JP6662408B2 - Outer packaging material for vacuum insulation, vacuum insulation, and articles with vacuum insulation - Google Patents

Description

  The present disclosure relates to an outer packaging material for a vacuum heat insulating material used for forming a vacuum heat insulating material.

  In recent years, vacuum heat insulating materials have been used for the purpose of energy saving of articles. The vacuum heat insulating material is a member in which a core material is disposed in a closed space of a bag body having a seal end formed by joining a peripheral edge of an outer packaging material, and the inside of the closed space is a vacuum having a pressure lower than the atmospheric pressure. Since the state is maintained, internal heat convection is suppressed, and good heat insulating performance can be exhibited. The outer packaging material used for the vacuum heat insulating material will be described as an outer packaging material for a vacuum heat insulating material or simply as an outer packaging material.

  The outer packaging material for vacuum heat insulating material has a gas barrier performance for suppressing the transmission of gases such as oxygen and water vapor in order to maintain a vacuum state inside the vacuum heat insulating material for a long period of time, and heat-welding the periphery of a pair of facing outer packaging materials. In order to form a bag having a seal end joined by the above method, physical properties such as heat welding properties for enclosing and sealing the core material are required. In order to satisfy these physical properties, as a vacuum heat insulating material outer packaging material, for example, a laminate having a gas barrier film provided with a gas barrier film made of a metal or an inorganic compound on a resin substrate, and a heat-sealable film, (Patent Documents 1 to 3).

JP 2003-262296 A JP 2006-70923 A JP 2004-036749 A Japanese Patent No. 4004279

The gas barrier film composed of a metal or an inorganic compound has good or bad water vapor barrier performance and good or bad oxygen barrier performance depending on the type. For example, the gas barrier film has good water vapor barrier performance, but the oxygen barrier performance is not sufficient, Is good, but the water vapor barrier performance is not sufficient.
On the other hand, as disclosed in Patent Document 4, it is known that an inorganic layered compound film containing an inorganic layered compound such as a clay mineral has good oxygen barrier performance. In order to improve the water vapor barrier performance and the oxygen barrier performance of the vacuum heat insulating material packaging material, the present inventors have developed a vacuum heat insulating material packaging material using a gas barrier film provided with an inorganic layered compound film on a gas barrier film. After examining the material, it was found that the gas barrier performance of the outer packaging material for a vacuum heat insulating material may deteriorate early in a high humidity environment.

  The present disclosure has been made in view of the above circumstances, and includes at least one gas barrier film having a gas barrier film made of a metal or an inorganic compound and a gas barrier film having an inorganic layered compound film, and has an effect of early deterioration of gas barrier performance under a high humidity environment. It is a main object to provide an outer packaging material for a vacuum heat insulating material, a vacuum heat insulating material, and an article with a vacuum heat insulating material that can be suppressed.

  The present disclosure provides a vacuum including: a heat-sealable film; and one or more gas barrier films located on the first main surface side of the heat-sealable film and having at least a gas barrier film made of a metal or an inorganic compound. An outer packaging material for a heat insulating material, wherein at least one of the gas barrier films further has an inorganic layered compound film on a first main surface side or a second main surface side of the gas barrier film, and In the thickness direction of the outer packaging material, the inorganic layered compound film located farthest from the heat-sealable film is more heat-sealable than the gas barrier film located farthest from the heat-sealable film. An outer packaging material for a vacuum insulation material is provided on the film side.

  Further, the present disclosure is a vacuum heat insulating material having a core material and an outer packaging material enclosing the core material, wherein the outer packaging material includes a heat-sealable film and a first main surface of the heat-sealable film. And at least one gas barrier film having at least a gas barrier film made of a metal or an inorganic compound, wherein at least one of the gas barrier films has a first main surface side or a second gas barrier film. Further having an inorganic layered compound film on the main surface side, in the thickness direction of the outer packaging material, the inorganic layered compound film at the position farthest from the heat-sealable film, the most remote from the heat-sealable film Vacuum heat insulating material is provided on the heat-sealable film side with respect to the gas barrier film in a position where the gas barrier film is positioned.

  Further, the present disclosure is an article having a heat insulating region and an article with a vacuum heat insulating material including a vacuum heat insulating material, wherein the vacuum heat insulating material has a core material and an outer packaging material for enclosing the core material, The material includes a heat-sealable film, and one or more gas barrier films that are located on the first main surface side of the heat-sealable film and have at least a gas barrier film made of a metal or an inorganic compound. At least one of the gas barrier films further has an inorganic layered compound film on the first principal surface side or the second principal surface side of the gas barrier film, and is formed from the heat-sealable film in the thickness direction of the outer packaging material. The inorganic layered compound film at the farthest position is closer to the heat-sealable film than the gas barrier film at the farthest position from the heat-sealable film. To provide a thermal material with the article.

  According to the present disclosure, in a packaging material for a vacuum heat insulating material including at least one gas barrier film having a gas barrier film made of a metal or an inorganic compound and a gas barrier film having an inorganic layered compound film, early deterioration of gas barrier performance under a high humidity environment is suppressed. It has the effect of being able to do so.

1 is a schematic cross-sectional view illustrating an example of an outer packaging material for a vacuum heat insulating material according to the present disclosure. 1 is a schematic cross-sectional view illustrating an example of an outer packaging material for a vacuum heat insulating material according to the present disclosure. 1 is a schematic cross-sectional view illustrating an example of an outer packaging material for a vacuum heat insulating material according to the present disclosure. 1 is a schematic cross-sectional view illustrating an example of an outer packaging material for a vacuum heat insulating material according to the present disclosure. 1 is a schematic cross-sectional view illustrating an example of an outer packaging material for a vacuum heat insulating material according to the present disclosure. It is a schematic perspective view and a sectional view showing an example of a vacuum heat insulating material of the present disclosure. 4 is a graph showing the change over time of the thermal conductivity of the vacuum heat insulating materials of Examples 1 to 4, Comparative Examples 1 and 2, and Reference Example 1 in an atmosphere where the temperature is 100 ° C and the humidity is not controlled. 4 is a graph showing the change over time in the thermal conductivity of the vacuum heat insulating materials of Examples 1 to 4, Comparative Examples 1 and 2, and Reference Example 1 in an atmosphere at a temperature of 40 ° C and a humidity of 90% RH.

  Hereinafter, embodiments of the present disclosure will be described with reference to the drawings and the like. However, the present disclosure can be implemented in many different modes, and should not be construed as being limited to the description of the embodiments illustrated below. Also, in order to make the description clearer, the width, thickness, shape, and the like of each part may be schematically illustrated as compared with the embodiments, but this is merely an example and the interpretation of the present disclosure is limited. It does not do. In the specification and the drawings, components similar to those described in regard to a drawing thereinabove are marked with like reference numerals, and a detailed description is omitted as appropriate. In addition, for convenience of description, the description may be made using the word “upward” or “downward”, but the vertical direction may be reversed.

  In this specification, there is no particular limitation when a certain structure such as a certain member or a certain region is “above (or below)” another structure such as another member or another region. To the extent that this includes not only directly above (or directly below) another configuration, but also above (or below) another configuration, i.e., separate (above or below) another configuration. This also includes the case where the component is included.

  Hereinafter, the outer packaging material for a vacuum heat insulating material, the vacuum heat insulating material, and the article with the vacuum heat insulating material according to the present disclosure will be described. In the present disclosure, “sheet” and “film” may be used synonymously.

I. An outer wrapping material for vacuum heat insulating material The outer wrapping material for vacuum heat insulating material of the present disclosure includes a heat-sealable film and a gas barrier film that is located on the first main surface side of the heat-sealable film and is made of a metal or an inorganic compound. And at least one gas barrier film having at least one gas barrier film, wherein at least one of the gas barrier films further includes an inorganic layered compound film on a first main surface side or a second main surface side of the gas barrier film. In the thickness direction of the vacuum insulating material outer packaging material, the inorganic layered compound film at a position farthest from the heat-sealable film is the gas barrier at a position farthest from the heat-sealable film. The heat-weldable film is located on the film side of the film.

  FIG. 1 is a schematic cross-sectional view illustrating an example of an outer packaging material for a vacuum heat insulating material according to the present disclosure. The outer packaging material 10 for a vacuum heat insulating material illustrated in FIG. 1 includes a heat-weldable film 12 and one gas barrier film 11 located on the first main surface 12a side of the heat-weldable film 12. An adhesive layer 13 is interposed between the gas barrier film 11 and the heat-weldable film 12. The gas barrier film 11 illustrated in FIG. 1 has an inorganic layered compound film 3, a gas barrier film 2 made of a metal or an inorganic compound, and a resin substrate 1 in this order from the heat-weldable film 12 side. Numeral 3 is formed directly on the first main surface 2a of the gas barrier film 2, and the resin substrate 1 is formed directly on the second main surface 2b of the gas barrier film 2. In FIG. 1, the inorganic layered compound film 3 at the position farthest from the heat-sealable film 12 in the thickness direction (TT ′ direction) of the vacuum insulation material outer packaging material 10 is separated from the heat-sealable film 12. It is on the side of the film 12 that can be thermally welded than the gas barrier film 2 at the farthest position.

  In the case where the inorganic layered compound film and the gas barrier film located farthest from the heat-sealable film in the thickness direction of the vacuum insulating material outer packaging material are respectively referred to as the outermost inorganic layered compound film and the outermost gas barrier film, There is.

  Outer packaging materials for vacuum heat insulating materials, including gas barrier films having an inorganic layered compound film on a gas barrier film made of a metal or inorganic compound, exhibit higher water vapor barrier performance due to the gas barrier film and higher oxygen barrier performance due to the inorganic layered film. can do. However, when such an outer packaging material for a vacuum heat insulating material is exposed to a high-humidity environment, the gas barrier performance may be deteriorated early. The following are speculated as the reason.

  Since the inorganic layered compound has a layered structure in which unit crystal layers are stacked on each other, the inorganic layered compound film formed of the inorganic layered compound absorbs moisture when exposed to a high humidity environment to form a layered layer of the inorganic layered compound. It is thought that water is retained in the gap between the structures. In particular, it is considered that the more the inorganic layered compound film is located in the thickness direction of the outer packaging material for a vacuum heat insulating material, the higher the water retention amount in the inorganic layered compound film is in the position where the inorganic layered compound film is easily in contact with moisture in the outside air. On the other hand, when the gas barrier film is in direct contact with such an inorganic layered compound film containing a large amount of moisture, the gas barrier film is always in contact with an excessive amount of moisture than when simply exposed to a high-humidity environment. It is presumed that it will be easier to progress. For example, when the gas barrier film is a metal aluminum film, metal aluminum is liable to undergo a property change in an aluminum compound such as aluminum hydroxide or aluminum oxide upon contact with moisture, and the water vapor barrier performance tends to deteriorate due to the property change. Therefore, if the metal aluminum film is always in contact with the moisture contained in the inorganic layered compound film, the progress of the property change is promoted, and as a result, the deterioration of the water vapor barrier performance of the entire outer packaging material for vacuum heat insulating material is reduced. It is thought to occur in time. It is presumed that such a phenomenon can occur not only when the gas barrier film is a metal aluminum film but also when it is another metal thin film or an inorganic compound film.

  Further, it is considered that when absorbing water, the inorganic layered compound film expands in volume by retaining water in gaps in the layered structure of the inorganic layered compound, and the gaps are considered to be enlarged. The inorganic layered compound film can exhibit oxygen barrier performance due to a so-called maze effect, which obstructs the passage of oxygen by the layered structure of the inorganic layered compound and lengthens the oxygen permeation path. It is considered that the layered structure collapses and oxygen easily passes therethrough, thereby deteriorating the oxygen barrier performance.

  In contrast, according to the present disclosure, in the thickness direction of the vacuum insulation material outer packaging material including the gas barrier film having the gas barrier film and the inorganic layered compound film, the inorganic layered compound film located farthest from the heat-sealable film is By arranging the gas barrier film located farthest from the heat-weldable film on the heat-weldable film side than the gas barrier film located farthest from the heat-weldable film, it is possible to suppress early deterioration of gas barrier performance in a high-humidity environment. . The reason is that by setting the outermost inorganic layered compound film and the outermost gas barrier film in a predetermined positional relationship, even when the vacuum insulating material outer packaging material is exposed to a high-humidity environment for a long time, the outermost It is presumed that the presence of the gas barrier film hinders contact between the outermost inorganic layered compound film and moisture in the outside air, thereby suppressing the outermost inorganic layered compound film from absorbing and retaining water.

  That is, according to the outer packaging material for a vacuum heat insulating material of the present disclosure, by setting the outermost inorganic layered compound film and the outermost gas barrier film in a predetermined positional relationship, the case is exposed to a high-humidity environment for a long time. In addition, it is possible to maintain the water vapor barrier performance by suppressing the moisture deterioration of the gas barrier film, and to maintain the oxygen barrier performance by suppressing the expansion of the gap in the outermost inorganic layered compound film due to water absorption and water retention. It is speculated that it can be done.

  In addition, the outermost gas barrier film is arranged at a position where it is easy to come into contact with moisture in the outside air in the thickness direction of the outer packaging material for vacuum heat insulating material, but is always directly in contact with the inorganic layered compound film containing a large amount of moisture. It is estimated that the degree of water deterioration is smaller than in the case of contact.

Hereinafter, the outer packaging material for a vacuum heat insulating material of the present disclosure will be described in detail.
In the following description, “the inorganic layered compound film is formed on the gas barrier film”, “the inorganic layered compound is in contact with the gas barrier film”, “the gas barrier film is formed on the resin base material”, or “the gas barrier film is The description such as "contacting with a resin base material" is not limited to "directly formed" or "directly contacting", but includes a case where another layer such as a coating layer such as an anchor coat is interposed.

1. Gas barrier film The gas barrier film in the envelope material for a vacuum heat insulating material according to the present disclosure is a member that is located on the first main surface side of the heat-sealable film and has at least a gas barrier film made of a metal or an inorganic compound. The outer packaging material for a vacuum heat insulating material of the present disclosure has one or more gas barrier films. At least one of the gas barrier films further has an inorganic layered compound film on the first main surface side or the second main surface side of the gas barrier film. In some cases, a gas barrier film further having an inorganic layered compound film is referred to as a gas barrier film with an inorganic layered compound film.

  Examples of the layer configuration of the gas barrier film include a layer configuration composed of a single gas barrier film, a layer configuration having a gas barrier film and a resin substrate formed on the second main surface of the gas barrier film, and the like.

  Examples of the layer configuration of the gas barrier film with an inorganic layered compound film include a layer configuration having a gas barrier film and an inorganic layered compound film formed on a first main surface of the gas barrier film (first layer configuration). A layer configuration (a second layer configuration) having a gas barrier film, an inorganic layered compound film formed on a first main surface of the gas barrier film, and a resin base material formed on a second main surface of the gas barrier film; Layer configuration comprising a gas barrier film, a resin substrate formed on the second main surface of the gas barrier film, and an inorganic layered compound film formed on the second main surface side of the gas barrier film via the resin substrate ( Third layer configuration). Among them, the gas barrier film with an inorganic layered compound film preferably has the first layer configuration or the second layer configuration.

(1) Gas barrier film The gas barrier film in the gas barrier film is made of a metal or an inorganic compound.

  The gas barrier film may be made of a metal or an inorganic compound, and may be a metal thin film or an inorganic compound film. When the gas barrier film is a metal thin film, examples of the metal constituting the gas barrier film include metals or alloys such as aluminum, nickel, stainless steel, iron, copper, and titanium. When the gas barrier film is an inorganic compound film, examples of the inorganic compound constituting the gas barrier film include silicon (silica), aluminum, stainless steel, titanium, nickel, iron, copper, magnesium, calcium, potassium, tin, sodium, Compounds such as oxides and nitrides such as boron, lead, zinc, zirconium and yttrium are exemplified.

  Among them, at least one gas barrier film is preferably a metal aluminum film, and at least the gas barrier film in contact with the inorganic layered compound film is more preferably a metal aluminum film, and the outermost gas barrier in contact with the outermost inorganic layered compound film It is particularly preferred that the film is a metal aluminum film. As described above, compared to other metal thin films and inorganic compound films, metallic aluminum is more likely to deteriorate in water vapor barrier performance due to contact with moisture. In addition, the metallic aluminum film in contact with the inorganic layered compound film containing a large amount of moisture due to moisture absorption is always in contact with an excessive amount of moisture than when simply exposed to a high-humidity environment, and the property change progresses more. It is presumed that it will be easier. Therefore, by defining the positional relationship between the outermost inorganic layered compound film and the outermost gas barrier film, the effect of suppressing the deterioration of the outermost metal aluminum film can be more remarkably exhibited.

  The gas barrier film may be a coating film by coating or the like, or may be a deposition film.

The thickness of the gas barrier film is not particularly limited as long as the desired gas barrier performance can be exhibited, and can be appropriately set according to the type of the gas barrier film. The thickness is, for example, preferably 5 nm or more and 1000 nm or less, and more preferably 10 nm or more and 500 nm or less.
When the gas barrier film is formed by vapor deposition a plurality of times, the thickness of the gas barrier film refers to the entire thickness after the vapor deposition a plurality of times.

(2) Inorganic layered compound film The gas barrier film may have an inorganic layered compound film on the first main surface side or the second main surface side of the gas barrier film.

  The inorganic layered compound film may be formed on the first main surface of the gas barrier film, or may be formed on the second main surface side of the gas barrier film via a resin base material. When the inorganic layered compound film is formed on the first main surface of the gas barrier film, no adhesive layer is interposed between the inorganic layered compound film and the gas barrier film. Note that the adhesive layer here does not include a coating layer such as an anchor coat.

  The inorganic layered compound film usually contains at least an inorganic layered compound and a binder resin.

(A) Inorganic layered compound The inorganic layered compound refers to an inorganic compound in which unit crystal layers are stacked on each other to have a layered structure. That is, the “layered compound” refers to a compound or substance having a layered structure. In addition, the “layered structure” refers to a structure in which planes in which atoms are strongly bonded by covalent bonds or the like and densely arranged are stacked in parallel by a weak bonding force such as van der Waals force.

  As the inorganic layered compound, any compound having a layered structure may be used, and examples thereof include graphite; phosphate derivative-type compounds (zirconium phosphate compounds); chalcogenides; and clay minerals. Among them, clay minerals are preferred.

Specific examples of clay minerals include phyllosilicate minerals such as hydrated silicates; kaolinite clay minerals such as halloysite, kaolinite, enderite, dickite, and nacrite; antigolite clays such as antigolite and chrysotile Minerals; smectite group clay minerals such as montmorillonite, iron montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, and stibnite; vermiculite group clay minerals such as vermiculite; mica such as muscovite and phlogopite; margarite; Examples include mica or mica group clay minerals such as lyric mica and teniolite; clay minerals of the chlorite group such as cocoaite, sudoite, clinochlore, chamosite, and nimite, or substituted or derivative products 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, phyllosilicate minerals and smectite group clay minerals are preferred, and montmorillonite and hectorite contained in smectite group clay minerals are particularly preferred.

The average particle size of the particles of the inorganic layered compound is preferably from 50 nm to 5 μm, more preferably from 100 nm to 4 μm, and particularly preferably from 500 nm to 3 μm.
This is because by setting the average particle size of the particles of the inorganic layered compound within the above range, the oxygen barrier performance of the inorganic layered compound film is further improved. The particle diameter of the particles of the inorganic layered compound is defined as the center diameter (major axis) determined by the photon correlation method based on dynamic light scattering measured using an ultrafine particle size analyzer at a temperature of 25 ° C. and in a water 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.
By setting the aspect ratio of the inorganic layered compound within the above range, the oxygen barrier performance of the inorganic layered compound film 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 size of the particles of the inorganic layered compound, and is calculated by the following equation (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 above-described method. The plane spacing (unit thickness) a of the inorganic layered compound is a value determined by, for example, powder X-ray diffraction measurement of the inorganic layered compound using an X-ray diffractometer. In addition, 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 interval of the inorganic layered compound is widened.

(B) Binder Resin The binder resin is not particularly limited, but a resin having a hydrogen bonding group or an ionic group is particularly preferable.

  The hydrogen-bonding group refers to a group having at least one hydrogen directly bonded to an atom other than carbon (hetero atom), and examples thereof include a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Can be

  An ionic group refers to a group having at least one charge of “positive or negative” localized to the extent that water molecules can be hydrated in water, such as a carboxylate group, a sulfonate ion group, and a phosphate ion. Group, ammonium group, phosphonium group and the like.

  Specific examples of the binder resin include polyvinyl alcohol (PVA); ethylene-vinyl alcohol copolymer (EVOH); polyacrylonitrile (PAN); hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, amylose, amylopectin, pullulan, curdlan, and xanthan. , Chitin, chitosan, cellulose, pullulan, chitosan and the like; polyacrylic acid or a salt thereof; polybenzenesulfonic acid or a salt thereof; polyethyleneimine, polyallylamine, polyglycerin and the like. In the present disclosure, among them, polyvinyl alcohol and polyacrylic acid are preferable.

(C) Others As the volume of the inorganic layered compound increases, the oxygen barrier performance of the inorganic layered compound film improves. 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.
By setting the volume ratio of the inorganic layered compound to the binder resin within the above range, an inorganic layered compound film having excellent oxygen barrier performance and bending resistance can be obtained.

The thickness of the inorganic layered compound film 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 film in the above range, it is possible to exhibit sufficient oxygen barrier performance, and since the hardness of the inorganic layered compound film can be made relatively small, the outer layer for vacuum heat insulating material is used. This is because the layered structure of the inorganic layered compound in the inorganic layered compound film can be maintained even when the material is subjected to bending stress.

(3) Resin base material The gas barrier film can have a resin base material formed on the second main surface of the gas barrier film. When the resin substrate is formed on the second main surface of the gas barrier film, no adhesive layer is interposed between the resin substrate and the gas barrier film. Note that the adhesive layer here does not include a coating layer such as an anchor coat.

The resin base material is not particularly limited as long as it can support the gas barrier film and the inorganic layered compound film. Examples thereof include polyolefin films such as polyethylene and polypropylene; polyethylene terephthalate (PET), polybutylene terephthalate (PBT). Polyester film such as polyethylene naphthalate (PEN); polystyrene film; polyamide film such as nylon; polyimide film; polyurethane film; polycarbonate film; poly (meth) acrylic film; ethylene-vinyl alcohol copolymer film; Cellulose films such as triacetyl cellulose; polyvinyl alcohol (PVA) films and the like.
In the present disclosure, a polyester film is preferable from the viewpoint of good dimensional stability, and a polyethylene terephthalate (PET) film is particularly preferable. This is because, since the melting point is relatively high, stable dimensional stability can be maintained even at high temperature conditions.

  The resin base material contains optional additives such as a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and a modifying resin. Is also good.

  The thickness of the resin base material is not particularly limited as long as it can have a desired strength, but can be, for example, 2 μm or more and 400 μm or less.

(4) Others At least one of the gas barrier films in the envelope material for a vacuum heat insulating material of the present disclosure is an inorganic layered compound further having an inorganic layered compound film on the first main surface side or the second main surface side of the gas barrier film. It is a gas barrier film with a film. When the outer packaging material for a vacuum heat insulating material has two or more gas barrier films, all the gas barrier films may be gas barrier films with an inorganic layered compound film, and one or more gas barrier films with an inorganic layered compound film, And at least one gas barrier film having no layered compound film.

2. Heat-Sealable Film The heat-sealable film in the outer packaging material for a vacuum heat insulating material of the present disclosure is a member that is positioned at the outermost side in one of the thickness directions of the outer packaging material for a vacuum heat insulating material and bears the outermost surface of the one. The heat-sealable film is in contact with the core when preparing the vacuum heat insulating material using the vacuum heat insulating material outer packaging material, and also, when sealing the core, a pair of the opposing members via the core. This is a member for joining the peripheral edges of the outer packaging material for vacuum heat insulating material by heat welding.

  As the heat-sealable film, a resin film that can be melted by heating and fused can be used. Examples of such a resin film include polyethylene such as linear short-chain branched polyethylene (LLDPE), polyolefin film such as undrawn polypropylene (CPP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate. Examples include polyester films such as (PBT), ethylene-vinyl alcohol copolymer film (EVOH), polyvinyl acetate film, polyvinyl chloride film, poly (meth) acryl film, urethane film and the like.

  The heat-weldable film preferably has a thickness capable of obtaining a desired adhesive force when joined, and the thickness can be, for example, 15 μm or more and 100 μm or less, and preferably 25 μm or more and 90 μm or less. The thickness is more preferably 30 μm or more and 80 μm or less.

3. Optional Configuration The outer packaging material for a vacuum heat insulating material of the present disclosure has a heat-sealable film on one outermost side in the thickness direction, and may have a protective film on the other outermost side. By having the protective film, the outermost material in the thickness direction of the outer packaging material for a vacuum heat insulating material can serve as the outermost surface, and components other than the protective film can be protected from damage and deterioration. As the protective film, a general-purpose resin film having a higher melting point than that of a heat-sealable film can be used, and examples thereof include a nylon film, a polyethylene terephthalate film, a polybutylene terephthalate film, and a polypropylene film. The thickness of the protective film is not particularly limited, and can be appropriately set.

  The outer packaging material for a vacuum heat insulating material of the present disclosure can be provided with an adhesive layer, for example, between a heat-sealable film and a gas barrier film, between two gas barrier films, between a gas barrier film and a protective film, and the like. As a material for the adhesive layer, a conventionally known pressure-sensitive adhesive, thermoplastic adhesive, curable adhesive, or the like can be used.

4. Others The outer packaging material for a vacuum heat insulating material of the present disclosure has the above-described heat-sealable film and one or more gas barrier films, and at least one of the gas barrier films is a gas barrier film with an inorganic layered compound film. In the thickness direction of the outer packaging material, the outermost inorganic layered compound film may have a laminated structure on the film side that can be thermally welded than the outermost gas barrier film, depending on the gas barrier performance of the vacuum insulation outer packaging material. The lamination structure can be appropriately designed.

  For example, when the outer packaging material for a vacuum heat insulating material has one gas barrier film, the lamination structure can be, for example, the lamination structure shown in FIG. Although not shown, the laminated structure shown in FIG. 1 may further include a protective film as an optional member on the side opposite to the heat-sealable film side of the gas barrier film.

  In the case where the outer packaging material for vacuum heat insulating material has two or more gas barrier films, the inorganic layered compound film (the outermost inorganic material) at the position farthest from the heat-sealable film in the thickness direction of the outer packaging material for vacuum heat insulating material. The layered compound film) is only required to be on the heat-bondable film side than the gas barrier film (outermost gas barrier film) located farthest from the heat-bondable film. The outermost inorganic layered compound film and the outermost gas barrier film The positional relationship between the inorganic layered compound film and the gas barrier film other than the above can be appropriately set.

Above all, the gas barrier film having two or more gas barrier films, and the gas barrier film at the position closest to the heat-sealable film in the thickness direction of the outer packaging material for vacuum heat insulating material is the inorganic layer at the position closest to the heat-sealable film. It is preferably on the side of the film that can be thermally welded rather than the compound film. In the case where the gas barrier film and the inorganic layered compound film located closest to the heat-sealable film in the thickness direction of the vacuum insulating material outer packaging material are the innermost gas barrier film and the innermost inorganic layered compound film, respectively. There is.
Since the innermost gas barrier film is positioned closer to the heat-sealable film than the innermost inorganic layered compound film, the first main surface of the heat-sealable film is included in the outer material for vacuum heat insulating material. All the inorganic layered compound films are sandwiched between the outermost gas barrier film and the innermost gas barrier film. With such a structure, for example, the movement of the innermost inorganic layered compound film that occurs when the outer packaging material for vacuum heat insulating material is subjected to heat or bending treatment is restricted, and the layered structure of the innermost inorganic layered compound film is collapsed. And the variation in thickness can be suppressed, and the oxygen barrier performance exerted by the inorganic layered compound film can be suppressed from deteriorating with time.

  As a laminated configuration in a case where the outer packaging material for a vacuum heat insulating material has two or more gas barrier films, for example, as illustrated in FIG. The first gas barrier film 11A and the second gas barrier film 11B are arranged in this order from the heat-weldable film 12 side, which is located on the surface 12a side, and the first gas barrier film 11A and the second gas barrier film 11B are respectively gas barrier films. Films 2A and 2B, inorganic layered compounds 3A and 3B directly formed on first main surface 2a of gas barrier films 2A and 2B, and resin base material directly formed on second main surface 2b of gas barrier films 2A and 2B A laminated structure which is a gas barrier film with an inorganic layered compound film having 1A and 1B is mentioned. An adhesive layer 13 is interposed between the first gas barrier film 11A and the heat-sealable film 12 and between the first gas barrier film 11A and the second gas barrier film 11B. Here, in the laminated configuration illustrated in FIG. 2, the outermost inorganic layered compound film refers to the inorganic layered compound film 3B of the second gas barrier film 11B, and the outermost gas barrier film refers to the gas barrier film of the second gas barrier film 11B. 2B. Therefore, in the laminated configuration illustrated in FIG. 2, the inorganic layered compound film 3B of the second gas barrier film 11B is closer to the film 12 that can be thermally welded than the gas barrier film 2B of the second gas barrier film 11B.

  2, the innermost inorganic layered compound film refers to the inorganic layered compound film 3A of the first gas barrier film 11A, and the innermost gas barrier film refers to the gas barrier film 2A of the first gas barrier film 11A. . Therefore, it is preferable that the gas barrier film 2A of the first gas barrier film 11A is closer to the film 12 that can be thermally welded than the inorganic layered compound film 3A of the first gas barrier film 11A. Although not shown, in the laminated configuration illustrated in FIG. 2, a protective film may be further provided as an optional member on the side opposite to the heat-sealable film side of the second gas barrier film.

  Further, as another example of the laminated structure in the case where the outer packaging material for vacuum heat insulating material has two or more gas barrier films, for example, as shown in FIG. The first gas barrier film 11A and the second gas barrier film 11B are arranged in this order from the heat-weldable film 12 side, which is located on the first main surface 12a side, and the first gas barrier film 11A is And a resin base material 1A directly formed on the second main surface 2b of the gas barrier film 2A, and the second gas barrier film 11B is formed directly on the gas barrier film 2B and the first main surface 2a of the gas barrier film 2B. A gas barrier film provided with an inorganic layered compound film, comprising: a layered inorganic layered compound film 3B; and a resin substrate 1B directly formed on the second main surface 2b of the gas barrier film 2B. Lamination structure that can be cited. Here, in the laminated configuration illustrated in FIG. 3, the outermost inorganic layered compound film refers to the inorganic layered compound film 3B of the second gas barrier film 11B, and the outermost gas barrier film refers to the gas barrier film of the second gas barrier film 11B. 2B. Therefore, in the laminated configuration illustrated in FIG. 3, the inorganic layered compound film 3B of the second gas barrier film 11B is closer to the film 12 that can be thermally welded than the gas barrier film 2B of the second gas barrier film 11B.

  In the laminated configuration illustrated in FIG. 3, the number of the inorganic layered compound films contained in the outer packaging material for a vacuum heat insulating material is one. For this reason, the inorganic layered compound film 3B of the second gas barrier film 11B is also the innermost inorganic layered compound film. On the other hand, the innermost gas barrier film refers to the gas barrier film 2A of the first gas barrier film 11A. Therefore, it is preferable that the gas barrier film 2A of the first gas barrier film 11A is on the side of the film 12 that can be thermally welded to the inorganic layered compound film 3B of the second gas barrier film 11B. Although not shown, in the laminated configuration illustrated in FIG. 3, a protective film may be further provided as an optional member on the side opposite to the heat-sealable film side of the second gas barrier film.

  Further, as another example of a laminated structure in which the outer packaging material for a vacuum heat insulating material has two or more gas barrier films, for example, as shown in FIG. The first gas barrier film 11A and the second gas barrier film 11B are arranged in this order from the heat-weldable film 12 side, which is located on the first main surface 12a side, and the first gas barrier film 11A is And an inorganic layered compound film 3A directly formed on the first main surface 2a of the gas barrier film 2A and a resin substrate 1A directly formed on the second main surface 2b of the gas barrier film 2A. A gas barrier film, wherein the second gas barrier film 11B comprises a gas barrier film 2B and a resin substrate 1B directly formed on the second main surface 2b of the gas barrier film 2B. Laminated structure that may be mentioned. Here, in the laminated structure illustrated in FIG. 4, the outermost inorganic layered compound film refers to the inorganic layered compound film 3A of the first gas barrier film 11A, and the outermost gas barrier film is the gas barrier film of the second gas barrier film 11B. 2B. Therefore, in the laminated configuration illustrated in FIG. 4, the inorganic layered compound film 3A of the first gas barrier film 11A is closer to the film 12 that can be thermally welded than the gas barrier film 2B of the second gas barrier film 11B.

  In the laminated configuration illustrated in FIG. 4, the number of the inorganic layered compound films included in the outer packaging material for a vacuum heat insulating material is one. For this reason, the inorganic layered compound film 3A of the first gas barrier film 11A is also the innermost inorganic layered compound film. On the other hand, the innermost gas barrier film refers to the gas barrier film 2A of the first gas barrier film 11A. Therefore, it is preferable that the gas barrier film 2A of the first gas barrier film 11A is on the side of the film 12 that can be thermally welded to the inorganic layered compound film 3A of the first gas barrier film 11A. Although not shown, in the laminated configuration illustrated in FIG. 4, a protective film may be further provided as an optional member on the side opposite to the heat-sealable film side of the second gas barrier film.

  Further, as another example of a laminated structure in which the outer packaging material for a vacuum heat insulating material has two or more gas barrier films, for example, as shown in FIG. A first gas barrier film 11A, a second gas barrier film 11B, and a third gas barrier film 11C, which are located on the first main surface 12a side and are arranged in this order from the heat weldable film 12 side; 11A, a second gas barrier film 11B and a third gas barrier film 11C are respectively formed by gas barrier films 2A, 2B and 2C, and an inorganic layered compound film 3A formed directly on the first main surface 2a of the gas barrier films 2A, 2B and 2C. 3B and 3C, and resin bases 1A and 1B directly formed on the second main surfaces 2b of the gas barrier films 2A, 2B and 2C. Lamination structure is an inorganic layered compound film with a gas barrier film having a 1C and the like. Here, in the laminated structure illustrated in FIG. 5, the outermost inorganic layered compound film refers to the inorganic layered compound film 3C of the third gas barrier film 11C, and the outermost gas barrier film refers to the gas barrier film of the third gas barrier film 11C. 2C. Therefore, in the laminated configuration illustrated in FIG. 5, the inorganic layered compound film 3C of the third gas barrier film 11C is closer to the film 12 that can be thermally welded than the gas barrier film 2C of the third gas barrier film 11C.

  In the laminated configuration illustrated in FIG. 5, the innermost layered compound film refers to the inorganic layered compound film 3A of the first gas barrier film 11A, and the innermost gas barrier film refers to the gas barrier film 2A of the first gas barrier film 11A. . Therefore, it is preferable that the gas barrier film 2A of the first gas barrier film 11A is closer to the film 12 that can be thermally welded than the inorganic layered compound film 3A of the first gas barrier film 11A.

  In the laminated configuration illustrated in FIG. 5, the second gas barrier film 11B is disposed such that the inorganic layered compound film 3B is closer to the film 12 that can be thermally welded than the gas barrier film 2B, but is not limited thereto. For example, the gas barrier film 2B may be arranged so as to be closer to the heat-weldable film 12 than the inorganic layered compound film 3B. Although not shown, in the laminated configuration illustrated in FIG. 5, a protective film may be further provided as an optional member on the side opposite to the thermally weldable film side of the third gas barrier film.

  When the outer packaging material for a vacuum heat insulating material has two or more gas barrier films, the laminated configuration is not limited to those illustrated in FIGS. 2 to 5 and can be appropriately designed.

The vacuum heat insulating material for outer material of the present disclosure, the lower the water vapor permeability preferably, for example, it is preferably 0.1g ^/ (m 2 · day) or less, preferably 0.05g ^/ (m 2 · day) or less In particular, it is preferably 0.01 g / (m ² · day) or less. The value of the water vapor permeability may be the initial water vapor permeability of the outer packaging material for a vacuum heat insulating material of the present disclosure.

The water vapor transmission rate of the outer packaging material for a vacuum heat insulating material is measured at a temperature of 40 ° C. and a relative humidity difference of 90% RH using a water vapor transmission rate measuring device in accordance with ISO 15106-5: 2015 (differential pressure method). Value. First, a sample of the vacuum heat insulating material outer packaging material cut into a desired size is placed on the high humidity side of the outermost surface opposite to the heat-sealable film in the outermost surface facing in the thickness direction (lamination direction). (Water supply side) so as to be mounted between the upper chamber and the lower chamber of the above-mentioned apparatus, with a permeation area of about 50 cm ² (permeation area: a circle having a diameter of 8 cm) at a temperature of 40 ° C. and a relative humidity difference of 90%. The measurement is performed under the condition of RH. As the water vapor transmission rate measuring apparatus, for example, “DELTAPERM” manufactured by Technologyox, UK can be used. The measurement of the water vapor transmission rate is performed on at least three samples for one envelope material for vacuum insulation material, and the average of the measured values is defined as the value of the water vapor transmission rate under the condition.

Further, the outer packaging material for a vacuum heat insulating material of the present disclosure is preferably as low as possible in oxygen permeability. For example, it is preferably 0.1 cc / (m ² · day · atm) or less, and particularly preferably 0.05 cc / (m ^2). * Day * atm) or less. The value of the oxygen permeability can be the initial oxygen permeability of the outer packaging material for a vacuum heat insulating material of the present disclosure.

The oxygen permeability of the outer packaging material for vacuum heat insulating material is determined according to JIS K7126-1: 2006 (Plastic film and sheet-Gas permeability test method-Part 2: Isobaric method, Appendix A: Oxygen gas permeability by electrolytic sensor method) The test method is referred to as a value measured using an oxygen gas permeability measuring apparatus under the conditions of a temperature of 23 ° C. and a humidity of 60% RH. In the above measurement, after a carrier gas was supplied at a flow rate of 10 cc / min for 60 minutes or more and purged, a test gas (at least 99.5% dry oxygen) was flowed, and a time period from the start of flow to the time when the equilibrium was reached was 12 hours After that, the transmission area is adjusted to about 50 cm ² (transmission area: a circle having a diameter of 8 cm), the conditions of the carrier gas and the test gas are adjusted to 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 of oxygen permeability is performed on at least three samples for one vacuum insulation material, and the average of the measured values is defined as the value of oxygen permeability under the condition.

  The thickness of the outer packaging material for a vacuum heat insulating material of the present disclosure is not particularly limited, and may be, for example, 30 μm or more, preferably 50 μm or more, and the thickness may be 200 μm or less, preferably 150 μm or less.

5. Manufacturing Method The manufacturing method of the outer packaging material for a vacuum heat insulating material of the present disclosure is not particularly limited, and a known method can be used. For example, a heat-weldable film and a gas barrier film are formed in advance, and a dry lamination method in which the film is bonded via an adhesive layer, or a heat-weldable film directly on one surface of the gas barrier film or via an adhesive layer. And the like.

6. Use The outer packaging material for a vacuum heat insulating material of the present disclosure can be used as an outer packaging material for covering a core material in a vacuum heat insulating material. The outer packaging material for a vacuum heat insulating material is disposed in a vacuum heat insulating material so that the outermost surface on the heat-sealable film side is located on the core material side with the core material interposed therebetween, and the peripheral edge is joined by heat welding. Used.

II. Vacuum Heat Insulating Material The vacuum heat insulating material of the present disclosure has a core material and an outer packaging material enclosing the core material, and the outer packaging material includes a heat-sealable film and a first heat-sealable film. And at least one gas barrier film having at least a gas barrier film made of a metal or an inorganic compound, wherein at least one of the gas barrier films has a first main surface side of the gas barrier film or An inorganic layered compound film further provided on the second principal surface side, wherein the inorganic layered compound film at a position farthest from the heat-sealable film in the thickness direction of the outer packaging material is the heat-sealable film; It is on the heat-weldable film side of the gas barrier film located farthest from the film.

  FIG. 6A is a schematic perspective view illustrating an example of the vacuum heat insulating material of the present disclosure, and FIG. 6B is a cross-sectional view taken along line XX of FIG. 6A. In FIGS. 6A and 6B, the illustration of the laminated structure of the outer packaging material 10 is omitted. The vacuum heat insulating material 20 illustrated in FIGS. 6A and 6B includes a core material 21 and an outer packaging material 10 for enclosing the core material 21, and a pair of outer packaging materials facing each other with the core material 21 interposed therebetween. 10 has a seal end 22 to which the peripheral edge is joined. Reference numeral 22a indicates an end face of the seal end portion 22.

  According to the vacuum heat insulating material of the present disclosure, since the outer material for enclosing the core material is the outer material for the vacuum heat insulating material described in the above section “I. The early deterioration of the gas barrier performance of the outer packaging material is suppressed, and high heat insulation performance can be exhibited for a long period of time.

  Hereinafter, the details of the vacuum heat insulating material of the present disclosure will be described.

1. Outer wrapping material The outer wrapping material in the vacuum heat insulating material of the present disclosure is a member for encapsulating a core material, and is arranged such that a film that can be thermally welded from the core material side and a gas barrier film are arranged in that order. The outer wrapping material is the same as the outer wrapping material for the vacuum heat insulating material described in the section “I. Outer wrapping material for vacuum heat insulating material”, and therefore, the description thereof is omitted here.

  Among them, the outer packaging material in the vacuum heat insulating material of the present disclosure has two or more gas barrier films, and in the thickness direction of the outer packaging material, the gas barrier film at the position closest to the heat-sealable film is formed from the heat-sealable film. It is preferably on the side of the film that can be heat-welded than the inorganic layered compound film at the closest position. The reason for this is the same as the reason described in the above section “I. Outer packaging material for vacuum heat insulating material”.

2. Core Material The core material in the vacuum heat insulating material of the present disclosure is a member that is enclosed by an outer packaging material. Note that “enclosed” means “sealed” inside a bag formed using an outer packaging material.

  The material of the core material preferably has a low thermal conductivity, and may be an inorganic material, an organic material, or a mixture of an organic material and an inorganic material. Specific examples of the core material include powders, foamed resins, fibers, and the like. These may be used alone or in a combination of two or more.

3. Others In the vacuum heat insulating material of the present disclosure, a core material is sealed in a bag formed of an outer packaging material, and the inside of the hermetically sealed interior is decompressed to be in a vacuum state. The degree of vacuum inside the vacuum heat insulating material is preferably, for example, 5 Pa or less. This is because heat conduction due to convection of air remaining inside can be reduced, and excellent heat insulating properties can be exhibited.

  The vacuum heat insulating material of the present disclosure is preferably as low as the thermal conductivity. This is because heat is not easily conducted to the outside, and a high heat insulating effect can be achieved. The thermal conductivity of the vacuum heat insulating material of the present disclosure is, for example, preferably 5 mW / (m · K) or less, more preferably 4 mW / (m · K) or less, and particularly preferably 3 mW / (m · K). ) Is more preferably the following. The thermal conductivity 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. in accordance with JIS A1412-2: 1999. For example, Auto Lambda HC-074 (manufactured by Eiko Seiki Co., Ltd.) can be used.

4. Manufacturing method The manufacturing method of the vacuum heat insulating material of the present disclosure is not particularly limited as long as it is a method using the vacuum heat insulating material outer packaging material described in the above section “I. Vacuum heat insulating material outer packaging material”. Method. First, two outer wrapping materials for vacuum heat insulating material described in the above section "I. Outer wrapping material for vacuum heat insulating material" are prepared, and the heat-sealable films are stacked one on top of the other, and the outer edges of the three sides are heated. Bonding (heat sealing) is performed by welding to obtain a bag body with one side opened. After a core material is put into the bag body from the opening, air is sucked from the opening, and the inside of the bag body is joined by heat welding and sealed in a state where the inside of the bag body is decompressed to obtain a vacuum heat insulating material. be able to.

III. Articles with Vacuum Insulation Material The articles with vacuum insulation material of the present disclosure include an article having a heat insulation region and a vacuum heat insulation material, wherein the vacuum heat insulation material includes a core material and an outer packaging material enclosing the core material. The outer packaging material has a heat-sealable film and one or more gas barrier films that are located on the first main surface side of the heat-sealable film and have at least a gas barrier film made of a metal or an inorganic compound. At least one of the gas barrier films further has an inorganic layered compound film on a first principal surface side or a second principal surface side of the gas barrier film, and the heat barrier film has a thickness in the thickness direction of the outer packaging material. The inorganic layered compound film at the position farthest from the weldable film is more heat-sealable than the gas barrier film at the position farthest from the heat-sealable film. On the Lum side.

  According to the article with the vacuum heat insulating material of the present disclosure, the outer wrapping material constituting the vacuum heat insulating material provided in the article is the same as that described in the above section “I. The early deterioration of the gas barrier performance of the outer packaging material is suppressed, and the vacuum heat insulating material can exhibit good heat insulating performance for a long time in a high humidity environment. By providing such a vacuum heat insulating material, energy saving of an article and an object using the article can be achieved.

  Hereinafter, the details of the article with the vacuum heat insulating material of the present disclosure will be described. The vacuum heat insulating material in the article with the vacuum heat insulating material of the present disclosure and the outer packaging material used for the vacuum heat insulating material are described in the above “II. Vacuum heat insulating material” and “I. Since the details have been described, the description here is omitted.

  The article in the article with the vacuum heat insulating material of the present disclosure has a heat insulating region. Here, the above-mentioned heat insulating region is a region thermally insulated by a vacuum heat insulating material, and is, for example, a region kept warm or cold, a region surrounding a heat source or a cooling source, a region isolated from a heat source or a cooling source. It is. These regions may be spaces or objects. As the above-mentioned articles, for example, electric equipment such as refrigerators, freezers, heat insulators, and coolers, heat insulators, cool containers, transport containers, containers, containers such as storage containers, vehicles such as vehicles, aircraft, ships, houses, warehouses, and the like Building materials such as buildings, wall materials and floor materials.

  Note that the present disclosure is not limited to the above embodiment. The above embodiment is an exemplification, and has substantially the same configuration as the technical idea described in the claims of the present disclosure, and any device having the same function and effect will not be described. It is within the technical scope of the disclosure.

  Hereinafter, the present disclosure will be described more specifically with reference to Examples and Comparative Examples.

[Preparation]
The details of the film used for producing the outer packaging material for vacuum heat insulating material are shown below.
PET12: polyethylene terephthalate film having a thickness of 12 μm (“E5120” manufactured by Toyobo Co., Ltd.)
・ ON15: Biaxially stretched nylon film with a thickness of 15 μm (“Emblem ONBC” manufactured by Unitika)
LLDPE50: Linear low-density polyethylene film having a thickness of 50 μm (“TUX (registered trademark) HC-E” manufactured by Mitsui Chemicals Tokyo Sero Co., Ltd.)
· SiO ₂ deposition PET12: PET12 one side to the silica-deposited film (SiO ₂ film) is directly formed film (Dai Nippon Printing Co., Ltd. "IBPET-UB")
· _Al 2 _{O 3} deposited PET 12: PET 12 sided aluminum oxide deposited film of _(Al 2 _{O 3} film) was formed directly film (Dai Nippon Printing Co., Ltd. "IBPET-PXB")

[Production of gas barrier film A]
PET12 was set as a resin base material in the unwinding device of a continuous vacuum evaporator (TopMet, manufactured by APPLIED MATERIALS), and an aluminum wire was applied to the resistance heating unit in the vacuum evaporator in which the pressure was reduced to less than 1.0 × 10 ^-1 Pa. The metal aluminum was fed and melted, and vaporized metallic aluminum was adhered and deposited on one surface of PET 12 traveling at a traveling speed of 300 m / min, and vapor deposition was performed once. The electric power value (evaporation board electric power value) supplied to the resistance heating unit when the aluminum wire was melted was in the range of 8.0 kW to 9.0 kW. Thus, a gas barrier film A in which a metal aluminum film (Al film) was directly formed on one surface of PET 12 was obtained.

[Preparation of gas barrier film B]
First, PVA (polyvinyl alcohol) granules (manufactured by Japan Vineyard Poval Co., Ltd .: JF-04, degree of saponification 98 to 99%, average degree of polymerization 400) are dissolved in ion-exchanged water, and polyvinyl alcohol of 20% by mass is dissolved. An alcohol aqueous solution was obtained. Montmorillonite (Kunimine Kogyo Co., Ltd .: Kunipia F) was added to this aqueous solution so as to be 10% by mass based on the solid mass, and stirred to prepare an inorganic layered compound-containing coating solution.
Next, the inorganic layered compound-containing coating solution is coated on the Al film of the gas barrier film A by a gravure coating method, and then heat-treated at 120 ° C., 140 ° C., and 150 ° C. for 20 seconds each to form the gas barrier film A. An inorganic layered compound film was directly formed on the Al film of A, and a gas barrier film B having an inorganic layered compound film, an Al film, and PET12 in this order was produced.

[Gas barrier film C]
The SiO ₂ deposited PET12 was gas barrier film C.

[Gas barrier film D]
The al ₂ O ₃ deposited PET12 was gas barrier film D.

[Gas barrier film E]
An inorganic layered compound film was directly formed on the SiO ₂ film of the gas barrier film C in the same manner as the gas barrier film B, and a gas barrier film E having an inorganic layered compound film, a SiO ₂ film, and PET12 in this order was produced.

[Examples 1 to 7, Comparative Examples 1 and 2, Reference Example 1]
An outer packaging material for a vacuum heat insulating material having a laminated structure shown in Table 1 below was obtained. [] Of the gas barrier film in Table 1 indicates the lamination order of the members constituting the gas barrier film. In Table 1, “/” indicates an interface directly laminated, and “//” indicates an interface laminated via an adhesive layer. The adhesive layer is composed of a main component mainly composed of polyester polyol (product name: RU-77T manufactured by Rock Paint), a curing agent containing an aliphatic polyisocyanate (product name: H-7 manufactured by Rock Paint), and acetic acid. One of two components to be bonded together using a two-component curable adhesive in which a solvent of ethyl is mixed such that a weight ratio of the main component: the curing agent: the solvent = 10: 1: 14. The adhesive was applied to the surface of the member so as to have a coating amount of 3.5 g / m ^2, and the other component was pressed with the adhesive layer interposed therebetween.

  Two pieces of the obtained outer packaging material for vacuum heat insulating material (dimensions: 360 mm × 450 mm) are prepared, and two sheets are stacked so that the heat-weldable films face each other, and three sides of a quadrilateral are heat-sealed to only one side. A bag was opened. After using glass wool of 290 mm × 300 mm × 30 mm as a core material and performing a drying treatment, the bag material was filled with 5 g of calcium oxide as a core material and a desiccant, and the inside of the bag material was evacuated. Thereafter, the opening of the bag was sealed by heat sealing to obtain a vacuum heat insulating material. The ultimate pressure was 0.05 Pa.

[Evaluation 1]
About the obtained vacuum heat insulating material, the thermal conductivity after holding | maintenance in 100 degreeC temperature and humidity uncontrolled atmosphere was measured with time. The measurement was performed in accordance with JIS A1412-2: 1999 (Method of measuring thermal resistance and thermal conductivity of thermal insulating material-Part 2: Heat flow meter method (HFM method)) in accordance with a thermal conductivity measuring device (Auto Lambda HC). −074, manufactured by Eiko Seiki Co., Ltd.), and the vacuum heat insulating material was arranged so that the main surface thereof was oriented in the up-down direction under the following conditions. The measurement was performed using at least three samples, and the average of the measured values was defined as the thermal conductivity of the vacuum insulating material.
(Measurement conditions of thermal conductivity)
-The time required for the steady state of the test: 15 minutes or more-Standard plate: EPS
・ Temperature of hot surface: 30 ° C
・ Cold surface temperature: 10 ℃
・ Average temperature of measurement sample: 20 ° C

  The results of Evaluation 1 are shown in Table 2 below. FIG. 7 shows changes over time in the thermal conductivity of the vacuum heat insulating materials of Examples 1 to 4, Comparative Examples 1 and 2, and Reference Example 1 in an atmosphere where the temperature is 100 ° C. and the humidity is not controlled.

[Evaluation 2]
About the obtained vacuum heat insulating material, the thermal conductivity after holding in an atmosphere of a temperature of 40 ° C. and a humidity of 90% RH was measured over time. The measurement method and the measurement conditions were the same as in Evaluation 1. The results of Evaluation 2 are shown in Table 3 below. FIG. 8 shows the change over time in the thermal conductivity of the vacuum heat insulating materials of Examples 1 to 4, Comparative Examples 1 and 2, and Reference Example 1 in an atmosphere at a temperature of 40 ° C. and a humidity of 90% RH.

  From the results of Evaluation 1 and Evaluation 2, and FIGS. 7 and 8, in a temperature of 100 ° C. and an uncontrolled humidity atmosphere, both the vacuum heat insulating materials of Examples 1 to 4 and the vacuum heat insulating materials of Comparative Examples 1 and 2 showed heat. Although there was no significant difference in the change with time of the conductivity, in a temperature of 40 ° C. and a humidity of 90% RH (high humidity environment), the vacuum heat insulating materials of Comparative Examples 1 and 2 were the same as those of Examples 1 to 4. An increase in thermal conductivity was confirmed earlier than the material. From this, it is considered that the gas barrier performance of the outer packaging materials for vacuum heat insulating materials of Comparative Examples 1 and 2 deteriorated early in a high humidity environment. The outer packaging material for vacuum heat insulating materials of Examples 1 to 4 was the film side on which the outermost inorganic layered compound film could be thermally welded than the outermost Al film, whereas the outer packaging material for vacuum heat insulating materials of Comparative Examples 1 and 2. The outer packaging material was on the film side where the outermost Al film could be thermally welded than the outermost inorganic layered compound film. From the above, the outer packaging material for a vacuum heat insulating material including at least one gas barrier film having an inorganic layered compound film on an Al film, the outermost inorganic layered compound film in the thickness direction can be more thermally welded than the outermost Al film. It was suggested that by arranging it on the film side, it is possible to suppress early deterioration of gas barrier performance in a high humidity environment.

1, 1A, 1B, 1C ... resin base material 2, 2A, 2B, 2C ... gas barrier film 2a ... first main surface of gas barrier film 2b ... second main surface of gas barrier film 3, 3A, 3B, 3C ... inorganic Layered compound film 10 ... outer packaging material for vacuum heat insulating material 11, 11A, 11B, 11C ... gas barrier film 12 ... heat-weldable film 12a ... first main surface of heat-weldable film 20 ... vacuum heat insulating material 21 ... core material 22 ... Seal end

Claims (3)

An outer package for a vacuum heat insulating material, comprising: a heat-sealable film; and two or more gas barrier films located on the first main surface side of the heat-sealable film and having at least a gas barrier film made of a metal or an inorganic compound. Wood,
At least one of the gas barrier films further includes an inorganic layered compound film on a first main surface side or a second main surface side of the gas barrier film,
In the thickness direction of the vacuum insulating material outer packaging material, the inorganic layered compound film at a position farthest from the heat-sealable film is more than the gas barrier film at a position farthest from the heat-sealable film. On the heat-sealable film side,
The gas barrier film closest to the heat-sealable film in the thickness direction of the vacuum insulating material outer packaging material has a higher thermal conductivity than the inorganic layered compound film closest to the heat-sealable film. On the side of the film that can be welded,
The gas barrier film at a position farthest from the heat-sealable film is in contact with the inorganic layered compound film at a position farthest from the heat-sealable film,
The gas barrier layer which is positioned farthest from the heat weldable film, Ri metallic aluminum film der,
An outer packaging material for a vacuum heat insulating material, wherein the heat-sealable film is a polyolefin film, an ethylene-vinyl alcohol copolymer film, a polyvinyl acetate film, a polyvinyl chloride film, a poly (meth) acryl film, or a urethane film . A vacuum heat insulating material having a core material and an outer packaging material enclosing the core material,
The outer packaging material includes a heat-sealable film, and two or more gas barrier films that are located on the first main surface side of the heat-sealable film and have at least a gas barrier film made of a metal or an inorganic compound. ,
At least one of the gas barrier films further includes an inorganic layered compound film on a first main surface side or a second main surface side of the gas barrier film,
In the thickness direction of the outer packaging material, the inorganic layered compound film at a position farthest from the heat-sealable film is more heat-sealable than the gas barrier film at a position farthest from the heat-sealable film. On the film side,
In the thickness direction of the outer packaging material, the gas barrier film closest to the heat-sealable film is the heat-sealable film than the inorganic layered compound film closest to the heat-sealable film. On the side,
The gas barrier film at a position farthest from the heat-sealable film is in contact with the inorganic layered compound film at a position farthest from the heat-sealable film,
The gas barrier layer which is positioned farthest from the heat weldable film, Ri metallic aluminum film der,
A vacuum heat insulating material, wherein the heat-sealable film is a polyolefin film, an ethylene-vinyl alcohol copolymer film, a polyvinyl acetate film, a polyvinyl chloride film, a poly (meth) acryl film or a urethane film . An article having a heat insulating region and an article with a vacuum heat insulating material including a vacuum heat insulating material,
The vacuum heat insulating material has a core material and an outer packaging material enclosing the core material,
The outer packaging material includes a heat-sealable film, and two or more gas barrier films that are located on the first main surface side of the heat-sealable film and have at least a gas barrier film made of a metal or an inorganic compound. ,
At least one of the gas barrier films further includes an inorganic layered compound film on a first main surface side or a second main surface side of the gas barrier film,
In the thickness direction of the outer packaging material, the inorganic layered compound film at a position farthest from the heat-sealable film is more heat-sealable than the gas barrier film at a position farthest from the heat-sealable film. On the film side,
In the thickness direction of the outer packaging material, the gas barrier film closest to the heat-sealable film is the heat-sealable film than the inorganic layered compound film closest to the heat-sealable film. On the side,
The gas barrier film at a position farthest from the heat-sealable film is in contact with the inorganic layered compound film at a position farthest from the heat-sealable film,
The gas barrier layer which is positioned farthest from the heat weldable film, Ri metallic aluminum film der,
The article with a vacuum heat insulating material, wherein the heat-sealable film is a polyolefin film, an ethylene-vinyl alcohol copolymer film, a polyvinyl acetate film, a polyvinyl chloride film, a poly (meth) acryl film or a urethane film .