Fire-resistant resin composition, fire-resistant sheet and fitting

Abstract

To provide a fire-resistant resin composition which enables manufacture of a fire-resistant sheet that can exhibit excellent fire resistance and cold resistance.SOLUTION: A fire-resistant resin composition contains a matrix resin, a thermally expandable graphite, and an inorganic filler. A content of the total of the thermally expandable graphite and the inorganic filler is 35 mass% or more, the matrix resin contains a rubber component, and a content of the rubber component is 15 mass% or more based on the total amount of the matrix resin.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a refractory resin composition containing thermally expandable graphite, a refractory sheet made of the refractory resin composition, and a fitting including the refractory sheet.

Background Art

[0002] In the construction field, for fire prevention, refractory materials are used for building materials such as fittings, columns, and wall materials. As the refractory material, a refractory sheet in which an inorganic filler, thermally expandable graphite, etc. are blended in a resin is used (see, for example, Patent Document 1). Such a refractory sheet expands by heating to form a combustion residue to form a refractory heat-insulating layer and exhibits refractory heat-insulating performance. The refractory sheet containing thermally expandable graphite is provided, for example, in the gap between a fitting such as a door or a window provided in an opening of a building and a frame such as a door frame or a window frame surrounding these. In the event of a fire, the sheet expands in the thickness direction to close the gap between the fitting and the frame material and prevent the spread of fire.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Generally, in order to exhibit fire resistance, a refractory sheet needs to contain many inorganic compounds such as thermally expandable graphite and inorganic fillers. Therefore, the refractory sheet tends to become brittle, and particularly when used in cold regions, this tendency becomes prominent, and problems such as breakage or surface cracking easily occur when attaching the refractory sheet to a fitting, resulting in poor handleability. In particular, in the case of a long refractory sheet, the above-mentioned problems easily occur, and improvement has been demanded. On the other hand, in order to improve the brittleness of the refractory sheet, it is conceivable to reduce the content of the inorganic compound. However, in this case, the fire resistance will decrease due to a decrease in the strength of the thermal expansion residue or the like. Therefore, an object of the present invention is to provide a fire-resistant resin composition capable of forming a refractory sheet that has improved brittleness, excellent cold resistance, and excellent fire resistance due to the high strength of the thermal expansion residue.

Means for Solving the Problems

[0005] As a result of intensive studies to solve the above problems, the present inventors have found that in a fire-resistant resin composition containing a matrix resin, expandable graphite, and an inorganic filler, by setting the total amount of the expandable graphite and the inorganic filler to a certain amount or more, and setting the amount of the rubber component in the matrix resin to a certain amount or more, the above problems can be solved, and the present invention has been completed. That is, the present invention is as follows in [1] to [8] below.

[0006] [1] A fire-resistant resin composition containing a matrix resin, expandable graphite, and an inorganic filler, wherein the total content of the expandable graphite and the inorganic filler is 35% by mass or more, the matrix resin contains a rubber component, and the content of the rubber component is 15% by mass or more based on the total amount of the matrix resin. [2] The fire-resistant resin composition according to [1] above, wherein the rubber component contains a rubber having an unsaturated bond. [3] The fire-resistant resin composition according to [1] or [2] above, wherein the matrix resin contains a resin component containing at least one of a halogen atom, or a structural unit derived from styrene or vinyl acetate. [4] The fire-resistant resin composition according to any one of [1] to [3] above, wherein the inorganic filler contains an inorganic filler A having a specific gravity of 2.5 or more. [5] The fire-resistant resin composition according to any one of [1] to [4] above, which does not contain a phosphorus component. [6] A refractory sheet comprising the fire-resistant resin composition according to any one of [1] to [5] above. [7] The refractory sheet according to [6] above, which is a long product having a length of 1 m or more. [8] A fitting equipped with the fireproof sheet described in [6] or [7] above.

Effect of the Invention

[0007] According to the present invention, it is possible to provide a fireproof resin composition capable of manufacturing a fireproof sheet excellent in cold resistance and fire resistance, and a fireproof sheet made of the same.

Embodiments for Carrying Out the Invention

[0008] [Fireproof Resin Composition] The fireproof resin composition of the present invention contains a matrix resin, expandable graphite, and an inorganic filler, the total content of the expandable graphite and the inorganic filler is 35% by mass or more, and the matrix resin contains a rubber component, and the content of the rubber component is 15% by mass or more based on the total amount of the matrix resin, and it is a fireproof resin composition.

[0009] [Matrix Resin] The fireproof resin composition of the present invention contains a matrix resin, and expandable graphite and an inorganic filler are dispersed in the matrix resin. The matrix resin contains a rubber component, and the content of the rubber component is 15% by mass or more based on the total amount of the matrix resin. When the content of the rubber component is less than 15% by mass, the fireproof sheet formed by the fireproof resin composition becomes brittle, and when used in cold regions, problems such as the sheet breaking or cracking on the surface are likely to occur, and the cold resistance deteriorates. From the viewpoint of improving the cold resistance, the content of the rubber component is preferably 25% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass or more, and even more preferably 100% by mass based on the total amount of the matrix resin.

[0010] The rubber component preferably includes a rubber having an unsaturated bond. By including a rubber having an unsaturated bond, the cold resistance and fire resistance of the fireproof sheet formed from the fireproof resin composition are improved. Although the reason for this is not clear, it is presumed as follows. By using a rubber having an unsaturated bond, the affinity between the rubber and the thermally expandable graphite is improved, thereby enhancing the dispersibility of the thermally expandable graphite in the fireproof sheet. As a result, it is possible to prevent the uneven distribution of the thermally expandable graphite and the embrittlement of the fireproof sheet, improving the cold resistance. In addition, since the dispersibility of the thermally expandable graphite and the interfacial adhesion between the expanded graphite and the matrix resin are good, the voids between the thermally expandable graphite and the matrix resin in the sheet are reduced. When burned, the resin carbide and the expanded graphite adhere firmly, increasing the strength of the thermal expansion residue and improving the fire resistance.

[0011] Here, the unsaturated bond is preferably a carbon-carbon unsaturated bond, more preferably a carbon-carbon double bond. Examples of the rubber having an unsaturated bond include, for example, diene rubbers and natural rubbers described later, among which diene rubbers are preferred. The details of the diene rubbers will be described later. The rubber having an unsaturated bond is preferably 25% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass or more, and even more preferably 100% by mass based on the total amount of the matrix resin.

[0012] The type of the rubber component is not particularly limited, and examples include diene rubbers and polyolefin rubbers. In addition to these, natural rubbers, butyl rubbers, chlorinated butyl rubbers, chlorosulfonated polyethylene, acrylic rubbers, epichlorohydrin rubbers, multi-vulcanized rubbers, non-vulcanized rubbers, silicone rubbers, fluorine rubbers, urethane rubbers, etc. can be mentioned. Among these, from the viewpoint of improving the cold resistance and fire resistance of the fireproof sheet, the rubber component preferably contains at least one selected from diene rubbers and polyolefin rubbers, and more preferably contains a diene rubber.

[0013] Examples of diene rubbers include isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), styrene-butadiene-styrene block copolymer (SBS), and the like. Among these diene rubbers, from the viewpoint of improving the dispersibility of thermally expandable graphite, at least one selected from butadiene rubber (BR), styrene-butadiene rubber (SBR), and chloroprene rubber (CR) is preferable, and at least one selected from styrene-butadiene rubber (SBR) and chloroprene rubber (CR) is more preferable. Also, from the viewpoint of enhancing the dispersibility of thermally expandable graphite and improving the cold resistance and fire resistance of the refractory sheet, it is preferable to use two or more different types of diene rubbers in combination. In particular, it is preferable to use styrene-butadiene rubber (SBR) and chloroprene rubber (CR) in combination. When styrene-butadiene rubber (SBR) and chloroprene rubber (CR) are used in combination, the content ratio (SBR / CR) thereof is preferably 90 / 10 to 10 / 90 by mass ratio, and more preferably 80 / 20 to 20 / 80.

[0014] The bound styrene content of styrene-butadiene rubber (SBR) is not particularly limited. However, from the viewpoint of improving the cold resistance of the refractory sheet, it is, for example, 10 to 60% by mass, preferably 15 to 55% by mass, and more preferably 20 to 50% by mass. The bound styrene content can be measured by 1 H-NMR. Also, the Mooney viscosity [ML(1+4)100°C] of styrene-butadiene rubber is not particularly limited. However, from the viewpoint of improving the cold resistance of the refractory sheet, it is, for example, 30 to 150, preferably 35 to 70, and more preferably 40 to 60.

[0015] The Mooney viscosity [ML(1+4) 100°C] of chloroprene rubber (CR) is not particularly limited, but from the viewpoint of improving the cold resistance of the refractory sheet, it is, for example, 25 to 150, preferably 30 to 100, and more preferably 35 to 75. In this specification, the Mooney viscosity is a value measured in accordance with JIS K6300.

[0016] Examples of the polyolefin rubber include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), and olefin-based thermoplastic elastomer (TPO). Generally, the above-mentioned olefin-based thermoplastic elastomer (TPO) has polyolefins such as polyethylene and polypropylene as hard segments and rubber components such as EPM and EPDM as soft segments. Any of the blend type, dynamic crosslinking type, and polymerization type of olefin-based thermoplastic elastomer (TPO) can be used. From the viewpoint of improving the cold resistance of the refractory sheet among the polyolefin rubbers, ethylene-propylene-diene rubber (EPDM), olefin-based thermoplastic elastomer (TPO), etc. are preferable.

[0017] From the viewpoint of increasing the strength of the thermal expansion residue of the refractory sheet and improving the fire resistance, the matrix resin of the present invention preferably contains a resin component containing at least any one of a halogen atom, or a structural unit derived from styrene or vinyl acetate. The resin component containing at least any one of the halogen atom, or a structural unit derived from styrene or vinyl acetate may be the above-mentioned rubber component or a non-rubber component described later.

[0018] The rubber component is preferably a resin component containing a halogen atom or a structural unit derived from styrene. Further, the non-rubber component compounded as necessary preferably contains a structural unit derived from the halogen atom, or styrene or vinyl acetate. Examples of the resin component containing at least one of a halogen atom, or a structural unit derived from styrene or vinyl acetate include the above-mentioned chloroprene rubber (CR), styrene-butadiene rubber (SBR), chlorinated butyl rubber, chlorosulfonated polyethylene, fluororubber, etc., and polyvinyl chloride-based resins (PVC), ethylene-vinyl acetate copolymer resins, polystyrene resins, etc. to be described later. Among these, chloroprene rubber (CR), styrene-butadiene rubber (SBR), polyvinyl chloride-based resins (PVC), ethylene-vinyl acetate copolymer resins, etc. are preferable.

[0019] In addition, the matrix resin may be composed of only one type of resin used as the rubber component, or may be composed of a plurality of resins. The case of being composed of a plurality of resins includes the case of using two or more types of rubber components, the case of using one type of rubber component and one or more types of non-rubber components in combination, etc. From the viewpoint of enhancing the dispersibility of the thermally expandable graphite in the matrix resin and improving the cold resistance and fire resistance, the matrix resin, whether it is composed of one type of resin or a plurality of resins, preferably has an SP value difference of 2.0 or less between the plurality of resins. The SP value difference is preferably 1.5 or less, more preferably 1 or less. Here, the SP value difference between the plurality of resins means the difference in the SP values between the resin having the largest SP value and the resin having the smallest SP value among the plurality of resins. The SP value is the solubility parameter and is a value measured by the Fedors method.

[0020] The matrix resin of the present invention may contain, in addition to the above-mentioned rubber component, a non-rubber component which is a resin other than the rubber component. The non-rubber component which is a resin other than the rubber component may be a thermoplastic resin or a thermosetting resin, but is preferably a thermoplastic resin. Examples of the thermoplastic resin include polyolefin resins such as polypropylene resin, polyethylene resin, poly(1-butene) resin, and polypentene resin; polyester resins such as polyethylene terephthalate; polystyrene resin; acrylonitrile-butadiene-styrene (ABS) resin; ethylene-vinyl acetate copolymer resin (EVA); polycarbonate resin; polyphenylene ether resin; (meth)acrylic resins; polyamide resins; polyvinyl chloride resins (PVC); novolak resins; polyurethane resins; polyisobutylene; and the like. Among the thermoplastic resins, from the viewpoint of improving the fire resistance of the fireproof sheet, polyvinyl chloride resins and ethylene-vinyl acetate copolymer resins are preferred, and polyvinyl chloride resins are more preferred.

[0021] Examples of the polyvinyl chloride resin (PVC) include a homopolymer of vinyl chloride monomer, a copolymer of vinyl chloride monomer and a monomer having an unsaturated bond copolymerizable with vinyl chloride monomer, a graft copolymer obtained by graft copolymerizing vinyl chloride monomer onto a polymer or copolymer other than vinyl chloride monomer, and the like. These may be used alone or in combination of two or more. In the present invention, chlorinated polyvinyl chloride resins, which are chlorinated products of polyvinyl chloride resins, are also included in the polyvinyl chloride resins. The degree of polymerization of the polyvinyl chloride resin is preferably 500 to 2,000, more preferably 800 to 1,500. In such a range, the fluidity of the resin component increases, and it becomes easy to adjust the expansion ratio to a desired range.

[0022] The ethylene-vinyl acetate copolymer resin (EVA) may be an uncrosslinked ethylene-vinyl acetate copolymer resin or a high-temperature crosslinked ethylene-vinyl acetate copolymer resin. Further, as the ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate modified resin such as a saponified product of ethylene-vinyl acetate copolymer or a hydrolyzate of ethylene-vinyl acetate can also be used. The ethylene-vinyl acetate copolymer resin preferably has a vinyl acetate content of 5 to 90% by mass, more preferably 8 to 50% by mass, and even more preferably 12 to 35% by mass, as measured in accordance with JIS K 6730 "Test Methods for Ethylene-Vinyl Acetate Resins". The melt flow rate (MFR) of the ethylene-vinyl acetate copolymer resin at 190 °C is preferably 0.5 to 15 g / 10 min, more preferably 1 to 8 g / 10 min. The melt flow rate of the ethylene-vinyl acetate copolymer at 190 °C is a measured value under a load of 2.16 kg and is measured in accordance with JIS K7210:1999.

[0023] The above thermosetting resin is not particularly limited, and examples thereof include epoxy resins, polyurethane resins, phenolic resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, thermosetting polyimides, etc. Among them, from the viewpoint of improving fire resistance, epoxy resins are preferred.

[0024] The epoxy resin may be an epoxy resin having an aromatic ring or an epoxy resin having no aromatic ring, but from the viewpoint of enhancing nonflammability, an epoxy resin having an aromatic ring is preferred. The epoxy resin is obtained, for example, by reacting an epoxy resin compound having an epoxy group with a curing agent. Examples of the epoxy resin compound used to obtain the above epoxy resin having an aromatic ring include bisphenol A type epoxy resin compounds, bisphenol F type epoxy resin compounds, biphenyl type epoxy resin compounds, naphthalene type epoxy resin compounds, phenol novolak type epoxy resin compounds, bisphenol A novolak type epoxy resin compounds, tetraphenol ethane type epoxy resin compounds, tetraglycidyl diaminodiphenylmethane type epoxy resin compounds, aminophenol type epoxy resin compounds, aniline type epoxy resin compounds, xylenediamine type epoxy resin compounds, etc. Among these, bisphenol A type epoxy resin compounds and bisphenol F type epoxy resin compounds are preferred.

[0025] As the curing agent, an addition polymerization type or a catalytic type one is used. Examples of the addition polymerization type curing agent include polyamines, acid anhydrides, polyphenols, polymercaptans, etc. Examples of the catalytic type curing agent include tertiary amines, imidazoles, Lewis acid complexes, etc. The curing method of the epoxy resin compound is not particularly limited and can be carried out by known methods. The content of the curing agent is preferably in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the above epoxy resin compound. When it is 50 parts by mass or more, the epoxy resin compound is likely to cure. When it is 150 parts by mass or less, the effect according to the blending amount of the curing agent can be obtained.

[0026] Based on the total amount of the refractory resin composition, the content of the matrix resin is preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 65% by mass or less, more preferably 60% by mass or less. When the content of the matrix resin is at least these lower limit values, the cold resistance of the refractory sheet is improved. When the content of the matrix resin is at most these upper limit values, the content of the thermally expandable graphite and the inorganic filler described later can be adjusted more, so the fire resistance is improved.

[0027] <Plasticizer> The refractory resin composition of the present invention may contain a plasticizer. When the refractory resin composition contains a plasticizer, the matrix resin becomes easier to flow and the refractory sheet becomes easier to expand. Further, when a polyvinyl chloride resin is used as the matrix resin, it is preferable to use a plasticizer in combination. By using a plasticizer in combination, the moldability is improved.

[0028] The plasticizer is not particularly limited, and examples thereof include phthalate plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), diisodecyl phthalate (DIDP), etc.; fatty acid ester plasticizers such as di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), dibutyl adipate (DBA), etc.; epoxidized ester plasticizers such as epoxidized soybean oil; adipic acid ester plasticizers such as adipic acid ester, adipic acid polyester, etc.; trimellitic acid ester plasticizers such as tri-2-ethylhexyl trimellitate (TOTM), triisononyl trimellitate (TINTM), etc.; process oils such as mineral oil. The plasticizer may be used alone or in combination of two or more.

[0029] When the fire-resistant resin composition of the present invention contains a plasticizer, the content thereof is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, based on 100 parts by mass of the matrix resin. When the content of the plasticizer is within the above range, the extrusion moldability tends to be improved, and it is possible to suppress the molded body from becoming too soft.

[0030] <Thermally expandable graphite, inorganic filler> The fire-resistant resin composition of the present invention contains thermally expandable graphite and an inorganic filler. The total content of the thermally expandable graphite and the inorganic filler in the fire-resistant resin composition is 35% by mass or more. When the total content of the thermally expandable graphite and the inorganic filler is less than 35% by mass, the fire resistance decreases, for example, the expansion ratio of the fire-resistant sheet decreases or the strength of the thermal expansion residue decreases. From the viewpoint of improving the fire resistance, the total content of the thermally expandable graphite and the inorganic filler is preferably 40% by mass or more, and from the viewpoint of increasing the blending amount of the matrix resin to improve the cold resistance, it is preferably 80% by mass or less, more preferably 75% by mass or less.

[0031] Thermally expandable graphite expands when heated and is obtained by treating powders such as natural flake graphite, pyrolytic graphite, and kish graphite with an inorganic acid and a strong oxidizing agent to form a graphite intercalation compound, which is a kind of crystalline compound that maintains the layered structure of carbon. Examples of the inorganic acid include concentrated sulfuric acid, nitric acid, and selenic acid. Examples of the strong oxidizing agent include concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, and hydrogen peroxide. In addition, the thermally expandable graphite obtained by the acid treatment as described above may be further neutralized with a neutralizing agent such as ammonia, lower aliphatic amines, alkali metal compounds, and alkaline earth metal compounds. Examples of the lower aliphatic amines include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, and butylamine. Examples of the alkali metal compounds and the above-mentioned alkaline earth metal compounds include hydroxides, oxides, carbonates, sulfates, and organic acid salts of potassium, sodium, calcium, barium, and magnesium.

[0032] The content of thermally expandable graphite in the refractory resin composition is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 45% by mass or less. When the content of thermally expandable graphite is at or above these lower limit values, it is easier to obtain expansion suitable for preventing the passage of fire. When it is at or below these upper limit values, the strength of the thermal expansion residue of the refractory sheet tends to be high, and the cold resistance of the refractory sheet is improved, and the processability is good.

[0033] The refractory resin composition of the present invention contains an inorganic filler. When the inorganic filler is heated to form an expansion heat-insulating layer, it increases the heat capacity, suppresses heat transfer, and acts as an aggregate to improve the strength of the thermal expansion residue.

[0034] From the perspective of improving the cold resistance of the refractory sheet, as the inorganic filler, it is preferable to include an inorganic filler A with a specific gravity of 2.5 or more. By containing the inorganic filler A, the amount of the matrix resin per unit volume can be increased, whereby the brittleness of the refractory sheet is improved and the cold resistance is likely to be enhanced. From such a perspective, the specific gravity of the inorganic filler A is preferably 3 or more, and more preferably 4 or more. For example, metal oxides, metal carbonates, etc. described later can be used as the inorganic filler A with a specific gravity of 2.5 or more. The inorganic filler A may be used alone or in combination of a plurality thereof. Based on the total amount of the inorganic filler, the content of the inorganic filler A is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass.

[0035] As the inorganic filler, it is preferable to use the inorganic filler A with a specific gravity of 2.5 or more described above, but it is also possible to use an inorganic filler with a specific gravity of less than 2.5. The inorganic filler that can be used in the present invention is not particularly limited. For example, metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrite; metal carbonates such as calcium carbonate, zinc carbonate, strontium carbonate, and barium carbonate; metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and hydrotalcite; calcium salts such as calcium sulfate, gypsum fiber, and calcium silicate; silica, diatomaceous earth, dacite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based balloon, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, metal phosphates such as sodium phosphate, potassium phosphate, magnesium phosphate, and aluminum phosphate; metal phosphites such as sodium phosphite, potassium phosphite, magnesium phosphite, and aluminum phosphite; ammonium polyphosphate, orthophosphate metal salts, metaphosphate metal salts, tripolyphosphate metal salts, etc. The inorganic filler may be used alone or in combination of two or more kinds.

[0036] Among these, as the inorganic filler, from the viewpoint of improving the fire resistance, metal oxides, metal hydroxides, metal carbonates, etc. are preferable, and at least one kind selected from iron oxide, aluminum hydroxide, and calcium carbonate is more preferable. More specifically, it is further preferable that the inorganic filler contains at least iron oxide, and it is particularly preferable to use iron oxide and calcium carbonate in combination. By using iron oxide, even when the expansion ratio of the refractory sheet is relatively large, it is easy to maintain the strength of the thermal expansion residue, and therefore the fire resistance is easily improved. When using iron oxide, its amount used is preferably 15% by mass or more, more preferably 25% by mass or more, and still more preferably 40% by mass or more, based on the total amount of the inorganic filler. When using iron oxide and calcium carbonate in combination, the mass ratio thereof (iron oxide / calcium carbonate) is preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 80 / 20.

[0037] The content of the inorganic filler in the fire-resistant resin composition is preferably 3% by mass or more, more preferably 8% by mass or more, still more preferably 13% by mass or more, and preferably 50% by mass or less, and more preferably 30% by mass or less.

[0038] <Other components> In addition to the above-described matrix resin, expandable graphite, and inorganic filler, the fire-resistant resin composition may contain various organic flame retardants such as bromine-containing flame retardants, nitrogen-containing flame retardants, and phosphate ester compounds, colorants, antioxidants, and other various additives.

[0039] Examples of the bromine-containing flame retardants include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene-bis(tetrabromophthalimide), tetrabromobisphenol A, and the like.

[0040] Examples of nitrogen-containing flame retardants include melamine derivatives such as melamine, butyl melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethyl melamine, and melamine phosphate; cyanuric acid derivatives such as cyanuric acid, methyl cyanurate, diethyl cyanurate, trimethyl cyanurate, and triethyl cyanurate; isocyanuric acid derivatives such as isocyanuric acid, methyl isocyanurate, N,N'-diethyl isocyanurate, tris-methyl isocyanurate, tris-ethyl isocyanurate, bis(2-carboxyethyl) isocyanurate, 1,3,5-tris(2-carboxyethyl) isocyanurate, and tris(2,3-epoxypropyl) isocyanurate; melamine cyanurate, melamine isocyanurate, ammonium carbonate, etc.

[0041] Examples of phosphate ester compounds include 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, etc.

[0042] <Phosphorus component> The fire-resistant resin composition of the present invention preferably does not contain a phosphorus component. By not containing a phosphorus component, the water resistance of the fire-resistant sheet formed from the fire-resistant composition is improved. Therefore, even after long-term exposure to water, excellent expansion ratio, residue hardness, and shape retention after expansion can be ensured. Here, the phosphorus component is a compound containing a phosphorus atom, and as the above-mentioned matrix resin, expandable graphite, inorganic filler, and additives such as an organic flame retardant, a colorant, and an antioxidant that are blended as necessary, it is preferable not to use a compound containing a phosphorus atom.

[0043] [Fire-resistant sheet] Using the fire-resistant resin composition of the present invention, a fire-resistant sheet made of the fire-resistant resin composition can be formed. The expansion ratio in the thickness direction of the fire-resistant sheet is not particularly limited, but from the viewpoints of fire resistance and water resistance, it is preferably 5 to 70 times, more preferably 10 to 60 times, and even more preferably 15 to 55 times. The fire-resistant sheet of the present invention preferably exhibits an expansion ratio within the above range even after being immersed in water for a long time. The expansion ratio is measured by the method described in the examples.

[0044] The thickness of the fire-resistant sheet is not particularly limited, but from the viewpoints of fire resistance and handleability, 0.2 to 10 mm is preferable, and 0.5 to 3.0 mm is more preferable.

[0045] The fire-resistant sheet of the present invention is excellent in cold resistance as described above, and it is difficult for problems such as cracking or surface cracking to occur during use. Therefore, even when the length of the sheet is long, it has excellent handleability and can be used, for example, as a long product with a length of 1 m or more.

[0046] The fire-resistant sheet of the present invention can be manufactured, for example, as follows. First, a predetermined amount of matrix resin, expandable graphite, and inorganic filler resin, and additives such as an organic flame retardant, a colorant, and an antioxidant that are blended as necessary are kneaded with a kneader such as a kneading roll to obtain a fire-resistant resin composition. Next, the obtained fire-resistant resin composition is formed into a sheet by a known forming method such as press molding, calender molding, extrusion molding, etc., whereby a fire-resistant sheet can be obtained.

[0047] The fire-resistant sheet can be used in various buildings such as single-family houses, apartment houses, high-rise houses, high-rise buildings, commercial facilities, and public facilities, various vehicles such as automobiles, trains, ships, airplanes, etc. When a fire breaks out in a building, vehicle, etc., the fire-resistant sheet expands by being heated and can block the flow of air and exhibit fire extinguishing properties. The fire-resistant sheet is used by being attached to the members constituting the above-mentioned buildings, vehicles, ships, airplanes, etc. For example, in a building, it can be attached to fittings such as windows, shoji doors, doors, doors, fusuma, walls such as columns and steel-reinforced concrete, floors, roofs, etc. to reduce or prevent the intrusion of fire and smoke. Among these, it is preferably used for fittings. That is, one embodiment of the present invention also provides a fitting provided with a fire-resistant sheet.

[0048] The fire-resistant sheet may be used alone as a fire-resistant sheet, or other members may be appropriately attached and used. For example, members other than the fire-resistant sheet may be laminated on the fire-resistant sheet, or a base material may be provided on at least one surface of the fire-resistant sheet. The base material may be a combustible material layer, a semi-incombustible material layer, or a non-combustible material layer. The thickness of the base material is not particularly limited, but is, for example, 5 μm to 1 mm. Examples of the material used for the combustible material layer include one or more of cloth materials, paper materials, wood, resin films, etc. When the base material is a semi-incombustible material layer or a non-combustible material layer, examples of the material used include metals, inorganic materials, etc. More specifically, woven or non-woven fabrics made of glass fiber, ceramic fiber, carbon fiber, graphite fiber, etc. may be mentioned. Also, a composite material of these fibers and metals may be used, and for example, alumiglass cloth is preferable. Also, an adhesive layer may be laminated on the sheet-shaped fire-resistant material. The adhesive layer may be provided on the above-mentioned base material or may be directly formed on the surface of the fire-resistant sheet.

Examples

[0049] The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

[0050] [Evaluation Method] (1) Elution Rate Five test pieces (length 50 mm, width 50 mm, thickness 1.5 mm) each made from the refractory sheets of the obtained examples and comparative examples were immersed in 200 g of pure water, immersed in a sealed container at 60°C for 1 week, then the samples were taken out, and the immersed pure water was evaporated and dried at 60°C for 96 hours, and the mass of the generated precipitate was measured. Using this value, the elution rate was calculated by the following formula and used as an index of water resistance. Elution rate (%) = [(mass of precipitate) / (mass of refractory sheet before immersion in pure water)] × 100 (2) Expansion Ratio A test piece (length 100 mm, width 100 mm, thickness 1.5 mm) made from the obtained refractory sheet was immersed in 500 mL of pure water in a sealed container at 60°C for 1 week, then the sample was taken out. The test piece created by evaporating and drying the sample at 60°C for 96 hours was placed on the bottom surface of a stainless steel holder (101 mm square, height 80 mm), supplied to an electric furnace, and heated at 600°C for 30 minutes. Then, the height (highest part), width, length, and thickness of the test piece were measured, and the expansion ratio was calculated by ((thickness of the test piece after heating) / (thickness of the test piece before heating)).

[0051] (3) Residue Hardness The test piece after heating for measuring the expansion ratio was supplied to a compression tester (manufactured by Kato Tech Co., Ltd., "Finger Filling Tester"), compressed at a speed of 0.1 cm / second with a 3-point indenter with a diameter of 1 mm, and the maximum stress from the upper surface of the residue to a compression of 10 mm was measured, and the compression strength (kgf / cm 2 ) of the test piece after combustion was measured.

[0052] (4) Cold Resistance (Brittleness) Using the wound body of the refractory sheet obtained by winding the long refractory sheets obtained in each example and comparative example, the refractory sheet was redeployed at 0 °C and -20 °C for evaluation. During the deployment process, the appearance of the sheet was observed to confirm whether cracks occurred on the surface or the sheet broke. Evaluation was carried out according to the following evaluation criteria. ◎: The sheet could be deployed without cracking or breaking. (-20 °C) 〇: The sheet could be deployed without cracking or breaking. (0 °C) △: Cracks occurred in the sheet during deployment. (0 °C) ×: The sheet broke during deployment. (0 °C)

[0053] (Examples 1 to 27, Comparative Examples 1 to 4) With the formulations shown in Tables 1 to 3 below, the matrix resin, expandable graphite, inorganic filler, plasticizer, and additive were put into a roll and kneaded at 150 °C for 5 minutes to obtain a refractory resin composition. The obtained refractory resin composition was press-molded at 150 °C for 3 minutes to obtain a refractory sheet with a thickness of 1.5 mm. Each component used in each example and comparative example is as follows.

[0054] (1) Matrix resin <Chloroprene rubber: CR> · CR "Y-20E" manufactured by Tosoh Corporation Mooney viscosity [ML(1+4)100 °C]: 43 - 53 · CR1 "E-20H" manufactured by Tosoh Corporation Mooney viscosity [ML(1+4)100 °C]: 54 - 74 · CR2 "R-10" manufactured by Tosoh Corporation Mooney viscosity [ML(1+4)100 °C]: 35 - 55

[0055] <Styrene-butadiene rubber: SBR> · SBR "JSR1500" manufactured by JSR Corporation Styrene content: 23.5% by mass, Mooney viscosity [ML(1+4)100℃]: 52 · SBR2 "JSR0202" manufactured by JSR Corporation Styrene content: 46% by mass, Mooney viscosity [ML(1+4)100℃]: 45 · SBR3 "JSR0122" manufactured by JSR Corporation Styrene content: 37% by mass, Mooney viscosity [ML(1+4)100℃]: 52

[0056] <Styrene-butadiene-styrene copolymer: SBS> · SBS "TR1086" manufactured by JSR Corporation Styrene content: 45% by mass

[0057] <Ethylene-propylene-diene rubber: EPDM> · EPDM "ENB-EPT X-3012P" manufactured by Mitsui Chemicals, Inc.

[0058] <Olefin thermoplastic elastomer: TPO> · TPO "Milastomer 5020BS" manufactured by Mitsui Chemicals, Inc.

[0059] <Ethylene-vinyl acetate copolymer resin: EVA> · EVA "EV460" of Mitsui DuPont Polychemical Co., Ltd. Vinyl acetate content: 19% by mass, MFR (190℃): 2.5 g / 10 min <Polyvinyl chloride resin: PVC> · PVC "TK-1000" manufactured by Shin-Etsu Chemical Co., Ltd., average degree of polymerization 1030

[0060] (2) Plasticizer · DOP Di-2-ethylhexyl phthalate, "DOP" manufactured by J Plus Co., Ltd.

[0061] (3) Thermally expandable graphite · Thermally expandable graphite "CA-60N" manufactured by Air Water

[0062] (4) Inorganic filler · Iron oxide: Titanium Industry Co., Ltd. "BL-100", specific gravity 5.1 · Calcium carbonate: Bihoku Powder Chemical Industry Co., Ltd. "Whitlon BF-300", specific gravity 2.93 · Aluminum hydroxide: Hayashi Kasei Co., Ltd. "C-305", specific gravity 2.42

[0063] (5) Additive · EDAP (ethylenediamine phosphate) manufactured by Albright & Wilson "Amgard EDAP"

[0064]

Table 1

[0065]

Table 2

[0066]

Table 3

[0067] As shown in the examples, the refractory sheet formed of a refractory resin composition in which the total content of the expandable graphite and the inorganic filler is 35% by mass or more and the content of the rubber component is 15% by mass or more based on the total amount of the matrix resin has good fire resistance because of the high value of the residual hardness, and it was also found to be excellent in cold resistance. On the other hand, a refractory sheet formed from a refractory resin composition in which the total content of the expandable graphite and the inorganic filler is less than 35% by mass or the content of the rubber component is less than 15% by mass based on the total amount of the matrix resin had deteriorated physical properties in at least one of fire resistance and cold resistance.

Claims

1. A refractory resin composition containing a matrix resin, thermally expandable graphite, and an inorganic filler, wherein the total content of the thermally expandable graphite and the inorganic filler is 35% by mass or more, and the matrix resin contains a rubber component, and the content of the rubber component is 15% by mass or more based on the total amount of the matrix resin.

2. The refractory resin composition according to Claim 1, wherein the rubber component contains a rubber having an unsaturated bond.

3. The refractory resin composition according to Claim 1 or 2, wherein the matrix resin contains a resin component containing at least one of a halogen atom, or a structural unit derived from styrene or vinyl acetate.

4. The refractory resin composition according to any one of Claims 1 to 3, wherein the inorganic filler contains an inorganic filler A having a specific gravity of 2.5 or more.

5. The refractory resin composition according to any one of Claims 1 to 4, which does not contain a phosphorus component.

6. A refractory sheet comprising the refractory resin composition according to any one of Claims 1 to 5.

7. The refractory sheet according to Claim 6, which is a long product having a length of 1 m or more.

8. A fitting comprising the refractory sheet according to Claim 6 or 7.

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