JP6056169B2 - Vacuum insulation - Google Patents

Description

  The present invention relates to a vacuum heat insulating packaging material and a vacuum heat insulating material using a laminate as a heat insulating packaging material.

  Currently, various laminates obtained by laminating various materials are used as packaging materials for heat insulating materials. Among them, much research has been conducted on packaging materials that can maintain a high vacuum state inside a material having a high heat insulating property. These vacuum heat insulating materials are used in refrigerators, vending machines, low temperature containers, and the like.

  Conventionally, there are three known ways of transferring heat, called heat conduction, radiant heat, and convection. Thermal conduction means that the motion of molecules and electrons becomes intense when an object is heated. The thermal vibration is spread in a spherical shape around the heat source, and heat is transmitted. Metals are considered to have high thermal conductivity because free electrons are responsible for thermal conduction.

  Radiant heat means that electromagnetic waves transmit heat as a heat medium in a vacuum state. The same goes for transferring heat from the sun in space. The emission and transmission of electromagnetic waves in this way is called radiation.

  Convection is a phenomenon in which water or air in a certain volume receives heat to expand its volume and reduce its density, thereby pushing away cold objects and circulating materials. As described above, there are three ways to conduct heat, and by preventing these, the heat insulation performance is increased.

Glass wool is a core material for vacuum heat insulating materials reported so far. This is a cotton-like material having glass (SiO ₂ ) of 10 μm or less, and it is said that heat insulation is improved by artificially making glass into a fiber. Furthermore, in order to lower the thermal conductivity, the vacuum heat insulating material is intended to suppress the heat conduction by evacuating the inside. This is considered to increase the heat insulation property because it has a configuration that can eliminate all of the above heat transfer methods. That is, the vacuum heat insulating material exterior material is required to have a configuration in which the internal vacuum degree does not change.

  The structure of the laminate of the vacuum heat insulating material reported so far is composed of three or more layers, and includes the outermost layer, the barrier layer, and the sealant layer, or the outermost layer 1, the intermediate layer, the barrier layer, and the sealant layer. (For example, refer to Patent Document 1).

JP 2007-313652 A Japanese Patent No. 4453512 JP 2011-163415 A

  There are many pouch-shaped packaging materials for vacuum heat insulating materials (see, for example, Patent Document 2). The reason for this is that aluminum or a metal-deposited film cannot be used for the portion having a barrier property for maintaining the degree of vacuum in the laminate unless the pouch shape is used.

  However, by using a convex mold called deep drawing to make a tray-shaped concave, the outer shape is easy and the molding method is excellent in filling suitability. In particular, it is known that the vacuum heat insulating material is required to be in a state of 10 Pa or less in the pressure reducing step of the vacuum heat insulating material, and time is required in the vacuuming step (see, for example, Patent Document 3). In the configuration mentioned so far, by using a tray-shaped concave method called deep drawing, aluminum or metal vapor deposition film is stretched and pinholes are generated, and the vacuum degree in the inner bag can not be maintained. End up.

  For the reasons described above, a vacuum insulation packaging material was developed in which a laminate comprising a barrier layer made of aluminum or a metal vapor-deposited film was molded by a deep drawing process excellent in filling suitability. More specifically, when deep drawing is performed, the development of a packaging material that does not have aluminum pinholes and does not change the degree of vacuum of the inner bag of the laminate for vacuum heat insulating material and does not have water vapor and oxygen permeability. went.

  The present invention relates to a packaging material for a vacuum heat insulating material that does not generate pinholes in the laminated body even when deep drawing is performed, does not change the vacuum degree of the inner bag of the laminated body, and has no water vapor and oxygen permeability. It aims at providing the vacuum heat insulating material using this.

The vacuum heat insulating material according to the first invention is made of the first laminated body, and includes a bottom material having a concave portion and a second laminated body, and a lid material for closing the open portion of the bottom material. A vacuum heat insulating material, wherein each of the first laminated body and the second laminated body includes an outermost layer, a barrier layer, and an innermost layer, and at least one layer from the outermost layer to the innermost layer is for lamination. The laminate adhesive is laminated through an adhesive, and the laminate adhesive is composed of a main agent and a curing agent. An acid component containing at least two or more selected from palmitic acid, and at least selected from ethylene glycol, hexanediol, and diethylene glycol It is a blend of a polyester resin comprising one type of alcohol component and a bisphenol A type epoxy resin, the curing agent is an adhesive layer comprising a polyisocyanate component, and the barrier layer of the first laminate the made of aluminum, the barrier layer of the second laminate, Ri Do from the film obtained by depositing a metal or nonmetal polyester or nylon film, the outermost layer of the thickness of said first laminate 6μm or more characterized in that there.

Vacuum heat insulating material according to the second invention, the outermost layer of the first laminate and the second laminate, characterized by comprising the film-forming polyamide by the biaxial stretching of the inflation process or cast .

Vacuum heat insulating material according to the third invention, the barrier layer before Symbol first stack, characterized by comprising the thickness 15μm more aluminum.

Vacuum heat insulating material according to the fourth invention, prior Symbol innermost layer of the first laminate and the second laminate, the thickness 10μm or more polyolefin resins, unsaturated carboxylic acid, ethylene, and, from among polypropylene It contains one type of polymer or two or more types of copolymers selected.

Vacuum heat insulating material according to the fifth invention, the in the recess of the base material and the core material having a heat insulating property is filled, within the recess of the base material in which the core material is filled is tightly sealed in a vacuum state It is characterized by.

  According to the above-described invention, it is possible to form a concave mold such as deep drawing, to provide a vacuum insulating material packaging material for a laminate that can be quickly filled and processed and has a high barrier property in a metal foil or a metal vapor-deposited film. can do. Moreover, the packaging material for vacuum heat insulating materials which performed the deep drawing process which does not change the atmospheric | air pressure of the content with time, and can be rich in heat insulation, and a vacuum heat insulating material using the same can be provided.

Sectional drawing which shows embodiment of this invention and shows the structure of a 1st laminated body Sectional drawing which shows embodiment of this invention and shows the structure of a 2nd laminated body Sectional drawing which shows embodiment of this invention and shows the structure of a vacuum heat insulating material

  The vacuum heat insulating packaging material according to the present invention will be described with reference to the drawings. FIG. 3 shows the entire vacuum heat insulating material, FIG. 1 shows a basic structure of a laminate formed by deep drawing, and FIG. 2 shows a structure provided with an intermediate layer.

  As a result of creative research, the inventor has found that the present invention solves the problem of the present invention by forming a multi-layered packaging material and a laminated body made of each material described below. The present invention has been completed. The vacuum heat insulating material according to the present invention includes a laminated body (hereinafter referred to as a bottom material 10) formed by deep drawing as shown in FIG. 3, and a laminated body for closing an open portion after putting the heat insulating material therein. (Hereafter, the lid material 8) is required. A vacuum heat insulating material is configured by placing a heat insulating material 9 made of a core material having high heat insulating properties in the two kinds of laminates and thermally welding the heat sealing portion 11 in a high vacuum state. The bottom material 10 and the lid material 8 are provided with a laminate of outermost layer / barrier layer / sealant layer. The laminated body of the bottom material 10 to be deep drawn may be heat-sealed and sealed with the laminated body of the lid material 8 having the same structure including the material, The laminated body of the lid material 8 which is not the same structure including material may be heat-sealed and sealed.

  In the laminate of FIG. 2, the outermost layer 1 and the barrier layer 5 are bonded to each other by the laminate adhesive layer 2, and the barrier layer 5 and the sealant layer 7 are bonded to each other by the laminate adhesive layer 6. Further, as shown in FIG. 1, the bottom material 10 and the lid material 8 may include a laminate of the outermost layer / intermediate layer / barrier layer / sealant layer. In the laminate of FIG. 1, the outermost layer 1 and the intermediate layer 3 are laminated by the laminate adhesive layer 2, the intermediate layer 3 and the barrier layer 5 are laminated by the laminate adhesive layer 4, and the barrier layer 5 and the sealant layer 7 are laminated. The adhesive layers 6 are bonded to each other.

  The outermost layer 1 having a configuration used for the bottom material 10 in the present invention is made of stretched nylon or stretched polyester. Examples of nylon include nylon 6, nylon 6, 6, nylon 6, 6 and nylon 6 copolymer, metaxylylene adipamide (MXD6), and the like having polyamide resin as a basic skeleton. Examples of the stretched polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polycarbonate.

  Although the outermost layer 1 of the bottom material 10 shown in FIG. 3 varies depending on the depth at which deep drawing is performed, it is necessary to have a thickness of at least 6 μm or more in consideration of the possibility of pinholes during film formation of a single film. Preferably, the thickness is from 12 μm to 25 μm, and the film formation method is desirably a film formed by stretching by inflation processing or cast biaxial stretching.

  The barrier layer 5 having a configuration used for the bottom material 10 and the lid material 8 in the present invention is a layer for particularly preventing air from entering, and a pinhole of the barrier layer 5 alone and a deep drawing process were performed. There is a need for a malleable metal such as aluminum with a thickness of 12 μm or more to prevent occasional pinholes. Preferably, aluminum having a thickness of 15 to 80 μm is required. In order to improve the occurrence of pinholes such as cracks in deep drawing, iron is contained in the range of 0.3% to 9.0%, preferably 0.7% to 2.0%. % Is desirable. When the iron content is less than 0.3%, there is no effect in preventing the generation of pinholes in deep drawing, and when it is 9.0% or more, the flexibility of aluminum is hindered, and the laminate As a result, the bag-making property becomes worse.

  Aluminum used for the barrier layer 5 of the bottom material 10 changes physical properties such as rigidity, flexibility, waist strength, and hardness under annealing (annealing treatment) conditions during manufacture in cold rolling. The aluminum used in this example is preferably a soft, soft treated product that has been appropriately annealed, rather than a product that has not been annealed (hard processed product). Moreover, it is desirable that the annealing conditions are appropriately selected from the appropriateness of deep drawing and filling.

  As the innermost sealant layer 7 in the bottom material 10 and the lid material 8, the sealant layer 7 of the bottom material 10 and the sealant layer 7 of the lid material 8 need to have heat sealability. A resin having heat welding properties is used depending on the environment in which the vacuum heat insulating material is used. Preferably, it is a resin containing polypropylene (hereinafter referred to as PP) when heat resistance of 100 ° C. or higher is required, and a resin containing polyethylene (hereinafter referred to as PE) or PP is desirable when it is 100 ° C. or lower. Furthermore, the thickness of the sealant layer 7 used for the bottom material 10 is preferably 10 μm to 100 μm, and the resin has a melting point of 70 ° C. or higher. However, it is desirable to use the sealant layer 7 of the bottom material 10 and the lid material 8 also in the vicinity of the same melting point. The sealant layer 7 can include one type of polymer or two or more types of copolymers selected from polyolefin resins having a thickness of 10 μm or more, unsaturated carboxylic acid, ethylene, and polypropylene.

  When the sealant layer 7 is 10 μm or less, the heat seal strength between the polyolefins is insufficient. Further, even if the thickness exceeds 100 μm, the heat seal strength does not change, but the thickness of the laminate is increased, so that the space saving of the present invention is lost.

  When the intermediate layer 3 is provided on the bottom material 10, the purpose is to prevent aluminum cracks and increase the waist strength of the bottom material 10. When aluminum is 20 μm or thinner, the waist strength is low, so that when deep drawing is performed and a vacuum heat insulating material is filled, the shape cannot be maintained. In order to improve this, as the material used for the intermediate layer 3, stretched polyester includes polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate and the like. The thickness is preferably 12 μm to 25 μm.

  The barrier layer 5 in the lid member 8 may be the same aluminum as the barrier layer 5 of the bottom member 10, but flexibility is not required because deep drawing is not performed. Therefore, it can be replaced by a film in which a metal or a nonmetal is vapor-deposited on a polyester or nylon film. In this case, it is preferable to use a film in which a metal or a nonmetal is deposited to a thickness of 1 μm or less.

  When aluminum is used for the barrier layer of the lid material 8, the thermal conductivity of the packaging material itself is increased, and heat conduction is performed with the aluminum of the bottom material 10. Therefore, it is desirable to use aluminum having a thickness of 6 μm to 20 μm, or a film on which metal or nonmetal is deposited.

  The vacuum heat insulating material packaging material is laminated by dry laminating using a laminating adhesive. This laminating adhesive requires a strong laminating strength between aluminum and a polymer film. Therefore, the adhesive preferably consists of a main agent and a curing agent. The main agent is 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, and ethylene glycol, hexanediol, and diethylene glycol. It is a blend of a polyester resin composed of an alcohol component containing at least one selected from the above, and a bisphenol A epoxy resin. As the curing agent, an adhesive made of a polyisocyanate component (TDI, MDI, IPDI, HDI, XDI) is used.

(A) The bottom material 10 is composed of outermost layer 1 / barrier layer 5 / sealant layer 7. These layers are laminated by dry lamination via a laminating adhesive. Nylon with a thickness of 25 μm (hereinafter referred to as “ONY”) subjected to inflation processing is used as the outermost layer 1, aluminum with a thickness of 40 μm as the barrier layer 5 (hereinafter referred to as “AL”), and a sealant layer 7. A laminate (1) was obtained using a linear low density polyethylene (hereinafter referred to as “LLDPE”) having a thickness of 40 μm and an adhesive. Here, the adhesive is a blend of an acid component containing isophthalic acid and terephthalic acid as a main component and a polyester resin composed of an alcohol component composed of diethyl glycol and a bisphenol A type epoxy resin, and a polyisocyanate component as a curing agent. An adhesive containing was used.
Laminate (1): ONY (25) / AL (40) / LLDPE (40)

(B) The bottom material 10 is composed of the outermost layer 1 / barrier layer 5 / sealant layer 7. These layers are laminated by dry lamination via a laminating adhesive. Lamination was performed using ONY having a thickness of 25 μm subjected to inflation processing as the outermost layer 1, AL having a thickness of 20 μm as the barrier layer 5, LLDPE having a thickness of 40 μm as the sealant layer 7, and the adhesive used in Example 1. Body (2) was obtained.
Laminate (2): ONY (25) / AL (20) / LLDPE (40)

(C) The bottom material 10 is composed of outermost layer 1 / intermediate layer 3 / barrier layer 5 / sealant layer 7. These layers are laminated by dry lamination via a laminating adhesive. An ONY having a thickness of 15 μm subjected to inflation processing is used as the outermost layer 1, a stretched polyethylene having a thickness of 25 μm (hereinafter referred to as “PET”) as the intermediate layer 3, an AL having a thickness of 20 μm as the barrier layer 5, and a sealant layer 7 A laminate (3) was obtained using LLDPE having a thickness of 40 μm and LX500 / KW-75 (trade name, manufactured by DIC) as the main agent of the adhesive.
Laminate (3): ONY (15) / PET (25) / AL (20) / LLDPE (40)

(D) The bottom material 10 is composed of outermost layer 1 / intermediate layer 3 / barrier layer 5 / sealant layer 7. These layers are laminated by dry lamination via a laminating adhesive. An ONY having a thickness of 15 μm subjected to inflation processing is used as the outermost layer 1, PET having a thickness of 12 μm as the intermediate layer 3, AL having a thickness of 30 μm as the barrier layer 5, and unstretched polypropylene having a thickness of 40 μm as the sealant layer 7 (hereinafter, “ Using the adhesive used in Example 1, a laminate (4) was obtained.
Laminate (4): ONY (15) / PET (12) / AL (30) / CPP (40)

(E) The bottom material 10 is composed of the outermost layer 1 / barrier layer 5 / sealant layer 7. These layers are laminated by dry lamination via a laminating adhesive. Lamination was performed using the ONY having a thickness of 25 μm subjected to inflation processing as the outermost layer 1, the AL having a thickness of 40 μm as the barrier layer 5, the CPP having a thickness of 40 μm as the sealant layer 7, and the adhesive used in Example 1. Body (5) was obtained.
Laminate (5): ONY (25) / AL (40) / CPP (40)

(F) The lid material 8 is composed of the outermost layer 1 / barrier layer 5 / sealant layer 7. These layers are laminated by dry lamination via a laminating adhesive. A 15 μm-thick ONY subjected to inflation processing is used as the outermost layer 1, a 12 μm-thick AL as the barrier layer 5, a 40 μm-thick CPP as the sealant layer 7, and the adhesive used in Example 1 are laminated. Body (6) was obtained.
Laminate (6): ONY (15) / AL (12) / CPP (40)

(G) The lid member 8 is composed of the outermost layer 1 / barrier layer 5 / sealant layer 7. These layers are laminated by dry lamination via a laminating adhesive. Using the PET of 16 μm thickness as the outermost layer 1, AL of 12 μm thickness as the barrier layer 5, LLDPE of 40 μm thickness as the sealant layer 7, and the adhesive used in Example 1, the laminate (7) Obtained.
Laminate (7): PET (16) / AL (12) / LLDPE (40)

(H) The lid material 8 is composed of the outermost layer 1 / intermediate layer 3 / barrier layer 5 / sealant layer 7. These layers are laminated by dry lamination via a laminating adhesive. 15 μm thick ONY subjected to inflation processing is used as the outermost layer 1, 12 μm thick PET as the intermediate layer 3, 12 μm thick AL as the barrier layer 5, 40 μm thick LLDPE as the sealant layer 7, and Example 1 A laminate (8) was obtained using the adhesive used in 1.
Laminate (8): ONY (15) / PET (12) / AL (12) / LLDPE (40)

(I) The lid member 8 is composed of the outermost layer 1 / barrier layer 5 / sealant layer 7. These layers are laminated by dry lamination via a laminating adhesive. A PET layer having a thickness of 16 μm is used as the outermost layer 1, a 12 μm-thick PET having a deposited SiOx thickness as the barrier layer 5, a LLDPE having a thickness of 40 μm as the sealant layer 7, and the adhesive used in Example 1. A body (9) was obtained.
Laminate (9): PET (16) / SiOx vapor-deposited PET (12) / LLDPE (40)

  Laminate satisfying all of the performance required for the vacuum heat insulating material packaging material constituted by the bottom material 10 mentioned in the laminates (1) to (5) and the lid material 8 mentioned in the laminates (6) to (9). Met.

  The present invention can be used as a barrier packaging material for vacuum heat insulating materials such as refrigerators, vending machines, and low temperature containers.

DESCRIPTION OF SYMBOLS 1 ... Outermost layer 2 ... Laminate adhesive layer 3 ... Intermediate layer 4 ... Laminate adhesive layer 5 ... Barrier layer 6 ... Laminate adhesive layer 7 ... Sealant layer 8 ..Ladder material 9 ... heat insulating material 10 ... bottom material 11 ... heat seal part

Claims (5)

A bottom material comprising a first laminate and having a recess;
A vacuum heat insulating material comprising a second laminated body and a lid material for closing the open portion of the bottom material,
The first laminate and the second laminate each include an outermost layer, a barrier layer, and an innermost layer,
At least one layer from the outermost layer to the innermost layer is laminated by dry lamination via a laminating adhesive,
Furthermore, the above laminating adhesive comprises a main agent and a curing agent,
The main agent is 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, hexanediol, and diethylene glycol An alcohol component containing at least one kind selected from the above, a polyester-based resin comprising a bisphenol A-type epoxy resin,
The curing agent is an adhesive layer composed of a polyisocyanate component,
The barrier layer of the first laminate is made of aluminum,
The barrier layer of the second laminate, Ri Do from the film obtained by depositing a metal or nonmetal polyester or nylon film,
The vacuum heat insulating material, wherein the outermost layer of the first laminate has a thickness of 6 µm or more .   2. The vacuum heat insulating material according to claim 1, wherein outermost layers of the first laminated body and the second laminated body are made of polyamide formed by inflation processing or cast biaxial stretching.   2. The vacuum heat insulating material according to claim 1, wherein the barrier layer of the first laminate is made of aluminum having a thickness of 15 μm or more.   The innermost layers of the first laminate and the second laminate are one type of polymer selected from polyolefin resin having a thickness of 10 μm or more, unsaturated carboxylic acid, ethylene, and polypropylene, or two or more types of polymers. The vacuum heat insulating material according to any one of claims 1 to 3, further comprising a copolymer.   The core material having a heat insulating property is filled in the concave portion of the bottom material, and the inside of the concave portion of the bottom material filled with the core material is sealed in a vacuum state. 4. The vacuum heat insulating material according to any one of 4.

Images