509626 五 、發明説明（ Λ7 B7 參考 本申請案件聲明美㈣時專心請案於而年 申请，序號60/049,822的利益。 月領域 2發，是關於多層氟聚合物薄膜，且更明確來説是， 。聚氯一 &乙晞（pCTFE)均聚物或共聚物樹脂的薄膜。 前技藝説明 =氟聚合物薄膜爲技藝中皆知的。這種聚合物對大省 刀、1子樂品是惰性的，耐高溫且具有低的摩擦係數。大畜 *氣聚合物’尤其是PCTFE及乙缔氣三氟乙晞⑽ :其絕佳的阻絕特性(Barrier properties)，特別地使它介 ί爲很好的阻絕包裝材料。然而由於它們成本相對的車 问’这種氟聚合物的使㈣制在特殊用途的包裝應用上。 -種由昂貴聚合物製成降低成本的包裝材料之適杏以 3 =薄膜結構的聚合物薄膜，該薄膜是由較：成4 ’口物璺層而來的。這種方法特別適合於氟聚合物包率 的應用，因爲氟聚合物的薄層—般便足以利用到 經濟部中央標準局員工消費合作社印製 時減少成本。然而，氣聚合物並不會強力: 在大多數的聚合物上；實際上，氟聚合物 性質而聞名的。已經有不同的生產方法用在多層薄 至少一層的氟聚合物與其它層如聚缔烴、逢 塑性均聚物或共聚物及特別是聚對苯二甲酸乙二: (PET)。這種多層薄膜結構已經被用來生產高定向 ® * 、令 -4 - 經濟部中央標準局員工消費合作社印製 Λ7 五、發明説明（2 構穩足的氟聚合物薄膜。在這二種結構中，黏接層或中間 黏接層用來提供良好的薄膜層接合。這種多層薄膜結構被 較佳地共擠押出，然後在單方向或兩方向被拉伸。包含 PCTFE及熱塑性聚合物的多層薄膜已被提出；例如見美國 專利申請案於1996年7月3 1曰申請，序號08/690,712號以 及於1996年12月10日申請，序號〇8/763，138號，其揭示内 容以參考方式併於本文。 雖然上述的多層薄膜結構有優越的特性，包括機械強 度，韌性及水蒸汽阻擋能力，在某些情況下多層薄膜的膜 層义間需要有較強的黏附性。因此提出一種增強pCTFE層 或其它氟聚合物層與熱塑性塑膠層之間黏附性質的多層薄 膜結構爲所需的。 "" 發明概述 根據本發明，係提供一種多層薄膜，其包括至少一層 氟聚合物層及至少一層包含熱塑性均聚物或共聚物的塑膠 層，該熱塑性塑膠層藉由中間黏接層黏接到氟聚合物層表 面上。中間黏接層包括：（1)選自由至少一個官能化的烯烴 聚合物；至少一個乙烯共聚物，及至少一個選自包括丙烯 酸、燒基丙烯酸、丙烯酸酯及丙烯酸燒酯的共單體及其摻 合物所組成之群，及（2)含苯乙烯的橡膠之摻合物。較佳 地，孩橡膠是氫化的苯乙晞_ 丁二烯_苯乙烯嵌段共聚物， 也可以視爲苯乙烯_乙烯_ 丁烯-苯乙烯嵌段共聚物。 典預期中發現，相較於只有-官能基化的聚烯烴中間黏接 層足類似多層薄膜結構中，含有相當少量的含苯乙烯橡膠 |__ -5- 本紙張尺度適CNS) (請先閲讀背面之注，意事項再填寫本頁)509626 V. Description of the invention (Λ7 B7 with reference to this application, when the United States and the United States declared that they were concentrating on applying for the benefit of the following year, serial number 60 / 049,822. The second issue of the field is about multilayer fluoropolymer films, and more specifically is , Polyvinyl Chloride & Acetyl Acetate (pCTFE) Homopolymer or Copolymer Resin Film. Former technical description = Fluoropolymer film is well-known in the art. This polymer is good for Dadaodao, 1 Zipin It is inert, resistant to high temperatures, and has a low coefficient of friction. Large animals' gas polymers, especially PCTFE and Ethyl trifluoroacetam: their excellent barrier properties, especially make it intermediary. It is a good barrier for packaging materials. However, due to their relatively low cost, 'this fluoropolymer makes it suitable for special-purpose packaging applications.-A suitable packaging material made of expensive polymers to reduce costs A polymer film with a 3 = film structure, the film is made up of: a 4 ′ layer. This method is particularly suitable for fluoropolymer encapsulation applications, because the thin layer of fluoropolymer is generally Is enough to make use of the central Prospective employees reduce costs when printing in consumer cooperatives. However, aeropolymers are not powerful: on most polymers; in fact, fluoropolymers are known for their properties. Different production methods have been used for multilayer thin films. At least one layer of fluoropolymer and other layers such as polyassociated hydrocarbons, homopolymers or copolymers, and especially polyethylene terephthalate: (PET). This multilayer film structure has been used to produce highly oriented® * 、 Order-4-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 V. Description of the invention (2) Stable fluoropolymer film. In these two structures, the adhesive layer or the intermediate adhesive layer is used to provide Good film layer bonding. This multilayer film structure is preferably co-extruded and then stretched in one or both directions. Multilayer films containing PCTFE and thermoplastic polymers have been proposed; see, for example, U.S. patent application in Application dated July 31, 1996, serial number 08 / 690,712, and application dated December 10, 1996, serial number 08 / 763,138, the disclosure of which is incorporated herein by reference. Although the above multilayer film structure has Superior properties, including mechanical strength, toughness and water vapor barrier ability, in some cases strong adhesion between the layers of the multilayer film is needed. Therefore, a reinforced pCTFE layer or other fluoropolymer layer and thermoplastic plastic are proposed A multilayer film structure with adhesive properties between layers is desirable. &Quot; " SUMMARY OF THE INVENTION According to the present invention, a multilayer film is provided that includes at least one fluoropolymer layer and at least one layer containing a thermoplastic homopolymer or copolymer. A plastic layer that is adhered to the surface of the fluoropolymer layer through an intermediate adhesive layer. The intermediate adhesive layer includes: (1) selected from at least one functionalized olefin polymer; at least one ethylene copolymer, and At least one selected from the group consisting of acrylic acid, acrylic acid, acrylate and acrylic acid comonomers and blends thereof, and (2) blends of styrene-containing rubber. Preferably, the rubber is a hydrogenated styrene-butadiene-styrene block copolymer, which can also be regarded as a styrene-ethylene-butene-styrene block copolymer. It is found in the code expectation that, compared with only -functionalized polyolefin intermediate adhesive layer, it is similar to a multilayer film structure, containing a relatively small amount of styrene-containing rubber | __ -5- This paper is suitable for CNS) (Please read first Note on the back, please fill in this page if you have any questions)
經濟部中央標準局員工消費合作社印製 509626 Λ7 --*~~ ---B7 五、發明説明（3 ) '~~ 的中間黏接層會大大的增加氟聚合物層及熱塑性塑膠層的 黏附性質。 故佳的具體實施例説明 本發明中的多層薄膜結構包含至少一層氟聚合物層及至 少一層包含至少一種熱塑性均聚物或共聚物的熱塑性塑膠 層’該熱塑性塑膠層藉由中間黏接層黏附到氟聚合物層表 面上。多層薄膜結構提供極佳的黏附特性。 適合形成本發明多層薄膜的氟聚合物層包括，但不限 於，ECTFE共聚物，乙烯-四氟乙烯共聚物，氟化乙烯丙 烯共聚物，過氟烷氧乙烯，PCTFE，聚四氟乙烯，聚氟乙 烯，聚二氟乙烯及共聚物與摻混。特別地，較佳的孰聚合 物包括氯三氟乙烯均聚物或共聚物與ECTFE的共聚物。這 種共聚物可以包含以重量計最多10%，較佳最多8%的^ 他種類共單體，例如二氟乙烯及四氟乙烯。大部分較好的 氟聚合物是氣三氟乙晞均聚物及氯三氟乙烯與二氟乙缔及 /或四氟乙烯之共聚物，這些氟聚合物可得自AHiedsignai 公司的Adon氟聚合物樹酯。氟聚合物薄膜層係描述於例 如美國專利 4,510,301 號，· 4,544,721 號及 5，139,878 號。、 又存在於多薄膜層結構是一層熱塑性塑膠層均聚物咬共 聚物。熱塑性塑膠層的材料選自由聚烯烴，聚酿胺\聚 酯，聚苯乙烯，聚碳酸酯，乙烯基聚合物，芬u ^ 1 J 次上述的共聚 物或摻合物，但是並不僅限於這些材料。知处α1 ” ^ 杈佳的熱塑性塑 膠層是聚缔煙’最好是聚（CC-7希煙）或心烯烴共聚物或其 摻合物，其α -烯烴單體約有2個到約χ ^ 八 υ聲原子，最好是約 -6- 本纸張尺度適用中標準（CNS ) Α4規格（210Χ297公釐^ ----- (請先閱讀背面之注意事項再填寫本頁) -一口 -Φ 斯626 經濟部中央標準局員工消費合作社印製 Λ7 B7 五、發明説明（4 ) 2個到約6個碳原子。非限定的聚烯烴例子包括聚乙烯， 具包含超低，低，線性且低，中，高及超高密度聚乙烯； 聚丙烯；聚丁烯；聚（1-丁稀）；聚（1-戊稀）；聚（3_甲基 -1 - 丁烯）·，聚（4 -甲基-1 -戊烯）；聚己烯；聚烯烴的共聚 物；烯烴與其它聚合物如聚氯乙烯、聚苯乙晞及聚胺基甲 酸酯等的共聚物，及此等的混合物。 介於氟聚合物層與熱塑性塑膠層之間是一層黏附層或習 於此技藝者所稱的黏接（tie)層。根據本發明之黏接層包 括聚合物質之摻合物，即（1)選自包括至少一個官能基化 聚晞烴之含晞烴聚合物；至少一個乙稀與至少一個選自包 括丙烯酸，垸基丙烯酸，丙烯酸酯及燒基丙烯酸酯之共單 體的共聚物；及其混合物，與（2)含苯乙烯的橡膠。一類 型的含烯烴聚合物係指含有至少一個官能基部份的晞烴聚 合物。可用在此處的官能基部份是不飽和羧酸、不飽和酸 奸、胺及環氧化物。用來製備改質聚烯烴的聚晞系範例包 括例如乙烯，丙烯，1 - 丁烯，1 -戊烯，1 _己烯，4 -甲基_ 1-戌烯及，1 -辛烯的α -烯烴均聚物或共聚物。用於改質 聚烯烴的不飽和酸酸及其酸酐包括順丁晞二酸及其酸奸， 甲酸及其酸酐，巴豆酸（crotonic acid)及其酸奸，衣康酸 (itactonic acid)及其酸纤及其類似物。其中順丁烯二酸酐 是最佳的選擇。適合的的胺類包括脂族或芳族的第一，第 二級及第三胺；例如2，4，6 -三溴苯胺，甲基胺，乙基 胺，丙基胺，二甲基胺，N 甲基苯胺，乙甲基胺，2_ (N_曱基胺）戍虎，第二丁基二甲基胺，N -乙基甲基 本紙張尺度適用中國國家標準（CNS ) A4規格公簸） --------«t------IT------0 (請先閱讀背面之注'意事項再填寫本頁) - . 509626 Λ7 Β7 五、發明説明（5 ) 苯胺，三甲基胺，N，N-二甲基苯胺及其類似物。適合的 環氧化物包括含約2至約2 0個碳原子的化合物。適合用於 本發明的改質聚烯烴，包含敘於美國專利3,481，910號、 3,480,580 號、4,612，155 號及 4,715,270 號之組成物，其 併於此爲參考。 較佳的改質聚烯烴組合物包括以改質聚烯烴總重量計約 0.001到約1 0重量百分比之官能基部份。更佳的是在約 0.005到約5重量百分比的範圍，且最佳的是在約〇 〇丨到 約2重量百分比的範圍。其它種類有用的含烯烴聚合物爲 乙烯與丙烯酸、烷基丙烯酸、丙烯酸酯、及/或烷基丙酸 酯的共聚物。烷基丙烯酸或是烷基丙烯酸酯所含的烷基最 好是約2到約4個碳原子。這些種類的聚合物當中較佳的 是乙晞基甲基丙烯酸酯共聚物。 同時，黏接層也有包含苯乙烯的橡膠。這些橡膠最好是 苯乙烯的嵌段共聚物，例如氫化的苯乙烯_ 丁二烯—苯乙烯 歆段共聚物，亦稱爲苯乙晞-乙烯-丁烯-苯乙烯（SEBS )嵌 段共聚物。其它如高熔融黏度聚烯烴的高分子材料也可以 使用在黏接層内。 經濟部中央標準局員工消費合作社印製 頃發現即使黏接層中含有相當少量的含苯乙烯橡膠也 會大大的增強氟聚合物層與熱塑性塑膠層之間的黏接性 質。含苯乙晞的橡膠可包括基於黏接層總重量約在丨到約 3 5重量百分比，而較佳的範圍是約在$到約2〇重量百分 比0 … 多層薄膜結構可以任何傳統的方法製備。較佳地，在用 _________ - 8 _ 本纸張尺度適用中國國家標準（CNS) Α7^γ^1〇χ297 509626 五、發明説明（6 於多層薄膜之共聚物之H度及其他條 250 C到約彻。(：下使料造或起泡成型薄膜技㈣^約在 同押出(__)出來。或者，也可 二：層： 而獲得多層薄膜。 層堆®在一起 可=前習技藝將多層薄膜在單方向或雙 向。同時，只要各聚合物層之間有黏接層存在 ς =數可以根據特定最後用途的要求來調整。例如 、:構可以是包含聚乙埽層_黏接層_氟聚合物層（例： PCTFE)-黏接層-聚乙埽層。此夕卜，本發明的多層薄膜之 厚度可爲任何一般的膜厚，例如總厚度約〇1密爾㈤ 到约25密爾。每層的厚度可改變，且可例如在約〇〇5麥 爾到約1〇密爾的範圍。這些只是很多種的氟聚合丄 塑性聚合物厚度與層數組和之其中幾種而已，當然包括任 何厚度與層數的改變。 藉由參考特定且具有代表性之具體實施例，本發明會更 加容易了解。但是必須了解的是本文探討特定的具體實施 例只是用來闡明本發明，並非用來侷限本發明之申請範 圍’可以更深入了解本發明除特別描述之實例外尚可應用 於發明所涵蓋之範圍。 經濟部中央標準局員工消費合作社印製 實例1 二層多層薄膜是由PCTFE均聚物（來自AlliedSingal公司 的Aclon HP1120)、線性低密度聚乙烯（來自道氏（Dow)化 學公司的Dowlex 2045A)和由（~1 )及（2)所摻合物的黏接層 共同押出，其中（1)爲官能化聚晞烴（來自Mitsui Chemicals _ 9 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 509626 Λ7 ___ 五、發明説明（7 )Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 509626 Λ7-* ~~ --- B7 V. Description of the invention (3) The intermediate adhesion layer of '~~ will greatly increase the adhesion of the fluoropolymer layer and the thermoplastic plastic layer nature. The preferred embodiment illustrates that the multilayer film structure in the present invention includes at least one fluoropolymer layer and at least one thermoplastic plastic layer including at least one thermoplastic homopolymer or copolymer. The thermoplastic plastic layer is adhered by an intermediate adhesive layer. Onto the surface of the fluoropolymer layer. The multilayer film structure provides excellent adhesion properties. Fluoropolymer layers suitable for forming the multilayer film of the present invention include, but are not limited to, ECTFE copolymer, ethylene-tetrafluoroethylene copolymer, fluorinated ethylene propylene copolymer, perfluoroalkoxyethylene, PCTFE, polytetrafluoroethylene, poly Fluorinated ethylene, polyvinylidene fluoride and copolymers are blended with. In particular, preferred amidine polymers include copolymers of chlorotrifluoroethylene homopolymers or copolymers and ECTFE. This copolymer may contain up to 10%, preferably up to 8% by weight of other kinds of comonomers, such as difluoroethylene and tetrafluoroethylene. Most of the preferred fluoropolymers are homopolymers of trifluoroacetamidine and copolymers of chlorotrifluoroethylene and difluoroethylene and / or tetrafluoroethylene. These fluoropolymers are available from Adon Fluoropolymer of Ahiedsignai Company. Property resin. Fluoropolymer film layers are described in, for example, U.S. Patents 4,510,301, 4,544,721 and 5,139,878. Also present in the multi-film layer structure is a thermoplastic plastic layer homopolymer bite copolymer. The material of the thermoplastic plastic layer is selected from polyolefins, polyurethanes, polyesters, polystyrenes, polycarbonates, vinyl polymers, fin ^ 1 J times the above copolymers or blends, but is not limited to these material. Knowing α1 ”^ The best thermoplastic plastic layer is poly-smoke ', preferably poly (CC-7 Greek smoke) or heart olefin copolymer or its blend. The α-olefin monomer is about 2 to about χ ^ Eight υ sound atoms, preferably about -6- This paper size applies the medium standard (CNS) Α4 size (210 × 297 mm ^ ----- (Please read the precautions on the back before filling this page)- Yikou-Φ Si 626 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 B7 V. Description of the invention (4) 2 to about 6 carbon atoms. Examples of non-limiting polyolefins include polyethylene, which contains ultra-low, low, Linear, low, medium, high and ultra-high density polyethylene; polypropylene; polybutene; poly (1-butane); poly (1-pentane); poly (3-methyl-1-butene) · , Poly (4-methyl-1 -pentene); polyhexene; copolymers of polyolefins; copolymers of olefins and other polymers such as polyvinyl chloride, polystyrene, and polyurethanes, And these mixtures. Between the fluoropolymer layer and the thermoplastic layer is an adhesive layer or a tie layer known to those skilled in the art. The adhesive according to the invention The layer comprises a blend of polymeric substances, ie (1) selected from a fluorene-containing polymer comprising at least one functionalized polyfluorene; at least one ethylene and at least one selected from the group consisting of acrylic acid, fluoracrylic acid, acrylate and Copolymers of acrylate-based comonomers; and mixtures thereof, and (2) styrene-containing rubbers. One type of olefin-containing polymer is a fluorene polymer containing at least one functional group moiety. It can be used in The functional groups here are unsaturated carboxylic acids, unsaturated acids, amines and epoxides. Examples of polyfluorene systems used to make modified polyolefins include, for example, ethylene, propylene, 1-butene, 1-pentene Olefin, 1-hexene, 4-methyl_1-pinene and 1-octene alpha-olefin homopolymers or copolymers. Unsaturated acids and their anhydrides used to modify polyolefins include cis-butene Carboxylic acid and its acid, formic acid and its anhydride, crotonic acid and its acid, itactonic acid and its acid fiber and the like. Among them, maleic anhydride is the best. Choice. Suitable amines include aliphatic or aromatic primary, secondary and tertiary amines ; For example 2,4,6-tribromoaniline, methylamine, ethylamine, propylamine, dimethylamine, N methylaniline, ethylmethylamine, 2_ (N_fluorenylamine), Second butyl dimethylamine, N-ethyl methyl This paper is in accordance with the Chinese National Standard (CNS) A4 specifications. -------- «t ------ IT ---- --0 (please read the notes on the back of the page and fill in this page)-. 509626 Λ7 B7 V. Description of the invention (5) Aniline, trimethylamine, N, N-dimethylaniline and the like. Suitable epoxides include compounds containing from about 2 to about 20 carbon atoms. Modified polyolefins suitable for use in the present invention include compositions described in U.S. Patent Nos. 3,481,910, 3,480,580, 4,612,155, and 4,715,270, which are incorporated herein by reference. The preferred modified polyolefin composition includes a functional group portion of about 0.001 to about 10 weight percent based on the total weight of the modified polyolefin. It is more preferably in the range of about 0.005 to about 5 weight percent, and most preferably in the range of about 0.00 to about 2 weight percent. Other types of useful olefin-containing polymers are copolymers of ethylene with acrylic acid, alkylacrylic acid, acrylates, and / or alkylpropionates. The alkyl group contained in the alkyl acrylate or alkyl acrylate is preferably about 2 to about 4 carbon atoms. Among these kinds of polymers, an ethyl methacrylate copolymer is preferred. At the same time, the adhesive layer also contains rubber containing styrene. These rubbers are preferably block copolymers of styrene, such as hydrogenated styrene-butadiene-styrene fluorene copolymers, also known as styrene-ethylene-butene-styrene (SEBS) block copolymers. Thing. Other polymer materials such as high melt viscosity polyolefins can also be used in the adhesive layer. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, it was found that even if the adhesive layer contains a relatively small amount of styrene-containing rubber, the adhesion between the fluoropolymer layer and the thermoplastic plastic layer will be greatly enhanced. The acetophenone-containing rubber may include from about 丨 to about 35 weight percent based on the total weight of the adhesive layer, and the preferred range is from about $ to about 20 weight percent. 0… The multilayer film structure can be prepared by any conventional method . Preferably, in use _________-8 _ This paper size applies Chinese National Standards (CNS) Α7 ^ γ ^ 1〇χ297 509626 V. Description of the invention (6 H degree of copolymers for multilayer films and other articles 250 C To Joch. (: The following technology for making materials or foaming films is about __). Or, you can also two: layer: to obtain a multi-layer film. Stacking ® together can be = previous practice skills The multilayer film is unidirectional or bidirectional. At the same time, as long as there is an adhesive layer between each polymer layer, the number can be adjusted according to the requirements of the specific end use. For example, the structure can include a polyethylene layer_adhesion Layer_fluoropolymer layer (example: PCTFE) -adhesive layer-polyethylenic layer. In addition, the thickness of the multilayer film of the present invention can be any general film thickness, for example, the total thickness is about 0.1 mil to About 25 mils. The thickness of each layer can vary, and can range, for example, from about 0.05 mils to about 10 mils. These are just a variety of fluoropolymer, plastic polymer thicknesses and layer arrays, among them Only a few, of course, including any change in thickness and number of layers. The specific embodiments of the present invention will be easier to understand. However, it must be understood that the specific specific embodiments discussed herein are only used to clarify the present invention, and are not intended to limit the scope of application of the present invention. Specially described examples can still be applied to the scope covered by the invention. Example printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Example 1 The two-layer multilayer film is made of PCTFE homopolymer (Aclon HP1120 from AlliedSingal), linear low-density polymer. Ethylene (Dowlex 2045A from Dow Chemical Company) and the adhesive layer blended by (~ 1) and (2) were co-extruded, of which (1) was a functionalized polyfluorene (from Mitsui Chemicals _ 9 This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 509626 Λ7 ___ 5. Description of the invention (7)
America，Inc·的 Admer SF700A，包含以重量計 68% 乙晞， 2 5 %丙烯，7 %乙酸乙烯酯和低於1 〇/〇的順丁烯二酸酐； (2)爲苯乙烯-乙烯-丁晞-苯乙烯嵌段共聚物（來自蜆殼化 學公司的Kraton G1657橡膠）。以摻·合物之總重計，橡膠 的重量佔10%。該多層薄膜結構被共同押出並铸造於一 個溫度維持在62T (17Ό )的鑄膜滾輪上，且聚乙烯層面向 鑄膜滾輪。 該多層薄膜的黏接強度是利用黏著膠帶剝落法測試 (ASTM F904)，其方法爲使用Scotch 610膠帶作爲基材， 以每分鐘12英吋（30.5公分），1 80度的速度撕落，以 PCTFE層爲上層。在膠帶兩側的平均黏接強度每英吋爲 600克重（每公分236克重），在膠帶pCTFE側面的平均黏 接強度爲每英吋3 6 0克重（每公分142克重）。相較之下， 多層薄膜若在相似的條件所製備，但若只使用Admer SF700A作爲黏結層，其膠帶兩侧平均键結強度每英吋37〇 克重（每公分1 47克重），在膠帶PCTFE側面則爲每英吋 220克重（每公分87克重）。由此可見，黏接層中存在含有 苯乙晞橡膠，則會大大改進多層膜結構的黏接強度。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 實例2 針對實例1利用數種不同型式的苯乙轉膠反覆實 驗’其餐膜滚輪溫度維持在80T(27,C)。所獲得的資料 -10 - 本紙張尺錢财_ —— 509626 Λ7 B7 五、發明説明（8 旨配方 表1 黏接強度克重/英对(克重/公分) (gm/crn) 聚合物基材 盖乙缔槔舰義皆有— % ^ mPE1 mPE1 mPE1 mPE1 mPE1 mPE1 mPE1 100% 90% 80% 95% 90% 80% 90% 10% 20% 5% 10% 20% 10% 198 (78) (SEBS)，線性2 221 (87) 經濟部中央標準局員工消費合作社印製 (SEBS)，線性 2 292(115) (SEBS)，雙嵌段3 260(102) (SEBS)，雙嵌段3 320(126) (SEBS)，雙嵌段3 315 (124) (SEBS)，線性 219(86) 1%馬來酸化作用 4 (maleation) 1 = Admer SF700A改質的聚乙烯 2 = Kraton G1650 3=KratonGl657 (35%雙嵌段，65% 線性） 4 = Kraton FG1921X 由表1中可見，雙嵌段SEBS對於增進黏著度爲 303(119) 340 (134) 584 (230) 520 (205) 603 (237) 650 (256) 359(141) 最有效 ^裝-- C請先閱讀背面之注意事項再填寫本頁) 11 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公漦） 509626 Λ7 五、發明説明（9 經濟部中央標準局員工消費合作社印製 實例 除改變黏接層樹脂中的聚合物基材且鑄膜滚輪的溫度爲 80°F (27。(：）外，重覆實例1。該黏接層樹脂含9 0 %乙烯丙 烯酸甲酯共聚物（來自Chevron化學公司的EMAC 2202 )， 和10%雙嵌段SEBS橡膠（Kraton G1657)。此種結構表現在 膠帶的兩側平均黏接強度爲每英吋5 7 5克重（每公分2 2 6 克重），及在膠帶PCTFE側，強度則爲每英吋183克重（每 公分7 2克重）。相較之下，只使用乙烯丙烯酸甲酯共聚物 作爲黏接層的多層膜，其在膠帶兩側的平均黏接強度爲每 英吋321克重（每公分126克重），而在PCTFE側黏接強 度則爲每英吋156克重（每公分61克重）。 實例4 重覆實例1，除改用聚（伸乙晞氯三氟乙烯）之交錯嵌段 共聚物（來自美國Ausimont公司的Halar 500 )之氟聚合物且 以P(ECTFE)與鑄膜滾輪接觸。此外，黏接層樹脂包含75% Admer SF700A (19(TC 下，每一次 ASTM D1238 測驗融熔流 動速率爲 0.1)，15% Admer AT1276(同樣來自 Mitsui Chemicals America，Inc.;與 SF700A 組成相同，融熔流動 速率爲 0.4 至 0.6)及 10% Kraton G1657(雙嵌段 SEBS)。 m薄膜在膠帶兩側的平均黏接強度每英吋55()克重（每 公分2 1 7克重），在膠帶單側則爲每英吋3 5 〇克重（每公分 1 3 8克重）。相對的P(ECTFE)的氟聚合物薄膜在膠帶兩側 的平均黏接強度爲每英吋4 5 5·克重（每公分179克重）而在 膠帶單側則爲每英吋2 5 0克重（每公分9 8克重）。 衣-- (請先閲讀背面之注_意事項再填寫本頁) -Φ -12America, Inc.'s Admer SF700A, containing 68% by weight acetamidine, 25% propylene, 7% vinyl acetate, and maleic anhydride less than 10/0; (2) styrene-ethylene- Butadiene-styrene block copolymer (Kraton G1657 rubber from Krypton Shell Chemical Company). Based on the total weight of the blend, the rubber accounts for 10%. The multilayer film structure was co-extruded and cast on a cast film roller maintained at a temperature of 62T (17Ό) with the polyethylene layer facing the cast film roller. The adhesive strength of this multilayer film was tested using the Adhesive Tape Peel Method (ASTM F904). The method used Scotch 610 tape as the substrate, peeled at a rate of 12 inches (30.5 cm) per minute at a rate of 80 degrees, and The PCTFE layer is the upper layer. The average adhesion strength on both sides of the tape was 600 grams per inch (236 grams per centimeter), and the average adhesion strength on the side of the tape pCTFE was 360 grams per inch (142 grams per centimeter). In contrast, if multilayer films are prepared under similar conditions, but if only Admer SF700A is used as the adhesive layer, the average bond strength on both sides of the tape is 37 grams per inch (147 grams per centimeter). The tape PCTFE side weighs 220 grams per inch (87 grams per cm). It can be seen that the presence of acetophenone rubber in the adhesive layer will greatly improve the adhesive strength of the multilayer film structure. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Example 2 For Example 1, repeated experiments using several different types of styrene-to-ethyl rubber were performed. 27, C). Obtained information -10-Paper rule money _ 509626 Λ7 B7 V. Description of the invention (8 purpose formula Table 1 Adhesive strength gram weight / British pair (gram weight / cm) (gm / crn) polymer base All materials are covered by the material cover —% ^ mPE1 mPE1 mPE1 mPE1 mPE1 mPE1 mPE1 100% 90% 80% 95% 90% 80% 90% 10% 20% 5% 10% 20% 10% 198 (78) ( SEBS), Linear 2 221 (87) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (SEBS), Linear 2 292 (115) (SEBS), Diblock 3 260 (102) (SEBS), Diblock 3 320 (126) (SEBS), diblock 3 315 (124) (SEBS), linear 219 (86) 1% maleation 4 (maleation) 1 = Admer SF700A modified polyethylene 2 = Kraton G1650 3 = KratonGl657 (35% diblock, 65% linear) 4 = Kraton FG1921X As can be seen in Table 1, the diblock SEBS has an improved adhesion of 303 (119) 340 (134) 584 (230) 520 (205) 603 (237) 650 (256) 359 (141) The most effective installation-C Please read the notes on the back before filling out this page) 11-This paper size applies to China National Standard (CNS) A4 size (210X297) 漦 509626 Λ7 V. Description of Invention (9 Member of Central Bureau of Standards, Ministry of Economic Affairs Except for changing the polymer base material in the adhesive layer resin and the temperature of the cast film roller is 80 ° F (27. (:)), the printed example of Industrial and Commercial Cooperatives repeats Example 1. The adhesive layer resin contains 90% Ethylene methyl acrylate copolymer (EMAC 2202 from Chevron Chemical Company), and 10% diblock SEBS rubber (Kraton G1657). This structure is manifested in the average adhesive strength of both sides of the tape of 5 7 5 grams per inch Weight (2 2 6 grams per centimeter), and on the PCTFE side of the tape, the strength is 183 grams per inch (72 grams per centimeter). In contrast, only ethylene methyl acrylate copolymer is used as the adhesive The average adhesion strength of the multilayer film on both sides of the tape is 321 grams per inch (126 grams per centimeter), and the adhesion strength on the PCTFE side is 156 grams per inch (61 centimeters per cm). Gram weight). Example 4 Repeat Example 1 except that the fluoropolymer of the interblock copolymer (Halar 500 from Ausimont, USA) was used instead of poly (ethylene trichloroethylene trifluoroethylene), and P (ECTFE) and Cast film roller contact. In addition, the adhesive layer resin contains 75% Admer SF700A (19 (at TC, melt flow rate of 0.1 per ASTM D1238 test), 15% Admer AT1276 (also from Mitsui Chemicals America, Inc .; same composition as SF700A, melt The melt flow rate is 0.4 to 0.6) and 10% Kraton G1657 (diblock SEBS). The average adhesive strength of m film on both sides of the tape is 55 () grams per inch (2 17 grams per cm), at One side of the tape is 350 grams per inch (138 grams per cm). The average adhesion strength of the relative P (ECTFE) fluoropolymer film on both sides of the tape is 4 5 5 · Gram weight (179 grams per centimeter) and 250 grams per inch (98 grams per centimeter) on one side of the tape. Page) -Φ -12
Λ7 —~~-_ B7 五、發明説明（10 ) 由此可見，此發明提供一多層氟聚合物結構，其增進氟 聚合物和熱塑性塑膠層之間的黏著性。此_結構也具有極 佳的機械強度，勃性及水蒸氣阻絕性，且具較佳的透明結 構，所以可見到包裝物的内容。 沒種多層薄膜結構可使用於各種的應用，包含包裝。其 中-種包裝形 <，特別適用於本發明的多層氟；合物薄膜 結構即爲醫藥上之藥物包裝及其類似包裝。基本上，在這 種形式的包裝中利用氟聚合物結構適當的黏著性使其在聚 氯乙婦層（PVC)並且視情況地在一層聚缔烴上疊層，其 熱塑性塑膠層（如，聚乙烯）面向Pvc層。然後此疊層結 構熱塑成所希望的形狀而氟聚合物（例如PCTFE)在疊層結 構之外側，具填滿藥物（如藥丸）且鋁箔黏著於pvc層。 經濟部中央標準局員工消費合作社印製 __-13- I紙張尺度適用中國國) A4規格（2ί()χ297公楚yΛ7 — ~~ -_ B7 V. Description of the invention (10) It can be seen that this invention provides a multilayer fluoropolymer structure, which improves the adhesion between the fluoropolymer and the thermoplastic plastic layer. This structure also has excellent mechanical strength, robustness and water vapor resistance, and has a better transparent structure, so the contents of the package can be seen. No multilayer film structure can be used for a variety of applications, including packaging. Among them, a package type < is particularly suitable for the multilayer fluorine of the present invention; the compound film structure is a pharmaceutical packaging for medicine and the like. Basically, in this form of packaging, the appropriate adhesion of the fluoropolymer structure is used to laminate it on a polyvinyl chloride layer (PVC) and optionally a layer of polyassociated hydrocarbon, whose thermoplastic plastic layer (eg, Polyethylene) facing the pvc layer. The laminated structure is then thermoformed into the desired shape while the fluoropolymer (such as PCTFE) is outside the laminated structure, filled with drugs (such as pills), and the aluminum foil is adhered to the PVC layer. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs __- 13- I Paper size applies to China) A4 size (2ί () χ297 公 楚 y