CN103842443B - Thermoplastic resin composition and formed body - Google Patents
Thermoplastic resin composition and formed body Download PDFInfo
- Publication number
- CN103842443B CN103842443B CN201280040012.6A CN201280040012A CN103842443B CN 103842443 B CN103842443 B CN 103842443B CN 201280040012 A CN201280040012 A CN 201280040012A CN 103842443 B CN103842443 B CN 103842443B
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- China
- Prior art keywords
- thermoplastic resin
- composition
- phenol
- flame retardant
- group
- 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.)
- Expired - Fee Related
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 62
- 239000011342 resin composition Substances 0.000 title claims abstract description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229920005610 lignin Polymers 0.000 claims abstract description 53
- 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 claims abstract description 37
- 239000003063 flame retardant Substances 0.000 claims abstract description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- 238000007493 shaping process Methods 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims description 43
- 229920005668 polycarbonate resin Polymers 0.000 claims description 40
- 239000004431 polycarbonate resin Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000005027 hydroxyaryl group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 150000003014 phosphoric acid esters Chemical class 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
- -1 poly(lactic acid) Polymers 0.000 description 42
- 238000000034 method Methods 0.000 description 35
- 150000002989 phenols Chemical class 0.000 description 28
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 10
- 239000002023 wood Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 229920000747 poly(lactic acid) Polymers 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 150000001896 cresols Chemical group 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229910052709 silver Inorganic materials 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920002522 Wood fibre Polymers 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- CFZAEHZKTCVBOQ-UHFFFAOYSA-N (2,3-dimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=CC(OP(O)(O)=O)=C1C CFZAEHZKTCVBOQ-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
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical class OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-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
- 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 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
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229920000229 biodegradable polyester Polymers 0.000 description 2
- 239000004622 biodegradable polyester Substances 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 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
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical group C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- BGGGMYCMZTXZBY-UHFFFAOYSA-N (3-hydroxyphenyl) phosphono hydrogen phosphate Chemical compound OC1=CC=CC(OP(O)(=O)OP(O)(O)=O)=C1 BGGGMYCMZTXZBY-UHFFFAOYSA-N 0.000 description 1
- GBZVNKQWXLVYNG-UHFFFAOYSA-N (3-phosphonooxyphenyl) dihydrogen phosphate Chemical compound OP(O)(=O)OC1=CC=CC(OP(O)(O)=O)=C1 GBZVNKQWXLVYNG-UHFFFAOYSA-N 0.000 description 1
- AAOADXIHXYIOMT-UHFFFAOYSA-N 1,1'-biphenyl;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=CC=C1C1=CC=CC=C1 AAOADXIHXYIOMT-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- XSXWOBXNYNULJG-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1O XSXWOBXNYNULJG-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- TVAJJUOMNRUGQA-UHFFFAOYSA-N 2-butoxyethyl dihydrogen phosphate Chemical compound CCCCOCCOP(O)(O)=O TVAJJUOMNRUGQA-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- PKXYFOQKRMBDCQ-UHFFFAOYSA-N 2-phenylpropan-2-yl dihydrogen phosphate Chemical compound OP(=O)(O)OC(C)(C)C1=CC=CC=C1 PKXYFOQKRMBDCQ-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
- 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
- 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 class CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=C(O)C=C1 KJMVGAOYRRKQPY-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
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 1
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- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
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- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- LAUIXFSZFKWUCT-UHFFFAOYSA-N [4-[2-(4-phosphonooxyphenyl)propan-2-yl]phenyl] dihydrogen phosphate Chemical compound C=1C=C(OP(O)(O)=O)C=CC=1C(C)(C)C1=CC=C(OP(O)(O)=O)C=C1 LAUIXFSZFKWUCT-UHFFFAOYSA-N 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 125000005127 aryl alkoxy alkyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 210000004292 cytoskeleton Anatomy 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 239000000539 dimer Substances 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
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000035611 feeding Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-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
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 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
- 230000035515 penetration Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 125000002444 phloroglucinyl group Chemical group [H]OC1=C([H])C(O[H])=C(*)C(O[H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- 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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The present invention relates to and there is lignin phenol 1 ~ 40 mass parts of ad hoc structure with the thermoplastic resin composition of (C) phosphorus flame retardant 0.5 ~ 30 mass parts and by its shaping formed body containing (A) thermoplastic resin 100 mass parts, (B).
Description
Technical field
The present invention relates to thermoplastic resin composition and utilize its formed body.More particularly, relating to by using life entity material, making its environmental performance excellent, and thermotolerance and flame retardant resistance excellent, in addition, the thermoplastic resin composition that molded appearance and humidity resistance are also excellent and utilize its formed body.
Background technology
In recent years, from the viewpoint of environment protection, the life entity materials such as Biodegradable polyester resin receive publicity.Representatively Biodegradable polyester resin, can enumerate poly(lactic acid).But life entity material usual physical strength compared with the general-purpose plastics of petroleum is low, and thermotolerance is also poor, and its purposes is restricted in very narrow and small scope.
So, the range of application of life entity material should be expanded, by coordinating the petroleum polymkeric substance such as aromatic polycarbonate resin in poly(lactic acid), or by coordinating the sponge carrying out delignification's process in Biodegradable resin, attempt the physical strength (for example, referring to patent documentation 1 or 2) improving resin-formed body.But the impact strength of these resin-formed bodies and thermotolerance are not necessarily enough high, can not fully meet the characteristic required by the basket of household appliances, office furniture and parts.
In the past, the present inventor etc. by coordinating the lignin phenol (lignophenol) with ad hoc structure in the polycarbonate resin containing polycarbonate resin or poly(lactic acid), have found environmental performance excellent, there is high workability and high-impact simultaneously, the poly carbonate resin composition (with reference to patent documentation 3 and 4) of flame retardant resistance and excellent heat resistance.But, when the resin combination that coordinates lignin phenol is shaping, occur that formed body is easily painted, and then the problem of the easy general silver color of formed body outward appearance.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-48067 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2005-60556 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2010-150424 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2010-202712 publication
Summary of the invention
The problem that invention will solve
The object of the invention is, provides environmental performance excellent, and while painted when suppressing shaping, mobility, molded appearance, humidity resistance are excellent, and the extremely excellent thermoplastic resin composition of flame retardant resistance and utilize its formed body.
Present inventors etc. are through carrying out found that of wholwe-hearted investigation, by coordinating (A) thermoplastic resin of specified quantitative, (B) lignin phenol and (C) phosphorus flame retardant, while painted when can be inhibited shaping, mobility, molded appearance, humidity resistance are excellent, the thermoplastic resin composition that flame retardant resistance is also extremely excellent in addition and utilize its formed body, completes the present invention.
That is, the invention reside in following thermoplastic resin composition and formed body are provided.
1. a thermoplastic resin composition, it is characterized in that, containing (A) thermoplastic resin 100 mass parts, (B) possesses lignin phenol 1 ~ 40 mass parts and (C) phosphorus flame retardant 0.5 ~ 30 mass parts of the structure that following general formula (I) represents.
(in general formula, R
1and R
4represent alkyl, aryl, alkoxyl group, aralkyl or phenoxy group, R
2represent hydroxyaryl or alkyl substituted hydroxy aryl, R
3represent hydroxyalkyl, alkyl, aryl, alkyl substituting aromatic base or-OR
5(R
5represent hydrogen atom, alkyl or aryl), the R beyond hydrogen atom
1~ R
5can have substituting group respectively, p and q represents the integer of 0 ~ 4.Be explained, when p is more than 2, multiple R
1can be identical or different respectively, in addition, when q is more than 2, multiple R
4can be identical or different respectively.〕
2. the thermoplastic resin composition as described in above-mentioned 1, wherein the thermoplastic resin of (A) composition comprises thermoplastic resin 60 ~ 0 quality % beyond polycarbonate resin 40 ~ 100 quality % and polycarbonate resin.
3. the thermoplastic resin composition as described in above-mentioned 1 or 2, wherein the phosphorus flame retardant of (C) composition is not containing halogen.
4., as the thermoplastic resin composition according to any one of above-mentioned 1 ~ 3, wherein the phosphorus flame retardant of (C) composition is phosphoric acid ester.
5. the formed body making the thermoplastic resin composition according to any one of above-mentioned 1 ~ 4 shaping.
Invention effect
According to the present invention, by using the life entity raw material of environmental protection and lignin phenol and phosphorus flame retardant, while painted when can be inhibited shaping, the excellent and thermoplastic resin composition that flame retardant resistance is extremely excellent of mobility, molded appearance, humidity resistance and use its formed body.When especially using polycarbonate resin as thermoplastic resin, while excellent thermotolerance and shock-resistance can be obtained, because the affinity of polycarbonate resin and lignin phenol is good, can not occur as immiscible polymer alloy that the top layer of formed body is peeled off, bad order.In addition, by improving life entity degree (vegetalization degree), environment-protecting thermoplastic resin combination and the formed bodys thereof such as low carbon dioxide discharge capacity, low fossil feedstock can be provided.
Embodiment
Thermoplastic resin composition of the present invention has the lignin phenol of ad hoc structure and the thermoplastic resin composition of (C) phosphorus flame retardant containing (A) thermoplastic resin and (B).Below, each composition and other can be described by added ingredients.
[(A) thermoplastic resin]
As (A) thermoplastic resin in the present invention, polycarbonate resin can be enumerated, phenylethylene resin series, polyvinyl resin, acrylic resin, plexiglass, polyvinyl chloride (PVC) RESINS, cellulose acetate resin, polyamide resin, vibrin (PET, PBT etc.), poly(lactic acid) and/or the multipolymer containing poly(lactic acid), polyacrylonitrile resin, acrylonitrile-butadiene-styrene resin (ABS resin), polyphenylene oxide resin (PPO), polyketone resin, polysulfone resin, polyphenylene sulfide (PPS), fluoro-resin, silicone resin, polyimide resin, polybenzimidazole resin, polyamide elastomer etc., and the multipolymer that these and other monomer is formed.
As (A) thermoplastic resin used in the present invention, from the viewpoint of the affinity between (B) composition and lignin phenol, there is in preferred molecular structure the thermoplastic resin of aromatic group, such as, aromatic polycarbonate resin, phenylethylene resin series, aromatic polyamide resin, aromatic polyester resins etc.
In addition, as (A) thermoplastic resin, by using polycarbonate resin, the excellent shock-resistance that polycarbonate resin can be had and thermotolerance give the composition obtained.Therefore, as thermoplastic resin, preferably use polycarbonate resin, or the mixture of polycarbonate resin and other thermoplastic resin.
Be described as the preferred polycarbonate resin of (A) thermoplastic resin below.
(polycarbonate resin)
As the polycarbonate resin of (A) thermoplastic resin, it can be aromatic polycarbonate resin, also can be aliphatic polycarbonate resin, but as mentioned above, from the viewpoint of the affinity between (B) composition, and the viewpoint of shock-resistance and thermotolerance, preferably use aromatic copolycarbonate tree.
< aromatic polycarbonate resin >
As aromatic polycarbonate resin, usually can use by the obtained aromatic polycarbonate resin of the reaction of dihydric phenol and carbonate precursor.Because aromatic polycarbonate resin is compared with other thermoplastic resins, thermotolerance, flame retardant resistance and shock-resistance are good, can as the main component of resin combination.
As dihydric phenol, can 4 be enumerated, 4 '-dihydroxybiphenyl; Two (4-hydroxy phenyl) alkane such as 1,1-bis-(4-hydroxy phenyl) methane, 1,1-bis-(4-hydroxy phenyl) ethane and 2,2-bis-(4-hydroxy phenyl) propane (dihydroxyphenyl propane); Two (4-hydroxy phenyl) naphthenic hydrocarbon; Two (4-hydroxy phenyl) oxide compound; Two (4-hydroxy phenyl) thioether; Two (4-hydroxy phenyl) sulfone; Two (4-hydroxy phenyl) sulfoxide; Two (4-hydroxy phenyl) ketone etc.Wherein preferred dihydroxyphenyl propane.As dihydric phenol, a kind of homopolymer in these dihydric phenols can be the use of, also can be the use of two or more multipolymers.In addition, also can be multi-functional aromatics and dihydric phenol and by the random branched polycarbonate resin of the thermoplasticity obtained.
As carbonate precursor, carbonyl halides, haloformate, carbonic ether etc. can be enumerated, specifically can enumerate carbonyl chloride, two haloformates of dihydric phenol, diphenyl carbonate, methylcarbonate and diethyl carbonate etc.
In the manufacturing processed of the aromatic polycarbonate resin used in the present invention, end terminator can be used as required, such as, the monohydric phenol compound that following general formula (II) represents can be exemplified as.
(in general formula, R
10represent the alkyl of carbon number 1 ~ 35, a represents the integer of 0 ~ 5.)
As the monohydric phenol compound that general formula (II) represents, preferred para-orientation body.The concrete example of monohydric phenol compound can enumerate phenol, p-cresol, p-tert-butylphenol, to tert-octyl phenol, p-cumylphenol, nonylphenol and Pentaphen etc.These monohydric phenols may be used alone, and also can use two or more combinations.
The aromatic polycarbonate resin that the present invention uses can have branched structure.Side chain agent can be used in order to import branched structure, such as, can use containing 1,1,1-tri-(4-hydroxy phenyl) ethane; α, α ', α "-three (4-hydroxy phenyl)-1,3,5-triisopropylbenzenes; 1-(Alpha-Methyl-α-(4 '-hydroxy phenyl) ethyl)-4-(α ', and α '-two (4 "-hydroxy phenyl) ethyl) benzene; The compound etc. of more than three in the functional groups such as Phloroglucinol, trimellitic acid and isatin two (ortho-cresol).
The viscosity-average molecular weight of aromatic polycarbonate resin that the present invention uses, from the viewpoint of the physical property of resin combination, preferably 10,000 ~ 40,000, more preferably 13,000 ~ 30,000.
In addition, in the present invention, as aromatic polycarbonate resin, at use aromatic copolycarbonate-poly organo alkyl copolymer, or when using containing the material of aromatic copolycarbonate-poly organo alkyl copolymer, the shock-resistance under flame retardant resistance and low temperature can be improved further.Form the organopolysiloxane of this multipolymer, consider from the angle of flame retardant resistance, preferred polydimethylsiloxane.
In the present invention, at use polycarbonate resin, preferably by aromatic polycarbonate resin and other thermoplastic resins used in combination time, more than 40 quality % are reached with polycarbonate resin, preferably the mode of 50 quality % uses, and can maintain physical strength (shock-resistance, thermotolerance etc.) thus.For polycarbonate resin, other thermoplastic resins preferably used in combination with aromatic polycarbonate resin, can select arbitrarily from described (A) thermoplastic resin, but from the viewpoint of the mutual solubility with polycarbonate resin, preferred polyester resin (PET, PBT etc.), poly(lactic acid) and/or the phenylethylene resin series such as multipolymer, acrylonitrile-butadiene-styrene resin containing poly(lactic acid).
[(B) lignin phenol]
(B) lignin phenol in the present invention has the structure shown in following general formula (I).
In general formula (I), R
1and R
4represent the alkyl (alkyl of preferred carbon number 1 ~ 4, be specially methyl, ethyl, propyl group etc.), aryl (the aryl of preferred carbon number 6 ~ 10, be specially phenyl etc.), alkoxyl group (alkoxyl group of preferred carbon number 1 ~ 4, is specially methoxyl group, oxyethyl group, propoxy-etc.), the aralkyl (aralkyl of preferred carbon number 12 ~ 20, be specially phenmethyl etc.), or phenoxy group.
R
2represent the hydroxyaryl (hydroxyaryl of preferred carbon number 6 ~ 14, specifically, represent 2-hydroxy phenyl, 3-hydroxy phenyl, 4-hydroxy phenyl etc.), or alkyl substituted hydroxy aryl (hydroxyaryl of preferred carbon number 7 ~ 18 is specially 2-hydroxy-5-methyl base phenyl, 3-hydroxy-5-methyl base phenyl, 4-hydroxy-5-methyl base phenyl etc.); R
3represent the hydroxyalkyl (hydroxyalkyl of preferred carbon number 1 ~ 4; be specially hydroxymethyl, hydroxyethyl etc.); alkyl (the alkyl of preferred carbon number 1 ~ 4; be specially methyl, ethyl, propyl group etc.); aryl (the aryl of preferred carbon number 6 ~ 10; be specially phenyl etc.), alkyl substituting aromatic base (aryl that the alkyl of preferred carbon number 1 ~ 10 replaces is specially toluyl, xylyl etc.) or-OR
5(R
5represent the aryl of the alkyl or aryl of hydrogen atom, alkyl, preferably carbon number 1 ~ 10, preferably carbon number 6 ~ 10).
R beyond hydrogen atom
1~ R
5can have substituting group respectively, p and q represents the integer of 0 ~ 4.
Be explained, when p is more than 2, multiple R
1can be identical or different respectively, in addition, when q is more than 2, multiple R
4can be identical or different respectively.
In the present invention, the structure optimization that above-mentioned general formula (I) represents derives from natural structure.
When deriving from natural structure, the R in above-mentioned general formula (I)
1and R
4determined by seeds, R
1and R
4the substituting group represented is methoxyl group, there is the structure that p and q is 1 or 2 respectively, or exists only not containing R
1and R
4the structure of one or both in the substituting group represented.
Such as, usually, softwood tree be containing 1 methoxyl group 3-replace body, in deciduous tree draft class plant containing 1 methoxyl group 3-replace body with containing 2 methoxyl groups 3,5-replace body with 1: 1 ratio exist.In addition, for any seeds and treelet, all may containing the structure do not had as the part in the above-mentioned substituting group of methoxyl group.
R
3during for deriving from natural structure, it is hydroxymethyl.
R
2during for deriving from natural structure, with equally above-mentioned, represent the hydroxyaryl (hydroxyaryl of preferred carbon number 6 ~ 14, be specially 2-hydroxy phenyl, 3-hydroxy phenyl, 4-hydroxy phenyl etc.) or alkyl substituted hydroxy aryl (hydroxyaryl of preferred carbon number 7 ~ 18 is specially 2-hydroxy-5-methyl phenyl, 3-hydroxy-5-methyl phenyl, 4-hydroxy-5-methyl phenyl etc.) etc.
In the present invention, by freely controlling the R deriving from natural structure
2, the conversion of (B) lignin phenol can be increased.
The weight-average molecular weight polystyrene conversion of the lignin phenol represented by above-mentioned general formula (I), preferably 1,000 ~ 200,000, more preferably 3,000 ~ 100,000.In addition, two preferred phenolic hydroxyl group of terminal group of lignin phenol of representing of above-mentioned general formula (I).
In addition, the concrete structure that the above-mentioned general formula (I) as operable in the present invention (B) composition represents, can enumerate the wooden cresols structure that such as following general formula (III) represents.
(lignin phenol)
Lignin phenol is derivative in the xylogen contained by timber, paper etc. and compound that is that come, and xylogen is between the gap of the carbohydrate of the cytoskeleton be such as filled in for forming wood, as the material that intercellular adhesive works.Because the structure of xylogen is very complicated, be not easy to use same as before, be transformed into lignin phenol and use very useful.
" B) manufacture method of lignin phenol)
Lignin phenol and carbohydrate are isolated with acid hydrolysis after can passing through to add phenol derivatives in the wood fibre such as timber, paper prime system material by (B) composition in the present invention.In addition, (B) composition contains the derivative of above-mentioned lignin phenol after alkaline purification, or containing the protected derivative of hydroxyl in above-mentioned lignin phenol or the above-mentioned lignin phenol derivative after alkaline purification.
The material that wood fibre prime system material has been lignifying, mainly as the various materials of timber, such as, can be exemplified as wood powder, wood is cut, waste wood and skirt materials etc.In addition, operable timber has any kind such as softwood tree, deciduous tree.In addition, various herbaceous plant or relative material also can be used, such as, agricultural waste etc.
When using these material separation lignin phenols, preferably use the material obtained without heating and pressurizing in sepn process.
As phenol derivatives, monohydric phenol derivative, diphenol derivative or trihydric phenol derivative etc. can be used.The concrete example of monohydric phenol derivative can be exemplified as phenol, naphthols, anthrol, oxanthranol etc., also can have the substituting group of more than 1 respectively.The concrete example of diphenol derivative can enumerate Resorcinol, Resorcinol etc., can have the substituting group of more than 1 respectively.The concrete example of trihydric phenol derivative can enumerate pyrogallol etc., also can have the substituting group of more than 1.
Such as, also can use as phenol derivatives containing above-mentioned compositions enumerated beyond derivative such as hydroxyl anthracene, methoxyphenol (Dan Ersan), methyl catechol, biphenyl, dimethyl hydroxyl aryl, trimethylammonium hydroxyaryl.
The substituent kind that phenol derivatives can contain is not particularly limited, any substituting group can be contained, but the group beyond preferred electron-withdrawing group (halogen atom etc.), such as can enumerate alkyl (methyl, ethyl, propyl group etc.), alkoxyl group (methoxyl group, oxyethyl group, propoxy-etc.), and aryl (phenyl etc.) etc.In addition, 1 is had at least not replace in 2 ortho positions of the phenolic hydroxyl group on preferred phenol derivatives.The particularly preferred example of phenol derivatives is cresols, especially meta-cresol or p-cresol.
As acid, preferably Mierocrystalline cellulose is had to the acid of swelling property.The concrete example of acid can be the sulfuric acid (such as, the sulfuric acid of 72 quality %) of such as more than concentration 65 quality %, the phosphoric acid of more than 85 quality %, the hydrochloric acid of more than 38 quality %, tosic acid, trifluoracetic acid, Tricholroacetic Acid and formic acid.
As the extraction separating method of the lignin phenol obtained as stated above, such as following 2 kinds of methods can be enumerated.
1st kind of method is the method described in patent No. 2895087 publication.Specifically, by wood fibre prime system penetration liquid phenol derivatives such as wood powders, make xylogen solvation in phenol derivatives, then add concentrated acid and carry out dissolving lignocellulose based material.Now, the positively charged ion on the side chain α position of xylogen basic structural unit is by phenol derivatives attack, and the lignin phenol having imported phenol derivatives in phenmethyl position generates mutually at phenol derivatives.Next be from phenol derivatives mutually extraction lignin phenol method.
For from phenol derivatives middle extraction lignin phenol mutually, undertaken by following manner: phenol derivatives is added in excessive ether, collect the throw out obtained and be dissolved in acetone again.The part being insoluble to acetone is removed by centrifugation, concentrated acetone-insoluble part.The part this being dissolved in acetone instills in excessive ether, collecting precipitation part.From this sediment fraction except after desolventizing, drying process, obtain lignin phenol with the form of dry thing.In addition, rugose wood element phenol obtains by means of only underpressure distillation removing phenol derivatives phase.In addition, acetone-insoluble part also can directly with the form of lignin phenol's solution, in the process (alkaline purification) of derivative materialization.
2nd kind of method is the method as described in Japanese Unexamined Patent Publication 2001-64494 publication.Specifically following method: after in wood fibre prime system material, the solvent of solid state or liquid phenol derivatives has been dissolved in infiltration, distillation is except desolventizing (absorption process of phenol derivatives), then, adding concentrated acid to this lignocellulose based material makes cellulose components dissolve, identical with the 1st kind of method, lignin phenol, in phenol derivatives middle generation mutually, extracts lignin phenol.
The extraction of lignin phenol can be carried out in the same manner as the 1st kind of method.Or use other following extracting process: add in excessive water by the total overall reaction liquid after concentrated acid process, collect insoluble part by centrifugation, dry after depickling.Acetone or alcohol extraction lignin phenol is added in this dry thing.Next, instilled in the same manner as the 1st kind of method by this soluble part in excess diethyl ether etc., lignin phenol obtains with the form of insoluble part.
In the 1st or the 2nd kind of these two kinds of methods, in the 2nd kind of method, the especially extracting process of the latter, that is, by the method for acetone or alcohol extracting and separating lignin phenol, the usage quantity of phenol derivatives is few so economy.In addition, because thus the method with a large amount of lignocellulose based material of a small amount of phenol derivatives process, can be applicable to a large amount of synthesis of lignin phenol.
(B) the of the present invention composition obtained by aforesaid method generally has following characteristics.Be explained, the feature of (B) used in the present invention composition is not by following restriction.
(1) weight-average molecular weight is about 1, and 000 ~ 200,000.
(2) substantially do not contain conjugated system in molecule, its tone is pole light color.
(3) derive from acerose fusing point and be about 170 DEG C, the fusing point deriving from deciduous tree is about 130 DEG C.
(4) result of phenol derivatives grafting selectively on side chain α position makes the amount of phenolic hydroxyl group very many, has been endowed the lignin derivative of height phenol characteristic.
(5) lignin structure unit aromatic proton with form ditan type structure at the aromatic proton of the phenol derivatives of side chain α position grafting, suppress from condensation.
(6) all kinds of SOLVENTS such as methyl alcohol, ethanol, acetone, diox, pyridine, THF (tetrahydrofuran (THF)), DMF (DIMETHYL FORMAMIDE) are easily dissolved in.
In addition, (B) composition obtained by aforesaid method can be used after derivative materialization by alkaline purification again.
The lignin phenol obtained by phase separation process by natural lignin, the α position of its activated carbon is closed by phenol derivatives, overall stability.But, in the basic conditions, the easy dissociation of its phenolic hydroxyl group, the phenonium ion β position carbon that possibility attack is adjacent in solid of generation.Like this, the aryl oxide bond rupture of β position, lignin phenol is degraded, and then the phenolic hydroxyl group imported on phenol nucleus shifts to xylogen parent.Therefore, expect that derivative through alkaline purification is compared with the lignin phenol before alkaline purification, hydrophobicity is better.
At this moment the alcoholate ion that is present on the carbon of γ position or the carbanion attack β position on xylogen aromatic proton is also expected, but this energy that needs are high far away compared with phenonium ion.Therefore, expect under the alkaline condition relaxed, the adjacent group importing the phenolic hydroxyl group of phenol core is preferentially embodied, under more extreme conditions, react further, the phenolic hydroxyl group regeneration of temporary transient etherfied cresols core, thus while making lignin phenol degraded further, because hydroxyl value increases, wetting ability also increases.
In addition, lignin phenol and the lignin phenol's derivative after alkaline purification thereof due to phenol and alcohol hydroxyl group existence and show diverse nature.By protecting this hydroxyl, the derivative showing other different qualities can be obtained.The method of protection hydroxyl can be enumerated such as, with protecting group protection hydroxyls such as acyl groups (such as can enumerate ethanoyl, propionyl, phenmethyl etc., preferred acyl group).In addition, by carrying out methylolation, producing new phenmethyl structure, its transition probabilities can be expanded further.
[(C) phosphorus flame retardant]
The phosphorus flame retardant of (C) phosphorus flame retardant in the present invention preferably not containing halogen.If containing halogen, then when formed body is burned in the generation of obnoxious flavour when likely causing shaping, mould burn into, the discharge of objectionable impurities, not preferred from the viewpoint of environmental pollution, security.
As not halogen-containing phosphorus flame retardant, there is not halogen-containing organic phosphorus flame retardant.As organic phosphorus flame retardant, if contain phosphorus atom and not halogen-containing organic compound, can use without particular limitation.Wherein, the phosphate compound of the ester Sauerstoffatom containing more than 1 and phosphorus atom Direct Bonding is preferably used.The phosphorus flame retardant not containing halogen beyond organophosphorus based compound has red phosphorus etc.
In addition, for phosphate compound, be not particularly limited, preferably not halogen-containing, the phosphate compound that such as following general formula (IV) represents.
(in general formula, R
11, R
12, R
13and R
14separately represent hydrogen atom or organic group; X represents the organic group of more than divalence; M represent 0 or 1, n represent more than 1 integer; R represents the integer of more than 0.)
In general formula (IV), organic group is the alkyl, cycloalkyl, aryl etc. that can be substituted or not be substituted.In addition, as substituting group when being substituted, there are alkyl, alkoxyl group, aryl, aryloxy, arylthio etc.In addition, by the group such as arylalkoxy alkyl etc. that these substituting groups form, or the aryl sulfonyl aryl etc. consisted of bondings such as Sauerstoffatom, nitrogen-atoms, sulphur atoms by these substituting groups also can be used as substituting group.
In addition, in general formula (IV), as organic group X more than divalence, refer to and can remove more than 1 group obtained with the hydrogen atom of carbon atom bonding from above-mentioned organic group.Such as, alkylidene group, (replacement) phenylene, the group that derives from the bisphenols as multinuclear phenols can be enumerated.Preferably enumerate dihydroxyphenyl propane, Resorcinol, Resorcinol, ditan, dihydroxydiphenyl and dihydroxy naphthlene etc.
Phosphate compound can be monomer, dimer, oligomer, polymer or these mixture.Specifically trimethyl phosphate can be enumerated, triethyl phosphate, Tributyl phosphate ester, trioctyl phosphate, three butoxyethyl phosphate, triphenyl, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, three (2-ethylhexyl) phosphoric acid ester, diisopropylbenzyl phosphoric acid ester, three (xylyl) phosphoric acid ester, three (cumyl) phosphoric acid ester, three naphthyl phosphates, bis-phenol A diphosphate, Resorcinol bisphosphate, resorcinol diphosphate, Resorcinol-diphenyl phosphoester, trisphenol triguaiacyl phosphate, toluene diphenyl phosphoester, or their replacement body, polymkeric substance etc.
Herein, as commercially available not halogen-containing phosphate compound, the TPP (triphenyl) that such as large eight chemical industrial companies manufacture can be enumerated, TXP (three (xylyl) phosphoric acid ester), CR-733S (Resorcinol two (diphenyl phosphoester)), CR-741 (phenol A bis-(diphenyl phosphoester)), PX-200 (1, 3-phenylene-four (2, 6-3,5-dimethylphenyl) phosphoric acid ester), PX-201 (1, 4-phenylene-four (2, 6-3,5-dimethylphenyl) phosphoric acid ester), PX-202 (4, 4 '-biphenylene-four (2, 6-3,5-dimethylphenyl) phosphoric acid ester) etc.
[mixing ratio of (A) thermoplastic resin, (B) lignin phenol and (C) phosphorus flame retardant]
(A) mixing ratio of thermoplastic resin, (B) lignin phenol and (C) phosphorus flame retardant is, relative to (A) composition 100 mass parts, (B) composition is 1 ~ 40 mass parts, and (C) composition is 0.5 ~ 30 mass parts.If (B) composition is less than 1 mass parts, then can not obtain the effect that flame retardant resistance improves, if more than 40 mass parts, then effect step-down painted when suppressing shaping, not preferably.Preferably (B) composition is 2 ~ 30 mass parts.In addition, if (C) composition is less than 0.5 mass parts, then effect step-down painted when suppressing shaping, the easy general silver color of formed body, not preferably, in addition, can not improve flame retardant resistance further.In addition, if (C) composition is more than 30 mass parts, then the reduction such as thermotolerance, shock-resistance, not preferably.Preferably (C) composition is 2 ~ 20 mass parts.
[additive component]
Thermoplastic resin composition of the present invention can add additive component as required while interpolation (A) composition, (B) composition and (C) composition.Such as, phenol system, phosphorus system, sulphur system antioxidant, static inhibitor, polyamide polyether block multipolymer (imparting permanent antistatic performance), benzotriazole system, benzophenone series UV light absorber, hindered amine system photostabilizer (weather agent), antiseptic-germicide, phase solvation, tinting material (dyestuff, pigment) etc.If the use level of additive component in the scope of characteristic keeping thermoplastic resin composition of the present invention, is then not particularly limited.
[mixing and molding]
Thermoplastic resin composition of the present invention by by above-mentioned (A) composition, (B) composition and (C) composition according to the above ratio, in addition as required by the additive component of use by proper ratio cooperation, mixingly to form.Cooperation now and the mixing apparatus can commonly used by use, such as ribbon blender, drum-type rotary drum (drumtumbler) etc. carry out pre-mixing, then by using the method for Henschel mixer (Henschelmixer), Banbury (Bumburymixer), single shaft screw extrusion press, biaxial screw forcing machine, multiaxis screw extrusion press and pugging extruder etc. to carry out.
Heating temperature time mixing can according to the kind of thermoplastic resin, suitable selection in the scope of 200 ~ 350 DEG C usually, but when as thermoplastic resin use polycarbonate resin, selects in the scope of 240 ~ 300 DEG C.
Thermoplastic resin composition of the present invention can pass through above-mentioned melting mixing forming machine, or with the particulate matter obtained for raw material, manufacture various formed body by injection molding method, compression molding method, extrinsion pressing, blow molding method, extrusion forming method, vacuum forming and foaming method etc.Particularly preferably by above-mentioned melting mixing method, manufacture granular shaping raw material, then utilize this particulate matter, manufacture injection-molded article by injection moulding or compression molding.
The present invention also provides a kind of by formed body shaping for the thermoplastic resin composition of the invention described above.
By formed body shaping for thermoplastic resin composition of the present invention, preferred injection-molded article (containing injection moulding compression) may be used in the OA machines such as duplicating machine, facsimile recorder, TV, receiving set, sound-track engraving apparatus, video recorder, computer, printing press, telephone set, information terminal, refrigerator, microwave oven, household appliances, the frame of electric and electronic apparatus, various parts etc.
Embodiment
The present invention is illustrated by embodiment, but these do not have any restriction to the present invention.
The performance test of the resin combination obtained in each example is performed as follows.
(1) melt index (MI): mobility
Condition determination resin temperature 260 DEG C, under load 21.18N, measures according to ASTM specification D-1238.
(2) heat-drawn wire (deformation under load temperature): thermotolerance
Measure according under ASTM specification D-648, load 1.8MPa.Heat-drawn wire represents thermotolerance benchmark.
(3) oxygen index value (LOI): flame retardant resistance
Measure according to ASTM specification D-2863.Oxygen index value is the value that the necessary minimum oxygen concentration of coupons maintenance burning represents in the capacity % in air.
(4) yellowness index (YI): tint permanence
Make the formed body after 5 the 13rd material feedings, adopt the spectral colorimetric meter ∑ 90 that Japanese electricity Se industrial manufactures, by measuring area 30
, C2 light source transmission method measure and try to achieve its mean value.Represent the tint permanence of formed body.
(5) molded appearance
Molded appearance by the tabular coupons (80mm × 80mm × 1mm) after injection moulding at visual judgement mold temperature 260 DEG C with or without occurring silver color.
Zero for not find general silver color.
× for finding general silver color.
(6) humidity resistance
Humidity resistance transfers horizontalization plate tensile sample sheet (80mm × 80mm × 1mm) after 300 hours with or without surface deformation by the environment of visual judgement 60 DEG C, humidity 80%.
Zero for not find surface deformation.
× for finding that surface is swelling, distortion.
(7) Ai Zuode impact strength (IZOD): shock-resistance
Use thickness is the coupons of 1/8 inch, according to ASTM specification D-256, measures at mensuration temperature 23 DEG C.
In addition, each composition used in each example is as follows.
(A) thermoplastic resin
Polycarbonate resin: aromatic polycarbonate resin (trade(brand)name TARFLONA1700, bright dipping Xing Chan company manufacture, viscosity-average molecular weight=17,800)
Poly(lactic acid): trade(brand)name LACEAH100, Mitsui Chemicals, Inc. manufacture
ABS: amorphousness phenylethylene resin series (acrylonitrile-styrene-divinyl copolymer, trade(brand)name AT-05, Japanese A & L Zhu Shihui company manufacture)
(B) lignin phenol
The wooden cresols that above-mentioned formula (III) represents:
The wood powder of Buna (rubber) is immersed in the acetone soln containing p-cresol, p-cresol is adsorbed on wood powder.The sulfuric acid vigorous stirring of 72 quality % is added to the wood powder after absorption.Stir after stopping and adding placement of purifying waste water, supernatant liquor is passed through repeatedly 6 decant operation except disacidify and excessive p-cresol.Throw out in drying receptacle, adds acetone, after the wooden cresols of the structure of extraction containing general formula (III), and distillation removing acetone.Specifically, carry out in the same manner as the embodiment 1 of Japanese Unexamined Patent Publication 2001-64494 publication.
(C) phosphorus flame retardant
Dihydroxyphenyl propane two (phenylbenzene) phosphoric acid ester (trade(brand)name PX-200, large eight chemical industrial companies manufacture)
Triphenyl (trade(brand)name TPP, large eight chemical industrial companies manufacture)
[embodiment 1 ~ 7 and comparative example 1 ~ 9]
Above-mentioned each composition is coordinated, supply extrusion machine (machine title: VS40, Tian Bian plastics machinery company manufactures), melting mixing at 240 DEG C, granulation in ratio shown in table 1.In addition, in all embodiments and comparative example, IRGANOX1076 (BASF AG's manufacture) 0.2 mass parts as phenol system antioxidant and ADEKASTABC (Co., Ltd. ADEKA System) 0.1 mass parts as phosphorous antioxidant are coordinated respectively.By the test portion sheet that obtains at 120 DEG C after drying in 12 hours, under the condition of injection moulding machine (Toshiba Machine Co. Ltd manufactures, pattern: IS100N) cylinder temperature 260 DEG C, die temperature 80 DEG C, obtain coupons by injection moulding.The performance of the coupons obtained by above-mentioned performance test evaluation, its result is as shown in table 1.
[table 1]
Learnt as follows by table 1.
Embodiment 1 ~ 7
If add (B) lignin phenol and (C) phosphorus flame retardant in the polycarbonate resin as (A) thermoplastic resin, then, while YI and flame retardant resistance can be improved, molded appearance and humidity resistance are also excellent.
Comparative example 1 ~ 9
If asynchronously use (B) lignin phenol and (C) phosphorus flame retardant, then YI reduces (comparative example 1, comparative example 3, comparative example 5, comparative example 7, comparative example 9), high flame retardant (comparative example 1, comparative example 2, comparative example 4) can not be realized, thermotolerance reduces (comparative example 4, comparative example 6, comparative example 8), and molded appearance and humidity resistance be enough high (comparative example 1, comparative example 3, comparative example 4, comparative example 7) also.
Use possibility in industry
Thermoplastic resin composition of the present invention is by using the life entity raw material wood element phenol and phosphorus flame retardant of environmental protection, painted when can prevent the forming process occurred when using lignin phenol, has excellent flame retardant resistance and thermotolerance simultaneously.And molded appearance, humidity resistance are also excellent.In addition, due to the environment-protecting thermoplastic resin combinations such as the output of carbonic acid gas reduces, fossil feedstock minimizing can be provided by use lignin phenol, therefore thermoplastic resin composition of the present invention goes for the field needing these characteristics, especially electronic apparatus tool, information communication apparatus, OA apparatus, automotive field, building materials field etc.
Claims (5)
1. a thermoplastic resin composition, is characterized in that, contains:
(A) thermoplastic resin 100 mass parts,
(B) have structure shown in following general formula (I) lignin phenol 1 ~ 40 mass parts and
(C) phosphorus flame retardant 0.5 ~ 30 mass parts,
In general formula, R
1and R
4represent alkyl, aryl, alkoxyl group, aralkyl or phenoxy group; R
2represent hydroxyaryl or alkyl substituted hydroxy aryl; R
3represent hydroxyalkyl, alkyl, aryl, alkyl substituting aromatic base or-OR
5, wherein R
5represent hydrogen atom, alkyl or aryl, the R beyond hydrogen atom
1~ R
5substituting group can be had respectively;
P and q represents the integer of 0 ~ 4, wherein, when p is more than 2, and multiple R
1can be identical or different respectively, when q is more than 2, multiple R
4can be identical or different respectively,
The thermoplastic resin of described (A) composition is the thermoplastic resin in molecular structure with aromatic group.
2. thermoplastic resin composition as claimed in claim 1, wherein,
(A) thermoplastic resin of composition comprises thermoplastic resin 60 ~ 0 quality % beyond polycarbonate resin 40 ~ 100 quality % and polycarbonate resin.
3. thermoplastic resin composition as claimed in claim 1, wherein,
(C) phosphorus flame retardant of composition is not containing halogen.
4. thermoplastic resin composition as claimed in claim 1, wherein,
(C) phosphorus flame retardant of composition is phosphoric acid ester.
5. a formed body, it is by shaping for the thermoplastic resin composition according to any one of Claims 1 to 4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011-138874 | 2011-06-22 | ||
| JP2011138874A JP5843310B2 (en) | 2011-06-22 | 2011-06-22 | Thermoplastic resin composition and molded body |
| PCT/JP2012/065656 WO2012176778A1 (en) | 2011-06-22 | 2012-06-19 | Thermoplastic resin composition and molded body |
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| CN103842443A CN103842443A (en) | 2014-06-04 |
| CN103842443B true CN103842443B (en) | 2016-04-20 |
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| CN (1) | CN103842443B (en) |
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| JP5942451B2 (en) * | 2012-02-06 | 2016-06-29 | 富士ゼロックス株式会社 | Lignophenol derivative, resin composition, resin molding |
| US9346922B2 (en) | 2013-11-26 | 2016-05-24 | International Business Machines Corporation | Flame retardant block copolymers from renewable feeds |
| US9284414B2 (en) | 2013-11-26 | 2016-03-15 | Globalfoundries Inc. | Flame retardant polymers containing renewable content |
| WO2017006986A1 (en) * | 2015-07-09 | 2017-01-12 | 出光ライオンコンポジット株式会社 | Resin composition and method for manufacturing same, and molded body |
| WO2017017875A1 (en) * | 2015-07-29 | 2017-02-02 | 出光ライオンコンポジット株式会社 | Highly reflective flame retardant thermoplastic resin composition, molded body, and reflector for lighting equipment |
| JP2020176213A (en) * | 2019-04-18 | 2020-10-29 | 清水建設株式会社 | Flame-retardant resin composition, molding and resin fiber |
| CN113897023A (en) * | 2021-09-18 | 2022-01-07 | 北京嘉诚瑞鑫科技有限公司 | Non-metal automobile body environment-friendly covering piece and manufacturing method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651478A (en) * | 2005-01-05 | 2005-08-10 | 福州大学 | Preparation of high boiling point alcohol lignin polyurethane |
| CN1817994A (en) * | 2006-02-07 | 2006-08-16 | 福州大学 | Modified rosin resin with high-boiling point alcohol lignin and its derivative and production thereof |
| CN101130627A (en) * | 2006-08-23 | 2008-02-27 | 富士施乐株式会社 | Resin composition, resin molding, package, production method of resin molding and recycling method of resin molding |
| WO2010074228A1 (en) * | 2008-12-25 | 2010-07-01 | 出光興産株式会社 | Polycarbonate resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04258672A (en) * | 1991-02-08 | 1992-09-14 | Oji Paper Co Ltd | Flame-retardant resin composition |
| JP3359718B2 (en) * | 1993-12-22 | 2002-12-24 | 株式会社竹中工務店 | Biodegradable resin composition |
| JP5572864B2 (en) * | 2008-12-25 | 2014-08-20 | 出光ライオンコンポジット株式会社 | Polycarbonate resin composition |
-
2011
- 2011-06-22 JP JP2011138874A patent/JP5843310B2/en not_active Expired - Fee Related
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2012
- 2012-06-19 WO PCT/JP2012/065656 patent/WO2012176778A1/en active Application Filing
- 2012-06-19 CN CN201280040012.6A patent/CN103842443B/en not_active Expired - Fee Related
- 2012-06-21 TW TW101122284A patent/TW201300455A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651478A (en) * | 2005-01-05 | 2005-08-10 | 福州大学 | Preparation of high boiling point alcohol lignin polyurethane |
| CN1817994A (en) * | 2006-02-07 | 2006-08-16 | 福州大学 | Modified rosin resin with high-boiling point alcohol lignin and its derivative and production thereof |
| CN101130627A (en) * | 2006-08-23 | 2008-02-27 | 富士施乐株式会社 | Resin composition, resin molding, package, production method of resin molding and recycling method of resin molding |
| WO2010074228A1 (en) * | 2008-12-25 | 2010-07-01 | 出光興産株式会社 | Polycarbonate resin composition |
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| JP2013006911A (en) | 2013-01-10 |
| WO2012176778A1 (en) | 2012-12-27 |
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