Laminated structure, and method for manufacturing a laminated structure

Abstract

A laminated structure is provided in which a heat-absorbing layer, a thermal foaming layer, and a decorative layer are laminated in that order on a base material, and the laminated structure is fixed to a specific area using fasteners, thereby enabling weight reduction by making the thickness thinner, and providing a laminated structure with excellent fire resistance by suppressing the detachment of the carbonized heat insulating layer and the decorative layer formed by thermal foaming in the event of a fire. [Solution] The present invention relates to a laminated structure in which a heat-absorbing layer, a heat-foaming layer, and a decorative layer are laminated in that order on a base material, wherein the base material is an axial base material with a polygonal cross-section, the heat-absorbing layer is formed from a heat-absorbing composition containing a binder and one or more selected from inorganic acids, hydroxide compounds, and hydrated compounds, the decorative layer is the outermost layer, and in a region where the distance from each corner of the decorative layer is 40% or less of the length of one side of the base material in the cross-sectional direction, a fastener is pressed in from the decorative layer toward the heat-absorbing layer to a thickness of 30% or more but less than 100% of the thickness of the heat-absorbing layer, and the fastener does not reach the organic base material.

Description

[Technical Field]

[0001] The present invention relates to a laminated structure in which a heat-absorbing layer, a thermal foaming layer, and a decorative layer are laminated in that order on an organic substrate, and to a method for manufacturing the laminated structure. [Background technology]

[0002] Traditionally, concrete has been widely used for the structural framework of buildings (columns, beams, walls, floors, and foundations).

[0003] While concrete structures like these generally have a lifespan of around 50 years, they can be damaged and deteriorated more quickly due to disasters such as earthquakes. Furthermore, because concrete itself has a large mass, there are concerns that it could be a contributing factor to human casualties during disasters.

[0004] Organic substrates such as wood-based and plastic-based materials are being used as alternatives to concrete in various structures. In particular, wood-based materials such as CLT (Cross Laminated Timber) and fiber-reinforced plastic-based materials are attracting attention for their use in various structural components due to their excellent specific strength.

[0005] However, organic substrates are prone to combustion, deformation, and loss of strength when exposed to high temperatures. Therefore, fire resistance is required to withstand fires that occur during disasters.

[0006] For example, if organic materials are used in the structural frame of a building, the heat from a fire could cause the organic materials to burn or deform, significantly reducing their strength and potentially leading to the collapse of the building. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2008-031802 [Patent Document 2] Japanese Patent Publication No. 2020-118022 [Overview of the project] [Problems that the invention aims to solve]

[0008] Patent Document 1 describes covering a wooden structural body with a heat-expandable fire-resistant coating using an adhesive and a stapler.

[0009] However, in Patent Document 1, since the staples reach the wooden structure itself, when the temperature rises due to fire or other reasons, heat is transferred to the wooden structure through the staples, which may accelerate the temperature rise of the wooden structure and lead to a decrease in fire resistance.

[0010] Furthermore, when the heat-expandable fire-resistant coating expands due to heat, the staples may come loose from the wooden structure, potentially causing the heat-expandable fire-resistant coating to become unsecured and fall off.

[0011] Patent Document 2 describes fire-resistant wood having a prismatic core made of wood material, a heat buffer, a fire-resistant material, and a finishing material. Figure 2 of Patent Document 2 shows that the finishing material and the fire-resistant material (foamed fire-resistant coating) are fixed to the heat buffer (steel material) part by fastening members.

[0012] In Patent Document 2, heat is transferred to the prismatic core material made of wood through the fastening member and thermal buffer (steel), which may lead to a decrease in fire resistance. In addition, the thermal buffer increases the thickness of the wood, which may encroach on the living space. [Means for solving the problem]

[0013] Therefore, as a result of intensive studies to solve the above problems, the present inventors have obtained a heat-absorbing layer, a thermal foaming layer, and a decorative layer having a specific density, which are obtained by using a heat-absorbing composition containing a specific raw material on an organic substrate having a specific shape, and are laminated in this order. In forming the laminated structure, a laminated structure fixed using a fixture in a specific range of regions can reduce the thickness, thereby achieving weight reduction. At the time of a fire, a carbonized heat-insulating layer formed by the thermal foaming of the thermal foaming layer and the detachment of the decorative layer are suppressed, and a laminated structure excellent in fire resistance has been found, leading to the completion of the present invention.

[0014] That is, the present invention has the following features. 1. A laminated structure in which a heat-absorbing layer, a thermal foaming layer, and a decorative layer are laminated in this order on a substrate, wherein the substrate is an axially-shaped substrate having a polygonal cross-section, the heat-absorbing layer is formed by a heat-absorbing composition containing a binder and at least one selected from inorganic acids, hydroxide compounds, and hydrated compounds, the decorative layer is the outermost layer, and in a region where the distance from each corner of the decorative layer is 40% or less of the length of one side of the substrate in the cross-sectional direction, a fixture is press-fitted from the decorative layer toward the heat-absorbing layer at 30% or more and less than 100% of the thickness of the heat-absorbing layer, and the fixture does not reach the substrate. 2. The laminated structure according to 1, wherein the inorganic acid contains boric acid. 3. The laminated structure according to 1, wherein the binder is a thermosetting resin. 4. The laminated structure according to 1, wherein the substrate is an organic substrate. 5. The laminated structure according to 4, wherein the organic substrate is a wood substrate and / or a plastic substrate. 6. A method for manufacturing the laminated structure according to any one of 1 to 5, wherein after laminating the heat-absorbing layer, the thermal foaming layer, and the decorative layer in this order on the substrate, the fixture is driven into the decorative layer and fixed to the heat-absorbing layer.

Advantages of the Invention

[0015] The laminated structure of the present invention can be made lighter by reducing its thickness, and in the event of a fire, it suppresses the detachment of the carbonized insulation layer and the decorative layer formed by the thermal expansion of the thermal foam layer, exhibiting excellent fire resistance and being useful. [Brief explanation of the drawing]

[0016] [Figure 1] This is a schematic diagram showing an example of the manufacturing process for the laminated structure of the present invention (Example 1). [Figure 2] This is an example of a cross-sectional view showing the laminated structure of the present invention (Example 1). [Figure 3] This is a schematic diagram showing an example of the manufacturing process for the laminated structure of the present invention (Example 2). [Figure 4] This is an example of a cross-sectional view showing the laminated structure of the present invention (Example 2). [Figure 5] This is a schematic diagram showing an example of the manufacturing process for the laminated structure of the present invention (Example 3). [Figure 6] This is an example of a cross-sectional view showing the laminated structure of the present invention (Example 3). [Figure 7] This is an example of a cross-sectional view showing a laminated structure (Comparative Example 1). [Figure 8] This is an example of a cross-sectional view showing a laminated structure (Comparative Example 2). [Explanation of Symbols]

[0017] P: Organic base material A: Heat-absorbing layer (Heat-absorbing layer (A), Heat-absorbing layer (A-1), Heat-absorbing layer (A-2)) B: Endothermic layer (endothermic layer (B)) C: Thermal foam layer D: Makeup layer E: Dowel material F: Seam G, G1, G2, G3, G4, G5, G6: Fixation with long shaft fixture (fixture) H: Fixation with adhesive [Modes for carrying out the invention]

[0018] The following describes embodiments for carrying out the present invention.

[0019] [Laminated structure] The present invention relates to a laminated structure in which a heat-absorbing layer, a heat-foaming layer, and a decorative layer are laminated in that order on a substrate, wherein the substrate is an axial substrate with a polygonal cross-section, the heat-absorbing layer is formed from a heat-absorbing composition containing a binder and one or more selected from inorganic acids, hydroxide compounds, and hydrated compounds (these are collectively referred to as "heat-absorbing compounds," and hydrated boric acid and / or hydrate borates are collectively referred to as "boric acid hydrate, etc."), the decorative layer is the outermost layer, and in a region where the distance from each corner of the decorative layer is 40% or less of the length of one side of the substrate in the cross-sectional direction, a fixing device is pressed in from the decorative layer toward the heat-absorbing layer to a thickness of 30% or more but less than 100% of the thickness of the heat-absorbing layer, and the fixing device does not reach the substrate. The laminated structure of the present invention can protect the substrate from fire and other disasters by a carbonized insulation layer formed by the foaming of the heat-foamed layer during a fire, and furthermore, it can suppress the detachment of the decorative layer and exhibit excellent fire resistance. In particular, the heat-foamed layer and the outermost decorative layer are usually fixed using adhesives or fasteners (nails, screws, etc.), but during a fire, the temperature rises and the fixing ability (adhesion) of adhesives may deteriorate, and with fasteners, the foaming of the heat-foamed layer may cause the fasteners to come loose (fall off), which may cause the carbonized insulation layer (heat-foamed layer) and decorative layer to detach, reducing the fire resistance performance. However, in the case of the laminated structure of the present invention, the heat-absorbing layer is obtained from a heat-absorbing composition containing specific raw materials, and the distance from each corner of the outermost decorative layer is a specific region relative to the length of one side of the base material in the cross-sectional direction, and the fixing device is pressed in (but not reached) from the decorative layer toward the heat-absorbing layer up to a specific range of the thickness of the heat-absorbing layer, thereby preventing it from falling out due to the foaming of the heat-foamed layer even in the event of a fire, etc., the heat-foamed layer and the decorative layer are firmly fixed, the detachment of the carbonized insulation layer (heat-foamed layer) and the decorative layer is suppressed, excellent fire resistance can be achieved, and at the same time, weight reduction can be achieved. Furthermore, because the fasteners do not reach the substrate, heat conduction to the substrate is suppressed, thereby suppressing the temperature rise of the substrate and resulting in excellent fire resistance. If the fasteners reach the substrate, heat is conducted to the substrate through the fasteners, reducing the fire resistance, which is undesirable.

[0020] Furthermore, the effects of the present invention can be particularly demonstrated when the substrate is an organic substrate. For this reason, the following description of embodiments will focus on the case where the substrate is an organic substrate, but the substrate is not limited to an organic substrate; for example, the substrate may be an inorganic substrate, etc. Specifically, examples of the substrate include inorganic substrates such as metal substrates and cement substrates, organic substrates such as wood substrates, plastic substrates, fiber-reinforced plastic substrates, paper substrates, and fiber-reinforced plastic substrates, or substrates that combine these. In the present invention, organic substrates such as wood substrates, plastic substrates, fiber-reinforced plastic substrates, paper substrates, and fiber-reinforced plastic substrates are particularly preferred, and among these, from the viewpoint of strength and lightness, it is preferable that the organic substrate is a wood substrate and / or a plastic substrate (wood substrate, plastic substrate, and fiber-reinforced plastic substrate, or a substrate that combines these).

[0021] [Endothermic layer] [Heat-absorbing layer (A)] The heat-absorbing layer is formed from a heat-absorbing composition containing a binder and a heat-absorbing compound (for example, boric acid, boric acid hydrate, etc.). By using the aforementioned binder, the endothermic compound (e.g., boric acid, boric acid hydrate, etc.) can be immobilized, and an endothermic layer with excellent heat absorption properties and lightweight properties can be formed. Furthermore, the heat-absorbing layer is formed from a heat-absorbing composition containing a binder and a heat-absorbing compound (for example, boric acid, boric acid hydrate, etc.), and here the heat-absorbing layer may be referred to as "heat-absorbing layer (A)". By using the heat-absorbing layer (A), in addition to fire resistance, it is possible to reduce the weight of the entire laminated structure, which is useful.

[0022] The heat-absorbing layer can be one that exhibits a heat-absorbing effect when the temperature rises. Such a heat-absorbing layer, through a synergistic effect with the heat-foaming layer described later, prevents heat transfer to the organic substrate (described later) when the temperature rises, such as during a fire, and plays a role in maintaining the shape of the organic substrate. As a result, the laminated structure in which the organic substrate is laminated (covered) in the order of the heat-absorbing layer, the heat-foaming layer, and the decorative layer becomes useful because the heat-absorbing effect of the heat-absorbing layer improves fire resistance and other properties.

[0023] (Binder) Examples of the aforementioned binders include organic binders and inorganic binders. From the viewpoint of weight reduction, manufacturability, and processability, organic binders are preferred, and from the viewpoint of heat absorption, inorganic binders are preferred. Among organic binders, thermosetting resins are particularly preferred.

[0024] (Organic binder) Examples of the organic binders include polyester resins, unsaturated polyester resins, vinyl ester resins, vinyl acetate resins, alkyd resins, epoxy resins, acrylic resins, acrylic silicone resins, urethane resins, silicone resins, phenolic resins, melamine resins, polycarbonate resins, fluororesins, acrylic vinyl acetate resins, acrylic urethane resins, acrylic epoxy resins, and ethylene vinyl acetate resins. Furthermore, these resins may be those made from biomass raw materials or resins modified with biomass raw materials. Among these, those obtained from polyols and isocyanates (the urethane resin obtained by reaction and curing), or those obtained from unsaturated polyesters and / or vinyl esters and unsaturated monomers (the unsaturated polyester resin and / or vinyl ester resin obtained by reaction and curing) are preferred, and in particular, those obtained from unsaturated polyesters and unsaturated monomers (the unsaturated polyester resin obtained by reaction and curing) are preferred. The unsaturated polyester resin is useful because it can be made thinner.

[0025] (Polyol) Examples of the aforementioned polyols include polyester polyols, polyether polyols, polycarbonate polyols, polylactone polyols, polybutadiene polyols, polypentadiene polyols, castor oil, castor oil-based polyols, and one or more of these can be used.

[0026] The hydroxyl value of the polyol in the present invention is not particularly limited, but is preferably 50 mg KOH / g or more and 500 mg KOH / g or less. The hydroxyl value is a value expressed by the number of mg of potassium hydroxide equivalent to the hydroxyl groups contained in 1 g of the sample, and is measured according to JIS K 1557-1:2007 Plastics - Polyurethane raw material polyol test method - Part 1: Method for determining hydroxyl value. The hydroxyl value of polyols is the value measured for all polyol mixtures.

[0027] (Isocyanate) The isocyanate has two or more isocyanate groups in one molecule and reacts with the polyol to form a molded product. Various isocyanates known in the field of polyurethanes can be used.

[0028] Examples of the isocyanates include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aromatic aliphatic diisocyanates, and derivatives of these obtained by alohanate formation, biuret formation, dimerization (urethidione), trimerization (isocyanurate), adductation, carbodiimide reaction, etc., as well as mixtures thereof, and copolymers of these with monomers that can be copolymerized. These can be used individually or in combination of two or more types.

[0029] In the present invention, it is preferable that the isocyanate index is 100 to 500 (more preferably 105 to 400, and even more preferably 110 to 300). By mixing the polyol and the isocyanate within this range, a urethane resin having excellent heat resistance and a heat-absorbing layer (heat-absorbing layer (A)) using the urethane resin can be obtained. The isocyanate index is expressed as 100 times the value obtained by dividing the equivalent number of isocyanate groups in the isocyanate by the total equivalent number of active hydrogens in the active hydrogen-containing component (polyol). Furthermore, water generated from endothermic compounds, as described later, shall not be included in the calculation of the active hydrogen-containing components used in the isocyanate index described above. Examples of such water include the crystal water or adsorbed water of inorganic acids (e.g., boric acid) and hydroxide compounds described later, and the hydrated water of hydrated compounds (e.g., boric acid hydrate), as described later.

[0030] (Unsaturated polyester) Examples of the unsaturated polyester include those produced by the esterification reaction of a polyhydric alcohol and a polybasic acid.

[0031] Examples of the aforementioned polyhydric alcohols include alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and neopentyl glycol, as well as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, 1,6-hexanediol, ester glycol, 1,4-cyclohexanedimethanol, and 1,3-butanediol, which can be used individually or in combination of two or more.

[0032] Examples of the aforementioned polybasic acids include unsaturated polybasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and citraconic acid. Phthalic acid (orthophthalic acid), isophthalic acid, terephthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, trimellitic acid, pyromellitic acid, etc., can also be used in combination, and one or more of these can be used.

[0033] (Vinyl ester) Examples of the vinyl ester include bisphenol A type vinyl ester, novolac type vinyl ester, bromination type vinyl ester, and specially modified vinyl ester, and one or more of these can be used. Among these, bisphenol A type vinyl ester is particularly preferred from the viewpoint of stable supply and cost.

[0034] (Unsaturated monomer) Examples of the unsaturated monomers include (meth)acrylic acid ester monomers such as methyl (meth)acrylate, aromatic monomers such as styrene, methylstyrene, and divinylbenzene, and one or more of these can be used. Among these, styrene and methyl methacrylate are particularly preferred from the viewpoint of curability.

[0035] In the present invention, the mixing ratio of the unsaturated polyester and / or vinyl ester to the unsaturated monomer is preferably 10 to 200 parts by mass of the unsaturated monomer, and more preferably 20 to 180 parts by mass, per 100 parts by mass of the unsaturated polyester and / or vinyl ester. By mixing the unsaturated polyester and / or vinyl ester and the unsaturated monomer within this range, and mixing an initiator or the like as needed, an unsaturated polyester resin and / or vinyl ester resin having excellent heat resistance, and a heat-absorbing layer (heat-absorbing layer (A)) using the unsaturated polyester resin and / or vinyl ester resin can be obtained.

[0036] (endothermic compound) The heat-absorbing layer is characterized by being formed from a heat-absorbing composition comprising a binder and one or more (heat-absorbing compounds) selected from the inorganic acid, the hydroxide compound, and the hydrate compound. The heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.) is a component that imparts heat-absorbing properties. In addition to its heat-absorbing performance, the heat-absorbing layer contains a heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.), which causes the heat-absorbing layer to expand slightly due to heat such as fire, making it more difficult for the fastener to come off.

[0037] Examples of the inorganic acid include boric acid, phosphoric acid, sulfuric acid, sulfurous acid, nitric acid, silicic acid, and carbonic acid. Examples of the boric acid include boric acid, metaboric acid, orthoboric acid, diboric acid, tetraboric acid, octaboric acid, and one or more of these can be used. From the viewpoint of endothermic properties and fire resistance, the content of the boric acid is preferably 80% by mass or more of the total inorganic acid, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass. In other words, it is particularly preferable that the inorganic acid contains only boric acid.

[0038] Examples of the hydroxide compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum hydroxide, titanium hydroxide, vanadium hydroxide, manganese hydroxide, iron hydroxide, nickel hydroxide, copper hydroxide, zinc hydroxide, zirconium hydroxide, tin hydroxide, etc., and one or more of these can be used. In the present invention, from the viewpoint of endothermic properties, magnesium hydroxide, aluminum hydroxide, etc. are preferred, and aluminum hydroxide is more preferred. From the viewpoint of endothermic properties and fire resistance, the content of aluminum hydroxide is preferably 80% by mass or more of the total hydroxide compound, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass. In other words, it is particularly preferred that the hydroxide compound contains only aluminum hydroxide.

[0039] As the hydrated compound, one or more can be selected from, for example, hydrates or inorganic salts of inorganic acids such as boric acid, sulfuric acid, sulfite, phosphoric acid, nitric acid, silicic acid, and carbonic acid; hydrates of organic salts such as benzoic acid, phthalic acid, maleic acid, succinic acid, salicylic acid, citric acid, acetic acid, oxalic acid, and sulfonic acid; and hydrates of chloride salts, bromide salts, iodide salts, hydroxide salts, etc. Furthermore, as the aforementioned metal, one or more selected from sodium, aluminum, calcium, zinc, manganese, lanthanum, titanium, zirconium, iron, cobalt, nickel, magnesium, and copper can be used.

[0040] From the viewpoint of endothermic properties, the hydrated compound preferably contains boric acid hydrate and / or borate hydrate (such as boric acid hydrate). From the viewpoint of endothermic properties and fire resistance, the content of boric acid hydrate, etc. is preferably 80% by mass or more of the total hydrated compound, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass. In other words, it is particularly preferable that the hydrated compound contains only boric acid hydrate, etc.

[0041] Examples of the boric acid hydrates include boric acid, metaboric acid, orthoboric acid, diboric acid, tetraboric acid, and octaboric acid, and one or more of these can be used. Furthermore, examples of the borate hydrates include hydrates of borate salts such as lithium salt, potassium salt, sodium salt, rubidium salt, cesium salt, magnesium salt, calcium salt, barium salt, zinc salt, aluminum salt, cobalt salt, and zirconium salt, and one or more of these can be used. More specifically, for example, boric acid monohydrate, boric acid dihydrate, boric acid trihydrate, lithium borate decahydrate, lithium metaborate dihydrate, lithium metaborate octahydrate, tetraborate lithium trihydrate, tetraborate lithium pentahydrate, tetraborate dilithium trihydrate, lithium perborate monohydrate, potassium borate dihydrate, potassium borate tetrahydrate, potassium metaborate 1.5hydrate, potassium perborate monohydrate, tetraborate potassium tetrahydrate, tetraborate potassium octahydrate, tetraborate potassium decahydrate, tetraborate dipotassium tetrahydrate, tetraborate potassium tetrahydrate, tetraborate sodium One or more of the following can be used: thorium pentahydrate, sodium tetraborate decahydrate, disodium octaborate tetrahydrate, sodium perborate monohydrate, sodium perborate tetrahydrate, rubidium borate decahydrate, cesium borate decahydrate, magnesium borate decahydrate, magnesium metaborate octahydrate, calcium borate hexahydrate, calcium borate decahydrate, calcium tetraborate tetrahydrate, zinc borate 3.5hydrate, zinc borate hexahydrate, barium borate decahydrate, barium metaborate monohydrate, barium metaborate dihydrate, etc. In particular, from the viewpoint of endothermic properties, one or more of the boric acid hydrates are preferred, selected from boric acid monohydrate, sodium tetraborate pentahydrate, and sodium tetraborate decahydrate.

[0042] Furthermore, the endothermic composition may also contain, as the hydrated compound, one or more selected from sulfate hydrates, sulfite hydrates, phosphate hydrates, nitrate hydrates, acetate hydrates, chloride salt hydrates, and hydroxide salt hydrates, together with or in place of the boric acid hydrate, etc. These hydrates specifically include, for example, sulfate hydrates such as ammonium aluminum sulfate dodecahydrate, sodium aluminum sulfate dodecahydrate, aluminum sulfate heptahydrate, aluminum sulfate 18hydrate, aluminum sulfate heptahydrate, aluminum sulfate decahydrate, aluminum sulfate hexahydrate, potassium aluminum sulfate dodecahydrate, iron sulfate heptahydrate, iron sulfate nipunahydrate, potassium iron sulfate dodecahydrate, magnesium sulfate heptahydrate, sodium sulfate decahydrate, nickel sulfate hexahydrate, zinc sulfate heptahydrate, beryllium sulfate tetrahydrate, zirconium sulfate tetrahydrate, etc.; sulfite hydrates such as zinc sulfite dihydrate, sodium sulfite heptahydrate, etc.; aluminum phosphate dihydrate, cobalt phosphate octahydrate, magnesium phosphate octahydrate, magnesium ammonium phosphate hexahydrate, Examples include hydrates of phosphates such as magnesium hydrogen phosphate trihydrate, magnesium hydrogen phosphate heptahydrate, zinc phosphate tetrahydrate, and zinc dihydrogen phosphate dihydrate; hydrates of nitrates such as aluminum nitrate nonahydrate, zinc nitrate hexahydrate, calcium nitrate tetrahydrate, cobalt nitrate hexahydrate, bismuth nitrate pentahydrate, zirconium nitrate pentahydrate, cerium nitrate hexahydrate, iron nitrate hexahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate, and magnesium nitrate hexahydrate; hydrates of acetates such as zinc acetate dihydrate and cobalt acetate tetrahydrate; hydrates of chloride salts such as cobalt chloride hexahydrate and iron chloride tetrahydrate; and hydrates of hydroxide salts such as aluminum hydroxide monohydrate, aluminum hydroxide trihydrate, magnesium hydroxide monohydrate, calcium hydroxide monohydrate, barium hydroxide monohydrate, and zirconium hydroxide monohydrate.

[0043] When the organic binder is a urethane resin, the heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.) is a component that, by mixing the polyol and the isocyanate, causes the free water from the hydrate such as boric acid hydrate to react with the isocyanate, generating carbon dioxide and foaming, thereby contributing to weight reduction and also contributing to the lightness of the heat-absorbing layer (heat-absorbing layer (A)).

[0044] The content of the heat-absorbing compound is preferably 5% by mass or more and 90% by mass or less (more preferably 10% by mass or more and 80% by mass or less, even more preferably 20% by mass or more and 70% by mass or less) of the entire heat-absorbing layer (A). Within such a range, a heat-absorbing layer (heat-absorbing layer (A)) that sufficiently combines both heat-absorbing property and lightness can be obtained. Also, the content of the boric acid hydrate, etc. is preferably 5% by mass or more and 90% by mass or less (more preferably 10% by mass or more and 80% by mass or less, even more preferably 20% by mass or more and 70% by mass or less) of the entire heat-absorbing layer (A). Within such a range, a heat-absorbing layer (heat-absorbing layer (A)) that more sufficiently combines both heat-absorbing property and lightness can be obtained.

[0045] The content of the heat-absorbing compound is 2.0 kg / m 2 , 2 , 2 , 2 , , 2 , 2 , 2 , 2 , 2 or more (more preferably 2.5 kg / m 2 or more and 20.0 kg / m 2 or less, even more preferably 3.0 kg / m 2 or more and 15.0 kg / m 2 or less) with respect to the heat-absorbing layer (A). Within such a range, a heat-absorbing layer (heat-absorbing layer (A)) that sufficiently combines both heat-absorbing property and lightness can be obtained. Also, when the hydrate compound contains the boric acid hydrate, etc., the content of the boric acid hydrate, etc. is 2.0 kg / m 2 or more (more preferably 2.5 kg / m 2 or more and 20.0 kg / m 2 or less, even more preferably 3.0 kg / m 2 or more and 15.0 kg / m 2The following is preferable. Within this range, a heat-absorbing layer (heat-absorbing layer (A)) that more sufficiently combines both heat absorption and lightweight properties can be obtained.

[0046] The amount of the endothermic compound mixed is preferably 30 parts by mass or more and 300 parts by mass or less (more preferably 40 parts by mass or more and 250 parts by mass or less, and even more preferably 45 parts by mass or more and 200 parts by mass or less) per 100 parts by mass of the organic binder. Furthermore, if the hydrated compound contains boric acid hydrate or the like, the amount of boric acid hydrate or the like mixed is preferably 30 parts by mass or more and 300 parts by mass or less (more preferably 40 parts by mass or more and 250 parts by mass or less, and even more preferably 45 parts by mass or more and 200 parts by mass or less) per 100 parts by mass of the organic binder.

[0047] When the organic binder is a urethane resin, the amount of the endothermic compound mixed is preferably 30 parts by mass or more and 300 parts by mass or less (more preferably 40 parts by mass or more and 250 parts by mass or less, and even more preferably 45 parts by mass or more and 200 parts by mass or less) per 100 parts by mass of the polyol. Furthermore, if the hydrated compound includes the boric acid hydrate, etc., and the organic binder is a urethane resin, it is particularly preferable that the amount of the boric acid hydrate, etc. mixed is 30 parts by mass or more and 300 parts by mass or less (more preferably 40 parts by mass or more and 250 parts by mass or less, and even more preferably 45 parts by mass or more and 200 parts by mass or less) per 100 parts by mass of the polyol.

[0048] When the organic binder is an unsaturated polyester resin and / or a vinyl ester resin, the amount of the endothermic compound mixed is preferably 30 parts by mass or more and 300 parts by mass or less (more preferably 40 parts by mass or more and 250 parts by mass or less, and even more preferably 45 parts by mass or more and 200 parts by mass or less) per 100 parts by mass of the unsaturated polyester resin and / or vinyl ester resin. Furthermore, if the hydrated compound includes the boric acid hydrate, etc., and the organic binder is an unsaturated polyester resin and / or a vinyl ester resin, it is particularly preferable that the amount of boric acid hydrate, etc. mixed is 30 parts by mass or more and 300 parts by mass or less (more preferably 40 parts by mass or more and 250 parts by mass or less, and even more preferably 45 parts by mass or more and 250 parts by mass or less) per 100 parts by mass of the unsaturated polyester resin and / or vinyl ester resin.

[0049] The heat-absorbing layer (heat-absorbing layer (A)) can be obtained by mixing other additives in addition to the components described above. Examples of these other additives include fillers, flame retardants, foaming agents, foam stabilizers, viscosity modifiers, curing accelerators, initiators, metal hydrates, colorants, dyes, film-forming aids, leveling agents, wetting agents, plasticizers, antifreeze agents, pH adjusters, preservatives, antifungal agents, antialgal agents, antibacterial agents, dispersants, surfactants, adsorbents, fibers, carbonizing agents, solvents, and internal mold release agents. Furthermore, the heat-absorbing layer (A) may also contain, in addition to the organic binder, an inorganic binder, as described later, to an extent that does not hinder the effects of the present invention.

[0050] Examples of the aforementioned fillers include heavy calcium carbonate, kaolin, diatomaceous earth, white carbon, clay, talc, barite powder, precipitated barium sulfate, barium carbonate, silica sand, vermiculite, ceramic beads, glass beads, silica gel, perlite, expanded vermiculite, pumice, vermiculite, ALC crushed material, hollow ceramic beads, hollow glass beads, shirasu balloons, charcoal, bamboo charcoal, seed husk charcoal, smoked seed husk charcoal, styrene foam, ethylene vinyl acetate foam, vinyl chloride foam, etc., and one or more of these can be used.

[0051] The amount of the filler to be mixed should be between 1 and 200 parts by mass (more specifically, between 3 and 150 parts by mass) per 100 parts by mass of the organic binder. Within this range, excellent strength can be achieved while ensuring lightness.

[0052] If the organic binder is a urethane resin, the amount of the filler to be mixed should be between 1 and 200 parts by mass (more specifically, between 3 and 150 parts by mass) per 100 parts by mass of the polyol. Within this range, excellent strength can be achieved while ensuring lightness.

[0053] If the organic binder is an unsaturated polyester resin and / or a vinyl ester resin, the amount of the filler to be mixed should be 1 to 200 parts by mass (more specifically, 3 to 150 parts by mass) per 100 parts by mass of the unsaturated polyester resin and / or vinyl ester resin.

[0054] In particular, in this invention, the filler has a bulk density of 0.01 g / cm³. 3 More than 1g / cm 3 Lightweight fillers weighing less than 100 kg can be used, and one or more of the following can be used: perlite, expanded vermiculite, pumice, vermiculite, ALC crushed material, ceramic hollow beads, hollow glass beads, charcoal, bamboo charcoal, seed husk charcoal, seed husk charcoal, styrene resin foam, ethylene vinyl acetate resin foam, vinyl chloride resin foam, etc. Furthermore, in the present invention, one or more non-combustible lightweight fillers selected from perlite, expanded vermiculite, pumice, vermiculite, ALC crushed material, ceramic hollow beads, hollow glass beads, charcoal, bamboo charcoal, seed husk charcoal, and seed husk charcoal can be used.

[0055] The amount of the lightweight filler to be mixed should be 200 parts by mass or less (more specifically, 150 parts by mass or less) per 100 parts by mass of the organic binder. Having the lightweight filler within this range is advantageous in terms of lightness and strength. Furthermore, if the lightweight filler is a non-combustible lightweight filler, it is also advantageous in terms of heat resistance.

[0056] If the organic binder is a urethane resin, the amount of the lightweight filler to be mixed should be 200 parts by mass or less (more specifically, 150 parts by mass or less) per 100 parts by mass of the polyol. Having the lightweight filler within this range is advantageous in terms of lightness and strength. Furthermore, if the lightweight filler is a non-combustible lightweight filler, it is also advantageous in terms of heat resistance.

[0057] If the organic binder is an unsaturated polyester resin and / or vinyl ester resin, the amount of the lightweight filler to be mixed should be 200 parts by mass or less (more specifically, 150 parts by mass or less) per 100 parts by mass of the unsaturated polyester and / or vinyl ester. Having the lightweight filler within this range is advantageous in terms of lightness and strength. Furthermore, if the lightweight filler is a non-combustible lightweight filler, it is also advantageous in terms of heat resistance.

[0058] The bulk density of the filler is measured by supplying lightweight colored particles to a cylindrical container and applying vertical vibration (tapping vibration) until the change in the volume of the lightweight colored particles inside the container is complete.

[0059] Furthermore, the average particle size of the filler is not particularly limited, but it should be between 50 μm and 1000 μm. The average particle size of the filler can be measured using a laser diffraction particle size distribution analyzer.

[0060] Examples of the aforementioned flame retardants include phosphorus-based flame retardants, halogen-based flame retardants, boron-based flame retardants, nitrogen-based flame retardants, and silicon-based flame retardants, and one or more of these can be used.

[0061] Examples of the phosphorus-based flame retardants include phosphate ester compounds, phosphate compounds, polyphosphate compounds, phosphate compounds, phosphoite compounds, phosphonate compounds, phosphonites, phosphinates, phosphinates, red phosphorus, phosphorus trichloride, phosphorus pentachloride, and the like.

[0062] Examples of the phosphate compounds include aluminum phosphate, sodium phosphate, potassium phosphate, calcium phosphate, zinc phosphate, ammonium phosphate, aluminum phosphite, sodium phosphite, potassium phosphite, calcium phosphite, zinc phosphite, ammonium phosphite, hypoaluminum phosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, zinc hypophosphite, ammonium hypophosphite, aluminum metaphosphate, sodium metaphosphate, potassium metaphosphate, calcium metaphosphate, and zinc metaphosphate.

[0063] Examples of the polyphosphate compounds include ammonium polyphosphate, ammonium polyphosphate amide, melamine polyphosphate, piperazine polyphosphate, melem polyphosphate, melam polyphosphate, melon polyphosphate, and aluminum polyphosphate.

[0064] Examples of the phosphonate compounds include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonic acid, 2,3-dimethylbutylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, and dioctyl phenylphosphonate.

[0065] Examples of the phosphinate compounds include dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, and bis(4-methoxyphenyl)phosphinic acid.

[0066] Examples of halogenated flame retardants include those containing fluorine, chlorine, bromine, iodine, and antimony, such as halogenated oxides, halogenated phosphazenes, halogenated alkanes, halogenated indanes, halogenated phosphate esters, and halogenated polystyrenes.

[0067] Examples of the boron-based flame retardants include boron oxide, lithium borate, sodium borate (excluding boric acid hydrate, etc.), potassium borate, cesium borate, magnesium borate, calcium borate, barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate.

[0068] The amount of the flame retardant mixed is preferably 1 to 200 parts by mass (more preferably 3 to 150 parts by mass, and even more preferably 5 to 100 parts by mass) per 100 parts by mass of the organic binder. By having the flame retardant within this range, it is possible to improve dispersibility and further achieve both heat resistance and light weight.

[0069] When the organic binder is a urethane resin, it is particularly preferable that the amount of the flame retardant mixed is 1 to 200 parts by mass (more preferably 3 to 150 parts by mass, and even more preferably 5 to 100 parts by mass) per 100 parts by mass of the polyol. By having the flame retardant within this range, it is possible to improve dispersibility and further achieve both heat resistance and lightweight properties. In particular, it is preferable to use castor oil-based polyols and / or castor oil (more preferably castor oil) as the polyol in the above-mentioned mixing ratio.

[0070] When the organic binder is an unsaturated polyester resin and / or vinyl ester resin, it is particularly preferable that the amount of the flame retardant mixed is 1 to 200 parts by mass (more preferably 3 to 150 parts by mass, and even more preferably 5 to 100 parts by mass) per 100 parts by mass of the unsaturated polyester and / or vinyl ester. By having the flame retardant within this range, it is possible to improve dispersibility and further achieve both heat resistance and lightweight properties.

[0071] Furthermore, in the present invention, it is preferable to use the flame retardant in combination with the endothermic compound (for example, boric acid, boric acid hydrate, etc.). By using them in combination, heat resistance can be further improved, and in particular, by using a liquid flame retardant in combination, the dispersion stability of the endothermic compound (for example, boric acid, boric acid hydrate, etc.) and the viscosity of the composition can be controlled, making it possible to obtain an endothermic layer with superior heat resistance and lightness.

[0072] The blowing agent is not particularly limited, but examples include hydrofluoroolefins, hydrochlorofluoroolefins, water, liquefied carbon dioxide, etc., and one or more of these can be used.

[0073] Examples of the hydrofluoroolefin (HFO) include pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), tetrafluoropropene such as 1,3,3,3-tetrafluoropropene (HFO1234ze), 2,3,3,3-tetrafluoropropene (HFO1234yf), and 3,3,3-trifluoropropene. Examples include trifluoropropenes such as (HFO1243zf), tetrafluorobutene (HFO1345), pentafluorobutene (HFO1354), hexafluorobutene (HFO1336), heptafluorobutene (HFO1327), heptafluoropentene (HFO1447), octafluoropentene (HFO1438), nonafluoropentene (HFO1429), or their isomers (cis and trans isomers).

[0074] Examples of the hydrochlorofluoroolefin (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), dichlorotrifluoropropene (HCFO1223), or their isomers (cis and trans forms).

[0075] In the present invention, one or more foaming agents selected from hydrofluoroolefins, hydrochlorofluoroolefins, and water are preferred. For example, a combination of each foaming agent can be used, such as hydrofluoroolefin and water, hydrochlorofluoroolefin and water, or hydrofluoroolefin and hydrochlorofluoroolefin and water.

[0076] In the case where the organic binder is a urethane resin, the amount of the foaming agent mixed is preferably 200 parts by mass or less, more preferably 20 parts by mass or more and 180 parts by mass or less, and even more preferably 30 parts by mass or more and 150 parts by mass or less, per 100 parts by mass of the polyol.

[0077] Examples of the foam stabilizers include silicone-based foam stabilizers such as polyether-modified silicone compounds, and fluorine-containing compound-based foam stabilizers. These can be used individually or in combination of two or more.

[0078] Examples of the polyether-modified silicone compound include graft copolymers of polydimethylsiloxane and polyoxyethylene glycol or polyoxyethylene-propylene glycol.

[0079] When the organic binder is a urethane resin, the amount of the foam stabilizer mixed is preferably 40 parts by mass or less, and more preferably 0.5 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the polyol.

[0080] Examples of viscosity modifiers include layered clay minerals such as smectite and vermiculite, amide wax, hydrophobic cellulose such as ethylcellulose and cellulose nitrate, and polyolefins such as polyethylene and polypropylene. One or more of these can be used. In particular, in the present invention, it is preferable to use layered clay minerals, and especially preferable to use layered clay minerals that have been organically treated with long-chain alkylammonium ions, etc. (organic smectite (organic montmorillonite, organic bentonite, etc.), organic vermiculite, etc.).

[0081] When the organic binder is a urethane resin, the amount of the viscosity modifier mixed is preferably 60 parts by mass or less, and more preferably 1.0 to 40 parts by mass, per 100 parts by mass of the polyol.

[0082] Examples of the curing accelerators include amines such as triethylamine, triethylenediamine, triethylamine, tetramethylbutanediamine, dimethylaminoethanol, dimer amine, and dimer acid polyamidoamine; tin carboxylates such as dibutyltin dilaurate, dibutyltin diacetate, and tin octate; metal carboxylates such as iron naphthenate, cobalt naphthenate, manganese naphthenate, zinc naphthenate, iron octyolate, cobalt octyolate, manganese octyolate, and zinc octyolate; carboxylates such as dibutyltin thiocarboxylate, dioctyltin thiocarboxylate, tributylmethylammonium acetate, and trioctylmethylammonium acetate; and aluminum compounds such as aluminum trisacetyl acetate. One or more of these can be used.

[0083] When the organic binder is a urethane resin, the amount of curing accelerator mixed is preferably 0.05 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, per 100 parts by mass of the polyol.

[0084] Examples of the initiators include organic peroxides such as hydroperoxides, dialkylperoxides, dialkylketone peroxides, diacylperoxides, ketone peroxides, peroxyesters, peroxyketals, and peroxydicarbonates, as well as azo compounds such as azobisisobutyronitrile, azobiscarbonamide, and 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile. One or more of these can be used.

[0085] When the organic binder is an unsaturated polyester resin and / or the vinyl ester resin, the amount of the initiator mixed is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, per 100 parts by mass of the unsaturated monomer.

[0086] The heat-absorbing layer (A) can be obtained by mixing the polyol, the isocyanate, and the heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.), adding other additives as needed, mixing, and curing to obtain a heat-absorbing layer (A) containing urethane resin and a heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.). In particular, a first liquid (first component) is prepared by mixing the polyol and the endothermic compound (e.g., boric acid, boric acid hydrate, etc.), and other additives as needed, and a second liquid (second component) containing isocyanate is prepared. The first liquid and the second liquid are mixed and reacted to obtain an endothermic layer (A). Alternatively, the endothermic compound (e.g., boric acid, boric acid hydrate, etc.) and other additives may be mixed only with the first component, or they may be mixed with the second component as needed. In such cases, it is particularly preferable to mix and react the materials at a temperature of 10°C to 150°C (more preferably 15°C to 120°C).

[0087] Furthermore, the heat-absorbing layer (A) can be obtained by mixing the unsaturated polyester and / or the vinyl ester, the unsaturated monomer, and the heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.), adding other additives as needed, mixing, and curing to obtain a heat-absorbing layer (A) containing an unsaturated polyester resin and a heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.). In particular, a first liquid (first component) is prepared by mixing the unsaturated polyester and / or vinyl ester, the unsaturated monomer, and the endothermic compound (e.g., boric acid, boric acid hydrate, etc.), and other additives as needed, and a second liquid (second component) containing an initiator is prepared. The first liquid and the second liquid are mixed and reacted to obtain an endothermic layer (A). The endothermic compound (e.g., boric acid, boric acid hydrate, etc.) and other additives may be mixed only with the first component, or they may be mixed with the second component as needed. In such cases, it is particularly preferable to mix and react the materials at a temperature of 10°C to 150°C (more preferably 15°C to 120°C).

[0088] [Endothermic layer (B)] Furthermore, the heat-absorbing layer may include, in addition to the heat-absorbing layer (A), a heat-absorbing layer formed by an inorganic binder (hereinafter sometimes referred to as "heat-absorbing layer (B)"). Unlike the heat-absorbing layer (A), the heat-absorbing layer (B) is a heat-absorbing layer that does not contain (substantially contains) endothermic compounds (e.g., boric acid, boric acid hydrate, etc.), and specifically, it is a heat-absorbing layer that does not contain (substantially contains) the organic binder (e.g., urethane resin, polyols and isocyanates constituting the urethane resin, unsaturated polyester resin, unsaturated polyesters and unsaturated monomers constituting the unsaturated polyester resin, and vinyl ester resin, vinyl esters and unsaturated monomers constituting the vinyl ester resin) or endothermic compounds (e.g., boric acid, boric acid hydrate, etc.). Furthermore, "effectively not included" means that it accounts for less than 5% by mass of the entire heat-absorbing layer (B).

[0089] (Inorganic binder) Examples of the inorganic binder include hydraulic inorganic binders, and among these, hydraulic inorganic binders are preferred from the viewpoint of endothermic properties.

[0090] Examples of the hydraulic inorganic binder include Portland cement, alumina cement, ultrafast-setting cement, expansive cement, acidic phosphate cement, silica cement, lime-mixed cement, blast furnace cement, fly ash cement, Keens cement, magnesia cement, dolomite, calcium silicate, hydraulic lime, gypsum, etc., and one or more of these can be used.

[0091] The hydraulic inorganic binder can form a large amount of bound water during bonding, allowing the heat-absorbing layer (B) to contain a large amount of bound water. As a result, when the temperature rises, it can utilize the latent heat of vaporization of the bound water to exhibit excellent heat absorption. Furthermore, the heat-absorbing layer (B) containing the hydraulic inorganic binder also has excellent strength, which can improve the strength of the laminated structure of the present invention.

[0092] The heat-absorbing layer (B) may contain other additives in addition to the inorganic binder. Examples of these other additives include water, fillers, water-reducing agents, setting regulators, flame retardants, metal hydrates, fibers, adhesion enhancers, water-repellent agents, dispersants, surfactants, defoamers, and rust inhibitors. The organic binder may also be included in an amount that does not impair the effects of the present invention.

[0093] The heat-absorbing layer (B) can be obtained by mixing the inorganic binder and, if necessary, other additives, and then curing the mixture. For example, the heat-absorbing layer (B) can be obtained by mixing the inorganic binder and other additives with water to form a slurry, and then curing and hardening the mixture. In addition, reinforcing materials such as glass nonwoven fabric, glass cloth, and ceramic paper can be embedded during manufacturing.

[0094] Examples of such heat-absorbing layers (B) include cement board, reinforced cement board, glass fiber reinforced cement board, calcium silicate board, glass fiber reinforced calcium silicate board, gypsum board, reinforced gypsum board, and glass fiber nonwoven gypsum board.

[0095] The laminated structure of the present invention can use a laminated structure in which multiple heat-absorbing layers, such as the heat-absorbing layer (A) and the heat-absorbing layer (B), are laminated together as the heat-absorbing layer.

[0096] The method for laminating the multiple heat-absorbing layers is not particularly limited, but the heat-absorbing layers can be manufactured by: (1) preparing heat-absorbing layer (A) and heat-absorbing layer (B) separately in advance and laminating them using an adhesive or the like; (2) pouring the components constituting heat-absorbing layer (A) into contact with the pre-prepared heat-absorbing layer (B) and curing them to form heat-absorbing layer (A); (3) pouring the components constituting heat-absorbing layer (B) into contact with the pre-prepared heat-absorbing layer (A) and curing them to form heat-absorbing layer (B); or by a combination of these methods.

[0097] Methods (2) and (3) described above allow for adhesive-free lamination (direct lamination without using adhesive), and can suppress heat generation caused by adhesives when exposed to high temperatures due to fire or other reasons. For example, method (2) exhibits excellent adhesion.

[0098] Examples of structures in which multiple heat-absorbing layers are stacked include, for example, a structure in which multiple heat-absorbing layers (A) are stacked, a structure in which heat-absorbing layer (A) and heat-absorbing layer (B) are stacked, and are not particularly limited, but include structures such as heat-absorbing layer (A) / heat-absorbing layer (A), heat-absorbing layer (A) / heat-absorbing layer (B), heat-absorbing layer (B) / heat-absorbing layer (A) / heat-absorbing layer (B), heat-absorbing layer (A) / heat-absorbing layer (B) / heat-absorbing layer (A), and heat-absorbing layer (B) / heat-absorbing layer (A) / heat-absorbing layer (B) / heat-absorbing layer (A).

[0099] Furthermore, the heat-absorbing layer (A) may include multiple heat-absorbing layers (A) such as heat-absorbing layer (A1), heat-absorbing layer (A2), etc., which contain different raw materials other than organic binders and heat-absorbing compounds (e.g., boric acid, boric acid hydrate, etc.) or which have different thicknesses, and the heat-absorbing layer (B) may include multiple heat-absorbing layers (B) such as heat-absorbing layer (B1), heat-absorbing layer (B2), etc., which contain different raw materials other than inorganic binders or which have different thicknesses.

[0100] The density of the heat-absorbing layer (A) is 1.0 g / cm³. 3 More than 2.0g / cm 3 The following is preferable: 1.1 g / cm³ 3 More than 1.8g / cm 3 The following are preferable. By setting the density of the heat-absorbing layer (A) to the aforementioned range and fixing the fastener by press-fitting it into the heat-absorbing layer (the fastener is pressed-fitted to a thickness of 30% or more but less than 100% of the thickness of the heat-absorbing layer), the heat-foamed layer will not fall out due to foaming even in the event of a fire, the heat-foamed layer (carbonized insulation layer) and the decorative layer will be firmly fixed, further suppressing the detachment of the heat-foamed layer (carbonized insulation layer) and the decorative layer, and demonstrating excellent fire resistance.

[0101] The density of the heat-absorbing layer (B) is 0.1 g / cm³. 3 More than 1.5g / cm 3 The following is preferable: 0.3 g / cm³ 3 More than 1.2g / cm 3 The following is more preferable: 0.5 g / cm³ 3 More than 1.0g / cm 3 The following is even more preferable.

[0102] Because the aforementioned heat-absorbing layers (heat-absorbing layer (A) and heat-absorbing layer (B)) have such densities, it is possible to obtain a heat-absorbing layer that is lightweight yet has excellent heat resistance, strength, and dimensional stability.

[0103] The thickness of the heat-absorbing layer (A) (1 layer) is preferably 3 mm or more and 60 mm or less (more preferably 4 mm or more and 50 mm or less, even more preferably 5 mm or more and 30 mm or less, and most preferably 6 mm or more and 25 mm or less).

[0104] The thickness of the heat-absorbing layer (B) (1 layer) is preferably 1 mm or more and 50 mm or less (more preferably 3 mm or more and 30 mm or less, and even more preferably 5 mm or more and 25 mm or less).

[0105] [Thermal foam layer] The laminated structure of the present invention is formed by laminating an organic substrate in the following order: a heat-absorbing layer, a thermally foamed layer, and a decorative layer. As the aforementioned heat-foamed layer, one can be used in which, when the ambient temperature rises due to a fire or the like and the temperature of the heat-foamed layer reaches a predetermined foaming temperature, the respective raw materials constituting the heat-foamed layer foam up and form a carbonized insulation layer.

[0106] The foaming temperature of the aforementioned heat-foamed layer is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200-400°C, from the standpoint of temperature rise due to flames or heat.

[0107] The aforementioned thermal foam layer can be formed, for example, by a thermal foam coating material or a thermal foam sheet, and these can be used by laminating one or more of them together.

[0108] The thermal foam layer is preferably composed of a mixture of components including a resin component, a flame retardant, a foaming agent, a carbonizing agent, and a filler. Each of these components can be used individually or in combination of two or more.

[0109] Examples of the resin components include thermoplastic resins such as polyester resin, polybutadiene resin, acrylic resin, styrene resin, acrylic styrene resin, vinyl acetate resin, vinyl acetate / vinyl versatate copolymer resin, vinyl acetate / ethylene copolymer resin, vinyl acetate / vinyl versatate copolymer resin, vinyl acetate / acrylic copolymer resin, polyethylene resin, vinyl chloride resin, polypropylene resin, and polystyrene resin, as well as thermosetting resins such as epoxy resin, urethane resin, alkyd resin, phenolic resin, and melamine resin.

[0110] Examples of the aforementioned flame retardants include organophosphorus compounds such as tricresyl phosphate and diphenylcresyl phosphate; chlorine compounds such as chlorinated polyphenyl, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, chlorinated paraffin, pentachloride fatty acid ester, perchloropentacyclodecane, chlorinated naphthalene, and tetrachlorophthalic anhydride; antimony compounds such as antimony trioxide and antimony pentachloride; phosphorus compounds such as phosphorus trichloride, phosphorus pentachloride, ammonium phosphate, ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, boron phosphate, boron polyphosphate, aluminum phosphate, and aluminum polyphosphate; and other inorganic compounds such as zinc borate.

[0111] Examples of the foaming agents include melamine and its derivatives, dicyandiamide and its derivatives, azobistetrasome and its derivatives, azodicarbonamide, urea, thiourea, and the like.

[0112] Examples of the carbonizing agent include pentaerythritol, dipentaerythritol, trimethylolpropane, starch, and casein.

[0113] Examples of the aforementioned fillers include talc, calcium carbonate, sodium carbonate, aluminum oxide (alumina), titanium oxide, zinc oxide, silica, clay, volcanic ash, mica, silica sand, silica powder, quartz powder, barium sulfate, and inorganic fibers.

[0114] The mixing ratio (mass ratio) of each component is preferably, in terms of solid content, 200 to 600 parts by mass of the flame retardant, 40 to 150 parts by mass of the foaming agent, 40 to 150 parts by mass of the carbonizing agent, and 50 to 160 parts by mass of the filler, per 100 parts by mass of the resin component. When used in this mixing ratio, the flame retardancy and fire resistance can be satisfied, resulting in a preferred configuration.

[0115] The mixture forming the thermal foam layer may, in addition to the above-mentioned components, optionally contain various additives. These additives should not significantly impede the effects of the present invention, and examples include pigments, fibers, wetting agents, plasticizers, lubricants, preservatives, antifungal agents, antialgal agents, antimicrobial agents, thickeners, dispersants, defoaming agents, crosslinking agents, ultraviolet absorbers, light stabilizers, antioxidants, diluent solvents, and the like.

[0116] The heat-expandable coating material used to form the heat-expandable layer can be used as a liquid mixture containing the aforementioned components and additives. Furthermore, the heat-expandable sheet used to form the heat-expandable layer can be a sheet formed from the mixture containing the aforementioned components and additives.

[0117] The thickness of the heat-foamed layer can be set appropriately depending on the application, but from the viewpoint of fire resistance, light weight, etc., it is preferably 0.1 to 10 mm, more preferably 0.3 to 8 mm, and even more preferably 0.5 to 6 mm.

[0118] The thermal foam layer may consist solely of a mixture containing the aforementioned components and additives, but from the viewpoint of productivity, workability, flexibility, etc., a fibrous sheet or the like may be laminated on the surface or back surface of the thermal foam layer. As such a fibrous sheet, for example, a known sheet containing organic fibers and / or inorganic fibers can be used.

[0119] [Cosmetic layer] The laminated structure of the present invention is characterized in that a heat-absorbing layer, a heat-foaming layer, and a decorative layer are laminated in that order on an organic substrate, the decorative layer being the outermost layer, and in a region where the distance from each corner of the decorative layer is 40% or less of the length of one side of the substrate in the cross-sectional direction, a fastener is pressed in from the decorative layer toward the heat-absorbing layer to a thickness of 30% or more but less than 100% of the thickness of the heat-absorbing layer, and the fastener does not reach the organic substrate.

[0120] The decorative layer can be provided on the surface of the heat-foamed layer. Examples of the decorative layer include woodblocks, various coating materials, sheet materials, and film materials. These can exhibit a variety of appearances, such as being transparent or opaque, colorless or colored, matte or glossy, single-colored or multi-colored, flat or uneven. In the present invention, providing the decorative layer enhances the aesthetics, water resistance, weather resistance, and other properties of the laminated structure, making it useful. Furthermore, if the decorative layer is made of wood, the wood will be carbonized in the event of a fire or other incident, forming a carbonized layer of wood and a carbonized insulating layer of the heat-expanded layer, which can be expected to improve fire resistance.

[0121] To make the parts where fasteners are driven into the surface of the decorative layer less noticeable, for example, (i) using decorative nails with painted heads to make them less noticeable, (ii) driving the fasteners into the surface of the decorative layer and then making the surface less noticeable with paint, putty, tape, etc., or (iii) creating recesses in the surface of the decorative layer in advance, driving the fasteners into the recesses, and then making the recesses less noticeable with paint, putty, etc.

[0122] In the laminated structure of the present invention, the locations where the fasteners are driven in are regions where the distance from each corner of the decorative layer is 40% or less of the length of one side of the base material in the cross-sectional direction, preferably 5% to 35%, and more preferably 10% to 30%.

[0123] In the laminated structure of the present invention, the depth to which the fastener is pressed in is such that the fastener is pressed in to a depth of 30% or more but less than 100% of the thickness of the heat-absorbing layer, preferably 40% or more but 95%, and more preferably 50% or more but 90% (not yet reached).

[0124] The areas near each corner of the decorative layer (areas of 40% or less) are areas where the temperature tends to rise during a fire. Furthermore, by press-fitting the fasteners at a thickness of 30% to less than 100% of the heat-absorbing layer, the detachment of the carbonized insulation layer and the decorative layer, which are formed by thermal expansion during a fire, is suppressed, and the conduction of heat to the organic substrate is further suppressed, resulting in a laminated structure with excellent fire resistance. If a fastener is pressed into the area near the corner of the decorative layer (area of ​​40% or less) with a thickness of less than 30% of the heat-absorbing layer, there is a risk that the fastener may fall out due to the foaming of the heat-foamed layer during a fire, etc., preventing the heat-foamed layer (carbonized insulation layer) and the decorative layer from being fixed together, making it difficult to prevent the heat-foamed layer, carbonized insulation layer, and decorative layer from falling off. Furthermore, if the fastener is pressed in to a thickness of 100% or more of the heat-absorbing layer, the fastener may reach the organic substrate, and heat may be conducted to the organic substrate through the fastener, potentially reducing the fire resistance performance. Furthermore, in areas where the length of one side of the substrate in the cross-sectional direction exceeds 40%, the temperature rises less during a fire than in areas where it is 40% or less. Therefore, when a fastener is pressed into such an area, there is no particular problem even if the fastener presses into the heat-absorbing layer and reaches the organic substrate.

[0125] [Other layers] The laminated structure of the present invention is constructed by laminating an organic substrate in the order of a heat-absorbing layer, a heat-foaming layer, and a decorative layer. However, other layers may be laminated as needed, as long as they do not significantly impair the effects of the present invention. Examples of such layers include an adhesive layer and other layers (e.g., a reinforcing layer, a heat-reflective layer, a heat-shielding layer, a waterproof layer, a water-repellent layer, a water-shielding layer, a heat-insulating layer, etc.).

[0126] Of these, the adhesive layer is formed by an adhesive used to bond each layer together. As the adhesive used for the adhesive layer, known adhesives such as water-dispersible, water-soluble, and solvent-based adhesives primarily composed of acrylic resin, silicone resin, epoxy resin, vinyl resin, phenolic resin, polyester resin, urethane resin, paraffin, etc., can be used. The adhesive may contain additives such as flame retardants, foaming agents, carbonizing agents, and fillers, as needed, similar to those incorporated into the aforementioned heat-foamed layer. In this invention, the adhesive also includes a tackifier.

[0127] The heat-reflective layer can be provided between the heat-foamed layer and the heat-absorbing layer, or between the heat-absorbing layer and the organic substrate, etc. As the heat-reflective layer, metal plates, sheets, tapes, etc. with high heat reflectivity can be used. Specifically, examples of heat-reflective layers include aluminum foil, aluminum tape, aluminum cloth, aluminum foil / glass nonwoven fabric laminated sheet, aluminum foil / mesh laminated sheet, aluminum foil / synthetic resin laminated sheet, etc.

[0128] By providing the heat-reflective layer between the heat-foaming layer and the heat-absorbing layer, the heat-foaming layer can foam smoothly, enabling the formation of an excellent carbonized heat-insulating layer.

[0129] The thickness of the heat-reflective layer can be set appropriately depending on the application, but from the viewpoint of fire resistance, light weight, etc., it is preferably 0.01 to 1 mm, more preferably 0.02 to 0.8 mm, and even more preferably 0.03 to 0.6 mm.

[0130] [Characteristics of laminates] In the laminated structure of the present invention, the total thickness of the laminate, which is the sum of the heat-absorbing layer, thermal foaming layer, decorative layer, and other layers excluding the organic substrate, can be made thinner than in the conventional technology. The thickness of the laminate (total thickness) is preferably 60 mm or less, more preferably 10 to 58 mm, and even more preferably 15 to 55 mm. By keeping the total thickness below the upper limit of the range, the burden on workers and the risk of injury during transportation and construction can be reduced, thereby improving work efficiency. When installed on columns, beams, floor slabs, walls, etc., inside a room, it is also possible to expand the interior space. If the total thickness is above the lower limit of the range, it is preferable in terms of heat insulation, fire resistance, strength, etc.

[0131] The mass per unit area of ​​the laminate is preferably 40 kg / m². 2 More preferably, 10-35 kg / m 2 More preferably 15-30 kg / m 2Laminates with these characteristics are lightweight, which reduces the burden on workers and the risk of injury during transportation and construction, thereby improving work efficiency. Furthermore, after application to organic substrates, it can also reduce the load on the organic substrates.

[0132] [Organic base material] The laminated structure of the present invention is characterized in that a heat-absorbing layer, a heat-foaming layer, and a decorative layer are laminated in that order on an organic substrate, and the organic substrate is an axial organic substrate with a polygonal cross-section.

[0133] Examples of the organic substrate include wood-based substrates, plastic substrates, fiber-reinforced plastic substrates, paper-based substrates, fibrous substrates, or substrates combining these. In particular, from the viewpoint of strength and lightness, it is preferable that the organic substrate is a wood-based substrate and / or a plastic substrate (wood-based substrate, plastic substrate, and fiber-reinforced plastic substrate, or a substrate combining these).

[0134] Examples of the aforementioned wood-based materials include lumber, plywood, laminated timber, LVL (Laminated Veneer Lumber), CLT (Cross Laminated Timber), particleboard, and fiberboard. The use of such wood-based materials also contributes to promoting carbon neutrality.

[0135] Of the aforementioned wood-based materials, CLT is a type of cross-laminated timber, which is a wood-based material made by arranging sawn boards (laminas) and then laminating and bonding them so that the fiber directions are perpendicular to each other. Specifically, CLT is defined in the Japanese Agricultural Standard JAS3079:2019 "Cross-laminated timber" as "timber having a structure of three or more layers, mainly by laminating and bonding sawn boards or small square timbers (including those that have been joined and bonded in the length direction with their fiber directions approximately parallel to each other) in the width direction with their fiber directions approximately parallel to each other." CLT can be applied to structural frames and the like.

[0136] The thickness of the aforementioned wood-based material can be set appropriately depending on the application and other factors.

[0137] As the aforementioned plastic substrate, a substrate mainly composed of a thermoplastic resin and / or a thermosetting resin can be used.

[0138] Examples of the thermoplastic resins include polyamide, polyacetal, polysulfone, polyester, polybutylene terephthalate, polycarbonate, polyethylene terephthalate, polyethylene, polypropylene, polyphenylene sulfide, polyether ether ketone, polyetherimide, polyether ketone ketone, polyvinyl chloride, acrylic resin, ABS resin, fluororesin, and silicone resin.

[0139] The thermosetting resins used can be those that form a three-dimensional crosslinked structure through a crosslinking reaction. Examples include unsaturated polyester resins, vinyl ester resins, epoxy resins, benzoxazine resins, phenolic resins, urethane resins, urea resins, melamine resins, and polyimide resins. These can be used individually or in combination of two or more.

[0140] In the present invention, a fiber-reinforced plastic substrate can be used as the plastic substrate. A fiber-reinforced plastic substrate is a composite of the resin and fibers described above, and is a substrate having properties such as high specific rigidity and high specific strength. By using a fiber-reinforced plastic substrate as the plastic substrate, the laminated structure of the present invention can be applied to structural frames and the like.

[0141] Examples of fibers used in the aforementioned fiber-reinforced plastic substrate include glass fibers, aramid fibers, Kevlar fibers, carbon fibers, graphite fibers, boron fibers, tyranno fibers, silicon carbide fibers, silicon nitride fibers, alumina fibers, and mineral fibers. Among these, glass fibers and carbon fibers are preferred from the viewpoint of improving mechanical strength, and the use of glass fibers is also preferable from a cost perspective. These can be used individually or in combination of two or more types.

[0142] The thickness of the aforementioned plastic substrate can be set appropriately depending on the application and other factors.

[0143] The aforementioned organic substrate is an axial organic substrate with a polygonal cross-section, and examples of polygons include rectangles and hexagons. These organic substrates are frequently used in flooring, wall materials, columns (such as square columns), and beams, and are preferred because they offer excellent workability.

[0144] [Method for manufacturing laminated structures] As a method for manufacturing the laminated structure of the present invention, the heat-absorbing layer, the heat-foaming layer, and the decorative layer are laminated on the organic substrate in that order, and then the fixing device is driven into the decorative layer to fix it to the heat-absorbing layer, thereby obtaining the laminated structure of the present invention. The heat-absorbing layer, the thermal foaming layer, and the decorative layer can each be sized to match the size of the layer to be laminated. Each layer can be laminated one by one or multiple layers can be laid side by side. When laying multiple layers side by side, each layer can be fitted together by providing a convex part (male part) and a concave part (female part) on its side surface, or by providing a projection and a groove. Furthermore, the adhesive layer and other layers can be laminated across the entire surface or partially. For example, a reinforcing layer, a heat reflective layer, a heat shielding layer, etc., can be laminated at the corners of a polygonal shape, or a waterproof layer, a water-repellent layer, a water-shielding layer, etc., can be laminated on the outer surface of a polygon.

[0145] When fixing the decorative layer onto the aforementioned heat-foamed layer using a fastener (long-axis fastener), the length of the fastener (long-axis fastener) can be selected and the fastener can be driven in so that the heat-absorbing layer does not reach the organic substrate. Furthermore, when fixing layers other than the decorative layer, the adhesives and fasteners used are not particularly limited, but if fasteners are used, they may or may not reach the organic substrate. Furthermore, the fasteners (long-axis fasteners) can be driven in and fixed perpendicularly to each surface, or they can be driven in and fixed at an angle to each surface.

[0146] The actual manufacturing process (construction procedure) for the laminated structure of the present invention will be described below with reference to the drawings.

[0147] Figures 1, 3, and 5 are schematic diagrams showing an example of the actual manufacturing process (construction procedure) of the laminated structure of the present invention. First, an organic substrate (axial organic substrate) is prepared, and then a heat-absorbing layer, a heat-foaming layer, and a decorative layer are sequentially laminated and fixed onto the organic substrate, thereby obtaining a laminated structure. The long-axis fixing device for fixing the decorative layer can be installed such that the head of the long-axis fixing device is embedded in the surface of the decorative layer so that the surface of the decorative layer is substantially flat (Figure 5), or a recess can be formed in which the head of the long-axis fixing device is embedded in the surface of the decorative layer, and this recess can be made using a dowel material so that the surface of the decorative layer is substantially flat (Figures 1 and 3).

[0148] Figures 2, 4, and 6 show cross-sectional views of a laminated structure in which an organic substrate (axial organic substrate) shown in Figures 1, 3, and 5, a heat-absorbing layer on the organic substrate, a heat-foaming layer on the heat-absorbing layer, and a decorative layer on the heat-foaming layer are sequentially laminated and fixed. In this invention, a cross-section refers to a cross-sectional view obtained by vertically cutting an axial laminated structure and viewing it from the side, showing the internal structure. While it is not possible to show all fasteners in a single cross-sectional view, they are shown in one for convenience.

[0149] The laminated structure of the present invention, when used as a building material, for example, can be used as a column, beam, It can be applied to walls, floors, foundations, etc., and is particularly suitable for use as axial structural elements such as columns and beams. [Examples]

[0150] Examples and comparative examples are shown below to further clarify the features of the present invention, but the invention is not limited to these examples.

[0151] The following materials were used to construct the laminated structure used as the test specimen.

[0152] Base material 1 (P): Wood-based base material (organic base material) (240mm x 240mm, height 3000mm, rectangular prism) Base material 2(P): Wood-based base material (organic base material) (300mm x 300mm, height 3000mm, rectangular prism) Heat-absorbing layer (Heat-absorbing layer (B)): Reinforced gypsum board (length 1820 mm, thickness 12.5 mm, density 0.75 g / cm³) 3 ) Heat-absorbing layer (Heat-absorbing layer (A-1)): A mixture of the first and second components of the heat-absorbing layer is poured into a mold (thickness 12.5 mm), reacted at 25°C for 3 hours, demolded, and the heat-absorbing layer (length 1500 mm, thickness 12.5 mm, density 1.4 g / cm³) is formed. 3 ) was obtained. First component of endothermic layer: Unsaturated polyester resin (unsaturated polyester / styrene (mass ratio 60 / 40)) 50 parts by mass 50 parts by mass of sodium borate decahydrate. Second component of endothermic layer: 1 part by mass of methyl ethyl ketone peroxide Heat-absorbing layer (Heat-absorbing layer (A-2)): A mixture of the first and second components of the heat-absorbing layer is poured into a mold (thickness 12.5 mm), reacted at 25°C for 3 hours, demolded, and the heat-absorbing layer (length 1500 mm, thickness 12.5 mm, density 1.4 g / cm³) is formed. 3 ) was obtained. First component of endothermic layer: Unsaturated polyester resin (unsaturated polyester / styrene (mass ratio 55 / 45)) 50 parts by mass 50 parts by mass of boric acid Second component of endothermic layer: 1 part by mass of methyl ethyl ketone peroxide Thermal foam layer (C): Thermal foam sheet [A mixture of 100 parts by mass of thermoplastic resin (ethylene vinyl acetate copolymer resin / acrylic resin), 60 parts by mass of foaming agent (melamine), 60 parts by mass of carbonizing agent (pentaerythritol), 300 parts by mass of flame retardant (ammonium polyphosphate), 75 parts by mass of filler (titanium dioxide), and other additives (fibers, plasticizers, etc.) is kneaded in a kneader heated to 120°C, rolled, and then cooled to room temperature to obtain a thermal foam sheet (thickness 3.0 mm, density 1.4 g / cm³)] 3 ] Decorative layer (D): Wood panel (length 3000mm, thickness 15mm) Long shaft fixing device 1 (G1): Screw (length 32 mm) (screw 1) Long shaft fixing device 2 (G2): Screw (length 45 mm) (2 screws) Long shaft fixing device 3 (G3): Screw (length 28 mm) (3 screws) Long shaft fixing bracket 4 (G4): Screw (length 22 mm) (4 screws) Long shaft fixing device 5 (G5): Screw (length 51 mm) (5 screws) Long shaft fixing bracket 6 (G6): Screw (length 38mm) (6 screws) Dowel material (E): Wooden dowel

[0153] (Fire resistance test) The test specimens prepared using the method described above were placed vertically in a test furnace, and a heating test was conducted for 90 minutes according to the standard heating curve of ISO 834. The surface temperature of the substrate when the surface of the test specimen was heated was measured using a thermocouple. Thermocouples were installed at a total of 24 locations on the substrate surface: both ends (corners) and the center in the horizontal direction, and the top, center, and bottom in the vertical direction. The evaluation criteria are as follows. The test results are shown in the table. Considering the practical risks of wood combustion, a rating of A or B according to the evaluation criteria is preferable for practical use. (Evaluation Criteria) A: Immediately after heating for 90 minutes, all parts should be below 200°C. B: Immediately after heating for 90 minutes, all parts are below 250°C. C: Immediately after heating for 90 minutes, one or more spots exceed 250°C.

[0154] (Example 1) The heat-absorbing layer (heat-absorbing layer (A-1)) was fixed to the four sides of the rectangular prism base material 1 using long axis fixing devices 1 (screw 1 (length 32 mm)). As shown in Figures 1 and 2, the long axis fixing devices 1 were fixed in one place at the center in the horizontal direction (cross-sectional direction), and in eight places in the vertical direction at intervals of approximately 600 mm (or approximately 300 mm) starting from the joint, for a total of eight fixing points on each side. Furthermore, the head of the long axis fixing device 1 (head of screw 1) was embedded in the surface of the heat-absorbing layer (heat-absorbing layer (A-1)), so that the surface of the heat-absorbing layer (heat-absorbing layer (A-1)) was approximately flat. Next, the heat-foamed layer was bonded using acrylic resin adhesive. Next, the decorative layers were bonded together using a polyvinyl chloride resin adhesive, and then fixed using a long axis fixing device 4 (screw 4 (length 22 mm)) and dowel material (wooden dowel) to obtain a test specimen. The long axis fixing devices 4 were fixed in two locations at a distance of 60 mm from the corner (approximately 20.0% of the distance from the corner (the length of one side in the cross-sectional direction of the decorative layer is 240 mm + 12.5 mm × 2 + 3 mm × 2 + 15 mm × 2 = 301 mm, so the distance from the corner is 60 / 301 = approximately 20.0%)) and in six locations at approximately 600 mm intervals in the vertical direction, for a total of 12 fixing locations per surface. Furthermore, the four heads of the long-axis fixing device (four screw heads) were embedded to a depth of 7 mm from the surface of the decorative layer, and dowel material (wooden dowel) was embedded in the resulting recess so that the surface of the decorative layer would be substantially flat, integrating it with the design of the decorative layer, and thus obtaining the test specimen. Screw 4 was press-fitted to 88% of the thickness of the heat-absorbing layer (heat-absorbing layer (A-1)), and the tip of the screw was located approximately 1.5 mm from the surface of the base material 1. The obtained test specimens underwent the fire resistance test described above, and the result was an evaluation of "A".

[0155] (Example 2) The heat-absorbing layer (heat-absorbing layer (B)) was fixed to the four sides of the rectangular prism base material 1 using long axis fixing devices 1 (screw 1 (length 32 mm)). As shown in Figures 3 and 4, the long axis fixing devices 1 were fixed in one place at the center in the horizontal direction (cross-sectional direction), and in seven places in the vertical direction at approximately 600 mm intervals starting from the joint, for a total of seven fixing points on each side. Furthermore, the head of the long axis fixing device 1 (head of screw 1) was embedded in the surface of the heat-absorbing layer (heat-absorbing layer (B)), so that the surface of the heat-absorbing layer (heat-absorbing layer (B)) was approximately flat. Next, the heat-absorbing layer (heat-absorbing layer (A-1)) was fixed using the long axis fixing device 2 (screw 2 (length 45 mm)). As shown in Figures 3 and 4, the long axis fixing devices 2 were fixed at two locations 60 mm from the corners, and at eight locations in the vertical direction starting from the joints at intervals of approximately 600 mm (or approximately 300 mm), for a total of 16 fixing points on each surface. Furthermore, the two heads of the long shaft fixing device (two screw heads) are embedded in the surface of the heat-absorbing layer (heat-absorbing layer (A-1)), and the surface of the heat-absorbing layer (heat-absorbing layer (A-1)) is made to be approximately flat. Next, the heat-foamed layer was bonded using acrylic resin adhesive. Next, the decorative layers were bonded together using a polyvinyl chloride resin adhesive, and then fixed using a long axis fixing device 3 (screw 3 (length 28 mm)) and dowel material (wooden dowel) to obtain a test specimen. The long axis fixing devices 3 were fixed in two locations at a distance of 72 mm from the corner (approximately 22.1% of the distance from the corner (the length of one side in the cross-sectional direction of the decorative layer is 240 mm + 12.5 mm × 2 + 12.5 mm × 2 + 3 mm × 2 + 15 mm × 2 = 326 mm, so the distance from the corner is 72 / 326 = approximately 22.1%)) and in six locations at approximately 600 mm intervals in the vertical direction, for a total of 12 fixing locations per surface. Furthermore, the three heads of the long-axis fixing device (three screw heads) were embedded to a depth of 7 mm from the surface of the decorative layer, and dowel material (wooden dowel) was embedded in the resulting recess so that the surface of the decorative layer would be substantially flat, integrating it with the design of the decorative layer, and thus obtaining the test specimen. Screw 3 was press-fitted to 68% of the thickness of the heat-absorbing layer (heat-absorbing layer (A-1) and heat-absorbing layer (B)), and the tip of screw 3 was located approximately 8.0 mm from the surface of base material 1. The obtained test specimens underwent the fire resistance test described above, and the result was an evaluation of "A".

[0156] (Example 3) A heat-absorbing layer (heat-absorbing layer (B)) was bonded to the four sides of the rectangular prism base material 2 using an acrylic resin adhesive. Next, the heat-absorbing layer (heat-absorbing layer (A-1)) was fixed using the long axis fixing device 2 (screw 2 (length 45 mm)). As shown in Figures 5 and 6, the long axis fixing devices 2 were fixed at two locations 80 mm from the corners, and at eight locations in the vertical direction starting from the joints at intervals of approximately 600 mm (approximately 300 mm), for a total of 16 fixing points on each surface. The heads of the long axis fixing devices 2 (screw heads) were embedded in the surface of the heat-absorbing layer, so that the surface of the heat-absorbing layer (heat-absorbing layer (A-1)) was approximately flat. Next, the heat-foamed layer was bonded using acrylic resin adhesive. Next, the decorative layer was bonded together and fixed using the long axis fixing device 5 (screw 5 (length 51 mm)) and the long axis fixing device 6 (screw 6 (length 38 mm)) to obtain the test specimen. The long axis fixing devices 5 were fixed at six locations on each surface, at intervals of approximately 600 mm in the vertical direction, with a total of six fixing locations per surface. These locations were 193 mm from the corner (the distance from the corner is 50.0% (the length of one side in the cross-sectional direction of the decorative layer is 300 mm + 12.5 mm × 2 + 12.5 mm × 2 + 3 mm × 2 + 15 mm × 2 = 386 mm), and the fixing positions were 193 / 386 = 50.0%) at a distance of 193 mm from the corner. Furthermore, the five heads of the long-axis fixing device (five screw heads) are embedded in the surface of the decorative layer, so that the surface of the decorative layer is approximately flat. Screw 5 had the heat-absorbing layers (heat-absorbing layer (A-1) and heat-absorbing layer (B)) pressed into it, and the end of screw 5 reached the base material 5. The long axis fixing devices 6 were fixed at 12 locations on each surface, at intervals of approximately 600 mm, with a total of 12 fixing locations on each surface. These locations were 90 mm from the corners (the distance from the corners is 23.3% (the length of one side in the cross-sectional direction of the decorative layer is 300 mm + 12.5 mm × 2 + 12.5 mm × 2 + 3 mm × 2 + 15 mm × 2 = 386 mm, so the distance from the corners is 90 / 386 = 23.3%)). Furthermore, the six heads of the long-axis fixing device (six screw heads) are embedded in the surface of the decorative layer, so that the surface of the decorative layer is approximately flat. Screw 6 was press-fitted to 80% of the thickness of the heat-absorbing layer (heat-absorbing layer (A-1) and heat-absorbing layer (B)), and the tip of screw 6 was located approximately 5.0 mm from the surface of the base material 2. The obtained test specimens underwent the fire resistance test described above, and the result was an evaluation of "A".

[0157] (Example 4) In the step of bonding the decorative layer, the test specimen was obtained in the same manner as in Example 2, except that the long axis fixing device 3 was fixed at two locations at a distance of 55 mm from the corner (approximately 16.9% of the distance from the corner (the length of one side in the cross-sectional direction of the decorative layer is 326 mm, and the distance from the corner is 55 / 326 = approximately 16.9%)) and at six locations in the vertical direction at approximately 600 mm intervals, for a total of 12 locations on one surface. Screw 3 was press-fitted to 68% of the thickness of the heat-absorbing layer (heat-absorbing layer (A-1) and heat-absorbing layer (B)), and the tip of screw 3 was located approximately 8.0 mm from the surface of base material 1. The obtained test specimens underwent the fire resistance test described above, and the result was an evaluation of "A".

[0158] (Example 5) In the step of bonding the decorative layer, the test specimen was obtained in the same manner as in Example 2, except that the long axis fixing device 3 was fixed in two places at a distance of 55 mm from the corner (approximately 16.9% of the distance from the corner (the length of one side in the cross-sectional direction of the decorative layer is 326 mm, and the distance from the corner is 55 / 326 = approximately 16.9%)) and in seven places at approximately 450 mm intervals in the vertical direction, for a total of 14 fixing points on one surface. Screw 3 was press-fitted to 68% of the thickness of the heat-absorbing layer (heat-absorbing layer (A-1) and heat-absorbing layer (B)), and the tip of screw 3 was located approximately 8.0 mm from the surface of base material 1. The obtained test specimens underwent the fire resistance test described above, and the result was an evaluation of "A".

[0159] (Example 6) A test specimen was obtained in the same manner as in Example 1, except that the heat-absorbing layer (A-1) was replaced with the heat-absorbing layer (A-2). The obtained test specimens underwent the fire resistance test described above, and the result was an evaluation of "A".

[0160] (Example 7) A test specimen was obtained in the same manner as in Example 2, except that the heat-absorbing layer (A-1) was replaced with the heat-absorbing layer (A-2). The obtained test specimens underwent the fire resistance test described above, and the result was an evaluation of "A".

[0161] (Comparative Example 1) A test specimen (Figure 7) was obtained in the same manner as in Example 1, except that the heat-absorbing layer (heat-absorbing layer (A-1)) was replaced with a heat-absorbing layer (heat-absorbing layer (B)). The obtained test specimens underwent the fire resistance test described above, and the result was an evaluation of "C".

[0162] (Comparative Example 2) A test specimen (Figure 8) was obtained in the same manner as in Example 1, except that the heat-absorbing layer (heat-absorbing layer (A-1)) was replaced with the heat-absorbing layer (heat-absorbing layer (B)), and the long shaft fixing device 4 (screw 4 (length 22 mm)) was replaced with the long shaft fixing device 1 (screw 1 (length 32 mm)). The long-axis fixing devices 1 used to secure the decorative layer were fixed at two locations 60 mm from the corners (approximately 20.0% of the distance from the corners (the length of one side in the cross-sectional direction of the decorative layer is 240 mm + 12.5 mm × 2 + 3 mm × 2 + 15 mm × 2 = 301 mm, so the distance from the corners is 60 / 301 = approximately 20.0%)) and at six locations approximately 600 mm apart in the vertical direction, for a total of 12 fixing points per surface. The screw 1 used to fix the decorative layer pressed the heat-absorbing layer (heat-absorbing layer (A-1)) into place and reached the base material 1. The obtained test specimens underwent the fire resistance test described above, and the result was an evaluation of "C".

Claims

1. A laminated structure in which a heat-absorbing layer, a heat-foaming layer, and a decorative layer are laminated in that order on a base material, The aforementioned substrate is an axial substrate with a polygonal cross-section, The heat-absorbing layer is formed from a heat-absorbing composition comprising a binder and one or more selected from inorganic acids, hydroxide compounds, and hydrated compounds. The aforementioned cosmetic layer is the outermost layer, A laminated structure in which, in a region where the distance from each corner of the decorative layer is 40% or less of the length of one side of the substrate in the cross-sectional direction, a fastener is press-fitted from the decorative layer toward the heat-absorbing layer to a thickness of 30% or more but less than 100% of the thickness of the heat-absorbing layer, and the fastener does not reach the substrate.

2. The laminated structure according to claim 1, wherein the inorganic acid comprises boric acid.

3. The laminated structure according to claim 1, wherein the binder is a thermosetting resin.

4. The laminated structure according to claim 1, wherein the substrate is an organic substrate.

5. The laminated structure according to claim 4, wherein the organic substrate is a wood-based substrate and / or a plastic substrate.

6. A method for manufacturing a laminated structure according to any one of claims 1 to 5, A method for manufacturing a laminated structure, comprising laminating the heat-absorbing layer, the heat-foaming layer, and the decorative layer on the substrate in that order, and then driving the fixing device into the decorative layer to fix it to the heat-absorbing layer.

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