1338018 九、發明說明： 【發明所屬之技術領域】 本發明係與橡膠改質笨乙烯系樹脂有關，特別是指一 種具有良好的光澤度及耐衝擊強度的物性平衡之橡膠改質 本乙稀系樹脂組成物。 【先前技術】 一般橡膠改質苯乙稀系樹脂，因其加工成型性、機械 性方面皆有良好之評價，尤其是成型品的良好外觀及光澤 性上更是其一大特色，所以被廣泛使用在電子、電器用品 及汽車零件上。 但對於橡膠改質苯乙烯系樹脂而言，為了要達到更大 的使用領域往往要求具有良好的高光澤及耐衝擊性的特 性，而一般的橡膠改質笨乙烯系樹脂係由笨乙烯系_丙烯腈 系共聚物及橡膠接枝共聚物混練而得。過去橡膠改質笨乙 烯系樹脂的聚合技術大部份為乳化聚合而得，因其橡膠粒 子的重量平均粒徑較小’具有高光澤及耐衝擊性的性質， 但由於乳化聚合技術其所衍生廢水廢液的問題，在近來環 保要求下’橡膠改質苯乙烯系樹脂的聚合技術改為總體 (Bulk)或溶液(Solution)聚合，但因總體或溶液聚合方式 所得之橡膠改質苯乙烯系樹脂成型品光澤度較低，無法滿 足使用者的要求，在環保的考量之下，如何獲得兼具高光 澤及耐衝擊特性之橡膠改質苯乙烯系樹脂乃變成急欲解決 的課題；本發明即針對此一課題，經銳意研究乃提供一種 具有高光澤及耐衝擊性物性的物性平衡之橡膠改質笨乙稀 系樹脂組成物。 5 1338018 【發明目的】 本發明之目的在於提供一種具有良好光澤及耐衝擊性 之物性平衡之橡膠改質笨乙烯系樹脂組成物。 【發明内容】 本案發明人經銳意研究後發明一種橡膠改質笨乙烯系 樹脂組成物，是由：（i-Ι)笨乙烯系單體5〇〜9〇重量份、 (i-2)腈化乙烤系單體50〜10重量份，以上（丨_1)、（卜2) 單體合計1GG 4量份及(i-3)G.l〜8.G重量份的丙稀酸g旨 系單體構成之共聚物連續相（A)與橡膠狀聚合物形成的橡 膠粒子分散相（B)所組成；其中，橡膠改質笨乙烯系樹脂組 成物之橡膠含有量1〜40重量％，該分散相（幻為内含吸藏 粒子構造（Salami)的橡膠粒子，其橡膠粒子之中位粒徑 (Median particle size)0· 25〜0.6"m，且橡膠粒子之粒 徑分佈寬幅0.3〜1.4。 本發明所使用之橡膠狀聚合物的具體例有：二烯系橡 膠、聚烯烴橡膠(例如：乙烯-丙烯橡膠）、聚丙烯酸酯系橡 膠、聚矽氧烷系橡膠等。前述二烯系橡膠乃爲：二稀系單 體成份經聚合後玻璃轉移溫度在以下的聚合體，二稀系 橡膠的具體例：丁二烯橡膠、異戊二烯橡膠、氣丁二烯橡 膠、乙烯-丙烯-二烯橡膠(EPDM橡膠）、苯乙烯-二稀系橡 膠、丙烤腈-一烯系橡膠等；其中，丁二烯橡膠有高順式 (Hi-Cis)含量及低順式(L〇w-Cis)含量的分別；高順式橡膠 中，其順式(Cis)/乙稀基(Vinyl)的典型重量組成爲（94〜 99%)/(0〜5%)，其餘組成則爲反式（Trans)結構；其木尼 (Mooney)黏度在20〜120間，分子量範圍以1〇〇 〇〇〇〜 6 1338018 800, 000爲佳；低順式橡膠中，順式/乙烯基的典型重量組 成範圍在(20〜40%)/(6〜20%)’其餘爲反式結構，其Mooney 黏度在20〜120間，分子量範圍以100, 000〜800, 000爲 佳。苯乙烯-二烯系橡膠的具體例如笨乙烯-丁二烯橡膠、 苯乙烯-異戊二烯橡膠等，橡膠聚合體構造中可具有均聚物 嵌段構造（Homopolymer block structure)、無規構造 (random structure)或組成漸增或漸減的構造（taper structure)，或前述構造之混合構造，例如：苯乙烯-丁二 稀-苯乙稀嵌段(S-B-S)、苯乙稀-無規苯乙稀/丁二稀-苯乙 烯嵌段(S-randomS/B-S)、笨乙稀-組成漸增或漸減苯乙稀 /丁二烯-笨乙烯嵌段(S-taper S/B-S)、丁二烯-組成漸增 或漸減苯乙浠/丁二稀-笨乙浠嵌段(β-taperS/B-S)、無規 苯乙烯/丁二烯嵌段(random S/B)、丁二烯-無規苯乙婦/丁 一稀-丁一*稀嵌段(B*~random S/B_B)、丁二稀-無規苯乙稀/ 丁二烯嵌段(B-random S/B)等，前述橡膠聚合物可為線性 或分歧構造，木尼(Mooney)黏度(MLih)為20〜80，25。(：之5 重里％的本乙稀半體溶液的黏度為3〜6〇cps ’而二稀系單體 中之1，2-乙烯基（1，2-vinyl)結構含有量佔8重量％以上， 聚苯乙烯嵌段之含量佔橡膠狀聚合物的5〜35重量％，分子 量範圍較佳爲50, 000〜600, 〇〇〇。 上述橡膠狀聚合物可以二種或二種以上之橡膠並用或 單獨使用皆可，例如：（1)單獨使用線性構造之具有漸增或 漸減之苯乙烯/丁二烯構造之橡膠、（2)分歧構造之丁二烯 -(無規笨乙烯/丁二烯)-丁二稀嵌段橡膠、（3)線性構造之 具有漸增或漸減笨乙烯/ 丁二烯構造之橡膠與分歧構造之 7 1338018 丁二烯橡膠並用，其中以單獨使用線性構造之具有漸增或 漸減苯乙烯/ 丁二烯構造之橡膠為佳。 上述橡膠狀聚合物之笨乙烯系單體的具體例 ，例如： 苯乙烯、α-甲基苯乙烯、對-甲基苯乙稀、間一甲基苯乙烯、 鄰-甲基苯乙稀、乙基笨乙烯、2, 4-二甲基笨乙烯、對-第 二丁基苯乙烯、曱基-對-甲基苯乙烯、溴_苯乙烯、二 溴-笨乙烯、2, 4, 6-三溴苯乙烯等，上述苯乙烯系單體可單 獨使用或數種合併使用。 上述橡膠狀聚合物之二烯系單體的具體例，例如：丨，3_ 丁二烯、甲基一1，3-丁二烯、2, 3-二甲基-1，3-丁二烯、i，3— 戊一稀、1,3-己一稀等，上述各具體例可單獨使用一種或 兩種以上混合使用，其中，又以1，3-丁二烯或2-甲基_丨，3_ 丁-稀為較佳。 本發明之共聚物連續相（A)包含（i-Ι)苯乙稀系單體5〇 〜90重量份、（i-2)腈化乙烯系單體50〜10重量份，以上 (i-l)、（i-2)單體合計100重量份及（i-3)〇. 1〜8 〇重量份 的丙烯酸酯系單體所構成’其中，（i-Ι)笨乙烯系單體之具 體例子如前述橡膠聚合物之苯乙烯系單體，不再重覆列舉 說明；本發明共聚物連續相（A)中之笨乙烯系單體構成成份 含量為50〜90重量份’較佳為60〜86重量份，更佳為65 〜84重量份。 本發明所使用的（i-2)腈化乙烯系單體的具體例子 如：丙烯腈、α-甲基丙烯腈等，其中以丙烯腈為較佳。基 於上述（i-1)、（i-2)合計100重量份，本發明的共聚物^ 續相(A)中，（i-2)腈化乙烯系單體構成成份含量爲5〇〜1〇 8 13380181338018 IX. Description of the invention: [Technical field of the invention] The present invention relates to a rubber modified stupid vinyl resin, in particular to a rubber modified with a good gloss and impact strength. Resin composition. [Prior Art] General rubber-modified styrene-based resin has a good evaluation for its formability and mechanical properties, especially for its good appearance and gloss, so it is widely used. Used in electronics, electrical appliances and automotive parts. However, for rubber-modified styrene-based resins, in order to achieve a larger field of use, it is often required to have good high gloss and impact resistance characteristics, and a general rubber-modified stupid vinyl resin is made of stupid vinyl _ The acrylonitrile-based copolymer and the rubber graft copolymer are obtained by kneading. In the past, the polymerization technology of rubber modified stupid vinyl resin was mostly obtained by emulsion polymerization, because the weight average particle diameter of rubber particles is small, which has high gloss and impact resistance, but it is derived from emulsion polymerization technology. The problem of wastewater waste liquid, under the recent environmental protection requirements, the polymerization technology of rubber-modified styrene resin is changed to bulk (Bulk) or solution polymerization, but the rubber modified styrene obtained by the whole or solution polymerization method The resin molded article has low glossiness and cannot meet the requirements of the user. Under environmental considerations, how to obtain a rubber-modified styrene-based resin having both high gloss and impact resistance becomes an urgent problem to be solved; That is, for this subject, it has been intensively studied to provide a rubber-modified stupid ethylene resin composition having a physical balance of high gloss and impact resistance. 5 1338018 [Object of the Invention] An object of the present invention is to provide a rubber-modified stupid vinyl resin composition having a balance of physical properties of good gloss and impact resistance. SUMMARY OF THE INVENTION The inventors of the present invention have intensively studied and invented a rubber modified stupid vinyl resin composition, which is composed of: (i-Ι) stupid vinyl monomer 5〇~9〇 parts by weight, (i-2) nitrile 50 to 10 parts by weight of the baking monomer, the above (丨_1), (b 2) monomer total 1GG 4 parts by weight, and (i-3) G1~8.G parts by weight of acrylic acid g a continuous phase (A) of a copolymer composed of a monomer and a rubber particle dispersed phase (B) formed of a rubbery polymer; wherein the rubber content of the rubber-modified ethylene resin composition is 1 to 40% by weight, A dispersed phase (a rubber particle containing a smear particle structure (Salami) having a median particle size of 0·25 to 0.6" m and a particle size distribution of 0.3 of a rubber particle. ～1.4. Specific examples of the rubbery polymer used in the present invention include a diene rubber, a polyolefin rubber (for example, an ethylene-propylene rubber), a polyacrylate rubber, a polyoxyalkylene rubber, and the like. The olefinic rubber is a polymer having a glass transition temperature of the following dilute monomer components after polymerization, and a dilute rubber Specific examples: butadiene rubber, isoprene rubber, gas butadiene rubber, ethylene-propylene-diene rubber (EPDM rubber), styrene-diuretic rubber, acrylic acid-acrylonitrile-monoethylene rubber, etc. Among them, butadiene rubber has high cis (Hi-Cis) content and low cis (L〇w-Cis) content; in high cis rubber, cis (Cis) / ethylene (Vinyl) The typical weight composition is (94~99%) / (0~5%), and the rest of the composition is trans (Trans) structure; its Mooney viscosity is between 20~120, and the molecular weight range is 1〇〇. 〇〇〇~ 6 1338018 800,000 is preferred; in low cis rubber, the typical weight composition of cis/vinyl is in the range of (20~40%) / (6~20%) 'the rest is trans structure, its Mooney has a viscosity of 20 to 120 and a molecular weight range of 100,000 to 800,000. Specific examples of styrene-diene rubber such as stupid ethylene-butadiene rubber, styrene-isoprene rubber, etc. The polymer structure may have a homopolymer block structure, a random structure, or a taper structure having an increasing or decreasing composition, or a hybrid structure of the structure, for example: styrene-butadiene-styrene block (SBS), styrene-random styrene/butadiene-styrene block (S-randomS/BS), Stupid ethylene - composition of increasing or decreasing styrene / butadiene - stupid ethylene block (S-taper S / BS), butadiene - composition of increasing or decreasing phenethyl hydrazine / dibutyl - stupid Block (β-taperS/BS), random styrene/butadiene block (random S/B), butadiene-random benzophenone/butadiene-butyl-*diluted block (B* ~random S/B_B), butyl diene-random styrene/butadiene block (B-random S/B), etc., the aforementioned rubber polymer may be linear or divergent structure, Mooney viscosity ( MLih) is 20 to 80, 25. (The viscosity of the Ethylene half solution of 5% is 3~6〇cps', and the content of 1,2-vinyl (1,2-vinyl) in the dicholine monomer is 8% by weight. The content of the polystyrene block is 5 to 35 wt% of the rubbery polymer, and the molecular weight range is preferably 50,000 to 600, 〇〇〇. The rubbery polymer may be two or more kinds of rubber. It can be used either alone or separately, for example: (1) a linearly constructed rubber with an increasing or decreasing styrene/butadiene structure, and (2) a divergent structure of butadiene- (a random stupid ethylene/butyl) a diene-butadiene block rubber, (3) a linearly structured rubber having an increasing or decreasing abrupt ethylene/butadiene structure and a divergent structure of 7 1338018 butadiene rubber, wherein a linear structure is used alone A rubber having an increasing or decreasing styrene/butadiene structure is preferred. Specific examples of the stupid vinyl monomer of the above rubbery polymer, for example, styrene, α-methylstyrene, p-methylphenylethyl Dilute, m-methylstyrene, o-methylstyrene, ethyl streptoethylene, 2,4-dimethyl Ethylene, p-butyl butyl styrene, mercapto-p-methyl styrene, bromine styrene, dibromo-phenylene, 2,4,6-tribromostyrene, etc., the above styrene monomer These may be used singly or in combination of several. Specific examples of the diene monomer of the above rubbery polymer, for example, hydrazine, 3 - butadiene, methyl - 1,3-butadiene, 2, 3-dimethyl 1,3-butadiene, i, 3, pentapon, 1,3-hexanthene, etc., each of the above specific examples may be used alone or in combination of two or more, of which 1,3- Butadiene or 2-methyl-hydrazine, 3-butane-diluted is preferred. The continuous phase (A) of the copolymer of the present invention comprises (i-fluorene) styrene monomer 5 〇 to 90 parts by weight, (i -2) 50 to 10 parts by weight of the nitrile vinyl monomer, 100 parts by weight of the above (il) and (i-2) monomers, and (i-3) 〇. 1 to 8 parts by weight of the acrylate series The specific composition of the (i-Ι) stupid vinyl monomer, such as the styrene monomer of the rubber polymer described above, is not repeatedly illustrated; the stupid phase in the continuous phase (A) of the copolymer of the present invention The content of the vinyl monomer component is 50 to 90 parts by weight. It is preferably 60 to 86 parts by weight, more preferably 65 to 84 parts by weight. Specific examples of the (i-2) nitridinated vinyl monomer used in the present invention are acrylonitrile, α-methacrylonitrile, and the like. Among them, acrylonitrile is preferred. Based on 100 parts by weight of the above (i-1) and (i-2), the copolymer of the present invention (S), (i-2) nitrileated vinyl series Body composition content is 5〇~1〇8 1338018
聚合 條件 進料組成 _1 實施例及比較例 Θ涞 雜雜 〇>>· EE- W* α 攪拌速度 反應器溫度 δ δ δ 7〇 δ δ 70 乙笨 甲基丙烯酸曱酯 正-丙烯酸丁酯 OD 笨乙烯 橡穋狀共聚物 (重量1¾ ) (rpm) (°C) 1 (重量份）1 r—V r«r >w/ 1 (重量份）1 1 (重量份）1 1 (重量份）1 1 (重量份）1 ς_π cn ro 00 S cn 05 <=> 1—1 ο ς〇 CJ1 43. 0 C5 Ο ο ui CO Γ° o 05 po o 112j 實施例1 cji (LH r〇 00 g i; CJi C3 ο i CO cn CO <=> Ο <=> ο CO ro cz> 05 oo o 1__I2J ro 〇1 ΟΊ ΓΟ oo S •U CJl σ3 o ο CD C-Π ο ς=> ο CD OJ ro o 05 oo 12.0 1實施例3| cn CJ1 ts〇 00 S 4^. cn s ο CO CJl 各 CO <=) ο <=) ro CJl CO Cn5 〇 05 〇〇 o 1 12. 〇| αι ΟΊ ΓΌ 00 g s oo cn i ζ〇 00 CO CD C2> C=> o tr» CO ro o 05 00 o t\D 〇 實施例5 cn CD ω CD <=> A CJl 1—^ on § <〇 Ο <〇 ·—^ CD oo <=> oo ro C3 [16. 〇| 實施例6 〇Ί 00 s g S s CO o Ν-— ο >—· ro ro CO a O CO oo 實施例7 c_n ζ-Π ro 00 s σ> CD 会 CZ5 ς〇 cr» 43.0 ο o 32.0 CT> OO 〇> __12j 比較例1 <ιη CJ1 ro 00 ro m s 1—^ Ο ς〇 cn [43.〇l o b [31.〇| 68.0 [12.0] 比較例2 cn ς_Π fs3 OO S & s CZS CO cn Γ 43. 〇] ο <0 32.0 05 po <=5 Γ 11-61 比較例3 ζ_π CJi cc CO s ο S C£5 ΟΊ 6 O ο ο C? oo DO 〇 cn 00 o 14.0 比較例4 t>丨〕荈铴St t舛6粢私萆舔荦许芽碲承3:知^效3:41畀蚪知讳岭系辛 (S ) 26 1338018Polymerization condition Feed composition _1 Examples and comparative examples Θ涞 〇 〇 · · · · · EE EE 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 反应 甲基 甲基Butyl ester OD Stupid ethylene rubbery copolymer (weight 13⁄4 ) (rpm) (°C) 1 (parts by weight) 1 r—V r«r >w/ 1 (parts by weight) 1 1 (parts by weight) 1 1 (parts by weight) 1 1 (parts by weight) 1 ς _π cn ro 00 S cn 05 <=> 1 - 1 ο ς〇 CJ1 43. 0 C5 Ο ο ui CO Γ ° o 05 po o 112j Example 1 cji ( LH r〇00 gi; CJi C3 ο i CO cn CO <=> Ο <=> ο CO ro cz> 05 oo o 1__I2J ro 〇1 ΟΊ ΓΟ oo S • U CJl σ3 o ο CD C-Π ο ς=> ο CD OJ ro o 05 oo 12.0 1Example 3| cn CJ1 ts〇00 S 4^. cn s ο CO CJl Each CO <=) ο <=) ro CJl CO Cn5 〇05 〇 〇o 1 12. 〇| αι ΟΊ ΓΌ 00 gs oo cn i ζ〇00 CO CD C2>C=> o tr» CO ro o 05 00 ot\D 〇Example 5 cn CD ω CD <=> A CJl 1—^ on § <〇Ο <〇·—^ CD oo <=> oo ro C3 [16. 〇| Example 6 〇Ί 00 sg S s CO o Ν-- ο >-· ro ro CO a O CO oo Example 7 c_n ζ-Π ro 00 s σ> CD will CZ5 ς〇cr» 43.0 ο o 32.0 CT> OO 〇> __12j Comparative Example 1 <ιη CJ1 ro 00 ro ms 1—^ Ο ς〇cn [43.〇lob [31.〇| 68.0 [12.0] Comparative Example 2 cn ς_Π fs3 OO S & s CZS CO cn Γ 43. 〇] ο < ;0 32.0 05 po <=5 Γ 11-61 Comparative Example 3 ζ_π CJi cc CO s ο SC£5 ΟΊ 6 O ο ο C? oo DO 〇cn 00 o 14.0 Comparative Example 4 t>丨]荈铴St t舛6粢私萆舔荦许芽碲3:知^效3:41畀蚪知讳岭系辛(S) 26 1338018
ρά ηχ, Λ^ί 之物性 i- 1之特性1 組成物 成份 中之組 組成物！ 實施例及比較例 耐衝擊強度 ίο ο ο ο° <ί 光澤度 S〇i 00 ·〇 ft) 3 S—✓ 橡膠中位粒徑 w ^ D ώ t 5? f 橡膠含量 甲基丙烯酸甲酯 正-丙烯酸丁酯 丙烯腈 笨乙烯 I Ο Ο 〇> 3 ρ 次 1 /*~S 曰 '—^ (重量份） (重量份） (重量份） (重量份） (重量％) 18. 50 ς〇 ζ_π CO oo 1. 18 <=> 〇 〇 <=> ΓΟ 〇〇 〇 72.0 14.0 實施例1 19.30 2.25 CO cn 1. 10 0.42 ♦〇 〇 CJ1 ro po ο 72.0 14.0 實施例2 20.20 «=> CO cn i •ο 〇 <=> IND CO 28.0 丨 72.0 1 13.9 實施例3 19.50 1 2.70 1 CD CT> s Ο 〇 <=> CO —J t\0 OO => £ 實施例4 16.50 2.00 CO ts〇 g 0.41 〇 〇 〇 —J to 00 o 72.0 14.0 1實施例5 18. 00 4.50 CO cn to 0.42 ·〇 〇 ΟΊ 18.0 82.0 17.9 實施例6 12.00 Γ° g CO 05 g 0.43 to ro CO o 11.0 1實施例7 16.90 CD c_r> ◦ ο ο 〇 〇 ro 00 o ?〇 14. 1 比較例1 17. 50 —J oo -0 cjl CJ1 0.45 to 1 <0.05 1 tsD <=s 〇 1比較例2 υι •05 g CO oo 0.85 ο CO •ο ο 1 14.3 | tN〇 oo <〇 72.0 12.9 比較例3 12.80 05 <LH CJT on 1 2.50 1 ♦ο CJ3 c_n ο ο CT) ro po o 〇 5 比較例4 27Ρά ηχ, Λ^ί Physical properties i- 1 characteristics 1 Compositions Compositions in the composition Composition! Examples and comparative examples Impact strength ίο ο ο ο° <ί Gloss S〇i 00 ·〇ft) 3 S—✓ Rubber median diameter w ^ D ώ t 5? f Rubber content methyl methacrylate Ortho-butyl acrylate acrylonitrile stupid ethylene I Ο 〇 〇> 3 ρ times 1 /*~S 曰'—^ (parts by weight) (parts by weight) (parts by weight) (parts by weight) (% by weight) 18. 50 Σ〇ζ_π CO oo 1. 18 <=>〇〇<=> ΓΟ 〇〇〇72.0 14.0 Example 1 19.30 2.25 CO cn 1. 10 0.42 ♦〇〇CJ1 ro po ο 72.0 14.0 Example 2 20.20 «=> CO cn i •ο 〇<=> IND CO 28.0 丨72.0 1 13.9 Example 3 19.50 1 2.70 1 CD CT> s Ο 〇<=> CO — J t\0 OO => £ Example 4 16.50 2.00 CO ts〇g 0.41 〇〇〇—J to 00 o 72.0 14.0 1 Example 5 18. 00 4.50 CO cn to 0.42 ·〇〇ΟΊ 18.0 82.0 17.9 Example 6 12.00 Γ° g CO 05 g 0.43 to ro CO o 11.0 1 Example 7 16.90 CD c_r> ◦ ο ο 〇〇ro 00 o 〇 14.1 Comparative Example 1 17. 50 —J oo -0 cjl CJ1 0.45 to 1 <0.05 1 tsD < =s 〇1Comparative example 2 Υι •05 g CO oo 0.85 ο CO •ο ο 1 14.3 | tN〇oo <〇72.0 12.9 Comparative Example 3 12.80 05 <LH CJT on 1 2.50 1 ♦ο CJ3 c_n ο ο CT) ro po o 〇5 Compare Example 4 27