Fire-resistant resin composition

Abstract

To provide a fire-resistant resin composition excellent in flame retardancy, surface finish and strength.SOLUTION: A fire-resistant resin composition comprising a matrix component which is a resin, an elastomer, a rubber, or a combination thereof, a thermally expandable graphite, and an inorganic filler, wherein the particle size ratio of the particle size of the thermally expandable graphite to the particle size of the inorganic filler is in the range of 1 to 1000, the total content of the thermally expandable graphite and the inorganic filler is 30% by weight or more, and the content of the thermally expandable graphite is 5% by weight or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a fire-resistant resin composition. [Background technology]

[0002] Resin materials containing thermally expandable graphite have been proposed as fire-resistant resin materials for use in the construction field (Patent Documents 1 to 4).

[0003] However, refractory materials containing thermally expandable graphite require a shorter processing time, as otherwise the components within the thermally expandable graphite will be removed, resulting in a decrease in the expansion ratio. On the other hand, refractory materials often contain large amounts of inorganic fillers and flame retardants in addition to the thermally expandable graphite, and thorough mixing is required to incorporate these into the binder resin. Insufficient mixing can result in problems such as the refractory material becoming brittle, its surface becoming dirty (powdery or blackening), and handling difficulties. Furthermore, variations in fire resistance performance can occur depending on the sampling position of the refractory material. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 9-227716 [Patent Document 2] Patent Publication No. 9-227747 [Patent Document 3] Patent Publication No. 10-95887 [Patent Document 4] Patent Publication No. 2000-143941 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a fire-resistant resin composition which has excellent expansibility, stably exhibits fire resistance, and is also excellent in surface finish and strength. [Means for solving the problem]

[0006] In order to achieve the above object, the present inventors have found that the above problems can be solved by making the particle size ratio of the thermally expandable graphite to the inorganic filler in a fire-resistant resin composition from 1 to 1000, making the total content of the thermally expandable graphite and the inorganic filler 30% by weight or more, and making the content of the thermally expandable graphite 5% by weight or more, and have completed the present invention.

[0007] The present invention includes the following aspects.

[0008] Item 1. A fire-resistant resin composition containing a matrix component which is a resin, an elastomer, a rubber, or a combination thereof, thermally expandable graphite, and an inorganic filler, A fire-resistant resin composition characterized in that the particle size ratio of the thermally expandable graphite to the inorganic filler is in the range of 1 to 1000, the total content of the thermally expandable graphite and the inorganic filler is 30% by weight or more, and the content of the thermally expandable graphite is 15% by weight or more.

[0009] Item 2: A fire-resistant resin composition containing a matrix component that is a resin, an elastomer, a rubber, or a combination thereof, thermally expandable graphite, and an inorganic filler, A fire-resistant resin composition characterized in that the particle size ratio of the thermally expandable graphite to the inorganic filler is in the range of 1 to 1000, the total content of the thermally expandable graphite and the inorganic filler is 30% by weight or more, and the content of the thermally expandable graphite is 5% by weight or more.

[0010] Item 3. The fire-resistant resin composition according to Item 1 or 2, wherein the thermally expandable graphite has an average particle size of 100 μm or more.

[0011] Item 4. The fire-resistant resin composition according to any one of Items 1 to 3, wherein the inorganic filler contains a phosphite.

[0012] Item 5. The fire-resistant resin composition according to any one of Items 1 to 4, further comprising a polyphosphate.

[0013] Item 6. The fire-resistant resin composition according to any one of Items 1 to 5, further comprising a plasticizer.

[0014] Item 7. The fire-resistant resin composition according to any one of Items 1 to 6, wherein the matrix component is a vinyl chloride resin or a polyolefin resin.

[0015] Item 8. A fire-resistant resin molded article made from the fire-resistant resin composition according to any one of items 1 to 7.

[0016] Item 9. A fitting comprising the fire-resistant resin molding according to item 8. [Effects of the Invention]

[0017] According to the present invention, there is provided a fire-resistant resin composition which is excellent in flame retardancy, surface finish and strength. [Brief explanation of the drawings]

[0018] [Figure 1] 1 is a schematic front view showing a fire-resistant window having a sash frame provided with a fire-resistant resin molded article made of the fire-resistant resin composition of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0019] Hereinafter, an embodiment of the present invention will be described.

[0020] The matrix component may be any of resins, elastomers, and rubbers, including thermoplastic and thermosetting resins.

[0021] Examples of thermoplastic resins include polyolefin resins such as polypropylene resin, polyethylene resin, poly(1-)butene resin, polypentene resin, ethylene-propylene copolymer, ethylene-butene copolymer resin, ethylene-4-methyl-1-pentene copolymer resin, ethylene-vinyl acetate copolymer resin (EVA), and ethylene-acrylic acid copolymer; and synthetic resins such as polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, polycarbonate resin, polyphenylene ether resin, (meth)acrylic resin, polyamide resin, polyvinyl chloride resin (PVC), chlorinated polyvinyl chloride resin (CPVC), novolac resin, polyurethane resin, and polyisobutylene.

[0022] Any of the above thermoplastic resins may be crosslinked or modified to the extent that the fire resistance of the resin composition is not impaired. The method for crosslinking the resin is not particularly limited, and examples thereof include ordinary crosslinking methods for thermoplastic resins, such as crosslinking using various crosslinking agents or peroxides, and crosslinking by electron beam irradiation.

[0023] Examples of thermosetting resins include synthetic resins such as polyurethane, polyisocyanate, polyisocyanurate, phenolic resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, polyimide, etc. Among these, epoxy resin is preferred.

[0024] 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 difunctional glycidyl ether type, glycidyl ester type, and polyfunctional glycidyl ether type monomers.

[0025] These epoxy group-containing monomers may be used alone or in combination of two or more.

[0026] The curing agent used may be a polyaddition type or a catalyst type. Examples of polyaddition type curing agents include polyamines, acid anhydrides, polyphenols, and polymercaptans. Examples of catalyst type curing agents include tertiary amines, imidazoles, and Lewis acid complexes. The method for curing the epoxy resin is not particularly limited, and can be performed by a known method.

[0027] Examples of the elastomer include olefin elastomers (TPO), styrene elastomers, ester elastomers, amide elastomers, vinyl chloride elastomers, and combinations thereof.

[0028] Examples of rubber materials 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, ethylene-propylene-diene rubber (EPDM), chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, multi-vulcanized rubber, non-vulcanized rubber, silicone rubber, fluororubber, urethane rubber, etc. Of these, butyl rubber is preferred.

[0029] These synthetic resins and / or rubber materials can be used singly or in combination of two or more.

[0030] Among these synthetic resins and / or rubber materials, polyvinyl chloride resins such as polyvinyl chloride resin and chlorinated polyvinyl chloride resin are preferred because they can contain a large amount of plasticizer and have excellent kneading efficiency. Also preferred are polyolefin resins such as ethylene-vinyl acetate copolymer resin (EVA), which can be kneaded at a low processing temperature without applying a load to the expanded graphite.

[0031] Thermally expandable graphite is a known substance that has the property of expanding when heated. It is produced by treating powders of natural flaky graphite, pyrolytic graphite, kish graphite, or the like with an inorganic acid such as concentrated sulfuric acid, nitric acid, or selenic acid, and a strong oxidizing agent such as concentrated nitric acid, perchloric acid, perchlorates, permanganates, dichromates, dichromates, or hydrogen peroxide to produce a graphite intercalation compound, which is a type of crystalline compound that maintains the layered structure of carbon.

[0032] The thermally 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.

[0033] The larger the particle size (particle diameter) of the thermally expandable graphite, the greater 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 longer it takes to knead. From the viewpoint of expansion ratio, the particle size of the thermally expandable graphite is preferably 100 μm or more, and more preferably 400 μm or more. There is no particular upper limit to the particle diameter of the thermally expandable graphite, but it is preferably 1500 μm or less, and more preferably 1000 μm or less. Since the particle size is reflected in the particle diameter of the graphite used, commercially available thermally expandable graphite is classified using a specified sieve. This can be controlled by using a 50% particle size distribution. The average particle size was determined as the particle size of 50% of the particles passing through from the small particle size side of the raw material used. Alternatively, the particle size distribution of the thermally expandable graphite can be determined by observing a cross-section of the prepared sheet with a scanning electron microscope (SEM), and the average particle size can be determined as the particle size of 50% of the particles passing through from the small particle size side in the volume-based particle size distribution obtained from this.

[0034] The content of thermally expandable graphite is not particularly limited, but is preferably 10 to 500 parts by weight per 100 parts by weight of the matrix component, and more preferably 50 to 300 parts by weight per 100 parts by weight of the matrix component. If the content is 10 parts by weight or more, the volume expansion coefficient is large, and fire prevention performance is exhibited, which can sufficiently fill in the burned-out parts of structures such as sashes, while if the content is 500 parts by weight or less, mechanical strength is maintained.

[0035] The inorganic filler increases the heat capacity and suppresses heat transfer when the expandable heat insulating layer is formed, and also acts as an aggregate to improve the strength of the expandable heat insulating layer. The inorganic filler is not particularly limited, and examples thereof include metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; hydrated inorganic substances such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and hydrotalcite; and metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate.

[0036] In addition to these, inorganic fillers include calcium salts such as calcium sulfate, gypsum fiber, and calcium silicate; silica, diatomaceous earth, dawsonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, 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 ("MOS") (trade name), lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, and dewatered sludge. These inorganic fillers may be used alone or in combination of two or more.

[0037] In one embodiment, the inorganic filler is selected from metal oxides, hydrous minerals, metal carbonates, silica, and combinations thereof. Hydrous minerals include alkaline earth metal hydroxides.

[0038] Flame-retardant compounds (flame retardants), such as phosphorus compounds, may be added as inorganic fillers. The addition of phosphorus compounds increases the strength of the expandable insulation layer and improves fire resistance. Examples of phosphorus compounds include, but are not limited to, red phosphorus; various phosphate esters such as triphenyl phosphate, tricresyl phosphate (TCP), trixylenyl phosphate, cresyl diphenyl phosphate, and xylenyl diphenyl phosphate; metal phosphates such as sodium phosphate, potassium phosphate, and magnesium phosphate; and compounds represented by the following chemical formula (1).

[0039] [ka]

[0040] In chemical formula (1), R 1 and R 3 R represents hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms. 2 is a hydroxyl group, carbon number 1 to 16 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.

[0041] As the red phosphorus, commercially available red phosphorus can be used, but from the viewpoint of safety, such as moisture resistance and prevention of spontaneous combustion during kneading, red phosphorus particles whose surfaces are coated with a resin are preferably used.

[0042] The compound represented by chemical formula (1) is not particularly limited, and examples thereof include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonic acid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, and bis(4-methoxyphenyl)phosphinic acid. Among these, t-butylphosphonic acid is preferred due to its high flame retardancy, although it is expensive. The phosphorus compounds may be used alone or in combination of two or more.

[0043] Alternatively, it may be a salt of a lower phosphoric acid, such as monophosphate, diphosphate, tertiary phosphoric acid, metaphosphate, phosphorous acid, or hypophosphorous acid. In this specification, the term "salt" includes alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; other metal salts such as aluminum salts; and ammonium salts. From the viewpoint of fire resistance, aluminum salts of phosphorous acid are preferred.

[0044] The particle size of the inorganic filler is preferably 0.5 to 200 μm, more preferably 1 to 10 μm. When the inorganic filler is added in small amounts, dispersibility significantly affects performance, so a small particle size is preferred, but a particle size of 0.5 μm or greater provides good dispersibility. When the addition amount is large, as the filling level increases, the viscosity of the resin composition increases and moldability decreases. However, increasing the particle size can reduce the viscosity of the resin composition, so a large particle size is preferred. However, a particle size of 100 μm or less is desirable in terms of the surface properties of the molded product and the mechanical properties of the resin composition. The average particle size was determined as the particle size of 50% of the particles passing through from the small particle side of the raw material used. Alternatively, the particle size distribution of the inorganic filler was determined by observing a cross-sectional SEM (scanning electron microscope) image of the prepared sheet, and the particle size of 50% of the particles passing through from the small particle side in the volume-based particle size distribution obtained from this can also be used as the average particle size.

[0045] In order to obtain a desired particle size, the aggregated inorganic filler may be broken down, dispersed in a solvent, or the like, and then added, and the particle size may be controlled by sieving or the like.

[0046] Examples of inorganic fillers include aluminum hydroxide such as "Hijilite H-31" (manufactured by Showa Denko K.K.) with a particle size of 18 μm and "B325" (manufactured by ALCOA Corporation) with a particle size of 25 μm, and calcium carbonate such as "Whiten SB Red" (manufactured by Bihoku Funka Kogyo Co., Ltd.) with a particle size of 1.8 μm and "BF300" (manufactured by Bihoku Funka Kogyo Co., Ltd.) with a particle size of 8 μm.

[0047] The content of the inorganic filler is not particularly limited, but is preferably 30 to 500 parts by weight per 100 parts by weight of the matrix component. A content of 30 parts by weight or more provides sufficient fire retardancy, while a content of 500 parts by weight or less maintains mechanical strength. The content of the inorganic filler is more preferably 40 to 350 parts by weight.

[0048] When a phosphorus compound is used as the inorganic filler, the content of the phosphorus compound is not particularly limited, but is preferably 30 to 300 parts by weight per 100 parts by weight of the matrix component. When the amount is 30 parts by weight or more, the effect of improving the strength of the expandable 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.

[0049] The fire-resistant resin composition of the present invention may further contain a polyphosphate as an inorganic filler. The polyphosphate also functions as a flame retardant. Examples of polyphosphates include ammonium polyphosphate, melamine polyphosphate, melam polyphosphate, and melem polyphosphate. Commercially available ammonium polyphosphates include "AP422" and "AP462" manufactured by Clariant, "Sumisafe P" manufactured by Sumitomo Chemical Co., Ltd., and "Terrage C60" manufactured by Chisso Corporation.

[0050] A preferred ammonium polyphosphate is surface-coated ammonium polyphosphate (also referred to as coated ammonium polyphosphate). Among coated ammonium polyphosphates, melamine-coated ammonium polyphosphate, which is surface-coated with melamine, is described in JP-A-9-286875, and silane-coated ammonium polyphosphate, which is surface-coated with silane, is described in JP-A-2000-63562. The melamine-coated ammonium polyphosphate is (a) melamine-coated ammonium polyphosphate in which melamine is added and / or adhered to the surface of powdered ammonium polyphosphate particles, (b) coated ammonium polyphosphate in which the particle surface is crosslinked by active hydrogen possessed by amino groups in melamine molecules present in the coating layer of the melamine-coated ammonium polyphosphate particles and a compound having a functional group reactive with the active hydrogen, and / or (c) powdered ammonium polyphosphate or the melamine-coated ammonium polyphosphate particles in which the surface is coated with a thermosetting resin. Commercially available melamine-coated ammonium polyphosphate particles include, for example, "AP462" manufactured by Clariant, "FR CROS 484" manufactured by Budenheim Iberica, and "FR Examples of commercially available silane-coated ammonium polyphosphate particles include "FR CROS 486" manufactured by Budenheim Iberica.

[0051] The average particle size of the coated ammonium polyphosphate is preferably 15 to 35 μm, and can be measured by laser diffraction particle size distribution measurement.

[0052] In the fire-resistant resin composition of the present invention, the particle size ratio of the particle size of the thermally expandable graphite to the particle size of the inorganic filler is 1 to 1000. By setting the particle size ratio within this range, the thermally expandable graphite with a large particle size can be efficiently dispersed in the matrix resin without being hindered by the inorganic filler, and the inorganic filler is dispersed among the thermally expandable graphite dispersed in the resin, resulting in improved dispersion of the inorganic filler, thereby improving kneading efficiency. The particle size ratio is preferably 3 to 500, more preferably 5 to 50. Setting the particle size ratio within this numerical range allows for efficient kneading in a short period of time. On the other hand, if the particle size ratio is outside this range, the thermally expandable graphite will not be sufficiently dispersed in the matrix, resulting in problems such as surface staining and variation.

[0053] In the fire-resistant resin composition of the present invention, the total content of the thermally expandable graphite and the inorganic filler is 30% by weight or more, preferably 50% by weight or more. There is no particular upper limit to the total content of the thermally expandable graphite and the inorganic filler, but it is 75% by weight or less, preferably 60% by weight or less. By setting the content within this range, excellent fire resistance can be achieved.

[0054] In addition, in the fire-resistant resin composition of the present invention, the content of thermally expandable graphite is 5% by weight or more, It is more preferably 15% by weight or more, even more preferably 20% by weight or more, and most preferably 25% by weight or more. There is no particular upper limit to the content of thermally expandable graphite, but it is 75% by weight or less, and 50% by weight or less. By setting it within this numerical range, excellent fire resistance can be achieved. In a preferred embodiment of the present invention, when the matrix components are synthetic resin and elastomer, the content of thermally expandable graphite is 15% by weight or more, preferably 20% by weight or more, and more preferably 25% by weight or more. In another preferred embodiment, when the matrix component is rubber, the content of thermally expandable graphite is 5% by weight or more, preferably 15% by weight or more, more preferably 20% by weight or more, and even more preferably 25% by weight or more.

[0055] The fire-resistant resin composition of the present invention may further contain a plasticizer.

[0056] Plasticizers are added to adjust the melt viscosity of matrix components, particularly thermoplastic resins. Plasticizers can also be referred to as softeners. As the plasticizer, one or a combination of two or more of the following plasticizers may be used: Phthalate ester plasticizers such as di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), or phthalate esters of higher alcohols or mixed alcohols having approximately 10 to 13 carbon atoms; aliphatic dibasic acid ester plasticizers such as di-2-ethylhexyl adipate, di-n-octyl adipate, di-n-decyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, and di-2-ethylhexyl sebacate; Trimellitate ester plasticizers such as tri-2-ethylhexyl trimellitate (TOTM), tri-n-octyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, and di-n-octyl-n-decyl trimellitate; Adipate plasticizers such as di-2-ethylhexyl adipate (DOA) and diisodecyl adipate (DIDA); Sebacate plasticizers such as dibutyl sebacate (DBS) and di-2-ethylhexyl sebacate (DOS); phosphate ester plasticizers such as tributyl phosphate, trioctyl phosphate, octyl diphenyl 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, and bis(chloropropyl)monoctyl phosphate; Biphenyltetracarboxylic acid tetraalkyl ester plasticizers such as 2,3,3',4'-biphenyltetracarboxylic acid tetraheptyl ester; Polyester polymer plasticizers; Epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, and liquid epoxy resins; chlorinated paraffins; Chlorinated fatty acid esters such as alkyl pentachloride stearates; and Process oils such as paraffinic process oil, naphthenic process oil, and aromatic process oil.

[0057] The content of the plasticizer in the fire-resistant resin composition is not particularly limited, but is preferably within the range of 25 to 100 parts by weight per 100 parts by weight of the thermoplastic resin.

[0058] The fire-resistant resin composition of the present invention may further contain a heat stabilizer, a lubricant, etc., within the range that does not impair the physical properties of the composition. , processing aids, thermal decomposition type foaming agents, antioxidants, antistatic agents, pigments, etc. may also be added.

[0059] Examples of the heat stabilizer include lead heat stabilizers such as tribasic lead sulfate, tribasic lead sulfite, dibasic lead phosphite, lead stearate, and dibasic lead stearate; organotin heat stabilizers such as organotin mercapto, organotin maleate, organotin laurate, and dibutyltin maleate; and metal soap heat stabilizers such as zinc stearate and calcium stearate. These may be used alone or in combination of two or more.

[0060] Examples of lubricants include waxes such as polyethylene, paraffin, and montanic acid; various ester waxes; organic acids such as stearic acid and ricinoleic 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.

[0061] Examples of processing aids include chlorinated polyethylene, methyl methacrylate-ethyl acrylate copolymer, and high molecular weight polymethyl methacrylate.

[0062] Examples of the thermal decomposition type blowing agent include azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), p,p-oxybisbenzenesulfonylhydrazide (OBSH), and azobisisobutyronitrile (AIBN).

[0063] The fire-resistant resin composition of the present invention can be melt-extruded in a conventional manner using an extruder such as a single-screw extruder or a twin-screw extruder to obtain a fire-resistant resin molded article. The melting temperature varies depending on the matrix component and is not particularly limited, but for example, in the case of polyvinyl chloride resin, it is 130 to 170°C.

[0064] The fire-resistant resin composition or fire-resistant resin molded article of the present invention can be used to impart fire resistance to structures such as windows, shoji screens, doors (i.e., doors), sliding doors, sliding doors, and transoms; ships; and elevators. Because the fire-resistant resin composition of the present invention has excellent moldability, it is easy to obtain a specially shaped molded article that conforms to the complex shape of a structure. FIG. 1 shows an example in which a fire-resistant resin molded article 4 of the present invention is applied to the sash frame of a window 1 as a fixture. In this example, the sash frame has two inner frames 2 and one outer frame 3 surrounding the inner frames 2, and the fire-resistant resin molded article 3 is attached inside the inner frames 2 and the outer frames 3 along each side of the frame bodies of the inner frames 2 and the outer frames 3. In this way, the application of the fire-resistant resin molded article 3 of the present invention to the window 1 can impart fire resistance.

[0065] The present invention is not limited to the above-described embodiment, and for example, the following embodiments can also be adopted. When rubber (e.g., butyl rubber) is used as the matrix resin, the content of thermally expandable graphite is preferably 5% by weight or more and 10% by weight or less, and the total content of thermally expandable graphite and inorganic filler is preferably 30% by weight or more and 70% by weight or less.

[0066] The particle size ratio between the particle size of the thermally expandable graphite and the particle size of the inorganic filler may be in the range of 1-1000, preferably 30-700, more preferably 50-200, and even more preferably 65-75.

[0067] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. [Example]

[0068] 1. Making fireproof sheets [Example 1] The synthetic resin (matrix component) was 100 parts by weight of polyvinyl chloride, the plasticizer was 80 parts by weight of diisodecyl phthalate (DIDP), the thermally expandable graphite (GREP-EG, manufactured by Tosoh Corporation, particle size: 800 μm), and the inorganic filler was 50 parts by weight of aluminum phosphite (particle size: 100 μm) in a kneader in the amounts shown in Table 1. The mixture was then formed into a sheet using a calendar roll to obtain a fire-resistant sheet as a fire-resistant resin molded product with a width of 1000 mm, a thickness of 1.5 mm, and a length of 1 m. The kneading time in the kneader was standardized to 5 minutes after adding the graphite, and the test was conducted.

[0069] [Examples 2 to 33 and Comparative Examples 1 to 4] For Examples 2 to 33 and Comparative Examples 1 to 4, the components were mixed in the amounts shown in Tables 1 to 3 in the same manner as in Example 1 and formed into sheets to obtain fire-resistant sheets.

[0070] 2.Fire resistance (expansion ratio) measurement Samples were taken from the resulting fireproof sheet at three points: the center and center of the front and back in the flow direction. The resulting test pieces (100 mm long, 100 mm wide, 1.5 mm thick) were placed in a designated holder, fed into an electric furnace, and heated at 600°C for 30 minutes. The thickness of the test piece was then measured and the expansion ratio was calculated as (thickness of test piece after heating) / (thickness of test piece before heating). Differences between the minimum and maximum values ​​were marked with a ◎ if they were within 5% of the average, a ○ if they were within 10%, and an × if they were 10% or more.

[0071] 3. Surface finish evaluation of fire-resistant sheets The surface finish of the fire-resistant sheets of Examples 1 to 10 and Comparative Examples 1 and 2 was evaluated by visually checking the surface roughness and staining. The surface roughness (presence or absence of cracks or creases) and staining (exposed powder) were evaluated by visual inspection. Cracks and cracks are defined as being 3 mm or larger in size, and exposed powder is defined as white on the black surface of the sheet, or an exposed area of ​​graphite of 4 mm or larger. 2 If there were five or fewer spots on the 100cm x 100cm sheet, it was marked as "○", and if there were three or more spots, it was marked as "×". ○: No cracks on the surface or 5 cracks of 3 mm or more per m 2 Within ×: 5 cracks of 3mm or more on the surface / m 2 That's all.

[0072] 4. Strength evaluation The breaking strength of the obtained fire-resistant sheet was measured in accordance with JIS K 7161, and the tensile strength in the machine direction of the roll was measured. Those that broke at the time of 110% strain were marked with ×, and those that did not break were marked with ○.

[0073] The fire-resistant sheets of Examples 1 to 33 had excellent surface finish and were prevented from deteriorating in quality.

[0074] [Table 1]

[0075] [Table 2]

[0076] Table 3

[0077] Table 4

Claims

1. A fire-resistant resin composition containing a matrix component which is a resin, an elastomer, a rubber, or a combination thereof, thermally expandable graphite, and an inorganic filler, A fire-resistant resin composition characterized in that the particle size ratio of the particle size of the thermally expandable graphite to the particle size of the inorganic filler is in the range of 1 to 1000, the total content of the thermally expandable graphite and the inorganic filler is 30% by weight or more, and the content of the thermally expandable graphite is 15% by weight or more.

2. A fire-resistant resin composition containing a matrix component which is a resin, an elastomer, a rubber, or a combination thereof, thermally expandable graphite, and an inorganic filler, A fire-resistant resin composition characterized in that the particle size ratio of the thermally expandable graphite to the inorganic filler is in the range of 1 to 1000, the total content of the thermally expandable graphite and the inorganic filler is 30% by weight or more, and the content of the thermally expandable graphite is 5% by weight or more.

3. 3. The fire-resistant resin composition according to claim 1, wherein the thermally expandable graphite has an average particle size of 100 μm or more.

4. 4. The fire-resistant resin composition according to claim 1, wherein the inorganic filler contains a phosphite.

5. 5. The fire-resistant resin composition according to claim 1, further comprising a polyphosphate.

6. 6. The fire-resistant resin composition according to claim 1, further comprising a plasticizer.

7. 7. The fire-resistant resin composition according to claim 1, wherein the matrix component is a polyvinyl chloride resin or a polyolefin resin.

8. A fire-resistant resin molding comprising the fire-resistant resin composition according to any one of claims 1 to 7.

9. A fitting comprising the fire-resistant resin molded article according to claim 8.

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