Thermal insulation materials and thermal insulation structures

Abstract

The present invention provides an insulating material comprising a foam layer and a gas barrier layer, wherein the gas barrier layer is less likely to peel off even when in contact with water or exposed to a high-temperature, high-humidity environment. [Solution] One embodiment of the present invention is a thermal insulation material comprising a foam layer containing a hydrocarbon gas and a composite layer laminated on at least one surface of the foam layer. The composite layer has a polyolefin layer in contact with the foam layer and a PET layer laminated on the polyolefin layer.

Description

[Technical Field]

[0001] This invention relates to thermal insulation materials and thermal insulation structures. [Background technology]

[0002] Insulation materials incorporating foam are becoming widespread. When foam is used as insulation, the gas sealed within the foam cells can contribute to a decrease in thermal conductivity, while this foaming gas can be replaced by air over time. Therefore, attempts are being made to prevent the replacement of the foaming gas with air by providing a gas barrier layer on the surface of the foam, thereby maintaining insulation performance for a long period of time.

[0003] For example, Patent Document 1 discloses a surface material for foamed insulation boards fixed to concrete, comprising a mixed paper and a gas barrier layer, without a metal layer. Patent Document 1 also discloses a gas barrier layer composed of an inorganic compound film and a resin substrate. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-14617 [Overview of the project] [Problems that the invention aims to solve]

[0005] Insulation materials may be exposed to high-temperature and high-humidity environments. When insulation materials are installed during building construction, they may get wet due to rain, etc. If insulation materials having a gas barrier layer and foam are exposed to high-temperature and high-humidity environments or come into contact with water, the adhesion of the gas barrier layer to the foam deteriorates significantly, making the gas barrier layer more prone to peeling, and making it difficult to maintain the insulation performance of the insulation material over a long period of time.

[0006] Therefore, the present invention aims to provide a thermal insulation material comprising a foam layer and a gas barrier layer, wherein the gas barrier layer is less likely to peel off even when in contact with water or exposed to a high-temperature, high-humidity environment. [Means for solving the problem]

[0007] One embodiment of the present invention is a thermal insulation material comprising a foam layer containing a hydrocarbon gas and a composite layer laminated on at least one surface of the foam layer. The composite layer has a polyolefin layer in contact with the foam layer and a PET layer laminated on the polyolefin layer.

[0008] It is preferable that the composite layer be provided on both sides of the foam layer. It is preferable that an outer layer is laminated onto the aforementioned composite layer. The foam layer is preferably a urethane-based foam layer. The aforementioned insulation material is preferably installed on the roof.

[0009] Another embodiment of the present invention is an insulating structure comprising a roof and the insulating material installed on the roof. [Effects of the Invention]

[0010] According to the present invention, a thermal insulation material comprising a foam layer and a gas barrier layer is provided, wherein the gas barrier layer is less likely to peel off even when in contact with water or exposed to a high-temperature, high-humidity environment. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1(a) is a conceptual side view of an example of an insulating material, and Figure 1(b) is a conceptual side view of another example of an insulating material. [Figure 2] Figure 2 is a conceptual side view of the composite layer. [Figure 3] Figure 3 is a conceptual side view of the outer layer. [Figure 4] Figure 4 is a conceptual side view showing an example of an insulating structure.

Best Mode for Carrying Out the Invention

[0012] In this specification, when an upper limit value and a lower limit value are separately described, a numerical range obtained by combining any upper limit value and any lower limit value shall be regarded as being substantially disclosed.

[0013] In this specification, unless otherwise specified, various measurements are carried out with the environmental temperature being room temperature (25°C).

[0014] Hereinafter, the structure, manufacturing method, uses, etc. of the heat insulating material according to the present disclosure will be described, but the present invention is not limited thereto.

[0015] <<<Structure of the Heat Insulating Material>>> FIG. 1(a) shows a conceptual side view of an example of a heat insulating material 10 according to the present disclosure. As shown in FIG. 1(a), the heat insulating material 10 according to the present disclosure includes a foam layer 100 and a composite layer 200 laminated on at least one surface of the foam layer 100. Further, as shown in FIG. 1(a), it is preferable that an outer layer 300 is laminated on the composite layer 200.

[0016] FIG. 2 shows a conceptual side view of an example of the composite layer 200. As shown in FIG. 2, the composite layer 200 has a polyolefin layer 201 and a PET layer 202 laminated on the polyolefin layer 201. Further, the polyolefin layer 201 abuts on the foam layer 100.

[0017] As described above, the thermal insulation material 10 according to this disclosure has a foam layer 100 and a PET layer 202 laminated together via a polyolefin layer 201. The PET layer 202 functions as a barrier layer to prevent gas leakage from the cells of the foam layer 100, thereby enhancing thermal insulation performance. Furthermore, the polyolefin layer 201 functions as an adhesive layer between the foam layer 100 and the PET layer 202, and even if the thermal insulation material 10 is exposed to an environment with water or a high-temperature, high-humidity environment, peeling of the PET layer 202 can be prevented, thus maintaining high thermal insulation performance. In addition, by laminating a composite layer 200 and an outer layer 300 onto the foam layer 100, when some pressure is applied to the thermal insulation material 10, the pressure is distributed in the planar direction through each layer, making it less likely for the foam layer 100 to break (destruction of cells), and thus making it easier to maintain the thermal insulation performance of the thermal insulation material 10.

[0018] Figure 1(b) shows a conceptual side view of another example of the thermal insulation material 10 according to this disclosure. While Figure 1(a) shows a thermal insulation material 10 in which a composite layer 200 is provided on only one side of the foam layer 100, Figure 1(b) shows a thermal insulation material 10 in which composite layers (first composite layer 210, second composite layer 220) are provided on both sides of the foam layer 100. More specifically, in the foam layer 100 shown in Figure 1(b), the first composite layer 210 is laminated on one side of the foam layer 100, and the second composite layer 220 is laminated on the other side of the foam layer 100. By providing composite layers on both sides of the foam layer 100 in this way, the effects described above can be further enhanced.

[0019] Furthermore, when composite layers are provided on both sides of the foam layer 100 in this manner, it is preferable that a first outer layer 310 is further laminated onto the first composite layer 210. It is also preferable that a second outer layer 320 is further laminated onto the second composite layer 220. In this case, the first composite layer 210 and the second composite layer 220 may be the same or different in terms of thickness, material, physical properties, layer structure, etc. Similarly, the first outer layer 310 and the second outer layer 320 may be the same or different in terms of thickness, material, physical properties, layer structure, etc. In the following, the first composite layer 210 and the second composite layer 220 will be described without distinction from the composite layer 200, and the first outer layer 310 and the first outer layer 310 will be described without distinction from the outer layer 300.

[0020] The following describes the specific materials and other characteristics of each layer. Note that each layer described below may undergo surface treatment (such as corona discharge treatment) to improve adhesion between layers. Furthermore, each layer may contain known additives, etc., to the extent that they do not impair the effects described herein.

[0021] <<Foam layer 100>> The foam layer 100 can be made from conventionally known foams used for thermal insulation applications. Examples of foam layers include polyurethane foams, phenolic foams, styrene foams, and polycarbonate foams.

[0022] The foam layer 100 contains a hydrocarbon gas. In other words, the cells constituting the foam layer 100 are filled with a hydrocarbon gas.

[0023] The hydrocarbon gas is not particularly limited, but C4-C6 hydrocarbons are examples. Specifically, the hydrocarbon gas is one or more selected from the group consisting of cyclopentane, n-pentane, isopentane, n-butane, isobutane, n-hexane, isohexane, and cyclohexane. Preferably, the hydrocarbon gas is one or more selected from the group consisting of cyclopentane, n-pentane, and isopentane.

[0024] In the thermal insulation material 10 according to this disclosure, a composite layer 200 containing a PET layer is laminated to a foam layer 100 containing a hydrocarbon gas. This prevents the release of hydrocarbon gas from the foam layer 100, and the excellent thermal insulation performance derived from the hydrocarbon gas, which has low thermal conductivity, can be maintained for a long time. Furthermore, since hydrocarbon gas has high compatibility with the polyolefin layer, it is less likely to impede the adhesion between the polyolefin layer and the foam layer 100 when laminating the polyolefin layer and the foam layer 100 (or when heat is applied to the thermal insulation material 10), etc. (or the adhesion can be enhanced).

[0025] The foam layer 100 is preferably a polyurethane foam. The following describes in detail the case where the foam layer is a polyurethane foam layer.

[0026] The polyurethane foam is, for example, a polyurethane foam or a polyisocyanurate foam, and is preferably a polyisocyanurate foam. By using such a foam layer, a good balance of adhesion to the polyolefin layer, heat insulation, heat resistance, etc., is achieved.

[0027] Polyisocyanurate foam contains isocyanurate rings in its molecular structure. Polyisocyanurate foam containing isocyanurate rings exhibits excellent flame retardancy and is less prone to thermal shrinkage, making it easier to maintain long-term thermal insulation. The isocyanurate ring content (nuration rate) in polyisocyanurate resin foam is not particularly limited and can be changed according to the application. The nuration rate can be adjusted by changing the ratio of polyol compounds and polyisocyanate compounds used as raw materials, the amount of trimerizing catalyst, etc.

[0028] The raw materials and other components that make up the polyurethane foam layer will be described later.

[0029] The density (apparent density) of the polyurethane foam layer is 25-70 kg / m³. 3It is preferable that it is. By setting the density of the polyurethane foam layer within such a range, adhesiveness, heat insulation properties, strength, etc. can be improved in a well-balanced manner.

[0030] <<Composite layer 200>> <Polyolefin layer 201> The polyolefin layer 201 is a layer composed of polyolefin.

[0031] The polyolefin that constitutes the polyolefin layer 201 is a homopolymer or copolymer mainly composed of olefins, and examples thereof include polyethylene, polypropylene, poly-α-olefin, ethylene vinyl acetate copolymer, etc.

[0032] The polyolefin is preferably polyethylene, more preferably medium-density polyethylene (MDPE) or low-density polyethylene (LDPE), still more preferably low-density polyethylene (LDPE), and particularly preferably linear low-density polyethylene (LLDPE). In addition, the classification of these polyethylenes is applied according to the classification method in JIS K 6922-1. For example, in the present disclosure, low-density polyethylene refers to polyethylene with a density of 910 kg / m 3 or more and 925 kg / m 3 less than, and medium-density polyethylene refers to polyethylene with a density of 925 kg / m 3 or more and 940 kg / m 3 less than. By using such a material for the polyolefin layer 201, the adhesiveness between the PET layer 202 and the foam layer 100 is improved, and the heat insulation property of the heat insulating material 10 is likely to be maintained for a long time. <0​​​​​​​​

[0035] The thickness of the PET layer 202 is not particularly limited as long as it has sufficient gas barrier properties. The thickness of the PET layer 202 is preferably, for example, 2 μm or more, 5 μm or more, or 10 μm or more, and also preferably 50 μm or less, 40 μm or less, 30 μm or less, or 20 μm or less.

[0036] From the viewpoint of achieving a good balance of adhesion and gas barrier properties, the thickness of the polyolefin layer 201 relative to the thickness of the PET layer 202 (polyolefin layer 201 / PET layer 202) is preferably 0.2 or more, 0.4 or more, or 0.5 or more, and preferably 2.0 or less, 1.0 or less, or 0.8 or less.

[0037] Here, the PET layer may have a vapor-deposited layer on the side to which the polyolefin layer is laminated. Examples of vapor-deposited layers include a metal vapor-deposited layer and an inorganic compound vapor-deposited layer. Examples of metals constituting the metal vapor-deposited layer include aluminum. Examples of inorganic compounds constituting the inorganic compound vapor-deposited layer include silicon oxides such as silica, aluminum oxides such as alumina, magnesium oxide, titanium oxide, tin oxide, silicon zinc alloy oxide, indium alloy oxide, silicon nitride, aluminum nitride, titanium nitride, silicon oxide nitride, zinc silicon oxide, etc. The inorganic compound may be a mixture of these.

[0038] <<Outer layer 300>> The outer layer 300 is not particularly limited, and its material, thickness, etc., should be determined considering the intended use of the insulation material 10.

[0039] The outer layer 300 may include functional layers having various functions. Examples of functional layers include metal layers, inorganic compound layers, paper layers, woven fabric layers, nonwoven fabric layers, printed layers, and water-repellent coating layers. The outer layer 300 preferably includes one or more layers selected from metal layers, paper layers, inorganic compound layers, woven fabric layers, and nonwoven fabric layers, more preferably includes one or more layers selected from metal layers, paper layers, and inorganic compound layers, and even more preferably includes one or more layers selected from metal layers and paper layers.

[0040] Examples of metals that make up the metal layer include aluminum. The metal layer may be a layer formed from metal foil or a layer formed by metal deposition. If the metal layer is a layer formed from metal foil, the thickness of the metal layer is, for example, 5 μm or more, and also 100 μm or less, 80 μm or less, or 50 μm or less, 22 μm or less, or 12 μm or less. If the metal layer is a layer formed by metal deposition, the thickness of the metal layer is, for example, 20 nm or more, 25 nm or more, or 30 nm or more, and also 1 μm or less, 200 nm or less, or 60 nm or less.

[0041] Examples of inorganic compounds constituting the inorganic compound layer include silicon oxides such as silica, aluminum oxides such as alumina, magnesium oxide, titanium oxide, tin oxide, silicon-zinc alloy oxide, indium alloy oxide, silicon nitride, aluminum nitride, titanium nitride, silicon oxide nitride, and zinc silicon oxide. The inorganic compound may also be a mixture of these. The inorganic compound layer may be a layer formed by vapor deposition of the inorganic compound.

[0042] Examples of fibers constituting the woven and nonwoven layers include resin fibers, glass fibers, carbon fibers, metal fibers, metal oxide fibers, and mineral fibers.

[0043] The paper layer may contain fillers and pigments (such as calcium carbonate). The paper used to constitute the paper layer is not particularly limited, and conventionally known papers such as kraft paper, fine paper, and medium-grade paper may be used. The basis weight of the paper layer is, for example, 50 g / m².2 70 g / m² or more 2 or 90 g / m² or more 2 and 180 g / m² or less 2 150 g / m² or less 2 or 120 g / m² or less 2 is what is described above.

[0044] When the outer layer 300 includes a plurality of layers, the stacking order of each layer is not particularly limited.

[0045] In the outer layer 300, a polyolefin layer may be provided as a layer that abuts on the composite layer 200 or as a layer that constitutes the interface between the functional layers that constitute the outer layer 300. By interposing a polyolefin layer between the layer that abuts on the composite layer 200 and the functional layers, the adhesion between the layers can be improved and the peeling between the layers can be prevented. For example, a laminate having excellent performance such as more effectively preventing the peeling of the PET layer can be easily formed by having a structure laminated in the order of the foam layer 100 / polyolefin layer (polyolefin layer 201) / PET layer 202 / polyolefin layer. Also, a polyolefin layer may be provided as the outermost surface layer of the outer layer 300. Regarding the polyolefin layer that constitutes the outer layer 300, since the matters described for the polyolefin layer 201 that constitutes the composite layer 200 are referred to and incorporated, the description is omitted.

[0046] By providing the outer layer 300, the strength (dimensional stability, dent resistance), heat shielding property, fire resistance, etc. of the heat insulating material 10 can be improved.

[0047] Hereinafter, based on FIG. 3, specific configuration examples of the outer layer 300 will be shown.

[0048] Figure 3 shows a conceptual side view of an example of the outer layer 300. The outer layer 300 shown in Figure 3 includes a paper layer 302 and a metal layer 303. The outer layer 300 shown in Figure 3 also has a polyolefin layer 301a as a layer that abuts the composite layer 200 (a layer that forms the interlayer between the composite layer 200 and the paper layer 302) (the composite layer 200 and the paper layer 302 are joined via the polyolefin layer 301a). Furthermore, it has a polyolefin layer 301b as a layer that forms the interlayer between the paper layer 302 and the metal layer 303 (the paper layer 302 and the metal layer 303 are joined via the polyolefin layer 301b).

[0049] If the outer layer 300 has multiple polyolefin layers (for example, polyolefin layer 301a and polyolefin layer 301b), the composition (thickness, material, physical properties, etc.) of each polyolefin layer may be the same or different. Also, if the outer layer 300 includes a polyolefin layer, the composition of the polyolefin layer included in the outer layer 300 and the composition of the polyolefin layer 201 included in the composite layer 200 may be the same or different.

[0050] <<<Manufacturing Method for Insulation Materials>>> Next, a specific method for manufacturing the thermal insulation material 10 will be described. Here, an example of a manufacturing method for the thermal insulation material 10 having a structure in which composite layers (first composite layer 210, second composite layer 220) and outer layers (first outer layer 310, second outer layer 320) are provided on both sides of the foam layer, as shown in Figure 1(b), will be described.

[0051] A foaming composition, which is the raw material for the foam layer 100, is prepared. The foaming composition comprises at least a foaming raw material composition that constitutes the framework of the foam layer and a physical blowing agent. The physical blowing agent causes the foaming raw material composition to foam, and at least a portion of it is sealed within the foam layer as a hydrocarbon gas. A first substrate is prepared, in which a first outer layer 310 is laminated on the PET layer 202 side of the first composite layer 210, and a second substrate is prepared, in which a second outer layer 320 is laminated on the PET layer 202 side of the second composite layer 220. The first substrate and the second substrate are placed in the upper and lower molds of a mold (mold frame) of predetermined dimensions, with the polyolefin layer 201 side of each composite layer facing inward (so that the foaming composition can come into contact with the polyolefin layer 201). Next, the foaming composition is injected into a mold (mold frame) containing the first and second substrates and allowed to foam and harden to form a foam layer 100. In this process, by using a hydrocarbon gas with high compatibility with polyolefin as a physical foaming agent, the hardening of the foaming composition proceeds while partially melting the polyolefin layer, which is thought to increase the adhesive strength between the polyolefin layer and the foam layer, and to facilitate the formation of an appropriate cell structure in the foam layer at the interface with the polyolefin layer. During foam curing, heating of the foaming composition and mold may be carried out as needed. Furthermore, drying may be carried out as needed after the formation of the foam layer 100. For continuous molding, a high-pressure injection machine can be used to form a flat plate by foam curing in a double conveyor at room temperature and atmospheric pressure. The basic manufacturing method for the laminate can be applied to conventionally known methods, such as those described in Japanese Patent Publication No. 2007-176990 and Japanese Patent Publication No. 2006-168360.

[0052] As described above, the thermal insulation material 10 is manufactured as a laminate in which the first outer layer 310, the first composite layer 210, the foam layer 100, the second composite layer 220, and the second outer layer 320 are stacked in this order.

[0053] Furthermore, in the method described above, by laminating a release film instead of the second substrate, and then peeling off the release film after foaming and curing the foaming composition, it is possible to manufacture a thermal insulation material 10 having a composite layer 200 and an outer layer 300 on only one side, as shown in Figure 1(a).

[0054] Furthermore, by using a substrate that does not have an outer layer 300 (composed only of a composite layer 200), it is possible to manufacture an insulating material 10 without an outer layer 300. Alternatively, after manufacturing a laminate having a foam layer 100 and a composite layer 200 without an outer layer 300, a process may be carried out to sequentially laminate each layer of the outer layer 300 onto the composite layer 200 to manufacture an insulating material 10 having a foam layer 100, a composite layer 200, and an outer layer 300.

[0055] The following details the case where the foam layer is a urethane-based foam layer.

[0056] When the foam layer is a urethane-based foam layer, the foaming raw material composition consists of a polyol-side foaming raw material liquid containing a polyol and a polyisocyanate-side foaming raw material liquid containing a polyisocyanate. The foaming raw material composition may also contain other components (optional components such as catalysts, foam stabilizers, foaming aids, and flame retardants). The other components are preferably contained in the polyol-side foaming raw material liquid, but may also be contained in the polyisocyanate-side foaming raw material liquid. The foaming composition can be produced by mixing the polyol-side foaming raw material liquid and the polyisocyanate component, then further mixing in a physical foaming agent, and, if necessary, by collision mixing using a general-purpose high-pressure foaming machine or the like.

[0057] The following describes the physical blowing agent, polyisocyanate, polyol, and other components that make up the foaming composition.

[0058] <<Physical foaming agent>> Examples of physical blowing agents include the hydrocarbon-based compounds mentioned above. Specifically, physical blowing agents are not particularly limited and include C4-C6 compounds, and more specifically, one or more selected from the group consisting of cyclopentane, n-pentane, isopentane, n-butane, isobutane, n-hexane, isohexane, and cyclohexane. Preferably, the physical blowing agent is one or more selected from the group consisting of cyclopentane, n-pentane, and isopentane.

[0059] <<Polyisocyanate>> The polyisocyanate is preferably an aromatic polyisocyanate. Examples include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

[0060] When mixing the polyol-side foaming raw material liquid and the polyisocyanate-side foaming raw material liquid, the isocyanate index of the mixture (foaming raw material composition) is preferably 150 to 1000, more preferably 200 to 800, and even more preferably 300 to 600. Here, the isocyanate index refers to the ratio (molar ratio of NCO / OH) of the number of moles of isocyanate groups in the polyisocyanate compound to the total number of moles of active hydrogen in the reaction mixture containing all raw materials. When multiple polyols are added, the weighted average obtained by multiplying the hydroxyl value of each polyol by the number of parts added for each polyol and dividing by the total number of parts added for all polyols is defined as the average hydroxyl value (average OHV).

[0061] The viscosity of the polyisocyanate foaming raw material liquid at 25°C is preferably 150 to 750 mPa·s. Here, the viscosity is measured in accordance with ASTM D4889.

[0062] <<Polyol>> The polyol is not particularly limited as long as it is a compound having multiple hydroxyl groups. For example, it is preferable to use in combination a difunctional or trifunctional polyether polyol or either one of them with an aromatic polyester polyol having two or more hydroxyl groups at its terminal or side chain. The aromatic polyester polyol can be obtained, for example, by condensing a difunctional or trifunctional polyether polyol or either one of them with a polybasic acid. The preferred embodiments will be described in detail below.

[0063] Examples of polyols that constitute a bifunctional, trifunctional, or either one-to-one polyether polyol include bifunctional polyols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, etc., or compounds obtained by addition polymerization of these with alkylene oxides such as ethylene oxide or propylene oxide, polyethylene glycol, polypropylene glycol, etc.) and trifunctional polyols (trimethylolpropane, glycerin, etc., or compounds obtained by addition polymerization of these with alkylene oxides, etc.). One or more of these may be used in combination.

[0064] Furthermore, examples of polybasic acids that constitute aromatic polyester polyols include orthophthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, trimellitic acid, and pyromellitic acid. Here, a polyester polyol obtained by condensing phthalic acid with one or more difunctional, trifunctional, or polyfunctional alcohols or alkylene oxide adducts thereof is preferred, and more preferably a polyester polyol obtained by condensing terephthalic acid with diethylene glycol. The hydroxyl group content of the aromatic polyester polyol is two or more, preferably two to three.

[0065] Here, the average hydroxyl value of the polyol is preferably 200 mgKOH / g or higher, with no particular upper limit, for example, 1200 mgKOH / g. More specifically, the average hydroxyl value of the polyol is particularly preferably between 400 mgKOH / g and 600 mgKOH / g. When the average hydroxyl value of the polyol is within this range, a polyisocyanurate foam with higher thermal insulation properties is obtained. Here, the average hydroxyl value is the value measured in accordance with JIS K1557-1 (Plastics - Test methods for polyol raw materials of polyurethane - Part 1: Method for determining hydroxyl value).

[0066] <<Other ingredients>> <Flame retardant> Examples of known flame retardants include red phosphorus; phosphorus compounds such as ammonium polyphosphate, melamine phosphate, and triphenylphosphine; melamine compounds such as melamine cyanurate and melamine; metal hydrates such as aluminum hydroxide and magnesium hydroxide; antimony compounds such as antimony trioxide and antimony pentoxide; and phosphate ester compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di2,6-xylenyl phosphate, tris(dichloropropyl) phosphate, tris(chloropropyl) phosphate, and tris(tribromoneopentyl) phosphate. Among these, phosphate ester compounds are preferred, and particularly preferred are tris(chloropropyl) phosphate, triethyl phosphate, and tricresyl phosphate. Here, the flame retardant is preferably contained in an amount of 2 to 21% by mass, more preferably 9 to 21% by mass, and particularly preferably 9 to 17% by mass, based on the solid content mass of the foam layer.

[0067] <Foaming agent> The foaming agent is not particularly limited, but is preferably water. A foam can be formed by using a physical foaming agent alone, but a predetermined amount of a foaming agent may also be added. When water is used in combination with the foaming agent, the amount of physical foaming agent (e.g., cyclopentane) added is preferably 3.0 to 15 parts by mass per 100 parts by mass of the foaming composition. The amount of foaming agent (e.g., water) added is preferably 0.5 parts by mass or less based on 100 parts by mass of the foaming composition. When the amount of foaming agent (e.g., water) added is 0.5 parts by mass or less, it is easy to form a foam that is not brittle, has good adhesion to surface materials, etc., and has excellent heat insulation properties.

[0068] <Catalyst> Examples of catalysts include trimerizing catalysts, resin-based catalysts, and foaming catalysts. The catalyst preferably contains a trimerizing catalyst, and preferably is a mixed catalyst of a trimerizing catalyst, a resin-based catalyst, and a foaming catalyst.

[0069] Examples of trimerization catalysts include: 1) metal oxides such as lithium oxide, sodium oxide, and potassium oxide; 2) alkoxides such as sodium methoxy, sodium ethoxy, sodium propoxy, sodium butoxy, potassium methoxy, potassium ethoxy, potassium propoxy, and potassium butoxy; 3) organometallic salts such as potassium acetate, potassium octoate, potassium caprylate, and iron oxalate; 4) tertiary amines such as 2,4,6-tris(dimethylaminomethyl)phenol, N,N',N''-tris(dimethylaminopropyl)hexahydrotriazine, and triethylenediamine; 5) derivatives of ethyleneimine; and 6) acetylacetone chelates of alkali metals, aluminum, and transition metals, as well as quaternary ammonium salts. The use of organometallic salts or quaternary ammonium salts is more preferable. The trimerization catalyst is preferably a combination of potassium acetate and potassium octoate.

[0070] Resination or foaming catalysts can be those used in the production of ordinary polyurethane foam. Examples of resination or foaming catalysts include monoamines (N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, triethylamine, N,N-dimethylbenzylamine, etc.), cyclic monoamines (pyridine, N-methylmorpholine, N-ethylmorpholine, etc.), diamines (N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N, N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-tetramethylhexanediamine, methylene-bis(dimethylcyclohexylamine), N,N,N',N'-tetraethylethylenediamine, etc., triamines (N,N,N',N',N''-pentamethyldiethylenetriamine, N,N,N',N',N''-pentamethyldipropylenetriamine, 2,4,6-tris(dimethylaminomethyl)pheno) Examples of amine catalysts include ether diamines (bis(2-dimethylaminoethyl) ether, 2-(N,N-dimethylamino)ethyl-3-(N,N-dimethylamino)propyl ether, 4,4'-oxydimethylenedimorpholine, etc.), cyclic polyamines (triethylenediamine, N,N'-dimethylpiperazine, N,N'-diethylpiperazine, N,N-dimethylaminoethylmorpholine, 1-isobutyl-2-methylimidazole, 1-butoxy-2-methylimidazole, etc.), and alkanolamines (N,N,N'-trimethylaminoethylethanolamine, N,N,N'-trimethylaminopropylethanolamine, 2-(2-dimethylamino-ethoxy)ethanol, N,N-dimethylaminoethanol, N,N-trimethyl-1,3-diamino-2-propanol, N-methyl-N'-(2-hydroxyethyl)-piperazine, etc.).

[0071] <Other additives> Other additive components include conventionally known additives such as foam stabilizers, viscosity reducers, surface adhesion improvers, and foam refining agents. These additives may be added when mixing the polyol-side foaming raw material liquid with the polyisocyanate component, or they may be included in the polyol-side foaming raw material liquid beforehand. Conventionally known nonionic surfactants, silicone surfactants, etc., can be used as foam stabilizers.

[0072] <<<Uses of insulation materials>>> The thermal insulation material described herein has excellent performance and can be used for a variety of applications. More specifically, the thermal insulation material described herein can be used as thermal insulation in houses, factories, and vehicles (automobiles, airplanes, trains, ship hulls).

[0073] The thermal insulation material according to this disclosure maintains its thermal insulation structure even when in contact with water, etc., so even if it rains during the installation of the thermal insulation material according to this disclosure or during periods when the work is interrupted, deterioration of thermal insulation performance is unlikely to occur. Therefore, it is preferably used when constructing thermal insulation structures in outdoor environments. Furthermore, since the thermal insulation material according to this disclosure mainly consists of a urethane foam layer, it is relatively lightweight and flexible, making installation easy. In addition, as mentioned above, the thermal insulation material according to this disclosure can be constructed so that the cell structure of the foam is not easily destroyed even when pressure is applied. Therefore, the thermal insulation material according to this disclosure is preferably applied as thermal insulation material for roofs. The thermal insulation material according to this disclosure may be installed under the roof or on top of the roof. The thermal insulation material according to this disclosure is resistant to peeling of the PET layer even when in contact with water (rain, etc.) or exposed to high temperature and high humidity environments, making it easy to maintain thermal insulation performance. Furthermore, since the thermal insulation material according to this disclosure has excellent strength, the thermal insulation structure is easily maintained even when a load is applied to the thermal insulation material during installation. Therefore, the thermal insulation material according to this disclosure is preferably used as thermal insulation material installed on roofs. Furthermore, the thermal insulation material according to this disclosure is more preferably used as thermal insulation material installed on steel-framed corrugated metal roofs or reinforced concrete flat roofs that can be used in buildings such as apartment buildings, factories, and warehouses. In this case, the thermal insulation material according to this disclosure can also function as a waterproof sheet. In addition, the thermal insulation material according to this disclosure can be used for double-layered roofs (for example, double corrugated metal roofs). The thermal insulation material according to this disclosure may also be used for roof repair, by being additionally laminated on top of an existing roof. In other words, the technology according to this disclosure may be provided as a roof repair method for laminating the thermal insulation material according to this disclosure on top of an existing roof.

[0074] The thermal insulation material relating to this disclosure may be provided as a thermal insulation structure comprising the thermal insulation material relating to this disclosure. A specific example of a thermal insulation structure is a thermal insulation structure comprising a roof and the thermal insulation material relating to this disclosure installed on the roof. As an example of a thermal insulation structure relating to this disclosure, Figure 4 shows a conceptual side view of a corrugated metal roof in which the thermal insulation material 10 relating to this disclosure is laminated on a corrugated metal roof. The thermal insulation structure shown in Figure 4 has a configuration in which the corrugated metal roof B is fixed to a beam A via a fixing frame C. Furthermore, the thermal insulation material 10 is provided on the corrugated metal roof B, and the thermal insulation material 10 is fixed by fasteners not shown. Desired fasteners may be used, such as screws, bolts, adhesive tape, and fixing frames. The thermal insulation material 10 can reduce the transfer of heat through the corrugated metal roof and can prevent corrosion of the corrugated metal roof due to moisture (rain, etc.). The thermal insulation structure may also have thermal insulation materials other than the thermal insulation material relating to this disclosure. [Examples]

[0075] The thermal insulation material will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following.

[0076] <<Example 1>> The thermal insulation material according to Example 1 was manufactured based on the following method.

[0077] <Preparation of polyol-based foaming raw material solution> As the polyol, 100 parts by mass of a polyester polyol (OHV 400 mg KOH / g, weight-average molecular weight 510) obtained by dehydration condensation of orthophthalic acid and diethylene glycol (DEG), and 15 parts by mass of diethylene glycol (DEG) were used. A polyol, foam stabilizer, catalyst, and flame retardant were mixed to obtain a polyol-based foaming raw material liquid. The content of the foam stabilizer, catalyst, and flame retardant used is as follows.

[0078] (Foam stabilizer) Based on the total mass of the foaming raw material composition (total weight of all materials excluding the foaming agent), Niax Slicone L-6635 (manufactured by MOMENTIVE) was added to a concentration of 1.5% by mass. (catalyst) Based on the total mass of the foaming raw material composition, potassium octylate (a trimerizing catalyst) was added at a concentration of 0.6% by mass, potassium acetate at 0.2% by mass, and Rubeac DMP-30 (manufactured by Nacalai Tesque) at 0.3% by mass. (Flame retardant) Tris(1-chloro-2-propyl)phosphate (TCPP) (trade name: ProFlame-PC1389, manufactured by ProFlame) was added to the total mass of the foaming raw material composition to a concentration of 15% by mass.

[0079] <Preparation of foaming composition> After weighing the polyol-side foaming raw material liquid, it was stirred for 30 seconds using a 3000 rpm propeller stirrer. Then, to the polyol-side foaming raw material liquid, which had been warmed to 20°C, polyisocyanate (CRUD MDI, product name: MR-200, manufactured by Tosoh Corporation), which had also been warmed to 20°C, was added to obtain a foaming raw material composition with an isocyanate index of 450. In addition, cyclopentane (product name: Marcazole FH, manufactured by Maruzen Petroleum Co., Ltd.), a physical foaming agent, was added in an amount of 6.5% by mass relative to the total mass of the foaming raw material composition. These mixtures were then rapidly stirred for 10 seconds using a 5000 rpm propeller stirrer to obtain a foaming composition.

[0080] <Manufacturing of insulation materials> A first substrate, consisting of a first composite layer and a first outer layer, and a second substrate, consisting of a second composite layer and a second outer layer, were prepared. Next, a 300mm x 300mm x 50mm mold frame consisting of an upper mold and a lower mold was prepared, and the first substrate and the second substrate were placed in the upper mold and lower mold, respectively. The materials of the first composite layer, the first outer layer, the second composite layer, and the second outer layer, as well as the order of lamination of each layer, are as shown in Table 1. Approximately 180g of the foaming composition was poured into the mold frame, which was temperature-controlled at 60°C, and foamed and cured. As described above, the thermal insulation material according to Example 1 was prepared.

[0081] As shown in Table 1, the thermal insulation material in Example 1 consists of a foamed layer (isocyanurate foam, 50 mm thick, 36 kg / m³ density). 3 The thermal insulation material according to Example 1 comprises a composite layer (first composite layer and second composite layer) including a polyolefin layer made of LLDPE (Long Life Depositionable Polyethylene) and a PET layer, with the composite layer provided on both sides of the foam layer, and the polyolefin layer contained in the composite layer in contact with the foam layer. Furthermore, the thermal insulation material according to Example 1 has outer layers (first outer layer and second outer layer) including a paper layer (kraft paper) and a metal layer (aluminum foil) laminated on the composite layer. Furthermore, the thermal insulation material according to Example 1 contains cyclopentane as a hydrocarbon gas in the foam layer.

[0082] <<Comparative Example 1-3>> The thermal insulation materials according to Comparative Examples 1-3 were manufactured in the same manner as in Example 1, except that the materials shown in Table 1 were used instead of the first and second composite layers.

[0083] As shown in Table 1, the thermal insulation material according to Comparative Example 1 has a structure in which only a PET layer is provided instead of the composite layer (first composite layer and second composite layer) in the thermal insulation material of Example 1.

[0084] As shown in Table 1, the thermal insulation material of Comparative Example 2 is characterized in that, in the thermal insulation material of Example 1, the composite layer (first composite layer and second composite layer) is replaced with an easily bondable PET layer (PET film with polyester urethane resin partially attached, bond amount 0.01 g / m²). 2 It has a structure that includes a )

[0085] As shown in Table 1, the thermal insulation material according to Comparative Example 3 has a structure in which only a polyethylene layer is provided instead of the composite layer (first composite layer and second composite layer) in the thermal insulation material of Example 1.

[0086] <<Physical Properties / Evaluation>> For each insulation material, we measured its adhesiveness, dimensional stability, resistance to denting / blistering, and long-term thermal conductivity.

[0087] <Adhesiveness> Each insulation material was cut to 40mm x 150mm to serve as a test sample.

[0088] (Measurement condition 1: Peel test) A 90-degree peel test was performed on the sample. The tests were conducted under two conditions: a low-speed condition (peeling speed of 50 mm / min) and a high-speed condition (peeling speed of 500 mm / min), with the peeling speed varied. The average peeling strength and maximum peeling strength were measured under each condition. The average peel strength under low-speed conditions is preferably 4.0 N / 40 mm or higher, or 6.0 N / 40 mm or higher. The average peel strength under high-speed conditions is preferably 6.0 N / 40 mm or higher, or 8.0 N / 40 mm or higher. The maximum peel strength under low-speed conditions is preferably 20.0 N / 40 mm or more, or 40.0 N / 40 mm or more. The maximum peel strength under high-speed conditions is preferably 10.0 N / 40 mm or more, or 20.0 N / 40 mm or more.

[0089] (Environmental condition 2: Flood) The sample was completely submerged in water and left to stand for one week. Subsequently, the composite layer and outer layer laminated to the foam were grasped by hand, and the peeled areas were identified when the composite layer and outer layer were separated from the foam, and evaluated as follows. A: Delamination occurred outside the interlayer between the foam layer and the composite layer. B: Delamination occurred between the foam layer and the composite layer.

[0090] (Measurement condition 3: High temperature and high humidity) The samples were cured for one week under conditions of 70°C and 90% humidity. Subsequently, the composite layer and outer layer laminated to the foam were grasped by hand, and the peeled areas were identified when the composite layer and outer layer were separated from the foam, and evaluated as follows. A: Delamination occurred outside the interlayer between the foam layer and the composite layer. B: Delamination occurred between the foam layer and the composite layer.

[0091] Under both measurement conditions 2 and 3, no delamination occurred between the foam layer and the composite layer in Example 1, but delamination occurred in the kraft paper layer. Therefore, it is understood that Example 1 exhibits excellent adhesion of the composite layer even when exposed to water or high temperature and high humidity environments.

[0092] <Dimensional Stability> Each insulation material was cut to 100mm x 100mm to serve as a test sample. Referring to the conditions described in JIS K 7249, the sample was left to stand at 80°C for 24 hours as Step 1, and the sample was left to stand at -30°C for 24 hours as Step 2. Steps 1 and 2 were performed consecutively for two cycles (in the order of first Step 1, first Step 2, second Step 1, second Step 2). The initial dimensions of the sample (length, width, thickness) were defined as the reference dimensions, and the dimensions of the sample after each step were defined as the changed dimensions. The dimensional change rate (%) was defined as the percentage change in the changed dimensions relative to the reference dimensions [(changed dimensions - reference dimensions) / reference dimensions × 100]. For each dimension of the sample, measurements were taken at three points for length, three points for width, and six points for thickness, and the average value was calculated. Furthermore, when measuring the dimensional change rate in each process, we measured the dimensional change rate A immediately after each process was performed, and the dimensional change rate B after the sample was left to stand for 1 hour at 23°C and 50% humidity after each process was performed. For each step (Step 1 of the first process, Step 2 of the first process, Step 1 of the second process, and Step 2 of the second process), dimensional change rates A and B were measured, and the average dimensional change rate, calculated as the average of these dimensional change rates, was used to determine dimensional stability. The results are shown in Table 1. As shown in Table 1, the thermal insulation material according to Example 1 was shown to have dimensional stability equivalent to that of the comparative example. In particular, the dimensional stability of the thickness was superior to that of Comparative Example 1. Furthermore, the dimensional stability in the length direction is preferably -1.00 to 1.00% or -0.50 to 0.50%. The dimensional stability in the width direction is preferably -1.00 to 1.00% or -0.50 to 0.50%. The dimensional stability in the thickness direction is preferably -1.00 to 1.00% or -0.50 to 0.50%.

[0093] <Dent resistance> The dent resistance measurement is performed by changing the curing and compression conditions. After curing the insulation material under the specified conditions (conditions 1 and 2), a steel ball is placed in the center of the surface that will be the upper side during installation. A load is applied through the steel ball, compressing the insulation material to the point just before the composite layer and outer layer rupture, and this is maintained for 10 minutes. More specifically, a preliminary test specimen with the same structure as the measurement sample is prepared, compressed in the same manner, and the depth of the compression mark (stroke) at which an abnormal sound occurs at the moment of material failure is recorded. The insulation material is then compressed to just before the depth of that compression mark and maintained for 10 minutes. After removing the iron ball, the compression marks on the surface of the insulation material are observed, and the depth of the compression marks is measured as D1. Furthermore, the insulation material, after the iron ball has been removed, is cured for 24 hours at 80°C. The compression marks on the surface of the insulation material after curing are observed, and the depth of the compression marks is measured as D2. The results are shown in Table 1. (Curing conditions) Condition 1: 23℃, 24 hours Condition 2: 80°C, 24 hours

[0094] <Long-term thermal conductivity> Each insulation material was cut to 200mm x 200mm to serve as a test sample. An accelerated 60°C test was conducted in accordance with JIS A 9521. Furthermore, the change in thermal conductivity was measured according to the number of days elapsed since the start of the test, using a heat flow meter method based on JIS A 1412-2. Compared to Comparative Example 3, Example 1 showed significantly lower changes in thermal conductivity, indicating that the low thermal conductivity at the time of manufacture was easily maintained. A change in thermal conductivity of 5% or less, or 4% or less, indicates excellent long-term thermal conductivity.

[0095] [Table 1] [Industrial applicability]

[0096] The thermal insulation material according to the present invention comprises a foam layer and a gas barrier layer, and the gas barrier layer is less likely to peel off even when in contact with water or exposed to a high-temperature, high-humidity environment. For this reason, it is preferably used as thermal insulation material installed on roofs and the like. [Explanation of Symbols]

[0097] 10. Insulation 100 foam layer 200 composite layers 201 Polyolefin layer 202 PET layer 210 First composite layer 220 Second composite layer 300 outer layer 310 First outer layer 320 Second outer layer 301a Polyolefin layer 302b Polyolefin layer 302 Paper layer 303 Metal layer

Claims

1. A foam layer containing hydrocarbon gases, The foam layer comprises a composite layer laminated on at least one surface of the foam layer, The composite layer comprises a polyolefin layer in contact with the foam layer, A PET layer laminated on the aforementioned polyolefin layer, An insulating material that has [the following characteristics].

2. The thermal insulation material according to claim 1, comprising the composite layer on both sides of the foam layer.

3. The thermal insulation material according to claim 1 or 2, wherein an outer layer is laminated on the composite layer.

4. The thermal insulation material according to claim 1 or 2, wherein the foam layer is a urethane-based foam layer.

5. An insulating material according to claim 1 or 2, which is installed on a roof.

6. An insulating structure comprising a roof and an insulating material according to claim 1 or 2 installed on the roof.

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