JPH04173857A - Stabilized resin composition - Google Patents
Stabilized resin compositionInfo
- Publication number
- JPH04173857A JPH04173857A JP29725690A JP29725690A JPH04173857A JP H04173857 A JPH04173857 A JP H04173857A JP 29725690 A JP29725690 A JP 29725690A JP 29725690 A JP29725690 A JP 29725690A JP H04173857 A JPH04173857 A JP H04173857A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- impact
- resin composition
- resin
- conjugated diene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 33
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 9
- 229920001890 Novodur Polymers 0.000 claims description 14
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 150000002148 esters Chemical class 0.000 abstract 1
- 125000005461 organic phosphorous group Chemical group 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 229920005669 high impact polystyrene Polymers 0.000 description 19
- 239000004797 high-impact polystyrene Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 238000005984 hydrogenation reaction Methods 0.000 description 15
- 229920001971 elastomer Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000005060 rubber Substances 0.000 description 12
- 239000005062 Polybutadiene Substances 0.000 description 10
- 229920002857 polybutadiene Polymers 0.000 description 10
- -1 polyphenylene Polymers 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052984 zinc sulfide Inorganic materials 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229910052950 sphalerite Inorganic materials 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004793 Polystyrene Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- BFIAIMMAHAIVFT-UHFFFAOYSA-N 1-[bis(2-hydroxybutyl)amino]butan-2-ol Chemical compound CCC(O)CN(CC(O)CC)CC(O)CC BFIAIMMAHAIVFT-UHFFFAOYSA-N 0.000 description 1
- HKGKYUVCADNOOC-UHFFFAOYSA-N 1-aminotetradecan-2-ol Chemical compound CCCCCCCCCCCCC(O)CN HKGKYUVCADNOOC-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- RJKPEKIHHFNMGS-UHFFFAOYSA-N 2,4-ditert-butyl-3-methylphenol Chemical compound CC1=C(C(C)(C)C)C=CC(O)=C1C(C)(C)C RJKPEKIHHFNMGS-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000005064 Low cis polybutadiene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- RLIPARRCKPWOIA-UHFFFAOYSA-N P(O)(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC Chemical compound P(O)(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC RLIPARRCKPWOIA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 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
- 230000009849 deactivation Effects 0.000 description 1
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 1
- NMAKPIATXQEXBT-UHFFFAOYSA-N didecyl phenyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OC1=CC=CC=C1 NMAKPIATXQEXBT-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- NOUUUQMKVOUUNR-UHFFFAOYSA-N n,n'-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1NCCNC1=CC=CC=C1 NOUUUQMKVOUUNR-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- RNNGKNBZYALDNU-UHFFFAOYSA-N phosphoric acid;triphenylene Chemical compound OP(O)(O)=O.C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 RNNGKNBZYALDNU-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、優れた耐衝撃性、熱安定性及び耐熱水性を有
する樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin composition having excellent impact resistance, thermal stability and hot water resistance.
さらに詳しくは、ポリフェニレン系樹脂を耐衝撃性スチ
レン系樹脂で補強するに際し、共役ジエン系ゴムの全二
重結合の一部が水添された部分水添共役ジエン系ゴムを
含む耐衝撃性スチレン系樹脂を用い、更に該耐衝撃性ス
チレン系樹脂を安定化するに十分な熱安定剤を配合して
なる耐衝撃性、熱安定性および耐熱水性が改良された樹
脂組成物に関する。More specifically, when reinforcing polyphenylene resin with impact-resistant styrene resin, we use impact-resistant styrene resin containing partially hydrogenated conjugated diene rubber in which a portion of all double bonds in the conjugated diene rubber is hydrogenated. The present invention relates to a resin composition with improved impact resistance, thermal stability, and hot water resistance, which uses a resin and further contains a heat stabilizer sufficient to stabilize the impact resistant styrenic resin.
ポリフェニレンエーテル樹脂は耐熱性、電気特性、耐酸
、耐アルカリ性等に優れ、しかも低比重、低吸水性であ
る等の優れた特性を有する樹脂であるが、一方流動性が
低いため溶融成形加工がし難く且つ衝撃強度が低いため
若干脆いという欠点も有している。そして、これらの欠
点を同時に改良するためにポリブタジェン成分を含む耐
衝撃性ポリスチレンを配合する技術が開発され、米国特
許第３３８３４３５号明細書に開示されている。又、こ
れとは別にミクロ構造を特定したポリブタジェンを用い
た耐衝撃性ポリスチレンを配合する技術も特公昭５４−
２０５３７号公報に開示されている。該特公昭の技術は
ポリブタジェンの全ミクロ構造中の１．４−シス結合及
びビニル基の含有量が、夫々５０重量％以上及び１０重
量％以下であることを特徴としている。Polyphenylene ether resin has excellent heat resistance, electrical properties, acid resistance, alkali resistance, etc., as well as low specific gravity and low water absorption. However, it has low fluidity and cannot be processed by melt molding. It also has the disadvantage of being somewhat brittle due to its low impact strength. In order to improve these drawbacks at the same time, a technique of blending high-impact polystyrene containing a polybutadiene component was developed and disclosed in US Pat. No. 3,383,435. In addition, a technology for compounding impact-resistant polystyrene using polybutadiene with a specified microstructure was developed in the Japanese Patent Publication Publication No. 1973-
It is disclosed in Japanese Patent No. 20537. The technology of Tokkosho is characterized in that the contents of 1,4-cis bonds and vinyl groups in the entire microstructure of polybutadiene are 50% by weight or more and 10% by weight or less, respectively.
しかし、これらの技術では、ミクロ構造の如何に係らず
二重結合の総量は変らないため、二重結合の持つ化学的
不安定さに基づく、酸化劣化等による物性変化の度合に
極端な違いはなく、溶融成形、熱曝露あるいは光曝露等
による物性の低下を回避することは非常に困難であった
。However, with these technologies, the total amount of double bonds does not change regardless of the microstructure, so there is no extreme difference in the degree of physical property change due to oxidative deterioration etc. due to the chemical instability of double bonds. Therefore, it was extremely difficult to avoid deterioration of physical properties due to melt molding, heat exposure, light exposure, etc.
一方、二重結合をほとんど含まない、水添されたスチレ
ン−ブタジェンブロック共重合体で補強する技術が、例
えば、特開昭５０−７１７４２号公報に開示されている
が、この技術でも熱安定性は優れるものの、耐衝撃性ス
チレン系樹脂のゴム粒子内にスチレン系重合体の分散粒
子を含まないため、ゴム効率が低く、耐衝撃性を改良す
るためには多量のゴム成分を添加する必要があった。し
かも水添されたスチレン−ブタジェンブロック共重合体
とポリフェニレンエーテル樹脂との親和性が必ずしも十
分でないため、しばしば成形品に剥離が生じていた。加
えてブタジェンブロック中の１．４−ブタジェン成分の
水添率が高くなる程、ゴム成分のガラス転移点が上昇す
るため、かかる技術では十分な低温衝撃性を得ることが
できないのである。On the other hand, a technology for reinforcing with a hydrogenated styrene-butadiene block copolymer containing almost no double bonds is disclosed, for example, in JP-A-50-71742; Although the rubber particles of the impact-resistant styrenic resin do not contain dispersed particles of styrene polymer, the rubber efficiency is low, and it is necessary to add a large amount of rubber component to improve impact resistance. was there. Furthermore, because the affinity between the hydrogenated styrene-butadiene block copolymer and the polyphenylene ether resin is not always sufficient, molded products often peel. In addition, the higher the hydrogenation rate of the 1,4-butadiene component in the butadiene block, the higher the glass transition point of the rubber component, making it impossible to obtain sufficient low-temperature impact resistance with this technique.
これとは別に、耐衝撃性スチレン系樹脂の剛性を保ちつ
＼衝撃強度を改良する技術が特開昭６４−９０２０８号
公報に開示され、実施例にはポリフェニレンエーテル樹
脂に配合した場合にも、従来の耐衝撃性スチレン系樹脂
に較べ衝撃強度が改良されることが示されている。しか
し、ポリフェニレンエーテル系樹脂を含む樹脂組成物は
耐熱性が高いことが特徴であり、該公報開示の技術の１
．２−ビニルの残基が多い領域では、高温で成形加工し
たり、熱曝露した場合、物性低下が大きくなるという問
題点がある。更に、水添率が高い領域では低温衝撃強度
が得られない等の問題点があり、ポリフェニレンエーテ
ル系樹脂の物性改良のために求められている耐衝撃性ス
チレン系樹脂の充分満足のいく技術範囲を示すものには
なり得ていない。Separately, a technique for improving the impact strength while maintaining the rigidity of impact-resistant styrene resin is disclosed in Japanese Patent Application Laid-open No. 64-90208. It has been shown that impact strength is improved compared to conventional impact styrenic resins. However, resin compositions containing polyphenylene ether resins are characterized by high heat resistance, and one of the techniques disclosed in this publication
．． In regions with a large number of 2-vinyl residues, there is a problem in that physical properties deteriorate significantly when molded at high temperatures or exposed to heat. Furthermore, there are problems such as not being able to obtain low-temperature impact strength in the region where the hydrogenation rate is high, and it is difficult to fully satisfy the technical range of impact-resistant styrene resins that are required to improve the physical properties of polyphenylene ether resins. It cannot be used as an indicator of
本発明の課題は、ポリフェニレンエーテル系樹脂に成形
加工性及び耐衝撃性を賦与するに際し、上記した問題点
が解決された溶融加工工程又は熱曝露等の加熱によって
物性低下が起こらず、しかも従来の樹脂組成物に較べ低
温衝撃性、剛性あるいは耐環境亀裂性等のバランスが優
れたポリフェニレンエーテル系樹脂組成物を得ることに
ある。The object of the present invention is to solve the above-mentioned problems when imparting moldability and impact resistance to polyphenylene ether-based resins, while preventing deterioration of physical properties due to melt processing or heating such as thermal exposure. The object of the present invention is to obtain a polyphenylene ether resin composition which has a better balance of low-temperature impact resistance, rigidity, environmental crack resistance, etc. than other resin compositions.
〔課題を解決するための手段及び作用〕本発明者らは研
究の結果、ポリフェニレンエーテル系樹脂を共役ジエン
系ゴムを含む耐衝撃性スチレン系樹脂によって補強する
場合に、共役ジエン系ゴム成分中の二重結合の量が多く
成る程、酸化劣化を受は易く物性低下が大きくなること
、更に二重結合の中でも１．２−ビニルの結合量が多く
成ると酸化劣化が促進されスチレン系樹脂成分の主鎖分
裂をも誘発し、物性低下をもたらすことを見出した。[Means and effects for solving the problem] As a result of research, the present inventors found that when reinforcing a polyphenylene ether resin with an impact-resistant styrene resin containing a conjugated diene rubber, The greater the amount of double bonds, the more susceptible it is to oxidative deterioration and the greater the decline in physical properties.Furthermore, as the amount of 1,2-vinyl bonds among double bonds increases, oxidative deterioration is accelerated and the styrenic resin component It was found that this also induces main chain splitting, resulting in a decrease in physical properties.
そして、二重結合の総量が必要以上に多くなると、熱安
定性及び剛性が低下し、必要以上に少くなると低温衝撃
強度が低下するため、物性バランスを保つための適切な
二重結合量が存在することを見出した。加えて、ポリフ
ェニレンエーテル系樹脂に部分水添された共役ジエン系
ゴムを含む耐衝撃性スチレン系樹脂を添加した場合、従
来の共役ジエン系ゴムを含む耐衝撃性スチレン系樹脂に
較べ大幅に高い耐衝撃性及び耐環境亀裂性を示すという
ことを見出した。If the total amount of double bonds is more than necessary, thermal stability and rigidity will decrease, and if it is less than necessary, low-temperature impact strength will decrease, so there is an appropriate amount of double bonds to maintain the balance of physical properties. I found out what to do. In addition, when an impact-resistant styrenic resin containing partially hydrogenated conjugated diene rubber is added to a polyphenylene ether resin, the resistance is significantly higher than that of a conventional impact-resistant styrene resin containing a conjugated diene rubber. It has been found that it exhibits impact strength and environmental cracking resistance.
更に、金属酸化物及び金属硫化物類の如き化合物を熱安
定剤として配合した場合、従来の共役ジエン系ゴムを含
む耐衝撃性スチレン系樹脂を用いた場合の効果からは予
想できない程、熱安定性が改良され、熱履歴による耐衝
撃性の低下も極めて少なく、且つ優れた成形安定性及び
耐熱水性を示すことを見出した。加えて、有機亜燐酸エ
ステル類、アルカノールアミン類の如き化合物を併用す
ることで、熱安定化効果が更に改良されることを見出し
て、本発明を完成した。Furthermore, when compounds such as metal oxides and metal sulfides are blended as heat stabilizers, the thermal stability is improved to a degree that cannot be expected from the effect of using impact-resistant styrenic resins containing conventional conjugated diene rubbers. It has been found that the material has improved properties, has very little decrease in impact resistance due to thermal history, and exhibits excellent molding stability and hot water resistance. In addition, the inventors have discovered that the heat stabilizing effect can be further improved by using compounds such as organic phosphites and alkanolamines in combination, and have completed the present invention.
即ち、本発明は、
（ａ） ポリフェニレンエーテル系樹脂１０〜９０重
量部、
（ｂ） 共役ジエン系ゴムの全二重結合のうち５〜７
０重量％が水添された部分水添共役ジエン系ゴムを含む
耐衝撃性スチレン系樹脂９０〜１０重量部、
（ｃ） スチレン系樹脂０〜８０重量部及び
（ｄ） 熱安定剤０．０１〜５重量部より成り、且つ
成分（ｂ）における部分水添共役ジエン系ゴム中に含ま
れる １．２−ビニル結合量及び１．４ −結合量が、
夫々３重量％以下及び３０重量％以上であり、成分（ｄ
）が金属酸化物及び金属硫化物又は両者にさらに有機亜
燐酸エステル類を加えた熱安定剤であることを特徴とす
る安定化された樹脂組成物を提供するものである。That is, the present invention comprises: (a) 10 to 90 parts by weight of a polyphenylene ether resin; (b) 5 to 7 of the total double bonds of the conjugated diene rubber;
90 to 10 parts by weight of an impact-resistant styrenic resin containing a partially hydrogenated conjugated diene rubber in which 0% by weight is hydrogenated, (c) 0 to 80 parts by weight of a styrenic resin, and (d) 0.01 parts by weight of a heat stabilizer. ~5 parts by weight, and the amount of 1.2-vinyl bonds and the amount of 1.4-bonds contained in the partially hydrogenated conjugated diene rubber in component (b) are:
3% by weight or less and 30% by weight or more, respectively, and the component (d
) is a heat stabilizer containing a metal oxide, a metal sulfide, or both together with an organic phosphite.
本発明の樹脂組成物は高温で成形機内に滞留させたり、
加熱変形温度付近で熱曝露しても物性低下が生じ難い。The resin composition of the present invention may be retained in a molding machine at high temperature,
Even if exposed to heat near the heating deformation temperature, physical property deterioration is unlikely to occur.
また、従来の技術に較べて、同一ゴム量による耐衝撃性
の増加が大きいため、同一耐衝撃強度を得るためには少
いゴム量で済み、元々、全二重結合量か少ない上に添加
するゴム量が少いために組成物が燃焼し難くなり、難燃
化する場合にも少い難燃剤量で目的を達成できるといい
う利点を有する。In addition, compared to conventional technology, the increase in impact resistance with the same amount of rubber is large, so in order to obtain the same impact resistance strength, a smaller amount of rubber is required. Since the amount of rubber is small, the composition becomes difficult to burn, and even when flame retardant is desired, it has the advantage that the objective can be achieved with a small amount of flame retardant.
更に、本発明の樹脂組成物は剛性、低温衝撃性あるいは
耐環境亀裂等の物性バランスにおいても、従来の技術で
は到達し得ない領域のものが得られるという特長を有す
る。Furthermore, the resin composition of the present invention has the advantage that it can achieve a balance of physical properties such as rigidity, low-temperature impact resistance, and environmental cracking resistance that cannot be achieved using conventional techniques.
本発明で用いるポリフェニレンエーテル系樹脂とは、−
数式
（式中、Ｒ１，Ｒ２、Ｒ３，Ｒｔ、、Ｒｓ 、Ｒｓは炭
素数１〜４のアルキル基、アリール基、ハロゲン、水素
等の一価の残基てあり、Ｒｓ 、 Ｒ６は同時に水素で
はない。）を繰返し単位とし、構成単位が上記ＣＡ）及
びＣＢ〕からなる単独重合体、あるいは共重合体が使用
できる。The polyphenylene ether resin used in the present invention is -
Numerical formula (in the formula, R1, R2, R3, Rt, Rs, Rs are monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen, hydrogen, etc., and Rs and R6 are hydrogen at the same time) A homopolymer or a copolymer consisting of CA) and CB as the repeating unit and the constituent units CA) and CB above can be used.
ポリフェニレンエーテル樹脂の単独重合体の代表例とし
ては、ポリ（２，６−シメチルー１．４−）ユニしン）
エーテル、ポリ（２−メチル−６−ニチルー１，４−）
ユニしン）エーテル、ポリ（２，６−ジニチルー１，４
−）ユニしン）エーテル、ポリ（２−エチル−６−ｎプ
ロピル−１，４−）ユニしン）エーテル、ポリ（２，６
−ジ−ｎプロピル−１，４−）ユニしン）エーテル、ポ
リ（２−メチル−６−ｎブチル−１，４−フェニレン）
エーテル、ポリ（２−エチル−６−イツプロビルー１．
４−）ユニしン）エーテル、ポリ（２−メチル−６−ク
ロル−１，４−フェニレン）エーテル、ポリ（２−メチ
ル−６−ヒドロキシエチル−１，４−）ユニしン）エー
テル、ポリ（２−メチル−６−クロロエチル−１，４−
）ユニしン）エーテル等のホモポリマーが挙げられる。A typical example of a homopolymer of polyphenylene ether resin is poly(2,6-dimethyl-1,4-)unishin).
Ether, poly(2-methyl-6-nityl-1,4-)
unishin) ether, poly(2,6-dinithyl-1,4
-) unicine) ether, poly(2-ethyl-6-npropyl-1,4-)unicine) ether, poly(2,6
-di-npropyl-1,4-)unicine)ether, poly(2-methyl-6-nbutyl-1,4-phenylene)
Ether, poly(2-ethyl-6-ituprobyl-1.
4-) unicine) ether, poly(2-methyl-6-chloro-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-)unicine) ether, poly (2-methyl-6-chloroethyl-1,4-
) Unishin) Homopolymers such as ether can be mentioned.
ポリフェニレンエーテル共重合体は、２，６−シメチル
フエノールと２．３．６−）リメチルフェノールとの共
重合体あるいは０−クレゾールとの共重合体あるいは２
．３．６−トリメチルフエノール及び０−クレゾールと
の共重合体等、ポリフェニレンエーテル構造を主体とし
てなるポリフェニレンエーテル共重合体を包含する。The polyphenylene ether copolymer is a copolymer of 2,6-dimethylphenol and 2.3.6-)limethylphenol or a copolymer of 0-cresol or 2.3.6-dimethylphenol.
．． It includes polyphenylene ether copolymers mainly having a polyphenylene ether structure, such as copolymers with 3.6-trimethylphenol and 0-cresol.
本発明において、ポリフェニレンエーテル系樹脂の含有
量は１０〜９０重量部の範囲が好ましい。含有量が１０
重量部を下回る場合には、ポリフェニレンエーテル系樹
脂による改良効果が十分発揮されないため好ましくなく
、９０重量部を超える場合、成形加工性あるいは耐衝撃
性を改良するに十分な量の耐衝撃性スチレン系樹脂を添
加することができなくなるため好ましくない。In the present invention, the content of the polyphenylene ether resin is preferably in the range of 10 to 90 parts by weight. Content is 10
If it is less than 90 parts by weight, the improvement effect of the polyphenylene ether resin will not be sufficiently exhibited, and it is not preferable. If it exceeds 90 parts by weight, the impact-resistant styrene resin will be used in an amount sufficient to improve moldability or impact resistance. This is not preferable because it becomes impossible to add resin.
本発明に用いる部分水添共役ジエン系ゴムは、公知の方
法で得られる共役ジエン系ゴムを部分的に水添させるこ
とによって得られる。公知の方法で得られる共役ジエン
系ゴムとは、通常、耐衝撃性スチレン系樹脂の製造に用
いられる全てのゴムが含まれる。例えば、ポリブタジェ
ン（ローシスポリブタジェン及びハイシスポリブタジェ
ン）スチレン−ブタジェン共重合体、ポリイソプレン、
ブタジェン−イソプレン共重合体、天然ゴム等であり、
中でも最も好ましいのはポリブタジェンである。The partially hydrogenated conjugated diene rubber used in the present invention can be obtained by partially hydrogenating a conjugated diene rubber obtained by a known method. Conjugated diene rubbers obtained by known methods include all rubbers normally used in the production of impact-resistant styrene resins. For example, polybutadiene (low-cis and high-cis polybutadiene), styrene-butadiene copolymer, polyisoprene,
Butadiene-isoprene copolymer, natural rubber, etc.
Among them, polybutadiene is most preferred.
共役ジエン系ゴムの全二重結合中に占める１、２−ビニ
ル結合の好ましい量は全二重結合の水添率によって異な
るため特に限定されるものではないが、−船釣には５重
量％以上であることが望ましい。熱安定性を向上させる
ため水添率を上げた場合、ゴム弾性が失われるが、１．
２−ビニル結合量の多いもの程ゴム弾性の低下の度合い
が小さくなるためである。The preferred amount of 1,2-vinyl bonds in the total double bonds of the conjugated diene rubber is not particularly limited as it varies depending on the hydrogenation rate of the total double bonds, but -5% by weight for boat fishing. The above is desirable. When the hydrogenation rate is increased to improve thermal stability, rubber elasticity is lost, but 1.
This is because the greater the amount of 2-vinyl bonds, the smaller the degree of decrease in rubber elasticity.
本発明において、部分水添共役ジエン系ゴムは全二重結
合のうち、５〜７０重量％が水添され、しかも１，２−
ビニル結合量が３重量％以下、好ましくは２重量％以下
であることが望ましく、１．４−結合の量は３０重量％
以上であることが望ましい。In the present invention, in the partially hydrogenated conjugated diene rubber, 5 to 70% by weight of all double bonds are hydrogenated, and 1,2-
It is desirable that the amount of vinyl bonds is 3% by weight or less, preferably 2% by weight or less, and the amount of 1.4-bonds is 30% by weight.
The above is desirable.
全二重結合の水添率が５重量％を下回る場合には、部分
水添の効果が十分に発揮されない。例えば、水添前の１
．２−ビニル量が８重量％の共役ジエン系ゴムを５重量
％水添しても１．２−ビニル量を３重量％以下にはでき
ないし、全二重結合量の５重量％を水添しても、耐衝撃
性及び耐環境亀裂性はほとんど改良できない。水添率が
７０重量％を上回る場合、耐衝撃性、中でも低温衝撃性
が十分に得られなくなるため好ましくない。部分水添共
役ジエン系ゴム中に含まれる １．２−ビニル結合量が
３重量％を上回る場合にはゴム成分が酸化され、更にス
チレン系樹脂の主鎖***を誘発し易くなるため熱安定性
を十分に改良し得ず好ましくない。更に、１．４−結合
量が３０重量％を下回る場合には耐衝撃性の改良効果が
乏しくなるため好ましくない。If the hydrogenation rate of all double bonds is less than 5% by weight, the effect of partial hydrogenation will not be sufficiently exhibited. For example, 1 before hydrogenation
．． Even if a conjugated diene rubber with a 2-vinyl content of 8% by weight is hydrogenated by 5% by weight, the 1.2-vinyl content cannot be reduced to 3% by weight or less, and 5% by weight of the total double bond content is hydrogenated. However, impact resistance and environmental cracking resistance can hardly be improved. If the hydrogenation rate exceeds 70% by weight, it is not preferable because impact resistance, especially low-temperature impact resistance, cannot be obtained sufficiently. If the amount of 1,2-vinyl bonds contained in the partially hydrogenated conjugated diene rubber exceeds 3% by weight, the rubber component will be oxidized and the main chain splitting of the styrene resin will be more likely to occur, resulting in poor thermal stability. It is not preferable because it cannot sufficiently improve the Furthermore, if the amount of 1.4-bonds is less than 30% by weight, the effect of improving impact resistance becomes poor, which is not preferable.
本発明で用いられる部分水添共役ジエン系ゴムは上述の
共役ジエン系ゴムを部分的に水添することによって得ら
れる。水添方法は、従来公知のいかなる方法を用いても
良く、例えば、Ｆ、 Ｌ、 Ｒａｍｐ。The partially hydrogenated conjugated diene rubber used in the present invention can be obtained by partially hydrogenating the above-mentioned conjugated diene rubber. Any conventionally known hydrogenation method may be used, for example, F, L, Ramp.
ｅｆ ａｌ、 １． Ａｍｅｔ、 Ｃｈｅｍ、 Ｓ
ａｃ、、 ８３． ４５７２（１９６１）。ef al, 1. Amet, Chem, S
ac,, 83. 4572 (1961).
記載のトリイソブチルボラン触媒を用いて水素添加する
方法、Ｈｕｎｇ Ｙｕ Ｃｈｅｎ、 Ｊ、 Ｐｏ１
７ｍ、 ＳｃｉＰｏ１７ｍ、 Ｌｅｔｔｅｒ Ｅｄ
、、 １５． ２７１０９７７） 、記載のトルエン
スルフォニルヒドラジドを用いて水素添加する方法、あ
るいは特公昭４２−８７０４号に記載の有機コバルト−
有機アルミニウム系触媒あるいは有機ニッケルー有機ア
ルミニウム系触媒を用いて水素添加する方法等を挙げる
ことができる。Method of hydrogenation using triisobutylborane catalyst as described, Hung Yu Chen, J, Po1
7m, SciPo17m, Letter Ed
,, 15. 2710977), a method of hydrogenation using toluenesulfonyl hydrazide, or an organic cobalt method described in Japanese Patent Publication No. 8704/1983.
Examples include a method of hydrogenation using an organic aluminum catalyst or an organic nickel-organoaluminum catalyst.
本発明の実施において特に好ましい水素添加の方法は、
１．２−ビニル結合を１．４−結合に先だって選択的に
水添できる触媒を使用する特開昭５２〜４１８９０号に
示される方法、あるいは低温、低圧の温和な条件下で水
添が可能な触媒を用いる特開昭５９−１３３２０３号、
特開昭６０−２２０１４７号に示される方法である。A particularly preferred method of hydrogenation in the practice of the present invention is:
Hydrogenation can be carried out by the method shown in JP-A-52-41890, which uses a catalyst that can selectively hydrogenate the 1,2-vinyl bond before the 1,4-bond, or under mild conditions at low temperature and low pressure. JP-A-59-133203 using a catalyst,
This is a method disclosed in Japanese Patent Application Laid-Open No. 60-220147.
本発明において、部分水添共役ジエン系ゴムを含む耐衝
撃性スチレン系樹脂の含有量は９０〜１０重量部の範囲
より選ばれることが好ましい。含有量が９０重量部を上
回る場合にはポリフェニレンエーテル系樹脂を必要量添
加できず、１０重量部を下回る場合には部分水添共役ジ
エン系ゴムを十分に含有させることができないため、耐
衝撃性及び耐環境亀裂性を十分に改良できず好ましくな
い。In the present invention, the content of the impact-resistant styrene resin containing partially hydrogenated conjugated diene rubber is preferably selected from the range of 90 to 10 parts by weight. If the content exceeds 90 parts by weight, the required amount of polyphenylene ether resin cannot be added, and if the content is less than 10 parts by weight, the partially hydrogenated conjugated diene rubber cannot be sufficiently contained, resulting in poor impact resistance. Also, the environmental cracking resistance cannot be sufficiently improved, which is not preferable.
本発明に用いるスチレン系樹脂とは、スチレン系化合物
、スチレン系化合物と共重合可能な化合物及びゴム質重
合体を挙げることができる。Examples of the styrene resin used in the present invention include styrene compounds, compounds copolymerizable with styrene compounds, and rubbery polymers.
スチレン化合物とは、−数式
（式中、Ｒは水素、低級アルキルまたはハロゲンを示し
、Ｚはビニル、水素、ハロゲン及び低級アルキルよりな
る群から選択され、ｐは０〜５の整数である。）で表さ
れる化合物を意味する。A styrene compound has the following formula: (wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer from 0 to 5.) means a compound represented by
これらの具体例としては、スチレン、α−メチルスチレ
ン、２，４−ジメチルスチレン、モノクロルスチレン、
ジクロルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ
−ブチルスチレン、エチルスチレン等が挙げられる。ま
た、スチレン系化合物と共重合可能な化合物としては、
メチルメタクリレート、エチルメタクリレート等のメタ
クリル酸エステル類、ブチルアクリレート、２−エチル
へキシルアクリレート等のアクリル酸エステル類：アク
リロニトリル、メタクリレートリル等の不飽和ニトリル
化合物類；無水マレイン酸等の酸無水物等か挙げられ、
スチレン系化合物と共に使用される。また、ゴム質重合
体としては共役ジエン系ゴムあるいはエチレン−プロピ
レン共重合体系ゴム等が挙げられるか、いずれも部分水
添共役ジエン系ゴムと合せて、ゴム中に含まれる１、２
−ビニル結合量及び１，４−結合量が夫々３重量％以下
及び３０重量％以上であることが必要である。Specific examples of these include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene,
Dichlorostyrene, p-methylstyrene, p-tert
-butylstyrene, ethylstyrene, etc. In addition, compounds that can be copolymerized with styrene compounds include:
Methacrylic esters such as methyl methacrylate and ethyl methacrylate; acrylic esters such as butyl acrylate and 2-ethylhexyl acrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylate; acid anhydrides such as maleic anhydride, etc. mentioned,
Used with styrenic compounds. Examples of rubbery polymers include conjugated diene rubbers and ethylene-propylene copolymer rubbers, which together with partially hydrogenated conjugated diene rubbers contain 1, 2
- It is necessary that the amount of vinyl bonds and the amount of 1,4-bonds be 3% by weight or less and 30% by weight or more, respectively.
本発明において、スチレン系樹脂は熱変形温度及び成形
加工性を調節するために用いられ、部分水添共役ジエン
系ゴムを含む耐衝撃性スチレン系樹脂によって目的が達
成されれば添加しなくても良いが、必要によって８０重
量部まで添加できる。In the present invention, the styrene resin is used to adjust the heat distortion temperature and moldability, and if the purpose is achieved by the impact-resistant styrene resin containing partially hydrogenated conjugated diene rubber, it may not be added. Good, but up to 80 parts by weight can be added if necessary.
８０重量部を上回る場合には、ポリフェニレンエーテル
系樹脂及び部分水添共役ジエン系ゴムを含む耐衝撃性ス
チレン系樹脂を必要量添加てきないため好ましくない。If it exceeds 80 parts by weight, it is not preferable because the required amount of impact-resistant styrene resin containing polyphenylene ether resin and partially hydrogenated conjugated diene rubber cannot be added.
本発明で用いる熱安定剤である金属酸化物及び金属硫化
物としては主に亜鉛の酸化物及び硫化物が用いられる。As the metal oxide and metal sulfide which are heat stabilizers used in the present invention, zinc oxide and sulfide are mainly used.
本発明で用いる熱安定剤である有機亜燐酸エステル類も
特に限定されるものではないが、その具体例としてはト
リフェニルホスファイト、トリノニルフェニルホスファ
イト、ジフェニルデシルホスファイト、ジデシルフェニ
ルホスファイト、トリデシルホスファイト、ジステアリ
ルペンタエリスリトールホスファイト、４．４’ −
イソプロピリデンジフェノールアルキルホスファイト、
トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイ
ト、トリドデシルトリチオホスファイト等を挙げること
ができる。The organic phosphite used as a heat stabilizer in the present invention is not particularly limited, but specific examples include triphenyl phosphite, trinonylphenyl phosphite, diphenyldecyl phosphite, and didecylphenyl phosphite. , tridecyl phosphite, distearyl pentaerythritol phosphite, 4.4'-
isopropylidene diphenol alkyl phosphite,
Tris(2,4-di-t-butylphenyl)phosphite, tridodecyltrithiophosphite, and the like can be mentioned.
本発明においては安定剤として■金属酸化物と金属硫化
物又は■金属酸化物、金属硫化物及び有機亜燐酸エステ
ル類を用いるが、これらにさらにアルカノールアミン類
又はアルキルアミン酸化アルキレン誘導体を加えたもの
を用いることができる。その場合用いられるアミン類及
びアミン置換体類は下記（Ｉ）式に代表されるアルカノ
ールアミン類、（Ｉ［） （Ｉ［） （ＩＶ）式に
代表されるアルキルアミン酸化アルキレン誘導体及び（
Ｖ）式に示されるアミン類の単品又は混合物である。In the present invention, (1) metal oxides and metal sulfides, or (2) metal oxides, metal sulfides, and organic phosphites are used as stabilizers, and in addition to these, alkanolamines or alkylamine alkylene oxide derivatives are added. can be used. The amines and amine substitutes used in this case include alkanolamines represented by the following formula (I), alkylamine oxide alkylene derivatives represented by the formula (I[) (I[) (IV)], and (
V) A single item or a mixture of amines represented by the formula.
（Ｉ） Ｎ（Ｒ４）３
（Ｒ４は各々独立に水素又は炭素数１〜４の低級アルカ
ノールであり、少なくとも２個のＲ４はアルカノールで
ある。）
（ＩＩ） ＲＮＨ−（Ｒ６０） 、 Ｈ（Ｒ５はアル
キル基、Ｒ６は炭素数２〜４のアルキル基、ｌは１〜５
０の整数である。）（Ｒ８０） ｍ Ｈ
（Ｒはアルキル基、Ｒ８，Ｒ９は炭素数２〜４のアルキ
ル基、ｍ、ｎは１〜５０の整数である。）（Ｒｌｏはア
ルキル基、Ｒ１１は炭素数１〜４のアルキル基、Ｒ１２
，Ｒ１３，Ｒ１４は炭素数２〜４のアルキル基、ｐ、
ｑ、 ｒは１〜５０の整数である。）（Ｖ） Ｎ
−ＣＨ−ＣＨ２−Ｎ骨格をアミン分子に含有する化合物
で下記（ｉ）、 （ｉｉ）で示される化合物
（ｉｉ） Ｈ２Ｎ （ＣＨ，、・ＣＨ２ＮＨ） 、
ＣＨ２ＣＨ２ＮＨ２（ｔ＝０〜２の整数）
その代表例はジェタノールアミン、トリエタノールアミ
ン、ジイソプロパツールアミン、トリイソプロパツール
アミン、ジェタノールアミン、トリブタノールアミン、
ドデシルエタノールアミン、（ｘ＋ｙ＝２）。(I) N(R4)3 (Each R4 is independently hydrogen or a lower alkanol having 1 to 4 carbon atoms, and at least two R4 are alkanols.) (II) RNH-(R60), H(R5 is an alkyl group, R6 is an alkyl group having 2 to 4 carbon atoms, l is 1 to 5
It is an integer of 0. ) (R80) m H (R is an alkyl group, R8 and R9 are alkyl groups having 2 to 4 carbon atoms, m and n are integers of 1 to 50.) (Rlo is an alkyl group, R11 is an alkyl group having 1 to 4 carbon atoms, and R11 is an alkyl group having 1 to 4 carbon atoms. 4 alkyl group, R12
, R13, R14 are alkyl groups having 2 to 4 carbon atoms, p,
q and r are integers from 1 to 50. )(V)N
Compounds containing a -CH-CH2-N skeleton in the amine molecule and shown in the following (i) and (ii) (ii) H2N (CH,,.CH2NH),
CH2CH2NH2 (t = integer of 0 to 2) Typical examples are jetanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, jetanolamine, tributanolamine,
Dodecylethanolamine, (x+y=2).
（ｘ＋ｙ＝７）。(x+y=7).
（ｘ＋ｙ＝２）。(x+y=2).
（ｘ＋ｙ＝４）。(x+y=4).
（ｘ十ｙ−１０）。(x10y-10).
（ｘ＋ｙ−２０）。(x+y-20).
（Ｒ；牛脂、ｘ＋ｙ十ｚ＝３）。(R; beef tallow, x + y + z = 3).
（Ｒ；牛脂、ｘ＋ｙ＋ｚ＝ｓ）。(R; beef tallow, x+y+z=s).
（ｘ＋ｙ＝２）。(x+y=2).
（ｘ＋ｙ＝４）。(x+y=4).
Ｎ、 Ｎ′ ジフェニルエチレンジアミン、トリエチ
ルテトラミン等が挙げられる。N, N' diphenylethylenediamine, triethyltetramine, and the like.
本発明において、熱安定剤の含有量は０．０１〜５重量
部の範囲が好ましい。含有量が０．０１重量部を下回る
場合は安定化効果がほとんどなく、５重量部を上回る場
合は加熱変形温度及び耐衝撃性の低下が著しくなるため
好ましくない。In the present invention, the content of the heat stabilizer is preferably in the range of 0.01 to 5 parts by weight. If the content is less than 0.01 parts by weight, there is almost no stabilizing effect, and if it exceeds 5 parts by weight, the heat deformation temperature and impact resistance will be significantly lowered, which is not preferable.
本発明の組成物には他の添加剤、例えば、可塑剤、紫外
線吸収剤、難燃剤、着色剤、離型剤及びガラス繊維、炭
素繊維等の繊維状補強剤、更にはガラスピーズ、炭酸カ
ルシウム、タルク等の充填剤を添加することができる。The composition of the present invention may contain other additives, such as plasticizers, ultraviolet absorbers, flame retardants, colorants, mold release agents, and fibrous reinforcing agents such as glass fibers and carbon fibers, as well as glass peas and calcium carbonate. Fillers such as , talc, etc. can be added.
難燃剤としては、芳香族リン酸エステル、赤リン、芳香
族ハロゲン化合物、三酸化アンチモン等が特に有効であ
る。Particularly effective flame retardants include aromatic phosphate esters, red phosphorus, aromatic halogen compounds, and antimony trioxide.
本発明を構成する各成分を混合する方法はいかなる方法
でもよいが、例えば、押出機、加熱ロール、バンバリー
ミキサ−、ニーダ−等を使用することができる。Any method may be used to mix the components constituting the present invention, and for example, an extruder, heated roll, Banbury mixer, kneader, etc. can be used.
本発明の安定化ポリフェニレンエーテル系樹脂組成物は
、耐衝撃性、熱安定性及び耐熱水性に優れている上に、
成形加工性及び電気的特性等にも優れるため有用な成形
材料である。The stabilized polyphenylene ether resin composition of the present invention not only has excellent impact resistance, thermal stability, and hot water resistance, but also has
It is a useful molding material because it has excellent moldability and electrical properties.
而して、本発明の該組成物の成形品は、自動車部品や給
排水設備等に、難燃化したものは家電部品や配電部品等
に好適であり、耐久性が優れるため製品寿命の延長に大
いに役立つものである。Therefore, molded products of the composition of the present invention are suitable for automobile parts, water supply and drainage equipment, etc., and flame-retardant products are suitable for home appliance parts, power distribution parts, etc., and are excellent in durability, so they can extend the product life. It is very helpful.
以下に実施例を示すが本発明は以下の例に限定されるも
のではない。以下、％及び部は、夫々重量％及び重量部
を表わす。Examples are shown below, but the present invention is not limited to the following examples. Hereinafter, % and parts represent weight % and parts by weight, respectively.
なお、以下の実施例及び比較例において用いた耐衝撃性
スチレン系樹脂は次に述べる製造方法によって調製した
ものである。又、実施例及び比較例で用いた、耐衝撃性
スチレン系樹脂とこれを調製するに際して用いた、共役
ジエン系ゴム及び部分水添共役ジエン系ゴムは表−■に
示す通りのものである。The impact-resistant styrene resin used in the following Examples and Comparative Examples was prepared by the manufacturing method described below. In addition, the impact-resistant styrenic resins used in the Examples and Comparative Examples, and the conjugated diene rubbers and partially hydrogenated conjugated diene rubbers used in preparing the resins are as shown in Table 2.
製造例１：部分水添共役ジエン系ゴムの製造実施例で用
いる部分水添共役ジエン系ゴムは、代表的には、次に述
べる方法で製造した。Production Example 1: Production of Partially Hydrogenated Conjugated Diene Rubber The partially hydrogenated conjugated diene rubber used in the examples was typically produced by the method described below.
内容積１ａｌの撹拌機付、ジャケット付オートクレーブ
を反応器として用いて、ブタジェン／ｎ−ヘキサン混合
液（ブタジェン濃度２０％）を２０Ｉ／ｈ＋てｎ−ブチ
ルリチウム／ｎ−ヘキサン溶液（濃度５％）を７０ｍ１
／ｈｒで導入し、重合温度１１０℃でブタジェンの連結
重合を実施した。得られた活性重合体をメタノールで失
活、別の内容積１０Ａ’の撹拌機付、ジャケット付の反
応器に重合体溶液８１を移し、温度６０℃にて、水添触
媒としてジ−ｐ−トリルビス（１−シクロペンタジェニ
ル）チタニウム／シクロヘキサン溶液（濃度１２ミリモ
ル／ｌ） ２５０ｍ１と、ｎ−ブチルリチウム溶液（
濃度６ミリモル／ｌ ） ５０ｍ１とを０℃、 ２．０
ｋｇ／ｄの水素圧下で混合したものを添加、水素分圧３
．０ｋｇ／ｃｄにて６０分間反応させた。得られた部分
水添重合体溶液は、酸化防止剤として２，６−ジ−ター
シャリ−ブチルヒドロキシトルエンを重合体当り ０．
５部添加して、溶剤を除去した。Using a jacketed autoclave with an internal volume of 1 al with a stirrer as a reactor, a butadiene/n-hexane mixture (butadiene concentration 20%) was converted into an n-butyllithium/n-hexane solution (concentration 5%) at 20 I/h+. 70m1
/hr, and coupling polymerization of butadiene was carried out at a polymerization temperature of 110°C. The obtained activated polymer was deactivated with methanol, and the polymer solution 81 was transferred to another jacketed reactor with an internal volume of 10 A', and at a temperature of 60°C, di-p- 250 ml of tolylbis(1-cyclopentagenyl) titanium/cyclohexane solution (concentration 12 mmol/l) and n-butyllithium solution (
Concentration 6 mmol/l) 50ml at 0℃, 2.0
Add the mixture under hydrogen pressure of kg/d, hydrogen partial pressure 3
．． The reaction was carried out at 0 kg/cd for 60 minutes. The obtained partially hydrogenated polymer solution contains 2,6-di-tert-butylhydroxytoluene as an antioxidant at a concentration of 0.0% per polymer.
5 parts were added and the solvent was removed.
メタノール失活後にサンプリングして得た部分水添前の
ポリブタジェン及び部分水添ポリブタジェンの分析値は
表−■に示す通りであった。The analytical values of polybutadiene before partial hydrogenation and partially hydrogenated polybutadiene obtained by sampling after methanol deactivation were as shown in Table 1.
製造例２：耐衝撃性スチレン系樹脂の製造実施例で用い
る耐衝撃性スチレン系樹脂は塊状重合法によって製造し
た。代表例を次に述べる。Production Example 2: Production of Impact-resistant Styrenic Resin The impact-resistant styrenic resin used in this example was produced by a bulk polymerization method. Representative examples are described below.
表−■の部分水添ポリブタジェン１０部をスチレン９０
部とエチルベンゼン８部に溶解し、更にスチレンに対し
て０．０５部のベンゾイルパーオキサイドと０．１０部
のα−メチルスチレン２量体を添加し、８０℃で４時間
、１１０℃で４時間、１５０℃で４時間、撹拌下に重合
を行った。更に２３０℃前後で３０分間加熱処理を行い
、その後、未反応スチレン及びエチルベンゼンの真空除
去を行い、耐衝撃性スチレン系樹脂を得た。Table - 10 parts of partially hydrogenated polybutadiene in 90 parts of styrene
1 part and 8 parts of ethylbenzene, and further added 0.05 part of benzoyl peroxide and 0.10 part of α-methylstyrene dimer based on styrene, and heated at 80°C for 4 hours and at 110°C for 4 hours. Polymerization was carried out at 150° C. for 4 hours with stirring. Further, heat treatment was performed at around 230° C. for 30 minutes, and then unreacted styrene and ethylbenzene were removed under vacuum to obtain an impact-resistant styrenic resin.
得られた耐衝撃性スチレン系樹脂中の部分水添ポリブタ
ジェンの含有量は１１％であり、ポリスチレンの分散粒
子を含んだ状態での部分水添ポリブタジェンの平均粒子
径は２．７μであった。The content of partially hydrogenated polybutadiene in the resulting impact-resistant styrenic resin was 11%, and the average particle diameter of the partially hydrogenated polybutadiene containing dispersed particles of polystyrene was 2.7 μm.
次に樹脂組成物の物性測定評価方法について説明する。Next, a method for measuring and evaluating physical properties of a resin composition will be explained.
（０） 試験片の調製
射出成形機〔東芝機械■社製、ＩＳ８０ＡＭ、 シリ
ンダー温度２８０℃、成形サイクル１分〕で試験片を作
成した。(0) Preparation of test piece A test piece was prepared using an injection molding machine [manufactured by Toshiba Machine Corporation, IS80AM, cylinder temperature 280°C, molding cycle 1 minute].
（１） アイゾツト衝撃強さ
ＡＳＴＭ Ｄ２５６．ノツチ：有り
温度：２３℃及び−３０°Ｃ
（２）成形安定性
射出成形温度２９０℃で成形した成形品のアイゾツト衝
撃強さに対する３２０℃で１０分間シリンダー内で滞留
させた後成形した成形品のアイゾツト衝撃強さの保持率
から判定した。(1) Izot impact strength ASTM D256. Notched: Temperature: 23°C and -30°C (2) Molding stability Izo impact strength of a molded product molded at an injection molding temperature of 290°C vs. a molded product molded after staying in a cylinder for 10 minutes at 320°C Judgment was made from the retention rate of Izot impact strength.
（３）耐熱水性
９０℃の熱水中に１０００時間浸漬した後のアイゾツト
衝撃強さの保持率から判定した。(3) Hot water resistance Judgment was made from the retention of Izot impact strength after being immersed in hot water at 90°C for 1000 hours.
実施例 １
極限粘度０．５０（クロロホルム中、３０℃にて測定）
のポリ（２，６−シメチルー１，４ −）ユニレン）エ
ーテル（以下ＰＰＥと略称する）４５部、表−■のｋｌ
の耐衝撃性ポリスチレン（以下、ＨＩＰＳと略称する）
５５部、Ｚｎ０Ｏ，ｌ！部及びＺｎＳ０．２部とを押出
機を用いて３００℃の温度にて溶融混練して樹脂組成物
を得た。該樹脂組成物の物性試験結果を表−■に示す。Example 1 Intrinsic viscosity 0.50 (measured in chloroform at 30°C)
45 parts of poly(2,6-dimethyl-1,4-)unilene) ether (hereinafter abbreviated as PPE), kl of Table-■
high impact polystyrene (hereinafter abbreviated as HIPS)
55 copies, Zn0O,l! and 0.2 parts of ZnS were melt-kneaded using an extruder at a temperature of 300°C to obtain a resin composition. The physical property test results of the resin composition are shown in Table-■.
実施例 ２
ＺｎＯ及びＺｎＳを夫々０．１５部に減らし、イルガフ
オス１６８（チバガイギー■社製有機亜燐酸エステル、
トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイ
ト）を０．１５部添加した以外は実施例１を繰返して樹
脂組成物を得た。該樹脂組成物の物性試験結果を表−■
に示す。Example 2 ZnO and ZnS were reduced to 0.15 parts each, and Irgafuos 168 (organic phosphite manufactured by Ciba Geigy ■,
A resin composition was obtained by repeating Example 1 except that 0.15 parts of tris(2,4-di-t-butylphenyl) phosphite) was added. The physical property test results of the resin composition are shown in Table-■
Shown below.
実施例 ３
トリエタノールアミンを２部添加した以外は実施例２を
繰返して樹脂組成物を得た。該樹脂組成物の物性試験結
果を表−■に示す。Example 3 A resin composition was obtained by repeating Example 2 except that 2 parts of triethanolamine was added. The physical property test results of the resin composition are shown in Table-■.
比較例 ｌ
ＺｎＯ及びＺｎＳを添加しなかった以外は実施例１を繰
返して樹脂組成物を得た。該樹脂組成物の物性試験結果
を表−■に示す。Comparative Example 1 A resin composition was obtained by repeating Example 1 except that ZnO and ZnS were not added. The physical property test results of the resin composition are shown in Table-■.
比較例 ２
表−■のＮα１のＨＩＰＳに替えて、表−■のＮα２の
ＨＩＰＳを用いた以外は比較例１を繰返して樹脂組成物
を得た。該樹脂組成物の物性試験結果を表−■に示す。Comparative Example 2 A resin composition was obtained by repeating Comparative Example 1, except that HIPS with Nα2 in Table -■ was used instead of HIPS with Nα1 in Table -■. The physical property test results of the resin composition are shown in Table-■.
比較例 ３
表−■のＮα１のＨＩＰＳに替えて、表−■のＮα２の
ＨＩＰＳを用いた以外は実施例１を繰返して樹脂組成物
を得た。該樹脂組成物の物性試験結果を表−■に示す。Comparative Example 3 A resin composition was obtained by repeating Example 1, except that HIPS with Nα2 in Table-■ was used instead of HIPS with Nα1 in Table-■. The physical property test results of the resin composition are shown in Table-■.
比較例 ４
表−■のＮα１のＨＩＰＳに替えて、表−■のＮα２の
ＨＩＰＳを用いた以外は実施例２を繰返して樹脂組成物
を得た。該樹脂組成物の物性試験結果を表−■に示す。Comparative Example 4 A resin composition was obtained by repeating Example 2, except that HIPS with Nα2 in Table -■ was used instead of HIPS with Nα1 in Table -■. The physical property test results of the resin composition are shown in Table-■.
比較例 ５
表−■のＮα１のＨＩＰＳに替えて、表−■のＮα２の
ＨＩＰＳを用いた以外は実施例３を繰返して樹脂組成物
を得た。該樹脂組成物の物性試験結果を表−■に示す。Comparative Example 5 A resin composition was obtained by repeating Example 3, except that HIPS with Nα2 in Table -■ was used instead of HIPS with Nα1 in Table -■. The physical property test results of the resin composition are shown in Table-■.
実施例 ４
実施例１と同一のＰＰＥ６０部、表−■のＮα３ＨＩＰ
Ｓ４０部、トリフェニレンホスフェート５部、ＺｎＯ及
びＺｎＳを夫々０．２５部及びイルガフオス１６８を０
．３部とを押出機を用いて３００℃の温度にて溶融混練
して樹脂組成物を得た。該樹脂組成物の物性試験結果を
表−■に示す。Example 4 60 parts of the same PPE as Example 1, Nα3HIP in Table-■
40 parts of S, 5 parts of triphenylene phosphate, 0.25 parts each of ZnO and ZnS, and 0 parts of Irgafuos 168.
．． 3 parts were melt-kneaded using an extruder at a temperature of 300°C to obtain a resin composition. The physical property test results of the resin composition are shown in Table-■.
比較例 ６
ＺｎＯＳＺｎＳ及びイルガフオス１６８に変えて、１部
のスミライサーＢＨＴ （住友化学■社製 立体障害フ
ェノール）を添加した以外は実施例４を繰返して樹脂組
成物を得た。該樹脂組成物の物性試験結果を表−■に示
す。Comparative Example 6 A resin composition was obtained by repeating Example 4 except that 1 part of Sumilizer BHT (sterically hindered phenol manufactured by Sumitomo Chemical ■) was added instead of ZnOSZnS and Irgafuos 168. The physical property test results of the resin composition are shown in Table-■.
比較例 ７
表−■のＮα３のＨＩＰＳに替えて、表−■のＮα４の
ＨＩＰＳを用いた以外は実施例４を繰返して樹脂組成物
を得た。該樹脂組成物の物性試験結果を表−■に示す。Comparative Example 7 A resin composition was obtained by repeating Example 4 except that HIPS of Nα4 in Table -■ was used instead of HIPS of Nα3 in Table -■. The physical property test results of the resin composition are shown in Table-■.
比較例 ８
表−■のＮα３のＨＩＰＳに替えて、表−■のＮα４の
ＨＩＰＳを用いた以外は比較例６を繰返して樹脂組成物
を得た。該樹脂組成物の物性試験結果を表−■に示す。Comparative Example 8 A resin composition was obtained by repeating Comparative Example 6 except that HIPS of Nα4 in Table -■ was used instead of HIPS of Nα3 in Table -■. The physical property test results of the resin composition are shown in Table-■.
実施例 ５
表−■のＮα１のＨＩＰＳに替えて、表−■のＮα５の
ＨＩＰＳを用いた以外は実施例２を繰返して樹脂組成物
を得た。該樹脂組成物の物性試験結果を表−■に示す。Example 5 A resin composition was obtained by repeating Example 2, except that HIPS with Nα5 in Table -■ was used instead of HIPS with Nα1 in Table -■. The physical property test results of the resin composition are shown in Table-■.
比較例 ９
表−■のＮα１のＨＩＰＳに替えて、表−■のＮα６の
ＨＩＰＳを用いた以外は実施例２を繰返して樹脂組成物
を得た。該樹脂組成物の物性試験結果を表−■に示す。Comparative Example 9 A resin composition was obtained by repeating Example 2, except that HIPS with Nα6 in Table -■ was used instead of HIPS with Nα1 in Table -■. The physical property test results of the resin composition are shown in Table-■.
実施例 ６
さらに３部のニッサンナイミーンＬ２Ｇ２ （日本油
脂■社製アルキルアミン酸化アルキルアミン誘導体）を
添加した以外は実施例５を繰返して樹脂組成物を得た。Example 6 A resin composition was obtained by repeating Example 5, except that 3 parts of Nissan Nymeen L2G2 (alkylamine oxide alkylamine derivative manufactured by NOF ■) was added.
該樹脂組成物の物性試験結果を表−■に示す。The physical property test results of the resin composition are shown in Table-■.
（以下余白）(Margin below)
Claims (1)
重量部、 （ｂ）共役ジエン系ゴムの全二重結合のうち５〜７０重
量％が水添された部分水添共役ジエン系ゴムを含む耐衝
撃性スチレン系樹脂９０〜１０重量部、 （ｃ）スチレン系樹脂０〜８０重量部 及び （ｄ）熱安定剤０．０１〜５重量部 より成り、且つ成分（ｂ）における部分水添共役ジエン
系ゴム中に含まれる１，２−ビニル結合量及び１，４−
結合量が、夫々３重量％以下及び３０重量％以上であり
、成分（ｄ）が金属酸化物及び金属硫化物又は金属酸化
物、金属硫化物及び有機亜燐酸エステル類であることを
特徴とする安定化樹樹脂組成物。(1) (a) Polyphenylene ether resin 10-90
parts by weight, (b) 90 to 10 parts by weight of an impact-resistant styrenic resin containing a partially hydrogenated conjugated diene rubber in which 5 to 70 weight % of all double bonds in the conjugated diene rubber are hydrogenated, (c ) 0 to 80 parts by weight of a styrene resin and (d) 0.01 to 5 parts by weight of a heat stabilizer, and the amount of 1,2-vinyl bonds contained in the partially hydrogenated conjugated diene rubber as component (b). and 1,4-
The amount of bonding is 3% by weight or less and 30% by weight or more, respectively, and component (d) is a metal oxide and a metal sulfide, or a metal oxide, a metal sulfide, and an organic phosphite. Stabilized resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29725690A JPH04173857A (en) | 1990-11-05 | 1990-11-05 | Stabilized resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29725690A JPH04173857A (en) | 1990-11-05 | 1990-11-05 | Stabilized resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04173857A true JPH04173857A (en) | 1992-06-22 |
Family
ID=17844175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29725690A Pending JPH04173857A (en) | 1990-11-05 | 1990-11-05 | Stabilized resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04173857A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005030872A1 (en) * | 2003-09-30 | 2005-04-07 | Asahi Kasei Chemicals Corporation | Process for producing polyphenylene ether resin composition |
-
1990
- 1990-11-05 JP JP29725690A patent/JPH04173857A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005030872A1 (en) * | 2003-09-30 | 2005-04-07 | Asahi Kasei Chemicals Corporation | Process for producing polyphenylene ether resin composition |
| JPWO2005030872A1 (en) * | 2003-09-30 | 2007-11-15 | 旭化成ケミカルズ株式会社 | Method for producing polyphenylene ether resin composition |
| US7541399B2 (en) | 2003-09-30 | 2009-06-02 | Asahi Kasei Chemicals Corporation | Process for producing polyphenylene ether resin composition |
| JP4794302B2 (en) * | 2003-09-30 | 2011-10-19 | 旭化成ケミカルズ株式会社 | Method for producing polyphenylene ether resin composition |
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