Stacked structure

Abstract

To provide a multilayer structure that has incombustibility and resists a dimensional change during heating at high temperature.SOLUTION: A multilayer structure 10 has a metal sheet 12 and a resin body 11. In an exothermic test using a cone calorimeter for heating from the metal sheet 12 side, a test piece 50 mm thick is not in contact with ignition and does not catch fire, with a gross calorific value of 8MJ / m2 or less for 20 minutes.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a laminated structure used in the field of construction and the like.

Background Art

[0002] In the fields of construction, civil engineering, electricity, vehicles, etc., resin bodies are widely used in various forms. For example, in the construction field, foams are used as heat insulators. In recent years, the required performance for safety of heat insulators has tended to increase, and non-combustibility and flame retardancy may be required. Therefore, conventionally, for example, a flame retardant may be blended into a foam to impart flame retardancy (see, for example, Patent Document 1). In addition, it has also been considered to form a laminate by laminating a metal sheet on one side of a resin body such as a foam.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, as in Patent Document 1, simply blending a flame retardant into a resin body such as a foam often cannot sufficiently impart non-combustibility. On the other hand, when a metal sheet is laminated on a resin body such as a foam, although non-combustibility is easily imparted, the gas generated from the foam during high-temperature heating may not escape sufficiently to the outside, and dimensional changes may occur in the laminate. When dimensional changes occur, deformation occurs during a fire, and for example, collapse of building materials is likely to occur. In addition, there is also a problem that in a heat generation test using a cone calorimeter, when it comes into contact with ignition, it is not recognized as a non-combustible material under the Building Standards Law.

[0005] Therefore, an object of the present invention is to impart incombustibility and suppress dimensional changes during high-temperature heating in a laminated structure having a metal sheet and a resin body.

Means for Solving the Problems

[0006] As a result of intensive studies, the present inventor has found that in a predetermined heat generation test using a laminated structure, a test piece with a thickness of 50 mm does not come into contact with ignition and does not catch fire, and the total heat generation amount in 20 minutes is 8 MJ / m 2 The present invention has been completed by finding that the above problems can be solved by the following, and the gist of the present invention is to provide the following [1] to

[12] . [1] Comprising a metal sheet and a resin body, A test piece is set so that the distance from ignition is 13 mm, and in a heat generation test using a cone calorimeter that heats from the metal sheet side at a radiant heat intensity of 50 kW / m 2 In the heat generation test using a cone calorimeter that heats from the metal sheet side at a radiant heat intensity of 50 kW / m 2 The following laminated structure in which a test piece with a thickness of 50 mm does not come into contact with ignition and does not catch fire, and the total heat generation amount in 20 minutes is 8 MJ / m [2] The laminated structure according to [1] above, wherein the resin constituting the resin body is a thermoplastic resin. [3] The laminated structure according to [1] or [2] above, wherein the resin constituting the resin body contains a polyolefin-based resin. [4] The laminated structure according to any one of [1] to [3] above, wherein the resin body is a crosslinked body. [5] The laminated structure according to any one of [1] to [4] above, wherein the resin body is a foam. [6] The laminated structure according to any one of [1] to [5] above, wherein the resin body contains a flame retardant. [7] The laminated structure according to any one of [1] to [6] above, wherein the metal sheet has a plurality of holes. [8] The laminated structure according to [7] above, wherein the aperture ratio of the metal sheet is 1 to 10%. [9] The laminated structure according to any one of [1] to [8] above, wherein the thickness of the metal sheet is 10 to 100 μm.

[10] The laminated structure according to any one of [1] to [9] above, wherein the metal sheet is an aluminum sheet.

[11] The laminated structure according to any one of [1] to

[10] above, further comprising a glass cloth disposed between the metal sheet and the resin body.

[12] The basis weight of the glass cloth is 20 to 300 g / m 2 The laminated structure according to

[11] above.

Effect of the Invention

[0007] According to the present invention, a laminated structure having nonflammability and capable of suppressing dimensional changes during high-temperature heating can be provided.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Mode for Carrying Out the Invention

[0009] [Laminated Structure] The laminated structure of the present invention is a laminated structure including a metal sheet and a resin body. In the heat generation test, a test piece with a thickness of 50 mm does not come into contact with ignition and does not catch fire, and the total heat generation amount in 20 minutes is 8 MJ / m 2 It is as follows. The laminated structure having the above configuration is excellent in flame retardancy and has nonflammability. Further, the laminated structure hardly undergoes dimensional changes such that it does not come into contact with ignition even during high-temperature heating, so deformation and the like are less likely to occur during a fire. In addition, in the heat generation test, the test piece is set so that the distance from ignition is 13 mm, and in accordance with the test method of ISO-5660, the radiant heat intensity is 50 kW / m 2This is a test using a cone calorimeter that heats from the metal sheet side. The specific method is as described in the examples below.

[0010] From the perspective of imparting high non-combustibility, the total heat release in the above heat release test for 20 minutes is 5 MJ / m 2 The following is preferable, and 4 MJ / m 2 The following is preferable, and 3 MJ / m 2 The following is even more preferable. On the other hand, the lower the above total heat release, the better, and it may be 0 MJ / m 2 or more, but in practical terms, it is 0.5 MJ / m 2 or more.

[0011] Also, the distance between the test piece and the ignition after heating for 20 minutes may be greater than 0 mm, and the greater this distance, the better. Preferably it is 2 mm or more, more preferably 3 mm or more, and even more preferably 4 mm or more. Also, the above distance is usually less than or equal to the distance between the test piece before heating and the ignition. Therefore, the above distance is usually 13 mm or less.

[0012] Hereinafter, the configuration of the laminated structure will be described in more detail. <Resin body> The resin body may be a foam or a non-foam, but it is preferably a foam. If it is a foam, heat insulation can be imparted to the laminated structure. Also, the resin constituting the resin body is preferably a thermoplastic resin. By using a thermoplastic resin for the resin body, the processability, workability, etc. of the resin body become good. The resin constituting the resin body is not particularly limited, but it is preferable to use a resin that can be used for foams. Specifically, polyvinyl chloride-based resins, silicone-based resins, acrylic-based resins, polyurethane-based resins, polyolefin-based resins, elastomers, styrene-based resins, etc. can be mentioned. The elastomer may be a thermoplastic elastomer or a rubber component other than the thermoplastic elastomer. Among these, polyolefin-based resins are preferable from the viewpoints of processability and moldability into foams.

[0013] (Degree of crosslinking) The resin body is preferably a crosslinked body, more preferably a crosslinked foam. Further, the resin body is preferably a crosslinked body crosslinked particularly by an electron beam. When the resin body is a crosslinked body, the degree of crosslinking represented by the gel fraction is preferably 20 to 70% by mass. By setting the degree of crosslinking of the resin body within the above range, particularly when the resin body is a foam, the mechanical strength, flexibility, and moldability can be improved well in balance, and the dimensional stability during high-temperature heating and the like also become good. From these viewpoints, the degree of crosslinking of the resin body is more preferably 25 to 60% by mass, and even more preferably 30 to 50% by mass. The method for measuring the degree of crosslinking is as described in the examples described later.

[0014] (Apparent density) When the resin body is a foam, the apparent density of the foam is preferably 0.015 to 0.20 g / cc. By setting the apparent density to 0.015 g / cc or more, a certain mechanical strength can be imparted to the foam, and the dimensional stability when heated to a high temperature also becomes good. Further, by setting it to 0.20 g / cc or less, appropriate heat insulation can be imparted. Also, the flexibility and the like become excellent, and the workability and the like also become good. From these viewpoints, the apparent density of the foam is more preferably 0.018 to 0.10 g / cc, and even more preferably 0.02 to 0.05 g / cc.

[0015] (Thickness of the resin body) The thickness of the resin body is not particularly limited, but is, for example, 3 to 50 mm. By setting the thickness to 3 mm or more, appropriate heat insulation can be imparted, for example, when it is a foam. Further, by setting it to 50 mm or less, the dimensional stability during high-temperature heating becomes good. Also, by setting the thickness within the above range, it becomes suitable for use as a building material. From these viewpoints, the thickness of the resin body is preferably 5 to 40 mm, and even more preferably 10 to 30 mm.

[0016] (Polyolefin resin) As the polyolefin resin used for the resin body, polypropylene resins, polyethylene resins, etc. are preferable. Among these, from the viewpoints of flexibility, processability, workability, etc., polyethylene resins are more preferable. Also, a polypropylene resin and a polyethylene resin may be used in combination.

[0017] (Polypropylene resin) Examples of the polypropylene resin include homopolypropylene which is a homopolymer of propylene, and copolymers of propylene and α-olefins other than propylene. Examples of the copolymer of propylene and α-olefins other than propylene include block copolymers, random copolymers, random block copolymers, etc. Among these, random copolymers (that is, random polypropylene) are preferable. Examples of the α-olefin other than propylene include α-olefins having about 4 to 10 carbon atoms such as ethylene having 2 carbon atoms, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, etc. Among these, from the viewpoints of moldability and heat resistance, ethylene is preferable. In the copolymer, these α-olefins can be used alone or in combination of two or more. Also, the polypropylene resin may be used alone or in combination of two or more.

[0018] Also, in the copolymer of propylene and α-olefins other than propylene, those obtained by copolymerizing 80 mass% or more and less than 100 mass% of propylene and 20 mass% or less of α-olefins other than propylene are preferable. Here, it is more preferable that propylene is 90 to 99.5 mass% and α-olefins other than propylene are 0.5 to 10 mass% with respect to all monomer components constituting the copolymer, and it is even more preferable that propylene is 95 to 99 mass% and α-olefins other than propylene are 1 to 5 mass%.

[0019] (Polyethylene resin) As the polyethylene resin, low-density polyethylene resin (LDPE, density: less than 0.930 g / cm 3 ), medium-density polyethylene resin (MDPE, density: 0.930 g / cm 3 or more and less than 0.942 g / cm 3 ), high-density polyethylene resin (HDPE, density: 0.942 g / cm 3 or more), linear low-density polyethylene resin (LLDPE), etc. may be mentioned. Among these, from the viewpoints of flexibility, processability, workability, etc., low-density polyethylene resin (LDPE) and linear low-density polyethylene resin (LLDPE) are preferable, and low-density polyethylene resin (LDPE) is more preferable.

[0020] The linear low-density polyethylene resin is usually a copolymer of ethylene and a small amount of α-olefin with ethylene as the main component (preferably 70% by mass or more, more preferably 90% by mass or more). Here, as the α-olefin, those having 3 to 12 carbon atoms, more preferably 4 to 10 carbon atoms are preferable, and specifically, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, etc. may be mentioned. In the copolymer, these α-olefins can be used alone or in combination of two or more. Further, the polyethylene resin may be used alone or in combination of two or more.

[0021] As the polyolefin resin, polyolefin resins other than the above-mentioned resins can also be used. Specific examples of such resin components include ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-(meth)alkyl acrylate copolymer, etc. These resin components may be appropriately added, for example, to a resin in which at least one of polypropylene resin and polyethylene resin is used.

[0022] The resin constituting the resin body may be composed of a polyolefin resin alone, but may contain resin components other than the polyolefin resin as long as the object of the present invention is not inhibited. The content of the polyolefin resin is, for example, 70% by mass or more, preferably 80 to 100% by mass, and more preferably 90 to 100% by mass with respect to the total amount of the resin constituting the resin body.

[0023] (Flame retardant) The resin body of the present invention preferably further contains a flame retardant. The flame retardant is preferably at least one selected from phosphorus-based flame retardants, halogen-based flame retardants, antimony-based compounds, and metal hydroxides. Such a flame retardant can appropriately improve the flame retardancy of the resin body. In addition, such a flame retardant does not cause the viscosity of the resin composition to become too high in relation to the foaming agent described later, so it is easy to adjust the apparent density of the foam to a suitable range. Therefore, by using the above flame retardant, it is easy to obtain a foam having both flame retardancy and heat insulation properties. From such a viewpoint, as the above flame retardant, at least one selected from phosphorus-based flame retardants, halogen-based flame retardants, and antimony-based compounds is more preferable, and at least one selected from halogen-based flame retardants and antimony-based compounds is even more preferable.

[0024] [[Phosphorus-based flame retardant]] Examples of phosphorus-based flame retardants include phosphates, polyphosphates, phosphazene-based compounds, and phosphorus-based spiro compounds. Among these, from the viewpoint of having a small influence on the viscosity of the foaming composition and being easy to adjust the foaming ratio, at least one selected from phosphates, polyphosphates, and phosphorus-based spiro compounds is preferable.

[0025] Examples of phosphates include melamine orthophosphate, piperazine orthophosphate, melamine pyrophosphate, piperazine pyrophosphate, calcium phosphate, and magnesium phosphate. Examples of polyphosphates include ammonium polyphosphate, melamine polyphosphate, melamine·melam·melem polyphosphate, and piperazine polyphosphate. In addition to the above, as orthophosphates, pyrophosphates, and polyphosphates, there are also N,N,N’,N’-tetramethyldiaminomethane, ethylenediamine, N,N’-dimethylethylenediamine, N,N’-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N,N’,N’-tetramethylethylenediamine, N,N,N’,N’-diethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, trans-2,5-dimethylpiperazine, 1,4-bis(2-aminoethyl)piperazine, 1,4-bis(3-aminopropyl)piperazine, acetoguanamine, benzoguanamine, acrylguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine, ammeline, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornenediguanamine, methylenediguanamine, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, 1,3-hexylenedimelamine, and salts thereof can also be used.

[0026] Among the above, one or more selected from melamine pyrophosphate salt, piperazine pyrophosphate salt, and ammonium polyphosphate salt are preferred, and it is also preferable to use the piperazine pyrophosphate salt and the melamine pyrophosphate salt in combination. In addition, as the phosphorus-based flame retardant, as the intumescent flame retardant, one or more selected from the above-mentioned phosphates and polyphosphates may be mixed with a metal oxide and used. Examples of the metal oxide to be used in combination with one or more selected from phosphates and polyphosphates include, for example, zinc oxide, magnesium oxide, calcium oxide, silicon dioxide, titanium oxide, manganese oxide (MnO, MnO2), iron oxide (FeO, Fe2O3, Fe3O4), copper oxide, nickel oxide, tin oxide, aluminum oxide, and calcium aluminate. Among these, zinc oxide, magnesium oxide, and calcium oxide are preferred. When one or more selected from phosphates and polyphosphates are mixed with a metal oxide and used, it is preferable to adjust their mass ratio as follows. The mass ratio of one or more selected from phosphates and polyphosphates to the metal oxide [total mass of phosphates and polyphosphates / mass of metal oxide] is preferably 4 or more and 100 or less, more preferably 6 or more and 50 or less, and still more preferably 10 or more and 35 or less from the viewpoint of improving flame retardancy.

[0027] Examples of commercially available products of the flame retardant containing one or more selected from the above-mentioned phosphates and polyphosphates include For example, "ADEKA STAB FP-2100J", "ADEKA STAB FP-2200S", "ADEKA STAB FP-2500S" manufactured by ADEKA CORPORATION, and "EXOLIT AP422", "EXOLIT AP462" manufactured by Clariant Japan Limited.

[0028] The phosphazene-based compound is an organic compound having a -P=N- bond in the molecule. As the phosphazene-based compound, a compound having a six-membered cyclic phosphazene skeleton composed of -P=N- is preferred. Examples of the phosphazene-based compound include "SPB-100" commercially available from Otsuka Chemical Co., Ltd. ​The phosphorus-based spiro compound is not particularly limited as long as it is a spiro compound having a phosphorus atom. The spiro compound is a compound having a structure in which two cyclic skeletons share one carbon atom. The phosphorus-based spiro compound is a compound in which at least one of the elements constituting the two cyclic skeletons is a phosphorus atom, and each cyclic skeleton preferably has a phosphorus atom. Examples of the phosphorus-based spiro compound include "Firegard FCX-210" of Teijin Limited.

[0029] <<Halogen-based flame retardant>> The halogen-based flame retardant stabilizes active OH radicals by the radical trapping effect in the gas phase. Also, during combustion, the active OH radicals and H radicals that promote combustion are trapped and stabilized by hydrogen halides generated from the halogen-based flame retardant. Furthermore, during combustion, the hydrogen halides generated from the halogen-based flame retardant are non-flammable, so they cause a dilution effect and also an oxygen barrier effect. The halogen-based flame retardant is not particularly limited as long as it is a flame retardant containing halogen in its molecular structure. Examples of the halogen-based flame retardant include bromine-based flame retardants and chlorine-based flame retardants, and among them, bromine-based flame retardants are preferred.

[0030] The brominated flame retardant is not particularly limited as long as it contains bromine in its molecular structure. Examples of brominated flame retardants include decabromodiphenyl ether, octabromodiphenyl ether, tetrabromobisphenol A (TBBA), TBBA epoxy oligomer, TBBA carbonate oligomer, TBBA bis(dibromopropyl ether), TBBA bis(aryl ether), bis(pentabromophenyl)ethane, 1,2-bis(2,4,6-tribromophenoxy)ethane, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, 2,6- or 2,4-dibromophenol homopolymer, brominated polystyrene, polybrominated styrene, ethylenebistetrabromophthalimide, hexabromocyclododecane, hexabromobenzene, pentabromobenzyl acrylate monomer, pentabromobenzyl acrylate polymer, and the like. Among these, bis(pentabromophenyl)ethane is preferred from the viewpoints of flame retardancy and foaming properties. These brominated flame retardants may be used alone or in combination of two or more.

[0031] <<Antimony-based compound>> Examples of antimony-based compounds include antimony trioxide, antimony pentoxide, and the like. Among these, antimony trioxide is preferred. When using a halogen-based flame retardant, it is also preferable to use an antimony-based compound in combination. The antimony-based compound can improve the flame retardancy of the foam sheet and reduce the content of the halogen-based flame retardant due to the synergistic effect with the halogen-based flame retardant. When using an antimony-based compound, it reacts with the halogen-based flame retardant during combustion to form an incombustible antimony halide, thereby producing an oxygen shielding effect.

[0032] <<Metal hydroxide>> Examples of the metal hydroxide include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, talc, and the like. Among these, at least one selected from aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and talc is preferable, and at least one selected from aluminum hydroxide and magnesium hydroxide is more preferable.

[0033] The content of the flame retardant in the resin body is preferably 1 to 150 parts by mass with respect to 100 parts by mass of the resin contained in the resin body. By being 1 part by mass or more, the flame retardancy can be appropriately imparted to the resin body. By being 150 parts by mass or less, the processability, mechanical properties, etc. of the resin body, particularly the foam, become good. From these viewpoints, the content of the flame retardant in the resin body is more preferably 2 to 40 parts by mass, further preferably 3 to 25 parts by mass, and even more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the resin.

[0034] The flame retardant may be used alone or in combination of two or more. For example, when using two or more in combination, a combination of a halogen-based flame retardant and an antimony-based compound is preferable as described above, and among them, it is more preferable to use a bromine-based flame retardant and an antimony-based compound in combination. When a halogen-based flame retardant and an antimony-based compound are used in combination, the ratio of the content of the antimony-based compound to the content of the halogen-based flame retardant (antimony-based compound / halogen-based flame retardant) is, from the viewpoint of the synergistic effect with the halogen-based flame retardant, for example, 0.1 to 1 by mass ratio, preferably 0.2 to 0.8, and more preferably 0.3 to 0.7.

[0035] (Blowing agent) When the resin body is a foam, the resin body may be obtained by foaming a resin composition containing the above resin components such as polyolefin resins. As methods for foaming the resin composition, there are a chemical foaming method and a physical foaming method. The chemical foaming method is a method of forming bubbles by the gas generated by the thermal decomposition of a compound (foaming agent) added to the resin composition, and the physical foaming method is a method of impregnating a resin composition with a low-boiling liquid (foaming agent) and then volatilizing the foaming agent to form cells. The foaming method is not particularly limited, but from the viewpoint of obtaining a uniform closed-cell foam, the chemical foaming method is preferred. As the foaming agent used in the chemical foaming method, a thermal decomposition type foaming agent is used. For example, an organic thermal decomposition type foaming agent or an inorganic thermal decomposition type foaming agent having a decomposition temperature of about 160 to 270 °C can be used.

[0036] Examples of the organic thermal decomposition type foaming agents include azo compounds such as azodicarbonamide, metal salts of azodicarboxylic acid (such as barium azodicarboxylate), azobisisobutyronitrile, nitroso compounds such as N,N'-dinitrosopentamethylenetetramine, hydrazodicarbonamide, hydrazine derivatives such as 4,4'-oxybis(benzenesulfonylhydrazide) and toluenesulfonylhydrazide, and semicarbazide compounds such as toluenesulfonyl semicarbazide.

[0037] Examples of the inorganic thermal decomposition type foaming agents include ammonium carbonate, sodium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, and monosodium anhydrous citrate. Among these, from the viewpoints of obtaining fine bubbles, economy, and safety, organic thermal decomposition type foaming agents are preferred, azo compounds and nitroso compounds are more preferred, azo compounds such as azodicarbonamide and azobisisobutyronitrile are even more preferred, and azodicarbonamide is even more preferred. These foaming agents may be used alone or in combination of two or more.

[0038] The compounding quantity of the thermal decomposition type foaming agent in the resin composition is preferably 2 to 40 parts by mass, more preferably 10 to 35 parts by mass, and still more preferably 15 to 32 parts by mass with respect to 100 parts by mass of the resin contained in the resin body. When the compounding quantity of the thermal decomposition type foaming agent is within this range, the foamability of the foam becomes appropriate, and a foam having a desired apparent magnification can be obtained.

[0039] (Other additives) The resin body may further contain additives other than the above. Specifically, antioxidants, decomposition temperature adjusters, crosslinking aids, metal poisoning preventives, antistatic agents, stabilizers, fillers, pigments, etc. can be mentioned. Examples of the antioxidant include phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. The content of the antioxidant in the resin body is, for example, 0.1 to 10 parts by mass, preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the resin. Examples of the decomposition temperature adjuster include zinc oxide, zinc stearate, urea, etc. The content of the decomposition temperature adjuster in the resin body is, for example, 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of the resin.

[0040] <Metal sheet> In the present invention, by having a metal sheet in the laminated structure, the laminated structure can be imparted with nonflammability. In addition, it exhibits a heat shielding effect, and particularly when the resin body is a foam, the heat insulation property of the laminated structure can be improved. Examples of the metal constituting the metal sheet include zinc, gold, silver, chromium, titanium, iron, aluminum, copper, nickel, tantalum, or alloys containing these, and examples of the alloy include stainless steels such as SUS, brass, beryllium copper, inconel, etc. These metals may be used alone or in combination of two or more. Among these, aluminum is preferable, and therefore, the metal sheet is preferably an aluminum sheet. By using an aluminum sheet, the flexibility of the laminated structure is ensured, and the workability and constructability are good. In addition, it is lightweight and not easily corroded.

[0041] As the metal sheet, one having a thickness on the order of what is generally called metal foil may be used, and the thickness of the metal sheet is, for example, 5 to 250 μm. By setting the thickness to 5 μm or more, it becomes easier to impart incombustibility and heat insulation properties to the laminated structure by the metal sheet. Also, by setting the thickness to 250 μm or less, it is possible to prevent the laminated structure from becoming unnecessarily thick due to the metal sheet. The thickness of the metal sheet is preferably 10 to 100 μm. By setting the thickness to 10 μm or more, the strength of the metal sheet becomes good, and problems such as the metal sheet being torn during construction are less likely to occur, improving workability. Also, by setting it to 100 μm or less, it becomes easier to ensure the flexibility of the entire laminated structure, and the workability of the laminated structure becomes good. From the viewpoint of workability and the like, the thickness of the metal sheet is more preferably 15 to 70 μm.

[0042] The metal sheet preferably has a plurality of holes. The holes are through-holes that penetrate in the thickness direction of the sheet. When the metal sheet has a plurality of holes, even if gas is generated when the resin body is thermally decomposed by heating, the gas is released through the holes. Therefore, it is possible to prevent the laminated structure from expanding during high-temperature heating and suppress the occurrence of dimensional changes.

[0043] The shape of the holes is not particularly limited, and may be a shape whose contour consists of a curve such as a circular shape or an elliptical shape, or may be a polygon such as a triangle, a quadrilateral, a pentagon, or a hexagon, or may have a shape in which the contour combines a curve and a straight line. Also, the diameter of each hole is not particularly limited, but is, for example, 0.05 to 5 mm, preferably 0.1 to 1 mm, and more preferably 0.2 to 0.8 mm. When the diameter of the holes is within the above range, it becomes possible to efficiently release the gas generated in the resin body during high-temperature heating to the outside through the holes. Also, by setting it to below the above upper limit value, it is possible to prevent the incombustibility, heat insulation property, etc. from deteriorating due to the voids formed by the holes. Note that the diameter of the holes means the maximum diameter of each hole.

[0044] Also, the holes may be regularly arranged or irregularly arranged. When regularly arranged, the holes may be arranged in a lattice pattern with equal intervals in the vertical and horizontal directions, or may be arranged in a staggered pattern or the like. Also, the number of holes is not particularly limited as long as the aperture ratio is within the range described later, and may be appropriately adjusted. For example, it is 1 to 150 holes / cm 2 , preferably 3 to 100 holes / cm 2 , more preferably 5 to 80 holes / cm 2 .

[0045] The aperture ratio of the metal sheet due to the provision of the above holes is preferably 1 to 10%. When the aperture ratio of the metal sheet is 1% or more, the gas generated from the resin body is appropriately discharged to the outside through the holes, and the dimensional change of the laminated structure during high-temperature heating can be appropriately suppressed. Also, by setting it to 10% or less, it is possible to prevent the nonflammability, heat insulation property, etc. of the laminated structure from being impaired due to the provision of the holes. From these viewpoints, the above aperture ratio is more preferably 1 to 9%, and even more preferably 2 to 8%.

[0046] <Glass cloth> The laminated structure of the present invention preferably further includes a glass cloth disposed between the metal sheet and the resin body. By providing the glass cloth, it becomes easier to impart nonflammability to the laminated structure. Also, since the glass cloth has appropriate voids, the gas generated in the resin body is appropriately discharged to the outside through the glass cloth and the holes of the metal sheet. The glass cloth is not particularly limited, and it is preferably composed of glass fibers having a filament diameter of, for example, about 1 to 10 μm. The glass cloth may be woven in any weaving method such as plain weave, twill weave, or satin weave. The basis weight of the glass cloth is not particularly limited, but is preferably 20 to 300 g / m 2 . When the basis weight of the glass cloth is equal to or more than the above lower limit value, it becomes easier to further impart nonflammability to the laminated structure. Also, when it is equal to or less than the above upper limit value, appropriate voids are formed in the glass cloth, and the gas generated in the resin body easily escapes to the outside. From the above viewpoints, the basis weight of the glass cloth is more preferably 20 to 280 g / m 2 , even more preferably 50 to 250 g / m2 It is.

[0047] <Laminated structure> As shown in FIG. 1, the laminated structure of the present invention is preferably a laminated structure 10 composed of a resin body 11 and a metal sheet 12 laminated on one surface of the resin body 11. Here, the metal sheet 12 may be directly laminated on the resin body 11, but is preferably laminated on the resin body 11 via an adhesive layer (not shown). The metal sheet 12 is difficult to ensure adhesiveness to the resin body 11, but can be adhered to the resin body 11 with high adhesive force by means of an adhesive layer.

[0048] Further, as shown in FIG. 2, the laminated structure is preferably a laminated structure 15 in which a glass cloth 13 is provided between the resin body 11 and the metal sheet 12, and the resin body 11, the glass cloth 13, and the metal sheet 12 are provided in this order. Also in the laminated structure 15, the glass cloth 13 may be directly laminated on the resin body 11, but is preferably laminated via an adhesive layer (not shown). Similarly, the metal sheet 12 may be directly laminated on the glass cloth 13, but is preferably laminated via an adhesive layer (not shown). Each of the glass cloth 13 and the metal sheet 12 can be adhered to the resin body 11 and the glass cloth 13 respectively with high adhesive force by using an adhesive layer.

[0049] As the adhesive layer for adhering the metal sheet to the resin body, the metal sheet to the glass cloth, and the glass cloth to the resin body, a known adhesive layer can be used. The adhesive layer may be a hot melt film or an adhesive.

[0050] <Method for manufacturing a laminated structure> The laminated structure of the present invention can be obtained by laminating a resin body on a metal sheet or a laminate of a metal sheet and a glass cloth. For example, when the resin body is a non-foam body, the resin body may be laminated on the metal sheet or the glass cloth while being molded by extrusion molding or the like on the metal sheet or the glass cloth. Alternatively, a laminated structure may be manufactured by laminating a foam or non-foam material and a metal sheet or a laminate of a metal sheet and a glass cloth via an adhesive layer.

[0051] [Method for manufacturing foam] As a method for manufacturing a foam according to a preferred embodiment of the present invention, for example, a method of extruding a resin composition containing a resin, a thermal decomposition type foaming agent, and additives such as a flame retardant optionally blended by an extruder, and then crosslinking and foaming the extruded resin composition can be mentioned. More specifically, it is preferably manufactured by the following steps (1) to (3). Step (1): A step of supplying a resin, a thermal decomposition type foaming agent, and additives such as a flame retardant optionally blended to an extruder, melt-kneading them, and then extruding them from the extruder to obtain a resin composition Step (2): A step of irradiating the resin composition obtained in step (1) with ionizing radiation to crosslink it Step (3): A step of foaming the resin composition crosslinked in step (2) to obtain a foam

[0052] Examples of the extruder used in this manufacturing method include a single-screw extruder and a twin-screw extruder. The resin temperature inside the extruder is preferably 120 to 195°C, more preferably 130 to 170°C. Also, the resin composition extruded from the extruder is preferably in the form of a sheet (resin sheet).

[0053] In step (2), the resin composition obtained in step (1) is irradiated with ionizing radiation to crosslink it. Examples of the ionizing radiation that can be used in step (2) include α-rays, β-rays, γ-rays, electron beams, etc. Among these, electron beams are preferred. The irradiation dose of the ionizing radiation only needs to be able to obtain a desired degree of crosslinking, but is preferably 1 to 10 Mrad, more preferably 3 to 7 Mrad. Since the progress of crosslinking by irradiation with ionizing radiation is affected by the composition of the resin composition, the irradiation dose may be adjusted while measuring the degree of crosslinking.

[0054] In step (3), it is preferable to foam the crosslinked resin composition by heating. The heating temperature during foaming is preferably a temperature equal to or higher than the decomposition temperature of the thermal decomposition type foaming agent. The specific heating temperature is usually 200 to 290 °C, and preferably 220 to 260 °C. Further, in step (3), the foam may be stretched in either one or both of the MD direction and the CD direction after or during foaming.

[0055] Note that the method for producing the foam of the present invention is not limited to the above production method, and it may be produced by other production methods. For example, instead of crosslinking by ionizing radiation, an organic peroxide may be previously blended in the resin composition, and the resin composition may be crosslinked by a method such as heating the resin composition to decompose the organic peroxide. At this time, the resin composition may be foamed while being crosslinked. Further, the foam may not be a crosslinked body, and in that case, step (2) may be omitted.

[0056] <Method of using the laminated structure> The laminated structure of the present invention can be used in various vehicles such as buildings, civil engineering, electronic products, electrical products, and automobiles, but it is preferably used in buildings. The above-mentioned heat generation test is a performance evaluation test related to the certification of Article 2, Paragraph 9 of the Building Standards Law. A test piece with a thickness of 50 mm does not come into contact with ignition and does not catch fire, and the total heat generation amount in 20 minutes is 8 MJ / m 2 It is certified as a non-combustible material by being the following. Therefore, the laminated structure of the present invention can be used as a non-combustible material in buildings and can be suitably used as a building material at various locations in buildings. Specifically, it may be used for roofs, walls, floors, ceilings, etc., or may be used at other locations. Further, the laminated structure of the present invention can be used as a heat insulating material because the resin body is a foam. Therefore, when the resin body is a foam, it can be particularly preferably used in buildings.

[0057] Also, the laminated structure may be used alone or may be used by being laminated on other materials. Examples of the other materials include metal materials such as metal plates. That is, the present invention also provides a structure in which the above laminated structure is laminated on a metal material such as a metal plate. The metal material such as a metal plate may be provided on the surface opposite to the surface on which the metal sheet of the resin body is provided. Therefore, the structure on which the metal material is laminated may be a structure having a metal sheet / resin body / metal material in this order, a structure having a metal sheet / glass cloth / resin body / metal material in this order, or the like.

[0058] In the present invention, by using the above laminated structure by laminating it on a metal plate or the like, it can be more preferably used as a non-combustible material. Further, when the laminated structure of the present invention is laminated and used on a metal plate or the like, it is particularly suitable for use on the roof, wall, floor, ceiling, etc. of a building. The thickness of the metal material such as a metal plate on which the laminated structure is laminated is not particularly limited, but is, for example, about 0.1 to 10 mm, preferably about 0.15 to 4 mm, and more preferably 0.2 to 2 mm. The material of the metal material is not particularly limited, and examples thereof include various steel materials such as galvanized steel sheets, galvannealed steel sheets, and stainless steels.

[0059] Further, the above laminated structure may be adhered to a metal material such as a metal plate via an adhesive layer or a double-sided adhesive tape. Therefore, an adhesive layer or a double-sided adhesive tape may be provided between the resin body and the metal material. The double-sided adhesive sheet includes a base material and adhesive layers provided on both surfaces of the base material. The double-sided adhesive sheet may be used to adhere one adhesive layer to the resin body and the other adhesive layer to the metal material. There is no particular limitation on the adhesive constituting the adhesive layer, and for example, an acrylic adhesive, a urethane adhesive, a rubber adhesive, or the like can be used. The thickness of each adhesive layer is preferably, for example, 1 to 100 μm, and more preferably 5 to 50 μm. In addition, the base material may be a non-woven fabric or various resin films. From the viewpoints of incombustibility, fire resistance, etc., it is better that the basis weight of the base material is small. For example, it is about 5 to 100 g / m 2 , preferably about 10 to 50 g / m 2 .

Examples

[0060] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples at all.

[0061] The measurement methods of each physical property and the evaluation method of the foam are as follows. (1) Crosslinking degree Collect about 100 mg of test pieces from the foam and accurately weigh the mass A (mg) of the test pieces. Next, immerse this test piece in 30 cm of xylene at 120 °C 3 for 24 hours, then filter through a 200-mesh wire mesh to collect the insoluble matter on the wire mesh, vacuum dry it, and accurately weigh the mass B (mg) of the insoluble matter. From the obtained values, the crosslinking degree (mass %) was calculated by the following formula. Crosslinking degree (mass %) = 100 × (B / A) (2) Density The density (apparent density) of the foam was measured in accordance with JIS K 7222. (3) Thickness of the foam Measured with a dial gauge.

[0062] (4) Heat generation test The laminated structures obtained in each example and comparative example were cut out into 99 mm × 99 mm. A double-sided adhesive tape (product name #570E, manufactured by Sekisui Chemical Co., Ltd.) was used to bond a galvanized steel sheet with a thickness of 0.27 mm to the surface of the foam (resin body) side of the cut laminated structure to obtain a test structure. The double-sided adhesive tape is a base material made of pulp non-woven fabric (basis weight 20 g / m 2It had acrylic adhesive layers (thickness: 30 μm) on both sides. At this time, when the test structure was 50 mm, the test structure was used as the test specimen as it was. When the thickness of the test structure exceeded 50 mm, before bonding, the foam was cut and thinned on the side opposite to the metal sheet side, and then bonded to a galvanized steel sheet (thickness: 0.27 mm) via a double-sided adhesive tape, and the test structure adjusted so that the overall thickness became 50 mm was used as the test specimen. Also, when the test structure was less than 50 mm, a non-combustible material (ceramic fiber) was placed under the galvanized steel sheet, and the combination of the non-combustible material and the test structure was used as the test specimen. At this time, the total thickness of the non-combustible material and the test structure was made to be 50 mm.

[0063] For the heat release test, a test equivalent to the performance evaluation test related to the certification of Article 2, No. 9 of the Building Standards Law was conducted. Specifically, the above test specimen was set in the heat release test apparatus with the metal sheet side as the upper surface. At this time, the distance between the test specimen and the ignition was 13 mm. The set test specimen was heated for 20 minutes from the metal sheet side at a radiant heat intensity of 50 kW / m 2 and the total heat release amount was measured with a cone calorimeter in accordance with the test method of ISO-5660. Also, in this test, it was confirmed whether the test specimen came into contact with the ignition due to heating, and when it came into contact with the ignition, it was recorded as 0 mm. Also, when it did not come into contact with the ignition, the distance (shortest distance) between the test specimen after heating and the ignition was measured. Furthermore, the presence or absence of ignition of the test specimen was confirmed.

[0064] (5) Workability The laminated structure was cut to an appropriate size with a cutter knife and attached to the metal surface of the metal duct via a double-sided tape to evaluate the workability. The metal duct had a curved surface portion, and the laminated structure was deformed into a curved shape accordingly. A: The workability was good without the metal surface being torn or unable to be cut well with the cutter knife. B: The metal surface was torn or unable to be cut well with the cutter knife, and the workability was not good.

[0065] Example 1 (Manufacture of Foam) In each of the examples and comparative examples, each component shown in the foam column of Table 1 was put into a single-screw extruder, melt-kneaded at 120° C. and extruded to obtain a resin sheet (resin composition) with a thickness of 2 mm. The resin sheet was crosslinked by irradiating both sides of the resin sheet with an electron beam at an acceleration voltage of 500 kV and an irradiation dose of 5.5 Mrad. Thereafter, the crosslinked resin sheet was heated at 240° C. for 3 minutes by a hot air oven, and foamed by the heating to obtain a foam with a thickness of 5 mm. The surface of the 5-mm foam was heated to 80° C. and sequentially laminated to obtain a 25-mm foam.

[0066] (Manufacture of Laminated Structure) Also, an aluminum sheet with a thickness of 18 μm provided with a large number of regularly arranged circular holes with a diameter of 0.5 mm in parallel, and a glass cloth (product name "EGW110TH", manufactured by Central Glass Fiber Co., Ltd., basis weight 110 g / m 2 ) were prepared. This laminate was obtained by heating and laminating a 30-μm hot melt film (product name "FA-3050", manufactured by Moribe Shoten Co., Ltd.) from the aluminum sheet side at 120° C. A 30-μm hot melt film (product name "FA-3050", manufactured by Moribe Shoten Co., Ltd.) was placed on the glass cloth side surface of the above laminate, and heated from the aluminum sheet side at 120° C. through the hot melt film and laminated with the foam to obtain a laminated structure.

[0067] Examples 2 and 3 The procedure was the same as in Example 1, except that the thickness of the foam obtained in the manufacture of the foam was changed as described in Table 1.

[0068] Examples 4 and 5 The procedure was the same as in Example 1, except that the aperture ratio was changed as described in Table 1 by adjusting the number of holes per unit area.

[0069] Examples 6, 8, and 9 The procedure of Example 1 was repeated, except that the thickness of the aluminum sheet was changed as described in Table 1.

[0070] Example 7 The procedure of Example 1 was repeated, except that the glass cloth was changed to a product name (product name: "EGW210TH", manufactured by Central Glass Fiber Co., Ltd., basis weight 210 g / m 2 ).

[0071] Comparative Example 1 The procedure of Example 1 was repeated, except that an aluminum sheet having no holes was used.

[0072] Comparative Examples 2 and 3 The procedure of Example 1 was repeated, except that the aperture ratio was changed as described in Table 1 by adjusting the number of circular holes per unit area.

[0073] The evaluation results of the foams of each Example and Comparative Example are shown in Table 1.

Table 1

[0074] Details of each component in Table 1 are as follows. LDPE: Manufactured by Ube Maruzen Polyethylene Co., Ltd., product name "522N" Brominated flame retardant: 1,2-bis(2,3,4,5,6-pentabromophenyl)ethane, manufactured by Albemarle Japan Co., Ltd., product name "SAYTEX8010" Antimony trioxide: Manufactured by Nippon Tungsten Co., Ltd., product name "PATOX-M" Zinc stearate: Manufactured by Sakai Chemical Co., Ltd., product name "SZ-2000" Antioxidant: Manufactured by BASF Japan Ltd., product name "Irganox 1010" ADCA: Azodicarbonamide, blowing agent

[0075] The laminated structures of the above examples each include an aluminum sheet and a resin body. In a heat generation test using a cone calorimeter that heats from the aluminum sheet side, a test piece with a thickness of 50 mm did not come into contact with ignition and did not catch fire, and the total heat generation amount in 20 minutes was 8 MJ / m 2 was as follows. Therefore, it had non-combustibility and could suppress dimensional changes during high-temperature heating, and could be recognized as a non-combustible material in the performance evaluation test related to the certification of Article 2, Paragraph 9 of the Building Standards Act. On the other hand, as is clear from the fact that the laminated structure of Comparative Example 1 came into contact with ignition in the heat generation test, the dimensional change during high-temperature heating was large. Also, in Comparative Examples 2 and 3, ignition occurred in the heat generation test, or the heat generation amount became large and non-combustibility could not be imparted, and it could not be recognized as a non-combustible material in the performance evaluation test related to the certification of Article 2, Paragraph 9 of the Building Standards Act.

Explanation of Symbols

[0076] 10, 15 Laminated structure 11 Resin body 12 Metal sheet 13 Glass cloth

Claims

1. Comprising a metal sheet and a resin body, wherein the resin body is a crosslinked foam, the metal sheet has a plurality of holes, the aperture ratio of the metal sheet is 1 to 10%, the diameter of the holes is 0.2 to 0.8 mm, further comprising a glass cloth disposed between the metal sheet and the resin body, The test specimen was set so that the distance from the ignition was 13 mm, and in the heat release test using a cone calorimeter that heats from the metal sheet side at a radiant heat intensity of 50 kW / m ２ in accordance with the test method of ISO-5660, a test specimen with a thickness of 50 mm did not come into contact with the ignition and did not catch fire, and the total heat release amount in 20 minutes was 8 MJ / m ２ The following laminated structure.

2. The laminated structure according to claim 1, wherein the resin constituting the resin body is a thermoplastic resin.

3. The laminated structure according to claim 1 or 2, wherein the resin constituting the resin body contains a polyolefin resin.

4. The laminated structure according to any one of claims 1 to 3, wherein the resin body contains a flame retardant.

5. The laminated structure according to any one of claims 1 to 4, wherein the thickness of the metal sheet is 10 to 100 μm.

6. The laminated structure according to any one of claims 1 to 5, wherein the metal sheet is an aluminum sheet.

7. The basis weight of the glass cloth is 20 to 300 g / m ２ The laminated structure according to any one of claims 1 to 6, wherein the basis weight is 20 to 300 g / m

8. The resin constituting the resin body is at least one selected from the group consisting of polyvinyl chloride resins, silicone resins, acrylic resins, polyurethane resins, polyolefin resins, elastomers, and styrene resins. The laminated structure according to any one of claims 1 to 7.

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