Thermally expandable fire-resistant material and method for manufacturing same

Abstract

Provided is a thermally expandable fire-resistant material comprising an expansion layer containing a binder resin and thermally expandable graphite. The thermally expandable fire-resistant material has a displacement amount of 5 mm or less when a test body comprising a sash body and a frame body having an opening, in which the thermally expandable fire-resistant material is attached to three sides of an outer peripheral surface of the sash body and the sash body is fitted into the opening, is heated according to a heating curve conforming to ISO 834 for 10 minutes in a state where a load of 10 N is applied to the sash body.

Description

Thermal expansion refractory material and method for producing the same

[0001] The present invention relates to a thermal expansion refractory material and a method for producing the same.

[0002] In the construction field, for fire prevention, refractory materials are used for building materials such as fittings, columns, and wall materials. Conventionally, various types of refractory materials have been developed. For example, Patent Document 1 discloses an invention related to a thermal expansion refractory material containing an elastomer composed of rubber and a styrene-based thermoplastic elastomer, thermally expandable graphite, and an inorganic phosphate compound. Such a thermal expansion refractory material expands upon heating to form a combustion residue as a refractory heat-insulating layer, thereby exhibiting refractory heat-insulating performance.

[0003] A thermal expansion refractory material containing thermally expandable graphite is provided, for example, in the gap between fittings such as doors and windows provided in openings of a building and frames such as door frames and window frames surrounding them. It expands in the thickness direction during a fire to close the gap between the fittings and the frame material, thereby preventing the spread of fire.

[0004] Japanese Patent Publication No. 7142139

[0005] However, in an actual fire, the temperature at the lower part of the fitting may not rise, for example, and may not reach the temperature assumed during a fire, and sufficient expansion performance may not be obtained. Further, even if it has good expansion characteristics capable of closing the gap during a fire, if the adhesiveness of the residue of the thermal expansion refractory material is low, it may be peeled off from the fitting by hot air or the like during a fire, resulting in the formation of a void and a problem of reduced fire resistance.

[0006] Therefore, an object of the present invention is to provide a thermal expansion refractory material having good expansion characteristics capable of closing the gap during a fire and having excellent adhesiveness of the residue.

[0007] As a result of diligent research, the inventors have found that the above problem can be solved by making a heat-expandable fire-resistant material having an expansion layer containing a binder resin and heat-expandable graphite such that the amount of displacement in a specific fire load test is below a certain level, and have completed the present invention as follows. That is, the present invention provides the following [1] to

[14] . [1] A heat-expandable fire-resistant material having a thickness of 1 to 3 mm and comprising an expansion layer containing a binder resin and heat-expandable graphite, wherein the test specimen comprises a shoji screen body and a frame body having an opening, and the shoji screen body, on which the heat-expandable fire-resistant material is attached to three sides of the outer surface, is fitted into the opening, and when heated according to a heating curve in accordance with ISO 834, and the shoji screen body is subjected to a load of 10 N and heated for 10 minutes, the amount of displacement is 5 mm or less. [2] The heat-expandable fire-resistant material described in [1] above, wherein the heat-expandable fire-resistant material, measuring 6.25 mm x 6.25 mm and 1 to 3 mm in thickness, is attached to the opposing surfaces of one of two opposing iron plates spaced three times the thickness of the heat-expandable fire-resistant material, and heated at 10°C / min from 40°C to 800°C, the temperature at which the expanded heat-expandable fire-resistant material reaches the other iron plate is 230°C or less. [3] The heat-expandable fire-resistant material described in [1] or [2] above, wherein the heat-expandable graphite comprises a first heat-expandable graphite and a second heat-expandable graphite. [4] The thermally expandable fire-resistant material according to [3] above, wherein the expansion ratio of the first thermally expandable graphite at 200°C is A1 and the expansion ratio at 500°C is A2, and the expansion ratio of the second thermally expandable graphite at 200°C is B1 and the expansion ratio at 500°C is B2, such that A1 > B1 and A2 < B2. [5] The thermally expandable fire-resistant material according to any one of [1] to [4] above, wherein the expansion layer contains a phosphorus-based flame retardant. [6] The thermally expandable fire-resistant material according to any one of [1] to [5] above, wherein the binder resin is a thermosetting resin. [7] The thermally expandable fire-resistant material according to [6] above, wherein the thermosetting resin contains an epoxy resin. [8] The thermally expandable fire-resistant material according to [7] above, wherein the epoxy resin contains a polysulfide. [9] The thermally expandable fire-resistant material according to [7] or [8] above, wherein the expansion layer contains a curing catalyst.

[10] The heat-expandable fire-resistant material according to [9] above, wherein the curing catalyst is an imidazole and has a pKa of 10 or more.

[11] The heat-expandable fire-resistant material according to any one of [1] to

[10] above, wherein the binder resin does not contain halogens in its molecular structure.

[12] The heat-expandable fire-resistant material according to any one of [1] to

[11] above, wherein the elution rate when immersed in water at 60°C for three days is 5% or less.

[13] The heat-expandable fire-resistant material according to any one of [1] to

[12] above, wherein the heat-expandable fire-resistant material is a wound body with a longitudinal length of 10 m or more.

[14] A method for producing the heat-expandable fire-resistant material according to any one of [1] to

[13] above, comprising coating a support with a fire-resistant resin composition containing a binder resin and heat-expandable graphite to form the expansion layer.

[0008] According to the present invention, it is possible to provide a heat-expandable fire-resistant material that has good expansion properties that can seal gaps in the event of a fire, and whose residue has excellent adhesive properties.

[0009] This is a side view illustrating the fire load test. This is a front view illustrating the fire load test.

[0010] <Thermally Expandable Fire-Resistant Material> The thermally expandable fire-resistant material of the present invention will be described below using embodiments. The thermally expandable fire-resistant material of the present invention comprises an expansion layer containing a binder resin and thermally expandable graphite.

[0011] (Binder Resin) The expansion layer constituting the heat-expandable fire-resistant material of the present invention includes a binder resin. A thermosetting resin is preferred as the binder resin, and an epoxy resin is more preferred among them. By using an epoxy resin as the thermosetting resin, it is easier to form an expansion layer that has good expansion properties that can seal gaps in the event of a fire, and the residue has excellent adhesive properties. Furthermore, the binder resin of the expansion layer is not particularly limited, but from the viewpoint of reducing environmental impact, it is preferable that it does not contain halogens in its molecular structure.

[0012] Examples of epoxy resins include epoxy compounds alone, or those consisting of an epoxy compound as the main component and a curing agent. The epoxy compound is a compound having an epoxy group, and specifically, glycidyl ether type and glycidyl ester type are examples. The glycidyl ether type may be bifunctional or polyfunctional (three or more functions). The same applies to the glycidyl ester type. The epoxy compound may also include monofunctional compounds to adjust the degree of crosslinking, etc. Among these, the bifunctional glycidyl ether type is preferred.

[0013] Examples of the above-mentioned bifunctional glycidyl ether-type epoxy compounds include alkylene glycol types such as polyethylene glycol type and polypropylene glycol type, neopentyl glycol type, 1,6-hexanediol type, and hydrogenated bisphenol A type aliphatic epoxy compounds. Furthermore, aromatic epoxy compounds containing aromatic rings, such as bisphenol A type, bisphenol F type, bisphenol AD ​​type, ethylene oxide-bisphenol A type, and propylene oxide-bisphenol A type, can be cited.

[0014] Examples of the glycidyl ester type epoxy compounds mentioned above include hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type, and p-oxybenzoic acid type epoxy compounds. Examples of trifunctional or more glycidyl ether type epoxy compounds include phenol novolac type, orthocresol novolac type, DPP novolac type, and dicyclopentadiene phenol type. These epoxy compounds may be used individually or in combination of two or more types.

[0015] Among the above, aromatic epoxy compounds such as bisphenol type, represented by bisphenol type A and bisphenol type F, are preferred, with bisphenol type F being more preferred. It is also preferable to use aromatic epoxy compounds and aliphatic epoxy compounds in combination. In this case, the aliphatic epoxy compound is preferably of the glycidyl ether type. In the present invention, by using aromatic epoxy compounds such as bisphenol type, a certain level of mechanical strength can be ensured and expansion performance can be improved, making it easier to reduce the amount of displacement in the fire load test described later. Furthermore, by using aromatic epoxy compounds and aliphatic epoxy compounds in combination, a certain level of flexibility can be ensured while maintaining high mechanical strength, making it less likely for wrinkles or folds to occur when rolled. When aromatic epoxy compounds and aliphatic epoxy compounds are used in combination, the ratio of the aliphatic epoxy compound to the aromatic epoxy compound (aliphatic / aromatic) is preferably 5 / 95 to 80 / 20, more preferably 10 / 90 to 50 / 50, and even more preferably 20 / 80 to 40 / 60 by mass, from the viewpoint of improving mechanical strength and flexibility and improving various performances.

[0016] When epoxy resin is used as the binder resin, a polyaddition type curing agent may be used. Examples of polyaddition type curing agents include polyamine-based curing agents, acid anhydride-based curing agents, polyphenol-based curing agents, polymercaptans, and polythiols. These may be used individually or in combination. In particular, when controlling highly different properties, it is preferable to use them in combination. The curing method for epoxy resin compounds is not particularly limited and can be carried out by known methods. Among these, polyamine-based curing agents or polythiols are preferred from the viewpoint of fire resistance. It is also preferable to use polyamine-based curing agents and polythiols in combination. Examples of polyamine-based curing agents include aliphatic amines, alicyclic amines, or aromatic amines having an aromatic ring skeleton. Among these, aromatic amines are preferred from the viewpoint of improving heat resistance as a fire-resistant material and improving various properties. Examples of polythiols include aromatic polysulfides and polysulfides represented by aliphatic polysulfides. Among these, aliphatic polysulfides are preferred from the viewpoint of improving various properties as a fire-resistant material.

[0017] The curing agent content in the expansion layer is preferably in the range of 30 to 150 parts by mass per 100 parts by mass of the epoxy resin compound. If the content is 30 parts by mass or more, the epoxy resin compound will harden more easily, and if it is 150 parts by mass or less, an effect corresponding to the amount of curing agent added will be obtained. The curing agent content in the expansion layer is more preferably in the range of 50 to 100 parts by mass per 100 parts by mass of the epoxy resin compound, and even more preferably in the range of 55 to 80 parts by mass.

[0018] As the thermosetting resin, thermosetting resins other than the epoxy resins mentioned above may be used. Specifically, urethane resins, phenolic resins, urea resins, melamine resins, unsaturated polyester resins, polyimides, etc., can be used.

[0019] When using a thermosetting resin, the expansion layer preferably contains a curing catalyst to accelerate curing. The curing catalyst is sometimes referred to as a curing accelerator. Using a curing catalyst increases the curing speed, allowing for proper dispersion of thermally expandable graphite and flame retardants during curing, and improving the adhesion of the residue. It can also increase the reaction rate of thermosetting resins such as epoxy resins. Therefore, it becomes easier to reduce the displacement in the load test described above, and also to improve water resistance. When using epoxy resin as the binder resin, it is even more preferable to use a curing accelerator (curing catalyst) in addition to the curing agent described above. Examples of curing accelerators for epoxy resins include tertiary amines, imidazoles, phosphorus compounds, and Lewis acid complexes, with imidazoles being preferred among these. The curing catalyst may be used alone or in combination of two or more types.

[0020] 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, and 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethylimidazole. Examples include tyl-s-triazine, 2,4-diamino-6-(2'-undecylimidazolyl-(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 isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-methylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Among these, 1,2-alkylimidazoles such as 1,2-dimethylimidazole and 2-ethyl-4-methylimidazole are preferred.

[0021] Furthermore, it is preferable that the imidazoles have a pKa of 10 or higher. A pKa of 10 or higher facilitates more appropriate curing and improves water resistance, expansion properties, etc. A pKa of 12 or higher is more preferable, and 13 or higher is even more preferable. The pKa is not particularly limited, but for example, it may be 20 or lower. The pKa can be measured by neutralization titration, spectrophotometric method, or capillary electrophoresis.

[0022] 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, per 100 parts by mass of the thermosetting resin (for example, in the case of epoxy resin, the total amount of epoxy compound and curing agent).

[0023] Furthermore, resins other than thermosetting resins may be used as the binder resin; for example, elastomer resins and thermoplastic resins are also preferred. Examples of elastomer resins are not particularly limited, but include diene-based 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, polyvulcanized rubber, non-vulcanized rubber, silicone rubber, fluororubber, and urethane rubber. Elastomer resins are preferably used in latex. Examples of thermoplastic resins include ethylene vinyl acetate (EVA). Thermoplastic resins are also preferably used in emulsions. When used in latex or emulsion, an expanded layer can be easily produced by coating, as described later.

[0024] As the elastomer resin or thermoplastic resin, chloroprene rubber and ethylene vinyl acetate (EVA) are preferred, with chloroprene rubber being more preferred, from the viewpoint of being usable as a latex or emulsion and ensuring mechanical strength while improving various properties. The above binder resins may be used individually or in combination of two or more.

[0025] Furthermore, 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, preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 42% by mass or less, based on the total amount of the expanded layer. If the binder resin content is above the lower limit, the shape retention of the expanded layer tends to improve. Also, if the binder resin content is below the upper limit, the amount of thermally expandable graphite can be increased, and fire resistance tends to improve. In this specification, the binder resin content refers to the total amount of the main component (epoxy compound in the case of epoxy resin) and the curing agent for curing the main component in the case of a thermosetting resin.

[0026] (Thermally Expandable Graphite) The expansion layer constituting the thermally expandable refractory material of the present invention contains thermally expandable graphite. Thermally expandable graphite is a conventionally known substance that expands when heated, and is produced by acid-treating raw material powders such as natural scaly graphite, pyrolysis graphite, and quiche graphite with a strong oxidizing agent to generate graphite intercalation compounds. Examples of strong oxidizing agents include inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, as well as concentrated nitric acid, perchloric acid, perchlorates, permanganates, dichromates, and hydrogen peroxide. Thermally expandable graphite is a crystalline compound that maintains a layered structure of carbon. Thermally expandable graphite may also be neutralized. That is, thermally expandable graphite obtained by treating it with a strong oxidizing agent as described above may be further neutralized with ammonia, aliphatic lower amines, alkali metal compounds, alkaline earth metal compounds, etc.

[0027] It is preferable to use at least two types of thermally expandable graphite with different expansion characteristics. Specifically, it is preferable that the thermally expandable graphite includes a first and a second type of thermally expandable graphite. The first and second types of thermally expandable graphite have different expansion ratios at 200°C, 500°C, or both. If the expansion ratio of the first thermally expandable graphite at 200°C is A1 and the expansion ratio at 500°C is A2, and the expansion ratio of the second thermally expandable graphite at 200°C is B1 and the expansion ratio at 500°C is B2, then it is preferable that A1 > B1 and A2 < B2. By using such two types of thermally expandable graphite, the thermally expandable fire-resistant material expands from relatively low temperatures and also expands appropriately when heated to high temperatures, thus providing the thermally expandable fire-resistant material with good expansion characteristics that allow it to properly seal gaps in the event of a fire. Therefore, it becomes easier to reduce the amount of displacement in the fire load test described later.

[0028] Here, the ratio of the expansion ratio A1 to the expansion ratio B1 (A1 / B1) is preferably 1 to 30, more preferably 2 to 20, and even more preferably 3 to 10. Also, the ratio of the expansion ratio A2 to the expansion ratio B2 (A2 / B2) is preferably 0.2 to 1, more preferably 0.3 to 0.9, and even more preferably 0.4 to 0.8.

[0029] Furthermore, the expansion ratio A1 is preferably 10 times or more, more preferably 11 to 30 times, and even more preferably 15 to 25 times. The expansion ratio A2 is preferably 30 to 60 times, more preferably 40 to 58 times, and even more preferably 45 to 55 times. Furthermore, the expansion ratio B1 is preferably 1 to 9 times, more preferably 2 to 8 times, and even more preferably 3 to 7 times. The expansion ratio B2 is preferably 60 times or more, more preferably 60 to 85 times, and even more preferably 65 to 80 times. The expansion ratio of thermally expandable graphite can be measured by heating thermally expandable graphite placed in a quartz test tube (inner diameter 15 mm, capacity 25 mL) under predetermined conditions and measuring its height. Specifically, 0.2 g of thermally expandable graphite was placed in a test tube and heated in an electric furnace at 200°C for 10 minutes and 500°C for 5 minutes, respectively. The height of the expanded graphite in the test tube was measured, the volume in the test tube was calculated, and the expansion ratio was obtained by dividing it by the weight.

[0030] The expansion initiation temperature of the first thermally expandable graphite is preferably 120°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 170°C or lower. The expansion initiation temperature of the second thermally expandable graphite is preferably 130°C or higher, more preferably 140°C or higher, even more preferably 150°C or higher, preferably 250°C or lower, more preferably 200°C or lower, and even more preferably 190°C or lower. The expansion initiation temperature of the thermally expandable graphite can be measured by raising the thermally expandable graphite to a constant temperature using a device with a temperature control function and a device for measuring normal force, and measuring the temperature at which the normal force rises. The measuring device is not limited as long as it is capable of controlling the measurement temperature and measuring normal stress, but for example, a rheometer can be used.

[0031] When the thermally expandable graphite contains first and second thermally expandable graphite, the ratio of the content of the second thermally expandable graphite to the content of the first thermally expandable graphite is, for example, 5 / 95 to 95 / 5 by mass, preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 80 / 20, and even more preferably 30 / 70 to 70 / 30. When the thermally expandable graphite contains first and second thermally expandable graphite, the thermally expandable graphite may consist of first and second thermally expandable graphite, but may also contain thermally expandable graphite other than first and second thermally expandable graphite as long as the effects of the present invention are not impaired. The content of such thermally expandable graphite is, for example, about 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less, relative to the total amount of thermally expandable graphite.

[0032] The content of thermally expandable graphite in the expansion layer is, for example, 30 to 200 parts by mass, preferably 40 to 150 parts by mass, more preferably 50 to 120 parts by mass, and even more preferably 60 to 100 parts by mass, per 100 parts by mass of binder resin. If the content of thermally expandable graphite is above the lower limit, it becomes easier to increase the expansion pressure of the thermally expandable fire-resistant material, for example, it becomes easier to exhibit excellent fire-resistant performance in the event of a fire. On the other hand, if the content of thermally expandable graphite is below the upper limit, shape retention and processability are improved.

[0033] (Flame retardant) The expansion layer preferably contains a flame retardant. By containing a flame retardant, the expansion layer can more effectively improve the fire resistance of the thermally expandable fire-resistant material. A phosphorus-based flame retardant is preferred as the flame retardant used in the present invention. The phosphorus-based flame retardant is preferably solid at room temperature (23°C) and normal pressure (1 atm), and specific examples include phosphates, phosphazene compounds, phosphate ester compounds, and phosphinate metal salts.

[0034] Specific examples of phosphates include monophosphates and polyphosphates. It should be noted that the term "phosphate" here includes not only orthophosphates but also phosphates and hypophosphates. 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 monoaluminum phosphate, dialuminum phosphate, trialuminum phosphate, 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 polyphosphate amide, and aluminum polyphosphate, with ammonium polyphosphate being preferred among these.

[0035] Phosphazene compounds are organic compounds in which phosphorus atoms and nitrogen atoms are alternately bonded. Examples of phosphazene compounds include cyclic phosphazene compounds, linear phosphazene compounds, and crosslinked phosphazene compounds crosslinked with crosslinking groups. Specifically, phosphazene compounds include those containing the constituent unit shown in the following general formula (1).

[0036] In the above general formula (1), X independently represents one of the following: 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 general formula (1), examples of substituents on the aryl group include alkyl groups, amino groups, and halogen atoms. X is preferably independently one of a phenyl group, a substituted phenyl group, a phenyloxy group, or a substituted phenyl group, and more preferably one of a phenyl group or a phenyloxy group.

[0037] The phosphate ester compound is not particularly limited as long as it is solid at room temperature (23°C), and examples 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. Examples of 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).

[0038] A metal phosphinate salt is a metal salt of an organic phosphinic acid. Specific examples of metal phosphinate salts include, for example, aluminum tris-diethylphosphinate, aluminum tris-methylethylphosphinate, aluminum tris-diphenylphosphinate, zinc bis-diethylphosphinate, zinc bis-methylethylphosphinate, zinc bis-diphenylphosphinate, titanyl bis-diethylphosphinate, titanium tetrakis-diethylphosphinate, titanium bis-methylethylphosphinate, titanium tetrakis-methylethylphosphinate, titanyl bis-diphenylphosphinate, and titanium tetrakis-diphenylphosphinate. Phosphorus-based flame retardants may be used alone or in combination of two or more. Among the phosphorus-based flame retardants listed above, phosphates are preferred, and ammonium polyphosphate and aluminum phosphite are more preferred.

[0039] As a flame retardant, other flame retardants besides the phosphorus-based flame retardants mentioned above may be included. For example, red phosphorus-based flame retardants, boron-containing flame retardants, bromine-based flame retardants, antimony-containing flame retardants, etc., may be used. Among these, boron-containing flame retardants are preferred. Examples of boron-containing flame retardants include borax, boron oxide, boric acid, and borates. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide. Examples of borates include alkali metals, alkaline earth metals, elements of Group 4, Group 12, and Group 13 of the periodic table, and ammonium borates. Specifically, examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate; alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate; zirconium borate, zinc borate, aluminum borate, and ammonium borate. The boron-containing flame retardant is preferably a borate, and more preferably zinc borate. The flame retardant may be used alone or in combination of two or more types. The flame retardant preferably contains at least a phosphorus-based flame retardant, but it is also preferable to use a combination of a phosphorus-based flame retardant and a boron-based flame retardant.

[0040] The amount of flame retardant in the expanded layer is preferably 30 to 200 parts by mass, more preferably 45 to 150 parts by mass, and even more preferably 60 to 100 parts by mass, per 100 parts by mass of binder resin. If the amount of flame retardant is above the lower limit, the fire resistance of the fire-resistant material tends to improve, and the amount of displacement in load tests tends to decrease. If the amount of flame retardant is below the upper limit, it tends to disperse more uniformly in the resin, resulting in better moldability and surface properties when rolled. Furthermore, in the expanded layer, the amount of phosphorus-based flame retardant is preferably above a certain level from the viewpoint of improving the fire resistance of the fire-resistant material and further reducing the amount of displacement in load tests. Specifically, it is preferably 20 to 150 parts by mass, more preferably 30 to 120 parts by mass, and even more preferably 40 to 100 parts by mass, per 100 parts by mass of binder resin.

[0041] (Filler) The expansion layer may further contain fillers other than the flame retardant and thermally expandable graphite described above. The fillers other than the flame retardant and thermally expandable graphite are not particularly limited and include, for example, metal hydroxides such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, etc., metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate, metal sulfates such as barium sulfate and magnesium sulfate, silica, diatomaceous earth, dawsonite, talc, Examples of fillers include clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fibers, glass beads, silica balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fibers, carbon balloons, charcoal powder, various metal powders, potassium titanate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fibers, various magnetic powders, slag fibers, fly ash, low-melting-point glass, alumina, and dewatered sludge. Preferred fillers include metal hydroxides, metal carbonates, and metal sulfates, with aluminum hydroxide, calcium carbonate, and barium sulfate being more preferred. Fillers may be used individually or in combination of two or more types.

[0042] When the expanded layer contains a filler, the filler content is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass, and even more preferably 35 to 120 parts by mass, per 100 parts by mass of the binder resin. When the filler content is within the above range, it is easier to improve the mechanical properties, fire resistance, etc., of the expanded layer.

[0043] (Plasticizer) The expanding layer may contain a plasticizer. The plasticizer is not particularly limited, but examples include phthalate-based plasticizers, adipic acid-based plasticizers, phosphate-based plasticizers, and alkyl sulfonic acid-based plasticizers.

[0044] examples of phthalate plasticizers include di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), or phthalic acid esters of higher alcohols or mixed alcohols having about 10 to 13 carbon atoms, etc. Examples of adipate 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, adipate-based polyesters, etc.

[0045] examples of phosphate plasticizers include phosphate esters, such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, octyldiphenyl 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) monooctyl phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate (TCP), trixylenyl phosphate, cresyldiphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, etc. Examples of alkyl sulfonic acid plasticizers include phenyl esters of alkyl sulfonic acids, N-butylbenzenesulfonamide, etc.

[0046] the content of the plasticizer in the expansion layer is not particularly limited, but is, for example, 100 parts by mass or less, preferably 70 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the binder resin. Also, the expansion layer may not contain a plasticizer, and thus the lower limit value of the plasticizer content is 0 parts by mass.

[0047] (Other additives) The expansion layer may contain various additive components as long as the object of the present invention is not impaired. The type of the additive component is not particularly limited, and various additives can be used. Examples of the additive include an adhesion promoter, an anti-shrinkage agent, a crystal nucleating agent, a colorant (pigment, dye, etc.), an ultraviolet absorber, an antioxidant, an anti-aging agent, a dispersant, a gelation promoter, a filler, a reinforcing agent, a flame retardant aid, an antistatic agent, a surfactant, and a surface treatment agent. The addition amount of the additive can be appropriately selected within a range that does not impair the moldability or the like. The additives may be used alone or in combination of two or more kinds.

[0048] In the present invention, the thickness of the expansion layer may be, for example, about 1 to 3 mm, preferably 1.2 to 2.5 mm, and more preferably 1.4 to 2.2 mm. When the thickness is 1 mm or more, appropriate expansion characteristics can be imparted to the thermally expandable refractory. Further, when it is 3 mm or less, the fit and the design freedom of furniture and the like are improved, and the handling property is also good, so that it can be suitably used for furniture and the like.

[0049] [Base material] The thermally expandable refractory of the present invention may be composed of only the expansion layer, but may also include a base material and an adhesive layer described later. Here, the base material is preferably provided on at least one side of the expansion layer. By providing the thermally expandable refractory with the base material, the expansion layer is protected or supported by the base material during high-temperature heating, and the dimensions of the thermally expandable refractory are stabilized even in a high-temperature environment. In addition, it is also possible to prevent the surface of the expansion layer from being roughened by high-temperature heat. The base material may be provided only on one side of the expansion layer or on both sides of the expansion layer, but it is preferable that the base material is provided only on one side. The base material is preferably laminated directly on the expansion layer, but may be laminated on the expansion layer through an adhesive layer for adhering the base material and the expansion layer if necessary.

[0050] The base material preferably contains at least a plastic. More preferably, it contains at least one selected from the group consisting of polyester resins such as polyethylene terephthalate (PET), polyvinyl chloride (PVC) resin, polyurethane resin, polyolefin resins such as polyethylene (PE) and polypropylene (PP), polycarbonate resin, polyamide, and acrylic resin. Among these, PET is even more preferred. The inclusion of a plastic in the base material imparts heat resistance to the base material, which improves the dimensional stability of the heat-expandable fire-resistant material in high-temperature environments.

[0051] Furthermore, the base material is preferably a plastic film made from the above-mentioned plastic, and among these, PET film is preferred. The plastic film may be a stretched film or an unstretched film, but from the viewpoint of dimensional stability, a stretched film is preferred, and among these, a biaxially oriented film is more preferred. In addition, it is preferable that the plastic film has been annealed. Annealing the plastic film improves the dimensional stability of the base material, and makes it easier to improve the dimensional stability of the entire thermally expandable fire-resistant material.

[0052] Furthermore, the base material may preferably include a fibrous structure. By using a fibrous structure, the binder resin of the expansion layer penetrates between the fibers, improving adhesion with the expansion layer and making it easier to improve the dimensional stability of the thermally expandable refractory material in high-temperature environments. Examples of fibrous structures include knitted fabrics, woven fabrics, or nonwoven fabrics, with woven or nonwoven fabrics being preferred. Examples of fibers used in the fibrous structure include glass fibers, ceramic fibers, cellulose fibers, polyester fibers, carbon fibers, and graphite fibers.

[0053] Furthermore, the base material may be a composite material of fibers and plastic, such as one in which a plastic layer is impregnated into a fiber layer to form a composite, for example, one in which a plastic layer is laminated onto a fiber layer and the plastic layer is partially impregnated. PET glass cloth is preferred as the fiber-plastic composite material. When using a fiber-plastic composite material as the base material, it is preferable that the fiber layer is on the expansion layer side and the plastic layer is on the outside. This configuration allows for good maintenance of the appearance of the heat-expandable fire-resistant material. Also, impregnating the fiber layer with the expansion layer makes it easier to laminate the base material and the expansion layer with high adhesion. The thickness of the base material is preferably 5 to 300 μm, and more preferably 10 to 100 μm.

[0054] [Adhesive Layer] The heat-expandable fire-resistant material of the present invention may be provided with an adhesive layer as described above. Providing an adhesive layer makes it easier to fix the heat-expandable fire-resistant material to an object such as building fixtures. The adhesive layer may be provided on only one side of the expansion layer or on both sides of the expansion layer, but it is preferable that it be provided on only one side of the expansion layer. Also, if the heat-expandable fire-resistant material has a base material on only one side of the expansion layer, it is preferable that the adhesive layer be provided on the side of the expansion layer opposite to the side on which the base material is provided. Therefore, it is preferable that the heat-expandable fire-resistant material has a layer structure of base material / expansion layer / adhesive layer. However, the adhesive layer may be provided on the side on which the base material is provided in the heat-expandable fire-resistant material, but in that case, it is preferable that it be placed outside of the base material. When an adhesive layer is provided, when attaching the heat-expandable fire-resistant material to an object such as building fixtures, it is preferable to attach the expansion layer to the object via the adhesive layer.

[0055] The adhesive layer is not particularly limited and can be any commonly used adhesive, such as acrylic adhesives, silicone adhesives, urethane adhesives, or rubber adhesives, with acrylic adhesives being preferred among these. The adhesive layer may consist of an adhesive layer alone, or a double-sided tape with adhesive layers on both sides of the substrate may be used. The thickness of the adhesive layer is, for example, 10 to 500 μm, preferably 20 to 200 μm.

[0056] In this invention, the thickness of the heat-expandable fire-resistant material is 1 to 3 mm. If the thickness is less than 1 mm, it becomes difficult to impart appropriate expansion characteristics to the heat-expandable fire-resistant material. If the thickness is greater than 3 mm, it becomes difficult to fit into fixtures and other components, and the degree of design freedom and handling are reduced, making it difficult to use suitably in fixtures and other components. The thickness of the heat-expandable fire-resistant material is the total thickness of the heat-expandable fire-resistant material, and if the heat-expandable fire-resistant material has a base material or adhesive layer, these are also included in the thickness. The thickness of the heat-expandable fire-resistant material is preferably 1.2 to 2.5 mm.

[0057] <Fire Resistance Load Test> The heat-expandable fire-resistant material of the present invention comprises a sash body and a frame body having an opening. A test specimen in which the sash body, to which the heat-expandable fire-resistant material is attached to three sides of its outer surface, is fitted into the opening is heated according to a heating curve compliant with ISO 834, and when a load of 10 N is applied to the sash body and heated for 10 minutes, the displacement is 5 mm or less. Here, the above displacement is an indicator of how well the heat-expandable fire-resistant material can suppress deformation in the shear direction due to heating when the test specimen is heated to simulate a fire. Therefore, if the expansion performance of the heat-expandable fire-resistant material is good and the adhesion of the residue is high, the displacement will be low. On the other hand, if the displacement is greater than 5 mm, the heat-expandable fire-resistant material does not have good expansion characteristics that can close gaps in the event of a fire, and the residue does not have good adhesion, making it difficult to impart excellent fire resistance to the heat-expandable fire-resistant material. From the viewpoint of ensuring good expansion performance and excellent adhesion to the residue, the above displacement is preferably 4.6 mm or less, more preferably 4 mm or less, and even more preferably 3 mm or less. Furthermore, the lower the above displacement, the better; it should be 0 mm or more, but in practical terms, for example, 0.5 mm or more is preferable.

[0058] The above displacement can be reduced by increasing the adhesive strength of the expansion residue, while ensuring that the thermally expandable refractory material expands to a certain extent at relatively low temperatures and also expands appropriately at high temperatures. Specifically, this can be adjusted as appropriate by the type and amount of thermally expandable graphite, the type of binder resin, the presence or absence of a curing catalyst, and the type and amount of flame retardant.

[0059] The fire load test will be described in detail with reference to Figures 1 and 2. The fire load test will be performed using a test specimen 10, which comprises a sliding door body 11 and a frame body 13 having an opening 12, as shown in Figures 1 and 2. The test specimen 10 was manufactured in reference to test specimen ISO 12472. The frame body 13 has a height of 1180 mm and a width of 1180 mm. The frame body 13 has an outer frame 14 formed by square metal columns with a thickness of 6 mm and a squareness of 50 mm, and a square frame portion 15 that forms the opening 12 is provided inside it. The square frame portion 15 and the outer frame 14 are connected by a connecting portion 18. The square frame portion 15 and the connecting portion 18 are formed by combining L-shaped metal angles with a thickness of 6 mm and a width of 50 mm. In the square frame portion 15 and the connecting portion 18, the L-shaped angles are arranged so that the outer surface of one main face of the L-shape faces towards the center. Furthermore, the frame 13 has a 50 mm thick calcium silicate board 16 fitted into the part other than the opening 12. In addition, a metal plate base 17 is provided on the same plane as the inner surface of the lower frame 15A of the square frame portion 15. The shoji screen 11 is a square metal plate with a thickness of 56 mm, a height of 40 cm, a width of 40 cm, and a weight of 10 kg. The metal used for the shoji screen 11 and the frame 13 is SS400.

[0060] Next, a heat-expandable fire-resistant material 20 cut to a width of 25 mm and a length of 40 cm is prepared, and the heat-expandable fire-resistant material 20 is attached to the outer surface of the shoji screen body 11. At this time, the heat-expandable fire-resistant material 20 is attached to three sides (the top side and both sides) of the outer surface of the shoji screen body 11, excluding the bottom side. If the heat-expandable fire-resistant material 20 has an adhesive layer, it is attached to the outer surface via the adhesive layer. On the other hand, if it does not have an adhesive layer, it is attached via double-sided tape with a thickness of 200 μm (for example, "4965" manufactured by Tesa Co., Ltd.). The heat-expandable fire-resistant material 20 is attached to the back side 10B (heating side) of the outer surface of each of the three sides of the shoji screen body 11. The shoji screen body 11, with the heat-expandable fire-resistant material 20 attached to three sides, has a movable pipe 19 and is supported from the rear by the pipe 19 at the center of the opening 12 of the frame body 13, and is installed to obtain the test specimen 10. The shoji screen body 11, to which the heat-expandable fire-resistant material 20 is bonded, is positioned so that the distance L between the outer surface of its four sides and the square frame portion 15 is 6 mm. The movable pipe 19 is supported, thereby fixing the shoji screen body 11 in the above position and allowing it to move along the axial direction together with the shoji screen body 11.

[0061] The test specimen 10 is positioned so that its back surface 10B faces a heating furnace (not shown), and the burner inside the heating furnace is ignited to heat it. The temperature of the test specimen 10 is measured by a thermocouple placed in the heating furnace at a position opposite the center of the shoji screen body 11 (6 mm away from the shoji screen body 11). When heating begins, the upper center of the shoji screen body is pressed down with a spring balance from the front surface 10A towards the back surface 10B to apply a load N of 10N, and the specimen is heated for 10 minutes according to a heating curve conforming to ISO 834, in response to the forward pressure generated by the heating. The amount of displacement of the shoji screen body relative to its initial forward position after 10 minutes of heating is measured and is taken as the amount of displacement when heated for 10 minutes as described above. The amount of displacement can be measured, for example, by a laser displacement meter. At this time, the amount of displacement of plate materials fixed to the shoji screen body 11 that displace along with the displacement of the shoji screen body 11 may also be measured.

[0062] <Expansion Temperature> The thermally expandable refractory material of the present invention preferably has an expansion temperature of 230°C or lower. By having an expansion temperature of 230°C or lower, the thermally expandable refractory material can expand by a certain amount at a relatively low temperature, and the amount of displacement in the above-mentioned fire resistance load test can be easily reduced. The expansion temperature is more preferably 210°C or lower, and even more preferably 200°C or lower. Furthermore, from the viewpoint of improving fire resistance at high temperatures, the expansion temperature is preferably 150°C or higher, more preferably 160°C or higher, and even more preferably 170°C or higher. The expansion temperature of the thermally expandable refractory material can be adjusted depending on the type of thermally expandable graphite. The expansion temperature of the heat-expandable fire-resistant material is defined as the temperature at which the expanded heat-expandable fire-resistant material reaches the other iron plate when a 6.25 mm x 6.25 mm heat-expandable fire-resistant material with a thickness of 1 to 3 mm is attached to one of two opposing iron plates separated by a distance three times the thickness of the heat-expandable fire-resistant material, and heated from 40°C to 800°C at a rate of 10°C / min. The expansion temperature can be measured in detail by the method described in the examples. The heat-expandable fire-resistant material can be adjusted to a size of 6.25 mm x 6.25 mm, for example, by punching it out.

[0063] <Leaching Rate> The thermally expandable fire-resistant material of the present invention preferably has a leaching rate of 5% or less when immersed in water at 60°C for three days. A leaching rate of 5% or less improves the water resistance of the thermally expandable fire-resistant material, preventing a decrease in fire resistance by suppressing the leaching of components constituting the thermally expandable fire-resistant material even when placed in environments with high humidity or contact with water. It also prevents the thermally expandable fire-resistant material from contaminating building materials, etc., during use. The above leaching rate of the thermally expandable fire-resistant material is more preferably 4% or less, and even more preferably 3% or less. The lower the leaching rate, the better, and the lower limit is 0%.

[0064] The elution rate can be adjusted by appropriately selecting each component incorporated into the thermally expandable refractory material. For example, compounds with low solubility in water should be used for the binder resin, thermally expandable graphite, flame retardants (if necessary), and other additives. More specifically, using a thermosetting resin as the binder resin tends to lower the elution rate. Furthermore, when using an epoxy resin as the thermosetting resin, the elution rate can be further reduced by accelerating curing with a curing catalyst. The elution rate can be measured by the method described in the examples.

[0065] [Method for Manufacturing Thermally Expandable Fire-Resistant Material] The thermally expandable fire-resistant material of the present invention can be manufactured, for example, as follows. First, thermally expandable graphite, a binder resin, and flame retardants, fillers, plasticizers, and other additives as needed are mixed in a mixer such as a stirring device to obtain a fire-resistant resin composition. The temperature during mixing, and the temperature when forming the expansion layer from the fire-resistant resin composition described later, are preferably below the expansion start temperature of the thermally expandable graphite. Specifically, the temperature during mixing is preferably 20 to 100°C, and more preferably 20 to 80°C. The fire-resistant resin composition may also be diluted with a diluent such as water or an organic solvent as needed, and if the binder resin is latex, water contained in the latex may be included.

[0066] Next, the refractory resin composition obtained as described above, which contains at least a binder resin and thermally expandable graphite, is coated onto a support to form an expansion layer. Here, the refractory resin composition coated onto the support may be press-molded, heat-dried, etc., as needed, or the coated refractory resin composition may be cured to form an expansion layer. The temperature during coating of the refractory resin composition, as well as the temperature during press molding and heat drying, is not particularly limited, but is preferably 20 to 100°C, and more preferably 20 to 80°C. Furthermore, when curing the refractory resin composition, it is preferable to heat it to a temperature of, for example, 50 to 150°C, preferably 80 to 140°C. In the present invention, by coating the refractory resin composition to form layers (sheets), an expansion layer can be formed without applying large shear forces to the refractory resin composition. Therefore, when the expansion layer is formed, the expansion properties of the thermally expandable graphite are not impaired by shear. For example, when two or more types of thermally expandable graphite are used in combination, the expansion properties of each type of thermally expandable graphite are fully exhibited, making it possible to provide a thermally expandable fire-resistant material with excellent expansion performance.

[0067] Furthermore, if the thermally expandable fire-resistant material has a base material, the support can be used as the base material, and if no base material is provided, the support can be used as a release sheet and the release sheet can be peeled off from the support. In addition, another base material may be laminated on the expansion layer laminated on the base material so that base materials are provided on both sides of the expansion layer. When base materials are provided on both sides of the expansion layer, the base materials on both sides of the expansion layer may be the same or different, but it is preferable that they be the same. In addition, an adhesive may be applied to the expansion layer or the expansion layer on which the base material is provided, or an adhesive layer may be transferred and an adhesive layer may be further laminated.

[0068] (Wound Body) The heat-expandable fire-resistant material of the present invention is preferably wound into a wound body. By forming it into a wound body, transportation efficiency is improved, and for example, a large amount of heat-expandable fire-resistant material can be transported at once to a construction site of a building. In addition, it becomes possible to store a large amount of heat-expandable fire-resistant material in a limited area such as in a warehouse. The heat-expandable fire-resistant material has a certain degree of flexibility and mechanical strength, so even when formed into a wound body, wrinkles and folds can be prevented. The length of the wound body is preferably 10 m or more in the longitudinal direction, and the sheet width in this case is preferably, for example, 0.01 to 2.0 m. The upper limit of the length is not particularly limited, and it may be 500 m or less.

[0069] (Applications) The heat-expandable fire-resistant material of the present invention can be used in various types of buildings such as detached houses, apartment buildings, high-rise buildings, commercial facilities, and public facilities, as well as various vehicles such as automobiles and trains, ships, and aircraft. Among these, it is preferable to use it in building components. Specifically, it can be used in walls, beams, columns, floors, bricks, roofs, boards, windows, shoji screens, doors, sliding doors, transoms, wiring, and piping, but is not limited to these. In particular, by applying the heat-expandable fire-resistant material of the present invention to gaps in building components such as windows, doors, and sliding doors, it can prevent flames from passing through and entering during a fire.

[0070] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0071] [Evaluation Method] The evaluation methods for the following examples and comparative examples are as follows: <Fire Load Test> Using the heat-expandable fire-resistant materials obtained in each example and comparative example, a fire load test was conducted in accordance with the description in the specification, and the amount of displacement was measured when heated for 10 minutes in the fire load test.

[0072] <Expansion Temperature> Using a high-temperature observation device (Sanyo Seikou Co., Ltd., "SMP SCOPE"), two iron plates were placed one above the other in the heating furnace of the high-temperature observation device at a distance of three times the thickness of the thermally expandable refractory material. A 6.25 mm x 6.25 mm piece of thermally expandable refractory material was punched out and attached to the upper surface of the lower iron plate via the adhesive layer of the thermally expandable refractory material. However, if the thermally expandable refractory material did not have an adhesive layer, it was attached via 200 μm thick double-sided tape (tesa Co., Ltd., "4965"). Subsequently, while observing with a video camera attached to the high-temperature observation device, the temperature was raised from 40°C to 800°C at a heating rate of 10°C / min, and the temperature at which the expanded thermally expandable refractory material reached the upper iron plate was measured and defined as the expansion temperature. At this time, the temperature at which the expanded thermally expandable refractory material contacted the upper iron plate for a width equal to or greater than its original width (6.25 mm) was defined as the expansion temperature.

[0073] <Surface Properties> The obtained heat-expandable fire-resistant material was wound around a 6-inch diameter core to a length of 10 m, and its surface properties were evaluated. A rating of "A" was given if there were no wrinkles or folds, and a rating of "B" was given if either wrinkles or folds were present.

[0074] <Leaching Rate> The obtained heat-expandable refractory material was cut into 1 cm x 5 cm pieces and immersed in 50 g of pure water. After immersion in a sealed container at 60°C for 3 days, the test pieces were removed, the pure water in which the material was immersed was evaporated and dried, and the mass of the precipitate that formed was measured. Using this value, the leaching rate was calculated using the following formula and used as an indicator of water resistance: Leaching rate (%) = [(Mass of precipitate) / (Mass of test piece before immersion in pure water)] × 100

[0075] The components used in each example and comparative example are as follows. [Binder Resins] ・Epoxy resin (1) Mitsubishi Chemical Corporation "jER807", bisphenol F type epoxy resin ・Epoxy resin (2) Nagase ChemteX Corporation "EX830", glycyl ether type epoxy resin ・Epoxy resin (3) Mitsubishi Chemical Corporation "FL052", aliphatic polyamine curing agent ・Epoxy resin (4) Mitsubishi Chemical Corporation "FL079", aliphatic polyamine curing agent ・Epoxy resin (5) Daito Sangyo Co., Ltd. "Daito Kral X-6105", modified aromatic curing agent, polyamine type ・Epoxy resin (6) Daito Sangyo Co., Ltd. "Daito Kral X-2864", modified aromatic curing agent, polyamine type ・Epoxy resin (7) Toray Fine Chemicals Co., Ltd. "Thiokol LP-2", polysulfide type curing agent ・Epoxy resin (8) Toray Fine Chemicals Co., Ltd. "Thiokol LP-3, Polysulfide-based curing agent / Chloroprene latex (1) Tosoh Corporation, "GFL820", concentration 50-56% by mass Chloroprene latex (2) Tosoh Corporation, "GFL890", concentration 50-56% by mass EVA emulsion (1) Resona Corporation, "EVA AD-18", concentration 56% by mass EVA emulsion (2) Resona Corporation, "EVA P-3PN", concentration 49% by mass

[0076] (Curing catalyst (curing accelerator)) ・1,2-dimethylimidazole (1,2-DMZ) Shikoku Chemicals Co., Ltd. "Cureazole 1.2DMZ", pKa = 7.76 ・2-ethyl-4-methylimidazole (2E4MEZ) Shikoku Chemicals Co., Ltd. "Cureazole 2E4MZ", pKa = 15.32

[0077] (Thermally Expandable Graphite) ・Thermally Expandable Graphite (1) CA-60N manufactured by Air Water Co., Ltd., expansion start temperature 200°C, expansion ratio 4x at 200°C, expansion ratio 47x at 500°C ・Thermally Expandable Graphite (2) EXP-42S160 manufactured by Fuji Graphite Industry Co., Ltd., expansion start temperature 160-170°C, expansion ratio 5x at 200°C, expansion ratio 70x at 500°C ・Thermally Expandable Graphite (3) EXP-50S150 manufactured by Fuji Graphite Industry Co., Ltd., expansion start temperature 150°C, expansion ratio 19x at 200°C, expansion ratio 52x at 500°C

[0078] (Flame retardants) - Ammonium polyphosphate "EXOLIT AP422" manufactured by Clariant Co., Ltd. - Aluminum phosphite "NSF" manufactured by Taihei Chemical Industry Co., Ltd. - Zinc borate "Firebrake ZB" manufactured by Borax Co., Ltd. (Fillers) - Calcium carbonate "Whiteon BF-300" manufactured by Bihoku Powdering Industry Co., Ltd. - Aluminum hydroxide "Aluminum hydroxide B303" manufactured by Nippon Light Metal Co., Ltd. - Barium sulfate "Barite Powder FBA" manufactured by Taihei Talc Co., Ltd.

[0079] [Example 1] A binder resin, curing catalyst, thermally expandable graphite, flame retardant, and filler were supplied to a planetary stirrer according to the formulation shown in Table 1 and mixed at room temperature at 1000 rpm for 1 minute to obtain a fire-resistant resin composition. The fire-resistant resin composition was then coated onto a PET film (product name: Lumirror #12-S10, manufactured by Toray Industries, Inc., thickness 12 μm) and press-molded at 10 MPa at room temperature to obtain a sheet-like molded body with a total thickness of 1.8 mm including the base material. The molded body was then placed in a constant temperature bath at 130°C for 12 minutes to cure, obtaining a sheet-like laminate (thickness 1.8 mm) composed of a PET film (base material) and an expansion layer. Next, a 200 μm thick double-sided tape (tesa "4965") was attached to the side of the obtained laminate opposite to the side with the base material to obtain a thermally expandable fire-resistant material. The evaluation results of the obtained thermally expandable fire-resistant materials are shown in Table 1.

[0080] [Examples 2-10, Comparative Examples 1-4] Thermally expandable fire-resistant materials were prepared in the same manner as in Example 1, except that the composition of the expansion layer (fire-resistant resin composition) was changed as shown in Tables 1 and 2.

[0081] [Examples 11-14] The process was carried out in the same manner as in Example 1, except that the composition of the expansion layer (fire-resistant resin composition) was changed as shown in Table 2, and instead of press-molding and curing the fire-resistant resin composition after coating, it was dried by placing it in a constant temperature bath at 130°C for 20 minutes after coating.

[0082]

[0083] *The latex and emulsion formulations were adjusted so that the amount of active ingredients is as shown in Table 2. *In Tables 1 and 2, the binder resin is listed as 100 parts by mass.

[0084] As described above, in Examples 1 to 14, we were able to provide a thermally expandable fire-resistant material that has good expansion characteristics that can seal gaps during a fire, and whose residue has excellent adhesive properties, as the displacement in the fire load test is 5 mm or less. In contrast, in Comparative Examples 1 to 4, the displacement in the fire load test is greater than 5 mm, so we were unable to provide a thermally expandable fire-resistant material that has good expansion characteristics that can seal gaps during a fire, and whose residue has excellent adhesive properties.

Claims

1. A heat-expandable fire-resistant material having a thickness of 1 to 3 mm, comprising an expansion layer containing a binder resin and heat-expandable graphite, wherein the material comprises a sash body and a frame body having an opening, and the sash body, on which the heat-expandable fire-resistant material is attached to three sides of the outer surface, is fitted into the opening, and when a test specimen is heated according to a heating curve compliant with ISO 834, and the sash body is subjected to a load of 10 N and heated for 10 minutes, the displacement is 5 mm or less.

2. The heat-expandable fire-resistant material according to claim 1, wherein the heat-expandable fire-resistant material, measuring 6.25 mm x 6.25 mm and 1 to 3 mm in thickness, is attached to the opposing surfaces of one of two opposing iron plates separated by a distance of three times the thickness of the heat-expandable fire-resistant material, and heated at 10°C / min from 40°C to 800°C, the temperature at which the expanded heat-expandable fire-resistant material reaches the other iron plate is 230°C or less.

3. The thermally expandable refractory material according to claim 1 or 2, wherein the thermally expandable graphite comprises a first thermally expandable graphite and a second thermally expandable graphite.

4. The thermally expandable fire-resistant material according to claim 3, wherein the expansion ratio of the first thermally expandable graphite at 200°C is A1 and the expansion ratio at 500°C is A2, and the expansion ratio of the second thermally expandable graphite at 200°C is B1 and the expansion ratio at 500°C is B2, such that A1 > B1 and A2 < B2.

5. The thermally expandable fire-resistant material according to any one of claims 1 to 4, wherein the expansion layer contains a phosphorus-based flame retardant.

6. The heat-expandable fire-resistant material according to any one of claims 1 to 5, wherein the binder resin is a thermosetting resin.

7. The heat-expandable fire-resistant material according to claim 6, wherein the thermosetting resin comprises an epoxy resin.

8. The heat-expandable fire-resistant material according to claim 7, wherein the epoxy resin contains polysulfide.

9. The thermally expandable fire-resistant material according to claim 7 or 8, wherein the expansion layer includes a curing catalyst.

10. The heat-expandable fire-resistant material according to claim 9, wherein the curing catalyst is an imidazole and has a pKa of 10 or more.

11. The heat-expandable fire-resistant material according to any one of claims 1 to 10, wherein the binder resin does not contain halogens in its molecular structure.

12. A heat-expandable fire-resistant material according to any one of claims 1 to 11, wherein the elution rate when immersed in water at 60°C for three days is 5% or less.

13. The heat-expandable fire-resistant material according to any one of claims 1 to 12, wherein the heat-expandable fire-resistant material is a wound body with a longitudinal length of 10 m or more.

14. A method for producing a heat-expandable refractory material according to any one of claims 1 to 13, comprising coating a refractory resin composition containing a binder resin and heat-expandable graphite onto a support to form the expansion layer.

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