JP2016070419A - Exterior materials for vacuum heat insulating material, and vacuum heat insulating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide exterior materials for a vacuum heat insulating material that can be used for a long time under a high-temperature environment and are excellent in heat resistance, and the vacuum heat insulating material using the same.SOLUTION: Exterior materials 10A and 10B for a vacuum heat insulating material comprise at least heat-sealed layers 1A and 1B, interlayer adhesion layers 2A and 2B, and gas barrier layers 3A and 3B. The interlayer adhesion layers include a cross-linked polyester urethane resin, and the heat-sealed layers include a polyphenylene sulfide-based resin.SELECTED DRAWING: Figure 3

Description

  The present invention relates to an exterior material for a vacuum heat insulating material excellent in heat resistance, and a vacuum heat insulating material using the same.

In recent years, reduction of greenhouse gases has been promoted in order to prevent global warming, and energy saving is required for electrical products, vehicles, equipment and buildings.
Among them, from the viewpoint of reducing power consumption, the use of vacuum heat insulating materials for articles such as electric products, vehicles, and buildings is being promoted. By providing these articles with a vacuum heat insulating material, it becomes possible to improve the heat insulation performance of the whole article, and an energy reduction effect is expected.

The vacuum heat insulating material is generally a bag body obtained by welding the peripheral edges of two facing exterior materials (hereinafter sometimes referred to as a pair of exterior materials) with heat, and foam resin, fiber material, etc. The core material is inserted, deaerated to make the inside vacuum, and the opening of the bag body is sealed and sealed.
Since the inside of the vacuum heat insulating material is in a high vacuum state, heat transfer due to air convection inside is blocked, so that high heat insulating performance can be exhibited.

In order to maintain the heat insulating performance of the vacuum heat insulating material for a long period of time, it is necessary to maintain the internal vacuum state. Therefore, the exterior material used for the vacuum heat insulating material is required to have various functions such as a gas barrier property for preventing gas from permeating from the outside and a thermal adhesive property for covering and sealing the core material. As the exterior material, usually, a laminate of a plurality of functional layers having these functions is used.
For example, Patent Documents 1 to 3 disclose an exterior material in which a heat-welded layer, a single-layer or multilayer gas barrier layer, and a single-layer or multilayer protective layer are laminated in this order from the core material side of the vacuum heat insulating material. ing. In addition, these functional layers constituting the exterior material are usually laminated via an interlayer adhesive layer.
In addition, in this specification, the layer which comprises the exterior | packing material (namely, exterior material for vacuum heat insulating materials) for vacuum heat insulating materials other than an interlayer contact bonding layer may be called a "functional layer."

JP 2010-255938 A JP 2011-89740 A JP 2006-194297 A

However, when the vacuum heat insulating material is used for a long time in a high temperature environment of 100 ° C. or higher, the heat resistance of the exterior material is low, and the vacuum state inside the vacuum heat insulating material cannot be maintained due to the deterioration of the exterior material. There is a problem that the heat insulation performance cannot be exhibited for a long time.
Among them, among the functional layers constituting the exterior material, the heat-welded layer is likely to be deteriorated by long-term exposure at a higher temperature than other functional layers, and some constituent materials generate gas by thermal decomposition. The gas generated from the heat-welded layer stays inside the vacuum heat insulating material and causes a decrease in the degree of vacuum inside. Moreover, since the adhesive force of the heat-welded layer is reduced due to thermal deterioration, peeling tends to occur at the end portion of the vacuum heat insulating material formed by bonding the heat-welded layers between the exterior materials. When the end portion is peeled off, gas such as air and moisture from the outside easily enters, so that the vacuum heat insulating material cannot maintain the internal vacuum state and the heat insulating performance is deteriorated. Thus, the deterioration of the heat-welded layer tends to cause a vacuum breakage of the vacuum heat insulating material.
Moreover, the adhesive force of the interlayer adhesive layer that bonds the functional layer constituting the exterior material also decreases due to thermal degradation. For this reason, peeling easily occurs between the layers of the exterior material. Furthermore, the thermal deterioration of the interlayer adhesive layer has a problem of promoting the deterioration of the functional layer constituting the exterior material in contact with the interlayer adhesive layer.

  The present invention has been made in view of the above circumstances, and provides a vacuum heat insulating material with excellent heat resistance that can be used for a long time in a high temperature environment, and a vacuum heat insulating material using the same. Main purpose.

  In order to solve the above problems, the present invention has at least a heat-welded layer, an interlayer adhesive layer, and a gas barrier layer, the interlayer adhesive layer contains a crosslinked polyester urethane resin, and the heat-welded layer has An exterior material for a vacuum heat insulating material, comprising a polyphenylene sulfide-based resin.

  According to the present invention, by using the interlayer adhesive layer and the heat welded layer having the above-described composition in combination, the interlayer adhesive layer and the heat welded layer can be thermally deteriorated even when exposed at a high temperature for a long time. It can suppress and can show high adhesive force, respectively. In addition, by improving the heat resistance of the interlayer adhesive layer, it is possible to suppress the deterioration of the functional layer constituting the vacuum heat insulating material exterior material of the present invention, and to improve the overall heat resistance of the vacuum heat insulating material external material. Can be improved.

  In the said invention, it is preferable that the protective layer is arrange | positioned through the said interlayer contact bonding layer in the surface side facing the surface by which the said heat welding layer of the said gas barrier layer is located. Functional layers such as a gas barrier layer and a heat welding layer can be protected by the protective layer, and the protective layer is disposed via the interlayer adhesive layer having the above composition, thereby promoting the deterioration of the protective layer by the interlayer adhesive layer. This is because the heat resistance and scratch resistance of the vacuum heat insulating exterior material of the present invention can be improved.

  The present invention is a vacuum heat insulating material having a core material and an exterior material disposed so as to cover the core material, and having a peripheral edge of the opposed exterior material sealed, and facing the exterior material At least one of them has at least a heat-welded layer, an interlayer adhesive layer, and a gas barrier layer, the interlayer adhesive layer contains a polyester urethane resin crosslinked body, and the heat-welded layer contains a polyphenylene sulfide-based resin. A vacuum heat insulating material is provided.

  According to the present invention, since at least one of the facing exterior materials covering the core material includes the interlayer adhesive layer and the heat welding layer having the above-described composition, even if the vacuum heat insulating material is exposed at a high temperature for a long time. Since the deterioration of the exterior material is suppressed, the overall heat resistance of the vacuum heat insulating material can be improved.

  In the said invention, it is preferable that the protective layer is arrange | positioned through the said interlayer contact bonding layer in the surface side facing the surface by which the said heat welding layer of the said gas barrier layer is located. Functional layers such as a gas barrier layer and a heat welding layer can be protected by the protective layer, and the protective layer is disposed via the interlayer adhesive layer having the above composition, thereby promoting the deterioration of the protective layer by the interlayer adhesive layer. This is because the heat resistance and scratch resistance of the exterior material and the vacuum heat insulating material can be improved.

  In the exterior material for a vacuum heat insulating material of the present invention, the heat resistance can be improved by a combination of the composition of the interlayer adhesive layer and the composition of the heat-welded layer, and the effect that it can be used for a long time in a high-temperature environment. Play.

It is a schematic sectional drawing which shows an example of the exterior material for vacuum heat insulating materials of this invention. It is a schematic sectional drawing which shows the other example of the exterior material for vacuum heat insulating materials of this invention. It is the schematic perspective view and sectional drawing which show an example of the vacuum heat insulating material of this invention.

  Hereinafter, the exterior material for a vacuum heat insulating material and the vacuum heat insulating material of the present invention will be described.

A. First, the exterior material for a vacuum heat insulating material of the present invention will be described. The packaging material for a vacuum heat insulating material of the present invention has at least a heat-welded layer, an interlayer adhesive layer, and a gas barrier layer, the interlayer adhesive layer includes a polyester urethane resin cross-linked body, A polyphenylene sulfide-based resin is included.

  The exterior material for a vacuum heat insulating material of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of a vacuum heat insulating material of the present invention. The vacuum heat insulating material exterior material 10 of the present invention is a laminated body having at least a heat welding layer 1, an interlayer adhesive layer 2, and a gas barrier layer 3. In FIG. 1, a thermal welding layer 1 and a gas barrier layer 3 that are functional layers are laminated via an interlayer adhesive layer 2. In the present invention, the heat welding layer 1 is a layer containing a polyphenylene sulfide-based resin, and the interlayer adhesive layer 2 contains a crosslinked polyester urethane resin.

  According to the present invention, by using the interlayer adhesive layer and the heat welded layer having the above-described composition in combination, the interlayer adhesive layer and the heat welded layer can be thermally deteriorated even when exposed at a high temperature for a long time. It can suppress and can show high adhesive force, respectively. In addition, by improving the heat resistance of the interlayer adhesive layer, it is possible to suppress the deterioration of the functional layer constituting the vacuum heat insulating material exterior material of the present invention, and to improve the overall heat resistance of the vacuum heat insulating material external material. Can be improved.

  Hereinafter, each structure of the exterior material for vacuum heat insulating materials in this invention is demonstrated in detail.

1. Interlayer Adhesive Layer The interlayer adhesive layer in the present invention includes a polyester urethane resin crosslinked body.

  The interlayer adhesive layer in the present invention is usually formed by a cross-linking polymerization reaction of the main agent and the curing agent, using a main component containing at least a polyester urethane and an epoxy component, and a two-component curable interlayer adhesive containing at least a curing agent. The

(1) Interlayer adhesive The interlayer adhesive includes at least a main agent including at least a polyester urethane and an epoxy component, and a curing agent.

(A) Main agent The main agent in the said interlayer adhesive agent contains at least polyesterurethane which is a main component, and an epoxy component.

(I) Polyester urethane Polyester urethane is generally a reaction product of a polyester polyol and an isocyanate compound.

  The polyester polyol is a reaction product of a polyhydric alcohol and a polybasic acid.

(Polyester polyol)
Although it does not specifically limit as polyhydric alcohol, For example, 2 such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. A trihydric alcohol such as hydric alcohol, glycerin or trimethylolpropane, bisphenol A, bisphenol F, bisphenol S, or the like can be used. In the present invention, 1,4-butanediol, bisphenol A and bisphenol F are particularly preferable.
In addition, these polyhydric alcohols may be used independently and may be used in combination of 2 or more types arbitrarily.

Examples of the polybasic acid include aliphatic polybasic acids and aromatic polybasic acids.
Examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, hexahydrophthalic acid, tetrahydrophthalic acid, maleic acid, fumaric acid 1,10-decamethylene dicarboxylic acid, dodecanedioic acid, cyclohexane dicarboxylic acid, dimer acid and the like.
Examples of the aromatic polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, orthophthalic acid, trimesic acid, pyromellitic acid, naphthalenedicarboxylic acid, benzoic acid, p-tertiary butylbenzoic acid, phthalic anhydride, and trimellitic anhydride. An acid etc. are mentioned. In the present invention, adipic acid is particularly preferable.
In addition, these polybasic acids may be used independently and may be used in combination of 2 or more types arbitrarily.

(Isocyanate compound)
As an isocyanate compound, aromatic isocyanate, aliphatic isocyanate, etc. are mentioned, for example. A polyisocyanate compound having two or more isocyanate groups is preferred.
As aromatic polyisocyanate compounds, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate (MXDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6 -Tolylene diisocyanate (2,6-TDI), 4,4) -diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), tetramethylxylylene diisocyanate ( TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), or isomers thereof.
Examples of the aliphatic polyisocyanate compound include 1,6-hexamethylene diisocyanate, hydrogenated methylene diphenyl diisocyanate (HMDI), ethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, lysine diisocyanate, trimethylhexamethylene. Examples include methylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and norbornylene diisocyanate.
Among them, 2,4-tolylene diisocyanate (2,4-TDI) and 2,6-tolylene diisocyanate (2,6-TDI) are preferable in the present invention.
In addition, the above-mentioned isocyanate compound may be used independently and may mix and use 2 or more types.

The reaction ratio between the polyester polyol and the isocyanate compound is not limited and can be set as appropriate according to the type of the compound used, but the polyester urethane is allowed to react at a ratio that allows the desired number of hydroxyl groups. Is preferred.
Further, in the reaction between the polyester polyol and the isocyanate compound, an optional component such as a chain extender may be included as necessary.

(Ii) Epoxy component Any epoxy component may be used as long as it has an epoxy group. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, aromatic epoxy resin, alicyclic epoxy resin, Mainly composed of aliphatic epoxy resins, glycidyl ester type epoxy resins and hydrogenated products thereof, glycidyl amine type epoxy resins and hydrogenated products thereof, copolymers of glycidyl (meth) acrylate and radical polymerizable monomers, and conjugated diene compounds A polymer obtained by epoxidizing an unsaturated carbon double bond of a polymer or a partially hydrogenated polymer thereof, and containing the above-mentioned epoxy group-containing resin with a rubber component such as NBR, CTBN, polybutadiene, or acrylic rubber. Rubber modified epoxy resin, etc., JP-A-2005-290 The epoxy component disclosed by No. 211 gazette is mentioned.
Of these, bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferred in the present invention.

  The content of the epoxy component in the main agent is within the range of 20% by weight to 50% by weight, particularly within the range of 30% by weight to 50% by weight, particularly within the range of 40% by weight to 50% by weight. It is preferable. By making content of the epoxy component in a main ingredient into the said range, since reaction with the hardening | curing agent mentioned later advances easily, it can be hardened in a short time. Moreover, since it has suitable crosslinking density by reaction with the hardening | curing agent mentioned later, the adhesive force of an interlayer contact bonding layer can be made high.

(Iii) Others The main agent may contain other monomer components and the like as necessary in addition to the materials described above. Examples of such a material include caprolactone.

The number average molecular weight of the main agent is preferably in the range of 25,000 to 95,000, and more preferably in the range of 30,000 to 90000. When the number average molecular weight of the main agent is smaller than the above range, the interlayer adhesive layer becomes hard and the adhesive strength may be lowered. On the other hand, if it is larger than the above range, it may not sufficiently react with the curing agent described later, and the heat resistance and the like of the interlayer adhesive layer may decrease.
The number average molecular weight is a value measured by gel permeation chromatography.

  The weight average molecular weight of the main agent is preferably in the range of 45,000 to 200,000, and more preferably in the range of 50,000 to 160000. If the weight average molecular weight of the main agent is smaller than the above range, the initial cohesive force of the interlayer adhesive may be insufficient and the interlayer adhesive layer may float. Therefore, there is a possibility that peeling occurs at the end portion where the vacuum heat insulating material exterior material is bonded. On the other hand, if it is larger than the above range, the initial cohesive force of the interlayer adhesive can be sufficiently obtained, but the viscosity becomes too high to be applied and the interlayer adhesive layer may not be formed. The weight average molecular weight is a value measured by gel permeation chromatography.

(B) Curing agent The curing agent contained in the interlayer adhesive is not particularly limited as long as it can form a cross-linked structure with the above-mentioned main agent. For example, polyisocyanate curing having at least two isocyanate groups. Agents are preferred. Among them, an aromatic polyisocyanate curing agent is preferable, and an aromatic polyisocyanate curing agent having a urethane bond is particularly preferable.
Examples of the aromatic polyisocyanate curing agent include the aromatic polyisocyanate compounds described in the above-mentioned section “(a) Main agent (i) Polyester urethane”, adducts of these various aromatic polyisocyanate compounds, or Multimers and the like can be used.
Among them, in the present invention, the curing agent may be 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), an adduct or a multimer thereof. preferable.

  The content of the curing agent in the interlayer adhesive is preferably an amount capable of sufficiently reacting with the main agent described above, and can be appropriately set according to the hydroxyl value of the main agent. Specifically, the content of the curing agent is preferably in the range of 5% by weight to 40% by weight, more preferably in the range of 10% by weight to 35% by weight, with respect to 100% by weight of the main agent. It is particularly preferable that the content be in the range of 15 to 30% by weight. By making content of the hardening | curing agent in an interlayer adhesive into the said range, it can fully react with a main ingredient, can form bridge | crosslinking, and the adhesive force of an interlayer adhesive layer can be made into a desired magnitude | size. Moreover, generation | occurrence | production of a crack etc. can be avoided in the exterior material for vacuum heat insulating materials of this invention.

(C) Other In addition to the above-mentioned main agent and curing agent, the interlayer adhesive contains any additive generally contained in the adhesive, such as a filler, a softener, a stabilizer, and an adhesion promoter. Also good.
The interlayer adhesive may be used as a solvent-type adhesive diluted with a volatile organic solvent, or may be used as a solvent-free type, that is, as an adhesive not containing a volatile solvent. The use of a solvent can be selected accordingly.

The melting point of the interlayer adhesive is preferably higher than the use environment temperature of the vacuum heat insulating exterior material of the present invention, and is in the range of 200 ° C. to 600 ° C., particularly in the range of 250 ° C. to 500 ° C. preferable. Moreover, as a glass transition temperature (Tg) of the said interlayer adhesive agent, it is preferable to exist in the range of -60 degreeC-30 degreeC, especially in the range of -50 degreeC-20 degreeC.
By setting the melting point and glass transition temperature of the interlayer adhesive within the above ranges, thermal degradation of the interlayer adhesive layer under the operating temperature can be suppressed, and delamination can be made difficult, and a vacuum heat insulating material exterior material is configured. It is possible to suppress deterioration of the functional layer. Moreover, even in an environment where a heat cycle (thermal shock) in which a low temperature and a high temperature are repeated occurs, deterioration of the vacuum heat insulating material exterior material can be suppressed.
In addition, the said melting | fusing point and glass transition temperature are the values measured by differential operation calorimetry (DSC).

The decomposition temperature of the interlayer adhesive is preferably in the range of 250 ° C to 600 ° C, and more preferably in the range of 300 ° C to 550 ° C. By setting the decomposition temperature of the interlayer adhesive within the above range, thermal degradation of the interlayer adhesive layer under the operating temperature can be suppressed, delamination can be made difficult, and the functional layer constituting the vacuum insulating material exterior material Deterioration can be suppressed.
The decomposition temperature is a value measured by differential thermal-thermogravimetric simultaneous measurement (TG-DTA).

(2) Interlayer adhesive layer The interlayer adhesive layer in the present invention is a layer containing a crosslinked polyester urethane resin. The interlayer adhesive layer is a layer formed by crosslinking a polyester urethane resin by the crosslinking polymerization reaction of the main agent and the curing agent described above.

  It is preferable that the interlayer adhesive layer exhibits high adhesiveness to each functional layer constituting the exterior material for a vacuum heat insulating material of the present invention. This is because it is possible to prevent the peeling between the layers of the vacuum heat insulating material exterior material of the present invention even when exposed for a long time at a high temperature. Specifically, the delamination strength between the interlayer adhesive layer and the functional layer in contact with the surface of the interlayer adhesive layer may be 0.5 N / 15 mm or more, particularly preferably 3 N / 15 mm or more. In particular, it is preferably 5 N / 15 mm or more. The delamination strength is measured based on JIS-Z-1707.

The thickness of the interlayer adhesive layer only needs to be a thickness that can exhibit a desired adhesive force, and can be appropriately set according to the composition of the interlayer adhesive layer. Usually, it is preferable that the thickness of which becomes 0.1g ^{/ m 2} ~10g ^/ m 2 approximately in a dry state.

The interlayer adhesive layer may be a layer formed separately in the form of a sheet or a film using the above-mentioned interlayer adhesive, and the interlayer adhesive is mixed with a desired solvent, and the vacuum insulating material exterior material of the present invention is used. It may be a layer formed by directly applying to the surface of each constituent layer.
In addition, as said solvent, the solvent of Unexamined-Japanese-Patent No. 2014-137136 can be used, for example.

  As an application method in the case of forming an interlayer adhesive layer by applying an interlayer adhesive, for example, a roll coating method, a gravure roll coating method, a kiss coating method, other coating methods, or the like can be used.

2. Heat-welded layer The heat-welded layer in the present invention contains a polyphenyl sulfide (hereinafter sometimes abbreviated as PPS) resin.
The said heat welding layer is a layer which bears the outermost layer in one side of the lamination direction of the exterior material for vacuum heat insulating materials of this invention normally.

  The heat-welding layer can suppress thermal degradation due to high-temperature exposure by including a PPS resin, and in the vacuum heat insulating material using the vacuum heat insulating material exterior material of the present invention, the end of the vacuum heat insulating material Adhesion can be strengthened. Moreover, generation | occurrence | production of delamination can be suppressed by combined use with the interlayer contact bonding layer of the composition mentioned above.

  Furthermore, the PPS resin has a feature that there is little degassing due to high temperature exposure. For this reason, in the vacuum heat insulating material using the vacuum heat insulating material exterior material of the present invention, it is possible to prevent the generation of gas from the heat-welded layer and the resulting decrease in the degree of vacuum inside, a high vacuum state over a long period of time Can be maintained.

  Any PPS-based resin may be used as long as it has a linear polymer skeleton in which sulfur is bonded to a benzene ring and may have any substituent.

  The heat welding layer is mainly composed of a PPS resin, and may contain an optional component such as an additive as necessary.

  The thickness of the heat-welded layer is not particularly limited as long as it has a desired adhesive force, and is preferably in the range of 20 μm to 100 μm, in particular in the range of 25 μm to 90 μm, particularly in the range of 30 μm to 80 μm. . If the thickness of the heat-welded layer is larger than the above range, the gas barrier property and appearance as the whole vacuum insulating material exterior material of the present invention may be deteriorated. The force may not be obtained, and peeling may occur during long-term use at high temperatures.

  A commercially available film or sheet may be used for the heat welding layer, or the composition of the heat welding layer may be applied to the surface of the layer in contact with the heat welding layer.

3. Gas Barrier Layer The gas barrier layer in the present invention is not particularly limited as long as it can exhibit a desired gas barrier property, and a gas barrier layer or a gas barrier film generally used in a vacuum heat insulating material can be used.
Specifically, metal foil such as aluminum, nickel, stainless steel, iron, copper, and titanium, metal such as aluminum, inorganic compound such as silicon oxide, and metal oxide such as aluminum oxide are deposited on one side of the resin film. Film, composite gas barrier film in which a gas barrier coating film composed of a gas barrier composition such as polyvinyl alcohol or vinylidene chloride is provided on the inorganic vapor-deposited film, gas barrier properties such as an ethylene vinyl alcohol copolymer (EVOH) film or MXD nylon Examples thereof include a gas barrier resin film.
Among them, it is inorganic from the viewpoint that it has excellent gas barrier properties and little deterioration with the passage of time, and when the vacuum heat insulating material exterior material of the present invention is used as a vacuum heat insulating material, it has low heat conductivity and high heat insulating performance. Vapor deposited films are preferred.
The metal foil and various films may be used alone, or the gas barrier layer may be a multilayer body by using a plurality of layers of the same or different types.

  The gas barrier layer may or may not have transparency, and can be appropriately selected according to the transparency required for the vacuum heat insulating exterior material of the present invention.

  The surface of the gas barrier layer may be subjected to a surface treatment in order to improve gas barrier performance and adhesion with other layers. Examples of the surface treatment method include corona discharge treatment, flame treatment, plasma treatment, and ozone treatment.

The thickness of the gas barrier layer can be appropriately set according to the type. When metal foil is used as the gas barrier layer, the thickness of the metal foil is preferably in the range of 5 μm to 40 μm. Moreover, when using gas barrier films other than metal foil as a gas barrier layer, it is preferable that the thickness of a gas barrier layer exists in the range of 9 micrometers-100 micrometers.
If the thickness of the gas barrier layer is smaller than the above range, pinholes and the like are likely to be generated, and the gas barrier property may be lowered. This is because when used as a heat insulating material, a heat bridge is likely to occur, and the heat insulating performance may be deteriorated.

The gas barrier properties of the gas barrier layer, the oxygen permeability ^0.5cc · m -2 · ^{day -1} or less, preferably among them ^0.1cc · m -2 · ^{day -1} or less. Further, the water vapor permeability ^0.2cc · m -2 · ^{day -1} or less, and preferably less inter alia ^0.1cc · m -2 · ^{day -1.} By setting the oxygen and water vapor permeability of the gas barrier layer within the above ranges, the vacuum insulating material exterior material of the present invention can exhibit high gas barrier properties.
In the present specification, the oxygen permeability is based on JIS-K-7126B under the conditions of a temperature of 23 ° C. and a humidity of 90% RH (Oxtran manufactured by MOCON, USA) It is the value measured using. Further, the water vapor permeability is a value measured using a water vapor permeability measuring apparatus (manufactured by MOCON, USA, PERMATRAN) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH.

4). Arbitrary functional layer Although the exterior material for vacuum heat insulating materials of this invention has a heat welding layer, an interlayer contact bonding layer, and a gas barrier layer at least, it may have the following functional layers as needed.

(1) Protective layer As for the exterior material for vacuum heat insulating materials of this invention, it is preferable that the protective layer is arrange | positioned at the surface side facing the surface of the side where the said heat welding layer of the said gas barrier layer is located.
In general, since the outermost material for a vacuum heat insulating material is one of the outermost layers in the stacking direction is a heat-welded layer and is provided with a protective layer on the outermost surface of the other, by disposing the protective layer also in the present invention, This is because functional layers such as a gas barrier layer and a heat welding layer can be protected by the protective layer, and scratch resistance of the vacuum heat insulating exterior material of the present invention can be improved.
In addition, the said protective layer has a function which protects an inside when covering a core material using the vacuum insulating material exterior material of this invention, and forming a vacuum heat insulating material, and bears the surface of a vacuum heat insulating material It becomes.

  FIG. 2 is a schematic cross-sectional view showing another example of the vacuum heat insulating material exterior material of the present invention, on the surface of the gas barrier layer 3 facing the surface adjacent to the heat welding layer 1 with the interlayer adhesive layer 2 interposed therebetween. The example in which the protective layer 4 was laminated | stacked is shown.

  As a protective layer, what is generally used with the exterior material for vacuum heat insulating materials can be used, For example, the various protective layers described in Unexamined-Japanese-Patent No. 2014-137136 are mentioned.

  The surface of the protective layer may be subjected to a surface treatment in order to improve adhesion with other functional layers and interlayer adhesive layers. The surface treatment method may be the same as the surface treatment method described in the section “3. Gas barrier layer”.

  The protective layer may or may not have transparency, and can be appropriately selected according to the transparency required for the vacuum heat insulating exterior material of the present invention.

  The thickness of the protective layer is not particularly limited as long as it is a thickness capable of protecting each layer constituting the exterior material for a vacuum heat insulating material of the present invention, and is preferably in the range of 5 μm to 80 μm, for example. .

  The protective layer is preferably disposed via an interlayer adhesive layer having the above composition. This is because it is possible to suppress the deterioration of the protective layer due to the deterioration of the interlayer adhesive layer and to prevent the protective layer from peeling off.

(2) Arbitrary functional layer The exterior material for a vacuum heat insulating material of the present invention may have an anchor coat layer, a pinhole-resistant layer, and the like as necessary.

5. Others The exterior material for a vacuum heat insulating material of the present invention may have a plurality of gas barrier layers and protective layers from the viewpoint of improving gas barrier properties and improving strength and scratch resistance.

The packaging material for a vacuum heat insulating material of the present invention has at least a heat-welded layer, an interlayer adhesive layer, and a gas barrier layer. As the stacking order of the heat-welded layer, the interlayer adhesive layer, and the gas barrier layer, the heat-welded layer is Although it will not specifically limit if it can bear one outermost layer of the exterior material for vacuum heat insulating materials, It is preferable that the said interlayer contact bonding layer is arrange | positioned between a heat welding layer and a gas barrier layer. In particular, it is preferable that one of the two opposing surfaces of the interlayer adhesive layer is in direct contact with the heat-welded layer. This is because the effects of the present invention are more easily exhibited. One of the two opposing surfaces of the interlayer adhesive layer may be in direct contact with the gas barrier layer.
Furthermore, when it has the above-mentioned arbitrary functional layers between the heat welding layer and the gas barrier layer, at least one of the two opposing surfaces of the interlayer adhesive layer may be in contact with the arbitrary functional layer.
Furthermore, it is preferable that the interlayer adhesive layer is also disposed between the functional layers of the vacuum heat insulating exterior material of the present invention other than between the heat welding layer and the gas barrier layer. That is, it is preferable that each functional layer is laminated | stacked through the interlayer contact bonding layer in the exterior material for vacuum heat insulating materials of this invention. This is because it is possible to suppress the deterioration of other functional layers due to the deterioration of the interlayer adhesive layer and to prevent the occurrence of peeling between the respective layers.

  The exterior material for a vacuum heat insulating material of the present invention preferably has high adhesive strength. This is because the occurrence of peeling can be suppressed even when exposed for a long time at high temperature. Specifically, the initial peel strength of the vacuum insulation material may be 3N / 15 mm or more, preferably 4N / 15 mm or more, and particularly preferably 5N / 15 mm or more. Further, the peel strength of the vacuum insulation material after exposure at 130 ° C. for 1000 hours may be 1 N / 15 mm or more, preferably 1.5 N / 15 mm or more, particularly 2 N / 15 mm or more. preferable. The peel strength is measured based on JIS-Z-1707.

The initial tensile strength at break of the vacuum heat insulating exterior material of the present invention is preferably 100 N or more, more preferably 130 N or more, and particularly preferably 150 N or more. Further, the tensile strength at break after exposure at 130 ° C. for 1000 hours is preferably 100 N or more, more preferably 130 N or more, and particularly preferably 150 N or more.
At this time, the decrease rate of the tensile break strength after 1000 hours exposure at 130 ° C. with respect to the initial tensile break strength is in the range of 0% to 30%, particularly in the range of 0% to 20%, particularly in the range of 0% to 10%. It is preferable to be within the range.
When the tensile breaking strength before and after deterioration under a predetermined exposure condition and the decrease rate of the tensile breaking strength are within the above-described range, the vacuum insulation exterior material of the present invention exhibits high heat resistance in a high temperature environment. Because it can. The tensile strength is a value measured based on JIS-Z-1707.

  The exterior material for a vacuum heat insulating material of the present invention has a high gas barrier property. The specific gas barrier property can be the same as the gas barrier property described in the above section “3. Gas barrier layer”.

  The exterior material for a vacuum heat insulating material of the present invention may be transparent or not. Here, unless otherwise specified, “transparent” or “transparency” refers to transparency that allows the inside to be visually confirmed in the vacuum heat insulating material using the vacuum heat insulating material of the present invention. . Therefore, the transparency includes colorless transparency and colored transparency that does not hinder visibility, is not defined by strict transmittance, and can be appropriately determined according to the use of the vacuum heat insulating material and the like.

6). Manufacturing method As a manufacturing method of the vacuum insulating material exterior material of the present invention, any method can be used as long as the heat-welding layer, the interlayer adhesive layer, and the gas barrier layer can be laminated in a desired order, and a known method can be used.

7). Applications The exterior material for a vacuum heat insulating material according to the present invention can be used as an exterior material for a vacuum heat insulating material used for articles such as electric appliances, buildings, cold insulation storage tanks, and automobiles. Especially, it can use suitably as an exterior material of the vacuum heat insulating material used for the part exposed to high temperature for a long period of time.

B. Next, the vacuum heat insulating material of the present invention will be described. The vacuum heat insulating material of the present invention is a vacuum heat insulating material having a core material and an exterior material disposed so as to cover the core material, the peripheral edge of the facing external material being sealed, At least one of the outer packaging materials includes at least a heat-welded layer, an interlayer adhesive layer, and a gas barrier layer, the interlayer adhesive layer includes a polyester urethane resin crosslinked body, and the heat-welded layer includes polyphenylene sulfide. It contains a resin.

The vacuum heat insulating material of this invention is demonstrated with reference to figures. Fig.3 (a) is a schematic perspective view which shows an example of the vacuum heat insulating material of this invention, FIG.3 (b) is XX sectional drawing of Fig.3 (a).
As illustrated in FIGS. 3A and 3B, the vacuum heat insulating material 20 of the present invention is sealed by thermally welding the peripheral edges of two facing exterior materials 10A and 10B. And the core material 11 is accommodated in the space sealed by 10B, and the inside is depressurized and is in a vacuum state. The sealing portions at the periphery of the exterior materials 10 </ b> A and 10 </ b> B become the end portions 12 of the vacuum heat insulating material 20.
In FIG. 3 (b), facing exterior materials 10 </ b> A and 10 </ b> B are the vacuum insulation material exterior materials described in the section “A. Vacuum insulation material exterior materials”. That is, it has heat welding layers 1A and 1B, interlayer adhesive layers 2A and 2B, gas barrier layers 3A and 3B from the exterior material 10A and 10B core material 11 side, and further interlayer adhesive layers 2A and 2B on gas barrier layers 3A and 3B. There are protective layers 4A and 4B, and the heat-welding layers 1A and 1B and the interlayer adhesive layers 2A and 2B each contain a desired composition.

  According to the present invention, at least one of the facing exterior materials covering the core material includes the interlayer adhesive layer and the heat-welded layer described in the section “A. Vacuum insulation material exterior material”. Even when exposed to a high temperature for a long time, deterioration of the exterior material is suppressed, so that the overall heat resistance of the vacuum heat insulating material can be improved.

  Hereinafter, each structure of the vacuum heat insulating material of this invention is demonstrated.

1. Exterior Material The exterior material in the present invention is disposed so as to cover the core material, and at least one of the opposing exterior materials is described in the section “A. Exterior material for vacuum heat insulating material”. It is an exterior material for a vacuum heat insulating material.

The exterior material in the present invention includes a “first exterior material” that is the exterior material for a vacuum heat insulating material described in the section “A. Exterior material for a vacuum heat insulating material”, and a “second exterior material” other than that. It can be divided into two aspects.
Hereinafter, each aspect will be described.

(1) 1st exterior material The 1st exterior material is the exterior material for vacuum heat insulating materials demonstrated in the term of the "A. exterior material for vacuum heat insulating materials".

  The interlayer adhesive layer in the first exterior material includes a polyester urethane resin cross-linked body, and the interlayer adhesive layer is usually a two-component curing including at least a main component including at least polyester urethane and an epoxy component, and a curing agent. It can be formed by a cross-linking polymerization reaction of the main agent and the curing agent using a mold interlayer adhesive.

  In addition to the thermal welding layer, the interlayer adhesive layer, and the gas barrier layer, the first exterior material includes a protective layer on the side of the gas barrier layer that faces the side where the thermal welding layer is located. It is preferable to arrange | position through. About the reason, it is the same as the reason demonstrated in the above-mentioned item of "A. Exterior material for vacuum heat insulating materials."

  The details of the first exterior material are the same as those described in the above-mentioned section “A. Exterior material for vacuum heat insulating material”, and thus the description thereof is omitted here.

(2) Second exterior material The second exterior material has at least a heat-welded layer, an interlayer adhesive layer, and a gas barrier layer from the core material side, and the composition of the heat-welded layer and the interlayer adhesive layer is not particularly limited. Except for the point, it can be the same as the first exterior material.
Moreover, about the heat welding layer and interlayer adhesion layer in a 2nd exterior material, it can be made to be the same as that of the heat welding layer and interlayer adhesion layer used with the exterior material for a general vacuum heat insulating material use.

(3) Others The exterior material in the present invention is disposed so that the heat-welded layer is in contact with the core material.
Further, at least one of the exterior materials disposed to face each other so as to cover the core material may be the above-described first exterior material, but both of the opposed exterior materials may be the first exterior material. preferable. Since both of the facing exterior materials exhibit excellent heat resistance, even if the vacuum heat insulating material of the present invention is exposed for a long time in a high-temperature environment, peeling between the end portions of the vacuum heat insulating material and the layers of the exterior material is possible. It is because generation | occurrence | production and deterioration can be suppressed and the inside of the vacuum heat insulating material of this invention can be maintained in a high vacuum state over a long period of time.
In addition, the presence or absence of the transparency of the said exterior material is not ask | required.

2. Core Material The core material in the present invention is covered and encapsulated by an opposing exterior material.
As a material for the core material, a material generally used for a core material of a vacuum heat insulating material can be used. Examples thereof include a porous material such as a powder such as silica, a foam such as urethane polymer, and a fiber such as glass wool. The porous body has a porosity of 50% or more, preferably 90% or more. It is because it can be set as a core material with low heat conductivity.

  The core material may include a getter agent for adsorbing a minute amount of gas entering from the outside. Examples of the getter agent include general materials used for vacuum heat insulating materials such as silica, alumina, zeolite, activated carbon and the like.

  The thickness of the core material is not particularly limited as long as a desired heat insulating effect can be exhibited. For example, the thickness is preferably in the range of 1 mm to 30 mm in a state after decompression.

3. Others The vacuum heat insulating material of the present invention preferably contains a detection agent inside when at least one of the facing exterior materials is transparent. This is because the vacuum state inside the vacuum heat insulating material can be confirmed from the change in the detection agent.
Here, the detection agent is a substance that undergoes discoloration or deformation when the presence of a gas such as air or moisture or a temperature change is detected. For example, a gas detection agent that detects a gas, a temperature detection agent that detects a temperature change, etc. There is.
Examples of the gas detection agent include a hygroscopic agent such as silica gel and the getter agent described in the above-mentioned section “2. Core material”. Examples of the temperature detecting agent include a commercially available temperature indicating agent.
The detection agent may be dispersed inside the vacuum heat insulating material, may be fixedly disposed at a desired position, and may be located at a position where it can be visually recognized from the outside.

  The degree of vacuum inside the vacuum heat insulating material of the present invention is preferably 5 Pa or less. It is because the convection of the air inside a vacuum heat insulating material can be interrupted | blocked and heat insulation performance can be improved.

The thermal conductivity (initial thermal conductivity) of the vacuum heat insulating material of the present invention is, for example, 10 mW · m ⁻¹ · K ⁻¹ or less, particularly 5 mW · m ⁻¹ · K ⁻¹ or less, particularly 3 mW in a 25 ° C. environment. ^-It is preferable that it is below m <^-1> * K < ^-1 >. This is because the vacuum heat insulating material is difficult to conduct heat to the outside, so that a high heat insulating effect can be achieved. In addition, the said heat conductivity is the value measured by the heat flow meter method using the heat conductivity measuring apparatus auto-lambda (Hideki Seiki HC-074) according to JIS-A-1412-3.

  The method for producing a vacuum heat insulating material of the present invention is a method in which a core material is enclosed in at least one of the exterior materials using the above-described first exterior material, and the inside is evacuated and sealed in a vacuum state. If it is, it will not specifically limit, A well-known method can be used.

  The vacuum heat insulating material of the present invention can be used in any place that requires heat insulation, such as a vacuum heat insulating material for electric appliances, a vacuum heat insulating material for buildings, a vacuum heat insulating material for a cold insulation box, a vacuum heat insulating material for automobiles, and the like. .

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  The present invention will be described more specifically with reference to the following examples.

[Example 1]
The exterior material for vacuum heat insulating materials was created in the following procedures.

(Preparation of interlayer adhesive A)
Polyester urethane (main component; prepared from tolylene diisocyanate, adipic acid and 1,4-butanediol) and an epoxy component, an aromatic polyisocyanate curing agent containing tolylene diisocyanate as a constituent material, and ethyl acetate Were mixed so that the weight blending ratio was main agent: curing agent: ethyl acetate = 10: 3: 10 to prepare an interlayer adhesive A (two-component curable epoxy adhesive).

(Lamination of vacuum insulation exterior materials)
As a first protective layer, an interlayer adhesive A prepared with the above-mentioned blending ratio is applied to an easy-adhesion surface of a 25 μm-thick nylon film (product name: ONM manufactured by Unitika Ltd.) that has been subjected to easy-adhesion treatment on both sides. It was applied using a die coater so as to have an amount of 3.5 g / m ² and dried to form an interlayer adhesive layer. On the interlayer adhesive layer, a PET film having a film thickness of 12 μm (product name: PET, manufactured by Unitika Co., Ltd.) whose both surfaces were easily adhered as a second protective layer was laminated.
Next, an interlayer adhesive A was applied to the PET film surface in the same manner at a coating amount of 3.5 g / m ² and dried to form an interlayer adhesive layer. An Al foil having a film thickness of 6 μm (product name: 1N30, manufactured by Sumikara Aluminum Foil Co., Ltd.) was laminated as a gas barrier layer on the interlayer adhesive layer.
Subsequently, on the obtained gas barrier layer, an interlayer adhesive A is applied at a coating amount of 3.5 g / m ² by the same method and dried to form an interlayer adhesive layer, and a heat welding layer is formed on the interlayer adhesive layer. As a result, a PPS film having a film thickness of 50 μm (product number: 3030 manufactured by Toray Industries, Inc.) was laminated to obtain a vacuum heat insulating material exterior material.

[Comparative Example 1]
A vacuum heat insulating material exterior material was obtained in the same manner as in Example 1 except that a CPP film having a film thickness of 50 μm (product name: RXC-22 manufactured by Mitsui Chemicals, Inc.) was used as the heat welding layer.

[Comparative Example 2]
A vacuum insulating material exterior material was obtained in the same manner as in Example 1 except that the interlayer adhesive B prepared by the following method was used instead of the interlayer adhesive A.
(Preparation of interlayer adhesive B)
A two-component curing type in which a main component containing polyester as a main component, a curing agent containing an aliphatic polyisocyanate, and ethyl acetate are mixed so that the weight ratio is main agent: curing agent: ethyl acetate = 10: 1: 10. An interlayer adhesive B, which is an adhesive, was prepared.

[Comparative Example 3]
A vacuum heat insulating material exterior material was obtained in the same manner as in Comparative Example 2 except that a CPP film having a film thickness of 50 μm (product name: RXC-22, manufactured by Mitsui Chemicals, Inc.) was used as the heat welding layer.

[Evaluation]
The vacuum heat insulating packaging material obtained in Example 1 and Comparative Examples 1 to 3 was exposed at 130 ° C. for 1000 hours, and after the initial, 200 hours, 400 hours, 600 hours, 800 hours, and 1000 hours. The tensile strength at break was measured. Moreover, the decreasing rate of the tensile breaking strength after 1000 hours with respect to the initial tensile breaking strength was calculated. The tensile strength at break was measured based on the standard of JIS-Z-1707.
The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 ... Thermal welding layer 2 ... Interlayer adhesion layer 3 ... Gas barrier layer 4 ... Protective layer 10, 10A, 10B ... Exterior material for vacuum heat insulating material, exterior material 11 ... Core material 20 ... Vacuum heat insulating material

Claims (4)

Having at least a heat welding layer, an interlayer adhesive layer, and a gas barrier layer;
The interlayer adhesive layer includes a polyester urethane resin crosslinked body,
The heat insulating layer includes a polyphenylene sulfide-based resin.   2. The vacuum heat insulating material according to claim 1, wherein a protective layer is disposed on the surface side of the gas barrier layer opposite to the surface on which the heat welding layer is located with the interlayer adhesive layer interposed therebetween. Exterior material. A vacuum heat insulating material having a core material and an exterior material disposed so as to cover the core material, wherein a peripheral edge of the facing exterior material is sealed,
At least one of the facing exterior materials facing at least has a heat welding layer, an interlayer adhesive layer, and a gas barrier layer,
The interlayer adhesive layer includes a polyester urethane resin crosslinked body,
The heat insulation layer includes a polyphenylene sulfide-based resin.   4. The vacuum heat insulating material according to claim 3, wherein a protective layer is disposed on the surface side of the gas barrier layer facing the surface on which the heat-welded layer is located, with the interlayer adhesive layer interposed therebetween.