1310401 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種含磷難燃硬化劑及其製造方法’尤指一種 含磷基基團的環氧樹脂之硬化劑及其製造方法。 【先前技術】 在所有高分子電子材料中，環氧樹脂具有便價格及高接著 性，最適合做印刷電路板以及積體電路封裝材料。含溴原子的環 氧樹脂特別適用於具有難燃特性的電路板。含溴樹脂可由 diglycidyl ether of bisphenol A (DGEBA)與 tetrabromobisphenol A (TBBA)的反應中得到。然而，這些含溴環氧樹脂在燃燒過程會釋 出漠化氫、dibenzo-p-dioxin及dibenzo-furan，其具有腐姓性及毒 性。 除了含齒素的化合物，另一種阻燃的方法便是在塑膠外再包 覆不可燃的外層。這些難燃化合物之中，具有高度阻燃性的反應 性有機磷化合物’例如含炔化合物及含磷化合物。含磷環氧樹脂 及硬化劑 DOPO (9，10-dihydro-9-oxa_10-phosphaphenaiitlirene 10-oxide)深受矚目，其具有一個可與貧電子化合物反應的活性氫 原子。貧電子化合物例如 benzoquinone、oxirane、maleic aeid、 bismaleimide、diaminobenzophenone、及 terephthaldicarboxaldehyde 〇 本發明因此提出一種新穎的含磷難燃硬化劑及其合成方法e 【發明說明】 本發明之目的在於提供一種難燃硬化劑，其具有較高的玻璃 轉移溫度及難燃性’並適用於積趙電路板及半導趙封裝材料。 本發明之另一目的在於提供一種製造難燃硬化劑之方法，可 藉由簡單的加成反應獲得。 1310401 因此’本發明之難燃硬化劑係具有如下之結構式：[Technical Field] The present invention relates to a phosphorus-containing flame retardant hardener and a method for producing the same, and particularly to a hardener for a phosphorus-containing group-containing epoxy resin and a method for producing the same. [Prior Art] Among all polymer electronic materials, epoxy resin has a high price and high adhesion, and is most suitable for printed circuit boards and integrated circuit packaging materials. The epoxy resin containing a bromine atom is particularly suitable for a circuit board having a flame retardant property. The bromine-containing resin can be obtained by the reaction of diglycidyl ether of bisphenol A (DGEBA) with tetrabromobisphenol A (TBBA). However, these bromine-containing epoxy resins release desert hydrogen, dibenzo-p-dioxin and dibenzo-furan during combustion, which have rot and toxicity. In addition to the dentate-containing compound, another flame retardant method is to coat the non-combustible outer layer outside the plastic. Among these flame retardant compounds, a reactive organophosphorus compound having high flame retardancy is, for example, an alkyne-containing compound and a phosphorus-containing compound. Phosphorus-containing epoxy resin and hardener DOPO (9,10-dihydro-9-oxa_10-phosphaphenaiitlirene 10-oxide) has attracted attention, and it has an active hydrogen atom which can react with an electron-poor compound. An electron-poor compound such as benzoquinone, oxirane, maleic aeid, bismaleimide, diaminobenzophenone, and terephthaldicarboxaldehyde 〇 The present invention therefore proposes a novel phosphorus-containing flame retardant hardener and a synthetic method thereof. e [Description of the Invention] It is an object of the present invention to provide a flame-retardant hardening The agent has a high glass transition temperature and flame retardancy and is suitable for use in the product board and the semiconductor package. Another object of the present invention is to provide a process for producing a flame retardant hardener which can be obtained by a simple addition reaction. 1310401 Therefore, the flame retardant hardener of the present invention has the following structural formula:
其中，R可為氫、CVC；6烷基、Cl_C6烷氧基、苯基、鹵素、硝基、 苯氧基或C3-C7環燒基；111為1、2、3或4;又為〇11或NH2。 上述之R較佳為氫；m較佳為4 ; X較佳為〇H或NH2。 本發明製造難燃硬化劑之方法，係將磷菲化合物與具有取代 基之三苯基甲烷化合物於有機溶劑中進行反應而獲得。 上述之鱗菲化合物較佳為9,1〇_二氫_9_氧_1〇-磷菲1〇_氧化物 (9，10-dihydro-9-oxa-10-phosphaphenanthrene 10-〇xide ;簡稱為 DOPO)。該具有取代基之三苯基甲烷化合物可為薔薇睃或氣化薔 薇本胺。該有機ί谷劑通常為乙醇、、異丙醇、tetrahydrofuran (THF)、 一 氣甲炫·、N，N-dimetiiyl formamide (DMF)、N，N dimethylacetamide (DMAc)、l-methyl-2-pyrrolidone (NMP)、dimethyl sulfone (DMSO) 或methyl-ethyl-ketone (MEK)等常見有機溶劑。該加成反應所需之 三苯基甲烷化合物與含磷單體之當量比較佳為約1:1。 上述之反應尚可包括有機鹼或無機鹼作為催化劑有機鹼可 為但不限於triethylamine、pyridine ;無機驗可為但不限於k2C03、 KOH、NaOH。在含氮溶劑中反應則甚至不需要觸媒，含氮溶劑例 如 N，N-dimethylformamide (DMF)、N，N-dimethylacetamide (DMAc)、1-methyl 2-pyrrolidone (NMP)等 〇 1310401 【實施方法】 >本發明提供之含鱗難燃硬化劑在和環氧樹樹脂硬化後，具有 較尚的玻璃轉移溫度及難燃性，因此適用於積體電路板及半導體 封裝材料。本說明書所舉之較佳實施例係藉由含磷單體9，1〇_二氫 -9-氧-10-碟菲 1〇_氧化物 dio-dihydro-Q-oxa-lO- phosphaphenanthrene 10-oxide ; 簡稱為 DOPO)與適當 物質經 由加成 反應而得。例如，結構式如下圖之D〇p〇_ta&D〇p〇_tri〇l，可分別 藉由DOPO/薔薇酸(rosolic acid)及DOPO/氣化薔薇苯胺 (pararosaniline chloride)的加成反應獲得。Wherein R can be hydrogen, CVC; 6 alkyl, Cl_C6 alkoxy, phenyl, halogen, nitro, phenoxy or C3-C7 cycloalkyl; 111 is 1, 2, 3 or 4; 11 or NH2. The above R is preferably hydrogen; m is preferably 4; X is preferably 〇H or NH2. The method for producing a flame retardant hardener according to the present invention is obtained by reacting a phosphophenanthrene compound with a triphenylmethane compound having a substituent in an organic solvent. The above scaly phenanthrene compound is preferably 9,1 〇 dihydro -9-oxyl 〇 磷 磷 氧化物 氧化物 氧化物 氧化物 oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-〇xide; For DOPO). The triphenylmethane compound having a substituent may be rose or carbaryl. The organic gluten is usually ethanol, isopropanol, tetrahydrofuran (THF), monomethophan, N, N-dimetiiyl formamide (DMF), N, N dimethylacetamide (DMAc), l-methyl-2-pyrrolidone ( Common organic solvents such as NMP), dimethyl sulfone (DMSO) or methyl-ethyl-ketone (MEK). The equivalent of the triphenylmethane compound and the phosphorus-containing monomer required for the addition reaction is preferably about 1:1. The above reaction may further comprise an organic base or an inorganic base as a catalyst. The organic base may be, but not limited to, triethylamine or pyridine; and the inorganic test may be, but not limited to, k2C03, KOH, NaOH. The reaction in a nitrogen-containing solvent does not even require a catalyst, and a nitrogen-containing solvent such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), 1-methyl 2-pyrrolidone (NMP), etc. 1310401 The scaly flame retardant hardener provided by the present invention has a relatively high glass transition temperature and flame retardancy after being cured with an epoxy resin, and is therefore suitable for use in an integrated circuit board and a semiconductor package material. The preferred embodiment of the present specification is based on a phosphorus-containing monomer 9,1 〇 dihydro-9-oxo-10-disphenanthrene quinone dio-dihydro-Q-oxa-lO-phosphaphenanthrene 10- Oxide (abbreviated as DOPO) is obtained by reacting an appropriate substance with an addition reaction. For example, D〇p〇_ta&D〇p〇_tri〇l of the following structure can be added by DOPO/rosolic acid and DOPO/gasoline pararosaniline chloride, respectively. obtain.
本發明實施例所使用之材質主要包括： (1) 雙紛A二環氧甘油謎（diglycidyl ether of bispheno.1 A ; DGEBA)，環氧當量(EEW)為187g/eq，購自南亞塑膠。 (2) 粉搭樹脂（phenol novolac ; PN)，OH當量為105 g/eq，購自長春 石油化學。 (3) DOPO購自東京化成(TCI)。 (4) 二氛基二苯基甲统(diphenyl diamino methane ; DDM)購自 Arcos ° (5) 薔薇酸(rosolic acid)賭自 Arcos。 (6) 氯化薔薇苯胺（pararosaniline chloride)購自 Arcos。 Ύ 1310401 本發明較佳實施例之詳細合成步驟說明如下： 實施例1 合成DOPO-triol 於設有加熱包(heating mantle)、擾拌器、熱電耗及溫度控制 器之四頸圓底燒瓶中，加入薔薇酸（29.0 g ’ 0·1 mole)、DOPO (21.6 g，0.1 mole)及乙醇（100 ml)。將反應混合物加熱，並於78°C下迴 流反應24小時。冷卻後，DOPO-triol之結晶自乙醇溶液中析出。 將結晶乾燥，並以熱差掃描分析（differential scanning calorimeter ; DSC)，測得明顯熔點為294°C。DOPO-triol之合成反應如下圖所The materials used in the examples of the present invention mainly include: (1) diglycidyl ether of bispheno.1 A (DGEBA), epoxy equivalent (EEW) of 187 g/eq, purchased from South Asia Plastic. (2) Phenol novolac (PN), OH equivalent of 105 g/eq, purchased from Changchun Petrochemical. (3) DOPO was purchased from Tokyo Chemical Industry (TCI). (4) Diphenyl diamino methane (DMM) was purchased from Arcos ° (5) rosolic acid was gambling from Arcos. (6) Pararosaniline chloride was purchased from Arcos. Ύ 1310401 Detailed synthetic steps of a preferred embodiment of the invention are as follows: Example 1 Synthesis of DOPO-triol in a four-necked round bottom flask equipped with a heating mantle, a scrambler, a thermoelectric consumption and a temperature controller, Rose oil (29.0 g '0·1 mole), DOPO (21.6 g, 0.1 mole) and ethanol (100 ml) were added. The reaction mixture was heated and refluxed at 78 ° C for 24 hours. After cooling, the crystals of DOPO-triol precipitated from the ethanol solution. The crystals were dried and subjected to differential scanning calorimeter (DSC) to find a clear melting point of 294 °C. The synthesis reaction of DOPO-triol is as shown in the figure below.
DOPO-triol之1H-NMR光譜如第1圖所示；13C-NMR如第2圖所 示；31PNMR光譜如第3圖所示。 φ 元素分析：C31H2305P:C，73.52 %;H，4.55%.Found:C，73.17%;H， 4.62%. W-NMR (DMSO-D6)，δ=6.52 (d，J = 5.4 Hz，6H，H4)，6.84 (dd，J = 8.4, 1.2 Hz，1H，H16)，7.04 (td，J =1·8, 1.2 Hz，1H, H14), 7.05 (d， J=5.4Hz, 6H, H3), 7.17 (td, J = 8.4, 1.8 Hz, 1H, H15), 7.28 (td, J = 7.8, 1.2 Hz，1H，H1。)，7.33 (td，J = 7.2, 4.8 Hz，1H,H9)，7.66 (td，J = 8.4, 1.2 Hz，1H，H8)，7.82(td，J = 8.4, 1.2 Hz，1H，H13)，8.05(dd，J = 8.4， 4.8 Hz, 1H, H7), 9.35(s, 3H). 13C-NMR (DMSO-D6), δ-62.8 (d, J = 91.7 Hz, C1), 114.4 (C4), 118.9 (C16), 120.4 (d, J - 8.6 Hz, C11), 123.2 (d, J = 9.2 Hz, C7), 123.4 (C14), 123.9 (d, J= 113.7 Hz, C6), Ί310401 125.0 (C13), 127.9 (C9), 130.0 (C15), 130.5 (C2), 131.5 (C3), 132.5(d, J = 9.2 Hz, C10), 133.3 (C8), 136.7 (C12), 150.3 (d, J=10.8 Hz, C17), 156.0 (C5). 31P-NMR, (DMSO-D6), δ =39.10(s). 實施例2 :合成DOPO-ta 於設有加熱包(heating mantle)、授拌器、熱電耗及溫度控制 器之四頸圓底燒瓶中，加入氯化薔薇苯胺（16.191g，0.05mole)、 00?0 (10.8075呂，0.05111〇16)及乙醇（10〇1111)。接著以超過2小時的 時間逐滴加入催化劑Triethylamine (8.08g，0.08mole)。將反應混 合物加熱，並於78°C下迴流反應12小時。反應完成後，將混合溶 液倒入水中產生沉澱物。於烘箱中將沉殿物乾燥，得產率為 74.51%。以熱差掃描分析（DSC)，測得明顯熔點為329°C。DOPO-ta 之合成反應如下圖所示。The 1H-NMR spectrum of DOPO-triol is shown in Fig. 1; 13C-NMR is shown in Fig. 2; and the 31P NMR spectrum is shown in Fig. 3. Elemental analysis of φ: C31H2305P: C, 73.52%; H, 4.55%. Found: C, 73.17%; H, 4.62%. W-NMR (DMSO-D6), δ=6.52 (d, J = 5.4 Hz, 6H, H4), 6.84 (dd, J = 8.4, 1.2 Hz, 1H, H16), 7.04 (td, J =1·8, 1.2 Hz, 1H, H14), 7.05 (d, J=5.4Hz, 6H, H3) , 7.17 (td, J = 8.4, 1.8 Hz, 1H, H15), 7.28 (td, J = 7.8, 1.2 Hz, 1H, H1.), 7.33 (td, J = 7.2, 4.8 Hz, 1H, H9), 7.66 (td, J = 8.4, 1.2 Hz, 1H, H8), 7.82 (td, J = 8.4, 1.2 Hz, 1H, H13), 8.05 (dd, J = 8.4, 4.8 Hz, 1H, H7), 9.35 ( s, 3H). 13C-NMR (DMSO-D6), δ-62.8 (d, J = 91.7 Hz, C1), 114.4 (C4), 118.9 (C16), 120.4 (d, J - 8.6 Hz, C11), 123.2 (d, J = 9.2 Hz, C7), 123.4 (C14), 123.9 (d, J = 113.7 Hz, C6), Ί310401 125.0 (C13), 127.9 (C9), 130.0 (C15), 130.5 (C2), 131.5 (C3), 132.5 (d, J = 9.2 Hz, C10), 133.3 (C8), 136.7 (C12), 150.3 (d, J = 10.8 Hz, C17), 156.0 (C5). 31P-NMR, (DMSO -D6), δ = 39.10(s). Example 2: Synthesis of DOPO-ta in a four-necked round bottom flask equipped with a heating mantle, a stirrer, a heat and power controller, and a chlorination Wei aniline (16.191g, 0.05mole), 00? 0 (10.8075 Lu, 0.05111〇16) and ethanol (10〇1111). The catalyst Triethylamine (8.08 g, 0.08 mole) was then added dropwise over a period of 2 hours. The reaction mixture was heated and refluxed at 78 ° C for 12 hours. After the reaction is completed, the mixed solution is poured into water to produce a precipitate. The dried matter was dried in an oven to give a yield of 74.51%. The difference in melting point was 329 ° C as measured by differential scanning analysis (DSC). The synthesis reaction of DOPO-ta is shown in the figure below.
DOPO-ta之1H-NMR光譜如第4圖所示；13C-NMR如第5圖所示； 31PNMR光譜如第6圖所示。 ^-NMR (DMSO-D6), δ= 5.41(s, 6H), 6.36 (d, J = 4.2 Hz, 6H, H4), 6.86 (dd, J = 8.4, 1.2 Hz, 1H, H16), 6.94 (s, broad, 6H, H3), 7.05 (td, J =8.4, 1.2 Hz, 1H, H14), 7.18 (td5 J = 8.4, 1.2 Hz, 1H, H15), 7.25 (td5 J =9.6, 1.2 Hz, 1H,H10), 7.31 (td, J = 7.8, 2.4 Hz, 1H, H9), 7.63(td, J = 7·2, 1.2 Hz, 1H，H8)，7.84(dd，J = 8.4, 1.2 Hz, 1H, H13). 8.03 (dd, J =7.8, 4.2 Hz, 1H, H7), 13C-NMR (DMSO-D6), 5=62.6 (d, J = 92.3 Hz, C1), 113.4 (C4), 118.9 (C16), 120.5 (d, J = 33.6 Hz, C11), 123.0 (C7), 1310401 123.1 (C14), 124.8 (d, J= 110.6 Hz, C6), 125.0 (C13), 127.9 (d,J=12.2 Hz, C9), 128.4 (C2), 129.9 (C15), 131.1 (d, J=4.8 Hz, C3), 131.8(d, J = 9.2 Hz, C10), 132.8 (C8), 136.3 (C12), 146.0 (C17), 150.1 (d, ' J=l〇.9,C5). 31P-NMR, (DMSO-D6), δ =39.49(s). 將上述實施例合成之DOPO-triol及DOPO-ta分別與龄搭樹 脂(PN)及二氨基二苯基甲烷(DDM)搭配，作為環氧樹脂雙酚A二 環氧甘油醚(DGEBA)的硬化劑，並藉由下列分析試驗其效果。 _ 1·熱差掃描分析（differential scanning calorimeter; DSC) 第7圖為含有不同成份比例的硬化後樣品dTq-DT 1()()(樣品編 號參見表1)在DSC掃描下的結果，其硬化後環氧樹脂的玻璃移轉 溫度（Tg)的範圍為13 8-15 9。(：。樣品DT()-DT8G的玻璃移轉温度並隨 著磷含量增加而升高，但樣品DT10()則持平。該圖顯示本發明之 DOPO_triol明顯地提高了玻璃移轉溫度；這與傳統含磷環氧樹脂 不同。傳統上’當難燃成分(例如磷)加入聚合物後，玻璃移轉溫度 將補微或明顯地隨著鱗含量增加而下降。但第7圖中，玻璃移轉 期間的ACp範圍為0.260-0.162 J/goC，並隨著DOPO-triol含量增 加而減少。ACp愈小，意即交鍵密度(crosslink density)愈大，而玻 φ 璃移轉溫度愈高。因此，玻璃移轉溫度隨DOPO-triol含量增加而 升高的原因在於硬化後環氧樹脂的膠鏈密度增加。此外，巨大的 DOPO基團亦阻卻分子鏈的流動性，導致玻璃移轉溫度升高。至 於DGEBA/DOPO-ta硬化系統，其玻璃移轉溫度則為171°C (見表 1)。 2.熱重分析（thermogravimetrie analysis ; TGA) TGA軌跡可顯示硬化樹脂的熱穩定性及熱降解現象。樣品 DT〇-DTi〇〇在大氣氮中的TGA熱曲線圖（thermogram)如表1所示。 5%的降解溫度(Td)範圍為350-404。(：，並隨著磷含量增加而略減， 1310401 這是由於DOPO-triol的熱穩定性較差。但含磷環氧樹脂的焦炭殘 餘量（charyield)則較高。然而’即便降解溫度會隨著磷含量増加 而降低’本發明含碟熱塑物的降解溫度仍高於其他具有P=〇開鏈 的含磷聚合物；因為0=P-0環的熱穩定性優於〇=P_〇開鏈，亦即 將雙股(doubly-stranded)單元引進主幹(backbone)可使其具有較佳 之熱穩定性。本發明含磷環氧樹脂因具有較高的降解溫度，更適 用於焊接溫度高達288°C之積體電路板。至於DGEBA/DOPO-ta硬 化系統，其降解溫度(Td)則為358°C，800°C時的焦炭殘餘量為 31% ;見表1。 —3.UL-94 測試 UL-94是一種測試難燃性的方法，聚合物樣品須經過兩次各 歷時10秒的燃燒過程。第一次燃燒後，將火焰移開並紀錄聚合物 自行熄滅所需的時間。若聚合物在測試期間有滴落現象 (dripping)，Cotton ignition would be noted。待樣品冷卻後，進行 第二次燃燒’並紀錄聚合物自行熄滅所需的時間（t2)及滴落現象。 若t!+t2少於10秒且無滴落現象，則根據難燃性的工業標準 (industrial standard for flame-retardancy)歸類為 V-0 等級，h+h 為 10〜30秒則屬V-1等級。表2顯示樣品DT(rDT1()()的UL-94測試結 Φ 果。如表2所示’硬化後環氧樹脂的難燃性隨碟含量增加而增加， 其中樣品DT60-DT100屬UL-94V-0等級。亦即l.87wt.0/〇的填含量 便足以達到UL-94 V-0等級。表3則為硬化後DGEBA/DOPO-ta/ DDM的UL-94測試結果。如表3所示’硬化後環氧樹脂的難燃性 隨著碟含量增加而增加，當鱗含量為1.80 wt·%時，便可達到UL-94 ν·ο等級。 * 4.介電常數及消散因子（dielectric constant and dissipation factor) 積體電路的訊號延遲時間與基材(matrix)的介電常數的平方 根成正比，而訊號衰減則正比於基材的介電常數的平方根及逸散 1310401 因子。因此’具有低介電常數及低消散因子的材料可減少訊號廷 遲時間及訊號衰減。硬化後樣品dt0-dt100的介電常數及消散因 子如表1所示；在1GHz及室溫時，介電常數的範圍為2.98-3.27。 ' ^明顯的介電特性-組成趨勢表示加入碟並不影響硬化後環氣樹 脂的介電特性。至於DGEBA/DOP〇_ta硬化系統，其介電常數 為3·14，消散因子為64.4〜85.7 mU。 後 D〇P〇_triol/盼搭樹脂的吸水率(m〇isture absorpti〇n) 吸水率可使離子性雜質游離，進而腐蝕積體電路；甚至增加 鲁封裝材料的介電常數。因此，電子材料的吸水率愈低愈好。樣品 DTo-DT^o在浸入水中5〇〇小時後的吸水率如表1所示其範圍為 1·62 wt’/〇-1.85 wt.%。硬化後環氧樹脂的吸水率隨磷含量增加而略 微增加但無明顯趨勢及差異。至於dgeba/d〇p〇_访硬化系統， 其吸水率則為1,76 wt. %。 表1 樣品 硬化劑組成 Tg Td 焦炭殘餘量 吸水率 Dka Dfb 編號 (DOPO-triol/PN) Γ〇 ro (wt.%) (Wt %、 (ΤΠ (mU) DT〇 0/100 138 404 18 1.62 3.27 62.3-64.3 DT20 20/80 145 383 25 1.70 3.23 49.7-59.3 DT4O 40/60 146 376 26 1.76 2.98 64.4 〜67.8 DT6〇 60/40 147 366 27 1.64 3.10 61·6 〜68·8 DTg〇 80/20 159 358 28 1.85 2.93 80.5-83.6 DT100 100/0 156 350 26 1.66 3.20 87.7-91.9 DGEBA/ DOPO-ta 171 358 31 1.76 64.4-85.7 DOPO-ta 3.14 a介電常數散因子 1310401The 1H-NMR spectrum of DOPO-ta is shown in Fig. 4; 13C-NMR is shown in Fig. 5; and the 31P NMR spectrum is shown in Fig. 6. ^-NMR (DMSO-D6), δ = 5.41 (s, 6H), 6.36 (d, J = 4.2 Hz, 6H, H4), 6.86 (dd, J = 8.4, 1.2 Hz, 1H, H16), 6.94 ( s, broad, 6H, H3), 7.05 (td, J = 8.4, 1.2 Hz, 1H, H14), 7.18 (td5 J = 8.4, 1.2 Hz, 1H, H15), 7.25 (td5 J = 9.6, 1.2 Hz, 1H, H10), 7.31 (td, J = 7.8, 2.4 Hz, 1H, H9), 7.63 (td, J = 7.2, 1.2 Hz, 1H, H8), 7.84 (dd, J = 8.4, 1.2 Hz, 1H, H13). 8.03 (dd, J = 7.8, 4.2 Hz, 1H, H7), 13C-NMR (DMSO-D6), 5=62.6 (d, J = 92.3 Hz, C1), 113.4 (C4), 118.9 (C16), 120.5 (d, J = 33.6 Hz, C11), 123.0 (C7), 1310401 123.1 (C14), 124.8 (d, J = 110.6 Hz, C6), 125.0 (C13), 127.9 (d, J= 12.2 Hz, C9), 128.4 (C2), 129.9 (C15), 131.1 (d, J=4.8 Hz, C3), 131.8 (d, J = 9.2 Hz, C10), 132.8 (C8), 136.3 (C12), </ RTI> <RTIgt; It was used as a hardener for epoxy resin bisphenol A diglycidyl ether (DGEBA) in combination with aged resin (PN) and diaminodiphenylmethane (DDM), and its effect was tested by the following analysis. _ 1·differential scanning calorimeter (DSC) Figure 7 shows the results of hardened sample dTq-DT 1()() (sample number see Table 1) under DSC scan. The glass transition temperature (Tg) of the post epoxy resin ranges from 13 8 to 15 9 . (: The glass shift temperature of sample DT()-DT8G increases with increasing phosphorus content, but sample DT10() is flat. This figure shows that DOPO_triol of the present invention significantly increases the glass transition temperature; Traditionally, phosphorus-containing epoxy resins are different. Traditionally, when a flame-retardant component (such as phosphorus) is added to a polymer, the glass transition temperature will decrease or significantly decrease as the scale content increases. However, in Figure 7, the glass shift The ACp range during the rotation is 0.260-0.162 J/goC, and decreases as the DOPO-triol content increases. The smaller the ACp, the larger the crosslink density, and the higher the glass transition temperature. Therefore, the reason why the glass transition temperature increases with the increase of the DOPO-triol content is that the epoxy chain density of the epoxy resin increases after hardening. In addition, the large DOPO group also blocks the mobility of the molecular chain, resulting in the glass transition temperature. As for the DGEBA/DOPO-ta hardening system, the glass transition temperature is 171 ° C (see Table 1). 2. Thermogravimetrie analysis (TGA) The TGA trace shows the thermal stability of the hardened resin and Thermal degradation phenomenon. Sample DT〇-DTi〇〇 The TGA thermogram in atmospheric nitrogen is shown in Table 1. The 5% degradation temperature (Td) ranges from 350 to 404. (:, and slightly decreases with increasing phosphorus content, 1310401 This is due to DOPO- The thermal stability of triol is poor. However, the coke residue of the phosphorus-containing epoxy resin is higher. However, even if the degradation temperature decreases with the increase of the phosphorus content, the degradation temperature of the dish-containing thermoplastic of the present invention is still high. Other phosphorus-containing polymers with P=〇 open chain; because the thermal stability of the 0=P-0 ring is better than that of the 〇=P_〇 open chain, and the double-stranded unit is also introduced into the backbone. It can make it have better thermal stability. The phosphorus-containing epoxy resin of the invention has higher degradation temperature and is more suitable for an integrated circuit board with a soldering temperature of up to 288 ° C. As for the DGEBA/DOPO-ta hardening system, The degradation temperature (Td) is 358 ° C, and the residual coke at 800 ° C is 31%; see Table 1. -3.UL-94 Test UL-94 is a method for testing flame retardancy, polymer samples must be After two cycles of burning for 10 seconds, after the first combustion, the flame is removed and the polymer is self-extinguishing. Time required. If the polymer has dripping during the test, the Cotton ignition would be noted. After the sample is cooled, perform a second combustion' and record the time required for the polymer to self-extinguish (t2) and drop If t!+t2 is less than 10 seconds and there is no dripping, it is classified as V-0 according to the industrial standard for flame-retardancy, h+h is 10~30 seconds. It is a V-1 rating. Table 2 shows the UL-94 test results of sample DT (rDT1()(). As shown in Table 2, the flame retardancy of the epoxy resin increases with the increase of the disc content, and the sample DT60-DT100 belongs to UL- 94V-0 grade, that is, the filling content of l.87wt.0/〇 is enough to achieve UL-94 V-0. Table 3 is the UL-94 test result of DGEBA/DOPO-ta/DDM after hardening. 3 shows that the flame retardancy of the epoxy resin increases with the increase of the disc content. When the scale content is 1.80 wt·%, the UL-94 ν·ο grade can be achieved. * 4. Dielectric constant and dissipation Dielectric constant and dissipation factor The signal delay time of an integrated circuit is proportional to the square root of the dielectric constant of the matrix, and the signal attenuation is proportional to the square root of the dielectric constant of the substrate and the dissipation factor of 1310401. Therefore, materials with low dielectric constant and low dissipation factor can reduce signal delay time and signal attenuation. The dielectric constant and dissipation factor of sample dt0-dt100 after hardening are shown in Table 1; at 1 GHz and room temperature, The range of electrical constants is 2.98-3.27. ' ^Significant dielectric properties - composition trend indicates that adding a disc does not affect The dielectric properties of the epoxy resin after hardening. As for the DGEBA/DOP〇_ta hardening system, the dielectric constant is 3.14, and the dissipation factor is 64.4~85.7 mU. After D〇P〇_triol/ Rate (m〇isture absorpti〇n) The water absorption rate can free the ionic impurities, thereby corroding the integrated circuit; even increasing the dielectric constant of the Lu package material. Therefore, the lower the water absorption of the electronic material, the better. Sample DTo-DT The water absorption rate of ^o after immersion in water for 5 hours is as shown in Table 1. The range is 1.62 wt' / 〇 - 1.85 wt.%. The water absorption of the epoxy resin after hardening increases slightly with the increase of phosphorus content. There is no obvious trend and difference. As for the dgeba/d〇p〇_ visit hardening system, the water absorption rate is 1,76 wt.%. Table 1 Sample hardener composition Tg Td coke residual water absorption rate Dka Dfb number (DOPO-triol /PN) Γ〇ro (wt.%) (Wt %, (ΤΠ (mU) DT〇0/100 138 404 18 1.62 3.27 62.3-64.3 DT20 20/80 145 383 25 1.70 3.23 49.7-59.3 DT4O 40/60 146 376 26 1.76 2.98 64.4 ~ 67.8 DT6〇60/40 147 366 27 1.64 3.10 61·6 ~68·8 DTg〇80/20 159 358 28 1.85 2.93 80.5-83. 6 DT100 100/0 156 350 26 1.66 3.20 87.7-91.9 DGEBA/ DOPO-ta 171 358 31 1.76 64.4-85.7 DOPO-ta 3.14 a Dielectric constant factor 1310401
表2 樣品 編號 磷含量 (wt.%) Τι (秒） T2 (秒） 滴落 現象 UL-94 等級 DT〇 0 109 -- 有 燃燒 dt2〇 0.67 16.7 9.3 無 V-1 DT40 1.29 12.3 1.9 無 Y-1 dt6〇 1.87 6.7 1.4 無 V-0 DTg〇 2.40 1.1 4.7 無 V-0 DTl〇〇 2.90 2.7 4.6 無 V-0 表3 硬化系統 磷含量 Τι τ2 滴落 UL-94 (wt.%) (秒） (秒） 現象 等級 DGEBA/DOPO-ta/DDM 1 12.2 16.6 無 V-1 DGEBA/DOPO-ta/DDM 1.5 7.85 12.0 無 V-1 DGEBA/DOPO-ta/DDM 1.8 2.67 3.1 無 V-0 以上所述之較佳實施例僅為說明本發明之原則，並非用以限 制其範圍；例如反應物中苯環之氫以其他官能基取代時，亦可經 由類似反應製得具有不同官能基之難燃硬化劑。因此，凡根據上 述實施例稍加修改或延伸所獲致者，自應屬本發明之範圍。 1310401 【圖式簡述】 第1〜3圖分別為DOPO-triol之1H-NMR光譜、13C_NMR光 譜及及31PNMR光譜； 第4〜6圖分別為DOPO-ta之1H-NMR光譜、13C-NMR光譜 及31P NMR光譜； 第7圖為硬化後樣品之DSC掃描結果。Table 2 Sample No. Phosphorus Content (wt.%) Τι (seconds) T2 (seconds) Dropping phenomenon UL-94 Grade DT〇0 109 -- Burning dt2〇0.67 16.7 9.3 No V-1 DT40 1.29 12.3 1.9 No Y- 1 dt6〇1.87 6.7 1.4 No V-0 DTg〇2.40 1.1 4.7 No V-0 DTl〇〇2.90 2.7 4.6 No V-0 Table 3 Phosphorus content of hardening system Τι τ2 Drop UL-94 (wt.%) (seconds) (seconds) Phenomena level DGEBA/DOPO-ta/DDM 1 12.2 16.6 No V-1 DGEBA/DOPO-ta/DDM 1.5 7.85 12.0 No V-1 DGEBA/DOPO-ta/DDM 1.8 2.67 3.1 No V-0 The preferred embodiments are merely illustrative of the principles of the present invention and are not intended to limit the scope thereof; for example, when the hydrogen of the benzene ring in the reactant is substituted with other functional groups, it is also possible to obtain a flame retardant hardening having different functional groups by a similar reaction. Agent. Therefore, any modifications or extensions made in accordance with the above-described embodiments are intended to be within the scope of the invention. 1310401 [Scheme description] Figures 1 to 3 are 1H-NMR spectrum, 13C_NMR spectrum and 31PNMR spectrum of DOPO-triol, respectively; Figures 4 to 6 are 1H-NMR spectrum and 13C-NMR spectrum of DOPO-ta, respectively. And 31P NMR spectrum; Figure 7 shows the DSC scan results of the sample after hardening.