WO2014104259A1

WO2014104259A1 - Outer bag for vacuum insulation structure and vacuum insulation structure using same

Info

Publication number: WO2014104259A1
Application number: PCT/JP2013/085008
Authority: WO
Inventors: 徳明黒川; 和司小田; 寛幸中島
Original assignee: 日本合成化学工業株式会社
Priority date: 2012-12-26
Filing date: 2013-12-26
Publication date: 2014-07-03

Abstract

The purpose of the present invention is to obtain a vacuum insulation structure, which exhibits excellent insulation performance and with which the decrease in insulation performance is very small even when used for long periods. Provided is an outer bag for a vacuum insulation structure obtained by using a laminate [I] comprising a vapor deposition film (A) for which, when light is irradiated on the vapor deposition film (A) from the side opposite to the vapor deposition surface and the number of the permeating light is measured as the number of bright spots, the number of bright spots is 200 per 4 mm × 3 mm film size or less.

Description

Exterior bag for vacuum insulation structure and vacuum insulation structure using the same

The present invention relates to an exterior bag for a vacuum heat insulation structure and a vacuum heat insulation structure using the same. More specifically, the present invention has excellent heat insulation performance. It is related with the exterior bag for vacuum heat insulation structures which can obtain a vacuum heat insulation structure with few.

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 foamed resin is used as a core material, which is sealed with a gas barrier laminate film and the inside is vacuumed, has begun to be used.

In such a vacuum heat insulating structure, a vinyl alcohol resin film or a multilayer film containing aluminum foil is used as the gas barrier laminate film, and as the vinyl alcohol resin film, an ethylene-vinyl alcohol resin film, A polyvinyl alcohol resin film is used.

For example, a vacuum heat insulating structure including a multilayer film containing an ethylene-vinyl alcohol-based resin film includes a core material and an outer bag envelope material that encloses the core material, and the outer bag has a vapor deposition layer. Laminate films having each other, or a laminate film having a vapor deposition layer, and a laminate film having a metal foil are formed into a bag shape by thermal welding, and the laminate film having the vapor deposition layer comprises a thermal welding layer and a gas barrier layer. And an outermost layer, wherein the gas barrier layer is formed by vapor-depositing aluminum on one side of a plastic film containing an ethylene-vinyl alcohol-based resin, and the aluminum-deposited surface is provided on the heat-welded layer side. A vacuum heat insulating structure has been proposed (see, for example, Patent Document 1).

Moreover, as a vacuum heat insulating structure including a multilayer film containing a polyvinyl alcohol-based resin film, a heat insulating material is a vacuum heat insulating structure obtained by sealing and packaging with a multilayer film including a polyvinyl alcohol-based resin film, As such a multilayer film, a vacuum heat insulating structure using a multilayer film in which a biaxially stretched polyvinyl alcohol-based resin film that may be deposited and a polyester film, a polyamide film, a polyolefin film or the like that may be deposited is laminated is proposed. (For example, refer to Patent Document 2).

JP-A-10-122477 Japanese Patent Application Laid-Open No. 2007-078176

However, in the disclosed technique of Patent Document 1, a vacuum heat insulating structure having excellent gas barrier properties and excellent heat insulating performance is obtained by using a vapor deposition film for a multilayer film, but the vapor deposition layer is uniform. When there was unevenness or vapor deposition was insufficient, the heat insulation performance deteriorated when used for a long period of time, and sufficient heat insulation performance could not be sustained. Further, in the disclosed technique of Patent Document 2, a vapor deposition layer is provided in order to improve gas barrier properties when using a biaxially stretched polyvinyl alcohol-based resin film. This caused a decrease in

Therefore, there is still room for improvement in the situation where advanced thermal insulation performance is required in recent years, and further improvement in durability is required such that the deterioration of thermal insulation performance is extremely small even after long-term use. ing.

Therefore, in such a background, the present invention has an excellent heat insulation performance, and in particular, a vacuum heat insulation structure outer bag capable of obtaining a vacuum heat insulation structure excellent in sustainability of the heat insulation performance, and uses the same. A vacuum insulation structure was provided.

However, as a result of intensive studies in view of such circumstances, the present inventors, as a result, in the exterior bag used for the vacuum heat insulating structure, the number of bright spots observed by light transmission is 200 or less per predetermined size. It has been found that by using a laminate including a film, a vacuum heat insulating structure excellent in gas barrier properties and excellent in heat insulation performance can be obtained.

That is, the gist of the present invention is that when the light is irradiated from the opposite side of the vapor deposition surface of the vapor deposition film (A) and the number of transmitted light is measured as the number of bright spots, the number of bright spots is the film size. The present invention relates to an exterior bag for a vacuum heat insulating structure using a laminate [I] containing 200 or less vapor deposited films (A) per 4 mm × 3 mm.

Furthermore, in the present invention, the present invention relates to a vacuum heat insulating structure formed by hermetically packaging a heat insulating material using the outer bag for a vacuum heat insulating structure.

In the present invention, in the relationship with the heat insulating performance of the vacuum heat insulating structure, attention was paid to the vapor deposited film contained in the laminate [I] constituting the outer bag for the vacuum heat insulating structure. We have determined that the vapor deposition state of the film affects the heat insulation performance, and by selecting a vapor deposition film with a smaller number of bright spots on the vapor deposition film, a vacuum of gas such as water vapor, nitrogen, oxygen, etc. It is presumed that the penetration into the heat insulating structure is extremely low, the vacuum state is maintained with high reliability even when used for a long period of time, and the heat insulating performance is hardly lowered.

In the present invention, when irradiating light from the opposite side of the vapor deposition surface of the vapor deposition film and measuring the number of transmitted light as the number of bright spots, the number of bright spots is 200 per 4 mm × 3 mm film size. By producing a vacuum heat insulation structure using an exterior bag for a vacuum heat insulation structure using a laminate [I] containing a vapor-deposited film, which shows excellent heat insulation performance, when used for a long time Also, it has an effect of excellent durability such that there is little decrease in heat insulation performance.

An image obtained by irradiating the film of Example 1 with light from the opposite side of the vapor deposition surface and observing under a microscope from the vapor deposition surface side is converted into an 8-bit monochrome image by image analysis software (ImageJ). An image obtained by irradiating the film of Comparative Example 1 with light from the opposite side of the vapor deposition surface and observing under a microscope from the vapor deposition surface side is converted into an 8-bit monochrome image by image analysis software (ImageJ).

The present invention is described in detail below.
The exterior bag for a vacuum heat insulating structure of the present invention is irradiated with light from the opposite side of the vapor deposition surface of the vapor deposition film (A), and the number of bright spots is measured when the number of transmitted light is measured as the number of bright spots. However, it consists of laminated body [I] containing the vapor deposition film (A) which is 200 or less per film size 4 mm x 3 mm.

In the present invention, the bright spot is a bright spot that is observed because light is transmitted through the film when irradiated with light from the opposite side of the vapor deposition surface of the vapor deposition film (A) and observed with a microscope from the vapor deposition surface side. Say that. This means that when there is a minute defect in the vapor deposition layer of the vapor deposition film or when the vapor deposition is uneven, light is transmitted only through the defective part or the thin part of the vapor deposition, and it is seen as a bright and bright spot when observed with a microscope. It is what

In the present invention, the size of the bright spot is about 1 to 10 μm in diameter, and is fine enough that it cannot be visually confirmed, and is generally distinguished from defects that can be visually observed such as cracks and pinholes. Use.

The number of bright spots is measured as follows.
That is, the vapor deposition film (A) is placed on a microscope stage with the vapor deposition surface up, covered with a slide glass from above, irradiated with light from the opposite side of the vapor deposition surface, and observed with a microscope from the vapor deposition surface side. The number of bright spots per 4 mm × 3 mm is measured using image analysis software.

The number of bright spots of the vapor-deposited film (A) is 200 or less per film size 4 mm × 3 mm, preferably 150 or less, particularly preferably 100 or less, and further preferably 70 or less. When the number of such bright spots is too large, gas such as water vapor and oxygen enters the inside of the vacuum heat insulating structure, and the heat insulating performance of the vacuum heat insulating structure tends to deteriorate. The smaller the number of bright spots, the better. However, the lower limit is usually one.

In the present invention, it is preferable to use a vapor-deposited film (A) having a bright spot area ratio of 0.05% or less, more preferably 0.04% or less, particularly preferably 0.03% or less, particularly preferably. Preferably, it is 0.02% or less. If the area ratio of the base point is too large, even when the number of bright spots is small, the total amount of water vapor and gas entering the inside tends to increase, and the heat insulating performance of the vacuum heat insulating structure tends to deteriorate. The smaller the area ratio of the bright spots, the better. However, the lower limit is usually 0.0000001%.

Here, the area ratio (%) is calculated as follows.
That is, the vapor deposition film (A) is placed on the microscope stage with the vapor deposition surface facing up, covered with a glass slide from above, irradiated with light from the opposite side of the vapor deposition surface, and observed with a microscope from the vapor deposition surface side. The total area of bright spots per 4 mm × 3 mm is calculated using image analysis software, and the area ratio of bright spots is obtained from the following equation.

Area ratio (%) = (total area of bright spots per film size 3 mm × 4 mm / area of film size 3 mm × 4 mm) × 100

In the present invention, the light to be irradiated may be light from an illumination device for a microscope, and for example, light in a region of 400 to 750 nm is used. The illuminance of the light source may be the illuminance that a general microscope illumination device has, and it is sufficient that it has an illuminance of about 100 to 50000 lux in the vicinity of the vapor deposition film to be observed. In addition, it is preferable to adjust the illuminance according to the vapor deposition film to be observed, and to adjust the illuminance so that a difference in luminance clearly appears between uneven deposition and fine defects and other portions. Examples of the light source of the lighting device include an LED, a halogen lamp, a fluorescent lamp, an incandescent lamp, and a xenon lamp.

First, the vapor deposition film (A) contained in the laminate [I] used in the outer bag for a vacuum heat insulating structure will be described.

The vapor-deposited film (A) of the present invention is obtained by subjecting a film used for a layer constituting an exterior bag for packaging a heat insulating material when a vacuum heat insulating structure is produced, for example, a base film. And those obtained by subjecting a gas barrier film to a vapor deposition treatment.

As the base film, a synthetic resin film that is usually used as a base film for an exterior bag for a vacuum heat insulating structure, for example, a polyester film, a polyolefin film, a polyamide film, a polyether film, a polyurethane film, etc. In the case where a resin film is used and the base film is used as the vapor-deposited film (A), a film obtained by forming a vapor-deposited layer by vapor deposition on the synthetic resin film can be exemplified. Among them, it is preferable to form a vapor deposition layer on a film such as a polyester film or a polyolefin film and use it as a base film from the viewpoint of processability, durability, and economy, and in particular, a polyethylene terephthalate film and a polybutylene terephthalate. What formed the vapor deposition layer in films, such as a film and a polypropylene film, and what formed the vapor deposition layer in films, such as a polyethylene terephthalate film, are especially preferable.

In addition, the synthetic resin film used for the base film is preferably a stretched film from the viewpoint of the smoothness of the film surface and the applicability to a continuous coating machine and a continuous laminating machine, In particular, it is preferable to use a biaxially stretched film.

In the present invention, the substrate film has an oxygen permeability of 10 ml / (m ² · day · when measured according to the method described in JIS K 7126 (isobaric method) under the condition of 23 ° C. × 50% RH. atm) or less, and particularly preferably 5 ml / (m ² · day · atm) or less. The lower the oxygen permeability, the better. However, the lower limit is usually 0.000001 ml / (m ² · day · atm).

In addition, the thickness of the base film is usually 5 to 80 μm, preferably 8 to 40 μm, particularly preferably 10 to 30 μm. In terms of cost and other films, the film is laminated when obtaining a laminate. It is preferable in that moderate flexibility can be given to the body. If the thickness is too thick, the laminate becomes hard and the shape followability at the time of vacuum packaging tends to be low, which tends to cause breakage. If the thickness is too thin, a part of the base film layer may be lost and a sufficient gas barrier There is a tendency not to get sex.

Examples of the gas barrier film include a synthetic resin film usually used as a gas barrier film of an exterior bag for a vacuum heat insulating structure, for example, a synthetic resin film such as a polyvinylidene chloride film, a nylon film, and a vinyl alcohol resin film. When the gas barrier film is used as the vapor deposition film (A), a film obtained by forming a vapor deposition layer by vapor deposition on the synthetic resin film can be exemplified. Among the synthetic resins, in the present invention, it is preferable to use a vinyl alcohol resin film in terms of gas barrier properties.

The vinyl alcohol resin is not particularly limited as long as it has 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. It is 97 mol% or more.

Examples of the vinyl alcohol resin may be abbreviated as a polyvinyl alcohol resin (hereinafter sometimes abbreviated as “PVA resin”) or an ethylene-vinyl alcohol resin (hereinafter referred to as “EVOH resin”). Among them, in the present invention, a PVA resin is preferable from the viewpoint of gas barrier properties.

<PVA resin>
First, the PVA resin will be described.
The PVA resin is a thermoplastic resin that can be dissolved in water (including warm water), and examples of the PVA resin used in the present invention include unmodified PVA and modified PVA. Unmodified PVA is produced by homopolymerizing vinyl acetate and further saponifying it. On the other hand, the modified PVA includes copolymer-modified PVA and post-modified PVA. The amount of modification is within the range not impairing the effects of the present invention, and is usually less than 10 mol%.

The copolymer-modified PVA is produced by copolymerization of vinyl acetate and an unsaturated monomer copolymerizable with vinyl acetate and then saponification.

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, 4- Hydroxyl group-containing α-olefins such as penten-1-ol and 5-hexen-1-ol and derivatives thereof such as acylates, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, undecylene Unsaturated acids such as acids, salts thereof, 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 Etc.

Further, as the copolymer-modified PVA, PVA having a 1,2-diol structure in the side chain can also be used. Such PVA having a 1,2-diol structure in the side chain includes, for example, (a) a method of saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene, and (b) vinyl acetate and vinyl. A method of saponifying and decarboxylating a copolymer with ethylene carbonate; and (c) saponifying and deketalizing a copolymer of vinyl acetate and 2,2-dialkyl-4-vinyl-1,3-dioxolane. And (d) a method of saponifying a copolymer of vinyl acetate and glyceryl monoallyl ether.

In the present invention, when PVA 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%.

Next, the post-modified PVA can be produced by post-modifying unmodified PVA. Examples of such post-modification methods include acetoacetate esterification, acetalization, urethanization, etherification, grafting, phosphate esterification, and oxyalkyleneation of unmodified or modified PVA.

In the present invention, the average degree of polymerization of the PVA resin is preferably 1100 or more, more preferably 1100 to 4000, and particularly preferably 1200 to 2600. If the average degree of polymerization is too low, the mechanical strength of the film tends to decrease. If the average degree of polymerization is too high, the workability during film formation and stretching tends to be reduced.

The average degree of saponification of the PVA resin is preferably 90 mol% or more, more preferably 95 to 100 mol%, and particularly preferably 99 to 100 mol%. If the average degree of saponification is too low, the water resistance is lowered, and the change of the gas barrier property due to humidity tends to be remarkable. Therefore, it is preferable to select a relatively high saponification degree.

The average polymerization degree and average saponification degree are measured according to JIS K6726.

The viscosity of the 4 wt% aqueous solution of the PVA resin is preferably 2.5 to 100 mPa · s (20 ° C.), more preferably 2.5 to 70 mPa · s (20 ° C.), particularly 2.5 to 60 mPa · s (20 ° C.) is preferable. If the viscosity is too low, mechanical properties such as film strength tend to be inferior, and if it is too high, film-forming properties on the film tend to be lowered.
The viscosity is measured according to JIS K6726.

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

<EVOH resin>
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 valelate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, caprin. Usually, an aliphatic vinyl ester such as vinyl acid, vinyl laurate, vinyl stearate and 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 May be an aliphatic vinyl ester having 4 to 7 carbon atoms. These monomers are usually used alone, but a plurality of these monomers may be used simultaneously as necessary.

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. Examples of other ethylenically unsaturated monomers include olefins such as propylene, 1-butene and 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.

It is also preferable to use an EVOH resin having a 1,2-diol structure in the side chain as the EVOH resin, and the content of the side chain 1,2-diol structure is 0.01 to 20 moles of the EVOH resin. % Is preferable from the viewpoint of obtaining good film formability, and is particularly preferably 0.2 to 15 mol%, more preferably 0.5 to 10 mol%.

The ethylene content of the EVOH-based resin is usually 20 to 60 mol%, but from the viewpoint of obtaining good stretchability, the ethylene content is preferably 25 mol% or more, and more preferably 30 mol% or more. It is particularly preferred. From the viewpoint of gas barrier properties, the ethylene content is particularly preferably 55 mol% or less, and 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), and is usually 90 to 100 mol%. The amount is preferably 95 to 100 mol%, particularly preferably 99 to 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 film-forming property tends to be unstable, and if it is too small, the viscosity is too high, resulting in poor flow and tending to cause poor appearance such as streaks and unevenness.

Such EVOH-based resin includes an antioxidant, a colorant, an ultraviolet absorber, a slip agent, an antistatic agent, a plasticizer, a crosslinking agent such as boric acid, an inorganic filler, 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 an inorganic desiccant, polyamide, polyolefin, and a super absorbent polymer.

Furthermore, a boron compound can be blended with an EVOH-based resin in order to improve 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 the 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, the EVOH resin used in the present invention may be “post-modified” such as urethanization, acetalization, cyanoethylation, oxyalkyleneation and the like by a known method.

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

<Production method of film>
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 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 draw ratio in the flow direction (MD direction) of such uniaxial and biaxially stretched films 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, or sequential biaxial stretching.

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

<Production method of biaxially stretched PVA resin film>
First, the manufacturing method of a biaxially stretched PVA-type resin film is demonstrated.
A PVA-based resin film (PVA-based resin film before stretching) is formed into a film using the PVA-based resin. Usually, as a stock solution for film formation, a PVA-based resin concentration is 5 to 70% by weight, Preferably, a composition of 10 to 60% by weight of PVA resin-water is prepared.

Such PVA-based resin-water compositions include plasticizers such as 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, coloring agents, fragrances, extenders, antifoaming agents, 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-based resin film is not particularly limited, but the PVA-based resin-water composition is supplied to an extruder and melt-kneaded, and then extruded and formed by the T-die method and the inflation method, followed by drying. The method is preferred.

In such a method, the melt kneading temperature in the extruder 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. In addition, drying of the film after film formation is preferably performed at 70 to 120 ° C., more preferably 80 to 100 ° C.

The biaxially stretched PVA resin film preferably used in the present invention is obtained by further biaxially stretching the PVA resin 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. Has a draw ratio in the MD direction of 3 to 5 times and a draw ratio in the TD direction 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 biaxial stretching, it is preferable to adjust the water content of the PVA resin film to 5 to 30% by weight, particularly 20 to 30% by weight. The moisture content can be adjusted by a method of continuously drying the PVA resin film before drying, a method of immersing a PVA resin film having a moisture content of less than 5% by weight in water, or adjusting the humidity. 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.

Further, after the biaxial stretching, it is preferable to perform heat setting, and it is preferable to select a temperature lower than the melting point of the PVA 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. On the other hand, when the temperature is higher than the melting point, the thickness variation of the film tends to be large. The heat setting time is preferably 1 to 30 seconds, more preferably 5 to 10 seconds.

Further, if necessary, for the purpose of further reducing the heat deformability, it is possible to subject the biaxially stretched PVA resin film to contact with an aqueous solution and to dry processing. 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 Preferably it is 60 seconds.

Examples of the contact method with the 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 water adhering to the surface in a non-contact manner with an air shower or the like, and then to remove the moisture in contact 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 resin film is again wound up into a roll after 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%. It is desirable to make it weight percent. 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 resin film is obtained.

<Production method of biaxially stretched EVOH resin film>
Next, a method for producing a biaxially stretched EVOH resin film will be described.
An EVOH resin film (an EVOH resin film before stretching) is formed using the EVOH resin.

When forming an EVOH resin 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-based resin film can be obtained. The film can be further biaxially stretched, preferably sequentially biaxially stretched to obtain a biaxially-stretched EVOH-based resin 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. 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.

In addition, it is possible to perform easy continuous stretching by pre-moisturizing 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. %, More preferably 10 to 30% by weight. 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. In particular, in simultaneous biaxial stretching, a biaxially stretched EVOH-based resin film with little thickness unevenness is easily obtained in the range of 70 to 100 ° C., and in sequential biaxial stretching, in the longitudinal direction with a roll, 70 to 100 is achieved. When the stretching in the width direction with a tenter at 80 ° C. is performed in a temperature range of 80 to 120 ° C., a biaxially stretched EVOH resin film with little thickness unevenness is easily obtained.

And as a further important factor regarding manufacture of a biaxially stretched EVOH resin film, there are the heat treatment after stretching and the density and moisture content of the biaxially stretched EVOH resin 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, and thus there is a tendency that heat resistance sufficient to withstand the vapor deposition process and sufficient gas barrier properties cannot be obtained. On the other hand, when the heat treatment temperature is too high, the stretching effect tends to be partially reduced.
Thus, a biaxially stretched EVOH resin film is obtained.

The gas barrier film has an oxygen permeability of 1 ml / (m ² · day · atm) or less when measured according to the method described in JIS K 7126 (isobaric method) under the condition of 23 ° C. × 50% RH. In particular, it is preferably 0.1 ml / (m ² · day · atm) or less. The lower the oxygen permeability, the better. However, the lower limit is usually 0.000001 ml / (m ² · day · atm).

The thickness of the gas barrier film is usually 5 to 100 μm, preferably 5 to 50 μm, 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-deposited film (A) used in the present invention is a vapor-deposited base film (A-1) obtained by subjecting the base film to a vapor deposition treatment, or a vapor-deposited gas barrier property obtained by subjecting the gas barrier film to a vapor deposition treatment. A film (A-2) is preferred.

The vapor deposition material may be a known general vapor deposition material used when producing a laminate used for a vacuum heat insulating structure, but a metal or a metal oxide is preferably used.

As the metal or metal oxide, for example, a metal such as aluminum, gold, silver, copper, nickel, cobalt, chromium, tin, or an oxide of such 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. In addition, silica vapor deposition can be performed instead of metal or metal oxide vapor deposition.

As a vapor deposition method, for example, a general vacuum vapor deposition method such as a sputtering method, an ion plating method, a resistance heating vapor deposition method, a high frequency induction heating vapor deposition method, or an electron beam heating vapor deposition method can be used. In order to make the number of bright spots of the vapor-deposited film (A) 200 or less, and further to make the area ratio of bright spots 0.05% or less, for example, the following vapor deposition is preferable. .

That is, in the present invention, it is preferable to perform deposition while keeping the degree of vacuum constant during the deposition process on the film, or to deposit at a relatively slow rate. Moreover, it is preferable that the heating temperature in the vapor deposition process is constant. Furthermore, in order to prevent the deposition surface from being scraped off during the winding or slitting process immediately after deposition, the number of rolls in contact with the deposition surface should be reduced as much as possible, and the material of the roll should be a material that does not place a load on the deposition surface. desirable. By these methods, the volatilization amount of the vapor deposition material becomes constant, and a vapor deposition layer without vapor deposition unevenness can be obtained. As a result, a deposited film having a small number of bright spots and a small area ratio of bright spots can be obtained.

Moreover, it is also preferable to pre-treat the surface of the film to be vapor-deposited before the film is vapor-deposited. Examples of such pre-treatment include a method for promoting activation of the substrate itself such as corona treatment, and polyethylene. And a method of forming a thin film layer with a coating agent that uses a polyether as a main component and a urethane-based curing agent.
Note that the vapor deposition may be obtained by a single vapor deposition treatment or may be obtained by repeating the vapor deposition treatment a plurality of times.

The thickness of the vapor deposition is usually 10 to 100 nm, particularly 30 to 80 nm. If it is too thin, there is a tendency that it is difficult to obtain heat radiation characteristics, and if it is too thick, the deposition time for obtaining the thickness becomes long, the thermal influence during deposition tends to increase and the cost tends to increase, There is an industrially unfavorable tendency.

The laminate [I] in the present invention includes at least one layer of the above-mentioned vapor-deposited film (A), but includes a base film / gas barrier film layer structure from the viewpoint of strength, gas barrier properties, and the like. It is preferable that at least one of the film and the gas barrier film is a vapor deposition film (A). When the base film or the gas barrier film does not have a vapor deposition layer, various films before vapor deposition can be used as they are.

In addition, a base film and a gas barrier film may each be used only one layer, and may laminate | stack two or more layers. Moreover, 1 type, or 2 or more types of films can be used for a base film and a gas-barrier film.

In the present invention, it is preferable to use a biaxially stretched PVA-based resin film and a biaxially stretched EVOH-based resin film in combination as the gas barrier film, and in particular, base film / biaxially stretched EVOH-based resin film / biaxially stretched. Each layer of the PVA-based resin film is preferably laminated in this order. That is, in addition to the base film, the gas barrier property of the biaxially stretched EVOH resin film, particularly the entry of water vapor, is suppressed to a very small amount, so that the biaxially stretched PVA resin film is extremely resistant to various gases such as oxygen and nitrogen. Excellent gas barrier performance will be exhibited sufficiently, and when the laminate [I] has a biaxially stretched PVA resin film inside and seals the heat insulating material to form a vacuum heat insulating structure, the gas barrier property is improved. Since the vacuum state is maintained with high reliability even when used for a long period of time, the heat insulation performance is hardly deteriorated, and a vacuum heat insulating structure excellent in long-term durability can be obtained.

The thickness ratio between the biaxially stretched EVOH resin film and the biaxially stretched PVA resin film is preferably biaxially stretched EVOH resin film / biaxially stretched PVA resin film = 1/3 to 3/1, more preferably It is 1/2 to 2/1, particularly preferably 1 / 1.5 to 1.5 / 1. Biaxially stretched EVOH-based resin film and biaxially-stretched PVA-based resin film are complementary to each other in their barrier properties, and are different from each other in gas types that can prevent intrusion, particularly in poor environments such as high-temperature and high-humidity conditions. Therefore, it is necessary for each of them to exhibit barrier properties with an appropriate thickness, and the thickness ratio is preferably within the above range.

Furthermore, the laminate [I] in the present invention is preferably formed by laminating a protective film on the outside of the base film and laminating a seal layer on the inside of the gas barrier film.

The protective film used in the present invention is a film mainly used for the purpose of protecting the outer layer when an exterior bag for a vacuum heat insulating structure is produced using the laminate [I]. For example, a polyester film, a polyamide Examples thereof include a system film, a polyolefin film, and a polyurethane film. Among them, it is preferable to use a polyolefin-based film, preferably a polypropylene film, a polyvinyl chloride film, a polyvinylidene chloride film, or a fluorine-based film because it has a water vapor barrier property.

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 are listed, and ethylene, butene-1, pentene-1, 4-methylpentene-1 containing propylene as a main component , Hexene-1, octene-1, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, copolymers with 1,4-hexadiene, styrene, etc., and also grafted with carboxylic acid such as maleic anhydride Modified ones, copolymers of ethylene, propylene, butene-2, isobutylene, butadiene, pentene-1, 4-methylpentene-1, hexene-1, octene-1 and the like mainly containing butene-1; Furthermore, graft-modified with carboxylic acid such as maleic anhydride, ethylene as the main component Propylene, butene-1,4-methylpentene-1,1-hexene, 1-octene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, styrene, vinyl acetate, methyl acrylate, ethyl acrylate , Copolymers with acrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid, glycidyl methacrylate, and the like, and those graft-modified with carboxylic acids such as maleic anhydride. Among these, it is particularly preferable to use polypropylene in terms of moisture resistance and industrial productivity.
Here, the main component means a component that occupies the majority of the whole, and includes the case where the whole consists of only the main component.

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

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

Further, the protective film 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 / day or less. It is preferable that The initial elastic modulus is a value at 23 ° C. × 60% RH measured in accordance with JIS K 7127, and the water vapor permeability is 23 ° C. × 90% measured in accordance with JIS Z 0208. Value at RH. The water vapor permeability is preferably as small as possible, but the lower limit is usually 0.0000001 g / m ² / day.

The seal layer used in the present invention is provided on the inner side when an outer bag for a vacuum heat insulating structure is produced using the laminate [I], and usually comprises a polyolefin resin layer from the viewpoint of seal strength. A layer is preferable, 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, in forming the seal layer, (1) using the resin for forming the seal layer, a separate film may be prepared and further laminated on the inner surface of the exterior bag. (2) Although it can be laminated by melt extrusion directly on the inner surface of the outer bag, (1) is preferred in terms of sealing properties.

The thickness of the sealing layer is usually preferably 10 to 100 μm, particularly 20 to 80 μm. If it is too thin, the sealing strength tends to decrease. If it is too thick, gas penetration from the end face of the sealing layer is promoted. There is a tendency for gas barrier property to fall.

In the present invention, as a method of laminating each layer constituting the laminate [I], for example, a non-solvent dry laminating method using an adhesive that uses an isocyanate-based curing agent with polyester or polyether as a main component, a solvent dry laminating method, Although there is a wet laminating method using an emulsion adhesive, there is no particular limitation to this method.

The thickness of the adhesive layer is preferably from 0.1 to 10 μm, particularly from 0.3 to 7 μm, more preferably from 0.5 to 5 μm from the viewpoint of adhesive strength. If the thickness of the adhesive layer is too thin, the adhesive force tends to be insufficient, and if it is too thick, delamination occurs due to the destruction of the adhesive layer itself, and the adhesive strength tends to decrease.

The total thickness of the laminate [I] in the present invention is usually 5 to 500 μm, and particularly preferably 10 to 200 μm.

Further, the water vapor permeability of the laminate [I] of the present invention is usually 1 g / m ² / day or less, and more preferably 0.5 g / m ² / day or less. If the water vapor permeability is too large, the gas barrier property is lowered, and thus the heat insulation performance of the vacuum heat insulation structure tends to be lowered. The water vapor permeability is preferably as small as possible, but is usually 0.00001 g / m ² / day as the lower limit.
The water vapor permeability is a value at 23 ° C. × 90% RH measured according to JIS Z 0208.

The oxygen permeability of the laminate [I] is usually 0.5 ml / (value when measured according to the method described in JIS K 7126 (isobaric method) under the condition of 23 ° C. × 50% RH. m ² · day · atm) or less, preferably 0.1 ml / (m ² · day · atm) or less. If the oxygen permeability is too high, as in the case of the water vapor, after the vacuum heat insulating structure is formed, an outside air constituent gas such as oxygen or nitrogen tends to enter the inside and the heat insulating performance tends to be remarkably lowered. The lower the oxygen permeability, the better. However, the lower limit is usually 0.000001 ml / (m ² · day · atm).

Furthermore, the laminate [I] of the present invention preferably has a moisture content in the laminate of 0.3% by weight or less, particularly preferably 0.2% by weight or less, and more preferably 0.1% by weight or less. It is particularly preferably 0.07% by weight or less, particularly preferably 0.05% by weight or less. If the moisture content is too high, the moisture contained in the laminate tends to lower the heat insulation performance of the vacuum heat insulation structure because the internal pressure of the vacuum heat insulation structure is lowered. The lower limit of the moisture content is usually 0.001% by weight.

In addition, the moisture content in laminated body [I] is measured as follows.
That is, the moisture content of the laminate [I] can be determined by, for example, using a Karl Fischer measuring device (moisture vaporizer: VA-100 type, trace moisture measuring device: CA-100 type) manufactured by Mitsubishi Chemical Corporation. Measure by coulometric titration method. The laminate [I] is cut into 4 cm × 1 cm strips, 10 are placed on a board, and the titration duration is 30 minutes at a heating temperature of 120 ° C.

When adjusting the moisture content in the laminate [I] to the above range, for example, in a state where the laminate [I] having the above layer configuration and the desiccant are hermetically packaged with an aluminum packaging material, the temperature is 40 ° C. or higher. By heating in an environment, it is possible to obtain a laminate [I] having a moisture content adjusted to 0.3% by weight or less.

The heating temperature is preferably 40 ° C. or higher, particularly 50 ° C. or higher, more preferably 70 ° C. or higher, and particularly preferably 80 ° C. or higher. If the heating temperature is too low, a satisfactory moisture content tends not to be obtained. The upper limit is usually 120 ° C. If the heating temperature is too high, the sealing layer tends to be fused.

Further, the heating time is preferably 0.5 hours or more, particularly preferably 1 to 96 hours, more preferably 3 to 72 hours. When the heating time is too short, there is a tendency that the moisture of the film cannot be sufficiently removed.

Examples of the desiccant include compounds or anhydrous compounds in which a part or all of the crystal water of the compound has been released, such as compounds or anhydrous compounds in which a part or all of 1/2 to 18 hydrate has been released. Can be used. Such hydrates include calcium sulfate hemihydrate, calcium chloride hexahydrate, magnesium chloride (2,4,6) hydrate, copper sulfate pentahydrate, magnesium sulfate heptahydrate. And aluminum sulfate 18 hydrate. Among them, as this type of desiccant, for example, calcium chloride-based desiccant using anhydrous calcium chloride or calcium chloride monohydrate, or magnesium chloride-based desiccant, tin chloride-based desiccant, sodium sulfate-based A desiccant etc. are mentioned.

As the desiccant, a desiccant that causes a chemical reaction with surrounding moisture, that is, a desiccant that becomes a different compound before and after drying can be used. Examples of this type of desiccant include phosphorus pentoxide and calcium oxide. Each of these compounds is dried by reacting with moisture to change into phosphoric acid, calcium hydroxide, or the like.

As a method for packaging these desiccants, the desiccant can be present in the form of powder or flakes, and can be packaged inside. Alternatively, only the desiccant can be individually packaged with a highly permeable packaging material, and the laminate It can also be packaged together with [I]. In this case, the highly permeable packaging material includes paper, non-woven fabric, woven fabric, cellophane film, and the like, and these can be used alone or in combination. It is also possible to form a composite by applying a desiccant to the surface of paper, nonwoven fabric or the like, and wrap this in an aluminum packaging material.

The amount of the desiccant used is 0.5 to 50 weights per 100 parts by weight of the inner laminate [I] (including the case of the outer bag for a vacuum heat insulating structure using the laminate [I]). Parts, preferably 1 to 20 parts by weight. If the amount of the desiccant is too small, the water removability tends to decrease. If the amount is too large, the entire volume tends to be large and transportation and storage tend to be difficult. In the present invention, conventionally used desiccants such as silica gel other than the desiccant may be used in combination.

In addition, it is preferable that it is a laminated body containing an aluminum foil layer as a packaging material used for aluminum packaging. The thickness of the arnium packaging material is preferably 10 to 1000 μm, particularly preferably 30 to 300 μm.

In addition, when adjusting the moisture content of the laminate [I], for example, a method of drying immediately before vacuum packaging and the like can be mentioned.

In the present invention, the laminate [I] and the desiccant are preferably sealed and packaged with an aluminum packaging material, heated in an environment of 40 ° C. or higher, and then stored or transported in sealed packaging. . Furthermore, in this invention, the exterior body for vacuum heat insulation structures is produced beforehand using laminated body [I] before adjusting a moisture content, and the obtained exterior bag for vacuum insulation structures and a desiccant are made into aluminum. It is also preferable to store or transport the sealed packaging as it is after heating in an environment of 40 ° C. or higher in a state of being sealed and packaged with a packaging material. As mentioned above, if it is heated in an environment of 40 ° C. or higher in a state of hermetically sealed with an aluminum packaging material, it can then be stored or transported as it is in hermetically sealed packaging and immediately vacuumed even after opening. If it uses for manufacture of the exterior bag for heat insulation structures, or manufacture of a vacuum heat insulation structure, it is very advantageous, without requiring a special drying process.

Thus, an exterior bag for a vacuum heat insulating structure is obtained using the above laminate [I]. In this invention, when forming an exterior bag, it is preferable to form with the sealing layer of laminated body [I] inside. In addition, when laminated body [I] does not have a sealing layer, it is preferable to form the exterior bag for vacuum heat insulation structures so that a gas barrier film may become inside. The vacuum heat insulating structure of the present invention can be obtained by sealing and packaging the heat insulating material using such an exterior bag.

<Vacuum insulation structure>
Next, the vacuum heat insulating structure of the present invention will be described.
In packaging the heat insulating material, for example, a method of forming an outer bag obtained by processing the laminate [I] into a bag shape and putting the heat insulating material therein can be used.

As a preferable layer structure when sealing and packaging the heat insulating material with the exterior bag for a vacuum heat insulating structure using the laminate [I] of the present invention, from the viewpoint of gas barrier properties and moisture resistance, and further long-term durability, From the outer layer side (the side opposite to the heat insulating material), for example,
(1) Protective film / adhesive layer / deposited polyester film (deposition surface) / adhesive layer / biaxially stretched polyvinyl alcohol resin film / adhesive layer / seal layer,
(2) Protective film / adhesive layer / deposited polyester film (deposited surface) / adhesive layer / (deposited surface) deposited biaxially stretched polyvinyl alcohol resin film / adhesive layer / seal layer,
(3) Deposition polyester film (deposition surface) / adhesive layer / deposition polyester film (deposition surface) / adhesive layer / biaxially stretched polyvinyl alcohol resin film / adhesive layer / seal layer,
(4) Deposition polyester film (deposition surface) / adhesive layer / biaxially stretched ethylene-vinyl alcohol copolymer resin film / adhesive layer / biaxial stretch polyvinyl alcohol resin film / adhesive layer / seal layer,
(5) Deposition polyester film (deposition surface) / adhesive layer / (deposition surface) Deposition biaxially stretched ethylene-vinyl alcohol copolymer resin film / adhesive layer / biaxially stretched polyvinyl alcohol resin film / adhesive layer / Sealing layer,
However, it is not limited to such a layer structure.
In the present invention, the layer configuration of (1), (3) or (4) is particularly preferred from the viewpoint of water vapor barrier properties.
Moreover, you may have other layers, such as a gas-barrier film and an adhesive (or adhesive) layer, between each layer.

When manufacturing a vacuum heat insulating structure, in order to adjust the organic volatile content, after obtaining the laminate [I] or once processing the laminate [I] into an outer bag shape, 70 ° C. or more It is preferable to perform additional drying in a constant temperature bath.

As additional drying, it is preferable to dry at 70 ° C. or higher and 150 ° C. or lower, particularly 80 ° C. or higher and 130 ° C. or lower, and further 80 ° C. or higher and 110 ° C. or lower. If the drying temperature is too low, it tends to take too much time to reach the predetermined amount of residual solvent. If the drying temperature is too high, the sealing layer of the outer bag is fused inside, and the inner space of the bag is reduced. There is a tendency to partially occlude.

Further, the additional drying is generally performed under normal pressure conditions, but can be performed under reduced pressure conditions. In this case, the drying time at the same temperature can be shortened by reducing the pressure as compared with the normal pressure condition.

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 such a heat-insulating material include urethane foam, carbon foam, phenol foam, phenol-urethane foam and other polymers having open cells, fine powders such as alumina, silica, pearlite, 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.

Also, 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 calcium oxide or calcium chloride.

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, a 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 made of the laminate [I], 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 the laminate [I] is included for one vacuum heat insulating structure, or the outer bag for one vacuum heat insulating structure. May be in a shape including a plurality of.

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.

Regarding 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, the vacuum heat insulating structure using the laminate [I] including the deposited film (A) in which the number of bright spots observed in the deposited film (A) is 200 or less per 4 mm × 3 mm film size. By using the body outer bag, it is possible to obtain a vacuum heat insulating structure having excellent heat insulating performance and having a very low decrease in heat insulating performance even when used for a long time. Such vacuum heat insulating structures include household appliances such as cooler boxes and bottle cases, household appliances such as refrigerators, electric pots, rice cookers, housing equipment such as water heaters, bathtubs, unit baths, toilet seats, floor heating, solar roofs, It can be effectively used as a heat insulating material for a housing system such as a low-temperature radiation plate, a housing building material such as a heat insulating panel for an outer wall, and the like. Among these, it can be particularly preferably used as a heat insulating material for refrigerators.

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.

<Example 1>
The following films were prepared.
[Deposited film (A)]
(Aluminum-deposited biaxially stretched polyester film (A-1))
Metal aluminum was vacuum evaporated on one smooth surface of a 12 μm thick biaxially stretched polyester film (trade name “Cosmo Shine” manufactured by Toyobo Co., Ltd.), and an aluminum-deposited biaxially stretched polyester film (A- 1) was obtained.

When the obtained aluminum vapor-deposited biaxially stretched polyester film (A-1) was measured as follows, the number of bright spots was 28, and the area ratio of bright spots was 0.04 (%).

<Measurement method of number of bright spots>
The aluminum-deposited biaxially stretched polyester film (A-1) obtained above is placed on the stage of a microscope (manufactured by Keyence Corporation, Digital Microscope VHX-1000) and covered with a slide glass from above, and from the opposite side of the deposition surface Irradiate light and observe with a microscope from the side of the deposition surface (magnification: 100 times), so that the image size is 4 mm x 3 mm at each of the five locations (upper right, upper left, lower right, lower left, center) of the film. Got an image. Each of the obtained images was converted into an 8-bit monochrome image by image analysis software (ImageJ), and then set so as to count a portion having a contrast of 100 to 255, and the number was measured. And the average value of the number of the measured five places was made into the number of the bright spots of a film.

In addition, FIG. 1 shows an image obtained by converting the image at the center of the obtained image into an 8-bit monochrome image using image analysis software (ImageJ).

<Measurement method of area ratio of bright spots>
Similar to the above method for measuring the number of bright spots, after obtaining an image of the aluminum-deposited biaxially stretched polyester film (A-1), the total area of the bright spots was measured using image analysis software (ImageJ), The area ratio (%) of the bright spots was determined. The total area of bright spots was also measured at five locations (upper right, upper left, lower right, lower left, and center) of the film, and the average value was taken as the number of bright spots on the film.

[Biaxially stretched PVA film]
From a hopper of a twin-screw extruder type kneader (screw L / D = 40) with the jacket temperature set to 60 to 150 ° C., a PVA (polymerization degree 1700, 4 wt% aqueous solution viscosity 40 mPa · s, saponification degree 99.7) Mol%, sodium acetate content 0.3%) and water at a PVA / water weight ratio of 40/60 were supplied by a metering pump, kneaded, and discharged under conditions of a discharge amount of 500 kg / hr.

This discharged material was immediately pumped to a single screw extruder (screw L / D = 30), kneaded at a temperature of 85 to 140 ° C., extruded from a T die onto a 5 ° C. cast roll, and then heated at 90 ° C. with a hot air dryer. The film was dried for 2 seconds to prepare a PVA film (thickness 150 μm) having a water content of 25%. Subsequently, the PVA film was stretched 3.8 times in the MD direction, then stretched 3.8 times in the TD direction with a tenter, and then heat-fixed at 180 ° C. for 8 seconds to obtain a biaxially stretched PVA film (thickness 12 μm). It was.

〔Protective film〕
(Biaxially oriented polypropylene film)
A biaxially stretched polypropylene film (trade name “Pyrene OT”, manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm was prepared. The water vapor transmission rate of this film at 23 ° C. × 90% RH was measured and found to be 7.2 g / m ² / day.

(Seal layer)
(Unstretched polypropylene film)
A non-stretched polypropylene film having a thickness of 30 μm (trade name “Pyrene CT” manufactured by Toyobo Co., Ltd.) was prepared.

Using each of the above films, a vacuum heat insulating structure was produced as follows.
On the surface of the aluminum vapor-deposited biaxially stretched polyester film (A-1) which has not been subjected to the vapor deposition treatment, 17 parts of an adhesive main agent “Takelac A626” (manufactured by Mitsui Chemicals) and an adhesive curing agent “Takenate A50” (Mitsui) (Chemical Co., Ltd.) A dry laminating adhesive in which 17 parts of ethyl acetate was mixed with 17 parts was applied by a gravure coater using a gravure roll with a mesh of 100 μm so that the coating amount was 10 g / m ^2. Biaxially oriented polypropylene film with a residence time of 12 seconds, a coating amount after drying of 3.4 g / m ² , and a laminating pressure of 3.5 kg / cm ² (0.35 MPa) through a heated dryer. And a laminated body (1) was obtained.

Next, on the surface of the biaxially stretched PVA film, ethyl acetate was added to 17 parts of the adhesive main agent “Takelac A626” (Mitsui Chemicals) and 17 parts of the adhesive curing agent “Takenate A50” (Mitsui Chemicals). 66 parts of the mixed adhesive for dry lamination was applied by a gravure coater using a gravure roll with a mesh of 100 μm so that the coating amount was 10 g / m ^2, and this was passed through a dryer heated to 80 ° C. After drying, the coating amount after drying was 3.4 g / m ^2, and then the aluminum vapor-deposited polyester film (A-) of the laminate (1) was laminated at a lamination pressure of 3.5 kg / cm ² (0.35 MPa). The laminated body (2) was obtained by laminating it with the aluminum-deposited surface of 1).

Next, on the surface of the biaxially stretched PVA film of the laminate (2) obtained above (surface on which the vapor-deposited polyester film is not laminated), 17 parts of the main agent for adhesive “Takelac A626” (manufactured by Mitsui Chemicals) And a hardener for adhesive “Takenate A50” (Mitsui Chemicals Co., Ltd.) using a gravure roll with a mesh of 100 μm so that a coating amount of 10 g / m ² is applied to an adhesive for dry lamination in which 66 parts of ethyl acetate is mixed with 17 parts of Mitsui Chemicals. The coating was applied with a gravure coater, passed through a drier heated to 80 ° C., and after a drying time of 3.4 g / m ² with a residence time of 12 seconds, a laminating pressure of 3.5 kg / cm ^2. A non-stretched polypropylene film having a thickness of 30 μm was bonded to the laminate [I-1] at (0.35 MPa).

Using the laminate [I-1] obtained above, an exterior bag for a vacuum heat insulating structure was produced as follows.
That is, the laminate [I-1] was cut into a 30 cm square sheet, and two sheets of the laminate [I-1] were used so that the surfaces of the unstretched propylene film were overlapped with each other. The sides were heat-sealed at a seal temperature of 130 ° C. to obtain a three-side sealed packaging bag (exterior bag for vacuum heat insulating structure).
(Layer structure = outside: biaxially stretched polypropylene film / adhesive layer / aluminum-deposited polyester film (deposited surface) / adhesive layer / biaxially stretched PVA film / adhesive layer / unstretched polypropylene film: inside)

Next, a commercially available fine glass wool (manufactured by Mag Izobale, “WR800”) is laminated to ² kg / m ² , heated to 630 ° C., and then compressed with a load until the thickness reaches 10 mm. And after cooling this slowly, it cut | judged to 20 square cm and obtained the heat insulating material.

The heat insulating material obtained above was dried again by leaving it in a thermostatic bath at 150 ° C. for 1 hour. On the other hand, the three-side sealed packaging bag (exterior bag for vacuum heat insulation structure) is left in a constant temperature bath at 100 ° C. for 1 hour with the mouth open, and the dried heat insulating material is inserted therein. Further, 3 g of quicklime desiccant contained in a polypropylene nonwoven fabric is enclosed in the inner edge of the three-side sealed packaging bag, immediately placed in a vacuum packaging machine, and sealed under reduced pressure at a pressure of 2 Pa in the vacuum packaging machine, A vacuum heat insulating structure [V-1] was obtained.

The obtained vacuum heat insulating structure [V-1] was evaluated as follows. The results are shown in Table 1 below.
<Insulation evaluation>
The vacuum heat insulating structure [V-1] was left in a constant temperature room at 20 ° C. × 40% RH for 24 hours, and then the thermal conductivity (W1) (mW / m · K) was measured. Then, after leaving in an environment of 70 ° C. × 90% RH for 13 days, the thermal conductivity (W2) (mW / m · K) was measured in the same manner, and the thermal conductivity deterioration due to the durability test (W3 = W2−W1) ) (MW / m · K) was obtained and evaluated as heat insulation performance.
The thermal conductivity was measured by a thermal conductivity measuring device (Hideki Seiki Co., Ltd., HC-074).

<Examples 2 to 4, Comparative Examples 1 and 2>
As shown in Table 1 below, a vacuum heat insulating structure was produced in the same manner as in Example 1 except that an aluminum vapor deposited polyester film having a different number of bright spots and different area ratios was used as the vapor deposited film (A). The structure was evaluated in the same manner as in Example 1.

In Comparative Example 1, among the images obtained when measuring the number of bright spots, the image of the central portion is converted into an 8-bit monochrome image by image analysis software (ImageJ) is shown in FIG. Comparing FIG. 1 which is the image of Example 1 and FIG. 2 which is the image of Comparative Example 1, in FIG. 1, white spots are hardly seen, whereas in FIG. 2, white spots are scattered. It was done. Thus, it can be seen that the number of white spots in the image can be measured as the number of bright spots.

As shown in Table 1 above, a laminate including a vapor deposition film (A) having a number of bright spots of 200 or less, preferably a vapor deposition film (A) having an area ratio of 0.05 (%) or less. The vacuum heat insulating structures of Examples 1 to 4 used have low initial thermal conductivity (W1), excellent thermal insulation performance, and further less thermal conductivity deterioration (W3) after the durability test. It was also excellent in sustainability. On the other hand, the vacuum heat insulating structures of Comparative Examples 1 and 2 using the laminate including the vapor deposition film having more than 200 bright spots have the same initial thermal conductivity as that of Examples 1 to 4. However, the thermal conductivity deterioration of the durability test is large and the heat insulation performance is remarkably lowered, and the vacuum heat insulation structures of the examples are superior in durability of the heat insulation performance and excellent in long-term durability. I understand that.

What used the vacuum heat insulation structure of the Example obtained as a heat insulating material of a refrigerator is superior in heat insulation performance and long-term durability compared with the one using the vacuum heat insulation structure of the comparative example. This can greatly reduce the consumption.

In addition, although the specific form in this invention was shown in the said Example, the said Example is only a mere illustration and is not interpreted limitedly. Various modifications apparent to those skilled in the art are contemplated to be within the scope of this invention.

When the vacuum heat insulating structure of the present invention is irradiated with light from the opposite side of the vapor deposition surface of the vapor deposition film (A) and the number of transmitted light is measured as the number of bright spots, the number of bright spots is It is an exterior bag for a vacuum heat insulation structure, characterized by using a laminate [I] containing a vapor-deposited film (A) of 200 or less per 4 mm × 3 mm size, and not only has excellent initial heat insulation performance Even when used for a long period of time, the heat insulation performance is hardly lowered, and it has excellent long-term durability. Therefore, household appliances such as cooler boxes, bottle cases, household appliances such as refrigerators, electric pots, rice cookers, housing equipment such as water heaters, bathtubs, unit baths, toilet seats, floor heating, solar roofs, low-temperature radiation plates, 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 suitably used as a heat insulating material for a refrigerator or a housing building material.

Claims

When irradiating light from the opposite side of the vapor deposition surface of the vapor deposition film (A) and measuring the number of transmitted light as the number of bright spots, the number of bright spots is 200 or less per 4 mm × 3 mm film size. An outer bag for a vacuum heat insulating structure, comprising a laminate [I] containing a certain vapor-deposited film (A).
The outer bag for a vacuum heat insulation structure according to claim 1, wherein the area ratio of the bright spots observed in the deposited film (A) is 0.05% or less.
The exterior bag for a vacuum heat insulating structure according to claim 1 or 2, wherein the deposited film (A) is a deposited polyester film.
The exterior bag for a vacuum heat insulating structure according to claim 1 or 2, wherein the deposited film (A) is a deposited biaxially stretched vinyl alcohol resin film.
The laminate [I] includes a layer structure of a base film / gas barrier film, and at least one of the base film and the gas barrier film is a deposited film (A). The exterior bag for a vacuum heat insulating structure according to one item.
The laminate [I] has a layer configuration of protective film / base film / gas barrier film / seal layer, and the exterior bag is formed so that the seal layer is on the inside. 5. The outer bag for a vacuum heat insulating structure according to 5.
The laminate [I] has a layer structure of a protective film / deposited polyester film / biaxially stretched vinyl alcohol resin film / seal layer from the outside, and the exterior for a vacuum heat insulating structure according to claim 6 bag.
The outer bag for a vacuum heat insulating structure according to any one of claims 1 to 7, wherein the moisture content of the laminate [I] is 0.3% by weight or less.
A vacuum heat insulating structure, wherein the heat insulating material is hermetically packaged using the outer bag for a vacuum heat insulating structure according to any one of claims 1 to 8.
The vacuum heat insulating structure according to any one of claims 1 to 9, wherein the vacuum heat insulating structure is used as a heat insulating material for a refrigerator.