TW322488B - Styrene resin composition modified by rubber - Google Patents

Styrene resin composition modified by rubber Download PDF

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Publication number
TW322488B
TW322488B TW85110020A TW85110020A TW322488B TW 322488 B TW322488 B TW 322488B TW 85110020 A TW85110020 A TW 85110020A TW 85110020 A TW85110020 A TW 85110020A TW 322488 B TW322488 B TW 322488B
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Taiwan
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rubber
rubber particles
styrene
weight
copolymer
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TW85110020A
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Chinese (zh)
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Chyuan-Ming Lin
Dong-Bih Shiue
Wenn-Bin Hwang
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Chi Mei Corp
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Abstract

A styrene resin composition modified by rubber comprising a continuous matrix phase of styrene copolymer (A) and 5 to 45 wt.% relative to the resin composition of rubber particles dispersed in the continuous matrix phase, where the styrene copolymer is obtained by polymerizing 90 to 50 wt.% of styrene monomer, 10 to 50 wt.% of acrylonitrile monomer and 0 to 40 wt.% of other copolymerizable monomer, and the rubber particles comprises: (1) emulsified rubber particle (B) having weight average diameter of 0.05 to 0.8 (muon)m, and (2) bulk (or solution) rubber particles (C) having weight average diameter of 0.1 to 10 (muon)m, the average thickness of the hard styrene copolymer obtained by grafting emulsified rubber particle (B) and polymerizing grafted polymerizable monomer being 30 to 160A, and the average thickness of the hard styrene copolymer obtained by grafting bulk (solution) rubber particle (C) and polymerizing grafted polymerizable monomer being 90 to 300A.

Description

^22488 A7 _B7_ 五、發明説明（丨） 本發明偽有關於一種經棰暖改質之苯乙烯糸樹脂組成 物，特別是指一種具有良好衝擊強度、光澤均一性及熱安 定性之樹脂组成物。 按，苯乙烯条樹脂（如ABS樹脂等）之所以被廣泛 使用在電器、電子及汽車零件上，主要是其加工成型性、 物理性及機械性質方面皆有良好的評價，尤其是成型品的 良好外觀及光澤性上更是一大待色；惟隨著使用者對品質 要求的不斷提高，一般苯乙烯条樹脂在衝擊強度及光澤性 上仍有改良之須求，尤其在加工成型品上常會在不同部位 或者同一部位因觀察角度不同，而產生搔大的光澤差異性 ，進而對產品之外觀產生不良之影鬱；另一方面，目前加 工成型業者為了改善射出成型品之澆口外觀，乃逐漸探用 針孔式澆口（Pin gate)來射出成型，此一趨勢亦使得苯乙 烯条樹脂在熱安定性上的要求相對提高；因此，如何使苯 乙烯条樹脂具有良好之衝擊強度，並降低成品光澤差異性 且改善樹脂加工熱安定性，乃為此領域極待改善之課題。 經濟部中央標準局貝工消費合作社印製 ---Ί.--Ί.----{装------訂 (請先閲讀背面之注意事項再填寫本頁) 爰是，本發明之主要目的僳在提供一種具有良好衝擊 強度、光澤均一性，並具有良好熱安定性之經橡膠改質的 苯乙烯糸樹脂組成物。 而，本發明之經橡膠改質的苯乙烯糸樹脂組成物，其 主要成份包含：苯乙烯条共聚物（A)之連績基質相，以及 分散在該連續基質相中，且佔樹脂組成物5〜45重量％的橡 膠粒子；上述苯乙烯糸共聚物（Α)偽由苯乙烯条單體、丙 烯睛条單體及其他可共聚合單體聚合而成；而橡膠粒子包 第03頁 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 322488 A7 B7___ 五、發明説明（二） 含： ./ .I. (1) 重量平均粒徑0.05〜0.8卿之乳化橡膠粒子（B);及 (2) 重量平均粒徑0.1〜10卿之塊狀（或溶液）橡膠粒子（C) 其中，接枝在乳化橡膠粒子（B)上且由接枝聚合單體 聚合而成之硬質苯乙烯条共聚物的平均厚度為30〜160 A ,而接枝於塊狀（或溶液）橡膠粒子（C)上且由接枝聚合單 體聚合而成之硬質苯乙烯条共聚物的平均厚度為90〜300 A 〇 本發明之苯乙烯糸共聚物（A)係由苯乙烯条單體90〜 50重量份、丙烯腈条單匾10〜50重量份，及視需要而選之 可共聚合單體0〜40重量份聚合而得，其可以塊狀、溶液 、懸濁或乳化聚合法製得，其中又以塊狀或溶液聚合法為 佳，前述苯乙烯条共聚物（A)之重量平均分子量在60,000 〜400,000之間，較佳為80,000〜300,000之間；本發明苯 乙烯条共聚物（A)中的苯乙烯条單體可為：苯乙烯、α-甲基苯乙烯、Ρ-氛苯乙烯、p-t -丁基苯乙烯、ρ-甲基苯乙烯、〇-氛苯乙烯、P -氣苯乙烯、2,5 -二氣 苯乙烯、3,4 -二氣苯乙烯、2,4,6 -三溴苯乙烯、以及 2,5 _二溴苯乙烯等，其中，以苯乙烯或α -甲基苯乙烯 較佳。 使用於本發明中之丙烯腈条單體可為：丙烯腈、α -甲基丙烯晴等，其中以丙烯腈較佳；本發明苯乙烯条共聚 物（Α)中使用之可共聚合單體可為：（甲基）丙烯酸酯糸單 __第04頁__ 本紙張尺度適用中國國家橾準（CNS ) Α4规格（210X297公釐） (請先閎讀背面之注意事項再填寫本頁} 訂 經濟部中央標準局員工消費合作社印製 322488 經濟部中央樣準局員工消费合作社印製 A7 ’ B7五、發明説明（3 ) 體、馬來醯亞胺糸單醱、丙熥酸、甲基丙烯酸、無水馬來 .·. 酸等，其中，（甲基）丙烯酸醏糸單體可為：甲基丙烯酸甲 酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯 、甲基丙烯酸苯甲酯、甲基丙烯酸己酯、甲基丙烯酸環己 酯、甲基丙烯酸十二烷酯、甲基丙烯酸2-羥乙酯、甲基 丙烯酸縮水甘油酯、甲基丙烯酸二甲氨基乙酯、丙烯酸甲 酯、丙烯酸丁酯等，其中以甲基丙烯酸甲酯、丙烯酸丁酯 為佳。 馬來醛亞胺糸單體可為：馬來醯亞胺、N-甲基馬來 醛亞胺、N -異丙基馬來醛亞胺、N - 丁基馬來醯亞胺、N -己基馬來醯亞胺、N -辛基馬來醛亞胺、H -十二基馬來 醛亞胺、N -環己基馬來酵亞胺、N -苯基馬來醛亞胺、N - 2,3 -甲苯基馬來醛亞胺、N - 2,4-甲苯基馬來醛亞胺 、N_2,3 -乙苯基馬來醯亞胺、N-2,4 -乙苯基馬來醛亞 胺、N-2,3 - 丁苯基馬來醯亞胺、N-2,4 -丁苯基馬來醛 亞胺、H-2,6-甲苯基馬來醯亞胺、N - 2,3-氛苯基馬來 醛亞胺、H—2,4 —氛苯基馬來醛亞胺、N -2,3 -溴苯基馬 來醛亞胺、N - 2,4—溴苯基馬來醒亞胺等，其中又以N -苯基馬來醛亞胺為最佳。 本發明分散在苯乙烯条共聚物（A)之連鑛基質相中的 橡膠粒子佔樹脂组成物的5〜45重量！ϋ ,而分散在基質相 中之橡膠粒子偽以橡膠接枝共聚物的形式存在，即其包含 乳化橡膠粒子（Β)之接枝共聚物，以及塊狀（或溶液）橡膠 粒子（C)之接枝共聚物。 第05頁 (請先閱讀背面之注意事項再填寫本頁) 装- 訂 本紙張尺度適用中國國家標準（CNS ) Α4规格（210Χ297公釐） A7 _B7_ 五、發明説明（4 ) 本發明之乳化橡膠粒子（BP所製成之接枝共聚物傺在 二烯条橡膠乳液50〜85重量份存在下，與由苯乙烯条單體 90〜50重量S：、丙烯睛条單體10〜50重量X,以及其他可共 聚合單體0〜40重量組成之單髏混合物50〜15重量份，接 枝聚合而得重量平均粒徑0.05〜0.8邮之乳化橡膠接枝共 聚物之乳液，再經凝結、脱水、乾燥等步驟，而製得粉粒 狀的乳化橡膠粒子（Β)的接枝共聚物；上述二烯糸橡膠乳 液偽指包含有100〜60重量S；之共軛二烯單醱，和0〜40重 量!ϋ可共聚合不跑和單醴所形成的均聚合物（honopolyner ),或其共聚物（copolymer),前述共軛二烯單體可以下式 表示：^ 22488 A7 _B7_ V. Description of the invention (丨) The present invention is about a warm-modified styrene resin composition, especially a resin composition with good impact strength, gloss uniformity and thermal stability . According to press, the reason why styrene strip resin (such as ABS resin, etc.) is widely used in electrical appliances, electronics and automotive parts, mainly because of its good processability, physical properties and mechanical properties, especially for molded products Good appearance and gloss are even more important; but with the continuous improvement of users' quality requirements, the general styrene strip resin still needs improvement in impact strength and gloss, especially in processing molded products Often, there will be a large gloss difference in different parts or the same part due to different observation angles, which will cause a bad shadow on the appearance of the product; on the other hand, the current processing and molding industry in order to improve the appearance of the gate of injection molded products, It is gradually exploring the use of pin gate gates (Pin gate) for injection molding. This trend also makes the thermal stability requirements of styrene strip resin relatively increase; therefore, how to make styrene strip resin have good impact strength, And to reduce the gloss difference of finished products and improve the thermal stability of resin processing, this is a subject that needs to be improved in this field. Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs --- Ί .-- Ί .---- {installed ------ ordered (please read the precautions on the back before filling out this page) The main purpose of the invention is to provide a rubber-modified styrene resin composition which has good impact strength, uniform gloss and good thermal stability. However, the rubber-modified styrene resin composition of the present invention, the main components of which include: the continuous matrix phase of the styrene strip copolymer (A), and are dispersed in the continuous matrix phase and account for the resin composition 5 ~ 45% by weight of rubber particles; the above-mentioned styrene copolymer (A) is pseudo-polymerized from styrene strip monomers, acrylonitrile strip monomers and other copolymerizable monomers; The paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm) 322488 A7 B7___ V. Description of the invention (2) Contains: ./ .I. (1) Emulsified rubber particles with a weight average particle size of 0.05 ~ 0.8 (B ); And (2) Lumped (or solution) rubber particles (C) with a weight average particle size of 0.1 to 10%, of which the hard rubber is grafted onto the emulsified rubber particles (B) and is polymerized by graft polymerization monomers The average thickness of the styrene strip copolymer is 30 ~ 160 A, and the average thickness of the hard styrene strip copolymer grafted on the bulk (or solution) rubber particles (C) and polymerized by the graft polymerized monomer It is 90 ~ 300 A. The styrene copolymer (A) of the present invention is composed of benzene 90 ～ 50 parts by weight of vinyl monomers, 10 ～ 50 parts by weight of acrylonitrile strips, and 0 ～ 40 parts by weight of copolymerizable monomers as required, which can be in the form of blocks, solutions, and suspensions Or emulsion polymerization method, which is preferably block or solution polymerization method, the weight average molecular weight of the aforementioned styrene bar copolymer (A) is between 60,000 and 400,000, preferably between 80,000 and 300,000; benzene of the present invention The styrene strip monomers in the ethylene strip copolymer (A) may be: styrene, α-methylstyrene, Ρ-ambient styrene, pt-butylstyrene, ρ-methylstyrene, 〇-ambient Styrene, P-gas styrene, 2,5-digas styrene, 3,4-digas styrene, 2,4,6-tribromostyrene, and 2,5_dibromostyrene, etc., of which , Preferably styrene or α-methylstyrene. The acrylonitrile strip monomers used in the present invention may be: acrylonitrile, α-methacrylonitrile, etc., among which acrylonitrile is preferred; the copolymerizable monomers used in the styrene strip copolymer (Α) of the present invention Can be: (meth) acrylate sheet __page 04__ The paper size is applicable to China National Standard (CNS) Α4 specification (210X297mm) (please read the precautions on the back before filling this page) Printed by the Ministry of Economy, Central Standards Bureau, Employee Consumer Cooperatives 322488 Printed by the Ministry of Economics, Central Prototype Bureau, Employee Consumer Cooperatives A7 'B7 V. Description of the invention (3) Body, maleimide, acetone, alanine, methyl Acrylic acid, anhydrous Malay acid, etc., where the (meth) acrylic acid methacrylate monomer can be: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methylmethacrylate Benzyl acrylate, hexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate Ester, methyl acrylate, butyl acrylate, etc., Among them, methyl methacrylate and butyl acrylate are preferred. The maleimide can be: maleimide, N-methylmaleimide, N-isopropylmaleimide Amine, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, H-dodecylmaleimide, N-cyclohexylmaleimide Amine, N-phenylmaleimide, N-2,3-tolylmalealdimine, N-2,4-tolylmalealdimine, N_2,3-ethylphenylmaleimide Imine, N-2,4-ethylphenylmaleimide, N-2,3-butylphenylmaleimide, N-2,4-butylphenylmaleimide, H- 2,6-tolylmaleimide, N-2,3-aminophenylmalealdimine, H-2,4-aminophenylmalealdimine, N-2,3-bromobenzene Base maleimide, N-2,4-bromophenylmaleimide, etc., among which N-phenylmaleimide is the best. The present invention is dispersed in styrene strip copolymer (A ) The rubber particles in the ore-bearing matrix phase account for 5 to 45 weight of the resin composition! Ϋ, and the rubber particles dispersed in the matrix phase are pseudo-existing in the form of rubber graft copolymers, that is, they contain Graft copolymers of chemical rubber particles (B) and graft copolymers of bulk (or solution) rubber particles (C). Page 05 (please read the precautions on the back before filling out this page) The paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) A7 _B7_ V. Description of the invention (4) The emulsified rubber particles of the present invention (the graft copolymer made of BP is contained in the diene rubber emulsion 50 ~ In the presence of 85 parts by weight, a single skull mixture 50 ~ 15 composed of styrene strip monomer 90 ~ 50 weight S :, acrylic eye strip monomer 10 ~ 50 weight X, and other copolymerizable monomer 0 ~ 40 weight Parts by weight, graft polymerization to obtain an emulsion of an emulsion rubber graft copolymer with a weight average particle size of 0.05 to 0.8, and then through the steps of coagulation, dehydration, drying, etc. to obtain powdered granular emulsified rubber particles (B) Graft copolymers; the above-mentioned diene shit rubber emulsion pseudo-finger contains 100 ~ 60 weights of S; the conjugated diene monohydrate, and 0 ~ 40 weights! (Honopolyner), or its copolymer (copolymer), the aforementioned conjugated diene monomer The following formula:

R I CHa=C-CH=CH, 其中，R可為氫基、甲基或氣基等，而可共聚合不飽 和單體可為苯乙烯条單髏、丙烯腈条單體、甲基丙烯酸酯 条單體、丙烯酸酯条單體或其混合物。 經濟部中央標準局貝工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 本發明所使用之二烯条橡謬乳液可為聚丁二烯、丁二 烯一苯乙烯共聚物、丁二烯一丙烯腈共聚物、丁二烯一甲 基丙烯酸甲酯共聚物、異戊間二烯一丙烯酸丁酯共聚物等 ;上述二烯条橡膠乳液可以前述單體直接聚合成重量平均 粒徑0.05〜0.8 之形態，亦可先聚合成0.0 5〜0.18j«m之 小粒徑橡膠乳液後，再以傳統的橡膠肥大法，將0.05〜 0.18_之小粒徑橡膠E大成0.2〜0.8扉的橡瞟乳液，前述 橡膠肥大法可為添加有機酸或金展鹽或含羧酸基之高分子 第06頁 本^張尺度通用中國國家標準（CNS ) A4規格（210X297公釐） ： 32^88 A7 ΒΊ_ 五、發明説明（5 ) 凝集劑的化學肥大法、機械擻挣之機械肥大法或者冷凍肥 大法等；前述化學肥大法所採用之高分子凝集劑可例如丙 烯酸丁酯-甲基丙烯酸共聚物。 上逑乳化橡醪粒子（B)所製成之接枝共聚物的製備通 常是利用習用的接枝聚合技術，在橡膠狀聚合體存在下， 與苯乙烯条單體、丙烯腈条單體，及視需要而加入之可共 聚合單體混合物進行接枝聚合反應，利用化學性的結合或 接枝至少一種前述接枝單體所構成之硬質苯乙烯条共聚物 於二烯条橡膠上；依單體與二烯条橡膠的比例及聚合條件 ，可同時獲得接枝在二烯条橡膠上而為所需接枝厚度的聚 合物；通常接枝聚合反應的聚合溫度、起始劑之種類、橡 膠狀聚合體的物理、化學性質（如橡膠膨潤度、橡膠之共 聚合成份、含量）、粒子大小、單體加入的速率、單鼸與 橡膠的預先含浸程度、鏈移轉劑、乳化劑用量及種類等種 種因素，都會影響硬質苯乙烯糸共聚物之接枝厚度。 前述乳化接枝聚合單體所聚合而成之硬質苯乙烯条共 聚物一部份係以化學鍵接在二烯条橡膠上，另一部份則形 成游離狀之共聚物（free copolymer);又以橡膠接枝共聚 物之電子顯微鏡相片來觀察，橡膠粒子内可以包封前述硬 質苯乙烯条共聚物（Occlusion),也可以完全不包封硬質 苯乙烯糸共聚物，其包封程度視物性而定；另有一部份硬 質苯乙烯条共聚物接枝在橡膠粒子表面，此部份之硬質苯 乙烯糸共聚物乃為構成本發明乳化橡膠粒子（B)接枝共聚 物之接枝厚度層。 _第07頁_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I--------1 策------^------1 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 經濟部中央標準局員工消费合作社印製 A7 ___B7 _ 五、發明説明（fc ) 前述接枝聚合反應所添加之起始劑或觸媒，通常可在 聚合單體的0.01〜5.0重量份範圍内，最好在0.1〜3.0重 量份；其添加量依單體及所須聚合條件而定，前述起始劑 $增量加入，俾利於接枝聚合反應之進行。 又前述接枝聚合物的分子量大小，可藉由接枝聚合反 應的溫度加以控制，和/或配合相當少比例習用的分子董 調節劑，例如：硫醇、鹵化劑或帖烯等加以調節，此分子 量調節劑較為具體之例子有：正一十二烷基硫醇、第三一 十二烷基硫醇、α —甲基苯乙烯二聚物。 上述接枝聚合反應可利用單體混合物以連鑛或增量地 加入聚合条統中，並最好同時連績或增量的加入起始劑； 前述起始劑可使用各種習知的乳化自由基聚合反窿起始劑 ，例如：過氣化物（peroxy)、偶氮化合物或過硫酸盏化合 物；適當的過氧化物起始劑例如：異丙苯基過氧化物（di-cunyl pero-xide)、第三丁基過氣化物（tert-butyl-per-oxide)、過氣化苯甲酸（benzoyl perox.ide)、異丙苯化過 氧化氣（cunene hydroperoxide)、第三丁基過氧化氫（tert -butyl hydroperoxide)^ 〇 前述二烯条橡膠乳液與單體混合物之聚合反應，乃在 20〜100 t的惰性氣體下攪拌，其亦可加壓至0〜100P.S. I.G.;反應中欲使90%的單體被聚合，其聚合時間通常 需要2〜10小時，而以3〜8小時為佳。 乳化橡膠粒子（B)所製成之接枝共聚物所使用的苯乙 烯条單體、丙烯腈条單體及可共聚合單體，和苯乙烯糸共 ______第 08頁_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ------^----一 衣--II--訂 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 A7 _B7_ 五、發明説明（了） 聚物（A)中之單臛舉例説明楫®，在此不再赘述。 .·* 經由前述接枝聚合反應即可製得重量平均粒徑0.05〜 0.8/ao之橡膠接枝共聚物乳液，且接枝在乳化橡膠粒子（B) 上之硬質苯乙烯条共聚物的平均厚度為30〜160 A,較佳 之重量平均粒徑為0.06〜0.6卿，接枝厚度為40〜140A, 更佳為40〜1〇〇 A ;當其接枝厚度低於30 A時，對於樹脂 之衝擊強度及伸長率沒有改善的效果，樹脂的流動性也變 差，若接枝厚度高於160 A，不僅樹脂的流動性變差，其 衝擊強度亦降低。 上述乳化橡謬粒子（B)之接枝共聚物乳液中必須再加 入適當的凝結劑來進行凝结，一般所使用之凝结劑有硫酸 、醋酸之酸類、鹺土族金颶鹽，例如：氣化鈣之鈣鹽、氣 化鎂、硫酸鎂之鎂鹽、硫酸鋁之鋁鹽，其中以鹼土族金屬 鹽為佳；凝結完成之聚合物漿液經脱水程序去水份，再經 乾燥的處理，即可製得粉粒狀乳化橡膠粒子（B)之接枝共 聚物。 本發明之塊狀（或溶液）橡膠粒子（C)所製成之接枝 共聚物，偽將橡膠狀聚合物5〜30重量份，以及總合100 重量份之下述單體混合物，以塊狀及/或溶液聚合法聚合 而得，上述單體混合物包含苯乙烯条單體90〜50重量份、 丙烯腈条單體10〜50重量份及可共聚合單體0〜40重量份 ，當聚合反應之轉化率到達40〜90重量％時，再使前述共 聚物溶液經脱揮發步驟移除.未反應單髏及揮發份，即可製 得重量平均粒徑0.1〜10/®之塊狀或溶液橡膠粒子（C)的接 __第09頁_ 本紙張尺度適用中國國家榇準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) ,ΤΓ 322488 A7 B7 五、發明説明U ) 枝共聚物。 ./ (請先閲讀背面之注意事項再填寫本頁) 本發明橡膠粒子（C)之接枝共聚物可藉由連績式塊狀 或溶液聚合反應之反應器來完成，上述反應器包括：柱狀 流式反應器、完全混合式（CSTR)反應器，或者含靜 止型混合元件之管反應器等，其中以完全混合式反應器為 佳；上述反應器數量可為一個，也可併用兩個或兩個以上 ;在製造本發明橡膠粒子（C)之接枝共聚物時，可將聚合 起始劑加入反應中，該聚合起始劑包括過氧化醯類、過氧 化酯類、過氧化縮酮類、過氣化硪酸酯類，以及具有硝基 與環己烷瓌之偶氮化合物等，前述聚合起始劑之添加量通 常基於1〇〇重量份之單體的〇.〇1〜1.〇重量ϋ；。 上述反匾器之反應溫度像控制在80〜200它，最好控 制在90〜16〇υ之範圍内，而反應器之壓力偽控制在1〜5 kg/cina之間，至於原料溶液滯留在反慝器内之時間宜在1 〜5小時間；另外，為了控制聚合物之分子量，可使用例 如正一十二烷基硫醇、第三一十二烷基硫醇、葙品油烯等 之鍵移轉剤。 經濟部中央樣隼局貝工消費合作社印製 在聚合物聚合终了後，通常僳將所得之共聚物溶液以 預熱器加熱至最高溫，然後再以脱揮發步驟移除未反應單 體及揮發份，一般脱揮發步费[可使用減壓脱氣槽之装置， 或押出機脱氣裝置脱除揮發份，之後以冷凝器將之收集成 回收液，並將回收液中之水份予以除去後，重新作為原料 溶液使用；而經脱揮發份之聚合熔融物，將其押出造粒即 可得到塊狀（或溶液）橡膠粒子（C)之接枝共聚物。 第10頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^^2488 A7 ’ B7_ 五、發明説明（3 ) (請先W讀背面之注意事項再填寫本頁) 適用於本發明塊狀（或溶液）橡膠粒子（C)之接枝共 聚物的橡膠狀聚合物有共軛二烯橡膠，較佳如丁二烯橡膠 、異戊間二烯橡膠、氛丁二烯橡膠等；其中，丁二烯橡膠 之類型有高順式（Hi-Cis)含量及低順式（Low -Cis)含量等 ;高順式橡膠中，其順式（C is)/乙烯基（Vinyl)之典聖重 S組成為94〜98ϋί/1〜5¾，其餘組成則為反式（Trans )結 構，其Mooney黏度在20〜120間，分子量範圍100,〇〇〇〜 800,000為佳；低順式橡膠中，順式/乙烯基之典型重量 組成在20〜403ί/1〜20¾，其餘為反式結構，其Mooney黏 度在20〜120間；其他適合的橡膠材料尚有：丙烯睛/丁 二烯橡膠、苯乙烯/丁二烯橡膠，或是上述不同橡驪之混 合；適合於本發明的苯乙烯/丁二烯共聚合橡醪，其聚合 型式可為二段式（di-block)共聚合、三段式（tri-block) 共聚合、無規則共聚合（random)或星式共聚合（star type );上述苯乙烯/丁二烯共聚合橡膠之苯乙烯/丁二烯重 量比例範圍較佳為5/95到80/20 ,分子量範圍較佳為50 ,000〜600,000;適合於本發明之橡膠以丁二烯橡膠及苯 乙烯/丁二烯橡膠為佳，其中又以丁二烯橡膠更佳。 經濟部中央標準局貝工消费合作社印製 至於本發明塊狀（或溶液）橡膠粒子（C)之接枝共聚物 所使用的苯乙烯条單體、丙烯腈条單體及其他可共聚合單 髏之種類，和苯乙烯条共聚物（A)中之單體舉例説明相同 ,在此不赘述。 本發明塊狀（或溶液）橡膠粒子（C)之接枝共聚物中 ,由接枝單體聚合成之硬質苯乙烯条共聚物之一部份偽以 第11頁 本紙張又度逋用中國國家橾準（CNS ) A4规格（210X297公釐） 322488 A7 B7 五、發明説明（) (請先閲讀背面之注意事項再填寫本頁) 化學鍵結在橡膠狀聚合物上，_ S —部份則形成游離狀之共 聚物（free copolymer);又橡膠粒子（C)内部可以包封前 述硬質苯乙烯条共聚物，其粒徑多在0.01〜0.5郷之間， 橡膠粒子内部之包封數可以是一艏（單一包封）或數傾以 上；另有一部份硬質苯乙烯条共聚物接枝在橡膠粒子（C) 表面，此部份之硬質苯乙烯糸共聚物乃為構成本發明塊狀 (或溶液）橡膠粒子（C)之接枝共聚物的接枝厚度層。前 逑接枝厚度之調控可依接枝聚合反應之溫度、滯留時間、 橡膠待性[如分子量、聚合成份、徹結構之1,2-乙烯基（v inyl)含量等]、鍵移轉劑及溶劑之種類、用置、起始劑的 種類、反應器的設計、攪拌轉速、相反轉前後之待定操作 條件等來達成。 由塊狀（或溶液）聚合反應而得之橡膠粒子（C)的接 枝共聚物，其製得橡膠重量平均粒徑為0.1〜10卿，且接 枝在橡膠上之硬質苯乙烯条共聚物的平均厚度為90〜300 A,較佳之重量平均粒徑為0.2〜7 接枝厚度為100〜 300 A ;當接枝厚度低於90A時，無法得到光澤均一性的 樹脂，且樹脂之熱安定性亦較差。 經濟部中央標準局員工消費合作社印製 本發明經橡膠改質之苯乙烯条樹脂組成物可由苯乙烯 条共聚物（A)、乳化橡膠粒子（B)之接枝共聚物，及塊狀（ 或溶液）橡膠粒子（C)之接枝共聚物混合押出製得；當乳化 橡膠粒子（B)與塊狀（或溶液）橡膠粒子（C)之含量總合低 於樹脂組成物5重量S!時，樹脂的衝擊強度及伸長率變差 ,若其含量高於45重量3：,樹脂的流動性及光澤均一性會 第12頁 本紙張尺度適用中國國家榇準（CNS ) A4規格（210X297公釐） 經濟部中央標準局負工消費合作社印製 A7 B7 五、發明説明（丨丨） 降低，樹脂之熱安定性亦較差β- 本發明所諝的橡膠粒子之重量平均粒徑，偽指將樹脂 超薄切片或乳液塗抹，經染色後以10, 〇〇〇倍率之穿透式電 子顯撖鏡照相，將相Η中所照得之橡膠分散粒子約200〜 1000個，各別测定其粒徑，再以下式求得重量平均粒徑卽 Σ n . D t 4 橡膠重置平均粒徑=—- Σ n i D i 3 ηί=橡膠粒子徑為Di之橡膠粒子數 本發明所讚的接枝在橡膠粒子上之硬質苯乙烯条共聚 物的平均厚度，傜將樹脂以丙酮溶解，並將可溶分以遠心 分離除去，再將所得凝膠分散於丙酮中形成分散液，接著 將數滴分散液滴入瓖氣樹脂糸接箸劑之主劑中，使主劑與 凝膠充份混合，再以真空乾燥除去丙酮後加入環氣樹脂条 接箸劑之硬化劑充份混合，混合後加熱使其硬化，邸可得 到凝膠在環氧樹脂中分散良好之試驗Η。 此處所使用之環氧樹脂糸接著劑為商品名Araldite R a p i d (C i b a - G e i g y公司製）之市售品。 所製得之試驗H以四氧化锇（〇sO«)染色後，以切片機 切片，再以60,000倍之穿透式電子顯微鏡照相；經由四氣 化餓染色後，橡膠部份及環氣樹脂被染成黑色，而硬質苯 乙烯糸共聚物之接枝層則不會被染色而為白色，將相Η中 所照得之橡膠分散粒子25値以上，以「描臛紙」描橡膠及 接枝層外形，再剪下稱重，依單體重童之相當面積可換算 出接枝層面積，再以該面積除以橡膠粒子周長而得橡膠粒 第13茛 本紙張尺度逋用中國國家標準（CNS ) Α4規格（210X297公釐） ---------- 衣------、玎------, (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製 A7 ， _B7__ 五、發明説明（P) 子之粒子徑（Dd的厚度層並依下式求出平均厚度： .·. η η Σ D.t./Σ Di3 i = 1 1 » 1 本發明可依需要進一步加入酚糸或碕丙酸酯条氧化防 止薄I,而得到具有預定特性之樹脂組成物，本發明亦可適 當添加用以改良苯乙烯糸樹脂成型性之光安定劑、紫外線 吸收劑、充填劑、著色劑、滑劑、可塑劑及帶電防止劑； 此外，本發明亦可混合聚合物合金用樹脂，例如：聚碩酸 酯、聚醛胺、聚酯（PET、PBT)、聚伸苯基謎、聚氣乙烯、 聚甲基丙烯酸甲酯、乙烯一甲基丙烯酸甲酯共聚物、聚丙 烯、苯乙烯一丁二烯塊狀共聚物、氫化丙烯睛一丁二烯共 聚物、氫化苯乙烯一丁二烯塊狀共聚物等而使用之，其諝 配量一般相對於樹脂組成物100重量份的5〜200重量份。 為得到本發明之樹脂組成物，其混合方法具代表性者 是：以一般使用之漢歇爾混合機乾混後再以諸如押出混合 機、捏合機或班伯立混練機等之混合機溶融混合。 本發明之樹脂组成物適用於射出成型法、押出成型法 、壓縮成型法、吹延成型法、熱成型法、真空成型法及中 空成型法等成型方法。 為更進一步詳細説明本發明，再以實施例與物性測試 説明如下，以下组成物之成份除非特別磬明，否則是以佔 全部組成重悬以重量百分計的份數和百分比來表示。 以下舉出實施例詳細説明本發明，但本發明之範圍並 不以此等實施例為限。 ____第14頁_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I I I I I ( 裝 I I I I I I 訂 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（U) &lt;製備例&gt; &lt;製備例I 一 1 &gt;苯乙烯一丙烯腈共聚物（A-ι)的製備： 以12 kg/hr的速度將苯乙烯76重量3!、丙烯腈24重量S； 之原料予以混合，再將乙撑二硬脂酵胺3.0 g/hr*、過氣化 苯甲醛、第三一十二烷基硫醇，以及後述反應所除去之揮 發份經冷凝後所形成之回收液合併作為餵給液，以供給入 内溫度保持在108 υ且容積45公升之附有攪拌器的連績式 釜型反應器，且使反應液中的甲苯比例保持在15« ,而聚 合率保持在55Χ。 當反應液通過脱揮發裝置除去揮發份後，可得到苯乙 烯一丙烯腈共聚物的顆粒；另一方面，所除去之揮發成份 以冷凝器凝縮作為回收液，並連績地與前述原料混合疲混 合再使用之；此方法傜由過氣化苯甲醯的量諏整反應速度 ，或調整第三一十二烷基硫醇之置，而以約12 kg/hr的速 度製成熔融流動指數為3.0的苯乙烯一丙烯腈共聚物（A-1) 〇 &lt;製備例I一2&gt;苯乙烯一丙烯腈一甲基丙烯酸甲酯共聚 物（A-2)的製備： 依&lt;製備例I_1&gt;的製備方法，不同之處在於：以 苯乙烯68重量X、丙烯腈22重量X、甲基丙烯酸甲酯10重量 !1：之原料進行反應，並製成熔融流動指數為2.0的苯乙烯-丙烯腈一甲基丙烯酸甲酯共聚物（Α-2)。 &lt;製備例I 一 3&gt;苯乙烯一丙烯腈一 α —甲基苯乙烯共聚 物（Α-3)的製備： ____第 15 頁_ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐) ~ -----^-----{ 装------訂 (請先閲讀背面之注意事項再填寫本頁) 五、發明説明（丨4 ) A7 B7 依&lt;製備例I一ι&gt;的製備方法，不同之處在於：以 苯乙烯68重董％、丙烯睛22重量3!、α —甲基苯乙烯10重暈 !«之原料進行反應，並製成熔融流動指數為1.5的苯乙烯一 丙烯睛一 α —甲基苯乙烯共聚物（Α-3)。 &lt;製備例I一4〉苯乙烯一丙烯腈一Ν—苯基馬來醯亞胺 共聚物（Α-4)的製備： 依&lt;製備例I一1&gt;的製備方法，不同之處在於：以 苯乙烯68重置：《、丙烯睛22重量!Κ、Ν —苯基馬來醯亞胺10 重量：1!之原料進行反應，並製成熔融流動指數為1.0的苯乙 烯一丙烯睛一 Ν —苯基馬來醛亞胺共聚物（Α-4)。 &lt;製備例1-1 &gt;乳化橡膠粒子（Β-1)之接枝共聚物的製造： 經濟部中央標準局負工消费合作社印製 成 重鼉衫 1,3-丁 二 烯 95.0 丙 烯 腈 5.0 過硫酸 鉀溶 液 15.0 焦 磷 酸 納 3.0 油 酸 鉀 1.5 蒸 餾 水 140.0 第三-十二烷基碕醇 0.2 -1- I. —^^1 ΐ^— 1^1 - In ^ I ml —^n 1·1 n^i 一 ^ (請先閱讀背面之注意事項再填寫本頁) 依以上配方在651C反應溫度下反應12小時，得到轉化 率為9U、固體含量約為40Χ、重量平均粒徑為0.1抑》的 合成橡膠膠乳。 另外，以下列成份製造含羧酸基的高分子凝集劑：^_iiL 童眚扮 _第16頁__ 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） Α7 Β7 經濟部中央橾準局員工消費合作社印製 五、發明説明（丨s ) η - 丙烯酸乙酯 丙烯酸 第三一十二烷基硫醇 油酸鉀 二辛基磺基琥珀酸鈉 異丙苯化過氧化氫 甲醛合次硫酸氫紡 蒸蹓 水 依以上配方在751C反應溫度下反應5小時，得到轉化 率95¾、pH值6.0的含羧酸基的高分子凝集薄ί。 之後，利用3重量份的含羧酸基的高分子凝集劑（乾重 )來肥大100重量份的合成橡膠膠乳（乾重），所得到的肥大 化橡膠乳液的pH值為8.5,重量·平均粒徑為0.30/an。 最後，再以肥大化橡膠乳液依下述配方進行接枝聚合 反應，以製造乳化橡膠粒子（B-1)接枝共聚物： 成_i£L 重最 松 肥大化橡膠乳液（乾重） 苯乙烯 丙 烯 腈 油酸鉀 第三一十二烷基碕醇 異丙苯化過氣化氫 硫酸亞鐵溶液（0.2S!) 甲醛化次硫酸納溶液（ιοχ) ______第 17 頁 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 35 15 0.32.01.0 0.4 0.3 200 (請先聞讀背面之注意事項再填寫本頁) 訂 100.0 25 3 咖488 A7 B7 五、發明説明（|b ) 乙二胺四醋酸溶液（0.25¾)^ 20.0 蒸餾水 200.0 (請先閲讀背面之注意事項再填寫本頁) 將上述配方中的苯乙烯/丙烯腈以連缳添加方式在5 小時内加入反應糸統中聚合，所製得之橡膠接枝乳液以氦 化鈣（CaCM凝結、脱水後，再乾燥至水份含量2¾以下， 就可製得本發明所箱要的乳化橡膠粒子（B-1)接枝共聚物（ 橡膠含量75重量S!),其橡膠粒子的重量平均粒徑為0.30»。 &lt;製備例Π - 2 &gt;乳化橡睡粒子（B-2)之接枝共聚物的裂造·· 以&lt; 製備例I -1 &gt;所製得之合成橡膠膠乳（橡膠重量 平均粒徑0.1卿），直接和下表配合進行接枝聚合反應，以 製得橡膠含置在50重量3!之乳化橡膠粒子（Β-2)之接枝共 聚物，其橡瞟粒子之重量平均粒徑0.1扉。 成 _iiL 菫暑松 合成橡膠膠乳（〇.1典）（乾重） 100.0 苯乙烯 75.0 丙烯睛 25.0 &gt; I 八 Amr* 油酸鉀 2.0 第三一十二烷基碇醇 0.6 異丙苯化過氣化氫 1.4 碇酸亞鐵溶液（0.2X) 8.6 甲醛化次硫酸鈉溶液（10¾) 8.6 乙二胺四醋酸溶液（0.25¾) 57.0 蒸餾水 200.0 經濟部中央標隼局貝工消費合作社印製 &lt;製備例1-3&gt;乳化橡_粒子（B-3)之接枝共聚物的製造： 第18頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 五、發明説明（丨7 ) A7 B7 以&lt; 製備例1-1 &gt;之製嫌^方法，不同之處在於接枝 聚合反應的配方及使用量，此接枝聚合反應之配方如下： s_&amp;. 肥大化橡膠乳液（乾重） 100. 苯 乙 烯 22.0 丙 烯 睛 8.3 甲基 丙烯酸 甲酯 3.0 油 酸 拥 1.2 經濟部中央揉準局貝工消費合作社印製 第三一十二烷基碇醇 異丙苯化過氣化氫 0.5 硫酸亞鐵溶液（0.2¾) 3.0 甲醛化次硫酸鈉溶液（10¾) 3 乙二胺四醋酸溶液（0.25¾) 20 蒸皤水 200 依上表配方所製得之橡膠接枝乳液以氣化鈣（CaCU) 凝結、脱水後，再乾燥至水份含量2¾以下，就可製得本發 明所需要的乳化橡膠粒子（B-3)之接枝共聚物（橡膠含量75 重量30,其橡膠粒子的重量平均粒徑為0.30wn〇 &lt;製備例1-4 &gt;乳化橡膠粒子（B-4)之接枝共聚物的製造： 以&lt; 製備例Π -1 &gt;的製備方法，不同之處在於接枝 聚合反應的配方及使用量，此接枝聚合反應之配方如下： 肥大化橡膠乳液（乾重） 苯乙烯 100. 22. (請先閲讀背面之注意事項再填寫本頁) 第19頁 本紙張尺度適用中國國家標準（CNS ) A4規格（2!0X297公釐） 經濟部中央標準局貝工消费合作社印製 A7 __B7 五、發明説明（IR ) 丙 烯 睛-/ 7. α _ 甲基苯乙烯 1. Ν - 苯基馬來醯亞胺 2. 油 酸 鉀 1. 第三一 十二烷基硫醇 0. 異丙苯化過氧化氩 0. 碕酸亞鐵溶液（0.23!) 3. 甲醛化次硫酸鈉溶液（10¾) 3. 乙二胺 四醋酸溶液（0.25¾) 20. 蒸 皤 水 200. 依上表配方所製得之橡膠接枝乳液以氯化鈣（CaC 1 a) 凝結、脱水後，再乾燥至水份含量以下，就可製得本發 明所需要的乳化橡膠粒子（B-4)的接枝共聚物（橡膠含量75 重量：《),其橡膠粒子的重量平均粒徑為0.30卿。 &lt;製備例]1-5&gt;乳化橡膠粒子（B-5)之接枝共聚物的製造： 以&lt; 製備例1-1 &gt;之製備方法，不同之處在於接枝 聚合反應的配方及使用量，此接枝聚合反應之配方如下： ^重畺份 肥大化橡膠乳液（乾重） 100.0 苯 乙 烯 8.4 丙 烯 腈 2.8 油 酸 鉀 2.0 第三 —十二烷基硫醇 0.1 異丙苯化過氧化氫 第20頁 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） --Ί.--------f 装------訂 (諳先閲讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（) 硫酸亞鐵溶液（0.2X) - / 1. 甲醛化次硫酸納溶液（10¾) 1. 乙二胺四醋酸溶液（0.255；) 7. 蒸皤水 200. 上表配方中之苯乙烯/丙烯睛以連绩添加方式在1 hr 中加入反應条統中聚合，所製得之橡膠接枝乳液以氯化鈣 (CaCK)凝結、脱水後，再乾燥至水份含量2¾以下，就可 製得本發明所需要的乳化橡膠粒子（B-5)之接枝共聚物（橡 膠含量90重量S：),其橡膠粒子的重量平均粒徑為0.30_。 &lt;製備例Κ-6&gt;乳化橡膠粒子（Β-6)之接枝共聚物的製造： 以&lt; 製備例1-1 &gt;之製備方法，不同之處在於接枝 聚合反應的配方及使用量，此接枝聚合反應之配方如下： 成 _ίΆ. 雷營松 ---Ί-------f 装-- (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 肥大化橡膠乳液（乾重） 100.0 苯乙烯 300.0 丙烯睛 100.0 油酸鉀 0.5 第三一十二烷基硫醇 2.2 異丙苯化過氧化氫 5.4 硫酸亞鐵溶液（0.2¾) 32.5 甲醛化次硫酸鈉溶液（10%) 32.5 乙二胺四醋酸溶液（0.25¾) 22.0 蒸餾水 200.0 上表配方中之苯乙烯/丙烯腈以連績添加方式在8 hr 第21頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 8 8 經濟部中央標準局負工消費合作社印装 A7 B7 i、發明説明（Μ ) 中加入反應条統中聚合，所裂得之橡膠接枝乳液以氣化鈣 (CaCM凝結、脱水後，再乾燥至水份含量2¾以下，就可 製得本發明所需要的乳化橡膠粒子（B-6)之接枝共聚物（橡 膠含量20重量!S),其橡膠粒子的重量平均粒徑為0.30/®。 &lt;製備例1-1 &gt;塊狀（或溶液）橡膠粒子（C-1)之接枝共聚 物的裂造： 以0.08重量份之過氣化苯甲酵作為起始劑，將6.6重量 份之聚丁二嫌（旭化成公司出品，商品名為Asadene 55AS )完全溶解於74.4重量份之苯乙烯、25.6重量份之丙烯猜 及30重量份之乙苯中，以形成進料溶液，之後將進料溶液 連缳送入髓積為45公升之第一反應器中，反應溫度為100 C、反應器内配置設有冷卻循環管之螺旋式攪拌器，其攪 拌速率為150 rpffl,在第一反應器之單體轉化率為15S：,將 經過第一反應器反應後之混合物連續取出並依序送入第二 、三、四反應器中，同時在第三反應器中加入0.1重童份 之第三一十二烷基硫醇，相反轉現象在第二反應器中產生 ，上述第二、三、四反應器之裝置與第一反應器相同，但 其反應溫度依序為105C、110 °C、125亡，而攪拌速率依 序為270 rpn、150rpn及ΙΙΟγρβ;俟混合物之轉化率達60¾ 時，將混合物取出送入脱揮發裝置中，移去未反應之單體 及揮發物，之後將其押出製粒，即可製得塊狀（或溶液）橡 膠粒子（C-1)之接枝共聚物，其橡膠粒子之重量平均粒徑 為0.95/an,橡膠含量為10重量S；。 &lt;製備例51 - 2 &gt;塊狀（溶液）橡膠粒子（C-2)之接枝共聚物 第22頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---J.--：----f^------IT (請先閲讀背面之注意事項再填寫本頁) 經濟部中央榡準局員工消費合作社印製 A7 __B7___ 五、發明説明（〉丨） 的製造：-/ 依&lt;製備例I-1&gt;的製備方法，不同之處在於作為 起始劑之過氣化苯甲酵為0.12重量J：，第一反應器之單體 轉化率為16 S!、轉速為140 rpn,而第二反應器之溫度為 llOt：、轉速為300 rpa,反應後將其押出製粒，即可製得 塊狀（或溶液）橡膠粒子（C-2)之接枝共聚物，其橡膠粒子 之重量平均粒徑為0.75卿，而橡膠含量為10重量X。 &lt;製備例皿-3&gt;塊狀（或溶液）橡膠粒子（C-3)之接枝共聚 物的製造： 依&lt;製備例I-1&gt;的製備方法，不同之處在於作為 起始劑之過氣化苯甲酵為0.05重量份，且將0.2重量份之 第三一十二烷基硫醇加入第二反應器中，而第一反應器之 單體轉化率為19 3!、轉速為270 rpm,第二反應器之轉速 為250 rpm ,相反轉發生在第一反應器中，反應後將其押 出製粒，即可製得塊狀（或溶液）橡膠粒子（C-3)之接枝共 聚物，其橡膠粒子之重量平均粒徑為1.0卿，而橡膠含量 為ίο重量。 &lt;製備例Π -4 &gt;塊狀（或溶液）橡膠粒子（C-4)之接枝共聚 物的製造： 使用第三一十二烷基硫醇及過氣化苯甲酵作為起始劑 ，將6.6重量份之聚丁二烯（旭化成公司所出品，商品名為 八33(^1^55&amp;5)完全溶解於74.4重量份之苯乙烯、25.6重 量份之丙烯睛及30重量份之乙苯中，以形成進料溶液，之 後將進料溶液連績送入體積為45公升之第一反應器中，反 ______第 23頁_ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） I-11^--Ί ；----{裝------訂 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 322488 A7 B7 五、發明説明（n) 應溫度為95它、反應器内配置設有冷卻循環管之螺旋式攪 拌器，其攪拌速率為120rpin,在第一反應器之單體轉化率 為14¾ ,將經過第一反應器反應後之混合物連續取出並依 序送人第二、三、四反應器中，同時在第二反應器中加入 0.08重量份之第三一十二烷基硫醇，相反轉現象在第二反 應器中產生，上述第二、三、四反應器之裝置與第一反應 器相同，但其反應溫部依序為105t、115 υ、130TC ,而 搜拌速率依序為200 r*pm、150 γρπ及llOrpm;俟混合物之 轉化率達60¾時，將混合物取出送入脱揮發裝置裝，移去 未反應之單體及揮發物，之後將其押出製粒，即可製得塊 狀（或溶液）橡膠粒子（04)之接枝共聚物，其橡膠粒子之 重量平均粒徑為3.3卿，而橡膠含量為10重量X。 本發明實施例與比較例所製得樹脂組成物之物性測試 標準如下： 一. 熔體流動指數（MI)： 依ASTM D-1238規定測試，以g/l〇 min表示。 二. X氏衝擊強度（IZOD)： 依ASTM D-256規定測試，以Kg ♦ cra/cn表示。 三. 伸長率： 依ASTM D-638法測試，以5{來表示。 四. 光澤梯度（光澤均一性）： 以加德纳（Gardner 60° Incidence angle)依 ASTM D-523規定測試，單位採％ ,測試試Η為一長300 ππ、 寬25 nn、厚3 nm之射出製品，其扇狀澆口距邊端15 第24頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） IΛ--------f ·裝-- (請先閲讀背面之注意事項再填寫本頁) -訂 經濟部中央標準局員工消費合作社印製 hi * _________B7_ 五、發明説明（θ ) βπ,而測其距繞口 5 cn(GkJss 1)、25 cn (Glass 2) 處之光澤度差值，可作為光澤梯度之判斷方法，梯度 愈小，表示光澤均一性愈佳。RI CHa = C-CH = CH, where R can be a hydrogen group, a methyl group or a gas group, etc., and the copolymerizable unsaturated monomer can be a styrene strip single skull, an acrylonitrile strip monomer, methacrylate Strip monomers, acrylate strip monomers or mixtures thereof. Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The diene strip rubber emulsion used in the present invention may be polybutadiene, butadiene-styrene copolymer , Butadiene-acrylonitrile copolymer, butadiene-methyl methacrylate copolymer, isoprene-butyl acrylate copolymer, etc .; the above-mentioned diene rubber emulsion can be directly polymerized into the weight average of the aforementioned monomers In the form of particle size 0.05 ~ 0.8, it can also be polymerized into a small particle size rubber emulsion of 0.0 5 ~ 0.18j «m, and then the small particle size rubber E of 0.05 ~ 0.18_ can be converted into 0.2 ~ For the rubber emulsion of 0.8 °, the aforementioned rubber hypertrophy method can be the addition of organic acids or gold-spreading salts or polymers containing carboxylic acid groups. Page 06 This ^ sheet size General Chinese National Standard (CNS) A4 specification (210X297 mm): 32 ^ 88 A7 ΒΊ_ V. Description of the invention (5) Chemical aggregating method of agglutinating agent, mechanical aggravating method or mechanical freezing method, etc .; the polymer agglutinating agent used in the aforementioned chemical aggregating method can be, for example, butyl acrylate Acrylic copolymer. The preparation of the graft copolymer made of the emulsified rubber mash particles (B) is usually made by conventional graft polymerization technology, in the presence of a rubber-like polymer, with styrene strip monomers, acrylonitrile strip monomers, And the copolymerizable monomer mixture added as needed for graft polymerization, using chemically combined or grafted at least one of the aforementioned graft monomers to form a hard styrene strip copolymer on the diene strip rubber; The ratio of monomer to diene rubber and the polymerization conditions can simultaneously obtain the polymer grafted on the diene rubber to the desired graft thickness; usually the polymerization temperature of the graft polymerization reaction, the type of initiator, The physical and chemical properties of rubber-like polymers (such as rubber swelling degree, rubber copolymerization content, content), particle size, monomer addition rate, pre-impregnation degree of monomer and rubber, chain transfer agent, emulsifier dosage Various factors, such as the type, will affect the grafting thickness of the hard styrene copolymer. A part of the rigid styrene strip copolymer polymerized by the foregoing emulsified graft polymerization monomer is chemically bonded to the diene strip rubber, and the other part forms a free copolymer; and Observed by the electron microscope photo of the rubber graft copolymer, the rubber particles can encapsulate the aforementioned hard styrene strip copolymer (Occlusion), or it can not encapsulate the hard styrene copolymer at all. ; Another part of the hard styrene strip copolymer is grafted on the surface of the rubber particles, and this part of the hard styrene copolymer is the graft thickness layer constituting the graft copolymer of the emulsified rubber particles (B) of the present invention. _ 第 07 页 _ This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) I -------- 1 policy ------ ^ ------ 1 (please first Read the precautions on the back and then fill out this page) Printed by the Ministry of Economy Central Standards Bureau Employee Consumer Cooperative Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative A7 ___B7 _ V. Invention Description (fc) The start of the aforementioned graft polymerization reaction The agent or catalyst can usually be in the range of 0.01 ~ 5.0 parts by weight of the polymerized monomer, preferably 0.1 ~ 3.0 parts by weight; the amount of addition depends on the monomer and the polymerization conditions required The addition is beneficial to the progress of graft polymerization. In addition, the molecular weight of the aforementioned graft polymer can be controlled by the temperature of the graft polymerization reaction, and / or it can be adjusted with a relatively small proportion of conventional molecular director regulators, such as mercaptans, halogenating agents, or vinylenes. More specific examples of this molecular weight regulator are: n-dodecyl mercaptan, third-dodecyl mercaptan, and α-methylstyrene dimer. The above-mentioned graft polymerization can use the monomer mixture to continuously or incrementally add to the polymerization system, and it is best to simultaneously or incrementally add the initiator; the aforementioned initiator can use various conventional emulsification free Initiator based on polymerized anti-smoke, for example: peroxy compounds, azo compounds or persulfate compounds; suitable peroxide initiators are for example: di-cunyl pero-xide ), Tert-butyl-per-oxide, benzoyl perox.ide, cumene hydroperoxide, tert-butyl hydroperoxide (Tert -butyl hydroperoxide) ^ 〇The polymerization reaction of the aforementioned diene strip rubber emulsion and monomer mixture is stirred under an inert gas of 20 ~ 100 t, which can also be pressurized to 0 ~ 100P.SIG; 90% of the monomers are polymerized, and the polymerization time usually takes 2 to 10 hours, and preferably 3 to 8 hours. The styrene strip monomers, acrylonitrile strip monomers and copolymerizable monomers used in the graft copolymer made of emulsified rubber particles (B), together with styrene strip ______ 第 08 页 _ This paper size Applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) ------ ^ ---- 一 衣 --II--book (please read the precautions on the back before filling in this page) Central Standard of the Ministry of Economic Affairs A7 _B7_ printed by Bureau Cooper Consumer Co., Ltd. V. Description of Invention (It's) The example of the polymer (A) is exemplified by 楫 ®, which will not be repeated here. . ** The rubber graft copolymer emulsion with a weight average particle diameter of 0.05 to 0.8 / ao can be prepared through the aforementioned graft polymerization reaction, and the average of the hard styrene bar copolymer grafted on the emulsified rubber particles (B) The thickness is 30 ~ 160 A, the preferred weight average particle size is 0.06 ~ 0.6%, the graft thickness is 40 ~ 140A, more preferably 40 ~ 100A; when the graft thickness is less than 30 A, for resin The impact strength and elongation have no effect of improvement, and the fluidity of the resin also deteriorates. If the graft thickness is higher than 160 A, not only does the fluidity of the resin deteriorate, but also the impact strength decreases. The graft copolymer emulsion of the above emulsified rubber particles (B) must be added with an appropriate coagulant for coagulation. Generally, the coagulants used are sulfuric acid, acetic acid, and Tulu gold hurricane salt, such as calcium carbonate Calcium salt, vaporized magnesium, magnesium sulfate magnesium salt, aluminum sulfate aluminum salt, which is preferably alkaline earth metal salt; the polymer slurry after condensation is dehydrated by dehydration process, and then dried. A graft copolymer of powdery and granular emulsified rubber particles (B) was prepared. The graft copolymer made of the block-shaped (or solution) rubber particles (C) of the present invention is composed of 5 to 30 parts by weight of the rubber-like polymer and a total of 100 parts by weight of the following monomer mixture to form a block It is obtained by polymerization in solution and / or solution polymerization method. The above monomer mixture contains 90-50 parts by weight of styrene strip monomer, 10-50 parts by weight of acrylonitrile strip monomer and 0-40 parts by weight of copolymerizable monomer. When the conversion rate of the polymerization reaction reaches 40 ~ 90% by weight, the copolymer solution can be removed through the devolatilization step. The unreacted single skeleton and the volatile matter can be obtained as a block with a weight average particle size of 0.1 ~ 10 / ® Or the solution rubber particle (C) connection__ 第 09 页 _ This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling this page), ΤΓ 322488 A7 B7 V. Description of invention U) Branch copolymer. ./ (Please read the precautions on the back before filling this page) The graft copolymer of the rubber particles (C) of the present invention can be completed by a continuous block or solution polymerization reactor. The above reactors include: Cylindrical flow reactors, complete mixing (CSTR) reactors, or tube reactors with static mixing elements, etc., of which the complete mixing reactor is preferred; the number of the above reactors may be one or two may be used in combination One or more than two; in the production of the graft copolymer of the rubber particles (C) of the present invention, a polymerization initiator may be added to the reaction, the polymerization initiator includes peroxoyl peroxides, peroxyesters, peroxide For ketals, pervaporated phosphoric acid esters, and azo compounds with nitro and cyclohexane, the addition amount of the aforementioned polymerization initiator is usually based on 100 parts by weight of monomers. ~ 1.0 Weight ϋ ;. The reaction temperature of the above-mentioned anti-plaque device is controlled at 80 ~ 200, preferably in the range of 90 ~ 16〇υ, and the pressure of the reactor is pseudo controlled at 1 ~ 5 kg / cina, as for the raw material solution to stay in The time in the reactor is preferably between 1 and 5 hours; in addition, in order to control the molecular weight of the polymer, for example, n-dodecyl mercaptan, third-dodecyl mercaptan, and terpinolene can be used. The key is transferred. Printed by the Beigong Consumer Cooperative of the Central Falcon Bureau of the Ministry of Economic Affairs. After the polymerization of the polymer is completed, the resulting copolymer solution is usually heated to the highest temperature with a preheater, and then the unreacted monomer and volatilization are removed by the devolatization step. Parts, the general devolatization step [can use a vacuum degassing tank device, or an extruder degassing device to remove volatiles, and then use a condenser to collect it into a recovery liquid, and remove the water in the recovery liquid After that, it is used again as a raw material solution; and after the devolatilized polymer melt is extruded and granulated, a graft copolymer of block (or solution) rubber particles (C) can be obtained. Page 10 This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297mm) ^^ 2488 A7 'B7_ V. Invention description (3) (Please read the precautions on the back side and fill in this page) The rubber-like polymer inventing the graft copolymer of block (or solution) rubber particles (C) is a conjugated diene rubber, preferably such as butadiene rubber, isoprene rubber, atmospheric butadiene rubber, etc. ; Among them, the type of butadiene rubber has high cis (Hi-Cis) content and low cis (Low-Cis) content, etc .; high cis rubber, its cis (C is) / vinyl (Vinyl) The composition of Shengdian S is 94 ~ 98ϋί / 1 ~ 5¾, and the rest of the composition is trans (Trans) structure, its Mooney viscosity is between 20 ~ 120, and the molecular weight range is 100,000 ~ 800,000; low cis In rubber, the typical weight composition of cis / vinyl is 20 ~ 403ί / 1 ~ 20¾, and the rest is trans structure, and its Mooney viscosity is between 20 ~ 120; other suitable rubber materials are: acrylonitrile / butadiene Rubber, styrene / butadiene rubber, or a mixture of the above different rubbers; suitable for the styrene of the present invention / Diene copolymerized mash, the polymerization type can be two-stage (di-block) copolymerization, three-stage (tri-block) copolymerization, random copolymerization (random) or star copolymerization (star type) The styrene / butadiene copolymerized rubber has a styrene / butadiene weight ratio range of preferably 5/95 to 80/20, and a molecular weight range of preferably 50,000 to 600,000; the rubber suitable for the present invention is Butadiene rubber and styrene / butadiene rubber are preferred, but butadiene rubber is more preferred. The styrene strip monomer, acrylonitrile strip monomer and other copolymerizable monomers used in the graft copolymer of the block (or solution) rubber particles (C) of the present invention printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The type of skull is the same as the monomer in the styrene strip copolymer (A), and will not be repeated here. In the graft copolymer of block (or solution) rubber particles (C) of the present invention, a part of the hard styrene strip copolymer polymerized by the graft monomer is pseudo-used in China on page 11 National Standard (CNS) A4 specification (210X297mm) 322488 A7 B7 V. Description of invention () (Please read the precautions on the back before filling in this page) Chemical bonding to rubber-like polymer, _ S — part Form a free copolymer (free copolymer); and the rubber particles (C) can encapsulate the aforementioned rigid styrene strip copolymer, the particle size of which is mostly between 0.01 ~ 0.5 m, the number of encapsulation inside the rubber particles can be One bow (single encapsulation) or more than a few degrees; another part of the hard styrene strip copolymer is grafted on the surface of the rubber particles (C), this part of the hard styrene copolymer is to form the block of the present invention ( Or solution) the grafted thickness layer of the graft copolymer of rubber particles (C). The thickness of the front graft can be adjusted according to the temperature of the graft polymerization, the residence time, the rubber properties [such as molecular weight, polymerization composition, the structure of 1,2-vinyl (vinyl) content, etc.], bond transfer agent And the type of solvent, use, type of initiator, reactor design, stirring speed, undetermined operating conditions before and after reverse rotation, etc. A graft copolymer of rubber particles (C) obtained by block (or solution) polymerization, a hard styrene strip copolymer with a rubber weight average particle size of 0.1 to 10% and grafted on rubber The average thickness is 90 ~ 300 A, and the preferred weight average particle size is 0.2 ~ 7. The graft thickness is 100 ~ 300 A; when the graft thickness is less than 90A, the resin with uniform gloss cannot be obtained, and the heat of the resin is stable Sex is also poor. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, the rubber-modified styrene strip resin composition can be a styrene strip copolymer (A), an emulsified rubber particle (B) graft copolymer, and a block (or Solution) The rubber particles (C) are obtained by mixing and extruding the graft copolymer; when the content of the emulsified rubber particles (B) and the bulk (or solution) rubber particles (C) is less than 5 weight S of the resin composition! , The impact strength and elongation of the resin become worse, if its content is higher than 45 weight 3 :, the fluidity and gloss uniformity of the resin will be on page 12. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm ) Printed by the Ministry of Economic Affairs Central Bureau of Standards, Consumer Cooperative A7 B7 V. Description of the invention (丨 丨) The thermal stability of the resin is reduced, and the thermal stability of the resin is also poor. Ultra-thin sections or emulsions are smeared, and after dyeing, they are photographed with a transmission electron microscope with a magnification of 10,000, and the dispersed rubber particles in phase H are about 200 ~ 1000, and the particle size is measured separately. , Then find the weight balance by the following formula The particle size is Σ n. D t 4 rubber reset average particle size = —- Σ ni D i 3 ηί = the number of rubber particles with a rubber particle diameter of Di The hard styrene strip grafted on the rubber particles praised by the present invention The average thickness of the copolymer, dissolve the resin in acetone, and separate and remove the soluble components by telecentricity, then disperse the resulting gel in acetone to form a dispersion, and then add a few drops of the dispersion into the urethane resin. In the main agent of the agent, the main agent and the gel are fully mixed, and then the acetone is removed by vacuum drying, and then the hardener added by the ring gas resin stripping agent is fully mixed, mixed and heated to harden, and the gel can be obtained. Test Η for good dispersion in epoxy resin. The epoxy resin adhesive used here is a commercially available product under the trade name Araldite R a p i d (C i b a-G e i g y). The prepared test H was dyed with osmium tetroxide (〇sO «), sliced with a microtome, and then photographed with a transmission electron microscope of 60,000 times; after dyeing through four gasification, the rubber part and the ring gas resin It is dyed black, and the graft layer of the rigid styrene copolymer will not be dyed but white. The rubber dispersed particles photographed in phase H are more than 25, and the rubber and the Cut the shape of the branch layer, and then cut and weigh it. The area of the graft layer can be converted according to the equivalent area of the single heavy child, and then the area is divided by the circumference of the rubber particle to obtain the rubber particle. Standard (CNS) Α4 specifications (210X297mm) ---------- clothing ------, 玎 ------, (please read the precautions on the back before filling this page) Printed by A7, _B7__, Employee Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (P) The particle diameter of the particle (Dd thickness layer and the average thickness is obtained according to the following formula: .. η η Σ Dt / Σ Di3 i = 1 1 »1 The present invention can further add phenol or propionate strips to prevent oxidation of thin I as needed, and obtain resins with predetermined characteristics For the composition, the present invention may appropriately add light stabilizers, ultraviolet absorbers, fillers, colorants, slip agents, plasticizers, and antistatic agents for improving the moldability of styrene resin; in addition, the present invention may also be mixed Resins for polymer alloys, such as: polyesters, polyaldehyde amines, polyesters (PET, PBT), polyphenylene phosphates, polyethylene gas, polymethyl methacrylate, ethylene methyl methacrylate copolymer Materials, polypropylene, styrene-butadiene block copolymers, hydrogenated acrylonitrile-butadiene copolymers, hydrogenated styrene-butadiene block copolymers, etc., the amount of the compound is generally relative to the resin 5 to 200 parts by weight of 100 parts by weight of the composition. In order to obtain the resin composition of the present invention, the typical mixing method is: dry-mixing with a general-purpose Hanshall mixer, followed by, for example, an extruder mixer, kneading Machine or Banbury mixer. The resin composition of the present invention is suitable for injection molding, extrusion molding, compression molding, blow molding, thermoforming, vacuum molding and hollow molding In order to explain the present invention in more detail, the following examples and physical property tests are used to explain the following. The components of the following composition are resuspended in parts by weight based on the total composition unless otherwise specified. It is expressed as a percentage. The following examples illustrate the present invention in detail, but the scope of the present invention is not limited to these examples. ____Page 14_ This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 ) IIIII (set IIIIII (please read the precautions on the back before filling in this page) A7 B7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of Invention (U) &lt; Preparation Examples &gt; &lt; Preparation Example I 1. Preparation of styrene-acrylonitrile copolymer (A-ι): The raw materials of styrene 76 weight 3 and acrylonitrile 24 weight S at a rate of 12 kg / hr are mixed, and then ethylene Stearic acid amine 3.0 g / hr *, pergasified benzaldehyde, 31-dodecyl mercaptan, and the volatiles removed by the reaction described later are condensed and the recovered liquid formed by condensation is used as a feeding liquid for supply The internal temperature is kept at 10 A continuous-type reactor with a stirrer and a volume of 45 liters and a volume of 45 liters, and the proportion of toluene in the reaction solution was kept at 15 «, and the polymerization rate was kept at 55X. When the reaction liquid is removed by the devolatilization device, particles of styrene-acrylonitrile copolymer can be obtained; on the other hand, the removed volatile components are condensed by the condenser as the recovery liquid, and are continuously mixed with the aforementioned raw materials. Mix and use again; this method is to adjust the reaction rate from the amount of pergasified benzoyl acetone, or adjust the placement of the 31st alkyl mercaptan, and make the melt flow index at a rate of about 12 kg / hr Styrene-acrylonitrile copolymer (A-1) of 3.0. <Preparation Example I-2> Preparation of styrene-acrylonitrile-methyl methacrylate copolymer (A-2): According to &lt; Preparation Example I_1> The preparation method is different, with 68 weight X of styrene, 22 weight X of acrylonitrile, and 10 weight of methyl methacrylate! 1: The raw materials are reacted and styrene with a melt flow index of 2.0 is prepared- Acrylonitrile-methyl methacrylate copolymer (Α-2). &lt; Preparation Example I-3 &gt; Preparation of styrene-acrylonitrile-α-methylstyrene copolymer (Α-3): ____Page 15_ This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297 Mm) ~ ----- ^ ----- {Packed ----- ordered (please read the precautions on the back before filling in this page) Fifth, the description of the invention (丨 4) A7 B7 by &lt; The preparation method of Preparation Example I ι &gt; is different: the raw materials of 68% by weight of styrene, 22% by weight of acrylonitrile 3 !, and 10% of α-methylstyrene are reacted, and melt flow is made Styrene-acrylonitrile-α-methylstyrene copolymer (Α-3) with an index of 1.5. &lt; Preparation Example I-4> Preparation of styrene-acrylonitrile-N-phenylmaleimide copolymer (Α-4): According to the preparation method of &lt; Preparation Example I-1 &gt;, the difference is that : Reset with styrene 68: ", 22 weight of acrylonitrile! K, N-phenylmaleimide 10 weight: 1! The raw materials are reacted, and styrene-acrylonitrile with a melt flow index of 1.0 is prepared. Ν—Phenylmaleimide copolymer (Α-4). &lt; Preparation Example 1-1 &gt; Production of graft copolymers of emulsified rubber particles (B-1): Printed by the Ministry of Economic Affairs, Central Standards Bureau, Negative Consumer Cooperative as a heavy-duty shirt 1,3-butadiene 95.0 acrylonitrile 5.0 Potassium persulfate solution 15.0 Sodium pyrophosphate 3.0 Potassium oleate 1.5 Distilled water 140.0 Third-dodecylbenzyl alcohol 0.2 -1- I. — ^^ 1 Ι ^ — 1 ^ 1-In ^ I ml — ^ n 1 · 1 n ^ i one ^ (Please read the notes on the back before filling in this page) According to the above formula, the reaction is carried out at a reaction temperature of 651C for 12 hours, and the conversion rate is 9U, the solid content is about 40X, and the weight average particle size is 0.1 Suppressed synthetic rubber latex. In addition, the following ingredients are used to produce a polymer coagulant containing carboxylic acid groups: ^ _iiL 童 眚 装 _ 第 16 页 __ This paper size is applicable to China National Standards (CNS) A4 specifications (210X297 mm) Α7 Β7 Central Ministry of Economic Affairs Printed by the Employees' Cooperative of the Prospective Bureau V. Description of Invention (丨 s) η-Ethyl acrylate Acrylic acid Thirteen-dodecyl mercaptan potassium oleate Sodium dioctylsulfosuccinate Cumene hydroperoxide formaldehyde The hydrogen sulfite spin-distilled water was reacted at the reaction temperature of 751C for 5 hours according to the above formula, to obtain a carboxylic acid group-containing polymer agglutination thinner with a conversion rate of 95¾ and a pH of 6.0. Thereafter, 100 parts by weight of synthetic rubber latex (dry weight) was enlarged using 3 parts by weight of polymer coagulant (dry weight) containing carboxylic acid group, and the pH of the resulting enlarged rubber emulsion was 8.5, weight · average The particle size is 0.30 / an. Finally, the hypertrophy rubber emulsion is grafted and polymerized according to the following formula to produce the emulsified rubber particles (B-1) graft copolymer: Cheng_i £ L the most bulky hypertrophy rubber emulsion (dry weight) benzene Ethylene acrylonitrile potassium oleate, 31st alkyl alkyl alcohol, cumene, pergasified ferrous hydrogen sulfate solution (0.2S!), Formaldehyde sodium hyposulfite solution (ιοχ) ______page 17 This paper size is applicable China National Standard (CNS) Α4 specification (210X297mm) 35 15 0.32.01.0 0.4 0.3 200 (please read the precautions on the back before filling this page) Order 100.0 25 3 Coffee 488 A7 B7 V. Description of invention (| b ) Ethylenediaminetetraacetic acid solution (0.25¾) ^ 20.0 Distilled water 200.0 (Please read the precautions on the back before filling in this page) Add the styrene / acrylonitrile in the above formula to the reaction mixture within 5 hours by continuous addition After polymerization in the system, the obtained rubber graft emulsion is calcium helium (CaCM is coagulated and dehydrated, and then dried to a moisture content of 2¾ or less to prepare the emulsified rubber particles (B-1) required by the present invention. Graft copolymer (rubber content 75 weight S!), Its rubber particles The weight average particle size is 0.30 ». &Lt; Preparation Example Π-2 &gt; Cracking of the graft copolymer of emulsified rubber particles (B-2) · Prepared by &lt; Preparation Example I -1 &gt; The synthetic rubber latex (rubber weight average particle size 0.1%), directly in conjunction with the following table for graft polymerization, to prepare a graft copolymer containing 50% by weight of 3! Emulsified rubber particles (Β-2) , The weight average particle size of its rubber particles is 0.1%. Cheng_iiL Suzuki Summer Pine Synthetic Rubber Latex (O.1 Code) (Dry Weight) 100.0 Styrene 75.0 Acrylic Eye 25.0 &gt; I Eight Amr * Potassium Oleate 2.0 Section Tris-dodecyl alcohol 0.6 Cumene pervaporated hydrogen 1.4 Ferrous oxalate solution (0.2X) 8.6 Sodium formaldehyde sulfoxylate solution (10¾) 8.6 Ethylenediaminetetraacetic acid solution (0.25¾) 57.0 Distilled water 200.0 Printed by the Central Standard Falcon Bureau Beigong Consumer Cooperative of the Ministry of Economic Affairs &lt; Preparation Example 1-3 &gt; Production of Graft Copolymer of Emulsified Rubber_Particles (B-3): Page 18 This paper scale applies the Chinese National Standard (CNS ) A4 specification (210X297mm) V. Description of the invention (丨 7) A7 B7 is manufactured under &lt; Preparation Example 1-1 &gt; ^ The difference is the formula and amount of graft polymerization reaction. The formula of this graft polymerization reaction is as follows: s_ &. Enlarged rubber emulsion (dry weight) 100. Styrene 22.0 Acrylonitrile 8.3 Methyl methacrylate 3.0 Oleic acid 1.2 Printed by the Ministry of Economic Affairs Central Bureau of Precision Industry Beigong Consumer Cooperatives, the 31st alkyl cumyl alcohol cumene pervaporized hydrogen 0.5 ferrous sulfate solution (0.2¾) 3.0 formaldehyde sodium sulfoxylate solution ( 10¾) 3 Ethylenediaminetetraacetic acid solution (0.25¾) 20 Distilled water 200 The rubber graft emulsion prepared according to the formula in the table above is coagulated and dehydrated with calcium carbonate (CaCU), and then dried to a moisture content below 2¾ , The graft copolymer of the emulsified rubber particles (B-3) required by the present invention (rubber content 75 weight 30), the weight average particle diameter of the rubber particles is 0.30wn. &Lt; Preparation Example 1-4 &gt;; Production of graft copolymers of emulsified rubber particles (B-4): The preparation method of &lt; Preparation Example Π-1 &gt; is different except for the formulation and amount of graft polymerization reaction, and the graft polymerization reaction The formula is as follows: Hypertrophic rubber emulsion (dry weight Styrene 100. 22. (Please read the precautions on the back before filling in this page) Page 19 This paper size is applicable to China National Standard (CNS) A4 specification (2! 0X297mm) Beigong Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs Printed A7 __B7 5. Description of the invention (IR) Acrylonitrile- / 7. α _ Methylstyrene 1. Ν-phenylmaleimide 2. Potassium oleate 1. Thirteen-dodecyl mercaptan 0. Cumene argon peroxide 0. Ferrous lanate solution (0.23!) 3. Formaldehyde sodium sulfoxylate solution (10¾) 3. Ethylenediaminetetraacetic acid solution (0.25¾) 20. Steamed water 200. The rubber graft emulsion prepared according to the formula in the table above is coagulated and dehydrated with calcium chloride (CaC 1 a), and then dried to below the moisture content to obtain the emulsified rubber particles (B-4) required by the present invention. ) Of the graft copolymer (rubber content 75 weight: "), the weight average particle diameter of the rubber particles is 0.30%. &lt; Preparation Example 1-5 &gt; Production of graft copolymers of emulsified rubber particles (B-5): The preparation method of &lt; Preparation Example 1-1 &gt; differs in the formulation of the graft polymerization reaction and The amount of use, the formula of this graft polymerization reaction is as follows: ^ weight of the thickening rubber emulsion (dry weight) 100.0 styrene 8.4 acrylonitrile 2.8 potassium oleate 2.0 third-dodecyl mercaptan 0.1 cumene Hydrogen Oxide Page 20 This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) --Ί .-------- f Packing ------ ordered (read first on the back) (Notes and fill in this page again) A7 B7 V. Description of invention () Ferrous sulfate solution (0.2X)-/ 1. Formaldehyde sodium hyposulfite solution (10¾) 1. Ethylenediaminetetraacetic acid solution (0.255;) 7. Steamed water 200. The styrene / acrylonitrile in the above formula was added to the reaction system in 1 hr by continuous addition, and the obtained rubber graft emulsion was coagulated and dehydrated with calcium chloride (CaCK) , And then dried to a moisture content of 2¾ or less, the graft copolymer (rubber) of the emulsified rubber particles (B-5) required by the present invention can be prepared An amount of 90 wt S :), weight average particle diameter of the rubber particles was 0.30_. &lt; Preparation Example K-6 &gt; Production of graft copolymers of emulsified rubber particles (Β-6): The preparation method of &lt; Preparation Example 1-1 &gt; is different in the formulation and use of the graft polymerization reaction The formula of the graft polymerization reaction is as follows: Cheng _ίΆ. Lei Yingsong --- Ί ------- f outfit-- (please read the precautions on the back before filling in this page) Bureau of Standards, Staff and Consumers Cooperative printed a rubber latex for hypertrophy (dry weight) 100.0 Styrene 300.0 Acrylonitrile 100.0 Potassium oleate 0.5 Thirteen behenyl mercaptan 2.2 Cumene hydroperoxide 5.4 Ferrous sulfate solution (0.2 ¾) 32.5 Formaldehyde sodium hyposulfite solution (10%) 32.5 Ethylenediaminetetraacetic acid solution (0.25¾) 22.0 Distilled water 200.0 The styrene / acrylonitrile in the formula in the table above is added continuously at 8 hr page 21 The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 8 8 Printed by the Ministry of Economic Affairs Central Standards Bureau Negative Consumer Cooperative A7 B7 i. The description of the invention (Μ) is added to the reaction system to polymerize, and the cracked rubber Grafted emulsion with vaporized calcium (CaCM coagulates and dehydrates, then dry After drying to a moisture content of 2¾ or less, the graft copolymer (rubber content 20 weight! S) of the emulsified rubber particles (B-6) required by the present invention can be prepared. The weight average particle diameter of the rubber particles is 0.30 / ®. &Lt; Preparation Example 1-1 &gt; Cracking of graft copolymers of bulk (or solution) rubber particles (C-1): Using 0.08 parts by weight of over-gasified benzoylase as an initiator, 6.6 parts by weight of polybutadiene (produced by Asahi Kasei Corporation, trade name Asadene 55AS) is completely dissolved in 74.4 parts by weight of styrene, 25.6 parts by weight of propylene and 30 parts by weight of ethylbenzene to form a feed solution, After that, the feed solution was continuously fed into the first reactor with a medullary volume of 45 liters. The reaction temperature was 100 C. The reactor was equipped with a spiral stirrer with a cooling circulation tube, and its stirring rate was 150 rpffl. The monomer conversion rate of the first reactor is 15S: the mixture after the first reactor reaction is continuously taken out and sent to the second, third, and fourth reactors in sequence, and 0.1 weight is added to the third reactor Tongfen's 31st-12-mercaptan mercaptan, the reverse conversion phenomenon is produced in the second reactor The equipment of the second, third, and fourth reactors is the same as the first reactor, but the reaction temperature is 105C, 110 ° C, 125 in sequence, and the stirring rate is 270 rpn, 150rpn, and ΙΙΟγρβ in sequence; 俟When the conversion rate of the mixture reaches 60¾, the mixture is taken out and sent to the devolatilization device to remove unreacted monomers and volatiles, and then it is extruded and granulated to obtain block (or solution) rubber particles (C -1) For the graft copolymer, the weight average particle diameter of the rubber particles is 0.95 / an, and the rubber content is 10 weight S ;. &lt; Preparation Example 51-2 &gt; Graft copolymer of bulk (solution) rubber particles (C-2) Page 22 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) --- J .--: ---- f ^ ------ IT (please read the notes on the back before filling in this page) A7 __B7___ printed by the employee consumer cooperative of the Central Bureau of Economics of the Ministry of Economy V. Description of the invention (〉 丨) Manufacturing:-/ According to the preparation method of &lt; Preparation Example I-1 &gt;, the difference is that the over-vaporized benzoylase as the starting agent is 0.12 weight J: the monomer conversion rate of the first reactor 16 S !, the rotation speed is 140 rpn, and the temperature of the second reactor is 110 t :, the rotation speed is 300 rpa, after the reaction, it is extruded and granulated, and the block (or solution) rubber particles (C-2) can be obtained In the graft copolymer, the weight average particle diameter of the rubber particles is 0.75%, and the rubber content is 10% by weight. &lt; Preparation Example 3-3 &gt; Production of graft copolymers of bulk (or solution) rubber particles (C-3): According to the preparation method of &lt; Preparation Example I-1 &gt;, the difference is that it is used as an initiator The over-gasified benzoylase is 0.05 parts by weight, and 0.2 parts by weight of the 31-dodecyl mercaptan is added to the second reactor, and the monomer conversion rate of the first reactor is 19 3 !, speed It is 270 rpm, and the rotation speed of the second reactor is 250 rpm. The reverse rotation takes place in the first reactor. After the reaction, it is extruded and granulated to obtain block (or solution) rubber particles (C-3). For the graft copolymer, the weight average particle diameter of the rubber particles is 1.0%, and the rubber content is 10% by weight. &lt; Preparation Example Π-4 &gt; Production of graft copolymers of bulk (or solution) rubber particles (C-4): Using the third one-dodecyl mercaptan and pergasified benzoylase as starting materials Agent, 6.6 parts by weight of polybutadiene (produced by Asahi Kasei Corporation, trade name Ba 33 (^ 1 ^ 55 &amp; 5) is completely dissolved in 74.4 parts by weight of styrene, 25.6 parts by weight of acrylonitrile and 30 parts by weight In the ethylbenzene, to form the feed solution, and then feed the feed solution successively into the first reactor with a volume of 45 liters, reverse _ page 23_ This paper size is applicable to the Chinese National Standard (CNS) Α4 Specifications (210X297mm) I-11 ^-Ί; ---- {installed ------ ordered (please read the notes on the back before filling this page) Printed by Beigong Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs 322488 A7 B7 5. Description of the invention (n) The temperature should be 95 ° C. The reactor is equipped with a spiral stirrer equipped with a cooling circulation tube. The stirring rate is 120rpin, and the monomer conversion rate in the first reactor is 14¾. , The mixture after the first reactor reaction is continuously taken out and sent to the second, third, and fourth reactors in sequence. 0.08 parts by weight of the third 121-mercaptan mercaptan is added to the reactor, and the reverse rotation phenomenon is generated in the second reactor. The above-mentioned second, third, and fourth reactors have the same equipment as the first reactor, but the reaction The temperature part is 105t, 115 υ, 130TC in sequence, and the search and mixing rate is 200 r * pm, 150 γρπ, and 110 rpm in sequence; once the conversion rate of the mixture reaches 60¾, the mixture is taken out and sent to the devolatilization device for removal The unreacted monomers and volatiles are then extruded and granulated to obtain a graft copolymer of block (or solution) rubber particles (04). The weight average particle diameter of the rubber particles is 3.3%, and The rubber content is 10% by weight X. The physical property test standards of the resin compositions prepared in the examples and comparative examples of the present invention are as follows: 1. Melt flow index (MI): tested according to ASTM D-1238, in g / l〇min Said. 2. X's impact strength (IZOD): tested according to ASTM D-256, expressed in Kg cra / cn. 3. Elongation: tested according to ASTM D-638 method, expressed as 5 {. 4. Gloss Gradient (uniformity of gloss): according to Gardner 60 ° Incidence angle ASTM D-523 stipulates the test, the unit is%, the test test H is an injection product with a length of 300 ππ, a width of 25 nn, and a thickness of 3 nm, and its fan gate is 15 inches away from the edge. Page 24 This paper size is applicable to Chinese national standards (CNS) A4 specification (210X297mm) IΛ -------- f · installed-- (please read the precautions on the back and then fill out this page)-Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs * _________B7_ V. Description of the invention (θ) βπ, and measure the difference in gloss at 5 cn (GkJss 1) and 25 cn (Glass 2) from the winding mouth, which can be used as a method of judging the gloss gradient. The gloss uniformity is better.

五.氣化起始溫度（OIT):以DSC儀器（Du Pont 2910-DSC) 測定，測定條件中，其升溫速率為10 / m in、0 IT 的數值越低，表示聚合物越早開始氣化，熱安定性越 差。 &lt;實施例&gt; &lt;實施例1 &gt; 將由 &lt; 製備例I -1 &gt;所製得之苯乙烯糸共聚物（A-1) 70重量!ϋ、由製備例Π - 1所製得乳化橡膠粒子（B-1)之接 枝共聚物20重量S：,以及由&lt; 製備例H — 1&gt;製得之塊狀（ 或溶液）橡膠粒子（C-1)的接枝共聚物10重童3!混合，再加 入1.5重量份之滑劑，並以Werner &amp; Pfleiderer ZSK 35 押出機於220t：混合押出製粒，即可得到橡膠含量16重量iS 之苯乙烯条樹脂組成物，然後在220 1C下以震雄公司出廠 编號SM-90之射出成型機射出試Η後，測置流動指數、艾 氏衝擊強度、伸長率、光澤均一性、0ΙΤ等物性，测得結 果載於附表一。 &lt;實施例2 &gt; 依附表一之配方將原料混合均勻後依實施例1之處理 方法，並成型測試用試Η,測得之物性亦載於附表一。 &lt;實施例3 &gt; 依附表一之配方將原料混合均勻後依實施例1之處理 _第25頁_ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 11— ^裝 I 訂 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央橾準局員工消費合作社印製 Α7 Β7 五、發明説明（^4 ) 方法，並成型濟試用試H,測得之物性亦載於附表一。 &lt;實施例4 &gt; 依附表一之配方將原料混合均勻後依實施例1之處理 方法，並成型測試用試片，測得之物性亦載於附表一。 &lt;實施例5 &gt; 依附表一之配方將原料混合均勻後依實施例1之處理 方法，並成型測試用試片，测得之物性亦載於附表一。 &lt;實施例6 &gt; 依附表一之配方將原料混合均勻後依實施例1之處理 方法，並成型測試用試Μ ,測得之物性亦載於附表一。 &lt; fcfc較例1 &gt; 同實施例1之操作條件，不同之處在於：乳化橡膠粒 子（B)之接枝共聚物改用（B-5),而塊狀（或溶液）橡膠粒子 (C)的接枝共聚物改用（C-3),所製得之試驗片同樣進行各 種物性之測試，測得之物性亦載於附表一。 &lt;比較例2 &gt; 同實施例1之操作條件，但乳化橡膠粒子（B)之接枝 共聚物改用（B-5),所製得之試驗Η同樣進行各種物性之 測試，測得之物性亦載於附表一。 &lt;比較例3 &gt; 同實施例1之操作條件，不同之處在於：乳化橡膠粒 子（Β)之接枝共聚物改用（Β-5),塊狀（或溶液）橡膠粒子（C )的接枝共聚物改用（C-2),所製得之試驗Κ同樣進行各種 物性之測試，测得之物性亦載於附表一。 第26頁 本紙張尺度適用中國國家揉準（CNS ) Α4規格（210X297公釐） (請先聞讀背面之注意事項再填寫本頁) 裝. 訂 Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明（25 ) &lt;比較例4 &gt; ..... 同實施例1之操作條件，不同之處在於：乳化橡膠粒 子（B)之接枝共聚物改用（B-2),而塊狀（或溶液）橡膠粒子 (C)的接枝共聚物改用（C-3),所製得之試驗片同樣進行各 種物性之测試，測得之物性亦載於附表一。 &lt;比較例5 &gt; 同實施例1之操作條件，不同之處在於：乳化橡膠粒 子（B)之接枝共聚物改用（B-6),而塊狀（或溶液）橡膠粒子 (C)的接枝共聚物改用（C-3),所製得之試驗Η同樣進行各 種物性之測試，測得之物性亦載於附表一。 &lt;實施例7 &gt; 依附表二之配方將原料混合均勻後依實施例1的處理 方法，不同之處在於：乳化橡膠粒子（Β)之接枝共聚物同 時採用（Β-1)及（Β-2),而為雙峰分佈，邸橡膠粒子之重量 平均粒徑分別為〇.1_和〇.3_,同樣形成試驗Η進行各種 物性測試，測得之物性亦載於附表二。 &lt;實施例8 &gt; 依附表二之配方將原料混合均勻後依實施例1的處理 方法，不同之處在於：乳化橡膠粒子（Β)之接枝共聚物同 時採用（Β-1)及（Β-2),而為雙峰分佈，卽橡膠粒子之重量 平均粒徑分別為〇.1_和〇.3卿，同樣形成試驗片進行各種 物性測試，测得之物性亦載於附表二。 &lt;實施例9 &gt; 依附表二之配方將原料混合均勻後依實施例1之處理 第27頁 — ^ ~ n f 裝 訂 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X297公釐） 32叫8 A7 ’ _B7_ 五、發明説明（4) 方法，並成型測試用試片，測得之物性亦載於附表二。 &lt;實施例1 〇 &gt; 依附表二之配方將原料混合均勻後依實施例1之處理 方法，並成型測試用試Η，测得之物性亦載於附表二。 &lt;實施例1 1 &gt; 依附表二之配方將原料混合均勻後依實施例1之處理 方法，並成型測試用試片，測得之物性亦載於附表二。 &lt;實施例1 2 &gt; 依附表二之配方將原料混合均勻後依實施例1的處理 方法，不同之處在於：乳化橡膠粒子（B)之接枝共聚物為 (B-1)及（B-2),而為雙峰分佈，即橡膠粒子之重量平均粒 徑分別為0.1//Π和0.3卿，同樣形成試驗片進行各種物性测 試，測得之物性亦載於附表二。 經濟部中央揉準局貝工消費合作社印裂 II------{裝-- (請先閲讀背面之注意事項再填寫本頁吣 由比較例1、2、3之試驗结果顯示，本發明樹脂组 成物中接枝在乳化橡膠粒子（B)上之硬質苯乙烯条共聚物 的接枝厚度低於30 A時，不僅衝擊強度、伸長率沒有獲得 改善，樹脂之流動性亦變差，而由比較例5之結果顯示， 當接枝在乳化橡膠粒子（B)上之硬質苯乙烯条共聚物的接 枝厚度高於160 A時，樹脂之流動性會爱差，其衝擊強度 亦稍為下降，再由比較例1、4、5之試驗結果顯示，當 接枝在塊狀（或溶液）橡膠粒子（C)上之硬質苯乙烯条共聚 物的接枝厚度低於90 A時，無法得到具有良好光澤均一性 及熱安定性之樹脂；反觀實施例1〜12,本發明經前述 各成份及使用量之限制，不僅可使樹脂組成物具有良好之 第28頁 本紙張尺度適用中國國家標準（CNS〉Α4規格（210X297公釐） S2^438 A7 ______B7 五、發明説明（1 ) 衝擊強度及光澤均一性，當樹脂作為成型品時，其熱安定 性亦獲得改善，而具有產業上之利用價值，爰依法提出發 明專利之申請。 惟以上所述僅為本發明數較佳可行實施例，舉凡熟悉 此項技g人仕，其依本發明精神範轉所做之修飾或變更， 均理應包含在本案申請專利範圍内。 (請先閣讀背面之注意事項再填寫本頁) 袈_ 訂 經濟部中央標準局身工消費合作社印^ 娜 準 橾 家 國 國 中 用 適 ^22488 851320 m. 藤 m N· m 凾 屮 w Itwlt _ m 狄 耷 a 牖 m m 猓 氣化起始溫度(0IT) m m ^ 苕 艾氏衝擊強度 裡 m 滿翻5 雜8蒗 雜一務 逯NJ·驪 mm 苯乙烯条共 聚物(A) 光澤梯度 Gloss 2 Gloss 1 塊狀(或溶液)橡膠粒子(C)之種類 茹茚 mm 葙蹢 寐 * m m m 书 橡謬粒子之重量平均粒徑0«) 重量；1； 乳化橡膠粒子(B)之種類 茄茚 顿潮 mm CM 弈 铕 3 书 橡醪粒子之重量平均粒徑〇m) 重 ft；)； 種類 重量％ 5 cb-25 cm ro cn o B cn o s (kg * cjb/cjb) (g/10 »in) ro Os3 tn O CO 97.6 97.9 ro 1.25 s ? I—1 o 0.95 s w I—» g 〇 〇〇 3&gt; 實施例1 to oo o cn 〇 97.5 VO 办 to oo 〇〇 1.36 s 〇 1 »—» o 0.95 N5 ϋΐ ςκ&gt; t—ι g 〇 oo &gt; 1 1—* cn 實施例2 ro w o *a&gt; CO 03 〇〇 CO •私 CO CJ1 30.5 1.05 ? t—* o 0.95 CO I—* g 〇 ro 备 0&gt; h-* cn ο 實施例3 ro 岩 o — 97.7 97.8 to CO 1.14 s 〇 1 PO ro CO o 0.75 5i 05 1 tO S ο μ-* ro CO 3&gt; 1 H-* cn a&gt; 實施例4 ro Ca3 CO 0 01 97.1 97.6 to oo 24.9 1.19 s 〇 t— o Ο CO cn S 09 1 CO ο &gt; Λ 實施例5 ro CO o 97.1 97.5 CO rsi 24.7 1.21 s ο 1 1—* o 0.95 S OO 1 办 05 ο W 0&gt; Λ 實施例6 〇〇 ro 89.6 97.8 tJl 05 0.91 s ο 1 ΟΟ g 1.00 OO 1 cn ο οο H-^ &gt; Λ 比較例1 ro ro CO ro cn 95.0 97.5 17.3 0.94 s Ο 1 μ-^ to o 0.95 -·0 σσ i Cn ο CO 于 1—k σ&gt; 比較例2 ro 容 ro N5 95.4 CO -a 05 s S Η-» 0.96 s Ο 1 ro N5 0.75 〇σ 1 CJl ο H-* ：&gt; 麵 — 比較例3 ro ς〇 05 N5 91.4 97.6 N5 CO ro CO b 55 ο 1 CO g 1.00 09 1 ro §? ο Η-* ro CO &gt; 瞧 I—» cn 05 比較例4 to to 1—k CJl 05 CO 97.3 | 21.5 0.92 | σί ο \ C0 g 1.00 | 05 1 05 V-* g ο Os2 s 比較例5V. Gasification onset temperature (OIT): measured with a DSC instrument (Du Pont 2910-DSC). Under the measurement conditions, the temperature increase rate is 10 / min, and the lower the value of 0 IT, the earlier the polymer starts to gas Heat, the worse the thermal stability. &lt; Examples &gt; &lt; Example 1 &gt; The styrene-toluene copolymer (A-1) prepared by &lt; Preparation Example I -1 &gt; 70 weight! ϋ, prepared by Preparation Example Π-1 Graft copolymer of emulsified rubber particles (B-1) 20 weight S :, and graft copolymer of block (or solution) rubber particles (C-1) prepared by &lt; Preparation Example H-1 &gt; 10 重 童 3! Mix, then add 1.5 parts by weight of slip agent, and use Werner &amp; Pfleiderer ZSK 35 extruder at 220t: mixed and extruded to obtain a styrene strip resin composition with a rubber content of 16 weight iS, Then, at 220 1C, the injection molding machine with the model number SM-90 of Zhenxiong Co., Ltd. was used to inject the test H, and then the physical properties such as flow index, Ehrlich impact strength, elongation, gloss uniformity, 0ΙΤ, etc. were measured. Schedule I. &lt; Example 2 &gt; After mixing the raw materials according to the formula in Table 1, the processing method of Example 1 is followed, and the test Η for molding test is performed. The measured physical properties are also shown in Table 1. &lt; Example 3 &gt; After mixing the ingredients according to the formula in Table 1 and then processing according to Example 1_Page 25_ The paper size is applicable to China National Standard (CNS) Α4 specification (210X297mm) 11— ^ 装 I Order (please read the precautions on the back before filling in this page) Printed Α7 Β7 by the Consumer Cooperative of the Central Provincial Bureau of the Ministry of Economic Affairs. 5. Description of invention (^ 4), and formed a trial test H. The measured physical properties are also set out In Schedule 1. &lt; Example 4 &gt; After mixing the raw materials according to the formula in Table 1, the processing method of Example 1 was followed, and a test piece was formed. The measured physical properties are also shown in Table 1. &lt; Example 5 &gt; After mixing the raw materials according to the formula in Table 1, the processing method of Example 1 is formed, and the test piece for molding is formed. The measured physical properties are also shown in Table 1. &lt; Example 6 &gt; After mixing the raw materials according to the formula in Table 1, the treatment method of Example 1 is followed, and the molding test is conducted. The measured physical properties are also shown in Table 1. &lt; Comparative example 1 of fcfc &gt; The operating conditions are the same as in Example 1, except that the graft copolymer of the emulsified rubber particles (B) is replaced with (B-5), while the bulk (or solution) rubber particles ( C) The graft copolymer was changed to (C-3), and the obtained test pieces were also tested for various physical properties. The measured physical properties are also shown in Appendix 1. &lt; Comparative Example 2 &gt; The operating conditions were the same as in Example 1, but the graft copolymer of the emulsified rubber particles (B) was changed to (B-5), and the obtained test H was similarly tested for various physical properties and measured The physical properties are also listed in Schedule 1. &lt; Comparative Example 3 &gt; The operating conditions are the same as in Example 1, except that the graft copolymer of the emulsified rubber particles (B) is replaced with (B-5), and the block (or solution) rubber particles (C) The graft copolymer of (C-2) was used, and the obtained test K was also tested for various physical properties. The measured physical properties are also shown in Appendix 1. Page 26 This paper size is applicable to China National Standard (CNS) Α4 specification (210X297mm) (please read the notes on the back before filling out this page). Order Α7 Β7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention (25) &lt; Comparative Example 4 &gt; ..... The same operating conditions as in Example 1, except that the graft copolymer of the emulsified rubber particles (B) is changed to (B-2) , And the graft copolymer of block (or solution) rubber particles (C) is changed to (C-3), the test pieces prepared are also tested for various physical properties, and the measured physical properties are also shown in Appendix 1. . &lt; Comparative Example 5 &gt; The operating conditions are the same as in Example 1, except that the graft copolymer of the emulsified rubber particles (B) is replaced with (B-6), while the bulk (or solution) rubber particles (C ) Graft copolymer was changed to (C-3), and the obtained test H was also tested for various physical properties. The measured physical properties are also shown in Appendix 1. &lt; Example 7 &gt; After mixing the raw materials according to the formula in Table 2, the processing method according to Example 1 is different, except that the graft copolymer of the emulsified rubber particles (B) uses both (B-1) and ( Β-2), and for the bimodal distribution, the weight average particle diameter of the Di rubber particles are 0.1_ and 0.3_, respectively. Test H is also formed to conduct various physical property tests, and the measured physical properties are also shown in Table 2. &lt; Example 8 &gt; After mixing the raw materials according to the formula in Table 2, the processing method according to Example 1 is different, except that the graft copolymer of the emulsified rubber particles (B) uses both (B-1) and ( Β-2), and for the bimodal distribution, the weight average particle diameter of the rubber particles is 0.1_ and 0.3, respectively, and the test piece is also formed for various physical property tests, and the measured physical properties are also shown in Table 2 . &lt; Example 9 &gt; After mixing the ingredients according to the formula in Table 2 and then processing according to Example 1 Page 27-^ ~ nf binding (please read the precautions on the back before filling in this page) This paper size is applicable to China Standard (CNS) Α4 specification (210 X297 mm) 32 called 8 A7 '_B7_ V. Description of the invention (4) Method, and forming test pieces for testing. The measured physical properties are also listed in Appendix 2. &lt; Example 1 〇 &gt; After mixing the raw materials uniformly according to the formulation in Table 2, the treatment method of Example 1 is followed, and the test Η for molding test is performed. The measured physical properties are also shown in Table 2. &lt; Example 1 1 &gt; After mixing the raw materials uniformly according to the formulation in Table 2, the treatment method of Example 1 is formed, and a test piece for testing is formed. The measured physical properties are also shown in Table 2. &lt; Example 1 2 &gt; The processing method according to Example 1 after mixing the raw materials uniformly according to the formula in Table 2 is different: the graft copolymer of the emulsified rubber particles (B) is (B-1) and ( B-2), but for the bimodal distribution, that is, the weight average particle diameter of the rubber particles are 0.1 // Π and 0.3%, respectively, and a test piece is also formed for various physical property tests, and the measured physical properties are also shown in Table 2. Printed by the Peking Consumer Cooperative Cooperative of the Central Bureau of Economic Development of the Ministry of Economic Affairs II ------ {installed-- (Please read the precautions on the back and then fill in this page. The test results of Comparative Examples 1, 2, and 3 show that this In the invention resin composition, when the graft thickness of the hard styrene strip copolymer grafted on the emulsified rubber particles (B) is less than 30 A, not only the impact strength and elongation are not improved, but also the fluidity of the resin becomes poor. The results of Comparative Example 5 show that when the graft thickness of the hard styrene strip copolymer grafted on the emulsified rubber particles (B) is higher than 160 A, the resin will have poor fluidity and its impact strength is slightly Decrease, and the test results of Comparative Examples 1, 4, and 5 show that when the graft thickness of the hard styrene bar copolymer grafted on the bulk (or solution) rubber particles (C) is less than 90 A, it cannot Obtain resin with good gloss uniformity and thermal stability; in contrast to Examples 1 ~ 12, the present invention is not only able to make the resin composition have a good page 28, this paper size is suitable for the country of China Standard (CNS> Α4 specification (210X297 ) S2 ^ 438 A7 ______B7 V. Description of the invention (1) Impact strength and gloss uniformity, when the resin is used as a molded product, its thermal stability is also improved, and it has industrial utilization value, and an application for an invention patent is filed according to law However, the above are only a few of the preferred and feasible embodiments of the present invention. Anyone who is familiar with this technology and whose modifications or changes are based on the spirit of the present invention should be included in the scope of the patent application in this case. Please read the precautions on the back first and then fill out this page) 袈 _ Ordered by the Ministry of Economic Affairs, Central Standards Bureau, Bodywork and Consumer Cooperatives ^ Na Junju home country junior high school ^ 22488 851320 m. Fuji m N · m 凾 屮 w Itwlt _ m 迪 耷 a 牖 mm enthalpy gasification onset temperature (0IT) mm ^ in the Ai-Ei impact strength m full turn 5 Miscellaneous 8 Miscellaneous services NJ · Limm styrene strip copolymer (A) Gloss gradient Gloss 2 Gloss 1 Type of block (or solution) rubber particles (C), Ru in mm mm, Twa Miao ** mmm, weight average particle size of rubber particles, 0 «) Weight; 1; Type of emulsified rubber particles (B), Indan Tide mm CM Yi Eu 3 Book of Oak Mash Particles Quantity average particle size 〇m) Weight ft;); species weight% 5 cb-25 cm ro cn o B cn os (kg * cjb / cjb) (g / 10 »in) ro Os3 tn O CO 97.6 97.9 ro 1.25 s ? I—1 o 0.95 sw I— »g 〇〇〇3> Example 1 to oo o cn 〇97.5 VO Office to oo 〇〇1.36 s 〇1» — »o 0.95 N5 ϋΐ ςκ> t—ι g 〇oo &gt; 1 1— * cn Example 2 ro wo * a &gt; CO 03 〇〇CO • Private CO CJ1 30.5 1.05? t— * o 0.95 CO I— * g 〇ro 备 0 &gt; h- * cn ο Example 3 ro Yano — 97.7 97.8 to CO 1.14 s 〇1 PO ro CO o 0.75 5i 05 1 tO S ο μ- * ro CO 3 &gt; 1 H- * cn a &gt; Example 4 ro Ca3 CO 0 01 97.1 97.6 to oo 24.9 1.19 s 〇t— o Ο CO cn S 09 1 CO ο &gt; Λ Example 5 ro CO o 97.1 97.5 CO rsi 24.7 1.21 s ο 1 1— * o 0.95 S OO 1 Office 05 ο W 0 &gt; Λ Example 6 〇〇ro 89.6 97.8 tJl 05 0.91 s ο 1 ΟΟ g 1.00 OO 1 cn ο οο H- ^ &gt; Λ Comparative Example 1 ro ro CO ro cn 95.0 97.5 17.3 0.94 s Ο 1 μ- ^ to o 0.95-· 0 σσ i Cn ο CO at 1-k σ> Comparative Example 2 ro Rong ro N5 95.4 CO- a 05 s S Η- »0.96 s Ο 1 ro N5 0.75 〇σ 1 CJl ο H- *: &gt; surface-comparative example 3 ro ς〇05 N5 91.4 97.6 N5 CO ro CO b 55 ο 1 CO g 1.00 09 1 ro §? ο Η- * ro CO &gt; See I— »cn 05 Comparative Example 4 to to 1—k CJl 05 CO 97.3 | 21.5 0.92 | σί ο \ C0 g 1.00 | 05 1 05 V- * g ο Os2 s Comparative Example 5

322488 附表二 實 驗 编 號 實施例7 實細8 實施例9 實施例10 實施例11 實施例12 成 Ά ^ M^iL 4f (K \ mm% 66 50 60 70 70 66 種類 A-l A-l A-l A-2 A-3 A-4 重量平均粒徑為0.1岬之橡謬粒子 群含置⑽獻） 12 8 - - - 12 4 乳化橡膠粒子⑻之 接枝共聚物 乳化橡膠粒子⑻之種類 B-2 B-2 - - - B-2 * 重量平均粒徑為0.1犀之橡膠粒子 群含量(*量幻 12 12 30 20 20 12 乳化橡膠粒子⑻之種類 B-l B-l B-2 B-l B-l B-l 接枝之硬質苯乙烯糸共聚物的平 均接枝厚度(A) 66 64 88 50 50 6r 重量％ 10 30 10 10 10 10 類(或溶液)橡膠 粒子(0之接枝共 聚物 橡謬粒子之重量平均觀0®) 0.95 0.95 3.3 0.95 0.95 0.95 接枝之硬質苯乙烯糸共聚物的平 均接枝厚度(A) 200 200 165 200 200 200 份 塊狀(或溶液)橡雜子(C)之觀 C-l C-l C-4 C-l C-l C-l 樹脂組成物的總橡謬董 mm% 16 16 16 16 16 16 樹 流 動指數 (g/10 min) 1.51 1.48 1.36 1.24 1.02 0.95 脂 艾氏衝擊強度 (kg ♦ cn/cffl) 28.0 27.4 23.2 24.8 25.0 27』一 組 伸 長 率 (%) 32 28 24 30 27 28 成 光 Gloss 1 5 CD 98.1 97.9 97.6 98.0 97.8 97.6 物 澤 Gloss 2 25 cm 97.9 97.6 96.2 97.6 97.3 97.2 物 度 光澤梯度 5 cb-25 cm 0.2 0.3 1.4 0.4 0.5 Μ 性 氣化起始溫度_ (V) 233 232 227 231 234 235322488 Attached Table 2 Experimental number Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Into ^ M ^ iL 4f (K \ mm% 66 50 60 70 70 66 Type Al Al Al A-2 A-3 A-4 Containing rubber particles with a weight-average particle size of 0.1 pt. (Contributed) 12 8---12 4 Types of emulsified rubber particles ⑻ graft copolymer emulsified rubber particles ⑻ B-2 B- 2---B-2 * The content of rubber particles with a weight-average particle size of 0.1 rhodium (* quantity 12 12 30 20 20 12 Type of emulsified rubber particles ⑻ Bl Bl B-2 Bl Bl Bl Grafted hard styrene The average graft thickness of the Shito copolymer (A) 66 64 88 50 50 6r wt% 10 30 10 10 10 10 Class (or solution) rubber particles (weight average view of 0 graft copolymer rubber particles 0®) 0.95 0.95 3.3 0.95 0.95 0.95 The average graft thickness of the grafted hard styrene copolymer (A) 200 200 165 200 200 200 Views of block (or solution) acorn (C) Cl Cl C-4 Cl Cl Total resin content of Cl resin composition mm% 16 16 16 16 16 16 Tree flow index (g / 10 min) 1.51 1.48 1.36 1.24 1.02 0.95 Grease Ehrlich impact strength (kg ♦ cn / cffl) 28.0 27.4 23.2 24.8 25.0 27 "A set of elongation (%) 32 28 24 30 27 28 Gloss Gloss 1 5 CD 98.1 97.9 97.6 98.0 97.8 97.6 Gloss 2 25 cm 97.9 97.6 96.2 97.6 97.3 97.2 Matter gloss gradient 5 cb-25 cm 0.2 0.3 1.4 0.4 0.5 Μ gasification onset temperature_ (V) 233 232 227 231 234 235

Claims (1)

的2488 Vi 於' C82488 Vi at 'C8 經濟部中央標準局員工消費合作社印製 六、申請專利範圍⑴ 第85110020號發明專利申請Jg-之申請專利範圍修正本 1. 一種經橡膠改質之苯乙烯条樹脂組成物，其組成包含 由笨乙烯条共聚物（A)之連續基質相，以及分散在該 連續基質相中，且佔樹脂组成物5〜45重量！K的橡膠粒 子；上逑苯乙烯条共聚物（Α)傜由苯乙烯条單體90〜 50重量份、丙烯睛糸單髏10〜50重量份及其他可共聚 合單體0〜40重置份聚合而成；而橡膠粒子包含： (1) 重量平均粒徑0.05〜0.8卿之乳化橡膠粒子（Β) :及 (2) 重量平均粒徑在0.1〜10郷之塊狀（或溶液）橡膠 粒子（C); 其中，接枝在乳化橡膠粒子（B)上且由接枝聚合 單體聚合而成之硬質苯乙烯糸共聚物的平均厚度為30 〜160A,而接枝於塊狀（或溶液）橡膠粒子（C)上且由 接枝聚合單體聚合而成之硬質苯乙烯為共聚物的平均 厚度為90〜300 A。 2. 依據申請專利範圍第1項所述經橡膠改質之荣乙烯糸 樹脂組成物，其中乳化橡膠粒子（B)之橡膠粒徑為雙 峰分佈，其重量平均粒徑分別為0.06〜0.15扉及0.17 〜0.6卿，而塊狀（或溶液）橡膠粒子（C)之重量平 均粒徑為0.2〜。 3. 依據申請專利範圍第1項所述經橡膠改質之苯乙烯条 樹脂组成物，其中乳化橡膠粒子（B)上接枝之硬質苯 乙烯条共聚物的平均厚度為40〜140A,而塊狀（或 第30頁 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ----------1.-----------^..... (請先閲讀背面之注意事項再填寫本頁) 訂- ABCD 322488 申請專利範圍 溶液）橡膠粒子（C)上接k枝之硬質苯乙烯条共聚物的 平均厚度為100〜300A。 4.依據申請專利範圍第2項所述經橡膠改質之苯乙烯糸 樹脂組成物，其中塊狀（或溶液）橡膠粒子（C)之重 量平均粒徑為0.2〜1.5_。 !…：……厂裝…： (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局員工消費合作社印製 第31頁 本紙張尺度適用中國國家標尊(CNS)A4規格(2Η)Χ 297公釐)Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 6. Scope of Patent Application ⑴ Amendment of Patent Scope for Patent Application Jg- No. 85110020 1. A rubber-modified styrene strip resin composition, which consists of The continuous matrix phase of the ethylene strip copolymer (A), and dispersed in the continuous matrix phase, and account for 5 to 45 weight of the resin composition! The rubber particles of K; the upper styrene strip copolymer (A) is reset from 90 to 50 parts by weight of styrene strip monomers, 10 to 50 parts by weight of acrylonitrile monomers, and other copolymerizable monomers 0 to 40. The rubber particles are composed of: (1) Emulsified rubber particles with a weight average particle size of 0.05 ~ 0.8 (B): and (2) Block (or solution) rubber with a weight average particle size of 0.1 ~ 10 mm Particles (C); wherein, the average thickness of the hard styrene-copolymer grafted on the emulsified rubber particles (B) and polymerized by the graft polymerized monomer is 30 ~ 160A, and grafted on the block (or Solution) The average thickness of the hard styrene copolymer on the rubber particles (C), which is polymerized by graft polymerization monomer, is 90 ~ 300 A. 2. The rubber-modified Rong ethylene Shitou resin composition according to item 1 of the patent application scope, in which the rubber particle diameter of the emulsified rubber particles (B) is bimodal, and the weight average particle diameter is 0.06 ~ 0.15 And 0.17 ~ 0.6 Qing, and the weight average particle size of the bulk (or solution) rubber particles (C) is 0.2 ~. 3. The rubber-modified styrene strip resin composition according to item 1 of the patent application scope, wherein the average thickness of the hard styrene strip copolymer grafted on the emulsified rubber particles (B) is 40 ~ 140A, and the block Form (or page 30 of this paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ---------- 1 .----------- ^. .... (Please read the precautions on the back before filling in this page) Order-ABCD 322488 Patent application solution) The average thickness of the k-grafted hard styrene strip copolymer on the rubber particles (C) is 100 ~ 300A. 4. The rubber-modified styrene resin composition according to item 2 of the patent application scope, wherein the mass average particle diameter of the bulk (or solution) rubber particles (C) is 0.2 to 1.5 mm. !… ： …… Factory installed… ： (Please read the precautions on the back before filling in this page) Order 31 printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper standard is applicable to China National Standard (CNS) A4 specifications ( 2Η) 297 mm)
TW85110020A 1996-08-16 1996-08-16 Styrene resin composition modified by rubber TW322488B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2460854A1 (en) 2010-12-03 2012-06-06 Chi Mei Corporation Rubber-modified polystyrene resin composition for making an electroplatable article
CN102485760A (en) * 2010-12-03 2012-06-06 奇美实业股份有限公司 Rubber modified polystyrene resin for electroplating
CN102977539A (en) * 2011-09-02 2013-03-20 奇美实业股份有限公司 Rubber modified styrene resin and molded article produced using the same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2460854A1 (en) 2010-12-03 2012-06-06 Chi Mei Corporation Rubber-modified polystyrene resin composition for making an electroplatable article
CN102485760A (en) * 2010-12-03 2012-06-06 奇美实业股份有限公司 Rubber modified polystyrene resin for electroplating
US8835559B2 (en) 2010-12-03 2014-09-16 Chi Mei Corporation Rubber-modified polystyrene resin composition for making an electroplatable article
CN102977539A (en) * 2011-09-02 2013-03-20 奇美实业股份有限公司 Rubber modified styrene resin and molded article produced using the same
TWI449740B (en) * 2011-09-02 2014-08-21 Chi Mei Corp Rubber modified styrene resin and molded article produced
CN102977539B (en) * 2011-09-02 2015-04-22 奇美实业股份有限公司 Rubber modified styrene resin and molded article produced using the same

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