經濟部中央標準扃負工消费合作社印簟 A7 B7 五、發明説明6 ) 發明背景 發明領域 本發明係有關於難燃性樹脂組成物，其無需用到含歯 素之火焰阻滯劑使具有優異難燃性，以及有關於使用此組 成物之叠層物。 相關技藝說明 熱固性樹脂（代表者爲環氧樹脂等）具有優異特性， 所以廣泛地甩於電氣與電子零件等，而在許多例子中，常 賦予這些熱固性樹脂難燃性，以確保對火災的安全性。爲 了使這些樹脂具有難燃性，通常利用含鹵素化合物，如， 溴化環氧化合物等·這些含鹵素化合物具有高難燃性；但 是，溴化芳族化合物不僅可能會在熱分解時釋出溴與溴化 氫（二者均具有腐蝕性），亦會於氧存在之分解時，形成 多溴苯並呋喃與多溴苯並載奧辛（二者均爲髙毒性）·再 者，含溴破碎物與再熔融廢棄物之處理均十分困難•基於 此理由，磷化合物已被廣泛地硏究來作爲火焰阻滯劑，進 而取代含溴之火焰阻滯劑•但是，當於環氧樹脂類之熱固 性樹脂中，單獨使用磷化合物時，必需添加大量的磷化合 物方能得到足夠的難燃性，而此舉將顯著地破壞機械，化 學與電特性。 本發明目的與簡述 本發明係由嚴密地硏究解決上述問題而完成。 • L1. (請先閏讀背面之注項再填寫本頁) 訂 線 本紙張尺度適用中國國家橾率（CNS ) A4规格（210X297公釐} Α7 Β7 經濟部中央標準局貝工消费合作社印簟 五、發明说明έ ) 本發明目的在於提出無需添加含鹵素化合物便可具有 高難燃性之難燃性樹脂組成物，且其不會破壞市售產品之 特性。 本發明另一目的在於提出使用上述樹脂組成物之叠層 物。 本發明之其他目的與優點將以下述說明而揭示。 本發明提出之難燃性樹脂組成物·其包括（Α ) 1 0 0重量份分子中具有至少兩個環氧基之未鹵化環氧樹 » 脂，（Β)20至205重置份分子中具有至少一個順丁 烯二醯亞胺基之順丁烯二醣亞胺化合物，（C)20至 6 5重量份具有胺基之固化劑，以及（D)以磷元素計， 佔每100重量份成分（A) ，（Β) ，（C)總重之 0.5至4.5重置份的磷化合物，且此組成物中氮元素 含量佔每1 0 0重置份總組成物的2 . 0至1 0 . 0重置 份- 本發明亦提出由上述難燃性樹脂組成物與基材所組成 之叠層物· 發明詳細說明： 如上所述，當於環氧樹脂類之熱固性樹脂中單獨使用 磷化合物時，得添加大量的磷化合物方能得到足夠的難燃 性，且此舉將顯著地破壞機械，化學與電特性。在本發明 中，爲了解決此問題，可以令氮元索與磷元索共存而得到 協乘功效，所以降低了磷元素的用纛而仍能得到難燃性。 ______了______良...： 1 .1 轉1_ (讀先《讀背面之注f項再填寫本I) 本紙張尺度逍用中國國家標率（CNS ) A4*L格（210X297公羞） -5- A7 B7 經濟部中央梂準局員工消费合作杜印氧 五、發明説明6 ) 再者，本發明技術一特徵點爲：將含氮環結構引入樹脂架 構中，進而提高難燃性與耐熱性，且進一步降低磷元素含 量以調合難燃性與耐熱性· 本發明中，分子中具有至少兩個環氧基之未鹵化環氧 樹脂〔成份（A)〕包括雙酚A型環氧樹脂，雯酚F型環 氧樹脂，雙酚S型環氧樹脂，苯酚醛淸漆型環氧樹脂，甲 酚醛淸漆型環氧樹脂，萘型環氧樹脂，聯苯型環氧樹脂， 以及N -縮水甘油基化合物，此化合物係由芳族胺與雜環 氮驗（如，N，N —二縮水甘油基苯胺，k氰尿酸三縮水 甘油酯，N，N，—四縮水甘油基二（對胺苯 基）甲烷等）而得。但是上述環氧樹脂（A )並不限於上 述樹脂·其可兩種或多種混合使用。但是本發明在於提出 不含火焰阻滯劑之樹脂組成物，所以不可用含鹵素之環氧 樹脂，如，溴化雙酚A型環氧樹脂，溴化酚醛淸漆型環氧 樹脂等。但是由於產製環氧樹脂的製程中，由作爲起始物 之表氯酵所生成的氯將無法避免地會含於環氧樹脂（A) 中，此氯含量爲此技藝領域所公知，即，數百個p pm之 可水解氯· 本發明中作爲成分（B )之分子中具有至少一個順丁 烯二醯亞胺基之順丁烯二醯亞胺化合物包括N-甲基順丁 烯二醯亞胺，N -丁基順丁烯二醯亞胺，N -辛基順丁烯 二醣亞胺，N-十二烷基順丁烯二醯亞胺，N —硬脂基順 丁烯二醢亞胺，N —環己基順丁烯二醣亞胺，N —苯基顒 丁烯二醯亞胺，N —（鄰甲苯基）順丁烯二醯亞胺，N_ (請先閱讀背面之注意事項再填寫本霣) 訂 線 本纸張尺度適用中國•家標準（CNS ) A4规格（210X297公漦） • 6· 趙濟部中央標準局另工消费合作社印製 A7 _B7 五、發明説明4 ) 十二烷苯基順丁烯二醯亞胺，N —（鄰一或對一羥苯基） 順丁烯二醣亞胺，N —（鄰-或對一甲氧苯基）順丁烯二 醯亞胺，N —(間羥羰苯基）頋丁烯二醣亞胺，n —（間 硝苯基）順丁烯二醣亞胺，1 一甲基一 2，4 一順丁烯二 醣亞胺基苯，N，N · —間伸苯基二順丁烯二醯亞胺，N ，N，一對伸苯基二順丁烯二醣亞胺，N，N·— 4， 4—一〔3 ’ 3 * —二甲基伸聯苯基〕二順丁烯二醯亞胺 ，N，N^ — 4，4^ 一〔3，3 / —二甲基二苯基甲烷 〕二順丁烯二醣亞胺，N，N< - 4，4^一〔3，3 -一二乙基二苯基甲烷〕二順丁烯二醯亞胺，N，N * — 4 • 4 / 一二苯基甲烷二順丁烯二醣亞胺，N，N — - 4， 4 一―二苯醚二順丁烯二酺亞胺，N，N - — 3，3 一-二苯碩二順丁烯二醣亞胺，N，N* — 4，4 - 一二苯砚 二順丁烯二醣亞胺，2，2_二〔4_ (4 一順丁烯二醣 亞胺基苯氧基）苯基〕丙院，2，2 —二〔3 -第三丁基 七4 一（ 4 一順丁烯二醣亞胺基苯氧基）苯基〕丙烷，2 ，2 —二〔3 —第二丁基一 4 一（4 一順丁烯二醯亞胺基 苯氧基）苯基〕丙烷，1，1 一二〔4 一（4 -順丁烯二 醯亞胺基苯氧基）苯基〕癸烷，1，1一二〔2—甲基-4 一（ 4 一順丁烯二醣亞胺基苯氧基_ 5 -第三丁基苯基 )一 2 —甲基丙烷，4，4 > —伸環己基二[1 一（4 一 順丁烯二醣亞胺基苯氧基）一2—（1，1_二甲乙基） 苯〕，4，4>一伸甲基一二〔1一（4一順丁烯二醣亞 胺基苯氧基）一 2，6 —二（1，1 一二甲乙基）苯〕， 本纸張尺度適用中國國家揉率（CNS ) Α4规格（210X297公漦） {請先《讀背面之注意事項再填邦本頁) 訂 經濟部中央標準扃貝工消费合作社印製 A7 ____ B7 五、發明说明) 4，一伸甲基一二〔1 一（4 一順丁烯二醯亞胺基苯 氧基）—2，6 —二第二丁基苯〕，4，4 > 一伸環己基 一二〔1_ (4 一順丁烯二醣亞胺基苯氧基）一 2 —環己 基苯〕，4，4 # —伸甲基一二〔1—(順丁烯二醯亞胺 基苯氧基）一 2 —壬基苯，4，4 #_( 1 一甲基伸乙基 )一二〔1 一（順丁烯二醣亞胺基苯氧基）一 2，6 -二 (1, 1_二甲乙基）苯〕，4，4< 一（2 —乙基伸己 基）一二〔1 一（順丁烯二醣亞胺基苯氧基）苯〕，4， 4 > 一（ 1 一甲基伸庚基）一二〔1- (bi 丁烯二醯亞胺 基苯氧基）苯〕，4，4"* 一伸環己基一二〔1一（順丁 烯二醣亞胺基苯氧基）一3 —甲基苯〕，2，2 ^ —二〔 4— (4 一順丁烯二醯亞胺基苯氧基）苯基〕丙烷，2， 2 > —二〔3 —甲基一 4 一〔 4 一順丁烯二醯亞胺基苯氧 基〕苯基〕丙烷，2，2 # —二（3 · 5 —二甲基 -順丁烯二醯亞胺基苯氧基 ） 苯基） 丙烷， 2 ， 2 ~ —二〔3 —乙基一 4 一（4 一頋丁烯二醣亞胺基苯氧基） 苯基〕丙烷，二〔3 —甲基（4 一順丁烯二醯亞胺基苯氧 基）苯基〕甲烷，二〔3，5 —二甲基一（4 一順丁烯二 醯亞胺基苯氧基）苯基〕甲烷•二〔3 —乙基一（4 一頋 丁烯二醯亞胺基苯氧基）苯基〕甲烷，3，8 -二〔4_ (4 一順丁烯二醢亞胺基苯氧基）苯基〕一三環〔5， 21，02 6〕癸烷，4，8 —二[4 - (4 一顒丁烯二 醯亞胺基苯氧基）苯基〕一三環〔5 * 2，1，02 β〕 癸烷，3，9 一二〔4 一（4 一順丁烯二醣亞胺基苯氧基 ΟΙ I I I 丁— I I I I I 良 匀------婢，ί (請先《讀背面之注意事項再填寫本頁) 本紙張尺度逋用中國國家揲率（CNS > Α4规格（210X297公釐） -8- A7 B7 五、發明说明6 ) )苯基〕一三環〔5，2，1，02·6〕癸烷，4，9 一 二〔4一（4 一順丁烯二醣亞胺基苯氧基）苯基〕一三環 〔5，2，1，02·6〕癸烷等：但是成分（B)並不限 於上述化合物。就耐熱性、價格、進料安定性，使用廣泛 度等，以芳族二頋丁烯二醣亞胺與N -取代芳族單順丁烯 二醃亞胺較佳，以N，N，一4，4 >一二苯基甲烷二順 丁烯二醯亞胺最佳•此外，亦可於控制順丁烯二醣亞胺在 溶劑中之交聯密度與溶解度時，使用與胺之Mickael加成以 及與烯丙基化合物之烯反應（ene reaction i 。 本發明中具有胺基之固化劑（C )包括C2 — C2〇直 鏈脂族二胺，如，乙二胺，丙二胺，丁二胺，己二胺等， 間苯二胺，對苯二胺，對苯二甲胺，4，4 < 一二胺基二 苯基甲烷，4，4 > 一二胺基二苯基丙烷，4，4 > 一二 胺基二苯基醚，4，4 二胺基二苯基硯，4，4 ―一 二胺基二環己烷，二（4 一胺苯基）苯基甲烷，1，5 -二胺基萘，間苯二甲胺，對苯二甲胺，1，1一二（4一 胺苯基）環己烷，二氰二醣胺等；但並不限於上述。就耐 熱性，價格，進料安定性，使用廣泛性等，以芳族二胺爲 佳，最佳爲4，4 < 一二胺基二苯基甲烷· 本發明所用磷化合物（D)包括磷酸酯，如，磷酸三 甲酯，磷酸三乙酯，磷酸三丁酯，磷酸三2 —乙己酯，磷 酸三丁氧乙酯，磷酸三苯酯，磷酸三苯酚酯，磷酸三二甲 苯酯磷酸（苯酚二苯）酯，磷酸（二甲苯基二苯基）酯， 磷酸（乙己基二苯基）酯，磷酸三（2，6 —二甲苯基） 本紙張尺度適用中两國家標準（CNS ) A4规格（210X297公羞） (請先Η讀背面之注f項再填寫本頁 订 經濟部中央標準局男工消费合作社印製 • 9 經濟部中央標準局貝工消費合作社印家 A7 ____B7___五、發明説明$ ) 酯，磷酸（松香基二苯基）酯等；縮合磷酸酯，如，多磷 酸銨，多磷醣胺鹽等：紅磷，磷酸胍，磷酸（二烷基羥甲 基）酯等；但並不特別限於上述。這些化合物可二個以上 合用。 本發明難燃性樹脂組成物如下製成：將成分（A)( 即，分子中具有至少兩個環氧基之未鹵化環氧樹脂）*成 分（B)(即，分子中具有至少一個順丁烯二醣亞胺基之 順丁烯二醣亞胺化合物），成分（C)(即，具有胺基之 固化劑），與成分（D )(即，磷化合物）混合*混合比 爲每1 0 0重量份成分（A)有2 0至2 0 5重量份成分 (B) ，20至65重量份成分（C);且成分（D)以 磷元素計，佔成分（A) ， （B) ， （C)每100重量 份總重之0.5至4.5重置份，且此組成物中氮元素含 量佔每1 0 0重量份組成物重總重的2 · 0至1 0 . 0重 量份。 當成分（B )低於2 0重量份/ 1 0 0重1:份成分（ A)，成分（B)對難燃性的功效變小，且耐熱性變差， 當其用量超過2 0 5重置份/ 1 0 0重量份成分（A )， 黏著性變差·所以這些用量是不預期的· 當成分（C )低於2 0重置份/1 0 0重量份成份（ A)，樹脂無法完全固化，若其量超過65重量份/ 10 0重量份成分（A) ’會殘留大量胺基’使得耐水氣 性質變差•所以這些用置是不預期的。 當成分（D)之磷元素量低於0·5重童份/100 本纸張尺度逍用中國國家楳率（CNS ) A4规格（210X297公釐）~. (請先閱讀背面之注$項再填寫本頁) 訂 線. 經濟部中央標準局員工消费合作社印製 A7 _B7_五、發明说明§ ) 重量份（成分（A) + (B) + (C))，成分（D)對 難燃性之功效變小，但若超過4 . 5重童份/1 0 0重童 份（成分（A) + (B) + (C))，耐熱性會變差•所 以這些用置是不預期的。 再者，當氮元素低於2 . 0重量份/1 0 0重量份總 組成物，氮元素對難燃性之功效變小，但若超過1 〇 . 〇 重量份/100重量份（成分（A) + (B) + (C)) ，耐水氣性質變差。所以這些用置是不預期的· 本發明難燃性樹脂組成物可以各種形k來應用，且當 用來浸溃基材時，通常會使用溶劑*此溶劑必須對組成物 中一些成分或全部成分具有良好溶解力。但是亦可使用不 良溶劑（poor solvent)，只要其不會對此組成物有不良影 響。可用於本發明的溶劑包括：酮類，如丙酮，甲乙酮， 甲異丁酮，環己酮等，芳族烴類，如，甲苯，二甲苯，來 等：各種二醇醚類，如，甲基溶纖素，乙基溶嫌素，丁基 溶嫌素，異丁基溶嫌素，二乙二醇單甲醚，三乙二醇單甲 醚，丙二醇單甲醚，二丙二醉單甲醚，丙二酵單丙醚，二 丙二酵單丙醚，乙二酵單異丙醚，二乙二酵單異丙醚，二 乙二醇單丁醚等；酯類，如，甲基溶繊素乙酸酯，乙基溶 纖素乙酸酯* 丁基溶嫌素乙酸酯，乙酸乙酯等；二伸烷基 二醇二烷醚類，如，二乙二酵二甲醚，二乙二酵二乙醚， 二乙二酵二丁醚等·•醯胺類，如，N，N —二甲基乙醢胺 ，N，N-二甲基甲薩胺，N-甲基一2 —吡咯烷酮等； 醇類，如，甲醇，乙醇等。其可以兩種以上合併使用· 本紙張尺度適用中國困家標率（CNS ) A4規格（2丨0X297公釐） ΤΛ {請先Μ讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消费合作社印装 A7 B7 _五、發明说明6 ) 將本發明樹脂組成物溶於上述溶劑中而製成淸漆，以 此淸漆塗覆與浸溃基材（如，玻璃雄造雄物’玻璃非嫌造 織物，紙或非玻璃成分所成雄物），然後將此沒溃基材置 於8 0°C至2 〇 or烘箱中乾燥，便製成印刷電路板之預 溃體（prepreg )。加熱壓製此預溃髖便可製成印刷電路板 。本發明樹脂組成物不添加鹵素化合物便具有高難燃性， 其含有不會對市售產品有不利影響之熱固性樹脂，所以適 合用在叠層物、金屬包覆之叠層物等之中* > ) 較佳具體例說明 實例1 將N，N —二甲基甲醣胺/甲乙酮之1/1混合溶劑 加入1 0 0重量份苯酚醛淸漆型環氧樹脂（DAINIPPON INK & CHEMICALS INC.製造（EPICLON N-770 ))， 1 9 3重量份N，N — 4，4 '一二苯基甲烷二順丁烯二 醯亞胺（K.I. CHEMICAL INDUSTRY CO.，LTD.製造，（BMI •Η)) ，6 1重置份4，4 ”一二胺基二苯基甲烷與1 00 重量份磷酸三苯酯而製成淸漆，且其中非揮發物質濃度爲 5 0% ·此時，磷元素佔毎1 0 0重置份環氧樹脂，順丁 烯二醣亞胺化合物與固化劑總重之2.7重置份· 取1 00重量份玻璃布（厚度爲0 . 1 8mm， NNITTO BOSEKI CO.，LTD.製造）以上述淸漆（用量以淸 漆固含量計爲8 0重量份）浸漬，然後於1 5 or烘箱乾 燥4分鐘而製成預溃镰（樹脂含置爲44.4wt%)· (讀先《讀背面之注意Ϋ項再填寫本頁) 訂 線 本紙張尺度適用中國國家揉率（CNS ) A4*l格（2丨0X297公釐） •12- Α7 Β7 五、發明说明ίο ) 將8片如此所得預溃《 —片一片叠好，所得組合體的最上 面與最下面各放置厚3 5 之電解銅箔，然後以4 0 kgi/ciri，170t，進行熱壓成形歷120分鐘， 得出厚1.6mm之雙面網包覆之叠層物· 所得叠層物之難燃性依U L — 9 4標準之垂直灼燒測 試法評估。另依JIS C 6481測試焊接熱抗性與 脫皮強度，在焊接熱抗性测量中，令叠層物沸朦2小時而 歷經水氣吸收處理，然後令其浮在2 6 Ot焊劑浴中 1 8 0秒，然後檢視外觀•再者，依黏彈法得出t a η 5峰線溫度而定出玻璃轉移溫度•所得結果示於表1· {請先閱讀背面之注f項再填寫本頁) 訂 線 經濟部中央標率局貝工消费合作社印It 本紙張又度適用中國國家標準（CNS ) A4規格（210Χ2Ϊ»7公釐）_ 13 _ ^88768 五、發明説明h ) 表1 項目 實例1 實例2 實例3 實例4 實例5 實例6 實例7 配合量(重 量份） EPICLON Ν-770 0 100 80 100 - 100 100 100 Ep 1001s - 20 - - - - - 異氰尿酸三縮水甘油酯 - - - 100 - - - BMI-H3) 193 193 193 88 54 24 22 4,4'-二胺基二苯基甲烷 61 61 61 36 32 26 23 縦三苯豳 100 100 - 46 15 42 65 CR-74 广 100 - - - - 磷元索(M份)5， 2.7 2.7 2.3 2.0 0.8 2.7 4.3 氮元索(M份)ύ 5.2 5.2 5.2 9.6 2.2 2.9 2.4 特性 難性測試(UL 94) V-0 V-0 ν·ο V-0 V-0 V-0 V-0 焊接織性;> 通過 通過 通過 通過 通過 通過 通過 脫皮強度(KN/cm) 1.5 1.8 1.5 1.7 1.9 1.8 1.6 Tg(DMA法Xt) 175 165 173 168 170 155 150 (讀先《讀背面之注意事項再填寫本頁 订 線 經濟部中央標準局員工消费合作社印製 本紙張尺度適用中困國家標準（CNS ) A4規格（210X297公嫠） -14- 888768_b7 __ 五'發明说明i2 ) 註： 1 ) : DIANIPPON INK & CHEMICALS INC製造之苯酚醛 淸漆型環氧樹脂· 2 ) : Yuka-Shell Epoxy Co·，Ltd.製造之雙 S&A 型環氧樹 脂。 3 ) : Keiai Kasei K.K.製造之 N，N' — 4，4一_ 二苯 基甲烷二順丁烯二醯亞胺· 4 ) : Daihachi Kagaku Kogyo K.K.製造之縮合碟酸酯· t 5) :每100重量份環氧樹脂，順丁嫌二臁亞胺化合物 與固化劑總重中，磷元索之重量份· 6) :每1 0 0重量份總組成物重置中，氮元素之重量份 〇 7) :試樣經沸騰2小時之水氣吸收處理*然後浮在 2 6 0 °C焊劑浴中1 8 0秒之後的外觀。 ------------ο------訂------線；'' {請先闐讀背面之注項再填寫本頁) 經濟部中央揉準局負工消费合作社印掣 本紙張尺度適用中國國家標率（CNS ) A4規格（210X297公釐） -15- 388柳 五、發明说明h ) 表2 項目 比較例_1 比較例2 比較例3 比娜 比較例5 比較例6 比較例7 配合1:(重 量份） EPICLON N-770 100 100 100 100 100 100 - 異縣酸36水甘油酯 - - • - - 100 ΒΜΙ·Η 15 88 210 88 88 88 110 4,4’-二胺基二苯基甲烷 22 36 61 36 15 70 38 讲酸三苯酯 46 10 100 145 46 46 - 紅辑 - - - _ - - 3 磷元素(M份） 3.2 0.4 2.6 6.1 2.2 1.7 1.2 氮元索(S*份） 2.3 5.1 5.3 3.2 3.6 5.5 11.2 特性 難燃性测試(UL 94) V-1 ν·1 V-0 V-0 V-0 V-0 V-0 焊接熱抗性71 通過 通過 起泡 起泡 起泡 起泡 起泡 脫皮強度(KN/cm) 1.9 1.6 1.1 1.2 1.3 1.3 1.2 Tg(DMA^Kt：) 140 175 185 121 138 156 156 (讀先《讀背面之注^.項再填寫本頁) 订 -H— 經濟部中央揉準局貝工消费合作社印簟 本紙張尺度逍用中國國家標率（CNS ) A4规格（210X297公1 ) 888768 :五、發明説明“） 實例2至7以及比較例1至7 重覆實例1之步驟，但使用表1與表2所示組成，而 製成銅包覆之叠層物•評估結果示於表1與表2 ·依實例 所示組成製成之叠曆物在難燃性、焊接熱抗性與黏附性質 上均爲優異v 本發明難燃性樹脂組成物不必添加鹵素化合物便具有 高難燃性，同時亦具有優異耐熱性以及優異黏附性質，所 以本發明提出之新穎難燃性熱固性樹脂組成物爲非鹵素材 料，且在將來會有很大需求· (請先《讀背面之注f項再填寫本頁) .裝. 訂 線 本紙張尺度適用中國國家梂车（0阳）八4*1格（210><297公釐）.Central Standard of the Ministry of Economic Affairs, Consumers' Cooperatives, India A7 B7 V. Description of the invention 6) Field of the invention The present invention relates to a flame retardant resin composition, which does not require the use of halogen-containing flame retarders to make it excellent. Flame retardancy, and laminates using this composition. Relevant technology shows that thermosetting resins (represented by epoxy resins, etc.) have excellent characteristics, so they are widely used in electrical and electronic parts. In many cases, these thermosetting resins are often given flame resistance to ensure safety against fire. Sex. In order to make these resins flame retardant, halogen-containing compounds such as brominated epoxy compounds are generally used. These halogen-containing compounds have high flame retardancy; however, brominated aromatic compounds may not only be released during thermal decomposition. Bromine and hydrogen bromide (both are corrosive) will also form polybromobenzofuran and polybromobenzooxacin (both are toxic) when decomposed in the presence of oxygen. Furthermore, containing Bromine bromide and remelted waste are very difficult to handle. • For this reason, phosphorus compounds have been widely investigated as flame retarders, replacing the flame retarders containing bromine. In a similar thermosetting resin, when a phosphorus compound is used alone, it is necessary to add a large amount of the phosphorus compound to obtain sufficient flame resistance, and this will significantly damage the mechanical, chemical and electrical characteristics. OBJECTS AND BRIEF DESCRIPTION OF THE INVENTION The present invention has been accomplished by rigorously researching and solving the above problems. • L1. (Please read the notes on the back before filling this page) The paper size of the booklet is applicable to China's National Standard (CNS) A4 specification (210X297 mm) Α7 Β7 Printed by the Beige Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention) The object of the present invention is to propose a flame-retardant resin composition that can have high flame-retardant properties without adding a halogen-containing compound, and which will not damage the characteristics of commercially available products. Another object of the present invention is to propose a laminate using the above resin composition. Other objects and advantages of the present invention will be revealed by the following description. The flame-retardant resin composition proposed by the present invention includes (A) 100 parts by weight of an unhalogenated epoxy resin having at least two epoxy groups in a molecule, and (B) 20 to 205 replacement parts in a molecule A maleimide compound having at least one maleimide group, (C) 20 to 65 parts by weight of a curing agent having an amine group, and (D) as a phosphorus element, per 100 weight Parts of components (A), (B), (C) 0.5 to 4.5 parts by weight of total phosphorus compounds, and the nitrogen content of this composition accounts for 2.0 to 100 parts per 100 parts of total composition 10.0 replacement parts-The present invention also proposes a laminate composed of the above-mentioned flame-retardant resin composition and a base material. · Detailed description of the invention: As described above, when used alone in an epoxy-based thermosetting resin In the case of phosphorus compounds, it is necessary to add a large amount of phosphorus compounds to obtain sufficient flame resistance, and this will significantly damage the mechanical, chemical and electrical characteristics. In the present invention, in order to solve this problem, the nitrogen element and the phosphorus element can coexist to obtain a synergistic effect, so the use of phosphorus element can be reduced and the flame retardancy can still be obtained. ______ 了 ______ Good ...: 1.1 .1 turn 1_ (read "Read the Note f on the back side and then fill out this I) This paper size is free of China National Standards (CNS) A4 * L grid (210X297) Shame) -5- A7 B7 Consumption cooperation between employees of the Central Bureau of Standards and Commerce of the Ministry of Economic Affairs Du Yinxian 5. Description of the invention 6) Furthermore, a feature of the technology of the present invention is: introducing a nitrogen-containing ring structure into the resin structure, thereby improving flame resistance Properties and heat resistance, and further reduce the phosphorus content to blend flame resistance and heat resistance. In the present invention, the non-halogenated epoxy resin having at least two epoxy groups in the molecule [component (A)] includes bisphenol A type Epoxy resin, phenol F-type epoxy resin, bisphenol S-type epoxy resin, phenol-formaldehyde lacquer-type epoxy resin, cresol-formaldehyde lacquer-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin , And N-glycidyl compounds, this compound is based on aromatic amines and heterocyclic nitrogen (such as, N, N-diglycidyl aniline, kyl cyanurate triglycidyl, N, N,-tetraglycidyl Di (p-aminophenyl) methane, etc.). However, the above-mentioned epoxy resin (A) is not limited to the above-mentioned resins, and they may be used in combination of two or more kinds. However, the present invention proposes a resin composition containing no flame retarder, so halogen-containing epoxy resins such as brominated bisphenol A type epoxy resin, brominated phenol novolak type epoxy resin, etc. cannot be used. However, in the production process of producing epoxy resin, the chlorine generated by the epichlorine fermentation as the starting material will inevitably be contained in the epoxy resin (A). This chlorine content is well known in the art, that is, Hundreds of p pm of hydrolyzable chlorine · The cis-butene-diimide compound having at least one cis-butene-diimide group in the molecule as the component (B) in the present invention includes N-methylcis-butene Diamidine, N-butyl maleimide diammonium, N-octyl maleimide diimide, N-dodecyl maleimide diimide, N-stearyl maleimide diimide Amine, N —cyclohexylmaleimide, N —Phenylbutenediimide, N — (o-tolyl) maleimide, N_ (Please read the notes on the back first Fill in this paper again) The paper size of the booklet is applicable to China • Home Standard (CNS) A4 specification (210X297 gigabytes) • 6. The printing of A7 _B7 printed by Zhaoji Central Standards Bureau and other consumer cooperatives V. Description of the invention 4) Dodecane Phenylmaleimide diimide, N — (o- or p-hydroxyphenyl) maleimide diimide, N — (o- or p-methoxyphenyl) Group) maleimide diimide, N- (m-hydroxycarbonylphenyl) ammonium diimide, n- (m-nitrophenyl) maleimide, 1-methyl-2, 4 maleimide diimidobenzene, N, N · -m-phenylene dimaleimide diimide, N, N, a pair of maleimide dimaleimide diimide, N, N · —4, 4 -— [3 ′ 3 * -dimethylphenylphenyl] dicis-butenedifluorene imine, N, N ^ —4,4 ^ — [3,3 / —dimethyl Diphenylmethane] bismaleimide diimide, N, N <-4,4 ^ a [3,3-diethyldiphenylmethane] dicis butene difluorenimine, N, N * — 4 • 4 / Mono-diphenylmethane-bis-maleimide diimide, N, N —-4, 4, mono-diphenyl ether di-maleimide diimide, N, N--3, 3 Mono-diphenylsuccinic maleic acid diimide, N, N * — 4,4-diphenylstilbene di maleic acid diimide, 2,2_di [4_ (4 mono maleic acid Sugar iminophenoxy) phenyl] propane, 2,2-di [3-third butyl hepta-1 (4-monosuccinimidophenoxy) phenyl] propane, 2 , 2 — two [3 — first Dibutyl-1,4-mono (4-cis-butenediamidinophenoxy) phenyl] propane, 1,1-1,2 [4-mono (4-cis-butenediamidinophenoxy) benzene Yl] decane, 1,1,2- [2-methyl-4 mono (4-monobutylenediiminophenoxy-5-tert-butylphenyl), 2-methylpropane, 4 , 4 > —Cyclohexylbis [1 ((4-mono-maleimidoiminophenoxy) —2— (1,1-Dimethylethyl) benzene], 4,4 >> Methylene-1 Two [1- (4-maleimidoimidophenoxy) -2,6-di (1,1-dimethylethyl) benzene], this paper size applies to China National Kneading Ratio (CNS) Α4 Specifications (210X297 Gong) {Please read the “Notes on the back side and then fill in the state page”) Order the central standard of the Ministry of Economic Affairs __Printing A7 __ B7 V. Description of the invention) 4. One methylated one two [1 Mono (4-monobutylene diamidophenoxy) -2,6-di-second butylbenzene], 4,4 > cyclohexyl bis [1_ (4- mono maleic acid Aminophenoxy)-2 -cyclohexylbenzene], 4, 4 #-methyl 1-2 [1 — (Cis-butenediaminimidophenoxy) —2—nonylbenzene, 4,4 #_ (1-methylendethyl) -di-2- [1- (maleimidoimidophenyl) (Oxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4 < mono (2-ethylhexyl) -di [1 ((maleicimidoiminophenoxy) ) Benzene], 4, 4 > mono (1-methylheptyl) -diphenyl [1- (bi butenediamidoiminophenoxy) benzene], 4,4 " * cyclohexyl-1,2 [1-mono (maleicimidophenoxy) -3-methylbenzene], 2,2 ^ -di [4- (4-monobutyleneimidophenoxy) phenyl ] Propane, 2, 2 > -di [3-methyl-1, 4-[[4-mono-butenediamidoiminophenoxy] phenyl] propane, 2,2 # -di (3 · 5-two Methyl-cis-butenediamidoiminophenoxy) phenyl) propane, 2, 2, 2-di [3-ethyl-4, 4- (4-butenediaminoiminophenoxy) benzene Propyl] propane, bis [3-methyl (4-monobutylenediamidophenoxy) phenyl] methane, bis [3,5-dimethyl-1 (4-one Cis-butenediiminophenoxy) phenyl] methane • di [3-ethylmono (4-monobutenediiminophenoxy) phenyl] methane, 3,8-di [ 4_ (4-monobutenediamidoiminophenoxy) phenyl] -tricyclo [5, 21,02 6] decane, 4,8-di [4-(4-monobutenedifluorene) Aminophenoxy) phenyl] -tricyclic [5 * 2,1,02 β] decane, 3,9 one two [4 one (4-monosuccinimide iminophenoxy III III butyl — IIIII Liangyun ------ 婢, ί (please read the “Notes on the back side before filling in this page”) This paper uses the Chinese national standard (CNS > Α4 size (210X297mm) -8- A7 B7 V. Explanation of the invention 6)) Phenyl] -tricyclic [5, 2, 1, 02 · 6] decane, 4, 9 di [4 1 (4- maleimide diiminophenoxy) Group) phenyl] -tricyclo [5,2,1,02 · 6] decane and the like: However, the component (B) is not limited to the above compounds. In terms of heat resistance, price, feed stability, wide range of use, etc., aromatic difluorene butene diimide and N-substituted aromatic monocis butylene di-imide are preferred, and N, N, one 4,4 > Mono-diphenylmethane-bis-butene-diimine is the best. • In addition, Mickael with amine can also be used to control the cross-linking density and solubility of maleimide in a solvent. Addition and ene reaction with allyl compounds (ene reaction i. In the present invention, the curing agent (C) having an amine group includes C2-C20 linear aliphatic diamines, such as ethylenediamine, propylenediamine, Butylenediamine, hexamethylenediamine, etc., m-phenylenediamine, p-phenylenediamine, p-xylylenediamine, 4,4 < monodiaminodiphenylmethane, 4,4 > monodiaminodiphenyl Propane, 4,4 > monodiaminodiphenyl ether, 4,4 diaminodiphenylphosphonium, 4,4-diaminoaminocyclohexane, bis (4-monoaminophenyl) benzene Methane, 1,5-diaminonaphthalene, m-xylylenediamine, p-xylylenediamine, 1,1-bis (4-aminophenyl) cyclohexane, dicyanodisamine, etc .; but not Limited to the above. In terms of heat resistance, price, feed Qualitative, widely used, etc., preferably aromatic diamine, most preferably 4,4 < diaminodiphenylmethane. The phosphorus compound (D) used in the present invention includes phosphate esters, such as trimethyl phosphate , Triethyl phosphate, tributyl phosphate, tri-2-hexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, triphenol phosphate, tricresyl phosphate phosphate (phenol diphenyl) phosphate, Xylyldiphenyl) ester, (Ethylhexyldiphenyl) phosphate, Tris (2,6-xylyl) phosphate This paper size applies to the two national standards (CNS) A4 specifications (210X297) (Please First read the note f on the back, then fill out this page and print it. Printed by the Men ’s Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Rosinyl diphenyl) ester, etc .; Condensed phosphate esters, such as ammonium polyphosphate, polyphosphosamine salt, etc .: red phosphorus, guanidine phosphate, (dialkylhydroxymethyl) phosphate, etc .; but not particularly limited to the above These compounds may be used in combination of two or more. The composition is prepared as follows: component (A) (that is, an unhalogenated epoxy resin having at least two epoxy groups in a molecule) * component (B) (that is, having at least one maleimide imine in a molecule Based maleimide compound), component (C) (ie, a curing agent having an amine group), and component (D) (ie, a phosphorus compound) are mixed * The mixing ratio is 100 parts by weight of the ingredient (A) There are 20 to 250 parts by weight of component (B) and 20 to 65 parts by weight of component (C); and component (D) is based on phosphorus and accounts for component (A), (B), (C) 0.5 to 4.5 parts per 100 parts by weight of total weight, and the nitrogen content in the composition accounts for 2.0 to 10 parts by weight per 100 parts by weight of the total weight of the composition. When the component (B) is less than 20 parts by weight / 100 parts by weight: 1: parts of the component (A), the effect of the component (B) on the flame retardancy becomes smaller and the heat resistance becomes worse. When the amount exceeds 2 0 5 Replacement parts / 100 parts by weight of the component (A), the adhesion becomes worse. So these amounts are unexpected. When the ingredient (C) is less than 20 reset parts / 100 parts by weight of the component (A), The resin cannot be completely cured. If the amount exceeds 65 parts by weight / 100 parts by weight of the component (A), 'a large amount of amine groups will remain' and the water vapor resistance property is deteriorated. Therefore, these applications are not expected. When the amount of phosphorus in ingredient (D) is less than 0.5 weight children / 100, this paper is not used in China National Standard (CNS) A4 specification (210X297 mm) ~. (Please read the note on the back first (Fill in this page again)) Thread. A7 _B7_ printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention §) Parts by weight (ingredient (A) + (B) + (C)) The flammability effect becomes small, but if it exceeds 4.5 weight children / 1 100 weight children (ingredient (A) + (B) + (C)), the heat resistance will be worsened. expected. In addition, when the nitrogen element is less than 2.0 parts by weight / 100 parts by weight of the total composition, the effect of the nitrogen element on the flame retardancy becomes small, but if it exceeds 10.0 parts by weight / 100 parts by weight (ingredient (component ( A) + (B) + (C)), and the water vapor resistance is deteriorated. Therefore, these uses are not expected. The flame-retardant resin composition of the present invention can be applied in various forms, and when used to impregnate a substrate, a solvent is usually used. * This solvent must be used for some or all of the components in the composition. The ingredients have good solubility. However, poor solvents can also be used as long as they do not adversely affect the composition. Solvents useful in the present invention include: ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc., aromatic hydrocarbons, such as toluene, xylene, etc .: various glycol ethers, such as Base cellolysin, ethyllysin, butyllysin, isobutyllysin, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene Di-fermented monopropyl ether, di-propanedio-mono-propyl ether, ethylene glycol mono-isopropyl ether, diethylene glycol mono-isopropyl ether, diethylene glycol monobutyl ether, etc .; esters, such as methyllysin Acetate, ethyl lysone acetate * butyllysin acetate, ethyl acetate, etc .; dialkylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, dioxanyl dibutyl ether, etc. • Amines, such as N, N-dimethylacetamide, N, N-dimethylmethoxamine, N-methyl-2-pyrrolidone, etc. ; Alcohols, such as methanol, ethanol, etc .; It can be used in combination of two or more types. · This paper size is applicable to the Chinese Standard for Household Standards (CNS) A4 specification (2 丨 0X297 mm). ΤΛ (Please read the precautions on the back before filling this page). Industrial and consumer cooperative printing A7 B7 _V. Description of the invention 6) The resin composition of the present invention is dissolved in the above-mentioned solvent to make a lacquer, and the lacquer is used to coat and impregnate a substrate (eg, a glass male's male ' Glass is not made of fabric, male material made of paper or non-glass components), and then the unbroken substrate is dried in an oven at 80 ° C to 200 ° C to prepare a prepreg of a printed circuit board. . The pre-ulcerated hip can be pressed to make a printed circuit board. The resin composition of the present invention has high flame resistance without adding a halogen compound, and contains a thermosetting resin that does not adversely affect commercially available products, so it is suitable for use in laminates, metal-clad laminates, etc. * >) Preferable specific examples Example 1 A mixed solvent of 1/1 of N, N-dimethylmethylamine / methyl ethyl ketone was added to 100 parts by weight of a phenol formaldehyde epoxy resin (DAINIPPON INK & CHEMICALS INC (Manufactured by EPICLON N-770)), 193 parts by weight of N, N — 4,4′-diphenylmethane dicis-butenediamidoimide (manufactured by KI CHEMICAL INDUSTRY CO., LTD., (BMI • Η)) ， 6 1 replacement parts 4,4 ”monodiaminodiphenylmethane and 100 parts by weight of triphenyl phosphate to make lacquer, and the non-volatile matter concentration is 50%. At this time, Phosphorus accounted for 1,0 reset parts of epoxy resin, 2.7 reset parts of the total weight of the maleimide compound and the curing agent. Take 100 parts by weight of glass cloth (thickness 0.18mm, NNITTO BOSEKI (Manufactured by CO., LTD.) Impregnated with the above lacquer (the amount is 80 parts by weight based on the solid content of the lacquer), and then dried in a 15 or oven 4 Made by Zhong Er (with resin content of 44.4wt%) · (Read "Notes on the back side before filling in this page") The size of the paper is applicable to the Chinese national kneading rate (CNS) A4 * l grid ( 2 丨 0X297mm) • 12- Α7 Β7 V. Description of the invention ί)) 8 pieces of the pre-crushed so obtained "-one piece is stacked, and the top and bottom of the obtained assembly are each placed with a thickness of 3 5 of electrolytic copper foil, Then, 40 kgi / ciri, 170t, hot-pressed for 120 minutes to obtain a double-sided mesh-clad laminate with a thickness of 1.6 mm. The flame retardancy of the obtained laminate is perpendicular to the UL-9 standard. Evaluation by ignition test method. Welding heat resistance and peeling strength are also tested in accordance with JIS C 6481. In the welding heat resistance measurement, the laminate is boiled for 2 hours and subjected to water vapor absorption treatment, and then allowed to float at 2 6 Ot solder bath for 180 seconds, then check the appearance. • Furthermore, determine the glass transition temperature based on the viscoelastic method to obtain the ta η 5 peak line temperature. • The results are shown in Table 1. {Please read the note f on the back first Please fill in this page again) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the Shellfish Consumer Cooperative, this paper is also applicable to Chinese national standards (CNS) A4 specification (210 × 2Ϊ »7mm) _ 13 _ ^ 88768 V. Description of the invention h) Table 1 Project example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Compounding amount (parts by weight) EPICLON Ν-770 0 100 80 100-100 100 100 Ep 1001s-20-----Triglycidyl isocyanurate---100---BMI-H3) 193 193 193 88 54 24 22 4,4'-diamino Diphenylmethane 61 61 61 36 32 26 23 Tris (triphenylene) 100 100-46 15 42 65 CR-74 Guang 100----Phosphorus cord (M parts) 5, 2.7 2.7 2.3 2.0 0.8 2.7 4.3 Nitrogen cord (M copies) 5.2 5.2 5.2 9.6 2.2 2.9 2.4 Characteristic difficulty test (UL 94) V-0 V-0 ν · ο V-0 V-0 V-0 V-0 Welding texture; > Passed Passed Passed Passed Peeling strength (KN / cm) 1.5 1.8 1.5 1.7 1.9 1.8 1.6 Tg (DMA method Xt) 175 165 173 168 170 155 150 (Read the "Notes on the back side before filling in this page and set the central standard of the Ministry of Economic Affairs" The paper size printed by the Bureau's Consumer Cooperatives is applicable to the National Standard for Difficulties (CNS) A4 (210X297). -14- 888768_b7 __ Five 'Invention Note i2) Note: 1): DIANIPPON INK & Phenolic lacquer type epoxy resin made by CHEMICALS INC. 2): Double S & A type epoxy resin made by Yuka-Shell Epoxy Co., Ltd .; 3): N, N '— 4,4-diphenylmethanebiscis-butenediamidoimide manufactured by Keiai Kasei KK · 4): Condensed discic acid ester made by Daihachi Kagaku Kogyo KK · t 5): per 100 parts by weight of epoxy resin, cis butadiene imine compound and curing agent, parts by weight of phosphorus element cable 6): parts by weight of nitrogen per 100 parts by weight of total composition reset 〇7): Appearance of the sample after boiling for 2 hours in water vapor * and then floating in a flux bath at 260 ° C for 180 seconds. ------------ ο ------ Order ------ line; '' (Please read the notes on the back before filling out this page) Central Government Bureau of the Ministry of Economic Affairs The paper size of the printed consumer cooperative is applicable to the Chinese national standard (CNS) A4 specification (210X297 mm) -15- 388 Liu V. Description of the invention h) Table 2 Project Comparative Example_1 Comparative Example 2 Comparative Example 3 Bina Comparative Example 5 Comparative Example 6 Comparative Example 7 Formulation 1: (parts by weight) EPICLON N-770 100 100 100 100 100 100-Isoxian acid 36 water glyceride--•--100 ΒΙ · Η 15 88 210 88 88 88 110 4,4'-Diaminodiphenylmethane 22 36 61 36 15 70 38 Triphenyl Ester 46 10 100 145 46 46-Red Series----_--3 Phosphorus (M parts) 3.2 0.4 2.6 6.1 2.2 1.7 1.2 Nitrogen cable (S * parts) 2.3 5.1 5.3 3.2 3.6 5.5 11.2 Characteristic flame resistance test (UL 94) V-1 ν · 1 V-0 V-0 V-0 V-0 V-0 Welding Thermal resistance 71 Foaming by foaming Foaming Foaming Peeling strength (KN / cm) 1.9 1.6 1.1 1.2 1.3 1.3 1.2 Tg (DMA ^ Kt :) 140 175 185 121 138 156 156 Note ^. Please fill in this page again) Order-H—The consumption of shellfish by the Central Bureau of the Ministry of Economic Affairs Copies of the printing press, paper size, Chinese National Standard (CNS) A4 (210X297 male 1) 888768: V. Description of the invention ") Examples 2 to 7 and Comparative Examples 1 to 7 Repeat the steps of Example 1, but use Copper-clad laminates with the compositions shown in Tables 1 and 2 • The evaluation results are shown in Tables 1 and 2 • The laminates made with the compositions shown in the examples have flame retardancy and soldering heat resistance Excellent in both adhesion and adhesion properties v The flame-retardant resin composition of the present invention has high flame retardancy without adding halogen compounds, and also has excellent heat resistance and excellent adhesion properties, so the novel flame-retardant thermosetting resin composition proposed by the present invention The material is non-halogen material, and there will be great demand in the future. (Please read "Note f on the back side before filling out this page.) 1 cell (210 > < 297 mm).