Thermally-expandable refractory material

Abstract

This thermally-expandable refractory material is provided with a base material on at least one side of an expansion layer containing a binder resin and thermally expandable graphite, wherein, when the thermally-expandable refractory material is heated at 185°C for 30 minutes, the rate of change in the thickness of the thermally-expandable refractory material is 20% or less, and the rate of change thereof in the TD and MD directions is 2% or less.

Description

thermally expandable fireproofing material

[0001] The present invention relates to a thermally expandable fire-resistant material.

[0002] In the construction industry, fireproof materials are used in building materials such as fittings, pillars, and wall materials for fire prevention. Various types of fireproof materials have been developed. For example, Patent Document 1 discloses an invention related to a thermally expandable fireproof material containing an elastomer consisting of rubber and a styrene-based thermoplastic elastomer, thermally expandable graphite, and an inorganic phosphate-based compound. Such a thermally expandable fireproof material expands upon heating, and the combustion residue forms a fireproof insulating layer, thereby exhibiting fireproof insulating performance. A thermally expandable fireproof material containing thermally expandable graphite is installed, for example, in the gap between fittings such as doors and windows installed in openings in buildings and the surrounding frames such as door frames and window frames. In the event of a fire, the sheet expands in the thickness direction to close the gap between the fittings and the frame material and prevent the fire from spreading.

[0003] Patent No. 7142139

[0004] When attaching a thermally expandable fire-resistant material, the fittings may be powder-coated. However, in recent years, the thermally expandable fire-resistant material may be attached to the fittings before the powder coating, and then the fittings may be powder-coated in this state. After powder coating, the fittings to which the thermally expandable fire-resistant material is attached must be cured at high temperatures (e.g., 180°C) to improve the adhesion of the paint. However, when conventional thermally expandable fire-resistant materials are exposed to high temperatures, the thermally expandable graphite expands, causing voids on the surface, or the resin constituting the fire-resistant material melts, resulting in surface roughness and shrinkage, resulting in a deterioration of the appearance. Therefore, thermally expandable fire-resistant materials are required to have dimensional stability so that they can maintain their appearance and performance even at high temperatures.

[0005] Therefore, an object of the present invention is to provide a thermally expandable fireproof material that exhibits a small rate of dimensional change even in a high-temperature environment.

[0006] As a result of extensive investigation, the present inventors have found that the above-mentioned problems can be solved by disposing a substrate on at least one side of an expandable layer containing a binder resin and thermally expandable graphite, and adjusting the rate of change in thickness, width, and length directions to be equal to or less than a certain level even when exposed to high temperatures for a certain period of time. That is, the present invention provides the following [1] to

[10] .

[0007] [1] A thermally expandable fire-resistant material comprising an expandable layer containing a binder resin and thermally expandable graphite, and a substrate provided on at least one side of the expandable layer, wherein, when the thermally expandable fire-resistant material is heated at 185°C for 30 minutes, the thickness change rate of the thermally expandable fire-resistant material is 20% or less and the thickness change rate in the TD and MD directions is 2% or less. [2] The thermally expandable fire-resistant material according to [1], further comprising an adhesive layer provided on the surface of the expandable layer opposite the surface on which the substrate is provided. [3] The thermally expandable fire-resistant material according to [1] or [2], wherein the substrate comprises at least a plastic. [4] The thermally expandable fire-resistant material according to [3], wherein the plastic comprises at least one selected from the group consisting of PVC, polyurethane resin, PE, PP, PC, polyester resin, polyamide resin, and acrylic resin. [5] The thermally expandable fire-resistant material according to any one of [1] to [4], wherein the substrate further comprises a fibrous structure. [6] The thermally expandable fireproof material according to any one of [1] to [5], wherein when the thermally expandable fireproof material having dimensions of 25 mm x 25 mm is attached to the surface of one of two facing SUS plates spaced apart at a distance three times the thickness of the expansion layer and then heated at 300°C for 10 minutes, the area of ​​the thermally expandable fireproof material as viewed perpendicular to the SUS plate is at least 3.0 times the area of ​​the thermally expandable fireproof material before heating. [7] The thermally expandable fireproof material according to any one of [1] to [6], wherein the binder resin is a thermosetting resin. [8] The thermally expandable fireproof material according to [7], wherein the thermosetting resin includes an epoxy resin. [9] The thermally expandable fireproof material according to any one of [1] to [8], wherein the expansion onset temperature of the thermally expandable graphite is 160°C or higher.

[10] The heat-expandable fire-resistant material according to any one of [1] to [9], wherein the heat-expandable fire-resistant material is a wound body having a length of 10 m or more.

[0008] According to the present invention, it is possible to provide a thermally expandable fireproof material that exhibits a small rate of dimensional change even in a high-temperature environment.

[0009] [Thermal-Expandable Fireproof Material] The thermal-expandable fireproof material of the present invention comprises an expansion layer containing a binder resin and thermally expandable graphite, and a substrate provided on at least one side of the expansion layer. When heated at 185°C for 30 minutes, the thickness change rate is 20% or less, and the thickness change rates in both the TD and MD directions are 2% or less. If the thickness change rate exceeds 20% or if either the TD or MD change rate exceeds 2%, the dimensions of the thermal-expandable fireproof material may become unstable in a high-temperature environment, resulting in problems such as a deterioration in the appearance of the thermal-expandable fireproof material. Note that the MD direction refers to the flow direction of the thermal-expandable fireproof material during production, and the TD direction refers to the direction perpendicular to the flow direction of the thermal-expandable fireproof material during production.

[0010] From the above viewpoints, the thickness change rate is preferably 5% or less, more preferably 3% or less. From the same viewpoints, the change rates in both the TD and MD directions are preferably 1.5% or less, more preferably 1% or less. Specifically, the change rate in the MD direction is preferably 1.5% or less, more preferably 1% or less. Furthermore, the change rate in the TD direction is preferably 1% or less, more preferably 0.7% or less. From the viewpoint of dimensional stability, the smaller these change rates are, the better, and all may be 0% or more. However, from the viewpoint of ensuring a certain degree of thermal expandability, the thickness change rate is, for example, 0.05% or more, preferably 0.1% or more. The change rate in the MD direction is, for example, 0.05% or more, preferably 0.1% or more. The change rate in the TD direction is, for example, 0.1% or more, preferably 0.3% or more.

[0011] Each rate of change can be calculated for each direction based on the following formula (1): Rate of change (%) = |Dimension before heating - Dimension after heating| / Dimension before heating x 100 (Formula (1)). For example, the rate of change in thickness can be calculated based on the following formula (2): Rate of change (%) = |Thickness of heat-expandable fire-resistant material before heating - Thickness of heat-expandable fire-resistant material after heating| / Thickness of heat-expandable fire-resistant material before heating (m) x 100 (Formula (2)). The rates of change in the TD and MD directions can also be calculated in a similar manner. In measuring each rate of change, the heat-expandable fire-resistant material can be provided with an adhesive layer on the outermost surface, or, if no adhesive layer is provided but the expansion layer itself has adhesive or adhesive properties, can be attached to the iron plate via the adhesive layer or expansion layer, and heated in this bonded state at 185°C. In this case, if both surfaces can be adhered to the iron plate, it is preferable to adhere the surface opposite to the side on which the substrate is provided to the iron plate. However, if substrates are provided on both sides, it is preferable to adhere any one surface to the iron plate. On the other hand, if no adhesive layer is provided on the outermost surface and the expansion layer itself does not have adhesive or tackiness and cannot adhere the heat-expandable fireproof material to the iron plate, it is preferable to heat the heat-expandable fireproof material placed on the iron plate with the surface opposite to the surface on which the substrate is provided in contact with the iron plate at 185°C. Furthermore, if substrates are provided on both sides of the expansion layer and both outermost surfaces cannot be adhered to the iron plate, it is preferable to place any one surface on the iron plate in contact with the iron plate. Note that each rate of change can be adjusted to a desired range by the type of substrate and the composition of the expansion layer, etc.

[0012] (Substrate) The thermally expandable fire-resistant material of the present invention has a substrate on at least one side of the expansion layer. By providing a substrate, the expansion layer is protected or supported by the substrate when heated at high temperatures, and the dimensions of the thermally expandable fire-resistant material are stable even in high-temperature environments. It is also possible to prevent the surface of the expansion layer from becoming roughened by high-temperature heat. The substrate may be provided on only one side of the expansion layer or on both sides of the expansion layer, but it is preferable that the substrate be provided on only one side of the substrate.

[0013] The substrate preferably contains at least plastic. Among these, it is more preferable to contain at least one selected from the group consisting of polyester resins such as polyethylene terephthalate (PET), polyvinyl chloride (PVC) resins, polyurethane resins, polyolefin resins such as polyethylene (PE) and polypropylene (PP), polycarbonate resins, polyamides, and acrylic resins. Of these, PET is even more preferable. By including plastic in the substrate, heat resistance is imparted to the substrate, which facilitates improving the dimensional stability of the thermally expandable fire-resistant material in high-temperature environments.

[0014] The substrate is preferably a plastic film made of the above plastics, and more preferably a PET film. The plastic film may be a stretched film or a non-stretched film, but from the viewpoint of dimensional stability, a stretched film is preferred, and a biaxially stretched film is more preferred. The plastic film is preferably annealed. By annealing the plastic film, the dimensional stability of the substrate is improved, and the dimensional stability of the entire heat-expandable fire-resistant material is also easily improved.

[0015] The substrate also preferably includes a fibrous structure. By using a fibrous structure, the binder resin of the expandable layer penetrates between the fibers, improving adhesion to the expandable layer and facilitating improved dimensional stability of the thermally expandable fireproof material in high-temperature environments. Examples of the fibrous structure include knitted fabric, woven fabric, and nonwoven fabric, with woven fabric and nonwoven fabric being preferred. Examples of fibers used in the fibrous structure include glass fiber, ceramic fiber, cellulose fiber, polyester fiber, carbon fiber, and graphite fiber.

[0016] The substrate may also be a composite material of fiber and plastic, such as a composite formed by impregnating a fiber layer with plastic, for example, a composite formed by laminating a plastic layer on a fiber layer and partially impregnating the plastic layer. As a composite material of fiber and plastic, PET glass cloth is preferred. When a composite material of fiber and plastic is used as the substrate, it is preferable to arrange the fiber layer on the expansion layer side and the plastic layer on the outside. This configuration allows the appearance of the thermally expandable fire-resistant material to be maintained in good condition. Furthermore, impregnating the fiber layer with the expansion layer makes it easier to laminate the substrate and the expansion layer with high adhesion.

[0017] The substrate preferably has a melting point of 180° C. or higher, more preferably 200° C. or higher, and even more preferably 220° C. or higher. Therefore, when the substrate is a plastic film, the melting point of the plastic constituting the substrate is preferably equal to or higher than the above-mentioned lower limit. When the melting point of the substrate is equal to or higher than the above-mentioned lower limit, the dimensions of the thermally expandable fire-resistant material tend to be stable even in a high-temperature environment.

[0018] (Binder Resin) The expandable layer constituting the thermally expandable fire-resistant material of the present invention contains a binder resin. The binder resin preferably contains a thermosetting resin, more preferably an epoxy resin. By using an epoxy resin as the binder resin, the thermally expandable fire-resistant material tends to maintain its dimensions stable even when exposed to a high-temperature environment, and each rate of change can be easily adjusted to a certain level or less.

[0019] Examples of epoxy resins include epoxy compounds alone, or compounds consisting of an epoxy compound as a main component and a curing agent. Epoxy compounds are compounds having an epoxy group, and specific examples include glycidyl ether types and glycidyl ester types. Glycidyl ether types may be bifunctional or multifunctional (trifunctional or higher). The same applies to glycidyl ester types. Epoxy compounds may contain monofunctional compounds to adjust the degree of crosslinking, etc. Among these, bifunctional glycidyl ether types are preferred.

[0020] Examples of the bifunctional glycidyl ether epoxy compound include alkylene glycols such as polyethylene glycol and polypropylene glycol, neopentyl glycol, 1,6-hexanediol, and hydrogenated bisphenol A. Further examples include aromatic epoxy compounds containing an aromatic ring, such as bisphenol A, bisphenol F, bisphenol AD, ethylene oxide-bisphenol A, and propylene oxide-bisphenol A. Among these, aromatic epoxy compounds such as bisphenol A and bisphenol F are preferred, and it is also preferred to use an aromatic epoxy compound in combination with an aliphatic epoxy compound. It is particularly preferred to use a bisphenol F epoxy compound in combination with an aliphatic epoxy compound. When a bisphenol F epoxy compound and an aliphatic epoxy compound are used in combination, the mixing ratio is not particularly limited, but a mass ratio of aliphatic epoxy compound:bisphenol F epoxy compound of 1:1 to 1:15 is preferred, and a mass ratio of 1:1.2 to 1:10 is more preferred.

[0021] Examples of the glycidyl ester type epoxy compounds include hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type, p-oxybenzoic acid type, etc. Examples of trifunctional or higher functional glycidyl ether type epoxy compounds include phenol novolac type, orthocresol novolac type, DPP novolac type, dicyclopentadiene phenol type, etc. These epoxy compounds may be used alone or in combination of two or more.

[0022] The curing agent may be a polyaddition type or a catalyst type. Examples of polyaddition type curing agents include polyamine curing agents, acid anhydride curing agents, polyphenol curing agents, and polymercaptan. Examples of catalyst type curing agents include tertiary amines, imidazoles, and Lewis acid complexes. The method for curing the epoxy compound is not particularly limited, and can be performed by a known method. The content of the curing agent is preferably within a range of 50 to 150 parts by mass per 100 parts by mass of the epoxy compound. When the content is 50 parts by mass or more, the epoxy compound is easily cured, and when it is 150 parts by mass or less, an effect corresponding to the amount of curing agent blended can be obtained.

[0023] As the thermosetting resin, a thermosetting resin other than the above-mentioned epoxy resin may be used. Specifically, a urethane resin, a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, a polyimide, etc. may be used. Furthermore, as the binder resin, a resin other than the thermosetting resin may be used, for example, an elastomer resin.

[0024] When a thermosetting resin is used, it is preferable to contain a curing accelerator that accelerates curing. The use of a curing accelerator increases the curing rate, allows the thermally expandable graphite and flame retardant to be cured in an appropriately dispersed state, and improves the adhesiveness of the thermally expandable fire-resistant material. This also makes it easier to increase the maximum shear load described above. Furthermore, when an epoxy resin is used as the binder resin, it is more preferable to use a curing accelerator in addition to the curing agent described above. Examples of curing accelerators for epoxy resins include tertiary amines, imidazoles, Lewis acid complexes, etc., and among these, imidazoles are preferred.

[0025] Examples of imidazoles include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethoxybenzoate ... undecylimidazolyl-(1'))-ethyl-s-triazine, 2,4-diamino-6-(2'-ethyl-4'-methylimidazolyl-(1'))-ethyl-s-triazine, 2,4-diamino-6-(2'-ethyl-4'-methylimidazolyl-(1'))-ethyl-s-triazine, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and the like.

[0026] The content of the curing accelerator in the expansion layer is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 1.2 to 6 parts by mass, relative to 100 parts by mass of the thermosetting resin (for example, in the case of an epoxy resin, the total amount of the epoxy compound and the curing agent).

[0027] Examples of elastomer resins include, but are not limited to, diene rubbers such as isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), hydrogenated styrene-butadiene copolymer rubber (HSBR), chloroprene rubber (CR), and acrylonitrile-butadiene rubber (NBR), as well as rubber components such as ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), natural rubber, butyl rubber, chlorinated butyl rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, multi-vulcanized rubber, non-vulcanized rubber, silicone rubber, fluororubber, and urethane rubber. The elastomer resin is preferably treated with a crosslinking agent or vulcanizing agent, as described below. Such treatments can suppress shrinkage due to residual stress during molding and improve thermal stability.

[0028] The above binder resins may be used alone or in combination of two or more. When an elastomer resin is used as the binder resin, from the viewpoint of dimensional stability in a high-temperature environment, it is preferable to use a rubber component, more preferably a diene rubber, and even more preferably NBR. The binder resin content is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less, based on the total amount of the expandable layer. When the binder resin content is equal to or greater than the lower limit, the shape retention of the expandable layer is likely to be improved. When the binder resin content is equal to or less than the upper limit, the content of thermally expandable graphite can be increased, and fire resistance is likely to be improved.

[0029] (Thermally Expandable Graphite) The expandable layer constituting the thermally expandable fireproof material of the present invention contains thermally expandable graphite. Thermally expandable graphite is a conventionally known substance that expands upon heating, and is obtained by treating raw material powder such as natural flaky graphite, pyrolytic graphite, or kish graphite with a strong oxidizing agent to produce a graphite intercalation compound. Examples of strong oxidizing agents include inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, concentrated nitric acid, perchloric acid, perchlorates, permanganates, dichromates, and hydrogen peroxide. Thermally expandable graphite is a crystalline compound that maintains the layered structure of carbon. The thermally expandable graphite may be neutralized. That is, the thermally expandable graphite obtained by treating with a strong oxidizing agent as described above may be further neutralized with ammonia, aliphatic lower amines, alkali metal compounds, alkaline earth metal compounds, or the like.

[0030] The thermally expandable graphite preferably has an expansion start temperature of 160°C or higher, more preferably 170°C or higher, even more preferably 180°C or higher, and even more preferably 190°C or higher. When the expansion start temperature is equal to or higher than the above lower limit, the dimensions of the thermally expandable fireproof material tend to be stable even in a high-temperature environment. From the viewpoint of fire prevention performance, the expansion start temperature is preferably 300°C or lower, more preferably 250°C or lower. The expansion start temperature of the thermally expandable graphite can be measured by raising the temperature of the thermally expandable graphite at a constant temperature using an apparatus with a temperature control function and capable of measuring normal direction force, and measuring the temperature at which the normal direction force rises. The measuring apparatus is not limited as long as it is capable of controlling the measurement temperature and measuring normal direction stress, and for example, a rheometer can be used.

[0031] The content of thermally expandable graphite in the expansion layer is preferably 40 to 300 parts by mass, more preferably 50 to 250 parts by mass, and even more preferably 60 to 200 parts by mass, per 100 parts by mass of the binder resin. When the content of thermally expandable graphite is equal to or greater than the above-mentioned lower limit, the expansion pressure of the thermally expandable fire-resistant material is easily increased, making it easier to exhibit excellent fire prevention performance in the event of a fire, for example. Furthermore, when the content of thermally expandable graphite is equal to or less than the above-mentioned upper limit, shape retention, processability, etc. are improved.

[0032] (Vulcanizing Agent) When an elastomer resin is used as the binder resin in the expandable layer, it is preferable to compound a vulcanizing agent, and it is particularly preferable to use acrylonitrile-butadiene rubber and a vulcanizing agent in combination. The use of a vulcanizing agent reduces the residual stress in the expandable layer, stabilizes the dimensions of the thermally expandable fire-resistant material even in a high-temperature environment, and makes it easier to adjust the rate of change in the TD and MD directions to a certain level or less.

[0033] Any known vulcanizing agent can be used without limitation, and examples thereof include sulfur-based vulcanizing agents, organic peroxides, and azo compounds. Examples of sulfur-based vulcanizing agents include inorganic agents such as sulfur, insoluble sulfur, precipitated sulfur, sulfur chloride, sulfur monochloride, and sulfur dichloride, but they may also be sulfur-containing organic crosslinking agents. Examples of sulfur-containing organic crosslinking agents include morpholine disulfide, alkylphenol disulfide, tetraalkylthiuram disulfide, N,N'-dithio-bis(hexahydro-2H-azepinone-2), thiuram polysulfide, N-cyclohexyl-2-benzothiazolylsulfenamide, and 2-(4'-morpholinodithio)benzothiazole. Examples of organic peroxides include 2,5-dimethylhexane, 2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 3-di-t-butyl peroxide, t-dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, dicumyl peroxide, α,α'-bis(t-butylperoxyisopropyl)benzene, n-butyl-4,4-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, t-butylperoxybenzoate; benzoyl peroxide; and t-butylperoxy-2-ethylhexyl carbonate. Examples of the azo compound include azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), etc. The vulcanizing agent may be used alone or in combination of two or more kinds.

[0034] Among the vulcanizing agents described above, those that readily undergo a crosslinking reaction with elastomer resins such as acrylonitrile-butadiene rubber when exposed to a high-temperature environment, for example, during curing, are preferred. Specifically, sulfur-based vulcanizing agents are preferred, and at least one selected from tetraalkylthiuram disulfide, N,N'-dithio-bis(hexahydro-2H-azepinone-2), and thiuram polysulfide is more preferred. When a vulcanizing agent is incorporated into the expandable layer, the amount of vulcanizing agent incorporated is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass, and even more preferably 0.5 to 7 parts by mass, per 100 parts by mass of the binder resin.

[0035] (Vulcanization Accelerator) The expandable layer may contain a vulcanization accelerator in addition to the vulcanizing agent. Examples of vulcanization accelerators include metal oxides such as zinc oxide, calcium oxide, and magnesium oxide, thiazole compounds, sulfenamide compounds, thiuram compounds, dithiocarbamate compounds, guanidine compounds, and thiourea compounds. One type of vulcanization accelerator may be used alone, or two or more types may be used in combination. When the expandable layer contains a vulcanization accelerator, the content of the vulcanization accelerator is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of the binder resin.

[0036] (Flame retardant) The expandable layer may contain a flame retardant. By containing a flame retardant, the thermally expandable fire-resistant material can be imparted with flame retardancy, and the performance of the fire-resistant material can be more effectively exhibited. The flame retardant used in the present invention preferably contains one that is solid at room temperature (23°C) and normal pressure (1 atmosphere), and more preferably contains a phosphorus-based solid flame retardant.

[0037] The phosphorus-based solid flame retardant is a compound that becomes solid at room temperature (23° C.) and atmospheric pressure (1 atmosphere), and specific examples thereof include phosphates, phosphazene compounds, phosphoric acid ester compounds, and metal phosphinates.

[0038] Specific examples of phosphates include monophosphates, polyphosphates, etc. The term "phosphates" as used herein includes not only orthophosphates but also phosphites, hypophosphites, etc. The same applies to polyphosphates. Examples of monophosphates include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite; and aluminum salts such as aluminum monophosphate, aluminum diphosphate, aluminum triphosphate, and aluminum hypophosphite. Among these, ammonium phosphate and aluminum phosphite are preferred, and aluminum phosphite is more preferred. Examples of polyphosphates include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate, with ammonium polyphosphate being preferred among these.

[0039] A phosphazene compound is an organic compound in which phosphorus atoms and nitrogen atoms are alternately bonded. Examples of the phosphazene compound include cyclic phosphazene compounds, chain phosphazene compounds, and crosslinked phosphazene compounds crosslinked by a crosslinking group. Specific examples of the phosphazene compound include those containing a structural unit represented by the following general formula (3):

[0040] In the general formula (3), each X independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, an amino group, or a halogen atom. In the general formula (3), examples of the substituent on the aryl group include an alkyl group, an amino group, and a halogen atom. Each X independently represents preferably a phenyl group, a substituted phenyl group, a phenyloxy group, or a substituted phenyloxy group, and more preferably a phenyl group or a phenyloxy group.

[0041] The phosphate ester compound is not particularly limited as long as it is solid at room temperature (23°C), and examples thereof include monophosphate esters and condensed phosphate esters. These phosphate ester compounds may be commercially available products. Examples of monophosphate esters include triphenyl phosphate and tris(tribromoneopentyl)phosphate. Commercially available monophosphate esters include "TPP," "CR-900," and "DAIGUARD-1000" (all manufactured by Daihachi Chemical Industry Co., Ltd.). The condensed phosphate ester may be a halogen-containing condensed phosphate ester, or a halogen-free condensed phosphate ester. More specifically, examples include alkyl-substituted aromatic condensed phosphate esters such as 1,3-phenylenebis(di-2,6-xylenyl phosphate).

[0042] The metal phosphinate is a metal salt of an organic phosphinic acid. Specific examples of the metal phosphinate include aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, and titanium tetrakisdiphenylphosphinate.

[0043] The flame retardant may contain a flame retardant other than the above-mentioned phosphorus-based solid flame retardant, such as a red phosphorus-based flame retardant, a boron-containing flame retardant, a bromine-based flame retardant, an antimony-containing flame retardant, a metal hydroxide, a low-melting glass, a needle-like filler, etc. The flame retardant may be used alone or in combination of two or more.

[0044] The content of the flame retardant in the expandable layer is preferably 30 to 200 parts by mass, more preferably 40 to 150 parts by mass, and even more preferably 50 to 100 parts by mass, per 100 parts by mass of the binder resin. When the content of the flame retardant is equal to or greater than the lower limit, the fire resistance of the fire-resistant material is likely to be improved. On the other hand, when the content of the flame retardant is equal to or less than the upper limit, the flame retardant is likely to be uniformly dispersed in the resin, resulting in excellent moldability.

[0045] (Plasticizer) The expandable layer may contain a plasticizer. By containing a plasticizer, a certain degree of flexibility or conformability is imparted to the thermally expandable fireproof material, and for example, when attached to a building fixture, the expandable layer can easily conform to the irregularities on the surface of the building fixture. The plasticizer is not particularly limited, but examples thereof include phthalic acid-based plasticizers, adipic acid-based plasticizers, phosphoric acid-based plasticizers, and alkylsulfonic acid-based plasticizers.

[0046] Examples of phthalic acid plasticizers include di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), and phthalate esters of higher alcohols or mixed alcohols having about 10 to 13 carbon atoms. Examples of adipic acid plasticizers include dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisopropyl adipate, diisobutyl adipate, bis(2-ethylhexyl adipate), dioctyl adipate, diisononyl adipate, diisodecyl adipate, bis(2-butoxyethyl adipate), and adipic acid polyesters.

[0047] Examples of the phosphoric acid plasticizer include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris(2-chloropropyl)phosphate, tris(2,3-dichloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate, tris(bromochloropropyl)phosphate, bis(2,3-dibromopropyl)-2,3-dichloropropyl phosphate, bis(chloropropyl)monoctyl phosphate, tris(2-ethylhexyl)phosphate, triphenyl phosphate, tricresyl phosphate (TCP), trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, and 2-ethylhexyl diphenyl phosphate. Examples of the alkylsulfonic acid plasticizer include alkylsulfonic acid phenyl ester and N-butylbenzenesulfonamide.

[0048] Adipic acid plasticizers or alkylsulfonic acid plasticizers are preferred, and among them, when an elastomer resin is used as the binder resin, alkylsulfonic acid plasticizers are more preferred. Furthermore, among alkylsulfonic acid plasticizers, alkylsulfonic acid phenyl esters are even more preferred.

[0049] When the expandable layer contains a plasticizer, the content of the plasticizer is not particularly limited, but is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 15 to 50 parts by mass, relative to 100 parts by mass of the binder resin.

[0050] (Filler) The expandable layer may further contain a filler other than the flame retardant and thermally expandable graphite. The filler other than the flame retardant and thermally expandable graphite is not particularly limited, and examples thereof include metal carbonates such as alumina, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate, silica, diatomaceous earth, dawsonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloons, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, and dewatered sludge. These fillers may be used alone or in combination of two or more.

[0051] The average particle size of the filler is preferably 0.5 to 100 μm, more preferably 1 to 50 μm. When the content of the filler is small, a small particle size is preferred from the viewpoint of improving dispersibility, but when the content is large, as the filling rate increases, the viscosity of the refractory material increases and the moldability decreases, so a large particle size is preferred.

[0052] When the expandable layer contains a filler, the content of the filler is preferably 20 to 200 parts by mass, more preferably 50 to 150 parts by mass, relative to 100 parts by mass of the binder resin. When the content of the filler is within the above range, the mechanical properties of the expandable layer are likely to be improved.

[0053] (Other Additives) The expandable layer may contain various additive components as long as the object of the present invention is not impaired. The type of additive component is not particularly limited, and various additives can be used. Examples of such additives include tackifiers, anti-shrinkage agents, crystal nucleating agents, colorants (pigments, dyes, etc.), UV absorbers, antioxidants, antiaging agents, dispersants, gelation accelerators, fillers, reinforcing agents, flame retardant assistants, antistatic agents, surfactants, and surface treatment agents. The amount of additive added can be appropriately selected within a range that does not impair moldability, etc. The additives may be used alone or in combination of two or more.

[0054] (Expansion Ratio) The thermally expandable fireproof material of the present invention preferably has an expansion ratio of 3.0 or more. By having an expansion ratio of 3.0 or more times the area before heating, the performance of the fireproof material can be fully exhibited, for example, when the fireproof material is placed in a space narrow in the thickness direction. From this perspective, the expansion ratio is more preferably 3.05 or more, and even more preferably 4.0 or more. The expansion ratio can be determined by the following method. First, the fireproof material is cut into a 25 mm x 25 mm piece. Next, the fireproof material cut as described above is attached to the surface of one of two SUS plates facing each other at a distance three times the thickness of the expansion layer constituting the fireproof material. Then, after heating the fireproof material at 300°C for 10 minutes, the area of ​​the fireproof material as viewed perpendicular to the SUS plate (hereinafter also referred to as the "area after heating") and the area of ​​the fireproof material before heating (hereinafter also referred to as the "area before heating") are determined, and the expansion ratio is calculated using the following formula (4): Expansion ratio (times) = area after heating (mm ２ ) / area before heating (mm ２ ) Equation (4) The method for heating the fire-resistant material is not particularly limited, but for example, the fire-resistant material may be attached to two SUS plates to prepare a structure having a heat-expandable fire-resistant material attached to the surface of one of the two SUS plates, and then the structure may be placed in a known electric furnace and heated.

[0055] Furthermore, the expansion ratio is not particularly limited, but from the viewpoint of ensuring a certain level of hardness in the event of a fire and making it easier to exhibit fire resistance, it is preferably 15 times or less, more preferably 10 times or less, and even more preferably 7 times or less.

[0056] (Shape, Thickness) The heat-expandable fireproof material of the present invention is preferably in the form of a sheet, more preferably a rectangular sheet. The thickness is not particularly limited, but from the viewpoints of fire resistance and ease of handling, it is preferably 0.3 to 5 mm, more preferably 0.5 to 3 mm, and even more preferably 1 to 3 mm. The thickness ratio of the expandable layer to the substrate is preferably 2 to 80, more preferably 5 to 50, and even more preferably 10 to 40. The thickness of the substrate is preferably 50 to 300 μm, more preferably 70 to 200 μm. The thickness of the expandable layer before heating is preferably 0.2 to 4 mm, more preferably 0.4 to 3 mm, and even more preferably 0.9 to 2.5 mm. When the thickness ratio and the thickness of the heat-expandable fireproof material and each layer are within the above ranges, the dimensions of the heat-expandable fireproof material tend to be stable even in high-temperature environments.

[0057] (Method for Producing Fire-Resistant Material) The thermally expandable fire-resistant material of the present invention can be produced, for example, as follows. First, thermally expandable graphite, a binder resin, and optionally, a flame retardant, a vulcanizing agent, a vulcanization accelerator, a plasticizer, a filler, and other additives are mixed in a kneader such as a kneading roll or a stirring device to obtain a fire-resistant resin composition. The temperature during mixing and the temperature for forming into a sheet are preferably lower than the expansion initiation temperature of the thermally expandable graphite. Furthermore, if the fire-resistant resin composition contains a vulcanizing agent, the temperature is preferably a temperature at which the vulcanizing agent does not easily crosslink. Therefore, the mixing temperature is preferably 30 to 100°C, more preferably 40 to 80°C. The temperature for forming into a sheet is preferably 70 to 110°C, more preferably 80 to 100°C. Next, the obtained fire-resistant resin composition is applied to a substrate to form a sheet, thereby obtaining an expandable layer laminated on the substrate. In addition, another substrate may be laminated on the expandable layer laminated on the substrate, so that the expandable layer has a substrate on both sides. When the expandable layer has a substrate on both sides, the substrates on both sides of the expandable layer may be the same or different, but are preferably the same.

[0058] (Adhesive Layer) The heat-expandable fireproof material of the present invention may be composed of only a substrate and an expansion layer, but preferably further comprises an adhesive layer. By providing an adhesive layer, the heat-expandable fireproof material is fixed to an adherend such as a building fixture, thereby facilitating dimensional stability even in high-temperature environments. For example, when the heat-expandable fireproof material has a substrate on only one side of the expansion layer, the adhesive layer may be provided on the side of the expansion layer opposite the side on which the substrate is provided. Therefore, the heat-expandable fireproof material preferably has a layer structure of substrate / expansion layer / adhesive layer. Furthermore, when attaching the heat-expandable fireproof material to an adherend such as a building fixture, the expansion layer may be attached so that it contacts the adherend via the adhesive layer. This facilitates dimensional stability of the heat-expandable fireproof material even in high-temperature environments. When the heat-expandable fireproof material has a substrate on both sides of the expansion layer, an adhesive layer may be provided on either side. The adhesive layer is not particularly limited and may be made of a commonly used adhesive, such as an acrylic adhesive, a silicone adhesive, a urethane adhesive, or a rubber adhesive. Of these, an acrylic adhesive is preferred. The adhesive layer may be made of a single adhesive layer made of an adhesive, or may be a double-sided tape in which adhesive layers are provided on both sides of a substrate. The thickness of the adhesive layer is, for example, 10 to 500 μm, and preferably 20 to 200 μm.

[0059] (Wound body) The thermally expandable fireproof material of the present invention is preferably wound into a wound body. By forming it into a wound body, transportation efficiency is improved, and a large amount of thermally expandable fireproof material can be transported at once, for example, to a construction site of a building. Furthermore, it becomes possible to store a large amount of thermally expandable fireproof material in a limited area, for example, in a warehouse. The length of the thermally expandable fireproof material in the wound body is preferably 10 m or more, and in this case, the sheet width is preferably, for example, 0.01 to 2.0 m. Furthermore, the upper limit of the length is not particularly limited, and it may be 500 m or less.

[0060] (Uses) The thermally expandable fireproof material of the present invention can be used specifically for various fittings in detached houses, apartment buildings, high-rise houses, high-rise buildings, commercial facilities, public facilities, etc., various vehicles such as automobiles and trains, ships, and aircraft, among which it is preferably used for fittings. Specific examples of fittings that can be used include, but are not limited to, walls, beams, pillars, floors, bricks, roofs, boards, windows, shoji screens, doors, sliding doors, transoms, wiring, and piping. The thermally expandable fireproof material of the present invention can be applied, in particular, to gaps in fittings such as windows and doors, to prevent flames from penetrating through the gaps in the event of a fire or the like.

[0061] Furthermore, the thermally expandable fireproof material of the present invention is preferably used on an object to be powder coated, and more preferably the fireproof material is attached to the object in advance, and the object to be coated with the fireproof material attached is powder coated, and then the object is cured in a high-temperature environment. Generally, in powder coating, the object to be coated needs to be cured in a high-temperature environment after painting to improve the adhesion of the paint to the object to be coated, but the thermally expandable fireproof material of the present invention has excellent dimensional stability in a high-temperature environment, so it is possible to cure the object to which the fireproof material is attached in a high-temperature environment.

[0062] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0063] [Evaluation Method] (1) Expansion Ratio (Occluded Expansion Test) The thermally expandable fireproof materials prepared in each Example and Comparative Example were cut into pieces measuring 25 mm x 25 mm (width x length) to prepare samples for the occluded expansion test. Next, the thermally expandable fireproof materials cut to 25 mm x 25 mm were attached to the center of the surface of one of the SUS plates via an adhesive layer. However, if the fireproof material did not have an adhesive layer, the attachment was performed using a 200 μm-thick double-sided tape ("4965" manufactured by Tesa). In this case, in the case of a thermally expandable fireproof material having a substrate on only one side, the side opposite the substrate was attached to the surface of the SUS plate using double-sided tape. Then, the two SUS plates were arranged facing each other at a distance three times the thickness of the expansion layer constituting the fireproof material. The size of each SUS plate was 0.3 mm thick, 100 mm wide, and 100 mm long. In this way, a structure was produced having two SUS plates and a heat-expandable fireproof material attached to the surface of one of the two SUS plates. The produced structure was heated in an electric furnace at 300°C for 10 minutes. The expansion ratio was calculated by dividing the area of ​​the heat-expandable fireproof material after heating by the area of ​​the heat-expandable fireproof material before heating.

[0064] (2) Change Rate in Thickness Direction, Change Rate in MD Direction, Change Rate in TD Direction The thermally expandable fireproof materials prepared in each Example and Comparative Example were cut to a size of 200 mm MD x 25 mm TD and attached to an iron plate. The iron plate with the attached fireproof material was preheated to 185°C and placed in an oven maintained at 185°C for 30 minutes to heat the fireproof material, and the change rates were calculated for each of the MD, TD, and thickness directions based on the following formula (5). When the thermally expandable fireproof material could not be attached to the iron plate, the thermally expandable fireproof material was placed on the iron plate and the same test was performed. In this case, if there was a surface without a substrate, the surface without the substrate was made to contact the iron plate. Change Rate (%) = |Dimension before heating (mm) - Dimension after heating (mm) | / Dimension before heating (mm) x 100... Formula (5)

[0065] The components used in each example and comparative example are as follows: (Binder Resin) 1. Thermosetting Resin Epoxy Resin (1) "jER807" manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin Epoxy Resin (2) "EX830" manufactured by Nagase ChemteX Corporation, aliphatic epoxy resin Curing Agent (1) "FL052" manufactured by Mitsubishi Chemical Corporation, amine curing agent Curing Agent (2) "FL079" manufactured by Mitsubishi Chemical Corporation, amine curing agent 2. Elastomer Components NBR (1) "Nipol DN401LL" manufactured by Nippon Zeon Co., Ltd. NBR (2) "Nipol DN401" manufactured by Nippon Zeon Co., Ltd.

[0066] (Curing accelerator) 1,2-dimethylimidazole (1,2-DMZ) "Curesol 1.2DMZ" manufactured by Shikoku Chemicals Corporation 2-ethyl-4-methylimidazole (2E4MEZ) "Curesol 2E4MZ" manufactured by Shikoku Chemicals Corporation

[0067] (Thermal Expandable Graphite) Thermal Expandable Graphite (1) "CA-60N" manufactured by Air Water Corporation, expansion start temperature 200°C Thermal Expandable Graphite (2) "EXP-50S150" manufactured by Fuji Graphite Industries Co., Ltd., expansion start temperature 150°C

[0068] (Flame retardant) Ammonium polyphosphate "AP422" manufactured by Clariant Aluminum phosphite "NSF" manufactured by Taihei Chemical Industry Co., Ltd.

[0069] (Filler) Calcium carbonate "Whiten BF-300" manufactured by Bihoku Funka Kogyo Co., Ltd. Barium sulfate "FBA" manufactured by Taihei Talc Co., Ltd.

[0070] (Vulcanizing agent) N-cyclohexyl-2-benzothiazolylsulfenamide "Accel CZ" manufactured by Kawaguchi Chemical Industry Co., Ltd. Tetramethylthiuram disulfide "Accel TMT-R" manufactured by Kawaguchi Chemical Industry Co., Ltd.

[0071] (Vulcanization accelerator) Zinc oxide (ZnO) manufactured by Sakai Chemical Industry Co., Ltd. Calcium oxide Vesta BS manufactured by Inoue Lime Industry Co., Ltd.

[0072] (Tackifier) ​​Alicyclic petroleum resin "P-125" manufactured by Arakawa Chemical Industries, Ltd.

[0073] (Plasticizer) Alkyl sulfonate ester "Mezamol" manufactured by LANXESS

[0074] (Substrate) PET film (1) Toray Industries, Inc. "Lumirror X60K", annealed, thickness 75 μm PET film (2) Toray Industries, Inc. "Lumirror #12-S10", not annealed, thickness 75 μm Glass cloth and PET laminated film (GC / PET) Maeda Glass Co., Ltd. "EP11", thickness 100 μm, and Tokyo Film Services Co., Ltd. "Mat Lumirror", thickness 80 μm, laminated with an acrylic adhesive, thickness 180 μm Nonwoven fabric Nippon Paper Papylia Co., Ltd. "SPC", 10 μm Glass cloth film (GC) Maeda Glass Co., Ltd. "EP11", 100 μm Aramid film Toray Industries, Inc. "Mictron", 12 μm

[0075] [Example 1] The binder resin, curing catalyst, thermally expandable graphite, flame retardant, and filler were fed into a planetary mixer according to the formulation shown in Table 1 and kneaded at room temperature at 1000 rpm for 1 minute to obtain a fire-resistant resin composition. The fire-resistant resin composition was then applied to a PET film (1) and press-molded at room temperature under 10 MPa to obtain a sheet-like molded product having a thickness of 1.8 mm. The molded product was then placed in a thermostatic oven at 100°C for 10 hours to cure, obtaining a sheet-like laminate (thickness 2 mm) composed of a PET film (1) and an expansion layer. Next, an adhesive layer (thickness 50 μm) made of an acrylic adhesive ("SK1717DT" manufactured by Soken Chemical & Engineering Co., Ltd.) was applied to the surface of the laminate opposite to the surface on which the PET film (1) was provided, to obtain a heat-expandable fire-resistant material. The evaluation results of the obtained heat-expandable fire-resistant material are shown in Table 1.

[0076] [Examples 2 to 5, Comparative Example 2] Thermally expandable fire-resistant materials were produced in the same manner as in Example 1, except that the formulation of the expandable layer was changed as shown in Table 1 and the substrate was changed from PET film (1) to the formulation shown in Table 1.

[0077] [Example 6, Comparative Example 3] A binder resin, thermally expandable graphite, a flame retardant, and other additives were placed in a roll according to the formulation shown in Table 1 and kneaded at 90°C for 15 minutes to obtain a fire-resistant resin composition. The obtained fire-resistant resin composition was press-molded at 100°C for 1 minute to obtain a sheet-like expanded layer having a thickness of 1.8 mm. A substrate shown in Table 1 was laminated on the fire-resistant material, and an adhesive layer made of an acrylic adhesive ("1717DT" manufactured by Soken Chemical & Engineering Co., Ltd.) was applied to the surface of the fire-resistant material opposite to the surface on which the substrate was laminated. The evaluation results are shown in Table 1.

[0078] [Comparative Example 1] A heat-expandable fire-resistant material was produced in the same manner as in Example 1, except that the formulation of the expandable layer was changed as shown in Table 1, the substrate was changed from PET film (1) to the formulation shown in Table 1, and no adhesive layer was applied.

[0079] *In each example and comparative example, the sample contracted in the TD direction and expanded in the MD and thickness directions.

[0080] As is clear from the above examples, it was found that the heat-expandable fire-resistant materials satisfying the requirements of the present invention have a rate of change in MD and TD, and a rate of change in thickness that are all below a certain level, and are able to exhibit excellent dimensional stability even in a high-temperature environment. In contrast, the rate of change in TD of the heat-expandable fire-resistant material produced in Comparative Example 1, the rate of change in thickness of the heat-expandable fire-resistant material produced in Comparative Example 2, and the rate of change in MD of the heat-expandable fire-resistant material produced in Comparative Example 3 are all above a certain level, and it was found that they are unable to exhibit excellent dimensional stability in a high-temperature environment.

Claims

1. A heat-expandable fire-resistant material comprising an expansion layer containing a binder resin and heat-expandable graphite, and a substrate provided on at least one side of the expansion layer, wherein when the heat-expandable fire-resistant material is heated at 185°C for 30 minutes, the thickness change rate of the heat-expandable fire-resistant material is 20% or less, and the thickness change rates in both the TD and MD directions are 2% or less.

2. The thermally expandable fire-resistant material according to claim 1, further comprising an adhesive layer provided on the surface of the expandable layer opposite to the surface on which the substrate is provided.

3. The thermally expandable fire-resistant material according to claim 1 or 2, wherein the substrate comprises at least a plastic.

4. The thermally expandable fire-resistant material according to claim 3, wherein the plastic comprises at least one selected from the group consisting of PVC, polyurethane resin, PE, PP, PC, polyester resin, polyamide resin, and acrylic resin.

5. The thermally expandable fire-resistant material according to claim 1 or 2, wherein the substrate further comprises a fibrous structure.

6. The heat-expandable fire-resistant material according to claim 1 or 2, wherein when the heat-expandable fire-resistant material having dimensions of 25 mm x 25 mm is attached to the surface of one of two opposing SUS plates at a distance three times the thickness of the expansion layer, and the heat-expandable fire-resistant material is then heated at 300°C for 10 minutes, the area of ​​the heat-expandable fire-resistant material as viewed from a direction perpendicular to the SUS plates is 3.0 times or more the area of ​​the heat-expandable fire-resistant material before heating.

7. The thermally expandable fire-resistant material according to claim 1 or 2, wherein the binder resin is a thermosetting resin.

8. The thermally expandable fire-resistant material according to claim 7, wherein the thermosetting resin comprises an epoxy resin.

9. The thermally expandable refractory material according to claim 1 or 2, wherein the thermally expandable graphite has an expansion initiation temperature of 160°C or higher.

10. The thermally expandable fire-resistant material according to claim 1 or 2, wherein the thermally expandable fire-resistant material is a wound body having a length of 10 m or more.

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