JP2004107511A - Resin composition and method for producing the same - Google Patents
Resin composition and method for producing the same Download PDFInfo
- Publication number
- JP2004107511A JP2004107511A JP2002272863A JP2002272863A JP2004107511A JP 2004107511 A JP2004107511 A JP 2004107511A JP 2002272863 A JP2002272863 A JP 2002272863A JP 2002272863 A JP2002272863 A JP 2002272863A JP 2004107511 A JP2004107511 A JP 2004107511A
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- group
- formula
- resin composition
- carbon atoms
- resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 19
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 28
- 229920001955 polyphenylene ether Polymers 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 150000002430 hydrocarbons Chemical group 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 238000004898 kneading Methods 0.000 abstract description 4
- 239000002801 charged material Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- -1 phosphorus compound Chemical class 0.000 description 21
- 230000000704 physical effect Effects 0.000 description 16
- 239000003063 flame retardant Substances 0.000 description 14
- 238000000465 moulding Methods 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 12
- 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 11
- 230000000052 comparative effect Effects 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 8
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 4
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920005668 polycarbonate resin Polymers 0.000 description 4
- 239000004431 polycarbonate resin Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene 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
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004992 fast atom bombardment mass spectroscopy Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- GRXOKDOOUFYKLX-UHFFFAOYSA-N 3,5-dichloro-7-oxabicyclo[2.2.1]hepta-1(6),2,4-triene Chemical compound ClC1=C(O2)C(Cl)=CC2=C1 GRXOKDOOUFYKLX-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- VKRWVLAGVUOYLB-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propylurea Chemical compound CCO[Si](C)(OCC)CCCNC(N)=O VKRWVLAGVUOYLB-UHFFFAOYSA-N 0.000 description 1
- MXDWUGFTSGOHRF-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propylurea Chemical compound CO[Si](C)(OC)CCCNC(N)=O MXDWUGFTSGOHRF-UHFFFAOYSA-N 0.000 description 1
- KXRLIZRDCCQKDZ-UHFFFAOYSA-N 3-ethyl-5-methyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(CC)=CC2=C1 KXRLIZRDCCQKDZ-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- NGNBLQAYJAKWKR-UHFFFAOYSA-N 5-methyl-3-phenyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound O1C=2C(C)=CC1=CC=2C1=CC=CC=C1 NGNBLQAYJAKWKR-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ATGKAFZFOALBOF-UHFFFAOYSA-N cyclohexyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCCC1 ATGKAFZFOALBOF-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、品質安定性に優れ、安価で、かつ流動性と難燃性と耐熱性と透明性と色調とダート衝撃性のバランスに優れる樹脂組成物とその製造方法に関するものである。
【0002】
【従来の技術】
易燃性合成樹脂の難燃化としては、一般には従来よりハロゲン系化合物、リン系化合物、およびこれらの併用やさらには三酸化アンチモンとを添加する等の難燃化手法が用いられてきた。
しかしながら、これら従来よりの難燃剤は有害であると言われており、最近では特に環境面からハロゲン、アンチモン、リンなどを含有しない難燃性樹脂組成物が求められている。
【0003】
環境に好ましい難燃性樹脂組成物としては、従来より金属水酸化物を多量に配合した材料が開発されているが材料の比重が大幅にアップするだけでなく、耐衝撃性や成形流動性の低下が大きく実用性に乏しいのが現状である。
特定のシリコーン化合物を配合することにより難燃化された樹脂組成物が開示されている。(例えば、特許文献1、特許文献2、特許文献3、特許文献4、特許文献5、特許文献6参照)
【0004】
さらに、シリコーン化合物を添加しても難燃性が得られ難いために、シリコーン化合物とパーフルオロアルカンスルホン酸金属塩とを併用したポリカーボネート樹脂系の難燃性樹脂組成物が開示されている。しかしながら、パーフルオロアルカンスルホン酸金属塩はフッ素を含んでおり、ハロゲンを用いない難燃樹脂組成物とは言えないだけでなく、ポリカーボネート樹脂以外では難燃効果がほとんど見られない。(特許文献7、特許文献8、特許文献9参照)
【0005】
ポリカーボネート樹脂以外のハロゲン系難燃剤を含まない代表的難燃樹脂として、リン系難燃剤を添加したポリフェニレンエーテルおよびそれとポリスチレンとのポリマーブレンド物が知られている。また、シリコーン化合物を配合したポリフェニレンエーテル系樹脂の難燃樹脂組成物が開示されているが、難燃性、流動性、耐衝撃性、耐熱性などのバランスにおいて、満足できるものではなかった。(特許文献10、特許文献11参照)
【0006】
一方、反応性基を含有する籠状シルセスキオキサンを、その反応性基においてポリマーと反応させることにより、籠状シルセスキオキサンを含有するポリマーを生成する方法が提案されているが、流動性と難燃性と耐熱性と透明性と色調とダート衝撃性バランスにおいて十分ではなかった。(特許文献12参照)
ポリフェニレンエーテル樹脂に官能基を有する籠状シルセスキオキサンを添加することにより流動性と難燃性を向上させる提案がなされているが、流動性と難燃性と耐熱性と透明性と色調とダート衝撃性バランスにおいて十分ではなかった。(特許文献13参照)
【0007】
【特許文献1】
特公昭62−60421号公報
【特許文献2】
特許第1684119号公報
【特許文献3】
特許第1935582号公報
【特許文献4】
特開平10−139964号公報
【特許文献5】
特開平11−140294号公報
【特許文献6】
特開平11−222559号公報
【特許文献7】
特許第2719486号公報
【特許文献8】
特許第2746519号公報
【特許文献9】
特開平11−217494号公報
【特許文献10】
特許第1935582号公報
【特許文献11】
特公平8−32825号公報
【特許文献12】
米国特許第5484867号明細書
【特許文献13】
国際公開第02/059208号パンフレット
【0008】
【発明が解決しようとする課題】
本発明は、品質安定性に優れ、安価で、かつ流動性と難燃性と耐熱性と透明性と色調とダート衝撃性のバランスに優れた樹脂組成物とその製造方法を提供することである。
【0009】
【課題を解決するための手段】
本発明者は上記課題を達成する技術を鋭意検討した結果、熱可塑性樹脂と、特定構造の籠状シルセスキオキサン部分開裂構造体と、特定のケイ素化合物を、特定の割合にて、押出機に投入して、溶融混練する方法をとることにより、品質安定性に優れ、安価で、かつ流動性と難燃性と耐熱性と透明性と色調とダート衝撃性のバランスに優れた樹脂組成物が得られることを見いだし、本発明を完成するに至った。
すなわち本発明は、
1.(a)熱可塑性樹脂と、式(1)で示される(b)籠状シルセスキオキサン部分開裂構造体と、式(2)および/または(3)で示される(c)ケイ素化合物を、(c)/(b)のモル比が0.5〜3になる割合で、押出機に投入し、溶融混練することにより得られる樹脂組成物、
【0010】
【化3】
【0011】
(Rは水素原子、炭素原子数1から20の置換又は非置換の炭化水素基又はケイ素原子数1から10のケイ素原子含有基から選ばれ、Rは全て同一でも複数の基で構成されていても良い。)
【0012】
Z−A−SiX3 …式(2)
Z−A−Si(Y)X2 …式(3)
(Aは、炭素数1〜10個の炭化水素基であって、分岐構造をしていても、していなくてもよく、主鎖中に、窒素原子あるいは酸素原子を含有していても、していなくてもよい。Xは、炭素数1〜6個のアルコキシ基である。Yは、炭素数1〜6個のアルコキシ基以外の炭化水素基である。Zは、アミノ基、アミド基、水酸基、チオール基、エポキシ基、イソシアネート基、ビニル基、ハロゲンのいずれかから選ばれる。)
【0013】
2.(a)熱可塑性樹脂がスチレン系樹脂であることを特徴とする上記1に記載の樹脂組成物、
3.(a)熱可塑性樹脂がポリフェニレンエーテル系樹脂であることを特徴とする上記1に記載の樹脂組成物、
4.(a)熱可塑性樹脂100重量部に対し、(b)籠状シルセスキオキサン部分開裂構造体1〜30重量部を用いることを特徴とする上記1〜3のいずれかに記載の樹脂組成物、
5.式(1)において、Rがイソブチル基であることを特徴とする上記1〜4のいずれかに記載の樹脂組成物、
6.(a)熱可塑性樹脂と、式(1)で示される(b)籠状シルセスキオキサン部分開裂構造体と、式(2)および/または(3)で示される(c)ケイ素化合物を、(c)/(b)のモル比が0.5〜3になる割合で、押出機に投入し、溶融混練することを特徴とする樹脂組成物の製造方法、
【0014】
【化4】
【0015】
(Rは水素原子、炭素原子数1から20の置換又は非置換の炭化水素基又はケイ素原子数1から10のケイ素原子含有基から選ばれ、Rは全て同一でも複数の基で構成されていても良い。)
【0016】
Z−A−SiX3 …式(2)
Z−A−Si(Y)X2 …式(3)
(Aは、炭素数1〜10個の炭化水素基であって、分岐構造をしていても、していなくてもよく、主鎖中に、窒素原子あるいは酸素原子を含有していても、していなくてもよい。Xは、炭素数1〜6個のアルコキシ基である。Yは、炭素数1〜6個のアルコキシ基以外の炭化水素基である。Zは、アミノ基、アミド基、水酸基、チオール基、エポキシ基、イソシアネート基、ビニル基、ハロゲンのいずれかから選ばれる。)
7.押出機のベントポートから95kPa以下の真空度で脱揮することを特徴とする上記6に記載の製造方法、を提供するものである。
【0017】
【発明の実施の形態】
以下、本願発明について具体的に説明する。
本発明の(a)熱可塑性樹脂とは、加熱により成形加工可能な熱可塑性を示す樹脂であって、例えば、スチレン系樹脂、ポリフェニレンエ−テル系樹脂、ポリアミド6やポリアミド66に代表されるポリアミド、ポリアセタール、ポリカーボネート、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、ポリエチレンテレフタレート、ポリサルホン、ポリエーテルサルホン、ポリフェニレンサルファイド、ポリアリレート、熱可塑性ポリイミド、熱可塑性ポリエーテルイミド、ポリエーテルエーテルケトン、液晶ポリエステル、ポリエチレン、ポリプロピレン、塩化ビニル樹脂、ポリメチルメタクリレート、ポリ塩化ビニリデン、エチレンビニルアルコール共重合体、ポリエステルエラストマー、ポリアミドエラストマー、エチレン−プロピレン共重合体に代表されるオレフィン系エラストマー、などが挙げられる。さらにPPE/PA、PA/PP、PC/ABSなどのポリマーアロイも挙げられる。
【0018】
特にこれらの熱可塑性樹脂の中でも、流動性、コスト、透明性の観点から、スチレン系樹脂が好ましい。ここでスチレン系樹脂とは、ビニル芳香族化合物の単独重合体および/またはビニル芳香族化合物を含む共重合体のことである。ビニル芳香族化合物は、特にスチレンが好ましい。スチレン系樹脂の例をあげると、アタクティックポリスチレン、シンジオタクティックポリスチレン、ハイインパクトポリスチレン、AS樹脂(アクリロニトリル−スチレン共重合体)、ABS樹脂(アクリロニトリル−ブタジエン−スチレン共重合体)、ビニル芳香族化合物−共役ジエン化合物ブロック共重合体、ビニル芳香族化合物−共役ジエン化合物ブロック共重合体の水素添加物などがあり、各々単独で用いてもよいし、混合して用いてもよい。
【0019】
一方、熱可塑性樹脂の中でも、透明性、難燃性、耐熱性、コストの観点から、ポリフェニレンエ−テル系樹脂が好ましい。
ここで、ポリフェニレンエーテル系樹脂とは、ポリフェニレンエーテル樹脂単独又はポリフェニレンエーテル樹脂と前述のスチレン系樹脂との混合物であり、さらに他の樹脂が混合されたものも含まれる。ポリフェニレンエーテル樹脂とスチレン系樹脂との混合物を用いる場合は、ポリフェニレンエーテル樹脂とスチレン系樹脂との合計量に対して、ポリフェニレンエーテル樹脂が50wt%以上、好ましくは70wt%以上、さらに好ましくは80wt%以上である。
ここで、ポリフェニレンエ−テル樹脂とは、
式(4)の繰り返し単位構造
【0020】
【化5】
【0021】
(R1、R4は、それぞれ独立して、水素、第一級もしくは第二級の低級アルキル、フェニル、アミノアルキル、炭化水素オキシを表わす。R2、R3は、それぞれ独立して、水素、第一級もしくは第二級の低級アルキル、フェニルを表わす。)からなり、還元粘度(0.5g/dl、クロロホルム溶液、30℃測定)が、0.15〜1.0dl/gの範囲にあるホモ重合体及び/または共重合体である。さらに好ましい還元粘度は、0.20〜0.70dl/gの範囲、最も好ましくは0.40〜0.60の範囲である。
【0022】
このポリフェニレンエーテル樹脂の具体的な例としては、ポリ(2,6−ジメチル−1,4−フェニレンエーテル)、ポリ(2−メチル−6−エチル−1,4−フェニレンエーテル)、ポリ(2−メチル−6−フェニル−1,4−フェニレンエーテル)、ポリ(2,6−ジクロロ−1,4−フェニレンエーテル)等が挙げられ、さらに、2,6−ジメチルフェノールと他のフェノール類(例えば、2,3,6−トリメチルフェノールや2−メチル−6−ブチルフェノール)との共重合体のようなポリフェニレンエーテル共重合体も挙げられる。中でもポリ(2,6−ジメチル−1,4−フェニレンエーテル)、2,6−ジメチルフェノールと2,3,6−トリメチルフェノールとの共重合体が好ましく、さらにポリ(2,6−ジメチル−1,4−フェニレンエーテル)が好ましい。
【0023】
本発明で使用するポリフェニレンエーテル樹脂の製造方法の例として、米国特許第3306874号明細書記載の第一銅塩とアミンのコンプレックスを触媒として用い、2,6−キシレノールを酸化重合する方法がある。
米国特許第3306875号明細書、米国特許第3257357号明細書および米国特許第3257358号明細書、特公昭52−17880号公報および特開昭50−51197号公報および特開昭63−152628号公報などに記載された方法もポリフェニレンエーテル樹脂の製造方法として好ましい。
本発明のポリフェニレンエーテル樹脂は、重合行程後のパウダーのまま用いてもよいし、押出機などを用いて、窒素ガス雰囲気下あるいは非窒素ガス雰囲気下、脱揮下あるいは非脱揮下にて溶融混練することでペレット化して用いてもよい。
【0024】
本発明のポリフェニレンエーテル系樹脂は、種々のジエノフィル化合物により官能化されたポリフェニレンエーテル樹脂も含まれる。種々のジエノフィル化合物には、例えば無水マレイン酸、マレイン酸、フマル酸、フェニルマレイミド、イタコン酸、アクリル酸、メタクリル酸、メチルアリレート、メチルメタクリレート、グリシジルアクリレート、グリシジルメタクリレート、ステアリルアクリレート、スチレンなどの化合物が挙げられる。さらにこれらジエノフィル化合物により官能化する方法としては、ラジカル発生剤存在下あるいは非存在下で押出機などを用い、脱揮下あるいは非脱揮下にて溶融状態で官能化してもよい。例えば特許第3289715号公報や特願2001−016550号公報に記載の方法により官能化してもよい。
本発明の(b)籠状シルセスキオキサン部分開裂構造体について以下に説明する。本発明に使用される籠状シルセスキオキサン部分開裂構造体は、以下の式(1)で表される籠の一部が開いた構造のシルセスキオキサンである。
【0025】
【化6】
【0026】
(Rは水素原子、炭素原子数1から20の置換又は非置換の炭化水素基又はケイ素原子数1から10のケイ素原子含有基から選ばれ、Rは全て同一でも複数の基で構成されていても良い。)
流動性、難燃性、ブリードアウトのしにくさの観点から、Rは炭素数1から10の炭化水素基が好ましく、さらには、アルキル基が好ましい。より具体的には、イソブチル基、イソオクチル基が好ましく、特にはイソブチル基が好ましい。
【0027】
籠状シルセスキオキサンの合成法としては例えばBrownらのJ.Am.Chem.Soc.1965,87,4313や、FeherらのJ.Am.Chem.Soc.1989,111,1741あるいはOrganometallics 1991,10,2526などが報告されている。例えばシクロヘキシルトリエトキシシランを水/メチルイソブチルケトン中で触媒にテトラメチルアンモニウムヒドロキサイドを加えて反応させることにより結晶として得られる。また式(1)で表される籠状シルセスキオキサン部分開裂構造体は、完全縮合型の籠状シルセスキオキサンを製造する際に同時に生成するか、完全縮合型の籠状シルセスキオキサンからトリフルオロ酸やテトラエチルアンモニウムヒドロキサイドによって部分切断することにより合成できることがFeherらのChem.Commun.,1998,1279によって報告されている。さらに、RSiT3(T=Clまたはアルコキシ基)型化合物から、直接合成することもできる。
【0028】
本発明の(c)ケイ素化合物は、式(2)および/または(3)で表されるケイ素化合物である。
Z−A−SiX3 …式(2)
Z−A−Si(Y)X2 …式(3)
(Aは、炭素数1〜10個の炭化水素基であって、分岐構造をしていても、していなくてもよく、主鎖中に、窒素原子あるいは酸素原子を含有していても、していなくてもよい。Xは、炭素数1〜6個のアルコキシ基である。Yは、炭素数1〜6個のアルコキシ基以外の炭化水素基である。Zは、アミノ基、アミド基、水酸基、チオール基、エポキシ基、イソシアネート基、ビニル基、ハロゲンのいずれかから選ばれる。)
【0029】
ここで、(c)ケイ素化合物におけるZは、アミノ基、アミド基、水酸基、チオール基、エポキシ基、イソシアネート基、ビニル基、ハロゲンのいずれかから選ばれるが、難燃性、耐熱性、透明性、色調の観点から、アミノ基、エポキシ基が好ましく、さらに好ましくはアミノ基である。
式(2)で表されるケイ素化合物の具体例としては、N−β(アミノエチル)γ−アミノプロピルトリメトキシシラン、N−β(アミノエチル)γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシシラン、γ−アミノプロピルトリエトキシシシラン、γ−ウレイドプロピルトリメトキシシラン、γ−ウレイドプロピルトリエトキシシランなどが挙げられる。流動性と難燃性と耐熱性と透明性と色調とダート衝撃性のバランスの観点から、特に、N−β(アミノエチル)γ−アミノプロピルトリメトキシシラン、N−β(アミノエチル)γ−アミノプロピルトリエトキシシランが好ましい。
【0030】
式(3)で表されるケイ素化合物の具体例としては、N−β(アミノエチル)γ−アミノプロピルメチルジメトキシシラン、N−β(アミノエチル)γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルメチルジメトキシシシラン、γ−アミノプロピルメチルジエトキシシシラン、γ−ウレイドプロピルメチルジメトキシシラン、γ−ウレイドプロピルメチルジエトキシシランなどが挙げられる。流動性と難燃性と耐熱性と透明性と色調とダート衝撃性のバランスの観点から、特に、N−β(アミノエチル)γ−アミノプロピルメチルジメトキシシラン、N−β(アミノエチル)γ−アミノプロピルメチルジエトキシシランが好ましい。
【0031】
(c)ケイ素化合物と(b)籠状シルセスキオキサン部分開裂構造体とのブレンドする割合(モル比)を、(c)/(b)のモル比と定義し、その値は0.5〜3が好ましく、さらに0.7〜2.0が好ましく、より好ましくは0.8〜1.5、さらにより好ましくは、0.9〜1.2である。
押出機は、樹脂を溶融混練できる能力を有する装置であれば特に制限はないが、二軸同方向回転押出機、単軸同方向回転押出機、二軸異方向回転押出機、単軸異方向回転押出機が挙げられ、得られる組成物の物性と生産性の観点から、二軸同方向回転押出機が好ましい。
【0032】
本発明の製造方法は、(a)熱可塑性樹脂と、上記にあげたように、(c)ケイ素化合物と(b)籠状シルセスキオキサン部分開裂構造体とのブレンドする割合、すなわち(c)/(b)のモル比が0.5〜3になる割合で押出機に投入し、溶融混練することを特徴とする製造方法である。この際、原料の投入の仕方は、以下の方法が挙げられる。1)全ての原料を第1フィード口からフィードする方法。2)(a)成分と(b)成分を第1フィード口からフィードし、さらに第2フィード口から(c)成分をフィードする方法。3)(a)成分と(c)成分を第1フィード口からフィードし、さらに第2フィード口から(b)成分をフィードする方法。押出機のトルクの観点から1)の方法が、より好ましい。
【0033】
押出機の設定温度は特に制限はないが、熱可塑性樹脂が溶融混練できる温度が好ましい。従って、200〜350℃が好ましく、250〜330℃がより好ましく、290〜320℃が特により好ましい。
押出機の回転数は特に制限はないが、得られる物性の観点から、50〜1500rpm、好ましくは100〜1200rpm、より好ましくは150〜1000rpmである。
【0034】
押出機のベントポートは、少なくとも(a)、(b)、(c)成分が全て投入された場所より、ダイ側に設定することが好ましく、大気開放型でもよいし、真空ポンプで減圧にするのもよい。ストランド安定性および後述する(b)成分と(c)成分の反応性の観点から真空ポンプで減圧にするのが好ましく、95kPa以下の真空度で脱揮するのが好ましく、さらに70kPa以下、特には50kPa以下がより好ましい。
これらの製造方法により、以下の反応式(1)が示すように、式(1)の籠状シルセスキオキサン部分開裂構造体が、完全にかごが閉じた構造の籠状シルセスキオキサン(式(5))に変換されることが推定される。
【0035】
【化7】
【0036】
同様に、以下の反応式(2)が示すように、式(1)の籠状シルセスキオキサン部分開裂構造体が、完全にかごが閉じていない構造の籠状シルセスキオキサン(式(6))に変換されることが推定される。
【0037】
【化8】
【0038】
従って、本発明の製造方法は、式(5)や式(6)に示される官能基を有する籠状シルセスキオキサンを合成して単離するプロセスを簡素化することができる。すなわち、反応式(1)と反応式(2)が示す反応プロセスと熱可塑性樹脂とのブレンドするプロセスを、押出し機による溶融混練プロセスにより同時に実施することができる製造方法である。これによりプロセスの簡略化と安価な樹脂組成物の製造が可能となる。
【0039】
なお、本発明においては(b)籠状シルセスキオキサン部分開裂構造体と(c)ケイ素化合物とは必ずしも100%反応している必要はなく、本発明の効果を損なわない範囲で未反応の(b)籠状シルセスキオキサン部分開裂構造体および(c)ケイ素化合物が樹脂組成物中に残存していてもかまわない。
本発明における(b)成分の籠状シルセスキオキサン部分開裂構造体の配合量は、(a)熱可塑性樹脂100重量部に対し、1〜30重量部が好ましく、さらに2〜20重量部が好ましく、さらに3〜10重量部がより好ましい。この配合量が1重量部より少ないと、十分な流動性、難燃性が得られにくい。またこの配合量が30重量部より多いと、十分な耐熱性が得られにくい。
ここで(c)成分は、前述したように、(c)ケイ素化合物と(b)籠状シルセスキオキサン部分開裂構造体とのブレンドする割合(モル比)、(c)/(b)のモル比を0.5〜3になるように配合することが好ましい。
【0040】
本発明では、上記の成分の他に、本発明の特徴および効果を損なわない範囲で必要に応じて他の附加的成分、例えば、無機充填剤(ガラス繊維、金属繊維、チタン酸カリウム、炭素繊維、炭化ケイ素、セラミック、窒化ケイ素、マイカ、ネフェリンシナイト、タルク、ウオラストナイト、スラグ繊維、フェライト、ガラスビーズ、ガラスパウダー、ガラスバルーン、石英、石英ガラスなど。形状は繊維状、板状、球状など任意。)、酸化防止剤、エラストマー(エチレン/プロピレン共重合体、エチレン/1−ブテン共重合体、エチレン/プロピレン/非共役ジエン共重合体、エチレン/アクリル酸エチル共重合体、エチレン/メタクリル酸グリシジル共重合体、エチレン/酢酸ビニル/メタクリル酸グリシジル共重合体およびエチレン/プロピレン−g−無水マレイン酸共重合体、ABSなどのオレフィン系共重合体、ポリエステルポリエーテルエラストマー、ポリエステルポリエステルエラストマー、ビニル芳香族化合物−共役ジエン化合物ブロック共重合体、ビニル芳香族化合物−共役ジエン化合物ブロック共重合体の水素添加物)、可塑剤(オイル、低分子量ポリエチレン、エポキシ化大豆油、ポリエチレングリコール、脂肪酸エステル類等)、耐候(光)性改良剤、ポリオレフィン用造核剤、スリップ剤、各種着色剤、離型剤等を添加してもかまわない。
【0041】
本発明により得られた樹脂組成物は、従来より公知の種々の方法、例えば、射出成形、押出成形、中空成形により各種部品の成形体として成形できる。これら成形体は、例えば、家電OA部品、自動車用部品、事務機器用部品、電子材料部品など、特に難燃性と耐熱性が要求される用途に適している。また、シート、フィルム、発泡体にも適している。
本発明を以下、実施例に基づいて説明する。但し本発明はその主旨を越えない限り以下の実施例に限定されるものではない。
【0042】
ポリフェニレンエーテル(PPE−1)
2,6−ジメチルフェノールを酸化重合して得た還元粘度0.42のパウダー状のポリ(2,6−ジメチル−1,4−フェニレンエーテル)である。
各樹脂組成物の成形と物性評価を、以下の方法に従って実施した。
(1)成形
得られたペレットを、シリンダー温度320/330/320/310℃、射速85%、金型温度90℃に設定した射出成形機[IS−80EPN:東芝機械(株)社製]を用いて成形を行った。
(2)流動性
得られたペレットを、上記(1)の成形条件にて、厚み1.6mm×長さ127mm×幅12.7mmのASTMタンザク試験片を成形するに際し、1mmショートするときのゲージ圧力を測定した。この圧力をSSP(MPa)(「Short Shot Pressure」を略した。)とし、この値が小さいほど流動性に優れる。
【0043】
(3)難燃性
(3−1)平均燃焼時間
厚み1.6mm×長さ127mm×幅12.7mmのASTMタンザク試験片に成形し、Underwriters LaboratoriesのUL−94垂直燃焼試験に基ずき、燃焼試験を実施した。すなわち、5本の試験片について燃焼試験を実施し、10秒間の接炎後、炎を離してから炎が消えるまでの燃焼時間をt1(秒)とし、再び10秒間の接炎後、炎を離してから炎が消えるまでの燃焼時間をt2(秒)とし、各5本について、t1とt2の平均燃焼時間を求めた。
(3−2)最大燃焼時間
上記燃焼試験時、各5本のt1とt2、すなわちあわせて10点の中から最大の燃焼時間を選んだ。
(3−3)UL−94
Underwriters LaboratoriesのUL−94に基準に従って、V−0、V−1、V−2の判定を実施した。
【0044】
(4)耐熱性(DTUL)
厚み3.2mm×長さ127mm×幅12.7mmのASTMタンザク試験片に成形した。得られた成形片を用いて、1.82MPa荷重下において、ASTM D648に準拠して、加熱変形温度を測定した。
(5)透明性
長さ90mm、幅50mm、厚さ2.5mmの平板状成形片を成形し、その試験片を、白地に黒インキで印刷された印刷物の上に置き、以下の判断基準に基づき、肉眼で観察することにより、その透明性を判定した。
○:印刷物の文字がはっきりと見える
△:印刷物の文字がぼんやりと見える。
×:印刷物の文字が全く見えない。
【0045】
(6)色調
長さ90mm、幅50mm、厚さ2.5mmの平板状成形片を成形し、その試験片を、(5)の透明性評価において○か△のものについて、肉眼で観察することにより、以下の判断基準に基づき、その色調を判定した。
○:淡黄色か無色
△:黄色〜淡褐色
×:褐色
【0046】
(7)ダート衝撃性
(7−1)全吸収エネルギー
長さ90mm、幅50mm、厚さ2.5mmの平板状成形片を成形し、ダートインパクトテスター(東洋精機(株)社製)を用い、落下荷重6.5kg、落下高さ100cmにて測定を行い、破壊の際の亀裂エネルギーと伝搬エネルギーの和である全吸収エネルギー(J)を測定した。この値が大きい方が、耐衝撃性に優れることを意味する。また、破壊試験後の平板試験片を厚み方向から見たときに、おもりの落下した部分が延びたように変形しているものを延性破壊、完全にくりぬかれ、変形がなく、フラットなものを脆性破壊と定義する。
(7−2)延性破壊数
延性破壊数を以下の式にて定義した。
(延性破壊数)=(延性破壊した枚数)/n
(ただし試験回数は、n=5で実施した。)
【0047】
【実施例1】
(a)ポリフェニレンエーテル(PPE−1)と(b)籠状シルセスキオキサン部分開裂構造体(式(1)において、Rはイソブチル基、白色固体、分子量=791.57、以下「P−1」と略すことがある。)と(c)ケイ素化合物(N−β(アミノエチル)γ−アミノプロピルメチルジメトキシシラン、無色液体、分子量=206.41、信越化学工業(株)製、KBM−602、以下「Si−1」と略すことがある。)を表1に示す割合(重量部)で配合して、トップフィードにより投入し、310℃に設定したベントポート付き二軸押出機(ZSK−25;WERNER&PFLEIDERER社製)を用い、スクリュー回転数300rpmにて溶融混練し、ベントポートから真空ポンプを用いて減圧にしたところ、圧力ゲージは、15kPaを示した。こうして得られたペレットを用い、上に示した方法により、成形加工し、物性評価を実施した。その結果を表1に示した。
【0048】
【比較例1】
(c)ケイ素化合物として、「Si−1」を用いなかったことと、表1に示す割合(重量部)に配合したこと以外は、実施例1と同様に実施し、成形加工し、物性評価を実施した。その結果を表1に示した。
【0049】
【比較例2】
(b)籠状シルセスキオキサン部分開裂構造体として、「P−1」を用いなかったこと以外は、実施例1と同様に実施し、成形加工し、物性評価を実施した。その結果を表1に示した。
【0050】
【比較例3】
(b)成分と(c)成分の代わりに、完全にかごが閉じていない構造の籠状シルセスキオキサン(式(7)、無色液体、分子量=933.88、このサンプルをNBAとglycerolと混ぜて、FAB−MS(Positive)を測定したところ、m/z=934[M+H]+が得られた。以下「P−2」と略すことがある。)を表1に示す割合(重量部)に配合したこと以外は、実施例1と同様に実施し、成形加工し、物性評価を実施した。その結果を表1に示した。
【0051】
【化9】
【0052】
【比較例4】
「P−2」を褐色瓶に栓をして、3週間室温にて保存したサンプル(無色液体、このサンプルをNBAとglycerolと混ぜて、FAB−MS(Positive)を測定したところ、m/z=934[M+H]+のピークの他に、m/z=1850[M+H]+のピークも得られた。以下「P−2‘」と略すことがある。)を比較例3と同様に、溶融混練してペレットを得たところ、ペレットは濁っていた。このペレットを用い、成形加工し、透明性の評価を実施したところ、あきらかに濁っていた。透明性:「△」。比較例3では透明であったことから、従来の添加方法では品質安定性が十分でないことがわかる。
【0053】
【実施例2】
実施例1で得られたペレットを室温にて3週間保存した後、実施例1と同様に成形加工し、物性評価を実施した。その結果を表1に示した。各物性は実施例1と同等の物性であり、本発明の製造方法が、品質安定性に優れることがわかる。
【0054】
【実施例3】
ケイ素化合物(N−β(アミノエチル)γ−アミノプロピルトリメトキシシラン、無色液体、分子量=222.41、信越化学工業(株)製、KBM−603、以下「Si−2」と略すことがある。)を用いることと、表1に示す割合(重量部)で配合すること以外は、実施例1と同様に実施し、成形加工し、物性評価を実施した。その結果を表1に示した。なお、押出機のベントポートの圧力ゲージは、16kPaを示した。
【0055】
【比較例5】
(b)籠状シルセスキオキサン部分開裂構造体として、「P−1」を用いなかったこと以外は、実施例3と同様に実施し、成形加工し、物性評価を実施した。その結果を表1に示した。
【0056】
【比較例6】
(b)成分と(c)成分の代わりに、完全にかごが閉じた構造の籠状シルセスキオキサン(式(8)、白色固体、分子量=917.83、このサンプルをNBAとglycerolと混ぜて、FAB−MS(Positive)を測定したところ、m/z=918[M+H]+が得られた。以下「P−3」と略すことがある。)を表1に示す割合(重量部)に配合したこと以外は、実施例3と同様に実施し、成形加工し、物性評価を実施した。その結果を表1に示した。
【0057】
【化10】
【0058】
【実施例4】
表1に示す割合(重量部)に配合することと、(c)成分の「Si−1」を第2フィード口から添加すること以外は、実施例1と同様に実施し、成形加工し、物性評価を実施した。その結果を表1に示した。なお、押出機のベントポートの圧力ゲージは、40kPaを示した。
【0059】
【実施例5】
表1に示す割合(重量部)に配合すること以外は、実施例3と同様に実施し、成形加工し、物性評価を実施した。その結果を表1に示した。なお、押出機のベントポートの圧力ゲージは、47kPaを示した。
【0060】
【比較例7】
高耐熱の変性ポリフェニレンエ−テル系樹脂のペレットとして、ザイロンX9102(旭化成(株)製、登録商標)(表中「X9102」と略した。)を用いて、成形加工し、物性評価を実施した。その結果を表1に示した。
【0061】
【比較例8】
ポリカーボネート樹脂のペレットとして、ワンダーライトPC−110(台湾国 旭美化成(株)製、登録商標)(表中「PC」と略した。)を用いて、成形加工し、物性評価を実施した。その結果を表1に示した。
【0062】
【表1】
【0063】
以上のことから、本発明の製造方法は、品質安定性に優れ、プロセスが簡素化されているため安価で、かつ流動性と難燃性と耐熱性と透明性と色調とダート衝撃性を高度なレベルで達成している樹脂組成物が得られる点で、極めて工業的価値が高いものである。
【0064】
【発明の効果】
本発明により、品質安定性に優れ、安価で、かつ流動性と難燃性と耐熱性と透明性と色調とダート衝撃性のバランスに優れた樹脂組成物とその製造方法を提供することが可能となった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a resin composition having excellent quality stability, being inexpensive, and having an excellent balance of fluidity, flame retardancy, heat resistance, transparency, color tone and dart impact resistance, and a method for producing the same.
[0002]
[Prior art]
As a method for making a flame-retardant synthetic resin flame-retardant, a flame-retardant method such as adding a halogen compound, a phosphorus compound, a combination thereof, or antimony trioxide has been generally used.
However, these conventional flame retardants are said to be harmful, and recently there has been a demand for a flame-retardant resin composition containing no halogen, antimony, phosphorus or the like, particularly from an environmental point of view.
[0003]
As a flame-retardant resin composition that is favorable for the environment, a material containing a large amount of metal hydroxide has been developed, but not only does the specific gravity of the material significantly increase, but also the impact resistance and molding fluidity At present, the reduction is large and the practicality is poor.
A resin composition flame-retarded by blending a specific silicone compound is disclosed. (For example, see Patent Literature 1, Patent Literature 2, Patent Literature 3, Patent Literature 4, Patent Literature 5, and Patent Literature 6)
[0004]
Furthermore, since flame retardancy is hardly obtained even when a silicone compound is added, a polycarbonate resin-based flame retardant resin composition using a silicone compound in combination with a perfluoroalkanesulfonic acid metal salt is disclosed. However, the perfluoroalkanesulfonic acid metal salt contains fluorine and cannot be said to be a flame-retardant resin composition using no halogen, and hardly exhibits any flame-retardant effect except for polycarbonate resin. (See Patent Literature 7, Patent Literature 8, and Patent Literature 9)
[0005]
As typical flame-retardant resins which do not contain halogen-based flame retardants other than polycarbonate resins, polyphenylene ethers to which phosphorus-based flame retardants are added and polymer blends thereof with polystyrene are known. Further, a flame-retardant resin composition of a polyphenylene ether-based resin containing a silicone compound is disclosed, but it is not satisfactory in balance of flame retardancy, fluidity, impact resistance, heat resistance and the like. (See Patent Documents 10 and 11)
[0006]
On the other hand, a method of producing a polymer containing a cage-like silsesquioxane by reacting a cage-like silsesquioxane containing a reactive group with a polymer at the reactive group has been proposed. It was not sufficient in balance of heat resistance, flame retardancy, heat resistance, transparency, color tone, and dart impact resistance. (See Patent Document 12)
It has been proposed to improve the fluidity and flame retardancy by adding a cage-like silsesquioxane having a functional group to the polyphenylene ether resin, but the fluidity, flame retardancy, heat resistance, transparency and color tone have been proposed. Not enough in dirt impact balance. (See Patent Document 13)
[0007]
[Patent Document 1]
JP-B-62-60421
[Patent Document 2]
Japanese Patent No. 1684119
[Patent Document 3]
Japanese Patent No. 1935582
[Patent Document 4]
JP-A-10-139964
[Patent Document 5]
JP-A-11-140294
[Patent Document 6]
JP-A-11-222559
[Patent Document 7]
Japanese Patent No. 2719486
[Patent Document 8]
Japanese Patent No. 2746519
[Patent Document 9]
JP-A-11-217494
[Patent Document 10]
Japanese Patent No. 1935582
[Patent Document 11]
Japanese Patent Publication No. 8-32525
[Patent Document 12]
U.S. Pat. No. 5,848,867
[Patent Document 13]
WO 02/059208 pamphlet
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide a resin composition which is excellent in quality stability, is inexpensive, and has an excellent balance of fluidity, flame retardancy, heat resistance, transparency, color, and dart impact resistance, and a method for producing the same. .
[0009]
[Means for Solving the Problems]
The inventor of the present invention has intensively studied a technique for achieving the above object, and as a result, a thermoplastic resin, a cage-like silsesquioxane partially-cleaved structure having a specific structure, and a specific silicon compound, in a specific ratio, an extruder Resin composition with excellent quality stability, low cost, and excellent balance of fluidity, flame retardancy, heat resistance, transparency, color tone, and dart impact property Have been obtained, and the present invention has been completed.
That is, the present invention
1. (A) a thermoplastic resin, (b) a cage-like silsesquioxane partially-cleaved structure represented by the formula (1), and (c) a silicon compound represented by the formula (2) and / or (3): (C) a resin composition obtained by being charged into an extruder at a molar ratio of (c) / (b) of 0.5 to 3 and melt-kneaded,
[0010]
Embedded image
[0011]
(R is selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a silicon atom-containing group having 1 to 10 silicon atoms. Is also good.)
[0012]
ZA-Six 3 … Equation (2)
ZA-Si (Y) X 2 … Equation (3)
(A is a hydrocarbon group having 1 to 10 carbon atoms and may or may not have a branched structure, and may contain a nitrogen atom or an oxygen atom in its main chain, X is an alkoxy group having 1 to 6 carbon atoms, Y is a hydrocarbon group other than an alkoxy group having 1 to 6 carbon atoms, Z is an amino group or an amide group. , A hydroxyl group, a thiol group, an epoxy group, an isocyanate group, a vinyl group, or a halogen.)
[0013]
2. (A) The resin composition according to the above (1), wherein the thermoplastic resin is a styrene-based resin,
3. (A) the resin composition according to the above (1), wherein the thermoplastic resin is a polyphenylene ether-based resin;
4. The resin composition according to any one of the above items 1 to 3, wherein (b) 1 to 30 parts by weight of a cage-like silsesquioxane partially cleaved structure is used per 100 parts by weight of the thermoplastic resin. ,
5. In the formula (1), R is an isobutyl group, wherein the resin composition according to any one of the above 1 to 4,
6. (A) a thermoplastic resin, (b) a cage-like silsesquioxane partially-cleaved structure represented by the formula (1), and (c) a silicon compound represented by the formula (2) and / or (3): (C) / (b) a method for producing a resin composition, wherein a molar ratio of 0.5 to 3 is applied to an extruder and melt-kneaded,
[0014]
Embedded image
[0015]
(R is selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a silicon atom-containing group having 1 to 10 silicon atoms. Is also good.)
[0016]
ZA-Six 3 … Equation (2)
ZA-Si (Y) X 2 … Equation (3)
(A is a hydrocarbon group having 1 to 10 carbon atoms and may or may not have a branched structure, and may contain a nitrogen atom or an oxygen atom in its main chain, X is an alkoxy group having 1 to 6 carbon atoms, Y is a hydrocarbon group other than an alkoxy group having 1 to 6 carbon atoms, Z is an amino group or an amide group. , A hydroxyl group, a thiol group, an epoxy group, an isocyanate group, a vinyl group, or a halogen.)
7. 7. The production method according to the above item 6, wherein devolatilization is performed at a degree of vacuum of 95 kPa or less from a vent port of the extruder.
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be specifically described.
The thermoplastic resin (a) of the present invention is a resin exhibiting thermoplasticity that can be molded by heating, and is, for example, a styrene resin, a polyphenylene ether resin, or a polyamide represented by polyamide 6 or polyamide 66. , Polyacetal, polycarbonate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, thermoplastic polyimide, thermoplastic polyetherimide, polyetheretherketone, liquid crystal polyester, polyethylene, polyethylene, Polypropylene, vinyl chloride resin, polymethyl methacrylate, polyvinylidene chloride, ethylene vinyl alcohol copolymer, polyester elastomer, polyamide elastomer, ethylene Down - olefin elastomer typified by propylene copolymers, and the like. Further, polymer alloys such as PPE / PA, PA / PP, and PC / ABS are also included.
[0018]
In particular, among these thermoplastic resins, a styrene-based resin is preferable from the viewpoint of fluidity, cost, and transparency. Here, the styrene resin is a homopolymer of a vinyl aromatic compound and / or a copolymer containing a vinyl aromatic compound. The vinyl aromatic compound is particularly preferably styrene. Examples of styrene resins include atactic polystyrene, syndiotactic polystyrene, high impact polystyrene, AS resin (acrylonitrile-styrene copolymer), ABS resin (acrylonitrile-butadiene-styrene copolymer), and vinyl aromatic compounds. A conjugated diene compound block copolymer, a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer, and the like, which may be used alone or as a mixture.
[0019]
On the other hand, among the thermoplastic resins, polyphenylene ether resins are preferred from the viewpoints of transparency, flame retardancy, heat resistance, and cost.
Here, the polyphenylene ether-based resin is a polyphenylene ether resin alone or a mixture of the above-described polyphenylene ether resin and the styrene-based resin, and includes a mixture of other resins. When a mixture of a polyphenylene ether resin and a styrene resin is used, the polyphenylene ether resin is at least 50 wt%, preferably at least 70 wt%, more preferably at least 80 wt%, based on the total amount of the polyphenylene ether resin and the styrene resin. It is.
Here, the polyphenylene ether resin is
Formula (4) repeating unit structure
[0020]
Embedded image
[0021]
(R 1 , R 4 Each independently represents hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl, or hydrocarbonoxy. R 2 , R 3 Each independently represents hydrogen, primary or secondary lower alkyl, or phenyl. And a homopolymer and / or copolymer having a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) in the range of 0.15 to 1.0 dl / g. A more preferred reduced viscosity is in the range of 0.20 to 0.70 dl / g, most preferably in the range of 0.40 to 0.60.
[0022]
Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether) and poly (2- Methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like. Further, 2,6-dimethylphenol and other phenols (for example, Polyphenylene ether copolymers such as copolymers with 2,3,6-trimethylphenol and 2-methyl-6-butylphenol) are also included. Among them, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1) is more preferable. , 4-phenylene ether) are preferred.
[0023]
As an example of the method for producing the polyphenylene ether resin used in the present invention, there is a method described in US Pat. No. 3,308,874, in which 2,6-xylenol is oxidatively polymerized using a complex of a cuprous salt and an amine as a catalyst.
U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357 and U.S. Pat. No. 3,257,358, JP-B-52-17880, JP-A-50-51197 and JP-A-63-152628. Is also preferable as a method for producing a polyphenylene ether resin.
The polyphenylene ether resin of the present invention may be used as it is after the polymerization process, or may be melted under an atmosphere of nitrogen or non-nitrogen gas, under devolatilization or under devolatilization using an extruder or the like. It may be pelletized and used by kneading.
[0024]
The polyphenylene ether-based resin of the present invention also includes a polyphenylene ether resin functionalized with various dienophile compounds. Various dienophile compounds include, for example, compounds such as maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, and styrene. No. Further, as a method of functionalization with these dienophile compounds, an extruder or the like may be used in the presence or absence of a radical generator, and may be functionalized in a molten state under devolatilization or non-devolatilization. For example, it may be functionalized by a method described in Japanese Patent No. 3289715 or Japanese Patent Application No. 2001-016550.
The cage-like silsesquioxane partially-cleaved structure (b) of the present invention will be described below. The cage-like silsesquioxane partially-cleaved structure used in the present invention is a silsesquioxane represented by the following formula (1) and having a partially open cage structure.
[0025]
Embedded image
[0026]
(R is selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a silicon atom-containing group having 1 to 10 silicon atoms. Is also good.)
From the viewpoints of fluidity, flame retardancy, and difficulty in bleeding out, R is preferably a hydrocarbon group having 1 to 10 carbon atoms, and more preferably an alkyl group. More specifically, an isobutyl group and an isooctyl group are preferable, and an isobutyl group is particularly preferable.
[0027]
As a method for synthesizing cage silsesquioxane, see, for example, Brown et al. Am. Chem. Soc. 1965, 87, 4313, and Feher et al. Am. Chem. Soc. 1989, 111, 1741 or Organometallics 1991, 10, 2526 and the like have been reported. For example, it can be obtained as crystals by reacting cyclohexyltriethoxysilane in water / methyl isobutyl ketone with the addition of tetramethylammonium hydroxide to the catalyst. Further, the cage-like silsesquioxane partially-cleaved structure represented by the formula (1) is produced simultaneously with the production of the complete condensation type cage-like silsesquioxane, or the cage-type silsesquioxane of complete condensation type is produced. It can be synthesized from the sun by partial cleavage with trifluoroacid or tetraethylammonium hydroxide in Feher et al., Chem. Commun. , 1998, 1279. Furthermore, RSiT 3 It can also be directly synthesized from a (T = Cl or alkoxy group) type compound.
[0028]
The silicon compound (c) of the present invention is a silicon compound represented by the formula (2) and / or (3).
ZA-Six 3 … Equation (2)
ZA-Si (Y) X 2 … Equation (3)
(A is a hydrocarbon group having 1 to 10 carbon atoms and may or may not have a branched structure, and may contain a nitrogen atom or an oxygen atom in its main chain, X is an alkoxy group having 1 to 6 carbon atoms, Y is a hydrocarbon group other than an alkoxy group having 1 to 6 carbon atoms, Z is an amino group or an amide group. , A hydroxyl group, a thiol group, an epoxy group, an isocyanate group, a vinyl group, or a halogen.)
[0029]
Here, (c) Z in the silicon compound is selected from any of an amino group, an amide group, a hydroxyl group, a thiol group, an epoxy group, an isocyanate group, a vinyl group, and a halogen, and is flame-retardant, heat-resistant, and transparent. From the viewpoint of color tone, an amino group or an epoxy group is preferable, and an amino group is more preferable.
Specific examples of the silicon compound represented by the formula (2) include N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, and γ-aminopropyl Trimethoxy silane, γ-aminopropyl triethoxy silane, γ-ureido propyl trimethoxy silane, γ- ureido propyl triethoxy silane and the like. From the viewpoint of the balance of fluidity, flame retardancy, heat resistance, transparency, color tone, and dart impact, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ- Aminopropyltriethoxysilane is preferred.
[0030]
Specific examples of the silicon compound represented by the formula (3) include N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-amino Propylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-ureidopropylmethyldimethoxysilane, γ-ureidopropylmethyldiethoxysilane and the like. From the viewpoint of the balance of fluidity, flame retardancy, heat resistance, transparency, color tone and dart impact resistance, in particular, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ- Aminopropylmethyldiethoxysilane is preferred.
[0031]
The blending ratio (molar ratio) of (c) the silicon compound and (b) the cage-like silsesquioxane partial cleavage structure is defined as the molar ratio of (c) / (b), and the value is 0.5. To 3, preferably 0.7 to 2.0, more preferably 0.8 to 1.5, and even more preferably 0.9 to 1.2.
The extruder is not particularly limited as long as it has a capability of melting and kneading the resin. A rotary extruder is mentioned, and a twin-screw co-rotating extruder is preferable from the viewpoints of physical properties and productivity of the obtained composition.
[0032]
According to the production method of the present invention, the blending ratio of (a) the thermoplastic resin and (c) the silicon compound and (b) the cage-like silsesquioxane partially-cleaved structure as described above, that is, (c) ) / (B) is introduced into an extruder at a molar ratio of 0.5 to 3 and melt-kneaded. At this time, the following methods can be used as a method of charging the raw materials. 1) A method in which all raw materials are fed from a first feed port. 2) A method in which the component (a) and the component (b) are fed from a first feed port and the component (c) is further fed from a second feed port. 3) A method in which the component (a) and the component (c) are fed from a first feed port, and the component (b) is further fed from a second feed port. The method 1) is more preferable from the viewpoint of the extruder torque.
[0033]
The set temperature of the extruder is not particularly limited, but is preferably a temperature at which the thermoplastic resin can be melt-kneaded. Therefore, 200 to 350 ° C is preferable, 250 to 330 ° C is more preferable, and 290 to 320 ° C is particularly preferable.
The number of revolutions of the extruder is not particularly limited, but is preferably 50 to 1500 rpm, preferably 100 to 1200 rpm, and more preferably 150 to 1000 rpm from the viewpoint of the obtained physical properties.
[0034]
The vent port of the extruder is preferably set on the die side from the place where at least the components (a), (b) and (c) are charged, and may be of an open-to-air type or reduced in pressure by a vacuum pump. Is also good. From the viewpoint of strand stability and the reactivity of the components (b) and (c) described below, the pressure is preferably reduced by a vacuum pump, and devolatilization is preferably performed at a degree of vacuum of 95 kPa or less. 50 kPa or less is more preferable.
According to these production methods, as shown in the following reaction formula (1), the cage-like silsesquioxane partially-cleaved structure of the formula (1) is converted into a cage-like silsesquioxane having a completely closed cage. It is estimated that the expression (5) is converted.
[0035]
Embedded image
[0036]
Similarly, as shown in the following reaction formula (2), the cage-like silsesquioxane partially-cleaved structure of the formula (1) has a cage-like silsesquioxane having a structure in which the basket is not completely closed (formula (1)). 6)).
[0037]
Embedded image
[0038]
Therefore, the production method of the present invention can simplify the process of synthesizing and isolating a cage silsesquioxane having a functional group represented by the formula (5) or (6). That is, this is a production method in which the reaction process represented by the reaction formulas (1) and (2) and the process of blending the thermoplastic resin can be simultaneously performed by a melt-kneading process using an extruder. This makes it possible to simplify the process and produce an inexpensive resin composition.
[0039]
In the present invention, (b) the cage-like silsesquioxane partially-cleaved structure and (c) the silicon compound do not necessarily have to react 100%, and unreacted as long as the effects of the present invention are not impaired. (B) The cage-like silsesquioxane partially-cleaved structure and (c) the silicon compound may remain in the resin composition.
The amount of the cage-like silsesquioxane partially-cleaved structure of the component (b) in the present invention is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, per 100 parts by weight of the thermoplastic resin (a). More preferably, 3 to 10 parts by weight is more preferable. If the amount is less than 1 part by weight, it is difficult to obtain sufficient fluidity and flame retardancy. When the amount is more than 30 parts by weight, it is difficult to obtain sufficient heat resistance.
Here, the component (c) is, as described above, a blending ratio (molar ratio) of (c) the silicon compound and (b) the cage-like silsesquioxane partially-cleaved structure, and (c) / (b) It is preferable to mix them in a molar ratio of 0.5 to 3.
[0040]
In the present invention, in addition to the above components, if necessary, other additional components such as inorganic fillers (glass fiber, metal fiber, potassium titanate, carbon fiber, etc.) as long as the characteristics and effects of the present invention are not impaired. , Silicon carbide, ceramic, silicon nitride, mica, nepheline sinite, talc, wollastonite, slag fiber, ferrite, glass beads, glass powder, glass balloon, quartz, quartz glass, etc. The shape is fibrous, plate, spherical Etc.), antioxidants, elastomers (ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / methacrylic Glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene / p Pyrene-g-maleic anhydride copolymer, olefin copolymer such as ABS, polyester polyether elastomer, polyester polyester elastomer, vinyl aromatic compound-conjugated diene compound block copolymer, vinyl aromatic compound-conjugated diene compound Hydrogenated block copolymer), plasticizer (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), weather (light) resistance improver, nucleating agent for polyolefin, slip agent, Various colorants and release agents may be added.
[0041]
The resin composition obtained according to the present invention can be molded into molded articles of various parts by various conventionally known methods, for example, injection molding, extrusion molding, and hollow molding. These molded articles are suitable for applications requiring particularly flame retardancy and heat resistance, such as home appliance OA parts, automobile parts, office equipment parts, electronic material parts, and the like. It is also suitable for sheets, films and foams.
Hereinafter, the present invention will be described based on examples. However, the present invention is not limited to the following examples as long as the gist is not exceeded.
[0042]
Polyphenylene ether (PPE-1)
Powdered poly (2,6-dimethyl-1,4-phenylene ether) having a reduced viscosity of 0.42 obtained by oxidative polymerization of 2,6-dimethylphenol.
Molding and physical property evaluation of each resin composition were performed according to the following methods.
(1) Molding
The obtained pellets were molded using an injection molding machine [IS-80EPN: manufactured by Toshiba Machine Co., Ltd.] set at a cylinder temperature of 320/330/320/310 ° C., a firing rate of 85%, and a mold temperature of 90 ° C. Was done.
(2) Liquidity
Under the molding conditions of the above (1), a gauge pressure at the time of short-circuiting by 1 mm was measured when molding an ASTM tank test piece having a thickness of 1.6 mm, a length of 127 mm and a width of 12.7 mm under the molding conditions of the above (1). This pressure is referred to as SSP (MPa) (abbreviated as “Short Shot Pressure”), and the smaller the value, the better the fluidity.
[0043]
(3) Flame retardancy
(3-1) Average burning time
An ASTM tank test specimen having a thickness of 1.6 mm, a length of 127 mm, and a width of 12.7 mm was formed, and a combustion test was performed based on the UL-94 vertical combustion test of Underwriters Laboratories. That is, a combustion test was performed on five test pieces, and after 10 seconds of flame contact, the burning time from when the flame was released until the flame disappeared was t. 1 (Seconds), and after the flame contact for 10 seconds again, the burning time from when the flame is released until the flame disappears is t. 2 (Seconds) and t 1 And t 2 The average burning time was determined.
(3-2) Maximum combustion time
At the time of the above combustion test, five t 1 And t 2 That is, the maximum burning time was selected from a total of 10 points.
(3-3) UL-94
V-0, V-1, and V-2 were determined according to UL-94 of Underwriters Laboratories.
[0044]
(4) Heat resistance (DTUL)
It was formed into an ASTM tank test piece having a thickness of 3.2 mm, a length of 127 mm and a width of 12.7 mm. Using the obtained molded piece, the heat deformation temperature was measured under a load of 1.82 MPa in accordance with ASTM D648.
(5) Transparency
A flat molded piece having a length of 90 mm, a width of 50 mm and a thickness of 2.5 mm is formed, and the test piece is placed on a printed material printed with black ink on a white background, and visually observed based on the following criteria. By doing so, its transparency was determined.
:: Letters on printed matter are clearly visible
Δ: The characters on the printed matter are blurred.
X: The characters on the printed matter are not visible at all.
[0045]
(6) Color
A flat molded piece having a length of 90 mm, a width of 50 mm, and a thickness of 2.5 mm was formed, and the test pieces were visually observed for those of ○ or △ in the evaluation of transparency in (5). The color tone was determined based on the criteria.
:: pale yellow or colorless
△: yellow to light brown
×: brown
[0046]
(7) Dart impact
(7-1) Total absorbed energy
A flat molded piece having a length of 90 mm, a width of 50 mm and a thickness of 2.5 mm is formed, and measured using a dirt impact tester (manufactured by Toyo Seiki Co., Ltd.) at a drop load of 6.5 kg and a drop height of 100 cm. Then, the total absorbed energy (J), which is the sum of the crack energy and the propagation energy at the time of fracture, was measured. A larger value means better impact resistance. In addition, when the flat test piece after the destruction test is viewed from the thickness direction, the one that is deformed so that the dropped part of the weight is extended is ductile fractured. Defined as brittle fracture.
(7-2) Number of ductile fractures
The number of ductile fractures was defined by the following equation.
(Number of ductile fractures) = (Number of ductile fractures) / n
(However, the number of tests was n = 5.)
[0047]
Embodiment 1
(A) polyphenylene ether (PPE-1) and (b) a cage-like silsesquioxane partially-cleaved structure (in the formula (1), R is an isobutyl group, a white solid, molecular weight = 791.57, hereinafter referred to as "P-1 ) And (c) a silicon compound (N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, colorless liquid, molecular weight = 206.41, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-602. , Hereinafter abbreviated as “Si-1”) in the proportions (parts by weight) shown in Table 1, charged by top feed, and set to 310 ° C. with a twin-screw extruder with vent port (ZSK-). 25; manufactured by Werner & Pfleiderer Co., Ltd.), melt-kneaded at a screw rotation speed of 300 rpm, and reduced in pressure from a vent port using a vacuum pump. 5 kPa was shown. Using the pellets thus obtained, molding was carried out by the method described above, and physical properties were evaluated. The results are shown in Table 1.
[0048]
[Comparative Example 1]
(C) Except that "Si-1" was not used as a silicon compound, and that it was blended in the ratio (parts by weight) shown in Table 1, the same procedure as in Example 1 was carried out, and molding was performed to evaluate physical properties. Was carried out. The results are shown in Table 1.
[0049]
[Comparative Example 2]
(B) Except not using "P-1" as a cage-like silsesquioxane partial cleavage structure, it carried out similarly to Example 1, shape-processed, and evaluated physical properties. The results are shown in Table 1.
[0050]
[Comparative Example 3]
Instead of the components (b) and (c), a cage-like silsesquioxane having a structure in which the basket is not completely closed (formula (7), a colorless liquid, molecular weight = 933.88). This sample was prepared using NBA and glycerol. After mixing, FAB-MS (Positive) was measured, and m / z = 934 [M + H]. + was gotten. Hereinafter, it may be abbreviated as “P-2”. ) In the proportions (parts by weight) shown in Table 1 were carried out in the same manner as in Example 1, molded, and evaluated for physical properties. The results are shown in Table 1.
[0051]
Embedded image
[0052]
[Comparative Example 4]
“P-2” was capped in a brown bottle and stored at room temperature for 3 weeks (colorless liquid, this sample was mixed with NBA and glycerol, and FAB-MS (Positive) was measured. = 934 [M + H] + M / z = 1850 [M + H] + Was also obtained. Hereinafter, it may be abbreviated as “P-2 ′”. Was melt-kneaded in the same manner as in Comparative Example 3 to obtain pellets. The pellets were cloudy. The pellets were molded and processed to evaluate the transparency. As a result, the pellets were clearly cloudy. Transparency: “△”. Comparative Example 3 was transparent, indicating that the conventional addition method had insufficient quality stability.
[0053]
Embodiment 2
After the pellets obtained in Example 1 were stored at room temperature for 3 weeks, they were molded in the same manner as in Example 1 and evaluated for physical properties. The results are shown in Table 1. Each physical property is equivalent to that of Example 1, and it is understood that the production method of the present invention is excellent in quality stability.
[0054]
Embodiment 3
Silicon compound (N-β (aminoethyl) γ-aminopropyltrimethoxysilane, colorless liquid, molecular weight = 222.41, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603, sometimes abbreviated as “Si-2” ) And blending in the proportions (parts by weight) shown in Table 1 were carried out in the same manner as in Example 1, molded, and evaluated for physical properties. The results are shown in Table 1. The pressure gauge at the vent port of the extruder indicated 16 kPa.
[0055]
[Comparative Example 5]
(B) Except not using "P-1" as the cage-like silsesquioxane partially-cleaved structure, the same procedure as in Example 3 was carried out, molding was performed, and physical properties were evaluated. The results are shown in Table 1.
[0056]
[Comparative Example 6]
Instead of the components (b) and (c), a cage-like silsesquioxane having a completely closed cage structure (formula (8), white solid, molecular weight = 917.83, this sample was mixed with NBA and glycerol) When FAB-MS (Positive) was measured, m / z = 918 [M + H] + was gotten. Hereinafter, it may be abbreviated as “P-3”. ) Was carried out in the same manner as in Example 3, except that it was blended in the ratio (parts by weight) shown in Table 1, and molded, and the physical properties were evaluated. The results are shown in Table 1.
[0057]
Embedded image
[0058]
Embodiment 4
Except that it was blended in the ratio (parts by weight) shown in Table 1 and that “c-1” of the component (c) was added from the second feed port, the same procedure as in Example 1 was carried out, and molding was performed. Physical properties were evaluated. The results are shown in Table 1. The pressure gauge at the vent port of the extruder indicated 40 kPa.
[0059]
Embodiment 5
Except for blending in the proportions (parts by weight) shown in Table 1, the same procedures as in Example 3 were carried out, and molding was performed, and physical properties were evaluated. The results are shown in Table 1. The pressure gauge at the vent port of the extruder indicated 47 kPa.
[0060]
[Comparative Example 7]
As pellets of modified polyphenylene ether resin having high heat resistance, molding was performed using Zylon X9102 (registered trademark, manufactured by Asahi Kasei Corporation) (abbreviated as “X9102” in the table), and physical properties were evaluated. . The results are shown in Table 1.
[0061]
[Comparative Example 8]
As a polycarbonate resin pellet, Wonderlight PC-110 (registered trademark, manufactured by Asami Kasei Co., Ltd., Taiwan) (abbreviated as “PC” in the table) was used for molding and physical property evaluation. The results are shown in Table 1.
[0062]
[Table 1]
[0063]
From the above, the production method of the present invention has excellent quality stability, is inexpensive because the process is simplified, and has high fluidity, flame retardancy, heat resistance, transparency, color tone, and dart impact resistance. This is extremely high in industrial value in that a resin composition that achieves a certain level can be obtained.
[0064]
【The invention's effect】
According to the present invention, it is possible to provide a resin composition excellent in quality stability, inexpensive, and excellent in balance between fluidity, flame retardancy, heat resistance, transparency, color, and dart impact resistance, and a method for producing the same. It became.
Claims (7)
Z−A−SiX3 …式(2)
Z−A−Si(Y)X2 …式(3)
(Aは、炭素数1〜10個の炭化水素基であって、分岐構造をしていても、していなくてもよく、主鎖中に、窒素原子あるいは酸素原子を含有していても、していなくてもよい。Xは、炭素数1〜6個のアルコキシ基である。Yは、炭素数1〜6個のアルコキシ基以外の炭化水素基である。Zは、アミノ基、アミド基、水酸基、チオール基、エポキシ基、イソシアネート基、ビニル基、ハロゲンのいずれかから選ばれる。)(A) a thermoplastic resin, (b) a cage-like silsesquioxane partially-cleaved structure represented by the formula (1), and (c) a silicon compound represented by the formula (2) and / or (3): A resin composition obtained by being charged into an extruder at a molar ratio of (c) / (b) of 0.5 to 3 and melt-kneaded.
Z-A-SiX 3 ... formula (2)
ZA-Si (Y) X 2 Formula (3)
(A is a hydrocarbon group having 1 to 10 carbon atoms and may or may not have a branched structure, and may contain a nitrogen atom or an oxygen atom in its main chain, X is an alkoxy group having 1 to 6 carbon atoms, Y is a hydrocarbon group other than an alkoxy group having 1 to 6 carbon atoms, Z is an amino group or an amide group. , A hydroxyl group, a thiol group, an epoxy group, an isocyanate group, a vinyl group, or a halogen.)
Z−A−SiX3 …式(2)
Z−A−Si(Y)X2 …式(3)
(Aは、炭素数1〜10個の炭化水素基であって、分岐構造をしていても、していなくてもよく、主鎖中に、窒素原子あるいは酸素原子を含有していても、していなくてもよい。Xは、炭素数1〜6個のアルコキシ基である。Yは、炭素数1〜6個のアルコキシ基以外の炭化水素基である。Zは、アミノ基、アミド基、水酸基、チオール基、エポキシ基、イソシアネート基、ビニル基、ハロゲンのいずれかから選ばれる。)(A) a thermoplastic resin, (b) a cage-like silsesquioxane partially-cleaved structure represented by the formula (1), and (c) a silicon compound represented by the formula (2) and / or (3): A method for producing a resin composition, wherein the mixture is charged into an extruder at a molar ratio of (c) / (b) of 0.5 to 3 and melt-kneaded.
Z-A-SiX 3 ... formula (2)
ZA-Si (Y) X 2 Formula (3)
(A is a hydrocarbon group having 1 to 10 carbon atoms and may or may not have a branched structure, and may contain a nitrogen atom or an oxygen atom in its main chain, X is an alkoxy group having 1 to 6 carbon atoms, Y is a hydrocarbon group other than an alkoxy group having 1 to 6 carbon atoms, Z is an amino group or an amide group. , A hydroxyl group, a thiol group, an epoxy group, an isocyanate group, a vinyl group, or a halogen.)
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