JP2023155975A - Thermoplastic resin and molded product thereof - Google Patents
Thermoplastic resin and molded product thereof Download PDFInfo
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- JP2023155975A JP2023155975A JP2022065514A JP2022065514A JP2023155975A JP 2023155975 A JP2023155975 A JP 2023155975A JP 2022065514 A JP2022065514 A JP 2022065514A JP 2022065514 A JP2022065514 A JP 2022065514A JP 2023155975 A JP2023155975 A JP 2023155975A
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- Prior art keywords
- thermoplastic resin
- parts
- resin according
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- mol
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 7
- 125000002015 acyclic group Chemical group 0.000 claims abstract description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 230000004580 weight loss Effects 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000000243 solution Substances 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000004431 polycarbonate resin Substances 0.000 description 24
- 229920005668 polycarbonate resin Polymers 0.000 description 24
- -1 diol compounds Chemical class 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 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 15
- 238000011156 evaluation Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 4
- 101100256651 Homo sapiens SENP6 gene Proteins 0.000 description 4
- 101150038317 SSP1 gene Proteins 0.000 description 4
- 101100125020 Schizosaccharomyces pombe (strain 972 / ATCC 24843) pss1 gene Proteins 0.000 description 4
- 101100018019 Schizosaccharomyces pombe (strain 972 / ATCC 24843) ssc1 gene Proteins 0.000 description 4
- 102100023713 Sentrin-specific protease 6 Human genes 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 101100532584 Clostridium perfringens (strain 13 / Type A) sspC1 gene Proteins 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 101100095550 Homo sapiens SENP7 gene Proteins 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 101150098865 SSP2 gene Proteins 0.000 description 3
- 102100031406 Sentrin-specific protease 7 Human genes 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical class CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- BPZIYBJCZRUDEG-UHFFFAOYSA-N 2-[3-(1-hydroxy-2-methylpropan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropan-1-ol Chemical compound C1OC(C(C)(CO)C)OCC21COC(C(C)(C)CO)OC2 BPZIYBJCZRUDEG-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-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
- 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
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 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 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006210 cyclodehydration reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229960002479 isosorbide Drugs 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 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 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- GNBRZRRANUHHGT-UHFFFAOYSA-N 1-phenylcyclohexa-2,4-dien-1-ol Chemical compound C=1C=CC=CC=1C1(O)CC=CC=C1 GNBRZRRANUHHGT-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CRJRLBBFSRNKLY-UHFFFAOYSA-N 2,2-bis(3-methylbutyl)propane-1,3-diol Chemical compound CC(C)CCC(CO)(CO)CCC(C)C CRJRLBBFSRNKLY-UHFFFAOYSA-N 0.000 description 1
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 1
- MAQOZOILPAMFSW-UHFFFAOYSA-N 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=C(CC=3C(=CC=C(C)C=3)O)C=C(C)C=2)O)=C1 MAQOZOILPAMFSW-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- JVZZUPJFERSVRN-UHFFFAOYSA-N 2-methyl-2-propylpropane-1,3-diol Chemical compound CCCC(C)(CO)CO JVZZUPJFERSVRN-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- 229940061334 2-phenylphenol Drugs 0.000 description 1
- 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
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- ICYDRUIZSPKQOH-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)decyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCCCCCC)C1=CC=C(O)C=C1 ICYDRUIZSPKQOH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RQTDWDATSAVLOR-UHFFFAOYSA-N 4-[3,5-bis(4-hydroxyphenyl)phenyl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC(C=2C=CC(O)=CC=2)=CC(C=2C=CC(O)=CC=2)=C1 RQTDWDATSAVLOR-UHFFFAOYSA-N 0.000 description 1
- VBFBWEWFTAZDJG-UHFFFAOYSA-N 5-methyl-2-(2-methylpropyl)hexane-1,3-diol Chemical compound CC(C)CC(O)C(CO)CC(C)C VBFBWEWFTAZDJG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QYFACSDTKGXDDM-UHFFFAOYSA-N OC.OC.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1 Chemical compound OC.OC.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1 QYFACSDTKGXDDM-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
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- 239000013307 optical fiber Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
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- 238000002076 thermal analysis method Methods 0.000 description 1
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Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、耐熱性および低線膨張係数に優れる熱可塑性樹脂およびその成形品に関するものである。 The present invention relates to a thermoplastic resin having excellent heat resistance and a low coefficient of linear expansion, and a molded article thereof.
近年、光学用部品や自動車部品をはじめとする様々な分野において、種々の性能に優れた透明性樹脂が要求されている。従来、透明樹脂としてはポリカーボネート樹脂（以下、ＰＣと称する）、メタクリル樹脂などが知られており、成形品、フィルムなどの形態で電気電子部品、光学部品、自動車部品、機械部品などの広い分野で用いられている。一方で、これらの樹脂は線膨張係数が十分低いとは言えず、精密部品や大型の成形部品などの使用には用途が制限される場合があった。 In recent years, transparent resins with excellent performance have been required in various fields including optical parts and automobile parts. Conventionally, polycarbonate resin (hereinafter referred to as PC), methacrylic resin, etc. are known as transparent resins, and they are used in a wide range of fields such as electrical and electronic parts, optical parts, automobile parts, and mechanical parts in the form of molded products and films. It is used. On the other hand, these resins cannot be said to have sufficiently low coefficients of linear expansion, and their use in precision parts and large molded parts may be limited.
また、従来からＰＣの原料であるビスフェノールＡに代わるモノマーとしてスピログリコール（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）やその他スピロ環骨格を有するモノマーが提案されている（特許文献１～４）。しかしながら、本発明者らの検討によれば、スピログリコールなどこれまでに報告されている構造体は耐熱性や線膨張係数が既存のビスフェノールＡ由来ポリカーボネートに対し、十分優れているとは言えないことが見出された。更に、重合時に副生するフェノールが残存することで臭気の課題や熱加工時の不良原因となりうる。 In addition, spiroglycol (3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5, 5] undecane) and other monomers having a spiro ring skeleton have been proposed (Patent Documents 1 to 4). However, according to the studies of the present inventors, the structures reported so far such as spiroglycol cannot be said to be sufficiently superior in heat resistance and coefficient of linear expansion to existing bisphenol A-derived polycarbonates. was discovered. Furthermore, residual phenol produced as a by-product during polymerization may cause odor problems and defects during thermal processing.
したがってこれまでに耐熱性に優れ、十分に低い線膨張率を示す樹脂および成形体は未だ提供されていなかった。 Therefore, no resin or molded body has been provided that has excellent heat resistance and a sufficiently low coefficient of linear expansion.
本発明の目的は、耐熱性および低線膨張係数に優れる熱可塑性樹脂およびその成形品を提供することである。 An object of the present invention is to provide a thermoplastic resin having excellent heat resistance and a low coefficient of linear expansion, and a molded article thereof.
本発明者らは、鋭意検討を行った結果、繰り返し単位（１）～（３）のいずれかを含むことで、耐熱性および低線膨張係数に優れる熱可塑性樹脂およびその成形品が得られることを究明し、本発明に至った。
すなわち、本発明は、以下の通りである。
As a result of extensive studies, the present inventors have found that by including any of repeating units (1) to (3), thermoplastic resins and molded products thereof having excellent heat resistance and low coefficient of linear expansion can be obtained. We investigated this and arrived at the present invention.
That is, the present invention is as follows.
１．下記式（１）、下記式（２）および下記式（３）で表される繰り返し単位からなる群より選ばれる少なくとも１つの繰り返し単位を全繰り返し単位中１～１００モル％含む熱可塑性樹脂。 1. A thermoplastic resin containing 1 to 100 mol% of at least one repeating unit selected from the group consisting of repeating units represented by the following formula (1), the following formula (2), and the following formula (3) based on all repeating units.
（式中、Ｒ１～Ｒ４はそれぞれ独立に、水素原子、炭素原子数１～１０の非環状炭化水素基、炭素原子数３～１０の脂環式炭化水素基、メトキシ基またはエトキシ基を表す。） (In the formula, R 1 to R 4 each independently represent a hydrogen atom, an acyclic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, a methoxy group, or an ethoxy group. represent.)
２．ガラス転移温度が８０℃～２００℃である前項１記載の熱可塑性樹脂。
３．２０℃の塩化メチレン溶液で測定された比粘度が０．１５～１．５である前項１または２に記載の熱可塑性樹脂。
４．線膨張係数が７０×１０－６・℃－１以下である前項１～３のいずれかに記載の熱可塑性樹脂。
５．飽和吸水率が２．５％以下である前項１～４のいずれかに記載の熱可塑性樹脂。
６．５％重量減少温度が３４０℃以上である前項１～５のいずれかに記載の熱可塑性樹脂。
７．フェノール含有量が５００重量ｐｐｍ以下である前項１～６のいずれかに記載の熱可塑性樹脂。
８．前項１～７のいずれかに記載の熱可塑性樹脂を素材とする成形品。
９．前項１～７のいずれかに記載の熱可塑性樹脂を素材とするフィルム。
2. The thermoplastic resin according to item 1 above, which has a glass transition temperature of 80°C to 200°C.
3. The thermoplastic resin according to item 1 or 2 above, which has a specific viscosity of 0.15 to 1.5 as measured in a methylene chloride solution at 20°C.
4. The thermoplastic resin according to any one of items 1 to 3 above, which has a linear expansion coefficient of 70×10 −6 ·° C. −1 or less.
5. The thermoplastic resin according to any one of items 1 to 4 above, which has a saturated water absorption rate of 2.5% or less.
The thermoplastic resin according to any one of items 1 to 5 above, which has a 6.5% weight loss temperature of 340°C or higher.
7. 7. The thermoplastic resin according to any one of items 1 to 6 above, which has a phenol content of 500 ppm by weight or less.
8. A molded article made from the thermoplastic resin according to any one of items 1 to 7 above.
9. A film made from the thermoplastic resin according to any one of items 1 to 7 above.
本発明の熱可塑性樹脂は、特定の構造を有する前駆物質を基本単位として用いることで、耐熱性および線膨張係数に優れるなどの特性を有することが可能となった。そのため、その奏する工業的効果は格別である。 By using a precursor having a specific structure as a basic unit, the thermoplastic resin of the present invention can have properties such as excellent heat resistance and linear expansion coefficient. Therefore, its industrial effects are exceptional.
以下、本発明を詳細に説明する。 The present invention will be explained in detail below.
＜熱可塑性樹脂＞
本発明の熱可塑性樹脂は、下記式（１）、下記式（２）および下記式（３）で表される繰り返し単位からなる群より選ばれる少なくとも１つの繰り返し単位を全繰り返し単位中１～１００モル％含む熱可塑性樹脂である。下記式（１）、下記式（２）および下記式（３）で表される繰り返し単位からなる群より選ばれる少なくとも１つの繰り返し単位を全繰り返し単位中好ましくは５～１００モル％含み、より好ましくは１０～１００モル％含み、さらに好ましくは１５～１００モル％含み、特に好ましくは２０～１００モル％含み、もっとも好ましくは２５～１００モル％含む。
<Thermoplastic resin>
The thermoplastic resin of the present invention contains at least one repeating unit selected from the group consisting of repeating units represented by the following formula (1), the following formula (2), and the following formula (3) in 1 to 100 of all repeating units. It is a thermoplastic resin containing mol%. It preferably contains at least one repeating unit selected from the group consisting of repeating units represented by the following formula (1), the following formula (2) and the following formula (3) in an amount of 5 to 100 mol% of all repeating units, and more preferably contains 10 to 100 mol%, more preferably 15 to 100 mol%, particularly preferably 20 to 100 mol%, and most preferably 25 to 100 mol%.
（式中、Ｒ１～Ｒ４はそれぞれ独立に、水素原子、炭素原子数１～１０の非環状炭化水素基、炭素原子数３～１０の脂環式炭化水素基、メトキシ基またはエトキシ基を表す。） (In the formula, R 1 to R 4 each independently represent a hydrogen atom, an acyclic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, a methoxy group, or an ethoxy group. represent.)
（他の繰り返し単位）
本発明において、上記式（１）～（３）で表される繰り返し単位以外の共重合構成単位を構成する繰り返し単位として、各種ジオール化合物から誘導される繰り返し単位が挙げられる。
(other repeat units)
In the present invention, repeating units constituting copolymerized structural units other than the repeating units represented by formulas (1) to (3) above include repeating units derived from various diol compounds.
かかるジオール化合物としては、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く、国際公開第２００４／１１１１０６号パンフレット、国際公開第２０１１／０２１７２０号パンフレットに記載のジオール化合物やジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコールなどのオキシアルキレングリコール類が挙げられる。 Such diol compounds may be any of aliphatic diol compounds, alicyclic diol compounds, and aromatic dihydroxy compounds, such as diol compounds and diethylene glycol described in WO 2004/111106 pamphlet and WO 2011/021720 pamphlet. , oxyalkylene glycols such as triethylene glycol, tetraethylene glycol, and polyethylene glycol.
前記脂肪族ジオール化合物としては、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、１，６－ヘキサンジオール、１，８－オクタンジオール、１．９－ノナンジオール、１，１０－デカンジオール、１，１２－ドデカンジオール、２－メチル－１，３－プロパンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオール、２－ｎ－ブチル－２－エチル－１，３－プロパンジオール、２，２－ジエチル－１，３－プロパンジオール、２，４－ジエチル－１，５－ペンタンジオール、１，２－ヘキサングリコール、１，２－オクチルグリコール、２－エチル－１，３－ヘキサンジオール、２，３－ジイソブチル－１，３－プロパンジオール、２，２－ジイソアミル－１，３－プロパンジオール、２－メチル－２－プロピル－１，３－プロパンジオールなどが挙げられる。 Examples of the aliphatic diol compounds include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1.9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-n-butyl-2-ethyl- 1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, 1,2-octyl glycol, 2-ethyl -1,3-hexanediol, 2,3-diisobutyl-1,3-propanediol, 2,2-diisoamyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, etc. Can be mentioned.
前記脂環式ジオール化合物としては、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、アダマンタンジオール、ペンタシクロペンタ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、イソソルビドなどが挙げられる。 Examples of the alicyclic diol compounds include cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol, pentacyclopentadecane dimethanol, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4, Examples include 8,10-tetraoxaspiro[5.5]undecane and isosorbide.
前記芳香族ジヒドロキシ化合物としては、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（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、４，４’－ジヒドロキシ－３，３’－ジメチルジフェニルスルフィド、ビスフェノールＡ、２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパン（ビスフェノールＣ）、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（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）デカンなどが挙げられる。 Examples of the aromatic dihydroxy compound include α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene (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, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, bisphenol A, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (bisphenol AF), and 1,1-bis(4-hydroxyphenyl)decane.
上記式（１）～（３）で表される繰り返し単位以外の共重合単位を構成する繰り返し単位は、０～９９モル％含み、好ましくは０～９５モル％含み、より好ましくは０～９０モル％含み、さらに好ましくは０～８５モル％含み、特に好ましくは０～８０モル％含み、もっとも好ましくは０～７５モル％含む。 The repeating units constituting the copolymerized units other than the repeating units represented by the above formulas (1) to (3) contain 0 to 99 mol%, preferably 0 to 95 mol%, and more preferably 0 to 90 mol%. %, more preferably 0 to 85 mol %, particularly preferably 0 to 80 mol %, and most preferably 0 to 75 mol %.
（原料）
上記式（１）～（３）で表される繰り返し単位を誘導する原料となるジオール成分は、主として下記式（１－１）、（２－１）、（３－１）で表されるジオール成分である。
(material)
The diol components that serve as raw materials for inducing the repeating units represented by the above formulas (1) to (3) are mainly diols represented by the following formulas (1-1), (2-1), and (3-1). It is an ingredient.
（式中、Ｒ１～Ｒ４はそれぞれ独立に、水素原子、炭素原子数１～１０の非環状炭化水素基、炭素原子数３～１０の脂環式炭化水素基、メトキシ基またはエトキシ基を表す。）
前記式（１－１）、（２－１）、（３－１）で表されるジオールは、下記式（１－１―１）、（２－１－１）、（３－１－１）で表される構造物と、下記式（４）で表されるペンタエリスリトールを脱水環化反応させることによって得られる。
(In the formula, R 1 to R 4 each independently represent a hydrogen atom, an acyclic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, a methoxy group, or an ethoxy group. represent.)
The diols represented by the formulas (1-1), (2-1), and (3-1) are represented by the following formulas (1-1-1), (2-1-1), and (3-1-1). ) and pentaerythritol represented by the following formula (4) are subjected to a cyclodehydration reaction.
（式中、Ｒ１～Ｒ４はそれぞれ独立に、水素原子、炭素原子数１～１０の非環状炭化水素基、炭素原子数３～１０の脂環式炭化水素基、メトキシ基またはエトキシ基を表す。） (In the formula, R 1 to R 4 each independently represent a hydrogen atom, an acyclic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, a methoxy group, or an ethoxy group. represent.)
前記式（１－１―１）、（２－１－１）、（３－１－１）で表される構造物のうち、具体例としては下記式（１－１―ａ）、（１－１―ｂ）、（２－１－ａ）、（３－１－ａ）が挙げられる。特に入手性の観点から（１－１―ａ）または（２－１－ａ）を用いることが好ましい。 Among the structures represented by the above formulas (1-1-1), (2-1-1), and (3-1-1), specific examples include the following formulas (1-1-a) and (1 -1-b), (2-1-a), and (3-1-a). Particularly from the viewpoint of availability, it is preferable to use (1-1-a) or (2-1-a).
本発明の前記式（１－１）、（２－１）、（３－１）で表されるジオール化合物の純度は９５％以上であると好ましく、９７％以上であるとより好ましく、９８％以上であるとさらに好ましい。純度はガスクロマトグラフで測定される。 The purity of the diol compounds represented by formulas (1-1), (2-1), and (3-1) of the present invention is preferably 95% or more, more preferably 97% or more, and 98% or more. It is more preferable that it is above. Purity is determined by gas chromatography.
（ジオール化合物の製造方法）
本発明の前記式（１－１）、（２－１）、（３－１）で表されるジオール化合物は、前記式（１－１―１）、（２－１－１）、（３－１－１）で表される構造物と上記式（４）で表されるペンタエリスリトールとを酸触媒および溶媒の存在下、脱水環化反応させることで得られる。
(Method for producing diol compound)
The diol compounds represented by the formulas (1-1), (2-1), and (3-1) of the present invention are the diol compounds represented by the formulas (1-1-1), (2-1-1), and (3-1); It can be obtained by subjecting the structure represented by -1-1) and pentaerythritol represented by the above formula (4) to a cyclodehydration reaction in the presence of an acid catalyst and a solvent.
前記式（１－１）、（２－１）、（３－１）で表されるジオール化合物の製造方法において、前記式（１－１―１）、（２－１－１）、（３－１－１）で表される構造物の使用比率は、上記式（４）で表されるペンタエリスリトール１モルに対して１．８～２．４モルが好ましく、１．９～２．１モルがより好ましい。 In the method for producing a diol compound represented by the above formula (1-1), (2-1), (3-1), the above formula (1-1-1), (2-1-1), (3 The usage ratio of the structure represented by -1-1) is preferably 1.8 to 2.4 mol, and 1.9 to 2.1 mol to 1 mol of pentaerythritol represented by the above formula (4). Mole is more preferred.
酸触媒として、シュウ酸、酢酸、塩酸、硫酸、リン酸、ベンゼンスルホン酸、ｐ－トルエンスルホン酸、メタンスルホン酸、ヘテロポリ酸が挙げられ、ベンゼンスルホン酸、ｐ－トルエンスルホン酸、メタンスルホン酸が好ましく、ｐ－トルエンスルホン酸がより好ましい。 Examples of acid catalysts include oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, and heteropolyacid; Preferred is p-toluenesulfonic acid, more preferred.
本発明で使用する酸触媒の使用量は、ペンタエリスリトール１モルに対して、０．００１～１モルが好ましく、０．００５～０．１モルがより好ましく、０．０１～０．０５モルがさらに好ましい。 The amount of the acid catalyst used in the present invention is preferably 0.001 to 1 mol, more preferably 0.005 to 0.1 mol, and 0.01 to 0.05 mol per mol of pentaerythritol. More preferred.
溶媒として、ベンゼン、トルエン、キシレン、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン、テトラヒドロフラン、ジオキサン、ジメチルスルホキシドが挙げられ、トルエン、ジメチルホルムアミドが好ましい。これら溶媒は単独で使用しても良く、２種類以上を併用しても良い。 Examples of the solvent include benzene, toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, dioxane, and dimethylsulfoxide, with toluene and dimethylformamide being preferred. These solvents may be used alone or in combination of two or more.
溶媒の量は、ペンタエリスリトールに対して、１～１００重量倍であると好ましく、３～５０重量倍であるとより好ましく、５～２０重量倍であるとさらに好ましい。 The amount of the solvent is preferably 1 to 100 times the weight of pentaerythritol, more preferably 3 to 50 times, and even more preferably 5 to 20 times the weight.
ジオール化合物の製造方法において、反応器の上にディーンスターク装置を付け、副生する水を系外に除去することが好ましい。 In the method for producing a diol compound, it is preferable to attach a Dean-Stark device on top of the reactor to remove by-product water from the system.
ジオール化合物の製造方法において、脱水縮合反応の反応温度は６０～１５０℃が好ましく、８０～１３０℃がより好ましく、１００～１２０℃がさらに好ましい。 In the method for producing a diol compound, the reaction temperature for the dehydration condensation reaction is preferably 60 to 150°C, more preferably 80 to 130°C, and even more preferably 100 to 120°C.
反応は大気下でも実施することができるが、安全性や色相の観点から、窒素、アルゴンなどの不活性ガス雰囲気下で行うことが好ましい。反応はガスクロマトグラフィーや液体クロマトグラフィーなどの分析手段で追跡することができる。 Although the reaction can be carried out in the atmosphere, from the viewpoint of safety and hue, it is preferable to carry out the reaction in an atmosphere of an inert gas such as nitrogen or argon. The reaction can be followed by analytical means such as gas chromatography or liquid chromatography.
（共重合組成）
本発明の熱可塑性樹脂は、前記式（１）～（３）で表される繰り返し単位のいずれかを含み、熱可塑性樹脂全体の繰り返し単位に占めるモル比は１～１００モル％であり、５～１００モル％がより好ましく、１５～１００モル％がさらに好ましく、２０～１００モル％が特に好ましく、２５～１００モル％がもっとも好ましい。上記範囲内では、耐熱性、および低線膨張係数に優れ好ましい。
なお、熱可塑性樹脂全体の繰り返し単位に占める前記式（１）～（３）で表される繰り返し単位のモル％は、日本電子社製ＪＮＭ－ＡＬ４００のプロトンＮＭＲにて測定し算出する。
(Copolymer composition)
The thermoplastic resin of the present invention contains any of the repeating units represented by formulas (1) to (3) above, and the molar ratio of the repeating units in the entire thermoplastic resin is 1 to 100 mol%, and 5 It is more preferably from 15 to 100 mol%, even more preferably from 15 to 100 mol%, particularly preferably from 20 to 100 mol%, and most preferably from 25 to 100 mol%. Within the above range, it is preferable because it has excellent heat resistance and a low coefficient of linear expansion.
The mol% of the repeating units represented by formulas (1) to (3) in the repeating units of the entire thermoplastic resin is calculated by measuring with proton NMR of JNM-AL400 manufactured by JEOL.
（ガラス転移温度：Ｔｇ）
本発明の熱可塑性樹脂のガラス転移温度（Ｔｇ）は、好ましくは８０℃以上２００℃以下であり、より好ましくは１００℃以上１９５℃以下であり、さらに好ましくは１２０℃以上１９０℃以下であり、特に好ましくは１３０℃以上１９０℃以下であり、もっとも好ましくは１４０℃以上１９０℃以下である。Ｔｇが下限以上であると、成形品として使用した際に、耐熱性（耐熱安定性）が良好とであり好ましい。またＴｇが上限以下では、成形性が良好であり好ましい。ガラス転移温度（Ｔｇ）はティー・エイ・インスツルメント・ジャパン（株）製２９１０型ＤＳＣを使用し、昇温速度２０℃／ｍｉｎにて測定する。
(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the thermoplastic resin of the present invention is preferably 80°C or more and 200°C or less, more preferably 100°C or more and 195°C or less, and even more preferably 120°C or more and 190°C or less, Particularly preferably the temperature is 130°C or more and 190°C or less, most preferably 140°C or more and 190°C or less. When Tg is at least the lower limit, heat resistance (heat resistance stability) is good when used as a molded article, which is preferable. Moreover, when Tg is below the upper limit, moldability is good and it is preferable. The glass transition temperature (Tg) is measured using a 2910 DSC manufactured by TA Instruments Japan Co., Ltd. at a temperature increase rate of 20° C./min.
（５％重量減少温度）
本発明の熱可塑性樹脂の５％重量減少温度は、窒素雰囲気下で昇温速度２０℃／分での５％重量減少温度であり、３４０℃以上であることが好ましく、３４５℃以上であるとより好ましく、３５０℃以上であるとさらに好ましく、３７０℃以上であると特に好ましく、３８０℃以上であるともっとも好ましい。５％重量減少温度が上記下限以上であると耐熱性（耐熱安定性）が高くなる。
(5% weight loss temperature)
The 5% weight loss temperature of the thermoplastic resin of the present invention is the 5% weight loss temperature at a heating rate of 20°C/min in a nitrogen atmosphere, preferably 340°C or higher, and preferably 345°C or higher. The temperature is more preferably 350°C or higher, even more preferably 370°C or higher, and most preferably 380°C or higher. When the 5% weight loss temperature is equal to or higher than the above lower limit, heat resistance (heat resistance stability) becomes high.
（飽和吸水率）
本発明の熱可塑性樹脂の飽和吸水率は、好ましくは２．５％以下であり、より好ましくは２．０％以下である。吸水率が上記上限以下であると成形品において吸水による寸法変化や反りが低減でき好ましい。
(saturated water absorption rate)
The saturated water absorption rate of the thermoplastic resin of the present invention is preferably 2.5% or less, more preferably 2.0% or less. It is preferable that the water absorption rate is below the above upper limit because dimensional changes and warping due to water absorption can be reduced in the molded product.
（比粘度：ηＳＰ）
本発明の熱可塑性樹脂の比粘度（ηＳＰ）としては、０．１５以上１．５０以下であることが好ましい。より好ましくは０．２以上１．０以下であり、さらに好ましくは０．２５以上０．８以下であり、特に好ましくは０．３以上０．７以下である。比粘度が下限以上では強度等が向上し、上限以下では成形加工特性が優れる。
(Specific viscosity: ηSP )
The specific viscosity (η SP ) of the thermoplastic resin of the present invention is preferably 0.15 or more and 1.50 or less. More preferably, it is 0.2 or more and 1.0 or less, still more preferably 0.25 or more and 0.8 or less, particularly preferably 0.3 or more and 0.7 or less. When the specific viscosity is above the lower limit, strength etc. are improved, and when the specific viscosity is below the upper limit, the molding properties are excellent.
本発明でいう比粘度は、２０℃で塩化メチレン１００ｍｌに熱可塑性樹脂０．７ｇを溶解した溶液からオストワルド粘度計を用いて求めた。
比粘度（ηＳＰ）＝（ｔ－ｔ０）／ｔ０
［ｔ０は塩化メチレンの落下秒数、ｔは試料溶液の落下秒数］
なお、本発明の熱可塑性樹脂の比粘度を測定する場合は、次の要領で行うことができる。すなわち、熱可塑性樹脂をその２０～３０倍重量の塩化メチレンに溶解し、可溶分をセライト濾過により採取した後、溶液を除去して十分に乾燥し、塩化メチレン可溶分の固体を得る。かかる固体０．７ｇを塩化メチレン１００ｍｌに溶解した溶液から２０℃における比粘度をオストワルド粘度計を用いて求める。
The specific viscosity as used in the present invention was determined from a solution of 0.7 g of thermoplastic resin dissolved in 100 ml of methylene chloride at 20° C. using an Ostwald viscometer.
Specific viscosity (η SP )=(t−t 0 )/t 0
[ t0 is the number of seconds that methylene chloride falls, t is the number of seconds that the sample solution falls]
In addition, when measuring the specific viscosity of the thermoplastic resin of the present invention, it can be performed in the following manner. That is, the thermoplastic resin is dissolved in methylene chloride 20 to 30 times its weight, and the soluble content is collected by filtration through Celite, and the solution is removed and thoroughly dried to obtain a solid of the methylene chloride soluble content. The specific viscosity at 20° C. of a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride is determined using an Ostwald viscometer.
（線膨張係数）
本発明で使用される熱可塑性樹脂は、３０℃～７０℃における線膨張係数の平均値が好ましくは７０×１０－６・℃－１以下であり、より好ましくは６５×１０－６・℃－１以下、さらに好ましくは６０×１０－６・℃－１以下である。上記上限を超えるものはビスフェノールＡから誘導される通常のポリカーボネート樹脂の線膨張係数に対する優位性を有さなくなる場合がある。
線膨張係数を低下させるメカニズムは詳細には解明されていないが、本発明の熱可塑性樹脂を構成する前記式（１）～（３）で表される繰り返し単位の特異な構造に起因するものと考えられ、その比率が多くなるほど線膨張係数は低くなる。
(linear expansion coefficient)
The thermoplastic resin used in the present invention preferably has an average linear expansion coefficient of 70×10 -6 ·°C -1 or less at 30°C to 70°C, more preferably 65×10 -6 ·°C - 1 or less, more preferably 60×10 −6 ·°C −1 or less. If it exceeds the above upper limit, it may not have superiority over the linear expansion coefficient of ordinary polycarbonate resins derived from bisphenol A.
Although the mechanism of decreasing the linear expansion coefficient has not been elucidated in detail, it is thought to be due to the unique structure of the repeating units represented by formulas (1) to (3) above that constitute the thermoplastic resin of the present invention. The higher the ratio, the lower the coefficient of linear expansion becomes.
（フェノール含有量）
本発明の熱可塑性樹脂中のフェノールの含有量は、５００重量ｐｐｍ以下であることが好ましく、４００重量ｐｐｍ以下であることがより好ましく、３００重量ｐｐｍ以下であることがさらに好ましい。フェノールの含有量を低減することにより、後の工程において臭気を抑制でき、また成形時の不良発生率を抑制できる。
(phenol content)
The content of phenol in the thermoplastic resin of the present invention is preferably at most 500 ppm by weight, more preferably at most 400 ppm by weight, even more preferably at most 300 ppm by weight. By reducing the content of phenol, it is possible to suppress odor in subsequent steps and also to suppress the incidence of defects during molding.
（熱可塑性樹脂の製造方法）
本発明における熱可塑性樹脂は、前記ジオール化合物とカーボネート前駆体とを反応させて得られるものである。反応の方法としては界面重縮合法、溶融エステル交換法、カーボネートプレポリマーの固相エステル交換法、および環状カーボネート化合物の開環重合法などを挙げることができる。界面重縮合の場合は通常一価フェノール類の末端停止剤が使用される。
(Method for manufacturing thermoplastic resin)
The thermoplastic resin in the present invention is obtained by reacting the diol compound and a carbonate precursor. Examples of reaction methods include interfacial polycondensation, melt transesterification, solid phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds. In the case of interfacial polycondensation, a terminal capping agent of monohydric phenols is usually used.
本発明における熱可塑性樹脂はカーボネート構造を有する。カーボネート構造を有するポリカーボネート樹脂は、芳香族または脂肪族（脂環式を含む）の二官能性カルボン酸を共重合したポリエステルカーボネートを含む。脂肪族の二官能性のカルボン酸は、α，ω－ジカルボン酸が好ましい。脂肪族の二官能性のカルボン酸としては例えば、セバシン酸（デカン二酸）、ドデカン二酸、テトラデカン二酸、オクタデカン二酸、およびイコサン二酸などの直鎖飽和脂肪族ジカルボン酸、並びにシクロヘキサンジカルボン酸などの脂環式ジカルボン酸が好ましく挙げられる。これらのカルボン酸は、目的を阻害しない範囲で共重合してもよい。また、ポリカーボネート樹脂は、必要に応じてポリオルガノシロキサン単位を含有する構成単位を共重合することもできる。 The thermoplastic resin in the present invention has a carbonate structure. The polycarbonate resin having a carbonate structure includes a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. The aliphatic difunctional carboxylic acid is preferably α,ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid, and cyclohexanedicarboxylic acid. Preferred examples include alicyclic dicarboxylic acids such as acids. These carboxylic acids may be copolymerized to the extent that the purpose is not impaired. Moreover, the polycarbonate resin can also be copolymerized with a structural unit containing a polyorganosiloxane unit, if necessary.
ポリカーボネート樹脂は、必要に応じて三官能以上の多官能性芳香族化合物を含有する構成単位を、共重合し、分岐ポリカーボネート樹脂とすることもできる。 The polycarbonate resin can also be made into a branched polycarbonate resin by copolymerizing a structural unit containing a trifunctional or higher polyfunctional aromatic compound, if necessary.
分岐ポリカーボネート樹脂に使用される三官能以上の多官能性芳香族化合物としては、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、２，４，６－トリメチル－２，４，６－トリス（４－ヒドロキシフェニル）ヘプタン、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（３，５－ジメチル－４－ヒドロキシフェニル）エタン、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、および４－｛４－［１，１－ビス（４－ヒドロキシフェニル）エチル］ベンゼン｝－α，α－ジメチルベンジルフェノール等のトリスフェノールが好適に例示される。中でも１，１，１－トリス（４－ヒドロキシフェニル）エタンが好ましい。かかる多官能性芳香族化合物から誘導される構成単位は、他の二価フェノール成分からの構成単位との合計１００モル％中、好ましくは０．０３～１．５モル％、より好ましくは０．１～１．２モル％、特に好ましくは０．２～１．０モル％である。 As the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl -2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1, 1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and 4-{4-[1,1-bis Preferred examples include trisphenol such as (4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The structural unit derived from such a polyfunctional aromatic compound preferably accounts for 0.03 to 1.5 mol%, more preferably 0.03 to 1.5 mol% of the total 100 mol% of the structural unit derived from other dihydric phenol components. The amount is 1 to 1.2 mol%, particularly preferably 0.2 to 1.0 mol%.
また分岐構造単位は、多官能性芳香族化合物から誘導されるだけでなく、溶融エステル交換法による重合反応時に生じる副反応の如き、多官能性芳香族化合物を用いることなく誘導されるものであってもよい。尚、かかる分岐構造の割合については１Ｈ－ＮＭＲ測定により算出することが可能である。 Furthermore, the branched structural unit is not only derived from a polyfunctional aromatic compound, but also derived without using a polyfunctional aromatic compound, such as a side reaction that occurs during a polymerization reaction by melt transesterification. It's okay. Note that the proportion of such branched structures can be calculated by 1H-NMR measurement.
カーボネート前駆物質として例えばホスゲンを使用する反応では、通常酸結合剤および溶媒の存在下に反応を行う。酸結合剤としては例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物またはピリジン等のアミン化合物が用いられる。溶媒としては例えば塩化メチレン、クロロベンゼン等のハロゲン化炭化水素が用いられる。また反応促進のために例えば第三級アミンまたは第四級アンモニウム塩等の触媒を用いることもできる。その際、反応温度は通常０～４０℃であり、反応時間は数分～５時間である。 In reactions using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or amine compounds such as pyridine are used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used to promote the reaction. At this time, the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.
カーボネート前駆物質として例えば炭酸ジエステルを用いるエステル交換反応は、不活性ガス雰囲気下所定割合の芳香族ジヒドロキシ成分を炭酸ジエステルと加熱しながら撹拌して、生成するアルコールまたはフェノール類を留出させる方法により行われる。反応温度は生成するアルコールまたはフェノール類の沸点等により異なるが、通常１２０～３００℃の範囲である。反応はその初期から減圧にして生成するアルコールまたはフェノール類を留出させながら反応を完結させる。また反応を促進するために通常エステル交換反応に使用される触媒を使用することもできる。前記エステル交換反応に使用される炭酸ジエステルとしては、例えばジフェニルカーボネート、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等が挙げられる。これらのうち特にジフェニルカーボネートが好ましい。 A transesterification reaction using, for example, a carbonic acid diester as a carbonate precursor is carried out by stirring a predetermined proportion of an aromatic dihydroxy component with a carbonic diester under an inert gas atmosphere while heating, and distilling off the alcohol or phenol produced. be exposed. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300°C. The reaction is completed under reduced pressure from the initial stage while distilling out the alcohol or phenol produced. Further, in order to promote the reaction, catalysts commonly used in transesterification reactions can also be used. Examples of the diester carbonate used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among these, diphenyl carbonate is particularly preferred.
末端停止剤として通常使用される単官能フェノール類を使用することができる。殊にカーボネート前駆物質としてホスゲンを使用する反応の場合、単官能フェノール類は末端停止剤として分子量調節のために一般的に使用され、また得られたポリカーボネート樹脂は、末端が単官能フェノール類に基づく基によって封鎖されているので、そうでないものと比べて熱安定性に優れている。前記単官能フェノール類の具体例としては、例えばフェノール、ｍ－メチルフェノール、ｐ－メチルフェノール、ｍ－プロピルフェノール、ｐ－プロピルフェノール、１－フェニルフェノール、２－フェニルフェノール、ｐ－ｔｅｒｔ－ブチルフェノール、ｐ－クミルフェノール、イソオクチルフェノール、ｐ－長鎖アルキルフェノール等が挙げられる。 Monofunctional phenols commonly used as terminal capping agents can be used. Particularly in the case of reactions using phosgene as carbonate precursor, monofunctional phenols are commonly used as end-stoppers for molecular weight control, and the resulting polycarbonate resins have terminals based on monofunctional phenols. Since it is blocked by a group, it has superior thermal stability compared to those that are not blocked. Specific examples of the monofunctional phenols include phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, Examples include p-cumylphenol, isooctylphenol, and p-long chain alkylphenol.
（添加剤、他の樹脂）
本発明の熱可塑性樹脂には、本発明の効果を損なわない範囲で通常使用される添加剤を配合することができる。また、他の樹脂と併用して使用することもできる。
(additives, other resins)
The thermoplastic resin of the present invention may contain commonly used additives within a range that does not impair the effects of the present invention. Moreover, it can also be used in combination with other resins.
＜成形品＞
本発明の熱可塑性樹脂を用いてなる成形品は、例えば射出成形法、圧縮成形法、押出成形法、溶液キャスティング法など任意の方法により成形される。本発明のポリカーボネート樹脂は、成形性および耐熱性に優れているので種々の成形品として利用することができる。殊に光学レンズ、光学ディスク、液晶パネル、光カード、シート、フィルム、光ファイバー、コネクター、蒸着プラスチック反射鏡、ディスプレイなどの光学部品の構造材料、パソコンや携帯電話の外装や前面板などの電気電子部品、自動車のヘッドランプや窓などの自動車用途、または機能材料用途に適した成形品として有利に使用することができる。
<Molded product>
A molded article using the thermoplastic resin of the present invention can be molded by any method such as an injection molding method, a compression molding method, an extrusion molding method, or a solution casting method. Since the polycarbonate resin of the present invention has excellent moldability and heat resistance, it can be used as various molded products. In particular, structural materials for optical components such as optical lenses, optical disks, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, and displays, and electrical and electronic components such as the exteriors and front panels of computers and mobile phones. It can be advantageously used as a molded product suitable for automotive applications such as automobile headlamps and windows, or functional material applications.
＜フィルム＞
本発明の熱可塑性樹脂を用いてなるフィルムは、具体的には、表面保護フィルム、加飾用フィルム、前面板、位相差フィルム、プラセル基板フィルム、偏光板保護フィルム、反射防止フィルム、輝度上昇フィルム、光ディスクの保護フィルム、拡散フィルム等の用途が挙げられる。
<Film>
Specifically, the film made using the thermoplastic resin of the present invention includes a surface protection film, a decorative film, a front plate, a retardation film, a plastic substrate film, a polarizing plate protective film, an antireflection film, and a brightness enhancement film. Applications include protective films for optical discs, diffusion films, etc.
フィルムの製造方法としては、例えば、溶液キャスト法、溶融押出法、熱プレス法、カレンダー法等公知の方法を挙げることが出来る。なかでも、溶液キャスト法、溶融押出法が好ましく、特に生産性の点から溶融押出法が好ましい。 Examples of the film manufacturing method include known methods such as solution casting, melt extrusion, hot pressing, and calendering. Among these, the solution casting method and the melt extrusion method are preferred, and the melt extrusion method is particularly preferred from the viewpoint of productivity.
溶融押出法においては、Ｔダイを用いて樹脂を押出し、冷却ロールに送る方法が好ましく用いられる。このときの温度は熱可塑性樹脂の分子量、Ｔｇ、溶融流動特性等から決められるが、１８０～３５０℃の範囲であり、２００℃～３２０℃の範囲がより好ましい。１８０℃より低いと粘度が高くなりポリマーの配向、応力歪みが残りやすく好ましくない。また、３５０℃より高いと熱劣化、着色、Ｔダイからのダイライン（筋）等の問題が起きやすい。 In the melt extrusion method, a method in which the resin is extruded using a T-die and sent to a cooling roll is preferably used. The temperature at this time is determined based on the molecular weight, Tg, melt flow characteristics, etc. of the thermoplastic resin, but is in the range of 180 to 350°C, more preferably in the range of 200 to 320°C. If the temperature is lower than 180° C., the viscosity becomes high and polymer orientation and stress distortion tend to remain, which is not preferable. Furthermore, if the temperature is higher than 350° C., problems such as thermal deterioration, coloring, and die lines from the T-die are likely to occur.
また、本発明の熱可塑性樹脂は、有機溶媒に対する溶解性が良好なので、溶液キャスト法も適用することが出来る。溶液キャスト法の場合は、溶媒としては塩化メチレン、１，２－ジクロロエタン、１，１，２，２－テトラクロロエタン、ジオキソラン、ジオキサン等が好適に用いられる。溶液キャスト法で獲られるフィルム中の残留溶媒量は２重量％以下であることが好ましく、より好ましくは１重量％以下である。残留溶媒量が２重量％を超えるとフィルムのガラス転移温度の低下が著しくなり耐熱性の点で好ましくない。
本発明の熱可塑性樹脂を用いてなる未延伸フィルムの厚みとしては、３０～４００μｍの範囲が好ましく、より好ましくは４０～３００μｍの範囲である。
Further, since the thermoplastic resin of the present invention has good solubility in organic solvents, a solution casting method can also be applied. In the case of the solution casting method, methylene chloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dioxolane, dioxane, etc. are preferably used as the solvent. The amount of residual solvent in the film obtained by the solution casting method is preferably 2% by weight or less, more preferably 1% by weight or less. If the amount of residual solvent exceeds 2% by weight, the glass transition temperature of the film will drop significantly, which is undesirable from the viewpoint of heat resistance.
The thickness of the unstretched film made using the thermoplastic resin of the present invention is preferably in the range of 30 to 400 μm, more preferably in the range of 40 to 300 μm.
以下実施例により本発明を詳細に説明するが、本発明はこれに限定されるものではない。なお、実施例中「部」とは「重量部」を意味する。実施例において使用した樹脂および評価方法は以下のとおりである。 The present invention will be explained in detail below with reference to Examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by weight." The resins and evaluation methods used in the examples are as follows.
１．ポリマー組成比（ＮＭＲ）
日本電子社製ＪＮＭ－ＡＬ４００のプロトンＮＭＲにて測定し、ポリマー組成比（モル比）を算出した。
1. Polymer composition ratio (NMR)
The polymer composition ratio (molar ratio) was calculated by measuring with proton NMR using JNM-AL400 manufactured by JEOL.
２．比粘度測定
２０℃で塩化メチレン１００ｍｌにポリカーボネート樹脂０．７ｇを溶解した溶液からオストワルド粘度計を用いて求めた。
比粘度（ηＳＰ）＝（ｔ－ｔ０）／ｔ０
［ｔ０は塩化メチレンの落下秒数、ｔは試料溶液の落下秒数］
2. Specific viscosity measurement It was determined using an Ostwald viscometer from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C.
Specific viscosity (η SP )=(t−t 0 )/t 0
[ t0 is the number of seconds that methylene chloride falls, t is the number of seconds that the sample solution falls]
３．ガラス転移温度測定
ポリカーボネート樹脂８ｍｇを用いてティー・エイ・インスツルメント（株）製の熱分析システム ＤＳＣ－２９１０を使用して、ＪＩＳ Ｋ７１２１に準拠して窒素雰囲気下（窒素流量：４０ｍｌ／ｍｉｎ）、昇温速度：２０℃／ｍｉｎの条件下で測定した。
3. Glass transition temperature measurement: Using 8 mg of polycarbonate resin, thermal analysis system DSC-2910 manufactured by TA Instruments was used under nitrogen atmosphere (nitrogen flow rate: 40 ml/min) in accordance with JIS K7121. The temperature was measured under the following conditions: temperature increase rate: 20° C./min.
４．５％重量減少温度
得られたポリカーボネート樹脂をＴＡインスツルメント製の示差熱・熱重量同時測定装置Ｄｉｓｃｏｖｅｒｙ ＳＤＴ６５０により、窒素雰囲気下で、昇温速度２０℃／ｍｉｎで測定し、５％重量減少温度を測定した。試料は５ｍｇ程度で測定した。
4.5% Weight Loss Temperature The obtained polycarbonate resin was measured at a heating rate of 20°C/min in a nitrogen atmosphere using a differential thermal/thermogravimetric simultaneous measuring device Discovery SDT650 manufactured by TA Instruments, and the weight loss was 5%. The decreasing temperature was measured. The sample was measured at approximately 5 mg.
５．飽和吸水率
吸水率は、ポリカーボネート樹脂パウダーまたはペレットを塩化メチレンに溶解後、塩化メチレンを蒸発させて得られた厚み２００μｍのキャストフィルムを用い、２３℃水中に浸漬させ重量変化が飽和した後の重量増加分を測定し、次式によって吸水率を求めた。
飽和吸水率（％）＝｛（吸水後の樹脂重量－吸水前の樹脂重量）／吸水後の樹脂重量｝×１００
5. Saturated water absorption rate Water absorption rate is the weight after dissolving polycarbonate resin powder or pellets in methylene chloride, then evaporating the methylene chloride, using a cast film with a thickness of 200 μm, and immersing it in water at 23°C until the weight change is saturated. The increase was measured, and the water absorption rate was determined using the following formula.
Saturated water absorption rate (%) = {(Resin weight after water absorption - Resin weight before water absorption) / Resin weight after water absorption} x 100
６．線膨張係数
ポリカーボネート樹脂パウダーまたはペレットを塩化メチレンに溶解後、塩化メチレンを蒸発させて得られた厚み２００μｍのキャストフィルムを用い、ＴＡインスツルメント社製 ＴＭＡ Ｑ４００にて、３０から７０℃の線膨張係数を測定し、その平均値を算出した。
6. Linear expansion coefficient: Dissolve polycarbonate resin powder or pellets in methylene chloride, then evaporate the methylene chloride. Using a cast film with a thickness of 200 μm, linear expansion was performed at 30 to 70°C using TMA Q400 manufactured by TA Instruments. The coefficients were measured and their average values were calculated.
７．フェノール含有量
ポリカーボネート樹脂パウダーまたはペレット１．５ｇを塩化メチレン１５ｍｌに溶解させた後、アセトニトリル１３５ｍｌを加え攪拌し、エバポレーターで濃縮した後、０．２μｍフィルターでろ過し、この測定溶液１０μｌを野村化学製Ｄｅｖｅｌｏｓｉｌ ＯＤＳ－７のカラムにて溶離液アセトニトリル／０．２％酢酸水とアセトニトリルとの混合液を用いて、カラム温度３０℃、検出器２７７ｎｍでグラジエントプログラムにてＨＰＬＣ分析した。
7. Phenol content After dissolving 1.5 g of polycarbonate resin powder or pellets in 15 ml of methylene chloride, 135 ml of acetonitrile was added and stirred, concentrated with an evaporator, filtered with a 0.2 μm filter, and 10 μl of this measurement solution was dissolved in 15 ml of methylene chloride. HPLC analysis was performed using a Develosil ODS-7 column using a mixture of acetonitrile/0.2% acetic acid and acetonitrile as an eluent, a column temperature of 30° C., and a gradient program at a detector of 277 nm.
［合成例１］
＜３，９－ビス（４－ヒドロキシ－３－メトキシフェニル）－２，４，８，１０，－テトラオキサスピロ［５．５］ウンデカンの合成＞
窒素雰囲気下、撹拌機、冷却器、ディーンスターク管、温度計を備え付けたフラスコにペンタエリスリトール、１２．５０ｇ、バニリン２７．９４ｇ、ｐ－トルエンスルホン酸１水和物０．７０ｇ、トルエン１４６ｇ、ジメチルホルムアミド１４．６ｇを仕込み、１１０℃で６時間反応した。反応終了後、反応液に酢酸エチル５００ｍｌを加え希釈した後、分液ロートへ移し、蒸留水で５回分液水洗した。分液水洗後の有機層を濃縮した後、トルエン４００ｍｌを加え９５℃で加熱溶解後、冷却すると結晶が析出し始めた。そのまま室温まで冷却後、析出した結晶を回収し、９０℃で２時間真空乾燥し、３，９－ビス（４－ヒドロキシ－３－メトキシフェニル）－２，４，８，１０，－テトラオキサスピロ［５．５］ウンデカン（以下、ＳＳＰ１と略す）の結晶を２９ｇ得た（収率：７９％）。この結晶の純度は９９．５２％であった。
[Synthesis example 1]
<Synthesis of 3,9-bis(4-hydroxy-3-methoxyphenyl)-2,4,8,10,-tetraoxaspiro[5.5]undecane>
Under a nitrogen atmosphere, 12.50 g of pentaerythritol, 27.94 g of vanillin, 0.70 g of p-toluenesulfonic acid monohydrate, 146 g of toluene, and dimethyl were placed in a flask equipped with a stirrer, condenser, Dean-Stark tube, and thermometer. 14.6 g of formamide was charged and reacted at 110° C. for 6 hours. After the reaction was completed, the reaction solution was diluted with 500 ml of ethyl acetate, transferred to a separating funnel, and washed five times with distilled water. After concentrating the organic layer after separating and washing with water, 400 ml of toluene was added and dissolved by heating at 95°C. When the mixture was cooled, crystals began to precipitate. After cooling to room temperature, the precipitated crystals were collected and dried under vacuum at 90°C for 2 hours to give 3,9-bis(4-hydroxy-3-methoxyphenyl)-2,4,8,10,-tetraoxaspiro. [5.5] 29 g of crystals of undecane (hereinafter abbreviated as SSP1) were obtained (yield: 79%). The purity of this crystal was 99.52%.
［合成例２］
＜３，９－ビス（３－ヒドロキシフェニル）－２，４，８，１０，－テトラオキサスピロ［５．５］ウンデカンの合成＞
窒素雰囲気下、撹拌機、冷却器、ディーンスターク管、温度計を備え付けたフラスコにペンタエリスリトール、１２．５０ｇ、３－ヒドロキシベンズアルデヒド２３．５２ｇ、ｐ－トルエンスルホン酸１水和物０．７０ｇ、トルエン１４６ｇ、ジメチルホルムアミド１４．６ｇを仕込み、１１０℃で６時間反応した。反応終了後、反応液に酢酸エチル５００ｍｌを加え希釈した後、分液ロートへ移し、蒸留水で５回分液水洗した。分液水洗後の有機層を濃縮した後、トルエン４００ｍｌを加え９５℃で加熱溶解後、冷却すると結晶が析出し始めた。そのまま室温まで冷却後、析出した結晶を回収し、９０℃で２時間真空乾燥し、３，９－ビス（３－ヒドロキシフェニル）－２，４，８，１０，－テトラオキサスピロ［５．５］ウンデカン（以下、ＳＳＰ２と略す）の結晶を３０ｇ得た（収率：７５％）。この結晶の純度は９９．１１％であった。
[Synthesis example 2]
<Synthesis of 3,9-bis(3-hydroxyphenyl)-2,4,8,10,-tetraoxaspiro[5.5]undecane>
Under a nitrogen atmosphere, 12.50 g of pentaerythritol, 23.52 g of 3-hydroxybenzaldehyde, 0.70 g of p-toluenesulfonic acid monohydrate, and toluene were placed in a flask equipped with a stirrer, condenser, Dean-Stark tube, and thermometer. 146g of dimethylformamide and 14.6g of dimethylformamide were charged, and the mixture was reacted at 110°C for 6 hours. After the reaction was completed, the reaction solution was diluted with 500 ml of ethyl acetate, transferred to a separating funnel, and washed five times with distilled water. After concentrating the organic layer after separating and washing with water, 400 ml of toluene was added and dissolved by heating at 95°C. When the mixture was cooled, crystals began to precipitate. After cooling to room temperature, the precipitated crystals were collected and vacuum dried at 90°C for 2 hours to give 3,9-bis(3-hydroxyphenyl)-2,4,8,10,-tetraoxaspiro[5.5 ] 30 g of crystals of undecane (hereinafter abbreviated as SSP2) were obtained (yield: 75%). The purity of this crystal was 99.11%.
［純度測定：ガスクロマトグラフ測定（ＧＣ／ＭＳ）］
アジレント・テクノロジー製シングル四重極ＧＣ／ＭＳ ５９７７Ｂを用い、下記測定条件で測定した。実施例中、特に断らない限り純度（％）はＧＣ／ＭＳにおける溶媒を除いて補正した面積百分率値である。
（ＧＣ）
カラム：ＤＢ－１（内径０．２５ｍｍ、長さ３０ｍ、膜厚０．２５μｍ）
注入量：１μｌ
注入法：スプリット比４０：１
注入口温度：２８０℃
オーブン：６０℃－１０℃／分－２８０℃（２８分）
キャリアガス：Ｈｅ、線速度 ３６．６ｃｍ／ｓ
（ＭＳ）
イオン源温度：２３０℃
イオン化モード：ＥＩ ７０ｅＶ
測定範囲：ｍ／ｚ ３３－７００
[Purity measurement: gas chromatography measurement (GC/MS)]
Measurement was performed using a single quadrupole GC/MS 5977B manufactured by Agilent Technologies under the following measurement conditions. In the examples, unless otherwise specified, purity (%) is an area percentage value corrected by excluding the solvent in GC/MS.
(GC)
Column: DB-1 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)
Injection volume: 1μl
Injection method: split ratio 40:1
Inlet temperature: 280℃
Oven: 60℃ - 10℃/min - 280℃ (28 minutes)
Carrier gas: He, linear velocity 36.6 cm/s
(MS)
Ion source temperature: 230℃
Ionization mode: EI 70eV
Measurement range: m/z 33-700
［実施例１］
＜熱可塑性樹脂の製造＞
温度計、撹拌機、還流冷却器付き反応器にイオン交換水１５２部、２５％水酸化ナトリウム水溶液４７部を入れ、二価フェノールとして合成例１で合成したＳＳＰ１ ３４部、およびハイドロサルファイト０．０７部を溶解した後、塩化メチレン８６部を加え、撹拌下１６～２４℃でホスゲン１１部を７０分要して吹き込んだ。その後、２５％水酸化ナトリウム水溶液７部を加え、さらにｐ－ｔｅｒｔ－ブチルフェノール０．４部を塩化メチレンに溶解した溶液を加え、攪拌させて乳化状態とした。かかる攪拌下、反応液が２８℃の状態でトリエチルアミン０．０２部を加えた後、温度２６～３１℃において１時間撹拌を続けたところで反応を終了した。反応終了後有機相を分離し、塩化メチレンで希釈してイオン交換水で水洗を繰り返し、洗浄液が中性になったところで塩酸酸性水にて水洗した。その後、イオン交換水で繰り返し洗浄し水相の導電率がイオン交換水と殆ど同じになったところで温水を張ったニーダーに投入して、攪拌しながら溶媒を蒸発させ、ポリカーボネート樹脂のパウダーを得た。脱水後、熱風循環式乾燥機により１００℃で１２時間乾燥した。得られたパウダーを用いて、前記の方法で各種評価を実施しその結果を表１に示した。
[Example 1]
<Manufacture of thermoplastic resin>
152 parts of ion-exchanged water and 47 parts of a 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and 34 parts of SSP1 synthesized in Synthesis Example 1 as dihydric phenol and 0.0 parts of hydrosulfite were added. After dissolving 07 parts of methylene chloride, 86 parts of methylene chloride were added, and 11 parts of phosgene was blown into the solution at 16 to 24° C. over 70 minutes while stirring. Thereafter, 7 parts of a 25% aqueous sodium hydroxide solution was added, and then a solution of 0.4 part of p-tert-butylphenol dissolved in methylene chloride was added and stirred to form an emulsified state. Under such stirring, 0.02 part of triethylamine was added to the reaction solution at 28°C, and stirring was continued for 1 hour at a temperature of 26 to 31°C, at which point the reaction was completed. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and washed repeatedly with ion-exchanged water. When the washing solution became neutral, it was washed with hydrochloric acid acid water. After that, it was washed repeatedly with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, it was poured into a kneader filled with warm water, and the solvent was evaporated while stirring to obtain a polycarbonate resin powder. . After dehydration, it was dried at 100° C. for 12 hours using a hot air circulation dryer. Using the obtained powder, various evaluations were carried out using the methods described above, and the results are shown in Table 1.
［実施例２］
＜熱可塑性樹脂の製造＞
ＳＳＰ１ １７部、ビスフェノールＡ（以下、ＢＰＡと略す）１０部を原料として用いた他は、実施例１と全く同様の操作を行いポリカーボネート樹脂のパウダーを得、実施例１と同様の評価を行った。その結果を表１に記載した。
[Example 2]
<Manufacture of thermoplastic resin>
Except that 17 parts of SSP1 and 10 parts of bisphenol A (hereinafter abbreviated as BPA) were used as raw materials, the same operation as in Example 1 was performed to obtain a polycarbonate resin powder, and the same evaluation as in Example 1 was performed. . The results are listed in Table 1.
［実施例３］
＜熱可塑性樹脂の製造＞
ＳＳＰ１ １０部、ＢＰＡ１３部を原料として用いた他は、実施例１と全く同様の操作を行いポリカーボネート樹脂のパウダーを得、実施例１と同様の評価を行った。その結果を表１に記載した。
[Example 3]
<Manufacture of thermoplastic resin>
Except for using 10 parts of SSP1 and 13 parts of BPA as raw materials, the same operation as in Example 1 was performed to obtain a polycarbonate resin powder, and the same evaluation as in Example 1 was performed. The results are listed in Table 1.
［実施例４］
＜熱可塑性樹脂の製造＞
温度計、撹拌機、還流冷却器付き反応器にイオン交換水１５２部、２５％水酸化ナトリウム水溶液４７部を入れ、二価フェノールとして合成例１で合成したＳＳＰ２ １３部、ＢＰＡ９部およびハイドロサルファイト０．０４部を溶解した後、塩化メチレン７９部を加え、撹拌下１６～２４℃でホスゲン１０部を７０分要して吹き込んだ。その後、２５％水酸化ナトリウム水溶液６部を加え、さらにｐ－ｔｅｒｔ－ブチルフェノール０．４部を塩化メチレンに溶解した溶液を加え、攪拌させて乳化状態とした。かかる攪拌下、反応液が２８℃の状態でトリエチルアミン０．０２部を加えた後、温度２６～３１℃において１時間撹拌を続けたところで反応を終了した。反応終了後有機相を分離し、塩化メチレンで希釈してイオン交換水で水洗を繰り返し、洗浄液が中性になったところで塩酸酸性水にて水洗した。その後、イオン交換水で繰り返し洗浄し水相の導電率がイオン交換水と殆ど同じになったところで温水を張ったニーダーに投入して、攪拌しながら溶媒を蒸発させ、樹脂のパウダーを得た。脱水後、熱風循環式乾燥機により１００℃で１２時間乾燥した。得られたパウダーを用いて、前記の方法で各種評価を実施しその結果を表１に示した。
[Example 4]
<Manufacture of thermoplastic resin>
152 parts of ion-exchanged water and 47 parts of 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, stirrer, and reflux condenser, and 13 parts of SSP2 synthesized in Synthesis Example 1 as dihydric phenol, 9 parts of BPA, and hydrosulfite were added. After dissolving 0.04 parts, 79 parts of methylene chloride was added, and 10 parts of phosgene was blown into the solution at 16 to 24° C. over 70 minutes while stirring. Thereafter, 6 parts of a 25% aqueous sodium hydroxide solution was added, and then a solution of 0.4 part of p-tert-butylphenol dissolved in methylene chloride was added and stirred to form an emulsified state. Under such stirring, 0.02 part of triethylamine was added to the reaction solution at 28°C, and stirring was continued for 1 hour at a temperature of 26 to 31°C, at which point the reaction was completed. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and washed repeatedly with ion-exchanged water. When the washing solution became neutral, it was washed with hydrochloric acid acid water. Thereafter, the mixture was washed repeatedly with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was poured into a kneader filled with warm water, and the solvent was evaporated while stirring to obtain a resin powder. After dehydration, it was dried at 100° C. for 12 hours using a hot air circulation dryer. Using the obtained powder, various evaluations were carried out using the methods described above, and the results are shown in Table 1.
［実施例５］
＜熱可塑性樹脂の製造＞
ＳＳＰ２ ８部、ＢＰＡ１２部を原料として用いた他は、実施例４と全く同様の操作を行いポリカーボネート樹脂のパウダーを得、実施例４と同様の評価を行った。その結果を表１に記載した。
[Example 5]
<Manufacture of thermoplastic resin>
Except that 8 parts of SSP2 and 12 parts of BPA were used as raw materials, the same operation as in Example 4 was performed to obtain a polycarbonate resin powder, and the same evaluation as in Example 4 was performed. The results are listed in Table 1.
［比較例１］
ビスフェノールＡ型ポリカーボネート樹脂（帝人化成社製 パンライトＬ１２２５）を使用して、実施例１と同様の評価を行った。その評価結果を表１に記載した。
[Comparative example 1]
The same evaluation as in Example 1 was performed using a bisphenol A type polycarbonate resin (Panlite L1225, manufactured by Teijin Chemicals). The evaluation results are listed in Table 1.
［比較例２］
＜熱可塑性樹脂の製造＞
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（以下ＳＰＧと略す）３１６部、ＢＰＡ５５３部ジフェニルカーボネート７５０部、および触媒としてテトラメチルアンモニウムヒドロキシド０．８×１０－２部と水酸化ナトリウム０．６×１０－４部を窒素雰囲気下２００℃に加熱し溶融させた。その後、３０分かけて減圧度を１３．４ｋＰａに調整した。その後、６０℃／ｈｒの速度で２６０℃まで昇温を行い、１０分間その温度で保持した後、１時間かけて減圧度を１３３Ｐａ以下とした。合計６時間撹拌下で反応を行い、反応槽の底より窒素加圧下吐出し、水槽で冷却しながら、ペレタイザーでカットしてポリカーボネート樹脂ペレットを得た。実施例１と同様の評価を行い、その評価結果を表１に記載した。
[Comparative example 2]
<Manufacture of thermoplastic resin>
316 parts of 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (hereinafter abbreviated as SPG), 553 parts of BPA, 750 parts of diphenyl carbonate , and 0.8×10 −2 parts of tetramethylammonium hydroxide and 0.6×10 −4 parts of sodium hydroxide as catalysts were heated to 200° C. and melted under a nitrogen atmosphere. Thereafter, the degree of pressure reduction was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 260° C. at a rate of 60° C./hr, held at that temperature for 10 minutes, and then the degree of pressure reduction was reduced to 133 Pa or less over 1 hour. The reaction was carried out under stirring for a total of 6 hours, and the mixture was discharged from the bottom of the reaction tank under pressure with nitrogen, and while being cooled in a water bath, it was cut with a pelletizer to obtain polycarbonate resin pellets. The same evaluation as in Example 1 was performed, and the evaluation results are listed in Table 1.
［比較例３］
＜熱可塑性樹脂の製造＞
ＳＰＧ３５４部、９，９－ビス（４－ヒドロキシ－３－メチルフェニル）フルオレン（以下ＢＣＦと略す）１５２部、ジフェニルカーボネート７５０部、および触媒としてテトラメチルアンモニウムヒドロキシド０．８×１０－２部と水酸化ナトリウム０．６×１０－４部を窒素雰囲気下２００℃に加熱し溶融させた。その後、３０分かけて減圧度を１３．４ｋＰａに調整した。その後、６０℃／ｈｒの速度で２８０℃まで昇温を行い、１０分間その温度で保持した後、１時間かけて減圧度を１３３Ｐａ以下とした。合計６時間撹拌下で反応を行い、反応槽の底より窒素加圧下吐出し、水槽で冷却しながら、ペレタイザーでカットしてポリカーボネート樹脂ペレットを得た。実施例１と同様の評価を行い、その評価結果を表１に記載した。
[Comparative example 3]
<Manufacture of thermoplastic resin>
354 parts of SPG, 152 parts of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter abbreviated as BCF), 750 parts of diphenyl carbonate, and 0.8 x 10 -2 parts of tetramethylammonium hydroxide as a catalyst. 0.6×10 −4 parts of sodium hydroxide was heated to 200° C. under a nitrogen atmosphere to melt it. Thereafter, the degree of pressure reduction was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 280°C at a rate of 60°C/hr, held at that temperature for 10 minutes, and then the degree of vacuum was reduced to 133 Pa or less over 1 hour. The reaction was carried out under stirring for a total of 6 hours, and the mixture was discharged from the bottom of the reaction tank under pressure with nitrogen, and while being cooled in a water bath, it was cut with a pelletizer to obtain polycarbonate resin pellets. The same evaluation as in Example 1 was performed, and the evaluation results are listed in Table 1.
［比較例４］
＜熱可塑性樹脂の製造＞
温度計、撹拌機、還流冷却器付き反応器にイオン交換水２５１部、２５％水酸化ナトリウム水溶液１３１部を入れ、二価フェノールとしてＢＣＦ３５部、ＢＰＡ３２部およびハイドロサルファイト０．１３部を溶解した後、塩化メチレン１９８部を加え、撹拌下１６～２４℃でホスゲン３０部を７０分要して吹き込んだ。その後、２５％水酸化ナトリウム水溶液２２部を加え、さらにｐ－ｔｅｒｔ－ブチルフェノール１．５部を塩化メチレンに溶解した溶液を加え、攪拌させて乳化状態とした。かかる攪拌下、反応液が２８℃の状態でトリエチルアミン０．０６部を加えた後、温度２６～３１℃において１時間撹拌を続けたところで反応を終了した。反応終了後有機相を分離し、塩化メチレンで希釈してイオン交換水で水洗を繰り返し、洗浄液が中性になったところで塩酸酸性水にて水洗した。その後、イオン交換水で繰り返し洗浄し水相の導電率がイオン交換水と殆ど同じになったところで温水を張ったニーダーに投入して、攪拌しながら溶媒を蒸発させ、ポリカーボネート樹脂のパウダーを得た。脱水後、熱風循環式乾燥機により１００℃で１２時間乾燥した。得られたパウダーを用いて、前記の方法で各種評価を実施しその結果を表１に示した。
[Comparative example 4]
<Manufacture of thermoplastic resin>
251 parts of ion-exchanged water and 131 parts of a 25% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, stirrer, and reflux condenser, and 35 parts of BCF, 32 parts of BPA, and 0.13 parts of hydrosulfite were dissolved as dihydric phenol. Thereafter, 198 parts of methylene chloride was added, and 30 parts of phosgene was blown into the mixture at 16 to 24° C. over 70 minutes while stirring. Thereafter, 22 parts of a 25% aqueous sodium hydroxide solution was added, followed by a solution of 1.5 parts of p-tert-butylphenol dissolved in methylene chloride, and the mixture was stirred to form an emulsion. Under such stirring, 0.06 part of triethylamine was added to the reaction solution at 28°C, and stirring was continued for 1 hour at a temperature of 26 to 31°C, at which point the reaction was completed. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and washed repeatedly with ion-exchanged water. When the washing solution became neutral, it was washed with hydrochloric acid acid water. After that, it was washed repeatedly with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, it was poured into a kneader filled with warm water, and the solvent was evaporated while stirring to obtain a polycarbonate resin powder. . After dehydration, it was dried at 100° C. for 12 hours using a hot air circulation dryer. Using the obtained powder, various evaluations were carried out using the methods described above, and the results are shown in Table 1.
［比較例５］
＜熱可塑性樹脂の製造＞
イソソルビド（以下ＩＳＳと略す）５０１部、ジフェニルカーボネート７５０部、および触媒としてテトラメチルアンモニウムヒドロキシド０．８×１０－２部と水酸化ナトリウム０．６×１０－４部を窒素雰囲気下１８０℃に加熱し溶融させた。その後、３０分かけて減圧度を１３．４ｋＰａに調整した。その後、６０℃／ｈｒの速度で２６０℃まで昇温を行い、１０分間その温度で保持した後、１時間かけて減圧度を１３３Ｐａ以下とした。合計６時間撹拌下で反応を行い、反応槽の底より窒素加圧下吐出し、水槽で冷却しながら、ペレタイザーでカットしてポリカーボネート樹脂ペレットを得、実施例１と同様の評価を行った。その評価結果を表１に記載した。
[Comparative example 5]
<Manufacture of thermoplastic resin>
501 parts of isosorbide (hereinafter abbreviated as ISS), 750 parts of diphenyl carbonate, and 0.8 x 10 -2 parts of tetramethylammonium hydroxide and 0.6 x 10 -4 parts of sodium hydroxide as catalysts were heated to 180°C under a nitrogen atmosphere. Heat and melt. Thereafter, the degree of pressure reduction was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 260° C. at a rate of 60° C./hr, held at that temperature for 10 minutes, and then the degree of pressure reduction was reduced to 133 Pa or less over 1 hour. The reaction was carried out under stirring for a total of 6 hours, and the mixture was discharged from the bottom of the reaction tank under nitrogen pressure, and while cooling in a water bath, it was cut with a pelletizer to obtain polycarbonate resin pellets, and the same evaluation as in Example 1 was performed. The evaluation results are listed in Table 1.
本発明の熱可塑性樹脂は、光学部品の構造材料、パソコンや携帯電話の外装や前面板などの電気電子部品、自動車内外装部品、位相差フィルム等のフィルム用途として有用である。 The thermoplastic resin of the present invention is useful as a structural material for optical parts, electrical and electronic parts such as exteriors and front panels of personal computers and mobile phones, interior and exterior parts of automobiles, and film applications such as retardation films.
Claims (9)
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| JP2022065514A JP2023155975A (en) | 2022-04-12 | 2022-04-12 | Thermoplastic resin and molded product thereof |
| PCT/JP2023/012089 WO2023199734A1 (en) | 2022-04-12 | 2023-03-27 | Thermoplastic resin and molded article thereof |
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| JP2022065514A JP2023155975A (en) | 2022-04-12 | 2022-04-12 | Thermoplastic resin and molded product thereof |
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