WO2020262462A1

WO2020262462A1 - Outer packaging member for vacuum heat-insulating member, vacuum heat-insulating member, and article provided with vacuum heat-insulating member

Info

Publication number: WO2020262462A1
Application number: PCT/JP2020/024838
Authority: WO
Inventors: 琢棟田; 将博今井
Original assignee: 大日本印刷株式会社
Priority date: 2019-06-24
Filing date: 2020-06-24
Publication date: 2020-12-30
Also published as: JP2022000591A; JP7247235B2; JPWO2020262462A1

Abstract

The present disclosure provides an outer packaging member (10) for a vacuum heat-insulating member, the outer packaging member having a heat-weldable film (1), and two or more inorganic layers (4) including a first inorganic layer and a second inorganic layer, wherein: the outer packaging member furthermore includes an inorganic-layer-type compound layer (5) that contains an inorganic-layer-type compound and a binder; the first inorganic layer, the inorganic-layer-type compound layer, and the second inorganic layer are positioned in the stated order, a metal layer not being positioned. Due to providing such an outer packaging member for a vacuum heat-insulating member, the present invention provides: an outer packaging member for a vacuum heat-insulating member that makes it possible to manufacture a vacuum heat-insulating member that can transmit electrical waves and maintain an excellent heat-insulation function; and a vacuum heat-insulating member and an article provided with a vacuum heat-insulating member in which the outer packaging member for a vacuum heat-insulating member is used.

Description

Outer packaging material for vacuum heat insulating material, vacuum heat insulating material, and articles with vacuum heat insulating material

The present disclosure relates to an outer packaging material for a vacuum heat insulating material, a vacuum heat insulating material, and an article with the vacuum heat insulating material capable of forming the vacuum heat insulating material.

In recent years, vacuum heat insulating materials have been used for the purpose of saving energy in articles. The vacuum heat insulating material is a member in which the core material is arranged inside the bag of the outer packaging material and the inside of the bag is held in a vacuum state where the pressure is lower than the atmospheric pressure, and the internal heat convection is suppressed, which is good. Can demonstrate excellent heat insulation performance. The outer packaging material used for the vacuum heat insulating material will be described as an outer packaging material for the vacuum heat insulating material, or simply an outer packaging material.

The outer packaging material for the vacuum heat insulating material has gas barrier performance to suppress the permeation of gas such as oxygen and steam in order to maintain the vacuum state inside the vacuum heat insulating material for a long period of time, and the ends are joined when wrapping the core material. Therefore, physical properties such as heat-welding property for sealing and sealing the core material are required. In order to satisfy these physical properties, the outer packaging material for the vacuum heat insulating material is generally configured to include a gas barrier film and a heat-weldable film as members.

The general vacuum heat insulating material outer packaging material uses a metal foil or a metal vapor deposition layer for the gas barrier film. For example, Patent Document 1 describes an outer packaging material using an 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 packaging material.

Japanese Unexamined Patent Publication No. 2003-262296 WO2013 / 125564

In recent years, since it is used for heat insulating boxes used in physical distribution, vacuum heat insulating materials that can transmit radio waves are required for the purpose of identification and traceability of contents. However, since the outer packaging material used for the conventional vacuum heat insulating material generally contains a metal foil or a metal vapor deposition layer, there is a problem that it blocks radio waves and is not suitable for applications requiring wireless communication inside and outside the space. It was.

The present disclosure is an invention made in view of the above problems, 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, and a vacuum using the same. The main purpose is to provide the heat insulating material and the article with the vacuum heat insulating material.

The present disclosure is an outer packaging material for a vacuum heat insulating material having a heat-weldable film and two or more inorganic layers including a first inorganic layer and a second inorganic layer. Further, the first inorganic layer, the inorganic layered compound layer, and the second inorganic layer are arranged in this order, including the inorganic layered compound layer containing the inorganic layered compound and the binder resin, and the metal layer is formed. Provided an outer packaging material for vacuum insulation which is not arranged.

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

Further, the present disclosure is an article having a heat insulating region and an article with a vacuum heat insulating material provided with the vacuum heat insulating material, and the vacuum heat insulating material has a core material and an outer packaging material in which the core material is enclosed. Provided is an article with a vacuum heat insulating material, wherein the outer packaging material is the above-mentioned vacuum heat insulating outer packaging material.

According to the present disclosure, it is possible to provide an outer packaging material for a vacuum heat insulating material capable of producing a vacuum heat insulating material capable of transmitting radio waves and maintaining good heat insulating performance.

It is the schematic sectional drawing which shows an example of the external packaging material for a vacuum heat insulating material of this disclosure. It is a schematic perspective view and sectional view which shows an example of the vacuum heat insulating material of this disclosure. It is the schematic sectional drawing which shows another example of the external packaging material for a vacuum heat insulating material of this disclosure. It is the schematic sectional drawing which shows another example of the external packaging material for a vacuum heat insulating material of this disclosure.

The present disclosure includes an outer packaging material for a vacuum heat insulating material, a vacuum heat insulating material, and an article with the vacuum heat insulating material in embodiments. Hereinafter, embodiments of the present disclosure will be described with reference to drawings and the like.
However, the present disclosure can be implemented in many different embodiments and is not construed as limited to the description of the embodiments exemplified below. Further, in order to clarify the explanation, the drawings may schematically represent the width, thickness, shape, etc. of each part as compared with the embodiment, but this is merely an example and the interpretation of the present disclosure is limited. It's not something to do. Further, in the present specification and each figure, the same elements as those described above with respect to the above-mentioned figures may be designated by the same reference numerals, and detailed description thereof may be omitted as appropriate. Further, for convenience of explanation, the phrase "upper" or "lower" may be used for explanation, but the vertical direction may be reversed.

Further, in the present specification, there is no particular limitation when a certain structure such as a certain member or a certain area is "above (or below)" another structure such as another member or another area. As long as this includes not only the case of being directly above (or directly below) the other configuration, but also the case of being above (or below) the other configuration, that is, separately above (or below) the other configuration. Including the case where the component of is included.

The present inventors considered using a metal oxide-deposited layer instead of a metal layer for the gas barrier film in order to make the outer packaging material for the vacuum heat insulating material transparent to radio waves. It was found that the performance was insufficient. Therefore, in order to improve the gas barrier performance, an attempt was made to increase the number of metal oxide layers to be laminated and to thicken the metal oxide layer per layer. However, it has been found that when the number of metal oxide layers is increased, the productivity is low, the flexibility as the exterior material is lost, and the barrier is easily broken when various bendings are applied. Further, it has been found that when the metal oxide layer per layer is thickened, it is not easy to improve the barrier performance because the barrier film is cracked even if the film is thickened in the first place.

Further, when the barrier of the gas barrier film is broken, the water vapor barrier performance and the oxygen barrier performance of the outer packaging material for the vacuum heat insulating material are lowered, but the water vapor barrier performance is lowered and the amount of water vapor flowing into the vacuum heat insulating material is increased. It is possible to suppress the increase in the internal vacuum degree and reduce the influence on the heat insulating performance of the vacuum heat insulating material only by adding an inexpensive desiccant together with the core material to the vacuum heat insulating material. it can. Therefore, as for the performance of the outer packaging material for the vacuum heat insulating material, the lowering of the oxygen barrier performance is more problematic for maintaining the heat insulating performance of the vacuum heat insulating material than the lowering of the water vapor barrier performance.

Then, as a result of diligent studies to solve the above problems, the present inventors have arranged an oxygen barrier by arranging a layer containing an inorganic layered compound instead of arranging a metal layer on the outer packaging material for the vacuum heat insulating material. We found that it is possible to suppress the deterioration of oxygen barrier performance by ensuring the performance and further sandwiching the layer containing the inorganic layered compound between the inorganic layers, and it is possible to transmit radio waves and provide good heat insulation performance. We have found that it is an outer packaging material for vacuum heat insulating materials that can produce a sustainable vacuum heat insulating material.
Hereinafter, the outer packaging material for the 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.

A. Outer packaging material for vacuum heat insulating material First, the outer packaging material for vacuum heat insulating material of the present disclosure will be described in detail.
The outer packaging material for a vacuum heat insulating material of the present disclosure is an outer packaging material for a vacuum heat insulating material having a heat-weldable 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 the same. It is characterized in that it is arranged in order and no metal layer is arranged.

FIG. 1 is a schematic cross-sectional view showing an example of the outer packaging material for the vacuum heat insulating material of the present disclosure. The vacuum heat insulating material outer packaging material 10 of the present disclosure is first from the heat-weldable film 1 arranged on one main surface side of the vacuum heat insulating material outer packaging material 10 and the heat-weldable film 1 side. It is characterized by including each layer arranged in the order of the inorganic layer 4, the inorganic layered compound layer 5 containing the inorganic layered compound and the binder resin, and the second inorganic layer 4.

In the example of FIG. 1, the vacuum heat insulating material outer packaging material 10 has a first gas barrier film 2a, a second gas barrier film 2b, and a third gas barrier film 2c, and each gas barrier film has an inorganic layer 4 respectively. Has. 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. Further, the inorganic layered compound layer 5 is contained in the first gas barrier film 2a. Specifically, the first gas barrier film 2a includes a first resin base material 3 and an inorganic layer 4 (first inorganic layer 4) arranged on one main surface side of the first resin base material 3. It has an inorganic layered compound layer 5 arranged on a main surface of the first inorganic layer 4 opposite to the first resin base material 3. The second gas barrier film 2b has an inorganic layer 4 (second inorganic layer 4) arranged on at least one main surface side of the second resin base material 3 and the second resin base material 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. Further, the third gas barrier film 2c having the third resin base material 3 and the third inorganic layer 4 on the opposite side of the second gas barrier film 2b from the first gas barrier film 2a is formed by the third inorganic layer 4. Is arranged so as to be on the side of the second gas barrier film 2b.

The outer packaging material for the 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 metal atom are bonded to each other by a metal bond and have radio wave blocking property. Examples of the metal layer include metal foils such as aluminum, nickel, stainless steel, iron, copper, and titanium, and metal thin films.

Since the outer packaging material for the vacuum heat insulating material of the present disclosure does not have a metal layer arranged, radio waves can be transmitted. Further, by having the inorganic layered compound layer instead of the metal layer, the inorganic layers are arranged on both sides of the inorganic layered compound layer while ensuring the oxygen barrier property, and the inorganic layered compound layer is sandwiched between the inorganic layers. Therefore, deterioration of the oxygen barrier performance of the inorganic layered compound layer can be suppressed. Therefore, it is an external packaging material for a vacuum heat insulating material that can transmit radio waves and can manufacture a vacuum heat insulating material that can maintain good heat insulating performance.

Hereinafter, each configuration of the outer packaging material for the vacuum heat insulating material in the present disclosure will be described in detail.
1. 1. Inorganic layer The outer packaging material for 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 is the first inorganic layer and the second inorganic layer. It is characterized by having a structure arranged between layers. The inorganic layer is a layer other than the metal layer such as a metal foil or a metal thin film, and is an inorganic compound film or an MOP bond (where M indicates a metal atom, O indicates an oxygen atom, and P is an oxygen atom. Examples thereof include a film having a phosphorus atom), a film containing a polyvalent metal salt of a polycarboxylic acid-based 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, particularly a metal oxide film.

Examples of the inorganic compound constituting the inorganic compound film include oxides of metal elements or non-metal elements such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, titanium, boron, yttrium, zirconium, cerium, and zinc. Examples thereof include oxidative nitrides, nitrides, oxidative carbides, and oxidative carbides. Specifically, silicon oxides such as SiO ₂ , aluminum oxides such as Al ₂ O ₃ , magnesium oxides, titanium oxides, tin oxides, silicon zinc alloy oxides, indium alloy oxides, and silicon nitrides. Examples thereof include aluminum nitride, titanium nitride, silicon oxide and zinc oxide. In particular, metal oxides, especially aluminum oxide (alumina) and silicon oxide (silica) are preferable. The inorganic compound may be used alone or may be used by mixing the above-mentioned materials in an arbitrary ratio.

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

Above all, a thin-film deposition film is preferable from the viewpoint of having high adhesion to a resin base material and exhibiting high gas barrier performance. One gas barrier film may be a single film formed by single vapor deposition, or may be formed by multiple vapor deposition and have a laminated structure.

As a film having an M-OP bond (where M represents a metal atom, O represents an oxygen atom, and P represents a phosphorus atom), for example, reaction products of metal oxides and phosphorus compounds can be used. Examples include 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; metals of Group 13 of the periodic table such as aluminum; metals of Group 14 of the periodic table such as silicon; oxides of metals such as transition metals such as titanium and zirconium. Of these, aluminum oxide (alumina) is preferable.

Examples of the phosphorus compound include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid and derivatives thereof. Of these, phosphoric acid is preferable. The specific reaction products of the metal oxide and the phosphorus compound can be, for example, the same as the reaction products disclosed in JP-A-2011-226644.

The presence of MOP bonds causes the maximum infrared absorption peak to appear within the range of 1080 cm ^-1 or more and 1130 cm ^-1 or less in the infrared absorption spectrum (measured wavenumber range; 800 cm ^-1 or more and 1400 cm ^-1 or less). You can check it by doing. The method for measuring the infrared absorption spectrum is not particularly limited, and for example, a measurement method by the total reflection measurement method (ATR method), a method of scraping a sample from the gas barrier film of the outer packaging material, and measuring the infrared absorption spectrum by the KBr method. A measurement method or the like can be used for the collected sample by microinfrared spectroscopy.

The thickness of the inorganic layer is not particularly limited, but is preferably 50 nm or less. By setting the thickness of the inorganic layer to the above value or less, sufficient flexibility can be maintained and barrier fracture is less likely to occur.

The composition and thickness of the two or more inorganic layers contained in the outer packaging material for the vacuum heat insulating material of the present disclosure may be the same or different.

2. 2. Inorganic layered compound layer The inorganic layered compound layer in the present disclosure is a layer arranged between a first inorganic layer and a second inorganic layer. As long as the inorganic layered compound layer is arranged between the first inorganic layer and the second inorganic layer, its arrangement position is not particularly limited, and one main surface of the resin base material or one of the inorganic layers Can be provided on the main surface of.

The inorganic layered compound layer contains at least an inorganic layered compound and a binder resin. Such an inorganic layered compound layer is different from one in which gas permeation is prevented by a continuous film such as a thin-film vapor deposition thin film, and innumerable inorganic layered compounds dispersed in the layer block the progress of gas and bypass it (maze). (Effect), it extends the path required for permeation and exerts barrier performance. Since the gas mainly travels in the binder resin in the inorganic layered compound layer, the gas barrier performance of the binder resin itself is important for exhibiting high barrier performance, but the gas barrier performance of the binder resin is lowered by water vapor. 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 each layer constituting the water vapor entering from the outside air and the outer packaging material for the vacuum heat insulating material is inside. The influence of the water vapor contained can be reduced. Therefore, in particular, in a configuration 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 material does not come into direct contact with the inorganic layered compound layer, so that the resin group 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, between the inorganic layered compound layer and the first inorganic layer and the second inorganic layer, a layer other than the adhesive layer and the overcoat layer (that is, a resin) It is preferable that the base material, etc.) is not arranged.

(A) Inorganic layered compound The inorganic layered compound means an inorganic compound having a layered structure in which unit crystal layers are stacked on each other. That is, the "layered compound" means a compound or substance having a layered structure. Further, the "layered structure" refers to a structure in which atoms are strongly bonded by a covalent bond or the like and closely arranged surfaces are stacked in parallel by a weak bonding force such as a van der Waals force.

The inorganic layered compound may be any compound having a layered structure, and examples thereof include graphite, phosphate-based derivative compounds (zoxide-based compounds), chalcogenides, and clay minerals. Of these, clay minerals are preferable.

Specifically, as clay minerals, phyllosilicate minerals such as hydrous silicates; kaolinite group clay minerals such as halloysite, kaolinite, enderite, deckite, and nacrite; antigolite group clays such as antigolite and chrysotile. Minerals; Smectite clay minerals such as montmorillonite, iron montmorillonite, byderite, nontronite, saponite, hectrite, soconite, and stibuncite; vermiculite clay minerals such as vermiculite; mica such as white mica and gold mica; margarite, tetrasi Mica or mica clay minerals such as lyric mica and teniolite; green mudstone clay minerals such as cuckeyite, sudowite, clinochloa, chamosite and nimate, or substitutions and derivatives thereof. These clay minerals may be natural clay minerals or synthetic clay minerals, and may contain two or more kinds in combination.

In the present disclosure, among them, phyllosilicate minerals and smectite group clay minerals are preferable, and montmorillonite and hectorite contained in smectite group clay minerals are particularly preferable.

The average particle size of the particles of the inorganic layered compound is preferably 50 nm or more and 5 μm or less, particularly 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 the oxygen barrier performance of the inorganic layered compound layer becomes better by setting the average particle size of the particles of the inorganic layered compound in the above range. The particle size of the particles of the inorganic layered compound is the center diameter (major axis) obtained from the photon correlation method by the dynamic light scattering method measured using an ultrafine particle size analyzer under the conditions of a temperature of 25 ° C. and an aqueous solvent. ..

The aspect ratio of the inorganic layered compound is preferably 50 or more and 5000 or less, particularly preferably 200 or more and 3000 or less, and particularly preferably 300 or more and 2500 or less.
This is because the oxygen barrier performance of the inorganic layered compound layer becomes better by setting the aspect ratio of the inorganic layered compound in the above range. 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 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 size of the inorganic layered compound, and a is the average interplanar spacing (average unit thickness) of the inorganic layered compound.)

The average particle size L of the inorganic layered compound is a value obtained by the method described above. The surface 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. From the powder X-ray diffraction measurement of the composition containing the inorganic layered compound and the binder resin, it can be confirmed that there is a portion where the surface 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 a salt thereof, polybenzenesulfonic acid or a salt thereof, polyethyleneimine, polyallylamine, poly Examples thereof include glycerin and the like, and further examples thereof include polysaccharides such as hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, amylose, amylopectin, curdlan, zantane, chitin, cellulose, pullulan and chitosan. In the present disclosure, polyvinyl alcohol and polyacrylic acid are particularly preferable.

In general, the hydrophilic resin tends to deteriorate its gas barrier performance due to water vapor, but the packaging material for the 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 reason described above, and it is possible to maintain a high barrier property against oxygen of the inorganic layered compound layer.

(C) Others In the inorganic layered compound layer, the larger the volume of the inorganic layered compound, the better the oxygen barrier performance. On the other hand, the larger the volume of the binder resin, the better the bending resistance. Therefore, the volume ratio of the inorganic layered compound to the binder resin (inorganic layered compound / resin) is preferably 5/95 to 90/10, and more preferably 5/95 to 50/50. preferable. This is because the inorganic layered compound layer having excellent oxygen barrier performance and bending resistance can be obtained by setting the volume ratio of the inorganic layered compound to the binder resin in the above range.

The thickness of the inorganic layered compound layer is preferably 1 μm or less, particularly 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, sufficient oxygen barrier performance can be exhibited, and the hardness of the inorganic layered compound layer can be made relatively small, so that the outer package for the vacuum heat insulating material can be used. This is because the layered structure of the inorganic layered compound in the inorganic layered compound layer can be maintained even when the material is subjected to bending stress.

3. 3. Heat-weldable film In the outer packaging material for vacuum heat insulating material of the present disclosure, a heat-weldable layer is arranged on one main surface side. Such a heat-weldable film is a film that can be welded by heating. The heat-weldable film is a member that bears one surface in the thickness direction of the vacuum heat insulating material outer packaging material, and is used as a core material when the vacuum heat insulating material outer packaging material of the present disclosure is used to produce the vacuum heat insulating material. It is a member that joins the ends of the outer packaging materials for vacuum heat insulating materials that are in contact with each other and that are opposed to each other when sealing the core material.

As the heat-weldable film, a resin film that can be melted and fused by heating can be used. For example, polyethylene such as linear short-chain branched polyethylene (LLDPE) and unstretched polypropylene (CPP) 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; poly ( Meta) Acrylic resin film; Urethane resin film and the like can be mentioned.

The heat-weldable film may contain other materials such as an anti-blocking agent, a lubricant, a flame retardant, and a filler.

The thickness of the heat-weldable film may be any thickness as long as it can obtain a desired adhesive force when the outer packaging materials for vacuum heat insulating materials are joined to each other. For example, it is in the range of 15 μm or more and 100 μm or less, preferably 25 μm. It can be within the range of 90 μm or more, more preferably 30 μm or more and 80 μm or less.

4. Resin base material The outer packaging material for the vacuum heat insulating material of the present disclosure is not particularly limited, but the above-mentioned inorganic layer or inorganic layered compound layer can usually be provided on one main surface of the resin base material. ..

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

The resin used for the resin base material is not particularly limited, and is, for example, a polyolefin resin such as polyethylene or polypropylene, a polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polybutylene terephthalate (PBT). , 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 the saponified product, various polyamide resins such as nylon, polyimide resin, polyurethane resin, acetal resin, and cellulose resin 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 the additive include a lubricant, a cross-linking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, a resin for modification and the like.

The resin base material may be surface-treated. This is because the adhesion with the inorganic layer can be improved. Examples of the surface treatment include an oxidation treatment, a roughening treatment (roughening treatment), and an easy-adhesion coating treatment disclosed in Japanese Patent Application Laid-Open No. 2014-180837.

The thickness of the resin base material 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 the present specification, the designations A to B indicate a range including A and B). It is.). Further, the resin base material may be a single layer or a multilayer body in which a plurality of resin layers are laminated. In the multilayer body, each resin layer 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 the resin base material made of a resin that is relatively more likely to contain water vapor than the inorganic layer between the two inorganic layers, it is possible to further suppress the invasion of water vapor into the inorganic layered compound layer. Is.
When the outer packaging material for the vacuum heat insulating material of the present disclosure contains a resin base material, a heat-weldable film, a resin base material, a first inorganic layer, an inorganic layered compound layer, and a second inorganic layer are used. , Are preferably included in this order.

5. Overcoat layer In the outer packaging material for vacuum heat insulating material of the present disclosure, the 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 more excellent gas barrier properties to the outer packaging material for the 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. The ratio of metal atoms to carbon atoms (number of metal atoms / number of carbon atoms) in the atoms constituting the overcoat layer is in the range of 0.1 or more and 2 or less, and among them, 0.5 or more and 1 It is preferably in the range of 9.9 or less, particularly in the range of 0.8 or more and 1.6 or less. If the ratio is less than the above range, the brittleness of the overcoat layer becomes large, and the water resistance and weather resistance of the obtained overcoat layer may decrease. On the other hand, if the ratio exceeds the above range, the gas barrier property of the obtained overcoat layer may decrease.

In the overcoat layer having the above-mentioned ratio, 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, 500 parts by mass with respect to 100 parts by mass of the total amount of alkoxide described later. It can be obtained by setting the blending ratio within the range of 20 parts by mass or more and 200 parts by mass or less. As an example of the composition for forming an overcoat layer, solution A (a mixed solution consisting of polyvinyl alcohol (PVA), isopropyl alcohol and ion-exchanged water) and solution B (tetraethoxysilane (TEOS), isopropyl alcohol) prepared in advance are added. , Hydrolyzed solution consisting of hydrochloric acid and ion-exchanged water) is added in a specific ratio of PVA to 100 parts by mass of TEOS and stirred to obtain a colorless and transparent overcoat layer forming composition obtained by a sol-gel method. Can be mentioned.

The film thickness of the overcoat layer is not particularly limited, but is preferably 200 nm or more. This is because if it is equal to or more than the above value, the gas barrier property of the outer packaging material for the vacuum heat insulating material can be surely improved.
In the present disclosure, an overcoat layer may be arranged particularly between the inorganic layered compound layer and the second inorganic layer. By arranging the overcoat layer, pinholes and the like existing in the inorganic layer can be filled, so that it is possible to further prevent the invasion of water vapor. However, what is a heat-weldable film of the inorganic layered compound layer? This is because 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 outer packaging material for vacuum heat insulating material of the present disclosure may have an adhesive layer between each barrier film or a heat-weldable layer. As the material of 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-component curable adhesive containing a main agent and a curing agent, but the adhesive is not limited thereto. For example, a one-component curable adhesive mixed with a main agent and a latent curing agent blocked by a known method so as not to react when mixed with the main agent, or a known curing agent so as not to react when mixed. It may be a one-component curable adhesive in which a latent main agent blocked by the method and a curing agent are mixed.

Specific examples of the adhesive constituting the adhesive layer include an epoxy adhesive, a polyvinyl acetate adhesive, a polyacrylic acid ester adhesive, a cyanoacrylate adhesive, an ethylene copolymer adhesive, 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, etc. can be used.

In particular, as the adhesive, a polyacrylic acid ester adhesive, a polyurethane adhesive and the like are preferable, and in particular, the adhesive is preferably a compound having an isocyanate group as a functional group, and specifically, a polyurethane adhesive. It is preferably an adhesive.

The adhesive constituting the adhesive layer may contain any material such as a curing accelerator, a catalyst, an antioxidant, a stabilizer, an ultraviolet absorber, a light stabilizer, and an antistatic agent.

The thickness of the adhesive layer may be any thickness as long as it can exhibit a desired adhesive force, and can be appropriately set according to the composition of the adhesive layer and the like. Usually, it is preferable that the thickness of which becomes ^{^{0.1g / m 2 ~ 10g / m}} 2 approximately in a dry state.

The adhesive layer may or may not have transparency, but when transparency is required as the outer packaging material for the vacuum heat insulating material, it is preferable that the adhesive layer has transparency.

As the adhesive layer, a sheet or film formed by the above-mentioned adhesive may be used, and a coating liquid prepared by mixing the above-mentioned adhesive with a desired solvent is prepared, and one surface of a heat-welable film or a gas barrier film is prepared. It may be applied directly to, dried and cured to form.
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 above-mentioned two or more inorganic layers and inorganic layered compound layers can be arranged on each gas barrier film which is a film having gas barrier performance and constitutes the outer packaging material for the 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 different gas barrier films, but a plurality of layers (for example, the first inorganic layer and the inorganic layered compound) are 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 composed of 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. Arranged between them, the first inorganic layer 4, the inorganic layered compound layer 5, and the second inorganic layer 4 are contained in the outer packaging material 10 for vacuum heat insulating material in this order, and the second gas barrier film 2b The second inorganic layer 4 in the above is arranged so as to face the inorganic layered compound layer 5 of the first gas barrier film 2a.

Specifically, such a first embodiment includes the following two aspects.
In the first aspect, a heat-weldable film, a first resin base material, a first inorganic layer, an inorganic layered compound layer, a second inorganic layer, and a second resin layer are arranged in this order. It is an arranged aspect.
In the second aspect, in addition to the first aspect, the third inorganic layer and the third resin base material are placed on the surface of the second resin base material opposite to the second inorganic layer. It is an aspect arranged in order.
Hereinafter, each configuration of this embodiment will be described in detail.

(1) First Gas Barrier Film The first gas barrier film in this embodiment is arranged on one main surface side of the heat-weldable film, and is arranged between the heat-weldable film and the second gas barrier film. It is a thing. In the present 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 a second inorganic layer of the second gas barrier film. It is arranged so as to face the. Usually, it is preferable that no other gas barrier film or protective film is arranged between the first gas barrier film and the heat-weldable film.

The first resin substrate is usually arranged so as to face the heat-weldable 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 as those exemplified in "5. Resin base material" can be mentioned.
Examples of 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 the present embodiment is arranged on the main surface side opposite to the heat-weldable film of the first gas barrier film, and has a second resin base material and a second gas barrier film. It has 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 similar to those exemplified in "5. Resin base material" described above. Examples of the second inorganic layer include those similar to 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 base material. In the present embodiment, the inorganic layered compound layer in the first gas barrier film is arranged so as to face the second inorganic layer in the second gas barrier film, so that the inorganic layered compound layer and the second inorganic layer are separated from each other. , Direct contact or arranged via the overcoat layer or adhesive layer described above. Examples of the overcoat layer and the adhesive layer include those similar to those exemplified in "5. Overcoat layer" and "6. Adhesive layer" described above.

Further, the above adhesion is made 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, and the like. Layers can be located.
Examples of the adhesive layer include those similar to those exemplified in "6. Adhesive layer" described above.

(3) Other Gas Barrier Film The outer packaging material for the vacuum heat insulating material of the present embodiment has at least a first gas barrier film and a second gas barrier film, but it is preferable to have at least one layer or more of the gas barrier film. Among them, the outer packaging material for the vacuum heat insulating material of the present disclosure preferably has three layers of gas barrier films, and specifically, as shown in FIG. 1, the first gas barrier film 2a and the second gas barrier film 2b In addition, it is preferable to have a third gas barrier film 2c. This is because the gas barrier property can be improved by having the gas barrier film having three layers in this way. 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 lowered.

The third gas barrier film is not particularly limited as long as it is a layer that does not contain a metal layer, and is typically a third gas barrier film arranged on one main surface side of the third resin base material and the third resin base material. It has 3 inorganic layers. Examples of the third resin base material and the third inorganic layer include those similar to those exemplified in "5. Resin base material" and "1. Inorganic layer" described above.

As the third inorganic layer, an inorganic compound film made of aluminum oxide (alumina) and silicon oxide (silica) is preferable. The thickness of the third inorganic layer is not particularly limited, but 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 fracture is less likely to occur. Further, the second gas barrier film and the third gas barrier film included in the outer packaging material for the vacuum heat insulating material of the present disclosure may be the same, and the type, layer structure, material and the like may be different.

The position of the third inorganic layer in the third gas barrier film is not particularly limited, but usually, the third inorganic layer is arranged so as to be closer to the second gas barrier film than the third resin base material.

(Second Embodiment)
In the present disclosure, the outer packaging material of the second embodiment as illustrated in FIG. 3 is also preferable. In the outer packaging material of the second embodiment, the resin base material 3 of the second gas barrier film 2b in the outer packaging 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 in such a manner. 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. From the heat-weldable film 1 side, the first inorganic layer 4, the inorganic layered compound layer 5, the resin base material 3, and the second inorganic layer 4 are contained in the outer packaging material 10 for vacuum heat insulating material in this order. ..

Specifically, such a second embodiment includes the following aspects.
That is, a heat-weldable film, a first resin base material, a first inorganic layer, an inorganic layered compound layer, a second resin base material, a second inorganic layer, and a third inorganic layer. The third resin base material 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 the same as the first gas barrier film and the second gas barrier film exemplified in the first embodiment.

The outer packaging material for the vacuum heat insulating material of this embodiment has at least a first gas barrier film and a second gas barrier film, but it is preferable to have at least one layer or more of the gas barrier film. Among them, the outer packaging material for the vacuum heat insulating material of the present embodiment preferably has three layers of gas barrier films, and specifically, as shown in the example of FIG. 3, the first gas barrier film 2a and the second gas barrier film In addition to 2b, it is preferable to have a third gas barrier film 2c. This is because the gas barrier property can be improved by having the gas barrier film having three layers in this way. 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 lowered. Examples of the other gas barrier film of the present embodiment include the same as the other gas barrier films exemplified in the first embodiment.

The adhesive layer is provided 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, and the like. Can be located. Examples of the adhesive layer include those similar to those exemplified in "6. Adhesive layer" described above.

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

Specifically, such a third embodiment 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 base material, a third inorganic layer, and a third resin base material. Is an embodiment arranged in this order.

In the present embodiment, the inorganic layered compound layer 5 in the first gas barrier film is composed of a first inorganic layer 4 provided on one main surface of a heat-weldable film 1 and a second inorganic layer 4. The first inorganic layer 4, the inorganic layered compound layer 5, and the second inorganic layer 4 are contained in the outer packaging material 10 for vacuum heat insulating material in this order from the side of the film 1 which is arranged between them and can be heat-welded. 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. In the present embodiment, the inorganic layered compound layer is one main surface of the heat-weldable film. It is arranged so as to face the first inorganic layer provided above. Examples of the inorganic layer provided on one main surface of the heat-weldable film include those similar to those exemplified in "1. Inorganic layer". The heat-weldable film provided with such an inorganic layer also has a function as a gas barrier film, and a known barrier sealant can be used as the outer packaging material. Specifically, an unstretched polypropylene film or the like provided with an inorganic vapor deposition layer can be used.

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

In the present embodiment, the adhesive layer is located 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 similar to those exemplified in "6. Adhesive layer" described above.

8. Characteristics The outer packaging material for vacuum heat insulating material of the present disclosure has excellent gas barrier performance. The gas barrier performance refers to the oxygen barrier performance defined by the oxygen permeability and the water vapor barrier performance defined by the water vapor permeability.

In particular, the outer packaging material for the vacuum heat insulating material of the present disclosure has an oxygen permeability of, for example, 0.1 cc / (m ² · day · atm) or less, particularly 0.05 cc, even though the metal layer is not arranged. It can be less than / (m ² · day · atm).

For oxygen permeability, refer to JIS K7126-2: 2006 (Plastic-Film and Sheet-Gas Permeability Test Method-Part 2: Isopressure Method, Annex A: Oxygen Gas Permeability Test Method by Electrolytic Sensor Method) , Oxygen gas permeability measuring device can be used for measurement under the conditions of temperature 23 ° C. and humidity 60% RH. As the oxygen gas permeability measuring device, for example, "OXTRAN" manufactured by MOCON of the United States can be used. In the measurement, the surface of the outermost layer of the outer packaging material cut to a desired size, which is the outermost layer of the two outermost layers facing the thickness direction and is opposite to the heat-weldable film, is oxygen. It is mounted in the above device so as to be in contact with the gas, and the measurement is performed under the conditions of a permeation area of about 50 cm ² (permeation area: a circle with a diameter of 8 cm), a temperature of 23 ° C. and a humidity of 60% RH. Do. At the time of the above measurement, the carrier gas is supplied into the apparatus at a flow rate of 10 cc / min for 60 minutes or more to purge. As the carrier gas, a nitrogen gas containing about 5% hydrogen can be used. After purging, the test gas is flowed into the above device, and the measurement is performed after securing 12 hours as the time from the start of the flow to the arrival of the equilibrium state. The test gas uses at least 99.5% dry oxygen. The measurement of oxygen permeability is performed for at least three samples under one condition, and the average of those measured values is taken as the value of oxygen permeability under that condition.

Further, the outer packaging material for the 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, particularly 0.01 g / (m ² · day) or less. This is because the outer packaging material having such water vapor permeability can maintain the heat insulating performance for a long period of time when the vacuum heat insulating material is used. The water vapor permeability can be a value measured under the 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 permeability can be measured by the following procedure. First, a sample of an outer packaging material cut to a desired size is sampled, and among the outermost surfaces facing each other in the thickness direction (lamination direction), the outermost surface layer located on the opposite side of the heat-weldable film, which is one of the outermost layers, It is mounted between the upper and lower chambers of the above device so that it is on the high humidity side (water vapor supply side), and has a permeation area of about 50 cm ² (permeation area: circular with a diameter of 8 cm), a temperature of 40 ° C, and a relative humidity. The measurement is performed under the condition of a difference of 90% RH. As the water vapor permeability measuring device, for example, "DELTAPERM" manufactured by Technolux of the United Kingdom can be used.

The outer packaging material for the vacuum heat insulating material in the present disclosure has radio wave transmission because the metal layer is not arranged. Here, the term "having radio wave transmission" is not particularly limited as long as the device in the compartment covered with the vacuum heat insulating material has radio wave transmission to the extent that it can be contacted with the outside by radio waves. For example, the electromagnetic wave shielding property in the range of 300 MHz to 30 GHz is preferably 10 dB or less. As a method for measuring radio wave transmission, it can be measured by far-field measurement. Specifically, a transmitting antenna can be placed in one anechoic chamber and a receiving antenna can be placed in the other anechoic chamber, and a shield material can be placed in the wall window that separates the two for evaluation.

The outer packaging material for the vacuum heat insulating material of the present disclosure may or may not have transparency, and is appropriately set according to the application of the vacuum heat insulating material in which the outer packaging material for the vacuum heat insulating material of the present disclosure is used. can do. The transparency of the outer packaging material for the vacuum heat insulating material is not specified by a strict transmittance, and can be appropriately determined according to the application and the like.

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

As a method for manufacturing the outer packaging material for the vacuum heat insulating material of the present disclosure, for example, a method of laminating each film manufactured in advance via the above-mentioned adhesive layer can be mentioned. Further, the external packaging material for the vacuum heat insulating material of the present disclosure may be produced by sequentially extruding and laminating the raw materials of the heat-melted films with a T-die or the like.

The outer packaging material for the vacuum heat insulating material of the present disclosure can be used as the vacuum heat insulating material. In the vacuum heat insulating material, the outer packaging material for the vacuum heat insulating material of the present disclosure can be used by arranging them so as to face each other via the core material so that the heat-weldable film is on the core material side.

B. Vacuum heat insulating material The vacuum heat insulating material of the present disclosure is a vacuum heat insulating material having a core material and an outer packaging material for encapsulating the core material, and the outer packaging material is the above-mentioned "A. Outer packaging material for vacuum heat insulating material". It is characterized in that it is the one explained in the section.

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

According to the present disclosure, the outer packaging material that encloses the core material is the outer packaging material for the vacuum heat insulating material described in the above-mentioned "A. Outer packaging material for vacuum heat insulating material", and thus has radio wave transmission property. It is 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. 1. Outer packaging material The outer packaging material in the present disclosure is a member that encloses the core material, and is the same as the outer packaging material for the vacuum heat insulating material described in the above section "A. Outer packaging material for vacuum heat insulating material". The description is omitted.

2. 2. Core material The core material in the present disclosure is a member enclosed by an outer packaging material. It should be noted that "sealing" means that the bag is sealed inside a bag formed by using the outer packaging material.

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

As the material constituting the core material, powder, foam, fiber, etc. can be used. The powder may be inorganic or organic, and for example, dry silica, wet silica, aggregated silica powder, conductive powder, calcium carbonate powder, pearlite, 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 in which the internal pressure rises, because the decrease in heat insulating performance due to the rise in the internal pressure of the vacuum heat insulating material is small. Further, when a substance having a small infrared absorption rate such as titanium oxide, aluminum oxide or indium-doped tin oxide is added to the above-mentioned material as a radiation suppressing material, the infrared absorption rate of the core material can be reduced.

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

The fiber body may be an inorganic fiber or an organic fiber, but it is preferable to use an inorganic fiber from the viewpoint of heat insulating 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 preferable in that they have low thermal conductivity and are easier to handle than powders.

The core material may be a composite material in which the above-mentioned materials are used alone or a mixture of two or more kinds of materials.

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

The lower the thermal conductivity of the vacuum heat insulating material, the more preferable. 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 can exert a high heat insulating effect. Above all, the initial thermal conductivity is more preferably 4 mW / (mK) or less. The thermal conductivity is based on JIS A1412-2: 1999, and can be a value measured under the conditions of a high temperature side of 30 ° C., a low temperature side of 10 ° C., and an average temperature of 20 ° C.

Further, since the vacuum heat insulating material of the present disclosure uses the above-mentioned external packaging material, deterioration of the heat insulating performance is suppressed.
Further, when the vacuum heat insulating material is used for an article that requires identification and traceability of the contents, for example, a container in physical distribution, the vacuum heat insulating material has a thin plate thickness and high heat insulation without squeezing the storage space. It is expected to exert its sexuality. In the vacuum heat insulating material of the present disclosure, the gas barrier film of the outer packaging material has two or three layers and can exhibit high heat insulating performance as well as radio wave transmission, so that the vacuum heat insulating material can be made thin.

As the method for producing the vacuum heat insulating material of the present disclosure, a general method can be used. For example, two sheets of the vacuum heat insulating material outer packaging material described in the above section "A. Vacuum heat insulating material outer packaging material" are prepared, and the heat-weldable films are overlapped with each other facing each other, and the outer edges of the three sides are overlapped. It is heat welded to obtain a bag body with one side open. A vacuum heat insulating material can be obtained by inserting a core material through the opening into the bag body, sucking air from the opening, and sealing the opening in a state where the inside of the bag body is depressurized.

The vacuum heat insulating material of the present disclosure can be used, for example, for articles that require thermal insulation and radio wave transmission. The above articles will be described later.

C. Article with vacuum heat insulating material The article with vacuum heat insulating material of the present disclosure is an article having a heat insulating region and an article with a vacuum heat insulating material provided with the vacuum heat insulating material, and the vacuum heat insulating material is enclosed in a core material and a core material. The outer packaging material is the outer packaging material for the vacuum heat insulating material described in the above section "A. Outer packaging material for vacuum heat insulating material".

According to the present disclosure, since the vacuum heat insulating material used in the article is composed of the outer packaging material described in the section "A. Outer packaging material for vacuum heat insulating material", the vacuum heat insulating material has good heat insulating performance for a long period of time. By providing the article with such a vacuum heat insulating material, it is possible to achieve energy saving of the article or the object in which the article is used in a high temperature and high humidity environment. Further, since the vacuum heat insulating material is capable of transmitting radio waves, it is possible to identify and traceability the contents of the article.

The vacuum heat insulating material in the present disclosure and the outer packaging material used therein have been described in detail in the sections "B. Vacuum heat insulating material" and "A. Outer packaging material for vacuum heat insulating material" described above, and thus the description thereof is omitted here. To do.

The article in the present disclosure has a heat insulating region. Here, the heat-insulated region is a region that is heat-insulated by the vacuum heat insulating material, for example, a region that is heat-retained or cooled, a region that surrounds the heat source or the cooling source, or a region that is isolated from the heat source or the cooling source. Is. These areas may be spaces or objects. Further, the above-mentioned article is preferably an article that requires radio wave transmission.

Examples of the above-mentioned articles include electric devices such as refrigerators, freezers, warmers, and coolers, heat-retaining containers, cold-retaining containers, transport containers, containers, containers such as storage containers, vehicles such as vehicles, aircraft, and ships, houses, and warehouses. Building materials such as buildings, wall materials, floor materials, etc.

The present disclosure is not limited to the above embodiment. The above embodiment is an example, and any object having substantially the same structure as the technical idea described in the claims of the present disclosure and exhibiting the same effect and effect is the present invention. Included in the technical scope of the disclosure.

Examples and comparative examples are shown below, and the present disclosure will be described in more detail.

[material]
The members and adhesives constituting the outer packaging material for the vacuum heat insulating material of Examples and Comparative Examples are shown below and in Table 1.
(Member: Gas barrier film)
-Gas barrier film A: A film in which the following overcoat layer A is provided on a vapor-deposited film of a film in which a silicon oxide film is deposited on one side of a nylon film (thickness: 15 μm) (manufactured by Dainippon Printing Co., Ltd. (trade name: IB-ON). -UB))

-Gas barrier film B: A film in which the following overcoat layer A is provided on a vapor-deposited film of a film in which a silicon oxide film is vapor-deposited on one side of a PET film (thickness: 12 μm) (manufactured by Dainippon Printing Co., Ltd. (trade name: IB-PET). -UB))

Gas barrier film C: Montmorillonite (manufactured by Kunimine Kogyo Co., Ltd .: Kunipia F) and PVA (polyvinyl alcohol) on the vapor-deposited film of a film in which alumina (thickness: 20 nm) is vapor-deposited on one side of a PET film (thickness: 12 μm). A film provided with an inorganic layered compound layer (thickness: 240 nm) containing JF-04, saponification degree 98-99%, average degree of polymerization 400) manufactured by Japan Vam & Poval Co., Ltd.

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

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

-Gas barrier film D: A film in which the following overcoat layer A is provided on a vapor-deposited film of a film in which alumina is vapor-deposited on one side of a PET film (thickness: 12 μm) (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. Clarista CF, thickness 12 μm)

-Gas barrier film F: A film in which the following overcoat layer A is provided on a vapor-deposited film of a film in which alumina is vapor-deposited on one side of a PET film (thickness: 12 μm) (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 in which a metallic aluminum (Al) film is vapor-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, thickness 12 μm)
-Gas barrier film J: A film in which a metallic aluminum film is vapor-deposited on one side of a PET film (thickness: 12 μm) (VM-PET1519 manufactured by Toray Film Processing Co., Ltd.)
Gas barrier film K: A film in which the following overcoat layer A is provided on a vapor-deposited film of a film in which a silicon oxide film is vapor-deposited on one side of a PET film (thickness: 12 μm).

(Overcoat layer)
・ Overcoat layer A
Solution A (mixed solution consisting of polyvinyl alcohol, isopropyl alcohol and water) prepared according to the composition shown below, and solution B (tetraethoxysilane (TEOS), isopropyl alcohol, hydrochloric acid and ion-exchanged water) prepared in advance according to the composition shown below. (Hydrolyzed solution consisting of) was added and stirred to obtain a colorless and transparent composition for an overcoat layer by the sol-gel method.
The composition for the overcoat layer is coated on the 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 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 a silicon element, an oxygen element and a polyvinyl alcohol resin.

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

(Member: Heat-weldable film)
・ Heat-weldable film A: Linear low-density polyethylene film (manufactured by Mitsui Chemicals Tohcello Co., Ltd.)
Product name: TUX HC-E, thickness 50 μm)

(adhesive)
-Adhesive A: Main agent containing polyester polyol as the main component (Rock Paint product name: RU-77T), curing agent containing aliphatic isocyanate (Rock Paint product name: H-7), and ethyl acetate A two-component curable adhesive in which the above solvents are mixed in a weight-blending ratio such that the main agent: curing agent: solvent = 10: 1: 14.

(Preparation of outer packaging material for vacuum heat insulating material)
[Example 1]
An external packaging material having a gas barrier film A as the first layer, a gas barrier film B as the second layer, a gas barrier film C as the third layer, and a heat-weldable film A as the fourth layer was obtained in this order. The vapor-deposited film (inorganic layer) of the second gas barrier film B was arranged so as to face the inorganic layered compound layer of the third gas barrier film C via the overcoat layer. That is, the inorganic layer of the gas barrier film B, the inorganic layered compound layer of the gas barrier film C, and the inorganic layer of the gas barrier film C were arranged in this order. The first layer was arranged so that the vapor-deposited film was on the film A side capable of heat welding with respect to the resin base material. 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 between the layers, and the other member is placed on the adhesive layer and pressed to bond. did.

[Example 2]
An external packaging material having a gas barrier film D as the first layer, a gas barrier film D as the second layer, a gas barrier film C as the third layer, and a heat-weldable film A as the fourth layer was obtained in this order. The vapor-deposited film (inorganic layer) of the second gas barrier film D was arranged so as to face the inorganic layered compound layer of the third gas barrier film C via the overcoat layer. That is, the inorganic layer of the gas barrier film D, the inorganic layered compound layer of the gas barrier film C, and the inorganic layer of the gas barrier film C were arranged in this order. The first layer was arranged so that the vapor-deposited film was on the film A side capable of heat welding with respect to the resin base material. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Example 3]
An external packaging material having a gas barrier film E as the first layer, a gas barrier film D as the second layer, a gas barrier film C as the third layer, and a heat-weldable film A as the fourth layer was obtained in this order. The vapor-deposited film (inorganic layer) of the second gas barrier film D was arranged so as to face the inorganic layered compound layer of the third gas barrier film C via the overcoat layer. That is, the inorganic layer of the gas barrier film D, the inorganic layered compound layer of the gas barrier film C, and the inorganic layer of the gas barrier film C were arranged in this order. The first layer was arranged so that the gas barrier film was on the film A side capable of heat welding with respect to the resin base material. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Example 4]
An external packaging material having a gas barrier film F as the first layer, a gas barrier film D as the second layer, a gas barrier film C as the third layer, and a heat-weldable film A as the fourth layer was obtained in this order. The vapor-deposited film (inorganic layer) of the second gas barrier film D was arranged so as to face the inorganic layered compound layer of the third gas barrier film C via the overcoat layer. That is, the inorganic layer of the gas barrier film D, the inorganic layered compound layer of the gas barrier film C, and the inorganic layer of the gas barrier film C were arranged in this order. The first layer was arranged so that the vapor-deposited film was on the film A side capable of heat welding with respect to the resin base material. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 1]
An external packaging material having a gas barrier film A as the first layer, a gas barrier film D as the second layer, a gas barrier film H as the third layer, and a heat-weldable film A as the fourth layer was obtained in this order. The vapor deposition film (inorganic layer) of the second gas barrier film D is arranged so as to face the vapor deposition film of the third gas barrier film H via the overcoat layer, and the vapor deposition film of the first layer is resin-based. It was arranged so as to be on the film A side where heat welding was possible rather than the material. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 2]
An external packaging material having a gas barrier film A as the first layer, a gas barrier film B as the second layer, a gas barrier film I as the third layer, and a heat-weldable film A as the fourth layer was obtained in this order. The vapor deposition film (inorganic layer) of the second gas barrier film B is arranged so as to face the gas barrier film I side of the third layer via the overcoat layer, and the vapor deposition film of the first layer is made of a resin base material. Was also arranged so as to be on the film A side where heat welding is possible. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

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

[Comparative Example 4]
An external packaging material having a gas barrier film A as the first layer, a gas barrier film B as the second layer, a gas barrier film K as the third layer, and a heat-weldable film A as the fourth layer was obtained in this order. The overcoat layer of the second gas barrier film B is arranged so as to face the overcoat layer of the third gas barrier film K, and the first layer is a film A in which the vapor-deposited film can be heat-welded more than the resin base material. Arranged so as to be on the side. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 5]
An external packaging material having a gas barrier film A as the first layer, a gas barrier film D as the second layer, a gas barrier film K as the third layer, and a heat-weldable film A as the fourth layer was obtained in this order. The overcoat layer of the second gas barrier film D is arranged so as to face the overcoat layer of the third gas barrier film K, and the first layer is a film A in which the vapor-deposited film can be heat-welded more than the resin base material. Arranged so as to be on the side. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 6]
An external packaging material having a gas barrier film F as the first layer, a gas barrier film J as the second layer, a gas barrier film H as the third layer, and a heat-weldable film A as the fourth layer was obtained in this order. The vapor deposition film of the second layer gas barrier film J is arranged so as to face the vapor deposition film of the third layer gas barrier film H, and the first layer is on the film A side where the vapor deposition film can be heat-welded more than the resin base material. Arranged so as to be. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

[Comparative Example 7]
An external packaging material having a gas barrier film D as the first layer, a gas barrier film D as the second layer, a gas barrier film D as the third layer, and a heat-weldable film A as the fourth layer was obtained in this order. The overcoat layer of the second gas barrier film D is arranged so as to face the third overcoat layer, and the first layer is on the film A side where the vapor deposition film can be heat-welded more than the resin base material. Placed in. Each layer was adhered with an adhesive layer in the same manner as in Example 1.

(Oxygen permeability)
Samples were taken out from each of the packaging materials obtained in Examples 1 to 4 and Comparative Examples 1 to 7, and the temperature was 23 ° C., according to the method and conditions described in the above section "A. Outer packaging material for vacuum heat insulating material VI. Characteristics". The oxygen permeability was measured under the condition of humidity 60% RH. The results are shown in Oxygen Permeability (Flat) in Table 2.
Further, for each of the outer packaging materials obtained in Examples 1 to 4 and Comparative Examples 1 to 7, rectangular test pieces having a width of 210 mm and a length of 297 mm (A4 size) were collected. In accordance with ASTM F392, each test piece was bent three times using a Gelboflex tester (manufactured by Tester Sangyo Co., Ltd., model name: BE1006).
For each test piece after the three-time bending treatment, the oxygen permeability under the conditions of a temperature of 23 ° C. and a humidity of 60% RH according to the method and conditions described in the above section "A. Outer packaging material for vacuum heat insulating material VI. Characteristics". (Oxygen permeability after bending treatment) was measured. The results are shown in Oxygen permeability (after bending) in Table 2.

(Making vacuum heat insulating 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 two sheets were stacked so that the heat-weldable films faced each other to form a quadrilateral three. The sides were heat-sealed to create a bag with only one side open. When 300 mm × 300 mm × 30 mm glass wool was used as the core material and dried, and then the core material and the outer packaging materials of Examples 1 and Comparative Examples 1 to 5 were used for the bag body, 5 g of a desiccant ( When the outer packaging materials of Examples 2 to 4 and Comparative Examples 6 and 7 were used as calcium oxide), 10 g of a desiccant (calcium oxide) was stored and the inside of the bag was exhausted. Then, the opening portion of the bag body was sealed with a heat seal to obtain a vacuum heat insulating material. The ultimate pressure was 0.05 Pa.

(Heat transfer rate of vacuum heat insulating material)
The thermal conductivity of the vacuum heat insulating material was measured according to the method and conditions described in the section "II. Vacuum heat insulating material" above. The measurement was carried out 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. The results are shown in Tables 2 and 3.

As shown in Tables 2 and 3, the vacuum heat insulating materials (Examples 1 to 4) having the outer packaging material for the vacuum heat insulating material of the present disclosure have radio wave transmission and can maintain the heat insulating performance for a long period of time. It became possible. On the other hand, since the outer packaging materials of Comparative Examples 1 and 6 have a metal layer, they do not transmit radio waves, and the outer packaging materials of Comparative Examples 2 to 5 and 7 are inferior in gas barrier property after the bending treatment, and this was used. The vacuum heat insulating material could not maintain good heat insulating performance.

1 ... Heat-weldable 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

An outer packaging material for a vacuum heat insulating material having a heat-weldable film and two or more inorganic layers including a first inorganic layer and a second inorganic layer.
The outer packaging material for the vacuum heat insulating material further contains 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.
Outer packaging material for vacuum heat insulating material without metal layer.
The outer packaging material for a vacuum heat insulating material according to claim 1, wherein a resin base material is not arranged between the inorganic layered compound layer and the first inorganic layer and the 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 packaging material for heat insulating material.
The heat-weldable film, the first resin base material, the first inorganic layer, the inorganic layered compound layer, the second inorganic layer, and the second resin layer were arranged in this order. , The outer packaging material for a vacuum heat insulating material according to claim 1.
The outer packaging material for a vacuum heat insulating material according to claim 4, wherein the third inorganic layer and the 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-weldable film, the first resin base material, the first inorganic layer, the inorganic layered compound layer, the second resin base material, the second inorganic layer, and the third inorganic layer. The outer packaging material for a vacuum heat insulating material according to claim 1, wherein the third resin base material and the third resin base material are arranged in this order.
The heat-weldable film, the first inorganic layer, the inorganic layered compound layer, the second inorganic layer, the second resin base material, the third inorganic layer, and the third resin base material. The outer packaging material for the vacuum heat insulating material according to claim 1, wherein the and are arranged in this order.
A vacuum heat insulating material having a core material and an outer packaging material in which the core material is enclosed.
The vacuum heat insulating material, wherein the outer packaging material is the vacuum heat insulating outer packaging material according to any one of claims 1 to 7.
An article having a heat insulating region and an article with a vacuum heat insulating material provided with the vacuum heat insulating material.
The vacuum heat insulating material has a core material and an outer packaging material in which the core material is enclosed.
An article with a vacuum heat insulating material, wherein the outer packaging material is the outer packaging material for vacuum heat insulating according to any one of claims 1 to 7.
The article with a vacuum heat insulating material according to claim 9, wherein the article with the vacuum heat insulating material has radio wave transmission.