201226178 六、發明說明： 【發明所屬之技術領域】 本發明係有關複層薄材、環狀帶及環狀帶的製造方 法。更詳細的是，本發明係有關於例如可用於工業相關之 耐熱性、^點著性及耐磨損性、止滑性良好的複層薄材、 由該複層薄材構成的環狀帶及環狀帶的製造方法。 【先前技術】 一直以來，已為所知的耐熱複合薄材係將耐熱性或非 黏著性良好的耐熱樹脂複合於耐熱性及拉張強度等良好 的耐熱性纖維織布，這些耐熱複合薄材係作為與工業相關 的耐熱、非黏著性薄材或耐熱、非黏著性搬送帶等使用。 用於上述耐熱複合薄材的耐熱性纖維織布，例如係使 用以平織、斜織等形成的玻璃纖維、芳香族聚醯胺纖維等 織布。 又’用於上述耐熱複合薄材的财熱樹脂，例如係使用 四氟乙烯樹脂（PTFE)等氟樹脂。 然而，一般’氟樹脂係具有良好的耐熱性、耐冷性、 非黏著性、耐藥品性（chemical resistance)、耐燃燒性（fjame resistance)、耐候性（weather resistance)、電絕緣性、低 摩擦性等’但因缺乏耐磨損性（wear reisistance )、具良好 低摩擦性，而容易有滑動的問題。 耐磨損性優於氟樹脂，而低摩擦性劣於氟樹脂、止滑 性（grip)優於氟樹脂，且難以滑動的耐熱材料例如為聚 201226178 醯亞胺系樹脂等。 作為提升薄材的耐磨損性之製造 方法係將耐熱性纖維織布含浸且附著於:被提出的 被分散在氣素樹脂水性懸浮液的混合液 :本特開2_姻3號公報（專利文㈣）。的 ”、、' ，記載於上述專利文獻丨的薄材 ::氣樹脂的混合材料，因此’雙方的二:= 夺難以獲传親亞㈣樹脂原本請的耐磨損性。對於搬 达用的環狀帶’其與驅動滾輪的接觸面即帶體的内側面星 ㈣當的止滑性及耐磨損性係重要的，但聚醯亞胺系樹脂 與氟樹脂的混合材料似乎難得使其兩全。 不為聚酸亞胺系樹脂與敦樹脂的混合材料，而係將聚 醯亞胺系樹脂與氟樹脂的層形成為管狀環狀帶（日本特開 平7-110632號公報（特許文獻2)、日本特開平7_178川 號公報（特許文獻3)、日本特開2002-178422號公報（特 許文獻4))亦被提出。然而，其製造方法係以圓筒狀金屬 模具壓製成形，為了對應各式各樣的尺寸，似乎使得設備 成本大增。 [專利文獻1]特開2006-21403號公報 [專利文獻2]特開平7_11〇632號公報 [專利文獻3]特開平7_178741號公報 [專利文獻4]特開2002-178422號公報 【發明内容】 201226178 本發明考慮到上述之事項而檢討，目的為提供一種複 層薄材、由該複層薄材所構成的環狀帶及環狀帶的製造方 法，使能得到良好的耐熱性、非黏著性，且具有所需的耐 磨損性或止滑性之薄材，其係將薄材裁切為所需尺寸且利 用將其環狀化，不須使用模具而可製造各式各樣尺寸的環 狀帶。 為了達成上述目的，依據本發明之一種複層薄材，其 包括由氟樹脂及耐熱纖維布所構成的至少一複合材層及 由聚醯亞胺系樹脂所構成的一表面層。其中，該表面層係 介由一處理面而形成，該處理面係藉由對該複合材層進行 表面活性化處理而形成。 作為本發明之複層薄材的較佳態樣，該表面活性化處 理包括無機粒子附著燒成處理、金屬鈉蝕刻處理、電漿放 電處理或電暈放電處理。 又，本發明之環狀帶係由上述複層薄材所形成的一帶 狀物之環狀體所構成。 接著，本發明之環狀帶的製造方法係將上述複層薄材 裁切為帶狀；接合此複層薄材之一帶狀物的相對二端部而 得一環狀體。 又，本發明之另一環狀帶的製造方法係將上述複層薄 材與一另一薄材所積層的一帶狀物，將該帶狀物的該複層 薄材之相對二端部及該環狀物的該另一薄材之相對二端 部分別接合或使其近接配置而得一環狀體。 依據本發明，能得到具有良好的耐熱性、非黏著性及 201226178 耐磨損性、止滑性的複層薄材。 此複層溥材之表面層為聚酸亞胺系樹脂，因此，能得 =用於所要用途、需求性能等的非黏著性、财磨損性 止滑性。 ，著依據本發明’係直接將此複層薄材積層或係將 ;一缚材積層後’再將此複層薄材裁切為帶狀或將另一薄 的切為帶狀，以形成所要的寬度及長度的環狀 :·宫片：到%<狀帶’因此’可容易製造對應用途之所 各層戶^的^層之構成的環狀帶。又’可在積層前準備 曰、見又、長度，將這些層積層後製造環狀帶。 抑又，根據情況不將同—複層薄材裁切，而係將寬度 —形成後，將此寬度寬的環狀帶裁切為所需寬 f，猎此，可同時製造複數個長度相同的環狀帶。又，在 :赴述寬度寬的環狀帶時，藉由調整寬度 且區分相異寬度的環狀帶。 勿卞風 表面2於藉由塗佈㈣亞㈣樹脂可進行複層薄材之 表面層的形成’ @此，在預先以薄材狀獲得表面層部分， 相較於猎由黏著劑等積層的情 因此可得強度㈣久性良好的m的接合強度高， 良野的歿層溥材及環狀帶， 易、效率地進行複層薄材或環狀帶的製造。 【實施方式】 本發明之複減材衫以、—層城_ 纖維織布所構成之複合材層及由聚醯亞胺系樹脂所構成 201226178 =對ΐ 層係介由—處理面而形成，該處理 面心措由對料合材層進行表面活性化處理而形成。 作為本發明之複層薄材的較佳具體例，例如可為圖 1、2所記載之例子。 。口 圖1所示之本發明的複層薄材10，係具有—層由氣樹 脂2a及耐熱性纖維織布㉛所.構成之複合材層2及由聚醯 亞胺系樹脂所構成之表面層3a的複層薄材，其中，該表面 層3a係介由一處理面4而形成，該處理面^係藉由/對該 複合材層2進行表面活性化處理而形成。 圖2所示之本發明的複層薄材n，係具有由聚酿亞胺 糸樹脂所構成之表面層於其兩面，且係具有一層由_脂 '及耐熱性纖維織布2b所構成之複合材層2及由聚醯亞 胺系樹脂所構成之表面層3a的複層薄材，其中，該表面 層3a係介由—-處理面4而形成，該處理面4係藉^該複 合材層2進行表面活性化處理而形成。 <合材層> 於本·υ之複層薄材的複合材層係由氟樹脂及耐執 性纖維織布所構成。 … 本發明之氟樹脂並無限定，其可係從聚四氟乙烯 (PTFE)、四氟乙烯-全氟烷基乙烯基醚共聚物（PFA)、四 I乙烯_六1丙烯共聚物（FEP)所構成的群選出的耐熱性 樹脂。在這之中，特別以聚四氟乙烯為佳。 該氟樹脂可對應所需而配合導電性粉末。藉此，可給 予導電性或提料電性，且可達到提升耐磨損性。導電性 201226178 粉末之較佳具體例為石炭黑（Carb〇n black)及 aitanmm Oxide)。其配合量相對i樹脂較佳為丨〜扣斯= 么卜〇 里 於本發财’耐祕纖維織布並無蚊，例如為 維、芳《«胺纖維。耐熱性纖維織布的厚度= 30〜_Mm’特別以3〇〜7〇〇㈣為佳。 4 此複合材層較佳例如係可將氟樹脂粒子的水性縣— 液含浸於耐熱性纖維織右，> ^〜☆ $ #丄#上、 心'吁 ’乾燥後再藉由燒成而形成。^ 製水性懸浮液時的溶媒你Ι4>τι Α ν & σ, 』 δ周201226178 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a laminated thin material, an endless belt, and an endless belt. More specifically, the present invention relates to a laminated layer which is useful for industrially relevant heat resistance, punctuation, abrasion resistance, and slip resistance, and an endless belt composed of the laminated thin material. And a method of manufacturing an endless belt. [Prior Art] Conventionally, a heat-resistant composite thin material which is known has a heat-resistant resin having good heat resistance or non-adhesive property, and is excellent in heat-resistant fiber woven fabrics having excellent heat resistance and tensile strength. It is used as a heat-resistant, non-adhesive thin material or a heat-resistant, non-adhesive conveyor belt related to industry. The heat-resistant fiber woven fabric used for the heat-resistant composite thin material is, for example, a glass fiber or an aromatic polyamide fiber which is formed by plain weave, twill weave or the like. Further, as the heat-treating resin used for the above heat-resistant composite thin material, for example, a fluororesin such as tetrafluoroethylene resin (PTFE) is used. However, general 'fluororesin has good heat resistance, cold resistance, non-adhesiveness, chemical resistance, fjame resistance, weather resistance, electrical insulation, and low friction. Waiting for 'but because of lack of wear reisistance, good low friction, and easy to slip. The heat resistance is superior to that of the fluororesin, and the low friction is inferior to the fluororesin, the grip is superior to the fluororesin, and the heat resistant material which is difficult to slide is, for example, a poly 201226178 yttrium imide resin. As a manufacturing method for improving the abrasion resistance of the thin material, the heat-resistant fiber woven fabric is impregnated and adhered to the proposed mixed liquid dispersed in the aqueous suspension of the gas-filled resin: Patent (4)). The ",," is described in the above-mentioned patent document 薄 Thin material: a mixture of gas and resin, so the two sides of the two: = won the hard to pass the pro-Asia (four) resin original wear resistance. For the transfer The endless belt's contact surface with the driving roller, that is, the inner side of the belt (4), is important for slip resistance and wear resistance, but the mixture of polyimine resin and fluororesin seems to be rare. It is not a mixed material of a polyamic acid imide resin and a dynasty resin, but a layer of a polyimide-based resin and a fluororesin is formed into a tubular endless belt (Japanese Patent Laid-Open No. Hei 7-106032) Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. 2002-178422 (Patent Document No. 4) and No. 2002-178422 (Patent Document No. 4) are also proposed. However, the manufacturing method is formed by press molding with a cylindrical metal mold. In the case of the various types of sizes, the cost of the device is increased. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. [Patent Document 4] JP-A-2002-178422 The present invention has been made in consideration of the above matters, and an object of the present invention is to provide a method for producing a laminated thin material and an endless belt and an endless belt composed of the composite thin material, which can provide good heat resistance. A non-adhesive material having a desired abrasion resistance or slip resistance, which is obtained by cutting a thin material into a desired size and using a mold to form a variety without using a mold. In order to achieve the above object, a multi-layered thin material according to the present invention comprises at least one composite layer composed of a fluororesin and a heat-resistant fiber cloth and a polyimide-based resin. The surface layer is formed by a processing surface formed by surface-activation of the composite layer. The preferred aspect of the multi-layered thin material of the present invention. The surface activation treatment includes an inorganic particle adhesion baking treatment, a metal sodium etching treatment, a plasma discharge treatment, or a corona discharge treatment. Further, the endless belt of the present invention is formed by the above-mentioned laminated thin material. Ring of matter Next, the manufacturing method of the endless belt of the present invention cuts the multi-layered thin material into a strip shape; and joins the opposite ends of one of the multi-layered thin materials to obtain an annular body Further, in another method of manufacturing the endless belt of the present invention, a strip of the above-mentioned multi-layered thin material and a further thin material is laminated, and the opposite ends of the multi-layered thin material of the strip are The opposite ends of the other thin material of the ring and the ring are respectively joined or arranged in close proximity to obtain an annular body. According to the invention, good heat resistance, non-adhesiveness and wear resistance of 201226178 can be obtained. A multi-layered thin material with a lossy or slippery property. The surface layer of the multi-layered coffin is a polyamicimide-based resin, so that it can be used for non-adhesiveness and wear resistance of a desired use, demand performance, and the like. Slippery. According to the invention, the layer is directly laminated or layered; after a layer of material is laminated, the layered material is cut into strips or another thin strip is cut into strips to form The desired width and length of the ring: · Palace piece: to the % < band 'so' can easily manufacture the endless belt of the layer of each layer of the corresponding use. In addition, it is possible to prepare 环状, see, and length before stacking, and laminate these layers to produce an endless belt. Moreover, depending on the situation, the same-layered thin material is not cut, but the width is formed, and the wide-width annular strip is cut into a desired width f, and the same length can be simultaneously produced. Looped band. Further, when the endless belt having a wide width is described, the endless belt having different widths is distinguished by adjusting the width. Do not hurricane surface 2 by coating (four) sub (four) resin can be used to form the surface layer of the multi-layered thin material '@this, the surface layer portion is obtained in advance in a thin material, compared to the layering of the adhesive by an adhesive or the like Therefore, the strength can be obtained. (4) The joint strength of m having a long-lasting property is high, and the enamel layer and the endless belt of Liangye are easy and efficient to manufacture a laminated thin material or an endless belt. [Embodiment] The composite material layer of the present invention is composed of a composite layer composed of a layer of _ fiber woven fabric and a layer composed of a polyimide resin; 201226178 = a layer of the layer is formed by treating the surface. The treated face center is formed by surface-treating the material layer. Preferred examples of the multi-layered thin material of the present invention are, for example, the examples described in Figs. . The multi-layered thin material 10 of the present invention shown in Fig. 1 has a composite layer 2 composed of a gas resin 2a and a heat-resistant fiber woven fabric 31, and a surface composed of a polyimide resin. The multi-layered thin layer of the layer 3a, wherein the surface layer 3a is formed by a processing surface 4 formed by surface-activation of the composite material layer 2. The multi-layered thin material n of the present invention shown in Fig. 2 has a surface layer composed of a polyacrylonitrile resin on both sides thereof, and has a layer composed of a grease and a heat-resistant fiber woven fabric 2b. a composite layer 2 and a multi-layered thin layer of a surface layer 3a composed of a polyimide-based resin, wherein the surface layer 3a is formed by treating the surface 4, and the treated surface 4 is formed by the composite The material layer 2 is formed by surface activation treatment. <Material layer> The composite layer of the multi-layered thin material of the present invention is composed of a fluororesin and a durable fiber woven fabric. The fluororesin of the present invention is not limited, and it may be from polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetra-ethylene-6 propylene copolymer (FEP). A heat resistant resin selected from the group consisting of. Among them, polytetrafluoroethylene is particularly preferred. The fluororesin can be blended with a conductive powder as needed. Thereby, electrical conductivity or material electrification can be imparted, and the abrasion resistance can be improved. Conductivity 201226178 Preferred examples of the powder are Carb〇n black and aitanmm Oxide. The amount of the compound is preferably 丨 扣 扣 = 么 = 么 于 于 ’ ’ ’ ’ ’ ’ ’ ’ ’ 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐 耐The thickness of the heat-resistant fiber woven fabric = 30 〜 Mm' is particularly preferably 3 〇 to 7 〇〇 (four). 4 The composite layer is preferably, for example, impregnated with a water-based county-liquid of fluororesin particles, and is woven by heat-resistant fibers, > ^~☆ $ #丄#上,心'', after drying, and then by firing form. ^ Solvents for aqueous suspensions Ι4>τι Α ν & σ, 』 δ weeks
懸浮液中的_粒子數係相對溶媒質量份，為二 質量份，特別以30〜60質量份為佳。 〜C 於本發明之複合材層係氟樹脂充份地浸透至耐熱性 維織布的内冑’且較佳地耐熱性纖維織布的表面係被氟 樹脂覆蓋。因此’將耐熱性纖維織布與氟樹脂的總量定^ 1()〇質量份，氟樹脂的施用量係3〇〜7〇質量份，特: 40〜60質量份為佳。 νλ <表面層> 成 酿 於本發明之複層薄材具有由聚醯亞胺系樹脂所構 的表面層。 於本發明中，聚醯亞胺系樹脂並無限定，較佳例如 1酿亞胺及聚酸胺酿亞胺（p〇lyamide imide)，特別以來 亞胺為佳。 ^ 本發明藉由塗佈表面層而形成時，為了容易塗佈可使 用液狀的1酿亞胺清漆（polyimide varnish )，且對應所需 201226178 可搭配溶劑。藉此，㈣健性Μ抑升塗佈效率。 又聚醯亞胺樹脂可對應所需而搭配導電性粉末。藉 此，例如給予導電性或熱傳導性或提升導電性或熱傳^ 性，且可達到提升耐磨損性。 上述表面層之形成係可將上述聚醯亞胺系樹脂塗佈 在複合材層的表面活性化處理面，乾燥後藉由燒成而進 行。聚醯亞胺系樹脂的燒成溫度較佳為300〜40(rc，特別 以330〜370°C為佳。 表面層的厚度可根據本發明之複層薄材及環狀帶的 具體用途或目的等而適當決定。例如，若係以製造特別適 用於搬送用途之環狀帶時所使用的複合薄材表示，聚酿亞 胺樹脂表面層的厚度較佳為1〜50/zm，特別以5〜20am為 佳。 ‘ <表面活性化處理> 於本發明之複層薄材中，上述表面層係介由—處理面 而形成，該處理面係藉由對該複合材層進行表面活性化處 理而形成。在此，表面活性化處理指的係藉由對本發明之 複合材層表面的氟樹脂進行處理而使其表面張力下降，以 使複合材層的氟樹脂與作為複層薄材之表面層而形成的 聚醯亞胺系樹脂為可接合，且產生充分之接合強度的處 理。若不進行此表面活性化處理’則無法在該複合材層形 成由聚亞胺系樹脂所構成的表面層，進而無法 ^ 明之目的。 χ 作為本發明之較佳表面活性化處理，例如可為二氧化 201226178 石夕粒子（silica particle)附著燒成處理、金屬鈉钱刻（Natrium etching)表面處理、電衆放電（plasma discharge)處理、 電暈放電（corona discharge)處理等，在這之中，特別以 二氧化矽粒子附著燒成處理為佳。 在此’本發明之表面活性化處理詳細如下所示。 —氧化發粒子附考燒成處理.係將二氧化砍粒子與氟 樹脂粒子的混合水性懸浮液塗佈於由氟樹脂及耐熱性纖 維織布所構成的複合材後，藉由進行燒成處理而提升複合 材表面之親水性的處理。 金屬鈉姓刻表面處理：係藉由金屬鈉溶液塗佈於氟樹 脂及耐熱性纖維織布所構成的複合材，而提升複合材表面 之親水性的處理。 電漿放電處理：係在由氟樹脂及耐熱性纖維織布所構 成的複合材之表面貝施輝光放電（gl〇w discharge)處理， 而提升複合材表面之親水性的處理。 電暈放電處理：係在由氟樹脂及耐熱性纖維織布所構 成的複合材之表面實施電暈放電處理，而提升複合材表面 之親水性的處理。 表面活性化處理較佳係對上述複合材層的表 面層之 形成部位全面進行，但亦可係對上述複合材層的表面層之 形成部分的一部分進行。 藉由實施此表面活性化處理，將純水滴在複合材層表 面的氟樹月曰上％•的接觸角（c〇ntact angle )(曰本工業標準 JIS，K6768)明顯減小。表面活性化處理前為1〇6度的接 11 201226178 觸角’，由二氧切粒子附著燒成處理接觸角$如〜列 度，而藉由金屬鈉蝕刻表面處理接觸角為5〇〜的度，“ 電漿放電處理則下降至50〜60度。 又猎 <環狀帶> 夺u之由上述㈣料所形成 Z環狀體而形成。因此，本發明之環狀帶具有上述複層薄 险，例如主要根據氣樹脂及耐熱性纖维織布所 :成的複&材層具有良好的耐熱性、形狀安定性、非黏著 各以及主要根據表面層的聚酿亞胺系樹脂具有 種特性（例如，耐磨損性、耐熱性、耐久性）。 接著’本糾之職帶㈣造方法，雜上述複 得=Γ;接合此複層薄材帶狀物的相對二端部;獲 :帶環狀體例如可係⑴藉由將複層薄 (圖3㈤ 部㈣邊範圍與另—端部重合而接合 接Α於1·(2)藉由將複層薄材帶狀物的二端部堅固地 物:二端圖3⑻);(3)藉由將複層薄材帶狀 得。又 接5於同一連接用薄材（圖3(C))而獲 用黏著劑：:的接合係可藉由熱封合一)或使 材與二ίΓ月之另一環狀帶的製造方法係將上述複層薄 :分別接合或近接配置而得一環狀:另::材::::二端 缚材積層薄材可❹係單層缝㈣所構 12 201226178 相。又’此另一薄材可使用單層及複層薄材。此另一薄材 例如亦包括上述複合材2及複層薄材1〇、η等。 圖4為顯示本發明之環狀帶的較佳具體例。圖4所示 的本發明之環狀帶12，係圖1所示的複層薄材10於外周 侧，而另一薄材5於内周側，此另一薄材5係使用與上述 複合材層2相同内容的薄材。本發明之環狀帶12，係複層 薄材1〇的相對二端部及此帶狀物的上述另—薄材5的二 對二端部在位置6、7,並分別使其接合或使其近接配置而 得一環狀體為環狀帶。 卜句令知听之核狀1的較佳具體例，亦包括圖1 所示的複層薄材Π)於内周侧，而另—薄材5於外周側。 糾生本發明與利用藉由習知模具所製成之無縫管狀物以 ，本發明係可對應用途而容易製造 所而克度、長度、層之構成的環狀帶。 的環將寬度宽 度’藉此，可同時製造複數個長度相同的Hit需寬 裁切上述寬度寬的環狀帶時，藉由調整寬产，二：’在 且區分相異寬度的環狀帶。 、又而谷易作成 本發明之I層薄材與另_薄材 由將複層薄材及另一薄材熱封合而得之積：薄材較佳係藉 劑將複層薄材及另一薄材接合:之，亦可係藉由黏著 [實施例] *積層薄材。 <實施例Al> 13 201226178 (1)形成聚醯亞胺樹脂表面層於複合材之一面的複 層薄材 首先，為了獲得氟樹脂及玻璃纖維的複合材，以連續 塗佈裝置將氟樹脂（PTFE)的水性懸浮液含浸且附著於平 織的玻璃纖維（厚度95 /z m)，以80°C乾燥後，再以350 °0的溫度燒成而得氟樹脂及玻璃纖維的複合材（厚度1.35 // m )。 接者’為了在敦樹脂及玻璃纖維的複合材進行表面活 性化處理，將PTFE樹脂的水性懸浮液100質量份混合於 二氧化矽的水性懸浮液100質量份，而得表面活性化處理 液。 接著，以連續塗佈裝置將表面活性化處理液塗佈在氟 樹脂及玻璃纖維之複合材的一面，以80°C乾燥後，再以 3 5 0 C的溫度燒成’使二氧化發附著燒成而得表面活性化 處理層。 接著，為了獲得液狀聚酿亞胺清漆，將溶劑（二曱基 乙醯胺（DMAC) 100質量份混合於市面販售的（東麗公 司製的「Toray neece #3000」（商品名））1〇〇質量份，而得 黏性50Cp (centipoise)的液狀聚酿亞胺清漆。 接著’以連續塗佈裝置將上述液狀聚醯亞胺清漆塗 佈、附著於上述氟樹脂及玻璃纖維之複合材（厚度l35/z m )已表面活性化處理的面’以8 0 C乾燥後，再以3 5 0。〇 的溫度燒成’而得一形成聚醯亞胺樹脂表面層於1樹脂及 玻璃纖維之複合材之一面的複層薄材（厚度14〇//m)(圖 14 201226178 以下列評價方法比較上述所得到的複合材之氟樹脂 層面及複層薄材之聚醯亞胺樹脂層面。評價結果表示於表 1 ° 1) 磨損試驗：根據JIS曰本工業標準H8682-1實施。 (使用SUGA磨損試驗機，以速度2.4m/分，載重350gf， 試驗轉動數1000次，作為對磨材的磨耗輪（abrading wheel)(直徑50mm、寬度12mm)，#4000而才水薄膜的條 件測定。） 2) 摩擦係數：根據JIS曰本工業標準K7218實施。（使 用Orientec公司製的摩擦磨損試驗機，以滑動速度 50mm/S，載重20N，試驗時間30分，及使用對磨材SUS304 環測定。） 3) 接觸角：根據JIS日本工業標準K6768實施。（使 用協和界面化學公司製的接觸角計（contact angle meter ) CA-D型，且使用蒸餾水作為試驗液測定。） 〔表1〕 試驗項目 氟樹脂層面 (PTFE) 聚酿亞胺樹脂層面 磨損量（mg ) 0.24 0.06 摩擦係数 0.18 0.20 接觸角（度） 106 95 根據上述評價結果，聚醯亞胺樹脂的耐磨損性優於氟 15 201226178 樹脂，而非黏著性、低摩擦性劣於氣樹脂。根據其結果， 可知聚酿亞胺樹脂比氟樹脂難以磨損、滑動。 a知例A1的構造較佳係將氣樹脂面用於非黏著性重 要、止滑性不重要的作業側’而將聚醯亞胺樹脂面用於耐 磨損性及止滑性重要的作業非接觸側，但不以此為限。 <實施例A2 > ⑵形成聚醯亞胺樹脂表面層於複合材之兩面的複 層薄材 、與實施例A1相同而得複層薄材。於此複層薄材的未 形成聚醯亞胺樹脂表面層之一面，與實施例ai相同操作 而進行表面活性化處理及聚醯亞胺樹脂表面層的形成，而 得-形成《亞胺樹脂表面層於複合材之㈣的複層薄 材（厚度145//m)(圖2)。 貫施例A2的構造係較佳為使用於耐磨損性、止滑性 重要’而非黏著性不重要之用途，但不以此為限。 <實施例A3> (3 )貫施例A1之複層薄材與另一薄材的積層薄材， 以及環狀帶 將實施例A1的複層薄材（厚度14〇“m)、氣樹脂及 玻璃纖維之複合材（厚度135//m)積層，且重疊同為氣 樹脂的層面，再以熱愿機且以35(TC的温度使其熱封合， 以使其為環狀’而得一形成氣樹脂表面層於其一面、聚酿 亞胺樹脂表面層於其另—面的環狀帶（厚度275鋒）（圖 4)〇 16 201226178 此實施例A3之環狀帶的構造較佳係 非黏著性重要、止滑性不重要的作業側，而面用於 脂面用於耐磨損性及止滑性重要的作 、^亞胺樹 滾輪側，但不以此為限。 /、接觸側的驅動 • <實施例A4> (4)將兩牧實施例A1之複層薄材穑 亞胺樹脂的環狀帶 、曰兩面為聚醯 準備兩個實施例A1之複層薄材（ ，將同為氣樹脂的層面重疊，再以熱‘且 μ度使其熱封合而積層，以使其為環狀，—/、、 亞胺樹脂表面層於其兩面的環狀帶 ^形成聚酿 4) 〇 φ w予度 28〇//m)(圖 此實施例A4之環狀帶的構造係較 性、止滑性重要、非黏著性不重要 '、^貝 颅。 文町用途上，但不以此為 /上述實施例A1〜A4’可提供具有耐熱性、耐磨損 ^非黏著性及止滑性的高機能複層薄材及由此複層薄材 構成的搬送帶，係給予對應所需的非黏著性、耐磨損性、 裁㈣所需尺寸且利用環狀方式，不須使用模具 可製造對應各式各樣尺寸的壤狀帶。 <比較例Al> .在實施例A1的複層薄材不進行表面活性化處理而係 塗佈液狀聚酸亞胺清漆，但無法接合，而無法獲得一具有 可使用之充份接合強度的複層薄材。 17 201226178 <實施例Cl〜C4> 於實施例A1〜A4中，取代二氧化矽附著燒成處理而藉 由進行金屬鈉蝕刻處理形成表面活性化處理層之外，其他 皆與實施例A1〜A4相同，而得本發明之複層薄材Cl、C2 及環狀帶C3、C4。 <實施例D1〜D4> 於實施例A1〜A4中，取代二氧化矽附著燒成處理而藉 由進行電漿處理形成表面活性化處理層之外，其他皆與實 施例A1〜A4相同，而得本發明之複層薄材Dl、D2及環狀 帶 D3、D4。 <接合強度試驗> 對藉由上述實施例A1〜A4、實施例C1〜C4及實施例 D1〜D4所得到的各複層薄材的聚醯亞胺表面層，根據曰本 工業標準JIS H5400實施劃格附著力試驗（cross cut adhesion test) ( lmmxl80.39L )，但從複層薄材剝離的方格 數在任何一個複層薄材皆為零。一方面，在未進行表面活 性化處理層的比較例A1中，剝離的方格數為100個。評 價結果表不於表2。 〔表2〕 剝離的方格數 實施例A1 0 實施例A2 0 實施例A3 0 18 201226178 實施例A4 0 ' 比較例A1 100 '''''' 實施例Cl -- 0 實施例C2 0 ^ 實施例C3 0 實施例C4 0 實施例D1 0 實施例D2 0 實施例D3 0 貫施例D4 0 ~ ----- [圖式簡單說明】 圖1為顯示本發明之複層薄材之構造的剖面圖. 圖2為顯示本發明之複層薄材之構造的剖面圖·’ 圖3為顯示本發明之環狀帶之構造的剖面圖；以及 圖4為顯示本發明之環狀帶之構造的剖面圖。 【主要元件符號說明】 2 :複合材層 2a :氟樹脂 2b :耐熱性纖維織布 3 a .表面層 4 .處理面 5 :另一薄材 19 201226178 6、7 :端部接合位置 10、11 :複層薄材 12 :環狀帶The number of _ particles in the suspension is two parts by mass based on the mass part of the solvent, and particularly preferably from 30 to 60 parts by mass. ～C The composite layer-based fluororesin of the present invention is sufficiently impregnated into the inner 胄' of the heat-resistant woven fabric, and preferably the surface of the heat-resistant fiber woven fabric is covered with the fluororesin. Therefore, the total amount of the heat-resistant fiber woven fabric and the fluororesin is set to 1 part by mass, and the application amount of the fluororesin is 3 〇 7 7 parts by mass, particularly preferably 40 to 60 parts by mass. Νλ <surface layer> The multi-layered thin material produced in the present invention has a surface layer composed of a polyimide pigment. In the present invention, the polyimine-based resin is not limited, and is preferably, for example, a flavonimide or a polyphosphonium imide, particularly preferably an imine. When the present invention is formed by coating a surface layer, a liquid imimental varnish can be used for easy coating, and a solvent can be used in accordance with 201226178. Thereby, (4) the physical properties are suppressed and the coating efficiency is increased. Further, the polyimide resin can be used in combination with a conductive powder as needed. Thereby, for example, conductivity or thermal conductivity or conductivity or heat transfer property is imparted, and the abrasion resistance can be improved. In the formation of the surface layer, the polyimine-based resin may be applied to the surface-treated surface of the composite layer, dried, and then fired. The polyiminoimide resin preferably has a firing temperature of 300 to 40 (rc, particularly preferably 330 to 370 ° C. The thickness of the surface layer may be according to the specific use of the laminated thin material and the endless belt of the present invention or For example, if the composite thin material used in the production of the endless belt which is particularly suitable for the transfer application is used, the thickness of the surface layer of the polyimide resin is preferably from 1 to 50/zm, particularly 5~20am is preferable. '<Surface activation treatment> In the multi-layered thin material of the present invention, the surface layer is formed by a treatment surface which is surface-treated by the composite layer Here, the surface activation treatment refers to the surface tension of the fluororesin on the surface of the composite layer of the present invention, so that the fluororesin of the composite layer is thin as a stratified layer. The polyimine-based resin formed by the surface layer of the material is a process capable of joining and producing sufficient joint strength. If the surface activation treatment is not performed, the polyimide layer cannot be formed in the composite layer. The surface layer that constitutes, and thus cannot For the purpose of the preferred surface activation treatment of the present invention, for example, dioxide dioxide 201226178 silica particle adhesion baking treatment, metal naphthalene surface treatment, plasma discharge (plasma) Among them, the cerium oxide particle adhesion baking treatment is particularly preferable. Here, the surface activation treatment of the present invention is as follows: - Oxidation The particle-attached calcination treatment is carried out by applying a mixed aqueous suspension of the oxidized chopped particles and the fluororesin particles to a composite material composed of a fluororesin and a heat-resistant fiber woven fabric, and then raising the composite by performing a baking treatment. The treatment of the hydrophilicity of the surface of the material. The surface treatment of the metal sodium is carried out by applying a metal sodium solution to a composite material composed of a fluororesin and a heat-resistant fiber woven fabric to enhance the hydrophilicity of the surface of the composite material. Slurry discharge treatment: on the surface of a composite material composed of a fluororesin and a heat-resistant fiber woven fabric, a glazing discharge treatment is performed, and the complex is lifted. Corrosion treatment of the surface of the composite material Corona discharge treatment: Corona discharge treatment is applied to the surface of the composite material composed of the fluororesin and the heat-resistant fiber woven fabric to enhance the hydrophilicity of the surface of the composite material. The activation treatment is preferably performed on the entire surface of the surface layer of the composite material layer, but may be performed on a part of the surface layer of the composite material layer. By performing the surface activation treatment, the purity is pure. The contact angle (c〇ntact angle) of the water droplets on the surface of the composite layer is significantly reduced (the standard JIS, K6768). The surface is 1 to 6 degrees before the surface activation treatment. 201226178 The antennae' is treated by the oxidized particles attached to the firing angle of the contact angle of $such as columnar, and the contact angle of the surface treated by the metal sodium etching is 5 〇, "the plasma discharge treatment is lowered to 50 to 60 degrees. And hunting <loop band> is formed by the Z ring formed by the above (4) material. Therefore, the endless belt of the present invention has the above-mentioned stratified thin layer risk, for example, mainly based on a gas resin and a heat-resistant fiber woven fabric: the composite material layer has good heat resistance, shape stability, non-adhesiveness, and The polyi-imide resin mainly based on the surface layer has various characteristics (for example, abrasion resistance, heat resistance, and durability). Then, 'the corrective action belt (four) method, the above-mentioned complex = Γ; the opposite ends of the lapped thin strip; the obtained ring-shaped body, for example, can be (1) by thinning the stratification ( Figure 3 (5) Part (4) The edge range coincides with the other end and the joint is joined by 1 (2) by solidifying the two ends of the multi-layered thin material strip: two ends Figure 3 (8)); (3) It is obtained by stripping the laminated thin material. Further, a method of manufacturing an adhesive tape using the same bonding material (Fig. 3(C)) can be obtained by heat sealing one or the other annular tape of the material and the bonding material. The above-mentioned multi-layer thin layer is respectively formed by joining or being closely connected to obtain a ring shape: another:: material:::: two-end binding material laminated thin material can be twisted single-layer seam (four) constructed 12 201226178 phase. Also, this other thin material can use a single layer and a multiple layer of thin material. The other thin material also includes, for example, the above composite material 2 and the composite thin materials 1〇, η, and the like. Fig. 4 is a view showing a preferred embodiment of the endless belt of the present invention. The endless belt 12 of the present invention shown in Fig. 4 is formed on the outer peripheral side of the multi-layered thin material 10 shown in Fig. 1, and the other thin material 5 is on the inner peripheral side, and the other thin material 5 is used in combination with the above. The thin layer of the same content of the material layer 2. The endless belt 12 of the present invention is a pair of two ends of the laminated thin material 1 及 and the two opposite ends of the other thin material 5 of the strip at positions 6 and 7, respectively, and are joined or The annular body is an endless belt. A preferred embodiment of the nucleus 1 of the sentence is also included on the inner peripheral side of the multi-layered thin metal material shown in Fig. 1, and the other thin material 5 is on the outer peripheral side. The present invention and the use of a seamless tubular body made by a conventional mold, the present invention is capable of easily producing an endless belt having a gradation, a length, and a layer in accordance with the use. The width of the ring will be 'by this, and it is possible to simultaneously manufacture a plurality of Hits of the same length to widen the wide band of the above width, by adjusting the width, and two: 'and distinguishing the annular bands of different widths . And the easy-to-inventure of the I-layer thin material and the other thin material are obtained by heat-sealing the multi-layer thin material and another thin material: the thin material is preferably a bulk material and the multi-layer thin material and Another thin material is bonded: it may be laminated by thin film [Example]. <Example Al> 13 201226178 (1) Forming a multi-layered thin layer of a surface layer of a polyimide resin on one side of a composite material First, in order to obtain a composite material of a fluororesin and a glass fiber, a fluororesin is continuously applied by a coating device The aqueous suspension of (PTFE) is impregnated and adhered to plain woven glass fiber (thickness 95 /zm), dried at 80 ° C, and then fired at a temperature of 350 ° 0 to obtain a composite of fluororesin and glass fiber (thickness). 1.35 // m ). In order to carry out the surface activation treatment of the composite material of the resin and the glass fiber, 100 parts by mass of the aqueous suspension of the PTFE resin is mixed with 100 parts by mass of the aqueous suspension of cerium oxide to obtain a surface-activated treatment liquid. Next, the surface active treatment liquid was applied to one surface of the composite material of the fluororesin and the glass fiber in a continuous coating apparatus, dried at 80 ° C, and then fired at a temperature of 350 ° C to cause adhesion of the oxidized hair. The surface-activated layer was obtained by firing. Next, in order to obtain a liquid polyimine varnish, a solvent (100% by mass of dimethyl acetamide (DMAC) was mixed and sold in the market (Toray neece #3000 (trade name) manufactured by Toray Industries, Inc.) 1 〇〇 by mass, and a 50 Cp (centipoise) liquid polyimide varnish is obtained. Next, the above liquid phthalocyanine varnish is applied and adhered to the fluororesin and glass fiber by a continuous coating device. The surface of the composite material (thickness l35/zm) which has been surface-activated is dried at 80 ° C and then fired at a temperature of 350 ° C to obtain a surface layer of the polyimide resin. And a laminated thin material (thickness of 14 〇 / / m) on one side of the composite of glass fiber (Fig. 14 201226178) The fluororesin layer of the composite material obtained above and the polyimine of the stratified thin material were compared by the following evaluation methods. Resin level. Evaluation results are shown in Table 1 ° 1) Abrasion test: According to JIS 曰 industrial standard H8682-1. (Using SUGA wear tester, speed 2.4m/min, load 350gf, test rotation number 1000 times, as Abrasing wheel for abrasive material (diameter 50mm, width) ), # 4000 and water was measured 12mm film strip member) 2) Friction coefficient: According to JIS K7218 embodiment said Industrial Standard. (The friction and wear tester manufactured by Orientec Co., Ltd. was used at a sliding speed of 50 mm/s, a load of 20 N, a test time of 30 minutes, and a ring of SUS304 for the abrasive material.) 3) Contact angle: It was carried out in accordance with JIS Japanese Industrial Standard K6768. (The contact angle meter CA-D type manufactured by Kyowa Interface Chemical Co., Ltd. was used, and distilled water was used as the test liquid.) [Table 1] Test item fluororesin layer (PTFE) (mg) 0.24 0.06 Coefficient of friction 0.18 0.20 Contact angle (degrees) 106 95 According to the above evaluation results, the abrasion resistance of the polyimide resin is better than that of the fluorine 15 201226178 resin, and the non-adhesiveness and low friction are inferior to the gas resin. . According to the results, it was found that the polyolefin resin was less likely to be worn and slipped than the fluororesin. The structure of the example A1 is preferably such that the gas-resin surface is used for the work side where the non-adhesive property is important and the slip resistance is not important, and the polyimide film surface is used for the wear resistance and the slip resistance. Non-contact side, but not limited to this. <Example A2 > (2) A multi-layered thin material in which the surface layer of the polyimide film was formed on both surfaces of the composite material, and a multi-layered thin material was obtained in the same manner as in Example A1. On one side of the surface layer of the multi-layered polyimide material on which the polyimine resin was not formed, the surface activation treatment and the formation of the surface layer of the polyimide film were carried out in the same manner as in Example ai, and the "imide resin" was formed. The surface layer is laminated to the composite layer (4) of the composite material (thickness 145 / / m) (Figure 2). The structure of the embodiment A2 is preferably used for the purpose of abrasion resistance and slip resistance, but not for the purpose of adhesion, but is not limited thereto. <Example A3> (3) The laminated thin material of the composite layer A1 and the other thin material, and the endless layer of the laminated layer of Example A1 (thickness 14 〇 "m), gas A composite of resin and glass fiber (thickness 135/m) is laminated, and the layers of the resin are superposed on each other, and then heat-sealed and sealed at 35 (TC temperature to make it ring-shaped) The formation of a gas resin surface layer on one side thereof, the surface layer of the polyimide resin surface layer on the other side of the annular belt (thickness 275 front) (Fig. 4) 〇16 201226178 The structure of the annular belt of this embodiment A3 It is preferred that the non-adhesive property is important, the slip-resistance is not important on the working side, and the surface is used for the grease surface which is important for wear resistance and slip resistance, and the imine tree roller side is not limited thereto. /, drive on the contact side • <Example A4> (4) Preparation of the two-layer A1 of the double-layered bismuth imide resin of the two animal husbandry examples A1 and the two sides of the enamel for the preparation of the two examples A1 The layer of thin material (will overlap the layer of the same gas resin, and then heat-sealed and μ degrees to heat-sealed and laminate it to make it ring-shaped, -/, and imine resin surface layer The annular band on both sides forms a brewing 4) 〇φ w predegree 28〇//m) (the structure of the annular belt of the embodiment A4 is relatively important, the slip resistance is important, and the non-adhesiveness is not important) , ^贝脑. The use of Wencho, but not the above, the above embodiments A1 to A4' can provide heat-resistant, wear-resistant ^ non-adhesive and slip-resistant high-performance multi-layer thin material and The conveyor belt consisting of a multi-layered thin material is given a required non-adhesiveness, abrasion resistance, and the required size (4), and is formed in a ring-shaped manner, and it is possible to manufacture a soil shape corresponding to various sizes without using a mold. <Comparative Example Al> The layered thin material of Example A1 was coated with a liquid polyimine varnish without surface activation treatment, but was not bonded, and it was not possible to obtain a sufficient sufficiency to be used. Composite layer thin material of bonding strength. 17 201226178 <Examples C1 to C4> In Examples A1 to A4, a surface-activated treatment layer was formed by performing a metal sodium etching treatment instead of the cerium oxide adhesion baking treatment. Others are the same as those of Examples A1 to A4, and the laminated thin materials Cl, C2 and the ring of the present invention are obtained. C3, C4. <Examples D1 to D4> In Examples A1 to A4, in addition to the cerium oxide adhesion baking treatment, the surface treatment treatment layer was formed by plasma treatment, and other examples and examples A1 to A4 are the same, and the laminated thin materials D1 and D2 and the endless belts D3 and D4 of the present invention are obtained. <Joint strength test> With the above Examples A1 to A4, Examples C1 to C4, and Examples The polyiminoimine surface layer of each of the multi-layered thin materials obtained from D1 to D4 is subjected to a cross cut adhesion test (lmmxl80.39L) according to the standard JIS H5400 of the standard, but from the laminated thin material. The number of squared strips is zero in any of the multiple layers. On the other hand, in Comparative Example A1 in which the surface active layer was not subjected to treatment, the number of squares peeled off was 100. The evaluation results are not shown in Table 2. [Table 2] Number of squares peeled off Example A1 0 Example A2 0 Example A3 0 18 201226178 Example A4 0 'Comparative Example A1 100 '''''' Example Cl - 0 Example C2 0 ^ Implementation Example C3 0 Embodiment C4 0 Embodiment D1 0 Embodiment D2 0 Embodiment D3 0 Embodiment D4 0 ~ ----- [Simplified Schematic] FIG. 1 is a view showing the construction of a multi-layered thin material of the present invention. Fig. 2 is a cross-sectional view showing the structure of a multi-layered thin material of the present invention. Fig. 3 is a cross-sectional view showing the structure of the endless belt of the present invention; and Fig. 4 is a view showing the structure of the endless belt of the present invention. Sectional view. [Description of main component symbols] 2: Composite layer 2a: fluororesin 2b: heat-resistant fiber woven fabric 3 a. Surface layer 4. Treatment surface 5: Another thin material 19 201226178 6, 7: End joint position 10, 11 :Multilayer thin material 12: annular belt