JP6859390B2 - Refractory resin composition - Google Patents

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, in the case of a fireproof material containing heat-expanded graphite, if the processing time is not shortened, the components in the heat-expanded graphite will be removed and the expansion ratio will decrease, so that the processing time needs to be shortened. On the other hand, refractory materials often contain a large amount of inorganic fillers and flame-retardant materials in addition to heat-expanded graphite, and it is necessary to knead them well in order to mix them with the binder resin, and kneading is insufficient. The refractory material becomes brittle, the surface becomes dirty (powder is blown and blackened), and handling is hindered. In addition, the refractory performance may vary depending on the sampling position of the refractory material.

Even if the kneading is insufficient, it has been proposed to solve the problem by laminating such as sandwiching between non-woven fabrics, but it is not always satisfactory due to cost increase and wrinkles.

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 little variation in refractory resistance and excellent surface finish and strength.

In order to achieve the above object, the present inventor added at least one substance selected from chlorinated polyolefin and acrylic polymer to 1 part by mass of heat-expandable graphite in a fire-resistant resin composition. It has been found that the above problem can be solved by including the mixture in a ratio of 02 to 1 part by mass, and the present invention has been completed.

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, a heat-expandable graphite, and an inorganic filler.
A refractory characterized by containing at least one selected from the group consisting of polymethylmethacrylate, modified polymethylmethacrylate and chlorinated polyethylene at a ratio of 0.02 to 1 part by mass with respect to 1 part by mass of thermally expandable graphite. Sex resin composition.

Item 2. Item 2. The fire-resistant resin composition according to Item 1, wherein the substance is at least one selected from the group consisting of chlorinated polyethylene, a methacrylic acid ester copolymer, and a modified product of the methacrylic acid ester copolymer. ..

Item 3. Item 2. The refractory resin composition according to Item 1 or 2, wherein the weight average molecular weight of the substance is 100,000 or more.

Item 4. Item 2. The refractory resin composition according to any one of Items 1 to 3, which contains phosphate as the inorganic filler.

Item 5. The refractory resin composition according to any one of Items 1 to 4, further comprising a polyphosphate.

Item 6. The refractory resin composition according to any one of Items 1 to 5, further comprising a plasticizer.

Item 7. Item 2. The refractory resin composition according to any one of Items 1 to 6, wherein the matrix component is a vinyl chloride resin.

Item 8. A refractory resin molded product comprising the refractory resin composition according to any one of Items 1 to 7.

Item 9. A fitting provided with the refractory resin molded product according to Item 8.

According to the present invention, there is provided a refractory resin composition having little variation in refractory resistance and excellent surface finish and strength.

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 the thermoplastic resin include polypropylene resin, polyethylene resin, poly (1-) butene resin, polypentene resin, ethylene-propylene copolymer, ethylene-butene copolymer resin, and ethylene-4-methyl-1-pentene. Polymer 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, (meth) ) Synthetic resins such as acrylic resin, polyamide resin, polyvinyl chloride resin, novolak resin, polyurethane resin and polyisobutylene can be mentioned.

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 synthetic resins such as polyurethane, polyisocyanurate, polyisocyanurate, phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, and polyimide. 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 the elastomer include olefin-based elastomers, styrene-based elastomers, ester-based elastomers, amide-based elastomers, vinyl chloride-based elastomers, and combinations thereof.

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, chlorosulfonated polyethylene, acrylic rubber. , Epichlorohydrin rubber, polyvulverable rubber, non-vulverable rubber, silicon rubber, fluororubber, urethane rubber and other rubber substances. Of these, butyl rubber is preferable.

One or more of these resins, elastomers, and / or rubber substances can be used.

Among these resins, elastomers, and / or rubber substances, polyvinyl chloride-based resins and polyolefin resins (for example, ethylene-vinyl acetate copolymers) are preferable from the viewpoint of dispersibility of expanded graphite in matrix resins.

The heat-expandable graphite is a conventionally known substance and has a property of expanding when heated. Powders such as natural scaly graphite, thermally decomposed graphite, and kiss graphite are mixed with inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, and concentrated nitric acid, perchloric acid, perchlorate, permanganate, and dichromate. A graphite interlayer compound is produced by treating with a strong oxidizing agent such as perchlorate or hydrogen peroxide, and is a kind of crystalline compound while maintaining a 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.

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 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 mass with respect to 100 parts by mass of the matrix component, and 50 parts by mass with respect to 100 parts by mass of the matrix component.
More preferably, it is ~ 300 parts by mass. When the content is 10 parts by mass 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 it is 500 parts by mass 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, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; calcium hydroxide, magnesium hydroxide. Hydrous inorganic substances such as aluminum hydroxide and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc 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, 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 carbon. Represents an aryloxy group of number 6-16.

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 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) with a particle size of 18 μm for aluminum hydroxide, "B325" (manufactured by ALCOA) with a particle size of 25 μm, and calcium carbonate. 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 mass with respect to 100 parts by mass of the matrix component. When the content is 30 parts by mass or more, sufficient fire protection performance is obtained, and when it is 500 parts by mass or less, the mechanical strength is maintained. The content of the inorganic filler is more preferably 40 to 350 parts by mass.

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 mass with respect to 100 parts by mass of the matrix component. When the blending amount is 30 parts by mass or more, the effect of improving the strength of the expanded heat insulating layer is sufficient, and when it is 300 parts by mass or less, the mechanical strength is maintained. The content of the phosphorus compound is more preferably 40 to 250 parts by mass.

Among the inorganic fillers, specific examples of aluminum hydroxide include, for example, "Heidilite H-31" (manufactured by Showa Denko Co., Ltd.) having a particle size of 18 μm and "B325" (manufactured by ALCOA) having a particle size of 25 μm. Calcium carbonate includes "Whiten SB Red" (manufactured by Bikita Powder Industry Co., Ltd.) with a particle size of 1.8 μm, "BF300" (manufactured by Bikita Powder Industry Co., Ltd.) with a particle size of 8 μm, and the like.

In one of the preferred embodiments 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 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 is insufficient, and problems such as surface contamination occur.

Further, in one of the preferred embodiments of the refractory resin composition of the present invention, the total content of the heat-expandable graphite and the inorganic filler is 30% by mass or more. It is preferably 50% by mass or more. By setting such a numerical range, excellent fire resistance can be exhibited.

Further, in one of the preferred embodiments of the refractory resin composition of the present invention, the content of the heat-expandable graphite is 15% by mass or more, preferably 20% by mass or more, and more preferably 25% by mass or more. By setting such a numerical range, excellent fire resistance can be exhibited.

The refractory resin composition of the present invention contains one or more substances selected from chlorinated polyolefins and acrylic polymers (hereinafter, may be referred to as "component (A)").

It is considered that by containing the component A, the component (A) interacts with both the matrix resin and the heat-expandable graphite, and the heat-expandable graphite can be efficiently dispersed in the matrix resin in a short time. ..

Examples of the chlorinated polyolefin include chlorinated polyethylene, chlorinated polypropylene, and chlorinated EVA. When the matrix resin is a polyvinyl chloride-based resin, dispersibility by chlorinated polyolefin is particularly preferable.

Acrylic polymers include acrylic acid esters such as acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, -2-ethylhexyl acrylate, and ethyl methacrylate, n-butyl methacrylate, It is a group of polymers composed of a copolymer containing at least one of methacrylic acid esters such as -2-ethylhexyl methacrylate as a main component.

Among acrylic polymers, a methacrylate copolymer is desirable from the viewpoint of dispersion effect.

As a methacrylate copolymer, the general formula,
(CH ₂ C (CH ₃ ) COOCH ₃ ) _n- (CH ₂ CHCOOR)
(In the formula, R is an alkyl group)
Or
{CH ₂ C (CH ₃ ) COOCH ₃ )-(CH ₂ CHCOOR)} _n
(In the formula, R is an alkyl group)
Can be mentioned.

Examples of the former include α-methylstyrene-acrylonitrile copolymer (Mitsubishi Rayon Metabrene H-605), methyl methacrylate-maleimide copolymer (Mitsubishi Rayon Metabrene H-630), and the latter (alkyl acrylate copolymer). Examples of the coalescence) include Mitsubishi Rayon Polymer P530 and Metabren P551.

Examples of the modified polymethyl methacrylate include acid-modified polymethyl methacrylate with maleic anhydride and the like. Examples thereof include a metal acrylate polytetrafluoroethylene resin (Mitsubishi Rayon Co., Ltd. A-3000).

In the present invention, it is preferable to use at least one selected from the group consisting of chlorinated polyethylene, a methacrylic acid ester copolymer, and a modified product of the methacrylic acid ester copolymer as the component (A).

The molecular weight of the component (A) is not particularly limited, but the mass average molecular weight is preferably 100,000 or more, and more preferably 1,000,000 or more.

The ratio of the mass of the component (A) to the heat-expandable graphite is 0.02 to 1 part by mass of the component (A) with respect to 1 part by mass of the heat-expandable graphite. The lower limit is preferably 0.03 parts by mass. The upper limit is preferably 0.5 parts by mass.

Further, two or more kinds of the component (A) can be used in combination, and in that case, the dispersion effect can be further improved.

Although not binding the present invention, in the refractory resin composition of the present invention, the component (A) functions as a dispersant for the heat-expandable graphite, so that the heat-expandable graphite is dispersed even by kneading for a short time. Is not insufficient, and it is considered that a good surface finish can be achieved.

As an embodiment of the component (A), polymethylmethacrylate (PMMA) having a weight average molecular weight of 1,000,000 or more can be used. It is preferable to use PMMA having a weight average molecular weight of 1,000,000 or more because the pseudo-crosslink points are increased and the strength of the molded product obtained from the refractory resin composition is improved.

As one embodiment of polymethylmethacrylate, PMMA having a weight average molecular weight of less than 1,000,000 can be used. It is preferable to use PMMA having a weight average molecular weight of less than 1,000,000 because the gelation rate of the refractory resin composition is improved.

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 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 preferable 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. The 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. Examples of commercially available products of melamine-coated ammonium polyphosphate particles include "AP462" manufactured by Clariant AG, "FR CROS 484" and "FR CROS 487" manufactured by Budenheim Ibica. 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 plasticizers such as epoxidized soybean oil, epoxidized linseed 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 mass with respect to 100 parts by mass 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. May be good.

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 the fire-resistant resin molded product of the present invention is used to impart fire resistance to structures such as windows, shoji screens, doors (that is, doors), doors, bran, and columns; ships; and structures such as elevators. Can be used. 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 attached 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 refractory 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.

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 mass of polyvinyl chloride as a synthetic resin (matrix component), 6 parts by mass of polymethylmethacrylate (PMMA), 80 parts by mass of diisodecyl phthalate (DIDP) as a plasticizer, and 100 parts of thermosetting graphite. After mixing 50 parts by mass, 50 parts by mass of ammonium polyphosphate, and 50 parts by mass of calcium carbonate as an inorganic filler with a kneader, the mixture is molded into a sheet with a calendar roll, and has a width of 150 mm, a thickness of 1.5 mm, and a length. A fire-resistant sheet as a fire-resistant resin molded product having a length of 5 m was obtained. In addition, the kneading time in the kneader was unified to 5 minutes after the graphite was added, and the test was conducted.
[Examples 2-36, Comparative Examples 1-2]
In Examples 2 to 36 and Comparative Examples 1 and 2, the components were mixed and extruded in the blending amounts shown in Table 1 to obtain a refractory sheet.

2. Measurement of fire resistance (expansion ratio) From the obtained fire resistance sheet, the first part in the length direction (0 to 1 m with one end as 0 m), the center part (2.5 m in the length direction), and the part of 4 to 5 m. The prepared test pieces (length 100 mm, width 100 mm, thickness 1.5 mm) were placed in a predetermined holder, supplied to an electric furnace, heated at 600 ° C. for 30 minutes, and then the thickness of each test piece. Was measured, and (thickness of the test piece after heating) / (thickness of the test piece before heating) was calculated as the expansion ratio. The difference between the minimum value and the maximum value of the sample prepared from 3 places varies within 5% of the average value of the expansion ratio of 3 places ◎, those within 10% ○, those exceeding 10% × And said.

3. 3. Evaluation of surface finish of the refractory sheet The surface finish of the obtained refractory sheet was evaluated by visually confirming the surface roughness (presence or absence of wrinkles). The definition of wrinkles was defined as a size of 3 mm or more. In the prepared sheet having a width of 15 cm × 500 cm, if the number of wrinkles was 4 or less, it was evaluated as ◯, and if it was 5 or more, it was evaluated as ×.

◯: No wrinkles on the surface of the preparation sheet or no wrinkles of 3 mm or more in 4 places ×: 5 or more wrinkles of 3 mm or more on the surface of the preparation sheet 4. Evaluation of strength The breaking strength of the obtained refractory sheet was measured, the measuring method was based on JIS K 7161, and the tensile strength in the flow direction of the roll was measured. Those that were not strained at 110% were marked with ◯, and those that were broken were marked with x.

Claims (6)

In a refractory resin composition containing a resin, an elastomer, a rubber, or a matrix component which is a combination thereof, a plasticizer, a heat-expandable graphite, and an inorganic filler.
The matrix component contains a thermoplastic resin and
The plasticizer is contained in a ratio of 25 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
A refractory resin composition comprising at least one substance selected from a chlorinated polyolefin and an acrylic polymer at a ratio of 0.02 to 0.5 parts by mass with respect to 1 part by mass of heat-expandable graphite. Stuff. The fire-resistant resin composition according to claim 1, wherein the substance is at least one selected from the group consisting of chlorinated polyethylene, a methacrylic acid ester copolymer, and a modified product of the methacrylic acid ester copolymer. Stuff. The refractory resin composition according to claim 1 or 2, wherein the inorganic filler contains phosphate. The refractory resin composition according to any one of claims 1 to 3, further comprising a polyphosphate. A refractory resin molded product comprising the refractory resin composition according to any one of claims 1 to 4. A fitting provided with the refractory resin molded product according to claim 5.

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