TWI229680B - Molding compositions with acrylonitrile-styrene-acrylate rubber copolymers having weathering resistance - Google Patents
Molding compositions with acrylonitrile-styrene-acrylate rubber copolymers having weathering resistance Download PDFInfo
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1229680 五、發明說明（1) 發明之背景: 使用於工程應用上的聚合摻合物， 已逐年增加中，依照使用的條件，這」 用量 合物常需要求具有耐候& ’同時也希用的聚合摻 性質及機械強度方面亦有良好的評價，不僅=後 有良好的性質’且經光照後還能維持相當的性質，^可稱 為具有良好的耐候性。&以’開發此種聚合摻合物為 明之目標。 已知在JAMES氏發表的美國專利第3, 1 1 8 855號中，揭 不以苯乙烯、丙烯腈共聚合物（SAN)與聚丙烯酸正丁酯、 丙烯腈、苯乙烯共聚合物，以此二共聚合物的掺合來改善 商業上聚合物SAN之拉伸率及耐衝擊強度。然而，Arthur 氏發表的美國專利第3, 944, 631號中，以另一種方式來製 備ASA聚合摻合物，用乳化聚合法先聚合出交鏈的亞克力 酸酯彈性體，然後再接枝聚合苯乙烯及丙烯腈單體，形成 一種多結構聚合物，最後再與乳化聚合的SAN摻合製成 ASA ° BRANDSTETTER等氏發表的美國專利第4, 442, 263號 中’揭示以一種硬質且交鏈的苯乙烯共聚物與苯乙晞、丙 婦腈共聚合物的摻合來製成。相似的SA卜PEi ting等人， 於美國專利第4, 731，414號中，揭示以三成分組成ASA聚合 捧合物’一種為耐衝擊改質劑，另一種為亞克力樹脂，最 後種為多型態接枝亞克力彈性體。相同的，SAI-PEI TING等人，也又再於美國專利第4,831，〇79號中，揭示以1229680 V. Description of the invention (1) Background of the invention: The polymer blends used in engineering applications have been increasing year by year. According to the conditions of use, this "dosage compound often requires weather resistance & The polymer blending properties and mechanical strength are also well evaluated, not only = good properties afterwards', but also maintain comparable properties after exposure to light, ^ can be said to have good weather resistance. & The goal is to develop such a polymer blend. It is known that in US Patent No. 3, 1 1 8 855 published by James, it is not disclosed that styrene, acrylonitrile copolymer (SAN) and poly-n-butyl acrylate, acrylonitrile, styrene copolymer are The blending of this di-copolymer improves the tensile strength and impact strength of the commercial polymer SAN. However, in U.S. Patent No. 3,944,631 published by Arthur's, another method is used to prepare ASA polymerization blends. The emulsion polymerization method first polymerizes the crosslinked acrylic acid ester elastomer, and then graft polymerization. Styrene and acrylonitrile monomers form a multi-structured polymer. Finally, it is blended with emulsified polymerized SAN to form ASA ° BRANDSTETTER et al., U.S. Patent No. 4,442,263. The chain styrene copolymer is made by blending acetophenone and acetonitrile copolymer. Similar SA, PEi ting, et al., In US Patent No. 4,731,414, disclosed that a three-component ASA polymerization complex is' one for impact modifier, the other is acrylic resin, and the last one is poly Type grafted acrylic elastomer. Similarly, SAI-PEI TING et al. Also disclosed in U.S. Patent No. 4,831, 〇79 that
第6頁 1229680 五、發明說明（2) 四成分組成ASA聚合摻合物，多加了苯乙烯、丙烯腈無規 則共聚物的摻合。發表於KAZUO KISH IDA等氏的美國專利 第4, 912, 162號中，以二烯橡膠及亞克力橡膠為核層合成 後’再以含有酸基共聚物接枝，達成分散相橡膠再與^^ 掺合，形成ASA聚合摻合物。r〇derick氏的美國專利第 5, 883, 191號中’說明含s AN樹脂以交鏈的亞克力酸酯接枝 聚合物的摻合來製備AS A之熱可塑掺合物。又於中華民國 專利第19, 803號中，酒井宏幸等人曾說明一種於非離子 性亞克力橡膠乳液之製造方法。而兒谷晃造等人於中華民 國專利第2 3 9，8 6 8號中，以紫外線吸收劑和次磷酸鹽的添 加劑於樹脂中，達到製成耐候性樹脂組成物。 發明之總結: 提供具有包括高光澤、高切口耐衝擊強度及高模數， 易流動性質和耐候性之優良組合的聚合摻合物為本發明 目標。Page 6 1229680 V. Description of the invention (2) The four-component ASA polymer blend is added with the addition of random copolymers of styrene and acrylonitrile. Published in U.S. Patent No. 4,912,162 by KAZUO KISH IDA et al., After the synthesis of diene rubber and acrylic rubber as the core layer, and then grafting with an acid-containing copolymer, a dispersed-phase rubber was then mixed with ^^ Blended to form an ASA polymer blend. Roderick's U.S. Patent No. 5,883,191 ' teaches the preparation of a thermoplastic blend of AS A by blending s AN resin with a crosslinked acrylic acid ester graft polymer. Also in the Republic of China Patent No. 19, 803, Hiroyuki Sakai and others have described a method for manufacturing a nonionic acrylic rubber emulsion. Kotani Kotaku et al., In the Republic of China Patent No. 239, 888, used ultraviolet absorbers and hypophosphite additives in the resin to achieve a weather-resistant resin composition. Summary of the Invention: It is an object of the present invention to provide a polymer blend having an excellent combination of high gloss, high notch impact strength and high modulus, flowability and weather resistance.
具有以上目標之聚合摻合物，為含有苯乙稀—丙稀睛 共聚合物及核殼型ASA接枝聚合物為主要組成物。然而， 在添加劑組成中，一般塑膠加工常用之安定劑、抗氧化劑 及紫外線吸收劑等成分也可應用於此一聚合摻合物中。更 簡而言之，基於SAN共聚合物及ASA接枝聚合物的全部重 量’而本發明的摻合組成物包括1〇至6〇%重量百分率的AMThe polymer blend with the above objectives is composed mainly of a styrene-acrylic copolymer and a core-shell type ASA graft polymer. However, in the additive composition, stabilizers, antioxidants, and ultraviolet absorbers commonly used in plastic processing can also be used in this polymer blend. More simply, based on the total weight of the SAN copolymer and the ASA graft polymer, the blend composition of the present invention includes 10 to 60% by weight of AM.
第7頁 !229680 、發明說明 接枝聚合物’其為核殼型多層結構之橡膠顆粒且以亞克力 酯系飽和橡膠為基質，又其亞克力系飽和橡膠含量為2〇至 6 0%重量百分率於ASA接枝聚合物，又橡膠核層中含有低於 10%重量百分率的多官能基。在於接枝殼層SAN共聚物組成 中’丙烯腈的含量為10至35%重量百分率於共聚物中可達 較佳效果。而摻合物主要成份之苯乙烯-丙烯腈共聚合 物’其含量為40〜90%重量百分率，其丙烯腈的含量為 20〜40%重量百分率〇 發明之詳細說明: % 本發明的聚合摻合物組成過程包含： (1) 亞克力酸s旨系橡移乳液之合成方法。 (2) 苯乙稀系列、丙稀臆系列與亞克力酸酯系橡膠乳液北 聚合之核殼型ASA接枝聚合物之合成方法。 (3) 苯乙烯-丙烯腈系共聚合物（SAN)與核殼型asa接枝聚人 物掺合之熱可塑性摻合物。 Ό 此摻合組合物呈現出高光澤良好的切口耐衝擊強度 優良的抗拉強度。 Λ _ (A)亞克力酸酯系橡膠乳液之合成：Page 7! 229680, Description of the invention The graft polymer 'is a core-shell multilayer rubber particle and uses acrylic ester saturated rubber as the matrix, and its acrylic saturated rubber content is 20 to 60% by weight. ASA grafted polymer, and the rubber core layer contains less than 10% by weight of polyfunctional groups. The content of the acrylonitrile in the composition of the grafted shell SAN copolymer is 10 to 35% by weight. A better effect can be achieved in the copolymer. The main component of the blend is styrene-acrylonitrile copolymer, whose content is 40 to 90% by weight, and the content of acrylonitrile is 20 to 40% by weight. Detailed description of the invention:% Polymerization blend of the present invention The composition process includes: (1) Acrylic acid s is a synthetic method of rubber shift emulsion. (2) Synthetic method of core-shell type ASA graft polymer of styrene, acrylic series and acrylic acid ester rubber emulsion. (3) Thermoplastic blend of styrene-acrylonitrile copolymer (SAN) and core-shell type asa graft polymer.掺 This blend composition exhibits high gloss, good notch impact strength, and excellent tensile strength. Λ _ (A) Synthesis of acrylic acid ester rubber emulsion:
第8頁 1229680 五、發明說明（4) 本發明之亞克力酸酯系橡膠乳液之合成法，可以是一 般熟知技藝中之乳化聚合法、懸浮聚合法及總體聚合法， 而這些製程組合反應物、聚合物、架橋劑、催化劑、缓衝 液、溶劑和條件是技藝中所熟知的。例如： 合適的亞克力酸酯系單體，可為C2〜C1G之烷基丙烯醯 基或C8〜C22之烷基甲基丙烯醯基與(：4〜(：8之烷基酯類組合單 體和它們的烷基或i化衍生物和它們的混合物，特別合適 的單體為丙烯酸正丁酯，所佔重量份89.0〜99.9%重量份。 合適的架橋劑單體可為：雙乙烯基苯（Divinyl benzene)、甲基丙烯酸丙稀酯（Allyl methacrylate)、雙 甲基丙浠酸乙二醇酯（Ethylene glycol dimethacrylate )、參丙烯酸三羥甲醇丙酯（Trimethylol propane triacrylate)、雙甲基丙烯酸丙二醇酯（Propylene glycol dimethacrylate)、甲基丙稀酸雙環戊烯酯 (Dicyclopentenyl methacrylate)、雙環戊二烯（Bicyclo pentadiene)、順-丁稀二酸二丙烯酯（Diallyl maleate)、反-丁烯二酸二丙烯酯（Diallyl fumarate)、 雙甲基丙烯酸異丁二醇酯（1，3 Butylene dimethacrylate )所佔重量份可為0. 01〜10. 0%重量份。 起始劑可使用各種習知的自由基聚合反應起始劑，例 如：過氧化物（peroxide)、偶氮化合物或過硫酸鹽化合 物，適當的起始劑如：過硫酸钟（KPS)、異丙苯基過氧化Page 8 1229680 V. Description of the invention (4) The method for synthesizing the acrylic acid ester rubber emulsion of the present invention can be an emulsion polymerization method, a suspension polymerization method and a general polymerization method which are generally known in the art, and these processes combine the reactants, Polymers, bridging agents, catalysts, buffers, solvents and conditions are well known in the art. For example: Suitable acrylic acid ester-based monomers may be C2 ~ C1G alkylpropenyl or C8 ~ C22 alkylmethacryloyl and (: 4 ~ (: 8 alkyl ester-based combination monomers) And their alkyl or i-derivatives and their mixtures, a particularly suitable monomer is n-butyl acrylate, which accounts for 89.0 to 99.9% by weight parts. Suitable bridging agent monomers can be: divinylbenzene (Divinyl benzene), Allyl methacrylate, Ethylene glycol dimethacrylate, Trimethylol propane triacrylate, propylene glycol dimethacrylate Propylene glycol dimethacrylate, Dicyclopentenyl methacrylate, Bicyclo pentadiene, Diallyl maleate, trans-butadiene acid 01〜10. 0% 重量 份。 Dipropylene (Diallyl fumarate), isobutyl glycol dimethacrylate (1,3 Butylene dimethacrylate) may be 0.01 to 10. 0% by weight. The initiator can use a variety of conventional Free radical polymerization The reaction initiator, such as: peroxide (peroxide), azo compound or a persulfate compound, such as a suitable initiator: through bell acid (KPS), cumyl peroxide
1229680 五、發明說明（5) 合物（Dicumyl peroxide)、第三丁基過氧化物 (Tert-buty1 peroxide)、過氧化苯甲醢（Benzoyl peroxide)、異丙苯 化過氧化氫（Cumene hydroperoxide)、第三丁基過氧化氳 (Tert-buty 1 hydroperoxide)所佔重量份可為〇· (Π 〜5%。 乳化劑可為·油酸卸（K - 〇 1 e a t e )、油酸納 (Na-oleate)、十二烷基硫酸鈉（Sls)、松香酸皂（R0Sin soap)、N-甲基庚基牛績酸納（Sodium N-methyl - N-oleoyl taurate)、十二酸息（Lauryl1229680 V. Description of the invention (5) Compound (Dicumyl peroxide), Tert-buty1 peroxide, Benzoyl peroxide, Cumene hydroperoxide 3. The weight part of Tert-buty 1 hydroperoxide can be 〇 (Π ~ 5%. Emulsifier can be K-〇1 eate), sodium oleate (Na -oleate), sodium lauryl sulfate (Sls), rosin acid soap (ROSin soap), Sodium N-methyl-N-oleoyl taurate, Lauryl
Soap)、烧基鈉萘磺酸脂（s〇diuin alkylarylnaphthalene sulfonate)所佔重量份可為〇· 〇卜1〇%重量份。 反應系統緩衝液可為碳酸鈉、碳酸氫鈉、硫酸鈉、硫 酸虱納、硫代硫酸鈉、填酸納、磷酸氫鈉、磷酸二氫納及 前述化合物之鉀鹽，所佔重量份可為〇〇卜3〇%重量份。 分子量之調節可藉反應溫 量調節劑加以控制。分子量調 醇、第三-十二烷基硫醇、α-量份可為0·01〜5·〇%重量份。 度加以控制或/和加入分子 節劑可為正-十二烷基硫 甲基苯乙稀二聚物，所佔重 聚合反應時間3到8小時，反應溫度55〜9〇 t，於 組成物合成所得乳膠，粒徑介於25〇〜55〇 nm、pH介於^ 1229680Soap) and sodiuin alkylarylnaphthalene sulfonate may be 0.1% by weight. The reaction system buffer may be sodium carbonate, sodium bicarbonate, sodium sulfate, sodium sulfate, sodium thiosulfate, sodium acid filling, sodium hydrogen phosphate, sodium dihydrogen phosphate, and potassium salts of the foregoing compounds. 〇〇 卜 30% by weight. The adjustment of molecular weight can be controlled by the reaction temperature regulator. The molecular weight adjustment alcohol, the third-dodecyl mercaptan, and the α-parts may be from 0.01 to 5.0% by weight. The degree of control or / and the addition of molecular agents may be n-dodecylthiomethyl styrene dimer, which accounts for a weight polymerization reaction time of 3 to 8 hours and a reaction temperature of 55 to 90 t. Synthesized latex with particle size between 25 ～ 55nm and pH between 1229680
表面張力35〜80 dyne/cm、Gel 5·5〜9·5、黏度4〜20cp、 Content 75% 以上 ° (B)亞克力酸酯系橡膠乳液與苯乙烯系列、丙烯腈系列共 聚合之核殼型ASA接枝聚合物之合成方法。 本發明之核殼型A S A接枝聚合法，可以是一般熟知技 藝中之乳化法、懸浮聚合法，而這些製程組合反應物、聚 合物、架橋劑、催化劑、緩衝液、溶劑和條件是技藝中所 熟知的。Surface tension 35 ~ 80 dyne / cm, Gel 5.5 · 5 ~ 9 · 5, Viscosity 4 ~ 20cp, Content 75% or more ° (B) Core-shell copolymerized acrylic acid ester rubber emulsion with styrene series and acrylonitrile series Method of ASA graft polymer. The core-shell type ASA graft polymerization method of the present invention may be an emulsification method or a suspension polymerization method which is generally known in the art, and these processes combine reactants, polymers, bridging agents, catalysts, buffers, solvents and conditions in the art. Well known.
合適的架橋劑單體可為：雙乙烯基苯（Divinyl benzene)、甲基丙烯酸丙烯酯（Allyl methacrylate)、雙 甲基丙稀酸乙二醇酯（Ethylene glycol dimethacrylate )、參丙稀酸三經甲醇丙酯（Trimethylol propane triacrylate)、雙甲基丙烯酸丙二醇醋（Propylene glycol dimethacrylate)、曱基丙烯酸雙環戊烯6旨 (Dicyclopentenyl methacrylate)、雙環戊二烯（Bicyclo pentadiene)、順-丁稀二酸二丙稀醋（Diallyl maleate)、反-丁烯二酸二丙烯酯（DiaHy1 fumarate)、 雙甲基丙烯酸異丁二醇酯u，3 Butylene dimethacrylate )所佔重量份可為0· 01〜1〇· 0%重量份。Suitable bridging agent monomers can be: Divinyl benzene, Allyl methacrylate, Ethylene glycol dimethacrylate, and tri-acrylic acid Trimethylol propane triacrylate, Propylene glycol dimethacrylate, Dicyclopentenyl methacrylate, Bicyclo pentadiene, maleic acid Diallyl maleate, DiaHy1 fumarate, 3 Butylene dimethacrylate (u, 3 Butylene dimethacrylate) may be from 0.01 to 1〇. 0% by weight.
第11頁 1229680 五、發明說明（7) 起始劑可使用各種習知的自由基聚合反應起始劑，例 如··過氧化物（peroxide)、偶氮化合物或過硫酸鹽化合 物，適當的起始劑如··過硫酸鉀（KPS)、異丙苯基過氧化 合物（Dicumyl peroxide)、第三丁基過氧化物 (Tert-buty1 peroxide)、過氧化苯甲醯（Benzoyi peroxide)、異丙笨 化過氧化氫（Cumene hydroperoxide)、第三丁基過氧化氫 (Tert-butyl hydroperoxide)所佔重量份可為 0.01 〜5%。 活化劑可使用各種習知，可形成氧化還原圈之化合 物’例如：硫酸亞鐵（Ferrous Sulfate)、甲酸合次硫酸 氫納（Sodium Formaldehyde Sulfoxylate)、葡萄糖 (Glucose)、乙二胺四醋酸納（Tetrasodium Ethylenediamine Tetra Acetate dihydrate)、焦磷酸四 鈉（Tetra sodium pyrophosphate anhydride)，所佔重量 份可為0· 01〜5%重量份。 乳化劑可為：油酸卸（K - ο 1 e a t e)、油酸鈉 (Na-oleate)、十二烷基硫酸鈉（SLS)、松香酸皂（R0Sin soap)、N-甲基-N-庚基牛磺酸鈉（Sodium N-methyl-N-oleoyl taurate)、十二酸皂（Lauryl Soap)、烧基鈉萘績酸脂（Sodium alkylarylnaphthalene sulfonate)所佔重量份可為〇· 〇1〜ι〇%重量份。Page 11 1229680 V. Description of the invention (7) Various conventional free radical polymerization initiators can be used, such as peroxides, azo compounds or persulfate compounds. Initiators such as potassium persulfate (KPS), cumyl peroxide, tert-buty1 peroxide, benzyl peroxide, isopropyl Cumene hydroperoxide and Tert-butyl hydroperoxide may be 0.01 to 5% by weight. The activator can use various conventional compounds that can form redox circles. For example: Ferrous Sulfate, Sodium Formaldehyde Sulfoxylate, Glucose, Sodium Ethylene Diamine Tetraacetate ( Tetrasodium Ethylenediamine Tetra Acetate dihydrate) and Tetra sodium pyrophosphate anhydride may be 0.01 to 5% by weight. Emulsifiers can be: K-ο 1 eate, sodium oleate, sodium dodecyl sulfate (SLS), rosin acid soap, N-methyl-N- Sodium N-methyl-N-oleoyl taurate, Lauryyl Soap, Sodium alkylarylnaphthalene sulfonate can be 0.001. ι0% by weight.
第12頁 1229680 五、發明說明（8) 反應系統緩衝液可兔 酸氫鈉、炉杆；^為酸鈉、碳酸氫鈉、硫酸鈉、；^ ‘ 啼代硫酸鈉、磷酸鈉、碰缺* 奶硫 刖述化合物之鉀鹽，所佔重量風鈉、磷酸二氫鈉及 里伤了為0· (Π〜3. 0%重量份。 量調藉反應溫度加以控制或/和加入分子 醇、第L Λ控二。/酿子㈣ 量份可為〇·〇1〜5·0%^量份=甲基求乙烯二聚物，所佔重 苯乙埽系單體可為苯乙烯、 乙烯、Ρ-卜丁其贫7 @ 甲基本乙烯、Ρ-氣苯 5--氣笨△膝％ 烯、Ρ_曱基苯乙冑、〇-氣苯乙烯、2, 5-: = :，4_二氣苯乙婦、2,4,6-三漠苯乙稀、2: 、本乙烯，所佔重量份可為20〜50重量百分率。 丙烯腈系單體可為丙烯腈、α—甲基丙烯腈等所佔 量份可為10〜35重量百分率。 本發明之ASA接枝聚合物係取由（a )所合成之亞克力乳 膠30〜60重量百分率並與苯乙烯系及丙烯腈系單體混合物 總合1 0 0重量份，並添加乳化劑、緩衝液、活化劑、氧化 劑、分子量調節劑等參與反應。 聚合反應時間3到8小時，反應溫度25〜90 °c，於上述 組合物合成所得乳膠粒徑大於5〇〇 nm、PH介於5. 5〜9. 5、 黏度4 〜35cp、表面張力 35 〜80 dyne/cm、Gel Content 80% nsPage 12 1229680 V. Description of the invention (8) The reaction system buffer solution can be sodium bicarbonate, furnace rod; ^ is sodium, sodium bicarbonate, sodium sulfate, ^ 'sodium thiosulfate, sodium phosphate, bump * The potassium salt of the milk sulfur compound is 0 · (Π ~ 3.0% by weight. The amount is adjusted by the reaction temperature to control or / and add molecular alcohol, No. L Λ Control II. / Brew ㈣ 量 Quantities can be 〇.〇1 ~ 5.0% ^ Quantities = methyl seeking ethylene dimer, the heavy styrene ethyl fluorene monomer can be styrene, ethylene , P-Bu Ding Qi Lean 7 @ methylbenzyl ethylene, P-gas benzene 5--air stupid △ Knee% ene, P-fluorenyl acetophenone, 0-gas styrene, 2, 5-: =:, 4 _ Digas acetophenone, 2,4,6-trimonyl styrene, 2: 2, and ethene, which can account for 20 to 50% by weight. The acrylonitrile monomer can be acrylonitrile, α-methyl The amount of acrylic acrylonitrile may be 10 to 35 weight percent. The ASA graft polymer of the present invention takes 30 to 60 weight percent of the acrylic latex synthesized from (a) and is the same as styrene and acrylonitrile. Body mixture total 100 parts by weight Emulsifiers, buffers, activators, oxidants, molecular weight regulators, etc. are added to participate in the reaction. The polymerization reaction time is 3 to 8 hours, and the reaction temperature is 25 to 90 ° C. , PH between 5. 5 ~ 9.5, viscosity 4 ~ 35cp, surface tension 35 ~ 80 dyne / cm, Gel Content 80% ns
Iran 第13頁 1229680 五、發明說明（9) 1 ---- 以上。 式上，乳膠液中必須再加入適當的凝聚劑進行凝聚，凝 = 1 = 7之漿液經脫水乾燥後，所得粉粒狀物質即為ASA 合物。而所用之凝聚劑可為-般常見之凝聚劑， 雄氣Ϊ酸、醋酸等酸類；鹼土族金屬帛，如氯化鈣等鈣 風，氣化錢、硫酸鎮等之鎖鹽、硫酸銘等之銘鹽。 (C )本乙稀〜而祕陡 摻和夕备 猜系共聚物（SAN)與核殼型ASA接枝聚合物 ^之熱可塑性塑膠摻合物。 本發明所用> 般熟知技蓺中，本乙烤-丙烯腈系共聚物（SAN)可以是一 " 之乳化聚合法、懸浮聚合法及總體聚合法。 乙締、ρ-卜為苯乙稀、α—甲基苯乙稀、ρ一氣苯 5-二氣苯乙 土苯乙烯、Ρ一甲基苯乙烯、〇-氣苯乙烯、2, 5-二溴贫r α、3’ 二氣苯乙烯、2, 4, 6_三溴苯乙烯、2, ’六尽G締等。 丙烯腈系單體 可為丙烯腈 α-甲基丙烯腈等Iran Page 13 1229680 V. Description of Invention (9) 1 ---- Above. In the formula, an appropriate coagulant must be added to the latex to coagulate. After the slurry of coagulation = 1 = 7 is dehydrated and dried, the obtained powdery granular material is an ASA compound. The coagulant used can be the common coagulants, such as maleic acid and acetic acid; alkaline earth metal rhenium, such as calcium chloride such as calcium chloride, gas salts, sulfate salts, etc. Zhiming salt. (C) This is a thermoplastic plastic blend of a mixture of polyisocyanate and copolymer (SAN) and core-shell type ASA graft polymer. In the general well-known technology used in the present invention, the acetonitrile-acrylonitrile copolymer (SAN) can be one of the emulsification polymerization method, suspension polymerization method, and overall polymerization method. Ethylene, ρ-B is styrene, α-methyl styrene, ρ monogas benzene 5-digas styrene bentonite styrene, P monomethyl styrene, 0-gas styrene, 2, 5-di Bromine-depleted r α, 3 'digas styrene, 2, 4, 6_tribromostyrene, 2,' Liu Ji G, etc. Acrylonitrile monomers can be acrylonitrile α-methacrylonitrile, etc.
不發明所坪 的含量為20〜40 乙烯-丙烯腈系共聚物（SAN)其丙烯腈 百分率。The content of the non-invention sheet is 20 to 40, and the percentage of acrylonitrile of the ethylene-acrylonitrile copolymer (SAN).
第14頁 1229680Page 14 1229680
苯乙烯-丙烯腈系共聚物（SAN)與核殼型ASA接枝聚合 物之摻和，其中主要成分之苯乙烯_丙烯腈系共聚物 (SAN)，其含量為5〇〜9〇%重量百分率。 此摻合物呈現出高光澤及良好的切口耐衝擊強度，並 能改善耐候及光照後物性之穩定性。 本發明所使用之各種量測方法及物性測試標準分述如 下： 1·融熔指數（MI): 依ASTM D-1 238 測試規定，220 °C X 10Kg，以g/l〇min 表 示0 2·懸臂式切口刻痕埃左衝擊強度（iz〇D): 依ASTM D-256測試規定，試片厚度1 / 4"。 3·熱撓曲變形溫度（〇1'): 依A S T M D - 6 4 8測試規定，試片厚度1 / 4 ”。 4·抗伸張強度模數及伸長率（T. s & EL): 依ASTM D - 638測試規定，試片厚度ι/g”。 5·色差（ΛΕ)及黃度（YI) : ^ 依ASTM D-2244(色差）、d-1925(黃度）測試規定。 6. 耐候性試驗： 依ASTM D - 4459測試規定。使用AtUs公司氙弧光燈耐候 試驗機’ Model : Ci-65A ;照射時間3〇〇小時。 7. 黏度測定：Blend of styrene-acrylonitrile copolymer (SAN) and core-shell ASA graft polymer. The main component is styrene-acrylonitrile copolymer (SAN), whose content is 50 to 90% by weight. percentage. This blend exhibits high gloss and good notch impact strength, and can improve the weatherability and stability of physical properties after light exposure. The various measurement methods and physical property test standards used in the present invention are described as follows: 1. Melt index (MI): According to ASTM D-1 238 test regulations, 220 ° CX 10Kg, expressed in g / l0min 0 2 · Cantilever notch nick left impact strength (iz〇D): According to ASTM D-256 test regulations, the thickness of the test piece is 1/4 ". 3. Heat deflection temperature (〇1 '): According to ASTMD-6 4 8 test regulations, the thickness of the test piece is 1/4 ". 4. · Tensile strength modulus and elongation (T. s & EL): according to The ASTM D-638 test stipulates that the thickness of the test piece is ι / g ". 5. Color difference (ΛΕ) and yellowness (YI): ^ According to ASTM D-2244 (color difference), d-1925 (yellowness) test regulations. 6. Weatherability test: According to ASTM D-4459 test regulations. AtUs Xenon arc lamp weathering tester 'Model: Ci-65A; Irradiation time was 300 hours. 7. Viscosity measurement:
12296801229680
使用BrookField公司Model:DV-n+之黏度古十。 8 ·粒徑測定： ^ ° 使用Malvern公司Model : Autos izer L〇〜c之粒徑分析儀 9 ·表面張力測定： & 使用LAUDA公司Model:TDl之表面張力計。 製備例 A1 :乳化橡膠粒子之聚合物的製造：重__* 成Using BrookField's Model: DV-n + viscosity ten. 8 · Particle size measurement: ^ ° Use Malvern's Model: Autosizer L0 ~ c particle size analyzer 9 · Surface tension measurement: & Use LAUDA's Model: TD1 surface tensiometer. Preparation Example A1: Production of polymer of emulsified rubber particles: heavy __ *
分 96· 〇 4. 0 〇. 15 〇· 1 0. 15 149· 7 丙烯酸正丁酯 甲基丙烯酸丙烯脂 十二烷基硫酸鈉 碳酸氫鈉 過硫酸鉀 蒸餾水 依以上配方在8 3 °C下’以半批量入料方式反應3小 時，得到固體含量3 9 · 3 %、轉化率9 8 · 〇 %、粒徑 367nm、Gel Content 73.9% 的合成橡膠乳液。 A2 :核殼型乳化接枝共聚物（AAS)的製造： 以A1所製得之橡膠乳液，直接與下表所列物質配合Points 96. 〇4.0. 0. 15 〇. 1 0. 15 149 · 7 n-butyl acrylate, methacrylate acrylate, sodium lauryl sulfate, sodium bicarbonate, potassium persulfate, distilled water according to the above formula at 8 3 ° C 'The reaction was carried out in a semi-batch mode for 3 hours to obtain a synthetic rubber emulsion with a solid content of 39 · 3%, a conversion of 98 · 0%, a particle size of 367nm, and a Gel Content of 73.9%. A2: Manufacture of core-shell type emulsion graft copolymer (AAS): The rubber emulsion prepared by A1 is directly mixed with the substances listed in the table below.
第16頁 1229680 五、發明說明（12) 進行接枝聚合反應： 成_^ 合成橡膠乳液（乾重） 丙烯腈 苯乙烯 十二烧基硫酸納 碳酸氫鈉 硫酸亞鐵（0· 2 %) 葡萄糖 焦磷酸四鈉 異丙苯化過氧化氫 蒸顧水 重量份 40. 0 15· 0 45. 0 1. 2 1. 0· 23 27 153· 依上述配方在反應溫度35 °C〜85 °C下，以半批量入 料方式反應5小時，得到固體含量39. 9 %、轉化率 99.9%、粒徑441nm、Gel Content 97.0% 的接枝 聚合物乳液。 B1 :乳化橡膠粒子之聚合物的製造： 參 成_重量份 97· 0 3. 0 0. 2 丙烯酸正丁酯 甲基丙烯酸乙二醇酯 十二烷基硫酸鈉 碳酸氫鈉Page 16 1229680 V. Description of the invention (12) Graft polymerization reaction: _ ^ Synthetic rubber emulsion (dry weight) acrylonitrile styrene lauryl sulfate sodium bicarbonate sodium ferrous sulfate (0.2%) glucose Tetrasodium pyrophosphate dicumyl hydroperoxide distilled water by weight 40. 0 15 · 0 45. 0 1. 2 1. 0 · 23 27 153 · According to the above formula at a reaction temperature of 35 ° C ~ 85 ° C The reaction was carried out in a semi-batch feed for 5 hours to obtain a graft polymer emulsion with a solid content of 39.9%, a conversion of 99.9%, a particle size of 441nm, and a Gel Content of 97.0%. B1: Manufacture of polymer of emulsified rubber particles: Participation_parts by weight 97 · 0 3. 0 0. 2 n-butyl acrylate ethylene glycol methacrylate sodium lauryl sulfate sodium bicarbonate
第17頁 1229680 五、發明說明（13) 過硫酸卸 0.15 蒸餾水 149.6 依以上配方在83 °C下，以半批量入料方式反應3小 時’得到固體含量38· 7 %、轉化率96. 3 %、粒徑 369nm、Gel Content 70.2% 的合成橡膠乳液。 B2 :核殼型乳化接枝共聚物（AAS)的製造： 以B1所製得之橡膠乳液，直接與下表所列物質配合 進行接枝聚合反應： I_± 重量 f 合成橡膠乳液（乾重） 40. 0 丙烯腈 15.0 苯乙烯 45· 0 十二烷基硫酸鈉 0.5 碳酸氫鈉 0. 11 硫酸亞鐵（0.2%) 1· 8 葡萄糖 0· 2 焦璘酸四納 〇· 23 異丙苯化過氧化氫 0. 27 蒸餾水 153. 2 依上述配方在反應溫度35 °C〜85 °C下，以半批量入 料方式反應5小時，得到固體含量38. 9 %、轉化率Page 17 1229680 V. Description of the invention (13) Persulfuric acid removal 0.15 Distilled water 149.6 According to the above formula at 83 ° C, the reaction was carried out in a semi-batch mode for 3 hours to obtain a solid content of 38.7% and a conversion rate of 96.3% A synthetic rubber emulsion with a particle size of 369nm and a Gel Content of 70.2%. B2: Manufacture of core-shell type emulsion graft copolymer (AAS): The rubber emulsion prepared by B1 is directly mixed with the substances listed in the following table for graft polymerization reaction: I_ ± weight f synthetic rubber emulsion (dry weight) 40.0 Acrylonitrile 15.0 Styrene 45.0 Sulfonic sodium sulfate 0.5 Sodium bicarbonate 0. 11 Ferrous sulfate (0.2%) 1 8 Glucose 0.2 Tetrahydropyrrolate 23 Cumene Hydrogen peroxide 0.27 distilled water 153.2 According to the above formula at a reaction temperature of 35 ° C ~ 85 ° C, the reaction was carried out in a semi-batch mode for 5 hours to obtain a solid content of 38.9%, conversion rate
第18頁 1229680 五、發明說明（14) 96.0%、粒徑5llnm、Gel Content 75.4% 的接枝 聚合物乳液。 C1 ·乳化橡膠粒子之聚合物的製造 成 分 丙婦酸正丁酯 甲基丙烯酸乙二醇S旨 甲基丙烯酸丙烯脂 十二烷基硫酸鈉 碳酸氫鈉 過硫酸鉀 蒸餾水 重量货 94. 0 0. 15 0. 1 0. 075 149· 7 # 依以上配方在83 °C下，以半批量入料方式反應3 λ!、 時，得到固體含量39· 1 %、轉化率97. 5 %、粒徑 403nm、Gel Content 96.9% 的合成橡膠乳液。 C2 :核殼型乳化接枝共聚物（AAS)的製造： 直接與下表所列物質配合 皇 量 份Page 18 1229680 V. Description of the invention (14) Graft polymer emulsion of 96.0%, particle size 5llnm, and Gel Content 75.4%. C1 · Production ingredient of polymer of emulsified rubber particles n-Butyl propionate Ethylene glycol methacrylate S purpose Acrylic acid methacrylate Sodium lauryl sulfate Sodium bicarbonate Sodium persulfate Distilled water 94.0 0. 15 0. 1 0. 075 149 · 7 # According to the above formula, at a temperature of 83 ° C, 3 λ! Was reacted in a semi-batch mode, and a solid content of 39.1%, a conversion rate of 97.5%, and a particle size were obtained. 403nm, Gel Content 96.9% synthetic rubber emulsion. C2: Manufacture of core-shell type emulsion graft copolymer (AAS): Directly mix with the substances listed in the table below.
以C1所製得之橡膠乳液 進行接枝聚合反應 Μ__Ί 合成橡膠乳液（乾重） 40· 0 丙烯腈 15. 0 苯乙烯 45. 0 第19頁 1229680 五、發明說明（15) 十二烷基硫酸鈉 碳酸氫鈉 過硫酸卸 蒸餾水G1 polymerization of rubber emulsion prepared by C1__Μ Synthetic rubber emulsion (dry weight) 40 · 0 acrylonitrile 15. 0 styrene 45.0 0 page 19 1229680 5. Description of the invention (15) dodecyl sulfuric acid Sodium bicarbonate
依上述配方在反應溫度35 °C〜85 t下，以半批量人 料方式反應5小時，得到固體含量39· 7 %、轉化率 99.8%、粒徑759nm、Gel Content 92.1% 的接枝 聚合物乳液。 D1 :乳化橡膠粒子之聚合物的製造：According to the above formula, at a reaction temperature of 35 ° C to 85 t, the reaction was conducted in a semi-batch manner for 5 hours to obtain a grafted polymer with a solid content of 39.7%, a conversion of 99.8%, a particle size of 759nm, and a Gel Content of 92.1% Emulsion. D1: Manufacture of polymers of emulsified rubber particles:
A__± 丙烯酸正丁酯 甲基丙烯酸乙二醇酯 甲基丙烯酸丙烯脂 十二烷基硫酸鈉 碳酸氫納 過硫酸鉀 蒸餾水 重量母 94· 0 0. 15 0. 1 0.125 149. 6 依以上配方在83 °C下，以半批量入料方式反應3小 時，得到固體含量39. 1 %、轉化率97. 5 %、粒徑 384nm、Gel Content 88.8% 的合成橡膠乳液。A__ ± n-butyl acrylate, ethylene glycol methacrylate, methacrylic acid acrylate, sodium lauryl sulfate, sodium hydrogen carbonate, sodium persulfate, potassium distillate, water weight 94 · 0 0. 15 0. 1 0.125 149.6 according to the above formula in At 83 ° C, the reaction was carried out in a semi-batch mode for 3 hours to obtain a synthetic rubber emulsion with a solid content of 39.1%, a conversion of 97.5%, a particle size of 384nm, and a Gel Content of 88.8%.
D2 :核殼型乳化接枝共聚物（AAS)的製造：D2: Manufacturing of core-shell emulsion graft copolymer (AAS):
第20頁 1229680 五、發明說明（17) 比較例 E1 採用市場上常見之不飽合雙烯系單體丁二烯 (Butadiene)作為乳化橡膠粒子之聚合物製造作為 比較例。 Μ_位 重量份 丁二稀 松香酸皂 碳酸氫鈉 過硫酸鉀 蒸餾水 98. 0 2. 0 1. 2 0. 5 80· 3 E2 依以上配方在8 5 °C下以全批加方式入料方式反應3 8 小時，得到固體含量48. 5%、轉化率90. 0°/◦、粒徑 280nm、Gel Content 70. 2% 的合成橡膠乳液。 核殼型乳化接枝共聚合物（ABS)的製造： 以E1所製得之橡膠乳液，直接與下表所列物質配合 進行接枝聚合反應： 重量份 成 份 合成橡膠乳液（乾重） 40. 0 丙烯腈 15. 0 苯乙烯 45. 0 十二烷基硫酸鈉 1. 2Page 20 1229680 V. Explanation of the invention (17) Comparative example E1 A polymer produced by using butadiene, an unsaturated diene monomer commonly used in the market, as a polymer for emulsified rubber particles, is used as a comparative example. Μ_Bits by weight of succinic acid soap, sodium bicarbonate, potassium persulfate, distilled water 98. 0 2. 0 1. 2 0. 5 80 · 3 E2 According to the above formula, feed in batches at 8 5 ° C. The reaction was carried out for 3 to 8 hours to obtain a synthetic rubber emulsion with a solid content of 48.5%, a conversion of 90. 0 ° / ◦, a particle size of 280nm, and a Gel Content of 70.2%. Manufacture of core-shell type emulsion graft copolymer (ABS): The rubber emulsion prepared by E1 is directly mixed with the substances listed in the following table for graft polymerization reaction: synthetic rubber emulsion (dry weight) by weight parts 40. 0 Acrylonitrile 15. 0 Styrene 45.0 0 Sodium lauryl sulfate 1.2
第22頁 1229680Page 22 1229680
0. 23 五、發明說明（18) 碳酸氫鈉 硫酸亞鐵（0 . 2 % ) 葡萄糖 焦磷酸四納 異丙苯化過氧化氫 0.27 蒸餾水 153.3 依上述配方在反應溫度3 5 °C〜8 5 °C下，以半批量Λ 料方式反應5小時，得到固體含量3 9 · 8 %、轉化率 9 9 · 7 %、粒徑3 4 0 n m的接枝聚合物乳液。 將上述接枝聚合物乳液，以氯化鈣凝聚脫水後再 燥至水份2%以下，所得粉狀物即為比 轧 枝聚合物基粉，取此基粉與苯乙烯〜丙彳j之核凱型ABS接 合，即為一般市場上常見之熱可塑性R騰共聚合物摻 較例則命名為AG15A1。 換合物，而此比 W述範例用於列舉本發明的實例， 點，常見 組合物範圍。在申請發明範圍内之另休f不侷限於本發明 於技藝中的一般技術中。 卜貫例及優 列 上述範例的摻合組成物的測試結果 1229680 五、發明說明（19) 表一 編 號 A1 B1 Cl D1 El 固體含量（％) 39. 3 38. 7 39. 1 39. 1 48. 5 轉化率（％ ) 98. 0 96. 3 97. 5 97. 5 90.0 粒徑（n m) 367 369 403 384 280 Gel content (%) 76. 1 70. 2 90. 1 88· 8 70. 2 其中 A1、B1、Cl 、D1為製備例編號 ;E1為比較例編號。 表二 • 編 號 A2 B2 C2 D2 E2 使用橡膠編號 A1 B1 Cl D1 El 固體含量（％) 39. 9 38. 9 39. 7 39· 7 39. 8 轉化率（％) 99. 9 96· 0 99. 8 99. 6 99. 7 粒徑（n m) 441 511 595 552 340 Gel content (%) 92. 1 75· 4 92.1 92. 9 82. 5 熔融指數 10. 5 44. 3 10. 0 6. 9 19.2 (2 2 0 °C x 1 0 kg， g/1Om i η ) • 埃左衝擊強度 (kg - cm / cm) 2. 2 1. 9 9. 3 19. 2 19.0 抗張強度（kg / cm 2 ) 6 0 5 588 479 489 480 伸長率（％) 25 17 56 16 20 光澤度（45度） 83. 7 81. 2 90. 3 92. 1 92. 30. 23 V. Description of the invention (18) Sodium bicarbonate ferrous sulfate (0.2%) Glucose pyrophosphate tetranacumene hydroperoxide 0.27 Distilled water 153.3 According to the above formula at a reaction temperature of 3 5 ° C ~ 8 5 The reaction was carried out in a semi-batch mode for 5 hours at ° C to obtain a graft polymer emulsion with a solid content of 39. 8%, a conversion of 99.7%, and a particle size of 34 nm. The above graft polymer emulsion is dehydrated with calcium chloride, and then dried to less than 2% of water content. The obtained powder is a specific polymer powder based on rolling. Take this base powder and styrene ~ The nuclear Kay type ABS joint, which is a common thermoplastic R Teng copolymer blending example in the general market, is named AG15A1. Alternatives, and the examples described above are used to list examples, points, and common composition ranges of the present invention. The rest of the invention is not limited to the general technology of the present invention in the art. Test results of the blended composition of the examples and excellent examples listed above 1229680 V. Description of the invention (19) Table 1 No. A1 B1 Cl D1 El Solid content (%) 39. 3 38. 7 39. 1 39. 1 48 5 Conversion rate (%) 98. 0 96. 3 97. 5 97. 5 90.0 Particle size (nm) 367 369 403 384 280 Gel content (%) 76. 1 70. 2 90. 1 88 · 8 70. 2 Among them, A1, B1, Cl, D1 are the numbers of the preparation examples; E1 is the number of the comparative examples. Table II • No. A2 B2 C2 D2 E2 Use rubber No. A1 B1 Cl D1 El Solid content (%) 39. 9 38. 9 39. 7 39 · 7 39. 8 Conversion rate (%) 99. 9 96 · 0 99. 8 99. 6 99. 7 Particle size (nm) 441 511 595 552 340 Gel content (%) 92. 1 75 · 4 92.1 92. 9 82. 5 Melt index 10. 5 44. 3 10. 0 6. 9 19.2 (2 2 0 ° C x 1 0 kg, g / 1Om i η) • Angstrom left impact strength (kg-cm / cm) 2. 2 1. 9 9. 3 19. 2 19.0 Tensile strength (kg / cm 2 ) 6 0 5 588 479 489 480 Elongation (%) 25 17 56 16 20 Gloss (45 degrees) 83. 7 81. 2 90. 3 92. 1 92. 3
第24頁 1229680 五、發明說明（20) 93 92 90 95 E 2 ( A G1 5 A1 )為比較例 熱撓曲變形溫度 91 (試片厚 J/4，°C) 其02、B2、C2、D2為製備例 編號。 ^ 由製備例A2中，得知粒栌去、去r λ λ 士 μ 7Α r- T仏禾達5 0 0nm時’則其埃左衝 擊強度僅2· 2強度不足。 矢及衡 由製備例B 2中，得知B1 > r。1 , , * . 卞力ίΗ之Gel content未達75〇/〇及B2之Page 24 1229680 V. Description of the invention (20) 93 92 90 95 E 2 (A G1 5 A1) is the heat deflection temperature of the comparative example 91 (strip thickness J / 4, ° C), 02, B2, C2 D2 is the preparation example number. ^ From Preparation Example A2, it was found that when the particles were removed, r λ λ ± μ 7Α r- T 仏 He reached 50 0nm ′, the impact strength of Angstrom left was only 2.2. The strength was insufficient. Yana Hiroshi From Preparation Example B2, B1 > r is known. 1,, *. The Gel content of 卞 力 ίΗ is less than 75〇 / 〇 and B2
Gel C〇ntent未達80%時，則其埃左衝擊強度僅19強度不 足° 採用5 Γ ”C2係採用熱分解型起始劑：而於製備例d2中則 抹用乳化逛原型起始系統。 本發明之具耐候性ASA共聚合物的組成物，When Gel Conntent is less than 80%, its Angstrom left impact strength is only 19 and the strength is insufficient. 5 Γ "C2 is used as a thermal decomposition type starter: In Preparation Example d2, the emulsification prototype starting system is used. The composition of the weather-resistant ASA copolymer of the present invention,
共聚合物夕知士仏、 興一般ABS 後物性之穩定性， ⑽^ 且成物相比較，呈現高光澤及改善耐候性及光 編號 Ε2 照光前 照光後 相關物性測試結果列於表二士 表三 I zod T. S YI ΔΕ 19. 0 480 17· 〇 16. 0 290 24. 〇 第25頁 1229680 (AG15A1)差異值 -3· 〇 -190 + 7. 0 + 4· 〇 照光前 9. 3 479 20. 6 C2 照光後 8. 7 451 21. 4 ( 差異值 -0· 6 - 28 + 0· 8 +1 · 5 照光前 19· 2 489 9.3 D2 照光後 18. 1 468 9. 5 差異值 -1· 1 - 21 + 0· 2 + 1· 2 其中IZ0D為埃左衝擊強度；τ· s為抗張強度；γι為黃 度；ΛΕ為色差。 ' 色差計算式係採用ΛΕ =〔（ /^)2 + ( Aa)H( Ab)2〕μ 計算式。比較例ABS係取自於台化公司自行生產之 AG15A1 。 由表三中可見，當於耐候試驗機中照光300小時後，The stability of the physical properties of the copolymers after Zhishi 仏 and Xing general ABS, ⑽ ^ and compared with the products, it shows high gloss and improved weather resistance and light number E2. The relevant physical property test results after exposure to light are listed in Table 2. Three I zod T. S YI ΔΕ 19. 0 480 17 · 〇 16.6.0 290 24. 〇 page 25 1229680 (AG15A1) difference -3 〇-190 + 7. 0 + 4 · 〇 before light 9.3 479 20. 6 C2 after light exposure 8. 7 451 21. 4 (difference value -0.6 6-28 + 0 · 8 +1 · 5 before light exposure 19 · 2 489 9.3 D2 after light exposure 18. 1 468 9. 5 difference value -1 · 1-21 + 0 · 2 + 1 · 2 where IZ0D is the Angstrom left impact strength; τ · s is the tensile strength; γι is the yellowness; ΛΕ is the color difference. 'The color difference calculation formula uses ΛΕ = [(/ ^) 2 + (Aa) H (Ab) 2] μ. The comparative example ABS is taken from the AG15A1 produced by Taihua Company. As can be seen from Table 3, after being exposed to light in a weathering test machine for 300 hours,
使用雙烯系橡膠之一般ABS(比較例中之AG15A1)於照光後 物性衰退嚴重，而使用本發明之亞克力酸酯系橡膠，所合 成之核殼型ASA接枝聚合物之熱可塑性摻合物的組成物 (C2、D 2 )則照光後之物性幾乎沒有衰退現象。 上述製備例中所使用之亞克力單體，經聚合後已成為 飽和之亞克力橡膠（A1、B1、C1、D1)，不再有殘存之不飽The general ABS using diene rubber (AG15A1 in the comparative example) has severe physical deterioration after light exposure, and the thermoplastic blend of the core-shell type ASA graft polymer synthesized by using the acrylic acid ester rubber of the present invention is severe The composition (C2, D 2) has almost no deterioration in physical properties after light exposure. The acrylic monomers used in the above preparation examples have become saturated acrylic rubbers (A1, B1, C1, D1) after polymerization, and there is no residual unsaturation.
第26頁 1229680 五、發明說明（22) 和雙鍵；此亦即其有優異耐候性之主因。而本發明之核殼 型接枝聚合物（A2、B2、C2、D2)，亦因與飽和之亞克力橡 膠接枝而成為本發明之關鍵技術，而此技術即為控制反應 系統之PH值。本發明之PH值可控制在3〜12之間。Page 26 1229680 V. Description of the invention (22) and double bond; this is the main reason for its excellent weather resistance. The core-shell graft polymer (A2, B2, C2, D2) of the present invention is also a key technology of the present invention because it is grafted with saturated acrylic rubber, and this technology is to control the pH value of the reaction system. The pH value of the present invention can be controlled between 3 and 12.
第27頁Page 27
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