JP2014081070A - Outer bag for vacuum insulation structure and vacuum insulation structure - Google Patents

Abstract

An outer bag for a vacuum heat insulating structure and a vacuum heat insulating structure that have peeling resistance and excellent heat insulating performance even when used for a long period of time.
Layer structure of base film (A) / deposition layer (B) made of metal or metal oxide / vinyl alcohol resin layer (C) / vinyl alcohol resin film (D) / sealing layer (E) A laminated body [I] having the above structure and a vacuum heat insulating structure using the same.
[Selection figure] None

Description

  The present invention relates to a vacuum heat insulating structure outer bag and a vacuum heat insulating structure, and more specifically, a vapor deposition layer of a base film having a vapor deposition layer made of a metal or a metal oxide and a vinyl alcohol film to be a gas barrier film. The present invention relates to an exterior bag for a vacuum heat insulation structure excellent in adhesiveness with a gas barrier layer laminated on a vapor deposition layer and also having excellent heat insulation performance, and a vacuum heat insulation structure using the same.

  Conventionally, heat insulating materials using polyurethane foam have been used as heat insulating materials for refrigerators and electric pots or heat insulating walls for houses, but in recent years, glass wool, silicon oxide have been used as excellent alternative materials. A vacuum heat insulating structure in which a heat insulating material such as a foaming resin is used as a core, this is sealed with a gas barrier laminate film, and the inside is vacuumed has come to be used.

  In such a vacuum heat insulating structure, a multilayer film provided with a vinyl alcohol resin film or a vapor deposition layer is used as a gas barrier laminate film. As the vinyl alcohol resin film, a film made of polyvinyl alcohol resin or ethylene-vinyl is used. A film made of an alcohol copolymer is used.

  As a vacuum heat insulating structure composed of a multilayer film using these vinyl alcohol-based resin films and vapor-deposited layers, for example, a heat insulating material and a jacket material enclosing the heat insulating material are provided, and the jacket material is In addition, a vacuum heat insulating structure, which is a bag-shaped multilayer structure obtained by laminating seal layers of a multilayer film composed of a vapor deposition base film, a gas barrier film, and a seal layer by heat fusion, has been proposed ( For example, see Patent Document 1.)

  Moreover, in the vacuum heat insulation structure which consists of a multilayer film containing the conventional vapor deposition layer, in order to improve the adhesiveness of a vapor deposition layer and the film layer laminated | stacked on it, it pre-processes on the surface of a vapor deposition layer or the film to bond together As such, a corona treatment is performed, or a thin film layer is provided with a coating agent that uses a urethane-based curing agent with a polyester resin or a polyether resin as a main component (see, for example, Patent Document 2).

JP2009-241328 JP2008-110604

  However, in the method of performing a corona treatment or providing a thin film layer with a coating agent using a urethane-based curing agent, the adhesion between the deposited layer of the deposited substrate film and the film laminated thereon is sufficient. However, when used for a long time, peeling of the adhesive surface may occur, and the heat insulation performance as a vacuum heat insulation structure may be deteriorated. Further, the vacuum heat insulation structure having excellent adhesiveness and heat insulation performance Is required.

  Therefore, in the present invention, under such a background, the vacuum insulation is excellent in adhesion between the vapor deposition layer of the vapor deposition base film and the gas barrier layer laminated thereon and excellent in heat insulation performance even when used for a long time. It is an object of the present invention to provide a structural outer bag and a vacuum heat insulating structure using the same.

  However, as a result of intensive studies in view of such circumstances, the present inventor has provided a vinyl alcohol-based resin layer on the vapor deposition layer of the vapor deposition base film, thereby providing such a vapor deposition layer and a vinyl alcohol type laminated thereon. The present invention was completed by discovering that an outer bag for a vacuum heat insulating structure having excellent adhesion to a gas barrier layer such as a resin film and having excellent heat insulating performance as a vacuum heat insulating structure can be obtained.

  That is, the gist of the present invention is that the base film (A) / deposition layer (B) made of metal or metal oxide / vinyl alcohol resin layer (C) / vinyl alcohol resin film (D) / sealing layer (E ), The outer bag for a vacuum heat insulating structure, which includes the laminate [I] having the layer structure.

  Furthermore, in this invention, the vacuum heat insulation structure by which a heat insulating material is packaged by the exterior bag for vacuum heat insulation structures containing the laminated body [I] which has said layer structure is also provided.

  The exterior bag for a vacuum heat insulating structure and the vacuum heat insulating structure according to the present invention are: base film (A) / deposition layer (B) / vinyl alcohol resin layer (C) / vinyl alcohol resin made of metal or metal oxide By including the laminate [I] having a layer configuration of film (D) / seal layer (E), it has excellent adhesion between the deposited layer and a layer laminated on the deposited layer, such as a vinyl alcohol film. Even when used for a long period of time, it exhibits an excellent effect on heat insulation performance.

The present invention is described in detail below.
The exterior bag for a vacuum heat insulating structure of the present invention contains a laminate [I] having a specific layer structure.

  Laminate [I] of the present invention comprises: base film (A) / vapor deposition layer (B) / vinyl alcohol resin layer (C) / vinyl alcohol resin film (D) / seal layer made of metal or metal oxide (E) It has a layer structure.

As a base film (A) in this invention, a well-known general base film can be used as a base film used when producing the exterior bag for vacuum heat insulation structures, for example, a polyester-type film, a polyolefin-type film , Polyamide film, polyether film, and polyurethane film. Among them, it is preferable to use a polyester film or a polyolefin film from the viewpoints of processability, durability and economy, particularly polyethylene terephthalate film, polybutylene terephthalate film and polypropylene film, particularly polyethylene terephthalate film. Is preferred.
In addition, it is preferable to use a film that has been subjected to stretching treatment from the viewpoint of the smoothness of the film surface and applicability to a continuous coating machine or continuous laminating machine, and in particular, a biaxially stretched film is used. Is preferred.

  The thickness of the base film is usually 5 to 100 μm, preferably 5 to 50 μm, and particularly preferably 5 to 30 μm. If this thickness is too thick, there is a tendency that the stress concentrated on the wrinkled part entering the exterior bag increases when the vacuum insulation structure is finished, and the possibility of generating pinholes tends to increase. When it is finished, the strength as an exterior bag is not sufficiently obtained, and the bag tends to be broken during processing and use.

  The vapor deposition layer (B) in the present invention is a layer formed by subjecting at least one surface of the base film (A) to vapor deposition treatment, and is a publicly known general material used when producing an exterior bag for a vacuum heat insulating structure. A vapor deposition layer may be used, and a vapor deposition layer made of metal or metal oxide is preferable.

  In addition, the above-mentioned vapor deposition layer (B) is a layer formed for the purpose of gas barrier properties in the layer structure of the vacuum insulation structure exterior bag, and has excellent gas barrier properties as a vacuum insulation structure, Insulates heat insulation performance.

  As the metal or metal oxide forming such a vapor deposition layer, for example, a metal such as aluminum, gold, silver, copper, nickel, cobalt, chromium, tin, indium, or zinc, or an oxide of such a metal can be used. . Among these, aluminum, gold, silver, and tin are preferably used, and aluminum is particularly preferably used from the viewpoint of cost.

  As a deposition method of such a metal or metal oxide, for example, a general vacuum deposition method such as a sputtering method, an ion plating method, a resistance heating deposition method, a high frequency induction heating deposition method, or an electron beam heating deposition method is used. it can.

  Moreover, the said vapor deposition layer (B) may be obtained by one vapor deposition process, and may be obtained by repeating vapor deposition process in multiple times.

  The thickness of the vapor deposition layer (B) formed by vapor deposition of such a metal or metal oxide is preferably 200 to 1000 mm, particularly preferably 300 to 800 mm. If the thickness of the vapor deposition layer (B) is too thin, thermal radiation characteristics tend to be difficult to obtain. If it is too thick, the vapor deposition time for obtaining the thickness is too long, and the thermal influence during vapor deposition becomes too great. Tend to be industrially unfavorable.

  In addition, it is possible to pre-treat the surface of the base film before performing the vapor deposition on the base film, and as such pre-treatment, for example, a method of promoting activation of the base material itself such as corona treatment And a method of forming a thin film layer with a coating agent using a urethane-based curing agent mainly composed of a polyester resin or a polyether resin.

  In the present invention, the most characteristic feature is to provide a vinyl alcohol-based resin layer (C) on the vapor-deposited layer (B), whereby the vinyl alcohol-based resin laminated on the vapor-deposited layer surface. It becomes what was excellent in adhesiveness with a film (D).

The vinyl alcohol resin layer (C) used in the present invention is formed using a vinyl alcohol resin.
The vinyl alcohol resin only needs to have a vinyl alcohol unit obtained by saponifying a vinyl ester unit, and preferably has an average saponification degree of 90 mol% or more, particularly preferably 95 mol% or more, and more preferably 97 mol%. More than mol%.
Examples of the vinyl alcohol resin include a polyvinyl alcohol resin (hereinafter sometimes abbreviated as PVA resin) and an ethylene-vinyl alcohol resin (hereinafter abbreviated as EVOH resin). Among them, a PVA resin is particularly preferable.

  First, the PVA resin will be described.

  The PVA-based resin is a thermoplastic resin that can be dissolved in water (including warm water), and examples of the PVA-based resin used in the present invention include PVA and modified PVA. And post-modified products. PVA is produced by homopolymerizing vinyl acetate and further saponifying it. The copolymer-modified PVA resin is produced by copolymerizing vinyl acetate and an unsaturated monomer copolymerizable with vinyl acetate and then saponifying, and the modification amount impairs the effects of the present invention. In the range, usually less than 10 mol%.

  Examples of the unsaturated monomer copolymerizable with vinyl acetate include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, 3-buten-1-ol, and 4-pentene. Derivatives such as hydroxy group-containing α-olefins such as -1-ol and 5-hexen-1-ol and acylated products thereof, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, undecylenic acid Unsaturated acids such as salts, monoesters, or dialkyl esters, amides such as diacetone acrylamide, acrylamide, and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid, or salts thereof Is mentioned.

  Further, as the PVA resin, a PVA resin having a 1,2-diol structure in the side chain can also be used, and the PVA resin having a 1,2-diol structure in the side chain is, for example, (a) acetic acid A method of saponifying a copolymer of vinyl and 3,4-diacetoxy-1-butene, (a) a method of saponifying and decarboxylating a copolymer of vinyl acetate and vinyl ethylene carbonate, and (c) vinyl acetate. Of saponifying and deketalizing a copolymer of 2,2-dialkyl-4-vinyl-1,3-dioxolane, and (d) saponifying a copolymer of vinyl acetate and glycerol monoallyl ether. Obtained by a method, etc.

  In the present invention, when a PVA resin having a 1,2-diol structure in the side chain is used, it is preferable that the content of the side chain 1,2-diol structure is 0.01 to 20 mol%. From the viewpoint of obtaining properties, it is particularly preferably 0.2 to 15 mol%, more preferably 0.5 to 12 mol%.

  Among the PVA-based resins, in the present invention, it is preferable in terms of adhesiveness to use a PVA-based resin having a 1,2-diol structure in the side chain.

  Furthermore, as modified PVA, it can also manufacture by post-modifying PVA. Examples of such post-modification methods include a method of converting PVA into acetoacetate ester, acetalization, urethanization, etherification, grafting, phosphoric esterification, and oxyalkylene.

  In the present invention, the average degree of polymerization of the PVA-based resin is preferably 300 to 4000, more preferably 500 to 3800, particularly preferably 1000 to 2600, and an average saponification degree of 90 to 100 mol. %, And a more preferable range is 95 to 100 mol%, and a particularly preferable range is 99 to 100 mol%. If the average degree of polymerization is too low, the cohesive force decreases, the strength of the formed resin layer itself tends to decrease and the adhesion to the deposited layer also tends to decrease. If the average degree of polymerization is too high, a resin layer is formed. Therefore, the viscosity increases at the stage of adjusting the resin solution to reduce the pot life, and it tends to be difficult to form a thin layer. When the average saponification degree is too low, the water resistance of the obtained resin layer tends to decrease.

Moreover, as a viscosity of the 4 weight% aqueous solution of the said PVA-type resin, 0.1-400 mPa * s (20 degreeC) is preferable, Furthermore, 2-200 mPa * s (20 degreeC), Especially 4-100 mPa * s ( 20 ° C.) is preferred. If the viscosity is too low, the strength and adhesion of the resin layer tend to decrease, and if it is too high, the resin layer becomes thick and it tends to be difficult to form stably at a desired thickness.
The viscosity is measured according to JIS K6726.

  These PVA resins can be used alone or in combination of two or more.

  Next, the EVOH resin will be described.

  The EVOH-based resin is a thermoplastic resin that is obtained by copolymerizing ethylene and a vinyl ester monomer and then saponifying, and does not dissolve in water (including warm water). The polymerization can be carried out by any known polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization and the like.

  As the vinyl ester monomer, vinyl acetate is generally used, but other vinyl ester monomers such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, capric acid. Usually, an aliphatic vinyl ester such as vinyl, vinyl laurate, vinyl stearate, vinyl versatate, and an aromatic vinyl ester such as vinyl benzoate, etc., usually 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, particularly preferably An aliphatic vinyl ester having 4 to 7 carbon atoms may be used. These monomers are usually used alone, but a plurality of these monomers may be used simultaneously as necessary.

The ethylene content of the EVOH-based resin is usually 20 to 60 mol%, particularly preferably the lower limit is 25 mol% or more, and more preferably 30 mol% or more. From the viewpoint of gas barrier properties, the ethylene content is preferably 55 mol% or less, more preferably 50 mol% or less. When there is too much ethylene content, there exists a tendency for gas barrier property to fall.
In addition, the ethylene content of the EVOH resin can be obtained by a nuclear magnetic resonance (NMR) method.

  The average saponification degree of the vinyl ester component in the EVOH-based resin is a value measured based on JIS K6726 (however, the EVOH resin is a solution uniformly dissolved in water / methanol solvent), usually 90 to 100 mol%, Preferably it is 95-100 mol%, Most preferably, it is 99-100 mol%. When the average saponification degree is too low, gas barrier properties, thermal stability, moisture resistance and the like tend to be lowered.

  The melt flow rate (MFR) (210 ° C., load 2160 g) of the EVOH resin is usually 0.5 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, particularly preferably 2 to 35 g / 10 minutes. It is. If the MFR is too large, the coatability tends to become unstable. If the MFR is too small, the viscosity is too high, resulting in poor flow and a tendency to cause appearance defects such as repellency and film thickness defects. is there.

  The EVOH resin includes an antioxidant, a colorant, an ultraviolet absorber, a slip agent, an antistatic agent, a plasticizer, a cross-linking agent such as boric acid, an inorganic filler, an inorganic substance, and the like within a range that does not interfere with the object of the present invention. You may mix | blend various resins, such as various additives, such as a desiccant, polyamide, polyolefin, and a super absorbent polymer.

  The EVOH-based resin may contain 0.0002 to 0.2 mol% of a vinyl silane compound as a copolymer component for improving stability when heated and melted. Here, examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and γ-methacryloxypropylmethoxysilane. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

  Furthermore, a boron compound can be blended with the EVOH-based resin in order to improve the stability when heated and melted within a range that does not interfere with the object of the present invention. Examples of the boron compound include boric acids, boric acid esters, borates, and borohydrides. Specifically, examples of boric acids include orthoboric acid, metaboric acid, and tetraboric acid. Examples of boric acid esters include triethyl borate and trimethyl borate. Examples of boric acid salts include those described above. Examples include alkali metal salts, alkaline earth metal salts, and borax of various boric acids. Among these compounds, orthoboric acid (hereinafter sometimes simply referred to as boric acid) is preferable.

  When a boron compound is blended with an EVOH-based resin, the content of the boron compound is preferably 20 to 2000 ppm, more preferably 50 to 1000 ppm in terms of boron element. By blending the boron compound within this range, it is possible to obtain an EVOH-based resin in which torque fluctuation during heating and melting is suppressed. If the content of the boron compound is too small, the effect of addition is small, and if it is too large, gelation tends to occur and the moldability may be poor.

  Furthermore, other ethylenically unsaturated monomers may be copolymerized in addition to ethylene and vinyl ester monomers as long as the effects of the present invention are not inhibited. Other ethylenically unsaturated monomers include, for example, olefins such as propylene, 1-butene, isobutene, 3-buten-1-ol, 4-penten-1-ol, 5-hexene-1,2- Hydroxyl group-containing α-olefins such as diols, derivatives thereof such as esterified products and acylated products, acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, etc. Examples thereof include saturated acids or salts thereof, mono- or dialkyl esters having 1 to 18 carbon atoms, and the like.

  Furthermore, the EVOH-based resin used in the present invention may be “post-modified” such as urethanization, acetalization, cyanoethylation, oxyalkyleneation and the like by a known method.

  Further, as the EVOH resin, it is also preferable to use an EVOH resin having a 1,2-diol structure in the side chain, and the content of the side chain 1,2-diol structure is preferably 0.01 to 20 mol%. It is preferable at the point which forms a resin layer, and 0.2-15 mol% is especially preferable, and also 0.5-10 mol% is preferable.

  Among the EVOH-based resins, in the present invention, it is preferable in terms of adhesiveness to use an EVOH-based resin having a 1,2-diol structure in the side chain.

  These EVOH resins can be used alone or in a mixture of two or more.

  In the present invention, the vinyl alcohol resin is laminated on the vapor deposition layer (B) to form the vinyl alcohol resin layer (C). Usually, the vinyl alcohol resin concentration is used as a stock solution for lamination. Is prepared in an amount of 5 to 70% by weight, preferably 10 to 60% by weight. For example, when the vinyl alcohol-based resin is a PVA-based resin, the concentration is usually adjusted with water, and when the vinyl alcohol-based resin is an EVOH-based resin, the concentration is usually adjusted with a mixed solvent of water-alcohol, particularly water-lower alcohol.

  Such a vinyl alcohol resin solution includes a plasticizer of polyhydric alcohols such as ethylene glycol, glycerin, polyethylene glycol, diethylene glycol, and triethylene glycol, and an antioxidant such as phenol and amine as long as the effects of the present invention are not impaired. Normal additives such as additives, stabilizers such as phosphate esters, colorants, fragrances, extenders, defoamers, release agents, UV absorbers, inorganic powders, surfactants, etc. Absent. Moreover, you may mix other water-soluble resins other than PVA-type resin, such as starch, carboxymethylcellulose, methylcellulose, and hydroxymethylcellulose.

  As for the method of laminating the vinyl alcohol resin layer (C), for example, (1) The vinyl alcohol resin resin is applied to the vapor deposition layer (B) with a gravure coater and dried. Examples of the coating method include a method of forming the layer (C) and a method of (2) melt extrusion of a vinyl alcohol resin using an extruder, and a method of forming the layer. Among them, the thickness uniformity of the resin layer (coat layer) From the viewpoint, the method (1) is preferable.

  The thickness of the vinyl alcohol resin layer (C) is preferably 0.5 to 30 μm, particularly preferably 1 to 28 μm. Furthermore, when the vinyl alcohol resin layer (C) is formed by a coating method. Is preferably 2 to 10 μm, in particular 3 to 8 μm. If the thickness of the vinyl alcohol resin layer (C) is too thin, the gas barrier property is lowered and the adhesion between the vapor deposition layer (B) and the vinyl alcohol resin film (D) tends to be lowered. The flexibility of the resin layer is impaired, and peeling tends to occur.

  The vinyl alcohol resin film used in the present invention (D) is a film for further improving gas barrier properties.

  Such a vinyl alcohol-based resin film (D) can be formed using the same one as the above-mentioned vinyl alcohol-based resin, and specific examples include a PVA-based resin and an EVOH-based resin.

  In the present invention, the average polymerization degree of the PVA resin used for the vinyl alcohol resin film (D) is preferably 1100 or more and the average saponification degree is 90 mol% or more, and the more preferable range of the average polymerization degree is 1100. ˜4000, particularly preferred range is 1200 to 2600, more preferred range of average saponification degree is 95 to 100 mol%, and particularly preferred range is 99 to 100 mol%. If the average degree of polymerization is too low, the mechanical strength of the film tends to be reduced, and if the average degree of polymerization is too high, the workability during film formation and stretching tends to be reduced. When the average saponification degree is too low, the water resistance is lowered, and the change of the gas barrier property due to humidity tends to be remarkable. The average polymerization degree and average saponification degree are measured according to JIS K6726.

Moreover, as a viscosity of the 4 weight% aqueous solution of the said PVA-type resin, 2.5-100 mPa * S (20 degreeC) is preferable, Furthermore, 2.5-70 mPa * s (20 degreeC), Especially 2.5- 60 mPa · s (20 ° C.) is preferable. If the viscosity is too low, mechanical properties such as film strength tend to decrease, and if it is too high, film-forming properties on the film tend to decrease.
The viscosity is measured according to JIS K6726.
These PVA resins can be used alone or in combination of two or more.

In the present invention, the ethylene content of the EVOH-based resin used for the vinyl alcohol-based resin film (D) is usually 20 to 60 mol%, and from the viewpoint of obtaining good stretchability, the ethylene content is 25 mol% or more, Furthermore, it is especially preferable that it is 30 mol% or more. From the viewpoint of gas barrier properties, the ethylene content is particularly preferably 55 mol% or less, and more preferably 50 mol% or less. If the ethylene content is too small, the melt moldability tends to decrease, and if it is too large, the gas barrier property tends to decrease.
In addition, the ethylene content of the EVOH resin can be obtained by a nuclear magnetic resonance (NMR) method.

Further, the average saponification degree of such EVOH-based resin is preferably 90% or more, more preferably 95% or more, and further preferably 99% or more. If the average saponification degree is too low, gas barrier properties under high humidity tend to be reduced.
A suitable MFR (230 ° C., 2160 g load) of such EVOH-based resin is usually 1 to 50 g / 10 minutes, more preferably 3 to 40 g / 10 minutes, and further preferably 5 to 30 g / 10 minutes. .
These EVOH resins can be used alone or in combination of two or more.

  In the present invention, the vinyl alcohol resin is used to form a film. However, such a film forming method may be a known one. For example, a vinyl alcohol resin solution is allowed to flow on a metal surface such as a drum or an endless belt. The film is formed by a cast molding method in which a film is formed by stretching, or a melt molding method in which melt extrusion is performed by an extruder.

  Such a vinyl alcohol-based resin film may be used as an unstretched film, but is usually preferably used as a uniaxially stretched film or a biaxially stretched film, and particularly preferably used as a biaxially stretched film from the viewpoint of gas barrier properties. The stretching ratio in the flow direction (MD direction) of the uniaxially or biaxially stretched film is preferably 2.5 to 5 times.

  Such a stretching treatment method can be performed according to a known method such as a uniaxial stretching method that is usually performed, simultaneous biaxial stretching, and sequential biaxial stretching.

  In the present invention, among such biaxially stretched vinyl alcohol resin films, a biaxially stretched PVA film and a biaxially stretched EVOH film are particularly preferably used, and a biaxially stretched PVA film is particularly preferably used. Hereinafter, the specific manufacturing method of these biaxially stretched films is demonstrated.

  First, the biaxially stretched PVA film will be described.

  A PVA-based film (PVA-based film before stretching) is formed using the PVA-based resin. Usually, a PVA-based resin concentration is 5 to 70% by weight, preferably as a stock solution for film formation. A composition of 10 to 60% by weight of PVA resin-water is prepared.

  Such PVA-based resin-water compositions include plasticizers of polyhydric alcohols such as ethylene glycol, glycerin, polyethylene glycol, diethylene glycol, and triethylene glycol, phenolic, amine-based, and the like as long as the effects of the present invention are not impaired. Add appropriate additives such as antioxidants, stabilizers such as phosphate esters, colorants, fragrances, extenders, defoamers, release agents, UV absorbers, inorganic powders, surfactants, etc. There is no problem. Moreover, you may mix other water-soluble resins other than PVA-type resin, such as starch, carboxymethylcellulose, methylcellulose, and hydroxymethylcellulose.

  The method for forming the PVA film is not particularly limited, but after the PVA resin-water composition is supplied to an extruder and melt-kneaded, the film is extruded by the T-die method or the inflation method and dried. Is preferred.

  The melt kneading temperature in the extruder in such a method is preferably 50 to 170 ° C, particularly 55 to 160 ° C. If the temperature is too low, the film skin will be defective, and if it is too high, the foaming phenomenon tends to occur. Moreover, about the drying of the film after film forming, it is preferable to carry out at 70-120 degreeC, and also it is preferable to carry out at 80-100 degreeC.

The biaxially stretched PVA film preferably used in the present invention is obtained by further biaxially stretching the PVA film obtained above.
For such biaxial stretching, the stretching ratio in the machine flow direction (MD direction) is preferably 2.5 to 5 times, and the stretching ratio in the width direction (TD direction) is preferably 2 to 4.5 times, particularly preferably. The MD has a stretching ratio of 3 to 5 times, and the TD direction has a stretching ratio of 2.5 to 4.5 times. If the draw ratio in the MD direction is too low, it is difficult to improve physical properties due to stretching and the heat resistance tends to be impaired. If it is too high, the film tends to tear in the MD direction. Further, if the stretching ratio in the TD direction is too low, it is difficult to obtain physical properties by stretching, and the heat resistance tends to be impaired. If it is too high, breakage during stretching tends to occur frequently when the film is industrially produced. is there.

  In performing such sequential biaxial stretching or simultaneous biaxial stretching, it is preferable to adjust the water content of the PVA-based film to 5 to 30% by weight, particularly 20 to 30% by weight. The moisture content can be adjusted by a method in which the PVA film before drying is subsequently dried, a method in which a PVA film having a moisture content of less than 5% by weight is immersed in water, or is conditioned. Even if the moisture content is too low or too high, there is a tendency that the stretching ratio in the MD direction and the TD direction cannot be increased in the stretching process.

  Furthermore, after performing biaxial stretching, it is preferable to perform heat setting, and the temperature of such heat setting is preferably selected to be lower than the melting point of the PVA-based resin, particularly 140 to 250 ° C. Is preferred. When the heat setting temperature is lower than the melting point by 80 ° C. or more, the dimensional stability tends to be poor and the shrinkage rate tends to be large. The heat setting time is preferably 1 to 30 seconds, and more preferably 5 to 10 seconds.

  In addition, for the purpose of further reducing the heat deformability, it is possible to subject the biaxially stretched PVA-based film to contact with an aqueous solution and to drying as necessary. In the contact with the aqueous solution, an aqueous solution of usually 5 to 60 ° C., preferably 10 to 50 ° C. is used, and the contact time with the aqueous solution is appropriately selected according to the temperature of the aqueous solution, but industrially 10 to 10 ° C. Preferably it is 60 seconds.

  Examples of the contact method with an aqueous solution include immersion in an aqueous solution, spraying of an aqueous solution, application of an aqueous solution, steam treatment, and the like, and these can be used in combination. After contact with the aqueous solution, industrially, it is preferable to remove the adhering water on the surface in a non-contact manner with an air shower or the like, and then to remove the moisture in a contact manner with a nip roll or the like. Moreover, as a kind of dryer, the method of using a non-contact dryer etc. etc. etc. which are directly contacted with a metal roll, a ceramic roll, etc., for example, are mentioned, for example.

When the obtained biaxially stretched PVA-based film is wound up again after the contact with the aqueous solution and drying, the water content of the film is usually 3% by weight or less, preferably 0.1 to 2% by weight. % Is desired. If the amount of moisture is too large, the films tend to adhere to each other in the film roll, and there is a risk of problems such as damage to the film when unwinding for processing again.
Thus, a biaxially stretched PVA film suitably used in the present invention is obtained.

Next, the biaxially stretched EVOH film will be described.
An EVOH film (an EVOH film before stretching) is formed using the EVOH resin.

When forming an EVOH film using the EVOH resin, melt molding is mainly used. The melt molding method will be described below.
The conditions at the time of melt molding are not particularly limited, but are usually formed by extrusion using a non-vented, screw-type extruder at a melting temperature of 190 to 250 ° C. Usually, a screw having a compression ratio of 2.0 to 4.5 is used to form a film using a T die or a round die.

  Thus, an EVOH film can be obtained, and the film can be further biaxially stretched, preferably sequentially biaxially stretched to obtain a biaxially stretched EVOH film.

  The area ratio of such biaxial stretching is preferably 3 times or more, more preferably 6 times or more, and particularly preferably 9 times or more from the viewpoint of gas barrier properties and mechanical strength. The upper limit is usually 25 times. As a stretching method, a known stretching method such as a uniaxial or biaxial stretching method such as a double bubble method, a tenter method, a roll method, etc. can be adopted. In the case of biaxial stretching, either simultaneous stretching or sequential stretching can be used. This method can also be adopted.

  Moreover, easy continuous stretching is possible by pre-hydrating the original film before stretching, and the moisture content of the original film before stretching is preferably 2 to 30% by weight, particularly 5 to 30% by weight. % Is preferable, and further 10 to 30% by weight is preferable. If the moisture content is too low, stretch spots are likely to remain, and particularly when stretched with a tenter, the stretch ratio in the portion close to the grip becomes high, so that tearing near the grip may easily occur. On the other hand, if the moisture content is too high, the elastic modulus of the stretched portion is low, the difference from the unstretched portion is not sufficient, and stretched spots may remain easily.

  The stretching temperature varies somewhat depending on the moisture content of the original film before stretching, but a range of 50 to 130 ° C. is generally applicable. Particularly in simultaneous biaxial stretching, a biaxially stretched EVOH-based film with little thickness unevenness is easily obtained in the range of 70 to 100 ° C., and in sequential biaxial stretching, 70 to 100 ° C. in longitudinal stretching with a roll. By performing the stretching in the width direction with a tenter in the temperature range of 80 to 120 ° C., a biaxially stretched EVOH-based film with few thickness spots is easily obtained.

Further, further important factors relating to the production of the biaxially stretched EVOH film include the heat treatment after stretching, and the density and moisture content of the biaxially stretched EVOH film obtained as a result of the heat treatment. The heat treatment is preferably performed at a temperature 5 to 40 ° C. lower than the melting point of EVOH for 5 to 20 seconds. If the heat treatment temperature is too low, the heat treatment is insufficient, so that heat resistance sufficient to withstand the vapor deposition process and sufficient gas barrier properties may not be obtained. On the other hand, if the heat treatment temperature is too high, the stretching effect may be partially reduced.
Thus, a biaxially stretched EVOH film suitably used in the present invention is obtained.

In the present invention, the vinyl alcohol resin film (D) may be subjected to a vapor deposition treatment for vapor deposition of metal or metal oxide.
The vapor deposition layer may be obtained by a single vapor deposition process or may be obtained by repeating the vapor deposition process a plurality of times.

  The thickness of the vapor deposition layer formed by vapor deposition of such metal or metal oxide is preferably 200 to 1000 mm, particularly preferably 300 to 800 mm. If the thickness of the deposited layer is too thin, thermal radiation characteristics tend to be difficult to obtain, and if too thick, the deposition time for obtaining the thickness is too long, and the thermal influence during deposition tends to be too great. , Industrially unfavorable.

  In addition, it is possible to pre-treat the surface of the film before subjecting the vinyl alcohol-based resin film (D) to vapor deposition treatment. And a method of forming a thin film layer with a coating agent using a polyester resin or a polyether resin as a main ingredient and using a urethane-based curing agent.

  The thickness of the vinyl alcohol resin film (D) used in the present invention is usually 5 to 100 μm, preferably 8 to 50 μm, particularly preferably 10 to 30 μm, which is advantageous in terms of industrial productivity. is there. The thickness of the film when using the biaxially stretched PVA film is preferably 5 to 50 μm, particularly preferably 8 to 30 μm, and more preferably 10 to 20 μm, and the film when using the biaxially stretched EVOH film. The thickness is preferably 5 to 50 μm, particularly preferably 10 to 40 μm, and further preferably 10 to 30 μm. If the thickness is too thick, the cost is increased industrially and the laminate [I] formed by laminating becomes too hard, the shape following property at the time of vacuum packaging is lowered, and partly damaged in some cases. There is a tendency for the possibility to increase, and if it is too thin, there is a tendency that a part of the film is damaged or an extreme thin film portion is generated, and it becomes difficult to obtain necessary barrier properties.

  In the present invention, as a method of laminating the vinyl alcohol resin film (D), for example, there is a wet laminating method using an adhesive of an aqueous solution in which a polyvinyl alcohol resin is dissolved. For example, water or polyvinyl alcohol resin is used. There is a wet laminating method using a dissolved aqueous solution, but it is not limited to this method.

  In general, the seal layer (E) in the present invention is preferably a layer composed of a polyolefin resin layer from the viewpoint of seal strength, and among them, polypropylene, high density polyethylene, and low density polyethylene are preferably used. In addition to polyolefin resins, ethylene-vinyl acetate copolymers and the like are also preferably used.

In the present invention, when forming the sealing layer (E), (1) using the resin forming the sealing layer, a separate film may be prepared and further laminated on the inner surface of the outer bag. Moreover, (2) Although it can also laminate | stack by the melt extrusion formation directly on the surface used as the inner side of an exterior bag, (1) is more preferable at the point of a sealing performance.
The thickness of the sealing layer (E) is usually 10 to 100 μm, particularly preferably 20 to 80 μm. If it is too thin, the sealing strength tends to decrease, and if it is too thick, gas penetration from the end face of the sealing layer is promoted. As a result, gas barrier properties tend to decrease.

  Thus, it has a layer structure of base film (A) / deposition layer (B) made of metal or metal oxide / vinyl alcohol resin layer (C) / vinyl alcohol resin film (D) / sealing layer (E). A laminate [I] is obtained. The overall thickness of the laminate [I] is usually from 30 to 900 μm, particularly preferably from 50 to 600 μm.

Moreover, although the laminated body [I] of this invention has said layer structure, you may have other layers, such as an adhesive agent (or adhesive) layer, between each layer further.
For example, when the sealing layer (E) is laminated as a film, it is also preferable to form an adhesive layer between the vinyl alcohol resin film (D) and the sealing layer (E). Examples of the adhesive serving as the adhesive layer include organic titanium compounds, isocyanate compounds, polyester compounds, and the like.

  The exterior bag for a vacuum heat insulating structure according to the present invention comprises a base film (A) / a vapor deposition layer (B) made of a metal or a metal oxide / a vinyl alcohol resin layer (C) / a vinyl alcohol resin film (D) / Although it includes the laminate [I] having the layer structure of the seal layer (E), it is also preferable to laminate the protective film (F) on the outside of the base film (A).

  The protective film (F) used in the present invention is a film used for the purpose of protecting the laminate [I], and examples thereof include a polyester film, a polyamide film, a polyolefin film, and a polyurethane film. . Among them, it is preferable to use a polyolefin film, preferably a polypropylene film, a polyvinyl chloride film, a polyvinylidene chloride film, or a fluorine film, in order to reduce water vapor reaching the main barrier layer.

A general-purpose polyolefin film can be used as the polyolefin film.
For example, homopolymers such as polypropylene, polybutene-1, high-density polyethylene, medium-density polyethylene, and low-density polyethylene may be mentioned, as well as ethylene, butene-1, pentene-1, 4-methylpentene-1 having propylene as a main component. , Hexene-1, octene-1, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1,4-hexadiene, copolymers with styrene, and also grafted with carboxylic acid such as maleic anhydride A modified one, a copolymer of ethylene, propylene, butene-2, isobutylene, butadiene, pentene-1, 4-methylpentene-1, hexene-1, octene-1 and the like mainly containing butene-1; Furthermore, ethylene is the main component that is graft-modified with carboxylic acid such as maleic anhydride. Propylene, butene-1, 4-methylpentene-1, 1-hexene, 1-octene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, styrene, vinyl acetate, methyl acrylate, acrylic acid Examples thereof include copolymers with ethyl, acrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid, glycidyl methacrylate, and the like and graft-modified with carboxylic acids such as maleic anhydride. Among these, it is particularly preferable to use polypropylene from the viewpoint of moisture resistance and industrial productivity.

  Further, it is also preferable to perform a stretching treatment and use a uniaxially stretched or biaxially stretched polyolefin film, and in particular, a biaxially stretched polyolefin film is preferably used from the viewpoint of obtaining a higher gas barrier property with a thinner film.

  The thickness of the protective film (F) is usually 5 to 200 μm, and particularly preferably 10 to 100 μm. If the film thickness is too thin, the filling property of the heat insulating material that becomes the core material of the vacuum heat insulating structure obtained is lowered, and if it is too thick, not only the workability is lowered but also economically disadvantageous.

Furthermore, the protective film (F) preferably has an initial elastic modulus of 1 to 100 GPa, more preferably 0.5 to 50 GPa, and a water vapor permeability of 10 g / m ² / day or less, further 8 g / m ² / It is preferably not more than day. The initial elastic modulus is 23 ° C. × 60% r.D. measured in accordance with JIS K 7127. h. The water vapor permeability is a value at 23 ° C. × Δ90% RH measured according to JIS Z 0208.

  Next, a vacuum heat insulating structure body in which a heat insulating material is hermetically packaged with the outer bag for a vacuum heat insulating structure and the vacuum bag for a heat insulating body containing the laminate [I] will be described.

  When forming an exterior bag with a laminated body, for example, an exterior bag can be obtained by bonding the seal layers together by heat welding with the seal layer of the laminate inside.

As a preferable layer structure of the outer bag for a vacuum heat insulating structure of the present invention containing the laminate [I] of the present invention, the outer layer side (the side opposite to the heat insulating material) from the viewpoint of gas barrier properties and moisture resistance. From, for example,
(1): Protective film (F) // (Adhesive layer) // PET film (A) / Aluminum vapor deposition layer (B) // Vinyl alcohol resin layer (C) // Vinyl alcohol resin film (D) // Seal layer (E)
(2): Protective film (F) // (Adhesive layer) // PET film (A) / Aluminum deposition layer (B) // Vinyl alcohol resin layer (C) // Vinyl alcohol resin film (D) // (Adhesive layer) // Seal layer (E)
Etc.

  As the heat insulating material sealed and packaged in the outer bag made of the laminate [I], for example, a polymer having open cells inside, or a fine powder of inorganic or metal is preferably used, and the inside of the outer bag is evacuated. However, the shape can be maintained. When the inside of the outer bag is evacuated and the opening is sealed, the heat insulating effect of the vacuum heat insulating structure is obtained when the polymer of the heat insulating material does not have bubbles or has closed cells. Reduced and not preferable.

  Specific examples of the heat insulating material include urethane foam, carbon foam, phenol foam, phenol-urethane foam, etc., polymer having open cells, fine powder such as alumina, silica, perlite, glass wool, rock wool, diatomaceous earth. Examples of the molded body include soil and calcium silicate.

  Among these, fibrous heat-insulating materials such as glass wool, granular heat-insulating materials such as granular silicon oxide and foamed resin bodies can retain the shape even when the inside of the outer bag is evacuated, and have bubbles. Therefore, it is preferable in that the heat insulating effect of the vacuum heat insulating structure can be maintained.

  In addition, since such a heat insulating material may cause a decrease in the degree of vacuum due to moisture, it is also preferable to use a mixture of a desiccant such as quick lime, calcium chloride, and calcium oxide.

The heat insulating material is put in an outer bag made of the laminate [I] and vacuum-packed to form a vacuum heat insulating structure. When the heat insulating material is put in the outer bag, the heat insulating material is predetermined. It is preferable to form in the shape (for example, a cube, a rectangular parallelepiped, etc.) in terms of heat insulation performance and workability.
In the present invention, the vacuum heat insulating structure can be obtained by reducing the pressure in a state where the heat insulating material is put in the outer bag and finally sealing and closing the opening of the bag. The degree of vacuum of the vacuum heat insulating structure is not particularly limited, but is preferably 100 Pa or less, more preferably 10 Pa or less, and particularly preferably 5 Pa or less.

  In the present invention, the shape and size of the vacuum heat insulating structure are not particularly limited, and may be determined according to the purpose. For example, the shape of the vacuum heat insulating structure may be a shape in which one outer bag made of a laminated body is included for one vacuum heat insulating structure, or a plurality of outer bags may be provided for one vacuum heat insulating structure. The thing of the shape contained may be sufficient.

In the case of a shape including a plurality of such exterior bags, the seal part that becomes a joint between the exterior bag parts becomes a thin part in the vacuum heat insulation structure, and deformation when the vacuum heat insulation structure is deformed Therefore, the vacuum heat insulating structure can be easily deformed, which is preferable.
Furthermore, even when a hole or the like is generated due to an external factor, and the vacuum property of the vacuum heat insulating structure is lost, the decrease in the heat insulating property is kept to a minimum if the shape includes a plurality of exterior bags. Can be preferable.

  As for the size of such a vacuum heat insulating structure, it is often processed into a rectangular parallelepiped shape having a thickness of 5 to 100 mm and a length and width of 100 to 1000 mm. If the volume of the vacuum insulation structure is unnecessarily large, the area that loses performance increases when a defect such as a hole occurs in the outer bag, which may reduce the performance of the final product using the vacuum insulation structure. Therefore, it is preferable to set the size appropriately.

  Thus, in the present invention, a vacuum heat insulating structure having excellent adhesion between the vapor deposition layer of the vapor deposition base film and the layer laminated thereon and excellent heat insulation performance even when used for a long period of time can be obtained. Such vacuum heat insulating structures include household appliances such as cooler boxes and bottle cases, household appliances such as refrigerators, jar pots, rice cookers, housing equipment such as water heaters, bathtubs, unit baths, toilet seats, floor heating, solar roofs, Although it can be effectively used as a heat insulating material for a housing system such as a low-temperature radiation plate and a housing building material such as a heat insulating panel for an outer wall, among them, it can be particularly suitably used as a heat insulating material for a refrigerator.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the examples, “parts” and “%” mean weight basis.

<Preparation of vinyl alcohol resin solution for forming vinyl alcohol resin layer (C)>
(PVA resin solution (1))
20 parts of PVA (average degree of polymerization 1700, average degree of saponification 98.0 mol%) was dispersed in 80 parts of water, the temperature was raised to 98 ° C. or higher with stirring, and the temperature was maintained at 98 ° C. and 30 parts. Stirring was continued for 5 minutes, and 5 parts of polyethylene glycol # 600 (manufactured by Toho Chemical Co., Ltd.) was added dropwise to obtain a PVA resin solution (1).

(EVOH resin solution (2))
Ethylene-vinyl alcohol resin (ethylene content 29 mol%, average degree of saponification 99.5 mol%, MFR = 3.5 g / min (210 ° C., load 2160 g), boric acid content (boron conversion) 0.015 weight Part, calcium dihydrogen phosphate content 0.005 part by weight (in terms of phosphoric acid)) was added to a mixed solvent of water: isopropanol = 1: 1 (weight ratio) so that the concentration was 15%, and refluxed. The mixture was stirred in a separable flask equipped with a tube to obtain an EVOH resin solution (2).

(Side-chain 1,2-diol structure-containing PVA resin solution (3))
A reaction vessel equipped with a reflux condenser, a dropping funnel and a stirrer was charged with 1000 g of vinyl acetate, 1500 g of methanol, and 100 g of 3,4-diacetoxy-1-butene, and 0.7 mol% of azobisisobutyronitrile (vs. acetic acid charged). Vinyl monomer) was added, and the temperature was increased while stirring under a nitrogen stream to initiate polymerization. Polymerization was performed until the polymerization rate of vinyl acetate reached 90%. When the polymerization rate reached 90%, 300 ppm of m-dinitrobenzene (as opposed to the charged vinyl acetate monomer) was charged as a polymerization inhibitor to complete the polymerization.
Subsequently, unreacted vinyl acetate monomer was removed from the system by a method of blowing methanol vapor to obtain a methanol solution of vinyl acetate-3,4-diacetoxy-1-butene copolymer.

  The methanol solution of the copolymer was adjusted to a 40% concentration methanol solution and charged into a kneader, and a 2% methanol solution of sodium hydroxide was combined with vinyl acetate and 3,4-diacetoxy-1-butene in the copolymer in a total amount of 1 It added in the ratio which will be 14 millimoles with respect to mol, saponification was performed maintaining the solution temperature at 40 degreeC, and the particulate saponified material was obtained.

  The obtained saponified product was separated by filtration, washed with methanol, and then dried in a hot air dryer to obtain a side chain 1,2-diol structure-containing PVA resin.

  The average degree of saponification of the obtained side chain 1,2-diol structure-containing PVA resin was analyzed by the alkali consumption required for hydrolysis of residual vinyl acetate and 3,4-diacetoxy-1-butene. The content of mol%, average polymerization degree 450 (measured according to JIS K 6726), and 1,2-diol structure was 5 mol%. For NMR measurement, “AVANCEDPX400” manufactured by Nippon Bruker Co., Ltd. was used.

  20 parts of the PVA resin containing the side chain 1,2-diol structure obtained above was dispersed in 80 parts of water, the reaction temperature was raised to 98 ° C. or higher while stirring, and then maintained at 98 ° C. for 30 minutes. Stirring was continued, and 5 parts of polyethylene glycol # 600 (manufactured by Toho Chemical Co., Ltd.) was added dropwise to obtain a side chain 1,2-diol structure-containing PVA resin solution (3).

(Side-chain 1,2-diol structure-containing EVOH resin solution (4))
A 1 m ³ polymerization can with a cooling coil is charged with 500 kg of vinyl acetate, 100 kg of methanol, 500 ppm of acetyl peroxide (vs. vinyl acetate), 20 ppm of citric acid (vs. vinyl acetate), and 14 kg of 3,4-diacetoxy-1-butene. After replacing the system once with nitrogen gas, it is then replaced with ethylene, injected until the ethylene pressure reaches 35 kg / cm ² , stirred and then heated to 67 ° C. until the polymerization rate reaches 50%. Polymerized for 6 hours. Thereafter, the polymerization reaction was stopped to obtain an ethylene-vinyl acetate-diacetoxybutene copolymer having an ethylene content of 29 mol%.

  Saponification is carried out by supplying a methanol solution containing 0.012 equivalents of sodium hydroxide to the methanol solution of the ethylene-vinyl acetate-diacetoxybutene copolymer with respect to the remaining acetate groups in the copolymer. To obtain a methanol solution of EVOH resin (1.0% EVOH resin, 70% methanol) containing 1.0 mol% of a structural unit having a side chain 1,2-diol structure. The average saponification degree of the vinyl acetate portion of the EVOH resin was 99.5 mol%.

  Subsequently, the obtained methanol solution of the side chain 1,2-diol structure-containing EVOH was supplied from the top of the methanol / water solution adjusting tower at 10 kg / hour, methanol vapor at 120 ° C. was 4 kg / hour, and steam was 2.5 kg. At the same time, methanol is distilled from the top of the tower at a rate of 8 kg / hour, and at the same time, 6 equivalents of methyl acetate with respect to the amount of sodium hydroxide used in the saponification is 95-110 ° C. A water / methanol solution of EVOH (resin concentration: 35%) was obtained from the bottom of the column.

  The obtained water / methanol solution of the side chain 1,2-diol structure-containing EVOH resin was put into cold water from a nozzle with a pore diameter of 4 mm, and the strand was put into a coagulation liquid tank maintained at 5 ° C. composed of 5% methanol and 95% water. The resulting strand (water-containing porous material) was cut with a cutter, and the porosity of EVOH resin containing side chain 1,2-diol structure having a diameter of 3.8 mm and a length of 4 mm and a water content of 45% was obtained. Pellets were obtained.

  After washing with 100 parts of water with respect to 100 parts of the porous pellets, the mixture was put into a mixed solution containing 0.032% boron and 0.007% calcium dihydrogen phosphate and stirred at 30 ° C. for 5 hours. did. Further, the porous pellets are dried in a batch-type ventilated box type dryer with nitrogen gas having a temperature of 70 ° C. and a moisture content of 0.6% for 12 hours to pellets of EVOH resin containing side chain 1,2-diol structure. Got.

  Such pellets contained 0.015 parts by weight of boric acid (in terms of boron) and 0.005 parts by weight of phosphoric acid (in terms of phosphoric acid) with respect to 100 parts by weight of EVOH containing the side chain 1,2-diol structure.

  The MFR of this side chain 1,2-diol structure-containing EVOH resin was 4.0 g / 10 min (210 ° C., load 2160 g).

  The content of the side chain 1,2-diol structure was calculated by measuring the ethylene-vinyl acetate copolymer before saponification with 1H-NMR (internal standard substance: tetramethylsilane, solvent: d6-DMSO). 2.5 mol%. In addition, “AVANCE DPX400” manufactured by Nippon Bruker Co., Ltd. was used for NMR measurement.

  The side chain 1,2-diol structure-containing EVOH resin pellets obtained above were added to a mixed solvent of water: isopropanol = 1: 1 (weight ratio) so that the concentration would be 15%, and a reflux tube was attached. The side-chain 1,2-diol structure-containing EVOH resin solution (4) was obtained.

<Base film (A) / Preparation of vapor deposition layer (B) made of metal or metal oxide>
Aluminum vapor-deposited PET film having an aluminum vapor-deposited layer with a thickness of 400 mm on one side of a polyethylene terephthalate film (“Tetron PC” manufactured by Teijin Ltd., film thickness: 12 μm) using a vacuum vapor deposition device using an electron beam heating method. Got.

<Preparation of Base Film (A) / Vapor Deposition Layer (B) / Vinyl Alcohol Resin Layer (C) Made of Metal or Metal Oxide>
(Intermediate laminate containing PVA resin layer (A))
The PVA resin solution (1) is applied on the aluminum vapor-deposited surface of the aluminum vapor-deposited PET film with a gravure coater to a thickness of 25 μm before drying, and dried at 100 ° C. for 3 minutes to form a PVA resin layer having a thickness of 5 μm. An intermediate laminate (a) having was obtained.

(Intermediate laminate (EV) having EVOH resin layer)
The EVOH resin solution (2) is applied on the aluminum vapor-deposited surface of the aluminum vapor-deposited PET film with a gravure coater so as to have a thickness of 25 μm before drying, and this is dried at 80 ° C. for 3 minutes. An intermediate laminate (I) having a layer was obtained.

(Intermediate laminate having a side chain 1,2-diol structure-containing PVA resin layer (U))
On the aluminum vapor-deposited surface of the aluminum vapor-deposited PET film, the side chain 1,2-diol structure-containing PVA resin solution (3) is applied with a gravure coater to a thickness of 25 μm before drying, and dried at 100 ° C. for 3 minutes. Thus, an intermediate laminate (U) having a side chain 1,2-diol structure-containing PVA resin layer having a thickness of 5 μm was obtained.

(Intermediate laminate having a side chain 1,2-diol structure-containing EVOH resin layer (D))
On the aluminum vapor-deposited surface of the aluminum vapor-deposited PET film, the side chain 1,2-diol structure-containing EVOH resin solution (4) is applied with a gravure coater to a thickness of 25 μm before drying, and this is dried at 80 ° C. for 3 minutes. As a result, an intermediate laminate (d) having a side chain 1,2-diol structure-containing EVOH resin layer having a thickness of 5 μm was obtained.

(Intermediate laminate having side chain 1,2-diol structure-containing PVA resin layer (v))
The PVA resin containing the side chain 1,2-diol structure obtained above was supplied to a biaxial simultaneous extruder, and pelletized under the following conditions.

Screw inner diameter 30mm
L / D 30
Screw rotation speed 100rpm
Extrusion temperature C1: 185 ° C
C2: 195 ° C
C3: 195 ° C
C4: 190 ° C
H (head): 190 ° C
D (die): 190 ° C

The obtained side chain 1,2-diol structure-containing PVA resin pellets were
Screw inner diameter 40mm
L / D 25
Screw compression ratio 3.2
Screw rotation speed 20rpm
Extrusion temperature 198 ° C
The aluminum laminate PET (e) having a side chain 1,2-diol structure-containing PVA resin layer was obtained by extruding the aluminum-deposited PET film so as to have a thickness of 25 μm.

<Example 1>
(Production of laminate [I-1] having a PVA resin layer and a biaxially stretched PVA film)
Biaxially stretched polyamide film (“Harden film N2100” manufactured by Toyobo Co., Ltd., thickness 25 μm), polyester adhesive (“Takelac A-3210” manufactured by Mitsui Chemicals) / isocyanate two-component polyurethane adhesive (manufactured by Mitsui Chemicals) After applying “Takenate A-3072” = 3/1 (weight ratio) and drying at 85 ° C., the aluminum vapor-deposited polyester film of “intermediate laminate (A) containing PVA resin layer” obtained above. The protective layer (F) was formed by bonding to the surface that was not subjected to the vapor deposition treatment, and an “intermediate laminate (A ′)” containing a PVA resin layer was obtained.

Next, a corona treatment was applied to one side of a biaxially stretched PVA film (“Boblon EX” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., thickness 12 μm), and a coating amount of 1 g / m ² was applied to the treated surface with a gravure coater. Immediately after application of pure water, it was bonded to the PVA resin layer surface of the “intermediate laminate (A ′) having a PVA resin layer” obtained above, and then dried at 100 ° C. for 1 minute. Polyester / isocyanate two-component polyurethane adhesive ("Takelac A-3210" manufactured by Mitsui Chemicals, Inc./"Takenate A-3072 "manufactured by Mitsui Chemicals) = 3/1 on the biaxially stretched PVA film side of the resulting laminate. (Weight ratio)) is applied and dried at 85 ° C., and then a polypropylene film (“Pyrene CTP1128” manufactured by Toyobo Co., Ltd., 30 μm thick) is bonded to form a seal layer (E). Yo And a laminate [I-1] ”having a biaxially stretched PVA film was obtained.
Layer structure of laminate [I-1] = [biaxially stretched polyamide film / adhesive layer / polyethylene terephthalate film / aluminum deposition layer / PVA resin layer / biaxially stretched PVA film / adhesive layer / polypropylene film]

(Preparation of vacuum insulation structure (V1))
From the laminate [I-1], a sheet of 30 mm × 400 mm is cut out, and two sheets are used to overlap the seal layers. Among the four circumferences, three sides other than one short side are 1 cm wide. Heat sealing was performed at a sealing temperature of 140 ° C. to obtain a bag-shaped laminate.
The obtained bag-like laminate was dried at 80 ° C. for 2 hours, and then heat-compressed to a glass wool piece (Mag Izobale: “Magroll WD800”) having a thickness of 80 mm cut into a 20 cm square to a thickness of 10 mm. 3 g of calcium oxide-based desiccant wrapped with non-woven material and non-woven fabric, and paste the other opening in the vacuum packaging device in a vacuum degree of 2.02 Pa under the same conditions as above And the vacuum heat insulation structure (V1) using laminated body [I-1] was obtained.

  The following evaluation was performed about the obtained vacuum heat insulation structure (V1). The results are also shown in Table 1.

<Insulation evaluation 1>
The vacuum heat insulating structure (V1) was placed at 20 ° C. × 40% r. h. Deterioration of thermal conductivity due to high temperature standing W3 = (W1) where W1 is the thermal conductivity when left for 24 hours under the above conditions and W2 is the thermal conductivity when left for 5 days under the high temperature condition of 100 ° C. -W2) was obtained and the heat insulation performance was evaluated.
The thermal conductivity was measured with “HC-074-304” (manufactured by Eiko Seiki Co., Ltd.).

<Insulation evaluation 2>
The vacuum heat insulating structure (V1) evaluated in the heat insulating evaluation 1 was further added to 30 ° C. × 90% r. h. The thermal conductivity at the time of being exposed to the cycle conditions of × 12 hours and 70 ° C. × 12 hours 10 times was defined as W4, further thermal conductivity deterioration W5 = (W1−W4) was determined, and the heat insulation performance was evaluated.
The thermal conductivity was measured with “HC-074-304” (manufactured by Eiko Seiki Co., Ltd.).

<Adhesion evaluation>
The vacuum heat insulating structure (V1) having undergone the heat resistance evaluation 2 is dismantled and has an acute angle of 15 degrees from the bag-like laminate made of the laminate [I-1] used therein, and has a long side. Cut into a 150 mm isosceles triangle, and heat-fuse a resin film having the same composition as the resin forming each surface on one surface and the other surface of the acute-angled tip. Pulled so as to spread perpendicularly to the surface direction of [I-1], peeling length (distance: mm) of the adhesion surface of the vapor deposition layer (B) and the vinyl alcohol-based resin film (D) of the laminated portion of the acute angle tip portion ) Was measured and the adhesion was evaluated. In addition, in the lamination | stacking part of a front-end | tip part, when peeling of 5 mm or more arises in the adhesive surface of a vapor deposition layer (B) and a vinyl alcohol-type resin film (D), adhesion | attachment with a vapor deposition layer and a vinyl alcohol-type resin film As a result, the heat insulation performance is deteriorated, and the heat insulation performance is deteriorated, so that sufficient performance as a vacuum heat insulation structure cannot be exhibited.

<Example 2>
(Production of laminate [I-2] having a PVA resin layer and a biaxially stretched EVOH film)
One side of a biaxially stretched ethylene-vinyl alcohol copolymer resin film (Kuraray "Eval XL", thickness 12 μm) is subjected to corona treatment, and 1 g / m ² is applied to the treated surface with a gravure coater. A 5% PVA resin aqueous solution having a saponification degree of 99.5% and a polymerization degree of 1700 was applied so that the amount was “immediately after the“ intermediate laminate (A ′) ”having a PVA resin layer” obtained in Example 1. After being bonded to the surface of the PVA resin layer, the laminate was dried at 100 ° C. for 1 minute, and on the biaxially stretched ethylene-vinyl alcohol copolymer resin film side of the obtained laminate, a polyester / isocyanate two-component polyurethane adhesive (Mitsui Chemicals “Takelac A-3210” / Mitsui Chemicals “Takenate A-3072” = 3/1 (weight ratio)) was applied and dried at 85 ° C. “Pyrene CTP1128” manufactured by Yobo Co., Ltd., having a thickness of 30 μm) was bonded to form a seal layer (E), and “a laminate [I-2] having a PVA resin layer and a biaxially stretched EVOH film” was obtained. .
Layer structure of laminate [I-2] = [biaxially stretched polyamide film / adhesive layer / polyethylene terephthalate film / aluminum vapor deposition layer / PVA resin layer / biaxially stretched ethylene-vinyl alcohol (EVOH) copolymer resin film / Adhesive layer / polypropylene film]

  Using the laminate [I-2] obtained above, a vacuum heat insulating structure (V2) was produced in the same manner as in Example 1, and the heat insulating evaluation was performed. Moreover, adhesiveness evaluation was performed like Example 1. FIG. The results are also shown in Table 1.

<Example 3>
(Intermediate laminate having EVOH resin layer and biaxially stretched PVA film [I-3])
Biaxially stretched polyamide film (“Harden film N2100” manufactured by Toyobo Co., Ltd., thickness 25 μm), polyester adhesive (“Takelac A-3210” manufactured by Mitsui Chemicals) / isocyanate two-component polyurethane adhesive (manufactured by Mitsui Chemicals) After applying “Takenate A-3072” = 3/1 (weight ratio) and drying at 85 ° C., an aluminum-deposited PET film of “intermediate laminate (b) containing EVOH resin layer” obtained above was obtained. The protective layer (F) was formed by bonding to the surface that was not subjected to the vapor deposition treatment, and an “intermediate laminate (A ′) containing a PVA resin layer” was obtained.

Next, corona treatment was applied to one side of a biaxially stretched PVA film (“Boblon EX” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., thickness: 12 μm), and the coating amount on the treated surface was 1 g / m ^{2 using} a gravure coater. The 5% PVA resin aqueous solution having a saponification degree of 99.5% and a polymerization degree of 1700 was applied so that the EVOH resin of the “intermediate laminate (i ′) having an EVOH resin layer” obtained above was immediately followed. After laminating with the layer surface, the laminate was dried at 100 ° C. for 1 minute, and a polyester / isocyanate two-component polyurethane adhesive (“Takelac A-3210, made by Mitsui Chemicals) was applied to the biaxially stretched PVA film side of the obtained laminate. / "Takenate A-3072" manufactured by Mitsui Chemicals Co., Ltd. = 3/1 (weight ratio)), dried at 85 ° C, and then polypropylene film ("Pyrene CTP1128" manufactured by Toyobo Co., Ltd., thickness 30 μm) ) Was formed to form a sealing layer (E), and “a laminate [I-3] having an EVOH resin layer and a biaxially stretched PVA film” was obtained.
Layer structure of laminate [I-3] = [biaxially stretched polyamide film / adhesive layer / polyethylene terephthalate film / aluminum vapor deposition layer / EVOH resin layer / biaxially stretched PVA film / adhesive layer / polypropylene film]

  Using the laminate [I-3] obtained above, a vacuum heat insulating structure (V3) was produced in the same manner as in Example 1, and the heat insulating evaluation was performed. Moreover, adhesiveness evaluation was performed like Example 1. FIG. The results are also shown in Table 1.

<Example 4>
(Preparation of laminate [I-4] having side chain 1,2-diol structure-containing PVA resin layer and biaxially stretched PVA film)
Biaxially stretched polyamide film (“Harden film N2100” manufactured by Toyobo Co., Ltd., thickness 25 μm), polyester adhesive (“Takelac A-3210” manufactured by Mitsui Chemicals) / isocyanate two-component polyurethane adhesive (manufactured by Mitsui Chemicals) After applying “Takenate A-3072” = 3/1 (weight ratio) and drying at 85 ° C., the “interlayer laminate having a side chain 1,2-diol structure-containing PVA resin layer ( A protective layer (F) is formed by bonding the aluminum-deposited PET film to the surface of the aluminum-deposited PET film of “c)”, and an intermediate laminate having a “side chain 1,2-diol structure-containing PVA resin layer ( ')'.

Next, corona treatment was applied to one side of a biaxially stretched PVA film (“Boblon EX” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., thickness: 12 μm), and the coating amount on the treated surface was 1 g / m ^{2 using} a gravure coater. Immediately after application of pure water, the side chain 1,2-diol structure of the “intermediate laminate (U ′) having a side chain 1,2-diol structure-containing PVA resin layer” obtained above is obtained. After laminating with the surface of the PVA resin layer, it was dried at 100 ° C. for 1 minute, and a polyester / isocyanate two-component polyurethane adhesive (“Takelac” manufactured by Mitsui Chemicals, Inc.) was formed on the biaxially stretched PVA film side of the obtained laminate. A-3210 "/" Takenate A-3072 "manufactured by Mitsui Chemicals Co., Ltd. = 3/1 (weight ratio)) and dried at 85 [deg.] C., followed by polypropylene film (" Pyrene CTP1128 "manufactured by Toyobo Co., Ltd., thickness 30 [mu] m) ) Was formed to form a sealing layer (E), and a “laminated body [I-4] having a side chain 1,2-diol structure-containing PVA resin layer” was obtained.
Layer structure of laminate [I-4] = [biaxially stretched polyamide film / adhesive layer / polyethylene terephthalate film / aluminum deposition layer / side chain 1,2-diol structure-containing PVA resin layer / biaxially stretched PVA film / adhesion Agent layer / polypropylene film)

  Using the laminate [I-4] obtained above, a vacuum heat insulating structure (V4) was produced in the same manner as in Example 1, and the heat insulation was evaluated. Moreover, adhesiveness evaluation was performed like Example 1. FIG. The results are also shown in Table 1.

<Example 5>
(Preparation of laminate [I-5] having side chain 1,2-diol structure-containing EVOH resin layer and biaxially stretched EVOH film)
Biaxially stretched polyamide film (“Harden film N2100” manufactured by Toyobo Co., Ltd., thickness 25 μm), polyester adhesive (“Takelac A-3210” manufactured by Mitsui Chemicals) / isocyanate two-component polyurethane adhesive (manufactured by Mitsui Chemicals) After applying “Takenate A-3072” = 3/1 (weight ratio) and drying at 85 ° C., the above-obtained intermediate laminate (with side chain 1,2-diol structure-containing EVOH resin layer ( It was bonded to the surface of the aluminum vapor-deposited PET film of “D)” which was not subjected to the vapor deposition treatment, to obtain “an intermediate laminate (D ′) having a side chain 1,2-diol structure-containing EVOH resin layer”.

Next, a corona treatment was applied to one side of a biaxially stretched ethylene-vinyl alcohol copolymer resin film (“EVAL XL” manufactured by Kuraray Co., Ltd., thickness 12 μm), and 1 g / m was applied to the treated surface with a gravure coater. 5% PVA resin aqueous solution having a saponification degree of 99.5% and a polymerization degree of 1700 was applied so that the coating amount was ² , and immediately after that, the “side-chain 1,2-diol structure-containing EVOH resin layer obtained above” was obtained. After being bonded to the side chain 1,2-diol structure-containing EVOH resin layer surface of the “intermediate laminate (D ′)”, the laminate is dried at 100 ° C. for 1 minute, and the resulting biaxially stretched ethylene-vinyl alcohol is obtained. Polyester / isocyanate two-component polyurethane adhesive (“Takelac A-3210” manufactured by Mitsui Chemicals / “Takenate A-3072” manufactured by Mitsui Chemicals = 3/1 (weight ratio)) is applied to the film side. After drying at 85 ° C., a polypropylene film (“Pyrene CTP1128” manufactured by Toyobo Co., Ltd., thickness of 30 μm) is bonded to form a seal layer (E), “EVOH containing side chain 1,2-diol structure” A laminate [I-5] having a resin layer and a biaxially stretched EVOH film was obtained.
Layer structure of laminate [I-5] = [biaxially stretched polyamide film / adhesive layer / polyethylene terephthalate film / aluminum vapor deposition layer / side chain 1,2-diol structure-containing EVOH resin layer / biaxially stretched ethylene-vinyl alcohol Copolymer film / Adhesive layer / Polypropylene film]

  Using the laminate [I-5] obtained above, a vacuum heat insulating structure (V5) was produced in the same manner as in Example 1, and the heat insulating evaluation was performed. Moreover, adhesiveness evaluation was performed like Example 1. FIG. The results are also shown in Table 1.

<Example 6>
(Production of laminate [I-6] having a side chain 1,2-diol structure-containing PVA resin layer and a biaxially stretched PVA film)
Biaxially stretched polyamide film (“Harden film N2100” manufactured by Toyobo Co., Ltd., thickness 25 μm), polyester adhesive (“Takelac A-3210” manufactured by Mitsui Chemicals) / isocyanate two-component polyurethane adhesive (manufactured by Mitsui Chemicals) After applying “Takenate A-3072” = 3/1 (weight ratio) and drying at 85 ° C., the “interlayer laminate having a side chain 1,2-diol structure-containing PVA resin layer ( It was bonded to the surface of the aluminum-deposited PET film that had not been subjected to the vapor deposition treatment of “e)” to obtain “an intermediate laminate (e ′) having a side chain 1,2-diol structure-containing PVA resin layer”.

Next, corona treatment was applied to one side of a biaxially stretched PVA film (“Boblon EX” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., thickness: 12 μm), and the coating amount on the treated surface was 1 g / m ^{2 using} a gravure coater. Immediately after the application of pure water, the side chain 1,2-diol structure of the “intermediate laminate (O ′) having a side chain 1,2-diol structure-containing PVA resin layer” obtained above is obtained. After laminating with the surface of the PVA resin layer, it was dried at 100 ° C. for 1 minute, and a polyester / isocyanate two-component polyurethane adhesive (“Takelac” manufactured by Mitsui Chemicals, Inc.) was formed on the biaxially stretched PVA film side of the obtained laminate. A-3210 "/" Takenate A-3072 "manufactured by Mitsui Chemicals Co., Ltd. = 3/1 (weight ratio)) and dried at 85 [deg.] C., followed by polypropylene film (" Pyrene CTP1128 "manufactured by Toyobo Co., Ltd., thickness 30 [mu] m) ) Was formed to form a sealing layer (E), and a “laminate [I-6] having a side chain 1,2-diol structure-containing PVA resin layer and a biaxially stretched PVA film” was obtained.
Layer structure of laminate [I-6] = [biaxially stretched polyamide film / adhesive layer / polyethylene terephthalate film / aluminum deposition layer / side chain 1,2-diol structure-containing PVA resin layer / biaxially stretched PVA film / adhesion Agent layer / polypropylene film)

  Using the laminate [I-6] obtained above, a vacuum heat insulating structure (V6) was produced in the same manner as in Example 1, and the heat insulating evaluation was performed. Moreover, adhesiveness evaluation was performed like Example 1. FIG. The results are also shown in Table 1.

<Example 7>
(Preparation of laminate [I-7] having side chain 1,2-diol structure-containing PVA resin layer and biaxially stretched EVOH film)
One side of a biaxially stretched ethylene-vinyl alcohol copolymer resin film (“Eval XL” manufactured by Kuraray Co., Ltd., thickness 12 μm) is subjected to corona treatment, and the coated surface is coated with a gravure coater at a coating amount of 1 g / m ² . Then, a 5% polyvinyl alcohol resin aqueous solution having a saponification degree of 99.5% and a polymerization degree of 1700 was applied, and immediately after that, the “side chain 1,2-diol structure-containing PVA resin layer obtained in Example 6 was applied. After pasting with the side chain 1,2-diol structure-containing EVOH resin layer surface of the “intermediate laminate (O ′)”, it is dried at 100 ° C. for 1 minute, and on the biaxially stretched PVA film side of the obtained laminate, Polyester / isocyanate two-component polyurethane adhesive (“Takelac A-3210” manufactured by Mitsui Chemicals, Inc./“Takenate A-3072 ”manufactured by Mitsui Chemicals = 3/1 (weight ratio)) is applied at 85 ° C. After drying, a polypropylene film (“Pyrene CTP1128” manufactured by Toyobo Co., Ltd., thickness 30 μm) is bonded to form a seal layer (E), and “side chain 1,2-diol structure-containing PVA resin layer and biaxial stretching A laminate [I-7] having an EVOH film ”was obtained.
Layer structure of laminate [I-7] = [biaxially stretched polyamide film / adhesive layer / polyethylene terephthalate film / aluminum deposition layer / side chain 1,2-diol structure-containing PVA resin layer / biaxially stretched ethylene-vinyl alcohol Copolymer resin film / adhesive layer / polypropylene film]

  Using the laminate [I-7] obtained above, a vacuum heat insulating structure (V7) was produced in the same manner as in Example 1, and the heat insulating evaluation was performed. Moreover, adhesiveness evaluation was performed like Example 1. FIG. The results are also shown in Table 1.

<Comparative Example 1>
On the aluminum vapor-deposited surface of the aluminum vapor-deposited PET film obtained above, a polyester-based adhesive ("Takelac A-3210" manufactured by Mitsui Chemicals) / isocyanate two-component polyurethane-based adhesive ("Takenate A-" manufactured by Mitsui Chemicals). 3072 "= 3/1 (weight ratio) was applied, dried at 85 ° C., and then bonded to a biaxially stretched PVA film (“ Boblon EX ”manufactured by Nippon Synthetic Chemical Industry Co., Ltd., thickness 12 μm), then 100 ° C. The polyester laminate / isocyanate two-component polyurethane adhesive (“Takelac A-3210” manufactured by Mitsui Chemicals, Inc./“Takenate A ”manufactured by Mitsui Chemicals, Inc.) was dried for 1 minute. −3072 ”= 3/1 (weight ratio)) and dried at 85 ° C., and then a polypropylene film (“ Pyrene CTP1128 ”manufactured by Toyobo Co., Ltd., thickness 30 μm) ) To form a seal layer (E).
Furthermore, a biaxially stretched polyamide film (“Harden film N2100” manufactured by Toyobo Co., Ltd., thickness 25 μm) and a polyester adhesive (“Takelac A-3210” manufactured by Mitsui Chemicals) / isocyanate two-component polyurethane adhesive (Mitsui Chemicals) After applying “Takenate A-3072” = 3/1 (weight ratio) manufactured by the company and drying at 85 ° C., the laminate obtained above was bonded to the surface not subjected to the vapor deposition treatment of aluminum vapor deposition PET. A laminated body [i-1] was produced, and a vacuum heat insulating structure (v1) was produced in the same manner as in Example 1 using the obtained laminated body [i-1], and the heat insulation property was evaluated. The adhesiveness was evaluated in the same manner as in Example 1. The results are also shown in Table 1.
Layer structure of laminate [i-1] = [biaxially stretched polyamide film / adhesive layer / polyethylene terephthalate film / aluminum deposition layer / adhesive layer / biaxially stretched PVA film / adhesive layer / polypropylene film]

<Comparative example 2>
The biaxially stretched PVA film of Comparative Example 1 (“Boblon EX” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., thickness 12 μm) is a biaxially stretched ethylene-vinyl alcohol copolymer resin film (“Eval XL” manufactured by Kuraray Co., Ltd., thickness 12 μm). The laminate [i-2] was prepared in the same manner except that it was changed to). Using the obtained laminate [i-2], a vacuum heat insulating structure (v2) was produced in the same manner as in Example 1, and the heat insulating property was evaluated. Moreover, adhesiveness evaluation was performed like Example 1. FIG. The results are also shown in Table 1.
Layer structure of laminate [i-2] = [biaxially stretched polyamide film / adhesive layer / polyethylene terephthalate film / aluminum deposition layer / adhesive layer / biaxially stretched ethylene-vinyl alcohol copolymer resin film / adhesive layer / Polypropylene film)

As shown in Table 1 above, the laminates obtained in the examples had a peel distance of 5 mm or less between the adhesion surface of the vapor deposition layer (B) and the vinyl alcohol-based resin film (D), and were excellent in adhesiveness. In contrast, the laminate obtained in the comparative example was peeled off by 5 mm or more, and was inferior in adhesiveness as compared with the examples.
Furthermore, in the heat insulation performance of the vacuum heat insulation structure, the vacuum heat insulation structure obtained in the comparative example was less in the heat insulation deterioration of the vacuum heat insulation structure produced using the laminate obtained in the example. In the body, the thermal conductivity deterioration is large, especially after a long cycle test, and it can be seen that the vacuum heat insulating structure using the laminate of the example is much superior in heat insulating performance.

  The vacuum heat insulating structure of the present invention comprises a base film (A) / a vapor deposition layer (B) comprising a metal or a metal oxide / a vinyl alcohol resin layer (C) / a vinyl alcohol resin film (D) / a seal layer ( E) A vacuum heat insulating structure including an outer bag for a vacuum heat insulating structure and a heat insulating material containing the laminated body [I] having the layer structure, and a vapor deposition layer of the laminated body and a seal layer laminated thereon Adhesiveness is high, and when it is used for a long time, it has excellent heat insulation performance. For this reason, household appliances such as cooler boxes and bottle cases, household appliances such as refrigerators, jar pots, rice cookers, housing equipment such as water heaters, bathtubs, unit baths, toilet seats, floor heating, solar roofs, low-temperature panels, etc. Although it can be effectively used as a heat insulating material for a housing system, a housing building material such as a heat insulating panel for an outer wall, etc., among these, it can be particularly preferably used as a heat insulating material for a refrigerator.

Claims (8)

  Laminate having layer structure of base film (A) / deposition layer (B) / vinyl alcohol resin layer (C) / vinyl alcohol resin film (D) / seal layer (E) made of metal or metal oxide An exterior bag for a vacuum heat insulating structure, comprising [I].   2. The vacuum according to claim 1, wherein the vapor-deposited layer (B) made of a metal or metal oxide and the vinyl alcohol resin film (D) are bonded using the vinyl alcohol resin layer (C) as an adhesive layer. Exterior bag for heat insulation structure.   The outer bag for a vacuum heat insulating structure according to claim 1 or 2, wherein the protective film (F) is laminated on the outside of the base film (A).   4. The vacuum heat insulation according to claim 1, wherein the vinyl alcohol resin constituting the vinyl alcohol resin layer (C) is a vinyl alcohol resin having a 1,2-diol structure in the side chain. Structure exterior bag.   A base film (A) is a polyethylene terephthalate film, The exterior bag for vacuum heat insulation structures in any one of Claims 1-4 characterized by the above-mentioned.   The vacuum insulation structure according to any one of claims 1 to 5, wherein the vinyl alcohol resin film (D) is a biaxially stretched polyvinyl alcohol film or a biaxially stretched ethylene-vinyl alcohol film. Body exterior bag.   The protective film (F) is a polyolefin-based film, and the outer bag for a vacuum heat insulating structure according to any one of claims 3 to 6.   A vacuum heat insulating structure, wherein the heat insulating material is packaged by the exterior bag for a vacuum heat insulating structure according to claim 1.