JPH0334781B2 - - Google Patents
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- Publication number
- JPH0334781B2 JPH0334781B2 JP59084781A JP8478184A JPH0334781B2 JP H0334781 B2 JPH0334781 B2 JP H0334781B2 JP 59084781 A JP59084781 A JP 59084781A JP 8478184 A JP8478184 A JP 8478184A JP H0334781 B2 JPH0334781 B2 JP H0334781B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- copolymer
- compound
- polycarbonate
- 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.)
- Expired - Lifetime
Links
- 229920001577 copolymer Polymers 0.000 claims description 18
- 229920000578 graft copolymer Polymers 0.000 claims description 17
- -1 aromatic vinyl compound Chemical class 0.000 claims description 15
- 239000004417 polycarbonate Substances 0.000 claims description 14
- 229920000515 polycarbonate Polymers 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 229920006015 heat resistant resin Polymers 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 229920003244 diene elastomer Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 238000000465 moulding Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- UGUYQBMBIJFNRM-UHFFFAOYSA-N but-2-en-2-ylbenzene Chemical compound CC=C(C)C1=CC=CC=C1 UGUYQBMBIJFNRM-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 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
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- PFASSPYFJVNBQQ-UHFFFAOYSA-N 3-ethoxyfuran-2,5-dione Chemical compound CCOC1=CC(=O)OC1=O PFASSPYFJVNBQQ-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-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
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 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
- 239000005357 flat glass Substances 0.000 description 1
- IDDSVMYOXWHSAK-UHFFFAOYSA-N furan-2,5-dione 5-phenylpenta-2,4-dienenitrile Chemical compound O=C1OC(=O)C=C1.N#CC=CC=CC1=CC=CC=C1 IDDSVMYOXWHSAK-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
〔〕 発明の目的
１ 技術分野
本発明は、耐光変色が少なく、かつ、耐衝撃性
および成形安定性に優れる新規な耐熱性樹脂組成
物に関する。
２ 従来の技術及び問題点
従来から自動車の内装材料或いは事務機器の外
カク材料として多く利用されている変性ポリフエ
ニレンエーテル（変性PPO）、ポリカーボネート
（PC）やα−メチルスチレンを用いた超耐熱性
ABS樹脂は、耐候性、成形安定性及び落球衝撃
強度に劣るという基本的な欠点を有している。更
に、自動車内装や事務機の様に窓ガラスによつて
大部分の紫外線を遮断しても透過する可視光線に
よつて変色ならびに機械的強度が低下する、いわ
ゆる耐光変色及び耐衝撃性にも重大な欠陥を有し
ている。この欠点を改良する目的で、例えばポリ
フエニレンエーテル（PPO）にEPDM系グラフ
ト重合体を用いる事が提案（特公昭47−43174、
47−43290）されているが、本来PPO自体が耐熱
老化性ならびに耐候性に劣るために改良の効果は
期待出来ない。又、同じEPDM系グラフト重合
体とα−メチルスチレンを用いた樹脂の組合せも
公知であるが、耐熱性ならびに落球衝撃強度が十
分ではなく、又、成形安定性にも劣り、実用上問
題がある。
本発明者等はかかる欠点を解決すべく鋭意研究
した結果本発明に到達したものである。
〔〕 発明の構成および効果
即ち、本発明は、非共役ジエン系ゴムに、芳香
族ビニル化合物およびまたは不飽和カルボン酸ア
ルキルエステル化合物をグラフト重合したグラフ
ト重合体(A)10〜80重量％、不飽和ジカルボン酸無
水物および芳香族ビニルまたはそれらとシアン化
ビニル化合物からなる共重合体(B)10〜80重量％お
よびポリカーボネート(C)10〜80重量％とからなる
事を特徴とする耐光変色が少なく、かつ耐衝撃
性、落球衝撃強度および成形安定性に優れる耐熱
性樹脂組成物を提供するものである。
以下に本発明について更に詳しく説明する。
１ グラフト重合体(A)
グラフト重合体(A)を構成する非共役ジエン系ゴ
ム質重合体とは、エチレン−プロピレン共重合
体、ジシクロペンタジエン、エチリデンノルボル
ネン、1.4−ヘキサジエン、1.4−シクロヘプタジ
エン、1.5−シクロオクタジエン等の非共役ジエ
ンを共重合させたエチレン−プロピレン−非共役
ジエン共重合体等のエチレン−プロピレン系重合
体(i)、アクリル酸メチル、アクリル酸エチル、ア
クリル酸ブチル、アクリル酸プロピル等のホモポ
リマーならびにスチレン、アクリロニトリル等の
他の共重合性化合物との共重合体等のアクリル酸
エステル系重合体(ii)、塩素化ポリエチレン(iii)およ
びエチレン−酢酸ビニル共重合体(iv)、からなる群
より選ばれた１種以上の重合体であり、物性バラ
ンス面より特にエチレン−プロピレン系重合体が
好ましい。
グラフト重合体を構成する芳香族ビニル化合物
としては、スチレン、α−メチルスチレン、メチ
ル−α−メチルスチレン、ビニルトルエン等を挙
げることができる。また、不飽和カルボン酸アル
キルエステル化合物としては、メチルアクリレー
ト、エチルアクリレート、ブチルアクリレート、
メチルメタクリレート、エチルメタクリレート、
ブチルメタクリレート、ヒドロキシエチルアクリ
レート、ヒドロキシエチルメタクリレート、ヒド
ロキシプロピルメタクリレート、更に、分子中に
エポキシ基を有するグリシジルアクリレート、グ
リシジルメタクリレート等を挙べることができ
る。
グラフト重合体(A)における非共役ジエン系ゴム
質重合体と化合物との組成比には特に制限はない
が、非共役ジエン系ゴム質重合体５〜70重量％、
化合物30〜95重量％であることが好ましい。
また、かかる重合体を構成する化合物における
各化合物の組成比にも特に制限はないが、芳香族
ビニル化合物単独又は芳香族ビニル化合物50〜80
重量％および不飽和カルボン酸アルキルエステル
化合物20〜50重量％であることが好ましい。
グラフト重合体(A)の製造方法としては乳化重合
法、懸濁重合法、塊状重合法、溶液重合法、乳化
−懸濁重合法、塊状−懸濁重合法等が挙げられ
る。
２ 共重合体(B)
共重合体(B)を構成する不飽和ジカルボン酸無水
物としては、無水マレイン酸、オキシ無水マレイ
ン酸、エトキシ無水マレイン酸、無水シトラコン
酸、無水フタール酸、無水イタコン酸等が挙げら
れる。また、芳香族ビニル化合物としては、スチ
レン、α−メチルスチレン、メチル−α−メチル
スチレン、ビニルトルエン等を挙げることができ
る。さらに、不飽和ジカルボン酸無水物及び芳香
族ビニル化合物と共に用いることのできるシアン
化ビニル化合物としてはアクリロニトリル、メタ
アクリロニトリル等を挙げることができる。
共重合体(B)を構成する各化合物の組成比にも特
に制限はないが、不飽和カルボン酸無水物が0.5
〜65重量％であることが好ましく、0.5重量％未
満では耐熱性が、又、65重量％を超えると成形安
定性が悪くなる傾向がある。さらに、芳香族ビニ
ル化合物とシアン化ビニル化合物との組成比も特
に制限はないが、好ましくは芳香族ビニル化合物
50〜100重量％およびシアン化ビニル化合物50〜
０重量％である。
共重合体(B)の製造方法としては塊状重合法、溶
液重合法、塊状−懸濁重合法等が挙げられる。
３ ポリカーボネート(C)
ポリカーボネート(C)としては、芳香族ポリカー
ボネート、脂肪族ポリカーボネート、脂肪族−芳
香族ポリカーボネート等々を挙げることができ
る。一般には、2.2−ビス（４−オキシフエニル）
アルカン系、ビス（４−オキシフエニル）エーテ
ル系、ビス（４−オキシフエニル）スルホン、ス
ルフイドまたはスルホキサイド系などのビスフエ
ノール類からなる重合体、もしくは共重合体であ
り、目的に応じてハロゲンで置換されたビスフエ
ノール類を用いた重合体である。
４ 組成比率
本発明の耐熱性樹脂組成物は、上述のグラフト
重合体(A)10〜80重量％、共重合体(B)10〜80重量％
およびポリカーボネート(C)10〜80重量％からな
る。
グラフト重合体(A)が10重量％未満又は共重合体
(B)が80重量％を超すと、最終組成物の耐光変色及
び耐衝撃性が劣る。共重合体(B)が10重量％未満又
はグラフト重合体(A)が80重量％を超すと耐熱性及
び成形安定性が劣る。また、ポリカーボネート(C)
が10重量％未満では耐熱性に劣り、80重量％を超
すと成形安定性が劣る。
グラフト重合体(A)、共重合体(B)およびポリカー
ボネート(C)の混合は公知の混合機で行うことが出
来る。又は、混合時に使用目的に応じてポリスチ
レン、スチレン−アクリロニトリル共重合体のよ
うなポリマーを始め、染顔料、安定剤、可塑剤、
帯電防止剤、紫外線吸収剤、滑剤、充填剤等の添
加も十分可能である。
以下に実施例を用いて本発明を具体的に説明す
るが本発明はこれらによつて何ら制限されるもの
ではない。
実施例 １〜４
１ グラフト重合体（Ａ−及び−）の製造方
法
ヨウ素価8.5、ムーニー粘度61、プロピレ
ン含有率43重量％、ジエン成分としてジシク
ロペンタジエンを含むエチレン−プロピレン
系ゴム500重量部をｎ−ヘキサン2500重量部
および二塩化エチレン1500重量部に溶解し、
スチレン450重量部および過酸化ベンゾイル
10重量部を仕込んだ後、67℃で10時間窒素雰
囲気中600r.p.mの撹拌下で重合した。
重合液を大過剰のメタノールと接触させ。
折出した沈殿物を分離乾燥後、ゴム含有量
52.6％のスチレングラフト重合体（Ａ−１）
を得た。
ヨウ素8.5、ムーニー粘度61、プロピレン
含有率43重量％、ジエン成分としてエチリデ
ンノルボルネンを含むエチレン−プロピレン
系ゴム500重量部をｎ−ヘキサン2500重量部
および二塩化エチレン1500重量部に溶解し、
スチレン700重量部、メチルメタクリレート
300重量部および過酸化ベンゾイル10重量部
を仕込んだ後、67℃で10時間、窒素雰囲気中
600r.p.m.の撹拌下で重合した。
重合液を大過剰のメタノールと接触させ、
折出した沈殿物を分離乾燥後、ゴム含有量
35.2％のスチレン−メチルメタクリレートグ
ラフト重合体（Ａ−）を得た。
２ 共重合体（Ｂ−及び−）の製造方法
スチレン70重量部、無水マレイン酸30重量部
にラウロイルパーオキサイド0.05重量部とｔ−
ドデシルメルカプタン0.4重量部を加え、窒素
置換しながら70℃で５時間塊状重合し、次いで
懸濁安定剤としてポリビニルアルコール0.14重
量部とメトローズ0.06重量部を溶解した水を
200重量部加え懸濁し、開始剤としてラウロイ
ルパーオキサイド0.5重量部、水相重合防止剤
として酸性亜硫酸ソーダ0.1重量部を加えて３
時間重合した。粒状重合体を分離し、洗浄乾燥
して無水マレイン酸−スチレン共重合体（Ｂ−
）を得た。
スチレン70重量部、アクリロニトリル15重量
部、無水マレイン酸15重量部にラウロイルパー
オキサイド0.05重量部とｔ−ドデシルメルカプ
タン0.4重量部を加え、窒素置換しながら70℃
で５時間塊状重合し、次いで懸濁安定剤として
ポリビニルアルコール0.14重量部とメトローズ
0.06重量部を溶解した水230重量部加え懸濁し、
開始剤としてラウロイルパーオキサイド0.5重
量部、水相重合防止剤として酸性亜硫酸ソーダ
0.1重量部を加えて３時間重合した。粒状重合
体を分離し、洗浄乾燥して無水マレイン酸−ス
チレン−アクリロニトリル共重合体（Ｂ−）
を得た。
３ ポリカーボネート(C)
帝人化成社製ポリカーボネート
“パンライト Ｌ−1250”
上述の方法により得られたグラフト重合体(A)お
よび共重合体(B)ならびに市販のポリカーボネート
(C)を用いて表−１に示す組成で65ミリ一軸押出機
にて混合し、各種組成物を得た。得られた組成物
ならびに比較品としての市販の変性ポリフエニレ
ンオキサイド樹脂および超耐熱ABS樹脂の耐光
変色、成形安定性、耐熱性、耐衝撃性、加工性お
よび落球衝撃強度を表−１に示す。なお、組成比
率は重量部を示す。
【表】DETAILED DESCRIPTION OF THE INVENTION [] Object of the Invention 1 Technical Field The present invention relates to a novel heat-resistant resin composition that exhibits little discoloration due to light resistance and is excellent in impact resistance and molding stability. 2. Conventional technologies and problems Super heat-resistant technology using modified polyphenylene ether (modified PPO), polycarbonate (PC), and α-methylstyrene, which have been widely used as interior materials for automobiles and exterior materials for office equipment. sex
ABS resin has basic drawbacks such as poor weather resistance, molding stability, and falling ball impact strength. Furthermore, even if most of the ultraviolet rays are blocked by window glass, such as in automobile interiors and office machines, the visible light that passes through can cause discoloration and reduce mechanical strength, which is important for so-called light discoloration and impact resistance. It has some defects. In order to improve this drawback, it has been proposed to use an EPDM-based graft polymer for polyphenylene ether (PPO) (Japanese Patent Publication No. 47-43174,
47-43290), but since PPO itself has poor heat aging resistance and weather resistance, no improvement can be expected. In addition, a combination of a resin using the same EPDM-based graft polymer and α-methylstyrene is also known, but it does not have sufficient heat resistance and falling ball impact strength, and is also poor in molding stability, which poses practical problems. . The present inventors have arrived at the present invention as a result of intensive research aimed at solving these drawbacks. [] Structure and Effects of the Invention That is, the present invention provides a graft polymer (A) in which 10 to 80% by weight of an aromatic vinyl compound and/or an unsaturated carboxylic acid alkyl ester compound is graft-polymerized to a non-conjugated diene rubber. A light-resistant discoloration characterized by comprising 10 to 80% by weight of a saturated dicarboxylic acid anhydride and an aromatic vinyl or a copolymer (B) consisting of them and a vinyl cyanide compound and 10 to 80% by weight of a polycarbonate (C). The object of the present invention is to provide a heat-resistant resin composition that has low heat resistance and excellent impact resistance, falling ball impact strength, and molding stability. The present invention will be explained in more detail below. 1. Graft polymer (A) The non-conjugated diene-based rubbery polymers constituting the graft polymer (A) include ethylene-propylene copolymer, dicyclopentadiene, ethylidene norbornene, 1.4-hexadiene, and 1.4-cycloheptadiene. , ethylene-propylene polymers (i) such as ethylene-propylene-non-conjugated diene copolymers copolymerized with non-conjugated dienes such as 1.5-cyclooctadiene, methyl acrylate, ethyl acrylate, butyl acrylate, Acrylic ester polymers (ii) such as homopolymers such as propyl acrylate and copolymers with other copolymerizable compounds such as styrene and acrylonitrile, chlorinated polyethylene (iii), and ethylene-vinyl acetate copolymers (iv) One or more polymers selected from the group consisting of, and ethylene-propylene polymers are particularly preferred from the viewpoint of physical property balance. Examples of the aromatic vinyl compound constituting the graft polymer include styrene, α-methylstyrene, methyl-α-methylstyrene, vinyltoluene, and the like. In addition, examples of unsaturated carboxylic acid alkyl ester compounds include methyl acrylate, ethyl acrylate, butyl acrylate,
Methyl methacrylate, ethyl methacrylate,
Examples include butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and glycidyl acrylate and glycidyl methacrylate having an epoxy group in the molecule. There is no particular restriction on the composition ratio of the non-conjugated diene-based rubbery polymer and the compound in the graft polymer (A), but 5 to 70% by weight of the non-conjugated diene-based rubbery polymer;
Preferably it is 30-95% by weight of the compound. In addition, there is no particular restriction on the composition ratio of each compound in the compounds constituting such a polymer, but the aromatic vinyl compound alone or the aromatic vinyl compound 50 to 80%
% by weight and the unsaturated carboxylic acid alkyl ester compound is preferably from 20 to 50% by weight. Examples of methods for producing the graft polymer (A) include emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, emulsion-suspension polymerization, and bulk-suspension polymerization. 2 Copolymer (B) The unsaturated dicarboxylic acid anhydride constituting the copolymer (B) includes maleic anhydride, oxymaleic anhydride, ethoxymaleic anhydride, citraconic anhydride, phthalic anhydride, and itaconic anhydride. etc. Further, examples of the aromatic vinyl compound include styrene, α-methylstyrene, methyl-α-methylstyrene, vinyltoluene, and the like. Furthermore, examples of vinyl cyanide compounds that can be used together with unsaturated dicarboxylic anhydrides and aromatic vinyl compounds include acrylonitrile and methacrylonitrile. There is no particular restriction on the composition ratio of each compound constituting the copolymer (B), but the proportion of unsaturated carboxylic acid anhydride is 0.5
The content is preferably 65% by weight. If it is less than 0.5% by weight, heat resistance tends to deteriorate, and if it exceeds 65% by weight, molding stability tends to deteriorate. Furthermore, the composition ratio of the aromatic vinyl compound and the vinyl cyanide compound is also not particularly limited, but it is preferable to use an aromatic vinyl compound.
50~100% by weight and vinyl cyanide compound 50~
It is 0% by weight. Examples of methods for producing the copolymer (B) include bulk polymerization, solution polymerization, and bulk-suspension polymerization. 3 Polycarbonate (C) Examples of polycarbonate (C) include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like. Generally, 2,2-bis(4-oxyphenyl)
A polymer or copolymer consisting of bisphenols such as alkanes, bis(4-oxyphenyl) ethers, bis(4-oxyphenyl)sulfones, sulfides, or sulfoxides, and is substituted with halogen depending on the purpose. It is a polymer using bisphenols. 4 Composition ratio The heat-resistant resin composition of the present invention comprises 10 to 80% by weight of the above-mentioned graft polymer (A) and 10 to 80% by weight of the copolymer (B).
and 10 to 80% by weight of polycarbonate (C). Graft polymer (A) less than 10% by weight or copolymer
If (B) exceeds 80% by weight, the final composition will have poor light discoloration and impact resistance. If the copolymer (B) is less than 10% by weight or the graft polymer (A) is more than 80% by weight, heat resistance and molding stability will be poor. In addition, polycarbonate (C)
If it is less than 10% by weight, the heat resistance will be poor, and if it exceeds 80% by weight, the molding stability will be poor. The graft polymer (A), copolymer (B) and polycarbonate (C) can be mixed using a known mixer. Alternatively, depending on the purpose of use during mixing, polymers such as polystyrene, styrene-acrylonitrile copolymer, dyes and pigments, stabilizers, plasticizers,
It is also possible to add antistatic agents, ultraviolet absorbers, lubricants, fillers, etc. The present invention will be specifically explained below using Examples, but the present invention is not limited thereto. Examples 1 to 4 1 Method for producing graft polymers (A- and -) Iodine number 8.5, Mooney viscosity 61, propylene content 43% by weight, 500 parts by weight of ethylene-propylene rubber containing dicyclopentadiene as the diene component. Dissolved in 2500 parts by weight of n-hexane and 1500 parts by weight of ethylene dichloride,
450 parts by weight of styrene and benzoyl peroxide
After charging 10 parts by weight, polymerization was carried out at 67° C. for 10 hours under stirring at 600 rpm in a nitrogen atmosphere. Bring the polymerization solution into contact with a large excess of methanol.
After separating and drying the precipitate, the rubber content
52.6% styrene graft polymer (A-1)
I got it. 500 parts by weight of ethylene-propylene rubber containing iodine 8.5, Mooney viscosity 61, propylene content 43% by weight, and ethylidene norbornene as the diene component was dissolved in 2500 parts by weight of n-hexane and 1500 parts by weight of ethylene dichloride,
700 parts by weight of styrene, methyl methacrylate
After adding 300 parts by weight and 10 parts by weight of benzoyl peroxide, the mixture was heated at 67°C for 10 hours in a nitrogen atmosphere.
Polymerization was carried out under stirring at 600 rpm. Bringing the polymerization solution into contact with a large excess of methanol,
After separating and drying the precipitate, the rubber content
A 35.2% styrene-methyl methacrylate graft polymer (A-) was obtained. 2. Method for producing copolymers (B- and -) 70 parts by weight of styrene, 30 parts by weight of maleic anhydride, 0.05 parts by weight of lauroyl peroxide and t-
Add 0.4 parts by weight of dodecyl mercaptan and carry out bulk polymerization at 70°C for 5 hours while purging with nitrogen, then add 0.14 parts by weight of polyvinyl alcohol and 0.06 parts by weight of Metrose in water as a suspension stabilizer.
Add 200 parts by weight and suspend, add 0.5 parts by weight of lauroyl peroxide as an initiator and 0.1 parts by weight of acidic sodium sulfite as an aqueous phase polymerization inhibitor.
Polymerized for hours. The particulate polymer is separated, washed and dried to obtain maleic anhydride-styrene copolymer (B-
) was obtained. 0.05 parts by weight of lauroyl peroxide and 0.4 parts by weight of t-dodecyl mercaptan were added to 70 parts by weight of styrene, 15 parts by weight of acrylonitrile, and 15 parts by weight of maleic anhydride, and the mixture was heated to 70°C while purging with nitrogen.
Bulk polymerization was carried out for 5 hours, and then 0.14 parts by weight of polyvinyl alcohol and Metrose were added as a suspension stabilizer.
Add 230 parts by weight of water in which 0.06 parts by weight was dissolved and suspend.
0.5 parts by weight of lauroyl peroxide as an initiator, acidic sodium sulfite as an aqueous phase polymerization inhibitor
0.1 part by weight was added and polymerized for 3 hours. Separate the particulate polymer, wash and dry to obtain maleic anhydride-styrene-acrylonitrile copolymer (B-)
I got it. 3 Polycarbonate (C) Polycarbonate manufactured by Teijin Kasei Co., Ltd. “Panlite L-1250” Graft polymer (A) and copolymer (B) obtained by the above method and commercially available polycarbonate
(C) was mixed in a 65 mm single screw extruder with the composition shown in Table 1 to obtain various compositions. Table 1 shows the light discoloration resistance, molding stability, heat resistance, impact resistance, processability, and falling ball impact strength of the obtained composition and commercially available modified polyphenylene oxide resin and super heat-resistant ABS resin as comparison products. . Note that the composition ratios indicate parts by weight. 【table】
Claims (1)
よび／または不飽和カルボン酸アルキルエステル
化合物をグラフト重合したグラフト重合体(A)10〜
80重量％、不飽和ジカルボン酸無水物および芳香
族ビニル化合物またはそれらとシアン化ビニル化
合物からなる共重合体(B)10〜80重量％およびポリ
カーボネート(C)10〜80重量％とからなる事を特徴
とする耐熱性樹脂組成物。 ２ 共重合体(B)中の不飽和ジカルボン酸無水物が
0.5〜65重量％である特許請求の範囲第１項記載
の耐熱性樹脂組成物。[Scope of Claims] 1. Graft polymer (A) 10-10 obtained by graft polymerizing an aromatic vinyl compound and/or an unsaturated carboxylic acid alkyl ester compound onto a non-conjugated diene rubber.
80% by weight, 10 to 80% by weight of an unsaturated dicarboxylic anhydride and an aromatic vinyl compound, or a copolymer (B) consisting of them and a vinyl cyanide compound, and 10 to 80% by weight of polycarbonate (C). Characteristic heat-resistant resin composition. 2 The unsaturated dicarboxylic anhydride in the copolymer (B)
The heat-resistant resin composition according to claim 1, wherein the content is 0.5 to 65% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8478184A JPS60226545A (en) | 1984-04-25 | 1984-04-25 | Heat-resistant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8478184A JPS60226545A (en) | 1984-04-25 | 1984-04-25 | Heat-resistant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60226545A JPS60226545A (en) | 1985-11-11 |
| JPH0334781B2 true JPH0334781B2 (en) | 1991-05-23 |
Family
ID=13840232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8478184A Granted JPS60226545A (en) | 1984-04-25 | 1984-04-25 | Heat-resistant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60226545A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101481489B1 (en) * | 2008-05-15 | 2015-01-12 | 동부대우전자 주식회사 | Control Device and Method for Defrosting of Refrigerator |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6065055A (en) * | 1983-08-22 | 1985-04-13 | モンサント・カンパニー | Polyblend |
-
1984
- 1984-04-25 JP JP8478184A patent/JPS60226545A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6065055A (en) * | 1983-08-22 | 1985-04-13 | モンサント・カンパニー | Polyblend |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101481489B1 (en) * | 2008-05-15 | 2015-01-12 | 동부대우전자 주식회사 | Control Device and Method for Defrosting of Refrigerator |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60226545A (en) | 1985-11-11 |
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