JP2021063233A - Fire-resistant resin composition - Google Patents

Abstract

To provide a fire-resistant resin composition that has excellent fire retardancy and is also excellent in expansion efficiency.SOLUTION: A fire-resistant resin composition comprises a matrix component comprising a resin, an elastomer, a rubber, or a combination of them, thermally expandable graphite, and an inorganic filler. The fire-resistant resin composition comprises a zinc compound by 0.5-10 pts.wt. relative to the thermally expandable graphite of 100 pts.wt. on a metal basis, and/or a manganese compound by more than 0 pts.wt. and 0.5 pts.wt. or less relative to the thermally expandable graphite of 100 pts.wt. on a metal basis.SELECTED DRAWING: None

Description

The present invention relates to a refractory resin composition.

As a resin material having fire resistance for use in the construction field, a resin material containing heat-expandable graphite has been proposed (Patent Documents 1 to 4).

However, the refractory material using heat-expandable graphite starts to expand from the surface part where the temperature rises quickly at the time of fire and forms a heat insulating layer on the surface, so that heat is not sufficiently transferred to the inside, and as a result, the inside is sufficiently sufficient. There was a problem that it did not expand. Therefore, when viewed as a whole, the expansion efficiency is poor with respect to the amount of thermally expandable graphite, which is inferior in economic efficiency.

In a refractory material using heat-expandable graphite, there is a demand for a means for achieving an improvement in expansion efficiency, particularly an improvement in internal expansion efficiency.

Japanese Patent Application Laid-Open No. 9-227716 Japanese Patent Application Laid-Open No. 9-227747 Japanese Patent Application Laid-Open No. 10-59887 Japanese Patent Application Laid-Open No. 2000-143941

An object of the present invention is to provide a refractory resin composition having excellent expansion efficiency.

As a result of diligent studies to achieve the above object, the present inventors have solved the above-mentioned problems by assuming that the fire-resistant resin composition contains a predetermined amount of a zinc compound and / or a manganese compound. We have found what we can do and have completed the present invention.

The present invention includes the following aspects.

Item 1. In a refractory resin composition containing a resin, an elastomer, a rubber, or a matrix component which is a combination thereof, and a heat-expandable graphite and an inorganic filler.
The amount of zinc compound is 0.5 to 10 parts by weight based on 100 parts by weight of heat-expandable graphite, and / or the amount of manganese compound is 0 parts by weight based on 100 parts by weight of heat-expandable graphite. A fire-resistant resin composition containing more than parts and 0.5 parts by weight or less.

Item 2. Item 2. The refractory resin composition according to Item 1, wherein the inorganic filler contains a polyphosphate.

Item 3. Item 2. The refractory resin composition according to Item 1 or 2, further comprising a phosphate.

Item 4. Item 2. The refractory resin composition according to any one of Items 1 to 3, further comprising a plasticizer.

Item 5. The refractory resin composition according to claim 4, wherein the plasticizer is a phosphoric acid-based plasticizer.

Item 6. Item 2. The refractory resin composition according to any one of Items 1 to 5, wherein the matrix component is a vinyl chloride resin.

Item 7. A refractory resin molded product comprising the refractory resin composition according to any one of Items 1 to 6.

Item 8. A fitting provided with the refractory resin molded product according to Item 7.

According to the present invention, it is possible to provide a refractory resin composition having excellent expansion efficiency.

It is a schematic front view which shows the refractory window which provided the refractory resin molded body made from the refractory resin composition of this invention in a sash frame.

Hereinafter, embodiments of the present invention will be described.

The matrix component may be any of resin, elastomer, and rubber. Resins include thermoplastic resins and thermosetting resins.

Examples of thermoplastic resins include polypropylene resins, polyethylene resins, poly (1-) butene resins, polypentene resins, ethylene-propylene copolymers, ethylene-butene copolymer resins, and ethylene-4-methyl-1-. Penten copolymer resin, ethylene-vinyl acetate copolymer resin (EVA), polyolefin resin such as ethylene-acrylic acid copolymer, polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, polycarbonate resin, polyphenylene ether resin, Examples thereof include (meth) acrylic resins, polyamide resins, polyvinyl chloride resins (including chlorinated vinyl chloride resins), novolak resins, polyurethane resins, and synthetic resins such as polyisobutylene. Of these, polyolefin-based resins or polyvinyl chloride resins are preferable.

Any of the above thermoplastic resins may be crosslinked or modified before use as long as the fire resistance performance of the resin composition is not impaired. The method for cross-linking the resin is also not particularly limited, and examples thereof include ordinary cross-linking methods for thermoplastic resins, for example, cross-linking using various cross-linking agents and peroxides, and cross-linking by electron beam irradiation.

Examples of the thermosetting resin include epoxy resin, phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, thermosetting polyimide and the like. Of these, epoxy resin is preferable.

The epoxy resin used in the present invention is not particularly limited, but is basically obtained by reacting a monomer having an epoxy group with a curing agent. Examples of the monomer having an epoxy group include a bifunctional glycidyl ether type, a glycidyl ester type, and a polyfunctional glycidyl ether type.

These epoxy group-containing monomers may be used alone or in combination of two or more.

As the curing agent, a heavy 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 catalyst-type curing agent include tertiary amines, imidazoles, and Lewis acid complexes. The method for curing the epoxy resin is not particularly limited, and a known method can be used.

Examples of elastomers include olefin-based elastomers (TPOs), styrene-based elastomers, ester-based elastomers, amide-based elastomers, vinyl chloride-based elastomers, and combinations thereof.

Examples of rubber substances include natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, ethylene-propylene rubber, and ethylene-propire diene rubber (EPDM). ), Chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polyvulture rubber, non-vulture rubber, silicon rubber, fluororubber, urethane rubber and other rubber substances. Of these, butyl rubber is preferable.

As these synthetic resins (resins, elastomers) and / or rubber substances, one kind or two or more kinds can be used.

Among these synthetic resins and / or rubber substances, polyvinyl chloride-based resins are preferable from the viewpoint that many plasticizers can be contained and the efficiency of kneading is excellent. Further, a polyolefin resin such as ethylene-vinyl acetate copolymer resin (EVA) is also preferable from the viewpoint of excellent processability and economy.

Thermally expandable graphite is a conventionally known substance that expands when heated. Thermally expandable graphite is a powder of natural scaly graphite, thermally decomposed graphite, kiss graphite, etc., with inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, and concentrated nitric acid, perchloric acid, perchlorate, and bicarbonate , Dichromate, hydrogen peroxide and other strong oxidizing agents to produce graphite interlayer compounds. Thermally expandable graphite is a kind of crystalline compound that maintains the layered structure of carbon.

The heat-expandable graphite obtained by the acid treatment as described above may be further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound or the like. Examples of commercially available products of heat-expandable graphite include "CA-60S" manufactured by Nihon Kasei Co., Ltd., "GREP-EG" manufactured by Tosoh Co., Ltd., and "GRAFGUARD" manufactured by GRAFTECH.

The larger the particle size (particle size) of the heat-expandable graphite, the larger the expansion performance and the more preferable the fire resistance. However, the larger the particle size, the more difficult it is to disperse in the matrix, and the more time is required for kneading. From the viewpoint of expansion coefficient, the particle size of the heat-expandable graphite is preferably 100 μm or more, and more preferably 400 μm or more. The upper limit of the average particle size of the heat-expandable graphite is not particularly limited, but is preferably 1500 μm or less, and more preferably 1000 μm or less. The particle size can be controlled by using a commercially available heat-expandable graphite classified by a predetermined sieve.

The content of the heat-expandable graphite is not particularly limited, but is preferably 10 to 500 parts by weight with respect to 100 parts by weight of the matrix component, and more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the matrix component. preferable. When the content is 10 parts by weight or more, the volume expansion coefficient is large and the fireproof performance for sufficiently filling the burnt-out portion of the structure such as the sash is exhibited, and when the content is 500 parts by weight or less, the mechanical strength is maintained.

When the expanded heat insulating layer is formed, the inorganic filler increases the heat capacity and suppresses heat transfer, and also acts as an aggregate to improve the strength of the expanded heat insulating layer. The inorganic filler is not particularly limited, and for example, metal oxides such as alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; calcium hydroxide, magnesium hydroxide, and hydroxide. Hydrous inorganic substances such as aluminum and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate and barium carbonate can be mentioned.

In addition to these, as inorganic fillers, calcium salts such as calcium sulfate, gypsum fiber, and calcium silicate; silica, diatomaceous earth, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, active white clay, and sepiolite. , Imogolite, sericite, glass fiber, glass beads, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate " Examples thereof include "MOS" (trade name), lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless fiber, zinc borate, various magnetic powders, slag fiber, fly ash, and dehydrated sludge. These inorganic fillers may be used alone or in combination of two or more.

In one embodiment, the inorganic filler is selected from metal oxides, hydrous inorganics, metal carbonates, silica, and combinations thereof. Hydrous inorganic substances include alkaline earth metal hydroxides.

As the inorganic filler, a flame retardant compound (flame retardant) such as a phosphorus compound may be added. The addition of the phosphorus compound increases the strength of the expansion insulation layer and improves the fire protection performance. The phosphorus compound is not particularly limited, and for example, various phosphoric acid esters such as red phosphorus; triphenyl phosphate, tricresyl phosphate (TCP), trixylenyl phosphate, cresildiphenyl phosphate, xylenyl diphenyl phosphate; phosphorus; Metal phosphates such as sodium phosphate, potassium phosphate, magnesium phosphate and the like; compounds represented by the following chemical formula (1) and the like can be mentioned.

In the chemical formula (1), it represents R ¹ and R ³ , hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms. R ² is a hydroxyl group and has 1 to 16 carbon atoms.
Represents a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or an aryloxy group having 6 to 16 carbon atoms.

As the red phosphorus, commercially available red phosphorus can be used, but from the viewpoint of moisture resistance and safety such as not spontaneously igniting during kneading, those in which the surface of the red phosphorus particles is coated with a resin are preferably used.

The compound represented by the chemical formula (1) is not particularly limited, and for example, methylphosphonate, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonate, propylphosphonate, butylphosphonic acid, 2-methylpropylphosphonate, t- Butylphosphonic acid, 2,3-dimethyl-butylphosphonate, octylphosphonate, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphonate, methylethylphosphonate, methylpropylphosphinic acid, diethylphosphonate, dioctylphosphonate, phenylphosphine Acids, diethylphenylphosphonates, diphenylphosphonates, bis (4-methoxyphenyl) phosphonates and the like can be mentioned. Among them, t-butylphosphonic acid is preferable in terms of high flame retardancy, although it is expensive. The above phosphorus compounds may be used alone or in combination of two or more.

Alternatively, it may be a salt of primary phosphoric acid, secondary phosphoric acid, tertiary phosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, etc., which are lower phosphoric acids. In the present specification, the salt includes alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt, other metal salts such as aluminum salt; ammonium salt and the like.

The particle size of the inorganic filler is preferably 0.5 to 200 μm, more preferably 1 to 10 μm. When the amount of the inorganic filler added is small, the dispersibility greatly affects the performance, so that the inorganic filler has a small particle size, but when it is 0.5 μm or more, the dispersibility is good. When the amount added is large, the viscosity of the resin composition increases and the moldability decreases as the high filling progresses, but the viscosity of the resin composition can be decreased by increasing the particle size. A particle having a large diameter is preferable, but a particle size of 100 μm or less is desirable from the viewpoint of the surface properties of the molded product and the mechanical properties of the resin composition.

Further, in order to obtain a desired particle size, it is also possible to control by adding, sieving or the like after the aggregated inorganic filler is finely dispersed or dispersed with a solvent or the like.

Examples of the inorganic filler include "Heidilite H-31" (manufactured by Showa Denko Co., Ltd.) having a particle size of 18 μm for aluminum hydroxide, "B325" (manufactured by ALCOA) having a particle size of 25 μm, and calcium carbonate having a particle size. Examples thereof include 1.8 μm “Whiten SB Red” (manufactured by Bikita Powder Industry Co., Ltd.) and “BF300” (manufactured by Bikita Powder Industry Co., Ltd.) having a particle size of 8 μm.

The content of the inorganic filler is not particularly limited, but is preferably 30 to 500 parts by weight with respect to 100 parts by weight of the matrix component. When the content is 30 parts by weight or more, sufficient fire protection performance is obtained, and when it is 500 parts by weight or less, the mechanical strength is maintained. The content of the inorganic filler is more preferably 40 to 350 parts by weight.

When the phosphorus compound is contained as the inorganic filler, the content of the phosphorus compound is not particularly limited, but is preferably 30 to 300 parts by weight with respect to 100 parts by weight of the matrix component. When the blending amount is 30 parts by weight or more, the effect of improving the strength of the expanded heat insulating layer is sufficient, and when it is 300 parts by weight or less, the mechanical strength is maintained. The content of the phosphorus compound is more preferably 40 to 250 parts by weight.

In a preferred embodiment of the refractory resin composition of the present invention, the particle size ratio of the particle size of the heat-expandable graphite to the particle size of the inorganic filler is 1 to 1000. It is preferably 3 to 300, more preferably 5 to 50. By setting such a numerical range, kneading can be performed efficiently in a short time. Further, if the particle size ratio is out of the range, the dispersion of expanded graphite in the matrix becomes insufficient, which may cause problems such as surface contamination.

Further, in a preferred embodiment of the refractory resin composition of the present invention, the total content of the heat-expandable graphite and the inorganic filler is 30% by weight or more, preferably 50% by weight or more. The upper limit of the total content of the heat-expandable graphite and the inorganic filler is not particularly limited, but is 75% by weight or less, preferably 65% by weight or less. By setting such a numerical range, excellent fire resistance can be exhibited.

Further, in a preferred embodiment of the refractory resin composition of the present invention, the content of the heat-expandable graphite is 15% by weight or more, preferably 20% by weight or more, and particularly preferably 25% by weight or more. The upper limit of the content of the heat-expandable graphite is not particularly limited, but is 50% by weight or less and 40% by weight or less. By setting such a numerical range, excellent fire resistance can be exhibited.

The refractory resin composition of the present invention has a zinc compound as a metal amount of 0.1 to 7.5 parts by weight with respect to 100 parts by weight of heat-expandable graphite, or a manganese compound as a metal amount and is thermally expanded. It contains more than 0 parts by weight and 0.5 parts by weight or less with respect to 100 parts by weight of graphite.

Examples of the zinc compound include zinc salts, oxides and hydroxides. Specific examples thereof include, but are not limited to, zinc oxide (zinc white), zinc stearate, zinc borate, zinc chloride, zinc sulfide, zinc chromate, zinc phosphate, zinc stannate, and the like.

Examples of the manganese compound include manganese salts, oxides and hydroxides. Specifically, manganese dioxide, manganese chloride, manganese sulfate, manganese nitrate, potassium permanganate and the like are exemplified.

When producing the fire-resistant resin composition of the present invention, zinc compounds and / or manganese compounds contained in raw materials and reaction reagents may be unintentionally mixed. Unless otherwise specified, the "zinc compound" and "manganese compound" in the fire-resistant resin composition of the present invention include zinc contained in the fire-resistant resin composition including those unintentionally mixed. Refers to compounds and manganese compounds.

The zinc compound is contained as a metal amount in an amount of 0.5 to 10 parts by weight with respect to 100 parts by weight of the heat-expandable graphite. The content of the zinc compound is preferably 0.5 to 5 parts by weight, more preferably 1.0 to 3.0 parts by weight with respect to 100 parts by weight of the heat-expandable graphite. The zinc compound may be contained in an amount of 0.1 to 7.5 parts by weight with respect to 100 parts by weight of the heat-expandable graphite as a metal amount.

The manganese compound is contained as a metal amount in an amount of more than 0 parts by weight and 0.5 parts by weight or less with respect to 100 parts by weight of the heat-expandable graphite. The content of the manganese compound is preferably 0.3 parts by weight or less with respect to 100 parts by weight of the heat-expandable graphite. The content of the manganese compound may be at least the measurement limit value. The lower limit of the content of the manganese compound is more than 0 parts by weight, preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more with respect to 100 parts by weight of the heat-expandable graphite. If it is contained in excess of the specified amount, the residual shape retention during combustion will be reduced.

The content of the zinc compound and / or the manganese compound in the fire-resistant resin composition as a metal amount is such that a fire-resistant resin molded body (for example, a sheet) made of the fire-resistant resin composition is subjected to heating-type sealed acid decomposition by microscopy. After being ionized, it can be quantified by high frequency inductively coupled plasma emission spectroscopy (ICP emission spectroscopy).

The content of the heat-expandable graphite contained in the refractory resin composition is determined by dissolving the sample in an organic solvent, water, etc., extracting the insoluble component containing the expanded graphite, ashing at a predetermined temperature, and ashing the ash. Measurement is possible due to the difference in the weight of the product.

In the refractory resin composition, 0.1 to 7.5 parts by weight of the zinc compound as a metal amount with respect to 100 parts by weight of the heat-expandable graphite, or the manganese compound as the metal amount of the heat-expandable graphite 100 By setting the amount to more than 0 parts by weight and 0.5 parts by weight or less with respect to the parts by weight, it is possible to improve the expansion efficiency, particularly the improvement of the expansion efficiency inside. If it is contained in excess of the specified amount, the residual shape retention during combustion will be reduced.

The refractory resin composition of the present invention may further contain a polyphosphate salt.

The polyphosphate functions as a flame retardant and contains ammonium polyphosphate, melamine polyphosphate, melam polyphosphate and the like. Examples of commercially available products of ammonium polyphosphate include "AP422" and "AP462" manufactured by Clariant, "Sumisafe P" manufactured by Sumitomo Chemical Co., Ltd., and "Terage C60" manufactured by Chisso.

A preferred ammonium polyphosphate is surface-coated ammonium polyphosphate (also referred to as coated ammonium polyphosphate). Among the coated ammonium polyphosphates, the melamine-coated ammonium polyphosphate surface-coated with melamine is described in JP-A-9-286875. A silane-coated ammonium polyphosphate surface-coated with silane is described in JP-A-2000-63562. The melamine-coated ammonium polyphosphate is (a) melamine-coated ammonium melamine-coated ammonium with melamine added and / or adhered to the surface of powdered ammonium polyphosphate particles, and (b) melamine molecules present in the coating layer of the melamine-coated ammonium polyphosphate particles. Coated ammonium polyphosphate whose particle surface is crosslinked by the active hydrogen contained in the amino group and a compound having a functional group capable of reacting with the active hydrogen, and / or (c) powdered ammonium polyphosphate or the melamine. Coated ammonium polyphosphate Coated ammonium polyphosphate whose surface is coated with a thermosetting resin. Commercially available products of melamine-coated ammonium polyphosphate particles include, for example, "AP462" manufactured by Clariant AG, "FR CROS 484" manufactured by Budenheim Ibica, and "FR".
CROS 487 "and the like. Examples of commercially available products of silane-coated ammonium polyphosphate particles include "FR CROS 486" manufactured by Budenheim Ibica.

The average particle size of the coated ammonium polyphosphate is preferably 15 to 35 μm. The average particle size of the coated ammonium polyphosphate can be measured by laser diffraction type particle size distribution measurement.

The refractory resin composition of the present invention may further contain a plasticizer. The plasticizer is added to adjust the melt viscosity of the matrix components, especially the thermoplastic resin. The plasticizer can also be rephrased as a softener. As the plasticizer, one kind or a combination of two or more kinds of plasticizers exemplified below may be used:
Di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diun decyl phthalate (DUP), or higher alcohols or mixed alcohols with about 10 to 13 carbon atoms. Phthalate-based plasticizers such as phthalates;
Aliphatic dibasic acids such as di-2-ethylhexyl adipate, di-n-octyl adipate, di-n-decyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate Ester-based plasticizer;
Trimerits such as tri-2-ethylhexyl trimerite (TOTM), tri-n-octyl trimerite, tridecyl trimerite, triisodecyl trimerite, di-n-octyl-n-decyl trimerilate, etc. Acid ester plasticizer;
Adipate ester plasticizers such as di-2-ethylhexyl adipate (DOA) and diisodecyl adipate (DIDA);
Sebacate ester-based plasticizers such as dibutyl sebacate (DBS) and di-2-ethylhexyl sebacate (DOS);
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 and other phosphate ester plasticizers;
Biphenyltetracarboxylic diantetraalkyl ester plasticizers such as 2,3,3', 4'-biphenyltetracarboxylic diantetraheptyl ester;
Polyester polymer plasticizer;
Epoxy-based plasticizers such as epoxidized soybean oil, epoxidized flaxseed oil, epoxidized cottonseed oil, and liquid epoxy resin;
Chlorinated paraffin;
Chlorinated fatty acid esters such as alkyl pentachloride stearic acid; and process oils such as paraffinic process oils, naphthenic process oils and aromatic process oils.

The content of the plasticizer in the refractory resin composition is not particularly limited, but is preferably in the range of 25 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

Further, to the fire-resistant resin composition of the present invention, a heat stabilizer, a lubricant, a processing aid, a pyrolysis foaming agent, an antioxidant, an antistatic agent, a pigment and the like are added as long as the physical properties are not impaired. You may.

Examples of the heat stabilizer include lead heat stabilizers such as lead tribasic lead sulfate, lead tribasic sulfite, lead dibasic lead phosphate, lead stearate, and lead dibasic stearate; organic tin mercapto and organic. Organic tin heat stabilizers such as tin malate, organic tin laurate, and dibutyltin malate; metal soap heat stabilizers such as zinc stearate and calcium stearate, etc., which may be used alone or in combination of two or more. It may be used together.

Examples of the lubricant include waxes such as polyethylene, paraffin and montanic acid; various ester waxes; organic acids such as stearic acid and ricinolic acid; organic alcohols such as stearyl alcohol; and amide compounds such as dimethylbisamide. , These may be used alone or in combination of two or more.

Examples of the processing aid include chlorinated polyethylene, methyl methacrylate-ethyl acrylate copolymer, high molecular weight polymethyl methacrylate and the like.

Examples of the pyrolytic foaming agent include azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), p, p-oxybisbenzenesulfonylhydrazide (OBSH), azobisisobutyronitrile (AIBN) and the like. Can be mentioned.

The refractory resin composition of the present invention can be obtained by melt extrusion with an extruder such as a single-screw extruder or a twin-screw extruder according to a conventional method to obtain a refractory resin molded product. The melting temperature varies depending on the matrix component and is not particularly limited, but is, for example, 130 to 170 ° C. in the case of a polyvinyl chloride resin.

The fire-resistant resin composition or fire-resistant resin molded product of the present invention imparts fire resistance to structures such as windows, shoji screens, doors (that is, doors), doors, bran, and balustrades; ships; and elevators. Can be used for. Since the refractory resin composition of the present invention has excellent moldability, it is possible to easily obtain a deformed molded product adapted to the complicated shape of the structure. FIG. 1 is an example in which the refractory resin molded body 4 of the present invention is applied to the sash frame of the window 1 as a fitting. In this example, the sash frame has two inner frames 2 and one outer frame 3 surrounding the inner frame 2, and the inner frame 2 is along each side of the inner frame 2 and the frame body of the outer frame 3. A fire-resistant resin molded body 3 is attached to the inside of the outer frame 3. By providing the refractory resin molded product 3 of the present invention in this way, it is possible to impart fire resistance to the window 1.

Further, since the refractory resin composition of the present invention is excellent in expandability inside, it can be used as an intermediate layer of a refractory material made of a laminated body. Specifically, a refractory material formed by laminating the fire-resistant resin composition of the present invention between the non-combustible material layer on the front surface and the non-combustible material layer on the back surface (for example, Patent No. 5979990).
Can be mentioned.

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

1. 1. Creation of refractory sheet [Example 1]
In the blending amount shown in Table 1, 100 parts by weight of polyvinyl chloride as a synthetic resin, 100 parts by weight of diisodecyl phthalate (DIDP) as a plasticizer, 100 parts by weight of heat-expandable graphite (“GREP-EG” manufactured by Tosoh Corporation), inorganic. As a filler, 100 parts by weight of calcium carbonate and 0.1 part by weight of manganese dioxide were mixed at 130 ° C. with a kneader. After mixing, the mixture was molded into a sheet with a calendar roll to obtain a refractory sheet as a refractory resin molded body having a width of 150 mm, a thickness of 1.5 mm, and a length of 50 cm.
[Examples 2 to 20, Comparative Example 1]
In Examples 2 to 20 and Comparative Example 1, the components were mixed and extruded in the blending amounts shown in Tables 1 to 3 to obtain a refractory sheet.

2. Measurement of Expansion Magnification of Refractory Sheet A test piece (length 100 mm, width 100 mm, thickness 1.5 mm) prepared from the obtained refractory sheet is supplied to an electric furnace, heated at 600 ° C. for 30 minutes, and then the test piece is subjected to. The thickness was measured, and (thickness of the test piece after heating) / (thickness of the test piece before heating) was calculated as the expansion ratio.

The refractory sheets of Examples 1 to 20 have excellent expandability.

Claims (8)

In a refractory resin composition containing a resin, an elastomer, a rubber, or a matrix component which is a combination thereof, and a heat-expandable graphite and an inorganic filler.
The amount of zinc compound is 0.5 to 10 parts by weight based on 100 parts by weight of heat-expandable graphite, and / or the amount of manganese compound is 0 parts by weight based on 100 parts by weight of heat-expandable graphite. A fire-resistant resin composition containing more than parts and 0.5 parts by weight or less. The refractory resin composition according to claim 1, wherein the inorganic filler contains a polyphosphate. The refractory resin composition according to claim 1 or 2, further comprising a phosphate. The refractory resin composition according to any one of claims 1 to 3, further comprising a plasticizer. The refractory resin composition according to claim 4, wherein the plasticizer is a phosphoric acid-based plasticizer. The refractory resin composition according to any one of claims 1 to 5, wherein the matrix component is a vinyl chloride resin. A refractory resin molded product comprising the refractory resin composition according to any one of claims 1 to 6. A fitting provided with the refractory resin molded product according to claim 7.

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