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2050^ a A6 B6 五、發明説明(》) 發明背景 發明範園 本發明偽關於一 -加強合成物質的 製産品具有優良的 擁有的良好處置性 鼷於這種預浸體的 相關技術敘述 以高強度、离彈 物質的進步合成物 域中,主要是利用 數》 • 這些离级合成物 預浸體的中間物霣 性樹脂,這樣可以 壓預浸體。 然而,雖然琛氣 性、耐溶劑性、機 的韌度使得它們具 合成物霣做為層製 限制於層舆層之間 的熱塑性樹脂作為 下降。因為這值原 (請先閲讀背面之注意事項再填寫本頁) 裝. 订_ 線- > ί 土 Ρ t 種以熱固性樹脂做為基 預浸龌,造種合成物質 顳度而不會·傷寄這類預 質與熱力、檐械性質, 製法以及所製得的層製 性棋數纖維(例如磺鑛 質已經被廣泛的應用於 它們具有優良的比強度 質來生産纖維 能使最後的模 浸體先天上所 另外本發明係 品〇 維)做為加強 浬動器材的領 以及比揮性棋 質的供應與使用型態是一種通常稱為 ,所以常做為基質樹脂 容易地給與適度的騵黏 的樹脂為熱固 性與撓性以層 樹脂所代表的熱固性樹 械性質的優良待想[,但 有較差的耐冲擊性。待 品時,耐沖擊性在許多 的碎面強度,如此使得 基質會造成高级合成物 因,使用高级合成物質 脂具有如耐熱 是由於其較差 別是,當高级 情況之下是受 使用較差韌度 質耐沖擊性的 做為结構性物 本紙張尺度遑《中家樣準(CHS) T4規格(210 X297公*) 2050M 五、發明説明(\) 質已經相當地受到限制。 為了改良這種熱塑性基質樹脂的缺陷,現在已知一種 加入橡睡成份的方法。然而,為了得到充份的改良韌度 的效果必須加入大量的橡睡成份,而這會形成耐熱性、 耐溶劑性等的大幅下降。 此外,有人提出一種加入热塑性樹脂的方法(Japanese Patent Application Kokai No. 61- 12543, No. 61-2 2 8 0 1 6,No. 58- 1 34 1 1 1 ,等)特別是有優良附熱性輿 耐溶劑性的工程塑膠。渣些文獻指出舆加入橡驂成份的 例子比較起來耐熱性、耐溶爾性的下降有受到抑制,但 是必須加入大蛋的熱塑性樹脂以得到足夠的蹰度。然而 ,即使在這項方法中,仍然有一些鼗重的問題,也就是 用於生産預沒鼸的樹脂的浸漬性質以及預浸釀的謬黏度 随箸整偁条统黏滞性的增加而降低。 此外逭些用於改良熱固性基質樹脂之韌度的嚐試從改 良層製品之層間脱皮強度的觀黏而言並非十分有效。同 時,有人提出在層與層之間均勻分佈熱塑性樹脂的撤細 頼粒的方法(Japanese. Patent Application Kokai No. 1 - 1 1 0 5 3 7),其目的在於有效改良層製品層舆層之間的 脱皮強度》然而,預沒饑謬黏度的大i降低似乎無法避 免,而且禊雜的製迪程序以及品質控制等厢題都進一步 發生了 •雖然想要將切碎的鑛維、壓緊的纖維等等定位 在層與層之間的《試也鎗經為了相同的目的被提出來, 本纸張尺度遑爾中國家樣準(CNS)甲4規格(?10X297公釐) (請先閲讀背面之注意事項再填寫本頁) 裝< 訂- 線< A 6 Β6 五、發明説明(¾ ) 然而同樣的問題並無法避免,而且疸些試驗的效果一般 也不足。 此外,有人提出一種在層與層之間插入一種稱為間葉 的吸沖擊層的方法(例如,USP No. 3 , 4 7 2,730, Japanese Patent Application Kokai N o . 5 1 - 58 484, No. 60-63229, No. 60-231738,等)p 在逭些文獻中 ,層與雇之間的厚度變大以降低預浸鼸的繼維比值,但 是卻使耐熱性與處理性質變差,使得逭種方法並沒有得 到廣泛與實際上的應用。 發明概逑 本發明的目的在於提供一種以熱固性樹脂做為基質來 生産_雒-加強的合成物質的預浸鼸,一種生産該預浸 體的方法以及以該預浸臛生産的層製品,而揸種雄維-加強的合成物霣能夠給與最後棋製産品槿佳的粝度而不' 傷軎到優良的處理性霣以及這類預浸钃原本就有的熱力 舆機械性質。 本發明侏籣於一種纖維-加強的合成物質,待別是鼸 於一種含有下列成份的預浸體。 (A) —種禪性棋數為2 0 0GPa或更高的加強鑛維, (B) —種揮性棋數為lOOGPa或更少的纖維性熱塑性樹 脂,以及 (C) 一種熱固性基質樹脂, 最好上述用於鑛維-加強的合成物質之預浸釀其待撖在 (請先閲讀背面之注意事項再填寫本頁) 裝- 訂- 線- 本紙»尺度遑用中爾家樣準(CMS)甲4規格(?10x297公釐) 2050k A 6 B6 五、發明説明(4 ) 於纖維性熱塑性樹脂(B)被定位在預浸饈的外表面,以 及一種生産該預浸體的方法。 本發明的第一項要黏在於混合一種底預浸醱,包括有 一種加強鑛維以及一種熱固性基質樹脂舆一種彈性模數 為lOOGPa或更少的熱塑性樹脂.的鐵維形産品。在將這種 雄維性熱塑性樹脂與底預浸體摻合時使得前者定位於後 者的外表面,我們可以得到一種鐵維-加強的物質,其 模製産品具有優良的籾度而不會傷害到該底預浸體原本 之優良處理性質以及熱力與機械性質。 圖例簡述 臞1顯示一種方法其中繼維性熱塑性樹脂安排在加強 鑛維與熱固性基質樹脂所得到的底預浸黼之上,之後進 行加熱舆浸潰作用。 國2顯示一 «方法其中鐵維性熱塑性樹脂同時安排在 底預漫體的兩邊之上》 圖3顯示一種方法其中加強繼雄與鐵維性熱塑性樹脂 同時供應至一覆蓋有熱固性基質樹脂的脱棋紙之上,之 後進行浸潰作用。 圈4顯示一種方法其中繼維性熱塑性樹脂被安排在並 固定至覆蓋有熱固性基霣樹脂的脱棋紙之上,然後再覆 ϋ上加強纖維,之後進行浸漬反鼴。 圃5顯示本發明的一個(實例輿一值對照實例所得到之 層層相叠的預漫體在進行懕熱器棋造之前的截面圔示。 (請先閲讀背面之注意事項再填寫本頁) 本纸張尺度遑用中家樣準(CNS)甲4規格(210 X297公釐) 205054 五、發明説明(4) 具黼施行例 本發明中揮性模數為100GP a或更少的覦維性热塑性樹 脂(B)是本發明之中最重要的成份*原因在於本發明的 目的是要提供一種用於繼維-加強的合成物霣的預漫龌 ,而能給與模迪産品槿佳的鄢·度而不會傷害到底預浸醴 之優良處理性質輿熱力及機械性霣,而這項目的的速成 只能利用織雒性熱塑性樹脂。也就是説,藉著将熱塑性 樹脂形塑為繼維,使得在預浸體的表面層之上有效的安 排熱塑性樹脂成為可能。結果,我們只用少量的熱塑性 樹脂就逹成了韌度的充分改良,同時預浸體的膠黏程度 還容易控制,使得先前技藹的缺黏之一的暖黏程度下降不 會發生。此外,與加入熱塑性樹脂撖粒的先前技藝比較 之下,我們得到了品質控制較為容易的優點。此外•傅 统的預浸鼸製进方法可以照舊使用。造些效果麵法經由 先前技β達到而只能藉著利用本發明中薄性棋數為100 GPa或更少的鑛維性熱塑性樹脂(Β)來連成β 由於本發明中的鐵維性熱塑性樹脂(Β)之®性棋數為 lOOGPa或更少,我們所常用的纖維狀産品為聚磨胺,聚 酯、聚乙烯、聚丙烯以及所謂的工程塑_輿_级工塑® 如聚碩酸酯、聚乙縮醛、聚芳基化物、聚M、聚 、聚黼亞胺、聚亞胺、聚醯胺亞胺、聚苯氧化物、聚硫 化苯、聚苯並眯唑等等β然而,本發明中的熱塑性樹脂 (Β)並不雄是限於逭些樹脂輿塑篇。但是某些液晶聚合 A 6 B6 (請先閲讀背面之注意事項再填寫本頁) 裝. 訂· -線< 本紙張尺度遑用中國國家樣毕(CNS)甲4規格(210X297公釐) it 20505^ 五、發明説明(备) (請先閲讀背面之注意事項再填寫本頁) 物的纖維狀産品,例如聚對苯苯並«瞎唑等等,以待殊 方法生産具有超高揮性模數的聚乙烯繼維以及某些 Kevlai· 49所代表的阿醯胺《維並不被使用.因為它們 的彈性模數超過lOOGPa而且對於韌度的改良效果不佳。 因為本發明中纖維狀的熱塑.性樹脂(B)的揮性樓數為 100GP a或更少,那些具有官能基而能夠舆熱固性基質樹 脂(C)在分子鍊上反臁的化合物特別受到歡迎,而且它 們是根據所要使用的熱固性基質樹脂而適當遘定的。官 能基的種類決定於所使用的熱固性基質樹脂。官能基的 實例包括氨基、睡胺基、粉式羥基、酵式羥基、缩水甘 油基、羧基、酸酐、氳硫基、烯丙基、乙烯基、順丁烯 二醯亞胺、氱酸酯基等等。然而,只要能夠與熱固性基 質樹脂反應,官能基並不受限於以上造些。 , 纖維狀熱塑性樹脂的形狀要求並不嚴格,只要樹脂的 長度夠長•纺鐵的抄線也可以使用,但是以單絲或多絲 較佳β絲徑最好是100 A 或更少,而以50#·或更少最 好。如果所使用的熱塑性樹脂是多絲狀的,那麽直徑结 數以1000旦(denier)較佳,而以500旦更好。 同時對於線絲的斷 面形狀没有待殊限制。 不同物質以及絲徑的兩種或多種供維狀熱塑性樹脂可 以組合使用。組合的方法並不一定,只要能夠適當的醮 用平行交替兩糧雄維的方法以及利用由交鎇而成的混合 絲線的方法就足夠了 *此外,我們也可以使用同時纺鐡 -8 - 本紙張尺度遠用中國祖家樣年(CNS)甲4規格(?10X297公*) 20505^1 Μ 五、發明説明(7) 兩種或多種雄雒狀熱塑性樹脂所生産具有套-核结構或 海-島结構的共轭绨線。使用兩種或多種性質不同且為 共扼絲線或混成絲線形態的兩種或多種鐵維是一種平衡 各種特擻的有效方法。 繼雒狀樹脂(B)的重量比以熱固性基質樹脂(C)的重量 為基準是0.5到4096較佳,而以0.5到20¾重量比更好。 若重量比少於0.5%,就無法得到足夠的鄹度改良效果 。若是超過40%,上述效果無法再曲缅增加而且預浸體 的醪黏度會下降而這是我們所不願意的〇 我們期望本發明中的雄維狀熱塑性樹脂(B)被定位在 預浸體外表面附近β若是熱塑性樹脂完金位於預浸體的 中央部份,那麽我們可能無法得到充份的®度改良效果 。然而,熱塑性樹脂完全與預浸饈外表面完全分離的狀 態也是我們所不願意的。我們希望纖維狀熱塑性樹脂一 部份位在热固性基質樹脂中而不至於在處理的時候會脱 落或移動》此外我們更希望鑛維狀熱塑性樹脂在一定的 方向上等距離平行排列。然而,定位於待定匾域的熱塑 性樹脂並不受此限。當然我們可以同時將熱塑性樹脂在 兩但或更多方向上平行排列以安排樹脂的交錯狀態。造 種方法能夠達成高粝度改良效果,但是會使製造程序變 得禊雜β平行排列的方向並没有特定的限制,而熱塑性 樹脂可以輿加強雄維形成任何角度,但是將樹脂與加強 鑛維安排在同一傾方向是最容易的。 (請先閲讀背面之注意事項再填窝本頁) 裝. 線- 本紙張疋度逡用中家樣率(CMS)甲4規格(?10Χ297公釐) 五、發明説明(β ) 由於本發明中的加強纖維(A)其揮性模數為200GP a或 更高,一般纖維-加強的合成物質所使用的加強雄維, 例如硪纖雒、石墨纖雒、硼缅維等都以它們原來的狀態 來使用。然而,最好是使用張力強度為3500 MPa或更离 的硪鐵雒與石墨纖嫌。其中,·最好使用高·強度、离延展 性的磺鑛維與石墨鑛維·其張力強度為4 5 0 0 MPa或更高 且延展度為1.7%或更高。 至於本發明之熱固性基質樹脂(C),則可以使用能經 外在能量熟化成至少部分地三雒熟化産品的樹脂。典型 實例包括琛氣樹脂、順丁烯二醯亞胺樹脂、聚醯亞胺樹 脂、酚醛樹脂、乙烯酯樹脂、未飽和聚醋樹脂、氰酸酯 樹脂、具乙炔端的樹脂、具乙烯端的樹脂、具烯丙基蛸 的樹脂、具nadic酸端的樹脂及其混合物。以上樹脂中 、琛氣樹脂中、顯丁烯二醯亞胺樹脂、気酸酯樹脂以及 顛丁烯二酵亞肢樹脂與気酸酯樹脂的混合物是較佳的樹 脂〇 可以使用任一種琛氧樹脂,但以前身為胺類或酚類的 樹脂較佳》逭類琛氣樹脂的實例包括四缩水甘油二氨基 二苯基甲烷、三缩水甘油-對-氛基酚、各種三编水甘油 氨基甲酚的異構物、二酚A型琛氣樹脂、二酚F型琛氣 樹脂、二酚S型琛氯樹脂、酚醛淸漆型琢氣樹脂、甲酚 澝漆型琢氣樹臢。然而,本發明琛氣樹脂並不限於此。 此外,澳化上述琛氣樹脂而産生之溴化環氣樹脂也可使 -1 0 - 本紙張尺度遑用中鼸國家樣手(CNS)甲4規格(210x297公釐) (請先閲讀背面之注意事項再填寫本頁) 裝- 訂_ 線- ^05054 A 6 B6 五、發明説明(9 ) (請先閲讀背面之注意事項再塡寫本頁) 用。這些琛氣樹脂可單獨使用或適當地混合其中二種或 更多種來使用。 環氣樹脂常與熟化劑組合使用。對於本發明中所使用 的熟化劑並無待殊限制,而任一含能與環氣樹脂作用之 官能基(如氨基、酸酐基)的化合物都能使用。然而以 各種二氛基二苯基确、二氰基二醛胺與二 氨基苯甲酸 酯之異構物所代表之芳香胺類較佳。 本發明中,順丁烯二醛亞胺樹脂指的是一種以多官能 顒丁烯二醯亞胺作為主成分的樹脂組成物,其中分子内 具兩種或更多種順丁烯二酵亞胺基的化合物佔樹脂組成 物的30%重置比或更多,最好是40%重量比或更多β如 果多官能順丁烯二醯亞胺的含量在上述範圍中,該樹脂 組成物S外邇可以含一種單官能順丁烯二醛亞胺或其它 可共,聚的反應性化合物,只要物理條件如耐熱性、韌度 不會降低。 下列化合物可以作為多官能順丁烯二醛亞胺: 1,2-雙順丁烯二醛亞胺乙烯、1, 6-雙顒丁烯二酵亞 胺己烷、1, 12-雙順丁烯二酵亞胺+二烷、1, 6-雙順 丁烯二醛亞胺(2, 2, 4-三甲基)己烷、1, 3-雙順丁 烯二醯亞胺苯、1, 4-雙順丁烯二醯亞胺苯、3,3'或4 ,4’-雙順丁烯二醯亞胺二苯基甲烷、3, 3’或4, 4'-雙 順丁烯二醯亞胺二苯基W、3, 3’或4, 4·-雙順丁烯二 醯亞胺二苯醚、2, 4'-, 2,6_-或3,4'-雙順丁烯二酵 -1 1- 本紙張尺度逍用中國家«準(CNS)甲4規格(210X297公*) d ύ οro ο 2 66 ΑΒ ίν 明 説 明 發 五 雙亞0 4 二 4,烯 、丁 物順 化雙 硫' 苯4 二 4’ 0 、 二烷 烯甲 丁基 顒己 雙環 二 4胺 4 亞 、醛 苯二 甲烯 胺丁 亞順 烷 己 基Ν, 己 、 環胺 二亞 胺醛 Ν Ν 胺 亞0 -Ρ棒 或康 Β-雙 -基 苯 J次 二 4 烯 , 丁 Τ 順Ν' 雙 基 甲二 苯 Ν 雙4- C L雙 2 、 、烷 胺丙 亞 3 醛基 檸苯 0 ) 雙基 基氣 苯苯 次胺 二亞 醯胺 二亞 烯醯 丁 二 順烯 4 丁 ί 順 基 氣 苯 基 苯 基 苯 m 雙雙 f 3 0 , 基苯 氣} 苯基 胺氣 亞苯 醯胺 二亞 烯醯 丁 二 順烯 3 丁 ί 順 雙- 3 N N ' 苯 \1/ 基 氣 苯 胺 亞 醯二 烯 丁 順 1, 3-次苯基-二-(2, 2-亞丙基)-二-P-次苯基〕-雙 順丁烯二醯亞胺,其混合物以及含順丁烯二醯亞胺與二 胺之預聚合物。至於預聚物中所用的二胺,以芳香二胺 如二氨基二苯基甲烷較好。而且,以4, 4·-雙順丁烯二 酵亞胺二苯基甲烷與4,4'-雙顒丁烯二醛亞胺二苯基甲 烷和1,6 -雙順丁烯二醛亞胺(2, 2,4 -三甲基)己烷 之共沸混合物以及雙順丁烯二醯亞胺甲苯特好。 與多官能順丁烯二醯亞胺化物共同聚合的反應性化合 物包括,例如,烯基酚如0, 二烯丙基雙酚A, 0, 0'-二烯丙基雙酚F等,三烯丙基氰尿酸酯、二乙烯基 苯,N -乙烯基吡咯烷酮,乙二酵二甲基丙烯酸酯等。這 些可共聚的反應化物可單獨使用或混合使用,其含量為 以多官能順丁烯二醛亞胺為主成分之基質樹脂的70 %重 量比或更少,最好是50%重量比或更少β這些可共聚的 -1 2 - 本紙張尺度逍用中國國家楳準(CNS)甲4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) A 6 B6 五、發明説明(") (請先閲讀背面之注意事項再塡寫本頁) 反應性化物中,烯基酚有改良熱固性基質榭脂掘度、可 加工度的效果,其使用量最好是基質樹脂的1096到50% 重量比。 以多官能順丁烯二醛亞胺為主成分的熱固性基質樹脂 能容另地加熱熟化,但仍可以·加入觸媒使熟化産物具有 所欲特性以及調整熟化特性。可作為觸媒的化物包括有 機膦、有機辚鹽、其錯合物、三氟化硼/胺錯合物以及 游離基聚合觸媒如有機過氧化物、偶氮異丁腈等。本發 明中所加入觸媒的分量並不受限制,但基於穩定度的要 求,最好佔全部基質樹脂成分的0.01到5¾重量比。 氰酸酯樹脂指的是一種樹脂组成物,其中含50%重量 比或更多的多官能氰酸樹脂,其化學式如下: Y-(-〇-C= N)n 其中η代代表一 2到5的整數,1代表芳香有機殘基, 及 以及其齊聚物。 可作為多官能氰酸酯者包括1, 3-或1, 4-二氰酵苯、 4, 4’-二氰醛二苯基、2, 2'-雙(4-氰醛苯基)-丙烷 、2, 2’-雙(4-氰醏苯基)-乙烷、雙(4-氰醏苯基) 甲烷、雙(4-氛酵苯基)W、雙(4-氰醯苯基)硫化物 、雙(3, 4 -二甲基-4-氰醯苯基)甲烷、一種下列化學 式(I )所代表之化物 -13- 本紙張尺度逍用中國困家榉毕(CNS)T4規格(210X297公*) 五 .·ϋο 5ο ί*Ί2050 ^ a A6 B6 V. Description of the invention (》) Background of the invention Fangyuan The present invention is pseudo-related to the one-strengthened synthetic material product with excellent possession and good disposability. The relevant technical description of this prepreg is described as high In the field of advanced composites of strength and elastomers, the number of applications is mainly "" • The intermediate resin of these off-grade composite prepregs is made of high-resin, so that the prepreg can be pressed. However, although the air quality, solvent resistance, and organic toughness make them have composites as the layer system, the thermoplastic resin between the layers and the layers is limited. Because this value is the original (please read the precautions on the back and fill in this page). Packing. _ 线-> ί soil Ρ t pre-impregnated with thermosetting resin as the base, making a kind of synthetic material temporality will not · This kind of pre-quality and thermal power, the properties of eaves machinery, the manufacturing method, and the layered fiber made of layers (for example, sulfonite has been widely used in their production of fibers with excellent specific strength to make the final The mold dipping body is innately provided by the present invention. The dimension (dimensional) is used to strengthen the collar of the moving equipment and the supply and use of the unique chess quality is commonly called, so it is often given as a matrix resin. The moderately viscous resin is thermosetting and flexible. The thermosetting properties represented by the layer resin are excellent [but have poor impact resistance. When the product is processed, the impact resistance is at the strength of many broken surfaces, so that the matrix will cause high-grade synthetics. The use of high-grade synthetic substances has such heat resistance as its heat resistance is due to its difference. The impact resistance is used as a structural object. The paper standard is "Zhongjia Sample Standard (CHS) T4 Specification (210 X297) *) 2050M. 5. Description of the invention (\) The quality has been quite limited. In order to improve the defects of this thermoplastic matrix resin, a method of adding rubber sleep ingredients is now known. However, in order to obtain a sufficient effect of improving the toughness, it is necessary to add a large amount of rubber sleeping ingredients, and this will result in a substantial decrease in heat resistance, solvent resistance, and the like. In addition, a method for adding a thermoplastic resin (Japanese Patent Application Kokai No. 61-12543, No. 61-2 2 8 0 1 6, No. 58-1 34 1 1 1, etc.) has been proposed, in particular, it has excellent thermal conductivity Engineering plastics resistant to solvents. Some slag literatures pointed out that the examples of adding the rubber component are relatively reduced in heat resistance and solubility resistance, but it is necessary to add a thermoplastic resin of large egg to obtain sufficient sag. However, even in this method, there are still some weight problems, that is, the impregnating properties of the resin used to produce the pre-mold and the false viscosity of the pre-prepared brew decrease with the increase of the viscosity of the whole system . In addition, some attempts to improve the toughness of thermosetting matrix resins are not very effective in terms of improving the apparent adhesion of the interlayer peeling strength of good layer products. At the same time, it has been proposed to uniformly distribute thermoplastic resin between the layers of fine particles removal method (Japanese. Patent Application Kokai No. 1-1 1 0 5 3 7), its purpose is to effectively improve the layer of the product layer "Peeling strength between rooms" However, it seems inevitable that the large i reduction of viscosity will not be avoided, and the complicated manufacturing procedures and quality control problems have occurred further. Although I want to compact and crush the mine, The fibers and so on are located between the layers. "The test is also proposed for the same purpose. This paper standard is in the Chinese National Standard (CNS) A 4 specifications (? 10X297 mm) (please first Read the precautions on the back and then fill out this page) Installation & Ordering-Line &A; A 6 Β6 V. Description of Invention (¾) However, the same problem cannot be avoided, and the effects of some jaundice tests are generally insufficient. In addition, a method of inserting an impact-absorbing layer called a mesenchyme between layers is proposed (for example, USP No. 3, 4 7 2,730, Japanese Patent Application Kokai No. 5 1-58 484, No. 60-63229, No. 60-231738, etc.) p In some of the literature, the thickness between the layer and the layer is increased to reduce the secondary dimension ratio of the prepreg, but it makes the heat resistance and processing properties worse, making This method has not been widely and practically applied. SUMMARY OF THE INVENTION The object of the present invention is to provide a prepreg with a thermosetting resin as a matrix to produce _ Luo-reinforced synthetic substances, a method for producing the prepreg and a layered product produced with the prepreg, and揸 种 雄 维 -Reinforced synthetic compound can give the final chess product Geun Jia's degree without hurting the excellent handling properties and the inherent thermal and mechanical properties of such prepreg metal. The gnome of the present invention is a fiber-reinforced synthetic substance, which is distinguished from a prepreg containing the following ingredients. (A)-a kind of reinforced ore dimension with a Zen performance of 200 GPa or higher, (B)-a fibrous thermoplastic resin with a swing performance of 100 GPa or less, and (C) a thermosetting matrix resin, It is best to use the pre-leaching of the above-mentioned synthetic materials for mineral dimension-strengthening to wait for it (please read the precautions on the back and then fill out this page). Packing-booking-line-this paper CMS) A4 specifications (? 10x297mm) 2050k A 6 B6 V. Description of the invention (4) The fibrous thermoplastic resin (B) is positioned on the outer surface of the prepreg and a method for producing the prepreg. The first aspect of the present invention is to stick a bottom prepreg, which includes a reinforced mineral dimension and a thermosetting matrix resin and a thermoplastic resin with an elastic modulus of 100 GPa or less. When this male dimensional thermoplastic resin is blended with the bottom prepreg so that the former is positioned on the outer surface of the latter, we can obtain an iron-reinforced substance whose molded product has excellent fen-degree without harming The original prepreg has excellent processing properties as well as thermal and mechanical properties. Brief description of legend Figure 1 shows a method in which the relay-dimensional thermoplastic resin is arranged on the bottom prepreg obtained by reinforcing the mineral dimension and the thermosetting matrix resin, and then subjected to heating and immersion. Country 2 shows a «method in which the iron-dimensional thermoplastic resin is arranged on both sides of the bottom pre-dispersion body at the same time» Figure 3 shows a method in which the reinforced secondary male and the iron-dimensional thermoplastic resin are simultaneously supplied to a stripper covered with a thermosetting matrix resin On the chess paper, then the dipping effect is carried out. Circle 4 shows a method in which the relay-dimensional thermoplastic resin is arranged and fixed on the release paper covered with thermosetting base resin, and then covered with reinforcing fibers, and then impregnated to react. Garden 5 shows a cross-section of a layered pre-diffusion body obtained by the example of the present invention (the example and the one-value control example before performing the heater chess. (Please read the precautions on the back before filling this page ) This paper uses the Chinese standard (CNS) A4 specifications (210 X297 mm) 205054 V. Description of the invention (4) Example of implementation of the stubborn thread The modulus of the invention is 100GP a or less The dimensional thermoplastic resin (B) is the most important component in the present invention * The reason is that the purpose of the present invention is to provide a pre-diffusion for the maintenance-reinforced synthetic compound, which can give the modal product Hibiscus It has a good temperature and does not harm the excellent processing properties of the prepreg, heat and mechanical properties, and the quick success of this purpose can only use woven shovel thermoplastic resin. That is to say, by molding the thermoplastic resin In order to maintain the dimension, it is possible to arrange the thermoplastic resin on the surface layer of the prepreg effectively. As a result, we have used only a small amount of thermoplastic resin to achieve a sufficient improvement in toughness, and at the same time, the degree of adhesion of the prepreg is still Easy to control, making previous skills lacking One of them will not decrease the degree of warm viscosity. In addition, compared with the previous technology of adding thermoplastic resin grains, we have the advantage of easier quality control. In addition • Fu Tong ’s prepreg production method can be used as usual The effect surface method is achieved by the previous technique β and can only be connected to β by using the mineral-dimensional thermoplastic resin (B) in the present invention whose thinness is 100 GPa or less. Due to the iron-dimensional thermoplastic in the present invention The number of resins (B) is about 100 GPa or less, and the fibrous products we commonly use are polyamelamine, polyester, polyethylene, polypropylene, and so-called engineering plastics. Ester, polyacetal, polyarylate, poly M, poly, polyimine, polyimide, polyimide, polyphenyl oxide, polysulfide benzene, polybenzoxazole, etc.β However, the thermoplastic resin (B) in the present invention is not limited to some resins and plastic articles. But some liquid crystal polymerization A 6 B6 (please read the precautions on the back before filling this page). Binding ·-line < This paper uses the Chinese National Standard (CNS) Grade 4 (210X2) 97mm) it 20505 ^ V. Description of the invention (preparation) (please read the precautions on the back before filling in this page). The fibrous products such as poly-p-benzobenzazole etc. are produced by special methods Polyethylene secondary dimensions with ultra-high volatility modulus and some acrylamides represented by Kevlai · 49 are not used. Because their elastic modulus exceeds 100 GPa and the effect of improving toughness is not good. Because In the present invention, the fibrous thermoplastic resin (B) has a volatility of 100 GP a or less, and those compounds having functional groups capable of reflecting the thermosetting matrix resin (C) on the molecular chain are particularly popular And, they are properly determined according to the thermosetting matrix resin to be used. The type of official function depends on the thermosetting matrix resin used. Examples of the functional group include amino group, sleep amine group, powdered hydroxyl group, fermented hydroxyl group, glycidyl group, carboxyl group, acid anhydride, thiosulfate group, allyl group, vinyl group, maleimide, carboxylate group and many more. However, as long as it can react with the thermosetting matrix resin, the functional group is not limited to the above. The shape requirements of the fibrous thermoplastic resin are not critical, as long as the length of the resin is long enough. Iron-spinning yarns can also be used, but it is preferable to use single or multi-filaments. The β-filament diameter is preferably 100 A or less, and The best is 50 # · or less. If the thermoplastic resin used is multifilamentous, the diameter is preferably 1000 denier, and more preferably 500 denier. At the same time, there is no special restriction on the cross-sectional shape of the wire. Two or more types of thermoplastic resins of different substances and wire diameters can be used in combination. The method of combination is not necessary, as long as the method of alternately alternating the two grains of male dimensions and the method of using mixed yarns made of crossovers are sufficient * In addition, we can also use simultaneous spinning -8-this The paper scale is far from the Chinese ancestral family sample year (CNS) A 4 specifications (? 10X297 g *) 20505 ^ 1 Μ 5. Description of the invention (7) Two or more male Luo-shaped thermoplastic resins have a sleeve-core structure or sea -Conjugated yarn of island structure. The use of two or more iron dimensions with different properties and in the form of conjugated wires or mixed wires is an effective way to balance various characteristics. The weight ratio of the secondary resin (B) is preferably 0.5 to 4096 based on the weight of the thermosetting matrix resin (C), and more preferably 0.5 to 20¾. If the weight ratio is less than 0.5%, it is impossible to obtain a sufficient improvement effect. If it exceeds 40%, the above effects can no longer be increased and the viscosity of the prepreg's mash will decrease, which is undesirable. We expect the male dimensional thermoplastic resin (B) in the present invention to be positioned outside the prepreg If β near the surface is a thermoplastic resin finish located in the central part of the prepreg, then we may not be able to obtain a sufficient improvement effect. However, it is undesirable that the thermoplastic resin is completely separated from the outer surface of the prepreg. We hope that part of the fibrous thermoplastic resin is located in the thermosetting matrix resin so as not to fall off or move during processing. In addition, we also hope that the mineral-dimensional thermoplastic resins are arranged in parallel in an equal distance in a certain direction. However, the thermoplastic resin positioned in the plaque area to be determined is not limited to this. Of course, we can arrange the thermoplastic resin in parallel in two but more directions to arrange the staggered state of the resin. The seed production method can achieve a high degree of improvement, but there will be no specific restrictions on the direction of the parallel arrangement of the manufacturing process. The thermoplastic resin can form any angle with the strengthening dimension, but the resin and the strengthening dimension It is easiest to arrange in the same tilt direction. (Please read the precautions on the back before filling the nest page). Thread-This paper uses a sample rate (CMS) A4 specification (? 10Χ297mm). 5. Description of the invention (β) Because of the invention The reinforced fiber (A) has a modulus of volatility of 200 GP a or higher, and the reinforced male dimensions used for general fiber-reinforced synthetic materials, such as fibrous fiber lozenges, graphite fiber lozenges, and boromethan To use. However, it is best to use graphite iron with a tensile strength of 3500 MPa or more. Among them, it is best to use high-strength, ductile sulfonite and graphite minerals whose tensile strength is 4 500 MPa or higher and the ductility is 1.7% or higher. As for the thermosetting matrix resin (C) of the present invention, it is possible to use a resin that can be cured by an external energy to at least partially cure the product. Typical examples include phenol resin, maleimide resin, polyimide resin, phenolic resin, vinyl ester resin, unsaturated polyester resin, cyanate resin, resin with acetylene end, resin with ethylene end, Resins with allyl chrysalis, resins with nadic acid ends and mixtures thereof. Among the above resins, phenol resins, butadiene diimide resins, tartaric acid ester resins, and mixtures of butadiene bisacrylic acid resins and tartaric acid resins are preferred resins. Any kind of phenolic oxygen can be used. Resin, but resins formerly known as amines or phenols are preferred "Examples of Japanese gas resins include tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, various triglycidyl glycerylamino Isomers of cresol, diphenol A type gas resin, diphenol F type gas resin, diphenol S type gas resin, phenolic resin lacquer type gas resin, cresol lacquer type gas resin. However, the inventive gas resin is not limited to this. In addition, the brominated ring gas resin produced by Australia's above-mentioned Chen gas resin can also be used at-10-This paper standard uses the Chinese National Handicraft (CNS) A4 specification (210x297 mm) (please read the back of the first Please fill in this page before paying attention.) Binding-Order _ Line-^ 05054 A 6 B6 5. Description of invention (9) (Please read the precautions on the back before writing this page). These Chen gas resins can be used alone or two or more of them can be appropriately mixed and used. Ring gas resins are often used in combination with curing agents. There is no particular restriction on the curing agent used in the present invention, and any compound containing a functional group (such as an amino group and an anhydride group) that can interact with the ring gas resin can be used. However, aromatic amines represented by various isomers of diaminodiphenyl, dicyandialdehyde and diaminobenzoate are preferred. In the present invention, maleimide resin refers to a resin composition with polyfunctional oxbutene diimide as the main component, in which there are two or more maleimides in the molecule. The amine-based compound accounts for 30% of the resin composition replacement ratio or more, preferably 40% by weight or more β. If the content of the multifunctional maleimide is within the above range, the resin composition S outer gel can contain a monofunctional maleimide or other copolymerizable, reactive compound as long as the physical conditions such as heat resistance and toughness are not reduced. The following compounds can be used as multifunctional maleimide: 1,2-bismaleimide ethylene, 1, 6-bisbenzidine butanediimide hexane, 1, 12-bismaleimide Dimerimine + dioxane, 1, 6-bismaleimide (2, 2, 4-trimethyl) hexane, 1, 3-bismaleimide benzene, 1 , 4-bis-cis-butadiene diimidebenzene, 3,3 'or 4,4'-bis-cis-butadiene diimide diphenylmethane, 3, 3' or 4, 4'-bis-cis-butene Diimide diphenyl W, 3, 3 'or 4, 4 · -bis-cis-butadiene diimide diphenyl ether, 2, 4'-, 2, 6_- or 3, 4'-bis-cis-butane Dien-1-1 1- This paper scale is used in the Chinese national standard quasi (CNS) A4 (210X297 g *) d ύ οro ο 2 66 ΑΒ ίν Clear instructions for the release of Wushuangya 0 4 2, 4, ene and butyl Disulfide 'benzene 4 di 4' 0, dialkylene butyl butyl sulfonate bicyclic di 4 amine 4 sub, aldehyde styrene enamine butadiene hexyl N, hexyl, cyclic amine diimide aldehyde Ν Ν amine sub 0- Ρ stick or Kang B-bis-ylbenzene J times di 4 ene, butyl T cis N ′ bismethyltoluene N bis 4-CL bis 2, alkylamine propylene 3 aldehyde citrus benzene 0) diyl Benzene amine phenylenediamine diimide diene acetylene butadiene 4 butyl cis phenyl phenyl benzene m bis bis f 3 0, phenyl benzene} phenylamine gas phenylene amine phenylene amine diene acetylene bis cis Ene 3 butyl cis- 3 NN 'benzene \ 1 / base gas aniline acetylenediene butadiene cis 1,3-phenylene-di- (2,2-propylene) -di-P-phenylene 〕 -Bismaleimide, its mixture and prepolymer containing maleimide and diamine. As for the diamine used in the prepolymer, aromatic diamines such as diaminodiphenylmethane are preferred. Moreover, with 4, 4 · -bis-butadiene diimine diphenylmethane and 4,4'-bis-butadiene dialdehyde iminodiphenyl methane and 1,6-bis-butadiene dialdehyde methylene Azeotropic mixtures of amine (2, 2, 4-trimethyl) hexane and bis-cis-butadiene diimide toluene are particularly good. Reactive compounds co-polymerized with polyfunctional maleimide diimide include, for example, alkenyl phenols such as 0, diallyl bisphenol A, 0, 0'-diallyl bisphenol F, etc. Allyl cyanurate, divinylbenzene, N-vinylpyrrolidone, glyoxyl dimethacrylate, etc. These copolymerizable reactants can be used singly or in combination, and the content thereof is 70% by weight or less of the matrix resin mainly composed of polyfunctional maleimide and preferably 50% by weight or more Less β these copolymerizable -1 2-This paper scale is easy to use China National Standard (CNS) A 4 specifications (210X297 mm) (please read the precautions on the back before filling this page) A 6 B6 V. Description of the invention (&Quot;) (Please read the precautions on the back before writing this page) Among the reactive compounds, alkenyl phenol has the effect of improving the degree of excavation and processability of the thermosetting matrix resin, and its use amount is preferably the matrix resin 1096 to 50% by weight. A thermosetting matrix resin containing polyfunctional maleimide as the main component can be cured by heating separately, but it is still possible to add a catalyst to make the cured product have desired characteristics and adjust the curing characteristics. Compounds that can be used as catalysts include organic phosphines, organic sulfonium salts, their complexes, boron trifluoride / amine complexes, and radical polymerization catalysts such as organic peroxides and azoisobutyronitrile. The amount of the catalyst added in the present invention is not limited, but based on the requirement of stability, it is preferably 0.01 to 55% by weight of the total matrix resin component. The cyanate ester resin refers to a resin composition containing 50% by weight or more of a multifunctional cyanic resin, the chemical formula of which is as follows: Y-(-〇-C = N) n where η represents a one to two An integer of 5, 1 represents an aromatic organic residue, and its oligomer. Can be used as polyfunctional cyanate, including 1, 3- or 1, 4- dicyanobenzene, 4, 4'-dicyanaldehyde diphenyl, 2, 2'-bis (4-cyanaldehyde phenyl)- Propane, 2, 2'-bis (4-cyanophenylphenyl) -ethane, bis (4-cyanophenylphenyl) methane, bis (4-cyanophenylphenyl) W, bis (4-cyanophenylphenyl) ) Sulfide, bis (3,4-dimethyl-4-cyanophenyl) methane, a chemical compound represented by the following chemical formula (I) -13 Specifications (210X297 g *) 5. ϋο 5ο ί * Ί
AB 明説 明發AB Mingshuo Mingfa
性基質樹脂也無妨,如此可給予熟化産品可欲的待性, 並諝節熟化待撤。至於酚,可使一般的烷類酚,而至於 觸媒,最好使用潛在熟化觸媒(如三氟化硼/胺錯合物 ),三级胺,有機過氣化物*,以及有機酸金臑鹽類如辛 酸餑、辛酸錫、環烷酸銅、璟烷酸鋅、環烷酸姑等。添 加觸媒量決定於目的,但是基於穩定度的觀點,以佔全 部基質樹脂成分的0.05到3%重量比較佳。 含多官能顒丁烯二醯亞胺(I)與多完能氰酸酯或其 齊聚物(II)的混合物,或含以(I)或(II)為主成 分的預反應産物之熱固性樹脂最好也能作為本發明之熱 固性基質樹脂。(I)對(Π)之比例在本發明中並不 受限制,但(I)對(Π)之比例以5: 95到15: 85較 佳。在以(I)或(II)之預反應産物或混合物為主成 分的熱固性基質樹脂中加入環氣樹脂或聚酯樹脂並不會 -1 4 - 本紙張尺度逍用中國《家橾準(CNS)甲4規格(210x297公*) (請先閲讀背面之注意事項再填寫本頁) 2〇δ〇^> a Α6 Β6 五、發明説明() 有任何問題,而是得到極佳的結果。至於環氣樹脂,可 從已知者適當選用,但較佳者為雙酚F型環氣樹脂、雙 酚A型環氣樹脂、二酚醇-烷(如二酚醇甲烷、二酚醇 乙烷、二酚醇丙烷等)的聚縮水甘油醱,多元酚(如酚 醛清漆、甲酚、甲階酚醛樹脂等)的聚縮水甘油醚,令 脂環化物(如環己烷、環戊二烯、二環戊二烯等)琛氧 化所得之環氣樹脂,脂肪多氣化物(如乙二醇、丙三醇 等)之聚(環氣烷基)酯,芳香或脂肪羧酸之環《烷基 酯,等等。此外,掲示於,例如,USP No. 3,390,037 、No.2 ,970,983與Νο·3 ,067,170之環氣樹脂與熟化劑之 預反應産物,或者兩者之混合物皆可使用。 至於聚酯化物,以下列化學式⑵與⑶所代表之化物較 佳,其中酸成分最好主要是對酞酸而甘酵成分最好主要 是新戊二醇或乙二醇。造些聚酯化物之數目平均分子量 為500到10,000,最好是500到3, 000時且軟化點101TC或 更少,最好是7 0 °C時,可得到最佳的結果: HO - Rx 0—f- c II οIt is no problem to use a matrix resin, so that it can give the desired properties of the cured product, and the curing is to be removed. As for phenols, general alkyl phenols can be used. As for the catalyst, it is best to use latent curing catalysts (such as boron trifluoride / amine complex), tertiary amines, organic pervaporates *, and organic acid gold Nitrogen salts such as tin octoate, tin octoate, copper naphthenate, zinc alkanoate, naphthenate, etc. The amount of catalyst added depends on the purpose, but from the viewpoint of stability, it is preferably 0.05 to 3% by weight of the entire matrix resin component. Thermosetting properties of mixtures containing polyfunctional oxobutadiene diimide (I) and polyfunctional cyanate esters or their oligomers (II), or pre-reaction products containing (I) or (II) as the main component Preferably, the resin can also be used as the thermosetting matrix resin of the present invention. The ratio of (I) to (Π) is not limited in the present invention, but the ratio of (I) to (Π) is preferably 5:95 to 15:85. Adding a ring gas resin or a polyester resin to a thermosetting matrix resin containing (I) or (II) pre-reaction products or mixtures as the main component will not -1 4-This paper scale is used in China's "Household Standard (CNS ) A4 specifications (210x297 g *) (please read the precautions on the back before filling in this page) 2〇δ〇 ^> a Α6 Β6 5. Description of the invention () If you have any questions, you will get excellent results. As for the ring gas resin, it can be appropriately selected from known ones, but the preferred ones are bisphenol F type ring gas resin, bisphenol A type ring gas resin, and diphenol alcohol-alkane (such as diphenol alcohol methane, diphenol alcohol ethyl) Alkane, bisphenol alcohol propane, etc.) polyglycidol, polyglycidyl ethers of polyphenols (such as novolac, cresol, resol, etc.), so that alicyclic compounds (such as cyclohexane, cyclopentadiene , Dicyclopentadiene, etc.) ring gas resin obtained by oxidation, poly (ring gas alkyl) esters of fatty gasification compounds (such as ethylene glycol, glycerol, etc.), aromatic or fatty carboxylic acid cycloalkyl Base esters, etc. In addition, as shown in, for example, USP No. 3,390,037, No. 2,970,983, and No. 3,067,170, pre-reaction products of ring gas resins and curing agents, or a mixture of both can be used. As for the polyester compound, the compounds represented by the following chemical formulas (2) and (3) are preferred. Among them, the acid component is preferably mainly terephthalic acid and the glycolytic component is preferably mainly neopentyl glycol or ethylene glycol. The number average molecular weight of these polyester compounds is 500 to 10,000, preferably 500 to 3,000 and a softening point of 101TC or less, preferably 70 ° C, the best results can be obtained: HO-Rx 0—f- c II ο
Ar CIIο Ο - Rl Ο. Η (2) (請先閲讀背面之注意事項再塡寫本頁) 或 HO- C-R2- C-O-Rx-O—f- C-Ar- C_〇-R]_-〇-'] C-R2~ C-OH il II II . tt II II 0 0 OO 〇 〇 (3) 其中Ar代表次苯基,Ri代表二價脂肪基且R2代表二價 本紙張尺度遣用中釅家揉毕(CNS)甲4規格(210x297公*) A 6 Β6 五、發明説明(丨4〇 芳香或脂肪基。 至於加到以(I)與(II)之混合物或預反應産物為 主成分之熱固性樹脂之環氣樹脂或聚酯樹脂,以100份 上述預反應産物或混合物的重置為基準,環氣樹脂的份 量為5到100份,而聚酯樹脂·為5到50份。許多倩況下 ,對任何環氣樹脂或聚酯樹脂而言30份就已足夠了。 根據以(I)與(II)之混合物或預反應産物為主成 分之熱固性基質樹脂的目的,可以加入觸媒。梅媒的適 當選擇,可以根據文中之前對以多官能順丁烯二酵亞胺 與多官能氡酸酯為主成分之熱固性基質樹脂之熟化作用 。添加之觸媒量也可根據該目的來決定,但佔全部基質 樹脂成分之2份或3份的數量對穩定度較佳。 至於本發明所使用的熱固性基質樹脂(C),可以使用 上述熱固性樹脂與一熱塑性樹脂或其齊聚物的摻合物。 特別是,就《熱性而言,所謂的工程塑驥如聚醛亞胺、 聚醚醒亞胺、聚硪、聚醚砠、聚醚醚酮較佳,而那些有 官能基能與熱固性樹脂在分子端或分子鏈上反醮者更好 。熱塑性樹脂可以溶解在熱固性基質樹脂中或以撤粉末 的型式混合。 以熱固性樹脂為準,加添之熱塑性樹脂麗以30%重量 比較佳,15%重*比更佳。若份*超過30%,条統的黏 滯性太高,這不只是在生産預浸體時造成較差的浸潰效 果,同時也降低預浸體的轱度特性與覆蓋特性^ -16- (請先閲讀背面之注意事項再填寫本頁) 本纸張尺度遑用中國國家標準(CNS)甲4規格(210X297公釐) 2〇5〇M 五、發明説明(fi) 另一方面,只要預浸鐮之特性、加工特性、力學特性 、熱力特性等不受改變,我們可以在熱固性樹脂内加入 少量的無機微粒(如矽氣撤粒)或揮性體成分(如丁二 烯/丙烯腈共聚物)。 彈性模數200GPa的加強纖維(A)與熱固性基質樹脂的 比值可以根據目的適當選定,但是(A)對(C)的tb值以在 5 5 : 4 5 到 8 5 : 1 5 較佳,6 0 : 4 0 到 7 5 : 2 5 更佳。 如果熱固性基質樹脂主要由琛《樹脂组成,(A)對(C) 的比值以60: 40到75·· 25較佳,而(B)對(C)為0.5: 1〇〇 到20: 100β若熱固性基質樹脂主要由多官能顒丁烯二 醛亞胺與多官能《酸酯之混合物或其預反應産物所組成 ,那麽最好(Α)對(C)的比值為60: 40到75: 25而(Β)對 (C)的比值為 0.5: 100 到 40: 100。 為了由彈性模數為200GPa或更高之加強鐵維(Α),熱 固性基質樹脂(C)以及》性模數為10DGP a或更少的纖維 性熱塑性樹脂生産出預浸鼸,我們可以使用以下方法。 然而,本發明不應當限定於渣些方法β 方法1 一種安嫌繼維性熱塑性樹脂(Β)於基礎預浸朦之上的 方法,其中預浸釀得自於加強性鑛維(Α)輿熱固性基Κ 樹脂(C),之後,進行加熱輿浸漬作用》 方法2 一棰闻時供應加強繼維(Α)與繼維性熱塑性樹脂(Β)至 -1 7- 本紙張尺度遑用中面B家樣準(CHS)甲4規格(210X297公*) C請先閱讀背面之注意事項再填窝本頁) -裝· 訂-Ar CIIο Ο-Rl Ο. Η (2) (Please read the precautions on the back before writing this page) or HO- C-R2- CO-Rx-O-f- C-Ar- C_〇-R] _-〇- '] C-R2 ~ C-OH il II II .tt II II 0 0 OO 〇〇 (3) where Ar represents phenylene, Ri represents a divalent fatty group and R2 represents a divalent paper size Finished with Zhongzhongjia (CNS) A 4 specifications (210x297 g *) A 6 Β6 V. Description of the invention (丨 4〇Aromatic or fatty group. As for the mixture or pre-reaction product added to (I) and (II) The ring gas resin or polyester resin of the thermosetting resin as the main component, based on the replacement of 100 parts of the above pre-reaction product or mixture, the ring gas resin part is 5 to 100 parts, and the polyester resin is 5 to 50 In many cases, 30 parts is enough for any ring-shaped resin or polyester resin. According to the purpose of the thermosetting matrix resin mainly composed of the mixture of (I) and (II) or the pre-reaction product, A catalyst can be added. The appropriate choice of plum media can be based on the maturation of thermosetting matrix resins with polyfunctional maleimide and polyfunctional radonate as the main components. The amount of catalyst can also be determined according to the purpose, but the amount of 2 or 3 parts of the total matrix resin component is better for stability. As for the thermosetting matrix resin (C) used in the present invention, the above thermosetting resins can be used Blended with a thermoplastic resin or its oligomer. In particular, in terms of thermal properties, the so-called engineering plastics such as polyaldimine, polyethersulfonimide, polyamine, polyether lipid, polyether ether Ketones are preferred, and those with functional groups can react with the thermosetting resin at the molecular end or molecular chain. The thermoplastic resin can be dissolved in the thermosetting matrix resin or mixed in the form of powder withdrawal. Based on the thermosetting resin, add It is better to add 30% by weight of the thermoplastic resin, and 15% by weight * is better. If the part * exceeds 30%, the viscosity of the system is too high, which is not only caused by poor impregnation in the production of prepreg Effect, and also reduce the prepreg's degree and coverage characteristics ^ -16- (please read the precautions on the back before filling this page) This paper standard uses the Chinese National Standard (CNS) A4 specification (210X297 %) 2〇5〇M V. Description of the invention (fi) On the other hand, as long as the characteristics, processing characteristics, mechanical characteristics, thermal characteristics, etc. of the prepreg sickle are not changed, we can add a small amount of inorganic particles (such as silicon gas to remove particles) or volatile components (such as Ding) into the thermosetting resin. Diene / acrylonitrile copolymer). The ratio of the reinforcing fiber (A) with a modulus of elasticity of 200 GPa to the thermosetting matrix resin can be appropriately selected according to the purpose, but the tb value of (A) to (C) ranges from 5 5: 4 5 to 8 5: 1 5 is better, and 6 0: 4 0 to 7 5: 2 5 is better. If the thermosetting matrix resin is mainly composed of resins, the ratio of (A) to (C) is preferably 60: 40 to 75 ·· 25, and (B) to (C) is 0.5: 100 to 20: 100β If the thermosetting matrix resin is mainly composed of a mixture of polyfunctional oxalimide and polyfunctional acid ester or its pre-reaction product, then the best ratio of (A) to (C) is 60: 40 to 75: 25. The ratio of (B) to (C) is from 0.5: 100 to 40: 100. In order to produce prepregs from reinforced iron (A) with a modulus of elasticity of 200 GPa or higher, thermosetting matrix resin (C) and fibrous thermoplastic resin with a modulus of 10 DGP a or less, we can use the following method. However, the present invention should not be limited to the slag method. Method 1 is a method that suspects that the secondary thermoplastic resin (B) is based on the basic pre-impregnation method, in which the pre-impregnation is derived from the reinforced mineral dimension (Α). Thermosetting base K resin (C), followed by heating and impregnation "Method 2 Immediately supply reinforced secondary dimension (Α) and secondary dimension thermoplastic resin (Β) to -1 7- This paper size uses the middle surface B home sample standard (CHS) A 4 specifications (210X297 g *) C Please read the precautions on the back before filling the nest page) -install · order-
2050M 五、發明説明(《ο 塗覆有熱固性基質樹脂(C)的脱模紙的方法,然後進行 浸漬作用β 方法3 一種方法,它安排並固定鐵維性熱塑性樹脂(Β)在塗 有熱固性基質樹脂的脱棋紙上·,終後在上面置放加強性 繼維(Α),之後進行浸潰作用。 顯示於麵1的方法可視為方法1的特例β 含加強雄維(Α)與熱固性基質樹脂(C)的基礎預浸體1 導向浸漬栝6 ,然後鑛雒性熱塑性樹脂(B)2經由諝節梳 3安排至預浸體上,並透過加熱壓滾桶4浸潰入並固定 於基礎預浸體上而得到預浸醣5。鐵維性熱塑性樹脂安 排到基礎預浸體上有兩種方法。其中一種,一邊上已經 安排熱塑性樹脂2的預浸《再一次如上地通通相同的程 序,而在另一邊安排熱塑性樹脂。另一淹方法中,如圃 2 ,熱塑性樹脂2同時在預浸體兩邊安排。任一種方法 都可使用。 更仔細參考顯示於麵2的方法,脱棋紙7從基礎預漫 艨1的背面剝落,纖雒性熱塑性樹脂2經由調節榇3安 排在基礎預漫«的兩邊,接著,兩邊上的熱塑性樹胞覆 蓋以脱棋紙8 ,之後,以熱壓滾桶對兩邊加熱、加壓。 如此,我Λ可以得到一種預浸*,其中鑛雒性熱塑性樹 脂定位於基礎預浸體的表面上,而己邇有一部分熱塑性 樹脂已經埋入基礎樹脂中β (請先閲讀背面之注意事項再填寫本頁) 裝- 訂_ 線· 本紙張尺度遑相中Β 家樣準(CNS)甲4規格(?10χ297公*) A 6 B6 五、發明説明(丨7) 至於要從加強纖維與熱固性基質樹脂中生産基礎預溲 體,我們可以直接使用一般生産預浸體的方法。這此方 法中,以所諝熱熔法較佳,其中不用溶劑而加熱、熔化 樹脂並塗在脱模紙上,之後進行加熱舆浸漬作用。然而 ,也可使用漆法,其中溶液内的樹脂塗在脱模紙上,浸 漬後再移除溶劑》 圖3所示之方法,可以視為方法2的待例。 塗有熱固性基質樹脂(C)的脱棋紙11之上,安排有經 過諏節梳13、3、3'的加強纖維(A)12與纖維性熱塑性樹 脂(B)2、2',使得鑛維12與樹脂2、2'之寬度與間距可 達到預定值,然後供應保護用的脱棋紙8 ,之後,以熱 壓滾桶4加壓、加熱以將熱固性基質樹脂浸潰到雄維内 。這樣就得到所欲得預浸體5。若只要在預浸醴一邊安 排鑛雒性熱塑性樹脂,我們只要供7應繼雒性熱塑性樹脂 2與2'其中之一就足夠了。 圔4中所示製造預浸體的方法,可視為方法3的特殊 實例,其中脱模紙15以塗覆機16塗上熱固性基質樹脂 (C)14,上面再安排並固定以鑼維性熱固性樹脂(B)2 , 之後,將加強織維置放於生成的樹脂膜17之上,接著以 一般方法進行浸漬作用。 本發明預浸體相對於以熱固性樹脂作為基質的預漫髏 ,不只擁有優艮的處理性質,而且可給予模造産品镘良 的細度而不損及熱力與力學性質β特別是,它對於受衝 -19- (請先閲讀背面之注意事項再填寫本頁) 裝. 订 線- 本紙張尺度进用中《覼家«準(CNS)甲4規格(210X297公釐) A 6 B6 五、發明説明(t?) 擊後層間的破碎有高度耐性,所以它可以作為飛機等之 結構材料β 本發明將以下列實例說明之。 實例中,所有的份數都以重量計。所用的環氣樹脂顯 示如下: 四縮水甘油二胺型環氣樹脂: YH434L(Toto Kasei Co., Ltd之商品名) 三縮水甘油二胺型琛氣樹脂: ELM-100 ( Sumitomo Che丨ical Co., Ltd之商品名) 雙酚A型環氣樹脂: Epikote 828 ( Yuka Shell Co.,Ltd之商品名) 雙酚F型環氣樹脂: Epikote 8 0 7 (Yuka Shell Co.,Ltd之商品名) 實例1至3 以熱熔法由表1所示之組成物與一種高強度、中彈性 模數之硪纖維(商品名,MR60P; Mitsubishi Rayon Co·, Ltd所生産;張力強度,5 6 0 0 MPa;揮彈性模數, 310GPa;斷點之延展度,1.9%)生産一單向基礎預浸 匾。該基礎預浸體的CF重量為145g/nf且其樹脂含量為 3 4 %重量比β 利用絲線捲糖法在基礎預浸兩邊捲上視厚度約40μα (總袋數90 d)(彈性模數,約2Gpa;絲線數,24)的 燹層尼龍12多絲(nultifilaBent),使得毎邊纖維重量 (請先閲讀背面之注意事項再填寫本頁) 裝< 訂 線- 本紙張尺度遑用中困家揉準(CNS)甲4規格(210x297公釐) A 6 B6 五、發明説明(<9) 為3 g/ nf β如此就得到本發明預浸體。得到之預浸體其 特擻在於尼龍多絲已經定位於它的兩邊而且一部分尼龍 多絲已經埋入基礎預浸體中。 根據 SACMA ( Suppliers of Advanced Composite M a t e r i a 1 s A s s o c i o t i ο η ,高级合成物質供應者協會) 所推薦之方法SRM2-88,該預浸體被切成預定尺度的小 塊,塊塊相叠以進行壓熱器模造作用,而得到施以衝擊 後用於置測壓縮強度的測試塊(熟化條件,180°CX2小 時)。接著,利用測試塊施以270 lb-in的衝擊後,量 測其壓縮強度,結果顯示於表1。 正如表1所示,與對照實例所得比較下,由本發明預 浸鱧所得之模造産品在施以衝擊後有高壓縮強度,耐衝 擊性佳。 對照實例1至3 以與實例1相同的方式生産一單向基礎預浸體,但是 所使用之樹脂膜的樹脂含量為36%重董比。評估程序與 實例1相同,但是尼龍12多絲並未附著在基礎預浸體上 。結果一起顯示於表1中。 -2 1- 本紙張尺度遑用中圃國家標準(CNS)甲4規格(210X297公藿) (請先閲讀背面之注意事項再填寫本頁) k' 五、發明說明(20 ) m 01 0 0 0呀 0οαcncvl 000 1 .0 <Ν1ε 02 脚 000 01 I—Il ®ιΛ‘σ3 00 0寸 一一 0CNJ①c\l艺 0 A6 B6 0 0 0 0 0·9 0 ·00 0 · 9 0 ·00 0 ·9 000 SU gr-Hg gg oos SCJi2050M V. Description of the invention (“ο Method of release paper coated with thermosetting matrix resin (C), followed by impregnation β method 3 A method which arranges and fixes iron-dimensional thermoplastic resin (B) coated with thermosetting On the release sheet of matrix resin, and finally place the reinforced secondary dimension (Α) on it, and then perform the impregnation effect. The method shown on the surface 1 can be regarded as a special case of the method 1 β with enhanced male dimension (Α) and thermosetting The basic prepreg 1 of the matrix resin (C) is directed to the impregnated root 6, and then the mineral-based thermoplastic resin (B) 2 is arranged on the prepreg through the knuckle comb 3 and is impregnated and fixed through the heated roller 4 On the basic prepreg to get prepreg sugar 5. There are two ways to arrange the iron-dimensional thermoplastic resin on the basic prepreg. One of them, one side has already arranged the prepreg of thermoplastic resin 2 "again the same as above. Procedure, and arrange the thermoplastic resin on the other side. In another flooding method, such as garden 2, the thermoplastic resin 2 is arranged on both sides of the prepreg at the same time. Either method can be used. Refer to the method shown on surface 2 for more details. Chess 7 The back side of the base pre-filling 1 is peeled off, and the fiber-based thermoplastic resin 2 is arranged on both sides of the base pre-filling 3 through the adjustment mechanism 3, and then, the thermoplastic tree cells on both sides are covered with release paper 8, and then, the roller is pressed with heat Heat and pressurize both sides. In this way, I can get a prepreg *, in which the mineral-based thermoplastic resin is positioned on the surface of the base prepreg, and some of the thermoplastic resin has been buried in the base resin β (please Read the precautions on the back first and then fill out this page) Binding-Order _ Line · The size of this paper is in the standard Β home sample standard (CNS) A 4 specifications (? 10χ297 g *) A 6 B6 V. Description of the invention (丨 7) As for the production of basic prepregs from reinforcing fibers and thermosetting matrix resins, we can directly use the general method of producing prepregs. In this method, the hot melt method is preferred, in which the resin is heated and melted without solvent It is coated on the release paper, and then heated and impregnated. However, the lacquer method can also be used, in which the resin in the solution is coated on the release paper, and then the solvent is removed after dipping. The method shown in Figure 3 can be regarded as Example of method 2 On the release paper 11 coated with the thermosetting matrix resin (C), the reinforcing fibers (A) 12 and the fibrous thermoplastic resins (B) 2, 2 'which are passed through the shuttle combs 13, 3, and 3' are arranged to make the mineral The width and spacing of the dimension 12 and the resins 2 and 2 'can reach a predetermined value, and then the protective release paper 8 is supplied, and then, the hot-pressing roller 4 is pressed and heated to impregnate the thermosetting matrix resin into the male dimension In this way, the desired prepreg 5 is obtained. If only the mineral-based thermoplastic resin is arranged on the side of the prepreg, we only need to supply one of the secondary thermoplastic resins 2 and 2 '. 7 圔 4 中The method of manufacturing the prepreg shown can be regarded as a special example of method 3, in which the release paper 15 is coated with the thermosetting matrix resin (C) 14 by the coating machine 16, and then arranged and fixed with a gauze thermosetting resin (B 2) After that, the reinforcing fabric is placed on the generated resin film 17 and then impregnated by a general method. The prepreg of the present invention not only possesses excellent processing properties compared to the pre-mantle with thermosetting resin as the matrix, but also can give the molded product a good fineness without compromising the thermal and mechanical properties. In particular, it is Chong-19- (please read the precautions on the back before filling in this page) Binding. Binding-The standard of this paper is "覼 家« Zhun (CNS) A 4 specifications (210X297 mm) A 6 B6 V. Invention Description (t?) The crushing between layers after hitting is highly resistant, so it can be used as a structural material for airplanes and the like. The present invention will be illustrated by the following examples. In the examples, all parts are by weight. The ring gas resin used is shown as follows: Tetraglycidyl diamine type ring gas resin: YH434L (trade name of Toto Kasei Co., Ltd) Triglycidyl diamine type gas resin: ELM-100 (Sumitomo Chelical Co. , Ltd. trade name) Bisphenol A type ring gas resin: Epikote 828 (Yuka Shell Co., Ltd. brand name) Bisphenol F type ring gas resin: Epikote 8 0 7 (Yuka Shell Co., Ltd brand name) Examples 1 to 3 The composition shown in Table 1 and a high-strength, medium-elasticity modular fiber (trade name, MR60P; produced by Mitsubishi Rayon Co., Ltd .; tensile strength, 5 6 0 0 MPa; swing modulus of elasticity, 310GPa; extension of breakpoint, 1.9%) produces a one-way foundation prepreg plaque. The CF weight of the basic prepreg is 145g / nf and its resin content is 34% by weight β. The thickness of the base prepreg is about 40μα (the total number of bags is 90 d) on the two sides of the basic prepreg by the silk-rolling sugar method. , About 2Gpa; the number of threads, 24) of the layered nylon 12 multifilament (nultifilaBent), which makes the weight of the edge fiber (please read the precautions on the back and then fill out this page). Installation < Threading-This paper is used Sleepy home kneading (CNS) A 4 specifications (210x297 mm) A 6 B6 V. Description of invention (< 9) 3 g / nf β As such, the prepreg of the present invention is obtained. The special feature of the obtained prepreg is that the nylon multifilament has been positioned on both sides and part of the nylon multifilament has been embedded in the base prepreg. According to the method SRM2-88 recommended by SACMA (Suppliers of Advanced Composite M ateria 1 s A ssocioti ο η, the Association of Advanced Synthetic Substances), the prepreg is cut into small pieces of a predetermined size, and the blocks are stacked to perform The autoclave is molded to obtain a test block for measuring the compressive strength after being impacted (mature condition, 180 ° CX2 hours). Next, the test block was applied with a 270 lb-in impact, and its compressive strength was measured. The results are shown in Table 1. As shown in Table 1, compared with the results obtained in the comparative example, the molded product obtained from the prepreg of the present invention has a high compressive strength after impact is applied, and is excellent in impact resistance. Comparative Examples 1 to 3 A unidirectional basic prepreg was produced in the same manner as in Example 1, but the resin content of the resin film used was 36% by weight. The evaluation procedure is the same as in Example 1, but the nylon 12 multifilament is not attached to the basic prepreg. The results are shown together in Table 1. -2 1- This paper uses the National Standards (CNS) A4 specifications (210X297 commonweed) of this paper (please read the precautions on the back before filling in this page) k '5. Description of the invention (20) m 01 0 0 0 呀 0οαcncvl 000 1 .0 < Ν1ε 02 pin 000 01 I—Il ®ιΛ′σ3 00 0 inch one one 0CNJ①c \ l art 0 A6 B6 0 0 0 0 0 · 9 0 · 00 0 · 9 0 · 00 0 · 9 000 SU gr-Hg gg oos SCJi
is SCVJSCNJ (請先閱讀背面之注意事頊再填驾本頁) sf.w郎屮史 μ ?;: 4^^^11^11¾ ¥逛 蝴枨 nwlMn US …>1α3) sBwMi«v 菡»( (001-W13) s ill»»剧逛Π活扭芩燥111 nm 5 ssaMM制挺Π涝扭关撰a ΐ/bo)Ht)c\lI iiaz 5 (edw)细猓镅H ?:滋鏘痤¾ 〔a〕 (¾¾始嚣懷锒)ah «镅倾嶙COS4J4V班蓖踣00£ SS雖撕诓^ _細刊翻tsffiJmlit 親$酬《舶距__鋰逛瓤蝴劫画蕊$001 0 .蛑, .線· m a -22- 本紙張尺度適用中0國家標準(CNS)甲4規格(210x297公嫠) ‘;:050·64_Be 五、發明説明(>丨) 實例4至6與對照實例4至6 與實例1方式相同,由MR60P與表2所示之樹脂組成 物得到一 CF重量為190g/n2且樹脂含量34 %重量比的基 礎預浸體。該基礎預浸體在兩邊以絲線捲嬈法捲上間距 3 mm的尼龍12多絲(81 d, 36 .fil)。如此得到本發明預 浸體。該預浸體的兩邊都有尼龍多絲定位其上且部分尼 龍多絲已經埋入基礎預浸體内。利用此預浸體,可在施 以衝擊後評估其壓縮強度,方式與實例1相同。 此外,利用樹脂含量為36%重置比的樹脂膜以類似方 式生産一預浸體。在未黏附尼龍多絲至預浸體的情況下 ,施以衝擊並評估其壓縮強度。 結果一起表示於表2中。 (請先閱讀背面之注意事項再填寫本頁) -23- 本紙張尺度逍用中國國家標毕(CNS)甲4規格(210X297公*)is SCVJSCNJ (please read the precautions on the back before filling in this page) sf.w 郎 屮 史 μ?;: 4 ^^^ 11 ^ 11¾ ¥ Shopping butterfly nwlMn US… > 1α3) sBwMi «v 菡» ((001-W13) s ill »» drama shopping Π live twisting Qinzao 111 nm 5 ssaMM control Π waterlogging twisted a ll / bo) Ht) c \ lI iiaz 5 (edw) fine 錓 镅 H?: AIDS Cong ¾ 〔a〕 (¾¾ Start arrogant) ah «America COS4J4V class cast iron 00 £ SS though torn up ^ _ fine magazine turn tsffiJmlit pro $ reward" ship distance __ lithium shopping 瓤 瓤 繤 画 理 $ 001 0. Insects, .Lines · ma -22- This paper scale is applicable to 0 National Standards (CNS) A 4 specifications (210x297 gong) ';: 050 · 64_Be V. Description of the invention (> 丨) Examples 4 to 6 and Comparative Examples 4 to 6 In the same manner as Example 1, a basic prepreg with a CF weight of 190 g / n2 and a resin content of 34% by weight was obtained from the resin composition shown in Table 2 and MR60P. The basic prepreg was wrapped on both sides by a silk winding method with nylon 12 multifilaments (81 d, 36 .fil) spaced 3 mm apart. Thus, the prepreg of the present invention is obtained. Nylon multifilaments are positioned on both sides of the prepreg and some nylon multifilaments have been embedded in the basic prepreg. With this prepreg, the compressive strength can be evaluated after impact is applied in the same manner as in Example 1. In addition, a prepreg was produced in a similar manner using a resin film with a resin content of 36% reset ratio. Without adhering the nylon multifilament to the prepreg, apply impact and evaluate its compressive strength. The results are shown in Table 2 together. (Please read the precautions on the back before filling out this page) -23- This paper scale is used in China National Standard (CNS) A4 specifications (210X297 public *)
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m m m CO to <S> <S G5 CD CS> ^ ^ cj in t-H <s> ①①⑤ P C\J to <s> cs> o <r> 々 CSJ 々 L〇 cs? <S> CD <S> ①⑤ 卜 co CM ① oo T~i to CVJ CM OCX ΙΛ' Cs3 卜 ΙΟ CS3 OO CSl m 镇 to m <S> CS? CD <S> -^r cm 10 t—» ① CD ①① cm ιο ①① ⑤① ^ C4 ^ LO c〇 r—1 CS) CO CO CO r QD CO r—i QD <〇 to L〇 CO CO 卜 CNJ CO OO CO oo i〇 csj co LO CsJ to c\i DtQ tex: d=c 靈 sg m m 剧 m m 逛 逛 5? —. ^ π π m^m «—.《—.醚 00 枨 tn^tn^mZu <_2蝴樓 缓=甥Ϊ菡二《s s ^ m s m s 11 ^ -C 、 a b〇 .'w. CSi T—* μ <us #—"V CD iX s: >W. m m m m •N 兹 餅 遐 t\ P >__i U1 ^ An 多 雜 S ..................................ί ............…装..............................訂…:….X .................终 {請先閲#卄面之注意事項再填寫本頁) 本紙張尺度適用中國國家樣準(CNS>甲4規格(2〗0χ297公嫠)mmm CO to < S > < S G5 CD CS > ^ ^ cj in tH < s > ①①⑤ PC \ J to < s > cs > o < r > 々CSJ 々L〇cs? < S > CD < S > ①⑤ bu co CM ① oo T ~ i to CVJ CM OCX ΙΛ 'Cs3 bu ΙΟ CS3 OO CSl m town to m < S > CS? CD < S >-^ r cm 10 t— »① CD ①① cm ιο ①① ⑤① ^ C4 ^ LO c〇r—1 CS) CO CO CO r QD CO r—i QD < 〇to L〇CO CO BU CNJ CO OO CO oo i〇csj co LO CsJ to c \ i DtQ tex: d = c spirit sg mm play mm wandering 5? —. ^ π π m ^ m «—. 《—. ether 00 枨 tn ^ tn ^ mZu < _2 Butterfly floor slow = 焥 Ϊ 菡 二 《 ss ^ msms 11 ^ -C, ab〇.'w. CSi T— * μ < us # — " V CD iX s: > W. mmmm • N zi pian yat \ P > __ i U1 ^ An Miscellaneous S ............................ L ............ … Pretend ........................ order ...: .... X ............ ..... end {please read # 卄 面 的 資訊 before filling in this page) This paper size is applicable to China National Standards (CNS> A4 specifications (2〗 0χ297 公 嫠)
實例7到1 8 以類似於實例4的方式生産一預浸體,但黾龍12多絲 的間距改變為如表3所示。施以衝搫後以實例1相同的 方式量測其壓縮強度。結果表示於表3。 表 3 (請先閲讀卄面之注意事項再填寫本頁) •^. •線· 實例11到1 5 以贲例4之方式生産一預浸體,但改變使用尼龍12多 絲的數目、間距如表4所示。施以衝擊後以實例1的方 式量測其壓縮強度。結果表示於表4。 -25- 實例 7 實例 8 實例 9 實例 10 成份(B ) 間距(m in) 1 2 4 5 (尼龍12) 重量 15 7 . 5 3.75 3.0 (g / nf ) 施以衝擊後之壓縮強 365 364 327 308 度 (MPa) Tg [t: ] 240 242 247 248 本紙張尺度適用中HS家標準(CNS)T4規格(210X297公釐)Examples 7 to 18 produced a prepreg in a manner similar to Example 4, but the pitch of the multifilaments of Strider 12 was changed as shown in Table 3. After the impact was applied, the compressive strength was measured in the same manner as in Example 1. The results are shown in Table 3. Table 3 (Please read the precautions before filling in this page) • ^. • Thread • Examples 11 to 1 5 Produce a prepreg by way of Example 4, but change the number and spacing of nylon 12 multifilaments As shown in Table 4. After the impact was applied, the compressive strength was measured in the same manner as in Example 1. The results are shown in Table 4. -25- Example 7 Example 8 Example 9 Example 10 Composition (B) Spacing (min) 1 2 4 5 (Nylon 12) Weight 15 7. 5 3.75 3.0 (g / nf) Compressive strength after impact 365 364 327 308 degrees (MPa) Tg [t:] 240 242 247 248 The paper size is applicable to the HS standard (CNS) T4 specification (210X297mm)
A6B6 五、發明説明{ 24 ) 寸 0 1〇 r*H 荜 m 'rr r—* m m ΓΟ r-H 荜 w CM r-H 荜 w r—4 r—· 荜 脚 <Σ> r-H r—< <S> l〇 CD 〇o 卜 c- tD <Σ> r~^> T~H t*Vi τΉ t〇 〇o CO L〇 CS) —r-H CO CM CO co ιο -5T to cs —CNJ to CM <〇 OO 11 r—« in gd 1—' CO 0〇 CM CO oo co CD *—4 CO CO CO co CO csj CO CO co CO oo CO CO co CM ΓΟ <NI CO 呀 CvJ L〇 呀 CM w E 、 ^ e w 3 m ^ w 舔_跬喇 黯癱漯SE鎰 CO cu 3E: m 珉 m m -N 斟 m 街 4~~> P S—J W >—»<· 一 CM CO 1-H 4TUU] έ ^ TS* '—· -26- (請先聞讀背面之注竞事項再填寫本頁) k. .線. 本紙張尺度適用中國國家標準(CNS)甲4規格(210x297公嫠) A 6 B6 五、發明説明(ν·0 實例16 (請先閱讀背面之注意事項再填寫本頁) 以實例4的方式生産—預浸體,但以尼龍6,12單絲 (彈性模數,約2 GPa;结旦,90 d)取代尼龍12多絲 。施以衝擊後量測到之壓縮強度β 實例1 7 六百八十克的雙酚F型環氣樹脂(Epikote 807), 477 克三縮水甘油二胺型琛氣樹脂(ELM-100)與426克四甲基 雙酚A裝入一反應器並在120*C反應8小時以得到預反鼴 混合物。三十五份此預反應産物,2 5份E p i It 〇 t e 8 0 7 , 40份四縮水甘油二胺型環氣樹脂(YH434L)與50份二氨基 二苯基隳摻合,並徹底混合至均勻。 由所得之樹脂組成物與一高強度、中彈性楔數碩纖雒 (M R60P)利用熱熔法得到一種單向基礎預浸體。這種預 浸體的CF重為19Qg/m 2 ,且其樹脂含量為34 %重董比。 該預浸體在其兩邊繞以間距3 的尼龍12多絲(81 d, 36 fil)以得到本發明預浸體。利用此預浸體,在施以 衝擊後以實例1的方式*測其壓縮強度並發現其為360 MPa〇 對照實例7 以實例17的方式生産一單向基礎預浸醍,但樹脂膜的 樹脂含量為36%重董比,以實例17的方式進行評估但尼 龍12多絲並未附著在基礎預浸釀之上。 施以衝擊強度之後的壓縮強度為2 7 4 MPa。 -2 7- 本纸張尺度遑用中國國家標毕(CNS)甲4規格(210X297公釐) A 6 B6 五、發明説明(>»〇 實例18 以實例17的方式生産一預浸體,但尼龍12多絲被不定 形尼龍(Dynaiit Nobel Co·, Ltd所生産的 Trogamid-T )多絲(彈性模數,約2 GPa;结旦,90 d;絲數,18 fil) »施以衝擊後量測到的壓縮強度為339 MPae 實例19 以實例17的方式生産一預浸鳗,但是以Troganid-T多 絲(90 d, 18 fil)與尼龍12多絲(81 d, 36 fil)的混成 絲線取代尼龍多絲12 (81 d, 36 fil),且繞線間距為 6 mm。施以衝擊後量測到的壓縮強度為341 MPae 實例20 以實例17相同的方式生産一預浸體,但是尼龍12多絲 以核部份為Troganid-T且鞘部份為尼龍12的共轭絲線 [9 0 d ; 1 8 f i 1 ;核 / 鞘=5 0 / 5 0 (重置比)’〕取代。 施以衝擊後的壓縮強度為3 4 2 MPa。 實例21 以實例17的方式生産一預浸匾,但以聚醛胺醛亞胺( Torlon 4 0 0 0 T,由 Aboco Co., Ltd所生産)的多絲(彈 性模數,約4 GPa;缠旦,240 d;絲數,24 fil)取代 尼龍12多絲,且鐃線間距為6 BB。施以衝擊後量測得之 壓编強度為336 MPa。 贲例2 2到2 4與bb較實例8到1 0 由表5所示之樹脂組成物與一高強度、中彈性棋數的 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度遑用中困國家搽準(CNS)甲4規格(?10X297公釐) A6 B6 公Ο δ的& 五、發明説明(>?) (請先閱讀背面之注意事項再填寫本頁) 碳鐡維(Mitsubishi Rayon Co·, Ltd所生産之 MR 50Κ ;張力強度,5600 MPa;彈性模數,300 GPa;斷點延 展度,1.8%)。基礎預浸體的CF重量為145g/nf,且其 樹脂含量為3 1 %重量比。 基礎預浸體的兩邊繞以聚醚·酷亞胺多絲(彈性模數, 約4 GPa;總旦,300 d;絲數24 fil)使邊之纖維重為 8 g/nf,如此可得本發明預浸體。 利用此預浸體,經實例1的方式量測其施以衝擊後之 壓縮強度,但熟化條件改為1 8 0 °C X 6小時,且後-熟化 作用在2 1 4 °C進行6小時。 施以衝擊後的壓縮強度顯示於表5。 此外,以實例22至24的方式生産一單向預浸體,但所 使用之樹脂膜其樹脂含量為36%重量比。在未使聚_醯亞 胺多絲附著於預浸體的情況下施以衝擊',測量其壓縮強 度。 施以衝擊後得到之壓縮強度顯示於表5 ^ -29- 本紙》•尺度遑用中國国家標毕(CNS) f 4規格(210x297公激) 五、發明説明(28 )A6B6 V. Description of invention {24) inch 0 1〇r * H 荜 m 'rr r— * mm ΓΟ rH 荜 w CM rH 荜 wr—4 r— · 荜 脚 < Σ > rH r— < < S > l〇CD 〇o 卜 c- tD < Σ > r ~ ^ > T ~ H t * Vi τΉ t〇〇o CO L〇CS) —rH CO CM CO co ιο -5T to cs —CNJ to CM < 〇OO 11 r— «in gd 1— 'CO 0〇CM CO oo co CD * —4 CO CO CO co CO csj CO CO co oo CO CO co CM ΓΟ < NI CO ah CvJ L〇 呀 CM w E 、 ^ ew 3 m ^ w licking _ 跬 拉 懬 是 SE 镒 CO cu 3E: m 珉 mm -N 斟 m street 4 ~~ > PS—JW > — »< · a CM CO 1- H 4TUU] έ ^ TS * '— · -26- (please read the remarks on the back and then fill out this page) k.. Line. This paper scale is applicable to the Chinese National Standard (CNS) Grade 4 (210x297) ) A 6 B6 V. Description of invention (ν · 0 Example 16 (please read the precautions on the back before filling in this page) Manufactured in the way of Example 4-prepreg, but with nylon 6,12 monofilament (elastic modulus , About 2 GPa; denier, 90 d) instead of nylon 12 multifilament. Compressive strength β measured after impact. Example 1 7 680 g Bisphenol F type ring gas resin (Epikote 807), 477 grams of triglycidyl diamine type Chen gas resin (ELM-100) and 426 grams of tetramethyl bisphenol A were charged into a reactor and reacted at 120 * C for 8 hours To obtain a mixture of pre-reaction moles. Thirty-five parts of this pre-reacted product, 25 parts of E pi It 〇te 8 0 7, 40 parts of tetraglycidyl diamine type ring gas resin (YH434L) and 50 parts of diaminodiphenyl Blended and blended thoroughly until homogeneous. From the resulting resin composition and a high-strength, medium-elastic wedge-numbered fiber fiber (M R60P), a one-way basic prepreg was obtained by hot-melt method. This prepreg Has a CF weight of 19Qg / m 2 and a resin content of 34% by weight. The prepreg is wrapped with nylon 12 multifilaments (81 d, 36 fil) with a pitch of 3 on both sides to obtain the prepreg of the present invention. Using this prepreg, after the impact was applied, the compressive strength was measured in the manner of Example 1 and found to be 360 MPa. Comparative Example 7 A unidirectional base prepreg was produced in the manner of Example 17, but the resin film was The resin content was 36% heavier than the ratio, evaluated in the manner of Example 17, but the nylon 12 multifilament was not attached to the base prepreg. The compressive strength after the impact strength was applied was 274 MPa. -2 7- This paper scale uses the Chinese National Standard (CNS) A4 specifications (210X297 mm) A 6 B6 5. Description of the invention (> »〇Example 18 A prepreg was produced in the manner of Example 17, But the nylon 12 multifilament is multifilament (Tromamid-T produced by Dynaiit Nobel Co., Ltd.) multifilament (elastic modulus, about 2 GPa; knot, 90 d; filament number, 18 fil) »Impact The compressive strength measured afterwards was 339 MPae. Example 19 A prepreg eel was produced in the same way as in Example 17, but with Troganid-T multifilament (90 d, 18 fil) and nylon 12 multifilament (81 d, 36 fil). The hybrid yarn replaces nylon multifilament 12 (81 d, 36 fil) with a winding pitch of 6 mm. The compressive strength measured after the impact is 341 MPae Example 20 A prepreg was produced in the same way as Example 17, However, the nylon 12 multifilament has a core part of Trojanid-T and a sheath part of nylon 12 conjugate filament [9 0 d; 18 fi 1; core / sheath = 5 0/5 0 (reset ratio) '] Replacement. The compressive strength after impact is 3 4 2 MPa. Example 21 A prepreg plaque was produced in the same manner as Example 17, but with polyaldimine aldimine (Torlon 4 0 0 0 T, by Aboco Co., Ltd. Place Production) of multi-filament (elastic modulus, about 4 GPa; twisted denier, 240 d; filament number, 24 fil) instead of nylon 12 multi-filament, and the spacing of the nab lines is 6 BB. Compression measurement measured after impact The strength is 336 MPa. Example 2 2 to 2 4 and bb are compared to examples 8 to 1 0. The resin composition shown in Table 5 and a high-strength, medium-elastic chess number (please read the precautions on the back before filling in this Page) This paper uses the standard of CNS Grade A 4 (? 10X297 mm) A6 B6 Ο δ of & V. Invention description (>?) (Please read the precautions on the back before (Fill in this page) Carbon dimensional (MR 50K produced by Mitsubishi Rayon Co., Ltd; tensile strength, 5600 MPa; modulus of elasticity, 300 GPa; elongation at break, 1.8%). The CF weight of the basic prepreg is 145g / nf, and its resin content is 3 1% by weight. Both sides of the basic prepreg are wrapped with polyether · imide multifilament (elastic modulus, about 4 GPa; total denier, 300 d; filament number 24 fil ) Make the edge fiber weight 8 g / nf, so that the prepreg of the present invention can be obtained. Using this prepreg, the compressive strength after impact is measured by the method of Example 1, but the curing condition is changed to 1 8 0 After C X 6 hours, and - curing is effected in 2 1 4 ° C 6 hours. Table 5 shows the compressive strength after impact. In addition, a unidirectional prepreg was produced in the manner of Examples 22 to 24, but the resin film used had a resin content of 36% by weight. The impact strength was applied without attaching poly-imide multifilaments to the prepreg, and the compression strength was measured. The compressive strength obtained after applying the impact is shown in Table 5 ^ -29- This paper "• The standard uses the Chinese National Standard (CNS) f 4 specifications (210x297 public shock) V. Invention description (28)
In撇 A6 B6 械 陛 m ① ΟΪ 〇〇 ①① od 1-H ⑤ LT3 LO <S> CO ① LO CD 卜 j—< CD CS) LO LD < CD 卜 r-H CS3 <3D Cs3 OO CO CO 卜 CO CD C\J CO 械 CSi cn cvj CM <M CD tO ΙΛ <S> CO f—* ①① CS **5J* ① LQ ①卜 r*H CD oo cs? 〇o <Σ> OO CD r—1 CM O CM CD ς〇 CM CO CO CO 卜 L〇 ro C4 r-H CO 11 兹 蝴 <Π 挺 鹅 冏 m 騮 ΦΚ II 挺 m ta H in < fc m umm 锕歧联sm »< -1 & h蝴糊 1猢鼷狀淞' ‘枨鰂π 11 °fe \ b〇 m 亞 u m m CO cu 2ε m m m m •N 兹 鉼 to 5SS. P to w <Π $ m 1g 刊 y—s >w' 枨&-蝴逛亞鱺111裝1.嫛鈉键钹11|(«1&1114^^)挺§5邐"《^鼷歜-9二 ♦igffi-糊枨Π蝴逛冏M:r践H®锕-一·々:菪<0蜓箧拔挺冏sin雎H1ISK··驟劫 • V / { ..................................(I .............…装..............................t…:…U .................疼 (請先閑讀背面之注意事項再填寫本頁) 本纸張尺度適用中0S家楳準(CNS)«F4規格(210x297公嫠) A 6 B6 五、發明説明(>9) 實例2 5與2 6 以實例22與2 3的方式得到本發明基礎預浸體,但聚醚 醯亞胺多絲被聚醯亞胺(Ciba Geigy Co.所産之 Matrimid 5218)多絲(彈性模數,約4 GPa;總旦, 250 d;絲數,24 fil)所取代,其中聚醯亞胺的酸成 分為二苯甲_四羧酸酐且二胺成分為5⑹-氛基-1- (4·-氨基苯)-1, 3 -三甲基IpiSUmdane)。量測其施以衝擊 後的壓縮強度。結果顯示於表6。 實例27與2 8 以實例22與23的方式得到本發明基礎預浸體,但聚醚 醛亞胺多絲以聚醯亞胺(LENZING AG所産之P-81)多絲 (彈性模數,約4 GPa;總旦,356 d;絲數,234 fil )取代之,其中聚醛亞胺的酸成分為二苯甲酮四羧酸酐 且二胺成分為甲苯二胺與4, 4’-二氨基二苯基甲烷的混 合物。量測施以衝擊後的壓縮強度《結果表示於表6 ^ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 -31- 本紙張尺度逍用中國國家標準(CNS)肀4規格(210 X 297公釐) (Λ (年 〔 Γ\Τ ϋΐΐίΐ______ ^ ιι in- γλλγIn skimming A6 B6 machine tool m ① ΟΪ 〇〇①① od 1-H ⑤ LT3 LO < S > CO ① LO CD Buj— < CD CS) LO LD < CD Bu rH CS3 < 3D Cs3 OO CO CO BU CO CD C \ J CO machine CSi cn cvj CM < M CD tO ΙΛ < S > CO f— * ①① CS ** 5J * ① LQ ① 卜 r * H CD oo cs? 〇o < Σ > OO CD r—1 CM O CM CD ς〇CM CO CO CO BU L〇ro C4 rH CO 11 zihu < Π 挺 鹅 冏 m 骝 ΦΚ II quite m ta H in < fc m umm actinic diversified sm »< -1 & h butterfly paste 1 錢 淞 淞 '' 枨 鲗 π 11 ° fe \ b〇m sub umm CO cu 2ε mmmm • N 鉉 to 5SS. P to w < Π $ m 1g 刊 y— s > w '枨 & -Australia annua 111 installed 1. Na sodium bond cymbal 11 | («1 & 1114 ^^) quite §5 逦 " 《^ 鼷 歜 -9 二Butterfly shopping M: r Practice H® Actinium-One · 々 : 菪 < 0 飏 繧 Pull out a sin H1ISK ·· Sudden robbery • V / {............... ................... (I ............. pretend .............. ................ t ...: ... U ................. pain (please read the notes on the back before filling in This page) This paper scale is applicable to the 0S Jiayu standard (CNS) «F4 Specification (210x297 gong) A 6 B6 V. Description of the invention (> 9) Examples 2 5 and 2 6 The basic prepreg of the present invention was obtained in the manner of Examples 22 and 2 3, but the polyether amide imine multifilament was polymerized Acetylene imide (Matrimid 5218 produced by Ciba Geigy Co.) multifilament (elastic modulus, about 4 GPa; total denier, 250 d; filament number, 24 fil), in which the acid component of polyimide is diphenyl Methyl tetracarboxylic anhydride and the diamine component is 5⑹-amino-1- (4 · -aminobenzene) -1,3-trimethyl IpiSUmdane). The compressive strength after impact is measured. The results are shown in Table 6. Examples 27 and 2 8 The basic prepreg of the present invention was obtained in the manner of Examples 22 and 23, but the polyether aldimide multifilament was polyimide (P-81 produced by LENZING AG) multifilament (elastic modulus, about 4 GPa; total denier, 356 d; filament number, 234 fil), where the acid component of polyaldimine is benzophenone tetracarboxylic anhydride and the diamine component is toluene diamine and 4, 4'-diamino A mixture of diphenylmethane. Measure the compressive strength after impact. The results are shown in Table 6 ^ (Please read the notes on the back before filling in this page) Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-31- Standard (CNS) Yuan 4 specifications (210 X 297 mm) (Λ (year [Γ \ Τ ϋll ίΙ ______ ^ ιι in- γλλγ
A B 五、發明説明(30) ω 擗 m w m m m 蓐 mA B 5. Description of the invention (30) ω 擗 m w m m m 蓐 m
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0Z.CNJ su (二3埘_骧ai?:班掛铤τί« 〔0。 η fr Μη^ΗΜί ^* ^ ^ η ^ S ^ η ^ Η ®5·'- ^ .· ^ ^ ^ ^ a ^ η ^ Η ®ϊ " » ^ (請先閑讀背面之注意事項再填寫本頁) •装· *訂· .線· 本紙張尺度適用中國a家榉準(CNS)子4規格(210x297公釐r0Z.CNJ su (二 3 埘 _ 骧 ai ?: Class hanging collar τί «[0. η fr Μη ^ ΗΜί ^ * ^ ^ η ^ S ^ η ^ Η ®5 · '-^. · ^ ^ ^ ^ A ^ η ^ Η ®ϊ " »^ (please read the precautions on the back before filling in this page) • Install · * Order ·. Thread · This paper size is suitable for China's a family of beech standard (CNS) sub 4 specifications (210x297 Mm
五、發明説明(¾丨) 實例2 9到3 2與對照實例1 1與1 2 由表7所示之組成物與一高強度、中彈性模數碩繼雒 (MR5QK)以表7所示之方法生産一單向基礎預浸體。此 基礎預浸體的CF重量為145g/nf,且其樹脂含量為34% 重量比。 此基礎預浸體以尼龍12多絲(彈性模數,約2 GPa;緦 旦,81 d;絲數,36 fil)在兩邊嬈線,使其每邊雄維 重為3 g/nf。如此,可得本發明預浸體。 利用此預浸體,以實例1之方式在施以衝擊後量測其 壓縮強度,結果顯示於表7。 此外,以實例29與30的方式生産一單向基礎預浸體, 但須諏節預浸體樹脂含量為36%重量比^未附箸尼龍12 多絲於預浸體的情況下,施以衝擊並量測其壓縮強度, 結果表示於表7。 實例33 以實例31的方式得到本發明預浸體,但調節基礎預浸 體的樹脂含量為31%重量比,且以聚_ SI (ICI所産之 VICTREX 5 0 0 3 )多絲(彈性模數,約4 GPa;總旦,250 d ;絲數,36 fil)取代尼龍12多絲,且嬈線需使基礎 預浸體毎邊所附著之聚醚硪為8 g/nf0施以衝擊後置測 到的壓縮強度為255 MPa。 實例34 以實例33的方式得到本發明基礎預浸體,但以聚醱醛 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度逍用中國國家樣準(CNS)甲4規格(210X297公*) 五、發明説明(4>)亞胺多絲(彈性模數, 2 4 f i 1)取代聚醚硪。 285 MPa〇V. Description of the invention (¾ 丨) Example 2 9 to 3 2 and comparative examples 1 1 and 1 2 The composition shown in Table 7 and a high-strength, medium-elasticity modulus master relay (MR5QK) are shown in Table 7 Method to produce a one-way basic prepreg. The CF weight of this basic prepreg is 145g / nf, and its resin content is 34% by weight. This basic prepreg is made of nylon 12 multifilament (elastic modulus, about 2 GPa; polyester, 81 d; filament number, 36 fil) on both sides, so that the male dimension on each side is 3 g / nf. In this way, the prepreg of the present invention can be obtained. Using this prepreg, the compressive strength was measured after the impact was applied in the same manner as in Example 1. The results are shown in Table 7. In addition, a one-way basic prepreg was produced in the manner of Examples 29 and 30, but the resin content of the sock prepreg was 36% by weight. ^ In the case where the filament was not attached to the nylon 12 and the prepreg was applied, The impact strength was measured and the compressive strength was measured. The results are shown in Table 7. Example 33 The prepreg of the present invention was obtained in the manner of Example 31, but the resin content of the basic prepreg was adjusted to 31% by weight, and the multi-filament (elastic modulus of poly_SI (VICTREX 5 0 0 3 produced by ICI)) , About 4 GPa; total denier, 250 d; filament number, 36 fil) to replace nylon 12 multifilament, and the thread needs to make the polyether base attached to the edge of the basic prepreg 8 g / nf0 after impact The measured compressive strength is 255 MPa. Example 34 The basic prepreg of the present invention was obtained in the form of Example 33, but with polyacetal (please read the precautions on the back before filling in this page). This paper scale is used in China National Standards (CNS) A4 specifications (210X297 (Public *) V. Description of the invention (4>) Imine multifilament (elastic modulus, 2 4 fi 1) replaces polyether. 285 MPa〇
66 AB 旦绝 量 後 a:擊 GP衝 4 以 約施 d 數為 絲度 強 縮 壓 其 測 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度逍用中國國家標毕(CNS)甲4規格(210X297公褒) XΙΑ Α6 Β6 五、發明説明(33 ) 濟 郎屮 f- 这) il t to CNJ CD <0 <S> <v c 脚 蘅 镑键 >s—·· GD T—*4 o CM r—♦ CSI CM 陛 辄 11 m m LO CSJ ① CD CD CSD 0) c o eg CsJ 卜 〇〇 r—* X CNJ 1 法 1EK) L〇 CSD <SD CM CO LO CO 藏 後链 S_^>- τ—«♦ CO m 您 to CM ① <S> CO① L〇 L〇 <s> <〇 L〇 〇 <s> to m CM CNJ 聃 CS3 CO 法 1 : ΜΕΚ) to CNJ <X> CO CD <S5 <s> to lO 卜 τ-Η m 礙 m .¾ CP Csl m 铵 L〇 CM CD C〇 ① <S) C£> CO <s> OO <s> OO r—H CM CM CO V-H TO cu 5E: 'w· CQ 定:二Ϊ 卜 jrsi J-Q OO 嫌碟 -s m ΰ 5 i二菡鐙氍 Csl m r~"\ P ο ο ο ^ «ug ig m m m °fe E5 bO m •N 酿 *s 兹 00 m w <□ 斟 m $鹚 ΰΰΤ m m s 制 -35- 本纸張尺度適用中國國家標準(CNS)甲4規格(210x297公釐) (請先W讀背面之注意事項再填寫本頁) •綠· A 6 _B_6_ 五、發明説明(¾今) 注釋: Aro Cy B-30: 2,21-雙(4-氯醯苯基)丙烷(Hi-Tek Polymers _Co.所産)之預聚合物。 Aro Cy M-30:雙(3,5-二甲基-4-氣醯苯基)甲烷 (Hi-Tek Polyners Co.所産)·之預聚合物。 Aro Cy L-10: 2, 2’-雙(4-気醛苯基)乙烷(Hi- Tek Polymers C〇.所産) XU71787:與化學式(I)代表相同之化合物(Dow Chemical Co.所産) 實例35至37與對照實例13至15 由顯示於表8之樹脂組成物與一高強度、中彈性模數 磺纖維MR5QK以熱熔法生産一單向基礎頊浸體。該基礎 預浸體的CF重量為145 g/nf,且樹脂含量為34 %重童比 〇 此基礎預浸體在其兩側嬈以尼龍12多絲(彈性模數, 約2 GPa;總旦,81 d;絲數,36 fil)使其每邊纖維 重為3 g/nfe如此可得本發明預浸體。 利用此預浸體,在施以衝擊後以實例1的方法量测其壓 縮強度。結果表示於表8。 實例38 以實例35的方式得到本發明基礎預浸體,但諏節基礎 預浸體的樹脂含置為31%重量比,且以聚醚硫明(ICI 所産之VICTREX 5 0 0 3)多絲(彈性模數,約4 MPa ; -3 6 - (請先閲讀背面之注意事項再塡寫本頁) 本紙張尺度边用中困國家標準(CNS)甲4規格(210X297公藿) 五、發明説明(>,) 總旦,250 d;絲數,36 fil)取代尼龍12多絲,同時 撓線時要使預浸體每邊附著之聚醚W為8 g/nf ^施以衝 擊後量测其壓縮強度為240 MPa。 實例39 以實例38的方式得到本發明基礎預駸體,但以聚醚醯 亞胺多絲(彈性模數,約4 GPa;绝旦,300 d;絲數, 24 fil)取代聚醚砠。施以衝擊後量測其壓縮強度為 278 MPa„ 實例40 以實例38的方式得到本發明基礎預浸體,但以聚芳基 fiJS (Amoco Co_,Ltd 所生産之 RADEL A-200)多絲(彈 性模數,約3 GPa;總旦300 d;絲數,50 fil)取代聚 醚硪》施以衡擊後測董其壓缩強度為265 MPa。 A 6 B6 (請先閱讀背面之注意事項再填寫本頁) 裝· 訂_ -37- 本紙張尺度遑用中國國家«罕(CNS)甲4規格(210X297公*)66 AB After the absolute amount a: hit the GP 4 and use the d-number as the silk to shrink the test (please read the precautions on the back and then fill out this page). The paper standard uses the Chinese National Standard (CNS) A4 specifications (210X297 public testimonials) XΙΑ Α6 Β6 V. Description of the invention (33) Jilang 冮 f- this) il t to CNJ CD < 0 < S > < vc foot step pound key > s— ·· GD T— * 4 o CM r— ♦ CSI CM 11 mm LO CSJ ① CD CD CSD 0) co eg CsJ 卜 〇〇r— * X CNJ 1 method 1EK) L〇CSD < SD CM CO LO CO Back chain S _ ^ >-τ— «♦ CO m you to CM ① < S > CO① L〇L〇 < s > < 〇L〇〇 < s > to m CM CNJ 聃 CS3 CO method 1: ΜΕΚ) to CNJ < X > CO CD < S5 < s > to lO 卜 τ-Η m would m .¾ CP Csl m ammonium L〇CM CD C〇① < S) C £ > CO < s > OO < s > OO r—H CM CM CO VH TO cu 5E: 'w · CQ fixed: two Ϊ 卜 jrsi JQ OO suspected disc-sm ΰ 5 i 二 握 镫 氍 Csl mr ~ " \ P ο ο ο ^ «ug ig mmm ° fe E5 bO m • N Brew * s tz 00 mw < □ 斟 m $ 鹚 ΰΰΤ mms made-35- This paper scale is applicable to the Chinese National Standard (CNS) A 4 specifications (210x297 mm) (please read the back side first (Notes to fill out this page) • Green · A 6 _B_6_ V. Description of the invention (¾Today) Notes: Aro Cy B-30: 2,21-bis (4-chlorophenyl) propane (Hi-Tek Polymers _Co. Produced). Aro Cy M-30: Prepolymer of bis (3,5-dimethyl-4-acetylphenyl) methane (manufactured by Hi-Tek Polyners Co.). Aro Cy L-10: 2, 2'-bis (4- 気 aldehydephenyl) ethane (manufactured by Hi-Tek Polymers Co.) XU71787: the same compound as the chemical formula (I) (manufactured by Dow Chemical Co.) Examples 35 to 37 and Comparative Examples 13 to 15 From the resin composition shown in Table 8 and a high-strength, medium-elasticity modulus sulfonate fiber MR5QK, a unidirectional base leaching body was produced by hot-melt method. The CF weight of the basic prepreg is 145 g / nf, and the resin content is 34%. The weight of the basic prepreg is nylon 12 on both sides of the basic prepreg (elastic modulus, about 2 GPa; total denier , 81 d; filament number, 36 fil) to make the fiber weight of each side 3 g / nfe so that the prepreg of the present invention can be obtained. Using this prepreg, the compression strength was measured by the method of Example 1 after the impact was applied. The results are shown in Table 8. Example 38 The basic prepreg of the present invention was obtained in the manner of Example 35, but the resin content of the Suwa basic prepreg was 31% by weight, and it was multifilament with polyether thiamine (VICTREX 5 0 0 3 produced by ICI). (Elastic modulus, about 4 MPa; -3 6-(Please read the precautions on the back before writing this page) This paper scale is used in the national standard (CNS) A 4 specifications (210X297 common potion). Description (>) Total denier, 250 d; number of filaments, 36 fil) instead of nylon 12 multifilaments, and at the same time, the polyether W attached to each side of the prepreg is 8 g / nf ^ after impact The compressive strength was measured to be 240 MPa. Example 39 The basic pre-prosthesis of the present invention was obtained in the same manner as in Example 38, but polyether amide imide multifilament (elastic modulus, about 4 GPa; denier, 300 d; filament number, 24 fil) was used instead of polyether. After impact, the compressive strength was measured to be 278 MPa. Example 40 The basic prepreg of the present invention was obtained in the manner of Example 38, but with polyaryl fiJS (RADEL A-200 produced by Amoco Co., Ltd.) multifilament ( Modulus of elasticity, about 3 GPa; total denier 300 d; filament number, 50 fil) replaces polyether tumbler. After applying a counterattack, the compression strength of Dong was measured to be 265 MPa. A 6 B6 (Please read the precautions on the back before filling in this Page) Binding · Order _ -37- This paper standard uses the Chinese National «Han (CNS) A 4 specifications (210X297 g *)
A6B6 五、發明説明(36 ) 000 經濟部屮央標H1-局対工消^合作杜卬1 1〇 LO l〇 L〇 CNJ CNJ CD CD CN3 C\3 r-t CD Csj OO T—1 1—! <3D cs> σ> r—* uri to CM m 陛 LO in ①①CNJ CM CD CS> CC CD 1—t CD r—4 05 CC <S5 〇 CM 〇· CM m to in tn cm ca ①① CN3 CO — ① r~H 〇) r-H t-H CS) CD CSJ CM CSJ L〇 CM un CO L〇 CM CM CO CS5 CM CM T—· 〇D CM CO t—i it <s> CD Id LO CSJ o CsJ ς〇 CO L〇 ①①CSJ 04 CS5 CS> CO CO t-h CD r—4 〇) ① CO CO ς〇 <m CNJ CM W irs co tn to ιο c\3 ca OD <S> CM CSJ r-H <s> r—· 0¾ »-H r-H cs> CO CM 〇0 CM LO CNJ 枨 聒 ssm jg| ** J m°° mm Ψξ <Z<^m 3氕=芻α齷W圮 锕糊3锕S齩π Π % to CM inuu3 ties tts CO D- 2ε: >w" 想 m m h 邀 鉍 i£T TO 遐 i~~» P v__/ if <Π Φ鹚 堪s r—». CO bo (奴ng榧:03 nsjav usdIH) US23V :伥a®aj>«u遐齩SPLO2滩龊与釤仞輙踣氍屮葙链騮-^芒捩杻:夂齷齩 歧Ε(*^^¥-{ο»-.<ΓΟ“:Ν3α3:®+Η (請先聞讀背面之注意事項再填寫本頁) 05 •訂· 槲 •線· 本纸張尺度適用中國g家標準(CHS)甲4規格(210x297公釐) Α6 Β6 實例4 1至4 3 由表9所示之樹脂組成物與一高強度、中彈性模數碩 纗維(MR60P)經由熱熔法製造一單向基礎預浸體。該基 礎預浸體的CF重為190 g/nf,且其樹脂含量為34%重董 bb 〇 利用國2所示之方法安排尼龍12多絲(90 d/ 36 fil)於基礎預浸體的兩邊且間距為3 ime 利用該預浸體,以實例1的方式在施以衝擊後量測其壓 縮強度,結果表示於表9。 39- 本紙張尺度逍用中國國家猱準(CNS)甲4規格(210x297公*) (請先閲讀背面之注意事項再填寫本頁) 裝· 訂' % τ- 丄f兩充 Α6 Β6 五、發明説明(38 ) 懈 CO ^r CQ CS> CS5 <3D <S ^ CM LO r-< <〇 CO 1 LO m CO CNJ CS3 ①① ⑤① ^ -^r cm ιο CD CO CO LO 做 CO CJ T-H •^r ①①① OD kj* CM 'ϊΤ LO Oi cn !0 KK CO CM g 鋰 麟 賴 m 铿 m m ^ <—*'- CO m 挺 w O- SE π π m « ^ ^鹏00枨 t~~\ ίπ ^ ίπ S ^ -2 11 禊 P '/ 务3务1 < j蝴寒 m 骧β缓Ϊ芻二贼趙 m m - m s s 11 ^ H 鉼 W· <0 h0 Φ 鹚 链 s 遐 -40- 本紙張尺度適用中國國家標準(CNS)甲4規格(2丨0><297公嫠) {請先閱讀背面之注意事項再填寫本頁) k. 訂- .線· A 6 B6 五、發明説明(巧) 實例4 4至4 6 利甩圖3所示的方法,以熱熔法生産本發明單向 預浸體,其中一高強度、中彈性模數碩纖雒(MR60P)與 尼龍12多絲(90 d/36 fil)同時供應至樹脂膜,樹脂膜 的樹脂組成物顯示於表10,並且覆蓋在脱膜紙上。此例 中,按排尼龍12多絲的間距為3 ππιβ 此預浸體的CF重為190 g/nf·且硪纖雒對熱固性基質 樹脂的重量比為6 6對3 4 β 利用此預浸體,以.實例1的方式量測施以衝擊後之壓 縮強度,結果表示於表10。 (請先閲讀背面之注意事項再塡寫本頁) -41- 本紙張尺度遑用中Β國家樣毕(CNS)甲4規格(210X297公釐) Α6 Β6 五、發明説明(40) 01 0 M濟部屮失標平局5=工消兑合作杜印1 CO to 敝 W <3D CD O CD CD ^ ^ 04 ΙΛ τ-Η cs cs5 <r> 〇 ^ cm ① CSD ①① 寸 C\J 呀 L〇 OJ Csi CO to T—Η 卜 CN3 CO CO in CN] m ιο csl ^r CSJ 婴 鋰 Wt Μ 醚 赌 剧翻 S m m 筠 ~ _ 11 π m^m μ 00 ^ 扭#扭S剧3 η 务3务1 < 蝴填 缓a=骧菡 s匕川S鈉S Π鉍 'W m m m m iM 邀 鉼 it? w 提 r~\ P »«___t bO ·»—% w <D 多 鹚 ig s (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家橾準(CNS)干4規格(210X297公嫠) A 6 B6 £〇50^/l- 五、發明説明(斗i) 實例4 7至4 9 利用圖4所示之方法,安排間距3删的尼龍多絲於樹 脂膜上以製造一樹脂膜,其中樹脂組成物表示於表Η並 塗覆於脱膜紙上。 由如此所得的樹脂膜與一高,強度、中彈性模數碩纖雒 MR60P經由一般之熱熔法製造本發明單向基礎預浸體。 此預浸體的C F重為1 9 0 g / nf ,且磺纖維與熱固性基質 樹脂的重量比為66對31 利用此預浸體,以實例1的方式量测施以衝擊後的壓 縮強度,結果表示於表11。 (請先閱讀背面之注意事項再填寫本頁) 裝· -43- 本紙張尺度遑用中國國家樣毕(CNS)甲4規格(210x297公*) A6 B6 五、發明説明(42 ) II 懈A6B6 V. Description of the invention (36) 000 The Ministry of Economy ’s central standard H1-Bureau of Industry and Commerce ^ Cooperation Du 卬 1 1〇LO l〇L〇CNJ CNJ CD CD CN3 C \ 3 rt CD Csj OO T-1 1—! < 3D cs > σ > r— * uri to CM m 陛 LO in ①①CNJ CM CD CS > CC CD 1—t CD r—4 05 CC < S5 〇CM 〇 · CM m to in tn cm ca ①① CN3 CO — ① r ~ H 〇) rH tH CS) CD CSJ CM CSJ L〇CM un CO L〇CM CM CO CS5 CM CM T— · 〇D CM CO t—i it < s > CD Id LO CSJ o CsJ ς 〇CO L〇①CSJ 04 CS5 CS > CO CO th CD r—4 〇) ① CO CO ς〇 < m CNJ CM W irs co tn to ιο c \ 3 ca OD < S > CM CSJ rH < s > r— · 0¾ »-H rH cs > CO CM 〇0 CM LO CNJ 枨 聒 ssm jg | ** J m °° mm Ψξ < Z < ^ m 3 氕 = 揉 α 龌 W 圮 锕 醕 3 锕 S 齩π Π% to CM inuu3 ties tts CO D- 2ε: > w " Think mmh invite bismuth i £ T TO xiai ~~ »P v __ / if < Π Φ 鹚 堪 sr—». CO bo (奴 ng 榧: 03 nsjav usdIH) US23V: 伥 a®aj > «u ya 鈩 SPLO2 beach 鰊 and 钐 丞 踙 鑮 鑮 chain prosperity-^ 鎮 捩 杻: 夂 龌 齩 銩 E (* ^^ ¥-{ο»- . < ΓΟ “: Ν3α3: ® + Η (please read the precautions on the back and then fill out this page) 05 • Order · Querce · Line · This paper scale is applicable to China's g Family Standard (CHS) A4 specification (210x297 Mm) Α6 Β6 Example 4 1 to 4 3 A unidirectional basic prepreg was manufactured by hot-melt method from the resin composition shown in Table 9 and a high-strength, medium-elasticity modulus (MR60P). The CF weight of the prepreg is 190 g / nf, and the resin content is 34%. The weight of the resin is bb. The nylon 12 multifilament (90 d / 36 fil) is arranged on both sides of the basic prepreg using the method shown in country 2. The spacing is 3 ime. Using this prepreg, the compressive strength was measured in the manner of Example 1 after impact was applied. The results are shown in Table 9. 39- The size of this paper is easy to use China National Standard (CNS) A4 (210x297 g *) (please read the precautions on the back before filling out this page) Binding · Order '% τ- 丄 ftwo charge Α6 Β6 5. Description of the invention (38) CO ^ r CQ CS > CS5 < 3D < S ^ CM LO r- < < 〇CO 1 LO m CO CNJ CS3 ①① ⑤① ^-^ r cm ιο CD CO CO LO do CO CJ TH • ^ r ①①① OD kj * CM 'ϊΤ LO Oi cn! 0 KK CO CM g Lilin Lai m 铿 mm ^ < — *'-CO m rect w O- SE π π m «^ ^ 鹏 00 枨t ~~ \ ίπ ^ ίπ S ^ -2 11 禊 P '/ Duty 3 Duty 1 < j Butterfly Hanm 骧 β slow Ϊ RU er thief Zhao mm-mss 11 ^ H 鉼 W · < 0 h0 Φ 鹚 链s ya-40- This paper scale is applicable to the Chinese National Standard (CNS) Grade 4 specifications (2 丨 0> < 297 gong) (Please read the precautions on the back before filling out this page) k. Order-.Line · A 6 B6 V. Description of invention (smart) Example 4 4 to 4 6 Using the method shown in FIG. 3, the unidirectional prepreg of the present invention is produced by the hot-melt method, one of which is a high-strength, medium-elastic modulus master fiber ( MR60P) and nylon 1 2 Multifilament (90 d / 36 fil) was supplied to the resin film at the same time. The resin composition of the resin film is shown in Table 10 and was covered on the release paper. In this example, the pitch of the nylon 12 multifilaments in a row is 3 ππιβ. The CF weight of the prepreg is 190 g / nf. The weight ratio of the fiber fiber to the thermosetting matrix resin is 6 6 to 3 4 β. Use this prepreg The compression strength after impact was measured in the manner of Example 1. The results are shown in Table 10. (Please read the precautions on the back before writing this page) -41- This paper uses the National Beta National Sample (CNS) A 4 specifications (210X297 mm) Α6 Β6 V. Description of the invention (40) 01 0 M The Ministry of Economic Affairs lost the draw and tie 5 = Cooperative Dumping Cooperation Du Yin 1 CO to DW < 3D CD O CD CD ^ ^ 04 ΙΛ τ-Η cs cs5 < r > ○ ^ cm ① CSD ①① inch C \ J ah L〇OJ Csi CO to T—Η Bu CN3 CO CO in CN] m ιο csl ^ r CSJ Infant Lithium Wt Μ Ether Gambling Turn S mm 筠 ~ _ 11 π m ^ m μ 00 ^ twitch #tws S 剧 3 η Service 3 Service 1 < Butterfly filling a = 雧 菡 s Daggerchuan S sodium S Π bismuth 'W mmmm iM invites it? W mention r ~ \ P »« ___t bO · »—% w < D s (Please read the precautions on the back before filling in this page) This paper size is applicable to China National Standard (CNS) dry 4 specifications (210X297 public daughter) A 6 B6 £ 〇50 ^ / l- V. Description of invention (Dou i ) Example 4 7 to 4 9 Using the method shown in FIG. 4, a nylon film with a pitch of 3 is arranged on the resin film to produce a resin film, in which the resin composition is shown in Table H and coated on the release paper. From the resin film thus obtained, a high-strength, medium-elasticity modulus fiberglass MR60P is used to manufacture the unidirectional basic prepreg of the present invention through a general hot-melt method. The CF weight of this prepreg was 190 g / nf, and the weight ratio of sulfonate fiber to thermosetting matrix resin was 66 to 31. Using this prepreg, the compressive strength after impact was measured in the manner of Example 1, The results are shown in Table 11. (Please read the precautions on the back and then fill out this page) 装 · -43- This paper uses Chinese National Sample (CNS) A4 specifications (210x297 g *) A6 B6 V. Invention description (42) II
坪斋"卜夂茗 A !·_? ·Τ·Γ-Ρ「ί .、,F 03 m 〇〇 m 卜 m <S CS) GD O CS5 ^ ^=r c^a in i—i CD ① ⑤ <=r 寸 cm l〇 CD CS> CS> CD cm ^ in 卜 CO CO cs> CO CO ΙΛ CO CO io LO CM LO CM CO CM m 鋰 B W _ m ® m m m m 逛 m 逛一._ ii π « ^ ^ w 00 枨 扭呀扭m剧+j Π '2 mm S匕111 s.锕s π齡 〇"— CO a. s: >·_"·. m m 撰 m 鉼 ffi? m /i P \__) to § <π 多 鹚 链 e (請先《讀背面之注意事項再填钙本页) .裝. •打· .線. 本紙張尺度適用中國g家楳準(CNS)甲4規格(210x297公釐) A 6 B6 -- 五、發明説明(▲$) 實例50 由表12所示之樹脂組成物舆一离強度、中彈性棋數硪 纖維MR60P經由一般之熱熔法製造一單向基礎預浸鼸》 此預浸體的CF重為190 g/#,·且其樹脂含量為34%*此 基礎預浸髖在兩邊境以間矩2.5 尼龍12多絡(45 d/36 fil)以得到本發明預浸。 利用此預溲體,以V例1的方式量拥> 施以衝擊後的壓 缩強度,結果表示於表12。 生成之組合物之截面以顯撤鏡檢査之,發現部分層與 層間等間距桉排的尼龍12多絲以融熔態侵入基礎預浸體 的表面(參考臞5 )。 對照實例16 以實例50的方式得到一對照預浸醍,但是預浸_製造 過程上要使尼龍12多絲(45 d/36 fil)完全埋在基礎預 浸體的内部。 利用此預浸鰌,以實例1的方式量測其施以衝擊後的 壓縮強度,結果顯示於表12。 不 f 層 絲部 於 多内 脂 12層 樹 龍各 性 尼於 塑。 現在 熱度 發存 性強 •地 維编 面距 鐵壓 截間 中的 的等 集後 物絲 ,擊 合多 現衝 組的 發受 成融 以良 生熔 可改 察但 們幅 觀,❶我大 鏡間}果以 撤靥5 结可 顯與H項間 以層考此層 在參由輿 本紙張疋度遑用中國·家樣準(CNS)T4規格(210x297公釐) (請先閲讀背面之注意事項再填寫本頁) 裝· 訂- 線- 妁年“/A ‘ κ·4 A6 B6 五、發明説明(44) 0Ping Zhai " Bu Su Ming A! · _? · Τ · Γ-Ρ 「ί. 、, F 03 m 〇〇m 卜 m < S CS) GD O CS5 ^ ^ = rc ^ a in i—i CD ① ⑤ < = r inch cm l〇CD CS > CS > CD cm ^ in BU CO CO cs > CO CO ΙΛ CO CO io LO CM LO CM CO CM m lithium BW _ m ® mmmm wander m wander one._ ii π «^ ^ w 00 戨 twist ah twist m drama + j Π '2 mm S dagger 111 s. actinium s π age 〇 " — CO a. s: > · _ " ·. mm 编 m 鉼 ffi? m / i P \ __) to § < π multi-branched chain e (please read “Notes on the back and then fill in the calcium page”). Install. • Strike.. Line. This paper size is suitable for China g Jiashu standard (CNS ) A 4 specifications (210x297 mm) A 6 B6-V. Description of the invention (▲ $) Example 50 The resin composition shown in Table 12 and the strength, medium elasticity of the fiber MR60P through general thermal fusion Method to produce a one-way basic prepreg "The CF weight of this prepreg is 190 g / #, and its resin content is 34% * This basic prepreg hip is 2.5 nylon 12 multi-collateral between the two borders (45 d / 36 fil) to obtain the prepreg of the present invention. Using this prepreg, measure the volume in the manner of V example 1 > apply compression strength after impact The results are shown in Table 12. The cross-section of the resulting composition was examined with a clear lens, and it was found that some layers of eucalyptus nylon 12 multifilaments with equal spacing between layers penetrated into the surface of the basic prepreg in the molten state (refer to 臞 5) Comparative Example 16 A comparative prepreg was obtained in the same manner as in Example 50, but the prepreg_manufacturing process required that the nylon 12 multifilament (45 d / 36 fil) be completely buried inside the base prepreg. Use this prepreg Chen, the compressive strength after impact was measured in the same manner as in Example 1. The results are shown in Table 12. The f-layer silk part is multi-lactone 12-layer tree dragon. The ground-knitting surface is separated from the iron pressure section by the same set of back filaments, and the combination of the multi-chongchong group's hair can be improved with good health. But our views can be changed, ❶My big mirror room} The fruit is to be removed. 5 The test can be taken as a layer between item H and item H. This document can be used in the Chinese version of the homepage standard (CNS) T4 (210x297mm) (please read the precautions on the back before filling out this page ) Binding · Ordering-Thread-妁 年 "/ A 'κ · 4 A6 B6 V. Description of the invention (44) 0
LZ ειLZ ει
LZ •Εϋ 0卜2 mLZ • Εϋ 0 卜 2 m
LZ ΠLZ Π
LZ εε Ε洎擗攻仞騸 蝤脏坊_ί<5锸 froaI ||3/农铌 (請先W讀背面之注意事項再填寫本頁)LZ εε Ε 洎 擗 攻 亟 靤 貤 坊 _ί < 5 锸 froaI || 3 / Agricultural niobium (please read the precautions on the back before filling this page)
SCO S3 '…襄· 經濟郎"?~^^平局朽工^-^^合作— ο % 窜糊淋η _ ® η (82003215 鋰逛贓醚剷V菡婀 (00I-W1S S 萆Μ® 到逛:!«.&考摆111 (m=A) 鋰 aKKg-tligΠ 爱扭关隳a 3ΐ雔蚂 (3)逛链 <Dms (3) (edK)tti(娌撰騙·Ν^2Ι«^^ 〔a〕 3一 •訂. •線· -46- 本纸張尺度適用中困國家標準(CNS)甲4規格(210X297公嫠)SCO S3 '... Xiang · Economy Lang'? ~ ^^ Drawing work ^-^^ Cooperation — ο% Fleece η _ ® η (82003215 lithium shopping shovel ether shovel V 叡 婀 (00I-W1S S 萆 Μ® to shopping:! «. &Amp; 考 放 111 (m = A) Lithium aKKg-tligΠ Love twisting Guana a 3l 雔 銔 (3) Chaining chain < Dms (3) (edK) tti (娌 訂 嬹 · Ν ^ 2Ι «^^ 〔a〕 3 一 • 定. • Line · -46- This paper scale is applicable to the national standard (CNS) A 4 specifications (210X297 public daughter)
Claims (1)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP33183490 | 1990-11-29 | ||
JP3610291 | 1991-03-01 | ||
JP5702591A JP3065685B2 (en) | 1991-03-20 | 1991-03-20 | Manufacturing method of prepreg |
JP5702391A JP3065683B2 (en) | 1991-03-20 | 1991-03-20 | Prepreg |
JP5702491A JP3065684B2 (en) | 1991-03-20 | 1991-03-20 | Prepreg |
Publications (1)
Publication Number | Publication Date |
---|---|
TW205054B true TW205054B (en) | 1993-05-01 |
Family
ID=51356707
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW080109339A TW205054B (en) | 1990-11-29 | 1991-11-27 |
Country Status (1)
Country | Link |
---|---|
TW (1) | TW205054B (en) |
-
1991
- 1991-11-27 TW TW080109339A patent/TW205054B/zh not_active IP Right Cessation
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