JP7247235B2 - Outer packaging for vacuum insulation, vacuum insulation, and articles with vacuum insulation - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to a vacuum insulation outer wrapping material capable of forming a vacuum insulation material, a vacuum insulation material, and an article with a vacuum insulation material.

In recent years, vacuum heat insulating materials have been used for the purpose of saving energy in articles. The vacuum insulation material is a member in which a core material is arranged in the bag of the outer packaging material, and the inside of the bag is held in a vacuum state with a pressure lower than the atmospheric pressure. good thermal insulation performance. The outer wrapping material used for the vacuum heat insulating material will be referred to as the outer wrapping material for the vacuum heat insulating material or simply as the outer wrapping material.

In order to maintain the vacuum state inside the vacuum insulation material for a long time, the outer packaging material for the vacuum insulation material has a gas barrier function to suppress the permeation of gases such as oxygen and water vapor, and the edges are joined when wrapping the core material. Therefore, physical properties such as thermal adhesion are required for sealing and sealing the core material. In order to satisfy these physical properties, the outer wrapping material for a vacuum heat insulating material generally employs a configuration including a gas barrier film and a heat-sealable film as members.

A general vacuum insulation outer wrapping material uses a metal foil or a metal deposition layer as a gas barrier film. For example, Patent Document 1 describes an outer packaging material using aluminum foil, and Patent Document 2 discloses a vapor-deposited film in which an aluminum vapor-deposited layer is formed on a polyvinyl alcohol-based polymer film as an outer wrapping material.

Japanese Patent Application Laid-Open No. 2003-262296 WO2013/125564

In recent years, there has been a demand for a vacuum heat insulating material that allows radio waves to pass through for the purpose of identification and traceability of contents for use in heat insulating boxes and the like used in physical distribution. However, the outer wrapping materials used for conventional vacuum insulation materials generally contain metal foil or a metal vapor deposition layer, which blocks radio waves and is unsuitable for applications requiring wireless communication inside and outside a space. rice field.

The present disclosure is an invention made in view of the above problems, and is capable of transmitting radio waves and capable of producing a vacuum heat insulating material that can maintain good heat insulating performance. The main purpose is to provide an article with thermal insulation and vacuum insulation.

The present disclosure is a vacuum insulation material outer packaging material having a heat-sealable film and two or more inorganic layers including a first inorganic layer and a second inorganic layer, wherein the vacuum insulation material outer packaging material is Furthermore, an inorganic layered compound layer containing an inorganic layered compound and a binder resin is included, the first inorganic layer, the inorganic layered compound layer, and the second inorganic layer are arranged in this order, and the metal layer is To provide an outer wrapping material for a vacuum heat insulating material, which is not arranged.

Further, the present disclosure provides a vacuum heat insulating material having a core material and an outer wrapping material in which the core material is enclosed, wherein the outer wrapping material is the vacuum heat insulating outer wrapping material described above. .

Further, the present disclosure is an article having a heat insulating region and an article with a vacuum insulation material including a vacuum insulation material, wherein the vacuum insulation material has a core material and an outer wrapping material in which the core material is enclosed. and an article with a vacuum heat insulating material, wherein the outer wrapping material is the vacuum heat insulating outer wrapping material described above.

Advantageous Effects of Invention According to the present disclosure, it is possible to provide an outer wrapping material for a vacuum heat insulating material that is capable of transmitting radio waves and capable of producing a vacuum heat insulating material that can maintain good heat insulating performance.

1 is a schematic cross-sectional view showing an example of an outer wrapping material for a vacuum heat insulating material of the present disclosure; FIG. 1A and 1B are a schematic perspective view and a cross-sectional view showing an example of a vacuum heat insulating material of the present disclosure; FIG. FIG. 4 is a schematic cross-sectional view showing another example of the outer wrapping material for vacuum heat insulating material of the present disclosure; FIG. 4 is a schematic cross-sectional view showing another example of the outer wrapping material for vacuum heat insulating material of the present disclosure;

Embodiments of the present disclosure include vacuum insulation envelopes, vacuum insulation, and articles with vacuum insulation. Embodiments of the present disclosure will be described below with reference to the drawings and the like.
However, the present disclosure can be embodied in many different forms and should not be construed as limited to the description of the embodiments exemplified below. In addition, in order to make the description clearer, the drawings may schematically represent the width, thickness, shape, etc. of each part compared to the embodiment, but this is only an example and limits the interpretation of the present disclosure. not something to do. In addition, in this specification and each figure, the same reference numerals may be given to the same elements as those described above with respect to the existing figures, and detailed description thereof may be omitted as appropriate. Also, for convenience of explanation, the terms "upper" and "lower" may be used, but the up-down direction may be reversed.

Also, in this specification, there is no particular limitation when a configuration such as a member or a region is “above (or below)” another configuration such as another member or another region. So far, this includes not only when directly above (or directly below) other structures, but also when above (or below) other structures, i.e. above (or below) other structures and between other structures. Including cases where the constituent elements of are included.

The present inventors considered using a vapor-deposited metal oxide layer instead of a metal layer for the gas barrier film in order to impart radio wave transmittance to the outer packaging material for a vacuum insulation material. It was found that the performance was inadequate. Therefore, in order to improve the gas barrier performance, an attempt was made to increase the number of stacked metal oxide layers and to increase the thickness of each metal oxide layer. However, it has been found that increasing the number of metal oxide layers results in low productivity, loss of flexibility as an exterior material, and barrier breakage that is likely to occur when various bendings are applied. In addition, it was found that when the thickness of each metal oxide layer is increased, cracking of the barrier film occurs even if the thickness is increased in the first place, and it is not easy to improve the barrier performance.

In addition, when the gas barrier film breaks down, the water vapor barrier performance and the oxygen barrier performance of the outer packaging material for the vacuum insulation material deteriorate, but the water vapor barrier performance deteriorates and the amount of water vapor flowing into the vacuum insulation material increases. Therefore, it is possible to suppress the increase in the degree of internal vacuum and reduce the effect on the insulation performance of the vacuum insulation material simply by adding an inexpensive desiccant together with the core material to the vacuum insulation material. can. Therefore, in terms of the performance of the outer packaging material for a vacuum heat insulating material, deterioration of the oxygen barrier performance poses a problem for maintaining the heat insulation performance of the vacuum heat insulation material rather than deterioration of the water vapor barrier performance.

As a result of intensive studies to solve the above problems, the present inventors have found that, instead of arranging a metal layer on the outer packaging material for a vacuum heat insulating material, a layer containing an inorganic layered compound is arranged to achieve an oxygen barrier. In addition to securing the performance, we found that it is possible to suppress the deterioration of the oxygen barrier performance by sandwiching the layer containing the inorganic layered compound between the upper and lower layers of the inorganic layer. The present inventors have found that the outer packaging material for a vacuum insulation material can produce a vacuum insulation material that can be maintained.
Hereinafter, the outer wrapping material for a vacuum heat insulating material, the vacuum heat insulating material, and the article with the vacuum heat insulating material of the present disclosure will be described respectively.

A. Exterior Wrapping Material for Vacuum Insulation Material First, the exterior packaging material for vacuum insulation material of the present disclosure will be described in detail.
The outer packaging material for a vacuum insulation material of the present disclosure is an outer packaging material for a vacuum insulation material having a heat-sealable film and two or more inorganic layers including a first inorganic layer and a second inorganic layer, The outer packaging material for a vacuum heat insulating material further includes an inorganic layered compound layer containing an inorganic layered compound and a binder resin, and the first inorganic layer, the inorganic layered compound layer, and the second inorganic layer are It is characterized in that they are arranged in order and that no metal layer is arranged.

FIG. 1 is a schematic cross-sectional view showing an example of the outer wrapping material for a vacuum heat insulating material of the present disclosure. The vacuum insulation outer wrapping material 10 of the present disclosure includes a heat-sealable film 1 arranged on one main surface side of the vacuum heat-insulating outer wrapping material 10, and a first an inorganic layer 4, an inorganic layered compound layer 5 containing an inorganic layered compound and a binder resin, and a second inorganic layer 4 arranged in this order.

In the example of FIG. 1, the outer packaging material 10 for vacuum insulation material has a first gas barrier film 2a, a second gas barrier film 2b, and a third gas barrier film 2c. have In this example, the first gas barrier film 2a contains the first inorganic layer 4, and the second gas barrier film 2b contains the second inorganic layer 4. As shown in FIG. In addition, the inorganic layered compound layer 5 is included in the first gas barrier film 2a. Specifically, the first gas barrier film 2a includes a first resin substrate 3, an inorganic layer 4 (first inorganic layer 4) arranged on one main surface side of the first resin substrate 3, and an inorganic layered compound layer 5 disposed on the main surface of the first inorganic layer 4 opposite to the first resin substrate 3 . The second gas barrier film 2 b has an inorganic layer 4 (second inorganic layer 4 ) disposed on the main surface side of at least one of the second resin substrate 3 and the second resin substrate 3 . The inorganic layered compound layer 5 in the first gas barrier film is arranged between the first inorganic layer 4 in the first gas barrier film 2a and the second inorganic layer 4 in the second gas barrier film 2b. Furthermore, a third gas barrier film 2c having a third resin base material 3 and a third inorganic layer 4 is provided on the opposite side of the second gas barrier film 2b to the first gas barrier film 2a. is located on the side of the second gas barrier film 2b.

The outer wrapping material for a vacuum heat insulating material of the present disclosure is characterized in that no metal layer is arranged. In the present disclosure, the metal layer is a metal layer in which metal atoms constituting the layer are bonded to each other by metal bonding and have radio wave shielding properties. Examples of the metal layer include metal foils and metal thin films of aluminum, nickel, stainless steel, iron, copper, titanium, and the like.

Since no metal layer is arranged in the outer packaging material for a vacuum heat insulating material of the present disclosure, radio waves can be transmitted therethrough. Furthermore, by having the inorganic layered compound layer instead of the metal layer, the inorganic layer is arranged on each side of the inorganic layered compound layer while securing the oxygen barrier property, and the inorganic layered compound layer is sandwiched between the inorganic layers. Thus, deterioration of the oxygen barrier performance of the inorganic layered compound layer can be suppressed. Therefore, it becomes an outer packaging material for a vacuum heat insulating material capable of producing a vacuum heat insulating material capable of transmitting radio waves and maintaining good heat insulating performance.

Hereinafter, each configuration of the outer wrapping material for a vacuum heat insulating material according to the present disclosure will be described in detail.
1. Inorganic layer The outer packaging material for a vacuum heat insulating material of the present disclosure has two or more inorganic layers including a first inorganic layer and a second inorganic layer, and the inorganic layered compound layer includes the first inorganic layer and the second inorganic layer. It is characterized by having a structure disposed between layers. The inorganic layer is a layer other than a metal layer such as a metal foil or a metal thin film, and an inorganic compound film or an MOP bond (where M represents a metal atom, O represents an oxygen atom, P represents represents a phosphorus atom), a film containing a polyvalent metal salt of a polycarboxylic acid polymer, and a mixed compound film containing a metal element, an oxygen element and a hydrophilic group-containing resin. In the present disclosure, the inorganic layer is preferably an inorganic compound film, especially a metal oxide film.

Examples of inorganic compounds constituting the inorganic compound film include oxides of metallic elements or non-metallic elements such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, titanium, boron, yttrium, zirconium, cerium, and zinc; Examples thereof include oxynitrides, nitrides, oxycarbides, oxycarbonitrides, and the like. Specifically, silicon oxides such as _SiO2 , aluminum oxides such as _Al2O3 , magnesium oxides _, titanium oxides, tin oxides, silicon-zinc alloy oxides, indium alloy oxides, silicon nitrides, Examples include aluminum nitride, titanium nitride, silicon oxynitride, and silicon zinc oxide. In particular, metal oxides, particularly aluminum oxide (alumina) and silicon oxide (silica) are preferred. The inorganic compound may be used alone, or may be used by mixing the above materials in an arbitrary ratio.

The inorganic compound film may be a deposited film formed by a vapor deposition method, or may be a coated film formed by a coating method such as coating. In the case of a deposited film, it may be formed by one-time deposition or the like, or may be formed by multiple-time deposition. The inorganic compound film can be formed using a conventionally known method such as a coating method, a vapor deposition method, and a pressure bonding method.

Among them, a deposited film is preferable from the viewpoint of high adhesion to the resin substrate and high gas barrier performance. One gas barrier film may be a single film formed by vapor deposition once, or may be formed by vapor deposition multiple times and have a laminated structure.

Examples of films having M—O—P bonds (where M represents a metal atom, O represents an oxygen atom, and P represents a phosphorus atom) include reaction products of metal oxides and phosphorus compounds. membranes containing

Examples of the metal oxide include oxides of metals having a valence of 2 or more. Specifically, metals of group 2 of the periodic table such as magnesium and calcium; group 12 of the periodic table such as zinc. metals of group 13 of the periodic table such as aluminum; metals of group 14 of the periodic table such as silicon; and oxides of metals such as transition metals such as titanium and zirconium. Among them, aluminum oxide (alumina) is preferable.

Examples of the phosphorus compound include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. Among them, phosphoric acid is preferred. A specific reaction product of a metal oxide and a phosphorus compound can be, for example, the same as the reaction product disclosed in JP-A-2011-226644.

The presence of the MOP bond is such that the maximum infrared absorption peak appears in the range of 1080 cm ^-1 to 1130 cm ^-1 in the infrared absorption spectrum (measurement wavenumber range: 800 cm ^-1 or more and 1400 cm ^-1 or less). You can check by doing The method for measuring the infrared absorption spectrum is not particularly limited, and examples thereof include a method of total reflection measurement (ATR method), a method of scraping a sample from the gas barrier film of the outer packaging material, and a method of measuring the infrared absorption spectrum by the KBr method. A measurement method or the like can be used for the collected sample by microscopic infrared spectroscopy.

Although the thickness of the inorganic layer is not particularly limited, it is preferably 50 nm or less. By setting the thickness of the inorganic layer to be equal to or less than the above value, sufficient flexibility can be maintained, and barrier destruction is less likely to occur.

The compositions and thicknesses of two or more inorganic layers included in the outer packaging material for a vacuum heat insulating material of the present disclosure may be the same or different.

2. Inorganic Layered Compound Layer The inorganic layered compound layer in the present disclosure is a layer arranged between the first inorganic layer and the second inorganic layer. The position of the inorganic layered compound layer is not particularly limited as long as it is arranged between the first inorganic layer and the second inorganic layer. can be provided on the main surface of

The inorganic stratiform compound layer contains at least an inorganic stratiform compound and a binder resin. Such an inorganic layered compound layer is different from a continuous film such as a vapor-deposited thin film that prevents gas permeation. effect), it extends the path necessary for permeation and exhibits barrier performance. Since gas travels mainly through the binder resin in the inorganic layered compound layer, the gas barrier performance of the binder resin itself is important in order to exhibit high barrier performance. There is

However, in the present disclosure, the inorganic layered compound layer has a structure located between the first inorganic layer and the second inorganic layer, and water vapor entering from the outside air and each layer constituting the outer packaging material for the vacuum heat insulating material are inside. The influence of moisture contained can be reduced. Therefore, particularly in a structure in which the inorganic layered compound layer is directly sandwiched between the first inorganic layer and the second inorganic layer, for example, the resin base does not come into direct contact with the inorganic layered compound layer. It is possible to suppress deterioration of the gas barrier performance of the binder resin due to water vapor contained in the material. For this reason, in the present disclosure, a layer other than an adhesive layer and an overcoat layer (that is, a resin base material, etc.) is preferably not placed.

(a) Inorganic layered compound An inorganic layered compound is an inorganic compound having a layered structure in which unit crystal layers are stacked on each other. In other words, the term "layered compound" means a compound or substance having a layered structure. The term "layered structure" refers to a structure in which planes in which atoms are strongly bonded by covalent bonds and arranged densely are stacked in parallel by weak bonding forces such as van der Waals forces.

Any inorganic layered compound may be used as long as it has a layered structure, and examples thereof include graphite, phosphate-based derivative-type compounds (zirconium phosphate-based compounds), chalcogenides, and clay minerals. Among them, clay minerals are preferred.

Specific examples of clay minerals include phyllosilicate minerals such as hydrous silicates; kaolinite group clay minerals such as halloysite, kaolinite, endellite, dickite and nacrite; antigorite group clays such as antigorite and chrysotile. Minerals; smectite group clay minerals such as montmorillonite, iron montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, and stevensite; vermiculite group clay minerals such as vermiculite; mica such as muscovite and phlogopite; margarite and tetrasi mica or mica group clay minerals such as lyric mica and teniolite; chlorite group clay minerals such as cookeite, pseudoite, clinochlore, chamosite and nimite; and substituted products and derivatives thereof. These clay minerals may be natural clay minerals or synthetic clay minerals, and may be contained in combination of two or more.

In the present disclosure, among others, phyllosilicate minerals and smectite clay minerals are preferred, and montmorillonite and hectorite contained in smectite clay minerals are particularly preferred.

The average particle size of the inorganic layered compound particles is preferably 50 nm or more and 5 μm or less, more preferably 100 nm or more and 4 μm or less, and particularly preferably 500 nm or more and 3 μm or less.
This is because by setting the average particle diameter of the particles of the inorganic layered compound within the above range, the oxygen barrier performance of the inorganic layered compound layer is further improved. The particle diameter of the inorganic layered compound particles is the center diameter (major diameter) determined by the photon correlation method by the dynamic light scattering method measured using an ultrafine particle particle size analyzer under the conditions of a temperature of 25 ° C. and a water solvent. .

The aspect ratio of the inorganic layered compound is preferably 50 or more and 5000 or less, more preferably 200 or more and 3000 or less, and particularly preferably 300 or more and 2500 or less.
This is because, by setting the aspect ratio of the inorganic layered compound within the above range, the oxygen barrier performance of the inorganic layered compound layer is further improved. The aspect ratio of the inorganic layered compound is the ratio of the average interplanar spacing (average unit thickness) to the average particle diameter of the particles of the inorganic layered compound, and is calculated by the following formula (1).

Z=L/a (1)
(In the above formula (1), Z is the aspect ratio, L is the average particle diameter of the inorganic layered compound, and a is the average interplanar spacing (average unit thickness) of the inorganic layered compound.)

The average particle diameter L of the inorganic layered compound is the value obtained by the method described above. Further, 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. In addition, it can be confirmed from the powder X-ray diffraction measurement of the composition containing the inorganic layered compound and the binder resin that there is a portion where the interplanar spacing of the inorganic layered compound is widened.

(b) Binder resin The binder resin is not particularly limited, but a hydrophilic resin containing a hydrophilic group is preferable. This is because the hydrophilic resin exhibits a high barrier property against oxygen. Specifically, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polyacrylic acid or its salts, polybenzenesulfonic acid or its salts, polyethyleneimine, polyallylamine, poly Glycerin and the like, and polysaccharides such as hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, amylose, amylopectin, curdlan, xanthan, chitin, cellulose, pullulan and chitosan. In the present disclosure, polyvinyl alcohol and polyacrylic acid are particularly preferred.

Hydrophilic resins are generally susceptible to deterioration in gas barrier performance due to water vapor, but the outer packaging material for a vacuum heat insulating material of the present disclosure has a structure in which a layered compound layer is sandwiched between a first inorganic layer and a second inorganic layer. Therefore, it is possible to suppress the deterioration of the hydrophilic resin for the reasons described above, and it is possible to maintain a high barrier property against oxygen of the layered inorganic compound layer.

(c) Others The oxygen barrier performance of the inorganic layered compound layer improves as the volume of the inorganic layered compound increases. On the other hand, as the volume of the binder resin increases, the bending resistance improves. Therefore, the volume ratio of the inorganic layered compound to the binder resin (inorganic layered compound/resin) is preferably from 5/95 to 90/10, more preferably from 5/95 to 50/50. preferable. By setting the volume ratio of the inorganic layered compound to the binder resin within the above range, it is possible to obtain an inorganic layered compound layer having excellent oxygen barrier performance and flex resistance.

The thickness of the inorganic layered compound layer is preferably 1 μm or less, more preferably 50 nm or more and 500 nm or less, and particularly preferably 100 nm or more and 300 nm or less.
By setting the thickness of the inorganic layered compound layer within the above range, it is possible to exhibit sufficient oxygen barrier performance, and the hardness of the inorganic layered compound layer can be made relatively small. This is because the layered structure of the inorganic layered compound in the inorganic layered compound layer can be maintained even when the material receives bending stress.

3. Heat-Sealable Film The outer wrapping material for a vacuum insulation panel of the present disclosure has a heat-sealable layer disposed on one main surface side. Such heat-sealable films are films that are heat-sealable. The heat-sealable film is a member that forms one surface in the thickness direction of the outer packaging material for vacuum insulation materials, and is used as a core material when producing a vacuum insulation material using the outer packaging material for vacuum insulation materials of the present disclosure. It is a member that joins the end portions of the outer wrapping materials for a vacuum heat insulating material that are opposed to each other when the core material is sealed.

As the heat-weldable film, a resin film that can be melted and fused by heating can be used. ) and other polyolefin resin films; polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT) and other polyester resin films; polyvinyl acetate resin films; polyvinyl chloride resin films; meth)acrylic resin film; urethane resin film and the like.

The heat-sealable film may contain other materials such as anti-blocking agents, lubricants, flame retardants, fillers, and the like.

The thickness of the heat-weldable film may be any thickness that allows obtaining a desired adhesive strength when the outer packaging materials for a vacuum insulation material are joined together. It can be in the range of 90 μm or less, more preferably in the range of 30 μm or more and 80 μm or less.

4. Resin substrate In the outer packaging material for a vacuum heat insulating material of the present disclosure, although not particularly limited, the above-described inorganic layer or inorganic layered compound layer can usually be provided on one main surface of the resin substrate. .

As such a resin substrate, for example, a resin film or the like is suitably used. When the resin substrate is a resin film, the resin film may be unstretched, or may be uniaxially or biaxially stretched. The resin substrate may or may not have transparency.

The resin used for the resin substrate is not particularly limited, and examples thereof include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT). , cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly(meth)acrylic resin, polycarbonate resin, ethylene-vinyl ester copolymer and Various resins such as saponified products thereof, polyamide resins such as various nylons, polyimide resins, polyurethane resins, acetal resins and cellulose resins can be used. Among the above resins, PET, PBT, nylon and the like are more preferably used.

The resin base material may contain various plastic compounding agents, additives, and the like. Examples of additives include lubricants, cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins.

The resin substrate may be surface-treated. This is because the adhesion to the inorganic layer can be improved. Examples of the surface treatment include oxidation treatment disclosed in JP-A-2014-180837, roughening treatment (roughening treatment), easy-adhesion coating treatment, and the like.

Although the thickness of the resin base material is not particularly limited, it 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 the range including A and B is.). Moreover, the resin base material may be a single layer, or may be a multilayer body formed by laminating a plurality of resin layers. Each resin layer in the multilayer body may be composed of different resins or may be composed of the same resin.

It is preferable that the resin base material described above is not arranged between the inorganic layered compound layer and the first inorganic layer or the second inorganic layer. By not arranging a resin base material made of a resin that relatively easily contains water vapor compared to the inorganic layer between the two inorganic layers, it is possible to further suppress the intrusion of water vapor into the inorganic layered compound layer. is.
Further, when the outer packaging material for a vacuum heat insulating material of the present disclosure includes a resin base material, the heat-sealable film, the resin base material, the first inorganic layer, the inorganic layered compound layer, and the second inorganic layer , are preferably included in this order.

5. Overcoat Layer In the outer packaging material for a vacuum heat insulating material of the present disclosure, an overcoat layer can be arranged on one main surface of the inorganic layer or one main surface of the inorganic layered compound layer. By providing the overcoat layer, it is possible to impart even better gas barrier properties to the outer packaging material for a vacuum heat insulating material.

Such an overcoat layer contains a hydrophilic group-containing resin. The presence or absence of the hydrophilic group-containing resin can be determined by, for example, an infrared absorption spectrum. In the atoms constituting the overcoat layer, the ratio of metal atoms to carbon atoms (number of metal atoms/number of carbon atoms) is in the range of 0.1 or more and 2 or less, especially 0.5 or more and 1 0.9 or less, preferably 0.8 or more and 1.6 or less. If the ratio is less than the above range, the brittleness of the overcoat layer may increase, and the resulting overcoat layer may have reduced water resistance, weather resistance, and the like. On the other hand, if the ratio exceeds the above range, the resulting overcoat layer may have reduced gas barrier properties.

The overcoat layer having the ratio as described above, for example, the content of the hydrophilic group-containing resin in the composition for forming the overcoat layer is 5 parts by mass or more and 500 parts by mass with respect to 100 parts by mass of the total amount of alkoxides described later. part or less, especially 20 parts by mass or more and 200 parts by mass or less. As an example of the composition for forming the overcoat layer, liquid A (mixture of polyvinyl alcohol (PVA), isopropyl alcohol and ion-exchanged water) is added to liquid B (tetraethoxysilane (TEOS), isopropyl alcohol , a hydrolyzate composed of hydrochloric acid and ion-exchanged water) is added to 100 parts by mass of TEOS so that PVA has a specific ratio, and the mixture is stirred to obtain a colorless and transparent composition for forming an overcoat layer by a sol-gel method. can be mentioned.

Although the film thickness of the overcoat layer is not particularly limited, it is preferably 200 nm or more. This is because, if it is at least the above value, it is possible to reliably improve the gas barrier properties of the outer packaging material for a vacuum heat insulating material.
In the present disclosure, an overcoat layer may be arranged particularly between the layered inorganic compound layer and the second inorganic layer. By arranging the overcoat layer, it is possible to fill the pinholes and the like existing in the inorganic layer, so that it is possible to further prevent the intrusion of water vapor. By arranging the overcoat layer with respect to the second inorganic layer arranged on the opposite side, it is possible to suppress the permeation of water vapor from the outside, where water vapor easily penetrates.

6. Adhesive Layer The vacuum insulation outer wrapping material of the present disclosure may have an adhesive layer between each barrier film or heat-sealable layer. As a material for such an adhesive layer, conventionally known pressure-sensitive adhesives, thermoplastic adhesives, curable adhesives, and the like can be used.

The adhesive constituting the adhesive layer is usually a two-liquid curable adhesive containing a main agent and a curing agent, but is not limited to this. For example, a one-component curable adhesive mixed with a main agent and a latent curing agent blocked by a known method so that it does not react when mixed with the main agent, or a known adhesive that does not react when mixed with the curing agent. It may be a one-liquid curable adhesive obtained by mixing a latent main agent blocked by a method and a curing agent.

Specific examples of adhesives constituting the adhesive layer include epoxy-based adhesives, polyvinyl acetate-based adhesives, polyacrylic acid ester-based adhesives, cyanoacrylate-based adhesives, ethylene copolymer-based adhesives, and cellulose. adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives, phenol resin adhesives, polyurethane adhesives, reactive (meth)acrylic acid adhesives, inorganic rubber adhesives Adhesives, silicone-based adhesives, inorganic adhesives made of alkali metal silicate, low-melting-point glass, or the like can be used.

In particular, as the adhesive, polyacrylic acid ester-based adhesives, polyurethane-based adhesives, etc. are preferable, and it is particularly preferable that the above-mentioned adhesives are compounds having an isocyanate group as a functional group, and specifically, polyurethane-based adhesives. An adhesive is preferred.

The adhesive constituting the adhesive layer may contain arbitrary materials such as curing accelerators, catalysts, antioxidants, stabilizers, ultraviolet absorbers, light stabilizers, and antistatic agents.

The thickness of the adhesive layer may be any thickness that can exhibit a desired adhesive strength, and can be appropriately set according to the composition of the adhesive layer. Generally, it is preferable that the thickness is about 0.1 g/m ² to 10 g/m ² in a dry state.

The adhesive layer may or may not have transparency, but if transparency is required for the outer packaging material for the vacuum heat insulating material, it is preferably transparent.

The adhesive layer may be a sheet or film formed of the adhesive described above. A coating solution is prepared by mixing the adhesive described above with a desired solvent, and one surface of the heat-weldable film or gas barrier film is prepared. may be applied directly to the surface, dried and cured.
The adhesive layer described above may be arranged between the inorganic layered compound layer and the first inorganic layer or the second inorganic layer.

7. Preferred Form The two or more inorganic layers and the inorganic layered compound layers described above can be disposed on each gas barrier film, which is a film having gas barrier performance and constitutes the outer packaging material for a vacuum heat insulating material of the present disclosure. In this case, the two or more inorganic layers and the inorganic layered compound layer may be present in separate gas barrier films, but a plurality of layers (e.g., the first inorganic layer and the inorganic layered compound layer) may be present in one gas barrier film. layer) may be present.

(First embodiment)
In FIG. 1 described above, the inorganic layered compound layer 5 in the first gas barrier film 2a is the first inorganic layer 4 in the first gas barrier film 2a and the second inorganic layer 4 in the second gas barrier film 2b. The first inorganic layer 4, the inorganic layered compound layer 5, and the second inorganic layer 4 are arranged in between, and are included in the outer packaging material 10 for a vacuum heat insulating material in this order, and the second gas barrier film 2b is arranged so as to face the inorganic layered compound layer 5 of the first gas barrier film 2a.

Such a first embodiment specifically includes the following two aspects.
In a first aspect, a heat-weldable film, a first resin substrate, a first inorganic layer, an inorganic layered compound layer, a second inorganic layer, and a second resin substrate are It is a mode arranged in order.
As a second aspect, in addition to the first aspect, a third inorganic layer and a third resin base are provided on the surface of the second resin base opposite to the second inorganic layer. It is a mode arranged in order.
Each configuration of this embodiment will be described in detail below.

(1) First gas barrier film The first gas barrier film in this embodiment is arranged on one main surface side of the heat-sealable film, and is arranged between the heat-sealable film and the second gas barrier film. It is a thing. In this embodiment, the first gas barrier film has at least a first resin base material, a first inorganic layer, and an inorganic layered compound layer, and the inorganic layered compound layer is the second inorganic layer of the second gas barrier film. are arranged to face the Normally, it is preferable that no other gas barrier film or protective film is arranged between the first gas barrier film and the heat-sealable film.

The first resin substrate is usually arranged so as to face the heat-sealable film. The first resin base material is not particularly limited as long as it can support the first inorganic layer described later. Specifically, the same materials as exemplified in "5. Resin base material" can be used.
The first inorganic layer and the inorganic layered compound layer are the same as those exemplified in "1. Inorganic layer" and "2. Inorganic layered compound layer", respectively.

(2) Second gas barrier film The second gas barrier film in this embodiment is arranged on the main surface side opposite to the heat-sealable film of the first gas barrier film, and comprises the second resin substrate and the second gas barrier film. and an inorganic layer, and the second inorganic layer is arranged so as to face the inorganic layered compound layer of the first gas barrier film.

Examples of the second resin base material include those exemplified in "5. Resin base material" described above. Examples of the second inorganic layer include those exemplified in “1. Inorganic layer”.

The second gas barrier film may have an overcoat layer on the main surface of the second inorganic layer opposite to the second resin substrate. In this embodiment, since the inorganic layered compound layer in the first gas barrier film is arranged to face the second inorganic layer in the second gas barrier film, the inorganic layered compound layer and the second inorganic layer are separated from each other. , in direct contact or through an overcoat layer or adhesive layer as described above. Examples of the overcoat layer and the adhesive layer include those exemplified in "5. Overcoat layer" and "6. Adhesive layer" described above.

Moreover, between the heat-weldable film and the first gas barrier film, between the first gas barrier film and the second gas barrier film, between the second gas barrier film and the third gas barrier film, etc. Layers can be laid.
Examples of the adhesive layer include those exemplified in "6. Adhesive layer" described above.

(3) Other Gas Barrier Films The outer packaging material for a vacuum heat insulating material of the present embodiment has at least a first gas barrier film and a second gas barrier film, and preferably has one or more layers of gas barrier films. Among them, it is preferable that the outer packaging material for a vacuum insulation material of the present disclosure has three layers of gas barrier films. Specifically, as shown in FIG. 1, a first gas barrier film 2a and a second gas barrier film 2b In addition, it is preferable to have a third gas barrier film 2c. This is because gas barrier properties can be improved when the gas barrier film has three layers. The gas barrier film may be provided with four or more layers, but if the layer structure is increased, the productivity may be low and the flexibility may be decreased.

The third gas barrier film is not particularly limited as long as it does not contain a metal layer. 3 inorganic layers. Examples of the third resin base material and the third inorganic layer include those exemplified in the above-mentioned "5. Resin base material" and "1. Inorganic layer".

As the third inorganic layer, among others, an inorganic compound film made of aluminum oxide (alumina) or silicon oxide (silica) is preferable. Although the thickness of the third inorganic layer is not particularly limited, it is preferably 50 nm or less. By setting the thickness of the third inorganic layer to the above value or less, the flexibility can be sufficiently maintained, and the barrier breakage is less likely to occur. In addition, the second gas barrier film and the third gas barrier film included in the outer packaging material for a vacuum insulation panel of the present disclosure may be the same, or may differ in type, layer structure, material, and the like.

Although the position of the third inorganic layer in the third gas barrier film is not particularly limited, it is usually arranged so that the third inorganic layer is closer to the second gas barrier film than the third resin substrate.

(Second embodiment)
In the present disclosure, the outer wrapping material of the second embodiment as illustrated in FIG. 3 is also preferred. In the outer wrapping material of the second embodiment, the resin base material 3 of the second gas barrier film 2b in the outer wrapping material of the first embodiment shown in FIG. 1 faces the inorganic layered compound layer 5 of the first gas barrier film 2a. It is the same as the first embodiment except that it is arranged as follows. That is, in this embodiment, at least the second resin base material 3 is interposed between the inorganic layered compound layer 5 in the first gas barrier film and the second inorganic layer 4 in the second gas barrier film 2b, A first inorganic layer 4, an inorganic stratiform compound layer 5, a resin base material 3, and a second inorganic layer 4 are included in this order from the heat-sealable film 1 side in the outer packaging material 10 for a vacuum heat insulating material. .

Such a second embodiment specifically includes the following aspects.
That is, a heat-weldable film, a first resin substrate, a first inorganic layer, an inorganic layered compound layer, a second resin substrate, a second inorganic layer, a third inorganic layer, and the third resin base material are arranged in this order.

Examples of the first gas barrier film and the second gas barrier film of the present embodiment include those similar to the first gas barrier film and the second gas barrier film exemplified in the first embodiment.

The outer packaging material for a vacuum heat insulating material of this embodiment has at least a first gas barrier film and a second gas barrier film, and preferably has one or more layers of gas barrier films. Above all, it is preferable that the outer packaging material for a vacuum insulation material of the present embodiment has three layers of gas barrier films. Specifically, as shown in the example of FIG. 3, a first gas barrier film 2a and a second gas barrier film. In addition to 2b, it is preferable to have a third gas barrier film 2c. This is because gas barrier properties can be improved when the gas barrier film has three layers. The gas barrier film may be provided with four or more layers, but if the layer structure is increased, the productivity may be low and the flexibility may be decreased. Other gas barrier films of the present embodiment include those similar to the other gas barrier films exemplified in the first embodiment.

The adhesive layer is provided between the heat-sealable film and the first gas barrier film, between the first gas barrier film and the second gas barrier film, between the second gas barrier film and the third gas barrier film, and the like. can be located. Examples of the adhesive layer include those exemplified in "6. Adhesive layer" described above.

(Third embodiment)
In the present disclosure, the outer wrapping material of the third embodiment illustrated in FIG. 4 is also preferred. The outer packaging material 10 for a vacuum heat insulating material of the present embodiment includes at least a heat-weldable film 1 having an inorganic layer 4 (first inorganic layer) provided on its main surface, and a first gas barrier film 2a. The gas barrier film 2a of 1 has at least a resin substrate 3, an inorganic layer 4 (second inorganic layer), and an inorganic layered compound layer 5, and the inorganic layered compound layer 5 is formed on the heat-weldable film 1. It is arranged so as to face the provided first inorganic layer 4 .

Such a third embodiment specifically includes the following aspects.
That is, a heat-weldable film, a first inorganic layer, an inorganic layered compound layer, a second inorganic layer, a second resin substrate, a third inorganic layer, a third resin substrate, are arranged in this order.

In this embodiment, the inorganic layered compound layer 5 in the first gas barrier film is composed of the first inorganic layer 4 provided on one main surface of the heat-weldable film 1 and the second inorganic layer 4. A first inorganic layer 4, an inorganic stratiform compound layer 5, and a second inorganic layer 4 are included in the outer packaging material 10 for a vacuum heat insulating material in this order from the heat-sealable film 1 side disposed therebetween. ing.

Examples of the first gas barrier film of the present embodiment include those similar to the first gas barrier film of the first embodiment. It is arranged so as to face the first inorganic layer provided thereon. Examples of the inorganic layer provided on one main surface of the heat-sealable film include those exemplified in "1. Inorganic layer". The heat-sealable film provided with such an inorganic layer also has a function as a gas barrier film, and known barrier sealants used for outer packaging materials can be used. Specifically, an unstretched polypropylene film or the like provided with an inorganic deposition layer can be used.

The outer packaging material for a vacuum heat insulating material of the present embodiment has at least a heat-sealable film provided with an inorganic layer (first inorganic layer) and a first gas barrier film, and in addition, one or more gas barrier layers. It is preferred to have a film. Above all, as shown in FIG. 4, it is preferable that the outer wrapping material for a vacuum heat insulating material of this embodiment has a second gas barrier film 2b in addition to the first gas barrier film 2a. The configuration of the other gas barrier film of this embodiment is the same as that of the other gas barrier film described in the first embodiment.

In this embodiment, the adhesive layer is positioned between the heat-weldable film provided with the inorganic layer and the first gas barrier film, between the first gas barrier film and the second gas barrier film, and the like. can do. Examples of the adhesive layer include those exemplified in "6. Adhesive layer" described above.

8. Properties The outer packaging material for vacuum insulation panels of the present disclosure has excellent gas barrier performance. Gas barrier performance refers to oxygen barrier performance defined by oxygen permeability and water vapor barrier performance defined by water vapor permeability.

In particular, the outer packaging material for a vacuum insulation material of the present disclosure has an oxygen permeability of, for example, 0.1 cc/(m ² ·day · atm) or less, especially 0.05 cc, even though no metal layer is arranged. /(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, Annex A: Oxygen gas permeability test method by electrolytic sensor method) , using an oxygen gas permeation measuring device 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, USA can be used. The measurement was performed by cutting the outer wrapping material to a desired size, and of the two outermost layers facing each other in the thickness direction, the surface of the outermost layer on the side opposite to the heat-sealable film, which is one of the outermost layers, was oxygenated. It was mounted in the above apparatus so as to be in contact with the gas, with a permeation area of about 50 cm ² (permeation area: a circle with a diameter of 8 cm), and the conditions of the carrier gas and the test gas were measured at a temperature of 23°C and a humidity of 60% RH. conduct. During the measurement, a carrier gas is supplied into the apparatus at a flow rate of 10 cc/min for 60 minutes or more to purge the apparatus. Nitrogen gas containing about 5% hydrogen can be used as the carrier gas. After purging, the test gas is allowed to flow through the apparatus, and measurements are taken after 12 hours have been secured from the start of the flow until reaching the equilibrium state. The test gas uses at least 99.5% dry oxygen. Oxygen permeability is measured for at least three samples under one condition, and the average of the measured values is taken as the value of oxygen permeability under that condition.

In addition, the outer packaging material for a vacuum heat insulating material of the present disclosure preferably has a water vapor permeability of, for example, 0.02 g/(m ² ·day) or less, especially 0.01 g/(m ² ·day) or less. This is because an outer wrapping material having such a water vapor permeability can maintain heat insulating performance for a long period of time when used as a vacuum heat insulating material. The water vapor transmission rate can be a value measured under conditions of a temperature of 40° C. and a relative humidity difference of 90% RH in accordance with ISO 15106-5:2015 (differential pressure method).

The water vapor transmission rate can be measured by the following procedure. First, a sample of the outer wrapping material cut to a desired size was cut into a desired size, and among the outermost surfaces facing each other in the thickness direction (laminating direction), the outermost surface layer located on the opposite side of the heat-sealable film, which is one of the outermost surface layers, was ^It is installed between the upper chamber and the lower chamber of the above apparatus so that it is on the high humidity side (water vapor supply side). Measurement is performed under the condition of RH difference of 90%. For example, "DELTAPERM" manufactured by Technolox, UK can be used as the water vapor transmission rate measuring device.

Since the outer packaging material for a vacuum heat insulating material according to the present disclosure does not have a metal layer disposed thereon, it has radio wave transparency. Here, having radio wave permeability is not particularly limited as long as the equipment in the compartment covered with the vacuum insulation material has radio wave permeability to the extent that it can be contacted by radio waves with the outside. For example, it is preferable that the electromagnetic wave shielding property in the range of 300 MHz to 30 GHz is 10 dB or less. As a method for measuring radio wave permeability, far-field measurement can be used. Specifically, a transmitting antenna is placed in one anechoic chamber, and a receiving antenna is placed in the other anechoic chamber.

The outer packaging material for vacuum insulation material of the present disclosure may or may not have transparency, and is appropriately set according to the application of the vacuum insulation material for which the outer packaging material for vacuum insulation material of the present disclosure is used. can do. The transparency of the outer packaging material for a vacuum heat insulating material is not strictly defined by the transmittance, and can be appropriately determined depending on the application.

When the outer wrapping material for a vacuum heat insulating material of the present disclosure has transparency, the inside of the vacuum heat insulating material using the outer wrapping material for a vacuum heat insulating material can be visually recognized. Therefore, by putting the detecting agent together with the core material inside the vacuum heat insulating material, it is possible to visually confirm the internal vacuum state from changes in the detecting agent.

As a method for manufacturing the outer packaging material for a vacuum heat insulating material of the present disclosure, for example, there is a method in which pre-manufactured films are pasted together via the above-described adhesive layer. Alternatively, the outer packaging material for the vacuum heat insulating material of the present disclosure may be manufactured by sequentially extruding and laminating the heat-melted raw materials of each film using a T-die or the like.

The outer wrapping material for a vacuum insulation panel of the present disclosure can be used for a vacuum insulation panel. In a vacuum heat insulating material, the outer packaging material for a vacuum heat insulating material of the present disclosure can be used by arranging them facing each other with the core material interposed therebetween, with the heat-sealable film facing the core material.

B. Vacuum insulation material The vacuum insulation material of the present disclosure is a vacuum insulation material having a core material and an outer wrapping material that encloses the core material, wherein the outer wrapping material is the above-described "A. outer wrapping material for vacuum insulation material". It is characterized by being what was explained in the paragraph.

FIG. 2(a) is a schematic perspective view showing an example of the vacuum heat insulating material of the present disclosure, and FIG. 2(b) is a cross-sectional view taken along line XX of FIG. 2(a). A vacuum heat insulating material 20 illustrated in FIG. 2 has a core material 11 and an outer wrapping material 10 that encloses the core material 11. The outer wrapping material 10 is the vacuum heat insulating outer wrapping material described in FIG. The vacuum heat insulating material 20 is a bag body in which two outer wrapping materials 10 face each other so that the heat-sealable films face each other, and the ends 12 are joined by heat welding. The core material 11 is enclosed, and the inside of the bag is decompressed.

According to the present disclosure, the outer wrapping material that encloses the core material is the outer wrapping material for the vacuum heat insulating material described in the above section "A. outer wrapping material for the vacuum heat insulating material", so that it has radio wave transparency, It becomes a vacuum heat insulating material that can maintain good heat insulating performance.
Hereinafter, the vacuum heat insulating material of the present disclosure will be described for each configuration.

1. Outer wrapping material The outer wrapping material in the present disclosure is a member that encloses the core material, and is the same as the outer wrapping material for the vacuum heat insulating material described in the above section "A. Outer wrapping material for vacuum heat insulating material". Description is omitted.

2. Core material The core material in the present disclosure is a member enclosed by the outer wrapping material. Note that "enclosed" means to be sealed inside a bag formed using an outer wrapping material.

The core material preferably has low thermal conductivity. Also, the core material can be a porous material having a porosity of 50% or more, particularly 90% or more.

Powders, foams, fibers, and the like can be used as the material constituting the core material. The powder may be inorganic or organic, and for example, dry silica, wet silica, agglomerated silica powder, conductive powder, calcium carbonate powder, perlite, clay, talc and the like can be used. Among them, a mixture of dry silica and conductive powder is advantageous when used in a temperature range where the internal pressure rises, because the heat insulating performance of the vacuum heat insulating material does not deteriorate as the internal pressure rises. Furthermore, by adding a substance having a low infrared absorptance, such as titanium oxide, aluminum oxide, or indium-doped tin oxide, to the above material as a radiation suppressing material, the infrared absorptance of the core material can be reduced.

Urethane foam, styrene foam, phenol foam, or the like can be used as the foam. Among them, a foam that forms open cells is preferable.

The fibrous body may be inorganic fibers or organic fibers, but inorganic fibers are preferably used from the viewpoint of heat insulation performance. Examples of such inorganic fibers include glass fibers such as glass wool and glass fibers, alumina fibers, silica-alumina fibers, silica fibers, ceramic fibers, and rock wool. These inorganic fibers are preferable in that they have low thermal conductivity and are easier to handle than powder.

The core material may be one of the materials described above, or may be a composite material in which two or more materials are mixed.

3. Others In the vacuum heat insulating material of the present disclosure, the core material is sealed inside the outer wrapping material, and the inside is decompressed to be 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 due to convection of air remaining inside can be reduced, and excellent heat insulating properties can be exhibited.

The lower the thermal conductivity of the vacuum heat insulating material, the better. For example, the thermal conductivity (initial thermal conductivity) is preferably 5 mW/(mK) or less. This is because the vacuum heat insulating material is less likely to conduct heat to the outside, and a high heat insulating effect can be achieved. Above all, the initial thermal conductivity is more preferably 4 mW/(mK) or less. The thermal conductivity can be a value measured in accordance with JIS A1412-2:1999 under conditions of a high temperature side of 30°C, a low temperature side of 10°C, and an average temperature of 20°C.

In addition, since the vacuum heat insulating material of the present disclosure uses the outer wrapping material described above, deterioration in heat insulating performance is suppressed.
Furthermore, when vacuum insulation materials are used for items that require content identification and traceability, such as containers in logistics, vacuum insulation materials are not only radio-wave transparent, but also have high thermal insulation properties due to their thin plate thickness and low pressure on storage space. expected to perform. With the vacuum heat insulating material of the present disclosure, the gas barrier film of the outer packaging material has two or three layers, and high heat insulating performance as well as radio wave transmission can be exhibited, so the vacuum heat insulating material can be made thin.

A general method can be used for the method of manufacturing the vacuum heat insulating material of the present disclosure. For example, prepare two sheets of the vacuum insulation outer packaging material described in the above section "A. Vacuum insulation outer packaging material", put the respective heat-sealable films facing each other, and wrap the outer edges of the three sides. To obtain a bag which is heat-sealed and one side of which is open. A vacuum heat insulating material can be obtained by putting a core material into this bag through an opening, sucking air through the opening, and sealing the opening while the inside of the bag is decompressed.

The vacuum insulation material of the present disclosure can be used, for example, in articles requiring thermal insulation and radio wave transparency. The article will be described later.

C. Article with Vacuum Insulation Material The article with vacuum insulation material of the present disclosure is an article with a vacuum insulation material having a heat insulation region and an article with a vacuum insulation material comprising a vacuum insulation material, wherein the vacuum insulation material includes a core material and a core material enclosed The outer wrapping material is the vacuum heat insulating material outer wrapping material described in the above section "A. Vacuum heat insulating material outer wrapping material".

According to the present disclosure, since the vacuum heat insulating material used for the article is composed of the outer wrapping material described in the section "A. outer wrapping material for vacuum heat insulating material", the vacuum heat insulating material has good heat insulating performance for a long period of time. can be exhibited, and when an article is provided with such a vacuum heat insulating material, it is possible to achieve energy saving in an article in a high-temperature and high-humidity environment or an object in which the article is used. In addition, since the vacuum heat insulating material can transmit radio waves, it is possible to identify and trace the contents of the article.

The vacuum heat insulating material and the outer wrapping material used therefor in the present disclosure have been described in detail in the above-mentioned sections "B. Vacuum heat insulating material" and "A. outer wrapping material for vacuum heat insulating material", so the description here is omitted. do.

Articles in the present disclosure have regions of thermal insulation. Here, the thermally insulated region is a region thermally insulated by a vacuum insulation material, and includes, for example, a heat-retained or cold-insulated region, a region surrounding a heat source or a cooling source, or a region isolated from a heat source or a cooling source. is. These regions can be space or objects. Moreover, the article is preferably an article that requires radio wave transparency.

Examples of the above-mentioned goods include electrical equipment such as refrigerators, freezers, heat insulators, cold insulators, etc.; buildings, wall materials, building materials such as floor materials, and the like.

The present disclosure is not limited to the above embodiments. The above embodiment is an example, and any device that has substantially the same configuration as the technical idea described in the claims of the present disclosure and achieves the same effect is the present invention. It is included in the technical scope of the disclosure.

Examples and comparative examples are shown below to describe the present disclosure in more detail.

[material]
The members and adhesives constituting the outer packaging materials for vacuum insulation panels of Examples and Comparative Examples are shown below and in Table 1.
(Component: gas barrier film)
・ Gas barrier film A: A film obtained by depositing a silicon oxide film on one side of a nylon film (thickness: 15 μm) and providing the following overcoat layer A on the deposited film (manufactured by Dai Nippon Printing Co., Ltd. (trade name: IB-ON -UB))

・Gas barrier film B: A film (manufactured by Dai Nippon Printing Co., Ltd. (trade name: IB-PET -UB))

・ Gas barrier film C: Montmorillonite (manufactured by Kunimine Industries Co., Ltd.: Kunipia F) and PVA (polyvinyl alcohol) ( A film provided with an inorganic layered compound layer (thickness: 240 nm) containing JF-04, saponification degree 98-99%, average polymerization degree 400) manufactured by Japan Vinyl Acetate & Poval Co., Ltd.

(Formation method)
First, PVA (polyvinyl alcohol) granules (manufactured by Nippon Acetate & Poval Co., Ltd.: JF-04, saponification degree 98-99%, average polymerization degree 400) are dissolved in ion-exchanged water, and 20% by mass of polyvinyl alcohol An aqueous alcohol solution was obtained. Montmorillonite (manufactured by Kunimine Industries Co., Ltd.: Kunipia F) was added to this aqueous solution so as to be 10% by mass of the solid mass, and the mixture was stirred to prepare an inorganic layered compound-containing coating solution.

Next, the inorganic layered compound-containing coating solution is coated on the alumina film by gravure coating, and then heat-treated at 120° C., 140° C. and 150° C. for 20 seconds each to obtain an inorganic coating solution on the metal aluminum film. A layered compound film was formed.

・Gas barrier film D: A film (manufactured by Dai Nippon Printing Co., Ltd. (trade name: IB-PET-PXB ))
Gas barrier film E: polyethylene terephthalate film having a transparent gas barrier film on one side (Kuraray Co., Ltd. Claristar CF, thickness 12 μm)

・Gas barrier film F: A film (manufactured by Dai Nippon Printing Co., Ltd. (trade name: IB-PET-PIR2 ))
・Gas barrier film G: Nylon film (manufactured by Unitika Ltd., Emblem ONBC, film thickness 25 μm)
・Gas barrier film H: Ethylene-vinyl alcohol copolymer (EVOH) film with a metal aluminum (Al) film deposited on one side (VM-XL manufactured by Kuraray Co., Ltd., thickness 12 μm)

・ Gas barrier film I: ethylene-vinyl alcohol copolymer (EVOH) film (EF-F manufactured by Kuraray Co., Ltd., thickness 12 μm)
・ Gas barrier film J: A film in which a metal aluminum film is deposited on one side of a PET film (thickness: 12 μm) (VM-PET1519 manufactured by Toray Advanced Film Co., Ltd.)
・Gas barrier film K: A film obtained by depositing a silicon oxide film on one side of a PET film (thickness: 12 μm) and providing the following overcoat layer A on the deposited film.

(overcoat layer)
・Overcoat layer A
Liquid B (tetraethoxysilane (TEOS), isopropyl alcohol, hydrochloric acid and ion-exchanged water) prepared in advance according to the composition shown below is added to liquid A (mixture of polyvinyl alcohol, isopropyl alcohol and water) prepared according to the composition shown below. A hydrolyzed solution consisting of the above) was added and stirred to obtain a colorless and transparent overcoat layer composition by a sol-gel method.
The overcoat layer composition was coated on the gas barrier film to be coated by gravure coating, and then heat-treated at 120° C., 140° C. and 150° C. for 20 seconds each to obtain the required thickness. An overcoat layer was formed and aged at 55° C. for 1 week to obtain an overcoat layer A which is a mixed compound layer containing silicon element, oxygen element and polyvinyl alcohol resin.

<Composition of composition for overcoat layer>
(A liquid)
・Polyvinyl alcohol: 1.81% by mass
・Isopropyl alcohol: 39.80% by mass
・Water: 2.09% by mass
(B liquid)
・ 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
(* A liquid and B liquid were combined and set to 100% by mass)

(Component: heat-sealable film)
・ Heat-weldable film A: Linear low-density polyethylene film (trade name: TUX HC-E manufactured by Mitsui Chemicals Tocello, thickness 50 μm)

(glue)
Adhesive A: Main agent mainly composed of polyester polyol (product name: RU-77T manufactured by Rock Paint Co., Ltd.), curing agent containing aliphatic isocyanate (product name manufactured by Rock Paint Co., Ltd.: H-7), and ethyl acetate A two-component curing adhesive in which the solvent is mixed so that the weight ratio of the main agent: curing agent: solvent = 10: 1: 14

(Preparation of outer wrapping material for vacuum insulation material)
[Example 1]
An outer wrapping material was obtained which had the gas barrier film A as the first layer, the gas barrier film B as the second layer, the gas barrier film C as the third layer, and the heat-sealable film A as the fourth layer in this order. The vapor-deposited film (inorganic layer) of the gas barrier film B as the second layer was arranged so as to face the inorganic layered compound layer of the gas barrier film C as the third layer via the overcoat layer. That is, the inorganic layer of gas barrier film B, the inorganic layered compound layer of gas barrier film C, and the inorganic layer of gas barrier film C were arranged in this order. The first layer was arranged so that the vapor-deposited film was located on the film A side, which can be thermally welded, rather than the resin substrate. Between each layer, the adhesive A is applied to the adherend surface of one member so that the coating amount is 3 g/m ² to form an adhesive layer, and the other member is placed on the adhesive layer and pressed to adhere. bottom.

[Example 2]
An outer wrapping material was obtained which had the gas barrier film D as the first layer, the gas barrier film D as the second layer, the gas barrier film C as the third layer, and the heat-sealable film A as the fourth layer in this order. The vapor-deposited film (inorganic layer) of the gas barrier film D as the second layer was arranged so as to face the layered inorganic compound layer of the gas barrier film C as the third layer via the overcoat layer. That is, the inorganic layer of gas barrier film D, the inorganic layered compound layer of gas barrier film C, and the inorganic layer of gas barrier film C were arranged in this order. The first layer was arranged so that the vapor-deposited film was located on the film A side, which can be thermally welded, rather than the resin substrate. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Example 3]
An outer wrapping material was obtained which had the gas barrier film E as the first layer, the gas barrier film D as the second layer, the gas barrier film C as the third layer, and the heat-sealable film A as the fourth layer in this order. The vapor-deposited film (inorganic layer) of the gas barrier film D as the second layer was arranged so as to face the layered inorganic compound layer of the gas barrier film C as the third layer via the overcoat layer. That is, the inorganic layer of gas barrier film D, the inorganic layered compound layer of gas barrier film C, and the inorganic layer of gas barrier film C were arranged in this order. The first layer was arranged so that the gas barrier film was on the side of the heat-sealable film A rather than the resin substrate. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Example 4]
An outer wrapping material was obtained which had the gas barrier film F as the first layer, the gas barrier film D as the second layer, the gas barrier film C as the third layer, and the heat-sealable film A as the fourth layer in this order. The vapor-deposited film (inorganic layer) of the gas barrier film D as the second layer was arranged so as to face the layered inorganic compound layer of the gas barrier film C as the third layer via the overcoat layer. That is, the inorganic layer of gas barrier film D, the inorganic layered compound layer of gas barrier film C, and the inorganic layer of gas barrier film C were arranged in this order. The first layer was arranged so that the vapor-deposited film was located on the film A side, which can be thermally welded, rather than the resin substrate. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 1]
An outer wrapping material was obtained, which had the gas barrier film A as the first layer, the gas barrier film D as the second layer, the gas barrier film H as the third layer, and the heat-sealable film A as the fourth layer in this order. The vapor-deposited film (inorganic layer) of the gas barrier film D as the second layer is arranged so as to face the vapor-deposited film of the gas barrier film H as the third layer via the overcoat layer, and the vapor-deposited film of the first layer is a resin base. It was arranged so as to be on the film A side that can be heat-sealed rather than the material. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 2]
An outer wrapping material was obtained which had Gas Barrier Film A as the first layer, Gas Barrier Film B as the second layer, Gas Barrier Film I as the third layer, and Heat-Sealable Film A as the fourth layer in this order. The vapor-deposited film (inorganic layer) of the second layer gas barrier film B is disposed so as to face the third layer gas barrier film I side via the overcoat layer, and the vapor-deposited film of the first layer is located above the resin base material. was arranged so as to be on the film A side which can be heat-sealed. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 3]
An outer packaging material was obtained which had the gas barrier film G as the first layer, the gas barrier film B as the second layer, the gas barrier film K as the third layer, and the heat-sealable film A as the fourth layer in this order. The overcoat layer of the gas barrier film B as the second layer was arranged so as to face the overcoat layer of the gas barrier film K as the third layer. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 4]
An outer wrapping material was obtained which had the gas barrier film A as the first layer, the gas barrier film B as the second layer, the gas barrier film K as the third layer, and the heat-sealable film A as the fourth layer in this order. The overcoat layer of the gas barrier film B, which is the second layer, is arranged so as to face the overcoat layer of the gas barrier film K, which is the third layer. placed on the side. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 5]
An outer wrapping material was obtained which had the gas barrier film A as the first layer, the gas barrier film D as the second layer, the gas barrier film K as the third layer, and the heat-sealable film A as the fourth layer in this order. The overcoat layer of the gas barrier film D, which is the second layer, is arranged so as to face the overcoat layer of the gas barrier film K, which is the third layer, and the vapor-deposited film of the first layer is the film A that can be heat-sealed rather than the resin substrate. placed on the side. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 6]
An outer wrapping material was obtained which had the gas barrier film F as the first layer, the gas barrier film J as the second layer, the gas barrier film H as the third layer, and the heat-sealable film A as the fourth layer in this order. The vapor-deposited film of the gas barrier film J as the second layer is arranged so as to face the vapor-deposited film of the gas barrier film H as the third layer. placed so that Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 7]
An outer packaging material was obtained which had the gas barrier film D as the first layer, the gas barrier film D as the second layer, the gas barrier film D as the third layer, and the heat-sealable film A as the fourth layer in this order. The overcoat layer of the gas barrier film D as the second layer is arranged so as to face the overcoat layer as the third layer, and the vapor-deposited film of the first layer is positioned on the film A side, which can be thermally welded, rather than the resin substrate. placed in Each layer was adhered with an adhesive layer in the same manner as in Example 1.

(oxygen permeability)
A sample was taken out from each of the outer wrapping materials obtained in Examples 1 to 4 and Comparative Examples 1 to 7, and was subjected to a temperature of 23° C., a temperature of 23° C., and a The oxygen permeability was measured at a humidity of 60% RH. The results are shown in Oxygen permeability (flat) in Table 2.
Further, a rectangular test piece of 210 mm width×297 mm length (A4 size) was taken from each of the outer wrapping materials obtained in Examples 1 to 4 and Comparative Examples 1 to 7. In accordance with ASTM F392, each test piece was subjected to bending treatment three times using a Gelboflex tester (manufactured by Tester Sangyo Co., Ltd., model name: BE1006).
For each test piece after flexing three times, the oxygen permeability was measured at a temperature of 23 ° C. and a humidity of 60% RH by the method and conditions described in the section "A. Outer wrapping material for vacuum insulation material VI. Characteristics". (Oxygen permeability after bending treatment) was measured. The results are shown in Oxygen permeability (after bending) in Table 2.

(Production of vacuum insulation material)
Two outer packaging materials (dimensions: 360 mm × 450 mm) obtained in Examples 1 to 4 and Comparative Examples 1 to 7 were prepared, and the heat-sealable films were placed facing each other to form a quadrilateral triangle. A bag having only one side opened was prepared by heat-sealing the sides. Glass wool of 300 mm × 300 mm × 30 mm was used as the core material, and after drying treatment, the core material and the outer wrapping materials of Example 1 and Comparative Examples 1 to 5 were used in the bag. Calcium oxide) was contained therein, and 10 g of desiccant (calcium oxide) was contained in the outer packaging materials of Examples 2 to 4 and Comparative Examples 6 and 7, and the inside of the bag was evacuated. After that, the opening of the bag was sealed by heat sealing to obtain a vacuum heat insulating material. The ultimate pressure was set to 0.05 Pa.

(Heat conductivity of vacuum insulation material)
The thermal conductivity of the vacuum insulation material was measured according to the method and conditions described in the above section "II. Vacuum insulation material". Measurements were taken at the initial stage, after a deterioration test at 100° C. for 500 hours, and after a deterioration test at 70° C. and 90% RH for 500 hours. Tables 2 and 3 show the results.

As shown in Tables 2 and 3, the vacuum insulation materials (Examples 1 to 4) having the outer packaging material for vacuum insulation materials of the present disclosure have radio wave permeability and can maintain heat insulation performance for a long period of time. became possible. On the other hand, the outer wrapping materials of Comparative Examples 1 and 6 have no radio wave transmittance due to having a metal layer, and the outer wrapping materials of Comparative Examples 2 to 5 and 7 are inferior in gas barrier properties after bending treatment, and these were used. Vacuum insulation could not maintain good insulation performance.

DESCRIPTION OF SYMBOLS 1... Heat-sealable film 2... Gas barrier film 3... Resin base material 4... Inorganic layer 5... Inorganic layered compound layer 10... Outer packaging material for vacuum heat insulating material 11... Core material 20... Vacuum heat insulating material

Claims (10)

An outer packaging material for a vacuum heat insulating material, comprising a heat-sealable film and two or more inorganic layers including a first inorganic layer and a second inorganic layer,
The outer packaging material for a vacuum heat insulating material further includes an inorganic layered compound layer containing an inorganic layered compound and a binder resin,
The first inorganic layer, the inorganic layered compound layer, and the second inorganic layer are arranged in this order,
The binder resin is polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyacrylic acid or its salt, polybenzenesulfonic acid or its salt, polyethyleneimine, polyallylamine, polyglycerin, hydroxymethylcellulose, hydroxyl at least one resin selected from the group consisting of ethyl cellulose, carboxymethyl cellulose, amylose, amylopectin, curdlan, xanthan, chitin, cellulose, pullulan, and chitosan;
An outer wrapping material for a vacuum heat insulating material in which no metal layer is arranged. 2. The outer packaging material for a vacuum heat insulating material according to claim 1, wherein no resin substrate is disposed between said inorganic layered compound layer and said first inorganic layer and said second inorganic layer. The vacuum according to claim 1, wherein the heat-weldable film, the resin base material, the first inorganic layer, the inorganic layered compound layer, and the second inorganic layer are arranged in this order. Outer wrapping material for thermal insulation. The heat-weldable film, the first resin substrate, the first inorganic layer, the layered inorganic compound layer, the second inorganic layer, and the second resin substrate are arranged in this order. 2. The outer packaging material for a vacuum heat insulating material according to claim 1. 5. The outer packaging material for a vacuum heat insulating material according to claim 4, wherein a third inorganic layer and a third resin base material are arranged in this order on the surface of the second resin base material opposite to the second inorganic layer. . The heat-sealable film, the first resin substrate, the first inorganic layer, the layered inorganic compound layer, the second resin substrate, the second inorganic layer, and the third inorganic layer and the third resin base material are arranged in this order. The heat-weldable film, the first inorganic layer, the layered inorganic compound layer, the second inorganic layer, the second resin substrate, the third inorganic layer, and the third resin substrate , and are arranged in this order. A vacuum insulation material having a core material and an outer wrapping material in which the core material is enclosed,
A vacuum heat insulating material, wherein the outer wrapping material is the outer wrapping material for a vacuum heat insulating material according to any one of claims 1 to 7. An article having a thermally insulated region and an article with vacuum insulation, comprising:
The vacuum insulation material has a core material and an outer wrapping material in which the core material is enclosed,
An article with a vacuum insulation material, wherein the outer packaging material is the outer packaging material for a vacuum insulation material according to any one of claims 1 to 7. 10. The article with a vacuum insulation material according to claim 9, wherein the article with a vacuum insulation material has radio wave transparency.

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