WO2016006191A1 - Laminate for packaging material, packaging material for vacuum heat-insulating material, and vacuum heat-insulating material - Google Patents

Abstract

Provided are a laminate for a packaging material capable of improving stiffness and bending resistance, a packaging material for a vacuum heat-insulating material which is formed of the laminate for a packaging material, and a vacuum heat-insulating material comprising the packaging material for a vacuum heat-insulating material. The laminate for a packaging material according to the present invention comprises a thermal fusion bonding layer, a gas barrier layer, and a protection layer stacked in that order. Two laminates for a packaging material are joined together at the outer peripheral sections thereof by thermal fusion bonding to form a packaging material for a vacuum heat-insulating material which has a space that can be filled with a core material in a vacuum state on the interior thereof. The protection layer is formed of a drawn nylon film having a flexural strength of 100 N/mm² or more in directions along four virtual lines (VL) which pass through a pre-set point at the center (P) in the width direction of a material film (MF) and extend radially on the surface of the protective film, and which have an interval of 45° between adjacent lines.

Description

Laminated body for packaging material, packaging material for vacuum heat insulating material and vacuum heat insulating material

This invention relates to the laminated body for packaging materials, the packaging material for vacuum heat insulating materials, and a vacuum heat insulating material.

As a packaging material laminate for forming a vacuum insulation material packaging material for forming a vacuum insulation material, for example, there are laminates described in Patent Documents 1 and 2. And this patent document 1 is disclosing the structure which improved rigidity and bending resistance as a structure which laminated | stacked two or more layers of nylon films excellent in mechanical characteristics, such as rigidity and bending resistance.
Moreover, as a laminate for a packaging material having a configuration substantially the same as that of the above-described laminate for a packaging material but having a different purpose of use, a laminate for packaging material forming a packaging material for a lithium ion battery (hereinafter simply referred to as “Li battery packaging material” Also referred to as a “laminated product”. The structure of this laminated body for Li battery packaging materials is described in Patent Documents 3 and 4, for example. And in this patent document 3, 4, if it is a laminated body for Li battery packaging materials described in the said patent document, it is possible to prevent the occurrence of pinholes and cracks during the molding of the packaging material for Li batteries. It is disclosed.

Japanese Patent No. 3482408 JP 2011-163415 A JP 2005-22336 A JP2011-181394

The nylon film constituting the laminate for packaging material generally has high hygroscopicity. For this reason, when the laminated body for packaging materials according to the prior art is laminated with two or more layers of nylon films as in the configuration disclosed in Patent Document 1, the rigidity and flex resistance of the laminated body are lowered early and packaging. Pinholes and cracks may occur when forming the material. For this reason, the vacuum heat insulating material manufactured using the said laminated body for packaging materials has the subject that sufficient heat insulation performance cannot be obtained.
Here, the case where the packaging material for vacuum heat insulating materials is formed using the laminated body for Li battery packaging materials described in patent documents 3 and 4 is assumed. In that case, when forming the vacuum insulation packaging material, pinholes and cracks may occur in the vacuum insulation packaging material, and the reduced pressure environment (high vacuum state) in the manufactured vacuum insulation material cannot be maintained. There is sex. As a result, the vacuum heat insulating material manufactured using the said laminated body for Li battery packaging materials may not be able to obtain sufficient heat insulation performance. Hereinafter, this point will be described in more detail.

Generally, the Li battery has a lower pressure than the atmospheric pressure (normal pressure) or the pressure in the vacuum heat insulating material. For this reason, the function (hereinafter also simply referred to as “pinhole prevention capability”) required for the laminated body for Li battery packaging material to prevent the occurrence of pinholes and cracks during the formation of the packaging material is an atmospheric pressure environment. It is sufficient if oxygen and moisture can be prevented from entering the underlying Li battery. On the other hand, the pinhole prevention capability required for the laminated body for packaging material forming the packaging material for vacuum insulation material is required to maintain the reduced pressure environment (high vacuum state) in the manufactured vacuum insulation material. This is higher than the pinhole prevention capability provided in the laminate for a Li battery packaging material according to the prior art. In other words, the laminated body for packaging material for forming the packaging material for vacuum heat insulating material prevents the occurrence of fine pinholes and fine cracks more than the laminated body for Li battery packaging material according to the prior art. Function is required. For this reason, when the packaging material for vacuum heat insulating materials was formed using the laminated body for Li battery packaging materials with low pinhole prevention capability described in patent documents 3 and 4, the reduced pressure environment ( There is a possibility that a vacuum heat insulating material that cannot maintain a high vacuum state) and does not have sufficient heat insulating performance may be manufactured.

The present invention is intended to solve such problems, and is a laminate for packaging material capable of improving rigidity and bending resistance, and a vacuum insulation material formed by the laminate for packaging material. It aims at providing the vacuum heat insulating material provided with the packaging material and the packaging material for the vacuum heat insulating material. More specifically, by improving rigidity and bending resistance, it is possible to prevent the occurrence of pinholes and cracks during the formation of packaging materials for vacuum insulation, and maintain the reduced pressure environment (high vacuum state) inside the vacuum insulation. It aims at providing the vacuum insulation material provided with the packaging material for vacuum insulation materials formed from the laminated body for packaging materials which can be formed, the lamination body for packaging materials, and the packaging material for vacuum insulation materials.

In order to achieve the above object, one embodiment of the present invention is a vacuum insulation in which two outer peripheral portions combined are joined together by heat welding, and a filling space in which a core material can be filled in a vacuum state is formed inside A laminate for packaging material forming a packaging material for material,
It is formed by laminating a heat welding layer, a gas barrier layer, and a protective layer in order,
The protective layer passes through one preset point, extends radially along the surface of the protective layer, and has a breaking strength in a direction along four imaginary lines having an interval of 45 ° between adjacent lines. Is formed of a stretched nylon film of 100 N / mm ² or more.

If it is one mode of the present invention, it passes through one preset point, extends radially along the surface of the protective layer, and has a direction along four imaginary lines having an interval of 45 ° between adjacent lines. A protective layer disposed outside the gas barrier layer is formed of a stretched nylon film having a breaking strength of 100 N / mm ² or more.
For this reason, a protective layer having a high breaking strength by a single layer of stretched nylon film having a breaking strength of 100 N / mm ² or more in eight directions radially extending through one preset point among the protective layers. Can be formed. Thereby, it becomes possible to improve the rigidity and bending resistance of the packaging material for a vacuum heat insulating material, and to suppress a decrease in rigidity and bending resistance of the protective layer due to moisture absorption.
With such a laminate for packaging material, it becomes possible to prevent the occurrence of pinholes and cracks during the formation of the packaging material for vacuum insulation material, and the reduced pressure environment (high vacuum state) in the manufactured vacuum insulation material ) Can be held. Therefore, if it is the laminated body for packaging materials which concerns on 1 aspect of this invention, the vacuum heat insulating material provided with sufficient heat insulation performance can be provided.

It is a top view which shows the vacuum heat insulating material which concerns on 1st embodiment of this invention. FIG. 2 is a sectional view taken along line II-II in FIG. FIG. 3 is an enlarged view of a range surrounded by a circle III in FIG. 2. FIG. 4 is an enlarged view of a range surrounded by a circle IV in FIG. 2. It is a figure which shows the measurement state of the average particle diameter of an aluminum crystal. It is a figure which shows the measurement state of the average particle diameter of an aluminum crystal. It is a figure which shows the structure of a stretched nylon film. It is a figure which shows the modification of 1st embodiment of this invention. It is a figure which shows the structure of a deep drawing verification machine.

Hereinafter, a first embodiment of the present invention will be described with reference to the drawings. In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of embodiments of the present invention. However, it will be apparent that one or more embodiments may be practiced without such specific details. In other instances, well-known structures and devices are schematically shown in order to simplify the drawing. Moreover, in each figure, the same referential mark is attached | subjected to the component which exhibits the same or similar function, and the overlapping description is abbreviate | omitted.

(First embodiment)
Hereinafter, a first embodiment of the present invention will be described with reference to the drawings.
(Constitution)
As shown in FIGS. 1 to 4, the vacuum heat insulating material 1 includes a vacuum heat insulating material packaging material 2 and a core material 4.
The packaging material 2 for vacuum heat insulating material combines two rectangular laminates 6 (laminates for packaging material), and joins the outer peripheral portions of the combined laminates 6 to seal the outer peripheral side in a plan view. It is divided into a region 8 and a filling space forming region 10 inside the seal region 8. In the following description, the two laminated bodies 6 forming the vacuum heat insulating material packaging material 2 are respectively arranged on the upper side in FIG. 2 and on the upper side in FIG. It may be indicated as 6d. In FIGS. 2 to 4, the thickness of the stacked body 6 is exaggerated for the sake of explanation. Moreover, 1st embodiment demonstrates the case where the laminated body 6 and the packaging material 2 for vacuum heat insulating materials are formed in the square by planar view as an example.

The seal region 8 is a region for forming a seal portion 80 that thermally welds and joins the heat-welding layers 20 included in the two laminates 6 at the outer peripheral portion of the two laminates 6.
The seal portion 80 is formed by four orthogonal straight lines surrounding the filling space forming region 10. That is, the seal part 80 is formed in a frame shape in plan view.
The filling space forming region 10 is a portion surrounded by the seal region 8 among the two laminated bodies 6 combined, and is disposed on the inner peripheral side of the seal region 8 and is formed in a rectangular shape in plan view. . In the first embodiment, as an example, a case where the filling space forming region 10 is formed in a square shape in a plan view will be described.
Further, unlike the seal region 8, the filling space forming region 10 is separated from the heat-welded layers 20 provided in the two laminates 6. In addition, a space formed by separating the heat-welding layers 20 provided in each of the two laminates 6 is a space in which the core material 4 can be filled in a vacuum state (hereinafter referred to as “filling space”). May be). That is, the filling space forming region 10 is a region in the filling material 2 for vacuum heat insulating material that forms a filling space.

The filling space forming region 10 corresponds to the filling space by performing press working (molding) on at least one of the two laminated bodies 6u and 6d before heat welding the heat welding layers 20 to each other. It can be formed into a shape (such as a deep drawing shape). That is, at least one of the two laminates 6 includes a filling space forming part 61 and a seal region forming part 62. More specifically, the filling space forming part 61 is formed into a shape corresponding to the filling space by pressing, and forms a portion corresponding to the filling space forming region 10 in the laminated body 6 subjected to pressing. Yes. Further, the seal region forming portion 62 is a flat plate-like portion formed on the outer peripheral side of the filling space forming portion 61 and forms a portion corresponding to the seal region 8.
In the first embodiment, as an example, a case will be described in which press working (molding) is performed on two stacked bodies 6u and 6d.

In the press working, the male mold and the female mold are closed in a state where the laminated body 6 is disposed between the male mold having the convex portion and the female mold having the concave portion, and the filling space forming region 10 in the laminated body 6 is closed. This is a process of deforming (stretching) the sectioned area to a shape corresponding to the filling space. Therefore, the convex part which a male type has, and the concave part which a female type have are made into the shape corresponding to filling space. In the first embodiment, as an example, the distance (depth of deep drawing) along the thickness direction of the stacked body 6 between the center of the filling space forming region 10 deformed by press working and the seal region 8 is as follows. The case where it is in the range of 5 mm or more and 10 mm or less will be described.

Moreover, the laminated body 6 and the filling space forming region 10 are rectangular in plan view.
Each laminate 6 is formed in a sheet shape, and includes a protective layer 12, a first adhesive layer 14, a gas barrier layer 16, a second adhesive layer 18, and a heat welding layer 20. In the following description, each component included in the stacked body 6u may be described with a symbol “u”. Similarly, in the following description, each component included in the stacked body 6d may be described with a symbol “d”.
The protective layer 12 is a layer for the purpose of protecting the gas barrier layer 16 when the vacuum insulating packaging material 2 is bent, and constitutes the outermost layer of the laminate 6. The detailed configuration of the protective layer 12 will be described later.
The first adhesive layer 14 is disposed between the protective layer 12 and the gas barrier layer 16 and adheres the protective layer 12 and the gas barrier layer 16.

The first adhesive layer 14 is a laminating adhesive that enables dry laminating, and requires a strong laminating strength between aluminum and a polymer film. Therefore, the adhesive is preferably composed of a main agent and a curing agent. An adhesive having a polyester polyurethane bond is used. More specifically, the main agent includes, for example, an acid component containing at least two or more selected from sebacic acid, isophthalic acid, terephthalic acid, octatanic acid, nonannic acid, undecanoic acid, and palmitic acid, ethylene glycol, It is a blend of a polyester resin composed of an alcohol component containing at least one selected from hexanediol and diethylene glycol, and a bisphenol A epoxy resin. The curing agent is an adhesive containing a polyisocyanate component (eg, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI). It is an agent.
The gas barrier layer 16 is a layer for the purpose of preventing water vapor or air from entering the filling space. As a material, for example, a film obtained by depositing a metal or an oxide on polyethylene terephthalate, an aluminum foil, or the like It is formed using the metal material which has the spreadability, and has airtightness. Hereinafter, an example of the gas barrier layer 16 will be described.

(Example of the configuration of the gas barrier layer 16)
An example of the configuration of the gas barrier layer 16 will be described with reference to FIGS. 1 to 4 and FIG.
The thickness of the gas barrier layer 16 is 7 μm or more. The thickness of the gas barrier layer 16 may be in the range of 7 μm to 40 μm, preferably in the range of 9 μm to 20 μm, and more preferably in the range of 9 μm to 12 μm. This is because if the thickness of the gas barrier layer 16 is less than 7 μm, there is a high possibility that pinholes are generated in the gas barrier layer 16 when the laminate 6 is pressed, and the thickness of the gas barrier layer 16 is increased. If the thickness exceeds 40 μm, the ductility and malleability of the gas barrier layer 16 with respect to the press working will be lower than values suitable for the press working.

In the first embodiment, as an example, a case where the thickness of the gas barrier layer 16 is in a range of 12 μm or more and 40 μm or less will be described.
The material of aluminum used as the material of the gas barrier layer 16 is preferably excellent in flexibility. For this reason, the material of the gas barrier layer 16 is, for example, in the range of 0.3% by mass or more and 9.0% by mass or less, preferably in the range of 0.7% by mass or more and 2.0% by mass or less, and more preferably. Uses an aluminum alloy containing iron within the range of 0.7 mass% or more and 1.7 mass% or less. This is because when the iron content is less than 0.3% by mass, the extensibility of the aluminum alloy is lost, and when the iron content exceeds 9.0% by mass, the flexibility of the aluminum alloy is hindered. This is because the manufacturing efficiency of the vacuum heat insulating material packaging material 2 is lowered.

In addition, the aluminum alloy used as the material of the gas barrier layer 16 is preferably a soft and flexible processed product that has been annealed.
The aluminum alloy used as the material for the gas barrier layer 16 is preferably, for example, if the average grain size of aluminum crystals is in the range of 6 μm to 12 μm and is in the range of 6 μm to 10 μm.
The reason why the average grain size of aluminum crystals is in the range of 6 μm or more and 12 μm or less is that when the average grain size is less than 6 μm, it is difficult to adjust the annealing temperature and time of the aluminum alloy. Furthermore, when the average grain size of the aluminum crystal exceeds 12 μm, the ductility and malleability of the aluminum alloy for press working are reduced from values suitable for press work.

In the first embodiment, JIS is used as the aluminum alloy that contains iron in the range of 0.7% by mass or more and 1.7% by mass or less and the average grain size of the aluminum crystals is in the range of 6 μm or more and 12 μm or less. “8079” or “8021” defined in H 4160 is used.
In the first embodiment, as an example, a case where the average particle diameter of aluminum crystals is equal to or less than the thickness of the gas barrier layer 16 will be described.

(Method of measuring the average particle size of aluminum crystals)
A method for measuring the average grain size of aluminum crystals will be described with reference to FIGS. 1 to 4 and FIGS. 5 and 6. FIG.
The average particle diameter of the aluminum crystal is a value measured by a fluorescent X-ray analyzer.
Specifically, as shown in FIGS. 5 and 6, an aluminum crystal Alc is obtained in a plan view of the gas barrier layer 16 using a fluorescent X-ray analyzer with respect to an aluminum alloy foil Alf that is a sheet-like aluminum alloy. The average particle size of is measured. In FIGS. 5 and 6, the length of “100 μm” is indicated by a bidirectional arrow as the length indicating the reference value.

The aluminum alloy foil Alf having a small average particle diameter of the aluminum crystal Alc shown in FIG. 5 is compared with the aluminum alloy foil Alf having a large average particle diameter of the aluminum crystal Alc shown in FIG. Is small.
For this reason, the aluminum alloy foil Alf having a small average particle size has a gap in which the aluminum crystal Alc moves during press working, that is, when the aluminum alloy foil is extended, as compared with the aluminum alloy foil Alf having a large average particle size. Since it is wide, ductility and malleability with respect to press working are increased.

The second adhesive layer 18 is disposed between the gas barrier layer 16 and the heat welding layer 20 and adheres the gas barrier layer 16 and the heat welding layer 20.
Further, the second adhesive layer 18 is a laminating adhesive that enables dry laminating processing similarly to the first adhesive layer 14, and preferably requires a strong laminating strength between aluminum and a polymer film. The adhesive consists of a main agent and a curing agent, and an adhesive having a polyester polyurethane bond is used. More specifically, the main agent and the curing agent may be the same as the main agent and the curing agent of the laminate adhesive constituting the first adhesive layer 14. That is, the main component of the laminating adhesive constituting the second adhesive layer 18 is, for example, at least two or more selected from sebacic acid, isophthalic acid, terephthalic acid, octatanic acid, nonannic acid, undecanoic acid, and palmitic acid. And a bisphenol A epoxy resin blended with a polyester resin composed of an acid component containing, an alcohol component containing at least one selected from ethylene glycol, hexanediol, and diethylene glycol. Further, the curing agent of the laminate adhesive constituting the second adhesive layer 18 is a polyisocyanate component (for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), An adhesive containing xylylene diisocyanate (XDI).

The heat welding layer 20 is a layer for sealing the core material 4 filled in the filling space in a vacuum state by forming the seal region 8, and has a material capable of heat welding, for example, thermoplasticity. It is formed using a polyolefin polymer material. Further, the heat-welded layer 20u included in the stacked body 6u is a heat-welded layer in which the surface opposite to the surface facing the second adhesive layer 18 is combined with the two stacked bodies 6u and 6d. In surface contact with layer 20d. In the first embodiment, as an example, a case where the material of the heat welding layer 20 is a polyolefin polymer material will be described.
Moreover, the material which can be heat-welded which forms the heat-welding layer 20 uses, for example, a resin containing cast polypropylene when heat resistance of 100 ° C. or higher is required as the use condition of the vacuum heat insulating material 1.

Furthermore, when the vacuum heat insulating material 1 is used as a bottom material of a house (heat insulating material or the like disposed in the floor), the thickness of the heat-welded layer 20 is in the range of 10 μm to 100 μm, and the melting point of the resin is 70 ° C. The above is preferred. This is because if the thickness of the heat-welded layer 20 is less than 10 μm, the heat seal strength in heat-welding is insufficient, so that cracks are easily generated with respect to impact. Further, when the thickness of the heat-welded layer 20 exceeds 100 μm, although the heat seal strength does not change, the barrier property of the heat-welded layer 20 is low, so there is a concern about permeation of oxygen and water vapor in a long-term storage environment. It is.
The core material 4 is formed using, for example, a material having fine voids such as glass wool, foamed polyurethane, and silica powder, and is filled in the filling space in a vacuum state.

(Detailed structure of the protective layer 12)
A detailed configuration of the protective layer 12 will be described with reference to FIGS. 1 to 4 and FIG.
The protective layer 12 is formed using a stretched nylon film as a material. As the stretched nylon film, for example, a nylon film having a polyamide resin as a basic skeleton is used.
The nylon film having a polyamide resin as a basic skeleton includes, for example, nylon 6, nylon 66, a copolymer of nylon 6 and nylon 66, metaxylylene adipamide (MXD6), and the like.
Moreover, the stretched nylon film which is the material of the protective layer 12 is manufactured by simultaneous biaxial stretching.
In addition, the simultaneous biaxial stretching process is performed by stretching the film simultaneously in the film flow direction (MD direction) and in the vertical direction (TD direction) perpendicular to the film flow direction when the film is stretched. It is the processing method to manufacture.

In the first embodiment, the stretched nylon film passes through one preset point, extends radially along the surface of the protective layer 12, and has four imaginary lines (virtual lines) having an interval of 45 ° between adjacent lines. Each stretch strength in the direction along the straight line) was 100 N / mm ² or more, and the stretched nylon film had an elongation percentage in the direction along the phantom line of 80% or more. In addition, the measuring method of the breaking strength (tensile strength) of the above-mentioned stretched nylon film will be described later.
Moreover, in 1st embodiment, as shown in FIG. 7, it passes along the width direction center P of the material film MF which is one point preset, and it extends radially along the surface of the protective layer 12, and is adjacent. Four imaginary lines VL that are 45 ° apart from the line pass through the center P in the width direction of the material film MF, and the four directions (0 ° direction, 45 degrees, 90 degrees, and 135 degrees directions).

The material film MF is a stretched nylon film before the protective layer 12 is formed.
Further, the center P in the width direction of the material film MF is set to an area of the laminate 6 that is partitioned into the filling space forming area 10.
In FIG. 7, for the sake of explanation, virtual lines VL in four directions are represented by a virtual line VLa in the 0 ° direction with respect to the MD direction, and a virtual line VLb in the 45 ° direction in the clockwise direction with reference to the MD direction. , A virtual line VLc in the 90 ° direction with respect to the MD direction, and a virtual line VLd in the 135 ° direction clockwise with respect to the MD direction.

That is, in the first embodiment, as an example, one of the four imaginary lines (VLa to VLd) (the imaginary line VLa) is, in plan view, the conveyance direction (MD direction) at the time of manufacturing the stretched nylon film. The case where it extends in parallel will be described.
The thickness of the protective layer 12 is at least 6 μm or more.
In the first embodiment, as an example, a case where the thickness of the protective layer 12 is in the range of 9 μm to 50 μm will be described. This is because if the thickness of the protective layer 12 is less than 9 μm, the stretched nylon film has insufficient elongation performance, and the gas barrier layer 16 is necked and broken when the vacuum heat insulating packaging material 2 is bent. Because.

(Measurement method of breaking strength of stretched nylon film)
The breaking strength of the stretched nylon film was measured in accordance with JIS K7127 under the conditions of a test piece of 15 mm, a chuck interval of 50 mm, and a test speed of 200 mm / min.

(Manufacturing method of the vacuum heat insulating material 1)
With reference to FIGS. 1-7, the manufacturing method of the vacuum heat insulating material 1 which concerns on 1st embodiment is demonstrated.
The manufacturing method of the vacuum heat insulating material 1 has a laminated body press process, the bag body production process which is a post process of a laminated body press process, and the vacuum filling process which is a post process of a bag body production process.
1. Laminate pressing step In the laminate pressing step, at least one of the two laminates 6u, 6d is pressed (molded) between the male die and the female die to form a filling space. The formation region 10 has a shape (such as a deep drawing shape) corresponding to the filling space.
As a result, a process of clearly partitioning the shape of the portion constituting the seal region 8 and the shape of the portion constituting the filling space forming region 10 is performed on the two stacked bodies 6u and 6d. In other words, in the laminated body pressing step, the shape of the portion constituting the seal region 8 (the seal region forming portion 62) and the filling space formation with respect to the laminated body 6 to be pressed out of the two laminated bodies 6u and 6d. A process of clearly partitioning the shape of the portion (filling space forming portion 61) constituting the region 10 is performed. Further, by pressing the laminate 6, an edge (edge) that is continuous in a frame shape in a plan view is formed in a portion constituting the filling space forming region 10 in the laminate 6 to be pressed. .

2. Bag body production process In the bag body production process, the two laminated bodies 6u and 6d are overlapped in a matched state, and the thermal welding layers 20 included in each of the three outer sides are opposed to each other. First heat welding is performed.
As a result, the heat-welded layers 20 are joined together to form a portion composed of three orthogonal straight lines in the seal portion 80 formed of four orthogonal straight lines surrounding the filling space forming region 10. Then, a bag body in which the other side of the outer peripheral portion is opened is created.

3. Vacuum filling process In the vacuum filling process, the core material 4 is inserted into the space formed between the two laminated bodies 6u and 6d from the opening formed in the bag body creation process, and the core material 4 is further inserted. For example, while the pressure in the space is reduced to 200 Pa or less, heat welding is performed on the remaining one side that has not been heat-welded in the bag forming process.
Thus, the filling space forming region 10, the filling space, and the frame-shaped seal portion 80 are formed, and the core material 4 is filled in the filling space in a vacuum state.

(Effects of the first embodiment)
(1) The protective layer 12 included in the laminated body 6 (laminated body for packaging material) extends radially along the surface of the protective layer 12 through the center P in the width direction of the material film MF, which is a preset point, In addition, each layer is formed of a stretched nylon film having a breaking strength of 100 N / mm ² or more in a direction along four virtual lines (VLa to VLd) having an interval of 45 ° between adjacent lines.
For this reason, only one layer of the protective layer 12 having a breaking strength of 100 N / mm ² or more in the eight directions radially extending through the center P in the width direction of the material film MF, which is a preset point. The nylon film makes it possible to form the protective layer 12 having a high breaking strength.
Thus, of the protective layer 12, a representative breaking strength of the eight directions extending radially, as 100 N / mm ² or more, the breaking strength of the entire protective layer 12, and can be a 100 N / mm ² or more Become.

As a result, it is possible to improve the rigidity and bending resistance of the vacuum heat insulating packaging material 2, and it is possible to suppress a decrease in the rigidity and bending resistance of the protective layer 12 due to moisture absorption.
In addition, since the durability and the bending resistance of the vacuum insulating material packaging material 2 can be maintained over a long period of time by suppressing the deterioration of the durability and the bending resistance of the protective layer 12, the gas barrier It becomes possible to suppress the occurrence of damage such as cracks in the layer 16.
With such a laminate for packaging material, it becomes possible to prevent the occurrence of pinholes and cracks during the formation of the packaging material for vacuum insulation material, and the reduced pressure environment (high vacuum state) in the manufactured vacuum insulation material ) Can be held. Therefore, if it is the laminated body 6 for packaging materials which concerns on 1st embodiment, the vacuum heat insulating material 1 provided with sufficient heat insulation performance can be provided.

(2) One of the four imaginary lines (VLa to VLd) (virtual line VLa) extends in parallel with the transport direction (MD direction) during production of the stretched nylon film in plan view.
For this reason, when the laminated body 6 is formed in a rectangular shape with reference to the conveying direction at the time of production of the stretched nylon film, and the filling space forming region 10 and the packaging material 2 for vacuum heat insulating material are formed in a rectangular shape, It is possible to form the vacuum heat insulating material packaging material 2 having a high breaking strength in eight directions extending radially from the center of the vacuum heat insulating material packaging material 2 by visual inspection.

(3) The stretched nylon film forming the protective layer 12 is a film having an elongation rate in the direction along the imaginary line VL of 80% or more.
For this reason, in the protective layer 12, it is possible to set the elongation rate in the representative eight directions extending radially to 80% or more and the overall elongation rate of the protective layer 12 to 80% or more.
(4) The thickness of the protective layer 12 is in the range of 9 μm to 50 μm.
For this reason, it becomes possible to form the highly durable protective layer 12 with only one layer of stretched nylon film.

(5) The stretched nylon film forming the protective layer 12 is manufactured by simultaneous biaxial stretching.
For this reason, it becomes possible to simplify the manufacturing process of the laminated body 6 compared with the case where a stretched nylon film is manufactured by sequential biaxial stretching, and the manufacturing process of the packaging material 2 for vacuum heat insulating materials is simplified. It becomes possible.
(6) The filling space forming region 10 is formed by pressing the stacked body 6.
For this reason, it becomes possible to manufacture the packaging material 2 for vacuum heat insulating materials by the continuous process with respect to the laminated body 6 conveyed.

(7) The vacuum heat insulating material 1 passes through the center P in the width direction of the material film MF, which is one point set in advance, and extends radially along the surface of the protective layer 12, and the distance between adjacent lines is 45 °. A packaging material 2 for vacuum heat insulating material including a protective layer 12 formed of a stretched nylon film having a breaking strength of 100 N / mm ² or more in a direction along four imaginary lines VL, and a filling space in a vacuum state A core material 4 to be filled is provided.
For this reason, while being able to improve the rigidity and bending resistance of the vacuum heat insulating material 1, it becomes possible to hold | maintain durability and bending resistance of the vacuum heat insulating material 1 over a long period of time.

(8) Since the laminate 6 (laminate for packaging material) has rigidity, bending resistance, and high breaking strength, the laminate 6 (laminate for packaging material) is press-molded (pressing and molding). Even if it is a case where it uses and is used for the packaging material 2 for vacuum heat insulating materials, it becomes possible to suppress generation | occurrence | production of a crack and a pinhole.
Therefore, durability and bending resistance over a long period can be imparted to the vacuum heat insulating material 1.

(9) The gas barrier layer 16 is formed of an aluminum alloy having an average particle diameter of aluminum crystals in the range of 6 μm to 12 μm and containing iron in the range of 0.7 mass% to 1.7 mass%. May be.
In this case, it becomes possible to increase the ductility and malleability of the aluminum alloy with respect to the press work, suppress the damage of the gas barrier layer 16 due to the press work, and form the filling space formed by the press work on the laminate 6. It becomes possible to improve the freedom degree of the shape of the part 61. FIG.
As a result, even if the requirements for the shape of the vacuum heat insulating material 1 differ depending on the use such as for home appliances, equipment, buildings, etc., the vacuum that can correspond to the shape of the vacuum heat insulating material 1 It becomes possible to form the packaging material 2 for heat insulating materials.
In addition, since the ductility and malleability of the gas barrier layer 16 can be increased, even if the gas barrier layer 16 is stretched when the seal region 8 is bent, generation of pinholes in the gas barrier layer 16 is prevented. It becomes possible to suppress.

(10) The thickness of the gas barrier layer 16 may be in the range of 9 μm to 20 μm.
In this case, compared with the case where the thickness of the gas barrier layer 16 is less than 9 μm, the possibility that pinholes are generated in the gas barrier layer 16 when the laminate 6 is pressed is reduced. It becomes possible. In addition to this, it is possible to reduce the thermal conductivity of the laminated body 6 and to improve the heat insulating performance of the vacuum heat insulating material 1 as compared with the case where the thickness of the gas barrier layer 16 exceeds 20 μm. .

(11) The average grain size of the aluminum crystals contained in the aluminum alloy forming the gas barrier layer 16 may be 10 μm or less.
In this case, it becomes possible to increase the ductility and malleability of the aluminum alloy with respect to press working, compared to the case where the average grain size of the aluminum crystal contained in the aluminum alloy exceeds 10 μm.
As a result, damage to the gas barrier layer 16 due to press working can be suppressed, so that the degree of freedom of the shape of the filling space forming region 10 formed by press working on the stacked body 6 can be improved. .

(12) The average particle diameter of the aluminum crystal contained in the aluminum alloy forming the gas barrier layer 16 may be a value measured by fluorescent X-ray diffraction with respect to the aluminum alloy in a plan view of the gas barrier layer 16.
In this case, the average particle diameter of the aluminum crystal contained in the aluminum alloy is measured by fluorescent X-ray diffraction before the laminated body 6 is manufactured, and the physical properties of the aluminum alloy are appropriate as the material of the gas barrier layer 16. It is possible to determine whether or not there is.

(13) The vacuum heat insulating material 1 includes the vacuum heat insulating packaging material 2 including the filling space forming portion 61 formed by pressing the laminated body 6 including the gas barrier layer 16 formed of an aluminum alloy, and in a vacuum state. You may provide the core material 4 with which filling space is filled. In addition to this, the gas barrier layer 16 is made of an aluminum alloy having an average grain size of aluminum crystals in the range of 6 μm to 12 μm and containing iron in the range of 0.7 mass% to 1.7 mass%. It may be formed.
In this case, the degree of freedom of the shape of the filling space forming portion 61 is different even when the requirements for the shape of the vacuum heat insulating material 1 differ depending on the use such as for home appliances, equipment, and buildings. It becomes possible to form the vacuum heat insulating material 1 of the shape according to a use using the packaging material 2 for vacuum heat insulating materials with high.

(Modification of the first embodiment)
Hereinafter, modifications of the first embodiment will be described.
(1) In the first embodiment, the stretched nylon film forming the protective layer 12 passes through a preset point and extends radially along the surface of the protective layer 12 and has an interval of 45 ° between adjacent lines. The stretched nylon film has a breaking strength of 100 N / mm ² or more in the direction along the four imaginary lines VL, but is not limited thereto.
That is, for example, as shown in FIG. 8, the stretched nylon film that forms the protective layer 12 passes through the center P in the width direction of the material film MF, which is a preset point, and is transported during production in a plan view. The stretched nylon film may have a breaking strength of 100 N / mm ² or more in the direction along two virtual lines VL inclined by 45 ° from the direction (MD direction).

In this case, when the laminate 6, the filling space forming region 10, and the vacuum heat insulating material packaging material 2 are formed in a rectangular shape based on the MD direction, the filling space forming region 10 of the filling space forming region 10 is folded when the vacuum heat insulating material packaging material 2 is bent. High rigidity can be exhibited with respect to the stress generated at the corner, that is, higher than the stress generated at other portions. For this reason, it becomes possible to improve the rigidity of the packaging material 2 for vacuum heat insulating materials.
In FIG. 8, for the sake of explanation, a virtual line VL indicating the MD direction is indicated by a reference symbol “VLMD”, and a virtual line VL inclined 45 ° clockwise (clockwise) from the MD direction is indicated by a reference symbol “VLMD”. A virtual line VL indicated by “VL1” and inclined by 45 ° counterclockwise (counterclockwise) from the MD direction is indicated by “VL2”.

(2) Although 1st embodiment demonstrated the case where the filling space formation area | region 10 was formed in the square by planar view, it does not limit to this. That is, you may form the filling space formation area | region 10 in a rectangle by planar view.
In this case, the stretched nylon film that forms the protective layer 12 passes through a preset point, extends radially along the surface of the protective layer 12, and is an imaginary line that overlaps the diagonal line of the filling space forming region 10 in plan view. It is good also as a stretched nylon film whose each breaking strength of the direction along is 100 N / mm < ² > or more.

(3) Although 1st embodiment demonstrated the case where the stretched nylon film was manufactured by simultaneous biaxial stretching, it is not limited to this. That is, if it is possible to form a stretched nylon film having a breaking strength of 100 N / mm ² or more at imaginary lines VL obtained by dividing the protective layer 12 at 45 ° intervals in plan view, the stretched nylon film is successively biaxially stretched. May be manufactured.
In the sequential biaxial stretching process, when stretching the film in the MD direction or the TD direction, the film is stretched in one of the MD direction and the TD direction without being simultaneously stretched. , MD direction and TD direction, it is the processing method which extends a film to the other and manufactures a stretched nylon film.
In this case, it becomes possible to form the protective layer 12 using a stretched nylon film manufactured with a device having a simple structure as compared with simultaneous biaxial stretching, and the manufacturing process of the packaging material 2 for vacuum heat insulating material It becomes possible to simplify.

(4) In the first embodiment, the case of performing press working (molding) on the two laminated bodies 6u and 6d has been described. However, the present invention is not limited to this. That is, press working may be performed on only one of the two laminated bodies 6u and 6d.
In this case, rigidity is required for the laminate 6 to be pressed. For this reason, the laminated body 6 to be pressed is the laminated body 6 of the first embodiment, that is, the protective layer 12 passes through the center P in the width direction of the material film MF, which is one point set in advance. A laminate that is formed of a stretched nylon film that extends radially along the surface and has a breaking strength of 100 N / mm ² or more in a direction along four imaginary lines that are 45 ° apart from adjacent lines. 6. Moreover, the laminated body 6 on the side not subjected to press working only needs to include the protective layer 12, the gas barrier layer 16, and the heat welding layer 20 having a configuration different from that of the first embodiment.

In addition, when the press processing to the laminated body 6 is not performed, the deformation due to the thickness of the core material 4 occurs in any of the two laminated bodies 6u and 6d. For this reason, the two laminated bodies 6u and 6d are both protected by the laminated body 6 of the first embodiment, that is, the protective layer 12 passes through the center P in the width direction of the material film MF, which is a preset point. Each layer is formed of a stretched nylon film having a breaking strength of 100 N / mm ² or more in a direction along four imaginary lines extending radially along the surface of the layer 12 and having an interval of 45 ° between adjacent lines. It is preferable to use the laminated body 6.

(5) In the first embodiment, the thickness of the gas barrier layer 16 is in the range of 9 μm to 20 μm, but is not limited thereto. That is, the upper limit value of the thickness of the gas barrier layer 16 may be 12 μm.
In this case, compared to the case where the upper limit value of the thickness of the gas barrier layer 16 exceeds 12 μm, the thermal conductivity of the laminate 6 can be reduced, and the heat insulating performance of the vacuum heat insulating material 1 can be improved. It becomes.

(6) In the first embodiment, as an aluminum alloy containing iron within a range of 0.7% by mass or more and 1.7% by mass or less, and having an average grain size of aluminum crystals of 6 μm or more and 12 μm or less, Although “8079” or “8021” defined in JIS H 4160 was used, the present invention is not limited to this. That is, the aluminum alloy forming the gas barrier layer 16 contains iron within the range of 0.7% by mass or more and 1.7% by mass or less, and the average grain size of the aluminum crystals is within the range of 6 μm or more and 12 μm or less. The alloy is not limited to “8079” or “8021” defined in JIS H 4160.

(Example of the first embodiment)
With reference to FIG. 1 to FIG. 8 of the first embodiment described above, FIG. 9 will be used to explain the vacuum heat insulating material 1 of the present invention example and the comparative example according to examples described below.
(Constitution)
As in the first embodiment described above, the vacuum heat insulating material 1 of the example has the same structure as the first embodiment described above, the protective layer 12, the first adhesive layer 14, the gas barrier layer 16, the second adhesive layer 18, the thermal welding layer 20, Each layer is formed by laminating by dry laminating. Moreover, the specific structure of each layer except the protective layer 12 shall be shown below.
First adhesive layer 14: A polyester polyurethane adhesive (LX500 manufactured by DIC) is used as a main agent, and an aromatic isocyanate (KW75 manufactured by DIC) is used as a curing agent.
-Gas barrier layer 16: The aluminum alloy (8021 by Toyo Aluminum Co., Ltd.) prescribed | regulated by JISH4000 is used as a material.
Second adhesive layer 18: A polyester polyurethane adhesive (LX500 manufactured by DIC) is used as a main agent, and an aromatic isocyanate (KW75 manufactured by DIC) is used as a curing agent.
-Thermal welding layer 20: Low density linear polyethylene (LLDPE: TUX-FCS manufactured by Mitsui Chemicals, Inc.) manufactured by casting is used as a material.

(Invention Example 1)
The vacuum heat insulating material 1 of Example 1 of the present invention was manufactured by an inflation method as a material of the protective layer 12 and had a thickness of 25 μm and passed through a preset point indicated as “stretched nylon 1” in Table 1. Then, the breaking strength in the direction along the four virtual lines VL extending radially along the surface of the protective layer 12 and having an interval of 45 ° between the adjacent lines, and the direction along the virtual line VL A stretched nylon film having an elongation rate is used.
In addition to this, the vacuum heat insulating material 1 of Example 1 of the present invention has a thickness of 12 μm as a material of the gas barrier layer 16 and contains 1.0 mass% of iron, and the average particle diameter of the aluminum crystal Alc is 10 μm. The aluminum alloy is used. The direction of the virtual line VL is the same as that in the first embodiment. Hereinafter, the aluminum alloy is also referred to as “aluminum alloy 1”. Further, “1” of the AL type shown in Table 2 refers to the aluminum alloy.

“0 °” shown in Table 1 indicates the direction along the imaginary line VLa in FIG. 7, and “45 °” shown in Table 1 indicates the direction along the imaginary line VLb in FIG. Show. Further, “90 °” shown in Table 1 indicates the direction along the virtual line VLc in FIG. 7, and “135 °” shown in Table 1 indicates the direction along the virtual line VLd in FIG. Show.

(Invention Example 2)
The vacuum heat insulating material 1 of Example 2 of the present invention was manufactured by an inflation method as a material of the protective layer 12 and had a thickness of 25 μm and passed through a preset point indicated as “stretched nylon 1” in Table 1. Then, the breaking strength in the direction along the four virtual lines VL extending radially along the surface of the protective layer 12 and having an interval of 45 ° between the adjacent lines, and the direction along the virtual line VL A stretched nylon film having an elongation rate is used.
In addition, the vacuum heat insulating material 1 of Example 2 of the present invention has a thickness of 20 μm as a material of the gas barrier layer 16 and contains 1.0% by mass of iron, and the average particle diameter of the aluminum crystal Alc is 10 μm. An aluminum alloy (aluminum alloy 1) is used. The direction of the virtual line VL is the same as that in the first embodiment.

(Invention Example 3)
The vacuum heat insulating material 1 of Example 3 of the present invention was manufactured by an inflation method as a material for the protective layer 12 and had a thickness of 25 μm and passed through a preset point indicated as “stretched nylon 1” in Table 1. Then, the breaking strength in the direction along the four virtual lines VL extending radially along the surface of the protective layer 12 and having an interval of 45 ° between the adjacent lines, and the direction along the virtual line VL A stretched nylon film having an elongation rate is used.
In addition, the vacuum heat insulating material 1 of Example 3 of the present invention is an aluminum alloy having a thickness of 20 μm and a very low iron content (for example, less than 0.1% by mass) as a material of the gas barrier layer 16. (For example, 1N30 defined in JIS H 4160) is used. The direction of the virtual line VL is the same as that in the first embodiment. Hereinafter, the aluminum alloy is also referred to as “aluminum alloy 2”. Further, “2” of the AL type shown in Table 2 refers to the aluminum alloy.

(Invention Example 4)
The vacuum heat insulating material 1 of Example 4 of the present invention was manufactured by an inflation method as a material of the protective layer 12 and had a thickness of 15 μm and passed through a preset point indicated as “stretched nylon 2” in Table 1. Then, the breaking strength in the direction along the four virtual lines VL extending radially along the surface of the protective layer 12 and having an interval of 45 ° between the adjacent lines, and the direction along the virtual line VL A stretched nylon film having an elongation rate is used.
In addition, the vacuum heat insulating material 1 of Example 4 of the present invention has a thickness of 20 μm as a material of the gas barrier layer 16 and contains 1.0% by mass of iron, and the average particle diameter of the aluminum crystal Alc is 10 μm. An aluminum alloy (aluminum alloy 1) is used. The direction of the virtual line VL is the same as that in the first embodiment.

(Invention Example 5)
The vacuum heat insulating material 1 of the invention example 5 is manufactured by an inflation method as a material of the protective layer 12 and has a thickness of 15 μm, and passes a preset one point indicated as “stretched nylon 2” in Table 1. Then, the breaking strength in the direction along the four virtual lines VL extending radially along the surface of the protective layer 12 and having an interval of 45 ° between the adjacent lines, and the direction along the virtual line VL A stretched nylon film having an elongation rate is used.
In addition, the vacuum heat insulating material 1 of Example 5 of the present invention is an aluminum alloy having a thickness of 40 μm and a very low iron content (for example, less than 0.1% by mass) as a material of the gas barrier layer 16. (For example, 1N30 defined in JIS H 4160) (aluminum alloy 2) is used. The direction of the virtual line VL is the same as that in the first embodiment.

(Invention Example 6)
The vacuum heat insulating material 1 of Example 6 of the present invention was manufactured by an inflation method as a material of the protective layer 12 and had a thickness of 15 μm and passed through a preset point indicated as “stretched nylon 2” in Table 1. Then, the breaking strength in the direction along the four virtual lines VL extending radially along the surface of the protective layer 12 and having an interval of 45 ° between the adjacent lines, and the direction along the virtual line VL A stretched nylon film having an elongation rate is used.
In addition, the vacuum heat insulating material 1 of Example 6 of the present invention is an aluminum alloy having a thickness of 20 μm and a very low iron content (for example, less than 0.1% by mass) as a material of the gas barrier layer 16. (For example, 1N30 defined in JIS H 4160) (aluminum alloy 2) is used. The direction of the virtual line VL is the same as that in the first embodiment.

(Invention Example 7)
The vacuum heat insulating material 1 of Example 7 of the present invention was manufactured by an inflation method as a material of the protective layer 12 and had a thickness of 15 μm and passed through a preset point indicated as “stretched nylon 2” in Table 1. Then, the breaking strength in the direction along the four virtual lines VL extending radially along the surface of the protective layer 12 and having an interval of 45 ° between the adjacent lines, and the direction along the virtual line VL A stretched nylon film having an elongation rate is used.
In addition, the vacuum heat insulating material 1 of Example 7 of the present invention has a thickness of 12 μm as a material of the gas barrier layer 16 and contains 1.0 mass% of iron, and the average particle diameter of the aluminum crystal Alc is 10 μm. An aluminum alloy (aluminum alloy 1) is used. The direction of the virtual line VL is the same as that in the first embodiment.

(Invention Example 8)
The vacuum heat insulating material 1 of Example 8 of the present invention was manufactured by an inflation method as a material for the protective layer 12 and had a thickness of 15 μm and passed through a preset point indicated as “stretched nylon 2” in Table 1. Then, the breaking strength in the direction along the four virtual lines VL extending radially along the surface of the protective layer 12 and having an interval of 45 ° between the adjacent lines, and the direction along the virtual line VL A stretched nylon film having an elongation rate is used.
In addition, the vacuum heat insulating material 1 of Example 8 of the present invention is an aluminum alloy having a thickness of 12 μm and a very low iron content (for example, less than 0.1% by mass) as a material of the gas barrier layer 16. (For example, 1N30 defined in JIS H 4160) (aluminum alloy 2) is used. The direction of the virtual line VL is the same as that in the first embodiment.

(Comparative Example 1)
The vacuum heat insulating material 1 of the comparative example 1 was manufactured by a casting method as a material of the protective layer 12 and had a thickness of 15 μm, and passed a preset one point indicated as “stretched nylon 3” in Table 1. The rupture strength in the direction along the four imaginary lines VL extending radially along the surface of the protective layer 12 and having an interval of 45 ° between adjacent lines, and the extension in the direction along the imaginary line VL A stretched nylon film having a rate is used.
In addition, the vacuum heat insulating material 1 of Comparative Example 1 is an aluminum alloy (as a material for the gas barrier layer 16) having a thickness of 20 μm and a very low iron content (for example, less than 0.1% by mass) ( For example, 1N30) (aluminum alloy 2) defined in JIS H 4160 is used. The direction of the virtual line VL is the same as that in the first embodiment.

(Comparative Example 2)
The vacuum heat insulating material 1 of Comparative Example 2 was manufactured by a casting method as a material for the protective layer 12 and had a thickness of 15 μm, and passed a preset one point indicated as “stretched nylon 3” in Table 1. The rupture strength in the direction along the four imaginary lines VL extending radially along the surface of the protective layer 12 and having an interval of 45 ° between adjacent lines, and the extension in the direction along the imaginary line VL A stretched nylon film having a rate is used.
In addition, the vacuum heat insulating material 1 of Comparative Example 2 has a thickness of 40 μm as a material of the gas barrier layer 16, contains 1.0 mass% of iron, and has an average particle diameter of aluminum crystal Alc of 10 μm. An aluminum alloy (aluminum alloy 1) is used. The direction of the virtual line VL is the same as that in the first embodiment.

(Comparative Example 3)
The vacuum heat insulating material 1 of Comparative Example 3 was manufactured by a casting method as a material of the protective layer 12 and had a thickness of 15 μm, and passed a preset one point indicated as “stretched nylon 3” in Table 1. The rupture strength in the direction along the four imaginary lines VL extending radially along the surface of the protective layer 12 and having an interval of 45 ° between adjacent lines, and the extension in the direction along the imaginary line VL A stretched nylon film having a rate is used.
In addition to this, the vacuum heat insulating material 1 of Comparative Example 3 is an aluminum alloy having a thickness of 40 μm and a very low iron content (for example, less than 0.1% by mass) as a material of the gas barrier layer 16 ( For example, 1N30) (aluminum alloy 2) defined in JIS H 4160 is used. The direction of the virtual line VL is the same as that in the first embodiment.

(Measurement result)
As the evaluation of the vacuum heat insulating material in each configuration, the maximum deep drawing distance 1 (mm), the state at the time of 6 mm deep drawing, the maximum deep drawing distance 2 (mm), the molding state and the thermal conductivity (W / mK) are calculated. did. Here, the “maximum deep drawing distance 1” indicates the maximum deep drawing distance when measured without applying a lubricant (erucic acid amide) to the surface of the vacuum heat insulating material 1. The “state during 6 mm deep drawing” indicates a pinhole situation when 6 mm deep drawing is performed without applying a lubricant to the surface of the vacuum heat insulating material 1. “Maximum deep drawing distance 2” indicates the maximum deep drawing distance when a lubricant (erucamide) is applied and measured in order to make the friction coefficient of the surface of the vacuum heat insulating material 1 uniform between samples. Is.
The results of each measurement are shown in Table 2. In Table 2, items indicated by “−” and blanks indicate that measurement was impossible or measurement was impossible. Further, Comparative Example 1 in Table 2 corresponds to the difference in the type of nylon of Example 3. Comparative Example 3 corresponds to the difference in the type of nylon of Example 5.

(Calculation of maximum deep drawing distance 1, 2)
The deep drawability of the laminate 6 was measured using a deep draw verifying machine 22 shown in FIG.
The deep drawing verifying machine 22 includes a male mold 24, a female mold 26, and a stripper plate 28.
The male mold 24 includes a convex portion 30 that protrudes downward toward the female mold 26.
The female die 26 is arranged below the male die 24, and a convex arrangement space 32 in which the convex part 30 can be arranged is formed.
The stripper plate 28 is a plate-like member for pressing the laminated body 6 against the flat portion 34 in which the convex arrangement space 32 is not formed in the female die 26, and is movable in the vertical direction.

When the deep drawability of the laminate 6 is measured using the deep drawing verification machine 22, first, the male die 24 and the female die 26 are opened with the male die 24 and the female die 26 opened (die opening state). The laminate 6 disposed between the two is pressed against the flat portion 34 by the stripper plate 28 and fixed. Then, the distance between the male mold 24 and the female mold 26 is decreased, and the stacked body 6 is pushed (pressed) downward by the convex portion 30, and further, the downward moving distance of the convex portion 30 in the convex portion arrangement space 32. (Deep drawing distance) is changed, and an average distance until a pinhole is generated in the gas barrier layer 16 is calculated. Thus, the deep drawing distance (mm) shown in Table 2 is calculated from the average distance until pinholes are generated in the gas barrier layer 16. In the present invention example and the comparative example, this deep drawing distance is determined when the lubricant is not applied to the surface of the vacuum heat insulating material 1 (maximum deep drawing distance 1) and when the lubricant is applied to the surface of the vacuum heat insulating material 1 (maximum depth). The measurement was performed separately for the aperture distance 2). Note that erucic acid amide was used as the lubricant.
In addition, the curvature radius R in the corner part of the convex part 30 and the convex part arrangement | positioning space 32 shall be 1 mm, and the hard type | mold 24 and the female type | mold 26 are hard-chrome plated. In all the comparative examples and the inventive examples, the change speed of the deep drawing distance (that is, the deep drawing speed) was constant (10 mm / min). The holding time of the laminated body 6 was 2 seconds, and the pressing pressure of the laminated body 6 was 0.8 MPa.

(State of pinhole at the time of 6mm deep drawing)
Using the deep drawing verifying machine 22 shown above, the pinhole generated in the laminate 6 with the male mold 24 lowered by 6 mm (the depth of entry of the convex portion 30 into the convex portion arrangement space 32 is 6 mm). Was visually observed using an LED light of 300 lux or more in a dark room.

(State of molding)
When the maximum deep drawing distance 2 is measured, that is, when the maximum deep drawing distance is measured by applying a lubricant (erucic amide) to the surface of the vacuum heat insulating material 1, the corners of the deep drawn region are crushed. Observed. The case where the corner was not crushed even after deep drawing was evaluated as “◯”, and the case where the corner was crushed by deep drawing was evaluated as “x”.
From the results of this example and the comparative example, it was found that when the aluminum foil provided in the gas barrier layer 16 was thin, the strength was insufficient, and the corners were rounded against the tension of the nylon provided in the protective layer 12, so that it could not be molded neatly. .

(Thermal conductivity)
The laminate 6 was heated periodically, and the thermal conductivity of the laminate 6 was measured using an AC heating method in which the response of heat according to the frequency and the amplitude at the distance from the measurement location was measured. When the thermal conductivity in the laminate 6 is high, a phenomenon that heat is conducted through the film (a phenomenon called a thermal bridge) occurs. Therefore, it is desirable that the thermal conductivity of the laminate 6 is low. The
Further, as shown in Table 2, it can be seen that Examples 1 to 6 of the present invention have a larger maximum deep drawing distance than Comparative Examples 1 and 2. It can also be seen that the maximum deep drawing distance is similarly increased by increasing the thickness of the aluminum foil as the gas barrier layer 16. However, when the thickness of the aluminum foil is increased by the gas barrier layer 16, the value of the thermal conductivity increases, which is not desirable.

As mentioned above, if it is the laminated body for packaging materials which concerns on 1st embodiment, the packaging material for vacuum heat insulating materials, and a vacuum heat insulating material, the subject which this invention will solve can be solved. Hereinafter, peripheral technologies and related technologies of the invention according to the first embodiment of the present invention will be described.

Energy savings in buildings such as home appliances, equipment, and houses, especially for residential use, with the aim of reducing energy for air conditioning in summer and winter Is required. In addition, it is excellent for the purpose of reducing the risk of myocardial infarction and cerebral infarction due to heat shock caused by temperature difference in bathroom, toilet, dressing room, etc. A heat insulating material having heat insulating performance is required.

As a heat insulating material having excellent heat insulating performance, a vacuum heat insulating material is provided with a packaging material for vacuum heat insulating material formed by combining two laminates having gas tightness (gas barrier properties) and a core material having fine voids. There is a vacuum heat insulating material formed by vacuum filling a core material inside the packaging material.
The vacuum heat insulating material exhibits high heat insulating performance by maintaining the inside of the vacuum heat insulating packaging material at a high degree of vacuum and suppressing heat transfer due to gas convection. For this reason, the packaging material for vacuum heat insulating materials is required to have high gas barrier properties.

Moreover, when vacuum-filling the core material such as glass wool into the vacuum insulating material packaging material, it is filled by applying pressure from above in the vacuum chamber. Here, glass wool is a material obtained by processing glass into a fiber shape of 10 μm or less.
However, if pressure is applied from above in the vacuum chamber and the core material is vacuum-filled inside the vacuum heat insulating packaging material, the core material may break through the laminate from the inside. For this reason, rigidity is requested | required of the packaging material for vacuum heat insulating materials.

In addition, when using a vacuum heat insulating material, it is necessary to bend the seal region. When a crack called a pinhole occurs in the barrier layer when the seal region is bent, the inside of the vacuum heat insulating material becomes atmospheric pressure, and heat insulation Performance decreases. For this reason, the vacuum insulation packaging material is required to have bending resistance.
In response to these requirements, for example, Patent Document 1 includes a configuration in which two or more layers of nylon films having excellent mechanical properties such as rigidity and bending resistance are laminated to improve rigidity and bending resistance. It is disclosed.

Although the present invention has been described above with reference to specific embodiments, it is not intended that the present invention be limited by these descriptions. From the description of the invention, other embodiments of the invention will be apparent to persons skilled in the art, along with various variations of the disclosed embodiments. Therefore, it is to be understood that the claims encompass these modifications and embodiments that fall within the scope and spirit of the present invention.

DESCRIPTION OF SYMBOLS 1 ... Vacuum heat insulating material, 2 ... Packaging material (packaging material for vacuum heat insulating material), 4 ... Core material, 6 ... Laminated body (laminated body for packaging material), 8 ... Sealing area, 10 ... Filling space formation area, 12 ... Protective layer, 14 ... first adhesive layer, 16 ... gas barrier layer, 18 ... second adhesive layer, 20 ... thermal weld layer, 22 ... deep drawing verifier, 24 ... male type, 26 ... female type, 28 ... stripper plate, DESCRIPTION OF SYMBOLS 30 ... Convex part, 32 ... Convex part arrangement space, 34 ... Plane part, 61 ... Filling space formation part, 62 ... Seal area formation part, 80 ... Seal part, VL ... Virtual line, MF ... Material film, P ... Material film Center of width direction of MF, Alf ... aluminum alloy foil, Alc ... aluminum crystal

Claims (13)

1. It is a laminate for packaging material that forms a packaging material for vacuum heat insulating material in which a filling space capable of filling a core material in a vacuum state is formed by joining the outer peripheral portions of the two combined by heat welding,
   It is formed by laminating a heat welding layer, a gas barrier layer, and a protective layer in order,
   The protective layer passes through one preset point, extends radially along the surface of the protective layer, and has a breaking strength in a direction along four imaginary lines having an interval of 45 ° between adjacent lines. Is formed of a stretched nylon film of 100 N / mm ² or more.
2. The laminate for packaging material according to claim 1, wherein one of the imaginary lines extends in parallel with a conveying direction when the stretched nylon film is produced in plan view.
3. The laminate for a packaging material according to claim 1 or 2, wherein the stretched nylon film has an elongation rate in a direction along the phantom line of 80% or more.
4. The laminate for a packaging material according to any one of claims 1 to 3, wherein a thickness of the protective layer is in a range of 9 µm to 50 µm.
5. The gas barrier layer is formed of an aluminum alloy containing iron within a range of 0.7% by mass or more and 1.7% by mass or less,
   The laminate for packaging material according to any one of claims 1 to 4, wherein an average particle diameter of aluminum crystals contained in the aluminum alloy is in a range of 6 µm to 12 µm.
6. The laminate for a packaging material according to claim 5, wherein the average particle diameter is 10 µm or less.
7. The laminate for a packaging material according to claim 5 or 6, wherein the average particle diameter is a value measured by fluorescent X-ray diffraction with respect to the aluminum alloy in a plan view of the gas barrier layer.
8. The laminate for a packaging material according to any one of claims 1 to 7, wherein the thickness of the gas barrier layer is in a range of 9 µm to 20 µm.
9. The laminate for packaging material according to claim 8, wherein the thickness of the gas barrier layer is 12 µm or less.
10. In plan view, it is divided into a seal area on the outer peripheral side for forming the seal part joined by the thermal welding, and a filling space forming area for forming the filling space,
    10. The filling space forming portion formed in a shape corresponding to the filling space is formed by pressing the filling space forming region. 11. Laminated body for packaging material.
11. It is a packaging material for a vacuum heat insulating material in which the outer peripheral portions of the two laminated bodies combined are joined together by heat welding, and a filling space in which a core material can be filled in a vacuum state is formed inside,
    The packaging material for vacuum heat insulating materials, wherein at least one of the two laminates is the packaging material laminate according to any one of claims 1 to 10.
12. The laminate for packaging material of at least one of the two laminates includes a filling space forming portion formed in a shape corresponding to the filling space by press working. Packaging material for vacuum insulation.
13. The vacuum insulation packaging material,
    A core material filled in the filling space in a vacuum state,
    A vacuum heat insulating material characterized in that at least one of the combined two laminates for packaging material is the laminate for packaging material according to any one of claims 1 to 10.

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