200825130 ^ 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晞系樹脂有關，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 苯乙烯系樹脂組成物。 ' 【先前技術】 一般橡膠改質本乙婦糸樹脂，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 _ 性上更疋其一大特色，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，而一般的橡膠改質苯乙烯系樹脂係由苯乙烯系_丙烯腈 ^ 系共聚物及橡膠接枝共聚物混練而得。過去橡膠改質苯乙 烯系樹脂的聚合技術大部份為乳化聚合而得，因其橡膠粒 子的重里平均粒徑較小，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，橡料質紅烯細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 所侍之橡觀質苯乙齡細旨細品光澤絲低，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 澤及耐衝料性之橡膠改質苯乙烯㈣脂乃變成急欲解決 的課題；本發聊針對此—課題，經銳意研究乃提供一種 具有而光澤及耐衝擊性物性的物性平衡之橡膠改 系樹脂組成物。 、本乙烯 5200825130 ^ IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a rubber-modified styrene-based resin, in particular to a rubber-modified styrene having a good balance of physical properties such as gloss and impact strength. A resin composition. 'Prior Art】 General rubber modification This Ethylene resin has a good evaluation for its formability and mechanical properties, especially the good appearance and gloss of the molded product. It is widely used in electronics, electrical appliances and automotive parts. However, for the rubber-modified styrene-based resin, in order to achieve a larger field of use, it is required to have a good high gloss and impact resistance, and the general rubber-modified styrene resin is made of styrene. The _acrylonitrile-based copolymer and the rubber graft copolymer are obtained by kneading. In the past, the polymerization technology of rubber-modified styrene resin was mostly obtained by emulsion polymerization, because the rubber particles have a small average particle size and high gloss and impact resistance, _ but due to emulsion polymerization technology The problem of the waste water waste liquid derived from the problem is that under the recent environmental protection requirements, the polymerization technology of the rubber red ene fine grease is changed to the bulk (Bulk) or solution polymerization, but the overall quality or solution polymerization mode The styrene-ethyl age fine product has a low gloss and can not meet the requirements of users. Under the environmental considerations, how to obtain rubber with high gloss and resistance to styrene (four) grease becomes an urgent solution. The subject of this research is to provide a rubber-modified resin composition having a physical balance of gloss and impact resistance. Benthene 5
200825130 J 【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苯乙烯系 樹脂組成物，是由：（i-Ι)苯乙烯系單體50〜90重量份、 (i-2)腈化乙烯系單體50〜10重量份，以上（丨―丨）、（卜2) 單體合計100重量份及（i-3)0.1〜8·0重量份的丙烯酸酯 • 系單體構成之共聚物連續相（Α)與橡膠狀聚合物形成的橡 膠粒子分散相（Β)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（Β)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〜，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：二稀系橡 膠、聚烯烴橡膠(例如：乙烯-丙烯橡膠）、聚丙烯酸酷系橡 鲁膠、聚石夕氧烧系橡膠等。前述二烯系橡膠乃爲：二婦系單 體成份經聚合後玻璃轉移溫度在〇°c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、氯丁二婦2 膠、乙烯-丙烯-二烯橡膠(EPDM橡膠）、苯乙烯-二烯系橡 膠、丙烯腈-二烯系橡膠等；其中，丁二烯橡膠有高順式 (Hi-Cis)含量及低順式(Low-Cis)含量的分別；高順式橡膠 中，其順式(Cis)/乙烯基(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1〇〇,〇〇〇二 6 200825130 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1〇〇, 〇〇〇〜8〇〇, 〇〇〇爲 佳。苯乙烯-二烯系橡膠的具體例如苯乙烯—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：苯乙婦-丁二 烯-苯乙烯嵌段(S-B-S)、苯乙烯-無規苯乙稀/丁二烯—苯乙 烯嵌段(S-random S/B-S)、苯乙烯-組成漸增或漸減苯乙烯 /丁二烯-苯乙烯嵌段(S—taper S/B-S)、丁二烯-組成漸增 或漸減本乙浠/丁二烯-笨乙浠嵌段(B-^aper S/b-s)、無規 苯乙烯/丁二烯嵌段(random S/B)、丁二烯-無規苯乙烯/丁 二烯-丁二烯嵌段(B—ran(i〇mS/B-B)、丁二烯-無規苯乙烯/ 丁二烯嵌段(B-rand〇m S/B)等，前述橡膠聚合物可為線性 或分歧構造，木尼(Mooney)黏度(MLm)為20〜80，25°C之5 重里/ό的本乙細早體溶液的黏度為3〜6〇cps，而二烯系單體 中之1，2-乙_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 卓獨使用白可，例如·（1)早獨使用線性構造之具有漸增咬 漸減之苯乙烯/丁二烯構造之橡膠、（2)分歧構造之丁二烯 -（無規苯乙烯/丁二烯)—丁二烯嵌段橡膠、（3)線性構造之 具有漸增或漸減苯乙烯/ 丁二烯構造之橡膠與分歧構造之 7 200825130 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苯乙烯系單體的具體例，例如： 苯乙烯、α-曱基苯乙烯、對-甲基苯乙烯、間—曱基苯乙烯、 鄰-甲基苯乙烯、乙基苯乙烯、2,4-二甲基苯乙烯、對-第 三丁基苯乙烯、α-甲基-對-甲基苯乙烯、溴-苯乙烯、二 溴-苯乙烯、2, 4, 6-三溴苯乙烯等，上述笨乙烯系單體可單 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·· 1，3-丁二烯、曱基-1，3-丁二烯、2, 3-二甲基-1，3-丁二烯、1，3-戊二烯、1，3-己二烯等，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-1，3-丁^一細為較佳。 本發明之共聚物連續相（Α)包含(i-Ι)苯乙烯系單體50 〜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1〇〇重量份及（卜3)0·丨〜8· 〇重量份 的丙烯酸酯系單體所構成，其中，（i-Ι)苯乙烯系單體之具 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1為50〜90重量份，較佳為6〇〜86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-曱基丙烯腈等，其中以丙烯腈為較佳。基 於上述（丨―1)、（i—2)合計1〇〇重量份，本發明的共聚物連 續相(A)中，（卜2)腈化乙烯系單體構成成份含量爲5〇〜1〇 8 200825130 重量份’較佳爲40〜144量份，更佳爲35〜16重量份。 本發明的丙烯_旨系單體具體例如：丙烯酸醋系單 體曱基丙烯酉夂酉旨系單體二種類，丙缚酸醋系單體的且體 例如：丙烯酸甲S旨、丙烯酸乙醋、丙烯酸異丙g|、正/丙婦 酸丁醋等，其中H丙騎τ§旨較佳。 本發明之共聚物賴相⑷巾，丙烯_旨轉體構成成 份之含量為相對於(i—1)、（i—2)合計⑽重量份之〇·卜8 重1份，較佳為〇· 2〜6重量份，更佳為〇· 2〜4重量份， 當其使用含量小於G·」重4辦，橡觀f苯乙烯系樹脂 組成物之光澤度不佳，制量大於8· Q重量糾，橡膠改 貝本乙烯糸樹脂組成物之耐衝擊強度不佳。 本發明之共聚物連續相(A)中，可視需要進一步包含其 他可共聚合單體0〜40重量份，較佳〇〜3〇重量份(基於 (i-1)、（i-2)單體合計1〇〇重量份），其單體種類並無特別 限制，具體例如：無水馬來酸、無水甲基順丁烯二酸、無 水甲基反丁細一酸、畐馬酸（fu_ric acid)、衣康酸 (itaconic acid)等不飽和羧酸系化合物以及前述羧酸系化 合物之醋化物（例如富馬酸二曱酯、衣康酸二丁醋等）、另 外例如：丙烯酸、曱基丙烯酸、曱基丙烯酸甲酯、甲基丙 烯酸乙酯、馬來醯亞胺、N-曱基馬來醯亞胺、N-異丙基馬 來醯亞胺、N-丁基馬來醯亞胺、N-己基馬來醯亞胺、N-辛 基馬來醯亞胺、N-十二烷基馬來醯亞胺、N-環己基馬來醯 亞胺、N-苯基馬來醯亞胺、另外例如：雙馬來醯亞胺系單體 等。 本發明之橡膠改質苯乙烯系樹脂組成物在聚合製造 200825130 時，可依需要添加單官能性及/或多官能性起始劑、單官能 性及/或多官能性鏈移轉劑。具體的單官能性起始劑乃例 如：過氧化二苯曱醯(benzoyl peroxide)、過氧化雙苯異 丙基（dicumyl peroxide)、過氧化叔丁基（t-butyl peroxide)、叔丁基氳過氧化物（t-butyl hydroperoxide)、 氫過氧化異丙苯(cumene hydroperoxide)、叔丁基過氧化 苯曱酸酯（tert-butyl-peroxy benzoate)、雙-2-乙基己基 過氧化二碳酸酯（bis-2-ethylhexyl peroxy dicarbonate)、叔丁基過氧化異丙基碳酸酯（tert-butyl peroxy isopropyl carbonate，簡稱BPIC)、過氧化環己酮 (cycolhexanone peroxide)、2, 2’ -偶氮-雙-異丁腈 (2, 2’ -azo-bis-isobutyronitrile)、1，Γ -偶氮雙環己烧 -1-羰腈（1，Γ -azo-biscyclohexane - 1-carbonitrile)、 2, 2’ -偶氮-雙-2-曱基丁腈（2, 2’ -azo-bis-2-methyl butyronitrile)等，其中，以過氧化二苯曱醯、過氧化雙 苯異丙基較佳。 本發明可使用的多官能性起始劑的具體例子有：1，1一 雙-叔丁基過氧化環己烧（1，1 -bis-t-butyl peroxy cyclohexane，簡稱 TX-22)、1，1-雙-叔丁基過氧化-3, 3, 5-三甲基環己烧（1，1 -bis-t-butylperoxy-3, 3, 5-trimethyl cyclohexane，簡稱 T1 -29A)、2, 5-二甲基-2, 5-雙-(2-乙基 過氧化 己醯） 己烷 [2, 5-dimethyl-2, 5-bis-(2-ethylhexanoxy peroxy)hexane]、4-(叔丁基過氧化羰基）-3-己基 -6-[7-(叔丁基過氧化幾基）庚基]環己烧{4-(t-butyl 200825130 peroxy carbony1)-3-hexy1-6-[7-(t-buty1 peroxy carbonyl)heptyl] cyclohexane}、二-叔丁基二過氧化壬 二酸酯（di-t-buty卜diperoxyazelate)、2, 5-二甲基-2, 5-雙（苯甲過氧化）-己烧[2, 5-dimethyl-2, 5-bis-(benzoyl peroxy) hexane]、二-叔丁基過氧化-六氫—對苯二酸酯 (di-t-butyl peroxy-hexabydro-terephthalate ，簡稱 HTP)、2, 2-雙（4, 4-二-叔丁基過氧化）環己基丙烷 [2, 2-bis-(4, 4-di-t-butyl peroxy) cyclohexyl propane，簡稱PX-12]、多官能性單過氧化碳酸酯 (multifunctional monoperoxycarbonate ，例如美國 AT0FINA 公司製，商品名 Luperox JWE B-50)等。 上述聚合使用之起始劑可單獨使用或二種或二種以上 並用；其使用量為相對於全部單體的〇〜1〇, 000ppm，較佳 為 10〜7000ppm。 本發明之橡膠改質苯乙烯系樹脂組成物在聚合製造 時，可依需要添加鏈轉移劑，鏈轉移劑可為單官能性鏈轉 移劑或多官能性鏈轉移劑，而具體的單官能性鏈轉移劑有： 1) 硫醇(mercaptan)類：甲基硫醇、正—丁基硫醇、環己基 石反醇、正h一烧基硫醇（n-dodecyl mercaptan，簡稱 NDM)、硬脂醯基硫醇（办町1 mercapfan)、叔十二烧 基硫醇（t-dodecyl mercaptan，簡稱TDM)、正-丙基硫 醇、正-辛基硫醇、叔-辛基硫醇、叔_壬基硫醇等。 2) 烷胺(alkyl amines)類：單乙基胺、二乙基胺、三乙基 胺、單異丙基胺、二異丙基胺、單丁基胺、二—正丁基 胺、三-正丁基胺等。 200825130 3)其他；例如，五苯基乙烧(pentaphenylethane)、α-甲 基苯乙稀二聚物（a-methyl styrene dimer)、萜品油 烯（terpinolene)，其中以硫醇類中的正-十二烷基硫 醇、叔十二烧基硫醇較佳。 多官能性鏈轉移劑乃例如：異戊四醇四（3-疏基丙酸 酯）[pentaerythritol tetrakis(3-mercapto propionate)]、異戊四醇四（2-疏基乙酸酯） [pentaerythritol tetrakis(2-mercapto acetate)]、三 -（2-疏基乙酸）三經曱基丙酯[trimethyi〇ipr〇pane tris(2 mercapto acetate)]、二-（3-疏基丙酸）三經曱基 丙 S旨 [tr i methy1ο1propane tr i s(3-mercapto propionate)，簡稱TMPT]、三-(6-巯基己酸)三羥曱基丙酯 [trimethylo卜propane tris(6-mercapto hexanate)]等； 上述所列舉者，以三-(3-疏基丙酸)三經甲基丙酯較佳。 上述使用鏈轉移劑，其使用量為相對於全部單體的〇 〜10, OOOppm，較佳為 1〇〜7, OOOppm。 本發明樹脂組成物之共聚物連續相（A)的重量平均分 子置並無特別的限制，一般為50, 〇〇〇〜3〇〇，Q〇〇，較佳為 10, 000〜200, 000。 本發明橡膠改質苯乙烯系樹脂組成物之分散相（B)中 橡膠粒子的中位粒徑(Median particle size)為〇· 25〜〇· 6 _，較佳為 0· 32//m〜〇· 55/zm，最佳為 〇· 36/zm〜〇 5/ζιη。 本發明之橡膠改質苯乙烯系樹脂組成物之分散相（Β) 為内含吸藏粒子構造(Salami)的橡膠粒子，所謂内含吸藏 粒子構造（Salami)係指橡膠粒子内含有吸藏粒子 12 200825130 (Occlusion)，而吸藏粒子包含苯乙稀系、猜化乙婦系、丙 烯酸_單體及視需要_之可共聚合單體軸之共聚物 所構成，吸藏粒子基本上為含有苯乙烯系單體成份之聚合 物’ 係與共聚物連續相(A)具有相同的組成，而橡膠粒 子内含有之吸藏粒子數量一般含有一個或一個以上，較佳 含有二個或二個以上，吸藏粒子之粒子徑一般在0.05#^ 以上。-般而言，以總體或溶液聚合法接枝聚合反應而得 之橡膠改質笨乙烯系樹脂組成物，其橡膠粒子多具有吸藏 粒子構造，另-方面，魏化聚合法紐聚合反應而得之 組成物，其橡膠粒子一般不具有吸藏粒子之構造。 々本發明之橡膠改質苯乙烯系樹脂組成物之橡膠粒徑分 佈寬幅〇· 3〜L 4為佳，較佳為〇· 81〜1· 35，更佳為1 01 〜1·3〇 本發明之橡膠改質苯乙烯系樹脂組成物在前述共聚物 連續相（Α)之丙烯酸酯系單體含量0· 1〜8重量份，且其橡 膠粒子之中位粒桉為〇· 25〜〇· 6#m，且橡膠粒子之粒徑分 佈寬幅0· 3〜1· 4時，可得到較佳之光澤度及耐衝擊強度之 物性平衡，特別是可得到良好光澤度之樹脂組成物。 一本發明之樹脂組成物之橡膠粒子之中位粒徑及橡膠粒 徑分佈寬幅可由聚合時加人特定含量之丙烯酸g旨系單體、 反應為之攪拌轉速及其他聚合條件來達成，其他聚合條件 例如：聚合反應溫度、聚合起始_使用麵及含量、相 反轉反應為之出口固體含量及橡膠含量等來調整，特別是 丙烯酸⑽'單料於達絲雜徑分佈寬幅0· 3〜1· 4有重 要貝獻。聚合時加入特定量之丙烯酸酯系單體的反應機構 13 200825130 並不很清楚，但依發明人的推測，加入丙烯酸酯系單體可 增加接技於橡膠粒子上之（i—l)、（i—2)及（i—3)單體所形成 共聚物的分子量，可能因此而促使橡膠粒子之中位粒徑及 橡膠粒徑分佈寬幅達成本發明之範圍。 本發明樹脂組成物之橡膠粒子中位粒徑及粒徑分佈寬 幅的測定方法係將橡膠改質笨乙烯系樹脂組成物樣品] 克，溶解於丙酮l〇ml中，並使用Malvern Mastersizer 儀器（雷射測粒儀)測得，並根據下列計算式計算而得: D(v，0· 5)中位粒徑（Median particle size, ώ❶ value)，由 小粒子到大粒子累積粒子量達50vol%之粒徑，亦 即50vol%的粒子之粒徑小於或等於此一中位粒 徑。 D(v，0· 1)由小粒子到大粒子累積粒子量達1〇v〇1%之粒徑 D(v，0· 9)由小粒子到大粒子累積粒子量達9〇v〇1%之粒徑 橡膠粒徑分布寬幅 Span=(D(v，0· 9)-D(v，0· 1))/D(v，0· 5)。 本發明之橡膠改質苯乙浠系樹脂組成物中，橡勝含量 為1〜40重量％，較佳為5〜3〇重量％，更佳為8〜25重量％， 當該含量低於1重量％時，樹脂組成物之耐衝擊強度會變 差，超過40重量％，樹脂組成物之光澤度會不佳。 本發明之橡膠改質苯乙烯系樹脂組成物的製造方法， 乃在橡膠狀聚合物存在下，（i-l)苯乙烯系單體、（i—2)腈 化乙烯系單體、（卜3)丙烯酸酯系單體及視需要而選之可共 聚合單體的適量频下，依需要並加人適量之聚合起始劑 及鏈轉移鮮，進雜式或連續式之塊狀或溶液聚合反 應。以連續式溶液聚合反應為例，首先將丨〜仙重量份橡 14 200825130 ，狀聚合，佳5〜3G重量份，紐6〜25重量份及(M) 笨乙烯系單體5G〜9G重量份，較佳6G〜86重量份，最佳 65〜84重量份及(卜2)腈化乙烯系單體50〜10重量份，較 ，4〇〜14重量份，最佳35〜16重量份，以上⑹）、（卜2) 單，合計1GG重量份、及(i-3)G.卜8. G重量份的丙稀酸醋 糸早體’較佳爲G. 2〜重量份，更佳爲〇. 2〜4· 〇重量 伤^可共♦合單體G〜4G重量份’較佳G〜3G重量份，及 視:要可加人適當的溶劑，聚合起始劑及鏈轉移劑等形成 原料混^溶液，前述補混合溶液可以在具錢拌的溶解 槽中進行鱗’將上述轉狀絲物完全轉成橡膠溶液 (即進料溶液）陳態，以方便㈣輸送至反應器的作業進 行。將前it祕溶歧/或前料体所域之單齡液連續 的银入第-反應器及/或第二反應器、及/或其後續之反應 器中、，β或各反應器間之連接管路中加入；另前述原料溶液 及/或單體溶液亦可選擇地餵入另一獨立之反應器，該反應 器之出口接續至視需要而選之反應器（例如前述之第一或 第二反應器）或各反應器之間的連接管路上。 上述在聚合時可使用的溶劑種類有··芳香族碳氫化合 物:酮類、酯類，其中，最好的芳香族碳氫化合物例如： 甲苯、乙苯及二甲苯為佳。此外本發明亦可使用正一己烧、 環己烧、正-庚烧等脂肪族碳氫化合物作為溶劑的一部份。 上述反應器可為連續攪拌式反應器（CSTR)、栓塞流式 反應器（Plug flow reactor)或靜力混合式（static react〇r) 反應器之同一種或不同種類之串聯或並聯之組合。其反應 溫度控制在70〜230 C，相反轉之反應器出口之固體含量約 15 200825130 在12〜40重量％，較佳為16〜35重量％，更佳為20〜32重 量％，最終反應器出口之固體含量可達30〜95%，但以40〜 90%為較佳，45〜90%為最佳。 本發明橡膠改質苯乙烯系樹脂組成物的聚合反應，所 使用反應器組合型態的具體例如： (1) 三個或四個或五個栓塞流式反應器（PFR)串聯 (2) 串聯之連續攪拌式反應器（CSTR)一（串聯）栓塞流式反 應器（PFR)-(串聯)栓塞流式反應器（pfr) (3) 串聯之連續攪拌式反應器（CSTR)-連續攪拌式反應器 (CSTR)-栓塞流式反應器（pfr) (4) 二個並聯連續攪拌式反應器（匚811〇出口合流後再串聯 至-連續攪拌式反應器（CSTR)-栓塞流式反應器（PFR) (5) 二個並聯連續攪拌式反應器（CSTR)出口合流後再串 聯至-栓塞流式反應器（PFR)-栓塞流式反應器（PFR) (6) 連續攪拌式反應器（CSTR)出口分流至二個並聯連續攪 拌式反應器(CSTR)，二反應器出口合流後再串聯栓塞 流式反應器（PFR); (7) 四個或五個栓塞流式反應器（PFR)串聯，另外，有一獨 立之栓塞流式反應器之出口連接至第二個與第三個栓 塞流式反應器間的管路或連接至第三個栓塞流式反應 器。 (8) 在各反應器之間，可加入使用一附有高剪切力（high shear force)攪拌器之反應器（或混合器）及/或具有回 流(recycle)的設備。 前述反應器可為連續攪拌式反應器（CSTR)、栓塞流式 16 200825130 反應器（Plug flow reactor)或靜力混合式反應器（static reactor) 〇 鈿述聚合反應之後從反應器中取出，經脫揮發裝置將 未反應的單體、溶劑專低揮發份脫除，經聚合物回收之後， 即可製得本發明之橡膠改質苯乙烯系樹脂組成物。 上述脫揮發裝置可為：單軸或雙軸附有脫揮口之押出 機’並可依需要於押出機中加入脫揮助劑，如：水、環己 烷、二氧化碳等。而押出機亦可依需要設有捏混區段 _ (kneading zone)、推送區段(pUmping z〇ne)等，螺桿轉速 為120〜350rpm，就本發明而言，以雙軸附有脫揮發口之押 出機為佳。另外，亦可使用附有抽真空設備之脫揮槽，上 述脫揮槽可一個或數個串聯使用，其溫度控制在18〇〜35〇 °C，較佳為200〜320°C，更佳為220〜300°C，而脫揮槽的 ^ 真空度控制在300 Torr以下，較佳為2〇〇 Torr 以下，更 佳為100 Torr以下；其他的脫揮設備如薄膜蒸發器（也化 film)亦可採用。 • 本發明之橡膠改質苯乙烯系樹脂組成物，在不顯著損 及本發明樹脂組成物之效果的範圍内，可視需要調配其他 成份，此等其他成份乃例如：著色劑、填充劑、難燃劑、 難燃助劑（二氧化銻等）、光安定劑、熱安定劑、可塑劑、 滑劑、離型劑、增黏劑、帶電防止劑、氧化防止劑、導電 劑等添加劑。上述添加劑可例如:礦物油，如··硬脂酸丁 酉旨之醋系可塑劑、聚g旨系可塑劑，如··聚二曱基碎氧烧之 有機聚石夕氧烧、高級脂肪酸及其金屬鹽、位阻胺系抗氧化 劑、玻璃纖維等，添加劑可單獨使用或混合使用。上述成 200825130 份依需要可於聚合反應階段或反應完成後添加混合。 前述聚酯系可塑劑或礦物油之使用量（基於樹脂組成 物）一般在0〜5重量份，較佳為〇· 〇5〜2重量份，而有機 聚石夕氧烧之使用量一般在〇〜〇· 5重量份，較佳為〇· _2〜 〇. 2重量份。 此外，在不顯著損及本發明樹脂組成物之物性狀況 下，可進一步调配其他的樹脂，而可添加的其他樹脂如： 苯乙烯系-甲基丙烯酸酯系―丙烯腈系共聚物、苯乙烯系一曱 基丙烯酸酯系共聚物、苯乙烯系—甲基丙烯酸酯系一丙烯腈 系-馬來酿亞胺系共聚物、苯乙稀系—曱基丙烯酸醋系-馬來 醯亞胺系共聚物、甲基丙烯酸酯系-馬來醯亞胺系共聚物， 或經二烯系橡膠改質（或接枝改質）之前述共聚物。 月ίι述添加其他樹脂使用量為相對於橡膠改質苯乙浠系 樹脂組成物之100重量份的〇〜2〇〇重量份，其可調整或提 高樹脂組成物的耐熱性、剛性或流動加工性。 本發明之橡膠改質苯乙烯純驗祕_途並無特 別的限制，其可適用於射出成型、壓縮成型之各種成型品、 押出成型、吹延成型、熱細、真空細及中空成型所製 成^成品，例如押板、薄職型品等，並可依配方調配達 成高流動性、高耐熱性等需求。 刚述其他成份或樹脂組成物之添加混合可藉由布拉本 德塑性儀、細域賴、捏合_混合機、賴機、單轴或 雙軸押出機等之-般混合混賴混合混練製得。通常藉這 些押出機等混合混練後，再將押製出的壓出物加以冷^、 粒化，上述混練一般是在16〇〜28〇ΐτ進行，而以18〇〜 200825130 250 C之溫度為佳，又各調配成份之混合混練並無順序上之 特別限制。 [物性測試] 1·橡膠改質苯乙烯系樹脂組成物之流動係數： 橡膠改質苯乙烯系樹脂組成物成形品於溫度20(TC、荷重 5kg所測得之MFR為MI(g/10分）。其中，MFR乃依ASTM D-1238法測定。 2·橡膠含有量及共聚物連續相(a)之單體組成測定： 取橡膠改質苯乙烯系樹脂組成物以四氫呋喃（Tatra hydrofuran)溶解後，經拉膜後以Nicolet公司製、型號 Nexus 470的傅立葉變換紅外線分光計（Fourier Transform Infrared Spectrometer)測試。單位：重量％。 3·耐衝擊性強度測定： 艾氏衝擊強度（IZ0D):依ASTMD-256法測定艾氏衝擊強 度(23°C附有缺口之1/4吋厚度試驗片）；單位：kg-cm/ cm ° 4·橡膠粒子的中位粒徑及橡膠粒子之粒徑分佈寬幅（印如) 測定： 取橡膠改質苯乙烯系樹脂組成物樣品丨克，溶解於丙酮 10ml中’並使用Malvern Master sizer儀器測得，並根 據下列計算式計算而得： D(v，0.5)中位粒控(如value)，由小粒子到大粒子累 積粒子量達50vol%之粒徑 D(v，0· 1)由小粒子到大粒子累積粒子量達1〇v〇1%之粒 200825130 D(v，0. 9)由小粒子到大粒子累積粒子量達9〇v〇1%之粒 徑 橡 膠 粒 徑 分 布寬幅200825130 J [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 styrene resin composition by: (i-Ι) styrene monomer 50 to 90 parts by weight, (i-2) nitrile ethylene 50 to 10 parts by weight of a monomer, a total of 100 parts by weight of the above monomers, and (i-3) 0.1 to 8.0 parts by weight of a copolymer composed of an acrylate monomer The continuous phase (Α) is composed of a rubber particle dispersed phase (Β) formed of a rubbery polymer; wherein the rubber content of the rubber-modified ethylene resin composition is 1 to 40% by weight, and the dispersed phase (Β) is The rubber particles containing the sorbent particle structure (Salami) have a median particle size of 0·25~ and a particle size distribution of the rubber particles of 0.3 to 1.4. Specific examples of the rubbery polymer used in the present invention include a di-thratic rubber, a polyolefin rubber (e.g., ethylene-propylene rubber), a polyacrylic rubber, a polysulfide rubber, and the like. The diene rubber is a polymer in which the glass transition temperature of the disaccharide monomer component is 〇°c or less after polymerization, and specific examples of the dilute rubber include butadiene rubber, isoprene rubber, and chlorine. Ding Erfu 2 rubber, ethylene-propylene-diene rubber (EPDM rubber), styrene-diene rubber, acrylonitrile-diene rubber, etc.; among them, butadiene rubber has high cis (Hi-Cis) The content and the low cis (Low-Cis) content; in the high cis rubber, the typical weight composition of cis (Cis) / vinyl (Vinyl) is (94 ~ 99%) / (0 ~ 5%) The remaining composition is a trans (Trans) structure; its Mooney viscosity is between 20 and 120, the molecular weight range is 1〇〇, and the second is 6 200825130 800,000; in the low cis rubber, cis The typical weight composition of /vinyl is in the range of (20~40%) / (6~20%), the rest is trans structure, the Mooney viscosity is between 20~120, and the molecular weight range is 1〇〇, 〇〇〇~8 Hey, hey is better. Specific examples of the styrene-diene rubber include styrene-butadiene rubber and styrene-isoprene rubber, and a rubber polymer structure may have a homopolymer block structure or a random structure. (random structure) or a tapered structure that constitutes an increasing or decreasing, or a mixed structure of the foregoing construction, such as: styrene-butadiene-styrene block (SBS), styrene-random styrene /butadiene-styrene block (S-random S/BS), styrene - composition of increasing or decreasing styrene / butadiene-styrene block (S-taper S / BS), butadiene - Composition of increasing or decreasing acetonitrile/butadiene-Bistule block (B-^aper S/bs), random styrene/butadiene block (random S/B), butadiene-free Styrene/butadiene-butadiene block (B-ran(i〇mS/BB), butadiene-random styrene/butadiene block (B-rand〇m S/B), etc. The rubber polymer may have a linear or divergent structure, a Mooney viscosity (MLm) of 20 to 80, and a viscosity of 5 to 6 〇 cps of 5 liters/min of the 25 ° C. And the 1,2-ethyl group in the diene monomer (1) 2-vinyl) has a structural content of 8% by weight or more, a polystyrene block content of 5 to 35% by weight of the rubbery polymer, and a molecular weight range of preferably 50,000 to 600, 〇〇〇. The polymer may be used in combination of two or more kinds of rubbers, or may be used alone. For example, (1) a linearly constructed rubber having a gradually increasing bite-grading styrene/butadiene structure, (2) a divergence Constructed butadiene-(random styrene/butadiene)-butadiene block rubber, (3) linearly constructed rubber with a progressive or decreasing styrene/butadiene structure and a divergent structure 7 200825130 A butadiene rubber is used in combination, and a rubber having an increasing or decreasing styrene/butadiene structure in a linear configuration is preferably used alone. Specific examples of the styrene monomer of the above rubbery polymer, for example, styrene, Α-mercaptostyrene, p-methylstyrene, m-nonylstyrene, o-methylstyrene, ethylstyrene, 2,4-dimethylstyrene, p-tert-butylbenzene Ethylene, α-methyl-p-methylstyrene, bromine-styrene, dibromo-styrene, 2, 4 6-tribromostyrene, etc., the above-mentioned stupid vinyl monomers may be used singly or in combination of several kinds. Specific examples of the diene monomer of the rubbery polymer, for example, 1,3-butadiene, Mercapto-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc., each of the above specific examples can be used alone One type or a mixture of two or more types may be used, and among them, 1,3-butadiene or 2-methyl-1,3-butylene is further preferred. The continuous phase (Α) of the copolymer of the present invention comprises 50 to 90 parts by weight of (i-Ι) styrene monomer, and 50 to 10 parts by weight of (i-2) a nitridinated vinyl monomer, and the above (il), ( I-2) A total of 1 part by weight of the monomer and an acrylate monomer having a weight fraction of (b), and a specific example of the (i-fluorene) styrene monomer. The styrene monomer of the rubber polymer described above is not repeatedly illustrated; the stupid vinyl monomer component in the continuous phase (A) of the copolymer of the present invention contains 1 to 50 to 90 parts by weight, preferably 6 〇~86 parts by weight, more preferably 65 to 84 parts by weight. Specific examples of the (i-2) nitrileated vinyl monomer used in the present invention are acrylonitrile, α-mercapto acrylonitrile, and the like, and acrylonitrile is preferred. Based on the above (丨-1), (i-2) total of 1 part by weight, in the continuous phase (A) of the copolymer of the present invention, the content of the nitrileated vinyl monomer is 5 〇 1 〇8 200825130 parts by weight 'preferably 40 to 144 parts by weight, more preferably 35 to 16 parts by weight. The propylene-based monomer of the present invention is specifically, for example, an acrylic vinegar-based monomer, a fluorenyl acrylonitrile-based monomer, and a acrylate-based vinegar-based monomer, for example, an acrylic styrene, an acrylic vinegar. , acrylic acid isopropyl g |, positive / propylene vinegar vinegar, etc., of which H propylene riding τ § preferred. The content of the copolymer lysate (4) towel of the present invention, the propylene-transfer component is 1 part by weight based on the total of (i-1) and (i-2) (10) parts by weight, preferably 〇. · 2 to 6 parts by weight, more preferably 2 to 4 parts by weight, when the content is less than G·”, the gloss of the rubber composition of the rubber styrene resin is not good, and the production amount is greater than 8· Q weight correction, the rubber modified Beiben ethylene resin composition has poor impact strength. In the continuous phase (A) of the copolymer of the present invention, if necessary, further comprising 0 to 40 parts by weight of other copolymerizable monomers, preferably 〇3 to 3 parts by weight (based on (i-1), (i-2) single The total amount of the monomers is 1 part by weight, and the monomer type thereof is not particularly limited, and specific examples thereof include anhydrous maleic acid, anhydrous methyl maleic acid, anhydrous methyl antibutanic acid, and humic acid (fu_ric acid). And an unsaturated carboxylic acid compound such as itaconic acid, and an acetate of the carboxylic acid compound (for example, dinonyl fumarate or dibutyl acetonate), and, for example, acrylic acid or sulfhydryl group. Acrylic acid, methyl methacrylate, ethyl methacrylate, maleimide, N-mercaptomaleimide, N-isopropyl maleimide, N-butyl maleimide , N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenyl malayan An amine, for example, a bismaleimide monomer or the like. When the rubber-modified styrene-based resin composition of the present invention is produced by polymerization in 200825130, a monofunctional and/or polyfunctional initiator, a monofunctional and/or a polyfunctional chain transfer agent may be added as needed. Specific monofunctional starters are, for example, benzoyl peroxide, dicumyl peroxide, t-butyl peroxide, t-butyl fluorene T-butyl hydroperoxide, cumene hydroperoxide, tert-butyl-peroxy benzoate, bis-2-ethylhexyl peroxydicarbonate Bis-2-ethylhexyl peroxy dicarbonate, tert-butyl peroxy isopropyl carbonate (BPIC), cycolhexanone peroxide, 2, 2'-azo -2,2'-azo-bis-isobutyronitrile, 1, Γ-azo-biscyclohexane- 1-carbonitrile, 2, 2 '- 2,2'-azo-bis-2-methyl butyronitrile, etc., among which diphenyl hydrazine peroxide and bisperoxy isopropyl peroxide are preferred. Specific examples of the polyfunctional starter which can be used in the present invention are: 1,1 -bis-t-butyl peroxy cyclohexane (TX-22), 1 1,1-bis-t-butylperoxy-3, 3, 5-trimethyl cyclohexane (T1 -29A), 2 , 5-dimethyl-2, 5-bis-(2-ethylhexano-peroxy hexane), 2-(4-dimethyl-2, 5-bis-(2-ethylhexanoxy peroxy)hexane, 4-( Tert-butylperoxycarbonyl)-3-hexyl-6-[7-(tert-butylperoxy)heptyl]cyclohexene{4-(t-butyl 200825130 peroxy carbony1)-3-hexy1-6- [7-(t-buty1 peroxy carbonyl)heptyl] cyclohexane}, di-t-buty diperoxyazelate, 2, 5-dimethyl-2, 5-double (2, 5-dimethyl-2, 5-bis-(benzoyl peroxy) hexane], di-tert-butylperoxide-hexahydro-terephthalate (di-t- Butyl peroxy-hexabydro-terephthalate (HTP), 2, 2-bis(4, 4-di-tert-butylperoxy)cyclohexylpropane [2, 2-bis-(4, 4-di-t-butyl peroxy) ) cyclohexyl propane, He said PX-12], polyfunctional monoperoxycarbonates (multifunctional monoperoxycarbonate, e.g. U.S. AT0FINA Corporation, trade name Luperox JWE B-50) and the like. The initiators used in the above polymerization may be used singly or in combination of two or more kinds; they are used in an amount of from 〇1 to 10,000 ppm, preferably from 10 to 7,000 ppm based on the total of the monomers. The rubber modified styrene resin composition of the present invention may be added with a chain transfer agent as needed during the polymerization, and the chain transfer agent may be a monofunctional chain transfer agent or a polyfunctional chain transfer agent, and the specific monofunctionality. Chain transfer agents are: 1) Mercaptans: methyl mercaptan, n-butyl mercaptan, cyclohexyl anti-alcohol, n-dodecyl mercaptan (NDM), hard Lipidyl mercaptan (1 mercapfan), t-dodecyl mercaptan (TDM), n-propyl mercaptan, n-octyl mercaptan, tert-octyl mercaptan, Tert-mercaptothiol and the like. 2) alkyl amines: monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, di-n-butylamine, three - n-butylamine and the like. 200825130 3) Others; for example, pentaphenylethane, a-methyl styrene dimer, terpinolene, among which are positive in thiols - Dodecyl mercaptan and tert-dodecyl mercaptan are preferred. A polyfunctional chain transfer agent is, for example, pentaerythritol tetrakis (3-mercapto propionate), pentaerythritol tetrakis (2-mercaptoacetate) [pentaerythritol] Tetrakis(2-mercapto acetate)], tri-(2-mercaptoacetic acid) trimethyi〇ipr〇pane tris(2 mercapto acetate), di-(3-sodium propionate) Tr 丙 S 旨 tr [tr i methy1ο1 propane tr is (3-mercapto propionate), referred to as TMPT], tris-(6-mercaptohexanoic acid) trimethyl propyl propyl ester The above-mentioned ones are preferably tris-(3-cyanopropionic acid) trimethyl propyl ester. The above-mentioned chain transfer agent is used in an amount of 〇 10, OOO ppm, preferably 1 〇 to 7, OOO ppm, based on the total monomers. The weight average molecular weight of the continuous phase (A) of the copolymer of the resin composition of the present invention is not particularly limited, and is usually 50, 〇〇〇~3〇〇, Q〇〇, preferably 10,000 to 200,000. . The median particle size of the rubber particles in the dispersed phase (B) of the rubber-modified styrene resin composition of the present invention is 〇· 25 〇·6 _ , preferably 0·32//m 〜 〇· 55/zm, the best is 〇·36/zm~〇5/ζιη. The dispersed phase (Β) of the rubber-modified styrene resin composition of the present invention is a rubber particle containing a sorbent particle structure (Salami), and the so-called occluded particle structure (Salami) means that the rubber particles contain occlusion Particle 12 200825130 (Occlusion), and the occluded particles are composed of a copolymer of styrene, a prostaglandin, an acrylic acid monomer, and, if necessary, a copolymerizable monomer axis, and the occluded particles are basically The polymer containing the styrene monomer component has the same composition as the continuous phase (A) of the copolymer, and the amount of the occluded particles contained in the rubber particle generally contains one or more, preferably two or two. Above, the particle diameter of the occluded particles is generally 0.05 or more. In general, a rubber-modified stupid vinyl resin composition obtained by graft polymerization of a bulk or a solution polymerization method has a rubber particle structure having a occluded particle structure, and another aspect, a Weihua polymerization method. In the resulting composition, the rubber particles generally do not have the structure of occluding particles. The rubber particle size distribution of the rubber-modified styrene resin composition of the present invention is preferably 宽·3 to L 4 , preferably 〇 81 to 1.35, more preferably 1 01 〜1·3 〇. The rubber-modified styrene-based resin composition of the present invention has a acrylate monomer content of 0. 1 to 8 parts by weight in the continuous phase of the copolymer, and the granule enthalpy of the rubber particles is 〇·25~ 〇·6#m, and when the particle size distribution of the rubber particles is 0·3 to 1·4, a balance of physical properties of a preferable glossiness and impact strength can be obtained, and in particular, a resin composition having a good gloss can be obtained. The median particle size and the rubber particle size distribution of the rubber particles of the resin composition of the present invention can be achieved by adding a specific amount of acrylic acid g-specific monomer during polymerization, stirring reaction speed and other polymerization conditions, and the like. The polymerization conditions are adjusted, for example, the polymerization reaction temperature, the polymerization start_use surface and the content, the reverse conversion reaction to the outlet solid content, and the rubber content, and the like, in particular, the acrylic (10)' single material has a wide distribution of the wire diameter of 0. ~1·4 has important benevolence. The reaction mechanism 13 200825130 in which a specific amount of the acrylate monomer is added during polymerization is not clear, but according to the inventors' speculation, the addition of the acrylate monomer can increase the (i-1) of the rubber particles. The molecular weight of the copolymer formed by the i-2) and (i-3) monomers may thereby contribute to the broad range of the rubber particle size and the rubber particle size distribution to the extent of the present invention. The method for measuring the median particle size and the particle size distribution of the rubber particles of the resin composition of the present invention is to dissolve the rubber-modified stupid vinyl resin composition sample in grams of acetone, and use a Malvern Mastersizer instrument ( The laser granulator is measured and calculated according to the following formula: D (v, 0 · 5) Median particle size (ώ❶ value), from small particles to large particles, cumulative particles up to 50 vol The particle size of %, that is, the particle diameter of 50 vol% of the particles is less than or equal to the median particle size. D(v,0·1) from small particles to large particles, the cumulative particle amount reaches 1〇v〇1% of the particle size D(v,0·9) from small particles to large particles, the cumulative particle amount reaches 9〇v〇1 % particle size rubber particle size distribution width Span = (D (v, 0 · 9) - D (v, 0 · 1)) / D (v, 0 · 5). In the rubber-modified styrene-based resin composition of the present invention, the rubber content is from 1 to 40% by weight, preferably from 5 to 3% by weight, more preferably from 8 to 25% by weight, when the content is less than 1 When the weight is %, the impact strength of the resin composition is deteriorated, and if it exceeds 40% by weight, the gloss of the resin composition may be poor. The method for producing a rubber-modified styrene-based resin composition of the present invention comprises (il) a styrene-based monomer, (i-2) a nitrile-vinyl monomer, and (b) in the presence of a rubbery polymer. The acrylate monomer and, if necessary, the appropriate amount of the copolymerizable monomer, if necessary, add an appropriate amount of polymerization initiator and chain transfer fresh, mixed or continuous block or solution polymerization . Taking continuous solution polymerization as an example, firstly, the weight of the rubber is 14200825130, the polymerization is good, preferably 5 to 3G parts by weight, 6 to 25 parts by weight of the New Zealand, and (M) the stupid vinyl monomer 5G to 9G parts by weight. Preferably, it is 6 to 86 parts by weight, preferably 65 to 84 parts by weight, and 50 to 10 parts by weight of the nitrile vinyl monomer, more preferably 4 to 14 parts by weight, most preferably 35 to 16 parts by weight. The above (6)), (b 2) single, a total of 1 GG parts by weight, and (i-3) G. 4.8 g parts by weight of acetoacetate 糸 early body 'preferably G. 2 parts by weight, more preferably 〇. 2~4· 〇 weight injury ^ can be a total of ♦ monomer G ~ 4G parts by weight 'preferably G ~ 3G parts by weight, and depending on: you can add appropriate solvent, polymerization initiator and chain transfer agent The raw material mixed solution is formed, and the above-mentioned supplementary mixed solution can be subjected to the scale in the dissolving tank with the money mixing, and the above-mentioned rotating filament material is completely converted into a rubber solution (ie, a feeding solution) to facilitate the transportation to the reactor. The homework is carried out. Continuous silver into a single reactor and/or a second reactor, and/or its subsequent reactor, or between β or each reactor, in a single-stage liquid in the domain of the former solution Adding to the connecting line; the foregoing raw material solution and/or monomer solution may also be selectively fed to another independent reactor, and the outlet of the reactor is connected to the reactor selected as needed (for example, the first one mentioned above) Or the second reactor) or the connecting line between the reactors. The types of solvents which can be used in the polymerization are: aromatic hydrocarbons: ketones and esters. Among them, preferred aromatic hydrocarbons are, for example, toluene, ethylbenzene and xylene. Further, in the present invention, an aliphatic hydrocarbon such as hexanone, cyclohexane or n-heptane may be used as a part of the solvent. The above reactor may be a combination of the same or different types of series or parallel of a continuous stirred reactor (CSTR), a plug flow reactor or a static react reactor. The reaction temperature is controlled at 70 to 230 C, and the solid content of the reactor outlet is about 15 200825130 at 12 to 40% by weight, preferably 16 to 35% by weight, more preferably 20 to 32% by weight, in the final reactor. The solid content of the outlet can reach 30 to 95%, but 40 to 90% is preferred, and 45 to 90% is preferred. For the polymerization of the rubber-modified styrene resin composition of the present invention, specific examples of the reactor combination type used are as follows: (1) Three or four or five plug flow reactors (PFR) in series (2) series connection Continuous stirred reactor (CSTR) - (series) plug flow reactor (PFR) - (series) plug flow reactor (pfr) (3) continuous stirred reactor (CSTR) in series - continuous stirring Reactor (CSTR)-plug flow reactor (pfr) (4) Two parallel continuous stirred reactors (匚811〇 outlet combined and then connected in series to a continuous stirred reactor (CSTR)-plug flow reactor (PFR) (5) Two parallel continuous stirred reactor (CSTR) outlets are combined and connected in series to a plug flow reactor (PFR)-plug flow reactor (PFR) (6) Continuous stirred reactor ( The CSTR) outlet is split to two parallel continuous stirred reactors (CSTR), and the two reactor outlets are combined and connected to a plug flow reactor (PFR); (7) four or five plug flow reactors (PFR) In series, in addition, an outlet of a separate plug flow reactor is connected to the second and third plugs The line between the plug flow reactors or connected to the third plug flow reactor. (8) Between each reactor, a reaction with a high shear force stirrer can be added. (or mixer) and/or equipment with a recycle. The foregoing reactor may be a continuous stirred reactor (CSTR), a plug flow type 16 200825130 (Plug flow reactor) or a static hybrid reactor (static reactor) After the polymerization reaction is taken out from the reactor, the unreacted monomer and the solvent-specific low volatile matter are removed by the devolatilization device, and after the polymer is recovered, the rubber modification of the present invention can be obtained. The styrene resin composition. The devolatilizer may be a uniaxial or biaxial extruder with a devolatilization and may be added with a devolatilization aid such as water or cyclohexane in the extruder as needed. , carbon dioxide, etc., and the extruder can also be provided with a kneading zone _ (kneading zone), a push section (pUmping z〇ne), etc., and the screw rotation speed is 120 to 350 rpm, and in the present invention, a double shaft It is better to have an extruder with a devolatilization port. It is also possible to use a devolatilization tank with a vacuuming device. The devolatilizer tank can be used in one or several series, and the temperature is controlled at 18 〇 to 35 ° C, preferably 200 to 320 ° C, more preferably 220. ~300 ° C, and the degree of vacuum of the devolatilization tank is controlled to be 300 Torr or less, preferably 2 Torr or less, more preferably 100 Torr or less; other devolatilization equipment such as a thin film evaporator (also a film) Can be used. • The rubber-modified styrene-based resin composition of the present invention may be blended with other components as needed within a range that does not significantly impair the effect of the resin composition of the present invention, such as colorants, fillers, and hardeners. Additives such as fuel, flame retardant (cerium oxide, etc.), light stabilizer, thermal stabilizer, plasticizer, slip agent, release agent, tackifier, antistatic agent, oxidation inhibitor, and conductive agent. The above additives may, for example, be mineral oils, such as vinegar-based plasticizers, polyg-type plasticizers, such as polydidecyl-based oxy-combustion, organic poly-stones, higher fatty acids and The metal salt, the hindered amine-based antioxidant, the glass fiber, etc., may be used singly or in combination. The above-mentioned 200825130 parts may be added as needed in the polymerization reaction stage or after completion of the reaction. The amount of the polyester-based plasticizer or mineral oil used (based on the resin composition) is generally 0 to 5 parts by weight, preferably 〜·〇 5 to 2 parts by weight, and the amount of the organic polyoxoxime is generally used. 〇~〇· 5 parts by weight, preferably 〇· _2~ 〇. 2 parts by weight. Further, other resins may be further blended without significantly impairing the physical properties of the resin composition of the present invention, and other resins which may be added are, for example, styrene-methacrylate-acrylonitrile copolymer, styrene. A mercapto acrylate copolymer, a styrene-methacrylate-acrylonitrile-maleimide copolymer, a styrene-mercapto acrylate-maleimide system A copolymer, a methacrylate-maleimide copolymer, or a copolymer modified (or graft modified) with a diene rubber. The amount of the other resin used is 〇 2 2 parts by weight relative to 100 parts by weight of the rubber-modified styrene-based resin composition, which can adjust or improve the heat resistance, rigidity or flow processing of the resin composition. Sex. The rubber modified styrene pure test method of the present invention is not particularly limited, and can be applied to various molded articles for injection molding and compression molding, extrusion molding, blow molding, hot fine, vacuum fine and hollow molding. Finished products, such as slabs, thin grades, etc., can be formulated according to the formula to achieve high fluidity, high heat resistance and other needs. The addition and mixing of other components or resin compositions can be carried out by mixing and mixing the Brabender plastometer, fine-domain lysing, kneading-mixing machine, smashing machine, uniaxial or biaxial extruder. . Usually, after mixing and kneading by these extruders, the pressed extrudate is cooled and granulated. The above-mentioned kneading is generally carried out at 16 〇 to 28 〇ΐτ, and the temperature at 18 〇 to 200825130 250 C is Good, and the mixing and mixing of the various ingredients is not particularly limited in order. [Physical property test] 1. Flow coefficient of rubber modified styrene resin composition: Rubber modified styrene resin composition molded article at a temperature of 20 (TC, load 5 kg, measured MFR is MI (g/10 min) Among them, MFR is determined according to ASTM D-1238. 2. Rubber content and continuous phase of copolymer (a) Determination of monomer composition: After the rubber modified styrene resin composition is dissolved in tetrahydrofuran (Tatra hydrofuran) After the film was pulled, it was tested by Fourier Transform Infrared Spectrometer, manufactured by Nicolet, Model Nexus 470. Unit: % by weight 3. Determination of impact strength: Izod impact strength (IZ0D): According to ASTM D -256 method for measuring Izod impact strength (23 ° C with a notched 1/4 inch thickness test piece); unit: kg-cm / cm ° 4 · median particle size of rubber particles and rubber particles have a wide particle size distribution Measure (printed as) Determination: Take a sample of rubber modified styrene resin composition, dissolved in acetone 10 ml ' and measured using a Malvern Master sizer instrument, and calculated according to the following formula: D (v, 0.5) ) median grain control (such as value) From small particles to large particles, the particle size of the cumulative particles up to 50 vol% D (v, 0 · 1) from small particles to large particles cumulative particles up to 1 〇 v 〇 1% of the particles 200825130 D (v, 0.9) Particle size distribution from small particles to large particles up to 9〇v〇1%
Span=(D(v，0· 9)-D(v，0· 1))/D(v，〇· 5)。 5.光澤度測定： 取橡膠改質苯乙烯系樹脂組成物在22〇°c射出成厚度 1/8”（3.17111111)，直徑5.5〇11之圓盤試片，並以儀器：腿 Micro-TRI (60度角）’根據ASTM D-2457方法測得，單 位％ 〇 【實施例之詳細說明】 [實施例1]Span = (D (v, 0 · 9) - D (v, 0 · 1)) / D (v, 〇 · 5). 5. Gloss measurement: Take a rubber modified styrene resin composition at 22 ° C to a thickness of 1 / 8" (3.17111111), a diameter of 5.5 〇 11 disc test piece, and instrument: leg Micro-TRI (60 degree angle) 'measured according to ASTM D-2457 method, unit % 〇 [Detailed Description of Embodiments] [Example 1]
'V 三個栓塞流式反應器（PFR)串聯，其各別容量為1〇〇公 升，將苯乙烯單體68重量份、丙烯腈單體32重量份、橡 膠狀聚合物為丁二烯—苯乙烯成分漸增之苯乙烯/ 丁二烯一 苯乙烯橡膠(B-taperS/B-S，苯乙烯/丁二烯重量比= 25/75 重量％ ’木尼(Mooney)黏度(ML!h)為45)12重量份、及相對 於苯乙烯單體、丙烯腈單體合計100重量份之正-丙烯酸丁 醋單體0· 5重量份，溶劑乙笨43重量份，聚合起始劑二一 弟二丁基過氧化-六氫-對苯二酸醋(HTP)450 ppm(基於全部 單体），鏈轉移劑叔-十二烧基硫醇(TDM)600 ppm(基於全部 單体)形成之混合溶液，以50 kg/小時之流量，連續地供给 至第一反應器進行聚合反應；將第一反應器反應所得之聚 合物溶液導入第二反應器；再將第二反應器反應所得之聚 合物溶液導入第三反應器進行聚合反應；其中，第一、第 二、第三反應器之溫度（反應器入口區域及出口區域二者之 20 200825130 , 平均溫度）分別為95、110、135°C，攪拌速率分別為6〇、 45、20rPm ;且第一反應器為相反轉區，其出口的固體含量 為28重量％，第三反應器出口的固體含量為55重量％。 在聚合終了後，將由第三反應器反應所得的共聚物溶 液導入脫揮裝置，移除未反應單體及其他揮發份；將其製 粒即可得到本發明的橡膠改質苯乙烯系樹脂組成物；測定 其橡膠成分含有量為14重量％，橡膠中位粒徑為〇 44#m， 該分散相（B)具有内含吸藏粒子構造的橡膠粒子，橡膠粒子 • 之吸藏粒子之數目多為二個或二個以上。橡膠粒徑分佈寬 幅(即an)為1.18 ;該橡膠改質苯乙烯系樹脂組成物的製造 配方及聚合條件列於表一及其特性、物性列於表二。 [實施例2〜4] 同實施例1之聚合配方及聚合條件，不同處在於正一丙 烯酸丁料體進料組成分顺h G重量份、丨.5重量份、2.5 重量份得到橡膠改質苯乙稀系樹脂組成物，其配方、聚合 餅顺表―’其所得之雖及鎌顺表二，所得之樹 • 酿成物之分散相⑻為具有内含吸藏粒子構造的橡膠粒 子0 [實施例5] 同實施例1之聚合方式並依據表一配方及聚合條件， 並且進料組成中聚合起始劑改成U|叔丁基過氧化 3,3,5 一甲基環己烷，簡稱τχ一瓢他卿及鍵轉移劑叔 -十-烧基硫醇(TDM)使用量550 ppm，得到橡膠改質苯乙蝉 系樹脂組成物’其财、聚合條件列於表-，其所得之特 性及物性顺表二，所得之細旨組成物讀散相⑻為具有 21 200825130 * 吸藏粒子構造的橡膠粒子。 [實施例6] 同實施例1之聚合方式並依據表一配方及聚合條件， 亚且進料組成巾聚麵始劑二_第三丁基過氧化_六氯 苯二酸酯（HTP)550 ppm及鏈轉移劑叔—十二燒基硫醇 ⑽靡得到橡膠改f苯乙烯嫌脂組成物，其配 方、聚合條件顺表-，其所得之躲及物性列於表二， 所得之樹馳成物之分雜⑻為具树齡子構造的橡 • 膠粒子。 [實施例7] 同實施例1之聚合方式並依據表一之配方及聚合條 件，並且橡膠狀聚合物使用（D丁二烯—苯乙烯成分漸增之 苯乙烯/丁二烯-苯乙烯橡膠（同實施1橡膠)9重量份與⑵ 低順式(Low-C i s)含量之分歧構造丁二烯橡膠(順式含量= 35% ’ Mooney黏度在45、5%苯乙烯單體溶液的黏度為 35cps)0· 8重量份，二種橡膠並用，並且進料組成中聚合起 始劑二—第三丁基過氧化-六氫-對苯二酸酯（HTP)400 ppm 及鏈轉移劑叔-十二烷基硫醇(TDM)650 ppm，得到橡膠改質 苯乙稀系樹脂組成物，其配方、聚合條件列於表一，其所 得之特性及物性列於表二，所得之樹脂組成物之分散相（B) 為具有吸藏粒子構造的橡膠粒子。 [比較例1 ] 三個栓塞流式反應器（PFR)串聯，其各別容量為100公 升，將苯乙烯單體68重量份、丙烯腈單體32重量份、丁 二烯-苯乙烯成分漸增之苯乙烯/丁二烯-苯乙烯橡膠12重 22 200825130 里伤（B-taperS/B-S’本乙烤/丁二稀重量比= 25/75重量 % ’木尼(Mooney)黏度(MLm)為45)、溶劑乙笨43重量份、 二-第三丁基過氧化-六氫-對苯二酸醋(ΗΤΡ)45〇_，鍵轉 移劑叔-十二烷基硫醇(TDM)650ppin形成之混合溶液，以5〇 kg/小時之流量，連續地供給至第一反應器進行聚合反應； 將第一反應器反應所得之聚合物溶液導入第二反應哭；再 將第二反應器反應所得之聚合物溶液導入第三反應器進行 聚合反應；其中’第-、第二、第三反應器之反應槽之溫 度（反應益入口區域及出口區域二者之平均溫度）分別為 95、110、140°C，攪拌速率分別為60、45、20rpm ;且第二 反應裔為相反轉區，其出口的固體含量為28重量％，第二 反應器出口的固體含量為55重量％。 在聚合終了後，將由第三反應器反應所得的共聚物溶 液導入脫揮裝置，移除未反應單體及其他揮發份；將其製 粒即可得到本發明的橡膠改質苯乙烯系樹脂組成物；測^ 其橡膠成分含有量為14· 1重量％，橡膠粒子的中位粒徑為 〇· 45_ ’橡膠粒徑分佈寬幅(span)為1· 47 ;得到橡膠改質 本乙浠系樹脂組成物，其配方、聚合條件列於表一，其所 得之特性及物性列於表二，所得之樹脂組成物之分散相（B) 為具有吸藏粒子構造的橡膠粒子。 [比較例2] 同實施例1之聚合方式並依據表一配方及聚合條件，並且 進料組成中聚合起始劑二-第三丁基過氧化—六氫—對苯二酸酯 (HTP)450 ppm及鏈轉移劑叔-十二烷基硫醇(TDM)650 ppm，得 到橡膠改質苯乙烯系樹脂組成物，其配方、聚合條件列於表 23 200825130 一，其所得之特性及物性列於表二，所得之樹脂組成物之分散 相（B)為具有吸藏粒子構造的橡膠粒子。 [比較例3] 同實施例1之聚合方式並依據表一配方及聚合條件，並且 進料組成中聚合起始劑二—第三丁基過氧化-六氫—對苯二 酉文西曰（HTP)450 ppm及鏈轉移劑叔—十二烧基硫醇(了膽)35〇 ppm ’得到橡膠改質苯乙烯系樹脂組成物，其配方、聚合條 件列於表一，其所得之特性及物性列於表二，所得之樹脂 # 組成物之分散相（B)為具有吸藏粒子構造的橡膠粒子。 [比較例4] 同實施例1之聚合方式並依據表一配方及聚合條件， 並且進料組成中聚合起始劑二—第三丁基過氧化—六氫一對 笨二酸酯（HTP)300 ppm及鏈轉移劑叔—十二烷基硫醇 < (TDM)600 PPm，第二反應器為相反轉區，其出口固體含量 45重1%’得到橡膠改質苯乙烯系樹脂組成物，其配方、聚 合條件列於表一，其所得之特性及物性列於表二，所得之 _ 树知組成物之分散相（B)為具有吸藏粒子構造的橡膠粒子。 由比較例1得知，橡膠改質苯乙烯系樹脂組成物聚合 時不含正-丙烯酸丁酯單體，所得到橡膠改質苯乙烯系樹脂 組成物的橡膠粒子之粒徑分佈寬幅大於丨· 4,其組成物之光 澤度不佳。由比較例2得知，橡膠改質苯乙烯系樹脂組成 物含有小於〇· 05重量份(小於〇·丨重量份）的正—丙烯酸丁 S曰所彳于到橡勝改質苯乙烯系樹脂組成物的橡膠粒子之粒 控分佈寬幅大於1· 4，且組成物之光澤度不佳。由比較例3 待知’橡膠改質笨乙烯系樹脂組成物含有14·3重量份(大 24 200825130 ，8.0重量份)正-丙烯酸獨，所得到橡膠改質苯乙婦系 树脂組成物的_擊強度變差。由比較例4得知，橡膠粒 子^中位粒徑〇· (大於G. 6_)，橡膠粒子之粒徑分 佈寬幅2.5(大於1.4) ’造雜祕之綺度不佳及單位橡 膠含量之耐衝擊效率不佳。 惟，以上所述僅為本發明數個較佳可行之實施例，舉 凡熟習此項技藝人仕，其依本發明精神範疇所作的修飾或 變更，均理應包含在本發明技方案範圍内。'V three plug flow reactors (PFR) in series, each with a capacity of 1 liter, 68 parts by weight of styrene monomer, 32 parts by weight of acrylonitrile monomer, and rubbery polymer is butadiene - Styrene/butadiene-styrene rubber with increasing styrene content (B-taperS/BS, styrene/butadiene weight ratio = 25/75 wt% 'Mooney' viscosity (ML!h) is 45) 12 parts by weight, and 100 parts by weight of the total amount of the styrene monomer and the acrylonitrile monomer, 0.5 parts by weight of the butyl acrylate monomer, 43 parts by weight of the solvent, and the polymerization initiator Dibutyl peroxy-hexahydro-terephthalic acid vinegar (HTP) 450 ppm (based on all monomers), chain transfer agent t-dodecyl mercaptan (TDM) 600 ppm (based on all monomers) The mixed solution is continuously supplied to the first reactor at a flow rate of 50 kg/hour to carry out a polymerization reaction; the polymer solution obtained by the first reactor reaction is introduced into the second reactor; and the polymerization obtained by the second reactor reaction is further carried out. The solution is introduced into the third reactor for polymerization; wherein the temperatures of the first, second, and third reactors (reactor inlet) The regional and export areas are 20, 2008,130,130, the average temperature is 95, 110, 135 ° C, respectively, the stirring rate is 6 〇, 45, 20 rPm; and the first reactor is the opposite transfer zone, the solid content of the outlet is 28% by weight, the solids content of the third reactor outlet was 55% by weight. After the end of the polymerization, the copolymer solution obtained by the third reactor reaction is introduced into a devolatilizer to remove unreacted monomers and other volatile components; and granulated to obtain the rubber-modified styrene resin composition of the present invention. The rubber component content is 14% by weight, the rubber median diameter is 〇44#m, the dispersed phase (B) has rubber particles containing the structure of the occluded particles, and the number of absorbing particles of the rubber particles More than two or more. The rubber particle size distribution width (i.e., an) was 1.18; the formulation and polymerization conditions of the rubber modified styrene resin composition are listed in Table 1 and its characteristics and physical properties are listed in Table 2. [Examples 2 to 4] The polymerization formulation and polymerization conditions of Example 1 were different in that the composition of the acrylonitrile butadiene feed was divided into parts by weight, 5% by weight, and 2.5 parts by weight to obtain a rubber modification. The composition of the styrene-based resin, the formulation and the polymerization of the cake are as follows - the obtained product is the same as that of the second, the obtained tree. The dispersed phase of the brewed material (8) is a rubber particle having the structure of the contained occluded particles. [Example 5] The polymerization method of Example 1 was carried out according to the formulation and polymerization conditions of Table 1, and the polymerization initiator was changed to U|tert-butylperoxide 3,3,5-methylcyclohexane in the feed composition. , referred to as τ χ 瓢 他 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿 卿The obtained characteristics and physical properties are shown in Table 2, and the obtained composition read-off phase (8) is a rubber particle having a structure of 21 200825130 * occlusion particles. [Example 6] The polymerization method of the same as in Example 1 and according to the formulation of Table 1 and the polymerization conditions, the sub-feed composition of the face-forming agent bis-tert-butylperoxide-hexachlorophthalate (HTP) 550 Ppm and chain transfer agent t-dodecyl mercaptan (10) 靡 obtained rubber modified styrene sulphate composition, its formulation, polymerization conditions are in accordance with the table - the resulting hiding properties are listed in Table 2, the resulting tree The inclusions (8) of the adult matter are rubber particles with a tree-age structure. [Example 7] The polymerization method of Example 1 was carried out according to the formulation and polymerization conditions of Table 1, and the rubbery polymer was used (the styrene/butadiene-styrene rubber having a gradually increasing D butadiene-styrene component) (same as the implementation of 1 rubber) 9 parts by weight and (2) low cis (Low-Cis) content of the divergent structure of butadiene rubber (cis content = 35% ' Mooney viscosity in 45, 5% styrene monomer solution viscosity 35 parts by weight), 8 parts by weight, two kinds of rubbers are used together, and the polymerization initiator in the feed composition is di-tert-butylperoxide-hexahydro-terephthalate (HTP) 400 ppm and the chain transfer agent - Dodecyl mercaptan (TDM) 650 ppm to obtain a rubber modified styrene resin composition. The formulation and polymerization conditions are listed in Table 1. The properties and physical properties obtained are listed in Table 2. The resulting resin composition The dispersed phase (B) is a rubber particle having a occluded particle structure. [Comparative Example 1] Three plug flow reactors (PFR) were connected in series, each having a capacity of 100 liters, and 68 parts by weight of styrene monomer. 32 parts by weight of acrylonitrile monomer, styrene/butadiene-styrene rubber with increasing butadiene-styrene content 12 Weight 22 200825130 Injury (B-taperS/B-S' Baked / Dilute weight ratio = 25/75 wt% 'Mooney viscosity (MLm) is 45), solvent B stupid 43 parts by weight, Di-t-butylperoxide-hexahydro-terephthalic acid vinegar (ΗΤΡ) 45〇_, a key transfer agent t-dodecyl mercaptan (TDM) 650ppin mixed solution, 5〇kg/hour The flow rate is continuously supplied to the first reactor for polymerization; the polymer solution obtained by the first reactor reaction is introduced into the second reaction crying; and the polymer solution obtained by the second reactor reaction is introduced into the third reactor. a polymerization reaction; wherein the temperatures of the reaction tanks of the first, second, and third reactors (the average temperatures of the reaction inlet and outlet regions) are 95, 110, and 140 ° C, respectively, and the stirring rates are 60, respectively. 45, 20 rpm; and the second reaction is the opposite transfer zone, the solid content of the outlet is 28% by weight, and the solid content of the outlet of the second reactor is 55% by weight. After the end of the polymerization, the reaction obtained by the third reactor is obtained. The copolymer solution is introduced into the devolatilizer to remove unreacted monomers and other volatiles; The rubber-modified styrene-based resin composition of the present invention can be obtained by granulation; the rubber component content thereof is 14.1% by weight, and the median diameter of the rubber particles is 〇·45_' The span is 1.47; the rubber modified acetal resin composition is obtained, and the formulation and polymerization conditions are listed in Table 1. The obtained properties and physical properties are listed in Table 2, and the obtained dispersed phase of the resin composition is obtained. (B) is a rubber particle having a occluded particle structure. [Comparative Example 2] The polymerization method of the same as in Example 1 and according to the formulation of Table 1 and the polymerization conditions, and the polymerization initiator di-t-butyl group in the feed composition Oxidation-hexahydro-terephthalate (HTP) 450 ppm and chain transfer agent t-dodecyl mercaptan (TDM) 650 ppm, to obtain a rubber modified styrene resin composition, its formulation, polymerization conditions In Table 23, 200825130, the properties and physical properties obtained are shown in Table 2. The dispersed phase (B) of the obtained resin composition is rubber particles having a structure of occluded particles. [Comparative Example 3] The polymerization method of Example 1 was carried out according to the formulation of Table 1 and the polymerization conditions, and the polymerization initiator in the feed composition was di-tert-butylperoxide-hexahydro-p-benzoquinone vinorelbine ( HTP) 450 ppm and chain transfer agent t-dodecyl mercaptan (breast) 35〇ppm' obtained rubber modified styrene resin composition, the formulation and polymerization conditions are listed in Table 1, the characteristics obtained and The physical properties are shown in Table 2. The obtained resin # composition dispersion phase (B) is a rubber particle having a occluded particle structure. [Comparative Example 4] The polymerization method of Example 1 was carried out in accordance with the formulation of Table 1 and the polymerization conditions, and the polymerization initiator di-t-butylperoxy-hexahydroperoxydiester (HTP) was used in the feed composition. 300 ppm and chain transfer agent t-dodecyl mercaptan < (TDM) 600 PPm, the second reactor is the opposite transfer zone, and its outlet solids content is 45 wt% 1% to obtain a rubber-modified styrene resin composition. The formulation and polymerization conditions are shown in Table 1. The properties and physical properties obtained are shown in Table 2. The obtained dispersed phase (B) of the composition is a rubber particle having a structure of a occluded particle. As is understood from Comparative Example 1, the rubber-modified styrene-based resin composition did not contain a n-butyl acrylate monomer during polymerization, and the rubber particles of the obtained rubber-modified styrene resin composition had a particle size distribution larger than that of 丨. · 4, the composition of the gloss is not good. As is understood from Comparative Example 2, the rubber-modified styrene-based resin composition contained less than 〇·05 parts by weight (less than 〇·丨 by weight) of the acryl-butyl styrene resin. The particle size distribution of the rubber particles of the composition is greater than 1.4, and the gloss of the composition is not good. From Comparative Example 3, it is known that the rubber-modified stupid vinyl resin composition contains 14.3 parts by weight (large 24 200825130, 8.0 parts by weight) of n-acrylic acid alone, and the obtained rubber-modified styrene-based resin composition is obtained. The impact strength is worse. It is known from the comparative example 4 that the rubber particle has a median particle diameter 〇· (greater than G. 6_), and the rubber particle has a particle size distribution width of 2.5 (greater than 1.4). Impact resistance is not good. However, the above description is only a few preferred embodiments of the present invention, and modifications or changes made by the skilled person in the spirit of the present invention are intended to be included in the scope of the present invention.
25 200825130 聚合 條件 進料組成 實施例及比較例 Θ論 龌跳 〇f K* 1Φ α 攪拌速度 反應器溫度 δ 2 δ s 2 s s 2 乙笨 -¾ 莓 EM 瑙 E34 ffitt 莓 繆 Η 3i 審 xm (重量％ ) 1 (rpm) (°C) (重量份）i 時 1φ (重量份） (重量份） (重量份） 鄉 1Φ cn CJ1 ΓΟ oo g Ol S I—* ◦ H—i o CO U1 43.0 ·〇 <〇 _〇 〇1 GO CO ·◦ oo ο 12.0 1—t CJ1 cn bO oo s cn g CD CD CO CJl CO ο CD CD H—t C3 CO tv〇 cz> CD OO CD 12.0 CO CJl cn ISD OO s 私 cn g ◦ 1—^ CD CO CJl 1 43.01 CD CD Η-* ΟΊ oo IND O oo CD ΓΟ CD i4 赛 GO cn cn to oo g CJl g )—l 私 Ο j—^ o CO cn 1 43.0| CD 〇 Γ° cn oo tv〇 o cr> oo CD 12.0 cn ϋΐ DO OO g 私 CJl g ►—l GO cn i—^ g CO oo 1 43. 〇| 〇> d> ο cn GO IND 〇 ⑦ 00 CD H-A IND c=> Xh en g CD CD 1—1 cn h—i g 1 43.01 CD o I—* ο 18.0 82.0 16.0 實施例6 CJl 〇〇 g g 1—* 含 ►~k g 43.0! i—^ o bO DO GO 5¾ c=> CO oo ^4 ΟΊ cn IND OO CJl g i—^ 含 CD CO CJl 1 43.01 CD CD 32.0 68.0 12.0 比較例1 cn cn tND OO g cn s i—i h—^ Q CO cn 1 43.01 o b oo o CT> oo o 12.0 比較例2 cn cn IND OO cn g ►—-l 〇 H—i CD CO CJl 1 43.0| ◦ CO 32.0 68.0 11.6 比較例3 Ol CJl IN3 CO g 私 CD CD CJr 1 43.01 CD CD o CO r° CD CD OO CD 1___14j 1比較例4| 〔洳丨〕25 200825130 Polymerization conditions Feed composition examples and comparative examples 龌 龌 f f f f * * * α α α α α α α α α α α α α α Weight %) 1 (rpm) (°C) (parts by weight) i 1 φ (parts by weight) (parts by weight) (parts by weight) Township 1Φ cn CJ1 ΓΟ oo g Ol SI—* ◦ H—io CO U1 43.0 ·〇 <〇_〇〇1 GO CO ·◦ oo ο 12.0 1—t CJ1 cn bO oo s cn g CD CD CO CJl CO ο CD CD H—t C3 CO tv〇cz> CD OO CD 12.0 CO CJl cn ISD OO s Private cn g ◦ 1—^ CD CO CJl 1 43.01 CD CD Η-* ΟΊ oo IND O oo CD ΓΟ CD i4 赛 GO cn cn to oo g CJl g ) —l Private Ο j—^ o CO cn 1 43.0| CD 〇Γ° cn oo tv〇o cr> oo CD 12.0 cn ϋΐ DO OO g Private CJl g ►—l GO cn i—^ g CO oo 1 43. 〇| 〇>d> ο cn GO IND 〇7 00 CD HA IND c=> Xh en g CD CD 1-1 cn h-ig 1 43.01 CD o I-* ο 18.0 82.0 16.0 Example 6 CJl 〇〇gg 1—* with ►~kg 43.0! i—^ o bO DO GO 53⁄4 c=> CO oo ^4 ΟΊ cn IND OO CJl gi ^ CD CO CJl 1 43.01 CD CD 32.0 68.0 12.0 Comparative Example 1 cn cn tND OO g cn si—ih—^ Q CO cn 1 43.01 ob oo o CT> oo o 12.0 Comparative Example 2 cn cn IND OO cn g ►— -l 〇H-i CD CO CJl 1 43.0| ◦ CO 32.0 68.0 11.6 Comparative Example 3 Ol CJl IN3 CO g Private CD CD CJr 1 43.01 CD CD o CO r° CD CD OO CD 1___14j 1Comparative Example 4| 〔 〕
26 200825130 ^SL· ^/4 之物性 1之特性I 組成物 成份 中之組 組成物 >4> rr 棼 耐衝擊強度 鎿 g 〇° 光澤度 壤 ir 邑 橡膠中位粒徑 s! 1- 7 D ί 橡膠含量 |K a 審 -¾ 1 a 莓 繆 Η £34 D3CT 審 1 ο g 0^ 1—* 3 >—» · p s '! /^N 1 (重量份）1 ㈣V _ (重量份）1 (重量％) 18.50 CO cn CO GO ；1. 18 1 0.44 | •ο ο <=> 1 28,0 1 fo 14.0 實施例1 19.30 po IND CJ1 CO cn H—* Η—1 C5 IND •CD Ο 1—* cn DO OO ο ro o 14.0 μ 20.20 •CO g CO cn t—* 〇 1 0.41 1 Ο ο Γ° ΟΟ IND OO Ο fo 。 第 U) 19.50 r° CO (X> Η—* g p •ο ◦ GO —α DO OO o fo ·<=> 1 13.9 1實施例4 16.50 丨 2.00 | CO CO ί—k s p H—l ο ο •ο -<ι CO oo o 72.0 O υ?ϊ 18.00 g CO 〇1 二 to CD tNO ρ CD Η—i cn 18.0 oo r° CD 1—* CO )a| 〇\ 12.00 to •cn <z> CO s o 私 CO Η—k CO 23.0 2 1 li.o 16.90 h—* CT> cn 〜;1 to »—fc 1 0.45 1 ο ο •CD CD t\D 00 <〇 ίο o 1 14· 1 比較例1 17. 50 h—1 -o oo s 1—* on 1 0.45 1 ΓΟ 1 <0.05 1 to ·-<! o o 14.1 1比較例2 5.20 6. 50 CO oo p> oo cn 1 0.34 1 C3 Ο L 14.3 1 28.0 i 72.0 I 12.9 匕較例3 12. 80 *—λ ⑦ ϋΐ CJ1 C71 to s 0.65 ρ ο CO oo <=> 72.0 1 16.1 I 比較例426 200825130 ^SL· ^/4 Characteristic of physical property 1 I Group composition in composition component >4> rr 棼 impact strength 鎿g 〇° gloss ir 邑 rubber median particle size s! 1- 7 D ί Rubber content|K a 审 -3⁄4 1 a 缪Η 缪Η £34 D3CT Review 1 ο g 0^ 1—* 3 >—» · ps '! /^N 1 (parts by weight) 1 (four) V _ (parts by weight 1 (% by weight) 18.50 CO cn CO GO; 1. 18 1 0.44 | • ο ο <=> 1 28,0 1 fo 14.0 Example 1 19.30 po IND CJ1 CO cn H—* Η—1 C5 IND • CD Ο 1—* cn DO OO ο ro o 14.0 μ 20.20 •CO g CO cn t—* 〇1 0.41 1 Ο ο Γ° ΟΟ IND OO Ο fo . U) 19.50 r° CO (X> Η—* gp •ο ◦ GO —α DO OO o fo ·<=> 1 13.9 1 Example 4 16.50 丨 2.00 | CO CO ί—ksp H—l ο ο •ο -<ι CO oo o 72.0 O υ?ϊ 18.00 g CO 〇1 二to CD tNO ρ CD Η—i cn 18.0 oo r° CD 1—* CO )a| 〇\ 12.00 to •cn <z> CO so Private CO Η-k CO 23.0 2 1 li.o 16.90 h—* CT> cn 〜1 to »-fc 1 0.45 1 ο ο • CD CD t\D 00 <〇ίο o 1 14· 1 Comparative Example 1 17. 50 h -1 -o oo s 1 -* on 1 0.45 1 ΓΟ 1 <0.05 1 to ·-<! oo 14.1 1 Comparative Example 2 5.20 6. 50 CO oo p> oo cn 1 0.34 1 C3 Ο L 14.3 1 28.0 i 72.0 I 12.9 匕 Comparative Example 3 12. 80 *—λ 7 ϋΐ CJ1 C71 to s 0.65 ρ ο CO oo <=> 72.0 1 16.1 I Comparative Example 4
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