TW201247853A - Flame retardant hardener and flame retardant hardener composition - Google Patents

Abstract

The present invention provides a flame retardant hardener which contains phosphorus and a special flame retardant chemical structure and can effectively reduce phosphorus content to reach the requirement of UL-94/V-O, decrease damage to the original physical properties, increase glass transition temperature and prevent hardened glass transition temperature of semi-hardened product from decreasing with time. The purpose of this invention is to provide a flame retardant hardener composition that contains: (a) flame retardant hardener, (b) epoxy resin and (c) hardening promoter; and is suitable to prepare adhesive sheets, composite material, laminates, printed circuit boards, substrates used in thickening method, adhesive used in copper foils, prepregs etc.

Description

201247853 六、發明說明： 【發明所屬之技術領域】 本發明提供一種耐燃性硬化劑及耐燃性硬化劑組成物，係用 於製造黏合片、複合材料、積層板、印刷電路板、增厚法之基板、 銅箔用之接著劑、預浸潰片等。 【先前技術】 近年來國際大廠規範、歐盟指令等環保要求，ώ素耐燃劑將 會逐漸被淘汰，這是由於齒素在受熱過程中會分解釋放出具有腐 蝕性的鹵化氫氣體及大量煙霧，雖然可以達到預期的耐燃效果， 但是卻會危害人體健康及臭氧層破壞，以其它耐燃元素取代鹵素 所發展出新型難燃劑，是近年來全球耐燃劑發展之趨勢。 磷系化合物做為新一代具有環保概念的難燃劑，已被廣泛地 研究和應用，例如直接以磷酸酯等來取代齒素之耐燃劑，以改善 樹脂燃燒特性，然而添加這些磷化合物在樹脂中，會造成磷化合 物在樹脂中移行性或劣解，磷化合物的高溫高溼水解問題，直接 影響到樹脂基材的電氣性質、力學特性。 因環保與安全實用考量，反應型磷系難燃劑已逐漸取得市場主流 地位，其中以9，1〇_二氫_9_氧雜_1〇 一磷雜菲一ι〇—氧化物 (9,l〇'Dihydro-9-〇xa-l〇- phosphaphanthrene-lO-oxide/簡稱D0P0)最為重要，在印刷電路 板走入無鹵化後，Dop〇型環氧樹脂因含有D0P0剛性基，使得D〇p〇 型壤氧樹脂比傳、统TBBA型漠系環氧樹脂更具脆性，在印刷電路板 201247853 加工過程中因裁邊、鑽孔等外力，造成不規則龜裂現象，使得製 成良率無法提高。 中華民國專利公告476771號揭示一種含磷難燃環氧樹脂組 成物中之含構化合物，該含構化合物部份係為雙酚A或雙酚與甲 醛' D0P0之反應物縮合而成，可做為含磷硬化劑使用；其缺點在 於其中之合成紐其反應率低、DGPG殘存量高、其與環氧樹脂固 化物吸水性高，不利於用於電子材料之用途。 中華民國專利公開200604239號揭示一種含磷化合物之製造 方法，包含使下述反應：（A)至少具有選自h—P=〇基、pH基及p_〇H 基之基之有機磷化物及(B)酚醛烷基醚樹脂；其缺點在於其環氧樹 脂半固化物之固化玻璃轉移溫度，會隨半固化物存放時間而下 降，及其環氧樹脂固化物之磷含量需要3. 〇%以上才會達到 UL-94/V-0耐燃效果。 中華民國專利公開201109371A域揭示-種製造具有阻燃性 及耐紐經姐質之_硬化敝綠，其包含丨）·麟化合物及 搭化合物在雜條齡在下絲，以製備—可溶_樹脂化合 物；及2).將驗製備之可溶祕樹脂化合物與一含碌化合物於溶 劑導引脫水，以便形成該經鱗改質的阻燃硬化劑；其缺點在於其 環氧樹脂伟化物之附溫度，會隨半物存放時間 而下降，及其環氧樹脂固化物之璘含量需要3. 〇%以上才會達到 UL-94/V-0财燃效果。 由以上可知目^所揭示之含磷硬化劑，應用在印刷電路板 201247853 上，軸克服了加工過程中因裁邊、鑽孔等外力所造成不規則龜 、1靖仁仍存在其環氧樹脂半固化物之固化玻璃轉移溫度，會 隨半雜物存放咖而下降問題，域環氧樹翻化物之鱗含量 需要3. 上才會翻IIL-94/V-0耐燃效果。 【發明内容】 土明所欲解決之問題，如目前公知技術範圍之含填硬化劑， 其存在的_為，先驗狀含♦更化_魏概半固化物之 固化玻璃轉移溫度’會隨半gj化物存放時間而下降；其被忽略的 問題為’含磷硬化劑與環氧樹脂固化物之碟含量需要請以上才 會達到UL-94/V-0耐燃效果。 解決之問題之技術手段，鑑於上述問題，本發明提供一種耐 燃性硬化劑，其具有如式（一）所示之化學結構： 式㈠201247853 VI. Description of the Invention: [Technical Field] The present invention provides a flame-resistant hardener and a flame-resistant hardener composition for use in the manufacture of adhesive sheets, composite materials, laminated sheets, printed circuit boards, and thickening methods. A substrate, an adhesive for copper foil, a prepreg, or the like. [Prior Art] In recent years, international environmental standards, EU directives and other environmental requirements, alfalfa flame retardant will be gradually eliminated, because the dentate will decompose during the heating process to release corrosive hydrogen halide gas and a large amount of smoke. Although it can achieve the expected flame resistance, it will endanger human health and the destruction of the ozone layer. The replacement of halogen with other flame-resistant elements has developed a new flame retardant, which is the trend of global flame retardant development in recent years. Phosphorus compounds have been widely studied and applied as a new generation of environmentally friendly flame retardants. For example, phosphoric acid esters are directly substituted by phosphoric acid esters to improve the combustion characteristics of resins. However, these phosphorus compounds are added in the resin. In this case, the phosphorus compound is caused to migrate or degrade in the resin, and the high-temperature and high-humidity hydrolysis of the phosphorus compound directly affects the electrical properties and mechanical properties of the resin substrate. Due to environmental protection and safety considerations, reactive phosphorus-based flame retardants have gradually gained market mainstream status, among which 9,1〇_dihydro_9_oxa-1〇-phosphonium phenanthrene-oxide (9) , l〇 'Dihydro-9-〇xa-l〇- phosphaphanthrene-lO-oxide/referred to as D0P0) is the most important, after the printed circuit board walks into the non-halogenated, Dop〇 type epoxy resin contains D0P0 rigid base, making D 〇p〇 type oxy-resin is more brittle than TBBA-type epoxy resin. In the process of printing circuit board 201247853, irregular cracking occurs due to external forces such as trimming and drilling. The rate cannot be increased. The Republic of China Patent Publication No. 476771 discloses a structural compound in a phosphorus-containing flame-retardant epoxy resin composition, which is obtained by condensing a reaction of bisphenol A or bisphenol with formaldehyde 'D0P0. It is used as a phosphorus-containing hardener; its disadvantage is that the synthesis reaction has low reaction rate, high residual amount of DGPG, and high water absorption with the cured epoxy resin, which is disadvantageous for use in electronic materials. A method for producing a phosphorus-containing compound comprising the following reaction: (A) an organic phosphide having at least a group selected from the group consisting of h-P=fluorenyl, pH, and p_〇H groups, and a method for producing a phosphorus-containing compound (B) A phenolic alkyl ether resin; a disadvantage of the cured glass transition temperature of the semi-cured epoxy resin, which decreases with the storage time of the semi-cured material, and the phosphorus content of the epoxy resin cured product needs to be 3. 〇% The above will achieve UL-94/V-0 flame resistance. The Republic of China Patent Publication No. 201109371A discloses a method for producing a flame retardant and refractory enamel, which comprises a ruthenium compound and a compound compound at the age of the mixed strands to prepare a soluble resin. a compound; and 2). The soluble resin compound prepared by the test and the hydrazine compound are dehydrated in a solvent to form the scaly modified flame retardant; the disadvantage is that the epoxy resin is attached The temperature will decrease with the storage time of the half material, and the content of the epoxy resin cured product needs to be more than 3. 〇% to achieve the UL-94/V-0 fuel economy effect. The phosphorus-containing hardener disclosed in the above can be applied to the printed circuit board 201247853. The shaft overcomes the irregular turtle caused by the external force such as trimming and drilling during the processing, and the Jingjing still has its epoxy resin half. The curing glass transition temperature of the cured product will decrease with the storage of the semi-mesh storage, and the scale content of the domain epoxy tree turning compound needs 3. The IIL-94/V-0 flame resistance effect will be turned on. SUMMARY OF THE INVENTION The problem that the soil is intended to solve, such as the hardening agent contained in the well-known technical scope, exists in the presence of a prior art, and the cured glass transition temperature of the semi-cured material is The semi-gj compound decreases in storage time; the neglected problem is that the disk content of the phosphorus-containing hardener and the epoxy resin cured product needs to be above the UL-94/V-0 flame resistance effect. Means for Solving the Problems In view of the above problems, the present invention provides a flame retardant hardener having a chemical structure as shown in the formula (I):

其中R為選自：Where R is selected from:

Α為選自： —NH·— 5 201247853Α is selected from: —NH·— 5 201247853

、共價鍵; B為選自：, covalent bond; B is selected from:

X為選自：X is selected from:

η為選自：1〜5的整數； m為選自：1〜5的整數。 本發明之-種4紐慨劑組成物 ，包括： (a) 财燃性硬化劑，其具有如式㈠所式之化學結構； (b) 環氧樹脂；（c)硬化促進劑。 對照先前技術之功效，先前技術之含罐硬化劑，雖然在產業 上已被大量使用，但對於高玻璃轉移溫度之需求仍有不足，半固 201247853 化物之祕破璃轉移溫度，有經時性破购移溫度下降等問題仍 待解決。 本發明之-獅雛硬_，其含有磷及特殊崎·性結構， 可以再包含氮，可以有效降低達到UL—94/Μ}·_含量，減 少對原有物性的破壞，提高玻璃轉移溫度，避免半固化物之固化 玻璃轉移溫度經時τ降，域前麟之賴硬倾所不及，可以 符合產業啟切之需求。 【實施方式】 本發明之目的在提供一種耐燃性硬化劑’其具有如式（一）所 示之化學結構： 式（一）η is an integer selected from: 1 to 5; m is an integer selected from the group consisting of 1 to 5. The invention relates to a composition of the invention, comprising: (a) a flammable hardener having a chemical structure of the formula (1); (b) an epoxy resin; and (c) a hardening accelerator. Compared with the efficacy of the prior art, the prior art can-containing hardener has been used in large quantities in the industry, but the demand for high glass transfer temperature is still insufficient, and the semi-solid 201247853 compound has a glass transition temperature, which is time-dependent. Problems such as the decline in the temperature of the purchase and removal have yet to be resolved. The lion's hard _, which contains phosphorus and a special sacrificial structure, can further contain nitrogen, can effectively reduce the content of UL-94/Μ}·_, reduce the damage to the original physical properties, and increase the glass transition temperature. , to avoid the semi-cured solidified glass transfer temperature over time τ drop, the domain before the Lin is hard to fall, can meet the needs of the industry. [Embodiment] The object of the present invention is to provide a flame-resistant hardener which has a chemical structure as shown in the formula (I):

7 201247853 ——CH2NH—^ NH—7 201247853 ——CH2NH—^ NH—

η為選自：1〜5的整數； m為選自：1〜5的整數。 本發明之一種耐燃性硬化劑，其特徵在於分子鏈具有如式(二) 所示之化學結構： 式(二）η is an integer selected from: 1 to 5; m is an integer selected from the group consisting of 1 to 5. A flame-resistant hardener of the present invention, characterized in that the molecular chain has a chemical structure as shown in the formula (II):

其具有耐燃性，可再導入三嗪類（Triazine )與D0P0 201247853 (9,10-Dihydro-9-oxa-10- phosphaphanthrene-10-oxide)之鱗，產生填氮财燃加成效果，賦 予聚合物多重阻燃機制，同時也降低聚合物中磷的使用量。 本發明合成一種耐燃性硬化劑，其所使用之二酚類包括：It has flame resistance and can be further introduced into the scale of Triazine and D0P0 201247853 (9,10-Dihydro-9-oxa-10- phosphaphanthrene-10-oxide) to produce a nitrogen-filled fuel-burning effect. Multiple flame retardant mechanisms, while also reducing the amount of phosphorus used in the polymer. The present invention synthesizes a flame retardant hardener, and the diphenols used therein include:

、雙酚A、雙酚等。 本發明合成一種耐燃性硬化劑，其所使用之三嗪類包括：三 聚氰胺、甲基胍胺、苯基胍胺、顯衍生物、三聚驗' 甲基三 聚氰酸酯、乙基三聚氰酸酯、乙醯基三聚氰酸酯、三聚氰酸衍生 物等。 本發=成-，耐燃性硬化劑，其所使用之 2二;;：:^:卜_、甲醇、乙醇、丙醇、， 醇甲_^旨等 丙二醇㈣、乙二醇甲醚、丙二 氫氧化鈉、氫U耐:說=劑所使用之鹼性觸媒包括: 級胺、氨等。 鎂、奴馱鈉、碳酸鉀、碳酸鈣、三 ㈣錢、檸檬酸、料酸、甲基苯續酸及 201247853 其它路易士酸等 本發明之目的在提供一種耐燃性硬化劑組成物，包括： (a)耐燃性硬化劑，其具有如式（一）所式之化學結構： 式㈠, bisphenol A, bisphenol, and the like. The invention synthesizes a flame retardant hardener, and the triazines used thereof include: melamine, methyl decylamine, phenyl decylamine, a derivative derivative, a trimerization test, a methyl methacrylate, an ethyl trimer. Cyanate ester, acetamyl cyanurate, cyanuric acid derivative, and the like. The hair ==-, a flame retardant hardener, which is used 2 2;;::^:Bu, methanol, ethanol, propanol, alcohol, propylene glycol (tetra), ethylene glycol methyl ether, C Two sodium hydroxide, hydrogen U resistance: said: the alkaline catalyst used in the agent includes: amine, ammonia and the like. Magnesium, sodium sulphate, potassium carbonate, calcium carbonate, tris(4) money, citric acid, acid, methyl benzoic acid and 201247853 Other Lewis acids and the like The object of the present invention is to provide a flame resistant hardener composition comprising: (a) a flame resistant hardener having a chemical structure of the formula (I):

其中R為選自：Where R is selected from:

A為選自：A is selected from:

▽ 、共價鍵； B為選自：▽ , covalent bond; B is selected from:

10 20124785310 201247853

x為選自 -C(CH3)2- 、 -CH2-;x is selected from the group consisting of -C(CH3)2-, -CH2-;

、氫； η為選自：1〜5的整數； m為選自：1〜5的整數. (b)環氧樹脂； (c)硬化促進劑。 ―本發明之—種耐燃性硬化劑組成物之環氧細旨，使用二個環 ，基以上之多宫能基環氧樹脂包括 :酚醛型環氧樹脂、甲酚醛型 '雙_^環氧翻旨、四苯絲水甘細基乙烧、三苯 基縮水=姆基ψ燒、三縮水甘絲對絲絲、三縮水甘油基 =聚異氰城、四縮水甘油基二絲二苯基找、四縮水甘油基 二甲苯二胺、四縮水甘油紅3_雙氨基甲基環己炫2甲醇基丙 Jc甘Ail、丙二醇二縮水甘油_、其它二個以上環氧基之 環氧樹脂、二個以上環氧基之環氧樹脂稀釋劑等。 —本發Θ之-種耐燃性硬化敝成物之環氧細旨，使用含二個 環氧基之魏_旨包括：雙_麵树响、频陳缩水甘油 驗、雙__水甘觸、氫化伽型縮水甘㈣、氫化雙咖 縮水甘_、鄰苯二曱酸縮水甘油§旨、海因縣樹脂、酿亞胺環 201247853 氧樹月曰、雙(2, 3環氧基環戍基)驗、3, 4環氧基-6-甲基j裒已基甲酸 -3，，4，-環氧基_6:甲基環己基甲醋、乙烯基環己稀二環氧化:物、 M環氧基環己基甲酸~3，，4，-環氧基環己基甲醋、二異戊二婦二環 氧化物、二了二烯二環氧化物、己二酸二(3, 4環氧基I甲基環己 基甲醋）、二縮水甘㈣、聚乙醇二縮水甘油醚、聚丙醇二縮水甘 油醚、聚丁醇二縮水甘油醚、丁醇二縮水甘純、二縮水甘油基 苯胺、對苯二甲酸二縮水甘油s旨、内次甲基四氫鄰苯二甲酸二縮 水甘油sa、鄰苯二m缩水甘油酯、四氫鄰苯二甲酸二縮水甘 油酉曰、間苯二曱酸二縮水甘油g旨、4,5環氧環己烧丨，2_二甲酸二缩 水甘油ia、鄰苯二辛酸二環氧秘、二氧化戊烯、二氧化雙環戊 二烯多元醇醚、其它二個環氧基之環氧樹脂、二個環氧基之環氧 樹脂稀釋劑等。 本發明之一種耐燃性硬化劑組成物之硬化促進劑包括已知之 一級胺、四級銨鹽、咪唑類、金屬有機鹽、膦類化合物、三氟硼 胺錯合物、酚類等。 本發明之一種耐燃性硬化劑組成物之共硬化劑包括已知之， 酚醛料脂、二氰二胺、馬林酸酐/苯乙烯共聚物、三嗓驗酿樹脂、 苯并号井（Benzoxazine)等。 本發明之目的在提供一種難耐燃性硬化劑組成物，其係用於 製造黏合片、複合材料、積層板、印刷電路板、增厚法之基板、 銅箔用之接著劑、預浸潰片等。 12 201247853 實施例1 將2 —苯基~3, 3—雙(4—羥苯基）苯幷吼咯酮393g(lmole)、 24°/〇曱酿水溶液287.5g (2. 3mole)、三乙胺1. Og，置入裝有機械 攪拌、冷凝管、蒸餾受器、氮氣之四口反應瓶中，將溫度升至 °C ’反應5小時後加入5〇〇g 丁醇，將溫度升至90¾，反應5小時 溫度後逐步加熱至12(TC共沸去除水份，再加入9,10-二氫-9-氧 雜-10-磷雜菲-10-氧化物432g (2mole)，將溫度升至180°C減壓 脫除溶劑’可得到耐燃硬化劑A，測量其磷含量為7. 27%，氮含 量為1. 64%，〇H當量為426。 實施例2 將紛酜 318g (lmole)、24%曱醛水溶液 287.5g (2.3mole)、三 乙胺1. 〇g，置入裝有機械授拌、冷凝管、蒸德受器、氮氣之四口 反應瓶中’將溫度升至70。(：，反應5小時後加入500g 丁醇，將溫 度升至90 C，反應5小時溫度後逐步加熱至i2(TC共沸去除水份， 再加入9,10-二氫-9-氧雜-ίο-破雜菲_ι〇_氧化物432g (2mole)， 將溫度升至180°C減壓脫除溶劑，可得到耐燃硬化劑β，測量其磷 含量為7.97%，〇η當量為389。 實施例3 將2—氫一3, 3-雙(4—羥苯基）苯幷β比咯酮317g (lmole)、 24%曱醛水溶液375g (3.0mole)、三乙胺i.0g，置入裝有機械攪 拌、冷凝管、蒸餾受器、氮氣之四口反應瓶中，將溫度升至7〇〇c， 反應5小時後加入500g 丁醇’將溫度升至9〇°c，反應5小時溫度 13 201247853 後逐步加熱至12(TC共沸去除水份，再加入9,10-二氫-9-氧雜-i〇— 磷雜菲-10-氧化物432g (2mole)，將溫度升至18(TC減壓脫除溶 劑’可得到耐燃硬化劑C ’測量其磷含量為9. 29%，氮含量為丨.4〇 % ’ OH當量為5〇〇。 實施例4 將酚酞 318g (lmole)、雙酚 A 228g (lmole)、24%曱醛水溶 液500g. (4mole)、三乙胺1. 0g，置入裝有機械撥拌、冷凝管、蒸 館受器、氣氣之四口反應瓶中’將溫度升至70 C，反應5小時後 加入500g 丁醇，將溫度升至9(TC，反應5小時溫度後逐步加熱至 120 C共彿去除水份，加入9,10-二氫-9-氧雜-10-鱗雜菲_ι〇__氧化 物432g (2mole) ’將溫度升至150°C脫除溶劑，再加入三聚氮胺 126g (lmole)將溫度升至180°C減壓脫除溶劑，可得到财燃硬化 劑D ’測量其鱗含量為5. 89%，氮含量為7. 29%，ojj當量為228。 實施例5 將2-苯基一3, 3-雙(4-羥苯基)苯幷吡咯_ 393g(；lmole)、 雙酚F 200g( lmole)、24%曱醛水溶液750g( 6mole )、三乙胺丨〇g， 置入裝有機械授拌、冷凝管、蒸餾受器、氮氣之四口反應瓶中， 將溫度升至70 C ’反應5小時後加入500g 丁醇，將溫度升至9〇 C ’反應5小時溫度後逐步加熱至120 C共沸去除水份，力0入9, ι〇_ 二氫-9-氧雜-10-峨雜菲-10-氧化物864g (4mole)，將溫度升至 150°C脫除溶劑，再加入苯基胍胺187g (lmole)將溫度升至180 °C減壓脫除溶劑’可得到耐燃硬化劑E，測量其磷含量為7 22%， 14 201247853 氮含量為4.90%，OH當量為429。 實施例6 將2—氩基一3, 3—雙(4一經苯基）苯幷α比B各闕393g(lmole)、 9, 9—雙(4一經苯基）芴350g (lmole)、24%曱齡水溶液i〇〇〇g (8mole)、三乙胺1· 0g，置入裝有機械攪拌、冷凝管、蒸餾受器、 氮氣之四口反應瓶中，將溫度升至70°C，反應5小時後加入5〇〇g 丁醇，將溫度升至90°C，反應5小時溫度後逐步加熱至i20°c共 沸去除水份，加入9,10-二氫-9-氧雜-10-填雜菲-10-氧化物i〇g〇g (5mole)，將溫度升至150°C脫除溶劑，再加入曱基胍胺i25g (lmole)將溫度升至180°C減壓脫除溶劑，可得到耐燃硬化劑f， 測量其磷含量為7· 56%，氮含量為3. 41%，0H當量為512。 比較例1 將雙酚 A 228g (lmole)、24%甲醛水溶液 287.5g (2.3mole)、 三乙胺1. 0g，置入裝有機械攪拌、冷凝管、蒸餾受器、氮氣之四 口反應瓶中，將溫度升至7〇°C，反應5小時後加入500g 丁醇，將 溫度升至90°C，反應5小時溫度後逐步加熱至12(TC共沸去除水 份，再加入9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物432g (2mole)，將溫度升至180°C減壓脫除溶劑，可得到耐燃硬化劑g， 測量其磷含量為9. 01% ’ 〇H當量為344。 實施例7〜14 將實施例1〜6及比較例1之耐燃硬化劑A〜G、N-680(DIC/環氧 樹脂/環氧當量=212)、酚醛樹脂(0H當量=105)、促進劑2E4MZ(2- 15 201247853 乙基四甲基米坐）以丁_2〇〇g溶解均句，靜置12小時，調製 成樹月^ 4卩！知方法製備積層板，該法係將獅玻璃纖維布 含浸上述清漆樹脂液’然後於崎（含浸機溫度），乾燥卜3分 鐘’藉由調整控制乾燥時間得預浸半固化片，最後將8片半固化 片層層相4於兩片35 厚之_間，在25kg/em2壓力下，其控 制升溫程式為溫度85。(：日_ 30miiw溫度贿時間服―溫度 220 C時間12Gmin~>冷壓降溫至80¾，經熱冷壓後即可得到積層壓 5板。而可得到1. 6mm彳之銅ϋ基板’樹脂含量係在—砸的範 圍内，然後以DSC測試層合物的玻璃轉移溫度（Tgl)、以TGA測 試層合物的熱分解溫度及UL-94難燃性；將預浸半固化片，放置 於溫度2(TC，相對濕度80%之環境下7日，再將8片半固化片層 層相疊於兩片35//um厚之銅箔間，在25kg/cm2壓力下，其控制升 溫程式為溫度85°C時間30min—溫度14(TC時間lOmirw溫度220 °C時間120min—冷壓降溫至8(TC ’經熱冷壓後即可得到積層壓合 板。而可得到1.6刪厚之銅箔基板，樹脂含量係在40 —45%的範圍 内’然後以DSC測試層合物的玻璃轉移溫度（Tg2)，其結果如表 一所示。 201247853 表一 配比（重) 實施例7 實施例8 實施例9 實施例ID 實施例11 實施例12 實施例13 實施例14 A硬化劑 B硬化劑 426 — — —— —— — 一一一 —— 389 — — —— —— ——— 一一一 C硬化劑 *--- — 250 — — — ——一 一—》 D硬化劑 — — — 228 — —— ——一 一一― E硬化劑 — — — — 214 — ——一 F硬化劑 G硬化劑 ---- — —— —— —— 256 — ______ ---- — —— — —— 344 PN 315 315 263 105 210 2Ϊ0 210 262 N680 848 848 636 424 530 530 636 742 2E4MZ 8 8 6 4 5 5 6 7 P % 1.95 2.00 2.02 1.77 1.62 1.94 2.6 2 3 N % 0.88 0.00 0.3 2.19 1.10 0.88 難燃性UL-94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-1 Td (°C) 373 372 380 375 374 372 383 372 Tgl ( C ) 205 186 199 207 200 203 197 194 Tg2 (°C) 205 186 198 206 200 202 186 184 △Tg=Tgl-Tg2 0 ~~ 0 1 1' 0 1 11 10 由表一可知實施例1〜6所合成之财燃硬化劑A〜F配製成實施 例7~12之硬化物表現出耐燃性(UL-94/V-0)，磷含量需求為丨.62 02%，低於已知耐燃硬化劑g之磷含量需求2· 6% ;實施例 7〜12^Tg為(H ’實施例13〜14zjg為l〇〜ii，表示本發明之耐燃 硬化劑組成物半固化物之經時安定性優於傳統已知者’適合用於 用於製造黏合片、複合材料、積層板、印刷電路板、增厚法之基 板、銅箔用之接著劑、預浸潰片等。 本發明已經配合上述具體實施例、比較例描述，熟悉本項技 藝人士將可基於以上描述作出多種變化’不因此而限制本發明之 申請專利範圍。 17 201247853 【圖式簡單說明】 無 【主要元件符號說明】 無And hydrogen is selected from: an integer selected from the group consisting of: 1 to 5; m is an integer selected from the group consisting of: 1 to 5; (b) an epoxy resin; (c) a hardening accelerator. - The epoxy resin of the composition of the flame-retardant hardener of the present invention, using two rings, the polyglycol-based epoxy resin of the above base: phenolic epoxy resin, cresol type 'double _ epoxy旨,四苯丝水甘基乙烧, Triphenyl shrinkage = M-based ψ, tri-n-n- s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s Find, tetraglycidyl xylene diamine, tetraglycidyl red 3 _ bis aminomethyl cyclohexan 2 methanol based C J Gan Ail, propylene glycol diglycidyl _, other two or more epoxy epoxy resin, Two or more epoxy epoxy resin diluents and the like. - The carbonaceous purpose of this kind of flame-resistant hardening composition, using Wei with two epoxy groups - includes: double _ tree sound, frequency ginseng glycerin test, double __ water touch Hydrogenated galvanose (4), hydrogenated bis-glycolate _, phthalic acid glycidyl §, Hein County resin, brewed imine ring 201247853 Oxygen tree, bis (2, 3 epoxy ring oxime , 3, 4-epoxy-6-methylj-carbyl carboxylic acid-3,, 4,-epoxy-6: methylcyclohexyl acetal, vinyl cyclohexane dicyclic oxidation: , M epoxycyclohexylcarboxylic acid ~3,, 4,-epoxycyclohexyl methyl acetonate, diisopentyl diepoxide, diadiene diepoxide, adipic acid bis (3, 4 Epoxy group I methylcyclohexyl methyl acetate), diglycidyl (tetra), polyglycol diglycidyl ether, polyglycol diglycidyl ether, polybutanol diglycidyl ether, butanol diglycidyl, diglycidyl Aniline, terephthalic acid diglycidyl s, endomethyltetrahydrophthalic acid diglycidyl sa, phthalic acid m-glycidyl ester, tetrahydrophthalic acid diglycidyl hydrazine, isophthalic acid Bismuth hexahydrate Oil g, 4,5 epoxy cycloheximide, 2_dicarboxylic acid diglycidyl ia, phthalic acid diepoxy secret, pentylene oxide, dicyclopentadiene dihydric alcohol ether, other two An epoxy group epoxy resin, two epoxy group epoxy resin diluents, and the like. The hardening accelerator of a flame-resistant hardener composition of the present invention includes known primary amines, quaternary ammonium salts, imidazoles, metal organic salts, phosphine compounds, trifluoroborane complexes, phenols and the like. The co-hardener of a flame-resistant hardener composition of the present invention includes known phenolic resin, dicyandiamide, malic anhydride/styrene copolymer, triterpene resin, Benzoxazine, etc. . An object of the present invention is to provide a flame-resistant hardener composition for producing an adhesive sheet, a composite material, a laminate, a printed circuit board, a substrate for thickening, an adhesive for copper foil, and a prepreg sheet. Wait. 12 201247853 Example 1 2- phenyl~3,3-bis(4-hydroxyphenyl)benzoquinone 393g (lmole), 24°/brewed aqueous solution 287.5g (2.3mole), triethyl The amine 1. Og, placed in a four-neck reaction flask equipped with mechanical stirring, condenser, distillation receiver, nitrogen, the temperature was raised to ° C 'reaction 5 hours, 5 〇〇g of butanol was added, the temperature was raised to 902⁄4, after reacting for 5 hours, gradually heat to 12 (TC azeotropically remove water, then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 432g (2mole), the temperature The flammable hardener A was obtained by increasing the solvent to a temperature of 180 ° C. The phosphorus content was 7.27%, the nitrogen content was 1.64%, and the 〇H equivalent was 426. Example 2 318g ( Lmole), 245% aqueous solution of furfural 287.5g (2.3mole), triethylamine 1. 〇g, placed in a four-reaction reaction flask equipped with mechanical mixing, condensing tube, steaming receiver, nitrogen To 70. (:, after 5 hours of reaction, add 500 g of butanol, raise the temperature to 90 C, and gradually heat to i2 after 5 hours of reaction (TC azeotropically remove water, then add 9,10-dihydro-9- Oxygen-ίο-破杂菲_ι〇_oxide 432g (2 Mole), the temperature was raised to 180 ° C to remove the solvent under reduced pressure, and the flame retardant β was obtained, and the phosphorus content was measured to be 7.97%, and the 〇η equivalent was 389. Example 3 2-Hydrogen-3, 3-double (4-hydroxyphenyl) phenylhydrazine β pyrone 317g (lmole), 24% aqueous solution of acetal 375g (3.0mole), triethylamine i.0g, placed in a mechanical stirring, condensing tube, distillation receiver, In a four-neck reaction flask of nitrogen, the temperature was raised to 7 ° C, and after 5 hours of reaction, 500 g of butanol was added to raise the temperature to 9 ° C, and the reaction was heated for 5 hours and then gradually heated to 12 (TC azeotropy). Remove the water, add 9,10-dihydro-9-oxa-i〇-phosphaphenanthrene-10-oxide 432g (2mole), and raise the temperature to 18 (TC decompression solvent to obtain 'flame resistance' The hardener C' was measured to have a phosphorus content of 9.29%, a nitrogen content of 丨.4〇% 'OH equivalent of 5 〇〇. Example 4 phenolphthalein 318g (lmole), bisphenol A 228g (lmole), 24% 500 g. of furfural solution (4mole), triethylamine 1. 0g, placed in a four-reaction reaction flask equipped with mechanical mixing, condensing tube, steaming device, gas, 'to raise the temperature to 70 C, reaction 5 Add 500g of butanol after hours, will The temperature is raised to 9 (TC, after reacting for 5 hours, gradually heating to 120 C to remove water, and adding 9,10-dihydro-9-oxa-10-fluorene phenanthrene__ oxide 432g ( 2mole) 'The temperature is raised to 150 ° C to remove the solvent, and then added to the diazonium 126g (lmole) to raise the temperature to 180 ° C to remove the solvent under reduced pressure, the flammable hardener D ' can be measured to measure the scale content 5. 89%, nitrogen content was 7.29%, and ojj equivalent was 228. Example 5 2-phenyl-3,3-bis(4-hydroxyphenyl)benzopyrrole_393g (;lmole), bisphenol F 200g (lmole), 24% aqueous solution of furfural 750g (6mole), three Ethylamine 丨〇g, placed in a four-neck reaction flask equipped with mechanical mixing, condensation tube, distillation receiver, nitrogen, the temperature was raised to 70 C 'reaction for 5 hours, then 500g of butanol was added to raise the temperature to 9 〇C 'reacted for 5 hours, gradually heated to 120 C azeotropically to remove water, force 0 into 9, ι〇_ dihydro-9-oxa-10-indene phenanthrene-10-oxide 864g (4mole), The temperature was raised to 150 ° C to remove the solvent, and then phenylglycolamine 187 g (lmole) was added to raise the temperature to 180 ° C to remove the solvent under reduced pressure. The flame retardant E was obtained, and the phosphorus content was measured to be 72%. 14 201247853 The nitrogen content is 4.90% and the OH equivalent is 429. Example 6 2-aryl- 3,3-bis(4-monophenyl)benzoquinone α ratio B 阙 393 g (lmole), 9, 9-bis (4-phenylene) 芴 350 g (lmole), 24 100% aqueous solution i〇〇〇g (8mole), triethylamine 1·0g, placed in a four-neck reaction flask equipped with mechanical stirring, condenser, distillation receiver, nitrogen, the temperature was raised to 70 ° C, After 5 hours of reaction, 5 〇〇g of butanol was added, the temperature was raised to 90 ° C, and after 5 hours of reaction, the temperature was gradually heated to i20 °c to azeotropically remove water, and 9,10-dihydro-9-oxa- was added. 10-filled phenanthrene-10-oxide i〇g〇g (5mole), the temperature is raised to 150 ° C to remove the solvent, then add guanidinoamide i25g (lmole) to raise the temperature to 180 ° C decompression The solvent-resistant hardener f was obtained, and the phosphorus content was measured to be 7.56%, the nitrogen content was 3.41%, and the 0H equivalent was 512. Comparative Example 1 228 g (lmole) of bisphenol A, 287.5 g (2.3 mole) of a 24% aqueous formaldehyde solution, and 1.0 g of triethylamine were placed in a four-neck reaction flask equipped with a mechanical stirring, a condenser, a distillation receiver, and nitrogen. In the middle, the temperature is raised to 7 ° C, after 5 hours of reaction, 500 g of butanol is added, the temperature is raised to 90 ° C, and after 5 hours of reaction, the temperature is gradually heated to 12 (TC azeotropically removes water, and then 9,10 is added. - Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 432g (2mole), the temperature is raised to 180 ° C to remove the solvent under reduced pressure, the flame retardant g can be obtained, and the phosphorus content is measured to be 9 01% '〇H equivalent is 344. Examples 7 to 14 The flame-resistant hardeners A to G and N-680 (DIC/epoxy resin/epoxy equivalent = 212) of Examples 1 to 6 and Comparative Example 1, Phenolic resin (0H equivalent = 105), accelerator 2E4MZ (2- 15 201247853 ethyl tetramethyl rice sitting) dissolved in Ding 2〇〇g, and allowed to stand for 12 hours, prepared into a tree month ^ 4 卩! To prepare a laminated board, the method is to impregnate the varnish resin liquid with the lion glass fiber cloth and then dry it at the temperature of the salt (the temperature of the impregnation machine for 3 minutes) to adjust the drying time to obtain the prepreg prepreg, and finally 8 sheets of prepreg layer 4 between two sheets of 35 thick, under the pressure of 25kg / em2, its temperature control program is the temperature of 85. (: Day _ 30miiw temperature bribe time service - temperature 220 C time 12Gmin ~> cold The temperature is lowered to 803⁄4, and after heat-cold pressing, a laminate of 5 sheets can be obtained, and a copper-ruthenium substrate of 1. 6 mm can be obtained, and the resin content is in the range of 砸, and then the glass transition of the laminate is tested by DSC. Temperature (Tgl), TGA test laminate thermal decomposition temperature and UL-94 flame retardancy; prepreg prepreg, placed in temperature 2 (TC, relative humidity 80% environment for 7 days, then 8 prepregs Layers are stacked between two 35//um thick copper foils. Under the pressure of 25kg/cm2, the temperature control program is controlled at a temperature of 85 °C for 30 min - temperature 14 (TC time lOmirw temperature 220 °C time 120 min - cold The pressure drop is up to 8 (TC' can be obtained by hot-cold pressing, and a 1.6-thick copper foil substrate can be obtained, and the resin content is in the range of 40-45%. Then the laminate is tested by DSC. Glass transition temperature (Tg2), the results are shown in Table 1. 201247853 Table 1 ratio (heavy) Example 7 Example 8 Example 9 Example ID Example 11 Example 12 Example 13 Example 14 A hardener B hardener 426 — ——— — — 11——————————————————————— A C hardener*----250 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — G Hardener ----- ———————————————————————————————————————— 344 PN 315 315 263 105 210 2Ϊ0 210 262 N680 848 848 636 424 530 530 636 742 2E4MZ 8 8 6 4 5 5 6 7 P % 1.95 2.00 2.02 1.77 1.62 1.94 2.6 2 3 N % 0.88 0.00 0.3 2.19 1.10 0.88 Flame retardant UL-94 V-0 V-0 V-0 V-0 V-0 V-0 V- ○Tg=Tgl-Tg2 0 ~ ~ 0 1 1' 0 1 11 10 It can be seen from Table 1 that the flammable hardeners A to F synthesized in Examples 1 to 6 are formulated into the cured products of Examples 7 to 12 to exhibit flame resistance (UL-94/V- 0), the phosphorus content requirement is 丨.62 02 %, lower than the phosphorus content requirement of the known flame retardant hardener g: 2.6%; Example 7~12^Tg is (H 'Examples 13 to 14zjg are l〇~ii, indicating the flame resistant hardener composition of the present invention The stability of the semi-cured material is better than that of the conventional ones. It is suitable for use in the manufacture of adhesive sheets, composites, laminates, printed circuit boards, substrates for thickening methods, adhesives for copper foils, prepreg. Film and so on. The present invention has been described in connection with the above specific embodiments and comparative examples, and those skilled in the art will be able to make various changes based on the above descriptions, and thus do not limit the scope of the invention. 17 201247853 [Simple description of the diagram] None [Key component symbol description] None

Claims (1)

201247853 七、申請專利範圍： 1. 一種耐燃性硬化劑，其具有如式（一）所示之化學結構: 式㈠201247853 VII. Patent application scope: 1. A flame retardant hardener having a chemical structure as shown in formula (1): 其中R為選自：Where R is selected from: 19 20124785319 201247853 -C(CH3)2- 、 -CH2--C(CH3)2-, -CH2- 、氫； n為選自：1〜5的整數； m為選自：1~5的整數。 2. —種财燃性硬化劑組成物，包括： (a)耐燃性硬化劑，其具有如式（一）所式之化學結構: 式㈠And hydrogen; n is an integer selected from: 1 to 5; m is an integer selected from: 1 to 5. 2. A flammable hardener composition comprising: (a) a flame retardant hardener having a chemical structure of the formula (I): 其中R為選自：Where R is selected from: 20 201247853 —ch2nh20 201247853 —ch2nh 、共價鍵； B為選自：, covalent bond; B is selected from: -C(CH3)2- 、 -CH2-; II —CH 厂 P 2 I n為選自:-C(CH3)2-, -CH2-; II-CH Plant P 2 I n is selected from: m為選自：1〜5的整數； (b) 環氧樹脂； (c) 硬化促進劑； 3.如申請專利範圍第2項之一種耐燃性硬化劑組成物，其中可再包 含其它共硬化劑。 1如申睛專利範圍第2項之一種難耐雛硬化劑組成物之用途，係 用於製造黏合片、複合材料、積層板'印刷電路板、增厚法之基 板、銅箔用之接著劑、預浸潰片等。 21m is an integer selected from: 1 to 5; (b) an epoxy resin; (c) a hardening accelerator; 3. a flame-resistant hardener composition according to claim 2, which may further comprise other co-hardening Agent. 1 The use of a difficult-to-harden hardener composition according to item 2 of the scope of the patent application is for the manufacture of adhesive sheets, composite materials, laminated boards 'printed circuit boards, substrates for thickening methods, and adhesives for copper foils, Pre-impregnated tablets, etc. twenty one