201211097 六、發明說明： 【發明所屬之技術領域】 本發明關於可給予難燃性優異，同時耐濕性、耐熱性 、與金屬基材的黏著性等亦優異之硬化物的環氧樹脂，其 中間體，硬化劑及使用彼等的環氧樹脂組成物以及其硬化 物。 【先前技術】 近年來，尤其隨著尖端材料領域的進歩，要求更高性 能的基礎樹脂之開發。例如，於半導體密封的領域中，由 於對應於近年來高密度安裝化的封裝之薄形化、大面積化 ，更且表面安裝方式之普及，封裝龜裂的問題係嚴重化， 作爲此等的基礎樹脂，強烈要求耐濕性、耐熱性、與金屬 基材的黏著性等之提高。再者，最近從環境負荷低減的觀 點來看，有排除鹵素系難燃劑的傾向，要求難燃性更優異 的基礎樹脂。 然而，於以往已知的環氧樹脂中，尙未知道能滿足‘此 等要求者。例如，周知的雙酚型環氧樹脂係在常溫爲液狀 ，由於操作性優異，或與硬化劑、添加劑等的混合係容易 ，而被廣泛使用，但在耐熱性、耐濕性之點有問題。又， 作爲改良耐熱性者，已知苯酚酚醛清漆型環氧樹脂，但在 耐濕性或耐衝撃性有問題，還有專利文獻1中以耐濕性、 耐衝撃性的提高爲目的，提出苯酚芳烷基樹脂的環氧化合 物，但在耐熱性或難燃性之點係不充分。 -5- 201211097 再者，專利文獻2中提出具有萘酚經對苯二甲基所連 結的構造之萘酚芳烷基型環氧樹脂，但依然在耐熱性、難 燃性之點係不充分。又，專利文獻3中提出具有萘酚經伸 萘基所連結的構造之萘酚芳烷基型環氧樹脂，但由於芳香 族構造皆爲萘環，而有黏度、軟化點變高，使操作性及成 形性降低之問題。 [先行技術文獻] [專利文獻] [專利文獻1]特開昭63 -23 8 1 22號公報 [專利文獻2]特開平3 -90075號公報 [專利文獻3]特開2004-59792號公報 【發明內容】 [發明所欲解決的問題] 因此，本發明之目的在於提供成形性優異，同時具有 耐濕性、耐熱性、難燃性等亦優異的性能，適合於層合、 成形、澆鑄、黏著等用途之環氧樹脂，及適用作爲環氧樹 脂硬化劑的多價羥基樹脂，更且彼等之製造方法，以及使 用彼等之環氧樹脂組成物，還有其硬化物。 [解決問題的手段] 即，本發明係以下述通式（1 )所表示， (1)201211097 【化1】201211097 VI. [Technical Field] The present invention relates to an epoxy resin which can provide a cured product which is excellent in flame retardancy and which is excellent in moisture resistance, heat resistance, adhesion to a metal substrate, and the like. Interstitials, hardeners and epoxy resin compositions using them and hardened materials thereof. [Prior Art] In recent years, in particular, with the advancement of cutting-edge materials, development of a higher-performance base resin has been demanded. For example, in the field of semiconductor sealing, the problem of package cracking is severed due to the thinning and large area of the package which has been installed in recent years, and the popularity of the surface mounting method. The base resin is strongly required to have improved moisture resistance, heat resistance, adhesion to a metal substrate, and the like. In addition, from the viewpoint of a reduction in environmental load, there has been a tendency to eliminate a halogen-based flame retardant, and a base resin having more excellent flame retardancy is required. However, among the epoxy resins known in the past, 尙 is not known to satisfy the ‘there are requirements. For example, a well-known bisphenol-type epoxy resin is liquid at room temperature, and is excellent in workability or easy to be mixed with a curing agent or an additive, and is widely used, but has heat resistance and moisture resistance. problem. In addition, as a phenol novolac type epoxy resin, a phenol novolak type epoxy resin is known, and there is a problem in moisture resistance and impact resistance, and Patent Document 1 proposes an improvement in moisture resistance and impact resistance. An epoxy compound of a phenol aralkyl resin, but insufficient in heat resistance or flame retardancy. -5- 201211097 Further, Patent Document 2 proposes a naphthol aralkyl type epoxy resin having a structure in which naphthol is bonded to p-xylylene, but the heat resistance and flame retardancy are insufficient. . Further, Patent Document 3 proposes a naphthol aralkyl type epoxy resin having a structure in which a naphthol is bonded to a naphthyl group, but since the aromatic structure is a naphthalene ring, the viscosity and the softening point become high, and the operation is performed. The problem of reduced sex and formability. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. 2004-59792. DISCLOSURE OF THE INVENTION [Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide excellent properties such as moisture resistance, heat resistance, flame retardancy, and the like, and is suitable for lamination, molding, casting, and the like. An epoxy resin for adhesion and the like, a polyvalent hydroxy resin suitable for use as an epoxy resin hardener, and a method for producing the same, and an epoxy resin composition using the same, and a cured product thereof. [Means for Solving the Problem] That is, the present invention is represented by the following general formula (1), (1) 201211097 [Chemical 1]
Η 人十人 (惟’Α表示萘環（Ν)或苯環（Β) ，η表示1〜15之數 )’以Ν/(Ν + Β)所計算的莫耳比爲0.2〜0.7，同時軟化 點爲75〜125°C，在150°C的熔融黏度爲2〜1〇Pa · s。 又’本發明係一種多價經基樹脂之製造方法，其特徵 爲相對於苯酚類與萘酚類的合計量i莫耳，使用0_10〜 〇·4〇莫耳的萘酚類，使〇.〇5〜0.35莫耳的下述通式（2) 所示的萘系縮合劑反應， 【化2】 X"CH2 (2) (惟’ X表示羥基、鹵素原子或碳數1〜6的院氧基）。 再者’本發明係—種環氧樹脂，其爲以下述通式（3 )所表示， 【化3】Η Ten people (only 'Α means naphthalene ring (Ν) or benzene ring (Β), η means the number of 1~15) 'The molar ratio calculated by Ν / (Ν + Β) is 0.2~0.7, The softening point is 75 to 125 ° C, and the melt viscosity at 150 ° C is 2 to 1 〇 Pa · s. Further, the present invention relates to a method for producing a multivalent warp-based resin, which is characterized in that a naphthol of 0_10~〇·4〇mol is used for the total amount of phenol and naphthol. 〇5~0.35 mol of a naphthalene-based condensing agent represented by the following formula (2), [Chemical 2] X"CH2 (2) (only 'X' represents a hydroxyl group, a halogen atom or a carbon number of 1 to 6 Oxy). Further, the present invention relates to an epoxy resin which is represented by the following general formula (3), [Chemical 3]
(3) (惟’A表示萘環（N)或苯環（β) ，〇表示環氧丙基’ π表示1〜15之數），n/(N + B)爲0.2〜0.7，同時軟化 點爲60〜100<>C，在150°C的熔融黏度爲0.2〜l.OPa . s。 201211097 再者，本發明係一種上述通式（3)所示的環氧樹脂 之製造方法，其特徵爲令上述通式（1)所示的多價羥基 樹脂與環氧氯丙烷反應。 還有，本發明係一種將上述環氧樹脂或多價羥基樹脂 中的至少任一者當作環氧樹脂成分或硬化劑成分的必要成 分摻合所成之環氧樹脂組成物，而且係一種將此環氧樹脂 組成物硬化所成之硬化物。 [發明的效果] 將由本發明的環氧樹脂或多價羥基樹脂所得之環氧樹 脂組成物硬化而得之硬化物，係耐濕性、耐熱性優異，而 且具有耐衝撃性等的機械特性優異之性能，可適用於層合 、成形’澆鑄、黏著等用途。 【實施方式】 [實施發明的形態] 以下詳細說明本發明。 本發明的多價羥基樹脂係以上述通式（i )所表示。 此處’ A表示萘環或苯環，具有萘環（n)與苯環（b) 共存的構造’萘環（N )佔A的比例（莫耳比）以N/ ( N + B)表示爲〇·2〜0.7的範圍。若小於此，則以萘構造爲 基礎的耐熱性 '耐濕性等之提高效果係小，若多於此，則 軟化點、黏度變高，成形性降低。此處，上述莫耳比係多 價經基樹脂中的萘環與苯環之平均莫耳比。 -8- 201211097 上述萘環及苯環亦可被碳數1〜6的烷基所取代， 較佳爲無取代或經甲基取代者。η表示平均的重複數（ 量平均），爲1〜15，較佳爲1·1〜5。η若小於此，則 耐熱性之點係不宜。又，若大於此，則軟化點、黏度變 ，成形性降低。本發明的多價羥基樹脂之軟化點爲75 125 °C的範圍，較佳爲 80〜120 °C的範圍。又，150 °C的 融黏度爲2〜10Pa· s的範圍，較佳爲3〜8Pa· s的範 〇 如此的多價羥基樹脂係可藉由使苯酚類及萘酚類與 式（2)所示的縮合劑反應而獲得。 此處所謂的苯酚類，就是碳數1〜6的烷基取代或 取代的苯酚，具體地可例示苯酚、鄰甲酚、間甲酚、對 酚、乙基苯酚類、異丙基苯酚類、第三丁基苯酚類、鄰 基苯酚、對苯基苯酚、2，6-二甲苯酚、2,6-二乙基苯酚 ，從所得之樹脂的低黏度性及高反應性等觀點來看，較 爲無取代的苯酚。又’所謂的萘酚類，就是碳數1〜6 烷基取代或未取代的萘酚’較佳爲無取代的萘酚’具體 爲1-萘酚、2-萘酚。上述苯酚類或萘酚類係可單獨使用 也可倂用2種以上。 反應時的苯酚類與萘酚類之使用比例，係相對於兩 的合計量1莫耳而言’可使用理論量的0·2〜0.7莫耳 萘酚類，但若考慮反應性的相異等，可使用0.10〜〇· 莫耳之萘酚類° 又，於通式（2)的萘系縮合劑中，X係羥基、鹵 但 數 在 高 熔 圍 通 未 甲 苯 等 佳 的 地 者 之 40 素 201211097 原子或碳數1〜6的烷氧基。從與苯酚性化合物的反應性 之觀點來看’較佳爲羥基或鹵素原子。鹵素原子宜爲氯原 子，烷氧基較佳爲甲氧基。對萘環的2個CHzX基之取代 位置可爲同一苯環上’也可爲各自的苯環上，較佳的取代 位置爲1，4 -位、1，5 -位、1，6 ·位、2，6 -位、2，7 -位。從耐熱 性、機械強度及韌性等物性的觀點來看，較佳爲1，4 -位及 1,5 -位。萘系縮合劑係可爲此等的混合物，萘系縮合劑中 的1，4 -二取代物與1，5 -二取代物之合計含有率較佳爲9〇 重量％以上。 通式（2 )所示的萘系縮合劑係沒有特別的限定，通 常可經由萘的氯甲基化反應或二甲基萘類的甲基之氯化反 應來製造。於縮合劑中，亦可含有在萘環上僅1個CH2X 基取代的單取代萘類，單體的含量爲10wt%以下，較佳爲 5wt%以下’更佳爲3wt%以下。若單體的含量多於此，則 使樹脂硬化時的交聯密度會降低，導致耐熱性的降低。 於苯酚性化合物與萘系縮合劑的反應中，對於萘系縮 合劑’使用過剩量的苯酚類及萘酚類。相對於苯酚類與萘 酚類的合計量1莫耳而言，萘系縮合劑的使用量爲0.05〜 〇_35莫耳的範圍，較佳爲0.1〜〇.3莫耳的範圍。若多於 此則樹脂的軟化點變高，對成形作業性造成障礙。又，若 少於此，則反應結束後，過剩地使用之苯酚類及萘酚類之 去除量變多’工業上不宜》萘系縮合劑由於使用比理論量 少的量’故實質上全量的萘系結合劑係在反應的時間點完 成反應。 -10- 201211097 此反應係可在酸觸媒的存在下進行，作爲此酸觸媒， 可由周知的無機酸'有機酸中適宜選擇。作爲如此的酸觸 媒，例如可舉出鹽酸、硫酸、磷酸等的礦酸，或甲酸、草 酸、三氟乙酸、對甲苯磺酸、二乙基硫酸等的有機酸，或 氯化鋅、氯化鋁、氯化鐵、三氟化硼等的路易士酸，或活 性白土、矽石-氧化鋁、沸石等的固體酸等。又，作爲通 式（2)所示的結合劑，使用雙氯甲基萘時，可在無觸媒 下使反應。 通常，此反應係在10〜250 °c進行1〜20小時。再者 ，作爲反應溶劑，可使用甲醇、乙醇、丙醇、丁醇、乙二 醇、甲基溶纖劑、乙基溶纖劑等的醇類，或苯、甲苯、氯 苯、二氯苯等。 反應結束後，視情況而定，可藉由中和、水洗等的方 法，去除觸媒，視需要藉由減壓餾去等的方法，將殘存的 溶劑及未反應苯酚性化合物去除到系外，而成爲多價羥基 樹脂。未反應苯酚性化合物通常爲3%以下，較佳爲1 %以 下。若多於此，則作爲硬化物時的耐熱性降低。惟，使用 2價以上的苯酚性化合物於反應時，亦可在反應後去除殘 存的苯酚性化合物。 本發明中，亦可含有在上述通式（1)所示的多價羥 基樹脂鍵結有萘基甲烷基者。例如，於與苯酚性化合物反 應的萘系縮合劑中，當含有單氯甲基萘、單羥基萘或單烷 氧基甲基萘時，成爲通式（1)的多價羥基樹脂與在通式 (1)的多價羥基樹脂之芳香族環附加有1個或其以上的 -11 - 201211097 萘基甲烷基之化合物的混合物。此等即使爲混合物，也可 沒有障礙地發揮本發明的效果，可使用此等當作環氧樹脂 硬化劑，而且可使用作爲本發明的環氧樹脂之原料。 本發明的環氧樹脂係以上述通式（3)所表示。此處 ，A及η係與通式（1)的多價羥基樹脂之說明相同。本 發明的環氧樹脂之軟化點爲60〜100°C的範圍，更佳爲75 〜95°C的範圍。又，在150°C的熔融黏度爲0.1〜l.OPa· s 的範圍，更佳爲0.2〜0.8Pa · s的範圍。 本發明的環氧樹脂係可藉由令上述通式（1)所示的 多價羥基樹脂與環氧氯丙烷反應而獲得。此反應係可與通 常的環氧化反應同樣地進行》 例如，於將上述通式（1)所示的多價羥基樹脂溶解 於過剩的環氧氯丙烷中後，在氫氧化鈉、氫氧化鉀等的鹼 金屬氫氧化物之存在下，於50〜150 °C，較佳60〜120 °C 的範圍，使反應1〜10小時之方法。此時，鹼金屬氫氧化 物的使用量，係相對於多價羥基樹脂中的羥基1莫耳之 0.8〜2莫耳，較佳爲0.9〜1.2莫耳的範圍。又，環氧氯 丙烷係對於多價羥基樹脂中的羥基過剩地使用，通常相對 於多價羥基樹脂中的羥基1莫耳之1.5〜15莫耳，較佳爲 2〜8莫耳的範圍。又，反應時，亦可添加四級銨鹽等。 作爲四級銨鹽，例如有氯化四甲錢、氯化四丁銨、氯化苄 基三乙銨等，其添加量較佳爲相對於多價羥基樹脂之0.1 〜2.0wt%的範圍。若少於此，則四級銨鹽的添加效果小， 若多於此，則難水解性氯的生成變多，高純度化變困難。 -12- 201211097 再者，亦可使用二甲亞碾、二甘醇二甲醚等的極性溶劑， 其添加量相對於多價羥基樹脂而言，較佳爲10〜20 0 wt% 的範圍。若少於此，則添加的效果小，若多於此，則容積 效率降低，經濟上不宜。反應結束後，可藉由餾去過剩的 環氧氯丙烷，將殘留物溶解於甲苯、甲基異丁基酮等的溶 劑中，過濾後，水洗以去除無機鹽，接著餾去溶劑，而得 到目的之環氧樹脂。此環氧樹脂係以通式（3)所示者爲 主成分，但亦可含有在通式（1)的多價羥基樹脂之芳香 族環附加有1個或其以上的萘基甲烷基之化合物的環氧丙 基醚化物。再者，亦可含有本發明的環氧樹脂中之環氧基 爲醚鍵的寡聚物化者。 本發明的環氧樹脂組成物係由環氧樹脂及硬化劑所構 成，摻合有作爲環氧樹脂成分的通式（3)所示之環氧樹 脂或作爲硬化劑成分的上述通式（1 )所示之多價羥基樹 脂的至少任一方當作必要成分者。特別地，摻合有作爲環 氧樹脂成分的通式（3)所示之環氧樹脂，摻合有作爲硬 化劑成分的通式（1)所示之多價羥基樹脂者，係具備高 度的難燃性、物性平衡而較佳。 作爲以通式（3)所示的環氧樹脂爲必要成分時的硬 化劑’ 一般可使用已知作爲環氧樹脂的硬化劑之全部者。 例如，有氰胍、多價苯酚類 '酸酐類、芳香族及脂肪族胺 類等。若具體地例示’作爲多價苯酚類，例如有雙酚A、 雙酚F、雙酚S、蒔雙酚、4,4’-聯苯酚、2,2，-聯苯酚、氫 醌、間苯二酚、萘二酚等的2價苯酚類，或三（4 -羥基苯 -13- 201211097 基）甲烷、1，1，2,2-四（4-羥基苯基）乙烷、苯酚酚 漆、鄰甲酚酚醛清漆、萘酚酚醛清漆、聚乙烯基苯酚 代表的3價以上之苯酚類，更且苯酚類、萘酚類，或 A、雙酚F、雙酚S、弗雙酚、4,4’-聯苯酚、2,2’-聯 、氫醌、間苯二酚、萘二酚等的2價之苯酚類經由甲 乙醛、苯甲醛、對羥基苯甲醛、對苯二甲基二醇等的 劑所合成的多價苯酚性化合物等，作爲酸酐，·有苯二 酐、四氫苯二甲酸酐、甲基四氫苯二甲酸酐、六氫苯 酸酐、甲基六氫苯二甲酸酐、甲基海明克（himic ) 、納狄克（nadic )酸酐、偏苯三酸酐等。又，作爲 ，有4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基丙 4，4’-二胺基二苯基颯、間苯二胺、對苯二甲基二胺等 香族胺類、乙二胺、己二胺、二伸乙三胺、三伸乙四 的脂肪族胺類，或通式（1)所示的多價羥基樹脂。 發明的樹脂組成物中，可混合此等硬化劑的1種或2 上而使用，但本發明的環氧樹脂之摻合量係環氧樹脂 中的5〜100 %之範圍。 作爲以通式（1 )所示的多價羥基樹脂爲硬化劑 的必要成分時之環氧樹脂，分子中具有2個以上的環 之一般環氧樹脂係皆可使用。舉例而言，有雙酚A、 S、荛雙酚、4,4’-聯苯酚、2，2’-聯苯酚、氫醌、間苯 等的2價苯酚類，或三（4-羥基苯基）甲烷、1,1，2, (4-羥基苯基）乙烷、苯酚酚醛清漆、鄰甲酚酚醛清 的3價以上之苯酚類，或由四溴雙酚A等的鹵素化 醛清 等爲 雙酚 苯酚 醛、 縮合 甲酸 二甲 酸酐 胺類 院、 的芳 胺等 於本 種以 全體 成分 氧基 雙酚 二酚 2-四 漆等 雙酚 -14- 201211097 類所衍生的環氧丙基醚化物，或上述通式（1)所示的多 官能環氧樹脂等。此等環氧樹脂係可混合1種或2種 而使用’但本發明的多價經基樹脂之慘合量係環氧樹脂全· 體中的5〜100%之範圍。 又’於以通式（3)所示的環氧樹脂或通式（〇所示 的多價經基樹脂或兩者爲必要成分的本發明之環氧樹脂糸且 成物中，可適宜摻合聚酯、聚醯胺、聚醯亞胺、聚酸、聚 胺甲酸酯、石油樹脂、茚-香豆酮樹脂、苯氧基樹脂等的 寡聚物或高分子化合物，也可摻合無機塡充劑、顔料、難 然劑、搖變性賦予劑、偶合劑、流動性改良劑等的添加劑 。作爲無機塡充劑，例如可舉出球狀或粉碎狀的熔融矽石 、結晶砂石等的砂石粉末、氧化銘粉末、玻璃粉末、或雲 母、滑石、碳酸鈣、氧化鋁、水合氧化鋁等，作爲顏料， 有有機系或無機系的體質顏料、鱗片狀顏料等。作爲搖變 性賦予劑，可舉出矽系、蓖麻油系、脂肪族醯胺蠟、氧化 聚乙烯躐、有機膨土系等》更視需要，可使用習知的硬化 促進劑。舉例而言，有胺類、咪唑類、有機滕類、路易士 酸等。添加量通常係相對於環氧樹脂100重量份之0.2〜5 重量份的範圍。再者視需要，於本發明的樹脂組成物中， 可使用巴西棕櫚蠟、OP蠟等的脫模劑、γ-環氧丙氧基丙 基三甲氧基矽烷等的偶合劑、碳黑等的著色劑、三氧化銻 等的難燃劑、矽油等的低應力化劑、硬脂酸鈣等的滑劑等 〇 本發明的硬化物係可藉由澆鑄、壓縮成形、轉移成形 -15- 201211097 等的方法，將上述環氧樹脂組成物成形加工而得。生成之 際的溫度通常爲120〜220°C的範圍。 [實施例] 以下以實施例及比較例爲基礎，具體地說明本發明。 實施例1 (多價羥基樹脂之製造） 於1L的四口可分離式燒瓶中，量取96g 1-萘酚、 251g苯酚、150g二氯甲基萘（1，4-二氯甲基體43.5%、 1，5-二氯甲基體55.3%、其它二氯甲基體1.2%)及450g 氯苯，在氮氣流下，邊攪拌邊徐徐升溫溶解，於約80°C照 那樣地反應2小時。然後，邊餾去氯苯邊升溫到180°C爲 止，照那樣地反應1小時。反應後，藉由減壓餾去而去除 溶劑與未反應單體後，得到褐色的樹脂23 5g (多價羥基 樹脂A)。所得之多價羥基樹脂的羥基當量爲230g/eq.， 軟化點爲123°C，在150°C的熔融黏度爲9.5Pa.s»根據 所回收的未反應單體之分析，倂入樹脂中的1-萘酚（N) 與苯酚（B)之比率（莫耳比）爲N/( N + B ) =0.57。圖1 中顯示GPC圖。此處，熔融黏度係使用BROOKFIELD公 司製CAP2000H ’ GPC測定係使用裝置：MODEL151 ( Waters (股）製）及管柱：3 支 TSK-GEL2000HX 及 1 支 TSK-GEL4 0 0 0HX (皆東曹（股）製），於溶劑：四氫呋 喃’流速：l_〇ml/分鐘，溫度：3 8°C，檢測器：RI的條件 下進行。 -16- 201211097 實施例2(多價羥基樹脂之製造） 使用2-萘酚代替1-萘酚，與實施例1同樣地使反應 ，而得到2 3 7g褐色的樹脂（多價羥基樹脂B )。所得之 多價羥基樹脂的羥基當量爲21 7g/eq.，軟化點爲1 2 PC， 在150°C的熔融黏度爲6.2Pa.s。根據所回收的未反應單 體之分析，倂入樹脂中的1-萘酚（N)與苯酚（B)之比 率爲N/(N + B) =0.50。圖2中顯示GPC圖。 實施例3 (多價羥基樹脂之製造） 於1L的四口可分離式燒瓶中，量取l〇〇gl-萘酚、 437g苯酚、18 0g二氯甲基萘（1，4-二氯甲基體43.5%、 1，5-二氯甲基體55.3°/。、其它二氯甲基體1.2%)及200g 氯苯，在氮氣流下，邊攪拌邊徐徐升溫溶解，於約8 0°C照 那樣地反應2小時。然後，邊餾去氯苯邊升溫到180°C爲 止，照那樣地反應1小時。反應後，藉由減壓餾去而去除 溶劑與未反應單體後，得到275 g褐色的樹脂（多價羥基 樹脂C)。所得之多價羥基樹脂的羥基當量爲206g/eq.， 軟化點爲l〇5°C，在150°C的熔融黏度爲3.4Pa.s。根據 所回收的未反應單體之分析，倂入樹脂中的1-萘酚（N) 與苯酚（B)之比率爲N/(N + B) =0.29。圖3中顯示GPC 圖。 實施例4(多價羥基樹脂之製造） -17- 201211097 於1L的四口可分離式燒瓶中，量取46g 2-萘酚、 27lg苯酚、215g二氯甲基萘（1，4-二氯甲基體43.5%、 1，5-二氯甲基體55.3%、其它二氯甲基體1.2%)及3 00g 氯苯，在氮氣流下，邊攪拌邊徐徐升溫溶解，於約80°C照 那樣地反應2小時。然後，邊餾去氯苯邊升溫到180 °C爲 止，照那樣地反應1小時。反應後，藉由減壓餾去而去除 溶劑與未反應單體後，得到306g褐色的樹脂（多價羥基 樹脂D)。所得之多價羥基樹脂的羥基當量爲213g/eq.， 軟化點爲115°C，在150°C的熔融黏度爲4.9Pa.s。根據 所回收的未反應單體之分析，倂入樹脂中的2-萘酚（N) 與苯酚（B)之比率爲Ν/(Ν + Β) =0·23»圖4中顯示GPC 圖。 實施例5 (多價羥基樹脂之製造） 於1L的四口可分離式燒瓶中，量取224g 2-萘酚、 272g苯酚、100g二氯甲基萘（1，4 -二氯甲基體43.5%、1 ，5-二氯甲基體55.3%、其它二氯甲基體1.2%)及300g 氯苯，在氮氣流下，邊攪拌邊徐徐升溫溶解，於約8 0 °C照 那樣地反應2小時。然後，邊餾去氯苯邊升溫到〗80〇C爲 止，照那樣地反應1小時。反應後，藉由減壓餾去而去除 溶劑與未反應單體後，得到2 0 7 g褐色的樹脂（多價羥基 樹脂E)。所得之多價羥基樹脂的羥基當量爲220g/eq.， 軟化點爲120°C，在150°C的熔融黏度爲6.2Pa · s。根據 所回收的未反應單體之分析，併入樹脂中的1-萘酚（N) -18- 201211097(3) (only 'A represents naphthalene ring (N) or benzene ring (β), 〇 represents epoxy propyl ' π represents the number of 1 to 15), n / (N + B) is 0.2 to 0.7, while softening The point is 60 to 100 <> C, and the melt viscosity at 150 ° C is 0.2 to 1. OPa.s. Further, the present invention provides a method for producing an epoxy resin represented by the above formula (3), which is characterized in that a polyvalent hydroxy resin represented by the above formula (1) is reacted with epichlorohydrin. Further, the present invention is an epoxy resin composition obtained by blending at least one of the above epoxy resin or polyvalent hydroxy resin as an essential component of an epoxy resin component or a hardener component, and is an epoxy resin composition. The cured epoxy resin composition is cured. [Effect of the Invention] The cured product obtained by curing the epoxy resin composition obtained from the epoxy resin or the polyvalent hydroxy resin of the present invention is excellent in moisture resistance and heat resistance, and excellent in mechanical properties such as impact resistance. The performance can be applied to lamination, forming, casting, adhesion and the like. [Embodiment] [Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. The polyvalent hydroxy resin of the present invention is represented by the above formula (i). Here, 'A represents a naphthalene ring or a benzene ring, and has a structure in which a naphthalene ring (n) and a benzene ring (b) coexist. 'The ratio of naphthalene ring (N) to A (mol ratio) is represented by N/(N + B) For the range of 〇·2~0.7. If it is less than this, the heat resistance based on the naphthalene structure, the effect of improving the moisture resistance and the like is small, and if it is more than this, the softening point and the viscosity are increased, and the moldability is lowered. Here, the above molar ratio is an average molar ratio of a naphthalene ring to a benzene ring in the polyvalent base resin. -8- 201211097 The above naphthalene ring and benzene ring may also be substituted by an alkyl group having 1 to 6 carbon atoms, preferably unsubstituted or substituted with a methyl group. η represents an average number of repetitions (amount of average), and is 1 to 15, preferably 1 to 1 to 5. If η is less than this, the point of heat resistance is not suitable. Further, when it is larger than this, the softening point and the viscosity are changed, and the formability is lowered. The polyvalent hydroxy resin of the present invention has a softening point in the range of 75 to 125 ° C, preferably 80 to 120 ° C. Further, the melt viscosity at 150 ° C is in the range of 2 to 10 Pa·s, preferably 3 to 8 Pa·s, and the polyvalent hydroxy resin can be obtained by using phenols and naphthols and formula (2). The condensing agent shown is obtained by reaction. The phenols referred to herein are phenols substituted or substituted with an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include phenol, o-cresol, m-cresol, p-phenol, ethylphenol, and isopropylphenol. From the viewpoints of low viscosity and high reactivity of the obtained resin, the third butyl phenol, o- phenol, p-phenyl phenol, 2,6-xylenol, and 2,6-diethyl phenol are Less unsubstituted phenol. Further, the so-called naphthols are a 1 to 6 alkyl substituted or unsubstituted naphthol. Preferably, the unsubstituted naphthol is specifically 1-naphthol or 2-naphthol. These phenols or naphthols may be used singly or in combination of two or more. The ratio of the phenol to the naphthol used in the reaction is 0 to 2 to 0.7 mol naphthol of the theoretical amount relative to the total of 1 mole of the two, but considering the difference in reactivity In the case of the naphthalene-based condensing agent of the formula (2), the X-based hydroxyl group and the halogen number are preferably high-melting and non-toluene. 40 素 201211097 Atom or alkoxy group having 1 to 6 carbon atoms. From the viewpoint of reactivity with a phenolic compound, it is preferably a hydroxyl group or a halogen atom. The halogen atom is preferably a chlorine atom, and the alkoxy group is preferably a methoxy group. The substitution positions of the two CHzX groups of the naphthalene ring may be on the same benzene ring or on the respective benzene rings, and the preferred substitution positions are 1,4-position, 1,5-position, 1,6-position. , 2,6-bit, 2,7-bit. From the viewpoint of physical properties such as heat resistance, mechanical strength and toughness, it is preferably 1,4 -position and 1,5 -position. The naphthalene-based condensing agent may be a mixture of these, and the total content of the 1,4-disubstituted product and the 1,5-disubstituted compound in the naphthalene-based condensing agent is preferably 9% by weight or more. The naphthalene-based condensing agent represented by the formula (2) is not particularly limited, and can be usually produced by a chloromethylation reaction of naphthalene or a chlorination reaction of a methyl group of dimethylnaphthalene. The condensing agent may further contain a monosubstituted naphthalene substituted with only one CH2X group on the naphthalene ring, and the content of the monomer is 10% by weight or less, preferably 5% by weight or less and more preferably 3% by weight or less. When the content of the monomer is more than this, the crosslinking density at the time of curing the resin is lowered, resulting in a decrease in heat resistance. In the reaction between the phenolic compound and the naphthalene-based condensing agent, an excessive amount of phenols and naphthols are used for the naphthalene-based condensing agent. The naphthalene-based condensing agent is used in an amount of from 0.05 to 3535 mol, preferably from 0.1 to 〇3 mol, based on 1 mol of the total amount of the phenol and the naphthol. If it is more than this, the softening point of the resin becomes high, which hinders the workability. In addition, if the amount is less than this, the amount of excess of phenols and naphthols used in the excess is increased, which is industrially unsuitable. The naphthalene-based condensing agent is substantially smaller than the theoretical amount, so substantially the entire amount of naphthalene is used. The binder system completes the reaction at the time of the reaction. -10- 201211097 This reaction can be carried out in the presence of an acid catalyst, and as the acid catalyst, it can be suitably selected from the well-known inorganic acid 'organic acid. Examples of such an acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, or organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, and diethylsulfuric acid, or zinc chloride or chlorine. A Lewis acid such as aluminum, ferric chloride or boron trifluoride, or a solid acid such as activated clay, vermiculite-alumina or zeolite. Further, when dichloromethylnaphthalene is used as the binder represented by the general formula (2), the reaction can be carried out without a catalyst. Usually, the reaction is carried out at 10 to 250 ° C for 1 to 20 hours. Further, as the reaction solvent, an alcohol such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve or ethyl cellosolve may be used, or benzene, toluene, chlorobenzene or dichlorobenzene may be used. Wait. After the completion of the reaction, the catalyst may be removed by a method such as neutralization or water washing, and the remaining solvent and unreacted phenolic compound may be removed from the system by distillation under reduced pressure, if necessary. And become a multivalent hydroxy resin. The unreacted phenolic compound is usually 3% or less, preferably 1% or less. If it is more than this, the heat resistance at the time of a hardened material falls. However, when a phenolic compound having two or more valences is used for the reaction, the remaining phenolic compound may be removed after the reaction. In the present invention, a naphthylmethyl group may be bonded to the polyvalent hydroxy resin represented by the above formula (1). For example, in the naphthalene-based condensing agent which reacts with a phenolic compound, when monochloromethylnaphthalene, monohydroxynaphthalene or monoalkoxymethylnaphthalene is contained, the polyvalent hydroxy resin of the formula (1) is A mixture of one or more compounds of -11 - 201211097 naphthylmethylalkyl group of the polyvalent hydroxy resin of the formula (1) is added. Even if it is a mixture, the effect of the present invention can be exerted without any hindrance, and these can be used as an epoxy resin hardener, and a raw material which is an epoxy resin of the present invention can be used. The epoxy resin of the present invention is represented by the above formula (3). Here, the A and η systems are the same as those described for the polyvalent hydroxy resin of the formula (1). The softening point of the epoxy resin of the present invention is in the range of 60 to 100 ° C, more preferably in the range of 75 to 95 ° C. Further, the melt viscosity at 150 ° C is in the range of 0.1 to 1.0 Paa·s, more preferably in the range of 0.2 to 0.8 Pa · s. The epoxy resin of the present invention can be obtained by reacting a polyvalent hydroxyl resin represented by the above formula (1) with epichlorohydrin. This reaction can be carried out in the same manner as a normal epoxidation reaction. For example, after dissolving the polyvalent hydroxy resin represented by the above formula (1) in excess epichlorohydrin, sodium hydroxide or potassium hydroxide is used. In the presence of an alkali metal hydroxide, the reaction is carried out at a temperature of from 50 to 150 ° C, preferably from 60 to 120 ° C, for a period of from 1 to 10 hours. In this case, the amount of the alkali metal hydroxide to be used is 0.8 to 2 moles, preferably 0.9 to 1.2 moles, per mole of the hydroxyl group in the polyvalent hydroxy resin. Further, the epichlorohydrin is excessively used for the hydroxyl group in the polyvalent hydroxy resin, and is usually in the range of 1.5 to 15 moles, preferably 2 to 8 moles, per mole of the hydroxyl group in the polyvalent hydroxy resin. Further, a quaternary ammonium salt or the like may be added during the reaction. The quaternary ammonium salt is, for example, tetramethyl chlorinated chloride, tetrabutylammonium chloride or benzyltriethylammonium chloride, and the amount thereof is preferably in the range of 0.1 to 2.0% by weight based on the polyvalent hydroxy resin. If it is less than this, the addition effect of the quaternary ammonium salt is small, and if it is more than this, the formation of the refractory chlorine becomes large, and it becomes difficult to become high purity. -12- 201211097 Further, a polar solvent such as dimethyl sulfite or diglyme can be used, and the amount thereof is preferably in the range of 10 to 20 0 wt% based on the polyvalent hydroxy resin. If it is less than this, the effect of addition is small, and if it is more than this, the volumetric efficiency is lowered and it is economically unsuitable. After the completion of the reaction, the excess epichlorohydrin can be distilled off, and the residue can be dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove an inorganic salt, and then the solvent is distilled off to obtain a solvent. The purpose of the epoxy resin. The epoxy resin is mainly composed of the formula (3), but may contain one or more naphthylmethyl groups in the aromatic ring of the polyvalent hydroxy resin of the formula (1). An epoxypropyl etherate of the compound. Further, an oligomerization agent in which the epoxy group in the epoxy resin of the present invention is an ether bond may be contained. The epoxy resin composition of the present invention is composed of an epoxy resin and a curing agent, and is blended with an epoxy resin represented by the formula (3) as an epoxy resin component or the above formula (1) as a hardener component. At least one of the polyvalent hydroxy resins shown is regarded as an essential component. In particular, an epoxy resin represented by the formula (3) as an epoxy resin component is blended with a polyvalent hydroxy resin represented by the formula (1) as a hardener component, and has a high degree. It is better for flame retardancy and physical balance. As the hardener when the epoxy resin represented by the formula (3) is an essential component, generally, all of the curing agents known as epoxy resins can be used. For example, there are cyanogen, polyvalent phenols, acid anhydrides, aromatic and aliphatic amines. Specifically, as the polyvalent phenol, there are, for example, bisphenol A, bisphenol F, bisphenol S, bisphenol, 4,4'-biphenol, 2,2,-biphenol, hydroquinone, and m-benzene. Divalent phenols such as diphenols, naphthalenediols, or tris(4-hydroxyphenyl-13-201211097) methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol phenol paint , o-cresol novolac, naphthol novolac, polyvinyl phenol represented by more than three phenols, and more phenols, naphthols, or A, bisphenol F, bisphenol S, bisphenol, 4 , divalent phenols such as 4'-biphenol, 2,2'-linked, hydroquinone, resorcinol, naphthalenediol, etc. via methyl acetal, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene A polyvalent phenolic compound synthesized by a diol or the like as an acid anhydride, including phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrobenzene Dicarboxylic anhydride, hemiic acid, nadic anhydride, trimellitic anhydride, and the like. Further, as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane 4,4'-diaminodiphenylphosphonium, m-phenylenediamine, p-benzene An aromatic amine such as dimethyldiamine, an ethylenediamine, hexamethylenediamine, diethylenetriamine or a tribasic aliphatic amine, or a polyvalent hydroxy resin represented by the formula (1). In the resin composition of the invention, one or two of these curing agents may be used in combination, but the blending amount of the epoxy resin of the present invention is in the range of 5 to 100% in the epoxy resin. The epoxy resin in the case where the polyvalent hydroxy resin represented by the formula (1) is an essential component of the curing agent can be used as a general epoxy resin having two or more rings in the molecule. For example, there are divalent phenols such as bisphenol A, S, bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, m-benzene, or tris(4-hydroxybenzene). a methane, 1,1,2, (4-hydroxyphenyl)ethane, a phenol novolac, an o-cresol novolac, a trivalent or higher phenol, or a halogenated aldehyde clear by tetrabromobisphenol A or the like. The arylamine which is bisphenol phenol aldehyde and condensed formic acid dimethyl anhydride is equivalent to the epoxy propyl group derived from bisphenol-14-201211097 such as oxybisphenol diphenol 2-tetralac. An etherified compound or a polyfunctional epoxy resin represented by the above formula (1). These epoxy resins may be used in combination of one type or two types. However, the amount of the polyvalent base resin of the present invention is in the range of 5 to 100% in the entire epoxy resin. Further, it can be suitably blended with an epoxy resin represented by the formula (3) or an epoxy resin of the present invention having a general formula (the polyvalent base resin represented by 〇 or both of them). An oligomer or a polymer compound of a polyester, a polyamide, a polyimine, a polyacid, a polyurethane, a petroleum resin, a quinone-coumarin resin, a phenoxy resin, or the like, may also be blended. An additive such as an inorganic chelating agent, a pigment, a refractory agent, a thixotropy-imparting agent, a coupling agent, or a fluidity improver. Examples of the inorganic chelating agent include spherical or pulverized molten vermiculite and crystal sand. As sandstone powder, oxidized powder, glass powder, or mica, talc, calcium carbonate, alumina, hydrated alumina, etc., as pigments, organic or inorganic body pigments, flaky pigments, etc. Examples of the imparting agent include a lanthanoid, a castor oil, an aliphatic guanamine wax, an oxidized polyethylene ruthenium, an organic bentonite, etc., and a conventional hardening accelerator can be used as needed. For example, there are amines. , imidazoles, organic terpenes, Lewis acid, etc. It is usually in the range of 0.2 to 5 parts by weight based on 100 parts by weight of the epoxy resin. Further, if necessary, a release agent such as carnauba wax or OP wax or a γ-ring can be used in the resin composition of the present invention. a coupling agent such as oxypropoxypropyltrimethoxydecane, a coloring agent such as carbon black, a flame retardant such as antimony trioxide, a low stress agent such as eucalyptus oil, or a slip agent such as calcium stearate. The cured product of the invention can be obtained by molding the epoxy resin composition by a method such as casting, compression molding, or transfer molding, such as -15 to 201211097. The temperature at the time of formation is usually in the range of 120 to 220 °C. [Examples] Hereinafter, the present invention will be specifically described based on examples and comparative examples. Example 1 (Production of polyvalent hydroxy resin) 96 g of 1-naphthol was weighed in a 1 L four-neck separable flask. 251 g of phenol, 150 g of dichloromethylnaphthalene (1,4-dichloromethyl form 43.5%, 1,5-dichloromethyl group 55.3%, other dichloromethyl group 1.2%) and 450 g of chlorobenzene in nitrogen Under the flow, the mixture was slowly heated and dissolved while stirring, and reacted at about 80 ° C for 2 hours. Then, the chlorobenzene was distilled off. The temperature was raised to 180 ° C, and the reaction was carried out for 1 hour. After the reaction, the solvent and the unreacted monomer were removed by distillation under reduced pressure to obtain 23 g of a brown resin (polyvalent hydroxy resin A). The hydroxy resin has a hydroxyl equivalent weight of 230 g/eq., a softening point of 123 ° C, and a melt viscosity at 150 ° C of 9.5 Pa·s» according to the analysis of the unreacted monomer recovered, 1 in the resin The ratio (molar ratio) of naphthol (N) to phenol (B) is N/( N + B ) = 0.57. The GPC chart is shown in Fig. 1. Here, the melt viscosity is a CAP2000H 'GPC measurement system manufactured by BROOKFIELD. Equipment used: MODEL151 (made by Waters) and column: 3 TSK-GEL2000HX and 1 TSK-GEL4 0 0 0HX (made by Tosoh Co., Ltd.), solvent: tetrahydrofuran 'flow rate: l_〇ml /min, temperature: 3 8 ° C, detector: RI conditions were carried out. -16-201211097 Example 2 (Production of polyvalent hydroxy resin) 2-naphthol was used instead of 1-naphthol, and the reaction was carried out in the same manner as in Example 1 to obtain 273 g of a brown resin (polyvalent hydroxy resin B). . The obtained polyvalent hydroxy resin had a hydroxyl equivalent of 21 7 g/eq., a softening point of 1 2 PC, and a melt viscosity at 150 ° C of 6.2 Pa·s. According to the analysis of the unreacted monomer recovered, the ratio of 1-naphthol (N) to phenol (B) incorporated into the resin was N/(N + B) = 0.50. The GPC chart is shown in Figure 2. Example 3 (Production of polyvalent hydroxy resin) In a 1 L four-neck separable flask, l〇〇gl-naphthol, 437 g of phenol, and 180 g of dichloromethylnaphthalene (1,4-dichloromethyl) were weighed. The substrate has a base of 43.5%, 1,5-dichloromethyl 55.3 °, and other dichloromethyl groups (1.2%) and 200 g of chlorobenzene. Under a nitrogen stream, the mixture is slowly heated and dissolved while stirring at about 80 ° C. The reaction was carried out as that for 2 hours. Then, the temperature was raised to 180 ° C while distilling off the chlorobenzene, and the reaction was carried out for 1 hour. After the reaction, the solvent and the unreacted monomer were removed by distillation under reduced pressure to obtain 275 g of a brown resin (polyvalent hydroxy resin C). The obtained polyvalent hydroxy resin had a hydroxyl equivalent of 206 g/eq., a softening point of 10 ° C, and a melt viscosity at 150 ° C of 3.4 Pa.s. According to the analysis of the unreacted monomers recovered, the ratio of 1-naphthol (N) to phenol (B) incorporated into the resin was N/(N + B) = 0.29. The GPC chart is shown in Figure 3. Example 4 (Production of Polyvalent Hydroxyl Resin) -17- 201211097 In a 1 L four-neck separable flask, 46 g of 2-naphthol, 27 g of phenol, and 215 g of dichloromethylnaphthalene (1,4-dichloro) were weighed. 43.5% of methyl, 55.3% of 1,5-dichloromethyl, 1.2% of other dichloromethyl, and 300 g of chlorobenzene were slowly heated and dissolved under stirring under a nitrogen stream at about 80 ° C. The reaction was carried out for 2 hours. Then, the temperature was raised to 180 °C while distilling off the chlorobenzene, and the reaction was carried out for 1 hour. After the reaction, the solvent and the unreacted monomer were removed by distillation under reduced pressure to obtain 306 g of a brown resin (polyvalent hydroxy resin D). The obtained polyvalent hydroxy resin had a hydroxyl equivalent of 213 g/eq., a softening point of 115 ° C, and a melt viscosity at 150 ° C of 4.9 Pa·s. According to the analysis of the unreacted monomers recovered, the ratio of 2-naphthol (N) to phenol (B) in the resin was Ν/(Ν + Β) = 0.23. The GPC chart is shown in Fig. 4. Example 5 (Production of polyvalent hydroxy resin) 224 g of 2-naphthol, 272 g of phenol, and 100 g of dichloromethylnaphthalene (1,4-dichloromethyl 43.5) were weighed in a 1 L four-neck separable flask. %, 1,5-dichloromethyl group (55.3%, other dichloromethyl group 1.2%) and 300 g of chlorobenzene were slowly heated to dissolve under a nitrogen stream with stirring, and reacted at about 80 °C. hour. Then, while the chlorobenzene was distilled off, the temperature was raised to 80 ° C, and the reaction was carried out for 1 hour. After the reaction, the solvent and the unreacted monomer were removed by distillation under reduced pressure to obtain 207 g of a brown resin (polyvalent hydroxy resin E). The obtained polyvalent hydroxy resin had a hydroxyl equivalent of 220 g/eq., a softening point of 120 ° C, and a melt viscosity at 150 ° C of 6.2 Pa · s. 1-naphthol (N) -18- 201211097 incorporated into the resin according to the analysis of the unreacted monomers recovered
與苯酚（B)之比率爲N/( N + B ) =0.70。圖5中顯示GPC 圖。 比較例1 (多價羥基樹脂之製造） 於1L的四口可分離式燒瓶中，量取251g 1-萘酚、 200g苯酚、131g二氯甲基萘（1，4-二氯甲基體43.5%、 1，5-二氯甲基體55.3%、其它二氯甲基體1.2%)及300g 氯苯，在氮氣流下，邊攪拌邊徐徐升溫溶解，於約80°C照 那樣地反應2小時。然後，邊餾去氯苯邊升溫到180°C爲 止，照那樣地反應1小時。反應.後，藉由減壓餾去而去除 溶劑與未反應單體後，得到25 5 g褐色的樹脂（多價羥基 樹脂F)。所得之多價羥基樹脂的羥基當量爲231 g/eq.， 軟化點爲130°C，在150°C的熔融黏度爲l〇.5Pa · s。根據 所回收的未反應單體之分析，倂入樹脂中的1-萘酚（N) 與苯酚（B)之比率爲N/(N + B) =0.74。圖6中顯示GPC 圖。 比較例2(多價羥基樹脂之製造） 於1L的四口可分離式燒瓶中，量取57g 2-萘酚、 150g苯酚、180g二氯甲基萘（1，4-二氯甲基體43.5%、 1，5-二氯甲基體55.3%、其它二氯甲基體 1.2%)及400g 氯苯，在氮氣流下，邊攪拌邊徐徐升溫溶解，於約8〇°C照 那樣地反應2小時。然後，邊餾去氯苯邊升溫到180°C爲 止，照那樣地反應1小時。反應後，藉由減壓餾去而去除 -19- 201211097The ratio to phenol (B) is N/(N + B) = 0.70. The GPC chart is shown in Figure 5. Comparative Example 1 (Production of polyvalent hydroxy resin) 251 g of 1-naphthol, 200 g of phenol, and 131 g of dichloromethylnaphthalene (1,4-dichloromethyl 43.5) were weighed in a 1 L four-neck separable flask. %, 1,5-dichloromethyl group (55.3%, other dichloromethyl group 1.2%) and 300 g of chlorobenzene were slowly heated to dissolve under a nitrogen stream with stirring, and reacted at about 80 ° C for 2 hours. . Then, the temperature was raised to 180 ° C while distilling off the chlorobenzene, and the reaction was carried out for 1 hour. After the reaction, the solvent and the unreacted monomer were removed by distillation under reduced pressure to obtain 25 5 g of a brown resin (polyvalent hydroxy resin F). The obtained polyvalent hydroxy resin had a hydroxyl equivalent of 231 g/eq., a softening point of 130 ° C, and a melt viscosity at 150 ° C of 10 Pa 5 Pa · s. According to the analysis of the unreacted monomers recovered, the ratio of 1-naphthol (N) to phenol (B) incorporated into the resin was N/(N + B) = 0.74. The GPC chart is shown in Figure 6. Comparative Example 2 (Production of polyvalent hydroxy resin) In a 1 L four-neck separable flask, 57 g of 2-naphthol, 150 g of phenol, and 180 g of dichloromethylnaphthalene (1,4-dichloromethyl 43.5) were weighed. %, 1,5-dichloromethyl group (55.3%, other dichloromethyl group 1.2%) and 400 g of chlorobenzene were slowly heated to dissolve under a nitrogen stream with stirring, and reacted at about 8 ° C. hour. Then, the temperature was raised to 180 ° C while distilling off the chlorobenzene, and the reaction was carried out for 1 hour. After the reaction, it is removed by distillation under reduced pressure. -19- 201211097
溶劑與未反應單體後，得到261g褐色的樹脂（多價羥基 樹脂G)。所得之多價羥基樹脂的羥基當量爲234g/eq. ’ 軟化點爲135°C，在150°C的熔融黏度爲14_8Pa.s。根據 所回收的未反應單體之分析，倂入樹脂中的2_萘酚（N) 與苯酚（B)之比率爲N/(N + B) =0.29。圖7中顯示GPC 圖。 比較例3 (多價羥基樹脂之製造） 於1L的四口可分離式燒瓶中，量取320g 2-萘酚、 100g二氯甲基萘（1,4-二氯甲基體43.5%、1，5-二氯甲基 體55.3%、其它二氯甲基體1.2%)及420g氯苯’在氮氣 流下，邊攪拌邊徐徐升溫溶解，於約95 °C照那樣地反應2 小時。然後，邊餾去氯苯邊升溫到180 °C爲止’照那樣地 反應1小時。反應後，藉由減壓餾去而去除溶劑與未反應 單體後，得到1 7 1 g褐色的樹脂（多價羥基樹脂Η )。所 得之多價羥基樹脂的羥基當量爲 25 3 g/eq. ’軟化點爲 174。(：，在150°C的熔融黏度爲50Pa· s以上。根據所回收 的未反應單體之分析，倂入樹脂中的1-萘酚（N)與苯酚 (B)之比率爲N/(N + B) =1_00。圖8中顯示GPC圖。 實施例6 將l〇〇g實施例2所得之多價羥基樹脂B溶解於298g 環氧氯丙烷及45g二甘醇二甲醚中’於減壓下（約 1 20mmHg )，在6 0 °C費4小時滴下3 8 g 4 8 %氫氧化鈉水溶 -20- 201211097 液。其間’所生成的水係藉由與環氧氯丙烷的共沸而去除 到系外，所餾出的環氧氯丙烷係返回系內。滴下結束後， 再繼續反應1小時。然後，減壓餾去環氧氯丙烷及二甘醇 二甲醚，溶解於295g甲基異丁基酮中後，藉由水洗來去 除所生成的鹽。然後，添加9g 4 8%氫氧化鈉水溶液，於 8 0°C反應2小時。反應後，進行水洗後，減壓餾去溶劑的 甲基異丁基酮，而得到121g褐色的環氧樹脂（環氧樹脂 A)。所得之環氧樹脂A的環氧當量爲26 8g/eq.，軟化點 爲 8 7°C，水解性氯爲120ppm，在150°C的熔融黏度爲 0.40Pa . s。圖9中顯示GPC圖。再者，此處的水解性氯 係藉由將〇.5g樹脂試料溶解於3 0ml的1，4-二噁烷中，於 1N-KOH/甲醇溶液5ml中煮沸回流30分鐘，以硝酸銀溶 液進行電位差滴定而求得。 實施例7 將l〇〇g實施例4所得之多價羥基樹脂D溶解於3 07g 環氧氯丙烷及4 8g二甘醇二甲醚中，使用4 0g 4 8 %氫氧化 鈉水溶液，與實施例6同樣地進行反應，而得到1 1 4g褐 色的環氧樹脂（環氧樹脂B)。所得之環氧樹脂B的環氧 當量爲261g/eq.，軟化點爲84°C，水解性氯爲200ppm’ 在150°C的熔融黏度爲〇.4Pa· s。圖10中顯示GPC圖。 實施例8 將100g實施例5所得之多價羥基樹脂E溶解於300g 201211097 環氧氯丙烷及45g二甘醇二甲醚中’使用38.5g 48%氫氧 化鈉水溶液’與實施例4同樣地進行反應’而得到1 1 1 g 褐色的環氧樹脂（環氧樹脂C) °所得之環氧樹脂C的環 氧當量爲262g/eq.，軟化點爲93°C’水解性氯爲UOppm ，在150°C的熔融黏度爲〇.6Pa· s。圖11中顯示Gpc圖 比較例4 將l〇〇g比較例1所得之多價羥基樹脂F溶解於280g 環氧氯丙烷及42g二甘醇二甲醚中，使用36.lg 4 8%氫氧 化鈉水溶液，與實施例3同樣地進行反應，而得到1 〇7g 褐色的環氧樹脂（環氧樹脂D) »所得之環氧樹脂的環氧 當量爲2 82g/eq.，軟化點爲102°C ’水解性氯爲320ppm， 在150°C的熔融黏度爲1.2Pa· s»圖12中顯示GPC圖。 比較例5 將l〇〇g比較例2所得之多價羥基樹脂G溶解於277g 環氧氯丙烷及42g二甘醇二甲醚中，使用35.6g 48%氫氧 化鈉水溶液，與實施例3同樣地進行反應，而得到丨i 0 g 褐色的環氧樹脂（環氧樹脂E)。所得之環氧樹脂的環氧 當量爲28 5 g/eq. ’軟化點爲1 20°C ’水解性氯爲290ppm， 在150C的溶融黏度爲2.5Pa. s。圖13中顯示GPC圖。 實施例9〜16及比較例5〜9 -22- 201211097 使用實施例1〜8、比較例1〜5所合成的多價羥基樹 脂及環氧樹脂、2-萘酚芳烷基型環氧樹脂（環氧當量280 ，軟化點84°C，在150°C的熔融黏度〇.38Pa· s; ESN-185 ，新日鐵化學製；環氧樹脂F) 、3,3’，5,5’-四甲基-4,4’-二羥基聯苯基的環氧化物（環氧當量195，水解性氯 4 5 0ppm，熔點 105°C，在 150°C 的熔融黏度 1 ImPa . s ; YX-4000HK，日本環氧樹脂製；環氧樹脂G)、苯酚芳烷 基樹脂（OH當量162，軟化點50°C，在150°C的熔融黏度 30mPa . s ; MEH-7800-4L，明和化成製；苯酚樹脂 A )、 1-萘酚芳烷基樹脂（OH當量208，軟化點74°C，在150°C 的熔融黏度35mPa · s ; SN-475，新日鐵化學製；多價羥 基樹脂I)，使用三苯基膦當作硬化促進劑，使用γ-環氧 丙氧基丙基三甲氧基矽烷當作矽烷偶合劑，以表1中所示 的配合，成爲樹脂組成物。 作爲樹脂組成物的物性測定，螺旋流動係以根據規格 (ΕΜΜΙ-1-66 )的螺旋流動測定用模具，在螺旋流動的注 入壓力（150kgf/cm2)、硬化溫度 W5°C、硬化時間3分 鐘的條件下，將環氧樹脂組成物成形，調査流動長度》膠 化時間係使環氧樹脂組成物流入預先經加熱到1 75 °C的膠 化試驗機（日新科學（股）製）之凹部，使用PTFE製的 攪拌棒，以一秒爲2轉的速度來攪拌，調査環氧樹脂組成 物到硬化爲止所需要的膠化時間。硬化物的物性係使用此 環氧樹脂組成物，在175 °C成形，在175t進行12小時的 後固化，得到硬化物試驗片後，供用於各種物性測定。玻 -23- 201211097 璃轉移點及熱膨脹係數的測定係藉由熱機械測定裝置，在 升溫速度7°C /分鐘的條件下求得。彎曲試驗係藉由3點彎 曲法進行240°C的高溫彎曲強度、彎曲彈性模數測定。黏 著強度係藉由壓縮成型機，在175 °C於2片42合金板之間 形成25mmxl2.5mmx0.5mm的成形物，在175°C進行12小 時的後固化後，求得拉伸剪切強度來評價。吸水率係使用 本環氧樹脂組成物，形成直徑50mm、厚度3mm的圓盤， 於後固化後，在85°C、85%RH的條件，使吸濕1〇〇小時 者。難燃性係將厚度1/16吋的試驗片成形，依照UL94V-〇規格來評價，以n = 5的試驗之合計燃燒時間來表示。表 2中彙總顯示結果。 -24- 201211097 【Is 比較例 9 LO csi LT5 〇 LO LO 1比?例 〇〇 CO C^3 oo s LO 168.5 I 1 81.5 ! o LO LO 比較例 6 m 0¾ in LO s 分 LO 比較例 5 LT3 LTD | 54.5 | s LO 比較例 4 LT5 0¾ LO LO o LTD LT? —； 實施例 :16 「70.5 | 「79.5 1 s 呀 UT5 實施例 15 CO s 呀 LO ψ- < 實施例 14 crj CO g ΙΛ 闺2 | 84.5 1 LTD Lri CO s 切 LH) » n 實施例 12 LO 〇〇 C3 ΙΛ CO C5 lh> Ln 實施例 11 Lrt CO 0¾ LO D； s LH> 實施例 10 1 92.5 | | 57.5 | <〇 LT3 呀 LO 實施例 9 Γ93.5] | 56. 5 | Ο LO LO 環氧樹脂A 丨環氧樹脂B 丨環氧樹脂c 品 an 艇 m 酹 w 婴 Μ 祕 m Sg M 碱 m o m EH3 M m < m 勘 n r> m3 m 糊 ίι 1¾ w 鋰 m tL. 幻m m 徽 n r> 1¾ ϋ m n m m ^fTTs 5m ΕΠ3 靼 m nTj\ 擊 丨苯酚樹脂A 丨矽石 硬化促進劑 -25- 201211097 【®】 比較例 9 3 CO 卜 LT3 •麵_ 卜 CO CO LO c^a 琴n 1 16.6 1 Cn3 r—^ I 0.25 I c·^ C^3 比較例 8 CO CO 0¾ LT3 CO LT? C^3 CO Ln oo 16.6 C^3 0. 21 比較例 7 oo CO 0¾ oo t·— ΓΟ CO CO CO OO CO ΙΛ CO 0. 21 •^r LT3 比較例 6 CD CO σί CO CO LO C>〇 CD CO CD 0¾ CM I 16. 6 J Lrt 0. 24 比較例 5 CO CO Ln oo CO CO CO OO σ» | 16.6 CO CO 0¾ c> CO 比較例 4 cc 令 c〇 Lrt »< LO oo LO S CO 切 oo C=5 CQ C^3 實施例 16 σ> CQ CO CO oo Ln CO LTD CO Lfi CO t— CO CO C^3 Ψ· i 0. 20 實施例 15 S _ H CO CO s CO ♦—H LT5 κτ isi CO 16.8 ! CO CO —· CO C^3 <=5 0¾ 實施例 14 CO oo CO CO CO oo ⑦ CO LT3 oo LT3 CO CO s —一 c^a c=> 實施例 13 CO CO σ> oo ITS ΙΛ LT3 1 16.6Π CO LTD CO *碡 c=> LO 實施例 12 oo oo CO CO CO LT3 CO ^r | 16.9 1 C^3 CO LO CIS CO 實施例 11 oo oo 05 T3* ^p 々 LTD LT> OO CO crs 0¾ OO —H CZ3 CO 實施例 10 CO oo oo CD oo C*J' ITS 卜 LT3 ΙΛ —丨_ 1 16.5 ] oo —— C^3 C=5 CO CM 實施例 9 oo σ> C<I oo oo LT3 Lf3 CO tri CO |16. 2 | ^r C3 CO 丨螺旋流動(cm) i M 酸 熱時硬度 1玻璃轉移點rc) 熱膨脹係數 (<Tg，10-5) 熱膨脹係數 OTg, l〇-5) fin 各 m tM 瞬 租 親> 彎曲彈性模數(GPa) c- S m m w 鋇 /—s % Sf 燃燒時間(sec) -26- 201211097 【圖式簡單說明】 圖1係多價羥基樹脂A的GPC圖。 圖2係多價羥基樹脂B的GPC圖。 圖3係多價羥基樹脂C的GPC圖。 圖4係多價羥基樹脂D的GPC圖。 圖5係多價羥基樹脂E的GPC圖。’ 圖6係多價羥基樹脂F的GPC圖。 圖7係多價羥基樹脂G的GPC圖。 圖8係多價羥基樹脂Η的GPC圖。 圖9係環氧樹脂Α的GPC圖。 圖10係環氧樹脂B的GPC圖。 圖1 1係環氧樹脂C的GPC圖。 圖12係環氧樹脂D的GPC圖。 圖13係環氧樹脂E的GPC圖。 -27- !；After the solvent and the unreacted monomer, 261 g of a brown resin (polyvalent hydroxy resin G) was obtained. The obtained polyvalent hydroxy resin had a hydroxyl equivalent of 234 g/eq. The softening point was 135 ° C, and the melt viscosity at 150 ° C was 14 - 8 Pa.s. According to the analysis of the unreacted monomers recovered, the ratio of 2-naphthol (N) to phenol (B) incorporated into the resin was N/(N + B) = 0.29. The GPC chart is shown in Figure 7. Comparative Example 3 (Production of polyvalent hydroxy resin) In a 1 L four-neck separable flask, 320 g of 2-naphthol and 100 g of dichloromethylnaphthalene (1,4-dichloromethyl group 43.5%, 1) were weighed. 5,5-dichloromethyl group (55.3%, other dichloromethyl group 1.2%) and 420 g of chlorobenzene' were heated and dissolved under a nitrogen stream with stirring, and reacted at about 95 ° C for 2 hours. Then, the temperature was raised to 180 °C while distilling off the chlorobenzene, and the reaction was carried out for 1 hour. After the reaction, the solvent and the unreacted monomer were removed by distillation under reduced pressure to obtain 171 g of a brown resin (polyvalent hydroxy resin oxime). The resulting polyvalent hydroxy resin had a hydroxyl equivalent of 25 3 g/eq. The softening point was 174. (: The melt viscosity at 150 ° C is 50 Pa·s or more. According to the analysis of the unreacted monomers recovered, the ratio of 1-naphthol (N) to phenol (B) incorporated into the resin is N/( N + B) =1_00. The GPC chart is shown in Fig. 8. Example 6 The polyvalent hydroxy resin B obtained in Example 2 was dissolved in 298 g of epichlorohydrin and 45 g of diglyme. Under reduced pressure (about 1 20 mmHg), 3 8 g of 4 8 % sodium hydroxide water-soluble -20-201211097 solution was added at 60 ° C for 4 hours. During the process, the water produced was co-produced with epichlorohydrin. The mixture was removed from the system by boiling, and the distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was further continued for 1 hour. Then, epichlorohydrin and diglyme were distilled off under reduced pressure, and dissolved. After 295 g of methyl isobutyl ketone, the salt formed was removed by washing with water, and then 9 g of a 48% aqueous sodium hydroxide solution was added thereto, and the mixture was reacted at 80 ° C for 2 hours. After the reaction, the mixture was washed with water and then decompressed. The solvent of methyl isobutyl ketone was distilled off to obtain 121 g of a brown epoxy resin (epoxy resin A). The obtained epoxy resin A had an epoxy equivalent of 26 8 g/eq., and the softening point was 8 7 ° C, hydrolyzable chlorine is 120 ppm, and the melt viscosity at 150 ° C is 0.40 Pa s. The GPC chart is shown in Fig. 9. Further, the hydrolyzable chlorine here is prepared by dissolving 〇. 5 g of the resin sample. The mixture was boiled and refluxed for 30 minutes in 10 ml of 1N-KOH/methanol solution in 30 ml of 1,4-dioxane, and titrated by potentiometric titration with a silver nitrate solution. Example 7 Example 10 was obtained. The polyvalent hydroxy resin D was dissolved in 3 07 g of epichlorohydrin and 48 g of diglyme, and reacted in the same manner as in Example 6 using 40 g of a 4 % aqueous sodium hydroxide solution to obtain 1 14 g of brown. Epoxy resin (epoxy resin B). The obtained epoxy resin B has an epoxy equivalent of 261 g/eq., a softening point of 84 ° C, and a hydrolyzable chlorine of 200 ppm. The melt viscosity at 150 ° C is 〇. 4Pa·s. The GPC chart is shown in Fig. 10. Example 8 100 g of the polyvalent hydroxy resin E obtained in Example 5 was dissolved in 300 g of 201211097 epichlorohydrin and 45 g of diglyme, using 38.5 g of 48% hydrogen. The sodium oxide aqueous solution 'reacted in the same manner as in Example 4' to obtain 11.1 g of a brown epoxy resin (epoxy resin C). The epoxy equivalent is 262 g/eq., the softening point is 93 ° C. The hydrolyzable chlorine is UOppm, and the melt viscosity at 150 ° C is 〇.6 Pa·s. The Gpc chart is shown in Figure 11 Comparative Example 4 g The polyvalent hydroxy resin F obtained in Comparative Example 1 was dissolved in 280 g of epichlorohydrin and 42 g of diglyme, and reacted in the same manner as in Example 3 using 36. lg of a 4 % aqueous sodium hydroxide solution. 1 〇7g brown epoxy resin (epoxy resin D) was obtained. The epoxy resin obtained had an epoxy equivalent of 2 82 g/eq., a softening point of 102 ° C. The hydrolyzable chlorine was 320 ppm at 150 ° C. The melt viscosity was 1.2 Pa·s». The GPC chart is shown in FIG. Comparative Example 5 The polyvalent hydroxy resin G obtained in Comparative Example 2 was dissolved in 277 g of epichlorohydrin and 42 g of diglyme, and the same as in Example 3, using 35.6 g of a 48% aqueous sodium hydroxide solution. The reaction was carried out to obtain a 丨i 0 g brown epoxy resin (epoxy resin E). The epoxy resin obtained had an epoxy equivalent of 28 5 g/eq. The softening point was 1 20 ° C. The hydrolyzable chlorine was 290 ppm, and the melt viscosity at 150 C was 2.5 Pa·s. A GPC chart is shown in FIG. Examples 9 to 16 and Comparative Examples 5 to 9 -22 to 201211097 The polyvalent hydroxy resin and epoxy resin, 2-naphthol aralkyl type epoxy resin synthesized in Examples 1 to 8 and Comparative Examples 1 to 5 were used. (epoxy equivalent 280, softening point 84 ° C, melt viscosity at 150 ° C 〇.38Pa· s; ESN-185, Nippon Steel Chemical; epoxy resin F), 3,3', 5, 5' - epoxide of tetramethyl-4,4'-dihydroxybiphenyl (epoxy equivalent 195, hydrolyzable chlorine 4500 ppm, melting point 105 ° C, melt viscosity at 150 ° C 1 ImPa . s ; YX -4000HK, Japan epoxy resin; epoxy resin G), phenol aralkyl resin (OH equivalent 162, softening point 50 ° C, melt viscosity at 150 ° C 30 mPa. s; MEH-7800-4L, Minghe formation Phenolic resin A), 1-naphthol aralkyl resin (OH equivalent 208, softening point 74 ° C, melt viscosity at 150 ° C 35 mPa · s; SN-475, Nippon Steel Chemical; polyvalent hydroxyl Resin I), using triphenylphosphine as a hardening accelerator, and using γ-glycidoxypropyltrimethoxydecane as a decane coupling agent, and blended as shown in Table 1, became a resin composition. As a physical property measurement of the resin composition, the spiral flow is a spiral flow measurement mold according to the specification (ΕΜΜΙ-1-66), an injection pressure (150 kgf/cm 2 ) at a spiral flow, a curing temperature of W 5 ° C, and a hardening time of 3 minutes. Under the conditions, the epoxy resin composition was formed, and the flow length was investigated. The gelation time was such that the epoxy resin composition was poured into a gelation test machine (manufactured by Nisshin Scientific Co., Ltd.) which was previously heated to 1 75 °C. The concave portion was stirred at a speed of 2 revolutions per second using a stir bar made of PTFE, and the gelation time required for the epoxy resin composition to harden was examined. The physical properties of the cured product were obtained by forming the epoxy resin composition at 175 ° C and post-curing at 175 t for 12 hours to obtain a cured test piece, which was used for various physical properties. Glass -23- 201211097 The glass transition point and the coefficient of thermal expansion were determined by a thermomechanical measuring device at a heating rate of 7 ° C / min. The bending test was carried out by a three-point bending method at a high temperature bending strength of 240 ° C and a bending elastic modulus. Adhesive strength was formed by forming a 25 mm x 1.5 mm x 0.5 mm formed product between two 42 alloy plates at 175 ° C by a compression molding machine, and after 12 hours of post curing at 175 ° C, tensile shear strength was determined. To evaluate. The water absorption rate was obtained by using the epoxy resin composition to form a disk having a diameter of 50 mm and a thickness of 3 mm, and after moisture curing, it was allowed to absorb moisture for 1 hour at 85 ° C and 85% RH. The flame retardancy was formed by forming a test piece having a thickness of 1/16 , and evaluating it according to the UL94V-〇 specification, and expressing it by the total burning time of the test of n=5. The results are summarized in Table 2. -24- 201211097 [Is Comparative Example 9 LO csi LT5 〇LO LO 1 ratio? Example 〇〇CO C^3 oo s LO 168.5 I 1 81.5 ! o LO LO Comparative Example 6 m 03⁄4 in LO s 分 LO Comparative Example 5 LT3 LTD | 54.5 | s LO Comparative Example 4 LT5 03⁄4 LO LO o LTD LT? —; Example: 16 “70.5 | “79.5 1 s ah UT5 Example 15 CO s 呀 LO ψ- < Example 14 crj CO g ΙΛ闺2 | 84.5 1 LTD Lri CO s Cut LH) » n Example 12 LO 〇〇C3 ΙΛ CO C5 lh> Ln Example 11 Lrt CO 03⁄4 LO D; s LH> Example 10 1 92.5 | | 57.5 | 〇LT3 呀LO Example 9 Γ93.5] | 56. 5 | Ο LO LO Epoxy Resin A 丨 Epoxy Resin B 丨 Epoxy Resin c 品an Boat m 酹w Baby Μ Secret m Sg M Alkaline mom EH3 M m < m survey n r> m3 m paste ίι 13⁄4 w Lithium m tL. Magic mm emblem n r> 13⁄4 ϋ mnmm ^fTTs 5m ΕΠ3 靼m nTj\ 丨 丨 phenol resin A 丨矽 stone hardening accelerator-25- 20121109 7 [®] Comparative Example 9 3 CO Bu LT3 • Face _ Bu CO CO LO c^a Qin n 1 16.6 1 Cn3 r—^ I 0.25 I c·^ C^3 Comparative Example 8 CO CO 03⁄4 LT3 CO LT? C ^3 CO Ln oo 16.6 C^3 0. 21 Comparative Example 7 oo CO 03⁄4 oo t·— ΓΟ CO CO CO OO CO ΙΛ CO 0. 21 •^r LT3 Comparative Example 6 CD CO σί CO CO LO C>〇CD CO CD 03⁄4 CM I 16. 6 J Lrt 0. 24 Comparative Example 5 CO CO Ln oo CO CO CO OO σ» | 16.6 CO CO 03⁄4 c> CO Comparative Example 4 cc Let c〇Lrt »< LO oo LO S CO Cut oo C=5 CQ C^3 Example 16 σ> CQ CO CO oo Ln CO LTD CO Lfi CO t- CO CO C^3 Ψ· i 0. 20 Example 15 S _ H CO CO s CO ♦-H LT5 κτ isi CO 16.8 ! CO CO —· CO C^3 <=5 03⁄4 Example 14 CO oo CO CO CO oo 7 CO LT3 oo LT3 CO CO s —一c^ac=> Example 13 CO CO σ> ; oo ITS ΙΛ LT3 1 16.6Π CO LTD CO *碡c=> LO Example 12 oo oo CO CO CO LT3 CO ^r | 16.9 1 C^3 CO LO CIS CO Example 11 oo oo 05 T3* ^p 々LTD LT> OO CO crs 03⁄4 OO —H CZ3 CO Example 10 CO oo oo CD oo C*J' ITS LT3 ΙΛ —丨_ 1 16 .5 ] oo —— C^3 C=5 CO CM Example 9 oo σ>C<I oo oo LT3 Lf3 CO tri CO |16. 2 | ^r C3 CO 丨Spiral flow (cm) i M Hardness 1 glass transition point rc) Thermal expansion coefficient (<Tg, 10-5) Thermal expansion coefficient OTg, l〇-5) fin m tM Instant renting parent> Flexural modulus (GPa) c- S mmw 钡/ s % Sf Burning time (sec) -26- 201211097 [Simple description of the drawing] Fig. 1 is a GPC chart of the polyvalent hydroxy resin A. Figure 2 is a GPC chart of the polyvalent hydroxy resin B. Figure 3 is a GPC chart of the polyvalent hydroxy resin C. Figure 4 is a GPC chart of the polyvalent hydroxy resin D. Fig. 5 is a GPC chart of the polyvalent hydroxy resin E. Fig. 6 is a GPC chart of the polyvalent hydroxy resin F. Fig. 7 is a GPC chart of the polyvalent hydroxy resin G. Figure 8 is a GPC chart of a polyvalent hydroxy resin oxime. Figure 9 is a GPC chart of epoxy resin ruthenium. Figure 10 is a GPC chart of epoxy resin B. Figure 11 is a GPC chart of epoxy resin C. Figure 12 is a GPC chart of epoxy resin D. Figure 13 is a GPC chart of epoxy resin E. -27- !;