JPS62207351A - Heat-resistant, impact-resistant resin composition having improved thermal stability - Google Patents
Heat-resistant, impact-resistant resin composition having improved thermal stabilityInfo
- Publication number
- JPS62207351A JPS62207351A JP5105186A JP5105186A JPS62207351A JP S62207351 A JPS62207351 A JP S62207351A JP 5105186 A JP5105186 A JP 5105186A JP 5105186 A JP5105186 A JP 5105186A JP S62207351 A JPS62207351 A JP S62207351A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- monomers
- monomer
- resin composition
- copolymer
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims description 23
- 239000000178 monomer Substances 0.000 claims abstract description 59
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 150000002825 nitriles Chemical class 0.000 claims abstract description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000005083 Zinc sulfide Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 10
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 8
- 239000005060 rubber Substances 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 1
- -1 dimethylaminoethyl Chemical group 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000003752 zinc compounds Chemical class 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- KYPOHTVBFVELTG-UPHRSURJSA-N (z)-but-2-enedinitrile Chemical compound N#C\C=C/C#N KYPOHTVBFVELTG-UPHRSURJSA-N 0.000 description 1
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- SNWNLRQYQRTOBP-UHFFFAOYSA-N [O--].[S--].[Zn++].[Zn++] Chemical compound [O--].[S--].[Zn++].[Zn++] SNWNLRQYQRTOBP-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 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
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は熱安定性の改良され几耐熱性耐衝撃性樹脂組成
物に関するものである。さらに詳しくは、高温加熱下で
の熱変色度が極めて小さく、かつ、滞留による機械的強
度の低下が改善された熱安定性に優れた樹脂組成物に関
するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a heat-resistant, impact-resistant resin composition with improved thermal stability. More specifically, the present invention relates to a resin composition that has extremely low degree of thermal discoloration under high-temperature heating, and has excellent thermal stability with improved mechanical strength reduction due to retention.
〈従来の技術〉
近年、ＡＢＳ樹脂等の耐熱性全改良する目的で共重合体
成分としてマレイミド系単量体を導入した樹脂の開発が
活発に進められている。<Prior Art> In recent years, resins incorporating maleimide monomers as copolymer components have been actively developed for the purpose of completely improving the heat resistance of ABS resins and the like.
（例えば、特開昭５７−９８５３６、特開昭５７−１０
０１０４、特開昭５ ｇ−１２９０４３）〈発明が解決
しようとしている問題点〉しかしながら、マレイミド系
単量体成分を導入した樹脂は耐熱性が高いため、通常の
ＡＢＳ樹脂等と比較してより高温下での成形加工が必要
である。このため、成形加工時に樹脂が黄色ないしは褐
色に変色し易いという問題がある。(For example, JP-A-57-98536, JP-A-57-10
0104, JP-A-5-129043) (Problems to be solved by the invention) However, since the resin into which the maleimide monomer component has been introduced has high heat resistance, it can withstand higher temperatures than ordinary ABS resin etc. It is necessary to perform the molding process at the bottom. For this reason, there is a problem in that the resin tends to discolor to yellow or brown during molding.
又、溶融樹脂が成形機内等に滞留すると変色はもとより
機械的強度も低下するという問題がある０
〈問題点を解決するための手段〉
本発明者らは上記の問題点を解決し、高温下での成形加
工時、特に滞留時に著しい変色及び機械的強度の低下を
起し難い耐熱性耐衝撃性樹脂組成物を得るべく鋭意検討
した結果、特定の亜鉛化合物を少量添加すると著しい効
果のあることを見出し、本発明に至った。In addition, if the molten resin remains in the molding machine, there is a problem that not only discoloration occurs but also mechanical strength decreases. <Means for solving the problem> The present inventors solved the above problem and As a result of intensive studies to obtain a heat-resistant and impact-resistant resin composition that does not easily cause significant discoloration or decrease in mechanical strength during molding, especially during retention, we found that adding a small amount of a specific zinc compound has a significant effect. This discovery led to the present invention.
すなわち、本発明は、マレイミド系単量体３〜７０重量
％および芳香族ビニル系単量体、不飽和二） ＋Ｊル系
単量体、不飽和カルボン酸およびそのエステル系単量体
の中から選ばれた１種ま′ｆｃは２種以上の重合体９７
〜３０重量％ならびにこれらの単量体と共重合可能な単
量体θ〜３０重量係とからなる共重合体（Ｎ１０〜９５
重量係および芳香族ビニル系単量体、不飽和ニトリル系
単量体、不飽和カルボン酸およびそのエステル系単量体
およびマレイミド系単量体の中から選ばれた１種ま友は
２種以上の単量体とゴム状重合体とからなるグラフト重
合体（Ｂ） ９０〜５重量％からなる組成物１００重量
部当り、硫化亜鉛および／または酸化亜鉛０．０２〜５
重量部含有することを特徴とする熱安定性の改良された
耐熱性耐衝撃性樹脂組成物に関するものである。That is, the present invention uses 3 to 70% by weight of a maleimide monomer, an aromatic vinyl monomer, an unsaturated monomer, an unsaturated carboxylic acid, and an ester monomer thereof. The selected one type or 'fc is a polymer of two or more types97
~30% by weight and a monomer θ~30% by weight copolymerizable with these monomers (N10~95
One type selected from weight ratio and aromatic vinyl monomer, unsaturated nitrile monomer, unsaturated carboxylic acid and its ester monomer, and maleimide monomer, or two or more types. graft polymer (B) consisting of a monomer of and a rubbery polymer: 0.02 to 5 parts by weight of zinc sulfide and/or zinc oxide per 100 parts by weight of a composition consisting of 90 to 5% by weight
The present invention relates to a heat-resistant and impact-resistant resin composition with improved thermal stability, characterized by containing part by weight of the composition.
以下本発明の樹脂組成物について具体的に説明する。The resin composition of the present invention will be specifically explained below.
０共重合体（５））
本発明の樹脂組成物の１成分である共重合体（Ａ）Ｕ、
上述のとおりマレイミド系単量体３〜７０重量％および
芳香族ビニル系単量体、不飽和ニトリル系単量体、不飽
和カルボン酸およびそのエステル系単量体の中から選ば
れた１種まとからなる共重合体である。各単量体は以下
のとおりである。0 copolymer (5)) Copolymer (A)U, which is one component of the resin composition of the present invention,
As mentioned above, 3 to 70% by weight of a maleimide monomer and one selected from aromatic vinyl monomers, unsaturated nitrile monomers, unsaturated carboxylic acids, and their ester monomers. It is a copolymer consisting of Each monomer is as follows.
マレイミド系単量体としては、マレイミド、Ｎ−メチル
マレイミド、Ｎ−エチルマレイミド、Ｎ−ブチルマレイ
ミド、Ｎ−ラウリルマレイミ）”、Ｎ−シクロヘキシル
マレイｊ）”、Ｎ−フェニルマレイミド、Ｎ Ｏ−ク
ロロフェニルマレイミドなどが挙げられ、１種または２
種以上用いることができる。これらのうち、通常はＮ
−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド
、Ｎ−ｏ−クロロフェニルマレイミドが好ましく使用さ
れる。Examples of maleimide monomers include maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide), N-cyclohexylmaleimide, N-phenylmaleimide, N-chlorophenyl Examples include maleimide, and one or two
More than one species can be used. Of these, usually N
-phenylmaleimide, N-cyclohexylmaleimide and N-o-chlorophenylmaleimide are preferably used.
芳香族ビニル系単量体としては、スチレン、α−メチル
スチレン、α−クロルスチレン、ｐ−メチルスチレン、
ｐ−ｔ−７’チルスチレン、０−クロルスチレン、ｐ−
クロルスチレン、２．５−ジクロルスチレン、３．４−
ジクロルスチレン、２．５−ジブロムスチレンなどがｌ
’られる。これらは１種または２種以上用いることがで
きる。これらのうち通常はスチレンおよびα−メチルス
チレンが好ましく使用される。Examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chlorostyrene, p-methylstyrene,
p-t-7'tylstyrene, 0-chlorostyrene, p-
Chlorstyrene, 2.5-dichlorostyrene, 3.4-
Dichlorostyrene, 2,5-dibromustyrene, etc.
'Can be done.' One or more types of these can be used. Among these, styrene and α-methylstyrene are usually preferably used.
不飽和ニトリル系単量体としては、アクリロニトリル、
メタシクロニトリル、マレオニトリル、フマロニトリル
などが挙げられ、１種または２種以上用いることができ
る。これらのうち通常はアクリロニトリルが好ましく使
用される。Examples of unsaturated nitrile monomers include acrylonitrile,
Examples include metacyclonitrile, maleonitrile, fumaronitrile, etc., and one or more types can be used. Among these, acrylonitrile is usually preferably used.
つぎに、不飽和カルボン酸およびそのエステル系単量体
としては、（メタ）アクリル酸およびそのメチル、エチ
ル、プロピル、ブチル、ラウリル、シクロヘキシル、２
−ヒドロキシエチル、グリシジルおよびジメチルアミノ
エチルなどの（メタ）アクリル酸エステル系単量体、な
らびに無水マレイン酸、無水イタコン酸、無水シトラコ
ン酸、無水ハイミック酸およびそれらのモノおよびジア
ルキルエステルなどが挙ケられる。これらは１種または
２種以上用いることができる。これらのうち、通常はメ
タクリル酸、メタクリル酸メチル、無水マレイン酸など
が好ましく使用される。Next, as unsaturated carboxylic acids and their ester monomers, (meth)acrylic acid and its methyl, ethyl, propyl, butyl, lauryl, cyclohexyl,
- (Meth)acrylic acid ester monomers such as hydroxyethyl, glycidyl and dimethylaminoethyl, as well as maleic anhydride, itaconic anhydride, citraconic anhydride, hymic anhydride and their mono- and dialkyl esters, etc. . One or more types of these can be used. Among these, methacrylic acid, methyl methacrylate, maleic anhydride and the like are usually preferably used.
さらに、これらの単量体以外に必要に応じてこれら単量
体と共重合可能な単量体０〜３０重量％を導入すること
ができる。この共重合可能な単量体として、例えばエチ
レン、塩化ビニル、塩化ビニリデン、アクリルアミド、
メタクリルアミド、酢酸ビニル、ビニルピロリドン、ビ
ニルピリジン、ビニルカルバゾール、アセナフチレンな
どが挙げられる。Furthermore, in addition to these monomers, 0 to 30% by weight of a monomer copolymerizable with these monomers can be introduced as necessary. Examples of the copolymerizable monomer include ethylene, vinyl chloride, vinylidene chloride, acrylamide,
Examples include methacrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, vinylcarbazole, and acenaphthylene.
共重合体（Ａ）は公知の塊状重合法、溶液重合法、塊状
−懸濁重合法、懸濁重合法、乳化重合法、乳化−懸濁重
合法、乳化−塊状重合法等によって製造することができ
る。The copolymer (A) can be produced by a known bulk polymerization method, solution polymerization method, bulk-suspension polymerization method, suspension polymerization method, emulsion polymerization method, emulsion-suspension polymerization method, emulsion-bulk polymerization method, etc. I can do it.
ここで、共重合体（Ｎにおけるマレイミド系単量体の量
全３〜７０重量％に限定しｔ理由は、マレイミド系単量
体の量が３重量％未満では耐熱性の高い樹脂組成物は得
られず、一方７０重量％全超えると衝繋強度の高いもの
が得られないばかりでなく、加工性が悪くなる。なお、
共重合体（４）の固有粘度（〔ワ〕、ジメチルホルムア
ミド溶液、３０℃で測定）には特に制限はないが機械的
強度と成形加工性のバランス面より０．３〜１．５の範
囲のもの、特に０．４〜１．０の範囲のものが好ましく
使用される。Here, the amount of maleimide monomers in the copolymer (N) is limited to 3 to 70% by weight in total.The reason is that if the amount of maleimide monomers is less than 3% by weight, the resin composition with high heat resistance cannot be obtained. On the other hand, if it exceeds 70% by weight, not only will it not be possible to obtain a product with high impact strength, but the workability will be poor.
The intrinsic viscosity of the copolymer (4) ([W], dimethylformamide solution, measured at 30°C) is not particularly limited, but it is in the range of 0.3 to 1.5 from the viewpoint of the balance between mechanical strength and moldability. Those in the range of 0.4 to 1.0 are preferably used.
０グラフト重合体（均
本発明の樹脂組成物の構成成分として用いられるグラフ
ト重合体（Ｂ）は、ゴム状重合体に芳香族ビニル系単量
体、不飽和ニトリル系単量体、不飽和カルボン酸および
そのエステル系単量体およびマレイミド系単量体の中か
ら選ばれた１種または２種以上の単量体をグラフト重合
させることによって製造されｍものである。0 graft polymer (uniform) The graft polymer (B) used as a constituent component of the resin composition of the present invention is a rubber-like polymer containing an aromatic vinyl monomer, an unsaturated nitrile monomer, an unsaturated carbon It is produced by graft polymerization of one or more monomers selected from acids, their ester monomers, and maleimide monomers.
ゴム状重合体は常温においてゴム状を呈するものである
。このゴム状重合体として、例えばポリブタジェン、ス
チレン−ブタジェンランダムま之はブロック共重合体、
水素化スチレン−ブタジェンランダム′！友はブロック
共重合体、アクリロニトリル−ブタジェン共重合体、ネ
オブレンゴム、クロロプレンゴム、インブチレンゴム、
天然ゴム、エチレンープロピレンゴム、エチレン−プロ
ピレン−共役ジエンゴム、塩素化ポリエチレン、塩素化
エチレン−プロピレン−共役ジエンゴム、アクリルゴム
、エチレン−酢酸ビニル共重合体、エチレン−（メタ）
アクリル酸メチル、エチル、プロピル、ブチル、グリシ
ジルまたはジメチルアミノエチルなどの（メタ）アクリ
ル酸エステル共重合体、エチレン−酢酸ビニル−メタク
リル酸グリシジル共重合体、エチレン−アクリル酸メチ
ル−メタクリル酸グリシジル共重合体、ポリビニルブチ
ラール、ポリエステルエラストマー、ポリアミドエラス
トマーなどが挙げられる。これらは架橋物、未架橋物の
いずｎも使用でき、また２種以上の混合物も使用するこ
とができる。A rubbery polymer exhibits a rubbery state at room temperature. Examples of the rubbery polymer include polybutadiene, styrene-butadiene random or block copolymers,
Hydrogenated styrene-butadiene random′! Friends are block copolymers, acrylonitrile-butadiene copolymers, neoprene rubber, chloroprene rubber, inbutylene rubber,
Natural rubber, ethylene-propylene rubber, ethylene-propylene-conjugated diene rubber, chlorinated polyethylene, chlorinated ethylene-propylene-conjugated diene rubber, acrylic rubber, ethylene-vinyl acetate copolymer, ethylene-(meth)
(Meth)acrylic acid ester copolymers such as methyl acrylate, ethyl, propyl, butyl, glycidyl or dimethylaminoethyl, ethylene-vinyl acetate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer Examples include polyvinyl butyral, polyester elastomer, and polyamide elastomer. Both crosslinked and uncrosslinked products can be used, and mixtures of two or more types can also be used.
ゴム状重合体にグラフト重合される芳香族ビニル系単量
体、不飽和ニトリル系単量体、不飽和カルボン酸、その
エステルおよび／またはマレイミド系単量体としては、
共重合体（ＡＪの項で述べられた各化合物が挙げられる
。The aromatic vinyl monomer, unsaturated nitrile monomer, unsaturated carboxylic acid, ester thereof, and/or maleimide monomer to be graft-polymerized to the rubbery polymer include:
Copolymers (including the compounds mentioned in the AJ section).
芳香族ビニル系単量体としてはスチレン、不飽和ニトリ
ル系単量体としてはアクリロニトリル、不飽和カルボン
酸としてはメタクリル酸および無水マレイン酸、不飽和
カルボン酸エステルとしてはメタクリル酸メチル、マレ
イミド系単量体としてはＮ−フェニルマレイミドが好ま
しい。Styrene is used as an aromatic vinyl monomer, acrylonitrile is used as an unsaturated nitrile monomer, methacrylic acid and maleic anhydride are used as unsaturated carboxylic acids, methyl methacrylate and maleimide monomer are used as unsaturated carboxylic acid esters. As the compound, N-phenylmaleimide is preferred.
ゴム状重合体に少なくとも芳香族ビニル系単量体と不飽
和ニトリル系単量体の２成分がグラフト重合してなるグ
ラフト重合体が特に好ましい０
グラフト重合体（均は前述の共重合体（ＡＩの項で挙げ
たような各種重合法によって製造することができる。な
お、グラフト重合体（Ｂ）のグラフトゴムの重量平均粒
子径は、通常０．０５〜３μｍの範囲のものが好ましい
。また、グラフト率は一般に１０〜１００重量％のもの
が、まｔグラフト重合体中のゴム含有量は５〜８０重量
％のものが好ましく使用さｎる。Particularly preferred is a graft polymer obtained by graft polymerizing at least two components, an aromatic vinyl monomer and an unsaturated nitrile monomer, onto a rubber-like polymer. It can be produced by various polymerization methods such as those listed in the above section.The weight average particle diameter of the graft rubber of the graft polymer (B) is usually preferably in the range of 0.05 to 3 μm. The grafting ratio is generally 10 to 100% by weight, and the rubber content in the graft polymer is preferably 5 to 80% by weight.
０硫化亜鉛および酸ｆヒ亜鉛
本発明の樹脂組成物には、硫化亜鉛および／または酸ｆ
ヒ亜鉛が含有される。The resin composition of the present invention contains zinc sulfide and/or acid f
Contains zinc.
硫化亜鉛および／または酸化亜鉛の添加により組成物の
熱安定性が著しく改善され、成形加工時の着色および滞
留時の機械的強度の低下といった問題が解決される。他
の亜鉛化合物ではかかる問題は解決されない。The addition of zinc sulfide and/or zinc oxide significantly improves the thermal stability of the composition and solves the problems of coloring during molding and loss of mechanical strength during retention. Other zinc compounds do not solve this problem.
なお、硫化亜鉛および／ま友は酸化亜鉛の平均粒子径に
は特に制限はないが、熱安定性改善の面より平均粒子径
が０．５μｍ以下で、かつ３５０メツシュ通過粒子が９
９９重量部上である粉末が好ましい。There is no particular restriction on the average particle size of zinc oxide for zinc sulfide and/or mayu, but in order to improve thermal stability, the average particle size should be 0.5 μm or less, and the particles passing through 350 mesh should be 9.
Powders that are above 99 parts by weight are preferred.
これら亜鉛化合物は単独で、ま友は混合して用いること
ができるが、特に硫化亜鉛単独および硫化亜鉛−酸化亜
鉛混合物が熱安定性改善の面より好ましい。These zinc compounds can be used alone or in combination, but zinc sulfide alone and a zinc sulfide-zinc oxide mixture are particularly preferred from the standpoint of improving thermal stability.
０樹脂組成物
本発明の樹脂組成物は前記の共重合体（Ａ）１０〜９５
重量係およびグラフト重合体（Ｂ）９０〜５重＠係から
なる組成物１００重量部当り硫化亜鉛および／または酸
化亜鉛０．０２〜５重量部含有してなる組成物である。0 resin composition The resin composition of the present invention contains the above-mentioned copolymer (A) 10-95
This composition contains 0.02 to 5 parts by weight of zinc sulfide and/or zinc oxide per 100 parts by weight of the composition consisting of 90 to 5 parts by weight of the graft polymer (B).
ここで共重合体（Ｎの量が、共重合体（Ａ）とグラフト
重合体（Ｂ）の合計当り１００重量部満（グラフト重合
体（Ｂ）９０重量％を超える）では耐熱性が劣り好まし
くない。一方９５重量％を超えると（グラフト重合体（
Ｂ）５重量％未満）耐衝撃性が劣り好ましくない。Here, a copolymer (in which the amount of N is less than 100 parts by weight (more than 90% by weight of the graft polymer (B)) based on the total of the copolymer (A) and the graft polymer (B)) has poor heat resistance and is therefore preferable. On the other hand, if it exceeds 95% by weight (graft polymer (
B) Less than 5% by weight) Impact resistance is poor and undesirable.
ま之、硫化亜鉛および／または酸化亜鉛の量が、共重合
体（Ｎとグラフト重合体（Ｂ）の合計１００重量部当り
０．０２重量部未満では樹脂組成物の熱変色に対する防
止効果が小さく、一方５重量部より多量に添加しても変
色改良にはそれ以上の効果がないばかりでなく、樹脂組
成物の機械的強度および加工性が低下し、好ましくない
。However, if the amount of zinc sulfide and/or zinc oxide is less than 0.02 parts by weight per 100 parts by weight of the copolymer (N and graft polymer (B)), the effect of preventing thermal discoloration of the resin composition will be small. On the other hand, even if it is added in an amount greater than 5 parts by weight, not only is there no further effect in improving discoloration, but also the mechanical strength and processability of the resin composition are reduced, which is not preferable.
熱変色に対する防止効果ならびに機械的強度および加工
性の面より硫化亜鉛および／または酸化亜鉛がＯ，１〜
０．５重量部であることが特に好ましい。Zinc sulfide and/or zinc oxide are O,1~
Particularly preferred is 0.5 part by weight.
樹脂組成物の製造は任意の方法で行なうことができる。The resin composition can be produced by any method.
例えば、共重合体（Ｎま友はグラフト重合体（Ｂ）の重
合工程あるいは後処理工程において亜鉛化合物全添加す
ることができる０得られた配合物は一般にバンバリーミ
キサ−、ロールミル、−軸または二軸押出機等、公知の
溶融混練機にて混練し、成形材料として供せられる。For example, the zinc compound can be completely added to the copolymer (N) during the polymerization or post-treatment step of the graft polymer (B). The mixture is kneaded in a known melt kneader such as a screw extruder and used as a molding material.
本発明の樹脂組成物に対し、必要に応じて酸化防止剤、
熱安定剤、光安定剤、滑剤、可塑剤、帯電防止剤、無機
および有機着色剤、発泡剤、無機および有機系充填剤、
難燃剤、表面光沢改良剤、艶消し剤などを添加すること
ができる。For the resin composition of the present invention, an antioxidant, if necessary,
heat stabilizers, light stabilizers, lubricants, plasticizers, antistatic agents, inorganic and organic colorants, blowing agents, inorganic and organic fillers,
Flame retardants, surface gloss improvers, matting agents, etc. can be added.
これらの各種添加剤は樹脂組成物の製造工程中あるいは
その後の加工工程において添加することができる。These various additives can be added during the manufacturing process of the resin composition or in subsequent processing steps.
性が非常に良いことから、ガラス繊維、金属繊維、炭素
繊維あるいはこｎらの粉末、炭酸カルシウム、メルク、
石こう、アルミナ、シリカ、雲母、窒化ホウ素、ジルコ
ニア、炭化ケイ素、チタン酸カリウムなどとの覆合材料
として使用することができる。Because of their excellent properties, glass fibers, metal fibers, carbon fibers, powders of these materials, calcium carbonate, Merck,
It can be used as a coating material with gypsum, alumina, silica, mica, boron nitride, zirconia, silicon carbide, potassium titanate, etc.
さらには、本発明の樹脂組成物にポリエチレン、ポリプ
ロピレン、ポリブテン−１、エチレン−ブテン−１共重
合体、プロピレン−ブテン−１共重合体、７’ロピレン
一エチレンブロツク共重合体、エチレン−プロピレン系
ゴム、無水マレイン酸グラフトポリオレフィン、塩素化
ポリオレフィン、エチレン−酢酸ビニル共重合体、エチ
レン−ビニルアルコール共重合体、エチレン−（メタ）
アクリル酸およびその金属塩共重合体、エチレン−（メ
タ）アクリル酸メチル、エチル、プロピル、ブチル、グ
リシジル、ジメチルアミンエチルなどの（メタ）アクリ
ル酸エステル共重合体、ポリビニルブチラール、ポリ塩
化ビニル、ブタジェンゴム、スチレン−ブタジェンラン
ダム′！友はブロック共重合体、水素化スチレン−ブタ
ジェンランダムｔ ７Ｃｔｆ’１７”ロツり共重合体、
アクリロニトリル−ブタジェンゴム、インブチレンゴム
、アクリルゴム、ポリカーボネート、ポリエステル、ポ
リアミド、ポリイミド、ポリアミドイミド、ポリエーテ
ルエーテルクトン、ポリサルホン、ポリエーテルサルホ
ン、ポリフェニレンオキサイド、ポリオキシメチレン等
の各種高分子材料を配合することにより、樹脂組成物あ
るいは積層体等として車両部品、船舶部品、航空機部品
、建築材料、電気部品、家具、事務用品等多くの分野に
広く使用することができる。Furthermore, the resin composition of the present invention may include polyethylene, polypropylene, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, 7' propylene-ethylene block copolymer, ethylene-propylene-based Rubber, maleic anhydride grafted polyolefin, chlorinated polyolefin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)
Acrylic acid and its metal salt copolymers, (meth)acrylic acid ester copolymers such as ethylene-methyl (meth)acrylate, ethyl, propyl, butyl, glycidyl, dimethylamine ethyl, polyvinyl butyral, polyvinyl chloride, butadiene rubber , styrene-butadiene random′! Friend is block copolymer, hydrogenated styrene-butadiene random t7Ctf'17'' rotary copolymer,
Compounding various polymeric materials such as acrylonitrile-butadiene rubber, inbutylene rubber, acrylic rubber, polycarbonate, polyester, polyamide, polyimide, polyamideimide, polyetheretherctone, polysulfone, polyethersulfone, polyphenylene oxide, polyoxymethylene, etc. Therefore, it can be widely used as a resin composition or a laminate in many fields such as vehicle parts, ship parts, aircraft parts, building materials, electrical parts, furniture, and office supplies.
以下に本発明を実施例でもって説明するが、本発明はこ
れによって限定されるものではない０実施例および比較
例
公知の乳化重合法により、第１表〜第２表に示し次共重
合体（ＡＪおよびグラフト重合体（Ｂ） ’に合成した
。この場合、乳化剤としてドデシルベンゼンスルホン酸
ナトリウム、重合開始剤として過硫酸カリウム、連鎖移
動剤としてｔ−ドデシルメルカプタンを用い、６５〜７
５℃で重合した０
これら重合体および亜鉛化付物を第３表〜第４表に示し
た割合で混合し、バンバＩＪ−ミキサーにて混練したの
ち、ベレット化した。このペレットヲ射出成形機にて２
９０℃で滞留させることなく試験片（１５０ｍｍＸ７０
胴×３閣）を作成した。又、射出成形機に２９０℃、１
０分間滞留させたのち各種特性評価用試験片を作成し友
０
評価結果全第３表〜第４表に示す。The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Examples and Comparative Examples (AJ and graft polymer (B)' were synthesized. In this case, sodium dodecylbenzenesulfonate was used as an emulsifier, potassium persulfate was used as a polymerization initiator, and t-dodecylmercaptan was used as a chain transfer agent.
These polymers and galvanized additives polymerized at 5° C. were mixed in the proportions shown in Tables 3 to 4, kneaded in a Bamba IJ-mixer, and then formed into pellets. This pellet is made into an injection molding machine.
A test piece (150 mm x 70
(Torso x 3 cabinets) was created. In addition, the injection molding machine was heated to 290℃, 1
After staying for 0 minutes, test pieces for various characteristic evaluations were prepared and the evaluation results are shown in Tables 3 to 4.
なお、熱変色による黄変はＹｅｌｌｏｗｎｅｓｓ Ｉｎ
ｄｅｘ（ＹＩ ）で示した。（ＡＳＴＭ Ｄ−１９２
５に準拠し、村上色彩技術研究新製ＣＡ−３５型高速分
光光度計を用い友。）
〈発明の効果〉
本発明の樹脂組成物は、優れｔ熱安定性を有しており、
高温加熱下での変色度が小さく、かつ滞留による機械的
強度の低下も小さい耐熱性耐衝堪性樹脂組成物である。In addition, yellowing due to heat discoloration is called Yellowness In
It is expressed as dex(YI). (ASTM D-192
5, using a new model CA-35 high-speed spectrophotometer manufactured by Murakami Color Technology Research. ) <Effects of the Invention> The resin composition of the present invention has excellent thermal stability,
It is a heat-resistant and impact-resistant resin composition that has a small degree of discoloration under high-temperature heating and a small decrease in mechanical strength due to retention.
Claims (2)
ビニル系単量体、不飽和ニトリル系単量体、不飽和カル
ボン酸およびそのエステル系単量体の中から選ばれた１
種または２種以上の単量体９７〜３０重量％ならびにこ
れらの単量体と共重合可能な単量体０〜３０重量％とか
らなる共重合体（Ａ）１０〜９５重量％および芳香族ビ
ニル系単量体、不飽和ニトリル系単量体、不飽和カルボ
ン酸およびそのエステル系単量体およびマレイミド系単
量体の中から選ばれた１種または２種以上の単量体とゴ
ム状重合体とからなるグラフト重合体（Ｂ）９５〜５重
量％からなる組成物１００重量部当り、硫化亜鉛および
／または酸化亜鉛０．０２〜５重量部含有することを特
徴とする熱安定性の改良された耐熱性耐衝撃性樹脂組成
物。(1) 1 selected from 3 to 70% by weight of a maleimide monomer and an aromatic vinyl monomer, an unsaturated nitrile monomer, an unsaturated carboxylic acid and its ester monomer
10-95% by weight of a copolymer (A) consisting of 97-30% by weight of a species or two or more monomers and 0-30% by weight of a monomer copolymerizable with these monomers, and an aromatic One or more monomers selected from vinyl monomers, unsaturated nitrile monomers, unsaturated carboxylic acids and their ester monomers, and maleimide monomers and rubber-like A thermally stable composition containing 0.02 to 5 parts by weight of zinc sulfide and/or zinc oxide per 100 parts by weight of a composition comprising 95 to 5% by weight of graft polymer (B) Improved heat resistant impact resistant resin composition.
１〜０．５重量部である特許請求の範囲第１項記載の熱
安定性の改良された耐熱性耐衝撃性樹脂組成物。(2) The content of zinc sulfide and/or zinc oxide is 0.
1-0.5 parts by weight of a heat-resistant, impact-resistant resin composition with improved thermal stability according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5105186A JPH0643538B2 (en) | 1986-03-07 | 1986-03-07 | Heat resistant and impact resistant resin composition with improved thermal stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5105186A JPH0643538B2 (en) | 1986-03-07 | 1986-03-07 | Heat resistant and impact resistant resin composition with improved thermal stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62207351A true JPS62207351A (en) | 1987-09-11 |
| JPH0643538B2 JPH0643538B2 (en) | 1994-06-08 |
Family
ID=12876001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5105186A Expired - Lifetime JPH0643538B2 (en) | 1986-03-07 | 1986-03-07 | Heat resistant and impact resistant resin composition with improved thermal stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643538B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020503402A (en) * | 2016-12-28 | 2020-01-30 | ロッテ アドバンスト マテリアルズ カンパニー リミテッド | Thermoplastic resin composition and molded article produced therefrom |
-
1986
- 1986-03-07 JP JP5105186A patent/JPH0643538B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020503402A (en) * | 2016-12-28 | 2020-01-30 | ロッテ アドバンスト マテリアルズ カンパニー リミテッド | Thermoplastic resin composition and molded article produced therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0643538B2 (en) | 1994-06-08 |
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