WO2013035439A1 - Composition de résine de polycarbonate et corps moulé - Google Patents
Composition de résine de polycarbonate et corps moulé Download PDFInfo
- Publication number
- WO2013035439A1 WO2013035439A1 PCT/JP2012/068288 JP2012068288W WO2013035439A1 WO 2013035439 A1 WO2013035439 A1 WO 2013035439A1 JP 2012068288 W JP2012068288 W JP 2012068288W WO 2013035439 A1 WO2013035439 A1 WO 2013035439A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- polycarbonate resin
- mass
- lignophenol
- resin composition
- Prior art date
Links
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 71
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 125000003118 aryl group Chemical group 0.000 claims abstract description 50
- 229920001225 polyester resin Polymers 0.000 claims abstract description 26
- 239000004645 polyester resin Substances 0.000 claims abstract description 20
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- -1 polyethylene terephthalate Polymers 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000005027 hydroxyaryl group Chemical group 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 238000005243 fluidization Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 description 30
- 238000000034 method Methods 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 229920005610 lignin Polymers 0.000 description 10
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- 239000002023 wood Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229920000747 poly(lactic acid) Polymers 0.000 description 7
- 239000004626 polylactic acid Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 238000004898 kneading Methods 0.000 description 6
- 239000012978 lignocellulosic material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 235000013312 flour Nutrition 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MUVQKFGNPGZBII-UHFFFAOYSA-N 1-anthrol Chemical compound C1=CC=C2C=C3C(O)=CC=CC3=CC2=C1 MUVQKFGNPGZBII-UHFFFAOYSA-N 0.000 description 2
- 125000004208 3-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C([H])C(*)=C1[H] 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 241000218631 Coniferophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 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
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- KDYHQAWOWCCBAJ-UHFFFAOYSA-N 1h-indole-2,3-dione;2-methylphenol Chemical group CC1=CC=CC=C1O.CC1=CC=CC=C1O.C1=CC=C2C(=O)C(=O)NC2=C1 KDYHQAWOWCCBAJ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KJMVGAOYRRKQPY-UHFFFAOYSA-N 4-[2,4,6-tri(propan-2-yl)phenyl]phenol Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=C(O)C=C1 KJMVGAOYRRKQPY-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
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- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
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- 210000004292 cytoskeleton Anatomy 0.000 description 1
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- 238000001212 derivatisation Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
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- 239000011121 hardwood Substances 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005732 intercellular adhesion Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 125000005590 trimellitic acid group Chemical group 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Definitions
- the present invention relates to a polycarbonate resin composition and a molded body using the same. More specifically, by using a biomass material, it has excellent environmental performance, high fluidity and high impact resistance, excellent heat resistance and flame resistance, and excellent solvent resistance and moisture and heat resistance, and molded appearance.
- the present invention also relates to a good polycarbonate resin composition and a molded body using the same.
- Polycarbonate resins are excellent in mechanical properties such as heat resistance and impact resistance, and thus are used as materials for various parts in the electric / electronic field, automobile field, and the like. Polycarbonate resins may be used in combination with polycarbonate resins. In order to make a composition in which a polyester resin is blended with such a polycarbonate resin, a flame retardant such as an organic phosphate is used instead of a halogen flame retardant because of a request for non-halogenation. .
- polylactic acid may be used as a biodegradable polyester resin.
- Patent Documents 1 and 2 by blending lignophenol having a specific structure with polycarbonate resin or polycarbonate resin containing polylactic acid, it has excellent environmental performance, and has high fluidity and high impact resistance. A polycarbonate resin composition having excellent flame retardancy and heat resistance is described.
- these documents do not describe blending polyester resins other than polylactic acid and the effects thereof.
- the low gloss of the polycarbonate resin and polylactic acid may result in a decrease in physical properties or a decrease in the dispersibility of lignophenol, resulting in a decrease in gloss of the molded product.
- the present invention relates to a resin composition in which a polyester resin is blended with a polycarbonate resin, and has a high degree of biomass (vegetation degree) without using a halogen-based flame retardant and a phosphorus-based flame retardant, reducing carbon dioxide emissions and fossil raw materials.
- a resin composition in which a polyester resin is blended with a polycarbonate resin, and has a high degree of biomass (vegetation degree) without using a halogen-based flame retardant and a phosphorus-based flame retardant, reducing carbon dioxide emissions and fossil raw materials.
- a resin composition in which a polyester resin is blended with a polycarbonate resin, and has a high degree of biomass (vegetation degree) without using a halogen-based flame retardant and a phosphorus-based flame retardant, reducing carbon dioxide emissions and fossil raw materials.
- it also has excellent heat and moisture resistance, fluidity, impact resistance and flame retardancy, and can be highly fluidized while maintaining high heat resistance, and can also improve solvent resistance.
- a polycarbonate resin composition in which the dispersibility of lignophenol is improved and the compatibility between a polycarbonate resin and a polyester resin is good, and a molded article having a transparent feeling and gloss can be obtained, and a molded article using the same.
- a polycarbonate resin composition in which the dispersibility of lignophenol is improved and the compatibility between a polycarbonate resin and a polyester resin is good, and a molded article having a transparent feeling and gloss can be obtained, and a molded article using the same.
- the present inventors have achieved the above object by blending (A) polycarbonate resin, (B) aromatic polyester resin, and (C) lignophenol at a specific ratio. As a result, the present invention has been completed. That is, the present invention provides the following polycarbonate resin composition.
- R 1 and R 4 represent an alkyl group, an aryl group, an alkoxy group, an aralkyl group or a phenoxy group
- R 2 represents a hydroxyaryl group or an alkyl-substituted hydroxyaryl group
- R 3 represents a hydroxyalkyl group or an alkyl group.
- Group, an aryl group, an alkyl-substituted aryl group or —OR 5 R 5 represents a hydrogen atom, an alkyl group or an aryl group
- R 1 to R 5 other than a hydrogen atom may have a substituent.
- p and q are integers from 0 to 4.
- the plurality of R 1 may be the same or different, and when q is 2 or more, the plurality of R 4 are the same or different. May be. ] 2.
- lignophenol which is an environmentally friendly biomass raw material, without using a halogen-based flame retardant and a phosphorus-based flame retardant
- a resin composition in which a polyester resin is blended with a polycarbonate resin, (Vegetable degree) is high, and it has excellent environmental performance such as carbon dioxide emission reduction and fossil raw material reduction. It also has excellent heat and moisture resistance, fluidity, impact resistance and flame resistance, and maintains high heat resistance. Fluidization is possible, solvent resistance can be improved, lignophenol dispersibility is improved, and compatibility between the polycarbonate resin and the polyester resin is good. can get.
- the polycarbonate resin composition of the present invention is a polycarbonate resin composition containing (A) a polycarbonate resin, (B) an aromatic polyester resin, and (C) a lignophenol.
- A a polycarbonate resin
- B an aromatic polyester resin
- C a lignophenol
- the (A) polycarbonate resin may be an aromatic polycarbonate resin or an aliphatic polycarbonate resin, but it is preferable to use an aromatic polycarbonate resin because it is more excellent in impact resistance and heat resistance.
- an aromatic polycarbonate resin usually produced by a reaction between a dihydric phenol and a carbonate precursor can be used.
- the aromatic polycarbonate resin can be a main component of the resin composition because it has better heat resistance, flame retardancy, and impact resistance than other thermoplastic resins.
- dihydric phenol examples include various compounds such as 4,4′-dihydroxydiphenyl; 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, And bis (4-hydroxyphenyl) alkanes such as 2,2-bis (4-hydroxyphenyl) propane [bisphenol A]; bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) oxide; bis (4 -Hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl) ketone. Of these, bisphenol A is preferred.
- the dihydric phenol may be a homopolymer using one of these dihydric phenols or a copolymer using two or more. Further, it may be a thermoplastic random branched polycarbonate resin obtained by using a polyfunctional aromatic compound in combination with a dihydric phenol.
- the carbonate precursor include carbonyl halide, haloformate, carbonate ester and the like, and specifically, phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate and the like.
- a terminal terminator can be used as necessary, and examples thereof include a monohydric phenol compound represented by the following general formula (II).
- R 10 represents an alkyl group having 1 to 35 carbon atoms, and a represents an integer of 0 to 5
- a para-substituted product is preferable.
- monohydric phenol compounds include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol. it can. These monohydric phenols may be used alone or in combination of two or more.
- the aromatic polycarbonate resin used in the present invention may have a branched structure.
- a branching agent may be used.
- the viscosity average molecular weight of the aromatic polycarbonate resin used in the present invention is preferably 10,000 to 40,000, more preferably 13,000 to 30,000, from the viewpoint of physical properties of the resin composition.
- an aromatic polycarbonate-polyorganosiloxane copolymer or a resin containing an aromatic polycarbonate-polyorganosiloxane copolymer is used so that the flame retardancy and low temperature are reduced.
- the impact resistance can be further improved.
- the polyorganosiloxane constituting the copolymer is more preferably polydimethylsiloxane from the viewpoint of flame retardancy.
- the (B) aromatic polyester-based resin is a component that improves the solvent resistance of the polycarbonate resin composition and increases the fluidity so as to obtain a molded article having a sense of transparency and gloss.
- aromatic polyester-based resin of the present invention various resins can be used, and a polyester resin obtained by polycondensation of a bifunctional carboxylic acid component and an alkylene glycol component is particularly preferable.
- a bifunctional carboxylic acid component and an alkylene glycol component can be mentioned as a bifunctional carboxylic acid component and an alkylene glycol component.
- bifunctional carboxylic acid examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.
- aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.
- terephthalic acid is preferable, and other difunctional carboxylic acids can be used in combination as long as the effects of the present invention are not impaired.
- the alkylene glycol component is not particularly limited. Specifically, ethylene glycol, propylene-1,2-glycol, propylene-1,3-glycol, butylene-1,4-glycol, butylene-2 , 3-glycol, hexane-1,6-diol, octane-1,8-diol, neopentyl glycol, decane-1,10-diol, aliphatic diol having 2 to 10 carbon atoms, etc. may be used. it can. Of these, ethylene glycol and butylene glycol are preferred.
- the (B) aromatic polyester-based resin includes polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyarylate, etc., among them, polyethylene terephthalate or polybutylene. Terephthalate is preferred.
- the production of the aromatic polyester resin as the component (B) can be carried out by a usual method in the presence or absence of a polycondensation catalyst containing titanium, germanium, antimony or the like.
- a polycondensation catalyst containing titanium, germanium, antimony or the like for example, polyethylene terephthalate usually undergoes an esterification reaction between terephthalic acid and ethylene glycol or transesterifies a lower alkyl ester such as dimethyl terephthalate with ethylene glycol to produce a glycol ester of terephthalic acid and / or its low weight. It is produced by a first stage reaction for producing a coalescence and a second stage reaction by further polymerizing the glycol ester and / or its low polymer to form a polymer having a high degree of polymerization.
- (C) lignophenol has a structure represented by the following general formula (I).
- R 1 and R 4 are alkyl groups (preferably alkyl groups having 1 to 4 carbon atoms, specifically methyl group, ethyl group, propyl group, etc.), aryl groups (preferably carbon atoms).
- an alkoxy group preferably an alkoxy group having 1 to 4 carbon atoms, specifically a methoxy group, an ethoxy group, a propoxy group, etc.
- An aralkyl group preferably an aralkyl group having 12 to 20 carbon atoms, specifically a benzyl group or the like) or a phenoxy group is shown.
- R 2 is a hydroxyaryl group (preferably a hydroxyaryl group having 6 to 14 carbon atoms, specifically 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, etc.) or alkyl-substituted hydroxyaryl Group (preferably a hydroxyaryl group having 7 to 18 carbon atoms, specifically 2-hydroxy-5-methylphenyl group, 3-hydroxy-5-methylphenyl group, 4-hydroxy-5-methylphenyl group, etc.
- R 3 represents a hydroxyalkyl group (preferably a hydroxyalkyl group having 1 to 4 carbon atoms, specifically hydroxymethyl group, hydroxyethyl group, etc.), an alkyl group (preferably having 1 to 4 carbon atoms).
- An alkyl group specifically a methyl group, an ethyl group, a propyl group, or the like) or an aryl group (preferably having 6 to 1 carbon atoms)
- R 5 represents a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group, preferably an aryl group having 6 to 10 carbon atoms).
- R 1 to R 5 other than a hydrogen atom may each have a substituent, and p and q each represents an integer of 0 to 4. However, when p is 2 or more, the plurality of R 1 may be the same or different, and when q is 2 or more, the plurality of R 4 are the same or different. May be.
- the structure represented by the general formula (I) is preferably a naturally derived structure.
- R 1 and R 4 in the above general formula (I) are determined by the tree species, the substituent represented by R 1 and R 4 is a methoxy group, and p and q are each 1 or 2
- R 1 and R 4 are determined by the tree species
- the substituent represented by R 1 and R 4 is a methoxy group
- p and q are each 1 or 2
- softwood is a 3-substituted product with one methoxy group
- broad-leaved trees and herbs are 1: 1 with a 3-substituted product with one methoxy group and two 3,5-substituted products with two methoxy groups.
- a structure that does not have a part of the substituent that is a methoxy group may be included.
- R 3 is a hydroxymethyl group in the naturally derived structure.
- R 2 is a hydroxyaryl group (preferably a hydroxyaryl group having 6 to 14 carbon atoms, specifically 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4 -Hydroxyphenyl group or the like) or alkyl-substituted hydroxyaryl group (preferably a hydroxyaryl group having 7 to 18 carbon atoms, specifically 2-hydroxy-5-methylphenyl group, 3-hydroxy-5-methylphenyl group) , 4-hydroxy-5-methylphenyl group and the like.
- the variation as (C) lignophenol can be increased by freely controlling R 2 of the naturally derived structure.
- the mass average molecular weight of the lignophenol represented by the general formula (I) is preferably 1,000 to 200,000, more preferably 3,000 to 100,000, in terms of polystyrene.
- the both end groups of lignophenol represented by the general formula (I) are preferably phenolic hydroxyl groups, that is, one is a hydroxyl group and the other is a hydrogen atom.
- the lignocresol structure represented, for example by following formula (III) is mentioned.
- Lignophenol is a compound derived from lignin contained in timber, paper, etc., and lignin, for example, acts as an intercellular adhesion substance filled in the gaps of carbohydrates that form the cytoskeleton of trees. is there. Since the structure of lignin is very complex and difficult to use as it is, it is useful to convert it to lignophenol.
- the component (C) of the present invention can be obtained by adding a phenol derivative to a lignocellulosic material such as wood or paper and then hydrolyzing it with an acid to separate it into lignophenol and a carbohydrate.
- the component (C) includes an alkali-treated derivative of the above lignophenol, or a derivative in which the hydroxyl group in the above-mentioned lignophenol or the above-mentioned alkali-treated derivative of lignophenol is protected.
- lignocellulosic substances include wooded materials, various materials mainly wood, such as wood flour, chips, waste materials, and mill ends. Moreover, as wood to be used, any kind of wood such as conifers and hardwoods can be used. Furthermore, various herbaceous plants and related samples such as agricultural wastes can be used. When lignophenol is separated using these materials, those obtained without heating and pressurization in the separation process are preferably used.
- a monovalent phenol derivative a divalent phenol derivative, a trivalent phenol derivative, or the like
- the monovalent phenol derivative include phenol, naphthol, anthrol, anthroquinoneol and the like, and each may have one or more substituents.
- the divalent phenol derivative include resorcinol, hydroquinone and the like, each of which may have one or more substituents.
- the trivalent phenol derivative include pyrogallol and the like, which may have one or more substituents.
- those including those other than those mentioned above such as hydroxyanthracene, methoxyphenol (mono-di-tri), methylcatechol, biphenyl, dimethylhydroxyaryl, trimethylhydroxyaryl, etc. can also be used as the phenol derivative.
- the type of substituent that the phenol derivative may have is not particularly limited, and may have any substituent, but is preferably a group other than an electron-withdrawing group (such as a halogen atom),
- an alkyl group methyl group, ethyl group, propyl group, etc.
- an alkoxy group methoxy group, ethoxy group, propoxy group, etc.
- an aryl group phenyl group etc.
- Particularly preferred examples of phenol derivatives are cresol, in particular m-cresol or p-cresol.
- an acid having swelling property with respect to cellulose is preferable.
- the acid include sulfuric acid having a concentration of 65% by mass or more (for example, 72% by mass sulfuric acid), 85% by mass or more of phosphoric acid, 38% by mass or more of hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid, Examples thereof include trichloroacetic acid and formic acid.
- Examples of the method for extracting and separating lignophenol obtained as described above include the following two methods.
- the first method is the method described in Japanese Patent No. 2895087. Specifically, lignin is solvated into a phenol derivative by infiltrating a lignocellulosic material such as wood flour, and then concentrated acid is added to dissolve the lignocellulosic material. At this time, the cation at the side chain ⁇ -position of the lignin basic structural unit is attacked by the phenol derivative, and lignophenol in which the phenol derivative is introduced at the benzyl position is generated in the phenol derivative phase. And it is the method of extracting lignophenol from a phenol derivative phase.
- the precipitate obtained by adding the phenol derivative phase to a large excess of ethyl ether is collected and dissolved in acetone.
- the acetone insoluble part is removed by centrifugation, and the acetone soluble part is concentrated.
- the acetone soluble part is dropped into a large excess of ethyl ether, and the precipitate section is collected.
- the crude lignophenol can be obtained by simply removing the phenol derivative phase by distillation under reduced pressure.
- an acetone soluble part can also be used for a derivatization process (alkali process) as a lignophenol solution as it is.
- the second method is a method described in Japanese Patent Laid-Open No. 2001-64494. Specifically, a lignocellulosic material is infiltrated with a solvent in which a solid or liquid phenol derivative is dissolved, and then the solvent is distilled off (phenol derivative sorption step). Next, a concentrated acid is added to this lignocellulosic material to dissolve the cellulose component, and lignophenol is produced in the phenol derivative phase and the lignophenol is extracted as in the first method. Extraction of lignophenol can be performed in the same manner as in the first method. Alternatively, as another extraction method, the entire reaction solution after the concentrated acid treatment is put into excess water, insoluble sections are collected by centrifugation, deoxidized and dried. Acetone or alcohol is added to the dried product to extract lignophenol. Further, as in the first method, this soluble segment is dropped into excess ethyl ether or the like to obtain lignophenol as an insoluble segment.
- the second method is the latter extraction method, in particular, the method of extracting and separating lignophenol with acetone or alcohol, the amount of phenol derivative used is It is economical because it requires less. Moreover, since this method can process many lignocellulosic materials with a small amount of a phenol derivative, it is suitable for large-scale synthesis of lignophenol.
- the component (C) of the present invention obtained by the above method generally has the following characteristics.
- the characteristics of the component (C) used in the present invention are not limited to the following.
- the mass average molecular weight is about 1,000 to 200,000.
- the component (C) obtained by the above method can be used after being derivatized by further alkali treatment.
- Lignophenol obtained from natural lignin by a phase separation process is stable as a whole because the ⁇ -position of its activated carbon is blocked with a phenol derivative.
- the phenolic hydroxyl group readily dissociates under alkaline conditions, and the resulting phenoxide ion attacks the ⁇ -position of the adjacent carbon when it is sterically possible.
- the ⁇ -position aryl ether bond is cleaved, the lignophenol is reduced in molecular weight, and the phenolic hydroxyl group in the introduced phenol nucleus moves to the lignin matrix.
- the alkali-treated derivative is expected to have improved hydrophobicity compared to lignophenol before the alkali treatment.
- the alkoxide ion present in the carbon at the ⁇ -position or the carbanion of the lignin aromatic nucleus is also expected to attack the ⁇ -position, but this requires much higher energy than the phenoxide ion. Therefore, the adjacent group effect of the phenolic hydroxyl group of the introduced phenol nucleus preferentially appears under mild alkaline conditions, and further reaction occurs under severer conditions, and the phenolic hydroxyl group of the once etherified cresol nucleus is regenerated. As a result, it is expected that lignophenol is further reduced in molecular weight and hydrophilicity is increased by increasing the number of hydroxyl groups.
- lignophenol and lignophenol derivatives obtained by alkali treatment thereof have various characteristics due to the presence of phenolic and alcoholic hydroxyl groups.
- a derivative having different characteristics can be obtained.
- Examples of the method for protecting the hydroxyl group include protecting the hydroxyl group with a protecting group such as an acyl group (eg, acetyl group, propionyl group, benzoyl group).
- a protecting group such as an acyl group (eg, acetyl group, propionyl group, benzoyl group).
- a blending ratio of (A) polycarbonate resin, (B) aromatic polyester resin and (C) lignophenol is a resin mixture 100 comprising 99 to 30% by mass of component (A) and 1 to 70% by mass of component (B).
- the component (C) is 1 to 50 parts by mass with respect to parts by mass.
- the component (A) is 90 to 70% by mass
- the component (B) is 10 to 30% by mass
- the component (A) is 95 to 70% by mass
- the component (B) is 5 to 30% by mass.
- the component (C) is less than 1 part by mass, flame retardancy and fluidity cannot be improved, and when it exceeds 50 parts by mass, the fluidity becomes extremely high, so that the moldability deteriorates and the molding is difficult. Since it becomes difficult, it is not preferable.
- Component (C) is preferably 3 to 35 parts by mass, and more preferably 10 to 30 parts by mass.
- the polycarbonate resin composition of the present invention may contain an additive component as necessary in addition to the components (A) to (C).
- an additive component for example, phenol-based, phosphorus-based, sulfur-based antioxidants, antistatic agents, polyamide polyether block copolymers (permanent antistatic performance imparted), benzotriazole-based or benzophenone-based UV absorbers, hindered amine-based light stabilizers (Weathering agent), antibacterial agent, compatibilizer, colorant (dye, pigment) and the like.
- the amount of additive component added is not particularly limited as long as the properties of the polycarbonate resin composition of the present invention are maintained.
- the polycarbonate resin composition of the present invention can be obtained by blending the components (A) to (C) in the above proportions, and adding the additive components used as necessary in an appropriate proportion and kneading. Mixing and kneading at this time are premixed with a commonly used equipment such as a ribbon blender, a drum tumbler, etc., then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder. This method can be performed by a method using a machine and a conider.
- the heating temperature at the time of kneading is usually appropriately selected within the range of 240 to 300 ° C.
- the polycarbonate resin composition of the present invention is obtained by using the above melt-kneading molding machine or the obtained pellet as a raw material, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method.
- Various molded bodies can be produced by a foam molding method or the like.
- the above-mentioned melt-kneading method can be used to produce a pellet-shaped molding raw material, and then use the pellet to suitably produce an injection-molded body by injection molding or injection compression molding.
- the present invention also provides a molded article obtained by molding the above-described polycarbonate resin composition of the present invention.
- a molded article formed by molding the polycarbonate resin composition of the present invention preferably an injection molded article (including injection compression), a copying machine, a fax machine, a television, a radio, a tape recorder, a video deck, a personal computer, a printer, a telephone, Used for OA equipment such as information terminals, refrigerators, microwave ovens, home appliances, housings and various parts of electrical / electronic equipment.
- Oxygen index (LOI) Flame retardancy Measured according to ASTM standard D-2863.
- the oxygen index is a value indicating the minimum oxygen concentration necessary for the test piece to maintain combustion in terms of volume% in air.
- Moisture and heat resistance The moisture and heat resistance was determined by visually observing the presence or absence of surface deformation after leaving a flat test piece (80 mm ⁇ 80 mm ⁇ 1 mm) in an environment of 60 ° C. and 80% humidity for 300 hours. ⁇ indicates no deformation of the surface. In x, surface swelling and deformation are recognized. (6) Molding appearance It observed visually.
- each component used in each example is as follows.
- (A) Polycarbonate resin Aromatic polycarbonate resin: Product name Toughlon A1900 [manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight 19,500]
- Examples 1 to 4 and Comparative Examples 1 to 5 The above components were blended in the proportions shown in Table 1, supplied to an extruder (model name: VS40, manufactured by Tanabe Plastic Machinery Co., Ltd.), melt-kneaded at 240 ° C., and pelletized.
- 0.2 parts by mass of Irganox 1076 manufactured by BASF
- Adekastab C manufactured by ADEKA
- the obtained pellets were dried at 120 ° C.
- Table 1 shows the following. Examples 1 to 4 (A) Addition of (B) aromatic polyester resin and (C) lignophenol to polycarbonate resin is excellent in fluidity, impact resistance and heat resistance, as well as flame resistance, solvent resistance and moisture and heat resistance. Moreover, a polycarbonate resin composition having a good molded appearance can be obtained. Comparative examples 1 to 5 (B) If an aromatic polyester resin is not used, fluidity and impact resistance are lowered, and silver is generated to cause poor appearance (Comparative Example 1).
- the polycarbonate resin composition of the present invention can be suitably used as various materials in electronic / electrical equipment, information / communication equipment, OA equipment, automobile field, building material field, and the like.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
L'invention concerne : une composition de résine de polycarbonate caractérisée par le fait qu'elle contient (C) 1-50 parties en masse d'un lignophénol ayant une structure particulière pour 100 parties en masse d'un mélange de résines comprenant (A) 99-30 % en masse d'une résine de polycarbonate aromatique et (B) 1-70 % en masse d'une résine de polyester aromatique; et un corps moulé formé par moulage de la composition de résine de polycarbonate. La composition de résine de polycarbonate a un degré de biomasse élevé (degré de végétation), une performance environnementale supérieure telle qu'une réduction de la quantité d'émission de dioxyde de carbone et une réduction des matières de départ fossiles, une résistance supérieure à la chaleur humide, une fluidité supérieure, une résistance au choc supérieure et une incombustibilité supérieure, tout en maintenant une résistance à la chaleur élevée; elle est apte à une fluidisation élevée; elle est apte à une augmentation de la résistance aux solvants; elle a une dispersivité accrue de lignophénol; elle a une compatibilité favorable avec les résines de polycarbonate et les résines de polyester; et elle permet d'obtenir un corps moulé ayant un brillant et une transparence.
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JP2011195086A JP5769247B2 (ja) | 2011-09-07 | 2011-09-07 | ポリカーボネート樹脂組成物及び成形体 |
JP2011-195086 | 2011-09-07 |
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WO2013035439A1 true WO2013035439A1 (fr) | 2013-03-14 |
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PCT/JP2012/068288 WO2013035439A1 (fr) | 2011-09-07 | 2012-07-19 | Composition de résine de polycarbonate et corps moulé |
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JP (1) | JP5769247B2 (fr) |
TW (1) | TW201311815A (fr) |
WO (1) | WO2013035439A1 (fr) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997038051A1 (fr) * | 1996-04-08 | 1997-10-16 | Kaneka Corporation | Composition de resine de plastique ignifuge |
JP2010150424A (ja) * | 2008-12-25 | 2010-07-08 | Idemitsu Kosan Co Ltd | ポリカーボネート樹脂組成物 |
JP2010202712A (ja) * | 2009-02-27 | 2010-09-16 | Idemitsu Kosan Co Ltd | ポリカーボネート樹脂組成物 |
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US20110294928A1 (en) * | 2008-12-25 | 2011-12-01 | Mie University | Polycarbonate resin composition |
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2011
- 2011-09-07 JP JP2011195086A patent/JP5769247B2/ja not_active Expired - Fee Related
-
2012
- 2012-07-19 WO PCT/JP2012/068288 patent/WO2013035439A1/fr active Application Filing
- 2012-07-23 TW TW101126512A patent/TW201311815A/zh unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997038051A1 (fr) * | 1996-04-08 | 1997-10-16 | Kaneka Corporation | Composition de resine de plastique ignifuge |
JP2010150424A (ja) * | 2008-12-25 | 2010-07-08 | Idemitsu Kosan Co Ltd | ポリカーボネート樹脂組成物 |
JP2010202712A (ja) * | 2009-02-27 | 2010-09-16 | Idemitsu Kosan Co Ltd | ポリカーボネート樹脂組成物 |
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JP5769247B2 (ja) | 2015-08-26 |
JP2013056970A (ja) | 2013-03-28 |
TW201311815A (zh) | 2013-03-16 |
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