JP2015092105A - Vacuum heat insulating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vacuum heat insulating material of high productivity and economical efficiency, superior in heat insulating performance and gas barrier property, capable of exhibiting excellent heat insulating performance for a long time, and employing an exterior material including a gas barrier material able to be directly laminated with a thermoplastic resin by extrusion coating.SOLUTION: In a vacuum heat insulating material 1 composed of a core material 2 and an exterior material 3 covering the core material, and of which inside is decompressed and sealed, the exterior material is composed of a gas barrier laminate composed of at least a heat welded layer and a gas barrier material, the gas barrier material is composed of at least a gas barrier layer including 1.4 wt.% or less of monovalent metallic element, 5.0-18.0 wt.% of polyvalent metallic element, and 0.01-3.0 wt.% to the total weight of nitrogen and carbon, of a nitrogen element, a deposition layer and a plastic base material. The thermal welded layer is formed by extrusion coating the gas barrier material with the thermoplastic resin.

Description

  The present invention relates to a vacuum heat insulating material, and more particularly, to a vacuum heat insulating material comprising a gas barrier laminate having excellent gas barrier properties and heat insulating performance as well as excellent productivity as an exterior material.

  After covering the core material of the porous structure with the exterior material, the vacuum heat insulating material formed by depressurizing and sealing the inside has almost no contribution of gas thermal conductivity, so compared to heat insulating materials such as glass wool, It is thin and can exhibit an excellent heat insulation effect, and is used in various fields such as life-related items such as refrigerators and rice cookers, and housing-related items such as floor heating and heat insulation panels.

In such a vacuum heat insulating material, the exterior material covering the core material is required to have high gas barrier properties capable of maintaining a reduced pressure state inside the vacuum heat insulating material as well as having excellent sealing properties. As an exterior material, a laminate including an aluminum foil has been widely used.
However, when a laminate including an aluminum foil is used as an exterior material, the heat conductivity of aluminum is high, and thus there is a problem that the heat insulation effect is reduced by the heat conduction by the aluminum foil.

In order to solve such problems caused by aluminum foil, it has been proposed to use a laminate comprising a deposited film formed by depositing a metal or an inorganic substance as an exterior material for a vacuum heat insulating material (Patent Document 1, 2) The deposited film has a problem that the gas barrier property is lowered due to the occurrence of cracks, pinholes and the like.
From such a viewpoint, as a vacuum heat insulating material exterior material, a vapor deposition layer, a polyacrylic acid resin layer having a gas barrier property, and a heat welding layer, which is a mixture of a polyalcohol polymer and a polyacrylic acid polymer. It has been proposed to use a laminate film having the same (Patent Documents 3 and 4).
The polyacrylic acid-based resin layer used for the exterior material is a dry coating film formed by casting a mixture solution of a polyalcohol-based polymer and a polyacrylic acid-based polymer on a vapor deposition layer at 100 ° C. or higher. After heat treatment at high temperature, it is formed by ionic crosslinking of free carboxylic acids of polyacrylic acid polymers that are not ester-bonded by immersing them in water containing metal ions, and has excellent gas barrier properties It is described.

JP 2004-172493 A JP 2004-130654 A JP 2005-337405 A Japanese Patent No. 3685206

However, since the polyacrylic acid-based resin described above needs to be highly crosslinked by heating at a high temperature of 100 ° C. or higher or for a long time, there is a problem that the influence on the vapor deposition layer is large. In addition, in order to improve the gas barrier property, a long immersion treatment is required for ionic crosslinking with metal ions, which results in inferior productivity and problems such as consuming a great deal of energy and water. Furthermore, it is not fully satisfactory in terms of flexibility, and the deposited layer cannot be sufficiently protected.
In addition, when a layer made of another thermoplastic resin is laminated on such a gas barrier material by extrusion coating, it is necessary to previously laminate another base material on the gas barrier material by dry lamination to protect the gas barrier material. However, the number of processes was large, and it was not yet satisfactory in terms of productivity and economy. In addition, an adhesive resin is used for dry lamination, and the solvent of this adhesive resin may remain in the gas barrier laminate, and the residual solvent may impair the reduced pressure inside the vacuum heat insulating material. It is desired to reduce the number of times of dry lamination when manufacturing a laminated body.
Accordingly, the object of the present invention is to produce using an exterior material containing a gas barrier material that has excellent heat insulation performance and gas barrier properties, can exhibit excellent heat insulation performance over a long period of time, and can be directly laminated with a thermoplastic resin by extrusion coating. It is providing the vacuum heat insulating material excellent in property and economy.
Another object of the present invention is to provide a vacuum heat insulating material that uses an exterior material that does not require heating at a high temperature and has excellent productivity.

  According to the present invention, a gas barrier laminate comprising a core material and an exterior material covering the core material, wherein the exterior material comprises at least a heat-welded layer and a gas barrier material. The gas barrier material is made of a polycarboxylic acid-based polymer, 1.4% by weight or less of a monovalent metal element, 5.0 to 18.0% by weight of a polyvalent metal element, nitrogen, carbon It consists at least of a gas barrier layer containing 0.01 to 3.0% by weight of nitrogen element with respect to the total weight, a vapor deposition layer, and a plastic substrate, and the heat welding layer is formed by extrusion coating a thermoplastic resin on the gas barrier material. The vacuum heat insulating material characterized by being formed is provided.

In the vacuum heat insulating material of the present invention,
1. The gas barrier layer is formed on a plastic substrate on which a vapor deposition layer is formed;
2. The carboxylic acid polymer is poly (meth) acrylic acid,
3. The carboxylic acid polymer is partially neutralized in a molar ratio to the carboxyl group of at most 4.5%,
4). The thermoplastic resin is an ethylene- (meth) acrylic acid copolymer or an ionomer resin;
5. The thermoplastic resin is a polyolefin polymerized using a single-site catalyst, an antioxidant-free polyolefin resin, or a polyolefin resin containing a reactive group capable of forming a chemical bond with a carboxyl group or a hydroxyl group;
6). The polyolefin resin has a density of 0.950 g / cm ³ or less,
7). The polyolefin resin is MFR 7.0 g / 10 min or more,
8). The gas barrier layer has a weight loss from 200 ° C. to 320 ° C. of 10% or less in thermogravimetric analysis (TGA) measurement at a heating rate of 10 ° C./min, and in dynamic viscoelasticity (DMS) measurement at 20 Hz. The difference when subtracting tan δ at 50 ° C. from tan δ at 200 ° C. is 0.010 or more,
9. The monovalent metal element is sodium or potassium;
10. The polyvalent metal element is at least one of calcium, magnesium, zinc and iron;
11. The nitrogen content relative to the total amount of carbon, oxygen and nitrogen in the surface layer of the gas barrier layer is 1 atm% or more;
12 The gas barrier material forms an undercoat layer containing an isocyanate compound having at least two isocyanate groups in one molecule on one surface of the vapor-deposited layer or the plastic substrate of the plastic substrate on which the vapor-deposited layer is formed. A gas barrier layer is formed on the undercoat layer,
13. At least one of the gas barrier layer or the undercoat layer is adjacent to the vapor deposition layer;
14 The gas barrier material has two vapor deposition layers, and a gas barrier layer and an undercoat layer are formed between the two vapor deposition layers;
15. Both the gas barrier layer and the undercoat layer are adjacent to the deposited layer;
16. Containing an alkaline compound of a polyvalent metal in the undercoat layer,
17. The alkaline compound of the polyvalent metal is composed of at least one of calcium, magnesium, zinc carbonate and hydroxide;
18. The isocyanate compound is a combination of a linear aliphatic isocyanate compound and an alicyclic isocyanate compound having an alicyclic ring structure in the skeleton;
19. The aliphatic isocyanate compound has an isocyanurate structure;
20. A region (x) not containing an alkali compound of a polyvalent metal is formed on the gas barrier layer side of the undercoat layer, and the content of nitrogen in the region (x) of the undercoat layer other than the region (x) More than the nitrogen content is preferred.

  Since the vacuum heat insulating material of the present invention uses a gas barrier laminate in which gas barrier layers having excellent gas barrier properties and flexibility are laminated as an exterior material, it can exhibit an excellent heat insulating effect over a long period of time. Moreover, in the conventional vacuum insulation material, it is not necessary to use an aluminum foil or the like that has been used to secure gas barrier properties and ability to block radiant heat (reflectance). There is no fear of reducing the heat insulation effect due to the heat bridge.

In addition, since this gas barrier laminate can directly laminate a thermoplastic resin on the gas barrier layer by extrusion laminating, it is previously dry-laminated by extrusion laminating to the gas barrier layer like a conventional gas barrier material made of a polycarboxylic acid polymer. It is not necessary to protect the gas barrier material by laminating other base materials, and it is excellent in productivity and economy, and since it is not necessary to use a solvent for the lamination, the gas barrier laminate is caused by the adhesive layer. There is no fear of residual solvent, and the residual solvent can impair the reduced pressure inside the vacuum heat insulating material. Therefore, the vacuum heat insulating material of the present invention can exhibit an excellent heat insulating effect for a long time.
That is, the gas barrier layer of the gas barrier laminate used for the vacuum heat insulating material of the present invention has heat decomposition resistance that does not cause thermal decomposition in the processing temperature range in the laminate by extrusion coating, and there is an uncrosslinked portion in this processing temperature range. Therefore, it is possible to ensure a certain molecular mobility due to thermal energy and relieve stress generated in the gas barrier layer, thereby ensuring crack resistance, and directly applying a thermoplastic resin to the gas barrier layer by extrusion coating It becomes possible to do.

  Thermal decomposition resistance in the processing temperature range can be expressed by weight loss in thermogravimetric analysis (TGA) measurement, while crack resistance in the processing temperature range is tan δ in dynamic viscoelasticity (DMS) measurement. In the present invention, the gas barrier layer composed of the polycarboxylic acid polymer of the gas barrier material can be expressed by a difference from 200 ° C. in thermogravimetric analysis (TGA) measurement at a layer heating rate of 10 ° C. /. Difference in weight loss up to 320 ° C. of 10% or less, especially 3 to 9%, and subtraction of tan δ at 50 ° C. from tan δ at 200 ° C. in dynamic viscoelasticity (DMS) measurement at 20 Hz Is preferably 0.010 or more, and particularly preferably in the range of 0.011 to 0.060, so that the thermoplastic resin is directly applied on the gas barrier layer. Ri becomes possible to suitably extrusion coating.

  In the gas barrier laminate used for the exterior material in the present invention, a polyolefin resin, an ethylene- (meth) acrylic copolymer, and an ionomer resin are used as the thermoplastic resin to be directly extruded and laminated to the gas barrier layer. When extruding the gas barrier layer, it does not cause thermal decomposition of the gas barrier layer, can exhibit excellent adhesion to the gas barrier layer, prevents delamination, and the gas barrier laminate is subjected to stress such as bending In addition, the occurrence of cracks in the gas barrier layer can be suppressed, and stable gas barrier properties can be exhibited.

In addition, this gas barrier material has excellent gas barrier properties, flexibility and water resistance even if the polycarboxylic acid polymer is not cross-linked by a covalent bond using a cross-linking agent, simplifying the heat treatment process required for the cross-linking reaction. Can be
Furthermore, by forming a gas barrier layer on the undercoat layer containing the polyvalent metal-containing composition, it is possible to increase the ionic crosslinking rate by the polyvalent metal without performing immersion treatment or spray treatment. It becomes possible to produce an exterior material having gas barrier properties with high productivity. Since this undercoat layer contains an isocyanate compound having at least two isocyanate groups in one molecule, there is an isocyanate compound in the vicinity of each interface of the gas barrier layer / undercoat layer and undercoat layer / substrate. In addition, interfacial reactions with functional groups such as carboxyl groups of polycarboxylic acid polymers and hydroxyl groups contained in plastic substrates, or electrical cohesion between polar groups at the interface occur, further improving interlayer adhesion It becomes possible to do.

It is a figure which shows the cross-section of an example of the vacuum heat insulating material of this invention. It is a figure which shows the laminated structure of an example of the gas barrier material used for the exterior material of the vacuum heat insulating material of this invention. It is a figure which shows the laminated structure of another example of the gas barrier material used for the exterior material of the vacuum heat insulating material of this invention. It is a figure which shows the laminated structure of an example of the exterior material of the vacuum heat insulating material of this invention. It is a figure which shows the laminated structure of other examples of the exterior material of the vacuum heat insulating material of this invention. It is a figure which shows the laminated structure of other examples of the exterior material of the vacuum heat insulating material of this invention. It is a figure which shows the laminated structure of other examples of the exterior material of the vacuum heat insulating material of this invention. It is a figure which shows the laminated structure of other examples of the exterior material of the vacuum heat insulating material of this invention. It is a figure which shows the laminated structure of other examples of the exterior material of the vacuum heat insulating material of this invention. It is a figure which shows the laminated structure of other examples of the exterior material of the vacuum heat insulating material of this invention.

As shown in FIG. 1, the vacuum heat insulating material 1 is composed of a core material 2 and an exterior material 3 that covers the core material 2. The exterior material is welded and sealed by heat sealing, and the internal decompressed state is reduced. In the present invention, it is an important feature that the gas barrier laminate having the specific gas barrier material described above is used as the exterior material to be used.
That is, a gas barrier material obtained by ion-crosslinking a polycarboxylic acid polymer with a polyvalent metal is conventionally known. In the present invention, in such a gas barrier material, a monovalent metal element, a polyvalent metal element, and It has been found that by controlling the nitrogen content within a predetermined range, excellent gas barrier properties, flexibility, water resistance, and water resistance after bending can be obtained, and such a gas barrier material is used as an exterior material for a vacuum heat insulating material. It has been found that the above-described effects can be exhibited by using in the above.

In addition, the monovalent metal element and the polyvalent metal element in the gas barrier layer in the gas barrier material of the present invention are respectively a monovalent metal-containing compound and a polycarboxylic acid used for partially neutralizing the polycarboxylic acid-based polymer. Derived from an alkaline compound of a polyvalent metal used for ionic crosslinking between carboxyl groups of a polymer, and the nitrogen element is derived from an isocyanate compound, and the content of these elements is in the above range. The above-described effects are exhibited.
The content of these metal elements can be measured by using an ICP mass spectrometer after ashing the gas barrier layer, and the nitrogen element in the gas barrier layer can be measured by a combustion method, Further, the content of carbon, oxygen and nitrogen atoms in the surface layer of the gas barrier layer can be measured by surface analysis using XPS (X-ray Photo-electronic Spectroscopy).

(Gas barrier material)
The gas barrier material used for the exterior material of the vacuum heat insulating material of the present invention is composed of a polycarboxylic acid polymer, 1.4% by weight or less of a monovalent metal element, and at least 5.0 to 18.0% by weight. A gas barrier layer containing a polyvalent metal element and nitrogen element of 0.01 to 3.0% by weight with respect to the total weight of nitrogen and carbon is formed on a plastic substrate on which a vapor deposition layer is formed, or through an undercoat layer. 2 is provided as a gas barrier material formed on a plastic substrate on which a vapor-deposited layer is formed. In particular, as shown in FIG. 2, the gas barrier layer 11 is a plastic in which a vapor-deposited layer 13a is formed via an undercoat layer 12. A gas barrier material formed on the base material 13b can be suitably used.
Further, the gas barrier material is further formed by forming a vapor deposition layer on the plastic substrate on which the vapor deposition layer is formed, or on the gas barrier layer formed on the plastic substrate on which the vapor deposition layer is formed through the undercoat layer. It can be preferably used, and a plastic base material on which a vapor-deposited layer is not formed is used, on the plastic base material or on the plastic base material through the undercoat layer, on the formed gas barrier layer A vapor deposition layer may be formed.

The gas barrier material used in the present invention comprises a polycarboxylic acid polymer as a main component, and the carboxyl group of this polycarboxylic acid polymer is ionically cross-linked with a polyvalent metal, and also due to the presence of a nitrogen element derived from an isocyanate compound. It is created as a gas barrier material having excellent gas barrier properties, flexibility and water resistance, and further water resistance and blocking resistance after bending processing. It is important that the contents of the metal element and the nitrogen element are within the above ranges.
A gas barrier layer having such characteristics is a composition for forming a gas barrier layer, which comprises a polycarboxylic acid polymer, a basic compound having a monovalent metal element necessary for partial neutralization of the polymer, and an isocyanate compound. Is applied to a plastic substrate having a vapor deposition layer, and the carboxyl group in the gas barrier layer can be ion-crosslinked with a polyvalent metal to form a gas barrier material.
Further, in a gas barrier material comprising a combination of a gas barrier layer and an undercoat layer, a layer is formed by applying a solution containing a polycarboxylic acid polymer on an undercoat layer containing an isocyanate compound and an alkali compound of a polyvalent metal. By forming, a polyvalent metal ion and an isocyanate compound are efficiently supplied from the undercoat layer to the polycarboxylic acid polymer, and the gas barrier layer on the undercoat layer, that is, the gas barrier layer on the plastic substrate through the undercoat layer. It can be set as the gas barrier material formed.

[Polycarboxylic acid polymer]
As the polycarboxylic acid polymer constituting the gas barrier layer, partial neutralization with a monovalent metal element can be performed within the following range in order to exhibit the above-described effect of water resistance. A polycarboxylic acid-based polymer that is partially neutralized in an amount of 4.5% or less, more preferably 4.0% or less, particularly in a molar ratio with respect to a carboxyl group, is partially neutralized by a monovalent metal element. It is desirable for controlling the amount of the monovalent metal element in the gas barrier material within the above range. When the neutralization amount is larger than the above range, the water resistance after bending and the gas barrier property under high temperature and high humidity conditions are inferior to those in the above range.
As the monovalent metal, sodium and potassium are particularly preferable, and it is preferable to neutralize the polycarboxylic acid polymer using these hydroxides as the monovalent metal compound.

Examples of the polycarboxylic acid-based polymer include homopolymers or copolymers of monomers having a carboxyl group, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, polyitaconic acid, and acrylic acid-methacrylic acid copolymer. Polyacrylic acid and polymethacrylic acid are preferred.
The “weight average molecular weight” of the polycarboxylic acid polymer is not particularly limited, but is preferably in the range of 2000 to 5,000,000, particularly 10,000 to 1,000,000.
In addition, the measurement of the above “weight average molecular weight” was carried out by using two columns, “TSK G4000PWXL” and “TSK G3000PWXL” (manufactured by Tosoh Corporation) as separation columns, using a 50 mmol phosphoric acid aqueous solution as an eluent, and a flow rate of 40 ° C. It was determined from a calibration curve of a standard polycarboxylic acid polymer at 1.0 ml / min.

[Isocyanate compound]
By containing an isocyanate compound in the gas barrier layer, nitrogen elements in the above-described range can be present in the gas barrier layer.
As the isocyanate compound, it can be used by appropriately selecting from the isocyanate compounds exemplified as the isocyanate curing agent used in the undercoat layer described later, but among the isocyanate compounds, the compatibility with the polycarboxylic acid polymer is poor. It is preferable to use those such as isophorone diisocyanate and derivatives thereof. As a result, the isocyanate compound can be effectively bleed out on the surface of the gas barrier material to allow chemical bonds derived from the isocyanate compound to exist on the surface of the gas barrier material, and water resistance after bending can be imparted to the gas barrier layer. It becomes possible.

[Gas barrier material containing no undercoat layer]
In a gas barrier material that does not contain an undercoat layer, a composition for forming a gas barrier layer containing a polycarboxylic acid polymer, a basic compound having a monovalent metal element when the polymer is partially neutralized, and an isocyanate compound A film, sheet or coating film comprising the composition for forming a gas barrier layer is formed by ion-crosslinking carboxyl groups of a polycarboxylic acid polymer with an alkaline compound-containing composition of a polyvalent metal. it can.
The composition for forming a gas barrier layer may be prepared by dissolving a polycarboxylic acid polymer and an isocyanate compound in a solvent containing water, or by mixing a water-containing solution of these components. It is a solution in which the acid polymer is dissociated.
The solvent for dissolving the polycarboxylic acid-based polymer may be only water, but may be a mixed solvent of water such as alcohol such as methanol, ethanol or isopropanol, ketone such as 2-butanone or acetone, or aromatic solvent such as toluene and water. In particular, a solvent having a boiling point lower than that of water can be used in combination with water.
From the viewpoint of bleeding out the isocyanate compound, the organic solvent is preferably blended in an amount of 10 to 400 parts by weight with respect to 100 parts by weight of water.

In addition to the above components, an inorganic dispersion can also be contained. Such an inorganic dispersion has a function of blocking moisture from the outside and protecting the gas barrier material, and can further improve gas barrier properties and water resistance.
Such inorganic dispersions may be spherical, needle-like, layered, etc., but may have any shape, but have wettability with respect to the polycarboxylic acid polymer, and those that disperse well in the composition for forming a gas barrier material are used. Is done. In particular, from the viewpoint that water can be blocked, a silicate compound having a layered crystal structure such as water-swellable mica and clay is preferably used. These inorganic dispersions preferably have an aspect ratio of 30 or more and 5000 or less in that they are dispersed in layers and block moisture.
The content of the inorganic dispersion is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the total of the polycarboxylic acid polymer and the isocyanate compound.

The amount of polycarboxylic acid-based polymer contained in the resin composition in the gas barrier layer forming composition, that is, the amount of free carboxyl groups, is preferably at least 150 KOHmg / g or more, particularly 250 to 970 KOHmg / g in terms of acid value. . Here, the acid value is obtained by determining the number of mg of potassium hydroxide necessary for neutralizing the acidic free functional group contained in 1 g of the resin by a conventional method based on alkali neutralization titration.
The isocyanate compound is preferably contained in an amount of 0.04 to 12 parts by weight, particularly 0.1 to 7 parts by weight, based on 100 parts by weight of the polycarboxylic acid polymer.
Depending on the type and content of the polycarboxylic acid polymer and isocyanate compound used or the coating amount of the gas barrier layer forming composition, the gas barrier layer forming composition is used at a temperature of 40 to 110 ° C. for 1 second to Heat for 1 minute (peak retention time) to form a sheet, film or coating. Subsequently, the gas barrier layer can be produced by ion-crosslinking carboxyl groups in the sheet, film or coating film with a polyvalent metal.

Ion cross-linking with a polyvalent metal is not limited to this, but the metal barrier can be easily treated by treating the gas barrier layer with water containing an alkali compound of a polyvalent metal or an alcohol solution containing an alkali compound of a polyvalent metal. A crosslinked structure can be formed.
The treatment with water containing an alkali compound of a polyvalent metal includes (i) immersion treatment of a gas barrier material in water containing an alkali compound of a polyvalent metal, (ii) water containing an alkaline compound of a polyvalent metal Spray treatment to gas barrier material, (iii) atmosphere treatment in which gas barrier material is placed under high humidity after treatment of (i) to (ii), (iv) retort treatment with water containing alkaline compound of polyvalent metal (preferably , A method in which the packaging material and hot water are in direct contact), and the like.
The process (iii) is a process that brings about the aging effect after the processes (i) to (ii), and enables the processes (i) to (ii) to be shortened. The treated water used in any of the above treatments (i) to (iii) may be cold water, but the alkalinity of the polyvalent metal so that the water containing the alkaline compound of the polyvalent metal can easily act on the gas barrier material. The temperature of the water containing the compound is set to 20 ° C. or higher, particularly 40 to 100 ° C. In the case of (i) to (ii), the processing time is preferably 3 seconds or more, particularly about 10 seconds to 4 days, and in the case of (iii), the processing time (i) to (ii) is 0. After the treatment for 5 seconds or more, particularly 1 second to 1 hour, it is preferable to perform an atmosphere treatment in which the gas barrier material is placed under high humidity for 1 hour or more, particularly 2 hours to 14 days. In the case of the treatment (iv), the treatment temperature is 101 ° C. or higher, particularly 120 to 140 ° C., and the treatment is performed for 1 second or longer, particularly 3 seconds to 120 minutes.
In any case, the water containing the alkali compound of the polyvalent metal is preferably neutral to alkaline.

In addition, as the treatment with the alcohol-based solution containing the polyvalent metal alkaline compound, the alcohol-based solution containing the polyvalent metal alkaline compound is applied onto the film, sheet, or coating film comprising the gas barrier material-forming composition described above. This can be done by coating. Since the alcohol-based solution is likely to soak into a film or the like made of the gas barrier material forming composition, the polyvalent metal can be efficiently impregnated in the gas barrier material forming composition, and the number of steps compared to treatment with water. Or processing time can be shortened and it is excellent in productivity.
Examples of the solvent used in the alcohol-based solution containing the polyvalent metal alkaline compound include methanol, ethanol, isopropanol, and the like, although they vary depending on the type of the polyvalent metal alkaline compound used.

The polyvalent metal ion is not particularly limited as long as the carboxyl group of the polycarboxylic acid polymer can be cross-linked. Alkaline earth metal (magnesium Mg, calcium Ca, strontium Sr, barium Ba, etc.), Group 8 metal of the periodic table Examples include metal ions such as iron (Fe, ruthenium Ru, etc.), periodic table group 11 metals (copper Cu, etc.), periodic table group 12 metals (zinc Zn, etc.), periodic table group 13 metals (aluminum Al, etc.), In particular, it is preferably 2 to 3 valent, and preferably a divalent metal ion such as calcium, magnesium ion or zinc can be used. Moreover, the said metal ion can be used 1 type or in combination of 2 or more types.
Examples of alkaline compounds of polyvalent metals include hydroxides (eg, magnesium hydroxide, calcium hydroxide, etc.), carbonates (eg, magnesium carbonate, calcium carbonate, etc.), organic acid salts, eg, carboxylic acids of the above metals. Salts (for example, acetates such as zinc acetate and calcium acetate, or lactates such as zinc lactate and calcium lactate) can be exemplified, but by-products when a metal ion bridge is formed from the viewpoint of safety In view of not staying in the gas barrier material, it is particularly preferable to use at least one of calcium or magnesium carbonate and hydroxide.

When an alkali compound of a polyvalent metal is contained in water, it is preferably 0.125 mmol / L or more, more preferably 0.5 mmol / L or more, in terms of metal atom in water, and 2.5 mmol / L. It is still more preferable that it is above.
Similarly, when an alkaline compound of a polyvalent metal is contained in an alcoholic solvent, the polyvalent metal used in the solution varies depending on the type of polyvalent metal alkaline compound used in the alcoholic solvent and the coating amount. In terms of metal atom, it is preferably 1 mmol / L or more, more preferably 10 mmol / L or more, and further preferably 30 mmol / L or more.
In the gas barrier material that has been treated with the solution containing the alkali compound of the polyvalent metal, the carboxyl groups of the polycarboxylic acid polymer are ion-crosslinked at a ratio of 20% or more, particularly 30% or more with polyvalent metal ions. It is desirable that

[Gas barrier material containing undercoat layer]
As described above, the gas barrier material containing the undercoat layer has a gas barrier layer on at least one surface of the plastic substrate on which the vapor deposition layer is formed, and between the vapor deposition layer or the plastic substrate and the gas barrier layer, An undercoat layer containing an isocyanate compound having at least two isocyanate groups in one molecule and an alkali compound of a polyvalent metal is formed.
An undercoat layer containing an isocyanate compound and an alkali compound of a polyvalent metal is formed on a plastic substrate on which a vapor-deposited layer is formed, and a solution containing a polycarboxylic acid polymer is applied onto the undercoat layer. A gas barrier layer is formed. As a result, the polyvalent metal ions and isocyanate compound present in the undercoat layer are supplied into the polycarboxylic acid-based polymer, so that a predetermined amount of the polyvalent metal element and nitrogen element can be present in the gas barrier layer. Become. As a result, the polycarboxylic acid polymer is cross-linked with metal ions, and most of the isocyanate compound supplied into the polycarboxylic acid polymer bleeds out to the surface of the gas barrier layer, and chemical bonds derived from the isocyanate compound are removed from the gas barrier layer. The remaining isocyanate compound remains in the vicinity of the interface with the undercoat layer, and mainly crosslinks between the component in the undercoat layer and the polycarboxylic acid-based polymer, or between the isocyanate compounds. react. As a result, it is possible to obtain a gas barrier laminate that has excellent gas barrier properties, flexibility, and water resistance, as well as excellent water resistance and blocking resistance after bending, as with the gas barrier material described above.

[Undercoat layer]
The undercoat layer is composed of a main material resin, an isocyanate curing agent having at least two isocyanate groups in one molecule, and an alkali compound of a polyvalent metal, but the main material resin contains a metal element in the resin skeleton. It is particularly preferred that the polyester polyol is a combination of a linear aliphatic isocyanate compound and an alicyclic isocyanate compound having an alicyclic ring structure in the skeleton.
That is, the polyester polyol containing a metal element as a main resin in the resin skeleton can itself be laminated with an adhesive as an undercoat agent on a plastic substrate, and also contains water by having a metal element. Since it swells easily with respect to the solvent, it can be swollen by applying a paint having a polycarboxylic acid polymer to effectively transfer polyvalent metal ions present in the undercoat layer into the barrier layer. It becomes possible.

In addition, by using a combination of a linear aliphatic isocyanate compound having different compatibility with the main material resin and an alicyclic isocyanate compound having an alicyclic ring structure in the skeleton as the isocyanate curing agent, It is possible to control the bleed-out behavior of the compound in the undercoat layer.
That is, since the linear aliphatic isocyanate compound is highly compatible with the main resin, it diffuses uniformly into the undercoat layer. In contrast, an alicyclic isocyanate compound having an alicyclic ring structure in the skeleton has poor compatibility with the main resin, and therefore bleeds out to the barrier layer side and the substrate side of the undercoat layer. As shown in FIG. 3, the undercoat layer 12 is formed with a region (x) 14 that does not contain an alkali compound of a polyvalent metal, and the nitrogen content in the region (x) 14 is the region. It is larger than the nitrogen content of the undercoat layer 12 other than (x).

[Main resin]
As the main material resin used for the undercoat layer, it is preferable to use a non-aqueous resin in which a metal element is contained in the resin skeleton, and urethane-based, epoxy-based, acrylic-based, polyester-based, etc. It is preferable that a metal element is introduced into the monomer constituting these polymers, so that a metal element can be included in the formed resin skeleton. The “non-aqueous resin” is a concept that excludes an emulsion or latex dispersed in a solvent containing water, or a water-soluble resin, and thereby an undercoat caused by excessive swelling that occurs upon contact with a water-containing solvent. A decrease in the mechanical strength of the layer is effectively prevented.
As the metal base suitable for introduction into the resin monomer, it is desirable to have a functional group having polarity in order to improve the dispersibility of the polyvalent metal. Etc. Examples of the metal element include lithium Li, potassium K, sodium Na, magnesium Mg, calcium Ca, copper Cu, and iron Fe. A monovalent metal element is particularly preferable, and the present invention. In particular, sodium sulfonate is preferably introduced.

  In the gas barrier material used in the present invention, an isocyanate curing agent is used in order to obtain excellent adhesion to the substrate and to increase the dispersibility of the alkali compound of the polyvalent metal. As the main material resin, it is preferable to use a polyol component such as polyester polyol, polyether polyol, or a modified urethane thereof, whereby a urethane bond is formed in the undercoat layer, and excellent adhesion to the substrate and The dispersibility of the polyvalent metal alkaline compound can be increased. In addition, when the weight of the isocyanate curing agent necessary for reacting the hydroxyl content in the polyol component is 1 equivalent, the isocyanate curing agent is preferably present so as to be at least 4 equivalents or more.

As the polyol component used for forming the urethane-based polymer, a polyester polyol or a urethane-modified product thereof is preferable. Examples of these polyester polyol components include polyester polyols obtained by reacting polyvalent carboxylic acids or their dialkyl esters or mixtures thereof with glycols or mixtures thereof.
The glass transition temperature of the polyester polyol is preferably -50 ° C to 100 ° C, more preferably -20 ° C to 80 ° C. The number average molecular weight of these polyester polyols is preferably from 1,000 to 100,000, more preferably from 3,000 to 80,000.
Examples of the polyvalent carboxylic acid include aromatic polyvalent carboxylic acids such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid, and aliphatic polyvalent carboxylic acids such as adipic acid, azelaic acid, sebacic acid, and cyclohexanedicarboxylic acid.
Examples of the glycol include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, and 1,6-hexanediol.

In the present invention, a non-aqueous resin having a metal element in the resin skeleton can be obtained by copolymerizing a component having a metal base introduced into the polyol component or the polyvalent carboxylic acid component.
Examples of the polyvalent carboxylic acid introduced with such a metal base include metals such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5 [4-sulfophenoxy] isophthalic acid. Mention may be made of salts. Examples of the polyol having a metal base introduced include metal salts such as 2-sulfo-1,4-butanediol and 2,5-dimethyl-3-sulfo-2,5-hexanediol. Particularly preferred is 5-sodium sulfoisophthalic acid.
The component into which the metal base has been introduced is desirably copolymerized in an amount of 0.01 to 10 mol%. When the amount is less than the above range, the migration of polyvalent metal ions cannot be sufficiently promoted. On the other hand, when the amount is more than the above range, the water resistance is poor.

Whether or not the metal element is contained in the resin skeleton of the non-aqueous resin can be detected, for example, by analyzing the raw material resin with fluorescent X-rays.
(Measurement conditions of X-ray fluorescence analyzer)
Equipment used: ZSX100e manufactured by Rigaku Corporation
Measurement conditions: Measurement object Na-Kα ray
Measurement diameter 30mm
X-ray output 50kV-70mA
Measurement time 40s

[Isocyanate curing agent]
As the isocyanate curing agent used in the undercoat layer, as described above, it is particularly preferable to use a combination of a linear aliphatic isocyanate compound and an alicyclic isocyanate compound having an alicyclic ring structure in the skeleton. .
The linear aliphatic isocyanate compound and the alicyclic isocyanate compound are desirably blended in a weight ratio of 60:40 to 15:85, particularly 55:45 to 30:70. When the linear aliphatic isocyanate compound is less than the above range, sufficient adhesion cannot be obtained, and when the alicyclic isocyanate compound is less than the above range, the region (x) is formed. May be difficult to do.

Examples of the linear aliphatic isocyanate include tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Among them, those having an isocyanurate structure are preferable. Specifically, an isocyanurate body having 1,6-hexamethylene diisocyanate as a structural unit can be preferably used.
Examples of the alicyclic isocyanate compound having an alicyclic ring structure in the skeleton include 1,3-cyclohexylene diisocyanate, 4-cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4. Examples include '-dicyclohexylmethane diisocyanate and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate. Among them, isophorone diisocyanate and derivatives thereof can be preferably used.
Examples of the linear aliphatic polyisocyanate compound and the alicyclic isocyanate compound include polyfunctional polyisocyanate compounds such as isocyanurate, burette and allophanate derived from the polyisocyanate monomer, or trimethylolpropane and glycerin. A polyfunctional polyisocyanate compound containing a terminal isocyanate group obtained by a reaction with a trifunctional or higher functional polyol compound can also be used.

  In the undercoat layer, the linear aliphatic isocyanate compound is easily diffused uniformly in the undercoat layer when diffusing with the solvent volatilization, so that the glass transition temperature (Tg) is −20 ° C. or less and the number average molecular weight. It is preferable that (Mn) is 1200 or less, particularly that the glass transition temperature (Tg) is −40 ° C. or less and the number average molecular weight (Mn) is 1100 or less. In addition, the alicyclic isocyanate compound remains on the barrier layer side of the undercoat layer or the plastic substrate side, and it is easy to form the region (x), so that the glass transition temperature (Tg) is 50. It is preferable that the number average molecular weight (Mn) is 400 or more, particularly the glass transition temperature (Tg) is 60 ° C. or more and the number average molecular weight (Mn) is 500 or more.

[Alkaline compound of polyvalent metal]
As the polyvalent metal alkaline compound to be contained in the undercoat layer, those mentioned above can be used, but the polyvalent metal alkaline compound transferred to the gas barrier layer composed of the polycarboxylic acid polymer is quickly dissolved. Thus, it is preferable that the surface of the particles of the alkali compound of the polyvalent metal is not subjected to chemical treatment.
In addition, the particles of the polyvalent metal alkaline compound may remain in a portion other than the region (x) in the undercoat layer, and the primary particle diameter of the particles is 0.5 μm depending on the amount of the remaining particles. If it exceeds, the transparency of the coating layer (undercoat layer and gas barrier layer) of the gas barrier material may slightly decrease. Therefore, the primary particle diameter of the alkali metal particles of the polyvalent metal is preferably 0.5 μm or less, and particularly preferably 0.4 μm or less. The primary particle diameter of the alkali compound particles of the polyvalent metal can be determined by observation with a secondary electron image of a scanning electron microscope.

In the present invention, in the composition for forming the undercoat layer (hereinafter referred to as “undercoat layer forming composition”), the content of the alkali compound of the polyvalent metal is carboxyl to one polyvalent metal ion. As two groups react, it is preferable to contain 0.3 equivalent or more with respect to the carboxyl group of the polycarboxylic acid polymer present in the gas barrier layer forming composition in terms of metal atoms, In particular, when used for applications under high-temperature and high-humidity conditions, the content is preferably 0.6 equivalent or more from the viewpoint of maintaining gas barrier properties under high-temperature and high-humidity conditions. If the content of the alkali compound of the polyvalent metal is less than the above range, the polycarboxylic acid polymer cannot be sufficiently crosslinked, and it becomes difficult to ensure gas barrier properties.
In the undercoat layer after supplying polyvalent metal ions to the polycarboxylic acid polymer, it is preferable that the amount of polyvalent metal alkaline compound particles remaining in the layer is small. Thereby, the risk that by-products are generated can be reduced, and the heat insulating performance can be maintained over a long period of time as an exterior material of the vacuum heat insulating material. Specifically, the residual amount (equivalent) which is the difference between the charged amount (equivalent) of the alkaline compound of the polyvalent metal and the amount (equivalent) used for ionic crosslinking is 1.1 or less, particularly 0.3 or less. Preferably there is.
The resin content in the composition for forming an undercoat layer is preferably 15 to 80% by weight, particularly 20 to 60% by weight.
In addition, the resin component in the undercoat layer forming composition is preferably non-aqueous, and can be prepared with a solvent such as toluene, 2-butanone, cyclohexanone, solvesso, isophorone, xylene, ethyl acetate, butyl acetate, In particular, it is preferable to use a low boiling point solvent in order to make it possible to form a layer at a low temperature. These solvents may be dissolved alone or in a mixed solution, or can be prepared by mixing solutions of respective components.
In addition to the above components, known curing accelerator catalysts, fillers, softeners, anti-aging agents, stabilizers, adhesion promoters, leveling agents, antifoaming agents, plasticizers, inorganic fillers, tackifying resins, fibers , Colorants such as pigments, usable time extenders and the like can also be used.

As the gas barrier layer-forming composition applied on the undercoat layer, the same composition as the gas barrier layer-forming composition in the gas barrier material not containing the undercoat layer described above can be used except that it does not contain an isocyanate compound. .
In the gas barrier layer forming composition, it is essential that the solvent contains water in order to dissolve the alkali compound of the polyvalent metal and transfer it to the gas barrier layer forming composition. Furthermore, it is desirable to mix a solvent having a good affinity with the undercoat layer with water in order to improve the affinity with the undercoat layer and promote the transition of the alkaline compound of the polyvalent metal to the gas barrier layer forming composition. The solvent having good affinity with the undercoat layer varies depending on the resin component used in the composition for forming the undercoat layer. For example, when a urethane polymer is used, alcohol such as methanol, ethanol, isopropanol, 2-butanone, A ketone such as acetone can be preferably used.
Furthermore, from the viewpoint of controlling the amount of the isocyanate compound transferred to the gas barrier layer forming composition, it is desirable to blend other solvent in an amount of 1900 parts by weight or less, particularly 5 to 900 parts by weight with respect to 100 parts by weight of water. It is further desirable to blend in an amount of 10 to 400 parts by weight.

[Plastic substrate]
In the present invention, the plastic substrate on which the gas barrier layer or the undercoat layer is formed is composed of a film or sheet made of a thermoformable thermoplastic resin, and in particular, one having a vapor deposition layer can be suitably used.
The vapor deposition layer may be formed on at least one surface of the plastic substrate, and the gas barrier layer or the undercoat layer may be formed on either the vapor deposition layer or the plastic substrate surface. Since it is excellent in crack resistance, it is preferably formed on the vapor deposition layer, whereby the occurrence of cracks and the like in the vapor deposition layer can be prevented.
Examples of the method for producing a film or sheet include conventionally known forming methods such as a T-die method, an inflation film forming method, and a cast film forming method.
The film or sheet can be used as a biaxially stretched film or sheet produced by biaxially stretching sequentially or simultaneously at a stretching temperature and heat-setting the stretched film or sheet.
Although the thickness of a film or a sheet | seat is not limited to this, It is suitable to exist in the range of 5-3000 micrometers.

  Suitable examples of the resin constituting the plastic substrate include low-, medium- or high-density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene-copolymer, ionomer, Olefin copolymers such as ethylene-vinyl acetate copolymer and ethylene-vinyl alcohol copolymer; polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate, polyethylene naphthalate; nylon 6, nylon 6,6 , Nylon 6,10, polyamide such as metaxylylene adipamide; polystyrene, styrene-butadiene block copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer (ABS resin), etc. Tylene copolymer; Vinyl chloride copolymer such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymer; Acrylic copolymer such as polymethyl methacrylate and methyl methacrylate / ethyl acrylate copolymer; is there.

These thermoplastic resins may be used alone or present in the form of a blend of two or more, and the plastic substrate may be in a single layer configuration or, for example, co-melt extrusion or other lamination It may be a laminated structure of two or more layers.
Of course, the melt-moldable thermoplastic resin may contain one or more additives such as pigments, antioxidants, antistatic agents, ultraviolet absorbers, lubricants, etc. as required per 100 parts by weight of the resin. The total amount can be added in the range of 0.001 to 5.0 parts.
In order to reinforce the gas barrier material, fiber reinforcement such as glass fiber, aromatic polyamide fiber, carbon fiber, pulp, cotton linter, etc., powder reinforcement such as carbon black, white carbon, glass flake, aluminum flake, etc. One or two or more types of flaky reinforcing materials such as the above can be blended in a total amount of 2 to 150 parts by weight per 100 parts by weight of the thermoplastic resin, and heavy or soft calcium carbonate for the purpose of increasing the amount. , Mica, talc, kaolin, gypsum, clay, barium sulfate, alumina powder, silica powder, magnesium carbonate and the like in an amount of 5 to 100 parts by weight as a total amount per 100 parts by weight of the thermoplastic resin Even if it mix | blends according to a prescription known per se, it does not interfere.
Furthermore, with the aim of improving gas barrier properties, a prescription known per se in the amount of 5 to 100 parts by weight as a total amount of scaly inorganic fine powders such as water-swellable mica and clay per 100 parts by weight of the thermoplastic resin There is no problem even if it is blended according to.

  The vapor deposition layer formed on the plastic substrate can be formed using a conventionally known physical or chemical vapor deposition method. For example, an inorganic vapor deposition layer such as silicon oxide or aluminum oxide, or aluminum can be used. A metal-based vapor deposition layer can be formed. Thereby, in combination with the presence of the gas barrier material, it is possible to improve at least one of the gas barrier property of the exterior material or the ability to block radiant heat (reflectance).

The gas barrier material containing an undercoat layer first applies the above-described composition for forming an undercoat layer to at least one surface of the plastic substrate on which the above-described vapor deposition layer is formed.
The coating amount of the composition for forming an undercoat layer is determined by the resin content in the composition for forming an undercoat layer and the charged amount of the alkali compound of the polyvalent metal. The resin content in the undercoat layer is in the range of 0.02 to 5.0 g / m ² , particularly 0.1 to 2.5 g / m ² , and then the polycarboxylic acid in the gas barrier layer forming composition solution to be applied As described above, it is preferable that the polyvalent metal ion is applied in an amount of 0.3 equivalent or more with respect to the carboxyl group of the acid polymer. If the resin content is less than the above range, it is difficult to fix the undercoat layer to the plastic substrate. On the other hand, even if the resin content is greater than the above range, it is inferior in economic efficiency and has no particular merit.
Further, the composition for forming an undercoat layer applied on a plastic substrate depends on the type and amount of paint used, and is at a temperature of 50 to 200 ° C. for 0.5 seconds to 5 minutes, particularly 60 to 140. It is possible to form an undercoat layer by drying at a temperature of 1 ° C. for 1 second to 2 minutes, whereby the undercoat layer can be formed economically without affecting the plastic substrate.

Next, a gas barrier layer forming composition is applied on the formed undercoat layer. The amount of the polycarboxylic acid-based polymer contained in the gas barrier layer forming composition, that is, the amount of free carboxyl groups, is preferably at least 150 KOHmg / g or more, particularly 250 to 970 KOHmg / g in terms of acid value.
The coating amount of the gas barrier layer-forming composition is 0.3 to 4.5 g / m ² , particularly 0.5 to 3.3 in the dry state of only the resin component before ionic crosslinking is formed in the gas barrier layer. It is preferable to apply in a range of 0 g / m ² . If the coating amount is less than the above range, sufficient gas barrier properties cannot be obtained. On the other hand, even if the resin content is larger than the above range, it is inferior in economic efficiency and has no particular advantage.
Next, the applied gas barrier layer forming composition is subjected to heat treatment. During this heat treatment, the polyvalent metal ions and isocyanate compound in the undercoat layer migrate into the gas barrier layer forming composition, A metal ion cross-linked structure is formed between the carboxyl groups of the carboxylic acid polymer, and the nitrogen element derived from the isocyanate compound is present in the vicinity of the interface between the surface layer of the gas barrier layer and the undercoat layer. In particular, most of the isocyanate compound that has migrated into the gas barrier layer-forming composition bleeds out to the surface layer of the gas barrier layer to form chemical bonds derived from the isocyanate compound on the surface of the gas barrier layer.
The heating condition of the gas barrier layer forming composition is preferably in the range of 1 second to 1 minute, preferably in the range of 2 seconds to 30 seconds, at a temperature of 40 to 110 ° C., particularly 50 to 100 ° C. More preferred.
It is desirable that the gas barrier layer be sufficiently dried to reduce the moisture content of the gas barrier layer. Thereby, it becomes possible to suppress generation | occurrence | production of water vapor | steam, and it becomes possible to maintain heat insulation performance over a long term as an exterior material of a vacuum heat insulating material.

Application | coating of the composition for undercoat layer formation and gas barrier layer formation composition which were mentioned above, and drying or heat processing can be performed by a conventionally well-known method.
The coating method is not limited to this, but for example, spray coating, dipping, or coating by a bar coater, roll coater, gravure coater or the like is possible.
The drying or heat treatment can be performed by oven drying (heating), infrared heating, high-frequency heating, or the like.

(Exterior material)
The exterior material used for the vacuum heat insulating material of the present invention is characterized by the use of a gas barrier laminate formed by laminating the thermoplastic resin constituting the heat-welded layer on the gas barrier material described above by extrusion coating. Yes, as long as this gas barrier laminate is used as a part of the exterior material, the other layers of the gas barrier laminate can be configured in the same manner as a conventionally known exterior material. A gas barrier laminate having a configuration can be preferably used.
That is, the preferred gas barrier laminate used for the exterior material used in the vacuum heat insulating material of the present invention is, as shown in FIG. 4, in order from the inner surface side, the thermal welding layer 4, the gas barrier material 5, the adhesive layer 6, and the protective layer 8. As shown in FIG. 5, in order from the inner surface side, a heat-welded layer 4, a gas barrier material 5, an adhesive layer 6a, a vapor-deposited film layer (plastic base material 7a and vapor-deposited layer 7b) 7, an adhesive layer 6b, and a protective layer A laminated structure of the layer 8 can be exemplified.

The gas barrier material 5 shown in FIG. 4 or FIG. 5 has a gas barrier layer 5d via an undercoat layer 5c on a base material composed of a PET film 5a and an aluminum deposited layer 5b deposited on the PET film 5a in order from the outer surface side. Since the gas barrier layer having flexibility is formed together with the vapor deposition layer, particularly excellent gas barrier properties can be expressed.
The laminated structure of the gas barrier material is not limited to the specific example shown in FIG. 4 or FIG. 5. For example, the gas barrier material 5 in FIG. 4 or 5 is formed in FIG. The layer structure shown in FIG. 7 in which the vapor deposition layer 5bii is formed also on the gas barrier layer 5d may be used, or the gas barrier layer 5d is formed on the base resin side of the vapor deposition film via the undercoat layer 5c. The layer configuration shown in FIG. 8 may be used, or the layer configuration shown in FIG. 9 in which the vapor deposition layer 5bii is formed on the gas barrier layer 5d may be used. From the viewpoint of thermal decomposition resistance and crack resistance, it is preferable that the heat-welded layer is directly extrusion-coated on the gas barrier layer. However, as shown in FIG. 10, the vapor barrier layer is not formed on the plastic substrate 5a. A vapor deposition layer 5bi may be formed on 5d by a known technique, and may be directly extrusion coated on this vapor deposition layer.
In the present invention, as a laminated structure of the gas barrier material, it is preferable that at least one of the gas barrier layer and the undercoat layer is adjacent to the vapor deposition layer. That is, the barrier property of the gas barrier layer may decrease due to molecular vibration under high temperature conditions, but by adjoining the vapor deposition layer, the molecular vibration of the gas barrier layer is suppressed, making it difficult for oxygen to dissolve in the gas barrier layer. The gas barrier property can be maintained even under conditions.
As a suitable laminated structure, the gas barrier material has two layers of vapor deposition layers, and a layer structure (FIGS. 7 and 9) in which a gas barrier layer and an anchor coat layer are formed between the two vapor deposition layers can be exemplified. In particular, a layer structure (FIG. 7) in which both the gas barrier layer and the undercoat layer are adjacent to the vapor deposition layer is suitable.

In the present invention, a gas barrier material in which a heat-welded layer is formed can be formed by extruding a thermoplastic resin melt-kneaded by an extruder from a T die or an annular die to a gas barrier material. When the plastic resin is extrusion coated, the adhesive layer and the heat welding layer may be coextruded.
In addition, the thermoplastic resin serving as the heat welding layer may be extrusion coated onto the gas barrier layer of the gas barrier material, and another layer made of the thermoplastic resin may be formed on the other surface of the gas barrier material, for example, via an adhesive resin. 4 can be extrusion coated with a sandwich laminate or a thermoplastic layer to form a protective layer, whereby the gas barrier laminate shown in FIG. 4 is never subjected to a dry lamination step. Can be manufactured.
At this time, if necessary, corona discharge treatment or plasma treatment on the gas barrier material or the substrate on the extrusion line, ozone treatment on the thermoplastic resin molten film, anchor coat application on the substrate, or the like may be performed.
Further, co-extrusion lamination in which different types of thermoplastic resins are laminated at the same time, or multiple times of extrusion lamination by a tandem extruder may be performed on the same line.

Examples of the resin constituting the heat-welded layer provided in the innermost layer of the gas barrier laminate can include conventionally known heat-sealable resins, including, but not limited to, low-, medium-, or high-density polyethylene, Examples include linear low density polyethylene, olefin resins such as polypropylene and ethylene-propylene copolymers, acid-modified polyolefin resins, polyester resins such as polyethylene terephthalate, and acrylic resins such as polyacrylonitrile. It is particularly preferable to use an ethylene- (meth) acrylic acid copolymer or ionomer resin that forms hydrogen bonds with the gas barrier layer.
Similarly, from the viewpoint of adhesion, an olefin resin with no antioxidant added, an olefin resin polymerized by a single-site catalyst, and an epoxy capable of forming a chemical bond with a polar group such as a carboxyl group or a hydroxyl group on the surface of a substrate or gas barrier layer An olefin resin containing a reactive group such as a group can also be suitably used. These are particularly suitable for applications where water resistance is required because the adhesive strength is less likely to decrease even under high humidity as compared to the ethylene- (meth) acrylic acid copolymer or ionomer resin.
Incidentally, the term “antioxidant-free” as used herein means that the antioxidant contained in the resin is 10 ppm or less, and the oxidation of the resin is promoted at the time of melt extrusion, so that polar groups increase in the resin. The cohesive force with the material and the gas barrier material can be increased. In the case of an olefin resin having the latter reactive group, not only the chemical reaction is carried out by utilizing the heat at the time of melt extrusion, but also by aging storage after extrusion lamination and heat treatment (curing) in an oven or a thermostat. It is possible to enhance the adhesion by promoting the reaction.
Examples of the olefin resin polymerized by a single site catalyst include linear low density polyethylene polymerized using a single site catalyst represented by a metallocene catalyst having a low molecular weight distribution and low density. it can. Such an olefin resin is particularly advantageous in terms of an anchor effect because crystallization hardly occurs during cooling after extrusion and distortion due to crystallization is small.

Among these olefin-based resins, the density (measurement conditions are 23 ° C., conforming to JIS-K6922-1) is preferably 0.950 g / cm ³ or less, and in view of the anchor effect, the density is particularly 0.920 g / cm ³ or less. preferable. In addition, the melt flow rate (MFR: measurement condition is 190 ° C., 2.16 kg load, conforming to JIS-K6922-1) is preferably 0.1 g / 10 min or more from the point of extrusion processability. MFR of 7.0 g / 10 min or more is particularly preferable from the viewpoint that it can easily penetrate into the gas barrier layer and easily obtain excellent adhesiveness.
Furthermore, the thermoplastic resin is sufficiently adhered to the gas barrier layer, and the more flexible the thermoplastic resin, the higher the effect of relaxing the stress when the laminate is subjected to stress such as bending or tension. Therefore, the occurrence of cracks in the gas barrier layer can be suppressed, which is effective in terms of oxygen / nitrogen barrier stability.

  In addition, as the adhesive layer formed between the gas barrier material, the vapor deposition film, and the protective layer as necessary, a conventionally known adhesive resin can be used, but is not limited thereto, but as described above, the adhesive resin is formed by sandwich lamination. When the other layer (for example, a protective layer) is laminated by extruding the resin onto the base resin, it is preferable to use the resin described above for the heat-welded layer. In the case of lamination by dry lamination, urethane is used. A system adhesive can be suitably used.

The resin constituting the protective layer provided in the outermost layer of the gas barrier laminate and improving the mechanical strength and water resistance of the exterior material is not limited to this, but nylon 6, nylon 6, 6, nylon 6, 10 Polyamide resins such as metaxylylene adipamide; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate, polyethylene naphthalate, or ethylene / tetrafluoroethylene copolymer resin, polypropylene, polyethylene, etc. Olefin-based resins can be used, and in particular, from the viewpoint of mechanical strength of the exterior material, puncture resistance, and the like, it is desirable to be made of a biaxially oriented film. The most suitable protective layer can include a biaxially stretched nylon film.
The vapor deposition film is not limited to this, but the base film made of the above-described polyester, polyolefin, polyamide, etc., silicon oxide, aluminum oxide, a mixture of silica and alumina, an inorganic vapor deposition layer such as diamond-like carbon, Or although the vapor deposition film which formed metal-type vapor deposition layers, such as aluminum, can be used conveniently, a vapor deposition layer can also be directly formed on a gas barrier material.
In the gas barrier laminate used as an exterior material in the present invention, the thicknesses of the heat-welded layer, the deposited film and the protective layer are not particularly limited, and those in the range conventionally used for the exterior material of the vacuum heat insulating material should be used. Specifically, it is preferable that the heat welding layer is 20 to 100 μm, the vapor deposition layer is 100 to 20000 mm, the base material forming the vapor deposition layer is 5 to 100 μm, and the protective layer is 5 to 100 μm. is there.

(Method for manufacturing vacuum insulation)
The vacuum heat insulating material of the present invention can be produced in the same manner as a conventionally known vacuum heat insulating material except that the above-described exterior material is used, and is not limited thereto, but the core material is covered with the above-described exterior material, After the heat-welded layers of the exterior material are overlapped with each other, the pressure is reduced in a vacuum chamber, and after reaching a predetermined internal pressure, the heat-welded layer is heat-welded and sealed.
The core material is not limited to this, but fiber such as glass wool, glass fiber, alumina fiber, silica alumina fiber, silica fiber, rock wool, silicon carbide fiber, or powder such as silica, pearlite, or carbon black should be used. Can do.

  The present invention is further illustrated by the following examples, but the invention is not limited in any way by the following examples. The various measurement methods and evaluation methods of the examples and comparative examples are as follows. The composition of the undercoat layer and the barrier layer of each example is shown in Table 1, the layer structure of the exterior material is shown in Table 2, and thermal welding is performed. Table 3 shows the resin types used for the layers.

The contents of monovalent metal element, polyvalent metal element and nitrogen element in the gas barrier layer were measured using the following method.
(Content of monovalent metal element and polyvalent metal element)
A gas barrier material composed of a polycarboxylic acid-based polymer is immersed in an alkaline solution and dissolved, and then the solid obtained by evaporating to dryness is incinerated in an oven. The obtained ash was analyzed with an ICP emission spectroscopic analyzer (iCAP6000 manufactured by Thermo Fisher Scientific Co., Ltd.), thereby analyzing the weight ratio of the monovalent metal element and the polyvalent metal element.

(Content of nitrogen element)
A gas barrier material composed of a polycarboxylic acid-based polymer is immersed in an alkaline solution to be dissolved, and then the solid obtained by evaporation to dryness is obtained by a combustion method using an organic element analyzer (Thermoquest EA1110 manufactured by CE Instruments). The weight ratio of nitrogen to the total weight of nitrogen and oxygen was determined by analysis.

(Content of nitrogen element in the surface layer of the gas barrier layer)
The surface layer of each gas barrier layer described in the examples was subjected to surface analysis using XPS (Quantum-2000 manufactured by ULVAC-PHI), and the nitrogen content relative to the total amount of carbon, oxygen and nitrogen in the surface layer was measured.

(Nitrogen content of undercoat layer and region (x))
Using the following method, the nitrogen content relative to the total amount of carbon, oxygen, and nitrogen in each region was measured.
Region (x): Each gas barrier material described in the examples was immersed in an alkaline aqueous solution to dissolve the gas barrier layer, and then the exposed surface was subjected to composition analysis by XPS.
Undercoat layer: Each gas barrier material described in the examples is subjected to inclined cutting, and the corresponding region is subjected to composition analysis by XPS.

(Ion crosslinking rate)
The ionic crosslinking rate is calculated by measuring with a Fourier transform infrared spectrophotometer using each gas barrier layer described in Examples after the formation of ionic crosslinking. The formation of ionic bridges converts the carboxylic acid to the carboxylate. In general, the characteristic absorption band of the carboxylic acid, 920～970Cm around ^-1, 1700～1710Cm around ^-1, the wavelength around 2500～3200Cm ^-1, at a wavelength of around 1770～1800Cm ^-1 in yet anhydride. In addition, the characteristic absorption band of the carboxylate is at a wavelength near 1480 to 1630 cm ⁻¹ . For the calculation of the ionic crosslinking rate, the peak height having a peak in the wavelength region of carboxylic acid and acid anhydride of 1600 to 1800 cm ⁻¹ and the peak having a peak in the wavelength region of carboxylate of 1480 to 1630 cm ⁻¹ are calculated. Use height. More preferably, peak heights having apexes in the wavelength regions of 1695 to 1715 cm ⁻¹ (i) and 1540 to 1610 cm ⁻¹ (ii) are used. The infrared absorption spectrum of each sample is detected, and the absorbance at the wavelengths (i) and (ii) is measured to obtain the peak height.
Assuming that the absorbance coefficients of the carboxylic acid and the carboxylate are the same, the salt conversion rate of the carboxyl group (the ratio of conversion from the carboxylic acid to the carboxylate), that is, the ionic crosslinking rate X is calculated by the following formula (1). Moreover, the alkaline compound equivalent Y of the polyvalent metal used for the ion crosslinking is calculated by the following formula (2).
X = peak height of (ii) / [peak height of (i) + peak height of (ii)] (1)
Y = X / 100 (2)
The peak heights (i) and (ii) refer to the difference in absorbance between the point where the skirt portion of the peak overlaps the baseline and the peak apex.
(Measurement conditions of Fourier transform infrared spectrophotometer)
Equipment used: Digilab FTS7000series
Measurement method: single reflection method using germanium prism Measurement wavelength region: 4000 to 700 cm ⁻¹

(Thermogravimetric analysis)
After the gas barrier layer is formed, the gas barrier layer is peeled off from the plastic substrate or the undercoat layer and thermogravimetric analysis (TGA, manufactured by Hitachi High-Tech Science Co., Ltd., TG / DTA7220) is performed. Calculated.
Temperature increase rate: 10 ° C / min Measurement temperature: 20 ° C to 900 ° C
% Weight loss from 200 ° C. to 320 ° C. = (Sample weight at 200 ° C.−sample weight at 320 ° C.) / Sample weight at start × 100

(Dynamic viscoelasticity measurement)
Using an environmentally controlled nanoindenter (Tribo Scope from Hysitron, E-sweep type composite device from SII Nanotechnology), the dynamic viscoelasticity (DMS) measurement of the gas barrier layer is carried out. The difference when subtracting tan δ was calculated.
Working indenter: Spherical indenter Measurement atmosphere: Vacuum (10 ^-3 Pa or less)
Measurement temperature: 23-300 ° C
Measurement frequency: 20Hz

Various measurement methods and evaluation methods for exterior materials are described.
(Oxygen transmission rate)
Each exterior material described in the Examples was measured using an oxygen permeation measuring device (manufactured by Modern Control, OX-TRAN 2/20). However, the measurement conditions were a temperature of 80 ° C. and a relative humidity of 0%.

(Nitrogen permeation)
Each exterior material described in the examples was measured according to the gas permeation test method A (differential pressure method) of JIS K7126. However, the measurement conditions were a temperature of 80 ° C. and a relative humidity of 0%.

(Water vapor transmission rate)
Each laminate described in the examples was measured using a water vapor transmission rate measuring device (manufactured by Modern Control, PERMATRAN-W 3/30). The measurement conditions were a temperature of 40 ° C. and a relative humidity of 90%.

Various measurement methods and evaluation methods for vacuum insulation are described.
(Thermal conductivity)
The thermal conductivity was measured before and after each vacuum heat insulating material described in the Examples was stored in a thermostatic bath at a temperature of 80 ° C. for 100 days. The difference in thermal conductivity was the difference between the values before and after. A small value of the difference means that the degree of vacuum inside the vacuum heat insulating material is kept high, and indicates that the heat insulating effect is maintained over time.

Example 1
(Polyacrylic acid (manufactured by Toagosei Co., Ltd., AC-10LHP, Mw = 250,000) as a polycarboxylic acid polymer, methanol / 2-propanol / MEK / water mixed solvent (25/25/40/10 by weight)) After dissolving so that the solid content was 6% by weight, a 20% by weight sodium hydroxide aqueous solution was added so that the degree of neutralization was 2% with respect to polyacrylic acid to obtain a main solution. Linear aliphatic polyisocyanate (manufactured by Sumika Bayer Urethane, Sumidur N3300, isocyanurate type based on 1,6-hexamethylene diisocyanate, solid content 100% by weight, Tg = −60 ° C., Mn = 680) 0.4 parts by weight based on polyacrylic acid, alicyclic polyisocyanate (manufactured by Sumika Bayer Urethane, Desmodur Z4470, isophorone diisocyanate) Nate-based isocyanurate type, butyl acetate dissolved product, solid content 70% by weight, Tg = 70 ° C., Mn = 1200) was added so that the weight excluding the solvent was 0.4 parts by weight with respect to polyacrylic acid. The coating liquid for barrier material precursor was applied to the aluminum vapor deposition surface of a polyethylene terephthalate film (Oike Kogyo, Tetrait PC) on which an aluminum vapor deposition layer was formed with a bar coater, A film having a barrier material precursor was obtained by heat treatment in an oven under the conditions of a set temperature of 105 ° C. and a pass time of 40 seconds, and 360 mmol (40 g) of calcium chloride was added in terms of metal to 1 L of tap water, Then, after adjusting the pH to 12.0 (value at a water temperature of 24 ° C.) by adding 11 g of calcium hydroxide, 0 ℃ to warm for 3 seconds immersed films with the barrier material precursor with good stirring. Dried taken out from the hot water, to obtain a gas-barrier material having a gas barrier layer of the coated amount 1.5 g / m ² .

A method for manufacturing the exterior material will be described.
The gas barrier layer of the gas barrier material is subjected to corona treatment, and a reactive group-containing low-density polyethylene resin (hereinafter referred to as “reactive group-containing LDPE”) (made by Nippon Polyethylene, Novatec ^™ LD LC605Y, MFR 7.3 g / A gas barrier laminate was obtained by extrusion laminating 50 μm for 10 minutes at a density of 0.918 g / cm ³ ) at 260 ° C. and a line speed of 100 m / min. On the PET film of the gas barrier laminate, a urethane adhesive having a thickness of 2 μm and a biaxially stretched nylon film serving as an outermost layer having a thickness of 15 μm were sequentially dry-laminated to obtain an exterior material. Table 2 shows the layer structure of the exterior material.
Using this exterior material, a vacuum heat insulating material was obtained by the method for manufacturing a vacuum heat insulating material described above.

(Example 2)
A coating treatment solution was prepared by adding 720 mmol (80 g) of calcium chloride to 1 L of water / ethanol mixed solvent (weight ratio 30/70) and then adding 22 g of calcium hydroxide. In place of the immersion treatment of Example 1, the coating treatment liquid was applied on the barrier material precursor of Example 1 with a bar coater and then dried to obtain a gas barrier material having a gas barrier layer. The exterior material and the vacuum heat insulating material were obtained by the same method as 1.

(Example 3)
In Example 2, potassium hydroxide is added instead of sodium hydroxide as the main solution, and magnesium chloride and magnesium hydroxide are added instead of calcium chloride and calcium hydroxide as the coating treatment solution. In the same manner, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained.

Example 4
Two polyester polyols with a weight ratio of 50/50, Byron 200 (manufactured by Toyobo Co., Ltd., non-aqueous resin containing no metal element in the resin skeleton: confirmed by fluorescent X-ray) and Byron GK570 (manufactured by Toyobo Co., Ltd., resin) Calcium carbonate (CS3N, manufactured by Ube Materials Co., Ltd.) was dissolved in a solution obtained by dissolving a non-aqueous resin containing a metal element in the skeleton: confirmed by fluorescent X-rays with an ethyl acetate / MEK mixed solvent (65/35 by weight). -A, primary particle size: 0.3 μm) was blended so as to be 280 parts by weight with respect to the polyester polyol to make the total solid content 35% by weight, and then glass beads (manufactured by Toshin Riko, BZ-04) To obtain a paste. To this paste, 20 parts by weight of linear aliphatic polyisocyanate (Sumijur Bayer Urethane, Sumidur N3300) is added to the polyester polyol, and alicyclic polyisocyanate (Suidia Bayer Urethane, Desmodur Z4470) is added. The undercoat layer containing a polyvalent metal alkaline compound prepared by adding the mixed solvent so that the weight excluding the solvent is 20 parts by weight with respect to the polyester polyol, and the total solid content is 25% by weight. An undercoat coating liquid comprising the forming composition was obtained.
After applying the coating liquid for undercoat on the aluminum vapor deposition layer of a polyethylene terephthalate film (Oike Kogyo, Tetrait PC) on which a 12 μm thick aluminum vapor deposition layer was formed by a bar coater, using a box-type electric oven, A film having an undercoat layer with a coating amount of 1.4 g / m ² was heat-treated under the conditions of a set temperature of 70 ° C. and a treatment time of 2 minutes.

Polyacrylic acid (manufactured by Toagosei Co., Ltd., AC-10LP, Mw = 25,000) is used as the polycarboxylic acid polymer, and the solid content is 10% by weight in a water / acetone mixed solvent (80/20 by weight). Then, a 20 wt% aqueous sodium hydroxide solution was added to obtain a main solution so that the degree of neutralization was 2.5% with respect to polyacrylic acid.
The main solution was applied by a bar coater onto the undercoat layer of the film having an undercoat layer so that the coating amount was 1.5 g / m ² to obtain a gas barrier material precursor layer. Here, the coating amount of the gas barrier material precursor layer means that the main solution was directly applied to a polyethylene terephthalate film (Oike Kogyo, Tetrait PC) on which an aluminum vapor deposition layer having a thickness of 12 μm was formed. It is the coating amount obtained by drying only the polyacrylic acid in the main solution without forming the.
A gas barrier layer in which ion crosslinking is formed in the gas barrier material precursor layer by heat-treating the film after applying the main solution by a conveyor-type electric oven under conditions of a set temperature of 80 ° C. and a pass time of 5 seconds. A film having an undercoat layer, that is, a gas barrier material was obtained. A heat welding layer was formed on the gas barrier layer of the gas barrier material, an outermost layer was formed on the PET film of the gas barrier material, and an exterior material was formed in the same manner as in Example 1. Using this exterior material, a vacuum heat insulating material was obtained in the same manner as in Example 1.

(Example 5)
In Example 4, the reactive group-containing LDPE of the heat-welded layer is an ethylene-methacrylic acid copolymer resin (hereinafter referred to as “EMAA”) (Mitsui / DuPont Polychemical, Nucrel AN42012C, MFR 7.0 g / 10 min, density) A gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the amount was 0.940 g / cm ³ ).

(Example 6)
In Example 4, the reactive group-containing LDPE of the heat-welded layer was changed to an ionomer resin (manufactured by Mitsui DuPont Polychemicals, Himiran 1652, MFR 5.5 g / 10 min, density 0.950 g / cm ³ ). 4 were used to obtain a gas barrier material, an exterior material, and a vacuum heat insulating material.

(Example 7)
In Example 4, the reactive group-containing LDPE of the heat-welded layer is a metallocene-based linear low-density polyethylene resin (hereinafter referred to as “acid-free m-LLDPE”) with no antioxidant added (Tosoh Corporation, LumiTac 08L51A, A gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that MFR was 21 g / 10 minutes and the density was 0.898 g / cm ³ .

(Example 8)
In Example 4, the reactive group-containing LDPE of the heat-welded layer is a metallocene linear low-density polyethylene (hereinafter referred to as “m-LLDPE”) (manufactured by Nippon Polyethylene, Kernel KC577T, MFR 15 g / 10 min, density 0.910 g). Gas barrier material, exterior material, and vacuum heat insulating material were obtained in the same manner as in Example 4 except that / cm ³ ).

Example 9
In Example 4, the reactive group-containing LDPE of the heat-welded layer is a low-density polyethylene (hereinafter referred to as “acid-free LDPE”) with no antioxidant added (made by Nihon Unicar, NUC-8080, MFR 7.5 g / 10). The gas barrier material, the exterior material, and the vacuum heat insulating material were obtained in the same manner as in Example 4 except that the density was 0.918 g / cm ³ ).

(Example 10)
In Example 4, the reactive group-containing LDPE of the heat-welded layer was changed to non-acid-protective LDPE (Nippon Polyethylene, Novatec LC520, MFR 3.6 g / 10 min, density 0.923 g / cm ³ ). A gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as described above.

(Example 11)
In Example 4, except that the reactive group-containing LDPE of the heat-welded layer is a metallocene polypropylene (hereinafter m-PP) (manufactured by Nippon Polypro, Wintech WFX4TA, MFR 7.0 g / 10 min, density 0.9 g / cm ³ ). Obtained the gas barrier material, the exterior material, and the vacuum heat insulating material in the same manner as in Example 4.

(Example 12)
In Example 4, the reactive group-containing LDPE of the heat-welding layer was changed to adhesive polyolefin (manufactured by Mitsui Chemicals, ADMERQE840, MFR 9.2 g / 10 min, density 0.89 g / cm ³ ). A gas barrier material, an exterior material, and a vacuum heat insulating material were obtained by the method.

(Example 13)
In Example 4, polyethylene terephthalate (made by Oike Kogyo Co., Ltd., Tetrait PC) on which an aluminum vapor deposition layer was formed was used as biaxially stretched nylon (hereinafter referred to as “AL vapor deposition-ONY”) on which an aluminum vapor deposition layer was formed. An exterior material having AL deposition-ONY as the outermost layer of the exterior bag was obtained. Table 2 shows the layer structure of the exterior material. Using this exterior material, a vacuum heat insulating material was obtained by the above-described method for manufacturing a vacuum heat insulating material.

(Example 14)
In Example 4, the calcium carbonate content of the undercoat coating solution is 100 parts by weight with respect to the polyester polyol, the coating amount of the undercoat layer (A) is 1.0 g / m ² , and the solution (B ′) A gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the coating amount was 2.0 g / m ² .

(Example 15)
In Example 4, the gas barrier was prepared in the same manner as in Example 4 except that the water / acetone mixed solvent (80/20 by weight) in the main solution was changed to water / acetone mixed solvent (20/80 by weight). A material, an exterior material, and a vacuum heat insulating material were obtained.

(Example 16)
In Example 4, a gas barrier material, an exterior material, and a vacuum heat insulating material are obtained in the same manner as in Example 4 except that the calcium carbonate in the undercoat coating solution is blended to 530 parts by weight with respect to the polyester polyol. It was.

(Example 17)
In Example 4, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that sodium hydroxide was not added to the main solution.

(Example 18)
In Example 4, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the degree of neutralization with respect to polyacrylic acid in the main solution was 4.5%.

(Example 19)
In Example 4, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the weight ratio of the water / acetone mixed solvent in the main solution was 90/10.

(Example 20)
In Example 4, 30 parts by weight of a linear aliphatic polyisocyanate (Sumitor N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) is added to the polyester polyol, and the weight of the alicyclic polyisocyanate excluding the solvent is added to the polyester polyol. In addition, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the weight ratio of the water / acetone mixed solvent in the main solution was 30/70, with the addition of 30 parts by weight. It was.

(Example 21)
In Example 4, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the sodium hydroxide aqueous solution in the main solution was changed to a potassium hydroxide aqueous solution.

(Example 22)
In Example 4, calcium carbonate in the undercoat coating solution is magnesium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), and the coating amount of the undercoat layer is 1.2 g / m ² . A gas barrier material, an exterior material, and a vacuum heat insulating material were obtained by the method.

(Example 23)
In Example 4, calcium carbonate in the undercoat coating solution is calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), and the coating amount of the undercoat layer is 1.1 g / m ^2. Thus, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained.

(Example 24)
In Example 4, the death module Z4470 was Takenate D110N (manufactured by Mitsui Chemicals, xylylene diisocyanate-based adduct type, solid content 75%), and the weight excluding the solvent was 20 parts by weight with respect to the polyester polyol. A gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4.

(Example 25)
In Example 4, Sumidur N3300 was Sumidur HT (manufactured by Sumika Bayer Urethane, 1,6-hexamethylene diisocyanate-based adduct type, solid content 75%), and the weight excluding the solvent was 20 with respect to the polyester polyol. A gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the weight percent was used.

(Example 26)
In Example 4, except that Byron GK570 in the coating liquid for undercoat is Byron 550 (manufactured by Toyobo Co., Ltd., non-aqueous resin not containing metal element in resin skeleton: confirmed by fluorescent X-ray), In the same manner as in Example 4, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained.

(Example 27)
In Example 4, the heat-welded layer was made of adhesive polyolefin (manufactured by Mitsui Chemicals, ADMER NE827, MFR 5.6 g / 10 min, density 0.909 g / cm ³ ) and low-density polyethylene (hereinafter referred to as LDPE) (Nippon Polyethylene). NOVATEC ^™ LD LC600A, MFR 7.0 g / 10 min, density 0.918 g / cm ³ ), 50 μm (adhesive polyolefin 5 μm, low density polyethylene 45 μm), 260 ° C., except for coextrusion lamination at a line speed of 100 m / min Obtained the gas barrier material, the exterior material, and the vacuum heat insulating material in the same manner as in Example 4.

(Example 28)
Example 4 is the same as Example 4 except that the coating liquid for undercoat is applied onto the polyethylene terephthalate of a polyethylene terephthalate film (manufactured by Oike Kogyo Co., Ltd., Tetraite PC) on which a 12 μm thick aluminum vapor deposition is formed by a bar coater. In the same manner, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained.

(Example 29)
In Example 4, the gas barrier material and the exterior were coated in the same manner as in Example 4 except that the coating liquid for undercoat was applied onto a PET film having a thickness of 12 μm by a bar coater and aluminum was deposited on the gas barrier layer (B). Materials and vacuum insulation were obtained.

(Example 30)
In Example 4, a 2 μm-thick urethane adhesive on a PET film as a gas barrier material, a PET film having a 12 μm-thick aluminum vapor deposition layer (Oike Kogyo, Tetrait PC), a 2 μm-thick urethane adhesive, A gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that dry lamination of 15 μm thick biaxially stretched nylon fill was sequentially performed.

(Example 31)
In Example 4, an exterior material and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that an aluminum vapor deposition layer was formed on the gas barrier layer of the gas barrier material to obtain a gas barrier material having two aluminum vapor deposition layers.

(Example 32)
In Example 28, an exterior material and a vacuum heat insulating material were obtained in the same manner as in Example 27 except that an aluminum vapor deposition layer was formed on the gas barrier layer of the gas barrier material to obtain a gas barrier material having two aluminum vapor deposition layers.

(Example 33)
A gas barrier material was prepared in the same manner as in Example 30, except that the coating liquid for undercoat in Example 30 was applied onto a 12 μm thick Tech Barrier TX (made by Mitsubishi Plastics, silica-deposited barrier film) using a bar coater. The exterior material and the vacuum heat insulating material were obtained.

(Comparative Example 1)
In Example 1, 20 parts by weight of a linear aliphatic polyisocyanate (Sumika Bayer Urethane, Sumidur N3300) was added to the polyester polyol, and an alicyclic polyisocyanate (Sumika Bayer Urethane, Desmodur Z4470). A gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 1 except that was not added.

(Comparative Example 2)
In Example 4, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the weight ratio of the water / acetone mixed solvent in the main solution was 15/85.

(Comparative Example 3)
In Example 4, instead of polyacrylic acid AC-10LP in the main solution, AC-10LHP was used, and 20% by weight sodium hydroxide aqueous solution was added so that the degree of neutralization was 2% with respect to polyacrylic acid. A gas barrier material was obtained in the same manner as in Example 4. Further, this gas barrier material was subjected to an immersion treatment for 3 seconds with good stirring in an immersion treatment solution which was heated to 40 ° C. by adding 40 g of calcium chloride and 11 g of calcium hydroxide to 1 L of tap water. 4 and the exterior material and the vacuum heat insulating material were obtained by the same method.

(Comparative Example 4)
In Example 4, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the weight ratio of the water / acetone mixed solvent in the main solution was set to 100/0.

(Comparative Example 5)
In Example 4, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the degree of neutralization with respect to polyacrylic acid in the main solution was 5.0%.

(Comparative Example 6)
In Example 4, 35% by weight of linear aliphatic polyisocyanate was added to the polyester polyol, and alicyclic polyisocyanate was added so that the weight excluding the solvent was 35% by weight with respect to the polyester polyol. A gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the weight ratio of the water / acetone mixed solvent in the solution was 30/70.

(Comparative Example 7)
Polyacrylic acid (manufactured by Toagosei Co., Ltd., AC-10LHP, Mw = 250,000) is dissolved in water to make an aqueous solution having a solid content of 15%, and then 20 wt. % Aqueous sodium hydroxide was added. To this partially neutralized polyacrylic acid aqueous solution, a soluble starch (made by Wako Pure Chemical Industries) aqueous solution having a solid content of 15% by weight was mixed at a weight ratio of 70:30 to obtain a mixed solution. This aqueous solution was applied to a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm using a bar coater, and heat-treated with a box-type electric oven at a set temperature of 200 ° C. for a treatment time of 10 minutes. An m ² gas barrier material was obtained, and an exterior material and a vacuum heat insulating material were obtained in the same manner as in Example 1.

(Comparative Example 8)
In Comparative Example 7, after heat treatment, the gas barrier material was immersed for 3 seconds in the immersion treatment liquid that was heated to 40 ° C. by adding 40 g of calcium chloride and 11 g of calcium hydroxide to 1 L of tap water. The exterior material and the vacuum heat insulating material were obtained in the same manner as in Example 1.

(Comparative Example 9)
In Example 1, a polyethylene terephthalate film in which an aluminum vapor deposition was formed without applying a coating solution for a barrier material precursor onto a polyethylene terephthalate film (Oike Kogyo, Tetrait PC) on which an aluminum vapor deposition layer having a thickness of 12 μm was formed. A vacuum heat insulating material was obtained in the same manner as in Example 1 except that reactive group-containing LDPE was extruded and laminated on aluminum vapor deposition (Teito PC, manufactured by Oike Kogyo Co., Ltd.).

(Comparative Example 10)
In Example 4, a gas barrier material, an exterior material, and a vacuum heat insulating material were obtained in the same manner as in Example 4 except that the coating liquid for undercoat was applied to a polyethylene terephthalate film having a thickness of 12 μm by a bar coater.

  The ionic crosslinking rate of the gas barrier layer obtained in the above examples and comparative examples, the content of monovalent metal elements and polyvalent metal elements determined from an ICP emission spectroscopic analyzer, and the nitrogen determined from an organic element analyzer, The nitrogen content with respect to the total amount of carbon, the nitrogen content with respect to the total amount of carbon, oxygen and nitrogen obtained from the composition analysis by XPS in the gas barrier layer surface, the undercoat layer, and the region (x), and the thermogravimetric analysis result of 200 Table shows the weight loss from ℃ to 320 ℃, the difference when subtracting tan δ from 50 ℃ from tan δ at 200 ℃ in dynamic viscoelasticity measurement, oxygen, nitrogen, water vapor transmission rate, and thermal conductivity measurement results 4 shows.

  In the examples, all the evaluations showed good results. However, Comparative Example 2 in which the amount of polyvalent metal elements was small. Comparative Example 5 in which the amount of oxygen and nitrogen permeation was large and the amount of monovalent metal elements was excessive was oxygen and nitrogen. Comparative Example 4 having a slightly higher permeation amount and a low nitrogen content relative to the total amount of nitrogen and carbon determined by the organic element analyzer has a slightly higher oxygen / nitrogen permeation amount, and nitrogen and carbon determined by the organic element analyzer Comparative Examples 1 and 6 in which the nitrogen content is excessive with respect to the total amount of oxygen have a large amount of oxygen and nitrogen permeation, and Comparative Example 9 in which no gas barrier material is used has a large amount of oxygen / nitrogen permeation and does not have an aluminum vapor deposition layer. Comparative Example 10 had a large amount of water vapor permeation, and all Comparative Examples showed high values in the difference in thermal conductivity between the initial stage and 100 days later.

  Since the vacuum heat insulating material of the present invention uses an exterior material having excellent gas barrier properties and water resistance, it can maintain an internal reduced pressure state over a long period of time, and can maintain excellent heat insulating performance. In addition to heat and cold insulation applications such as refrigerators and cooler boxes, it can also be suitably used for residential building materials. Moreover, since the exterior material used for the vacuum heat insulating material of this invention is excellent in productivity and economical efficiency, it can be used also for the use to a general purpose product.

1 vacuum heat insulating material, 2 core material, 3 exterior material, 4 heat welding layer,
5 Gas barrier material,
5a polyethylene terephthalate,
5b _i , 5b _ii aluminum vapor deposition layer 5c undercoat layer, 5d gas barrier layer 6 adhesive layer,
7 Deposition film,
7a base resin, 7a _i polyethylene terephthalate,
7b vapor deposition layer, 7b _i aluminum vapor deposition layer,
8 protective layer, 11 gas barrier layer, 12 undercoat layer.

Claims (21)

In a vacuum heat insulating material consisting of a core material and an exterior material covering the core material, the inside of which is sealed under reduced pressure,
The exterior material is composed of a gas barrier laminate comprising at least a heat welding layer and a gas barrier material,
The gas barrier material is composed of a polycarboxylic acid polymer, and the total weight of nitrogen and carbon is 1.4% by weight or less of a monovalent metal element, 5.0 to 18.0% by weight of a polyvalent metal element. It comprises at least a gas barrier layer containing 0.01 to 3.0% by weight of nitrogen element, a vapor deposition layer, and a plastic substrate,
The vacuum heat insulating material, wherein the heat welding layer is formed by extrusion coating a thermoplastic resin on the gas barrier material.   The vacuum heat insulating material according to claim 1, wherein the gas barrier layer is formed on a plastic substrate on which a vapor deposition layer is formed.   The vacuum heat insulating material according to claim 1 or 2, wherein the polycarboxylic acid-based polymer is poly (meth) acrylic acid.   The vacuum heat insulating material according to any one of claims 1 to 3, wherein the polycarboxylic acid-based polymer is partially neutralized in a molar ratio to a carboxyl group of at most 4.5%.   The vacuum heat insulating material according to any one of claims 1 to 4, wherein the thermoplastic resin is a polyolefin resin, an ethylene- (meth) acrylic acid copolymer, or an ionomer resin.   The thermoplastic resin is any one of a polyolefin resin polymerized using a single-site catalyst, a polyolefin resin without addition of an antioxidant, and a polyolefin resin containing a carboxyl group or a reactive group capable of forming a chemical bond with a hydroxyl group. The vacuum heat insulating material in any one of Claims 1-5. The vacuum heat insulating material according to claim 5 or 6, wherein the polyolefin resin has a density of 0.950 g / cm ³ or less.   The vacuum heat insulating material according to any one of claims 5 to 7, wherein the polyolefin resin is MFR 7.0 g / 10 min or more.   The gas barrier layer has a weight loss from 200 ° C. to 320 ° C. of 10% or less in thermogravimetric analysis (TGA) measurement at a heating rate of 10 ° C./min, and dynamic viscoelasticity (DMS) measurement at 20 Hz. The vacuum heat insulating material according to claim 1, wherein a difference when subtracting tan δ at 50 ° C. from tan δ at 200 ° C. is 0.010 or more.   The vacuum heat insulating material according to any one of claims 1 to 9, wherein the monovalent metal element is sodium or potassium.   The vacuum heat insulating material according to any one of claims 1 to 10, wherein the polyvalent metal element is at least one of calcium, magnesium, zinc, and iron.   The vacuum heat insulating material according to any one of claims 1 to 11, wherein a content of nitrogen with respect to a total amount of carbon, oxygen, and nitrogen in a surface layer of the gas barrier layer is 1 atm% or more.   The gas barrier material forms an undercoat layer containing an isocyanate compound having at least two isocyanate groups in one molecule on one surface of the vapor-deposited layer or the plastic substrate of the plastic substrate on which the vapor-deposited layer is formed. The vacuum heat insulating material according to claim 1, wherein a gas barrier layer is formed on the undercoat layer.   The vacuum heat insulating material according to claim 13, wherein at least one of the gas barrier layer and the undercoat layer is adjacent to the vapor deposition layer.   The vacuum heat insulating material according to claim 13 or 14, wherein the gas barrier material has two vapor deposition layers, and a gas barrier layer and an undercoat layer are formed between the two vapor deposition layers.   The vacuum heat insulating material according to claim 15, wherein both the gas barrier layer and the undercoat layer are adjacent to the vapor deposition layer.   The vacuum heat insulating material according to any one of claims 13 to 16, wherein the undercoat layer contains an alkaline compound of a polyvalent metal.   The vacuum heat insulating material according to claim 17, wherein the alkaline compound of the polyvalent metal comprises at least one of calcium, magnesium, zinc carbonate and hydroxide.   The vacuum heat insulating material according to any one of claims 13 to 18, wherein the isocyanate compound is a combination of a linear aliphatic isocyanate compound and an alicyclic isocyanate compound having an alicyclic ring structure in the skeleton.   The vacuum heat insulating material according to claim 19, wherein the aliphatic isocyanate compound has an isocyanurate structure.   A region (x) not containing an alkali compound of a polyvalent metal is formed on the gas barrier material side of the undercoat layer, and the content of nitrogen in the region (x) of the undercoat layer other than the region (x) The vacuum heat insulating material according to any one of claims 13 to 22, wherein the content of the vacuum heat insulating material is greater than the content of nitrogen.