JP2007313652A - Barrier facing material for vacuum heat insulating material and vacuum heat insulating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier facing material for a vacuum heat insulating material causing no desorption of water vapor with the elapse of time even if a heat insulating core material absorbs moisture, excellent in pinhole resistance and high barrier properties and developing an excellent heat insulating effect having long-term reliability, and the vacuum heat insulating material using the facing material. <P>SOLUTION: The barrier facing material 10 for the vacuum heat insulating material filled with the heat insulating core material so as to house the same is constituted by successively laminating at least a resin layer which contains a moisture absorbent and a sealant layer on the vapor deposition thin film layer or coating layer of an oxygen barrier film obtained by forming at least an aluminum foil 4, the vapor deposition thin film layer or the coating layer on one side of a plastic base material having a thrust-resistant strength or a laminated plastic film base material. The vacuum heat insulating material is obtained using this facing material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention is suitable for a barrier external packaging material for a vacuum heat insulating material filled and stored with needle-like short fiber powder having a small bulk density formed by cutting inorganic fibers such as glass wool, or a molded heat insulating core material such as calcium silicate. Used for. And the heat insulation core material absorbs moisture over time, and has excellent pinhole resistance, high barrier performance, long-term reliability and excellent heat insulation barrier properties. The present invention relates to an exterior material and a vacuum heat insulating material using the exterior material.

Conventionally, various heat insulating materials are used in vending machines, electric refrigerators, low temperature containers, and the like. In particular, as an insulation material with excellent heat insulation performance, the inside of the exterior body that forms an airtight chamber is filled with a heat insulating core material such as glass fiber, rock wool, polyurethane foam, and polystyrene foam, and the airtight chamber is evacuated. Constructed vacuum insulation is used.

  In order to keep the inside in a vacuum state for a long time and to prevent gas from entering from the outside, this exterior body uses a material having excellent gas barrier properties.

  As a material having excellent gas barrier properties, an aluminum foil or an aluminum vapor deposition film has been generally employed. The material satisfies the gas barrier properties when used as a barrier material, but further imparts puncture strength, and therefore a polyamide film such as a nylon film having excellent mechanical strength such as puncture and heat resistance on the outside of the barrier material. By using a polyester film, the occurrence of pinholes in the barrier material was prevented.

  Also, when filling the heat-tight chamber of needle-like short fiber powder with a small bulk density formed by cutting inorganic fibers such as glass wool and evacuating the hermetic chamber, the needle-like short fiber powder breaks through the sealant layer, and the aluminum foil There was a problem that pinholes were generated in the film, the degree of vacuum was lowered, and the heat insulation was impaired.

  Further, when a heat insulating core material such as calcium silicate is filled and the hermetic chamber is evacuated, the corners and corner portions of the heat insulating core material break through the sealant layer, thereby causing a pinhole in the aluminum foil. And there existed a problem that a vacuum degree fell and heat insulation property was impaired.

  Further, there is a problem that the heat-insulating core material filled absorbs moisture and water vapor is desorbed over time, or the degree of vacuum is lowered due to gas intrusion from the outside and the heat insulating property is impaired.

  In order to solve the above-described problem of a decrease in the degree of vacuum, a vacuum heat insulating pack having stable performance (for example, see Patent Document 1) is known.

  As shown in FIGS. 9 and 10, the vacuum heat insulating pack 100 includes a molding material 105 made of a plastic laminate film 104 having a recess 103 for providing an adsorbent 102, a barrier material made of a plastic-metal foil laminate film, and open cells. The lid member 110 is composed of a core material 108 having a structure and a plastic laminate film 109.

However, there is a problem that the adsorbent 102 also absorbs moisture with the passage of time and the adsorption capacity is lowered, and the degree of vacuum is lowered and the heat insulation performance is impaired.

  In addition, there is a problem that it takes time and effort to store the adsorbent 102 in a container or bag, and the work process becomes complicated. And there is a problem that the packaging cost increases.

  Therefore, as a barrier exterior material for vacuum heat insulating materials, it is filled and stored with needle-shaped short fiber powder with a small bulk density formed by cutting inorganic fibers such as glass wool, or a heat insulating core material of a molded body such as calcium silicate. Even in the case of a vacuum insulation material, the filled and stored insulation core material absorbs moisture and does not desorb water vapor over time, and has puncture resistance, pinhole resistance and high barrier properties. There has been a demand for a barrier external packaging material for vacuum heat insulating material and a vacuum heat insulating material that have excellent and long-term reliability that can exhibit an excellent heat insulating effect.

Prior art documents are shown below.
JP-A-5-209700

  The present invention has been made to solve the above-described problems, and the heat-insulating core material filled and stored absorbs moisture and does not desorb water vapor over time, and has a puncture-resistant strength and is pin-resistant. An object of the present invention is to provide a barrier external packaging material for a vacuum heat insulating material and a vacuum heat insulating material which are excellent in hall properties and high barrier properties and have long-term reliability capable of exhibiting an excellent heat insulating effect.

In order to achieve the above object, that is, the invention according to claim 1,
A barrier external packaging material for vacuum heat insulating material filled and stored with needle-like short fiber powder with a small bulk density formed by cutting inorganic fibers such as glass wool, or a heat insulating core material of calcium silicate,
Moisture on the vapor-deposited thin film layer or coating coating layer of the oxygen barrier film in which at least one aluminum foil, vapor-deposited thin film layer or coating coating layer is formed on one side of the plastic film substrate or laminated plastic film substrate having puncture resistance A barrier external packaging material for a vacuum heat insulating material, wherein a resin layer containing an adsorbent and a sealant layer are sequentially laminated.

The invention according to claim 2
The plastic film substrate is a film substrate of either a polyester film alone, a laminated film of the polyester films, or a laminated film formed by laminating a stretched nylon film on the polyester film alone. The barrier exterior material for a vacuum heat insulating material according to claim 1.

The invention according to claim 3
3. The barrier external packaging material for a vacuum heat insulating material according to claim 1, wherein the deposited thin film layer is a deposited thin film layer made of a metal oxide.

The invention according to claim 4
The barrier coating material for a vacuum heat insulating material according to claim 1 or 2, wherein the coating coating layer is a coating coating layer composed of an inorganic stratiform compound and a water-soluble polymer.

The invention according to claim 5
The barrier metal exterior material for a vacuum heat insulating material according to claim 3, wherein the metal oxide is one of aluminum oxide, silicon oxide, and magnesium oxide, or a composite thereof.

The invention according to claim 6
It is a vacuum heat insulating material characterized by using the barrier outer packaging material for a vacuum heat insulating material according to any one of claims 1 to 5 in a bag shape.

The invention according to claim 7 provides:
It is a vacuum heat insulating material characterized by using the barrier outer packaging material for a vacuum heat insulating material according to any one of claims 1 to 5 in a container shape.

The barrier exterior material for vacuum heat insulating material of the present invention is
Due to the above structure, the heat insulating core material absorbs moisture, does not desorb water vapor over time, and has a long-term reliability capable of exhibiting an excellent heat insulating effect, and a barrier external packaging material for vacuum heat insulating material and the exterior material thereof The vacuum heat insulating material using can be provided.

  Further, it is possible to provide a barrier external packaging material for a vacuum heat insulating material having a puncture resistance, excellent pinhole resistance, and high barrier properties, and a vacuum heat insulating material using the external packaging material.

  In addition, since the barrier external packaging material for vacuum heat insulating material of the present invention has the above-described configuration, when the heat insulating core material is stored and filled, the packaged hygroscopic material or adsorbent is stored or filled. There is no need for troublesome work, and there is no need for trouble and the work process is not complicated.

  And there is no cost increase. Furthermore, even if it is used for a long time, the degree of vacuum is not lowered and the heat insulation performance is not impaired.

  The vacuum heat insulating material using the barrier outer packaging material for the vacuum heat insulating material of the present invention can be widely applied as a normal heat insulating and cold insulating heat insulating material such as a vending machine, an electric refrigerator, a low temperature container, a prefab panel, and the like. .

  Preferred embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing a cross section of one embodiment of a barrier exterior material for a vacuum heat insulating material according to the present invention. FIG. 2 is a schematic cross-sectional view showing a cross section of another embodiment of the barrier exterior material for a vacuum heat insulating material of the present invention.

  As shown in FIG. 1, a barrier exterior material 10 for a vacuum heat insulating material as an embodiment of the present invention comprises a first plastic film substrate 1 and a second plastic film substrate 2 having puncture resistance. An aluminum foil 4 is formed on one side of the laminated film base 3.

  And it is a laminated material which consists of the structure by which the film base material 7 formed by laminating | stacking the resin layer 5 containing a water absorbent and the sealant resin layer 6 was laminated | stacked one by one.

  The sealant resin layer 6 used in the present invention is laminated as an adhesive layer in order to form a package.

The sealant resin layer 6 is an adhesive thermoplastic resin that can be heat-sealed, and may be any material that can be melted by heat and fused to each other. For example, low-density polyethylene, medium-density polyethylene, high-density Polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer Polyolefin resins such as copolymers, ethylene-propylene copolymers, methylpentene polymers, polyethylene or polypropylene, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Use acid-modified polyolefin resin modified with acid, etc. It can be.

And as the sealant resin layer 6 used for the structure of the said laminated material of this invention, a linear low density polyethylene resin (LLDPE) with a density of 0.930 g / cm < ³ > or more is desirable. And although thickness is suitably determined according to the objective, generally it exists in the range of 15-50 micrometers.

  Further, as shown in FIG. 2 as well, FIG. 1 shows that the barrier exterior material 20 for vacuum heat insulating material is formed by laminating a first plastic film substrate 1 and a second plastic film substrate 2 having puncture resistance. An aluminum foil 4 is formed on one side of the film substrate 3.

  And it is a laminated material of the structure formed by laminating | stacking the film base material 7 formed by laminating | stacking the resin layer 5 containing a moisture absorber, and the sealant resin layer 6 sequentially.

  Further, the sealant resin layer 6 used in the present invention is laminated as an adhesive layer in order to form a package as described above with reference to FIG.

  The sealant resin layer 6 is an adhesive thermoplastic resin that can be heat-sealed and can be melted by heat and fused to each other. For example, low-density polyethylene, medium-density polyethylene, high-density Polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer Polyolefin resins such as copolymers, ethylene-propylene copolymers, methylpentene polymers, polyethylene or polypropylene, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Use acid-modified polyolefin resin modified with acid, etc. Can.

Moreover, as the sealant resin layer 6 used for the structure of the laminated material of the present invention shown in FIG. 2, a high density polyethylene resin (HDPE) having a density of 0.940 g / cm ³ or more is desirable. And although thickness is suitably determined according to the objective, generally it exists in the range of 15-50 micrometers.

  Next, FIG. 3 is a schematic cross-sectional view showing a cross section of still another embodiment of the barrier external packaging material for vacuum heat insulating material of the present invention. FIG. 4 is a schematic cross-sectional view showing a cross-section of still another embodiment of the barrier exterior material for vacuum heat insulating material of the present invention.

  As shown in FIG. 3, the barrier exterior material 30 for vacuum heat insulating material as still another embodiment of the present invention includes a first plastic film substrate 1 and a second plastic film substrate having puncture resistance. An aluminum foil 4 is formed on one side of a film base 3 formed by laminating 2.

Then, a resin layer 5 containing a moisture absorbent and a sealant resin layer are formed on the deposited thin film layer 9 or the coating coating layer 9 of the oxygen barrier film 10 having the deposited thin film layer 9 or the coating coating layer 9 formed on the film base 8. 6 is a laminated material having a structure in which a film base 7 formed by laminating 6 is sequentially laminated.

  The sealant resin layer 6 shown in FIG. 3 used in the present invention is laminated as an adhesive layer in order to form a package as described above with reference to FIGS.

And as the sealant resin layer 6 used for the structure of the said laminated material shown in FIG. 3 of this invention, a linear low density polyethylene resin (LLDPE) with a density of 0.930 g / cm < ³ > or more is desirable. And although thickness is suitably determined according to the objective, generally it exists in the range of 15-50 micrometers.

Furthermore, as the sealant resin layer 6 used in the configuration of the above-described laminated material shown in FIG. 4 of the present invention, a high density polyethylene resin (HDPE) having a density of 0.940 g / cm ³ or more is desirable. And although thickness is suitably determined according to the objective, generally it exists in the range of 15-50 micrometers.

  As the first plastic film substrate 1 used in the present invention, a stretched polyester film is preferably used.

  The resin material for the polyester resin film includes a polyethylene terephthalate (PET) resin of a homopolyester resin, a polyester resin having a polyethylene terephthalate structure based on the following copolymer polyester resin, for example, terephthalic acid and ethylene glycol, and two bases. Isophthalic acid, phthalic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, etc. as the acid are glycols such as diethylene glycol, polyethylene glycol, polypropylene glycol, polypropylene glycol, polybutylene glycol, and bisphenol derivatives. Copolymerized ethylene oxide adducts such as polyethylene naphthalate (PEN) resin and polybutylene terephthalate (PBT) resin Etc. can be mentioned.

  In addition, as the first plastic film substrate 1, the stretched nylon film listed below can be used.

  As the second plastic film substrate 2 used in the present invention, a stretched nylon film is preferably used.

  Specific examples of the resin material for the nylon resin film include polycaproamide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-9-aminononanoic acid (nylon 9), and polyundecanamide. (Nylon 11), polylaurin lactam (nylon 12), polyethylenediamine adipamide (nylon 2, 6), polytetramethylene adipamide (nylon 4, 6), polyhexamethylene didipamide (nylon 6, 6) , Polyhexamethylene sebamide (nylon 6,10), polyhexamethylene dodecamide (nylon 6,12), polyoctamethylene adipamide (nylon 8,6), polydecamethylene adipamide (nylon 10,6 ), Polydecamethylene sebacamide (nylon 10, 10), polydodecamethylene Dekamido (nylon 12,12), meta-xylene diamine -6 nylon (MXD6) and the like.

Examples of nylon copolymer resins include caprolactam / laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate / hexa. Examples include methylene diammonium sebacate copolymer, ethylene diammonium adipate / hexamethylene diammonium adipate copolymer, caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer, and the like.

  As a 1st plastic film base material used by this invention shown in FIGS. 1-4, the polyester-type resin film single-piece | unit is used. A stretched nylon film alone is used as the second plastic film substrate 2.

  And as the film base 3 formed by laminating the first plastic film base 1 and the second plastic film base 2, a laminated film obtained by laminating a stretched nylon film alone on a polyester film alone or Any film substrate 3 of a laminated film of stretched nylon films is used.

  For the above film base material, for example, ultraviolet absorbers, antistatic agents, flame retardants, fireproofing agents, fungicides, pigments, fillers, and the like can be used as general additives. The addition amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose.

  The ultraviolet absorber is used to absorb ultraviolet (light of 400 nm or less) energy, consume it for the internal change of the absorbent molecule, and not give energy to the polymer.

  In addition, since the film base is generally very excellent in electrical insulation, charging easily occurs when it is rubbed or overlapped. As a result, an antistatic agent is used because dust adheres to the aesthetic appearance, and an electric shock is given to the worker at the manufacturing site, sometimes causing a fire.

And there are a kneading type and a coating type as the usage method, but the kneading type is more preferable because of its long-lasting preventive effect.
In addition, as the antistatic agent to be used, any known nonionic or cationic one can be used.

Colored pellets (colored pellets), master batches, dry colors, etc. are used when coloring the film substrate. The master batch has a pigment dispersed in a high concentration in the same kind of material as the resin to be colored. Therefore, it is preferably used because it is easy to measure and easy to handle.

  In addition, the dry color is a powdery product whose surface is treated to improve dispersibility. And when a film base material is polyethylene (PE), polystyrene (PS), polyamide (PA) acrylic resin, etc., it is used.

  Next, the thickness of the aluminum foil 4 used in the present invention needs to be 6 to 20 μm in order to ensure workability and prevent oxygen from entering.

  When the thickness is less than 6 μm, the aluminum foil is likely to break during vacuum insulation processing (vacuum insulation bag making, container processing), and pin holes are likely to occur even when it is not broken. The risk of getting higher.

On the other hand, when the thickness exceeds 20 μm, neither the effect of improving the breakage during processing nor the effect of preventing the generation of pinholes is particularly improved, so it is desirable to avoid the increase in the total thickness of the laminate and the increase in weight. .

  As the material of the aluminum foil, an aluminum-iron alloy (soft material) is used. It is desirable that the iron content is 0.3 to 9.0%, preferably 0.7 to 2.0%.

  When the iron content is less than 0.3%, the effect of preventing the occurrence of pinholes is not recognized, and when the iron content of the aluminum exceeds 9.0%, flexibility as aluminum is not achieved. It is obstructed and the processability of the laminate is deteriorated.

  In addition, aluminum produced by cold rolling changes its flexibility, waist strength and hardness under annealing (so-called annealing treatment) conditions, but aluminum is slightly more than the so-called hard-treated product that is not annealed. Alternatively, flexible aluminum that has been completely annealed is preferred.

The degree of flexibility, waist strength and hardness of the aluminum, that is, the conditions for annealing, may be appropriately selected according to the processing suitability (vacuum insulation bag making, container processing).
For example, in order to prevent wrinkles and pinholes, it is desirable to use flexible aluminum annealed according to the degree of processing.

  Next, the oxygen barrier film 10 formed on the film base 8 by the deposited thin film layer 9 or the coating coating layer 9 used in the present invention will be described.

  First, as the fill substrate 8 for forming the vapor deposition thin film layer 9 or the coating covering layer 9, in the case of the substrate for forming the vapor deposition thin film layer, polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, Polyethylene naphthalate, etc.), polyamide (nylon 6, nylon 66, etc.), or a copolymer of these polymers is used.

  Moreover, in the case of the base material which forms the coating coating layer 9, a stretched polypropylene is used preferably. Examples of polypropylene include polypropylene homopolymers based on propylene homopolymers, and polypropylene resin films based on propylene-α-olefin copolymers obtained by random or block copolymerization of α-olefins mainly composed of propylene. Or a sheet can be used. In the above, as the α-olefin, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 5-ethylidene-2-norbonene, 5-methyl-2-norbonene An olefin monomer such as 1.4-hexadiene can be used.

Furthermore, in this invention, what was graft-modified with carboxylic acids, such as maleic anhydride, can be used as an alpha olefin, for example. The biaxially oriented polypropylene film preferably has a film thickness of 20 to 40 μm and a density of 0.89 to 0.91 g / cm ³ .

  Corona treatment, low-temperature plasma treatment, plasma treatment using reactive ion etching (RIE), ion bombardment treatment, on the film surface of the film base 8 on the side on which the deposited thin film layer 9 or the coating coating layer 9 is formed, Any treatment such as chemical treatment or solvent treatment may be performed.

Examples of the metal oxide constituting the vapor deposition thin film layer 9 in the present invention include metal oxides composed of oxides such as silicon, aluminum, titanium, zirconium, and tin, or composites thereof. Silicon oxide, magnesium oxide alone, or a composite thereof is preferably used.

  The optimum thickness of the vapor-deposited thin film layer 9 varies depending on the type and configuration of the metal oxide to be used, but is generally preferably in the range of 5 to 300 nm, and the value is appropriately selected. However, if the film thickness is less than 5 nm, a uniform film may not be obtained or the film thickness may not be sufficient, and the function as a gas barrier material may not be sufficiently achieved.

  Further, when the film thickness exceeds 300 nm, the thin film cannot be kept flexible, and there is a problem because the thin film may be cracked due to external factors such as bending and pulling after the film formation. More preferably, it exists in the range of 10-150 nm.

  There are various methods for forming the vapor-deposited thin film layer 9 made of a metal oxide on the plastic substrate 8, and it can be formed by a normal vacuum vapor deposition method.

  In addition, other thin film forming methods such as sputtering, ion plating, and plasma vapor deposition (CVD) can also be used. However, considering productivity, the vacuum deposition method is the best at present.

  As the heating means of the vacuum deposition method, it is preferable to use any one of an electron beam heating method, a resistance heating method, and an induction heating method, but the electron beam heating method is used in consideration of the wide selection of evaporation materials. It is more preferable.

  Further, in order to improve the adhesion between the deposited thin film layer 9 and the base material and the denseness of the deposited thin film layer 9, it is possible to perform deposition using a plasma assist method or an ion beam assist method. Moreover, in order to raise the transparency of a vapor deposition film, you may use the reactive vapor deposition which blows in various gases, such as oxygen, in the case of vapor deposition.

In addition to the vapor-deposited thin film made of the metal oxide, an oxygen barrier film on which a metal thin film is formed can be used without departing from the spirit of the present invention.
Further, the metal vapor deposition material is not particularly limited, such as aluminum, cobalt, nickel, lead, copper, silver, or a mixture thereof.

Next, the coating coating layer 9 in the present invention basically comprises an inorganic layered compound and a resin, and the kind, particle size, aspect ratio, etc. of the inorganic layered compound are appropriately selected and are not particularly limited. Montmorillonite is preferred.
The montmorillonite easily incorporates a resin between the layers of the inorganic layered compound to easily form a composite, and is excellent in stability in a molten state and coatability.

  The resin used is not particularly limited as long as the resin is easily incorporated into the inorganic layered compound to form a composite, but a water-soluble polymer is preferably used.

  Examples of the water-soluble polymer include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate. Particularly when polyvinyl alcohol is used, the gas barrier property is most excellent, which is preferable.

Polyvinyl alcohol as used herein is generally obtained by saponifying polyvinyl acetate.
As the polyvinyl alcohol, for example, a complete PVA in which only a few percent of acetic acid groups remain can be used from so-called partially saponified PVA in which several tens of percent of acetic acid groups remain. Well, not particularly limited.

  Next, the resin used for the resin layer 5 containing a moisture absorbent is an adhesive thermoplastic resin that can be heat-sealed, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) ) Low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer Acid-modified polyolefins obtained by modifying polyolefin resins such as methylpentene polymer, polyethylene or polypropylene with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Resins such as resins can be used.

And preferably, resin based on low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), ethylene methacrylic acid copolymer (EMAA), ionomer (IO), etc. is mentioned.
Further, the water absorbent used in the resin layer 5 containing the water absorbent includes sulfate compounds such as zeolite, calcium oxide, calcium chloride, magnesium sulfate, alumina, activated carbon, viscosity minerals, silica gel inorganic compounds, poly Poly α-, β-unsaturated carboxylic acid such as acrylic acid, sodium polyacrylate or ionic cross-linked product thereof, ethylene-vinyl acetate copolymer or polyvinyl acetate partially or completely saponified product, cellulose such as carboxymethyl cellulose, hydroxyethyl cellulose It is preferable to select at least one from water-soluble organic substances such as polyalkylene oxide derivatives such as polyethylene derivatives and polyethylene oxide or polypropylene oxide, polyesters and polyamides, and use a plurality of moisture absorbents in combination. Is also possible.

  In particular, the combined use of an inorganic water absorbent and an organic water absorbent is particularly preferred because the water absorption capacity is increased.

  Further, the amount added to the resin is not particularly limited, but if it exceeds 50% by weight, flexibility or strength necessary for the outer bag for a vacuum heat insulating material may be impaired, which is preferable. Absent.

  The method of laminating each of the above laminated materials constituting the barrier exterior material for vacuum heat insulating material of the present invention is a dry lamination method in which an adhesive such as a two-component curable urethane resin is used, or a solventless adhesive. Using the non-solvent lamination method for laminating and laminating by a known method such as laminating by a non-solvent lamination method, extruding and laminating a resin to form a curtain, the barrier outer packaging material for vacuum heat insulating material of the present invention is used. Obtainable.

  In particular, in the bonding of the sealant layer in the barrier exterior material for a vacuum heat insulating material of the present invention, it is preferable to apply a dry lamination method in which bonding is performed using an adhesive for dry lamination.

  As the adhesive for dry lamination, it is possible to use a two-component curing type vinyl type, (meth) acrylic type, polyamide type, polyester type, polyether type, polyurethane type, epoxy type adhesive or the like. However, a two-component curable urethane adhesive is preferably used.

Examples of the adhesive coating method include a direct gravure roll coat method, a gravure roll coat method, a kiss coat method, a reverse roll coat method, a Fonten method, and a transfer method. -It can apply | coat by methods, such as a roll coat method and others.
The coating amount is preferably about 0.1 to 10 g / m ² (dry state), more preferably about 1 to 5 g / m ² (dry state).

  Although not shown in the drawing, a printing layer can also be provided on the outermost layer in the barrier exterior material for a vacuum heat insulating material of the present invention. This printed layer is formed for practical use as a packaging material, a packaging bag, or the like.

As the printing layer, for example, an ordinary gravure ink composition, an offset ink composition, a relief printing ink composition, a screen ink composition, and other ink compositions are used on the first substrate. For example, a printing method such as a gravure printing method, an offset printing method, a relief printing method, a silk screen printing method, or the like is used.
For example, it can be configured by forming a desired printed picture made up of characters, figures, pictures, symbols, etc.

  In the above, various ink compositions include, for example, as a vehicle constituting the ink composition, for example, polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, poly (meth) acrylic resins, polyvinyl chloride Resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, Polyvinyl butyral resin, polybutadiene resin, polyester resin, polyamide resin, alkyd resin, epoxy resin, unsaturated polyester resin, thermosetting poly (meth) acrylic resin, melamine resin, urea Resin, polyurethane resin, phenol resin, xylene resin, Inic acid resin, nitrocellulose, ethyl cellulose, acetylbutyl cellulose, cellulose resin such as ethyloxyethyl cellulose, rubber resin such as chlorinated rubber and cyclized rubber, petroleum resin, rosin, casein A natural resin such as linseed oil, fats and oils such as linseed oil and soybean oil, and a mixture of one or more resins such as others can be used.

  Then, one or two or more of the above-mentioned vehicles are used as a main component, and one or more of coloring agents such as dyes and pigments are added to this, and if necessary, for example, a filler, Add stabilizers, plasticizers, antioxidants, UV stabilizers and other light stabilizers, dispersants, thickeners, desiccants, lubricants, antistatic agents, crosslinking agents, etc. Ink compositions having various forms obtained by sufficiently kneading with a diluent or the like can be used.

Next, a vacuum heat insulating material using the barrier external packaging material for a vacuum heat insulating material of the present invention as an outer cover material will be described with reference to the drawings.
FIG. 5 is a perspective view showing an external appearance of an embodiment of a vacuum heat insulating material in which a heat insulating core material is filled and stored in a bag using a barrier external packaging material for a vacuum heat insulating material as an outer covering material. FIG. 6 is a cross-sectional view taken along the line AA ′ of FIG.

  In the present invention, the shape, the structure, the form, and the like of the outer cover material of the vacuum heat insulating material 50 are appropriately selected depending on the purpose, location, and the like for which the vacuum heat insulating material 50 is used.

  For example, a rectangular film is folded in the length direction at the center, and a side-sealed bag in which both sides are heat sealed, or a rectangular film is folded in the length direction at the center and orthogonal A two-side sealed bag in which two sides are heat-sealed, and a three-side sealed bag in which two sides of the film are overlapped and the concave three sides are sealed.

In addition, a center-gap seal-type bag with a T-shaped cross-section of the bag seal section, with a pleat on both sides of the bag, and a bottom fold-type bag with a single seal (solid seal), the bottom of the bag Heat insulation core material is stored in a flat bottom bag or a square bottom bag (with folds) that forms a surface instead of a line.
Filled. Then, the inside of the bag is evacuated and the storage opening is sealed by heat sealing or the like, whereby the vacuum heat insulating material 50 is formed.

  Also, there is no particular limitation, such as a self-standing packaging bag having a rectangular flat bottom surface at the bottom, or a self-standing packaging bag (standing pouch) having a gusset portion inside the bottom of the front and back sides of the bag. And the heat insulating material core 12 can be accommodated and filled in said appropriate bag 13. FIG.

  After the heat insulating material core 12 is stored and filled in the bag 13, the inside of the bag is evacuated and the storage port is sealed by heat sealing to form the vacuum heat insulating material 50.

  For heat fusion of the storage port, a heat seal such as a heat seal bar or a rotary seal, an impulse seal, a high frequency seal, an ultrasonic seal, a hot jet seal or the like can be used.

  Further, the bag 13 using the barrier external packaging material for vacuum heat insulating material of the present invention absorbs moisture so that the heat insulating core material 12 filled and stored in the bag 13 absorbs moisture and does not desorb water vapor over time. The vacuum degree of the vacuum heat insulating material 60 does not decrease for a long period of time without introducing a packaging body such as an agent. And heat insulation performance does not fall.

Next, a vacuum heat insulating material composed of a container and a cover material using the barrier external packaging material for a vacuum heat insulating material of the present invention as a covering material will be described with reference to the drawings.
FIG. 7 is an explanatory diagram for explaining a state in which the vacuum heat insulating material 60 is manufactured using the barrier external packaging materials 10 to 40 for the vacuum heat insulating material as the covering material of the container and the lid material. Moreover, FIG. 8 is sectional drawing which shows the cross section of the vacuum heat insulating material 60 which used the barriering exterior materials 10-40 for vacuum heat insulating materials of this invention as a covering material of a container and a lid | cover material.

As shown in FIG. 7, the heat insulating core material 12 is filled and stored in a container 14 in which a recess having substantially the same shape as the outer shape of the heat insulating material core material 12 is formed using the barrier external packaging material for vacuum heat insulating material of the present invention. The
And the barriering exterior material for vacuum heat insulating materials of this invention is mounted in the flange part 16 of the container 14 as the cover material 15, and is partially heat-bonded.

  Furthermore, the air in the container 14 is evacuated from the outer peripheral edge of the flange portion 16 that is partially thermally bonded. And the vacuum heat insulating material 60 of this invention is obtained because the location thermally bonded partially seals and seals completely.

  Further, the container 14 using the barrier external packaging material for vacuum heat insulating material of the present invention absorbs moisture so that the heat insulating core material 12 filled and stored in the container 14 absorbs moisture and does not desorb water vapor over time. The vacuum degree of the vacuum heat insulating material 60 does not decrease for a long period of time without introducing a packaging body such as an agent. And heat insulation performance does not fall.

  Moreover, the container 14 in which the concave portion is formed by using the barrier external packaging material for a vacuum heat insulating material of the present invention is manufactured by a known vacuum forming method, a pressure forming method, or the like.

  Next, although it does not specifically limit as the heat insulation core material 12, For example, a calcium silicate or the acicular short fiber powder with a small bulk density, etc. are used.

  The calcium silicate is usually obtained by hydrothermal synthesis reaction of a calcareous raw material and a siliceous raw material.

  Examples of the calcareous raw material include quick lime and slaked lime. And a calcareous raw material is normally used by adjusting to lime milk containing bulky lime particles.

  Further, the siliceous raw material may be non-crystalline or crystalline, and specific examples include natural products such as diatomaceous earth, meteorite and quartz, and industrial by-products such as silicon dust.

As a method for producing calcium silicate, taking zonotlite as an example, a water slurry containing a calcareous raw material and a siliceous raw material having a molar ratio of CaO: SiO ₂ of 4: 5 to 13:10 under pressure is 160 ° C. The method of hydrothermal synthesis for 2 to 48 hours is mentioned above.

  The calcium silicate slurry obtained by hydrothermal synthesis can be dehydrated and molded into a calcium silicate molded body as it is, and the dried calcium silicate is added to water to form a slurry, which is dehydrated and molded. A calcium compact may be used.

The solid content concentration of calcium silicate in the slurry for preparing a calcium silicate molded body is not particularly limited, but is usually 5% or less.
And when manufacturing the low specific gravity calcium silicate molded object whose specific gravity is 0.05 or less, 2 to 4% is preferable.

  The calcium silicate molded body thus obtained has a specific gravity of 0.1 or less, preferably 0.07 to 0.03.

  In addition, the needle-like short fiber powder having a small bulk density is, for example, a bulk density formed by cutting inorganic fibers such as glass wool, glass fiber, alumina fiber, silica alumina fiber, silica fiber, rock wool, and silicon carbide fiber. Small needle-like short fiber powder.

The barrier external packaging material for vacuum heat insulating material according to the present invention can be suitably used as an external packaging material for vacuum heat insulating material using needle-like short fiber powder having a small bulk density as described above or calcium silicate as a heat insulating material core material. is there.
The barrier external packaging material for a vacuum heat insulating material of the present invention is also used as a vacuum heat insulating material external material using foamed polyurethane, expanded polystyrene or the like as a heat insulating material core material.

  The heat insulating material exterior body using the barrier external material for vacuum heat insulating material of the present invention is not limited to general refrigeration equipment, cooling / heating equipment, refrigerators, electric refrigerators using electronic cooling, vending machines, etc. It can be widely applied to cold and hot equipment that uses hot and cold heat up to higher temperatures, equipment that does not require power, such as cold cars, gas equipment, cooler boxes, and prefabricated thermal insulation materials. Further, the barrier exterior material for a vacuum heat insulating material can be used in the medical / pharmaceutical field and the precision instrument / machine field in addition to the heat insulating material exterior body.

It is a cross-sectional schematic diagram which shows the cross section of one Example of a structure of the barriering exterior material for vacuum heat insulating materials of this invention. It is a cross-sectional schematic diagram which shows the cross section of another Example of the structure of the barrier type exterior material for vacuum heat insulating materials of this invention. It is a cross-sectional schematic diagram which shows the cross section of another Example of the structure of the barriering exterior material for vacuum heat insulating materials of this invention. It is a cross-sectional schematic diagram which shows the cross section of another Example of the structure of the barriering exterior material for vacuum heat insulating materials of this invention. It is a perspective view which shows the external appearance of one Example of the vacuum heat insulating material with which the heat insulation core material was filled and accommodated in the bag which used the barriering exterior material for vacuum heat insulating materials of this invention as a jacket material. It is sectional drawing which shows the AA 'line cross section of FIG. It is explanatory drawing for demonstrating the vacuum heat insulating material which consists of the container using the barriering exterior material for vacuum heat insulating materials of this invention as a jacket material, a cover material, and a heat insulating material core material. It is sectional drawing which shows the cross section of one Example of the vacuum heat insulating material by which the heat insulation core material was filled and accommodated in the container using the barriering exterior material for vacuum heat insulating materials of this invention as a jacket material. It is explanatory drawing for demonstrating the structure of the vacuum heat insulating material pack used conventionally. It is sectional drawing which shows the cross section of the vacuum heat insulating material pack currently used conventionally.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... 1st plastic film base material 2 ... 2nd plastic film base material 3 ... Laminated film base material 4 ... Aluminum foil 5 ... Resin containing moisture absorbent Layer 6 ... Sealant layer 7 ... Laminate 8 ... Film substrate layer 9 ... Deposition thin film layer or coating coating layer 10 ... Barrier exterior material for vacuum heat insulating material 11 ... Oxygen barrier Film 12 ... Thermal insulation core material 13 ... Bag 14 ... Container 15 ... Lid material 16 ... Flange 20 ... Barrier exterior material for vacuum insulation material 30 ... Barrier for vacuum insulation material 40 ... Vacuum insulation material 50 ... Vacuum insulation material 60 ... Vacuum insulation material

Claims (7)

A barrier external packaging material for vacuum heat insulating material filled and stored with needle-like short fiber powder with a small bulk density formed by cutting inorganic fibers such as glass wool, or a heat insulating core material of calcium silicate,
Moisture on the vapor-deposited thin film layer or coating coating layer of the oxygen barrier film in which at least one aluminum foil, vapor-deposited thin film layer or coating coating layer is formed on one side of the plastic film substrate or laminated plastic film substrate having puncture resistance A barrier external packaging material for a vacuum heat insulating material, wherein a resin layer containing an adsorbent and a sealant layer are sequentially laminated.   The plastic film substrate is a film substrate of either a polyester film alone, a laminated film of the polyester films, or a laminated film formed by laminating a stretched nylon film on the polyester film alone. The barrier exterior material for a vacuum heat insulating material according to claim 1.   3. The barrier external packaging material for a vacuum heat insulating material according to claim 1, wherein the deposited thin film layer is a deposited thin film layer made of a metal oxide.   The barrier coating material for a vacuum heat insulating material according to claim 1 or 2, wherein the coating coating layer is a coating coating layer made of an inorganic layered compound and a water-soluble polymer.   4. The barrier exterior material for a vacuum heat insulating material according to claim 3, wherein the metal oxide is any one of aluminum oxide, silicon oxide, and magnesium oxide, or a composite thereof.   A vacuum heat insulating material, wherein the barrier external packaging material for a vacuum heat insulating material according to any one of claims 1 to 5 is molded into a bag shape and used.   A vacuum heat insulating material, wherein the barrier external packaging material for a vacuum heat insulating material according to any one of claims 1 to 5 is molded into a container shape and used.

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