593462593462
本發明係有關一種強化或者裹覆材料之製作程序，該材 料尤其是平面狀結構體且浸潰或塗佈有反應樹脂，該反應 树脂在室溫時雖無黏性但尚未硬化。此種平面狀結構體例 如為預浸潰體或預塗佈膜，尤其是預塗佈金屬膜，被用來 製作複合材料，尤其是製作有金屬塗佈或無塗佈之電疊 片。 由於良好的化學、機械及電特性，環氧樹脂被優先使用 作為該平面狀結構體之反應樹脂。 習知技術中（比較塑料手冊第1 〇冊「熱固性塑料」，第2 版（1988) ’第3 8 7頁）浸潰或塗佈有熱固性塑料之平面狀載 體材料被乾燥及預硬化。此種所謂的預浸潰體被切割成同 等大小的塊狀、堆疊起來並以鋼板或壓模加熱壓製。使用 的樹脂溶在一有機溶劑中，該溶劑在浸潰後需被蒸發掉。 此外樹脂的預硬化狀態（B狀態）難以設定。 專利EP-A 0 142 463曾提出一種預浸漬體之製作程序，其以 一液態混合物浸潰強化材料，該液態混合物包含一環氧樹 脂、一光聚合化合物、一環氧樹脂之熱反應硬化劑及一光 聚合化合物之光聚合催化劑。浸漬後結構體被曝光，故光 聚合化合物聚合。如此而產生一基本上無黏性之預浸潰 體，其環氧樹脂基可在稍後被硬化，故可由此預浸漬體製 作出複合材料。 此種程序不使用溶劑且可以光聚合進入B狀態。但如此 製作出之複合材料缺點在於，機械強度，尤其是疊層内之 抗剪強度不足以使用於高級用途。 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐）The present invention relates to a process for manufacturing a reinforcing or coating material. The material is especially a planar structure and is impregnated or coated with a reaction resin. The reaction resin is not viscous but not hardened at room temperature. Such planar structures, such as pre-impregnated bodies or pre-coated films, especially pre-coated metal films, are used to make composite materials, especially metal laminates with or without coating. Due to good chemical, mechanical and electrical properties, epoxy resins are preferably used as the reaction resin for this planar structure. In conventional techniques (Comparative Plastics Handbook Volume 10 "Thermosetting Plastics", 2nd edition (1988) 'p. 37 8), flat carrier materials impregnated or coated with thermosetting plastics are dried and pre-hardened. This so-called prepreg is cut into pieces of equal size, stacked, and heated and pressed with a steel plate or a stamper. The resin used is dissolved in an organic solvent, which must be evaporated after immersion. In addition, the pre-hardened state (state B) of the resin is difficult to set. Patent EP-A 0 142 463 has proposed a process for making a prepreg, which impregnates the reinforcing material with a liquid mixture containing an epoxy resin, a photopolymerizable compound, and a thermally reactive hardener for the epoxy resin. And a photopolymerization catalyst for a photopolymerization compound. The structure is exposed after the immersion, so the photopolymerizable compound is polymerized. In this way, a substantially non-sticky prepreg is produced, the epoxy resin base of which can be hardened later, so the composite can be made from the prepreg system. This procedure uses no solvents and can photopolymerize into the B state. However, the disadvantage of the composite material produced in this way is that the mechanical strength, especially the shear strength in the laminate is not sufficient for advanced applications. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)
裝 f -4 - 五、發明説明（ 本發明之目的因此在於提供一種以樹脂處理過的強化或 ^裹覆材料之製作程序，其不使用溶劑，尤其是以一反應 树脂度潰或塗佈平面狀結構體，例如預浸潰體或塗佈樹脂 金屬膜，其樹脂B狀態之設定簡單、精確且可重複，樹脂 在B狀態存放穩定，以熱壓平面狀結構體而製作出的複合 材料具良好電特性、高機械強度及良好化學藥品耐抗性。 本目的由下述而達成：申請專利範圍第1至5項所述以樹 脂處理過的強化或者裹覆材料，尤其是預浸潰體或裹覆金 屬膜或以樹脂處理過的絲束及絞絲，之製作程序，申請專 利範圍第6至8項所述.以此製作程序製出之預浸潰體或裹覆 金屬膜或以樹脂處理過的絲束及絞絲，以及申請專利範圍 第9項所述使樹脂處理過的強化或者裹覆材料製成的成形 件熱硬化之複合材料製作程序。 本發明發現使用含有具一或多缔不飽和碳酸之二及/或 水環氧化合物偏酯、縮水甘油丙缔酸醋及/或縮水甘油甲 基丙婦酸酯以及引發光聚合及使環氧基硬化之硬化催化劑 及/或硬化劑的樹脂系統製作以樹脂處理過的強化或者裹 覆材料可達到此目的。以此種樹脂系統浸潰或塗佈過的平 面狀結構體被可見光，尤其是紫外線光照射時，缔不飽和 基聚合。此樹脂系統精確進入熱塑性B狀態，並可在該狀 怨下保持存放穩定，直至其被加熱超過環氧基硬化反應之 起始溫度。藉硬化催化劑之選擇可大範圍改變該起使溫 度。起始溫度以上環氧基硬化，樹脂系統成為不可熔化。 以此種樹脂系統製作出之平面狀結構體可在該起始溫度以 本紙張尺度如中圏國家標準(CNS) L規格(21GX297公着） 593462 A7 _______B7 五、發明説明（3 )~' ' 上被互相擠壓而結合成具良好電特性、高機械強度及良好 化學藥品耐抗性之複合材料。 具一或多晞不飽和碳酸之二及/或聚環氧化合物偏酯習 知為具至少兩環氧基分子之環氧化合物與一或多烯不飽和 酸之反應產物。 此種酸例如為丙缔酸、甲基丙缔酸、肉桂酸或糠基丙缔 酸。在此種習知反應中環氧基與烯不飽和酸的比例需適當 選擇，以使產生的偏酯至少含一環氧基及一晞不飽和基分 子。故例如使二環氧化合物與量相當於環氧基之4 0至5 0 % 的晞不飽和酸反應。使用聚環氧化合物時，環氧基與晞不 飽和酸的莫耳比在2 :0.5至2 :1.5之間。 此反應之環氧樹脂成份可是具至少兩環氧基分子之所有 環氧化合物，而且是脂族及芳族聚碳酸之聚縮水甘油醚以 及聚縮水甘油酯。優先的是以苯酚或甲酚酚醛清漆為基的 聚環氧化合物及室溫下為液態的聚苯酚縮水甘油醚，例如 表氯醇與雙苯齡A或雙苯紛F之反應產物。此種環氧樹脂 之環氧當量為160-〉700。此外亦為優先的是單體芳族或脂族 二及三環氧化合物，例如丁二烯-、二甲基戊二烯-、葶烯 -、二乙烯苯-或乙晞環己烯-二氧化物以及脂族、芳脂族、 環脂族或芳族二醇或胺之二縮水甘油醚及三縮水甘油醚， 尤其是乙二醇、二乙二醇、丙二醇、丁二醇、己二醇、間 苯二S分或苯胺之二縮水甘油謎及甘油或三甲基丙炫*之二 縮水甘油醚。 為降低黏度，二及/或聚環氧化合物之偏酯中加入2 · 5至 -6 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 593462 A7 B7 五、發明説明 2 5重量百分比之縮水甘油丙烯酸酯及/或縮水甘油甲基丙 埽酸酯。縮水甘油丙烯酸酯及/或縮水甘油甲基丙烯酸酯 優先之使用量為偏酯之5-20重量百分比。令人驚奇的是， 極為活潑的單體縮水甘油丙締酸酯及/或縮水甘油甲基丙 烯酸酯在光聚合及環氧基熱硬化時皆未導致不受控制的反 應或聚合樹脂混合物之不利高熱。 受處理的強化或者裹覆材料為織造或非織造之平面狀纖 維材料或無定向及連續或切斷之纖維或絞絲及薄膜，尤其 是金屬膜。纖維材料可是天然或合成纖維，尤其是纖維 素、破璃、硼、鋼、碳化矽、碳、或芳族聚醯胺纖維。優 先之強化材料為織物、無定向纖維網、絲束或绞絲狀態之 玻璃纖維。 為使晞不飽和基光聚合，本發明所使用的樹脂混合物中 加入習知（例如專利DE-A 27 06 638)之光聚合催化劑，尤其是 照射時進入一刺激狀態且生成引發聚合之基的光聚合催化 劑（光引發劑），以及照射產生之刺激能量直接傳輸至晞不 飽和基而導致光聚合之光聚合催化劑（光敏劑）。優先的是 光引發劑，例如苯偶姻、苯偶姻醚、苯偶醯二甲基縮酮、 二苯甲酮、二硫代-雙（苯並4唑）、氧代磷烷及芳族磺醯氯 與二硫化物或黃原酸酯之混合。此光聚合催化劑之使用量 為偏酯與縮水甘油（甲基）丙烯酸酯混合物之〇·5至1 0重量百 分比。 為使環氧基熱硬化，本發明所使用樹脂混合物含有潛伏 催化劑，其在室溫時不會使環氧基交聯，但在起始溫度以 本紙張尺度適用中國國家標準(CNS) Μ規格(⑽χ 297公爱) 593462 A7 B7 五、發明説明（5 ) 上會快速導致硬化。其例如為二氰二醯胺、適當之衍生 物、BF3 -或BCL3 -胺錯合物、酸酐或其加合物、咪唑、酚 硬化劑及金屬錯合催化劑。 特別優先的是可作為光引發劑使烯不飽和基交聯且可作 為硬化催化劑使熱硬化之潛伏催化劑。其例如為米蚩酮型 化合物，尤其是通式I至III之金屬錯合化合物： 通式I: MLxBy 通式 11: M[SR]XBZ 通式 III: M(PHal)m(N)n 其中Μ是一形成錯合之金屬的陽離子， SR是一有機或無機酸殘基， L是一形成螯合之配合基， Β是一路易氏基， PHal是一假鹵化物之離子， N是一氮基， X是一在1至8範圍中之數， y是一在1至5範圍中之數， z是一在7至8範圍中之數， m是一在2至3範圍中之數， η是一在1至6範圍中之數。 已述錯合物習知用作環氧樹脂之硬化催化劑。通式MLxBy 及M[SR]XBZ之錯合物首度由專利WO 91/13925提出，通式 錯合物則由德國專利申請案198 48 329.5提出。 其特徵為，與環氧樹脂混合時可確保極佳之室溫存放穩定 -8- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 593462 五、發明説明（6 性，具低起始溫度，且硬化之環氧樹脂具良妤機械、化 學、電特性及高Tg-值。 本發月發現，以紫外線光照射時，此金屬錯合化合物在 本發明所使用由具-或多婦不飽和碳酸之二及/或聚環氧 化合物偏酯、縮水甘油丙埽酸酯及/或縮水甘油甲基丙埽 酸酿所構成樹脂系統中亦可催化埽不飽和基的光聚合。但 令人驚奇的；％，此聚合反應尸、限於埽不飽和S，而不會使 環氧基硬化，故紫外線照射後本發明樹脂系統處於一存放 穩定的B狀態。到需要的時間時才進行樹脂處理過之強化 或裹覆材料之熱處理而使得環氧基硬化。 金屬錯合化合物之使用量為樹脂系統之〇1至5〇 ,尤其是 1至1 0重量百分比。 本發明所使用黏合劑混合物可含有習知之添加劑，例如 填充物及添加物，尤其是不使用浸潰程序而例如採取抹、 刮或滾壓處理裹覆材料時。 為製作預浸潰體或浸潰過之絞絲或絲束，本發明黏合劑 混合物通常使用浸潰程序，例如浸泡或噴塗。為此黏合劑 之黏度被設定在··.·至.··· mPas之使用黏度範圍中。該黏 度之設定不使用溶劑而只改變各成份的種類及組成。 本發明以樹脂處理過的強化或者裹覆材料之製作程序適 用於製作下述之所有材料··使強化或裹覆材料浸潰或塗佈 一黏合劑混合物，接著使該黏合劑混合物進入一無黏性、 預硬化，但仍為熱塑性的狀態（Β狀態），再使此中間產物 (成形件）視用途而定彼此或與其他材料一起接受加壓成形 9- 本紙張尺度適用中國國家標準(CNS) Α4規格(21〇 X 297公釐） 裝 訂 593462 A7 B7 五、發明説明（8 實例3 (浸潰混合物1 ) 使實例1之偏酯被其重量2 0 %之縮水甘油甲基丙晞酸酯 稀釋。得到2 5 °C時黏度為750 mPa’s環氧當量為235 g/當量的 樹脂溶液。 使該樹脂溶液與1 %苯偶醯二甲基縮酮（光引發劑）及6 〇/〇 二氰二醯胺（硬化劑）均勻混合。 實例4(預浸潰體） 以實例3的浸潰混合物浸潰玻璃織物（織物181/Interglas 91745)。浸潰後以紫外線（360-400 nm)照射織物。產生之預 浸潰體在室溫下無黏性。其不繼續硬化。 實例5(浸潰混合物2) 使實例2之偏酯被其重量3 5 %之縮水甘油甲基丙婦酸酯 稀釋。得到2 5 °C時黏度為950 mPa，s環氧當量為200 g/當量的 樹脂溶液。 使該樹脂溶液與1 %苯偶醯二甲基縮酮（光引發劑）及6 % 二氰二醯胺（硬化劑）均勻混合。 實例6(預浸潰體） 以實例5的浸潰混合物浸潰玻璃織物（織物181/Interglas 91745)。浸潰後以紫外線（360-400 nm)照射織物。產生之預 浸潰體在室溫下無黏性。其不繼續硬化。 實例7(預浸潰體；比較例） 使〇 -甲酚酚醛清漆環氧樹脂（RUtapox⑧VE 2510)被甲基乙 基甲酮稀釋至固體含量為6 5 %。該溶液黏度（2 5 °C )為800 mPa’s環氧當量為275 g /當量。 將5 %二氰二醯胺加入該溶液中。以得到之混合物浸潰 -11 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)装 f -4-5. Description of the invention (The purpose of the present invention is therefore to provide a resin-reinforced or coated material manufacturing process, which does not use solvents, especially with a reactive resin degree or coating surface Structures, such as prepregs or resin-coated metal films, are simple, accurate, and repeatable for setting the B state of the resin. The resin is stable when stored in the B state. It is a composite material produced by hot pressing a flat structure. Good electrical properties, high mechanical strength, and good chemical resistance. This objective is achieved by: resin-reinforced or coating materials, especially prepregs, as described in claims 1 to 5 of the scope of patent applications. The production procedure of the coated film or the resin-treated tow and skein is described in item 6 to 8. The pre-impregnated body or the coated metal film or the Resin-treated tow and skein, and a composite material manufacturing process for thermosetting a molded part made of a resin-treated reinforcing or coating material as described in item 9 of the patent application scope. The present invention finds the use of One or more unsaturated unsaturated carbonic acid bis and / or water epoxy compound partial esters, glycidyl propionate and / or glycidyl methyl propionate, and a hardening catalyst that initiates photopolymerization and hardens epoxy groups And / or hardener resin systems can be made with resin-treated reinforcement or coating materials. The planar structure impregnated or coated with this resin system is exposed to visible light, especially ultraviolet light, Unsaturated group polymerization. This resin system accurately enters the thermoplastic B state, and can be kept stable under this condition, until it is heated beyond the initial temperature of the epoxy-based hardening reaction. The choice of the hardening catalyst can be widely changed. The starting temperature is above. The epoxy group hardens above the starting temperature, and the resin system becomes infusible. The planar structure made with this resin system can be at this starting temperature at the paper scale such as the Chinese National Standard (CNS) L specification (published by 21GX297) 593462 A7 _______B7 V. Description of the invention (3) ~ '' are squeezed together to form good electrical properties, high mechanical strength and good chemicals Resistant composite materials. One or more polyunsaturated unsaturated carbonic acid and / or polyepoxide partial esters are known as the reaction product of an epoxy compound with at least two epoxy molecules and one or more olefinic unsaturated acids. Such an acid is, for example, acrylic acid, methyl acrylic acid, cinnamic acid, or furfuryl acrylic acid. In this conventional reaction, the ratio of epoxy group to ethylenically unsaturated acid needs to be appropriately selected so that the produced The partial ester contains at least one epoxy group and one fluorene unsaturated group molecule. Therefore, for example, a diepoxy compound is reacted with fluorene unsaturated acid in an amount equivalent to 40 to 50% of the epoxy group. When using a polyepoxide compound The molar ratio of epoxy groups to hydrazone unsaturated acids is between 2: 0.5 to 2: 1.5. The epoxy resin component of this reaction can be all epoxy compounds with at least two epoxy molecules, and they are aliphatic and Polyglycidyl ethers and polyglycidyl esters of aromatic polycarbonates. Preference is given to phenol or cresol novolac-based polyepoxides and polyphenol glycidyl ethers that are liquid at room temperature, such as the reaction product of epichlorohydrin and bisphenol age A or bisphenol F. The epoxy equivalent of this epoxy resin is 160-> 700. Preference is also given to monomeric aromatic or aliphatic di- and tri-epoxy compounds, such as butadiene-, dimethylpentadiene-, pinene-, divinylbenzene- or ethenecyclohexene-di Oxides and diglycidyl ethers and triglycidyl ethers of aliphatic, araliphatic, cycloaliphatic or aromatic diols or amines, especially ethylene glycol, diethylene glycol, propylene glycol, butanediol, adipic acid Diglycidyl mystery of alcohol, m-xylylene or aniline and diglycidyl ether of glycerol or trimethylpropane *. In order to reduce viscosity, 2 and 5 or -6 are added to the partial esters of di- and / or polyepoxide compounds.-This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 593462 A7 B7 5. Description of the invention 2 5 weight percent of glycidyl acrylate and / or glycidyl methyl propionate. Glycidyl acrylate and / or glycidyl methacrylate are preferably used in an amount of 5-20% by weight of the partial ester. Surprisingly, the extremely reactive monomers glycidyl acrylate and / or glycidyl methacrylate did not cause uncontrolled reactions or the disadvantage of polymerized resin mixtures during photopolymerization and epoxy-based thermosetting High fever. The reinforced or coated material to be treated is woven or non-woven flat fiber material or non-oriented and continuous or cut fiber or skein and film, especially metal film. The fibrous material may be natural or synthetic fibers, especially cellulose, broken glass, boron, steel, silicon carbide, carbon, or aramid fibers. The preferred reinforcing materials are woven fabrics, non-oriented webs, tows or stranded glass fibers. In order to photopolymerize the fluorene unsaturated group, a conventional (for example, patent DE-A 27 06 638) photopolymerization catalyst is added to the resin mixture used in the present invention, especially when it enters a stimulating state upon irradiation and generates a base that initiates polymerization. Photopolymerization catalysts (photoinitiators), and photopolymerization catalysts (photosensitizers) that cause the stimulus energy generated by irradiation to be transmitted directly to the fluorene unsaturated group and cause photopolymerization. Preference is given to photoinitiators such as benzoin, benzoin ether, benzoin dimethyl ketal, benzophenone, dithio-bis (benzo4azole), oxophosphorane, and aromatic Mixture of sulfonium chloride and disulfide or xanthate. The photopolymerization catalyst is used in an amount of 0.5 to 10% by weight of the mixture of the partial ester and the glycidyl (meth) acrylate. In order to thermally harden the epoxy group, the resin mixture used in the present invention contains a latent catalyst, which does not crosslink the epoxy group at room temperature, but the Chinese National Standard (CNS) M specification is applied at the initial temperature at this paper scale. (⑽χ 297 public love) 593462 A7 B7 V. Invention description (5) will cause hardening quickly. They are, for example, dicyandiamide, suitable derivatives, BF3- or BCL3-amine complexes, acid anhydrides or adducts thereof, imidazoles, phenol hardeners and metal complex catalysts. Particularly preferred are latent catalysts that can be used as photoinitiators to crosslink ethylenically unsaturated groups and can be used as hardening catalysts to thermally harden. It is, for example, a chrysene compound, especially a metal complex compound of the general formulae I to III: General formula I: MLxBy General formula 11: M [SR] XBZ General formula III: M (PHal) m (N) n where M is a cation forming a complex metal, SR is an organic or inorganic acid residue, L is a chelating complexing group, B is a Lewis group, PHal is a pseudohalide ion, and N is a Nitrogen, X is a number in the range of 1 to 8, y is a number in the range of 1 to 5, z is a number in the range of 7 to 8, m is a number in the range of 2 to 3 , Η is a number in the range of 1 to 6. It has been described that the complex is conventionally used as a curing catalyst for epoxy resins. The complex of the general formula MLxBy and M [SR] XBZ was first proposed by the patent WO 91/13925, and the complex of the general formula was proposed by the German patent application 198 48 329.5. It is characterized in that it can ensure excellent storage stability at room temperature when mixed with epoxy resin. -8- This paper size applies Chinese National Standard (CNS) A4 specifications (210X 297 mm) 593462 5. Description of the invention (6 properties, with Low initial temperature, and hardened epoxy resin has good mechanical, chemical, electrical properties and high Tg-values. This month, it was found that when irradiated with ultraviolet light, this metal complex compound is used in the present invention. Or polyunsaturated unsaturated carbonic acid and / or polyepoxide partial esters, glycidyl propionate and / or glycidyl methyl propionate can also catalyze the photopolymerization of pyrene unsaturated groups. But surprisingly,%, the polymerization reaction is limited to hydrazone unsaturated S, which does not harden the epoxy group, so the resin system of the present invention is in a stable B state after ultraviolet irradiation. When the time required Only the resin-treated reinforcing or coating material is heat-treated to harden the epoxy group. The amount of metal complex compound used is 0-1 to 50, especially 1 to 10 weight percent of the resin system. Used in the present invention Adhesive mixture It may contain conventional additives, such as fillers and additives, especially when the coating material is not treated using an impregnation procedure such as wiping, scraping or rolling. For the preparation of prepregs or impregnated strands or wires At present, the adhesive mixture of the present invention usually uses an impregnation procedure, such as dipping or spraying. To this end, the viscosity of the adhesive is set in the range of use viscosity of mPas. The viscosity is set without using a solvent Only the type and composition of each component are changed. The resin-treated strengthening or coating material manufacturing process of the present invention is applicable to the production of all of the following materials: • impregnating or coating the strengthening or coating material with an adhesive mixture Then, the adhesive mixture is brought into a non-sticky, pre-hardened, but still thermoplastic state (B state), and then this intermediate product (formed part) is subjected to compression molding with each other or with other materials depending on the application. 9- This paper size is in accordance with China National Standard (CNS) A4 specification (21 × 297 mm) binding 593462 A7 B7 5. Description of the invention (8 Example 3 (impregnated mixture 1) The partial ester of Example 1 is Its weight is 20% of glycidyl methylpropionate diluted. A resin solution having a viscosity of 750 mPa's epoxy equivalent weight of 235 g / equivalent at 25 ° C is obtained. The resin solution is mixed with 1% benzoin dimethylformate The ketal (photoinitiator) and 60/0 dicyandiamide (hardener) are mixed uniformly. Example 4 (pre-impregnated body) Impregnate the glass fabric with the impregnation mixture of Example 3 (fabric 181 / Interglas 91745 ). After impregnation, the fabric is irradiated with ultraviolet rays (360-400 nm). The resulting prepreg is non-sticky at room temperature. It does not continue to harden. Example 5 (impregnation mixture 2) The partial ester of Example 2 was Its weight is 35% of glycidyl methyl propionate diluted. A resin solution having a viscosity of 950 mPa at 25 ° C and an epoxy equivalent of 200 g / equivalent was obtained. This resin solution was uniformly mixed with 1% benzophenamine dimethyl ketal (photoinitiator) and 6% dicyandiamide (hardener). Example 6 (pre-impregnated body) The glass fabric (Fabric 181 / Interglas 91745) was impregnated with the impregnation mixture of Example 5. After impregnation, the fabric was irradiated with ultraviolet (360-400 nm). The resulting prepreg was non-sticky at room temperature. It does not continue to harden. Example 7 (prepreg; comparative example) A 0-cresol novolac epoxy resin (RUtapox (R) VE 2510) was diluted with methyl ethyl ketone to a solids content of 65%. The viscosity of the solution (25 ° C) was 800 mPa's and the epoxy equivalent was 275 g / equivalent. 5% dicyandiamide was added to the solution. Impregnated with the obtained mixture -11-This paper size applies to China National Standard (CNS) A4 (210X 297 mm)
裝 訂 f 593462 A7 B7 五、發明説明（9 ) 玻璃織物（織物181/Interglas 91745)。將浸潰過的織物放入一 爐中在8 0 °C下乾燥3 0分鐘。 實例8 (疊片製作） 使8層實例4，6及7之預浸潰體在170°C下各被互相壓緊及 硬化6 0分鐘。得到2 m m厚的疊片。測試該疊片之下述機 械特性：抗彎強度、彈性模數（E-Modul)、層内抗剪強度 (ILS)及玻璃轉化溫度（Tg)。其值如表1所示： 表1 預浸潰體 實例4 實例6 實例7 抗彎強度[MPa] 450 480 450 彈性模數[MPa] 18,000 22,000 25,000 ILS [MPal 35 38 40 Tg(DSC)[°C] 140 160 165 實例9(裹覆膜） 使100 g實例3之浸潰混合物與5 0 g滑石、5 0 g矽烷化石 英粉及3 g高度分散的矽酸（Aerosil⑧200)混合成一糊狀黏合 料。使用一刮板將該黏合料塗到一銅膜上並使塗層厚度為 5 0 μ m。以紫外線（360^400 n m)照射塗佈妤的銅膜。得到 一存放穩定且在室溫下無黏性的裹覆銅膜。 實例1〇(裹覆膜） 使100 g實例5之浸潰混合物與5 0 g滑石、5 0 g矽烷化石 英粉及3 g高度分散的碎酸（Aerosil⑧200)混合成一糊狀黏合 料。使用一刮板將該黏合料塗到一銅膜上並使塗層厚度為 -12- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 593462 A7 B7 五、發明説明（1〇 ) 5 Ο μ m。以紫外線（36〇4〇〇舰）照射塗佈好的銅膜。得到一 存放穩定且在室溫下無黏性的裹覆銅膜。 實例1 1 (裹覆膜；比較例） 使100 g實例7之浸潰混合物（〇-甲酚酚醛清漆環氧樹脂 (Rίitapox®VE2510)被甲基乙基甲酮稀釋至固體含量為65% 並與5%二氰二醯胺混合）與50 g滑石、50 g矽烷化石英粉 及3 g高度分散的矽酸（Aerosil® 200)混合成一糊狀黏合料。 使用一刮板將該黏合料塗到一銅膜上並使乾燥塗層厚度為 50 μπι。在80 °C下乾燥塗佈好的銅膜30分鐘。 實例1 2 (黏合強度） 使數片實例9，10及11各具一浸潰過環氧樹脂之預浸潰 體（FR4基礎材料）疊片的裹覆銅膜在170 °C下被壓緊6 0分 鐘，以測量黏合強度。然後以滾剥試驗測試黏合強度及測 定玻璃轉化溫度（Tg)。得到之值如表2所示： 表2 裹覆銅膜 實例9 實例10 實例11 黏合強度 1.0 1.2 0.8 Tg[°C] 140 160 165 -13- 本紙張尺度適用中國國家標準(CNS) Α4规格(210 X 297公釐）Binding f 593462 A7 B7 V. Description of the invention (9) Glass fabric (fabric 181 / Interglas 91745). The impregnated fabric was dried in an oven at 80 ° C for 30 minutes. Example 8 (Laminate Production) Eight layers of the prepregs of Examples 4, 6, and 7 were each pressed and hardened at 170 ° C for 60 minutes. A 2 mm thick laminate was obtained. The following mechanical properties of the laminate were tested: flexural strength, elastic modulus (E-Modul), intra-layer shear strength (ILS), and glass transition temperature (Tg). The values are shown in Table 1: Table 1 Example of prepreg 4 Example 6 Example 7 Flexural strength [MPa] 450 480 450 Elastic modulus [MPa] 18,000 22,000 25,000 ILS [MPal 35 38 40 Tg (DSC) [° C] 140 160 165 Example 9 (coated film) 100 g of the impregnated mixture of Example 3 was mixed with 50 g of talc, 50 g of silylated quartz powder, and 3 g of highly dispersed silicic acid (Aerosil 200) to form a paste-like adhesive material. This adhesive was applied to a copper film using a doctor blade and the coating thickness was 50 μm. The coated copper film was irradiated with ultraviolet rays (360 ^ 400 n m). A copper-clad film that was stable to storage and non-sticky at room temperature was obtained. Example 10 (coated film) 100 g of the impregnated mixture of Example 5 was mixed with 50 g of talc, 50 g of silanite powder, and 3 g of highly dispersed crushed acid (Aerosil 200) to form a paste-like binder. Use a scraper to apply this adhesive to a copper film and make the coating thickness -12- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 593462 A7 B7 V. Description of the invention (1〇 ) 5 Ο μ m. The coated copper film was irradiated with ultraviolet rays (3,600,000 ships). A clad copper film was obtained which was stable in storage and non-adhesive at room temperature. Example 11 (coated film; comparative example) 100 g of the impregnated mixture of Example 7 (0-cresol novolac epoxy resin (Rίitapox® VE2510) was diluted with methyl ethyl ketone to a solids content of 65% and Mix with 5% dicyandiamide) with 50 g of talc, 50 g of silylated quartz powder, and 3 g of highly dispersed silicic acid (Aerosil® 200) to form a paste-like binder. This adhesive was applied to a copper film using a doctor blade and the dry coating thickness was 50 μm. The coated copper film was dried at 80 ° C for 30 minutes. Example 1 2 (Adhesive strength) Several pieces of Examples 9, 10, and 11 each had an epoxy resin-impregnated prepreg (FR4 base material) laminated copper-clad film that was compacted at 170 ° C 60 minutes to measure the bond strength. The peel strength test was then used to test the bond strength and glass transition temperature (Tg). The obtained values are shown in Table 2: Table 2 Example 9 of coated copper film Example 10 Example 11 Adhesive strength 1.0 1.2 0.8 Tg [° C] 140 160 165 -13- This paper size applies to China National Standard (CNS) Α4 specifications ( 210 X 297 mm)