JP2012236956A - Branched polycarbonate resin - Google Patents
Branched polycarbonate resin Download PDFInfo
- Publication number
- JP2012236956A JP2012236956A JP2011108591A JP2011108591A JP2012236956A JP 2012236956 A JP2012236956 A JP 2012236956A JP 2011108591 A JP2011108591 A JP 2011108591A JP 2011108591 A JP2011108591 A JP 2011108591A JP 2012236956 A JP2012236956 A JP 2012236956A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- bis
- hydroxyphenyl
- tris
- weight
- 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
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 47
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 47
- 239000006085 branching agent Substances 0.000 claims abstract description 20
- -1 hydroxy-3,5-dimethylphenyl Chemical group 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 12
- 230000004580 weight loss Effects 0.000 claims description 11
- 239000007983 Tris buffer Substances 0.000 claims description 8
- 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 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- FIGVNZUQNIUGPD-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxy-3-methylphenyl)ethyl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C(C)(C=2C=C(C)C(O)=CC=2)C=2C=C(C)C(O)=CC=2)=C1 FIGVNZUQNIUGPD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 abstract description 21
- 229960002479 isosorbide Drugs 0.000 abstract description 21
- 239000002028 Biomass Substances 0.000 abstract description 11
- 229920002472 Starch Polymers 0.000 abstract description 5
- 235000019698 starch Nutrition 0.000 abstract description 5
- 239000008107 starch Substances 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000004417 polycarbonate Substances 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
- 229920000515 polycarbonate Polymers 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 150000004650 carbonic acid diesters Chemical class 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002685 polymerization catalyst Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- KLDXJTOLSGUMSJ-UNTFVMJOSA-N (3s,3ar,6s,6ar)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-UNTFVMJOSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- CUAWUNQAIYJWQT-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxy-3,5-dimethylphenyl)ethyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C=2C=C(C)C(O)=C(C)C=2)C=2C=C(C)C(O)=C(C)C=2)=C1 CUAWUNQAIYJWQT-UHFFFAOYSA-N 0.000 description 2
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 2
- UJCYBTZHUJWCMB-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-4-propan-2-ylcyclohexyl]phenol Chemical compound C1CC(C(C)C)CCC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UJCYBTZHUJWCMB-UHFFFAOYSA-N 0.000 description 2
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical group 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229960002920 sorbitol Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 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 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical class CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- XKMCVHMWMWTINX-UHFFFAOYSA-N (2,3,4-trichlorophenyl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC=C(Cl)C(Cl)=C1Cl XKMCVHMWMWTINX-UHFFFAOYSA-N 0.000 description 1
- OKJFKPFBSPZTAH-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O OKJFKPFBSPZTAH-UHFFFAOYSA-N 0.000 description 1
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- GPFJHNSSBHPYJK-UHFFFAOYSA-N (3-methylphenyl) hydrogen carbonate Chemical compound CC1=CC=CC(OC(O)=O)=C1 GPFJHNSSBHPYJK-UHFFFAOYSA-N 0.000 description 1
- RKIMETXDACNTIE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorocyclohexane Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F RKIMETXDACNTIE-UHFFFAOYSA-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
- PHJMLWHPHSYYQI-UHFFFAOYSA-N 1,1-bis(2,6-ditert-butyl-4-ethylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)CC)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)CC)C(C)(C)C PHJMLWHPHSYYQI-UHFFFAOYSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- OSZQBLPOQBBXQS-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-(2,4-ditert-butylphenoxy)-5h-benzo[d][1,3,2]benzodioxaphosphocine Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OC2=C(C(C)(C)C)C=C(C(C)(C)C)C=C2CC(C=C(C=C2C(C)(C)C)C(C)(C)C)=C2O1 OSZQBLPOQBBXQS-UHFFFAOYSA-N 0.000 description 1
- MRMCMJOXMLGUFT-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-(2-tert-butyl-4-methylphenoxy)-5h-benzo[d][1,3,2]benzodioxaphosphocine Chemical compound CC(C)(C)C1=CC(C)=CC=C1OP1OC2=C(C(C)(C)C)C=C(C(C)(C)C)C=C2CC(C=C(C=C2C(C)(C)C)C(C)(C)C)=C2O1 MRMCMJOXMLGUFT-UHFFFAOYSA-N 0.000 description 1
- 229940084778 1,4-sorbitan Drugs 0.000 description 1
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- SMIZARYCGYRDGF-UHFFFAOYSA-N phenyl dipropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC1=CC=CC=C1 SMIZARYCGYRDGF-UHFFFAOYSA-N 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
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- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
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- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- QFGXDXGDZKTYFD-UHFFFAOYSA-N tris[2,3-di(propan-2-yl)phenyl] phosphite Chemical compound CC(C)C1=CC=CC(OP(OC=2C(=C(C(C)C)C=CC=2)C(C)C)OC=2C(=C(C(C)C)C=CC=2)C(C)C)=C1C(C)C QFGXDXGDZKTYFD-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、バイオマス資源であるデンプンなどの糖質から誘導することができる構成単位を含有するポリカーボネート樹脂を含有し、高荷重下での流動性が改良された分岐化ポリカーボネート樹脂に関する。 The present invention relates to a branched polycarbonate resin containing a polycarbonate resin containing a structural unit that can be derived from a carbohydrate such as starch, which is a biomass resource, and having improved fluidity under high load.
近年、石油資源の枯渇の懸念や、地球温暖化を引き起こす空気中の二酸化炭素の増加の問題から、原料を石油に依存せず、また燃焼させても二酸化炭素を増加させないカーボンニュートラルが成り立つバイオマス資源が大きく注目を集めるようになり、ポリマーの分野においても、バイオマス資源から生産されるバイオマスプラスチックが盛んに開発されている。 In recent years, due to concerns about the depletion of petroleum resources and the problem of increased carbon dioxide in the air that causes global warming, biomass resources that do not depend on petroleum as a raw material and that do not increase carbon dioxide even when burned are formed. In the polymer field, biomass plastics produced from biomass resources are actively developed.
バイオマスプラスチックの代表例がポリ乳酸であり、バイオマスプラスチックの中でも比較的高い耐熱性、機械特性を有するため、食器、包装材料、雑貨などに用途展開が広がりつつあるが、更に、工業材料としての可能性も検討されるようになってきた。
しかしながら、ポリ乳酸は、工業材料として使用するに当っては、その耐熱性が不足し、また生産性の高い射出成形によって成形品を得ようとすると、結晶性ポリマーとしてはその結晶性が低いため成形性が劣るという問題がある。
A representative example of biomass plastic is polylactic acid, which has relatively high heat resistance and mechanical properties among biomass plastics, so its application is expanding to tableware, packaging materials, general merchandise, etc. Sexuality has also been considered.
However, polylactic acid is insufficient in heat resistance when used as an industrial material, and when a molded product is obtained by injection molding with high productivity, the crystalline polymer has low crystallinity. There is a problem that moldability is inferior.
バイオマス資源を原料として使用し、かつ耐熱性が高い非晶性のポリカーボネート樹脂として、糖質から製造可能なエーテルジオール残基から得られる原料を用いたポリカーボネート樹脂が検討されている。特に、モノマーとしてイソソルビドを中心に用いてポリカーボネートに組み込むことが検討されてきた。特にイソソルビドのホモポリカーボネートについて記載されている（特許文献１、非特許文献１）。このうち特許文献１では、溶融エステル交換法を用いて２０３℃の融点を持つホモポリカーボネートを報告している。また非特許文献１では、酢酸亜鉛を触媒として用いた溶融エステル交換法において、ガラス転移温度が１６６℃のホモポリカーボネートを得ているが、熱分解温度（５％重量減少温度）が２８３℃と熱安定性は充分でない。また、イソソルビドと脂肪族ジヒドロキシ化合物とを共重合することにより、耐熱性と成型性に優れたポリカーボネート樹脂が提案されている（特許文献２）。しかしながら得られたポリカーボネート樹脂は溶融成型時の溶融強度、ブロー成形性などに問題があった。 As an amorphous polycarbonate resin that uses biomass resources as a raw material and has high heat resistance, a polycarbonate resin using a raw material obtained from an ether diol residue that can be produced from a saccharide has been studied. In particular, it has been investigated to incorporate isosorbide as a monomer mainly in polycarbonate. In particular, isosorbide homopolycarbonate is described (Patent Document 1, Non-Patent Document 1). Among these, Patent Document 1 reports a homopolycarbonate having a melting point of 203 ° C. using a melt transesterification method. In Non-Patent Document 1, a homopolycarbonate having a glass transition temperature of 166 ° C. is obtained in the melt transesterification method using zinc acetate as a catalyst, but the thermal decomposition temperature (5% weight loss temperature) is 283 ° C. Stability is not enough. Also, a polycarbonate resin excellent in heat resistance and moldability has been proposed by copolymerizing isosorbide and an aliphatic dihydroxy compound (Patent Document 2). However, the obtained polycarbonate resin has problems in melt strength and blow moldability during melt molding.
一般的にビスフェノールAからなるポリカーボネートの溶融強度の改良法として、分岐剤をポリマー骨格に導入する方法が知られている（特許文献３）。しかしながら、溶融法で分岐剤を用いて重合すると、分岐剤が高温で分解を起こして、目的の溶融強度が得られなかったり、色相が悪化する問題があった。 In general, as a method for improving the melt strength of polycarbonate composed of bisphenol A, a method of introducing a branching agent into a polymer skeleton is known (Patent Document 3). However, when polymerization is performed using a branching agent in the melting method, the branching agent is decomposed at a high temperature, and there is a problem that the intended melt strength cannot be obtained or the hue deteriorates.
本発明者は、上記目的を達成するために、鋭意検討した結果、植物由来のモノマーであるイソソルビドからなるポリカーボネート樹脂に分岐構造を導入することにより、溶融強度や色相が大幅に改良されることを見出し、本発明を完成するに至った。 As a result of intensive investigations to achieve the above object, the present inventor has shown that melt strength and hue are greatly improved by introducing a branched structure into a polycarbonate resin made of plant-derived monomer isosorbide. The headline and the present invention were completed.
上記課題は、次に挙げる手段を採用することにより達成することができる。すなわち、本発明によれば、
１．植物由来の下記式（１）で表されるエーテルジオール残基１５〜１００モル％を占める分岐化ポリカーボネート樹脂。
３．ＪＩＳ Ｋ７１２０で求められる５％重量減少開始温度が２４０℃以上４００℃以下である分岐剤を用いる前記１または２に記載のポリカーボネート樹脂。
４．分岐剤が原料のジヒドロキシ化合物に対して、０．０１ｍｏｌ％以上３ｍｏｌ％以下である前記１〜３のいずれかに記載のポリカーボネート樹脂。
５．分岐剤がペンタエリトリトール、１，１，１−トリス（４−ヒドロキシフェニル）エタン、１，１，１−トリス（４−ヒドロキシ−３−メチルフェニル）エタン、１，１，１−トリス(４−ヒドロキシ−３，５−ジメチルフェニル)エタンで表される化合物である前記１〜４のいずれかに記載のポリカーボネート樹脂。
６．ポリカーボネート樹脂の構造粘性指数Ｎが１．４〜８である前記１〜５のいずれかに記載のポリカーボネート樹脂。
The above-mentioned subject can be achieved by adopting the following means. That is, according to the present invention,
1. A branched polycarbonate resin occupying 15 to 100 mol% of an ether diol residue represented by the following formula (1) derived from a plant.
3. 3. The polycarbonate resin according to the above 1 or 2, which uses a branching agent having a 5% weight loss start temperature determined by JIS K7120 of 240 ° C. or more and 400 ° C. or less.
4). 4. The polycarbonate resin according to any one of 1 to 3, wherein the branching agent is 0.01 mol% or more and 3 mol% or less with respect to the raw material dihydroxy compound.
5. The branching agent is pentaerythritol, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,1-tris (4- 5. The polycarbonate resin according to any one of 1 to 4 above, which is a compound represented by hydroxy-3,5-dimethylphenyl) ethane.
6). The polycarbonate resin according to any one of 1 to 5 above, wherein the structural viscosity index N of the polycarbonate resin is 1.4 to 8.
本発明は、バイオマス資源であるデンプンなどの糖質から誘導することができる構成単位を含有する分岐化ポリカーボネート樹脂であって、溶融強度やブロー成形性および色相が大幅に改良された分岐化ポリカーボネート樹脂を提供する。 The present invention relates to a branched polycarbonate resin containing a structural unit that can be derived from a carbohydrate such as starch, which is a biomass resource, and has greatly improved melt strength, blow moldability and hue. I will provide a.
以下、本発明のポリカーボネート樹脂について以下詳細に説明する。
本発明のポリカーボネート樹脂は、植物由来のエーテルジオール残基を含み、下記式（ａ）で表されるエーテルジオールおよび炭酸ジエステルと分岐剤から溶融重合法により製造したポリカーボネート樹脂である。
Hereinafter, the polycarbonate resin of the present invention will be described in detail.
The polycarbonate resin of the present invention is a polycarbonate resin containing a plant-derived ether diol residue and produced by a melt polymerization method from an ether diol and a carbonic acid diester represented by the following formula (a) and a branching agent.
エーテルジオールとしては、具体的には下記式（ｂ）、（ｃ）および（ｄ）で表されるイソソルビド、イソマンニド、イソイディッドなどが挙げられる。 Specific examples of the ether diol include isosorbide, isomannide, and isoidide represented by the following formulas (b), (c), and (d).
これら糖質由来のエーテルジオールは、自然界のバイオマスからも得られる物質で、再生可能資源と呼ばれるものの１つである。イソソルビドは、でんぷんから得られるＤーグルコースに水添した後、脱水を受けさせることにより得られる。その他のエーテルジオールについても、出発物質を除いて同様の反応により得られる。 These saccharide-derived ether diols are substances obtained from natural biomass and are one of so-called renewable resources. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials.
特に、カーボネート構成単位がイソソルビド（１，４；３，６ージアンヒドローＤーソルビトール）由来のカーボネート構成単位を含んでなるポリカーボネート樹脂が好ましい。イソソルビドはでんぷんなどから簡単に作ることができるエーテルジオールであり資源として豊富に入手することができる上、イソマンニドやイソイディッドと比べても製造の容易さ、性質、用途の幅広さの全てにおいて優れている。 In particular, a polycarbonate resin in which the carbonate structural unit includes a carbonate structural unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is preferable. Isosorbide is an ether diol that can be easily made from starch, and can be obtained in abundant resources, and is superior in all ease of manufacture, properties, and versatility of use compared to isomannide and isoidide. .
全ジオール残基中、式（１）で表されるジオール残基が好ましくは１５〜１００モル％、より好ましくは３０〜１００モル％、さらに好ましくは４０〜１００モル％、特に好ましくは５０〜１００モル％を占めるポリカーボネートである。
一方、本発明に用いるに適した共重合構成単位のジオール化合物としては、直鎖脂肪族ジオール化合物、脂環式ジオール化合物、芳香族ジヒドロキシ化合物のいずれでも良い。
Among all diol residues, the diol residue represented by the formula (1) is preferably 15 to 100 mol%, more preferably 30 to 100 mol%, still more preferably 40 to 100 mol%, and particularly preferably 50 to 100 mol%. Polycarbonate occupying mol%.
On the other hand, the diol compound having a copolymerization structural unit suitable for use in the present invention may be any of a linear aliphatic diol compound, an alicyclic diol compound, and an aromatic dihydroxy compound.
直鎖脂肪族ジオール化合物として、例えばエチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオール、１，７−ヘプタンジオール、１，８−オクタンジオール、２−エチル−１，６−ヘキサンジオール、２,２,４−トリメチル−１，６−ヘキサンジオール、１，１０−デカンジオール、水素化ジリノレイルグリコール，水素化ジオレイルグリコールなどを挙げることができる。これらのうち、１，３−プロパンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、１，１０−デカンジオールが好ましい。これらの直鎖脂肪族ジオール類は単独または二種以上組み合わせて用いてもよい。 Examples of linear aliphatic diol compounds include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated And dioleyl glycol. Of these, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol are preferable. These linear aliphatic diols may be used alone or in combination of two or more.
また、本発明に使用できる脂環式ジオールとしては、例えば１，２-シクロヘキサンジオール、１，３−シクロヘキサンジオール、１，４−シクロヘキサンジオール、２−メチル−１，４−シクロヘキサンジオールなどのシクロヘキサンジオール類、１，２-シクロヘキサンジメタノール、１，３−シクロヘキサンジメタノール、１，４−シクロヘキサンジメタノールなどのシクロヘキサンジメタノール類、２，３−ノルボルナンジメタノール、２，５−ノルボルナンジメタノールなどのノルボルナンジメタノール類、トリシクロデカンジメタノール、ペンタシクロペンタデカンジメタノール、１，３−アダマンタンジオール、２，２−アダマンタンジオール、デカリンジメタノール、及び３，９−ビス（２−ヒドロキシ−１，１−ジメチルエチル）−２，４，８，１０−テトラオキサスピロ［５．５］ウンデカンなどが挙げられる。これらのうち、１，４−シクロヘキサンジメタノール、トリシクロデカンジメタノール、３，９−ビス（２−ヒドロキシ−１，１−ジメチルエチル）−２，４，８，１０−テトラオキサスピロ［５．５］ウンデカンが好ましい。これらの脂環式ジオール類は単独または二種以上組み合わせて用いてもよい。 Examples of the alicyclic diol that can be used in the present invention include cyclohexanediol such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol. , 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanedimethanol such as 1,4-cyclohexanedimethanol, norbornane such as 2,3-norbornanedimethanol, 2,5-norbornanedimethanol Dimethanols, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2,2-adamantanediol, decalin dimethanol, and 3,9-bis (2-hydroxy-1,1-dimethyle) Le) -2,4,8,10-spiro [5.5] undecane. Among these, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5. 5] Undecane is preferred. These alicyclic diols may be used alone or in combination of two or more.
また本発明で使用きる芳香族ジヒドロキシ化合物としては、４’−ビフェノール、３，３’，５，５’−テトラフルオロ−４，４’−ビフェノール、α，α’−ビス（４−ヒドロキシフェニル）−ｏ−ジイソプロピルベンゼン、α，α’−ビス（４−ヒドロキシフェニル）−ｍ−ジイソプロピルベンゼン（通常“ビスフェノールＭ”と称される）、α，α’−ビス（４−ヒドロキシフェニル）−ｐ−ジイソプロピルベンゼン、α，α’−ビス（４−ヒドロキシフェニル）−ｍ−ビス（１，１，１，３，３，３−ヘキサフルオロイソプロピル）ベンゼン、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、９，９−ビス（３−フルオロ−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−トリフルオロメチルフェニル）フルオレン、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、１，１−ビス（４−ヒドロキシフェニル）−４−イソプロピルシクロヘキサン、１，１−ビス（３−シクロヘキシル−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）シクロペンタン、１，１−ビス（３−フルオロ−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）パーフルオロシクロヘキサン、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、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スルホキシド、４，４’−ジヒドロキシジフェニルスルフィド、３，３’−ジメチル−４，４’−ジヒドロキシジフェニルスルフィド、３，３’−ジメチル−４，４’−ジヒドロキシジフェニルスルフォン、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−３，３’−ジフェニルスルフィド、４，４’−ジヒドロキシ−３，３’−ジフェニルスルホキシド、４，４’−ジヒドロキシ−３，３’−ジフェニルスルホン、１，１−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）プロパン（通常“ビスフェノールＡ”と称される）、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン（通常“ビスフェノールＣ”と称される）、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）ペンタン、２，２−ビス（４−ヒドロキシー３−フェニルフェニル）プロパン、２，２−ビス（３−イソプロピル−４−ヒドロキシフェニル）プロパン、２，２−ビス（３−ｔ−ブチル−４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシフェニル）ブタン、４，４−ビス（４−ヒドロキシフェニル）ヘプタン、２，２−ビス（４−ヒドロキシフェニル）オクタン、１，１−ビス（４−ヒドロキシフェニル）デカン、１，１−ビス（３−メチル−４−ヒドロキシフェニル）デカン、１，１−ビス（２，３−ジメチルー４−ヒドロキシフェニル）デカン、２，２−ビス（３−ブロモ−４−ヒドロキシフェニル）プロパン、ビス（４−ヒドロキシフェニル）ジフェニルメタン、１，１−ビス（４−ヒドロキシフェニル）−４−イソプロピルシクロヘキサン、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（通常“ビスフェノールＡＦ”と称される）、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）−１，１，１，３，３，３−ヘキサフルオロプロパン、２，２−ビス（３，５−ジメチル−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、２，２−ビス（３−フルオロ−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、および２，２−ビス（３，５−ジフルオロ−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、２，２−ビス（３，５−ジブロモー４−ヒドロキシフェニル）プロパン、２，２−ビス（３，５−ジクロロー４−ヒドロキシフェニル）プロパン、２，２−ビス（３，５−ジメチルー４−ヒドロキシフェニル）プロパン、および２，２−ビス（３−シクロヘキシル−４−ヒドロキシフェニル）プロパンが挙げられる。 The aromatic dihydroxy compounds that can be used in the present invention include 4'-biphenol, 3,3 ', 5,5'-tetrafluoro-4,4'-biphenol, and α, α'-bis (4-hydroxyphenyl). -O-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene (usually referred to as "bisphenol M"), α, α'-bis (4-hydroxyphenyl) -p- Diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-bis (1,1,1,3,3,3-hexafluoroisopropyl) benzene, 9,9-bis (4-hydroxyphenyl) fluorene 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (3-fluoro-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-trifluoromethylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5- Trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane 1,1-bis (3-fluoro-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) perfluorocyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy -3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy Phenylsulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, 3,3′-dimethyl-4,4′-dihydroxy Diphenyl sulfone, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-diphenyl sulfide, 4,4′-dihydroxy-3,3′-diphenyl sulfoxide, 4,4′-dihydroxy-3 , 3′-diphenylsulfone, 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (usually “bisphenol A” ), 1,1-bis (4-hydroxyphenyl)- -Phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane (usually referred to as "bisphenol C"), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-t -Butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, , 1-bis (4-hydroxyphenyl) decane, 1,1-bis (3-methyl-4-hydroxyphenyl) decane, 1,1-bis (2, 3-dimethyl-4-hydroxyphenyl) decane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -4- Isopropylcyclohexane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (usually referred to as “bisphenol AF”), 2,2-bis (4- Hydroxy-3-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -1,1,1,3 3,3-hexafluoropropane, 2,2-bis (3-fluoro-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 2,2-bis (3,5-difluoro-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) Propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, and 2,2-bis (3-cyclohexyl-4) -Hydroxyphenyl) propane.
上記の中でも、ビスフェノールＭ、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、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、３，３’−ジメチル−４，４’−ジヒドロキシジフェニルスルフィド、ビスフェノールＡ、ビスフェノールＣ、ビスフェノールＡＦ、および１，１−ビス（４−ヒドロキシフェニル）デカンが好ましい。これらの芳香族ジオール類は単独または二種以上組み合わせて用いてもよい。 Among the above, bisphenol M, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3 , 3,5-trimethylcyclohexane, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, bisphenol A, bisphenol C, bisphenol AF, and 1,1-bis (4-hydroxyphenyl) decane are preferred. These aromatic diols may be used alone or in combination of two or more.
分岐化剤として、一分子中に３個以上の官能基を有する化合物を用いる。官能基としては、ヒドロキシル基やカルボキシル基やカルボン酸エステル基またはハルカルボニル基やアミノ基、イミノ基を含む化合物が好ましい。具体的には、ソルビトール、１，２，３，６−ヘキサンテトロール、１，４−ソルビタン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、１，２，４−ブタントリオール、１，２，５−ペンタントリオール、グリセリン、２−メチルプロパントリオール、２−メチル−１，２，４−ブタントリオール、トリメチロールエタン、トリメチロールプロパン、１，２，６−ヘキサントリオール、２，５−ジメチル−１．２．６−ヘキサントリオール、ジペンタエリトリトール、トリメチロールエタン、トリメチロールプロパン、１，３，５−シクロヘキサントリオールフロログルシン、メリト酸、トリメリト酸、トリメリト酸クロリド、無水トリメリト酸、没食子酸、没食子酸ｎ−プロピル、プロトカテク酸、ピロメリト酸、ピロメリト酸第二無水物、α−レゾルシン酸、β−レゾルシン酸、レゾルシンアルデヒド、トリメリチルクロリド、トリメチルトリクロリド、４−クロロホルミルフタル酸無水物、ベンゾフェノンテトラカルボン酸、２，４，４'−トリヒドロキシベンゾフェノン、２，２',４，４'−テトラヒドロキシベンゾフェノン、２，４，４'−トリヒドロキシフェニルエーテル、２，２',４，４'−テトラヒドロキシフェニルエーテル、２，４，４'−トリヒドロキシジフェニル−２−プロパン、２，２'−ビス（２，４−ジヒドロキシ）プロパン、２，２', ４，４'−テトラヒドロキシジフェニルメタン、２，４，４'−トリヒドロキシジフェニルメタン、１−〔α−メチル−α−(４'−ヒドロキシフェニル)エチル〕−４−〔α',α'−ビス（４"−ヒドロキシフェニル）エチル〕ベンゼン、α，α', α"−トリス（４−ヒドロキシフェニル）−１，３，５−トリイソプロピルベンゼン、２,６−ビス（２'−ヒドロキシ−５'−メチルベンジル）−４−メチルフェノール、４,６−ジメチル−２，４，６−トリス（４'−ヒドロキシフェニル）−ヘプテン−２、４，６−ジメチル−２，４，６−トリス（４'−ヒドロキシフェニル）−ヘプタン−２、１，３，５−トリス(４'−ヒドロキシフェニル)−ベンゼン、１，１，１−トリス（４'−ヒドロキシフェニル）−エタン、１，１，１−トリス（４−ヒドロキシ−３−メチルフェニル）エタン、１，１，１−トリス(４−ヒドロキシ−３，５−ジメチルフェニル)エタン、２，２−ビス〔４，４−ビス（４'−ヒドロキシフェニル）シクロヘキシル〕−プロパン、２，６−ビス（２'−ヒドロキシ−５'−イソプロピルベンジル）−４−イソプロピルフェノール、ビス〔２−ヒドロキシ−３−（２'−ヒドロキシ−５'−メチルベンジル）−５−メチルフェニル〕メタン、ビス〔２−ヒドロキシ−３−（２'−ヒドロキシ−５'−イソプロピルベンジル）−５−メチルフェニル〕メタン、テトラキス（４−ヒドロキシフェニル）メタン、トリス（４−ヒドロキシフェニル）フェニルメタン、２',４',７−トリヒドロキシフラバン、２，４，４−トリメチル−２',４',７−トリヒドロキシフラバン、１,３−ビス（２',４'−ジヒドロキシフェニルイソプロピル）ベンゼン、トリス（４'−ヒドロキシアリール）−アミル−ｓ−トリアジン、１−〔α−メチル−α−（４'−ヒドロキシフェニル）エチル〕−３−〔α'，α'−ビス（４"−ヒドロキシフェニル）エチル〕ベンゼン、イサチンビス（Ｏ−クレゾール）等があげられる。これらの中でも、ペンタエリトリトール、グリセリン、１，１，１−トリス（４−ヒドロキシフェニル）エタン、１，１，１−トリス（４−ヒドロキシ−３−メチルフェニル）エタン、１，１，１−トリス(４−ヒドロキシ−３，５−ジメチルフェニル)エタンが特に好ましい。分岐剤はそれぞれ単独で用いてもよいし、二種以上組み合わせて用いてもよい。 As a branching agent, a compound having 3 or more functional groups in one molecule is used. As the functional group, a compound containing a hydroxyl group, a carboxyl group, a carboxylic acid ester group, a hull carbonyl group, an amino group, or an imino group is preferable. Specifically, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5 -Pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, 2,5-dimethyl-1. 2.6-hexanetriol, dipentaerythritol, trimethylolethane, trimethylolpropane, 1,3,5-cyclohexanetriol phloroglucin, mellitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, gallic acid n-propyl, protocatechuic acid, pyro Lithic acid, pyromellitic acid dianhydride, α-resorcinic acid, β-resorcinic acid, resorcinaldehyde, trimellityl chloride, trimethyltrichloride, 4-chloroformylphthalic anhydride, benzophenonetetracarboxylic acid, 2,4,4 '-Trihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,4,4'-trihydroxyphenyl ether, 2,2 ', 4,4'-tetrahydroxyphenyl ether, 2,4 , 4'-trihydroxydiphenyl-2-propane, 2,2'-bis (2,4-dihydroxy) propane, 2,2 ', 4,4'-tetrahydroxydiphenylmethane, 2,4,4'-trihydroxy Diphenylmethane, 1- [α-methyl-α- (4'-hydroxyphenyl) ethyl] -4- [α ', α'-bis (4 "-hydro Cyphenyl) ethyl] benzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 2,6-bis (2′-hydroxy-5′-methylbenzyl)- 4-methylphenol, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -Heptane-2,1,3,5-tris (4'-hydroxyphenyl) -benzene, 1,1,1-tris (4'-hydroxyphenyl) -ethane, 1,1,1-tris (4-hydroxy -3-methylphenyl) ethane, 1,1,1-tris (4-hydroxy-3,5-dimethylphenyl) ethane, 2,2-bis [4,4-bis (4'-hydroxyphenyl) cyclohexyl]- Propane, 2 , 6-bis (2′-hydroxy-5′-isopropylbenzyl) -4-isopropylphenol, bis [2-hydroxy-3- (2′-hydroxy-5′-methylbenzyl) -5-methylphenyl] methane, Bis [2-hydroxy-3- (2′-hydroxy-5′-isopropylbenzyl) -5-methylphenyl] methane, tetrakis (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) phenylmethane, 2 ′, 4 ′, 7-trihydroxyflavan, 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan, 1,3-bis (2 ′, 4′-dihydroxyphenylisopropyl) benzene, tris (4 '-Hydroxyaryl) -amyl-s-triazine, 1- [α-methyl-α- (4'-hydroxyphenyl) ethyl] -3- [α', α'-bis 4 "- hydroxyphenyl) ethyl] benzene, isatin bis (O-cresol) and the like. Among these, pentaerythritol, glycerin, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,1-tris (4-Hydroxy-3,5-dimethylphenyl) ethane is particularly preferred. The branching agents may be used alone or in combination of two or more.
分岐剤の５％重量減少温度の下限が２４０℃以上が好ましく、より好ましくは２５０℃以上であり、さらに好ましくは２６０℃以上である。５％重量減少温度が２４０℃以下であると、溶融重合中で分解し、目的の溶融強度が得られなかったり、色相が悪化する。また、５％重量減少温度の上限は４００℃以下である。上限温度は高いほうが好ましいが、実際に重合や成型する温度は４００℃以下であることと、４００℃以上の化合物は分子量が高くなりやすく、分岐剤として好ましくない。 The lower limit of the 5% weight loss temperature of the branching agent is preferably 240 ° C or higher, more preferably 250 ° C or higher, and further preferably 260 ° C or higher. If the 5% weight loss temperature is 240 ° C. or lower, it will decompose during melt polymerization and the desired melt strength will not be obtained, or the hue will deteriorate. The upper limit of the 5% weight loss temperature is 400 ° C. or less. Although the upper limit temperature is preferably higher, the actual polymerization or molding temperature is 400 ° C. or lower, and compounds having a temperature of 400 ° C. or higher tend to have a high molecular weight, which is not preferable as a branching agent.
反応温度は、エーテルジオールの分解を抑え、着色が少なく高粘度の樹脂を得るために、できるだけ低温の条件を用いることが好ましいが、重合反応を適切に進める為には重合温度は１８０℃〜２８０℃の範囲であることが好ましく、より好ましくは１８０℃〜２６０℃の範囲である。ビスフェノールＡからなるポリカーボネートの一般的な重合温度は２８０〜３４０℃と非常に高温のため、分岐剤が熱分解し、色相が悪化したり、目的の溶融強度が得られなかった。 また、反応初期にはエーテルジオールと炭酸ジエステルとを常圧で加熱し、予備反応させた後、徐々に減圧にして反応後期には系を１．３×１０ー３〜１．３×１０ー５ＭＰａ程度に減圧して生成するアルコールまたはフェノールの留出を容易にさせる方法が好ましい。反応時間は通常０．５〜４時間程度である。 The reaction temperature is preferably as low as possible in order to suppress decomposition of the ether diol and obtain a highly viscous resin with little coloration, but the polymerization temperature is 180 ° C. to 280 ° C. in order to proceed the polymerization reaction appropriately. It is preferably in the range of ° C, more preferably in the range of 180 ° C to 260 ° C. Since the general polymerization temperature of polycarbonate composed of bisphenol A is very high at 280 to 340 ° C., the branching agent thermally decomposes, the hue deteriorates, and the intended melt strength cannot be obtained. Further, the reaction initially with ether diol and a carbonic acid diester by heating under normal pressure, after pre-reacted, the system to 1.3 × 10 -3 gradually to the reaction late in the vacuum ~ 1.3, × 10 over A method of facilitating the distillation of alcohol or phenol produced by reducing the pressure to about 5 MPa is preferred. The reaction time is usually about 0.5 to 4 hours.
炭酸ジエステルとしては、水素原子が置換されていてもよい炭素数６〜１２のアリール基またはアラルキル基、もしくは炭素数１〜４のアルキル基などのエステルが挙げられる。具体的にはジフェニルカーボネート、ビス（クロロフェニル）カーボネート、ｍークレジルカーボネート、ジナフチルカーボネート、ビス（ジフェニル）カーボネート、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネートなどが挙げられ、なかでも反応性、コスト面からジフェニルカーボネートが好ましい。 Examples of the carbonic acid diester include esters such as an aryl group or aralkyl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms, in which a hydrogen atom may be substituted. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Diphenyl carbonate is preferred.
炭酸ジエステルはエーテルジオールに対してモル比で１．０２〜０．９８となるように混合することが好ましく、より好ましくは１．０１〜０．９８であり、さらに好ましくは１．０１〜０．９９である。炭酸ジエステルのモル比が１．０２より多くなると、炭酸エステル残基が末端封止として働いてしまい充分な重合度が得られなくなってしまい好ましくない。また炭酸ジエステルのモル比が０．９８より少ない場合でも、充分な重合度が得られず好ましくない。 The carbonic acid diester is preferably mixed so as to have a molar ratio of 1.02 to 0.98 with respect to the ether diol, more preferably 1.01 to 0.98, and still more preferably 1.01 to 0.8. 99. If the molar ratio of the carbonic acid diester is more than 1.02, the carbonic acid ester residue acts as a terminal block and a sufficient degree of polymerization cannot be obtained, which is not preferable. Even when the molar ratio of carbonic acid diester is less than 0.98, a sufficient degree of polymerization cannot be obtained, which is not preferable.
重合触媒としては、水酸化ナトリウム、水酸化カリウム、水酸化セシウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素セシウム、二価フェノールのナトリウム塩、カリウム塩またはセシウム塩等のアルカリ金属化合物、水酸化カルシウム、水酸化バリウム、水酸化マグネシウム等のアルカリ土類金属化合物、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチルアミン、トリエチルアミン等の含窒素塩基性化合物、などが挙げられる。これらは単独で使用してもよいし、２種以上組み合わせて使用してもよい。なかでも、含窒素塩基性化合物とアルカリ金属化合物とを併用して使用することが好ましい。これらの触媒を用いて重合したものは、５％重量減少温度が十分高く保たれるため好ましい。 Polymerization catalysts include sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium salt of dihydric phenol, potassium salt or cesium salt Alkali metal compounds such as calcium hydroxide, barium hydroxide, alkaline earth metal compounds such as magnesium hydroxide, nitrogen-containing bases such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylamine and triethylamine And the like, and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use a nitrogen-containing basic compound and an alkali metal compound in combination. Those polymerized using these catalysts are preferred because the 5% weight loss temperature is kept sufficiently high.
これらの重合触媒の使用量は、それぞれ炭酸ジエステル成分１モルに対し、好ましくは１×１０-９〜１×１０-３当量、より好ましくは１×１０-８〜５×１０-４当量の範囲で選ばれる。また反応系は窒素などの原料、反応混合物、反応生成物に対し不活性なガスの雰囲気に保つことが好ましい。窒素以外の不活性ガスとしては、アルゴンなどを挙げることができる。更に、必要に応じて酸化防止剤等の添加剤を加えてもよい。 The amount of these polymerization catalysts used is preferably in the range of 1 × 10 −9 to 1 × 10 −3 equivalents, more preferably 1 × 10 −8 to 5 × 10 −4 equivalents, per 1 mol of the carbonic acid diester component. Chosen by The reaction system is preferably maintained in an atmosphere of a gas inert to the raw material such as nitrogen, the reaction mixture, and the reaction product. Examples of inert gases other than nitrogen include argon. Furthermore, you may add additives, such as antioxidant, as needed.
上記のごとく反応を行う事により得られるイソソルビド系ポリカーボネート樹脂は、その末端構造はヒドロキシ基または、炭酸ジエステル残基となるが、本発明のベースポリマー基材で用いるポリカーボネート樹脂は、その特性を損なわない範囲で別途末端基を導入しても良い。かかる末端基は、モノヒドロキシ化合物を重合時に添加することにより導入することができる。モノヒドロキシ化合物としては下記式（２）または（３）で表されるヒドロキシ化合物が好ましく用いられる。 The isosorbide-based polycarbonate resin obtained by performing the reaction as described above has a hydroxyl group or a carbonic acid diester residue as the terminal structure, but the polycarbonate resin used in the base polymer substrate of the present invention does not impair the characteristics. You may introduce | transduce a terminal group separately in the range. Such end groups can be introduced by adding a monohydroxy compound during polymerization. As the monohydroxy compound, a hydroxy compound represented by the following formula (2) or (3) is preferably used.
上記式（２），（３）中、Ｒ１は炭素原子数４〜３０のアルキル基、炭素原子数７〜３０のアラルキル基、炭素原子数４〜３０のパーフルオロアルキル基、または下記式（４）
また、上記式（４）中、Ｒ２，Ｒ３，Ｒ４，Ｒ５及びＲ６は、夫々独立して炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のシクロアルキル基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１０のアリール基及び炭素原子数７〜２０のアラルキル基からなる群から選ばれる少なくとも一種の基であり、好ましくは夫々独立して炭素原子数１〜１０のアルキル基及び炭素原子数６〜１０のアリール基からなる群から選ばれる少なくとも一種の基であり、特に夫々独立してメチル基及びフェニル基からなる群から選ばれる少なくとも一種の基が好ましい。ｂは０〜３の整数であり、１〜３の整数が好ましく、特に２〜３の整数が好ましい。ｃは４〜１００の整数であり、４〜５０の整数が好ましく、特に８〜５０の整数が好ましい。 In the above formula (4), R 2 , R 3 , R 4 , R 5 and R 6 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, It is at least one group selected from the group consisting of an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, preferably each independently a carbon atom. And at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, and particularly at least one group selected from the group consisting of a methyl group and a phenyl group, respectively. Is preferred. b is an integer of 0 to 3, an integer of 1 to 3 is preferable, and an integer of 2 to 3 is particularly preferable. c is an integer of 4 to 100, preferably an integer of 4 to 50, and particularly preferably an integer of 8 to 50.
本発明に用いるモノヒドロキシ化合物もまた植物などの再生可能資源から得られる原料であることが好ましい。植物から得られるモノヒドロキシ化合物としては、植物油から得られる炭素数１４以上の長鎖アルキルアルコール類（セタノール、ステアリルアルコール、ベヘニルアルコール）などが挙げられる。 The monohydroxy compound used in the present invention is also preferably a raw material obtained from renewable resources such as plants. Examples of monohydroxy compounds obtained from plants include long-chain alkyl alcohols having 14 or more carbon atoms (cetanol, stearyl alcohol, behenyl alcohol) obtained from vegetable oils.
本発明のイソソルビド系ポリカーボネート樹脂は、ＡＳＴＭ Ｄ６８６６ ０５に準拠して測定された生物起源物質含有率が２５％〜１００％が好ましく、３０％〜１００％がより好ましい。 The isosorbide-based polycarbonate resin of the present invention preferably has a biogenic substance content of 25% to 100%, more preferably 30% to 100%, as measured according to ASTM D686605.
分岐剤を含まないイソソルビド系ポリカーボネート樹脂の構造粘性指数Ｎは１．２〜１．３であるのに対し、本発明のポリカーボネート樹脂の構造粘性指数Ｎは１．４〜８であるものが好ましく、より好ましくは１．４〜３である。この構造粘性指数Ｎはポリカーボネート樹脂の溶融特性は式Ｑ＝Ｋ・ｐＮ脂｛式中Ｑは溶融樹脂の流動性（ｍｌ／ｓｅｃ）、Ｋは定数、ｐは圧力（ｋｇ／ｃｍ２）、Ｎは構造粘性指数｝から求められる。Ｎ＝１のときニュートン流動挙動を示し、Ｎが大きくなるほど非ニュートン挙動を示す。 The structural viscosity index N of the isosorbide-based polycarbonate resin containing no branching agent is 1.2 to 1.3, whereas the structural viscosity index N of the polycarbonate resin of the present invention is preferably 1.4 to 8, More preferably, it is 1.4-3. This structural viscosity index N is the melting characteristic of the polycarbonate resin in the formula Q = K · pN fat {where Q is the fluidity of the molten resin (ml / sec), K is a constant, p is the pressure (kg / cm 2 ), N Is obtained from the structural viscosity index}. When N = 1, Newtonian flow behavior is exhibited, and as N increases, non-Newtonian behavior is exhibited.
本発明のイソソルビド系ポリカーボネート樹脂は、樹脂０．７ｇを塩化メチレン１００ｍｌに溶解した溶液の２０℃における比粘度としては０．１４〜０．５０のものを用いることができる。比粘度の好ましい範囲は、下限は０．２０以上が好ましく、０．２２以上がより好ましい。また上限は０．４５以下が好ましく、０．３７以下がより好ましく、０．３５以下が特に好ましい。また比粘度が０．１４より低くなると本発明のポリカーボネート樹脂より得られた積層フィルムが充分な機械強度を持たせることが困難となる。また比粘度が０．５０より高くなると溶融流動性が高くなりすぎて、成形に必要な流動性を有する溶融温度が分解温度より高くなってしまう。 As the isosorbide-based polycarbonate resin of the present invention, those having a specific viscosity at 20 ° C. of 0.14 to 0.50 of a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride can be used. The lower limit of the specific viscosity is preferably 0.20 or more, and more preferably 0.22 or more. The upper limit is preferably 0.45 or less, more preferably 0.37 or less, and particularly preferably 0.35 or less. On the other hand, if the specific viscosity is lower than 0.14, it becomes difficult for the laminated film obtained from the polycarbonate resin of the present invention to have sufficient mechanical strength. On the other hand, if the specific viscosity is higher than 0.50, the melt fluidity becomes too high, and the melting temperature having the fluidity necessary for molding becomes higher than the decomposition temperature.
本発明のイソソルビド系ポリカーボネート樹脂は、そのガラス転移温度（Ｔｇ）の下限が８０℃以上が好ましく、より好ましくは９０℃以上であり、また上限は１６５℃以下が好ましい。Ｔｇが８０℃未満だと耐熱性に劣り、１６５℃を超えると本発明のポリカーボネート樹脂を用いて成形する際の溶融流動性に劣り、ポリマー分解が少ない温度範囲で射出成形ができなくなる。ＴｇはＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製 ＤＳＣ （型式 ＤＳＣ２９１０）により測定される。 The lower limit of the glass transition temperature (Tg) of the isosorbide-based polycarbonate resin of the present invention is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and the upper limit is preferably 165 ° C. or lower. When Tg is less than 80 ° C., the heat resistance is inferior, and when it exceeds 165 ° C., the melt fluidity when molding using the polycarbonate resin of the present invention is inferior, and injection molding cannot be performed in a temperature range in which polymer decomposition is small. Tg is measured by DSC (model DSC2910) manufactured by TA Instruments.
また、イソソルビド系ポリカーボネート樹脂は、その５％重量減少温度の下限が３３０℃以上が好ましく、より好ましくは３４０℃以上であり、さらに好ましくは３５０℃以上である。５％重量減少温度が上記範囲内であると、本発明のポリカーボネート樹脂を用いて成形する際の樹脂の分解がほとんど無く好ましい。５％重量減少温度を上昇させるためには、前述の通り溶融重合触媒として好ましい化合物を選択することが有効である。５％重量減少温度はＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製 ＴＧＡ （型式 ＴＧＡ２９５０）により測定される。 The lower limit of the 5% weight reduction temperature of the isosorbide-based polycarbonate resin is preferably 330 ° C. or higher, more preferably 340 ° C. or higher, and further preferably 350 ° C. or higher. It is preferable that the 5% weight loss temperature is within the above range since there is almost no decomposition of the resin when molding using the polycarbonate resin of the present invention. In order to increase the 5% weight loss temperature, it is effective to select a preferable compound as the melt polymerization catalyst as described above. The 5% weight loss temperature is measured by TA Instruments TGA (model TGA2950).
本発明のイソソルビド系ポリカーボネート樹脂においては、さらに良好な色相かつ安定した流動性を得るため、熱安定剤を含有する事が好ましい。熱安定剤としては、リン系安定剤を含有することが好ましく、殊にリン系安定剤として、下記一般式（５）に示すペンタエリスリトール型ホスファイト化合物を配合することが好ましい。 The isosorbide-based polycarbonate resin of the present invention preferably contains a heat stabilizer in order to obtain a better hue and stable fluidity. As the heat stabilizer, it is preferable to contain a phosphorus stabilizer, and it is particularly preferable to blend a pentaerythritol phosphite compound represented by the following general formula (5) as the phosphorus stabilizer.
前記ペンタエリスリトール型ホスファイト化合物としては、より具体的には、例えば、ジステアリルペンタエリスリトールジホスファイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−ｔｅｒｔ−ブチル−４−エチルフェニル）ペンタエリスリトールジホスファイト、フェニルビスフェノールＡペンタエリスリトールジホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ジシクロヘキシルペンタエリスリトールジホスファイトなどが挙げられ、中でも好適には、ジステアリルペンタエリスリトールジホスファイト、およびビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジホスファイトが挙げられる。 More specifically, examples of the pentaerythritol type phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like are preferable. Among them, distearyl pentaerythritol diphosphite and bis (2,4-di-te) are preferable. Include t- butylphenyl) pentaerythritol diphosphite.
他のリン系安定剤としては、前記以外の各種ホスファイト化合物、ホスホナイト化合物、およびホスフェート化合物が挙げられる。
ホスファイト化合物としては、例えば、トリフェニルホスファイト、トリス（ノニルフェニル）ホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジデシルモノフェニルホスファイト、ジオクチルモノフェニルホスファイト、ジイソプロピルモノフェニルホスファイト、モノブチルジフェニルホスファイト、モノデシルジフェニルホスファイト、モノオクチルジフェニルホスファイト、２，２−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）オクチルホスファイト、トリス（ジエチルフェニル）ホスファイト、トリス（ジ−ｉｓｏ−プロピルフェニル）ホスファイト、トリス（ジ−ｎ−ブチルフェニル）ホスファイト、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、およびトリス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイトなどが挙げられる。
Examples of other phosphorus stabilizers include various other phosphite compounds, phosphonite compounds, and phosphate compounds.
Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (diethylphenyl) phos Phyto, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite Ito, and tris (2,6-di -tert- butylphenyl) phosphite and the like.
さらに他のホスファイト化合物としては二価フェノール類と反応し環状構造を有するものも使用できる。例えば、２，２’−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、２，２’−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）（２−ｔｅｒｔ−ブチル−４−メチルフェニル）ホスファイト、２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェニル）（２−ｔｅｒｔ−ブチル−４−メチルフェニル）ホスファイト、２，２’−エチリデンビス（４−メチル−６−ｔｅｒｔ−ブチルフェニル）（２−ｔｅｒｔ−ブチル−４−メチルフェニル）ホスファイトなどを挙げることができる。 Still other phosphite compounds that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.
ホスフェート化合物としては、トリブチルホスフェート、トリメチルホスフェート、トリクレジルホスフェート、トリフェニルホスフェート、トリクロルフェニルホスフェート、トリエチルホスフェート、ジフェニルクレジルホスフェート、ジフェニルモノオルソキセニルホスフェート、トリブトキシエチルホスフェート、ジブチルホスフェート、ジオクチルホスフェート、ジイソプロピルホスフェートなどを挙げることができ、好ましくはトリフェニルホスフェート、トリメチルホスフェートである。 Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.
ホスホナイト化合物としては、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，３’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−３，３’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−４，３’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−３，３’−ビフェニレンジホスホナイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４−フェニル−フェニルホスホナイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−３−フェニル−フェニルホスホナイト、ビス（２，６−ジ−ｎ−ブチルフェニル）−３−フェニル−フェニルホスホナイト、ビス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−４−フェニル−フェニルホスホナイト、ビス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−３−フェニル−フェニルホスホナイト等があげられ、テトラキス（ジ−ｔｅｒｔ−ブチルフェニル）−ビフェニレンジホスホナイト、ビス（ジ−ｔｅｒｔ−ブチルフェニル）−フェニル−フェニルホスホナイトが好ましく、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−ビフェニレンジホスホナイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−フェニル−フェニルホスホナイトがより好ましい。かかるホスホナイト化合物は上記アルキル基が２以上置換したアリール基を有するホスファイト化合物との併用可能であり好ましい。 Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.
ホスホネイト化合物としては、ベンゼンホスホン酸ジメチル、ベンゼンホスホン酸ジエチル、およびベンゼンホスホン酸ジプロピル等が挙げられる。
上記のリン系安定剤は、単独でまたは２種以上を併用して使用することができ、少なくともペンタエリスリトール型ホスファイト化合物を有効量配合することが好ましい。リン系安定剤はポリカーボネート樹脂１００重量部当たり、好ましくは０．００１〜１重量部、より好ましくは０．０１〜０．５重量部、さらに好ましくは０．０１〜０．３重量部配合される。
Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.
Said phosphorus stabilizer can be used individually or in combination of 2 or more types, It is preferable to mix | blend an effective amount of a pentaerythritol type | mold phosphite compound at least. The phosphorus stabilizer is preferably added in an amount of 0.001 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the polycarbonate resin. .
本発明のイソソルビド系ポリカーボネート樹脂には各種帯電防止剤を添加、共重合することが好ましい。かかる帯電防止剤としては、アニオン系、カチオン系、非イオン系、両性の各種公知のものを用いることが可能である。中でも特に耐熱性などの点からはアニオン系帯電防止剤のアルキルスルホン酸Ｎａ、アルキルベンゼンスルホン酸Ｎａを用いることが好ましい。 It is preferable to add and copolymerize various antistatic agents to the isosorbide-based polycarbonate resin of the present invention. As such an antistatic agent, various known anionic, cationic, nonionic and amphoteric ones can be used. Among these, from the viewpoint of heat resistance, it is preferable to use anionic antistatic agent Na alkyl sulfonate and Na alkylbenzene sulfonate.
またこれらの帯電防止剤を重合時に添加する際には、併せて酸化防止剤を添加することが、取り扱い性などの点から好ましい。かかる酸化防止剤としては、フェノール系酸化防止剤、フォスファイト系酸化防止剤、チオエーテル系酸化防止剤などの各種公知のものを用いることができ、さらにこれらの混合の化合物なども用いることが可能である。 Moreover, when adding these antistatic agents at the time of superposition | polymerization, it is preferable from points, such as handleability, to add antioxidant together. As such an antioxidant, various known compounds such as a phenolic antioxidant, a phosphite antioxidant, a thioether antioxidant, and a mixture of these compounds can be used. is there.
本発明のイソソルビド系ポリカーボネート中には、目的や用途に応じて各種の粒子を添加することができる。添加する粒子は、本発明のイソソルビド系ポリカーボネート樹脂に不活性なものであれば特に限定されないが、無機粒子、有機粒子、架橋高分子粒子、重合系内で生成させる内部粒子などを挙げることができる。これらの粒子を２種以上添加しても構わない。かかる粒子の添加量は、フィルムの全重量に対して０．０１〜１０重量％が好ましく、さらに好ましくは０．０５〜３重量％である。 Various particles can be added to the isosorbide-based polycarbonate of the present invention depending on the purpose and application. The particles to be added are not particularly limited as long as they are inert to the isosorbide-based polycarbonate resin of the present invention, and examples thereof include inorganic particles, organic particles, crosslinked polymer particles, and internal particles generated in the polymerization system. . Two or more kinds of these particles may be added. The amount of such particles added is preferably 0.01 to 10% by weight, more preferably 0.05 to 3% by weight, based on the total weight of the film.
以下、実施例により本発明を詳述する。ただし、本発明はこれらに限定されるものではない。なお参考例、実施例および比較例中の物性測定は以下のようにして行ったものである。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these. In addition, the physical-property measurement in a reference example, an Example, and a comparative example was performed as follows.
（１）比粘度
ペレットを塩化メチレンに溶解、濃度を約０．７ｇ／ｄＬとして、温度２０℃にて、オストワルド粘度計（装置名：ＲＩＧＯ ＡＵＴＯ ＶＩＳＣＯＳＩＭＥＴＥＲ ＴＹＰＥ ＶＭＲ−０５２５・ＰＣ）を使用して測定した。なお、比粘度ηｓｐは下記式から求められる。
ηｓｐ＝ｔ／ｔｏ−１
ｔ ：試料溶液のフロータイム
ｔｏ ：溶媒のみのフロータイム
(1) Specific viscosity Measured using an Ostwald viscometer (apparatus name: RIGO AUTO VISCOSIMETER TYPE VMR-0525 · PC) at a temperature of 20 ° C. with the pellet dissolved in methylene chloride at a concentration of about 0.7 g / dL. did. In addition, specific viscosity (eta) sp is calculated | required from a following formula.
η sp = t / t o −1
t: Flow time of sample solution t o : Flow time of solvent only
（２）色相（ｂ値）
ポリカーボネートペレット（短径×長径×長さ（ｍｍ）＝２．５×３．３×３．０）のＬ，ａ，ｂ値を日本電色工業製ＮＤ−１００１ＤＰを用いて反射法で測定した結果の内、黄色度の尺度としてｂ値を用いた。
(2) Hue (b value)
L, a, and b values of polycarbonate pellets (minor axis x major axis x length (mm) = 2.5 x 3.3 x 3.0) were measured by a reflection method using ND-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. Among the results, b value was used as a measure of yellowness.
（３）構造粘性指数
構造粘性指数は、ポリカーボネートのペレットを高化式フローテスター（島津製作所（株）製）シリンダー；ノズル径１ｍｍノズル長１０ｍｍに仕込み、温度２８０℃に一定にして、加えた圧力、Ｐ（１００〜２００ｋｇ／ｃｍ２）と、それに対する溶融樹脂の留出量Ｑ（ｍＬ／ｓｅｃ）を測定し、それぞれの値を両対数グラフにプロットして得られる回帰直線の勾配から求めた。
(3) Structural Viscosity Index The structural viscosity index is the pressure applied to polycarbonate pellets with a Koka type flow tester (manufactured by Shimadzu Corporation); nozzle diameter 1 mm, nozzle length 10 mm, constant temperature 280 ° C. , P (100 to 200 kg / cm 2 ) and the molten resin distillate amount Q (mL / sec) relative to it were measured, and the respective values were determined from the slope of the regression line obtained by plotting on a log-log graph. .
（４）ブロー成形性
８０℃で、２４時間乾燥したポリカーボネート組成物を、押出機により溶融し、金型に供給した後、１８Ｌのボトルをブロー成形し、成形性を評価した。得られた成型品の外観を評価した。成型品を通して文字を目視したときにはっきりと見えるものを良好とし、ぼやけて見えるものを目視不良とし、ボトルの形状が不良の場合、成型不良とした。
(4) Blow moldability After the polycarbonate composition dried at 80 ° C. for 24 hours was melted by an extruder and supplied to a mold, an 18 L bottle was blow molded to evaluate the moldability. The appearance of the obtained molded product was evaluated. When the characters were clearly seen through the molded product, the one that was clearly visible was considered good, and the one that looked blurry was regarded as a poor visual inspection.
［実施例１］
イソソルビド１０９６重量部とヘキサンジオール２９５重量部とジフェニルカーボネート２１３８重量部とペンタエリトリトール（５％重量減少温度 ２６２℃）４．１重量部とを反応器に入れ、重合触媒としてテトラメチルアンモニウムヒドロキシドを０．３６重量部、および水酸化ナトリウムを４×１０−４重量部仕込んで窒素雰囲気下常圧で１８０℃に加熱し溶融させた。
撹拌下、反応槽内を３０分かけて徐々に減圧し、生成するフェノールを留去しながら１３．３×１０−３ＭＰａまで減圧した。この状態で２０分反応させた後に２００℃に昇温した後、２０分かけて徐々に減圧し、フェノールを留去しながら４．００×１０−３ＭＰａで２０分間反応させ、さらに、２２０℃に昇温し３０分間、２５０℃に昇温し３０分間反応させた。
[Example 1]
1096 parts by weight of isosorbide, 295 parts by weight of hexanediol, 2138 parts by weight of diphenyl carbonate, and 4.1 parts by weight of pentaerythritol (5% weight reduction temperature 262 ° C.) were placed in a reactor, and tetramethylammonium hydroxide was added as a polymerization catalyst. .36 parts by weight and 4 × 10 −4 parts by weight of sodium hydroxide were charged and heated to 180 ° C. and melted at normal pressure in a nitrogen atmosphere.
Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 −3 MPa while the produced phenol was distilled off. After reacting in this state for 20 minutes, the temperature was raised to 200 ° C., then the pressure was gradually reduced over 20 minutes, and the reaction was carried out at 4.00 × 10 −3 MPa for 20 minutes while distilling off the phenol. The mixture was heated to 250 ° C. for 30 minutes and reacted for 30 minutes.
次いで、徐々に減圧し、２．６７×１０−３ＭＰａで１０分間、１．３３×１０−３ＭＰａで１０分間反応を続行し、さらに減圧し、４．００×１０−５ＭＰａに到達したら、徐々に２６０℃まで昇温し、最終的に２６０℃、６．６６×１０−５ＭＰａで１時間反応せしめた。反応後のポリマーをペレット化した。得られたポリマーの比粘度、ガラス転移温度を測定し、その結果を表１に示した。また、得られたポリマーを用いて、シリンダー温度２５０℃の条件で金型に供給した後、１８Ｌのボトルをブロー成形し、成形性を評価した。１８Ｌのボトルをブロー成形し、成形性を評価した。 Next, the pressure was gradually reduced, and the reaction was continued at 2.67 × 10 −3 MPa for 10 minutes and 1.33 × 10 −3 MPa for 10 minutes, and further reduced in pressure to reach 4.00 × 10 −5 MPa. The temperature was gradually raised to 260 ° C., and the reaction was finally carried out at 260 ° C. and 6.66 × 10 −5 MPa for 1 hour. The polymer after the reaction was pelletized. The specific viscosity and glass transition temperature of the obtained polymer were measured, and the results are shown in Table 1. Moreover, after supplying to a metal mold | die on the conditions of cylinder temperature 250 degreeC using the obtained polymer, the 18L bottle was blow-molded and the moldability was evaluated. An 18 L bottle was blow-molded to evaluate moldability.
［実施例２］
ペンタエリトリトール４．１重量部の代わりに１，１，１−トリス（４−ヒドロキシフェニル）エタン（５％重量減少温度 ３３４℃）９．２重量部を用いた以外は実施例１と同様にしてポリカーボネートの溶融重合を行った。得られたポリマーを実施例１と同様に評価した。
[Example 2]
Example 1 was used except that 9.2 parts by weight of 1,1,1-tris (4-hydroxyphenyl) ethane (5% weight loss temperature 334 ° C.) was used instead of 4.1 parts by weight of pentaerythritol. Polycarbonate was melt polymerized. The obtained polymer was evaluated in the same manner as in Example 1.
［実施例３］
イソソルビド７３１重量部とシクロヘキサンジメタノール７２０重量部とジフェニルカーボネート２１３８重量部とペンタエリトリトール４．１重量部以外は実施例１と同様にしてポリカーボネートの溶融重合を行った。得られたポリマーを実施例１と同様に評価した。
[Example 3]
Polycarbonate was melt polymerized in the same manner as in Example 1 except that 731 parts by weight of isosorbide, 720 parts by weight of cyclohexanedimethanol, 2138 parts by weight of diphenyl carbonate, and 4.1 parts by weight of pentaerythritol were used. The obtained polymer was evaluated in the same manner as in Example 1.
［実施例４］
ペンタエリトリトール４．１重量部の代わりに１，１，１−トリス（４−ヒドロキシフェニル）エタン９．２重量部を用いた以外は実施例３と同様にしてポリカーボネートの溶融重合を行った。得られたポリマーを実施例１と同様に評価した。
[Example 4]
Polycarbonate was melt polymerized in the same manner as in Example 3 except that 9.2 parts by weight of 1,1,1-tris (4-hydroxyphenyl) ethane was used instead of 4.1 parts by weight of pentaerythritol. The obtained polymer was evaluated in the same manner as in Example 1.
［実施例５］
ペンタエリトリトール６．８重量部を用いた以外は実施例１と同様にしてポリカーボネートの溶融重合を行った。得られたポリマーを実施例１と同様に評価した。
[Example 5]
Polycarbonate was melt polymerized in the same manner as in Example 1 except that 6.8 parts by weight of pentaerythritol was used. The obtained polymer was evaluated in the same manner as in Example 1.
［比較例１］
ペンタエリトリトール４．１重量部を用いなかった以外は実施例１と同様にしてポリカーボネートの溶融重合を行った。得られたポリマーを実施例１と同様に評価した。
[Comparative Example 1]
Polycarbonate was melt polymerized in the same manner as in Example 1 except that 4.1 parts by weight of pentaerythritol was not used. The obtained polymer was evaluated in the same manner as in Example 1.
［比較例２］
ビスフェノールＡ１１４０重量部とジフェニルカーボネート１１０３重量部と１，１，１−トリス（４−ヒドロキシフェニル）エタン９．２重量部とを反応器に入れ、重合触媒としてテトラメチルアンモニウムヒドロキシドを０．３６重量部、および水酸化ナトリウムを４×１０−４重量部仕込んで窒素雰囲気下常圧で１８０℃に加熱し溶融させた。
撹拌下、反応槽内を３０分かけて徐々に減圧し、生成するフェノールを留去しながら１３．３×１０−３ＭＰａまで減圧した。この状態で２０分反応させた後に２００℃に昇温した後、２０分かけて徐々に減圧し、フェノールを留去しながら４．００×１０−３ＭＰａで２０分間反応させ、さらに、２４０℃に昇温し、３０分間反応させた。
[Comparative Example 2]
1140 parts by weight of bisphenol A, 1103 parts by weight of diphenyl carbonate, and 9.2 parts by weight of 1,1,1-tris (4-hydroxyphenyl) ethane are put in a reactor, and 0.36 weight of tetramethylammonium hydroxide is used as a polymerization catalyst. 4 × 10 −4 parts by weight of sodium hydroxide and sodium hydroxide were heated to 180 ° C. and melted at normal pressure in a nitrogen atmosphere.
Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 −3 MPa while the produced phenol was distilled off. After reacting in this state for 20 minutes, the temperature was raised to 200 ° C., then the pressure was gradually reduced over 20 minutes, and the reaction was carried out at 4.00 × 10 −3 MPa for 20 minutes while distilling off the phenol. The temperature was raised to 30 minutes and reacted for 30 minutes.
次いで、徐々に減圧し、２．６７×１０−３ＭＰａで１０分間、１．３３×１０−３ＭＰａで１０分間反応を続行し、さらに減圧し、４．００×１０−５ＭＰａに到達したら、徐々に３００℃まで昇温し、６．６６×１０−５ＭＰａで１時間反応せしめた。反応後のポリマーをペレット化した。得られたポリマーの比粘度、ガラス転移温度を測定し、その結果を表１に示した。また、得られたポリマーを用いて、シリンダー温度３００℃にした以外は実施例１と同様にブロー成型し、評価した。 Next, the pressure was gradually reduced, and the reaction was continued at 2.67 × 10 −3 MPa for 10 minutes and 1.33 × 10 −3 MPa for 10 minutes, and further reduced in pressure to reach 4.00 × 10 −5 MPa. The temperature was gradually raised to 300 ° C., and the reaction was performed at 6.66 × 10 −5 MPa for 1 hour. The polymer after the reaction was pelletized. The specific viscosity and glass transition temperature of the obtained polymer were measured, and the results are shown in Table 1. Further, the obtained polymer was blow-molded and evaluated in the same manner as in Example 1 except that the cylinder temperature was 300 ° C.
［比較例３］
ビスフェノールＡ１１４０重量部とジフェニルカーボネート１１０３重量部とを反応器に入れ、重合触媒としてテトラメチルアンモニウムヒドロキシドを０．３６重量部、および水酸化ナトリウムを４×１０−４重量部仕込んで窒素雰囲気下常圧で１８０℃に加熱し溶融させた。
撹拌下、反応槽内を３０分かけて徐々に減圧し、生成するフェノールを留去しながら１３．３×１０−３ＭＰａまで減圧した。この状態で２０分反応させた後に２００℃に昇温した後、２０分かけて徐々に減圧し、フェノールを留去しながら４．００×１０−３ＭＰａで２０分間反応させ、さらに、２４０℃に昇温し、３０分間反応させた。
[Comparative Example 3]
1140 parts by weight of bisphenol A and 1103 parts by weight of diphenyl carbonate are placed in a reactor, and 0.36 parts by weight of tetramethylammonium hydroxide and 4 × 10 −4 parts by weight of sodium hydroxide are charged as a polymerization catalyst under a nitrogen atmosphere. The mixture was melted by heating to 180 ° C. under pressure.
Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 −3 MPa while the produced phenol was distilled off. After reacting in this state for 20 minutes, the temperature was raised to 200 ° C., then the pressure was gradually reduced over 20 minutes, and the reaction was carried out at 4.00 × 10 −3 MPa for 20 minutes while distilling off the phenol. The temperature was raised to 30 minutes and reacted for 30 minutes.
次いで、徐々に減圧し、２．６７×１０−３ＭＰａで１０分間、１．３３×１０−３ＭＰａで１０分間反応を続行し、さらに減圧し、４．００×１０−５ＭＰａに到達したら、徐々に３００℃まで昇温し、６．６６×１０−５ＭＰａで１時間反応せしめた。反応後のポリマーをペレット化した。得られたポリマーの比粘度、ガラス転移温度を測定し、その結果を表１に示した。また、得られたポリマーを用いて、シリンダー温度３００℃にした以外は実施例１と同様にブロー成型し、評価した。 Next, the pressure was gradually reduced, and the reaction was continued at 2.67 × 10 −3 MPa for 10 minutes and 1.33 × 10 −3 MPa for 10 minutes, and further reduced in pressure to reach 4.00 × 10 −5 MPa. The temperature was gradually raised to 300 ° C., and the reaction was performed at 6.66 × 10 −5 MPa for 1 hour. The polymer after the reaction was pelletized. The specific viscosity and glass transition temperature of the obtained polymer were measured, and the results are shown in Table 1. Further, the obtained polymer was blow-molded and evaluated in the same manner as in Example 1 except that the cylinder temperature was 300 ° C.
本発明によれば、重合温度を制御し、特定の分岐剤を導入することにより、大幅に色相が改善され、通常の溶融法でのポリカーボネートでは得られない溶融強度が得られた。
また、ブロー成形が良好な上に、バイオマス由来のため、カーボンニュートラルな成形品を効率良く生産することが可能な、分岐化ポリカーボネート樹脂が得ることができる。
According to the present invention, by controlling the polymerization temperature and introducing a specific branching agent, the hue is greatly improved, and a melt strength that cannot be obtained by a polycarbonate by a normal melting method is obtained.
Further, a branched polycarbonate resin capable of efficiently producing a carbon-neutral molded product because it is derived from biomass and has good blow molding can be obtained.
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| WO2013125540A1 (en) * | 2012-02-20 | 2013-08-29 | 三菱化学株式会社 | Resin composition and molded body of same |
| WO2014084327A1 (en) * | 2012-11-30 | 2014-06-05 | 出光興産株式会社 | Polycarbonate resin, polycarbonate resin composition and molded article |
| KR101679596B1 (en) | 2013-07-02 | 2016-11-25 | 주식회사 삼양사 | Isosorbide-aromatic polycarbonate copolymer and method for preparing the same |
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| WO2013125540A1 (en) * | 2012-02-20 | 2013-08-29 | 三菱化学株式会社 | Resin composition and molded body of same |
| JP2013199636A (en) * | 2012-02-20 | 2013-10-03 | Mitsubishi Chemicals Corp | Resin composition and molding thereof |
| US9193824B2 (en) | 2012-02-20 | 2015-11-24 | Mitsubishi Chemical Corporation | Resin composition and molded body of same |
| WO2014084327A1 (en) * | 2012-11-30 | 2014-06-05 | 出光興産株式会社 | Polycarbonate resin, polycarbonate resin composition and molded article |
| JP2014108981A (en) * | 2012-11-30 | 2014-06-12 | Idemitsu Kosan Co Ltd | Polycarbonate resin, polycarbonate resin composition and molded article |
| KR101679596B1 (en) | 2013-07-02 | 2016-11-25 | 주식회사 삼양사 | Isosorbide-aromatic polycarbonate copolymer and method for preparing the same |
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