JP7095985B2 - Refractory resin composition - Google Patents

Description

The present invention relates to a refractory resin composition.

Fine powders of phosphorus compounds and boron compounds are added to the fire-resistant resin using heat-expandable graphite in order to prevent the expanded graphite from scattering during combustion and to stabilize the shape of the residue. However, since these additives are solid particles, there is a problem that general physical properties such as tensile properties of the refractory resin are deteriorated.

Patent Documents 1 and 2 realize excellent fire resistance and workability by blending a phosphorus-based plasticizer with a fire-resistant resin composition.

WO2016 / 117699 WO2016 / 117702

An object of the present invention is to provide a refractory resin composition having excellent residue stability and general physical characteristics.

The present invention provides the following refractory resin compositions.
Item 1. A fire resistant resin composition comprising a matrix resin, a heat-expandable graphite, a phosphorus compound having a melting point lower than the molding temperature of the matrix resin, a solid metal (sub) phosphate and / or a solid boron compound that solidifies during combustion.
Item 2. Item 2. The refractory resin composition according to Item 1, wherein the matrix resin is a thermoplastic resin.
Item 3. The term is characterized in that the phosphorus compound having a melting point lower than the molding temperature of the matrix resin is a phosphate ester or a phosphite ester, and the solid metal (sub) phosphate that solidifies during combustion is a phosphite. The fire-resistant resin composition according to 1 or 2.
Item 4. With respect to 100 parts by mass of the matrix resin, 3 to 300 parts by mass of thermally expandable graphite, 1 to 200 parts by mass of a phosphorus compound having a melting point lower than the molding temperature of the matrix resin, and a solid metal (sub) phosphate that solidifies during combustion. Item 6. The fire resistant resin composition according to any one of Items 1 to 3, which comprises 3 to 300 parts by mass of a total amount of the solid boron compound.
Item 5. (Phosphorus compound having a melting point lower than the molding temperature of the matrix resin) / (Solid metal (sub) phosphate that solidifies during combustion) has a mass ratio of 0.05 to 100, any one of Items 1 to 4. The fire resistant resin composition according to.
Item 6. Item 2. The fire resistance according to any one of Items 1 to 4, wherein (a phosphorus compound having a melting point lower than the molding temperature of the matrix resin) / (a solid boron compound that solidifies during combustion) has a mass ratio of 0.05 to 100. Resin composition.
Item 7. Item 6. The refractory resin composition according to any one of Items 1 to 4, wherein the residual hardness of the molded product of the refractory resin composition is 0.11 kgf / cm ² or more and the tensile elongation is 150% or more.
Item 8. A molded product provided with a molded portion of the refractory resin composition according to any one of Items 1 to 7.

Phosphorus compounds whose melting point is lower than the molding temperature of the matrix resin are solid metal (sub) phosphates that solidify during combustion and solid boron that solidifies during combustion, which are conventionally used as residue shape stabilizers after combustion of refractory resins. By introducing it into a resin in combination with a compound, it has the effect of synergistically enhancing the effect of stabilizing the shape of the residue. Phosphorus compounds, which have a melting point lower than the molding temperature of the matrix resin, have both fire resistance and general physical properties even when the amount of solid metal (phosphorus) phosphate that solidifies during combustion and the amount of solid boron compound that solidifies during combustion are reduced. It will be possible.

The fire-resistant resin composition of the present invention comprises a matrix resin, a heat-expandable graphite, a phosphorus compound having a melting point lower than the molding temperature of the matrix resin, a solid metal (sub) phosphate and / or a solid boron compound that solidifies during combustion. These components and other additives contained as necessary can be obtained by melt-kneading using a known kneading device. Examples of other additives include oils, vulcanization accelerators, vulcanization aids, heat stabilizers, lubricants, processing aids, pyrolytic foaming agents, antioxidants, antioxidants, pigments and the like. Both "solid metal (sub) phosphate" and "solid boron compound" are solid at the molding temperature of the matrix resin.

Examples of the kneading device include an extruder, a kneader mixer, a double roll, a Banbury mixer, and a plast mill.

Examples of the matrix resin include polyvinyl chloride resin (PVC), chlorinated polyvinyl chloride resin (chlorinated PVC), ethylene vinyl acetate copolymer resin (EVA), olefinic elastomer (TPO), polyethylene (PE), and polypropylene (PP). ), Ethylene-propylene-diene copolymer (EPDM), polybutene, chloroprene (CR), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene-acrylonitrile copolymer (ASA), acrylonitrile / ethylene-propylene -Diene / styrene copolymer (AES) and the like can be mentioned, and EPDM resin is preferable. The diene monomer for cross-linking used in the EPDM resin is not particularly limited, and is, for example, 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-. Cyclic diene such as 2-norbornene, 5-isopropyridene-2-norbornene, norbornadiene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl- Examples thereof include chain non-conjugated diene such as 1,5-heptadiene, 6-methyl-1,5-heptadiene and 6-methyl-1,7-octadien.

Thermally expandable graphite is a conventionally known substance, and powders such as natural scale-like graphite, thermally decomposed graphite, and kiss graphite are mixed with an inorganic acid such as concentrated sulfuric acid, nitric acid, and selenic acid, and concentrated nitric acid, perchloric acid, and perchlorine. A graphite interlayer compound is produced by treating with a strong oxidizing agent such as an acid salt, a permanganate salt, a dichromate salt, and hydrogen peroxide. The produced thermally expandable graphite is a crystalline compound that maintains the layered structure of carbon.

In the heat-expandable graphite used in the present invention, the heat-expandable graphite obtained by acid treatment may be neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound or the like.

Examples of the aliphatic lower amine include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like.

Examples of the alkali metal compound and the alkaline earth metal compound include hydroxides such as lithium, potassium, sodium, calcium, barium and magnesium, oxides, carbonates, sulfates and organic acid salts.

Specific examples of the heat-expandable graphite include "CA-60S" and "CA-60N" manufactured by Nihon Kasei Corporation.

When the amount of the heat-expandable graphite added is small, the fire resistance and foamability tend to decrease. Further, when the amount is increased, it becomes difficult to extrude, the surface property of the obtained molded body is deteriorated, and the mechanical properties tend to be deteriorated. Therefore, the amount of the heat-expandable graphite added to 100 parts by mass of the matrix resin is about 3 to 300 parts by mass, preferably about 10 to 200 parts by mass.

As the phosphorus compound having a melting point lower than the molding temperature of the matrix resin, a phosphoric acid ester or a phosphite ester is preferable. Specific examples of phosphorus compounds having a melting point lower than the molding temperature of the matrix resin include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, and tricresyl. Triorganophosphates (phosphates) such as phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, and tributoxyethyl phosphate, (mono or di) methyl acid phosphate, (mono or di). Di) Ethyl acid phosphate, (mono or di) butyl acid phosphate, (mono or di) butoxyethyl acid phosphate, (mono or di) octyl acid phosphate, (mono or di) decyl acid phosphate, (mono or di) lauryl acid Phosphate, (mono or di) stearyl acid phosphate, (mono or di) oleyl acid phosphate, (mono or di) behenyl acid phosphate, (mono or di) phenyl acid phosphate, (mono or di) nonylphenyl acid phosphate, (mono or di) Or acid phosphates such as di) cyclohexyl acid phosphate, (mono or di) phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate and bisphenol A acid phosphate (the organic groups in the phosphate monoester or phosphate diester, acid phosphate are mono-substituted. , Disubstituted, and mixtures thereof.), Trialkyl phosphites such as tridecylphosphite, dialkylmonoarylphosphites such as didecylmonophenylphosphite, monobutyldiphenylphosphite. Triaryl phosphites such as monoalkyldiarylphosphite, triphenylphosphite, and tris (2,4-di-tert-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2,4-di). -Tert-Butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythrito Pentaerythritol phosphite such as rudiphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, and 2,2'-methylenebis (4,6-di-tert-butylphenyl). Phosphite containing cyclic phosphite such as (2,4-di-tert-butylphenyl) phosphite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, and bis (di-di-). Preferably tert-butylphenyl) -phenyl-phenylphosphonite, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, and bis (2,4-di-tert-butylphenyl)-. Examples thereof include phosphonite such as phenyl-phenylphosphonite, phosphonate such as dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate, and tertiary phosphine such as triphenylphosphine. These may be used alone or in combination of two or more.

The amount of the phosphorus compound having a melting point lower than the molding temperature of the matrix resin is about 1 to 200 parts by mass, preferably about 1 to 100 parts by mass with respect to 100 parts by mass of the matrix resin.

As the solid metal (sub) phosphate that solidifies during combustion, at least one metal selected from various phosphates / phosphites, metals of Group IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. Alternatively, a phosphate / subphosphate consisting of a salt with a compound can be mentioned. Examples of various phosphoric acid / phosphoric acid include phosphoric acid, phosphoric acid, pyrophosphoric acid, and polyphosphoric acid.

Examples of the metal of Group IA to IVB of the Periodic Table include lithium, sodium, potassium, magnesium, calcium, barium, iron (II), iron (III), zinc and aluminum.

Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like.

Examples of the aromatic amine include pyridine, triazine, melamine, ammonium and the like.

The above solid metal (phosphorous acid) phosphate may be subjected to a known water resistance improving treatment such as a silane coupling agent treatment or a coating with a melamine resin, or a known foaming aid such as melamine or pentaerythritol may be added. May be.

Examples of the phosphate / phosphite constituting the solid metal (sub) phosphate that solidifies during combustion include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate, and monosodium phosphate. , Sodium phosphate, disodium phosphate, monosodium phosphite, dissodium phosphite, sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, phosphite Potassium salts such as monopotassium acid, dipotassium phosphite, potassium hypophosphite, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, hypophosphite Lithium salt such as lithium phosphate, barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, barium salt such as barium hypophosphite, magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, next Magnesium salts such as magnesium phosphite, calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium salts such as calcium hypophosphite, zinc phosphate, zinc phosphite, zinc hypophosphite and the like. Examples thereof include salts, aluminum salts such as primary aluminum phosphate, secondary aluminum phosphate, tertiary aluminum phosphate, aluminum phosphite, and aluminum hypophosphite.

Examples of the polyphosphate include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, aluminum polyphosphate and the like.

The solid metal (sub) phosphate that solidifies during combustion is preferably a phosphite, with aluminum phosphite being particularly preferred. As the solid metal (sub) phosphate, one kind or two or more kinds can be used.

The amount of the solid metal (sub) phosphate added is about 3 to 300 parts by mass, preferably about 50 to 200 parts by mass with respect to 100 parts by mass of the matrix resin.

Examples of the solid boron compound that solidifies during combustion include borax, boron oxide, boric acid, and borate. Examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide and the like. Examples of the borate include alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the Periodic Table, and ammonium borates, and specific examples thereof include lithium borate and borate. Alkaline borate metal salts such as sodium, potassium borate, cesium borate, alkaline earth metal borates such as magnesium borate, calcium borate, barium borate, zirconium borate, zinc borate, aluminum borate, Examples include ammonium borate. The solid boron compound that solidifies during combustion is preferably boric acid or borate, more preferably boric acid. As the solid boron compound, one kind or two or more kinds can be used.

The amount of the solid boron compound added during combustion is about 3 to 300 parts by mass, preferably about 50 to 200 parts by mass with respect to 100 parts by mass of the matrix resin.

(Phosphorus compound having a melting point lower than the molding temperature of the matrix resin) / (solid metal (sub) phosphate) is preferably 0.05 to 100, more preferably 0.1 to 20 in terms of mass ratio.

The mass ratio of (phosphorus compound having a melting point lower than the molding temperature of the matrix resin) / (solid boron compound that solidifies during combustion) is preferably 0.05 to 100, more preferably 0.1 to 20.

In the present invention, by blending a phosphorus compound having a melting point lower than the molding temperature of the matrix resin, the blending amount of the solid metal (sub) phosphate / solid boron compound can be suppressed, and the physical properties can be improved.

Examples of the oil include paraffin-based process oils, naphthen-based process oils and other process oils, dibutylphthalate, dioctylphthalate, di- (2-ethylhexyl) tetrahydrophthalate, di-n-butyl adipate, and petrolatum. , Liquid paraffin, castor oil, cottonseed oil, etc., and these can be used alone or in combination of two or more. Preferred oils are process oils and liquid paraffin.

The oil content is preferably about 25 to 40% by mass with respect to the matrix resin of the refractory resin composition. Examples of the sulfide agent include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dithiocarbamate and the like, and sulfur and tetramethylthiuram disulfide are preferable.

As the vulcanizing agent, one kind or two or more kinds can be used.

When the amount of the vulcanizing agent added is small, the stability at the time of heat tends to decrease. Moreover, when the amount increases, it tends to be difficult to mold. Therefore, the amount of the vulcanizing agent added to 100 parts by mass of the matrix resin is about 0.1 to 10 parts by mass, preferably about 0.5 to 5 parts by mass.

When a vulcanizing agent is used, a vulcanization accelerator can be used in combination.

Examples of the vulcanization accelerator include thiazole-containing vulcanization accelerator, guanidine-containing vulcanization accelerator, aldehyde amine-containing vulcanization accelerator, imidazoline-containing vulcanization accelerator, thiourea-containing vulcanization accelerator, and thiuram-containing vulcanization accelerator. Examples thereof include a dithiolate-containing vulcanization accelerator, a thiourea-containing vulcanization accelerator, and a zantate-containing vulcanization accelerator.

Examples of the thiazole-containing vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide and N-oxydiethylene-2-benzothiazolesulfenamide.

Examples of the guanidine-containing vulcanization accelerator include diphenylguanidine and triphenylguanidine.

Examples of the aldehyde amine-containing vulcanization accelerator include acetaldehyde / aniline condensate.

Examples of the imidazoline-containing vulcanization accelerator include 2-mercaptoimidazoline.

Examples of the thiourea-containing vulcanization accelerator include diethyl thiourea and dibutyl thiourea.

Examples of the thiuram-containing vulcanization accelerator include tetramethylthium monosulfide and tetramethylthium disulfide.

Examples of the dithioate-containing vulcanization accelerator include zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate.

Examples of the thiourea-containing vulcanization accelerator include ethylene thiourea and N, N'-diethyl thiourea.

Examples of the zantate-containing vulcanization accelerator include zinc dibutyl phthalate.

As the vulcanization accelerator, one kind or two or more kinds can be used.

The amount of the vulcanization accelerator added to 100 parts by mass of the matrix resin is preferably about 0.1 to 20 parts by mass. By using a vulcanization accelerator, vulcanization can proceed efficiently. The amount of the vulcanization accelerator added is preferably about 0.1 to 10 parts by mass.

When a vulcanizing agent is used, a vulcanization aid can be used in combination.

Examples of the vulcanization aid include quinonedioxime-based vulcanization aids such as p-quinonedioxime, acrylic-containing vulcanization aids such as ethylene glycol dimethacrylate and trimethylolpropanetrimethacrylate, diallyl phthalate, and triallyl isosia. Examples thereof include an allyl-containing vulcanization aid such as nurate, a maleimide-containing vulcanization aid, divinylbenzene, zinc oxide, magnesium oxide, and zinc flower.

The amount of the vulcanization aid added to 100 parts by mass of the matrix resin is preferably about 1 to 50 parts by mass. By using a vulcanization aid, vulcanization can proceed efficiently. The vulcanization reaction can be carried out at a temperature of about 150 to 250 ° C., preferably 200 to 230 ° C.

Examples of the cross-linking accelerator include tellurium diethyldithiocarbamate, N, N, N', N'-tetraethylthiuram disulfide, benzyl diethyldithiocarbamate and the like.

The inorganic filler is not particularly limited, and for example, silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, etc. Aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawn night, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite , Active white clay, sebiolite, 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, titanium acid Potassium, magnesium sulfate, lead zirconia titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, dehydrated sludge, etc. Water-containing inorganic substances such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide having a heat absorbing effect are preferable. Further, antimony oxide is preferable because it has an effect of improving flame retardancy.

One kind or two or more kinds of inorganic fillers can be used.

When the amount of the inorganic filler added is small, the fire resistance performance tends to be deteriorated, and when the amount is large, extrusion molding becomes difficult, the surface property of the obtained molded body is deteriorated, and the mechanical properties tend to be deteriorated. It is 3 to 200 parts by mass, preferably 10 to 150 parts by mass with respect to 100 parts by mass of the matrix resin.

The plasticizer is not particularly limited, and is, for example, a phthalate ester plasticizer such as di-2-ethylhexylphthalate (DOP), dibutylphthalate (DBP), diheptylphthalate (DHP), and diisodecylphthalate (DIDP), di-2. -Fatigal ester plasticizers such as ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), dibutyl adipate (DBA), epoxidized ester plasticizers such as epoxidized soybean oil, polyester plasticizers such as adipic acid ester and polyester adipate, Examples thereof include trimellitic acid ester plasticizers such as tri-2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM).

One type or two or more types of plasticizer can be used.

When the amount of the plasticizer added is small, the extrusion moldability tends to decrease, and when the amount is large, the obtained molded product tends to be too soft. Therefore, the amount of the plasticizer added is 20 to 200 parts by mass with respect to 100 parts by mass of the matrix resin.

Examples of the thermoplastic modifier include a fluororesin-based viscosity modifier such as a PTFE (polytetrafluoroethylene) -based viscosity modifier.

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 materials. Examples thereof include organic tin heat stabilizers such as tin malate, organic tin laurate and dibutyl tin malate, and metal soap heat stabilizers such as zinc stearate and calcium stearate.

One type or two or more types of heat stabilizers can be used.

Examples of the lubricant include waxes such as polyethylene, paraffin and montanic acid, various ester waxes, organic acids such as stearic acid and lysynolic acid, organic alcohols such as stearyl alcohol, and amide compounds such as dimethylbisamide. Be done.

One or more lubricants can be used.

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

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

Examples of the antioxidant include phenol compounds and the like.

Examples of the antistatic agent include amino compounds and the like.

Examples of the pigment include organic pigments such as azo-based, phthalocyanine-based, slene-based, and dye lake-based pigments, and inorganic pigments such as oxide-based, molybdenum chromate-based, sulfide / selenium-based, and ferrocyanine-based pigments. Be done.

The refractory resin composition used in the present invention can be preferably used for extrusion molding. A molded body of a fire-resistant resin composition can be obtained by melting and extruding the resin composition at 130 to 170 ° C. with an extruder such as a single-screw extruder or a twin-screw extruder according to a conventional method. ..

The molded product of the refractory resin composition of the present invention can be used in combination with a window plate material. A refractory sash can be obtained by installing a molded body of the refractory resin composition on the outer periphery of the window plate material.

Further, the molded product of the refractory resin composition of the present invention can also be used in combination with a non-combustible frame material.

Examples of the material of the non-combustible frame material include aluminum alloys, metals such as stainless steel, and inorganic substances such as glass and ceramics.

The molded body of the fire-resistant resin composition and the non-combustible frame material can be adhered to each other by, for example, an adhesive, double-sided adhesive tape, or the like.

Further, for the molded body of the fire-resistant resin composition and the non-combustible frame material, for example, a slide rail portion and a slide rail receiving portion that can slide with each other are installed on the molded body and the non-combustible frame material of the fire-resistant resin composition, respectively. It can be fixed by combining the slide rail portion and the slide rail receiving portion.

The expansion ratio of the molded product of the refractory resin composition of the present invention is 20 times or more, preferably 25 times or more. The residual hardness of the molded product provided with the molded portion of the fire-resistant resin composition of the present invention is preferably 0.12 kgf / cm ² or more, more preferably 0.15 kgf / cm ² or more, still more preferably 0.18 kgf / cm. ² or more, particularly preferably 0.23 kgf / cm ² or more. The tensile elongation of the molded product provided with the molded portion of the refractory resin composition of the present invention is preferably 130% or more, more preferably 150% or more, still more preferably 200% or more, and particularly preferably 300% or more. .. The upper limit of tensile elongation is 3000%.

Examples of the molded product provided with the molded portion of the refractory resin composition include a multilayer molded product containing the refractory resin composition and other layers.

Hereinafter, the present invention will be described in detail with reference to Examples. The present invention is not limited to these examples.
[Examples 1 to 5 and Comparative Examples 1 to 3]
A refractory resin composition containing each component with the components and blending amounts shown in Table 1 was kneaded and pressed at 60 ° C. and 19 MPa for 4 minutes to form a sheet having a thickness of 1 mm. Next, heat for 4 minutes at 80 ° C without pressure to alleviate the strain, and finally vulcanize with a press at 160 ° C without pressure for 4 minutes to prepare a 1 mm thick sheet sample. Created.

-Ingredients of refractory resin composition
(i) Matrix resin (EPDM)
Product name: EP35 manufactured by JSR Corporation
(ii) Thermally expandable graphite Product name: GREP-EG manufactured by Tosoh Corporation
(iii) Vulcanization accelerator Product name: Dibenzothiazyldisfurido (Sanshin Kagaku Sunseller DM-G)
(iv) Phosphorus compound whose melting point is lower than the molding temperature of the matrix resin Trade name: Phoslex A-13 (mixture of isotridecylphosphoric acid monoester and diester, hereinafter abbreviated as "TDP") manufactured by SC Organic Chemistry.

Since TDP does not have plasticizer performance, process oil was used in combination as a plasticizer.

As aluminum phosphite (Al phosphite, solid metal (sub) phosphate that solidifies during combustion) and boric acid (solid boron compound that solidifies during combustion), commercially available products were used.

[Examples 6 to 11]
The refractory resin composition containing each component with the components and blending amounts shown in Tables 2 to 3 was kneaded and pressed under the conditions of 150 ° C. and 19 MPa for 3 minutes to form a sheet having a thickness of 1 mm.

(i) Matrix resin Olefin elastomer (TPO) (Product name: Mirastromer 5020BS, manufactured by Japan Polyethylene Corporation)
EVA (Product name: Evaflex EV460, Mitsui DuPont Polychemical Co., Ltd.)
PVC (Product name: TK-1000, Shin-Etsu Chemical Co., Ltd.)
Chlorinated PVC (Product name: HA53F, Tokuyama Sekisui Kogyo Co., Ltd.)
(ii) Phosphorus compound triethyl phosphate having a melting point lower than the molding temperature of the matrix resin (trade name: No. 8 Chemical Industry, TEP)
Cresyldiphenyl phosphate (trade name: Eighth Chemical Industry, CDP)

[Test Example 1]
For the molded bodies of the refractory resin compositions of Examples 1 to 11 and Comparative Examples 1 to 3, the expansion ratio, the residual hardness, the breaking strain, and the tensile stress were measured under the conditions of (i) to (iii) below. The results are shown in Tables 1 to 3.

(i) Expansion Magnification A sample impregnated in a 200-mesh wire mesh / aluminum glass cloth was placed in a SUS box frame in an electric furnace preheated to 600 ° C, and heated for 30 minutes. The residual thickness of the sample taken out was measured with a caliper, and the expansion ratio was calculated by the following formula.
Expansion ratio (times) = Thickness of residue after combustion / Initial thickness of refractory rubber composition sheet

(ii) Residual hardness Using a tensile tester (Tensilon RTC, manufactured by Orientec), the residue is compressed with an indenter of 0.25 cm ² at a compression rate of 0.1 cm / min, and the maximum point load that appears first is the residual hardness. I made it.

(iii) Tensile elongation (%)
Using a tensile tester (Tensilon RTC, manufactured by Orientec Co., Ltd.), a test piece (JIS No. 3 dumbbell) was punched out from the sheet samples of Examples 1 to 11 and Comparative Examples 1 to 3 obtained in the above Examples, and tensile and stretched. Degrees and tensile stresses were measured according to JIS K6251. The tensile elongation of the test piece at 23 ° C was measured under the conditions of a chuck distance of 60 mm, a marked line distance of 20 mm, and a tensile speed of 500 mm / min (strengthening). The tensile elongation was calculated by the ratio of the elongation (displacement) at break to the distance between the marked lines.

Claims (6)

Containing matrix resin, thermally expandable graphite, phosphorus compounds having a melting point lower than the forming temperature of the matrix resin, solid metal (sub) phosphate and / or solid boron compounds that solidify during combustion.
The matrix resin is either EPDM, TPO, EVA, PVC, or chlorinated PVC.
Phosphorus compounds having a melting point lower than the molding temperature of the matrix resin are phosphoric acid esters and / or subphosphates.
The solid metal (sub) phosphate that solidifies during combustion is aluminum phosphite .
A refractory resin composition in which the solid boron compound that solidifies during combustion is boric acid . With respect to 100 parts by mass of the matrix resin, 3 to 300 parts by mass of thermally expandable graphite, 1 to 200 parts by mass of a phosphorus compound having a melting point lower than the molding temperature of the matrix resin, and a solid metal (sub) phosphate that solidifies during combustion. The fire-resistant resin composition according to claim 1, which comprises a total amount of 3 to 300 parts by mass of the solid boron compound. The fire resistance according to claim 1 or 2 , wherein (a phosphorus compound having a melting point lower than the molding temperature of the matrix resin) / (a solid metal (sub) phosphate that solidifies during combustion) has a mass ratio of 0.05 to 100. Sex resin composition. The fire-resistant resin composition according to claim 1 or 2 , wherein (a phosphorus compound having a melting point lower than the molding temperature of the matrix resin) / (a solid boron compound that solidifies during combustion) has a mass ratio of 0.05 to 100. The refractory resin composition according to claim 1 or 2 , wherein the residual hardness of the molded product of the refractory resin composition is 0.11 kgf / cm ² or more and the tensile elongation is 150% or more. A molded product provided with a molded portion of the refractory resin composition according to any one of claims 1 to 5 .