JP4835975B2 - Method for producing phosphorus-containing flame retardant, phosphorus-containing flame retardant, flame retardant polyester and method for producing flame retardant polyester - Google Patents
Method for producing phosphorus-containing flame retardant, phosphorus-containing flame retardant, flame retardant polyester and method for producing flame retardant polyester Download PDFInfo
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- JP4835975B2 JP4835975B2 JP2005516649A JP2005516649A JP4835975B2 JP 4835975 B2 JP4835975 B2 JP 4835975B2 JP 2005516649 A JP2005516649 A JP 2005516649A JP 2005516649 A JP2005516649 A JP 2005516649A JP 4835975 B2 JP4835975 B2 JP 4835975B2
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- Prior art keywords
- flame retardant
- phosphorus
- containing flame
- polyester
- producing
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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 title claims description 148
- 239000003063 flame retardant Substances 0.000 title claims description 147
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 107
- 239000011574 phosphorus Substances 0.000 title claims description 107
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 104
- 229920000728 polyester Polymers 0.000 title claims description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 55
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 108
- -1 alkylene glycol Chemical compound 0.000 claims description 46
- 239000003963 antioxidant agent Substances 0.000 claims description 35
- 230000003078 antioxidant effect Effects 0.000 claims description 32
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 29
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 18
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 18
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 9
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 9
- 241001550224 Apha Species 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical group C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 claims 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 150000008064 anhydrides Chemical class 0.000 description 9
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229940119177 germanium dioxide Drugs 0.000 description 3
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- UQZPTVULCJDKIV-UHFFFAOYSA-N CCC.O[PH2]=O Chemical compound CCC.O[PH2]=O UQZPTVULCJDKIV-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 101000766096 Halorubrum sodomense Archaerhodopsin-3 Proteins 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ISWLRMQDZDXXBC-UHFFFAOYSA-N O[PH2]=O.CCCC Chemical compound O[PH2]=O.CCCC ISWLRMQDZDXXBC-UHFFFAOYSA-N 0.000 description 2
- ZCAUYTYTNDUKQS-UHFFFAOYSA-N O[PH2]=O.CCCCC Chemical compound O[PH2]=O.CCCCC ZCAUYTYTNDUKQS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- PHWXYKUZSUKPCM-ALCCZGGFSA-N (z)-2-pentan-3-ylbut-2-enedioic acid Chemical compound CCC(CC)C(\C(O)=O)=C\C(O)=O PHWXYKUZSUKPCM-ALCCZGGFSA-N 0.000 description 1
- IHWDIGHWDQPQMQ-UHFFFAOYSA-N 1-octadecylsulfanyloctadecane Chemical compound CCCCCCCCCCCCCCCCCCSCCCCCCCCCCCCCCCCCC IHWDIGHWDQPQMQ-UHFFFAOYSA-N 0.000 description 1
- RUNJHCZDNSMWGF-UHFFFAOYSA-N 1-propylphosphonoylpropane Chemical compound CCCP(=O)CCC RUNJHCZDNSMWGF-UHFFFAOYSA-N 0.000 description 1
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HAOFWBRPURXAQK-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)N(N)C(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HAOFWBRPURXAQK-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- WLLLTBGMZHYHEJ-UHFFFAOYSA-N CC.O[PH2]=O Chemical compound CC.O[PH2]=O WLLLTBGMZHYHEJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 241001483078 Phyto Species 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- HVPNHVYDDAGZOE-UHFFFAOYSA-N [PH2](O)=O.C1(=CC=CC=C1)CC Chemical compound [PH2](O)=O.C1(=CC=CC=C1)CC HVPNHVYDDAGZOE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 1
- JMCNGFNJWDJIIV-UHFFFAOYSA-N dibutyl(oxo)phosphanium Chemical compound CCCC[P+](=O)CCCC JMCNGFNJWDJIIV-UHFFFAOYSA-N 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- YVXVNGVYXSQARS-UHFFFAOYSA-N diethyl(oxo)phosphanium Chemical compound CC[P+](=O)CC YVXVNGVYXSQARS-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- WQAWEUZTDVWTDB-UHFFFAOYSA-N dimethyl(oxo)phosphanium Chemical compound C[P+](C)=O WQAWEUZTDVWTDB-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical class C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- PYFJQRSJTZCTPX-UHFFFAOYSA-N tris(2,3-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC(OP(OC=2C(=C(C=CC=2)C(C)(C)C)C(C)(C)C)OC=2C(=C(C=CC=2)C(C)(C)C)C(C)(C)C)=C1C(C)(C)C PYFJQRSJTZCTPX-UHFFFAOYSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は含リン難燃剤の製造方法、含リン難燃剤及び該含リン難燃剤を構成単位として含む難燃性ポリエステルに関する。 The present invention relates to a method for producing a phosphorus-containing flame retardant, a phosphorus-containing flame retardant, and a flame-retardant polyester containing the phosphorus-containing flame retardant as a constituent unit.
近年人命尊重の立場から、繊維を初めとする種々の成型品において難燃化が要求特性として挙げられ、様々な研究が行なわれている。線状ポリエステルから製造される成型品においても、難燃剤をポリマー製造時に添加して共重合あるいはブレンドさせる方法や、成型時にポリエステル中に練り込む方法、さらには成型品を後加工して難燃性、耐炎性を付与する方法等が提案されている。これらの方法の中で工業的価値を考慮した場合、最も簡便でしかも得られる成型品の諸性能を損なわないという点で、ポリマー製造時に難燃剤を添加して共重合させる方法が有利である。ポリエステル製造時に共重合させる難燃剤としてはリン化合物が多く用いられている。しかしながら、多くのリン化合物は、ポリエステルの重縮合における高温、減圧下という条件では、熱分解を起こす、系外に飛散する、ポリエステル生成反応中に重合体のゲル化を引き起こす、等の問題を有するため、改善が要求されていた。 In recent years, from the standpoint of respecting human life, flame retardancy has been cited as a required characteristic in various molded products including fibers, and various studies have been conducted. Even in molded products manufactured from linear polyester, flame retardant is added at the time of polymer production, copolymerized or blended, kneaded into polyester at the time of molding, and molded products are post-processed to be flame retardant A method for imparting flame resistance has been proposed. In view of industrial value among these methods, a method of adding a flame retardant at the time of polymer production and copolymerizing is advantageous in that various performances of the molded product which is the simplest and obtainable are not impaired. Phosphorus compounds are often used as flame retardants for copolymerization during polyester production. However, many phosphorus compounds have problems such as thermal decomposition, scattering outside the system, and gelation of the polymer during the polyester formation reaction under the conditions of high temperature and reduced pressure in the polycondensation of polyester. Therefore, improvement was required.
係る問題を生じない含リン難燃剤であるポリエステルに共重合可能なリン化合物としては、エチレングリコールの存在下に９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキシドとイタコン酸とから製造される含リン化合物が公知である（特許文献１）。
しかし、特許文献１に開示された含リン化合物のエチレングリコール溶液には顕著な着色があり、これを用いて製造した難燃性ポリエステルは色調が悪いという問題を有しており、さらなる改善が求められていた。 However, the ethylene glycol solution of the phosphorus-containing compound disclosed in Patent Document 1 is markedly colored, and the flame-retardant polyester produced using this solution has a problem that the color tone is poor, and further improvement is required. It was done.
本発明は、ポリエステル製造時に共重合する含リン難燃剤であって、ポリエステルの重縮合における高温、減圧下という条件では、熱分解を起こす、系外に飛散する、ポリエステル生成反応中に重合体のゲル化を引き起こす、等の問題を起こさず、しかも製造した難燃性ポリエステルの色調が良好な含リン難燃剤及びその製造方法並びに該含リン難燃剤を共重合した難燃性ポリエステルを提供することを目的とする。 The present invention is a phosphorus-containing flame retardant that is copolymerized at the time of polyester production. Under the conditions of high temperature and reduced pressure in polyester polycondensation, thermal decomposition occurs. To provide a phosphorus-containing flame retardant having good color tone of a flame-retardant polyester produced without causing problems such as gelation, a method for producing the same, and a flame-retardant polyester copolymerized with the phosphorus-containing flame retardant With the goal.
本発明者らは、鋭意研究した結果、有機リン化合物と不飽和カルボン酸及び／又はその無水物をアルキレングリコール中で反応させて含リン難燃剤を製造する方法において、酸化防止剤を有機リン化合物に対し特定の割合となるように含有させる含リン難燃剤の製造方法により前記の課題を解決できることを見出し、本発明を完成した。 As a result of diligent research, the present inventors have determined that an antioxidant is an organophosphorus compound in a method for producing a phosphorus-containing flame retardant by reacting an organophosphorus compound with an unsaturated carboxylic acid and / or its anhydride in an alkylene glycol. As a result, the inventors have found that the above-mentioned problems can be solved by the method for producing a phosphorus-containing flame retardant contained in a specific ratio.
すなわち本発明の含リン難燃剤の製造方法は、有機リン化合物と不飽和カルボン酸及び／又はその無水物をアルキレングリコール中で反応させて含リン難燃剤を製造する方法において、少なくとも１種の酸化防止剤を、有機リン化合物に対して合計０．００１〜１０重量％の割合となるように含有させて反応させることを特徴とする。 That is, the method for producing a phosphorus-containing flame retardant according to the present invention is a method for producing a phosphorus-containing flame retardant by reacting an organic phosphorus compound with an unsaturated carboxylic acid and / or an anhydride thereof in alkylene glycol. It is characterized by making it contain and react an inhibitor so that it may become a total ratio of 0.001-10 weight% with respect to an organophosphorus compound.
係る製造方法により得られる含リン難燃剤は、含リン難燃剤化合物、酸化防止剤及びアルキレングリコールを含む組成物であり、含リン難燃剤化合物はカルボキシル基を含有し、重合後において難燃性ポリエステルの重合体構成単位となる。 The phosphorus-containing flame retardant obtained by such a production method is a composition containing a phosphorus-containing flame retardant compound, an antioxidant, and an alkylene glycol, and the phosphorus-containing flame retardant compound contains a carboxyl group and is a flame retardant polyester after polymerization. It becomes a polymer structural unit.
本発明の含リン難燃剤は、含リン難燃剤、酸化防止剤及びアルキレングリコールを含有し、色相（ＡＰＨＡ）が１２０以下であることを特徴とする。係る難燃剤は、本発明の含リン難燃剤の製造方法によって得られたものであることが好ましい。含リン難燃剤の組成物は、そのまま難燃性ポリエステルの製造に使用する。 The phosphorus-containing flame retardant of the present invention contains a phosphorus-containing flame retardant, an antioxidant, and an alkylene glycol, and has a hue (APHA) of 120 or less. Such a flame retardant is preferably obtained by the method for producing a phosphorus-containing flame retardant of the present invention. The phosphorus-containing flame retardant composition is used as it is for the production of flame retardant polyester.
係る含リン難燃剤は、ポリエステルの重縮合における高温、減圧下という条件では、熱分解を起こす、系外に飛散する、ポリエステル生成反応中に重合体のゲル化を引き起こす、等の問題を起こさず、しかも製造した難燃性ポリエステルの色調が良好である。 Such a phosphorus-containing flame retardant does not cause problems such as thermal decomposition, scattering out of the system, and gelation of the polymer during the polyester formation reaction under the conditions of high temperature and reduced pressure in the polycondensation of polyester. Moreover, the color tone of the flame-retardant polyester produced is good.
また本発明の難燃性ポリエステルは、本発明の含リン難燃剤を使用して製造され、重合体構成単位として含有することを特徴とする。 The flame-retardant polyester of the present invention is produced using the phosphorus-containing flame retardant of the present invention, and is contained as a polymer constituent unit.
本発明の製造方法により製造された含リン難燃剤のアルキレングリコール溶液は、着色が効果的に防止されている。また得られた含リン難燃剤のアルキレングリコール溶液を用いて製造される難燃性ポリエステルは色調が改善されたものである。 The alkylene glycol solution of the phosphorus-containing flame retardant produced by the production method of the present invention is effectively prevented from being colored. Moreover, the flame-retardant polyester produced using the obtained alkylene glycol solution of the phosphorus-containing flame retardant has an improved color tone.
本発明の含リン難燃剤の製造方法は、有機リン化合物と不飽和カルボン酸及び又はその酸無水物（以下、不飽和カルボン酸類という）をアルキレングリコール中で反応させる反応系に、少なくとも１種の酸化防止剤を含リン難燃剤を含有させることを特徴とするものである。含リン難燃剤の製造時に反応系に酸化防止剤を含有させる方法は、特に限定されるものではないが、例えば、
１）有機リン化合物、不飽和カルボン酸類及びアルキレングリコールに酸化防止剤を含有させて反応させて含リン難燃剤を製造する方法
２）有機リン化合物と不飽和カルボン酸類に酸化防止剤を含有させて反応させ、更にアルキレングリコールと反応させて含リン難燃剤を製造する方法
３）不飽和カルボン酸類とアルキレングリコールに酸化防止剤を含有させて反応させ、更に有機リン化合物を添加して反応させて含リン難燃剤を製造する方法
等が挙げられる。The method for producing a phosphorus-containing flame retardant according to the present invention includes at least one kind of reaction system in which an organophosphorus compound and an unsaturated carboxylic acid and / or an acid anhydride thereof (hereinafter referred to as unsaturated carboxylic acid) are reacted in alkylene glycol. An antioxidant is contained in a phosphorus-containing flame retardant. The method of adding an antioxidant to the reaction system during the production of the phosphorus-containing flame retardant is not particularly limited, for example,
1) A method for producing a phosphorus-containing flame retardant by reacting an organic phosphorus compound, an unsaturated carboxylic acid and an alkylene glycol with an antioxidant 2) An organic phosphorus compound and an unsaturated carboxylic acid containing an antioxidant A method of producing a phosphorus-containing flame retardant by reacting with an alkylene glycol 3) An antioxidant is added to an unsaturated carboxylic acid and an alkylene glycol to react, and an organophosphorus compound is further added to react. Examples thereof include a method for producing a phosphorus flame retardant.
本発明において使用可能な有機リン化合物とは、不飽和カルボン酸類と反応してカルボキシル基を有するリン化合物を形成可能な含リン化合物であれば特に限定されるものではないが、例えば、
１）ジメチルホスフィンオキシド、ジエチルホスフィンオキシド、ジプロピルホスフィンオキシド、ジブチルホスフィンオキシド、ジフェニルホスフィンオキシド等のホスフィンオキシド誘導体
２）９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキシド、メチルメタンホスフィネート、エチルメタンホスフィネート、メチルエタンホスフィネート、エチルエタンホスフィネート、メチルプロパンホスフィネート、エチルプロパンホスフィネート、メチルブタンホスフィネート、エチルブタンホスフィネート、メチルベンゼンホスフィネート、エチルベンゼンホスフィネート等のホスフィネート誘導体
等が挙げられる。これら例示化合物のなかでも、難燃効果が優れている点でホスフィネート誘導体を使用することが好ましく、とりわけ９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキシド（以下、ＤＯＰという）を使用することが好ましい。The organic phosphorus compound that can be used in the present invention is not particularly limited as long as it is a phosphorus-containing compound that can react with unsaturated carboxylic acids to form a phosphorus compound having a carboxyl group.
1) Phosphine oxide derivatives such as dimethylphosphine oxide, diethylphosphine oxide, dipropylphosphine oxide, dibutylphosphine oxide, diphenylphosphine oxide 2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide , Methyl methane phosphinate, ethyl methane phosphinate, methyl ethane phosphinate, ethyl ethane phosphinate, methyl propane phosphinate, ethyl propane phosphinate, methyl butane phosphinate, ethyl butane phosphinate, methyl benzene phosphinate, ethyl benzene phosphinate, etc. Phosphinate derivatives and the like. Among these exemplified compounds, it is preferable to use a phosphinate derivative in view of excellent flame retardancy, and in particular, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as “the phosphinate derivative”). (Referred to as DOP).
本発明において使用可能な不飽和カルボン酸としては、
１）アクリル酸、メタクリル酸、クロトン酸等の不飽和モノカルボン酸
２）アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチル、クロトン酸メチル、クロトン酸エチル等の不飽和モノカルボン酸アルキル
３）マレイン酸、フマル酸、メサコン酸、シトラコン酸、イタコン酸等の不飽和ジカルボン酸
４）マレイン酸ジメチル、マレイン酸ジエチル、フマル酸ジメチル、フマル酸ジエチル、メサコン酸ジメチル、メサコン酸ジエチル、シトラコン酸ジメチル、シトラコン酸ジエチル、イタコン酸ジメチル、イタコン酸ジエチル等の不飽和ジカルボン酸アルキル
５）無水マレイン酸、無水シトラコン酸、無水イタコン酸等の不飽和ジカルボン酸の酸無水物が挙げられる。上記例示化合物のなかでも不飽和ジカルボン酸、不飽和ジカルボン酸の酸無水物から選択される少なくとも１種の使用が好ましく、イタコン酸、無水イタコン酸の使用がより好ましい。As the unsaturated carboxylic acid that can be used in the present invention,
1) Unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid 2) Unsaturated monocarboxylic acid alkyl such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl crotonate, ethyl crotonate 3) Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid 4) Dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl mesaconic acid, diethyl mesaconic acid, citraconic acid Unsaturated dicarboxylic acid alkyl such as dimethyl, diethyl citraconic acid, dimethyl itaconate and diethyl itaconate 5) Acid anhydrides of unsaturated dicarboxylic acids such as maleic anhydride, citraconic anhydride and itaconic anhydride. Among the above exemplified compounds, at least one selected from unsaturated dicarboxylic acids and unsaturated dicarboxylic acid anhydrides is preferable, and itaconic acid and itaconic anhydride are more preferable.
本発明の含リン難燃剤の製造方法に使用可能な酸化防止剤は、特に限定されるものではないが、例えば、１）ヒンダードフェノール系酸化防止剤、２）リン系酸化防止剤、３）イオウ系酸化防止剤等が挙げられるなどである。 The antioxidant that can be used in the method for producing the phosphorus-containing flame retardant according to the present invention is not particularly limited. For example, 1) a hindered phenol-based antioxidant, 2) a phosphorus-based antioxidant, and 3) And sulfur-based antioxidants.
ヒンダードフェノール系酸化防止剤としては、４−ｔ−ブチルカテコール、３，５−ジ−ｔ−ブチル−４−ヒドロキシートルエン、ｎ−オクタデシル−β−（４’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）プロピオネート、テトラキス〔メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート〕メタン、１，３，５−トリメチル−２，４，６’−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、カルシウム（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ベンジル−モノエチル−フォスフェート）、トリエチレングリコール−ビス〔３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート〕、ペンタエリスリチル−テトラキス〔３−（３，５−ジ−ｔ−ブチルアニリノ）〕−１，３，５−トリアジン、３，９−ビス〔１，１−ジメチル−２−｛β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝エチル〕２，４，８，１０−テトラオキサスピロ〔５，５〕ウンデカン、ビス〔３，３−ビス（４’−ヒドロキシ−３’−ｔ−ブチルフェニル）酪酸〕グリコールエステル、トリフェノール、２，２’−エチリデンビス（４，６−ジ−ｔ−ブチルフェノール）、Ｎ，Ｎ−ビス〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニル〕ヒドラジン、２，２’−オキサミドビス〔エチル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、１，１，３−トリス（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシベンジル）−Ｓ−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、１，３，５−トリス（４−ｔ−ブチル−３−ヒドロキシ−２，６−ジメチルベンジル）イソシアヌレート、３，５−ジ−ｔ−ブチル−４−ヒドロキシヒドロシンナミックアシドトリエステルウイズ−１，３，５−トリス（２−ヒドロキシエチル）−Ｓ−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）、Ｎ，Ｎ−へキサメチレンビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ヒドロシンナアミド）等が挙げられる。 Examples of hindered phenol antioxidants include 4-t-butylcatechol, 3,5-di-t-butyl-4-hydroxy-toluene, and n-octadecyl-β- (4′-hydroxy-3 ′, 5 ′. -Di-t-butylphenyl) propionate, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4 , 6'-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, calcium (3,5-di-t-butyl-4-hydroxy-benzyl-monoethyl-phosphate), triethylene glycol -Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5- -T-butylanilino)]-1,3,5-triazine, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy } Ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis [3,3-bis (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, triphenol, 2,2′-ethylidenebis (4,6-di-tert-butylphenol), N, N-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2 '-Oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris (3', 5'-di-t-butyl-4'- Hydroxybe Gil) -S-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic acid triester with-1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4,6 (1H, 3H, 5H ), N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like.
またリン系酸化防止剤としては、トリス（ミックスド、モノ及びジノニルフェニル）フォスファイト、トリス（２，３−ジ−ｔ−ブチルフェニル）フォスファイト、４，４’−ブチリデン−ビス（３−メチル−６−ｔ−ブチルフェニル−ジ−トリデシル）フォスファイト、１，１，３−トリス（２−メチル−４−ジ−トリデシルフォスファイト−５−ｔ−ブチルフェニル）ブタン、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトール−ジ−フォスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレンフォスファナイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリストール−ジ−フォスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）４，４’−ビフェエレンジホスフォナイト、トリフェニルホスファイト、ジフェニルデシルホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリドデシルホスファイト、トリオクタデシルフォスファイト、トリノニルフェニルホスファイト、トリドデシルトリチオホスファイト等を挙げることができる。 Examples of phosphorus antioxidants include tris (mixed, mono and dinonylphenyl) phosphite, tris (2,3-di-t-butylphenyl) phosphite, 4,4′-butylidene-bis (3- Methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl) butane, tris (2, 4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4 '-Biphenylene phosphanite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol di-phosphite, tetrakis ( , 4-di-t-butylphenyl) 4,4′-biphenylene phosphinite, triphenyl phosphite, diphenyl decyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite Phyto, trinonyl phenyl phosphite, tridodecyl trithiophosphite and the like can be mentioned.
またイオウ系酸化防止剤としては、ジラウリル−３，３’−チオジプロピオン酸エステル、ジミリスチル−３，３’−チオジウロビオン酸エステル、ジステアリル−３，３’−チオジプロピオン酸エステル、ラウリルステアリル−３，３’−チオジプロピオン酸エステル、ジラウリルチオジプロピオネ−ト、ジオクタデシルサルファイド、ペンタエリストリール−テトラ（β−ラウリル−チオプロピオネート）エステル等が挙げられる。なかでも含リン難燃剤のアルキレングリコール溶液の着色防止効果が優れている点でヒンダードフェノール系酸化防止剤が好ましく、４−ｔ−ブチルカテコールが特に好ましい。 Examples of the sulfur antioxidant include dilauryl-3,3′-thiodipropionic acid ester, dimyristyl-3,3′-thiodiurobionic acid ester, distearyl-3,3′-thiodipropionic acid ester, lauryl stearyl- 3,3′-thiodipropionic acid ester, dilauryl thiodipropionate, dioctadecyl sulfide, pentaerythritol tetra (β-lauryl-thiopropionate) ester and the like. Among these, a hindered phenol antioxidant is preferable, and 4-t-butylcatechol is particularly preferable from the viewpoint of excellent coloring prevention effect of the phosphorus-containing flame retardant alkylene glycol solution.
上記の酸化防止剤は、そのままでも添加、使用できるが、アルキレングリコールに溶解した溶液として反応系に添加しても構わない。また、酸化防止剤は単独で用いてもよく、２種以上を併用してもよい。本発明においては、酸化防止剤の含有割合は有機リン化合物に対して、合計０．００１〜１０重量％とする。酸化防止剤の含有割合が０．００１重量％より少ないと、反応生成物溶液の着色を十分に抑制することができない。また含有割合が１０重量％を超えて使用してもそれに見合う効果はなく、逆にこの酸化防止剤を導入した後のポリエステル中の異物となり、溶融樹脂のろ過性を悪化させる原因となる場合がある。酸化防止剤の含有割合は、有機リン化合物に対して、合計０．０５〜１重量％とすることがより好ましい。 The above antioxidant can be added and used as it is, but it may be added to the reaction system as a solution dissolved in alkylene glycol. Moreover, antioxidant may be used independently and may use 2 or more types together. In this invention, the content rate of antioxidant shall be 0.001 to 10 weight% in total with respect to an organophosphorus compound. When the content of the antioxidant is less than 0.001% by weight, coloring of the reaction product solution cannot be sufficiently suppressed. Moreover, even if it uses more than 10 weight%, there is no effect corresponding to it, and it will become a foreign substance in polyester after introducing this antioxidant on the contrary, and may cause the filterability of molten resin to deteriorate. is there. As for the content rate of antioxidant, it is more preferable to set it as 0.05 to 1 weight% in total with respect to an organophosphorus compound.
本発明においては、含リン難燃剤の製造において酸化防止剤の添加時期は、含リン難燃剤のアルキレングリコール溶液の着色が抑制される限り特に限定されるものではないが、有機リン化合物と不飽和カルボン酸及び／又はその無水物とアルキレングリコールとを反応させる前に添加することが好ましい。 In the present invention, the timing of addition of the antioxidant in the production of the phosphorus-containing flame retardant is not particularly limited as long as the coloring of the alkylene glycol solution of the phosphorus-containing flame retardant is suppressed, but the organic phosphorus compound and the unsaturated It is preferable to add the carboxylic acid and / or anhydride thereof before reacting with the alkylene glycol.
本発明において使用するアルキレングリコールは、ポリエステル構成成分であるアルキレングリコールを使用することが好ましく、具体的にはエチレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール、ネオペンチルグリコールなどの炭素数が２〜５のグリコールが例示される。 As the alkylene glycol used in the present invention, it is preferable to use an alkylene glycol which is a polyester component, and specifically, carbon such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and neopentyl glycol. Examples are glycols having 2 to 5 numbers.
本発明の含リン難燃剤の製造方法としては、１工程で含リン難燃剤を製造する製造方法であることが好ましい。具体的には有機リン化合物と不飽和カルボン酸及び／又はその無水物とアルキレングリコールとを、酸化防止剤の存在下に不活性ガス雰囲気下で加熱撹拌して反応させることによって行なわれる。この反応は、１００℃以上に加熱することによって進行するが、あまり低い温度では反応の完結に時間がかかり、逆に加熱温度が高すぎると有機リン化合物や不飽和カルボン酸が熱分解してしまうため、１２０〜２００℃とすることが好ましい。有機リン化合物と不飽和カルボン酸もしくはその無水物の反応比は実質的には等モルで行なうが、リン化合物に対して不飽和カルボン酸及び／又はその無水物をモル比にて１．０〜１．１倍仕込むことが好ましい。 As a manufacturing method of the phosphorus-containing flame retardant of this invention, it is preferable that it is a manufacturing method which manufactures a phosphorus-containing flame retardant at 1 process. Specifically, it is carried out by reacting an organophosphorus compound, an unsaturated carboxylic acid and / or anhydride thereof, and an alkylene glycol with heating and stirring in an inert gas atmosphere in the presence of an antioxidant. This reaction proceeds by heating to 100 ° C. or higher, but it takes time to complete the reaction at a very low temperature. Conversely, when the heating temperature is too high, the organic phosphorus compound and the unsaturated carboxylic acid are thermally decomposed. Therefore, it is preferable to set it as 120-200 degreeC. The reaction ratio between the organophosphorus compound and the unsaturated carboxylic acid or its anhydride is substantially equimolar, but the unsaturated carboxylic acid and / or its anhydride with respect to the phosphorus compound in a molar ratio of 1.0 to It is preferable to charge 1.1 times.
アルキレングリコールの使用量は、不飽和カルボン酸もしくはその無水物に対してモル比にて１．５〜２０倍、好ましくは２〜５倍の範囲である。アルキレングリコールの使用量が不飽和カルボン酸及び／又はその無水物に対してモル比にて１．５倍より少ない場合には、不飽和カルボン酸及び／又はその無水物によるカルボキシル基とのエステル化反応が不充分となり、反応溶液の粘度も高くなるため好ましくない。アルキレングリコールの使用量が２０倍を超える場合には反応溶液の粘度が低くなって取扱いは容易となるが、不経済である。 The amount of alkylene glycol used is in the range of 1.5 to 20 times, preferably 2 to 5 times in terms of molar ratio to the unsaturated carboxylic acid or anhydride thereof. When the amount of alkylene glycol used is less than 1.5 times in molar ratio to the unsaturated carboxylic acid and / or its anhydride, esterification with the carboxyl group by the unsaturated carboxylic acid and / or its anhydride This is not preferable because the reaction becomes insufficient and the viscosity of the reaction solution increases. When the amount of alkylene glycol used exceeds 20 times, the viscosity of the reaction solution becomes low and handling becomes easy, but it is uneconomical.
上述の本発明の含リン難燃剤の製造方法により得られる本発明の含リン難燃剤は、分子中に水酸基を一つ又は二つ有する含リン難燃剤のアルキレングリコール溶液であって、酸化防止剤を含有するものである。本発明の含リン難燃剤は、上記酸化防止剤を添加することにより着色が少なく、高白度が必要とされるポリエステルに難燃性を付与するものとして非常に有用である。本発明の含リン難燃剤のアルキレングリコール溶液中の濃度は特に限定されるものではないが、１０〜９０重量％である。 The phosphorus-containing flame retardant of the present invention obtained by the method for producing the phosphorus-containing flame retardant of the present invention described above is an alkylene glycol solution of a phosphorus-containing flame retardant having one or two hydroxyl groups in the molecule, and an antioxidant. It contains. The phosphorus-containing flame retardant of the present invention is very useful for imparting flame retardancy to a polyester that is less colored and requires high whiteness by adding the above antioxidant. Although the density | concentration in the alkylene glycol solution of the phosphorus-containing flame retardant of this invention is not specifically limited, It is 10 to 90 weight%.
本発明の難燃性ポリエステルは、難燃性ポリエステルを製造する原料の少なくとも一部として本発明の含リン難燃剤を用いるものである。難燃性ポリエステルを製造する原料として用いる場合、本発明の含リン難燃剤のアルキレングリコール溶液として用いることが好ましい。難燃性ポリエステルを製造する原料としては、ポリエステルの原料として用いられる従来公知の原料化合物から適宜選択することができる。例えば、エチレングリコール、プロピレングリコール、ネオペンチルグリコール等のジオール化合物、フタル酸、テレフタル酸、イソフタル酸、５−スルホイソフタル酸ナトリウム、アジピン酸等のジカルボン酸、フタル酸ジメチル、テレフタル酸ジメチル、イソフタル酸ジメチル、イソフタル酸ジメチル−５−スルホン酸ナトリウム、アジピン酸ジメチル等のジカルボン酸のエステル形成性化合物等が挙げられる。また難燃性ポリエステルを製造する縮重合反応としてはそれ自体公知の方法が適用できる。 The flame-retardant polyester of the present invention uses the phosphorus-containing flame retardant of the present invention as at least a part of a raw material for producing the flame-retardant polyester. When used as a raw material for producing a flame retardant polyester, it is preferably used as an alkylene glycol solution of the phosphorus-containing flame retardant of the present invention. As a raw material which manufactures a flame-retardant polyester, it can select suitably from the conventionally well-known raw material compound used as a raw material of polyester. For example, diol compounds such as ethylene glycol, propylene glycol and neopentyl glycol, dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, sodium 5-sulfoisophthalate and adipic acid, dimethyl phthalate, dimethyl terephthalate and dimethyl isophthalate And ester-forming compounds of dicarboxylic acids such as sodium dimethyl-5-sulfonate, dimethyl adipate, and the like. In addition, as a condensation polymerization reaction for producing a flame-retardant polyester, a method known per se can be applied.
本発明の難燃性ポリエステルは、含リン難燃剤から形成される構成単位をポリエステルに対してリン濃度として０．１．〜５．０重量％の割合で含有するものである。リン濃度が０．１重量％未満の場合には十分な難燃効果が得られず、５．０重量％を超えると難燃効果がそれ程高くならずにポリエステルの強度などに影響がでる場合がある。 The flame-retardant polyester of the present invention has a structural unit formed from a phosphorus-containing flame retardant having a phosphorus concentration of 0.1. It is contained at a ratio of ˜5.0% by weight. When the phosphorous concentration is less than 0.1% by weight, a sufficient flame retardant effect cannot be obtained, and when it exceeds 5.0% by weight, the flame retardant effect is not so high and the strength of the polyester may be affected. is there.
本発明の含リン難燃剤の製造方法、含リン難燃剤及び難燃性ポリエステルにおいて、光安定剤、帯電防止剤、滑剤、分子量調整剤、金属不活性化剤、有機及び無機系の核剤、中和剤、制酸剤、防菌剤、蛍光増白剤、充填剤、難燃剤、難燃助剤、有機及び無機系の顔料など添加剤を必要に応じて適宜組み合わせて使用しても構わない。 In the method for producing a phosphorus-containing flame retardant of the present invention, a phosphorus-containing flame retardant and a flame-retardant polyester, a light stabilizer, an antistatic agent, a lubricant, a molecular weight modifier, a metal deactivator, an organic and inorganic nucleating agent, Additives such as neutralizers, antacids, antibacterial agents, fluorescent brighteners, fillers, flame retardants, flame retardant aids, organic and inorganic pigments may be used in appropriate combinations as necessary. Absent.
本発明の含リン難燃剤の製造方法及び含リン難燃剤として好適な特に実施形態は、次の１）〜３）である。
１）ＤＯＰとイタコン酸をアルキレングリコール中で反応させて含リン難燃剤を製造する方法において、酸化防止剤として４−ｔ−ブチルカテコールを、ＤＯＰに対して合計で０．０１重量％の割合となるように含有させる含リン難燃剤の製造方法、並びに該方法によって得られた含リン難燃剤。
２）ＤＯＰとイタコン酸をアルキレングリコール中で反応させて含リン難燃剤を製造する方法において、酸化防止剤として４−ｔ−ブチルカテコールを、ＤＯＰに対して合計で０．１重量％の割合となるように含有させる含リン難燃剤の製造方法、並びに該方法によって得られた含リン難燃剤。
３）ＤＯＰとイタコン酸をアルキレングリコール中で反応させて含リン難燃剤を製造する方法において、酸化防止剤として４−ｔ−ブチルカテコールを、ＤＯＰに対して合計１重量％の割合となるように含有させる含リン難燃剤の製造方法、並びに該方法によって得られた含リン難燃剤。Particularly preferred embodiments as the method for producing the phosphorus-containing flame retardant and the phosphorus-containing flame retardant of the present invention are the following 1) to 3).
1) In the method for producing a phosphorus-containing flame retardant by reacting DOP and itaconic acid in an alkylene glycol, 4-t-butylcatechol as an antioxidant and a total proportion of 0.01% by weight with respect to DOP A method for producing a phosphorus-containing flame retardant to be contained, and a phosphorus-containing flame retardant obtained by the method.
2) In the method for producing a phosphorus-containing flame retardant by reacting DOP and itaconic acid in an alkylene glycol, 4-t-butylcatechol as an antioxidant and a ratio of 0.1% by weight in total with respect to DOP; A method for producing a phosphorus-containing flame retardant to be contained, and a phosphorus-containing flame retardant obtained by the method.
3) In the method for producing a phosphorus-containing flame retardant by reacting DOP and itaconic acid in an alkylene glycol, 4-t-butylcatechol as an antioxidant is adjusted to a total proportion of 1% by weight with respect to DOP. A method for producing a phosphorus-containing flame retardant to be contained, and a phosphorus-containing flame retardant obtained by the method.
本発明の難燃性ポリエステルの好適な実施形態は、ポリエステルの構成単位として、前記した１）〜３）の含リン難燃剤から形成される構成単位をポリエステルに対してリン濃度として０．１〜５．０重量％の割合で含有することを特徴とする。 In a preferred embodiment of the flame-retardant polyester of the present invention, the structural unit formed from the phosphorus-containing flame retardants 1) to 3) described above is 0.1 to 0.1 in terms of phosphorus concentration with respect to the polyester. It contains in the ratio of 5.0 weight%, It is characterized by the above-mentioned.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれらの実施例等に限定されるというものではない。尚、以下の実施例及び比較例において、部は重量部を、また％は重量％を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples and the like. In the following Examples and Comparative Examples, “part” means “part by weight” and “%” means “% by weight”.
本発明及び以下の実施例において、含リン難燃剤の色相（ＡＰＨＡ）は、ＪＩＳ Ｋ １５５７−１９７０記載のＡＰＨ標準液との比較で測定した。 In the present invention and the following examples, the hue (APHA) of the phosphorus-containing flame retardant was measured by comparison with an APH standard solution described in JIS K 1557-1970.
＜含リン難燃剤の製造例＞
（実施例１）含リン難燃剤（Ｐ−１）の製造
撹拌装置、温度計、窒素ガス導入管、留出管を装備した１Ｌの４つ口反応フラスコに、エチレングリコール３００ｇ（４．８３モル）、ＤＯＰ１８７ｇ（０．８７モル）、イタコン酸１１３ｇ（０．８７モル）、４−ｔ−ブチルカテコール（酸化防止剤（Ａ−１））０．０６ｇ（０．０１重量％）を仕込み、窒素ガス雰囲気下、加熱撹拌してエステル化反応を行った。反応温度は約６時間をかけて室温から１９０℃とし、同温度でさらに４時間反応を続けて、含リン難燃剤（Ｐ−１）を６６重量％含有するエチレングリコール溶液を得た。この反応においてエステル化によって生成した水の量は約３２ｍｌであった。得られた含リン難燃剤（Ｐ−１）のエチレングリコール（ＥＧ）溶液の色相は、ＡＰＨＡカラー標準を用いて、目視で評価した結果、色相（ＡＰＨＡ）が９０であった。<Production example of phosphorus-containing flame retardant>
Example 1 Production of Phosphorus-containing Flame Retardant (P-1) Into a 1 L four-necked reaction flask equipped with a stirrer, thermometer, nitrogen gas introduction tube, and distillation tube was charged 300 g (4.83 mol) of ethylene glycol. ), 187 g (0.87 mol) of DOP, 113 g (0.87 mol) of itaconic acid, 0.06 g (0.01 wt%) of 4-t-butylcatechol (antioxidant (A-1)), and nitrogen. Under a gas atmosphere, the esterification reaction was performed by heating and stirring. The reaction temperature was changed from room temperature to 190 ° C. over about 6 hours, and the reaction was further continued for 4 hours at the same temperature to obtain an ethylene glycol solution containing 66% by weight of the phosphorus-containing flame retardant (P-1). The amount of water produced by esterification in this reaction was about 32 ml. The hue of the obtained phosphorous-containing flame retardant (P-1) in an ethylene glycol (EG) solution was visually evaluated using an APHA color standard. As a result, the hue (APHA) was 90.
（実施例２、３）含リン難燃剤（Ｐ−２）、（Ｐ−３）の製造
酸化防止剤の添加量を変更した以外は実施例１と同様にして、含リン難燃剤（Ｐ−２）、（Ｐ−３）（実施例２、３）の製造を行った。得られた含リン難燃剤（Ｐ−２）、（Ｐ−３）のエチレングリコール（ＥＧ）溶液の色相（ＡＰＨＡ）は、（Ｐ−２）が７０，（Ｐ−３）が６０であった。結果をまとめて表１に示した。
(Examples 2 and 3) Production of phosphorus-containing flame retardants (P-2) and (P-3) Phosphorus-containing flame retardants (P-) were prepared in the same manner as in Example 1 except that the addition amount of the antioxidant was changed. 2) and (P-3) (Examples 2 and 3) were produced. The hue (APHA) of the obtained phosphorus-containing flame retardants (P-2) and (P-3) in an ethylene glycol (EG) solution was 70 for (P-2) and 60 for (P-3). . The results are summarized in Table 1.
（実施例４）含リン難燃剤（Ｐ−４）の製造
酸化防止剤としてテトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（酸化防止剤（Ａ−２）を０．６ｇ（０．１重量％）添加した以外は実施例１と同様にして、含リン難燃剤（Ｐ−４）（実施例４）の製造を行った。得られた含リン難燃剤（Ｐ−４）のエチレングリコール（ＥＧ）溶液の色相（ＡＰＨＡ）は１００であった。結果をまとめて表１に示した。(Example 4) Production of phosphorus-containing flame retardant (P-4) Tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane (oxidation) as an antioxidant A phosphorus-containing flame retardant (P-4) (Example 4) was produced in the same manner as in Example 1 except that 0.6 g (0.1% by weight) of the inhibitor (A-2) was added. The hue (APHA) of the ethylene glycol (EG) solution of the obtained phosphorus-containing flame retardant (P-4) was 100. The results are shown in Table 1.
（比較例１）含リン難燃剤（Ｒ−１）の製造
撹拌装置、温度計、窒素ガス導入管、留出管を装備した１Ｌの４つ口反応フラスコに、エチレングリコール３００ｇ（４．８３モル）、ＤＯＰ１８７ｇ（０．８７モル）、イタコン酸１１３ｇ（０．８７モル）を仕込み、窒素ガス雰囲気下、加熱撹拌した。反応温度は約６時間をかけて室温から１９０℃とし、この温度で更に４時間反応を続けて含リン難燃剤（Ｒ−１）を６６重量％含有するエチレングリコール溶液を得た。反応系は加熱を開始してすぐに着色が確認された。この反応においてエステル化反応によって生成した水の量は約３２ｍｌであった。得られた含リン難燃剤（Ｒ−１）のエチレングリコール溶液は色相（ＡＰＨＡ）が２００であり、着色が著しいものであった。Comparative Example 1 Production of Phosphorus-containing Flame Retardant (R-1) Into a 1 L four-necked reaction flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a distilling tube, 300 g (4.83 mol) of ethylene glycol was added. ), 187 g (0.87 mol) of DOP and 113 g (0.87 mol) of itaconic acid, and heated and stirred in a nitrogen gas atmosphere. The reaction temperature was changed from room temperature to 190 ° C. over about 6 hours, and the reaction was further continued at this temperature for 4 hours to obtain an ethylene glycol solution containing 66% by weight of the phosphorus-containing flame retardant (R-1). The reaction system was colored immediately after heating was started. In this reaction, the amount of water produced by the esterification reaction was about 32 ml. The obtained ethylene glycol solution of the phosphorus-containing flame retardant (R-1) had a hue (APHA) of 200, and was markedly colored.
＜難燃性ポリエステルの製造例＞
（実施例５）難燃性ポリエステル（ＡＰ−１）の製造
撹拌機、蒸留塔、圧力調整器を備えた５Ｌステンレス製オートクレーブにテレフタル酸１２４２ｇ（７．４８モル）、難燃剤製造例で製造した含リン難燃剤（Ｐ−１）のエチレングリコール溶液２００ｇ（含リン難燃剤として０．３０モル）とエチレングリコール８５０ｇ（１３．７１モル）を仕込み、更に三酸化アンチモンを１４ｇ／Ｌのエチレングリコ−ル溶液として２．４１ｇ、二酸化ゲルマニウムを８ｇ／Ｌのエチレングリコール溶液として１５ｇ及びトリエチルアミン５．２ｇを加えた後、２３０℃、ゲージ圧２．５ｋｇ／ｃｍ２ の条件にて水を逐次留去しながら２時間エステル化反応を行った。次いで１時間かけて反応系の温度を２７５℃まで昇温しつつ、系の圧力を徐々に減じて０．１ｍｍＨｇとし、この条件下で１時間重縮合反応を行って難燃性ポリエステル（ＡＰ−１）を得た。得られた難燃性ポリエステル（ＡＰ−１）は、分析により含リン難燃剤から形成される構成単位をポリエステルに対してリン濃度として０．６０重量％の割合で含有するものであった。また得られた難燃性ポリエステル（ＡＰ−１）のハンター型色差計によるＬ値及びｂ値は、Ｌ値が７５、ｂ値が１０．３であった。ここで、Ｌ値が大きい程、ポリエステルの白度が向上していることを示し、ｂ値が大きい程、ポリエステルの黄色味の強いことを示している。即ち、Ｌ値が大きく、ｂ値が小さいほど色調が良好であることを示す。<Production example of flame-retardant polyester>
Example 5 Production of Flame Retardant Polyester (AP-1) Manufactured in a flame retardant production example, 1242 g (7.48 mol) of terephthalic acid in a 5 L stainless steel autoclave equipped with a stirrer, distillation tower and pressure regulator. 200 g of an ethylene glycol solution of phosphorus-containing flame retardant (P-1) (0.30 mol as a phosphorus-containing flame retardant) and 850 g (13.71 mol) of ethylene glycol were added, and further antimony trioxide was added at 14 g / L of ethylene glyco- After adding 2.41 g as a solution, 15 g as germanium dioxide solution at 8 g / L and 5.2 g as triethylamine, water was successively distilled off at 230 ° C. and a gauge pressure of 2.5 kg / cm 2. The esterification reaction was carried out for 2 hours. Next, while raising the temperature of the reaction system to 275 ° C. over 1 hour, the pressure of the system is gradually reduced to 0.1 mmHg, and a polycondensation reaction is carried out for 1 hour under these conditions, to obtain a flame-retardant polyester (AP- 1) was obtained. The obtained flame-retardant polyester (AP-1) contained a structural unit formed from a phosphorus-containing flame retardant by analysis in a proportion of 0.60% by weight as a phosphorus concentration with respect to the polyester. Moreover, L value and b value by the Hunter type | mold color difference meter of the obtained flame-retardant polyester (AP-1) were L value 75 and b value 10.3. Here, it shows that the whiteness of polyester is improving, so that L value is large, and it shows that yellowness of polyester is strong, so that b value is large. That is, the larger the L value and the smaller the b value, the better the color tone.
（実施例６〜８）難燃性ポリエステル（ＡＰ−２）〜（ＡＰ−４）の製造
使用する含リン難燃剤ＥＧ溶液を変更した以外は難燃性ポリエステル（ＡＰ−１）の製造例と同様にして、難燃性ポリエステル（ＡＰ−２）〜（ＡＰ−４）（実施例６〜８）の製造を行った。結果をまとめて表２に示した。(Examples 6 to 8) Production of flame retardant polyesters (AP-2) to (AP-4) Production examples of flame retardant polyester (AP-1) except that the phosphorus-containing flame retardant EG solution used was changed. Similarly, flame-retardant polyesters (AP-2) to (AP-4) (Examples 6 to 8) were produced. The results are summarized in Table 2.
（比較例２）難燃性ポリエステル（ＡＲ−１）の製造
撹拌機、蒸留塔、圧力調整器を備えた５Ｌステンレス製オートクレーブにテレフタル酸１２４２ｇ（７．４８モル）、含リン難燃剤製造例で製造した含リン難燃剤（Ｒ−１）のエチレングリコール溶液２００ｇ（０．３０モル）とエチレングリコール８５０ｇ（１３．７１モル）を仕込み、更に三酸化アンチモンを１４ｇ／Ｌのエチレングリコール溶液として２４．１ｇ、二酸化ゲルマニウムを８ｇ／Ｌのエチレングリコール溶液として１５ｇ及びトリエチルアミン５．２ｇを加えた後、２３０℃、ゲージ圧２．５ｋｇ／ｃｍ２の条件にて水を逐次留去しながら２時間エステル化反応を行った。次いで１時間かけて反応系の温度を２７５℃まで昇温しつつ、系の圧力を徐々に減じて０．１ｍｍＨｇとし、この条件下で１時間重縮合反応を行って、難燃性ポリエステル（ＡＲ−１）を得た。得られた難燃性ポリエステル（ＡＲ−１）は、分析により含リン難燃剤から形成される構成単位をポリエステルに対してリン濃度として０．６０重量％の割合で含有するものであった。また得られた難燃性ポリエステル（ＡＲ−２）のハンター型色差計によるＬ値及びｂ値は、Ｌ値が７４、ｂ値が１９．７であった。Comparative Example 2 Production of Flame Retardant Polyester (AR-1) In a 5 L stainless steel autoclave equipped with a stirrer, distillation tower and pressure regulator, 1242 g (7.48 mol) of terephthalic acid was produced in a production example of a phosphorus-containing flame retardant. 200 g (0.30 mol) of an ethylene glycol solution of the produced phosphorus-containing flame retardant (R-1) and 850 g (13.71 mol) of ethylene glycol were charged, and further antimony trioxide was added as a 14 g / L ethylene glycol solution. 1 g, 15 g of germanium dioxide as an 8 g / L ethylene glycol solution and 5.2 g of triethylamine were added, followed by esterification for 2 hours while sequentially distilling off water at 230 ° C. and a gauge pressure of 2.5 kg / cm 2 . Reaction was performed. Next, while raising the temperature of the reaction system to 275 ° C. over 1 hour, the pressure of the system is gradually reduced to 0.1 mmHg, and a polycondensation reaction is performed for 1 hour under these conditions to obtain a flame-retardant polyester (AR -1) was obtained. The obtained flame retardant polyester (AR-1) contained a structural unit formed from a phosphorus-containing flame retardant by analysis in a proportion of 0.60% by weight as a phosphorus concentration with respect to the polyester. Moreover, L value and b value by the Hunter type color difference meter of the obtained flame-retardant polyester (AR-2) were L value 74 and b value 19.7.
（比較例４）難燃性ポリエステル（ＡＲ−２）の製造
撹拌機、蒸留塔、圧力調整器を備えた５Ｌステンレス製オートクレープにテレフタル酸１２４２ｇ（７．４８モル）、含リン難燃剤製造例で製造した含リン難燃剤（Ｒ−１）のエチレングリコール２００ｇ（０．３０モル）とエチレングリコ−ル（ＥＧ）８５０ｇ（１３．７１モル）と酸化防止剤として４−ｔ−ブチルカテコール１．３２ｇ（含リン難燃剤に対し１％）を仕込み、更に三酸化アンチモンを１４ｇ／Ｌのエチレングリコール溶液として２４．１ｇ、二酸化ゲルマニウムを８ｇ／Ｌのエチレングリコール溶液として１５ｇ及びトリエチルアミン５．２ｇを加えた後、２３０℃、ゲージ圧２．５ｋｇ／ｃｍ２ の条件にて水を逐次留去しながら２時間エステル化反応を行った。次いで１時間かけて反応系の温度を２７５℃まで昇温しつつ、系の圧力を徐々に減じて０．１ｍｍＨｇとし、この条件下で１時間重縮合反応を行って、難燃性ポリエステル（ＡＲ−２）を得た。得られた難燃性ポリエステル（ＡＲ−２）は、分析により含リン難燃剤から形成される構成単位をポリエステルに対してリン濃度として０．６０重量％の割合で含有するものであった。また得られた難燃性ポリエステル（ＡＲ−２）のハンター型色差計によるＬ値及びｂ値は、Ｌ値が７４、ｂ値が１８．６であった。(Comparative example 4) Manufacture of flame-retardant polyester (AR-2) 1242 g (7.48 mol) of terephthalic acid in a 5 L stainless steel autoclave equipped with a stirrer, a distillation column and a pressure regulator, and a phosphorus-containing flame retardant production example 200 g (0.30 mol) of the ethylene-containing flame retardant (R-1) and 850 g (13.71 mol) of ethylene glycol (EG) and 4-t-butylcatechol as an antioxidant. 32 g (1% with respect to the phosphorus-containing flame retardant) was added, and 24.1 g of antimony trioxide as an ethylene glycol solution of 14 g / L, 15 g of germanium dioxide as an ethylene glycol solution of 8 g / L, and 5.2 g of triethylamine were added. Then, the esterification reaction was carried out for 2 hours while successively distilling off water at 230 ° C. and a gauge pressure of 2.5 kg / cm 2. Next, while raising the temperature of the reaction system to 275 ° C. over 1 hour, the pressure of the system is gradually reduced to 0.1 mmHg, and a polycondensation reaction is performed for 1 hour under these conditions to obtain a flame-retardant polyester (AR -2) was obtained. The obtained flame-retardant polyester (AR-2) contained a structural unit formed from a phosphorus-containing flame retardant by analysis in a proportion of 0.60% by weight as a phosphorus concentration with respect to the polyester. The L value and b value of the obtained flame-retardant polyester (AR-2) by a Hunter-type color difference meter were L value 74 and b value 18.6.
（比較例４）難燃性ポリエステル（ＡＲ−３）の製造
難燃性ポリエステル（ＡＲ−２）において４−ｔ−ブチルカテコール１．５ｇに代えて、テトラキス〔メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート〕メタン１．３２ｇとした以外は比較例３と同様にして、難燃性ポリエステル（ＡＲ−３）の製造を行った。得られた難燃性ポリエステルの色調評価結果をまとめて表２に示した。Comparative Example 4 Production of Flame Retardant Polyester (AR-3) In the flame retardant polyester (AR-2), tetrakis [methylene-3- (3 ′, 5) was used instead of 1.5 g of 4-t-butylcatechol. ['-Di-t-butyl-4'-hydroxyphenyl) propionate] Flame retardant polyester (AR-3) was produced in the same manner as Comparative Example 3 except that 1.32 g of methane was used. Table 2 summarizes the color tone evaluation results of the obtained flame-retardant polyester.
本発明の含リン難燃剤はポリエステルの製造に使用でき、該含リン難燃剤は、本発明の含リン難燃剤の製造方法により製造することができる。 The phosphorus-containing flame retardant of the present invention can be used for the production of polyester, and the phosphorus-containing flame retardant can be produced by the method for producing a phosphorus-containing flame retardant of the present invention.
Claims (4)
前記有機リン化合物が、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキシドであり、
前記不飽和カルボン酸がイタコン酸であり、前記不飽和カルボン酸の酸無水物が無水イタコン酸であり、
酸化防止剤としてのｔ−ブチルカテコールを、前記有機リン化合物に対して合計０．００１〜１０重量％含有させることを特徴とする含リン難燃剤の製造方法。In a method for producing a phosphorus-containing flame retardant by reacting an organic phosphorus compound with an unsaturated carboxylic acid and / or an acid anhydride thereof in an alkylene glycol,
The organophosphorus compound is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
The unsaturated carboxylic acid is itaconic acid, and the unsaturated carboxylic acid anhydride is itaconic anhydride,
The method of manufacturing phosphorus-containing flame retardant, characterized in that the t- butyl catechol as an acid antioxidant, is contained total 0.001 wt% with respect to the organophosphorus compound.
酸化防止剤及びアルキレングリコールを含有し、色相（ＡＰＨＡ）が１２０以下であることを特徴とする含リン難燃剤。A phosphorus-containing flame retardant produced by the method for producing a phosphorus-containing flame retardant according to claim 1 ,
A phosphorus-containing flame retardant containing an antioxidant and an alkylene glycol and having a hue (APHA) of 120 or less .
前記工程Ａで製造された含リン難燃剤と、ジオール化合物と、ジカルボン酸とを少なくとも仕込み、重縮合反応を行なって難燃性ポリエステルを得る工程Ｂ Step B in which a phosphorus-containing flame retardant produced in Step A, a diol compound, and a dicarboxylic acid are charged at least and a polycondensation reaction is performed to obtain a flame-retardant polyester.
を有することを特徴とする難燃性ポリエステルの製造方法。A method for producing a flame-retardant polyester, comprising:
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| PCT/JP2004/019363 WO2005063922A1 (en) | 2003-12-26 | 2004-12-24 | Process for producing phosphorus compound flame retardant, phosphorus compound flame retardant, and flame-retardant polyester |
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| JP5115172B2 (en) * | 2007-12-13 | 2013-01-09 | 株式会社カネカ | Resin composition |
| CN101613374B (en) * | 2009-07-22 | 2012-03-14 | 中国科学技术大学 | Polymeric phosphorus-containing flame retardant with DOPO as lateral group and preparation method thereof |
| DE102009037631A1 (en) * | 2009-08-14 | 2011-02-17 | Schill + Seilacher "Struktol" Gmbh | Phosphorus-containing flame retardant |
| CN101792530A (en) * | 2010-03-19 | 2010-08-04 | 苏州兰特纳米材料科技有限公司 | Polymer type halogen-free flame retardant (PDPTP) and preparation method thereof |
| CN103333205A (en) * | 2013-06-28 | 2013-10-02 | 青岛富斯林化工科技有限公司 | Phosphorus flame retardant 2,3-dicarboxylic propyl diphenyl phosphine oxide, preparation method and flame-retardant polyester composition thereof |
| CN110343413B (en) * | 2019-07-17 | 2021-01-08 | 烟台大学 | Nitrogen-phosphorus intumescent flame retardant and preparation method thereof in application of waterborne polyurethane coating |
| CN110903512B (en) * | 2019-11-21 | 2021-12-17 | 浙江大学宁波理工学院 | Efficient halogen-free phosphorus gas-phase flame retardant and high polymer material containing same |
| CN112812285B (en) * | 2020-12-28 | 2022-05-06 | 湖南美莱珀科技发展有限公司 | Macromolecular flame retardant and preparation method and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5247891A (en) * | 1975-10-14 | 1977-04-16 | Toyobo Co Ltd | Phosphorus-containing flame retarders |
| JPS5297981A (en) * | 1976-02-13 | 1977-08-17 | Toyobo Co Ltd | Novel organic phosphorus compounds |
| JPS62172017A (en) * | 1986-01-23 | 1987-07-29 | Nippon Ester Co Ltd | Production of fire-resistant polyester |
| JPH0776648A (en) * | 1993-06-29 | 1995-03-20 | Herberts Gmbh | Binder and coating composition and its production and use |
| JPH08176171A (en) * | 1994-10-10 | 1996-07-09 | Hoechst Ag | Production of dicarboxylic acid containing phosphorus |
| JPH1025338A (en) * | 1996-07-10 | 1998-01-27 | Toray Ind Inc | Phosphorus-containing polyester polymer and resin composition |
| JP2000212266A (en) * | 1999-01-26 | 2000-08-02 | Nippon Ester Co Ltd | Preparation of flame-retardant polyester |
| JP2000302848A (en) * | 1999-04-23 | 2000-10-31 | Toyobo Co Ltd | Fire-retardant polyester elastomer resin composition |
| JP2001117274A (en) * | 1999-10-22 | 2001-04-27 | Canon Inc | Color toner and method of producing color toner |
| EP1238997A1 (en) * | 2001-03-07 | 2002-09-11 | Ucb S.A. | Phosphorus containing materials, their preparation and use |
| JP2003155402A (en) * | 2001-11-21 | 2003-05-30 | Katsuta Kako Kk | Polyester resin composition for calendering and its sheet |
| WO2003071014A1 (en) * | 2002-02-22 | 2003-08-28 | Kaneka Corporation | Flame-retardant polyester fiber and artificial hair comprising the same |
| JP2005531660A (en) * | 2002-07-01 | 2005-10-20 | サーフェース スペシャリティーズ、エス．エイ． | Water-dilutable polymer precursors, their preparation and use |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127590A (en) * | 1975-10-14 | 1978-11-28 | Toyo Boseki Kabushiki Kaisha | Phosphorus-containing compounds |
| US5571888A (en) * | 1995-06-14 | 1996-11-05 | Industrial Technology Research Institute | Process for preparing flame-retardant phosphorus-containing unsaturated polyester |
| JPH107918A (en) * | 1996-06-28 | 1998-01-13 | Nippon Shokubai Co Ltd | Resin composition |
| TW445276B (en) * | 1998-08-13 | 2001-07-11 | Otsuka Chemical Co Ltd | Crosslinked phenoxyphosphazene compounds, process for the preparation thereof, flame retardants, flame-retardant resin compositions, and moldings of flame-retardant resins |
| JP2004161890A (en) * | 2002-11-13 | 2004-06-10 | Nippon Ester Co Ltd | Polyester resin for adhesive, adhesive, and laminated body |
-
2004
- 2004-12-24 CN CN2004800387644A patent/CN1910263B/en active Active
- 2004-12-24 JP JP2005516649A patent/JP4835975B2/en active Active
- 2004-12-24 WO PCT/JP2004/019363 patent/WO2005063922A1/en active Application Filing
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5247891A (en) * | 1975-10-14 | 1977-04-16 | Toyobo Co Ltd | Phosphorus-containing flame retarders |
| JPS5297981A (en) * | 1976-02-13 | 1977-08-17 | Toyobo Co Ltd | Novel organic phosphorus compounds |
| JPS62172017A (en) * | 1986-01-23 | 1987-07-29 | Nippon Ester Co Ltd | Production of fire-resistant polyester |
| JPH0776648A (en) * | 1993-06-29 | 1995-03-20 | Herberts Gmbh | Binder and coating composition and its production and use |
| JPH08176171A (en) * | 1994-10-10 | 1996-07-09 | Hoechst Ag | Production of dicarboxylic acid containing phosphorus |
| JPH1025338A (en) * | 1996-07-10 | 1998-01-27 | Toray Ind Inc | Phosphorus-containing polyester polymer and resin composition |
| JP2000212266A (en) * | 1999-01-26 | 2000-08-02 | Nippon Ester Co Ltd | Preparation of flame-retardant polyester |
| JP2000302848A (en) * | 1999-04-23 | 2000-10-31 | Toyobo Co Ltd | Fire-retardant polyester elastomer resin composition |
| JP2001117274A (en) * | 1999-10-22 | 2001-04-27 | Canon Inc | Color toner and method of producing color toner |
| EP1238997A1 (en) * | 2001-03-07 | 2002-09-11 | Ucb S.A. | Phosphorus containing materials, their preparation and use |
| JP2003155402A (en) * | 2001-11-21 | 2003-05-30 | Katsuta Kako Kk | Polyester resin composition for calendering and its sheet |
| WO2003071014A1 (en) * | 2002-02-22 | 2003-08-28 | Kaneka Corporation | Flame-retardant polyester fiber and artificial hair comprising the same |
| JP2005531660A (en) * | 2002-07-01 | 2005-10-20 | サーフェース スペシャリティーズ、エス．エイ． | Water-dilutable polymer precursors, their preparation and use |
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| Publication number | Publication date |
|---|---|
| CN1910263A (en) | 2007-02-07 |
| CN1910263B (en) | 2010-05-05 |
| JPWO2005063922A1 (en) | 2007-12-20 |
| WO2005063922A1 (en) | 2005-07-14 |
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