JP6776618B2 - Outer packaging material for vacuum heat insulating material, vacuum heat insulating material, and equipment with vacuum heat insulating material - Google Patents

Description

The present disclosure relates to an external packaging material for a vacuum heat insulating material that can form a vacuum heat insulating material that can maintain the heat insulating performance for a long period of time.

In recent years, reduction of greenhouse gases has been promoted to prevent global warming, and energy saving of electric appliances, vehicles, equipment and buildings is required. Above all, from the viewpoint of reducing power consumption, the adoption of vacuum heat insulating materials in electric appliances and the like is being promoted. For equipment that has a heat generating part inside the main body such as electrical products and equipment that has a heat retention function that uses heat from the outside, it is possible to improve the heat insulation performance of the entire equipment by providing a vacuum heat insulating material. It becomes. For this reason, efforts are being made to reduce the energy of equipment such as electrical products by using vacuum heat insulating materials.

The vacuum heat insulating material is a bag body formed of an outer packaging material in which a core material is arranged, the inside of the bag body in which the core material is arranged is depressurized to create a vacuum state, and the end portion of the bag body is heat-welded. It was formed by sealing. By creating a vacuum inside the heat insulating material, convection of gas is blocked, so that the vacuum heat insulating material can exhibit high heat insulating performance. Further, in order to maintain the heat insulating performance of the vacuum heat insulating material for a long period of time, it is necessary to keep the inside of the bag formed by using the outer packaging material in a high vacuum state for a long period of time. Therefore, the outer packaging material is required to have various functions such as a gas barrier property for preventing gas from permeating from the outside and a heat bonding performance for covering and tightly sealing the core material.

Therefore, the outer packaging material is configured as a laminate having a plurality of films having each of these functional characteristics. As a general aspect of the outer packaging material, a heat-weldable film, a gas barrier film, and a protective film are laminated, and each layer is bonded with an adhesive or the like (see Patent Documents 1 and 2). ). Patent Document 1 describes that two nylon films are used as the outer packaging material for the purpose of preventing a decrease in the vacuum state due to the generation of pinholes in the gas barrier film due to skewering or the like. Further, Patent Document 2 aims to prevent the gas barrier film from being directly affected by bending at the end portion where the outer packaging materials are bonded to each other when the vacuum heat insulating material is formed using the outer packaging material. , It is described that protective films having a high tensile elastic modulus are arranged on both sides of the gas barrier film.

Japanese Unexamined Patent Publication No. 2003-262296 Japanese Unexamined Patent Publication No. 2013-103343

However, in the outer packaging materials of Patent Document 1 and Patent Document 2, the vacuum heat insulating material was formed by using the outer packaging material even when it was confirmed that the outer packaging material alone exhibited sufficient gas barrier properties. In some cases, there is a problem that the vacuum state cannot be sufficiently maintained and the heat insulating performance cannot be maintained for a long period of time. This is because the outer packaging material constituting the vacuum heat insulating material is deteriorated by various stresses such as mechanical and thermal applied to the vacuum heat insulating material during use, and the gas barrier property of the outer packaging material is lowered. It is possible that there is. The deterioration of the outer packaging material as described above can be suppressed by constructing the outer packaging material using a material having high mechanical strength and heat resistance, but many of such materials have a high glass transition point. Therefore, when such a material is used for a heat-weldable film, it is necessary to raise the heat-welding temperature, which causes problems such as a decrease in material selectivity for the outer packaging material and an increase in manufacturing cost.

The present disclosure has been made in view of the above problems, and an object of the present disclosure is to provide an outer packaging material for a vacuum heat insulating material capable of forming a vacuum heat insulating material capable of maintaining heat insulating performance for a long period of time.

That is, the present disclosure is an outer packaging material for a vacuum heat insulating material having at least a heat-weldable film and a gas barrier film, and the heat-weldable film contains an amorphous copolymerized polyester resin. Provided a characteristic outer packaging material for a vacuum heat insulating material.

According to the present disclosure, among copolymerized polyester resins having a desired tensile elastic modulus for a heat-weldable film of an outer packaging material, an amorphous one has a desired tensile elastic modulus and is used. It is possible to realize a heat-weldable film that can be heat-welded at a desired temperature.

In the present disclosure, it is preferable that the heat welding temperature of the resin constituting the heat welding film is 120 ° C. or higher. Since the outer packaging material can be heat-welded at a desired temperature, deterioration of the material constituting the outer packaging material due to heat can be suppressed, and the range of selection of the material constituting the outer packaging material can be expanded. Because it can be done.

In the present disclosure, the tensile elastic modulus of the heat-weldable film is preferably in the range of 1.0 GPa or more and 5.0 GPa or less. This is because the tensile elastic modulus of the outer packaging material can be set within a desired range, and the occurrence of cracks in the gas barrier film can be suppressed. Further, it is possible to suppress the occurrence of pinholes due to piercing from the core material used for the vacuum heat insulating material.

In the present disclosure, it is preferable to have a protective film on the surface side of the gas barrier film opposite to the heat-weldable film. This is because when the outer packaging material has a protective film, each film used together as the outer packaging material, such as a heat-weldable film and a gas barrier film, can be protected from damage and deterioration.

In the present disclosure, the gas barrier film is preferably a metal foil. Since the metal foil has high gas barrier properties and excellent bending resistance, by using the metal foil as the gas barrier film, an outer packaging material having high gas barrier properties can be obtained, and high gas barrier properties are maintained. Because it can be done.

In the present disclosure, it is preferable that the gas barrier film has a resin base material and a gas barrier layer arranged on at least one surface side of the resin base material. This is because by forming the gas barrier film from a resin base material and a gas barrier layer, the amount of inorganic substances used in the gas barrier film can be reduced and heat conduction due to the inorganic substances can be suppressed.

The present disclosure is a vacuum heat insulating material having a core material and an outer packaging material for the vacuum heat insulating material that encloses the core material, and the outer packaging material for the vacuum heat insulating material is the outer packaging material for the vacuum heat insulating material described above. Provide a characteristic vacuum heat insulating material. According to the present disclosure, since the outer packaging material for the vacuum heat insulating material is the above-mentioned outer packaging material for the vacuum heat insulating material, it can be a vacuum heat insulating material capable of maintaining the heat insulating performance for a long period of time.

The present disclosure is a device having a heat source portion or a heat insulating portion inside or a main body, and a device with a vacuum heat insulating material provided with a vacuum heat insulating material. The vacuum heat insulating material is a core material and a vacuum that encloses the core material. Provided is an apparatus with a vacuum heat insulating material, which has a heat insulating material outer packaging material, and the vacuum heat insulating material outer packaging material is the vacuum heat insulating material outer packaging material described above. According to the present disclosure, since the vacuum heat insulating material outer packaging material is the vacuum heat insulating material outer packaging material, the vacuum heat insulating material can maintain the heat insulating performance for a long period of time, and therefore, in an apparatus having a heat source portion. Insulates the heat from the heat source portion by the vacuum heat insulating material to prevent the temperature of the entire device from becoming high, while in the device having the heat insulating portion, the vacuum heat insulating material is used to heat the heat insulating portion. The temperature state can be maintained. As a result, it is possible to obtain a device having high energy saving characteristics with reduced power consumption.

In the present disclosure, it is possible to provide an outer packaging material for a vacuum heat insulating material that can form a vacuum heat insulating material that can maintain the heat insulating performance for a long period of time.

It is the schematic sectional drawing which shows an example of the external packaging material for a vacuum heat insulating material of this disclosure. It is the schematic sectional drawing which shows an example of the vacuum heat insulating material of this disclosure. It is the schematic sectional drawing which shows the other example of the external packaging material for a vacuum heat insulating material of this disclosure. It is the schematic sectional drawing which shows the other example of the external packaging material for a vacuum heat insulating material of this disclosure. It is a graph which shows the deterioration amount of the thermal conductivity of the vacuum heat insulating material produced in an Example and a comparative example. It is a graph which shows the deterioration amount of the thermal conductivity of the vacuum heat insulating material produced in an Example and a comparative example.

Hereinafter, the outer packaging material for the vacuum heat insulating material, the vacuum heat insulating material, and the device with the vacuum heat insulating material of the present disclosure will be described in detail.
In this specification, the "external packaging material for vacuum heat insulating material" may be abbreviated as "external packaging material".
Further, when the term "gas barrier property" is described, unless otherwise specified, it means a feature having a barrier property against gas such as oxygen and / or water vapor.
Further, when the vacuum heat insulating material is formed using the outer packaging material, the heat-weldable film side that is the inside of the vacuum heat insulating material is the "inside of the outer packaging material", and the heat-weldable film that is the outside of the vacuum heat insulating material. The side far from the may be described as "outside of the outer packaging material".

A. Outer packaging material for vacuum heat insulating material First, the outer packaging material for vacuum heat insulating material of the present disclosure will be described.
The outer packaging material of the present disclosure is an outer packaging material for a vacuum heat insulating material having at least a heat-weldable film and a gas barrier film, and the heat-weldable film contains an amorphous copolymer polyester resin. It is characterized by.

The outer packaging material of the present disclosure will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the outer packaging material of the present disclosure. As illustrated in FIG. 1, the outer packaging material 10 of the present disclosure has a heat-weldable film 1 and a gas barrier film 2, and the heat-weldable film 1 contains an amorphous copolymer polyester resin. To do.

Further, FIG. 2 is a schematic cross-sectional view showing an example of the vacuum heat insulating material using the outer packaging material of the present disclosure. As illustrated in FIG. 2, the vacuum heat insulating material 20 has a core material 11 and an outer packaging material 10 that encloses the core material 11. In the vacuum heat insulating material 20, the two outer packaging materials 10 are opposed to each other so that the heat-weldable films 1 face each other, the core material 11 is arranged between them, and then the outer periphery of the core material 11 is arranged. By heat-welding the ends 12 of the outer packaging materials 10 on the other three sides with one as an opening, a bag body formed of the two outer packaging materials 10 and having the core material 11 arranged inside is prepared. Then, the core material 11 is sealed in the outer packaging material 10 by sealing the opening in a state where the internal pressure of the bag body is reduced. The reference numerals not described in FIG. 2 indicate the same members as those in FIG. 1, and thus the description thereof will be omitted here.

The stress applied to the vacuum heat insulating material during use includes, for example, the piercing stress received from glass wool used as the core material, the bending stress when the vacuum heat insulating material is arranged along the surface of the device having a curved surface, and the like. Can be mentioned. Such stress causes pinholes and cracks in the gas barrier film, which may lead to a decrease in the gas barrier property of the outer packaging material. Further, depending on the temperature of the environment in which the vacuum heat insulating material is arranged, the outer packaging material is thermally shrunk and expanded, so that cracks may occur in the gas barrier film, which may lead to deterioration of the gas barrier property of the outer packaging material.

A material having a large tensile elastic modulus has high resistance to stress as described above, and tends to have a small expansion / contraction rate due to heat. Therefore, by using a material having a large tensile elastic modulus as an outer packaging material, the above machine It is possible to suppress the deterioration of the gas barrier property of the outer packaging material due to the target and thermal stress. However, since a material having a high tensile elastic modulus tends to have a high glass transition point, when such a material is used for a heat-weldable film of an outer packaging material, it is necessary to raise the heat-welding temperature, and the outer packaging material must be used. Problems such as thermal deterioration of other constituent materials, deterioration of material selectivity, and increase in manufacturing cost occur.

As a result of diligent research by the present inventor, it has been found that even if the resin has a similar glass transition point, the amorphous resin tends to have a lower heat welding temperature than the crystalline resin. We have completed the invention disclosed in. That is, according to the present disclosure, among copolymerized polyester resins having a desired tensile elastic modulus for a heat-weldable film of an outer packaging material, an amorphous one has a desired tensile elastic modulus. Moreover, it is possible to realize a heat-weldable film that can be heat-welded at a desired temperature.

The outer packaging material of the present disclosure includes at least a heat-weldable film and a gas barrier film. Hereinafter, each configuration of the outer packaging material of the present disclosure will be described.

1. 1. Heat-weldable film The heat-weldable film in the present disclosure is characterized by containing an amorphous copolymer polyester resin. The phrase "the heat-weldable film contains an amorphous copolymer resin" means that the heat-weldable film is a film containing an amorphous copolymer resin. It is preferable that the film is mainly composed of an amorphous copolymer resin.

A copolymerized polyethylene terephthalate (PET) film, which is a typical example of a film composed of a copolymerized polyester resin, is formed by forming a PET resin and then stretching (biaxially stretching) the PET resin in the biaxial direction of XY to orient the molecules. As a result, the crystallized product is widely used in various applications. The "amorphous copolymerized polyester resin" in the present disclosure refers to a film that has not been crystallized as described above, and is preferably a non-stretched film.

Whether the copolymerized polyester resin is amorphous or crystalline can be determined by observing the molecular orientation of the resin by an X-ray diffraction method. It is preferable that the molecules of the amorphous copolymer polyester resin are not oriented in a certain direction, and the orientation state of most of the molecules is random. When the measurement by the X-ray diffraction method does not show a dominant peak above the background level, it can be determined that the resin is amorphous. The above measurement can be performed, for example, using RINT-1100 manufactured by Rigaku Co., Ltd. as an X-ray diffractometer under the following conditions.
<X-ray diffraction measurement conditions>
Source: CuKα ray (wavelength; 1.5418A)
Scanning axis; 2θ / θ
Tube voltage; 45 kV
Tube current; 200mA
Slit; soler slit 5.0 degrees Scan speed; 5.5 degrees / minute Scan step; 0.05 degrees

The tensile elastic modulus of the heat-weldable film is not particularly limited, but is preferably 1.0 GPa or more, and above all, 1.0 GPa or more and 5.0 GPa or less. It is preferable, and in particular, it is preferably in the range of 1.0 GPa or more and 3.0 GPa or less. When the tensile elastic modulus of the heat-weldable film is within the above range, the tensile elastic modulus of the outer packaging material can be within a desired range, and the occurrence of cracks in the gas barrier film is suppressed. Because it can be done. Further, it is possible to suppress the occurrence of pinholes due to piercing from the core material used for the vacuum heat insulating material.

The method for measuring the tensile elastic modulus conforms to JIS K7161, and after cutting the heat-weldable film into strips having a width of 15 mm and a length of 120 mm, a tensile tester is used to pull the distance between chucks to 100 mm. A method of measuring the tensile elastic modulus at a speed of 100 mm / min can be used. The measurement conditions of the tensile elastic modulus can be 23 ° C. and 55% humidity. As the tensile tester, for example, a tensile tester (Tensilon universal tester RTC-1250A) can be used.

The glass transition point of the amorphous copolymer resin is not particularly limited, but is, for example, in the range of 50 ° C. or higher and 90 ° C. or lower, particularly in the range of 60 ° C. or higher and 80 ° C. or lower. can do. The glass transition point can be measured by differential scanning calorimetry (DSC) in accordance with ISO 11357. The adjustment of the glass transition point can be appropriately performed by changing the mixing ratio, the degree of polymerization, etc. of the polyvalent carboxylic acid and the polyhydric alcohol used as raw materials according to the chemical structure and the like.

The above-mentioned tensile elastic modulus and glass transition point are unique to the material, but even if the resin has the same tensile elastic modulus, the amorphous resin tends to have a lower heat welding temperature than the crystalline resin. It is in. Therefore, by using an amorphous copolymer resin as a heat-weldable film, a heat-weldable film having a desired tensile elastic modulus can be heat-welded at a lower temperature. The heat welding temperature of the resin constituting such a heat-weldable film is not particularly limited, and is, for example, in the range of 120 ° C. or higher, particularly in the range of 150 ° C. or higher and 220 ° C. or lower, particularly 150 ° C. As mentioned above, the temperature can be within the range of 200 ° C. or lower. When the heat welding temperature is within the above range, the outer packaging material can be heat-welded at a desired temperature, so that the material constituting the outer packaging material can be suppressed from being deteriorated by heat, and the outer packaging material can be prevented from being deteriorated. This is because the range of selection of materials constituting the material can be expanded. The heat welding temperature can be set to a temperature at which 15 N or more can be obtained in the heat seal strength measurement based on the JIS Z 0238 standard.

A typical example of the copolymerized polyester resin that can be used in the present disclosure is a copolymerized polyethylene terephthalate (PET) resin. Such a copolymerized PET resin contains terephthalic acid and ethylene glycol as main components, and a polyhydric carboxylic acid other than terephthalic acid and / or a polyhydric alcohol other than ethylene glycol as copolymerization components. A modified PET resin obtained by adding and copolymerizing so as to exhibit properties can be used.

Polyvalent carboxylic acids added as copolymerization components include isophthalic acid, orthophthalic acid, adipic acid, azelaic acid, sebacic acid, and dimer acid (mainly a dimer of unsaturated fatty acid or a hydrogenated product thereof). , Diphenylcarboxylic acid, trimellitic acid, pyromellitic acid, sodium 5-sulfoisophthalate and the like. Examples of the polyhydric alcohol added as a copolymerization component include diethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, neopentyl glycol, 1,4-butanediol, and 1,5-pentanediol. Examples thereof include 1,6-hexanediol, pentaerythritol, and bisphenol A ethylene oxide adduct.

Specific examples of the above-mentioned copolymerized PET include cocondensation of a combination of terephthalic acid, isophthalic acid and ethylene glycol, terephthalic acid and ethylene glycol and 1,4-cyclohexanedimethanol, terephthalic acid and isophthalic acid, ethylene glycol and propylene glycol. PET resin made of a polymer can be mentioned.

The mixing ratio of the main component and the copolymerization component is not particularly limited as long as an amorphous substance can be obtained. For example, 50 mol% or more of the polyvalent carboxylic acid as a raw material is terephthalic acid. In addition, 50 mol% or more of the polyhydric alcohol as a raw material can be ethylene glycol. If the amount of terephthalic acid and ethylene glycol as raw materials is smaller than the above, the impact resistance and non-adsorption property may be impaired.

Further, the total amount of terephthalic acid and ethylene glycol, which are the main components, is within the range of 50 mol% or more and 95 mol% or less with respect to the total amount of the polyvalent carboxylic acid and the polyhydric alcohol which are the raw materials. It is preferable that the total amount of the copolymerization components is in the range of 5 mol% or more and 50 mol% or less. If the total amount of the copolymerization components is less than 5 mol%, the amorphous property may be lost and the seal strength may be impaired.

The amorphous copolymer polyester resin as described above is also commercially available, and examples thereof include Byron manufactured by Toyobo Co., Ltd. and Eastar PETG manufactured by Eastman Chemical Company. Further, the analysis of the mixing ratio of the polyester component and the copolymerization component can be analyzed by an FT-IR or a nuclear magnetic resonance (NMR) device.

The heat-weldable film may contain an anti-blocking agent in the range of 1% by mass or more and 10% by mass or less, more preferably in the range of 3% by mass or more and 5% by mass or less. This is because the slipperiness of the film can be improved by containing the anti-blocking agent within the above range without impairing the heat welding strength and the like. Examples of such anti-blocking agents include oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide and zinc oxide, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, and magnesium carbonate. Carbonates such as calcium carbonate, sulfates such as calcium sulfate and barium sulfate, silicates such as magnesium silicate, aluminum silicate, calcium silicate and aluminosilicate, and other inorganic compounds such as kaolin, talc and silica soil. Examples include system anti-blocking agents and mixtures consisting of two or more of these.

Further, if necessary, the heat-weldable film can be used as an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a lubricant (fatty acid amide, etc.), and flame retardant as long as the effects of the present disclosure are not impaired. It may contain one or more kinds of agents, inorganic or organic fillers, cross-linking agents, dyes, colorants such as pigments, and additives such as modifying resins.

The thickness of the heat-welded layer is preferably, for example, 20 μm or more and 100 μm or less, particularly preferably 25 μm or more and 90 μm or less, and particularly preferably 30 μm or more and 80 μm or less. If the thickness of the heat-weldable film is larger than the above range, the gas barrier property of the outer packaging material may be lowered, while if it is smaller than the above range, the adhesive strength may not be obtained.

2. Gas barrier film The gas barrier film is arranged outside the heat-weldable film described above, and mainly contributes to the gas barrier property of the outer packaging material. The gas barrier film is not particularly limited as long as it can obtain the desired gas barrier property, and a metal foil may be used as the gas barrier film (first aspect), and the resin base material and at least the resin base material A laminate having a gas barrier layer arranged on one surface side may be used as the gas barrier film (second aspect). Hereinafter, each aspect of the gas barrier film will be described.

(1) First Aspect The first aspect in the present disclosure is a mode in which the gas barrier film is a metal foil. Examples of such a metal foil include metal foils such as aluminum, nickel, stainless steel, iron, copper, and titanium, and among them, aluminum foil is preferably used. Since the metal foil has high gas barrier properties and excellent bending resistance, by using the metal foil as the gas barrier film, an outer packaging material having high gas barrier properties can be obtained, and high gas barrier properties are maintained. can do.

The metal foil may be a single layer, or may be a multilayer body in which layers made of the same material or layers made of different materials are laminated. The thickness of the metal foil is preferably, for example, within the range of 3 μm or more and 50 μm or less, particularly preferably within the range of 6 μm or more and 12 μm or less. If the thickness of the metal foil is smaller than the above range, pinholes and the like are likely to occur in the metal foil, and the gas barrier property may be lowered. On the other hand, if the thickness is larger than the above range, the external packaging material of the present disclosure is used. This is because the heat bridge is likely to occur in the formed vacuum heat insulating material, and when the outer packaging material is bent, pinholes or the like are likely to occur at the bent portion, and the heat insulating performance may be deteriorated.

As for the gas barrier property of the metal foil, the oxygen permeability is preferably 0.01 cc / m ² / day / atm or less, and more preferably 0.005 cc / m ² / day / atm or less. It is preferable that water vapor permeability is not more than 0.01g ^/ m 2 ^/ day, preferably at most among them 0.005g ^/ m 2 ^/ day. When the oxygen and water vapor permeability of the metal foil is within the above range, it is possible to make it difficult for water, gas, etc. that have permeated from the outside to permeate into the core material inside. The oxygen permeability can be a value measured using an oxygen permeability measuring device under the conditions of a temperature of 23 ° C. and a humidity of 60% RH based on JIS K 7126B. Examples of the oxygen permeability measuring device include OXTRAN manufactured by MOCON, USA. Further, the water vapor permeability can be measured according to ISO 151065 using a water vapor permeability measuring device (DELTAPERM manufactured by Technolux, UK) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH.

When the gas barrier film in the outer packaging material is of the first aspect, it is preferable that a protective film such as a resin film is arranged on the outside of the gas barrier film (on the side opposite to the heat-weldable film). This is because the gas barrier film can be protected from exposure to water vapor and physical stress. Since such a protective film is the same as that described in "3. Protective film" described later, the description thereof is omitted here.

(2) Second Aspect The gas barrier film of the second aspect in the present disclosure has a resin base material and a gas barrier layer arranged on at least one surface side of the resin base material. The outer packaging material having the gas barrier film of this embodiment will be described with reference to the drawings. FIG. 3 is a schematic cross-sectional view showing another example of the packaging material of the present disclosure. As illustrated in FIG. 3, the outer packaging material 10 having the gas barrier film 2'of this embodiment is the same as the outer packaging material having the gas barrier film of the first aspect described above, the heat-weldable film 1 and the gas barrier film 2'. It has. The gas barrier film 2'of this embodiment has a resin base material 3 and a gas barrier layer 4 arranged on one surface side of the resin base material 3.

Since inorganic substances such as metals have high thermal conductivity, if the amount of inorganic substances used in the outer packaging material is large, it is not possible to reduce the thermal conductivity of the vacuum heat insulating material formed using such the outer packaging material. Have difficulty. In this embodiment, by forming the gas barrier film from the resin base material and the gas barrier layer, the amount of the inorganic substance used in the gas barrier film can be reduced and the heat conduction by the inorganic substance can be suppressed. Hereinafter, the gas barrier film of this embodiment having such a structure will be described.

(A) Gas Barrier Layer The gas barrier layer is arranged on at least one surface side of the resin base material, and mainly contributes to the gas barrier property of the gas barrier film. The gas barrier layer is not particularly limited as long as it can exhibit a desired gas barrier property, and may or may not have transparency. As the layer having such a gas barrier property, for example, a metal layer, a layer containing an inorganic compound as a main component, or the like can be used. Examples of the metal layer include a metal vapor deposition film composed of a metal such as aluminum, stainless steel, titanium, nickel, iron, and copper, or an alloy containing these.

Further, the inorganic compound of the layer containing the above-mentioned inorganic compound as a main component may be any material that can exhibit a desired gas barrier property, for example, an inorganic oxide, an inorganic oxidative nitride, an inorganic nitride, an inorganic oxidative carbide, or an inorganic substance. Examples thereof include one or more inorganic compounds selected from oxidative carbide and zinc oxide. Specifically, an inorganic compound containing one or more elements selected from silicon (silica), aluminum, magnesium, calcium, potassium, tin, sodium, titanium, boron, yttrium, zirconi, muserium, and zinc. Can be mentioned. More specifically, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, silicon zinc alloy oxide, indium alloy oxide, silicon nitride, aluminum nitride, titanium nitride, oxidation. Examples thereof include silicon nitride. The above-mentioned inorganic compound may be used alone, or the above-mentioned materials may be mixed and used in an arbitrary ratio.

The thickness of the gas barrier layer is not particularly limited as long as it can exhibit the desired gas barrier property, and it depends on the type of the gas barrier layer, but is, for example, in the range of 5 nm or more and 200 nm or less. Is preferable, and above all, it is preferably in the range of 10 nm or more and 150 nm or less. If the thickness of the gas barrier layer is less than the above range, film formation may be insufficient and the desired gas barrier property may not be exhibited. If the thickness exceeds the above range, cracks are likely to occur and the flexibility may decrease. Further, when the gas barrier layer contains a metal or an alloy, a heat bridge may occur in the vacuum heat insulating material formed by using the outer packaging material of the present disclosure.

The gas barrier layer may be a single layer, or may be a stack of two or more so that the total thickness is within the above range. When two or more gas barrier layers are used, gas barrier layers having the same composition may be combined, or gas barrier layers having different compositions may be combined. Further, the gas barrier layer may be subjected to surface treatment such as corona discharge treatment from the viewpoint of improving the gas barrier property and the adhesion with other layers.

As a method for forming the gas barrier layer on one surface side of the resin base material, a conventionally known method can be used depending on the type of the gas barrier layer. For example, a method of forming a gas barrier layer on a resin substrate by using a dry film forming method such as a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method, specifically, an electron beam (EB). A vacuum vapor deposition method or the like based on a heating method can be used. Further, a method of thermocompression bonding a resin base material and a preheated thin film using a ready-made gas barrier thin film, a method of adhering to the resin base material or the thin film via an adhesive layer, and the like can be mentioned. As a specific method for forming a gas barrier layer by the PVD method and the CVD method, for example, the method disclosed in Japanese Patent Application Laid-Open No. 2011-5835 can be used.

It Examples of the gas barrier properties of the gas barrier layer alone (one layer) is preferably an oxygen permeability is less than ^{0.5cc / m 2 / day / atm} , or less among others 0.1cc ^/ m 2 ^/ day ^/ atm Is preferable. Further, the water vapor permeability is preferably 0.5 g / m ² / day or less, and more preferably 0.1 g / m ² / day or less. When the oxygen and water vapor permeability of the gas barrier layer is within the above range, it is possible to make it difficult for water vapor, gas, etc. that have permeated from the outside to permeate into the core material inside the vacuum heat insulating material. Since the method for measuring the oxygen permeability and the water vapor permeability is the same as the description in the section of "(1) First aspect", the description thereof is omitted here.

(B) Resin base material The resin base material is not particularly limited as long as it can support the gas barrier layer. For example, a resin film is preferably used. When the resin base material is a resin film, the resin film may be unstretched or may be uniaxially or biaxially stretched. The resin base material may or may not have transparency.

The resin used for the resin base material is not particularly limited, and is, for example, a polyolefin resin such as polyethylene or polypropylene, a polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polybutylene terephthalate (PBT). , Cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyvinyl alcohol (PVA) and ethylene- Polyvinyl alcohol resin such as vinyl alcohol copolymer (EVOH), ethylene-vinyl ester copolymer saponified product, polyamide resin such as various nylons, polyimide resin, polyurethane resin, acetal resin, cellulose resin and other various resins. Can be used. In the present disclosure, among the above resins, PET, polypropylene and the like are preferably used, and PET is more preferably used from the viewpoints of toughness, oil resistance, chemical resistance, availability and the like.

Since the resin base material is close to the gas barrier layer, when the dimensions of the resin base material expand and contract, compressive / tensile stress is also applied to the gas barrier layer, and cracks are likely to occur. Therefore, in the present disclosure, it is preferable that the resin base material has a small dimensional change rate in a high temperature environment.

The resin base material may contain various plastic compounding agents, additives and the like. Examples of the additive include a lubricant, a cross-linking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, a resin for modification and the like. Further, the resin base material may be surface-treated. This is because the adhesion with the gas barrier layer can be improved. Examples of the surface treatment include an oxidation treatment, a roughening treatment (roughening treatment), and an easy-adhesion coating treatment disclosed in JP-A-2014-180837.

The thickness of the resin base material is not particularly limited, but is, for example, in the range of 6 μm or more and 200 μm or less, more preferably in the range of 9 μm or more and 100 μm or less.

(C) Overcoat Layer The gas barrier film may have an overcoat layer on the surface side of the gas barrier layer opposite to the resin base material. This is because the gas barrier property of the gas barrier film can be improved. Such an overcoat layer is not particularly limited, and those generally used as an overcoat agent can be used. For example, a mixed compound containing an organic moiety and an inorganic moiety can be used as the main component of the overcoat layer.

The thickness of the overcoat layer can be appropriately set according to the type of overcoating agent used, and is not particularly limited as long as the desired gas barrier property can be obtained. For example, it can be used in the range of 50 nm or more and 500 nm or less, particularly in the range of 100 nm or more and 400 nm or less.

There are various types of the above mixed compounds. For example, an alumina-based mixed compound such as Clarista CF (registered trademark) manufactured by Claret Co., Ltd., Besera (registered trademark) manufactured by Letterpress Printing Co., Ltd., etc. A gas barrier resin composition composed of a zinc acrylate-based mixed compound, a resin and an inorganic layered compound, and the general formula R ¹ _n M (OR ² ) _m (however, in the formula, R ¹ and R ² have carbon atoms. 1 or more and 8 or less organic groups, 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 solgel compound obtained from a raw material solution containing at least one alkoxide represented by (1) and a water-soluble polymer and further subjected to polycondensation by the solgel method can be used. Examples of the water-soluble polymer include polyvinyl alcohol-based resins, ethylene / vinyl alcohol copolymers, acrylic acid-based resins, natural polymer-based methyl celluloses, carboxymethyl celluloses, cellulose nanofibers, and polysaccharides. Patent No. 4961054 for the alumina-based mixed compound of phosphate, Patent No. 4373797 for the mixed compound of zinc acrylate, and Japanese Patent Application Laid-Open No. 4, for the gas barrier resin composition composed of the resin and the inorganic layered compound. Since it can be the same as that disclosed in 11-257574, the description thereof is omitted here.

In the present disclosure, among the above-mentioned mixed compounds, the general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ^{2 in the} formula represent organic groups having 1 or more carbon atoms and 8 or less carbon atoms, and M is , N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M.) At least one kind of alkoxide represented by, and polyvinyl. It contains an alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, and is further obtained by polycondensation by the sol-gel method in the presence of, for example, a sol-gel method catalyst, an acid, water, and an organic solvent. It is preferable to use a compound (hereinafter, may be referred to as “solgel compound”) in the overcoat layer. This is because the sol-gel compound has high adhesive strength at the interface, and the treatment at the time of film formation can be performed at a relatively low temperature, so that deterioration of the resin base material or the like due to heat can be suppressed. Since the sol-gel compound can be the same as that disclosed in Japanese Patent No. 5568897, the description thereof is omitted here.

(D) Others The outer packaging material of the present disclosure may have a plurality of gas barrier films as described above. This is because the gas barrier property of the outer packaging material can be improved. When the outer packaging material has a plurality of gas barrier films, the composition of each gas barrier film may be the same or different.

The order of the resin base material and the gas barrier layer described above is not particularly limited, and may be appropriately set according to the layer structure of each layer other than the gas barrier film and the number of gas barrier films used together for the outer packaging material. Can be done. For example, as illustrated in FIG. 3, when the vacuum heat insulating material is formed using the outer packaging material 10, the gas barrier layer 4 may be arranged so as to be inside the resin base material 3, and the figure also shows. As illustrated in 4 (a), when the outer packaging material 10 has the protective film 5, the gas barrier layer 4 may be arranged so as to be outside the resin base material 3. Further, when the outer packaging material 10 has two gas barrier films 2', even if the gas barrier layers 4 are arranged so as to face each other as illustrated in FIG. 4 (b), FIG. 4 (c) Although both gas barrier layers 4 are arranged so as to be inside the resin base material 3 as illustrated in FIG. 4 (d), both gas barrier layers 4 are resin groups as illustrated in FIG. 4 (d). It may be arranged so as to be on the outside of the material 3. Further, as illustrated in FIGS. 4 (e) and 4 (f), when the gas barrier film 2'is arranged on the outermost layer of the vacuum heat insulating material, the outermost layer is provided from the viewpoint of protecting the gas barrier layer 4. The gas barrier layer 4 of the above is preferably arranged so as to be inside the resin base material 3. Note that FIG. 4 is a schematic cross-sectional view showing another example of the outer packaging material of the present disclosure. When forming the vacuum heat insulating material, usually, two outer packaging materials are arranged so that the heat-weldable films 1 face each other.

3. 3. Protective film The outer packaging material of the present disclosure may have a protective film in addition to the above-mentioned heat-weldable film and gas barrier film. This is because when the outer packaging material has a protective film, each film used together as the outer packaging material, such as a heat-weldable film and a gas barrier film, can be protected from damage and deterioration. The protective film can be distinguished from each of the above-mentioned films in that a layer having a gas barrier property is not arranged on any of the surfaces thereof. The arrangement position of the protective film in the outer packaging material is not particularly limited, but the outermost layer (outermost layer) when forming the vacuum heat insulating material, such as the surface side of the gas barrier film opposite to the heat-weldable film. ), It is preferable that the protective film is arranged at the position.

The protective film may be in the form of a sheet or a film as long as it uses a resin having a melting point higher than that of a heat-weldable film. As such a protective film, for example, thermosetting resin such as nylon resin, polyester resin, polyamide resin, polypropylene resin, polyurethane resin, amino resin, silicone resin, epoxy resin, polyimide (PI) and the like Resins, polyvinyl chloride (PVC), polypropylene (PC), polystyrene (PS), polyvinyl alcohol (PVA), ethylene / vinyl acetate copolymer (EVAL), polyacrylonitrile (PAN), cellulose nanofibers (CNF), etc. Examples thereof include sheets and films, and among them, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), biaxially stretched polypropylene (OPP), polyvinyl chloride (PVC) and the like are preferably used.

The protective film has sufficient strength to protect the inside of the vacuum heat insulating material when the vacuum heat insulating material is formed using the outer packaging material of the present disclosure, and has heat resistance, pinhole resistance, and puncture resistance. It is preferable that the material has excellent properties. Further, the protective film preferably has gas barrier properties such as oxygen barrier properties and water vapor barrier properties.

The protective film may be a single layer, or may be a multi-layered film in which layers made of the same material or layers made of different materials are laminated. Further, the protective film may be subjected to a surface treatment such as a corona discharge treatment from the viewpoint of improving the adhesion with other layers. The thickness of the protective film is not particularly limited as long as it can protect each of the other films used together with the outer packaging material, but is generally within the range of 5 μm or more and 80 μm or less. Degree.

4. Outer packaging material for vacuum heat insulating material The outer packaging material in the present disclosure preferably has the characteristics described later.

(1) Relationship between tensile elastic modulus and thickness of outer packaging material for vacuum insulation material Generally, regarding the amount of deformation when stress is applied to an object, the object has a characteristic of tensile elastic modulus E, and its shape is When it is a rectangular body having a width b and a thickness h and the position where the stress F is applied is a position at a distance L from the end supporting the rectangular object, the deformation amount v is generally v = 4FL ³ / (. It is represented by bEh ³ ). On the other hand, if the product of the tensile elastic modulus E of the outer packaging material and the cube of the thickness h of the outer packaging material is a function M, the function M is represented by M = Eh ³ and is between the deformation amount v. , Inversely proportional. Therefore, the smaller the value of the function M, the larger the amount of deformation when the same stress is applied, which is an index of the softness of the outer packaging material. Therefore, the fact that the value of the function M is equal to or less than a predetermined value indicates that the outer packaging material has a predetermined flexibility.

Further, as described above, when the value of the function M is equal to or less than a predetermined value, the bent portion is bent when the outer packaging material is bent as compared with the value of the function M larger than the predetermined value. In addition, the number of wrinkles formed substantially parallel to the direction along the forming direction of the bent portion increases. For this reason, when the value of the function M is larger than a predetermined value and the outer packaging material is a hard material, the outer packaging material cannot be bent unless a strong stress is applied, and the gas barrier film. If there is even one point where the strength is weak, stress may be concentrated and cracks may occur when trying to bend at that point. On the other hand, when the value of the function M is equal to or less than a predetermined value and the outer packaging material is a soft material, the outer packaging material can be bent with a small stress, so that even if the gas barrier film has a weak strength. It is considered that bending is possible in other places without stress being concentrated in the place where the strength is weak, and the stress concentration can be dispersed. When the value of the function M is smaller than a predetermined value, the stress is dispersed in a plurality of places and bending occurs in many places, and as a result, the number of wrinkles formed in the bending portion is the value of the function M. Is more than the one larger than the predetermined value.

Therefore, in the present disclosure, the value of the function M, that is, the product of the tensile elastic modulus of the outer packaging material and the cube of the thickness of the outer packaging material is in the range of 3.0 MPa · mm ³ or less. Preferably, among them, within the range of 0.5 MPa · mm ³ or more and 2.5 MPa · mm ³ or less, particularly within the range of 0.5 MPa · mm ³ or more, 2.0 MPa · mm ³ or less, and further 0.5 MPa · mm. It is preferably in the range of ³ or more and 1.0 MPa · mm ³ or less. This is because when the value of the function M is within the above range, the occurrence of cracks in the gas barrier film can be suppressed more effectively. The effect of suppressing the occurrence of cracks is particularly remarkable for the outer packaging material having the gas barrier film of the first aspect, in which the gas barrier film is a metal foil. Therefore, when the outer packaging material has the gas barrier film of the first aspect described above, it is particularly preferable that the function M is within the above range. Further, since the amorphous copolymer resin has a large tensile elasticity, the heat-weldable film contains the amorphous copolymer resin, so that the value of the function M of the outer packaging material is desired. Can be.

The thickness of the outer packaging material in the function M refers to the thickness of the outer packaging material per sheet. For example, the outer packaging material in the vacuum heat insulating material formed by using the two outer packaging materials. Even when the function M of the above is calculated, the thickness used in the calculation refers to the thickness of one of the above-mentioned packaging materials.

The tensile elastic modulus of the outer packaging material is not particularly limited as long as the value of the function M can be set to a predetermined value or less, but is within the range of 1500 MPa or more and 5000 MPa or less. Of these, it is preferably in the range of 2000 MPa or more and 4000 MPa or less, and particularly preferably in the range of 2500 MPa or more and 3500 MPa or less. This is because it is easy to set the value of the function M to a predetermined value or less. Since the method for measuring the tensile elastic modulus is the same as that described in the above section "1. Heat-weldable film", the description thereof is omitted here.

(2) Dimensional Change Rate of Outer Packaging Material for Vacuum Insulation Material When the gas barrier film used for the outer packaging material is of the second aspect described above, that is, the gas barrier film is at least one of the resin base material and the resin base material. When the size of the resin base material shrinks in a high temperature environment, the gas barrier layer formed on the resin base material is also subjected to compressive stress when the gas barrier layer is composed of the gas barrier layer arranged on the surface side of the resin base material. When the size of the resin base material is increased, tensile stress is also applied to the gas barrier layer, so that cracks are likely to occur in the gas barrier layer. Further, when a layer used together with the gas barrier film in the outer packaging material such as a heat-weldable film or a protective film expands and contracts, compressive / tensile stress is also applied to the adjacent gas barrier layer, so that cracks are likely to occur as well.

Therefore, when the gas barrier film used for the outer packaging material is the one of the second aspect described above, it is preferable that the dimensional change rate of the outer packaging material is small in a high temperature environment. That is, based on the dimensions of the outer packaging material when the temperature of the atmosphere is 20 ° C., the temperature of the atmosphere is changed from 20 ° C. to 145 ° C., and the temperature of the atmosphere is maintained at 145 ° C. for 1 hour. The dimensional change rate of the outer packaging material when the temperature of the atmosphere is changed from 145 ° C. to 20 ° C. (hereinafter, may be referred to as "the dimensional change rate of the outer packaging material before and after maintaining a high temperature") is 1% or less. Above all, it is preferably 0.5% or less, particularly 0.4% or less, and further preferably 0.3% or less.

Further, when the temperature of the atmosphere is changed from 20 ° C. to 145 ° C. (hereinafter, may be referred to as “heating process”), the dimensional change rate of the outer packaging material is 1% or less, particularly 0.7%. Below, it is particularly preferable that it is 0.5% or less. Further, when the temperature of the atmosphere of the outer packaging material is maintained at 145 ° C. for 1 hour (hereinafter, may be referred to as “constant temperature process”), the dimensional change rate of the outer packaging material is 0.5% or less, especially. It is preferably 0.3% or less, particularly 0.1% or less. Further, when the temperature of the atmosphere of the outer packaging material is changed from 145 ° C. to 20 ° C. (hereinafter, may be referred to as "temperature lowering process"), the dimensional change rate of the outer packaging material is 1% or less, particularly. It is preferably 0.7% or less, particularly 0.5% or less. When each dimensional change rate of the outer packaging material is within the above range, the stress applied to the gas barrier film can be suppressed even when the outer packaging material is exposed to heat, so that the occurrence of cracks in the gas barrier film can be suppressed. This is because it is possible to use an external packaging material capable of forming a vacuum heat insulating material that can maintain the heat insulating performance for a long period of time even at a high temperature. Since the amorphous copolymer polyester resin has a small dimensional change rate in a high temperature environment, the heat-welding film contains the amorphous copolymer polyester resin, so that the dimensional change rate of the outer packaging material as a whole can be increased. It can be made smaller.

Here, the dimensional change rate of the outer packaging material means that the measurement sample is heated by a thermomechanical analyzer (TMA) under the following conditions at 20 ° C. to 145 ° C. and subsequently at 145 ° C. In each of the constant temperature process for 1 hour and the subsequent temperature lowering process from 145 ° C to 20 ° C, the initial value (before temperature rise) of the continuous film forming direction; the direction perpendicular to the longitudinal direction of the film; the width direction of the film). The dimensional change rate with respect to the dimension at 20 ° C.) was measured. As the thermomechanical analyzer, for example, TMA / SS6100 manufactured by Hitachi High-Tech Science Corporation can be used.

Measurement mode: Tensile mode, load 100mN
Sample length: 20 mm
Sample width: 5 mm
Temperature rise start temperature: 20 ° C
Temperature rise end temperature: 145 ° C (holding time at 145 ° C: 1 hour)
Temperature lowering end temperature: 20 ° C
Temperature rise and fall rate: 10 ° C / min
Measurement atmosphere: Under nitrogen purge

The dimensional change rate before and after holding at a high temperature is defined by the following formula (1). However, the size of the outer packaging material at 20 ° C. before the temperature rise is L ₀ of the formula (1), and the size of the outer packaging material that has undergone the temperature raising process, the constant temperature process and the temperature lowering process is L ₁ of the formula (1).
Dimensional change rate (%) before and after high temperature holding = | L _0- L ₁ | / L ₀ x 100 (1)
Further, the dimensional change rate in each process of the temperature raising process, the constant temperature process, and the temperature lowering process is defined by the following equation (2). However, the dimension of the outer packaging material at 20 ° C. before the temperature rise is L ₀ in the formula (2), and the minimum dimension of the outer packaging material obtained in the measurement process is L ₂ in the formula (2). The maximum dimension of the outer packaging material is L ₃ of the formula (2).
Dimensional change rate (%) in each process = (L _3- L ₂ ) / L ₀ × 100 (2)

(3) Others The thickness of the outer packaging material is not particularly limited as long as it can obtain desired gas barrier properties and strength, but is, for example, within the range of 30 μm or more and 200 μm or less. It is preferable that it is in the range of 50 μm or more and 150 μm or less. The tensile strength of the outer packaging material is preferably 50 N or more, and more preferably 80 N or more. This is because the vacuum heat insulating material formed by using the outer packaging material of the present disclosure is less likely to break when bent. The tensile strength is a value measured based on JIS Z 1707.

The method for laminating the outer packaging material is not particularly limited as long as the outer packaging material having a desired constitution can be obtained, and a known method can be used. For example, a dry lamination method in which each film formed in advance is bonded using an adhesive, or a laminate obtained by extruding and bonding each material such as a heat-melted gas barrier film using a T-die or the like. Examples thereof include a method of laminating a heat-weldable film via an adhesive.

The outer material, the oxygen permeability of 0.1cc ^/ m 2 ^/ day ^/ atm or less, and preferably less inter alia ^{0.05cc / m 2 / day / atm} . Further, the vacuum heat insulating material for outer material water vapor permeability of 0.5g ^/ m 2 ^/ day or less, preferably 0.1g ^/ m 2 ^/ day or less, particularly equal to or less than 0.05g ^/ m 2 ^/ day Is preferable. This is because the vacuum heat insulating material having high heat insulating performance can be formed because the outer packaging material has a gas barrier property within the above range. The method for measuring the oxygen permeability and the water vapor permeability of the outer packaging material is the same as the method for measuring each permeability described in the section "2. Gas barrier film, (1) First aspect". The explanation in is omitted.

B. Vacuum heat insulating material Next, the vacuum heat insulating material of the present disclosure will be described. The vacuum heat insulating material of the present disclosure is a vacuum heat insulating material having a core material and an outer packaging material for the vacuum heat insulating material that encloses the core material, and the outer packaging material for the vacuum heat insulating material is the outer packaging material for the vacuum heat insulating material described above. It is characterized by being.

The vacuum heat insulating material of the present disclosure can be the same as that illustrated in FIG. 2 described above. According to the present disclosure, since the outer packaging material for the vacuum heat insulating material is the above-mentioned outer packaging material for the vacuum heat insulating material, it can be a vacuum heat insulating material capable of maintaining the heat insulating performance for a long period of time.

The vacuum heat insulating material of the present disclosure has at least an outer packaging material and a core material for the vacuum heat insulating material.
Hereinafter, the vacuum heat insulating material of the present disclosure will be described for each configuration.

1. 1. Outer packaging material for vacuum heat insulating material The outer packaging material in the present disclosure encloses the core material. The outer packaging material is the above-mentioned outer packaging material. Since such an outer packaging material can be the same as the content described in the section "A. Outer packaging material for vacuum heat insulating material", the description thereof is omitted here.
In addition, sealing means that the bag is sealed inside the bag formed by using the outer packaging material.

2. Core material The core material in the present disclosure is enclosed by the above-mentioned outer packaging material for vacuum heat insulating material.
The core material preferably has a low thermal conductivity. The core material is preferably a porous material having a porosity of 50% or more, particularly 90% or more.

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

Further, examples of the above-mentioned foam include urethane foam, styrene foam, phenol foam, and the like, and among these, a foam that forms open cells is preferable.

Further, the fiber body may be an inorganic fiber or an organic fiber, but it is preferable to use an inorganic fiber from the viewpoint of heat insulating performance. Examples of such inorganic fibers include glass fibers such as glass wool and glass fiber, alumina fibers, silica-alumina fibers, silica fibers, ceramic fibers, and rock wool. These inorganic fibers are preferable in that they have low thermal conductivity and are easier to handle than powders.

The core material may be a composite material obtained by using the above-mentioned materials alone or by mixing two or more kinds of materials.

3. 3. Vacuum heat insulating material The vacuum heat insulating material of the present disclosure is a vacuum heat insulating material in which the inside sealed with the outer packaging material for the vacuum heat insulating material is vacuum-sealed. The degree of vacuum inside the vacuum heat insulating material is preferably 5 Pa or less. By setting the degree of vacuum inside the vacuum heat insulating material within the above range, it is possible to reduce the heat conduction due to the convection of the air remaining inside, and it is possible to exhibit excellent heat insulating properties.

Further, the thermal conductivity of the vacuum heat insulating material is preferably low. For example, the thermal conductivity (initial thermal conductivity) of the vacuum heat insulating material at 25 ° C. is preferably 5 mW / m · K or less. It is preferably 4 mW / m · K or less, and particularly preferably 3 mW / m · K or less. By setting the thermal conductivity of the vacuum heat insulating material within the above range, the vacuum heat insulating material is less likely to conduct heat to the outside, so that a high heat insulating effect can be obtained. The thermal conductivity can be a value measured by a heat flow metering method using a thermal conductivity measuring device according to JIS A 14123. Examples of the thermal conductivity measuring device include a thermal conductivity measuring device Autolambda (product name HC-074, manufactured by Eiko Seiki).

The vacuum heat insulating material preferably has a high gas barrier property. This is because it is possible to prevent a decrease in the degree of vacuum due to the intrusion of moisture, oxygen, etc. from the outside. The gas barrier property of the vacuum heat insulating material is the same as the oxygen permeability and water vapor permeability described in the above-mentioned "A. Outer packaging material for vacuum heat insulating material, 4. Outer packaging material for vacuum heat insulating material, (3) Others". Therefore, the description here will be omitted.

4. Manufacturing Method As the manufacturing method of the vacuum heat insulating material of the present disclosure, a general method can be used. For example, the above-mentioned outer packaging material of the present disclosure is prepared in advance, and the two above-mentioned outer packaging materials are opposed to each other so that the heat-weldable films face each other inward, and the core material is arranged between them to form a bag making machine or the like. By heat-welding the ends of the outer packaging materials on the remaining three sides with one of the outer circumferences of the core material as an opening, the bag body is formed by the two outer packaging materials and the core material is arranged inside. Then, the bag body is attached to a vacuum sealer, and the opening is sealed with the internal pressure of the bag body reduced, so that the core material is sealed by the outer packaging material. Insulation is obtained.

Further, in the above manufacturing method, one sheet of the outer packaging material is opposed to the inside so that the heat-weldable film faces inward, the core material is arranged between them, and one of the outer circumferences of the core material is placed by a bag making machine or the like. By making an opening and heat-welding the ends of the remaining two outer packaging materials to each other, a bag body formed of one of the outer packaging materials and having the core material arranged inside is prepared, and then the above-mentioned This is a method of obtaining a vacuum heat insulating material in which the core material is sealed by the external packaging material by mounting the bag body on a vacuum sealer and sealing the opening in a state where the internal pressure of the bag body is reduced. You may.

5. Applications The vacuum heat insulating material of the present disclosure has low thermal conductivity and is excellent in heat insulating properties and durability even at high temperatures. Therefore, the vacuum heat insulating material can be used in a portion that has a heat source and generates heat, or a portion that becomes hot due to being heated from the outside. Applications of the present disclosure include, for example, equipment described in "C. Equipment with vacuum heat insulating material", cooler box, transportation container, fuel tank such as hydrogen, system bath, hot water tank, heat insulator, residential wall, automobile, and the like. Examples include airplanes, ships, trains, etc.

C. Equipment with Vacuum Heat Insulation Next, the equipment with vacuum heat insulating material of the present disclosure will be described. The device with the vacuum heat insulating material of the present disclosure is a device having a heat source part or a heat insulating part inside the main body or the device, and a device with a vacuum heat insulating material provided with the vacuum heat insulating material. The vacuum heat insulating material includes a core material and the above. It has an outer packaging material for a vacuum heat insulating material that encloses a core material, and is characterized in that the outer packaging material for the vacuum heat insulating material is the outer packaging material for the vacuum heat insulating material described above.

Here, the "heat source unit" refers to a portion that generates heat in the main body of the device or inside the device when the device itself is driven, and refers to, for example, a power supply or a motor. Further, the "heat-insulated portion" refers to a portion where the device itself or the inside does not have a heat source section, but the device receives heat from an external heat source and becomes hot.

According to the present disclosure, the vacuum heat insulating material is the vacuum heat insulating material described above, and the heat insulating performance can be maintained for a long period of time. Therefore, in a device having a heat source portion, the heat from the heat source portion is generated by the vacuum heat insulating material. The heat insulation is performed to prevent the temperature of the entire device from becoming high, while in the device having the heat insulating portion, the temperature state of the heat insulating portion can be maintained by the vacuum heat insulating material. As a result, it is possible to obtain a device having high energy saving characteristics with reduced power consumption.

Since the vacuum heat insulating material in the present disclosure is the same as the content described in the section "B. Vacuum heat insulating material" described above, the description thereof is omitted here.

The device in the present disclosure is a main body or a device having a heat source portion or a heat insulating portion inside the main body. The equipment in the present disclosure includes, for example, electric equipment such as a natural refrigerant heat pump water heater (registered trademark "EcoCute"), a refrigerator, a vending machine, a rice cooker, a pot, a microwave oven, a commercial oven, an IH cooking heater, and an OA equipment. Examples include automobiles, residential walls, and transportation containers. Above all, in the present disclosure, it is preferable that the above-mentioned equipment uses the above-mentioned vacuum heat insulating material in the present disclosure for a natural refrigerant heat pump water heater, a commercial oven, a microwave oven, an automobile, a residential wall, and a shipping container.

As a mode of attaching the vacuum heat insulating material to the device, the vacuum heat insulating material may be directly attached to the heat source portion or the heat insulating portion of the device, and the vacuum heat insulating material may be attached between the heat insulating portion and the heat source portion or the external heat source. It may be attached so as to sandwich the.

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

The present disclosure will be described in more detail with reference to Examples, Comparative Examples and Reference Examples.

[Example 1]
(Preparation of interlayer adhesive)
A main agent containing polyester as a main component, a curing agent containing an aliphatic polyisocyanate, and ethyl acetate are mixed so that the weight mixing ratio is main agent: curing agent: ethyl acetate = 10: 1:10, and two-component curing is performed. A mold interlayer adhesive was prepared.

(Preparation of outer packaging material for vacuum heat insulating material)
An outer packaging material having a layer structure of a first gas barrier film / a second gas barrier film / a third gas barrier film / a heat-weldable film was produced. As the first gas barrier film, a nylon film (IB-ON-UB manufactured by Dai Nippon Printing Co., Ltd.) having a silica film deposited on one surface side was used.
As the second gas barrier film and the third gas barrier film, a group in which an aluminum film having a thickness of 40 nm is vapor-deposited on a polyethylene terephthalate (PET) film and has an overcoat layer on the surface side opposite to the PET film of the aluminum film, respectively. The material was used. As the heat-weldable film, a PET film having a thickness of 30 μm (manufactured by Kurabo Industries Ltd.) was used. In each of the above layers, an interlayer adhesive prepared with the above-mentioned compounding ratio was laminated on the surface side of the lower layer by a dry laminating method so as to have a coating amount of 3.5 g / m ² .

(Making vacuum heat insulating material)
Two of the obtained outer packaging materials were stacked and heat-sealed in three rectangular directions to prepare a bag body in which only one direction was open. A glass wool of 300 mm × 300 mm × 30 mm was used as the core material, and after the drying treatment, the core material was stored in the bag body and the inside of the bag body was evacuated. Then, the opening portion of the bag body was sealed with a heat seal to obtain a vacuum heat insulating material. The ultimate pressure was 0.05 Pa.

[Comparative Example 1]
An external packaging material and a vacuum heat insulating material were obtained in the same manner as in Example 1 except that an unstretched polypropylene film having a thickness of 50 μm (manufactured by Toray Film Processing Co., Ltd., 3301) was used as the heat-weldable film.

[Comparative Example 2]
As the second gas barrier film and the third gas barrier film, a base material (Dainippon Printing Co., Ltd.) in which a silica film is vapor-deposited on the PET film and an overcoat layer is provided on the surface side of the silica film opposite to the PET film. An outer packaging material and a vacuum heat insulating material were obtained in the same manner as in Comparative Example 1 except that IB-PET) was used.

[Comparative Example 3]
As the first gas barrier film and the second gas barrier film, PET films having a thickness of 12 μm (VMPET1519 manufactured by Toray Film Processing Co., Ltd.) on which an aluminum film was vapor-deposited were used, respectively, and as the third gas barrier film, one surface side was used. The outer packaging material and the vacuum heat insulating material were used in the same manner as in Comparative Example 1 except that an ethylene-vinyl alcohol copolymer (EVOH) film (manufactured by Kuraray Co., Ltd., VMXL) having a thickness of 15 μm on which an aluminum film was vapor-deposited was used. Obtained.
[Comparative Example 4]
A nylon film (IB-ON-UB, manufactured by Dainippon Printing Co., Ltd.) with a silica film deposited on one side is used as the first gas barrier film, and the second gas barrier film is overcoated on one side. An outer packaging material and a vacuum heat insulating material were obtained in the same manner as in Comparative Example 3 except that a PET film having a layer and a thickness of 12 μm (Mitsui Chemicals Tohcello Co., Ltd., Max Barrier) was used.

[Example 2]
An outer packaging material having a layer structure of a protective film / gas barrier film / heat-weldable film was prepared. A PET film having a thickness of 16 μm (PTMB, manufactured by Unitika Ltd.) was used as the protective film, and an aluminum foil (UACJ Corporation, 8021) having a thickness of 6 μm was used as the gas barrier film. As the heat-weldable film, the same film as in Example 1 was used. The outer packaging material having the above layer structure was produced in the same manner as in Example 1, and two obtained outer packaging materials were laminated to obtain a vacuum heat insulating material in the same manner as in Example 1.

[Comparative Example 5]
Two films, a nylon film with a thickness of 25 μm on the outside (ONBC, manufactured by Unitica Co., Ltd.) and a PET film with a thickness of 12 μm on the inside (PTMB, manufactured by Unitica Co., Ltd.) are used as protective films as a heat-weldable film. An outer packaging material and a vacuum heat insulating material were obtained in the same manner as in Example 2 except that an unstretched polypropylene film having a thickness of 50 μm (manufactured by Toray Film Co., Ltd., 3301) was used.

[Evaluation]
(Amount of deterioration of thermal conductivity of vacuum heat insulating material heat)
The time course of the thermal conductivity of the vacuum heat insulating materials obtained in each of the above Examples and Comparative Examples was measured in an atmosphere at a temperature of 145 ° C. and no humidity control. The thermal conductivity of each vacuum heat insulating material is a value measured by a heat flow meter method using a thermal conductivity measuring device according to JIS A 14123. As the thermal conductivity measuring device, a thermal conductivity measuring device Autolambda (product name HC-074, manufactured by Hidehiro Seiki) was used. The measurement results of Example 1 and Comparative Examples 1 to 4 are shown in FIG. 5, and the measurement results of Example 2 and Comparative Example 5 are shown in FIG. In addition, in FIG. 5 and FIG. 6, the difference between the thermal conductivity at each elapsed time and the thermal conductivity (initial value) after 0 hours has elapsed is shown as "the amount of deterioration of thermal conductivity".

(Measurement of dimensional change rate of outer packaging material for vacuum heat insulating material)
The dimensional change rate at high temperature was measured for the outer packaging materials obtained in Example 1 and Comparative Examples 1 to 4. The dimensional change rate is determined by the method and conditions described in "A. Dimensional change rate of vacuum heat insulating material outer packaging material, 4. Vacuum heat insulating material outer packaging material, (2) Vacuum heat insulating material outer packaging material". The size of the outer packaging material was measured and the rate of change in size was determined. The dimensional change rate in each process of each of the above-mentioned packaging materials is shown in Table 1 below.

(Calculation of function M of outer packaging material for vacuum heat insulating material)
For the outer packaging materials obtained in Example 2 and Comparative Example 5, the tensile elastic modulus of the outer packaging material and the thickness of the outer packaging material were measured, and the function M was calculated. The tensile elastic modulus of each packaging material is measured by the method for measuring the tensile elastic modulus of a heat-welding film described in the above section "A. Outer packaging material for vacuum heat insulating material, 1. Heat-weldable film".・ The procedure was the same as for the conditions and equipment. The tensile elastic modulus, thickness, and function M value of each packaging material are shown in Table 2 below.

(Summary)
The vacuum heat insulating materials of Examples 1 and 2 in which the film of the amorphous copolymer polyester resin is used as the heat-weldable film are the vacuum heat insulating materials of Comparative Examples 1 to 5 even after a long time in a high temperature environment. It can be seen that the amount of deterioration of thermal conductivity is significantly smaller than that of the heat insulating material. Further, the outer packaging material of Example 1 has a small dimensional change rate in a high temperature environment, and the outer packaging material of Example 2 has a small value of the function M. For these reasons, by using an amorphous copolymer polyester resin film as the heat-weldable film, cracks in the gas barrier film of the outer packaging material are suppressed, leading to a reduction in the amount of deterioration in thermal conductivity. It is speculated.

1 ... Heat-weldable film 2, 2'... Gas barrier film 3 ... Resin base material 4 ... Gas barrier layer 5 ... Protective film 10 ... Outer packaging material for vacuum heat insulating material 11 ... Core material 12 ... End 20 ... Vacuum heat insulating material

Claims (6)

An external packaging material for a vacuum heat insulating material having at least a heat-weldable film and a gas barrier film.
Wherein the heat weldable film, contains a copolymerized polyester resin amorphous,
The gas barrier film has a resin base material and a gas barrier layer arranged on at least one surface side of the resin base material.
Based on the dimensions of the outer packaging material for the vacuum heat insulating material when the temperature of the atmosphere is 20 ° C., the temperature of the atmosphere is changed from 20 ° C. to 145 ° C., and the temperature of the atmosphere is maintained at 145 ° C. for 1 hour. The outer packaging material for the vacuum heat insulating material is characterized in that the dimensional change rate of the outer packaging material for the vacuum heat insulating material is 1% or less when the temperature of the atmosphere is changed from 145 ° C. to 20 ° C. The outer packaging material for a vacuum heat insulating material according to claim 1, wherein the heat welding temperature of the resin constituting the heat-welding film is 120 ° C. or higher. The outer packaging material for a vacuum heat insulating material according to claim 1 or 2, wherein the tensile elastic modulus of the heat-weldable film is within the range of 1.0 GPa or more and 5.0 GPa or less. The outer package for a vacuum heat insulating material according to any one of claims 1 to 3, wherein the gas barrier film has a protective film on the surface side opposite to the heat-weldable film. Material. A vacuum heat insulating material having a core material and an outer packaging material for the vacuum heat insulating material that encloses the core material.
The outer packaging material for the vacuum heat insulating material has at least a heat-weldable film and a gas barrier film.
Wherein the heat weldable film, contains a copolymerized polyester resin amorphous,
The gas barrier film has a resin base material and a gas barrier layer arranged on at least one surface side of the resin base material.
Based on the dimensions of the outer packaging material for the vacuum heat insulating material when the temperature of the atmosphere is 20 ° C., the temperature of the atmosphere is changed from 20 ° C. to 145 ° C., and the temperature of the atmosphere is maintained at 145 ° C. for 1 hour. The vacuum heat insulating material is characterized in that the dimensional change rate of the outer packaging material for the vacuum heat insulating material when the temperature of the atmosphere is changed from 145 ° C. to 20 ° C. is 1% or less . Equipment that has a heat source part or heat insulation part inside the main body or inside, and equipment with a vacuum heat insulating material that has a vacuum heat insulating material.
The vacuum heat insulating material has a core material and an outer packaging material for the vacuum heat insulating material that encloses the core material.
The outer packaging material for the vacuum heat insulating material has at least a heat-weldable film and a gas barrier film.
Wherein the heat weldable film, contains a copolymerized polyester resin amorphous,
The gas barrier film has a resin base material and a gas barrier layer arranged on at least one surface side of the resin base material.
Based on the dimensions of the outer packaging material for the vacuum heat insulating material when the temperature of the atmosphere is 20 ° C., the temperature of the atmosphere is changed from 20 ° C. to 145 ° C., and the temperature of the atmosphere is maintained at 145 ° C. for 1 hour. A device with a vacuum heat insulating material, wherein the dimensional change rate of the outer packaging material for the vacuum heat insulating material is 1% or less when the temperature of the atmosphere is changed from 145 ° C. to 20 ° C.