JPS6365222B2 - - Google Patents
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- JPS6365222B2 JPS6365222B2 JP58125229A JP12522983A JPS6365222B2 JP S6365222 B2 JPS6365222 B2 JP S6365222B2 JP 58125229 A JP58125229 A JP 58125229A JP 12522983 A JP12522983 A JP 12522983A JP S6365222 B2 JPS6365222 B2 JP S6365222B2
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- 150000001875 compounds Chemical class 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- -1 polyethylenes Polymers 0.000 claims description 17
- 239000011342 resin composition Substances 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 15
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 229920003244 diene elastomer Polymers 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 150000008360 acrylonitriles Chemical class 0.000 claims description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229920006222 acrylic ester polymer Polymers 0.000 claims 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 150000001993 dienes Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 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
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- 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 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- GWYPDXLJACEENP-UHFFFAOYSA-N 1,3-cycloheptadiene Chemical compound C1CC=CC=CC1 GWYPDXLJACEENP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- NMSZFQAFWHFSPE-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)but-3-enoic acid Chemical class OC(=O)CC(=C)C(=O)OCC1CO1 NMSZFQAFWHFSPE-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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-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
- 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
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- UGUYQBMBIJFNRM-UHFFFAOYSA-N but-2-en-2-ylbenzene Chemical compound CC=C(C)C1=CC=CC=C1 UGUYQBMBIJFNRM-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- GOAJGXULHASQGJ-UHFFFAOYSA-N ethene;prop-2-enenitrile Chemical group C=C.C=CC#N GOAJGXULHASQGJ-UHFFFAOYSA-N 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
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 239000008188 pellet Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Description
本発明は優れた艶消し効果を有する耐候性熱可
塑性樹脂組成物に関する。
AES樹脂（アクリロニトリル−エチレン・プ
ロピレン系ゴム−スチレン重合体）で代表される
非共役ジエン系ゴム強化重合体は、耐候性、成形
性、機械的特性等に優れており、車両分野をはじ
め多くの分野への利用が期待されている。
車両分野、特に自動車内装部品は、安全性ある
いは他の部品との調和を重視する傾向より、艶消
しが要望されている。
艶消し部品を得る方法としては、細いエンボス
加工等、金型面から改良する方法および材料を改
質する方法が挙げられる。金型面からの改良では
成形時樹脂を完全に金型に密着させるため、金型
面の磨耗が激しく、エンボス加工を頻繁に実施す
る必要があり、また、成形条件によつて艶の状態
が左右される。
一方、材料面からの改質として、樹脂へのフイ
ラーまたはゴム質重合体の添加が提案されている
が、フイラー添加は、物性および外観の面で好ま
しくなく、ゴム質重合体添加は、成形品表面への
フローマークやウエルドマークが著しく、良好な
成形品が得られないのが現状である。
本発明者等は、非共役ジエン系ゴム強化樹脂が
有する優れた特性を損うことなく、表面特性（艶
消し）に優れる組成物につき鋭意研究した結果、
本発明に到達したものである。
すなわち、本発明は、非共役ジエン系ゴムの存
在下化合物を重合して得られる重合体（耐候性樹
脂）又は該重合体と共重合体とからなる耐候性樹
脂組成物100重量部当り、エポキシ基含有オレフ
イン共重合体0.1〜40重量部配合したことを特徴
とする表面特性（艶消し）に優れる耐候性樹脂組
成物を提供するものである。
以下に本発明について詳細に説明する。
耐候性樹脂又は耐候性樹脂組成物(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。
重合体ならびに共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
ン等が挙げられ、一種又は二種以上用いることが
できる。特にスチレンが好ましい。シアン化ビニ
ル化合物としては、アクリロニトリル、メタクリ
ロニトリル等々が挙げられ、一種又は二種以上用
いることができる。特にアクリロニトリルが好ま
しい。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
クリレート等々が挙げられ、一種又は二種以上用
いることができる。特にメチルメタクリレートが
好ましい。
上述の３種の化合物からなる群より選ばれる２
種以上の化合物が重合体及び共重合体重合時に用
いられる。
重合体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、重合体
単独でもつて耐候性樹脂(A)とする場合は非共役ジ
エン系ゴム質重合体５〜60重量％、化合物40〜95
重量％が好ましく、又、重合体と共重合体の混合
物をもつて耐候性樹脂組成物(A)とする場合は、該
重合体は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50〜80重量％およびシアン化ビニル
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20〜50重量％であることが好まし
い。
共重合体を構成す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50〜80重量％
およびシアン化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20〜50重量
％であることが好ましい。
共重合体は、重合体の重合時に同一反応器中で
作つてもよく、また、別途の反応器で作つてもよ
い。
耐候性樹脂(A)は、上述の重合体単独（第１発
明）、又耐候性樹脂組成物(A)は、上述の重合体５
重量％と共重合体95重量％以下からなる組成物
（第２発明）である。
耐候性樹脂組成物における重合体が５重量％未
満では最終組成物の耐衝撃性が劣り好ましくな
い。最終組成物の耐衝撃性と加工性のバランスな
らびに耐候性樹脂組成物の生産面より、耐候性樹
脂(A)又は耐候性樹脂組成物(A)における非共役ジエ
ン系ゴム質重合体の含有量が５〜60重量％である
ことが好ましい。
さらに、本発明において用いられるエポキシ基
含有オレフイン共重合体とは、不飽和エポキシ化
合物とオレフインまたは、これらとエチレン系不
飽和化合物からなる共重合体である。エポキシ基
含有オレフイン共重合体の組成比には特に制限は
ないが、不飽和エポキシ化合物0.05〜95重量％で
あることが好ましい。
不飽和エポキシ化合物としては、分子中にオレ
フインおよびエチレン系不飽和化合物と共重合し
うる不飽和基と、エポキシ基をそれぞれ有する化
合物である。
例えば、下記一般式（）、（）および（）
で表わされるような不飽和グリシジルエステル
類、不飽和グリシジルエーテル類、エポキシアル
ケン類、Ｐ−グリシジルスチレン類などの不飽和
エポキシ化合物である。
（Ｒはエチレン系不飽和結合を有するC2〜18の炭
化水素基である。）
（Ｒはエチレン系不飽和結合を有するC2〜18の炭
化水素基である。ＸはCH2−Ｏ−、
The present invention relates to weatherable thermoplastic resin compositions having excellent matte effects. Non-conjugated diene rubber-reinforced polymers, represented by AES resin (acrylonitrile-ethylene/propylene rubber-styrene polymer), have excellent weather resistance, moldability, mechanical properties, etc., and are used in many applications including the vehicle field. It is expected to be used in various fields. In the vehicle field, particularly for automobile interior parts, matte finish is desired due to the tendency to emphasize safety or harmony with other parts. Methods for obtaining matte parts include methods of improving the mold surface, such as fine embossing, and methods of modifying the material. When improving the mold surface, the resin completely adheres to the mold during molding, which causes severe wear on the mold surface, requiring frequent embossing, and the gloss condition may vary depending on the molding conditions. Depends on it. On the other hand, the addition of fillers or rubbery polymers to resins has been proposed as a material modification, but adding fillers is unfavorable in terms of physical properties and appearance, and adding rubbery polymers does not improve the quality of molded products. Currently, flow marks and weld marks on the surface are significant, making it difficult to obtain good molded products. As a result of intensive research into a composition that has excellent surface properties (matte) without impairing the excellent properties of non-conjugated diene rubber-reinforced resins, the present inventors found that
This has led to the present invention. That is, the present invention provides epoxy resin per 100 parts by weight of a polymer (weather-resistant resin) obtained by polymerizing a compound in the presence of a non-conjugated diene rubber or a weather-resistant resin composition consisting of the polymer and a copolymer. The present invention provides a weather-resistant resin composition with excellent surface properties (matte), which is characterized by containing 0.1 to 40 parts by weight of a group-containing olefin copolymer. The present invention will be explained in detail below. The non-conjugated diene-based rubbery polymer constituting the weather-resistant resin or weather-resistant resin composition (A) includes ethylene-propylene copolymer, dicyclopentadiene, ethylidene norbornene, 1.4-hexadiene, 1.4-
Ethylene-propylene polymers (i) such as ethylene-propylene-non-conjugated diene copolymer copolymerized with non-conjugated dienes such as cycloheptadiene and 1.5-cyclooctadiene, methyl acrylate, ethyl acrylate, acrylic Acrylic acid ester polymers (ii), such as homopolymers such as butyl acrylate and propyl acrylate, and copolymers with other copolymerizable compounds such as styrene and acrylonitrile, chlorinated polyethylene (iii), and ethylene-vinyl acetate. copolymer
One or more polymers selected from the group consisting of (iv), and ethylene-propylene polymers are particularly preferred from the viewpoint of physical property balance. Examples of the aromatic vinyl compound constituting the polymer and copolymer include styrene, α-methylstyrene, methyl-α-methylstyrene, vinyltoluene, etc., and one or more types can be used. Styrene is particularly preferred. Examples of vinyl cyanide compounds include acrylonitrile, methacrylonitrile, etc., and one or more types can be used. Acrylonitrile is particularly preferred. Examples of the unsaturated carboxylic acid alkyl ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc., and one or more of them may be used. be able to. Particularly preferred is methyl methacrylate. 2 selected from the group consisting of the above three types of compounds
More than one type of compound may be used during polymerization of polymers and copolymers. There is no particular restriction on the composition ratio of the non-conjugated diene-based rubbery polymer and the compound in the polymer, but when using the polymer alone as a weather-resistant resin (A), the non-conjugated diene-based rubbery polymer 5- 60% by weight, compounds 40-95
% by weight is preferable, and when the weather-resistant resin composition (A) is made of a mixture of a polymer and a copolymer, the polymer is 5 to 70% by weight of a non-conjugated diene rubbery polymer, a compound Preferably, it is 30 to 95% by weight. In addition, there is no particular restriction on the composition ratio of each compound in the compounds constituting such a polymer; Preferably, it is % by weight. There are no particular restrictions on the composition ratio of each compound constituting the copolymer, but the aromatic vinyl compound should be 50 to 80% by weight.
and vinyl cyanide compound and/or unsaturated carboxylic acid alkyl ester compound is preferably 20 to 50% by weight. The copolymer may be produced in the same reactor during polymerization, or may be produced in a separate reactor. The weather-resistant resin (A) is the above-mentioned polymer alone (first invention), and the weather-resistant resin composition (A) is the above-mentioned polymer 5.
This is a composition (second invention) consisting of 95% by weight or less of a copolymer. If the amount of the polymer in the weather-resistant resin composition is less than 5% by weight, the final composition will have poor impact resistance, which is not preferred. The content of the non-conjugated diene-based rubbery polymer in the weather-resistant resin (A) or the weather-resistant resin composition (A) is determined from the viewpoint of the balance between impact resistance and processability of the final composition and the production of the weather-resistant resin composition. is preferably 5 to 60% by weight. Furthermore, the epoxy group-containing olefin copolymer used in the present invention is a copolymer consisting of an unsaturated epoxy compound and an olefin, or these and an ethylenically unsaturated compound. Although there is no particular restriction on the composition ratio of the epoxy group-containing olefin copolymer, it is preferably 0.05 to 95% by weight of the unsaturated epoxy compound. The unsaturated epoxy compound is a compound having an epoxy group and an unsaturated group copolymerizable with an olefin and an ethylenically unsaturated compound in the molecule. For example, the following general formulas (), () and ()
These are unsaturated epoxy compounds such as unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxy alkenes, and P-glycidyl styrenes. (R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond.) (R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond. X is CH2 -O-,
【式】または[expression] or
【式】であ
る。）
（Ｒはエチレン系不飽和結合を有するC2〜18の炭
化水素基である。R′は水素またはメチル基であ
る。）
具体的にはグリシジルアクリレート、グリシジ
ルメタクリレート、イタコン酸グリシジルエステ
ル類、ブテンカルボン酸エステル類、アリルグリ
シジルエーテル、２−メチルアリルグリシジルエ
ーテル、スチレン−Ｐ−グリシジルエーテル、
3.4−エポキシブテン、3.4−エポキシ−３−メチ
ル−１−ブテン、3.4−エポキシ−１−ペンテン、
3.4−エポキシ−３−メチルペンテン、5.6−エポ
キシ−１−ヘキセン、ビニルシクロヘキセンモノ
オキシド、Ｐ−グリシジルスチレンなどが挙げら
れ、一種又は二種以上用いることができる。特に
グリシジルメタクリレートが好ましい。
オレフインとしては、エチレン、プロピレン、
ブテン−１、４−メチルペンテン１などが挙げら
れ、一種又は二種以上用いることができる。特に
エチレンおよびプロピレンが好ましい。
また、エチレン系不飽和化合物としては、オレ
フイン類、飽和カルボン酸成分にC2〜6を含むビニ
ルエステル類、飽和アルコール成分にC1〜8を含む
アクリル酸およびメタクリル酸エステル類および
マレイン酸エステル類、ハロゲン化ビニル類、ビ
ニルエーテル類、Ｎ−ビニルラクタム類、カルボ
ン酸アミド類などが挙げられ、一種又は二種以上
用いることができる。
これらのエチレン系不飽和化合物は、不飽和エ
ポキシ化合物とオレフインとの共重合の際、全化
合物に対して50重量％以下、特に0.1〜45重量％
共重合される。
エポキシ基含有オレフイン共重合体は種々の方
法で作ることができる。例えば、不飽和エポキシ
化合物とオレフイン、場合によつてはエチレン系
不飽和化合物をラジカル発生剤の存在下、50〜
4000気圧、40〜300℃で接触させる方法、ポリプ
ロピレンに不飽和エポキシ化合物を混合し、高真
空下ガンマ線を照射して重合体を作る方法等が挙
げられる。
エポキシ基含有オレフイン共重合体の配合量
は、耐候性樹脂(A)又は耐候性樹脂組成物(A)100重
量部当り0.1〜40重量部である。
0.1重量部未満では分散性に問題があり、また、
40重量部を超えると成形品に層剥離が発生する傾
向がある。
本発明の耐候性熱可塑性樹脂組成物は耐候性樹
脂（組成物）とエポキシ基含有オレフイン共重合
体とを通常の混合技術、例えば一軸又は二軸押出
機、バンバリーミキサー等によつて得ることがで
きる。
また、耐候性樹脂（組成物）100重量部とエポ
キシ基含有オレフイン共重合体0.1〜40重量部を
超す多量の該共重合体を配合し、艶消しマスーバ
ツチを作成した後、それを添加剤として耐候性樹
脂（組成物）と混合して艶消し特性に優れた耐候
性熱可塑性樹脂組成物を得ることも可能である。
なお、混合に際して公知の安定剤、帯電防止
剤、滑剤、染願料などの添加剤を適宜配合しても
よい。
以下に実施例を挙げて説明するが、本発明はこ
れらによつて何ら制限されるものでない。
実施例
耐候性樹脂（組成物）にエポキシ基含有オレフ
イン共重合体または一般的な公知の艶消し剤を配
合し、バンバリーミキサーで混練後、ペレツト化
した。
得られたペレツトより常法に基づき各種試験片
を作成し、物性ならびに表面光沢を測定した。
各組成物の組成ならびに物性、表面光沢を表−
１に示す。
なお、本実施例で用いられた耐候性樹脂（組成
物）及びエポキシ基含有オレフイン共重合体は以
下の方法により得られた共重合体である。
Γ耐候性樹脂（組成物）
エチレン−プロピレン−エチリデンノルボル
ネン（ヨウ素価8.5、ムーニー粘度61、プロピ
レン含有量43重量％）20重量％、スチレン55重
量％およびアクリロニトリル25重量％を公知の
溶液重合法により重合を行いAES樹脂を得た。
また、エチレン−プロピレン−エチリデンノ
ルボルネン30重量部、スチレン50重量％および
アクリロニトリル20重量％を公知の懸濁重合法
により重合を行い、別途懸濁重合されたスチレ
ン−アクリロニトリル共重合体（70／30）と
１：１の割合にてビーズ状で混合しAES樹脂
組成物を得た。
Γエポキシ基含有オレフイン共重合体
通常のオートクレープ型ポリエチレン製造装
置に2000Kg／cm2まで圧縮されたエチレンモノマ
ーおよびグリシジルメタクリレート、またはそ
れらと酢酸ビニルを触媒（ジ−ｔ−ブチルパー
オキサイド）とともに加え、撹拌しながら150
〜300℃に維持して数分間塊状重合させ、セパ
レーターを通して共重合体を分離し、取り出し
た。[Formula]. ) (R is a C2-18 hydrocarbon group having an ethylenically unsaturated bond. R' is hydrogen or a methyl group.) Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxyl acid esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-P-glycidyl ether,
3.4-epoxybutene, 3.4-epoxy-3-methyl-1-butene, 3.4-epoxy-1-pentene,
Examples include 3.4-epoxy-3-methylpentene, 5.6-epoxy-1-hexene, vinylcyclohexene monoxide, and P-glycidylstyrene, and one or more of them can be used. Glycidyl methacrylate is particularly preferred. Olefins include ethylene, propylene,
Examples include butene-1, 4-methylpentene-1, etc., and one or more types can be used. Particularly preferred are ethylene and propylene. In addition, as ethylenically unsaturated compounds, olefins, vinyl esters containing C 2 to 6 in the saturated carboxylic acid component, acrylic and methacrylic esters and maleic esters containing C 1 to 8 in the saturated alcohol component , vinyl halides, vinyl ethers, N-vinyl lactams, carboxylic acid amides, etc., and one or more types can be used. When copolymerizing an unsaturated epoxy compound and an olefin, these ethylenically unsaturated compounds are added in an amount of 50% by weight or less, especially 0.1 to 45% by weight based on the total compound.
Copolymerized. Epoxy group-containing olefin copolymers can be made by various methods. For example, an unsaturated epoxy compound and an olefin, in some cases an ethylenically unsaturated compound, are combined in the presence of a radical generator for 50 to
Examples include a method of contacting at 4000 atm and 40 to 300°C, and a method of preparing a polymer by mixing an unsaturated epoxy compound with polypropylene and irradiating it with gamma rays under high vacuum. The blending amount of the epoxy group-containing olefin copolymer is 0.1 to 40 parts by weight per 100 parts by weight of the weather-resistant resin (A) or the weather-resistant resin composition (A). If it is less than 0.1 part by weight, there will be problems with dispersibility, and
If it exceeds 40 parts by weight, layer peeling tends to occur in the molded product. The weather-resistant thermoplastic resin composition of the present invention can be obtained by mixing the weather-resistant resin (composition) and the epoxy group-containing olefin copolymer using a conventional mixing technique, such as a single-screw or twin-screw extruder, a Banbury mixer, etc. can. In addition, 100 parts by weight of a weather-resistant resin (composition) and a large amount of the epoxy group-containing olefin copolymer (more than 0.1 to 40 parts by weight) are blended to create a matte mass batch, and then used as an additive. It is also possible to obtain a weather-resistant thermoplastic resin composition with excellent matte properties by mixing it with a weather-resistant resin (composition). In addition, known additives such as stabilizers, antistatic agents, lubricants, dyes, etc. may be appropriately blended during mixing. Examples will be described below, but the present invention is not limited thereto. EXAMPLE An epoxy group-containing olefin copolymer or a commonly known matting agent was blended with a weather-resistant resin (composition), and the mixture was kneaded with a Banbury mixer and pelletized. Various test specimens were prepared from the obtained pellets according to conventional methods, and physical properties and surface gloss were measured. The composition, physical properties, and surface gloss of each composition are shown.
Shown in 1. The weather-resistant resin (composition) and epoxy group-containing olefin copolymer used in this example were copolymers obtained by the following method. Γ Weather-resistant resin (composition) 20% by weight of ethylene-propylene-ethylidenenorbornene (iodine value 8.5, Mooney viscosity 61, propylene content 43% by weight), 55% by weight of styrene and 25% by weight of acrylonitrile by a known solution polymerization method. Polymerization was performed to obtain AES resin. In addition, 30 parts by weight of ethylene-propylene-ethylidenenorbornene, 50% by weight of styrene and 20% by weight of acrylonitrile were polymerized by a known suspension polymerization method, and a styrene-acrylonitrile copolymer (70/30) was separately polymerized by suspension polymerization. AES resin composition was obtained by mixing the resin in the form of beads at a ratio of 1:1. Γ Epoxy group-containing olefin copolymer Add ethylene monomer and glycidyl methacrylate compressed to 2000 kg/cm 2 , or both and vinyl acetate together with a catalyst (di-t-butyl peroxide) to a normal autoclave type polyethylene manufacturing equipment. 150 while stirring
Bulk polymerization was maintained at ~300°C for several minutes, and the copolymer was separated through a separator and taken out.
【表】【table】
Claims (1)
族ビニル化合物、シアン化ビニル化合物および不
飽和カルボン酸アルキルエステル化合物からなる
群より選ばれる２種以上の化合物を重合して得ら
れる重合体である耐候性樹脂(A)100重量部当り、
不飽和エポキシ化合物とオレフイン又はそれらと
エチレン系不飽和単量体とからなるエポキシ基含
有オレフイン共重合体(B)0.1〜40重量部配合した
ことを特徴とする耐候性熱可塑性樹脂組成物。 ２ 非共役ジエン系ゴム質重合体がエチレン−プ
ロピレン系重合体、アクリル酸エステル系重合
体、塩素化ポリエチレンおよびエチレン−酢酸ビ
ニル共重合体からなる群より選ばれた１種以上の
重合体である特許請求の範囲第１項記載の組成
物。 ３ 非共役ジエン系ゴム質重合体の存在下、芳香
族ビニル化合物、シアン化ビニル化合物および不
飽和カルボン酸アルキルエステル化合物からなる
群より選ばれる２種以上の化合物を重合して得ら
れる重合体(a)５重量％以上および芳香族ビニル化
合物、シアン化ビニル化合物および不飽和カルボ
ン酸アルキルエステル化合物からなる群より選ば
れる２種以上の化合物を重合して得られる共重合
体(b)95重量％以下からなる耐候性樹脂組成物(A)
100重量部当り、不飽和エポキシ化合物とオレフ
イン又はそれらとエチレン系不飽和単量体とから
なるエポキシ基含有オレフイン共重合体(B)0.1〜
40重量部配合したことを特徴とする耐候性熱可塑
性樹脂組成物。 ４ 非共役ジエン系ゴム質重合体がエチレン−プ
ロピレン系重合体、アクリル酸エステル系重合
体、塩素化ポリエチレンおよびエチレン−酢酸ビ
ニル共重合体からなる群より選ばれた１種以上の
重合体である特許請求の範囲第３項記載の組成
物。[Scope of Claims] 1. Two or more compounds selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated carboxylic acid alkyl ester compounds are polymerized in the presence of a nonconjugated diene rubbery polymer. Per 100 parts by weight of weather-resistant resin (A), which is a polymer obtained by
1. A weather-resistant thermoplastic resin composition comprising 0.1 to 40 parts by weight of an epoxy group-containing olefin copolymer (B) consisting of an unsaturated epoxy compound and an olefin, or an ethylenically unsaturated monomer. 2. The non-conjugated diene rubbery polymer is one or more polymers selected from the group consisting of ethylene-propylene polymers, acrylic ester polymers, chlorinated polyethylenes, and ethylene-vinyl acetate copolymers. A composition according to claim 1. 3. A polymer obtained by polymerizing two or more compounds selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, and an unsaturated carboxylic acid alkyl ester compound in the presence of a nonconjugated diene rubbery polymer ( Copolymer (b) 95% by weight obtained by polymerizing a) 5% by weight or more and two or more compounds selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated carboxylic acid alkyl ester compounds Weather-resistant resin composition (A) consisting of the following:
Epoxy group-containing olefin copolymer (B) consisting of an unsaturated epoxy compound and olefin or these and an ethylenically unsaturated monomer (B) 0.1 to 100 parts by weight
A weather-resistant thermoplastic resin composition characterized by containing 40 parts by weight. 4. The non-conjugated diene rubbery polymer is one or more polymers selected from the group consisting of ethylene-propylene polymers, acrylic ester polymers, chlorinated polyethylenes, and ethylene-vinyl acetate copolymers. A composition according to claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12522983A JPS6018536A (en) | 1983-07-08 | 1983-07-08 | Weather-resistant thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12522983A JPS6018536A (en) | 1983-07-08 | 1983-07-08 | Weather-resistant thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6018536A JPS6018536A (en) | 1985-01-30 |
| JPS6365222B2 true JPS6365222B2 (en) | 1988-12-15 |
Family
ID=14905013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12522983A Granted JPS6018536A (en) | 1983-07-08 | 1983-07-08 | Weather-resistant thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6018536A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0730228B2 (en) * | 1987-08-18 | 1995-04-05 | 住友ダウ株式会社 | Matte thermoplastic resin composition |
| US5827608A (en) * | 1996-10-28 | 1998-10-27 | Minnesota Mining And Manufacturing Company | Method of forming a thermoplastic layer on a flexible two-dimensional substrate and powder for preparing same |
| NZ506357A (en) | 1998-03-11 | 2003-03-28 | Minnesota Mining & Mfg | Method of forming a thermoplastic layer on a layer of adhesive |
| US20110077355A1 (en) | 2007-08-21 | 2011-03-31 | Yoshifumi Shikisai | Method Of Producing Enlarged Rubber, Graft Copolymer, Thermoplastic Resin Composition And Molded Article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49109432A (en) * | 1973-02-21 | 1974-10-17 | ||
| JPS5034645A (en) * | 1973-07-25 | 1975-04-03 | ||
| JPS5989346A (en) * | 1982-11-12 | 1984-05-23 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition |
-
1983
- 1983-07-08 JP JP12522983A patent/JPS6018536A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49109432A (en) * | 1973-02-21 | 1974-10-17 | ||
| JPS5034645A (en) * | 1973-07-25 | 1975-04-03 | ||
| JPS5989346A (en) * | 1982-11-12 | 1984-05-23 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6018536A (en) | 1985-01-30 |
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