JP2007501307A - 難燃性熱可塑性樹脂組成物 - Google Patents
難燃性熱可塑性樹脂組成物 Download PDFInfo
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- JP2007501307A JP2007501307A JP2006522500A JP2006522500A JP2007501307A JP 2007501307 A JP2007501307 A JP 2007501307A JP 2006522500 A JP2006522500 A JP 2006522500A JP 2006522500 A JP2006522500 A JP 2006522500A JP 2007501307 A JP2007501307 A JP 2007501307A
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- phosphate
- rubber
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 24
- 239000011342 resin composition Substances 0.000 title claims abstract description 22
- 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 title claims abstract description 21
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 13
- 239000000178 monomer Substances 0.000 claims abstract description 63
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 28
- -1 oxaphospholane compound Chemical class 0.000 claims abstract description 24
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 18
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- 239000010452 phosphate Substances 0.000 claims abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- 229920001890 Novodur Polymers 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 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 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- FXPDGSSSQUFIPW-UHFFFAOYSA-N oxaphospholane Chemical compound C1COPC1 FXPDGSSSQUFIPW-UHFFFAOYSA-N 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 229920003244 diene elastomer Polymers 0.000 claims description 5
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 4
- 229920002943 EPDM rubber Polymers 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- OJUVOJCIHNPHSA-UHFFFAOYSA-N bis(2,6-dimethylphenyl) (3-hydroxyphenyl) phosphate Chemical compound CC1=CC=CC(C)=C1OP(=O)(OC=1C(=CC=CC=1C)C)OC1=CC=CC(O)=C1 OJUVOJCIHNPHSA-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 2
- 229920000800 acrylic rubber Polymers 0.000 claims description 2
- GUDSEWUOWPVZPC-UHFFFAOYSA-N bis(2,4-ditert-butylphenyl) hydrogen phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(O)(=O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C GUDSEWUOWPVZPC-UHFFFAOYSA-N 0.000 claims description 2
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 claims description 2
- 229940106691 bisphenol a Drugs 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229920003049 isoprene rubber Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- KZGROEDUAFPSGN-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphate Chemical compound CC(C)(C)C1=CC=C(OP(O)(O)=O)C(C(C)(C)C)=C1 KZGROEDUAFPSGN-UHFFFAOYSA-N 0.000 claims 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 abstract 1
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- 238000000034 method Methods 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 150000002366 halogen compounds Chemical class 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- WZZNZLTYLRKPII-UHFFFAOYSA-N bis(2,4-ditert-butylphenyl) (3-hydroxyphenyl) phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(=O)(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=CC(O)=C1 WZZNZLTYLRKPII-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical group OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000479 mixture part Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
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Abstract
芳香族ビニル系単量体35〜95重量部、前記芳香族ビニル系単量体と共重合可能な単量体1〜20重量部、ならびに加工性及び耐熱性を付与する単量体0〜15重量部をグラフト重合させて得られたグラフト共重合体樹脂20〜100重量%;ならびに(a2)芳香
族ビニル系単量体60〜90重量部、前記芳香族ビニル系単量体と共重合可能な単量体10〜40重量部、ならびに加工性及び耐熱性を付与する単量体0〜30重量部を共重合させて得られた共重合体樹脂0〜80重量%からなるゴム変性ポリスチレン樹脂100重量部;(B)オキサホスホラン系化合物0.1〜15重量部;ならびに(C)芳香族リン酸エステル化合物0〜20重量部を含んでいる。
Description
本発明のさらに他の目的は、ハロゲン系化合物を用いないことにより環境親和的で人体に無害な難燃性熱可塑性樹脂組成物を提供することにある。
部、芳香族ビニル系単量体35〜95重量部、前記芳香族ビニル系単量体と共重合可能な単量体1〜20重量部、及び加工性及び耐熱性を付与する単量体0〜15重量部をグラフト重合させて得られたグラフト共重合体樹脂20〜100重量%;ならびに(a2)芳香
族ビニル系単量体60〜90重量部、前記芳香族ビニル系単量体と共重合可能な単量体10〜40重量部、及び加工性及び耐熱性を付与する単量体0〜30重量部を共重合させて得られた共重合体樹脂0〜80重量%からなるゴム変性スチレン系樹脂100重量部に対して、(B)オキサホスホラン系化合物0.1〜15重量部、ならびに(C)芳香族リン酸エステル化合物0〜20重量部を含むことを特徴とする。
本発明に係る樹脂組成物に用いるゴム変性スチレン系樹脂は、ビニル芳香族系重合体からなるマトリックス(連続相)中にゴム状重合体(ゴム相重合体、rubber polymer、rubber phase polymer)が粒子形態で分散して存在する重合体であり、その製造方法はゴム状重合体に芳香族ビニル系単量体、及び必要に応じて選択的に前記芳香族ビニル系単量体とグラフト共重合可能な単量体を添加して重合するというものである。このようなゴム変性スチレン系樹脂は、乳化重合法、懸濁重合法、塊状重合法のような周知の重合方法により製造でき、通常、このグラフト共重合体樹脂と共重合体樹脂とを混合押出することにより生産される。塊状重合法の場合は、グラフト共重合体樹脂と共重合体樹脂とを別々に製造せず、1つの反応工程のみでゴム変性スチレン系樹脂を製造する。いずれの重合方法によって製造する場合でも、最終のゴム変性スチレン系樹脂成分中のゴム含量は、ベース樹脂全体に対して5〜30重量%であるのが好ましい。
本発明で用いられるグラフト共重合体樹脂は、ゴム状重合体、芳香族ビニル系単量体、この芳香族ビニル系単量体と共重合可能な単量体、及び加工性及び耐熱性を付与する単量体をグラフト共重合させて得る。
(EPDM)などを挙げることができる。この中では、ジエン系ゴムとブタジエン系ゴムが好ましく、ブタジエン系ゴムがより好ましい。ゴム状重合体の含量は5〜65重量部が好ましい。
(a2)共重合体樹脂
本発明に用いられる共重合体樹脂は、前記グラフト共重合体樹脂(a2)の成分の中で
ゴム以外の単量体の割合および相溶性に応じて製造され、芳香族ビニル系単量体、この芳香族ビニル系単量体と共重合可能な単量体、及び加工性及び耐熱性を付与する単量体を共重合させて得られる。
本発明で用いられるオキサホスホラン系化合物は、下記化学式(I)のオキサホスホラン系構造を有する化合物である:
本発明で用いられる芳香族リン酸エステル化合物は下記化学式(II)の構造を有する化合物である:
り、XはC6−C20のアリール基またはアルキル置換のC6−C20のアリール基であり、このアルキル置換のC6−C20のアリール基はレソルシノール、ヒドロキノール、ビスフェ
ノール−Aなどのジアルコールからの誘導体であり、nは0〜4である。)。
ェート、ヒドロキノールビス(2,6−ジメチルフェニル)ホスフェート、ヒドロキノールビス(2,4−ジt−ブチルフェニル)ホスフェートなどがある。これら芳香族リン酸エステル化合物は単独で用いることができ、またこれら化合物の混合物として用いることも可能である。
難燃性熱可塑性樹脂組成物を製造するために実施例1−3及び比較例1−2で用いられた成分は以下のとおりある:
(A)ゴム変性スチレン系樹脂
(a1)グラフト共重合体樹脂
ブタジエンゴムラテックスの固形分50重量部、スチレン36重量部、グラフト共重合可能な単量体であるアクリロニトリル14重量部、及び脱イオン水150重量部の混合物に、この混合物の総固形分に対してオレイン酸カリウム1.0重量部、クメンヒドロペルオキシド0.4重量部、メルカプタン系連鎖移動剤0.2重量部、ブドウ糖0.4重量部、硫酸鉄水和物0.01重量部、及びピロリン酸ナトリウム0.3重量部を添加して、5時間75℃に維持して反応を完了し、グラフト共重合体(g−ABS)ラテックスを製造した。この結果の樹脂組成物固形分に対して硫酸0.4重量部を付加し凝固させて、グラフト共重合体樹脂(g−ABS)を粉末状態で得た。
スチレン75重量部、アクリロニトリル25重量部、及び脱イオン水120重量部の混合物に、必要な添加剤であるアゾビスイソブチロニトリル0.2重量部、トリカルシウムホスフェート0.4重量部、及びメルカプタン系連鎖移動剤0.2重量部を添加して、室温から80℃まで90分間昇温させた後、この温度で180分に維持してスチレン/アクリロニトリル共重合体樹脂(SAN)を製造した。これを水洗、脱水及び乾燥して粉末状態のスチレン/アクリロニトリル共重合体樹脂(SAN)を製造した。
融点が102〜104℃である2−メチル−2,5−ジオキソ−1−オキサ−2−ホスホランを用いた。
日本大八化学(株)の商品名PX200であるレソルシノールビス(2,6−ジメチルフェニル)ホスフェートを用いた。
前記成分(A)〜(C)を下記表1に示す量で混ぜて、通常の二軸押出機で180〜2
50℃の温度範囲で押出してペレットを製造した。製造されたペレットを80℃で3時間乾燥した後、6 Oz射出機で成形温度180〜280℃、金型温度40〜80℃の条件
で射出して難燃試験片及び物性試験片を製造した。
て測定し、耐熱度をASTM D1525に準じて5kgf荷重で測定した。
比較例1は、前記オキサホスホラン系化合物を用いないことを除いて実施例1と同様な方法で行った。比較例2は、前記オキサホスホラン系化合物の代わりに、芳香族リン酸エステルを難燃剤として用いたことを除いて実施例1と同様な方法で行った。試験結果を表1に示す。
Claims (5)
- (A)(a1)ゴム状重合体5〜65重量部、芳香族ビニル系単量体35〜95重量部、
前記芳香族ビニル系単量体と共重合可能な単量体1〜20重量部、及び加工性及び耐熱性を付与する単量体0〜15重量部をグラフト重合させて得られたグラフト共重合体樹脂20〜100重量%;ならびに
(a2)芳香族ビニル系単量体60〜90重量部、前記芳香族ビニル系単量体と共
重合可能な単量体10〜40重量部、及び加工性及び耐熱性を付与する単量体0〜30重量部を共重合させて得られた共重合体樹脂0〜80重量%;
からなるゴム変性スチレン系樹脂100重量部;
(B)下記化学式(I)の構造を有するオキサホスホラン系化合物0.1〜15重量部:
(C)下記化学式(II)の構造を有する芳香族リン酸エステル化合物0〜20重量部;
を含むことを特徴とする難燃性熱可塑性樹脂組成物:
キル基であり、XはC6−C20のアリール基またはアルキル置換のC6−C20のアリール基であり、このアルキル置換のC6−C20のアリール基はレソルシノール、ヒドロキノール
、ビスフェノール−Aなどのジアルコールからの誘導体であり、nは0〜4である。)。 - 前記グラフト共重合体樹脂(a1)に用いられるゴム状重合体は、ジエン系ゴム、前記
ジエン系ゴムに水素を添加した飽和ゴム、イソプレンゴム、アクリル系ゴム、及びエチレン−プロピレン−ジエン単量体の三元共重合体(EPDM)よりなる群から一つ以上選択され;前記芳香族ビニル系単量体は、スチレン、α−メチルスチレン、及びp−メチルスチレンよりなる群から一つ以上選択され;前記芳香族ビニル系単量体と共重合可能な単量体はシアン化ビニル系化合物及び不飽和ニトリル系化合物よりなる群から一つ以上選択され;前記加工性及び耐熱性を付与する単量体は、アクリル酸、メタクリル酸、無水マレイン酸、及びN−置換マレイドよりなる群から一つ以上選択されることを特徴とする、請求
項1に記載の難燃性熱可塑性樹脂組成物。 - 前記オキサホスホラン系化合物(B)は、2−メチル−2,5−ジオキソ−1−オキサ−2−ホスホラン及び2−フェニル−2,5−ジオキソ−1−オキサ−2−ホスホランよりなる群から一つ以上選択されることを特徴とする、請求項1に記載の難燃性熱可塑性樹脂組成物。
- 前記芳香族リン酸エステル化合物(C)は、トリフェニルホスフェート、トリ(2,6−ジメチル)ホスフェート、レソルシノールビス(ジフェニル)ホスフェート、レソルシノールビス(2,6−ジメチルフェニル)ホスフェート、レソルシノールビス(2,4−ジt−ブチルフェニル)ホスフェート、ハイドロキノールビス(2,6−ジメチルフェニル)ホスフェート、及びハイドロキノールビス(2,4−ジt−ブチルフェニル)ホスフェートよりなる群から一つ以上選択されることを特徴とする、請求項1に記載の難燃性熱可塑性樹脂組成物。
- 前記芳香族リン酸エステル化合物(C)は、0.1〜15重量部であることを特徴とする、請求項1に記載の難燃性熱可塑性樹脂組成物。
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KR100654525B1 (ko) * | 2005-12-30 | 2006-12-05 | 제일모직주식회사 | 카르복시에틸 포스피네이트 에스테르 염 화합물과 이를함유하는 난연성 열가소성 수지조성물 |
KR100962174B1 (ko) * | 2007-12-10 | 2010-06-10 | 제일모직주식회사 | 입체 장애적 페놀계 포스포네이트 난연제 및 이를 포함한난연성 폴리카보네이트계 수지 조성물 |
KR101411008B1 (ko) * | 2010-12-22 | 2014-06-23 | 제일모직주식회사 | 신규 인계 화합물, 그 제조방법 및 이를 포함하는 난연성 열가소성 수지 조성물 |
CN102532191B (zh) | 2010-12-22 | 2014-11-12 | 第一毛织株式会社 | 新型磷化合物、其制备方法以及包括该磷化合物的阻燃热塑性树脂组合物 |
KR101465476B1 (ko) * | 2011-12-06 | 2014-11-26 | 제일모직주식회사 | 새로운 구조를 갖는 인계 화합물, 이의 제조방법, 및 이를 포함하는 난연성 열가소성 수지 조성물 |
JP2014177596A (ja) * | 2013-03-15 | 2014-09-25 | Ricoh Co Ltd | 再生樹脂組成物、成形品、画像形成装置及び再生樹脂組成物の製造方法 |
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CN110938234B (zh) * | 2018-09-25 | 2021-06-08 | 中山台光电子材料有限公司 | 阻燃性化合物、其制造方法、树脂组合物及其制品 |
KR20230037218A (ko) * | 2021-09-09 | 2023-03-16 | 롯데케미칼 주식회사 | 열가소성 수지 조성물 및 이로부터 형성된 성형품 |
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