經濟部中央標準局貝工消費合作杜印装 > c O q 、·、4 A7 _—___ B7 五、發明説明（1 ) ' 本發明有關具改良抗污性之丙烯腈-苯乙烯-两缔酸醋 (ASA)共聚物與改良ASA共聚物抗污性之方法。 丙缔赌/苯乙婦/丙缔fe S旨（ASA)共聚物係耐候化、^^ uv 之熱塑性聚合物，其曝於室外仍可保有顏色與適當安定 性。此等共聚物應用於汽車、建築與休間市場。例如， ASA共聚物係用以製造車體模製品、外部與内部設備零 件、保險槓零件、小貨車棚蓋與休間汽車零件；家用外牆 板與設備 '排水溝與下水道、百葉窗以及窗框；以及用於 游泳池與泵組件、室外家具、浴缸、淋浴分隔襴與礦泉。 —般而言，ASA共聚物之耐候化性良好，其係用以製造室 外用物件之優良候選者。 某些ASA共聚物適用之應用中，所形成之物件可與水、 溶劑或其他可能傷害該物件表面之物質接觸。例如，ASA 共聚物可用以製造汽車格架，諸如擋風玻璃下方之儀表板 部分通風孔格架。儀表板部分通風孔格架的考量之—係該 塑料對於水及/或擋風玻璃清洗溶液中之化學物質，或與 該塑料格架接觸之其他產物的抵抗性。考量之產物包括清 潔與磨光物質°已發現習用之ASA於此等應用中會沾？亏。 亦可於有關曝於水或其他藥劑之含水混合物的其他ASA 最終用途應用觀察到ASA之沾污現象。例如，已發現熱礦 泉浴缸會出現污垢。顏料、染料與水處理 '化學物質可能會 導致此等應用中之ASA沾污。 本文所使用之”沾污M包括被色、變紅、失去光澤、候化 及/或白化，其係表面瑕麻。此等沾污或候化通常係曝於 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) 装. 經漓部中央標準局員工消費合作社印製 五、發明説明（2 水或水與其他藥劑（諸如化學物 人物之下所锊 、顏料與染料）混 “匆之下所致ϋ會經由標示該聚 觀顯示。雖然沾污可能於任何時候發 （水斑狀外 室外或經候化之零件更易顯示沾污。Μ已發現曝於 經候化零件之沾序外觀椏爲不利， AO* JL φ , 馬有許多可能使用 ASA共聚物製造（零件可能會與海或包 ,,m L,, "上迷樂劑之產物 接觸。因此，極需要製造具有抗污性盥 、 發生之外觀問題的ASA物件。 〃、他於使用期間 已發現一包括特定氣或以砂爲底質添加劑之规共聚物組 合物具有南度抗污性、抗斑性與耐候化性。 本發明組合物包括ASA共聚物盥一種盏 , κ^、梗吼或以矽爲底質添 加劑’或此等添加劑之混合物，丨用量足以改善該組合物 之抗污性。有效量係指可顯示可測量或可觀察差異之用 量。該氟爲底質添加劑係一種經氟化化合物，以氟界面活 性劑爲佳^該矽爲底質添加劑係一種聚合矽物質，以聚矽 氧烷爲佳。以可自該ASA基質移至所形成物件表面之疏水 非離子化合物爲佳。 本發明ASA共聚物係本技藝中已知者，而且可由習知方 法製備’例如根據美國專利第3,944,631號；4,111,876 號；4,528,328 號；4,537,933 號；5,068,285 號與 5,070，H2 號所述之方法，本文中提出每種揭示以供參考。ASA共聚 物包括至少一種包含丙烯酸橡膠粒子之苯乙烯-丙烯腈共 聚物基質。該苯乙烯部分可能包括選自苯乙烯與烷基笨乙 烯（諸如λ -曱基苯乙烯、對-甲基苯乙烯、乙基苯乙烯、 本紙張尺度適用中國國家標準（CNS ) Λ4規格P10X297公釐） ϋ ί I- In I 8 - - * I _ I -I I n----- 丁 (請先閱讀背面之注意事項再填寫本頁) A7 ----------Β7 五、發^^明（3 ) " ---- 異丙基苯乙烯等）以及經_化經取代苯乙埽（諸如氣笨乙稀 寺）及其混合物之乙晞基芳族單體。以丙烯腈與^ _甲基苯 乙埽之共聚物基質爲佳。ASA共聚物通常爲無規非晶相三 聚物’其係由大塊共聚或乳化共聚方法製造，或將苯乙缔 -丙烯腈接枝於丙烯酸彈性體主幹製造。 孩兩烯酸橡膠粒子可接枝於該苯乙埽-丙晞腈共聚物基 質’而且以此爲佳。該聚合作用期間，可藉由殘留於該橡 膠中之不飽和反應接枝於該聚苯乙烯/丙烯腈（SAN)基質， 或添加額外之丙晞酸橡膠粒子與該經聚合SAN基質，藉由 另外之不飽和反應於聚合作用後接枝於該San基質上。 以聚苯乙晞標準測量，孩A S A共聚物之重量平均分子 量自大約50,000至大約120,000。 經濟部中央標準局員工消費合作社印製 H - I - n n I . 艮—-I I _1 n I T ' ,1 (請先閱讀.背面之注意事項再填寫本頁) 該丙烯酸橡膠粒子可至少部分交聯，而且以此爲佳。本 發明具體化實例之一中，該ASA共聚物可以先乳化聚合丙 晞酸貌酯或甲基丙烯酸燒酯或其混合物與至少 < 種交聯單 體，形成一種經交聯丙烯酸酯彈性體，隨後乳化聚合該笨 乙晞單體、該丙烯腈與該丙烯酸酯橡膠之混合物。前二步 驟之順序可交換，因此該丙烯酸彈性體可於存在已形成經 交聯苯乙晞-丙烯腈共聚物下聚合之。 一般而言，形成該丙烯酸橡膠時，該丙締酸酯及/或甲 基丙烯酸酯單體可選自具有<^至Cl2；^基'之丙烯酸烷酯與 甲基丙滞燒醋’以C4至C!◦爲佳。以c4至Ce两烯酸燒醋 及此等丙烯酸船與其他丙稀酸酿或甲基丙稀酸酿之混合物 爲佳。適用之丙烯酸單體包括但不受限於丙缔酸乙酯、丙 本紙張尺度適用中國圃家標準（CNS ) A4規格（2I0X297公釐） A7 B7 經濟部中央榡準局員工消費合作社印製 五、發明説明（4 烯酸異丙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸己醋、 丙烯酸2 -乙基己酯、丙稀酸十二酯、丙烯酸3 -曱基·丁 酿、丙晞酸異丁醋、丙稀酸異癸酷以及對應之甲基丙缔酸 酯。該交聯單體係聚烯基不飽和單體，以二乙烯基、二两 烯酸酯、三丙烯酸酯或四丙烯酸酯單體爲佳。 該丙烯酸聚合作用之交聯單體係個別單體混合物重量之 大約0.05至大約1〇百分比爲佳，以01至5百分比更佳。 適用之交聯單體包括但不受限於二乙烯基苯、三丙缔酸三 羥甲酯、甲基丙烯酸烯丙酯、延胡索酸二烯丙酯、順式丁 烯二酸二烯丙酯、二甲基丙烯酸〗，3_伸丁酯、二甲基两缔 酸二伸乙酯、二甲基丙烯酸乙二醇酯、三甲基丙烯酸三和 甲基丙烷、三丙烯酸三羥甲基丙烷、的丙烯酸二甘醇酯、 二乙烯基酸、自太酸二烯丙酯、二乙烯基山梨糖醇、二甲基 丙晞酸三乙二醇酯、二丙烯酸三甲二醇 '二丙烯酸丁二醇 酯、二丙烯酸五甲二醇酯、三丙烯酸縮水如油酯與季戍四 醇之三丙烯酸酯。 該乳化聚合作用可以本技藝中習用之方式進行，例如使 用用量自大約該乳液之〇· 5至大約5重量％之陰離子、非 離子或陽離子乳化劑。可使用習用幻發劑與鏈轉移劑，其 包括但不受限於氫乳化物與有機過氧化物，並且可使用氧 化還原觸媒。以該單體之重量爲基準，該'引發劑之用量可 自大約0.005至大約2重量百分比。 笨乙烯與丙烯腈之聚合作用製得—種硬性基質组份。丙 晞腈對於苯乙晞之較佳比率自大約〗至3丙烯腈至大約1 關家標準（CNS ) A4g ( 21GX 297公釐 1^1 II- - ml -I - - I— I I ^^1 I m ^^1 —ϋ I I— , 牙 、-& f請先閱讀背面之注意事項再填寫本頁j 442533 A7 B7 經濟部中央榇隼局負工消费合作社印製 五、發明説明（ 至7苯乙烯，其以重量計。該丙晞腈-笨乙烯基質必須在 自大約20至大約60重量百分比之ASA共聚物範圍内，自 大約20至大約40重量百分比之ASA共聚物爲佳。具有 〇 c -甲基苯乙烯之組合物爲佳。 該A S A共聚物包括自大約5至大約95重量百分比之丙 烯酸單體、自〇至大約35重量百分比之經交聯苯乙埽-丙 烯腈共聚物，以及自大約5至大約95重量百分比之未經 交聯聯苯乙烯-丙烯腈共聚物基質。諸如例如使用大塊聚 合作用製備该ASA共聚物時，該丙晞酸橡勝粒子可包含 熱塑性聚合物吸藏。 適用之ASA共聚物物質爲市售者。市售產物中較佳者 係 LURAN S 778T ’由 BASF Corporation, 3000 Continental Drive North, Mt, Olive, New Jersey 07828 所售。 較佳之氟爲底質添加劑係疏水氟界面活性劑。氟界面活 性劑之特徵係其具有疏水部分_CnF2n+i與親水部分。該氟 界面活性劑具有F(CF2CFx)n之氟碳基，其中n係3至8。 該疏水氟界面活性劑可添加於ASA共聚物組合物t，其 用量高達大約0_5重量百分比，自大約0.005至大約’0.15 重量百分比爲佳，自大約〇·〇8至大約〇.〗2重量百分比尤 佳°氟界面活性劑係市售者，例如來自DuPont Specialty Chemicals，Wilmington, Delaware,商標爲 ZONYL® 者。其中 以 ZONYL® FSN 100 與 FSO 100 爲佳。 較佳之矽爲底質添加劑係聚矽氧流體與脂類。其中以聚 甲基矽氧烷類、聚苯基甲基矽氧烷類與聚二苯基矽氧烷類 I I I - - —I - I— I --*衣 I —I - --------------- I、订 (請先閲讀背面之注意事項再填寫本y〕 良紙張尺度適财ϋ財縣（CNS) A4規格 (210X 297公釐） 經濟部中央梯準局員工消費合作杜印製 A7 ___B7 五、發明説明（6 ) 特別適用。尤佳者係聚笨基曱基秒氧境類。 本發明之聚矽氧物質之黏度可介於大約50與大約 250,000厘史。使用黏度自大約5〇,〇〇〇至大約150,000厘 史之聚碎氧坑類爲佳。此等聚矽氧燒類係市售者，例如來 自 Dow Corning Corp.，Midland, Michigan and General Electric,The Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China Cooperating with Dumplings > c O q 、 ·, 4 A7 _—___ B7 V. Description of the Invention (1) '' The present invention relates to acrylonitrile-styrene- Method for improving acid resistance of ASA copolymer and ASA copolymer. Acrylic acid / acetophenone / acrylic acid (ASA) copolymer is a weather-resistant, ^^ uv thermoplastic polymer, which can maintain its color and proper stability when exposed to the outdoors. These copolymers are used in the automotive, construction and leisure markets. For example, ASA copolymers are used to make car body moldings, external and internal equipment parts, bumper parts, van covers and rest car parts; household exterior wall panels and equipment 'drains and sewers, shutters and window frames ; And for swimming pool and pump assemblies, outdoor furniture, bathtubs, shower partitions and mineral springs. -In general, ASA copolymers have good weathering resistance, and they are excellent candidates for manufacturing outdoor articles. In some applications where ASA copolymers are suitable, the formed object can be in contact with water, solvents, or other substances that may harm the surface of the object. For example, ASA copolymers can be used to make automotive grids, such as the dashboard vents grid under the windshield. Some considerations for the vent grille of the instrument panel are the resistance of the plastic to chemicals in water and / or windshield cleaning solutions, or other products that come into contact with the plastic grille. Products considered include cleaning and polishing materials ° Has the conventional ASA found to be contaminated in these applications? deficit. Contamination of ASA can also be observed in other ASA end-use applications related to exposure to water or aqueous mixtures of other agents. For example, dirt has been found in hot mineral bathtubs. Pigments, Dyes, and Water Treatment 'Chemicals may cause ASA contamination in these applications. As used herein, "staining M" includes discoloration, redness, tarnishing, weathering, and / or whitening, which is a blemishes on the surface. Such stains or weathering are usually exposed to this paper's standard and apply Chinese national standards ( CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling out this page). Packed. Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Foreign Affairs of the People's Republic of China. 5. Description of the invention (2 Water or water and other agents (such as chemical Underneath the objects, pigments and dyes) will be displayed by marking the view. Although the contamination may occur at any time (water spots outside or weathered parts are more likely to show contamination) M has been found to be unfavorable for exposure to weathered parts. AO * JL φ, Ma has many possible uses of ASA copolymers (parts may be mixed with the sea or package ,, m L ,, " The product of the psychedelic agent is in contact. Therefore, it is extremely necessary to manufacture an ASA article having antifouling and appearance problems. 发生 He has discovered a regular copolymer combination including a specific gas or a sand-based additive during use. Anti-fouling The composition of the present invention includes a ASA copolymer, κ ^, stalk or silicon-based additives' or a mixture of these additives, and the amount is sufficient to improve the composition. Antifouling. Effective amount refers to the amount that can show measurable or observable differences. The fluorine as a substrate additive is a fluorinated compound, and a fluorine surfactant is preferred ^ The silicon as a substrate additive is a polymeric silicon The substance is preferably polysiloxane. The hydrophobic nonionic compound that can be moved from the ASA substrate to the surface of the formed object is preferred. The ASA copolymer of the present invention is known in the art and can be prepared by conventional methods. For example, each of the disclosures are set forth herein for reference by the methods described in U.S. Patent Nos. 3,944,631; 4,111,876; 4,528,328; 4,537,933; 5,068,285 and 5,070, H2. ASA copolymers include at least one kind of acrylic rubber particles. A styrene-acrylonitrile copolymer matrix. The styrene portion may include a material selected from the group consisting of styrene and alkyl styrene (such as λ-fluorenylstyrene, p-methylstyrene, Basic styrene, the size of this paper applies Chinese National Standard (CNS) Λ4 specification P10X297 mm) ϋ ί I- In I 8--* I _ I -II n ----- D (Please read the precautions on the back first (Fill in this page again) A7 ---------- Β7 V. Send ^^ Ming (3) " ---- Isopropylstyrene, etc.) and phenyl hydrazone (such as Acetylenic stilbene) and its mixtures. Acetyl aromatic monomers are preferred. The copolymer matrix of acrylonitrile and ^ -methylphenethylhydrazone is preferred. ASA copolymers are usually random amorphous phase terpolymers. It is made by bulk copolymerization or emulsion copolymerization, or by grafting styrene-acrylonitrile-acrylonitrile onto the backbone of acrylic elastomer. The bis-acrylic acid rubber particles can be grafted onto the styrene-acrylic acid-propionitrile copolymer matrix 'and it is preferred. During the polymerization, the polystyrene / acrylonitrile (SAN) matrix can be grafted by the unsaturated reaction remaining in the rubber, or additional propionate rubber particles and the polymerized SAN matrix can be added by Another unsaturated reaction is grafted onto the San substrate after polymerization. The weight average molecular weight of the ASA copolymer is from about 50,000 to about 120,000 as measured by polystyrene. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economy H-I-nn I. Gen — -II _1 n IT ', 1 (Please read first. Note on the back before filling this page) The acrylic rubber particles can be at least partially crosslinked , And this is better. In one of the embodiments of the present invention, the ASA copolymer can be firstly emulsified and polymerized with propionate or methacrylic acid ester or a mixture thereof with at least < crosslinking monomers to form a crosslinked acrylate elastomer. Then, a mixture of the acrylonitrile monomer, the acrylonitrile and the acrylate rubber is emulsified and polymerized. The order of the first two steps is interchangeable, so that the acrylic elastomer can be polymerized in the presence of a cross-linked acetofluorene-acrylonitrile copolymer. Generally speaking, when the acrylic rubber is formed, the acrylic and / or methacrylic acid ester monomers can be selected from alkyl acrylates and methyl propylene scorched vinegar having ^ to Cl2; C4 to C! ◦ are preferred. C4 to Ce dienoic acid vinegar and mixtures of these acrylic vessels with other acrylic or methyl acrylic acids are preferred. Applicable acrylic monomers include, but are not limited to, ethyl acrylate, and acrylic paper sizes. Applicable to China Garden Standard (CNS) A4 specifications (2I0X297 mm) A7 B7 Description of the invention (4 Isopropyl acrylate, propyl acrylate, n-butyl acrylate, hexanoic acid acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, 3-acrylic acid · butyl acrylate, propyl methacrylate Acid isobutyl vinegar, isodecyl acrylic acid, and the corresponding methyl acrylate. The crosslinked single system polyalkenyl unsaturated monomer is divinyl, dihexenoate, triacrylate or Tetraacrylate monomers are preferred. About 0.05 to about 10 percent by weight of the individual monomer mixture of the crosslinking monomer system of the acrylic polymerization is preferred, and more preferably from 01 to 5 percent. Suitable crosslinking monomers include but Not limited to divinylbenzene, trimethylol triacrylate, allyl methacrylate, diallyl fumarate, diallyl cis butyrate, dimethacrylic acid, 3_ Butyl ester, dimethyl ethionate, ethylene dimethacrylate Esters, tris and methylpropane trimethacrylate, trimethylolpropane triacrylate, diethylene glycol acrylate, divinyl acid, diallyl oleate, divinyl sorbitol, dimethyl Triethylene glycol propionate, trimethyl glycol diacrylate butylene glycol diacrylate, pentamethyl glycol diacrylate, triacrylate triacrylate such as oleyl ester and quaternary tetraol triacrylate. The emulsion polymerization This can be done in a manner customary in the art, such as using an anionic, non-ionic or cationic emulsifier in an amount of from about 0.5 to about 5 weight percent of the emulsion. Conventional phlegmats and chain transfer agents can be used, including but not Limited to hydrogen emulsions and organic peroxides, and redox catalysts can be used. Based on the weight of the monomer, the amount of the 'initiator can be from about 0.005 to about 2 weight percent. Styrene and acrylonitrile It is made by polymerization—a kind of hard matrix component. The preferred ratio of propionitrile to acetofluorene is from about 3 to 3 acrylonitrile to about 1 Guanshang Standard (CNS) A4g (21GX 297 mm 1 ^ 1 II- -ml -I--I— II ^^ 1 I m ^^ 1 —ϋ II—, teeth,-& f Please read the notes on the back before filling out this page j 442533 A7 B7 Printed by the Central Government Bureau of the Ministry of Economic Affairs and Consumer Cooperatives (To 7 styrene, by weight. The propionitrile-benzyl vinylene must be in the range of from about 20 to about 60 weight percent of the ASA copolymer, and preferably from about 20 to about 40 weight percent of the ASA copolymer. A composition having oc-methylstyrene is preferred. The ASA copolymer includes from about 5 to about 95 weight percent of an acrylic monomer, and from 0 to about 35 weight percent of cross-linked acetophenone-acrylonitrile. Copolymers, and from about 5 to about 95 weight percent of an uncrosslinked styrene-acrylonitrile copolymer matrix. For example, when the ASA copolymer is prepared using bulk polymerization, the acrylic acid propionate particles may include a thermoplastic polymer occlusion. Suitable ASA copolymer materials are commercially available. The better commercially available product is LURAN S 778T ', sold by BASF Corporation, 3000 Continental Drive North, Mt, Olive, New Jersey 07828. The preferred fluorine is a substrate-based hydrophobic fluorine surfactant. The fluorosurfactant is characterized by having a hydrophobic portion _CnF2n + i and a hydrophilic portion. The fluorosurfactant has a fluorocarbon group of F (CF2CFx) n, where n is 3 to 8. The hydrophobic fluorosurfactant can be added to the ASA copolymer composition t in an amount of up to about 0-5 weight percent, preferably from about 0.005 to about '0.15 weight percent, and from about 0.008 to about 0.2 weight percent. Particularly preferred fluorosurfactants are commercially available, for example from DuPont Specialty Chemicals, Wilmington, Delaware, under the trademark ZONYL®. Among them, ZONYL® FSN 100 and FSO 100 are preferred. The preferred silicon is a polysiloxane fluid and a lipid. Among them, polymethylsiloxanes, polyphenylmethylsiloxanes and polydiphenylsiloxanes III---I-I- I-* 衣 I -I------ ---------- I. Order (please read the precautions on the back before filling in this form) Good paper size suitable for financial and financial county (CNS) A4 specification (210X 297 mm) Central Ministry of Economic Affairs A7 ___B7 produced by the Bureau ’s consumer cooperation 5. The invention description (6) is particularly applicable. The best is polybenzyl-based second oxygen environment. The viscosity of the polysiloxane material of the present invention may be between about 50 and about 250,000 It is preferred to use polyoxygen pits having a viscosity from about 50,000 to about 150,000 centimeters. These polysiloxanes are commercially available, for example from Dow Corning Corp., Midland, Michigan and General Electric,
Scenectady，New York。其中較佳者係由D〇w c〇rmng所售之 710 Fluid。 該聚矽氧可添加於ASA共聚物，其用量可高達5重量百 分比，自大約0.1至大約3重量百分比爲佳，自大約〇1 至大約1重量百分比尤佳。 除ASA共表物與該氟或妙爲底質添加劑之外，本發明之 ASA共聚物組合物可包括另外聚合物組份或添加劑。例 如，該ASA共聚物可與一或多種不同熱塑性聚合物摻和， 其包括但不受限於與聚笨乙烯、聚酯、未經改良之苯乙缔 -丙烯赌共聚物、聚氣化乙烯、聚甲基丙烯酸酯甲酯與聚 醋（諸如聚對酞酸伸丁酯與聚對酞酸伸乙酯）之摻和物。 可與本發明ASA共聚物組合物併用整另外添加劑包括但 不受限於受阻胺安定劑（HALS)、苯並uv吸收劑 '有機與 無機顏料、染料與填料，熱塑性安定劑、抗氧化劑 '潤滑 劑、處理助劑與增塑劑，諸如c7至cn醇類之苯基二羧酸 醋類，諸如酞酸二辛酯與酞酸二異壬酯s [本發明組合物包 括自大約0.1至大約1.0重量百分比之HALS或HALS之混 合物爲佳。 該ASA組合物可以任何本技藝中習知方式摻和或化合。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ^1. - I !-- - I - -I I - - ---1 I m I (請先Μ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（7 ) 例如但不受限於，可於一個單或雙螺旋擠製器中混合、 於輥磨機或Banbury混合機中以高溫碾磨 '連續熔融摻和 或砑光製備聚合物摻和物。所有此等摻和製備方法可在例 如Herschel型混合機中混合之前進行。摻和作用可於用以 製造最終物件之相同設備中進行，例如螺旋型擠製器。或 者，該摻和物可於隨後之熱成型中，藉由例如熔融混合或 擠製模製技術製成丸粒。化合與粒化作用可以本技藝中各 種習知方法任一者進行。 本發明组合物可由任何熱成型技術製造，例如注模模 製、壓縮模製與擠模模製技術^模製條件與一般模製ASA 共聚物组合物所使用之條件相同。特定化合物與設備之模 製條件可根據所使用之方法直接試驗使其最適化。 本發明組合物有利於製造汽車組件，諸如儀表板部分通 風孔格架等，以及建築組件，室外物件與曝於水之零件浴 缸、淋浴分隔欄與礦泉。 以下列實例説明本發明。該實例僅作爲舉例用，並非用 以限制本發明所述與申請專利之範圍。除非另有所述，否 則所有份數均爲重量份數α 實施例1 本發明係根據 Ford Motor Company Test Procedure No. 84-52509試驗。使用具有標準UV安定劑'包裝，由BASF Corporation 所售之 ASA (LURAN® S 778T)作爲該 ASA。使用 不具uv安定劑包裝相同之物質作爲不具uv安定劑包裝 之ASA。所有樣本包含根據BASF Corporation的Color Code -ίο- 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） I - - - --I -- I I I - -I -- k ·- - - I -I ----- ^—► _ ，1· (請先閲讀背面之注意事項再填寫本頁) A7 B7 五 '發明説明（8 ) BLK-31261之碳黑。將不同用量本發明之氟界面活性劑或 含秒添加劑添加於所述ASA。於Herschel型混合機中混合 該组合物之组份，隨後於雙螺旋40 mm擠製器中化合。 使用下列標準注模模製技術製造樣本板。於24小時室 溫陳化期間之後，對該板進行Xenon Arc Weatherometer per SAE J1960程序。於2500 kJ/m2後，進行下列沾污試驗。Scenectady, New York. The better one is 710 Fluid sold by Dow cormng. The polysiloxane can be added to the ASA copolymer in an amount of up to 5 weight percent, preferably from about 0.1 to about 3 weight percent, and more preferably from about 0.01 to about 1 weight percent. The ASA copolymer composition of the present invention may include additional polymer components or additives in addition to the ASA co-forms and the fluorine or substrata additive. For example, the ASA copolymer can be blended with one or more different thermoplastic polymers including, but not limited to, polyethylene, polyester, unmodified styrene-propylene copolymer, polygasified ethylene , Blend of polymethyl methacrylate and polyacetate (such as polybutylene terephthalate and polyethyl terephthalate). Additional additives that can be used in combination with the ASA copolymer composition of the present invention include, but are not limited to, hindered amine stabilizers (HALS), benzouv absorbents 'organic and inorganic pigments, dyes and fillers, thermoplastic stabilizers, antioxidants', and lubricant Agents, processing aids, and plasticizers, such as phenyl dicarboxylic acid esters of c7 to cn alcohols, such as dioctyl phthalate and diisononyl phthalate [The composition of the present invention includes from about 0.1 to about 1.0% by weight of HALS or a mixture of HALS is preferred. The ASA composition can be blended or compounded in any manner known in the art. This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297mm) ^ 1.-I!--I--II----- 1 I m I (Please read the precautions on the back before filling (This page) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 __B7_ V. Description of the Invention (7) For example, but not limited to, it can be mixed in a single or double screw extruder, in a roll mill or a Banbury mixer The polymer blend is prepared by high temperature milling 'continuous melt blending or calendering. All such blending methods can be performed before mixing, for example, in a Herschel type mixer. Blending can be performed in the same equipment used to make the final article, such as a screw-type extruder. Alternatively, the admixture can be pelletized in subsequent thermoforming by, for example, melt mixing or extrusion molding techniques. Combining and granulating can be performed by any of various conventional methods in the art. The composition of the present invention can be manufactured by any thermoforming technique, such as injection molding, compression molding, and extrusion molding techniques. ^ The molding conditions are the same as those used for general molding of the ASA copolymer composition. The molding conditions of specific compounds and equipment can be directly tested and optimized according to the method used. The composition of the present invention is advantageous for manufacturing automobile components, such as an instrument panel partial vent hole grid, and the like, as well as building components, outdoor objects and water-exposed parts, bathtubs, shower dividers, and mineral springs. The following examples illustrate the invention. This example is for illustration purposes only and is not intended to limit the scope of the invention described and claimed. Unless otherwise stated, all parts are parts by weight α Example 1 The present invention is tested according to Ford Motor Company Test Procedure No. 84-52509. As the ASA, a ASA (LURAN® S 778T) sold by BASF Corporation was used with a standard UV stabilizer package. Use the same material without UV stabilizer as the ASA without UV stabilizer. All samples include according to the Color Code of the BASF Corporation -ίο- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) I-----I-III--I-k ·-- -I -I ----- ^ —► _, 1 · (Please read the notes on the back before filling this page) A7 B7 Five 'Invention Note (8) BLK-31261 carbon black. Different amounts of the fluorine surfactant or the second-containing additive of the present invention are added to the ASA. The components of the composition were mixed in a Herschel mixer, and then combined in a twin-screw 40 mm extruder. Sample boards were manufactured using the following standard injection molding techniques. After a 24-hour room temperature aging period, the plate was subjected to the Xenon Arc Weatherometer per SAE J1960 procedure. After 2500 kJ / m2, the following contamination tests were performed.
In - I- - I ^^^1 —^ϋ. - - n^l —ϋ In ^^^1 , 5.-5 (請先閱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 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（9 ) A7 B7 經濟部中央標準局員工消費合作社印装 表1 組合物 具UV包裝 之ASA 不具UV包裝 之ASA 恭加劑 用量 A X -0- -0- B X -0- -0- C X DUPONT ZONYL® FSO 100 0.1 D X DUPONT ZONYL® FSO 100 0.1 E X DUPONT ZONYL® FSO 100 0.1 F1 X DUPONT ZONYL® FSO 100 0.1 G X DUPONT ZONYL® FSO 100 0.1 Η X FSO 100 0.1 I X -0- -0- J X2 FSO 100 0.1 K X DOW CORNING SILICONE 710 FLUID 0.5 L X FSN 100 0.1 1 =1/2標準UV包裝 =經母體混合物濃縮而非擠製導入之碳黑 -12- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ϋ 1· - I- - ί --- , 丨队 -I I I - I T (請先閲讀背面之注意事項再填寫本頁) 442533 A7 ___B7_ 五、發明説明（10 ) 表2 觀察試樣本板上之斑點 使用吸管將Ford Motor Company市售之播風玻璃清洗流 體、具有橡膠清洗萃取物之擋風玻璃清洗流體與具有耐綸 清洗萃取物之擋風玻璃清洗流體各者滴一滴於製備之樣本 板上。於三（3)分鐘後觀察所滴上之液體斑點外觀。 樣本 試樣上之斑點外觀 A 斑點未擴散開 B 斑點未擴散開 C 斑點極均勻；稍微擴散 D 斑點擴散開，並彼此相連；油狀斑點外觀(彩虹狀） E 斑點擴散開，並彼此相連(彩虹狀） F 斑點擴散開，並彼此相連(彩虹狀） G 如控制組Β中一般，斑點均勻，僅稍微擴散(非彩虹狀） Η 斑點立刻擴散(稍微彩色） I 斑點明顯擴散但仍保持圓形（彩虹狀） J 斑點明顯擴散(彩虹狀） κ 斑點保持形狀；但未擴散 丄 斑點明顯擴散；高溫（彩虹狀） 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 表3 去除斑點並以溫水清洗1 5秒隨後乾燥後之試樣外觀 歸納表〗所述之觀察後，於溫水下清洗該試樣，並以壓 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 五、發明説明（11 ) 縮氮乾燥之。然後檢視該表面之沾污與斑點情形。 樣本 試樣表面外觀 分級法 (0=最差;10=最佳） A 斑點 0,0 B 斑點 0,0 C 有些斑點 3,2 D 稍微有斑點 5,4 E 梢微有斑點 7,5 F 稍微有斑點 7,5 G 斑點 2,2 Η 稍微有斑點 6,6 I 無斑點 10,10 J 無斑點 10,9 K 斑點 8,8 __ L 無斑點 10,9 - --.n I I H. - 1 I I 丁 W · 5-" . · (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 分級法：0表示有明顯白色殘留；10表示無可觀察到 之殘留 可看出本發明組合物提供抗污性與抗斑性之優點。 已參考較佳具體化實例詳細説明本發明。然而，必須注In-I--I ^^^ 1 — ^ ϋ.--N ^ l —ϋ In ^^^ 1, 5.-5 (Please read the precautions on the back before filling this page) Staff of the Central Standards Bureau of the Ministry of Economic Affairs The paper size printed by the consumer cooperative is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) V. Description of the invention (9) A7 B7 Printed by the Consumer Cooperative of the Central Standard Bureau of the Ministry of Economic Affairs. UV packaging of ASA additives AX -0- -0- BX -0- -0- CX DUPONT ZONYL® FSO 100 0.1 DX DUPONT ZONYL® FSO 100 0.1 EX DUPONT ZONYL® FSO 100 0.1 F1 X DUPONT ZONYL® FSO 100 0.1 GX DUPONT ZONYL® FSO 100 0.1 Η X FSO 100 0.1 IX -0- -0- J X2 FSO 100 0.1 KX DOW CORNING SILICONE 710 FLUID 0.5 LX FSN 100 0.1 1 = 1/2 standard UV packaging = concentrated by the mother mixture and Non-extruded carbon black-12- This paper size applies to China National Standard (CNS) A4 (210X297 mm) ϋ 1 ·-I--ί ---, 丨 Team-III-IT (Please read the back first (Notes on this page, please fill out this page) 442533 A7 ___B7_ V. Description of the invention (10) Table 2 Observation The spots on the sample plate were prepared by using a straw to prepare a drop of windshield glass cleaning fluid commercially available from Ford Motor Company, a windshield glass cleaning fluid with a rubber cleaning extract, and a windshield glass cleaning fluid with a nylon cleaning extract. On the sample board. After three (3) minutes, observe the appearance of the liquid spots dropped. The appearance of the spots on the sample A spots are not diffused B spots are not diffused C spots are extremely uniform; slightly diffused D spots are diffused and connected to each other; oily spots appearance (rainbow-shaped) E spots are diffused and connected to each other ( (Rainbow-shaped) F The spots spread apart and are connected to each other (Rainbow-shaped) G As in the control group B, the spots are uniform and spread only slightly (non-rainbow-shaped) Η The spots spread immediately (slightly colored) I The spots spread obviously but remain round (Rainbow-shaped) J spots are obviously diffused (Rainbow-shaped) κ spots remain in shape; but not diffused 丄 Spots are significantly diffused; high temperature (Rainbow-shaped) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) (Fill in this page) Table 3 After removing the spots and washing with warm water for 15 seconds and then drying the sample appearance summary table as described in the table, wash the sample under warm water, and apply this paper to China Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of invention (11) Nitrogen drying. Then inspect the surface for stains and spots. Surface appearance grading method of sample (0 = worst; 10 = best) A spot 0,0 B spot 0,0 C some spots 3,2 D slightly spotted 5,4 E slightly spotted 7,5 F Slightly spotted 7,5 G, spotted 2,2 Η Slightly spotted 6,6 I Stainless 10,10 J Stained 10,9 K Stained 8,8 __ L Stained 10,9--. N II H. -1 II DING W · 5- ". · (Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs: Classification method: 0 means there is obvious white residue; 10 means no observable To the residue, it can be seen that the composition of the present invention provides the advantages of stain resistance and spot resistance. The invention has been described in detail with reference to preferred specific examples. However, it must be noted
I 意在本發明及申請專利項目之精神與範圍内可製造多種變 化與改良。 -14- 本紙張尺度適用中囤國家標準（CNS ) A4規格（210X297公釐）I intend to make many changes and improvements within the spirit and scope of the present invention and patent application. -14- This paper size applies to the national standard (CNS) A4 specification (210X297 mm)