Fire-resistant resin compositions, fire-resistant sheets, and building components

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 fire-resistant resin composition containing thermally expandable graphite, a fire-resistant sheet formed of the fire-resistant resin composition, and a fitting including the fire-resistant sheet.

Background Art

[0002] In the construction field, fire-resistant materials are used for building materials such as fittings, columns, and wall materials for fire prevention. As fire-resistant materials, fire-resistant sheets or the like obtained by blending a resin with an inorganic filler, thermally expandable graphite and the like are used (see, for example, Patent Document 1). Such a fire-resistant sheet expands upon heating, the combustion residue forms a fire-resistant heat-insulating layer, and exhibits fire-resistant heat-insulating performance. A fire-resistant sheet containing thermally expandable graphite is provided, for example, in a gap between fittings such as doors and windows provided in an opening of a building and a frame such as a door frame or window frame surrounding the fittings. In the event of a fire, the sheet expands in the thickness direction to close the gap between the fitting and the frame material, thereby preventing the spread of fire.

Prior Art Literature

Patent Literature

[0003]

Patent Document 1

Summary of the Invention

Problem to be Solved by the Invention

[0004] Generally, a fire-resistant sheet needs to contain many inorganic compounds such as thermally expandable graphite and inorganic fillers in order to exhibit fire resistance. As a result, the fire-resistant sheet tends to become brittle, and this tendency is particularly pronounced when used in cold regions. When attaching the fire-resistant sheet to a fitting, problems such as breakage and cracking on the surface are likely to occur, leading to problems in handleability. In particular, in the case of a long fire-resistant sheet, the above-described problems are likely to occur, and improvements have been demanded. On the other hand, reducing the content of the above-mentioned inorganic compound could be considered to improve the brittleness of the fire-resistant sheet, but in this case, the fire resistance would decrease due to factors such as a reduction in the strength of the thermal expansion residue. Therefore, the present invention aims to provide a fire-resistant resin composition that can form a fire-resistant sheet having improved brittleness, excellent cold resistance, and high strength of thermally expandable residue, thus also having excellent fire resistance. [Means for solving the problem]

[0005] As a result of diligent research to solve the above problems, the inventors have found that the above problems can be solved by providing a fire-resistant resin composition containing a matrix resin, thermally expandable graphite, and an inorganic filler, where the total amount of thermally expandable graphite and inorganic filler is set to a certain amount or more, and the amount of rubber component in the matrix resin is set to a certain amount or more, thereby completing the present invention. That is, the present invention is as described in [1] to [8] below.

[0006] [1] A fire-resistant resin composition comprising 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, wherein 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 rubber having unsaturated bonds. [3] The fire-resistant resin composition according to [1] or [2] above, wherein the matrix resin comprises a resin component containing at least one of halogen atoms or structural units 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] A fire-resistant resin composition according to any of [1] to [4] above, which does not contain phosphorus. [6] A fire-resistant sheet made of any of the fire-resistant resin compositions described in [1] to [5] above. [7] A fire-resistant sheet as described in [6] above, which is a long product with a length of 1 meter or more. [8] A door or window fitted with the fire-resistant sheet described in [6] or [7] above. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a fire-resistant resin composition that can be used to produce a fire-resistant sheet with excellent cold resistance and fire resistance, and a fire-resistant sheet made therefrom. [Modes for carrying out the invention]

[0008] [Fire-resistant resin composition] The fire-resistant resin composition of the present invention contains 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, wherein the content of the rubber component is 15% by mass or more based on the total amount of the matrix resin.

[0009] <Matrix resin> The fire-resistant resin composition of the present invention contains a matrix resin in which thermally expandable graphite and an inorganic filler are dispersed. The matrix resin contains a rubber component, with the rubber component content being 15% by mass or more based on the total amount of the matrix resin. If the rubber component content is less than 15% by mass, the fire-resistant sheet formed from the fire-resistant resin composition becomes brittle, making it prone to problems such as bending or cracking on the surface when used in cold regions, resulting in poor cold resistance. From the viewpoint of improving cold resistance, the rubber component content is preferably 25% by mass or more, more preferably 50% by mass or more, even 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 contains rubber having unsaturated bonds. Including rubber having unsaturated bonds improves the cold resistance and fire resistance of the fire-resistant sheet formed from the fire-resistant resin composition. The reason for this is not entirely clear, but it is presumed to be as follows: By using rubber having unsaturated bonds, the affinity between the rubber and the thermally expandable graphite is improved, thereby increasing the dispersibility of the thermally expandable graphite in the fire-resistant sheet. As a result, it is possible to prevent the thermally expandable graphite from being unevenly distributed and making the fire-resistant sheet brittle, thus improving cold resistance. In addition, because 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, and when burned, the resin carbide and expanded graphite adhere firmly, increasing the strength of the thermally expanded residue and improving fire resistance.

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

[0012] The types of rubber components are not particularly limited, but examples include diene rubber and polyolefin rubber. In addition to these, other examples include natural rubber, butyl rubber, chlorinated butyl rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polyvulcanized rubber, non-vulcanized rubber, silicone rubber, fluororubber, and urethane rubber. Among these, from the viewpoint of improving the cold resistance and fire resistance of the fire-resistant sheet, it is preferable that the rubber component includes at least one selected from diene-based rubber and polyolefin-based rubber, and more preferably includes diene-based rubber.

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

[0014] The amount of styrene bound to styrene-butadiene rubber (SBR) is not particularly limited, but from the viewpoint of improving the cold resistance of the fire-resistant sheet, it is, for example, 10 to 60% by mass, preferably 15 to 55% by mass, and more preferably 20 to 50% by mass. 1 It can be measured by 1H-NMR. Furthermore, the Mooney viscosity [ML(1+4)100℃] of the styrene-butadiene rubber is not particularly limited, but from the viewpoint of improving the cold resistance of the fire-resistant 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 fire-resistant sheet, it is, for example, 25 to 150, preferably 30 to 100, and more preferably 35 to 75. In the present specification, the Mooney viscosity is a value measured in accordance with JIS K6300.

[0016] Examples of the polyolefin-based rubber include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), and olefin-based thermoplastic elastomer (TPO). The above olefin-based thermoplastic elastomer (TPO) generally has a polyolefin such as polyethylene or polypropylene as a hard segment, and a rubber component such as EPM or EPDM as a soft segment. Any of a blend type, a dynamically crosslinked type, and a polymerization type can be used for the olefin-based thermoplastic elastomer (TPO). Among polyolefin-based rubbers, ethylene-propylene-diene rubber (EPDM) and olefin-based thermoplastic elastomer (TPO) are preferable from the viewpoint of improving the cold resistance of the fire-resistant sheet.

[0017] The matrix resin of the present invention preferably contains a resin component containing at least one of a halogen atom, or a structural unit derived from styrene or vinyl acetate, from the viewpoint of increasing the strength of the thermal expansion residue of the fire-resistant sheet and improving fire resistance. The resin component containing at least one of a halogen atom, or a structural unit derived from styrene or vinyl acetate may be the rubber component described above, or may be 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 blended as needed preferably contains the halogen atom, or a structural unit derived from styrene or vinyl acetate. Examples of resin components containing halogen atoms or structural units derived from styrene or vinyl acetate include the above-mentioned chloroprene rubber (CR), styrene-butadiene rubber (SBR), chlorinated butyl rubber, chlorosulfonated polyethylene, fluororubber, and polyvinyl chloride resins (PVC), ethylene-vinyl acetate copolymer resins, and polystyrene resins, which will be described later. Among these, chloroprene rubber (CR), styrene-butadiene rubber (SBR), polyvinyl chloride resins (PVC), and ethylene-vinyl acetate copolymer resins are preferred.

[0019] Furthermore, the matrix resin may consist of only one type of resin used as a rubber component, or it may consist of multiple resins. Examples of cases where multiple resins are used include cases where two or more types of rubber components are used, or cases where one type of rubber component and one or more non-rubber components are used in combination. From the viewpoint of improving the dispersibility of thermally expandable graphite in the matrix resin and thereby improving cold resistance and fire resistance, it is preferable that the matrix resin is composed of one type of resin, or, if composed of multiple resins, that the difference in SP values ​​of the multiple resins be 2.0 or less. Preferably, the difference in SP values ​​is 1.5 or less, and more preferably 1 or less. Here, the difference in SP values ​​of the multiple resins refers to the difference in SP values ​​between the resin with the largest SP value and the resin with the smallest SP value among the multiple resins. Note that the SP value is a 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 rubber component described above, 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 a thermoplastic resin is preferred. Examples of the thermoplastic resins mentioned above include polypropylene resin, polyethylene resin, poly(1-)butene resin, polypentene resin and other polyolefin resins, 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 resin, polyamide resin, polyvinyl chloride resin (PVC), novolac resin, polyurethane resin, and polyisobutylene. Among thermoplastic resins, polyvinyl chloride resin and ethylene-vinyl acetate copolymer resin are preferred from the viewpoint of providing good fire resistance for fire-resistant sheets, with polyvinyl chloride resin being more preferred.

[0021] Examples of polyvinyl chloride resins (PVCs) include homopolymers of vinyl chloride monomer, copolymers of vinyl chloride monomer and monomers having unsaturated bonds copolymerizable with vinyl chloride monomer, and graft copolymers obtained by graft copolymerizing vinyl chloride monomer with polymers or copolymers other than vinyl chloride monomer. These may be used individually or in combination of two or more types. In this invention, chlorinated polyvinyl chloride resins, which are chlorinated products of polyvinyl chloride resins, are also included in the category of polyvinyl chloride resins. The degree of polymerization of the polyvinyl chloride resin is preferably 500 to 2,000, and more preferably 800 to 1,500. Within this range, the fluidity of the resin component increases, making it easier to adjust the expansion ratio to the desired range.

[0022] The ethylene-vinyl acetate copolymer resin (EVA) may be a non-crosslinked ethylene-vinyl acetate copolymer resin or a high-temperature crosslinked ethylene-vinyl acetate copolymer resin. Furthermore, ethylene-vinyl acetate modified resins, such as saponified ethylene-vinyl acetate copolymers or hydrolyzed ethylene-vinyl acetates, can also be used as the ethylene-vinyl acetate copolymer resin. 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 Method for Ethylene-Vinyl Acetate Resin". The melt flow rate (MFR) of the ethylene-vinyl acetate copolymer resin at 190°C is preferably 0.5 to 15 g / 10 min, and more preferably 1 to 8 g / 10 min. The melt flow rate of the ethylene-vinyl acetate copolymer at 190°C is measured under a load of 2.16 kg and is measured in accordance with JIS K7210:1999.

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

[0024] The epoxy resin may be an epoxy resin having an aromatic ring or an epoxy resin without an aromatic ring, but from the viewpoint of enhancing non-flammability, an epoxy resin having an aromatic ring is preferred. The epoxy resin can be obtained, for example, by reacting an epoxy resin compound having an epoxy group with a curing agent. Examples of epoxy resin compounds used to obtain the epoxy resin having the aromatic ring described above include bisphenol A type epoxy resin compounds, bisphenol F type epoxy resin compounds, biphenyl type epoxy resin compounds, naphthalene type epoxy resin compounds, phenol novolac type epoxy resin compounds, bisphenol A novolac type epoxy resin compounds, tetraphenolethane type epoxy resin compounds, tetraglycidyldiaminodiphenylmethane type epoxy resin compounds, aminophenol type epoxy resin compounds, aniline type epoxy resin compounds, and xylenediamine type epoxy resin compounds. Among these, bisphenol A type epoxy resin compounds and bisphenol F type epoxy resin compounds are preferred.

[0025] Polyaddition-type or catalytic-type curing agents can be used. Examples of polyaddition-type curing agents include polyamines, acid anhydrides, polyphenols, and polymercaptans. Examples of catalytic-type curing agents include tertiary amines, imidazoles, and Lewis acid complexes. The curing method for epoxy resin compounds is not particularly limited and can be carried out by known methods. The curing agent content is preferably in the range of 50 to 150 parts by mass per 100 parts by mass of the epoxy resin compound. If the content is 50 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.

[0026] The matrix resin content, relative to the total amount of the fire-resistant resin composition, is preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 65% ​​by mass or less, and more preferably 60% by mass or less. If the matrix resin content is above these lower limits, the cold resistance of the fire-resistant sheet is improved. If the matrix resin content is below these upper limits, the content of the thermally expandable graphite and inorganic filler described later can be adjusted to be larger, thus improving fire resistance.

[0027] <Plasticizer> The fire-resistant resin composition of the present invention may contain a plasticizer. The inclusion of a plasticizer in the fire-resistant resin composition makes the matrix resin more fluid, and the fire-resistant sheet more easily expands. Furthermore, when using a polyvinyl chloride-based resin as the matrix resin, it is preferable to use a plasticizer in combination. The use of a plasticizer improves moldability.

[0028] Examples of plasticizers are not particularly limited, but include phthalate ester plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), and diisodecyl phthalate (DIDP); fatty acid ester plasticizers such as di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), and dibutyl adipate (DBA); epoxidized ester plasticizers such as epoxidized soybean oil; adipate ester plasticizers such as adipate esters and adipate polyesters; trimellitate ester plasticizers such as tory 2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM); and process oils such as mineral oil. Plasticizers may be used individually or in combination of two or more.

[0029] When the fire-resistant resin composition of the present invention contains a plasticizer, the content is preferably 10 to 90 parts by mass, and more preferably 20 to 80 parts by mass, per 100 parts by mass of the matrix resin. When the plasticizer content is within the above range, the extrusion moldability tends to improve, and it is possible to suppress the molded article 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 thermally expandable graphite and inorganic filler in the fire-resistant resin composition is 35% by mass or more. If the total content of thermally expandable graphite and inorganic filler is less than 35% by mass, the fire resistance will decrease due to a lower expansion ratio of the fire-resistant sheet and a decrease in the strength of the thermal expansion residue. From the viewpoint of improving fire resistance, the total content of thermally expandable graphite and inorganic filler is preferably 40% by mass or more, and from the viewpoint of improving cold resistance by increasing the amount of matrix resin blended, it is preferably 80% by mass or less, and more preferably 75% by mass or less.

[0031] Thermally expandable graphite is a type of crystalline compound that expands when heated. It is produced by treating powders of natural scaly graphite, pyrolytic graphite, or quiche graphite with inorganic acids and strong oxidizing agents to create graphite intercalation compounds, while maintaining the layered structure of carbon. Examples of inorganic acids include concentrated sulfuric acid, nitric acid, and selenic acid. Examples of strong oxidizing agents include concentrated nitric acid, perchloric acid, perchlorates, permanganates, dichromates, and hydrogen peroxide. Furthermore, the thermally expandable graphite obtained by acid treatment as described above may be further neutralized with a neutralizing agent such as ammonia, aliphatic lower amines, alkali metal compounds, or alkaline earth metal compounds. Examples of aliphatic lower amines include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, and butylamine. Examples of 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, magnesium, etc.

[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, even more preferably 30% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less. When the content of thermally expandable graphite is above these lower limits, it becomes easier to obtain expansion suitable for preventing the passage of fire, and when it is below these upper limits, the strength of the thermally expanded residue of the refractory sheet tends to increase, as does the cold resistance of the refractory sheet and the processability.

[0033] The fire-resistant resin composition of the present invention contains an inorganic filler. When heated and an expanding heat-insulating layer is formed, the inorganic filler increases the heat capacity and suppresses heat transfer, while also acting as an aggregate to improve the strength of the thermal expansion residue.

[0034] From the viewpoint of improving the cold resistance of the fire-resistant sheet, it is preferable to include inorganic filler A with a specific gravity of 2.5 or higher as the inorganic filler. By including inorganic filler A, the amount of matrix resin per unit volume can be increased, thereby improving the brittleness of the fire-resistant sheet and making it easier to improve its cold resistance. From this viewpoint, the specific gravity of the inorganic filler A is preferably 3 or higher, and more preferably 4 or higher. For example, metal oxides, metal carbonates, etc., described later, can be used as inorganic filler A with a specific gravity of 2.5 or higher. Inorganic filler A may be used alone or in combination of multiple types. The content of inorganic filler A relative to the total amount of inorganic filler is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass.

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

[0036] Among these, from the viewpoint of improving fire resistance, metal oxides, metal hydroxides, and metal carbonates are preferred as inorganic fillers, and at least one selected from iron oxide, aluminum hydroxide, and calcium carbonate is more preferred. More specifically, it is even more 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, it is easier to maintain the strength of the thermal expansion residue even when the expansion ratio of the fire-resistant sheet is relatively large, and thus fire resistance is easily improved. When iron oxide is used, the amount used is preferably 15% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more, based on the total amount of inorganic filler. When iron oxide and calcium carbonate are used in combination, the mass ratio (iron oxide / calcium carbonate) is preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 80 / 20.

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

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

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

[0040] Examples of nitrogen-containing flame retardants include melamine, butylmelamine, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, melamine phosphate, and other melamine derivatives; cyanuric acid, methyl cyanurate, diethyl cyanurate, trimethyl cyanurate, triethyl cyanurate, and other cyanuric acid derivatives; isocyanuric acid, methyl isocyanurate, N,N'-diethyl isocyanurate, trismethyl isocyanurate, trisethyl isocyanurate, bis(2-carboxyethyl) isocyanurate, 1,3,5-tris(2-carboxyethyl) isocyanurate, tris(2,3-epoxypropyl) isocyanurate, and other isocyanuric acid derivatives; melamine cyanurate, melamine isocyanurate, and ammonium carbonate.

[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, and xylenyldiphenyl phosphate.

[0042] <Phosphorus component> The fire-resistant resin composition of the present invention preferably does not contain phosphorus. By not containing phosphorus, the water resistance of the fire-resistant sheet formed from the fire-resistant composition is improved. Therefore, even after prolonged exposure to water, excellent expansion ratio, residue hardness, and shape retention after expansion can be ensured. Here, phosphorus refers to a compound containing phosphorus atoms, and it is preferable not to use compounds containing phosphorus atoms in the matrix resin, thermally expandable graphite, inorganic filler, and additives such as organic flame retardants, colorants, and antioxidants that are added as needed.

[0043] [Fireproof sheet] A fire-resistant sheet made from the fire-resistant resin composition of the present invention can be formed using the fire-resistant resin composition of the present invention. The expansion ratio in the thickness direction of the fire-resistant sheet is not particularly limited, but from the viewpoint 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. It is preferable that the fire-resistant sheet of the present invention 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 viewpoint of fire resistance and ease of handling, 0.2 to 10 mm is preferred, and 0.5 to 3.0 mm is more preferred.

[0045] As described above, the fire-resistant sheet of the present invention has excellent cold resistance and is less prone to problems such as bending or cracking on the surface during use. Therefore, it is easy to handle even when the sheet is long, and can be used as a long product of, for example, 1 meter or more in length.

[0046] The fire-resistant sheet of the present invention can be manufactured, for example, as described below. First, a predetermined amount of matrix resin, thermally expandable graphite, and inorganic filler resin, along with additives such as organic flame retardants, colorants, and antioxidants as needed, are kneaded in a kneader such as a kneading roll to obtain a fire-resistant resin composition. Next, the obtained fire-resistant resin composition can be formed into a sheet using known molding methods such as press molding, calendering, or extrusion molding to obtain a fire-resistant sheet.

[0047] Fire-resistant sheets 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, trains, ships, and aircraft. When a fire breaks out in a building or vehicle, the fire-resistant sheet expands when heated, blocking the flow of air and thus providing fire-extinguishing properties. Fire-resistant sheets are used by being attached to components that make up the above-mentioned buildings, vehicles, ships, aircraft, etc. For example, in buildings, they can be attached to fittings such as windows, shoji screens, doors, sliding doors, etc., columns, walls made of reinforced concrete, floors, roofs, etc., to reduce or prevent the intrusion of fire and smoke. Among these, use in fittings is preferred. That is, one embodiment of the present invention also provides fittings equipped with fire-resistant sheets.

[0048] A fire-resistant sheet may be used on its own, or it may be used with other components attached as appropriate. For example, a fire-resistant sheet may have other components laminated to it, or a base material may be provided on at least one side of the fire-resistant sheet. The base material may be a combustible material layer, a semi-noncombustible material layer, or a noncombustible material layer. The thickness of the base material is not particularly limited, but is for example 5 μm to 1 mm. Examples of materials used for the combustible material layer include one or more types such as cloth, paper, wood, and resin film. When the base material is a semi-noncombustible material layer or a noncombustible material layer, examples of materials used include metals and inorganic materials, and more specifically, woven or nonwoven fabrics made of glass fibers, ceramic fibers, carbon fibers, and graphite fibers. Alternatively, composite materials of these fibers and metals may be used, for example, aluminum glass cloth is preferred. Furthermore, an adhesive layer may be laminated to the sheet-like fire-resistant material. The adhesive layer may be provided on top of the base material, or it may be formed directly on the surface of the fire-resistant sheet. [Examples]

[0049] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0050] [Evaluation Method] (1) Elution rate Five test pieces (50 mm long, 50 mm wide, 1.5 mm thick) prepared from the refractory sheets of each example and comparative example were immersed in 200 g of pure water in a sealed container at 60°C for one week. After that, the samples were removed, the pure water in which the samples were immersed was evaporated and dried at 60°C for 96 hours, and the mass of the precipitate that formed was measured. Using this value, the elution rate was calculated using the following formula and used as an indicator of water resistance. Elution rate (%) = [(Mass of precipitate) / (Mass of refractory sheet before immersion in pure water)] × 100 (2) Expansion ratio A test specimen (100 mm long, 100 mm wide, 1.5 mm thick) prepared from the obtained refractory sheet was immersed in 500 mL of pure water at 60°C in a sealed container for one week, after which the sample was removed. The sample was evaporated and dried at 60°C for 96 hours to prepare a test specimen, which was placed on the bottom of a stainless steel holder (101 mm square, 80 mm high), supplied to an electric furnace, and heated at 600°C for 30 minutes. After that, the height (highest part), width, length, and thickness of the test specimen were measured, and the expansion ratio was calculated by ((thickness of the test specimen after heating) / (thickness of the test specimen before heating)).

[0051] (3) Residue hardness The heated test specimens, whose expansion ratio was measured, were fed into a compression testing machine (Kato Tech Co., Ltd., "Finger Feeling Tester"), compressed at a speed of 0.1 cm / second with a 1 mm diameter three-point indenter, and the maximum stress up to 10 mm of compression from the top surface of the residue was measured to determine the compressive strength (kgf / cm²) of the burnt test specimens. 2 ) was measured.

[0052] (4) Cold resistance (brittleness) The fire-resistant sheets obtained by winding up the long lengths of fire-resistant sheets from each example and comparative example were evaluated by redeploying the fire-resistant sheets at 0°C and -20°C. During the redeployment process, the appearance of the sheets was observed to check whether cracks or fractures occurred on the surface. The evaluation was performed according to the following criteria. ◎: The sheet could be deployed without cracking or tearing. (-20℃) ○: The sheet could be deployed without cracking or tearing. (0℃) △: Cracks appeared in the sheet when it was unfolded. (0℃) ×: The sheet tore when unfolded. (0℃)

[0053] (Examples 1-27, Comparative Examples 1-4) A refractory resin composition was obtained by mixing a matrix resin, thermally expandable graphite, inorganic filler, plasticizer, and additives in a roll at 150°C for 5 minutes, according to the formulations shown in Tables 1 to 3 below. 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. The components used in each example and comparative example are as follows.

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

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

[0056] <Styrene-butadiene-styrene copolymer: SBS> • SBS JSR Corporation's "TR1086" Bound styrene content: 45% by mass

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

[0058] <Olefin-based thermoplastic elastomer: TPO> • TPO Mitsui Chemicals, Inc.'s "Milastomer 5020BS"

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

[0060] (2) Plasticizers • DOP Di-2-ethylhexylphthalate, manufactured by J-Plus Co., Ltd.

[0061] (3) Thermally expandable graphite • Thermally expandable graphite, Air Water Co., Ltd. "CA-60N"

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

[0063] (5) Additives • EDAP (Ethylenediamine Phosphate) "Amgard EDAP" manufactured by Albright & Wilson

[0064] [Table 1]

[0065] [Table 2]

[0066] [Table 3]

[0067] As shown in the examples, a fire-resistant sheet formed from a fire-resistant resin composition having a total content of 35% by mass or more of thermally expandable graphite and inorganic filler, and a rubber component content of 15% by mass or more based on the total amount of matrix resin, was found to have good fire resistance due to its high residue hardness value, and also to have excellent cold resistance. On the other hand, fire-resistant sheets formed from fire-resistant resin compositions in which the total content of thermally expandable graphite and inorganic fillers is less than 35% by mass, or in which the rubber component content is less than 15% by mass based on the total amount of matrix resin, showed deterioration in at least one of the physical properties of fire resistance and cold resistance.

Claims

1. It contains a matrix resin, thermally expandable graphite, and an inorganic filler. The total content of the aforementioned thermally expandable graphite and inorganic filler is 35 to 80% by mass on a basis of the total amount of the fire-resistant resin composition for building fixtures. The content of the aforementioned thermally expandable graphite is 20 to 60% by mass on a basis of the total amount of the fire-resistant resin composition for building materials. The content of the inorganic filler is 3 to 50% by mass on a basis of the total amount of the fire-resistant resin composition for building fixtures. The inorganic filler contains an inorganic filler A having a specific gravity of 2.5 or more and 5.1 or less, and the inorganic filler A is a metal oxide (excluding antimony trioxide). The matrix resin contains a rubber component, and the content of the rubber component is 15% by mass or more and 100% by mass or less based on the total amount of the matrix resin. A fire-resistant resin composition for building fixtures (excluding those containing polyphosphates) wherein the rubber component contains at least one of a halogen atom or a styrene-derived structural unit.

2. The fire-resistant resin composition for building fixtures according to claim 1, wherein the rubber component contains rubber having unsaturated bonds.

3. The fire-resistant resin composition for building fixtures according to claim 1 or 2, wherein the matrix resin comprises a resin component containing at least one of halogen atoms or structural units derived from styrene or vinyl acetate.

4. A fire-resistant resin composition for building fixtures according to any one of claims 1 to 3, which does not contain phosphorus.

5. A fire-resistant sheet for building components comprising the fire-resistant resin composition for building components described in any one of claims 1 to 4.

6. The fire-resistant sheet for building components according to claim 5, wherein the length is 1 meter or more.

7. A joinery piece equipped with a fire-resistant sheet for joinery as described in claim 5 or 6.

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