JP7007424B2 - Refractory resin composition, refractory sheet and fittings - Google Patents

Description

The present invention relates to a refractory resin composition containing heat-expandable graphite, a refractory sheet made of the refractory resin composition, and a fitting provided with the refractory sheet.

In the building field, refractory materials are used for building materials such as fittings, pillars, and wall materials for fire protection. As the refractory material, a refractory sheet or the like in which an inorganic filler, a heat-expandable graphite, or the like is mixed with a resin is used (see, for example, Patent Document 1). Such a refractory sheet expands by heating and the combustion residue forms a refractory heat insulating layer to exhibit the refractory heat insulating performance.
The refractory sheet containing the heat-expandable graphite is provided, for example, in the gap between the fittings such as doors and windows provided in the opening of the building and the frame such as the door frame and the window frame surrounding them, and is provided in the event of a fire. The sheet expands in the thickness direction, closing the gap between the fitting and the frame material, and preventing the spread of fire.

Japanese Unexamined Patent Publication No. 2017-141463

Generally, a refractory sheet needs to contain many inorganic compounds such as heat-expandable graphite and an inorganic filler in order to exhibit fire resistance. Therefore, the refractory sheet tends to be brittle, and this tendency is particularly noticeable when used in cold regions, and problems such as breakage and cracks on the surface when the refractory sheet is attached to fittings are likely to occur. , There was a problem with handleability. In particular, in the case of a long refractory sheet, the above-mentioned problems are likely to occur, and improvement has been sought.
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, but in this case, the refractory resistance is lowered due to a decrease in the strength of the thermal expansion residue and the like.
Therefore, it is an object of the present invention to provide a refractory resin composition capable of forming a refractory sheet having improved brittleness, excellent cold resistance, and high strength of a heat-expandable residue, which is also excellent in fire resistance. And.

As a result of diligent studies to solve the above problems, the present inventor has made a total amount of the heat-expandable graphite and the inorganic filler in the fire-resistant resin composition containing the matrix resin, the heat-expandable graphite, and the inorganic filler. The present invention has been completed by finding that the above problems can be solved by setting the amount of rubber to a certain amount or more and setting the amount of the rubber component in the matrix resin to a certain amount or more. That is, the present invention is as described in [1] to [8] below.

[1] The matrix resin, the heat-expandable graphite, and the inorganic filler are contained, the total content of the heat-expandable graphite and the inorganic filler is 35% by mass or more, and the matrix resin contains a rubber component. A fire-resistant resin composition having a rubber component content of 15% by mass or more based on the total amount of the matrix resin.
[2] The refractory resin composition according to the above [1], wherein the rubber component contains a rubber having an unsaturated bond.
[3] The refractory resin composition according to the above [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 the above [1] to [3], wherein the inorganic filler contains the inorganic filler A having a specific gravity of 2.5 or more.
[5] The refractory resin composition according to any one of the above [1] to [4], which does not contain a phosphorus component.
[6] A refractory sheet comprising the refractory resin composition according to any one of the above [1] to [5].
[7] The refractory sheet according to the above [6], which is a long product having a length of 1 m or more.
[8] Joinery provided with the fireproof sheet according to the above [6] or [7].

According to the present invention, it is possible to provide a refractory resin composition capable of producing a refractory sheet having excellent cold resistance and fire resistance, and a refractory sheet made of the same.

[Refractory resin composition]
The fire-resistant resin composition of the present invention contains a matrix resin, a heat-expandable graphite, and an inorganic filler, and the total content of the heat-expandable graphite and the inorganic filler is 35% by mass or more, and the matrix. A fire-resistant resin composition in which the 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.

<Matrix resin>
The fire-resistant resin composition of the present invention contains a matrix resin, in which the heat-expandable graphite and the inorganic filler are dispersed.
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. If the content of the rubber component is less than 15% by mass, the refractory sheet formed by the refractory resin composition becomes brittle, and when used in cold regions, the sheet may be broken or the surface may be cracked. Is likely to occur, and cold resistance deteriorates. From the viewpoint of improving 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, based on the total amount of the matrix resin. More preferably, it is 100% by mass.

The rubber component preferably contains a rubber having an unsaturated bond. By including the rubber having an unsaturated bond, the cold resistance and the fire resistance of the refractory sheet formed from the refractory resin composition are improved. The reason for this is not clear, but it is presumed as follows. By using a rubber having an unsaturated bond, the affinity between the rubber and the heat-expandable graphite is improved, thereby increasing the dispersibility of the heat-expandable graphite in the refractory sheet, and as a result, the heat-expandable graphite is produced. It is possible to prevent the fireproof sheet from being unevenly distributed and becoming brittle, and the cold resistance is improved. Further, since the dispersibility of the heat-expandable graphite and the interfacial adhesion between the expanded graphite and the matrix resin are good, the voids between the heat-expandable graphite and the matrix resin in the sheet are reduced, and the resin carbide is reduced when burned. The expanded graphite adheres firmly, the strength of the thermal expansion residue increases, and the fire resistance improves.

Here, the unsaturated bond is preferably a carbon-carbon unsaturated bond, and more preferably a carbon-carbon double bond. Examples of the rubber having an unsaturated bond include diene-based rubber and natural rubber, which will be described later, and among them, diene-based rubber is preferable. Details of the diene rubber 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, still more preferably 100% by mass, based on the total amount of the matrix resin. be.

The type of rubber component is not particularly limited, and examples thereof include diene rubber and polyolefin rubber. In addition to these, natural rubber, butyl rubber, chlorinated butyl rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, and polyvulase rubber are used. , Non-vulverized rubber, silicone rubber, fluororubber, urethane rubber and the like.
Among these, from the viewpoint of improving the cold resistance and fire resistance of the refractory sheet, the rubber component preferably contains at least one selected from diene-based rubber and polyolefin-based rubber, and more preferably contains diene-based rubber. preferable.

Examples of the diene rubber 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) and the like.
Among these diene rubbers, at least one selected from butadiene rubber (BR), styrene-butadiene rubber (SBR), and chloroprene rubber (CR) from the viewpoint of improving the dispersibility of heat-expandable graphite. Is preferable, and at least one selected from styrene-butadiene rubber (SBR) and chloroprene rubber (CR) is preferable.
Further, from the viewpoint of improving the dispersibility of the heat-expandable graphite and improving the cold resistance and the fire resistance of the refractory sheet, it is preferable to use two or more different diene rubbers in combination, and in particular, styrene-butadiene rubber (stylene-butadiene rubber). It is preferable to use 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) of these is preferably 90/10 to 10/90 in terms of mass ratio, and is 80/20. It is more preferably to 20/80.

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

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

Examples of the polyolefin-based rubber include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), and olefin-based thermoplastic elastomer (TPO). The olefin-based thermoplastic elastomer (TPO) generally has polyolefins such as polyethylene and polypropylene as hard segments and rubber components such as EPM and EPDM as soft segments. As the olefin-based thermoplastic elastomer (TPO), any of a blend type, a dynamic cross-linking type, and a polymerization type can be used.
Among the polyolefin-based rubbers, ethylene-propylene-diene rubber (EPDM), olefin-based thermoplastic elastomer (TPO), and the like are preferable from the viewpoint of improving the cold resistance of the fire-resistant sheet.

The matrix resin of the present invention contains a halogen atom or a resin component containing at least one of a structural unit derived from styrene or vinyl acetate from the viewpoint of increasing the strength of the thermal expansion residue of the refractory sheet to improve the fire resistance. Is preferable. The resin component containing at least one of the halogen atom or a structural unit derived from styrene or vinyl acetate may be the above-mentioned rubber component or the non-rubber component described later.

The rubber component is preferably a resin component containing a halogen atom or a structural unit derived from styrene. Further, the non-rubber component to be blended as needed preferably contains the halogen atom or a structural unit derived from 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, and chlorosulfonated polyethylene. Examples thereof include fluororubber, polyvinyl chloride resin (PVC), ethylene-vinyl acetate copolymer resin, and polystyrene resin, which will be described later. Among these, chloroprene rubber (CR), styrene-butadiene rubber (SBR), polyvinyl chloride resin (PVC), ethylene-vinyl acetate copolymer resin and the like are preferable.

Further, the matrix resin may be composed of only one kind of resin used as a rubber component, or may be composed of a plurality of resins. The case of being composed of a plurality of resins includes a case where two or more kinds of rubber components are used, a case where one kind of rubber component and one kind or more of non-rubber components are used in combination, and the like.
From the viewpoint of increasing the dispersibility of the heat-expandable graphite in the matrix resin and improving the cold resistance and the fire resistance, the matrix resin may be composed of one kind of resin or a plurality of resins. If so, it is preferable that the SP value difference between the plurality of resins is 2.0 or less. The SP value difference is preferably 1.5 or less, and more preferably 1 or less. Here, the SP value difference of the plurality of resins means the difference in SP value 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 a solubility parameter and is a value measured by the Fedors method.

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

Examples of the polyvinyl chloride resin (PVC) include a homopolymer of a vinyl chloride monomer, a copolymer of a vinyl chloride monomer and a monomer having an unsaturated bond commutable with the vinyl chloride monomer, and a polymer other than the vinyl chloride monomer. Alternatively, a graft copolymer obtained by graft-copolymerizing a vinyl chloride monomer to the copolymer may be mentioned, and these may be used alone or in combination of two or more.
In the present invention, the chlorinated polyvinyl chloride resin, which is a chlorinated product of the polyvinyl chloride resin, is also included in the polyvinyl chloride resin.
The degree of polymerization of the polyvinyl chloride resin is preferably 500 to 2,000, more preferably 800 to 1500. Within such a range, the fluidity of the resin component is increased, and it becomes easy to adjust the expansion ratio to a desired range.

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. May be good. Further, as the ethylene-vinyl acetate copolymer resin, an ethylene-vinyl acetate modified resin such as a saponified product of an ethylene-vinyl acetate copolymer and 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, as measured in accordance with JIS K 6730 “Ethylene-vinyl acetate resin test method”. More preferably, it is 12 to 35% by mass.
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 a measured value under a load of 2.16 kg, and is measured in accordance with JIS K7210: 1999.

The thermosetting resin is not particularly limited, and examples thereof include epoxy resin, polyurethane resin, phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, and thermosetting polyimide, and among them, fire resistance. Epoxy resin is preferable from the viewpoint of improving the property.

The epoxy resin may be an epoxy resin having an aromatic ring or an epoxy resin having no aromatic ring, but an epoxy resin having an aromatic ring is preferable from the viewpoint of enhancing nonflammability. The epoxy resin can be obtained, for example, by reacting an epoxy resin compound having an epoxy group with a curing agent.
The epoxy resin compound used to obtain the above-mentioned epoxy resin having an aromatic ring is, for example, a bisphenol A type epoxy resin compound, a bisphenol F type epoxy resin compound, a biphenyl type epoxy resin compound, a naphthalene type epoxy resin compound, and the like. Phenol novolak type epoxy resin compound, bisphenol A novolak type epoxy resin compound, tetraphenol ethane type epoxy resin compound, tetraglycidyl diaminodiphenylmethane type epoxy resin compound, aminophenol type epoxy resin compound, aniline type epoxy resin compound , Xylenidamine type epoxy resin compounds and the like. Among these, bisphenol A type epoxy resin compounds and bisphenol F type epoxy resin compounds are preferable.

As the curing agent, a double addition type or a catalytic type is used. Examples of the heavy addition type curing agent include polyamines, acid anhydrides, polyphenols, and polymercaptans. Examples of the catalytic curing agent include tertiary amines, imidazoles, and Lewis acid complexes. The method for curing the epoxy resin compound is not particularly limited, and a known method can be used.
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 epoxy resin compound. When it is 50 parts by mass or more, the epoxy resin compound is easily cured, and when it is 150 parts by mass or less, an effect according to the blending amount of the curing agent can be obtained.

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, based on the total amount of the refractory resin composition. Is. 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 not more than these upper limit values, the content of the heat-expandable graphite and the inorganic filler described later can be adjusted in a large amount, so that the fire resistance is improved.

<Plasticizer>
The refractory resin composition of the present invention may contain a plasticizer. When the refractory resin composition contains a plasticizer, the matrix resin tends to flow and the refractory sheet tends to expand. When a polyvinyl chloride resin is used as the matrix resin, it is preferable to use a plasticizer together. Moldability is improved by using a plasticizer together.

The plasticizer is not particularly limited, but is a phthalate ester plasticizer such as di-2-ethylhexylphthalate (DOP), dibutylphthalate (DBP), diheptylphthalate (DHP), diisodecylphthalate (DIDP), di-2- Fatty acid ester plasticizers such as ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), dibutyl adipate (DBA), epoxidized ester plasticizers such as epoxidized soybean oil, adipic acid ester plasticizers such as adipic acid ester and adipate polyester. , Trimellitic phthalate plasticizers such as Tory 2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM), process oils such as mineral oil and the like. The plasticizer may be used alone or in combination of two or more.

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 with respect to 100 parts by mass of the matrix resin. When the content of the plasticizer is within the above range, the extrudability tends to be improved, and it is possible to prevent the molded product from becoming too soft.

<Thermal expandable graphite, inorganic filler>
The refractory resin composition of the present invention contains thermally expandable graphite and an inorganic filler. The total content of the heat-expandable graphite and the inorganic filler in the refractory resin composition is 35% by mass or more. When the total content of the heat-expandable graphite and the inorganic filler is less than 35% by mass, the expansion ratio of the refractory sheet is lowered, the strength of the heat-expanded residue is lowered, and the fire resistance is lowered. The total content of the heat-expandable graphite and the inorganic filler is preferably 40% by mass or more from the viewpoint of improving the fire resistance, and preferably from the viewpoint of increasing the blending amount of the matrix resin to improve the cold resistance. It is 80% by mass or less, more preferably 75% by mass or less.

Thermally expandable graphite expands when heated, and is obtained by treating powders such as natural scaly graphite, thermally decomposed graphite, and kiss graphite with an inorganic acid and a strong oxidizing agent to form a graphite intercalation compound. It 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, hydrogen peroxide and the like.
Further, the heat-expandable graphite obtained by the acid treatment as described above may be further neutralized with a neutralizing agent such as ammonia, an aliphatic lower amine, an alkali metal compound, and an alkaline earth metal compound. Examples of the aliphatic lower amine include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like. Examples of the alkali metal compound and the alkaline earth metal compound include hydroxides such as potassium, sodium, calcium, barium and magnesium, oxides, carbonates, sulfates and organic acid salts.

The content of the heat-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, still more preferably 45% by mass or less. When the content of the heat-expandable graphite is more than these lower limit values, it becomes easier to obtain expansion suitable for blocking the passage of fire, and when it is less than these upper limit values, the strength of the heat-expandable residue of the refractory sheet becomes high. There is a tendency, and the cold resistance of the refractory sheet is improved, and the workability is improved.

The refractory resin composition of the present invention contains an inorganic filler. When the inorganic filler is heated to form an expanded heat insulating layer, the inorganic filler acts as an aggregate to improve the strength of the heat-expanded residue while increasing the heat capacity and suppressing heat transfer.

From the viewpoint of improving the cold resistance of the refractory sheet, the inorganic filler preferably contains the inorganic filler A having 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, thereby improving the brittleness of the refractory sheet and facilitating the improvement of cold resistance. From such a viewpoint, the specific gravity of the inorganic filler A is preferably 3 or more, more preferably 4 or more. For example, metal oxides, metal carbonates, etc., which will be described later, can be used as the inorganic filler A having a specific gravity of 2.5 or more. The inorganic filler A may be used alone or in combination of two or more.
The content of the inorganic filler A is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 100% by mass with respect to the total amount of the inorganic filler.

As the inorganic filler, it is preferable to use the above-mentioned inorganic filler A having a specific gravity of 2.5 or more, but an inorganic filler having a specific gravity of less than 2.5 can also be used.
The inorganic filler that can be used in the present invention is not particularly limited, and for example, metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrite, calcium carbonate, and the like. Metallic carbonates such as zinc carbonate, strontium carbonate and barium carbonate, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide and hydrotalcite, calcium sulfates, gypsum fibers, calcium salts such as calcium silicate, Silica, diatomaceous earth, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, active white clay, sepiolite, imogolite, phosphoric acid, glass fiber, glass beads, silica 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 fibers, frying Metal phosphates such as ash, sodium phosphate, potassium phosphate, magnesium phosphate, aluminum phosphate, metal phosphates such as sodium phosphite, potassium phosphite, magnesium phosphite, aluminum phosphite. , Ammonium polyphosphate, metal orthophosphoric acid salt, metal metal phosphate salt, metal tripolyphosphate metal salt and the like. The inorganic filler may be used alone or in combination of two or more.

Among these, as the inorganic filler, metal oxides, metal hydroxides, metal carbonates and the like are preferable from the viewpoint of improving fire resistance, and among them, at least selected from iron oxide, aluminum hydroxide and calcium carbonate. One or more is more preferable. More specifically, the inorganic filler preferably 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 easy to maintain the strength of the thermal expansion residue even when the expansion ratio of the refractory sheet is relatively large, and therefore it is easy to improve the fire resistance.
When iron oxide is used, the amount used is preferably 15% by mass or more, more preferably 25% by mass or more, still more preferably 40% by mass or more, based on the total amount of the 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, more preferably 20/80 to 80/20.

The content of the inorganic filler in the refractory resin composition is preferably 3% by mass or more, more preferably 8% by mass or more, further preferably 13% by mass or more, and preferably 50% by mass or less. More preferably, it is 30% by mass or less.

<Other ingredients>
In addition to the above-mentioned matrix resin, heat-expandable graphite, and inorganic filler, the fire-resistant resin composition includes various organic flame retardants such as bromine-containing flame retardants, nitrogen-containing flame retardants, and phosphoric acid ester compounds, colorants, and oxidations. It may contain various additives such as an inhibitor.

Examples of the brominated flame retardant include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether and bis (pentabromophenoxy). Examples thereof include ethane, ethylene-bis (tetrabromophthalimide), tetrabromobisphenol A and the like.

Examples of the nitrogen-containing flame retardant include melamine derivatives such as melamine, butyl melamine, trimethyl melamine, hexamethylol melamine, hexamethoxymethyl melamine, and melamine phosphate, cyanuric acid, methyl cyanurate, diethyl cyanurate, and trimethyl cyanurate. Cyanuric acid derivatives such as triethyl cyanurate, isocyanuric acid, methyl isocyanurate, N, N'-diethyl isocyanurate, trismethyl isocyanurate, trisethyl isocyanurate, bis (2-carboxyethyl) isocyanurate, 1,3,5 -Isocyanuric acid derivatives such as tris (2-carboxyethyl) isocyanurate and tris (2,3-epoxypropyl) isocyanurate, melamine cyanurate, melamine isocyanurate, ammonium carbonate and the like can be mentioned.

Examples of the phosphate ester compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, and 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 Examples thereof include (2 ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate (TCP), trixylenyl phosphate, cresyldiphenyl phosphate, xylenyl diphenyl phosphate and the like.

<Phosphorus component>
The refractory resin composition of the present invention preferably does not contain a phosphorus component. By not containing the phosphorus component, the water resistance of the refractory sheet formed from the refractory composition is improved. Therefore, even after long-term exposure to water, excellent expansion ratio, residual hardness, and shape retention after expansion can be ensured. Here, the phosphorus component is a compound containing a phosphorus atom, and is a above-mentioned matrix resin, a heat-expandable graphite, an inorganic filler, and an organic flame retardant, a colorant, an antioxidant, etc., which are blended as needed. It is preferable not to use a compound containing a phosphorus atom as the additive.

[Fireproof sheet]
The refractory resin composition of the present invention can be used to form a refractory sheet made of the refractory resin composition.
The expansion ratio in the thickness direction of the refractory sheet is not particularly limited, but is preferably 5 to 70 times, more preferably 10 to 60 times, still more preferably 15 to 55 times, from the viewpoint of fire resistance and water resistance. Is. It is preferable that the refractory sheet of the present invention exhibits an expansion ratio in the above range even after being immersed in water for a long time. The expansion factor is measured by the method described in the examples.

The thickness of the refractory sheet is not particularly limited, but is preferably 0.2 to 10 mm, more preferably 0.5 to 3.0 mm from the viewpoint of fire resistance and handleability.

As described above, the refractory sheet of the present invention has excellent cold resistance and is unlikely to have problems such as breakage or cracks on the surface during use. Therefore, even if the sheet is long, it is easy to handle, for example, the length. It can be used as a long product of 1 m or more.

The refractory sheet of the present invention can be manufactured, for example, as follows.
First, a predetermined amount of matrix resin, heat-expandable graphite, and inorganic filler resin, and additives such as organic flame retardants, colorants, and antioxidants, which are blended as necessary, are mixed with a kneading machine such as a kneading roll. Knead with to obtain a fire resistant resin composition.
Next, a refractory sheet can be obtained by molding the obtained refractory resin composition into a sheet by a known molding method such as press molding, calender molding, extrusion molding or the like.

The fireproof sheet can be used for various buildings such as detached houses, apartment houses, high-rise houses, high-rise buildings, commercial facilities, public facilities, various vehicles such as automobiles and trains, and various vehicles such as ships and aircraft. When a fire breaks out in a building, a vehicle, or the like, the refractory sheet expands by being heated to block the flow of air and exhibit fire extinguishing properties.
The refractory sheet is used by being attached to a member constituting the building, a vehicle, a ship, an aircraft, or the like. For example, in a building, it can be attached to windows, shoji screens, doors, doors, fittings such as bran, pillars, walls such as steel-framed concrete, floors, roofs, etc. to reduce or prevent the invasion of fire and smoke. Among these, it is preferable to use it for fittings. That is, one embodiment of the present invention also provides fittings provided with a refractory sheet.

The refractory sheet may be used as a single refractory sheet, or may be used with other members attached as appropriate. For example, the refractory sheet may be laminated with members other than the refractory sheet, or a base material may be provided on at least one surface of the refractory sheet. The base material may be a flammable 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 type or two or more types of cloth material, paper material, wood, resin film and the like. When the base material is a quasi-non-woven material layer or a non-woven material layer, examples of the material used include metal, inorganic material and the like, and more specifically, glass fiber, ceramic fiber, carbon fiber and the like. Examples thereof include woven fabrics and non-woven fabrics made of graphite fibers. Further, a composite material of these fibers and a metal may be used, and for example, aluminum glass cloth is preferable. Further, the adhesive layer may be laminated on the sheet-shaped refractory material. The pressure-sensitive adhesive layer may be provided on the base material or may be formed directly on the surface of the refractory sheet.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

[Evaluation methods]
(1) Evaporation rate Five test pieces (length 50 mm, width 50 mm, thickness 1.5 mm) prepared from the obtained fireproof sheets of Examples and Comparative Examples were immersed in 200 g of pure water, and 60. After soaking in a closed container at ° C. for 1 week, the sample was taken out, and the soaked pure water was evaporated and dried at 60 ° C. for 96 hours, and the mass of the generated precipitate was measured. Using that 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)] x 100
(2) Expansion ratio A test piece (length 100 mm, width 100 mm, thickness 1.5 mm) prepared from the obtained refractory sheet is immersed in 500 mL of pure water at 60 ° C. in a closed container for 1 week, and then the sample is prepared. I took it out. The test piece prepared 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. did. After that, the height (highest part) of the test piece is measured in width, length, and thickness, and expanded by ((thickness of test piece after heating) / (thickness of test piece before heating)). The magnification was calculated.

(3) Residual hardness The heated test piece whose expansion ratio was measured was supplied to a compression tester (“Finger Filling Tester” manufactured by Kato Tech Co., Ltd.), and a 3-point indenter with a diameter of 1 mm was used at 0.1 cm / sec. It was compressed at a rate, the maximum stress from the upper surface of the residue to 10 mm compression was measured, and the compressive strength (kgf / cm ² ) of the test piece after combustion was measured.

(4) Cold resistance (brittleness)
The evaluation was made by redeploying the refractory sheet at 0 ° C. and −20 ° C. using the wound body of the refractory sheet obtained by winding the long refractory sheet obtained in each Example and Comparative Example. In the process of unfolding, the appearance of the sheet was observed to confirm whether the surface was cracked or broken. It was evaluated according to the following evaluation criteria.
⊚: The sheet could be unfolded without cracking or breaking.
(-20 ° C)
〇: The sheet could be unfolded without cracking or breaking.
(0 ° C)
Δ: The sheet was cracked during unfolding.
(0 ° C)
X: The sheet broke during unfolding.
(0 ° C)

(Examples 1 to 27, comparative examples 1 to 4)
In the formulation shown in Tables 1 to 3 below, the matrix resin, the heat-expandable graphite, the inorganic filler, the plasticizer, and the additive are put into a roll and kneaded at 150 ° C. for 5 minutes to obtain a refractory resin composition. Obtained. The obtained refractory resin composition was press-molded at 150 ° C. for 3 minutes to obtain a refractory sheet having a thickness of 1.5 mm. The components used in each example and comparative example are as follows.

(1) Matrix resin <Chloroprene rubber: CR>
・ CR Tosoh Co., Ltd. "Y-20E"
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

<Styrene-butadiene rubber: SBR>
・ "JSR1500" manufactured by SBR JSR Corporation
Amount of bound styrene: 23.5% by mass, Mooney viscosity [ML (1 + 4) 100 ° C.]: 52
・ SBR2 "JSR0202" manufactured by JSR Corporation
Amount of bonded styrene: 46% by mass, Mooney viscosity [ML (1 + 4) 100 ° C.]: 45
・ SBR3 "JSR0122" manufactured by JSR Corporation
Amount of bound styrene: 37% by mass, Mooney viscosity [ML (1 + 4) 100 ° C.]: 52

<Styrene-butadiene-styrene copolymer: SBS>
・ "TR1086" manufactured by SBS JSR Corporation
Amount of bound styrene: 45% by mass

<Ethylene-Propene-Diene Rubber: EPDM>
・ EPDM "ENB-EPT X-3012P" manufactured by Mitsui Chemicals, Inc.

<Olefin-based thermoplastic elastomer: TPO>
・ "Milastomer 5020BS" manufactured by TPO Mitsui Chemicals, Inc.

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

(2) Plasticizer / DOP Di-2-ethylhexyl phthalate, "DOP" manufactured by J-PLUS Co., Ltd.

(3) Thermally expandable graphite / Thermally expandable graphite "CA-60N" manufactured by Air Water Inc.

(4) Inorganic filler / iron oxide: Titan Kogyo Co., Ltd. "BL-100", specific density 5.1
-Calcium carbonate: Bikita Powder Industry Co., Ltd. "Whiten BF-300", specific density 2.93
-Aluminum hydroxide: Hayashi Kasei Co., Ltd. "C-305", specific density 2.42

(5) Additives-EDAP (Ethylenediamine Phosphate) "Amgard EDAP" manufactured by Albright & Wilson

As shown in Examples, a refractory resin composition in which the total content of the heat-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. It was found that the refractory sheet formed by the above method has good fire resistance and also excellent cold resistance because the residual hardness value is high.
On the other hand, it was formed from a refractory resin composition in which the total content of the heat-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. The refractory sheet has deteriorated physical properties of at least one of fire resistance and cold resistance.

Claims (5)

It contains a matrix resin, a heat-expandable graphite, and an inorganic filler other than the heat-expandable graphite.
The total content of the heat-expandable graphite and the inorganic filler is 35% by mass or more, and the content is 35% by mass or more.
The content of the heat-expandable graphite is 15% by mass or more, and the content is 15% by mass or more.
The matrix resin contains a rubber component, and the content of the rubber component is 80% by mass or more based on the total amount of the matrix resin.
Does not contain phosphorus component
The inorganic filler contains 50% by mass or more of the inorganic filler A having a specific gravity of 2.5 or more based on the total amount of the inorganic filler.
A refractory resin composition for fittings, wherein the rubber component is a rubber component containing at least one of a halogen atom or a structural unit derived from styrene. The refractory resin composition for fittings according to claim 1, wherein the rubber component contains a rubber having an unsaturated bond. A refractory sheet for fittings comprising the refractory resin composition for fittings according to claim 1 or 2. The fireproof sheet for fittings according to claim 3, which is a long product having a length of 1 m or more. A fitting provided with the fireproof sheet for fitting according to claim 3 or 4.