JP5912265B2 - Thermal insulation laminate - Google Patents

Description

  The present invention relates to a heat insulating laminate.

  In general, as one of means for energy saving of a building, heat insulation construction is performed on a concrete wall surface. As a heat insulating material used for heat insulation construction in a reinforced concrete structure or a steel reinforced concrete structure, for example, a foam of a hard synthetic resin such as a phenol foam is often used, such as a heat insulating material for a formwork described in Patent Document 1. .

In addition, as disclosed in Patent Document 2, for example, there is also a mold and heat insulating material using a calcium silicate plate having a density of 0.05 g / cm ^{3 to} 0.20 g / cm ³ .

Japanese Patent No. 2655947 JP 09-88214 A

  However, although the heat insulating material combined with a mold described in Patent Document 1 can obtain a predetermined heat insulating performance, the heat insulating material tends to burn. For this reason, when it uses for the place which receives interior restrictions, such as fire prevention equipment, there exists a problem that post-construction is needed. Moreover, since the heat insulating material for molds described in Patent Document 2 is inorganic, it has excellent incombustibility but is inferior in heat insulating performance. For this reason, there is a problem that the thickness has to be increased, design is restricted, and it is heavy, inconvenient to handle, and inferior in workability.

  Then, this invention aims at providing the heat insulation laminated body which shows the high nonflammability performance while being lightweight.

  That is, the present invention provides the following [1] to [5].

[1] metal layer on the resin foam layer (A) (B), thermal expansion layer containing a foaming or expanding material upon heating (C), and inorganic sheet (D) are stacked in this order, heat expandable layer (C) A heat insulating laminate (noncombustible material ) in which (C) includes an adhesive and 30 to 50 g / m ² of thermally expandable graphite as a material that expands or expands when heated .
[2] The heat insulating laminate according to [1], wherein the total amount of the adhesive and the thermally expandable graphite is 100 to 130 g / m ² in the heat expansion layer (C) .
[3] The heat insulating laminate according to [1] or [2], wherein the total amount of the heat expansion layer (C) is 100 to 380 g / m ² .
[4] The heat insulating laminate (nonflammable material) according to any one of [1] to [3], wherein the adhesive is a vinyl acetate adhesive or an epoxy adhesive .
[5] The heat insulating laminate (noncombustible material) according to any one of [1] to [4], wherein the resin foam layer (A) is a phenol resin foam.
[6] The heat insulating laminate (noncombustible material) according to any one of [1] to [ 5 ], wherein the metal layer (B) is aluminum.
[7] The total calorific value when applying radiant heat of 50 kW / m ² for 20 minutes from the inorganic sheet (D) side is less than 8 MJ / m ² , according to any one of [1] to [ 6 ]. Thermal insulation laminate.
[8] A metal layer (B) is laminated on the resin foam layer (A), and then a material that foams or expands when heated is applied on the metal layer (B) to produce a heat expansion layer (C). Furthermore, an inorganic sheet (D) is laminated, and the heat expansion layer (C) includes an adhesive and 30 to 50 g / m ² of thermally expandable graphite as a material that expands or expands when heated . The manufacturing method of the heat insulation laminated body as described in any one of [ 7 ].

  ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the heat insulation laminated body which shows high nonflammability performance while being lightweight.

It is a schematic cross section which shows one Embodiment of the heat insulation laminated body which concerns on this invention. It is a schematic cross section which shows another embodiment of the heat insulation laminated body which concerns on this invention.

  Hereinafter, preferred embodiments of the heat insulating laminate of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments. In the drawings, the same elements are denoted by the same reference numerals, and some of the reference numerals of the same elements are omitted. The dimensional ratio of each heat insulating laminate is not limited to that shown in the drawings.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of a heat insulating laminate 10 according to the present invention. As shown in FIG. 1, a heat insulating laminate 10 is formed by laminating a metal layer 2, a heat expansion layer 3 containing a material that expands or expands when heated, and an inorganic sheet 4 in this order on a resin foam layer 1. It has a configuration.

  In the heat insulation laminated body which employ | adopted such a structure, by laminating | stacking the metal layer 2 on the resin foam layer 1, high nonflammability performance can be shown, without impairing heat insulation performance. As a result, since the heat insulating performance can be maintained without increasing the thickness of the heat insulating laminate itself, a heat insulating laminate showing high incombustibility while being lightweight can be obtained. However, a heat insulating material used for a concrete wall is strongly required to have a gray to white color similar to concrete. Therefore, the heat insulating laminate 10 employs a configuration in which the heat expansion layer 3 containing a material that expands or expands upon heating and the inorganic sheet 4 are further laminated on the metal layer 2.

  The inventors have found an unexpected function of the heat expansion layer 3 as described below, and have reached the above-described configuration. That is, when the heat insulating material in which the metal layer 2 is laminated on the resin foam layer 1 is used as a finished surface of the concrete wall as it is, a configuration in which a gray or white inorganic sheet 4 is further laminated on the metal layer 2 is considered. It is done. However, when the present inventors use a heat insulating material having such a configuration, when the inorganic sheet 4 or the adhesive between the inorganic sheet 4 and the metal layer 2 burns when heated, the resin foam layer 1 is heated. It was found that the cracked gas generated by the combustion burns and the incombustible performance cannot be obtained. As a result, the inventors have adopted the above configuration based on this finding.

  Hereinafter, each layer will be described in detail.

As the resin foam layer 1, a phenol resin foam, a polyurethane resin foam, a polyisocyanurate resin foam, an epoxy resin foam, a polyethylene resin foam, a polyphenylene resin foam, a polystyrene resin foam, or the like can be used. Among them, a phenol resin foam is used. Is preferred. The thickness of the resin foam layer 1 is preferably 5 to 150 mm, and the density is preferably 20 to 60 kg / m ³ . The resin foam layer 1 may have a resin, inorganic, or paper face material bonded to one or both surfaces of the resin foam described above.

  As the metal layer 2, what processed the metal simple substance into the sheet form, foil shape, plate shape, a vapor deposition film, etc. is mentioned. Moreover, as a kind of metal which comprises the metal layer 2, iron, aluminum, stainless steel, copper, titanium, etc. can be used, and aluminum is preferable from the surface of rust prevention performance, cost, etc. By providing the metal layer 2, when the heat insulating laminate 10 is heated from the inorganic sheet 4 side, the decomposition gas generated by the decomposition of the resin foam layer 1 leaks to the heating surface side (inorganic sheet 4 side). Can be suppressed. One or both sides of the metal layer 2 may be reinforced with glass mesh, glass fiber, ceramic fiber, or the like. The thickness of the metal layer 2 can be 1 μm to 1 mm, preferably 2 μm to 500 μm, and more preferably 4 μm to 200 μm. When the thickness of the metal layer 2 is less than 1 μm, it functions to prevent the decomposition gas of the resin foam layer 1 from leaking to the heating surface side when the heat insulating laminate 10 is heated from the inorganic sheet 4 side. It becomes insufficient. Further, when the thickness of the metal layer 2 is larger than 1 mm, processing such as cutting becomes inconvenient.

  As a method of laminating the metal layer 2 on the resin foam layer 1, a method of bonding using an adhesive may be used, or a method of mechanically bonding using a rivet or the like may be used. . Examples of adhesives include vinyl acetate adhesives, urethane adhesives, epoxy adhesives, acrylic adhesives, silicone adhesives, rubber adhesives, phenol resin adhesives, melamine resin adhesives, Adhesives such as cement adhesives and water glass adhesives can be used.

The heat expansion layer 3 is a layer containing a material that foams or expands when heated. The heat expansion layer 3 functions as a heat insulating layer by foaming or expanding during heating, and prevents heat conduction from the inorganic sheet 4 side to the resin foam layer 1 side when the inorganic sheet 4 side is heated. It can prevent that 1 becomes high temperature. Thereby, since the decomposition gas generated from the resin foam layer 1 is dramatically reduced and the resin foam layer 1 is hardly combusted, the heat generation amount of the heat insulating laminate 10 can be significantly reduced. Examples of the material that foams or expands when heated include melamine compounds such as melamine, N-nitroso compounds such as urea, thiourea, dinitrosopentamethylenetetramine, N, N-dinitroso-N, N-dimethylterephthalamide, Azo compounds such as azobisisobutyronitrile, azodicarbonamide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, sulfone hydrazide compounds such as p, p-oxy-bis (benzenesulfonyl hydrazide), chlorinated paraffin, or these Derivatives, thermally expandable graphite, leechite, nacre, obsidian and the like. These may be used alone or in combination of two or more. Among these, melamine-based compounds such as melamine and heat-expandable graphite are preferable and heat-expandable graphite is more preferable because of easy handling and availability. Here, “thermally expandable graphite” refers to graphite having the property of expanding upon heating. As the heat-expandable graphite, one having an expansion start temperature of 160 to 300 ° C. is preferably used, and heat-expandable graphite exhibiting an expansion degree of 100 to 300 cc / g is preferably used. The expansion start temperature here refers to the temperature at which the temperature is increased from 100 ° C. at + 5 ° C./min and the volume becomes 1.1 times. Moreover, the expansion degree said here means the volume (cc) per gram at the time of hold | maintaining at 1000 degreeC for 10 second. The amount of the material which foams or expands upon heating is preferably 5 to 200 g / ^{m 2,} more preferably 15 to 100 / ^{m 2,} more preferably 20 to 80 g / ^{m 2.} If it is less than 5 g / m ^2, the effect of foaming or expanding during heating to form a heat insulating layer is insufficient. On the other hand, when the amount is more than 200 g / m ² , the non-flammable performance becomes insufficient because it expands too much at the time of heating and the shape of the heat expansion layer 3 is not maintained and collapses.

  As a means for producing the heating expansion layer 3, a method in which a composition in which a material that foams or expands upon heating is mixed with the above-described adhesive may be sandwiched between the metal layer 2 and the inorganic sheet 4, or heating may be used. A method in which a material that is sometimes foamed or expanded into a sheet shape by a known method may be sandwiched between the metal layer 2 and the inorganic sheet 4 by an adhesive or a mechanical joining method.

  In addition to these components, the heat-expandable layer 3 contains various additives such as a filler, a diluent, a flame retardant, and a carbonizer as necessary within a range that does not reduce the effects of the present invention. It may be included. Examples of fillers include titanium dioxide, silicon dioxide, aluminum oxide, zinc oxide, calcium carbonate, sodium carbonate, barium carbonate, calcium sulfate, barium sulfate, calcium silicate, magnesium silicate, fly ash, silica fume, talc, clay, Examples include clay, kaolin, shirasu, mica, pearlite, diatomaceous earth, glass fiber, glass flake, quartz sand, quartzite powder, and sand. Examples of the diluent include benzene, toluene, xylene, mineral spirit, acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, and water. Examples of the flame retardant include brominated flame retardants such as tetrabromobisphenol A, decabromodiphenyl ether, hexabromocyclododecane, tribromophenol, ethylene bistetrabromophthalimide, brominated polystyrene, ethylene bispentabromodiphenyl, and chlorine. Chlorinated flame retardants such as chlorinated paraffin, chlorinated polyethylene, chlorinated alicyclic compounds, and chlorinated phosphoric esters, inorganic phosphorus flame retardants such as red phosphorus, phosphorus trichloride, phosphorus pentachloride, ammonium phosphate, and ammonium polyphosphate , Organophosphorous flame retardants such as phosphate esters, antimony flame retardants such as antimony trioxide and antimony pentoxide, and aluminum hydroxide, magnesium hydroxide, borate compounds, molybdenum compounds, tin compounds, metal oxides, etc. Inorganic flame retardants. In addition, examples of the carbonizing agent include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, trimethylolpropane and other polyhydric alcohols, starch, and casein.

The inorganic sheet 4 is a sheet mainly composed of an inorganic substance excluding a single metal. By providing the inorganic sheet 4, the shape of the heat expansion layer 3 can be maintained even when the heat insulating laminate 10 is heated. Further, since the heat insulating laminate 10 may be used as a finished surface as it is, it is required to have a gray to white color similar to concrete, and the L ^* value defined in JIS Z8729 is 70 for the color. That is essential. The inorganic sheet 4 is preferably free from metallic luster. Examples of the material of the inorganic sheet 4 include titanium dioxide paper, silicon dioxide paper, aluminum oxide paper, zinc oxide paper, calcium carbonate paper, barium carbonate paper, calcium sulfate paper, barium sulfate paper, calcium silicate paper, and magnesium silicate paper. Examples thereof include paper, aluminum hydroxide paper, magnesium hydroxide paper, fly ash paper, talc paper, kaolin paper, and glass paper. The inorganic sheet 4 may contain organic components such as pulp and other organic fibers and a binder for forming the sheet itself. Moreover, 50 micrometers-1 mm are preferable, and, as for the thickness of the inorganic material sheet 4, 100 micrometers-500 micrometers are more preferable. When the thickness of the inorganic sheet 4 is smaller than 50 μm, it becomes easy to break against tension, and the effect of maintaining the shape of the heat expansion layer 3 cannot be obtained. On the other hand, when the thickness of the inorganic material sheet 4 is larger than 1 mm, the calorific value at the time of heating becomes large, and the nonflammability performance is poor.

  As mentioned above, although preferred embodiment of the manufacturing method of the heat insulation laminated body 10 which concerns on this invention was described in detail, this invention is not limited to the said embodiment. FIG. 2 is a schematic cross-sectional view showing another embodiment of the heat insulating laminate according to the present invention. As a modification of the heat insulating laminate 10, as shown in FIG. 2, the metal layer 2, the heat expansion layer 3, and the inorganic sheet 4 are laminated on both surfaces of the resin foam layer 1 in order from the resin foam layer 1. The heat insulation laminated body 20 which has is mentioned.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

In addition, the raw material used by the Example and the comparative example is as follows.
Resin foam layer: Phenol resin foam Asahi Kasei building material, Neoma foam, 25 mm thickness, density 40 kg / m ³ , polyethylene terephthalate face material adhesive on both sides (resin foam layer-metal layer):
Epoxy adhesive 1 Konishi, EP431C
Epoxy adhesive 2 Cemedine, EP20
Ammonium polyphosphate Clariant Japan, AP422
Metal layer: Metal layer (AL) 30 μm thick aluminum foil Metal layer (GFAL) 20 μm thick aluminum foil, glass fiber reinforced 85 g / m ²
Heat expansion layer: Vinyl acetate adhesive J Chemical, Isocyanic modified vinyl acetate adhesive
Thermally expanded graphite Suzuhiro Chemical, GREP-EG, expansion start temperature 200-220 ° C., expansion 180-230 cc / g
Calcium carbonate Nitto Flour Industries, SS # 30
Kaolin Hayashi Kasei, ASP400P
Magnesium silicate Sakai Industry, Sepiolite
Zinc borate Hayakawa Shoji, Fire Break ZB
Inorganic sheet: Inorganic sheet 1 Grandex, non-combustible paper (GP), the main component is magnesium silicate, color value L ^* = 83.5, no metallic luster
Inorganic sheet 2 Olivest, GT-2, the main component is magnesium silicate, color value L ^* = 82.9, no metallic luster
Inorganic sheet 3 Awa Paper, inorganic sheet prototype, color value L ^* = 94.4, no metallic luster

  For Examples 1 to 10 and Comparative Examples 2 to 4, Table 1 was similarly cut out to 100 mm × 100 mm using the type and amount of adhesive shown in Table 1 on one side of the phenol resin foam cut out to 100 mm × 100 mm. A metal layer of the type shown in FIG. Furthermore, the heat expansion layer was apply | coated on the metal layer with the mixing | blending shown in Table 1, and the inorganic substance sheet shown in Table 1 cut out to 100 mm x 100 mm was adhere | attached on it. In the composition of the heat expansion layer, those using a vinyl acetate adhesive were added with an appropriate amount of water as a diluent to improve the fluidity so that they could be easily applied. Thereafter, the adhesive and the heat expansion layer were cured to complete the heat insulating laminate.

  About the comparative example 1, the inorganic sheet | seat shown in Table 1 cut out to 100 mm x 100 mm was apply | coated to the phenol resin foam on the single side | surface of the phenol resin foam cut out to 100 mm x 100 mm on the phenol resin foam by the mixing | blending shown in Table 1. Glued. For the heat-expandable layer, an appropriate amount of water was added as a diluent to improve the fluidity so that it could be easily applied. Thereafter, the adhesive and the heat expansion layer were cured to complete the heat insulating laminate.

(Nonflammable performance)
About the heat insulation laminated body obtained by the Example and the comparative example, the emitted-heat amount measurement was performed and hard to generate | occur | produce these heat | fever (nonflammability performance) was evaluated. Specifically, radiant heat of 50 kW / m ² was applied to the heat insulating laminate from the inorganic sheet side, and the total calorific value of the heat insulating laminate for 20 minutes after the start of heating was measured with a cone calorimeter. If the total calorific value for 20 minutes is less than 8 MJ / m ² , it will be nonflammable (pass: ○), and if the total calorific value for 20 minutes is 8 MJ / m ² or more, it will be nonflammable. Not included (failed: x).

As a result of the calorific value measurement, the total calorific value was less than 8 MJ / m ² for Examples 1 to 10 and passed, but the total calorific value for Comparative Examples 1 to 4 greatly exceeded 8 MJ / m ^2. It was a failure.

  DESCRIPTION OF SYMBOLS 1 ... Resin foam layer, 2 ... Metal layer, 3 ... Heat expansion layer, 4 ... Inorganic sheet, 10, 20 ... Heat insulation laminated body.

Claims (8)

On the resin foam layer (A), a metal layer (B), a heat expansion layer (C) containing a material that expands or expands when heated, and an inorganic sheet (D) are laminated in this order ,
The heat-insulating laminate, wherein the heat-expandable layer (C) includes an adhesive and 30 to 50 g / m ² of heat-expandable graphite as a material that foams or expands when heated . In the heat-expandable layer (C), the total amount of the adhesive and the thermally expandable graphite is 100 to 130 g / m. ² The heat insulation laminated body of Claim 1 which is. The total amount of the heat expansion layer (C) is 100 to 380 g / m. ² The heat insulating laminate according to claim 1 or 2, wherein The heat insulating laminate according to any one of claims 1 to 3, wherein the adhesive is a vinyl acetate adhesive or an epoxy adhesive. The said resin foam layer (A) is a heat insulation laminated body as described in any one of Claims 1-4 which is a phenol resin foam. The said metal layer (B) is a heat insulation laminated body as described in any one of Claims 1-5 which is aluminum. Wherein a inorganic sheet gross calorific value of less than 8 MJ / ^{m 2} when given radiant heat 20 min 50 kW / ^{m 2} from (D) side, the heat insulating laminate according to any one of claims 1 to 6 . A metal layer (B) is laminated on the resin foam layer (A), and then a material that foams or expands when heated is applied onto the metal layer (B) to produce a heat-expandable layer (C), and further an inorganic sheet (D) is laminated,
The heating expansion layer (C) is an adhesive, and a 30 to 50 g / m ² of the thermally expandable graphite as a material which foams or expands upon heating, according to any one of claims 1-7 Manufacturing method of heat insulation laminated body.

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