JP2007327619A - Laminate for vacuum insulation material, and vacuum insulation material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate for a vacuum-insulation material having improved gas-barrier functionality and low thermal-conductivity, the vacuum insulation material which is formed by sealing an insulating core-material into an outer enclosure formed of the laminate, and evacuating the inside of the outer enclosure so as to have low thermal conductivity through the outer enclosure and sufficient insulation properties, to prevent as far as possible deterioration of the gas-barrier functionality, to hold a vacuum in the inside of the outer enclosure, and to preserve the insulation properties for a long period of time. <P>SOLUTION: In the laminate A for a vacuum insulation material and the vacuum insulation material, the insulating core material is enclosed in the outer enclosure comprising the laminate, and the sealed inside of the outer enclosure is evacuated. The laminate for a vacuum insulation material comprises a heat-sealable resin layer 6 as the innermost layer, and one or more gas-barrier layer 1. In the gas barrier layer 1, one or more layers of deposits 3, 4 are laminated, which comprises carbon-containing silicon oxide formed on a base material 2 comprising a plasma film by plasma chemical vapor-deposition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a laminate for a vacuum heat insulating material and a vacuum heat insulating material, and more specifically, a refrigerator, a rice cooker, a pot, a cooler box, a transport container, a fuel tank for hydrogen, a system bath, an eco-cute hot water tank, a heat storage, a house. The present invention relates to a vacuum heat insulating material used for a wall and a heat insulating wall around a heat generating part of a car, an airplane, a ship, a train, and an OA device.

  Conventionally, a vacuum heat insulating material has been used as a heat insulating layer for a refrigerator or a heat storage. Such a vacuum heat insulating material is used by enclosing a heat insulating core material in an outer packaging material, evacuating the inside of the outer packaging material, and thermally bonding the end of the outer packaging material. In order to maintain the heat insulation performance of the vacuum heat insulating material for a long time, it is necessary to maintain the inside of the outer packaging material at a high vacuum for a long time, and the laminate for vacuum heat insulating material used for the outer packaging material has an excellent gas barrier property. Required. Therefore, it is known to use a laminate in which an aluminum foil having a gas barrier property or aluminum-deposited polyethylene terephthalate is laminated on an outer packaging material that wraps a vacuum heat insulating material (see, for example, Patent Document 1).

  However, as described in Patent Document 1, an excellent gas barrier property can be obtained by using a laminate in which aluminum foil is laminated, and there is an advantage that the inside of the outer packaging material is maintained at a high degree of vacuum over a long period of time. Since the thermal conductivity of aluminum itself is large, there is a problem that sufficient heat insulation performance cannot be obtained due to thermal conduction through the outer packaging material. In order to solve this problem, a method of using a ceramic vapor-deposited layer as an outer packaging material has been invented (see, for example, Patent Document 2).

  However, the method of using a ceramic vapor deposition layer has solved the problem of thermal conductivity, but when the inside of the outer packaging material is evacuated, stress such as bending or elongation of the outer packaging material laminate is caused at the edge of the heat insulating core material. In addition, cracks were generated in the ceramic vapor-deposited film, the gas barrier properties were deteriorated and the heat insulation performance was insufficient, and it was difficult to maintain the inside of the outer packaging material at a high vacuum for a long period of time. In order to solve this problem, a vapor-deposited thin film layer, an intermediate film layer obtained by applying a coating agent containing a water-soluble polymer to a base material made of a plastic material and heat-drying, and then a vapor-deposited thin film layer are sequentially formed A vacuum heat insulating material using a laminated body characterized by being laminated has been proposed (see, for example, Patent Document 3).

However, the vacuum heat insulating material disclosed in Patent Document 3 also needs to bend the heat-bonded end of the outer packaging material when the heat insulating material is fitted into the walls of the inner box and the outer box as a heat insulating layer such as a refrigerator. Further, cracks are easily generated by bending, the gas barrier property is deteriorated with time, and the gas barrier property is not sufficient.
Japanese Unexamined Patent Publication No. 63-279083 JP-A-8-152258 JP 2004-130654 A

  The present invention has been made to solve the above problems, and provides a laminate for a vacuum heat insulating material having excellent gas barrier properties and low thermal conductivity, and encapsulating a heat insulating core material in an outer packaging material using the same. In addition, the vacuum insulation material is formed by evacuating the inside of the outer packaging material, and sufficient heat insulation performance is obtained through the outer packaging material with little heat conduction, and the gas barrier property of the outer packaging material is less deteriorated with time, and the gas barrier property is excellent. The object of the present invention is to provide a vacuum heat insulating material in which the inside of the outer packaging material is maintained at a high vacuum and the heat insulating performance is maintained for a long time.

  In order to achieve the above object, according to the present invention, the heat-insulating core material is enclosed with an outer packaging material made of a laminate, and the interior enclosed with the outer packaging material is deaerated to be in a vacuum state. In a laminate for a vacuum insulation material used for a vacuum insulation material, the laminate for a vacuum insulation material has a heat-adhesive resin layer as an innermost layer, and is formed by a plasma chemical vapor deposition method on a substrate made of a plastic film. In addition, it includes at least one gas barrier layer in which one or more vapor deposition layers made of carbon-containing silicon oxide are laminated.

  Moreover, this invention of Claim 2 contains the ethylene-vinyl alcohol copolymer in which the aluminum vapor deposition layer was formed in the laminated body for vacuum heat insulating materials in the laminated body for vacuum heat insulating materials of Claim 1. It is a feature.

  Further, the present invention according to claim 3 is a vacuum heat insulation formed by encapsulating a heat insulating core material in an outer packaging material using the laminate for a vacuum heat insulating material according to claim 1 or 2, and evacuating the inside of the outer packaging material. It is characterized by being a material.

  The present invention provides at least one gas barrier layer in which one or more vapor-deposited layers made of carbon-containing silicon oxide formed by a plasma chemical vapor deposition method are laminated on a substrate made of a plastic film on a laminate for a vacuum heat insulating material. In addition, there is an excellent effect that it is possible to provide a laminate for a vacuum heat insulating material that is less likely to cause cracking due to bending, has little deterioration in gas barrier properties, and is excellent in gas barrier properties. Furthermore, the vacuum insulation material, in which the insulation core material is enclosed in the outer packaging material using the laminate for vacuum insulation material and the inside of the outer packaging material is evacuated, has low heat conduction through the outer packaging material and has sufficient insulation performance. As a result, the inside of the outer packaging material is maintained at a high vacuum, and the heat insulating performance can be maintained for a long time.

The above-described present invention will be described in detail below with reference to the drawings.
1 is a cross-sectional view showing an embodiment of a laminate for a vacuum heat insulating material according to the present invention, FIG. 2 is a cross-sectional view showing another embodiment of a laminate for a vacuum heat insulating material according to the present invention, and FIG. It is sectional drawing which shows one Embodiment of the vacuum heat insulating material which used the laminated body for vacuum heat insulating materials for outer packaging material, A and B in the figure are the laminated bodies for vacuum heat insulating materials, C is a vacuum heat insulating material, 1 is a gas barrier 1, 2 is a base material, 3 is a vapor deposition layer, 5 is an outer layer, 6 is a thermoadhesive resin layer, 7 is an aluminum vapor deposition layer, 8 is an ethylene-vinyl alcohol copolymer, 10 is an outer packaging material, and 11 seal part , 12 indicate heat insulating cores, respectively.

  As shown in FIG. 1, the laminate A for vacuum heat insulating material according to the present invention is a vapor deposition layer made of carbon-containing silicon oxide formed by a plasma chemical vapor deposition method on a base material 2 made of a plastic film as a gas barrier layer 1. A laminate in which one or more layers 3 and 4 are laminated is used. For example, the outer layer 5, the gas barrier layer 1, the gas barrier layer 1, and the innermost layer are sequentially laminated with the heat-adhesive resin layer 6. Although FIG. 1 shows an example in which two gas barrier layers are laminated, the present invention includes at least one gas barrier layer.

  Since the base material 2 used for the gas barrier layer 1 is a base material that holds a vapor-deposited film of carbon-containing silicon oxide, it can withstand the conditions of their formation, processing, etc., and without impairing their characteristics. It can be held well, and in addition, it is excellent in various physical properties such as workability, heat resistance, slipperiness, pinhole resistance, etc. Furthermore, a resin film or sheet that can satisfy other conditions can be used. In the present invention, specific examples of the resin film or sheet include polyolefin resins such as polyethylene resins and polypropylene resins, cyclic polyolefin resins, polystyrene resins, and acrylonitrile-styrene copolymer. Polyester such as coalescence (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate Films or papers of various resins such as polyamide resins, polyamide resins such as various nylon resins, polyurethane resins, acetal resins, cellulose resins, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, etc. -Can be used. In the present invention, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet among the resin films or sheets.

  In the present invention, the film thickness of various resin films or sheets used for the substrate 2 is preferably about 6 to 200 μm, more preferably about 9 to 100 μm.

  Next, in the present invention, the vapor deposition layers 3 and 4 made of carbon-containing silicon oxide formed by the plasma chemical vapor deposition method provided in the gas barrier layer 1 will be described. For example, the vapor deposition layers 3 and 4 are formed by depositing carbon-containing silicon oxide using a chemical vapor deposition method (CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method. Among them, plasma chemical vapor deposition is preferable, and it is particularly desirable to manufacture by film formation using low temperature plasma chemical vapor deposition. . Specifically, on one surface of the substrate 2 using a low temperature plasma chemical vapor deposition apparatus, a monomer gas for film formation composed of one or more organic silicon compounds is used as a raw material, and argon gas, helium as a carrier gas. Use of an inert gas such as gas, further use oxygen gas as an oxygen supply gas, and carbon containing silicon oxide using low temperature plasma chemical vapor deposition using a low temperature plasma generator etc. The gas barrier layer 1 can be manufactured by forming a silicon oxide film. In the above, as the low-temperature plasma generator, for example, a generator such as high-frequency plasma, pulse wave plasma, or microwave plasma can be used. Thus, in the present invention, highly active and stable plasma is obtained. For this purpose, it is desirable to use a high-frequency plasma generator. In addition, when forming the vapor deposition layer 4 on the vapor deposition layer 3 made of carbon-containing silicon oxide, plasma treatment (described later) is performed on the vapor deposition layer 3 and vapor deposition is performed via a coating layer (not shown). A carbon-containing silicon oxide film to be the layer 4 is formed, and further a plasma treatment is performed on the vapor deposition layer 4 to provide a coat layer (not shown).

  Further, in the plasma chemical vapor deposition method described above, the carbon-containing silicon oxide film made of silicon oxide or the like is formed on the base material 2 while oxidizing the plasma-formed source gas with oxygen gas. Therefore, the carbon-containing silicon oxide film made of the silicon oxide to be formed has a multilayered structure, and each layer is dense and has few gaps. Therefore, the gas barrier property of the carbon-containing silicon oxide layer made of silicon oxide is from silicon oxide formed by a conventional vacuum deposition method or the like. Compared to the silicon oxide layer, the layer is much higher, and since it is composed of a multilayered structure, an extremely high and sufficient gas barrier property can be obtained. Further, the film thickness of the carbon-containing silicon oxide film of the vapor deposition layers 3 and 4 of the gas barrier layer 1 is preferably about 50 to 1000 mm, and if it exceeds 1000 mm, cracks and the like are likely to occur in the film. Therefore, it is not preferable, and if it is less than 50 mm, the gas barrier property is inferior, which is not preferable. In the above, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation.

  Next, in the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyl Disiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, Phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used. In the present invention, among the organic silicon compounds as described above, use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is easy to handle and formed continuous film. In view of the above characteristics and the like, it is a particularly preferable raw material. Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.

  The vapor deposition layers 3 and 4 should just be laminated | stacked at least 1 layer or more of plasma chemical vapor deposition, and can also be combined with the vapor deposition layer which formed the inorganic oxide into a film by physical vapor deposition. As an inorganic oxide vapor-deposited film by such physical vapor deposition, a plasma-treated surface with an inert gas is provided on one surface of the substrate 2, and, for example, a vacuum vapor deposition method, a sputtering method, or an ion plating is provided on this surface. A vapor deposition film of an inorganic oxide can be formed using a physical vapor deposition method (PVD method) such as an ion cluster beam method. For example, a method for providing a vapor deposition film by the PVD method on the vapor deposition layer 3 will be described. A metal or metal oxide is used as a raw material, and this is heated and vaporized, and this is provided on one surface of the base film. Vacuum deposition method for vapor deposition on the surface of the plasma-treated surface by gas, or by using an inert gas provided on one surface of the substrate 2 by using a metal or metal oxide as a raw material and introducing oxygen to oxidize The vapor deposition film can be formed using an oxidation reaction vapor deposition method for vapor deposition on the surface of a plasma treatment surface (not shown), a plasma-assisted oxidation reaction vapor deposition method for further assisting the oxidation reaction with plasma, or the like. In the above, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used.

  The plasma treatment is provided on one surface of the base material 2 and improves the close adhesion between the base material 2 and the vapor-deposited layer 3 of the inorganic oxide by physical vapor deposition. In order to prevent the occurrence of delamination or the like, the two are firmly adhered to each other. Thus, in the present invention, the plasma processing surface by an inert gas will be described. As the plasma processing surface, the plasma is subjected to surface modification by using plasma gas generated by ionizing gas by arc discharge. A plasma treatment surface can be formed by using a surface treatment method or the like. That is, in the present invention, the plasma processing surface can be formed by performing plasma processing by a plasma surface processing method using an inert gas such as nitrogen gas, argon gas, helium gas or the like as the plasma gas. In the present invention, as the plasma gas, a mixed gas obtained by adding oxygen gas to the above inert gas can also be used. In addition, in the present invention, when forming a plasma treatment surface with an inert gas, plasma treatment is performed inline immediately before forming an inorganic oxide vapor deposition film by physical vapor deposition on one surface of the substrate 2. This is desirable because it removes moisture, dust, and the like from the surface of the substrate 2 and enables surface treatment such as smoothing, activation, and the like of the surface. A similar plasma treatment is performed on the vapor deposition layer 3 and the vapor deposition layer 4 to provide a coating layer. In the present invention, as a method for generating plasma, for example, a direct current glow discharge, a high frequency discharge, a microwave discharge, or the like can be used.

Further, the coating layer provided on the plasma-treated surface provided on the vapor deposition layer 3 and the vapor deposition layer 4 includes at least one alkoxide, a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer ( EVOH) and a coating film made of a gas barrier composition obtained by polycondensation by a sol-gel method is preferably used. The polyvinyl alcohol resin or ethylene / vinyl alcohol copolymer and one or more alkoxides constituting this coating film chemically react with each other to form a very strong three-dimensional network composite polymer layer, Thus, it is possible to produce a gas barrier layer 1 that is synergistic with the vapor-deposited film of the inorganic oxide, stably maintains extremely high gas barrier properties, and has impact resistance and the like. In the alkoxide, a general formula R1nM (OR ₂ ) m (wherein R1 and R2 represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents an integer of 0 or more). , M represents an integer of 1 or more, and n + m represents an atomic valence of M).

  Next, the outer layer 5 constituting the laminate A for a vacuum heat insulating material has excellent properties in mechanical, physical, chemical, etc., has excellent strength, and further has heat resistance, moisture resistance, A resin film or sheet excellent in pinhole property, puncture resistance, and the like can be used. Specifically, a film or sheet of tough resin such as polyester resin, polyamide resin, polypropylene resin, or the like can be used. These films or sheets can be used as unstretched films, or stretched films stretched in a uniaxial direction or biaxial direction, but biaxially stretched films are used in terms of mechanical or heat resistance. preferable. The outer layer 5 is laminated in order to improve the physical properties such as strength of the outer packaging material, and the order of lamination is not limited to the outside, and it is between the gas barrier layer 1 and the thermoadhesive resin layer 6 or the gas barrier. It can be interposed between the layer 1 and the gas barrier layer 1, and more than one outer layer 5 can be provided depending on the required quality. Thickness is 9-50 micrometers, and is determined according to the material structure and required quality which are used for the laminated body for vacuum heat insulating materials.

  Next, as the heat-adhesive resin layer 6, it plays the role of the adhesive layer at the time of bag making as an outer packaging material, and a heat-adhesive resin can be used. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ethylene-methacrylic acid Copolymers, ethylene-methacrylic acid ester copolymers, ionomers, polypropylene and the like are used. The thickness is determined according to the required quality, but is usually 15 to 150 μm. These heat-adhesive resins may be used as a film, or may be directly melt-extruded from the T-die and laminated by the extrusion lamination method on the outer layer 5 or the gas barrier layer 1. When the extrusion lamination method is used, an anchor agent may be applied to the laminate surface of the outer layer 5 or the gas barrier layer 1.

The outer layer 5, the gas barrier layer 1, and the heat-adhesive resin layer 6 are laminated by a known method to produce a laminate A for vacuum heat insulating material. Lamination methods include polyester-isocyanate-based, polyether-isocyanate-based, polyurethane-isocyanate-based dry lamination methods, and thermoplastic resin hot melt extrusion from T-die for extrusion. A lamination method is used. Moreover, the laminated body A for vacuum heat insulating materials can be provided with a printing layer on the outer layer 5 or the gas barrier layer 1 or both. In order to use the laminate A for a vacuum heat insulating material as an outer packaging material of the vacuum heat insulating material, the oxygen permeability and the water vapor permeability are 0.5 (cc / m ² · day) and 0.2 (g, respectively) as gas barrier properties. / M ² · day) or less, preferably 0.1 (cc / m ² · day) or 0.1 (g / m ² · day) or less.

  Next, other embodiment of the laminated body for vacuum heat insulating materials concerning this invention is described using FIG. As shown in FIG. 2, the laminate B for vacuum heat insulating material of the present invention has an outer layer 5, a vapor deposition layer 3 made of carbon-containing silicon oxide formed by plasma chemical vapor deposition on a base material 2 made of a plastic film, 4 is formed by sequentially laminating a gas barrier layer 1 in which one or more layers 4 are laminated, an ethylene-vinyl alcohol copolymer 8 in which an aluminum vapor deposition layer 7 is formed on one surface, and a thermal adhesive resin layer 6 in the innermost layer. .

  The aluminum vapor deposition layer 7 is provided by forming an aluminum vapor deposition film by a physical vapor deposition method (PVD method) such as a vacuum vapor deposition method, a sputtering method, an ion plating method, an ion cluster beam method, or the like. Yes. In the above, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used. The gas barrier layer 1, the outer layer 5, and the thermoadhesive resin layer 6 are the same as in the embodiment of the laminate A for vacuum heat insulating material, and the description thereof is omitted. As a lamination method, a dry lamination method and an extrusion lamination method can be used, but a dry lamination method in which the aluminum vapor deposition layer 7 is less deteriorated is preferable. By having such a configuration, the gas barrier property is further improved, the vacuum heat insulating material formed by evacuating the inside of the outer packaging material, enclosing the heat insulating core material, using the laminate B for vacuum heat insulating material as the outer packaging material, The inside of the outer packaging material can be maintained at a high vacuum, and the heat insulating performance can be maintained for a long time.

  Next, the vacuum heat insulating material C which used the laminated body for vacuum heat insulating materials of this invention for the outer packaging material 10 is demonstrated using FIG. As shown in FIG. 3, the vacuum heat insulating material C of the present invention is, for example, heat-sealed at the three peripheral edges except for one end that becomes an opening with the heat-adhesive resin layer 6 of the laminate for vacuum heat insulating material facing. After the heat insulating core material 12 is accommodated from the opening in the outer packaging material 10 that is formed into a bag shape by providing the seal portion 11, the outer packaging material 10 is closely attached to the heat insulating core material 12 by evacuating the inside of the outer packaging material 10. And the opening is heat sealed.

  As the heat insulating core material 12, an inorganic material such as silica, pearlite or calcium silicate, or an organic material such as polyurethane foam is used. Moreover, as a form of the heat insulation core material 12, fine powder, porous, a fiber, etc. are mentioned.

The inside of the outer packaging material 10 of the vacuum heat insulating material C of the present invention is usually evacuated to 5 Pa or less to minimize heat conduction by convection. When the degree of vacuum is higher than 5 Pa, air remaining in the outer packaging material 10 is convected and heat insulation performance is deteriorated, which is not preferable.
Hereinafter, the present invention will be described in more detail with reference to examples.

<Production of gas barrier layer>
(1) A biaxially-stretched polyethylene terephthalate film (hereinafter referred to as PET) having a thickness of 12 μm and subjected to double-sided corona treatment is used as a substrate, and is mounted as a winding on a plasma chemical vapor deposition apparatus. The inside of the chamber of the apparatus was depressurized. On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organic silicon compound, is volatilized as a raw material in a raw material volatilization supply device, and oxygen gas and inert gas helium, argon supplied from the gas supply device, The raw material gas was obtained by mixing. As the raw material gas used in the film forming chamber, the mixing ratio of the raw material gas is HMDSO: O 2: He: Ar = 1.2: 0.5: 0.5: 0.5 (unit: slm, amount per minute) Is shown in liters). Using the raw material gas as described above, each of the raw material gases is introduced into the film forming chamber, and then the film forming output of 15 kW is applied while the PET having a thickness of 12 μm is conveyed at a line speed of 200 m / min. A first layer made of carbon-containing silicon oxide having a thickness of 300 mm is formed on one corona-treated surface of PET having a thickness of 12 μm at a vacuum degree of 5 Pa in the deposition chamber, and then a magnetron sputtering apparatus is used. Then, 600 sccm of argon gas was introduced, plasma treatment was performed at an output of 20 kW, and a plasma treatment surface with an inert gas was formed on the surface of the vapor deposition layer of the above-mentioned first layer carbon-containing silicon oxide. .
(2) On the other hand, according to the composition shown below, an EVOH solution (composition a) in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water was prepared in advance with ethyl silicate 40, isopropyl A hydrolyzed liquid (composition b) comprising alcohol, acetylacetone aluminum and ion-exchanged water is added and stirred, and further comprises a pre-prepared polyvinyl alcohol aqueous solution, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol and ion-exchanged water. A mixed solution (composition c) was added and stirred to prepare a colorless and transparent coating solution.
〔composition〕
a. EVOH (ethylene copolymerization rate 29%) 0.610 (wt%)
Isopropyl alcohol 3.294
H ₂ O 2.196
b. Ethyl silicate 40 11.460
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
c. Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Total 100.000 (wt%)
Next, the coating liquid prepared above is used for the plasma treatment surface of the first layer formed in (1) above, and this is coated by the gravure roll coating method, and then heated at 100 ° C. for 30 seconds. The coating was applied to form a coat layer having a coating amount of 0.4 g / m 2 (in a dry state) and wound up.
(3) Next, using the winding of the PET on which the coating layer was formed in the above (2), this was again mounted on the unwinding roll of the plasma chemical vapor deposition apparatus, and then the line speed was 200 mm / In this case, a magnetron sputtering apparatus is used, an argon gas of 600 sccm is introduced, a plasma treatment is performed at an output of 20 kW, and a plasma treatment surface with an inert gas is formed on the surface of the coating layer. A second layer made of carbon-containing silicon oxide having a thickness of 300 mm is formed on the plasma-treated surface under the conditions shown below. Next, using a magnetron sputtering apparatus, argon gas is introduced at 600 sccm, and plasma is output at an output of 20 kW. A treatment is performed to form a plasma treatment surface with an inert gas on the surface of the vapor deposition layer of the second layer carbon-containing silicon oxide, and winding It was.
(Deposition conditions)
Reaction gas mixture ratio: HMDSO: oxygen gas: helium = 1.2: 5.0: 2.5 (unit: Slm)
Ultimate pressure: 5.0 × 10 ^-5 mbar
Film forming pressure: 7.0 × 10 ⁻² mbar
Line speed; 200m / min power; 35kW
(4) Next, a coat layer is formed on the plasma treatment surface of the second layer formed in the above (3) in the same manner as in the above (2). A gas barrier film (α) constituting a gas barrier layer was prepared by laminating two vapor-deposited layers made of carbon-containing silicon oxide having a thickness of 300 mm and a total film thickness of 600 mm.

<Production of laminate for vacuum heat insulating material>
Polyester-using a biaxially stretched nylon film (ON) with a thickness of 15 μm as the outer layer, a low density polyethylene film (PE) with a thickness of 50 μm as the thermal adhesive resin layer, and the gas barrier film (α) described above as the gas barrier layer Each layer is laminated by dry lamination using an isocyanate-based adhesive, and ON 15 μm / gas barrier film (α) (second layer carbon-containing silicon oxide vapor deposition layer / first layer carbon-containing silicon oxide vapor deposition layer / PET 12 μm) / gas barrier film ( α) (second layer carbon-containing silicon oxide vapor deposition layer / first layer carbon-containing silicon oxide vapor deposition layer / PET 12 μm) / PE 50 μm The laminate for a vacuum heat insulating material shown in FIG. 1 was produced.

<Production of vacuum insulation material>
The laminate for vacuum heat insulating material was cut into a rectangular shape, the heat-adhesive resin layer was made to face, the periphery was heat-sealed, and an outer packaging material having an opening at one end was made into a bag. Using a molded body of silica powder as the heat insulating core material, this is put through the opening of the outer packaging material, the inside of the outer packaging material is evacuated to 3 Pa, and the opening is heat-sealed, as shown in FIG. 3 300 mm × 400 mm × 10 mm A rectangular parallelepiped vacuum heat insulating material was prepared.

<Production of gas barrier layer>
(1) A biaxially-stretched polyethylene terephthalate film (hereinafter referred to as PET) having a thickness of 12 μm and subjected to double-sided corona treatment is used as a substrate, and is mounted as a winding on a plasma chemical vapor deposition apparatus. The inside of the chamber of the apparatus was depressurized. Next, while transporting the above PET having a thickness of 12 μm at a line speed of 200 m / min, on one corona-treated surface of the PET under the same conditions as the vapor deposition layer of the first layer carbon-containing silicon oxide formed in Example 1. Then, a first layer made of carbon-containing silicon oxide having a thickness of 300 mm is formed, and then a magnetron sputtering apparatus is used to introduce an argon gas of 600 sccm, and a plasma treatment is performed at an output of 20 kW. A plasma-treated surface with an inert gas was formed on the surface of the vapor-deposited layer of silicon oxide, and winding was performed.
(2) Next, a coating layer is formed using the coating liquid used in Example 1 on the plasma-treated surface formed on the surface of the first carbon-containing silicon oxide vapor deposition layer formed in (1) above. And it was taken up.
(3) Next, using the winding of the PET on which the coating layer is formed in the above (2), this is mounted as a winding on a winding type vacuum vapor deposition apparatus, and then the PET is mounted at a line speed of 600 mm / min. Conveyed, using a magnetron sputtering apparatus, introduced argon gas 500 sccm (in which the amount per minute is expressed in milliliters), plasma treatment was performed at an output of 20 kW, and the surface of the coating layer was inactive A plasma-treated surface by gas is formed, and then, by using vacuum as an electron beam (EB) heating method while supplying oxygen gas to the plasma-treated surface using aluminum as a deposition source, the following deposition conditions are used. Then, a vapor deposition layer of aluminum oxide having a thickness of 300 mm as the second layer is formed, and then argon gas 50 is used using a magnetron sputtering apparatus. By introducing sccm, and plasma treatment at an output 20 kW, the surface of the deposition layer of aluminum oxide of the second layer described above was collected by winding to form a plasma treated surface with an inert gas.
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ^-4 mbar
Degree of vacuum in winding chamber; 2 × 10 ^-2 mbar
Electron beam power: 25 kW
Film conveyance speed: 600 m / min (4) Next, using the coating liquid used in Example 1 on the plasma-treated surface formed on the aluminum oxide vapor deposition layer of the second layer formed in (3) above A gas barrier is formed by forming a coating layer, laminating a vapor deposition layer thickness of 300 nm of the carbon-containing silicon oxide of the first layer, a vapor deposition layer thickness of 300 mm of the second aluminum oxide, and a total deposition thickness of 600 mm. A gas barrier film (β) constituting the layer was produced.

<Production of laminate for vacuum heat insulating material>
A biaxially stretched nylon film (ON) with a thickness of 15 μm as an outer layer, a low-density polyethylene film (PE) with a thickness of 50 μm as a heat-adhesive resin layer, the gas barrier film (β) described above as a gas barrier layer, and Example 1 were prepared. Each layer is laminated by a dry lamination method using a polyester-isocyanate adhesive using a gas barrier film (α), and ON 15 μm / gas barrier film (α) (second layer carbon-containing silicon oxide vapor deposition layer / first layer carbon) Containing silicon oxide vapor deposition layer / PET 12 μm) / gas barrier film (β) (second layer aluminum oxide vapor deposition layer / first layer carbon-containing silicon oxide vapor deposition layer / PET 12 μm) / PE 50 μm laminate shown in FIG. Was made.

<Production of vacuum insulation material>
The same vacuum heat insulating material as Example 1 was produced using the said laminated body for vacuum heat insulating materials.

<Production of laminate for vacuum heat insulating material>
Biaxially stretched nylon film (ON) with a thickness of 15 μm for the outer layer, a low-density polyethylene film (PE) with a thickness of 50 μm for the heat-adhesive resin layer, the gas barrier film (α) prepared in Example 1 for the gas barrier layer, and a gas barrier Polyester-isocyanate-based adhesion using a 12 μm thick ethylene-vinyl alcohol copolymer film (EVOH; manufactured by Kuraray Co., Ltd., VM-XL) on which a vapor-deposited layer made of aluminum having a thickness of 400 mm is formed as a conductive film Each layer is laminated by a dry lamination method using an agent, and ON 15 μm / gas barrier film (α) (second layer carbon-containing silicon oxide deposition layer / first layer carbon-containing silicon oxide deposition layer / PET 12 μm) / aluminum deposition EVOH (aluminum deposition) / EVOH 12 μm) / PE 50 μm configuration shown in FIG. To prepare a wood laminate for.

<Production of vacuum insulation material>
The same vacuum heat insulating material as Example 1 was produced using the said laminated body for vacuum heat insulating materials.

[Comparative Example 1]
<Production of gas barrier layer>
(1) Use PET having a thickness of 12 μm on both sides as the base material, attach it to a take-up vacuum deposition device as a take-up, and then transport the PET at a line speed of 600 mm / min. In use, argon gas 500 sccm is introduced, plasma treatment is performed at an output of 20 kW, a plasma treatment surface with an inert gas is formed on one surface of PET, and aluminum is then deposited on the plasma treatment surface. Using the vacuum deposition method by electron beam (EB) heating method while supplying oxygen gas, an aluminum oxide vapor deposition layer having a thickness of 300 mm as the first layer is formed under the following vapor deposition conditions. Using a sputtering device, introducing argon gas 500 sccm, performing plasma treatment with an output of 20 kW, The surface of the deposition layer of aluminum oxide serial first layer of, was collected by winding to form a plasma treated surface with an inert gas.
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ^-4 mbar
Degree of vacuum in winding chamber; 2 × 10 ^-2 mbar
Electron beam power: 25 kW
Film conveyance speed: 600 m / min (2) Next, using the coating liquid used in Example 1, on the plasma treatment surface formed on the vapor deposition layer of the first layer aluminum oxide formed in (1) above, A coat layer was formed and wound up.
(3) Next, using the winding of the PET on which the coating layer was formed in the above (2), it is mounted again on the winding roll of the winding type vacuum vapor deposition apparatus, and then conveyed at a line speed of 600 mm / min. Then, using a magnetron sputtering apparatus, an argon gas of 500 sccm is introduced, plasma treatment is performed at an output of 20 kW, and a plasma treatment surface with an inert gas is formed on the surface of the coating layer, and then the plasma treatment is performed. A second layer made of aluminum oxide having a thickness of 300 mm is formed on the surface by vacuum deposition using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a deposition source. Next, using a magnetron sputtering apparatus, argon gas 500 sccm was introduced and plasma treatment was performed at an output of 20 kW. I, on the surface of the deposition layer of the second layer of aluminum oxide above, was the winding to form a plasma treated surface with an inert gas.
(Deposition conditions)
Reaction gas mixture ratio: HMDSO: oxygen gas: helium = 1.2: 5.0: 2.5 (unit: Slm)
Ultimate pressure: 5.0 × 10 −5 mbar
Film forming pressure: 7.0 × 10 −2 mbar
Line speed; 200m / min power; 35kW
(4) Next, a coating layer is formed on the plasma treatment surface of the second layer formed in the above (3) using the coating liquid used in Example 1, and a vapor deposition layer film of the first layer of aluminum oxide A gas barrier film (γ) constituting a gas barrier layer was produced by laminating two vapor-deposited layers having a thickness of 300 mm, a second aluminum oxide vapor-deposited film thickness of 300 mm, and a total film thickness of 600 mm.

<Production of laminate for vacuum heat insulating material>
Using an outer layer of a biaxially stretched nylon film (ON) having a thickness of 15 μm, a high-density polyethylene film (PE) having a thickness of 50 μm as a heat-adhesive resin layer, and the above gas barrier film (γ) as a gas barrier layer, polyester- Each layer is laminated by dry lamination using an isocyanate-based adhesive, and ON15 μm / gas barrier film (γ) (second layer aluminum oxide deposition layer / first layer aluminum oxide deposition layer / PET 12 μm) / gas barrier film (γ) (first A laminate for a vacuum heat insulating material having a structure of two layers aluminum oxide vapor deposition layer / first layer aluminum oxide vapor deposition layer / PET 12 μm) / PE 50 μm was produced.

<Production of vacuum insulation material>
The same vacuum heat insulating material as Example 1 was produced using the said laminated body for vacuum heat insulating materials.

[Comparative Example 2]
<Production of laminate for vacuum heat insulating material>
The outer layer is 15 μm thick ON, the thermal adhesive resin layer is 50 μm thick PE, the gas barrier layer is the gas barrier film (γ) prepared in Comparative Example 1, and the gas barrier film is 12 μm thick used in Example 3. Using aluminum vapor deposition EVOH, each layer is laminated by a dry lamination method using a polyester-isocyanate adhesive, and ON15 μm / gas barrier film (γ) (second layer aluminum oxide vapor deposition layer / first layer aluminum oxide vapor deposition layer / A laminate for a vacuum heat insulating material having a structure of PET 12 μm / aluminum vapor deposition EVOH (aluminum vapor deposition / EVOH 12 μm) / PE 50 μm was produced.

<Production of vacuum insulation material>
The same vacuum heat insulating material as Example 1 was produced using the said laminated body for vacuum heat insulating materials.

<Experimental example>
About the laminated body for vacuum heat insulating materials produced in said Examples 1-3 and Comparative Examples 1-2, oxygen permeability and water vapor permeability were measured. Moreover, about the vacuum heat insulating material produced in said Examples 1-3 and Comparative Examples 1-2, thermal conductivity was measured.
(1) Measurement of oxygen permeability Based on JIS-K7126B, it measured on the conditions of temperature 23 degreeC and humidity 90% RH.
Measuring instrument: Measured with a measuring instrument (model name, OXTRAN) manufactured by MOCON, USA.
(2) Measurement of water vapor permeability Measurement was performed with a measuring instrument (model name, PERMATRAN) manufactured by MOCON, USA, under conditions of a temperature of 40 ° C. and a humidity of 90% RH.
(3) Measurement of thermal conductivity About the manufactured vacuum heat insulating material, the thermal conductivity immediately after the manufacturing (initial stage) and after leaving at 40 ° C. and 90% RH for 10 days and after standing for 1 month is measured under the condition of the measurement ambient temperature of 20 ° C. It was measured.
Measuring instrument: Eihiro Seiki thermal conductivity measuring instrument Table 1 shows the measurement results.

  As shown in Table 1, with respect to oxygen permeability and water vapor permeability, all of the laminates for vacuum heat insulating materials of Examples 1 to 3 and Comparative Examples 1 and 2 showed good gas barrier properties. Regarding the thermal conductivity, the vacuum heat insulating materials of Examples 1 to 3 are good both in the initial stage and after one month, and the thermal conductivity after one month is small and less changed with time than the initial thermal conductivity. there were. On the other hand, the vacuum heat insulating materials of Comparative Examples 1 and 2 had good initial thermal conductivity, but the thermal conductivity after one month was larger than that in the initial stage, and the change with time was large. From this, it is possible to obtain excellent gas barrier properties by laminating one or more gas barrier layers in which one or more vapor-deposited layers made of carbon-containing silicon oxide are laminated on the laminate for vacuum heat insulating material. The vacuum heat insulating material using the laminated body has an excellent vacuum heat insulating material in which the thermal conductivity is little changed with time, the inside of the outer packaging material is maintained at a high vacuum, and the heat insulating performance can be maintained for a long time.

It is sectional drawing which shows one Embodiment of the laminated body for vacuum heat insulating materials concerning this invention. It is sectional drawing which shows other embodiment of the laminated body for vacuum heat insulating materials concerning this invention. It is sectional drawing which shows one Embodiment of the vacuum heat insulating material which used the laminated body for vacuum heat insulating materials of this invention for the outer packaging material.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Gas barrier layer 2 Base material 3, 4 Evaporation layer 5 Outer layer 6 Thermal adhesive resin layer 7 Aluminum vapor deposition layer 8 Ethylene-vinyl alcohol copolymer 10 Outer packaging material 11 Sealing part 12 Thermal insulation core material A, B Laminate for vacuum thermal insulation materials C Vacuum insulation

Claims (3)

In a vacuum insulation material laminate used for a vacuum insulation material in which a heat insulation core material is enclosed with an outer packaging material made of a laminate and the inside enclosed with the outer packaging material is evacuated to a vacuum state, the laminate for vacuum insulation material Has at least one gas barrier layer in which at least one vapor-deposited layer made of carbon-containing silicon oxide formed by plasma chemical vapor deposition is formed on a base material made of a plastic film. The laminated body for vacuum heat insulating materials characterized by including the layer or more. The laminate for a vacuum heat insulating material according to claim 1, comprising an ethylene-vinyl alcohol copolymer in which an aluminum vapor deposition layer is formed on the laminate for a vacuum heat insulating material. The vacuum heat insulating material formed by enclosing a heat insulation core material in the outer packaging material using the laminated body for vacuum heat insulating materials according to claim 1 or 2, and evacuating the inside of the outer packaging material.

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