JPH11257573A - Vacuum insulation material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vacuum insulation material which has an excellent heat insulating property, and can maintain the heat insulating property for a long period. SOLUTION: This vacuum insulation material is composed by vacuum exhausting a core member including hollow part covered by a resin laminate body which has at least one layer of a gas barrier type resin composite layer consisting of a resin and an inorganic layer form compound, and the hollow part includes a getter agent. In this case, the getter agent is an agent to absorb a gas such as the carbon dioxide, oxygen, and nitrogen, and the steam, and the iron powder; a resin composite including a bellet from or a sheet form iron powder; a synthetic zeolite an alloy including zilconium, and a varium-litium alloy; are used as this agent. In the zeolite system getter agent, it is favorable not to dehydrate by the heating and the like beforehand, in the view point of the heat insulating property, and the synthetic zeolite having the hole diameter 8 to 13 Å is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a vacuum heat insulating material.

[0002]

2. Description of the Related Art A method of evacuating the inside of a structure sealed with a container or an outer wrapping material formed of a gas barrier material to enhance the heat insulating effect has been conventionally known. A vacuum heat insulating material in which a core material is filled in the inside of the structure and evacuated is also known. In such a vacuum heat insulating material, the gas heat transfer is reduced by maintaining the inside at a high degree of vacuum to improve the heat insulating property.In order to maintain the heat insulating property for a long time, for example, the above-described structure is used. It is necessary to use a material having extremely excellent gas barrier properties for the body.

As such a material, a resin, particularly a thermoplastic resin, is preferably used from the viewpoint of moldability, but PVDC (polyvinylidene chloride) or EVOH (ethylene-vinyl acetate copolymer) which is a typical example of a resin having excellent gas barrier properties is used. However, the gas barrier properties of the unified saponified product and the like are insufficient as a vacuum heat insulating material, and it has been difficult to maintain the heat insulating property of the obtained structure for a long period of time. Therefore, for the purpose of improving the gas barrier properties of the resin, for example, Japanese Patent Application Laid-Open
JP-A-279083 and JP-A-63-233284 describe a metal laminate in which an aluminum foil is laminated on a thermoplastic resin film.

[0004] However, a vacuum heat insulating material comprising the above-mentioned metal laminate can maintain a high degree of vacuum for a long period of time, but a metal such as aluminum has a high thermal conductivity (for example, aluminum has a thermal conductivity of about 200 W). / MK
Whereas, the polypropylene resin is about 0.23 W /
m · K, about 0.02 W / m · K in air), a so-called heat bridge in which heat moves along the metal part was generated, and the heat insulation performance was greatly reduced. Although it has been considered to reduce the thickness of the metal layer for the purpose of suppressing heat bridges, generally, when laminating a metal on a thermoplastic resin layer, a metal such as aluminum is vaporized once at a high temperature and then the surface of the resin layer is formed. In order to deposit a metal foil separately by rolling, etc., and then laminate it to a resin layer, in these methods, when the thickness of the metal layer is reduced, many pinholes are generated,
Despite providing a metal layer, gas barrier properties are reduced,
As a result, the long-term insulation performance was reduced.

[0005] In particular, in applications such as refrigerators and the like, a long-term (for example, 10 years or more) heat insulation performance is required. Even if the amount of gas generated and the amount of gas permeating from the sealant resin layer are very small, they cannot be ignored, resulting in a problem that the degree of vacuum inside is reduced and the heat insulation performance is also reduced. Therefore, for the purpose of absorbing and adsorbing the gas passing therethrough and the generated gas, for example, JP-A-8-159377, JP-A-8-338683
JP-A-7-269780 and JP-A-4-225775 disclose the use of a getter agent, but they are still insufficient in maintaining the heat insulating performance for a long time.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that a resin composition layer composed of a resin and an inorganic layered compound has high gas barrier properties and low thermal conductivity. The present inventors have further found that excellent heat break performance can be maintained over a long period of time by using a getter agent in combination.

That is, the present invention provides a vacuum heat insulating material obtained by evacuating a hollow portion containing a core material covered with a resin laminate having at least one gas barrier resin composition layer composed of a resin and an inorganic layered compound. Accordingly, the present invention provides a vacuum heat insulating material in which the hollow portion further contains a getter agent. Hereinafter, the present invention will be described in detail.

BEST MODE FOR CARRYING OUT THE INVENTION

The inorganic stratiform compound used in the present invention includes:
An inorganic compound in which unit crystal layers are stacked on each other to have a layered structure. The layered structure refers to a structure in which planes in which atoms are strongly bonded by covalent bonds or the like and densely arranged are stacked substantially in parallel by a weak bonding force such as van der Waals force. As the inorganic layered compound, the aspect ratio measured by the method described below is 5 from the viewpoint of gas barrier properties, economic efficiency and availability of the obtained resin laminate.
It is preferably 0 or more and 5000 or less, more preferably 100 or more, and particularly preferably 200 or more and 3000 or less. Also,
From the viewpoint of the moldability of the resin laminate described below, the particle size measured by the method described below is preferably 5 μm or less, more preferably 3 μm or less.

Specific examples of such an inorganic layered compound include:
Graphite, phosphate derivative type compound (zirconium phosphate compound), chalcogenide [Group IV (Ti,
Zr, Hf), a dichalcogen compound of group V (V, Nb, Ta) and Group VI (Mo, W), the formula MX _2. Here, X is a chalcogen (S, Se, Te)
Is shown. And clay-based minerals.

The aspect ratio (Z) of the inorganic layered compound used in the present invention is a ratio determined from the relationship of Z = L / a. Here, L is the particle size (volume-based median diameter) of the inorganic layered compound in the dispersion obtained by the particle size measurement method by the diffraction / scattering method described above, and a is the unit thickness of the inorganic layered compound. is there. The “unit thickness a” is a value determined based on the measurement of the inorganic stratiform compound alone by a powder X-ray diffraction method or the like described later. More specifically, as shown schematically in the graph of FIG. 1 in which the horizontal axis indicates 2θ and the vertical axis indicates the intensity of the X-ray diffraction peak, it corresponds to the lowest angle peak among the observed diffraction peaks. From the angle θ
gg (nλ = 2D sin θ, n = 1, 2, 3,...)
) Is defined as “unit thickness a” (for details of the powder X-ray diffraction method, see, for example, Jiro Shiokawa, “Guidance for Instrumental Analysis (a)”, p. 69 (1985)
Year) can be referred to issued by Kagaku Doujinsha).

When the resin composition obtained by removing the solvent from the dispersion liquid is subjected to powder X-ray diffraction, it is usually possible to determine the interplanar spacing d of the inorganic layered compound in the resin composition. More specifically, as shown in the graph of FIG. 2 in which the horizontal axis indicates 2θ and the vertical axis indicates the intensity of the X-ray diffraction peak,
Of the diffraction peaks observed on the lower angle (larger interval) side than the diffraction peak position corresponding to the above “unit thickness a”, the interval corresponding to the peak at the lowest angle side is referred to as “plane interval d” (a <D). As schematically shown in the graph of FIG. 3, when it is difficult to detect the peak corresponding to the “surface distance d” by overlapping with a halo (or background), the baseline on the lower angle side than 2θd is detected. The area of the portion excluding is set as a peak corresponding to the “surface distance d”. Here, “θd” is “(unit length a) +
(The width of a single resin chain) "(for details of the method of determining the spacing d, see, for example, Shuichi Iwami et al.," Encyclopedia of Clay ", p. 35 or less and p. 271 or less,
1985, Asakura Shoten Co., Ltd. can be referred to).

As described above, the “integrated intensity” of the diffraction peak (corresponding to the plane distance d) observed in the powder X-ray diffraction of the resin composition is the same as the reference diffraction peak (corresponding to the “plane distance d”). The relative ratio to the integrated intensity is preferably 2 or more (more preferably 10 or more). Usually, the above-mentioned surface distance d
And the value of k = (da) (when converted to “length”) is equal to or larger than the width of a single resin chain constituting the resin composition. (K = (d
-A) ≧ resin single-chain width). Such “width of single resin chain” can be determined by simulation calculation or the like (for example, “Introduction to Polymer Chemistry”, 103-1)
10, page 1981, Kagaku Doujin), and in the case of polyvinyl alcohol, it is 4 to 5 angstroms (2 to 3 angstroms for water molecules).

It is extremely difficult to directly measure the "true aspect ratio" of the inorganic layered compound in the resin composition. The above aspect ratio Z = L / a is not always equal to the “true aspect ratio” of the inorganic layered compound in the resin composition.
It is appropriate to approximate “true aspect ratio” with

The relation a <d is established between the spacing d determined by the powder X-ray diffraction method of the resin composition and the “unit thickness a” determined by the powder X-ray diffraction measurement of the inorganic layered compound alone. And the value of (da) is less than the value of resin 1 in the composition.
If the width of the main chain or more, in the resin composition,
The resin is inserted between the layers of the inorganic layered compound. Therefore, to approximate the thickness of the inorganic layered compound in the resin composition by the above “unit thickness a”, that is, the “true aspect ratio” in the resin composition, The approximation with the "aspect ratio Z" has sufficient validity.

As described above, it is extremely difficult to measure the true particle size in the resin composition. However, the particle size of the inorganic stratiform compound in the resin is determined in the dispersion (resin / inorganic stratiform compound / solvent). Can be considered to be quite close to the particle size of the inorganic layered compound. However, since the particle diameter L in the dispersion obtained by the diffraction / scattering method is considered to be very unlikely to exceed the major axis Lmax of the inorganic layered compound, the true aspect ratio (Lmax / a) of the present invention is not so high. The probability of being lower than the “aspect ratio Z” used in (Lmax / a <Z) is theoretically quite low. From the above two points, it is considered that the definition Z of the aspect ratio used in the present invention has sufficient validity. In the present specification, “aspect ratio” or “particle size” means “aspect ratio Z” defined above or “particle size L determined by a diffraction / scattering method”.

From the viewpoint of the aspect ratio as described above,
As the inorganic layered compound, an inorganic layered compound which swells or cleaves in a solvent is preferably used. The degree of swelling or cleavage of the inorganic layered compound used in the present invention in a solvent can be evaluated by the following swelling and cleavage test. The degree of swelling of the inorganic stratiform compound is preferably about 5 or more (more preferably about 20 or more) in the following swellability test. On the other hand, the degree of cleavage of the inorganic layered compound is preferably about 5 or more (more preferably about 20 or more) in the following cleavage test. However, in these measurements, a solvent having a density smaller than the density of the inorganic layered compound is used as a solvent.For example, when the inorganic layered compound is a natural swellable clay mineral, water may be used as the solvent. preferable.

<Swellability test>: 2 g of the inorganic layered compound was added to 100 mL of a solvent (for example, using a 100 mL graduated cylinder as a container), stirred, and allowed to stand at 23 ° C. for about 1 day. The volume of the former (inorganic layered compound dispersed layer) is read from the scale of the interface. It can be said that the larger the value is, the higher the swelling property is.

<Cleaving test>: 30 g of inorganic layered compound
Was slowly added to 1500 mL of a solvent, sufficiently dispersed with a dispersing machine (23 ° C.), 100 mL of the dispersion was taken, and allowed to stand for about 1 hour, and the volume of the inorganic layered compound dispersed layer was measured from the scale at the interface with the supernatant in the same manner as described above. I Read. It can be said that the larger this value is, the higher the cleavage is.

As the inorganic layered compound which swells or cleaves in a solvent, a clay mineral swelling or cleaving in a solvent can be suitably used. Clay-based minerals generally have a two-layer structure having an octahedral layer with aluminum or magnesium as the central metal on top of a silica tetrahedral layer, and a silica tetrahedral layer containing aluminum or magnesium. It is classified into a type having a three-layer structure in which an octahedral layer serving as a central metal is sandwiched from both sides.

Examples of the former include kaolinites and antigolites, and the latters include smectites, vermiculites, and vermiculites depending on the number of interlayer cations.
Mica and the like can be mentioned.

Specifically, kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilyl mica, sodium teniolite, muscovite, margarite, talc, vermiculite Phlogopite, zansophilite, chlorite and the like.

The solvent for swelling the inorganic layered compound is, for example, in the case of a natural swelling clay mineral, water, alcohols such as methanol, dimethylformamide, dimethylsulfoxide, acetone and the like, and alcohols such as water and methanol. More preferred.

Examples of the resin used in the gas barrier resin composition layer comprising the inorganic layered compound and the resin include modified polyvinyl alcohol resins such as polyvinyl alcohol (PVA) and cross-linked polyvinyl alcohol, and ethylene-vinyl alcohol. Polymer (EVO
H) and modified ethylene-vinyl alcohol resins such as cross-linked ethylene-vinyl alcohol copolymer, polyvinylidene chloride (PVDC), polyacrylonitrile (P
AN), polysaccharides, polyacrylic acid and esters thereof, and the like.

Further, as a preferred example, the weight percentage of the hydrogen bonding group or the ionic group per unit weight of the resin is 2%.
A high hydrogen bonding resin satisfying a ratio of 0% to 60% is exemplified. More preferred examples include those in which the weight percentage of the hydrogen bonding group or the ionic group per unit weight of the high hydrogen bonding resin satisfies the ratio of 30% to 50%. Examples of the hydrogen bonding group of the high hydrogen bonding resin include a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like, and examples of the ionic group include a carboxylate group, a sulfonic acid ion group, and a phosphoric acid group. Examples include an ionic group, an ammonium group, and a phosphonium group.

Among the hydrogen bonding groups or ionic groups of the high hydrogen bonding resin, more preferred are a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonic acid ionic group, an ammonium group,
And the like.

As specific examples, for example, polyvinyl alcohol, an ethylene-vinyl alcohol copolymer having a vinyl alcohol fraction of 41 mol% or more, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, amylose, amylopectin, pullulan, curdlan, xanthan Polysaccharides such as, chitin, chitosan, cellulose, pullulan, chitosan, etc., polyacrylic acid, sodium polyacrylate, polybenzenesulfonic acid, sodium polybenzenesulfonate, polyethyleneimine, polyallylamine, its ammonium salt polyvinyl thiol, poly Glycerin, and the like.

More preferred examples of the high hydrogen bonding resin include polyvinyl alcohol and polysaccharides.
Polyvinyl alcohol is obtained by hydrolyzing (saponifying) an acetic ester portion of a vinyl acetate polymer, and is precisely a copolymer of vinyl alcohol and vinyl acetate. Here, the saponification ratio is preferably 70% or more in terms of mole percentage, and more preferably 85% or more. The degree of polymerization is preferably 100 or more and 5000 or less.

The polysaccharide is a biopolymer synthesized in a biological system by polycondensation of various monosaccharides, and herein includes those chemically modified based on them. Examples include cellulose and cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose and carboxymethylcellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan and the like.

In the present invention, the composition ratio (weight ratio) of the inorganic layered compound to the resin is (inorganic layered compound / resin) in a weight ratio of 5/95 to 90/10 from the viewpoint of the heat insulating effect and moldability.
Is preferred, and more preferably in the range of 5/95 to 50/50.

From the viewpoint of maintaining the heat insulating properties of the obtained vacuum heat insulating material over a long period, the gas barrier resin composition layer 2
The oxygen permeability at 3 ° C. and 50% RH is 0.2 cc / m ² · d
ay · atm or less is preferable, 0.1 cc / m ² · day · atm or less is more preferable, and 0.0001 cc / m ² · day · atm or less is particularly preferable. The oxygen permeability at 23 ° C. may be measured directly, or the oxygen permeability at a high temperature may be measured and measured by an Arrhenius plot.
It may be obtained by extrapolating to 3 ° C.

The method for producing the gas-barrier resin composition layer comprising the above-mentioned inorganic layered compound and a resin is not particularly limited, but the dispersibility and the operability of the inorganic layered compound in the obtained gas-barrier resin composition layer are not limited. From the viewpoint, for example, a method in which a liquid in which a resin is dissolved and a dispersion in which an inorganic layered compound is swollen or cleaved in advance are mixed, and then the solvent is removed (method 1), a dispersion in which the inorganic layered compound is swollen or cleaved Is added to the resin to remove the solvent (method 2), a method in which an inorganic layered compound is added to a liquid in which the resin is dissolved to form a dispersion in which the inorganic layered compound is swollen or cleaved, and the solvent is removed (method 3). And a method of hot-kneading the organic layered compound with the inorganic layer compound (method 4). From the viewpoint that a large aspect ratio of the inorganic layered compound can be easily obtained,
Are preferably used. In the former three cases, it is preferable to perform treatment using a high-pressure dispersion device from the viewpoint of dispersibility of the inorganic layered compound.

As a high-pressure dispersion device, for example, Micro
There is an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Fluidics Corporation or a Nanomizer manufactured by Nanomizer. Other examples include a Manton-Gaulin type high-pressure dispersion device, such as a homogenizer manufactured by Izumi Food Machinery.

Further, various additives such as an ultraviolet absorber, a coloring agent, and an antioxidant may be blended in the gas barrier resin composition layer as long as the effects of the present invention are not impaired.

The vacuum heat insulating material of the present invention has a core material-containing hollow portion covered with a resin laminate having at least one gas barrier resin composition layer, and the hollow portion further contains a getter agent. Things.

The hollow portion may be entirely covered with the resin laminate, or may have a region not covered with the laminate, but the hollow portion is covered with the laminate. When there is no region, the region is covered with another gas barrier material, or the area of the region is negligible from the viewpoint of gas barrier properties with respect to the area covered by the laminate. It is preferable from the viewpoint of maintaining heat insulation.

The core material is not particularly limited as long as it has heat insulation properties. For example, a core material having a thermal conductivity of less than 0.1 W / m · K as measured according to JIS R 2618 is preferable. Specific examples of the core material include pearlite powder, silica powder, precipitated silica powder, glass wool, rock wool, and a communicating resin foam. Especially 100%
The communicating urethane foam is preferable from the viewpoint of light weight.

The vacuum heat insulating material of the present invention contains a getter agent in the above-mentioned hollow portion. The getter agent means a substance that absorbs gas such as carbon dioxide, oxygen and nitrogen and / or water vapor, and includes, for example, iron powder, resin molded articles containing iron powder such as pellets and sheets, molecular sieves and the like. Commercially available getter agents such as synthetic zeolites, zirconium-containing alloys and barium-lithium alloys. Specific examples of alloy-based getters include COMBOGETTER
(Manufactured by SAES Getter Co., Ltd.). In the case of a zeolite-based getter agent, from the viewpoint of absorption performance, the getter agent is preferably dehydrated in advance by heating or the like, and a synthetic zeolite having a pore size of 8 to 13 ° is more preferable.

In the hollow portion of the vacuum heat insulating material of the present invention,
It may have a hollow structure. The shape of the hollow structure is not particularly limited, and includes a rectangular parallelepiped, a cube, a sphere, and the like.
In light of heat insulation, the thickness of the wall forming the hollow structure is preferably equal to or less than 10 mm, more preferably equal to or less than 5 mm,
Particularly preferred is 1 mm or less. The constituent material is not particularly limited, but is preferably made of resin from the viewpoint of the heat insulating property of the obtained vacuum heat insulator.

Examples of such a resin include low-density or high-density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene, and ethylene-acetic acid. Polyolefin resin such as vinyl copolymer, ethylene-methyl methacrylate copolymer, ionomer resin, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, nylon-6, nylon-
6,6, meta-xylene diamine-adipic acid condensation polymer,
Amide resins such as polymethyl methacrylimide, acrylic resins such as polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene and acrylonitrile resins such as polyacrylonitrile, cellulose triacetate , Cellulose-based hydrophobic resins such as cellulose diacetate, halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and Teflon; hydrogen-bonding resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and cellulose derivatives , Liquid crystalline polymers such as liquid crystal polyester resin, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyphenyleneoxy Resins, polymethylene oxide resins,
Engineering plastic resins such as aramid resins are exemplified.

Further, the hollow structure may have a getter agent and / or a core material as described above therein.

Examples of the resin laminate in the present invention include a laminate comprising a gas-barrier resin composition layer and a heat-sealing layer, or a laminate comprising a heat-sealing layer, a substrate layer and a gas-barrier resin composition layer. Although it is possible, the layer configuration is not particularly limited.

The method of evacuating the hollow portion covered with the resin laminate is not particularly limited. For example, the laminate is formed into a bag by heat fusion or the like, and a core material or the like is placed in the bag. For example, a method in which a hollow structure containing a core material or the like is inserted, the inside of the bag-shaped material is evacuated, and then the bag is sealed.

The pressure in the hollow part of the vacuum heat insulating material of the present invention is:
Usually, it is 1 Torr or less. From the standpoint of the heat insulating effect, 0.
1 Torr or less is more preferable, and 0.01 Torr or less is particularly preferable.

As the thermoplastic resin used as another layer such as a base layer other than the above-mentioned gas barrier resin composition layer, polyethylene (low density, high density),
Ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin, etc. Polyolefin resins, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; amide resins such as nylon-6, nylon-6,6, polycondensed methaxylenediamine-adipic acid, and polymethylmethacrylimide; Acrylic resin such as polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene and acrylonitrile such as polyacrylonitrile Cellulose resin, cellulose triacetate, hydrophobic cellulose resin such as cellulose diacetate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, halogen-containing resin such as Teflon, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose Hydrogen bonding resins such as derivatives, engineering resins such as polycarbonate resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, polyphenylene oxide resins, polymethylene oxide resins, and liquid crystal polyester resins. Among them, biaxially stretched polypropylene, polyethylene terephthalate, nylon, etc.
Biaxially-stretched polypropylene coated with polyvinylidene chloride called a coat, polyethylene terephthalate, nylon, etc., various vapor-deposited films such as aluminum-deposited films, alumina-deposited films, silica-deposited films, liquid crystal polyester resins, and aramid resins are preferably used. You.

When a heat-sealing layer is provided on the resin laminate, the resin used for the heat-sealing layer is made of polyethylene (low density, high density), Ethylene-vinyl alcohol copolymer,
Ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-octene copolymer, polypropylene, ethylene-vinyl acetate copolymer, Polyethylene resins such as ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, ionomer resin, polyamide resins such as nylon 6, nylon 66, and acrylonitrile / butadiene / styrene Examples include polymers, acrylonitrile / styrene copolymers, acrylonitrile copolymers, and polyacrylates such as polymethyl methacrylate.

The method for laminating the resin composition composed of the resin and the inorganic layered compound on another layer such as a base layer is not particularly limited. When the other layer is a film or sheet, for example, a coating solution of the composition is applied to the substrate surface,
A coating method of performing drying and heat treatment, and a method of laminating a composition film later are preferable. Examples of the coating method include a direct gravure method, a reverse gravure method, a microgravure method, a roll coating method such as a two roll beat coating method, a bottom feed three reverse coating method, a doctor knife method, a die coating method, a dip coating method, and a bar coating method. Examples of the method include a coating method and a coating method combining these methods.

The method of laminating the heat-sealing layer is not particularly limited, but a preferable example is a method of dry laminating on the other layer or the gas barrier resin composition layer. Further, each layer may be subjected to a treatment such as a corona treatment, an ozone treatment, an electron beam treatment, or an anchor coat agent from the viewpoint of the adhesion strength between the layers.

Further, the vacuum heat insulating material of the present invention may be provided with a detector for checking the degree of vacuum inside as required.

Each layer may contain various additives such as a crosslinking agent, an ultraviolet absorber, a coloring agent, an antioxidant and the like, which are commonly available in resins, as long as the effects of the present invention are not impaired. Is also good.

The vacuum heat insulating material of the present invention has excellent heat insulating performance,
Refrigerated (10 ° C or less) refrigerator or refrigerator (0 ° C or less)
It can be used for refrigeration or freezing use as a heat insulating material for walls such as a refrigerator or a freezer compartment. Further, the vacuum heat insulating material of the present invention can be used for building materials used as heat insulating materials for ceilings, walls, floors and the like.

[0051]

The vacuum heat insulating material of the present invention has excellent heat insulating properties as compared with conventional ones and maintains the heat insulating properties for a long period of time. Further, the vacuum heat insulating material of the present invention can be used for various applications that require heat insulation such as cold insulation, heat insulation (for example, refrigerators, freezers, cool cars, car ceilings, batteries, refrigerated or refrigerated boats, heated containers, refrigerated or refrigerated displays. Case,
Portable cooler, cooking warm case, vending machine, solar water heater, floor heating, underfloor, wall or inside the wall, ceiling, attic, building materials, piping of hot or cooling water, conduit for transferring low-temperature fluid In addition, it can be suitably used as a heat insulator for plant equipment, clothing, bedding, etc.).

[0052]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

The methods for measuring various physical properties are described below. [Measurement of Thermal Conductivity] The measurement was performed according to JIS A1412.

[Heat Sealing Conditions] Temperature 208 ° C., time 0.5 second, heat seal width 10 mm (heat sealer:
FUJI IMPULSE T230: FUJI IM
PULSE CO. LTD).

[Thickness Measurement] A thickness of 0.5 μm or more was measured with a digital thickness gauge. Less than 0.5 μm is determined by a gravimetric analysis method (the measured value of the weight of a film having a certain area is divided by the area and further divided by the specific gravity of the composition), or the laminate of the gas barrier resin composition layer and the substrate layer In some cases, the ratio of the resin composition layer of the present invention to the base material is determined from the elemental analysis method (the specific inorganic element analysis value of the laminate (derived from the composition layer) and the specific element fraction of the inorganic layered compound alone). According to).

[Measurement of Particle Size] Ultrafine particle size analyzer (BI-
90, manufactured by Brookhaven) at a temperature of 25 ° C. and in a water solvent. The center diameter determined by the photon correlation method based on the dynamic light scattering method was defined as the particle diameter L.

[Calculation of Aspect Ratio] X-ray diffractometer (XD
-5A (manufactured by Shimadzu Corporation), the diffraction measurement of the inorganic layered compound alone and the resin composition by the powder method was performed. Thereby, the plane spacing (unit thickness) a of the inorganic layered compound was determined, and further, from the diffraction measurement of the resin composition, it was confirmed that there were portions where the plane spacing of the inorganic layered compound was widened. Using the particle diameter L obtained by the above method, the aspect ratio Z
Was determined by the equation of Z = L / a.

[Coating liquid 1] Dispersion pot (trade name: Despa MH)
-L, manufactured by Asada Tekko Co., Ltd.) and ion-exchanged water (0.7 μS / cm)
3551 g) and 200 g of polyvinyl alcohol (PVA117H; manufactured by Kuraray Co., Ltd., degree of saponification; 99.6%, degree of polymerization: 1700), and under low-speed stirring (1500 rpm)
m, the peripheral speed is 4.10 m / min) and the temperature is raised to 95 ° C.
Stir for hours to dissolve. Next, after lowering the temperature to 60 ° C. while stirring, natural montmorillonite (Kunipia G;
100 g of Kunimine Industries Co., Ltd.) as a powder was added, and after confirming that montmorillonite had substantially precipitated in the solution, high-speed stirring was performed (3100 rpm, peripheral speed 8.47 m / min).
Was carried out for 90 minutes to obtain a resin composition mixed solution (A) having a total solid content of 8 wt%. The mixed solution (A) was cast into a film, and X-ray analysis was performed. The bottom distance from the peak was 41.2 angstroms, indicating that the cleavage was sufficiently cleaved. The particle size of the natural montmorillonite (Kunipia F) determined by dynamic light scattering was 560 nm, the a value obtained from powder X-ray diffraction was 1.2156 nm, and the aspect ratio (Z) was 461.

Further, a silicone-based surfactant SH37
A liquid to which 0.38 g of No. 46 (manufactured by Dow Corning Toray Co., Ltd.) was added was used as Coating Liquid 1.

Example 1 A biaxially oriented polypropylene having a thickness of 20 μm (Pyrene p2102; manufactured by Toyobo Co., Ltd.) treated with a surface corona was used as a substrate layer, and an anchor coat agent (E ) (Adcoat AD335 /
CAT10 = 15/1 (weight ratio): Toyo Morton Co., Ltd.
Gravure coating (test coater; Yasui Seiki Co., Ltd.)
Manufacture: microgravure coating method, coating speed 3 m / min, drying temperature 80 ° C.). The dry thickness of the anchor coat layer was 0.15 μm. The coating liquid 1 was coated on the anchor coat layer by a gravure coating method (test coater; manufactured by Yasui Seiki Co., Ltd .: microgravure coating method, coating speed 6 m / min, drying temperature 100 ° C.). The dry thickness of the coating layer was 0.5 μm.

Then, the surface layer of the LLDPE treated with a urethane-based adhesive (Eunoflex J3: Sanyo Kasei) was applied to the coating layer of the coating film obtained above.
(KF101: thickness 40 μm, manufactured by Seki-Fill Corporation) was dry-laminated on the coating layer to obtain a laminated film. [Reference Example 1] Using two laminated films obtained above, the three sides of the LLDPE layer as the inner layer were heat-sealed at 250 mm ×
A 250 mm bag was produced. Then, a 100% communicating urethane foam (average cell diameter of 75
μ, manufactured by Kurabo Industries, Ltd.) at 120 ° C. for 1 hour and COMBOGETTER (SAES Getters).
(Made by NPC), and the inside of the bag is further sealed with a vacuum sealer (NPC).
The other one of the bag-shaped materials is heat-sealed so that the internal pressure becomes 0.01 Torr to obtain a vacuum heat insulating material.
The thermal conductivity of the obtained vacuum heat insulating material is extremely low, and the heat insulating property during aging is extremely low.

Example 2 Biaxially stretched polyethylene terephthalate having a thickness of 12 μm (Lumilar Q27; Toray Industries, Inc.)
The surface corona-treated layer of the above is used as a substrate layer, and an anchor coat agent (E) (Adcoat AD3
35 / CAT10 = 15/1 (weight ratio): Toyo Morton Co., Ltd.) by gravure coating (test coater; Yasui Seiki Co., Ltd .: microgravure coating method, coating speed 3 m /
(Min., Drying temperature: 80 ° C.). The dry thickness of the anchor coat layer was 0.15 μm. Gravure coating method for coating liquid 1 (test coater; manufactured by Yasui Seiki Co., Ltd .: microgravure coating method, coating speed 6 m / min, drying temperature 100)
° C) on the anchor coat layer. The dry thickness of the coating layer was 0.5 μm.

Then, a surface corona treated LLDPE was applied to the coating layer of the coating film obtained above using a urethane-based adhesive (Eunoflex J3: manufactured by Sanyo Chemical Industries, Ltd.).
(KF101: 80 μm in thickness, manufactured by Seki-Fill Corporation) was dry-laminated on the coating layer to obtain a laminated film. [Reference Example 2] Using the two laminated films obtained above, the three sides of the LLDPE layer as the inner layer were thermally fused to 250 mm ×
A 250 mm bag was produced. Then, a 100% communicating urethane foam (average cell diameter of 75
μ, manufactured by Kurabo Industries, Ltd.) at 120 ° C. for 1 hour and COMBOGETTER (SAES Getters).
(Made by NPC), and the inside of the bag is further sealed with a vacuum sealer (NPC).
The other one of the bag-shaped materials is heat-sealed so that the internal pressure becomes 0.01 Torr to obtain a vacuum heat insulating material.
The thermal conductivity of the obtained vacuum heat insulating material is extremely low, and the heat insulating property during aging is extremely low.

[Example 3] Aluminum deposition 2 having a thickness of 12 µm
Axial stretched polyethylene terephthalate (VM-PET, E
7075; manufactured by Toyobo Co., Ltd.) as a base material layer, and an anchor coating agent (E) (Adcoat AD335 /
CAT10 = 15/1 (weight ratio): Toyo Morton Co., Ltd.
Gravure coating (test coater; Yasui Seiki Co., Ltd.)
Manufacture: microgravure coating method, coating speed 3 m / min, drying temperature 80 ° C.). The dry thickness of the anchor coat layer was 0.15 μm. The coating liquid 1 was coated on the anchor coat layer by a gravure coating method (test coater; manufactured by Yasui Seiki Co., Ltd .: microgravure coating method, coating speed 6 m / min, drying temperature 100 ° C.). The dry thickness of the coating layer was 0.5 μm.

Then, a surface corona-treated LLDPE was applied to the coating layer of the coating film obtained above using a urethane-based adhesive (Eunoflex J3: manufactured by Sanyo Chemical Industries, Ltd.).
(KF101: 80 μm in thickness, manufactured by Seki-Fill Corporation) was dry-laminated on the coating layer to obtain a laminated film. [Reference Example 3] Using the two laminated films obtained above, the three sides of the LLDPE layer as the inner layer were thermally fused to 250 mm ×
A 250 mm bag was produced. Then, a 100% communicating urethane foam (average cell diameter of 75
μ, manufactured by Kurabo Industries, Ltd.) at 120 ° C. for 1 hour and COMBOGETTER (SAES Getters).
(Made by NPC), and the inside of the bag is further sealed with a vacuum sealer (NPC).
The other one of the bag-shaped materials is heat-sealed so that the internal pressure becomes 0.01 Torr to obtain a vacuum heat insulating material.
The thermal conductivity of the obtained vacuum heat insulating material is extremely low, and the heat insulating property during aging is extremely low.

Example 4 Vapor deposition of silica having a thickness of 12 μm 2
Axial stretching polyethylene terephthalate (Tech Barrier S;
An anchor coat agent (E) (Adcoat AD335 / CAT10) was used as a base material layer on a silica-deposited surface.
= 15/1 (weight ratio): Toyo Morton Co., Ltd.) by gravure coating (test coater; Yasui Seiki Co., Ltd.): microgravure coating method, coating speed 3 m / min, drying temperature 80
° C). The dry thickness of the anchor coat layer is 0.15
μm. Gravure coating method for coating liquid 1 (test coater; manufactured by Yasui Seiki Co., Ltd .: microgravure coating method
The coating was performed on the anchor coat layer at a coating speed of 6 m / min and a drying temperature of 100 ° C.). The dry thickness of the coating layer is 0.5
μm.

Then, a surface corona-treated LLDPE was applied to the coating layer of the coating film obtained above using a urethane-based adhesive (Eunoflex J3: manufactured by Sanyo Chemical Industries, Ltd.).
(KF101: 80 μm in thickness, manufactured by Seki-Fill Corporation) was dry-laminated on the coating layer to obtain a laminated film. [Reference Example 4] Using the two laminated films obtained above, the three sides of the LLDPE layer as the inner layer were thermally fused to 250 mm ×
A 250 mm bag was produced. Then, a 100% communicating urethane foam (average cell diameter of 75
μ, manufactured by Kurabo Industries, Ltd.) at 120 ° C. for 1 hour and COMBOGETTER (SAES Getters).
(Made by NPC), and the inside of the bag is further sealed with a vacuum sealer (NPC).
The other one of the bag-shaped materials is heat-sealed so that the internal pressure becomes 0.01 Torr to obtain a vacuum heat insulating material.
The thermal conductivity of the obtained vacuum heat insulating material is extremely low, and the heat insulating property during aging is extremely low.

Example 5 Biaxially stretched polyethylene terephthalate having a thickness of 12 μm (Lumilar Q27, Toray Industries, Inc.)
Co., Ltd.) as a base layer, and an anchor coat agent (E) (Adcoat AD335 / CAT10 = 15/1) on the corona-treated surface.
(Weight ratio): Toyo Morton Co., Ltd.) was gravure coated (test coater; Yasui Seiki Co., Ltd .: microgravure coating method, coating speed 3 m / min, drying temperature 80 ° C.).
The dry thickness of the anchor coat layer was 0.15 μm. Gravure coating method of coating liquid 1 (test coater; manufactured by Yasui Seiki Co., Ltd .: microgravure coating method, coating speed 6)
m / min at a drying temperature of 100 ° C.) on the anchor coat layer. The dry thickness of the coating layer was 0.5 μm.

Then, using a urethane-based adhesive (Eunoflex J3: manufactured by Sanyo Chemical Industries), a vapor deposition CPP (Meiwa Pax Co., Ltd.) was applied to the coating layer of the coating film obtained above.
(VM-CPP, FKB: thickness 60 μm) was dry-laminated on the coating layer to obtain a laminated film. [Reference Example 5] Using two laminated films obtained above, the three sides of the CPP layer as the inner layer were thermally fused to 250 mm × 25.
A 0 mm bag was produced. Then, a 100% communicating urethane foam (average cell diameter 75 μ,
Heat-treated at 120 ° C. for 1 hour and COMBOGETTER (manufactured by SAES Getters Co., Ltd.)
And the other side of the bag is heat-sealed with a vacuum sealer (manufactured by NPC) so that the internal pressure becomes 0.01 Torr to obtain a vacuum heat insulating material. The thermal conductivity of the obtained vacuum heat insulating material is extremely low, and the heat insulating property during aging is extremely low.

Example 6 Vapor deposition of silica having a thickness of 12 μm 2
Axial stretching polyethylene terephthalate (Tech Barrier S;
An anchor coat agent (E) (Adcoat AD335 / CAT10) was used as a base material layer on a silica-deposited surface.
= 15/1 (weight ratio): Toyo Morton Co., Ltd.) by gravure coating (test coater; Yasui Seiki Co., Ltd.): microgravure coating method, coating speed 3 m / min, drying temperature 80
° C). The dry thickness of the anchor coat layer is 0.15
μm. Gravure coating method for coating liquid 1 (test coater; manufactured by Yasui Seiki Co., Ltd .: microgravure coating method
The coating was performed on the anchor coat layer at a coating speed of 6 m / min and a drying temperature of 100 ° C.). The dry thickness of the coating layer is 0.5
μm.

Then, using a urethane-based adhesive (Eunoflex J3: manufactured by Sanyo Chemical Co., Ltd.), a vapor deposition CPP (Meiwa Pax Co., Ltd.) was applied to the coating layer of the coating film obtained above.
(VM-CP, FKB: thickness 60 μm) was dry-laminated between the coated surface and the deposited surface to obtain a laminated film. [Reference Example 6] Using two laminated films obtained above, three sides of a CPP layer as an inner layer were thermally fused to 250 mm × 25.
A 0 mm bag was produced. Then, a 100% communicating urethane foam (average cell diameter 75 μ,
Heat-treated at 120 ° C. for 1 hour and COMBOGETTER (manufactured by SAES Getters Co., Ltd.)
And the other side of the bag is heat-sealed with a vacuum sealer (manufactured by NPC) so that the internal pressure becomes 0.01 Torr to obtain a vacuum heat insulating material. The thermal conductivity of the obtained vacuum heat insulating material is extremely low, and the heat insulating property during aging is extremely low.

Example 7 Vapor deposition of silica having a thickness of 12 μm 2
Axial stretching polyethylene terephthalate (Tech Barrier S;
An anchor coat agent (E) (Adcoat AD335 / CAT10) was used as a base material layer on a silica-deposited surface.
= 15/1 (weight ratio): Toyo Morton Co., Ltd.) by gravure coating (test coater; Yasui Seiki Co., Ltd.): microgravure coating method, coating speed 3 m / min, drying temperature 80
° C). The dry thickness of the anchor coat layer is 0.15
μm. Gravure coating method for coating liquid 1 (test coater; manufactured by Yasui Seiki Co., Ltd .: microgravure coating method
The coating was performed on the anchor coat layer at a coating speed of 6 m / min and a drying temperature of 100 ° C.). The dry thickness of the coating layer is 0.5
μm.

Then, an aluminum foil (8 μm thick, manufactured by Showa Aluminum Co., Ltd.) was applied to the coating layer of the coating film obtained above using a urethane-based adhesive (Eunoflex J3: manufactured by Sanyo Chemical Industries, Ltd.). Dry-laminated so as not to cover the heat-sealed portion, and further, a surface corona-treated LLDPE (manufactured by Seki-Fill Corporation: KF101: thickness 8)
0 μm) was dry-laminated on the coating layer to obtain a laminated film. [Reference Example 7] Using two laminated films obtained above, the three sides of the LLDPE layer as the inner layer were thermally fused to 250 mm ×
A 250 mm bag was produced. Then, a 100% communicating urethane foam (average cell diameter of 75
μ, manufactured by Kurabo Industries, Ltd.) at 120 ° C. for 1 hour and COMBOGETTER (SAES Getters).
(Made by NPC), and the inside of the bag is further sealed with a vacuum sealer (NPC).
The other one of the bag-shaped materials is heat-sealed so that the internal pressure becomes 0.01 Torr to obtain a vacuum heat insulating material.
The thermal conductivity of the obtained vacuum heat insulating material is extremely low, and the heat insulating property during aging is extremely low.

Comparative Example 1 A gas barrier layer was formed of a polyvinylidene chloride film (Saran UB, manufactured by Asahi Kasei Corporation).
5 μ), and a biaxially stretched OPP (20
μ) using a urethane-based adhesive (Eunoflex J3: manufactured by Sanyo Kasei Co., Ltd.), and then, on the opposite surface, a surface corona-treated LLDPE (manufactured by Seki-Fill Corporation: KF101: (Thickness: 40 μm) was dry-laminated as an inner layer to obtain a laminated film. [Comparative Reference Example 2] Further, a vacuum heat insulating material can be obtained under the same conditions as in Example 1, but the heat insulating property is significantly reduced by aging.

[Brief description of the drawings]

FIG. 1 shows the X-ray diffraction peaks of an inorganic layered compound,
It is a graph which shows the relationship with the "unit thickness a" of this compound typically.

FIG. 2 is a graph showing X of a resin composition containing an inorganic layered compound;
4 is a graph schematically showing a relationship between a line diffraction peak and “plane spacing d” of the composition.

FIG. 3 is an X-ray diffraction peak of a resin composition when a peak corresponding to “plane spacing d” overlaps a halo (or background) and is difficult to detect;
It is a graph which shows typically the relationship with the "plane spacing d" of this composition. In this figure, the area of the portion excluding the base line on the lower angle side than 2θd is set as the peak corresponding to “surface interval d”.

Claims (12)

[Claims] 1. A vacuum heat insulating material obtained by evacuating a core material-containing hollow portion covered with a resin laminate having at least one gas barrier resin composition layer comprising a resin and an inorganic layered compound, Vacuum insulation material whose hollow part further contains a getter agent. 2. The vacuum heat insulating material according to claim 1, wherein the getter agent has been dehydrated in advance. 3. The vacuum heat insulating material according to claim 1, wherein the getter agent is iron powder. 4. The vacuum heat insulating material according to claim 1, wherein the getter agent is a resin molding containing iron powder. 5. The vacuum heat insulating material according to claim 1, wherein the getter agent is a synthetic zeolite. 6. The vacuum heat insulating material according to claim 5, wherein the pore size of the synthetic zeolite is 8 ° to 13 °. 7. The vacuum heat insulating material according to claim 1, wherein the getter agent is an alloy-based getter agent. 8. The gas barrier resin composition layer having a temperature of 23.degree.
The vacuum heat insulating material according to any one of claims 1 to 7, wherein the oxygen permeability at% RH is 0.1 cc / m ² · day · atm or less. 9. An inorganic layered compound having an aspect ratio of 50 to 50.
The vacuum heat insulating material according to any one of claims 1 to 8, which is 00. 10. An inorganic layered compound having an aspect ratio of 200.
The vacuum heat insulating material according to any one of claims 1 to 8, wherein 11. The vacuum heat insulating material according to claim 1, which is used for refrigeration or freezing. 12. The vacuum heat insulating material according to claim 1, which is used for building materials.