. It is the schematic perspective view and sectional drawing which show an example of the vacuum heat insulating material of this indication. It is a graph which shows the time-dependent change of the heat conductivity of the vacuum heat insulating material obtained in Examples 1 and 5 and Comparative Examples 1-2. It is process drawing which shows an example of the manufacturing method of a vacuum heat insulating material.

  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 explanation, the drawings may be schematically represented with respect to the width, thickness, shape, and the like of each part as compared to the embodiment, but are merely examples and limit the interpretation of the present disclosure. Not what you want. In addition, in the present specification and each drawing, elements similar to those described above with reference to the previous drawings are denoted by the same reference numerals, and detailed description may be omitted as appropriate. 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.

I. The outer packaging material for vacuum heat insulating material The outer packaging material for vacuum heat insulating material of the present disclosure is an outer packaging material for vacuum heat insulating material having at least a heat-weldable film and a gas barrier layer, and the heat-weldable film is polypropylene (PP) The dynamic friction coefficient of the surface opposite to the gas barrier layer of the heat-weldable film is 0.5 or less, and the indentation elastic modulus is 1.0 GPa or more.

  FIG. 1 is a schematic cross-sectional view illustrating an example of an outer packaging material for a vacuum heat insulating material according to the present disclosure. The outer packaging material 10 of the present disclosure includes a heat-weldable film 1 and a gas barrier layer 2. The gas barrier layer 2 in FIG. 1 is a gas barrier film having a resin base material 3 and a gas barrier film 4 disposed on at least one surface side of the resin base material 3. The heat-weldable film 1 is a PP film, the dynamic friction coefficient of the surface opposite to the gas barrier layer 2 is within a predetermined range, and the indentation elastic modulus is within a predetermined range.

  According to the outer packaging material for a vacuum heat insulating material of the present disclosure, the dynamic friction of the surface opposite to the gas barrier layer of the PP film used as a heat-weldable film, that is, the surface in contact with the core material when forming the vacuum heat insulating material. When the coefficient is within the predetermined range, when the core material is inserted into the bag body of the outer packaging material, the slipping property between the outer packaging material and the core material becomes good, and the outer packaging material is damaged by rubbing. Can be suppressed. In addition, the indentation elastic modulus of the PP film used as a heat-weldable film is within a predetermined range, so that even if the core material pierces the heat-weldable film, pinholes are unlikely to occur and damage is suppressed. Can do. Thus, the outer packaging material for a vacuum heat insulating material according to the present disclosure is such that the PP film, which is a heat-weldable film, has a predetermined dynamic friction coefficient on the surface opposite to the gas barrier layer, and the PP film has a predetermined By having indentation elastic modulus, the damage by contact with the core material at the time of forming a vacuum heat insulating material can be prevented, and the heat insulation performance of the obtained vacuum heat insulating material can be prevented from being lowered.

  Hereinafter, the configuration and characteristics of the vacuum insulation outer packaging material of the present disclosure will be described in detail.

A. Heat-weldable film The heat-weldable film in the outer packaging material of the present disclosure is a PP film, and the dynamic friction coefficient of the surface opposite to the gas barrier layer of the heat-weldable film is 0.5 or less, The indentation elastic modulus is 1.0 GPa or more. Since the outer packaging material of the present disclosure has one or more gas barrier layers laminated on one side of the heat-weldable film, the gas barrier layer is opposite to the surface opposite to the gas barrier layer of the heat-weldable film. It is a surface that is not laminated, that is, one outermost surface in the thickness direction of the outer packaging material.

1. Characteristics The heat-weldable film in the outer packaging material of the present disclosure has a dynamic friction coefficient on a surface opposite to the gas barrier layer within a predetermined range, and an indentation elastic modulus within a predetermined range.

(1) Coefficient of dynamic friction The heat-weldable film in the outer packaging material of the present disclosure has a coefficient of dynamic friction on the surface opposite to the gas barrier layer of 0.5 or less. Among them, the dynamic friction coefficient can be set to 0.45 or less, particularly 0.4 or less. Further, the dynamic friction coefficient can be set to 0.15 or more, and more preferably to 0.2 or more. When the core material is inserted into the bag body of the outer packaging material by setting the dynamic friction coefficient of the surface of the thermally weldable film opposite to the gas barrier layer within the above range, the outer packaging material and the core material The slipperiness between the core material and the outer packaging material at the time of insertion can be suppressed.

  The dynamic friction coefficient can be measured by a method based on JIS K7125: 1999 (Friction coefficient test method). The method for measuring the dynamic friction coefficient is, for example, using a load-fluctuating friction and wear test system (HEIDON Type HHS2000 manufactured by Shinto Kagaku Co., Ltd.) or a tensile tester (Tensilon Universal Tester “RTC-1250A”). This can be measured under the conditions of a load of 200 g and a speed of 5 mm / sec. The value of the dynamic friction coefficient is measured at five points at different positions on the surface opposite to the gas barrier layer of the heat-weldable film, and is taken as an average value of the measured values.

  In the case of a vacuum heat insulating material using the outer packaging material of the present disclosure, the dynamic friction coefficient of the surface of the heat-weldable film on the side opposite to the gas barrier layer is such that the outer packaging material is not thermally welded in the vacuum heat insulating material. The test piece is sampled to a desired size from the area (for example, the area in contact with the core material), and the above-described measurement method is applied to the surface of the heat-weldable film on the test piece opposite to the gas barrier layer. Can be measured.

(2) Indentation elastic modulus The heat-weldable film in the outer packaging material of the present disclosure has an indentation elastic modulus of 1.0 GPa or more. The indentation elastic modulus can be 10.0 GPa or less, and can be 5.0 GPa or less. By setting the indentation elastic modulus of the heat-weldable film within the above range, even if the core material is pierced into the heat-weldable film, pinholes hardly occur and damage can be suppressed. Moreover, when the outer packaging material for a vacuum heat insulating material is bent, it is possible to prevent the occurrence of cracks due to stress applied to the bent portion.

  The indentation elastic modulus can be measured by using a method of conforming to ISO 14577: 2015 using an ultra micro load hardness tester. The measurement is performed by cutting a sample of a desired size from the outer packaging material and applying a Vickers indenter (a square pyramid diamond with a face angle of 136 ° to the cross section in the thickness direction or the surface opposite to the gas barrier layer of the heat-weldable film. Using an ultra-micro load hardness tester equipped with an indenter), the indentation speed is 0.1 μm / second, the indentation depth is 2 μm, the holding time is 5 seconds, and the drawing speed is 0.1 μm / second. The above measurement is performed under conditions of a temperature of 23 ° C. ± 2 ° C. and a humidity of 60% RH ± 5% RH. As the ultra micro hardness tester, for example, Picodenter HM500 (manufactured by Fisher Instruments) can be used. When measuring the indentation elastic modulus in the cross section of the heat-weldable film, the outer periphery of the sample is fixed with a cured resin and fixed, and the fixed sample is cut in the thickness direction with a diamond knife, and the exposed heat-weldable Measure the cross section of the film. In addition, when measuring the indentation elastic modulus on the surface opposite to the gas barrier layer of the heat weldable film, the outermost surface of the outer packaging material opposite to the heat weldable film is thickened with a cured resin adhesive. It is fixed to a 1.1 mm flat glass plate and the surface of a film that can be heat-welded is measured. The thickness of the layer when calculating the indentation elasticity index can be measured by measurement with an optical microscope of the cut section. Under one condition, in one sample cut out from the outer packaging material, measurement is performed at at least five different points on the surface or cross section opposite to the gas barrier layer of the heat-weldable film, and the average of these measured values is measured. It is set as the value of the indentation elastic modulus of the weldable film under the conditions.

(3) Other characteristics Although the film which can be heat-welded in the outer packaging material of this indication should just have the two characteristics mentioned above, it can further have the following characteristics.

(A) Static friction coefficient The heat-weldable film in the outer packaging material of the present disclosure preferably has a static friction coefficient of 0.15 or more on the surface opposite to the gas barrier layer, and more preferably 0.2 or more. In particular, 0.25 or more. Moreover, the upper limit of the static friction coefficient is not particularly limited, but can be, for example, 0.5 or less. When the core material is inserted into the bag body of the outer packaging material by setting the coefficient of static friction of the surface opposite to the gas barrier layer in the heat-weldable film within the above range, the outer packaging material and the core material The slippage between the core material and the outer packaging material at the time of insertion and the damage due to the core material piercing the outer packaging material can be suppressed.

  The static friction coefficient can be measured by a method based on JIS K7125: 1999 (Friction coefficient test method). The measurement is carried out using a stainless steel hard ball having a diameter of 10 mm using a load-fluctuating friction and wear test system (HEIDON Type HHS2000 manufactured by Shinto Kagaku Co., Ltd.) and a tensile tester (Tensilon universal tester “RTC-1250A”). The static friction coefficient can be measured at a load of 200 g and a speed of 5 mm / sec. The value of the static friction coefficient is measured at five points at different positions on the surface opposite to the gas barrier layer of the heat-weldable film, and is taken as an average value of the measured values.

  In the case of a vacuum heat insulating material using the outer packaging material of the present disclosure, the static friction coefficient of the surface of the heat-weldable film on the side opposite to the gas barrier layer is such that the outer packaging material is not thermally welded in the vacuum heat insulating material. The test piece is sampled to a desired size from the area (for example, the area in contact with the core material), and the above-described measurement method is applied to the surface of the heat-weldable film on the test piece opposite to the gas barrier layer. Can be measured.

2. PP film In the outer packaging material of the present disclosure, the heat-weldable film is a PP film. The PP film is a resin film mainly composed of polypropylene resin. The “main component” means that the proportion of the polypropylene resin in the total mass of the PP film is 90% by mass or more, and preferably 95% by mass or more.

  The polypropylene resin of the PP film may be, for example, a homopolypropylene resin (homo PP) that is a propylene homopolymer, or a random polypropylene resin (random PP) that is a random copolymer of propylene and an α-olefin. It may be a block polypropylene resin (block PP) which is a block copolymer. The PP film may contain one or more of the various polypropylene resins described above. Among these, the PP film is preferably composed mainly of a homopolypropylene resin, that is, the film capable of being thermally welded is preferably a homopolypropylene film, because the above-described characteristics are easily provided and the amount of volatile gas is small.

  The PP film may contain additives such as an antiblocking agent, a lubricant, a flame retardant, and an organic filler in addition to the polypropylene resin. The content of the additive can be, for example, 3% by mass or less with respect to 100% by mass of the total mass of the PP film.

  The PP film may be stretched or non-stretched. Among these, a stretched PP film (CPP film) is preferable from the viewpoint of excellent heat sealability.

  The thickness of the PP film is not particularly limited as long as the desired properties and functions can be exhibited. For example, the thickness can be 20 μm or more and 100 μm or less, particularly 25 μm or more and 90 μm or less, and particularly 30 μm or more and 80 μm or less. can do. When the thickness is larger than the above range, in the vacuum heat insulating material using the outer packaging material of the present disclosure, gas may easily enter from the side surface of the joint end portion, and the degree of vacuum inside the vacuum heat insulating material may be impaired. On the other hand, if the thickness is smaller than the above range, a desired adhesive force may not be obtained at the joint portion.

  The PP film may be subjected to a surface treatment so that the dynamic friction coefficient described above can be provided on the surface opposite to the gas barrier layer. As the surface treatment method, a surface treatment method generally used for surface modification of a resin film can be used, and examples thereof include corona treatment and plasma treatment.

B. Gas Barrier Layer The gas barrier layer in the outer packaging material of the present disclosure is disposed on one surface side of a heat-weldable film. The gas barrier layer is not particularly limited as long as it is a layer capable of exhibiting gas barrier performance. For example, a gas barrier film having a metal foil, a resin base material, and a gas barrier film disposed on one surface side of the resin base material may be used. Can be mentioned. The gas barrier film may be a thin film that can exhibit gas barrier properties, and examples thereof include a metal thin film, an inorganic compound film, and an organic-inorganic hybrid film. As the metal foil and the resin base material and gas barrier film in the gas barrier film, known ones can be used.

C. Protective film The outer packaging material of this indication can have a protective film other than the heat-weldable film and gas barrier layer mentioned above. The protective film may have a gas barrier layer located farthest from the heat-weldable film on the side opposite to the heat-weldable film, and in the thickness direction (lamination direction) of the outer packaging material of the present disclosure , It can be a layer that bears the outermost surface opposite to the heat-weldable film. Thereby, the structural member of outer packaging materials other than a protective film can be protected from damage and deterioration. As the protective film, a general-purpose resin film can be used, and among them, a resin film having a higher melting point than a heat-weldable film can be used.

D. Adhesive Layer The outer packaging material of the present disclosure can have an adhesive layer between members constituting the outer packaging material. Examples of the members constituting the outer packaging material include, for example, between a heat-weldable film and a gas barrier layer, between a gas barrier layer and another gas barrier layer adjacent thereto, and between a gas barrier layer and a protective film. It is done. The adhesive layer can be formed using a known adhesive used for lamination. Although it does not specifically limit as said adhesive agent, For example, a pressure sensitive adhesive, a thermoplastic adhesive, a curable adhesive etc. are mentioned.

E. Others The outer packaging material of the present disclosure has one or more gas barrier layers on one side of a heat-weldable film, and the number of gas barrier layers (the number of stacked layers) as long as the above-described characteristics can be achieved. Is not particularly limited, and can be set as appropriate according to the type and specification of the gas barrier layer.

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

Outer cover material of the present disclosure, the lower the water vapor permeability preferably, for example, preferably water vapor permeability is 0.1g ^/ (m 2 · day) or less, preferably 0.05g ^/ (m 2 · day) or less, In particular, it can be 0.01 g / (m ² · day) or less.

The water vapor transmission rate can be measured using a water vapor transmission rate 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. The measurement is carried out by measuring the outermost layer on the opposite side to the heat-weldable film that is one of the outermost layers facing the thickness direction of the outer packaging material cut to a desired size. Mounted between the upper chamber and lower chamber of the apparatus so as to be on the humidity side (water vapor supply side), with a permeation area of about 50 cm ² (permeation region: a circle with a diameter of 8 cm), a temperature of 40 ° C., a relative humidity The difference is 90% RH. As the water vapor transmission rate measuring apparatus, for example, “DELTAPERM” manufactured by Technolox, UK can be used. The measurement of water vapor permeability is performed on at least three samples under one condition, and the average of the measured values is taken as the value of water vapor permeability under that condition.

The outer packaging material of the present disclosure is preferably as the oxygen permeability is low. For example, the oxygen permeability is preferably 0.1 cc / (m ² · day · atm) or less, and in particular, 0.05 cc / (m ² · day · atm) or less.

For oxygen permeability, refer 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) Using an oxygen gas permeability measuring device, it can be measured under conditions of a temperature of 23 ° C. and a humidity of 60% RH. As the oxygen gas permeability measuring device, for example, “OXTRAN” manufactured by MOCON of the United States can be used. The measurement is carried out by measuring the outermost layer on the opposite side of the outermost layer, which is one of the outermost layers facing the thickness direction, of the outer packaging material that is cut to a desired size. Mounted in the apparatus so as to be in contact with the gas, and measured with a permeation area of about 50 cm ² (permeation region: circular with a diameter of 8 cm) under conditions of a carrier gas and a test gas at a temperature of 23 ° C. and a humidity of 60% RH. Do. During the measurement, 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 measurement is performed after 12 hours have been secured as the time from the start of flowing until the equilibrium state is reached. The test gas uses at least 99.5% dry oxygen. The measurement of oxygen permeability is performed for at least three samples under one condition, and the average of those measured values is taken as the value of oxygen permeability under that condition.

  As a manufacturing method of the outer packaging material of this indication, the method of bonding each film manufactured previously through the adhesive layer mentioned above is mentioned, for example. Alternatively, the raw material of each film that has been heat-melted may be sequentially extruded with a T-die or the like and laminated to produce an outer packaging material.

  The outer packaging material of this indication can be used for a vacuum heat insulating material. In the vacuum heat insulating material, the outer packaging material of the present disclosure can be used by being disposed so as to face each other through the core material such that the heat-weldable film is on the core material side.

II. Vacuum heat insulating material The vacuum heat insulating material of the present disclosure is a vacuum heat insulating material having a core material and an outer packaging material that encloses the core material, and the outer packaging material is the above-mentioned “I. External packaging material for vacuum heat insulating material”. It is what was demonstrated by the term.

  2A and 2B are a schematic perspective view and a cross-sectional view taken along the line XX showing an example of the vacuum heat insulating material of the present disclosure. The vacuum heat insulating material 20 illustrated in FIGS. 2A and 2B includes a core material 11 and an outer packaging material 10 that encloses the core material 11, and the outer packaging material 10 is the vacuum heat insulating material described in FIG. It is the outer packaging material 10. The vacuum heat insulating material 20 is a bag body in which two outer packaging materials 10 face each other so that the respective heat-weldable films face each other, and end portions 12 are joined by heat welding. The material 11 is enclosed, and the bag body is depressurized.

  According to the vacuum heat insulating material of the present disclosure, the outer packaging material that encloses the core material is the outer packaging material for vacuum heat insulating material described in the above-mentioned section “I. External packaging material for vacuum heat insulating material”, and the outer packaging material is the core material. It is difficult to break due to contact with the surface, so that good heat insulation performance can be exhibited for a long time.

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

1. Outer packaging material The outer packaging material in the vacuum heat insulating material of the present disclosure is a member that encloses a core material, and is the same as the outer packaging material for vacuum heat insulating material described in the above-mentioned section “I. Outer packaging material for vacuum heat insulating material”. Explanation here is omitted.

2. Core material The core material in the vacuum heat insulating material of this indication is a member enclosed with an outer packaging material. The term “enclosed” refers to sealing inside a bag formed using an outer packaging material.

  The said core material should just be a material with low heat conductivity, for example, a granular material, foamed resin, a fiber, etc. are mentioned. The core material may be formed of one of the materials described above, or may be a composite material formed by mixing two or more materials. The core material may be made of an inorganic material, may be made of an organic material, or may be a mixture of an organic material and an inorganic material.

  The core material may be a non-molded body in which materials such as powder, foamed resin, and fiber are directly enclosed in a bag body of an outer packaging material, and materials such as powder, foamed resin, and fiber are desired. It may be a molded body formed into a shape. Among these, the core material is preferably a molded body, and particularly preferably a sheet shape among the molded bodies. Sheet-like core material is easy to handle, but when inserted into a bag formed using outer packaging material, it has a large contact area with the surface of the outer packaging material that can be heat-welded and can be heat-welded Damage is likely to occur due to contact between a thin film and a core material. For this reason, the slip property between the heat-weldable film is particularly required, and the effect of using the vacuum insulation material outer packaging material described in the section “I. Vacuum insulation material outer packaging material” is more exhibited. Because.

  The sheet-like core material refers to a molded body obtained by molding the above-described material into a sheet shape. For example, a fiber sheet in which fibers are entangled, a foamed sheet formed by foaming a foamed resin, and a powdered body are hot-press molded. The granular material sheet | seat etc. which were formed in this way are mentioned. Among these, a fiber sheet is preferable. This is because the thermal conductivity of the vacuum heat insulating material can be lowered. About the thickness per sheet-like core material, it can set suitably according to the heat insulation performance of a vacuum heat insulating material, or the number of lamination | stacking of a sheet-like core material.

  The vacuum heat insulating material of the present disclosure only needs to contain one or more sheet-shaped core materials, and the number of sheet-shaped core materials in the vacuum heat insulating material may be one or two or more. . When there are two or more sheet-shaped core materials, the vacuum heat insulating material of the present disclosure can enclose a laminate in which the two or more sheet-shaped core materials are stacked, and the two or more sheet-shaped core materials can be encapsulated. The number of laminated layers made of the core material can be appropriately set according to the heat insulating performance required for the vacuum heat insulating material and the thickness per sheet-shaped core material.

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 is preferably 5 mW / (mK) 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 thermal conductivity is more preferably 4 mW / (mK) or less, and further preferably 3 mW / (mK) 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 (product name: HC-074, manufactured by Eihiro Seiki Co., Ltd.) can be used. The measurement is performed under the following conditions so that both main surfaces of the measurement sample (vacuum heat insulating material) 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 The manufacturing method of the vacuum heat insulating material of this indication can use the manufacturing method of a general vacuum heat insulating material. For example, two outer packaging materials for vacuum heat insulating material described in the section of “I. Vacuum insulating material outer packaging material” described above are prepared, the respective heat-weldable films are faced to each other, and the outer edges of the three sides are overlapped. The bag body which heat-welds and opens one side is obtained. 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.

III. Article with vacuum heat insulating material Article with vacuum heat insulating material of the present disclosure is an article with 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 enclosed The outer packaging material is the one described in the above-mentioned section “I. Outer packaging material for vacuum heat insulating material”.

  According to the article with a vacuum heat insulating material of the present disclosure, the outer packaging material constituting the vacuum heat insulating material used for the article is the outer packaging material for vacuum heat insulating material described in the section of “I. The vacuum heat insulating material can exhibit good heat insulating performance for a long period of time because the outer packaging material is not easily damaged by contact with the core material. By providing the article with such a vacuum heat insulating material, it is possible to achieve energy saving of the article used in the article or article that becomes a high-temperature and high-humidity environment.

  Since the vacuum heat insulating material and the outer packaging material used in the present disclosure have been described in detail in the above-mentioned sections of “II. Vacuum heat insulating material” and “I. Vacuum heat insulating material outer packaging material”, description thereof is omitted here. To do.

  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.

  The present invention will be described more specifically with reference to the following examples and comparative examples.

[Preparation]
The detail of each member used in Examples 1-5 and Comparative Examples 1-2 is as follows.
-Film A that can be heat-welded: Unstretched PP film (thickness: 50 μm, product name: SC, manufactured by Mitsui Chemicals, Inc.)
-Film B that can be heat-welded: Unstretched PP film (thickness: 50 μm, product name: P1128, manufactured by Toyobo Co., Ltd.)
Heat-weldable film C: Unstretched PP film (thickness: 50 μm, product name: P1111, manufactured by Toyobo Co., Ltd.)
Heat-weldable film D: Unstretched PP film (thickness: 50 μm, product name: GLC, manufactured by Mitsui Chemicals, Inc.)
-Film E that can be heat-welded: Unstretched PP film (thickness: 50 μm, product name: Treffan 3301, manufactured by Toray Film Processing Co., Ltd.)
Heat-weldable film F: Unstretched PP film (thickness: 50 μm, product name: Treffan 3951, manufactured by Toray Film Processing Co., Ltd.)
Heat-weldable film G: Unstretched PP film (thickness: 50 μm, product name: RXC-22, manufactured by Mitsui Chemicals, Inc.)
Gas barrier layer A: aluminum foil (thickness 6 μm, product name: 8021, manufactured by UACJ Foil Company)
Protective film A: Nylon film (thickness: 25 μm, product name: Emblem ONBC, manufactured by Unitika)
Protective film B: PET film (thickness: 12 μm, product name: Emblet PTMB, manufactured by Unitika)
Adhesive A: A main component mainly composed of polyester, a curing agent containing an aliphatic polyisocyanate, and ethyl acetate are mixed so that the weight ratio is main agent: curing agent: ethyl acetate = 10: 1: 10. Two-part curable adhesive

[Example 1]
A heat-weldable film A, a gas barrier layer A, a protective film A, and a protective film B were laminated in this order to obtain an outer packaging material. Adhesive A is applied between two adjacent members using a die coater so that the coating amount is 3.5 g / m ² on the surface of one member on the outer packaging material on the side of the heat-weldable film. It dried and formed the contact bonding layer, and laminated | stacked by laminating the other member.

(Preparation of vacuum insulation)
Two sheets of the obtained outer packaging material were stacked and heat sealed in the three directions of the rectangle to create a bag body opened in only one direction. 300 mm × 300 mm × 30 mm glass wool was used as the core material, and after drying, the core material was housed in the bag body and the bag body was evacuated. Then, the opening part of the said bag body was sealed by heat sealing, and the vacuum heat insulating material was obtained. The ultimate pressure was 0.05 Pa.

[Example 2]
An outer packaging material was prepared in the same manner as in Example 1 except that a thermally weldable film B was used in place of the thermally weldable film A, and the obtained outer packaging material was used in the same manner as in Example 1. A vacuum heat insulating material was prepared.

[Example 3]
An outer packaging material was prepared in the same manner as in Example 1 except that a thermally weldable film C was used in place of the thermally weldable film A, and the obtained outer packaging material was used in the same manner as in Example 1. A vacuum heat insulating material was prepared.

[Example 4]
An outer packaging material was prepared in the same manner as in Example 1 except that a thermally weldable film D was used in place of the thermally weldable film A, and the obtained outer packaging material was used in the same manner as in Example 1. A vacuum heat insulating material was prepared.

[Example 5]
An outer packaging material was prepared in the same manner as in Example 1 except that a thermally weldable film E was used in place of the thermally weldable film A, and the obtained outer packaging material was used in the same manner as in Example 1. A vacuum heat insulating material was prepared.

[Comparative Example 1]
An outer packaging material was prepared in the same manner as in Example 1 except that the thermally weldable film F was used in place of the thermally weldable film A, and the obtained outer packaging material was used in the same manner as in Example 1. A vacuum heat insulating material was prepared.

[Comparative Example 2]
An outer packaging material was prepared in the same manner as in Example 1 except that a thermally weldable film G was used in place of the thermally weldable film A, and the obtained outer packaging material was used in the same manner as in Example 1. A vacuum heat insulating material was prepared.

[Evaluation 1: Measurement of friction coefficient]
About the outer packaging material obtained in Examples 1-5 and Comparative Examples 1-2, the dynamic friction coefficient and static friction coefficient of the surface on the opposite side to the gas barrier layer of the film which can be heat-welded were measured. The dynamic friction coefficient and the static friction coefficient were measured using a load-variable friction and wear test system (HEIDON Type HHS2000, manufactured by Shinto Kagaku Co., Ltd.) in accordance with JIS K7125: 1999 (friction coefficient test method). The measurement was carried out using a 10 mm stainless hard sphere under the conditions of a load of 200 g and a speed of 5 mm / sec. The values of the dynamic friction coefficient and the static friction coefficient were measured at five points at different positions on the surface opposite to the gas barrier layer of the heat-weldable film, and the average value of the measured values was used. The results are shown in Table 1.

[Evaluation 2: Measurement of indentation elastic modulus]
About the outer packaging material obtained in Examples 1-5 and Comparative Examples 1-2, the indentation elastic modulus of the heat-weldable film was measured. The indentation elastic modulus is a film that can be heat-welded by cutting out a sample from the outer packaging material with an ultra-micro load hardness tester / Picodenter HM500 (manufactured by Fischer Instruments Co., Ltd.) according to a method based on ISO 14577: 2015. Using a Vickers indenter (a regular quadrangular pyramid diamond indenter with a facing angle of 136 °) against the surface opposite to the gas barrier layer at a temperature of 23 ° C. ± 2 ° C. and a humidity of 60% RH ± 5% RH Five points were measured at different positions under the conditions of 0.1 μm / second, indentation depth of 2 μm, holding time of 5 seconds, and drawing speed of 0.1 μm / second to obtain an average value of the measured values. The results are shown in Table 1.

[Evaluation 3: Measurement of thermal conductivity]
About the vacuum heat insulating material obtained in Examples 1-5 and Comparative Examples 1-2, thermal conductivity (initial stage) was measured according to the method demonstrated in the term of "II. Vacuum heat insulating material." Under one condition, three samples were measured, and the average of the measured values was taken as the value of thermal conductivity. The results are shown in Table 2. Moreover, about the vacuum heat insulating material obtained in Examples 1 and 5 and Comparative Examples 1 and 2, according to the method described in the section of “II. Vacuum heat insulating material”, the temperature is 90 ° C. and the humidity is not controlled for 0 hours. The thermal conductivity was measured over time every 100 hours during the holding process. Under one condition, three samples were measured, and the average of the measured values was taken as the value of thermal conductivity. The results are shown in FIG.

[Discussion]
From the results of evaluation 3, as shown in Table 2, the thermal conductivity (initial) of the vacuum heat insulating materials obtained in Examples 1 to 5 is the thermal conductivity (initial value) of the vacuum heat insulating materials obtained in Comparative Examples 1 and 2. ) Was lower. Moreover, as shown in FIG. 3, the vacuum heat insulating materials obtained in Examples 1 and 5 were compared with the vacuum heat insulating materials obtained in Comparative Examples 1 and 2 in an environment where the temperature was 90 ° C. and humidity was not controlled. An increase in thermal conductivity over time was suppressed, and a result showing low thermal conductivity over the same elapsed time was obtained.

  The vacuum heat insulating materials of Examples 1 to 5 and the vacuum heat insulating materials of Comparative Examples 1 and 2 are films capable of being thermally welded as outer packaging materials constituting the vacuum heat insulating materials. Whereas PP films having respective rates within a predetermined range were used, Comparative Examples 1 and 2 differ in that at least one of a dynamic friction coefficient and an indentation elastic modulus was used within a predetermined range. Therefore, the result of evaluation 3 is presumed to be due to the characteristics of the PP film used as a heat-weldable film. That is, in Examples 1 to 5, the dynamic friction coefficient of the PP film in the outer packaging material is set to 0.5 or less, so that when the core material is inserted into the bag body of the outer packaging material at the time of manufacturing the vacuum heat insulating material, it is rubbed. It is presumed that pinholes are less likely to be generated even if the core material is pierced into the PP film by suppressing the damage of the outer packaging material due to the above, and by setting the indentation elastic modulus of the PP film to 1.0 GPa or more. And in Examples 1-5 in which the dynamic friction coefficient and the indentation elastic modulus of the surface of the heat-weldable film of the outer packaging material are each in a predetermined range, the film and the core material that can be heat-welded at the time of manufacturing the vacuum heat insulating material Since defects due to contact are less likely to occur, it is presumed that invasion of gas from the defective portion at the initial stage and over time is suppressed, and a decrease in the degree of vacuum inside the vacuum heat insulating material can be prevented for a long period of time.

DESCRIPTION OF SYMBOLS 1 ... Film which can be heat-welded 2 ... Gas barrier layer 3 ... Resin base material 4 ... Gas barrier film 10 ... Outer packaging material for vacuum heat insulating materials 11 ... Core material 12 ... End part 20 ... Vacuum heat insulating material

Claims (4)

An outer packaging material for a vacuum heat insulating material having at least a heat-weldable film and a gas barrier layer,
The heat-weldable film is a polypropylene film,
An outer packaging material for a vacuum heat insulating material, wherein a coefficient of dynamic friction on a surface opposite to the gas barrier layer of the heat-weldable film is 0.5 or less and an indentation elastic modulus is 1.0 GPa or more. A vacuum heat insulating material having a core material and an outer packaging material in which the core material is enclosed,
The vacuum heat insulating material whose said outer packaging material is the outer packaging material for vacuum heat insulating materials of Claim 1.   The vacuum heat insulating material according to claim 2, wherein at least one sheet-shaped core material is enclosed. 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 in which the core material is enclosed,
An article with a vacuum heat insulating material, wherein the outer packaging material is the vacuum heat insulating material outer packaging material according to claim 1.