Outer packaging material for vacuum insulation, vacuum insulation material, articles with vacuum insulation material, and barrier film

Abstract

The present invention provides an outer packaging material for vacuum insulation materials that can suppress a decrease in gas barrier properties even when partial stretching or other modifications are performed. [Solution] The present disclosure provides an outer packaging material for vacuum insulation material having a barrier layer containing a resin and an inorganic layered compound, wherein the resin has a lamellar structure having a two-phase structure of a crystalline portion and an amorphous portion, and when the thickness of the crystalline portion in the lamellar structure is taken as 1, the thickness of the amorphous portion is 1.080 or more.

Description

Technical Field

[0001] The present disclosure relates to an outer packaging material for a vacuum insulation material capable of forming a vacuum insulation material, a vacuum insulation material, an article with a vacuum insulation material, and further to a barrier film.

Background Art

[0002] In recent years, for the purpose of energy conservation of articles, vacuum insulation materials have been used. A vacuum insulation material is a member in which a core material is disposed in a bag body of an outer packaging material, and the inside of the bag body is maintained in a vacuum state where the pressure is lower than the atmospheric pressure, and since internal heat convection is suppressed, good heat insulation performance can be exhibited. Hereinafter, the above outer packaging material used for a vacuum insulation material will be described as an outer packaging material for a vacuum insulation material or simply an outer packaging material.

[0003] As such a gas barrier film used for the outer packaging material, for example, a vapor deposition film in which a metal or a metal oxide is vapor-deposited on a base material may be used. However, such a vapor deposition film has a problem that the gas barrier performance deteriorates when it is stretched. Specifically, when the above outer packaging material is made into a vacuum insulation material, it becomes a mode in which the core material is disposed in the packaging bag as described above. In the process of using the packaging bag as a vacuum insulation material, the end portions of the outer packaging material are overlapped and bent to form the end portions of the packaging bag by so-called gusset folding. Further, grooving may be performed when it is used as a vacuum insulation material.

[0004] Since such gusset folding and grooving partially stretch the outer packaging material, when the above-described vapor deposition film is used, there is a problem that the heat insulation property may deteriorate. In order to solve such a problem, for example, as shown in Patent Document 1, a method of suppressing a decrease in gas barrier properties due to stretching by setting the average particle diameter of a metal vapor deposition film to a predetermined value or less has been proposed, but it is only applicable to a metal vapor deposition film and has a problem that it cannot be applied to a vapor deposition film of an inorganic oxide.

[0005] Furthermore, while ethylene vinyl alcohol copolymer resins are sometimes used as gas barrier films that do not employ such vapor-deposited films, they have drawbacks such as potential problems with physical properties like heat resistance and being relatively expensive. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2013 / 125564 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] This disclosure is an invention made in view of the above circumstances, and its main purpose is to provide an outer packaging material for vacuum insulation materials that can suppress a decrease in gas barrier properties even when partial stretching or the like is performed. [Means for solving the problem]

[0008] This disclosure provides an outer packaging material for vacuum insulation material having a barrier layer containing a resin and an inorganic layered compound, wherein the resin has a lamellar structure having a two-phase structure of a crystalline portion and an amorphous portion, and when the thickness of the crystalline portion in the lamellar structure is taken as 1, the thickness of the amorphous portion is 1.080 or more.

[0009] Furthermore, this disclosure provides a vacuum insulation material having a core material and an outer packaging material in which the core material is enclosed, wherein the outer packaging material is the vacuum insulation outer packaging material described above.

[0010] Furthermore, this disclosure provides an article having a thermally insulating region and an article with vacuum insulation, wherein the vacuum insulation comprises a core material and an outer packaging material in which the core material is enclosed, and the outer packaging material is the vacuum insulation outer packaging material described above.

[0011] Furthermore, the present disclosure provides a barrier film having a barrier layer comprising a resin and an inorganic layered compound, wherein the resin has a lamellar structure having a two-phase structure of a crystalline portion and an amorphous portion, and when the thickness of the crystalline portion in the lamellar structure is taken as 1, the thickness of the amorphous portion is 1.080 or more. [Effects of the Invention]

[0012] According to this disclosure, it is possible to provide an outer packaging material for vacuum insulation materials that can suppress a decrease in gas barrier properties even when stretched. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic cross-sectional view showing an example of a barrier layer used in the outer packaging material for vacuum insulation material in this disclosure. [Figure 2] This is a conceptual diagram showing the lamellar structure in the resin used in the barrier layer. [Figure 3] This is a schematic cross-sectional view showing an example of an outer packaging material for vacuum insulation material in this disclosure. [Figure 4] These are schematic perspective views and cross-sectional views illustrating an example of a vacuum insulation material in this disclosure. [Figure 5] These are photographs showing the SEM image and the state after binarization. [Modes for carrying out the invention]

[0014] The present disclosure includes, in embodiments, an outer package material for a vacuum insulation material, a vacuum insulation material, an article with a vacuum insulation material, and a barrier film. Hereinafter, embodiments of the present disclosure will be described with reference to the drawings and the like. However, the present disclosure can be implemented in many different modes and is not construed as being limited to the description of the embodiments exemplified below. Further, for the purpose of making the description clearer, the drawings may schematically represent the width, thickness, shape, etc. of each part as compared with the embodiments, but this is merely an example and does not limit the interpretation of the present disclosure. Also, in this specification and each drawing, elements similar to those described above with respect to the already shown drawings may be denoted by the same reference numerals, and detailed description may be omitted as appropriate. Also, for convenience of explanation, the terms "upper" or "lower" may be used in the description, but the vertical direction may be reversed.

[0015] Also, in this specification, when a certain configuration of a certain member or a certain region or the like is said to be "above (or below)" another configuration of another member or another region or the like, unless there is a special limitation, this includes not only the case where it is directly above (or directly below) the other configuration, but also the case where it is above (or below) the other configuration, that is, the case where another component is included between above (or below) the other configuration.

[0016] Hereinafter, the outer package material for a vacuum insulation material, the vacuum insulation material, the article with a vacuum insulation material, and the barrier film of the present disclosure will be described respectively.

[0017] A. Outer package material for a vacuum insulation material The outer package material for a vacuum insulation material of the present disclosure is an outer package material for a vacuum insulation material having a barrier layer containing a resin and an inorganic layered compound, wherein the resin has a lamellar structure having a two-phase structure of a crystalline part and an amorphous part, and when the thickness of the crystalline part in the lamellar structure is taken as 1, the thickness of the amorphous part is 1.080 or more.

[0018] FIG. 1 is a schematic diagram showing an example of a barrier layer used in the outer package material for a vacuum insulation material of the present disclosure. As shown in FIG. 1, the barrier layer 10 has a resin 1 and an inorganic layered compound 2 dispersed in the resin 1.

[0019] The resin in the present disclosure has a lamellar structure having a two-phase structure of a crystalline part and an amorphous part. When the thickness of the crystalline part in the lamellar structure is taken as 1, the thickness of the amorphous part is 1.080 or more.

[0020] FIG. 2 schematically shows the lamellar structure in the resin. In the resin 1, there are a crystalline part 21 and an amorphous part 22 of the lamellar structure. In the present disclosure, when the thickness L1 of the crystalline part 21 in the lamellar structure is taken as 1, the thickness L2 of the amorphous part 22 is 1.080 or more.

[0021] Generally, the gas permeability of the amorphous part is higher than that of the crystalline part. Therefore, it is considered that the gas permeating through the resin in the barrier layer permeates along the amorphous part. Here, when the outer wrapping material for the vacuum insulation material having the barrier layer is subjected to a process such as pleating and stretched, in the resin, stress is applied to the resin while the shape of the crystalline part with high cohesive force is maintained, so the shape of the amorphous part changes, and for this reason, it is expected that the molecular chains in the amorphous part will be in a distorted state. In the amorphous part in such a distorted state of the molecular chains, a large number of voids between the molecular chains through which gas passes will occur, so it is expected that the gas permeability will increase.

[0022] When the thickness of the amorphous part with respect to the thickness of the crystalline part is large, the molecular chains in the amorphous part can move relatively freely, so the above-described distorted state of the molecular chains does not occur, and the generation of voids can be made relatively small. Therefore, it is possible to suppress the decrease in gas barrier properties due to stretching.

[0023] In the present disclosure, from the above-described points and the results of the examples described later, the resin included in the barrier layer used in the present disclosure has a lamellar structure having a two-phase structure of a crystalline part and an amorphous part. When the thickness of the crystalline part in the lamellar structure is taken as 1, the thickness of the amorphous part being 1.080 or more makes it possible to suppress a decrease in gas barrier properties during stretching of the outer wrapping material for the vacuum insulation material using the barrier layer.

[0024] 1. Barrier layer The barrier layer used in the outer packaging material for vacuum insulation material according to this disclosure comprises a resin and an inorganic layered compound.

[0025] (1) Resin The resin used in the barrier layer has a lamellar structure having a two-phase structure of crystalline and amorphous parts, and when the thickness of the crystalline part in the lamellar structure is taken as 1, the thickness of the amorphous part is 1.080 or more.

[0026] a) Crystalline and amorphous regions i) Thickness ratio The resin used in this disclosure has a thickness of 1.080 or more of the amorphous portion, with the thickness of the crystalline portion being 1, and is particularly preferably 1.085 or more, and more preferably 1.090 or more. This range makes it possible to suppress large strains on the amorphous portion even when the outer packaging material for vacuum insulation is partially stretched, thereby suppressing a decrease in gas barrier properties.

[0027] On the other hand, if the thickness of the crystalline portion is taken as 1, the thickness of the amorphous portion is preferably 1.25 or less, and particularly preferably 1.15 or less. This is because if the ratio of the thickness of the amorphous portion becomes too large, the proportion of the volume of the crystalline portion in the resin will decrease, which may lead to a decrease in the gas barrier properties of the resin.

[0028] One method for changing the thickness ratio of the amorphous portion to the crystalline portion is to change the conditions when forming the barrier layer. Specifically, the thickness ratio of the amorphous portion to the crystalline portion can be changed by controlling the degree of freedom of movement of the polymer constituting the resin during coating.

[0029] For example, by increasing the cooling rate after applying the coating solution for forming the barrier layer, it is possible to increase the thickness of the amorphous portion. When a solvent is used, the thickness of the amorphous portion can be increased by increasing the solid content concentration, increasing the drying speed, or the like. Furthermore, by setting the temperature of the coating solution during coating to a certain extent lower, it is also possible to increase the thickness of the amorphous portion. Specifically, when a solvent is used, the thickness of the amorphous portion can be increased by setting the drying temperature to a certain extent lower.

[0030] Also, in the heat treatment after coating and drying the coating solution for forming the barrier layer, by controlling the degree of freedom of movement of the polymer constituting the resin, the ratio of the thickness of the amorphous portion to the crystalline portion can be changed. For example, by lowering the heat treatment temperature or not performing the heat treatment, the thickness of the amorphous portion can be increased.

[0031] <Measurement method> The measurement of the ratio of the thicknesses of the crystalline portion and the amorphous portion in the present disclosure is obtained by exposing the surface of the resin in the target barrier layer and obtaining an image by a scanning electron microscope (hereinafter sometimes referred to as SEM) of the resin surface, and performing image processing on this.

[0032] <Sample preparation> Procedure 1: In order to expose the surface of the resin in the barrier layer, use a scalpel under a stereomicroscope to peel off other layers such as the adhesive layer laminated on the barrier layer at the interface. Procedure 2: In order to expose the surface of the barrier layer, use a scalpel or the like to remove other layers such as the adhesive layer. Procedure 3: In order to be able to distinguish the amorphous portion and the crystalline portion by staining, leave the sample with the resin exposed under an atmosphere of ruthenium tetroxide vapor for 12 hours for staining. Procedure 4: Cut the sample with the resin surface in the barrier layer exposed into a 5 mm square, attach it to the SEM sample stage attached to the SEM device with carbon tape, and obtain an SEM image of the resin surface of the stained sample.

[0033] <SEM pixel observation conditions> Device: SU9000 manufactured by Hitachi High-Tech Corporation Accelerating voltage: 1.5 kV Emission current: 20 mA Mode: High Detector: HABSE W.D.: 8 mm Magnification: 200k

[0034] <SEM Image Processing Conditions> [Image Processing Conditions] Using ImageJ Fiji, an image analysis freeware developed by the National Institutes of Health (NIH) in the United States, the STEM image is binarized into black and white according to the following procedure and input parameters, with the white part being the low-density part (amorphous part) of the lamellar structure and the black part being the high-density part (crystalline part) of the lamellar structure. The SEM image and the binarized image are shown in Figure 5.

[0035] [Image Processing Procedure] Step 1: Run Despeckle from the Noise menu in the Process menu Step 2: Run BandPassFilter from the FFT menu in the Process menu (set the upper limit of the filter to 30 px and the lower limit to 3 px) Step 3: Run GaussianBlur from the filter menu in the Process menu (set the siguma value to 1 px) Step 4: Run AutoLocalThreshold from the Adjust menu in the Image menu (set Method to Mean, radius to 15 px, and parameter1 and parameter2 to 0) Step 5: Run Despeckle from the Noise menu in the Process menu Step 6. For the white part of the binary image, calculate Local Thickness (Complete Process) in the Analysis menu of ImageJ. For the value of Local Thickness of each pixel where the value of Local Thickness is non-zero, calculate the average value of the entire white part area in the image. For this average value, convert it from the magnification at the time of imaging to nanometers and define it as the average lamellar thickness of the low-density part (amorphous part). Step 7. Similarly, calculate Local Thickness for the black part of the binary image, and for the value of Local Thickness of each pixel where the value of Local Thickness is non-zero, calculate the average value of the entire black part area in the image. For this average value, convert it from the magnification at the time of imaging to nanometers and define it as the average lamellar thickness of the high-density part (crystalline part).

[0036] ii) Thickness variation In the present disclosure, it is preferable that the thickness variation of the above amorphous part is within a predetermined range. This is because the smaller the variation, the better the effect of suppressing the decrease in gas barrier properties during stretching described above. Specifically, the standard deviation of the thickness of the amorphous part is preferably 2 nm or less.

[0037] As a measurement method, in the same manner as the above <Measurement method>, <Sample preparation>, and <SEM pixel observation conditions>, calculate the standard deviation of the entire white part area in the image, and convert it from the magnification at the time of shooting to nanometers and define it as the standard deviation of the low-density part (amorphous part).

[0038] b) Material The resin material used in the present disclosure is not particularly limited as long as it has a lamellar structure having a two-phase structure of a crystalline part and an amorphous part, and the ratio of the thickness of the above crystalline part and amorphous part falls within the above range. Whether the resin has a lamellar structure having a two-phase structure of a crystalline part and an amorphous part is determined by whether a binary image can be obtained when the above SEM image processing is performed.

[0039] Examples of such resin materials include polyethylene such as linear short-chain branched polyethylene (LLDPE) and high-density polyethylene (HDPE), polyolefin resins such as unstretched polypropylene (CPP), polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), polyamide resins such as nylon, polyvinyl alcohol resins and ethylene-vinyl alcohol copolymer (EVOH) resins, polyphenylene sulfide (PPS) resins, and polyether ether ketone (PEEK).

[0040] In this disclosure, hydrophilic resins are particularly preferred. Hydrophilic resins generally have hydrophilic functional groups, and hydrogen bonds are often formed between these hydrophilic functional groups within the resin. In the amorphous portion of the resin, such hydrogen bonds play a role in improving gas barrier properties. However, when such a hydrophilic resin is stretched, strain is applied to the amorphous portion as described above, causing the hydrogen bonds to break and leading to a decrease in gas barrier properties. Therefore, the effect of keeping the thickness of the crystalline portion and the amorphous portion within a predetermined range becomes particularly noticeable when a hydrophilic resin is used as the resin.

[0041] In this disclosure, a hydrophilic resin is defined as a resin having hydrophilic functional groups. Specific examples of such hydrophilic functional groups include hydroxyl groups, carboxyl groups, amino groups, and carbonyl groups.

[0042] Whether or not a substance has hydrophilic functional groups is determined by whether or not functional groups are detected by functional group analysis using XPS with chemical modification.

[0043] In this disclosure, examples of hydrophilic resins used in the above resin include polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), and polysaccharides such as hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, amylose, amylopectin, curdlan, zantan, chitin, cellulose, pullulan, and chitosan. In this disclosure, polyvinyl alcohol is preferred among these.

[0044] (2) Inorganic layered compounds The barrier layer in this disclosure includes an inorganic layered compound. This is because it is possible to improve gas barrier properties through a so-called labyrinth effect.

[0045] Here, an inorganic layered compound refers to an inorganic compound that has a layered structure in which unit crystal layers are stacked on top of each other. In other words, a "layered compound" refers to a compound or substance that has a layered structure. Furthermore, a "layered structure" refers to a structure in which planes in which atoms are strongly bonded together by covalent bonds or the like and densely arranged are stacked in parallel by weak bonding forces such as van der Waals forces.

[0046] Any inorganic layered compound having a layered structure is acceptable, and examples include graphite, phosphate derivative compounds (zirconium phosphate compounds), chalcogenides, and clay minerals. Clay minerals are preferred among these.

[0047] Specifically, clay minerals include phyllosilicate minerals such as hydrated silicates; kaolinite clay minerals such as halloysite, kaolinite, endelite, dickite, and nacrite; antigorite clay minerals such as antigorite and chrysotile; smectite clay minerals such as montmorillonite, iron montmorillonite, beidelite, nontronite, saponite, hectorite, souconite, and stevensite; vermiculite clay minerals such as vermiculite; micas such as muscovite and phlogopite; mica or mica clay minerals such as margalite, tetrasilicic mica, and teniolite; chlorite clay minerals such as cuquerite, sudoite, clinochlore, chamosite, and nimite, or their substitutions and derivatives. These clay minerals may be natural or synthetic, and may be included in combination of two or more types.

[0048] In this disclosure, phyllosilicate minerals and smectite clay minerals are preferred, and montmorillonite and hectorite contained in smectite clay minerals are particularly preferred.

[0049] The average particle size of the inorganic layered compound particles is preferably 50 nm to 5 μm, more preferably 100 nm to 4 μm, and particularly preferably 500 nm to 3 μm. This is because setting the average particle size of the inorganic layered compound particles within the above range improves the oxygen barrier performance of the inorganic layered compound layer. The particle size of the inorganic layered compound particles is defined as the central diameter (major axis) determined by photon correlation using dynamic light scattering, measured with an ultrafine particle size analyzer under conditions of 25°C and aqueous solvent.

[0050] The aspect ratio of the inorganic layered compound is preferably 50 to 5000, more preferably 200 to 3000, and particularly preferably 300 to 2500.

[0051] This is because setting the aspect ratio of the inorganic layered compound within the above range improves the oxygen barrier performance of the inorganic layered compound layer. The aspect ratio of the inorganic layered compound is the ratio of the average interplanar spacing (average unit thickness) to the average particle size of the inorganic layered compound particles, and is calculated using the following formula (1).

[0052] Z = L / a … (1) (In equation (1) above, Z is the aspect ratio, L is the average particle size of the inorganic layered compound, and a is the average interplanar spacing (average unit thickness) of the inorganic layered compound.)

[0053] The average particle size L of the inorganic layered compound shall be the value obtained by the method described above. The interplanar spacing (unit thickness) a of the inorganic layered compound is, for example, a value obtained by powder X-ray diffraction measurement of the inorganic layered compound using an X-ray diffractometer. Furthermore, powder X-ray diffraction measurement of a composition containing the inorganic layered compound and a binder resin can confirm the presence of areas where the interplanar spacing of the inorganic layered compound is widened.

[0054] (3) Others The barrier performance of the barrier layer improves as the volume of the inorganic layered compound increases relative to the resin. Conversely, the flexibility improves as the volume of the resin increases. Therefore, the volume ratio of the inorganic layered compound to the resin (inorganic layered compound / resin) is preferably 5 / 95 to 90 / 10, and more preferably in the range of 5 / 95 to 50 / 50. This is because by setting the volume ratio of the inorganic layered compound to the binder resin within the above range, a barrier layer with excellent barrier performance and flexibility can be obtained.

[0055] Furthermore, the thickness of the barrier layer is preferably 4 μm or less, particularly 2 μm or less, and more preferably 1 μm or less. On the other hand, it is preferably 50 nm or more, particularly 100 nm or more, and more preferably 150 nm or more.

[0056] By setting the thickness of the barrier layer within the above range, it becomes possible to achieve flexibility, excellent bending resistance, and sufficient barrier performance.

[0057] 2. Barrier film The outer packaging material for vacuum insulation materials of this disclosure preferably has a barrier film in which a resin substrate, an inorganic layer, and the barrier layer are laminated in this order. The barrier layer is the same as described in "1. Barrier Layer" above, so its explanation is omitted here.

[0058] (1) Inorganic layer The inorganic layer used in this disclosure is not particularly limited as long as it can exhibit the desired gas barrier properties, and may or may not be transparent. Examples of such gas barrier layers include metal layers and layers mainly composed of inorganic compounds. In this disclosure, layers mainly composed of inorganic compounds are preferred.

[0059] Examples of the above-mentioned metal layer include metal vapor-deposited films composed of metals such as aluminum, stainless steel, titanium, nickel, iron, and copper, or alloys containing these metals.

[0060] Furthermore, the inorganic compound in the layer mainly composed of the above inorganic compound can be any material capable of exhibiting the desired gas barrier properties. Examples include one or more inorganic compounds selected from inorganic oxides, inorganic oxidized nitrides, inorganic nitrides, inorganic oxidized carbides, inorganic oxidized carbidides, and zinc silicon oxide. Specifically, examples include inorganic compounds containing one or more atoms selected from silicon, aluminum, magnesium, calcium, potassium, tin, sodium, titanium, boron, yttrium, zirconium, cerium, and zinc. More specifically, examples include silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, silicon-zinc alloy oxide, indium alloy oxide, silicon nitride, aluminum nitride, titanium nitride, and silicon oxidized nitride. Aluminum oxide (alumina) and silicon oxide (silica) are particularly preferred. The above inorganic compounds may be used individually or mixed in any proportion. In this disclosure, the inorganic layer is preferably aluminum, aluminum oxide, or silicon oxide.

[0061] The inorganic layer may be a vapor-deposited film formed by a vapor deposition method, or a coated film formed by a coating method. Among these, a vapor-deposited film is preferred from the viewpoint of high adhesion to the resin substrate and the ability to exhibit high gas barrier performance. If it is a vapor-deposited film, it may be formed by a single vapor deposition or by multiple vapor depositions. That is, one inorganic layer may be a single film formed by a single vapor deposition, or it may be formed by multiple vapor depositions and have a laminated structure.

[0062] The thickness of the inorganic layer is not particularly limited, but it is preferably in the range of 10 nm to 300 nm. By keeping the thickness of the inorganic layer within this range, barrier properties can be maintained while ensuring sufficient flexibility, making barrier failure less likely.

[0063] (2) Resin base In the vacuum insulation material packaging material of this disclosure, although not particularly limited, the inorganic layer and the barrier layer can usually be provided on one main surface of the resin substrate.

[0064] Suitable resin substrates include, for example, resin films. When the resin substrate is a resin film, the resin film may be unstretched, uniaxially or biaxially stretched, or otherwise. The resin substrate may or may not be transparent.

[0065] The resin used for the resin substrate is not particularly limited, and various resins can be used, such as polyolefin resins like polyethylene and polypropylene, polyester resins like polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), poly(meth)acrylic resins, polycarbonate resins, ethylene-vinyl ester copolymers and their saponifies, polyamide resins such as various types of nylon, polyimide resins, polyurethane resins, acetal resins, and cellulose resins. Among the above resins, PET, PBT, and nylon are more preferably used.

[0066] The above-mentioned resin substrate may contain various plastic compounding agents and additives. Examples of additives include lubricants, crosslinking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins.

[0067] The above resin substrate may be subjected to surface treatment, as this can improve adhesion with the inorganic layer. Examples of such surface treatments include oxidation treatment, surface roughening treatment, and easy-adhesion coating treatment, as disclosed in Japanese Patent Application Publication No. 2014-180837.

[0068] The thickness of the resin substrate is not particularly limited, but is, for example, in the range of 6 μm to 200 μm, more preferably 9 μm to 100 μm (in this specification, the notation A to B indicates a range including A and B). The resin substrate may be a single layer or a multilayer body formed by laminating multiple resin layers. In the above multilayer body, each resin layer may be composed of a different resin or of the same resin.

[0069] (3) Others In the outer packaging material for vacuum insulation material of this disclosure, it is sufficient to have at least one layer of the barrier film, but from the viewpoint of gas barrier properties, it is preferable to have two or three layers.

[0070] Furthermore, in addition to the above-mentioned barrier film, there may also be a second barrier film having at least a resin substrate and an inorganic layer, but without the above-mentioned barrier layer. The resin substrate and inorganic layer of the second barrier film are the same as those of the barrier film, so their explanation is omitted here.

[0071] 3. Heat-sealable film In the vacuum insulation material outer packaging material of this disclosure, a heat-sealable film is typically arranged on one main surface side. Such a heat-sealable film is a film that can be welded by heating. The heat-sealable film is a component that forms one surface in the thickness direction of the vacuum insulation material outer packaging material, and is in contact with the core material when manufacturing a vacuum insulation material using the vacuum insulation material outer packaging material of this disclosure, and is also a component that joins the ends of opposing vacuum insulation material outer packaging materials when sealing the core material.

[0072] As materials for the heat-sealable film described above, thermoplastic resins are preferred because they can be melted and fused by heating. Examples include polyethylene such as linear short-chain branched polyethylene (LLDPE) and high-density polyethylene (HDPE), polyolefin resins such as unstretched polypropylene (CPP), polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT), polyvinyl acetate resins, polyvinyl chloride resins, poly(meth)acrylic resins, urethane resins, polyvinyl alcohol resins and ethylene-vinyl alcohol copolymer (EVOH) resins, polyphenylene sulfide (PPS) resins, and tetrafluoroethylene (C2F4)·ethylene (C2H4) copolymer (ETFE) resins.

[0073] In this disclosure, the resin can be appropriately selected from the above-mentioned resins depending on the set melting point of the heat-sealable film. For example, linear short-chain branched polyethylene (LLDPE) is highly versatile and can be heat-sealed at relatively low temperatures.

[0074] The melting point of the heat-sealable 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. Furthermore, the melting point is preferably 300°C or lower, more preferably 290°C or lower, and more preferably 280°C or lower. By setting the melting point of the heat-sealable film to 145°C or higher, thermal degradation and dimensional changes of the heat-sealable film itself can be suppressed even when the vacuum insulation material outer packaging is exposed to high-temperature environments for extended periods. This suppresses dimensional changes in the entire vacuum insulation material outer packaging caused by dimensional changes in the heat-sealable film. Moreover, the higher the melting point of the heat-sealable film, the more effectively peeling of the sealing surface due to exposure to ambient temperature can be suppressed when the vacuum insulation material outer packaging is used in the manufacture of the vacuum insulation material. Therefore, a vacuum insulation material that can withstand use in higher-temperature environments can be obtained. From this perspective, the melting point of the heat-sealable film can be set to, for example, a range of 145°C to 300°C, a range of 145°C to 290°C, or a range of 145°C to 280°C.

[0075] The melting point of the heat-sealable film in the outer packaging material for vacuum insulation can be measured by the following method. First, approximately 10 mg of the heat-sealable film is peeled off the outer packaging material for vacuum insulation to obtain a sample. This sample is placed in an aluminum cell and heated from 20°C to 300°C at a heating rate of 10°C / min using a differential scanning calorimeter (NETZSCH DSC204) in a nitrogen atmosphere, and held at that temperature for 10 minutes. It is then cooled to 20°C at a cooling rate of 10°C / min, held at that temperature for 10 minutes, and then heated again to 300°C at a heating rate of 10°C / min (second heating). The intersection of the tangent at the melting point observed during the second heating and the baseline of the DSC curve on the lower side of the melting point can be considered the melting point of the heat-sealable film.

[0076] The heat-sealable film described above may contain other materials such as antiblocking agents, lubricants, flame retardants, and fillers.

[0077] The thickness of the heat-sealable film is preferably in the range of 20 μm to 100 μm, more preferably in the range of 25 μm to 90 μm, and particularly preferably in the range of 30 μm to 80 μm. If the thickness of the heat-sealable film is greater than the above range, the gas barrier performance of the outer packaging material for vacuum insulation may decrease, and if the thickness is less than the above range, the desired adhesive strength may not be obtained.

[0078] 4. Protective film The vacuum insulation material outer packaging according to this disclosure preferably has a protective film in addition to the heat-sealable film and the barrier film. The position of the protective film in the vacuum insulation material outer packaging is not particularly limited, but it is preferable that the protective film be positioned at a location that becomes the outermost layer (surface layer) when forming the vacuum insulation material, such as on the side of the barrier film opposite to the heat-sealable film.

[0079] The protective film mentioned above can be any film made of a resin with a higher melting point than a heat-sealable film, and may be in sheet or film form. Specifically, the protective film described in Japanese Patent Publication No. 2017-180822 can be used, so a detailed explanation is omitted here.

[0080] 5. Regarding the layer structure The outer packaging material for vacuum insulation material of this disclosure is not particularly limited as long as it has the barrier layer described above, but it is preferable that it has at least one of the barrier films described above.

[0081] As a specific layer configuration of the outer packaging material for vacuum insulation material of this disclosure, for example, as shown in Figure 3(a), an example can be given in which a barrier film 5 is formed by laminating a resin substrate 3, an inorganic layer 4, and a barrier layer 10 in that order, a heat-sealable film 6 disposed on one side of the barrier film 5, and a protective film 7 disposed on the side of the barrier film 5 opposite to the heat-sealable film 6.

[0082] Another example of an outer packaging material for vacuum insulation is shown in Figure 3(b), in which a second barrier film 8 having a resin substrate 3 and an inorganic layer 4 disposed on one side of the resin substrate 3 is placed between the protective film 7 and the barrier film 5.

[0083] 6. Characteristics of outer packaging materials for vacuum insulation. (1) Radio wave transparency The outer packaging material for vacuum insulation materials described herein preferably has radio wave transparency. Vacuum insulation materials using the above-mentioned outer packaging material may be used in insulated boxes used in logistics, and in such cases, there is a need for a vacuum insulation material that can transmit radio waves for the purpose of identifying the contents and traceability.

[0084] Here, "having radio wave transparency" is not particularly limited as long as the equipment inside the compartment covered with vacuum insulation material has enough radio wave transparency to allow radio wave contact with the outside. However, it is preferable that the electromagnetic shielding performance in the range of 300 MHz to 30 GHz is 10 dB or less. Radio wave transparency can be measured by far-field measurement. Specifically, a transmitting antenna is placed in one anechoic chamber and a receiving antenna in the other anechoic chamber, and the shielding material is placed in the wall window separating the two for evaluation. One method for providing the aforementioned radio wave transparency is to not use a layer containing metal in the outer packaging material for vacuum insulation material according to this disclosure.

[0085] (2) Gas barrier properties The vacuum insulation material packaging disclosed herein has excellent gas barrier performance. Specifically, the water vapor permeability of the vacuum insulation material packaging in an atmosphere of 40°C and 90% RH is 0.01 g / m³. 2 It is preferable that the oxygen permeability of the outer packaging material for vacuum insulation after 10% stretching is 1.5 cc / (m²) in an atmosphere of 70°C and 0% RH. 2 It is preferable that it be less than or equal to (day·atm), and especially 1.0 cc / (m³). 2 It is preferable that the temperature is less than or equal to (day·atm). This is because it is possible to create an outer packaging material for vacuum insulation that can maintain high gas barrier performance even after stretching. Therefore, the above outer packaging material for vacuum insulation can be made capable of forming a vacuum insulation material that can maintain its insulation performance for a long period of time even in actual use conditions that have a folded portion.

[0086] The water vapor permeability of the above-mentioned vacuum insulation outer packaging material can be measured in accordance with ISO-15106-5:2015 (differential pressure method) using a water vapor permeability measuring device (DELTAPERM, manufactured by Technolox, UK) under an atmosphere of 40°C and 90% RH humidity. The measurement is performed by installing the outer packaging material between the upper and lower chambers of the device, with the surface of the outer packaging material located on the barrier film side relative to the heat-sealable film in the thickness direction of the outer packaging material being the high-humidity side (water vapor supply side), and measuring a permeability area of ​​64 cm². 2 The measurement is carried out under the following conditions. At least three samples are measured under one condition, and the average of these measurements is taken as the water vapor transmission value under that condition. The water vapor transmission values ​​described herein can be measured using the same method as described above.

[0087] The oxygen permeability of the outer packaging material for the above-mentioned vacuum insulation material can be measured using a high-temperature measurement system (Hitachi High-Tech Science, TH-85) under conditions of a measurement temperature of 70°C and humidity of 0%RH, with an oxygen gas permeability measuring device (MOCON, USA, OXTRAN), in reference to JIS K 7126-2A:2006 (Plastics - Films and sheets - Gas permeability test methods - Part 2: Isobaric method, Annex A: Test method for oxygen gas permeability by electrolytic sensor method).

[0088] The measurement is performed at 70°C using an outer packaging material for vacuum insulation that has been stretched by 10% using a tensile testing machine. The surface of the outer packaging material for vacuum insulation is placed in the apparatus so that the surface located on the barrier film side relative to the heat-sealable film in the thickness direction of the outer packaging material for vacuum insulation is in contact with oxygen gas, with a permeable area of ​​50 cm². 2The measurement will be carried out under the following conditions. The above measurement will be performed in the following procedure. First, the apparatus will be purged by supplying a carrier gas at a flow rate of 10 cc / min for 60 minutes or more. The carrier gas can be nitrogen gas containing approximately 5% hydrogen. After purging, the test gas will be flowed into the apparatus, and the measurement will begin after 12 hours have passed to reach equilibrium. The test gas will be at least 99.5% dry oxygen. At least three samples will be measured under each condition, and the average of these measurements will be taken as the oxygen permeability value for that condition.

[0089] 7. Other The thickness of the outer packaging material for vacuum insulation material in this disclosure is not particularly limited as long as it can obtain the desired gas barrier performance and strength, but is preferably in the range of 30 μm to 200 μm, and more preferably in the range of 50 μm to 150 μm.

[0090] The vacuum insulation material packaging material disclosed herein may or may not be transparent, and can be appropriately determined depending on the application of the vacuum insulation material in which the vacuum insulation material packaging material disclosed herein is used. The transparency of the vacuum insulation material packaging material described above is not defined by a strict transmittance, but can be appropriately determined depending on the application, etc.

[0091] If the outer packaging material for vacuum insulation material described herein is transparent, the vacuum insulation material using the above-mentioned outer packaging material will allow for visual inspection of its interior. Therefore, by placing a detection agent together with the core material inside the vacuum insulation material, it becomes possible to visually confirm the vacuum state inside from changes in the detection agent.

[0092] The method for manufacturing the outer packaging material for vacuum insulation material according to this disclosure is not particularly limited as long as it can produce an outer packaging material for vacuum insulation material with the desired configuration, and known methods can be used. For example, this could be a dry lamination method in which each layer that has been pre-formed is bonded together using the interlayer adhesive described above, or a method in which each material of a heat-melted gas barrier film is extruded and bonded together using a T-die or the like, and a heat-sealable film is bonded to the resulting laminate via an interlayer adhesive.

[0093] The vacuum insulation material outer packaging material of this disclosure can be used with vacuum insulation materials. In a vacuum insulation material, the vacuum insulation material outer packaging material of this disclosure can be used by arranging it opposite the core material with the heat-sealable film facing the core material.

[0094] B. Vacuum insulation material The vacuum insulation material of this disclosure is a vacuum insulation material having a core material and an outer packaging material for vacuum insulation material that encloses the core material, characterized in that the outer packaging material for vacuum insulation material is the one described in section "A. Outer packaging material for vacuum insulation material" above.

[0095] Figure 4(a) is a schematic perspective view showing an example of the vacuum insulation material of this disclosure, and Figure 4(b) is a cross-sectional view of Figure 4(a). The vacuum insulation material 50 illustrated in Figure 4 has a core material 11 and an outer packaging material 20 for vacuum insulation material that encloses the core material 11, and the outer packaging material 20 for vacuum insulation material is the outer packaging material for vacuum insulation material described in Figure 3. The vacuum insulation material 50 is a bag in which two outer packaging materials 20 for vacuum insulation material are facing each other with their respective heat-sealable films facing each other, and their ends 12 are joined by heat welding, with the core material 11 enclosed inside the bag and the inside of the bag under reduced pressure.

[0096] According to this disclosure, if the outer packaging material for vacuum insulation material that encloses the core material is the outer packaging material for vacuum insulation material described in section "A. Outer packaging material for vacuum insulation material" above, then even if the end portion 12 is used in a folded state, for example, it is possible to suppress the decrease in gas barrier properties at the folded portion, and the vacuum insulation material can maintain good insulation performance. The vacuum insulation material of this disclosure will be described below for each component.

[0097] 1. Outer packaging material for vacuum insulation The outer packaging material for vacuum insulation material in this disclosure is a component that encloses the core material, and is the same as the outer packaging material for vacuum insulation material described in section "A. Outer packaging material for vacuum insulation material" above, so a further explanation is omitted here.

[0098] 2. Core material In this disclosure, the core material is a component enclosed by an outer packaging material for vacuum insulation. Enclosing means being sealed inside a bag formed using the outer packaging material for vacuum insulation.

[0099] The core material preferably has low thermal conductivity. Furthermore, the core material can be a porous material with a void ratio of 50% or more, particularly 90% or more.

[0100] The core material can be made from materials such as powders, foams, or fibers. The powder can be either inorganic or organic, and examples include dry silica, wet silica, agglomerated silica powder, conductive powder, calcium carbonate powder, perlite, clay, and talc. In particular, a mixture of dry silica and conductive powder is advantageous when used in a temperature range where internal pressure increases, because the decrease in thermal insulation performance due to the increase in internal pressure of the vacuum insulation material is small. Furthermore, by adding substances with low infrared absorption rates, such as titanium oxide, aluminum oxide, or indium-doped tin oxide, as radiation suppressants to the above materials, the infrared absorption rate of the core material can be reduced.

[0101] The foams used can include urethane foam, styrene foam, phenolic foam, and the like. Among these, foams that form open cells are preferred.

[0102] The fibrous material described above may be inorganic or organic, but inorganic fibers are preferred from the viewpoint of thermal insulation performance. Examples of such inorganic fibers include glass fibers such as glass wool and glass fiber, alumina fibers, silica-alumina fibers, silica fibers, ceramic fibers, and rock wool. These inorganic fibers are preferred because they have low thermal conductivity and are easier to handle than powders.

[0103] The core material may be one of the materials described above, or it may be a composite material made by mixing two or more materials.

[0104] 3. Others The vacuum insulation material of this disclosure has a core material sealed inside an outer packaging material for vacuum insulation material, and the inside is reduced in pressure to create a vacuum. The degree of vacuum inside the vacuum insulation material is preferably, for example, 5 Pa or less. This is because it is possible to reduce heat conduction due to convection of the air remaining inside, thereby enabling excellent insulation performance.

[0105] The lower the thermal conductivity of the vacuum insulation material, the better. For example, a thermal conductivity (initial thermal conductivity) of 5 mW / (mK) or less is preferable. This is because the vacuum insulation material will be less likely to conduct heat to the outside, thus achieving a high insulation effect. In particular, an initial thermal conductivity of 4 mW / (mK) or less is more preferable. The thermal conductivity can be the value measured in accordance with JIS A1412-2:1999, under conditions of a high temperature of 30°C, a low temperature of 10°C, and an average temperature of 20°C.

[0106] Furthermore, in this disclosure, it is preferable that the increase in thermal conductivity before and after storage at 70°C for 4 weeks is 3.5 mW / mK or less, and particularly preferable that it is 3.0 mW / mK or less.

[0107] The manufacturing method for the vacuum insulation material of this disclosure can be a general method. For example, two outer packaging materials for vacuum insulation material, as described in section A. Outer packaging material for vacuum insulation material above, are prepared, and the heat-sealable films of each are placed facing each other and overlapped. The outer edges of three sides are heat-sealed to obtain a bag with one side open. After inserting a core material into this bag through the opening, air is sucked in through the opening, and the opening is sealed while the inside of the bag is under reduced pressure to obtain a vacuum insulation material.

[0108] The vacuum insulation material disclosed herein can be used, for example, in articles requiring thermal insulation. Such articles will be described later.

[0109] C. Items with vacuum insulation The vacuum-insulated article of this disclosure is an article having a thermally insulating region and a vacuum-insulated article comprising a vacuum-insulated material, wherein the vacuum-insulated material comprises a core material and an outer packaging material for the vacuum-insulated material in which the core material is enclosed, and the outer packaging material for the vacuum-insulated material is the outer packaging material for the vacuum-insulated material described in section A. Outer packaging material for vacuum-insulated material above.

[0110] According to this disclosure, since the vacuum insulation material used in the article is made of the outer packaging material for vacuum insulation material described in section "A. Outer packaging material for vacuum insulation material", the vacuum level of the vacuum insulation material can be maintained for a long period of time, and good insulation performance can be achieved. By equipping the article with such vacuum insulation material, energy saving can be achieved for the article and the object in which the article is used.

[0111] The vacuum insulation material and the outer packaging material used therein in this disclosure have been described in detail in sections "B. Vacuum Insulation Material" and "A. Outer Packaging Material for Vacuum Insulation Material" above, so a detailed explanation is omitted here.

[0112] The articles in this disclosure have thermally insulated regions. These thermally insulated regions are regions that are thermally insulated by a vacuum insulating material, and include, for example, regions that are kept warm or cold, regions that surround a heat source or cooling source, and regions that are isolated from a heat source or cooling source. These regions may be spaces or objects.

[0113] Examples of the above-mentioned items include electrical equipment such as refrigerators, freezers, warmers, and coolers; containers such as insulated containers, cooler containers, transport containers, containers, and storage containers; vehicles such as cars, aircraft, and ships; buildings such as houses and warehouses; and building materials such as wall materials and floor materials.

[0114] D. Barrier film The barrier film of this disclosure is a barrier film having a barrier layer containing a resin and an inorganic layered compound, wherein the resin has a lamellar structure having a two-phase structure of a crystalline portion and an amorphous portion, and when the thickness of the crystalline portion in the lamellar structure is taken as 1, the thickness of the amorphous portion is 1.080 or more.

[0115] The barrier film described herein is the same as that described in "2. Barrier Film" of "A. Outer Packaging Material for Vacuum Insulation Material" above, so a further explanation is omitted here.

[0116] Furthermore, the gas barrier properties of the above barrier film are the same as those described in section (2) Gas Barrier Properties in section (6) Characteristics of Outer Packaging for Vacuum Insulation Material, under "A. Outer Packaging Material for Vacuum Insulation Material" above, so the explanation is omitted here.

[0117] This disclosure is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of this disclosure and achieves similar effects is included within the technical scope of this disclosure. [Examples]

[0118] Examples and comparative examples are shown below to further illustrate this disclosure.

[0119] (Barrier film) Barrier film A: A film in which a metallic aluminum layer (thickness: 40 nm) is vapor-deposited on one side of a PET film (thickness: 12 μm), and then Exevia (trade name, manufactured by Sumitomo Chemical, containing inorganic layered compounds) is coated to a thickness of 200 μm on the vapor-deposited film. <Port Conditions> A coating solution prepared with a water:isopropyl alcohol = 2:1 mixture to achieve a solid content concentration of 4% under room temperature conditions was applied using a gravure coater at a line speed of 10 m / min and a drying temperature of 80°C.

[0120] Barrier film A-2: A film made by depositing a metallic aluminum layer (thickness: 40 nm) onto one side of a PET film (thickness: 12 μm), then coating the deposited film with Exevia (product name, manufactured by Sumitomo Chemical, containing inorganic layered compounds) to a thickness of 200 μm, and finally heat-treating the film. <Port Conditions> The coating liquid prepared to have a solid content concentration of 4% with a solvent of water:isopropyl alcohol = 2:1 at room temperature was coated using a gravure coater under the conditions of a line speed of 10 m / min and a drying temperature of 80°C. <Heat treatment conditions (post-heating)> The film after coating was placed in a thermostatic bath set at 130°C and allowed to stand for 30 minutes.

[0121] · Barrier film B: A film obtained by coating a vapor deposition film of a film in which a metal aluminum layer (thickness: 40 nm) is vapor-deposited on one side of a PET film (thickness: 12 μm) with Strata (trade name, manufactured by Sumitomo Chemical, containing an inorganic layered compound) to a thickness of 200 μm <Coating conditions> The coating liquid prepared to have a solid content concentration of 4% with a solvent of water:ethanol = 2:1 at room temperature was coated using a gravure coater under the conditions of a line speed of 10 m / min and a drying temperature of 80°C.

[0122] · Barrier film B-2: A film obtained by coating a vapor deposition film of a film in which a metal aluminum layer (thickness: 40 nm) is vapor-deposited on one side of a PET film (thickness: 12 μm) with Strata (trade name, manufactured by Sumitomo Chemical, containing an inorganic layered compound) to a thickness of 200 μm <Coating conditions> The coating liquid prepared to have a solid content concentration of 4% with a solvent of water:ethanol = 2:1 at room temperature was coated using a gravure coater under the conditions of a line speed of 4 m / min and a drying temperature of 50°C.

[0123] · Barrier film C: A film provided with a UB coat layer (PVA + TEOS layer: 250 nm) on a vapor deposition film of a film in which a metal aluminum layer (thickness: 40 nm) is vapor-deposited on one side of a PET film (thickness: 12 μm) <UB coat layer> To the solution A (a mixed solution composed of polyvinyl alcohol, isopropyl alcohol, and water) prepared according to the composition shown below, the solution B (a hydrolysis solution composed of tetraethoxysilane (TEOS), isopropyl alcohol, hydrochloric acid, and ion-exchanged water) prepared in advance according to the composition shown below was added and stirred, and a colorless and transparent coating layer composition was obtained by the sol-gel method. The above coating layer composition was coated on a gas barrier film to be coated by the gravure coating method, and then heat-treated at 120 °C, 140 °C, and 150 °C for 20 seconds each, and aged at 55 °C for 1 week to obtain a coating layer (PVA + TEOS layer) as the second barrier layer.

[0124] <Composition of the Composition for the PVA + TEOS Layer> (Solution A) · Polyvinyl alcohol: 1.81% by mass · Isopropyl alcohol: 39.80% by mass · Water: 2.09% by mass (Solution B) · Tetraethoxysilane: 21.49% by mass · Isopropyl alcohol: 5.03% by mass · 0.5N hydrochloric acid aqueous solution: 0.69% by mass · Ion-exchanged water: 29.10% by mass (*The total of Solution A and Solution B was made 100% by mass)

[0125] · Barrier film D: A film obtained by vapor-depositing a metal aluminum layer (thickness: 40 nm) on one side of an ethylene-vinyl alcohol copolymer resin (EVOH) film (thickness: 12 μm)

[0126] · Barrier film E: A film obtained by coating Excevia (trade name, manufactured by Sumitomo Chemical, containing an inorganic layered compound) to a thickness of 200 μm on the vapor-deposited film of a film obtained by vapor-depositing alumina on one side of a PET film (film thickness: 12 μm) <Coating Conditions> A coating solution prepared with a water:isopropyl alcohol = 2:1 mixture to achieve a solid content concentration of 4% under room temperature conditions was applied using a gravure coater at a line speed of 10 m / min and a drying temperature of 80°C.

[0127] (glue) • Adhesive: A two-component curing adhesive consisting of a main component primarily composed of polyester polyol (Rock Paint Co., Ltd., product name: RU-77T), a hardener containing an aliphatic isocyanate (Rock Paint Co., Ltd., product name: H-7), and an ethyl acetate solvent, mixed by weight in a ratio of main component:hardener:solvent = 10:1:14.

[0128] (Fabrication of outer packaging material for vacuum insulation) [Example 1] A vacuum insulation outer packaging material was fabricated by laminating a 30 μm thick biaxially oriented polypropylene (OPP), a PET film (12 μm thick) with a metallic aluminum layer (40 nm thick) deposited on one side, a barrier film A, and a 50 μm thick linear low-density polyethylene (LLDPE) in this order via an adhesive.

[0129] [Example 4] An outer packaging material for vacuum insulation was prepared in the same manner as in Example 1, except that barrier film B-2 was used instead of barrier film A in Example 1.

[0130] [Comparative Example 1] An outer packaging material for vacuum insulation was prepared in the same manner as in Example 1, except that barrier film B was used instead of barrier film A in Example 1.

[0131] [Comparative Example 2] An outer packaging material for vacuum insulation was prepared in the same manner as in Example 1, except that barrier film C was used instead of barrier film A in Example 1.

[0132] [Comparative Example 3] An outer packaging material for vacuum insulation was prepared in the same manner as in Example 1, except that barrier film A-2 was used instead of barrier film A in Example 1.

[0133] [Reference example] An outer packaging material for vacuum insulation was prepared in the same manner as in Example 1, except that barrier film D was used instead of barrier film A in Example 1.

[0134] (Oxygen permeability OTR) Samples were taken from each vacuum insulation material packaging obtained in Example 1, Comparative Examples 1-2, and Reference Example, and the oxygen permeability of the vacuum insulation material packaging at 70°C after 10% stretching was measured using the method and conditions described in section (2) Gas Barrier Properties of the vacuum insulation material packaging in section (6) Characteristics of Vacuum Insulation Material Packaging above. The results are shown in Table 1.

[0135] (Thickness of crystalline and amorphous regions) The measurements were taken using the method described in section (1) Resin under "(1) Barrier Layer" of "A. Outer Packaging Material for Vacuum Insulation Material". The results are shown in Table 1. Note that the reference example is the value for the EVOH film surface.

[0136] (Fabrication of vacuum insulation material) Two sheets of vacuum insulation outer packaging material (dimensions: 300mm x 500mm) obtained in Examples 1-4, Comparative Examples 1-3, and Reference Example were prepared. The two sheets were stacked with heat-sealable films facing each other, and three sides of the quadrilateral were heat-sealed to create a bag with an opening on only one side. A 230mm x 380mm x 20mm sheet of glass wool was used as the core material. After drying, the core material and 5g of desiccant (calcium oxide) were placed in the bag, and the inside of the bag was evacuated. Then, the opening of the bag was sealed by heat sealing to obtain a vacuum insulation material. The achieved pressure was 0.05 Pa.

[0137] (Increase in thermal conductivity of vacuum insulation material) The increase in thermal conductivity of the vacuum insulation material was determined by measuring the thermal conductivity of the vacuum insulation material using the outer packaging material obtained in Example 1, Comparative Examples 1-2, and the Reference Example using the method described in Section 3. Others of "B. Vacuum Insulation Material". Then, the thermal conductivity of the vacuum insulation material was measured again using the same method after being stored at 70°C for 4 weeks, and the difference was taken as the increase. The results are shown in Table 1.

[0138] [Table 1]

[0139] From the results in Table 1, it was confirmed that when a resin with an amorphous region thickness of 1.080 or more (with the crystalline region thickness set to 1) was used, the oxygen permeability after 10% stretching was low, and the increase in thermal conductivity was also kept low. In Example 4, since the oxygen permeability after 10% stretching is low, it is expected that the increase in thermal conductivity will be low, similar to Example 1.

[0140] From Example 1 and Comparative Example 3, it was found that the thickness of the amorphous portion tends to increase when heat treatment is not performed after coating and drying, while the thickness of the crystalline portion tends to increase when the heat treatment temperature after coating and drying is increased. Furthermore, from Example 4 and Comparative Example 1, it was found that the thickness of the amorphous portion tends to increase when the drying temperature is lowered to a certain extent.

[0141] (Fabrication of outer packaging material for vacuum insulation) [Example 2] A vacuum insulation outer packaging material was fabricated by laminating a 30 μm thick biaxially oriented polypropylene (OPP), a PET film (12 μm thick) with a metallic aluminum layer (40 nm thick) deposited on one side, a barrier film E, and a 50 μm thick linear low-density polyethylene (LLDPE) in this order via an adhesive.

[0142] [Example 3] A vacuum insulation outer packaging material was fabricated by laminating a 30 μm thick biaxially oriented polypropylene (OPP), a PET film (thickness: 12 μm) with alumina vapor-deposited on one side, a film with a UB coating layer (thickness 250 nm, the same as that used in barrier film C) on the vapor-deposited film, barrier film E, and a 50 μm thick linear low-density polyethylene (LLDPE) in this order via an adhesive.

[0143] (Electromagnetic shielding properties) A transmitting antenna was placed in one anechoic chamber and a receiving antenna in the other, and shielding material was placed in the wall window separating the two chambers for evaluation. Using the above evaluation method, the electromagnetic shielding rate in the range of 300 MHz to 13.5 GHz was measured, and it was confirmed that it was 5 dB or less across the entire measurement frequency range.

[0144] (Thickness of crystalline and amorphous regions) The thickness of the crystalline and amorphous portions of barrier film E is the same as that of barrier film A.

[0145] [Table 2]

[0146] Thus, the present disclosure provides, for example, the following inventions.

[0147] [1] An outer packaging material for vacuum insulation material having a barrier layer containing a resin and an inorganic layered compound, wherein the resin has a lamellar structure having a two-phase structure of a crystalline portion and an amorphous portion, and when the thickness of the crystalline portion in the lamellar structure is taken as 1, the thickness of the amorphous portion is 1.080 or more. [2] The outer packaging material for vacuum insulation material according to [1], wherein the thickness of the barrier layer is 4 μm or less. [3] An outer packaging material for vacuum insulation material according to [1] or [2], having a barrier film in which a resin substrate, an inorganic layer, and the above barrier layer are laminated in this order. [4] The outer packaging material for vacuum insulation material according to [3], wherein the inorganic material constituting the above inorganic layer is aluminum, aluminum oxide, or silicon oxide. [5] The outer packaging material for vacuum insulation material according to [3] or [4], further comprising a second barrier film in addition to the barrier film described above. [6] The vacuum insulation outer packaging material described in any of [1] to [5], wherein the electromagnetic shielding rate of the vacuum insulation outer packaging material is 5.0 dB or less. [7] The oxygen permeability at 70°C after 10% stretching is 1.5 cc / m². 2 Outer packaging material for vacuum insulation material, which is less than or equal to / day / atm, as described in any of [1] to [6]. [8] A vacuum insulation material having a core material and an outer packaging material in which the core material is enclosed, A vacuum insulation material wherein the above-mentioned outer packaging material is the vacuum insulation outer packaging material described in any of claims [1] to [7]. [9] Articles having a thermally insulating region and articles with vacuum insulation material, The above vacuum insulation material comprises a core material and an outer packaging material in which the core material is enclosed. An article with vacuum insulation, wherein the above-mentioned outer packaging material is the vacuum insulation outer packaging material described in any of claims [1] to [7].

[10] A barrier film having a barrier layer containing a resin and an inorganic layered compound, The above resin is a barrier film having a lamellar structure with a two-phase structure of a crystalline portion and an amorphous portion, wherein when the thickness of the crystalline portion in the lamellar structure is taken as 1, the thickness of the amorphous portion is 1.080 or more.

[11] The barrier film according to

[10] , wherein the barrier layer is arranged on a resin substrate. [Explanation of Symbols]

[0148] 1… resin 2… Inorganic layered compounds 3… Resin base material 4 … Inorganic layer 5… Barrier film 6… Heat-sealable film 7… Protective film 8. Second barrier film 10 … Barrier layer 20… Outer packaging material for vacuum insulation 21 ... Crystalline layer 22 … Amorphous layer 50… Vacuum insulation material

Claims

1. An outer packaging material for vacuum insulation material having a barrier layer containing a resin and an inorganic layered compound, wherein the resin has a lamellar structure having a two-phase structure of a crystalline portion and an amorphous portion, and when the thickness of the crystalline portion in the lamellar structure is taken as 1, the thickness of the amorphous portion is 1.080 or more.

2. The outer packaging material for vacuum insulation material according to claim 1, wherein the thickness of the barrier layer is 4 μm or less.

3. The outer packaging material for vacuum insulation material according to claim 1, comprising a barrier film in which a resin substrate, an inorganic layer, and the barrier layer are laminated in this order.

4. The outer packaging material for vacuum insulation material according to claim 3, wherein the inorganic material constituting the inorganic layer is aluminum, aluminum oxide, or silicon oxide.

5. The outer packaging material for vacuum insulation material according to claim 3, further comprising a second barrier film in addition to the aforementioned barrier film.

6. The vacuum insulation material outer packaging material according to claim 5, wherein the electromagnetic shielding rate of the outer packaging material for the vacuum insulation material is 5.0 dB or less.

7. The oxygen permeability at 70°C after 10% stretching is 1.5 cc / (m ２ The outer packaging material for vacuum insulation material according to claim 5, wherein the temperature is less than or equal to (day atm).

8. A vacuum insulation material having a core material and an outer packaging material in which the core material is enclosed, A vacuum insulation material wherein the outer packaging material is the vacuum insulation outer packaging material described in any one of claims 1 to 7.

9. Articles having a thermally insulating region and articles with vacuum insulation material, The vacuum insulation material comprises a core material and an outer packaging material in which the core material is enclosed. An article with a vacuum insulation material, wherein the outer packaging material is the vacuum insulation outer packaging material described in any of claims 1 to 7.

10. A barrier film having a barrier layer containing a resin and an inorganic layered compound, The resin has a lamellar structure having a two-phase structure of a crystalline portion and an amorphous portion, and when the thickness of the crystalline portion in the lamellar structure is taken as 1, the thickness of the amorphous portion is 1.080 or more, making it a barrier film.

11. The barrier film according to claim 10, wherein the barrier layer is disposed on a resin substrate.

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