201111408 六、發明說明： C 明所屬^_技冬好領域;3 發明領域 本發明係相關於一種硬化劑摻合物，其包括—胺系固 化劑與一酚類固化劑，並相關於一種包含該硬化劑摻合物 之樹脂組成物。 C :^tr才支4标】 發明背景 嚴格的熱力學要求與潛在環境保護考量，使得不含鹵 素之阻燃劑已被考慮用於取代舊有技術之某些鹵化化合 物，如四溴雙酚-A之各種衍生物。例如，目前已使用與含 磷及/或氮之阻燃劑共價性聯結之環氧樹脂，以確保安全性 與可相容性’並達到UL 94 v〇之可燃性要求，與其他重要 之物理特性。 用於複合材射，如預浸物(pr>e_pi，eg)，環氧樹脂系統 需要在儲存時有良好之樹脂穩定度。適當與值定之反應 性’以及最適化與-致之樹脂流動特性，為環氧樹脂系統 進行壓模製程製備積層板，如多層電路板前之前置要求。 然而，目前已證實不含函素之環氧樹脂系統之可加工 性相當難以達成，與傳統樹脂系統相較。為了達雜94 V〇 標準、高熱力學穩定性，以及抗陽極導電細絲(Μ)之要 求’便發展出不含_素之印刷電路板，其使㈣類固化劑 並具有馬磷含量。所使用之多官能基_固化劑，通常可 在〜階段預浸物(卿eg)製備過程中，產生高黏度增層 201111408 (build-up)。然而，該高填含量（如至多3·5% ’以100%總配 方固體成分為基礎）通常會導致預浸物(pre-preg)產生較高_ 之濕度敏感性，與傳統FR-4系統相較。在預浸物(Pre-preg) 吸收濕氣後，該預浸物（pre-preg)粉末之最低溶融黏度 (MMV)傾向於降低，而層板壓製時，流動性便會隨著老化 時間而增高。不含鹵素樹脂之此不良儲存穩定性，為積層 板製程中之關鍵問題。 t考务明内溶L】 發明概要 本發明之一觀點係提供一種組成物’包含一環氧樹 脂’其任擇地包含碟或氮之至少一者，以及一硬化劑摻合 物’包含一胺系固化劑與一酚類固化劑。該組成物之特徵 為由該組成物製備之預浸物(pre-preg)粉末’置於100%相對 濕度及25°C之條件下24小時後，其AMMV不大於20%。此 包括由該組成物製備之預浸物(pre-preg)粉末，置於1 〇〇°/0相 對濕度及25°C之條件下24小時後，其AMMV不大於15%， 且更包括由該組成物製備之預浸物（pre-preg)粉末，置於 100%相對濕度及25。〇之條件下24小時後，其ΔΜΜν^Ο%。 該組成物可任擇地包括一或多種阻燃劑或固化劑，包括含 磷固化劑。在某些實施例中，該組成物不含卤化物。 在某些實施例中，該組成物中硬化劑摻合物比環氧樹 脂之重量比為0.5:1至1:1，以該組成物之固體含量總重量為 基礎’且酚類固化劑比胺系固化劑之重量比為10:1與3:1， 以胺與盼固化劑之固體含量總重量為基準。 4 201111408 該紛類固化劑可包含破。例如，該驗類固化劑可包含 含鱗之雙盼A可溶齡醒·(resole)樹脂，且可更包含一紛酸清 漆(novolac)樹脂。 胺系固化劑範例包括DETDA與DICY。 環氧樹脂可為如環氧盼酸清漆樹脂。 在該組成物之一特定實施例中，胺系固化劑包含一含 有疏水性基團之芳香胺，該酚類固化劑包含一含磷化合 物，該組成物之特徵為由該組成物製備之預浸物(pre-preg) 粉末’置於100%相對濕度及25。(：之條件下24小時後，其 △MMV < 0%。 較佳該組成物可符合UL 94 V0阻燃劑標準。 本發明之另一觀點係提供一種由該組成物製備之複合 材料。此複合材料之一實施例係包含一孔狀強化物，以及 一用於浸潰該孔狀強化物之上述組成物。該孔狀強化物可 為如複數個纖維。 另一複合材料包含一金屬基板與一塗覆於該金屬基板 上之上述組成物。該金屬基板可為如銅箱。 本發明之又一觀點係提供一種積層板，可加入該組成 物或複合材料。在一實施例中，該積層板係包含第一層， 包含一孔狀強化物、第二層，包含_金屬；以及結合該第 一層與該第二層之連續環氧樹脂基質，該環氧樹脂基質包 含一已固化之組成物，其包括含有磷或氮之至少一者之環 氧樹脂’以及硬化劑摻合物’包含—以胺為主的固化劑以 及-盼類ID化劑。在此實施例中，該組成物之特徵為由該 201111408 組成物製備之予貝浸物(pi_epi_eg)粉末， 置於100%相對濕度及 25C之條件下24小時後，其ΔΜΜν不大於2〇0/。。 I：實施令式】 較佳貫她例之詳細說明 定義 f 卜有陳述、内文指示或技術上習知，所有分重 與百料尔量核據，且所有檢财法料本揭示申 請曰前之現行方法。就美國專利實務而言任何專利文獻、 專利申請書或公開文獻之内容，係完整併人本案作為參考 資料(或以其等同之美國版本併人參考資料），尤其是有關於 合成技術、定義（與本揭示特別提供之定義無不一致者）， 及習知一般技術之揭示。 數字表示範圍包括較低值與較高值，以一單位形式遞 增’其中任何較低值與較高值之間存在至少兩單位之間 距。舉例而言’若組成性、物理性或其他性質或加工參數， 如熔融黏度、溫度等，範圍由刚至⑽，則其意義為所 有個別的數值如1〇〇、101、1〇2等，與子範圍如1〇〇至144、 服Π0、197至200等’可盡數列出。針對數值範圍内有 小於1或包含大於1之小數時(如L1、i 5等），其最小單位依 情況可為0_0001、〇·_ ' 0.01或0」。針對數值範圍内包含 小於10之-位數時(如！至5)，其最小單位—般駭為〇」。 以上僅作為本說明書特定指出之範例，且最大值與最小值 數字間之所有可能組合，均可視為本發明揭示之内容。 術語“包含”與其衍生詞並非排除任何其他成分、步驟 201111408 或私序之存在，是否㈣料別揭示。 所有申請專職圍内❹“包含，,^ =何疑慮， 可包括任何其他步驟、裝置、添加劑'佐劑 不論是聚合性或其他形式，除非有另外說明==物^ 語“必須由…組成”1則排除任何後續_ 立他 成分、步㈣程料，除非其非騎制、^之:由 :成”一詞排除未特定描述或列舉之任何成分二:程 序。術語“或”1，除非特別說明，意指 獨 員以及其組合。 心谷早獨成 術έ吾聚合物”一詞音指由；(；日ρη十丁门』 曰由相冋或不同類型之聚合單體 製備而成之聚合性化合物。—般術語聚合物包括同元聚合 物(h〇m〇P〇lymers)，—般用於指稱僅由一種單體製備之二 合物，而術語異分子共聚物（interp〇lymers)則如下述定義。 “異分子共聚物”一詞意指由至少兩種類型之單體聚合 而成之聚合物。此術語包括共聚物，其通常代表由兩種不 同類型之單體製成之聚合物，以及由兩種以上不同形式之 單體製備之聚合物，如三聚物或四聚物等。 術語“預浸物(pre-preg)”係指具有預浸有可固化樹脂組 成物之孔狀強化物複合材料。孔狀強化物之預先浸潰可以 各種方式進行，包括將孔狀強化物浸入可固化樹脂組成物 中、喷灑該可固化樹脂組成物至孔狀強化物上、將該孔狀 強化物暴露於可固化樹脂組成物流中，以及將可固化樹脂 組成物真空滲入至該孔狀強化物中。浸潰後，排出孔狀強 化物上多餘之樹脂組成物，或以其他方式移除，以提供“預 201111408 浸物(pre-preg)”。由預浸物(pre-preg)製備之孔狀強化物範例 可為織品’包括含纖維材料如纖維、織布、纖維網、纖維 塾，以及不織芳綸強化物如商標名為THERMOUNT，得自 DuPont, Wilmington, Del者。較佳為，此類材料係製備自玻 璃、玻璃纖維、石英、纖維素性或合成性紙張、熱塑性樹 脂基板’芳綸強化物、聚乙烯、聚（對苯二甲醯對苯二胺）、 聚酯、聚四氟乙烯與聚（對-伸苯基苯併雙噻唑）、間規聚苯 乙烯、碳、石墨、陶瓷或金屬。較佳之材料包括玻璃或玻 璃纖維，為織布形式或塾形式。 術語“B-階段預浸物（pre-preg)”係指一預浸物 (pre-preg)，其係於高溫下加工，使得該預浸物(pre-preg)進 行部分固化。 術語“環氧化物預浸物(pre-preg)”係指一由預浸有環氧 樹脂之孔狀強化物複合材料製備之預浸物(Pre-Preg)。 術語“積層板”係指一在高溫與壓力下，將包括至少一 預浸物(pre-preg)層之多層結構中之複數層壓製在一起，而 使該預浸物(pre-preg)層可完全或實質上完全固化之物件。 預浸物(Pre-Preg)粉末之“最低熔融黏度”(MMV)，係指 當預浸物(pre-preg)粉末之溫度增加至某一溫度時，使預浸 物(pre-preg)粉末之黏度達到最低。預浸物(pre-preg)粉末為 當強化物以篩除或以其他方式自預浸物上移除後’仍維持 粉末狀態之粉末。係進行預浸物（Pre_Preg)粉末之黏度測 量，使得強化物不會影響該值。最低熔融黏度為會導致預 浸物(pre-preg)粉末黏度下降之溫度增加’以及會導致黏度 201111408 增加之熱固化作用’兩者間競爭之結果。就本發明之目的 而言，MMV係依據下列範例一節所述之流程與條件測量。 預浸物(pre-preg)粉末之“delta改變量”(ΔΜΜν) ’係指 當該預浸物(Pre_PreS)粉末於1 〇〇%相對濕度’及25 C條件下 儲存24小時後，預浸物(Pre-Preg)粉末之MMV改變量。預浸 物(pre-preg)粉末之初始MMV值，可於預浸物(pre-preg)製造 後立即得到之預浸物（Pre-Preg)樣本上進行。 本發明之一觀點係提供一種雙重-固化硬化劑摻合 物，用於不含函素之環氧樹脂組成物中。本發明之其他觀 點係提供一種由該雙重-固化硬化劑摻合物製備之樹脂組 成物，以及由該樹脂組成物製備之複合材料。該雙重-固化 硬化劑摻合物係以具有至少一胺系固化劑與至少一酚類固 化劑之掺合物為基礎。該雙重-固化硬化劑摻合物可用於含 填及/或氮之非鹵素環氧樹脂，由於其可增進B-階段預浸物 (pre-preg)之儲存穩定性，以及環氧樹脂組成物加工時之可 濕潤性與流動性。尤其是，由該環氧樹脂組成物所製備之 預浸物(pre-preg)粉末，及該雙重-固化硬化劑摻合物之特徵 為其AMMV為20%或更低。此包括預浸物(pre_preg)粉末之 特徵為ΔΜΜν S 15%之實施例，更包括預浸物(pre_preg)粉 末之特徵為ΔΜΜν<0%之實施例。此外，由其製備之該組 成物及複合材料可符合UL 94 V0之可燃性要求。 “UL-94” 為 Underwriters’ Laboratory (UL)公告 94 號古式 驗，係針對裝置與電器局部塑膠材料之可燃性檢測。受測 材料若為UL 94 V-0等級之條件為： 201111408 •當移去火源時五個受測樣品皆未燃燒超過10秒者。 •十次點火試驗之總燃燒時間未超過50秒。 •夾鉗上未有受測樣品燃燒，不論是出現火焰或餘 爐。 •任何受測樣品未出現燃燒滴漏現象’其將導致下方 棉布起火。 •未有受測樣品之餘燼起燃時間超過30秒。 欠測材料若為UL94V]等級之條件為： •當移去火源時五個受測樣品皆未燃燒超過30秒者。 •十-欠點火試驗之總燃燒時間未超過250秒。 •夾甜上未有受測樣品燃燒，不論是出現火焰或餘 墙。 •任何受測樣品未出現燃燒滴漏現象’其將導致下方 棉布起火。 •未有受測樣品之餘燼起燃時間超過60秒。 又測材料若為UL94V_2等級之條件為： •當移去火源時五個受測樣品皆未有燃燒超過30秒 者。 •十次點火試驗之總燃燒時間未超過250秒。 •夹甜上未有受測樣品燃燒，不論是出現火焰或餘 燼。 •又測樣品中僅有短暫燃燒之燃殘片出現滴漏，且其 中某些使下方棉布起火。 未有文測樣品之餘燼起燃時間超過60秒。， 201111408 由於本發明之組成物之基本實施例包括一環氧樹脂， 其任擇地包含至少一填或氮，以及一硬化劑摻合物，其包 含一胺系固化劑與一醅類固化劑。這些成分之每一者皆於 下進行更詳細之描述。 環氧樹脂： 本發明之組成物包括至少一環氧樹脂。在某些實施例 中，該環氧樹脂為含磷或含氮之環氧樹脂。這些為經阻燃 化合物共價性修飾，不論是側鏈或作為聚合物骨架之一部 分，之環氧樹脂(較佳符合UL 94 V0之表現度要求）。含磷或 含氮環氧樹脂係揭示於美國專利號6,645,631、6,617,029與 5,756,638，以及歐洲專利號EP 1，592,746。美國專利號 5，112,932描述了適用之經噚唑酮修飾之環氧樹脂。 該環氧樹脂可經修飾，如藉由與含磷元素或含氮元素 之化合物或單體反應，在環氧樹脂進行聚合反應之時或之 後。可用於本發明之含磷與含氮元素之化合物或單體，一 般含有反應性基團，如盼基團、酸基團、胺基團與酸針基 團、亞磷酸基團，或亞膦酸(phosphinate)基團，其可與環氧 樹脂上之環氧基團反應。含填化合物之範例包括如，下列 化合物之一或多者：P-Η官能基化合物如HCa、亞磷酸二甲 酯、亞磷酸二苯酯、乙基膦酸、二乙基亞膦酸、甲基乙基 亞膦酸、苯基膦酸、苯基亞磷酸、乙烯基磷酸、酚類 (HCA--HQ) ’及類似物；三(4-羥基苯基)氧化膦、雙(2-羥基 苯基）苯基氧化膦、雙(2-羥基苯基)苯基膦酸酯、三(2-經基 -5-甲基苯基）氧化膦；酸肝化合物，如MifAH，及其類似 11 201111408201111408 VI. Description of the invention: C. The field of the invention is related to a hardener blend comprising an amine-based curing agent and a phenolic curing agent, and is related to a A resin composition of the hardener blend. C: ^tr才支四标] Background of the Invention Strict thermodynamic requirements and potential environmental considerations, such that halogen-free flame retardants have been considered to replace some of the halogenated compounds of the prior art, such as tetrabromobisphenol - Various derivatives of A. For example, epoxy resins covalently bonded to phosphorus and/or nitrogen containing flame retardants have been used to ensure safety and compatibility' and to meet UL 94 v〇 flammability requirements, and other important Physical characteristics. For composite shots, such as prepregs (pr>e_pi,eg), epoxy systems require good resin stability during storage. Appropriate and valued reactivity' and optimum resin flow characteristics are used to prepare laminates for epoxy resin systems, such as pre-layered boards. However, the processability of epoxy-free epoxy systems has proven to be quite difficult to achieve, compared to conventional resin systems. In order to meet the standard of 94 V〇, high thermodynamic stability, and the requirement for anti-anode conductive filaments (Μ), a printed circuit board containing no element was developed, which gave a (four) type of curing agent and a horse phosphorus content. The polyfunctional group-curing agent used can usually produce a high viscosity build-up layer 201111408 (build-up) during the preparation of the ~stage prepreg. However, this high fill content (eg, up to 3.5% 'based on 100% total formulation solids) usually results in higher pre-preg moisture sensitivity, compared to conventional FR-4 systems. Compared. After the pre-preg absorbs moisture, the minimum melt viscosity (MMV) of the pre-preg powder tends to decrease, and when the laminate is pressed, the fluidity will follow the aging time. Increase. This poor storage stability of halogen-free resins is a key issue in the lamination process. BRIEF DESCRIPTION OF THE INVENTION One aspect of the present invention provides a composition 'comprising an epoxy resin' which optionally comprises at least one of a dish or a nitrogen, and a hardener blend comprising one An amine curing agent and a phenol curing agent. The composition is characterized in that the pre-preg powder prepared from the composition is placed at 100% relative humidity and 25 ° C for 24 hours, and its AMMV is not more than 20%. This includes a pre-preg powder prepared from the composition, which has an AMMV of no more than 15% after being placed at a temperature of 1 〇〇/0 relative humidity and 25 ° C for 24 hours, and further includes The composition prepared pre-preg powder was placed at 100% relative humidity and 25. After 24 hours under the conditions of 〇, its ΔΜΜν^Ο%. The composition may optionally include one or more flame retardants or curing agents, including phosphorus-containing curing agents. In certain embodiments, the composition is free of halides. In certain embodiments, the weight ratio of the hardener blend to the epoxy resin in the composition is from 0.5:1 to 1:1, based on the total weight of the solid content of the composition, and the ratio of the phenolic curing agent is The weight ratio of the amine curing agent is 10:1 and 3:1, based on the total weight of the solid content of the amine and the curing agent. 4 201111408 This class of curing agents can be broken. For example, the test curing agent may comprise a scaly double-looking A resole resole resin, and may further comprise a novolac resin. Examples of amine curing agents include DETDA and DICY. The epoxy resin may be, for example, an epoxy acid varnish resin. In a specific embodiment of the composition, the amine curing agent comprises an aromatic amine containing a hydrophobic group, the phenolic curing agent comprising a phosphorus-containing compound, the composition being characterized by a preparation prepared from the composition The pre-preg powder was placed at 100% relative humidity and 25. After 24 hours, the ΔMMV < 0%. Preferably, the composition conforms to the UL 94 V0 flame retardant standard. Another aspect of the present invention provides a composite material prepared from the composition. An embodiment of the composite material comprises a porous reinforcement, and a composition for impregnating the porous reinforcement. The porous reinforcement may be, for example, a plurality of fibers. The other composite material comprises a metal. a substrate and a composition coated on the metal substrate. The metal substrate may be, for example, a copper box. Yet another aspect of the present invention provides a laminate that can be incorporated into the composition or composite. In an embodiment The laminated board comprises a first layer comprising a porous reinforcement, a second layer comprising a metal, and a continuous epoxy matrix bonded to the first layer and the second layer, the epoxy matrix comprising The cured composition, which comprises an epoxy resin containing at least one of phosphorus or nitrogen, and a hardener blend, comprises an amine-based curing agent and an anti-ID IDing agent. In this embodiment The composition is characterized by 201111408 The pi_epi_eg powder prepared by the composition is placed at 100% relative humidity and 25C for 24 hours, and its ΔΜΜν is not more than 2〇0/. I: the implementation formula is better. The detailed description defines the statement, the internal instructions or the technical know-how, all the weights and the amount of the evidence, and all the prosecution laws disclose the current method before the application. For the US patent practice The contents of any patent document, patent application or publication are hereby incorporated by reference in its entirety in its entirety, in its entirety, in its entirety in its entirety, in its Definitions are not inconsistent, and the disclosure of conventional general techniques. The numerical representation range includes lower and higher values, incremented by one unit, where there is at least two units between any lower and higher values. For example, 'if constitutive, physical or other properties or processing parameters, such as melt viscosity, temperature, etc., range from just to (10), then the meaning is all individual values such as 1〇〇, 10 1, 1 〇 2, etc., with sub-ranges such as 1〇〇 to 144, service 0, 197 to 200, etc. can be listed. For a range of values less than 1 or containing a fraction greater than 1 (such as L1, i 5 Etc.), the minimum unit may be 0_0001, 〇·_ '0.01 or 0". For the range of values containing less than 10 digits (such as ! to 5), the minimum unit is generally "〇". The above is only an example of what is specifically indicated in the specification, and all possible combinations between the maximum and minimum numbers can be regarded as the disclosure of the present invention. The term "comprising" and its derivatives are not exclusive of any other components, steps 201111408 or private order. The existence, whether (4) is not disclosed. All applications for full-time ❹ "include, ^ ^ what doubts, may include any other steps, devices, additives 'adjuvants whether it is polymerized or other forms, unless otherwise stated == The word "must be composed of" 1 excludes any subsequent _ 立 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 program. The term "or" 1 means, unless otherwise stated, a member and a combination thereof. "The heart of the early morning singularity of the scorpion polymer" refers to the word; (; ρη十丁门) 聚合 a polymerized compound prepared from a different type or a different type of polymerizable monomer. Homopolymers (h〇m〇P〇lymers) are generally used to refer to dimers prepared from only one monomer, and the term heteromeric copolymers (interp〇lymers) are as defined below. "Isomeric Copolymers" The term means a polymer polymerized from at least two types of monomers. The term includes copolymers, which generally represent polymers made from two different types of monomers, and in two or more different forms. Monomer-prepared polymers, such as terpolymers or tetramers, etc. The term "pre-preg" refers to a porous reinforcement composite having a composition pre-impregnated with a curable resin. Pre-impregnation of the material can be carried out in various ways, including immersing the pore-shaped reinforcement in the curable resin composition, spraying the curable resin composition onto the pore-shaped reinforcement, and exposing the pore-shaped reinforcement to the curable resin In the composition of the stream, and will be curable The resin composition is vacuum infiltrated into the pore-shaped reinforcement. After the impregnation, the excess resin composition on the pore-shaped reinforcement is discharged or otherwise removed to provide "pre-preg". An example of a porous reinforcement prepared from a pre-preg may be a fabric comprising fiber-containing materials such as fibers, woven fabrics, webs, fiber strands, and non-woven aramid reinforcements such as the trademark THERMOUNT. From DuPont, Wilmington, Del. Preferably, such materials are prepared from glass, fiberglass, quartz, cellulosic or synthetic paper, thermoplastic resin substrates 'aramid reinforcement, polyethylene, poly(p-xylylene) P-phenylenediamine), polyester, polytetrafluoroethylene and poly(p-phenylene benzothiazole), syndiotactic polystyrene, carbon, graphite, ceramic or metal. Preferred materials include glass or fiberglass. , in the form of weaving or enamel. The term "pre-preg" refers to a pre-preg that is processed at high temperatures to make the prepreg (pre- Preg) partial curing. The term "epoxide prepreg (pr E-preg)" means a prepreg prepared from a resinous prepreg impregnated epoxy resin composite (Pre-Preg). The term "laminated board" means at least a high temperature and pressure will include at least A plurality of layers in a multilayer structure of a pre-preg layer are pressed together such that the pre-preg layer can be completely or substantially completely cured. Prepreg (Pre-Preg) The "Minimum Melt Viscosity" (MMV) of a powder means that the viscosity of the pre-preg powder is minimized when the temperature of the pre-preg powder is increased to a certain temperature. A pre-preg powder is a powder that remains in a powder state after the reinforcement has been removed or otherwise removed from the prepreg. The viscosity of the prepreg (Pre_Preg) powder is measured so that the reinforcement does not affect this value. The lowest melt viscosity is the result of a competition between the temperature increase which leads to a decrease in the viscosity of the pre-preg powder and the heat curing effect which leads to an increase in viscosity 201111408. For the purposes of the present invention, MMV is measured according to the procedures and conditions described in the following example sections. The "delta change amount" (ΔΜΜν) of the pre-preg powder refers to the prepreg after the prepreg (Pre_PreS) powder is stored at 1 〇〇% relative humidity' and 25 C for 24 hours. The amount of MMV change in the Pre-Preg powder. The initial MMV value of the pre-preg powder can be carried out on a pre-preg (Pre-Preg) sample obtained immediately after the pre-preg is produced. One aspect of the present invention is to provide a dual-curing hardener blend for use in an epoxy resin composition that is free of elements. Another aspect of the present invention is to provide a resin composition prepared from the dual-curing hardener blend, and a composite material prepared from the resin composition. The dual-curing hardener blend is based on a blend having at least one amine based curing agent and at least one phenolic curing agent. The dual-curing hardener blend can be used for non-halogen epoxy resins containing and/or nitrogen, as it enhances the storage stability of B-stage pre-pregs, and epoxy resin compositions. Wetability and fluidity during processing. In particular, the pre-preg powder prepared from the epoxy resin composition and the dual-curing hardener blend are characterized by having an AMMV of 20% or less. This includes embodiments in which the pre-preg powder is characterized by ΔΜΜν S 15%, and further includes an embodiment in which the pre-preg powder is characterized by ΔΜΜν < 0%. In addition, the compositions and composites prepared therefrom can meet the flammability requirements of UL 94 V0. “UL-94” is the Underwriters’ Laboratory (UL) Announcement No. 94, which is a flammability test for local plastic materials for devices and appliances. The conditions for the material to be tested are UL 94 V-0: 201111408 • None of the five tested samples were burned for more than 10 seconds when the source of ignition was removed. • The total burning time of the ten ignition tests did not exceed 50 seconds. • There is no sample to be burned on the clamp, whether it is a flame or a residual flame. • No test dripping occurs in any of the samples tested. This will cause the lower cotton cloth to catch fire. • The remaining time of the test sample is less than 30 seconds. The conditions for the under-tested material to be UL94V] are: • The five tested samples were not burned for more than 30 seconds when the source of ignition was removed. • The total burn time of the ten-under ignition test does not exceed 250 seconds. • There is no sample to be burned on the sweetness, whether it is a flame or a wall. • No test dripping occurs in any of the samples tested. This will cause the lower cotton cloth to catch fire. • There is no test sample remaining after the ignition time exceeds 60 seconds. The conditions for measuring the material to UL94V_2 are as follows: • None of the five tested samples burned for more than 30 seconds when the source of ignition was removed. • The total burning time of the ten ignition tests did not exceed 250 seconds. • There is no sample to be burned on the sweetness, whether it is a flame or a stagnation. • In the sample, only the short-burning burnt pieces in the sample showed dripping, and some of them caused the lower cotton to ignite. There is no sample test and the ignition time is more than 60 seconds. , 201111408 Since a basic embodiment of the composition of the present invention comprises an epoxy resin, optionally comprising at least one filler or nitrogen, and a hardener blend comprising an amine curing agent and a oxime curing agent . Each of these components is described in more detail below. Epoxy Resin: The composition of the present invention comprises at least one epoxy resin. In certain embodiments, the epoxy resin is a phosphorus or nitrogen containing epoxy resin. These are covalently modified with a flame retardant compound, either as a side chain or as part of a polymer backbone, which is preferably in compliance with UL 94 V0 performance requirements. Phosphorus- or nitrogen-containing epoxy resins are disclosed in U.S. Patent Nos. 6,645,631, 6,617,029 and 5,756,638, and European Patent No. EP 1,592,746. U.S. Patent No. 5,112,932 describes suitable oxazolone-modified epoxy resins. The epoxy resin may be modified, for example, by reacting with a compound or a monomer containing a phosphorus element or a nitrogen-containing element, at or after the polymerization of the epoxy resin. A compound or monomer containing phosphorus and a nitrogen-containing element which can be used in the present invention, generally containing a reactive group such as a desired group, an acid group, an amine group and an acid needle group, a phosphorous acid group, or a phosphine. A phosphinate group that reacts with an epoxy group on the epoxy resin. Examples of the filler-containing compound include, for example, one or more of the following compounds: a P-oxime functional compound such as HCa, dimethyl phosphite, diphenyl phosphite, ethylphosphonic acid, diethylphosphinic acid, A Ethyl phosphinic acid, phenylphosphonic acid, phenylphosphite, vinyl phosphoric acid, phenols (HCA--HQ) 'and analogues; tris(4-hydroxyphenyl)phosphine oxide, bis(2-hydroxyl Phenyl)phenylphosphine oxide, bis(2-hydroxyphenyl)phenylphosphonate, tris(2-yl-5-methylphenyl)phosphine oxide; acid liver compounds such as MifAH, and the like 201111408
物；以及胺基官能基化合物如雙⑷胺基笨基)碟酸笨 其混合物。 該環氧樹脂含有至少一鄰近之環氧基團。該環匕 可為如飽和或不飽和、脂肪族、環脂族、芳香族或雜产&月日 且可經取代。該環氧樹脂亦可為單體性或聚合性γ 樹脂可為聚環氧化物。聚環氧化物使用於此係指含^環氧 以上環氧基片段之化合物，或該化合物之混合物。 個 用於本發明組成物中之環氧樹脂可為如由環氧南 烷(epihalohydrin)與一酚類或酚型化合物製備 s 素丙 丙烷（epihalohydrin)與一胺類製備、由環氧 ’、 、_素丙坑 (epihalohydrin)與羧酸製備，或由不飽和化合物氧化 ， 之環氧樹脂或環氧樹脂組合物。 在一實施例中，本發明組成物中所使用之環氧樹浐勺 括由環氧鹵素丙烷(epihalohydrin)與一酚類或酚型化八物 製備者。該酚型化合物包括每分子具有平均大於一個芳香 羥基團之化合物。酚型化合物之範例包括二羥基盼、聯笨 (biphenols)、雙酚(bisphenol)、氫化雙酚、烷基化聯笨、俨 基化雙酚、三酚、酚-醛樹脂、酚醛清漆樹脂（其為酚類與 簡單醛類，較佳為曱醛之反應產物）、酚醛清漆樹脂、萘盼 酿清漆樹脂、經取代之酌酸清漆樹脂、龄-烴類樹脂、經取 代之酚-烴類樹脂、酚-羥基苯甲醛樹脂、烷基化酚-羥基苯 曱醛樹脂、烴類-酚樹脂、烴類-烷基化酚樹脂，或其組合 物。 在某些實施例中，本發明組成物中所使用之環氧樹脂 12 201111408 較佳包括由環氧鹵素丙院(epihalohydrin)與雙酌·、氫化雙 酚、酚醛清漆樹脂，以及聚二醇類，或其組合物製得之樹 脂。用於本發明之雙酚A-系環氧樹脂包括商業上可購得之 樹脂，如D.E_R.TM 300系列，以及D.E.RJM 600系列，可貝冓 自The Dow Chemical Company。可用於本發明之環氧紛酸 清漆樹脂包括商業上可購得之樹脂，如D.E.NJM 4〇〇系列， 可賭自 The Dow Chemical Company。 在某些實施例中，本發明組成物中所使用之環氧樹脂 包括製備自環氧鹵素丙烧(epihalohydrin)與間苯二盼、兒茶 酚、對苯二酚、聯苯、雙酚A、雙酚AP (1，1-雙(4-羥基苯基 苯基乙烧）、雙紛F、雙酌·Κ、雙盼C、盼-甲路盼酸清漆樹脂、 經烷基取代之酚-甲醛樹脂、酚-羥基苯曱醛樹脂、甲酚_羥 基苯曱酸樹脂、萘盼搭清漆樹脂、二環戊二浠_盼樹脂、經 二環戊二烯取代之酚樹脂、四曱基聯苯，或其組合之樹脂。 此類化合物之製備為技術上習知。請見Kirk_〇thmer，And a mixture of amino functional compounds such as bis(4)aminophenyl) discoic acid. The epoxy resin contains at least one adjacent epoxy group. The cyclic oxime may be, for example, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or miscellaneous & The epoxy resin may also be a monomeric or polymerizable γ resin which may be a polyepoxide. By polyepoxide, it is meant herein a compound containing an epoxy group or higher, or a mixture of such compounds. The epoxy resin used in the composition of the present invention may be prepared by preparing epihalohydrin and an amine from epihalohydrin and a phenolic or phenolic compound, from epoxy', , an epihalohydrin with a carboxylic acid, or an oxidized epoxy compound or an epoxy resin composition. In one embodiment, the epoxy tree spoon used in the compositions of the present invention comprises an epoxyhalohydrin and a phenol or phenolic octant. The phenolic compound includes a compound having an average of more than one aromatic hydroxyl group per molecule. Examples of phenolic compounds include dihydroxy, biphenols, bisphenol, hydrogenated bisphenol, alkylated, thiolated bisphenol, trisphenol, phenol-formaldehyde, novolac resin ( It is a reaction product of a phenol and a simple aldehyde, preferably a furfural, a novolak resin, a naphtha varnish resin, a substituted acid varnish resin, an age-hydrocarbon resin, a substituted phenol-hydrocarbon. Resin, phenol-hydroxybenzaldehyde resin, alkylated phenol-hydroxybenzaldehyde resin, hydrocarbon-phenol resin, hydrocarbon-alkylated phenol resin, or a combination thereof. In certain embodiments, the epoxy resin 12 201111408 used in the compositions of the present invention preferably comprises epihalohydrin and a combination of hydrogenated bisphenol, novolac resin, and polyglycols. Or a resin made by the composition thereof. The bisphenol A-based epoxy resin used in the present invention includes commercially available resins such as D.E_R.TM 300 series, and D.E.RJM 600 series, available from The Dow Chemical Company. Epoxy acid varnish resins useful in the present invention include commercially available resins such as the D.E.NJM 4(R) series, which can be marketed by The Dow Chemical Company. In certain embodiments, the epoxy resins used in the compositions of the present invention include those prepared from epihalohydrin and meta-phenylene, catechol, hydroquinone, biphenyl, bisphenol A. , bisphenol AP (1,1-bis(4-hydroxyphenylphenyl), double F, double discreet, anticipation, anti-hyalonic acid varnish resin, alkyl-substituted phenol - Formaldehyde resin, phenol-hydroxybenzaldehyde resin, cresol hydroxybenzoate resin, naphthalene varnish resin, dicyclopentadiene hydrazine resin, phenol resin substituted with dicyclopentadiene, tetradecyl a resin of biphenyl, or a combination thereof. The preparation of such compounds is well known in the art. See Kirk_〇thmer,
Encyclopedia of Chemical Technology，3rd Ed.，Vol. 9, pp 267-289。適用於本發明組成物之環氧樹脂與其前驅物之範 例亦描述於如美國專利號5,137,990與6,451,898中。 在某些實施例中，本發明組成物中所使用之環氧樹脂 包括製備自環氧鹵素丙院(epihalohydrin)與胺之樹脂。適用 之胺類包括二胺基二苯基曱烷、胺基酚、對二甲苯二胺、 苯胺或其組合物。 在某些實施例中’本發明組成物中所使用之環氧樹脂 包括由環氧鹵素丙烷(epihalohydrin)與羧酸製備之樹脂。適 13 201111408 用之羧酸包括酞酸、異酞酸、對酞酸、四氫-及/或六氫酞 酸、内伸曱基四氫酞酸、異酞酸、甲基六氫酞酸，或其組 合物。 該環氧樹脂可為半固化(advanced)環氧樹脂，其為一或 多種上述環氧樹脂成分，與一或多種酌型化合物，及/或一 或多種上述每分子具有平均大於一個脂肪族羥基之化合物 之反應產物。此外，該環氧樹脂可與經羧基取代之烴類， 其描述於此為一種具有碳氫骨架之化合物，較佳為具有 CrC40碳氫骨架以及一或多個羧基片段之化合物，反應。 在某些實施例中，該環氧樹脂為聚環氧化物與含有一 個以上之異氰酸酯片段或聚異氰酸酯之化合物之反應產 物。較佳為，由此反應製備之環氧樹脂為具環氧末端之聚 哼唑酮。較佳為，該組成物之環氧樹脂成分含有至少一經 0号°坐酮修飾之環氧樹脂。 含環氧樹脂之預浸物（pre-preg)之樹脂含量，以經處理 重量為基準，可依據IPCTM-650 2.3.16.1C^jS。 胺系固化劑： 術語“胺系固化劑”係指一化合物，不論是聚合性或單 體性，具有至少一胺基或亞胺基，可與環氧樹脂上之環氧 基團反應。片語“具有至少一胺基或亞胺基”，係指該胺系 固化劑可具有至少一胺基及/或至少一亞胺基，且可具有一 或多種基團。該胺系固化劑可為如脂肪族聚胺、芳香聚胺 或脂環聚胺。 脂環脂肪族聚胺系固化劑之特定範例包括乙二胺、二 14 201111408 乙二胺、二乙三胺、三乙四胺、四乙五胺、五乙六胺、丙 二胺、二丙三胺、六曱基二胺、三乙二胺、2,5-二甲基六曱 二胺、三曱基六甲二胺，以及雙（六伸甲基）三胺。環脂肪族 聚胺系固化劑之特定範例包括1，2-環己二胺、1,3-雙（胺基乙 基環己烧）、異佛爾K二胺（isophoronediamine)、N-胺基乙 基哌畊、雙(4-胺基-3-曱基環己基）曱烷、雙(4-胺基環己基) 甲烷，以及1，3,5-三（胺基曱基）苯。芳香族聚胺系固化劑之 特定範例包括二乙基甲苯二胺(DETDA)、二甲基甲苯二胺 (DMTDA)、二曱基硫代甲苯二胺(DETTDA)、m-伸苯二胺、 間二甲苯二胺、二胺基二苯基曱烷，以及二胺基二苯基砜。 二氰二醯胺(DICY)為胺系固化劑之另一特定範例。在某些 實施例中，較佳之胺系固化劑為含疏水基團之芳香胺（如 DETDA)與DICY。 盼類固化劑： 術語“酚類固化劑”係指一化合物，不論是聚合性或單 體性’其具有一或多個酚上羥基(-OH)，可在高溫下與環氧 樹脂上之環氧基反應，或可產生一或多個酚基羥基，其可 在高溫下與環氧樹脂上之環氧基反應。本組成物較佳包括 至少一含磷酚類固化劑。 該酚類固化劑可為如酚醛清漆樹脂、雙酚A酚醛清漆樹 脂、甲酚酚醛清漆，或為酚類、雙酚A、甲酚、萘酚、二甲 酚及/或其他烷基酚，與甲醛進行縮合反應而得之萘酚酚醛 清漆。酚類可溶性酚醛樹脂，如雙酚A可溶性酚醛樹脂，亦 可使用作為酚類固化劑。含磷雙酚A可溶性酚醛樹脂亦適用 15 201111408 於作為本發明之酚類固化劑。 適用之酚類固化劑包括二羥基酚、聯苯、雙酚、燒基 化聯苯、烷基化雙酚、三酚、酚_醛樹脂、酚醛清漆樹脂、 經取代之酚醛清漆樹脂、酚-烴樹脂、經取代之酚-烴樹脂、 紛-經基苯甲醒·樹脂、烧基化紛一經基苯甲酸樹脂、烴__酶樹 脂、烴-烷基化酚樹脂，或其組合物。較佳為，該酚類固化 劑包括經取代或未經取代之盼類、聯苯、雙齡、酴酸清漆、 可溶性酚醛樹脂或其組合。該酚類固化劑亦可包括多官能 基酚類交聯劑’如美國專利號6,645,631，第4欄，第57-67 行，至第6攔第1-57行所描述。 可產生酚類羥基官能基之酚類固化劑範例為苯倂π号啡 與聚苯倂噚畊。“產生”於此係指加熱該固化劑化合物後， 該固化劑化合物會轉換為另一具有酚類羥基官能基之化合 物，其可作為固化劑。 商業上可購得之酚類固化劑範例包括DEH 85、DEH 87 與DEH 90 ’ 靖自 Dow Chemical Company。 在某些實施例中，該酚類固化劑比胺系固化劑之重量 比介於80:1至1:8〇間，較佳介於50:^1:50間，更佳介於3〇:1 至1:30間，更佳介於10:1至1:10間。在某些實施例中，該組 成物包含25至55%重之酚類固化劑’以該組成物固體含量 之總重量為基準。此包括其中該組成物含有30至5〇%重之 盼類固化物’以該組成物固體含量之總重量為基準之實施 例’更包括其中該組成物包含35至45%重之酚類固化劑， 以該組成物固體含量之總重量為基準之實施例。在某些實 201111408 施例中，該組成物包含1至15%重之胺系固化劑，以該組成 物固體含量之總重量為基準。此包括其中該組成物含有2至 12%重之胺系固化劑，以該組成物固體含量之總重量為基 準之貫施例，更包括其中該組成物含有3至1〇%重之胺系固 化劑，以該組成物固體含量之總重量為基準之實施例。 額外之固化劑： 該組成物可更包括亦可作為阻燃劑之額外固化劑。例 如，該組成物可包括含磷固化劑，如酞酸二辛酯（D〇p)系之 固化劑（如DOP-BN與DOP-HQ)'三聚氰胺聚(磷酸酯），以及 聚(1,3-伸苯基曱基嶙酸酯）（Fyrol PMP)。歐洲專利號EP 1，753,772與美國專利號6,403,220，係描述適當之含磷固化 劑，包括D0P-BN)。 固化催化劑： 本組成物可更選擇性包括一或多種固化催化劑（亦稱 之為固化加速劑或固化活化劑）。此類催化劑包括含氮化合 物，其可催化環氧樹脂與固化劑之反應。該含氮催化劑化 合物可與固化劑作用，形成固化劑與環氧樹脂間之難熔性 反應產物，為製造流程中之最終物件，如結構性複合材料 或積層板。難熔性反應產物係指該環氧樹脂實質上完全固 化，如在二連續Tg測量間（ΔΤε)僅有些微或無變化時。 在一實施例中，該含氮化合物為雜環氮化合物、胺類 或錢類化合物。較佳為，該含氮催化劑為D米嗤、°米°坐衍生 物’或其混合物。適當之味α坐範例包括2-甲基咪唾(2-MI)、 2·苯基咪唑(2-ΡΙ)、2-乙基-4-甲基咪唑，及其組合。適當催 17 2011H408 化劑化合物範例亦包括列於歐洲專利說明書Ep。954⑸ B1上之化合物。 本發明含氮催化劑化合物可單獨使用、相互組合，或 與其他技術上習知之加速劑或固化催化劑化合物組合。其 他已知之-般催化劑化合物包括，但不侷限於膦化合物、 鏔鹽、料鹽類、胺類、敍鹽，與二。丫雙環化合物，以及 其四苯基硼酸鹽、酚鹽與酚類酚醛清漆鹽類。可用於與本 發明含氮催化劑化合物結合之適當催化劑化合物範例，亦 包括列於美國專利號6,255,365中之化合物。 本發明組成物中催化劑之使用量為可有效催化環氧樹 脂與固化劑反應之量。催化劑之使用量取決於組成物中所 使用之成分，以及待製造之物件之目標表現度。在一實施 例中’所使用之固化加速劑量較佳自0 〇〇1%至小於10〇/〇重 (以組成物之總固體含量為基礎），更佳自0 01%至5%重，尤 佳自0.02%至2%重，最佳自0.04%至1%重。 固化劑比環氧樹脂之比例： 固化劑比環氧樹脂之比例較佳可提供完全或實質上完 全固化之樹脂。其中存在之固化劑量可依據所使用之特定 固化劑而變化（取決於固化化學特性與固化劑等價重量）。 在一實施例中’環氧樹脂與酚類與胺系固化劑間之重量比 介於0.1:1至1:〇_1，較佳介於1:0.5至0.5:1間，更佳介於1:0.8 至0_8:1間。在某些實施例中，該組成物包含30至55%重固 化劑，以組成物總固體含量為基礎。此包括其中該組成物 含有35至55%重之固化劑，以組成物總固體含量為基礎之 18 201111408 實施例’更包括其中該組成物含有40至50%重固化劑，以 組成物總固體含量為基礎之實施例。在某些實施例中，該 組成物包含40至70%重之環氧樹脂，以組成物總固體含量 為基礎。此包括其中該組成物含有45至65%重之環氧樹 脂，以組成物總固體含量為基礎之實施例，更包括其中組 成物含有40至60%重之環氧樹脂，以組成物總固體含量為 基礎之實施例。 其他添加物與溶劑： 選擇性地’本發明之組成物可更包含其他一般用於環 氧樹脂組成物中之成分，尤其是用於製造預浸物(pre_preg) 與積層板；且不會對於本發明組成物，或其最終固化產物 之表現度有不良影響者。例如，其他可用於該組成物之選 擇性成分包括韌化劑；固化抑制劑；填充劑；濕潤劑；增 色劑；阻燃劑；溶劑；熱塑劑；加工輔助劑；螢光化合物， 如四酚乙烷(TPE)或其衍生物；UV阻隔化合物；以及其他 添加物。本發明組成物亦可包括其他選擇性成分，如無機 填充物與其他阻燃劑，如氧化銻、八溴二苯基氧化物、十 >臭二苯基氧化物、填酸與其他此類組成包括，但不侷限於， 染料、顏料、界面活性劑、流動控制劑與塑化劑。 本發明組成物亦可選擇性地包含一溶劑；或組成物之 任何其他成分，如環氧樹脂、固化劑，及/或催化劑化合物， 可選擇性地用於組合或單獨溶於溶劑中。較佳為，溶劑中 之固體濃度至少50%，不大於90%固體，較佳介於55%至8〇% 間，以及更佳介於60%至7〇%固體。適當溶劑之非限制性範 19 201111408 例包括酮類、醇類、水、醇醚類、芳香烴與其混合物，較 佳之溶劑包括酮類、甲基乙基酮、曱基異丁基酮、環己酮、 甲基°比咬嗣、丙二醇單曱基醚、丙二醇單乙基醚醋酸酯、 乙二醇單甲基醚、曱基戊烷基酮、甲醇、異丙醇、曱苯、 二甲苯、二曱基甲醛(DMF)。可使用單一溶劑，但亦可使 用個別溶劑作為一或多種成分。 本發明組成物之各成分可以任何順序互相混合。例 如’ s亥組成物可由含環氧樹脂之第一組成物，以及含酚類 與胺系固化劑之第二組成物製備。不論是第一或第二組成 物’皆可包含一固化催化劑。所有其他成分皆可存在於同 一組成物中’或可部分存在於第一組成物，部分存在於第 二組成物中。之後該第一組成物可與第二組成物混合，以 製得可固化、阻燃性之環氧樹脂組成物。 複合材料： 本發明組成物可用於製備複合材料，利用如拉擠、鑄 杈成形、封裝或塗佈等技術^在一實施例中，本發明係提 供一種製備樹脂塗覆物件之方法。該方法步驟包括將一物 件或基板與一樹脂組成物接觸。該組成物可以任何技術上 習知之方法與一物件接觸。此類接觸方法範例包括粉末塗 佈、喷霧塗佈、鋼模塗佈、滾輪塗佈、樹脂灌注法，以及 將s亥物件與含有該組成物之水浴接觸。在另一實施例中， 本發明係提供一種由本發明方法製備之物件，尤其是預浸 物(pre-preg)與積層板。 同時提供以本發明環氧樹脂組成物浸潰該孔狀強化物 20 201111408 而製備之預浸物(Pre-Preg)。本發明亦提供金屬塗覆箔，係 將金屬箔塗覆上本發明環氧樹脂組成物而製備。本發明更 提供一種具有強化特性之積層板，藉由將上述預浸物 (pre-preg)及/或上述金屬塗覆猪層壓而得。 如上所述，本發明組成物可用於浸潰各種強化物，包 括孔狀強化物。可以本發明組成物塗覆之強化材料包括可 用於形成複合材料、預浸物(pre-preg)及/或積層板之材料。 適當之基板範例包括含纖維材料，如織布、纖維網、纖維 墊’以及不織芳論強化物，如商標名為THERMOUNT，得 自DuPont，Wilmington，De卜較佳為，此類材料係製備自玻 璃、玻璃纖維、石英、纖維素性或合成性紙張、熱塑性樹 脂基板如芳綸強化物、聚乙烯、聚（對苯二曱醯對苯二胺）、 聚酯、聚四氟乙烯與聚（對·伸苯基苯併雙噻唑）、間規聚苯 乙烯、奴、石墨、陶瓷或金屬。較佳之材料包括玻璃或玻 璃纖維，為織布或墊形式。 在一實施例中’該強化材料係以樹脂組成物塗覆(如藉 —將其與組成物浴接觸）、溶解並與溶劑或溶劑混合物混 合該塗覆步驟可於使該強化材料可塗覆上該樹脂組成物 ^、下進行。之後該經塗覆之強化材料可加熱至足以使 露 之处度，但該溫度需低於可使樹脂組成物在熱暴 n生月顯固化之溫度，儘管環氧樹脂成分(B-階段)在熱 暴露過程巾已產生部分固化。 —=¾. ^ U 7 有6預浸物(Pre-Preg)可加工為積層板，選擇性具 或多片導電材料，如銅。在此類再加工製程中，該經 21 201111408 塗覆強化材料之一或多個片段或部分，係與另一強化材料 及/或一導電材料接觸。之後，該接觸部分係暴露於高壓與 高溫下，其足以導致環氧樹脂固化，其中鄰近部分之樹脂 會互相作用形成一連續之環氧樹脂基質。在固化前，可切 割下部分並重叠，或折豐後重疊為希望之形狀與厚度。在 某些實施例中，較佳該積層板或最終產物進行壓製外之後 固化作用。此步驟係設計用以完成固化反應。此後固化步 驟可於真空下進行，以移除任何可揮發之成分。 範例 測量： 預浸物(pre-preg)之穩定性為MMV之特徵，係以Ant〇n PearphysicaMGR-301流變儀，配備有CP25_2錐板，於固定 剪切速率下測量。用於MMV測量目的，樣本係依下製備： 粉碎預浸物(pre-preg)並以120微米篩網過濾。此提供已移除 玻璃強化物之預浸物(pre-preg)粉末。之後將所得之〇 32§粉 末置於已預熱至160 C之溫度控制板(peltier plate)上。前1〇〇 秒的剪切速率設定為26 rpm/min，最後250秒調整為13 rpm/mm。監測熔融黏度對時間之關係。將預浸物(pre_preg) 我末存放於濕度經控制之腔室中24小時，相對濕度為 100%，溫度為25°c，以製備老化樣本，之後測量其MMV， 以決定ΔΜΜ V值。 材料· 在下例中，XZ 92748.〇〇為環氧酚醛清漆樹脂，含85 wt0/〇之1-甲氧基-2-丙醇(PM)固體；XZ 92740.00為高Tg環氧 22 201111408 酴酸清漆樹脂’得自 Dow Chemical Company ; XZ 92749.00 為含麟盼類固化劑，得自Dow Chemical Company (其為XZ 92535、含50 wt%曱氧基丙基(PMA)固體之酚類酚醛清漆樹 脂，與XZ 92741，一種含磷雙酚A可溶性酚醛樹脂，含57 wt% PM 固體之摻合物。）。DETDA得自 Albemarle Co。DICY 得自 Darong Co. Ltd。其他材料為得自 Aldrich Chemical Co. 之2-苯基咪唑（10 wt%固體，Dowanol™，PM)與2-甲基咪 唑，係使用作為催化劑。 範例1 :控制組 控制組樣本係製備為不含雙重-固化硬化劑摻合物。控 制組樣本係以不同成分之混合物製成，具表13所列之比 例。將該混合物置於搖晃器上混合。 預浸物(pre-preg)係製備自控制組樣本，藉由人工將玻 璃網(E-7628 type)塗在樣本上，並於17〇。(：烘箱中烘烤數分 鐘，以控制預浸物（pre-preg)的成膠時間，以便進行進一步 之穩定性測試。MMV係以Anton Pear MCR 301流變儀，依 據上述方法測量。結果列於表it。 控制組樣本的成膠時間為280秒，預浸物(pre_preg)的 烘烤時間為270秒，預浸物(pre-preg)成膠時間為5丨秒。 表la 成分 固體含量(Wt.°/o) 固體重量(g) 溶液(g) XZ92748 85 45 105.88 XZ92749 50 55 220 〇〇 2-PI 10 0.16 (phr) 3.20 23 201111408 表lb MMV(PaS) 初始 48.1 24小時後，100% R.H. 35.1 Δ 27.0 範例2 :發明範例1 本發明阻燃環氧樹脂組成物之工作樣本，係以混合表 2a上之成分而製備，依據範例1所述之方法。MMV如上述 方法紀錄，結果列於表2b。 工作樣本的成膠時間為297秒，預浸物(pre-preg)的烘 烤時間為330秒，預浸物(pre-preg)的成膠時間為45秒。該 組成物具有磷含量（“P%’）為3.12%，以組成物之固體含量為 基礎，環氧樹脂之化學計量莫耳重量（“Epo. Mol.”）為 0·31，以及固化基團（包括-OH與-NH)之化學計量莫耳重量 (“Hard. Mol·，，）為0.30。 表2a 成i 固體含量(wt.%) 固體重量(g) 溶液(g) XZ92748 85 55 132.65 XZ92741 57 35 125.88 DETDA 100 10 20.50 2-PI 10 0.18 (phr) 3.69 表2b MMV(PaS) 成分 46.5 24hrJ|_，100%R.H. 49 Δ -5.4 24 201111408 範例3 :比較範例1 阻燃環氧樹脂組成物之比較樣本，傳以混合表3a上之 成分而製備，依據範例i所述之方法。MMV如上述方法紀 錄，結果列於表3b。 比較樣本的成膠時間為251秒，預浸物（pre preg)的烘 烤時間為235秒、，預浸物(Pre-Preg)的成膠時間為75秒。 表3a 成分 固體含量(wt.%) 固體重量(g) 溶液(g) XZ92740 85 64 150.6 XZ92741 57 36 126.3 DICY 12 2.4 40.0 2-MI ^ 10 1.1 22.0 表3b '----___ MMV(PaS) 初始 ----- 34.7 > 100%R.H. 21.1 Δ ^ 39.2 __ 範例4 :發明範例2 阻燃環氧樹脂組成物之比較樣本，係以混合表如上之 成分而製備’依據範例1所述之方法。MMV如上述方法紀 錄’結果列於表仆。 比杈樣本的成膠時間為253秒，預浸物(pre-preg)的烘 烤時間為现秒，預浸物(pre_preg)的成膠時間為60秒。該 組成物具有磷含量(“P%，)為3.13%，以組成物之固體含量為 基礎’ ％氧樹脂之化學計量莫耳重量（“Ep〇· Mol.”）為 25 201111408 0·36,以及固化基團（包括-OH與-NH)之化學計量莫尊重量 (“Hard. Mol.”）為 0 31。 _ 表4a 成分 ·*'— ____ ________ 固體含量(wt·%) 固體重量(g) 溶液(g) ΧΖ92748 85 64 75.29 ΧΖ92741 57 36 63.16 _____ DICY 20 2.4 12 2-ΜΙ 10 0.7 7 表4b MMV(PaS) 初始 42 _^1、時後，i〇〇%R H. 38.6 Δ --—— 8.1 範例5 :發明範例3 本發明阻燃環氧樹脂組成物之工作樣本，係以混合表 5 a上之成分而製備，依據範例1所述之方法。薄膜玻璃轉換 溫度係以DSC(差示掃瞄熱分析儀）測量，待溶劑移除並於 190°C加熱板上固化90分鐘後。MMV如上述方法紀錄’結 果列於表5b。 工作樣本的成膠時間為235秒，預浸物(Pre_preg)的烘 烤時間為200秒，預浸物(pre-preg)的成膠時間為58秒。該 組成物具有磷含量（“P%，）為3.12%，以組成物之固體含量為 基礎，環氧樹脂之化學計量莫耳重量（“EP0· M〇K”）為 0.29，以及固化基團（包栝_〇H與-NH)之化學計量莫耳重量 (“Hard. Mol·，，)為 〇·28。 26 201111408 表5a 成分 ___---------1 固體含量(wt.%) 固體重量(g) 溶液$) _ XZ92748 85 52 125.41 XZ92741 57 35 125.88 DETDA 100 6.5 13.33 XZ92535 50 6.5 26.65 2-PI 10 0.17 (phr) 3.35 ------1 表5b MMV(PaS) 初始 28.8 24小時後，i〇〇%r.h. 25.4 Δ 11.8 範例6 :發明範例4 本發明阻燃環氧樹脂組成物之工作樣本，係以混合表 6a上之成分而製備，依據範例丨所述之方法。薄膜玻璃轉換 /皿度係以DSC (differential scanning calorimetry)測量，待溶 劑移除並於190°C加熱板上固化90分鐘後。MMV如上述方 法紀錄，結果列於表6b。 工作樣本的成膠時間為334秒，預浸物(pre-preg)的烘 烤時間為260 s。該組成物具有鱗含量(“P%’）3.05%，以組 成物之固體含量為基礎，環氧樹脂之化學計量莫耳重量 (‘‘％〇. Mol.’’)為0.326,以及固化基團（包括-OH與-NH)化 學計量莫耳重量(“Hard. Mol·，，)為0.331。 27 201111408 表6a 成分 固體含量(wt·%) 固體重量(g) 溶液(g) XZ92748 85 58 68.24 XZ92741 57 35 61.40 XZ92535 50 7 14.00 DICY 100 2 2.00 2-PI 10 0 (phr) 0.00 MEK/PM 0 0 6.34 表6b MMV(PaS) 初始 25.9 24 小時後，100%R.H. 24.6 Δ 5.0 範例7 :發明範例5 本發明阻燃環氧樹脂組成物之工作樣本，係以混合表 7a上之成分而製備，依據範例1所述之方法。MMV如上述 方法紀錄，結果列於表7b。 工作樣本的成膠時間為294秒，預浸物（pre-preg)的烘 烤時間為255秒，預浸物(pre-preg)的成膠時間為41秒。該 組成物具有磷含量（“P%’）為2.93%，以組成物之固體含量為 基礎，環氧樹脂之化學計量莫耳重量（“Epo. Mol.”）為 0.331，以及固化基團（包括-OH與-NH)之化學計量莫耳重 量（“Hard. Mol.，，)為 0.343。 28 201111408 表7a 成分 固體含量(wt.%) 固體重量(g) 溶液(g) XZ92748 85 59 69.41 XZ92741 57 33 57.89 XZ92535 50 4 8.00 DICY 100 2 2.00 DETDA 100 2 2.00 2-PI 10 0.08 (phr) 0.80 PM 0 0 16.00 表7b MMV(PaS) 初始 39.6 24 小時後，100%R.H. 39.7 Δ 0.3 範例8 :比較範例2 阻燃環氧樹脂組成物之比較樣本，係以混合表8a上之 成分而製備，依據範例1所述之方法。MMV如上述方法紀 錄，結果列於表8b。 比較樣本的成膠時間為257秒，預浸物(pre-preg)的烘 烤時間為315秒，預浸物（pre-preg)的成膠時間為77秒。該 組成物具有磷含量（“P%’）為3.03%，以組成物之固體含量為 基礎，環氧樹脂之化學計量莫耳重量（“Epo. Mol.”）為 0.275，以及固化基團（包括-OH與-NH)之化學計量莫耳重 量（“Hard. Mol.’’)為 0.277。 29 201111408 表8a 成为 固體含量(wt_%) 固體重量(g) 溶液(g) XZ92748 85 49 57.65 XZ92741 57 34 59.65 DDS 100 7 7 XZ92535 50 10 20 2-PI 10 0.15 (phr) 1.5 PM 11 表8b MMV(PaS) 初始 49.8 24 小時後，100%R.H. 38 Δ 23.7 (DDS=二胺基二苯基颯) 範例9 :比較範例3 阻燃環氧樹脂組成物之比較樣本’係以混合表9a上之 成分而製備，依據範例1所述之方法。MMV如上述方法紀 錄，結果列於表9b。 比較樣本的成膠時間為252秒，預浸物(Pre_preg)的烘 烤時間為265秒，預浸物(Pre-Preg)的成膠時間為45秒。該 組成物具有填含量（“P%’）為3 ·03% ’以組成物之固體含直為 基礎，環氧樹脂之化學計量莫耳重量（“EP〇. Mo1.”）為 0·292，以及固化基團（包括-OH與-NH)之化學計量莫耳重 量(“Hard. Mol.，，)為0.299。 30 201111408 表9a 成分 _—-Ί 固體含量(wt.%) 固體重點(g) XZ92748 85 52 XZ92741 57 34 59.65 SAA 100 7 7 _一_ XZ92535 50 7 14 2-PI 10 0.3 (phr) 3 ----* PM 12 -----— (SAA =胺苯續醢胺) 表9b MMV(PaS) 初始 51.6 24小時後，100% R.H. 34.9 Δ 32.4 範例10 :比較範例4 阻燃環氧樹脂組成物之比較樣本，係以混合表10a上之 成分而製備，依據範例1所述之方法。MMV如上述方法紀 錄，結果列於表1 〇b » 比較樣本的成膠時間為272秒，預浸物(pre-preg)的烘烤 時間為305秒，預浸物(pre_preg)的成膠時間為84秒。該組成 物具有磷含量（“p%，）為3 〇3%，以組成物之固體含量為基 礎，環氧樹脂之化學計量莫耳重量(“Ερο. Μ〇1·”)為0.264， 以及固化基團（包括-OH與-ΝΗ)之化學計量莫耳重量 (“Hard.M〇l.，％〇27〇。 31 201111408 表10a 成·^ 固體含量(wt.%) 固體重量(g) 溶液(g) XZ92748 85 47 55.29 XZ92741 57 34 59.65 MDA 100 2 2 XZ92535 50 17 34 2-PI 10 0.05 (phr) 0.5 PM 6 (MDA = m-伸苯基二胺) 表10b MMV(PaS) 初始 37.3 24 小時後，100%R.H. 22 Δ 41.0 應注意到本發明並未受到各實施例與說明限制，並包括這 些實施例與說明之修飾形式，包括實施例之各部分，以及不同 實施例之元件組合，這些都包含於下列申請專利範圍中。 I：圖式簡單說明3 (無） 【主要元件符號說明】 (無） 32Encyclopedia of Chemical Technology, 3rd Ed., Vol. 9, pp 267-289. Examples of epoxy resins and their precursors suitable for use in the compositions of the present invention are also described in U.S. Patent Nos. 5,137,990 and 6,451,898. In certain embodiments, the epoxy resins used in the compositions of the present invention include resins prepared from epihalohydrin and amines. Suitable amines include diaminodiphenylnonane, aminophenol, p-xylenediamine, aniline or combinations thereof. The epoxy resin used in the composition of the present invention in certain embodiments includes a resin prepared from epihalohydrin and a carboxylic acid. Benzene 13 201111408 The carboxylic acid used includes citric acid, isophthalic acid, p-citric acid, tetrahydro- and/or hexahydrononanoic acid, intrinsic mercaptotetrahydrofurfuric acid, isodecanoic acid, methyl hexahydrofurfuric acid, Or a composition thereof. The epoxy resin may be an advanced epoxy resin which is one or more of the above epoxy resin components, and one or more discretionary compounds, and/or one or more of the above having an average of more than one aliphatic hydroxyl group per molecule. The reaction product of the compound. Further, the epoxy resin may be reacted with a carboxyl group-substituted hydrocarbon, which is described as a compound having a hydrocarbon skeleton, preferably a compound having a CrC40 hydrocarbon skeleton and one or more carboxyl groups. In certain embodiments, the epoxy resin is a reaction product of a polyepoxide with a compound containing more than one isocyanate segment or polyisocyanate. Preferably, the epoxy resin prepared by the reaction is a polyoxazolone having an epoxy end. Preferably, the epoxy resin component of the composition contains at least one epoxy resin modified with ketone. The resin content of the epoxy-containing pre-preg is based on the treated weight and can be based on IPCTM-650 2.3.16.1 C^jS. Amine curing agent: The term "amine curing agent" means a compound which, whether polymerizable or monomeric, has at least one amine group or imine group and is reactive with an epoxy group on the epoxy resin. The phrase "having at least one amino or imine group" means that the amine-based curing agent may have at least one amine group and/or at least one imine group, and may have one or more groups. The amine curing agent may be, for example, an aliphatic polyamine, an aromatic polyamine or an alicyclic polyamine. Specific examples of the alicyclic aliphatic polyamine curing agent include ethylenediamine, di 14 201111408 ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylene Triamine, hexamethylenediamine, triethylenediamine, 2,5-dimethylhexamethylenediamine, tridecylhexamethyldiamine, and bis(hexamethyl)triamine. Specific examples of the cycloaliphatic polyamine curing agent include 1,2-cyclohexanediamine, 1,3-bis(aminoethylcyclohexene), isophoronediamine, and N-amino group. Ethyl piped, bis(4-amino-3-indolylcyclohexyl)decane, bis(4-aminocyclohexyl)methane, and 1,3,5-tris(aminomercapto)benzene. Specific examples of the aromatic polyamine curing agent include diethyltoluenediamine (DETDA), dimethyltoluenediamine (DMTDA), dimercaptothiotoluenediamine (DETTDA), m-phenylenediamine, Meta-xylene diamine, diaminodiphenyl decane, and diaminodiphenyl sulfone. Dicyanoguanamine (DICY) is another specific example of an amine curing agent. In certain embodiments, preferred amine based curing agents are hydrophobic groups containing a hydrophobic group (e.g., DETDA) and DICY. Refractory-type curing agent: The term "phenolic curing agent" means a compound, whether polymerizable or monomeric, which has one or more phenolic hydroxyl groups (-OH), which can be used at high temperatures and on epoxy resins. The epoxy group reacts or can produce one or more phenolic hydroxyl groups which can react with the epoxy groups on the epoxy resin at elevated temperatures. The composition preferably includes at least one phosphorus-containing phenol type curing agent. The phenolic curing agent may be, for example, a novolac resin, a bisphenol A novolak resin, a cresol novolac, or a phenol, bisphenol A, cresol, naphthol, xylenol, and/or other alkylphenols. A naphthol novolak obtained by a condensation reaction with formaldehyde. Phenolic soluble phenolic resins, such as bisphenol A soluble phenolic resins, can also be used as phenolic curing agents. Phosphorus-containing bisphenol A soluble phenolic resin is also suitable for use as a phenolic curing agent of the present invention. Suitable phenolic curing agents include dihydric phenol, biphenyl, bisphenol, alkylated biphenyl, alkylated bisphenol, trisphenol, phenolic-aldehyde resin, novolak resin, substituted novolac resin, phenol- A hydrocarbon resin, a substituted phenol-hydrocarbon resin, a phthalic acid styrene resin, an alkylated benzoic acid resin, a hydrocarbon-based resin, a hydrocarbon-alkylated phenol resin, or a combination thereof. Preferably, the phenolic curing agent comprises substituted or unsubstituted, biphenyl, double age, phthalic acid varnish, resol phenolic resin or a combination thereof. The phenolic curing agent may also include a polyfunctional phenolic crosslinking agent as described in U.S. Patent No. 6,645,631, col. 4, lines 57-67, to pp. 1-57. An example of a phenolic curing agent which can produce a phenolic hydroxyl functional group is benzoquinone π morphine and polyphenyl hydrazine. By "produced" herein is meant that upon curing of the curing agent compound, the curing agent compound is converted to another compound having a phenolic hydroxyl functional group which acts as a curing agent. Commercially available examples of phenolic curing agents include DEH 85, DEH 87 and DEH 90' Jing from Dow Chemical Company. In some embodiments, the weight ratio of the phenolic curing agent to the amine curing agent is between 80:1 and 1:8, preferably between 50:1:50, more preferably between 3:1. Between 1 and 30, better between 10:1 and 1:10. In certain embodiments, the composition comprises from 25 to 55% by weight of the phenolic curing agent' based on the total weight of the solids content of the composition. This includes the embodiment in which the composition contains 30 to 5% by weight of the desired cured product 'based on the total weight of the solid content of the composition', and further includes the phenolic curing in which the composition contains 35 to 45% by weight. An example based on the total weight of the solids content of the composition. In some embodiments of 201111408, the composition comprises from 1 to 15% by weight of the amine based curing agent, based on the total weight of the solids content of the composition. This includes the embodiment in which the composition contains 2 to 12% by weight of the amine-based curing agent, based on the total weight of the solid content of the composition, and further includes an amine system in which the composition contains 3 to 1% by weight. The curing agent is an example based on the total weight of the solid content of the composition. Additional Curing Agent: The composition may further include an additional curing agent that may also act as a flame retardant. For example, the composition may include a phosphorus-containing curing agent such as a dioctyl phthalate (D〇p)-based curing agent (such as DOP-BN and DOP-HQ) 'melamine poly(phosphate), and poly(1, 3-phenylphenyl decanoate) (Fyrol PMP). European Patent No. EP 1,753,772 and U.S. Patent No. 6,403,220, the disclosure of each of each of each of each of each of each of Curing Catalyst: The present composition may more optionally include one or more curing catalysts (also referred to as curing accelerators or curing activators). Such catalysts include a nitrogen-containing compound that catalyzes the reaction of the epoxy resin with a curing agent. The nitrogen-containing catalyst compound acts with a curing agent to form a refractory reaction product between the curing agent and the epoxy resin, and is the final article in the manufacturing process, such as a structural composite or laminate. The refractory reaction product means that the epoxy resin is substantially completely cured, such as when there is little or no change between two consecutive Tg measurements (ΔΤε). In one embodiment, the nitrogen-containing compound is a heterocyclic nitrogen compound, an amine or a money compound. Preferably, the nitrogen-containing catalyst is D m 嗤, 米 ° sitting derivative ‘ or a mixture thereof. Examples of suitable taste alpha sitting include 2-methylmeridene (2-MI), 2-phenylimidazole (2-indole), 2-ethyl-4-methylimidazole, and combinations thereof. Appropriate reminders 17 Examples of 2011 H408 chemical compounds are also included in the European patent specification Ep. 954(5) Compound on B1. The nitrogen-containing catalyst compounds of the present invention may be used singly, in combination with each other, or in combination with other accelerators or curing catalyst compounds conventionally known in the art. Other known catalyst compounds include, but are not limited to, phosphine compounds, phosphonium salts, salt salts, amines, salts, and two. Bis-ring compounds, as well as their tetraphenylborates, phenates and phenolic novolac salts. Examples of suitable catalyst compounds that can be used in combination with the nitrogen-containing catalyst compounds of the present invention also include those listed in U.S. Patent No. 6,255,365. The amount of the catalyst used in the composition of the present invention is an amount effective to catalyze the reaction of the epoxy resin with the curing agent. The amount of catalyst used depends on the ingredients used in the composition and the target performance of the item to be manufactured. In one embodiment, the curing acceleration dose used is preferably from 0 〇〇 1% to less than 10 〇 / 〇 (based on the total solids content of the composition), more preferably from 0 01% to 5% by weight. It is especially preferred from 0.02% to 2% by weight, preferably from 0.04% to 1% by weight. Ratio of Curing Agent to Epoxy Resin: The ratio of curing agent to epoxy resin is preferred to provide a fully or substantially fully cured resin. The amount of curing agent present therein will vary depending upon the particular curing agent used (depending on the curing chemistry and the equivalent weight of the curing agent). In one embodiment, the weight ratio of the epoxy resin to the phenolic to amine curing agent is from 0.1:1 to 1:?_1, preferably from 1:0.5 to 0.5:1, more preferably between 1: 0.8 to 0_8:1. In certain embodiments, the composition comprises from 30 to 55% re-curing agent based on the total solids content of the composition. This includes wherein the composition contains 35 to 55% by weight of a curing agent based on the total solids content of the composition. 18 201111408 Example 'More includes wherein the composition contains 40 to 50% of a curing agent to total solids of the composition A content based embodiment. In certain embodiments, the composition comprises 40 to 70% by weight epoxy resin based on the total solids content of the composition. This includes embodiments in which the composition contains 45 to 65% by weight of epoxy resin based on the total solids content of the composition, and further includes an epoxy resin having a composition containing 40 to 60% by weight of the total solids of the composition. A content based embodiment. Other additives and solvents: Optionally, the composition of the present invention may further comprise other components generally used in epoxy resin compositions, especially for the manufacture of prepregs and laminates; The composition of the present invention, or the final cured product thereof, has an adverse effect on the performance. For example, other optional ingredients useful in the composition include toughening agents; curing inhibitors; fillers; wetting agents; colorants; flame retardants; solvents; thermoplastics; processing aids; Phenolethane (TPE) or a derivative thereof; a UV blocking compound; and other additives. The composition of the present invention may also include other optional ingredients such as inorganic fillers and other flame retardants such as cerium oxide, octabromodiphenyl oxide, decyl diphenyl oxide, acid filling and the like. Compositions include, but are not limited to, dyes, pigments, surfactants, flow control agents, and plasticizers. The composition of the present invention may optionally further comprise a solvent; or any other component of the composition, such as an epoxy resin, a curing agent, and/or a catalyst compound, optionally used in combination or separately dissolved in a solvent. Preferably, the solids concentration in the solvent is at least 50%, no greater than 90% solids, preferably between 55% and 8%, and more preferably between 60% and 7% solids. Non-limiting examples of suitable solvents 19 201111408 Examples include ketones, alcohols, water, alcohol ethers, aromatic hydrocarbons and mixtures thereof. Preferred solvents include ketones, methyl ethyl ketone, decyl isobutyl ketone, cyclohexane Ketone, methyl ratio, propylene glycol monodecyl ether, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, decylpentanone, methanol, isopropanol, toluene, xylene, Dimercaptoformaldehyde (DMF). A single solvent can be used, but individual solvents can also be used as one or more ingredients. The components of the composition of the present invention may be mixed with each other in any order. For example, the composition may be prepared from a first composition comprising an epoxy resin and a second composition comprising a phenolic and amine based curing agent. Both the first or second composition' may contain a curing catalyst. All other ingredients may be present in the same composition' or may be partially present in the first composition and partially in the second composition. The first composition can then be mixed with the second composition to produce a curable, flame retardant epoxy resin composition. Composite material: The composition of the present invention can be used to prepare a composite material by a technique such as pultrusion, cast molding, encapsulation or coating. In one embodiment, the present invention provides a method of preparing a resin coated article. The method step includes contacting an object or substrate with a resin composition. The composition can be contacted with an article by any method known in the art. Examples of such contact methods include powder coating, spray coating, steel die coating, roller coating, resin infusion, and contacting a sigma object with a water bath containing the composition. In another embodiment, the invention provides an article, especially a pre-preg and laminate, prepared by the method of the invention. At the same time, a prepreg (Pre-Preg) prepared by impregnating the pore-shaped reinforcement 20 201111408 with the epoxy resin composition of the present invention is provided. The present invention also provides a metal coated foil prepared by coating a metal foil with the epoxy resin composition of the present invention. The present invention further provides a laminate having reinforced properties obtained by laminating the above-mentioned pre-preg and/or the above-mentioned metal coated pig. As noted above, the compositions of the present invention can be used to impregnate various reinforcements, including porous reinforcements. Reinforcing materials which may be coated with the compositions of the present invention include materials which can be used to form composites, pre-pregs and/or laminates. Examples of suitable substrates include fibrous materials such as woven fabrics, fibrous webs, fiber mats, and non-woven reinforcements, such as the trademark THERMOUNT, available from DuPont, Wilmington, Deb, and the preparation of such materials. From glass, fiberglass, quartz, cellulosic or synthetic paper, thermoplastic resin substrates such as aramid reinforcement, polyethylene, poly(p-phenylene terephthalamide), polyester, polytetrafluoroethylene and poly( P-phenylbenzobisthiazole, syndiotactic polystyrene, slave, graphite, ceramic or metal. Preferred materials include glass or glass fibers in the form of a woven or mat. In one embodiment, the reinforcing material is coated with a resin composition (eg, by contacting it with a bath of the composition), dissolved, and mixed with a solvent or solvent mixture. The coating step can be used to coat the reinforcing material. The resin composition was applied to the lower layer. The coated reinforcing material can then be heated to a level sufficient to provide a dew point, but at a temperature below the temperature at which the resin composition can be cured during the thermal storm, despite the epoxy resin composition (B-stage). The towel has been partially cured during the heat exposure process. —=3⁄4. ^ U 7 There are 6 prepregs (Pre-Preg) that can be processed into laminates with selective or multiple conductive materials such as copper. In such a reprocessing process, one or more segments or portions of the coated coating material are contacted with another reinforcing material and/or a conductive material. Thereafter, the contact portion is exposed to high pressures and temperatures which are sufficient to cause the epoxy to cure, wherein adjacent portions of the resin interact to form a continuous epoxy matrix. Prior to curing, the lower portions can be cut and overlapped, or folded to the desired shape and thickness. In some embodiments, it is preferred that the laminate or final product be subjected to compression followed by curing. This step is designed to complete the curing reaction. Thereafter the curing step can be carried out under vacuum to remove any volatile components. EXAMPLES Measurements: Pre-preg stability is characterized by MMV and is measured with an Ant〇n Pearphysica MGR-301 rheometer equipped with a CP25_2 cone plate at a fixed shear rate. For MMV measurement purposes, the samples were prepared as follows: The prepreg was comminuted and filtered through a 120 micron screen. This provides a pre-preg powder from which the glass reinforcement has been removed. The resulting crucible 32 § powder was then placed on a peltier plate that had been preheated to 160 C. The shear rate for the first 1 second is set to 26 rpm/min, and the last 250 seconds is adjusted to 13 rpm/mm. Monitor the relationship of melt viscosity to time. The prepreg (pre_preg) was stored in a humidity controlled chamber for 24 hours, the relative humidity was 100%, and the temperature was 25 ° C to prepare an aged sample, and then the MMV was measured to determine the ΔΜΜ V value. Materials · In the following example, XZ 92748.〇〇 is an epoxy novolac resin containing 85 wt0/〇 1-methoxy-2-propanol (PM) solid; XZ 92740.00 is a high Tg epoxy 22 201111408 tannic acid Varnish resin 'from Dow Chemical Company; XZ 92749.00 is a lining-type curing agent available from Dow Chemical Company (which is XZ 92535, a phenolic novolac resin containing 50 wt% of decyloxypropyl (PMA) solids, And XZ 92741, a phosphorus-containing bisphenol A soluble phenolic resin containing a blend of 57 wt% PM solids.). DETDA is available from Albemarle Co. DICY is from Darong Co. Ltd. The other material was 2-phenylimidazole (10 wt% solids, DowanolTM, PM) and 2-methylimidazole from Aldrich Chemical Co., used as a catalyst. Example 1: Control Group The control group samples were prepared without a dual-curing hardener blend. The control group samples were made from a mixture of different ingredients with the ratios listed in Table 13. The mixture was placed on a shaker and mixed. The pre-preg was prepared from the control group sample by manually applying a glass mesh (E-7628 type) to the sample at 17 Torr. (: Baking in an oven for a few minutes to control the pre-preg gelation time for further stability testing. The MMV was measured with an Anton Pear MCR 301 rheometer according to the above method. In the table it. The gelation time of the control group sample was 280 seconds, the pre-preg (pre_preg) baking time was 270 seconds, and the pre-preg gelation time was 5 丨 seconds. Table la Component solid content (Wt.°/o) Solid Weight (g) Solution (g) XZ92748 85 45 105.88 XZ92749 50 55 220 〇〇2-PI 10 0.16 (phr) 3.20 23 201111408 Table lb MMV(PaS) Initial 48.1 24 hours later, 100 % RH 35.1 Δ 27.0 Example 2: Invention Example 1 A working sample of the flame retardant epoxy resin composition of the present invention was prepared by mixing the components of Table 2a according to the method described in Example 1. The MMV was recorded as described above, and the result was as follows. Listed in Table 2b. The working sample has a gelation time of 297 seconds, a pre-preg baking time of 330 seconds, and a pre-preg gelation time of 45 seconds. Has a phosphorus content ("P%') of 3.12% based on the solids content of the composition, epoxy resin The stoichiometric molar weight ("Epo. Mol.") was 0.31, and the stoichiometric molar weight ("Hard. Mol.,") of the curing group (including -OH and -NH) was 0.30. Table 2a Solid content (wt.%) Solid weight (g) Solution (g) XZ92748 85 55 132.65 XZ92741 57 35 125.88 DETDA 100 10 20.50 2-PI 10 0.18 (phr) 3.69 Table 2b MMV(PaS) Composition 46.5 24hrJ|_ , 100% RH 49 Δ -5.4 24 201111408 Example 3: Comparative Example 1 A comparative sample of a flame retardant epoxy resin composition was prepared by mixing the components of Table 3a according to the method described in Example i. MMV is as described above The results are shown in Table 3b. The comparison sample has a gelation time of 251 seconds, a prepreg has a baking time of 235 seconds, and a prepreg (Pre-Preg) has a gelation time of 75 seconds. Table 3a Solids content (wt.%) Solid weight (g) Solution (g) XZ92740 85 64 150.6 XZ92741 57 36 126.3 DICY 12 2.4 40.0 2-MI ^ 10 1.1 22.0 Table 3b '----___ MMV(PaS) Initial ----- 34.7 > 100%RH 21.1 Δ ^ 39.2 __ Example 4: Invention Example 2 Comparative sample of flame retardant epoxy resin composition, mixed The method described in Example 1 was prepared by combining the above components. The results of MMV as described above are listed in the table servant. The gelation time of the sample was 253 seconds, the pre-preg baking time was seconds, and the pre-preg (pre_preg) gelation time was 60 seconds. The composition has a phosphorus content ("P%") of 3.13%, based on the solid content of the composition, 'the stoichiometric molar weight of the % oxygen resin ("Ep〇· Mol.") is 25 201111408 0·36, And the stoichiometric amount of the curing group (including -OH and -NH) is 0 31. _ Table 4a Ingredients·*'- ____ ________ Solid content (wt·%) Solid weight ( g) Solution (g) ΧΖ92748 85 64 75.29 ΧΖ92741 57 36 63.16 _____ DICY 20 2.4 12 2-ΜΙ 10 0.7 7 Table 4b MMV(PaS) Initial 42 _^1, after, i〇〇%R H. 38.6 Δ - - 8.1 Example 5: Invention Example 3 A working sample of the flame-retardant epoxy resin composition of the present invention was prepared by mixing the components of Table 5 a according to the method described in Example 1. The conversion temperature of the film glass was DSC. (Differential Scanning Thermal Analyzer) measurement, after the solvent was removed and cured on a hot plate at 190 ° C for 90 minutes. The MMV was recorded as described above. The results are listed in Table 5b. The gelation time of the working sample was 235 seconds. The prepreg (Pre_preg) has a baking time of 200 seconds, and the pre-preg has a gelation time of 58 seconds. The composition has The phosphorus content ("P%") is 3.12%, based on the solid content of the composition, the stoichiometric molar weight of the epoxy resin ("EP0·M〇K") is 0.29, and the curing group (package _ The stoichiometric molar weight of 〇H and -NH) ("Hard. Mol·,,)) is 〇·28. 26 201111408 Table 5a Ingredients ___---------1 Solids content (wt.%) Solid Weight (g) Solution $) _ XZ92748 85 52 125.41 XZ92741 57 35 125.88 DETDA 100 6.5 13.33 XZ92535 50 6.5 26.65 2-PI 10 0.17 (phr) 3.35 ------1 Table 5b MMV(PaS) Initial 28.8 24 After hours, i〇〇%rh 25.4 Δ 11.8 Example 6: Inventive Example 4 A working sample of the flame-retardant epoxy resin composition of the present invention was prepared by mixing the components of Table 6a, according to the method described in Example 。. The glass conversion/dishness was measured by DSC (differential scanning calorimetry) after the solvent was removed and cured on a hot plate at 190 ° C for 90 minutes. The MMV is recorded as described above and the results are shown in Table 6b. The gelation time of the working sample was 334 seconds, and the pre-preg baking time was 260 s. The composition has a scale content ("P%") of 3.05%, based on the solids content of the composition, the stoichiometric molar weight of the epoxy resin ("% 〇. Mol.") is 0.326, and the solidification group The stoichiometric molar weight ("Hard. Mol.,") of the group (including -OH and -NH) was 0.331. 27 201111408 Table 6a Solids content (wt·%) Solid weight (g) Solution (g) XZ92748 85 58 68.24 XZ92741 57 35 61.40 XZ92535 50 7 14.00 DICY 100 2 2.00 2-PI 10 0 (phr) 0.00 MEK/PM 0 0 6.34 Table 6b MMV (PaS) Initial 25.9 24 hours, 100% RH 24.6 Δ 5.0 Example 7: Inventive Example 5 The working sample of the flame retardant epoxy resin composition of the present invention was prepared by mixing the components of Table 7a. According to the method described in Example 1. The MMV is recorded as described above and the results are shown in Table 7b. The gelation time of the working sample was 294 seconds, the pre-preg baking time was 255 seconds, and the pre-preg gelation time was 41 seconds. The composition has a phosphorus content ("P%') of 2.93%, based on the solids content of the composition, the stoichiometric molar weight of the epoxy resin ("Epo. Mol.") is 0.331, and the curing group ( The stoichiometric molar weight ("Hard. Mol.,"), including -OH and -NH, was 0.343. 28 201111408 Table 7a Solids content (wt.%) Solids weight (g) Solution (g) XZ92748 85 59 69.41 XZ92741 57 33 57.89 XZ92535 50 4 8.00 DICY 100 2 2.00 DETDA 100 2 2.00 2-PI 10 0.08 (phr) 0.80 PM 0 0 16.00 Table 7b MMV (PaS) Initial 39.6 After 24 hours, 100% RH 39.7 Δ 0.3 Example 8: Comparative Example 2 A comparative sample of the flame retardant epoxy resin composition was prepared by mixing the components of Table 8a. According to the method described in Example 1. The MMV is recorded as described above and the results are shown in Table 8b. The gelation time of the comparative samples was 257 seconds, the pre-preg baking time was 315 seconds, and the pre-preg gelation time was 77 seconds. The composition has a phosphorus content ("P%') of 3.03%, based on the solids content of the composition, the stoichiometric molar weight of the epoxy resin ("Epo. Mol.") is 0.275, and the curing group ( The stoichiometric molar weight ("Hard. Mol.") including -OH and -NH) was 0.277. 29 201111408 Table 8a Solid content (wt_%) Solid weight (g) Solution (g) XZ92748 85 49 57.65 XZ92741 57 34 59.65 DDS 100 7 7 XZ92535 50 10 20 2-PI 10 0.15 (phr) 1.5 PM 11 Table 8b MMV (PaS) Initial 49.8 24 hours, 100% RH 38 Δ 23.7 (DDS = diaminodiphenyl hydrazine) Example 9: Comparative Example 3 Comparative sample of flame retardant epoxy resin composition was mixed on Table 9a Prepared according to the ingredients, according to the method described in Example 1. The MMV is recorded as described above and the results are shown in Table 9b. The gelation time of the comparative sample was 252 seconds, the baking time of the prepreg (Pre_preg) was 265 seconds, and the gelation time of the prepreg (Pre-Preg) was 45 seconds. The composition has a filling content ("P%') of 3 · 03% 'based on the solid content of the composition, and the stoichiometric molar weight of the epoxy resin ("EP〇. Mo1.") is 0.292 And the stoichiometric molar weight of the curing groups (including -OH and -NH) ("Hard. Mol.,") was 0.299. 30 201111408 Table 9a Composition _--Ί Solid content (wt.%) Solid focus (g) XZ92748 85 52 XZ92741 57 34 59.65 SAA 100 7 7 _一_ XZ92535 50 7 14 2-PI 10 0.3 (phr) 3 -- --* PM 12 -----— (SAA = Aminobenzoguanamine) Table 9b MMV (PaS) Initial 51.6 After 24 hours, 100% RH 34.9 Δ 32.4 Example 10: Comparative Example 4 Flame Retardant Epoxy Resin Composition Comparative samples of the materials were prepared by mixing the components of Table 10a according to the method described in Example 1. The MMV was recorded as described above and the results are shown in Table 1 〇b » The comparison sample has a gelation time of 272 seconds, a pre-preg baking time of 305 seconds, and a pre-preg (pre_preg) gelation time. It is 84 seconds. The composition has a phosphorus content ("p%") of 3 〇 3%, based on the solid content of the composition, and the stoichiometric molar weight of the epoxy resin ("Ερο. Μ〇1·") is 0.264, and The stoichiometric molar weight of the curing group (including -OH and -ΝΗ) ("Hard.M〇l.,%〇27〇. 31 201111408 Table 10a 成·^ Solid content (wt.%) Solid weight (g) Solution (g) XZ92748 85 47 55.29 XZ92741 57 34 59.65 MDA 100 2 2 XZ92535 50 17 34 2-PI 10 0.05 (phr) 0.5 PM 6 (MDA = m-phenylene diamine) Table 10b MMV (PaS) Initial 37.3 After 24 hours, 100% RH 22 Δ 41.0 It should be noted that the present invention is not limited by the examples and the description, and includes the modifications of the examples and the description, including the parts of the embodiments, and the combinations of the different embodiments. These are included in the scope of the following patent application. I: Simple description of the diagram 3 (none) [Description of main component symbols] (none) 32