TW200411015A

TW200411015A - Molding compositions with acrylonitrile-alkyldiene rubber-styrene terpolymer having weathering resistance

Info

Publication number: TW200411015A
Application number: TW91136238A
Authority: TW
Inventors: Wen-Chih Lu; Yuh-Nong Lin
Original assignee: Formosa Chemicals & Fibre Corp
Priority date: 2002-12-16
Filing date: 2002-12-16
Publication date: 2004-07-01

Abstract

The invention relates to compositions comprising Acrylonitrile/Diene Rubber/Styrene (ABS) Terpolymer process and method for making such compositions have excellent weathering resistance. The ABS Terpolymer is core-shell type resin and contains in blends have 10~99.9% by weight percent. There are 10~70% by weight percent diene rubber component in core and there are maximum 10% by weight percent multi-functional group monomer in core. And the shell component contains Acrylonitrile 10~35% by weight in ABS Terpolymer. In blends, the main components is Poly (Styrene-co-Acrylonitrile) and it contains 0~90% by weight. The main blends components it contains Acrylonitrile 20~40% by weight in itself. In particular to a polymer blends including UV stabilizer 0.01~2.0% having a high gloss and superior notched impact strength to the molded articles formed therefrom, while retaining excellent impact resistance and weathering resistance.

Description

200411015 五、發明說明（1) 發明之背景：工程應用上的聚合摻合物，增加中，依照使用的條件，、* ; 卜之用量已逐年需要求具有耐候性，同時也^戶外使用的聚合摻合物常質及機械強度方面亦有良好 J在：：$形性、物理性的性質，且經光照後還能維二在成形後有良好良好的耐候性。一般ABS塑膠相虽的性貝，才可稱為具有 a修的耐候性均不甚良其應用於室外功能備受限制，良好使付合物為本發明之目標。 “開心此種耐候性聚合摻 φ 氏發表的中華民國專利第77m25〇號中，揭不使用友腈橡膠（NBR)及丙晞腈_ 丁二烯苯乙稀共聚物（ABS)，加氯化環戊二烯與環辛二烯的狄爾斯阿德耳 (Diels-Alder)加成物和氧化銻的摻合組成物，來改善對 uv呈穩定態及防火性。然而在0ki tsu氏等發表的美國專利第60486 1 7號中，用亞克力樹脂及草酸醯苯胺（〇xalic anilide)、苯并三噚唑系（Benzotriaz〇les)、苯酮系 (Benzophenones)、三畊系（Triazines)等單品化合物或其混合物，採表面被覆（Surface-coated)方式增強樹脂耐久耐候性。Andrews氏發表的美國專利第5990208號中揭示於 PC/ABS樹脂中添加具立體障礙型胺系及苯并三噚唑系 (Benzotr iazoles)、苯酮系（Benz ophenone s )、三 D井系 (Triazines)等UV吸收劑，提昇樹脂之穩定性。Hoffmann 氏等發表的美國專利第5804623及5 643985號中，揭示回收200411015 V. Description of the invention (1) Background of the invention: Polymer blends for engineering applications are increasing, in accordance with the conditions of use, *; the amount of Bu has been required to have weather resistance year by year, and at the same time ^ polymerization for outdoor use The blends also have good properties in terms of normality and mechanical strength. They are: $ shape, physical properties, and also have good weather resistance after forming after being illuminated. In general, ABS plastic can be said to have a weather resistance, but its weather resistance is not very good. Its application in outdoor functions is very limited, so that the compound is the object of the present invention. "Kai Kai's weather-resistant polymerization blended with φ's published in the Republic of China Patent No. 77m250, reveals that no nitrile rubber (NBR) and propionitrile butadiene styrene copolymer (ABS) are used, and chlorination is added Diels-Alder adduct of cyclopentadiene and cyclooctadiene and antimony oxide blend composition to improve the stability to UV and fire resistance. However, at 0kitsu Published US Patent No. 60486 17 uses acrylic resin and oxalic anilide, Benzotriazoles, Benzophenones, Triazines, etc. A single product compound or a mixture thereof is surface-coated to enhance the durability and weatherability of the resin. U.S. Patent No. 5,990,208 published by Andrews discloses that PC / ABS resin is added with a sterically hindered amine and benzotris UV absorbers such as Benzotr iazoles, Benz ophenone s, and Triazines improve the stability of the resin. US Patent Nos. 5,804,623 and 5,643985 issued by Hoffmann et al., Reveal recycling

200411015200411015

塑膠，加有機性磷酸鹽或亞磷酸鹽系（Organic phosphite 滅f 〇S、Ph〇ni te)與立體障礙型紛系混合物以及添加脂肪 "增加回收塑膠穩定性，減緩熱氧化之劣化現象。 HerbSt氏等發表的美國專利第60 7789 1號中，揭示已劣化塑膠經添加多官能基之環氧化物（p〇lyfuncti〇nal epoxide)或立體障礙型酚系化合物，可增強劣化塑膠之強度，提昇回收再利用之價值。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。具有以上目標之聚合摻合物，為含有苯乙烯—丙烯共聚合物及核殼型ABS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、抗氧化及紫外線吸收劑等成分也可應用於此一聚合摻合物中。^ 簡而言之’基於SAN共聚合物及ABS接枝聚合物的全部重量’本發明的摻合組成物包括1〇至99· 9%重量百分率的Αβ 接枝聚合物’其為核殼型多層結構且以二烯系橡膠為芙質，又其核層中二烯橡膠之含量為10至7〇%重量百分;率"^ ABS接枝聚合物晨’又橡谬核層中含有低於重量百分; 的多官能基。在於接枝殼層SAN共聚物組成中，丙缔膳""的^Plastic, add organic phosphate or phosphite series (Organic phosphite, f 0S, Phonite) and steric obstacles, and add fat " increase the stability of recycled plastic, slow down the degradation of thermal oxidation. In US Patent No. 60 7789 1 published by HerbSt and others, it is disclosed that the degraded plastic can be enhanced by the addition of a polyfunctional epoxide or sterically hindered phenolic compound. Increase the value of recycling. 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. The polymer blend having the above objectives is composed mainly of a styrene-propylene copolymer and a core-shell ABS 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. ^ In short, 'based on the total weight of the SAN copolymer and the ABS graft polymer' The blend composition of the present invention includes 10 to 99.9% by weight of the Aβ graft polymer 'which is a core-shell type Multilayer structure with diene rubber as the texture, and the content of the diene rubber in the core layer is 10 to 70% by weight; the rate " ^ ABS graft polymer Chen 'and the rubber core layer contain Less than percent by weight; polyfunctional. In the composition of the grafted shell SAN copolymer, Binglian " "

200411015 五、發明說明（3) 含3：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笨乙烯-丙烯腈共聚合物，其含量為 0〜90%重量百分率，其丙烯腈的含量為20〜40%重量百分率。又相對於聚合摻合物之總重量，紫外光吸收劑之含量為〇· (Π 〜2· 0%。螢明之詳細說明：本發明的聚合摻合物組成過程包含：〇)二烯系橡膠乳液之合成方法。 (2 )笨乙烯系列、丙烯腈系列與二烯系橡膠乳液共聚合之核殼型ABS接枝聚合物之合成方法。 (3)笨乙烯-丙烯腈系共聚合物（SAN)與核殼型ABS接枝聚合物摻合及添加安定劑、紫外線吸收劑之熱可塑性摻合物。此摻合組合物呈現出高光澤良好的切口耐衝擊強度及優良的抗拉強度以及良好的耐候性。 (A )二烯系橡膠乳液之合成：本發明之二烯系橡膠乳液之合成法，可以是一般熟知，藝中之乳化聚合法、懸浮聚合法及總體聚合法，而^: 製程組合反應物、聚合物、架橋劑、催化劑、溶劑和條ς200411015 V. Description of the invention (3) Containing 3: 10 to 35% by weight can achieve better results in the copolymer. The stupid ethylene-acrylonitrile copolymer, which is the main component of the blend, has a content of 0 to 90% by weight and an acrylonitrile content of 20 to 40% by weight. With respect to the total weight of the polymer blend, the content of the ultraviolet light absorber is 0 · (Π ~ 2 · 0%. Detailed description of Yingming: The composition process of the polymer blend of the present invention includes: 0) diene rubber Synthesis of emulsion. (2) Synthetic method of core-shell ABS graft polymer copolymerized by stupid ethylene series, acrylonitrile series and diene rubber emulsion. (3) Blends of stupid ethylene-acrylonitrile copolymers (SAN) and core-shell ABS graft polymers, and thermoplastic blends containing stabilizers and ultraviolet absorbers. This blend composition exhibits high gloss, good notch impact strength, excellent tensile strength, and good weather resistance. (A) Synthesis of diene rubber emulsion: The method for synthesizing the diene rubber emulsion of the present invention can be generally known, the emulsification polymerization method, suspension polymerization method and overall polymerization method in the art, and ^: process combination reactants , Polymers, bridging agents, catalysts, solvents and strips

200411015 五、發明說明（4) 是技藝中所熟知的。例如：合適的二烯系單體，可為c4〜c12之烷基二烯系單體或其衍生物或其鹵化衍生物單體或其氰化合物衍生物單體及上述單體混合物’ 一烯糸單體可為共耗式結構（C ο n j u g a t e structure)或非共軛式結構；其亦可為上述單體與丙烯腈系或苯乙烯系單體所形成之二元塊型（Di-block)或三元塊型（Tri-block)共聚物’特別合適的單體為丁二烯，所佔重量份為90. 0〜99. 9%重量份。200411015 V. Description of Invention (4) is well known in the art. For example: A suitable diene-based monomer may be an alkyldiene-based monomer or a derivative thereof or a halogenated derivative monomer or a cyanide derivative monomer thereof and a mixture of the above monomers.糸 The monomer may be a co-njugate structure or a non-conjugated structure; it may also be a binary block (Di-block) formed by the above monomers and an acrylonitrile or styrene monomer. 9% 重量份。) or a tri-block (Tri-block) copolymer 'especially suitable monomer is butadiene, accounting for 90. 0 ~ 99. 9% by weight parts by weight.

合適的架橋劑單體可為：雙乙烯基苯（Di vinyl benzene)、曱基丙烯酸丙稀酉旨（Allyl methacrylate)、雙甲基丙烤酸乙二醇酯（Ethylene glycol dimethacrylate )、參丙稀酸三經曱醇丙酯（Trimethylol propane triacrylate)、雙甲基丙稀酸丙二醇酯（Propylene glycol dimethacrylate)、曱基丙烯酸雙環戊稀酯 (Dicyclopentenyl methacrylate)、雙環戊二晞（Bicyclo pentadiene)、順-丁烯二酸二丙烯酯（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 dimethacrylateSuitable bridging agent monomers may be: Di vinyl benzene, Allyl methacrylate, Ethylene glycol dimethacrylate, and propylene glycol Trimethylol propane triacrylate, Propylene glycol dimethacrylate, Dicyclopentenyl methacrylate, Bicyclo pentadiene, cis- Diallyl maleate, Diallyl fumarate, 1,3 Butylene dimethacrylate

)所佔重量份可為0〜10. 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：過硫酸鉀（KPS)、異丙苯基過氧化合物（Dicumyl peroxide)、第二丁基過乳化物 (Tert-butyl peroxide)、過氧化本甲酿（Benz〇yl0% 重量份。 The weight part may account for 0 ~ 10. 0% parts by weight. As the initiator, various conventional radical polymerization initiators can be used, for example, peroxide, azo compound or persulfate compound. Suitable initiators such as potassium persulfate (KPS), isopropyl Dicumyl peroxide, Tert-butyl peroxide, Benzoyl peroxide

第9胃 200411015 五、發明說明（5) peroxide)、異丙苯化過氧化氫（Cumene hydroperoxide)、第三丁基過氧化氫（Tert-butyl hydroperoxide)所佔重量份可為〇· 〜5%。乳化劑可為：油酸鉀（K - 〇 1 e a t e )、油酸納 (Na-oleate)、十二燒基硫酸納（SLS)、松香酸皂（Rosin soap)、N-甲基-N -庚基牛石黃酸鈉（Sodium N-methy 1-N-oleoyl t aura t e )、十二酸皂（Lauryl Soap)、烧基納萘石黃酸脂（Sodium alkylarylnaphthalene sulfonate)所佔重量份可為0·01〜10%重量份。分子量之調節可藉反應溫度加以控制或/和加入分子量調節劑加以控制。分子量調節劑可為正—十二烷基硫醇、弟二—十二烧基硫醇、正—四燒基硫醇、異-四燒基硫醇、正-八烷基硫醇、α —甲基苯乙烯二聚物，所佔重量份可為0 · 0 1〜5 · 0 %重量份。 cm 聚合反應時間1 0到4 0小時，反應溫度“〜g 〇它，於上述組成物合成所得乳膠其結構可為順式（c丨s )、反式 (Trans)或乙烯基式（Vinyl)之分子結構或其混合結構，粒徑介於200〜450 nm，粒徑分佈可為單或多分佈粒徑、pH介於5.LU.0、黏度100〜350cp、表面張力3〇〜7〇 Gel Content 45〜95% 〇 (B) 二烯系橡膠乳液與苯乙烯系列、核殼型ABS接枝聚合物之合成方丙烯腈系列共聚合之法0No. 9 stomach 200411015 V. Description of the invention (5) peroxide), Cumene hydroperoxide, Tert-butyl hydroperoxide The weight part can be 0 · ~ 5% . Emulsifiers can be: potassium oleate (K-〇1 eate), sodium oleate (Na-oleate), sodium dodecyl sulfate (SLS), rosin acid soap (Rosin soap), N-methyl-N- The heptyl sodium taurine sodium (Sodium N-methy 1-N-oleoyl t aura te), lauryl soap, and sodium alkylarylnaphthalene sulfonate may be 0 · 01 ~ 10% by weight. The adjustment of the molecular weight can be controlled by the reaction temperature or / and the addition of a molecular weight modifier. The molecular weight regulator can be n-dodecyl mercaptan, di-dodecyl mercaptan, n-tetracathyl mercaptan, iso-tetracathyl mercaptan, n-octadecyl mercaptan, α- The methylstyrene dimer may be from 0. 0 1 to 5. 0% by weight. cm The polymerization reaction time is 10 to 40 hours, and the reaction temperature is "~ g. It can be cis (c 丨 s), trans (vin) or vinyl (vinyl). Molecular structure or its mixed structure, the particle size is between 200 ~ 450 nm, the particle size distribution can be single or multiple, the pH is between 5.LU.0, the viscosity is 100 ~ 350cp, and the surface tension is 30 ~ 7. Gel Content 45 ~ 95% 〇 (B) Copolymerization of acrylonitrile series of diene rubber emulsion with styrene series and core-shell ABS graft polymer

第10頁 200411015 五、發明說明（6) 本發明之核殼型ABS接枝聚合法，可以是一般熟知技藝中之乳化法、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、溶劑和條件是技藝中所熟知的。Page 10 200411015 V. Description of the invention (6) The core-shell ABS graft polymerization method of the present invention can be the emulsifying method, suspension polymerization method and overall polymerization method which are generally known in the art, and these processes combine reactants and polymers , Bridging agents, catalysts, solvents and conditions are well known in the art.

合適的架橋劑單體可為：雙乙烯基苯（Divinyl benzene)、曱基丙浠酸丙稀醋（Allyl methacrylate)、雙甲基丙烯酸乙二醇酯（Ethylene glycol dimethacrylate )、參丙烯酸三經曱醇丙酯（Trimethylol propane triacrylate)、雙甲基丙稀酸丙二醇酯（Propylene glycol dimethacrylate)、甲基丙烯酸雙環戊稀酯 (Dicyclopentenyl methacrylate)、雙環戊二烯（Bicyclo pen tad i ene )、順-丁烯二酸二丙烯酷（Diallyl maleate)、反-丁稀二酸二丙晞 S旨（Diallyl fumarate)、雙曱基丙烤酸異丁二醇酉旨（1，3 Butylene dimethacrylate )所佔重量份可為0〜1 0. 0 %重量份。Suitable bridging agent monomers can be: Divinyl benzene, Allyl methacrylate, Ethylene glycol dimethacrylate, and three-acid acrylic acid Trimethylol propane triacrylate, Propylene glycol dimethacrylate, Dicyclopentenyl methacrylate, Bicyclo pen tad i ene, cis-butyl Diallyl maleate, diallyl fumarate, diallyl fumarate, and 1,3 butylene dimethacrylate 0 至 1 0. 0% 重量份。 May be 0 ~ 1 0. 0% by weight.

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，適當的起始劑如二過硫酸鉀（KPS)、異丙苯基過氧化合物（Die umyl peroxide)、第三丁基過氧化物 (Tert-butyl peroxide)、過氧化苯甲醯（Benzoyl peroxide)、異丙苯化過氧化氫（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As the initiator, various conventional radical polymerization initiators can be used, for example, a peroxide, an azo compound, or a persulfate compound, and an appropriate initiator such as potassium dipersulfate (KPS), Die umyl peroxide, Tert-butyl peroxide, Benzoyl peroxide, Cumene hydroperoxide, 01〜5%。 Tributyl hydroperoxide (Tert-butyl hydroperoxide) may be 0.01 to 5% by weight. Various activators can be used to form a combination of redox circles

第11頁 200411015 五、發明說明（7) 物，例如··硫酸亞鐵（F e r r 〇 u s S u 1 f a t e )、曱酸合次硫酸氫納（Sodium Formaldehyde Sulfoxylate)、葡萄糖 (Glucose)、乙二胺四醋酸納（Tetrasodium Ethylenediamine Tetra Acetate dihydrate)、焦碟酸四鈉（Tetra sodium pyrophosphate anhydride)，所佔重量份可為0. 01〜5%重量份。乳化劑可為：油酸鉀（K - ο 1 e a t e )、油酸納 (Na-oleate)、十二烧基硫酸鈉（SLS)、松香酸皂（Rosin soap)、N-曱基-N-庚基牛磺酸納（Sodium N-methy 1-N-oleoy 1 taurate)、十二酸皂（LaurylPage 11 200411015 V. Description of the invention (7), such as ... Ferrous 〇us Su 1 fate, Sodium Formaldehyde Sulfoxylate, Glucose, Glycol 01〜5% 重量份。 Tetrasodium Ethylenediamine Tetra Acetate dihydrate, Tetra sodium pyrophosphate anhydride (Tetrasodium pyrophosphate anhydride), which may account for 0.01 to 5% by weight. Emulsifiers can be: potassium oleate (K-ο 1 eate), sodium oleate (Na-oleate), sodium dodecyl sulfate (SLS), rosin acid soap (Rosin soap), N-fluorenyl-N- Sodium N-methy 1-N-oleoy 1 taurate, Lauryl soap

Soap)、烧基鈉萘石黃酸脂（Sodium alkylarylnaphthalene sulfonate)所佔重量份可為〇· (Π〜i〇%重量份。分子量之調節可藉反應溫度加以控制或/和加入分子量調節劑加以控制。分子量調節劑可為正—十二院基硫醇、第三-十二烷基硫醇、正—四烷基硫醇、異〜四烷基硫醇、正-八烷基硫醇、α -曱基苯乙烯二聚物，所佔ι旦鼠可為0· (Π〜5· 0%重量份。 S & 苯乙烯系單體可為苯乙烯、α _甲基苯乙烯、乙烯、P-t- 丁基苯乙烯、ρ—曱基苯乙烯、氣檢1 5-二氯苯乙烯、3, 4-二氯苯乙烯、2, 4, 6_三溴' ， 5 -二溴苯乙烯，所佔重量份可為2〇〜5Q重量百分、2, 丙烯腈系單體可為丙烯腈、α—甲基丙烯耸辦量份可為10〜35%重量百分率。自寺所佔重本發明之ABS接枝聚合物係取由（Α)所合一乂夂二烯系乳Soap), Sodium alkylarylnaphthalene sulfonate may be in the range of 0. (Π ~ i0% by weight). The molecular weight can be adjusted by controlling the reaction temperature or / and adding a molecular weight regulator. Control. Molecular weight regulators can be n-dodecyl mercaptan, third-dodecyl mercaptan, n-tetraalkyl mercaptan, iso ~ tetraalkyl mercaptan, n-octadecyl mercaptan, α-fluorenyl styrene dimer, which can be 0 · (Π ~ 5.0% by weight). S & styrenic monomers can be styrene, α_methylstyrene, ethylene , Pt-butylstyrene, p-fluorenylstyrene, gas detection 1 5-dichlorostyrene, 3, 4-dichlorostyrene, 2, 4, 6_tribromo ', 5-dibromostyrene The weight part can be 20 ~ 5Q weight percent, 2, the acrylonitrile monomer can be acrylonitrile, and the amount of α-methacrylic acid can be 10 ~ 35% by weight. The ABS graft polymer of the present invention is a diene-based milk combined with (A)

200411015 五、發明說明（8) 膠20〜60 %重量百分垄* t / 77丰亚與苯乙烯系及丙烯腈系單體混合物總合1 0 0 %重量份，潘、灭丄兀杂加乳化劑、活化劑' 氧化劑、分子量調節劑等參與反應。聚合反應時間3 Μ 0 , _ _ 叮门3到8小時，反應溫度2 5〜9 0 °C，於上述組合物合成所得乳勝& ^ 匕膠板徑20 0〜40 0 nm、PH介於6.0〜12.0、黏度3〜40cp、表面張力q 刀35〜80 dyne / cm 〇上述礼膠液中必須再加入適當的凝聚劑進行凝聚，凝聚後所付之聚液經脱水乾燥後，所得粉粒狀物質即為abs 接枝共聚合物。而所用之凝聚劑可為一般常見之凝聚劑，200411015 V. Description of the invention (8) Glue 20 ~ 60% by weight 100% ridge * t / 77 100% by weight of Fengya and styrene and acrylonitrile monomer mixture. Emulsifiers, activators' oxidants, molecular weight regulators, etc. participate in the reaction. Polymerization reaction time 3 Μ 0, _ _ Dingmen 3 to 8 hours, reaction temperature 2 5 ~ 90 ° C, Rusheng obtained from the above composition synthesis ^ Dagger rubber plate diameter 20 0 ~ 40 0 nm, PH media At 6.0 ~ 12.0, viscosity 3 ~ 40cp, surface tension q knife 35 ~ 80 dyne / cm 〇The above-mentioned gift gum solution must be added with appropriate coagulant for coagulation. The polymer solution after coagulation is dehydrated and dried, and the resulting powder is The granular material is the abs graft copolymer. The coagulant used can be a common coagulant,

例如··硫酸、醋酸等酸類；鹼土族金屬鹽，如氯化鈣等鈣鹽；氣化鎮、硫酸鎂等之鎂鹽、硫酸鋁等之鋁鹽。 (C)苯乙烯-丙烯腈系共聚合物（SAN)與核殼型ABS接枝聚合物掺合及添加安定劑、紫外線吸收劑之熱可塑性塑膠摻合物。本發明所用之苯乙烯—丙烯腈系共聚物（SAN)可以是— 般熟知技藝中之乳化聚合法、懸浮聚合法及總體聚合法。For example, acids such as sulfuric acid and acetic acid; alkaline earth metal salts such as calcium salts such as calcium chloride; magnesium salts such as gasification ballast, magnesium sulfate, and aluminum salts such as aluminum sulfate. (C) Blends of styrene-acrylonitrile copolymers (SAN) and core-shell ABS graft polymers and thermoplastic plastic blends with stabilizers and UV absorbers added. The styrene-acrylonitrile copolymer (SAN) used in the present invention may be an emulsification polymerization method, a suspension polymerization method, or a general polymerization method in a generally known technique.

苯乙烯系單體可為苯乙烯、甲基苯乙烯、P—氯笨乙烯、p-t- 丁基苯乙烯、p—曱基苯乙烯、0-氯苯乙烯、2, 二氯苯乙烯、3, 4-二氣苯乙烯、2, 4, 6 —三溴苯乙烯、2, 5 -二溴苯乙烯等。 ’ 丙烯腈系單體可為丙烯腈、α -曱基丙烯腈等。本發明所用之苯乙烯〜丙烯腈系共聚物（SAN)其丙烯腈Styrene-based monomers can be styrene, methylstyrene, P-chlorostyrene, pt-butylstyrene, p-fluorenylstyrene, 0-chlorostyrene, 2, dichlorostyrene, 3, 4-Digas styrene, 2, 4, 6-tribromostyrene, 2, 5-dibromostyrene, etc. The acrylonitrile-based monomer may be acrylonitrile, α-fluorenyl acrylonitrile, or the like. The styrene ~ acrylonitrile copolymer (SAN) used in the present invention has acrylonitrile

第13頁 200411015 、五、發明說明（9) 的含量為20〜40%重量百分率。苯乙烯-丙烯腈系共聚物（SAN)與核殼型ABS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) ’其含量為〇〜90%重量百分率。添加的加工助劑可為安定劑及紫外線吸收劑。安定劑可為酚系或胺系或臘系之熱安定劑，當加上磷酸鹽或磺酸鹽時，可達到綜合安定劑之相乘效果。可使用之範例為Cyanamid公司所生產的Antioxidant80、 Antioxidant425 、 Antioxidant2246 、 Plastanox LTDP 、 Plastanox STDP等，或是Ciba-Geigy公司所生產的 Irganoxl68 、 IrganoxlOlO 、 Irganoxl076 、 Irganoxl093 等，或是Monsanto公司所生產的Santowhite powder、 Santonox R等，或是I.C.I公司所生產的Topanol CA等，或是Shell公司所生產的I〇nox330等，或是Ethyl公司所生產Ant i oxidant 72 0等，或是丸善油化公司所生產的BHT。其所佔重量份可為0· 01至5. 0%重量份。紫外線吸收劑可為苯并三曙峻系（B e η ζ 〇 t r i a ζ ο 1 e s)、三哄系（"Triazines)、苯酮系（Benzophenones)、苯亞稀丙基醋系（Cinnamate)、鄰經T基酯系（Salicylate)等及其衍生物，可使用之範例為Tinuvin326、Tinuvin327、 Tiruivin328 、Tinuvin P 、JF-77 、JF-78 、Advastab45 、 Advas tab48、Rylex H、Unistatl2、Unistat247、 U n i s t a 12 21 1、U v i n u 1 4 0 0、U v i n u 1 41 0、U v i n u 1 M - 4 0、 Cyasorb UV-9 、Cyasorb UV-287 、Cyasorb UV-314 、 IIHI ISM：第14頁 200411015 、五、發明說明（ίο) 'Page 13 200411015, V. Description of the invention (9) The content is 20 ~ 40% by weight. Blend of styrene-acrylonitrile copolymer (SAN) and core-shell type ABS graft polymer. The content of styrene-acrylonitrile copolymer (SAN) as the main component is 0 to 90% by weight. The added processing aids can be stabilizers and UV absorbers. The stabilizer can be a phenol-based, amine-based, or wax-based thermal stabilizer. When a phosphate or sulfonate is added, the multiplicative effect of the comprehensive stabilizer can be achieved. Examples that can be used are Antioxidant80, Antioxidant425, Antioxidant2246, Plastanox LTDP, Plastanox STDP, etc. produced by Cyanamid Company, or Irganoxl68, IrganoxlOlO, Irganoxl076, Irganoxl093, etc. produced by Ciba-Geigy, or Sansanto powder manufactured by Sansanto , Santonox R, etc., or Topanol CA, etc. produced by ICI, or Ionox330, etc. produced by Shell, or Ant i oxidant 72 0, etc. produced by Ethyl, or Marunzen Petrochemical Co., Ltd. BHT. Its weight part may be from 0.01 to 5.0% by weight. Ultraviolet absorbers can be benzotriene (B e η ζ 〇tria ζ ο 1 es), Triazines, Benzophenones, Cinnamate , T-esters (Salicylate), etc. and their derivatives, examples that can be used are Tinuvin326, Tinuvin327, Tiruivin328, Tinuvin P, JF-77, JF-78, Advastab45, Advas tab48, Rylex H, Unistatl2, Unistat247, U nista 12 21 1, U vinu 1 4 0 0, U vinu 1 41 0, U vinu 1 M-4 0, Cyasorb UV-9, Cyasorb UV-287, Cyasorb UV-314, IIHI ISM: Page 14 200411015, V. Description of Invention (ίο) ''

Cyasorb UV-1084 、StabiliZer bx—721 'Eastman inhibitor OPS、Ferro AM-1 〇ι。其所佔重量份可為〇· 〇1 至5. 0%重量份。此摻合物於添加加工助劑後能大幅提昇耐候及光照後顏色及物性之穩定且呈現出高光澤及良好的切口耐衝擊強度。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（Μ I ): 依ASTM D- 1 2 38 測試規定，220。〇 X 10Kg，以g/l〇min 表示 ° 2 ·懸臂式切口刻痕埃左衝擊強度（I z 〇 ])): 依A S T M D - 2 5 6測試規定，試片厚度1 / 4 ”。 3·熱撓曲變形溫度（HDT ): 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1 / 8”。 5·色差（ΛΕ)及黃度（ΥΙ): 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At las公司氙狐光燈耐候試驗機，Model : Ci-65A ;照射時間300小時。Cyasorb UV-1084, StabiliZer bx-721 'Eastman inhibitor OPS, Ferro AM-1 〇ι. Its weight part may be 0.001 to 5.0% by weight. After adding the processing aid, this blend can greatly improve the weather resistance and the stability of color and physical properties after exposure to light, and exhibit high gloss and good notch impact strength. The various measurement methods and physical property test standards used in the present invention are summarized as follows: 1. Melt index (M I): According to ASTM D-1 2 38 test regulations, 220. 〇X 10Kg, expressed in g / l0min ° 2 · Cantilever-notch nick left impact strength (I z 〇))): According to ASTMD-2 5 6 test regulations, the thickness of the test piece is 1/4 ". 3 · Thermal Deflection Temperature (HDT): According to ASTMD-6 4 8 test, the thickness of the test piece is 1/4 ". 4 · Tensile strength modulus and elongation (ts & EL): According to ASTM D-638 test regulations, the thickness of the test piece is 1/8 ". 5. · Color difference (ΛΕ) and yellowness (ΥΙ): According to ASTM D- 2244 (color difference), D-1925 (yellowness) test regulations. 6 · Weather resistance test: According to ASTM D-4459 test regulations. Use At las Xenon fox light weathering tester, Model: Ci-65A; Irradiation time 300 hour.

第15頁 200411015 '五、發明說明（π) ^ 下列範例係進一步列舉本發明的特殊實例，除非特別註明，使用於範例中的百分率為重量百分率。列舉之實例係為詳細說明本發明，但本發明之範圍並不以此等實施為限。』西ABS接枝聚合物··採分段式核殼型乳化聚合法，聚合 ^度由25 °C〜90。(：以氧化還原起始法聚合，首段先聚合橡膠核層橡膠核層採熱分解起始法，聚合溫度由4 5 °C〜9 〇殼層之聚合添加苯乙烯及丙烯腈，為調節接枝率及 /刀子里’有時會加入少量的鏈轉移劑及多官能基等，又於多層=構時，就必需分成多次聚合反應。本乙稀''丙烯腈共聚合物（SAN):採連續式總體聚合反 A ° ’聚合溫度約1 5 0 °C，採熱分解起始法聚合，在中:/ T加入少量的溶劑及鏈轉移劑，在單體進料比 3〇%’丙_歸腈含量為2〇〜40%，其中SAN-1為丙烯腈含量2〇〜物°。之組表成物，而SAN-2為丙烯腈含量30.1〜40%之組成本2明之摻合組成物，可由如雙螺桿押出機、混合滾 5 内展合器的傳統混合及化合裝置所製造。二^範例用於列舉本發明之實例，但不侷限於本發明之組电p iWI » ' 姑丄。在申請專利範圍内，另外之實例及優點常見於技藝中的一般技術中。則歹，&例的換合組成物之測試結果列於表一；表二〜表五貝歹i出經耐候試驗後各相關物性之衰減現象，耐候試驗條Page 15 200411015 'V. Description of the invention (π) ^ The following examples are further specific examples of the present invention. Unless otherwise specified, the percentages used in the examples are weight percentages. The examples are given to illustrate the present invention in detail, but the scope of the present invention is not limited to these implementations. 』West ABS graft polymer ·· Segmented core-shell type emulsion polymerization method, polymerization degree from 25 ° C ~ 90. (: Polymerization by redox initiation method. The first step is to polymerize the rubber core layer. The rubber core layer adopts thermal decomposition initiation method. The polymerization temperature is from 45 ° C to 90 °. The polymerization of the shell layer adds styrene and acrylonitrile. Graft ratio and / in the knife sometimes add a small amount of chain transfer agent and polyfunctional groups, etc., and when the multilayer = structure, it must be divided into multiple polymerization reactions. This ethylene `` acrylonitrile copolymer (SAN ): Adopt continuous overall polymerization inverse A ° 'Polymerization temperature is about 150 ° C, polymerization using thermal decomposition initiation method, in: / T add a small amount of solvent and chain transfer agent, in the monomer feed ratio of 30. % 'Propionitrile nitrile content is 20 to 40%, of which SAN-1 is an acrylonitrile content of 20 to 40 °° C, and SAN-2 is an acrylonitrile content of 30.1 to 40%. Mingzhi blending composition can be made by the traditional mixing and compounding device such as twin screw extruder and mixing roller 5. The example is used to list the examples of the present invention, but it is not limited to the group electric p iWI »'Aunt. Within the scope of patent application, other examples and advantages are common in the general technology in the art. , &Amp; results change the composition of the combined embodiments are listed in Table I; Table II - Table V i after the shell was bad weathering test dependent attenuation properties of various phenomena, weathering test strip

200411015 五、發明說明（12) 件採：濕度： 55 ± 2 %RH 光源：氣弧燈喷注水：每120分鐘喷18分鐘照射時間： 3 00小時表一編號 A B C D ABS-1 33.079 — 33.079 - ABS-2 — 29.426 — 29.426 SAN-1 65.666 - 65.666 - SAN-2 - 69.319 - 69.319 安定劑 1.217 1.217 1.217 1.217 紫外線吸收劑 0. 038 0. 038 — - 總量 100.000 100.000 99.962 99.962 MI 23. 2 24. 1 23. 4 24. 2 IZ0D 19. 5 20. 1 19. 4 20.0 TS 480 491 485 494 EL 19. 0 19. 5 19. 2 19. 6 GLOSS 95 96 96 96200411015 V. Description of the invention (12) Collection: Humidity: 55 ± 2% RH Light source: Gas arc lamp spray water: 18 minutes spray every 120 minutes Irradiation time: 3 00 hours Table No. ABCD ABS-1 33.079 — 33.079-ABS -2 — 29.426 — 29.426 SAN-1 65.666-65.666-SAN-2-69.319-69.319 Stabilizer 1.217 1.217 1.217 1.217 UV absorber 0. 038 0. 038 —-Total 100.000 100.000 99.962 99.962 MI 23. 2 24. 1 23. 4 24. 2 IZ0D 19. 5 20. 1 19. 4 20.0 TS 480 491 485 494 EL 19. 0 19. 5 19. 2 19. 6 GLOSS 95 96 96 96

第17頁Page 17

200411015 '五、發明說明（13) HDT 90 92 91 92 其中： SAN-1 ••台化SAN TAIRISAN NF2200 SAN-2 ••台化SAN TAIRISAN NX3200 ABS-1 ··台>ί匕ABS基粉BP608 ABS-2 :台化ABS基粉ΒΡ618 安定劑二 N，r -雙硬脂醯胺乙烯+二硬脂醯季戊四醇二亞磷酸鹽+硬脂酸鎂紫外線吸收劑：2-(2，羥基-3,，5,-雙三級丁基苯）-5-氣苯并三曙T7坐 MI : 溶融指數（220 °Cx 10 kg，g/10min) IZ0D 埃左衝擊強度（kg- cm/ cm) TS 抗張強度（kg / cm2 ) EL 伸長率（％) GLOSS 光澤度（4 5度） HDT 熱撓曲變形〗显度（試片厚1 / 4 ” ，°C ) 表一（埃左衝擊強度IZ0D ;單位 :kg- cm/ cm) 編5虎 A B C D 照光前 19. 5 20. 1 19· 4 20. 0 照光後 19. 0 19. 5 17. 1 17. 0 差異值 -0.5 -0.6 ~ 2. 3 ~ 3. 0 第18頁 200411015 、五、發明說明（14) 表三（抗張強度TS，單位：故/ cm2) 編號 A B C D 照光前 480 491 485 494 照光後 4 6 2 467 321 365 差異值 -18 -24 -164 -129 表IZ3 (黃度 YI) A B C D 照光前 11.4 13. 5 11.6 13. 7 照光後 12. 6 14. 1 17. 4 19. 8 差異值 + 1· 2 + 0.6 + 5. 8 + 6.1 表五（色差 ΔΕ) 編號 A Β C D 差異值 + 1.4 + 1. 5 + 3.1 + 3 · 4 色差計算式係採用 ΛΕ =〔（ + ( + ( Δ1))2〕1/2 計算式。總體而論，沒有添加紫外線吸收劑者（範例c、之物性衰退程度較大，而有添加紫外線吸收劑 j ) 較無明顯之衰退。 ’其物性200411015 'Fifth, the description of the invention (13) HDT 90 92 91 92 Among them: SAN-1 •• Taiwan SAN TAIRISAN NF2200 SAN-2 •• Taiwan SAN TAIRISAN NX3200 ABS-1 ·· Taiwan > ABS base powder BP608 ABS-2: Taihua ABS-based powder BP618 stabilizer di-N, r-distearylamine ethylene + distearyl pentaerythritol diphosphite + magnesium stearate UV absorber: 2- (2, hydroxyl-3 ,, 5, -Bis tertiary butyl benzene) -5-Gas Benzo Sanshu T7 seat MI: Melt index (220 ° Cx 10 kg, g / 10min) IZ0D Angstrom left impact strength (kg-cm / cm) TS Tensile strength (kg / cm2) EL elongation (%) GLOSS gloss (45 degrees) HDT heat deflection deformation (signal thickness 1/4 ", ° C) Table 1 (Angstrom left impact strength IZ0D (Unit: kg-cm / cm) 5 Tiger ABCD before light 19. 5 20. 1 19 · 4 20. 0 After light 19. 0 19. 5 17. 1 17. 0 Difference -0.5 -0.6 ~ 2. 3 ~ 3. 0 Page 18 200411015 V. Description of the invention (14) Table III (tensile strength TS, unit: cm / cm2) No. ABCD Before light 480 491 485 494 After light 4 6 2 467 321 365 Outliers -18 -24 -164 -129 Table IZ3 (Yellowness YI) ABCD Before Illumination 11.4 13. 5 11.6 13. 7 After Illumination 12. 6 14. 1 17. 4 19. 8 Difference + 1 · 2 + 0.6 + 5. 8 + 6.1 Table 5 (color difference ΔΕ) No. A Β CD difference value + 1.4 + 1. 5 + 3.1 + 3 · 4 The color difference calculation formula uses ΛΕ = [(+ (+ (Δ1)) 2] 1 / 2 Calculation formula. In general, those who did not add ultraviolet absorbent (example c, the degree of physical deterioration is greater, and the ultraviolet absorbent j was added) had less obvious decline. 'Its physical properties

Claims

200411015

1. The composition of a weather-resistant abs copolymer contains: I a core-shell ABS graft polymer with a weight percentage of from 10 · 0 to 9 · 9%. 2. Styrene-acrylonitrile copolymer (SAN) from 0 to 90% by weight. 3 · Ultraviolet absorbent from 0 · 0 1 to 2 · 0% by weight, this weight is relative to the total weight of the resin. 22 According to Article 1 of the scope of the patent application, the core-shell type graft polymer is composed of the following: • Binary method is obtained by emulsification polymerization, and the feeding method can be batch or semi-batch addition. Material way. • The rubber series is obtained from diene monomers, and can be obtained by emulsification polymerization or block polymerization. The feeding method can be batch feeding or semi-batch feeding. 4 = The acrylonitrile content in the layer may be 10 ~ 35% by weight. • The particle size of the I compound can be single or multiple. = The 2nd member of the scope of the patent application, the shell layer 4 is one of the group τ composed of 0 to 10.0% by weight of multifunctional monomers in Oak Shengli. The rubber particle 彳 k distribution may be a single or multiple distribution rubber particle size.

Page 20 200411015 6. Scope of patent application 4. According to the first item 2 of the scope of patent application, the styrene-acrylonitrile copolymer (SAN) contains acrylonitrile in an amount of 20 to 40% by weight. 5. According to the first item 3 of the scope of the patent application, the ultraviolet absorber is selected from the group consisting of benzosanshuowa, sankeng, benzophenone, phenylene allyl ester, o-hydroxy T-based ester, etc. and At least ^ species of the group derived from the composition.

Page 21