JPS62257964A - Polyester imide composition - Google Patents
Polyester imide compositionInfo
- Publication number
- JPS62257964A JPS62257964A JP10218586A JP10218586A JPS62257964A JP S62257964 A JPS62257964 A JP S62257964A JP 10218586 A JP10218586 A JP 10218586A JP 10218586 A JP10218586 A JP 10218586A JP S62257964 A JPS62257964 A JP S62257964A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- sulfonate
- component
- polyesterimide
- potassium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920003055 poly(ester-imide) Polymers 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract 2
- 150000001340 alkali metals Chemical group 0.000 claims abstract 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract 2
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract 2
- 125000005843 halogen group Chemical group 0.000 claims abstract 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims 1
- 125000001174 sulfone group Chemical group 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 26
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 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 abstract description 9
- 150000002009 diols Chemical class 0.000 abstract description 6
- 241000790917 Dioxys <bee> Species 0.000 abstract description 5
- 229920000728 polyester Polymers 0.000 abstract description 3
- QXCFFLGAAJDPTG-UHFFFAOYSA-M sodium;2,3-dichlorobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC(Cl)=C1Cl QXCFFLGAAJDPTG-UHFFFAOYSA-M 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 150000003457 sulfones Chemical group 0.000 abstract description 2
- -1 Polyethylene terephthalate Polymers 0.000 description 42
- 229920000642 polymer Polymers 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 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 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- KIXKLKMUPZUMFB-UHFFFAOYSA-M potassium;2,3,4-trichlorobenzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=C(Cl)C(Cl)=C1Cl KIXKLKMUPZUMFB-UHFFFAOYSA-M 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-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
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 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
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- DRPLRPSXUUSFOB-UHFFFAOYSA-M potassium;2,4,5-trichlorobenzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC(Cl)=C(Cl)C=C1Cl DRPLRPSXUUSFOB-UHFFFAOYSA-M 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical class OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- KMFXMUYBJLJRGA-UHFFFAOYSA-M sodium;2,3,4-trichlorobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(Cl)C(Cl)=C1Cl KMFXMUYBJLJRGA-UHFFFAOYSA-M 0.000 description 2
- SPCSAIAKCMKSJN-UHFFFAOYSA-M sodium;2-chlorobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1Cl SPCSAIAKCMKSJN-UHFFFAOYSA-M 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- LJQVLJXQHTULEP-UHFFFAOYSA-N (3-hydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC(O)=C1 LJQVLJXQHTULEP-UHFFFAOYSA-N 0.000 description 1
- XWJNPEZTTCJZSX-UHFFFAOYSA-N 1,1,2,2,2-pentachloroethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Cl)C(Cl)(Cl)Cl XWJNPEZTTCJZSX-UHFFFAOYSA-N 0.000 description 1
- GKNWQHIXXANPTN-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-N 0.000 description 1
- XBWQFDNGNOOMDZ-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F XBWQFDNGNOOMDZ-UHFFFAOYSA-N 0.000 description 1
- ARRQNZZBVOIEQQ-UHFFFAOYSA-N 1,3-dioxoisoindole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2C(=O)NC(=O)C2=C1 ARRQNZZBVOIEQQ-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZHUGVSYKQYXYMI-UHFFFAOYSA-N 2,3-dichloronaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=C(Cl)C(Cl)=CC2=C1 ZHUGVSYKQYXYMI-UHFFFAOYSA-N 0.000 description 1
- FKWOGPPGVRDIRZ-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=CC=C1O FKWOGPPGVRDIRZ-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- XBQRPFBBTWXIFI-UHFFFAOYSA-N 2-chloro-4-[2-(3-chloro-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(Cl)=CC=1C(C)(C)C1=CC=C(O)C(Cl)=C1 XBQRPFBBTWXIFI-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical class C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- SWKVSFPUHCMFJY-UHFFFAOYSA-N 6-methyl-2-oxo-5-pyridin-4-yl-1h-pyridine-3-carboxamide Chemical compound N1C(=O)C(C(N)=O)=CC(C=2C=CN=CC=2)=C1C SWKVSFPUHCMFJY-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FDVCPALSMZOSEA-UHFFFAOYSA-L ClC1=C(C=CC=C1)S(=O)(=O)[O-].[Ca+2].ClC1=C(C=CC=C1)S(=O)(=O)[O-] Chemical compound ClC1=C(C=CC=C1)S(=O)(=O)[O-].[Ca+2].ClC1=C(C=CC=C1)S(=O)(=O)[O-] FDVCPALSMZOSEA-UHFFFAOYSA-L 0.000 description 1
- BVIXQDLJPVABSR-UHFFFAOYSA-M ClC=1C(=C(C=CC=1)S(=O)(=O)[O-])[N+](=O)[O-].[Na+] Chemical compound ClC=1C(=C(C=CC=1)S(=O)(=O)[O-])[N+](=O)[O-].[Na+] BVIXQDLJPVABSR-UHFFFAOYSA-M 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GKRYRFHTHKMGMQ-UHFFFAOYSA-N FC(C(F)(F)[S+](F)F)(F)F Chemical compound FC(C(F)(F)[S+](F)F)(F)F GKRYRFHTHKMGMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical class C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CKJFPVNRRHVMKZ-UHFFFAOYSA-L calcium;naphthalene-1-sulfonate Chemical compound [Ca+2].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 CKJFPVNRRHVMKZ-UHFFFAOYSA-L 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical class C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- QESVBYKECHLZTB-UHFFFAOYSA-M potassium 2-fluorobenzenesulfonate Chemical compound FC1=CC=CC=C1S(=O)(=O)[O-].[K+] QESVBYKECHLZTB-UHFFFAOYSA-M 0.000 description 1
- PRWAOSWYQVZORA-UHFFFAOYSA-M potassium trichloromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(Cl)(Cl)Cl PRWAOSWYQVZORA-UHFFFAOYSA-M 0.000 description 1
- DUCGQSYLYWVEBW-UHFFFAOYSA-M potassium;2-bromobenzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1Br DUCGQSYLYWVEBW-UHFFFAOYSA-M 0.000 description 1
- VBKYLLXGAYULIT-UHFFFAOYSA-M potassium;2-bromonaphthalene-1-sulfonate Chemical compound [K+].C1=CC=C2C(S(=O)(=O)[O-])=C(Br)C=CC2=C1 VBKYLLXGAYULIT-UHFFFAOYSA-M 0.000 description 1
- ZVDOJGPDWSMSTB-UHFFFAOYSA-M potassium;2-chlorobenzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1Cl ZVDOJGPDWSMSTB-UHFFFAOYSA-M 0.000 description 1
- ZFDMVEOVDOINLW-UHFFFAOYSA-M potassium;2-nitrobenzenesulfonate Chemical compound [K+].[O-][N+](=O)C1=CC=CC=C1S([O-])(=O)=O ZFDMVEOVDOINLW-UHFFFAOYSA-M 0.000 description 1
- IZHYRVRPSNAXGV-UHFFFAOYSA-M potassium;naphthalene-1-sulfonate Chemical compound [K+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 IZHYRVRPSNAXGV-UHFFFAOYSA-M 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HWDIRMKMGCHDBF-UHFFFAOYSA-M sodium;2-bromobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1Br HWDIRMKMGCHDBF-UHFFFAOYSA-M 0.000 description 1
- QRAHTOAXCUTAKU-UHFFFAOYSA-M sodium;2-fluorobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1F QRAHTOAXCUTAKU-UHFFFAOYSA-M 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940035339 tri-chlor Drugs 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
ａ、産業上の利用分野
本発明はポリエステルイミド組成物に関するものであり
、更に詳しくは特定構造のポリエステルイミドに有機ス
ルホネート金属塩を少量含有せしめてなる難燃性に優れ
たポリエステルイミド組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to a polyesterimide composition, and more specifically to a polyesterimide composition having a specific structure containing a small amount of an organic sulfonate metal salt and having excellent flame retardancy. The present invention relates to a polyesterimide composition.
ｂ、従来技術
ポリエチレンテレフタレートは機械的特性に優れ、繊維
、フィルム、プラスチックス等として広く用いられてい
る。しかし、近年、技術の高度化により、より高い機械
的特性、耐熱性を有し、かつ難燃性の良好な素材が望ま
れている。b. Prior Art Polyethylene terephthalate has excellent mechanical properties and is widely used as fibers, films, plastics, etc. However, in recent years, with the advancement of technology, materials with higher mechanical properties, heat resistance, and flame retardancy are desired.
かかる素材として、溶融状態で光学的に異方性を示すポ
リマー、いわゆる液晶性ボリアリレートが提案されてい
るが、この液晶性ボリアリレートは確かに高い顔械特性
、耐熱性を有しているが、その高い分子間力の故に溶融
成形すると一軸方向に配向し゛つすく、例えばポリエチ
レンテレフタレー１〜で１７られるような二軸配向フィ
ルムを通常の溶融成形方法で製造することが極めて困難
であるという欠点を有する。As such a material, a polymer that exhibits optical anisotropy in the molten state, so-called liquid crystalline polyarylate, has been proposed. Although this liquid crystalline polyarylate certainly has high facial properties and heat resistance, Due to its high intermolecular force, it tends to be uniaxially oriented when melt-molded, and it is said that it is extremely difficult to produce biaxially oriented films such as those made of polyethylene terephthalate 1 to 17 using normal melt-molding methods. It has its drawbacks.
一方、溶融上光学的に等方性でかつポリエチレンテレフ
タレートより芳香族性２分子の剛直陛の高いものとして
ポリエチレン２，６−ナフタレートや、４．４’−（エ
チレンジオキシ）ジオール成分とエヂレングリコール成
分とを縮合して（７られるポリエステルが知られている
。しかし、これらについては上述の特性が未だ十分とは
言えない。On the other hand, polyethylene 2,6-naphthalate, which is optically isotropic in melting and has higher rigidity and rigidity than polyethylene terephthalate, has two aromatic molecules, and 4,4'-(ethylenedioxy)diol component and ethylene diol component. Polyesters formed by condensing a glycol component (7) are known. However, the above-mentioned properties of these still cannot be said to be sufficient.
また、一般にポリエステルイミドと呼ばれるポリマーと
して、（１）脂肪族ジアミンとトリメリット酸とのイミ
ドジカルボン酸成分と脂肪族グリコール成分とのエステ
ルよりなるポリエステルイミド；（２）芳香族ジアミン
とトリメリット酸とのイミドジカルボン酸を主たる酸成
分とするポリエステルイミド：（３）Ｎ−Ｐ−カルボキ
シフェニルトリメリットイミドを主たる酸成分とするポ
リエステルイミド；（４）アミノアルコールとトリメリ
ット酸よりなるイミドヒドロキシカルボン酸を含むポリ
エステルイミド等が知られている。しかしながら、上記
（１）のポリエステルイミドは融点あるいは結晶性が低
いという問題があり、上記（２）のポリエステルイミド
は溶融粘度が高く、通常の溶融成形に供することが困難
で必り。上記（３）のポリエステルイミドは高融点、高
粘度のため成形困難であり、また上記（３）のポリエス
テルイミドのうちＮ−Ｐ−カルボキシフェニルトリメリ
ット成分と芳香族ジオール成分とのエステルよりなるポ
リエステルイミドは高融点、高粘度のため成形困難であ
り、またこの芳香族ジオール成分を脂肪族ジオール成分
に代えたものは溶融重合ないし成形時にイミド基が分解
し易いという問題がある。更に、また上記（４）のポリ
エステルイミドは非品性乃至結晶性が低く、耐熱性に劣
るという問題がおる。これら従来のポリエステルイミド
はワニス。In addition, as a polymer generally called polyesterimide, (1) a polyesterimide consisting of an ester of an imidodicarboxylic acid component of an aliphatic diamine and trimellitic acid and an aliphatic glycol component; (2) a polyesterimide consisting of an ester of an imidodicarboxylic acid component and an aliphatic glycol component; Polyesterimide containing imidodicarboxylic acid as the main acid component: (3) Polyesterimide containing N-P-carboxyphenyl trimellitimide as the main acid component; (4) Imidohydroxycarboxylic acid consisting of amino alcohol and trimellitic acid. Polyesterimide containing the above is known. However, the polyesterimide (1) has a problem of a low melting point or crystallinity, and the polyesterimide (2) has a high melt viscosity, making it difficult to subject it to ordinary melt molding. The polyesterimide (3) above is difficult to mold due to its high melting point and high viscosity, and among the polyesterimides (3) above, a polyester consisting of an ester of an N-P-carboxyphenyl trimellitic component and an aromatic diol component Imide is difficult to mold due to its high melting point and high viscosity, and when the aromatic diol component is replaced with an aliphatic diol component, there is a problem in that the imide group is easily decomposed during melt polymerization or molding. Furthermore, the polyesterimide (4) above has a problem of poor quality, low crystallinity, and poor heat resistance. These traditional polyester imides are varnishes.
エナメル等として使用されているが、溶融成形に適用す
ることは困難であった。そこで本発明者等は、通常の溶
融成形が可能で、かつ優れた機械的特性、耐熱性１寸法
安定性を有する素材としてイミドジカルボン酸と芳香族
ジオキシ化合物よりなるポリエステルイミドを既に提案
した。しかし、該ポリエステルイミドはこれら優れた特
性を有してはいるが、難燃性に関しては未だ不十分であ
った。Although it has been used as enamel, it has been difficult to apply it to melt molding. Therefore, the present inventors have already proposed a polyesterimide made of imidodicarboxylic acid and an aromatic dioxy compound as a material that can be melt-molded and has excellent mechanical properties, heat resistance, and 1-dimensional stability. However, although the polyesterimide has these excellent properties, its flame retardance is still insufficient.
Ｃ６発明の目的
そこで本発明者らは、該ポリエステルイミドの特性をそ
まま有し、かつ難燃性に優れた組成物を提供することを
目的として鋭意研究を行った結果、本発明に到達したも
のである。C6 Purpose of the Invention Therefore, the present inventors conducted extensive research with the aim of providing a composition that possesses the properties of the polyesterimide and has excellent flame retardancy, and as a result, the present invention was achieved. It is something.
ｄ０発明の構成および効果
ずなわら、本発明は、下記式（Ｉ）
［ここでｎは２〜１２の整数を示す。］で示されるイミ
ドジカルボン酸を主たる酸成分とし、芳香族ジオキシ化
合物を主たるジオール成分とするポリエステルイミド１
００重量部に下記式（Ｉｌｌ）および／または下記式（
Ｉ［Ｉ）Ｒ−３ＯＥＭ ・・・・・・
（Ｉｆ）（Ｒ−３Ｏ３）２ Ｍ’ ……（
ＩＩＩ）で示される有機スルホネート金属塩０．１〜１
０単量部を含有せしめてなるポリエステルイミド組成物
である。d0 In addition to the structure and effects of the invention, the present invention provides the following formula (I) [where n represents an integer of 2 to 12]. ] Polyester imide 1 containing imidodicarboxylic acid as the main acid component and an aromatic dioxy compound as the main diol component
The following formula (Ill) and/or the following formula (
I[I)R-3OEM ・・・・・・
(If) (R-3O3)2 M'......(
III) Organic sulfonate metal salt 0.1-1
This is a polyesterimide composition containing 0 parts by weight.
式（Ｉ＞で示されるイミドジカルボン酸は、トリメリッ
ト酸無水物と対応するジアミン（８２Ｎ（−ＣＩ−１２
−）Ｎｔ（２）とを従来公知のイミド化反応によって反
応させることで、極めて容易に合成することができる。The imidodicarboxylic acid represented by the formula (I>) is composed of trimellitic anhydride and the corresponding diamine (82N(-CI-12
-) Nt(2) by a conventionally known imidization reaction, it can be synthesized extremely easily.
式（１）におけるｎは２〜１２の整数でおり、これらの
うち偶数が好ましく、特に６と１２の数が好ましい。n in formula (1) is an integer of 2 to 12, preferably even numbers, and particularly preferably 6 and 12.
本発明では上記イミドジカルボン酸以外に他種ジカルボ
ン酸および／またはオキシカルボン酸を少量共重合する
こともできる。該ジカルボン酸としてはテレフタル酸、
イソフタル酸、ジフェニルジカルボン１，４．４’−ジ
フェニルエーテルジカルボン
２、６−ナフタレンジカルボンＭ，１．５ーナフタレン
ジカルボン酸， ２．７−ナフタレンジカルボン酸。In the present invention, other types of dicarboxylic acids and/or oxycarboxylic acids may be copolymerized in small amounts in addition to the above imidodicarboxylic acids. As the dicarboxylic acid, terephthalic acid,
Isophthalic acid, diphenyl dicarboxylic 1,4,4'-diphenyl ether dicarboxylic 2,6-naphthalenedicarbone M, 1.5 naphthalenedicarboxylic acid, 2.7-naphthalenedicarboxylic acid.
４、４′−フェノキシエタンジカルボン酸，コハク酸。4,4'-phenoxyethanedicarboxylic acid, succinic acid.
アジピン酸，セパチン酸，ドデカン酸， １．４−シク
ロヘキサンジカルボン酸等、オキシカルボン酸としては
Ｐ−オキシ安息香ｆｆ．、 ｍ−オキシ安息香酸，６−
オキシ−２−ナフトエ酸，ε−オキシカプロン酸等が挙
げられる。これらジカルボン酸および／またはオキシカ
ルボン酸の使用母はイミドジカルボン酸に対し、好まし
くは３０モル％以下、より好ましくは２０モル％以下、
特に好ましくは１０モル％以下である。Adipic acid, cepatic acid, dodecanoic acid, 1,4-cyclohexanedicarboxylic acid, etc.; examples of oxycarboxylic acids include P-oxybenzoic acid; , m-oxybenzoic acid, 6-
Examples include oxy-2-naphthoic acid and ε-oxycaproic acid. The base of these dicarboxylic acids and/or oxycarboxylic acids is preferably 30 mol% or less, more preferably 20 mol% or less, based on the imidodicarboxylic acid.
Particularly preferably, it is 10 mol% or less.
次に本発明で用いる芳香族ジオキシ化合物としては具体
的にはハイドロキノン、置換ハイドロキノン、レゾルシ
ン、２，６−シヒドロキシナフタレン、４．４’−ジヒ
ドロキシジフェニル、４．４’−ジヒドロキシジフェニ
ルエーテル、フェノールフクレイン，２．２ービス（４
−ヒドロキシフェニル）プロパン（ビスフェノールＡ＞
、１．１−ビス（４−ヒドロキシフェニル）シクロへキ
リン、４．４’−ジヒドロキシジフェニルスルホン、４
．４’−ジヒドロキシジフェニルエーテル、３．４’−
ジヒドロキシジフェニルエーテル、４．４’−ジヒドロ
キシベンゾフェノン、４．４’−ジヒドロキシジフェニ
ルメタン。Next, specific examples of aromatic dioxy compounds used in the present invention include hydroquinone, substituted hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, and phenolfucrein. ,2.2bis(4
-Hydroxyphenyl)propane (bisphenol A>
, 1.1-bis(4-hydroxyphenyl)cyclohekiline, 4.4'-dihydroxydiphenylsulfone, 4
．． 4'-dihydroxydiphenyl ether, 3.4'-
Dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane.
３、４′−ジヒドロキシジフェニルメタン、３．４’−
ジヒドロキシベンゾフェノン、２．２’−ジメチルビス
フェノールＡ，２．２’−ジクロロビスフェノールＡ。3,4'-dihydroxydiphenylmethane, 3,4'-
Dihydroxybenzophenone, 2,2'-dimethylbisphenol A, 2,2'-dichlorobisphenol A.
２、２′−ジブロモビスフェノールＡ， ２．２’，６
． ６’−テトラメチルビスフェノールＡ， ２．２’
， ６．６’−テトラクロルビスフェノールＡ， ２．
２’，８． ６’−テトラブロモビスフェノールＡ，１
．４−ビス［２−（Ｐ−ヒドロキシフェニル）プロピル
］ベンゼン。2,2'-dibromobisphenol A, 2.2',6
．． 6'-tetramethylbisphenol A, 2.2'
, 6.6'-tetrachlorobisphenol A, 2.
2', 8. 6'-tetrabromobisphenol A,1
．． 4-bis[2-(P-hydroxyphenyl)propyl]benzene.
１、３−ビス［２− （Ｐ−ヒドロキシフェニル）プロ
ピル］ベンゼン等が好ましく埜げられる。1,3-bis[2-(P-hydroxyphenyl)propyl]benzene and the like are preferably used.
また上記置換ハイドロキノンの置換基としては、炭素数
１〜１０のアルキル、例えばメチル、エチル。Further, as a substituent of the above-mentioned substituted hydroquinone, alkyl having 1 to 10 carbon atoms, such as methyl and ethyl.
プロピル、イソプロピル、ブチル、イソブチル。Propyl, isopropyl, butyl, isobutyl.
ｔ−ブチル、ペンチル、ｔ−アミノ、ヘキシル等、炭素
数５〜１０のシクロアルキル例えばシクロペンチル、シ
クロヘキシル等、炭素数６〜１０のアリール、例えばフ
ェニル、トリル等、炭素数７〜１２のアラルキル例えば
ベンジル、メチルベンジル、ジメチルベンジル等、炭素
数１〜１０のアルコキシ例えばメトキシ、エトキシ、フ
ェノキシ等、ハロゲン例えば塩素，臭素等などが挙げら
れる。この置換ハイドロキノンの具体例としては、メチ
ルハイドロキノン、ｔ−ブチルハイドロキノン、ｔ−ア
ミルハイドロキノン、クロルハイドロキノン等が好まし
く挙げられる。上記芳香族ジオキシ化合物のうち、ハイ
ドロキノン、メチルハイドロキノン。cycloalkyl having 5 to 10 carbon atoms, such as t-butyl, pentyl, t-amino, hexyl, etc. Aryl having 6 to 10 carbon atoms, such as cyclopentyl, cyclohexyl, etc., aralkyl having 7 to 12 carbon atoms, such as benzyl , methylbenzyl, dimethylbenzyl, alkoxy having 1 to 10 carbon atoms such as methoxy, ethoxy, phenoxy and the like, halogen such as chlorine, bromine and the like. Preferred examples of the substituted hydroquinone include methylhydroquinone, t-butylhydroquinone, t-amylhydroquinone, and chlorohydroquinone. Among the above aromatic dioxy compounds, hydroquinone and methylhydroquinone.
℃ーブチルハイドロキノン、ビスフェノールＡ。°C-butylhydroquinone, bisphenol A.
４、４′−ジヒドロキシジフェニルスルホンが好ましい
。4,4'-dihydroxydiphenyl sulfone is preferred.
本発明のポリエステルイミドは上記酸成分およびジオー
ル成分を従来公知の不縮合反応により１９ることができ
るが、特にジカルボン酸成分のジアリールエステル、好
ましくはジフェニルニスデルとジオールとの反応、ある
いはジカルボン酸とジオールの低級カルボン酸エステル
、好ましくは耐酸エステルとの反応により好ましり１ｑ
ることかできる。また、本発明のポリエステルイミドで
は、得られるポリマーが実質的に線状である範囲内で多
官能性化合物心よび／または単官能性化合物を添加して
もよい。The polyesterimide of the present invention can be prepared by reacting the acid component and the diol component with a conventionally known non-condensation reaction, but in particular, the reaction of a diaryl ester of a dicarboxylic acid component, preferably diphenylnisder, with a diol, or the reaction of a dicarboxylic acid with a diaryl ester, preferably a diaryl ester of a dicarboxylic acid component. Lower carboxylic acid ester of diol, preferably 1q by reaction with acid-resistant ester
I can do that. Further, in the polyesterimide of the present invention, a polyfunctional compound core and/or a monofunctional compound may be added to the extent that the obtained polymer is substantially linear.
該多官能性化合物としては、トリメシン酸，トリメリツ
ート酸，ベンゾフェノンテトラカルボン酸。Examples of the polyfunctional compound include trimesic acid, trimellitutic acid, and benzophenonetetracarboxylic acid.
ピロメリット酸，グリセリン、トリメチロール。Pyromellitic acid, glycerin, trimethylol.
プロパン、ペンタエリスリトール等、単官能性化合物と
しては、安息香酸，ベンゾイル安息＠酸。Monofunctional compounds such as propane and pentaerythritol include benzoic acid and benzoylbenzoic acid.
ナフトエ酸等が挙げられる。Examples include naphthoic acid.
上記多官能性および／または単官能性化合物の添加量は
ジカルボン酸成分に対して好ましくは５モル％以下、よ
り好ましくは３モル％以下、特に好ましくは１モル％以
下である。The amount of the polyfunctional and/or monofunctional compound added is preferably 5 mol% or less, more preferably 3 mol% or less, particularly preferably 1 mol% or less based on the dicarboxylic acid component.
本発明のポリエステルイミドはフェノール／テトラクロ
ルエタン混合溶媒（重量比６０／ ４０ ）を用いて３
５℃で測定した固有粘度が０．４以上であることが好ま
しく、０．５以上であることがより好ましく、０．６以
上であることが特に好ましい。The polyesterimide of the present invention is prepared using a mixed solvent of phenol/tetrachloroethane (weight ratio 60/40).
The intrinsic viscosity measured at 5° C. is preferably 0.4 or more, more preferably 0.5 or more, and particularly preferably 0.6 or more.
下記式（ｆｆ＞および（ＩＩＩ）
ＲＳＯ３Ｍ ……（ＩＩ）（Ｒ−８Ｏ
３）２ Ｍ’ ……（ＩＩＩ）で示される有
機スルホネート金属塩としては具体的には、ペンビンス
ルホン酸ナトリウム、ベンゼンスルホン酸カリウム、ペ
ンピンスルホン酸カルシウム、ペンビンスルホン酸マグ
ネシウム、クロルベンゼンスルホン酸ナトリウム、クロ
ルベンゼンスルホン酸カリウム、クロルベンゼンスルホ
ン酸カルシウム、クロルベンゼンスルホンシウム、ジク
ロルベンゼンスルホン酸ナトリウム。The following formula (ff> and (III) RSO3M ... (II) (R-8O
3) 2M'...Specifically, the organic sulfonate metal salt represented by (III) includes sodium pembenesulfonate, potassium benzenesulfonate, calcium pembenesulfonate, magnesium pembenesulfonate, and chlorobenzenesulfone. Sodium chlorobenzenesulfonate, potassium chlorobenzenesulfonate, calcium chlorobenzenesulfonate, sodium chlorbenzenesulfonate, sodium dichlorobenzenesulfonate.
ジクロルベンゼンスルホン酸カリウム、ジクロルベンゼ
ンスルホン酸カルシウム、ジクロルペンビンスルホン酸
マグネシウム、トリクロルベンビンスルホン酸ナトリウ
ム、トリクロルベンゼンスルホン酸カリウム、トリクロ
ルベンゼンスルホン酸カルシ「クロルニトロベンゼンス
ルホン酸カリウム、ニトロベンゼンスルホン酸カリウム
、ニトロペンピンスルホン酸カルシウム、ナフタレンス
ルホン酸ナトリウム、ナフタレンスルホン酸カリウム、
ナフタレンスルホン酸カルシウム、ジクロルナフタレン
スルホン酸ツートリウム、ジクロルナフタレンスルホン
酸カリウム、トリクロルナフタレンスルホン酸ナトリウ
ム、トリクロルベンゼンスルホン酸カリウム、ブロムベ
ンゼンスルホン酸ナトリウム、ブロムベンゼンスルホン
酸カリウム。Potassium dichlorobenzene sulfonate, calcium dichlorobenzene sulfonate, magnesium dichloropendine sulfonate, sodium trichlorobenzene sulfonate, potassium trichlorobenzene sulfonate, potassium trichlorobenzene sulfonate, potassium chlornitrobenzene sulfonate, potassium nitrobenzene sulfonate , calcium nitropenpine sulfonate, sodium naphthalene sulfonate, potassium naphthalene sulfonate,
Calcium naphthalene sulfonate, dichlornaphthalene sulfonate, potassium dichloronaphthalene sulfonate, sodium trichloronaphthalene sulfonate, potassium trichlorobenzenesulfonate, sodium bromobenzene sulfonate, potassium bromobenzene sulfonate.
ブロムペンビンスルホン酸カルシウム、ジブロムベンゼ
ンスルホン酸ナトリウム、ジブロムベンゼンスルホン酸
カルシウム、ジブロムベンゼンスルホン酸カリウム、ト
リブロムベンゼンスルホン酸ナトリウム、トリブロムベ
ンゼンスルホン酸カリウム、トリブロムベンゼンスルホ
ン酸カルシウム。Calcium bromobenzene sulfonate, sodium dibromobenzene sulfonate, calcium dibromobenzene sulfonate, potassium dibromobenzene sulfonate, sodium tribromobenzene sulfonate, potassium tribromobenzene sulfonate, calcium tribromobenzene sulfonate.
クロルニトロベンゼンスルホン酸ナトリウム、クロルニ
トロベンゼンスルホン酸カリウム、クロルニトロベンゼ
ンスルホン酸カルシウム、ジクロルニトロペンビンスル
ホン酸ナトリウム、ジクロルニトロペンビンスルホン酸
カリウム、ジクロルニトロベンゼンスルホン酸カルシウ
ム、ジフェニルスルホンスルホン酸ナトリウム、ジフェ
ニルスルホンスルホン酸カリウム、ブロモナフタレンス
ルホン酸ナトリウム、ブロモナフタレンスルホン酸カリ
ウム、ジブロモナフタレンスルホン酸ナトリウム、ジブ
ロモナフタレンスルホン酸カリウム。Sodium chlornitrobenzenesulfonate, potassium chlornitrobenzenesulfonate, calcium chlornitrobenzenesulfonate, sodium dichlornitrobenzenesulfonate, potassium dichlornitrobenzenesulfonate, calcium dichlornitrobenzenesulfonate, sodium diphenylsulfonesulfonate, diphenylsulfonesulfone Potassium acid, sodium bromonaphthalene sulfonate, potassium bromonaphthalene sulfonate, sodium dibromonaphthalene sulfonate, potassium dibromonaphthalene sulfonate.
フルオロベンゼンスルホン酸ナトリウム、フルオロベン
ゼンスフレホン酸カリウム、フルオロベンゼンスルホン
ルホン酸ナトリウム、ジフルオロペンぜンスルホン酸カ
リウム、ジフルオロベンゼンスルホン酸カルシウム、ジ
クロルジフェニルスルホンスルホン酸ナトリウム、ジク
ロルジフェニルスルホンスルホン酸カリウム、トリクロ
ルメチルスルホン酸ナトリウム、トリクロルメチルスル
ホン酸カリウム。Sodium fluorobenzenesulfonate, potassium fluorobenzenesulfonate, sodium fluorobenzenesulfonesulfonate, potassium difluoropenzenesulfonate, calcium difluorobenzenesulfonate, sodium dichlorodiphenylsulfonesulfonate, potassium dichlordiphenylsulfonesulfonate, trichlor Sodium methylsulfonate, potassium trichloromethylsulfonate.
トリクロルメチルスルホン酸カルシウム、トリフルオロ
メチルスルホン酸ナトリウム、トリフルオロメチルスル
ホン
ルスルホン酸カルシウム、パークロルエチルスルホン酸
す１ヘリウム、パーフルオロエチルスルホン酸カリウム
、パーフルオロエチルスルホンシウム、パーフルオ［１
１０ピルスルホン酸ナトリウム、パーフルオロプロピル
スルボン酸カリウム。Calcium trichloromethylsulfonate, sodium trifluoromethylsulfonate, calcium trifluoromethylsulfonesulfonate, monohelium perchloroethylsulfonate, potassium perfluoroethylsulfonate, perfluoroethylsulfonium, perfluoro[1]
10 Sodium pyl sulfonate, potassium perfluoropropyl sulfonate.
ニトロメチルスルホン酸ナトリウム、ニトロメチルスル
ホン酸カルウム、ニトロメチルスルホン酸カルシウム等
を挙げることができる。Examples include sodium nitromethylsulfonate, potassium nitromethylsulfonate, calcium nitromethylsulfonate, and the like.
これらのうちジクロルベンゼンスルホン酸ナトリウム、
ジクロルベンゼンスルホン
トリクロルベンゼンスルホン酸ナトリウム、トリクロル
ベンゼンスルホン酸カリウムが好ましい。Among these, sodium dichlorobenzenesulfonate,
Dichlorobenzene sulfone, sodium trichlorobenzene sulfonate, and potassium trichlorobenzene sulfonate are preferred.
本発明では、前記ポリエステルイミドに上記有機スルホ
ネート金属塩の１種または２種以上を含有せしめる。含
有せしめる方法としては、ポリエステルイミドの重縮合
時に前もって添加し、右改スルホネート金属塩の存在下
に重合する方法、重合後のポリエステルイミド溶融ポリ
マー中に有機スルホネート金属塩を添加する方法、ポリ
エステルイミドチップに有機スルホネート金属塩をトラ
イブレンドし、次いで溶融混合する方法等各種の方法が
適用できる。有機スルホネート金属塩の添加量はポリエ
ステルイミド１００重最部に対してｏ、ｉ〜１０重量部
とする。添加量が０．１重量部に満たない場合は、得ら
れた組成物の難燃性が不十分でおり、また１０重量部を
越えた場合には、機械的特性等が低下して好ましくない
。添加量として好ましくは０．２〜８重量部、特に好ま
しくは０．３〜６重母部である。In the present invention, the polyesterimide contains one or more of the organic sulfonate metal salts. Methods for containing the organic sulfonate metal salt include adding it in advance during polycondensation of polyesterimide and polymerizing it in the presence of the right-modified sulfonate metal salt, adding the organic sulfonate metal salt to the molten polyesterimide polymer after polymerization, and adding the organic sulfonate metal salt to the molten polyesterimide polymer after polymerization. Various methods can be applied, such as a method of triblending an organic sulfonate metal salt and then melt-mixing. The amount of the organic sulfonate metal salt added is from o to 10 parts by weight based on 100 parts by weight of the polyesterimide. If the amount added is less than 0.1 part by weight, the resulting composition will have insufficient flame retardancy, and if it exceeds 10 parts by weight, the mechanical properties etc. will deteriorate, which is undesirable. . The amount added is preferably 0.2 to 8 parts by weight, particularly preferably 0.3 to 6 parts by weight.
本発明のポリエステルイミド組成物は難燃性に優れ、ま
た難燃剤である有機スルホネート金属塩の添加量が比較
的少量でよいため、ポリエステルイミドそのものの機械
的特性、耐熱性２寸法安定性、更には成形性ををのまま
有している。本発明のポリエステルイミド組成物は、例
えば押出し成形、射出成形等通常の溶融成形が可能で、
繊維。The polyesterimide composition of the present invention has excellent flame retardancy, and since only a relatively small amount of organic sulfonate metal salt, which is a flame retardant, can be added, the polyesterimide itself has excellent mechanical properties, heat resistance, two-dimensional stability, and has the same moldability. The polyesterimide composition of the present invention can be subjected to conventional melt molding such as extrusion molding, injection molding, etc.
fiber.
フィルム、プラスチックス等として極めて有効に利用で
きる。It can be used extremely effectively as films, plastics, etc.
また、本発明のポリエステルイミド組成物には上記有機
スルホネー１〜金属塩以外にガラス繊維。In addition to the above-mentioned organic sulfones 1 to metal salts, the polyesterimide composition of the present invention also contains glass fibers.
アラミド繊維、炭素繊維等の補強繊維、シリカ等のフィ
ラーその仙滑剤、核剤、離型剤、酸化安定剤、紫外線吸
収剤、顔料２着色剤等を適宜配合してもよい。Reinforcing fibers such as aramid fibers and carbon fibers, fillers such as silica, lubricants, nucleating agents, mold release agents, oxidation stabilizers, ultraviolet absorbers, pigments, coloring agents, etc. may be blended as appropriate.
以下、実施例を挙げて本発明を詳述するが実施例中「部
」は「重量部」を意味する。ポリマーの固有粘度はフェ
ノール／テトラクロルエタン混合溝ａ￥（重唱比６０／
４０ ）を用いて３５℃で測定した。Hereinafter, the present invention will be described in detail with reference to Examples, where "parts" means "parts by weight". The intrinsic viscosity of the polymer is phenol/tetrachloroethane mixed groove a￥ (mass ratio 60/
40) at 35°C.
また融点はＤＳＣを用い１０℃／分の昇温速度にて測定
した。Further, the melting point was measured using DSC at a heating rate of 10° C./min.
実施例１および比較例１
Ｎ、Ｎ’−へキサメチレンビストリメリットイミドジフ
ェニルエステル６１６部、ハイドロキノン７９部、ビス
フェノールＡ６８部、 ２，４．５−トリクロルベンゼ
ンスルホン酸カリウム６部およびテトラブチルチタネー
ト０．１部を留出系を備えた攪拌装置付き反応器に仕込
み、反応器をよく窒素置換した後、常圧下２４０’Ｃで
３０分、次いで２部℃に昇温して３０分、更に３３０℃
に昇温しで３０分反応させた。Example 1 and Comparative Example 1 616 parts of N,N'-hexamethylenebistrimeritimid diphenyl ester, 79 parts of hydroquinone, 68 parts of bisphenol A, 6 parts of potassium 2,4.5-trichlorobenzenesulfonate, and 0.0 parts of tetrabutyl titanate. One part was charged into a reactor equipped with a stirring device equipped with a distillation system, and after the reactor was thoroughly purged with nitrogen, the temperature was raised to 240'C for 30 minutes under normal pressure, then the temperature was raised to 2 parts Celsius for 30 minutes, and further to 330°C.
The temperature was raised to 30 minutes, and the reaction was carried out for 30 minutes.
次に反応系を約１５分間かけて約１５ｍｍ１ｇまで徐々
に真空とし、次いで０．３ｍｍ１ｌ（］の高真空として
約２０分間反応させた。得られたポリマーは融点３０８
℃。Next, the reaction system was gradually evacuated to about 15 mm 1 g over about 15 minutes, and then the reaction was carried out at a high vacuum of 0.3 mm 1 l (] for about 20 minutes. The obtained polymer had a melting point of 308
℃.
固有粘度０１８０であった。、得られたポリマーを１５
０°Ｃで４時間乾燥後、ポリマ一温度３３０ °ｃ、
谷型温度、約１５０℃で射出成形し、得られた成形品を
用いて限界酸素指数（ＬＯＩ）を測定したところ２９゜
０であった。The intrinsic viscosity was 0180. , the obtained polymer was 15
After drying at 0°C for 4 hours, the polymer temperature was 330°C,
Injection molding was carried out at a valley mold temperature of about 150°C, and the limiting oxygen index (LOI) of the obtained molded product was measured and found to be 29°0.
比較として２，４．５−トリクロルベンゼンスルホン酸
カリウムを添加しない以外は実施例１と同様にして重合
、成形した成形品（固有粘度０．８４）のＬＯＩを測定
したところ２４．０であった。これより本発明のポリエ
ステルイミド組成物が極めて難燃性に優れていることが
わかる。For comparison, the LOI of a molded article (intrinsic viscosity 0.84) that was polymerized and molded in the same manner as in Example 1 except that potassium 2,4.5-trichlorobenzenesulfonate was not added was 24.0. . This shows that the polyesterimide composition of the present invention has extremely excellent flame retardancy.
実施例２〜５
Ｎ、Ｎ’−へキサメチレンビストリメリットイミドジフ
ェニルエステル６１６部、ハイドロキノン６９部、ビス
フェノールＡ４６部、ｔ−ブチルハイドロキノン３３部
、酢酸第１錫０．０９部および表１に示した有機スルホ
ネート金属塩の所定量を実施例１と同じ反応器に入れ、
実施例１と同様の条件下で重合した。得られたポリマー
の固有粘度おにびＬＯＩを表１に示す。表１には比較と
して有機スルホネート金属塩を添加しない以外は同様に
重合したものについてＬＯＩを示したが、本発明の組成
物が難燃性に優れていることがわかる。Examples 2 to 5 616 parts of N,N'-hexamethylene bistrimeritimid diphenyl ester, 69 parts of hydroquinone, 46 parts of bisphenol A, 33 parts of t-butylhydroquinone, 0.09 part of stannous acetate and the components shown in Table 1. A predetermined amount of organic sulfonate metal salt was placed in the same reactor as in Example 1,
Polymerization was carried out under the same conditions as in Example 1. Table 1 shows the intrinsic viscosity and LOI of the obtained polymer. For comparison, Table 1 shows the LOI of a polymerized product in the same manner except that no organic sulfonate metal salt was added, and it can be seen that the composition of the present invention has excellent flame retardancy.
表 １
実施例６
比較例１で得られたポリ了−チツブ１００部に表２に示
した有機スルホネート金属塩の所定量をトライブレンド
し、該ブレンドチップを一軸エクストルーダーを用いて
ポリマ一温度３３０ ’Ｃ１平均滞留時間約５分でスト
ランド状に溶融押出した。得られたストランドを用いて
ＬＯＩを測定した結果を表２に示したが、本発明の組成
物が少量の有機スルホネート金属塩により難燃性が向上
しているのがわかる。Table 1 Example 6 100 parts of the polyolefin chips obtained in Comparative Example 1 were triblended with a predetermined amount of the organic sulfonate metal salt shown in Table 2, and the blend chips were heated to a polymer temperature of 330°C using a uniaxial extruder. 'C1 was melt extruded into a strand with an average residence time of about 5 minutes. The results of LOI measurements using the obtained strands are shown in Table 2, and it can be seen that the flame retardance of the composition of the present invention is improved by a small amount of organic sulfonate metal salt.
表 ２Table 2
Claims (1)
香族ジオキシ化合物を主たるジオール成分とするポリエ
ステルイミド１００重量部に下記式（II）および／また
は下記式（III） Ｒ−ＳＯ＿３Ｍ……（II） （Ｒ−ＳＯ＿３）＿２Ｍ′……（III） 〔ここでＭはアルカリ金属、Ｍ′はアルカリ土類金属、
Ｒはハロゲン原子、ニトロ基およびスルホン基で置換し
ていてもよい脂肪族残基および芳香族残基を示す。〕 で示される有機スルホネート金属塩０．１〜１０重量部
を含有せしめてなるポリエステルイミド組成物。[Claims] The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [Here, n represents an integer from 2 to 12. ] The following formula (II) and/or the following formula (III) R-SO_3M...(II) (R-SO_3)_2M'...(III) [Here, M is an alkali metal, M' is an alkaline earth metal,
R represents an aliphatic residue or an aromatic residue which may be substituted with a halogen atom, a nitro group, or a sulfone group. ] A polyesterimide composition containing 0.1 to 10 parts by weight of an organic sulfonate metal salt represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10218586A JPS62257964A (en) | 1986-05-06 | 1986-05-06 | Polyester imide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10218586A JPS62257964A (en) | 1986-05-06 | 1986-05-06 | Polyester imide composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62257964A true JPS62257964A (en) | 1987-11-10 |
Family
ID=14320608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10218586A Pending JPS62257964A (en) | 1986-05-06 | 1986-05-06 | Polyester imide composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62257964A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007502347A (en) * | 2003-08-11 | 2007-02-08 | ゼネラル・エレクトリック・カンパニイ | Flame retardant fiber reinforced composition with improved fluidity |
-
1986
- 1986-05-06 JP JP10218586A patent/JPS62257964A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007502347A (en) * | 2003-08-11 | 2007-02-08 | ゼネラル・エレクトリック・カンパニイ | Flame retardant fiber reinforced composition with improved fluidity |
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