426697 A7 B7 經濟部中央標隼局貝工消贤合作社印取 五、發明説明（1 ) 技術範疇 本發明係有關一種以聚環氧烷增韌之改質酚醛樹脂及 其製法。 發明背景 由於酚醛樹脂具有良好之熱安定性、電絕緣性、尺寸 安定性、耐化學性等特點，已廣泛地應用於電路積層板、 絕熱材料、塗裝與接著劑等.。再者，酚醛樹脂基之複合材 料因具有防火、難燃、發煙量低等特性，已成爲重要的防 火材料用樹脂之一。目前、國外已推出的酚醛樹脂基複合 材料有酚醛樹脂爲基材之塊狀模造材料（Bulk Molding Compound’BMC)及板狀模造材料（Sheet Molding Compound, SMC)。這些產品主要應用在公共建築的裝潢、隔間及運 輸系統的零組件；至於酚醛樹脂爲基材的複合材料拉擠成 型製品則不多見。其主要原因在於酚醛樹脂的反應速率通 常較慢、製程不穩定、樹脂與纖維間之鍵結情形較差，且 酚醛樹脂其本身性質較脆、韌性差，與其它樹脂系統比較， 酚醛樹脂應用在拉擠成型製程之難度較高，因此其應用不 如環氧樹脂與不飽合聚脂樹脂普及，其品質與性能亦還有 待進一步的提昇。 ' 過去已發展出幾種技術來增加酚醛樹脂的韌性。例如 日本專利特公昭297595號使用松脂，美國專利5,459,223號 使用奈酚（naphthol)，美國專利5,432,24〇號使用瀝青 (pitch)，美國專利4,6 11，020號使用三聚氰胺（melamine)， 本紙诙尺度適用中國國家標隼（CNS ) A4規格（210X297公漦） I— y^衣 I n ii n n r 來 (請先閱讀背面之注意事項再填穷本買} 經濟部中央標準局貝工消費合作社印製 426697 . A7 B7 五、發明説明（2 ) 美國專利4，166，166號使用苯乙酮（acetophenone)，美國專 利2,675,3 3 5號使用烷基酚及美國專利4,1 57,324號使用高鄰 乙醚化（high ortho etherified)可溶型酚醛樹脂。但這些技 術都必需將改質劑和酚醛樹脂預先反應才能達到改質的目 的。 酚醛樹脂和一般纖維的表面鍵結均欠佳，因此造成在 製作酚醛樹脂基複合材料時常需使用經特殊表面處理的纖 維，對複合材料製造業者而言，生產時需投入更高的成本 更換不同的纖維。因此所加入的改質劑若能改善酚醛樹脂 和一般纖維的表面鍵結，必能降低製造所需的成本。 聚環氧烷，例如聚環氧乙烷（簡稱PEO)爲一高結晶度 之水溶性塑膠，以鹼土族（Ca ' Ba、Sr)化合物（氧化物、碳 酸鹽類）或有機金屣化合物和水形成共催化劑（co-catalyst) 而聚合，屬於配位聚合反應機構（Coordination polymerization mechanism)。高分子量之 PEO ( 1 05- 1 07)具 高度結晶的固體可用押出法製造。主要應用在水溶性包裝 膜 '界面活性劑、上漿劑、混凝劑、導電性複合材料、生 醫材料、增稠劑（thickening agent)等。 到目前爲止尙無人建議以聚環氧烷來增韌酚醛樹脂、 或改善酚醛樹脂與其它材質之間的界面鍵結。_ 發明之總結 本發明同時揭示了以聚環氧烷增韌之改質可溶型酚醛 樹脂及改質淸漆型酚醛樹脂。 -4- 本紙浪尺度適用中國國家標隼（CNS ) Α4規格（2Ι0Χ297公釐） --------->裝------訂------r 入請先Μ-讀背面之注意事項再填湾本頁) 經濟部中央標绛局員工消费合作社印製 426697^ J A7 B7 五、發明説明（3 ) 該改質可溶型酚醛樹脂，包含：（a)—重量平均分子量 釋 100，000·8，000,000的聚環氧烷（poly (alkylene oxide)); (b) —酚類：（c)—酸催化劑；及（d)—可溶型酚醛樹脂（Res〇l type phenolic resin)，其具有6O-75重量。/。固體成份及5-10重量％ 的自由甲醛；其中以成分（d)的重量爲基準，成分（a)、（b) 及（c)的含量分別爲2-10%、2-15%及2-10%。較佳地，成分 (a)及（b)的含量約相等，及成分（a)的含量爲4-8%，以成分（d) 的重量爲基準。 本發明之改質淸漆型酚醛樹脂，包含：上述成分（a); 成分（b);及（d’）一淸漆型酣醒樹脂（Novolac type phenolic resin)，其在25°C具有200-2000的黏度，以約300cps爲較佳， 其中以成分（d’）的重量爲基準，成分（a)及（b)的含量分別爲 2-10%及2-1 5%。較佳地，成分（a)及（b)的含量約相等，及 成分（a)的含量爲4-8%，以成分（d’）的重量爲基準。此改質 淸漆型酚醛樹脂可進一步含有2·〗5%，以約10%爲較佳， 的硬化劑，以成分（d’）淸漆型酚醛樹脂的重量爲基準。此 硬化劑可爲習知技藝中已知之任何一種適用於淸漆型酚醛 樹脂，例如多胺類的六伸甲基四胺（Hexamethylene Tetramine，簡稱 Hexamine)及 S-三胺（S-triamine);縮醒 類和一些非醛類的硬化劑如含磷鹽類（三甲醇基次磷酸鹽 (Trimethylol phosphine oxide))。較佳地，該硬化劑爲六伸 甲基四胺。 較佳地，該聚環氧烷爲聚環氧乙烷或聚環氧丙烷或它 們兩者的混合物。 本紙孩尺度適用中國國家標準（CNS ) Λ4規格（210X 297公髮） --------^裝------訂------r 〆請先閱讀背面之注意事項再填寫本頁) 4 266 9 經濟部中央標準局貝工消費合作社印策 A7 B7 五、發明说明（4 ) 本發明亦揭示此等改質酚醛樹脂的製法。 一適合用於製備該改質可溶型酚醛樹脂的方法，包含 下列步驟： (A) 將上述成分（a)與成分（b)依1.5 :1 -1:1的重量比例混 合後，於一昇高溫度，較佳地約l〇(TC，攪拌均勻，於是 獲得一高黏度混合物： (B) 將該酸催化劑[成分（c)]與步驟（A)的高黏度混合物 混合而獲得一黏度大幅減低.的低黏性混合物；及 (C) 將步驟（B)的低黏性混合物與該成分（d)可溶型酚醛 樹脂混合而形成一聚環氧烷增韌之改質可溶型酚醛樹脂， 其中該成分（a)及（C)的用量，以成分（d)的重量爲基準，分 別爲 2-10%及 2-10%。 本案發明人很意外的發現前述步驟（A)的高黏度混合 物在加入該酸催化劑後其黏度會大幅降低，吾人相信此乃 該催化劑可使該聚環氧烷帶電而有利於其分散於帶極性的 酚類中。因此將一額外的電解質加入步驟（A)的高黏度混 合物的技術手段應被視爲與本發明的酸催化劑功能性相等 的。 一適合用於製備該改質淸漆型酚醛樹脂的方法，包含 下列步驟： (A)將上述成分（a)與成分（b)依1.5:1-1:1的重量比例混 合後，於一昇高溫度，較佳地約100°C，攪拌均勻，於是 獲得一高黏度混合物；及 (B’）將步驟（A)的高黏度混合物與該成分（d，）淸漆型酚 -6- 度適用中國國家標準（CNS ) Λ4規格（210X297公釐） ---------y 裝------訂------r (諳先"讀背面之注意事項再填寫本頁) 426697, A7 _B7 五、發明説明（5 ) 醛樹脂混合而形成一聚環氧烷增韌之改質淸漆型酚醛樹 月旨，其中該成分（a)的用量’以成分（d，）的重量爲基準，爲 2-10%。 該改質淸漆型酚醛樹脂的製備方法可進一步包含： (C’）將2-15%的一硬化劑，以成分（d’）淸漆型酚醛樹脂 的重量爲基準，與該步驟（B’）的改質淸漆型酚醛樹脂混合 而形成一進一步含有一硬化劑的改質淸漆型酚醛樹脂。 由於聚環氧烷具有良好的黏著效果，若未與該酚類在 一昇高溫度預先混合，而直接將聚環氧烷摻混於本發明之 低黏度淸漆型酚醛樹脂中將獲得一黏度相當高、麵糰狀混 合物，而不適用於在一般複合材料、塗料或黏著劑的製造。 當然一般之高分子量（黏度）的市售淸漆型酚醛樹脂更不適 用於製備本發明之改質淸漆型酚醛樹脂。 發明之詳細敘沭 本案發明人率先發展出一種技術成功的將聚環氧烷摻 混於酚醛樹脂中來改質酚醛樹脂，而達到增韌酚醛樹脂及 改善酚醛樹脂與其它材質之間的界面鍵結爲目的。 經濟部中央標準局負工消资合作社印製 (請先閱讀背面之注意事項再填寫本頁) 酚醛樹脂具有大量的苯環基，結構較剛硬（Rigid)，但 也由於苯環分子造成太大的空隙，在受到外力時，力量很 容易從排列較鬆散的縫隙傳遞，造成酚醛樹脂韌性不佳。 由於聚環氧烷上之醚基可.以和酚醛樹脂上的OH官能基形 成分子間氫鍵，使兩者的相容性十分良好，同時藉由這種 氫鍵引力的存在，使具柔軟鏈段的熱可塑性樹脂緊密地穿 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210X 297公錢） 426697 經濟部中央標準局貝工消費合作社印" A7 B7 五、發明説明（6 ) 梭在酚醛樹脂空隙中，使酚醛樹脂之自由體積減少，增加 分子間的密實度。在受到外力衝擊時，柔軟鏈段不但可以 延長破壞所需的路徑長度，還可以增加能量的吸收，達到 增韌的效果。 由於聚環氧烷含有大量的醚基可使該聚環氧烷改質的 酚醛樹脂在應用於塗裝、黏著、及纖維強化樹脂複合材料 方面時’具有改善的界面鍵結情形。尤其，在製作纖維強 化樹脂複合材料時，聚環氧烷可增加改質的酚醛樹脂和纖 維之間的含浸及黏著效果，此外聚環氧烷在纖維強化樹脂 複合材料的製作中也具有潤滑劑的作用，因此本發明之改 質酚醛樹脂特別適用於作爲纖維強化樹脂複合材料之製 作。 製備使用於本發明的可溶型酚醛樹脂的一合適方法包 含在一鹼性觸媒存在下將過量甲醛或其類似物與酚進行縮 合而得。此製備方法爲業界所熟知，例如在美國專利 4,4 1 9,400號即載有一詳細製備方法，該專利的內容在此爲 本案發明的參考資料。 上述酸催化劑，已爲業界所習知，例如可參考英國專 利1，363,277號的資料，而以對位甲苯磺酸（p-toluene sulfonic acid)，酣碼酸（phenol sulfonic acid)，安息香酸 (benzoic acid)及磷酸爲較佳，其含量佔全部可溶型酚醛樹 脂的2-10重量％，而以5重量％爲最佳。 該酸催化劑亦可以與同重量的胍類化合物促進劑一起 使用，例如二苯胍（diphenylguanidine)。 本紙伖尺度適用中囷國家標準（CNS ) Α4见格（210Χ297公釐} _(請先Μ.讀背面之注意事項再填寫本頁) ί >裝· ，-° 4266 9 A7 B7 五、發明説明.（7 ) 在本發明的一較佳實施例中，聚環氧烷和酚係在loot 被充分攪拌混合而獲得一稠狀物（Glutinous Material)。對 位甲苯磺酸催化劑及二苯基胍被預先於l〇〇°c互溶，再被 加入該稠狀物攪拌混合而獲得黏度約25〇CpS(l 00°C )的似水 溶液。再將此似水溶液與預熱至10〇°C的該可溶型酚醛樹 脂充分攪拌混合，即獲得本發明的改質可溶型酚醛樹脂。 此改質可溶型酚醛樹脂剛製備完成時並冷卻至30°c時具有 800〜2000cps的黏度。於本發明中所有的黏度均係依ASTM D2 393方法以布汝克菲黏度計（Brookfield Viscometer)測量 而得。 經濟部中央糅準局負工消费合作社印製 (請先閱讀背面之注^一^項再填寫本頁) 製備使用於本發明的淸漆型酚醛樹脂的一合適方法包 含在一酸性觸媒存在下將酚與甲醛或其類似物以約1:0.8莫 耳比的比例進行縮合反應一段時間，加入一鹼而中和反應 混合物，將該反應混合物的水層及樹脂層分離，及揮發移 除所獲得樹脂層中的水分及小分子。在本發明的另一較佳 實施例中，該縮合反應係在100°C進行約30分鐘，所製得 淸漆型酚醛樹脂具有一數平均分子量約492及重量平均分 子量約20 32*並且含0.15重量％的自由酚（free phenol)及90 重量％的固體含量，其中19%爲鄰-鄰，57%爲鄰-對和24 %爲對-對位甲基架橋的雜排酚環連結架橋結構。 於本發明的該另一較佳實施例中，聚環氧烷和酚係在 100 t；被充分攪拌混合而獲得一稠狀物（Glutinous Material)。將此稠狀物與l〇〇°C的該淸漆型酚醛樹脂充分攪 拌混合’再置入於80°C烘箱中約30分鐘即獲得一黏度較低 本紙张尺度適用中國國家標準（CNS ) Λ4規格（210X 297公漦） 4266 9 經濟部中央標準局員工消费合作社印聚 A7 B7 、發明説明（8 ) 似水狀的改質淸漆型酚醛樹脂。此改質淸漆型酚醛樹脂剛 製備完成時並冷卻至25°C時具有約200-2000cps的黏度。 由於合成淸漆型酚醛樹脂所使用的酚多於释，所以淸 漆型酣醒樹脂不含具反應性的甲醇基（methanol group,- ch2〇h) > 的酚醛樹脂，因此，加工時必須加入硬化劑，使之形成網 狀結構。一般較常用的硬化劑爲六伸甲基四胺，若要提高 其耐燃性，則可再使用含磷的鹽類來提昇其耐燃性。 市場上主要供應之淸漆型酚醛樹脂爲固態，不適合以 拉擠成型製作纖維強化樹脂複合材料，而分子量較高的溶 液型淸漆型酚醛樹脂固體含量約爲86wt%，約14wt%之溶 劑易造成有機揮發物（VOC)之污染，也不適合拉擠成型製 程。本發明所自行合成之液體狀淸漆型酚醛樹脂水份可在 真空烘箱內完全去除，同時未添加任何會造成污染的溶 劑，加工性良好，製程穩定，·因此可以適用在拉擠成型製 程上。 適用於本發明的酚類包括（但不限定於）苯酚，鄰-甲 酣，間·甲酚，對-甲酚，二甲酚，乙苯酚，對苯基苯酚， 對丁基苯酚，對戊基苯酚，雙酚A及間苯二酚。 上述以聚環氧烷增韌之改質可溶及淸漆型酚醛樹脂可 進一步加入礦物塡充劑（filler)，例如碳酸鈣、矽石及滑石 粉以增進其物理性質及機械性質，其含量約佔全部樹脂重 量的 10-20%。 本發明的改質可溶及淸漆酚醛樹脂在交聯時放出的水 -10· 本紙張尺度適用中國囡家標準（CNS)A4規格（ 210X297公簸） --------y 裝------訂------.r - _(諳先軋讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消f合作社印衆 426697, A7 _B7__ 五、發明説明（9 ) 氣會明顯減少，尤其是聚環氧烷改質之淸漆型酚醛樹脂放 出的水氣非常少，空孔率也因而降低。改質之酚醛樹脂其 韌性及機械強度均大幅增加，複合材料亦具有優異之防火 難燃性質。在每一種應用上面均可以得到上述改善的結 果。在本發明中謹以拉擠成型複合材料的實施例來示範說 明本發明的優點。 以下實施例的溫度以攝氏表示，成份比例則以重量爲 基準。 實施例1 :聚環氧乙烷改質之可溶型酚醛樹脂 聚環氧乙烷和可溶型酚醛樹脂混練之配方如表1所 示： 表1 成份 重量，克 製造廠 (1)聚環氧乙烷， 8 Union Carbide Co,美國 200,000 (2)酚 8 聯工所，台灣 (3)對位甲苯磺酸 5 第一化學，台灣 (4)二苯胍 5 和光化學，日本 (5)可溶型酚醛樹脂 100 長舂樹脂，台灣 首先將8克的聚環氧乙院與8克的酸在通氮氣的情形 下，溫度保持100T：下以攪拌機攪拌1小時’使之達到充份 互溶，形成黏度極高的黏稠液’將預先準備好的硬化劑（5426697 A7 B7 Printed by the Bei Gong Xiaoxian Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (1) Technical scope The present invention relates to a modified phenolic resin toughened with polyalkylene oxide and its preparation method. BACKGROUND OF THE INVENTION Because phenolic resins have good thermal stability, electrical insulation, dimensional stability, chemical resistance and other characteristics, they have been widely used in circuit laminates, thermal insulation materials, coatings and adhesives. In addition, phenolic resin-based composite materials have become one of the important resins for fireproofing materials due to their properties such as fire resistance, flame resistance, and low smoke generation. At present, phenolic resin-based composite materials that have been launched abroad include bulk molding materials (Bulk Molding Compound'BMC) and sheet molding materials (SMC) based on phenolic resins. These products are mainly used in the decoration, compartments and components of transportation systems of public buildings; pultrusion of phenolic resin-based composite materials is rare. The main reasons are that the reaction rate of phenolic resin is usually slow, the process is unstable, the bonding between the resin and the fiber is poor, and the phenolic resin itself is relatively brittle and poor in toughness. Compared with other resin systems, phenolic resins are used in The extrusion process is more difficult, so its application is not as popular as epoxy resins and unsaturated polyester resins, and its quality and performance need to be further improved. '' Several technologies have been developed in the past to increase the toughness of phenolic resins. For example, Japanese Patent Publication No. 297595 uses turpentine, U.S. Patent No. 5,459,223 uses naphthol, U.S. Patent No. 5,432,240 uses pitch, and U.S. Patent No. 4,6 11,020 uses melamine. The standard is applicable to China National Standard (CNS) A4 (210X297). I— y ^ clothing I n ii nnr (please read the precautions on the back before filling in the poor purchase) Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative Printed 426697. A7 B7 5. Description of the invention (2) US Patent No. 4,166,166 uses acetophenone, US Patent No. 2,675,3 3 uses alkylphenol and US Patent No. 4,1,57,324 High ortho etherified soluble phenolic resin. However, these technologies all require the modifier and phenolic resin to react in advance to achieve the purpose of modification. The surface bonding of phenolic resin and general fiber is not good, so As a result, fibers with special surface treatment are often used when making phenolic resin-based composite materials. For composite material manufacturers, it is necessary to invest a higher cost to replace different fibers during production. Therefore, if the added modifier can improve the surface bonding of phenolic resin and general fiber, it will definitely reduce the cost required for manufacturing. Polyalkylene oxide, such as polyethylene oxide (PEO for short) is a high crystal Degree of water-soluble plastic, polymerized with alkaline-earth (Ca 'Ba, Sr) compounds (oxides, carbonates) or organic gold compounds and water to form a co-catalyst, belongs to the coordination polymerization reaction mechanism ( Coordination polymerization mechanism). PEO (1 05- 1 07) with high molecular weight can be manufactured by extrusion method. It is mainly used in water-soluble packaging films, such as surfactants, sizing agents, coagulants, and conductive composite materials. , Biomedical materials, thickening agent, etc. So far, no one has suggested using polyalkylene oxide to toughen phenolic resins, or to improve the interface bonding between phenolic resins and other materials. _ Summary of the invention The invention also discloses modified modified phenolic resin toughened with polyalkylene oxide and modified lacquered phenolic resin. -4- The paper scale is applicable to China National Standard (CNS) A4 specification (2Ι0 × 2 97 mm) --------- > Loading ------ Ordering --- r Please enter M-, read the notes on the back, and then fill in this page) Ministry of Economic Affairs Central Standard Printed by the Bureau ’s Consumer Cooperatives 426697 ^ J A7 B7 V. Description of the invention (3) The modified soluble phenolic resin contains: (a) —polyalkylene oxide with a weight-average molecular weight release of 100,000 · 8,000,000 (Poly (alkylene oxide)); (b)-phenols: (c)-acid catalyst; and (d)-soluble type phenolic resin, which has a weight of 60-75. /. Solid content and 5-10% by weight of free formaldehyde; of which, based on the weight of component (d), the content of components (a), (b) and (c) are 2-10%, 2-15% and 2 -10%. Preferably, the contents of components (a) and (b) are approximately equal, and the content of component (a) is 4-8%, based on the weight of component (d). The modified varnish-type phenolic resin of the present invention comprises: the above-mentioned component (a); component (b); and (d ') a Novolac type phenolic resin, which has a temperature of 200 at 25 ° C. The viscosity of -2000 is preferably about 300 cps, and based on the weight of the component (d '), the contents of the components (a) and (b) are 2-10% and 2-1 5%, respectively. Preferably, the contents of components (a) and (b) are approximately equal, and the content of component (a) is 4-8%, based on the weight of component (d '). The modified lacquer-type phenolic resin may further contain 2.5%, preferably about 10%, a hardener based on the weight of the component (d ') lacquer-type phenolic resin. This hardener can be any of the known phenolic resins known in the art, such as polyamines such as Hexamethylene Tetramine (Hexamine) and S-triamine (S-triamine); Awake and some non-aldehyde hardeners such as phosphorus salts (Trimethylol phosphine oxide). Preferably, the hardener is hexamethylene tetramine. Preferably, the polyalkylene oxide is polyethylene oxide or polypropylene oxide or a mixture of both. The size of this paper is applicable to the Chinese National Standard (CNS) Λ4 specification (210X 297). -------- ^ Installation ------ Order ------ r 〆Please read the notes on the back first (Fill in this page again) 4 266 9 Imprint A7 B7, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (4) The present invention also discloses a method for preparing these modified phenolic resins. A method suitable for preparing the modified soluble phenolic resin includes the following steps: (A) mixing the above component (a) and component (b) in a weight ratio of 1.5: 1 to 1: 1, and then Raise the temperature, preferably about 10 (TC, stir well, so as to obtain a high viscosity mixture: (B) Mix the acid catalyst [ingredient (c)] with the high viscosity mixture of step (A) to obtain a viscosity Substantially reduced low-viscosity mixture; and (C) mixing the low-viscosity mixture of step (B) with the component (d) soluble phenolic resin to form a modified polyalkylene oxide toughened soluble type Phenolic resin, wherein the amounts of the components (a) and (C) are 2-10% and 2-10%, respectively, based on the weight of the component (d). The inventor of the present case has unexpectedly found the aforementioned step (A) After adding the acid catalyst, the viscosity of the highly viscous mixture will be greatly reduced. I believe that this catalyst can charge the polyalkylene oxide and facilitate its dispersion in polar phenols. Therefore, an additional electrolyte is added The technical means of the high-viscosity mixture of step (A) should be considered as the acid catalyst of the present invention. The chemical agents have the same functionality. A method suitable for preparing the modified lacquer-type phenolic resin includes the following steps: (A) The above-mentioned component (a) and component (b) according to 1.5: 1-1: 1 After mixing the weight ratios, stir at an elevated temperature, preferably about 100 ° C, to obtain a high-viscosity mixture; and (B ') combine the high-viscosity mixture of step (A) with the component (d,)淸 Lacquer type phenol-6-degree applies to Chinese National Standard (CNS) Λ4 specification (210X297 mm) --------- y equipment -------- order ------ r (谙 先" Read the notes on the back side and fill in this page again) 426697, A7 _B7 V. Description of the invention (5) Modified lacquer type phenolic tree toughened by aldehyde resin mixed to form a polyalkylene oxide, in which the component ( The amount of a) is 2-10% based on the weight of the component (d,). The method for preparing the modified varnish-type phenolic resin may further include: (C ') 2-15% of a hardener Based on the weight of the component (d ') lacquer-type phenolic resin, it is mixed with the modified lacquer-type phenolic resin in this step (B') to form a modification further containing a hardener. Lacquer-type phenolic resin. Because the polyalkylene oxide has a good adhesion effect, if it is not pre-mixed with the phenol at an elevated temperature, the polyalkylene oxide is directly blended into the low-viscosity lacquer-type phenolic resin of the present invention. The admiral obtains a rather viscous, dough-like mixture, which is not suitable for the manufacture of general composite materials, coatings or adhesives. Of course, general high molecular weight (viscosity) commercially available lacquer-type phenolic resins are even less suitable for the preparation of this product. Modified lacquer-type phenolic resin of the invention. Detailed description of the invention The inventor took the lead in developing a technologically successful blending of polyalkylene oxide in phenolic resin to modify the phenolic resin to achieve toughening and improvement of the phenolic resin. The purpose of interfacial bonding between phenolic resin and other materials. Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Consumer Goods Cooperative (please read the precautions on the back before filling out this page) Phenolic resin has a large number of benzene ring groups, and the structure is relatively rigid (Rigid). Large gaps, when subjected to external forces, force is easily transmitted from the looser gaps, resulting in poor toughness of phenolic resin. Because the ether group on the polyalkylene oxide can form intermolecular hydrogen bonds with the OH functional group on the phenolic resin, the compatibility between the two is very good, and at the same time, the existence of this hydrogen bonding attractive force makes it soft. The thermoplastic resin of the chain is tightly worn. The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X 297 public money) 426697 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs " A7 B7 V. Description of the invention (6) Shuttle In the phenolic resin space, the free volume of the phenolic resin is reduced, and the compactness between the molecules is increased. When subjected to external force, the soft segment can not only lengthen the path length required for damage, but also increase the absorption of energy to achieve the effect of toughening. Since the polyalkylene oxide contains a large amount of ether groups, the modified phenolic resin of the polyalkylene oxide has an improved interface bonding condition when applied to coating, adhesion, and fiber-reinforced resin composite materials. In particular, when making fiber-reinforced resin composite materials, polyalkylene oxide can increase the impregnation and adhesion effect between modified phenolic resin and fibers. In addition, polyalkylene oxide also has a lubricant in the production of fiber-reinforced resin composite materials. Therefore, the modified phenolic resin of the present invention is particularly suitable for making fiber-reinforced resin composite materials. A suitable method for preparing the soluble phenolic resin to be used in the present invention comprises the step of condensing an excess of formaldehyde or the like with phenol in the presence of a basic catalyst. This preparation method is well known in the industry, for example, a detailed preparation method is contained in U.S. Patent No. 4,41,400, the content of which is the reference material of the present invention. The above acid catalysts are well known in the industry. For example, refer to the information of British Patent No. 1,363,277, and p-toluene sulfonic acid, phenol sulfonic acid, benzoic acid ( Benzic acid) and phosphoric acid are more preferred, and their content accounts for 2-10% by weight of the total soluble phenolic resin, and 5% by weight is most preferred. The acid catalyst can also be used with guanidine compound accelerators of the same weight, such as diphenylguanidine. The size of this paper applies to the Chinese National Standard (CNS) Α4 See the standard (210 × 297 mm) _ (Please read the precautions on the back before filling in this page) ί > Loading ·,-° 4266 9 A7 B7 V. Invention Explanation. (7) In a preferred embodiment of the present invention, polyalkylene oxide and phenol are thoroughly stirred and mixed in a lot to obtain a thick material (Glutinous Material). P-toluenesulfonic acid catalyst and diphenyl The guanidine is mutually miscible at 100 ° C in advance, and then the thick substance is added and stirred to obtain an aqueous solution with a viscosity of about 25CpS (100 ° C). The aqueous solution is preheated to 100 ° C. The soluble phenolic resin is thoroughly stirred and mixed to obtain the modified soluble phenolic resin of the present invention. The modified soluble phenolic resin has a viscosity of 800 to 2000 cps when the modified soluble phenolic resin is just prepared and cooled to 30 ° C. All the viscosities in the present invention are measured by Brookfield Viscometer according to ASTM D2 393 method. Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs, Consumer Work Cooperative (please read the note on the back ^^ ^ Please fill in this page again) Preparation of lacquer type phenolic tree for use in the present invention A suitable method includes performing a condensation reaction of phenol and formaldehyde or the like at a ratio of about 1: 0.8 mole ratio in the presence of an acidic catalyst for a period of time, adding a base to neutralize the reaction mixture, and The water layer and the resin layer are separated, and the moisture and small molecules in the obtained resin layer are removed by volatilization. In another preferred embodiment of the present invention, the condensation reaction is performed at 100 ° C for about 30 minutes. The lacquer type phenolic resin has a number average molecular weight of about 492 and a weight average molecular weight of about 20 32 *, and contains 0.15% by weight of free phenol and 90% by weight of solid content, of which 19% is ortho-ortho, 57% Hetero-p- and p-p-methyl bridged heterocyclic phenolic rings link the bridging structure. In another preferred embodiment of the present invention, the polyalkylene oxide and phenol are at 100 t; Stir and mix to obtain a thick material (Glutinous Material). This thick material is thoroughly stirred and mixed with the lacquer-type phenolic resin at 100 ° C, and then placed in an 80 ° C oven for about 30 minutes to obtain a The viscosity of this paper is lower than the Chinese national standard (C NS) Λ4 specification (210X 297 gong) 4266 9 Yin Ju A7 B7, Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, Invention Description (8) Water-like modified lacquer-type phenolic resin. This modified lacquer-type phenolic resin It has a viscosity of about 200-2000 cps when it is just prepared and cooled to 25 ° C. Since synthetic lacquer type phenolic resin uses more phenol than release, the lacquer type awakening resin does not contain reactive methanol groups ( methanol group,-ch2〇h) > phenolic resin, so hardener must be added during processing to form a network structure. Generally, the more commonly used hardener is hexamethylenetetramine. If its flame resistance is to be improved, then phosphorus-containing salts can be used to improve its flame resistance. The lacquer-type phenolic resins mainly supplied on the market are solid and are not suitable for fiber-reinforced resin composites by pultrusion. The solution-type lacquer-type phenolic resins with a high molecular weight have a solid content of about 86% by weight and a solvent content of about 14% by weight. Pollution of organic volatiles (VOC) is not suitable for pultrusion process. The liquid lacquer-type phenolic resin water synthesized by the present invention can be completely removed in a vacuum oven without adding any solvent that will cause pollution. The processability is good and the process is stable. Therefore, it can be applied to the pultrusion process . Phenols suitable for use in the present invention include, but are not limited to, phenol, o-cresol, m-cresol, p-cresol, xylenol, ethylphenol, p-phenylphenol, p-butylphenol, p-pentyl Phenol, bisphenol A and resorcinol. The modified modified lacquer-type phenolic resin toughened with polyalkylene oxide can further be added with mineral fillers such as calcium carbonate, silica and talc to improve its physical and mechanical properties. About 10-20% of the total resin weight. The water released by the modified soluble and lacquer phenolic resin of the present invention during cross-linking -10 · This paper size is applicable to the Chinese Standard (CNS) A4 specification (210X297 mm) -------- y ------ Order ------. R-_ (谙 Please read the notes on the back before filling in this page) Staff of the Central Standards Bureau of the Ministry of Economic Affairs, Cooperative Cooperatives, Printed Public 426697, A7 _B7__ V. Description of the Invention (9) The gas will be significantly reduced, especially the water vapor released from the varnish-type phenolic resin modified by polyalkylene oxide is very small, and the porosity is reduced accordingly. The modified phenolic resin has greatly increased its toughness and mechanical strength, and the composite material also has excellent fire and flame retardant properties. The above improvements can be obtained for each application. In the present invention, the advantages of the present invention are exemplified by examples of pultrusion composite materials. In the following examples, the temperature is expressed in degrees Celsius, and the component ratio is based on weight. Example 1: Polyoxyethylene modified soluble phenolic resin Polyethylene oxide and soluble phenolic resin blended formula is shown in Table 1: Table 1 Ingredient weight, grams of manufacturing plant (1) polycyclic ring Oxyethane, 8 Union Carbide Co, US 200,000 (2) Phenol 8 United Laboratories, Taiwan (3) p-toluenesulfonic acid 5 First Chemical, Taiwan (4) Diphenylguanidine 5 and Photochemical, Japan (5) may Soluble phenolic resin 100 long resin, Taiwan first 8 grams of polyethylene oxide and 8 grams of acid under the condition of nitrogen flow, the temperature is maintained at 100T: stirring with a blender for 1 hour 'to achieve full mutual solubility, Forming a very viscous viscous liquid 'will prepare a hardener (5
本紙张尺度適用中囷國家標準（CNS ) Λ4規格（210X297公楚） --------γ裝------訂------.r _(請先¾.讀背面之注意事項再填寫本頁) 42669 經濟部中央標準局貝工消费合作社印製 A7 B7 五、發明説明（1G ) 克對位甲苯磺酸和5克二苯胍於100°C真空烘箱內互溶半小 時）加入該黏稠液中使之充份溶解，約3分鐘可得黏度約爲 250cPs(100°C)之似水溶液，迅速倒入保持在100°C的可溶 型酚醛樹脂中均勻攪伴，而製得一用於拉擠成型製程的含 浸樹脂。 除了使用不同重量的聚環氧乙烷外，依上述步驟可製 備出含不同重量成份的聚環氧乙烷改質之可溶型酚醛樹 實施例2 :聚環氧乙烷改質之淸漆型酚醛樹脂 聚環氧乙烷和淸漆型酚醛樹脂混練之配方如表2所 示： 表2 成份 重量，克 製造廠 (1)聚環氧乙烷 8 Union Carbide Co,美國 & = 200,000 (2)酚 8 聯工所，台灣 (3)六伸甲基四胺 10 長春樹脂，台灣 (4)淸漆型酚酸樹脂 100 於本實施例自行合成 將1694克的酚（Phenol, 18mol)和121 7.5克的福馬林水 溶液（3 7wt%，15 mol的甲醛），置於5.0升的三頸反應瓶中， 並以稀釋的硫酸水溶液（4克濃硫酸溶於20ml的水中）爲催 化劑，反應約30分鐘後，以NaOH(aq)將酸中和掉，並將中 -12- 本紙張尺度適用中國國家標準（CMS ) A4規格（210X297公發） yiti衣 . -訂 贫 _ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消f合作社印製 426697 , A7 B7 五、發明説明（11 ) 和後的反應混合物的水層及樹脂層分離 > 再以旋轉揮發儀 將殘存於樹脂層中的水分及小分子去除，而自行合成黏度 約爲300cps(25°C)之液狀淸漆型酚醛樹脂。 該淸漆型酚醛樹脂經分析含有0.15重量％的自由酚 (free phenol)及90重量％的固體含量，其中丨9%爲鄰-鄰， 57%爲鄰-對和24%爲對-對位甲基架橋的雜排酚環連結架 橋結構，並經由GPC圖譜鑑定其具有一數平均分子量約492 及重量平均分子量約2032。 將8克的聚環氧乙烷與8克的酚在通氮氣的情形下，溫 度保持100°C下以攪拌機攪拌1小時，使之達到充份互溶， 形成黏度極高的黏稠液。將此黏稠液迅速倒入該自行合成 之淸漆型酚醛樹脂（100°C)中均勻攪伴，置入80°c烘箱中半 小時，此時可獲得一黏度較低的似水狀混合物，再加入六 伸甲基四胺當硬化劑後，而製得一用於拉擠成型製程的含 浸樹脂。 除了使用不同重量的聚環氧乙烷外，依上述步驟可製 備出含不同重量成份的聚環氧乙烷改質之淸漆型酚醛樹 實施例3 :拉擠成型操作及測試 拉擠成型操作： 將上述含浸樹脂置於含浸槽並維持在30°C下，以PPG Co.製造之764-NT-218玻璃纖維20束含浸通過，其纖維比 重爲2.54，單根纖維直徑1 3.1 μπι，抗拉強度2.2 X 1 05psi -13- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） y裝 訂.r '(請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消f合作社印製 4 266 9 7 4 A? ___________ΒΊ___ 五、發明説明（12 ) (1621.5MPa”通過一預成型孔以移除多餘之樹脂及空氣* 再導入一具有內模孔及尺寸爲82cm X 1.27cm X 0.3 3 cm兩片 對稱夾緊電熱式模具，並控制爲二段式加熱，其中第一段 及第二段加熱區之長度分別爲30公分，第一段加熱溫度爲 220°C，而第二段加熱溫度爲240°C。拉擠速度爲30cm/min。 以改質之可溶及淸漆型酚醛樹脂所製成的拉擠成型產品的 纖維含量分別爲60及70體積％。 拉擠成型品之後硬化處理： 由於在拉擠成型的過程中，樹脂停留在模具內時間有 限，因此在模具內進行聚合反應的時間較短，造成反應不 夠完全。所以輔以後硬化處理來使聚合反應較完全並去除 反應產生的揮發物<本實施例所採用的後硬化條件爲在真 空烘箱中1 80°C烘1小時。後硬化處理後之試片亦作相同之 機械性質測試，以便和未經後硬化處理者做比較。 拉擠成型品之性質測試： 以萬能材料試驗機（Universal Testing Machine)及衝擊 強度試驗機（Impact Strength Tester)測其機械性質。 (a) 抗拉強度：抗拉測試遵循ASTM D-3039測試規範來 進行，試片的尺寸爲25.6 X 1.2 1 X 0.29cm，其拉伸速度 爲 2.5 mm/min 〇 (b) 抗折強度：抗折強度測試遵循ASTM D-790測試規範 進行，試片的尺寸爲12.6 X 1.21 X 0.29cm，其測試速度 14- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) y裝 I ^ 皮 {請先閱讀背面之注意事項再填寫本頁) 426697 Λ 42^β97. Α7 Β7 五、發明説明（13 ) 爲 2.8 mm/min、跨距爲 9.3 cm。 (c) 耐衝擊強度：衝擊強度測試遵循ASTM D-256測試規 範來進行，其試片的尺寸爲6.3 X 1,21 X0.29cm，並以10 磅的擺錘來測試。 防火難燃測試： (d) 根據ASTM D-28 63之規範，燃燒至少3 min或50 mm， 調整氧氣、氮氣混合系統中的比例，測試火焰在拉擠 成型之纖維強化淸漆與可溶型酚醛樹脂複合材料試片 上持續燃燒所需的最低氧氣，以極限氧氣指數（Limit Oxygen Index)表示。 (e) 根據UL-94耐燃性測試規範中的垂直燃燒法，分別測 試拉擠成型之纖維強化淸漆與可溶型酚醛樹脂複合材 料試片，以測其耐燃程度爲94V-0、94V-1或94V-2。 纖維強化淸漆與可溶型酚醛樹脂複合材料之機械性質 與防火難燃性質分別如表3、表4所示： 11 n fl ^ I n ^ {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费合作社印製 -15- 本紙張尺度適用肀國國家標準（CNS ) A4规格（2丨0 X297公釐） 426697 A7 B7 五、發明説明（14 ) 表3 聚環氧 乙烷 重量％ 淸漆型酚醛樹脂3 可溶型酚醛樹脂b 抗折 (G 模數 Pa) 增加百分比 (%) 抗折 (G 模數 Pa) 增加百分比 (%) U P U P U P U P 0 31.00 33.10 29.50 30.57 2 32.02 34.50 3.29 4.23 30.17 32.14 2.27 5.14 4 33.00 36.77 6.45 11.1 60.57 32.81 3.63 7.33 6 33.51 37.46 8.10 13.2 31.11 33.61 5.46 9.94 8 32.16 34.56 3.61 4.41 30.92 33.00 4.81 7.95 衝擊強度 (KJ/m) 增加百分比 (%) 衝擊強度 (KJ/m) 增加百分比 (%) U P U P U P U P 0 1.382 1.606 1.338 1.554 2 1.578 1.761 14.2 9.71 1.500 1.694 12.1 8.96 4 1.618 1.986 17.1 23.7 1.551 1.886 15.9 21.3 6 1.828 2.179 32.3 35.7 1.737 2.041 29.8 31.3 8 1.698 2.025 22.9 26.1 1.627 1.912 21.6 23.0 t請先閱讀背面之注項再填寫本肓) 經濟部中央標準局—工消费合作社印策 a:玻離纖維含量70重量％ b:玻離纖維含量60重量％ U:未後硬化處理 P:後硬化處理（180°C，lhr) 16 - 本紙iML度適用中囡國家標準（CNS ) Α4規格（210Χ297公处） UL-94 L.O.I 94V-0 >55 94V-0 >55 A26697 , A7 B7 五、發明説明（15 ) 表4 聚環氧乙院改質可溶型酚醛樹脂複合材料 聚環氧乙烷改質淸漆型酚醛樹脂複合材 抗折模數與耐衝擊強度隨著聚環氧乙烷樹脂的含量增 加而大幅提高，當聚環氧乙烷含量爲6重量％時有最高値。 玻纖強化可溶型與淸漆型酚醛樹脂摻混複合材料之機械性 質經後硬化處理後均大幅提昇，由抗折模數與耐衝擊強度 的變化可知’加入少量的聚環氧乙烷即可達到增韌酚醛樹 脂的目的。 由UL-94和L.〇丄之測試結果可知玻纖強化酚醛樹脂 拉擠成型複合材料確實是一種相當耐火、發煙量低、使用 安全性高的防火材料。 }裝 訂.fer (請先閲t背面之注意事項再填寫本頁) 經濟部中央棕準局貝工消费合作社印掣 本紙張尺度適;种晒轉準（CNS ) A4· ( 2|GX297公们This paper size is applicable to the China National Standard (CNS) Λ4 specification (210X297). -------- γ Pack -------- Order ------. R _ (Please read ¾. Note on the back, please fill in this page again) 42669 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed A7 B7 V. Description of the invention (1G) Gram p-toluenesulfonic acid and 5 g diphenylguanidine are mutually soluble in a 100 ° C vacuum oven (Half an hour) add this viscous solution to dissolve it fully. An aqueous solution with a viscosity of about 250 cPs (100 ° C) can be obtained in about 3 minutes. Pour into the soluble phenolic resin kept at 100 ° C and stir evenly. , And an impregnated resin is prepared for the pultrusion process. In addition to using different weights of polyethylene oxide, a soluble phenolic tree modified with polyethylene oxide can be prepared according to the above steps. Example 2: Polyethylene oxide modified varnish The mixing formula of the phenolic resin polyethylene oxide and the lacquer-type phenolic resin is shown in Table 2: Table 2 Ingredient weight, gram manufacturer (1) polyethylene oxide 8 Union Carbide Co, United States & 200,000 ( 2) Phenol 8 United Laboratories, Taiwan (3) Hexamethyltetraamine 10 Changchun resin, Taiwan (4) Lacquer-type phenolic resin 100 In this example, 1694 grams of phenol (Phenol, 18mol) and 121 7.5 g of a formalin aqueous solution (37 wt%, 15 mol of formaldehyde) was placed in a 5.0-liter three-necked reaction flask, and a diluted sulfuric acid aqueous solution (4 g of concentrated sulfuric acid dissolved in 20 ml of water) was used as a catalyst to react After about 30 minutes, neutralize the acid with NaOH (aq) and neutralize the -12- This paper size applies the Chinese National Standard (CMS) A4 specifications (210X297 public) yiti clothing.-Order poor_ (Please read first Note on the back, please fill out this page) 7, A7 B7 V. Description of the invention (11) The water layer and resin layer of the reaction mixture after the separation are removed by using a rotary volatilizer to remove the water and small molecules remaining in the resin layer, and the self-synthesized viscosity is about 300cps. (25 ° C) liquid lacquer type phenolic resin. The lacquer-type phenolic resin was analyzed to contain 0.15% by weight of free phenol and 90% by weight of solid content, of which 9% were ortho-ortho, 57% were ortho-para and 24% were para-para The methyl-bridged heterophenolic ring was linked to the bridge structure and was identified by GPC spectroscopy to have a number average molecular weight of about 492 and a weight average molecular weight of about 2032. 8 grams of polyethylene oxide and 8 grams of phenol were stirred at a temperature of 100 ° C with a stirrer for 1 hour while maintaining nitrogen at a temperature of 100 ° C, so that they were fully miscible to form a highly viscous viscous liquid. Quickly pour this viscous solution into the self-synthesized lacquer-type phenolic resin (100 ° C) and stir evenly, and place it in an 80 ° c oven for half an hour. After adding hexamethylenetetramine as a hardener, an impregnated resin is prepared for the pultrusion process. In addition to using different weights of polyethylene oxide, a modified lacquer-type phenolic tree containing polyethylene oxide with different weight components can be prepared according to the above steps. Example 3: Pultrusion operation and test pultrusion operation : The above impregnating resin was placed in an impregnation tank and maintained at 30 ° C, and was impregnated with 20 bundles of 764-NT-218 glass fiber manufactured by PPG Co., and the fiber specific gravity was 2.54, and the single fiber diameter was 1 3.1 μπι. Tensile strength 2.2 X 1 05psi -13- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) y binding. R '(Please read the precautions on the back before filling this page) Staff of the Central Bureau of Standards, Ministry of Economic Affairs Printed by the Consumer Cooperative 4 266 9 7 4 A? ___________ ΒΊ ___ V. Description of the Invention (12) (1621.5MPa "through a pre-formed hole to remove excess resin and air * Re-introduce an inner mold hole with a size of 82cm X 1.27cm X 0.3 3 cm two symmetrically clamped electric heating molds and controlled for two-stage heating. The length of the first and second heating zones is 30 cm and the first heating temperature is 220 ° C. The second stage heating temperature is 240 ° C. The extrusion speed is 30cm / min. The fiber content of pultrusion products made of modified soluble and lacquer-type phenolic resins is 60 and 70% by volume, respectively. Hardening treatment after pultrusion products: During the molding process, the resin stays in the mold for a limited time, so the polymerization reaction time in the mold is short, resulting in incomplete reaction. Therefore, the subsequent hardening treatment is used to complete the polymerization reaction and remove the volatiles produced by the reaction. ≪ The post-hardening conditions used in this example are 1 hour at 180 ° C in a vacuum oven. The test piece after the post-hardening treatment is also tested for the same mechanical properties for comparison with those without post-hardening treatment. Testing of the properties of the molded products: The mechanical properties are measured by the Universal Testing Machine and the Impact Strength Tester. (A) Tensile strength: The tensile test is performed in accordance with ASTM D-3039 test specifications. The size of the test piece is 25.6 X 1.2 1 X 0.29cm, and the tensile speed is 2.5 mm / min. 〇 (b) Flexural strength: The flexural strength test follows the ASTM D-790 test specification. Yes, the size of the test piece is 12.6 X 1.21 X 0.29cm, and its test speed is 14- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) y pack I ^ Leather {Please read the precautions on the back first (Fill in this page) 426697 Λ 42 ^ β97. Α7 Β7 5. Description of the invention (13) is 2.8 mm / min, and the span is 9.3 cm. (c) Impact resistance: The impact strength test was performed in accordance with the ASTM D-256 test specification. The size of the test piece was 6.3 X 1,21 X 0.29 cm, and it was tested with a 10-pound pendulum. Fire and flame resistance test: (d) According to ASTM D-28 63, burn for at least 3 min or 50 mm, adjust the proportion in the oxygen and nitrogen mixed system, and test the flame-resistant fiber-reinforced paint and soluble type in pultrusion. The minimum oxygen required for continuous combustion on a phenolic resin composite test piece is expressed by the Limit Oxygen Index. (e) According to the vertical combustion method in the UL-94 flame resistance test specification, test the pultruded fiber-reinforced lacquer and the soluble phenolic resin composite material test specimens to measure the flame resistance of 94V-0, 94V- 1 or 94V-2. The mechanical properties and fire and flame resistance of fiber-reinforced concrete and soluble phenolic resin composite materials are shown in Tables 3 and 4, respectively: 11 n fl ^ I n ^ {Please read the precautions on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives -15- This paper size applies to the national standard (CNS) A4 (2 丨 0 X297 mm) 426697 A7 B7 V. Description of the invention (14) Table 3 Polyepoxy Ethane weight% lacquer-type phenolic resin 3 Soluble phenolic resin b Anti-fold (G modulus Pa) Percent increase (%) Anti-fold (G modulus Pa) Percent increase (%) UPUPUPUP 0 31.00 33.10 29.50 30.57 2 32.02 34.50 3.29 4.23 30.17 32.14 2.27 5.14 4 33.00 36.77 6.45 11.1 60.57 32.81 3.63 7.33 6 33.51 37.46 8.10 13.2 31.11 33.61 5.46 9.94 8 32.16 34.56 3.61 4.41 30.92 33.00 4.81 7.95 Impact strength (KJ / m) Increase percentage (KJ / m) Impact (KJ) Impact percentage (%) Impact (KJ) / m) Percent increase (%) UPUPUPUP 0 1.382 1.606 1.338 1.554 2 1.578 1.761 14.2 9.71 1.500 1.694 12.1 8.96 4 1.618 1.986 17.1 23.7 1.551 1.886 15.9 21.3 6 1.828 2.1 79 32.3 35.7 1.737 2.041 29.8 31.3 8 1.698 2.025 22.9 26.1 1.627 1.912 21.6 23.0 tPlease read the notes on the back before filling in this note)) Central Bureau of Standards of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives India Printing a: 70% by weight of glass fiber content b : Glass fiber content 60% by weight U: Unpost-cured P: Post-cured (180 ° C, lhr) 16-The iML of this paper is in accordance with the National Standard (CNS) A4 (210 × 297) UL-94 LOI 94V-0 > 55 94V-0 > 55 A26697, A7 B7 V. Description of the invention (15) Table 4 Polyethylene oxide modified soluble phenolic resin composite material Polyethylene oxide modified lacquer type phenolic The flexural modulus and impact strength of the resin composite material increase greatly with the increase of the content of polyethylene oxide resin. When the content of polyethylene oxide is 6% by weight, it has the highest 値. The mechanical properties of glass fiber reinforced soluble and lacquer-type phenolic resin blended composite materials are greatly improved after post-hardening treatment. From the changes in the flexural modulus and impact strength, it can be known that 'a small amount of polyethylene oxide is added. Can achieve the purpose of toughening phenolic resin. From the test results of UL-94 and L.〇 丄, we can know that glass fiber reinforced phenolic resin pultrusion composite material is indeed a fire-resistant material that is quite fire-resistant, has low smoke generation, and is highly safe to use. } Binding.fer (please read the notes on the back of t before filling out this page) Printed by the Central Brown Standard Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives This paper is of the right size; the type is transferred to the standard (CNS) A4 · (2 | GX297