JP2008231324A - Sulfonated aromatic polycarbonate oligomer and thermoplastic resin composition containing the same - Google Patents
Sulfonated aromatic polycarbonate oligomer and thermoplastic resin composition containing the same Download PDFInfo
- Publication number
- JP2008231324A JP2008231324A JP2007075516A JP2007075516A JP2008231324A JP 2008231324 A JP2008231324 A JP 2008231324A JP 2007075516 A JP2007075516 A JP 2007075516A JP 2007075516 A JP2007075516 A JP 2007075516A JP 2008231324 A JP2008231324 A JP 2008231324A
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- JP
- Japan
- Prior art keywords
- aromatic polycarbonate
- group
- polycarbonate resin
- molecular weight
- sulfonated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 162
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 63
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 63
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 38
- 239000011342 resin composition Substances 0.000 title claims abstract description 20
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 111
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 111
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 150000004010 onium ions Chemical class 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 26
- 229920005989 resin Polymers 0.000 abstract description 20
- 239000011347 resin Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 description 52
- -1 sulfone compounds Chemical class 0.000 description 32
- 239000002994 raw material Substances 0.000 description 23
- 238000005809 transesterification reaction Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 238000006277 sulfonation reaction Methods 0.000 description 16
- 239000000956 alloy Substances 0.000 description 15
- 229910045601 alloy Inorganic materials 0.000 description 15
- 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 description 14
- 239000000047 product Substances 0.000 description 11
- 239000000155 melt Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 208000016261 weight loss Diseases 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 7
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 7
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 239000013585 weight reducing agent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000002216 antistatic agent Substances 0.000 description 6
- 150000004650 carbonic acid diesters Chemical class 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920001955 polyphenylene ether Polymers 0.000 description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- MPWGZBWDLMDIHO-UHFFFAOYSA-N 3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1 MPWGZBWDLMDIHO-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000004429 atom Chemical group 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000005027 hydroxyaryl group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WZHKDGJSXCTSCK-FNORWQNLSA-N (E)-Hept-3-ene Chemical compound CCC\C=C\CC WZHKDGJSXCTSCK-FNORWQNLSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
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- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
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- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
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- HZRGZVAPEZNGSR-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexachloro-2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C1=CC(O)=CC=C1C(C(Cl)(Cl)Cl)(C(Cl)(Cl)Cl)C1=CC=C(O)C=C1 HZRGZVAPEZNGSR-UHFFFAOYSA-N 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- 229910052788 barium Inorganic materials 0.000 description 1
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- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
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- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- SJDACOMXKWHBOW-UHFFFAOYSA-N oxyphenisatine Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2NC1=O SJDACOMXKWHBOW-UHFFFAOYSA-N 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
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- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000012763 reinforcing filler Substances 0.000 description 1
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- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-O selenonium Chemical compound [SeH3+] SPVXKVOXSXTJOY-UHFFFAOYSA-O 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HISNRBVYBOVKMB-UHFFFAOYSA-N stibonium Chemical compound [SbH4+] HISNRBVYBOVKMB-UHFFFAOYSA-N 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
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- 125000004434 sulfur atom Chemical group 0.000 description 1
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- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、分子中にスルホ基及び／又はその誘導体を有する、新規なスルホン化芳香族ポリカーボネートオリゴマー、及びそれを含有する熱可塑性樹脂組成物に関する。本発明のスルホン化芳香族ポリカーボネートオリゴマーは、分子量が低く、種々の樹脂改質剤、添加剤、プライマー等として好適に使用される。特に芳香族ポリカーボネート樹脂に対しては親和性が高く、分散性に優れているので、芳香族ポリカーボネート樹脂の難燃剤、帯電防止剤、表面改質剤、相溶化剤等として優れた効果が期待できる。 The present invention relates to a novel sulfonated aromatic polycarbonate oligomer having a sulfo group and / or a derivative thereof in the molecule, and a thermoplastic resin composition containing the same. The sulfonated aromatic polycarbonate oligomer of the present invention has a low molecular weight and is suitably used as various resin modifiers, additives, primers and the like. Especially for aromatic polycarbonate resins, it has high affinity and excellent dispersibility, so it can be expected to have excellent effects as a flame retardant, antistatic agent, surface modifier, compatibilizer, etc. for aromatic polycarbonate resins. .
従来、熱可塑性樹脂の塗装性や密着性等の濡れ性を改善することを目的とした樹脂改質剤や、難燃剤、帯電防止剤、更には他の熱可塑性樹脂との相溶性改善剤として、スルホン酸アルカリ金属塩やスルホン酸オニウム塩等のスルホン化合物を用いることが知られている。中でも芳香族ポリカーボネート樹脂に難燃性や帯電防止性を付与する為に、上述した様なスルホン化合物を添加する方法が提案されている。 Conventionally, as a resin modifier for improving wettability such as paintability and adhesion of thermoplastic resins, flame retardants, antistatic agents, and compatibility improvers with other thermoplastic resins It is known to use sulfone compounds such as alkali metal sulfonates and onium sulfonates. Among them, a method of adding a sulfone compound as described above has been proposed in order to impart flame retardancy and antistatic properties to an aromatic polycarbonate resin.
難燃剤や耐電防止剤用途においては、従来からスルホン酸金属塩化合物が一般的に用いられている。しかしこの様な化合物は、一般的に芳香族ポリカーボネート樹脂への分散性が悪く、比較的少量添加した場合であっても、しばしば芳香族ポリカーボネート樹脂が本来有する、優れた透明性を損なうという問題があった。 For flame retardants and antistatic agents, sulfonic acid metal salt compounds have been generally used. However, such a compound is generally poorly dispersible in an aromatic polycarbonate resin, and even when added in a relatively small amount, there is a problem that the transparency inherent in the aromatic polycarbonate resin is often impaired. there were.
この様な透明性低下については、例えばホスホニウム塩等のオニウム塩を用いる方法が提案されている（例えば特許文献１参照）。しかしこの方法では、用いる化合物が低分子量である為に樹脂成形体からブリードアウトし易く、効果が持続し難いという、新たな問題が生じていた。 For such a decrease in transparency, a method using an onium salt such as a phosphonium salt has been proposed (see, for example, Patent Document 1). However, this method has a new problem that the compound to be used has a low molecular weight, so that it tends to bleed out from the resin molded body and the effect is difficult to sustain.
一方、ポリエチレンやポリスチレンをスルホン化したスルホン化ポリオレフィン（例えば、特許文献２参照）や、スルホン化ポリオキシエチレン、スルホン化された特定のポリエステル構造を含む芳香族ポリエステルポリカーボネート共重合体（例えば、特許文献３参照）等の高分子型スルホン化合物を使用する方法も、提案されている。 On the other hand, a sulfonated polyolefin obtained by sulfonating polyethylene or polystyrene (see, for example, Patent Document 2), a sulfonated polyoxyethylene, an aromatic polyester polycarbonate copolymer containing a specific sulfonated polyester structure (for example, Patent Document) A method using a polymer type sulfone compound such as 3) has also been proposed.
しかしこの様な高分子型スルホン化合物を用いた場合でも、樹脂成形体からのブリードアウト抑制効果は期待できる反面、スルホン化合物の基本骨格が芳香族ポリカーボネート樹脂と大きく異なる為に、芳香族ポリカーボネート樹脂との相溶性が悪く、かつ分子量が大きい為に芳香族ポリカーボネート樹脂への分散性が低く、芳香族ポリカーボネート樹脂の優れた透明性や機械物性を損なうという問題があった。 However, even when such a polymer type sulfone compound is used, the suppression effect of bleeding out from the resin molded product can be expected, but the basic skeleton of the sulfone compound is greatly different from the aromatic polycarbonate resin. In addition, since the compatibility is poor and the molecular weight is large, the dispersibility in the aromatic polycarbonate resin is low, and the excellent transparency and mechanical properties of the aromatic polycarbonate resin are impaired.
一方で、重量平均分子量３１０００のスルホン化ポリカーボネート樹脂を難燃剤として用いる方法が提案されている（例えば特許文献４参照）。しかし実際には、芳香族ポリカーボネート樹脂への分散性は低く、好適に使用することが出来なかった。 On the other hand, a method using a sulfonated polycarbonate resin having a weight average molecular weight of 31000 as a flame retardant has been proposed (see, for example, Patent Document 4). However, in practice, the dispersibility in the aromatic polycarbonate resin is low, and it could not be suitably used.
また特許文献４においては、粉末状の芳香族ポリマーに直接、無水硫酸（ＳＯ３）ガスを接触させて芳香族ポリマーをスルホン化しているので、この様な方法では芳香族ポリカーボネート樹脂粉末内部にまでスルホン基が導入され難い為、非効率であるだけでなく、スルホン化反応自体の制御が極めて困難であり、得られるスルホン化芳香族ポリカーボネート樹脂の品質がばらつくという問題があった。 In Patent Document 4, since the aromatic polymer is sulfonated by bringing sulfuric anhydride (SO 3 ) gas into direct contact with the powdered aromatic polymer, such a method allows the aromatic polycarbonate resin powder to reach the inside. Since it is difficult to introduce a sulfone group, it is not only inefficient but also the control of the sulfonation reaction itself is extremely difficult, and the quality of the resulting sulfonated aromatic polycarbonate resin varies.
更に、この様な粉体へのスルホン化の問題点を克服するために、本発明者らは、原料として高分子量の芳香族ポリマーを用いて、特許文献４に記載の、有機溶媒中でのスルホン化を行ったが、得られたスルホン化芳香族ポリカーボネート樹脂の品質がばらついてしまい、熱可塑性樹脂、特に芳香族ポリカーボネート樹脂の添加剤として好ましいものではなかった。 Furthermore, in order to overcome the problem of sulfonation to such a powder, the present inventors have used a high molecular weight aromatic polymer as a raw material and described in Patent Document 4 in an organic solvent. Although sulfonation was performed, the quality of the obtained sulfonated aromatic polycarbonate resin varied, and it was not preferable as an additive for thermoplastic resins, particularly aromatic polycarbonate resins.
この様に、熱可塑性樹脂、特に芳香族ポリカーボネート樹脂に添加した際、芳香族ポリカーボネート樹脂が本来有する、優れた透明性、機械物性を損なうことなく、芳香族ポリカーボネート樹脂中に高度に分散して、難燃性や帯電防止性等の優れた効果を奏するスルホン化合物が強く望まれていた。 In this way, when added to a thermoplastic resin, particularly an aromatic polycarbonate resin, the aromatic polycarbonate resin inherently has excellent transparency, without being spoiled mechanical properties, and highly dispersed in the aromatic polycarbonate resin, A sulfone compound having excellent effects such as flame retardancy and antistatic properties has been strongly desired.
本発明者らは、上述の課題について鋭意検討した。その結果、特定の低分子量芳香族ポリカーボネート樹脂（以下、芳香族ポリカーボネート樹脂オリゴマーということがある。）をスルホン化する際、意外なことに、スルホン化に際して生ずる芳香族ポリカーボネート樹脂の分子量低下が、従来の一般的な（具体的には例えば、分子量が１２０００〜３０００００の）芳香族ポリカーボネート樹脂におけるスルホン化時に比べて、抑制されていることを見出した。 The present inventors diligently studied the above-described problems. As a result, when a specific low molecular weight aromatic polycarbonate resin (hereinafter sometimes referred to as an aromatic polycarbonate resin oligomer) is sulfonated, the molecular weight of the aromatic polycarbonate resin that occurs upon sulfonation is unexpectedly reduced. It was found that this was suppressed compared to the time of sulfonation in a general (specifically, for example, a molecular weight of 12,000 to 300,000) aromatic polycarbonate resin.
そして芳香族ポリカーボネート樹脂の分子量低下が抑制されることで、連続的な、化学工業規模での製造が容易となり、且つこれらの分子量低下が引き起こす二次的な分子量低下、例えば熱可塑性樹脂、特に芳香族ポリカーボネート樹脂の添加剤として使用し、溶融混練する場合における樹脂組成物の分子量低下や、得られた樹脂組成物を成形してなる樹脂成形体の長期物性（例えば環境試験等による分子量低下等。）をも抑制できることを見出した。 Further, by suppressing the molecular weight reduction of the aromatic polycarbonate resin, it becomes easy to produce continuously on the chemical industrial scale, and secondary molecular weight reduction caused by these molecular weight reductions, for example, thermoplastic resins, particularly aromatics. When used as an additive for a group polycarbonate resin and melt kneaded, the molecular weight of the resin composition is lowered, or the long-term physical properties of the resin molded product obtained by molding the obtained resin composition (for example, the molecular weight is lowered by an environmental test or the like). ) Was also found to be suppressed.
更に、この様にして得られた、スルホン化芳香族ポリカーボネート樹脂オリゴマーは新規なものであり、芳香族ポリカーボネート樹脂と親和性が高く、これを含有した芳香族ポリカーボネート樹脂組成物が、従来から用いられてきた低分子量のスルホン化号物を含有する芳香族ポリカーボネート樹脂に対して、優れた透明性を有することを見出し、本発明を完成させた。 Furthermore, the sulfonated aromatic polycarbonate resin oligomer thus obtained is novel and has high affinity with the aromatic polycarbonate resin, and an aromatic polycarbonate resin composition containing this has been conventionally used. The present inventors have found that the aromatic polycarbonate resin containing the low molecular weight sulfonated compound has excellent transparency, and completed the present invention.
即ち本発明の要旨は、数平均分子量１０００〜１００００であり、分子鎖にスルホ基および／又はその誘導体を有するスルホン化芳香族ポリカーボネートオリゴマーに関する。 That is, the gist of the present invention relates to a sulfonated aromatic polycarbonate oligomer having a number average molecular weight of 1,000 to 10,000 and having a sulfo group and / or a derivative thereof in the molecular chain.
また本発明の別の要旨は、上述したスルホン化芳香族ポリカーボネートオリゴマーを含有することを特徴とする熱可塑性樹脂組成物、特に芳香族ポリカーボネート樹脂組成物に存する。 Another gist of the present invention resides in a thermoplastic resin composition, particularly an aromatic polycarbonate resin composition, containing the sulfonated aromatic polycarbonate oligomer described above.
本発明のスルホン化芳香族ポリカーボネートオリゴマーは、熱可塑性樹脂への帯電防止剤、表面改質剤、相溶化剤等として、優れた効果を奏することが期待できる。 The sulfonated aromatic polycarbonate oligomer of the present invention can be expected to exhibit excellent effects as an antistatic agent, a surface modifier, a compatibilizer, etc. for thermoplastic resins.
例えば帯電防止剤としては、（芳香族）ポリカーボネート樹脂、ポリエチレン樹脂やポリプロピレン樹脂、ポリスチレン樹脂、アクリロニトリルーブタジエンースチレン共重合体（ＡＢＳ）、アクリロニトリルースチレン共重合体（ＡＳ）、環状シクロオレフィン樹脂（ＣＯＰ）等に代表されるポリオレフィン樹脂、ポリエチレンテレフタラート樹脂やポリブチレンテレフタラート樹脂等に代表されるポリエステル樹脂、ポリアミド樹脂、ポリフェニレンエーテル樹脂等に代表されるポリエーテル樹脂、ポリアセタール樹脂等、従来公知の熱可塑性樹脂又はこれらのアロイへの適用が期待される。 For example, as an antistatic agent, (aromatic) polycarbonate resin, polyethylene resin or polypropylene resin, polystyrene resin, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), cyclic cycloolefin resin ( COP) and the like, polyester resins typified by polyethylene terephthalate resins and polybutylene terephthalate resins, polyamide resins, polyether resins typified by polyphenylene ether resins, and polyacetal resins. Application to thermoplastic resins or their alloys is expected.
表面改質剤用途としては、上述の熱可塑性樹脂又はこれらのアロイに添加することにより、表面の濡れ性等を向上させ、インク、塗料等の印刷・塗装性、他の樹脂や金属、ハードコート等に対する密着性を向上させることが期待される。また芳香族ポリカーボネート樹脂とポリアミド樹脂との相溶性向上も期待できる。 As a surface modifier, it can be added to the above-mentioned thermoplastic resins or their alloys to improve surface wettability, etc., and can be printed and painted on inks and paints, other resins and metals, and hard coats. It is expected to improve the adhesion to such as. Moreover, the compatibility improvement of aromatic polycarbonate resin and polyamide resin can also be expected.
中でも本発明のスルホン化芳香族ポリカーボネートオリゴマーは、特に芳香族ポリカーボネート樹脂に対して高い親和性を有するので、芳香族ポリカーボネート樹脂中での分散性に優れ、且つ樹脂成形体中からのブリードアウト抑制も期待できる、優れたスルホン化合物であることを特徴とする。 Among them, the sulfonated aromatic polycarbonate oligomer of the present invention has a particularly high affinity for the aromatic polycarbonate resin, so that it has excellent dispersibility in the aromatic polycarbonate resin and also suppresses bleed out from the resin molded product. It is an excellent sulfone compound that can be expected.
また本発明の芳香族ポリカーボネート樹脂組成物は、芳香族ポリカーボネート樹脂が本来有する透明性や機械物性を損なうことなく、スルホン化芳香族ポリカーボネートオリゴマーによって付与される、難燃性、帯電防止性、表面改質性、更には第三の樹脂とのアロイ化における相溶性等の改質効果が期待できるので、幅広い分野に適用することが期待できる。 Further, the aromatic polycarbonate resin composition of the present invention has flame retardancy, antistatic property, surface modification imparted by a sulfonated aromatic polycarbonate oligomer without impairing the transparency and mechanical properties inherent in the aromatic polycarbonate resin. It can be expected to be applied to a wide range of fields because it can be expected to improve quality and compatibility with the third resin.
以下、本発明を更に詳細に説明する。尚、各種化合物が有する「基」は、本発明の趣旨を逸脱しない範囲内において、置換基を有していてもよいことを意味する。 Hereinafter, the present invention will be described in more detail. In addition, the “group” possessed by various compounds means that it may have a substituent without departing from the scope of the present invention.
（１）スルホン化芳香族ポリカーボネートオリゴマー
先ず本発明のスルホン化芳香族ポリカーボネートオリゴマーについて説明する。本発明のスルホン化芳香族ポリカーボネートオリゴマーは、数平均分子量が１０００〜１００００であり、分子鎖にスルホ基および／又はその誘導体を有するものである。
(1) Sulfonated aromatic polycarbonate oligomer First, the sulfonated aromatic polycarbonate oligomer of the present invention will be described. The sulfonated aromatic polycarbonate oligomer of the present invention has a number average molecular weight of 1000 to 10,000 and has a sulfo group and / or a derivative thereof in the molecular chain.
中でも好ましくは、芳香族ポリカーボネートオリゴマーの分子鎖が、下記一般式（１）で表される繰り返し単位から成るものである。 Among them, the molecular chain of the aromatic polycarbonate oligomer is preferably composed of a repeating unit represented by the following general formula (1).
本発明のスルホン化芳香族ポリカーボネートオリゴマーの数平均分子量は、中でも１１００〜８０００、更には１２００〜５０００、特に１５００〜４０００であることが好ましい。 The number average molecular weight of the sulfonated aromatic polycarbonate oligomer of the present invention is preferably 1100 to 8000, more preferably 1200 to 5000, and particularly preferably 1500 to 4000.
尚、本発明のスルホン化芳香族ポリカーボネートオリゴマー、およびこの製造に用いる芳香族ポリカーボネート樹脂（以下、「原料芳香族ポリカーボネート樹脂」ということがある。）の数平均分子量（Ｍｎ）は、ＧＰＣ（ゲルパーミエーションクロマトグラフ）を用いて測定した値を、ポリスチレン換算分子量（数平均分子量：Ｍｎ）として換算した値であり、展開溶媒にはクロロホルムを用い、カラム温度４０℃で測定した値である。 The number average molecular weight (Mn) of the sulfonated aromatic polycarbonate oligomer of the present invention and the aromatic polycarbonate resin used in the production thereof (hereinafter sometimes referred to as “raw material aromatic polycarbonate resin”) is GPC (gel permeation). The value measured by using an association chromatograph) is a value converted as a polystyrene-converted molecular weight (number average molecular weight: Mn), and is a value measured at a column temperature of 40 ° C. using chloroform as a developing solvent.
本発明のスルホン化芳香族ポリカーボネートオリゴマーにおける、本発明のポリカーボネートオリゴマーは、上述した一般式（１）で表される繰り返し単位から成る。その製造方法は任意であり、従来公知の任意の方法によって得られるものを使用できる。 The polycarbonate oligomer of the present invention in the sulfonated aromatic polycarbonate oligomer of the present invention is composed of a repeating unit represented by the above general formula (1). The manufacturing method is arbitrary, and a product obtained by any conventionally known arbitrary method can be used.
本発明のスルホン化芳香族ポリカーボネートオリゴマーは、分子鎖にスルホ基（−ＳＯ２（ＯＨ））及び／又はその誘導体を有する。スルホ基の誘導体とはスルホ基のＯＨやＨが他の原子又は分子に置換されたスルホ残基を示し、具体的には例えば、スルホン酸塩（−ＳＯ３（Ｍ）ｎ）、スルホン酸エステル（−ＳＯ３Ｒ）、スルフィン酸（−ＳＯ２Ｈ）、スルホニルクロライド（−ＳＯ２Ｃｌ）、スルホン酸アミド（−ＳＯ２ＮＨＲ）、スルフィン酸エステル（−ＳＯ２Ｒ）（これらの式中、Ｍは１価又は２価の金属原子及び／又はオニウム化合物を、Ｒは炭化水素基を示し、ｎは０．５又は１を示す。）等の、スルホ残基が挙げられる。 The sulfonated aromatic polycarbonate oligomer of the present invention has a sulfo group (—SO 2 (OH)) and / or a derivative thereof in the molecular chain. A derivative of a sulfo group means a sulfo residue in which OH or H of the sulfo group is substituted with another atom or molecule. Specifically, for example, a sulfonate (—SO 3 (M) n ), a sulfonate ester (—SO 3 R), sulfinic acid (—SO 2 H), sulfonyl chloride (—SO 2 Cl), sulfonic acid amide (—SO 2 NHR), sulfinic acid ester (—SO 2 R) (in these formulas, M represents a monovalent or divalent metal atom and / or onium compound, R represents a hydrocarbon group, and n represents 0.5 or 1.).
上述のスルホ基誘導体において、Ｍで示される１価又は２価の金属としては、具体的には例えば、リチウム（Ｌｉ）、ナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）等のアルカリ金属；マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）等のアルカリ土類金属；アルミニウム（Ａｌ）、亜鉛（Ｚｎ）、スズ（Ｓｎ）、アンチモン（Ｓｂ）等が挙げられる。中でもＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ等のアルカリ金属が好ましく、中でもＮａ、Ｋ、Ｃｓが好ましい。 In the above-mentioned sulfo group derivative, as the monovalent or divalent metal represented by M, specifically, for example, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs Alkaline metals such as magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba); aluminum (Al), zinc (Zn), tin (Sn), antimony (Sb) ) And the like. Among them, alkali metals such as Li, Na, K, Rb, and Cs are preferable, and Na, K, and Cs are particularly preferable.
また、同じくＭで示されるオニウム化合物としては、具体的には例えば、フルオニウム、クロロニウム、ブロモニウム、ヨードニウム、オキソニウム、スルホニウム、セレノニウム、テレロニウム、アンモニウム、ホスホニウム、アルソニウム、スチボニウム、ボイストニウム等が挙げられる。中でもホスホニウム、アンモニウムが好ましく、特にホスホニウムが好ましい。 Similarly, specific examples of the onium compound represented by M include fluoronium, chloronium, bromonium, iodonium, oxonium, sulfonium, selenonium, telelonium, ammonium, phosphonium, arsonium, stibonium, and voicetonium. Of these, phosphonium and ammonium are preferable, and phosphonium is particularly preferable.
また、上述のＲで示される炭化水素基としては、具体的には例えば、炭素数１〜２０のアルキル基、炭素数２〜２０のアラルキル基、または炭素数５〜１５のアリール基等が挙げられる。中でもメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ターシャリーブチル基、フェニル基等が好ましい。 Specific examples of the hydrocarbon group represented by R include an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 2 to 20 carbon atoms, or an aryl group having 5 to 15 carbon atoms. It is done. Of these, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tertiary butyl group, phenyl group and the like are preferable.
本発明のスルホン化芳香族ポリカーボネートオリゴマーにおいて、スルホ基やその誘導体の導入位置は任意であり、芳香族ポリカーボネートオリゴマーの分子骨格中に導入されていれば、主鎖（例えば先述の一般式（１）における芳香環やＡ等）に直接導入されていても、又は、主鎖に結合する末端基（例えば先述の一般式（１）におけるＲ１、Ｒ２、Ｒ３及びＲ４等）に導入されていてもよい。 In the sulfonated aromatic polycarbonate oligomer of the present invention, the introduction position of the sulfo group or its derivative is arbitrary, and if it is introduced into the molecular skeleton of the aromatic polycarbonate oligomer, the main chain (for example, the general formula (1) described above) Or directly into a terminal group (for example, R 1 , R 2 , R 3 and R 4 in the general formula (1) described above) bonded to the main chain. It may be.
本発明のスルホン化芳香族ポリカーボネートオリゴマーにおけるスルホ基及び／またはその誘導体の含有量は任意であり、適宜選択して決定すればよい。含有量は通常、硫黄含有量（重量％）で表すことが出来る。硫黄含有量は燃焼イオンクロマト法を用いてＳＯ４の量を検出し、スルホン化芳香族ポリカーボネートオリゴマー中の硫黄原子含有量（重量％）換算値で指す。 The content of the sulfo group and / or the derivative thereof in the sulfonated aromatic polycarbonate oligomer of the present invention is arbitrary and may be appropriately selected and determined. The content can usually be represented by the sulfur content (% by weight). The sulfur content is determined by detecting the amount of SO 4 using combustion ion chromatography and converting the sulfur atom content (% by weight) in the sulfonated aromatic polycarbonate oligomer.
スルホン化芳香族ポリカーボネートオリゴマーにおいて、スルホ基及び／またはその誘導体の含有量が低すぎると、スルホ基及び／またはその誘導体の効果が不十分であり、逆に多すぎてもスルホン化芳香族ポリカーボネートオリゴマーの製造が困難となり、また得られたスルホン化芳香族ポリカーボネートオリゴマーの熱可塑性樹脂への分散性が低下する場合がある。 In the sulfonated aromatic polycarbonate oligomer, if the content of the sulfo group and / or the derivative thereof is too low, the effect of the sulfo group and / or the derivative thereof is insufficient. In some cases, and the dispersibility of the obtained sulfonated aromatic polycarbonate oligomer in a thermoplastic resin may be reduced.
よって本発明のスルホン化芳香族ポリカーボネートオリゴマーにおける、スルホ基及び／またはその誘導体の含有量は、硫黄含有量換算で通常、０．００１〜２０重量％であり、中でも０．０１〜１０重量％、特に０．０５〜５重量％であることが好ましい。 Therefore, the content of the sulfo group and / or derivative thereof in the sulfonated aromatic polycarbonate oligomer of the present invention is usually 0.001 to 20% by weight in terms of sulfur content, and among them, 0.01 to 10% by weight, In particular, it is preferably 0.05 to 5% by weight.
次にスルホン化芳香族ポリカーボネートオリゴマーの製造方法について説明する。本発明のスルホン化芳香族ポリカーボネートオリゴマーの製造方法は任意であり、芳香族ポリカーボネート樹脂を、従来公知の任意のスルホン化方法によりスルホン化すればよい。 Next, a method for producing a sulfonated aromatic polycarbonate oligomer will be described. The production method of the sulfonated aromatic polycarbonate oligomer of the present invention is arbitrary, and the aromatic polycarbonate resin may be sulfonated by any conventionally known sulfonation method.
スルホン化反応としては、具体的には例えば、無水硫酸法、発煙硫酸法、クロルスルホン酸法、ポリアルキルベンゼンスルホン酸法等が挙げられる。中でもクロルスルホン酸法や、ポリアルキルベンゼンスルホン酸法は、比較的温和な条件下で反応させることができるので、芳香族ポリカーボネート樹脂等の原料の劣化や、不純物の混入を低減し易いので好ましい。 Specific examples of the sulfonation reaction include a sulfuric anhydride method, a fuming sulfuric acid method, a chlorosulfonic acid method, and a polyalkylbenzenesulfonic acid method. Among them, the chlorosulfonic acid method and the polyalkylbenzenesulfonic acid method are preferable because they can be reacted under relatively mild conditions, and it is easy to reduce deterioration of raw materials such as aromatic polycarbonate resin and contamination of impurities.
中でもポリアルキルベンゼンスルホン酸法は、環境負荷の多い、脂肪族系ハロゲン溶媒を大量使用する必要がない点や、廃酸の少ない点で、特に好ましい Among them, the polyalkylbenzene sulfonic acid method is particularly preferable because it has a large environmental burden, does not require the use of a large amount of an aliphatic halogen solvent, and has little waste acid.
更に本発明においては、上述の方法で芳香族ポリカーボネート樹脂をスルホン化してスルホン化芳香族ポリカーボネートオリゴマーとした後、中和反応や塩素化反応、還元反応、エステル化、アミド化反応、フリーデルクラフト反応、アルキル化等の反応により、スルホ基を種々のスルホ基誘導体に変換されていてもよい。尚、これらスルホ基誘導体の生成反応は、バッチ式操作又は連続式操作で行ってもよい。 Furthermore, in the present invention, the aromatic polycarbonate resin is sulfonated by the above-mentioned method to obtain a sulfonated aromatic polycarbonate oligomer, and then neutralization reaction, chlorination reaction, reduction reaction, esterification, amidation reaction, Friedel-Craft reaction The sulfo group may be converted into various sulfo group derivatives by a reaction such as alkylation. In addition, you may perform the production | generation reaction of these sulfo group derivatives by batch type operation or continuous type operation.
本発明の原料芳香族ポリカーボネート樹脂は適宜選択して決定すればよく、その製造方法も任意であり、従来公知の任意の方法を採用すればよい。 The raw material aromatic polycarbonate resin of the present invention may be appropriately selected and determined, and the production method thereof is arbitrary, and any conventionally known arbitrary method may be adopted.
本発明に用いる原料芳香族ポリカーボネート樹脂分子量は任意であるが、スルホン化により、本発明の数平均分子量１０００〜１００００のスルホン化芳香族ポリカーボネートオリゴマーを得るためには、数平均分子量（Ｍｎ）が小さいものを用いることが重要となる。 Although the raw material aromatic polycarbonate resin molecular weight used for this invention is arbitrary, in order to obtain the sulfonated aromatic polycarbonate oligomer of the number average molecular weight 1000-10000 of this invention by sulfonation, a number average molecular weight (Mn) is small. It is important to use things.
このＭｎは通常、１０００〜３００００である。Ｍｎが小さすぎると、得られるスルホン化芳香族ポリカーボネートオリゴマーの耐熱性が不十分となる傾向にあり、また熱可塑性樹脂に添加してもブリードアウトし易くやすくなる傾向にある。逆にＭｎが高すぎても溶媒中でのスルホン化反応の際に粘度が著しく高い為に製造が困難となり、また熱可塑性樹脂に添加しても分散性が不十分となる場合がある。 This Mn is usually 1000 to 30000. If Mn is too small, the resulting sulfonated aromatic polycarbonate oligomer tends to have insufficient heat resistance, and even when added to a thermoplastic resin, it tends to be easy to bleed out. On the other hand, if Mn is too high, the viscosity is remarkably high during the sulfonation reaction in the solvent, making it difficult to produce, and even when added to the thermoplastic resin, the dispersibility may be insufficient.
よって、本発明に用いる原料芳香族ポリカーボネート樹脂の数平均分子量は、中でも１５００〜２５０００、特に２０００〜１００００であることが好ましい。特に数平均分子量１００００以下のものを用いることによって、スルホン化反応時の分子量低下が抑制され、安定して製造することができ、更には熱可塑性樹脂に添加する場合、熱可塑性樹脂に悪影響を及ぼす可能性がある不純物や劣化物が少なくなる傾向にあるので、好ましい。 Therefore, the number average molecular weight of the raw material aromatic polycarbonate resin used in the present invention is preferably 1500 to 25000, particularly 2000 to 10,000. In particular, by using a polymer having a number average molecular weight of 10,000 or less, a decrease in molecular weight at the time of the sulfonation reaction can be suppressed and stable production can be achieved. Further, when added to a thermoplastic resin, the thermoplastic resin is adversely affected. This is preferable because there is a tendency to reduce possible impurities and deteriorated products.
尚、原料芳香族ポリカーボネート樹脂は、数平均分子量の異なる、２種類以上の芳香族ポリカーボネート樹脂を混合して用いてもよく、この際、数平均分子量が上述した好ましい範囲を外れるものをも含んでいてもよい。 In addition, the raw material aromatic polycarbonate resin may be used by mixing two or more types of aromatic polycarbonate resins having different number average molecular weights. In this case, the raw material aromatic polycarbonate resins include those whose number average molecular weights are outside the above-mentioned preferred ranges. May be.
原料芳香族ポリカーボネート樹脂は、具体的には例えば、芳香族ジヒドロキシ化合物とカーボネート前駆体とを、又はこれらに併せて少量のポリヒドロキシ化合物等を反応させてなる、直鎖または分岐の熱可塑性芳香族ポリカーボネート重合体、又は共重合体である。 Specifically, the raw material aromatic polycarbonate resin is, for example, a linear or branched thermoplastic aromatic obtained by reacting an aromatic dihydroxy compound and a carbonate precursor, or a small amount of a polyhydroxy compound in combination therewith. Polycarbonate polymer or copolymer.
本発明に用いる原料芳香族ポリカーボネート樹脂の製造方法は、特に限定されるものではなく、従来公知の任意の方法を採用できる。具体的には例えば、界面重合法、溶融エステル交換法、ピリジン法、環状カーボネート化合物の開環重合法、プレポリマーの固相エステル交換法等が挙げられる。 The manufacturing method of the raw material aromatic polycarbonate resin used for this invention is not specifically limited, A conventionally well-known arbitrary method is employable. Specific examples include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
これら原料芳香族ポリカーボネート樹脂の製造方法において使用される芳香族ジヒドロキシ化合物としては、具体的には例えば、２，２−ビス（４−ヒドロキシフェニル）プロパン（＝ビスフェノ−ルＡ）、２，２−ビス（３，５−ジブロモ−４−ヒドロキシフェニル）プロパン（＝テトラブロモビスフェノ−ルＡ）、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（４−ヒドロキシフェニル）オクタン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、１，１−ビス（３−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、２，２−ビス（３−ブロモ−４−ヒドロキシフェニル）プロパン、２，２−ビス（３，５−ジクロロ−４−ヒドロキシフェニル）プロパン、２，２−ビス（３−フェニル−４−ヒドロキシフェニル）プロパン、２，２−ビス（３−シクロヘキシル−４−ヒドロキシフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、ビス（４−ヒドロキシフェニル）ジフェニルメタン、２，２−ビス（４−ヒドロキシフェニル）−１，１，１−トリクロロプロパン、２，２−ビス（４−ヒドロキシフェニル）−１，１，１，３，３，３−ヘキサクロロプロパン、２，２−ビス（４−ヒドロキシフェニル）−１，１，１，３，３，３−ヘキサフルオロプロパン等のビス（ヒドロキシアリ−ル）アルカン類； Specific examples of the aromatic dihydroxy compound used in the production method of these raw material aromatic polycarbonate resins include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2- Bis (3,5-dibromo-4-hydroxyphenyl) propane (= tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2 -Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert- Butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2 Bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4- Hydroxyphenyl) -1,1,1-trichloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) ) -1,1,1,3,3,3-hexafluoropropane and other bis (hydroxyaryl) alkanes;
１，１−ビス（４−ヒドロキシフェニル）シクロペンタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン等のビス（ヒドロキシアリ−ル）シクロアルカン類； Bis such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Hydroxyaryl) cycloalkanes;
９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン等のカルド構造含有ビスフェノ−ル類；４，４’−ジヒドロキシジフェニルエ−テル、４，４’−ジヒドロキシ−３，３’−ジメチルジフェニルエ−テル等のジヒドロキシジアリールエーテル類； Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 4,4′-dihydroxydiphenyl ether; Dihydroxy diaryl ethers such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether;
４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジヒドロキシ−３，３’−ジメチルジフェニルスルフィド等のジヒドロキシジアリ−ルスルフィド類；４，４’−ジヒドロキシジフェニルスルホキシド、４，４’−ジヒドロキシ−３，３’−ジメチルジフェニルスルホキシド等のジヒドロキシジアリ−ルスルホキシド類； Dihydroxydiaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3 Dihydroxydiaryl sulfoxides such as 3,3'-dimethyldiphenyl sulfoxide;
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−３，３’−ジメチルジフェニルスルホン等のジヒドロキシジアリ−ルスルホン類；ハイドロキノン、レゾルシン、４，４’−ジヒドロキシジフェニル等が挙げられる。 Examples include dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like.
これらの中でもビス（４−ヒドロキシフェニル）アルカン類が好ましく、特に耐衝撃性の点から２，２−ビス（４−ヒドロキシフェニル）プロパン［＝ビスフェノ−ルＡ］が好ましい。これらの芳香族ジヒドロキシ化合物は、１種または任意の割合で２種以上を併用してもよい。 Among these, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is particularly preferable from the viewpoint of impact resistance. These aromatic dihydroxy compounds may be used alone or in combination of two or more in any proportion.
芳香族ジヒドロキシ化合物と反応させるカーボネート前駆体としては、カルボニルハライド、カーボネートエステル、ハロホルメート等が使用される。具体的には例えば、ホスゲン；ジフェニルカーボネート、ジトリルカーボネート等のジアリールカーボネート類； As the carbonate precursor to be reacted with the aromatic dihydroxy compound, carbonyl halide, carbonate ester, haloformate and the like are used. Specifically, for example, phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate;
ジメチルカーボネート、ジエチルカーボネート等のジアルキルカーボネート類；二価フェノールのジハロホルメート等が挙げられる。これらのカーボネート前駆体もまた、１種または任意の割合で２種以上を併用してもよい。 Examples include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; dihaloformates of dihydric phenols, and the like. These carbonate precursors may also be used alone or in combination of two or more in any proportion.
本発明に用いる原料芳香族ポリカーボネート樹脂の製造方法は、従来公知の任意の方法、具体的には例えば、界面重合法や溶融エステル交換法等を採用することが出来る。芳香族ポリカーボネート樹脂の製造方法のうち、まず界面重合法について説明する。 As a method for producing the raw material aromatic polycarbonate resin used in the present invention, any conventionally known method, specifically, for example, an interfacial polymerization method or a melt transesterification method can be employed. Of the methods for producing an aromatic polycarbonate resin, the interfacial polymerization method will be described first.
この製造方法における重合反応は、反応に不活性な有機溶媒、及びアルカリ水溶液の存在下で、通常ｐＨを９以上に保ち、芳香族ジヒドロキシ化合物と、必要に応じて分子量調整剤（末端停止剤）および芳香族ジヒドロキシ化合物の酸化防止のための酸化防止剤を用い、ホスゲンと反応させた後、第三級アミンまたは第四級アンモニウム塩等の重合触媒を添加し、界面重合を行うことによってポリカーボネートを得る。 In this production method, the polymerization reaction is usually carried out in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and the pH is usually kept at 9 or higher, with an aromatic dihydroxy compound and, if necessary, a molecular weight modifier (end stopper). And an antioxidant for preventing the oxidation of aromatic dihydroxy compounds, reacting with phosgene, adding a polymerization catalyst such as tertiary amine or quaternary ammonium salt, and conducting interfacial polymerization to produce polycarbonate. obtain.
分子量調節剤の添加はホスゲン化時から重合反応開始時までの間であれば特に限定されない。なお、反応温度は、例えば、０〜４０℃で、反応時間は、例えば、数分（例えば、１０分）〜数時間（例えば、６時間）である。 The addition of the molecular weight regulator is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction. In addition, reaction temperature is 0-40 degreeC, for example, and reaction time is several minutes (for example, 10 minutes)-several hours (for example, 6 hours), for example.
反応に不活性な有機溶媒としては、具体的には例えば、ジクロロメタン、１，２−ジクロロエタン、クロロホルム、モノクロロベンゼン、ジクロロベンゼン等の塩素化炭化水素等；ベンゼン、トルエン、キシレン等の芳香族炭化水素等；が挙げられる。またアルカリ水溶液に用いられるアルカリ化合物としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物が挙げられる。 Specific examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene. Etc .; Examples of the alkali compound used in the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
分子量調節剤としては、例えば一価のフェノール性水酸基を有する化合物が挙げられ、具体的には、ｍ−メチルフェノール、ｐ−メチルフェノ−ル、ｍ−プロピルフェノール、ｐ−プロピルフェノール、ｐ−ｔｅｒｔ−ブチルフェノール、及びｐ−長鎖アルキル置換フェノ−ル等が挙げられる。分子量調節剤の使用量は、芳香族ジヒドロキシ化合物１００モルに対して５０〜０．５モルであることが好ましく、中でも３０〜１モルであることが好ましい。 Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group. Specifically, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert- Examples include butylphenol and p-long chain alkyl-substituted phenol. The amount of the molecular weight regulator used is preferably 50 to 0.5 mol, more preferably 30 to 1 mol, per 100 mol of the aromatic dihydroxy compound.
重合触媒としてはトリメチルアミン、トリエチルアミン、トリブチルアミン、トリプロピルアミン、トリヘキシルアミン、ピリジン等の第三級アミン類；トリメチルベンジルアンモニウムクロライド、テトラメチルアンモニウムクロライド、トリエチルベンジルアンモニウムクロライド等の第四級アンモニウム塩等；が挙げられる。 Polymerization catalysts include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, pyridine; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. ;
次に、溶融エステル交換法について説明する。この製造方法における重合反応は、例えば炭酸ジエステルと芳香族ジヒドロキシ化合物とのエステル交換反応である。炭酸ジエステルとしては、具体的には例えばジメチルカーボネート、ジエチルカーボネート、ジ−ｔｅｒｔ−ブチルカーボネート等の炭酸ジアルキル化合物、ジフェニルカーボネート及びジトリルカーボネート等の置換ジフェニルカーボネート等が挙げられる。炭酸ジエステルとしては中でもジフェニルカーボネートや置換ジフェニルカーボネート等が好ましく、特にジフェニルカーボネートが好ましい。 Next, the melt transesterification method will be described. The polymerization reaction in this production method is, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound. Specific examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate, and substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate. Among them, diphenyl carbonate and substituted diphenyl carbonate are preferable as the carbonic acid diester, and diphenyl carbonate is particularly preferable.
また本発明に用いる芳香族ポリカーボネート樹脂は、その末端水酸基量が熱安定性、加水分解安定性、色調等に大きな影響を及ぼすので、従来公知の任意の方法によって適宜調整してもよい。溶融エステル交換反応においては、通常、炭酸ジエステルと芳香族ジヒドロキシ化合物との混合比率や、エステル交換反応時の減圧度を調整して、所望の分子量および末端水酸基量を調整した芳香族ポリカーボネートを得ることができる。 Further, the aromatic polycarbonate resin used in the present invention may be appropriately adjusted by any conventionally known method because the amount of terminal hydroxyl groups greatly affects the thermal stability, hydrolysis stability, color tone and the like. In the melt transesterification reaction, usually, the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound and the degree of pressure reduction during the transesterification reaction are adjusted to obtain an aromatic polycarbonate having the desired molecular weight and terminal hydroxyl group content adjusted. Can do.
通常、溶融エステル交換反応においては、芳香族ジヒドロキシ化合物１モルに対して、炭酸ジエステルを等モル量以上、中でも１．０１〜１．３０モル用いることが好ましい。更により積極的な調整方法として、反応時に別途、末端停止剤を添加する方法が挙げられる、この際の末端停止剤としては、一価フェノール類、一価カルボン酸類、炭酸ジエステル類が挙げられる。 Usually, in the melt transesterification reaction, it is preferable to use an equimolar amount or more, particularly 1.01-1.30 mol of the carbonic acid diester per 1 mol of the aromatic dihydroxy compound. As a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is added separately during the reaction. Examples of the terminal terminator in this case include monohydric phenols, monovalent carboxylic acids and carbonic acid diesters.
溶融エステル交換法によりポリカーボネートを製造する際には、通常、エステル交換触媒が使用される。エステル交換触媒は従来公知の任意のものを使用でき、中でも具体的には例えば、アルカリ金属化合物および／またはアルカリ土類金属化合物が好ましい。また補助的に、塩基性ホウ素化合物、塩基性リン化合物、塩基性アンモニウム化合物またはアミン系化合物などの塩基性化合物を併用してもよい。 When producing polycarbonate by the melt transesterification method, a transesterification catalyst is usually used. Any conventionally known transesterification catalyst can be used. Specifically, for example, alkali metal compounds and / or alkaline earth metal compounds are preferred. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination.
上記原料を用いたエステル交換反応は、通常、１００〜３２０℃の温度で反応を行い、最終的には２ｍｍＨｇ以下の減圧下、芳香族ヒドロキシ化合物等の副生成物を除去しながら溶融重縮合反応を行えばよい。 The transesterification reaction using the above raw materials is usually a reaction at a temperature of 100 to 320 ° C., and finally a melt polycondensation reaction while removing by-products such as aromatic hydroxy compounds under a reduced pressure of 2 mmHg or less. Can be done.
溶融重縮合は、バッチ式、連続式の何れの方法でも行うことができる。中でも、本発明に用いる芳香族ポリカーボネート樹脂や、本発明の樹脂組成物の安定性等を考慮すると、連続式で行うことが好ましい。溶融エステル交換法に用いる触媒失活剤としては、該エステル交換反応触媒を中和する化合物、例えばイオウ含有酸性化合物またはそれより形成される誘導体を使用することが好ましい。 The melt polycondensation can be performed by either a batch method or a continuous method. Among these, in consideration of the stability of the aromatic polycarbonate resin used in the present invention and the resin composition of the present invention, it is preferable to carry out in a continuous manner. As the catalyst deactivator used in the melt transesterification method, it is preferable to use a compound that neutralizes the transesterification reaction catalyst, such as a sulfur-containing acidic compound or a derivative formed therefrom.
この様な、触媒を中和する化合物の添加量は、該触媒が含有するアルカリ金属に対して０．５〜１０当量、中でも１〜５当量であることが好ましく、更にはポリカーボネートに対して、１〜１００ｐｐｍ、中でも１〜２０ｐｐｍであることが好ましい。 The addition amount of such a compound that neutralizes the catalyst is preferably 0.5 to 10 equivalents, more preferably 1 to 5 equivalents relative to the alkali metal contained in the catalyst, and further to the polycarbonate. It is preferably 1 to 100 ppm, particularly 1 to 20 ppm.
本発明に用いるポリカーボネート樹脂として、分岐ポリカーボネートを用いる際、その製造方法は特に制限はなく、従来公知の任意の製造方法を用いることが出来る。具体的には例えば、特開平８−２５９６８７号公報、特開平８−２４５７８２号公報等に記載の様に、溶融法（エステル交換法）により芳香族ジヒドロキシ化合物と炭酸のジエステルとを反応させる際、触媒の条件または製造条件を選択することにより、分岐剤を添加することなく、構造粘性指数が高く、加水分解安定性に優れた芳香族ポリカーボネート樹脂を得ることができる。 When a branched polycarbonate is used as the polycarbonate resin used in the present invention, the production method is not particularly limited, and any conventionally known production method can be used. Specifically, for example, as described in JP-A-8-259687, JP-A-8-245782, etc., when an aromatic dihydroxy compound and a carbonic diester are reacted by a melting method (transesterification method), By selecting the catalyst conditions or the production conditions, an aromatic polycarbonate resin having a high structural viscosity index and excellent hydrolysis stability can be obtained without adding a branching agent.
また他の方法として、上述のポリカーボネート樹脂の原料である、芳香族ジヒドロキシ化合物とカーボネート前駆体の他に、三官能以上の他官能性芳香族化合物を用い、ホスゲン法、又は溶融法（エステル交換法）にて、これらを共重合する方法が上げられる。 As another method, in addition to the aromatic dihydroxy compound and the carbonate precursor, which are the raw materials for the polycarbonate resin described above, a trifunctional or higher functional aromatic compound is used, the phosgene method, or the melting method (transesterification method). ), A method of copolymerizing them is raised.
三官能以上の多官能性芳香族化合物としては、具体的には例えば、フロログルシン、４，６−ジメチル−２，４，６−トリ（４−ヒドロキシフェニル）ヘプテン−２、４，６−ジメチル−２，４，６−トリ（４−ヒドロキシフェニル）ヘプタン、２，６−ジメチル−２，４，６−トリ（４−ヒドロキシフェニル）ヘプテン−３、１，３，５−トリ（４−ヒドロキシフェニル）べンゼン、１，１，１−トリ（４−ヒドロキシフェニル）エタン等のポリヒドロキシ化合物類； Specific examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl- 2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) ) Polyhydroxy compounds such as benzene, 1,1,1-tri (4-hydroxyphenyl) ethane;
３，３−ビス（４−ヒドロキシアリ−ル）オキシインド−ル（＝イサチンビスフェノ−ル）、５−クロロイサチン、５，７−ジクロロイサチン、５−ブロムイサチン等が挙げられる。中でも１，１，１−トリ（４−ヒドロキシフェニル）エタンが好ましい。 3,3-bis (4-hydroxyallyl) oxyindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred.
多官能性芳香族化合物は、前記芳香族ジヒドロキシ化合物の一部を置換して使用することができ、その使用量は芳香族ジヒドロキシ化合物に対して０．０１〜１０モル％、中でも０．１〜３モル％であることが好ましい。 The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is 0.01 to 10 mol%, particularly 0.1 to 0.1 mol, based on the aromatic dihydroxy compound. It is preferably 3 mol%.
溶融法（エステル交換法）によって得られた芳香族ポリカーボネート樹脂に含まれる分岐構造は、具体的には例えば、以下の一般式（２）〜（５）の構造が挙げられる。 Specific examples of the branched structure contained in the aromatic polycarbonate resin obtained by the melting method (transesterification method) include the following general formulas (2) to (5).
本発明に用いる芳香族ポリカーボネート樹脂の末端水酸基濃度は任意であり、適宜選択して決定すればよいが、通常、１０００ｐｐｍ以下であり、中でも８００ｐｐｍ以下、特に６００ｐｐｍ以下であることが好ましい。またその下限は、特にエステル交換法で製造する芳香族ポリカーボネート樹脂では１０ｐｐｍ以上、中でも３０ｐｐｍ以上、特に４０ｐｐｍ以上であることが好ましい。 The terminal hydroxyl group concentration of the aromatic polycarbonate resin used in the present invention is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, particularly preferably 600 ppm or less. Further, the lower limit is preferably 10 ppm or more, particularly 30 ppm or more, particularly 40 ppm or more in the case of an aromatic polycarbonate resin produced by a transesterification method.
末端水酸基濃度を１０ｐｐｍ以上とすることで、分子量低下を抑制し、樹脂組成物の機械的特性が、より向上する傾向にあるので好ましい。また末端基水酸基濃度を１０００ｐｐｍ以下にすることで、樹脂組成物の滞留熱安定性や色調がより向上する傾向にあるので好ましい。 It is preferable that the terminal hydroxyl group concentration be 10 ppm or more because molecular weight reduction is suppressed and the mechanical properties of the resin composition tend to be further improved. Moreover, it is preferable for the terminal group hydroxyl group concentration to be 1000 ppm or less because the residence heat stability and color tone of the resin composition tend to be further improved.
尚、末端水酸基濃度の単位は、芳香族ポリカーボネート樹脂重量に対する、末端水酸基の重量をｐｐｍで表示したものであり、測定方法は、四塩化チタン／酢酸法による比色定量（Ｍａｃｒｏｍｏｌ．Ｃｈｅｍ．８８ ２１５（１９６５）に記載の方法）である。 In addition, the unit of the terminal hydroxyl group density | concentration is what displayed the weight of the terminal hydroxyl group with respect to the weight of aromatic polycarbonate resin in ppm, and the measuring method is the colorimetric determination (Macromol. Chem. 88 215) by a titanium tetrachloride / acetic acid method. (Method of (1965)).
更に本発明に用いる原料芳香族ポリカーボネート樹脂は、いわゆるバージン原料だけでなく、使用済みの製品から再生された芳香族ポリカーボネート樹脂、いわゆるマテリアルリサイクルされた芳香族ポリカーボネート樹脂を使用してもよい。 Furthermore, as the raw material aromatic polycarbonate resin used in the present invention, not only a so-called virgin raw material but also an aromatic polycarbonate resin regenerated from a used product, a so-called material recycled aromatic polycarbonate resin may be used.
使用済みの製品としては、光学ディスク等の光記録媒体、導光板、自動車窓ガラス・自動車ヘッドランプレンズ・風防等の車両透明部材、水ボトル等の容器、メガネレンズ、防音壁・ガラス窓・波板等の建築部材等が好ましく挙げられる。 Used products include optical recording media such as optical disks, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields, and other vehicle transparent members, water bottle containers, glasses lenses, soundproof walls, glass windows, waves, etc. A building member such as a plate is preferred.
また製品の不適合品やスプルー、ランナー等から得られた粉砕品等、そしてこれらを溶融して得られるペレット等を用いてもよい。本発明に用いる原料芳香族ポリカーボネート樹脂において、この様な再生芳香族ポリカーボネート樹脂の含有量は８０重量％以下、中でも５０重量％以下であることが好ましい。 Further, non-conforming products, pulverized products obtained from sprues, runners, etc., and pellets obtained by melting these may be used. In the raw material aromatic polycarbonate resin used in the present invention, the content of such a regenerated aromatic polycarbonate resin is preferably 80% by weight or less, more preferably 50% by weight or less.
（２）熱可塑性樹脂
本発明に用いる熱可塑性樹脂は、本発明のスルホン化芳香族ポリカーボネートオリゴマーを含有することで、難燃性や帯電防止性等が改善されれば、特に制限はない。
(2) Thermoplastic resin The thermoplastic resin used in the present invention is not particularly limited as long as flame retardancy and antistatic properties are improved by containing the sulfonated aromatic polycarbonate oligomer of the present invention.
本発明に用いる熱可塑性樹脂としては、具体的には例えば、ポリカーボネート樹脂（ＰＣ）、シロキサンーポリカーボネート共重合体（ＳｉＰＣ）、ポリアリレート樹脂（ＰＡＲ）、アクリロニトリルーブタジエンースチレン共重合体（ＡＢＳ）、アクリロニトリルースチレン共重合体（ＡＳ）、ポリスチレン（ＰＳ）、ポリ塩化ビニル（ＰＶＣ）、ポリフェニレンエーテル（ＰＰＥ）、ポリエチレンテレフタラート（ＰＥＴ）、ポリブタジエンテレフタラート（ＰＢＴ）、熱可塑性エラストマー（ＴＰＥ）、ポリスルホン（ＰＳＦ）、ポリアミド（ＰＡ）、ポリ乳酸（ＰＬＡ）、ポリカプロラクトン（ＰＣＬ）等が挙げられる。 Specific examples of the thermoplastic resin used in the present invention include polycarbonate resin (PC), siloxane-polycarbonate copolymer (SiPC), polyarylate resin (PAR), and acrylonitrile-butadiene-styrene copolymer (ABS). , Acrylonitrile-styrene copolymer (AS), polystyrene (PS), polyvinyl chloride (PVC), polyphenylene ether (PPE), polyethylene terephthalate (PET), polybutadiene terephthalate (PBT), thermoplastic elastomer (TPE), Examples include polysulfone (PSF), polyamide (PA), polylactic acid (PLA), and polycaprolactone (PCL).
また本発明に用いる熱可塑性樹脂は、これらを単独、又は２種以上を任意の割合で併用した混合物（アロイ）であってもよい。またその平均分子量は特に制限はなく、その用途に応じて適宜選択して決定すればよい。そして流動性を調整する目的などから、２種類以上の平均分子量の異なる熱可塑性樹脂を併用してもよい。 Moreover, the thermoplastic resin used for this invention may be the mixture (alloy) which used these individually or in combination of 2 or more types in arbitrary ratios. The average molecular weight is not particularly limited, and may be appropriately selected and determined according to the use. For the purpose of adjusting fluidity, two or more types of thermoplastic resins having different average molecular weights may be used in combination.
本発明に用いる熱可塑性樹脂としては、中でもＰＣ、ＰＣ／ＡＢＳアロイ、ＰＣ／ＰＥＴアロイ、ＰＣ／ＰＢＴアロイ、ＰＣ／ＰＣＬアロイ、ＰＣ／ＳｉＰＣアロイ、ＰＢＴ、ＰＢＴ／ＰＥＴアロイ、ＳｉＰＣ、ＰＡＲ、ＰＰＥ、ＰＰＥ／ＰＳが好ましい。更には、本発明のスルホン化芳香族ポリカーボネートオリゴマーとの相溶性や効果が顕著なことから、ＰＣ、ＰＣ／ＡＢＳアロイ、ＰＣ／ＰＢＴアロイ、ＰＣ／ＰＥＴアロイ、ＰＣ／ＰＣＬアロイが好ましく、特にＰＣ、ＰＣ／ＡＢＳアロイが好ましい。 Among the thermoplastic resins used in the present invention, PC, PC / ABS alloy, PC / PET alloy, PC / PBT alloy, PC / PCL alloy, PC / SiPC alloy, PBT, PBT / PET alloy, SiPC, PAR, PPE PPE / PS is preferred. Furthermore, PC, PC / ABS alloy, PC / PBT alloy, PC / PET alloy, and PC / PCL alloy are preferable because the compatibility and effects with the sulfonated aromatic polycarbonate oligomer of the present invention are remarkable. PC / ABS alloys are preferred.
以下に、本発明に用いる熱可塑性樹脂として、ポリカーボネート樹脂を例にして説明する。本発明に用いるポリカーボネート樹脂としては、従来公知の任意のポリカーボネート樹脂を使用できるが、中でも芳香族ポリカーボネート樹脂が好ましい。 Hereinafter, a polycarbonate resin will be described as an example of the thermoplastic resin used in the present invention. As the polycarbonate resin used in the present invention, any conventionally known polycarbonate resin can be used, and among them, an aromatic polycarbonate resin is preferable.
本発明に用いる芳香族ポリカーボネート樹脂の分子量は任意であり、所望の用途に応じて適宜選択して決定すればよい。一般的には、溶液粘度から換算した粘度平均分子量で１００００〜４００００のものが好ましい。粘度平均分子量が１００００以上であると機械的強度が向上する傾向にある。一方、粘度平均分子量を４００００以下とすることで、流動性低下が抑制される傾向にあるので、成型加工性が容易となるので好ましい。 The molecular weight of the aromatic polycarbonate resin used in the present invention is arbitrary, and may be appropriately selected and determined according to the desired application. Generally, a viscosity average molecular weight converted from solution viscosity is preferably 10,000 to 40,000. When the viscosity average molecular weight is 10,000 or more, the mechanical strength tends to be improved. On the other hand, it is preferable that the viscosity average molecular weight is 40,000 or less, since a decrease in fluidity tends to be suppressed, so that moldability becomes easy.
粘度平均分子量は中でも１６０００〜４００００、特に１８０００〜３００００であることが好ましい。また粘度平均分子量の異なる２種類以上の芳香族ポリカーボネート樹脂を混合して、混合物の粘度平均分子量がこの様な数値範囲のものとしてもよく、この際、上述した様な好ましい粘度平均分子量範囲外のものを用いてもよい。 The viscosity average molecular weight is preferably 16,000 to 40,000, particularly preferably 18,000 to 30,000. Further, two or more types of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed, and the viscosity average molecular weight of the mixture may be in such a numerical value range. A thing may be used.
本発明に用いる芳香族ポリカーボネート樹脂は、ポリカーボネート樹脂単独（ポリカーボネート樹脂単独とは、ポリカーボネート樹脂の１種のみを含む態様に限定されず、例えば、モノマー組成や分子量が互いに異なる複数種のポリカーボネート樹脂を含む態様を含む意味で用いる。）や、ポリカーボネート樹脂と他の熱可塑性樹脂とのアロイ（混合物）の他、例えば、シロキサン構造を有するオリゴマーまたはポリマーとの共重合体等の、ポリカーボネート樹脂を主体とする共重合体をも含むものである。 The aromatic polycarbonate resin used in the present invention is not limited to a polycarbonate resin alone (a polycarbonate resin alone is an embodiment containing only one type of polycarbonate resin, and includes, for example, a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. In addition to alloys (mixtures) of polycarbonate resins and other thermoplastic resins, for example, polycarbonate resins such as oligomers or polymers having a siloxane structure are mainly used. A copolymer is also included.
更に、本発明に用いる芳香族ポリカーボネート樹脂は、スルホン化芳香族ポリカーボネートオリゴマーの原料芳香族ポリカーボネート樹脂と同様、バージン原料だけでなく、いわゆるマテリアルリサイクルされた芳香族ポリカーボネート樹脂を使用してもよい。 Further, as the aromatic polycarbonate resin used in the present invention, not only the virgin raw material but also a so-called material recycled aromatic polycarbonate resin may be used, like the raw material aromatic polycarbonate resin of the sulfonated aromatic polycarbonate oligomer.
マテリアルリサイクルされた芳香族ポリカーボネート樹脂としては、上述した、原料芳香族ポリカーボネート樹脂におけるものと同様であり、また製品の不適合品等から再生し得られたものも用いることが出来る。そして再生された芳香族ポリカーボネート樹脂は、本発明に用いる芳香族ポリカーボネート樹脂のうち８０重量％以下、中でも５０重量％以下であることが好ましい。 The material recycled aromatic polycarbonate resin is the same as that in the above-mentioned raw material aromatic polycarbonate resin, and can also be used that is regenerated from a non-conforming product. The regenerated aromatic polycarbonate resin is preferably 80% by weight or less, more preferably 50% by weight or less of the aromatic polycarbonate resin used in the present invention.
本発明の熱可塑性樹脂組成物における、スルホン化芳香族ポリカーボネートオリゴマーの含有量は任意であり、その用途に応じて適宜選択して決定すればよい。通常、芳香族ポリカーボネート樹脂組成物中におけるスルホン化芳香族ポリカーボネートオリゴマーの含有量は、芳香族ポリカーボネート樹脂１００重量部に対して０．０００１〜３０重量部であり、中でも０．００１〜２０重量部、更には０．０１〜１５重量部、特に０．１〜１０重量部であることが好ましい。 The content of the sulfonated aromatic polycarbonate oligomer in the thermoplastic resin composition of the present invention is arbitrary and may be appropriately selected and determined according to the use. Usually, the content of the sulfonated aromatic polycarbonate oligomer in the aromatic polycarbonate resin composition is 0.0001 to 30 parts by weight, particularly 0.001 to 20 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin. Further, it is preferably 0.01 to 15 parts by weight, particularly preferably 0.1 to 10 parts by weight.
スルホン化芳香族ポリカーボネートオリゴマーの含有量が少なすぎると芳香族ポリカーボネート樹脂等の熱可塑性樹脂に対して難燃性、帯電防止性等の機能を付与が不十分となる。効果的に機能を付与させる為には、スルホン化芳香族ポリカーボネートオリゴマーのスルホ基（誘導体）の導入率を極端に大きくしなければならず、このようなスルホン化芳香族ポリカーボネートオリゴマーは製造上、品質上現実的ではない。逆に多すぎても、熱可塑性樹脂組成物の流動性等の機械的性質や耐熱性等の諸物性が低下する場合がある。 When the content of the sulfonated aromatic polycarbonate oligomer is too small, the functions such as flame retardancy and antistatic property are insufficiently imparted to a thermoplastic resin such as an aromatic polycarbonate resin. In order to effectively impart a function, the introduction rate of the sulfo group (derivative) of the sulfonated aromatic polycarbonate oligomer must be extremely increased. Not realistic. On the other hand, if the amount is too large, mechanical properties such as fluidity of the thermoplastic resin composition and various physical properties such as heat resistance may deteriorate.
本発明の熱可塑性樹脂組成物においては、上述した、本発明のスルホン化芳香族ポリカーボネートオリゴマーの他に、従来公知の任意の各種添加剤を含有してもよい。従来公知の各種添加剤としては、熱安定剤、酸化防止剤、離型剤、紫外線吸収剤、染顔料、難燃剤、滴下防止剤、帯電防止剤、防曇剤、滑剤・アンチブロッキング剤、流動性改良剤、可塑剤、分散剤、防菌剤、強化剤、フィラー等が挙げられ、これらから適宜選択して決定し、使用すればよく、これらは２種以上を併用してもよい。 The thermoplastic resin composition of the present invention may contain any conventionally known various additives in addition to the above-described sulfonated aromatic polycarbonate oligomer of the present invention. Conventionally known various additives include heat stabilizers, antioxidants, mold release agents, ultraviolet absorbers, dyes and pigments, flame retardants, anti-dripping agents, antistatic agents, antifogging agents, lubricants and antiblocking agents, and flow. Examples thereof include property improvers, plasticizers, dispersants, antibacterial agents, reinforcing agents, fillers and the like, which may be appropriately selected and determined from these, and these may be used in combination of two or more.
本発明の熱可塑性樹脂組成物の製造方法は特に制限はなく、従来公知の任意の、樹脂組成物の製造方法を採用することが出来る。 The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and any conventionally known method for producing a resin composition can be employed.
具体的には例えば、上述した熱可塑性樹脂、及びスルホン化ポリカーボネートオリゴマー成分、更に必要に応じてその他の添加成分を、タンブラーやヘンシェルミキサ−などの各種混合機を用い予め混合した後、バンバリーミキサー、ロール、ブラベンダー、単軸混練押出機、二軸混練押出機、ニーダーなどで溶融混練する方法が挙げられる。 Specifically, for example, after previously mixing the thermoplastic resin described above and the sulfonated polycarbonate oligomer component, and other additive components as necessary, using various mixers such as a tumbler and a Henschel mixer, a Banbury mixer, Examples thereof include a melt kneading method using a roll, a brabender, a single screw kneading extruder, a twin screw kneading extruder, a kneader, and the like.
また各成分を予め混合せずに、又は一部の成分のみ予め混合して、フィーダーを用いて押出機に供給し溶融混練して、樹脂組成物を製造してもよい。更には、一部の成分を予め混合し押出機に供給して溶融混練することで得られる樹脂組成物をマスターバッチとし、再度、他の成分と混合し溶融混練することによって樹脂組成物を製造することもできる。 Alternatively, the resin composition may be produced by mixing each component in advance, or by mixing only a part of the components in advance, supplying the mixture to an extruder using a feeder, and melt-kneading the mixture. Furthermore, a resin composition obtained by mixing some components in advance, supplying them to an extruder and melt-kneading is used as a master batch, and the resin composition is manufactured by mixing again with other components and melt-kneading. You can also
また、本発明におけるスルホン化芳香族ポリカーボネートオリゴマーは、単独又は熱可塑性樹脂と混合して、有機溶剤等の溶媒に溶解して使用することもできる。 In addition, the sulfonated aromatic polycarbonate oligomer in the present invention can be used alone or mixed with a thermoplastic resin and dissolved in a solvent such as an organic solvent.
以下に実施例を示し、本発明を更に具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。尚、「部」は「重量部」を示す。またスルホン化芳香族ポリカーボネートオリゴマーを「ＳＰＣ」と略記することがある。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. “Part” means “part by weight”. The sulfonated aromatic polycarbonate oligomer may be abbreviated as “SPC”.
実施例１ ＳＰＣ１
原料芳香族ポリカーボネート樹脂として、数平均分子量３６００のビスフェノールＡ型芳香族ポリカーボネート樹脂オリゴマーを用い、１，２−ジクロロエタン溶媒中、スルホン化剤にクロルスルホン酸を用い（クロルスルホン酸法）、スルホン基を導入し、更に中和反応を行い、ナトリウム塩型（−ＳＯ３Ｎａ）のスルホン化芳香族ポリカーボネートオリゴマーを得た。結果を表１に示す。
Example 1 SPC1
As a raw material aromatic polycarbonate resin, a bisphenol A type aromatic polycarbonate resin oligomer having a number average molecular weight of 3600 is used, and in a 1,2-dichloroethane solvent, chlorosulfonic acid is used as a sulfonating agent (chlorosulfonic acid method), and a sulfone group is formed. Then, a neutralization reaction was further performed to obtain a sulfonated aromatic polycarbonate oligomer of a sodium salt type (—SO 3 Na). The results are shown in Table 1.
実施例２ ＳＰＣ２
スルホン化反応をポリアルキルベンゼンスルホン酸法とした他は実施例１と同様にして、スルホン化芳香族ポリカーボネートオリゴマーを得た。尚、ポリアルキルベンゼンスルホン酸法は、特許２８８４１８９号公報に従い、１，２−ジクロロベンゼン溶媒中、スルホン化剤に１，３，５―トリメチルベンゼン−２−スルホン酸を用いて行った。結果を表１に示す。
Example 2 SPC2
A sulfonated aromatic polycarbonate oligomer was obtained in the same manner as in Example 1 except that the sulfonation reaction was changed to the polyalkylbenzenesulfonic acid method. The polyalkylbenzenesulfonic acid method was carried out according to Japanese Patent No. 2884189 using 1,3,5-trimethylbenzene-2-sulfonic acid as a sulfonating agent in a 1,2-dichlorobenzene solvent. The results are shown in Table 1.
実施例３ ＳＰＣ３
原料芳香族ポリカーボネート樹脂として数平均分子量２０４００のビスフェノールＡ型芳香族ポリカーボネート樹脂を用いた他は、実施例１と同様にしてスルホン化芳香族ポリカーボネートオリゴマーを得た。結果を表１に示す。
Example 3 SPC3
A sulfonated aromatic polycarbonate oligomer was obtained in the same manner as in Example 1 except that a bisphenol A type aromatic polycarbonate resin having a number average molecular weight of 20400 was used as the raw material aromatic polycarbonate resin. The results are shown in Table 1.
実施例４ ＳＰＣ４
原料に、数平均分子量２０４００のビスフェノールＡ型芳香族ポリカーボネート樹脂を用い、ポリアルキルベンゼンスルホン酸法によってスルホン化反応を行った以外は、実施例１と同様にして表１に記載のスルホン化芳香族ポリカーボネートオリゴマーを得た。結果を表１に示す。
Example 4 SPC4
The sulfonated aromatic polycarbonate described in Table 1 was used in the same manner as in Example 1 except that a bisphenol A type aromatic polycarbonate resin having a number average molecular weight of 20400 was used as a raw material and the sulfonation reaction was performed by the polyalkylbenzenesulfonic acid method. An oligomer was obtained. The results are shown in Table 1.
数平均分子量（Ｍｎ）
ＧＰＣ（Ｓｈｏｄｅｘ ＧＰＣ ｓｙｓｔｅｍ ２１、カラム温度４０℃）を用い、ポリスチレン換算分子量（数平均分子量：Ｍｎ）として求めた。展開溶媒には、クロロホルムを用いた。
Number average molecular weight (Mn)
Using GPC (Shodex GPC system 21, column temperature 40 ° C.), the molecular weight was calculated as polystyrene-reduced molecular weight (number average molecular weight: Mn). Chloroform was used as the developing solvent.
分子量低下率
スルホン化反応による分子量低下率（％）は、［分子量低下率（％）＝（スルホン化反応前のＭｎ−スルホン化反応後のＭｎ）／スルホン化反応前のＭｎ］の式にて算出した。尚、分子量低下率が小さい方が、反応によって生じる分子量低下が小さいことを意味し、好ましい。
Molecular weight reduction rate The molecular weight reduction rate (%) due to the sulfonation reaction is expressed by the formula: [Molecular weight reduction rate (%) = (Mn before the sulfonation reaction-Mn after the sulfonation reaction) / Mn before the sulfonation reaction]. Calculated. In addition, the one where a molecular weight fall rate is small means that the molecular weight fall produced by reaction is small, and preferable.
硫黄含有量
試料燃焼装置（ＤＩＡ ＩＮＳＴＲＵＭＥＮＴＳ ＱＦ−０２）及びイオンクロマトグラフシステム（ＤＩＯＮＥＸ ＩＣＳ−９０）を用いて、燃焼イオンクロマト法により、硫黄含有量（ｗｔ％）を求めた。
The sulfur content (wt%) was determined by combustion ion chromatography using a sulfur content sample combustion apparatus (DIA INSTRUMENTS QF-02) and an ion chromatograph system (DIONEX ICS-90).
実施例５〜８及び比較例１〜２
表２に記した各成分を、表３に記した割合（重量比）で配合し、タンブラーにて２０分混合後、１ベントを備えた田辺精機社製の４０ｍｍ単軸押出機（ＶＳ−４０）に供給し、３００℃で混練、ストランド状に押出された溶融樹脂を水槽にて急冷し、ペレタイザーを用いてペレット化した。得られたペレットを１２０℃、５時間乾燥後、日本製鋼所製のＪ５０−ＥＰ型射出成形機を用いて、シリンダー温度３００℃、金型温度８０℃、成形サイクル３０秒の条件で３ｍｍ厚の平板を成形した。尚、実施例では、スルホン化芳香族ポリカーボネートオリゴマーを、比較例には、低分子型のスルホン酸化合物を添加している。
Examples 5-8 and Comparative Examples 1-2
Each component shown in Table 2 was blended in the ratio (weight ratio) shown in Table 3, mixed for 20 minutes with a tumbler, and then a 40 mm single screw extruder (VS-40) manufactured by Tanabe Seiki Co., Ltd. equipped with 1 vent. The molten resin that was kneaded at 300 ° C. and extruded into a strand shape was quenched in a water bath and pelletized using a pelletizer. The obtained pellets were dried at 120 ° C. for 5 hours, and then using a J50-EP type injection molding machine manufactured by Nippon Steel Works, the cylinder temperature was 300 ° C., the mold temperature was 80 ° C., and the molding cycle was 30 seconds. A flat plate was formed. In the examples, a sulfonated aromatic polycarbonate oligomer is added, and in the comparative example, a low molecular weight sulfonic acid compound is added.
スルホ基（誘導体）含有率
スルホン化芳香族ポリカーボネートオリゴマーの硫黄含有量及び低分子スルホン化合物の分子量と添加量の関係から熱可塑性樹脂中のスルホン化合物（−ＳＯ３Ｎａ基）の割合（重量％）を算出した。尚、各元素の原子量は、Ｓ＝３２．０７、Ｏ＝１６．００、Ｎａ＝２２．９９、Ｃ＝１２．０１、Ｈ＝１．００８として計算した。）
Sulfo group (derivative) content rate Sulfur compound (—SO 3 Na group) ratio (wt%) in thermoplastic resin from relationship between sulfur content of sulfonated aromatic polycarbonate oligomer and molecular weight and addition amount of low molecular sulfone compound Was calculated. In addition, the atomic weight of each element was calculated as S = 32.07, O = 16.00, Na = 29.99, C = 12.01, and H = 1.008. )
透明性評価
ＪＩＳ Ｋ−７１０５に準拠し、厚み３ｍｍのプレート状成形品を試験片とし、日本電色工業社製のＮＤＨ−２０００型ヘイズメーターで測定した。Ｈａｚｅ（ヘイズ）は、樹脂の濁度の尺度として用いられる値であり、数値が小さい程、透明性が高いことを示す。
Transparency Evaluation In accordance with JIS K-7105, a plate-shaped molded product having a thickness of 3 mm was used as a test piece, and measured with an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. Haze is a value used as a measure of the turbidity of a resin, and the smaller the value, the higher the transparency.
表１にから明らかな通り、本発明の実施例１〜４では、数平均分子量１０００〜１００００のスルホン化芳香族ポリカーボネートオリゴマーが提供できる。更に実施例１、２と、３、４とを比較すると、原料芳香族ポリカーボネート樹脂の数平均分子量が１０００〜１００００であると、分子量低下率が抑制されることが判る。 As apparent from Table 1, in Examples 1 to 4 of the present invention, a sulfonated aromatic polycarbonate oligomer having a number average molecular weight of 1000 to 10,000 can be provided. Further, when Examples 1, 2, and 3, 4 are compared, it can be seen that when the number average molecular weight of the raw aromatic polycarbonate resin is 1000 to 10,000, the molecular weight reduction rate is suppressed.
また表３の結果から明らかな通り、本発明のスルホン化芳香族ポリカーボネートオリゴマーを添加した熱可塑性樹脂組成物（実施例５〜８）は、従来用いられる低分子型スルホン酸化合物を添加したもの（比較例１、２）と比べて透明性に優れたものであることが判る。このことは、スルホ基（誘導体）含有率と、Ｈａｚｅの関係からも明らかである。 Moreover, as is clear from the results in Table 3, the thermoplastic resin compositions (Examples 5 to 8) to which the sulfonated aromatic polycarbonate oligomer of the present invention was added were those to which a conventionally used low molecular weight sulfonic acid compound was added ( It turns out that it is excellent in transparency compared with Comparative Examples 1 and 2. This is also clear from the relationship between the sulfo group (derivative) content and Haze.
Claims (6)
−ＳＯ３（Ｍ）ｎ （２）
（式中、Ｍはアルカリ金属、アルカリ土類金属、オニウム化合物からなる群より選ばれる少なくとも１種を示し、ｎは０．５又は１を示す。） The sulfonated aromatic polycarbonate oligomer according to claim 1, which has a sulfo group derivative represented by the following general formula (2).
-SO 3 (M) n (2 )
(In the formula, M represents at least one selected from the group consisting of alkali metals, alkaline earth metals, and onium compounds, and n represents 0.5 or 1.)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009060986A1 (en) * | 2007-11-08 | 2009-05-14 | Teijin Chemicals Ltd. | Resin composition |
| JP2011105931A (en) * | 2009-10-22 | 2011-06-02 | Mitsubishi Chemicals Corp | Polycarbonate resin |
| WO2023100260A1 (en) * | 2021-11-30 | 2023-06-08 | 日清紡ホールディングス株式会社 | Marine biodegradable polymer compound, marine biodegradation promoter, and marine biodegradable resin composition |
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| JPS6270420A (en) * | 1985-08-22 | 1987-03-31 | ゼネラル・エレクトリツク・カンパニイ | Manufacture of sulfonated polycarbonate and use as flame retardant |
| JP2007063514A (en) * | 2005-09-02 | 2007-03-15 | Sony Corp | Method for sulfonating aromatic compound and sulfonic acid compound |
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| JPS6270420A (en) * | 1985-08-22 | 1987-03-31 | ゼネラル・エレクトリツク・カンパニイ | Manufacture of sulfonated polycarbonate and use as flame retardant |
| JP2007063514A (en) * | 2005-09-02 | 2007-03-15 | Sony Corp | Method for sulfonating aromatic compound and sulfonic acid compound |
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| WO2009060986A1 (en) * | 2007-11-08 | 2009-05-14 | Teijin Chemicals Ltd. | Resin composition |
| JP5436219B2 (en) * | 2007-11-08 | 2014-03-05 | 帝人株式会社 | Resin composition |
| JP2011105931A (en) * | 2009-10-22 | 2011-06-02 | Mitsubishi Chemicals Corp | Polycarbonate resin |
| WO2023100260A1 (en) * | 2021-11-30 | 2023-06-08 | 日清紡ホールディングス株式会社 | Marine biodegradable polymer compound, marine biodegradation promoter, and marine biodegradable resin composition |
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