經濟部智慧財產局員工消費合作社印製 576844 A7 ___B7 五、發明說明（2 ) ’特別是做爲良好電氣特性之玻璃環氧樹脂層合板、半導 體密封材料等之電氣電子材料亦被廣泛應用之。 電氣電子材料所使用之環氧樹脂成形材料中，除優良 之電氣特性，更需要良好之耐熱性、難燃性、耐水性、耐 濕性等’更有硬化性、成形物之強度等重要功能被嚴格要 求之。 針對此要求，特開昭6 4 — 7 9 2 5 3號公報中，以 ^胺變性苯酚漆用酚醛樹脂做爲環氧樹脂之硬化劑使用者 與以漆用酚醛苯酚樹脂做爲硬化劑使用時相比後，前者較 可提供良好之耐熱性、耐濕性、硬化性之密封材用之環氧 樹脂成形材料者。 又’於特開平8 — 3 1 1 4 2號公報、 特開平8 - 1 83827號公報、 特開平8 - 2 5 3 5 5 7號公報、. 特開平8 — 2 5 3 5 5 8號公報、 特開平8 — 2 5 3 5 5 9號公報、 特開平9一124897號公報、 特開平9 一 1 2 4 7 7 5號公報、 特開平10 — 152547號公報、 特開平1 〇 — 1 9 5 1 7 8號公報、 特開平10 — 306200號公報、 特開平1 〇 — 3 2 4 7 9 1號公報等中亦嘗試取得具良好 耐熱性、耐水性、難燃性之密封材、層合板用等環氧樹脂 成形材料、以具有苯酚性氫氧基之化合物與三嗪衍生物之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------訂·!---*----線 (請先閱讀背面之注意項再濟寫本頁) -5- 經濟部智慧財產局員工消費合作社印製 576844 A7 _ B7 五、發明說明（3 ) 混合物及其反應物做爲環氧樹脂硬化劑之使用亦被嘗試之 〇 惟，此嘗試仍無法充份取得良好之耐熱性、耐水性， 且’成形物之強度亦不足、硬化性不良等問題均在。 本發明目的係提供一種具良好耐熱性、耐水性、難燃 性、強度、硬化性等之酚-胺縮合樹脂者。 本發明其他目的係提供一種具良好耐熱性、耐水性、 難燃性、強度、硬化性等之酚-胺縮合樹脂可有效製造且 生產性良好之酚-胺縮合樹脂之製造方法者。 本發明之另外目的係提供具良好耐熱性、耐水性、耐 濕性、難燃性、強度、硬化性等之環氧樹脂組成物者。 本發明更有其他目的係提供一種製造具良好耐熱性、 難燃性、耐水性、耐濕性、強度、硬化性等之層合板所使 用之預漬體及使用預漬體後取得之層合板者。 本發明係有關由苯酚衍生物、醛及三嗪衍生物所成之 縮合物者，數平均分子量（Μη )與重量平均分子量（ Mw)之比Mw/Mn爲1·6〜15之酚一胺縮合樹脂 者。 又’本發明係有關苯酚衍生物與醛之縮合物存在下， 三嗪衍生物及醛相互反應者爲特徵之由苯酚衍生物、醛及 三嗪衍生物所成之縮合物者，數平均分子量（Μη )與重 量平均分子量（Mw)之比Mw/Mn爲1 · 6〜1 5之 酚-胺縮合樹脂之製造方法者。 本發明係有關環氧樹脂及苯酚衍生物、醛及三嗪衍生 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ♦" --------------------訂 -----.----線 (請先閱讀背面之注音？W項再凑寫本頁) -6 - 576844 A7 B7 五、發明說明（4 ) 請 先 閱 讀 背 & 之 注 意 事_ 項 再 凑 本 頁 物所組成之縮合物者，數平均分子量（Μη )與重量平均 分子量（Mw)之比Mw/Mn爲1·6〜15之含酌一 胺縮合樹脂者爲特徵之環氧樹脂組成物者。 又，本發明係有關將該環氧樹脂組成物浸漬於薄片狀 基材後所成之預漬體者。 另外，本發明係有關該預漬體之複數片層合之層合物 或於此層合物之單面或雙面上重疊銅箔之銅箔層合物經加 熱成形後組成之層合板者。 〔發明實施之最佳形態〕 本發明酚-胺縮合樹脂係由苯酚衍生物、醛及三嗪衍 生物所組成之縮合物、數平均分子量（Μη)與重量平均 分子量（Mw)之比Mn/Mw爲1 · 6〜1 5，較佳者 爲1 · 8〜1 2者。當此比小於1 . 6則耐熱性、耐水性 、難燃性、強度、硬化性等均不良，反之，大於1 5則不 易合成。 經濟部智慧財產局員工消費合作社印製 本發明之酚-胺縮合樹脂之數平均分子量（Μη)( 於凝膠滲透色譜法下。進行測定後，換算成標準聚苯乙烯 之値，其重量平均分子量亦相同）以300〜1，500 者宜，350〜1，200者爲更佳，特別以380〜 1 ’ 0 0 0爲最理想。若小於3 0 0時所取得硬化物強度 則不良，反之，大於1，5 0 0則不易合成，處理亦不易 本發明酚-胺縮合樹脂之重量平均分子量（Mw)爲 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 576844 A7 ___ B7 五、發明說明（5 ) 650〜10，000者宜，700〜8，000者爲更 佳，特別以8 0 0〜9，0 0 0者爲最理想者。當小於 6 5 0則取得硬化物強度不良，反之，大於1 〇，〇 〇 〇 則合成不易，處理性亦差。 本發明酚-胺縮合樹脂由耐熱性、耐水性、難燃性、 強度等面觀之，對應標準聚苯乙烯之分子量2，0 5 0之 點（凝膠滲透色譜法下進行測定之曲線圖上）中，對應強 度a與分子量6 5 5之點之強度b相互之比a/b爲 0 · 2〜1 · 2者宜，較佳者爲0 · 3〜1 · 0者。 本發明酚-胺縮合樹脂其苯酚衍生物之2核體含量爲 1 5〜4 0重量％者宜，更佳者爲2 0〜4 0重量％者。 當小於2 0重量％時，軟化點有變高傾向，反之大於4 0 重量％則難燃性變差。 本發明酚一胺縮合樹脂其軟化點以4 0〜1 5 0 t者 宜，6 0〜1 0 0 °C者爲更佳。若小於4 CTC則硬化物強 度變差，大於1 5 0 °C則合成時作業進行不易。 由安全衛生面及臭味面觀之，含於本發明酚-胺縮合 樹脂之未反應苯酚衍生物以3重量％以下者宜。 又，本發明酚-胺縮合樹脂之氮含率以1〜2 0重量 %者由難燃性、易合成性等面觀之爲較理想者。 本發明酚-胺縮合樹脂以苯酚衍生物、醛及三氮衍生 物做爲必須原料者，藉由此等各原料相互反應後可製造之 〇 做爲苯酚衍生物之例如：苯酚、甲酚、二甲苯酚、乙 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） ------------4------- 丨訂-----------線j (請先閱讀背面之注音义事項再填寫本頁) -8- 經濟部智慧財產局員工消費合作社印製 576844 Α7 --- Β7 五、發明說明（6 ) 基苯酚、丁基苯酚、壬基苯酚、辛基苯酚等之烷基苯酚、 雙酚A、雙酚F、雙酚S、雷瑣辛、兒茶等多價酚、苯基 苯酚、胺酚、α -萘酚、/3 -萘酚、二羥基萘，此等化合 物鹵化之化合物等例，此等可單獨或2種以上合倂使用之 〇 做爲醛之例者如：甲醛、甲醛水、多聚甲醛等例。 三氮衍生物係分子中具有三氮核之化合物者，例如： 蜜胺、苯並鳥糞胺、甲基胍胺等之鳥糞胺衍生物、三聚氰 酸、甲基三聚氰酸酯等之三聚氰酸衍生物等例，此等可單 獨或2種以上合倂使用之。其中由耐熱性等面觀之，又， 以蜜胺、苯並鳥糞胺等之鳥糞胺衍生物爲更佳。 此等各原料之反應順序並無特別限定，例如：將苯酣 衍生物、醛及三氮衍生物一起混合後反應後製造酚一胺縮 合樹脂（第1方法）亦可，惟，由分子量控制之容易性之 面觀之，以苯酚衍生物與醛之縮合物之存在下，使三D秦衍: 生物及醛反應後製造酚-胺縮合樹脂（第2方法）者爲較 佳，此係首先使苯酚衍生物與醛相互反應後產生縮合物， 再於此添加三嗪衍生物及醛使反應後進行之。 (第1方法）中，各原料之使用比例係當1莫耳苯_ 衍生物時，醛爲0·01〜0·9莫耳者宜，更佳者爲 0 · 0 5〜0 · 7莫耳。若小於0 · 0 1莫耳時，反應則 不足、分子量無法上昇、耐熱性、耐水性、難燃性、強g 、硬化性等有不良傾向，反之，大於0 · 9莫耳則合成φ 出現凝膠化傾向。另外，當1莫耳苯酚衍生物時，三η奉伤: 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） * 參 --------------------訂 ----------線 (請先閱讀背面之注咅？W項再凑寫本頁) -9 - 576844 A7 ---- B7 五、發明說明（7 ) 者宜，較佳者爲0·01〜 1莫耳時，則反應不足、分 、難燃性、強度、硬化性等 則耐熱性、混煉性等不良。 °C者宜，80〜170°C者 應不足、分子量降低、耐熱 硬化性等不良，反之，大於 衍生物之共縮含有不足傾向 〇 莫耳之苯酚衍生物時使用 耳之三甲胺、三乙胺等胺系 之鹼觸媒、磷酸、對一甲苯 反應系之pH爲1〜10者 請 先 閱 讀 背 面 之 注 意 事_ 項 再 填- 本 頁 I 訂 生物爲0.01〜0.9莫耳 〇 · 5莫耳者。若小於0 · 0 子量不上昇，耐熱性、耐水性 不良，反之，大於0.9莫耳 反應溫度以5 0 — 2 5 0 爲更佳。小於5 0 °C時，則反 性、耐水性、難燃性、強度、 2 5 〇 t則苯酚衍生物與三嗪 ’反應時間爲1〜3 0小時者 另外，必要時亦可針對1 0.00001 〜0.01 莫 觸媒、氫氧化鈉、氫氧化鉀等 磺酸、草酸等之酸觸媒。又， 線 經濟部智慧財產局員工消費合作社印製 如此，使苯酚衍生物、醛及三嗪衍生物相互反應後， 可於加熱減壓下去除未反應之苯酚衍生物、醛、水等；惟 ，其條件以其溫度爲80〜180 °C，壓力爲100 m m H g以下；理想者以6 0 m m H g以下，時間爲 0 · 5〜1 0小時者佳。 (第2方法）中，苯酚衍生物與醛反應後產生縮合物 時，其苯酚衍生物與醛之使用比例爲當1莫耳苯酚衍生物 時醛爲0 · 0 1〜2莫耳者宜，更佳者爲〇 · 〇5〜1莫 耳者。若小於0 · 0 1莫耳則反應不足，分子量無法上昇 、耐熱性、耐水性、難燃性、強度等不良，反之，大於2 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -10- 576844 A7 B7 i、發明說明（8 ) 莫耳則分子量太高，混煉性不良。 此反應溫度爲80〜220 °C者宜，100〜180 °C者更爲理想。若小於8 0 °C時，反應性則不足’生產性 不良，反之，大於2 5 0 °C則對於生產設備不利。反應時 間爲1〜3 0小時。 又，必要時亦可於1莫耳苯酚衍生物時使用 0 · 0000 1〜0 · 0 1莫耳之三甲胺、三乙胺等之胺 系觸媒、對-甲苯磺酸、草酸等之酸觸媒、氫氧化鈉、氨 等之鹼觸媒等。又，反應系之pH爲1〜10。 如此，使苯酚衍生物及醛相互反應後，必要時將未反 應之苯酚衍生物、醛、水等於加熱減壓下去除之，惟，其 條件爲溫度8 0〜2 2 0 °C者，較理想者爲1 0 0〜 180°C，壓力爲lOOmmHg以下，較佳者爲60 /·' m m H g以下，時間爲0 · 5〜1 0小時者宜。 於苯酚衍生物與醛之縮合物中添加三嗉衍生物及醛之 後，反應時三嗪衍生物及醛之使用比例係針對1 0 0 g之 苯酚衍生物、與醛三縮合物（加熱減壓下去除未反應之苯 酚衍生物）、醛、水等者，或末進行該去除者（此時，未 反應苯酚亦含縮合物之重量））時，三嗪衍生物爲3〜 5 0 g者宜，更佳者爲4〜3 0 g者。又，醛針對1 〇 〇 g之縮合物時爲5〜1 0 0 g者宜，更佳者爲6〜5 0 g 者。三嗪衍生物及醛於上述範圍者最後取得之酚-胺縮合 樹脂之分子量分佈、氮含量可容易調整其所期待之範圍者 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------—— (請先閱讀背面之注音？•事項再琅寫本頁) 訂----*----線j 經濟部智慧財產局員工消費合作社印製 11 576844 A7 B7 五、發明說明（9 ) 請 先 閱 讀 背 面 之 注 意 事_ 項 再 凑 寫 本 頁 反應溫度以50〜250 °C者宜，80〜170 °C者 爲更佳。當小於5 0 °C時，則反應不足，分子量不提昇、 耐熱性、耐水性、難燃性、強度、硬化性等呈現不良傾向 。反之，大於2 5 0 °C則不利生產設備。反應時間爲1〜 3 0小時。 又，必要時亦可於1莫耳之苯酚衍生物時使用 0 · 0000 1〜0 · 0 1莫耳之三甲胺、三乙胺等胺系 觸媒、草酸等酸觸媒。另外，反應系之pH爲1〜1〇者 苯酚衍生 後，可於加熱 ，惟，其條件 m m H g以下 0 · 5 〜1 0 如此取得 合無機塡充劑 強度、難燃性 、粘合劑、密 氧樹脂組成物 做爲本發 用苯酚漆用酚 型環氧樹脂、 之環氧樹脂， 使用均可。 經濟部智慧財產局員工消費合作社印製 物與醛之縮合物與三嗪衍生物及醛相互反應 減壓下去除未反應之苯酚衍生物、醛、水等 爲溫度80〜180 °C者，壓力100 者，較佳者爲6 0 m m H g以下，時間以 小時者。 之酚-胺縮合樹脂配合環氧樹脂，必要時配 、硬化促進劑等之後，可做爲用於耐熱性、 等良好之成形材料、摩擦材、塗料、塗層材 封材、層合材、FRP及碳製品原料等之環 〇 明環氧樹脂組成物所使用之環氧樹脂者可使 醛樹脂、甲酚漆用酚醛型環氧樹脂、雙酚A 雙酚F型環氧樹脂、脂肪族環氧樹脂等一般 其他並無特別限定，此等可單獨或數種合倂 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -12- 576844 A7 --- B7 五、發明說明（10 ) (請先閱讀背面之注咅？事項再瘡寫本頁) 對於環氧樹脂之酚-胺縮合樹脂之配合量並無特別限 定’通常當1 0 0重量份之環氧樹脂時以2 0〜2 0 0重 量份者宜，更佳者爲5 0〜1 5 0重量份。若酚一胺樹脂 之配合量大於2 0 0重量份時，則成形物之耐水性、耐濕 性等特性將降低，反之，小於2 0重量份則反應性、強度 、難燃性等特性將降低。 本發明環氧樹脂組成物中，爲附與難燃效果之目的可 配合磷酸、磷酸酯、含鹵磷酸酯、縮合磷酸酯、聚磷酸酯 等含磷化合物者。含磷化合物針對1 〇 〇重量份之環氧樹 脂以1 0 0重量份以下之比例配合者宜。當配合量大於 1 0 0重量份則成形物之吸水率將變高，耐水性、耐濕性 等特性降低，較佳者以2 0〜1 0 0重量份配合之。又， 未配合含磷化合物時，比起未配合者，其成形物之難燃性 雖降低，卻不影響其他特性。 經濟部智慧財產局員工消費合作社印製 本發明環氧樹脂組成物中可適當倂用無機塡充材、硬 化促進劑。做爲無機塡充材者如：二氧化矽、石英玻璃粉 、碳酸鈣、矽酸鈣、鋁氧粉、氫氧化鋁、氫氧化鎂、粘土 、雲母、玻璃纖維等例。使用此等時，通常當1 0 0重量 份之環氧樹脂時爲3 0 0重量份以下使用之。較理想者爲 100〜300重量份者。又，硬化促進劑之例如：2-乙基一 4 一甲基咪唑等咪唑類、3級胺、B F 3 -胺絡合物 、有機磷類等例。此等當1 0 0重量份之環氧樹脂時以 0 · 0 1〜2 · 0重量份使用者宜。 本發明環氧樹脂組成物於玻璃布、玻璃不織布之薄片 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -13- 576844 A7 __ B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（11 ) 狀基材中必要時浸漬 之預漬體。所使用環 無特別限定。例如針 之樹脂固形份以1 〇 將此預漬體藉由 單面或雙面重疊銅箔 得貼銅層合板等之層 以下以本發明之 發明，惟，本發明並 重量份，％代表重量 甲苯、甲醇等溶劑後，取得層合板用 氧樹脂組成物之量依條件適當選取， 對薄片狀基材總計其環氧樹脂組成物 〜9 0重量％使用之。 於複數片層合之層合物或此層合物之 之銅箔層合物進行加熱成形後，可取 合板。 實施例及其比較例顯示更具體說明本 非僅限於此實施例中。例中之份即指 %之意。 (酚-胺縮合樹脂之合成） 合成例1 於附 9 4 g ( 之3 7 % 流脫水之 °C下進行 m m H g 後，取得 0.06 3 7 %甲 於1 4 0 、未反應 有攪拌器 1莫耳） 甲醛水後 同時昇溫 反應6小 之減壓下 2 1.7 4莫耳） 醛水後， °C下以6 甲醛及水 、回流冷卻 之苯酚、及 ，以 1 0 % 至 1 2 0 t： 時。之後， 去除未反應 g之苯酚樹 之蜜胺、2 於 1 0 0 〇C 0 m m H g 。所精製之 器及溫度計之燒 3 2 · 4 g ( 0 草酸調整P Η爲 進行8小時後， 於1 2 CTC下以 之苯酚、未反應 脂。更加入8 . 4 · 3 g ( 0 · 下進行反應8小 之減壓下去除未 酚-胺縮合樹脂 瓶中置入 • 4莫耳） 2之後，回 再於1 2 0 6 0 之甲醛及水 0 g ( 3莫耳）之 時。之後， 反應之苯酚 請 先 閱 讀 背 面 之 注 盡· 事 項 再 填· 本 頁 I I I I I 訂 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -14 - 576844 A7 B7 五、發明說明（12 )Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 576844 A7 ___B7 V. Description of the Invention (2) ’Electrical and electronic materials such as glass epoxy laminates and semiconductor sealing materials, which are good electrical properties, are also widely used. Among the epoxy resin molding materials used in electrical and electronic materials, in addition to excellent electrical characteristics, good heat resistance, flame retardancy, water resistance, moisture resistance, etc. are required. They also have important functions such as hardening and strength of the molded product. Be strictly required. In response to this requirement, Japanese Patent Application Laid-Open No. Sho 6 4-7 9 2 5 3 uses phenol modified phenolic resin for amine resin as hardener for epoxy resin and phenolic phenolic resin for lacquer as hardener. Compared with later, the former is more suitable for providing epoxy resin molding materials for sealing materials with good heat resistance, moisture resistance, and hardenability. Also disclosed in Japanese Unexamined Patent Publication No. 8-3 1 1 4 2, Japanese Unexamined Patent Publication No. 8-1 83827, Japanese Unexamined Patent Publication No. 8-2 5 3 5 5 7, Japanese Unexamined Patent Publication No. 8-2 5 3 5 5 Japanese Unexamined Patent Publication No. 8 — 2 5 3 5 5 9, Japanese Unexamined Patent Publication No. 9-124897, Japanese Unexamined Patent Publication No. 9 1 1 4 4 7 7 Japanese Unexamined Patent Publication No. 10 — 152547, Japanese Unexamined Patent Publication No. 10- 1 9 Japanese Unexamined Patent Publication No. 5 1 7, Japanese Unexamined Patent Publication No. 10-306200, Japanese Unexamined Patent Publication No. 10- 3 2 4 7 9 and other attempts have also been made to obtain sealing materials and laminates having good heat resistance, water resistance, and flame resistance. With the epoxy resin molding materials, the paper size of the compound with phenolic hydroxyl groups and triazine derivatives is applicable to China National Standard (CNS) A4 (210 X 297 mm) -------- Order! --- * ---- line (please read the note on the back before writing this page) -5- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 576844 A7 _ B7 V. Description of Invention (3) The use of mixtures and their reactants as epoxy hardeners has also been tried. However, this attempt has not been able to fully achieve good heat resistance and water resistance, and There are also problems such as insufficient strength of the molded article and poor curing properties. The object of the present invention is to provide a phenol-amine condensation resin having good heat resistance, water resistance, flame retardancy, strength, hardenability, and the like. Another object of the present invention is to provide a method for producing a phenol-amine condensation resin having good heat resistance, water resistance, flame resistance, strength, hardening properties, and the like, which can be efficiently produced and has good productivity. Another object of the present invention is to provide an epoxy resin composition having good heat resistance, water resistance, moisture resistance, flame retardancy, strength, hardenability, and the like. The present invention has still other objects to provide a pre-stained body used for manufacturing a laminated board having good heat resistance, flame resistance, water resistance, moisture resistance, strength, hardening and the like, and a laminated board obtained after using the pre-stained body. By. The present invention relates to a phenol monoamine having a condensate formed from a phenol derivative, an aldehyde, and a triazine derivative, and having a ratio of a number average molecular weight (Mη) to a weight average molecular weight (Mw) Mw / Mn of 1.6 to 15 Condensation resin. In addition, the present invention relates to a condensate formed by a phenol derivative, an aldehyde and a triazine derivative which is characterized by a reaction between a triazine derivative and an aldehyde in the presence of a condensate of a phenol derivative and an aldehyde. The number-average molecular weight A method for producing a phenol-amine condensation resin having a ratio (Mη) to a weight average molecular weight (Mw) of Mw / Mn of 1.6 to 15. The present invention relates to epoxy resin and phenol derivatives, aldehyde and triazine derivatives. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm). ♦ " ----------- --------- Order -----.---- line (please read the phonetic on the back? W to write this page) -6-576844 A7 B7 V. Description of the invention (4) Please read back & Precautions _ before condensing the condensate of this page. The ratio of the number average molecular weight (Mη) to the weight average molecular weight (Mw) Mw / Mn is 1.6 ~ 15. Monoamine condensation resin is characterized by epoxy resin composition. The present invention relates to a prepreg formed by immersing the epoxy resin composition in a sheet-like substrate. In addition, the present invention relates to a laminate in which a plurality of laminated sheets of the prestained body or a copper foil laminate in which copper foil is overlapped on one or both sides of the laminate is formed by heating. . [The best form of the invention] The phenol-amine condensation resin of the present invention is a condensate composed of a phenol derivative, an aldehyde and a triazine derivative, and a ratio of a number average molecular weight (Mη) to a weight average molecular weight (Mw) Mn / Mw is from 1 · 6 to 15 and more preferably from 1 · 8 to 12. When this ratio is less than 1.6, heat resistance, water resistance, flame retardancy, strength, hardenability, etc. are all inferior. On the other hand, if it is more than 15, it is difficult to synthesize. The number-average molecular weight (Mη) of the phenol-amine condensation resin of the present invention is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (under gel permeation chromatography. After measurement, it is converted into a standard polystyrene resin, and its weight average The molecular weight is also the same.) 300 ~ 1,500 is preferred, 350 ~ 1,200 is more preferred, and 380 ~ 1'0 0 0 is most preferred. If the strength of the hardened material obtained is less than 300, it is not good. On the contrary, it is not easy to synthesize more than 1,500, and it is not easy to handle and handle. The weight average molecular weight (Mw) of the phenol-amine condensation resin of the present invention is based on the paper standard. Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 576844 A7 ___ B7 V. Description of the invention (5) 650 ~ 10,000, preferably 700 ~ 8,000, more Good, especially those with 8 ~ 9, 0 0 as the most ideal. When it is less than 6,50, the strength of the hardened material is poor. On the other hand, when it is more than 1,000,000, the synthesis is not easy, and the handleability is also poor. The phenol-amine condensation resin of the present invention has a heat resistance, water resistance, flame retardancy, strength and other aspects, and corresponds to a molecular weight of standard polystyrene of 2,0 50 (a graph of measurement under gel permeation chromatography) In the above), the ratio a / b of the intensity b corresponding to the intensity a and the point of molecular weight 6 5 5 is 0 · 2 ~ 1 · 2, and more preferably 0 · 3 ~ 1 · 0. The phenol-amine condensation resin of the present invention preferably has a nucleus content of 15 to 40% by weight of the phenol derivative, and more preferably 20 to 40% by weight. When it is less than 20% by weight, the softening point tends to be high, and when it is more than 40% by weight, the flame retardancy is deteriorated. The phenol-amine condensation resin of the present invention preferably has a softening point of 40 to 150 t, and more preferably 60 to 100 ° C. If it is less than 4 CTC, the strength of the hardened material will be deteriorated, and if it is more than 150 ° C, the work will not be easy during synthesis. From the viewpoints of safety and health, and odor, the unreacted phenol derivative contained in the phenol-amine condensation resin of the present invention is preferably 3% by weight or less. The nitrogen content of the phenol-amine condensation resin of the present invention is preferably 1 to 20% by weight from the aspects of flame retardancy and ease of synthesis. The phenol-amine condensation resin of the present invention uses a phenol derivative, an aldehyde, and a triazine derivative as essential raw materials, and can be manufactured by reacting these raw materials with each other. As examples of phenol derivatives: phenol, cresol, The size of xylenol and ethyl paper is applicable to China National Standard (CNS) A4 (210 X 297 public love) ------------ 4 ------- 丨 order ---- ------- line j (please read the note and meaning on the back before filling out this page) -8- printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 576844 Α7 --- Β7 V. Description of Invention (6) Alkyl phenols such as phenol, butylphenol, nonylphenol, octylphenol, bisphenol A, bisphenol F, bisphenol S, raloxine, polyvalent phenols such as catechin, phenylphenol, aminephenol, α -Naphthol, / 3-naphthol, dihydroxynaphthalene, halogenated compounds of these compounds, etc. These can be used alone or in combination of two or more. Examples of aldehydes are: formaldehyde, formalin, Examples of polyoxymethylene. Trinitrogen derivatives are compounds with a trinitrogen nucleus in the molecule, for example: guanamine derivatives such as melamine, benzoguanamine, methylguanamine, cyanuric acid, methyl cyanurate Examples of cyanuric acid derivatives and the like can be used alone or in combination of two or more kinds. Among them, heat resistance and the like, and guanamine derivatives such as melamine and benzoguanamine are more preferable. The reaction order of these raw materials is not particularly limited. For example, the phenol-amine condensation resin (the first method) may be produced by mixing the phenylhydrazone derivative, the aldehyde, and the triazine derivative together and reacting, but it is controlled by the molecular weight. In terms of easiness, in the presence of a condensate of a phenol derivative and an aldehyde, it is better to make three-D Qin Yan: biological and aldehyde reaction to produce a phenol-amine condensation resin (second method), this system First, a phenol derivative and an aldehyde are reacted with each other to produce a condensate, and then a triazine derivative and an aldehyde are added thereto to perform the reaction. In the first method, when the ratio of each raw material is 1 mole benzene derivative, the aldehyde is preferably from 0.01 to 0.9 mole, and more preferably from 0 to 0.5 to 0 to 7 mole. ear. If it is less than 0.01 mole, the reaction will be insufficient, the molecular weight will not rise, heat resistance, water resistance, flame retardancy, strong g, hardening and other bad tendencies. On the other hand, if it is greater than 0.9 mole, the synthetic φ will appear. Gelation tendency. In addition, when 1 mol phenol derivative is used, three η is injured: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) * see ------------- ------- Order ---------- line (please read the note on the back? W to write this page) -9-576844 A7 ---- B7 V. Description of the invention (7) It is preferable, and when it is 0.01 to 1 mol, the reaction is insufficient, and the flame retardancy, strength, and hardening properties are poor, such as heat resistance and kneading properties. ° C is suitable, 80 ~ 170 ° C should be inadequate, molecular weight lowered, heat-hardening resistance, etc. Conversely, greater than the co-condensation of the derivative contains a tendency to be inadequate. Use trimethylamine and triethyl for phenol derivatives For amines such as amines, alkali catalysts, phosphoric acid, and p-toluene, the pH is 1 ~ 10, please read the notes on the back _ item, then fill in-on page I. The ordering organism is 0.01 ~ 0.9 mole Ears. If the amount is less than 0 · 0, the heat resistance and water resistance are not good. On the other hand, the reaction temperature is more than 0.9 mol, preferably 50-2 50. When the temperature is lower than 50 ° C, the reactivity, water resistance, flame retardancy, strength, and 250 kt are the reaction time of phenol derivative and triazine 'is 1 ~ 30 hours. In addition, if necessary, it can also target 1 0.00001 ~ 0.01 Mo catalyst, acid catalysts such as sulfonic acid such as sodium hydroxide and potassium hydroxide, and oxalic acid. In addition, the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Online Economics has printed this so that after reacting phenol derivatives, aldehydes and triazine derivatives with each other, unreacted phenol derivatives, aldehydes, water, etc. can be removed under heat and pressure; The conditions are that the temperature is 80 ~ 180 ° C, the pressure is 100 mm H g or less; ideally, it is 60 mm H g or less, and the time is 0 · 5 ~ 10 hours. In the second method, when a phenol derivative is reacted with an aldehyde to produce a condensate, the use ratio of the phenol derivative to the aldehyde is 0. 0 1 to 2 mol when the phenol derivative is 1 mol, More preferably, it is 0.5 to 1 mole. If it is less than 0 · 0 1 mol, the reaction is insufficient, the molecular weight cannot be increased, heat resistance, water resistance, flame resistance, strength and other defects, otherwise, the paper size is greater than 2 Chinese national standard (CNS) A4 (210 X 297) (Mm) -10- 576844 A7 B7 i. Description of the invention (8) Mol is too high in molecular weight and poor in kneading properties. The reaction temperature is preferably 80 ~ 220 ° C, more preferably 100 ~ 180 ° C. If the temperature is lower than 80 ° C, the reactivity will be insufficient, and the productivity will be poor. On the other hand, if it is higher than 250 ° C, it will be disadvantageous to the production equipment. The reaction time is 1 to 30 hours. In addition, when necessary, it is also possible to use amine catalysts such as trimethylamine, triethylamine, p-toluenesulfonic acid, and oxalic acid in the presence of 1 mole of phenol derivatives. Catalysts, alkali catalysts such as sodium hydroxide, ammonia, etc. The pH of the reaction system is 1 to 10. In this way, after the phenol derivative and aldehyde are reacted with each other, if necessary, the unreacted phenol derivative, aldehyde, and water are removed under heating and reduced pressure. However, the condition is that the temperature is 80 ° to 220 ° C, which is Ideally, it is 100 to 180 ° C, and the pressure is 100 mmHg or less, preferably 60 / · 'mm H g or less, and the time is preferably 0.5 to 10 hours. After adding triamidine derivative and aldehyde to the condensate of phenol derivative and aldehyde, the proportion of triazine derivative and aldehyde used in the reaction is 100 g of phenol derivative and aldehyde tricondensate (heating and decompressing) When the unreacted phenol derivative), aldehyde, water, etc. are removed, or the removal is not performed (in this case, the unreacted phenol also contains the weight of the condensate), the triazine derivative is 3 to 50 g It is better, more preferably 4 to 30 g. In addition, when the aldehyde is directed to a condensate of 100 g, it is preferably 5 to 100 g, and more preferably 6 to 50 g. The molecular weight distribution and nitrogen content of the phenol-amine condensation resin finally obtained by the triazine derivatives and aldehydes in the above range can be easily adjusted in the expected range. This paper size applies the Chinese National Standard (CNS) A4 (210 X 297) (Li) ----------------- (Please read the phonetic on the back? • Matters before writing this page) Order ---- * ---- line j Intellectual Property Bureau of the Ministry of Economic Affairs Printed by employee consumer cooperatives 11 576844 A7 B7 V. Description of the invention (9) Please read the notes on the back _ item before writing the page. The reaction temperature should be 50 ~ 250 ° C, preferably 80 ~ 170 ° C. . When it is lower than 50 ° C, the reaction is insufficient, the molecular weight does not increase, heat resistance, water resistance, flame retardancy, strength, hardenability, etc. exhibit a poor tendency. Conversely, greater than 250 ° C is disadvantageous to production equipment. The reaction time is 1 to 30 hours. When necessary, it is also possible to use amine catalysts such as trimethylamine and triethylamine, and acid catalysts such as oxalic acid in the case of 1 mole of phenol derivatives. In addition, after the reaction system has a pH of 1 to 10, it can be heated after derivatization with phenol. However, the conditions are below mm H g 0 · 5 ~ 1 0. In this way, the strength, flame retardancy, and adhesive of the inorganic filler are obtained. The dense oxygen resin composition can be used as the phenol type epoxy resin for the phenol paint used in the present invention, or the epoxy resin. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer consortium, printed products, condensates of aldehydes, triazine derivatives, and aldehydes interact with each other to remove unreacted phenol derivatives, aldehydes, water, etc. under reduced pressure. 100, preferably less than 60 mm H g, and time in hours. The phenol-amine condensation resin is mixed with epoxy resin, and if necessary, a hardening accelerator, etc., it can be used as a molding material, friction material, coating material, coating material sealing material, laminated material, etc. with good heat resistance. Rings such as FRP and carbon products. The epoxy resin used in the epoxy resin composition can be aldehyde resin, phenolic epoxy resin for cresol paint, bisphenol A, bisphenol F epoxy resin, and aliphatic. There are no special restrictions on epoxy resins, etc. These can be used individually or in combination. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -12- 576844 A7 --- B7 V. Description of the invention (10) (Please read the note on the back? Matters before you write this page) There is no particular limitation on the blending amount of the phenol-amine condensation resin for epoxy resins. Usually when it is 100 parts by weight of epoxy resin In this case, it is preferably 20 to 200 parts by weight, and more preferably 50 to 150 parts by weight. If the blending amount of the phenol-amine resin is more than 200 parts by weight, the properties such as water resistance and moisture resistance of the molded article will be reduced. On the other hand, if it is less than 20 parts by weight, the properties such as reactivity, strength, and flame resistance will be reduced. reduce. In the epoxy resin composition of the present invention, phosphorous compounds such as phosphoric acid, phosphoric acid esters, halogenated phosphoric acid esters, condensed phosphoric acid esters, and polyphosphoric acid esters can be blended for the purpose of imparting a flame retardant effect. The phosphorus-containing compound is preferably blended in an amount of 100 parts by weight or less with respect to 100 parts by weight of the epoxy resin. When the compounding amount is more than 100 parts by weight, the water absorption of the formed article will be high, and the water resistance and moisture resistance characteristics will be lowered. It is preferable to mix it with 20 to 100 parts by weight. When the phosphorus-containing compound is not blended, the flame retardancy of the molded product is lower than that of the non-blended compound, but other characteristics are not affected. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In the epoxy resin composition of the present invention, inorganic fillers and hardening accelerators can be appropriately used. As inorganic filler materials such as: silicon dioxide, quartz glass powder, calcium carbonate, calcium silicate, aluminum oxide powder, aluminum hydroxide, magnesium hydroxide, clay, mica, glass fiber and other examples. When using these, usually when the epoxy resin is 100 parts by weight, it is used in an amount of 300 parts by weight or less. More preferably, it is 100 to 300 parts by weight. In addition, examples of the hardening accelerator include imidazoles such as 2-ethyl-4-methylimidazole, tertiary amines, B F 3 -amine complexes, and organic phosphorus. When 100 parts by weight of epoxy resin is used, 0 · 0 1 ~ 2 · 0 parts by weight are suitable for users. The epoxy resin composition of the present invention is applied to a sheet of glass cloth or glass non-woven cloth. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 5. Preparation of the invention (11) Pre-stained body impregnated in a substrate as necessary. The ring used is not particularly limited. For example, the solid content of the needle is 10%. This pre-stained body is laminated with copper foil on one or both sides to obtain copper laminates. The invention of the present invention is as follows. However, the present invention does not include parts by weight.% Represents weight. After the solvent such as toluene and methanol, the amount of the oxygen resin composition for the laminated board is appropriately selected according to the conditions, and the epoxy resin composition is used in a total amount of ~ 90% by weight for the sheet-like substrate. After a plurality of laminated laminates or copper foil laminates of this laminate are heat-formed, the laminate may be obtained. The examples and their comparative examples are shown in more detail. The present invention is not limited to these examples. The part in the example means%. (Synthesis of Phenol-Amine Condensation Resin) Synthesis Example 1 After carrying out mm H g at ° C with 9 4 g (of 37% flow dehydration), 0.06 3 7% of formic acid was obtained at 1 40 and unreacted with a stirrer. 1 mol) After the formaldehyde water is heated at the same time, the reaction temperature is 6 hours under reduced pressure 2 1.7 4 mol) After the aldehyde water, the temperature is 6 ° C with formaldehyde and water, phenol cooled under reflux, and 10% to 1 2 0 t: hour. After that, unreacted g of melamine in the phenol tree, 2 at 100 mc0 Hm. The refined device and thermometer burned 3 2 · 4 g (0 oxalic acid adjusted P Η for 8 hours, then phenol and unreacted fat at 1 2 CTC. 8.4 · 3 g (0 · under Perform the reaction for 8 hours under reduced pressure to remove the non-phenol-amine condensation resin bottle and put it in 4 mol) 2. Then, return to 1 2 0 60 formaldehyde and water at 0 g (3 mol). After that, For the reaction of phenol, please read the notes on the back of the page, and then fill in the notes. IIIII of this page The paper size of this edition applies to China National Standard (CNS) A4 (210 X 297 mm) -14-576844 A7 B7 V. Description of the invention ( 12)
0 °C 3 5 · 6 g，軟化點爲1 請 先 閱 讀 背 之 注 I 項 再 填- 本 頁 口 於附有擾泮器、回流冷卻益及溫度g十之燒瓶中置入 94g (1莫耳）之苯酚、48g (0 · 6莫耳）之37 %甲醛水後，以1 〇 %草酸調整P Η爲2之後，回流脫水 之同時，昇溫至1 4 0 °C進行8小時後，再於1 4 0 °C下 進行反應6小時。更加入4 · 345g (0 · 034莫耳 )之蜜胺及8 · 〇g (0 · 1莫耳）之37%甲醛水後， 回流脫水之同時昇溫至1 4 0 °C進行4小時後，再於 1 4 0 °C下進行反應8小時。之後，於1 4 0 °C下以6 0 mmH g之減壓下去除未反應之醛及水。精製之酚-胺縮 合樹脂量爲72g，軟化點爲90°C。 合成例3 經濟部智慧財產局員工消費合作社印製 於附有攪拌器、回流冷卻器及溫度計之燒瓶中加入 94g (1莫耳）之苯酚、64 · 8g (0 · 8莫耳）之 3 7%甲醛水，以1 〇%草酸調整pH爲2，回流脫水之 同時昇温至1 4 0 °C進行8小時，再於1 4 0 °C下進行反 應6小時。之後，於1 4 0 °C下以6 0 m m H g之減壓下 去除未反應之苯酚，未反應之甲醛及水之後，取得 53 · 8g苯酚樹脂。更置入20 · 6g (0 · 1 1莫耳 )之苯並鳥糞胺、33. 6g (0.42莫耳）之37% 甲醛水後，於1 0 0 °C下進行8小時反應之。之後，於 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15- 576844 A7 -—_ B7 五、發明說明（13 ) 1 4 〇°C下以6 OmmHg之減壓下去除未反應之醛及水 °精製之酚一胺縮合樹脂量爲83 · 2g，軟化點爲 1 〇 〇 oc。 合成例4 於附有 9 4 g ( 1 3 7 %甲醛 水之同時昇 進行反應6 減壓下去除 5 3 · 8 g 耳）之蜜胺 ,16.0 1 0 0 °C 下 m m H g 之 樹脂之量爲 攪拌器、回 莫耳）之苯 水後，以1 溫至1 4 0 小時。之後 未反應苯酚 之苯酚樹脂 、4 · 3 g g ( 0 . 2 進行反應8 減壓下去除 8 8 . 6 g 請 先 閱 讀 背 面 之 注 意 事 項 再 凑 本 頁 流冷卻器及溫度計之燒瓶中置入 酚、84.8g(〇.8莫耳）之 〇%草酸調整pH爲2後，回流脫 °C進行8小時後，再於1 4 0 °C下 ，於140°C下以6〇mmHg之 ，未反應甲醛及水之後，取得 。更加入2.9g(0.023莫 (0.023莫耳）之苯並烏糞胺 莫耳）之3 7 %甲醛水後，於 小時。之後，於1 4 0 °C下以6 0 未反應醛及水。精製之酚-胺縮合 ，軟化點爲9 0 °C者。 經濟部智慧財產局員工消費合作社印製 合成例5 於附有攪拌器、回流冷卻器及溫度計之燒瓶中置入 94g (1莫耳）之苯酚、32 · 4g (〇 . 4莫耳）之 3 7 %甲醛水後，以三乙胺調整p Η爲9後，回流脫水之 同時，昇溫至1 4 0 °C進行8小時後，再於1 4 0 °C下進 行反應6小時。之後，於1 4 0 C下以6 0 m m H g之減 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -16- 576844 A7 _ B7 五、發明說明（14 ) 壓下去除未反應之苯酚、未反應之甲醛及水後，取得 21 · 7g之苯酚樹脂。更加入1 · 89g (〇 · 015 莫耳）之蜜胺、3·2g(0·04莫耳）之37%甲醛 水，以草酸調整p Η爲2後，於1 0 0 °C下進行反應8小 時。之後，於1 4 0 t：下以6 0 m m H g之減壓下去除未 反應之醛及水。精製之酚-胺縮合樹脂之量爲18·5g ’軟化點爲9 5 °C者。 比較合成例1 於附攪拌器、回流冷卻器及溫度計之燒瓶中加入9 4 g (1莫耳）之苯酚、25 . lg (0 · 3莫耳）之甲醛 水、4 .34g之蜜胺（0.034莫耳），以三乙胺調 整P Η爲8後，回流脫水之同時昇溫至1 4 0 t進行4小 時後，再於1 4 0 t下進行反應5小時。之後，於1 4 0 t下以6OmmHg之減壓下去除未反應醛、未反應苯酚 及水。精製之樹脂量爲40 · 8g，軟化點爲80 °C者。 比較合成例2 於附攪拌器、回流冷卻器及溫度計之燒瓶中置入9 4 g之苯酚、36g之41·5%之甲醛水、及〇·47g 之三乙胺，於8 0 °C下進行反應3小時。再加入1 4 g之 蜜胺、1 4 g之苯並鳥糞胺後’進行反應2小時之後，常 壓下去除水同時昇溫至1 8 0 °C進行2小時，再於6 0 m m H g之減壓下去除未反應之苯酚後’取得示於特開平 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公爱） 請 先 閱 讀 背 面 之 注 意- 事 項 再 填· % 本 頁 I I I I I 訂 經濟部智慧財產局員工消費合作社印製 -17- 576844 A7 _ B7 五、發明說明（15 ) 8〜3 1 1 42號公報（實施例3)之樹脂。 合成例1〜5及比較合成例1〜2取得之樹脂數平均 分子量、重量平均分子量、重量平均分子量/數平均分子 量、標準聚苯乙烯之分子量2 · 0 5 0所對應之點（保持 時間=2 6 m i η )中強度a與分子量6 5 5所對點之點 (保持時間=3〇mi η)中強度b之比a/b，苯酚2 核體含量、軟化點及氮含有率之結果示於表2。 其中，數平均分子量、重量平均分子量係利用凝膠滲 透色譜法以標準聚苯乙烯藉由檢量線換算後算取之。又， 重量平均分子量/數平均分子量、苯酚2核體量及未反應 苯酚量亦以凝膠滲透色譜法，於面積法算取之。 又，由軟化點與元素分析法求取氮含量之結果示於表 另外，凝膠滲透色譜法係由以下條件進行之。 柱體：凝膠包（日立化成工業（股份公司）製） GL-R4 2 0+GL-R4 3 0+GL-R4 4 0 柱體溫度：4 0 t：0 ° C 3 5 · 6 g, softening point is 1. Please read the note I of the back first and then fill in-the mouth of this page is placed in a flask with a scrambler, reflux cooling temperature and temperature g ten (1 Mo Ear) of phenol, 48 g (0.6 mol) of 37% formaldehyde water, adjust P Η to 2 with 10% oxalic acid, and then dehydrate under reflux while heating to 14 0 ° C for 8 hours, then The reaction was carried out at 140 ° C for 6 hours. After adding 4.345 g (0. 034 mol) of melamine and 8. 0 g (0. 1 mol) of 37% formaldehyde water, the solution was heated to 14 0 ° C while refluxing for 4 hours. The reaction was further carried out at 140 ° C for 8 hours. Thereafter, unreacted aldehyde and water were removed under a reduced pressure of 60 mmH g at 140 ° C. The amount of the purified phenol-amine condensation resin was 72 g, and the softening point was 90 ° C. Synthesis Example 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In a flask with a stirrer, reflux cooler and thermometer, 94 g (1 mole) of phenol, 64 · 8 g (0 · 8 mole) of 3 7 % Formaldehyde water, adjust the pH to 2 with 10% oxalic acid, and raise the temperature to 140 ° C for 8 hours while dehydrating under reflux, and then perform the reaction at 140 ° C for 6 hours. After that, unreacted phenol was removed at 140 ° C under a reduced pressure of 60 m m H g, and unreacted formaldehyde and water were then obtained to obtain 53.8 g of a phenol resin. After placing 20.6 g (0.11 mol) of benzoguanamine and 33.6 g (0.42 mol) of 37% formaldehyde in water, the reaction was performed at 100 ° C for 8 hours. After that, the Chinese standard (CNS) A4 specification (210 X 297 mm) is applied to this paper standard -15- 576844 A7 ----- B7 V. Description of the invention (13) 1 4 0 ° C decompression at 0 ° C The amount of the phenol-amine condensation resin purified by removing unreacted aldehyde and water ° was 83.2 g, and the softening point was 100 oc. Synthesis Example 4 A reaction was carried out with 94 g (1 37% formaldehyde in water) and 6 melamine was removed under reduced pressure. 5 3 · 8 g ears of melamine, 16.0 mm H g of resin at 100 ° C After measuring the amount of benzene in a stirrer, return the temperature to 1 to 140 hours. After that, the phenol resin with unreacted phenol and 4 · 3 gg (0.2 was reacted. 8 was removed under reduced pressure. 8 8. 6 g. Please read the precautions on the back before putting the phenol into the flask of the flow cooler and thermometer. 84.8 g (0.8 mole) of 0% oxalic acid after adjusting the pH to 2, after refluxing at ° C for 8 hours, and then at 140 ° C and 140 ° C at 60 mmHg. Obtained after reacting formaldehyde and water. After adding 2.9 g (0.023 mol (0.023 mol) of benzocotonamine mol) in 37% formaldehyde water, it was added after 1 hour. After that, it was cooled at 140 ° C to 60 0 Unreacted aldehydes and water. Refined phenol-amine condensation with a softening point of 90 ° C. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Synthesis Example 5 In a flask with a stirrer, reflux cooler, and thermometer After putting 94 g (1 mol) of phenol and 33.4 g (0.4 mol) of 37% formaldehyde in water, p Η was adjusted to 9 with triethylamine, and the temperature was raised to 1 4 while refluxing and dehydrating. After 8 hours at 0 ° C, the reaction is performed for 6 hours at 140 ° C. After that, the paper size is reduced by 60 mm H g at 140 ° C. National Standard (CNS) A4 (210 X 297 mm) -16- 576844 A7 _ B7 V. Description of the invention (14) After removing unreacted phenol, unreacted formaldehyde and water under pressure, obtain 21.7 g of Phenol resin. Add 1.89g (0.015 mol) of melamine and 3.2g (0.004 mol) of 37% formaldehyde water, adjust p Η to 2 with oxalic acid, and then at 100 ° C The reaction was carried out for 8 hours. After that, unreacted aldehyde and water were removed under a reduced pressure of 60 mm H g at 140 t: The amount of the refined phenol-amine condensation resin was 18.5 g. The softening point was 9 5 ° C. Comparative Synthesis Example 1 In a flask with a stirrer, reflux cooler, and thermometer, 9 4 g (1 mol) of phenol, 25. lg (0 · 3 mol) of formaldehyde water, 4 .34g of melamine (0.034 moles), after adjusting P 乙 to 8 with triethylamine, the temperature was raised to 14 0 t while refluxing and dehydrating for 4 hours, and then the reaction was performed at 14 0 t for 5 hours. Remove unreacted aldehyde, unreacted phenol, and water under a reduced pressure of 60 mmHg at 14 0 t. The amount of refined resin is 40 · 8 g, and the softening point is 80 ° C. Comparative Synthesis Example 2 A flask of a reflux cooler and a thermometer was charged with 94 g of phenol, 36 g of 41.5% formaldehyde water, and 0.47 g of triethylamine, and the reaction was carried out at 80 ° C for 3 hours. After adding 14 g of melamine and 14 g of benzoguanamine, the reaction was performed for 2 hours. After removing water under normal pressure, the temperature was raised to 180 ° C for 2 hours, and then 60 mm H g After removing unreacted phenol under reduced pressure, the paper size shown in JP-A flat is applicable to Chinese National Standard (CNS) A4 (210 x 297 public love). Please read the note on the back first-matters to be filled in.% This page IIIII Ordered by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-17- 576844 A7 _ B7 V. Resin of the invention description (15) 8 ~ 3 1 1 42 (Example 3). Responsive points of Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 2 Average molecular weight, weight average molecular weight, weight average molecular weight / number average molecular weight, molecular weight of standard polystyrene 2 · 0 5 0 (Retention time = 2 6 mi η) The ratio a / b of the intensity b at the point opposite to the molecular weight 6 5 5 (holding time = 30 mi η), the results of the phenol 2 core content, softening point, and nitrogen content Shown in Table 2. Among them, the number average molecular weight and the weight average molecular weight are calculated by gel permeation chromatography with standard polystyrene and calculated by a calibration curve. The weight-average molecular weight / number-average molecular weight, the amount of phenol dinuclear bodies, and the amount of unreacted phenol were also calculated by gel permeation chromatography using the area method. The results of determining the nitrogen content by the softening point and elemental analysis are shown in the table. The gel permeation chromatography was performed under the following conditions. Column: gel pack (manufactured by Hitachi Chemical Industries, Ltd.) GL-R4 2 0 + GL-R4 3 0 + GL-R4 4 0 Column temperature: 4 0 t:
檢出器：R I 溶離液：四氫呋喃 流量：1·6ml/min 又，檢量線係使用表1所示之分子量之標準聚苯乙烯 (商品名T S K standard、東曹（股份公司）製），作成 橫軸取保持時間（分鐘）、縱軸取分子量之對數。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 請 先 閱 讀 背 面 之 注 意· 事 項 再 填 本 頁 訂 ▲ 經濟部智慧財產局員工消費合作社印製 -18- )76844 A7 B7 五、發明說明〇6 ) 美 1 番 分子量 - 2 0 1 8 6，0 0 0 ^__F — 4 4 3，9 0 0 __F — 1 1 0，3 0 0 2 5 0 0 2，8 0 0 A - 3 0 0 平均456 (5個部份爲578、 402 、370、266 及 162 經濟部智慧財產局員工消費合作社印制衣 B_ 2 項目 合成例 比較 合成 例1 比較 合成 例2 1 2 3 4 5 數平均分子量 710 470 770 740 500 340 510 重量平均分子量 6560 900 2770 3400 1300 470 730 重量平均分子量/數 平均分子量 9.3 1.8 3.6 4.5 2.6 1.3 1.4 a/b 0.8 0.6 0.9 0.6 0.5 0.03 0.16 苯酚2核體量 30 20 25 20 35 32 31 軟化點（°c ) 110 90 100 90 95 80 130 氮含有率（％) 15 4 9 4 6 7 23 氫氧基當量（％) 130 115 121 115 117 118 143 又，比較合成例1取得之酚-胺縮合樹脂及合成例1 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------訂 ----------線 (請先閱讀背面之注音仏事項再资寫本頁) 19- 576844 A7 _ B7 五、發明說明（17 ) 取得之酚-胺縮合樹脂之GP C圖表做爲圖1示之 應用例1 環氧基當量2 2 0、軟化點7 8 °C之甲酚漆用酚醛型 環氧樹脂1 〇 〇重量份配合製造例1所合成之蜜胺變性苯 酚樹脂50重量份、1·5重量份之苄甲胺、2重量份之 巴西棕櫚蠘、8重量份之三氧化銻、1·5重量份之炭黑 、3重量份之r —環氧丙氧基三甲氧基矽烷、3 6 0重量 份之熔融二氧化矽後，使用1 0 inch直徑之加熱滾輥，於 混煉溫度8 0 °C〜9 0 °C，混煉時間7分鐘之條件下進行 混煉。之後，利用朋來式粉碎機、粉碎後製成環氧樹脂成 形材料。其特性示於表4。 應用例2〜3及比較應用例1、2 與應用例1同法製成成形材料。其配合例如表3所示 。另外，此等特性示於表4。 又，塗膜之試驗方法如下。 (1 )凝膠時間；利用今中製作所（股份公司）製 J S R製Curast meter，於溫度1 8 0 °C下進行測定。 (2 )螺旋流動；依Ε Μ Μ I 1 - 6 6爲基準，於模 具溫度1 8 0 °C下，傳送壓7 0 K G F / C Μ 2下進行測 定。 (3) Tg ;使用理學電氣（股份公司）製ΤΜΑ裝 置，以溫度-熱膨脹曲線之屈撓點溫度做爲T g。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 請 先 閱 讀 背 之 注 $- 項 再 填” 寫 本 頁 I I I I I 訂 經濟部智慧財產局員工消費合作社印製 -20- 576844 A7 B7 五、發明說明（18 ) (4 )難燃性；依U L — 9 4爲基準藉由V B法進行 評定。（1 / 8 inch試驗片） (5 )懸背樑式衝擊；A S T Μ — D 2 5 6爲基準之 方法進行之。C V刻痕、1 / 8 inch試驗片） 請 先 閱 讀 背 面 之 注 意· 事 項 再 寫 本 頁 訂 線 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -21 - 576844 A7 B7 五、發明說明（19 ) 經濟部智慧財產局員工消費合作社印製 表 3 應用例 比較應用例 1 2 3 4 5 1 2 甲酚漆用酚醛型 環氧樹脂 100 100 100 100 100 100 100 合成例1之樹脂 50 一 _ 合成例2之樹脂 - 50 . - 肇 合成例3之樹脂 50 _ 晒 合成例4之樹脂 _ 50 合成例5之樹脂 _ 50 _ 比較合成例1之 樹脂 - - - - - 50 - 比較合成例2之 樹脂 - - - - - - 50 苄胺 1.5 1.5 1.5 1.5 1.5 1.5 1.5 巴西棕櫚蠟 2.0 2.0 2.0 2.0 2.0 2.0 2.0 三氧化銻 8.0 8.0 8.0 8.0 8.0 8.0 8.0 炭黑 1.5 1.5 1.5 1.5 1.5 1.5 1.5 r -環氧丙氧基三 甲氧基矽烷 3.0 3.0 3.0 3.0 3.0 3.0 3.0 熔融二氧化矽 360 360 360 360 360 360 360 ---------------- (請先閱讀背面之注音气事項再療寫本頁) 訂---------線一 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -22- 576844 A7 B7 五、發明說明㊇） 表 4 應用例 比較應用例 1 2 3 4 5 1 2 凝膠時間（秒） 25 28 35 30 40 60 60 螺旋流動（cm) 96 95 110 100 100 100 95 Tg(TMA)(°C ) 115 120 120 115 120 120 120 燃燒無焰時間（秒） 4.0 5.0 6.0 5.5 5.5 10.0 試驗火種之滴下 >fnrr ιΓιΓ J\\\ Μ 川N Μ M ^\\\ 4nr ΊΙΤΙΓ 燃燒 Μ j\\\ 判定 V-0 V-0 V-0 V-0 V-0 V-l 懸背樑式衝擊 (KG/CM) 15.0 14.0 14.9 15.0 14.0 14.5 14.5 請 先 閱 讀 背 面 之 注 意_ 事 項 再 寫 本 頁 經濟部智慧財產局員工消費合作社印製 實施例1 將1 0 脂、9 2重 0 . 1重量 之混合溶劑 將此混合溶 5 0重量％ 預漬體。此 銅箔，於壓 行加壓加熱 後，調整不揮發 液於玻璃布中使 浸漬之，於1 8 預漬體層合8片 力 4 0 k g / c 成形後，製成貼 實施例2〜7及比較例1〜5 0重量份之環氧當量11〇之雙酚A型環氧樹 量份之合成例1所合成之蜜胺變性苯酚樹脂、 份之2 —乙基一 4 一甲基咪唑溶於甲苯/甲醇 份6 0 %之混合溶液。之後， 樹脂固形份爲與玻璃布合計爲 〇°C下乾燥3分鐘之後，取得 後，更於兩面重疊3 5 //m之 m 2，溫度1 7 0 °C之條件下進 銅層合板。其特性示於表6。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -23- 576844 A7 ------ B7 五、發明說明) 與實施例1同法以表5之配合製成環氧樹脂組成物、 預漬體及貼銅層合板。此等特性如表6所示。 又，環氧樹脂組成物及貼銅層合板之試驗方法如下。 (1 )凝膠時間；使用今中製作所（股份公司）製 J S R製Curast meter，於溫度1 8 0 t：下進行測定之。 (2 ) T g ;使用精工Instur mants製Τ Μ A裝置，以 溫度-熱膨脹曲線之屈撓點溫度做爲T g。 (3 )柱腳強度；使用島津製作所性自動曲線圖 A G S - 1 〇 〇 B，進行測定之。 (4)壓力屈撓（PCT)試驗；於12〇°C， 1 0 0 % R Η之水蒸氣中所定時間（2，4，6小時）處 理後之吸水率。 (5 )耐濕耐焊錫性；將評定之P C Τ性（2 · 4小 時）試驗片於2 6 0 °C之焊錫浴中浸漬2 0秒後評定其外 dfctf 觀0 〇 ;無變化 Δ ;稍變色 ，出現膨脹 X ;變色， 明顯膨脹 經濟部智慧財產局員工消費合作社印製 (6 )難燃性；依U L — 9 4爲基準。藉由v b法進 行評定。（1 / 8 inch試驗片） 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） 24- 576844 A7 _B7 五、發明說明P2 ) 經濟部智慧財產局員工消費合作社印製 表 5 實 施 例 比 較 例 1 2 3 4 5 6 7 1 2 3 4 5 雙酚A型環 氧樹脂 100 100 100 100 100 100 100 100 100 100 100 100 合成例1之 樹脂 100 - - 合成例2之 樹脂 - 89 - - 合成例3之 樹脂 - - 94 94 合成例4之 樹脂 - - - - 89 89 - - - - - - 合成例5之 樹脂 - - - - - - 91 - - - - - 比較合成例1 之樹脂 92 92 - - - 比較合成例2 之樹脂 - 110 - - 苯酚漆用酚 醛樹脂 - - 85 85 三苯基磷酸酯 - _ 10 10 10 10 2-乙基4-甲 基咪唑 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -25 - 576844 A7R7 五、發明說明P ) 經濟部智慧財產局員工消費合作社印製 實 施 例 1 2 3 4 5 6 7 凝膠時間（秒） 112 189 135 146 126 137 163 Tg(TMA)(°C ) 1290 112 122 120 127 125 115 柱腳強度（N /cm) 0.27 0.19 0.22 0.22 0.24 0.24 0.20 PCT試驗；2h 0.35 0.46 0.39 0.41 0.37 0.41 0.44 ;4h 0.50 0.66 0.55 0.56 0.52 0.54 0.65 (吸水率％);6h 0.57 0.80 0.60 0.64 0.59 0.61 0.81 耐濕性焊錫性；PCT2h後 〇 〇 〇 〇 〇 〇 〇 :PCT4h 後 〇 〇 〇 Δ 〇 Δ 0 難燃性 V-1 V-1 V-1 V-0 V-1 V-0 V-1 比 較 例 1 2 3 4 5 凝膠時間（秒） 274 288 269 286 350 Tg(TMA)(°C ) 106 104 105 105 110 柱腳強度（N /cm) 0.18 0.18 0.18 0.17 0.17 PCT;2h 0.48 0.50 0.50 0.52 0.55 試驗；4 h 0.69 0.71 0.70 0.69 0.70 (吸水率％);6h 0.85 0.88 0.85 0.86 0.89 耐濕性焊錫性；PCT2h後 Δ X X △ X :PCT4h 後 X X X X X 難燃性 V-1 V-0 V-1 燃燒 燃燒 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再资寫本頁) -26- 576844 A7 _B7 五、發明說明口4 ) (產業上可利用性） 本發明之酚-胺縮合樹脂係具有良好之耐熱性、耐水 性、難燃性、強度、硬化性等者。 本發明之酚-胺縮合樹脂之製造法可製造生產性、收 率均佳之耐熱性、耐水性、難燃性、強度、硬化性均良好 之酚-胺縮合樹脂。 本發明之環氧樹脂組成物係具有良好之耐熱性、耐水 性、難燃性、強度、硬化性等者。 本發明之預漬體可製造生產性、收率均良好之優異之 耐熱性、耐水性、難燃性、強度、硬化性等者。 〔圖面之簡單說明〕 圖1係於合成例1取得之酚-胺縮合樹脂之G P C圖 表。 圖2係於比較合成例1取得之酚-胺縮合樹脂之 G P C圖表。 ,¾------- — 訂---1---線 (請先閱讀背面之注意Ϋ"項再资寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -27-Detector: RI Eluent: Tetrahydrofuran Flow rate: 1.6 ml / min The calibration line was made using standard polystyrene (trade name: TSK standard, manufactured by Tosoh Corporation) of the molecular weight shown in Table 1. The horizontal axis is the holding time (minutes) and the vertical axis is the logarithm of the molecular weight. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) Please read the notes on the back and fill in this page before ordering. V. Description of the invention 〇6) US 1 molecular weight-2 0 1 8 6, 0 0 0 ^ __ F — 4 4 3, 9 0 0 __F — 1 1 0, 3 0 0 2 5 0 0 2, 8 0 0 A -3 0 0 Average 456 (five parts are 578, 402, 370, 266, and 162. Printed clothing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. B_ 2 Project Synthesis Example Comparative Synthesis Example 1 Comparative Synthesis Example 2 1 2 3 4 5 Number average molecular weight 710 470 770 740 500 340 510 Weight average molecular weight 6560 900 2770 3400 1300 470 730 Weight average molecular weight / number average molecular weight 9.3 1.8 3.6 4.5 2.6 1.3 1.4 a / b 0.8 0.6 0.9 0.6 0.5 0.03 0.16 Phenol 2 core mass 30 20 25 20 35 32 31 Softening point (° c) 110 90 100 90 95 80 130 Nitrogen content rate (%) 15 4 9 4 6 7 23 Hydroxyl equivalent (%) 130 115 121 115 117 118 143 Phenol-amine condensation resin obtained in Example 1 and Synthesis Example 1 Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -------- Order ---------- line (please read the note on the back before writing this page) ) 19- 576844 A7 _ B7 V. Description of the invention (17) The GP C chart of the phenol-amine condensation resin obtained is used as the application example shown in Figure 1 1 epoxy equivalent 2 2 0, softening point 7 8 ° C 100 parts by weight of phenolic epoxy resin for phenol paint is blended with 50 parts by weight of melamine modified phenol resin synthesized in Production Example 1, 1.5 parts by weight of benzylmethylamine, 2 parts by weight of carnauba tincture, and 8 parts by weight. After antimony trioxide, 1.5 parts by weight of carbon black, 3 parts by weight of r-glycidoxytrimethoxysilane, and 360 parts by weight of fused silica, use a 10-inch diameter heating roller The roller is kneaded at a mixing temperature of 80 ° C to 90 ° C and a mixing time of 7 minutes. After that, it is pulverized by a pulverizer to obtain an epoxy resin molding material. Its characteristics are shown TABLE 4. Application Examples 2 to 3 and Comparative Application Examples 1, 2 and Application Example 1 were used to form a molding material. Its cooperation is shown in Table 3. These characteristics are shown in Table 4. The test method of the coating film is as follows. (1) Gel time; measured with a Curast meter manufactured by JS R, manufactured by Imaka Manufacturing Co., Ltd., at a temperature of 180 ° C. (2) Spiral flow; the measurement is performed at a mold temperature of 180 ° C and a transfer pressure of 70 K G F / C Μ 2 based on E Μ I 1-66. (3) Tg; TMA device manufactured by Rigaku Electric Co., Ltd. was used, and the temperature at the flexure point of the temperature-thermal expansion curve was used as Tg. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm). Please read the note at the back of $-and fill it out. ”Write this page. IIIII Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives. A7 B7 V. Description of the invention (18) (4) Flame resistance; evaluated by the VB method in accordance with UL-9 4 (1/8 inch test piece) (5) suspension beam impact; AST M — D 2 5 6 is based on the method. CV score, 1/8 inch test piece) Please read the notes and notes on the back before writing this page. China National Standard (CNS) A4 Specification (210 X 297 mm) -21-576844 A7 B7 V. Description of Invention (19) Printed by Employee Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 3 Application Examples Comparative Application Examples 1 2 3 4 5 1 2 Phenolic epoxy resin for cresol paint 100 100 100 100 100 100 100 100 Resin of Synthesis Example 50-_ Resin of Synthesis Example 2-50.-Resin of Zhao Synthesis Example 3 _ Resin of Synthesis Example 4 _ 50 Craft Resin of 5 _ 50 _ Resin of Comparative Synthesis Example 1-----50-Resin of Comparative Synthesis Example 2------50 Benzylamine 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Carnauba wax 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Antimony trioxide 8.0 8.0 8.0 8.0 8.0 8.0 8.0 Carbon black 1.5 1.5 1.5 1.5 1.5 1.5 1.5 r-Glycidoxytrimethoxysilane 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Fused silica 360 360 360 360 360 360 360- --------------- (Please read the phonetic notes on the back before writing this page for treatment) Order --------- Line 1 paper size applies Chinese national standards ( CNS) A4 specification (210 X 297 mm) -22- 576844 A7 B7 V. Description of invention ㊇) Table 4 Application examples Comparative application examples 1 2 3 4 5 1 2 Gel time (seconds) 25 28 35 30 40 60 60 Spiral flow (cm) 96 95 110 100 100 100 95 Tg (TMA) (° C) 115 120 120 115 120 120 120 Burning flameless time (seconds) 4.0 5.0 6.0 5.5 5.5 10.0 Drop of test flame > fnrr ιΓιΓ J \ \\ Μ 川 N Μ M ^ \\\ 4nr ΊΙΤΙΓ Combustion Μ j \\\ Judgment V-0 V-0 V-0 V-0 V-0 Vl Suspension beam impact (KG / CM) 15.0 14.0 14.9 15.0 14.0 14.5 14.5 Please read the note on the back _ Matters before writing this page Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 1 1 10 fat, 9 2 weight 0.1 mixed solvent mixed with 5 0 Pre-stained body by weight. After the copper foil was pressurized and heated, the non-volatile liquid was adjusted and impregnated in a glass cloth, and 8 pieces of a force of 4 pieces were laminated on a 1 8 prestained body. After forming, it was made into sticking examples 2 to 7 And Comparative Example 1 to 50 parts by weight of epoxy equivalent of 11 bisphenol A type epoxy tree amount of synthetic melamine denatured phenol resin synthesized in Example 1, 2 parts of ethyl ethyl 4-methyl imidazole Dissolved in a mixed solution of 60% toluene / methanol. After that, the solid content of the resin was dried at 0 ° C for 3 minutes in total with the glass cloth. After obtaining, the two sides were overlapped with m 2 of 3 5 // m on both sides and the temperature was 170 ° C into the copper laminate. The characteristics are shown in Table 6. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -23- 576844 A7 ------ B7 V. Description of the invention) The same method as in Example 1 is used to form a ring with the combination of Table 5. Oxygen resin composition, pre-stained body and copper-clad laminate. These characteristics are shown in Table 6. The test methods of the epoxy resin composition and the copper-clad laminate are as follows. (1) Gel time; a Curast meter manufactured by JS R, manufactured by Imaka Manufacturing Co., Ltd., and measured at a temperature of 180 ° C. (2) T g; T MG device manufactured by Seiko Instur Mants was used, and the temperature at the flexure point of the temperature-thermal expansion curve was used as T g. (3) Column foot strength: Shimadzu's automatic curve A G S-100 B was used to measure it. (4) Pressure flexion (PCT) test; water absorption after treatment at 120 ° C, 100% R Η for a predetermined time (2, 4, 6 hours). (5) Moisture resistance and solder resistance; the evaluated PC T (2.4 hours) test piece was immersed in a solder bath at 260 ° C for 20 seconds, and the external dfctf observation was evaluated. 0; no change Δ; Slight discoloration, swelling X; discoloration, obvious swelling, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (6) flame retardancy; according to UL-9 4 as the benchmark. Evaluation was performed by the v b method. (1/8 inch test piece) This paper size is applicable to Chinese National Standard (CNS) A4 (210 x 297 mm) 24- 576844 A7 _B7 V. Description of Invention P2) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economy 5 Examples Comparative Example 1 2 3 4 5 6 7 1 2 3 4 5 Bisphenol A epoxy resin 100 100 100 100 100 100 100 100 100 100 100 100 100 Resin of Synthesis Example 100--Resin of Synthesis Example-89 --Resin of Synthesis Example 3--94 94 Resin of Synthesis Example 4----89 89-------Resin of Synthesis Example 5------91-----Comparison of Synthesis Example 1 Resin 92 92---Resin of Comparative Synthesis Example 2-110--Phenolic resin for phenol paint--85 85 Triphenyl phosphate-_ 10 10 10 10 2-ethyl 4-methylimidazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -25-576844 A7R7 V. Description of the invention P) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 1 2 3 4 5 6 7 gel Time (seconds) 112 189 135 146 126 137 163 Tg (TMA) (° C) 1290 112 122 120 127 125 115 Column strength (N / cm) 0.27 0.19 0.22 0.22 0.24 0.24 0.24 0.20 PCT test; 2h 0.35 0.46 0.39 0.41 0.37 0.41 0.44; 4h 0.50 0.66 0.55 0.56 0.52 0.54 0.65 (water absorption%); 6h 0.57 0.80 0.60 0.64 0.59 0.61 0.81 moisture resistance solderability; after PCT 2h 00: 00: 00: after PCT 4: 0 0 Δ 〇 Δ 0 Flame retardancy V-1 V-1 V-1 V-0 V-1 V-0 V-1 Comparative example 1 2 3 4 5 Gel time (seconds) 274 288 269 286 350 Tg (TMA) (° C) 106 104 105 105 110 Column foot strength (N / cm) 0.18 0.18 0.18 0.17 0.17 PCT; 2h 0.48 0.50 0.50 0.52 0.55 test; 4 h 0.69 0.71 0.70 0.69 0.70 (water absorption rate%); 6h 0.85 0.88 0.85 0.86 0.89 moisture resistance Solderability; After PCT2h Δ XX △ X: After PCT4h XXXXX Flame retardant V-1 V-0 V-1 Combustion This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read first Remarks on the back page will be rewritten on this page) -26- 576844 A7 _B7 V. Description of the invention 4) (Industrial applicability) The present invention The phenol-amine condensation resin is one having good heat resistance, water resistance, flame retardancy, strength, hardenability, and the like. The method for producing a phenol-amine condensation resin of the present invention can produce a phenol-amine condensation resin with excellent heat resistance, water resistance, flame resistance, strength, and hardenability, which are excellent in productivity and yield. The epoxy resin composition of the present invention has good heat resistance, water resistance, flame retardancy, strength, hardenability, and the like. The prepreg according to the present invention can be produced with excellent heat resistance, water resistance, flame retardancy, strength, hardenability, etc., which are excellent in productivity and yield. [Brief Description of Drawings] Figure 1 is a GPC chart of a phenol-amine condensation resin obtained in Synthesis Example 1. Fig. 2 is a G P C chart of a phenol-amine condensation resin obtained in Comparative Synthesis Example 1. , ¾ ------- — Order --- 1 --- line (please read the note on the back Ϋ " and then write this page) Printed on paper standards applicable to China National Standard (CNS) A4 Specification (210 X 297 Public Love) -27-