JP2023155974A - Thermoplastic resin and molded product thereof - Google Patents
Thermoplastic resin and molded product thereof Download PDFInfo
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- JP2023155974A JP2023155974A JP2022065513A JP2022065513A JP2023155974A JP 2023155974 A JP2023155974 A JP 2023155974A JP 2022065513 A JP2022065513 A JP 2022065513A JP 2022065513 A JP2022065513 A JP 2022065513A JP 2023155974 A JP2023155974 A JP 2023155974A
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- Prior art keywords
- thermoplastic resin
- resin according
- mol
- formula
- acid
- 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.)
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000010521 absorption reaction Methods 0.000 claims abstract description 22
- 239000002028 Biomass Substances 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 66
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 229920005668 polycarbonate resin Polymers 0.000 description 23
- 239000004431 polycarbonate resin Substances 0.000 description 23
- -1 acrylic ester Chemical class 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000005259 measurement Methods 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
- 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 9
- 238000011156 evaluation Methods 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 7
- 239000002994 raw material Substances 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002989 phenols Chemical class 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
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 4
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 4
- 235000012141 vanillin Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 229960002479 isosorbide Drugs 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000003786 synthesis reaction 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
- 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-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
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 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
- 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000005587 carbonate group Chemical group 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
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006210 cyclodehydration reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 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
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 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
- 230000001965 increasing effect Effects 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
- 229920005610 lignin Polymers 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
- 239000013307 optical fiber Substances 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000009467 reduction Effects 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
- 239000000758 substrate Substances 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-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
- 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 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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Landscapes
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Abstract
Description
本発明は、耐熱性に優れ、表面硬度が高く、低線膨張係数及び低吸水性に優れるバイオマス由来の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 biomass-derived thermoplastic resin that has excellent heat resistance, high surface hardness, low coefficient of linear expansion, and low water absorption, and molded products 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。ＰＣは高い破断伸度を持ち、耐衝撃性に優れているが、表面が非常にやわらかく（鉛筆硬度４Ｂ～２Ｂ）、傷つきやすいという問題がある。そのため、ポリカーボネート基板表面にアクリル酸エステルを塗布して紫外線硬化によって保護膜を形成する方法が提案されている（特許文献１）。しかしながら、硬化時の収縮によるひび割れや工程が煩雑となる問題がある。また、主鎖に芳香環を含むため、耐候性を付与する工程も必要となる。 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. PC has a high elongation at break and is excellent in impact resistance, but the problem is that the surface is very soft (pencil hardness 4B to 2B) and easily scratches. Therefore, a method has been proposed in which an acrylic ester is applied to the surface of a polycarbonate substrate and a protective film is formed by curing with ultraviolet light (Patent Document 1). However, there are problems such as cracking due to shrinkage during curing and complicated processes. Furthermore, since the main chain contains an aromatic ring, a step of imparting weather resistance is also required.
一方、ポリメチルメタクリレートなどのメタクリル酸樹脂は、高い透明性と硬い表面硬度（鉛筆硬度Ｈ～３Ｈ）を持ち、レンズ・光ファイバーなどの光学材料として多く用いられている。しかしながら、吸水率が高く、さらに耐衝撃性が低いために使用される用途が制限されているという問題がある。 On the other hand, methacrylic acid resins such as polymethyl methacrylate have high transparency and hard surface hardness (pencil hardness of H to 3H), and are often used as optical materials such as lenses and optical fibers. However, there are problems in that it has a high water absorption rate and low impact resistance, which limits its applications.
最近では、植物由来モノマーであるイソソルビドを使用し、炭酸ジフェニルとのエステル交換により、耐候性、表面硬度に優れたポリカーボネートを得ることが提案されている（特許文献２）。しかしながら、イソソルビド骨格に由来する吸水性の高さから、高温多湿下の環境では寸法変化が大きく、また一般のポリカーボネート樹脂と同様、線膨張係数が十分低く無く、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る。 Recently, it has been proposed to obtain polycarbonate with excellent weather resistance and surface hardness by using isosorbide, which is a plant-derived monomer, and transesterifying it with diphenyl carbonate (Patent Document 2). However, due to its high water absorption derived from its isosorbide skeleton, it undergoes large dimensional changes in high temperature and humid environments, and like general polycarbonate resin, its linear expansion coefficient is not low enough, making it suitable for precision parts and large molded parts. There may be restrictions on usage.
その為、耐熱性、高表面硬度、低線膨張係数、低吸水率の全てをバランスよく満足する熱可塑性樹脂および成形体は未だ提供されていなかった。 Therefore, thermoplastic resins and molded articles that satisfy all of heat resistance, high surface hardness, low coefficient of linear expansion, and low water absorption in a well-balanced manner have not yet been provided.
他方、植物由来のモノマーとしてバニリンから誘導された各種モノマーが報告されている。それらを原料として用いたポリエステル樹脂やエポキシ樹脂での報告例はあるが（特許文献３、４や非特許文献１、２）、ポリカーボネート構造を含む樹脂はこれまでに報告されていない。 On the other hand, various monomers derived from vanillin have been reported as plant-derived monomers. Although there are reports on polyester resins and epoxy resins using these as raw materials (Patent Documents 3 and 4 and Non-Patent Documents 1 and 2), no resins containing a polycarbonate structure have been reported so far.
本発明の目的は、耐熱性に優れ、表面硬度が高く、低線膨張係数及び低吸水性に優れるバイオマス由来の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 biomass-derived thermoplastic resin having excellent heat resistance, high surface hardness, low coefficient of linear expansion, and low water absorption, 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）を含むことで、耐熱性、表面硬度、低線膨張係数及び低吸水性に優れる熱可塑性樹脂および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 the repeating unit (1), thermoplastic resins and molded products having excellent heat resistance, surface hardness, low coefficient of linear expansion, and low water absorption can be obtained. This research led to the present invention.
That is, the present invention is as follows.
１．下記式（１）で表される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 repeating units represented by the following formula (1) based on all repeating units.
（式中、Ｒ１とＲ２はそれぞれ独立に、水素原子もしくはメトキシ基を表す。） (In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methoxy group.)
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．前記式（１）におけるＲ１がメトキシ基であり、Ｒ２が水素原子である前項１～３のいずれかに記載の熱可塑性樹脂。
５．鉛筆硬度がＨＢ以上である前項１～４のいずれかに記載の熱可塑性樹脂。
６．線膨張係数が７０×１０－６・℃－１以下である前項１～５のいずれかに記載の熱可塑性樹脂。
７．飽和吸水率が２．５％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．バイオマス度が５％以上である前項１～７のいずれかに記載の熱可塑性樹脂。
９．フェノール含有量が２，０００重量ｐｐｍ以下である前項１～８のいずれかに記載の熱可塑性樹脂。
１０．前項１～９のいずれかに記載の熱可塑性樹脂を素材とする成形品。
１１．前項１～９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. 4. The thermoplastic resin according to any one of items 1 to 3 above, wherein R 1 in the formula (1) is a methoxy group and R 2 is a hydrogen atom.
5. The thermoplastic resin according to any one of items 1 to 4 above, which has a pencil hardness of HB or higher.
6. 6. The thermoplastic resin according to any one of items 1 to 5 above, which has a coefficient of linear expansion of 70×10 −6 ·° C. −1 or less.
7. 7. The thermoplastic resin according to any one of items 1 to 6 above, which has a saturated water absorption rate of 2.5% or less.
8. 8. The thermoplastic resin according to any one of items 1 to 7 above, which has a biomass degree of 5% or more.
9. 9. The thermoplastic resin according to any one of items 1 to 8 above, which has a phenol content of 2,000 ppm or less by weight.
10. A molded article made from the thermoplastic resin according to any one of items 1 to 9 above.
11. A film made from the thermoplastic resin according to any one of items 1 to 9 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、高表面硬度、低線膨張係数及び低吸水性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 material with a specific structure as a basic unit, the thermoplastic resin of the present invention can have properties such as excellent heat resistance, high surface hardness, low coefficient of linear expansion, and low water absorption. Ta. 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）で表される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）で表される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 is a thermoplastic resin containing 1 to 100 mol% of repeating units represented by the following formula (1) based on all repeating units. It preferably contains 5 to 100 mol% of all repeating units, more preferably 10 to 100 mol%, still more preferably 15 to 100 mol%, and particularly preferably 20 to 100 mol% of the repeating unit represented by the following formula (1). It contains 100 mol%, most preferably 25 to 100 mol%.
（式中、Ｒ１とＲ２はそれぞれ独立に、水素原子もしくはメトキシ基を表す。）
前記式（１）の構造の具体例としては、下記構造式（１－１）、（１－２）、（１－３）で表されるものが挙げられ、これらのうち、Ｒ１がメトキシ基であり、Ｒ２が水素原子である３，９－ビス（４－オキシ－３－メトキシフェニル）－２，４，８，１０，－テトラオキサスピロ［５．５］ウンデカンから誘導される下記構造式（１－１）構造が特に好ましい。
(In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methoxy group.)
Specific examples of the structure of formula (1) include those represented by the following structural formulas (1-1), (1-2), and (1-3), among which R 1 is methoxy The following group derived from 3,9-bis(4-oxy-3-methoxyphenyl)-2,4,8,10,-tetraoxaspiro[5.5]undecane in which R 2 is a hydrogen atom The structure of structural formula (1-1) is particularly preferred.
（他の繰り返し単位）
本発明において、上記式（１）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。
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。
(other repeat units)
In the present invention, repeating units constituting copolymerized units other than the repeating unit represented by the above formula (1) include repeating units derived from various diol compounds.
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）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 formula (1) contain 0 to 99 mol%, preferably 0 to 95 mol%, more preferably 0 to 90 mol%, and It preferably contains 0 to 85 mol%, particularly preferably 0 to 80 mol%, and most preferably 0 to 75 mol%.
（原料）
上記式（１）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－ａ）で表されるジオール成分である。
(material)
The diol component serving as a raw material for inducing the repeating unit represented by the above formula (1) is mainly a diol component represented by the following formula (1-a).
（式中、Ｒ１とＲ２はそれぞれ独立に、水素原子もしくはメトキシ基を表す。）
前記式（１－ａ）のジオール構造の具体例としては、下記構造式（１－ａ－１）、（１－ａ－２）、（１－ａ－３）で表されるものが挙げられ、これらのうち、Ｒ１がメトキシ基であり、Ｒ２が水素原子である下記構造式（１－ａ－１）の３，９－ビス（４－オキシ－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、が特に好ましい。
(In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methoxy group.)
Specific examples of the diol structure of the formula (1-a) include those represented by the following structural formulas (1-a-1), (1-a-2), and (1-a-3). , among these, 3,9-bis(4-oxy-3-methoxyphenyl)-2,4 of the following structural formula (1-a-1) where R 1 is a methoxy group and R 2 is a hydrogen atom ,8,10,-tetraoxaspiro[5.5]undecane is particularly preferred.
上記式（１－ａ）で表されるジオールは、下記式（２）で表される構造物と、下記式（３）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。 The diol represented by the above formula (1-a) can be obtained by subjecting a structure represented by the following formula (2) and pentaerythritol represented by the following formula (3) to a cyclodehydration reaction.
（式中、Ｒ１とＲ２はそれぞれ独立に、水素原子もしくはメトキシ基を表す。） (In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methoxy group.)
上記式（２）で表される構造物は植物を構成するリグニンから誘導される成分として知られる。リグニンから誘導される構造物の具体例としては、バニリン［下記式（２－１）］、４－ヒドロキシベンズアルデヒド［下記式（２－２）］、シリンガアルデヒド［下記式（２－３）］が挙げられる。特に入手性の観点からバニリンを用いることが好ましい。 The structure represented by the above formula (2) is known as a component derived from lignin, which constitutes plants. Specific examples of structures derived from lignin include vanillin [formula (2-1) below], 4-hydroxybenzaldehyde [formula (2-2) below], and syringaldehyde [formula (2-3) below]. can be mentioned. In particular, it is preferable to use vanillin from the viewpoint of availability.
本発明においては、石油由来ではない原料を用いることが好ましい。本発明の前記式（１－ａ）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。 In the present invention, it is preferable to use raw materials that are not derived from petroleum. The purity of the diol compound represented by the formula (1-a) of the present invention is preferably 95% or more, more preferably 97% or more, and even more preferably 98% or more. 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－ａ）で表されるジオール化合物は、上記式（２）で表される構造物と上記式（３）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 compound represented by the above formula (1-a) of the present invention is prepared by combining the structure represented by the above formula (2) and the pentaerythritol represented by the above formula (3) in the presence of an acid catalyst and a solvent. , obtained by cyclodehydration reaction.
前記式（１－ａ）で表されるジオール化合物の製造方法において、上記式（２）で表される構造物の使用比率は、上記式（３）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 the diol compound represented by the above formula (1-a), the usage ratio of the structure represented by the above formula (2) is based on 1 mole of pentaerythritol represented by the above formula (3). The amount is preferably 1.8 to 2.4 mol, more preferably 1.9 to 2.1 mol.
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）で表される繰り返し単位を含み、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、表面硬度に優れ、低線膨張係数であり、低吸水性にも優れるため好ましい。
(Copolymer composition)
The thermoplastic resin of the present invention contains the repeating unit represented by the above formula (1), and the molar ratio of the repeating units in the entire thermoplastic resin is 1 to 100 mol%, more preferably 5 to 100 mol%. , more preferably 15 to 100 mol%, particularly preferably 20 to 100 mol%, and most preferably 25 to 100 mol%. Within the above range, it is preferable because it has excellent heat resistance, surface hardness, low linear expansion coefficient, and low water absorption.
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）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。 The mol% of the repeating unit represented by the formula (1) 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 still more preferably 120°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.
（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、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１．５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。比粘度が上記下限以上では強度等が向上し、上記上限以下では成形加工特性が優れる。
(Specific viscosity: η SP )
The specific viscosity (η SP ) of the thermoplastic resin of the present invention is preferably 0.15 or more and 1.5 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 above-mentioned lower limit, strength etc. are improved, and when the specific viscosity is below the above-mentioned 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.
（鉛筆硬度）
本発明で使用される熱可塑性樹脂は、鉛筆硬度が好ましくはＨＢ以上である。耐傷性に優れるという点で、Ｆ以上がより好ましく、Ｈ以上がさらに好ましい。鉛筆硬度は全繰り返し単位を基準として前記式（１）で表される繰り返し単位のモル％を増加させることで硬くすることができる。本発明において、鉛筆硬度とは、本発明の樹脂を特定の鉛筆硬度を有する鉛筆で樹脂を擦過した場合に擦過しても擦過痕が残らない硬さのことであり、ＪＩＳ Ｋ－５６００に従って測定できる塗膜の表面硬度試験に用いる鉛筆硬度を指標とする。鉛筆硬度は、９Ｈ、８Ｈ、７Ｈ、６Ｈ、５Ｈ、４Ｈ、３Ｈ、２Ｈ、Ｈ、Ｆ、ＨＢ、Ｂ、２Ｂ、３Ｂ、４Ｂ、５Ｂ、６Ｂの順で柔らかくなり、最も硬いものが９Ｈ、最も軟らかいものが６Ｂである。
(Pencil hardness)
The thermoplastic resin used in the present invention preferably has a pencil hardness of HB or higher. In terms of excellent scratch resistance, the number is preferably F or higher, and even more preferably H or higher. The pencil hardness can be increased by increasing the mole % of the repeating unit represented by the formula (1) based on all repeating units. In the present invention, pencil hardness refers to the hardness that does not leave scratch marks when the resin of the present invention is rubbed with a pencil having a specific pencil hardness, and is measured according to JIS K-5600. The pencil hardness used in the surface hardness test of the resulting paint film is used as an index. Pencil hardness decreases in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B, with 9H being the hardest and 9H being the hardest. The soft one is 6B.
（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以下であり、特に好ましくは５５×１０－６・℃－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。
(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, particularly preferably 55×10 −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.
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）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。 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 unit represented by the formula (1) above that constitutes the thermoplastic resin of the present invention. The larger the ratio, the lower the linear expansion coefficient.
（バイオマス度）
本発明の熱可塑性樹脂のバイオマス度は５％以上であると好ましく、１０％以上であるとより好ましく、１５％以上であるとさらに好ましく、２０％以上であると特に好ましい。
(Biomass degree)
The biomass degree of the thermoplastic resin of the present invention is preferably 5% or more, more preferably 10% or more, even more preferably 15% or more, and particularly preferably 20% or more.
本発明において、熱可塑性樹脂におけるバイオマス度は、熱可塑性樹脂を構成する全構造単位のうち、植物由来資源から合成された構造単位の炭素の重量比率と定義する。なお、熱可塑性樹脂中のバイオマス度は１００％である必要はない。一部にでもバイオマス由来の原料が用いられていれば、化石燃料の使用量を削減し環境負荷を低減するという本発明の趣旨に沿うためである。また、植物由来の資源から製造されたものであるかどうかは、例えば、放射性炭素（１４Ｃ）の濃度測定により確認することが可能である。大気中の二酸化炭素には、１４Ｃが一定割合（１０５．５ｐＭＣ）で含まれているため、大気中の二酸化炭素を取り入れて成長する植物、例えばトウモロコシ中の１４Ｃ含有量も１０５．５ｐＭＣ程度であることが知られている。また、化石燃料中には１４Ｃが殆ど含まれていないことも知られている。したがって、熱可塑性樹脂中の全炭素原子中に含まれる１４Ｃの割合を測定することにより、バイオマス由来の炭素の割合を算出することができる。 In the present invention, the degree of biomass in a thermoplastic resin is defined as the weight ratio of carbon in structural units synthesized from plant-derived resources among all structural units constituting the thermoplastic resin. Note that the degree of biomass in the thermoplastic resin does not need to be 100%. This is because if biomass-derived raw materials are used even in part, the purpose of the present invention is to reduce the amount of fossil fuel used and the environmental load. Further, whether or not the product is manufactured from plant-derived resources can be confirmed by, for example, measuring the concentration of radioactive carbon ( 14 C). Since atmospheric carbon dioxide contains 14 C at a certain rate (105.5 pMC), the 14 C content in plants that grow by taking in atmospheric carbon dioxide, such as corn, is also around 105.5 pMC. It is known that It is also known that fossil fuels contain almost no 14C . Therefore, by measuring the proportion of 14 C contained in all carbon atoms in the thermoplastic resin, the proportion of carbon derived from biomass can be calculated.
（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、２，０００重量ｐｐｍ以下であることが好ましく、１，５００重量ｐｐｍ以下であることがより好ましく、１，０００重量ｐｐｍ以下であることが更に好ましい。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 2,000 ppm by weight, more preferably at most 1,500 ppm by weight, and even more preferably at most 1,000 ppm by weight. preferable. 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としては、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. Polycarbonate resins having a carbonate structure include polyester carbonates copolymerized with aromatic or aliphatic (including alicyclic) bifunctional carboxylic acids. 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 to distill 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。 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.
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。 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．鉛筆硬度
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、ＪＩＳ Ｋ５６００の鉛筆硬度試験方法によって測定した。
4. Pencil hardness It was measured according to the JIS K5600 pencil hardness test method using a cast film with a thickness of 200 μm obtained by dissolving polycarbonate resin powder or pellets in methylene chloride and then evaporating the methylene chloride.
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、３０～７０℃の線膨張係数を測定し、その平均値を算出した。
6. Coefficient of Linear Expansion Using a cast film with a thickness of 200 μm obtained by dissolving polycarbonate resin powder or pellets in methylene chloride and evaporating the methylene chloride, 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．バイオマス度
ポリカーボネート樹脂を構成する全構造単位のうち、植物由来資源から合成された構造単位における炭素原子の重量比率を計算した。
7. Biomass degree Among all the structural units constituting the polycarbonate resin, the weight ratio of carbon atoms in the structural units synthesized from plant-derived resources was calculated.
８．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。
8. 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］
＜３，９－ビス（４－オキシ－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９３℃で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－オキシ－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、ＳＳＰと略す）の結晶を２９ｇ得た（収率：７９％）。この結晶の純度は９９．５２％、ＤＳＣによる吸熱ピークは１８１℃であった。
[Synthesis example]
<Synthesis of 3,9-bis(4-oxy-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 cooled, crystals began to precipitate at 93°C. After cooling to room temperature, the precipitated crystals were collected and vacuum dried at 90°C for 2 hours to give 3,9-bis(4-oxy-3-methoxyphenyl)-2,4,8,10,-tetraoxaspiro. [5.5] 29 g of crystals of undecane (hereinafter abbreviated as SSP) were obtained (yield: 79%). The purity of this crystal was 99.52%, and the endothermic peak by DSC was 181°C.
［ＳＳＰの純度測定：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
[SSP 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
［ＳＳＰの融点測定：示差走査熱量測定（ＤＳＣ）］
ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ製Ｄｉｓｃｏｖｅｒｙ ＤＳＣ２５を用い、窒素フロー下、昇温速度：２０℃／ｍｉｎで測定した。
[Measurement of melting point of SSP: Differential scanning calorimetry (DSC)]
Measurement was performed using Discovery DSC25 manufactured by TA Instruments under a nitrogen flow at a temperature increase rate of 20° C./min.
［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ＳＳＰ３４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 25% sodium hydroxide aqueous solution were placed in a reactor equipped with a thermometer, stirrer, and reflux condenser, and 34 parts of SSP synthesized in Synthesis Example 1 as dihydric phenol and 0.07 parts of hydrosulfite were added. 86 parts of methylene chloride were added, and 11 parts of phosgene was blown into the mixture 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＞
ＳＳＰ１７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 for using 17 parts of SSP and 10 parts of bisphenol A (hereinafter abbreviated as 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３］
＜熱可塑性樹脂の製造＞
ＳＳＰ１０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 SSP 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＞
ＳＳＰ１７部、ビスフェノールＣ（以下、ＢＰＣと略す）１１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 4]
<Manufacture of thermoplastic resin>
Except that 17 parts of SSP and 11 parts of bisphenol C (hereinafter abbreviated as BPC) 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.
［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 bisphenol A type polycarbonate resin (Teijin Panlite L1225). The evaluation results are listed in Table 1.
［比較例２］
＜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 2]
<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 (11)
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