JP2006297620A - Method of manufacturing recovered polystyrene-compounded polyphenylene ether resin composition - Google Patents
Method of manufacturing recovered polystyrene-compounded polyphenylene ether resin composition Download PDFInfo
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- JP2006297620A JP2006297620A JP2005118427A JP2005118427A JP2006297620A JP 2006297620 A JP2006297620 A JP 2006297620A JP 2005118427 A JP2005118427 A JP 2005118427A JP 2005118427 A JP2005118427 A JP 2005118427A JP 2006297620 A JP2006297620 A JP 2006297620A
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- Prior art keywords
- polyphenylene ether
- extruder
- resin composition
- based resin
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- -1 polyphenylene Polymers 0.000 claims description 45
- 238000004898 kneading Methods 0.000 claims description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 38
- 239000002994 raw material Substances 0.000 claims description 19
- 239000008188 pellet Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 15
- 239000003063 flame retardant Substances 0.000 claims description 15
- 239000012760 heat stabilizer Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 2
- 229920001890 Novodur Polymers 0.000 abstract description 4
- 229920001400 block copolymer Polymers 0.000 description 33
- 238000000034 method Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 229920002554 vinyl polymer Polymers 0.000 description 21
- 239000004793 Polystyrene Substances 0.000 description 20
- 229920002223 polystyrene Polymers 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 229920005669 high impact polystyrene Polymers 0.000 description 14
- 239000004797 high-impact polystyrene Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 9
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920005990 polystyrene resin Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 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
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 1
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- FDBMBOYIVUGUSL-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FDBMBOYIVUGUSL-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 238000002845 discoloration Methods 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
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- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
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- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 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
- 150000003738 xylenes Chemical class 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/57—Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
- B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
- B29C48/83—Heating or cooling the cylinders
- B29C48/832—Heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
- B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
Abstract
Description
本発明は、循環社会に貢献できる、高生産時にも衝撃強度、表面外観に優れる、回収ポリスチレン配合ポリフェニレンエーテル系樹脂組成物の製造方法に関するものである。 The present invention relates to a method for producing a recovered polystyrene-containing polyphenylene ether-based resin composition that can contribute to a recycling society and has excellent impact strength and surface appearance even during high production.
家電リサイクル法が施行され、家電ＯＡ分野におけるポリスチレンの回収も多く発生している。この回収家電品の筐体等を粉砕して粉砕ペレットが利用されるようになった。しかしながらこの粉砕ペレットを用いた組成物は、物性低下が大きく、成形品の強度、表面外観等が著しく低下する。家電リサイクル法によって回収される家電樹脂には、ハロゲンやアンチモン、電気配線、電子回路などに用いられた材料の粉砕品も混合されており、特に金属の混入は、回収粉砕ペレットを用いて製造された製品の強度、表面外観等を著しく低下させる。回収粉砕ペレットは設置環境により、長期に渡り太陽光などで経年劣化の可能性もあり、さらに再溶融による熱履歴により熱劣化の可能性も否定できない。溶融濾別時にできる限り低温で濾別し、熱安定剤を添加することで樹脂の劣化を防止することができる。ところで、特許文献１〜２には回収ポリスチレン配合ポリフェニレンエーテル系樹脂組成物が開示されているが、特許文献１では、主に発泡体についての製法記載であり、特許文献２には、粉砕品の形状、金属異物が押出機に与える影響の記載はあるが、樹脂材料に与える影響についての記載はない。
The Home Appliance Recycling Law has been enforced, and many polystyrene collections have occurred in the home appliance OA field. Crushed pellets have been used by crushing the housing of the collected household appliances. However, the composition using the pulverized pellets is greatly deteriorated in physical properties, and the strength, surface appearance and the like of the molded product are remarkably reduced. Home appliance resin recovered by the Home Appliance Recycling Law is mixed with pulverized products of materials used for halogen, antimony, electrical wiring, electronic circuits, etc. Especially metal contamination is produced using recovered pulverized pellets. The product strength and surface appearance are significantly reduced. Depending on the installation environment, the recovered pulverized pellets may deteriorate over time due to sunlight or the like, and the possibility of thermal deterioration due to heat history due to remelting cannot be denied. It is possible to prevent deterioration of the resin by filtering at a temperature as low as possible during melt filtration and adding a heat stabilizer. Incidentally,
本発明は、市場から回収されるポリスチレン系樹脂を用い、特に家電及びＯＡ機器からの回収ポリスチレン樹脂を含有するポリフェニレンエーテル系樹脂組成物の改善された製造方法を提供することを目的とする。 An object of this invention is to provide the improved manufacturing method of the polyphenylene ether-type resin composition which uses the polystyrene-type resin collect | recovered from a market, and contains especially the collection | recovery polystyrene resin from a household appliance and OA apparatus.
本発明者らは、上記課題を解決するため、鋭意検討をかさねた結果、市場回収ポリスチレンを用い、さらに溶融濾別した市場回収ポリスチレンを原料とし、二軸押出機の特定条件において、衝撃強度、表面外観の悪化がなく、且つ高生産時も衝撃強度、表面外観が悪化しない製造方法を見出した。
すなわち、本発明は、
［１］ （Ａ）ポリフェニレンエーテル樹脂、（Ｂ）ハロゲン含有量が３重量％以下で、且つアンチモン原子、銅原子、鉄原子の含有量がそれぞれ１重量％以下である回収スチレン系樹脂、及び（Ｃ）未使用スチレン系樹脂を含む樹脂組成物を製造するに際し、（Ｂ）成分を押出機後段にある第２供給口、及び／又は第３供給口より供給し、前段のバレル設定温度が２３０℃〜３４０℃、後段のバレル設定温度が２２０℃〜３００℃であり、後段バレル温度が前段バレル温度より低いことを特徴とするポリフェニレンエーテル系樹脂組成物の製造方法、
In order to solve the above-mentioned problems, the present inventors have intensively studied.As a result, using market-recovered polystyrene, further using melt-filtered market-recovered polystyrene as a raw material, under specific conditions of a twin-screw extruder, impact strength, The present inventors have found a production method in which the surface appearance is not deteriorated and the impact strength and the surface appearance are not deteriorated even at high production.
That is, the present invention
[1] (A) a polyphenylene ether resin, (B) a recovered styrene resin having a halogen content of 3% by weight or less and an antimony atom, a copper atom, or an iron atom content of 1% by weight or less, and ( C) When producing a resin composition containing an unused styrene-based resin, the component (B) is supplied from the second supply port and / or the third supply port in the latter stage of the extruder, and the barrel set temperature in the previous stage is 230. A method for producing a polyphenylene ether-based resin composition, characterized in that the barrel setting temperature of the rear stage is 220 ° C. to 300 ° C., and the rear stage barrel temperature is lower than the front stage barrel temperature,
［２］ （Ａ）成分もしくは（Ａ）成分と（Ｃ）成分の一部を押出機の第１供給口より供給し、（Ｂ）成分および残りの（Ｃ）成分を押出機の第２供給口及び／又は第３供給口より供給することを特徴とする［１］に記載のポリフェニレンエーテル系樹脂組成物の製造方法、
［３］ 押出機の前段に、前段ニーディングセクションを１ヶ所設け（Ｌ１）、該前段
ニーディングセクション有効長／スクリュー外径が２〜１０であり、該押出機の後段に、後段ニーディングセクションを１ヶ所もしくは２ヶ所設け（Ｌ２，Ｌ３）、それぞれ後段ニーディングセクション有効長／スクリュー外径が２〜１０であることを特徴とする［１］又は［２］に記載のポリフェニレンエーテル系樹脂組成物の製造方法、
［４］ 前段ニーディングセクションを一ケ所（Ｌ１）、後段ニーディングセクションを２ヶ所（Ｌ２、Ｌ３）設けることを特徴とする［１］〜［３］のいずれかに記載のポリフェニレンエーテル系樹脂組成物の製造方法、
[2] Component (A) or part of component (A) and component (C) is supplied from the first supply port of the extruder, and component (B) and the remaining component (C) are supplied to the second of the extruder. The method for producing a polyphenylene ether-based resin composition according to [1], wherein the polyphenylene ether-based resin composition is supplied from a mouth and / or a third supply port,
[3] One front kneading section is provided in the front stage of the extruder (L1), the effective length of the front kneading section / screw outer diameter is 2 to 10, and the rear kneading section is in the rear stage of the extruder. 1 or 2 (L2, L3), the latter kneading section effective length / screw outer diameter is 2 to 10, respectively, The polyphenylene ether resin composition according to [1] or [2] Manufacturing method,
[4] The polyphenylene ether-based resin composition according to any one of [1] to [3], wherein one front kneading section (L1) and two rear kneading sections (L2, L3) are provided. Manufacturing method,
［５］ 押出機の後段に、さらにニーディングセクション（Ｌ４）を設け、後段ニーディングセクション有効長／スクリュー外径＝０．５〜５であることを特徴とする［４］に記載のポリフェニレンエーテル系樹脂組成物の製造方法、
［６］ （Ｂ）成分として、押出機入り口及び／又は裁断ペレット出口にマグネットを、ダイス部にスクリーンメッシュを装備した押出機を用い、２７０℃以下のバレル温度に設定し、押出裁断したリペレットを用いることを特徴とする［１］〜［５］のいずれかに記載のポリフェニレンエーテル系樹脂組成物の製造方法、
［７］ （Ｂ）成分をリペレットする際、原料ホッパー投入口、及び押出機入り口と裁断したリペレット出口に６０００ガウス以上のマグネットを設置することを特徴とする［６］に記載のポリフェニレンエーテル系樹脂組成物の製造方法、
[5] The polyphenylene ether according to [4], wherein a kneading section (L4) is further provided in the latter stage of the extruder, and the latter kneading section effective length / screw outer diameter = 0.5 to 5 Process for producing a resin-based resin composition,
[6] As the component (B), using an extruder equipped with a magnet at the extruder inlet and / or the cutting pellet outlet and a screen mesh in the die part, set to a barrel temperature of 270 ° C. or less, A method for producing a polyphenylene ether-based resin composition according to any one of [1] to [5], wherein
[7] The polyphenylene ether resin according to [6], wherein when re-pelletizing the component (B), a magnet of 6000 gauss or more is installed at a raw material hopper input port and a re-pellet outlet cut from an extruder inlet. Production method of the composition,
［８］ （Ｂ）成分をリペレットする際、熱安定剤を添加することを特徴とする［６］又は［７］に記載のポリフェニレンエーテル系樹脂組成物の製造方法、
［９］ （Ｂ）成分を、押出機後段にある第２供給口、及び／又は第３供給口より供給時、同時に熱安定剤を添加することを特徴とする［１］〜［８］のいずれかに記載のポリフェニレンエーテル系樹脂組成物の製造方法、
［１０］ （Ｂ）回収スチレン系樹脂が、家電及びＯＡ機器から回収されたスチレン系樹脂であることを特徴とする［１］〜［９］のいずれかに記載のポリフェニレンエーテル系樹脂組成物製造方法、
[8] A method for producing a polyphenylene ether-based resin composition according to [6] or [7], wherein a heat stabilizer is added when repelletizing the component (B).
[9] The heat stabilizer is added at the same time when the component (B) is supplied from the second supply port and / or the third supply port in the latter stage of the extruder, according to [1] to [8] A method for producing the polyphenylene ether-based resin composition according to any one of the above,
[10] The polyphenylene ether-based resin composition production according to any one of [1] to [9], wherein (B) the recovered styrene-based resin is a styrene-based resin recovered from home appliances and OA equipment. Method,
［１１］ （Ｂ）回収スチレン系樹脂が、市場から回収されたスチレン系樹脂であって、且つガラス転移温度の少なくとも一つが−６０℃以下であること特徴とする［１］〜［１０］のいずれかに記載のポリフェニレンエーテル系樹脂組成物製造方法、
［１２］ 更に（Ｄ）難燃剤を押出機の途中より供給することを特徴とする［１］〜［１１］のいずれかに記載のポリフェニレンエーテル系樹脂組成物製造方法、
［１３］ （Ｄ）難燃剤としてリン系化合物を含むことを特徴とする［１２］に記載のポリフェニレンエーテル系樹脂組成物製造方法、
［１４］ 更に（Ｅ）ゴム状物質を押出機の第２供給口及び／又は第３供給口より供給することを特徴とする［１］〜［１３］のいずれかに記載のポリフェニレンエーテル系樹脂組成物製造方法、
である。
[11] (B) The recovered styrene resin is a styrene resin recovered from the market, and at least one of the glass transition temperatures is −60 ° C. or lower. A method for producing a polyphenylene ether-based resin composition according to any one of the above,
[12] The method for producing a polyphenylene ether-based resin composition according to any one of [1] to [11], further comprising (D) supplying a flame retardant from the middle of the extruder.
[13] (D) The method for producing a polyphenylene ether-based resin composition according to [12], comprising a phosphorus compound as a flame retardant,
[14] The polyphenylene ether resin according to any one of [1] to [13], wherein (E) the rubber-like substance is further supplied from the second supply port and / or the third supply port of the extruder. Composition manufacturing method,
It is.
本発明は、市場から回収されたポリスチレンを用い、押出機の特定な条件下で溶融混練することで、衝撃強度、成形品の表面外観の悪化を抑制でき、高生産時も衝撃強度、表面外観性を損なわない製造方法を提供することができる。 The present invention can suppress impact strength and deterioration of the surface appearance of the molded product by melt kneading under specific conditions of the extruder using polystyrene recovered from the market. Impact strength and surface appearance even during high production The manufacturing method which does not impair the property can be provided.
本発明について、以下具体的に説明する。
本発明で（Ａ）成分のポリフェニレンエーテルは、本発明の樹脂組成物に耐熱性および難燃性を付与するうえで必須な成分であり、
該ＰＰＥは、結合単位：
In the present invention, the polyphenylene ether of the component (A) is an essential component for imparting heat resistance and flame retardancy to the resin composition of the present invention.
The PPE is a binding unit:
本発明のポリフェニレンエーテルの具体的な例としては、例えば、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）との共重合体のごとき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。 Specific examples of the polyphenylene ether of the present invention include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols ( Examples thereof include polyphenylene ether copolymers such as copolymers with 2,3,6-trimethylphenol and 2-methyl-6-butylphenol. Of these, 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 , 4-phenylene ether).
本発明で用いるポリフェニレンエーテルの製造方法は公知の方法で得られるものであれば特に限定されるものではなく、例えば、米国特許第３３０６８７４号明細書に記載されているように第一塩化銅とアミンのコンプレックスを触媒として用い、例えば２，６−ジメチルフェノールを酸化重合することにより容易に製造でき、そのほかにも米国特許第３３０６８７５号明細書、同第３２５７３５７号明細書及び同第３２５７３５８号明細書、特公昭５２−１７８８０号公報及び特開昭５０−５１１９７号公報及び同６３−１５２６２８号公報等に記載された方法で容易に製造できる。 The method for producing the polyphenylene ether used in the present invention is not particularly limited as long as it can be obtained by a known method. For example, as described in US Pat. No. 3,306,874, cuprous chloride and amine are used. For example, and can be easily produced by oxidative polymerization of 2,6-dimethylphenol. In addition, U.S. Pat. Nos. 3,306,875, 3,257,357, and 3,257,358, It can be easily produced by the methods described in JP-B-52-17880, JP-A-50-51197 and JP-A-63-152628.
本発明で使用することのできるポリフェニレンエーテルの還元粘度（０．５ｇ／ｄｌ、クロロホルム溶液、３０℃測定）は、０．１５〜０．７０ｄｌ／ｇの範囲であることが好ましく、さらに好ましくは０．２０〜０．６０ｄｌ／ｇの範囲、より好ましくは０．４０〜０．５５ｄｌ／ｇの範囲である。
これらは、２種以上の還元粘度の異なるポリフェニレンエーテルをブレンドしたものであっても、何ら問題なく使用することができる。例えば、還元粘度０．４５ｄｌ／ｇ以下のポリフェニレンエーテルと還元粘度０．５０ｄｌ／ｇ以上のポリフェニレンエーテルの混合物、還元粘度０．４０ｄｌ／ｇ以下の低分子量ポリフェニレンエーテルと還元粘度０．５０ｄｌ／ｇ以上のポリフェニレンエーテルの混合物等が挙げられるが、もちろん、これらに限定されることはない。
The reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) of the polyphenylene ether that can be used in the present invention is preferably in the range of 0.15 to 0.70 dl / g, more preferably 0. The range is from 20 to 0.60 dl / g, more preferably from 0.40 to 0.55 dl / g.
These can be used without any problem even if they are blends of two or more polyphenylene ethers having different reduced viscosities. For example, a mixture of a polyphenylene ether having a reduced viscosity of 0.45 dl / g or less and a polyphenylene ether having a reduced viscosity of 0.50 dl / g or more, a low molecular weight polyphenylene ether having a reduced viscosity of 0.40 dl / g or less, and a reduced viscosity of 0.50 dl / g or more. A mixture of polyphenylene ethers, etc., of course, is, of course, not limited to these.
また、本発明に使用できるポリフェニレンエーテルは、重合溶媒に起因する有機溶剤が、ポリフェニレンエーテル１００重量部に対して５重量％未満の量で残存していても構わない。これら重合溶媒に起因する有機溶剤は、重合後の乾燥工程で完全に除去するのは困難であり、通常数百ｐｐｍから数％の範囲で残存しているものである。ここでいう重合溶
媒に起因する有機溶媒としては、トルエン、キシレンの各異性体、エチルベンゼン、炭素数１〜５アルコール類、クロロホルム、ジクロルメタン、クロルベンゼン、ジクロルベンゼン等の１種以上が挙げられる。
また、本発明で使用できる（Ａ）ポリフェニレンエーテルは、全部又は一部が変性されたポリフェニレンエーテルであっても構わない。
ここでいう変性されたポリフェニレンエーテルとは、分子構造内に少なくとも１個の炭素−炭素二重結合または、三重結合及び少なくとも１個のカルボン酸基、酸無水物基、アミノ基、水酸基、又はグリシジル基を有する、少なくとも１種の変性化合物で変性されたポリフェニレンエーテルを指す。
In the polyphenylene ether that can be used in the present invention, the organic solvent derived from the polymerization solvent may remain in an amount of less than 5% by weight based on 100 parts by weight of the polyphenylene ether. These organic solvents resulting from the polymerization solvent are difficult to remove completely in the drying step after polymerization, and usually remain in the range of several hundred ppm to several percent. Examples of the organic solvent resulting from the polymerization solvent include one or more of toluene, xylene isomers, ethylbenzene, C1-5 alcohols, chloroform, dichloromethane, chlorobenzene, dichlorobenzene and the like.
Further, the polyphenylene ether (A) that can be used in the present invention may be a polyphenylene ether that is modified in whole or in part.
The modified polyphenylene ether here means at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl in the molecular structure. The polyphenylene ether modified with at least one modifying compound having a group.
該変性されたポリフェニレンエーテルの製法としては、（１）ラジカル開始剤の存在下、非存在下で１００℃以上、ポリフェニレンエーテルのガラス転移温度未満の範囲の温度でポリフェニレンエーテルを溶融させることなく変性化合物と反応させる方法、（２）ラジカル開始剤の存在下、非存在下でポリフェニレンエーテルのガラス転移温度以上３６０℃以下の範囲の温度で変性化合物と溶融混練し反応させる方法、（３）ラジカル開始剤の存在下、非存在下でポリフェニレンエーテルのガラス転移温度未満の温度で、ポリフェニレンエーテルと変性化合物を溶液中で反応させる方法等が挙げられ、これらいずれの方法でも構わないが、（１）及び、（２）の方法が好ましい。更に、ポリフェニレンエーテルに添加することが可能な公知の添加剤等もポリフェニレンエーテル１００重量部に対して１０重量部未満の量で添加しても構わない。 The method for producing the modified polyphenylene ether includes (1) a modified compound without melting the polyphenylene ether at a temperature in the range of 100 ° C. or higher in the presence or absence of a radical initiator and lower than the glass transition temperature of the polyphenylene ether. (2) a method in which a modified compound is melt-kneaded and reacted at a temperature in the range of the glass transition temperature of polyphenylene ether to 360 ° C. in the presence or absence of a radical initiator, and (3) a radical initiator. In the presence or absence, a method of reacting a polyphenylene ether and a modifying compound in a solution at a temperature lower than the glass transition temperature of the polyphenylene ether may be mentioned. Any of these methods may be used, (1) and The method (2) is preferred. Further, known additives that can be added to polyphenylene ether may be added in an amount of less than 10 parts by weight based on 100 parts by weight of polyphenylene ether.
本発明でいう（Ｂ）成分の回収スチレン系樹脂とは、各種成形加工法により加工されたポリスチレン成形体を市場より回収して得られたものであり、ポリスチレンシート、発泡スチロール成形体、発泡ポリスチレンシート、ＣＤなどの各種ケース類、ＴＶハウジング筐体、ＣＲＴハウジング、プリンター、複写機外装、エアコン等で、主な成分は、ジェネラルパーパスポリスチレン（ＧＰＰＳ）、ゴム変性ポリスチレン（ＨＩＰＳ）、スチレン−アクリロニトリル共重合体（ＡＳ樹脂）、スチレン−ゴム質重合体−アクリロニトリル共重合体（ＡＢＳ樹脂）、シンディオタクティックポリスチレン等であるが、本発明に好適なものとしては主な成分はジェネラルパーパスポリスチレン（ＧＰＰＳ）、ゴム変性ポリスチレン（ＨＩＰＳ）である。共役ジエンブロック共重合体、芳香族ビニル−共役ジエンブロック共重合体などのゴム状改質剤を含んでもよい。本発明において、衝撃性の確保から（Ｂ）成分のガラス転移温度の少なくとも一つが−１００℃以上、−６０℃以下に存在することが好ましい。（Ｂ）成分は、０．５ｇ／１００ｍｌのトルエンで測定される還元粘度が０．５ｄｌ／ｇ以上、０．９ｄｌ／ｇ以下のものが良い。また、ハロゲンの含有量が３重量％以下、好ましくは２重量％以下、更に好ましくは１重量％以下である。ハロゲンの含有量が３重量％を越えると、ポリフェニレンエーテルの組成物としての成形品外観や物性が著しく劣るため好ましくない。ここで言うハロゲンとは、主に塩素、及び臭素を言い、ハロゲン含有量とは、主に化合物として含まれている塩素及び臭素の合計の含有量を言う。（Ｂ）成分に含まれる、アンチモン原子、及び銅原子の含有量はそれぞれ１重量％以下であることが必要である。アンチモンと銅の共存状態では、物性低下を促進する上、有毒なスビチンガス、ハロゲン化水素ガスを発生させることから、作業環境上好ましくない。また、銅は燃焼を促進する活性点としての働きもあり、難燃性をもたせる材料には好ましくない。本発明において、アンチモン原子、銅原子とは、単体として存在するもの、及び化合物として存在するものの両方を包含する。これら市場から回収されたポリスチレン系樹脂は、最終組成物成形品の表面外観、塗装性、組成物生産時の安定性の面から金属等の異物を除去後小片に破砕され、更に溶融濾別し異物除去し、リペレットとしたものがよい。特に溶融濾別することで均一な原料特性、粒度を確保出来ることから異物除去したリペレットが好ましい。市場から回収されたポリスチレン系樹脂は金属等の異物除去後、小片に粉砕される。しかしながら、金属等の異物除去は完全ではなく、そのままの使用では、最終組成物の特性、押出機へのダメージ等の影響を与えることとなる。 The recovered styrene-based resin of the component (B) in the present invention is obtained by recovering from the market a polystyrene molded product processed by various molding methods, and is a polystyrene sheet, a polystyrene foam molded product, a foamed polystyrene sheet. , CD and other cases, TV housings, CRT housings, printers, copier exteriors, air conditioners, etc. Main components are general purpose polystyrene (GPPS), rubber-modified polystyrene (HIPS), styrene-acrylonitrile co-polymer The polymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin), syndiotactic polystyrene and the like, but as main components suitable for the present invention, general-purpose polystyrene (GPPS), Rubber modified polystyrene (HIPS)A rubbery modifier such as a conjugated diene block copolymer or an aromatic vinyl-conjugated diene block copolymer may be included. In the present invention, it is preferable that at least one of the glass transition temperatures of the component (B) is present at −100 ° C. or higher and −60 ° C. or lower in order to ensure impact properties. The component (B) preferably has a reduced viscosity of 0.5 dl / g or more and 0.9 dl / g or less measured with 0.5 g / 100 ml of toluene. The halogen content is 3% by weight or less, preferably 2% by weight or less, and more preferably 1% by weight or less. When the halogen content exceeds 3% by weight, the appearance and physical properties of the molded product as a polyphenylene ether composition are remarkably inferior. The halogen mentioned here mainly means chlorine and bromine, and the halogen content means the total content of chlorine and bromine mainly contained as a compound. (B) Content of an antimony atom and a copper atom contained in a component needs to be 1 weight% or less, respectively. The coexistence of antimony and copper is not preferable in terms of the working environment because it promotes a decrease in physical properties and generates toxic suvitin gas and hydrogen halide gas. Copper also serves as an active point that promotes combustion, and is not preferable for a material having flame retardancy. In the present invention, the antimony atom and the copper atom include both those present as a simple substance and those present as a compound. Polystyrene resins recovered from these markets are crushed into small pieces after removing foreign substances such as metals from the viewpoint of surface appearance, paintability, and stability during composition production of the final composition molded product, and further melt filtered. It is preferable to remove foreign matter and make a repellet. In particular, a repellet from which foreign matter has been removed is preferred because uniform raw material characteristics and particle size can be ensured by melt filtration. The polystyrene resin collected from the market is crushed into small pieces after removing foreign substances such as metal. However, the removal of foreign matters such as metals is not complete, and if it is used as it is, it will affect the properties of the final composition, damage to the extruder, and the like.
また、市場回収ポリスチレン系樹脂粉砕品は、原料として使用する場合、特性のバラツキを管理する必要がある。溶融濾別時の具体的な工程としては、押出機の原料ホッパー、或いは押出機に原料供給するフィーダーホッパーの投入口、及び押出機の入口部に、磁力を利用した金属分離用マグネットを設置し、押出機にて溶融濾別を行い、冷却後、ストランドカッターにてペレットに裁断しリペレットとする。ストランドカッターの出口にもマグネットを設置し、金属の分離を行う。マグネットは、６０００ガウス以上が好ましく、より好ましくは１００００ガウス以上、特に好ましくは１２０００ガウス以上、２００００ガウス以下である。回収ポリスチレン系樹脂の濾別の具体的な加工機械としては、例えば、単軸押出機、二軸押出機、ニーダー等のスクリーンメッシュで濾別する方法が挙げられるが、これらに限定されるものではない。金属等の異物を除去後小片に破砕された回収スチレン系樹脂を、これらの加工機械により熱安定剤と２７０℃以下で溶融混錬し、５０メッシュ（目開き３２８μｍ）〜３００メッシュ（目開き４５μｍ）、好ましくは８０メッシュ（目開き２１８μｍ）〜２５０メッシュ（目開き７２μｍ）、より好ましくは８０メッシュ（目開き２１８μｍ）〜２００メッシュ（目開き７７μｍ）のスクリーンメッシュで濾別後、冷却し長さ約３ｍｍ×径約３ｍｍのペレットに切断する。スクリーンメッシュは平織り、平畳織り等あるが、特に限定されるものではない。目開きの小さい濾過網を中心にしその前後に補強網として目開きの大きいメッシュを重ね、メッシュの枚数は２〜５枚を１セットとすることが好ましい。メッシュの材質は、特に限定されるものではないが、ステンレス、真鍮、銅、鉄を亜鉛メッキしたもの等がある。本発明に好適な回収ポリスチレンは、３０℃で測定された０．５ｇ／１０ｍｌトルエン溶液の還元粘度が０．５ｄｌ／ｇ以上、０．９ｄｌ／ｇ以下のものが好ましい。トルエン還元粘度は、（Ｂ）成分をトルエンに溶解し、遠心分離した上澄みを濾別した濾過液の粘度を測定することで求められる。 Moreover, when using a market-recovered polystyrene resin pulverized product as a raw material, it is necessary to manage variation in characteristics. As a specific process at the time of melt filtration, a metal separation magnet using magnetic force is installed at the raw material hopper of the extruder or the feeder hopper feeding the raw material to the extruder and the inlet of the extruder. Then, melt filtration is performed with an extruder, and after cooling, it is cut into pellets with a strand cutter to form repellets. A magnet is also installed at the exit of the strand cutter to separate the metal. The magnet is preferably 6000 gauss or more, more preferably 10000 gauss or more, particularly preferably 12000 gauss or more and 20000 gauss or less. Specific processing machines for filtering the recovered polystyrene resin include, for example, methods of filtering with a screen mesh such as a single screw extruder, twin screw extruder, kneader, but are not limited thereto. Absent. The recovered styrene resin crushed into small pieces after removing foreign substances such as metal is melted and kneaded with a heat stabilizer at 270 ° C. or less with these processing machines, and 50 mesh (mesh opening 328 μm) to 300 mesh (mesh opening 45 μm). ), Preferably filtered through a screen mesh of 80 mesh (aperture 218 μm) to 250 mesh (aperture 72 μm), more preferably 80 mesh (aperture 218 μm) to 200 mesh (aperture 77 μm), followed by cooling and length Cut into pellets of about 3 mm × diameter about 3 mm. Screen meshes include plain weave and flat tatami weave, but are not particularly limited. It is preferable to place a mesh having a large mesh as a reinforcing mesh on the front and back of the filtration mesh having a small mesh, and 2 to 5 meshes as one set. The material of the mesh is not particularly limited, and examples thereof include stainless steel, brass, copper, and iron galvanized. The recovered polystyrene suitable for the present invention preferably has a reduced viscosity of 0.5 dl / g or more and 0.9 dl / g or less of a 0.5 g / 10 ml toluene solution measured at 30 ° C. Toluene reduced viscosity is calculated | required by measuring the viscosity of the filtrate which melt | dissolved (B) component in toluene and filtered the supernatant liquid which carried out centrifugation.
（Ｃ）成分の未使用スチレン系樹脂とは、樹脂メーカーで製造された、一度も加工されていない未使用ポリスチレンである。本発明で用いられる未使用のポリスチレンとしては、ジェネラルパーパスポリスチレン（ＧＰＰＳ）、ゴム変性ポリスチレン（ＨＩＰＳ）をいう。ゴム変性ポリスチレン（ＨＩＰＳ）のゴム種は、熱安定性の高い１，４結合を有するポリブタジエンが好ましく、ポリブタジエン含有量が、８重量％以上がより好ましい。マトリックスポリスチレンの３０℃で測定された０．５ｇ／１０ｍｌトルエン溶液の還元粘度が０．５ｄｌ／ｇ以上が好ましく、０．５５〜０．９０ｄｌ／ｇがより好ましい。（Ｂ）成分と（Ｃ）成分の割合は、（Ｂ）／（Ｃ）が重量比で５／９５〜９０／１０、好ましくは１０／９０〜６０／４０、より好ましくは２０／８０〜４０／６０である。 The unused styrenic resin (C) is an unused polystyrene that has been produced by a resin manufacturer and has never been processed. The unused polystyrene used in the present invention refers to general purpose polystyrene (GPPS) and rubber-modified polystyrene (HIPS). The rubber type of rubber-modified polystyrene (HIPS) is preferably polybutadiene having 1,4 bonds with high thermal stability, and the polybutadiene content is more preferably 8% by weight or more. The reduced viscosity of the 0.5 g / 10 ml toluene solution of the matrix polystyrene measured at 30 ° C. is preferably 0.5 dl / g or more, more preferably 0.55 to 0.90 dl / g. The ratio of the component (B) to the component (C) is such that (B) / (C) is in a weight ratio of 5/95 to 90/10, preferably 10/90 to 60/40, more preferably 20/80 to 40. / 60.
（Ｄ）成分である難燃剤は、環境の面からハロゲンを含まないリン系化合物が用いられることが好ましい。リン系化合物としては、ポリリン酸化合物、赤燐、ホスファゼン化合物、下記（２−ａ）或いは（２−ｂ）で代表されるリン酸エステル系化合物などがある。
熱安定性、耐加水分解性の観点から、より好ましくは式（２−ａ）に示されるリン酸エステルが好適である。
一般式（２−ａ）においてｎ１、ｎ２が０で、Ｒ３，Ｒ４がメチル基であることが好ましい。また、一般式（２−ａ）においてｍ１、ｍ２、ｍ３、ｍ４が０か１である。つまり、末端のフェニル基へのアルキル基の置換がないか、又はＱ１、Ｑ２、Ｑ３、Ｑ４がメチル基である。（２−ａ）に示されるリン酸エステル化合物は特定の二官能フェノールによる結合構造と、特定の単官能フェノールによる末端構造を有す。二官能フェノールとしては、２，２−ビス（４−ヒドロキシフェニル）プロパン〔通称ビスフェノールＡ〕、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、ビス（４−ヒドロキシフェニル）メタン、ビス（４−ヒドロキシ−３，５−ジメチルフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタンなどのビスフェノール類が挙げられるが、特にビスフェノールＡが好ましい。単官能フェノールとしては、無置換フェノール、モノアルキルフェノール、ジアルキルフェノール、トリアルキルフェノールを単独又は２種以上の混合
物として使用できる。特にフェノール、クレゾール、ジメチルフェノール（混合キシレノール）、２，６−ジメチルフェノール、トリメチルフェノールが好ましい。式（２−ａ）で表されるリン酸エステル化合物は、加工時の熱安定性、耐加水分解性、低ガス性に優れている。また、ポリフェニレンエーテル樹脂との間で反応を起こしてゲル化するようなこともなく、ポリフェニレンエーテル樹脂の分解を促進することもなく、成形加工機の内部金属部品や金型等を腐食させることなく好適に用いられる。
From the viewpoints of thermal stability and hydrolysis resistance, a phosphate ester represented by the formula (2-a) is more preferable.
In general formula (2-a), n1 and n2 are preferably 0, and R3 and R4 are preferably methyl groups. In the general formula (2-a), m1, m2, m3, and m4 are 0 or 1. That is, there is no substitution of the alkyl group to the terminal phenyl group, or Q1, Q2, Q3, and Q4 are methyl groups. The phosphate ester compound shown in (2-a) has a binding structure with a specific bifunctional phenol and a terminal structure with a specific monofunctional phenol. As the bifunctional phenol, 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A], 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) methane, Bisphenols such as bis (4-hydroxy-3,5-dimethylphenyl) methane and 1,1-bis (4-hydroxyphenyl) ethane are exemplified, and bisphenol A is particularly preferable. As the monofunctional phenol, unsubstituted phenol, monoalkylphenol, dialkylphenol, or trialkylphenol can be used alone or as a mixture of two or more. In particular, phenol, cresol, dimethylphenol (mixed xylenol), 2,6-dimethylphenol, and trimethylphenol are preferable. The phosphate ester compound represented by the formula (2-a) is excellent in thermal stability during processing, hydrolysis resistance, and low gas properties. In addition, there is no reaction with polyphenylene ether resin, no gelation, no degradation of polyphenylene ether resin, no corrosion of internal metal parts or molds of molding machine Preferably used.
本発明組成物における（Ａ）ポリフェニレンエーテル、［（Ｂ）＋（Ｃ）］スチレン系樹脂及び（Ｄ）リン系難燃剤の配合割合は、（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）＝１００重量部に対して、（Ａ）／［（Ｂ）＋（Ｃ）］／（Ｄ）＝（１０〜７０重量部）／（９０〜３０重量部）／（０〜３５重量部）が好ましく、（１５〜５０重量部）／（８０〜２０重量部）／（５〜３０重量部）がより好ましい。 The blending ratio of (A) polyphenylene ether, [(B) + (C)] styrene resin and (D) phosphorus flame retardant in the composition of the present invention is (A) + (B) + (C) + (D ) = 100 parts by weight (A) / [(B) + (C)] / (D) = (10-70 parts by weight) / (90-30 parts by weight) / (0-35 parts by weight) Is preferable, and (15 to 50 parts by weight) / (80 to 20 parts by weight) / (5 to 30 parts by weight) is more preferable.
本発明の樹脂組成物を外装材料若しくは筐体材料等に用いる場合は、優れた成形流動性と難燃性能が特に要求され、ＵＬ９４：Ｖ−１／３ｍｍ以上の条件を満たす必要がある。この条件を満たすためには、例えば式（２−ａ）で示される難燃剤を用いる場合、本発明の樹脂組成物１ｋｇに含まれる、ポリフェニレンエーテルの酸素原子と難燃剤のリン原子のモル積が１．１以上の条件が推奨される。
この難燃レベルを保つための条件は、式（２−ａ）の難燃剤を用いた場合、（Ａ）＋（Ｂ）＋（Ｃ）＋（Ｄ）＝１００重量部に対して、（Ａ）ポリフェニレンエーテル／（Ｄ）難燃剤＝（１０〜６０重量部）／（４６．６〜７．６重量部）、好ましくは（１５〜５０重量部）／（３０〜１０重量部）、更に好ましくは（２０〜４０重量部）／（２５〜１１．４重量部）である。
When the resin composition of the present invention is used for an exterior material or a casing material, excellent molding fluidity and flame retardancy are particularly required, and UL94: V-1 / 3 mm or more must be satisfied. In order to satisfy this condition, for example, when the flame retardant represented by the formula (2-a) is used, the molar product of the oxygen atom of the polyphenylene ether and the phosphorus atom of the flame retardant contained in 1 kg of the resin composition of the present invention is A condition of 1.1 or higher is recommended.
The conditions for maintaining this flame retardant level are as follows: (A) + (B) + (C) + (D) = 100 parts by weight when (A) + (B) flame retardant is used. ) Polyphenylene ether / (D) Flame retardant = (10-60 parts by weight) / (46.6-7.6 parts by weight), preferably (15-50 parts by weight) / (30-10 parts by weight), more preferably Is (20-40 parts by weight) / (25-11.4 parts by weight).
本発明で使用することのできる（Ｅ）ゴム状物質としては、ポリイソプレン、ポリブタジエン、芳香族ビニル−共役ジエンブロック共重合体、ポリエチレン、ポリプロピレン、エチレン−１−ブテン共重合体、エチレン−１−オクテン共重合体などのエチレン−１−アルケン共重合体、エチレン−メタクリル酸メチル共重合体、エチレン−メタクリル酸エチル共重合体、酢酸ビニル共重合体などが挙げられる。本発明のゴム状物質としては、芳香族ビニル−共役ジエンブロック共重合体（Ｅ−１）、及び／又はオレフィン系エラストマー（Ｅ−２）であり、（Ｅ−１）成分としては、少なくとも１個の芳香族ビニル化合物を主体とする重合体ブロックと少なくとも１個の共役ジエン化合物を主体とする重合体ブロックからなるブロック共重合体及び、または水素添加されたブロック共重合体である。好ましくは、芳香族化合物−共役ジエン共重合体、芳香族化合物−共役ジエン共重合体の水素添加物が挙げられる。これらの中では、芳香族化合物−共役ジエンブロック共重合体の水素添加物が最も好ましい。 Examples of the rubber-like substance (E) that can be used in the present invention include polyisoprene, polybutadiene, aromatic vinyl-conjugated diene block copolymer, polyethylene, polypropylene, ethylene-1-butene copolymer, and ethylene-1- Examples thereof include ethylene-1-alkene copolymers such as octene copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, and vinyl acetate copolymer. The rubber-like substance of the present invention is an aromatic vinyl-conjugated diene block copolymer (E-1) and / or an olefin elastomer (E-2), and the component (E-1) is at least 1 A block copolymer comprising a polymer block mainly comprising one aromatic vinyl compound and a polymer block mainly comprising at least one conjugated diene compound, or a hydrogenated block copolymer. Preferably, a hydrogenated product of an aromatic compound-conjugated diene copolymer or an aromatic compound-conjugated diene copolymer is used. Of these, a hydrogenated product of an aromatic compound-conjugated diene block copolymer is most preferable.
ここでいう芳香族化合物−共役ジエンブロック共重合体とは、芳香族ビニル化合物を主体とする重合体ブロック（ａ）と共役ジエン化合物を主体とする重合体ブロック（ｂ）から構成されるブロック共重合体であり、各ブロックの結合形式がａｂ型、ａｂａ型、ａｂａｂ型のいずれかであるブロック共重合体が好ましい。
また、ブロック共重合体中の芳香族ビニル化合物と共役ジエン化合物との重量比は、１０／９０〜９０／１０であることが望ましい。より好ましくは、１５／８５〜５５／４５である。更に、これらは芳香族ビニル化合物と共役ジエン化合物との重量比が異なるものを２種以上ブレンドしても構わない。
芳香族ビニル化合物の具体例としてはスチレン、α−メチルスチレン、ビニルトルエン等が挙げられ、これらから選ばれた１種以上の化合物が用いられるが、中でもスチレンが特に好ましい。
The aromatic compound-conjugated diene block copolymer here is a block copolymer composed of a polymer block (a) mainly composed of an aromatic vinyl compound and a polymer block (b) mainly composed of a conjugated diene compound. A block copolymer in which the binding mode of each block is any of ab type, aba type, and abab type is preferable.
The weight ratio of the aromatic vinyl compound to the conjugated diene compound in the block copolymer is preferably 10/90 to 90/10. More preferably, it is 15/85 to 55/45. Furthermore, these may be blended in two or more types having different weight ratios of the aromatic vinyl compound and the conjugated diene compound.
Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like, and one or more compounds selected from these are used, and among them, styrene is particularly preferable.
共役ジエン化合物の具体例としては、ブタジエン、イソプレン、ピペリレン、１，３−
ペンタジエン等が挙げられ、これらから選ばれた１種以上の化合物が用いられるが、中でもブタジエン、イソプレンおよびこれらの組み合わせが好ましい。
ブロック共重合体の共役ジエン化合物としてブタジエンを使用する場合は、ポリブタジエンブロック部分のミクロ構造は１，２−ビニル含量もしくは１，２−ビニル含量と３，４−ビニル含量の合計量が５〜８０％が好ましく、さらには１０〜５０％がより好ましい。
また、芳香族ビニル化合物と共役ジエン化合物のブロック共重合体の水素添加物とは、上述の芳香族ビニル化合物と共役ジエン化合物のブロック共重合体を水素添加処理することにより、ジエン化合物を主体とする重合体ブロックの脂肪族二重結合を０を越えて１００％の範囲で制御したものをいう。該ブロック共重合体の水素添加物の好ましい水素添加率は５０％以上であり、より好ましくは８０％以上、最も好ましくは９８％以上である。
Specific examples of the conjugated diene compound include butadiene, isoprene, piperylene, 1,3-
Pentadiene and the like can be mentioned, and one or more compounds selected from these can be used. Of these, butadiene, isoprene and combinations thereof are preferred.
When butadiene is used as the conjugated diene compound of the block copolymer, the microstructure of the polybutadiene block portion is 1,2-vinyl content or the total amount of 1,2-vinyl content and 3,4-vinyl content is 5-80. % Is preferable, and further 10 to 50% is more preferable.
In addition, the hydrogenated product of the block copolymer of the aromatic vinyl compound and the conjugated diene compound is mainly composed of the diene compound by subjecting the block copolymer of the aromatic vinyl compound and the conjugated diene compound to a hydrogenation treatment. In the polymer block, the aliphatic double bond of the polymer block is controlled in the range of more than 0 to 100%. A preferable hydrogenation rate of the hydrogenated product of the block copolymer is 50% or more, more preferably 80% or more, and most preferably 98% or more.
また、本発明における芳香族ビニル化合物と共役ジエン化合物のブロック共重合体及びその水素添加物の分子量としては、昭和電工製ＧＰＣ装置［ＳＹＳＴＥＭ２１］で、クロロホルムを溶媒とし、４０℃、ポリスチレンスタンダードで測定した数平均分子量（Ｍｎ）が、１０，０００〜５００，０００のものが好ましく、３０，０００〜２５０，０００のものが最も好ましい。
これら芳香族ビニル化合物−共役ジエン化合物のブロック共重合体は、結合形式の異なるもの、芳香族ビニル化合物種の異なるもの、共役ジエン化合物種の異なるもの、１，２−結合ビニル含有量もしくは１，２−結合ビニル含有量と３，４−結合ビニル含有量の異なるもの、芳香族ビニル化合物成分含有量の異なるもの、水素添加率の異なるもの等混合して用いても構わない。
The molecular weight of the block copolymer of the aromatic vinyl compound and the conjugated diene compound in the present invention and the hydrogenated product thereof was measured by Showa Denko GPC [SYSTEM21] using chloroform as a solvent at 40 ° C. and polystyrene standard. The number average molecular weight (Mn) is preferably 10,000 to 500,000, and most preferably 30,000 to 250,000.
These aromatic vinyl compound-conjugated diene compound block copolymers have different bond types, different aromatic vinyl compound types, different conjugated diene compound types, 1,2-bonded vinyl content or 1, A mixture having a different 2-bond vinyl content and a 3,4-bond vinyl content, a different aromatic vinyl compound component content, a different hydrogenation rate, or the like may be used in combination.
また、本発明で使用するブロック共重合体は、全部又は一部が変性されたブロック共重合体であっても構わない。
ここでいう変性されたブロック共重合体とは、分子構造内に少なくとも１個の炭素−炭素二重結合または、三重結合及び少なくとも１個のカルボン酸基、酸無水物基、アミノ基、水酸基、又はグリシジル基を有する、少なくとも１種の変性化合物で変性されたブロック共重合体を指す。
該変性されたブロック共重合体の製法としては、（１）ラジカル開始剤の存在下、非存在下でブロック共重合体の軟化点温度以上２５０℃以下の範囲の温度で変性化合物と溶融混練し反応させる方法、（２）ラジカル開始剤の存在下、非存在下でブロック共重合体の軟化点以下の温度で、ブロック共重合体と変性化合物を溶液中で反応させる方法、（３）ラジカル開始剤の存在下、非存在下でブロック共重合体の軟化点以下の温度で、ブロック共重合体と変性化合物を溶融させることなく反応させる方法等が挙げられ、これらいずれの方法でも構わないが、（１）の方法が好ましく、更には（１）の中でもラジカル開始剤存在下で行う方法が最も好ましい。
Further, the block copolymer used in the present invention may be a block copolymer in which all or part of the block copolymer is modified.
The modified block copolymer as used herein refers to at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group in the molecular structure. Alternatively, it refers to a block copolymer modified with at least one modifying compound having a glycidyl group.
The modified block copolymer can be produced by (1) melt-kneading with a modifying compound at a temperature in the range of the softening point of the block copolymer to 250 ° C. in the presence or absence of a radical initiator. A method of reacting, (2) a method of reacting a block copolymer and a modifying compound in a solution at a temperature below the softening point of the block copolymer in the presence or absence of a radical initiator, and (3) radical initiation. In the presence of the agent, in the absence of the block copolymer at a temperature equal to or lower than the softening point of the block copolymer, a method of reacting without melting the block copolymer and the like, and any of these methods may be used, The method (1) is preferable, and the method (1) performed in the presence of a radical initiator is most preferable.
ここでいう分子構造内に少なくとも１個の炭素−炭素二重結合または、三重結合及び少なくとも１個のカルボン酸基、酸無水物基、アミノ基、水酸基、又はグリシジル基を有する少なくとも１種の変性化合物とは、変性されたポリフェニレンエーテルで述べた変性化合物と同じである。
また、本発明のブロック共重合体中には、パラフィンを主成分とするオイルをあらかじめ混合したものを用いても構わない。パラフィンを主成分とするオイルをあらかじめ混合する事により、成形品強度、表面外観に効果的である。この際の好ましいパラフィンを主成分とするオイルの量はブロック共重合体１００重量部に対して、１〜７０重量部である。７０重量部を越えて混合すると取り扱い性に劣る。
At least one modification having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure referred to herein. The compound is the same as the modified compound described in the modified polyphenylene ether.
In addition, the block copolymer of the present invention may be prepared by previously mixing an oil mainly composed of paraffin. By premixing oil mainly composed of paraffin, it is effective for the strength of the molded product and the surface appearance. In this case, the preferred amount of oil mainly composed of paraffin is 1 to 70 parts by weight with respect to 100 parts by weight of the block copolymer. If it exceeds 70 parts by weight, the handleability is poor.
本発明で用いる（Ｅ−２）成分であるオレフィン系エラストマーは、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、高密度ポリエチレン（ＨＤ
ＰＥ）、ポリプロピレン（ＰＰ）、エチレン−１−ブテン共重合体、エチレン−１−オクテン共重合体、エチレン−１−アルケン共重合体、エチレン−メタクリル酸メチル共重合体、エチレンメタクリル酸エチル共重合体、無水マレイン酸変性ポリエチレン、エチレン−プロピレン共重合体などが挙げられるが、これらに限定されるものではない。
The olefin elastomer which is the component (E-2) used in the present invention is low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HD).
PE), polypropylene (PP), ethylene-1-butene copolymer, ethylene-1-octene copolymer, ethylene-1-alkene copolymer, ethylene-methyl methacrylate copolymer, ethylene ethyl methacrylate copolymer Examples thereof include, but are not limited to, polymers, maleic anhydride-modified polyethylene, and ethylene-propylene copolymers.
（Ｂ）成分を、スクリーンメッシュを装備した押出機で異物を濾別除去時、及び／又は二軸押出機の第２供給口、及び／又は第３供給口より供給時に添加する熱安定剤として、例えば、フォスフェート系化合物、ヒンダードフェノール系化合物などが挙げられる。フォスフェート系化合物としては、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジフォスファイトなどが挙げられ、ヒンダードフェノール系化合物としては、ペンタエリスリチル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、２，４−ビス−（ｎ−オクチルチオ）−６−（４−ヒドロキシ−３，５−ジ−ｔ−ブチルアニリノ）−１，３，５−トリアジンなどが挙げられるが、これらに限定されるものでない。これらの安定剤は単独、２種以上を併用することもできる。 The component (B) is added as a heat stabilizer at the time of removing and removing foreign matters by an extruder equipped with a screen mesh and / or at the time of supply from the second supply port and / or the third supply port of the twin screw extruder. Examples thereof include phosphate compounds and hindered phenol compounds. Examples of the phosphate compound include tris (2,4-di-t-butylphenyl) phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, and the like. As hindered phenol compounds, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and the like. However, it is not limited to these. These stabilizers can be used alone or in combination of two or more.
本発明では、上記した成分のほかに、本成分の効果を損なわない範囲で必要に応じて付加的成分を添加しても構わない。付加的成分の例を以下に挙げる。すなわち、無機充填材（タルク、カオリン、ゾノトライト、ワラストナイト、酸化チタン、チタン酸カリウム、炭素繊維、ガラス繊維など、）、無機充填材と樹脂との親和性を高める為の公知のシランカップリング剤、滴下防止効果を示すフッ素系ポリマ−、オレフィン系ポリマー、可塑剤（オイル、低分子量ポリオレフィン、ポリエチレングリコ−ル、脂肪酸エステル類等）及び、カーボンブラック等の帯電防止剤、各種過酸化物、酸化亜鉛、硫化亜鉛、酸化防止剤、紫外線吸収剤、光安定剤等である。 In the present invention, in addition to the above-described components, additional components may be added as necessary within a range that does not impair the effects of this component. Examples of additional components are listed below. In other words, inorganic fillers (talc, kaolin, zonolite, wollastonite, titanium oxide, potassium titanate, carbon fibers, glass fibers, etc.), known silane couplings for increasing the affinity between inorganic fillers and resins Agent, fluorine polymer showing anti-drip effect, olefin polymer, plasticizer (oil, low molecular weight polyolefin, polyethylene glycol, fatty acid ester, etc.), antistatic agent such as carbon black, various peroxides, Zinc oxide, zinc sulfide, antioxidant, ultraviolet absorber, light stabilizer and the like.
本発明の具体的な加工機械としては、例えば、単軸押出機、二軸押出機、多軸押出機、ロール、ニーダー、ブラベンダープラストグラフ、バンバリーミキサー等が挙げられるが、中でも単軸押出機、二軸押出機が好ましく、ポリフェニレンエーテル系樹脂組成物の加工に際しては、特に二軸押出機が好ましい。 Specific processing machines of the present invention include, for example, a single screw extruder, a twin screw extruder, a multi screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. A twin-screw extruder is preferable, and a twin-screw extruder is particularly preferable when processing the polyphenylene ether-based resin composition.
本発明の組成物の製造方法において用いられる、（Ｂ）成分は、好ましくは単軸、又は二軸押出機を用い、押出機原料ホッパー、及び原料が押出機へ供給される押出機入り口に６０００ガウス以上、好ましくは１００００ガウス以上、より好ましくは１２０００ガウス以上、２００００ガウス以下のマグネットを設置し、金属除去を行う。また、（Ｂ）成分の溶融押出に際しては、５０メッシュ（目開き３２８μｍ）〜３００メッシュ（目開き４５μｍ）、好ましくは８０メッシュ（目開き２１８μｍ）〜２５０メッシュ（目開き７２μｍ）、より好ましくは８０メッシュ（目開き２１８μｍ）〜２００メッシュ（目開き７７μｍ）のスクリーンメッシュで異物を濾別除去後、冷却しストランドカッターにて長さ約３ｍｍ×径約３ｍｍのペレットに切断する、該カッター出口にも６０００ガウス以上、好ましくは１００００ガウス以上、より好ましくは１２０００ガウス以上、２００００ガウス以下のマグネットを設置し、更に金属分離を行う（図１参照）。スクリーンメッシュは平織り、平畳織り、綾織り等あるが、特に限定されるものではない。目開きの小さい濾過網を中心にし、その前後に補強網として目開きの大きいメッシュを重ね、メッシュの枚数は２〜５枚を１セットとすることが好ましい。メッシュの材質は、特に限定されるものではないがステンレス、真鍮、銅、鉄を亜鉛メッキしたもの等がある。この（Ｂ）成分の上記メッシュによる濾別は、押出機のＬ／Ｄ（スクリュー長／スクリュー外径）＝１５〜５０、バレル設定温度を２７０℃以下、好ましくは２００℃〜２６０℃、より好ましくは２２０℃〜２６０℃に設定し、スクリュー回転数１００rpm〜１２００rpmにて、未溶融異物を濾別し、その際、熱安定剤を添加することが好ましい。 The component (B) used in the method for producing the composition of the present invention is preferably 6000 at the extruder raw material hopper and the extruder inlet to which the raw material is supplied to the extruder using a single-screw or twin-screw extruder. Metal removal is performed by installing a magnet of Gauss or higher, preferably 10,000 Gauss or higher, more preferably 12000 Gauss or higher and 20000 Gauss or lower. In the melt extrusion of the component (B), 50 mesh (aperture 328 μm) to 300 mesh (aperture 45 μm), preferably 80 mesh (aperture 218 μm) to 250 mesh (aperture 72 μm), more preferably 80 Foreign matter is removed by filtration with a screen mesh of mesh (aperture 218 μm) to 200 mesh (aperture 77 μm), then cooled and cut into pellets with a length of about 3 mm × diameter of about 3 mm with a strand cutter. A magnet of 6000 gauss or more, preferably 10000 gauss or more, more preferably 12000 gauss or more and 20000 gauss or less is installed, and further metal separation is performed (see FIG. 1). Screen meshes include plain weave, flat tatami weave, twill weave, etc., but are not particularly limited. It is preferable that a mesh with a large mesh is overlapped as a reinforcing mesh before and after the filter mesh having a small mesh, and 2 to 5 meshes are set as one set. The material of the mesh is not particularly limited, and examples thereof include stainless steel, brass, copper, and iron galvanized. The filtration of the component (B) with the mesh described above is such that the extruder L / D (screw length / screw outer diameter) = 15-50, and the barrel set temperature is 270 ° C. or less, preferably 200 ° C.-260 ° C., more preferably Is set to 220 ° C. to 260 ° C., and unmelted foreign matters are filtered off at a screw rotation speed of 100 rpm to 1200 rpm, and at that time, a heat stabilizer is preferably added.
本発明の樹脂組成物の製造方法は、特に好ましくは二軸押出機を用い、二軸押出機に原料を供給するための原料供給装置（原料フィーダー）は、特に限定はされないが、単軸スクリューフィーダー、２軸スクリューフィーダー、テーブルフィーダー、ロータリーフィーダーなどが使用できる。中でもロスインウエイトフィーダーが、原料供給の変動誤差が少なく好ましい。
本発明においては（Ｂ）成分は、押出機の第２供給口、及び／又は第３供給口より供給される。また、前段のバレル設定温度は２３０℃〜３４０℃、好ましくは２５０℃〜３４０℃、より好ましくは２７０℃〜３２０℃であり、後段のバレル設定温度は２２０℃〜３００℃、好ましくは２４０℃〜３００℃、より好ましくは、２５０℃〜２９０℃である。更に、後段のバレル設定温度は、前段バレル設定温度より低くすることが必要である。
The production method of the resin composition of the present invention is particularly preferably using a twin screw extruder, and the raw material supply device (raw material feeder) for supplying the raw material to the twin screw extruder is not particularly limited. A feeder, a twin screw feeder, a table feeder, a rotary feeder, or the like can be used. Of these, the loss-in-weight feeder is preferable because of less fluctuation error in the raw material supply.
In the present invention, the component (B) is supplied from the second supply port and / or the third supply port of the extruder. Moreover, the barrel set temperature of the front | former stage is 230 to 340 degreeC, Preferably it is 250 to 340 degreeC, More preferably, it is 270 to 320 degreeC, The barrel set temperature of the back | latter stage is 220 to 300 degreeC, Preferably it is 240 to It is 300 degreeC, More preferably, it is 250 to 290 degreeC. Furthermore, it is necessary to set the barrel setting temperature in the subsequent stage lower than the barrel setting temperature in the previous stage.
（Ａ）成分、もしくは（Ａ）成分と（Ｃ）成分の一部を押出機の第１供給口より供給し、（Ｂ）成分と（Ｃ）成分、もしくは残りの（Ｃ）成分と（Ｂ）成分を、押出機の第２供給口、及び／又は第３供給口より供給することが好ましい。（Ｂ）成分を押出機後段の第２供給口、及び／又は第３供給口より供給すると、押出機の第１供給口から供給した場合に比べ、前段バレル部での樹脂温度、滞留時間などの熱履歴が少なく、良好な特性が得られる。
（Ｄ）成分の供給は、押出機バレル途中より供給される。また、（Ｅ）成分は押出機の第２供給口、及び／又は第３供給口より供給することが好ましい。
Component (A) or a part of component (A) and component (C) is supplied from the first supply port of the extruder, and component (B) and component (C), or the remaining component (C) and (B ) Component is preferably supplied from the second supply port and / or the third supply port of the extruder. When the component (B) is supplied from the second supply port and / or the third supply port at the rear stage of the extruder, the resin temperature, residence time, etc. at the front stage barrel portion are compared with those supplied from the first supply port of the extruder. Thus, good characteristics can be obtained.
Component (D) is supplied from the middle of the extruder barrel. The component (E) is preferably supplied from the second supply port and / or the third supply port of the extruder.
押出機前段に、前段ニーディングセクション（Ｌ１）を１ヶ所設け、Ｌ１／Ｄ１（前段ニーディングセクション有効長／スクリュー外径）＝２〜１０が好ましく、より好ましくは３〜８であり、押出機の後段に、後段ニーディングセクションを1ヶ所もしくは２ケ所（Ｌ２、Ｌ３）を設け、Ｌ２／Ｄ１（後段ニーディングセクション１有効長／スクリュー外径）＝２〜１０が好ましく、より好ましくは３〜８、Ｌ３／Ｄ１（後段ニーディングセクション２有効長／スクリュー外径）＝２〜１０が好ましく、より好ましくは３〜８である。後段ニーディングセクションは２ヶ所設けるのが好ましい。さらにニーディングセクション（Ｌ４）、Ｌ４／Ｄ１（後段ニーディングセクション３有効長／スクリュー外径）＝０．５〜５を設けることが好ましい。後段のニーディングセクションは、（Ｂ）成分、添加剤などを、第２供給口又は第３供給口のみより供給する場合は、１カ所でもかまわない。前段ニーディングセクション（Ｌ１）、後段ニーディングセクション（Ｌ２，Ｌ３）のニーディングセクション有効長／スクリュー外径は成形品の表面外観の観点から２以上、１０以下が好ましい。
One front kneading section (L1) is provided in the front stage of the extruder, and L1 / D1 (effective length of the front kneading section / screw outer diameter) = 2 to 10 is preferable, more preferably 3 to 8. In the rear stage, one or two rear kneading sections (L2, L3) are provided, and L2 / D1 (effective length of
押出機のスクリュー回転数は１００〜１２００ｒｐｍであり、（Ｂ）成分を二軸押出機の第２供給口、及び／又は第３供給口より供給時、熱安定剤を添加する。第２供給口、第３供給口への原材料供給方法は、特に限定されるものでは無いが、上部開放口よりの単なる落下添加供給よりも、押出機サイド開放口から強制サイドフィーダーを用いて供給する方が安定で好ましい。二軸押出機第２供給口、第３供給口の上部開放口は同搬する空気を抜くため開放ベントとすることが好ましく、第２、第３供給口上部開放部は、樹脂のベントアップ、サイドフィーダーからの原料の飛散を防ぐために、第２、第３供給口の直上よりも上流側に設けるほうが、より好ましい（図２参照）。 The screw rotation speed of the extruder is 100 to 1200 rpm, and the thermal stabilizer is added when component (B) is supplied from the second supply port and / or the third supply port of the twin screw extruder. Although the raw material supply method to the 2nd supply port and the 3rd supply port is not specifically limited, it supplies using a forced side feeder from an extruder side opening port rather than the mere dropping addition supply from an upper opening port. It is more stable and preferable. It is preferable that the upper opening of the second supply port and the third supply port of the twin screw extruder is an open vent in order to remove the air to be carried, and the second and third supply port upper openings are vent-up of the resin, In order to prevent scattering of the raw material from the side feeder, it is more preferable to provide it upstream rather than directly above the second and third supply ports (see FIG. 2).
本発明の製造方法においては、前段ニーディングセクション、及び後段ニーディングセクションには、１枚当たりの羽根の厚みＬ５／Ｄ１（ニーディングディスク羽根１枚の長さ／スクリュー外径）が０．０５〜２．０であり、ねじれ角度が１０〜７５度のニーディングディスクや、ねじれ角度が８０〜１１０度のニーディングディスク、ねじれ角度が１２０〜１６０度のニーディングディスクが１組以上組み込まれ（図３参照）、さらにスクリューフライト部が１リード中に５〜１５箇所切りかかれたミキシングスクリューや、逆
フライトスクリューで組み合わせ構成され、且つ上記ニーディングディスクのねじれ角度が８０〜１１０度、ねじれ角度が１２０〜１６０度、または逆フライトスクリュー、バリスターリングを１組以上組み合わせたもので構成される。
In the manufacturing method of the present invention, the blade thickness L5 / D1 (length of one kneading disk blade / screw outer diameter) per sheet is 0.05 in the front kneading section and the rear kneading section. One or more sets of a kneading disk having a twist angle of 10 to 75 degrees, a kneading disk having a twist angle of 80 to 110 degrees, and a kneading disk having a twist angle of 120 to 160 degrees are incorporated ( 3), and the screw flight part is composed of a mixing screw with 5-15 cuts in one lead or a reverse flight screw, and the kneading disk has a twist angle of 80 to 110 degrees and a twist angle of 120 to 160 degrees or one or more pairs of reverse flight screw and varistor ring It consists of what was.
このようにして得られる本発明の組成物は、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。
これら各種部品としては、例えば、家電、ＯＡ機器、電気電子部品、建材、日用品、玩具、ゲーム機器、雑貨類、情報通信機器、自動車部品などが挙げられる。
家電、ＯＡ機器、電気電子部品としては、ＴＶ筐体、偏向ヨーク、プリンター筐体、パソコンモニター筐体、エアコン部品、洗濯機部品、パソコンハウジング、液晶プロジェクター部品、電話ハウジング、複写機ハウジング等が挙げられる。
建材、日用品、玩具、ゲーム機器、雑貨類としては、浴槽部材、洗面台部品、シャワーヘッド、ポンプ部材、おもちゃ類、ＴＶゲーム、携帯ゲーム、スポーツ用品、化粧品容器等が挙げられる。
情報通信機器としては、ターミナルアダプター、ルーター、モデム、デジタルカメラ部品、メモリーカード部品等が挙げられる。
自動車部品としては、インストゥルメントパネル、コンソールボックス、トリム等の内装部品が挙げられる。
The composition of the present invention thus obtained can be molded as various parts by various conventionally known methods such as injection molding, extrusion molding and hollow molding.
Examples of these various parts include home appliances, OA equipment, electrical and electronic parts, building materials, daily necessities, toys, game equipment, miscellaneous goods, information communication equipment, and automobile parts.
Household appliances, OA equipment, and electrical / electronic parts include TV cases, deflection yokes, printer cases, PC monitor cases, air conditioner parts, washing machine parts, PC housings, LCD projector parts, telephone housings, copier housings, etc. It is done.
Examples of building materials, daily necessities, toys, game machines, and miscellaneous goods include bathtub members, wash basin parts, shower heads, pump members, toys, TV games, portable games, sporting goods, cosmetic containers, and the like.
Information communication equipment includes terminal adapters, routers, modems, digital camera parts, memory card parts, and the like.
Examples of automobile parts include interior parts such as instrument panels, console boxes, and trims.
以下、本発明を実施例及び比較例により、本発明を更に詳細に説明する。
各成分として、以下のものを使用した。
（１）ＰＰＥ：ポリフェニレンエーテル、０．５ｇ／１００ｍｌクロロホルムでの還元粘度が３０℃で０．４２ｄｌ／ｇのものを使用した（以下ＰＰＥと略記）
（２）回収ＨＩＰＳ−１：市場回収され、家電リサイクルプラントで分別工程を経てチップ状とされたものを、スクリュー径６５ｍｍの単軸押出機を用い、バレル設定温度２３０℃で加熱溶融し、石川金網製５０メッシュ（目開き３２８μｍ）／８０メッシュ（目開き２１８μｍ）／５０メッシュ（目開き３２８μｍ）の３枚重ねのステンレス製スクリーンメッシュで異物を濾別除去し、冷却後ストランドカッターにて約３ｍｍ径×３ｍｍ長の均一化されたペレットに裁断した。
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples.
The following were used as each component.
(1) PPE: Polyphenylene ether, 0.5 g / 100 ml having a reduced viscosity of 0.42 dl / g at 30 ° C. (hereinafter abbreviated as PPE)
(2) Recovered HIPS-1: Recovered in the market and made into chips after separation at a home appliance recycling plant, using a single screw extruder with a screw diameter of 65 mm, heated and melted at a barrel set temperature of 230 ° C., Ishikawa Foreign matter is filtered and removed with a stainless steel screen mesh of 50 mesh (mesh opening 328 μm) / 80 mesh (mesh opening 218 μm) / 50 mesh (mesh opening 328 μm), and after cooling, it is about 3 mm with a strand cutter. It cut | judged to the uniform pellet of a diameter x 3 mm length.
（３）回収ＨＩＰＳ−２：市場回収され、家電リサイクルプラントで分別工程を経てチップ状とされたものを、スクリュー径６５ｍｍの単軸押出機を用い、バレル設定温度２３０℃で加熱溶融し、石川金網製５０メッシュ（目開き３２８μｍ）／８０メッシュ（目開き２１８μｍ）／５０メッシュ（目開き３２８μｍ）の３枚重ねのステンレス製スクリーンメッシュで異物を濾別除去し、冷却後ストランドカッターにて約３ｍｍ径×３ｍｍ長の均一化されたペレットに裁断した。押出機原料ホッパー及び押出機入り口、ストランドカッター出口に１２０００ガウスのマグネットによる金属分離も実施した。 (3) Recovered HIPS-2: Recovered in the market and made into chips after separation at a home appliance recycling plant, using a single screw extruder with a screw diameter of 65 mm, heated and melted at a barrel setting temperature of 230 ° C., Ishikawa Foreign matter is filtered and removed with a stainless steel screen mesh of 50 mesh (mesh opening 328 μm) / 80 mesh (mesh opening 218 μm) / 50 mesh (mesh opening 328 μm), and after cooling, it is about 3 mm with a strand cutter. It cut | judged to the uniform pellet of a diameter x 3 mm length. Metal separation was also carried out with a 12,000 gauss magnet at the extruder raw material hopper, extruder inlet, and strand cutter outlet.
（４）回収ＨＩＰＳ−３：市場回収され、家電リサイクルプラントで分別工程を経てチップ状とされたものを、スクリュー径６５ｍｍの単軸押出機を用い、バレル設定温度２３０℃で加熱溶融し、石川金網製５０メッシュ（目開き３２８μｍ）／１２０メッシュ（目開き１３２μｍ）／５０メッシュ（目開き３２８μｍ）の３枚重ねのステンレス製スクリーンメッシュで異物を濾別除去し、冷却後ストランドカッターにて約３ｍｍ径×３ｍｍ長の均一化されたペレットに裁断した。濾別時に熱安定剤としてフォスフェート系化合物（アデカ社製、ＰＥＰ−３６）、ヒンダードフェノール系化合物（チバスペシャルティケミカルズ株式会社のＩｒｇｎｏｘ１０１０）を、それぞれ０．２重量部添加した。押出機原料ホッパー及び押出機入り口、ストランドカッター出口に１２０００ガウスのマグネットによる金属分離も実施した。 (4) Recovered HIPS-3: The material recovered in the market and processed into a chip shape through a sorting process at a home appliance recycling plant is heated and melted at a barrel set temperature of 230 ° C. using a single screw extruder with a screw diameter of 65 mm. Foreign matter is removed by filtration with a stainless steel screen mesh of 50 mesh (mesh opening 328 μm) / 120 mesh (mesh opening 132 μm) / 50 mesh (mesh opening 328 μm), and after cooling, it is about 3 mm with a strand cutter. It cut | judged to the uniform pellet of a diameter x 3 mm length. At the time of filtration, 0.2 parts by weight of a phosphate compound (manufactured by Adeka Co., PEP-36) and a hindered phenol compound (Irgnox 1010 from Ciba Specialty Chemicals Co., Ltd.) were added as heat stabilizers. Metal separation was also carried out with a 12,000 gauss magnet at the extruder raw material hopper, extruder inlet, and strand cutter outlet.
（５）回収ＨＩＰＳ−４：市場回収され、家電リサイクルプラントで分別工程を経てチップ状とされたものを、スクリュー径６５ｍｍの単軸押出機を用い、バレル設定温度２３０℃で加熱溶融し、スクリーンメッシュを通さずに、冷却後ストランドカッターにて約３ｍｍ径×３ｍｍ長の均一化されたペレットに裁断した。
回収ＨＩＰＳの分析は、以下の方法により行った。表１に分析結果を示す。
（ａ）回収ＨＩＰＳの異物量測定
回収ＨＩＰＳのペレット５ｇをテトラヒドロフラン溶剤１００ｍｌに溶解後、３２メッシュ（目開き５００μｍ）のフィルター２枚重ねしたもので濾別し、乾燥後濾過残渣の重量を求めた。
(5) Recovered HIPS-4: Recovered on the market and made into a chip shape through a separation process at a home appliance recycling plant, using a single screw extruder with a screw diameter of 65 mm, heated and melted at a barrel set temperature of 230 ° C., and screened Without passing through the mesh, after cooling, it was cut into a uniform pellet of about 3 mm diameter × 3 mm length with a strand cutter.
The recovered HIPS was analyzed by the following method. Table 1 shows the analysis results.
(A) Foreign matter measurement of recovered HIPS After collecting 5 g of recovered HIPS pellets in 100 ml of tetrahydrofuran solvent, the mixture was filtered with two 32 mesh (aperture 500 μm) overlapped filters, and the weight of the filtration residue was determined after drying. .
（ｂ）回収ＨＩＰＳのハロゲン、金属分析
回収ＨＩＰＳの金属分析は蛍光Ｘ線分析装置 島津製ＳＸＦ−１１００を用い、Ｒｈ管球
４０ｋＶ ６０ｍＡの条件で定量分析を実施した。ハロゲンの分析は、ペレット５０ｍｇを重量分析用濾紙（ＡＤＶＡＮＴＥＣ製、５Ｂ濾紙）に包んだものを白金籠に入れ、純酸素で置換した１．５リットルの燃焼フラスコ中で完全燃焼させ、ガス成分を１００ｍｌの純水に吸収させて、イオンクロマトグラフで測定する。
（ｃ）回収ＨＩＰＳの物性測定
回収ＨＩＰＳの物性の評価は、東芝機械（株）製のＩＳ−８０Ｃ型射出成形機を用いて成形し、それぞれＡＳＴＭ試験法に準じてメルトフローレート（ＭＦＲ：２００℃、５ｋｇ荷重）、アイゾッド衝撃強度（Ｉｚｏｄ：３．２ｍｍ厚み）、熱変形温度（ＨＤＴ：１．８２Ｍｐａ荷重）、引張り伸度（ＴＥ：試験速度５ｍｍ／分）を測定した。
(B) Halogen of recovered HIPS and metal analysis Metal analysis of recovered HIPS was carried out using a fluorescent X-ray analyzer SXF-1100 manufactured by Shimadzu under the conditions of Rh tube 40 kV 60 mA. For halogen analysis, 50 mg of pellets wrapped in gravimetric filter paper (ADVANTEC, 5B filter paper) are placed in a platinum bowl and completely combusted in a 1.5 liter combustion flask substituted with pure oxygen. The sample is absorbed in 100 ml of pure water and measured with an ion chromatograph.
(C) Measurement of physical properties of recovered HIPS Evaluation of physical properties of recovered HIPS was performed using IS-80C injection molding machine manufactured by Toshiba Machine Co., Ltd., and melt flow rate (MFR: 200) according to ASTM test method. C, 5 kg load), Izod impact strength (Izod: 3.2 mm thickness), heat distortion temperature (HDT: 1.82 Mpa load), and tensile elongation (TE:
（６）未使用スチレン系樹脂
（ａ）未使用ＨＩＰＳ：ゴムの平均粒子径が１．５μｍ、ゴム含有量が１０重量％、ＭＦＲがＩＳＯ Ｒ１１３３ ２００℃、５ｋｇ荷重での値が１０ｇ／１０分、マトリックスの重量平均分子量が１７５，０００、ゲル含有量は、２２．８重量％のものを用いる。ＨＩＰＳのゴム粒子径はジメチルスルフォキシド（ＤＭＦ）溶媒中、２３℃でコールターカウンターにて測定。
（ｂ）未使用ＧＰＰＳ：Ｖｉｃａｔ軟化温度がＡＳＴＭ−Ｄ１５２５で１０６℃、メルトフローが７．０ｇ／１０分のものを用いる。
(6) Unused styrenic resin (a) Unused HIPS: average particle diameter of rubber is 1.5 μm, rubber content is 10% by weight, MFR is ISO R1133 at 200 ° C., 5 kg load, 10 g / 10 min. A matrix having a weight average molecular weight of 175,000 and a gel content of 22.8% by weight is used. The rubber particle size of HIPS was measured with a Coulter counter at 23 ° C. in a dimethyl sulfoxide (DMF) solvent.
(B) Unused GPPS: Use a Vicat softening temperature of ASTM-D1525 at 106 ° C. and a melt flow of 7.0 g / 10 min.
（７）ゴム状物質（ブロック共重合体）：（Ｅ−１）ポリスチレン−水素添加ポリブタジエン−ポリスチレン−水素添加ポリブタジエンの構造をもち、結合スチレン量が６０％、ビニル含量の合計量が３８％、ポリブタジエン部の水素添加率が９９．６％、数平均分子量が８５，０００の水添ブロック共重合体。
（Ｅ−２）オレフィン系エラストマー：エチレン−１アルケン共重合体、三井化学（株）製、 商品名 タフマーＡ４０７０を用いる。
（８）リン系難燃剤：リン系難燃剤として大八化学（株）製、商品名 ＣＲ７４１（ビスフェノールＡ−ビスジフェニルフォスフェート）を用いる。
（９）熱安定剤：熱安定剤−１としてフォスフェート系化合物（アデカ社製、ＰＥＰ−３６）、熱安定剤−２としてヒンダードフェノール系化合物（チバスペシャルティケミカルズ株式会社のＩｒｇｎｏｘ１０１０）を用いた。
(7) Rubber-like substance (block copolymer): (E-1) Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure having a bound styrene content of 60% and a total vinyl content of 38%. A hydrogenated block copolymer having a polybutadiene portion hydrogenation ratio of 99.6% and a number average molecular weight of 85,000.
(E-2) Olefin-based elastomer: ethylene-1 alkene copolymer, manufactured by Mitsui Chemicals, Inc., trade name TAFMER A4070 is used.
(8) Phosphorous flame retardant: Daihachi Chemical Co., Ltd. product name CR741 (bisphenol A-bisdiphenyl phosphate) is used as the phosphorus flame retardant.
(9) Heat stabilizer: A phosphate compound (manufactured by Adeka, PEP-36) was used as heat stabilizer-1, and a hindered phenol compound (Irgnox 1010 from Ciba Specialty Chemicals Co., Ltd.) was used as heat stabilizer-2. .
組成物の評価は以下の方法で実施した。
（ａ）アイゾッド衝撃強度
ＡＳＴＭ−Ｄ−２５６に従い、厚み３．２ｍｍの試験片を用いて測定した。
（ｂ）難燃性
ＵＬ−９４に準じて測定を行った。厚み２．５ｍｍの試験片を用いて測定した。
（ｃ）落錘衝撃強度
ROSAND社製Instrumented Falling Weight Impact Tester Type 5H.V.を使用し、厚さ２
ｍｍ、及び２−１ｍｍ段差について測定を行った。表２〜３中の落錘衝撃強度２ｍｍとは、厚さ２ｍｍの平板を用い、直径３０ｍｍに両面より固定し、直径３０ｍｍの中央部に直径１０ｍｍ、荷重３．２ｋｇの落錘を、高さ７０ｃｍより落下させ破壊エネルギーを測定した。表中の落錘衝撃強度１−２ｍｍとは、縦８４ｍｍ×横２５ｍｍ、厚さ２ｍｍと１ｍｍの段差のついた平板を用い、厚さ２ｍｍ部分を固定し片持支持した。その時段差が固定部と落錘が落下する位置のちょうど中心にくるように支持し、厚さ１ｍｍの部分の中央部に直径１０ｍｍ、荷重３．２ｋｇの落錘を３０ｃｍの高さから落下させ２ｍｍと１ｍｍの段差部が応力集中により破壊されたときの破壊エネルギーを測定した。
The composition was evaluated by the following method.
(A) Izod impact strength It was measured using a test piece having a thickness of 3.2 mm according to ASTM-D-256.
(B) Flame retardancy Measurement was performed according to UL-94. It measured using the test piece of thickness 2.5mm.
(C) Drop weight impact strength
Using ROSAND Instrumented Falling Weight Impact Tester Type 5H.V.,
Measurements were made for mm and 2-1 mm steps. The drop weight impact strength of 2 mm in Tables 2 to 3 is a flat plate with a thickness of 2 mm, fixed to both sides with a diameter of 30 mm, a drop weight with a diameter of 10 mm and a load of 3.2 kg at the center of the diameter of 30 mm, The fracture energy was measured by dropping from 70 cm. The drop weight impact strength of 1-2 mm in the table is a cantilever in which a 2 mm thick portion is fixed using a flat plate having a height of 84 mm × width of 25 mm and a thickness of 2 mm and 1 mm. At that time, the step is supported so that it comes to the center of the position where the fixed part and the falling weight drop, and a falling weight with a diameter of 10 mm and a load of 3.2 kg is dropped from a height of 30 cm to the central part of the 1 mm thick part. The fracture energy was measured when a step part of 1 mm was broken due to stress concentration.
（ｄ）成形品表面外観
縦７２ｃｍ×横１３５ｃｍ×厚み１０．２ｃｍの５面箱形成形品を用い表面外観を評価した。縦７２ｃｍ×横１３５ｃｍの面には５１ｃｍ×９１ｃｍの切り抜きが施されており、側４面が厚さ１．５ｍｍ、切り抜きのある面の厚さは２ｍｍである。なお射出成形のゲートは、４カ所であり、各側４面の縁の中心に設けてある。金型キャビティのテーパは２°である。射出成形の樹脂温度は２８０℃で実施する。
このようにして得られた成形筐体の表面を目視で観察する。外観の判定は色むら及び変色、フローマーク、シルバーの発生程度を判定した。非常に良好を◎、良好を○、良好でないを×、非常に悪いを××で示した。
(D) Surface appearance of molded product A surface appearance was evaluated using a 5-sided box-shaped product measuring 72 cm long × 135 cm wide × 10.2 cm thick. Cutouts of 51 cm × 91 cm are made on the surface of 72 cm long × 135 cm wide, the thickness of the side 4 surface is 1.5 mm, and the thickness of the cut surface is 2 mm. Note that there are four injection molding gates, which are provided at the center of the edge of the four surfaces on each side. The taper of the mold cavity is 2 °. The resin temperature for injection molding is 280 ° C.
The surface of the molded casing thus obtained is visually observed. Appearance was determined by determining the degree of color unevenness and discoloration, flow marks, and silver. Very good is indicated by ◎, good is indicated by ○, poor is indicated by ×, and very bad is indicated by XX.
［実施例１〜１３、比較例１〜５］
表２、及び表３記載の組成で、Ｃｏｐｅｒｉｏｎ Ｗｅｒｎｅｒ＆Ｐｆｌｅｉｄｅｒｅｒ社製ＺＳＫ４０ＭＣ二軸押出機（Ｌ／Ｄ＝４８）を用いて組成物を調整した。押出機への各原料の供給は表２及び表３記載の通りである。第１供給口（トップ）から、Ｌ／Ｄ＝２２の第２供給口までの前段バレル設定温度、及びＬ／Ｄ＝２２以降の後段バレル設定温度は表２及び表３記載の温度で溶融混練し、第２供給口へは、ＰＰＥと回収ＨＩＰＳ、及び未使用ポリスチレンと難燃剤の合計１００重量部に対し、滴下防止剤として三菱レーヨン（株）製のメタブレンＡ３０００を０．３重量部を、また実施例３では、更に、ホスファイト系熱安定剤としてアデカ社製のＰＥＰ−３６とフェノール系熱安定剤としてＩｒｇｎｏｘ１０１０をそれぞれ０．２重量部添加したブレンド物を供給した。更にＬ／Ｄ＝４０の位置よりリン系難燃剤を液体注入し、表２及び表３記載のスクリュー回転数、吐出量、各ニーディングセクション長で押出を行い、約３ｍｍ径×３ｍｍ長の円柱状ペレットを得た。組成物の特性を表２及び表３に示す。
[Examples 1 to 13, Comparative Examples 1 to 5]
With the compositions shown in Tables 2 and 3, the compositions were prepared using a ZSK40MC twin screw extruder (L / D = 48) manufactured by Coperion Werner & Pfleiderer. The supply of each raw material to the extruder is as shown in Tables 2 and 3. The first barrel setting temperature from the first supply port (top) to the second feeding port with L / D = 22 and the second barrel setting temperature after L / D = 22 are melt kneaded at the temperatures shown in Table 2 and Table 3. Then, to the second supply port, 0.3 parts by weight of Metablene A3000 manufactured by Mitsubishi Rayon Co., Ltd. as an anti-dripping agent is added to 100 parts by weight of PPE and recovered HIPS, and unused polystyrene and flame retardant. In Example 3, blends were further added in which 0.2 parts by weight of PEP-36 manufactured by Adeka as a phosphite heat stabilizer and Irgnox 1010 as a phenol heat stabilizer were added. Further, a phosphorus-based flame retardant is injected from the position of L / D = 40, and extrusion is performed with the screw rotation speed, discharge amount, and kneading section length shown in Tables 2 and 3, and a circle of about 3 mm diameter x 3 mm length. Columnar pellets were obtained. The properties of the composition are shown in Tables 2 and 3.
資源の有効活用を目的として、変性ポリフェニレンエーテルに本発明は活用できうるものであり、本発明の成形体は、ブラウン管ＴＶ筐体、薄型ＴＶ（液晶、プラズマ）ハウジング、プロジェクションＴＶ筐体、プリンター筐体、パソコンモニター筐体、パソコンハ
ウジング、電話ハウジング、複写機ハウジング等に適している。
The present invention can be used for modified polyphenylene ether for the purpose of effective utilization of resources. The molded product of the present invention includes a cathode ray tube TV casing, a thin TV (liquid crystal, plasma) housing, a projection TV casing, and a printer casing. Suitable for body, PC monitor housing, PC housing, telephone housing, copier housing, etc.
１ 原料ホッパー
２ マグネット
３ 押出機
４ スクリーンメッシュ
５ ストランドカッター
６ 第一供給口
７ ベント
８ 第２供給口
９ 第３供給口
１０ 液体注入
１１〜１４ ニーディングセクション
１５ 前段バレル部
１６ 後段バレル部
Ｌ１〜Ｌ４ ニーディングセクション有効長
Ｌ５ ニーディングディスク羽根長さ
Ｄ１ 押出機スクリュー径
DESCRIPTION OF
Claims (14)
ス転移温度の少なくとも一つが−６０℃以下であること特徴とする請求項１〜１０のいずれかに記載のポリフェニレンエーテル系樹脂組成物製造方法。 (B) The recovered styrene-based resin is a styrene-based resin recovered from the market, and at least one of the glass transition temperatures is −60 ° C. or lower. A method for producing a polyphenylene ether-based resin composition.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012040868A (en) * | 2010-07-20 | 2012-03-01 | Fp Corp | Polystyrene-based resin composition, polystyrene-based resin foamed sheet, laminate sheet, and packaging vessel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012040868A (en) * | 2010-07-20 | 2012-03-01 | Fp Corp | Polystyrene-based resin composition, polystyrene-based resin foamed sheet, laminate sheet, and packaging vessel |
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