A 6 B 6 199902 五、發明説明（1 ) (請先閲讀背面之注意事項再塡"本頁) 本發明關於一種可用於覆蓋还料（capstock )及其他 應用領域之樹脂組成物。更具體地說，本發明提供之樹脂 •組成物特別適用於作爲共擠出於或疊積於構造用塑膠—— 如聚（氯乙烯）——上的材料，本發明亦關於這些複合材 料之製造以及其製成之物品。 茲先參照本發明在複合材料——包含一層表面材料而 黏附於一層聚（氣乙烯）構造用塑膠者一製造方面的適 用性加予說明。由以下說明可知，本發明具有較大的適用 性° 衆所週知地，聚C氯乙烯）樹脂（以下簡稱PVC )具 有許多良好的性質，使它特別適宜作爲構造用材料。在強 調構造用塑膠之衝擊強度的運用場合，PVC能與衝擊改良 劑樹脂摻配使用，而使形成的組成物具有較佳的衝攀強度 。這些衝擊強度高的PVC組成物，卽可利用擠壓或其他方 式製成各種物品，它可擁有優越的衝擊強度、靱度、以及 其他所欲的機械及化學性質。例擧的這些物品包括：建築 物-特別是住宅建物——之外壁板（siding )、百葉 窗、窗戶及門框之製作輪题（technical prof i le )、雨水排 一，一 放系統、以及圍牆。 經濟部中央標準局印製 這些PVC組成物之缺點是它的耐候性質較差，特別是 呈褐色及藍色等較深的顔色時，它的顔色保留性（Color retention )較爲不足。由一般背景觀之，可知帶有顔色 之PVC組成物已被廣泛地用於美學方面，而pvc組成物 则係藉著使用諸如顔料及/或染料等色料使它帶有顔色。 —3 ~ 甲 4 (210X297公釐） A 6 B 6A 6 B 6 199902 V. Description of the invention (1) (Please read the precautions on the back before reading this page) This invention relates to a resin composition that can be used for capstock and other applications. More specifically, the resin / composition provided by the present invention is particularly suitable as a material that is coextruded or stacked on structural plastics such as poly (vinyl chloride), and the present invention also relates to these composite materials Manufacturing and the articles made from it. The applicability of the present invention in terms of manufacturing of a composite material containing a layer of surface material and adhered to a layer of poly (gaseous vinyl) structural plastics will be described first. As can be seen from the following description, the present invention has great applicability. It is well known that polyvinyl chloride (PVC) resin (hereinafter referred to as PVC) has many good properties, making it particularly suitable as a material for construction. In applications where the impact strength of structural plastics is emphasized, PVC can be blended with impact modifier resins so that the resulting composition has better impact strength. These high-strength PVC compositions can be made into various articles by extrusion or other methods. It can have excellent impact strength, sag, and other desired mechanical and chemical properties. Examples of these items include: buildings—especially residential buildings—technical pro fi le (siding), shutters, windows and door frames (technical prof i le), rainwater drainage, one-release systems, and enclosure walls. The disadvantage of these PVC compositions printed by the Central Standards Bureau of the Ministry of Economic Affairs is that its weather resistance is poor, especially when it is darker in color such as brown and blue, and its color retention is insufficient. From a general background view, it can be seen that colored PVC compositions have been widely used in aesthetics, while pvc compositions are colored by using pigments such as pigments and / or dyes. —3 ~ A 4 (210X297mm) A 6 B 6
^999〇K 五、發明説明（2) 不過在曝露於陽光後會導致顔色的改變，這一變化則會破 壞美感。且較深的顔色較淺色C如白色及淸淡色）在顔色 •改變方面更爲嚴重。 爲克服或減輕此一非所欲的狀況，習知的方法是在 PVC組成物中加入可產生安定化的添加劑，譬如，紫外線 吸收劑、熱安定劑、二氧化鈦等。雖然此一方式可使問題 獲得改善，但改善的程度尙不足以符合工業界廣泛的要求 標準。 解決問題的另一途徑是將另一種樹脂材料塗壚在PVC 構造用塑膠上，以形成可承受陽光及其他環境條件造成之 種種不利影_的一個表面層。此種表面材料稱爲“塗浚坯 料” Ccapstock)。塗檀坯料的厚度通常遠低於構造用塑 膠，一般佔包含塗檀坯料與構造用塑膠層在內之複合材料 總厚度之大約10.至大約25. %之間。譬如，塗複坯料之厚度 爲大約〇·2至大約2· 5毫米，而構造用塑膠jg之厚度則爲 大約〇·75至大約10.毫米之間。 包含一層樹脂塗檀坯料及一層底層PVC槌造用塑膠在 內之複合材料，可依數種不同方式形成之。譬如，PVC構 造用塑膠及塗覆坯料之預先成型薄片或薄膜，可藉著熱熔 化或適當的黏着劑，予以疊積一起。或者，在適當的情況 下，可將PVC構造用塑膠與樹脂塗覆坯料予以共擠壓，分 隔給料共濟歷（feedblock coextrusion)往往是在製站.複 合材料薄片時所選用的方法。然後，再將複合材料溥片藉 熱成型製成諸如外壁板及百葉窗等物品。成者，可利用多 -4 - 甲 4 (210X297公~ '~~ …：...............-..........................裝...........................玎.......................緣 (請先閲讀背面之注意氺项再填寫本頁) 經濟部中央標準局印製 A 6 13 6 ^9990¾ 五、發明説明（3 ) 歧管塑模（mult imani fold die)以製成共擠壓製作輪廓 ，再經切割、銲接成窗戶、門等之框架。 包含塗覆坯料在內的樹脂材料必須具有多種良好性質 ，譬如，加工性質以及其他的物理、化學、及美觀性質， 方能成爲塗覆坯料之適當材料。爲使PVC構造用塑膠有效 地維持其適用性，它不但要具有特殊的耐候特性，包括梭 越的顔色保留性，而且也不可使PVC之所以被廣泛地作爲 建築材料所具有的一些性質受到不利的影響。 本發明提供之樹脂組成物，特別適於供P VC及其他種 類的構造用塑膠作爲塗覆坯料。 前案中已揭示可作爲塗覆坯料之許多種類之樹脂組成 物，這其中包括PVC系組成物（PVC - based compos i t ions ) 以及丙烧酸酯樹脂系組成物C acrylic resin-based composi t ion ) 〇 美國專利笫4，169，180號揭示之複合材料，其底M係 由樹脂--如PVC __所製成，它在室外曝露後會受到不 利的影響；而保趦表凼層則含有樹脂，它係由一系列的聚 合反應製成，且包含經過交聯的丙烯酸酯及/或甲基丙烯 酸酯部份C segment )、經過交聯的苯乙烯-丙烯腈部份 、以及未經交聯的苯乙烯-丙烯腈部份。 美國專利第4,183,777號揭示一種用於PVC構造用塑 膠之PVC系塗湲坯料。塗湲坯料中含有大遗的氙乙烯聚合 物以及少量的二氧化鈦及可塑劑，如酞酸酯可塑劑。 美國堪利第4，229，549號掲示一種耐候性及衝聰強度 甲 4 (210X297公釐） ......................................... .....裝...........................tr.......................%· (請先閲讀背而之注意事項再構寫本頁) 經濟部中央標苹局印製 A 6 B 6 19990¾ 五、發明説明（4 ) (請先閲讀背面之注意事項再塡寫本頁) 均極爲優越之樹脂組成物。組成物中含有701至97重量％之 硬質熱塑性樹脂C如PVC )以及3至30.重量％之彈性烷基 •丙烯酸酯共聚物；後者係由60.至99· 5重量％之烷基丙烯酸 酯，0· 1至10.重量％之帶有一個或更多個共軛雙鍵以及一 個或更多個非共軛雙鍵之多功能單體，以及，亦可使用高 達35.重量％之共單體所製成。例擧之後兩者單體分別爲辛 三稀C octat r ienes )及1,3 -丁二_。而樹脂組成物則 被推荐作爲多層模製品之外層。 _訂· 美國專利第4,511,695號亦掲示一種丙烯酸樹脂系接 枝共聚物，它可作爲塗覆坯料，且據稱它對老化及化學溶 劑均具有較佳的抗性。該專利提供之疊積物係由前述共聚 物之薄膜疊積於一層含有ABS - P VC混合物之材料上而製 成者。 由前述樹脂組成物所形成之塗覆坯料，就起始的顔色 保留而言，迎常具有較差的耐候性。與某些前案組成物# 關的另一缺點是修剪（tr imm i ng )等再加工以節省材料 及符合經濟。含有某些前案之塗擾坯料的一些樹脂組成物 ，它與構成複合材料之權造用塑膠層的樹脂組成物，刚者 並不具有良好的溶混性（miscibility)。這使得它很難 囘收再使用修剪等處理。 經濟部中央標準局印製 本發明提供之樹脂組成物可供PVC及其他構造用塑膠 作爲塗覆坯料，它具有各種所欲的性質，特別是耐候及耐 衝擊性質。 根據本發明，其提供之樹脂組成物包含： —6 — 曱 4 (210X297公釐） A 6 B 6^ 999〇K 5. Description of the invention (2) However, after exposure to sunlight, it will cause a change in color, and this change will destroy the beauty. And the darker color is lighter than the color C (such as white and light). The color changes more seriously. In order to overcome or alleviate this undesirable situation, a conventional method is to add stabilizers that can produce stabilizers, such as ultraviolet absorbers, heat stabilizers, titanium dioxide, etc., to the PVC composition. Although this method can improve the problem, the degree of improvement is not enough to meet the wide requirements of the industry. Another way to solve the problem is to apply another resin material to the plastic for PVC construction to form a surface layer that can withstand the adverse effects caused by sunlight and other environmental conditions. This kind of surface material is referred to as "catch stock" (Ccapstock). The thickness of the sandalwood-coated blank is usually much lower than that of the structural plastic, which generally accounts for about 10. to about 25.% of the total thickness of the composite material including the sandalwood-coated blank and the structural plastic layer. For example, the thickness of the coated blank is about 0.2 to about 2.5 mm, and the thickness of the plastic jg for construction is between about 0.75 to about 10. mm. A composite material containing a layer of resin-coated sandalwood blank and a layer of PVC mallet-making plastic can be formed in several different ways. For example, PVC construction plastics and preformed sheets or films coated with blanks can be stacked together by heat fusion or suitable adhesives. Or, under appropriate circumstances, PVC construction plastics and resin-coated blanks can be co-extruded. Separating the feedblock coextrusion is often the method of choice when laminating materials in manufacturing stations. Then, the composite material Pu sheet is thermoformed into articles such as outer wall panels and shutters. For the successful, you can use Duo-4-A 4 (210X297 ~~~~~ ...: ...............-.............. ............................................................ .............. Fate (please read the notes on the back before filling in this page) A 6 13 6 ^ 9990¾ printed by the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (3) Mult imani fold die is made into a co-extruded profile, and then cut and welded into a frame for windows, doors, etc. The resin material including the coated blank must have a variety of good properties, such as processing properties As well as other physical, chemical, and aesthetic properties, it can be an appropriate material for coating blanks. In order to effectively maintain the applicability of PVC structural plastics, it must not only have special weather resistance characteristics, including shuttle color retention In addition, some properties of PVC, which is widely used as a building material, can not be adversely affected. The resin composition provided by the present invention is particularly suitable for coating plastics for P VC and other types of construction plastics. In the previous case, many types of coating blanks have been disclosed Resin composition, which includes PVC-based composition (PVC-based compos it ions) and propionate resin-based composition C acrylic resin-based composi t ion) Compound disclosed in U.S. Patent No. 4,169,180 Material, the bottom M is made of resin-such as PVC __, it will be adversely affected after outdoor exposure; and the protective surface layer contains resin, it is made of a series of polymerization reactions, And it includes the cross-linked acrylate and / or methacrylate portion (C segment), the cross-linked styrene-acrylonitrile portion, and the uncross-linked styrene-acrylonitrile portion. U.S. Patent No. 4,183,777 discloses a PVC-based coating blank for plastics for PVC construction. The coating blank contains a large amount of xenon ethylene polymer and a small amount of titanium dioxide and plasticizers, such as phthalate plasticizers. Kanley No. 4,229,549 of the United States shows a weather resistance and Chongcong strength A 4 (210X297mm) ............................... ............................ pretend ........................ tr ................. %% (please read the precautions before constructing this page) A 6 printed by the Central Standardization Bureau of the Ministry of Economic Affairs B 6 19990¾ V. Description of the invention (4) (Please read the precautions on the back before writing this page) These are extremely superior resin compositions. The composition contains 701 to 97% by weight of a rigid thermoplastic resin C such as PVC) and 3 to 30.% by weight of an elastic alkyl • acrylate copolymer; the latter is from 60. to 99 · 5% by weight of an alkyl acrylate , 0.1 to 10.% by weight of multifunctional monomers with one or more conjugated double bonds and one or more non-conjugated double bonds, and up to 35% by weight of total Made of monomers. After exemplifying, the two monomers are octatriene (Coctat r ienes) and 1,3-butane-2. The resin composition is recommended as the outer layer of the multilayer molded product. _ 定 · US Patent No. 4,511,695 also shows an acrylic resin-based graft copolymer, which can be used as a coating blank, and it is said to have better resistance to aging and chemical solvents. The laminate provided by this patent is made by stacking the film of the aforementioned copolymer on a layer of material containing an ABS-P VC mixture. The coating blank formed from the foregoing resin composition usually has poor weather resistance in terms of initial color retention. Another disadvantage related to some previous case composition # is that trimming (tr imm i ng) and other reprocessing to save materials and meet the economy. Some resin compositions containing the coating blanks of some previous cases do not have good miscibility with the resin composition constituting the plastic layer of the composite material. This makes it difficult to recycle and use pruning and other processes. Printed by the Central Bureau of Standards of the Ministry of Economic Affairs. The resin composition provided by the present invention can be used as a coating material for PVC and other structural plastics. It has various desired properties, especially weather resistance and impact resistance. According to the present invention, the resin composition provided includes: — 6 — 曱 4 (210X297 mm) A 6 B 6
X9990S 五、發明説明（5) ⑴大約20.至大約50.重量％之聚（氣乙烯）樹脂（PVC) ⑵大約50.至大約75重量％之多數的多層且依序製成的 丙烯酸樹脂系高分子顆粒，它擁有由多數的高分子外殼（ shel 1)予以包覆的彈性體交聯核心（elastomeric crosslinked core )，其樹脂部份卽在此分離，樹脂的分 離部份能與該PVC相容或溶混者；（ί) (3-1)大約17.至大約38.重量％之熱塑性樹脂（除該 PVC以外者），它擁有耐候性質且能與該PVC相容或溶 混者；(ίί £}; (3-2)大約12至大約33.重量％之呈離散顆粒狀態之 丙烯酸酯系、硬質核心之衝擊改良劑樹脂；ΓΪ) (3 - 3 )大約12至大約33.重跫％之呈離散粒狀態的 丙嫌酸酯系，不可分離（non- dissociabl e )的、軟質核 心之衝擊改良劑樹脂； 其中，上述⑴及（3-1 )的樹脂（若使用時）以及以 上第⑵種樹脂的分離部份，會構成該組成物之連續相，分 散（若使用時）在其中的是以上第⑵種成份的殘留顆粒以 及以上第C 3 - 2 )及第（3 - 3 )種成份之樹脂顆粒。 在理想的型態中，本發明組成物之PVC成份係包含 氯乙稀之均聚物（homopolymer)，特別是Fi ken tscher K値介於大約62.至大約70.之間，更理想的情形是介於大約 6ά至大約69.之間的均聚物；且包含熱塑性樹脂C 3 - 1 )， 其分子量至少爲大約80，000 dal ton，它係爲甲基丙烯酸 -7 - 甲 4 (210X297公釐） ........................................- …袭...........................^...................... ¥ 〈請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局印製 A 6 B 6 19990¾ 五、發明説明（6) (請先閲讀背面之注意事項再填寫本頁) 甲酯樹脂，或爲甲基丙烯酸甲酯與Q〜C4烷基丙烯酸酯 之共聚物。在特別理想的型態中，成份（3-1)係爲一 種由大量的甲基丙烯酸甲酯與少量的低級烷基丙烯酸酯（ 最理想的是丙烯酸乙酯）經過聚合所製成之共聚物，而共 聚物之分子量係介於大約80,000至大約130,000 dalton 之間或更高，較理想的情形是介於大約90,000至大約 120,000 dal ton 之間者。 本說明書中，“分子量”一詞係指重量平均分子量。 分子量係使用傳統的凝膠滲透色層分析法估算之，而以聚 (甲基丙烯酸甲酯）標準作校正。而“ dalton ” 一詞係指 原子質量單位。 丁 在理想的型態中，丙烯酸樹脂系聚合物成份(2)係爲美 國專利第4，141，935號所掲示之樹脂，而丙烯酸系、硬質 核心之衝擊改良劑樹脂成份C 3 - 2 )則爲美國專利第 3,793,402號所揭示之多層樹脂顆粒。 本發明另一方面係提供由本發明之組成物所形成之塗 镋坯料及由此製成之其他物品C包括独片、褪膜），以及 由本發明之組成物覆於或整體結合於下層的構造用塑膠層 —特別是由PVC形成的一層一所形成之塑膠複合材料。 經濟部中央標準局印製 其次，本發明亦提供用以製造塑膠複合材料——它包 #由本發明之組成物所形成之表面材料，以及下層的塑膠 材料，特別是PVC——的方法。理想之用以製造塑膠複合 材料的方法，在欲製成薄片或薄片狀產品時，係使用分隔 給料共擠壓法。在製造具有複雜形狀之製作輪廓時，則以 _ Ο 一X9990S V. Description of the invention (5) ⑴ About 20. to about 50.% by weight of poly (gas ethylene) resin (PVC) ⑵ about 50. to about 75% by weight of the majority of multi-layer and sequentially made acrylic resin Polymer particles, which have an elastomer crosslinked core (elastomeric crosslinked core) covered by a majority of polymer shells (shel 1), the resin part of which is separated here, and the separated part of the resin can be combined with the PVC Content or miscible; (ί) (3-1) about 17. to about 38.% by weight of thermoplastic resin (other than the PVC), which has weather resistance and is compatible or miscible with the PVC; (ίί £); (3-2) about 12 to about 33.% by weight of acrylate-based, hard core impact modifier resin in the form of discrete particles; ΓΪ) (3-3) about 12 to about 33. A propionate system in the form of discrete particles, non-dissociabl e non-dissociabl e soft-core impact modifier resin; wherein, the resins of (1) and (3-1) above (if used) and The separated part of the above-mentioned second resin will constitute the continuous phase of the composition and be dispersed If used) in the residual particles which are more kinds of components as well ⑵ more of C 3 - 2) and the second (3 - 3) kinds of ingredient resin particles. In an ideal form, the PVC component of the composition of the present invention comprises a homopolymer of vinyl chloride (homopolymer), especially the Fi ken tscher K value is between about 62. to about 70., a more ideal situation It is a homopolymer between about 6 to about 69 .; and contains thermoplastic resin C 3-1), its molecular weight is at least about 80,000 dal ton, it is methacrylic acid-7-A 4 (210X297 Mm) ............................................................... ...................... ^ ......................... ¥ 〈please first Read the precautions on the back and fill in this page) A 6 B 6 19990¾ printed by the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) (Please read the precautions on the back before filling in this page) Methyl ester resin, or methyl Copolymer of methyl acrylate and Q ~ C4 alkyl acrylate. In a particularly desirable form, component (3-1) is a copolymer made by polymerizing a large amount of methyl methacrylate and a small amount of lower alkyl acrylate (the most ideal is ethyl acrylate) The molecular weight of the copolymer is between about 80,000 and about 130,000 dalton or higher, and ideally between about 90,000 and about 120,000 dalton. In this specification, the term "molecular weight" refers to the weight average molecular weight. The molecular weight is estimated using traditional gel permeation chromatography and corrected with poly (methyl methacrylate) standards. The term "dalton" refers to the unit of atomic mass. D. In the ideal form, the acrylic resin polymer component (2) is the resin shown in US Patent No. 4,141,935, and the acrylic, hard core impact modifier resin component C 3-2) It is the multilayer resin particles disclosed in US Patent No. 3,793,402. Another aspect of the present invention is to provide a ytterbium-coated blank formed by the composition of the present invention and other articles C made therefrom (including single-piece and exfoliated film), and a structure covered or integrally bonded to the lower layer by the composition of the present invention Plastic layer—especially a layer of plastic composite material formed by PVC. Printed by the Central Bureau of Standards of the Ministry of Economic Affairs. Secondly, the present invention also provides a method for manufacturing a plastic composite material which includes the surface material formed by the composition of the present invention and the underlying plastic material, especially PVC. The ideal method for manufacturing plastic composite materials is to use a separate feed co-extrusion method when making sheets or sheet-like products. When manufacturing contours with complex shapes, use _ Ο one
A 6 B 6 19990¾ 五、發明説明（7) 多歧管塑模共擠壓技術較爲理想。 由本發明之改良組成物製成之物品，具有優越的耐候 特性，包括顏色保留性。摻配淺色色料或深色色料之組成 物均可獲得優越的顔色保留性。本發明可獲得的其他優點 ，包括較隹的經濟性、較佳的耐燃特性，以及較佳的再加 工性。與再加工性較佳有關的是，當本發明之組成物與構 成複合材料之塑膠材料及/或與構成榴造用塑膠層之材料 ，在牽渉到這些材料之再硏磨及再擠壓等囘收技術中，予 以混合時，卽可顯示彼此之間具有良好的相容性（ compatabi1i ty )。 在參照以下詳細說明後，當可對本發明獲得進一步的 瞭解。 本發明組成物之主要成份係爲PVC，它榀成組成物之 連續相，在此往往稱之爲“基質樹脂” （ma t rix resiq ) 〇 在本發明之迎作中，PVC成份係爲廣泛貤川於製造M膠物 品之同一類型的氯乙烯之熱塑性均聚物或共聚物。本說明 書中，“聚（氯乙烯）樹脂”或“ PVC ” 一詞，係指經過 氯化的PVC或指氯乙烯之均聚物或共聚物，而以氣乙烯作 爲主成份（超過50.重量％)者。因此，PVC成份可爲聚（ 氯乙烯）之均聚物，或爲氯乙烯與一種或更多種其他單體 之共聚物，這些單體包括，譬如：醋酸乙烯等；亞乙烯基 鹵（vinylidene halides )如氣亞乙烯；羧酸之烷基酯， 如丙烯酸、丙烯酸乙酯、2 _乙基己基丙烯酸酯等；不飽 和烴，如乙烯、丙烯、異丁烯等；烯丙基化合物，如醋酸 -9 — 甲 4 (210X297公釐） ..............................................裝...........................#....................... 爆. (請先閲讀背面之注意-1E項再填寫本頁) 經濟部中央標準局印製 A6 B6 19990¾ 五、發明説明（8 ) {請先閱磧计面之注意事硕再填坷本頁) 烯丙酯等。在使用氯乙烯之共聚物時，較理想的是使铤乙 烯含量佔共聚物之至少大約80重量％。PVC成份可爲氯乙 烯及/或經過氯化之PVC的均聚物與一種或更多種共聚物 所組成之混合物，或爲氯乙烯及/或經過氯化之PVC的 兩種或更多種共聚物所組成之混合物。 PVC之分子量及分子量分佈可有很大的變化。在運用 擠壓製成之建築產品時，PVC的Fikentscher K値以介於 大約62至大約701之間爲宜，更理想的情形則是介於大約6ά 至大約69.之間。Fikentscher K値係由下式決定之 L〇gqrel/c= (75 X 1〇τ6ίί)/( 1 + 1.5ΧΚΓ3 KC) + 10_3K 式中，C代表聚合物在溶劑內之濃度，〇*5g/100ml ; 〔^Drel代表在環己酮內之相對黏度（25.1C);而K代表 Fikentscher 値 〇 在理想的型態中，PVC成份係爲氣乙烯之均聚物。 如以上所述，本發明包含：在一個實體中，組成物包 括作爲主成份的TVC〗，以及多層、依序製造之丙嫌發JiUE- ·--------------------^ 系聚合物的顆粒，它的彈性體交聯核心被多數的高分子外 殼所包覆，其外部可與(此處亦稱爲_“置泣麗.的 核心改良劑”，dissociable soft core modifier )相分離 1— I ___m 經濟部屮央標屮局Η-7-"'1'·合作杜印製 ;而在第二個及第三個實體中，組成物則包括作爲主成份 之由至少兩種基質樹脂--卽PVC以及具有耐候性質且能 與PVC相容或混溶之熱塑性樹脂--所組成之混合物，且 包括丙烯酸酯系、硬質核心之衝擊改良劑樹脂或丙烯酸酯 系、不可分離的軟質核心、衝擊改良劑樹脂（在此亦分別 —10.— 本紙張尺度適用中國S家標準（CNS)f彳規格（210X297公釐} A6 B6 19990¾ 五、發明說明（9 ) 稱爲“硬質核心改良劑”，hard core modifier，以及“ {請先聞讀背面之注意事硕再填"本頁) 不可分雜0^勢.'質核心改良劑，non-dissociable soft core mod i f i eV八公/前者組成物在此稱爲“ f YC /旦分 質核心組成物” C PVC/dissoc.iable sof t core conposition ) _____ ,-. ^ f ，而後者組成物在此則可分別P.VC / ^屬核丄α姐^ 物” （PVC/hard core compos i t i o对變 P VC /不可汾 離的軟質核心組成物” （PVC/non-dissociable soft core compo sition)。這些組成物在以下將作詳細說明。 PVC /可分離的軟質核心組成物 由上述可知，此實體之組成物包含可分離的軟質核心改 良劑及PVC，而P VC成份係爲前述種類之樹脂。 可分離的、軟質核心改良劑，它的本質是可使PVC系 組成物具有改良的耐候特性，以及改良的衝擊強度。例擧 之能使PVC系組成物具有此綜合性質之可分離的、軟質核 心改良劑係爲一種共聚物顆粒，其彈性體交聯核心係被多 數的高分子外殼所包镫，而這些外殼中有一部份具有能自 顆粒中予以分離之能力者。由以下更詳細的說明可知，這 些顆粒中有一部份可在熔融加工條件下產生分離，而外面 的外殼部份與裏面部份相分離，且仍呈離散顆粒。本發明 經濟部屮处桴中总巧工消竹合作杜印·" 中使用之較理想的這類樹脂已掲示於前述美國專利第(4，141，9i| 11 1 ~一-............. 號，其掲示內容在此列入參考。 在美幽¥利笫ί.4,141，935;號中所揭示之樹脂，係爲一 種丙烯酸酯樹脂系共聚物顆粒，其彈性體交聯核〇被三層 硬度遞增的熱塑性共聚物外殻所包涩者。Μ類樹脂係爲多 — 11· 本纸張尺度適用中Η困家標準（CNS) f 4規格（210x297公釐） A6 B6 19990¾ 五、發明说明（l〇.) 級、依序製成之聚合物 C mu 1 t iple stage，sequent ia 1 ly produced polymers)，此卽，聚合物係在水性分散液或 乳化液內製成，聚合反應係在預成型膠乳（preformed latex )存在下進行，此一膠乳係由先前的單體進料製成 ，且往後每一級聚合物均附着於或緊密地結合玲前一級聚_ 合物之上者。樹脂中包含： (A)第一彈性體型態之較軟的第一級聚合物，它係由含 下述成份之水性乳化單體系統製成：⑴大約75至大約99· 8 重量％，較理想的情形是介於大約94至大約99· 8重量％之 至少一種C2〜C8烷基丙烯酸酯；⑵大約0· 1至大約5重 量％，較理想的情形是大約〇· 25至大約1· 5重量％之至少 —種交聯的聚烯類不飽和單體；⑶大約〇·1至大約1重量 %之至少一種接枝連結（graf tl inking )的聚稀屬不飽和 單體；以及⑷其餘部份卽使第一級單體系統總量達到100重 量％的部份係爲一種或更多種可共聚合之單烯屬不飽和單 體，而單體系統之選擇係使最高的玻璃化溫度不超過-2α X：者； ⑻第二級聚合物，它係於第一級聚合所形成之水性系 統存在下，由下述成份之水性乳化單體系統聚合而成：⑸ 大約10.至大約90重量％之至少一種c2〜C8烷基丙烯酸酯 ;⑹大約9至大約89.9重董％之至少一種G〜C4烷基甲 基丙烯酸酯；以及⑺大約0 · 1至大約1重适％之至少一 _ 接枝連結之聚烯屬不飽和單體； (0第三級聚合物，它係於第二級聚合物所形成之水性 —12 — 本纸張尺度適用中0囷家標準（CNS)f4規格（210x297公釐） L . 一——____________ * .......................................................装..............................訂·…V.:· .................線·. ·. (請先閱請卄面之注意事邛再填辉本页) A6 B6 19990¾ 五、發明說明（U·) 系統存在下，由下述成份之水性乳化單體系統聚合而成： ⑻大約5至大約40l重量％之至少一種<：2〜（：8烷基丙烯酸 酯；以及⑼大約601至大約95.重量％之至少一種Q〜C4烷 基甲基丙烯酸酯；以及 (D)最終的一種玻璃化溫度至少爲6Q*C之第四級聚合物 ，它係於第三級聚合所形成之水性系統存在下，由下速成 份之水性乳化單體系統聚合而成：⑽大約80至大約伽重量 %之至少一種C:〜C4烷基甲基丙烯酸酯；以及(11)其餘部 份，卽使第四級單體系統總量達到1〇〇重量％之部份，係爲 至少一種（^〜C8烷基丙烯酸酯。 本說明書中，“交砩的聚烯屬不飽和單體” （crosslinking polyethyleni cal ly unsaturated monomer )或“交聯單體”（ cross 1 inking monomer ) — _ 係指一M 共衆合的取 ， 其中含有至少兩個可產生加成聚合之不飽和功能基，每一 個不飽和功能基均能以大致相同的速率進行聚合者。交聯 單體包括：多元醇之丙烯酸酯或甲基丙烯酸酯，譬如，二 丙烯酸丁二醇酯（butylene diacrylate )、二甲基丙烯酸 丁二醇酯、三經甲基丙院三甲基丙瑞酸酷（trimethylolpropane trimethacrylate )等；二-及三乙烯基苯等；乙烯基酯類 ，如丙稀酸乙稀（vinyl acrylate );以及其他交聯單體 。院撞二丙稀酸酷C alky lene diacrylate )用於與第一級 的烷基丙烯酸酯進行交聯較爲理想。 本說明書中，“接枝連結的聚烯屬不飽和單體“（ graf 11 inking polyethy1enica11y unsaturated monomer ) —13.— 本纸》尺度適用中國國家櫺準（CMS) f 4規格（210x297公釐） (請先聞讀背面之注意事項再填·"本頁) 裝· * Λϊτ· 經濟部屮央標个局约工消';'合作杜印製 A6 B6 199902 五、發明說明（12·) i 或“接枝連結單體” （graft 1 inking monomer ) —詞係指 —種可共聚合的單體，其中含有至少兩個可加成聚合之不 飽和功能基，而每一個功能基均以彼此有相當差異的速率 進行聚合者。例擧之在本發明中適用的接枝連結單體包括： 卢-不飽和單羧酸及二羧酸之烯丙基、甲基烯丙基（ methallyl)、及巴豆基酯，譬如，甲基丙烯酸烯丙酯及 丙烯酸烯丙酯；以及馬來酸二烯丙酯、富馬酸二烯丙酯、 及衣康酸二烯丙酯。其中以甲基丙烯酸烯丙酯及丙烯酸烯 丙酯較爲理想。 例擧之可在以上(A)⑷所示之第一級單體系統中使用之 可共聚合的、單烯Μ不飽和單體，係爲氣亞乙烯（ vinyl idene chloride )、氯乙稀、丙稀腈、乙烧基醋， 以及鄰-、間-、對-甲基苯乙烯及-烷基苯乙烯等。 第一級聚合物可佔所形成之四級聚合物總重垃之大約 10.至大約75 %，其餘部份則平均或不平均地分佈於其他各 級，但前提是其他單一級的存在量，不得在剩餘各級的總 重量中低於2α%或超過75%。 多級聚合物的熔融指數値，一般介於大約0·01至大 約20.之間，但以大約3至大約8之間的數値較爲理想。聚 合物之最低薄膜形成溫度（minimum film-forming temperatun ，MFT)宜介於大約6〇L至大約lDQlC之間。且第一級聚合物 的平均粒徑宜介於大約500至大約4000 °Α Γ|ϊ位之冏。 在用於製造可分離的軟質核心改良劑的第一級與笫四 級反應中，有若干與其有關的理想實體。笫一級反應宜使 —14.— 本纸張尺度通用中Η®家《準（CNS) Ή規格（210x297公釐） (請先閱讀卄面之注龙事硕再填艿本页) •装· •訂· 經濟部十央桴中局工消贽合作杜印¾ A6 B6 19990¾ 五、發明説明（13.) 用大約94至大約99· 8重量％之丙烯酸丁酯、大約0·25至 大約1·5重量％之交聯單體、以及大約0·1至大約1道Μ %之接枝連結單體。第四級反應則宜使用甲基丙烯酸甲酯。 本案發明人相信，最廣泛使用之組成物乃爲含有大約 20.至大約50.重量％之PVC、以及大約50.至大約75重量％之 可分離的軟質核心改良劑者，而較理想的用量則爲含有大 約3&至大約48.重量％之PVC、以及大約50.至大約6Q重垃％ 之改良劑者。 可以解釋（未經確認）的是在本發明之PVC /可分離 的軟質核心組成物進行熱處理期間，下述情形相信會發生 ，至少一部份會促使本發明此一實體之使用能獲得優越的 效果。當PVC /可分離的軟質核心組成物藉熔融擠Μ予以 配料時，外面邰份的四級丙烯酸酯高分子顆粒，基於長久 以來對聚（烷基甲基丙烯酸酯）與PVC具有溶混性的瞭解 ，相信它會與PVC形成一個均質的合金基質相（alloy matrix phase )，分散在其間的是呈離散顆粒態之由外面 部份分解後所流出的裏ώ部份（包括核心）之顆粒。此一 不包含任何交聯樹脂之合金基質相，含有在熔融加工期間 所生成之“可流動” （flowable )邰份之組成物。第四級 的軟質核心，可分離的樹脂顆粒，它大致未接枝於笫三級 ，在熔融加工條件下，會全部存在而與裏面邰份的顆粒相 分離，且會形成PVC /丙烯酸酯合金基質相。而且，一 部份（譬如，大約一半）的第三級，因僅部份接枝於第二 級，故會自該級中分離出來，而被納入合金基質相。耐候 —15.— 本纸張尺度適用中囲a家標準（CNS)«F4規格（210x297公釐） (請先閱讀背面之注意事項再填穷本页) •裝· .ίτ· •線· A6 B6 19990¾ 五、發明說明（14.) {請先閑讀计面之注意事項再填寫本頁) 性較高的丙烯酸酯聚合物鏈，它的存在會分離及稀釋耐候 性較低的基質內之PVC部份，相信這會使PVC的光化學 分解現象顯著地獲得穩定，而使組成物顯現的耐候性能十 分優越。 由此，可將可分離的軟質核心改良劑視爲，它包含多 層的、依序製成之丙烯酸酯樹脂系聚合物，其中之彈性體 交聯核心被多數的高分子外殼予以包镋，這其間包含外ώ 的外殼邰份，此一聚合物的外殼部份中有相當的比例，亦 卽在聚合物之總重量中至少佔大約20_重量％以上，係具有 一種在熔融加工條件下會自其中分散並與PVC形成均質的 合金基質相之能力。較理想的情形是，至少有大約30.重量 %之聚合物的外殼部份能依前述方式進行分離。一般而言 *這種分離並不超過聚合物總重Μ之大約50. .打· 娉浒部屮央標肀局ϊ：:工消*(?合作杜印¾ •線· 在理想的型態下，軟質核心改良劑之可分離部份係能 與組成物之驻質相的PVC成份相溶Μ。“溶浞” （miscible) —詞，在此係指樹脂一譬如，改良劑之可分離部份—— 具有與PVC共同形成分子混合物（molecular mixture ) 之能力，而此種分子混合物係爲在顯微鏡下呈均質狀態者 ，臀如，一種均匀摻合物，特徵是並無含大量個別樹脂成 份之這種顯微鏡區域或領域（domain )存在者。樹脂之 這種均匀摻合物，特徵是其玻璃化溫度係介於樹脂個別成 份之玻璃化溫度的中間者。因此，樹脂個別成份之玻璃化 溫度無法以差示掃瞄、量熱學或動態機械分析等傳統的技 術予以測得。前述美國專利第4,141,935號掲示之可分離 —16.— 本纸張尺度適用中國a家標準(CNS)甲4規格(210x297公嫠） A6 B6 19990¾ 五、發明说明（15.) 部份的高分子顆粒卽能與PVC相溶混。 (請先閱讀卄面之注意事項再填坏本頁) 本發明的範圍亦包括在可分離部份能與組成物基質相 之PVC成份相容之一種可分離的軟質核心改良劑。在本說 明書中，“相容” （__ compat i bl e ) —詞係指樹脂-譬如 ，改良劑之可分離邰份——具有與PVC共同形成緊密混合 物之能力，在此，PVC與可分離部份於混合物內彼此牢牢 黏附一起，但不槭於均質狀態，卽其中有戚微銳區域成領 域且含有大量的樹脂個別成份。這種混合物可加予確認， 因混合物中樹脂個別成份之玻璃化溫度，可藉差示掃瞄、 量熱學或動態機械分析等傳統技術予以測定之。 PVC /硬質核心及不可分離的軟質核心組成物 本發明之這些實體的組成物，主要係含基質樹脂（爲 PVC與一些具有耐候性質而能與PVC相溶混或與PVC相 容之熱塑性樹脂形成之混合物），且含少M：之丙烯酸酯系 、硬質核心、衝擊改良劑樹脂，或丙烯酸酯系•不可分離 的軟質核心、衝擊改良劑樹脂，或彼等之混合物。而 PVC成份係爲前述種類之樹脂。 與PVC共同構成本發明組成物之基質部份時所使用之 熱塑性樹脂，可選自任一種業界公認之具有良好耐候特性 的熱塑性樹脂，此卽，樹脂本身在置於室外條件下仍能保 留其化學及/或物理性質，這些室外條件通常包含曝露於 :太陽射線；達到80 - 90 °F或更高之溫度；冷凍以下之 溫度；溫度的起伏較大；以及雨水、雪、雹等。例擧之被 認爲耐候性特別良好之熱塑性樹脂，包括：α-屮基苯乙 -17.- 本紙張尺度適用中國8家標準(CNS) F4規格（210x297公釐) 19990¾ Λ 6 13 6 經濟部中央櫺準局貝工消費合作社印製 五、發明説明（16.) 烯/甲基丙烯酸酯樹脂，甲基丙烯酸酯/丙烯酸酯樹脂， 甲基丙烯酸酯樹脂，及聚C氟乙烯）樹脂。例擧之被認爲 耐候性質良好——卽耐候性質優於PVC但遜於前述樹脂一 一之樹脂，包括：苯乙烯/甲基丙烯酸酯樹脂，及苯乙烯 /丙烯腈樹脂。 除具有良好的耐候性質外，熱塑性樹脂亦能與組成物 基質相之PVC成份相容。較理想的情形是，熱塑性樹脂能 與組成物基質相之PVC成份相溶混。“溶混”（miscible) 及“相容” C compatible )之意義與先前對軟質核心改良 劑之可分離部份所作的討論相同。甲基丙烯酸酯樹脂以及 甲基丙烯酸酯/丙烯酸酯樹脂係爲例擧之能與pvc相溶混 且擁有優越的耐候性質之樹脂。苯乙烯/甲基丙烯酸酯樹 脂（包括α -甲基苯乙烯）以及苯乙烯/丙烯腈樹脂則爲 例舉之能與PVC相容之樹脂，而前審較後:¾爲優，因;U: Α· 有較佳的綜合性質。 在本發明之運作中，特別理想之熱塑性樹脂包含：由 主成份爲甲基丙烯酸甲酯及少量之烷基（)丙烯酸 酯——較理想的是丙烯酸甲酯或丙烯酸乙酯，而以丙烯酸 乙酯最爲理想——經過聚合所製成之經聚合的甲基丙烯酸 甲酯或共聚物。共聚物中可含有大約85.至大約99.9重; 之甲基丙烯酸甲酯，以及大約〇.1至大約15.重量％之烷基 丙烯酸酯。較理想的情形是，共聚物中之烷基丙烯酸酯成 份介於大約5至大約15.重量％之間，而以大約8至大約13. 重量％之間最爲理想，共聚物之其他成份則爲甲基丙烯酸 —18.— 本紙張尺度逍用中困國家標準（CNS)甲4規格(210x297公發） (請先閲讀背面之注意卞項再堝寫本頁) 裝. 訂 線· 經濟部中央梂準局貝工消費合作社印製 X9990S Λ 6 _;_Β6_ 五、發明説明（17.) 甲酯。 提高共聚物中之烷基丙烯酸酯成份，會增加熔融流動 指數（melt flow index )及降低共聚物之熔融黏度，若 它爲樹脂組成物之部份時亦然。使烷基丙烯酸酯成份減至 最低，亦會增加硬度、耐刮性（scratch resistance )、 以及覆蓋坯料受到化學品侵蝕的耐性。 理想之丙烯酸酯基質樹脂，其分子量宜至少爲大約 80，000 da It on。其範圍可達到130,000 da It on甚至更高 。較理想的情形是使分子量介於大約90,000至大約120,000 之間，而以介於大約90,000至大約105,000 dal ton之間最 爲理想。提高共聚物之分子量，其餘均保持相同時，會降 低熔融流動指數及提高共聚物之熔融黏度，若它爲樹脂組 成物之部份成份時亦然。提高分子量亦可改良組成物之耐 化學性及抗張性質。 通常，前述丙烯酸酯共聚物係爲一種不規則共聚物（ random copolymer )，它宜由兩槌單體之混合物，在迪 續流動的攪拌槽反應器內，與有機過氧化物進行自由基催 化的整體聚合反應製成，轉化率約爲50. %。將聚合物-單 體混合物泵至去揮發之雙螺桿擠壓機，在此將殘留單體去 除，且可加入其他添加劑。進行此項聚合的技術，可由文 獻査知，且爲熟知此項技術之人士所瞭解者。不規則共聚 物亦可由整體鑄模（bulk casting )或者利用懸浮或乳 化聚合製成，而以後者最爲理想。乳化製成之共聚物可藉 -19. - · (請先閲讀背面之注意事項再埙寫本頁) 裝- 訂- 線· 本紙ίί：尺度逍用中S B家樣準（CNS)甲4規格（210x297公¢) 經濟部中央櫺毕局员工消費合作社印製 χ999^ Λ 6 _Β6_ 五、發明説明（18.) 噴霧乾燥或凝結、淸洗、及乾燥予以分離，或藉凝結分離 後，再經淸洗及濟壓去揮發（extrusion devolatilization )將它製成顆粒（pellet )。 本案發明人相信，組成物中所使用之具有耐候性質之 熱塑性基質樹脂，可改進它對光化學分解、氧化、及以他 機構——會導致傳統的室外級PVC配方產生的全部分解者 -之耐性。 除了具有耐候性質之熱塑性樹脂外，PVC系組成物中 亦含有硬質核心或不可分離的軟質核心衝擊改良劑。這些 改良劑係爲含丙烯酸酯之多級樹脂或聚合物的顆粒，而此 多層樹脂之中央或最內部份（稱爲“核心”，core )係被 —層或多層樹脂層或外殼（shell )連續予以包覆。如衆 所週知者，這些多層樹脂一般係由依序進行的多級聚合（ multi-stage polymerization )所製成 0 —般所熟知的是，在PVC中加入本發明提供的這類硬 質核心或不可分離的軟質核心多級依序製成之丙烯酸酯樹 脂系聚合物，可提高彼等之耐衝擊性。通常，這些組成物 含有PVC連續相，而前述種類樹脂之離散顆粒則分散於其 間。一般而言，含硬質核心改良劑之PVC組成物，較含有 不可分離的軟質核心改良劑之PVC組成物具有更佳的耐候 特性，而含有不可分離的軟質核心組成物之PVC組成物則 較含有硬質核心改良劑之PVC組成物具有更佳的耐衝擊性 。硬質核心及不可分離的軟質核心改良劑，兩者均有幾層 外殼或外層，彼此各自獨立，且隨着用途及最終所欲的性 —20. 一 本紙ft尺度边用中8國家標準(CNS) f 4規格(210X297公址） (請先閲讀背面之注意市項再蜞寫本頁) 裝· -?τ- 線- 經濟部中央榣準局貝工消f合作社印製 199302 Λ6 ___BJB 五、發明説明（19.) 質而定，在交聯及/或接枝連結層、或在聚合物或共聚物 組成物等彼此之間可具有不同程度的硬度或柔軟度（由 Tg測之）。 在構造方面，一般而言，硬質核心改良劑通常有一個 由非彈性®聚合物或共聚物構成之核心，這些聚合物成共 聚物係經過交聯及/或接枝連結，且其玻璃化溫度一般均 高於室溫（25. °C )，往往會超過40.° C。例擧之在製備硬質 核心聚合物時大量使用之單體，包括：苯乙燃，烧基苯乙 烯，以及匕-。烷基甲基丙烯酸酯。而其他單體一般均少 量使用。 —般而言，不可分離的軟質核心改良劑通常亦有一個 由聚合物或共聚物構成之核心，而此聚合物或共聚物係經 過交聯及/或接枝連結而使核心具有橡膠般或彈性體性質 者，且其玻璃化溫度通常均爲或低於室溫，迈常兒的惝形 是低於o°c。例擧之在製備不可分離的軟質核心改良劑時 常用於作爲主要成份之單體，包括：丁二烯及其他二炕類 ;乙烯-丙烯-二烯組合物，丁二烯-苯乙烯，以及Cl—C8院 基丙烯酸酯。其他的單體則少量使用。一般而言，不可分 離的軟質核心改良劑有異於可分離的軟質核心改良劑，因 其各層係依化學方式彼此相連結，或由於各層聚合物之交 聯而纏結或鎖定於界面處，並形成中間滲透（interpenetrating ) 的聚合 物網路 （ pol ymer network ) 。 硬質核心及不可分離的軟質核心改良劑，主要功用在 於增強組成物之物理性質，譬如，韌性及耐衝擊性。改良 -21.- (請先閲讀背面之注意事項再填寫本頁) 裝. 線. 本紙張尺度边用中困國家楳準(CNS)甲4規格(210x297公¢) 19990¾ Λ 6 Β6 經濟部中央標準局A工消費合作社印製 五、發明説明（2Q) 劑之使用亦可改進尉氣候變造成之應力變白（stress whitening )及褪色的耐性◊這些樹脂之製造、接合及使 用均爲一般所熟知者。 本發明之理想的PVC /可耐候的熱塑性樹脂/衝擊改 良劑組成物，其中係包含硬質核心衝擊改良劑。這些組成 物較一些由不可分離的軟質核心改良劑製成之類似組成物 ，通常具有較佳的綜合性質。 以下就PVC /硬質核心組成物及PVC /不可分離的軟 質核心組成物加予說明，它包括理想之硬質核心及不可分 離的軟質核心改良劑之說明。 PVC /硬質核心組成物 本發明運作中所使用之理想類別的硬質核心改良劑， 係爲以上美國專利第3,793 ,402號所揭示者，其揭示內容 在此列入參考。如同此一專利所述者，改良劑樹脂包含多 級高分子顆粒。這種樹脂，與前述可分離的軟質核心丙烯 酸酯樹脂相似，亦由多級依序聚合反應製成。 更明確地說，這些多級高分子顆粒，至少包含三級依 序爲非彈性體之第一級聚合物、彈性體之第二級聚合物、 以及較硬之第三級聚合物，製造每一級樹脂所使用之單體 (共單體）均依以上美國專利第3,793,402號所述予以選 擇，使不同的各級或各層皆具有前述之非彈性、彈性及堅 硬性質。在第一級聚合反應中形成之非彈性體聚合物，玻 璃化溫度超過大約25. °C，它係連結於下一級由玻璃化溫度 爲大約25. °C或更低，較理想的情形是低於大約10. °C之單體 —22.— (請先閲讀背面之注意事項再项寫本頁) 裝· 訂- 線· 本紙張尺度逍用中國國家標準(CNS)甲4規格(210X297公;li·) Λ 6 Β6 經濟部中央榡準局貝工消費合作社印製 五、發明説明（21.) 成份所製成之彈性體聚合物上。而此彈性體聚合物本身則 X連結於下一級由單體所製成之聚合物上，使聚合物之玻 璃化溫度較理想的情形是超過大約25. °C，最理想的情形則 至少爲大約60l°C。 理想的顆粒是其中的核心層以及外層係藉甲蕋丙烯酸 烯丙酯接枝連結單體予以連結，且核心層及外層均包含與 用於製造組成物之理想的丙烯酸酯基質樹脂相同的一種或 多種單體所製成之樹脂，此卽，甲基丙烯酸甲酯之均聚物 或甲基丙烯酸甲酯與Ci - c4烷基丙烯酸酯（最理想的是丙 烯酸乙酯）之不規則共聚物，或者在其中亦可含有多功能 性的交聯單體。當基質樹脂中含有甲基丙烯酸甲酯與丙烯 酸乙酯之共聚物時，相當理想的惝形是侦颗粒之银一個核 心層及外層均含有大約96.重量％之甲基丙烯酸甲酯及大約 4重量％之丙烯酸乙酯，而接枝連結單體則佔大約1 IE记 %。根據前述美國專利第3,793,402號揭露，有許多種單 體均可用以製造中間層之顆粒。例擧之中間屑係含有丙烯 酸丁酯、苯乙烯以及大約2重：i; %之交聯及接枝迎結單腮 的一種不規則共聚物。 由依序分級聚合製成之產品係含有膠乳（1 atex )， 此卽有多層高分子顆粒分散於其間之一種水性組成物。鍩 户W·高由噴霧乾燥或藉凝結及乾燥，而自膠乳中囘收這些顆粒。 嗯霧乾燥宜在乾燥助劑存在下進行，此乾燥助劑谈爲W如 ，一種丙烯酸酯系樹脂，它可與此處所述之基質樹脂相同 或互異。當然，“乾燥助劑” （drying-aid )樹脂應能與 樹脂組成物之其他成份相容，且不會對組成物或其製成 -23.- (請先閱讀背面之注意事項再填寫本頁) 訂_ 本紙張尺度边用中國β家標準（CNS)甲4規格(210X297公龙) 經濟部中央楳準局貝工消費合作社印製 19930¾ Λ 6 _Β_6_ 五、發明説明（22) 物品之化學、物理或美觀性質造成不良的影響。理想的“ 乾燥助劑”樹脂係爲甲基丙烯酸甲酯與烷基C Q-C4 )丙 烯酸酯之不規則共聚物，其中含有大約9α至大約99.9重 量％之甲基丙烯酸甲酯，以及大約〇. 1至大約10.重量％之 丙燃酸醋，較理想的是丙嫌酸乙酷。共聚物之分子量可有 大幅度的變化，譬如，介於大約95,000至大約200,000 da 1 ton之間。分子量以介於大約95,000至大約110,000 dal ton之間較爲理想。此樹脂由可保留一些顆粒，作爲 丙烯酸酯基質樹脂之一部份。 誠然，在組成物中亦可含有其他的熱塑性丙烯酸酯系 樹脂，以獲得所欲之效應或作爲加工助劑C Processing aids )，譬如，分子量至少爲大約1，〇〇〇β〇〇之高分子“ 的甲基丙烯酸甲酯-.丙烯酸乙酯共聚物。 其他類別的丙烯酸酯系硬質核心、添加衝掣改良劑之 樹脂亦可用於本發明之組成物內，它可用於取代前述美國 專利第3,793,402號所揭示之理想樹脂，或用於與其形成 混合物。這些用以使組成物製成之物品提高耐衝擊性之樹 脂，係爲多層的高分子顆粒，它由多級依序聚合製成，-¾ 中之硬質（非彈性體）核心宜包含大量的甲基丙烯酸甲酯 之均聚物或甲基丙烯酸甲酯與烷莲丙烷酸酯之共聚物。例 擧之這些硬質核心、添加衝·改良劑之樹脂係爲揭示於美 國專利第4,052,525號及第4,4 33,103號、日本專利公告 (kokai )第58-180514號、以及歐洲專利申誚案第 270,865 號者。 一 24. 一 本紙張尺度边用中《國家楳準(CNS)甲4規格(210X297公釐) (請先閲讀背面之注意事項再项寫本頁) 裝- ^9990¾ Λ 6 Β6 經濟部中央標準局β工消費合作社印製 五、發明説明（23.) 本案發明人相信，使用範圍最廣之組成物，其中係包 含大約20·至大約50.重量％之PVC、大約17.至大約38.重量％ 之耐候性樹脂、以及大約12至大約Π重量％之硬質核心丙 烯酸酯系樹脂；較理想的情形則是含有大約40.至大約50.重 量％之PVC、大約25.至大約35.重量％之耐候性樹脂、以及 大約15.至大約25.重量％之硬質核心丙烯酸酯系樹脂。 不可分離之軟質核心組成物 本發明中所使用之理想種類的不可分離之軟質核心改 良劑係爲揭示於美國專利第3，808,180號者，其揭示內容 在此列入參考。如該專利所揭示者，改良劑係爲多層高分 子顆粒。這些樹脂，如同前述之硬質核心樹脂，亦由多級 依序聚合製成。 更明確地說，這些多層高分子顆粒包含至少兩層，其 彈性體核心係以化學方式連結於堅硬的熱塑性樹脂層。這 些多層顆粒可由乳化聚合製成，以彈性體爲離散相，其核 心係爲一種單體混合物，它包含至少大約50.重量％之烷基 -及/或芳烷基丙烯酸酯，大約至大約5重量％之聚 -不飽和交聯單體，大約0.05至大約5重量％之接枝連結 共單體，以及大約〇至大約10.重量％之親水性單體。較理 想的情形是，彈性體相的單體混合物中含有大約〇 · 1至大 約1重量％之交聯共單體，大約0.1至大約1重量％之接 枝連結共單體，大約0.5至大約5重量％之親水性共單體 ，以及至少大約50.重蛩％之烷基及/或芳烷基丙烯酸酯。 —旦彈性體相完成聚合後，卽在起始聚合混合物內之 -25.- 本紙張尺度边用中Β «家楳準(CNS)甲4規格(210x297公龙） (請先閲讀背面之注意事項再堪寫本頁) 裝· 訂· 線< 19990^ Λ6 B 6 經濟部中央榣準局貝工消費合作社印製 五、發明説明（24.) 單體大致消耗完畢後，再於含有至少大約50.重量％之<^-C4烷基甲基丙烯酸酯之單體混合物的同一種乳化液內， 利用聚合以形成堅硬的熱塑性樹脂。形成複合材料之堅硬 熱塑性樹脂相等，其聚合使用之單體係依照使幾乎所有的 堅硬相材料均形成於彈性體相表面的方式予以加入，且使 最低黏附水準C minimum attaclment level )，如以下所 述，達到大約20. %。 在製造彈性體核心時，可使用丙烯酸之烷基酯，其中 之烷基係指含有1至大約15.個碳原子者，較理想的是含有 1至大約8個碳原子，而以含有2至8個碳原子者爲最佳 。烷基鏈較長者亦可使用。其他的丙烯酸酯單體亦可使用 ，其用量可達到大約50.重量％，但較其他包含物爲低，譬 如，使用丙烯酸之芳烷基酯，其中之環狀部份含有5、6 或7個碳原子，它可帶有或不帶有其他的烷基橋架（alkyl bridge )，丙芳烷基之烷基部份則可含有高達大約15.個碳 原子。此外，亦可使用經取代之丙烯酸酯或甲基丙烯酸酯 ，包括：烷基硫烷基丙烯酸酯，如乙基硫乙基丙烯酸酯（ ethylthioethyl acylate )等；烷氧基烷基丙烯酸酯，如 甲氧基乙基丙烯酸酯等。與這些丙烯酸酯形成之共聚物， 其中亦可含有高達大約40.重量％之一種或更多種其他可產 生加成聚合之單體，如苯乙烯，甲基苯乙烯，乙烯基醚、 醯胺、及酯，乙烯基鹵及亞乙烯基鹵等。 在一個更理想的配方中，彈性體核心係由下述成份製 成：大約50.至大約80.重量％之烷基丙烯酸酯，其中之烷基 -26.- 本紙張尺度边用中國β家標準（CNS)甲4規格（210X297公龙) (請先閲讀背面之注意事項再填寫本頁) 裝- 訂_ 經濟部中央櫺準局S工消费合作社印製 χ999υ j_____Β6___ 五、發明説明（25·) 係含有2至4個碳原子，而以含有4個碳原子較爲理想； 大約0.1至大約10.重量％之其他丙烯酸酯單體；大約0·1 至大約1重量％之交聯單體；大約0.1至大約1重量％之 接枝連結單體；大約〇至5重量％，較理想的情形是〇·5 至5重量％之親水性單體；而其他部份爲其他非丙烯酸酯 類不飽和單體，而以苯乙烯、甲基苯乙烯及鹵化苯乙烯較 爲理想。 較理想的是玻璃化溫度低於25. °C之一些彈性體。更理 想的爲玻璃化溫度低於10. °C之彈性體，而以玻璃化溫度低 於一 25.。<：之一些彈性體最爲理想。在所有的情形下，這些 玻璃化溫度係指改良劑之彈性體部份而已，並不包含以物 理或化學方式附着在彈性體顆粒上之任何後來形成的相或 其他聚合物。 特別理想的彈性體核心係爲由：大約50.至大約80.份爪 量之烷基丙烯酸酯單體，其中之烷基爲含有1至8個碳原 子者；大約〇至大約40.份重量之其他烯屬不飽和單體；大 約0.05至大約5份重量之至少一種聚不飽和交聯單體；大 約0.05至大約5份重量之接枝連結單體；以及大約〇至大 約10.份重量之至少一種親水性單體所製成之共聚物。理想 的這類丙烯酸酯彈性體係爲聚合物中含有大約50.至大約100L 份重量之烷基丙烯酸酯單體1其中之烷基含有1至8個碳 原子），大約1至大約2(λ份重ϋ之其他丙烯酸酯單體，大 約5至大約20.份重量之其他烯騰不飽和單體（這些其他的 烯屬不飽和單元係爲芳烴者，如苯乙烯及經取代之苯乙烯 —27.— (請先閲讀背面之注意事項再璜寫本頁) -裝· 本紙張尺度边用中國Η家標準（CNS)甲4規格（210X297公龙） Λ 6 Β6 經濟部中央標準局員工消費合作社印製 五、發明説明（26·) )，大約〇·1至大約1份重量之至少一種聚烯屬不飽和交 聯單體單元，大約0.1至大約1份重量之接枝連結單體， 以及大約0.5至大約5份重量之至少一種親水性單體者。 丙烯酸酯彈性體包括，能使彈性體產生交聯之多功能 不飽和單體，如聚丙烯酸酯及衆甲基丙烯酸酯等聚烯姆不 飽和單體；以及能使酸基、有機及無機鹼以及其他電子給 予基（electronic donating group )產生離子及配位交聯 ，且能與適當的親離子試劑產生配位結合之單體。而聚烯 屬不飽和單體則包括：多元醇之聚丙烯酸酯與聚甲基丙烯 酸酯，如丁二醇-二丙烯酸酯及丁二醇-二甲基丙烯酸酯 ，三經甲基丙烧三甲基丙嫌酸酷（trimethylolpropane trimethacrylate )等；二乙烯基苯及三乙烯基苯，丙烯 酸乙烯及甲基丙烯酸乙烯，以及其他交聯單體。 至於接枝連結單體，係以含有烯丙基（allyl group ) 之化合物較爲理想，特別是烯屬不飽和酸之唏丙基酯。最 理想的是丙烯酸烯丙酯，甲莊丙烯酸烯丙酯，馬來酸二烯 丙酯，富馬酸二烯丙酯，衣康酸二烯丙酯，酸式馬來酸烯 丙酷（al lyl acid maleate )，酸式富馬酸燒丙酷，以及 酸式衣康酸烯丙酯。 在使用親水性單體時，宜選用甲基丙烯酸酯化合物， 特別是甲基丙烯酸之醯胺及羥基烷基酯。 不可分離的軟質核心改良劑之堅硬熱塑性樹脂相係爲 丙烯酸酯聚合物，而在聚合物內含有大量c卽50.〜ιοα % ) 的烷基甲基丙烯酸酯單元者。這些丙烯酸酯聚合物之熱扭—28.— (請先閲讀背面之注意事項再塡寫本頁) 本紙張尺度边用中81國家標準(CNS)甲4規格(210x297公；《：) 19990¾ Λ 6 Β6 經濟部中央標準局貝工消費合作社印製 五、發明説明（27.) 變溫度大於約20. °C，而以超過大約50. °C者較爲理想。 顆粒之堅硬熱塑性樹脂部份宜含有：大約50.至大約100. 重量％之烷基甲基丙烯酸酯，其中之烷基係含有1至4個 (以1個爲宜）碳原子；0至大約50.重量％之一種或更多 種丙烯酸_共單體，如其他的烷基-及芳基-甲基丙烯酸 酯，烷基·-及芳基丙烯酸酯，烷基-及芳基-丙烯醯胺， 經取代之烷基-及芳基-甲基丙烯酸酯及丙烯酸酯，譬如 ，鹵素、烷氧基、烷硫基、氰烷基、烷硫赶酯（alkylthiol esters )及其他取代物；以及0至大約40重量％之其他 不飽和單體，包含丙烯腈及甲基丙烯膪、苯乙烯單體及經 取代之苯乙烯單體、乙烯基酯、乙烯基醚、乙烯基醯胺、 乙烯基酮、乙烯基鹵、亞乙烯基鹵、及烯烴。通常，若選 用較軟之共單體系統，它的用量會較少以保留所欲的堅硬 特性。 可用於製造丙烯酸酯聚合物之理想單體包括：甲基丙 烯酸及丙烯酸之烷基酯，其中之烷基係含有1至4個碳原 子者。理想的甲基丙烯酸及丙烯酸之環烷基酯則爲在環烷 基中含有4至14.個碳原子者。 不可分離的軟質核心改良劑可運用多級或順序技術（ sequential technique )由懸浮或乳化聚合步驟製成。最 簡單的形式乃於第一級形成彈性體相，再於第二級形成堅 硬熱塑性樹脂相。而彈性體相或堅硬相亦可依序予以聚合。 其他類型之丙烯酸酯系、不可分離的軟質核心衝擊改 良劑樹脂，可替代前述美國專利第3,808,180號所述之理 一 29.— (請先閲讀背面之注意事項再堝寫本頁) 本紙張尺度逍用中S B家樣準（CNS)甲4規格(210X297公;a：) 經濟部中央楳準局貝工消費合作社印製 五、發明説明（28.) 想樹脂或與其形成混合物，而用於本發明之組成物內。如 以上所述，用於使組成物製成之物品提高耐衝擊性之這些 樹脂，亦爲多層高分子顆粒，它係由多級依序聚合製成。 例擧之這些不可分離的軟質核心改良劑乃爲掲示於美國專 利第 4,096,202 號、第 4，18〇,529 號、第 4,508,875 號、及 第4,730,023號，以及日本專利公告（kokai )第59-124916 號者。 本案發明人相信，最廣泛使用之組成物係含有：大約 20.至大約50.重量％之PVC，大約17.至大約38.重量％之耐候 性樹脂，以及大約12至大約33.重量％之不可分離的軟質核 心改良劑。而以含有大約40.至大約50.重量％之PVC、大約 25.至大約35.重量％之耐候性樹脂、以及大約15.至大約25.重 量％之不可分離的軟質核心改良劑者更爲理想。 本發明之若干實體的說明 在某些運用場合，宜在PVC /可分離的軟質核心組成 物及PVC /硬質核心組成物中加入其他樹脂，它可進一步 改進這些組成物之耐衝擊性。譬如，在運用於塑膠複合材 料之總厚度較薄——如達到1毫米或更薄一的揚合，宜 使用更多的耐衝擊改良劑。此時，所使用之衝擊改良劑宜 爲一種多層、依序製成之丙烯酸酯樹脂系聚合物，它有一 彈性體（軟質）核心以及一層或更多層外面的樹脂層，而 不會或很少會形成分離（倘若會分離，亦低於大約10.重垃 %)者。理想之不可分離的軟質核心改良劑，推薦使用前 述美國專利第3,808,180號所揭示者。其他類別的丙烯酸 —30.— Λ 6 Β6 (請先閲讀背面之注意事項再塡寫本頁) 装. 訂- 線， 本紙張尺度边用中a «家樣準(CNS)甲4規格（210X297公龙) 19990¾ Λ 6 Β6 經濟部中央標準局貝工消費合作社印製 五、發明説明（29.) 酯系不可分離的軟質核心改良劑，譬如，以上所述者，均 可用於取代前述美國專利第3，808，180號所揭示之理想的 樹脂，或與其相混合。 不可分離的軟質核心改良劑，其用量一般均不超過組 成物之大約5重量％，譬如，在組成物中佔大約1至大約 5重量％之間。較理想的用量係介於大約1.75至大約3.5 重量％之間。 在組成物中含有可分離的軟質核心改良劑之運用場合 ，組成物可簡便地由預混物製成，在此預混物中包含這狴 樹脂以及依序加入PVC成份及可在組成物中加入之其他成 份。就PVC /可分離的軟質核心組成物而言，預混物中可 含有大約9Q至大約98.重贵％之可分離的軟質核心改良劑以 及大約2至大約10.重量％之不可分離的軟質核心改良劑； 較理想的用量範圍則分別爲大約94.至大約9&重量％以及大 約2至大約6重量％之間。就硬質核心組成物而言，預混 物中含有大約30.至大約70.重量％之一種具有耐候性質之熱 塑性樹脂（PVC除外）、大約20.至大約60.重量％之硬質核 心改良劑以及大約1至大約10.重ϋ· %之不可分離的軟質核 心改良劑；較理想的用量範圍則分別爲大約55.至大約65.重 量％、大約35.至大約45.重量％、以及大約2至大約5重量 %之間。 本發明組成物之各個實體中均可含有其他一些成份， 譬如；染料及顔料；潤滑劑；紫外線及熱安定劑；加工助 劑；無機塡料；平光劑；熱扭變改良劑；耐燃劑；以及烟 一 31. 一 (請先閲讀背面之注意事項再填寫本頁) 裝- 訂_ 本紙张尺度边用中Η Β家標準(CHS)甲4規格(210X297公泄) 經濟部中央櫺準局貝工消費合作社印製 19990¾ Λ 6 __Β6_ 五、發明説明（30.) 霧抑制劑（smoke suppressants )。通常’這些選擇性成 份的添加總量不致超過組成物之大約10.重量％，譬如，添 加大約4至大約8重量％之這些成份。 相信本發明組成物最廣泛的用途，係在複合材料中作 爲覆蓋坯料，其中被覆蓋坯料覆蓋的一層係爲PVC，這包 含經過氯化之PVC以及氯乙烯之均聚物及共聚物，如以上 所述。本發明之覆蓋坯料可用以使其他構造用塑膠具有所 欲之性質，這些構造用塑膠包括，譬如：由其他乙烯基鹵 聚合物製成之塑膠；丙烯酸酯樹脂；丙烯膪/丁二烯/苯 乙烯（ABS )樹脂；聚苯乙烯；ABS與PVC之摻合物； PVC與丙烯酸酯-醯亞胺共聚物——如甲基丙烯酸酯-戊 二醯亞胺共聚物或丙烯酸酯/馬來醯亞胺共聚物——之摻 合物；聚烯烴，如聚丙烯；苯乙烯/(甲基）丙烯酸酯及 C甲基）丙烯酸酯多級聚合物；聚醯胺，聚醯胺-多級聚 合物摻合物，如聚醯胺/ ABS ;聚醯胺/聚碳酸酯摻合物 ;苯乙烯/丙烯腈共聚物及苯乙烯/丙烯腈-多級聚合物 摻合物；乙烯/丙烯/二烯橡膠與苯乙烯/丙烯腈共聚物 或與聚丙烯之摻合物；《 -甲基苯乙烯/丙烯腈，《 -甲 基苯乙烯/苯乙烯/丙烯腈，α-甲基苯乙烯/甲基丙烯 酸甲酯/丙烯酸乙酯；聚碳酸酯，聚碳酸酯-ABS摻合物 ，聚碳酸酯-多級聚合物摻合物；聚酯，如聚對苯二酸-乙二醇酯，聚對苯二酸-丁二醇酯，聚對苯二酸-丁二醇 酯-聚碳酸酯摻合物，聚對苯二酸-丁二醇酯-多級聚合 物摻合物，聚對苯二酸-丁二醇酯/聚四氫呋喃，聚氯乙 —32.— (請先閲讀背面之注意事項再填窝本頁) 裝· 訂- 本紙張尺度边用中國8家標準（CNS)甲4規格(210X297公婕) __ 136_ Λ 6 經濟部中央標準局貝工消費合作社印製 .. 五、發明説明（31·) 烯-多級聚合物摻合物，聚氯乙烯-（甲基）丙烯酸酯摻 合物，經過氯化的聚氯乙烯，丙烯腈/(甲基）丙烯酸酯 -多級聚合物摻合物，丙烯腈/ C甲基）丙烯酸酯/苯乙 烧，聚己酸內醒（polycaprolactone)，聚丙嫌酸酷’聚 (甲基）丙烯酸酯，聚縮醛，耐衝擊聚苯乙烯（HIPS )， 苯乙烯/馬來酑，苯乙烯/馬來醯亞胺，聚氟亞乙烯（ polyvinylidene f luo ride )，聚氣亞乙__多級聚合物摻 合物，纖維質，聚醯胺-醯亞胺（polyamideimide )，聚 醚酯（polyetherester )，聚醚酯醯胺（polyetheresteramide )及聚酸醯胺（polyetheramide ) ’ 聚苯撑氧 C polypheny lene oxides ) 及聚砚 。摻合物·亦可由其他 聚合物 糸統製 成，這包括：聚苯撑硫C polyphenylene sulfide )，聚苯 ’撐氧，聚磁，聚苯撐氧-苯乙烯摻合物，聚苯撐氧-耐衝 擊聚苯乙烯摻合物，聚氯亞乙烯，聚氯亞乙烯/ C甲蕋） 丙烯腈，聚氯亞乙烯/(甲基）丙烯酸酯，聚醋酸乙烯， 聚酸酸 _ ( polyetheretherketone)，聚酸醜亞胺 C poiyetherimide )，熱塑性聚醒亞胺，聚烯烴如聚乙烯、 聚丙燃及共聚煙〔copo i yo 1 ei ins」，以及其仙籼別的 聚合物。結合不同功能性的不規則（random )或整體（ bl 〇ck )共聚物亦可使用，而三成份或更多成份的摻合物 ，可由這些類別之聚合物的任何組合製成，以作爲本發明 之覆蓋坯料的基質。（在上述例擧之共聚物中，以及在一 般業者所使用的情形“ / ”符號代表由其中各種成份經過 共聚合所製成之共聚物，另一方面，摻合物及混合物則逕 -33.- (請先閲讀背面之注意事項再填寫本頁) 裝· 訂_ 本紙張尺度边用中國國家橾準(CNS)甲4規格(210X297公龙) χ9990^ Λ 6 Β 6 經濟部中央#準局員工消費合作社印製 五、發明説明（32.) 予標明。而且，“甲基”一詞譬如在“甲基”丙烯酸酯中 所示者，它與傳統的業者中廣泛使用的情形相同，係包含 “丙烯酸酯或甲基丙烯酸酯”。）因此，種類繁多的構造 用樹脂，在業界一般稱爲“堅硬熱塑性樹脂” （rigid thermo plastics )者，可隨着本發明之覆蓋坯料作爲底 層或基質。這些構造用塑膠可單獨使用，卽隨着本發明之 覆蓋坯料作爲構造用塑膠，或者可同時使用一種以上，或 以兩種或更多種聚合物或共聚物之摻合物形成一種構造用 塑膠摻合物。若使用一種以上的基質層時，另可使用接着 劑（或“結合”，tie )層。且在聚合物、構造用塑膠以 及摻合物中，可含有丙烯酸酯或（甲基）丙烯酸酯/ 丁二 烯/苯乙烯C “ MBS ”）或乙烯/丙烯/二烯（“ EPDM ” )聚合物衝擊改良劑。此外，可在其中加入下述塡料。本 發明之覆蓋坯料亦可作爲發泡塑膠（foamed plastic )， 如發泡PVC及發泡ABS之表面材料。 作爲覆蓋坯料時，組成物宜不使紫外線及可視光線（ < 520 nm )穿透。在本發明範圍內之組成物樣品係不透 明者C譬如，對光線之不透明度至少爲95. % )。若有必要 ，可在組成物中加入遮光劑及/或顏料，使它呈不透明。 必須瞭解的是，本發明組成物可運用於在組成物無法 與下層的構造用塑膠材料——如聚烯烴或聚苯乙烯——相 容的場合。這種類型的複合材料可藉着在镫蓋材料與構造 用塑膠之間加入可互相共容之黏着劑而將彼此不相容的材 料黏着一起予以有效地製成。 一 34·— (請先閱讀背面之注意事項再填寫本页) 本紙張尺度边用中國《家楳準（CNS) f 4規格（210x297公址) x999〇^ Λ 6 B 6 經濟部中央橾準局員工消費合作社印製 五、發明説明（33.) 本發明之樹脂組成物可利用傳統的設備予以躋壓、模 製、成型或壓製而形成巨大（monolithic )薄片或薄膜， 包括镫盖坯料。組成物亦可根據傳統技術予以製成。構造 用塑膠中可運用標準的凝積（lamination )或共携壓（ coextrus ion )技術及設備，臂如，加腿逊秸、雙擠腿（ bi-extrusion )及共班光（co-calendering )，而在終 端加入前述的樹脂組成物；此外，溶液鑄模法（solution casting methods )亦可用以製成本發明之疊積·材料。 較理想的情形是使用分隔給料共擠壓以製成本發明之 薄片及薄片般的複合材料。在此，“分隔給料共擠腿’’一 詞係指一製程，其中將作爲第一種塑膠材料（甓如，構造 用塑膠材料）的樹脂進料及作爲第二種塑膠材料（臂如， 覆蓋坯料材料）的樹脂進料均在不同流股中予以加熱至熔融狀 況，再注入分隔給料區（f eedb 1 〇ck )，在此將各流股滙 聚一起作面對面的表面接觸以形成雙層流股（two-ply stream )，然後再注入一薄片模具（sheet die )內，使 雙層流股在層流（1 aminar f 1 ow )條件下沿側面分佈成 雙層薄片，薄片的熔融樹脂層自模具流出時係呈面對面的 表面接觸，隨之將成型後之雙層薄片予以冷却及固化，形 成之複合材料，其每一層的薄片係藉構成薄片之固化樹脂 使它彼此形成整體結合。如業界所習知者，分隔給料共擠 Μ Μ程可用以製成多於兩層的溥片，其所使用之分隔給料 區在設計上卽可容納兩股以上的樹脂流股，或可在分隔給 料區將兩股樹脂分離並在多數的轉換層C alternating -35.- (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 線· 本紙張尺度遑用中Η國家標準（CNS)甲4規格（210x297公址) Λ 6 Β 6 五、發明説明（34.) (請先閲讀背面之注意事項再堝寫本頁) 1 ayers )中將它再雁合。 經濟部中央標準局貝工消t合作社印製 本發明之覆蓋坯料組成物，其例擧的其他使用場合包 括：汽車用途，如裝飾外門頭線（decorative exterior trim )，模製側邊頭線（molding side trim )及四分儀 頭線板（quarter panel trim panels )，檔泥板伸出部 份，百葉窗，後端板，輕便卡車蓋，後視鏡座，儀錶旋鈕 ，裏門或外門頭線之握把C snap-on )及其他扣件，卡車 、客車、露營車（campers )、客貨兩用車（vans )及 大衆運輸車輛之附件，柱伸出部份（b-pi 1 lar extens ions )等；家電及工具，如草地及花園用具與籬笆，活動房屋 之浴室裝置，遊艇組件、活動房屋之室外組件、草地傢倶 如椅子及桌架，管線及管端蓋，行李箱，活動房屋之淋浴 間，馬桶座，標識板，溫水池，冷氣機及熱泵組件，野餞 冷却器（bead-molded picnic coolers )，野餐盤及壺， 以及廢物罐；軟百葉簾組件；運動用品，如帆板，帆船， 滑水板；水管零件如盥洗零件等；及前述以外之建築組件 ，這種種組件包括建築模板、門模板、百葉窗、擋門、活 動房屋壁邊，庭院門，周邊附件，窗戶護套，屋頂窗架， 天窗架，簏槽之端蓋，遮陽及停車屋頂等。這些淸單例示 本發明之覆蓋坯料材料的運用類別及用途。 在本發明之組成物中尙可加入之其他成份，係爲濃縮 色料，譬如，染料及顔料，潤滑劑，紫外線安定劑，熱安 定劑，抗氧化劑，熱扭變溫度改良劑，抗靜電劑，去光劑 一 36. 一 本k張尺度边用中B «家標準(CNS)甲4規格(210x297公龙) Λ 6 13 6 經濟部中央標準局貝工消费合作社印製 五、發明説明<35·) (matting agent )，耐燃劑，以及加工助劑。迎常，适 些選擇性添加的成份，它的總量一般均不超過組成物之大 約.5重量％，甓如，使用大約1至大約5 m迓％之這些成 份。這些選用的成份可加入覆蓋坯料組成物或構造用盥膠 內，亦可於兩者中均予加入。此外，諸如木材纖維、碳纖 維及玻璃纖維等塡料亦可視需要將它加入本發明之組成物 內，但預期這些特殊塡料的耐候性會較差。而且，玻璃粒 及一些無機物質如碳酸鈣、滑石、二氧化鈦、硫酸鋇等亦 可視需耍將它加入本發明之組成物內。迎常，這些選川的 塡料，其總量在覆蓋坯料中將不會超過大約15.重量％，而 在構造用塑膠或基質中則不會超過大約65.重量％ ° 以下實施例係用以例示本發明。 實施例 實施例1之組成物係含有基質樹脂與硬質核心、衝擊 改良劑樹脂之混合物。 實施例1——硬質核心組成物 實施例1之組成物係由以下代號㈧、⑻及(C)之三種不 同基質樹脂之混合物製成。 基質樹脂（Matrix resins ) (A)此一基質樹脂係爲PVC，它的來源是一種完全配方 的PVC組成物，含有下述成份，.其用量以毎百份中之份數 (phr )表之。 -37.- (請先閲讀背面之注意事項再塡寫本頁) 本紙張尺度边用中國《家標準(CNS)甲4規格(210X297公龙) 19990½ Λ 6 B 6 五、發明説明（36.) 成_ί&_ 用量，phr (1) PVC，K69 100 ⑵含80.重量％之丙烯酸丁酯核心及20.重量％之 5 甲基丙烯酸甲酯外殼之不可分離的軟質核心 、衝擊改良劑樹脂 ⑶羧酸錫安定劑 3 ⑷潤滑劑混合物——1.2 phr硬脂酸鈣，0.4 2.35 phr石蠟，0.15 phr聚乙嫌蠟，及0.6 phr 潤滑加工助劑（高分子量的丙烯酸酯/苯乙 烯聚合物）丙烯酸乙烯樹脂 ⑸熔融助劑——高分子量的丙烯酸酯加工助劑 1 ⑹三唑類紫外線安定劑 0.17 (請先閲讀背面之注意事項再填寫本頁) 裝< 經濟部中央櫺準局貝工消費合作社印製 上述PVC組成物係由各種成份在高強度混合器內摻合 而製成。 ⑻此一基質樹脂係爲含有91.重量％之甲基丙烯酸甲酯 與9重量％之丙烯酸乙酯、且分子量大約爲95,000 dal ton 之一種不規則共聚物。此共聚物係在有機過氧化物存在下 於連續流動之攪拌槽反應器內製成。 (C)此一基質樹脂係爲含有91.重量％之甲基丙烯酸甲酯 與9重量％之丙烯酸乙酯、且分子量大約爲100,000 dal ton 之一種不規則共聚物。此共聚物係由乳化聚合製成，先在 系統內形成種子（seed )，再藉反應器/批式法，形成聚 合物的其餘部份。 在實施例1之組成物中所使用之衝擊改良劑樹脂如下 —38.— 訂 線- 本紙張尺度边用中國a家標準（CNS)甲4規格（210x297公釐） 經濟部中央楳準局員工消費合作社印製 3l99 撕 λ6 _Β6 _ 五、發明説明（37.) 硬質核心、衝擊改良劑樹脂 改良劑樹脂包含三層高分子顆粒，它係依前述美國專 利第3,793,402號所揭示之多級、依序步驟製成。核心層 及^各爲含有大約96.重量％甲基丙烯酸甲醒與4重量 丙烯酸乙酯之不規則共聚物，而核心層共聚物係與0.2重 量％之甲基丙烯酸烯丙酯形成接枝連結。中間層係爲含有 大約81·重量％之丙烯酸丁酯與18.重量％之苯乙烯的一種不 規則共聚物，它與大約1重量％之甲基丙烯酸烯丙酯形成 接枝連結核心、中間及外層的比例分別爲35. %、45. %及20. %。改良樹脂之粒徑介於大約250至大約350 nm之間。 樹脂成份之接合_ 上述各種樹脂成份依以下方式予以摻合，以形成實施 例1之組成物，其含有表中列示用量之下述成份。 (請先閱讀背面之注念事項再填寫本頁) 實施例1之組成 成_份 重量％ PVC 樹脂 44.8 MMA/EA 樹脂(B) 25 r i ly 'V\ ；；'- l^MA/EA、Wg(C) 5 < - .. t τ 硬質核心、擊改良劑樹脂 20 不可分離的軟質核心、衝擊改良劑樹脂 2.2 羧酸錫安定劑 1.4 潤滑劑 1.1 熔融助劑 0.4 紫外線安定劑 0.1 -39.- 本紙張尺度边用中國《家標準（CNS) f 4規格（210x297公址） 19S902 Λ 6 Β 6 經濟部中央標準局貝工消費合作社印製 五、發明説明（38·) 在製造實施例1之組成物時，係先配製基質樹脂(C)與 硬質核心、衝擊改良劑樹脂之混合物，再令它與基質樹脂 ⑻相混合。此時係在裝有攪掸器之槽內，以20.重量％之膠 乳（內含50.重量％之前述樹脂(C))及80·重量％之衝擊改良 劑樹脂相混合，並摻合均匀以製成一混合物。將摻合物噴 霧乾燥並分離成自由流動粉末。取50.份重量之此一混合物 ，以人工方式與50.份重量之基質樹脂⑻相混合，以製成含 有50.重量％基質樹脂⑻、〗0.重量％基質樹脂(C)，及40.重量 %衝擊改良劑樹脂之一種組成物。將此組成物於傳統的擠 壓機內予以熔融摻合，並予擠壓成粒。令這些塑膠粒與完 全配方之PVC組成物依50. /50.重量比例，混合加入聚乙烯 袋內，在此以人工攪拌予以混合。然後，將乾燥摻合物加 入單螺桿擠壓機（25.毫米直徑X 600毫米有效螺旋長度） ，予以熔解及分散混合。本體區（barrel zone )及模具 區（die zone )均控制於196 °C，熔融擠壓出之長條，在 水中冷却後再予切粒。 以下實施例係用以例示與實施例1相似之組成物，但 各種成份之含量不同。 實施例2——硬質核心組成物 本實施例之組成物係使用不同比例之下述成份製成。 所製成之粒狀組成物，含下述成份： -40.— 本紙張尺度遑用中囲Η家樣準(CNS)甲4規格(210X297公龙) (請先閱讀背面之注意事項再填寫本頁) 裝· 訂_ 199902 Λ 6 Β6 五、發明説明（39.) _實施例2之組成物 成_§_ 重量％ PVC 22.4 ΜΜΑ/ΕΑ 基質樹脂(Β) 37.5 ΜΜΑ/ΕΑ基質樹脂(C) 7.5 硬質核心、衝擊改良劑樹脂 30 不可分離的軟質核心、衝擊改良劑樹脂 1.13 羧酸錫安定劑 0.7 潤滑劑 〇_52 熔融助劑 0.2 紫外線安定劑 0.05 實施例2之組成物係由含有基質樹脂之塑膠粒與實施 例1所示之PVC組成物，依75. / 25.重量比例相混合而製成。 實施例3及4 -硬質核心組成物 以下兩個實施例係例示與實施例1及2相似之組成物 ，但其中僅以一種類別的丙烯酸酯樹脂作爲基質樹脂，此 卽上述之樹脂(C)。組成物中含下列成份： (請先閲讀背面之注意事項再蜞寫本頁) 經濟部中央櫺準局貝工消費合作社印製 -41.- 本紙張尺度逍用中Β國家楳毕（CNS)甲4規格（210X297公;¢) ^9990¾ Λ 6 Β6 五、發明説明（40.) 用量，重量％ 成 份 實施例3 實施例4 PVC 44.8 22.4 ΜΜΑ/ΕΑ基質樹脂(C) 30 45 硬質核心、衝擊改良劑樹脂 20 30 不可分離的軟質核心、衝擊改良劑樹脂 2. 2 1.13 羧酸錫安定劑 1.4 0.7 潤滑劑 1.1 0.52 熔融助劑 0.4 0.2 紫外線安定劑 0.1 0.05 (請先閲讀背面之注意事項再蜞寫本頁) 經濟部中央橾準局貝工消费合作社印製 實施例3之組成物係由6Q份重量之實施例1所示之 MMA / Ε Α型膠乳與40.份重量之硬質核心、衝擊改良劑樹脂 (其來源亦爲一種膠乳）相摻合而製成。形成之均匀摻合 物，隨後再予噴霧乾燥。取50.份重量之形成的樹脂粉末與 50.份重量之PVC組成物相混合，再依實施例1之方式予以 造粒。實施例4之組成物係依與實施例3相同的方式製成 ，但其中係以75.份重量之樹脂粉末與25.份重量之PVC組成 物相混合。 以下實施例亦例示本發明之組成物，但其中係使用軟 質核心、衝擊改良劑樹脂。 實施例5 -可分離的軟質核心組成物 本實施例之組成物包含類似前述美國專利第4，14 1，935 號之實施例1中所示之可分離的軟質核心樹脂，如該專利 所揭示者，樹脂係由下述成份，依所示用量，於四級依序聚 -42.- 本紙張尺度边用中困Η家楳半(CNS)甲4規格(210X297公龙) Λ 6 U6 五、發明説明（41.) 合所製成：第一級——25·〔丙烯酸丁酯（BA)/1，3 - 丁二 醇二丙烯酸酯（BDA ) /甲基丙烯酸烯丙酯（ALMA )- 98.5/1.0/0.5〕；第二級——25.〔 BA /甲莲丙烯酸（ MA ) / ALMA — 40/60/0..5〕；第三級-** 25·〔甲基丙嫌酸 甲酯C MMA ) / BA/正十二烷基硫醇（n - DDM ) — 90/ 10/0.5〕；第四級一25.〔 MMA/BA/n-DDM — 90. / 10· /1.5〕 。囘收之樹脂係呈膠乳型態，其固體含量約爲45.重量％。 實施例5之組成物含下列成份： 成 份 重量％ PVC 44.8 可分離的軟質核心改良劑樹脂 50 軟質核心、衝擊改良劑樹脂 2.2 羧酸錫安定劑 1.4 潤滑劑 1.1 熔融助劑 0.4 紫外線安定劑 0.1 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂- 線· 經濟部中央標準局貝工消費合作社印製 實施例5之組成物係由f分離印軟質核心、改良劑樹脂 與前述之完全配方的PVC組成物，依50./50.重量比例，在 聚乙烯袋內，藉人工攪拌予以混合而製成。隨後，將此乾 燥摻合物加入單螺桿擠壓機（25.毫米直徑X 600毫米有效 螺旋長度），予以熔解及分散混合。本體區及模具區均控 制於180 °C，熔融擠壓之長條於水中予以冷却，並予切粒。 在實施例1至5之各種組成物中，加入含有21.8重 —43.— 本紙張尺度边用中困Η家標準（CNS)甲4規格(210 X297公址） 19990¾ Λ 6 Β 6 經濟部中央櫺準局貝工消費合作社印製A 6 B 6 19990¾ V. Description of the invention (7) Multi-manifold mold co-extrusion technology is ideal. Articles made from the improved composition of the present invention have superior weather resistance characteristics, including color retention. The composition blended with the light color material or the dark color material can obtain superior color retention. Other advantages that can be obtained by the present invention include the economical efficiency of the clam, better flame resistance, and better reworkability. Related to the better reworkability, when the composition of the present invention and the plastic material constituting the composite material and / or the material constituting the plastic layer for grenades are involved in the re-grinding and re-extrusion of these materials In the recycling technology, when mixed, it can show good compatibility with each other (compatabi1ty). After referring to the following detailed description, the present invention can be further understood. The main component of the composition of the present invention is PVC, which forms the continuous phase of the composition, which is often referred to herein as "matrix resin" (mat rix resiq). In the welcome work of the present invention, the PVC component system is extensive Zhichuan manufactures thermoplastic homopolymers or copolymers of vinyl chloride with the same type of M-glue items. In this specification, the term "poly (vinyl chloride) resin" or "PVC" refers to chlorinated PVC or homopolymers or copolymers of vinyl chloride, with gas ethylene as the main component (over 50. weight %)By. Therefore, the PVC component can be a homopolymer of poly (vinyl chloride) or a copolymer of vinyl chloride and one or more other monomers, such monomers include, for example: vinyl acetate, etc .; vinylidene halide (vinylidene) halides) such as gas vinylene; alkyl esters of carboxylic acids such as acrylic acid, ethyl acrylate, 2-ethylhexyl acrylate, etc .; unsaturated hydrocarbons such as ethylene, propylene, isobutylene, etc .; allyl compounds such as acetic acid- 9 — A 4 (210X297mm) ............................................... ................................... # ................ ....... Explosion. (Please read the note -1E on the back and fill in this page) A6 B6 19990¾ printed by the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (8) {Please read the note of the moraine plan first Please fill in this page again) Allyl ester etc. When a copolymer of vinyl chloride is used, it is desirable that the content of collard ethylene is at least about 80% by weight of the copolymer. The PVC component may be a mixture of homopolymer of vinyl chloride and / or chlorinated PVC and one or more copolymers, or two or more of vinyl chloride and / or chlorinated PVC A mixture of copolymers. The molecular weight and molecular weight distribution of PVC can vary greatly. When using extruded construction products, the Fikentscher K value of PVC is preferably between about 62 and about 701, and more ideally is between about 6 and about 69. Fikentscher K value is determined by the following formula: L〇gqrel / c = (75 X 1〇τ6ίί) / (1 + 1.5ΧΚΓ3 KC) + 10_3K where C represents the concentration of the polymer in the solvent, 〇 * 5g / 100ml ; [^ Drel represents the relative viscosity in cyclohexanone (25.1C); and K represents Fikentscher. In the ideal form, the PVC component is a homopolymer of ethylene. As described above, the present invention includes: in one entity, the composition includes TVC as the main component, and multilayer, sequentially manufactured JiUE- · ------------- ------- ^ The particles of the polymer, whose elastomer cross-linked core is covered by most polymer shells, the outside of which can be combined with (also referred to as _ "Chili" here. Agent ”, dissociable soft core modifier) phase separation 1—I ___m Ministry of Economic Affairs Biaoyang Biao Bureau H-7- " '1' · Cooperative Du Printed; and in the second and third entities, the composition It includes as a main component a mixture of at least two matrix resins— 卽 PVC and a thermoplastic resin that has weather resistance and is compatible or miscible with PVC—and includes impact improvement of acrylates and hard cores Resin resin or acrylate system, inseparable soft core, impact modifier resin (herein also respectively—10.—This paper scale is applicable to China S Family Standard (CNS) f 彳 specifications (210X297 mm) A6 B6 19990¾ V. Description of the invention (9) Called "hard core modifier", hard core modifier, and "{please first Read the notes on the back of the page and fill in the "quote" page) inseparable 0 ^ potential. 'Quality core improver, non-dissociable soft core mod ifi eV Hachiko / former composition is referred to here as "f YC / denier quality Core composition "C PVC / dissoc.iable sof t core conposition) _____,-. ^ F, and the latter composition can be P.VC / ^ 是 核 丄 α 姐 ^ 物" (PVC / hard core compos Itio's "P / VC / non-dissociable soft core compo sition" (PVC / non-dissociable soft core compo sition). These components will be described in detail below. PVC / separable soft core composition is known from the above, The composition of this entity includes a separable soft core modifier and PVC, and the P VC component is the aforementioned type of resin. A separable, soft core modifier, its essence is to make the PVC-based composition have improved weather resistance Characteristics, and improved impact strength. For example, a separable, soft core modifier that can make the PVC-based composition have this comprehensive property is a copolymer particle whose elastomer cross-linked core is covered by most polymer shells Wrapped stirrup And some of these shells have the ability to be separated from the particles. As can be seen from the following more detailed description, some of these particles can be separated under melt processing conditions, and the outer shell part and the inner part The phases are separated and still present as discrete particles. The ideal resins used in the cooperation of the General Department of Industrial Engineering, Bamboo, and Bamboo in Duan · " of the Ministry of Economic Affairs of the present invention have been shown in the aforementioned U.S. Patent No. (4,141,9i | 11 1 ... .......... No., the content of which is shown here for reference. The resin disclosed in No. 4,141,935; is a kind of acrylate resin copolymer particles , Whose elastomer cross-linked core is enclosed by a three-layer thermoplastic copolymer shell with increasing hardness. The M-type resin system is more — 11 · The paper standard is applicable to the CNH f 4 standard ( 210x297 mm) A6 B6 19990¾ V. Description of the invention (l ..) Graded, sequentially made polymer C mu 1 t iple stage, sequential ia 1 ly produced polymers). Here, the polymer is in an aqueous dispersion Or made in emulsion, the polymerization reaction is carried out in the presence of preformed latex (preformed latex), this latex is made from the previous monomer feed, and every subsequent polymer is attached or tightly bonded Those who are above the first level of Ling. The resin contains: (A) The softer first-stage polymer of the first elastomer type, which is made of an aqueous emulsified monomer system containing the following components: (1) about 75 to about 99.8% by weight, A more ideal situation is between about 94 to about 99.8% by weight of at least one C2 ~ C8 alkyl acrylate; ⑵ about 0.1 to about 5% by weight, more preferably about 0.25 to about 1 At least 5% by weight—a cross-linked polyethylenically unsaturated monomer; ⑶ about 0.1 to about 1% by weight of at least one graft-linked (graf tl inking) poly rare unsaturated monomer; and ⑷The rest of the part is that the total amount of the first-stage monomer system reaches 100% by weight is one or more copolymerizable monoethylenically unsaturated monomers, and the choice of monomer system is the highest If the glass transition temperature does not exceed -2α X: ⑻Second-stage polymer, which is polymerized by aqueous emulsified monomer system of the following components in the presence of the aqueous system formed by the first-stage polymerization: ⑸ about 10 . To about 90% by weight of at least one C2 ~ C8 alkyl acrylate; ⑹ about 9 to about 89.9% by weight of at least one G ~ C4 alkyl methacrylate; and ⑺ about 0.1 to about 1% by weight of at least one _ graft-linked polyethylenically unsaturated monomer; (0 third level Polymer, it is water-based formed by the second-level polymer-12-This paper scale is applicable to the Chinese standard (CNS) f4 specification (210x297 mm) L. One-____________ * ..... .................................................. Pretend ..................... Order ... V.: ............... ..... 线 · ... (please read the attention to the face and then fill in this page) A6 B6 19990¾ V. Description of the invention (U ·) In the presence of the system, the water-based emulsification unit of the following ingredients The body system is polymerized into: ⑻ at least one of about 5 to about 40% by weight <: 2 ~ (: 8 alkyl acrylate; and ⑼ about 601 to about 95.% by weight of at least one Q ~ C4 alkyl methacrylate; and (D) the final one has a glass transition temperature of at least 6Q * The fourth-stage polymer of C is formed by the polymerization of the aqueous emulsified monomer system of the lower rate component in the presence of the aqueous system formed by the third-stage polymerization: ⑽ at least one C of about 80 to about gal weight%: ~ C4 alkyl methacrylate; and (11) the rest, so that the total amount of the fourth-stage monomer system reaches 100% by weight, it is at least one (^ ~ C8 alkyl acrylate. In this specification, "crosslinking polyethyleni cal ly unsaturated monomer" (crosslinking polyethyleni cal ly unsaturated monomer) or "cross-linking monomer" (cross 1 inking monomer) — _ refers to a total of one M taken, where Contains at least two unsaturated functional groups that can produce addition polymerization, and each unsaturated functional group can be polymerized at approximately the same rate. Crosslinking monomers include: polyacrylate acrylate or methacrylate, such as , Butylene glycol diacrylate butylene diacrylate), butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, etc .; di- and trivinylbenzene, etc .; vinyl esters, such as acrylic acid Vinyl acrylate; and other cross-linking monomers. C alky lene diacrylate is ideal for cross-linking with the first-level alkyl acrylate. In this manual, "connect Branch-linked polyethylenically unsaturated monomer "(graf 11 inking polyethy1enica11y unsaturated monomer) —13.— This paper” applies to China National Standard (CMS) f 4 specifications (210x297 mm) (please read the back page first Matters needing attention and refill · " this page) Install · * Λϊτ · Ministry of Economics and Trademark Office of the Ministry of Economic Affairs ';' Cooperative Du Printed A6 B6 199902 V. Description of Invention (12 ·) i or "graft link list" "Body" (graft 1 inking monomer) — word refers to a copolymerizable monomer containing at least two unsaturated functional groups that can be polymerized, and each functional group proceeds at a rate that is quite different from each other Aggregator. Examples are here Suitable graft link monomers in the Ming include: Lu-unsaturated mono- and dicarboxylic acid allyl, methallyl, and crotyl esters, such as allyl methacrylate and Allyl acrylate; and diallyl maleate, diallyl fumarate, and diallyl itaconic acid. Among them, allyl methacrylate and allyl acrylate are preferred. Exemplified are the copolymerizable, monoethylenic M unsaturated monomers that can be used in the first-stage monomer system shown in (A) ⑷ above, which are vinyl idene chloride, vinyl chloride, Acrylonitrile, ethyl vinegar, and o-, m-, p-methylstyrene and -alkylstyrene. The first-stage polymer can account for about 10. to about 75% of the total weight of the formed four-stage polymer, and the rest is evenly or unevenly distributed at other levels, but only if the amount of other single levels exists , Must not be less than 2α% or more than 75% of the total weight of the remaining levels. The melt index value of a multi-stage polymer is generally between about 0.01 and about 20. However, a value between about 3 and about 8 is preferable. The minimum film-forming temperatun (MFT) of the polymer is preferably between about 60L and about 1DQlC. And the average particle size of the first-stage polymer is preferably between about 500 to about 4000 ° A Γ | ϊ position. There are a number of ideal entities associated with the first-stage and fourth-stage reactions used to make separable soft core modifiers. The first-level response should be -14.— This paper standard is commonly used in the “standard” (CNS) Ή specification (210x297 mm) of the Η® family (please read the note of Long Shishuo before filling in this page) • Install · • Order · The Ministry of Economic Affairs Shiyang Central Bureau of Industry and Consumers Cooperation Du Yin ¾ A6 B6 19990¾ V. Description of the invention (13.) Use about 94 to about 99.8% by weight of butyl acrylate, about 0.25 to about 1 5% by weight of crosslinking monomer, and about 0.1 to about 1 M of graft linking monomer. For the fourth reaction, methyl methacrylate should be used. The inventor of the present application believes that the most widely used composition is one containing about 20. to about 50.% by weight of PVC and about 50. to about 75% by weight of a separable soft core improver, and the more ideal amount It is those containing about 3% to about 48.5% by weight of PVC and about 50% to about 6% by weight of modifier. It can be explained (unconfirmed) that during the heat treatment of the PVC / separable soft core composition of the present invention, the following situation is believed to occur, at least part of which will promote the use of this entity of the present invention to obtain superior effect. When PVC / separable soft core composition is compounded by melt extrusion, the outer part of the four-stage acrylate polymer particles is based on the long-term miscibility of poly (alkyl methacrylate) with PVC Understand, it is believed that it will form a homogeneous alloy matrix phase with PVC. Dispersed between them are particles in the form of discrete particles, which are the particles (including the core) that flow out after the outer part is decomposed. This alloy matrix phase, which does not contain any cross-linked resin, contains a “flowable” component formed during melt processing. The soft core of the fourth level, separable resin particles, which is not grafted to the third level, will all exist under melt processing conditions and will separate from the inner part of the particles, and will form a PVC / acrylate alloy Matrix phase. Moreover, a part (for example, about half) of the third stage, because it is only partially grafted to the second stage, will be separated from the stage and incorporated into the alloy matrix phase. Weather resistance—15.— This paper scale is applicable to the China Standard (CNS) «F4 specification (210x297 mm) (please read the precautions on the back and then fill in this page) • Installation · .ίτ · • Line · A6 B6 19990¾ V. Description of the invention (14.) (please read the precautions of the plan first and then fill in this page) The acrylic polymer chain with higher performance will separate and dilute it in the matrix with lower weather resistance For the PVC part, it is believed that this will significantly stabilize the photochemical decomposition of PVC, and the weather resistance performance of the composition is very superior. Therefore, the separable soft core modifier can be considered as a multi-layer, sequentially made acrylate resin-based polymer, in which the elastomer cross-linked core is covered by most polymer shells. There is a large portion of the outer shell of the outer shell. This polymer has a considerable proportion of the outer shell, and it also accounts for at least about 20% by weight of the total weight of the polymer. It has a kind of The ability to disperse from it and form a homogeneous alloy matrix phase with PVC. Ideally, at least about 30% by weight of the polymer can be separated in the aforementioned manner. Generally speaking * this separation does not exceed about 50 of the total weight of the polymer M. .. ································································ Next, the separable part of the soft core modifier can be miscible with the PVC component of the resident phase of the composition M. "Missible" (miscible)-the term, here refers to resin-for example, the separable modifier Part —— It has the ability to form a molecular mixture with PVC, and this molecular mixture is a homogenous state under the microscope, like a hip, a homogeneous blend, characterized by not containing a large amount of individual resin The presence of such a microscope area or domain of components. This homogeneous blend of resins is characterized by a glass transition temperature intermediate between the glass transition temperatures of individual resin components. Therefore, the glass of individual resin components The temperature can not be measured by traditional techniques such as differential scanning, calorimetry or dynamic mechanical analysis. The aforementioned US Patent No. 4,141,935 is separable — 16. This paper scale is applicable to China National Standard (CNS) A 4 specifications (21 0x297 公 嫠) A6 B6 19990¾ V. Description of the invention (15.) Part of the polymer particles can be miscible with PVC. (Please read the notes on the surface before filling in this page) The scope of the invention also includes A separable soft core modifier that is compatible with the PVC component of the matrix phase of the separable part. In this specification, "compatible" (__compat i bl e)-the term refers to the resin-for example, The separable Tai component of the modifier-has the ability to form a close mixture with PVC. Here, PVC and the separable part are firmly adhered to each other in the mixture, but they are not in a homogeneous state. It contains a large number of individual resin components. This mixture can be confirmed, because the glass transition temperature of the individual resin components in the mixture can be determined by traditional techniques such as differential scanning, calorimetry or dynamic mechanical analysis. PVC / Hard core and inseparable soft core composition The composition of these entities of the present invention mainly contains matrix resin (for PVC and some with weather resistance, it can be miscible with PVC or phase with PVC A mixture of thermoplastic resins) and containing less than M: acrylates, hard cores, impact modifier resins, or acrylates • inseparable soft cores, impact modifier resins, or mixtures thereof. The PVC component is the aforementioned type of resin. The thermoplastic resin used when forming the matrix part of the composition of the present invention together with PVC can be selected from any industry-recognized thermoplastic resin with good weather resistance. It can retain its chemical and / or physical properties when exposed to outdoor conditions. These outdoor conditions usually include exposure to: sun rays; temperatures of 80-90 ° F or higher; temperatures below freezing; and large fluctuations in temperature; And rain, snow, hail, etc. Examples of thermoplastic resins that are considered to be particularly good weather resistance include: α-Phenylstyrene-17.- This paper scale is applicable to 8 Chinese standards (CNS) F4 specifications (210x297 mm) 19990¾ Λ 6 13 6 Economy Printed by the Ministry of Trade and Industry, Beigong Consumer Cooperative V. Description of the invention (16.) Ethylene / methacrylate resin, methacrylate / acrylate resin, methacrylate resin, and polyvinyl fluoride resin) resin. For example, it is considered that the weather resistance property is good-the weather resistance property is better than PVC but inferior to one of the aforementioned resins, including: styrene / methacrylate resin, and styrene / acrylonitrile resin. In addition to having good weather resistance properties, the thermoplastic resin is also compatible with the PVC component of the matrix phase of the composition. Ideally, the thermoplastic resin is miscible with the PVC component of the matrix phase of the composition. The meanings of "miscible" and "compatible" are the same as the previous discussion on the separable part of the soft core modifier. Methacrylate resins and methacrylate / acrylate resins are examples of resins that are miscible with PVC and have excellent weather resistance. Styrene / methacrylate resins (including α-methylstyrene) and styrene / acrylonitrile resins are examples of resins that are compatible with PVC, but after pre-trial comparison: ¾ is superior, because; U : Α · has better comprehensive properties. In the operation of the present invention, particularly desirable thermoplastic resins include: the main components are methyl methacrylate and a small amount of alkyl () acrylate-more preferably methyl acrylate or ethyl acrylate, and ethyl acrylate Ester is the most ideal-polymerized methyl methacrylate or copolymer made by polymerization. The copolymer may contain about 85. to about 99.9% by weight of methyl methacrylate, and about 0.1 to about 15.% by weight of alkyl acrylate. Ideally, the alkyl acrylate component of the copolymer is between about 5 to about 15. wt%, and about 8 to about 13. wt% is most ideal, the other components of the copolymer are It is methacrylic acid—18.—This paper scale is used in the national standard (CNS) A4 specification (210x297 public issue) (please read the notes on the back first and then write this page). Binding. Ministry of Economic Affairs Printed X9990S Λ 6 _; _ Β6_ by the Beigong Consumer Cooperative of the Central Bureau of Precinct V. Description of the invention (17.) Methyl ester. Increasing the alkyl acrylate content of the copolymer will increase the melt flow index (melt flow index) and reduce the melt viscosity of the copolymer, if it is part of the resin composition. Minimizing the alkyl acrylate composition will also increase the hardness, scratch resistance (scratch resistance), and the resistance of the covering blank to chemical attack. Ideally, the acrylate matrix resin should have a molecular weight of at least about 80,000 da It on. Its range can reach 130,000 da It on or even higher. Ideally, the molecular weight is between about 90,000 and about 120,000, and most preferably between about 90,000 and about 105,000 dal ton. Increasing the molecular weight of the copolymer and keeping the others the same will reduce the melt flow index and increase the melt viscosity of the copolymer, even if it is part of the resin composition. Increasing the molecular weight can also improve the chemical resistance and tensile properties of the composition. Generally, the aforementioned acrylate copolymer is a random copolymer, which is preferably a mixture of two hammer monomers in a continuously flowing stirred tank reactor for free radical catalysis with organic peroxides The overall polymerization reaction is made, the conversion rate is about 50.%. The polymer-monomer mixture is pumped to a devolatilizing twin-screw extruder, where residual monomers are removed and other additives can be added. The technique for performing this aggregation can be found in the literature and is known to those familiar with this technique. Irregular copolymers can also be made by bulk casting or by suspension or emulsion polymerization, the latter being the most ideal. The copolymer made by emulsification can be borrowed -19.-· (Please read the precautions on the back before writing this page) Binding-Order-Line · This paper ί ： Standard Xiaozhong SB Family Standard (CNS) A 4 specifications (210x297 g) Printed by the Ministry of Economic Affairs, Central Bureau of Employee Consumer Cooperatives χ999 ^ Λ 6 _Β6_ V. Description of the invention (18.) Spray drying or coagulation, washing, and drying to separate, or after separation by coagulation, and then by It is washed and pressed to eliminate evaporation (extrusion devolatilization) to make it into pellets. The inventor of this case believes that the thermoplastic matrix resin with weather resistance used in the composition can improve its photochemical decomposition, oxidation, and other mechanisms-which will lead to all the decomposition of traditional outdoor-grade PVC formulations- patience. In addition to weather-resistant thermoplastic resins, PVC-based compositions also contain hard core or inseparable soft core impact modifiers. These modifiers are particles of multi-level resins or polymers containing acrylate, and the central or innermost part of the multilayer resin (called "core") is coated by a layer or multilayer resin layer or shell ) Continuously coated. As is well known, these multi-layer resins are generally made of multi-stage polymerization in sequence. It is generally known that adding such hard cores provided by the present invention to PVC may not Acrylic resin-based polymers made of separated soft cores in multiple stages can improve their impact resistance. Generally, these compositions contain a continuous phase of PVC, and discrete particles of the aforementioned resins are dispersed therebetween. Generally speaking, PVC compositions containing hard core modifiers have better weather resistance than PVC compositions containing non-separable soft core modifiers, while PVC compositions containing non-separable soft core compositions contain more The PVC composition of the hard core modifier has better impact resistance. Hard core and inseparable soft core modifiers, both of which have several layers of outer shell or outer layer, are independent of each other, and with the use and the final desired sex-20. A paper ft scale is used in the 8 national standard (CNS ) f 4 specifications (210X297 public address) (Please read the notes on the back of the page before writing this page) Installed--? τ- Line-Printed by the Ministry of Economic Affairs, Central Bureau of Economic and Trade, Beigongxiao f cooperative, 199302 Λ6 ___BJB V. Description of the invention (19.) Depending on the quality, the cross-linked and / or graft-linked layer, or the polymer or copolymer composition, etc. may have different degrees of hardness or softness (measured by Tg). In terms of construction, in general, hard core modifiers usually have a core made of non-elastic® polymers or copolymers, which are copolymerized by crosslinking and / or grafting, and their glass transition temperature It is generally higher than room temperature (25. ° C), and often exceeds 40. ° C. Exemplary monomers used in large quantities in the production of hard core polymers include: styrene, styrene, and benzene. Alkyl methacrylate. Other monomers are generally used in small amounts. Generally speaking, an inseparable soft core modifier usually also has a core composed of a polymer or copolymer, and this polymer or copolymer is cross-linked and / or grafted to make the core rubber-like or The nature of the elastomer, and its glass transition temperature is usually at or below room temperature, Mai Changer's 抝 shape is lower than o ° c. Exemplary monomers used as main components in the preparation of inseparable soft core modifiers include: butadiene and other kangs; ethylene-propylene-diene compositions, butadiene-styrene, and Cl-C8 hospital-based acrylate. Other monomers are used in small amounts. Generally speaking, inseparable soft core modifiers are different from separable soft core modifiers, because the layers are chemically linked to each other, or entangled or locked at the interface due to the cross-linking of the polymers in the layers. And form an intermediate penetration (interpenetrating) polymer network (pol ymer network). Hard core and inseparable soft core modifiers are mainly used to enhance the physical properties of the composition, such as toughness and impact resistance. Improvement-21.- (please read the precautions on the back before filling in this page) Pack. Line. This paper is used in the middle of the troubled countries (CNS) A 4 specifications (210x297 g) 19990¾ Λ 6 Β6 Central Ministry of Economic Affairs Printed by the Bureau of Standards, Industry and Consumer Cooperatives 5. The description of the invention (2Q) The use of the agent can also improve the resistance to stress whitening and fading caused by climate change ◊ The manufacture, bonding and use of these resins are generally Familiar. The ideal PVC / weatherable thermoplastic resin / impact modifier composition of the present invention contains a hard core impact modifier. These compositions generally have better overall properties than similar compositions made of inseparable soft core modifiers. The following is a description of the PVC / hard core composition and the PVC / inseparable soft core composition, which includes descriptions of the ideal hard core and inseparable soft core modifiers. PVC / hard core composition The ideal type of hard core modifier used in the operation of the present invention is disclosed in the above US Patent No. 3,793,402, the disclosure content of which is incorporated herein by reference. As described in this patent, the modifier resin contains multi-stage polymer particles. This resin, similar to the aforementioned separable soft core acrylic resin, is also made by a multi-stage sequential polymerization reaction. More specifically, these multi-level polymer particles include at least three levels of non-elastomeric first-level polymer, elastomer second-level polymer, and harder third-level polymer, each manufactured The monomers (comonomers) used in the first-grade resins are selected according to the above-mentioned US Patent No. 3,793,402, so that different levels or layers have the aforementioned non-elastic, elastic and hard properties. The non-elastomeric polymer formed in the first-stage polymerization reaction has a glass transition temperature of more than about 25. ° C. It is connected to the next stage with a glass transition temperature of about 25. ° C or lower. The ideal case is Monomer lower than about 10. ° C—22.— (please read the precautions on the back before writing this page) Binding · Binding-Line · This paper standard uses the Chinese National Standard (CNS) A 4 specifications (210X297 Public; li ·) Λ 6 Β6 Printed by the Beigong Consumer Cooperative of the Central Bureau of Economics of the Ministry of Economy V. Description of invention (21.) The elastomeric polymer made from the ingredients. And this elastomeric polymer itself X is connected to the next-stage polymer made of monomers, so that the glass transition temperature of the polymer is more than about 25. ° C, the most ideal case is at least About 60l ° C. The ideal particle is that the core layer and the outer layer are connected by grafting monomer of allyl methacrylate acrylate, and the core layer and the outer layer both contain the same one or the same acrylate matrix resin used for manufacturing the composition. Resin made of multiple monomers, this is a homopolymer of methyl methacrylate or an irregular copolymer of methyl methacrylate and Ci-c4 alkyl acrylate (the most ideal is ethyl acrylate), Or it may contain a multifunctional crosslinking monomer. When the matrix resin contains a copolymer of methyl methacrylate and ethyl acrylate, the ideal shape is that the core layer and the outer layer of the silver of the particle contain about 96.% by weight of methyl methacrylate and about 4 The weight percentage of ethyl acrylate, and the graft link monomer accounted for about 1% of the IE. According to the aforementioned U.S. Patent No. 3,793,402, there are many types of monomers that can be used to make the particles of the intermediate layer. Exemplary intermediate crumb is an irregular copolymer containing butyl acrylate, styrene, and about 2 weight percent; i;% of cross-linked and grafted knots. The product made by sequential gradation polymerization contains latex (1 atex), which is an aqueous composition in which multiple layers of polymer particles are dispersed. On the other hand, these particles are recovered from the latex by spray drying or by coagulation and drying. The mist drying should be carried out in the presence of a drying aid. This drying aid is Wru, an acrylate resin, which may be the same as or different from the matrix resin described here. Of course, the "drying aid" (drying-aid) resin should be compatible with the other ingredients of the resin composition, and it will not be used for the composition or its manufacture -23.- (Please read the precautions on the back before filling in this Page) Order _ This paper is printed on China's β Family Standard (CNS) Grade A 4 (210X297 gong). Printed by the Central Bureau of Economics, Ministry of Economic Affairs, Beigong Consumer Cooperatives 19930¾ Λ 6 _Β_6_ V. Description of the invention (22) Chemistry of the article , Physical or aesthetic properties cause adverse effects. The ideal "drying aid" resin is an irregular copolymer of methyl methacrylate and alkyl CQ-C4) acrylate, which contains about 9α to about 99.9% by weight of methyl methacrylate, and about 0. . 1 to about 10.% by weight of propionic acid vinegar, ideally propionic acid ethyl cool. The molecular weight of the copolymer can vary widely, for example, between about 95,000 to about 200,000 da 1 ton. The molecular weight is preferably between about 95,000 and about 110,000 dal ton. This resin can retain some particles as part of the acrylate matrix resin. It is true that other thermoplastic acrylate resins may be included in the composition to obtain the desired effect or as a processing aid (C Processing aids), for example, a polymer with a molecular weight of at least about 1,000.000. "Methyl methacrylate-ethyl acrylate copolymer. Other types of acrylate-based hard core resins with impact modifier added can also be used in the composition of the present invention, which can be used to replace the aforementioned US Patent No. 3,793,402 The ideal resin disclosed by No. or used to form a mixture with them. These resins used to improve the impact resistance of the articles made of the composition are multi-layer polymer particles, which are made by multi-stage sequential polymerization,- ¾ The hard (non-elastomeric) core should contain a large amount of homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and alkane propionate. Examples of these hard cores, add punch and improve The resin of the agent is disclosed in U.S. Patent Nos. 4,052,525 and 4,4 33,103, Japanese Patent Publication (kokai) No. 58-180514, and European Patent Application No. 270,865 One 24. A paper for the standard use of the "National Standard (CNS) A 4 specifications (210X297 mm) (please read the precautions on the back before writing this page).-^ 9990¾ Λ 6 Β6 Central Ministry of Economic Affairs Printed by the Bureau of Standards and Technology β-Consumer Cooperative V. Description of the invention (23.) The inventor of this case believes that the most widely used composition contains about 20 · to about 50.% by weight of PVC, about 17. to about 38 .% By weight of weather-resistant resin, and about 12 to about Π% by weight of hard core acrylate resin; ideally, it contains about 40. to about 50.% by weight of PVC, about 25. to about 35. The weather resistant resin by weight, and the hard core acrylate resin of about 15. to about 25. weight%. Inseparable soft core composition The ideal kind of inseparable soft core modifier used in the present invention is: It is disclosed in U.S. Patent No. 3,808,180, the disclosure content of which is hereby incorporated by reference. As disclosed in the patent, the modifier is a multilayer polymer particle. These resins, like the hard core resin mentioned above, are also made of It is made by sequential polymerization. More specifically, these multilayer polymer particles contain at least two layers, and the elastomer core is chemically connected to the hard thermoplastic resin layer. These multilayer particles can be made by emulsification polymerization, with elastomer It is a discrete phase, the core of which is a monomer mixture, which contains at least about 50.% by weight of alkyl- and / or aralkyl acrylates, and about to about 5% by weight of poly-unsaturated crosslinking monomers, About 0.05 to about 5% by weight of graft-linked comonomers, and about 0 to about 10.% by weight of hydrophilic monomers. Ideally, the monomer mixture of the elastomer phase contains about 0.1 to 1 Approximately 1% by weight of cross-linked comonomer, approximately 0.1 to approximately 1% by weight of graft-linked comonomer, approximately 0.5 to approximately 5% by weight of hydrophilic comonomer, and at least approximately 50% by weight of alkanes Base and / or aralkyl acrylate. -Once the elastomer phase has been polymerized, it should be within -25 of the initial polymerization mixture.- This paper is used in the standard B «Household Standard (CNS) A 4 specifications (210x297 male dragon) (please read the notes on the back first Matters can be written on this page) Pack · Book · Line < 19990 ^ Λ6 B 6 Printed by the Beigong Consumer Cooperative of the Central Bureau of Economics of the Ministry of Economy V. Description of the invention (24.) After the monomers are almost completely consumed, they must contain at least about 50. < ^-C4 alkyl methacrylate monomer mixture in the same emulsion, using polymerization to form a hard thermoplastic resin. The hard thermoplastic resins forming the composite material are equal, and the single system used for polymerization is added in such a way that almost all the hard phase materials are formed on the surface of the elastomer phase, and the minimum adhesion level (C minimum attaclment level), as shown below As mentioned, it reached about 20.%. In the manufacture of elastomer cores, alkyl esters of acrylic acid can be used, where alkyl refers to those containing 1 to about 15. carbon atoms, preferably 1 to about 8 carbon atoms, and 2 to The one with 8 carbon atoms is the best. Longer alkyl chains can also be used. Other acrylate monomers can also be used, the amount of which can reach about 50.% by weight, but it is lower than other inclusions, for example, aralkyl acrylate is used, in which the cyclic part contains 5, 6 or 7 Carbon atoms, which may or may not have other alkyl bridges (alkyl bridges), and the alkyl portion of the proparalkyl group may contain up to about 15. carbon atoms. In addition, substituted acrylates or methacrylates can also be used, including: alkylsulfanyl acrylates, such as ethylthioethyl acrylate (ethylthioethyl acylate), etc .; alkoxyalkyl acrylates, such as methyl Oxyethyl acrylate, etc. Copolymers formed with these acrylates, which may also contain up to about 40% by weight of one or more other monomers that can produce addition polymerization, such as styrene, methylstyrene, vinyl ether, amide , And ester, vinyl halide and vinylidene halide, etc. In a more ideal formulation, the elastomer core is made of the following ingredients: about 50. to about 80.% by weight of alkyl acrylate, of which the alkyl-26. Standard (CNS) A4 specifications (210X297 male dragon) (please read the precautions on the back before filling in this page) Binding-Order _ Printed by the Ministry of Economic Affairs, Central Bureau of Industry and Commerce, Co., Ltd. χ999υ j _____ Β6 ___ V. Description of invention (25 · ) Contains 2 to 4 carbon atoms, and preferably contains 4 carbon atoms; about 0.1 to about 10.% by weight of other acrylate monomers; about 0.1 to about 1% by weight of crosslinking monomers ; About 0.1 to about 1% by weight of graft linking monomer; about 0 to 5% by weight, ideally 0.5 to 5% by weight of hydrophilic monomer; and other parts are other non-acrylates Unsaturated monomers, but styrene, methylstyrene and halogenated styrene are more ideal. Ideally, some elastomers with a glass transition temperature lower than 25. ° C. More ideal is an elastomer with a glass transition temperature below 10. ° C, and a glass transition temperature below 25 °. <: Some of the elastomers are ideal. In all cases, these glass transition temperatures refer to the elastomer portion of the modifier and do not include any subsequently formed phases or other polymers that are physically or chemically attached to the elastomer particles. A particularly desirable elastomer core is from: about 50. to about 80. parts by weight of alkyl acrylate monomer, wherein the alkyl group contains 1 to 8 carbon atoms; about 0 to about 40. parts by weight Other ethylenically unsaturated monomers; about 0.05 to about 5 parts by weight of at least one polyunsaturated crosslinking monomer; about 0.05 to about 5 parts by weight of graft linking monomer; and about 0 to about 10. parts by weight A copolymer made of at least one hydrophilic monomer. The ideal acrylate elastic system of this type is that the polymer contains about 50. to about 100 parts by weight of alkyl acrylate monomer 1 in which the alkyl group contains 1 to 8 carbon atoms), about 1 to about 2 (λ parts Other acrylate monomers with a weight of ϋ, about 5 to about 20 parts by weight of other ethylenically unsaturated monomers (these other ethylenically unsaturated units are aromatic hydrocarbons, such as styrene and substituted styrene-27 .— (please read the precautions on the back before writing this page) -installation · This paper uses the Chinese standard (CNS) A4 specification (210X297 male dragon) as the paper standard. Λ 6 Β6 Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Printing 5. Description of the invention (26 ·)), about 0.1 to about 1 part by weight of at least one polyethylenically unsaturated crosslinking monomer unit, about 0.1 to about 1 part by weight of graft linking monomer, and From about 0.5 to about 5 parts by weight of at least one hydrophilic monomer. Acrylate elastomers include polyfunctional unsaturated monomers that can crosslink the elastomer, such as polyacrylates and polymethacrylates. Unsaturated monomer; and acid , Organic and inorganic bases and other electron donating groups (electronic donating group) produce ions and coordination cross-linking, and can be coordinated with suitable ionophilic reagents. Monoethylenically unsaturated monomers include: Polyacrylates and polymethacrylates of polyols, such as butanediol-diacrylate and butanediol-dimethacrylate, trimethylolpropane trimethacrylate, etc. ; Divinylbenzene and trivinylbenzene, vinyl acrylate and vinyl methacrylate, and other cross-linking monomers. As for the graft-linking monomers, compounds containing allyl (allyl group) are more ideal, especially It is an ethyl ester of ethylenically unsaturated acid. The most ideal ones are allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconic acid Ester, allyl acid maleate (al lyl acid maleate), acid fumaric acid propionyl alcohol, and acid itaconic acid allyl ester. When using hydrophilic monomers, methacrylate is preferred Compounds, especially methyl Acrylic amine and hydroxyalkyl ester. The hard thermoplastic resin phase of the inseparable soft core modifier is an acrylate polymer, and the polymer contains a large amount of c. 50. ~ ιοα%) alkyl methacrylate Ester units. Hot twist of these acrylate polymers—28.— (Please read the precautions on the back before writing this page) This paper is used in the 81 National Standard (CNS) A 4 specifications (210x297; ":") 19990¾ Λ 6 Β6 Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (27.) The variable temperature is greater than about 20. ° C, and more than about 50. ° C is more ideal. The hard thermoplastic resin part of the particles preferably contains: about 50. to about 100.% by weight of alkyl methacrylate, wherein the alkyl group contains 1 to 4 (preferably 1) carbon atoms; 0 to about 50.% by weight of one or more acrylic-comonomers, such as other alkyl- and aryl-methacrylates, alkyl- and arylacrylates, alkyl- and aryl-acrylic Amines, substituted alkyl- and aryl-methacrylates and acrylates, such as halogen, alkoxy, alkylthio, cyanoalkyl, alkylthiol esters and other substitutes; and 0 to about 40% by weight of other unsaturated monomers, including acrylonitrile and methacrylic acid, styrene monomers and substituted styrene monomers, vinyl esters, vinyl ethers, vinyl amides, vinyl groups Ketones, vinyl halides, vinylidene halides, and olefins. Generally, if a softer comonomer system is used, it will be used in smaller amounts to retain the desired hard characteristics. Ideal monomers that can be used to make acrylate polymers include: methacrylic acid and alkyl esters of acrylic acid, where the alkyl group contains 1 to 4 carbon atoms. The ideal cycloalkyl esters of methacrylic acid and acrylic acid are those containing 4 to 14. carbon atoms in the cycloalkyl group. Non-separable soft core modifiers can be made from suspension or emulsification polymerization steps using a multi-stage or sequential technique. In the simplest form, an elastomer phase is formed in the first stage, and a hard thermoplastic resin phase is formed in the second stage. The elastomer phase or the hard phase can also be polymerized in sequence. Other types of acrylate-based, non-separable soft core impact modifier resins can replace the first reason described in the aforementioned US Patent No. 3,808,180. 29 (Please read the precautions on the back before writing this page) This paper size The SB Family Sample Standard (CNS) A4 specification (210X297); a :) Printed by the Ministry of Economic Affairs, Central Bureau of Precision Industry, Beigong Consumer Cooperative V. Description of the invention (28.) Think resin or form a mixture with it, and use it Within the composition of the invention. As mentioned above, these resins used to improve the impact resistance of articles made of the composition are also multilayer polymer particles, which are made by multi-stage sequential polymerization. Examples of these inseparable soft core modifiers are shown in US Patent Nos. 4,096,202, 4,18〇, 529, 4,508,875, and 4,730,023, and Japanese Patent Publication (kokai) No. 59-124916 Number. The present inventor believes that the most widely used composition contains: about 20. to about 50. wt.% PVC, about 17. to about 38. wt.% Weatherable resin, and about 12 to about 33. wt.% An inseparable soft core modifier. However, those containing about 40. to about 50.% by weight of PVC, about 25. to about 35.% by weight of weather-resistant resin, and about 15. to about 25.% by weight of an inseparable soft core modifier are even more ideal. Description of certain entities of the present invention In certain applications, it is advisable to add other resins to the PVC / separable soft core composition and PVC / hard core composition, which can further improve the impact resistance of these compositions. For example, when the total thickness of plastic composite materials used is relatively thin-such as reaching 1 mm or less, it is advisable to use more impact modifiers. At this time, the impact modifier used is preferably a multi-layer, sequentially made acrylate resin polymer, which has an elastomer (soft) core and one or more resin layers on the outside, without or very Less likely to form a separation (if it does, it will be less than about 10.%). The ideal non-separable soft core modifier is recommended to be disclosed in the aforementioned U.S. Patent No. 3,808,180. Other types of acrylic—30.— Λ 6 Β6 (Please read the precautions on the back before writing this page) Binding. Binding, line, this paper is used in the standard a «Home Sample Standard (CNS) A 4 specifications (210X297 Gonglong) 19990¾ Λ 6 Β6 Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Invention description (29.) Ester-based inseparable soft core modifiers, such as those mentioned above, can be used to replace the aforementioned US patents The ideal resin disclosed in No. 3,808,180, or mixed with it. The amount of the non-separable soft core modifier is generally not more than about 5% by weight of the composition, for example, it is about 1 to about 5% by weight in the composition. The preferred amount is between about 1.75 and about 3.5% by weight. In applications where the composition contains a separable soft core improver, the composition can be easily made from a premix. The premix contains this resin and the PVC components are added sequentially and can be included in the composition Other ingredients added. For PVC / separable soft core compositions, the premix may contain about 9Q to about 98.% by weight of separable soft core modifier and about 2 to about 10.% by weight of non-separable soft core Core modifiers; more ideal dosage ranges are between about 94. to about 9% by weight and between about 2 to about 6% by weight. As for the hard core composition, the premix contains about 30. to about 70. wt.% Of a thermoplastic resin with weather resistance (except PVC), about 20. to about 60. wt.% Of the hard core modifier and About 1 to about 10. Non-separable soft core modifier with a weight of ϋ ·%; the ideal dosage ranges are about 55. to about 65. wt%, about 35. to about 45. wt%, and about 2 To between about 5% by weight. Each entity of the composition of the present invention may contain other ingredients, such as; dyes and pigments; lubricants; ultraviolet rays and heat stabilizers; processing aids; inorganic materials; smoothing agents; heat distortion modifiers; flame retardants; And Yanyi 31. 1. (Please read the precautions on the back before filling out this page) Binding-Order _ This paper is used in the standard Η Β home standard (CHS) A 4 specifications (210X297 public) The Ministry of Economic Affairs Central Bureau of Quarantine Printed by Beigong Consumer Cooperatives 19990¾ Λ 6 __Β6_ V. Description of the invention (30.) Smoke suppressants. Generally, the total amount of these optional components added does not exceed about 10.% by weight of the composition, for example, about 4 to about 8% by weight of these components are added. It is believed that the most versatile use of the composition of the present invention is as a covering blank in composite materials, where the layer covered by the covering blank is PVC, which includes chlorinated PVC and homopolymers and copolymers of vinyl chloride, as above Said. The covering blank of the present invention can be used to provide other structural plastics with desired properties. These structural plastics include, for example: plastics made from other vinyl halide polymers; acrylate resins; propylene halide / butadiene / benzene Ethylene (ABS) resin; polystyrene; blend of ABS and PVC; PVC and acrylate-imide copolymer—such as methacrylate-glutamine copolymer or acrylate / maleimide Blends of imine copolymers; polyolefins, such as polypropylene; styrene / (meth) acrylate and C meth) acrylate multi-stage polymers; polyamide, polyamide-multistage polymerization Blends, such as polyamide / ABS; polyamide / polycarbonate blends; styrene / acrylonitrile copolymers and styrene / acrylonitrile-multi-stage polymer blends; ethylene / propylene / bis Ethylene rubber and styrene / acrylonitrile copolymer or polypropylene blend; "-methylstyrene / acrylonitrile," -methylstyrene / styrene / acrylonitrile, α-methylstyrene / methyl Methyl acrylate / ethyl acrylate; polycarbonate, polycarbonate-ABS blend, polycarbonate-poly Polymer blends; polyesters, such as polyterephthalic acid-ethylene glycol ester, polyterephthalic acid-butylene glycol ester, polyterephthalic acid-butylene glycol ester-polycarbonate blend, Polyterephthalate-butylene glycol-multi-stage polymer blend, polybutylene terephthalate-polytetrahydrofuran, polychloroethylene—32.— (please read the precautions on the back before filling Nest Page) Binding · Ordering-This paper scale is printed with 8 Chinese Standards (CNS) A4 specifications (210X297 Gongjie) __ 136_ Λ 6 Printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economy .. V. Description of Invention ( 31 ·) Olefin-multi-stage polymer blend, polyvinyl chloride- (meth) acrylate blend, chlorinated polyvinyl chloride, acrylonitrile / (meth) acrylate-multi-stage polymer blend Compound, acrylonitrile / C meth) acrylate / styrene, polycaprolactone, polyacrylic acid poly (meth) acrylate, polyacetal, impact polystyrene (HIPS) ), Styrene / maleimine, styrene / maleimide, polyvinylidene f luo ride, polyethylene ethylene__multi-stage polymer blend, fiber , Polyamide - acyl imine (Polyamideimide), poly ether ester (polyetherester), polyether ester Amides (polyetheresteramide) and polyacid Amides (polyetheramide) 'polyphenylene oxide C polypheny lene oxides) and poly Yan. Blends can also be made from other polymer systems, including: polyphenylene sulfide (C polyphenylene sulfide), polyphenylene oxide, polymagnetic, polyphenylene oxide-styrene blend, polyphenylene oxide -Impact-resistant polystyrene blends, polyvinyl chloride, polyvinyl chloride / C formazan) acrylonitrile, polyvinyl chloride / (meth) acrylate, polyvinyl acetate, polyacid_ (polyetheretherketone) , Polyimide (C poiyetherimide), thermoplastic polyimide, polyolefins such as polyethylene, polypropylene and co-cigarettes [copo i yo 1 ei ins ", and its other polymers. Random or bl ck copolymers with different functionalities can also be used, and blends of three or more components can be made from any combination of these types of polymers as The substrate of the invention covers the blank. (In the copolymers exemplified above, and in the case used by general practitioners, the "/" symbol represents a copolymer made by copolymerizing various components, on the other hand, the blend and the mixture are -33 .- (Please read the precautions on the back before filling in this page) Binding · Order _ This paper uses the Chinese National Standard (CNS) A 4 specifications (210X297 male dragon) χ9990 ^ Λ 6 Β 6 Ministry of Economic Affairs Central #quasi Printed by the Bureau ’s Consumer Cooperatives 5. The description of the invention (32.) is indicated. Moreover, the term “methyl” is shown in “meth” acrylate, for example, as it is widely used in traditional industries. It contains "acrylate or methacrylate".) Therefore, a wide variety of structural resins, generally known as "rigid thermoplastics" (rigid thermoplastics) in the industry, can be used as a base layer or Matrix. These structural plastics can be used alone, but with the covering blank of the present invention as a structural plastic, or more than one type can be used at the same time, or a blend of two or more polymers or copolymers can be used to form a structural plastic Blend. If more than one matrix layer is used, an adhesive (or "tie") layer can also be used. And in polymers, construction plastics and blends, it may contain acrylate or (meth) acrylate / butadiene / styrene C (MBS)) or ethylene / propylene / diene ("EPDM") polymerization Impact modifier. In addition, the following materials can be added to it. The covering blank of the present invention can also be used as the surface material of foamed plastic, such as foamed PVC and foamed ABS. When covering the blank, the composition should not be exposed to ultraviolet light and visible light ( < 520 nm) penetration. The sample of the composition within the scope of the present invention is opaque C (for example, the opacity to light is at least 95.%). If necessary, opacifiers and / or pigments can be added to the composition to make it opaque. It must be understood that the composition of the present invention can be used where the composition is not compatible with the underlying plastic material for construction, such as polyolefin or polystyrene. This type of composite material can be effectively produced by bonding mutually incompatible materials by adding a mutually compatible adhesive between the stirrup cover material and the structural plastic. 1.34 · — (Please read the precautions on the back and then fill out this page) The standard of this paper is the Chinese Standard of Family Support (CNS) f 4 (210x297 public address) x999〇 ^ Λ 6 B 6 Central Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 5. Description of the invention (33.) The resin composition of the present invention can be pressed, molded, formed, or pressed using conventional equipment to form a monolithic sheet or film, including stirrup cap blanks. The composition can also be made according to conventional techniques. Standard lamination or coextrusion technology and equipment can be used in plastics for construction, such as arms, bi-extrusion and co-calendering In addition, the aforementioned resin composition is added to the terminal; in addition, solution casting methods (solution casting methods) can also be used to make the stacking material of the present invention. It is more desirable to use co-extrusion of separate feedstock to make the sheet and sheet-like composite material of the present invention. Here, the term "divided feed co-extruded legs" refers to a process in which the resin as the first plastic material (Yuan Ru, plastic material for construction) is fed and used as the second plastic material (Bao Ru, The resin feed material covering the blank material) is heated in different streams to a molten state, and then injected into the divided feed zone (feedb 1 〇ck), where the streams are brought together for face-to-face surface contact to form a double layer Stream (two-ply stream), and then injected into a sheet die (sheet die), so that the two-layer stream under the condition of laminar flow (1 aminar f 1 ow) distributed along the side into a double-layer sheet, the molten resin of the sheet When the layers flow out of the mold, they are in face-to-face surface contact, and then the formed two-layer sheets are cooled and solidified to form a composite material. Each layer of the sheets is integrated with each other by the cured resin constituting the sheets. As is known in the industry, the split feed co-extrusion process can be used to make more than two layers of Pu sheets. The split feed zone used in the design can accommodate more than two resin streams, or it can be used in Separate the two strands of resin in the feeding area and separate them in the majority of the conversion layer C alternating -35.- (please read the precautions on the back before filling in this page) Binding · Threading · This paper standard uses the Chinese National Standard (CNS) A 4 specifications (210x297 public address) Λ 6 Β 6 V. Description of the invention (34.) (Please read the notes on the back before writing this page) 1 ayers). Gongxiaot Cooperative prints the cover blank composition of the present invention. Examples of other uses include automotive applications, such as decorative exterior trim, molding side trim, and molding side trim. Quarter panel trim panels (quarter panel trim panels), fender extensions, shutters, rear panel, light truck cover, rear view mirror seats, instrument knobs, inner or outer door headline grips C snap -on) and other fasteners, accessories for trucks, buses, campers, vans and public transportation vehicles, pillar extensions (b-pi 1 lar extens ions), etc .; And tools, such as lawn and garden utensils and fences, mobile homes Bathroom fixtures, yacht components, outdoor components for mobile homes, lawn furniture such as chairs and table stands, piping and pipe end covers, luggage, showers for mobile homes, toilet seats, signage plates, warm water pools, air conditioners and heat pump components , Bead-molded picnic coolers, picnic trays and pots, and waste cans; venetian blind components; sporting goods, such as windsurfing boards, sailing boats, water skis; water pipe parts such as toilet parts; and others Building components, these components include building templates, door templates, shutters, shutters, mobile house walls, courtyard doors, peripheral accessories, window jackets, roof window frames, skylight frames, end covers for sunroofs, shading and parking Roof etc. These bills exemplify the application type and application of the covering blank material of the present invention. Other ingredients that can be added to the composition of the present invention are concentrated colorants, such as dyes and pigments, lubricants, ultraviolet stabilizers, heat stabilizers, antioxidants, heat distortion temperature modifiers, antistatic agents ， Matting agent 36. A copy of k sheets of standard B «Home Standard (CNS) A 4 specifications (210x297 male dragon) Λ 6 13 6 Printed by Beigong Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs < 35 ·) (matting agent), flame retardant, and processing aid. Normally, the total amount of the selectively added ingredients generally does not exceed about 0.5% by weight of the composition. For example, about 1 to about 5 m% of these ingredients are used. These optional ingredients can be added to the covering blank composition or construction gel, or both. In addition, base materials such as wood fiber, carbon fiber, and glass fiber may also be added to the composition of the present invention as needed, but it is expected that the weather resistance of these special base materials will be poor. Furthermore, glass particles and some inorganic substances such as calcium carbonate, talc, titanium dioxide, barium sulfate, etc. can also be added to the composition of the present invention as needed. Normally, the total amount of these selected Sichuan materials will not exceed about 15.5% by weight in the covering blank, and will not exceed about 65.% by weight in the plastic or matrix for construction. The following examples are used To illustrate the invention. EXAMPLES The composition of Example 1 contains a mixture of matrix resin, hard core, and impact modifier resin. Example 1-Hard core composition The composition of Example 1 is made of a mixture of three different matrix resins of the following codes (A), (8) and (C). Matrix resin (Matrix resins) (A) This matrix resin is PVC, its source is a fully formulated PVC composition, containing the following ingredients, its dosage is expressed in parts per hundred (phr) . -37.- (Please read the precautions on the back before writing this page) This paper uses the Chinese National Standard (CNS) A 4 specifications (210X297 male dragon) 19990½ Λ 6 B 6 V. Invention description (36. ) Cheng_ί & _ dosage, phr (1) PVC, K69 100 ⑵ contains 80.% by weight of butyl acrylate core and 20.% by weight of inseparable soft core of 5 methyl methacrylate shell, impact modifier Resin ⑶ tin carboxylate stabilizer 3 ⑷ lubricant mixture-1.2 phr calcium stearate, 0.4 2.35 phr paraffin wax, 0.15 phr polyethylene wax, and 0.6 phr lubricant processing aid (high molecular weight acrylate / styrene polymerization ) Acrylic vinyl resin ⑸ Melting aid-high molecular weight acrylate processing aid 1 ⑹ Triazole ultraviolet stabilizer 0.17 (please read the precautions on the back before filling this page) < Printed by the Beigong Consumer Cooperative of the Central Bureau of Economics of the Ministry of Economic Affairs The above PVC composition is made by blending various ingredients in a high-strength mixer. ⑻This matrix resin is an irregular copolymer containing 91.% by weight of methyl methacrylate and 9% by weight of ethyl acrylate and having a molecular weight of approximately 95,000 dal ton. This copolymer is made in a continuously flowing stirred tank reactor in the presence of organic peroxides. (C) This matrix resin is an irregular copolymer containing 91.% by weight of methyl methacrylate and 9% by weight of ethyl acrylate and having a molecular weight of approximately 100,000 dal ton. This copolymer is made by emulsification polymerization. Seed is formed in the system first, and then the rest of the polymer is formed by the reactor / batch method. The impact modifier resins used in the composition of Example 1 are as follows-38.-Threading-This paper uses the Chinese a standard (CNS) A 4 specifications (210x297 mm). Printed by the consumer cooperative 3l99 tear λ6 _Β6 _ V. Description of the invention (37.) Hard core, impact modifier resin The modifier resin contains three layers of polymer particles, which is based on the multi-level, according to the aforementioned US Patent No. 3,793,402 Made in sequence. The core layer and ^ are each an irregular copolymer containing approximately 96. wt% methylmethacrylate and 4 wt% ethyl acrylate, and the core layer copolymer forms a graft link with 0.2 wt% allyl methacrylate . The intermediate layer is an irregular copolymer containing about 81% by weight of butyl acrylate and 18.% by weight of styrene. It forms a grafted connection core, middle and intermediate with about 1% by weight of allyl methacrylate The proportions of the outer layer are 35.%, 45.% and 20.% respectively. The particle size of the modified resin is between about 250 to about 350 nm. Bonding of resin components_ The above various resin components are blended in the following manner to form the composition of Example 1, which contains the following components in the amounts shown in the table. (Please read the notes on the back before filling this page) The composition of Example 1 is _ parts by weight PVC resin 44.8 MMA / EA resin (B) 25 ri ly 'V \ ;;'-l ^ MA / EA 、 Wg (C) 5 <-.. t τ Hard core, impact modifier resin 20 Inseparable soft core, impact modifier resin 2.2 Tin carboxylate stabilizer 1.4 Lubricant 1.1 Melting aid 0.4 Ultraviolet stabilizer 0.1 -39.- This paper size While using China ’s “CNS” f 4 specification (210x297 public address) 19S902 Λ 6 Β 6 Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy V. Invention description (38 ·) When manufacturing the composition of Example 1 It is to prepare the mixture of matrix resin (C), hard core and impact modifier resin, and then mix it with matrix resin ⑻. At this time, in a tank equipped with a stirrer, 20.wt% latex (containing 50.wt% of the aforementioned resin (C)) and 80 · wt% impact modifier resin are mixed and blended Homogenize to make a mixture. The blend was spray dried and separated into free flowing powder. Take 50. parts by weight of this mixture, and manually mix with 50. parts by weight of matrix resin ⑻, to make 50.% by weight of matrix resin ⑻,〗 0.% by weight of matrix resin (C), and 40 . A composition of% by weight impact modifier resin. This composition is melt blended in a conventional extruder and extruded into pellets. These plastic granules and the fully formulated PVC composition are mixed in a polyethylene bag according to a weight ratio of 50./50. Here, they are mixed by manual stirring. Then, the dry blend was added to a single screw extruder (25. mm diameter X 600 mm effective spiral length) to be melted and dispersed and mixed. Both the barrel zone and the die zone are controlled at 196 ° C. The strips melted and extruded are cooled in water and then cut into pellets. The following examples are used to illustrate compositions similar to those in Example 1, but the contents of various components are different. Example 2-Hard core composition The composition of this example was made using the following ingredients in different proportions. The resulting granular composition contains the following ingredients: -40.— This paper uses the standard size (CNS) A4 specification (210X297 male dragon) (please read the precautions on the back before filling in This page) Binding · Order_ 199902 Λ 6 Β6 V. Description of the invention (39.) _ Composition of Example 2 _§_ Weight% PVC 22.4 ΜΜΑ / ΕΑ matrix resin (Β) 37.5 ΜΜΑ / ΕΑ matrix resin (C ) 7.5 Hard core, impact modifier resin 30 Inseparable soft core, impact modifier resin 1.13 Tin carboxylate stabilizer 0.7 Lubricant 〇_52 Melting aid 0.2 Ultraviolet stabilizer 0.05 The composition of Example 2 consists of a matrix The plastic pellets of the resin and the PVC composition shown in Example 1 are prepared by mixing at a weight ratio of 75/25. Examples 3 and 4-Hard core composition The following two examples exemplify compositions similar to Examples 1 and 2, but in which only one type of acrylate resin is used as the matrix resin, this is the above resin (C) . The composition contains the following ingredients: (Please read the precautions on the back before writing this page) Printed by the Ministry of Economic Affairs, Central Bureau of Economic and Technical Affairs, Beigong Consumer Cooperatives-41.- This paper is used in the national beta (CNS) A 4 specifications (210X297; ¢) ^ 9990¾ Λ 6 Β6 V. Description of the invention (40.) Dosage, weight% Composition Example 3 Example 4 PVC 44.8 22.4 ΜΜΑ / ΕΑ matrix resin (C) 30 45 Hard core, impact Modifier resin 20 30 Inseparable soft core, impact modifier resin 2. 2 1.13 Tin carboxylate stabilizer 1.4 0.7 Lubricant 1.1 0.52 Melting aid 0.4 0.2 Ultraviolet stabilizer 0.1 0.05 (Please read the precautions on the back side first (Write this page) The composition of Example 3 printed by the Ministry of Economic Affairs, Central Bureau of Industry and Fisheries Cooperative Cooperatives is composed of 6Q parts by weight of the MMA / ΕΑ type latex shown in Example 1 and 40. parts by weight of hard core, impact The modifier resin (the source of which is also a latex) is made by blending. The resulting homogeneous blend is subsequently spray dried. 50. parts by weight of the formed resin powder was mixed with 50. parts by weight of the PVC composition, and granulated as in Example 1. The composition of Example 4 was prepared in the same manner as in Example 3, except that 75. parts by weight of resin powder was mixed with 25. parts by weight of the PVC composition. The following examples also illustrate the composition of the present invention, but a soft core and an impact modifier resin are used. Example 5-Separable soft core composition The composition of this example contains a separable soft core resin similar to that shown in Example 1 of the aforementioned US Patent No. 4,14 1,935, as disclosed in the patent In addition, the resin is composed of the following ingredients, according to the amount shown, in the fourth grade in order -42.- This paper scale is used in the middle of the sleep Η Jiayuban (CNS) A 4 specifications (210X297 male dragon) Λ 6 U6 five 3. Description of the invention (41.) Made by the joint venture: the first level-25 · [butyl acrylate (BA) / 1,3-butanediol diacrylate (BDA) / allyl methacrylate (ALMA) -98.5 / 1.0 / 0.5]; second level-25. [BA / methacrylate (MA) / ALMA — 40/60 / 0..5]; third level-** 25 · [methylpropylene Methyl acid ester C MMA) / BA / n-dodecyl mercaptan (n-DDM) — 90/10 / 0.5]; fourth level one 25. [MMA / BA / n-DDM — 90. / 10 · / 1.5〕. The recovered resin is in the form of latex, and its solid content is about 45% by weight. The composition of Example 5 contains the following ingredients: Ingredient weight% PVC 44.8 Separable soft core modifier resin 50 Soft core, impact modifier resin 2.2 Tin carboxylate stabilizer 1.4 Lubricant 1.1 Melting aid 0.4 Ultraviolet stabilizer 0.1 ( Please read the precautions on the back before filling out this page) Binding · Order-Line · The Ministry of Economic Affairs Central Standards Bureau Beigong Consumer Cooperative Printed Example 5 The composition is separated from the f soft core, improver resin and the above complete The PVC composition of the formula is made in a polyethylene bag according to a 50./50. Weight ratio and mixed by manual stirring. Subsequently, this dry blend was added to a single-screw extruder (25. mm diameter X 600 mm effective spiral length) to be melted and dispersed and mixed. Both the body area and the mold area are controlled at 180 ° C. The melt-extruded strips are cooled in water and pelletized. In the various compositions of Examples 1 to 5, add 21.8 weight-43.-This paper standard is used in the middle of the family standard (CNS) A 4 specifications (210 X297 public address) 19990¾ Λ 6 Β 6 Central Ministry of Economic Affairs Printed by the Pui Pui Consumer Cooperative
五、發明説明（42.) 量 ％ 褐色顔料 C Cibe Geigy 公司之 Chromophtha 1 5R )、 7.2重量％紫色染料、及71.重量％丙烯酸酯樹脂分散助劑 之一種褐色濃縮液。濃縮液的添加量係於每100份重量之 實施例1至5所示之各種組成物中，加入4份重量之濃縮 液。以形成之組成物作爲PVC樹脂基質上之覆蓋坯料，這 些組成物各含有下列成份。 PVC構造用塑膠之成份 用量，Phr PVC, K69 (Geon 103EPF76) 100 不可分離的軟質核心、衝擊改良劑樹脂 5 (Rohm and Haas 公司之 KM-334) Ti02顏料 4 CaC03塡料 5 潤滑劑混合物一 1.9 phr硬脂酸弼，1.3 phr 3·5 石蠟，及0.3 phr丙烯酸乙烯樹脂 硫醇錫安定劑 I·1 丙烯酸酯加工助劑樹脂 Q·5 上述組成物係由各種成份在高強度混合器內予以摻合 而製成。 複合材料係由PVC構造用塑膠組成物與實施例1至5 之覆蓋坯料組成物，以傳統的分隔給料共擠壓方式製成。 將適當量的加料注入個別擠壓機之給料斗（hopper )內。 供PVC構造用塑膠組成物用之擠壓機爲一種25.毫米圓錐形 反向旋轉之雙螺桿擠壓機。而供覆蓋坯料組成物用之擠壓 II I (請先閲讀背面之注意事項再填寫本頁) 裝- 訂 線- 本紙悵尺度边用中H a家標準（CNS)甲4規格（210x297公釐） 經濟部中央標準局貝工消費合作社印製 上 999ί):’> λ 6 __ Β6 _ 五、發明説明（43.) 機則爲25.毫米單螺桿擠壓機。熔融流股之滙流係藉一擁有 3.2毫米X 3.2毫米細孔之分隔給料區爲之，此細孔使熔 融流股垂直地對準供構造用塑膠組成物用之擠壓機的模具 ，藉此使覆蓋坯料組成物流動並分佈成4吋寬的複合材料 ，隨後再利用空氣冷却並予切成試驗用之長度。 分隔給料區溫度爲160〜177 °C，而模具溫度爲177 〜193 °C。與覆蓋坯料組成物用之擠壓機有關的各項溫度 如下. * 本體溫度，°C 覆蓋坯料組成物 熔融溫度，°c 第1區第2區第3區 (請先閲讀背面之注意事項再艰寫本頁) 實施例 1、2、3 及 4 205 188 189 193 實施例 5 196 177 182 188 經過擠壓之複合材料，其覆蓋坯料厚度介於大約5至 大約10.密爾（0.125至0.25毫米）之間，而PVC構造用 塑膠層之厚度則介於大約30.至大約35.密爾（0.76至0.90 毫米）之間，整個複合材料之總厚度係介於大約40.至大約 45.密爾（1.0至1. 14毫米）之間。這些複合材料係爲住宅 外壁板工業使用之典型材料。 以下表1顯示由實施例1、2及5之覆蓋坯料組成物 製成之這些覆蓋坯料/ PVC基質複合材料的未加浮雕樣品 之衝擊強度。 —45· 一 本紙張尺度逍用中S a家標準(CNS)甲4規格(210x297公址) 19990^ Λ 6 Β6 經濟部中央櫺準局員工消費合作社印製 五、發明説明（44.) 表 1 覆蓋坯料組成物 衝擊強度（ASTM D4226A-85), Joule/mm 實施例 1 13.5(50.5) 實施例 2 9.8(^1.5 ) 實施例2 (第二樣品） 10.5 ( 5 2.2 ) 實施例 5 13.4((51.6) 住宅外壁板之工業標準，最低値爲8.9 Joule/mm ( 未加以浮雕）。PVC基質C無覆蓋坯料）得到之數値，一 般介於大約10.〜R Joule/mm厚度的範圍。因此，可知複 合材料之衝擊強度對其意旨運用的場合業已足夠，且事實 上，覆蓋坯料亦不致對它造成不利的影響。 以下表2顯示以表2之覆蓋坯料組成物根據本發明所 製成之複合材料的顔色保留特性。經過共擠壓之覆蓋坯料 / PVC 基質複合材料，利用 ASTM Method G26，Method A之氙弧/耐候試驗法，使用BH-型裝置予以測試。照射 源係使用S型硼矽鹽過濾器（內、外相同），設定於0.35 W/w2，波長帶爲340 nm。黑板溫度（black panel temperature )設定於63.°C ;週期爲102分鐘光線，18.分 鐘光線+水噴霧（16. °C ± 5 °C );乾燥週期（dry cycle ) 設定於50. %相對濕度。Hunter顔色總變化之差異（Delta E )係依ASTM Method D 2244的步驟，以積分球形比色 計（Hunter D25-9 )予以計算。在排除反射成份的情況 下，對樣品加予評估。 一 46. (請先閲讀背面之注意事項再塡寫本頁) 本紙ίί·尺度边用中困困家楳準（CMS)中4規格（210x297公此) ^993(,¾ 五、發明説明（45.) Λ 6 Β6 表 2 在氙弧/耐候試驗（ASTM G26 )中V. Description of the invention (42.) A brown concentrate of brown pigment C% Chromophtha 1 5R (C Cibe Geigy), 7.2% by weight purple dye, and 71.% by weight acrylic resin dispersion aid. The amount of the concentrated liquid added was 4 parts by weight of the concentrated liquid per 100 parts by weight of the various compositions shown in Examples 1 to 5. The formed compositions are used as covering blanks on the PVC resin substrate. These compositions each contain the following ingredients. The amount of plastic components used in PVC construction, Phr PVC, K69 (Geon 103EPF76) 100 Inseparable soft core, impact modifier resin 5 (KM-334 from Rohm and Haas) Ti02 pigment 4 CaC03 base material 5 Lubricant mixture-1.9 phr stearic acid, 1.3 phr 3 · 5 paraffin, and 0.3 phr acrylic vinyl resin thiol tin stabilizer I · 1 acrylate processing aid resin Q · 5 The above composition is composed of various ingredients in a high-strength mixer Made by blending. The composite material is made of a plastic composition for PVC construction and the cover blank composition of Examples 1 to 5 in a conventional separate feed co-extrusion method. Inject the appropriate amount of feed into the hopper of the individual extruder. The extruder for the plastic composition for PVC construction is a 25. mm conical twin-screw extruder with reverse rotation. Extrusion II I for covering the blank composition (please read the precautions on the back before filling in this page) Binding-Binding-This paper is used in the Ha Ha standard (CNS) A 4 specifications (210x297 mm ) Printed on 999ί by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs: '> λ 6 __ Β6 _ 5. Description of the invention (43.) The machine is a 25. mm single screw extruder. The confluence of the molten stream is obtained by a separate feed zone with 3.2 mm X 3.2 mm fine holes that vertically align the molten stream with the mold of the extruder for the plastic composition for construction, thereby The cover billet composition was flowed and distributed into a 4 inch wide composite material, which was then cooled with air and pre-cut to the test length. The temperature in the separate feed zone is 160 ~ 177 ° C, while the mold temperature is 177 ~ 193 ° C. The various temperatures related to the extruder for covering the blank composition are as follows. * Body temperature, ° C Covering the melting temperature of the blank composition, ° c Zone 1 Zone 2 Zone 3 (Please read the precautions on the back first (This page is hard to write) Examples 1, 2, 3, and 4 205 188 189 193 Example 5 196 177 182 188 Extruded composite material, covering the blank thickness between about 5 to about 10. mil (0.125 to 0.25 Mm), and the thickness of the plastic layer for PVC construction is between about 30. to about 35. mil (0.76 to 0.90 mm), the total thickness of the entire composite material is between about 40. to about 45. Mill (1.0 to 1.14 mm). These composite materials are typical materials used in the residential exterior siding industry. Table 1 below shows the impact strength of the unembossed samples of these covering blanks / PVC matrix composites made from the covering blank compositions of Examples 1, 2 and 5. —45 · A paper standard for the use of Sa Family Standards (CNS) Grade 4 (210x297 public address) 19990 ^ Λ 6 Β6 Printed by the Employee Consumer Cooperative of the Central Bureau of Economic Development of the Ministry of Economy V. Description of Invention (44.) Table 1 Covering blank composition impact strength (ASTM D4226A-85), Joule / mm Example 1 13.5 (50.5) Example 2 9.8 (^ 1.5) Example 2 (second sample) 10.5 (5 2.2) Example 5 13.4 ( (51.6) The industry standard for residential exterior siding, the minimum value is 8.9 Joule / mm (not embossed). The PVC matrix C is not covered by the blank). The value obtained is generally in the range of about 10. ~ R Joule / mm thickness. Therefore, it can be seen that the impact strength of the composite material is sufficient for its intended application, and in fact, the covering blank will not cause adverse effects on it. Table 2 below shows the color retention characteristics of the composite material made according to the present invention with the cover blank composition of Table 2. The co-extruded covering blank / PVC matrix composite material was tested using the BH-type device using ASTM Method G26, Method A's xenon arc / weather resistance test method. The irradiation source is an S-type borosilicate salt filter (the same inside and outside), set at 0.35 W / w2, and the wavelength band is 340 nm. The black panel temperature is set at 63. ° C; the period is 102 minutes light, 18. minute light + water spray (16. ° C ± 5 ° C); the drying cycle (dry cycle) is set at 50.% relative humidity. The difference in total Hunter color change (Delta E) is calculated according to the steps of ASTM Method D 2244, using an integral spherical colorimeter (Hunter D25-9). In the case of excluding reflective components, the sample is evaluated. 1. 46. (Please read the precautions on the back before writing this page.) This paper is for 4 specifications (210x297) in the CMS standard (210x297) ^ 993 (, ¾ V. Invention description ( 45.) Λ 6 Β6 Table 2 In xenon arc / weather resistance test (ASTM G26)
覆蓋坯料組成物 經過下列小數後之總顔色變化（DELTA E )値 500 2000 3500 5000 實施例1 1.15 2.9 3.9 5-8 if 2 0.75 1·7 2.7 5.5 ” 5 0.74 1.9 2.5 2.8 PVC系及其他覆蓋坯料材料如樹脂中含有苯乙烯/丙 烯腈（SAN )聚合物或共聚物、SAN接枝聚合物或共聚物 、以及含有前述SAN聚合物與其他聚合物之摻合物者，通 常其DELTA E値，在2000小時後爲大約2至大約3之間 ，4000小時後爲大約4至大約11.之間，而在5000小時後 則爲大約4至大約11.之間。 綜而言之，本發明提供一種能有效地作爲覆蓋坯料之 組成物，它具有優越的性質，特別是具有優越的耐候性質 者。 (請先閲讀背面之注意事項再填寫本頁) 裝< 訂· 經濟部中央楳準局貝工消費合作社印製 本紙張尺度边用中H a家楳準（CNS)甲4規格（210x297公¢)The total color change of the covering blank composition after the following decimals (DELTA E) value 500 2000 3500 5000 Example 1 1.15 2.9 3.9 5-8 if 2 0.75 1 · 7 2.7 5.5 ”5 0.74 1.9 2.5 2.8 PVC series and other covering blanks Materials such as resins containing styrene / acrylonitrile (SAN) polymers or copolymers, SAN graft polymers or copolymers, and blends containing the aforementioned SAN polymers and other polymers, usually the DELTA E value, It is between about 2 and about 3 after 2000 hours, between about 4 and about 11. after 4000 hours, and between about 4 and about 11. after 5000 hours. In summary, the present invention provides A kind of composition that can be effectively used as a covering blank, it has superior properties, especially those with superior weather resistance. (Please read the precautions on the back before filling out this page) Install &Order; Beigong Consumer Cooperative printed this paper on the standard side of the Ha Family Standard (CNS) A 4 specifications (210x297 g)