JP2017008310A - Fire proof resin molded body and fitting having the same - Google Patents
Fire proof resin molded body and fitting having the same Download PDFInfo
- Publication number
- JP2017008310A JP2017008310A JP2016121052A JP2016121052A JP2017008310A JP 2017008310 A JP2017008310 A JP 2017008310A JP 2016121052 A JP2016121052 A JP 2016121052A JP 2016121052 A JP2016121052 A JP 2016121052A JP 2017008310 A JP2017008310 A JP 2017008310A
- Authority
- JP
- Japan
- Prior art keywords
- plasticizer
- resin
- resin component
- fireproof
- resin molded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 109
- 239000011347 resin Substances 0.000 title claims abstract description 109
- 239000004014 plasticizer Substances 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 23
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 18
- 239000001205 polyphosphate Substances 0.000 claims abstract description 18
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 18
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 239000011342 resin composition Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 230000009970 fire resistant effect Effects 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 230000008021 deposition Effects 0.000 abstract 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 23
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 21
- 239000004114 Ammonium polyphosphate Substances 0.000 description 20
- 239000002245 particle Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 19
- 235000019198 oils Nutrition 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- -1 polypropylene Polymers 0.000 description 15
- 239000011256 inorganic filler Substances 0.000 description 12
- 229910003475 inorganic filler Inorganic materials 0.000 description 12
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- 238000012360 testing method Methods 0.000 description 7
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
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- 239000010410 layer Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
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- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 2
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- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
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- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
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- 238000007654 immersion Methods 0.000 description 2
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- GUSFEBGYPWJUSS-UHFFFAOYSA-N pentaazanium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O GUSFEBGYPWJUSS-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229960001147 triclofos Drugs 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- JZZBTMVTLBHJHL-UHFFFAOYSA-N tris(2,3-dichloropropyl) phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Cl)CCl)OCC(Cl)CCl JZZBTMVTLBHJHL-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- LKOCAGKMEUHYBV-UHFFFAOYSA-N tris(3-bromo-3-chloropropyl) phosphate Chemical compound ClC(Br)CCOP(=O)(OCCC(Cl)Br)OCCC(Cl)Br LKOCAGKMEUHYBV-UHFFFAOYSA-N 0.000 description 1
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 description 1
- SMYKBXMWXCZOLU-UHFFFAOYSA-N tris-decyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCCCC)C(C(=O)OCCCCCCCCCC)=C1 SMYKBXMWXCZOLU-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Special Wing (AREA)
- Building Environments (AREA)
Abstract
Description
本発明は、耐火樹脂成型体およびそれを備えた建具に関する。 The present invention relates to a fireproof resin molded body and a fitting including the fireproof resin molded body.
防火サッシおよび防火ドアには熱膨張性耐火シートが用いられているものがあり、熱膨張性耐火シートには難燃剤としてポリリン酸塩が配合されている場合がある。そのような例として、特許文献1には、平均粒子径15〜35μmである被覆ポリリン酸アンモニウムを用いた、合成樹脂をバインダーとする発泡耐火材が開示されている。 Some fireproof sashes and fireproof doors use a heat-expandable fireproof sheet, and the heat-expandable fireproof sheet may contain a polyphosphate as a flame retardant. As such an example, Patent Document 1 discloses a foam refractory material using a synthetic resin as a binder and using coated ammonium polyphosphate having an average particle diameter of 15 to 35 μm.
サッシまたはドアが取り付けられる場所によっては、熱膨張性耐火シートが結露や風雨に晒される環境に置かれる場合があるところ、ポリリン酸塩は難燃性には非常に優れているが、水分に弱く、加水分解後、熱膨張性シートの表面に白色の析出物が生じ(ブリードアウトし)、発生した析出物によりシート外観を損なう場合があった。熱膨張性シートの表面の耐水性が向上すれば、析出物の発生も抑制される。 Depending on where the sash or door is installed, the heat-expandable refractory sheet may be placed in an environment where it is exposed to condensation or wind and rain, but polyphosphate is very flame retardant but weak against moisture After the hydrolysis, a white precipitate was generated on the surface of the thermally expandable sheet (bleeded out), and the appearance of the sheet was sometimes impaired by the generated precipitate. If the water resistance of the surface of the thermally expandable sheet is improved, the generation of precipitates is also suppressed.
本発明の目的は、難燃性および耐水性に優れた耐火樹脂成型体を提供することにある。 An object of the present invention is to provide a fire-resistant resin molded article excellent in flame retardancy and water resistance.
本発明者らは、上記の目的を達成すべく、耐火樹脂成形体を構成する耐火樹脂組成物中の可塑剤の量を従来よりも過剰量にする事により、可塑剤が耐火樹脂成形体の表面に油膜を形成して、それにより表面を撥水するため耐水性が顕著に向上することを見出し、本発明を完成するに至った。 In order to achieve the above object, the inventors of the present invention have made the plasticizer in the refractory resin molded body by making the amount of the plasticizer in the refractory resin composition constituting the refractory resin molded body excessive as compared with the conventional one. An oil film was formed on the surface, thereby repelling the surface, so that the water resistance was remarkably improved and the present invention was completed.
本発明は以下の通りである。
[1]樹脂成分と、ポリリン酸塩とを含む耐火樹脂成型体であって、表面に可塑剤の油膜を備えた耐火樹脂成型体。
[2]可塑剤が、樹脂成分に対する相溶性の異なる複数の可塑剤である項1に記載の耐火樹脂成型体。
[3]前記樹脂成分と前記可塑剤とのsmall法で計算される相溶性パラメーターの差が0.5より大きい可塑剤と、
前記樹脂成分と前記可塑剤とのsmall法で計算される相溶性パラメーターの差が0.5以下の可塑剤とを含有することを特徴とする項1又は2に記載の耐火樹脂成型体。
[4]前記樹脂成分と前記可塑剤とのsmall法で計算される相溶性パラメーターの差が0.5より大きい可塑剤の含有量が、前記樹脂成分と前記可塑剤とのsmall法で計算される相溶性パラメーターの差が0.5以下の可塑剤の含有量よりも多いことを特徴とする項3に記載の耐火樹脂成型体。
[5]前記可塑剤の含有量が前記樹脂成分の含有量よりも多い項1〜4のいずれか一項に記載の耐火樹脂成型体。
[6]樹脂成分と、ポリリン酸塩とを含む耐火樹脂成型体であって、可塑剤の含有量が前記樹脂成分の含有量よりも多い耐火樹脂成型体。
[7]熱膨張性黒鉛をさらに含有する項1〜6のいずれかに記載の耐火樹脂成型体。
[8]可塑剤がリン系の可塑剤を含有する項1〜7のいずれかに記載の耐火樹脂成型体。
[9]項1〜8のいずれか一項に記載の耐火樹脂成形体を備えた建具。
[10]樹脂成分と、ポリリン酸塩とを含む耐火樹脂組成物の表面に可塑剤の被膜を形成することを含む、耐火樹脂組成物におけるポリリン酸塩の加水分解による析出物の発生の抑制方法。
The present invention is as follows.
[1] A fire-resistant resin molded body containing a resin component and a polyphosphate, and having a plasticizer oil film on the surface.
[2] The fire resistant resin molded article according to item 1, wherein the plasticizer is a plurality of plasticizers having different compatibility with the resin component.
[3] a plasticizer having a difference in compatibility parameter calculated by the small method between the resin component and the plasticizer of more than 0.5;
Item 3. The fireproof resin molded article according to item 1 or 2, comprising a plasticizer having a difference in compatibility parameter calculated by the small method between the resin component and the plasticizer of 0.5 or less.
[4] The plasticizer content in which the difference in the compatibility parameter calculated by the small method between the resin component and the plasticizer is greater than 0.5 is calculated by the small method between the resin component and the plasticizer. Item 6. The fireproof resin molded article according to Item 3, wherein the difference in compatibility parameter is greater than the content of a plasticizer of 0.5 or less.
[5] The fireproof resin molded article according to any one of Items 1 to 4, wherein the plasticizer content is greater than the resin component content.
[6] A fire-resistant resin molded body containing a resin component and a polyphosphate, wherein the plasticizer content is higher than the resin component content.
[7] The fire-resistant resin molded article according to any one of Items 1 to 6, further containing thermally expandable graphite.
[8] The fire resistant resin molded article according to any one of Items 1 to 7, wherein the plasticizer contains a phosphorus plasticizer.
[9] A joinery comprising the fireproof resin molded article according to any one of items 1 to 8.
[10] A method for suppressing generation of precipitates due to hydrolysis of polyphosphate in a refractory resin composition, comprising forming a plasticizer film on the surface of the refractory resin composition containing a resin component and a polyphosphate .
本発明によれば、難燃性に優れ、かつ析出物の発生が抑制された耐火樹脂成型体を提供することが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the fireproof resin molding which was excellent in the flame retardance and the generation | occurrence | production of the precipitate was suppressed.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
本発明の耐火樹脂成形体は、樹脂成分と、ポリリン酸塩とを含有し、表面に可塑剤の油膜を備える。樹脂成分は、樹脂、エラストマー、ゴム、またはこれらの組み合わせからなる。なお、表面に可塑剤の油膜を備えるとは、耐火樹脂成形体の表面全体に可塑剤の油膜を備えることに限られず、耐火樹脂成形体の表面の一部に可塑剤の油膜を備えることも含む。 The fireproof resin molded article of the present invention contains a resin component and a polyphosphate, and is provided with a plasticizer oil film on the surface. The resin component is made of resin, elastomer, rubber, or a combination thereof. The provision of a plasticizer oil film on the surface is not limited to the provision of a plasticizer oil film over the entire surface of the fireproof resin molded article, and a plasticizer oil film may be provided on a part of the surface of the fireproof resin molded article. Including.
樹脂成分としての樹脂は、熱可塑性樹脂であっても熱硬化性樹脂であってもよい。 The resin as the resin component may be a thermoplastic resin or a thermosetting resin.
熱可塑性樹脂の例としては、ポリプロピレン樹脂、ポリエチレン樹脂等のポリオレフィン樹脂、ポリ(1−)ブテン樹脂、ポリペンテン樹脂、ポリスチレン樹脂、ポリ酢酸ビニル樹脂、アクリロニトリル−ブタジエン−スチレン樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、アクリル樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリブタジエン樹脂、ポリイミド樹脂、ポリ塩化ビニル樹脂(塩素化塩化ビニル樹脂を含む)、これらの組み合わせ等が挙げられる。なかでも、ポリオレフィン樹脂、ポリスチレン樹脂、ポリ酢酸ビニル樹脂、またはポリ塩化ビニル樹脂が好ましい。 Examples of thermoplastic resins include polypropylene resins, polyolefin resins such as polyethylene resins, poly (1-) butene resins, polypentene resins, polystyrene resins, polyvinyl acetate resins, acrylonitrile-butadiene-styrene resins, polycarbonate resins, polyphenylene ether resins. , Acrylic resin, polyamide resin, polyamideimide resin, polybutadiene resin, polyimide resin, polyvinyl chloride resin (including chlorinated vinyl chloride resin), and combinations thereof. Among these, polyolefin resin, polystyrene resin, polyvinyl acetate resin, or polyvinyl chloride resin is preferable.
上記熱可塑性樹脂はいずれも、樹脂組成物としての耐火性能を阻害しない範囲で、架橋、変性して用いてもよい。樹脂の架橋方法についても、特に限定はなく、熱可塑性樹脂の通常の架橋方法、例えば、各種架橋剤、過酸化物を使用する架橋、電子線照射による架橋等が挙げられる。 Any of the above thermoplastic resins may be used after being crosslinked or modified within a range not impairing the fire resistance performance of the resin composition. The crosslinking method of the resin is not particularly limited, and examples thereof include a usual crosslinking method for thermoplastic resins, such as crosslinking using various crosslinking agents and peroxides, and crosslinking by electron beam irradiation.
熱硬化性樹脂の例としてはエポキシ樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂、不飽和ポリエステル樹脂、アルキド樹脂、ポリウレタン、熱硬化性ポリイミド等が挙げられる。なかでも、エポキシ樹脂が好ましい。 Examples of the thermosetting resin include epoxy resin, phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, thermosetting polyimide, and the like. Among these, an epoxy resin is preferable.
本発明で用いられるエポキシ樹脂は、特に限定されないが、基本的にはエポキシ基をもつモノマーと硬化剤とを反応させることにより得られる。上記エポキシ基をもつモノマーとしては、例えば、2官能のグリシジルエーテル型、グリシジルエステル型、多官能のグリシジルエーテル型等のモノマーが例示される。 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 monomers such as a bifunctional glycidyl ether type, a glycidyl ester type, and a polyfunctional glycidyl ether type.
これらのエポキシ基をもつモノマーは、単独で用いられてもよく、2種以上が併用されてもよい。 These monomers having an epoxy group may be used alone or in combination of two or more.
上記硬化剤としては、重付加型または触媒型のものが用いられる。重付加型の硬化剤としては、例えば、ポリアミン、酸無水物、ポリフェノール、ポリメルカプタン等が例示される。また、上記触媒型の硬化剤としては、例えば、3級アミン、イミダゾール類、ルイス酸錯体等が例示される。エポキシ樹脂の硬化方法は、特に限定されず、公知の方法によって行うことができる。 As the curing agent, a polyaddition type or a catalyst type is used. Examples of the polyaddition type curing agent include polyamine, acid anhydride, polyphenol, and polymercaptan. Examples of the catalyst-type curing agent include tertiary amines, imidazoles, and Lewis acid complexes. The curing method of the epoxy resin is not particularly limited, and can be performed by a known method.
エラストマーの例としてはオレフィン系エラストマー、スチレン系エラストマー、エステル系エラストマー、アミド系エラストマー、塩化ビニル系エラストマー、これらの組み合わせ等が挙げられる。 Examples of elastomers include olefin elastomers, styrene elastomers, ester elastomers, amide elastomers, vinyl chloride elastomers, combinations thereof, and the like.
ゴムの例の例としては、天然ゴム、シリコーンゴム、スチレン・ブタジエンゴム、イソプレンゴム、ブタジエンゴム、クロロプレンゴム、アクリロニトリル・ブタジエンゴム、ニトリルブタジエンゴム、ブチルゴム、エチレン・プロピレンゴム、エチレン・プロピレン・ジエンゴム、ウレタンゴム、シリコーンゴム、フッ素ゴム、これらの組み合わせ等が挙げられる。なかでも、ブチルゴムが好ましい。 Examples of rubber include natural rubber, silicone rubber, styrene / butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, acrylonitrile / butadiene rubber, nitrile butadiene rubber, butyl rubber, ethylene / propylene rubber, ethylene / propylene / diene rubber, Examples thereof include urethane rubber, silicone rubber, fluororubber, and combinations thereof. Of these, butyl rubber is preferred.
ポリリン酸塩は、難燃剤として機能し、ポリリン酸アンモニウム、ポリリン酸メラミン等が含まれる。ポリリン酸塩は好ましくはポリリン酸アンモニウムである。ポリリン酸アンモニウムの市販品としては、クラリアント社製「AP422」、「AP462」、住友化学工業社製「スミセーフP」、チッソ社製「テラージュC60」が挙げられる。 The polyphosphate functions as a flame retardant and includes ammonium polyphosphate, melamine polyphosphate, and the like. The polyphosphate is preferably ammonium polyphosphate. Commercially available products of ammonium polyphosphate include “AP422” and “AP462” manufactured by Clariant, “Sumisafe P” manufactured by Sumitomo Chemical Co., Ltd., and “Terrage C60” manufactured by Chisso.
好ましいポリリン酸アンモニウムは、表面被覆されたポリリン酸アンモニウム(被覆ポリリン酸アンモニウムとも称する)であり、被覆ポリリン酸アンモニウムのうち、メラミンで表面被覆されたメラミン被覆ポリリン酸アンモニウムについては特開平9-286875に記載されており、シランで表面被覆されたシラン被覆ポリリン酸アンモニウムについては特開2000-63562に記載されている。メラミン被覆ポリリン酸アンモニウムは、(a)粉末状ポリリン酸アンモニウム粒子表面にメラミンを付加および/または付着したメラミン被覆ポリリン酸アンモニウム、(b)前記メラミン被覆ポリリン酸アンモニウム粒子の被覆層に存在するメラミン分子中のアミノ基が持つ活性水素と、該活性水素と反応しうる官能基を有する化合物とによって該粒子表面が架橋された被覆ポリリン酸アンモニウム、および/または(c)粉末状ポリリン酸アンモニウムまたは前記メラミン被覆ポリリン酸アンモニウム粒子表面を熱硬化性樹脂で被覆した被覆ポリリン酸アンモニウムである。メラミン被覆ポリリン酸アンモニウム粒子の市販品としては、例えば、クラリアント社製「AP462」、Budenheim Iberica社製「FR CROS 484」、「FR CROS 487」等が挙げられる。シラン被覆ポリリン酸アンモニウム粒子の市販品としては、例えば、Budenheim Iberica社製「FR CROS 486」が挙げられる。 A preferred ammonium polyphosphate is a surface-coated ammonium polyphosphate (also referred to as a coated ammonium polyphosphate). Of the coated ammonium polyphosphates, melamine-coated ammonium polyphosphate surface-coated with melamine is disclosed in JP-A-9-286875. JP-A-2000-63562 describes a silane-coated ammonium polyphosphate surface-coated with silane. The melamine-coated ammonium polyphosphate is composed of (a) melamine-coated ammonium polyphosphate obtained by adding and / or adhering melamine to the surface of powdered ammonium polyphosphate particles, and (b) melamine molecules present in the coating layer of the melamine-coated ammonium polyphosphate particles. And / or (c) powdered ammonium polyphosphate or the melamine in which the particle surface is crosslinked with an active hydrogen possessed by an amino group therein and a compound having a functional group capable of reacting with the active hydrogen This is a coated ammonium polyphosphate in which the surface of the coated ammonium polyphosphate particles is coated with a thermosetting resin. Examples of commercially available melamine-coated ammonium polyphosphate particles include “AP462” manufactured by Clariant, “FR CROS 484” and “FR CROS 487” manufactured by Budenheim Iberica. Examples of commercially available silane-coated ammonium polyphosphate particles include “FR CROS 486” manufactured by Budenheim Iberica.
被覆ポリリン酸アンモニウムの平均粒子径は好ましくは15〜35μmである。なお、被覆ポリリン酸アンモニウムの平均粒子径はレーザー回折式粒度分布測定にて測定できる。 The average particle diameter of the coated ammonium polyphosphate is preferably 15 to 35 μm. The average particle diameter of the coated ammonium polyphosphate can be measured by laser diffraction particle size distribution measurement.
可塑剤としては、下記に例示する1種または2種以上の可塑剤を組み合わせて使用し得る:ジ−2−エチルヘキシルフタレート(DOP)、ジ−n−オクチルフタレート、ジイソノニルフタレート(DINP)、ジイソデシルフタレート(DIDP)、ジウンデシルフタレート(DUP)、または炭素原子数10〜13程度の高級アルコールまたは混合アルコールのフタル酸エステル等のフタル酸エステル系可塑剤;
ジ−2−エチルヘキシルアジペート、ジ−n−オクチルアジペート、ジ−n−デシルアジペート、ジイソデシルアジペート、ジ−2−エチルヘキシルアゼレート、ジブチルセバケート、ジ−2−エチルヘキシルセバケート等の脂肪族二塩基酸エステル系可塑剤;
トリ−2−エチルヘキシルトリメリテート(TOTM)、トリ−n−オクチルトリメリテート、トリデシルトリメリテート、トリイソデシルトリメリテート、ジ−n−オクチル−n−デシルトリメリレート等のトリメリット酸エステル系可塑剤;
アジピン酸ジ−2−エチルヘキシル(DOA)およびアジピン酸ジイソデシル(DIDA)等のアジピン酸エステル系可塑剤;
セバシン酸ジブチル(DBS)およびセバシン酸ジ−2−エチルヘキシル(DOS)等のセバシン酸エステル系可塑剤;
トリブチルホスフェート、トリオクチルホスフェート、オクチルジフェニルホスフェート、トリブトキシエチルホスフェート、トリクロロエチルホスフェート、トリス(2−クロロプロピル)ホスフェート、トリス(2,3−ジクロロプロピル)ホスフェート、トリス(2,3−ジブロモプロピル)ホスフェート、トリス(ブロモクロロプロピル)ホスフェート、ビス(2,3−ジブロモプロピル)−2,3−ジクロロプロピルホスフェート、ビス(クロロプロピル)モノオクチルホスフェート等のリン酸エステル系可塑剤;
2,3,3',4'−ビフェニルテトラカルボン酸テトラヘプチルエステル等のビフェニルテトラカルボン酸テトラアルキルエステル系可塑剤;
ポリエステル系高分子可塑剤;
エポキシ化大豆油、エポキシ化亜麻仁油、エポキシ化綿実油、液状エポキシ樹脂等のエポキシ系可塑剤;
塩素化パラフィン;
五塩化ステアリン酸アルキルエステル等の塩素化脂肪酸エステル;および
常温で液状のリン化合物等。
As the plasticizer, one or more plasticizers exemplified below may be used in combination: di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), or a phthalate plasticizer such as a phthalate of higher alcohol or mixed alcohol having about 10 to 13 carbon atoms;
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 plasticizers;
Trimerits such as tri-2-ethylhexyl trimellitate (TOTM), tri-n-octyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, di-n-octyl-n-decyl trimellitate Acid ester plasticizers;
Adipate plasticizers such as di-2-ethylhexyl adipate (DOA) and diisodecyl adipate (DIDA);
Sebacic acid ester plasticizers such as dibutyl sebacate (DBS) and di-2-ethylhexyl sebacate (DOS);
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 Phosphate ester plasticizers such as tris (bromochloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, bis (chloropropyl) monooctyl phosphate;
Biphenyltetracarboxylic acid tetraalkyl ester plasticizers such as 2,3,3 ′, 4′-biphenyltetracarboxylic acid tetraheptyl 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 pentastearate; and phosphorus compounds that are liquid at room temperature.
リン化合物としては、特に限定されず、例えば、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリス(2エチルヘキシル)ホスフェート、トリフェニルホスフェート(TPP)、トリクレジルホスフェート(TCP)、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート等の各種リン酸エステル等が挙げられる。 The phosphorus compound is not particularly limited. For example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2 ethylhexyl) phosphate, triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate, cresyl Examples include various phosphate esters such as diphenyl phosphate and xylenyl diphenyl phosphate.
好ましい可塑剤は、リン系の可塑剤である。リン系の可塑剤には、リンを含む任意の可塑剤が含まれ、上記のリン酸エステル系可塑剤及びリン化合物が含まれる。 A preferred plasticizer is a phosphorus plasticizer. The phosphorus plasticizer includes any plasticizer containing phosphorus, and includes the above phosphoric ester plasticizers and phosphorus compounds.
好ましくは、可塑剤は、樹脂成分に対する相溶性の異なる複数の可塑剤を含む。 Preferably, the plasticizer includes a plurality of plasticizers having different compatibility with the resin component.
さらに好ましくは、可塑剤は、樹脂成分と前記可塑剤とのsmall法で計算される相溶性パラメーターの差が、0.5より大きい可塑剤と、樹脂成分と前記可塑剤とのsmall法で計算される相溶性パラメーターの差が0.5以下の可塑剤とを含む。 More preferably, in the plasticizer, the difference in the compatibility parameter calculated by the small method between the resin component and the plasticizer is greater than 0.5, and the plasticizer is calculated by the small method between the resin component and the plasticizer. And a plasticizer having a compatibility parameter difference of 0.5 or less.
相溶性の異なる複数の可塑剤を使用し、さらには樹脂成分と前記可塑剤とのsmall法で計算される相溶性パラメーターの差が0.5より大きい可塑剤と0.5以下の可塑剤とを使用すれば、難燃性及び耐水性に優れた耐火樹脂成形体の製造が容易となる。 A plurality of plasticizers having different compatibility are used, and a plasticizer having a difference in compatibility parameter calculated by the small method between the resin component and the plasticizer of more than 0.5 and a plasticizer of 0.5 or less If it is used, manufacture of the fire-resistant resin molding excellent in the flame retardance and water resistance becomes easy.
樹脂成分と前記可塑剤とのsmall法で計算される相溶性パラメーターの差が0.5より大きい可塑剤及び0.5以下の可塑剤の含有量は特に限定されないが、相溶性パラメーターの差が0.5より大きい可塑剤の含有量が多いことが好ましい。相溶性パラメーターの差が0.5より大きい可塑剤の含有量が多いと、難燃性及び耐水性に優れた耐火樹脂成形体をより容易に製造することができる。 The content of the plasticizer having a difference in the compatibility parameter calculated by the small method between the resin component and the plasticizer of more than 0.5 and the plasticizer of 0.5 or less is not particularly limited, but the difference in the compatibility parameter is A high plasticizer content greater than 0.5 is preferred. When the content of the plasticizer having a difference in compatibility parameter larger than 0.5 is large, a fire-resistant resin molded article having excellent flame retardancy and water resistance can be produced more easily.
可塑剤は、本発明の耐火樹脂成形体を構成する耐火樹脂組成物に、樹脂成分の量よりも多量に含有される。可塑剤を樹脂成分の量よりも多量に含有させることにより、可塑剤が耐火樹脂組成物の表面に浮き出し、耐火樹脂組成物の表面に油膜を形成する。表面全体に油膜をかかる油膜は肉眼で観察可能である。例えば、耐火樹脂成形体がシート状である場合、油膜をシートの幅広の一表面に少なくとも設けられるようにする。好ましくは可塑剤の含有量は、可塑剤の合計量で、樹脂成分100重量部に対し60重量部以上、300重量部以下、より好ましくは80重量部以上、300重量部以下である。より好ましい可塑剤の含有量は、樹脂成分100重量部に対し80〜200重量部である。 The plasticizer is contained in the fireproof resin composition constituting the fireproof resin molded article of the present invention in a larger amount than the amount of the resin component. By containing the plasticizer in a larger amount than the amount of the resin component, the plasticizer is raised on the surface of the refractory resin composition, and an oil film is formed on the surface of the refractory resin composition. The oil film covering the entire surface can be observed with the naked eye. For example, when the fireproof resin molded body is in a sheet form, an oil film is provided at least on one wide surface of the sheet. Preferably, the content of the plasticizer is 60 parts by weight or more and 300 parts by weight or less, more preferably 80 parts by weight or more and 300 parts by weight or less based on 100 parts by weight of the resin component as the total amount of the plasticizer. A more preferable content of the plasticizer is 80 to 200 parts by weight with respect to 100 parts by weight of the resin component.
本発明の耐火樹脂成形体を構成する耐火樹脂組成物は、熱膨張性黒鉛をさらに含有してもよい。耐火樹脂組成物が熱膨張性黒鉛を含有する場合、耐火樹脂組成物は、加熱により膨張する熱膨張性耐火樹脂組成物となる。 The fire resistant resin composition constituting the fire resistant resin molded article of the present invention may further contain thermally expandable graphite. When the refractory resin composition contains thermally expandable graphite, the refractory resin composition becomes a thermally expandable refractory resin composition that expands by heating.
熱膨張性黒鉛は、従来公知の物質であり、天然鱗状グラファイト、熱分解グラファイト、キッシュグラファイト等の粉末を濃硫酸、硝酸、セレン酸等の無機酸と濃硝酸、過塩素酸、過塩素酸塩、過マンガン酸塩、重クロム酸塩、過酸化水素等の強酸化剤とで処理してグラファイト層間化合物を生成させたもので、炭素の層状構造を維持したままの結晶化合物である。 Thermally expandable graphite is a conventionally known substance, and powders such as natural scaly graphite, pyrolytic graphite, and quiche graphite are mixed with inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, concentrated nitric acid, perchloric acid, and perchlorate. In addition, a graphite intercalation compound is produced by treatment with a strong oxidant such as permanganate, dichromate, hydrogen peroxide, etc., and is a crystalline compound that maintains a carbon layered structure.
熱膨張性黒鉛は任意選択で中和処理されてもよい。つまり、上記のように酸処理して得られた熱膨張性黒鉛を、更にアンモニア、脂肪族低級アミン、アルカリ金属化合物、アルカリ土類金属化合物等で中和する。上記脂肪族低級アミンとしては、例えば、モノメチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、プロピルアミン、ブチルアミン等が挙げられる。上記アルカリ金属化合物およびアルカリ土類金属化合物としては、例えば、カリウム、ナトリウム、カルシウム、バリウム、マグネシウム等の水酸化物、酸化物、炭酸塩、硫酸塩、有機酸塩等が挙げられる。中和処理した熱膨張性黒鉛の具体例としては、例えば、日本化成社製「CA−60S」、東ソー社製「GREP−EG」等が挙げられる。 The thermally expandable graphite may optionally be neutralized. That is, the thermally expandable graphite obtained by acid treatment as described above is further 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, and butylamine. Examples of the alkali metal compound and alkaline earth metal compound include hydroxides such as potassium, sodium, calcium, barium, and magnesium, oxides, carbonates, sulfates, and organic acid salts. Specific examples of the heat-expandable graphite subjected to the neutralization treatment include “CA-60S” manufactured by Nippon Kasei Co., Ltd. and “GREP-EG” manufactured by Tosoh Corporation.
本発明で用いられる熱膨張性黒鉛の粒度は、20〜200メッシュのものが好ましい。粒度が200メッシュより大きいと、黒鉛の膨張度が大きく、望む耐火断熱層が得られ、粒度が20メッシュより小さいと、樹脂と混練する際の、分散性が良好である。 The particle size of the thermally expandable graphite used in the present invention is preferably 20 to 200 mesh. When the particle size is larger than 200 mesh, the degree of expansion of graphite is large and a desired fireproof heat insulating layer is obtained. When the particle size is smaller than 20 mesh, the dispersibility when kneading with the resin is good.
熱膨張性黒鉛の含有量は特に限定されないが、樹脂成分100重量部に対して10〜500重量部であることが好ましく、樹脂成分100重量部に対して50〜300重量部であることがより好ましく、樹脂成分100重量部に対して50〜200重量部であることさらに好ましい。含有量が10重量部以上であると、体積膨張率が大きく樹脂サッシを構成する合成樹脂製部材が焼失した部分を十分埋めきることができ防火性能が発揮され、500重量部以下であると機械的強度が維持される。 The content of the thermally expandable graphite is not particularly limited, but is preferably 10 to 500 parts by weight with respect to 100 parts by weight of the resin component, and more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the resin component. Preferably, it is 50-200 weight part with respect to 100 weight part of resin components. When the content is 10 parts by weight or more, the volume of the volume expansion coefficient is large and the synthetic resin member constituting the resin sash can sufficiently fill the burned-out portion. Strength is maintained.
本発明の耐火樹脂成形体を構成する耐火樹脂組成物は、無機充填剤をさらに含有してもよい。 The fire resistant resin composition constituting the fire resistant resin molded article of the present invention may further contain an inorganic filler.
無機充填剤は、膨張断熱層が形成される際、熱容量を増大させ伝熱を抑制するとともに、骨材的に働いて膨張断熱層の強度を向上させる。無機充填剤としては特に限定されず、例えば、アルミナ、酸化亜鉛、酸化チタン、酸化カルシウム、酸化マグネシウム、酸化鉄、酸化錫、酸化アンチモン、フェライト類等の金属酸化物;水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、ハイドロタルサイト等の含水無機物;塩基性炭酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、炭酸ストロンチウム、炭酸バリウム等の金属炭酸塩等が挙げられる。 When the expanded heat insulating layer is formed, the inorganic filler increases the heat capacity and suppresses heat transfer, and works as an aggregate to improve the strength of the expanded 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; calcium hydroxide, magnesium hydroxide And water-containing 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.
また、無機充填剤としては、これらの他に、硫酸カルシウム、石膏繊維、ケイ酸カルシウム等のカルシウム塩;シリカ、珪藻土、ドーソナイト、硫酸バリウム、タルク、クレー、マイカ、モンモリロナイト、ベントナイト、活性白土、セピオライト、イモゴライト、セリサイト、ガラス繊維、ガラスビーズ、シリカ系バルン、窒化アルミニウム、窒化ホウ素、窒化ケイ素、カーボンブラック、グラファイト、炭素繊維、炭素バルン、木炭粉末、各種金属粉、チタン酸カリウム、硫酸マグネシウム「MOS」(商品名)、チタン酸ジルコン酸鉛、アルミニウムボレート、硫化モリブデン、炭化ケイ素、ステンレス繊維、ホウ酸亜鉛、各種磁性粉、スラグ繊維、フライアッシュ、脱水汚泥等が挙げられる。これらの無機充填剤は単独で用いても、2種以上を併用してもよい。 In addition to these, inorganic fillers include calcium salts such as calcium sulfate, gypsum fiber, calcium silicate; silica, diatomaceous earth, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite. , Imogolite, sericite, glass fiber, glass beads, silica 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, dehydrated sludge and the like. These inorganic fillers may be used alone or in combination of two or more.
無機充填剤の粒径としては、0.5〜100μmが好ましく、より好ましくは1〜50μmである。無機充填剤は、添加量が少ないときは、分散性が性能を大きく左右するため、粒径の小さいものが好ましいが、0.5μm未満になると二次凝集が起こり、分散性が悪くなる。添加量が多いときは、高充填が進むにつれて、樹脂組成物の粘度が高くなり成形性が低下するが、粒径を大きくすることで樹脂組成物の粘度を低下させることができる点から、粒径の大きいものが好ましい。粒径が100μmを超えると、成形体の表面性、樹脂組成物の力学的物性が低下する。 As a particle size of an inorganic filler, 0.5-100 micrometers is preferable, More preferably, it is 1-50 micrometers. When the addition amount of the inorganic filler is small, the dispersibility largely affects the performance, so that the particle size is preferably small. However, when it is less than 0.5 μm, secondary aggregation occurs and the dispersibility deteriorates. When the addition amount is large, the viscosity of the resin composition increases and moldability decreases as the high filling progresses, but the viscosity of the resin composition can be decreased by increasing the particle size. A thing with a large diameter is preferable. When the particle size exceeds 100 μm, the surface properties of the molded body and the mechanical properties of the resin composition are lowered.
一つの実施形態では、無機充填剤は金属酸化物、含水無機物、金属炭酸塩、シリカ、およびこれらの組み合わせから選択される。含水無機物は、アルカリ土類金属水酸化物を含む。 In one embodiment, the inorganic filler is selected from metal oxides, hydrous minerals, metal carbonates, silica, and combinations thereof. The hydrous inorganic substance contains an alkaline earth metal hydroxide.
無機充填剤としては、例えば、水酸化アルミニウムでは、粒径18μmの「ハイジライトH−31」(昭和電工社製)、粒径25μmの「B325」(ALCOA社製)、炭酸カルシウムでは、粒径1.8μmの「ホワイトンSB赤」(備北粉化工業社製)、粒径8μmの「BF300」(備北粉化工業社製)等が挙げられる。 As the inorganic filler, for example, for aluminum hydroxide, “Hijilite H-31” (manufactured by Showa Denko) having a particle size of 18 μm, “B325” (manufactured by ALCOA) having a particle size of 25 μm, and calcium carbonate, Examples include 1.8 μm “Whiteon SB Red” (manufactured by Bihoku Powdered Industries Co., Ltd.), “BF300” (manufactured by Bihoku Powdered Industries Co., Ltd.) having a particle size of 8 μm, and the like.
無機充填剤の含有量は特に限定されないが、樹脂成分100重量部に対して30〜500重量部であることが好ましい。含有量が30重量部以上であると、十分な防火性能が得られ、500重量部以下であると機械的強度が維持される。無機充填剤の含有量は、より好ましくは40〜350重量部である。 Although content of an inorganic filler is not specifically limited, It is preferable that it is 30-500 weight part with respect to 100 weight part of resin components. When the content is 30 parts by weight or more, sufficient fireproof performance is obtained, and when it is 500 parts by weight or less, the mechanical strength is maintained. The content of the inorganic filler is more preferably 40 to 350 parts by weight.
また、本発明の耐火樹脂成形体を構成する耐火樹脂組成物には、その物性を損なわない範囲で、熱安定剤、滑剤、加工助剤、熱分解型発泡剤、酸化防止剤、帯電防止剤、顔料等が添加されてもよい。 Further, the fireproof resin composition constituting the fireproof resin molded article of the present invention includes a heat stabilizer, a lubricant, a processing aid, a pyrolytic foaming agent, an antioxidant, and an antistatic agent as long as the physical properties are not impaired. A pigment or the like may be added.
熱安定剤としては、例えば、三塩基性硫酸鉛、三塩基性亜硫酸鉛、二塩基性亜リン酸鉛、ステアリン酸鉛、二塩基性ステアリン酸鉛等の鉛熱安定剤;有機錫メルカプト、有機錫マレート、有機錫ラウレート、ジブチル錫マレート等の有機錫熱安定剤;ステアリン酸亜鉛、ステアリン酸カルシウム等の金属石鹸熱安定剤等が挙げられ、これらは単独で用いられもよいし、二種以上が併用されてもよい。 Examples of the heat stabilizer include lead heat stabilizers such as tribasic lead sulfate, tribasic lead sulfite, dibasic lead phosphite, lead stearate, dibasic lead stearate; organotin mercapto, organic Organotin heat stabilizers such as tin malate, organotin laurate, dibutyltin malate; metal soap heat stabilizers such as zinc stearate and calcium stearate; these may be used alone or in combination of two or more You may use together.
滑剤としては、例えば、ポリエチレン、パラフィン、モンタン酸等のワックス類;各種エステルワックス類;ステアリン酸、リシノール酸等の有機酸類;ステアリルアルコール等の有機アルコール類;ジメチルビスアミド等のアミド化合物等が挙げられ、これらは単独で用いられもよいし、二種以上が併用されてもよい。 Examples of the lubricant 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.
加工助剤としては、例えば、塩素化ポリエチレン、メチルメタクリレート−エチルアクリレート共重合体、高分子量のポリメチルメタクリレート等が挙げられる。 Examples of the processing aid include chlorinated polyethylene, methyl methacrylate-ethyl acrylate copolymer, and high molecular weight polymethyl methacrylate.
熱分解型発泡剤としては、例えば、アゾジカルボンアミド(ADCA)、ジニトロソペンタメチレンテトラミン(DPT)、p,p−オキシビスベンゼンスルホニルヒドラジド(OBSH)、アゾビスイソブチロニトリル(AIBN)等が挙げられる。 Examples of the pyrolytic foaming agent include azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), p, p-oxybisbenzenesulfonylhydrazide (OBSH), azobisisobutyronitrile (AIBN), and the like. Can be mentioned.
上記の耐火樹脂組成物を、常法に従って、一軸押出機、二軸押出機等の押出機で溶融押出することにより、本発明の耐火樹脂成形体を得ることができる。溶融温度は、樹脂成分によって異なり、特に限定されないが、例えばポリ塩化ビニル樹脂の場合130〜170℃である。 The refractory resin molded article of the present invention can be obtained by melt-extruding the refractory resin composition with an extruder such as a single screw extruder or a twin screw extruder according to a conventional method. The melting temperature varies depending on the resin component and is not particularly limited. For example, in the case of a polyvinyl chloride resin, it is 130 to 170 ° C.
本発明の耐火樹脂成形体は、窓、障子、扉(すなわちドア)、戸、ふすま、および欄間等の建具;船舶;並びにエレベータ等の構造体に耐火性を付与するために使用され得る。上記の耐火樹脂組成物は成形性に優れているので、シート状の他、構造体の複雑な形状に適合させた異型成形体を容易に得ることができる。 The fire-resistant resin molded body of the present invention can be used to impart fire resistance to structures such as windows, shojis, doors (that is, doors), doors, brans, and balustrades; ships; and elevators. Since the above-mentioned refractory resin composition is excellent in moldability, it is possible to easily obtain an atypical molded body adapted to the complex shape of the structure in addition to the sheet shape.
図1は、建具としての窓1のサッシ枠に本発明の耐火樹脂成形体4を付与した例である。この例では、サッシ枠は2つの内枠2と、内枠2を包囲する1つの外枠3とを有し、内枠2および外枠3の枠本体の各辺に沿って、内枠2および外枠3の内部に耐火樹脂成形体3が取り付けられている。このようにして、本発明の耐火樹脂成形体4を設けることにより、窓1に耐火性を付与することができる。 FIG. 1 is an example in which a fireproof resin molded body 4 of the present invention is applied to a sash frame of a 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 and the outer frame 3 along each side of the frame main body 2. And the fireproof resin molding 3 is attached to the inside of the outer frame 3. Thus, fire resistance can be imparted to the window 1 by providing the fireproof resin molded body 4 of the present invention.
本発明は、樹脂成分と、ポリリン酸塩とを含む耐火樹脂組成物の表面に可塑剤の被膜を形成することを含む、耐火樹脂組成物におけるポリリン酸塩の加水分解による析出物の発生の抑制方法も包含する。耐火樹脂組成物中の各成分については耐火樹脂組成物について上述した通りである。 The present invention suppresses generation of precipitates due to hydrolysis of polyphosphate in a refractory resin composition, including forming a plasticizer film on the surface of the refractory resin composition containing a resin component and a polyphosphate. Methods are also encompassed. Each component in the refractory resin composition is as described above for the refractory resin composition.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はこれらに限定されない。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
1.耐火シートの作成
実施例1
表1に示した配合量で、合成樹脂としてポリ塩化ビニル100重量部、可塑剤としてトリクレジルホスフェート(TCP)75重量部およびジ−2−エチルヘキシルフタレート(DOP)75重量部、難燃剤としてポリリン酸アンモニウム(APP)(クラリアント社製「AP422」)20重量部、熱膨張性黒鉛(東ソー社製「GREP−EG」)、および無機充填剤として炭酸カルシウム(備北粉化社製「ホワイトンBF−300」)30重量部をニーダーにて混合した後、その混合物をカレンダーロールにてシート化に成型し、厚さ1.5mmの耐火樹脂成形体としての耐火シートを得た。
実施例2〜11、比較例1
実施例2〜11および比較例1についても、表1に示した配合量で成分を混合および押出成形し、耐火シートを得た。比較例1では2つの可塑剤の合計量をポリ塩化ビニルと同じ100重量部とした。
1. Preparation of fireproof sheet Example 1
100 parts by weight of polyvinyl chloride as a synthetic resin, 75 parts by weight of tricresyl phosphate (TCP) and 75 parts by weight of di-2-ethylhexyl phthalate (DOP) as a plasticizer, and polyphosphorus as a flame retardant 20 parts by weight of ammonium oxide (APP) ("Cl422" manufactured by Clariant), thermally expandable graphite ("GREP-EG" manufactured by Tosoh Corporation), and calcium carbonate ("Whiteon BF-" manufactured by Bihoku Flour Chemical Co., Ltd.) as an inorganic filler 300 ") 30 parts by weight were mixed with a kneader, and then the mixture was formed into a sheet with a calender roll to obtain a fireproof sheet as a fireproof resin molded body having a thickness of 1.5 mm.
Examples 2-11, Comparative Example 1
Also in Examples 2 to 11 and Comparative Example 1, the components were mixed and extruded at the blending amounts shown in Table 1 to obtain fireproof sheets. In Comparative Example 1, the total amount of the two plasticizers was 100 parts by weight, the same as that of polyvinyl chloride.
樹脂と可塑剤については、small法で計算される相溶性パラメーター(SP値)を記載した。
2.油膜の形成の確認
実施例1〜11の耐火シートについて、その表面に油膜が形成されていることを以下の方法で確認した。当該油膜の主成分は可塑剤であった。一方、比較例1では、その表面に油膜は形成されていなかった。
<表面に油膜が形成されている点の確認方法>
油性ペンで耐火シートの表面に5本線を描き、0℃、室温、及び50℃で1週間静置後、いずれの条件でもにじみがあるものを○(油膜あり)、そうでないものを×(油膜なし)とした。
<油膜に可塑剤が含まれていることの確認>
上記静置前後の耐火シートの表面を赤外分光法にて分析し、樹脂成分由来のピークに対して、可塑剤由来のピークが増加していることで油膜に可塑剤が含まれていることを確認した。
3.耐火シートの耐水性評価
実施例1〜11および比較例1の耐火シートに水滴をスポイトにて2ml落とし、終夜(24時間)放置し、水滴を乾燥させ、翌日、シートの表面を観察し、耐水性を目視で評価した。◎は非常に良好(水滴を落とした部分の表面に白色物が見えない)、○を良好(水滴を落とした部分の表面に一部白色物はあるが概ねなし)、△をやや良好(水滴を落とした部分の表面に○よりも多く一部白色物はあるが概ねなし)、×を不良(水滴を落とした部分の表面に白色析出物発生)とした。
For the resin and plasticizer, the compatibility parameter (SP value) calculated by the small method is described.
2. Confirmation of formation of oil film About the fireproof sheets of Examples 1 to 11, it was confirmed by the following method that an oil film was formed on the surface. The main component of the oil film was a plasticizer. On the other hand, in Comparative Example 1, no oil film was formed on the surface.
<Method for confirming that oil film is formed on the surface>
Draw 5 lines on the surface of the refractory sheet with an oil-based pen, and after standing at 0 ° C, room temperature, and 50 ° C for 1 week, ○ (oil film) indicates that there is bleeding under any condition, × (oil film) otherwise None).
<Confirmation that oil film contains plasticizer>
The surface of the refractory sheet before and after standing is analyzed by infrared spectroscopy, and the plastic film is contained in the oil film due to the increase in the peak derived from the plasticizer relative to the peak derived from the resin component. It was confirmed.
3. Water resistance evaluation of fireproof sheets
2 ml of water drops were dropped on the fireproof sheets of Examples 1 to 11 and Comparative Example 1 with a dropper and left overnight (24 hours), the water drops were dried, and the surface of the sheets was observed the next day, and the water resistance was visually evaluated. . ◎ is very good (no white matter can be seen on the surface of the part where the water drops have been dropped), ○ is good (the surface of the part where the water drops have been dropped is partly white), and △ is somewhat good (water drops) In the surface of the part where the water drops were dropped, there were some white matters more than ○, but there was almost no white matter), and x was regarded as bad (white precipitates were generated on the surface of the parts where the water drops were dropped).
実施例1〜11の耐火シートは耐水性に優れており、耐火シート表面における白色の析出物の発生が抑制された。
4.耐火性評価
実施例及び比較例の耐火シートを10cm角に切り出し、300gの水道水に浸漬し、23℃で1週間浸漬した。
(膨張倍率)
水浸漬後のサンプルを50℃で3日間乾燥の後、浸漬前後の重量差より、溶出率を算出した。さらに、乾燥後の試験片を厚みを測定し、電気炉に供給し、600℃で30分間加熱した後、試験片の厚さを測定し、(加熱後の試験片の厚さ)/(加熱前の試験片の厚さ)を膨張倍率として算出した。
(残渣硬さ)
膨張倍率を測定した加熱後の試験片を圧縮試験機(カトーテック社製、「フィンガーフイリングテスター」)に供給し、0.25cm2の圧子で0.1cm/秒の速度で圧縮し、破断点応力を測定した。
(形状保持性)
膨張倍率を測定した加熱後の試験片を90°に傾け、試験片が崩れず、形状保持ができたものを○、崩れてしまったものを×と評価した。
The fireproof sheets of Examples 1 to 11 were excellent in water resistance, and generation of white precipitates on the fireproof sheet surface was suppressed.
4). Fire resistance evaluation The fireproof sheets of Examples and Comparative Examples were cut into 10 cm squares, immersed in 300 g of tap water, and immersed at 23 ° C. for 1 week.
(Expansion magnification)
The sample after water immersion was dried at 50 ° C. for 3 days, and the elution rate was calculated from the weight difference before and after immersion. Furthermore, after measuring the thickness of the test piece after drying, supplying it to an electric furnace and heating it at 600 ° C. for 30 minutes, the thickness of the test piece is measured and (thickness of the test piece after heating) / (heating) The thickness of the previous test piece) was calculated as the expansion ratio.
(Residue hardness)
The heated test piece whose expansion ratio was measured was supplied to a compression tester (“Finger Filling Tester” manufactured by Kato Tech Co., Ltd.), compressed at a speed of 0.1 cm / sec with a 0.25 cm 2 indenter, and fractured. Point stress was measured.
(Shape retention)
The heated test piece whose expansion ratio was measured was tilted at 90 °, and the test piece did not collapse and the shape could be retained was evaluated as ◯, and the broken specimen was evaluated as x.
Claims (10)
前記樹脂成分と前記可塑剤とのsmall法で計算される相溶性パラメーターの差が0.5以下の可塑剤とを含有することを特徴とする請求項1又は2に記載の耐火樹脂成型体。 A plasticizer having a difference in compatibility parameter calculated by the small method between the resin component and the plasticizer of greater than 0.5;
The fireproof resin molded article according to claim 1 or 2, comprising a plasticizer having a difference in compatibility parameter calculated by the small method between the resin component and the plasticizer of 0.5 or less.
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WO2018164095A1 (en) * | 2017-03-06 | 2018-09-13 | 積水化学工業株式会社 | Multicolor molded article molding material with excellent rigidity and fire resistance |
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JP2019019665A (en) * | 2017-01-25 | 2019-02-07 | 積水化学工業株式会社 | Thermally expandable fireproof sheet |
JP2019019666A (en) * | 2017-01-25 | 2019-02-07 | 積水化学工業株式会社 | Thermally expandable fireproof sheet |
JPWO2018139494A1 (en) * | 2017-01-25 | 2019-02-07 | 積水化学工業株式会社 | Thermal expansion fireproof sheet |
WO2018164095A1 (en) * | 2017-03-06 | 2018-09-13 | 積水化学工業株式会社 | Multicolor molded article molding material with excellent rigidity and fire resistance |
JPWO2018164095A1 (en) * | 2017-03-06 | 2019-03-14 | 積水化学工業株式会社 | Multicolor molding material with excellent rigidity and fire resistance |
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