JP2020034156A - Outer packing material for vacuum heat insulating material, vacuum heat insulating material, and article with vacuum heat insulating material - Google Patents

Abstract

To provide an outer packing material for a vacuum heat insulating material, a vacuum heat insulating material using the same, and an article with the vacuum heat insulating material.SOLUTION: An outer packing material 10 for a vacuum heat insulating material has a gas barrier film 11 having a metal aluminum film 1, and an adhesive layer 12 directly arranged on the metal aluminum film 1. The adhesive layer 12 comprises an adhesive component, and a silicon-containing compound in which at least one of a hydrolyzable group or a hydroxyl group is directly bonded to a silicon atom. The adhesive layer 12 has an atomic ratio of silicon atoms of 1.5 at% or more and 7.0 at% or less.SELECTED DRAWING: Figure 1

Description

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

  In recent years, vacuum heat insulating materials have been used for the purpose of energy saving of articles. The vacuum heat insulating material is a member in which a core material is disposed in a bag body of an outer packaging material, and the bag body is held in a vacuum state in which the pressure is lower than the atmospheric pressure, and the internal heat convection is suppressed. It can exhibit excellent heat insulation performance. 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. Thus, physical properties such as heat welding properties for sealing and sealing the core material are required. In order to satisfy these physical properties, a laminate including a gas barrier film and a heat-sealable film as constituent members is generally employed as an outer packaging material for a vacuum heat insulating material (Patent Documents 1 to 5).

  As the gas barrier film, for example, a configuration in which an inorganic thin film such as a metal film or a metal oxide film is formed on a surface of a base material such as a plastic film is known. Above all, a gas barrier film having a metal aluminum film as the inorganic thin film can have high water vapor barrier performance at a relatively low cost.

JP 2005-351405 A JP 2008-023932 A JP-A-2004-130654 JP-A-2005-075182 Patent No. 6149997

  When the vacuum heat insulating material outer packaging material including the gas barrier film having the metal aluminum film is exposed to a high-temperature and high-humidity environment for a long period of time, the property change of the metal aluminum film occurs. May deteriorate in a short time.

  The present disclosure includes a gas barrier film having a metal aluminum film, even when exposed to a high-temperature and high-humidity environment for a long period of time, and a vacuum insulation material outer packaging material capable of suppressing deterioration of water vapor barrier performance, and A main object is to provide a vacuum heat insulating material and an article with a vacuum heat insulating material using the same.

  The present disclosure includes a gas barrier film having a metal aluminum film, and an adhesive layer directly disposed on the metal aluminum film, wherein the adhesive layer includes an adhesive component and at least one of a hydrolyzable group or a hydroxyl group. And a silicon-containing compound directly bonded to a silicon atom, wherein the adhesive layer provides an outer packaging material for a vacuum heat insulating material, wherein the atomic ratio of the silicon atom is 1.5 at% or more and 7.0 at% or less. .

  In the following description, the “atom ratio of silicon atoms” may be described as “silicon atom ratio (in the adhesive layer)”. In addition, the “atomic ratio of organosilicon atoms” in the specification may also be referred to as “organic silicon atom ratio (in the adhesive layer)”.

  Further, the present disclosure is a vacuum heat insulating material having a core material and an outer packaging material in which the core material is sealed, wherein the outer packaging material is a gas barrier film having a metal aluminum film, and directly on the metal aluminum film. An adhesive layer disposed, wherein the adhesive layer includes an adhesive component and a silicon-containing compound in which at least one of a hydrolyzable group or a hydroxyl group is directly bonded to a silicon atom. And a vacuum heat insulating material having an atomic ratio of the silicon atoms of 1.5 at% or more and 7.0 at% or less.

  Further, the present disclosure relates to an article having a heat insulating region and an article with a vacuum heat insulating material provided with a vacuum heat insulating material, wherein the vacuum heat insulating material has a core material and an outer packaging material in which the core material is sealed. The outer packaging material has a gas barrier film having a metal aluminum film, and an adhesive layer directly disposed on the metal aluminum film, and the adhesive layer has an adhesive component, a hydrolyzable group or a hydroxyl group. A silicon-containing compound in which at least one kind is directly bonded to a silicon atom, and the adhesive layer is an article with a vacuum heat insulating material, wherein the atomic ratio of the silicon atom is 1.5 at% or more and 7.0 at% or less. provide.

  According to the envelope material for a vacuum heat insulating material of the present disclosure, an adhesive layer containing a silicon-containing compound in which at least one of a hydrolyzable group or a hydroxyl group is directly bonded to a silicon atom, and having a silicon atom ratio in a predetermined range. However, by directly disposing the gas barrier film having a metal aluminum film on the metal aluminum film, it is possible to suppress the deterioration of the water vapor barrier performance even when the gas barrier film is exposed to a high-temperature and high-humidity environment for a long time. It works.

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 schematic sectional view showing an example of the vacuum heat insulating material of the present disclosure.

  The present disclosure includes, in an embodiment, an outer packaging material for vacuum insulation, a vacuum insulation, and an article with vacuum insulation. 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.

I. The outer wrapping material for vacuum heat insulating material The outer wrapping material for vacuum heat insulating material of the present disclosure (hereinafter, may be referred to as the outer wrapping material of the present disclosure) is disposed directly on a gas barrier film having a metal aluminum film and the metal aluminum film. The adhesive layer comprises an adhesive component and a silicon-containing compound in which at least one of a hydrolyzable group or a hydroxyl group is directly bonded to a silicon atom. The atomic ratio of silicon atoms is within a predetermined range.

  FIG. 1 is a schematic cross-sectional view illustrating an example of the outer packaging material of the present disclosure. An outer packaging material 10 for a vacuum heat insulating material shown in FIG. 1 includes a metal aluminum film 1, a gas barrier film 11 having a base material 2 disposed on one surface of the metal aluminum film 1, and a gas barrier film 11 having the other surface of the metal aluminum film 1. And an adhesive layer 12 directly disposed on the substrate. In FIG. 1, a film 13 that can be thermally welded is arranged on the surface of the adhesive layer 12 opposite to the surface in contact with the metal aluminum film 1. The adhesive layer 12 includes an adhesive component and a silicon-containing compound in which at least one of a hydrolyzable group or a hydroxyl group is directly bonded to a silicon atom. The adhesive layer 12 has an atomic ratio of silicon atoms within a predetermined range.

  In the outer packaging material of the present disclosure, “the adhesive layer is directly arranged on the metal aluminum film” means that one surface of the adhesive layer is in contact with one surface of the metal aluminum film in the thickness (lamination) direction of the outer packaging material. It means that no other layer is interposed between the metal aluminum film and the adhesive layer.

  When the metal aluminum film is exposed to air, it reacts with oxygen in the air to form an oxide film on the surface, and the oxide film reacts with water molecules in the air to cover the surface with hydroxyl groups. It has been known. For this reason, in an outer packaging material for a vacuum heat insulating material including a gas barrier film having a metal aluminum film in its configuration, a hydroxyl group usually exists on the surface of the metal aluminum film. Here, since the hydroxyl group is a hydrophilic group, when the outer packaging material for vacuum heat insulating material is exposed to a high-humidity environment for a long period of time, the hydroxyl groups present on the surface of the metal aluminum film cause water molecules in the air permeating the outer packaging material to pass through. When the metal aluminum film is adsorbed to form a hydrogen bond and the surface of the metal aluminum film is covered with a large amount of water molecules, the property change to the aluminum compound further proceeds to the inside of the film. Then, with the change in the properties of the metal aluminum film, the water vapor barrier performance deteriorates, and as a result, the water vapor barrier performance of the entire outer packaging material for vacuum heat insulating material also deteriorates. It is not clear why the water vapor barrier performance deteriorates due to the property change of the metal aluminum film, but the distorted property change from the metal aluminum film to the aluminum compound proceeds throughout the film, so that the aluminum compound and the metal aluminum Is mixed, and a fine water vapor passage is formed at the interface between the aluminum compound and metallic aluminum.

  In addition, in a high-temperature environment in addition to a high-humidity environment, water molecules in the air are more likely to pass through the outer packaging material, so that the metal aluminum film is more likely to come in contact with the water molecules, and the property change of the metal aluminum film progresses. Is promoted. Therefore, the water vapor barrier performance of the entire metal aluminum film and the outer packaging material for a vacuum heat insulating material deteriorates in a shorter time than when exposed to a normal temperature environment.

  As described above, in some cases, it is difficult for the vacuum heat insulating material outer packaging material including the gas barrier film having the metal aluminum film to exhibit the water vapor barrier performance in a high-temperature and high-humidity environment for a long period of time. In addition, when a vacuum heat insulating material using such a vacuum heat insulating material outer packaging material is used in a high-temperature and high-humidity environment, the degree of internal vacuum is rapidly reduced, and it becomes difficult to exhibit heat insulating performance for a long time. There is.

  In contrast, according to the outer packaging material of the present disclosure, an adhesive layer containing a silicon-containing compound in which at least one of a hydrolyzable group or a hydroxyl group is directly bonded to a silicon atom, and having a silicon atom ratio in a predetermined range. However, by being disposed in direct contact with the metal aluminum film of the gas barrier film having a metal aluminum film, it is possible to suppress the deterioration of the water vapor barrier performance even when exposed to a high-temperature and high-humidity environment for a long time. It is possible. This is presumed to be due to the following reasons. That is, the hydrolyzable group or the hydroxyl group of the silicon-containing compound contained in the adhesive layer becomes a silanol group directly or by a hydrolysis reaction with a water molecule, and becomes a hydroxyl group existing on the surface of the metallic aluminum film on the adhesive layer side. A hydrogen bond can be formed, or a covalent bond can be formed through a dehydration condensation reaction with the above hydroxyl group. Thereby, the hydroxyl groups present on the surface of the metal aluminum film on the adhesive layer side are blocked, and the adsorption of water molecules can be prevented, and the property change of the metal aluminum film and the accompanying deterioration of the water vapor barrier performance can be suppressed. . Further, by setting the silicon atom ratio in the adhesive layer to a predetermined range, a sufficient amount of a silicon-containing compound to form a desired bond with a hydroxyl group present on the surface of the metallic aluminum film on the adhesive layer side is sufficient for the adhesive layer. Will be inside. Thereby, the hydroxyl groups existing on the surface of the metal aluminum film on the side of the adhesive layer can be sufficiently blocked. Further, when the silicon-containing compound bonded to the metal aluminum film has a hydrophobic functional group, the hydrophobicity of the film surface of the metal aluminum film is increased, so that the probability of the presence of water molecules on the film surface can be reduced. For these reasons, the above-described effects can be sufficiently exerted.

  The outer packaging material of the present disclosure is exposed to a high-temperature and high-humidity environment for a long time, so that a hydroxyl group bonded to a silicon atom of a silicon-containing compound and a hydroxyl group present on the surface of the metal aluminum film are formed between the adhesive layer and the metal aluminum film. It is presumed that a hydrogen bond or a Si—O—Al bond (covalent bond) is formed between them. Such a guess is obtained, for example, by applying a silicon-containing compound to the surface of the metal aluminum film, removing the silicon-containing compound by ultrasonic cleaning with acetone, and analyzing the ratio of silicon atoms remaining on the surface of the metal aluminum film after cleaning by X-ray photoelectron spectroscopy. It is based on indirect confirmation that the metal aluminum film and the silicon-containing compound are bonded when analyzed by (XPS). For example, when a silicon-containing compound is applied to the surface of a polyethylene terephthalate (PET) film, a desired bond is not formed between the PET film and the silicon-containing compound coating film. No silicon atoms remain on the surface of the PET film after ultrasonic cleaning.

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

A. Adhesive layer The adhesive layer in the envelope material of the present disclosure is disposed directly on the metal aluminum film of the gas barrier film having the metal aluminum film, and the adhesive component and at least one of the hydrolyzable group or the hydroxyl group is directly bonded to the silicon atom. And a silicon-containing compound bound thereto.

  In the adhesive layer in the outer packaging material of the present disclosure, the atomic ratio of silicon atoms (silicon atom ratio in the adhesive layer) is within a predetermined range. Here, the silicon atom ratio in the adhesive layer means the carbon atom, oxygen atom, nitrogen atom, and silicon atom (inorganic silicon atom and organic silicon atom) on the surface of the adhesive layer, as measured by X-ray photoelectron spectroscopy (XPS). ) Is the atomic ratio of silicon atoms when the total number of atoms is 100 at%. Further, as described later, when the silicon-containing compound is an organic silicon compound, the atomic ratio of organic silicon atoms (organic silicon atom ratio in the adhesive layer) is measured by X-ray photoelectron spectroscopy (XPS). The atomic ratio of organic silicon atoms when the total number of carbon atoms, oxygen atoms, nitrogen atoms, and organic silicon atoms on the surface of the adhesive layer is 100 at%.

  The silicon atom ratio in the adhesive layer may be 7.0 at% or less. By setting the silicon atom ratio to 7.0 at% or less, it is possible to sufficiently suppress the adsorption of water molecules to the metal aluminum film and the property change while the adhesive layer exhibits a sufficient adhesive force. . Above all, the silicon atom ratio in the adhesive layer is preferably 5.0 at% or less, more preferably 4.5 at% or less, and particularly preferably 4.0 at% or less. By setting the silicon atom ratio to 5.0 at% or less, the amount of gas such as alcohol gas generated by the reaction between the hydrolyzable group of the silicon-containing compound and the hydroxyl group of the metal aluminum film can be further reduced, Higher heat insulation performance can be maintained. Further, the silicon atom ratio in the adhesive layer may be 1.5 at% or more, preferably 2.0 at% or more, and more preferably 2.5 at% or more.

  Accordingly, the silicon atom ratio in the adhesive layer is within a predetermined range, specifically, when the atomic ratio of silicon atoms is 1.5 at% or more and 7.0 at% or less, and 1.5 at% or more and 5 at% or less. 0.0 at% or less, more preferably 2.0 at% or more and 5.0 at% or less. When the silicon atom ratio in the adhesive layer is within the above range, the adsorption of water molecules to the metal aluminum film and the change in properties can be sufficiently suppressed, and the adhesive layer exhibits a sufficient adhesive force. Because you can do it.

  As described later, when the silicon-containing compound is an organosilicon compound, the organosilicon atom ratio in the adhesive layer can be set within the above-described silicon atom ratio. That is, when the silicon-containing compound is an organosilicon compound, the adhesive layer preferably has an atomic ratio of organosilicon atoms of 1.5 at% or more and 7.0 at% or less, and 1.5 at% or more and 5.0 at% or less. %, More preferably 2.0 at% or more and 5.0 at% or less. The reason for this is the same as the case where the silicon atom ratio in the adhesive layer is set in a predetermined range, and a description thereof will be omitted.

  When the organosilicon atom ratio in the adhesive layer greatly exceeds the above range, a high concentration of the organosilicon compound in the adhesive layer causes a condensation reaction between the organosilicon compounds to proceed, and the organic layer in the adhesive layer Since the proportion occupied by the condensate (siloxane oligomer) of the silicon compound increases, the adhesive strength may decrease, and peeling may easily occur between the adhesive layer and the metal aluminum film.

The silicon atom ratio or the organosilicon atom ratio in the adhesive layer can be determined by performing composition analysis on the surface of the adhesive layer by X-ray photoelectron spectroscopy (XPS). More specifically, it can be determined by the following procedure. First, the outer layer of the vacuum heat insulating material is peeled between the adhesive layer and the metal aluminum film in contact with the adhesive layer to expose the adhesive layer, and the adhesive layer is exposed using an X-ray photoelectron spectrometer under the following conditions. X-rays are irradiated from the surface in the depth direction, and the X-ray photoelectron spectrum is measured. As the X-ray photoelectron spectrometer, for example, Theta-Probe manufactured by Thermo can be used. When the silicon atom ratio in the adhesive layer is measured, C, O, N, inorganic Si, and organic Si are used as elements to be analyzed, and the background determined by the Shirley method is subtracted from the obtained spectrum to obtain a peak area. By using the relative sensitivity coefficient method, the atomic number ratio (at%) of silicon atoms when the total number of carbon atoms, oxygen atoms, nitrogen atoms, and silicon atoms is 100 at% can be determined. When measuring the organosilicon atom ratio in the adhesive layer, C, O, N, and organic Si are used as analysis target elements, and the background determined by the Shirley method is subtracted from the obtained spectrum, and the peak area is calculated. Using the relative sensitivity coefficient method, the atomic number ratio (at%) of the organic silicon atoms can be determined when the total number of carbon atoms, oxygen atoms, nitrogen atoms, and organic silicon atoms is 100 at%. Note that, in the C1s spectrum, the charging of the spectrum is corrected so that the peak attributed to the CC bond is in the range of 284.6 eV to 285.0 eV. Regarding the Si2p peak, a peak appearing in the range of 101.5 eV to 102.5 eV in the spectrum is defined as a peak derived from organic Si, and a peak appearing in the range of 103.0 eV to 103.8 eV is defined as a peak derived from inorganic Si. I do.
(Measurement condition)
-Incident X-ray: Monochromated Al-Kα ray (monochromatic X-ray, Hν = 1486.6 eV)
・ X-ray irradiation area (measurement area); 400 μmφ
・ X-ray output: 100W (15kV ・ 6.7mA)
-Photoelectron take-up angle: 53 ° (sample normal is 0 °)
・ Charge neutralization conditions: electron neutralization gun (+6 V, 0.05 mA), low acceleration Ar ⁺ ion irradiation ・ Measurement peaks: Al2p, Si2p, C1s, N1s, O1s, F1s

  Hereinafter, the composition of the adhesive layer will be described.

1. Silicon-Containing Compound In the silicon-containing compound contained in the adhesive layer, at least one of a hydrolyzable group and a hydroxyl group is directly bonded to a silicon atom.

  Examples of the silicon-containing compound include an inorganic silicon compound, an organic silicon compound, and a mixture thereof.

  Here, the “organic silicon compound” means an organic compound containing a silicon (Si) atom as a constituent atom. The organic silicon compound has at least one direct chemical bond between a silicon atom and a carbon atom, and a silicon atom chemically bonded to a carbon atom is referred to as an organic silicon atom. On the other hand, an inorganic compound containing a silicon (Si) atom as a constituent atom is called an “inorganic silicon compound” and is distinguished from an organic silicon compound. The silicon atom in the inorganic silicon compound is referred to as an inorganic silicon atom. Since the inorganic silicon atom and the organic silicon atom have different binding energies, they appear separately in the Si2p spectrum in the analysis by X-ray photoelectron spectroscopy (XPS). According to the peak separation analysis, a peak appearing on the high binding energy side is a peak derived from Si (inorganic Si) of the inorganic silicon atom, and a peak appearing on the low binding energy side is a peak derived from Si (organic Si) of the organic silicon atom. be able to.

  That is, the organosilicon compound in the present disclosure refers to a compound in which at least one of a hydrolyzable group and a hydroxyl group is directly bonded to an organosilicon atom. In addition, the inorganic silicon compound in the present disclosure refers to a compound in which at least one of a hydrolyzable group and a hydroxyl group is directly bonded to an inorganic silicon atom.

  In the present disclosure, it is particularly preferable that the silicon-containing compound is an organic silicon compound. The organosilicon compound often contains a hydrophobic organic functional group, and such an organosilicon compound forms a bond with a metal aluminum film, whereby the film surface of the metal aluminum film can be made more hydrophobic. . Thereby, the probability of the presence of water molecules on the surface of the metal aluminum film is reduced, and the adsorption reaction and the property change are less likely to occur.

Examples of the organosilicon compound include a monomer represented by the following formula (1).
R _n -SiX _4-n (1)
(In the above formula (1), n is an integer of 1 to 3, X is a hydrolyzable group or a hydroxyl group, and R is an organic functional group or a hydrocarbon group containing an organic functional group.)

  In the above formula (1), n is an integer of 1 to 3, and it is particularly preferable that n = 1. By setting n in the above formula (1) to the above integer, that is, by including three hydrolyzable groups or hydroxyl groups, the reactivity with the hydroxyl groups on the surface of the metal aluminum film is enhanced and the property change of the metal aluminum film is suppressed. This is because the effect and the effect of suppressing the deterioration of the gas barrier performance are further exhibited.

  X in the above formula (1) represents a hydrolyzable group or a hydroxyl group. When n in the above formula (1) is 1 or 2, two or more Xs may be the same or different. X in the above formula (1) becomes a silanol group directly or by a hydrolysis reaction with a water molecule to form a hydrogen bond with a hydroxyl group existing on the surface of the metal aluminum film on the adhesive layer side, or dehydrates with the hydroxyl group. It has the function of forming a covalent bond via a condensation reaction. Specifically, when the hydroxyl group is directly bonded to the organosilicon atom, the organosilicon compound has a silanol group, so that the silanol group is hydrogen-bonded or covalently bonded to the hydroxyl group present on the surface of the metal aluminum film on the adhesive layer side. Can be formed. When the hydrolyzable group is directly bonded to an organosilicon atom, the hydrolyzable group of the organosilicon compound reacts with surrounding water molecules to be hydrolyzed to be a silanol group, and the silanol group is A hydrogen bond or a covalent bond can be formed with a hydroxyl group existing on the surface of the metal aluminum film on the adhesive layer side.

  Examples of the hydrolyzable group represented by X include, for example, an alkoxy group, an acyloxy group, an alkenoxy group, a ketoxime group, an alkoxyalkoxy group, a halogen group, an isocyanate group, a ketoximate group, an amide group, an amideoxy group, a mercapto group, and an alkenyloxy group. , A fernoxy group, and an unsubstituted or substituted amino group.

  The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, specifically, a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group. And the like. The alkoxy group may include a substituted alkoxy group such as an alkoxy-substituted alkoxy group.

  The acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms, and specific examples include an acetoxy group and a benzoyloxy group.

  Specific examples of the alkenoxy group include an isopropenoxy group. Specific examples of the ketoxime group include a methylethylketoxime group.

  Specific examples of the alkoxyalkoxy group include a methoxymethoxy group and a methoxyethoxy group.

  Specific examples of the halogen group include a fluoro group, a chloro group, a bromo group, and an iodo group.

  Examples of the isocyanate group include an isocyanate group bonded to an alkyl group, an isocyanate group bonded to a cycloalkyl group, an isocyanate group bonded to an aryl group, an isocyanate group bonded to an alkyl group substituted by a cycloalkyl group, and an aryl group. Examples include an isocyanate group bonded to a substituted alkyl group.

  Among them, the above hydrolyzable group is preferably an alkoxy group, particularly preferably a methyloxy group or an ethyloxy group.

  R in the above formula (1) is an organic functional group or a hydrocarbon group containing an organic functional group. In other words, R in the above formula (1) represents an organic functional group having a carbon atom directly bonded to an organic silicon atom, or a hydrocarbon group containing an organic functional group and having a carbon atom directly bonded to the organic silicon atom. It is. When n in the above formula (1) is 2 or more, two or more Rs may be the same or different. Examples of the organic functional group include a vinyl group, an epoxy group, a styryl group, a (meth) acryl group, a methacryloxy group, an amino group, a ureide group, an isocyanate group, a mercapto group, a hydroxy group, a halogen group, a cyano group, and a sulfide. And the like. In addition, (meth) acryl means that it is either acryl or methacryl. When R is a hydrocarbon group containing an organic functional group, the number of carbon atoms in the hydrocarbon group is not particularly limited, but may be, for example, in the range of 1 to 30.

  The organosilicon compound is not particularly limited as long as it is a compound represented by the above formula (1) and having the above R and the above X. Among them, a silane coupling agent is preferable.

  Specific examples of the organosilicon compound include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, Pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyldimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane , Vinyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, 3- (3-methyl-3-oxetanemeth B) propyltrimethoxysilane, oxacyclohexyltrimethoxysilane, methyltri (meth) acryloxysilane, methyl [2- (meth) acryloxyethoxy] silane, methyl-triglycidyloxysilane, methyltris (3-methyl-3-oxetane) Methoxy) silane, vinyltrichlorosilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -Glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldi Toxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and the like.

  Further, as the organosilicon compound, for example, (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate Acrylic esters; carboxylic acids such as (meth) acrylic acid, itaconic acid and fumaric acid; and acid anhydrides such as maleic anhydride; epoxy compounds such as glycidyl (meth) acrylate; diethylaminoethyl (meth) acrylate, aminoethyl vinyl ether and the like Amide compounds such as (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (meth) acrylamide; acrylonitrile, styrene, α-methyls A compound having a vinyl-based polymer obtained by copolymerizing a vinyl-based compound selected from tylene, vinyl chloride, vinyl acetate, vinyl propionate and the like as R in the above formula (1) is exemplified.

  In the adhesive layer, the organosilicon compound may be contained alone or in combination of two or more.

  When the silicon-containing compound is an organosilicon compound, the content of the organosilicon compound in the adhesive layer may be an amount such that the organosilicon atom ratio in the adhesive layer is in the above-described range, and the type of the adhesive component And the type of the organosilicon compound can be appropriately set. For example, the content of the organosilicon compound is, in terms of solid content, 0.5 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the adhesive component, among which 0.5 part by mass or more and 5 parts by mass or less. It is particularly preferable that the content is 1 part by mass or more and 4 parts by mass or less. When the content of the organosilicon compound with respect to 100 parts by mass of the adhesive component exceeds the above range, the organosilicon compounds are likely to undergo a condensation reaction with each other to form a siloxane oligomer, which may hinder the original adhesiveness of the adhesive. is there. Further, the amount of gas such as alcohol gas generated by the reaction between the hydrolyzable group of the organosilicon compound and the hydroxyl group of the metal aluminum film or the condensation reaction between the organosilicon compounds increases, and the vacuum using the envelope material of the present disclosure increases In the process of exposing the heat insulating material to a high-temperature and high-humidity environment for a long time, the heat insulating performance may be reduced. On the other hand, if the content of the organosilicon compound with respect to 100 parts by mass of the adhesive component does not satisfy the above range, an amount of the organosilicon compound capable of sufficiently forming a bond with a hydroxyl group present on the surface of the metal aluminum film on the adhesive layer side is used. Is not contained, and the above-mentioned hydroxyl group remains, so that adsorption of water molecules and change in properties may not be sufficiently suppressed.

  When the silicon-containing compound is an organosilicon compound, in the adhesive layer, the organosilicon compound is present as a monomer represented by the formula (1), but is a siloxane having a siloxane bond (Si—O—Si). It may be present as an oligomer. The siloxane oligomer is a condensate of the monomer represented by the formula (1). The siloxane oligomer has at least a siloxane bond (Si-O-Si), and preferably has at least one kind of a hydrolyzable group or a hydroxyl group directly bonded to an organic silicon atom. This is because the hydrolyzable group or hydroxyl group of the siloxane oligomer can form a hydrogen bond or a covalent bond with a hydroxyl group on the surface of the metal aluminum film. If the proportion of the siloxane oligomer in the adhesive layer is too large, problems such as clouding of the adhesive layer, deterioration of the adhesive force of the adhesive layer, and easy occurrence of delamination tend to occur. Therefore, the content of the siloxane oligomer is preferably 5 parts by mass or less based on 100 parts by mass of the adhesive component in terms of solid content.

  On the other hand, when the silicon-containing compound is an inorganic silicon compound, examples of the inorganic silicon compound include silicic acid, disiloxane, trisiloxane, tetramethoxysilane (TMOS), and tetraethoxysilane (TEOS). When the silicon-containing compound is an inorganic silicon compound, the content of the inorganic silicon compound in the adhesive layer is the same as the content of the organic silicon compound in the adhesive layer when the silicon-containing compound is an organic silicon compound. It can be.

  When the silicon-containing compound is a mixture of an inorganic silicon compound and an organic silicon compound, the content of the silicon compound (the sum of the content of the inorganic silicon compound and the content of the organic silicon compound) in the adhesive layer is determined by When the contained compound is an organosilicon compound, the content can be the same as the content of the organosilicon compound in the adhesive layer. Further, the content of the siloxane oligomer in the adhesive layer in the above case can be the same as the content of the siloxane oligomer when the silicon-containing compound is an organic silicon compound.

2. Adhesive component As the adhesive component in the adhesive layer, a general adhesive can be used, and the type is not particularly limited. Examples of the adhesive include a polyether adhesive, a polyester adhesive, a polyurethane adhesive, a vinyl adhesive, a (meth) acrylic adhesive, a polyamide adhesive, an epoxy adhesive, and a rubber adhesive. Agents and the like. The adhesive may be a one-part curing type or a two-part curing type. Only one kind of these adhesive components may be contained in the above-mentioned adhesive layer, or two or more kinds thereof may be contained.

3. Others The adhesive layer may contain one or more additives as necessary. Examples of the additives include a vulcanizing agent (crosslinking agent), a vulcanization accelerator, a vulcanization aid (crosslinking aid), a bulking agent, a reinforcing agent, a processing aid, an antioxidant, a plasticizer, and an ultraviolet absorber. Agents, lubricants and the like.

  As the thickness of the adhesive layer, the silicon atom ratio (organic silicon atom ratio) in the adhesive layer can be set in the above range, and the thickness is particularly large as long as the desired adhesive force can be exhibited. Although not limited, the thickness can be, for example, 1 μm or more and 10 μm or less, preferably 2 μm or more and 5 μm or less, and more preferably 3 μm or more and 5 μm or less. By setting the thickness of the adhesive layer in the above range, it is possible to further reduce the outgas amount derived from the adhesive layer while exhibiting a sufficient adhesive force.

As described above, in the high-temperature and high-humidity environment, the adhesive layer reacts with the hydrolyzable group of the silicon-containing compound and the hydroxyl group of the metal aluminum film, or a gas such as an alcohol gas due to a condensation reaction between the organosilicon compounds. appear. If the amount of gas generated from the adhesive layer is too large, in the process of exposing the vacuum heat insulating material using the outer packaging material including the adhesive layer to a high-temperature and high-humidity environment for a long time, the gas generated from the outer packaging material becomes It may stay inside and the heat insulation performance may be reduced. Therefore, it is preferable that the amount of gas generated in the adhesive layer in a high-temperature and high-humidity environment is small. Specifically, the amount of heat generated gas per one of the adhesive layers is preferably 10 mg / m ² or less, more preferably 5 mg / m ² or less, and more preferably 3 mg / m ² or less. Particularly preferred. When the amount of gas generated by heating is within the above range, the gas generated from the outer wrapping material stays inside the vacuum insulating material in the process of exposing the vacuum insulating material using the outer wrapping material of the present disclosure to a high-temperature and high-humidity environment for a long time. This is because the heat insulation performance can be prevented from being reduced.

  The amount of heat generated gas per one adhesive layer can be a value measured under predetermined measurement conditions by a head space gas chromatography (HS-GC) method. Specifically, an adhesive sheet was prepared in which a single layer of an adhesive layer was formed on one side of a release paper, a sample (size: 10 cm × 10 cm) was cut out from the adhesive sheet, and a test piece from which the release paper was peeled was used as a sample. It is sealed in a tube, heated at 120 ° C. for 60 minutes with a headspace sampler, the generated gas is analyzed by gas chromatography, and the amount of gas generated by heating can be quantified by a calibration curve method using a peak area. Regarding the measurement conditions at the time of measurement by the headspace gas chromatography (HS-GC) method, the measurement at the time of measuring the amount of gas generated by heating in the entire outer packaging material described later by the headspace gas chromatography (HS-GC) method is described. Since the conditions can be the same, the description is omitted here.

B. Gas barrier film having a metal aluminum film The gas barrier film having a metal aluminum film in the outer packaging material of the present disclosure has at least a metal aluminum film.

1. Metal Aluminum Film The metal aluminum film is a thin film having a thickness of several nm to several hundred nm as described later, and is distinguished from a metal aluminum foil having a thickness of several μm to several tens μm. The metal aluminum film is distinguished from an aluminum compound film formed by an aluminum compound, such as an aluminum oxide film or an aluminum hydroxide film. Note that the metal aluminum film may contain impurities.

  The thickness of the metal aluminum film is not particularly limited, but specifically, is preferably 200 nm or less, more preferably 150 nm or less, more preferably 100 nm or less, and more preferably 80 nm or less. Particularly preferred. Further, the metal aluminum film preferably has a thickness capable of exhibiting a desired gas barrier performance, and is not particularly limited, but may be, for example, 10 nm or more, and particularly preferably 20 nm or more. In particular, it is preferably 30 nm or more. As the thickness of the metal aluminum film is smaller, the time required for the property change to progress from the film surface to the inside of the film is shorter, and the property change is more likely to occur in a high-temperature and high-humidity environment in a shorter time. For this reason, when a thinner film is used as the metal aluminum film, the effect of directly disposing the adhesive layer in the present disclosure can be more remarkably exhibited.

  The metal aluminum film may be a coating film by coating or a vapor deposition film. The metal aluminum film can be formed by a conventionally known method such as a coating method, an evaporation method, and a pressure bonding method depending on the material and the type.

2. Substrate The gas barrier film having a metal aluminum film may be a metal aluminum film alone, or may have a substrate on the surface of the metal aluminum film opposite to the surface in contact with the adhesive layer. In this case, the metal aluminum film is usually arranged directly in contact with the surface of the substrate. The substrate is not particularly limited as long as it is a member that supports the metal aluminum film. For example, a resin substrate is suitably used. Specific examples of the resin substrate include polyolefin resin films such as polyethylene (PE) and polypropylene (PP); polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); Cyclic olefin copolymer film; cyclic olefin polymer film; polystyrene resin film; acrylonitrile-styrene copolymer (AS resin) film; acrylonitrile-butadiene-styrene copolymer (ABS resin) film; poly (meth) acrylic resin film; polycarbonate resin Film; polyvinyl alcohol-based resin film such as polyvinyl alcohol (PVA) and ethylene-vinyl alcohol copolymer (EVOH); ethylene-vinyl ester Saponified copolymer film; various polyamide resin films such as nylon; polyimide resin film; polyurethane resin film; acetal resin film; cellulose resin film such as triacetyl cellulose (TAC); Can be mentioned. Among them, a polyester resin film is preferable, and a PET film is more preferable. This is because the metal aluminum film is easily formed because it has heat resistance and is stiff.

  The thickness of the base material can be a size having a strength capable of supporting the metal aluminum film, and is not particularly limited, but can be, for example, 2 μm or more and 400 μm or less.

  The base material preferably has flexibility. Further, the base material may or may not have light transmittance, may be transparent, may be translucent, may be opaque.

  The base material may be subjected to a surface treatment on a surface in contact with the metal aluminum film, and an arbitrary layer such as a primer layer or an undercoat layer may be disposed on the surface in contact with the metal aluminum film. This is because the adhesion to the metal aluminum film can be improved.

3. Other gas barrier film having a metal aluminum film, may be composed of only a metal aluminum film, may be a configuration having a metal aluminum film on one surface of the substrate, a metal aluminum film on both surfaces of the substrate May be provided.

When the gas barrier film having a metal aluminum film has a base material, the base material may have an overcoat film on the surface where the metal aluminum film is not formed. This is because the gas barrier performance exhibited by the gas barrier film having the metal aluminum film can be further enhanced. The material of the overcoat film is not particularly limited, but has, for example, an MOP bond (here, M represents a metal atom, O represents an oxygen atom, and P represents a phosphorus atom). A gas barrier resin composition comprising a metal oxide phosphoric acid, zinc acrylate, a resin and an inorganic layer compound, a general formula R ¹ nM (OR ² ) m (where R ¹ and R ^{2 each} have 1 to 1 carbon atoms) Represents an organic group of 8, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M.) A sol-gel polycondensate of at least one or more alkoxides and a water-soluble polymer is exemplified.

  In the outer packaging material of the present disclosure, at least one gas barrier film having the metal aluminum film may be provided, and two or more gas barrier films may be provided. The number of the gas barrier films having the metal aluminum film depends on the configuration of the gas barrier film having the metal aluminum film, the gas barrier performance of the outer packaging material, and the like within a range in which the outer packaging material of the present disclosure can have desired characteristics. Can be set appropriately. When the outer packaging material of the present disclosure has two or more gas barrier films having a metal aluminum film, at least one of the gas barrier films having a metal aluminum film is provided on the metal aluminum film in the above section “A. Adhesive layer”. In particular, in the above case, in each of the gas barrier films having a metal aluminum film, the specific adhesion layer described in the above section “A. Adhesion layer” is formed on the metal aluminum film. Preferably, the layers are arranged directly.

C. Other members The outer packaging material of the present disclosure can have other members. Hereinafter, other members in the outer packaging material of the present disclosure will be described.

1. Heat-Sealable Film The outer packaging material of the present disclosure may have a heat-sealable film on one outermost side in the thickness direction of the outer packaging material. The heat weldable film is a film that can be welded by heating. The heat-sealable film is a member that bears one surface in the thickness direction of the outer packaging material, and is in contact with the core material when producing a vacuum heat insulating material using the outer packaging material of the present disclosure, and seals the core material. When stopping, it is a member that joins the ends of the facing outer packaging materials.

  As the heat-sealable 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) or unstretched polypropylene (CPP) ), A polyester resin film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT); a polyvinyl acetate resin film; a polyvinyl chloride resin film; (Meth) acrylic resin films, urethane resin films and the like.

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

  The thickness of the heat-sealable film may be any thickness as long as a desired adhesive strength can be obtained when the outer packaging materials are joined to each other, for example, within a range of 15 μm to 100 μm, preferably 25 μm to 90 μm. It can be in the range, more preferably in the range from 30 μm to 80 μm.

2. Protective film The outer packaging material of the present disclosure can have a protective film on the other outermost side in the thickness direction of the outer packaging material. By having the protective film, the protective film becomes a member that bears the other surface in the thickness direction of the outer packaging material. Therefore, it can be a layer that bears the other surface in the thickness direction of the outer packaging material. The components of the material can be protected from damage and deterioration.

  As the protective film, a general-purpose resin film having a higher melting point than a heat-weldable film can be used. Among them, the protective film is preferably at least one selected from the group consisting of a nylon film, a PET film, a PBT film, and a PP film. The thickness of the protective film is not particularly limited, and can be appropriately set.

3. Other adhesive layers The outer packaging material of the present disclosure may have other adhesive layers that are not directly disposed on the metal aluminum film. Examples of the other adhesive layer include, for example, an adhesive layer in contact with the substrate of a gas barrier film having a metal aluminum film on one surface of the substrate, and two layers other than the gas barrier film having the metal aluminum film of the outer packaging material. For example, an adhesive layer between members may be used.

  The other adhesive layer may be an adhesive layer having the composition described in the section “A. Adhesive layer”, or an adhesive layer having a different composition from the adhesive layer described in the section “A. It may be. That is, in the outer packaging material of the present disclosure, the other adhesive layer may further include a silicon-containing compound as long as the adhesive layer includes the adhesive component described in the section “A. Adhesive layer”. The compound may not be contained.

4. Optional Configuration The outer packaging material of the present disclosure may include a layer capable of exhibiting gas barrier properties in addition to the gas barrier film having the metal aluminum film. Examples of such a layer include a metal foil, a film having a thin film formed of a metal other than metal aluminum or an inorganic compound on at least one surface of a substrate, and the like.

D. Others The thickness of the outer packaging material of the present disclosure is not particularly limited, and can be appropriately set. The thickness is preferably a size capable of having the above-described properties, and may be, for example, 30 μm or more, preferably 50 μm or more, depending on the layer configuration, and the thickness is, for example, 200 μm or less, Preferably, it can be 150 μm or less.

Water vapor permeability of the outer cover material of the present disclosure, preferably as low, for example, is preferably 0.1g ^/ (m 2 · day) or less, preferably 0.05g ^/ (m 2 · day) or less, particularly 0. It is preferably at most 01 g / (m ² · day). The value of the water vapor permeability is an initial water vapor permeability before exposure to a high temperature and high humidity environment.

The water vapor transmission rate can be measured using a water vapor transmission rate measuring device at a temperature of 40 ° C. and a relative humidity difference of 90% RH in accordance with ISO 15106-5: 2015 (differential pressure method). The measurement of the initial water vapor permeability can be performed according to the following procedure. First, a sample of the outer packaging material cut to a desired size was mounted between the upper chamber and the lower chamber of the above-mentioned apparatus, and the permeation area was 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. The measurement is performed under the condition of 90% RH. When the outer packaging material for vacuum insulation material to be measured has a heat-sealable film, the outermost layer of the outer packaging material for vacuum insulation material opposite to the heat-sealable film is on the high humidity side (water vapor supply side). And attach it. As the water vapor transmission rate measuring apparatus, for example, "DELTAPERM" manufactured by UK TechnoX can be used.

  The measurement of the water vapor permeability is performed on at least three samples under one condition, and the average of the measured values is defined as the value of the water vapor permeability under the condition. Hereinafter, the water vapor transmission rate in the present specification can be measured by a method similar to the method described above.

The oxygen permeability of the outer cover material of the present disclosure is so low that preferably, for example, is preferably ^{0.1cc / (m 2 · day ·} atm) or less, preferably ^{0.05cc / (m 2 · day ·} atm It is more preferred that: The value of the oxygen permeability is an initial oxygen permeability before exposure to a high temperature and high humidity environment.

  The oxygen permeability is based on JIS K7126-1: 2006 (Plastic film and sheet-Gas permeability test method-Part 2: Isobaric method, Appendix A: Test method of oxygen gas permeability by electrolytic sensor method) It can be measured at a temperature of 23 ° C. and a humidity of 60% RH using an oxygen gas permeability measuring device. As the oxygen gas permeability measuring device, for example, “OXTRAN” manufactured by MOCON, USA can be used. The measurement of the oxygen permeability can be performed on at least three samples under one condition, and the average of the measured values can be used as the value of the oxygen permeability under the condition.

The outer packaging material of the present disclosure is more preferable as the total amount of generated gas is smaller. Specifically, the heat generation gas amount of the outer packaging material of the present disclosure is preferably 30 mg / m ² or less, more preferably 15 mg / m ² or less, and particularly preferably 10 mg / m ² or less. preferable. When the amount of gas generated by heating the outer packaging material is within the above range, the gas generated from the outer packaging material is subjected to vacuum insulation in the process of exposing the vacuum insulating material using the outer packaging material of the present disclosure to a high-temperature and high-humidity environment for a long time. This is because it is possible to prevent the heat insulation performance from being reduced due to stagnation inside the material.

  The amount of gas generated by heating the outer packaging material can be a value measured by the headspace gas chromatography (HS-GC) method under the following conditions. Specifically, a test piece (size: 10 cm × 10 cm) was cut out from the outer packaging material, the test piece was sealed in a sample tube, heated at 120 ° C. for 60 minutes with a headspace sampler, and the generated gas was subjected to gas chromatography. And the amount of gas generated by heating can be quantified by the calibration curve method using the peak area.

<Measurement conditions>
・ Headspace gas chromatography device; Model HS7694-GC6890 manufactured by Agilent Technologies ・ Headspace heating conditions: 120 ° C. for 60 minutes ・ GC inlet temperature: 280 ° C.
GC inlet mode; split GC inlet split ratio; 20: 1
・ Column: DB-5 or equivalent ・ Carrier gas: Helium ・ Column flow rate: 2.0 ml / min ・ Column heating condition: 40 ° C. × 3 minutes (holding) → 15 ° C./min (heating) → 320 ° C. × 5 .33 minutes (hold)
-Total time: 27 minutes-Detector: Flame ionization detector (FID)
・ Detector temperature: 300 ° C

  When the outer packaging material of the present disclosure has two or more gas barrier films having a metal aluminum film, the first surface of the adhesive layer described in the above section “A. Adhesive layer” has a first gas barrier film having a metal aluminum film. A second surface opposed to the first surface of the adhesive layer, which is in direct contact with the metal aluminum film of the film, is disposed so as to directly contact the metal aluminum film of the second gas barrier film having the metal aluminum film; Is preferred. With one adhesive layer described in the above section “A. Adhesive layer”, it is possible to prevent water molecules from being adsorbed to the metallic aluminum films of the two gas barrier films each having the metallic aluminum film, and to prevent each metallic aluminum film from adsorbing. This is because it is possible to suppress the progress of the property change of the film and the deterioration of the water vapor barrier performance.

  The outer packaging material of the present disclosure can be used for a vacuum heat insulating material. In the vacuum heat insulating material, the outer packaging material of the present disclosure is used in such a manner that the heat-sealable film is on the core material side, and is disposed to face through the core material.

II. Vacuum Heat Insulating Material The vacuum heat insulating material of the present disclosure is a vacuum heat insulating material having a core material and an outer packaging material in which the core material is encapsulated, wherein the outer packaging material is the same as that of “I. It is an outer packaging material for a vacuum heat insulating material described in the section.

  FIG. 2A is a schematic perspective view illustrating an example of the vacuum heat insulating material of the present disclosure, and FIG. 2B is a cross-sectional view taken along line XX of FIG. 2A. The vacuum heat insulating material 20 illustrated in FIGS. 2A and 2B includes a core material 21 and an outer packaging material 10 for enclosing the core material 21, and the outer packaging material 10 is the vacuum heat insulating material illustrated in FIG. 1. It is an outer packaging material. In the vacuum heat insulating material 20 illustrated in FIGS. 2A and 2B, a pair of outer wrapping materials 10 are arranged so as to face each other via a core material 21 such that respective heat-sealable films face each other. The core material 21 is enclosed by joining and sealing the outer peripheral end 22 of the outer packaging material 10. The internal pressure of the vacuum heat insulating material 20 is reduced, and the vacuum heat insulating material 20 is in a pressure state lower than the atmospheric pressure.

  According to the vacuum heat insulating material of the present disclosure, the outer material for enclosing the core material is the vacuum heat insulating material described in the above section “I. Even when used in a high humidity environment, deterioration of the water vapor barrier performance of the outer packaging material is suppressed, so that a low vacuum state inside can be maintained for a long time. Thereby, the vacuum heat insulating material of the present disclosure can exhibit good heat insulating performance for a long time in a high temperature and high humidity environment.

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

A. 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 the same as the outer wrapping material for vacuum heat insulating material described in the section “I. The description here is omitted.

B. 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 core material may be any material having a low thermal conductivity, and examples thereof include powders, foamed resins, and fibers. The core material may be formed of one of the above-described materials, or may be a composite material formed by mixing two or more materials. The core material may be made of an inorganic material, may be made of an organic material, or may be a mixture of an organic material and an inorganic material.

C. Vacuum Insulation Material In the vacuum insulation material of the present disclosure, a core material is sealed in a bag body of an outer packaging material, and the inside of the sealed interior is decompressed to be in a vacuum state. The degree of vacuum inside the vacuum heat insulating material of the present disclosure is preferably, for example, 5 Pa or less. This is because heat conduction due to the convection of air remaining inside hardly occurs, so that excellent heat insulating properties can be exhibited.

  The vacuum heat insulating material of the present disclosure is preferably as low as the thermal conductivity. The thermal conductivity is preferably, for example, 5 mW / (m · K) or less. This is because heat is not easily conducted to the outside, and a high heat insulating effect can be achieved. Among them, the thermal conductivity is more preferably 4 mW / (m · K) or less, further preferably 3 mW / (m · K) or less. The thermal conductivity can be a value measured under the conditions of 30 ° C. on the high temperature side, 10 ° C. on the low temperature side, and 20 ° C. average temperature in accordance with JIS A1412-2: 1999.

D. Others A known method can be used for the method for manufacturing the vacuum heat insulating material of the present disclosure. For example, two pieces of the outer material for vacuum heat insulating material described in the section of "I. Outer material for vacuum heat insulating material" are prepared, the heat-sealable films are faced to each other, and the outer edges of the three sides are overlapped. Heat welding (heat sealing) is performed to obtain a bag having one side open. After the core material is put into this bag through the opening, air is sucked through the opening, and the opening is sealed in a state where the inside of the bag is decompressed, whereby a vacuum heat insulating material can be obtained.

III. Articles with Vacuum Heat Insulation The articles with vacuum heat insulation according to the present disclosure are articles having a heat insulation area and articles with vacuum heat insulation provided with vacuum heat insulation, wherein the vacuum heat insulation is a core material and a core material enclosed. And the outer wrapping material is the outer wrapping material for a vacuum heat insulating material described in the section “I. Outer wrapping material for vacuum heat insulating material”.

  According to the article with the vacuum heat insulating material of the present disclosure, since the outer wrapping material constituting the vacuum heat insulating material provided in the article is the outer wrapping material for the vacuum heat insulating material described in the section “I. Even when used in a high-temperature and high-humidity environment for a long period of time, good heat insulating performance can be exhibited for a long period of time. When the article is provided with such a vacuum heat insulating material, energy saving of the article and an object to which the article is used can be achieved.

  The vacuum heat insulating material and the outer packaging material used in the present disclosure have been described in detail in the above sections “II. Vacuum heat insulating material” and “I. .

  Articles in the present disclosure have a thermally 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, Reference Examples and Reference Comparative Examples, and Examples and Comparative Examples are shown, and the present disclosure will be described more specifically.

[Reference Examples 1 to 8 and Reference Comparative Examples 1 to 3]
(Preparation of adhesive composition)
Using the following materials, adhesive compositions AA1 to AA5, BA1 to BA4, and BB1 to BB2 were prepared according to the formulations shown in Table 1.

<Adhesive>
Adhesive A: 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 Two-part curable adhesive in which a solvent of ethyl is mixed such that the weight ratio becomes main agent: curing agent: solvent = 10: 1: 14 ・ Adhesive B: a polyester-based resin as a main component, a methoxysilane component (Toyo Morton Co., Ltd. product name: TM-556-S), a curing agent containing a polyisocyanate resin (Toyo Morton Co., Ltd. product name, CAT-56), and a solvent of ethyl acetate, the weight ratio of which is a main component. : Two-part curable adhesive mixed so that curing agent: solvent = 17: 3: 30

<Silane coupling (SC) agent>
-Silane coupling agent A (SC agent A): 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Silicone Co., Ltd.)
-Silane coupling agent B (SC agent B): vinyltrimethoxysilane (KBM-1003 manufactured by Shin-Etsu Silicone Co., Ltd.)

On the aluminum-deposited film surface of a gas barrier film A (manufactured by Toray Film Processing Co., Ltd., product name: TAF1590, base material: PET film, hereinafter sometimes simply referred to as film A) having an aluminum-deposited film (thickness: 70 nm) on one side. One of the adhesive compositions prepared above was applied so as to have a coating amount of 3.5 g / m ² to form an adhesive layer. A polyethylene terephthalate (PET) substrate was disposed on the surface of the adhesive layer opposite to the surface in contact with the aluminum vapor-deposited film, and aged at 40 ° C. for 3 days to obtain samples (Reference Examples 1 to 8 and Reference Comparative Examples 1 to 3).

[Evaluation]
The following evaluations 1 to 4 were performed on the samples obtained in Reference Examples 1 to 8 and Reference Comparative Examples 1 to 3.

(Evaluation 1: Organosilicon atom ratio in adhesive layer)
With respect to each of the samples obtained in Reference Examples 1 to 8 and Reference Comparative Examples 1 to 3, the composition of the surface of the adhesive layer was analyzed by X-ray photoelectron spectroscopy (XPS) to determine the organosilicon atom ratio in the adhesive layer. First, each sample was peeled between the adhesive layer and the metal aluminum film to expose the adhesive layer, and the adhesive layer was exposed using an X-ray photoelectron spectrometer (Theta-Probe manufactured by Thermo) under the following conditions. X-rays were irradiated from the exposed surface in the depth direction, and the X-ray photoelectron spectrum was measured using C, O, N, and organic Si as the analysis elements. From the obtained spectrum, the background determined by the Shirley method was subtracted, and the total number of carbon atoms, oxygen atoms, nitrogen atoms, and organosilicon atoms in the adhesive layer was calculated from the peak area using the relative sensitivity coefficient method. The atomic number ratio (at%) of the organosilicon atoms when 100 at% was determined. In the C1s spectrum, the charging of the spectrum was corrected so that the peak attributed to the CC bond was in the range of 284.6 eV to 285.0 eV. Further, regarding the Si2p peak, a peak appearing in the range of 101.5 eV to 102.5 eV in the spectrum is a peak derived from the organic Si element, and a peak appearing in the range of 103.0 eV to 103.8 eV is derived from the inorganic Si element. Peaked.
<Measurement conditions>
-Incident X-ray: Monochromated Al-Kα ray (monochromatic X-ray, Hν = 1486.6 eV)
・ X-ray irradiation area (measurement area); 400 μmφ
・ X-ray output: 100W (15kV ・ 6.7mA)
-Photoelectron take-up angle: 53 ° (sample normal is 0 °)
Charge neutralization conditions; electron neutralizing gun (+ 6V, 0.05mA), low acceleration Ar ⁺ ion irradiation and measurement _{peaks; Al2p, Si2p, C 1s,} N1s, O1s, F1s

  In the composition analysis of the surface of the adhesive layer of each of the samples obtained in Reference Examples 1 to 8 and Comparative Examples 1 to 3, no spectrum of inorganic Si was detected. It was the same as the silicon atom ratio.

(Evaluation 2: Evaluation of delamination occurrence)
For each of the samples obtained in Reference Examples 1 to 8 and Reference Comparative Examples 1 to 3, the appearance was confirmed from the PET substrate side arranged on the surface opposite to the surface in contact with the metal aluminum film of the adhesive layer, The presence or absence of delamination was confirmed. A case where no delamination was observed between the metal aluminum film and the PET substrate was evaluated as “○”, and a case where delamination was observed at one or more locations between the metal aluminum film and the PET substrate was evaluated as “x”.

(Evaluation 3: Water vapor permeability at initial stage and after holding at high temperature and high humidity)
The initial water vapor permeability of each sample obtained in Reference Examples 1 to 6 and Reference Comparative Examples 1 to 3 was measured. The water vapor transmission rate was measured at a temperature of 40 ° C. and a relative humidity difference of 90% RH using a water vapor transmission rate measuring apparatus (PERMATRAN, manufactured by MOCON, USA) in accordance with JIS K7129: 2008 (Appendix B: Infrared sensor method). It measured on condition of. In the measurement, first, a test piece was cut out to a desired size from each sample, and the metal aluminum film surface of the test piece was on the high humidity side (water vapor supply side). The measurement was carried out under conditions of a temperature of 40 ° C. and a relative humidity difference of 90% RH with a transmission area of about 50 cm ² (transmission area: a circle having a diameter of 8 cm). For each sample, the water vapor transmission rate was measured for at least three test pieces, and the average of the measured values was taken as the value of the water vapor transmission rate of the sample.

  Next, the samples obtained in Reference Examples 1 to 6 and Reference Comparative Example 1 were kept in an environment of a temperature of 85 ° C. and a relative humidity of 85% for 28 days, and then the same as the above-described method of measuring the initial water vapor permeability. Then, the water vapor permeability after holding at high temperature and high humidity was measured.

(Evaluation 4: OD value at initial stage and after holding at high temperature and high humidity)
The initial OD value of each sample obtained in Reference Examples 1 to 6 and Comparative Comparative Examples 1 to 3 was measured using a transmission densitometer (portable transmission densitometer 341 manufactured by X-rite).

  Next, the samples obtained in Reference Examples 1 to 6 and Reference Comparative Examples 1 to 3 were kept in an environment of a temperature of 85 ° C. and a relative humidity of 85% for 28 days, and then the same as the above-described method of measuring the initial OD value. The OD value after holding at high temperature and high humidity was measured.

  Table 2 shows the results of the evaluations 1 to 4.

[Discussion 1]
From Table 2 above, Reference Examples 1 to 6 and Reference Comparative Example 1 did not show a significant difference in the initial water vapor transmission rate, but Reference Comparative Example 1 showed that the water vapor transmission rate after long-term holding in a high-temperature and high-humidity environment. The degree greatly increased as compared with Reference Examples 1 to 6. This suggests that the higher the organosilicon atom ratio in the adhesive layer, the more the deterioration of the water vapor barrier performance is suppressed even when the temperature is maintained in a high temperature and high humidity environment for a long period of time. On the other hand, in Reference Comparative Examples 2 and 3, the organosilicon atom ratio in the adhesive layer was more than 7.0 at%, and generation of delamination was confirmed in the process of holding in a high temperature and high humidity environment. Further, in Reference Comparative Examples 2 and 3, it was observed that the adhesive layer was clouded.

  Reference Examples 1 to 8 and Reference Comparative Examples 1 to 3 did not show a large difference in the initial OD value, but Reference Comparative Example 1 in which the organosilicon atom ratio in the adhesive layer was less than a predetermined range was The OD value after long-term holding in a high-temperature, high-humidity environment was sharply reduced as compared with Reference Examples 1 to 8. This is because a large number of hydroxyl groups that could not form a bond with the organosilicon compound in the adhesive layer remained on the surface of the metal aluminum film, and the hydroxyl groups adsorbed a large amount of water molecules. It is presumed that it became an aluminum compound film.

[Examples 1 and 2 and Comparative Example 1]
(Preparation of outer packaging material for vacuum insulation)
A film having a metal oxide phosphoric acid layer shown below (hereinafter sometimes simply referred to as a film B), a gas barrier film having a metal aluminum film (hereinafter sometimes simply referred to as a film C), and heat welding are possible. Prepared a new film.
-Film having a metal oxide phosphate layer (film B): PET film having a metal oxide phosphate layer having an Al-OP bond on one side (12 [mu] m thick, Kuraray CF Clarister CF)
Gas barrier film having a metal aluminum film (Film C): EVOH film (12 μm thick, TMXL manufactured by Kuraray Co., Ltd.) with a metal aluminum (Al) film deposited on one side
-Film capable of heat welding: linear (linear) low-density polyethylene (LLDPE) film (thickness: 50 m, TUX-HC-E manufactured by Mitsui Chemicals Tosello Co.)

Using the film A, the film B and the film C used in Reference Examples 1 to 6 and Reference Comparative Example 1, and the heat-weldable film, a film B // film A // film C // heat welding An outer packaging material for vacuum insulation having a possible film stacking order was obtained. “//” in the above-mentioned lamination order means a lamination interface via an adhesive layer. In the outer packaging material for a vacuum heat insulating material, the film B is a layer capable of exhibiting gas barrier properties. The adhesive layer is, in the above-mentioned lamination order, one of AA1 to AA3 of each of the adhesive compositions prepared and obtained on the surface of one of the two layers adjacent via the adhesive layer. And an application amount of 3.5 g / m ² . In addition, the films A to C are arranged such that the film A has the metal aluminum film surface facing the film B side, and the film B has the metal oxide phosphoric acid layer side surface facing the film C side. The film C was arranged such that the surface on the metal aluminum film side faced the film B side.

(Preparation of vacuum insulation material)
Two pieces (dimensions: 360 mm × 450 mm) cut out from the obtained outer packaging material for vacuum heat insulating material are prepared, and two pieces are overlapped so that the heat-weldable films face each other. A sealed bag was formed with only one side open. After using glass wool (dimensions: 290 mm x 300 mm x 30 mm) as a core material and performing a drying treatment, 5 g of calcium oxide as a core material and a desiccant was stored in the bag, and the inside of the bag 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]
The following evaluations 5 to 6 were performed on the outer packaging material for vacuum heat insulating material and the vacuum heat insulating material obtained in Examples 1 and 2 and Comparative Example 1.

(Evaluation 5: Amount of gas generated by heating)
The amount of gas generated by heating of the outer packaging material for a vacuum heat insulating material obtained in Examples 1 and 2 and Comparative Example 1 was measured by a head space gas chromatography (HS-GC) method. First, a test piece (size: 10 cm × 10 cm) was cut out from each outer packaging material for vacuum heat insulating material, the test piece was sealed in a sample tube, and heated at 120 ° C. for 60 minutes using a headspace sampler. The gas generated from the test piece was subjected to measurement by gas chromatography. The amount of gas generated by heating was determined by a calibration curve method using a peak area. The measurement conditions are shown below.
<Measurement conditions>
・ HS-GC device; HS7694 type-GC6890 type manufactured by Agilent Technologies ・ Headspace heating condition: 120 ° C, 60 minutes ・ GC inlet temperature: 280 ° C
GC inlet mode; split GC inlet split ratio; 20: 1
・ Column: DB-5 or equivalent ・ Carrier gas: Helium ・ Column flow rate: 2.0 ml / min ・ Column heating condition: 40 ° C. × 3 minutes (holding) → 15 ° C./min (heating) → 320 ° C. × 5 .33 minutes (hold)
-Total time: 27 minutes-Detector: Flame ionization detector (FID)
・ Detector temperature: 300 ° C

(Evaluation 6: Thermal conductivity)
Regarding the vacuum heat insulating materials obtained in Examples 1 and 2 and Comparative Example 1, the initial thermal conductivity (A) (temperature before holding in an atmosphere of 70 ° C. and 90% RH), the temperature of 70 ° C. and the humidity of 90% The thermal conductivity (B) after holding for 15 days in an atmosphere of RH and the thermal conductivity (C) after holding for 50 days in an atmosphere of 70 ° C. and 90% humidity were measured. The thermal conductivity was measured using a thermal conductivity measuring device (product name: Auto Lambda HC-074, manufactured by Eiko Seiki) according to JIS A1412-2: 1999 (Method of measuring thermal resistance and thermal conductivity of thermal insulating material-2nd Part: heat flow meter method (HFM method)). For each vacuum insulator, the thermal conductivity was measured for at least three samples, and the average of the measured values was taken as the value of the thermal conductivity of the vacuum insulator.
<Measurement conditions>
・ Size: width 29cm ± 0.5cm, length 30cm ± 0.5cm
-The time required for the steady state of the test: 15 minutes or more-Type of standard plate: EPS
・ Temperature of hot surface: 30 ° C
・ Cold surface temperature: 10 ℃
・ Average temperature of measurement sample: 20 ° C

  Table 3 shows the results of the evaluations 5 and 6.

[Discussion 2]
From the above Table 3, it was confirmed that the time required for the thermal conductivity to decrease in Example 2 after being placed in an environment of a temperature of 70 ° C. and a humidity of 90% RH was shorter than that in Example 1. This is presumed to be because the organosilicon atom ratio in the adhesive layer of the outer packaging material for a vacuum heat insulating material of Example 2 was more than 5.0 at%, and the amount of gas generated by heating from the adhesive layer increased.

DESCRIPTION OF SYMBOLS 1 ... Metal aluminum film 2 ... Base material 10 ... Outer wrapping material for vacuum heat insulating materials 11 ... Gas barrier film having a metal aluminum film 12 ... Adhesive layer 13 ... Heat-weldable film 20 ... Vacuum heat insulating material 21 ... Core material

Claims (9)

A gas barrier film having a metal aluminum film, and an adhesive layer directly disposed on the metal aluminum film,
The adhesive layer includes an adhesive component and a silicon-containing compound in which at least one of a hydrolyzable group or a hydroxyl group is directly bonded to a silicon atom,
The outer packaging material for a vacuum heat insulating material, wherein the adhesive layer has an atomic ratio of the silicon atoms of 1.5 at% or more and 7.0 at% or less. The silicon-containing compound is an organic silicon compound in which at least one of the hydrolyzable group or the hydroxyl group is directly bonded to an organic silicon atom,
2. The outer packaging material for a vacuum heat insulating material according to claim 1, wherein the adhesive layer has an atomic ratio of the organosilicon atoms of 1.5 at% or more and 7.0 at% or less.   The outer packaging material for a vacuum heat insulating material according to claim 2, wherein the atomic ratio of the organosilicon atoms is 1.5 at% or more and 5.0 at% or less. Core material, a vacuum heat insulating material having an outer packaging material in which the core material is enclosed,
The outer packaging material has a gas barrier film having a metal aluminum film, and an adhesive layer directly disposed on the metal aluminum film,
The adhesive layer includes an adhesive component and a silicon-containing compound in which at least one of a hydrolyzable group or a hydroxyl group is directly bonded to a silicon atom,
The vacuum heat insulating material, wherein the adhesive layer has an atomic ratio of the silicon atoms of 1.5 at% or more and 7.0 at% or less. The silicon-containing compound is an organic silicon compound in which at least one of the hydrolyzable group or the hydroxyl group is directly bonded to an organic silicon atom,
The vacuum heat insulating material according to claim 4, wherein the adhesive layer has an atomic ratio of the organosilicon atoms of 1.5 at% or more and 7.0 at% or less.   The vacuum heat insulating material according to claim 5, wherein the atomic ratio of the organosilicon atoms is 1.5 at% or more and 5.0 at% or less. 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 in which the core material is enclosed,
The outer packaging material has a gas barrier film having a metal aluminum film, and an adhesive layer directly disposed on the metal aluminum film,
The adhesive layer includes an adhesive component and a silicon-containing compound in which at least one of a hydrolyzable group or a hydroxyl group is directly bonded to a silicon atom,
The article with a vacuum heat insulating material, wherein the adhesive layer has an atomic ratio of the silicon atoms of 1.5 at% or more and 7.0 at% or less. The silicon-containing compound is an organic silicon compound in which at least one of the hydrolyzable group or the hydroxyl group is directly bonded to an organic silicon atom,
The article with a vacuum heat insulating material according to claim 7, wherein the adhesive layer has an atomic ratio of the organosilicon atoms of 1.5 at% or more and 7.0 at% or less.   The article with a vacuum heat insulating material according to claim 8, wherein the atomic ratio of the organosilicon atoms is 1.5 at% or more and 5.0 at% or less.