Laminates and covering structures

Abstract

To provide a laminate that includes a heat-absorbing layer, formed by a binder and sodium tetraborate, and a thermally expandable layer, allowing for a thinner and lighter structure with enhanced workability, safety, and fire resistance, as well as a coated structure with an organic substrate coated with the laminate.SOLUTION: The present invention provides a laminate that includes a heat-absorbing layer and a thermally expandable layer, where the heat-absorbing layer is formed by a binder and sodium tetraborate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate including a heat-absorbing layer and a thermal foaming layer, and a coating structure in which an organic substrate is covered by the laminate. [Background technology]

[0002] Traditionally, concrete has been widely used in the structural framework of buildings (columns, beams, floors, and foundations), as well as in civil engineering structures such as tunnels and bridges.

[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.

[0007] Patent Document 1 describes how to improve the fire resistance of wood materials by using a laminate of gypsum board, panel insulation material (such as phenolic foam), and non-combustible material (such as calcium silicate board) in addition to the wood material. [Prior art documents] [Patent Documents]

[0008] Patent Document 1 Japanese Patent Application Laid-Open No. 2019-150389 Summary of the Invention Problems to be Solved by the Invention

[0009] However, in Patent Document 1, the specifically disclosed laminate has a large overall thickness, and the inorganic non-combustible materials such as gypsum board and calcium silicate board that occupy most of the thickness have a large specific gravity. Therefore, the laminate has a heavy mass per unit area, is inferior in workability and constructability during transportation and construction, may induce accidents, and has a large load between the base materials used, and has problems. In addition, due to the large thickness of the laminate, when used for columns and walls, there is a risk of compressing the room volume. Furthermore, when used for floorboards, it will lead to a narrower floor height and may interfere with the facility plan.

[0010] Therefore, the problem to be solved by the present invention is to provide a laminate that includes an endothermic layer and a thermal foam layer using specific raw materials, can be made thin and lightweight, and is excellent in workability, safety, and fire resistance, and a coating structure in which an organic base material is coated with the laminate. Means for Solving the Problems

[0011] Therefore, as a result of intensive studies by the present inventors to solve the above problems, they have found that a laminate including an endothermic layer and a thermal foam layer, in which the endothermic layer is formed by a binder and sodium tetraborate, can be made thin and lightweight, and is excellent in workability, safety, and fire resistance, and thus completed the present invention.

[0012] That is, the present invention has the following features. 1. A laminate including an endothermic layer and a thermal foam layer, wherein the endothermic layer is formed by a binder and sodium tetraborate. 2. The laminate according to 1, wherein the binder is an organic binder, and the sodium tetraborate comprises sodium tetraborate decahydrate. 3. The laminate according to 2, wherein the organic binder is obtained by a polyol and an isocyanate. 4. The laminate according to 2, wherein the organic binder is obtained from an unsaturated polyester and an unsaturated monomer. 5. The laminate according to 1, wherein the heat-absorbing layer comprises at least an heat-absorbing layer formed of an organic binder and sodium tetraborate, and a heat-absorbing layer formed of an inorganic binder. 6. The density of the heat-absorbing layer is 0.05 g / cm³. 3 More than 1.5g / cm 3 The laminate described in 1. is less than the specified value. 7. The laminate according to 1., wherein the thickness of the laminate is 60 mm or less. 8. The mass per unit area of ​​the laminate is 40 kg / m². 2 The laminate described in 1. below. 9. A coated structure in which an organic substrate is covered with a laminate described in any of 1. to 8. 10. The covering structure according to 9, wherein the organic substrate is a wood substrate and / or a plastic substrate. 11. The coating structure according to 9, wherein the heat-absorbing layer and the organic substrate are in contact. 12. The covering structure according to 9, wherein the organic substrate is a flat plate or an axial member having a rectangular or circular cross-section. [Effects of the Invention]

[0013] The laminate of the present invention is thin and lightweight, and is useful because it offers excellent workability, safety, and fire resistance. [Brief explanation of the drawing]

[0014] [Figure 1] This is an example of a model diagram (cross-sectional view) showing the covering structure of the present invention. [Figure 2] This is an example of a model diagram (cross-sectional view) showing the covering structure of the present invention. [Figure 3] This is an example of a model diagram (cross-sectional view) showing the covering structure of the present invention. [Figure 4] This is an example of a model diagram (cross-sectional view) showing the covering structure of the present invention. [Figure 5] This is an example of a model diagram (cross-sectional view) showing the covering structure of the present invention. [Figure 6] This is a cross-sectional view showing the laminate (Example 1-1). [Figure 7] This is a cross-sectional view showing the laminate (Examples 1-2). [Figure 8] This is a cross-sectional view showing the laminate (Examples 1-3). [Figure 9] This is a cross-sectional view showing the laminate (Examples 1-4). [Figure 10] This is a cross-sectional view showing the laminate (Examples 1-5). [Figure 11] This is a cross-sectional view showing the laminate (Examples 1-6). [Figure 12] This is a cross-sectional view showing the laminate (Examples 1-7). [Figure 13] This is a cross-sectional view showing the laminate (Examples 1-8). [Figure 14] This is a cross-sectional view showing the laminate (Examples 1-9). [Figure 15] This is a cross-sectional view showing the laminate (Comparative Example 1-1). [Figure 16] This is a cross-sectional view showing the laminate (Comparative Example 1-2). [Figure 17] This is a cross-sectional view showing the covering structure (Example 2-1). [Figure 18] This is a cross-sectional view showing the covering structure (Example 2-2). [Figure 19] This is a cross-sectional view showing the covering structure of (Example 2-3). [Figure 20] This is a cross-sectional view showing the coating structure (Example 2-4). [Figure 21] This is a cross-sectional view showing the coating structure (Example 2-5). [Figure 22] This is a cross-sectional view showing the covering structure (Example 2-6). [Figure 23]This is a cross-sectional view showing the covering structure (Example 2-7). [Figure 24] This is a cross-sectional view showing the coating structure (Example 2-8). [Figure 25] This is a cross-sectional view showing the coating structure of (Comparative Example 2-1). [Figure 26] This is a cross-sectional view showing the coating structure of (Comparative Example 2-2). [Figure 27] This is a cross-sectional view showing the coating structure (Comparative Example 2-3). [Figure 28] This is a cross-sectional view showing the prismatic covering structure of the organic substrate in (Example 3-1). [Figure 29] This is a cross-sectional view showing the prismatic covering structure of the organic substrate in (Example 3-1). [Figure 30] This is a cross-sectional view showing the prismatic coating structure of the organic substrate in (Example 3-2). [Figure 31] This is a cross-sectional view showing the prismatic coating structure of the organic substrate in (Example 3-2). [Figure 32] This is a cross-sectional view showing the prismatic covering structure of the organic substrate in (Example 3-3). [Figure 33] This is a cross-sectional view showing the prismatic covering structure of the organic substrate in (Example 3-3). [Figure 34] This is a cross-sectional view showing the case where the organic substrate of the covering structure of the present invention is a rectangular prism. [Figure 35] This is a cross-sectional view showing the case where the organic substrate of the covering structure of the present invention is a rectangular prism. [Figure 36] This is a cross-sectional view showing the case where the organic substrate of the covering structure of the present invention is a rectangular prism. [Figure 37] This is a cross-sectional view showing the case where the organic substrate of the covering structure of the present invention is a rectangular prism. [Explanation of Symbols]

[0015] 1: Organic base material (base material 11~12) 2A: Endothermic layer (A) (endothermic layer 2A1~2A8) 2B: Endothermic layer (B) (endothermic layer 2B1~2B3, 2Ba, 2Bb) 3: Heat-foamed layer (heat-foamed layer 31-32) 4: Laminate (heat-absorbing layer (A), heat-absorbing layer (B), thermal foaming layer) 5: Makeup layer P: Composite layer (endothermic layer (A), endothermic layer (B)) Q: Composite layer (heat-absorbing layer (B), thermal foaming layer) R: Composite layer (heat-absorbing layer (A), thermal foaming layer) [Modes for carrying out the invention]

[0016] The following describes embodiments for carrying out the present invention.

[0017] [Laminated structure] The present invention relates to a laminate comprising a heat-absorbing layer and a thermal foaming layer, wherein the heat-absorbing layer is formed of a binder and sodium tetraborate.

[0018] [Endothermic layer] The laminate of the present invention is a laminate including a heat-absorbing layer, wherein the heat-absorbing layer is formed of a binder and sodium tetraborate. By using the binder, the sodium tetraborate can be immobilized, and a heat-absorbing layer with excellent heat absorption and lightweight properties can be formed.

[0019] 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 thermal 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 coated structure in which the organic substrate is covered by the laminate becomes more useful, with improved fire resistance and other properties due to the heat-absorbing effect of the heat-absorbing layer.

[0020] (Binder) Examples of the aforementioned binders include organic binders and inorganic binders. From the viewpoint of weight reduction, organic binders are preferred, and from the viewpoint of endothermic properties, inorganic binders are preferred.

[0021] [Heat-absorbing layer (A)] Furthermore, it is preferable that the heat-absorbing layer includes at least an organic binder and a heat-absorbing layer formed of sodium tetraborate (hereinafter sometimes referred to as "heat-absorbing layer (A)"). Using such a heat-absorbing layer (A) is useful because, in addition to fire resistance, it is possible to reduce the weight of the entire laminate.

[0022] (Organic binder) Examples of the organic binders include polyether resins, polyester resins, unsaturated polyester resins, vinyl acetate resins, alkyd resins, epoxy resins, acrylic resins, acrylic silicone resins, urethane resins, phenolic resins, melamine resins, polycarbonate resins, fluororesins, acrylic vinyl acetate resins, acrylic urethane resins, acrylic epoxy resins, silicone-modified acrylic resins, and ethylene vinyl acetate resins. Among these, from the viewpoint of weight reduction, those obtained from polyols and isocyanates (the urethane resin obtained by reaction and curing), or those obtained from unsaturated polyesters and unsaturated monomers (the unsaturated polyester resin obtained by reaction and curing) are preferred. The urethane resin is useful for weight reduction of the resulting laminate because its density can be reduced, and the unsaturated polyester resin is useful for weight reduction of the resulting laminate because its thickness can be reduced.

[0023] (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.

[0024] Examples of the polyester polyols include aromatic polyester polyols, aliphatic polyester polyols, and aromatic / aliphatic polyester polyols.

[0025] Specifically, the aliphatic polyester polyol is a polyol having an aliphatic hydrocarbon in one molecule. Examples include condensed polyester polyols obtained by reacting saturated aliphatic polybasic acids such as succinic acid, adipic acid, azelaic acid, and sebacic acid with polyhydric alcohols, and condensed polyester polyols obtained by reacting unsaturated aliphatic polybasic acids such as maleic acid and fumaric acid with polyhydric alcohols.

[0026] The aforementioned aromatic polyester polyol is a polyol having an aromatic hydrocarbon in one molecule. Examples include condensed polyester polyols obtained by reacting aromatic polybasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride with polyhydric alcohols, and phthalic acid-based polyester polyols obtained by decomposing phthalic acid-based polyester molded products such as polyethylene terephthalate. Examples of polyhydric alcohols include alcohols with a valency of two or more and their derivatives, phenols with a valency of two or more, and polyols.

[0027] The aforementioned aromatic / aliphatic polyester polyols are polyols having an aliphatic hydrocarbon and an aromatic hydrocarbon in one molecule, and examples include condensed polyester polyols obtained by reacting aromatic polybasic acids and aliphatic polybasic acids with polyhydric alcohols.

[0028] Examples of the polyether polyols include aromatic polyether polyols, phosphorus-containing polyether polyols, glycerin-based polyether polyols, and amino group-containing polyether polyols.

[0029] Examples of the aromatic polyether polyols include bisphenol A type polyether polyols obtained by adding an alkylene oxide (e.g., ethylene oxide, propylene oxide, etc.) using bisphenol A as an initiator, and aromatic amine-based polyether polyols obtained by adding an alkylene oxide using an aromatic amine (e.g., toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, Mannich condensate, etc.) as an initiator.

[0030] Examples of the phosphorus-containing polyether polyol include dialkyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate, which is a diol having a phosphate ester structure.

[0031] Examples of the glycerin-based polyether polyol include polyether polyols obtained by adding alkylene oxide with glycerin as an initiator.

[0032] Examples of the amino group-containing polyether polyols include those obtained by adding an alkylene oxide using a low molecular weight amine (e.g., ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc.) as an initiator.

[0033] The castor oil-based polyol is a polymer derived from castor oil or castor oil fatty acids, and examples include alkylene oxide adducts of castor oil or castor oil fatty acids, epoxidized castor oil or castor oil fatty acids, halogenated castor oil or castor oil fatty acids, transesterified castor oil or castor oil fatty acids with polyhydric alcohols, and hydrogenated products thereof. In the present invention, castor oil-based polyols and / or castor oil are particularly preferred, and it is even more preferable to include castor oil.

[0034] In particular, in the present invention, the polyol is preferably a castor oil-based polyol and / or containing castor oil, and more preferably a polyol containing castor oil.

[0035] Furthermore, the mixing ratio (solid content mass ratio) of the castor oil-based polyol and the castor oil is preferably 0:100 to 50:50, and more preferably 0:100 to 30:70.

[0036] 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.

[0037] (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.

[0038] 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.

[0039] Examples of the aliphatic diisocyanates include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate. Examples include anneates, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, lysine diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, etc.

[0040] Examples of the alicyclic diisocyanates include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, 1,4-bis(isocyanate methyl)cyclohexane, isophorone diisocyanate (IPDI), norbornane diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate.

[0041] Examples of the aromatic diisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 2,4-tolylenediisocyanate (TDI), 2,6-tolylenediisocyanate (TDI), naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4,4'-diphenyldiisocyanate, 4,4'-diphenylmethanediisocyanate (MDI), 2,4'-diphenylmethanediisocyanate, Examples include 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, and tetramethylene xylylene diisocyanate.

[0042] Examples of the aforementioned aromatic aliphatic diisocyanates include 1,3-xylylene diisocyanate (XDI), 1,4-xylylene diisocyanate (XDI), ω,ω'-diisocyanate-1,4-diethylbenzene, 1,3-bis(1-isocyanate-1-methylethyl)benzene, 1,4-bis(1-isocyanate-1-methylethyl)benzene, and 1,3-bis(α,α-dimethylisocyanatemethyl)benzene.

[0043] In the present invention, it is particularly preferable to use aliphatic diisocyanates such as HMDI and its derivatives, aromatic diisocyanates such as MDI and its derivatives, etc. Furthermore, in the present invention, it is preferable to use the aliphatic diisocyanate or the aromatic diisocyanate that has been trimerized (isocyanurate), and in particular in the present invention, it is preferable to use the trimerized (isocyanurate) aliphatic diisocyanate.

[0044] 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, the free water from the sodium tetraborate hydrate, as described later, will not be included in the calculation of the active hydrogen-containing components used in the above isocyanate index.

[0045] (Unsaturated polyester) Examples of the unsaturated polyester include those produced by the esterification reaction of a polyhydric alcohol and a polybasic acid.

[0046] 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.

[0047] 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.

[0048] (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.

[0049] In the present invention, the mixing ratio of the unsaturated polyester and the unsaturated monomer is preferably 10 to 200 parts by mass of the unsaturated monomer, and more preferably 20 to 180 parts by mass of the unsaturated monomer, per 100 parts by mass of the unsaturated polyester. By mixing the unsaturated polyester and the unsaturated monomer within this range, and optionally mixing in an initiator, an unsaturated polyester resin having excellent heat resistance and a heat-absorbing layer (heat-absorbing layer (A)) using the unsaturated polyester resin can be obtained.

[0050] (4. Sodium borate) The sodium tetraborate mentioned above is an endothermic component. From the viewpoint of endothermic properties, the sodium tetraborate is preferably sodium tetraborate hydrate, more preferably sodium tetraborate pentahydrate or sodium tetraborate decahydrate, and among these, sodium tetraborate decahydrate is particularly preferred because it releases a large amount of hydrate water from the hydrate, and the temperature at which this water is released is relatively low (about 60°C), thus providing excellent endothermic properties.

[0051] The aforementioned sodium tetraborate pentahydrate is a substance that releases water of hydration at around 100-150°C. Furthermore, the aforementioned sodium tetraborate decahydrate is a substance that releases water of hydration at around 60°C. Furthermore, if the organic binder is a urethane resin, the sodium tetraborate hydrate, when mixed with the polyol and the isocyanate, releases free water from the sodium tetraborate hydrate, which reacts with the isocyanate to produce carbon dioxide and cause foaming, thus contributing to weight reduction. It is also a component that contributes to the lightness of the heat-absorbing layer (heat-absorbing layer (A)).

[0052] The content of sodium borate is preferably 5% by mass or more and 90% by mass or less of the total heat-absorbing layer (A) (more preferably 10% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 70% by mass or less). Within this range, a heat-absorbing layer (heat-absorbing layer (A)) that sufficiently combines both heat absorption and lightness can be obtained.

[0053] The sodium borate content is 2.0 kg / m³ relative to the heat-absorbing layer (A). 2 (More than 2.5 kg / m 2 More than 20.0kg / m 2 More preferably, 3.0 kg / m 2 More than 15.0kg / m 2 The following is preferable. Within this range, a heat-absorbing layer (heat-absorbing layer (A)) that sufficiently combines both heat absorption and lightweight properties can be obtained.

[0054] The amount of sodium borate mixed is preferably 5 parts by mass or more and 2000 parts by mass or less (more preferably 10 parts by mass or more and 1800 parts by mass or less, and even more preferably 20 parts by mass or more and 1500 parts by mass or less) per 100 parts by mass of the organic binder.

[0055] When the organic binder is a urethane resin, it is particularly preferable that the amount of sodium 4-borate mixed is 30 parts by mass or more and 2000 parts by mass or less (more preferably 50 parts by mass or more and 1800 parts by mass or less, and even more preferably 100 parts by mass or more and 1500 parts by mass or less) per 100 parts by mass of the polyol.

[0056] When the organic binder is an unsaturated polyester resin, the amount of sodium 4-borate mixed is preferably 40 parts by mass or more and 2000 parts by mass or less (more preferably 80 parts by mass or more and 1800 parts by mass or less, and even more preferably 120 parts by mass or more and 1500 parts by mass or less) per 100 parts by mass of the unsaturated polyester.

[0057] 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 the like. 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.

[0058] 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.

[0059] The mixing amount of the filler may be 10 parts by mass or more and 500 parts by mass or less (more preferably 20 parts by mass or more and 400 parts by mass or less) with respect to 100 parts by mass of the organic binder. Within such a range, excellent strength can be exhibited while ensuring lightness.

[0060] When the organic binder is a urethane resin, in particular, the mixing amount of the filler may be 30 parts by mass or more and 500 parts by mass or less (more preferably 50 parts by mass or more and 400 parts by mass or less) with respect to 100 parts by mass of the polyol. Within such a range, excellent strength can be exhibited while ensuring lightness.

[0061] When the organic binder is an unsaturated polyester resin, in particular, the mixing amount of the filler may be 40 parts by mass or more and 500 parts by mass or less (more preferably 80 parts by mass or more and 400 parts by mass or less) with respect to 100 parts by mass of the unsaturated polyester.

[0062] Particularly in the present invention, as the filler, a lightweight filler having a bulk density of 0.01 g / cm 3 or more and less than 1 g / cm 3 can be used. For example, one or more of perlite, expanded vermiculite, pumice, vermiculite, ALC crushed material, ceramic hollow beads, hollow glass beads, charcoal, bamboo charcoal, seed shell charcoal, seed shell smoked charcoal, styrene resin foam, ethylene vinyl acetate resin foam, vinyl chloride resin foam, etc. can be used. 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 shell charcoal, and seed shell smoked charcoal can be used.

[0063] The mixing amount of the lightweight filler may be 300 parts by mass or less (more preferably 250 parts by mass or less) with respect to 100 parts by mass of the organic binder. When the lightweight filler is within such a range, it is advantageous in terms of lightness and strength. Also, when the lightweight filler is a non-combustible lightweight filler, it is advantageous in terms of heat resistance.

[0064] If the organic binder is a urethane resin, the amount of the lightweight filler to be mixed should be 300 parts by mass or less (more specifically, 250 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.

[0065] If the organic binder is an unsaturated polyester resin, the amount of the lightweight filler to be mixed should be 300 parts by mass or less (more specifically, 250 parts by mass or less) per 100 parts by mass of the unsaturated polyester. 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.

[0066] 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.

[0067] 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.

[0068] Examples of the aforementioned flame retardants include phosphorus-based flame retardants, halogen-based flame retardants, boron-based flame retardants, metal hydroxide-based flame retardants, nitrogen-based flame retardants, silicon-based flame retardants, etc., and one or more of these can be used.

[0069] 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.

[0070] Specifically, the phosphate ester compounds include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trisnonylphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresylphenyl phosphate, cresyldiphenyl phosphate, octyldiphenyl phosphate, trixylenyl phosphate, diisopropylphenyl phosphate, tris(2-ethylhexyl) phosphate, resorcinol bisdiphenyl phosphate, bisphenol A bis(diphenyl phosphate), resorcinol bisdixylenyl phosphate, tris(chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, bis(2, Examples include 3-dibromopropyl)-2,3-dichloropropyl phosphate, tris(2,3-dibromopropyl) phosphate, bis(chloropropyl)monooctyl phosphate, hydroquinonyldiphenyl phosphate, phenylnonylphenylhydroquinonyl phosphate, phenyldinonylphenyl phosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphate, diphenyl-4-hydroxy-3,5-dibromobenzyl phosphate, trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, resorcinol poly(di-2,6-xylyl) phosphate, and hydroquinone poly(2,6-xylyl) phosphate.

[0071] 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.

[0072] Examples of the polyphosphate compounds include ammonium polyphosphate, ammonium polyphosphate amide, melamine polyphosphate, piperazine polyphosphate, melem polyphosphate, melam polyphosphate, melon polyphosphate, and aluminum polyphosphate.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] Examples of the boron-based flame retardants include boron oxide, boric acid, lithium borate, sodium borate (excluding sodium tetraborate), potassium borate, cesium borate, magnesium borate, calcium borate, barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate.

[0077] Examples of the aforementioned metal hydroxide-based flame retardants include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, zinc hydroxide, titanium hydroxide, copper hydroxide, tin hydroxide, and vanadium hydroxide.

[0078] The amount of the flame retardant mixed is preferably 5 to 1000 parts by mass (more preferably 10 to 500 parts by mass, even more preferably 15 to 200 parts by mass, even more preferably 20 to 100 parts by mass, and most preferably 25 to 80 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 achieve both heat resistance and light weight.

[0079] When the organic binder is a urethane resin, the amount of the flame retardant mixed is preferably 10 to 1000 parts by mass (more preferably 15 to 500 parts by mass, even more preferably 20 to 200 parts by mass, even more preferably 25 to 100 parts by mass, and most preferably 30 to 80 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.

[0080] When the organic binder is an unsaturated polyester resin, the amount of the flame retardant mixed is preferably 10 parts by mass or more and 1000 parts by mass or less (more preferably 15 parts by mass or more and 500 parts by mass or less, even more preferably 20 parts by mass or more and 200 parts by mass or less, even more preferably 25 parts by mass or more and 100 parts by mass or less, and most preferably 30 parts by mass or more and 80 parts by mass or less) per 100 parts by mass of the unsaturated polyester. By having the flame retardant within this range, it is possible to improve dispersibility and further achieve both heat resistance and light weight. In particular, it is preferable to use, as the unsaturated polyester, one produced by the esterification reaction of a polyhydric alcohol selected from ethylene glycol and propylene glycol with a polybasic acid selected from maleic acid, maleic anhydride, fumaric acid, and isophthalic acid, and as the unsaturated monomer, (meth)acrylic acid ester monomer and / or aromatic monomer in the above-mentioned mixed proportions.

[0081] Furthermore, in the present invention, it is preferable to use the flame retardant and sodium tetraborate in combination. 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 sodium tetraborate and the viscosity of the composition can be controlled, making it possible to obtain a heat-absorbing layer with superior heat resistance and lightness.

[0082] 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.

[0083] 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).

[0084] 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).

[0085] 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.

[0086] 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.

[0087] 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.

[0088] Examples of the polyether-modified silicone compound include graft copolymers of polydimethylsiloxane and polyoxyethylene glycol or polyoxyethylene-propylene glycol.

[0089] 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.

[0090] 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.).

[0091] 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.

[0092] 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.

[0093] 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.

[0094] Examples of the initiators include organic peroxides such as hydroperoxides, dialkyl peroxides, diacyl peroxides, 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.

[0095] When the organic binder is an unsaturated polyester resin, the amount of the initiator mixed is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 80 parts by mass, per 100 parts by mass of the unsaturated monomer.

[0096] Furthermore, the heat-absorbing layer (A) may also contain other metal hydrates in addition to the sodium tetraborate. Examples of such metal hydrates include sulfates such as ammonium aluminum sulfate dodecahydrate, sodium aluminum sulfate dodecahydrate, aluminum sulfate heptahydrate, aluminum sulfate octahydrate, aluminum sulfate hectahydrate, aluminum sulfate decahydrate, aluminum sulfate hexahydrate, potassium aluminum sulfate dodecahydrate, iron sulfate heptahydrate, iron sulfate nipatahydrate, potassium iron sulfate dodecahydrate, magnesium sulfate heptahydrate, sodium sulfate decahydrate, nickel sulfate heptahydrate, zinc sulfate heptahydrate, beryllium sulfate tetrahydrate, zirconium sulfate tetrahydrate, etc.; sulfites such as zinc sulfite dihydrate, sodium sulfite heptahydrate, etc.; aluminum phosphate dihydrate, cobalt phosphate octahydrate, magnesium phosphate Examples include phosphates such as zinc octahydrate, magnesium ammonium phosphate hexahydrate, magnesium hydrogen phosphate trihydrate, magnesium hydrogen phosphate heptahydrate, zinc phosphate tetrahydrate, and zinc dihydrogen phosphate dihydrate; 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; acetates such as zinc acetate dihydrate and cobalt acetate tetrahydrate; chlorides such as cobalt chloride hexahydrate and iron chloride tetrahydrate; and metal hydrates such as disodium octaborate tetrahydrate and zinc borate 3.5hydrate.

[0097] The heat-absorbing layer (A) can be obtained by mixing the polyol, the isocyanate, and the sodium tetraborate, adding other additives as needed, mixing, and curing to obtain a heat-absorbing layer (A) containing urethane resin and sodium tetraborate. In particular, a first liquid (first component) is prepared by mixing the polyol, the sodium tetraborate, 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). In addition, the sodium tetraborate 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 70°C (more preferably 15°C to 50°C).

[0098] Furthermore, the heat-absorbing layer (A) can be obtained by mixing the unsaturated polyester, the unsaturated monomer, and the sodium tetraborate, adding other additives as needed, mixing, and curing to obtain a heat-absorbing layer (A) containing an unsaturated polyester resin and sodium tetraborate. In particular, a first liquid (first component) is prepared by mixing the unsaturated polyester, the unsaturated monomer, and the sodium tetraborate, and optionally other additives, 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). In addition, the sodium tetraborate 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 70°C (more preferably 15°C to 50°C).

[0099] [Endothermic layer (B)] Furthermore, it is preferable that the heat-absorbing layer includes, 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) does not contain (substantially contains) sodium tetraborate. Specifically, it is a heat-absorbing layer that does not contain (substantially contains) the organic binder (urethane resin, polyols and isocyanates constituting the urethane resin, and unsaturated polyester resin, unsaturated polyesters and unsaturated monomers constituting the unsaturated polyester resin) or sodium tetraborate (including sodium tetraborate decahydrate). Note that "substantially contains" means that it accounts for less than 5% by mass of the entire heat-absorbing layer (B).

[0100] (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.

[0101] 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.

[0102] The aforementioned hydraulic inorganic binder can form a large amount of bound water during bonding, creating an absorbent layer. (B) can contain a large amount of bound water. As a result, when the temperature rises, it can exhibit excellent endothermic properties by utilizing the latent heat of vaporization of the bound water. Furthermore, the endothermic layer (B) containing the hydraulic inorganic binder also has excellent strength, which can make the strength of the laminate of the present invention excellent.

[0103] 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.

[0104] 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. (B) can be obtained. In addition, reinforcing materials such as glass nonwoven fabric, glass cloth, and ceramic paper can be embedded during manufacturing.

[0105] 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.

[0106] The laminate of the present invention can use a laminate 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.

[0107] 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.

[0108] Methods (2) and (3) described above allow for adhesive-free lamination (direct lamination without using adhesive), and when exposed to high temperatures due to fire or other reasons, heat generation caused by the adhesive can be suppressed. For example, method (2) exhibits excellent adhesion.

[0109] 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).

[0110] 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 the organic binder and sodium tetraborate, 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 the inorganic binder, or which have different thicknesses.

[0111] The density of the heat-absorbing layer (A) is 0.05 g / cm³. 3 More than 1.5g / cm 3 Less than (more preferably 0.08 g / cm³) 3 More than 1.2g / cm 3 More preferably, 0.1 g / cm³ 3 More than 1.0g / cm 3 The following is preferable: The density of the heat-absorbing layer (B) is 0.1 g / cm³. 3 More than 1.5g / cm 3 Below (more preferably 0.3 g / cm³) 3 More than 1.2g / cm 3 More preferably, 0.5 g / cm³ 3 More than 1.0g / cm 3 The following is preferable: The aforementioned heat-absorbing layers (heat-absorbing layer (A) and heat-absorbing layer (B)) have such densities, making it possible to obtain a heat-absorbing layer that is lightweight yet excellent in heat resistance, strength, and dimensional stability.

[0112] Furthermore, if the heat-absorbing layer (B) is included in addition to the heat-absorbing layer (A), the total density of the heat-absorbing layer is 0.05 g / cm³. 3 More than 1.5g / cm 3 Less than (more preferably 0.08 g / cm³) 3 More than 1.2g / cm 3 More preferably, 0.1 g / cm³ 3 More than 1.0g / cm 3 The following is preferable:

[0113] 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). 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).

[0114] [Thermal foam layer] The laminate of the present invention includes a heat-absorbing layer and a thermal foaming layer. As the thermal foaming layer, a material can be used that, when the ambient temperature rises due to a fire or the like and the temperature of the thermal foaming layer reaches a predetermined foaming temperature, foams up due to the respective raw materials constituting the thermal foaming layer, forming a carbonized heat insulating layer.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] Examples of the foaming agents include melamine and its derivatives, dicyandiamide and its derivatives, azobistetrasome and its derivatives, azodicarbonamide, urea, thiourea, and the like.

[0121] Examples of the carbonizing agent include pentaerythritol, dipentaerythritol, trimethylolpropane, starch, and casein.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] (Other layers) The laminate of the present invention includes (is formed by laminating) the heat-absorbing layer and the heat-foaming layer, but 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 adhesive layers, decorative layers, and other layers (e.g., reinforcing layers, heat-reflective layers, heat-shielding layers, waterproof layers, water-repellent layers, water-shielding layers, heat-insulating layers, etc.).

[0129] 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.

[0130] 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 laminate, making it useful.

[0131] 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.

[0132] By providing the heat-reflective layer between the heat-foaming layer and the heat-absorbing layer, the heat-foaming layer expands smoothly, enabling the formation of an excellent carbonized heat-insulating layer.

[0133] 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.

[0134] (Characteristics of laminates) The laminate of the present invention can be made thinner than the conventional technology, and 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 thickness of the laminate below the upper limit of the above range, the burden on workers and the risk of injury during transportation and construction can be reduced, and work efficiency can be improved. When installed on columns, beams, floor slabs, walls, etc. inside a room, it is also possible to expand the interior space. If the thickness of the laminate is above the lower limit of the above range, it is preferable in terms of heat insulation, fire resistance, strength, etc.

[0135] The mass per unit area of ​​the laminate of the present invention 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.

[0136] [Covered structure] The present invention relates to a coated structure in which an organic substrate is covered by the laminate. The coated structure is preferable because the organic substrate is covered by the laminate which includes the heat-absorbing layer and the heat-foaming layer, resulting in excellent fire resistance.

[0137] Furthermore, it is preferable that the heat-absorbing layer and the organic substrate are in contact with each other in the coating structure of the present invention. When the heat-absorbing layer contained in the laminate is in contact with the organic substrate, the temperature rise of the organic substrate can be suppressed when the temperature rises, such as during a fire, resulting in excellent fire resistance, which is preferable.

[0138] (Organic base material) Examples of the organic substrate include wood substrates, plastic substrates, fiber-reinforced plastic substrates, paper substrates, fibrous substrates, or substrates that combine these. From the viewpoint of strength and lightness, wood substrates, plastic substrates, fiber-reinforced plastic substrates, or substrates that combine these are preferable.

[0139] 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.

[0140] 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 "wood 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 substantially parallel to each other) in the width direction with their fiber directions substantially parallel to each other." By using CLT as the wood-based material, the laminate of the present invention can be applied to structural members (structural frames), etc.

[0141] The thickness of the aforementioned wood-based material can be set appropriately depending on the application and other factors.

[0142] As the aforementioned plastic substrate, a substrate mainly composed of a thermoplastic resin and / or a thermosetting resin can be used.

[0143] 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.

[0144] 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.

[0145] 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 laminate of the present invention can be applied to structural members (structural frames) and the like.

[0146] 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.

[0147] The thickness of the aforementioned plastic substrate can be set appropriately depending on the application and other factors.

[0148] Examples of the organic substrate include flat plates or axial members with a rectangular or circular cross-section. Flat plates and axial members with a rectangular or circular cross-section are preferred because they are frequently used in flooring, wall materials, columns (square columns, round columns, etc.), and beams, respectively, and offer excellent workability.

[0149] The following describes a coated structure in which the organic substrate (hereinafter sometimes simply referred to as "substrate") is covered with the laminate, using the drawings as a reference.

[0150] Figures 1 to 5 show an example (cross-sectional view) of the coating structure of the present invention. In the following, the heat-absorbing layer 2A etc. corresponds to the heat-absorbing layer (A), and the heat-absorbing layer 2B etc. corresponds to the heat-absorbing layer (B). Also, the heat-absorbing layer 2Ba and heat-absorbing layer 2Bb in Figure 5 correspond to the heat-absorbing layer (B), and it is shown that the heat-absorbing layer (B) has multiple layers.

[0151] In the coating structure shown in Figure 1, a heat-absorbing layer 2A, a heat-absorbing layer 2B, and a thermal foaming layer 3 are sequentially laminated on an organic substrate 1 as a laminate 4. That is, the heat-absorbing layer 2A side of the laminate 4 is fixed in contact with the organic substrate 1. In this invention, two or more materials can be laminated as the materials constituting each layer. A coating structure with such a laminate 4 can exhibit excellent fire resistance. Specifically, when the thermal foaming layer 3 side is exposed to high temperatures due to fire or the like, the heat-absorbing layer 2B exhibits a heat-absorbing effect, and the thermal foaming layer 3 foams up to form a carbonized insulating layer, thereby suppressing the transfer of heat to the heat-absorbing layer 2A located inside it, and thus maintaining the shape of the heat-absorbing layers 2B and 2A. The heat-absorbing layer 2A then sufficiently suppresses the temperature rise of the organic substrate 1 due to its performance. In this invention, the synergistic effect of these three layers prevents combustion, deformation, and strength reduction of the organic base material 1 due to heat, thereby exhibiting excellent fire resistance.

[0152] The covering structure may include cases where the organic base material 1 is a flat plate or an axial member with a rectangular or circular cross-section. As an example of the covering structure of the present invention (cross-sectional view), when the organic base material 1 is an axial member (prism) with a rectangular cross-section, for example, the covering structures shown in Figures 28 to 37 can be cited.

[0153] Furthermore, as shown in the coating structure of Figure 2, the organic substrate 1 can be laminated in a laminate 4 in which a heat-absorbing layer 2B, a heat-absorbing layer 2A, and a thermal foaming layer 3 are sequentially laminated. In the coating structure of Figure 2, the heat-absorbing layer 2B side of the laminate 4 is fixed so as to be in contact with the organic substrate 1. In the present invention, the synergistic effect of these three layers can also prevent combustion, deformation, and strength reduction of the organic substrate 1 due to heat, thereby exhibiting excellent fire resistance.

[0154] When a wood-based substrate such as CLT or a fiber-reinforced plastic substrate is used as the organic substrate 1, it becomes possible to use it as a structural member (structural frame) while taking advantage of its lightweight material properties. In particular, when a wood-based substrate such as CLT is used as the organic substrate 1, it is also preferable in terms of promoting carbon neutrality.

[0155] For example, the following methods can be used to form the coating structure of the present invention. (1) A method of manufacturing a laminate 4 having a heat-absorbing layer 2A, a heat-absorbing layer 2B, and a thermal foaming layer 3, or a laminate 4 having a heat-absorbing layer 2B, a heat-absorbing layer 2A, and a thermal foaming layer 3, and fixing it so that the heat-absorbing layer 2A side or the heat-absorbing layer 2B side in the laminate 4 is in contact with the organic substrate 1 (Figures 1 and 2). (2) A method of fixing the heat-absorbing layer 2A, the heat-absorbing layer 2B, and the heat-foaming layer 3 to the organic substrate 1 in order, or a method of fixing the heat-absorbing layer 2B, the heat-absorbing layer 2A, and the heat-foaming layer 3 to the organic substrate 1 in order (Figures 1 and 2). (3) A composite layer P having a heat-absorbing layer 2A and a heat-absorbing layer 2B is manufactured in advance, the composite layer P is fixed to the organic substrate 1, and then the heat-foamed layer 3 is fixed (Figure 3). (4) A composite layer Q having a heat-absorbing layer 2B and a thermal foaming layer 3 is manufactured in advance, and the heat-absorbing layer 2A is fixed to the organic substrate 1, and then the composite layer Q is fixed, or a composite layer R having a heat-absorbing layer 2A and a thermal foaming layer 3 is manufactured in advance, and the heat-absorbing layer 2B is fixed to the organic substrate 1, and then the composite layer R is fixed (Figure 4). (5) A method in which a composite layer P having a heat-absorbing layer 2A and a heat-absorbing layer 2Ba, and a composite layer Q having a heat-absorbing layer 2Bb and a heat-foaming layer 3 are manufactured in advance, and the composite layer P is fixed to the organic substrate 1, and then the composite layer Q is fixed (Figure 5).

[0156] For fixing each of the above-mentioned layers, composite layers, and laminates, fasteners such as nails, screws, rivets, pins, bolts, staples, or adhesives can be used. Furthermore, the heat-expanded layer 3 can also be formed, for example, by applying a heat-expandable coating material to the surface of the heat-absorbing layer 2B (or the heat-absorbing layer 2A).

[0157] In the present invention, even when a heat-conductive material such as a metal fastener is used as the fastener, the thermal foam layer 3 foams up to form a carbonized insulating layer when the temperature rises, such as during a fire, thereby suppressing the thermal bridging effect caused by the fastener.

[0158] In the present invention, it is preferable that each of the above-mentioned layers, composite layers, and laminates are made of plate-like material (plate material), either or all of them. This improves workability during construction. In particular, because the laminate of the present invention is lightweight, the covering structure of the present invention can be formed in one or two fixing steps, which is efficient. For example, the covering structure of the present invention can be formed in one step using method (1) above, and in two steps using methods (3) to (5) above.

[0159] When using board materials in the manner described in (2) to (5) above, the joints between multiple board materials constituting the lower layer (lower layer joints) and the joints between multiple board materials constituting the upper layer (upper layer joints) may be in the same position. However, in terms of improving fire resistance, it is desirable to offset the joints between the lower layer and the upper layer so that they are in different positions.

[0160] The thermal foaming layer 3 is provided on the surface of the heat-absorbing layer 2B (or the heat-absorbing layer 2A), but it can also be provided on the sides of the laminate. For example, when using plate materials by the methods (1) to (5) described above, by providing the thermal foaming layer 3 along the sides of the plate materials, the thermal foaming layer can also be provided at the joints (butt joints) between multiple plate materials, thereby improving fire resistance.

[0161] The laminate of the present invention can be applied to applications requiring fire resistance in various fields such as architecture, civil engineering, ships, vehicles, and aircraft. When used as a building material, it can be applied to ceiling materials, roofing materials, wall materials, flooring materials, columns, beams, eaves, doors, partitions, etc., and is particularly preferably applied to structural frames such as wall materials, flooring materials, columns, and beams.

[0162] Furthermore, since the coating structure of the present invention is made by coating an organic substrate with the aforementioned laminate, it has excellent fire resistance and other properties, and can suppress the temperature of the surface of the organic substrate when the temperature rises, such as during a fire. [Examples]

[0163] 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.

[0164] The following materials were used to construct the laminate used as the test specimen.

[0165] • Base material 11: Wood-based base material (organic base material) (600mm x 450mm, 25mm thick, in board form) • Base material 12: Wood-based base material (organic base material) (210mm x 210mm, height 800mm, rectangular prism)

[0166] • Decorative layer 5: Wood panel (thickness 10mm, mass 3.8kg / m) 2 )

[0167] ·Thermoabsorption layer 2A1 constituents: Endothermic layer 2A1 first component: Castor oil (hydroxyl value: 160 mg KOH / g, solids content 100% by mass) 28 parts by mass 58 parts by mass of sodium borate decahydrate. Tris(chloropropyl)phosphate (100% solids by mass) 14 parts by mass Dibutyltin dilaurate (solid content 100% by mass) 0.5 parts by mass Endothermic layer 2A1 second component 25 parts by mass of HMDI-based polyisocyanurate (NCO%: 20, solids content 100% by mass) (Isocyanate index: 150)

[0168] ·Heat absorbing layer 2A2 constituents: Endothermic layer 2A2 first component: Castor oil (hydroxyl value: 160 mg KOH / g, solids content 100% by mass) 28 parts by mass 4. Sodium borate pentahydrate 58 parts by mass Tris(chloropropyl)phosphate (100% solids by mass) 14 parts by mass Dibutyltin dilaurate (solid content 100% by mass) 0.5 parts by mass Endothermic layer 2A2 second component 25 parts by mass of HMDI-based polyisocyanurate (NCO%: 20, solids content 100% by mass) (Isocyanate index: 150)

[0169] · Endothermic layer 2A3 constituents: Endothermic layer 2A3 first component: Castor oil (hydroxyl value: 160 mg KOH / g, solids content 100% by mass) 28 parts by mass 58 parts by mass of aluminum hydroxide Tris(chloropropyl)phosphate (100% solids by mass) 14 parts by mass Dibutyltin dilaurate (solid content 100% by mass) 0.5 parts by mass Endothermic layer 2A3 second component 25 parts by mass of HMDI-based polyisocyanurate (NCO%: 20, solids content 100% by mass) (Isocyanate index: 150)

[0170] ·Heat absorbing layer 2A4 constituents: Endothermic layer 2A4 first component Castor oil (hydroxyl value: 160 mg KOH / g, solids content 100% by mass) 18 parts by mass Castor oil-based polyol (hydroxyl value: 220 mg KOH / g, solids content 100% by mass) 10 parts by mass 58 parts by mass of sodium borate decahydrate. Tris(chloropropyl)phosphate (100% solids by mass) 14 parts by mass Dibutyltin dilaurate (solid content 100% by mass) 0.05 parts by mass Endothermic layer 2A4 second component MDI-based polyisocyanurate (NCO%: 20, solids content 100% by mass) 20 parts by mass (Isocyanate index: 160)

[0171] ·Heat absorbing layer 2A5 constituents: Endothermic layer 2A5 first component Castor oil-based polyol (hydroxyl value: 220 mg KOH / g, solids content 100% by mass) 10 parts by mass 67 parts by mass of sodium borate decahydrate. Tris(chloropropyl)phosphate (100% solids by mass) 30 parts by mass Dibutyltin dilaurate (solid content 100% by mass) 0.05 parts by mass Additive (dispersant): 3 parts by mass Heat absorbing layer 2A5 second component 10 parts by mass of HMDI-based polyisocyanurate (NCO%: 20, solids content 100% by mass) (Isocyanate index: 190)

[0172] ·Heat absorbing layer 2A6 constituents: Endothermic layer 2A6 first component Terephthalic acid-based polyester polyol (hydroxyl value: 180 mg KOH / g, solids content 100% by mass) 9 parts by mass 40 parts by mass of sodium borate decahydrate Tris(chloropropyl)phosphate (100% solids by mass) 58 parts by mass Dibutyltin dilaurate (solid content 100% by mass) 0.7 parts by mass Additives (silicone-based foam stabilizer, dispersant): 1 part by mass Endothermic layer 2A6 second component 12 parts by mass of HMDI-based polyisocyanurate (NCO%: 20, solids content 100% by mass) (Isocyanate index: 180)

[0173] · Endothermic layer 2A7 constituents: Endothermic layer 2A7 first component Unsaturated polyester resin (unsaturated polyester / styrene (mass ratio 60 / 40)) 50 parts by mass 50 parts by mass of sodium borate decahydrate. Endothermic layer 2A7 second component 1 part by mass of methyl ethyl peroxide

[0174] ·Heat absorbing layer 2A8 constituents: Endothermic layer 2A8 first component Unsaturated polyester resin (unsaturated polyester / styrene (mass ratio 58 / 42) 48 parts by mass) 52 parts by mass of sodium borate decahydrate. Endothermic layer 2A8 second component 1 part by mass of methyl ethyl peroxide

[0175] • Heat-absorbing layer 2B1: Glass fiber nonwoven gypsum board (thickness 8mm, weight 6.8kg / m) 2 ) • Heat-absorbing layer 2B2: Glass fiber nonwoven gypsum board (thickness 5mm, mass 4.2kg / m) 2 ) • Heat-absorbing layer 2B3: Glass fiber reinforced gypsum board (thickness 12.5 mm, mass 11.0 kg / m) 2 )

[0176] • Heat-expanded layer 31: Heat-expandable sheet [A heat-expandable sheet obtained by kneading 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.) in a kneader heated to 120°C, rolling, and then allowing it to cool to room temperature. Thickness 1.1 mm, mass 1.5 kg / m 2 ] • Heat-expanded layer 32: Heat-expandable sheet [A heat-expandable sheet obtained by kneading a mixture of thermoplastic resin (ethylene vinyl acetate copolymer resin / acrylic resin) 100 parts by mass, foaming agent (melamine) 60 parts by mass, carbonizing agent (pentaerythritol) 60 parts by mass, flame retardant (ammonium polyphosphate) 300 parts by mass, filler (titanium dioxide) 75 parts by mass, and other additives (fibers, plasticizers, etc.) in a kneader heated to 120°C, rolling, and then allowing to cool to room temperature. Thickness 3 mm, mass 4.2 kg / m 2 ]

[0177] • Organic insulation layer: Flame retardant-containing polystyrene foam board (30mm thick, thermal conductivity 0.038 W / (m·K), density 40 kg / m³) 3, mass 1.2kg / m 2 ISO-5660 (Radiant heat intensity 50kW / m 2 Total heat output of 8 MJ / m³ (burned for 5 minutes) 2 below)

[0178] • Acrylic resin adhesive (water-based reactive curing acrylic adhesive)

[0179] [Example 1-1] (Test specimen 1-1) A heat-absorbing layer 2B1 was placed inside a mold (100 mm x 100 mm), a mixture of the first component and the second component of the heat-absorbing layer 2A1 was poured onto the heat-absorbing layer 2B1, a load of 1 MPa was applied, and the mixture was reacted at 40°C for 1 hour. The mold was then removed to obtain a laminate of the heat-absorbing layer 2B1 and the heat-absorbing layer 2A1. Furthermore, a thermal foaming layer 31 was bonded to the heat-absorbing layer 2B1 side of the laminate using an acrylic resin adhesive to obtain test specimen 1-1. The sodium tetraborate hydrate content of the heat-absorbing layer 2A1 was 4.2 kg / m². 2 This was the case. Test specimen 1-1 is in the form shown in Figure 6.

[0180] [Examples 1-2] (Test specimens 1-2) A heat-absorbing layer 2B1 was placed inside a mold (100 mm x 100 mm), a mixture of the first component and the second component of the heat-absorbing layer 2A2 was poured onto the heat-absorbing layer 2B1, a load of 1 MPa was applied, and the mixture was reacted at 40°C for 1 hour. The mold was then removed to obtain a laminate of the heat-absorbing layer 2B1 and the heat-absorbing layer 2A2. Furthermore, a thermal foaming layer 31 was bonded to the heat-absorbing layer 2A2 side of the laminate using an acrylic resin adhesive to obtain test specimens 1-2. The sodium tetraborate hydrate content of the heat-absorbing layer 2A2 was 4.2 kg / m². 2 This was the case. Test specimen 1-2 is in the form shown in Figure 7.

[0181] [Examples 1-3] (Test specimens 1-3) A heat-absorbing layer 2B1 was placed in a mold (100 mm x 100 mm), a mixture of the first component of heat-absorbing layer 2A1 and the second component of heat-absorbing layer 2A1 was poured onto the heat-absorbing layer 2B1, another heat-absorbing layer 2B1 was laminated on top of that, a load of 1 MPa was applied, the mixture was reacted at 40°C for 1 hour, and the mold was removed to obtain a laminate of heat-absorbing layer 2B1 / heat-absorbing layer 2A1 / heat-absorbing layer 2B1. Furthermore, a thermal foaming layer 31 was bonded to one side of the laminate (heat-absorbing layer 2B1 / heat-absorbing layer 2A1 / heat-absorbing layer 2B1) using an acrylic resin adhesive to obtain test specimens 1-3. The sodium tetraborate hydrate content of heat-absorbing layer 2A1 was 4.2 kg / m². 2 This was the case. Test specimen 1-3 is in the form shown in Figure 8.

[0182] [Examples 1-4] (Test specimens 1-4) A heat-absorbing layer 2B1 was placed in a mold (100 mm x 100 mm), a mixture of the first component and the second component of the heat-absorbing layer 2A4 was poured onto the heat-absorbing layer 2B1, another heat-absorbing layer 2B1 was laminated on top of that, a load of 1 MPa was applied, the mixture was reacted at 40°C for 1 hour, and the mold was removed to obtain a laminate of heat-absorbing layer 2B1 / heat-absorbing layer 2A4 / heat-absorbing layer 2B1. Furthermore, a thermal foaming layer 31 was bonded to one side of the laminate (heat-absorbing layer 2B1 / heat-absorbing layer 2A4 / heat-absorbing layer 2B1) using an acrylic resin adhesive to obtain test specimens 1-4. The sodium tetraborate hydrate content of heat-absorbing layer 2A4 was 3.9 kg / m². 2 This was the case. Test specimen 1-4 is in the form shown in Figure 9.

[0183] [Examples 1-5] (Test specimens 1-5) A heat-absorbing layer 2B1 was placed in a mold (100 mm x 100 mm), a mixture of the first component of heat-absorbing layer 2A1 and the second component of heat-absorbing layer 2A1 was poured onto the heat-absorbing layer 2B1, another heat-absorbing layer 2B1 was laminated on top of that, a load of 1 MPa was applied, the mixture was reacted at 40°C for 1 hour, and the mold was removed to obtain a laminate of heat-absorbing layer 2B1 / heat-absorbing layer 2A1 / heat-absorbing layer 2B1. Furthermore, a thermal foaming layer 31 was bonded to one side of the laminate (heat-absorbing layer 2B1 / heat-absorbing layer 2A1 / heat-absorbing layer 2B1) using an acrylic resin adhesive to obtain test specimens 1-5. The sodium tetraborate hydrate content of heat-absorbing layer 2A1 was 3.2 kg / m². 2 This was the case. Test specimens 1-5 are in the configuration shown in Figure 10.

[0184] [Examples 1-6] (Test specimens 1-6) A heat-absorbing layer 2B1 was placed inside a mold (100 mm x 100 mm), a mixture of the first component and the second component of the heat-absorbing layer 2A1 was poured onto the heat-absorbing layer 2B1, a load of 1 MPa was applied, and the mixture was reacted at 40°C for 1 hour. The mold was then removed to obtain a laminate of heat-absorbing layer 2B1 / heat-absorbing layer 2A1. Furthermore, the heat-absorbing layer 2B1 and the thermal foaming layer 31 were sequentially bonded to the heat-absorbing layer 2B1 side of the laminate (heat-absorbing layer 2B1 / heat-absorbing layer 2A1) using an acrylic resin adhesive to obtain test specimens 1-6. The sodium tetraborate hydrate content of the heat-absorbing layer 2A1 was 4.2 kg / m². 2 This was the case. Test specimen 1-6 is in the form shown in Figure 11.

[0185] [Examples 1-7] (Test specimens 1-7) A mixture of the first component and the second component of the heat-absorbing layer 2A7 was poured into a mold (100 mm x 100 mm), a load of 1 MPa was applied, and the mixture was reacted at 40°C for 1 hour. After demolding, the heat-absorbing layer 2A7 was obtained. Another heat-absorbing layer 2A7 was obtained using the same method, and the two heat-absorbing layers 2A7 were bonded together using an acrylic resin adhesive. Furthermore, a heat-foamed layer 31 was bonded to them using an acrylic resin adhesive to obtain test specimen 1-7 (heat-absorbing layer 2A7 / heat-absorbing layer 2A7 / heat-foamed layer 31). The total sodium tetraborate hydrate content in the two heat-absorbing layers 2A7 is 11.6 kg / m². 2 This was the case. Test specimen 1-7 is in the form shown in Figure 12.

[0186] [Examples 1-8] (Test specimens 1-8) A mixture of the first component and the second component of the heat-absorbing layer 2A8 was poured into a mold (100 mm x 100 mm), a load of 1 MPa was applied, and the mixture was reacted at 40°C for 1 hour. After demolding, the heat-absorbing layer 2A8 was obtained. Another heat-absorbing layer 2A8 was obtained using the same method, and the two heat-absorbing layers 2A8 were bonded together using an acrylic resin adhesive. Furthermore, a heat-foamed layer 31 was bonded to them using an acrylic resin adhesive to obtain test specimen 1-8 (heat-absorbing layer 2A8 / heat-absorbing layer 2A8 / heat-foamed layer 31). The total sodium tetraborate hydrate content in the two heat-absorbing layers 2A8 is 12.2 kg / m². 2 This was the case. Test specimen 1-8 is in the form shown in (Figure 13).

[0187] [Examples 1-9] (Test specimens 1-9) A mixture of the first component and the second component of the heat-absorbing layer 2A8 was poured into a mold (100 mm x 100 mm), a load of 1 MPa was applied, and the mixture was reacted at 40°C for 1 hour. After demolding, the heat-absorbing layer 2A8 was obtained. The heat-absorbing layer 2A8 was then bonded onto the heat-absorbing layer 2B1, and the heat-foamed layer 31 was further bonded using an acrylic resin adhesive to obtain test specimen 1-9 (heat-absorbing layer 2B1 / heat-absorbing layer 2A8 / heat-foamed layer 31). The total sodium tetraborate hydrate content in the heat-absorbing layer 2A8 is 6.1 kg / m². 2 This was the case. Test specimen 1-9 is in the form shown in (Figure 14).

[0188] [Comparative Example 1-1] (Test specimens 1-10) A heat-absorbing layer 2B1 was placed inside a mold (100 mm x 100 mm), a mixture of the first component and the second component of the heat-absorbing layer 2A3 was poured onto the heat-absorbing layer 2B1, a load of 1 MPa was applied, and the mixture was allowed to react at 40°C for 1 hour. The mold was then removed to obtain a laminate of heat-absorbing layer 2B1 / heat-absorbing layer 2A3. Furthermore, a thermal foaming layer 31 was bonded to the heat-absorbing layer 2A3 side of the laminate using an acrylic resin adhesive to obtain test specimen 1-10. This test specimen 1-10 is in the configuration shown in Figure 15.

[0189] [Comparative Example 1-2] (Test specimen 1-11) Test specimen 1-11 was obtained by bonding the heat-absorbing layer 2B1 and the heat-foaming layer 31 in order using an acrylic resin adhesive. This test specimen 1-11 is in the configuration shown in Figure 16.

[0190] [Example 2-1] (Test specimen 2-1) A heat-absorbing layer 2B2 was placed inside a mold (600mm x 450mm), a mixture of the first component and the second component of the heat-absorbing layer 2A1 was poured onto the heat-absorbing layer 2B2, a load of 1 MPa was applied, and the mixture was allowed to react at 40°C for 1 hour. The mold was then removed to obtain a composite layer P21 of heat-absorbing layer 2B2 / heat-absorbing layer 2A1. Furthermore, the heat-absorbing layer 2B2 and the thermal foaming layer 32 were bonded together using an acrylic resin adhesive to obtain a composite layer Q21 of the heat-absorbing layer 2B2 / thermal foaming layer 32. Composite layer P21 and composite layer Q21 were stacked on the base material 11 (layered in the order of base material 11, heat-absorbing layer 2B2, heat-absorbing layer 2A1, heat-absorbing layer 2B2, and heat-foamed layer 32), and fixed with screws to obtain test specimen 2-1. The sodium tetraborate hydrate content of heat-absorbing layer 2A1 was 5.1 kg / m². 2 In addition, a thermocouple was installed between the base material 11 and the heat-absorbing layer 2B2 in contact with the base material 11. This test specimen 2-1 is in the configuration shown in Figure 17.

[0191] [Example 2-2] (Test specimen 2-2) A heat-absorbing layer 2B1 was placed inside a mold (600mm x 450mm), a mixture of the first component and the second component of the heat-absorbing layer 2A1 was poured onto the heat-absorbing layer 2B1, a load of 1 MPa was applied, and the mixture was reacted at 40°C for 1 hour. The mold was then removed to obtain a composite layer P22 of heat-absorbing layer 2B1 / heat-absorbing layer 2A1. Furthermore, the heat-absorbing layer 2B1 and the thermal foaming layer 32 were bonded together using an acrylic resin adhesive to obtain a composite layer Q22 of the heat-absorbing layer 2B1 / thermal foaming layer 32. The composite layer P22 and the composite layer Q22 were overlapped on the base material 11 (laminated in the order of the base material 11, the heat absorption layer 2B1, the heat absorption layer 2A1, the heat absorption layer 2B1, and the thermal foam layer 32), and fixed using screws to obtain the test piece 2-2. The content of sodium tetraborate hydrate in the heat absorption layer 2A1 was 4.2 kg / m 2 Therein. A thermocouple was installed between the base material 11 and the heat absorption layer 2B1 in contact with the base material 11. This test piece 2-2 is in the mode shown in FIG. 18.

[0192] [Example 2-3] (Test piece 2-3) The heat absorption layer 2B1 was placed in a mold (600 mm × 450 mm), and a mixed solution of the first component of the heat absorption layer 2A1 and the second component of the heat absorption layer 2A1 was poured onto the heat absorption layer 2B1, a load of 1 MPa was applied, and the reaction was carried out at 40°C for 1 hour, and then demolded to obtain the composite layer P23 of the heat absorption layer 2A1 / heat absorption layer 2B1. Also, the heat absorption layer 2B1 and the thermal foam layer 32 were bonded together using an acrylic resin adhesive to obtain the composite layer Q23 of the heat absorption layer 2B1 / thermal foam layer 32. The composite layer P23 and the composite layer Q23 were overlapped on the base material 11 (laminated in the order of the base material from 11, the heat absorption layer 2A1, the heat absorption layer 2B1, the heat absorption layer 2B1, and the thermal foam layer 32), and fixed using screws to obtain the test piece 2-3. The content of sodium tetraborate hydrate in the heat absorption layer 2A1 was 4.2 kg / m 2 Therein. A thermocouple was installed between the base material 11 and the heat absorption layer 2A1. This test piece 2-3 is in the mode shown in FIG. 19.

[0193] [Example 2-4] (Test piece 2-4)​​​​​Composite layers P24 and Q24 were stacked on the base material 11 (layered in the order of base material 11, heat-absorbing layer 2B2, heat-absorbing layer 2A4, heat-absorbing layer 2B2, heat-absorbing layer 2B1, and thermal foaming layer 32), and fixed with screws to obtain test specimen 2-4. The sodium tetraborate hydrate content of heat-absorbing layer 2A4 was 4.8 kg / m². 2 In addition, a thermocouple was installed between the base material 11 and the heat-absorbing layer 2B2 in contact with the base material 11. This test specimen 2-4 is in the configuration shown in Figure 20.

[0194] [Examples 2-5] (Test specimens 2-5) A heat-absorbing layer 2B2 was placed in a mold (600mm x 450mm), a mixture of the first component and the second component of the heat-absorbing layer 2A5 was poured onto the heat-absorbing layer 2B2, another heat-absorbing layer 2B2 was added on top, a load of 1 MPa was applied, and the mixture was reacted at 40°C for 1 hour. After demolding, a composite layer P25 of heat-absorbing layer 2B2 / heat-absorbing layer 2A5 / heat-absorbing layer 2B2 was obtained. Furthermore, the heat-absorbing layer 2B2 and the thermal foaming layer 32 were bonded together using an acrylic resin adhesive to obtain a composite layer Q25 of the heat-absorbing layer 2B2 / thermal foaming layer 32. Composite layers P25 and Q25 were stacked on the base material 11 (layered in the order of base material 11, heat-absorbing layer 2B2, heat-absorbing layer 2A5, heat-absorbing layer 2B2, heat-absorbing layer 2B2, and thermal foaming layer 32), and fixed with screws to obtain test specimen 2-5. The sodium tetraborate hydrate content of heat-absorbing layer 2A5 was 6.7 kg / m². 2 In addition, a thermocouple was installed between the base material 11 and the heat-absorbing layer 2B2 in contact with the base material 11. This test specimen 2-5 is in the configuration shown in Figure 21.

[0195] [Examples 2-6] (Test specimen 2-6) A heat-absorbing layer 2B2 was placed inside a mold (600mm x 450mm), a mixture of the first component and the second component of the heat-absorbing layer 2A6 was poured onto the heat-absorbing layer 2B2, a load of 1 MPa was applied, and the mixture was allowed to react at 40°C for 1 hour. The mold was then removed to obtain a composite layer P26 of heat-absorbing layer 2B2 / heat-absorbing layer 2A6. Furthermore, the heat-absorbing layer 2B2 and the thermal foaming layer 32 were bonded together using an acrylic resin adhesive to obtain a composite layer Q26 of the heat-absorbing layer 2B2 / thermal foaming layer 32. Composite layer P26 and composite layer Q26 were stacked on the base material 11 (layered in the order of base material 11, heat-absorbing layer 2B2, heat-absorbing layer 2A6, heat-absorbing layer 2B2, and heat-foamed layer 32), and fixed with screws to obtain test specimen 2-6. The sodium tetraborate hydrate content of heat-absorbing layer 2A6 was 4.6 kg / m². 2 In addition, a thermocouple was installed between the base material 11 and the heat-absorbing layer 2B2 in contact with the base material 11. This test specimen 2-6 is in the configuration shown in Figure 22.

[0196] [Examples 2-7] (Test specimen 2-7) A mixture of the first component and the second component of the heat-absorbing layer 2A7 was poured into a mold (600mm x 450mm), a load of 1 MPa was applied, and the mixture was reacted at 40°C for 1 hour. After demolding, the heat-absorbing layer 2A7 was obtained. The heat-absorbing layer 2B1, heat-absorbing layer 2A7, and thermal foam layer 32 were layered on the base material 11 (in the order of base material 11, heat-absorbing layer 2B1, heat-absorbing layer 2A7, and thermal foam layer 32), and fixed with screws to obtain test specimen 2-7. The sodium tetraborate hydrate content of the heat-absorbing layer 2A7 was 8.7 kg / m². 2 A thermocouple was installed between the base material 11 and the heat-absorbing layer 2B1. This test specimen 2-7 is in the configuration shown in Figure 23.

[0197] [Examples 2-8] (Test specimen 2-8) A mixture of the first component and the second component of the heat-absorbing layer 2A8 was poured into a mold (600mm x 450mm), a load of 1 MPa was applied, and the mixture was reacted at 40°C for 1 hour. After demolding, the heat-absorbing layer 2A8 was obtained. The heat-absorbing layer 2A8, heat-absorbing layer 2B1, and heat-foamed layer 32 were layered on the base material 11 (in the order of base material 11, heat-absorbing layer 2A8, heat-absorbing layer 2B1, and heat-foamed layer 32), and fixed with screws to obtain test specimen 2-8. The sodium tetraborate hydrate content of the heat-absorbing layer 2A8 was 9.2 kg / m². 2A thermocouple was installed between the base material 11 and the heat-absorbing layer 2A8. This test specimen 2-8 is in the configuration shown in Figure 24.

[0198] [Comparative Example 2-1] (Test specimen 2-9) The organic insulation layer and the thermal foam layer 32 were bonded together using an acrylic resin adhesive to obtain a composite layer 27. A composite layer 27 was fixed to the base material 11 with screws (layered in the order of base material 11, organic insulation layer, and thermal foam layer 32) to obtain test specimen 2-9. A thermocouple was installed between the base material 11 and the organic insulation layer. This test specimen 2-9 is in the configuration shown in Figure 25.

[0199] [Comparative Example 2-2] (Test specimen 2-10) An organic insulation layer and a heat-absorbing layer 2B1 were bonded together using an acrylic resin adhesive to obtain a composite layer 28. A composite layer 28 was fixed to the base material 11 with screws (layered in the order of base material 11, organic insulation layer, and heat absorption layer 2B1) to obtain test specimen 2-10. A thermocouple was installed between the base material 11 and the organic insulation layer. This test specimen 2-10 is in the configuration shown in Figure 26.

[0200] [Comparative Example 2-3] (Test specimen 2-11) The heat-absorbing layer 2B1 and the thermal foaming layer 32 were bonded together using an acrylic resin adhesive to produce a composite layer Q29. The composite layer Q29 was fixed to the base material 11 with screws (layered in the order of base material 11, heat-absorbing layer 2B1, and thermal foaming layer 32) to obtain test specimen 2-11. A thermocouple was installed between the base material 11 and the heat-absorbing layer 2B1. This test specimen 2-11 is in the configuration shown in Figure 27.

[0201] [Example 3-1] (Test specimen 3-1) On the four side surfaces of the base material 12 which is a corner post, the heat absorption layers 2A7 were overlapped, fixed using screws, and further, the heat foam layer 32 was bonded using an acrylic resin adhesive (Fig. 28). Subsequently, the decorative layer 5 was bonded using a vinyl acetate resin adhesive to obtain the test piece 3-1. A thermocouple was installed between the base material 12 and the heat absorption layer 2A7 in contact with the base material 11. This test piece 3-1 is in the form shown in Fig. 29.

[0202] [Example 3-2] (Test piece 3-2) On the four side surfaces of the base material 12 which is a corner post, the heat absorption layers 2B3 and 2A7 were overlapped, fixed using screws, and further, the heat foam layer 32 was bonded using an acrylic resin adhesive (Fig. 30). Subsequently, the decorative layer 5 was bonded using a vinyl acetate resin adhesive to obtain the test piece 3-2. A thermocouple was installed between the base material 12 and the heat absorption layer 2B3. This test piece 3-2 is in the form shown in Fig. 31.

[0203] [Example 3-3] (Test piece 3-3) On the four side surfaces of the base material 12 which is a corner post, the heat absorption layers 2A7 and 2B3 were overlapped, fixed using screws, and further, the heat foam layer 32 was bonded using an acrylic resin adhesive (Fig. 32). Subsequently, the decorative layer 5 was bonded using a vinyl acetate resin adhesive to obtain the test piece 3-3. A thermocouple was installed between the base material 12 and the heat absorption layer 2A7. This test piece 3-3 is in the form shown in Fig. 33.

[0204] [Comparative Example 3-1] (Test piece 3-4) On the four side surfaces of the base material 12 which is a corner post, the organic heat insulating material layer and the heat foam layer 32 were bonded using an acrylic resin adhesive to obtain the test piece 3-4. A thermocouple was installed between the base material 12 and the organic heat insulating material layer.

[0205] (Laminated form of test piece, etc.) The laminated form, thickness (mm) of the laminate, and mass per unit area (kg / m 2The following are shown in Tables 1 to 3 below.

[0206] (Fire resistance test 1) Each test specimen 1-1 to 1-11 (laminated structure) prepared using the method described above was subjected to a fire resistance test using a cone calorimeter as specified in ISO 5660. The heating intensity was 50 kW / m². 2 The heating time was 90 minutes. In the fire resistance test, the temperature of the back surface of the test specimen was measured during heating, and the highest temperature reached was used for evaluation. The back surface of the test specimen here refers to the side with the heat-absorbing layer (the unheated side). The evaluation criteria are as follows. The test results are shown in Table 1. Generally, wood begins to decompose at around 200°C, generating flammable gases, and the risk of combustion increases above 250°C. Therefore, for practical use, it is preferable to meet the evaluation criteria of AA, A, or B. (Evaluation Criteria) AA: Maximum temperature reached is 125℃ or less A: The maximum temperature reached is between 125°C and 150°C. B: The maximum temperature reached exceeds 150°C but is 200°C or less. C: Maximum temperature reached exceeds 200°C but is 250°C or less. D: The maximum temperature reached exceeds 250°C.

[0207] (Fire resistance test 2) Each test specimen 2-1 to 2-11 (covered structure) prepared using the method described above was placed in a test furnace (positioned downwards with the substrate side facing upwards), and a heating test was conducted for 120 minutes according to the standard heating curve of ISO 834. The surface temperature of the wood substrate when the surface of the test specimen was heated was measured using a thermocouple. Evaluation was performed by measuring the surface temperature immediately after the 120-minute heating test and again 120 minutes after heating stopped. The evaluation criteria are as follows. The test results are shown in Table 2. Considering the practical risks of wood combustion, a practical level of AA, A, or B according to the evaluation criteria is preferable. (Evaluation Criteria) AA: Below 110°C immediately after 120 minutes of heating, and below 130°C 120 minutes after heating stops. A: Temperatures above 110°C but below 150°C immediately after 120 minutes of heating, and below 150°C 120 minutes after heating stops. B: Temperatures exceeding 150°C but below 250°C immediately after 120 minutes of heating, and below 250°C 120 minutes after heating stops. C: Heating for 120 minutes, immediately exceeding 250°C

[0208] (Fire resistance test 3) Each test specimen 3-1 to 3-4 (coating structure) prepared using the method described above was 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 12 when the surface of the test specimen was heated was measured using thermocouples. Thermocouples were installed at a total of eight locations: four at each corner of the substrate 12 at a height of 400 mm, and four at the center of each surface between the corners. The evaluation criteria are as follows. The test results are shown in Table 3. 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: After 90 minutes of heating, one or more spots exceed 250°C.

[0209] [Table 1]

[0210] [Table 2]

[0211] [Table 3]

[0212] From the evaluation results in Table 1 above, it was confirmed that in Examples 1-1 to 1-9 (test specimens 1-1 to 1-9), by using a laminate in which a heat-absorbing layer and a heat-foamed layer are stacked in sequence, the mass per unit area can be kept low, resulting in weight reduction, and furthermore, the fire resistance is at a practical level.

[0213] On the other hand, as shown in the evaluation results in Table 1 above, it was confirmed that in Comparative Example 1-1 (test specimen 1-10), the fire resistance was not at a practical level because the heat-absorbing layer of the present invention was not used. Furthermore, in Comparative Example 1-2 (test specimen 1-11), it was confirmed that the fire resistance was not at a practical level because the laminate comprising the heat-absorbing layer and the thermal foaming layer of the present invention was not used.

[0214] From the evaluation results in Table 2 above, it was confirmed that in Examples 2-1 to 2-8 (test specimens 2-1 to 2-8), by using a laminate in which a heat-absorbing layer and a heat-foamed layer are sequentially laminated on a wood-based organic substrate, the mass per unit area can be kept low, resulting in weight reduction, excellent workability and constructability, and furthermore, the fire resistance is at a practical level.

[0215] On the other hand, as shown in the evaluation results in Table 2 above, it was confirmed that in Comparative Examples 2-1 to 2-3 (test specimens 2-9 to 2-11), the heat-absorbing layer of the present invention was not used on the wood substrate, which is an organic substrate, and therefore the fire resistance was not at a practical level.

[0216] From the evaluation results in Table 3 above, it was confirmed that in Examples 3-1 to 3-3 (test specimens 3-1 to 3-3), by using a laminate in which a heat-absorbing layer and a heat-foamed layer are sequentially laminated on an organic wood base material, the fire resistance is at a practical level.

[0217] On the other hand, as shown in the evaluation results in Table 3 above, it was confirmed that in Comparative Example 3-1 (Test Specimen 3-4), the heat-absorbing layer of the present invention was not used on the wood substrate, which is an organic substrate, and therefore the fire resistance was not at a practical level.

Claims

1. A laminate comprising a heat-absorbing layer and a thermal foaming layer, The heat-absorbing layer is formed of a binder and sodium tetraborate. The aforementioned binder includes an organic binder, A laminate in which the organic binder is an unsaturated polyester resin.

2. The laminate according to claim 1, wherein the sodium tetraborate comprises sodium tetraborate decahydrate.

3. The laminate according to claim 1, wherein the heat-absorbing layer comprises at least an heat-absorbing layer formed of an organic binder and sodium tetraborate, and a heat-absorbing layer formed of an inorganic binder.

4. The density of the heat-absorbing layer is 0.05 g / cm³. ３ 1.5g / cm or more ３ The laminate according to claim 1, which is less than [amount missing].

5. The laminate according to claim 1, wherein the thickness of the laminate is 60 mm or less.

6. The mass per unit area of ​​the laminate is 40 kg / m². ２ The laminate according to claim 1, which is as follows:

7. A coated structure in which an organic substrate is coated with a laminate according to any one of claims 1 to 6.

8. The covering structure according to claim 7, wherein the organic substrate is a wood substrate and / or a plastic substrate.

9. The coating structure according to claim 7, wherein the heat-absorbing layer and the organic substrate are in contact.

10. The covering structure according to claim 7, wherein the organic substrate is a flat plate or an axial member having a rectangular or circular cross-section.

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