JPH0477553A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH0477553A JPH0477553A JP18722090A JP18722090A JPH0477553A JP H0477553 A JPH0477553 A JP H0477553A JP 18722090 A JP18722090 A JP 18722090A JP 18722090 A JP18722090 A JP 18722090A JP H0477553 A JPH0477553 A JP H0477553A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyphenylene ether
- formula
- saturated polyester
- resin composition
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 20
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 10
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 66
- 229920000728 polyester Polymers 0.000 claims abstract description 39
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 23
- 239000002904 solvent Substances 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 125000005370 alkoxysilyl group Chemical group 0.000 abstract description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- -1 poly(2,6-dimethyl-1,4-phenylene ether) Polymers 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical group CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- RTJCABIRIJFMDG-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]-n-[3-[dimethoxy(methyl)silyl]propyl]-n-(oxiran-2-ylmethyl)propan-1-amine Chemical compound CO[Si](C)(OC)CCCN(CCC[Si](C)(OC)OC)CC1CO1 RTJCABIRIJFMDG-UHFFFAOYSA-N 0.000 description 1
- QACUUGBVDGMIQH-UHFFFAOYSA-N 4-(1-carboxybutoxy)benzoic acid Chemical compound CCCC(C(O)=O)OC1=CC=C(C(O)=O)C=C1 QACUUGBVDGMIQH-UHFFFAOYSA-N 0.000 description 1
- ZOPFZPGPAKRUFE-UHFFFAOYSA-N 4-(1-carboxyethoxy)benzoic acid Chemical compound OC(=O)C(C)OC1=CC=C(C(O)=O)C=C1 ZOPFZPGPAKRUFE-UHFFFAOYSA-N 0.000 description 1
- IKRCKEUYLJBWHG-UHFFFAOYSA-N 4-(1-carboxypropoxy)benzoic acid Chemical compound CCC(C(O)=O)OC1=CC=C(C(O)=O)C=C1 IKRCKEUYLJBWHG-UHFFFAOYSA-N 0.000 description 1
- LABJFIBQJFPXHZ-UHFFFAOYSA-N 4-(carboxymethoxy)benzoic acid Chemical compound OC(=O)COC1=CC=C(C(O)=O)C=C1 LABJFIBQJFPXHZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PJFPFKALGCPVLG-UHFFFAOYSA-N cyclohexane;3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound C1CCCCC1.O=C1OCCOC(=O)C2=CC=C1C=C2 PJFPFKALGCPVLG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 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
- 239000002270 dispersing agent Substances 0.000 description 1
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- CSPNRCRYDHKODL-UHFFFAOYSA-N n-(oxiran-2-ylmethyl)-3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(CCC[Si](OC)(OC)OC)CC1CO1 CSPNRCRYDHKODL-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229940094537 polyester-10 Drugs 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000417 polynaphthalene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ポリフェニレンエーテルと飽和ポリエステル
との樹脂組成物を得るに際し、ポリフェニレンエーテル
にアルコキシシラン化合物を反応させて製造された末端
変性ポリフェニレンエーテルと飽和ポリエステルを配合
したことにより、ポリフェニレンエーテルの特徴である
耐熱性、機穢的強度及び寸法精度並に飽和ポリエステル
の機械的性質、電気的性質及び耐瀉剤性を兼ね備えた高
性能な熱可塑性樹脂組成物に関する。本樹脂組成物は、
ますます多様化、高度化している自動車電気・電子分野
に応用展開する材料として有用である。Detailed Description of the Invention (Industrial Field of Application) The present invention provides a method for obtaining a resin composition of polyphenylene ether and saturated polyester using terminal-modified polyphenylene ether produced by reacting polyphenylene ether with an alkoxysilane compound. By blending saturated polyester, we have created a high-performance thermoplastic resin composition that combines the heat resistance, mechanical strength, and dimensional accuracy that are characteristic of polyphenylene ether, as well as the mechanical properties, electrical properties, and antidiathermia properties of saturated polyester. relating to things. This resin composition is
It is useful as a material for application in the automotive electrical and electronic fields, which are becoming increasingly diverse and sophisticated.
（従来の技術）
フェニレン環に非置換又は置換基を有するポリフェニレ
ンエーテル、特にポリ（２，６−シメチルー１．４−フ
ェニレンエーテル）は耐熱性及び機械的強度が優れ、い
わゆるエンジニアリングプラスチックとして有用である
が、溶融粘度が高いので、射出成形等による成形加工が
困難であるという望ましくない性質を有することは良く
知られている。また、同樹脂の耐衝撃強度及び耐溶剤性
もエンジニアリングプラスチックとしての多くの用途分
野で不充分である。単独の樹脂材料では、所望の諸性質
を充分に満たすことができない場合の試みの一つとして
、他の樹脂材料を混合することにより、不充分な性質を
補うという考え方は良く知られている。ポリフェニレン
エーテルと相溶性が良く、成形加工性の良好なポリスチ
レンを配合してポリフェニレンエーテルの成形性を改良
した材料は、広く実用されている。しかし、この場合、
同成分とも耐溶剤性は良好でなく、混合組成物も、耐溶
剤性が充分ではない。(Prior art) Polyphenylene ether having an unsubstituted or substituent group on the phenylene ring, particularly poly(2,6-dimethyl-1,4-phenylene ether), has excellent heat resistance and mechanical strength, and is useful as a so-called engineering plastic. However, it is well known that it has an undesirable property of being difficult to mold by injection molding or the like because of its high melt viscosity. Furthermore, the impact strength and solvent resistance of the same resin are insufficient in many fields of use as engineering plastics. The idea of supplementing the insufficient properties by mixing other resin materials is well known as one of the attempts when desired properties cannot be fully satisfied with a single resin material. Materials in which the moldability of polyphenylene ether is improved by blending polystyrene, which has good compatibility with polyphenylene ether and has good moldability, are widely used. But in this case,
Both of the same components do not have good solvent resistance, and the mixed composition also does not have sufficient solvent resistance.
飽和ポリエステルは、機械的性質、電気的性質、耐溶剤
性などが優れた代表的なエンジニア′１゛ングプラスチ
ックの一つとじて、自動車部品、電気 電子部品等の用
途に広く使用されでいる。しかしながら本樹脂は、成形
４ヌ縮率及び線膨張率が大きく、また高荷重下での耐転
安定性が劣るという欠点を有するため、その使用用途は
、制限されている。このため、ガラス繊維などの強化剤
を充填する方法が提案されているが、成形品の外りが悪
化することから、要求分野によっては、その使用が制限
されるという問題を有する。このため、ポリフェニレン
エーテルと飽和ポリエステルの良好な性質を併せ持ち、
望ましくない性質を補う組成物が得られれば、利用分野
の広い優れた樹脂材料の提供が可能となり、その工業的
意味は非常に大きいものといえる。そこで両者の長所を
損なわずに欠点を相補った成形材料を提供する目的で、
例えば、同樹脂を羊純に溶融混合した組成物が、特公昭
５１−２１６６４号、特開昭４９−５００５０号、同４
９−７５６６２号、同５９−１５９８４７号各公報等に
開示されている。しかしながら、このような単純なブレ
ンド系では、ボッフェニレンエーテルと飽和ポリエステ
ルとは、本質的に相溶性に乏しいため、この二相構造の
界面の接着性は良好ではなく、この二相は均一かつ微細
な形態となり難く、射出成形などの成形加工時の剪断応
力を受けたとき、層状剥離（デラミネーション）を生し
易く、得られた成形品の外観が悪化したり、二相界面が
欠陥部となり、寸法精度、耐熱性、剛性等の機械的特性
及び耐溶剤性等の物理的特性が優れた組成物は得られな
い。Saturated polyester is a typical engineering plastic with excellent mechanical properties, electrical properties, and solvent resistance, and is widely used in applications such as automobile parts and electrical and electronic parts. However, this resin has the drawbacks of high molding shrinkage and linear expansion coefficient, and poor rolling stability under high loads, so its uses are limited. For this reason, a method of filling reinforcing agents such as glass fibers has been proposed, but this has the problem that the molded product's deterioration deteriorates, which limits its use depending on the required fields. Therefore, it combines the good properties of polyphenylene ether and saturated polyester,
If a composition that compensates for undesirable properties can be obtained, it will be possible to provide an excellent resin material that can be used in a wide range of fields, and it can be said to have great industrial significance. Therefore, in order to provide a molding material that compensates for the disadvantages without compromising the advantages of both,
For example, compositions in which the same resin is melt-mixed with sheep pure are disclosed in Japanese Patent Publication No. 51-21664, Japanese Patent Application Publication No. 49-50050,
It is disclosed in Publications No. 9-75662 and No. 59-159847. However, in such a simple blend system, bophenylene ether and saturated polyester are essentially incompatible, so the adhesion at the interface of this two-phase structure is not good, and this two-phase structure is uniform and fine. When subjected to shear stress during molding processes such as injection molding, delamination is likely to occur, resulting in deterioration of the appearance of the resulting molded product and the formation of defects at the two-phase interface. However, it is not possible to obtain a composition that has excellent mechanical properties such as dimensional accuracy, heat resistance, and rigidity, and physical properties such as solvent resistance.
−数的に非相溶のポリマーブレンドにおいて、上記の問
題点を解決するために考えられる方法の一つは、二成分
相互の親和性を改良するために、ポリフェニレンエーテ
ルを飽和ポリエステルと反応すると考えられる官能基で
変性し、高温で溶融混練して反応させることにより、化
学結合を介したブロック又はグラフト共重合体を得る方
法である。ポリフェニレンエーテルと飽和ポリエステル
の組成物の場合、飽和ポリエステルの末端に存在する水
酸基又はカルボキシル基、あるいは主鎖のエステル構造
単位と反応が考えられる官能基をボッフェニレンエーテ
ルに付加させる必要がある。- One possible way to solve the above problems in numerically incompatible polymer blends is to react the polyphenylene ether with the saturated polyester in order to improve the mutual affinity of the two components. This is a method of obtaining a block or graft copolymer through chemical bonding by modifying the polymer with a functional group, melt-kneading it at high temperature, and reacting it. In the case of a composition of polyphenylene ether and saturated polyester, it is necessary to add to bophenylene ether a functional group that can react with the hydroxyl group or carboxyl group present at the end of the saturated polyester, or the ester structural unit of the main chain.
そのような観点から、ポリフェニレンエーテルの反応性
を高める目的で、多くの官能化ポリフェニレンエーテル
が提案されている。例えば、その官能化例は、カルボキ
シル基又はカルボン酸無水物官能化ポリフェニレンエー
テルを用いる方法（特開昭６２−２５７９５８号、同６
３−５４４２７号、特表昭６３−５００８０３号各公報
等）、エポキシ基官能化ポリフェニレンエーテルを用い
る方法（特開昭６２−２５７９５８号、特表昭６３−５
０３３８８号各公報等）、アルコキシシリル基官能化ポ
リフェニレンエーテルを用いる方法（特表昭６３−５０
３３９２号公報等）等が開示され、各種始和ポリエステ
ルとの樹脂組成物が提案されている。しかし、これらの
方法を用いてもポリフェニレンエーテルと飽和ポリエス
テルの両者の相溶性を改良するためには不充分である場
合が多く、また、得られた組成物の機械的特性も未だ充
分といえず、より一層の改良が望まれている。From this point of view, many functionalized polyphenylene ethers have been proposed for the purpose of increasing the reactivity of polyphenylene ethers. For example, examples of the functionalization include a method using carboxyl group- or carboxylic anhydride-functionalized polyphenylene ether (JP-A-62-257958, JP-A-62-257958;
3-54427, Japanese Patent Publication No. 63-500803, etc.), method using epoxy group-functionalized polyphenylene ether (Japanese Patent Application Laid-Open No. 62-257958, Japanese Patent Publication No. 1983-500803, etc.)
03388 publications, etc.), a method using alkoxysilyl group-functionalized polyphenylene ether (Japanese Patent Publication No. 1983-50),
No. 3392, etc.), and resin compositions with various Shiwa polyesters have been proposed. However, even if these methods are used, it is often insufficient to improve the compatibility of both polyphenylene ether and saturated polyester, and the mechanical properties of the resulting compositions are still insufficient. , further improvements are desired.
（発明が解決しようとする課題）
本発明は、特に優れた耐熱剛性、寸法積度、成形加工性
、耐溶剤性、分散構造を有する、ポリフェニレンエーテ
ルと飽和ポリエステルとを配合した熱可塑性樹脂組成物
を提供することを目的とする。(Problems to be Solved by the Invention) The present invention provides a thermoplastic resin composition blended with polyphenylene ether and saturated polyester, which has particularly excellent heat-resistant rigidity, dimensional bulk, moldability, solvent resistance, and dispersion structure. The purpose is to provide
（課題を解決するための手段）
本発明者らは、上記問題点を解決するために鋭意検討を
重ねた結果、特定の手法により極めて容易に変性された
官能化ポリフェニレンエーテルと飽和ポリエステルを配
合した熱可塑性樹脂組成物は、上記目的を達成し得るこ
とを見出し、本発明に到達した。(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have developed a blend of functionalized polyphenylene ether and saturated polyester that are extremely easily modified using a specific method. It has been discovered that a thermoplastic resin composition can achieve the above object, and the present invention has been achieved.
すなわち、本発明は、下記の成分（Ａ）及び（Ｂ）から
なることを特徴とする熱可塑性樹脂組成物である。That is, the present invention is a thermoplastic resin composition characterized by comprising the following components (A) and (B).
（Ａ）−数式
（式中、Ｑｌは各々ハロゲン原子、第−級若しくは第二
級アルキル基、フェニル基、アミノアルキル基、炭化水
素オキシ基又はハロ炭化水素オキシ基を表し、Ｑ２は各
々水素原子、ハロゲン原子、第−級若しくは第二級アル
キル基、フェニル基、ハロアルキル基、炭化水素オキシ
基又はハロ炭化水素オキシ基を表し、ｎは１０以上の数
を表し、Ｘは酸素原子又は窒素原子を表し、Ｒ１は炭素
数１〜１２のアルキレン基を表し、Ｒ２及びＲ３は各々
炭素数１〜６の炭化水素基を表す。ＳはＸが酸素原子の
ときは１、Ｘが窒素原子のときは２であり、ｔは１〜３
の整数である）で示される末端基変性されたポリフェニ
レンエーテル １０〜９０重量％
（Ｂ）飽和ポリエステル ９０〜ｌＯ重量％本発明の
上記構造を有する官能化ポリフェニレンエーテル（以下
、官能化ポリフェニレンエーテルという）（Ａ）と飽和
ポリエステル（Ｂ）との組成物は、ポリフェニレンエー
テルの特徴と飽和ポリエステルの特徴を兼ね備えた優れ
た耐熱剛性、寸法精度、成形加工性、耐溶剤性、分散構
造を有する成形材料として、極めて有用なものである。(A) - Formula (wherein Ql each represents a halogen atom, a secondary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, and Q2 each represents a hydrogen atom) , represents a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, n represents a number of 10 or more, and X represents an oxygen atom or a nitrogen atom. R1 represents an alkylene group having 1 to 12 carbon atoms, R2 and R3 each represent a hydrocarbon group having 1 to 6 carbon atoms, S is 1 when X is an oxygen atom, and 1 when X is a nitrogen atom. 2, and t is 1 to 3
10 to 90% by weight of end group-modified polyphenylene ether represented by
(B) Saturated polyester 90-10% by weight The composition of the functionalized polyphenylene ether (hereinafter referred to as functionalized polyphenylene ether) having the above structure of the present invention (A) and the saturated polyester (B) has the characteristics of polyphenylene ether. It is extremely useful as a molding material that has excellent heat resistance, dimensional accuracy, moldability, solvent resistance, and a dispersion structure, all of which have the characteristics of saturated polyester.
以下１本発明の熱可塑性樹脂組成物の構成について説明
する。The structure of the thermoplastic resin composition of the present invention will be explained below.
成ｊＬＡＪＯ−官能化ポリフェニレンエーテル本発明で
使用する官能化ポリフェニレンエーテルは、下記の方法
により製造される。以下にその詳細を記載する。LAJO-Functionalized Polyphenylene Ether The functionalized polyphenylene ether used in the present invention is produced by the following method. The details are described below.
一般式（ＩＩ）で示されるポリフェニレンエーテル
数式（ＩＩＩ ）で示されるアルコキシシリル基とグリ
シジル基を同一分子内に持つ化合物
（Ｉｌｌ ）
（式中、Ｘ、Ｒ’、Ｒ２、Ｒ３、Ｓ及びｔは前述と同し
）を反応させて一般式（Ｉ）で示される官能化ポリフェ
ニレンエーテル（Ａ）が得られる。Polyphenylene ether represented by general formula (II) A compound (Ill) having an alkoxysilyl group and a glycidyl group represented by formula (III) in the same molecule (wherein, X, R', R2, R3, S and t are (same as above) is reacted to obtain the functionalized polyphenylene ether (A) represented by the general formula (I).
ポリフェニレンエーテルは、式（ＩＩ）の構造よりなる
単独重合体又は共重合体である。Polyphenylene ether is a homopolymer or copolymer having the structure of formula (II).
Ｑｌ及びＱ２の第一級アルキル基の好適な例は、メチル
、エチル、ｎ−プロピル、ｎ−ブチル、ｎ−アミル、イ
ソアミル、２−メチルブチル、ｎ−ヘキシル、２．３−
ジメチルブチル、２−１３−若しくは４−メチルペンチ
ル又はヘプチルである。第二級アルキル基の例は、イソ
プロピル、５ｅｅ−ブチル又は１−エチルプロピルであ
る。多くの場合、各Ｑ’はアルキル基又はフェニル基、
特に炭素数１〜４のアルキル基であり、各（式中、Ｑ’
、Ｑ”及びｎは前述と同じ）に、Ｑ２は水素原子である
。Suitable examples of primary alkyl groups for Ql and Q2 are methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2.3-
Dimethylbutyl, 2-13- or 4-methylpentyl or heptyl. Examples of secondary alkyl groups are isopropyl, 5ee-butyl or 1-ethylpropyl. In many cases, each Q' is an alkyl group or a phenyl group,
In particular, it is an alkyl group having 1 to 4 carbon atoms, and each (in the formula, Q'
, Q'' and n are the same as above), and Q2 is a hydrogen atom.
好Ｊなポリフェニレンエーテルの単独重合体としては、
例えば、２．６−シメチルー１．４−フェニレンエーテ
ル単位からなるものである。好適な共重合体としては、
上記単位と２．３．６−ドリメチルー１．４−フェニレ
ンエーテル単位との組合せからなるランダム共重合体で
ある。多くの好適な単独重合体及びランダム共重合体が
、特許、文献に記載されている。例えば、分子量、溶融
粘度及び／又は衝撃強度等の特性を改良する分子構成部
分を含むポリフェニレンエーテルも、また好適である。As a homopolymer of polyphenylene ether with good J,
For example, it is composed of 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include:
It is a random copolymer consisting of a combination of the above units and 2,3,6-drimethyl-1,4-phenylene ether units. Many suitable homopolymers and random copolymers are described in the patent literature. Also suitable are polyphenylene ethers containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and/or impact strength.
例えばアクリロニトリル又はスチレン等のビニル芳香族
化合物などのビニルモノマーあるいはポリスチレン又は
そのエラストマーなどのポリマーをポリフェニレンエー
テル上にグラフト重合させたポリフェニレンエーテル等
である。For example, polyphenylene ether is obtained by graft polymerizing a vinyl monomer such as a vinyl aromatic compound such as acrylonitrile or styrene, or a polymer such as polystyrene or an elastomer thereof onto polyphenylene ether.
ポリフェニレンエーテルの分子量は通常クロロホルム中
で、３０℃の極限粘度が０．２〜０．８ａ／ｇ程度のも
のである。The molecular weight of polyphenylene ether is usually such that the intrinsic viscosity at 30° C. in chloroform is about 0.2 to 0.8 a/g.
ポリフェニレンエーテルは、通常前記のモノマーの酸化
カップリングにより製造される。ポリフェニレンエーテ
ルの酸化カップリング重合に関しては、数多（の触媒系
が知られている。触媒の選択に関しては特に制限はなく
、公知の触媒のいずれも用いることができる。例えば、
銅、マンガン、コバルト等の重金属化合物の少なくとも
一種を通常は種々の他の物質との組合せで含むもの等で
ある。Polyphenylene ethers are usually produced by oxidative coupling of the monomers described above. Regarding the oxidative coupling polymerization of polyphenylene ether, a large number of catalyst systems are known. There are no particular restrictions on the selection of the catalyst, and any known catalyst can be used. For example,
These include at least one heavy metal compound such as copper, manganese, cobalt, etc., usually in combination with various other substances.
ポリフェニレンエーテルの官能化に用いる一般式（ＩＩ
Ｉ ）の同一分子内にグリシジル基とアルコキシシリル
基をもつ化合物の具体例を挙げると、Ｎ−グリシジル−
Ｎ、Ｎ−ビス［３−（メチルジメトキシシリル）プロピ
ル〕アミン、Ｎ−グリシジル−Ｎ、Ｎ−ビス［３−（ト
リメトキシシリル）プロピル］アミン、３−グリシジル
オキシプロピル（メチル）ジメトキシシラン、３−グリ
シジルオキシプロピルトリメトキシシラン、３−グリシ
ジルオキシプロピル（メチル）ジェトキシシラン等が挙
げられる。特に好ましくは、３−グリシジルオキシプロ
ピルトリメトキシシラン又は３−グリシジルオキシプロ
ピル（メチル）ジェトキシシランである。General formula (II) used for functionalization of polyphenylene ethers
Specific examples of compounds having a glycidyl group and an alkoxysilyl group in the same molecule of I) include N-glycidyl-
N, N-bis[3-(methyldimethoxysilyl)propyl]amine, N-glycidyl-N, N-bis[3-(trimethoxysilyl)propyl]amine, 3-glycidyloxypropyl(methyl)dimethoxysilane, 3 -glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyl(methyl)jethoxysilane, and the like. Particularly preferred is 3-glycidyloxypropyltrimethoxysilane or 3-glycidyloxypropyl(methyl)jethoxysilane.
一般式（Ｉ）で示される官能化ポリフェニレンエーテル
（Ａ）は、−Ｍ式（ＩＩ）で示されるポリフェニレンエ
ーテルと一般式（Ｉｌｌ ）で示されるアルコキシシリ
ル基とグリシジル基を同一分子内に持つ化合物を塩基性
触媒の存在下、有機溶媒中で反応させることにより容易
に製造することができる。The functionalized polyphenylene ether (A) represented by the general formula (I) is a compound having a polyphenylene ether represented by the -M formula (II) and an alkoxysilyl group and a glycidyl group represented by the general formula (Ill) in the same molecule. It can be easily produced by reacting in an organic solvent in the presence of a basic catalyst.
ここで使用する有機溶媒は、ポリフェニレンエーテルを
溶解できることが望ましい。具体的には、ベンゼン、ト
ルエン、キシレン等の芳香族系溶媒：クロルベンゼン、
ジクロルベンゼン等のハロゲン化芳香族系溶媒；クロロ
ホルム、トリクロルエチレン、四塩化炭素等のハロゲン
化炭化水素系溶媒；Ｎ−メチル−２−ピロリドン、１．
３−ジメチル−２−イミダゾリジノン等の非プロトン性
の極性溶媒等が挙げられる。前記の塩基性触媒としては
、ナトリウムメトキシド、ナトリウムエトキシド等のア
ルコラード、ペンシルジメチルアミン、トリブチルアミ
ン等の第三級アミン、水酸化ナトリウム、水酸化カリウ
ム等のアルカリ金属水酸化物等が挙げられる。The organic solvent used here is desirably capable of dissolving polyphenylene ether. Specifically, aromatic solvents such as benzene, toluene, and xylene: chlorobenzene,
Halogenated aromatic solvents such as dichlorobenzene; halogenated hydrocarbon solvents such as chloroform, trichloroethylene, carbon tetrachloride; N-methyl-2-pyrrolidone; 1.
Examples include aprotic polar solvents such as 3-dimethyl-2-imidazolidinone. Examples of the basic catalyst include alcoholades such as sodium methoxide and sodium ethoxide, tertiary amines such as pencil dimethylamine and tributylamine, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. .
本反応は、ポリフェニレンエーテルの末端フェノール性
水酸基１モルに対し、 ｆＱＱ式（ＩＩＩ ）で示され
る官能化剤２〜５０モル、好ましくは５〜２０モルを用
いる。有機溶媒は、ポリフェニレンエーテル１００重量
部に対して５００〜１０００重量部使用する。塩基性触
媒は使用するポリフェニレンエーテル１００重量部あた
り１〜３重量部使用する。In this reaction, 2 to 50 moles, preferably 5 to 20 moles of the functionalizing agent represented by the fQQ formula (III) are used per mole of the terminal phenolic hydroxyl group of polyphenylene ether. The organic solvent is used in an amount of 500 to 1000 parts by weight per 100 parts by weight of polyphenylene ether. The basic catalyst is used in an amount of 1 to 3 parts by weight per 100 parts by weight of the polyphenylene ether used.
官能化ポリフェニレンエーテル（Ａ）の−ＩｌΩ的製造
手順は、ポリフェニレンエーテル（ＩＩ）を有ｅｌｌ溶
媒に加熱して溶解させ、次いで少量のエタノール又はメ
タノールに溶解させた塩基性触媒を添加し、５０〜２０
０℃の温度で官能化剤（ｎＢを加え、更に反応が完結す
るまで加熱するものである。The -IlΩ production procedure for functionalized polyphenylene ether (A) is to heat and dissolve polyphenylene ether (II) in a well-containing solvent, then add a basic catalyst dissolved in a small amount of ethanol or methanol, 20
The functionalizing agent (nB) was added at a temperature of 0° C. and further heated until the reaction was completed.
成ｊ辷ｍ−飽和ポリエステル
本発明において用いる成分（Ｂ）の飽和ポリエステルと
しては、種々のポリエステルが使用可能である。Saturated polyester Various polyesters can be used as the saturated polyester of component (B) used in the present invention.
例えば、その一つとして、通常の方法に従って、ジカル
ボン酸又はその低級アルキルエステル、酸ハライド若し
くは酸無水物誘導体と、グリコールとを縮合させること
により製造された熱可塑性ポリエステルが挙げられる。For example, one example is a thermoplastic polyester produced by condensing dicarboxylic acid or its lower alkyl ester, acid halide, or acid anhydride derivative with glycol according to a conventional method.
このポリエステルを製造するに適した芳香族又は脂肪族
ジカルボン酸の具体例としては、蓚酸、マロン酸、コハ
ク酸、グルタル酸、アジピン酸、スペリン酸、アゼライ
ン酸、セバシン酸、テレフタル酸、イソフタル酸、ｐ、
ｐ′−ジカルボキシジフェニルスルホン、ｐ−カルボキ
シフェノキシ酢酸、ｐ−カルボキシフェノキシプロピオ
ン酸、ｐ−カルボキシフェノキシ酪酸、ｐ−カルボキシ
フェノキシ吉草酸、２．６−ナフタリンジカルボン酸又
は２．７−ナフタリンジカルボン酸等あるいはこれらの
カルボン酸の混合物が挙げられる。Specific examples of aromatic or aliphatic dicarboxylic acids suitable for producing this polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, superric acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p,
p'-dicarboxydiphenyl sulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, 2.6-naphthalene dicarboxylic acid or 2.7-naphthalene dicarboxylic acid, etc. Alternatively, a mixture of these carboxylic acids may be used.
またポリエステルの製造に適する脂肪族グリコールとし
ては、炭素数２〜１２の直鎖アルキレングリコール、例
えばエチレングリコール、１．３−プロピレングリコー
ル、１．４−ブテングリコール、１，６−ヘキセングリ
コール、１１２−ドデカメチレングリコール等が例示さ
れる。また、芳香族グリコール化合物としては、ｐ−キ
シリレングリコール、ピロカテコール、レゾルシノール
、ヒドロキノン又はこれらの化合物のアルキル置換誘導
体がある。他の適当なグリコルとしては、ｌ、４−シク
ロヘキサンジメタツールも挙げられる。Also, examples of aliphatic glycols suitable for producing polyester include linear alkylene glycols having 2 to 12 carbon atoms, such as ethylene glycol, 1,3-propylene glycol, 1,4-butene glycol, 1,6-hexene glycol, 112- Examples include dodecamethylene glycol. Examples of aromatic glycol compounds include p-xylylene glycol, pyrocatechol, resorcinol, hydroquinone, and alkyl-substituted derivatives of these compounds. Other suitable glycols include 1,4-cyclohexane dimetatool.
他の好ましいポリエステルとしては、ラクトンの開環重
合によるポリエステルも挙げられる。例えば、ポリビバ
ロラクトン、ポリ（ε−カプロラクトン）等である。Other preferred polyesters include polyesters produced by ring-opening polymerization of lactones. For example, polyvivalolactone, poly(ε-caprolactone), and the like.
また 更に他の好ましいポリエステルとしては、瀉融状
態で液晶を形成するポリマー（Ｔｈｅｒｍ。Still other preferable polyesters include polymers that form liquid crystals in a molten state (Therm).
ｔｒｏｐｉｃ Ｌｉｑｕｉｄ Ｃｒｙｓｔａｌ Ｐｏｌ
ｙｍｅｒ； ＴＬＣＰＩとしてのポリエステルがある。tropic Liquid Crystal Pol
ymer; There is polyester as TLCPI.
これらの範晴に入るポリエステルとしては、イーストマ
ンコダック社のＸ７Ｇダ一トコ社のＸｙｄａｒ （ザイ
ダー）、住友化学社のエコノール、セラニーズ社のベク
トラ等が代表的な商品である。Typical polyesters that fall into these categories include Eastman Kodak Company's X7G Datco's Xydar, Sumitomo Chemical Company's Econol, and Celanese Company's Vectra.
以上、（Ｂ）成分として挙げたポリエステルの中でも、
ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレン
テレフタレート（ＰＢＴ）、ポリナフタレンテレフタレ
ート（ＰＥＮ）、ポリ１．４シクロヘキサンジメチレン
テレフタレート（ＰＣＴ）又は液晶性ポリエステル等が
、本発明の熱可塑性樹脂組成物に好適な飽和ポリエステ
ルである。Among the polyesters mentioned above as component (B),
Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polynaphthalene terephthalate (PEN), poly1.4 cyclohexane dimethylene terephthalate (PCT), liquid crystalline polyester, etc. are suitable saturated polyesters for the thermoplastic resin composition of the present invention. It is polyester.
成 Ａ び Ｂ の Ａ
本発明の熱可塑性樹脂組成物の成分（Ａ）及び（Ｂ）の
配合比の選択は、最終成形品の用途の要求性能によって
決定される。Formulation A and B The selection of the blending ratio of components (A) and (B) of the thermoplastic resin composition of the present invention is determined by the required performance of the intended use of the final molded product.
すなわち、成形加工性、機械的強度、耐溶剤性、寸法精
度、高温剛性等の性質は、各構成成分の特徴とその配合
比で調整できる場合が多いものの、例えば剛性と衝撃強
度のように、発現機構の相反する性質は、両立させるの
が困難な場合が多い。実用上の目的のためには、通常、
成形性、機械的強度、高温剛性等の諸性質の調和を適切
にするという駅点から行われる。従って、本発明におけ
る組成物の各成分の配合比には、本質的に限界的なもの
は存在しないが、実用的には下記の範囲が有用であると
言える。That is, although properties such as moldability, mechanical strength, solvent resistance, dimensional accuracy, and high-temperature rigidity can often be adjusted by the characteristics of each component and their blending ratio, for example, rigidity and impact strength, etc. The contradictory properties of expression mechanisms are often difficult to reconcile. For practical purposes, usually
This is done from the point of achieving an appropriate balance of various properties such as formability, mechanical strength, and high-temperature rigidity. Therefore, although there is essentially no limit to the blending ratio of each component in the composition of the present invention, it can be said that the following ranges are practically useful.
成分（Ａ）：官能化ポリフェニレンエーテル９０〜１０
重量％
成分（Ｂ） 飽和ポリエステル
１０〜９０重量％
また、本発明で用いる成分（Ａ）は単独であっても良い
し、官能化ポリフェニレンエーテルと未官能化ポリフェ
ニレンエーテルとの混合物であっても良い。Component (A): Functionalized polyphenylene ether 90-10
Weight% Component (B) Saturated polyester 10 to 90% by weight Component (A) used in the present invention may be used alone or may be a mixture of functionalized polyphenylene ether and unfunctionalized polyphenylene ether. .
住皿煎風±
本発明による樹脂組成物には、他の付加的成分を添加す
ることができる。例えば、飽和ポリエステルに周知の酸
化防止剤、耐候性改良剤、可塑剤、流動性改良剤、離形
剤、造核剤等、ポリフエニレンエーテルに周知の酸化防
止剤、耐候性改良剤、可塑剤、スチレン系樹脂、流動性
改良剤等を付加的成分として使用できる。また有機・無
機充填剤、補強剤、特にガラス繊維、マイカ、タルク、
ワラストナイト、チタン酸カリウム、炭酸カルシウム、
シリカ等の添加は剛性、耐熱性、寸法精度等の向上に有
効である。実用のために各種着色剤及びそれらの分散剤
なども周知のものが使用できる。Other additional ingredients can be added to the resin composition according to the present invention. For example, well-known antioxidants, weather resistance improvers, plasticizers, fluidity improvers, mold release agents, nucleating agents, etc. for saturated polyester; well-known antioxidants, weather resistance improvers, plasticizers, etc. for polyphenylene ether. additives, styrenic resins, flow modifiers, etc. can be used as additional ingredients. Also, organic/inorganic fillers, reinforcing agents, especially glass fiber, mica, talc,
Wollastonite, potassium titanate, calcium carbonate,
Addition of silica etc. is effective in improving rigidity, heat resistance, dimensional accuracy, etc. For practical purposes, various known colorants and dispersants thereof can be used.
更に耐衝撃強度向上剤の添加、特に不飽和エポキシ化合
物とエチレンからなる共重合体又は不飽和エポキシ化合
物、エチレン及びエチレン系不飽和化合物からなる共重
合体の添加、スチレン−ブタジェン共重合体ゴム及びそ
の水素化物、エチレン重合体及びエチレン−プロピレン
−（ジエン）共重合体ゴム、更には、それらのα、β−
不飽和カルボン酸無水物変性体及び不飽和グリシジルエ
ステル若しくは不飽和グリシジルエーテルとの変性体の
添加は組成物の衝撃強度向上に有効である。上記の耐衝
撃強度向上剤は、単独で用いても良いし、２種又はそれ
以上併用しても良い。耐衝撃強度向上剤の配合量は、目
標とする物性値−二より異なるが、例えば組成物の剛ｊ
生と衝撃強度のバランスの改良の場合は１組成物の樹脂
成分１００重量部当り、５〜３０重量部である。Furthermore, the addition of an impact strength improver, in particular the addition of a copolymer consisting of an unsaturated epoxy compound and ethylene or an unsaturated epoxy compound, a copolymer consisting of ethylene and an ethylenically unsaturated compound, styrene-butadiene copolymer rubber and Its hydrides, ethylene polymers and ethylene-propylene-(diene) copolymer rubbers, as well as their α, β-
Addition of an unsaturated carboxylic acid anhydride modified product and an unsaturated glycidyl ester or unsaturated glycidyl ether modified product is effective for improving the impact strength of the composition. The above impact strength improvers may be used alone, or in combination of two or more. The blending amount of the impact strength improver differs depending on the target physical property value, for example, the stiffness of the composition.
In order to improve the balance between raw strength and impact strength, the amount is 5 to 30 parts by weight per 100 parts by weight of the resin component of one composition.
粧虜隻凹工豆１１
本発明の熱可塑性樹脂組成物の混合方法としでは、上記
の各成分を、各種混線機、例えば−軸押出機、二軸押出
機、バンバリーミキサ−等で混線混合する方法、各種成
分の？８液又は懸濁液を混合した後に溶剤を除去するか
、共通非忍媒を加えて沈澱、決別し回収する方法などい
ずれの方法も用いることができる。また混合の順序は、
可能ないずれの順序によっても良いが、溶融混線法によ
って混合する場合には、粘度の高いものから逐次混合す
る方法は好ましい方法である。As a method for mixing the thermoplastic resin composition of the present invention, the above-mentioned components are mixed in various mixers, such as a screw extruder, twin screw extruder, Banbury mixer, etc. Method, various ingredients? Any method can be used, such as removing the solvent after mixing the 8 liquid or suspension, or adding a common non-toxic medium to precipitate, separate and recover. Also, the order of mixing is
Any possible order may be used, but when mixing by melt cross-fertilization, a preferred method is to sequentially mix the components starting from the one with the highest viscosity.
（実施例）
以下、実施例により、本発明の詳細な説明するが、これ
により、本発明の範囲は、特に限定されるものではない
。(Examples) Hereinafter, the present invention will be explained in detail with reference to Examples, but the scope of the present invention is not particularly limited thereby.
官能化ポリフェニレンエーテルの調製例：ポリフェニレ
ンエーテル及びトルエンを表１に記載の配合量で反応器
に仕込み、加熱撹拌して、ポリフェニレンエーテルを溶
解した。同表記載の反応温度迄加熱した後、ナトリウム
エトキシドをエタノールに溶解して添加し、続いて、同
表記載の官能化剤を所定量添加し、加熱撹拌して反応し
た。反応終了後、反応混合物を２５１２のアセトニトリ
ル中に注ぎ、生成した官能化ポリフェニレンエーテルを
沈澱させた。ｉ戸別後、再びアセトニトリル２５Ｉ２で
洗浄し、８０℃で減圧乾燥させ、官能化ポリフェニレン
エーテルを得た。これら得られた樹脂を官能化ポリフェ
ニレンエーテル（ａ）及び（ｂ）として、その結果を表
１に示す。Preparation example of functionalized polyphenylene ether: Polyphenylene ether and toluene were charged into a reactor in the amounts shown in Table 1, and the mixture was heated and stirred to dissolve the polyphenylene ether. After heating to the reaction temperature listed in the same table, sodium ethoxide was dissolved in ethanol and added, followed by a predetermined amount of the functionalizing agent listed in the table, and the mixture was heated and stirred to react. After the reaction was completed, the reaction mixture was poured into 2512 acetonitrile to precipitate the functionalized polyphenylene ether formed. After being separated, it was washed again with acetonitrile 25I2 and dried under reduced pressure at 80°C to obtain a functionalized polyphenylene ether. These obtained resins were designated as functionalized polyphenylene ethers (a) and (b), and the results are shown in Table 1.
実施例１．２及び比較例
官能化ポリフェニレンエーテル（ａ）
（ｂ）、飽和ポリエステル（三菱化成社製ポリブチレン
テレフタレート、商品名 ツバドール５０１０）及び未
官能化ポリフェニレンエーテル（日本ポリエーテル社製
、クロロホルムの３０°Ｃての固有粘度０．３ｄＩ／ｇ
）を使用して、内容積６０ｃｃの東洋精機社製のブラス
トミルに表２に示す組成で、２６０℃、回転数６Ｏｒｐ
ｍの条件にて、６分間溶融混練した。得られた樹脂組成
物を分析評価した。Example 1.2 and Comparative Examples Functionalized polyphenylene ether (a) (b), saturated polyester (polybutylene terephthalate manufactured by Mitsubishi Kasei Co., Ltd., trade name: Tubadol 5010) and unfunctionalized polyphenylene ether (manufactured by Nippon Polyether Co., Ltd., chloroform). Intrinsic viscosity at 30°C 0.3dI/g
) with the composition shown in Table 2 in a blast mill manufactured by Toyo Seiki Co., Ltd. with an internal volume of 60 cc, at 260°C and at a rotation speed of 6 Orp.
The mixture was melt-kneaded for 6 minutes under the conditions of m. The obtained resin composition was analyzed and evaluated.
結果を表２に示す。本結果からも明らかなように、官能
化ポリフェニレンエーテルと飽和ポリエステルを配合し
た場合は、非常に細かい球状に近いポリフェニレンエー
テルの分散が認められると共に、グラフト共重合したポ
リフェニレンエーテルが認められた。The results are shown in Table 2. As is clear from the present results, when functionalized polyphenylene ether and saturated polyester were blended, very fine, almost spherical polyphenylene ether dispersion was observed, as well as graft copolymerized polyphenylene ether.
なお、分析評価法は次の通り。The analysis and evaluation method is as follows.
（１）分散形態
得られた樹脂組成物の二相分散状態を調べるために、日
立製作所製Ｓ−２４００型走査型電子顕微鏡により断面
を観察した。(1) Dispersion Form In order to examine the two-phase dispersion state of the obtained resin composition, a cross section was observed using a scanning electron microscope model S-2400 manufactured by Hitachi, Ltd.
（２）樹脂組成物の分析
得られた樹脂組成物から一部を取り出し、０−クロルフ
ェノールとテトラクロルエチレンの３対２（容積比）の
混合液に溶解させた。この溶液をクロロホルム中に注ぎ
不溶分を決過して取り出り乾燥した。この不溶物中のポ
リフェニレンエーテルの量を該樹脂組成物にグラフト結
合したポリフェニレンエーテルの量比として、使用した
ポリブチレンテレフタレートに対する百分率で表した変
性率として求めた。また、先に得られたクロロホルム溶
液を多量のメタノール中に投入し、析出した樹脂を乾燥
し、赤外線分光分析法で分析した。(2) Analysis of Resin Composition A portion of the obtained resin composition was taken out and dissolved in a 3:2 (volume ratio) mixed solution of 0-chlorophenol and tetrachlorethylene. This solution was poured into chloroform to remove insoluble matter, taken out and dried. The amount of polyphenylene ether in the insoluble matter was determined as the ratio of the amount of polyphenylene ether grafted to the resin composition, and as the modification rate expressed as a percentage of the polybutylene terephthalate used. In addition, the chloroform solution obtained earlier was poured into a large amount of methanol, and the precipitated resin was dried and analyzed by infrared spectroscopy.
（発明の効果）
以上のように、官能化ポリフェニレンエーテルと飽和ポ
リエステルを配合した本発明の熱可塑性樹脂組成物は表
２に示したように、同樹脂が共重合した優れた分散構造
を有している。(Effects of the Invention) As shown in Table 2, the thermoplastic resin composition of the present invention containing functionalized polyphenylene ether and saturated polyester has an excellent dispersion structure in which the same resin is copolymerized. ing.
第１百の続き 市市東邦町１番地 三菱油化株式会社四日市総 合研光所内Continuation of the 100th part 1 Tohocho, City Mitsubishi Yuka Co., Ltd. Yokkaichiso Inside Gokenkosho
Claims (1)
熱可塑性樹脂組成物。 （Ａ）一般式 ▲数式、化学式、表等があります▼（ I ） （式中、Ｑ＾１は各々ハロゲン原子、第一級若しくは第
二級アルキル基、フェニル基、アミノアルキル基、炭化
水素オキシ基又はハロ炭化水素オキシ基を表し、Ｑ＾２
は各々水素原子、ハロゲン原子、第一級若しくは第二級
アルキル基、フェニル基、ハロアルキル基、炭化水素オ
キシ基又はハロ炭化水素オキシ基を表し、ｎは１０以上
の数を表し、Ｘは酸素原子又は窒素原子を表し、Ｒ＾１
は炭素数１〜１２のアルキレン基を表し、Ｒ＾２及びＲ
＾３は各々炭素数１〜６の炭化水素基を表す。ｓはＸが
酸素原子のときは１、Ｘが窒素原子のときは２であり、
ｔは１〜３の整数である） で示される末端基変性されたポリフェニレンエーテル１
０〜９０重量％ （Ｂ）飽和ポリエステル９０〜１０重量％[Scope of Claims] A thermoplastic resin composition comprising the following components (A) and (B). (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, Q^1 is each a halogen atom, a primary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbon oxy group or halohydrocarbonoxy group, Q^2
each represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, n represents a number of 10 or more, and X is an oxygen atom Or represents a nitrogen atom, R^1
represents an alkylene group having 1 to 12 carbon atoms, R^2 and R
^3 each represents a hydrocarbon group having 1 to 6 carbon atoms. s is 1 when X is an oxygen atom, 2 when X is a nitrogen atom,
t is an integer of 1 to 3) Terminal group-modified polyphenylene ether 1
0-90% by weight (B) Saturated polyester 90-10% by weight
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18722090A JPH0477553A (en) | 1990-07-17 | 1990-07-17 | Thermoplastic resin composition |
| EP19910108052 EP0457351A3 (en) | 1990-05-17 | 1991-05-17 | Process for producing silane-modified polyphenylene ether and thermoplastic resin composition containing the same |
| US07/701,910 US5177156A (en) | 1990-05-17 | 1991-05-17 | Process for producing silane-modified polyphenylene ether and thermoplastic resin composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18722090A JPH0477553A (en) | 1990-07-17 | 1990-07-17 | Thermoplastic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0477553A true JPH0477553A (en) | 1992-03-11 |
Family
ID=16202175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18722090A Pending JPH0477553A (en) | 1990-05-17 | 1990-07-17 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0477553A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020017412A1 (en) * | 2018-07-20 | 2020-01-23 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminated plate, resin sheet, and printed-wiring board |
-
1990
- 1990-07-17 JP JP18722090A patent/JPH0477553A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020017412A1 (en) * | 2018-07-20 | 2020-01-23 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminated plate, resin sheet, and printed-wiring board |
| JPWO2020017412A1 (en) * | 2018-07-20 | 2021-08-12 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board |
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