Laminate and coated structure
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- KAJIMA CORP
- Filing Date
- 2026-01-22
- Publication Date
- 2026-07-30
Smart Images
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Abstract
Description
Laminates and covering structures
[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.
[0002] Traditionally, concrete has been widely used in the structural framework of buildings (columns, beams, floors, 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 substrates such as CLT (Cross Laminated Timber) and fiber-reinforced plastic substrates 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.
[0008] Japanese Patent Publication No. 2019-150389
[0009] However, the laminate specifically disclosed in Patent Document 1 consists mostly of inorganic non-combustible materials such as gypsum board or calcium silicate board, and because of its overall thickness, the laminate has a heavy mass per unit area, which makes it difficult to handle and install during transportation and construction, potentially leading to accidents. It also places a large load on the substrates used, posing problems. Furthermore, the thickness of the laminate may reduce the room volume when used for columns or walls. Moreover, when used for floorboards, it may further reduce the floor height, potentially hindering equipment planning.
[0010] Therefore, the problem that the present invention aims to solve is to provide a laminate that can be made thinner and lighter by using a laminate containing a heat-absorbing layer and a thermal foaming layer made of specific raw materials, and that is excellent in workability, safety and fire resistance, as well as a coated structure in which a base material is covered with the laminate.
[0011] Therefore, the present inventors diligently studied to solve the above problems and found that by using a laminate including a heat-absorbing layer and a thermal foaming layer, wherein the heat-absorbing layer is formed of a binder and one or more selected from inorganic acids, hydroxide compounds, and hydrated compounds (excluding sodium tetraborate hydrate), the thickness can be reduced and the weight reduced, and it is possible to achieve excellent workability, safety, and fire resistance, thus completing the present invention.
[0012] In other words, the present invention has the following features: 1. A laminate comprising an endothermic layer and a thermal foaming layer, wherein the endothermic layer is formed of a binder and one or more selected from inorganic acids, hydroxide compounds, and hydrated compounds (excluding sodium tetraborate hydrate). 2. The laminate according to 1, wherein the inorganic acid comprises boric acid. 3. The laminate according to 1, wherein the binder is an organic binder. 4. The laminate according to 3, wherein the organic binder is obtained from unsaturated polyester and unsaturated monomers. 5. The laminate comprising at least an endothermic layer formed of an organic binder and one or more selected from inorganic acids, hydroxide compounds, and hydrated compounds (excluding sodium tetraborate hydrate), and an endothermic layer formed by an inorganic binder. 6. The laminate according to 5, wherein the inorganic acid comprises boric acid. 7. The substrate is one of 1 to 6. A covering structure covered by a laminate as described in any one of the items. 8. The covering structure according to item 7, wherein the base material is an organic base material. 9. The covering structure according to item 8, wherein the organic base material is a wood base material and / or a plastic base material. 10. The covering structure according to item 7, wherein the heat-absorbing layer and the base material are in contact. 11. The covering structure according to item 7, wherein the base material is a flat plate or an axial member having a polygonal or circular cross-section.
[0013] The laminate of the present invention is thin and lightweight, and is useful because it offers excellent workability, safety, and fire resistance.
[0014] This is an example of a model diagram (cross-sectional view) showing the coating structure of the present invention. This is an example of a model diagram (cross-sectional view) showing the coating structure of the present invention. This is an example of a model diagram (cross-sectional view) showing the coating structure of the present invention. This is an example of a model diagram (cross-sectional view) showing the coating structure of the present invention. This is an example of a model diagram (cross-sectional view) showing the coating structure of the present invention. This is an example of a model diagram (cross-sectional view) showing the coating structure of the present invention. This is an example of a model diagram (cross-sectional view) showing the coating structure of the present invention. This is an example of a model diagram (cross-sectional view) showing the coating structure of the present invention.
[0015] 1: Organic base material (base material 11-12) 2A: Heat-absorbing layer (A) (heat-absorbing layers 2A1-2A8) 2B: Heat-absorbing layer (B) (heat-absorbing layers 2B1-2B3, 2Ba, 2Bb) 3: Thermal foam layer (thermal foam layers 31-32) 4: Laminate (heat-absorbing layer (A), heat-absorbing layer (B), thermal foam layer) P: Composite layer (heat-absorbing layer (A), heat-absorbing layer (B)) Q: Composite layer (heat-absorbing layer (B), thermal foam layer) R: Composite layer (heat-absorbing layer (A), thermal foam layer)
[0016] The following describes embodiments for carrying out the present invention.
[0017] [Laminate] The present invention relates to a laminate comprising an endothermic layer and a thermal foaming layer, wherein the endothermic layer is formed of a binder and one or more selected from inorganic acids, hydroxide compounds, and hydrated compounds (excluding sodium tetraborate hydrate) (these are collectively referred to as "endothermic compounds" below).
[0018] [Heat-absorbing layer] The laminate of the present invention is a laminate including a heat-absorbing layer, wherein the heat-absorbing layer is formed by a binder and a heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.). By using the binder, the heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.) 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 substrate (described later) when the temperature rises, such as during a fire, and plays a role in maintaining the shape of the substrate. As a result, the coated structure in which the 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] Furthermore, the effects of the present invention can be particularly demonstrated when the substrate is an organic substrate. For this reason, the following description of embodiments will focus on the case where the substrate is an organic substrate, but the substrate is not limited to an organic substrate; for example, the substrate may be an inorganic substrate, etc. Specifically, examples of the substrate include inorganic substrates such as metal substrates and cement substrates, organic substrates such as wood substrates, plastic substrates, fiber-reinforced plastic substrates, paper substrates, and fiber-reinforced plastic substrates, or substrates that combine these. In the present invention, organic substrates such as wood substrates, plastic substrates, fiber-reinforced plastic substrates, paper substrates, and fiber-reinforced plastic substrates are particularly preferred, and among these, from the viewpoint of strength and lightness, it is preferable that the organic substrate is a wood substrate and / or a plastic substrate (wood substrate, plastic substrate, and fiber-reinforced plastic substrate, or a substrate that combines these).
[0021] (Binder) Examples of the binder include organic binders and inorganic binders. From the viewpoint of weight reduction, manufacturability and processability, organic binders are preferred, and from the viewpoint of endothermic properties, inorganic binders are preferred.
[0022] [Heat-absorbing layer (A)] It is also preferable that the heat-absorbing layer includes at least an organic binder and a heat-absorbing compound (for example, boric acid, boric acid hydrate, etc.) (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 overall thickness and weight of the laminate.
[0023] (Organic binder) Examples of the organic binder include polyester resin, unsaturated polyester resin, vinyl ester resin, vinyl acetate resin, alkyd resin, epoxy resin, acrylic resin, acrylic silicone resin, urethane resin, silicone resin, phenolic resin, melamine resin, polycarbonate resin, fluororesin, acrylic vinyl acetate resin, acrylic urethane resin, acrylic epoxy resin, and ethylene vinyl acetate resin. These resins may also be made from biomass raw materials or resins modified with biomass raw materials. Among these, those obtained from polyols and isocyanates (urethane resin obtained by reaction and curing), or those obtained from unsaturated polyesters and / or vinyl esters and unsaturated monomers (unsaturated polyester resin and / or vinyl ester resin obtained by reaction and curing) are preferred, and those obtained from unsaturated polyesters and unsaturated monomers (unsaturated polyester resin obtained by reaction and curing) are particularly preferred. The unsaturated polyester resin is useful because it allows for a thinner thickness.
[0024] (Polyol) Examples of the polyol include polyester polyol, polyether polyol, polycarbonate polyol, polylactone polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil-based polyol, and one or more of these can be used.
[0025] The hydroxyl value of the polyol in this 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 equimolar to the hydroxyl groups contained in 1 g of the sample, and is measured based on JIS K 1557-1:2007 Plastics - Test methods for polyols in polyurethane raw materials - Part 1: Method for determining hydroxyl value. The hydroxyl value of the polyol is the value measured for all polyol mixtures.
[0026] (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.
[0027] 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.
[0028] In the present invention, it is preferable that the isocyanate index is 100 or more and 500 or less (more preferably 105 or more and 400 or less, and even more preferably 110 or more and 300 or less). 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 of the isocyanate by the total equivalent number of active hydrogens in the active hydrogen-containing component (polyol). Furthermore, water generated from the heat-absorbing compound described later is not included in the calculation of the active hydrogen-containing component used in the isocyanate index. Examples of the water include the inorganic acids described later (e.g., boric acid), crystal water or adsorbed water of hydroxide compounds, and the hydrated water of the hydrated compounds described later (e.g., boric acid hydrate).
[0029] (Unsaturated polyester) Examples of the unsaturated polyester include those produced by the esterification reaction of a polyhydric alcohol and a polybasic acid.
[0030] As the polyhydric alcohol, for example, alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, 1,6 - hexanediol, ester glycol, 1,4 - cyclohexanedimethanol, 1,3 - butanediol, etc. can be mentioned, and these can be used alone or in combination of two or more kinds.
[0031] As the polybasic acid, for example, unsaturated polybasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, etc. can be mentioned, and 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 kinds of these can be used.
[0032] (Vinyl ester) As the vinyl ester, for example, bisphenol A type vinyl ester, novolac type vinyl ester, bromine - added type vinyl ester, special modified type vinyl ester, etc. can be mentioned, and one or more kinds of these can be used. Among them, from the viewpoints of stable supply and cost, bisphenol A type vinyl ester is particularly preferable.
[0033] (Unsaturated monomer) As the unsaturated monomer, for example, (meth)acrylic acid ester monomers such as methyl (meth)acrylate, aromatic monomers such as styrene, methylstyrene, divinylbenzene, etc. can be mentioned, and one or more kinds of these can be used. Among them, from the viewpoint of curability, styrene and methyl methacrylate are particularly preferable.
[0034] In the present invention, the mixing ratio of the unsaturated polyester and / or the vinyl ester and the unsaturated monomer is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 20 parts by mass or more and 180 parts by mass or less of the unsaturated monomer with respect to 100 parts by mass of the unsaturated polyester and / or the vinyl ester. By mixing the unsaturated polyester and / or the vinyl ester and the unsaturated monomer within such a range, and optionally mixing an initiator or the like, an unsaturated polyester resin and / or a vinyl ester resin having excellent heat resistance, and an endothermic layer (endothermic layer (A)) using the unsaturated polyester resin and / or the vinyl ester resin can be obtained. In particular, as the unsaturated polyester, those produced by an esterification reaction of a polyhydric alcohol selected from ethylene glycol and propylene glycol and a polybasic acid selected from maleic acid, maleic anhydride, fumaric acid, and isophthalic acid, and as the unsaturated monomer, it is preferable to use a (meth)acrylic acid ester monomer and / or an aromatic monomer in the above mixing ratio.
[0035] (Endothermic compound) The inorganic acid, the hydroxide compound, and the hydrated compound are components that impart endothermic properties.
[0036] Examples of the inorganic acid include inorganic acids such as boric acid, phosphoric acid, sulfuric acid, sulfurous acid, nitric acid, silicic acid, and carbonic acid. Examples of the boric acid include boric acid, metaboric acid, orthoboric acid, diboric acid, tetraboric acid, octaboric acid, etc., and one or more of these can be used. From the viewpoints of endothermic properties and fire resistance, the content of the boric acid is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass of the total inorganic acid. That is, it is particularly preferable that the inorganic acid contains only boric acid.
[0037] Examples of the hydroxide compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, aluminum hydroxide, titanium hydroxide, vanadium hydroxide, manganese hydroxide, iron hydroxide, nickel hydroxide, copper hydroxide, zinc hydroxide, zirconium hydroxide, and tin hydroxide, and one or more of these can be used. In the present invention, from the viewpoint of endothermic properties, it is preferable to use magnesium hydroxide, aluminum hydroxide, etc., and it is more preferable to use aluminum hydroxide. From the viewpoint of endothermic properties and fire resistance, the content of aluminum hydroxide is preferably 80% by mass or more of the total hydroxide compound, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass. In other words, it is particularly preferable that the hydroxide compound contains only aluminum hydroxide.
[0038] Furthermore, as the hydrated compound, one or more selected from, for example, hydrates or inorganic acid salts such as boric acid, sulfuric acid, sulfurous acid, phosphoric acid, nitric acid, silicic acid, oxalic acid, and carbonic acid; hydrates of organic acid salts such as benzoic acid, phthalic acid, maleic acid, succinic acid, salicylic acid, citric acid, acetic acid, oxalic acid, and sulfonic acid; and hydrates of chloride salts, bromide salts, iodide salts, hydroxide salts, etc., can be used. Furthermore, as the metal, one or more selected from sodium, aluminum, calcium, zinc, manganese, lanthanum, titanium, zirconium, iron, cobalt, nickel, magnesium, and copper can be used.
[0039] The hydrated compound preferably contains boric acid hydrate and / or borate hydrate (collectively referred to as "boric acid hydrate, etc.") from the viewpoint of endothermic properties. From the viewpoint of endothermic properties and fire resistance, the content of boric acid hydrate, etc. is preferably 80% by mass or more of the total hydrated compound, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass. In other words, it is particularly preferable that the hydrated compound contains only boric acid hydrate, etc.
[0040] Examples of the boric acid hydrate and / or borate hydrate include boric acid hydrates such as boric acid, metaboric acid, and tetraboric acid, and / or borate hydrates such as lithium salt, potassium salt, magnesium salt, calcium salt, barium salt, aluminum salt, zinc salt, and cobalt salt of boric acid, and one or more of these can be used. In the present invention, from the viewpoint of endothermic properties, it is preferable to use boric acid monohydrate, potassium tetraborate tetrahydrate, magnesium borate hexahydrate, zinc borate 3.5hydrate, zinc borate hexahydrate, cobalt borate hexahydrate, etc.
[0041] Furthermore, the heat-absorbing layer (A) may also contain, as the hydrated compound, one or more selected from sulfate hydrates, sulfite hydrates, phosphate hydrates, nitrate hydrates, acetate hydrates, chloride salt hydrates, and hydroxide salt hydrates, together with or in place of the boric acid hydrates, etc. These hydrates specifically include sulfate hydrates such as ammonium aluminum sulfate dodecahydrate, sodium aluminum sulfate dodecahydrate, aluminum sulfate heptahydrate, aluminum sulfate octahydrate, aluminum sulfate octahydrate, aluminum sulfate heptahydrate, aluminum sulfate decahydrate, aluminum sulfate hexahydrate, potassium aluminum sulfate dodecahydrate, iron sulfate heptahydrate, iron sulfate noctuahydrate, potassium iron sulfate dodecahydrate, magnesium sulfate heptahydrate, sodium sulfate decahydrate, nickel sulfate hexahydrate, zinc sulfate heptahydrate, beryllium sulfate tetrahydrate, zirconium sulfate tetrahydrate, etc.; sulfite hydrates such as zinc sulfite dihydrate, sodium sulfite heptahydrate, etc.; aluminum phosphate dihydrate, cobalt phosphate octahydrate, magnesium phosphate octahydrate, magnesium ammonium phosphate hexahydrate, phosphorus Examples include hydrates of phosphates such as magnesium hydrogen oxyhydrogen trihydrate, magnesium hydrogen phosphate heptahydrate, zinc phosphate tetrahydrate, and zinc dihydrogen phosphate dihydrate; hydrates of nitrates such as aluminum nitrate nonahydrate, zinc nitrate hexahydrate, calcium nitrate tetrahydrate, cobalt nitrate hexahydrate, bismuth nitrate pentahydrate, zirconium nitrate pentahydrate, cerium nitrate hexahydrate, iron nitrate hexahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate, and magnesium nitrate hexahydrate; hydrates of acetates such as zinc acetate dihydrate and cobalt acetate tetrahydrate; hydrates of chloride salts such as cobalt chloride hexahydrate and iron chloride tetrahydrate; and hydrates of hydroxide salts such as aluminum hydroxide monohydrate, aluminum hydroxide trihydrate, magnesium hydroxide monohydrate, calcium hydroxide monohydrate, barium hydroxide monohydrate, and zirconium hydroxide monohydrate.
[0042] Furthermore, the heat-absorbing layer (A) may also contain other inorganic compounds different from the heat-absorbing compound. Examples of other inorganic compounds include sodium tetraborate hydrates such as sodium tetraborate pentahydrate and sodium tetraborate decahydrate.
[0043] The content of the endothermic compound is preferably 5% by mass or more and 90% by mass or less of the total endothermic 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, an endothermic layer (endothermic layer (A)) that sufficiently combines both endothermic properties and lightweight properties can be obtained. If the hydrated compound includes boric acid hydrate, etc., the content of boric acid hydrate, etc. is preferably 5% by mass or more and 90% by mass or less of the total endothermic 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, an endothermic layer (endothermic layer (A)) that more sufficiently combines both endothermic properties and lightweight properties can be obtained.
[0044] The amount of the endothermic compound mixed is preferably 30 parts by mass or more and 300 parts by mass or less (more preferably 40 parts by mass or more and 250 parts by mass or less, and even more preferably 45 parts by mass or more and 200 parts by mass or less) per 100 parts by mass of the organic binder. If the hydrated compound contains boric acid hydrate or the like, the amount of boric acid hydrate or the like mixed is preferably 30 parts by mass or more and 300 parts by mass or less (more preferably 40 parts by mass or more and 250 parts by mass or less, and even more preferably 45 parts by mass or more and 200 parts by mass or less) per 100 parts by mass of the organic binder.
[0045] If the organic binder is an unsaturated polyester resin and / or vinyl ester resin, it is particularly preferable that the amount of the endothermic compound mixed is 30 parts by mass or more and 300 parts by mass or less (more preferably 40 parts by mass or more and 250 parts by mass or less, and even more preferably 45 parts by mass or more and 200 parts by mass or less) per 100 parts by mass of the unsaturated polyester and / or vinyl ester. If the hydrated compound includes the boric acid hydrate, etc., and the organic binder is an unsaturated polyester resin and / or vinyl ester resin, it is particularly preferable that the amount of the boric acid hydrate, etc. mixed is 30 parts by mass or more and 300 parts by mass or less (more preferably 40 parts by mass or more and 250 parts by mass or less, and even more preferably 45 parts by mass or more and 200 parts by mass or less) per 100 parts by mass of the unsaturated polyester and / or vinyl ester.
[0046] 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.
[0047] 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.
[0048] The amount of the filler to be mixed should be between 1 and 200 parts by mass (more specifically, between 3 and 150 parts by mass) per 100 parts by mass of the organic binder. Within this range, excellent strength can be achieved while ensuring lightness.
[0049] If the organic binder is an unsaturated polyester resin and / or a vinyl ester resin, the amount of the filler to be mixed should be 1 to 200 parts by mass (more specifically, 3 to 150 parts by mass) per 100 parts by mass of the unsaturated polyester and / or vinyl ester.
[0050] Examples of the flame retardants include phosphorus-based flame retardants, halogen-based flame retardants, nitrogen-based flame retardants, and silicon-based flame retardants, and one or more of these can be used.
[0051] 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.
[0052] 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.
[0053] Examples of the polyphosphate compounds include ammonium polyphosphate, ammonium polyphosphate amide, melamine polyphosphate, piperazine polyphosphate, melem polyphosphate, melam polyphosphate, melon polyphosphate, and aluminum polyphosphate.
[0054] 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.
[0055] 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.
[0056] 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.
[0057] The amount of the flame retardant mixed is preferably 1 to 200 parts by mass (more preferably 3 to 150 parts by mass, and even more preferably 5 to 100 parts by mass) per 100 parts by mass of the organic binder. By having the flame retardant within this range, dispersibility can be improved, and both heat resistance and light weight can be better achieved.
[0058] When the organic binder is an unsaturated polyester resin and / or a vinyl ester resin, it is particularly preferable that the amount of the flame retardant mixed is 1 part by mass or more and 200 parts by mass or less (more preferably 3 parts by mass or more and 150 parts by mass or less, and even more preferably 5 parts by mass or more and 100 parts by mass or less) per 100 parts by mass of the unsaturated polyester and / or vinyl ester. By having the flame retardant within this range, it is possible to improve dispersibility and further achieve both heat resistance and lightweight properties.
[0059] 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.).
[0060] When the organic binder is an unsaturated polyester resin and / or a vinyl ester resin, the amount of the viscosity modifier mixed is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the unsaturated monomer.
[0061] Examples of the initiators include organic peroxides such as hydroperoxides, dialkylperoxides, dialkylketone peroxides, diacylperoxides, ketone peroxides, peroxyesters, peroxyketals, and peroxydicarbonates, as well as azo compounds such as azobisisobutyronitrile, azobiscarbonamide, and 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile. One or more of these can be used.
[0062] When the organic binder is an unsaturated polyester resin and / or a vinyl ester resin, the amount of the initiator mixed is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, per 100 parts by mass of the unsaturated monomer.
[0063] If the organic binder is an unsaturated polyester resin and / or vinyl ester resin, the heat-absorbing layer (A) can be obtained by mixing the unsaturated polyester and / or vinyl ester, the unsaturated monomer, and the heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.), adding other additives as needed, mixing, and curing to obtain a heat-absorbing layer (A) containing an unsaturated polyester resin and / or vinyl ester resin and a heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.). In particular, a first liquid (first component) can be prepared by mixing the unsaturated polyester and / or vinyl ester, the unsaturated monomer, and the heat-absorbing compound (e.g., boric acid, boric acid hydrate, etc.), and other additives as needed, and a second liquid (second component) containing an initiator can be prepared, and the first liquid and the second liquid can be mixed and reacted to obtain a heat-absorbing layer (A). Furthermore, endothermic compounds (e.g., boric acid, boric acid hydrate, etc.) and other additives may be mixed only with the first component, or they may be mixed with the second component as needed. In such cases, it is particularly preferable to mix, react, and cure at a temperature of 10°C to 150°C (more preferably 15°C to 130°C). The size and shape can also be adjusted using molds or dies.
[0064] [Heat-absorbing layer (B)] It is also 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) endothermic compounds (e.g., boric acid, boric acid hydrate, etc.). Specifically, it is a heat-absorbing layer that does not contain (substantially contains) the organic binder (unsaturated polyester resin, unsaturated polyester constituting the unsaturated polyester resin, and unsaturated monomers, as well as the vinyl ester resin, vinyl ester constituting the vinyl ester resin, and unsaturated monomers) or endothermic compounds (e.g., boric acid, boric acid hydrate, etc.). "Substantially contains" means that it is less than 5% by mass of the entire heat-absorbing layer (B).
[0065] (Inorganic binder) Examples of the inorganic binder include hydraulic inorganic binders, and among them, hydraulic inorganic binders are preferred from the viewpoint of endothermic properties.
[0066] 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.
[0067] The hydraulic inorganic binder can form a large amount of bound water during bonding, allowing the heat-absorbing layer (B) to contain a large amount of bound water. As a result, when the temperature rises, it can utilize the latent heat of vaporization of the bound water to exhibit excellent heat absorption. Furthermore, the heat-absorbing layer (B) containing the hydraulic inorganic binder also has excellent strength, which can improve the strength of the laminate of the present invention.
[0068] 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.
[0069] The heat-absorbing layer (B) can be obtained by mixing the inorganic binder and, if necessary, other additives, and then curing the mixture. For example, the heat-absorbing layer (B) can be obtained by mixing the inorganic binder and other additives with water to form a slurry, and then curing and hardening the mixture. In addition, reinforcing materials such as glass nonwoven fabric, glass cloth, and ceramic paper can be embedded during manufacturing.
[0070] 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.
[0071] 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.
[0072] 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.
[0073] In the methods of the above-mentioned method (2) and method (3), lamination can be performed without an adhesive (direct lamination without using an adhesive), and when exposed to high temperatures due to a fire or the like, heat generation by the adhesive can be suppressed. For example, in the above-mentioned method (2), the adhesion is excellent.
[0074] As the structure in which the plurality of heat absorption layers are laminated, for example, a structure in which a plurality of heat absorption layers (A) are laminated, a structure in which a heat absorption layer (A) and a heat absorption layer (B) are laminated, etc. are used, and although not particularly limited, heat absorption layer (A) / heat absorption layer (A), heat absorption layer (A) / heat absorption layer (B), heat absorption layer (B) / heat absorption layer (A) / heat absorption layer (B), heat absorption layer (A) / heat absorption layer (B) / heat absorption layer (A), heat absorption layer (B) / heat absorption layer (A) / heat absorption layer (B) / heat absorption layer (A), etc. Structures laminated in such a structure are exemplified.
[0075] In addition, the heat absorption layer (A) may include a plurality of heat absorption layers (A) such as a heat absorption layer (A1), a heat absorption layer (A2), etc. that contain different raw materials other than an organic binder and a heat absorption compound (for example, boric acid, boric acid hydrate, etc.), or have different thicknesses. The heat absorption layer (B) may include a plurality of heat absorption layers (B) such as a heat absorption layer (B1), a heat absorption layer (B2), etc. that contain different raw materials other than an inorganic binder, or have different thicknesses.
[0076] The density of the heat absorption layer (A) is 0.1 g / cm ３ , ３ , ３ , ３ , ３ , ３ , ３ , ３ , ３ , ３ , , ３ ,
[0076] , ３ to less than 2.0 g / cm ３ (more preferably 0.3 g / cm ３ or more and 1.8 g / cm ３ or less, and even more preferably 0.5 g / cm ３ or more and 1.6 g / cm ３ or less). The density of the heat absorption layer (B) is 0.1 g / cm ３ or more and 1.5 g / cm ３ or less (more preferably 0.3 g / cm ３ or more and 1.2 g / cm ３ or less, and even more preferably 0.5 g / cm ３ or more and 1.0 g / cm ３The following is preferable. By having such a density for the heat-absorbing layer (heat-absorbing layer (A) and heat-absorbing layer (B)), it is possible to obtain a heat-absorbing layer that is lightweight yet has excellent heat resistance, strength, and dimensional stability.
[0077] 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, even more preferably 5 mm or more and 25 mm or less).
[0078] [Thermal Foam Layer] The laminate of the present invention includes a heat-absorbing layer and a thermal foam layer. As the thermal foam 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 foam layer reaches a predetermined foaming temperature, foams up due to the respective raw materials constituting the thermal foam layer, forming a carbonized heat insulating layer.
[0079] 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 to 400°C, from the standpoint of preventing temperature rise due to flames or heat.
[0080] 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.
[0081] 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 types.
[0082] Examples of the resin component 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.
[0083] 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, melamine polyphosphate, melamine polyphosphate, boron phosphate, boron polyphosphate, aluminum phosphate, and aluminum polyphosphate; and other inorganic compounds such as zinc borate.
[0084] Examples of the foaming agents include melamine and its derivatives, dicyandiamide and its derivatives, azobistetrasome and its derivatives, azodicarbonamide, urea, thiourea, and the like.
[0085] Examples of the carbonizing agent include pentaerythritol, dipentaerythritol, trimethylolpropane, starch, and casein.
[0086] 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.
[0087] 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 the above mixing ratio, flame retardancy and fire resistance can be satisfied, and this is a preferred embodiment.
[0088] 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.
[0089] 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.
[0090] 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.
[0091] 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.
[0092] (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, reinforcing layers, flame-retardant layers, and other layers (e.g., heat-reflective layers, heat-shielding layers, waterproof layers, water-repellent layers, water-shielding layers, heat-insulating layers, etc.).
[0093] 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.
[0094] The decorative layer can be provided on the surface of the heat-foamed layer. For example, the decorative layer can be made of wood, organic resin, inorganic resin, metal, or the like, such as boards or sheets. In this invention, providing the decorative layer enhances the aesthetics, water resistance, and weather resistance of the laminate, making it useful. Furthermore, the decorative layer can be provided after installing furring strips, spacers, etc., in advance.
[0095] The reinforcing layer is a layer used to reinforce the laminate by improving strength, fire resistance, or shielding against heat, flames, smoke, water, water vapor, etc., and can be provided between the heat-foamed layer and the heat-absorbing layer, between the heat-absorbing layer and the organic substrate, or on the entire surface or part of the surface of the heat-foamed layer. In the present invention, it is particularly preferable to provide the layer so as to span across the butt joints (seams, corners, etc.) of each layer. Examples of reinforcing materials that constitute the reinforcing layer include glass fiber sheets, glass fiber cloth, glass fiber tape, etc.
[0096] The thickness of the reinforcing layer can be set appropriately depending on the application, but 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.
[0097] For example, gypsum board, cement board, etc., can be used as the flame-retardant layer.
[0098] 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 sheets, aluminum foil / mesh laminated sheets, and aluminum foil / synthetic resin laminated sheets.
[0099] 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.
[0100] (Characteristics of the Laminate) The laminate of the present invention can be made thinner than the conventional technology, and the thickness of the laminate (total thickness) is preferably 200 mm or less, more preferably 10 to 120 mm, and even more preferably 20 to 80 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 work can be reduced, and work efficiency can be increased. When installed in 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.
[0101] [Coated Structure] The present invention relates to a coated structure in which an organic substrate is coated by the laminate. The coated structure is preferable because the organic substrate is coated by the laminate including the heat-absorbing layer and the heat-foaming layer, resulting in excellent fire resistance.
[0102] 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.
[0103] (Organic base material) Examples of the organic base material include wood base material, plastic base material, fiber-reinforced plastic base material, paper base material, fiber base material, or base materials that combine these. From the viewpoint of strength and lightness, wood base material, plastic base material, fiber-reinforced plastic base material, or base materials that combine these are preferred.
[0104] 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.
[0105] Of the aforementioned wood-based materials, CLT is a type of cross-laminated timber, which is a wood-based material made by arranging sawn timbers (laminae) 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 JAS 3079:2019 "Cross-laminated timber" as "wood with a structure of three or more layers, mainly by laminating and bonding sawn timbers 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) and the like.
[0106] The thickness of the aforementioned wood-based material can be set appropriately depending on the application and other factors.
[0107] As the aforementioned plastic substrate, a substrate mainly composed of a thermoplastic resin and / or a thermosetting resin can be used.
[0108] 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, silicone resin, and the like.
[0109] 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.
[0110] 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.
[0111] 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.
[0112] The thickness of the aforementioned plastic substrate can be set appropriately depending on the application and other factors.
[0113] Examples of the base material include flat plates, or axial members with a polygonal (rectangular, etc.) or circular cross-section. Flat plates and axial members with a polygonal 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.
[0114] 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.
[0115] Figures 1 to 8 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 layers 2Ba and 2Bb in Figures 7 and 8 correspond to the heat-absorbing layer (B), indicating that there are multiple layers of heat-absorbing layer (B).
[0116] 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 so as to be 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 heat 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 substrate 1 due to heat, thereby exhibiting excellent fire resistance.
[0117] The covering structure may include cases where the organic base material 1 is a flat plate or an axial member with a polygonal or circular cross-section.
[0118] Furthermore, as shown in the coating structure of Figure 2, the organic substrate 1 can be configured with 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 in contact with the organic substrate 1. In the present invention, the synergistic effect of these three layers can also prevent combustion, deformation, and loss of strength of the organic substrate 1 due to heat, thereby exhibiting excellent fire resistance.
[0119] When a wood-based material such as CLT or a fiber-reinforced plastic material is used as the organic base material 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 material such as CLT is used as the organic base material 1, it is also preferable in terms of promoting carbon neutrality.
[0120] As a method for forming the coating structure of the present invention, for example, the following methods can be employed: (1) 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, is manufactured in advance and fixed 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 in which the heat-absorbing layer 2A, a heat-absorbing layer 2B, and a thermal foaming layer 3 are fixed to the organic substrate 1 in order, or a method in which the heat-absorbing layer 2B, a heat-absorbing layer 2A, and a thermal foaming layer 3 are fixed 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 thermal foaming layer 3 is fixed (Figures 3 and 4). (4) A composite layer Q having a heat-absorbing layer 2B and a heat-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 heat-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 (Figures 5 and 6). (5) 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 (Figures 7 and 8).
[0121] 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).
[0122] 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.
[0123] In the present invention, it is preferable that each of the above-mentioned layers, composite layers, and laminates, or any or all thereof, are made of sheet-like or plate-like (board, etc.) materials. 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.
[0124] 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.
[0125] 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 side surfaces 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 side surfaces 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.
[0126] 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.
[0127] 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.
[0128] 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.
[0129] The following materials were used to construct the laminate used as the test specimen.
[0130] - Organic base material 11: Laminated cedar wood (240mm x 240mm, 3000mm high, square column) - Organic base material 12: Laminated cedar wood (150mm x 150mm, 3000mm high, square column)
[0131] • Heat-absorbing layer 2A1: Heat-absorbing board [A heat-absorbing board obtained by curing a mixture of 50 parts by mass of unsaturated polyester resin (unsaturated polyester / styrene (mass ratio 60 / 40)), 50 parts by mass of boric acid monohydrate, and 1 part by mass of methyl ethyl ketone peroxide in a mold (25°C, 3 hours), and then demolding. Thickness 13 mm, mass 18.0 kg / m ２ ] ・Heat-absorbing layer 2A2: Heat-absorbing board [A mixture of 45 parts by mass of unsaturated polyester resin (unsaturated polyester / styrene (mass ratio 55 / 45)), 55 parts by mass of boric acid monohydrate, and 1 part by mass of methyl ethyl ketone peroxide is applied to a glass nonwoven fabric (450 g / m ２ A heat-absorbing board obtained by impregnating a material with ) into one layer, stacking seven layers of this material, heat-curing it in a mold (60°C, 1 hour), and then demolding. Thickness 13 mm, mass 17.0 kg / m ２] ・Heat-absorbing layer 2A3: Heat-absorbing board [A heat-absorbing board obtained by curing a mixture of 50 parts by mass of unsaturated polyester resin (unsaturated polyester / styrene (mass ratio 60 / 40)), 50 parts by mass of boric acid, and 1 part by mass of methyl ethyl ketone peroxide in a mold (25°C, 3 hours), and then demolding. Thickness 13 mm, mass 18.0 kg / m ２ ]
[0132] • Heat-absorbing layer 2B1: Reinforced gypsum board (thickness 12.5 mm, mass 10.0 kg / m) ２ ) ・Heat-absorbing layer 2B2: Reinforced gypsum board (thickness 21 mm, mass 16.8 kg / m) ２ )
[0133] • 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 mm, mass 1.4 kg / m ２ ] ・Thermal foaming layer 32: Thermoplastic sheet [A thermoplastic 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 3 mm, mass 4.2 kg / m ２ ] ・Thermal foaming layer 33: Thermoplastic sheet [A thermoplastic 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 1.5 mm, mass 2.1 kg / m ２ ]
[0134] • Decorative layer 1: Laminated cedar wood (15 mm thick, 5.2 kg / m mass) ２ ) ・Decorative layer 2: Cedar paneling (thickness 12 mm, effective width 105 mm, mass 4.2 kg / m) ２ )
[0135] • Reinforcement layer 1: Glass fiber tape (thickness 0.2 mm)
[0136] Adhesive: Acrylic resin adhesive
[0137] [Example 1] A heat-absorbing layer 2B1 (100 mm x 100 mm) was bonded to a heat-absorbing layer 2A1 (100 mm x 100 mm), and then a heat-foamed layer 31 (100 mm x 100 mm) was bonded to it using an adhesive to obtain a test specimen 1 (heat-absorbing layer 2B1 / heat-absorbing layer 2A1 / heat-foamed layer 31).
[0138] [Example 1A] A heat-absorbing layer 2B1 (100 mm x 100 mm) was bonded to a heat-absorbing layer 2A3 (100 mm x 100 mm), and then a thermal foam layer 32 (100 mm x 100 mm) was bonded to it using an adhesive to obtain a test specimen 1A (heat-absorbing layer 2B1 / heat-absorbing layer 2A3 / thermal foam layer 32).
[0139] [Comparative Example 1] A heat-absorbing layer 2B1 (100 mm x 100 mm) and a heat-foaming layer 31 (100 mm x 100 mm) were bonded in order to a heat-absorbing layer 2B1 (100 mm x 100 mm) using an acrylic resin adhesive to obtain test specimen 2 (heat-absorbing layer 2B1 / heat-absorbing layer 2B1 / heat-foaming layer 31).
[0140] [Comparative Example 2] A heat-absorbing layer 2B1 (100 mm x 100 mm), a heat-absorbing layer 2B1 (100 mm x 100 mm), a heat-absorbing layer 2B1 (100 mm x 100 mm), and a heat-foaming layer 31 (100 mm x 100 mm) were bonded in order to a heat-absorbing layer 2B1 (100 mm x 100 mm) using an acrylic resin adhesive to obtain a test specimen 3 (heat-absorbing layer 2B1 / heat-absorbing layer 2B1 / heat-absorbing layer 2B1 / heat-absorbing layer 2B1 / heat-foaming layer 31).
[0141] (Fire Resistance Test 1) Fire resistance test 1 was performed on the test specimens (test specimens 1 to 3) prepared using the method described above, using a cone calorimeter as specified in ISO 5660. The heating intensity was 50 kW / m². ２The 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 refers to the side with the heat-absorbing layer (the non-heated side). As a result, in Example 1 and Example 1A, the highest temperature reached was 125°C or less (100°C or more and 125°C or less), showing excellent fire resistance. On the other hand, in Comparative Example 1, the highest temperature reached exceeded 250°C, showing inferior fire resistance. In Comparative Example 2, the highest temperature reached was 200°C or less (150°C or more and 200°C or less), showing fire resistance, but the thickness was greater and the mass was heavier. From these results, it was confirmed that the laminate according to the present invention can keep the mass per unit area low, achieve weight reduction, and furthermore, the fire resistance is at a practical level.
[0142] [Example 2] Heat-absorbing layers 2B1 were butted together and screwed to the entire four sides of the organic substrate 11. Next, heat-absorbing layers 2A1 were butted together and screwed in place. Next, heat-foamed layers 32 were butted together and applied using adhesive. Next, reinforcing layers 1 were heat-fused and attached to the joints (seams and corners) of the heat-foamed layers 32. Finally, decorative layers 1 were screwed in place to obtain the test specimen 4. Each heat-absorbing layer 2A, each heat-absorbing layer 2B, each heat-foamed layer 3, and decorative layer were appropriately adjusted to a size that facilitated installation, and each reinforcing layer was adjusted to a width of approximately 50 to 100 mm across the joints. The same procedure was followed for subsequent examples.
[0143] [Example 3] The heat-absorbing layer 2B1 was butted against the four sides of the organic substrate 12 and fastened with screws, then the heat-absorbing layer 2A2 was butted against the sides and fastened with screws, then the heat-foamed layer 32 was butted against the sides using adhesive, then the reinforcing layer 1 was heat-fused and attached to the joints (seams and corners) of the heat-foamed layer 32, and then the decorative layer 2 was attached with finishing nails to obtain the test specimen 5.
[0144] [Example 4] The heat-absorbing layer 2B2 was butted against the four sides of the organic substrate 12 and fastened with screws, then the heat-absorbing layer 2A2 was butted against the sides and fastened with screws, then the heat-foamed layer 32 was butted against the sides using adhesive, then the reinforcing layer 1 was heat-fused and attached to the joints (seams and corners) of the heat-foamed layer 32, and then the decorative layer 2 was attached with finishing nails to obtain the test specimen 6.
[0145] [Example 5] The heat-absorbing layer 2B2 was butted against the four sides of the organic substrate 12 and fastened with screws, then the heat-absorbing layer 2A2 was butted against the sides and fastened with screws, then the heat-foamed layer 33 was butted against the sides using adhesive, then the reinforcing layer 1 was heat-fused and attached to the joints (seams and corners) of the heat-foamed layer 33, and then the decorative layer 2 was attached with finishing nails to obtain the test specimen 7.
[0146] [Example 6] The heat-absorbing layer 2A3 was butted against the four sides of the organic substrate 12 and fastened with screws, then the heat-absorbing layer 2A3 was butted against the sides and fastened with screws, then the heat-foamed layer 32 was butted against the sides using adhesive, then the reinforcing layer 1 was heat-fused and attached to the joints (seams and corners) of the heat-foamed layer 32, and then the decorative layer 2 was attached with finishing nails to obtain the test specimen 8.
[0147] [Comparative Example 3] The heat-absorbing layer 2B1 was butted against the four side surfaces of the organic substrate 12 and fastened with screws, then the heat-absorbing layer 2B1 was butted against the surface and fastened with screws, then the reinforcing layer 1 was heat-fused and attached to the joints (seams and corners) of the heat-absorbing layer 2B1, and then the decorative layer 2 was installed with finishing nails to obtain the test specimen 9.
[0148] (Fire Resistance Test 2) The test specimens (test specimens 4-9) prepared using the method described above were placed vertically in a test furnace, and a heating test was conducted for 90 minutes according to the standard heating curve of ISO 834. The surface temperature of the organic substrate was measured using thermocouples until 270 minutes after heating. Thermocouples were placed at a total of 24 locations on the surface of the organic substrate: both ends (corners) and the center in the horizontal direction, and the top, center, and bottom in the vertical direction. The evaluation criteria are as follows. The test results are shown in the table. In consideration of the dangers of wood combustion in practical use, it is preferable that the evaluation criteria be A or B for practical use. (Evaluation Criteria) A: All parts remain below 200°C for 90 minutes of heating and for 270 minutes thereafter. B: All parts remain below 250°C for 90 minutes of heating and for 270 minutes thereafter. C: One or more parts exceed 250°C for 90 minutes of heating and for 270 minutes thereafter. As a result, Examples 2, 3, 4, 5, and 6 received an evaluation of A, demonstrating excellent fire resistance. On the other hand, Comparative Example 3 received an evaluation of C, demonstrating inferior fire resistance.
Claims
1. A laminate comprising a heat-absorbing layer and a thermal foaming layer, wherein the heat-absorbing layer is formed of a binder and one or more selected from inorganic acids, hydroxide compounds, and hydrated compounds (excluding sodium tetraborate hydrate).
2. The laminate according to claim 1, wherein the inorganic acid contains boric acid.
3. The laminate according to claim 1, wherein the binder is an organic binder.
4. The laminate according to claim 3, wherein the organic binder is obtained from an unsaturated polyester and an unsaturated monomer.
5. The laminate according to claim 1, wherein the heat-absorbing layer comprises at least one heat-absorbing layer formed of an organic binder and one or more selected from an inorganic acid, a hydroxide compound, and a hydrated compound (excluding sodium tetraborate hydrate), and a heat-absorbing layer formed of an inorganic binder.
6. The laminate according to claim 5, wherein the inorganic acid contains boric acid.
7. A coated structure in which a substrate is coated with a laminate according to any one of claims 1 to 6.
8. The coating structure according to claim 7, wherein the substrate is an organic substrate.
9. The covering structure according to claim 8, wherein the organic substrate is a wood substrate and / or a plastic substrate.
10. The coating structure according to claim 7, wherein the heat-absorbing layer and the substrate are in contact.
11. The covering structure according to claim 7, wherein the base material is a flat plate or an axial member having a polygonal or circular cross-section.