[go: up one dir, main page]

TW201120085A - Latent hardener for epoxy compositions - Google Patents

Latent hardener for epoxy compositions Download PDF

Info

Publication number
TW201120085A
TW201120085A TW099118990A TW99118990A TW201120085A TW 201120085 A TW201120085 A TW 201120085A TW 099118990 A TW099118990 A TW 099118990A TW 99118990 A TW99118990 A TW 99118990A TW 201120085 A TW201120085 A TW 201120085A
Authority
TW
Taiwan
Prior art keywords
epoxy resin
curing agent
epoxy
particles
compound
Prior art date
Application number
TW099118990A
Other languages
Chinese (zh)
Other versions
TWI425023B (en
Inventor
Yu-Rong Ying
John J Mcnamara
Jing Liang
Rong-Chang Liang
Original Assignee
Trillion Science Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/497,040 external-priority patent/US8044154B2/en
Priority claimed from US12/762,892 external-priority patent/US8067484B2/en
Application filed by Trillion Science Inc filed Critical Trillion Science Inc
Publication of TW201120085A publication Critical patent/TW201120085A/en
Application granted granted Critical
Publication of TWI425023B publication Critical patent/TWI425023B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/241—Preventing premature crosslinking by physical separation of components, e.g. encapsulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Analytical Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Sealing Material Composition (AREA)

Abstract

Disclosed herein is a curing agent for epoxy resins that is comprised of the reaction product of an amine, an epoxy resin, and an elastomer epoxy adduct. Additionally disclosed is a process comprising agitating a solution of an amine, an epoxy resin, and an elastomer epoxy adduct as a dispersant at an elevated temperature in an organic medium.

Description

201120085 、發明說明： 【相關申請案的交互資訊】 本申請案主張於2009年6月12日申請之美國臨時申請案第 61/186,547號、於2009年7月2日申請之美國申請案第 12/497,040號、於2010年3月12日申請之美國臨時申請案 第61/313，199號以及於2010年4月19日申請之美國申請案 第12/762,892號的優先權。 【發明所屬之技術領域】 本發明係有關於一種環氧樹脂的潛伏性硬化劑，更特 別是，有關於一種由被封裝或包覆在殼材料中之核材料所 組成的潛伏性硬化劑。 【先前技術】 環氧樹脂黏著劑已知達超過50年，且是其中一種被用 於商業化之第一高溫黏著劑。一旦被固化，材料在大範圍 的溫度内保留其黏著性能，具有高的剪切強度，並耐風化、 油、溶劑和渔氣。黏著劑是以單組分（1 -part)黏著劑或雙組 分(2-part)黏著劑在市場上銷售，且以數種形式在市場上銷 售，如膏、溶劑溶液、以及支撐膜。在這三種形式中，單 組分黏著劑膜普遍提供良好的黏著強度並具有較好的厚度 均勻性，且已被實際使用於電子學中各向異性導電膜的發 展，最常見的是平版顯示器。 建構單組分黏著劑膜時，典型是將下列各者全部一次 201120085 結合：潛伏性硬化劑、多官能縣編、苯氧基樹脂 加劑、以及可選之填料。此—紐成物接著於離型層上洗鑄 成為膜。在接合製程巾’黏著劑被轉判-特定的表面， f移除該離型層H面與該膜接觸，並通過熱及/或壓 力之施加，使黏者劑硬化或固化成強力熱固性黏著劑。在 這個例子中，使材料固化成為熱固性黏著劑的兩種黏著劑 組成分是硬化劑和多官能環氧樹脂。後者建立了交聯網 絡，但前者係致使這種情況發生。在固化過程中，潛伏性 硬化劑啟動多官能環氧樹脂的聚合仙，藉由與環氧樹脂 的環氧乙烷(oxiranes)先形成開環加成物。一旦產出，額外 產物係導致通過黏著劑傳播之開環物種的級聯（cascade)， 最終產生交聯熱固性材料。 硬化劑的活性成分通常是由胺類化合物（如咪唑）和環 氧樹脂的反應產物所組成。這種加成物是眾所周知用於啟 動和加速環氧樹脂的固化（Heise，M.S.; Martin，G.C. Macromolecules, 1989, 22 99-104; Heise, M.S.; Martin, G.C. J- Poly. ScL: Part C: Polym. Lett. 1988, 26, 153-157; Barton, J-M, Shepherd, P.M.; Die Makromolekular Chemie 1975 176? 919-930)。但這些的缺點是由於他們非常有效的固化物，不 能直接使用於單組分黏著劑，因為一旦加入，他們在相對 短的時間間隔内將開始固化。因此，在試圖使黏著劑及其 薄膜作為硬化劑而繼續加快環氧樹脂基團的開環聚合反應 之同時，將會看到組成物黏度之緩慢增加。這種現象是最 常見的被稱為減少可行生命期，換句話說，因為過早硬化， 4 201120085 大大減少了可用來組合黏著劑及製膜的時間。因此，為 止這種情況發生，人們通常不❹胺·環氧樹脂加成物本身 作為硬化典型賴法是藉由保魏殼材料來封 包覆胺-環氧樹脂加成物，以隔離胺_環氧樹脂加成物盘黏著 劑環境。一旦納入黏著劑，通過施加熱及/或壓力，胺、-環 樹脂加成物將由其保賴釋放。此處敘述的這種潛伏性硬 化劑，俗稱為核殼潛伏性硬化劑，其中的核在這種情況下 是指胺-環氧樹脂加成物，以及殼是指該保護殼。 核殼潛伏性硬化劑經常遇到的顯著折中是固化速产往 ，是緩慢的，且固化溫度往往由於納人保護殼而增加(ς護 设必須被打破或被視為是可渗透的，以使核材料被釋放到 黏著劑環境或介質）。不受限於特定理論，已知#使用如增 加殼厚度、交聯密度、或殼之“、或藉由增加殼與核材^ ，黏著劑基質之間之非相容性的方式而使殼材料的障壁性 此增加時’將需要更多的能量來將胺_環氧樹脂加成物釋放 黏著劑糾。因此其是—種硬化劑，當調配成單組分黏 者』日可具有增加儲存#命穩之期望屬性，但代價是較 f的固化溫度和降低固化速度。因此，恰好足夠使保護性 吸在正¥儲存條件保護核材料，但不會過多而減缓黏著劑 化速度’對於製備核_殼潛伏性硬化劑而言仍^是一種 :平衡。此外，核材料之釋放可能會於合理的低溫觸發 並且於較窄的溫度範圍内完成。 ϋ其中最巾用的Hm更化劑是由核·殼材料所組 述於 US 4,833,226、us 5,219,956、US 2〇06/〇n8835、 201120085 US 2007/0010636 . Us 2007/0055039 &gt; US 2007/0244268 ^ EP 1,557,438^EP 1,731,545 ^ EP1,852,452 ^ EP 1,980,580〇 所述硬化劑之獲得，首先是合成整塊核材料，然後被粉碎 成不規卿狀的微米級粒子。核㈣是胺類化合物和環氧 ,並且該核材料之功能是作為環氧樹脂組 成物的硬化劑’諸如黏著劑和塗料中所發現者。為了提高 核材料的儲存穩定性並防止過早固化，其係独材料 裝，殼材料滲透環氧樹脂組成物組成分，如溶劑、稀釋 劑、低分子量環氧樹脂化合物和添加劑。要做到這一點， 粉狀固⑨體被添加到多官能異紐、活性氫化合物(例如， 水)和環氧_之混合物巾。該㈣程序之化學作用依賴的 聚異亂㈣化合物之㈣反應及/或水解，以形成粒子周圍 的交聯殼塗層。殼的典型交聯結構包括但不·:尿素、 聚胺醋、胺基甲酸®旨、雙縮脲、脲甲酸料。但交聯反應， 於連續相和界面係無差別地隨機發生。有—些核粒子極可 能無法被充分封I’而同時於連續相中產生非期望之副產 品’如㈣聚脲粒子。此外，這個製程製備雜粒子是不 規則的形狀，*且有非常廣泛的分佈形狀和粒子大小，形 成於其上之殼的厚度均自性和交職歧差。目此，封裝 的硬化劑粒子通常顯示很廣泛分佈_放性質，且使用這 種類型硬化师囊之單組絲著雜U現惡劣的儲存壽 命穩定性和緩慢固化特性或高固化溫度。 逛有另一組的發明’即 EP 4:59,745、EP 552,976、us 5,357，_、US 5,480,957、US 5，M8,058、US 5,554,714、 6 201120085 5,561，204、US 5,567,792、及 US 5,591，814，也說明核殼潛 ,!·生硬化劑’它不像上述那些具有球形形狀。核材料是以 ^粒子彳i付’且是在有機介質巾與存在分散劑之狀況下 由胺與活性氫原子(如咪旬和軌樹賴反應所合成。胺、 =樹脂和分散劑可溶於有機介質中，而反應產物(核材料） ’其結果是核粒子從溶液沉殿成為具有相對較窄 =/布，定分散物。使理想教徑具有窄粒度分佈的穩 :取Ϊ要的，素是分散劑的性質’且發明人顯示的 取产^ 1自丙烯酸酯、聚丙烯醯胺、聚乙酸乙烯酯、 、聚苯乙烯、和聚氯乙狀接枝類分散劑。一 劑球面核材料被異氰酸黯縣以製備球形核殼潛 密度陷、，、空洞、薄區、或由不足交聯 無二在# 2缺陷將會使核過早逃離保護殼， 二：伏：儲存的過程中。無論哪種方式，核從 =::藉由在原有的殼施力，外和材: 來克額外的層殼材料填補和塗敷缺陷。 而改進其是在ΐ圖使保護殼更不透水從 俜被勿略:月b，周圍環氧樹脂組成物的相容性 選二酸醋之封裝，以及可 ^ 9 乂時得到的是由交聯聚胺酯和 的錢所組成之殼。當調配成環氧樹脂黏著劑時，此 201120085 能更父聯的殼與周11的環氧樹脂可能具有不良性 配，ΐ- §例是殼表面和環氧樹脂之間的表面張力不匹 $ 蔣 t 、&quot;去渴現象（dewetting phenomenon)，其中環 ·=未此充分濕潤並分佈在殼材料的表面上。因此，會 兩 去^過固化之後黏著劑包含空洞和非均勻固化區域， 者都：導致黏合強度的降低。 止過早有必要針對核殼潛伏性硬化劑改良阻隔性能，以防 卢^μ固化。此外’還需要封裝游伏性硬化劑具有改善的 壞氧樹脂相容性。 【發明内容】 本發明涉及熱固性塑料（如環氧樹脂）的潛伏性硬化劑 ，催化#丨更特別是，其潛伏性硬化劑或催化劑是包括封 或塗有Λ又材料的核材料。核材料，是一種環氧樹脂之固 ^物’其疋包括胺（如，。米唑、派嗪、一級脂肪胺、和二級 月曰肪胺)和環氧樹脂的反應產物。在一實施型態中，核材料 疋在有機介質中以及在分散劑存在在之狀況下合成，該分 散劑是羧基封端之聚（丁二烯_共_丙烯腈)(CTBN)和環氧樹 脂的反應產物。在一實施型態中，CTBN和環氧樹脂的反 應產物是能夠提供具有窄粒度分佈的球形核粒子之穩定分 散。在另一實施型態中，藉由使用輕微過量之環氧樹脂得 到接近100%的轉換。在另一實施型態中，藉由與多官= 異氰酸酯或異硫氰酸酯（thioisocyanate)的反應來封裴球形 核粒子。可選的是，在異氰酸酯建立封裝殼厚度的同時添 8 201120085 加壞乳樹脂。在又另一實施型態中，—旦形成，核 ^或更多之殼材料完全封裝’藉由步進方式塗敷，使用 夕吕能異氰酸醋’或異氰酸較多官能環氧樹 物，或異氰_和環氧樹脂相容材料(如CTB ,= 醋改質環氧樹脂)的混合物，或異氰酸g|、多官能:= 脂、以及環氧樹脂相容的材料之混合物。固化組^= 用具有良好儲存穩定性和改良固化特性的粒子製備。’、吏 本揭露之-方面係有關改善潛伏性硬化劑 &lt; 催 阻隔性能和耐溶劑性。 次催化劑之 ^㈣之另-方面係有關潛伏性硬化劑或催 隔性能和耐溶劑性之改良。 … 請另—方面係有關潛伏性硬化劑或催化劑盘環 氧秘月曰或組成物之相容性的改良。 /、f 本揭露之另一方面係有關—種球 性硬化劑或催化劑。 对我之/曰伙 心路之丨$面係有關-種以期望溫度、壓力戋兩 者組合釋^核材料之潛伏性硬化劑或催化劑。 或催化:丨路2#面係有關一種潛伏核殼潛伏性硬化劑 ^子所”。〃’硬化劑或催化劑包括—穩定分散之球形 坊轨ΐ Γ : ί另；方面係有關—種使用分散劑製造球形- :瞅πτρΓ “、中戎分散劑是—羧基-封端之丁二烯_丁腈 橡料CTBN)和環氧樹脂之反應產物(加成物）。 本揭露之另—方面係有關一種包括胺類化合物、環氧 201120085 樹脂、及分散劑之固化劑，其中該分散劑是CTBN和環氧 樹脂的加成物。 本揭露之另一方面係有關一種製造固化劑之製程。 本揭露之另一方面係有關一種包括固化劑之母粒。 本揭露之另一方面係有關一種電子裝置或平版顯示 盗，包含本文揭露之固化劑之組成物。例如用來連接驅動 積體電路(ic)到電子裝置或平版顯示器之常見方法是藉由 使用晶片玻璃接合（chip-〇n-glass)(COG)或晶片軟膜接合 (chip-on-fiim)(COF)。在建構c〇G和c〇F時各向異性導 電膜黏著劑(ACF)及非導電薄膜黏著劑(NCF)通常用來使 COG或COF黏附至驅動ic ’且固化劑是使黏著劑固化和 使組件之間產生永久性接合。因此，在一實施型態中，積 體電路晶片或其他電子組件之黏附是使用包含本文所述固 化劑之環氧樹脂黏著劑。 尽揭露之另 万面係有關一種包含固化劑之組成物 其中該組成物是黏著劑、導絲著劑、複合物、模塑料 各向異H導電薄膜(ACT)黏著冑,|、非隨機矩陣(acf) } 電黏著劑膜(NCF)、塗層、包覆劑、底膠材料、或無錯焊料 =露之另-方面係麵—種包含本文所揭露固㈣ 衣氧树脂黏著劑組成物的電路板。傳統上，電子組件， ^口 ..電t器、和IC’係藉由焊接製程被組裝到電路板 此過程需要高溫並產生浪費 acf、ncf或導雷料能 13_路固化劑戈 右主MM A導電 仏供—種無須使用高溫、浪費禾 有毋重金屬來將電子組件安置至料板之#代方法 201120085 應財，ACF及NCF提供電接觸並使組件固定於基板。 本揭露之另一方面係有關一種電子裝置或顯示器，其 =用包含本文所揭露固化劑之環氧樹脂黏著劑組成物來 =之另一方面係有關一種包含本文所揭露固化劑 =黏著劑組成物之覆晶晶片（flipehip)。傳駐，覆曰曰曰 此晶黏菩而先，晶片是藉由桿接或 心至基材。底膠材料’通常為液態形式，接 露固化劑之二基^ 成第-步的代焊接或共晶黏著製程是完 板時之優勢，著财料健供遇到電路 板之間F也作為底膠材料填補了晶片和基 步驟）。、&quot;、從而達到了單一步驟製程（以前是使用兩個 本揭路之另一方面係有關一種電 中組=經固化、部分固化或未固化，且是 =劑其 版顯示器裝置’如包括平 揭露固化劑之映機和行動電話，其中包含本文所 本描• 树月曰黏著劑係如上所述使用。 定陣列上::面係有關一種固定陣列ACF，其中固 的ACF，例：二、，子以預定的模式分散在黏著劑膜中 A1 ,其中含有:L ; TnUi〇n的專利申請案2006/0280912 文所揭露固化劑的環氧樹脂黏著劑係用於 201120085 建構陣列。 本揭露之另一方面係有關一種包含受保護酚類化合物 的高Tg單組分模塑料，敘述於2008年1月1〇日提出之美 國專利申請案第12/008,375號，其係納入本文作為參考， 其中該受保護酚類化合物包括芳基環氧丙基碳酸酯基團和 本文所揭露之固化劑。 本揭露之又另一方面係一種單組分複合材料，包含半 固化片複合材料和模塑料，如片狀模塑料(SMC)、塊狀模 塑料(BMC)、團狀模塑料(DMC)，其中的固化劑是本文所 揭露的固化劑。 本揭露之又另一方面係一種黏著劑和塗料的應用，包 括焊接遮罩和浸潰塗料，其中的固化劑是本文所揭露的固 化劑。 本揭露之另一方面係採用含有本文所揭露固化劑的環 氧樹脂來組裝和封裝半導體的應用，如描述於Colclaser， Roy A.; ^Microelectronics Processing and Device Design^; John Wiley &amp; Sons, Publishers: New York, 1980; Chapter 8, page pp. 163-181。 本揭露之另一方面係涉及一種電路板，其中組成物係 經固化、部分固化、或未固化，且是由本文所揭露固化劑 組成。 本揭露之另一方面係涉及一種覆晶晶片，其中環氧樹 脂黏著劑組成物係經固化、部分固化、或未固化，且是由 本文所揭露固化劑組成。 201120085 本揭露之另-方面係涉及-種包含含有固化劑之組成 物的半導體元件。本揭露之另一方面係涉及—種半導體元 件，其中組成物係經固化、部分固化、或未固化，且是包 括本文所揭露之固化劑。 本揭露之另-方面係涉及-種組成物，其中該組成物 是在儲存條件下具有實質上長貨架壽命的單組分黏著劑组 成物，且該組成物不論是在固化溫度或成型溫度下皆有反 應性，且該組成物包含本文所揭露之固化劑。 本揭露之另一方面係涉及一種含有固化劑之組成物， 在固化後的組成物在界面具有黏附性、低固化收縮率、以 及低的熱膨脹係數(CTE)。 本揭露之另一方面係涉及一種含有固化劑之組成物， 其中该組成物是複合材料或模塑料之基質。 【實施方式】 實施型態，固化劑是下列各者之加成物：⑴胺， (^)裒氧彳f知化合物，及（出)彈性體與環氧樹脂之加成物。 彈I1生體/環氧;^旨力α成物之功能係作為反應性分散劑，以使 在反應：『中球形未封裝的粒子分散。 δ月之另一方面是一種製備固化劑之精細球形核粒 子的=去，包括在提高之溫度與攪拌狀態下於速續相使胺 八_物/、環氣樹脂/彈性體加成物及後續之環氧樹脂化 口物，=以及回收從反應混合溶液形成的精細球形粒 子可遥地，回收之粒子可經過濾以去除黏聚粒子並藉由 13 201120085 =力分m _、場流分離、和場 :員’以移除小型衛星粒子。連續相是^^ 合物，包含能夠溶解胺類化合物、環氧樹脂化=== 樹脂/彈性體加成物但無法溶解由三個反應物所 j 成物的溶劑、或㈣㈣溶劑之混合物，其巾溶劑=力: 解胺類化合物、環氧樹脂化合物、環氧續性體的力 無法溶解從三個反祕_叙加錢粒子^合物t 非溶劑為胺類化合物、環氧樹脂化合物、環氧樹脂/彈性體 加成物'及由三個反應物所形成之加成物粒子的非溶劑。 連續相的選擇影響分散穩定性和粒徑及粒徑分佈。 本發明的另一實施型態是一種可熱固化組成物，它包 括作為其主要組成分之環氧樹脂組成物和固化劑的球形粒 子。在此型態中，本發明之固化劑球形粒子不溶於或膨脹 於環氧樹脂組成物。在一實施型態中，粒子有至少約5〇(&gt;c 之熔融流動溫度，粒子直徑為01#m至3〇仁m。這些粒子 係以每100重量份之環氧樹脂約丨至6〇重量份之數量被併 入黏著劑中。 在一實施型態中，本發明還包括環氧樹脂之固化劑母 粒，其中母粒包括固化劑之精細球形粒子被均勻分散其中 的液體環氧樹脂。在某一特定實施型態中，粒子已與i到 100重里伤之多官能異氣酸化合物反應，且可選地與1_1〇〇 重呈伤之環氧樹脂化合物反應，基於100重量份之該粒 子。這些粒子然後允許以連續步驟與丨到1〇()重量份之多 官能異氰酸化合物反應一或更多額外次數，和可選地與 14 201120085 1 -1 〇〇重量十、 量份之環多官能環氧樹脂化合物’和可選與M〇〇重 ^氣彳对墙相容材 於1〇〇重量份之該粒201120085, invention description: [interaction information of related applications] This application claims the US provisional application No. 61/186,547 filed on June 12, 2009, and the US application filed on July 2, 2009 U.S. Provisional Application No. 61/313,199, filed on March 12, 2010, and the priority of US Application Serial No. 12/762,892, filed on Apr. 19, 2010. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a latent hardener for an epoxy resin, and more particularly to a latent hardener composed of a core material encapsulated or coated in a shell material. [Prior Art] Epoxy resin adhesives have been known for more than 50 years and are one of the first high temperature adhesives that have been commercialized. Once cured, the material retains its adhesive properties over a wide range of temperatures, with high shear strength and resistance to weathering, oils, solvents and fish. Adhesives are marketed as one-part (1-part) adhesives or two-part (2-part) adhesives and are marketed in several forms, such as pastes, solvent solutions, and support films. Among these three forms, one-component adhesive films generally provide good adhesion strength and good thickness uniformity, and have been practically used in the development of anisotropic conductive films in electronics, the most common being lithographic displays. . When constructing a one-component adhesive film, it is typical to combine all of the following: 201120085: latent hardener, multi-functional county, phenoxy resin additive, and optional filler. This - the bond is then cast into a film on the release layer. In the bonding process towel, the adhesive is transferred to a specific surface, f is removed from the surface of the release layer and contacted with the film, and the adhesive is hardened or cured into a strong thermosetting adhesive by heat and/or pressure application. Agent. In this example, the two adhesive components that cure the material into a thermosetting adhesive are hardeners and multifunctional epoxy resins. The latter established a network of contacts, but the former caused this to happen. During the curing process, the latent hardener initiates the polymerization of the multifunctional epoxy resin by first forming a ring-opening adduct with ethylene oxide (oxiranes) of the epoxy resin. Once produced, the additional product results in a cascade of open-loop species that propagate through the adhesive, ultimately producing a cross-linked thermoset material. The active ingredient of the hardener is usually composed of the reaction product of an amine compound such as imidazole and an epoxy resin. Such adducts are well known for starting and accelerating the curing of epoxy resins (Heise, MS; Martin, GC Macromolecules, 1989, 22 99-104; Heise, MS; Martin, GC J-Poly. ScL: Part C: Polym. Lett. 1988, 26, 153-157; Barton, JM, Shepherd, PM; Die Makromolekular Chemie 1975 176? 919-930). However, these disadvantages are due to their very effective curing properties and cannot be used directly with one-component adhesives because once added, they will begin to cure in relatively short intervals. Therefore, while attempting to accelerate the ring-opening polymerization of the epoxy resin group by using the adhesive and its film as a hardener, a slow increase in the viscosity of the composition will be observed. This phenomenon is most commonly known as reducing the viable lifetime, in other words, because of premature hardening, 4 201120085 greatly reduces the time available for combining adhesives and film making. Therefore, as a result of this, people usually do not use the amine/epoxy resin adduct itself as a typical method of hardening by sealing the amine-epoxy resin adduct to protect the amine. Epoxy resin adduct disk adhesive environment. Once the adhesive is incorporated, the amine, -cyclic resin adduct will be released by its application by the application of heat and/or pressure. The latent hardening agent described herein is commonly referred to as a core-shell latent hardener, wherein the core in this case refers to an amine-epoxy resin adduct, and the shell refers to the protective shell. A significant compromise often encountered with core-shell latent hardeners is solidification, which is slow, and the cure temperature is often increased by the protective shell of the man (the guard must be broken or considered permeable, In order to release the nuclear material to the adhesive environment or medium). Without being limited to a particular theory, it is known to use a shell such as increasing shell thickness, crosslink density, or shell, or by increasing the incompatibility between the shell and the core material and the adhesive matrix. When the barrier property of the material is increased, 'more energy will be needed to correct the amine-epoxy resin adduct release adhesive. Therefore, it is a hardener, which can be increased when blended into a single-component adhesive. Stores the desired properties of #命稳, but at the cost of a curing temperature of f and a lower curing speed. Therefore, it is just enough to protect the protective material in the positive storage conditions, but not too much to slow the rate of adhesion. For the preparation of core-shell latent hardeners, there is still one: balance. In addition, the release of nuclear material may be triggered at a reasonable low temperature and completed in a narrow temperature range. The agent is composed of a core/shell material as described in US 4,833,226, us 5,219,956, US 2〇06/〇n8835, 201120085 US 2007/0010636. Us 2007/0055039 &gt; US 2007/0244268 ^ EP 1,557,438^EP 1,731,545 ^ EP1, 852,452 ^ EP 1,980,580〇hard The agent is obtained by first synthesizing a whole piece of nuclear material and then pulverizing it into irregularly shaped micron-sized particles. The core (4) is an amine compound and epoxy, and the function of the core material is as a hardening of the epoxy resin composition. Agents, such as those found in adhesives and coatings. In order to improve the storage stability of nuclear materials and prevent premature curing, they are made of a separate material, and the shell material penetrates the composition of the epoxy resin composition, such as solvent, diluent, and low. Molecular Weight Epoxy Resin Compounds and Additives. To do this, a powdery solid 9 is added to a mixture of polyfunctional isotonic, active hydrogen compounds (eg, water) and epoxy. The chemical dependence of the (4) procedure (4) The reaction and/or hydrolysis of the compound (4) to form a cross-linked shell coating around the particle. The typical cross-linked structure of the shell includes but not: urea, polyurethane, urethane, bismuth Urea, urea formic acid. However, the cross-linking reaction occurs randomly in the continuous phase and the interfacial system. There are some nuclear particles that are most likely to be unable to be adequately sealed while producing undesirable unproductive by-products in the continuous phase. (4) Polyurea particles. In addition, the preparation of the hetero-particles in this process is an irregular shape, * and has a very wide distribution shape and particle size, and the thickness of the shell formed thereon is self-consistent and the duty difference. The encapsulated hardener particles usually show a very broad distribution, and the use of this type of hardener bag is a single set of wires that are now poor in shelf life stability and slow cure characteristics or high cure temperatures. The invention of EP 4:59,745, EP 552,976, US 5,357, _, US 5,480, 957, US 5, M8,058, US 5,554,714, 6 2011 20085 5,561,204, US 5,567,792, and US 5,591,814 , · Hardener 'It does not have a spherical shape like those mentioned above. The nuclear material is prepared by the reaction of an amine with an active hydrogen atom (such as imiline and orbital lysine) in the presence of an organic medium towel and a dispersant. The amine, = resin and dispersant are soluble. In the organic medium, and the reaction product (nuclear material) 'the result is that the nuclear particles from the solution sink into a relatively narrow = / cloth, a fixed dispersion. The ideal diameter of the ideal teaching diameter has a narrow particle size distribution: , the prime is the nature of the dispersant' and the inventors show the production of acrylates, polyacrylamide, polyvinyl acetate, polystyrene, and polychloroethane-like grafting dispersants. The nuclear material is prepared by the isocyanate county to prepare the spherical core shell latent density trap, , void, thin zone, or by insufficient cross-linking. The #2 defect will cause the core to escape the protective shell prematurely, two: volt: storage Either way, the core from =:: by applying force in the original shell, the outer material: the extra layer of shell material is filled and coated with defects. And the improvement is in the map to make the protective shell More impervious to the water from the 俜 勿 :: month b, the compatibility of the surrounding epoxy resin composition The package of vinegar, and the shell that can be obtained by cross-linking urethane and money can be used as the epoxy resin adhesive, this 201120085 can be more father's shell and week 11 epoxy resin. May have a bad match, ΐ- § Example is the surface tension between the shell surface and the epoxy resin is not the same as the "dewetting phenomenon", in which the ring = = not fully wet and distributed in the shell On the surface of the material, therefore, the adhesive will contain voids and non-uniform solidified areas after both curing, which will result in a decrease in the bonding strength. It is necessary to improve the barrier properties against the core-shell latent hardener too early. In addition, it is required to encapsulate the barrier curing agent to have improved bad oxygen resin compatibility. SUMMARY OF THE INVENTION The present invention relates to a latent hardener for thermosetting plastics (such as epoxy resin), catalyzing #丨More particularly, the latent hardener or catalyst is a core material comprising a seal or a material coated with a crucible. The core material is a solid of an epoxy resin, and the niobium includes an amine (eg, azole, pyrazine). ,One a reaction product of a fatty amine, and a secondary sulfanthrene) and an epoxy resin. In one embodiment, the core material is synthesized in an organic medium and in the presence of a dispersing agent, the dispersing agent being a carboxyl group. a reaction product of a poly(butadiene-co-acrylonitrile) (CTBN) and an epoxy resin. In one embodiment, the reaction product of CTBN and epoxy resin is capable of providing spherical core particles having a narrow particle size distribution. Stable dispersion. In another embodiment, nearly 100% conversion is obtained by using a slight excess of epoxy resin. In another embodiment, by multi-guaner = isocyanate or isothiocyanate ( The reaction of thioisocyanate) to seal the spherical core particles. Alternatively, the isocyanate is added to the thickness of the encapsulating shell while adding 8 201120085 plus bad latex resin. In yet another embodiment, once formed, the core or more of the shell material is completely encapsulated 'by stepwise coating, using yucyl isocyanate vinegar' or isocyanate more functional epoxy a mixture of trees, or isocyanide- and epoxy-compatible materials (such as CTB, = vinegar-modified epoxy), or isocyanate g|, polyfunctional: = fat, and epoxy-compatible materials a mixture. Curing group ^ = Prepared with particles with good storage stability and improved curing characteristics. </ br> </ br> This aspect is related to the improvement of latent hardener &lt; barrier properties and solvent resistance. The other aspect of the sub-catalyst is the improvement of the latent hardener or the barrier properties and solvent resistance. ... Please also improve the compatibility of the latent hardener or catalyst ring oxysperm or composition. /, f Another aspect of the disclosure is related to a spheroidal hardener or catalyst. For me / 曰 心 心 心 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面 面Or catalyzed: 丨路2#面面 is related to a latent core-shell latent hardener.” 〃' hardener or catalyst includes—stable dispersion of spherical square ΐ : 另 another; aspect related - use dispersion The agent produces a spherical-: 瞅πτρΓ ", a medium-sized dispersant is a carboxy-terminated butadiene-butyronitrile rubber CTBN) and an epoxy resin reaction product (adduct). Another aspect of the present disclosure relates to a curing agent comprising an amine compound, an epoxy 201120085 resin, and a dispersing agent, wherein the dispersing agent is an adduct of CTBN and an epoxy resin. Another aspect of the disclosure relates to a process for making a curing agent. Another aspect of the disclosure relates to a masterbatch comprising a curing agent. Another aspect of the present disclosure relates to an electronic device or lithographic display pirate comprising the composition of the curing agent disclosed herein. For example, a common method for connecting a driver integrated circuit (ic) to an electronic device or a lithographic display is by using a chip-on-glass (COG) or a chip-on-fiim ( COF). Anisotropic conductive film adhesives (ACF) and non-conductive film adhesives (NCF) are commonly used to bond COG or COF to drive ic' while the c〇G and c〇F are constructed, and the curing agent cures the adhesive and A permanent bond between the components. Thus, in one embodiment, the adhesion of the integrated circuit wafer or other electronic component is the use of an epoxy adhesive comprising a curing agent as described herein. The other aspects of the disclosure relate to a composition comprising a curing agent, wherein the composition is an adhesive, a wire guide, a composite, a molding compound, an alternating H conductive film (ACT), |, a non-random matrix (acf) } Electro-adhesive film (NCF), coating, coating agent, primer material, or error-free solder = dew-other aspect - the type includes the solid (iv) epoxy resin adhesive composition disclosed herein. Circuit board. Traditionally, electronic components, ^ port, electric tweezers, and IC's have been assembled to the board by soldering processes. This process requires high temperatures and wastes acf, ncf, or guided materials. MM A Conductive 仏 — 种 无 无 无 无 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 Another aspect of the present disclosure relates to an electronic device or display that is based on an epoxy resin adhesive composition comprising a curing agent as disclosed herein. Another aspect relates to a curing agent/adhesive composition as disclosed herein. A flip-chip wafer. Passing through, covering the crystal, first, the wafer is connected by a rod or a heart to the substrate. The primer material is usually in a liquid form, and the second step of the curing agent is the first step of the soldering or eutectic bonding process, which is the advantage of the board when it comes to the board. The primer material fills the wafer and the base step). , &quot;, thus achieving a single-step process (previously used on the other side of the road is related to an electric group = cured, partially cured or uncured, and is the agent version of the display device' including Flat-covering curing agent and mobile phone, including the description of this article • Tree Moonk Adhesive is used as described above. Array on:: Facial system related to a fixed array ACF, which is solid ACF, for example: , the sub-dispersion in the adhesive film A1, which contains: L; TnUi〇n patent application 2006/0280912 The epoxy resin adhesive disclosed in the curing agent is used in 201120085 to construct an array. In another aspect, a high-Tg single-component molding compound comprising a protected phenolic compound is described in U.S. Patent Application Serial No. 12/008,375, filed on Jan. 1, 2008, which is incorporated herein by reference. Wherein the protected phenolic compound comprises an aryl epoxypropyl carbonate group and a curing agent as disclosed herein. In another aspect, the present invention is a one-component composite comprising a prepreg composite Materials and molding compounds, such as sheet molding compound (SMC), bulk molding compound (BMC), bulk molding compound (DMC), wherein the curing agent is the curing agent disclosed herein. An adhesive and coating application, including a solder mask and a dipping coating, wherein the curing agent is a curing agent as disclosed herein. Another aspect of the present disclosure is to assemble and employ an epoxy resin containing the curing agent disclosed herein. Applications for packaging semiconductors are described in Colclaser, Roy A.; Microelectronics Processing and Device Design^; John Wiley &amp; Sons, Publishers: New York, 1980; Chapter 8, page pp. 163-181. Aspect relates to a circuit board in which the composition is cured, partially cured, or uncured, and is composed of a curing agent as disclosed herein. Another aspect of the disclosure relates to a flip chip, wherein an epoxy resin adhesive The composition is cured, partially cured, or uncured, and is composed of a curing agent as disclosed herein. 201120085 Another aspect of the disclosure relates to a composition comprising a curing agent. Semiconductor component. Another aspect of the disclosure relates to a semiconductor component wherein the composition is cured, partially cured, or uncured, and includes a curing agent as disclosed herein. a composition, wherein the composition is a one-component adhesive composition having a substantially long shelf life under storage conditions, and the composition is reactive at either a curing temperature or a molding temperature, and the composition comprises The curing agent disclosed herein. Another aspect of the present disclosure relates to a composition containing a curing agent having an adhesive property at the interface, a low cure shrinkage ratio, and a low coefficient of thermal expansion (CTE). Another aspect of the present disclosure is directed to a composition comprising a curing agent, wherein the composition is a matrix of a composite or molding compound. [Embodiment] In the embodiment, the curing agent is an adduct of (1) an amine, (^) an antimony compound, and an adduct of an elastomer and an epoxy resin. The function of the I1 organism/epoxy; the function of the α-form is used as a reactive dispersant to disperse the particles in the reaction: "the spherical unpackaged particles. Another aspect of δ month is a kind of fine spherical nucleus particles for preparing a curing agent, which comprises a combination of an amine octane/, a cycloolefin resin/elastomer adduct at a temperature and a stirring state. Subsequent epoxy resinized mouth, = and recovered fine spherical particles formed from the reaction mixture solution can be remotely removed, and the recovered particles can be filtered to remove the cohesive particles and separated by 13 201120085 = force division m _, field flow , and the field: the staff 'to remove small satellite particles. The continuous phase is a compound comprising a solvent capable of dissolving an amine compound, epoxy resin === resin/elastomer addition but incapable of dissolving the three reactants, or a mixture of (iv) (iv) solvent. Its towel solvent = force: the amine compound, epoxy resin compound, epoxy continuum force can not be dissolved from three anti-secret _ _ _ _ _ _ _ _ _ _ _ _ _ _ , epoxy resin / elastomer adduct ' and non-solvent of adduct particles formed from three reactants. The choice of continuous phase affects dispersion stability and particle size and particle size distribution. Another embodiment of the present invention is a heat curable composition comprising spherical particles as an epoxy resin composition and a curing agent as main components thereof. In this form, the spherical particles of the curing agent of the present invention are insoluble or swellable in the epoxy resin composition. In one embodiment, the particles have a melt flow temperature of at least about 5 Torr (the diameter of the particles is from 01 #m to 3 〇min m. These particles are about 6 to about 6 parts by weight of the epoxy resin. The amount of bismuth by weight is incorporated into the adhesive. In one embodiment, the present invention further comprises a curing agent masterbatch of the epoxy resin, wherein the masterbatch comprises a liquid epoxy in which the fine spherical particles of the curing agent are uniformly dispersed. Resin. In a particular embodiment, the particles have been reacted with a polyfunctional isophthalic acid compound that is i to 100 mils, and optionally reacted with a 1 〇〇 heavy epoxy resin compound, based on 100 parts by weight. The particles are then allowed to react in a continuous step with one to more than one part by weight of the polyfunctional isocyanate compound for one or more additional times, and optionally with 14 201120085 1 -1 〇〇 weight ten, Quantities of ring polyfunctional epoxy resin compound 'and optional M 〇〇 ^ 彳 彳 彳 墙 墙 墙 墙 墙 墙

本發明進〜A 包括在低於i 步包含製備環氧樹脂固化劑母粒之方法， 粒子分5力f球形粒子炼融流動溫度之溫度將固化劑球形 月環氣樹脂中之步驟。 口^氡樹脂加胺類化合物 樹脂化可用於製備固化劑之胺類化合物和環氧 化學結構、疋係基於其藉由陰離子聚合促進固化反應 其熔點、其與環氧樹脂之相容性(將於熔融或塑 痒了固化）、其快速固化率及其反應性。本文中熔融 /瓜：/皿又係被定義為物質開始作為熔融流體流動之溫度， =¾知彳定。用於本發日月特定實施型態之胺和環氧樹 脂化合物之實例係揭露於EP 459,745、ΚΡ 552,970、US 5,357,008 ^ US 5,480,957 &gt; US 5,548,058 ^ US 5,554,714 ^ 5,561，204、US 5,567,792、及 US 5,591，814，其已載入本文 作為參考。 胺類化合物 雖然可以使用任何胺類化合物，胺類之選擇將根據環 氧樹脂化合物陳質。選擇與環氧樹疏合物反應但使反 應無=全聚合的胺類。當單官能環氧樹脂化合物反應 時，實質上可以使用任何胺類化合物，但當多官能環氧樹 脂化合物反應時，只有—個活性氫，即二級絲之胺類化 15 201120085 合物有助於環氧基團的反應^使用具 物，即無活性氫，也是被允許的。以/下二級胺基之化合 與雙官能雙酚A二環氧丙基醚結人=舉之化合物係可 類，以2-曱基咪唑和2,4_二甲其二〇, *胺類化合物：咪唑 N-曱基哌嗪和N_羥基乙基彳代表；哌嗪類，以 (anabasines) ’以假木賊鹼為代表；吡唑代表；毒藜鹼類 t坐為代表；嘴呤類，以四曱基胍或H以3,5-二曱基 以吡唑為代表；以及三唾類，以i 7马代表；吡唑類， 以1，2,3·三氮唑為代表等。 環氧樹脂化合物 環氧樹脂化合物之例子是單官 正丁基環氧丙基喊、苯環氧乙燒和苯基^月曰化合物，如 能環氧樹脂化合物’如雙酚A二環氧丙“丙;雙官 氧丙基趟，雙盼S二環氧丙基峻和二兩雙齡F二環 官能化合物，如甘油酯異氰 =基耿酸醋；三 官能化合物，如四環氧丙=苯甘二醋對胺基酚;四 胺暴二苯基甲垸;及有更多官二:==: 聚%、^基⑱，崎料漆聚環氧㈣醚等 月曰之選擇运取決於欲結合胺類化合物的類型。環氧樹： 合物也可㈣形成加成物 二曰 脂在嫁融狀H n 化％氧樹The present invention comprises a method comprising preparing a masterbatch of an epoxy resin curing agent in a step less than i, the step of granulating the flow temperature of the spherical particles by a force of 5 deg. Resin-based resin-amine compound resinization can be used to prepare a curing agent amine compound and epoxy chemical structure, based on its melting point by anionic polymerization to promote the curing reaction, its compatibility with epoxy resin (will It cures by melting or itching, its rapid cure rate and its reactivity. In this paper, the melt/melon: / dish is defined as the temperature at which the material begins to flow as a molten fluid, = 3⁄4. Examples of the amine and epoxy resin compounds used in the specific embodiments of the present invention are disclosed in EP 459,745, 552 552,970, US 5,357,008, US 5,480,957 &gt; US 5,548,058 ^ US 5,554,714 ^ 5,561,204, US 5,567,792, and US 5,591,814, which is incorporated herein by reference. Amine Compounds Although any amine compound can be used, the choice of amines will depend on the epoxy resin compound. The amines which react with the epoxy tree complex but have no reaction = total polymerization are selected. When the monofunctional epoxy resin compound is reacted, substantially any amine compound can be used, but when the polyfunctional epoxy resin compound is reacted, only one active hydrogen, that is, the amine of the secondary filament 15 is helpful. The reaction of the epoxy group, that is, the use of a substance, that is, an inactive hydrogen, is also allowed. The compound of the lower/secondary amine group and the bifunctional bisphenol A diglycidyl ether group can be used as a compound, 2-mercaptoimidazole and 2,4-dimethyl bismuth, *amine Class of compounds: imidazole N-mercaptopiperazine and N-hydroxyethyl hydrazine; piperazines, (anabasines) 'represented by pseudoepithedine; pyrazole; muscarinic t sitting as representative; a class of tetradecyl hydrazine or H with 3,5-dimercapto as a representative of pyrazole; and a trisaloid, represented by i 7 horses; pyrazoles, represented by 1,2,3·triazole Wait. Examples of epoxy resin compounds Epoxy resin compounds are mono-n-butyl butyl acrylate, benzene epoxicone and phenyl oxime compounds, such as epoxy resin compounds such as bisphenol A diepoxypropyl "C; bis-oxypropyl hydrazine, bis-S diepoxypropyl sulphate and two-two-old F bicyclic functional compounds, such as glyceride isocyanide = bismuth citrate; trifunctional compounds, such as tetraglycol = Benzene diacetate to aminophenol; tetramine storm diphenylformamidine; and more official two: ==: poly%, ^ base 18, raw material paint polyepoxy (tetra) ether, etc. Depending on the type of amine compound to be bound. Epoxy tree: Compound can also (4) form adduct bismuth in marryled H n % oxygen tree

樹脂包括雙齡A t選擇。由於待固化之大部分環氧 制一％氧丙基醚，這種化合物是最典型作A =::::有始原料。在-實施―，通常採心 戽有環氧當量，最多约〗000，且較佳最多約 16 201120085 500。 溶劑 選擇一種可溶解作為起始材料之胺類化合物和環氧樹 脂化合物，但可以不溶性粒子之形式沉澱而不溶解加成物 之溶劑系統也很重要。可用於本發明某些實施形態之溶劑 實例是曱基異丁基酮、甲基異丙基酮、曱基乙基酮、丙酮、 乙酸正丁酯、醋酸異丁酯、醋酸乙酯、醋酸曱酯、四氫呋 喃、1,4-二氧陸圜（dioxane)、溶纖劑、乙二醇單乙醚、二 乙二醇二曱醚、苯曱醚、曱苯、p-二曱苯、苯、二氣曱烷、 氯仿、三氯乙烯、氯苯和吡啶。這些溶劑可單獨使用，或 二或更多之的溶劑可以一起使用。 非溶劑 額外地，可能需要添加非溶劑以協助迫使胺類化合物 與分散穩定劑和環氧樹脂的環氧官能基發生反應。此情況 中之非溶劑是任何不溶於胺類化合物、分散穩定劑、或環 氧樹脂之溶劑。可作為非溶劑之可能的化合物種類是線性 或分枝脂肪族化合物，如庚烷、己烷、辛烷、異辛烷、石 油醚等。非溶劑結合溶劑之一實例是庚烷和曱基異丁基酮 (MIBK)之混合物。除上述溶劑和非溶劑之外，稀釋劑或弱 溶劑可選地用於放寬配方或製程容許度。 分散穩定劑或分散劑 17 201120085 劑或分散劑使加成物粒子在反應介質中穩定 H/λΓ讀分散敎劑，㈣成之加成錄子可能會 破开間，聚和沉澱成為黏塊’從而不能獲得所需精細 1。最佳分散賴㈣備具有窄粒徑分佈之穩定分 ^要的。反應性分散劑往往比非反應性分散劑更有 1 nt 3 *旦與粒子相反應，要從粒子表面脫附或遷移分 H疋不大可&amp;的。彈性體/環氧樹脂加成物被用作根據本 反應性分散劑。反紐分散劑之合適分子量範圍是 ^ 、l000 至 300,000，較佳從大約 2,000 至 100,000，最 佳從約3,〇〇〇至1〇,〇〇〇。 環氧Jit脂丨彈性體加成物作為反應性分散劑 抑環氧樹脂/彈性體加成物本身一般包括約 1:5至5:1份 之環氧树脂或其他聚合物(相對於彈性體），更佳約1:3至 3.1份之環氧樹脂(相對於彈性體）。更典型，加成物包括至 少約5%，更典型，至少約12%，甚至更典型，至少約18 /6之彈性體，並通常包括不超過，甚至更典型不大於 40%和更典型不大於35%之彈性體，雖然較高或較低的百 分比是可能的。適合加成物之彈性體，不論是在主鏈或側 鏈皆可官能化。適合之官能基包括但不限於，_c〇〇H、 -NH2、-NH-、-OH、-SH、-CONH2、-CONH-、-NHCONH-、 -NCO、-NCS、以及環氧乙烷或氧化丙烯基團等。彈性體可 任選地為可硫化的或可後交聯的。示範性彈性體包括但不 限於：天然橡膠、丁苯橡膠、聚異戊二烯、聚異丁烯、聚 201120085 一： 異戊一烯丁二烯共聚物、氣平橡膠、腈橡膠、丁 η:烯腈共聚物、丁基橡膠、多硫化物彈性體、丙烯酸 _ :叫腈彈性體、#橡膠、聚魏燒、聚g旨橡膠、 二異，交聯縮合彈性體、EpDM(乙烯-丙烯二烯橡 膠)、氯石頁化聚乙烯、氟化烴、熱塑性彈性體、如(AB)及(ΑΒΑ) 類型的苯乙烯和丁二烯或異戊二烯嵌段共聚物 ，和（ΑΒ)η 類型之聚胺酯或聚酯多段嵌段共聚物等。在羧基封端之丁 二烯丙烯腈(CTBN)被用來作為官能化彈性體之案例中，較 佳之腈含量由12-35重量％，更佳是從2〇_33重量％。 %氧官能化環氧樹脂/彈性體加成物的較佳實例係以 與環氧樹脂之外加劑（商品名稱HyP〇xrMRK84(圖5)，以 CTBN彈性體改質之雙酚a環氧樹脂，商品名稱⑽丁M RA1340(圖6)，以CTBN彈性體改質之環氧樹脂盼祕清 漆樹脂)-起銷售，皆購自cvc孔簡咖⑽碰以公 ^穆f斯敦’新澤西州。除了伽A環氧樹脂之外，其 可用於製備環氧樹脂/彈性體加成物，如正丁基 樹脂化合物，如雙心二^麵氧丙麵；雙官能環氧 喊、魏S二環氧丙基叫=基醚、雙❹二環氧丙基 合物，如三環氧丙基異氛‘氣=酸；；三：能化 四官能化合物，如四環氧^二*氧丙基對胺基紛； 二胺基二苯基甲炫；及苯二胺和四環氧丙基 酸清漆聚環氧丙基㈣、基的化合物’如甲騎 於本發明之額外或替代環氣^㈣氧丙細等。適用 乳細如/彈性體和其他加成物之 19 201120085 實例揭露於Czaplicki，Michael之美國專利6,846,559、美國專 利公開號20〇4/〇2〇4551，兩者都被納入本文參考。 胺類化合物加反應性分散劑 為了製備固化劑，在一非限制性製程中，所選胺類化 合物和環氧-官能化反應性分散劑首先被反應以確保分散 劑是完全納入。反應性分散劑被溶於選定溶劑系統中，並 使用加熱和攪拌之組合來反應，從約2分鐘到約3小時， 較佳從大約4分鐘到約2小時和最佳從約5分鐘到1小時 左右。因此，本發明可以採用之反應溫度通常是4〇°c至9〇 °C，較佳是50°C至80°C，起始原料，即胺類化合物和環氧 官能反應性分散劑之濃度，通常約2至40重量％較佳約5 至30重量％。反應性分散劑之量，以反應性分散劑和胺類 化合物之總重量為基準計是由大約1至7〇%(w/w)，以反應 性分散劑和胺類化合物之總重量為基準計較佳是從大約5 至5 0 % (w/w)及以反應性分散劑和胺類化合物之總重量為 基準計最佳自約9至35%(w/w)。在環氧-官能化反應性分 散劑包含未鍵結到彈性體之殘餘環氧樹脂化合物之特殊情 形下，如圖5和6,採用額外純化步驟，由自該反應性分 政劑移除未反應環氧樹脂化合物所組成。該純化步驟尤為 重要，以避免在添加環氧樹脂化合物後形成黏聚和塊狀固 體材料（見下文）。 環氧樹脂相容材料 20 201120085 環氧樹脂相容材料是任何包含與環氧樹脂相容之一官 能基或多數官能基的環氧樹脂-功能材料。環氧官能化環氧 樹脂/彈性體加成物的一實例係以與環氧樹脂之外加劑（商 品名稱HyPoxTMRK84(圖5)，以及商品名稱HyPox™ RA1340(圖 6)) — 起銷售，購自 CVC Thermoset Specialties 公司，穆爾斯敦，新澤西州。該HyPox彈性體包含環氧樹 脂容單體(compatibilizingmonomer)丙稀腈。其他例子將包 括但不僅限於，包含環氧樹脂相容共單體之環氧-官能化聚 丙稀酸酉旨，像丙稀腈和曱基丙烯酸曱醋。 胺類化合物加環氧-官能化反應性分散劑加環氧樹脂 化合物，未-封裝粒子之形成 胺類化合物與環氧-官能化分散劑反應後，開始添加環 氧樹脂化合物以形成未封裝潛伏性硬化劑粒子。環氧樹脂 化合物之溶液慢慢添加到胺類化合物-分散穩定劑溶液之 攪拌加熱溶液，歷經從大約5分鐘至6小時，較佳從大約 10分鐘至4小時和最佳自約15分鐘到2小時，使用允許 固定不間斷添加環氧樹脂溶液之設備，如注射器泵或蠕動 泵或類似者。環氧樹脂化合物之量是由約10至90% (w/w)，基於胺類化合物、反應性分散劑、與環氧樹脂化合 物之總重量，較佳是從約30至85%(w/w)，基於胺類化合 物、反應性分散劑、與環氧樹脂化合物之總重量，和最佳 從大約50至80%(w/w)，基於胺類化合物、反應性分散劑、 與環氧樹脂化合物之總重量。在一實例中，反應性分散劑 21 201120085 和胺的溶液在加熱之同時攪拌，在惰性痛a 牙&lt; 乳下，並於預定 =二 =^_内添加環氧樹脂化合物溶液。 备壞氧树知化合物開始反應時，原本清晰之 透明。隨著反應的進行’反應祕的不透明程度逐步辦加， 最終發生特定乳白色渾濁分散物。 曰 當反應溫度和濃度起始材料過高，可 物’即使存在有適量的反應性分散劑。因“用= 應Γ度通常為4叱至9Gt ’較佳5Gt至_，起 =声即=合物、反應性分散劑、和環氧樹脂化合 物之辰度’通书為2至40重量％ ’較佳5至30重量％。 =綠:域物的粒子大顿料邱敎濃度增加而 乓加，但Ik者反應性分散劑之濃度增加而降低。 封裝 夕粒子後續以塗覆在粒子上之各層封裝或保護殼在一或 =個連續步驟—。封裝球_化劑之各種已知方法可 於此4月在一貫施型態中，加成物粒子可與封裝劑以 2方式反應，以形成二或更多之保護殼，其中該封裝劑 括多ΐ能異㈣sl化合物，或多官能異級醋化合物 口：了„脂化合物之混合物，或多官能異氰酸酯和 二氣Μ月曰，谷化合物(例如，丙烯腈)之混合物，或多官能異 =酸g旨、、環氧樹脂化合物、和環氧樹脂相容化合物之混合 斤、.且成適5之多官能異氰酸酯化合物，包括單核和多 X種甲苯二異氰酸酯、二苯基甲烷二異氰酸酯 、氫化二苯 22 201120085 基曱烷二異氰酸酉旨、☆萘二異氰酸醋、異佛爾酮二異氰酸 醋、六亞甲基二異氰酸醋、二甲笨二異氰酸§旨、氫化二甲 苯二異氰酸酯、四曱基二曱苯二異氰酸酯、U，6-六亞曱基 三異氰酸S旨、賴氨酸二異氰酸自旨、三苯基乙烧三異氰酸醋、 藉由添加該等化合物所形成之多官能異氰酸S旨化合物和豆 他活性含氫化合物，和其任何混合物。 夕B能環，樹脂之代表實例包括亞曱基雙環氧丙基 ^ HELOXY μ Μο·Γ 48咖⑹㈣卿㈤ 接贱f ^騎甲㈣·環氧樹脂 之多:^^^^:^細目容共單體） 用於封I未封Μ 4 Ί多官能環氧樹脂。 和固化劑母粒的率。^封I劑的量係影響儲存穩定性 裝劑的增加量改善儲存：：同粒子之添加產物而言，封 具有直徑約G.1微米至部降低固化率。因此，針對 裝劑比率為核粒子相=之加成物粒子’所採用之封 較佳為核粒子相對於^裝劑從約5Q:5()至95 和最佳比率為核、大約6_至，j， 9〇:l〇(w/w)。此外，當封於封裴劑自約7〇:3〇至 ^合物或異氰_旨化合:=氰動旨化合物和環氧樹脂 :寺，所”環氧樹脂化合物：二,脂相容化合物之混合物 目對於環氧樹脂化合物 ♦、比率為異氰酸g旨化合物 氰酸酯化合物相對 約1:99至99:1(w/w) 心叫峨樹脂化合物從大約〇= 為異級料合物㈣於環氧樹月t 201120085 醋二合二=2()和99:1(W/W)。此外，當封裝劑是異、 合物，所使物、和環氧樹脂相容化合物:ί 於環氧樹脂化“自H9物之量係異氰義化合物相_ 異氰酸料合物相對；^r i 99:1(w/w)的比率，較佳為 合物相對於環氧樹脂化合::)二最;氰酸賴化 此，儲存穩定性和固化„ 8〇·20和&quot;·1(，。因 小，較小的粒徑需要折中取決於加成物教子的大 酸，樣：二=料的量’如多官能異氮 子藉::==4粒子形成反應完成後’未封裂牴 些粒子然後在後分離’鮮溶μ淨。這 母粒 9〇%(,，較佳氧樹脂之總重量為基準範圍從5到 在約以與液體環氧樹脂之總重量為基準 〜f 4基#在约2G至70⑽/w)範圍。 “曰 月漆娘氧樹脂等的環氧樹脂。 在一實施型態φ，&amp; , ,, _ 被機械性地分散在環氧=:=: = 24 201120085 輥軋機摻合。 在另一實施型態中，在封裝製程完成後，停止加熱和 攪拌’並將環氧樹脂添加到分散物。混合物再次被擾摔， 足以使環氧樹脂均等地分散在分散物中。然後，利用真空 蒸餾或類似方式移除溶劑，以使總固體含量約6〇黾1〇〇% (W/W)，較佳約70至100%(重量/重量），和最佳約8〇至1〇〇 %(w/w)。然後這些粒子進一步被分散在環氧樹脂中，使用 於所屬技術領域中具有通常知識者所熟知之技術，如三輥 軋機，或類似。 隹另一貫施型態中 田久愿元烕後民q具空瘵餾去 =浴劑至100%(w/w)的固體含量。然後固體粒子被添加到 環氧樹脂中，且該粒子進—步被分散在環氧樹脂中，使用 .於所屬技術領域中具有通常知識者所熟知之技術，如三報 軋機，或類似。 聽實_態中’ #反應^成後’藉由過濾、粒子分 離粒子。新鮮溶劑被用來洗掉黏附在粒子表面的 的起始材料。環氧樹脂然後被添加到固體粒子中， 步被分散’使用於所屬技術領域中具有通常 者所熟知之技術，如三輥軋機，或類似。 在導之崎劑成分潛在有益於各種應用，包括 Θ、複合材料、模塑料、各向異性導電膜(ACF) 射裝二非^機陣列ACF、非導電黏著劑膜(NCF)、塗層、 ’ 、底取材料、無錯焊料等。 為4田述本兔明之細節，本發明將以下列非限制性實例 25 201120085 加以說明。 實例 形成未封裝核粒子之實例： 實施例1，從2-曱基咪唑、DGEBA、和HyPoxTMRK 84(1) 合成未封裝核粒子。 市售材料 HyPox RK84 [CVC Thermoset Specialties 之 市售材料，雙酚A環氧樹脂及其與CTBN之加成物之混合 物（圖5)]被用作為分散穩定劑。具有pTFE氟聚合半月形頂 置式攪拌器、迴流冷凝器、加料漏斗及氬氣入口之三頸圓 底燒瓶加入0.93克CTBN-環氧樹脂加成物、ι·64克(0.02 mole)2-曱基咪唑和48克4-曱基-2-戊酮(ΜΙΒΚ)。該反應器 被置於80。(：浴，並吹入氬氣。經過丨小時後，3 39克(0.019The resin includes a two-year A t choice. Due to the majority of the epoxy to be cured, a compound such as % oxypropyl ether, this compound is most typically used as A =:::: starting material. In-implementation, it is generally preferred to have an epoxy equivalent of up to about 10,000, and preferably up to about 16 201120085 500. Solvent It is also important to select a solvent system which dissolves the amine compound and the epoxy resin compound as a starting material, but which can be precipitated in the form of insoluble particles without dissolving the adduct. Examples of solvents which may be used in certain embodiments of the invention are mercaptoisobutyl ketone, methyl isopropyl ketone, mercapto ethyl ketone, acetone, n-butyl acetate, isobutyl acetate, ethyl acetate, cesium acetate Ester, tetrahydrofuran, 1,4-dioxane, cellosolve, ethylene glycol monoethyl ether, diethylene glycol dioxime ether, benzoquinone, toluene, p-diphenyl, benzene, Gas decane, chloroform, trichloroethylene, chlorobenzene and pyridine. These solvents may be used singly or two or more solvents may be used together. Non-Solvents Additionally, it may be desirable to add a non-solvent to assist in forcing the amine compound to react with the dispersion stabilizer and the epoxy functional groups of the epoxy resin. The non-solvent in this case is any solvent which is insoluble in an amine compound, a dispersion stabilizer, or an epoxy resin. Possible types of compounds which can be used as non-solvents are linear or branched aliphatic compounds such as heptane, hexane, octane, isooctane, petroleum ether and the like. An example of a non-solvent binding solvent is a mixture of heptane and mercaptoisobutyl ketone (MIBK). In addition to the solvents and non-solvents described above, diluents or weak solvents are optionally used to relax the formulation or process tolerance. Dispersion Stabilizers or Dispersants 17 201120085 Agents or dispersants stabilize the H/λ reading dispersion of the adduct particles in the reaction medium. (4) Addition of the recordings may break apart, and the polycondensation and precipitation become sticky blocks' Thus, the required fineness 1 cannot be obtained. The best dispersion (4) is stable with a narrow particle size distribution. The reactive dispersant tends to have 1 nt 3 *denier than the non-reactive dispersant, and it will not be able to desorb or migrate from the surface of the particle. An elastomer/epoxy resin adduct is used as the reactive dispersant according to the present invention. Suitable molecular weight ranges for the anti-dispersing agent are from ^, from 1 000 to 300,000, preferably from about 2,000 to 100,000, and most preferably from about 3, 〇〇〇 to 1 〇, 〇〇〇. Epoxy Jit Lipid Elastomer Addition as Reactive Dispersant The epoxy resin/elastomer adduct itself generally comprises from about 1:5 to 5:1 parts of epoxy resin or other polymer (relative to elastomer) More preferably, it is about 1:3 to 3.1 parts of epoxy resin (relative to the elastomer). More typically, the adduct comprises at least about 5%, more typically, at least about 12%, even more typically, at least about 18/6 of the elastomer, and typically includes no more than, even more typically no more than 40% and more typically no More than 35% elastomer, although higher or lower percentages are possible. Elastomers suitable for adducts can be functionalized either in the main chain or in the side chain. Suitable functional groups include, but are not limited to, _c〇〇H, -NH2, -NH-, -OH, -SH, -CONH2, -CONH-, -NHCONH-, -NCO, -NCS, and ethylene oxide or An oxypropylene group or the like. The elastomer may optionally be vulcanizable or post-crosslinkable. Exemplary elastomers include, but are not limited to, natural rubber, styrene butadiene rubber, polyisoprene, polyisobutylene, poly 201120085 one: isoprene-butadiene copolymer, gas flat rubber, nitrile rubber, butylene: ene Nitrile copolymer, butyl rubber, polysulfide elastomer, acrylic acid _: nitrile elastomer, #橡胶, polywei, rubber, diiso, crosslinked condensed elastomer, EpDM (ethylene-propylene diene Rubber), chlorinated polyethylene, fluorinated hydrocarbons, thermoplastic elastomers, styrene and butadiene or isoprene block copolymers of the type (AB) and (ΑΒΑ), and (ΑΒ)η type Polyurethane or polyester multi-block copolymers and the like. In the case where the carboxyl terminated butadiene acrylonitrile (CTBN) is used as the functionalized elastomer, the preferred nitrile content is from 12 to 35% by weight, more preferably from 2 to 33% by weight. A preferred example of a % oxygen functional epoxy resin/elastomer adduct is a bisphenol a epoxy resin modified with an epoxy resin (trade name HyP〇xrMRK84 (Fig. 5), modified with CTBN elastomer. , the product name (10) Ding M RA1340 (Figure 6), modified with CTBN elastomer epoxy resin varnish resin) - from the sale, are purchased from cvc Kong Jane (10) hit the public ^ Mu fstown 'New Jersey . In addition to gamma A epoxy resin, it can be used to prepare epoxy resin/elastomer adducts, such as n-butyl resin compounds, such as double-sided bismuth oxypropylene; difunctional epoxy shout, Wei S bicyclo Oxypropyl group is a base ether, a biguanide diepoxypropyl compound, such as a trisepoxypropyl iso-'a gas = acid; three: a tetrafunctional compound such as tetraepoxy^dioxypropyl Amino group; diaminodiphenylmethyl choline; and phenylenediamine and tetraepoxypropyl acid varnish polyepoxypropyl (tetra), based compound 'such as A riding on the additional or alternative ring gas of the present invention ^ (4) Oxygen propylene fine and so on. Suitable for use in the form of a lotion, such as an elastomer and other adducts. 19 201120085 An example is disclosed in Czaplicki, U.S. Patent No. 6,846,559 to Michael, U.S. Patent Publication No. 20, 4/2,455, the entire disclosure of which is incorporated herein by reference. Amine Compounds plus Reactive Dispersants To prepare the curing agent, the selected amine compound and the epoxy-functional reactive dispersant are first reacted in a non-limiting process to ensure complete incorporation of the dispersant. The reactive dispersant is dissolved in a selected solvent system and reacted using a combination of heat and agitation, from about 2 minutes to about 3 hours, preferably from about 4 minutes to about 2 hours and optimally from about 5 minutes to 1 Hours or so. Therefore, the reaction temperature which can be employed in the present invention is usually from 4 ° C to 9 ° C, preferably from 50 ° C to 80 ° C, and the starting materials, that is, the concentrations of the amine compound and the epoxy functional reactive dispersant It is usually from about 2 to 40% by weight, preferably from about 5 to 30% by weight. The amount of the reactive dispersant is from about 1 to 7 % by weight (w/w) based on the total weight of the reactive dispersant and the amine compound, based on the total weight of the reactive dispersant and the amine compound. Preferably, it is from about 5 to 50% (w/w) and preferably from about 9 to 35% (w/w) based on the total weight of the reactive dispersant and the amine compound. In the special case where the epoxy-functional reactive dispersant comprises residual epoxy resin compound not bonded to the elastomer, as in Figures 5 and 6, an additional purification step is employed, from which the reactive component is removed. The reaction epoxy resin compound is composed. This purification step is especially important to avoid the formation of cohesive and bulk solid materials after the addition of the epoxy resin compound (see below). Epoxy Resin Compatible Materials 20 201120085 Epoxy Resin Compatible Materials are any epoxy-functional materials that contain one or more functional groups compatible with epoxy resins. An example of an epoxy functional epoxy resin/elastomer adduct is sold with an epoxy resin addition agent (trade name HyPoxTM RK84 (Fig. 5) and trade name HyPoxTM RA1340 (Fig. 6)). Since CVC Thermoset Specialties, Moorestown, NJ. The HyPox elastomer comprises an epoxy resin monomer (compatibilizing monomer) acrylonitrile. Other examples will include, but are not limited to, epoxy-functionalized polyacrylates containing epoxy compatible comonomers, such as acrylonitrile and decyl acrylate vinegar. An amine compound plus an epoxy-functional reactive dispersant plus an epoxy resin compound, an amine-based compound formed by the un-encapsulated particles is reacted with an epoxy-functionalized dispersant, and an epoxy resin compound is added to form an unencapsulated latent Sclerosing agent particles. The solution of the epoxy resin compound is slowly added to the stirred heating solution of the amine compound-dispersion stabilizer solution for from about 5 minutes to 6 hours, preferably from about 10 minutes to 4 hours, and most preferably from about 15 minutes to 2 For hours, use equipment that allows for the uninterrupted addition of epoxy resin solutions, such as syringe pumps or peristaltic pumps or the like. The amount of the epoxy resin compound is from about 10 to 90% (w/w) based on the total weight of the amine compound, the reactive dispersant, and the epoxy resin compound, preferably from about 30 to 85% (w/ w) based on the total weight of the amine compound, the reactive dispersant, and the epoxy resin compound, and most preferably from about 50 to 80% (w/w) based on the amine compound, the reactive dispersant, and the epoxy The total weight of the resin compound. In one example, the reactive dispersant 21 201120085 and the amine solution are stirred while heating, under an inert pain a tooth &milk; and an epoxy resin compound solution is added within a predetermined = two = ^_. When the compound is prepared, the compound is clear and transparent. As the reaction proceeds, the degree of opacity of the reaction is gradually increased, and a specific milky white turbid dispersion eventually occurs.曰 When the reaction temperature and concentration of the starting material are too high, the object 'even if there is an appropriate amount of reactive dispersant. Because "use = should generally be 4 叱 to 9 Gt', preferably 5 Gt to _, from = sound = compound, reactive dispersant, and epoxy compound's degree - 2 to 40% by weight 'Optimum 5 to 30% by weight. = Green: The particle size of the domain is increased by the increase in the concentration of Qiu, but the concentration of the reactive dispersant in Ik is decreased. The encapsulated Xi particle is subsequently coated on the particle. Each layer of the encapsulation or protective shell is in one or a continuous step - various known methods of encapsulating the ball-incorporating agent can be carried out in a consistent manner in April, and the adduct particles can react with the encapsulant in a two-way manner. To form two or more protective shells, wherein the encapsulant comprises a poly(4-)sl compound, or a polyfunctional hetero-salt compound: a mixture of fatty compounds, or a polyfunctional isocyanate and a gas a mixture of a compound (for example, acrylonitrile), or a polyfunctional iso-acid, an epoxy resin compound, and an epoxy resin-compatible compound, and a polyfunctional isocyanate compound, including a single core. And many X kinds of toluene diisocyanate, diphenylmethane diisocyanate Ester, hydrogenated diphenyl 22 201120085 decane diisocyanate, ☆ naphthalene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dimethyl stupid Cyanate cyanate, hydrogenated xylene diisocyanate, tetradecyldiphenylene diisocyanate, U,6-hexa-indenyl triisocyanate, lysine diisocyanate, triphenylethane Triisocyanate, a polyfunctional isocyanate S compound formed by the addition of such compounds, and a benzoic active hydrogen-containing compound, and any mixture thereof.夕B can ring, representative examples of resin include yttrium-based bis-epoxypropyl group ^ HELOXY μ Μ ο Γ 48 coffee (6) (four) Qing (five) 贱 f ^ riding armor (four) · epoxy resin: ^ ^ ^ ^: ^ details Capacitor monomer) Used to seal I unpacked 4 Ί multi-functional epoxy resin. And the rate of curing agent masterbatch. The amount of the agent I affects the storage stability. The increase in the amount of the agent improves the storage:: with the added product of the particles, the seal has a diameter of about G.1 micron to a portion to lower the curing rate. Therefore, the seal used for the additive particle ratio of the core particle phase = preferably the core particle relative to the charge agent from about 5Q: 5 () to 95 and the optimum ratio is the core, about 6_ To, j, 9〇: l〇(w/w). In addition, when sealed in a sealant from about 7 〇: 3 〇 to ^ compound or isocyanide _ combination: = cyanide compound and epoxy resin: Temple, "epoxy resin compound: two, fat compatible The mixture of the compounds is for the epoxy resin compound ♦, the ratio is isocyanate g, the compound cyanate compound is relatively about 1:99 to 99:1 (w/w), the sputum resin compound is from about 〇= is a heterogeneous material. Compound (iv) in Epoxy Tree t 201120085 vinegar in two = 2 () and 99: 1 (W / W). In addition, when the encapsulant is a heterogeneous compound, the resulting substance, and the epoxy resin compatible compound : ί epoxide "the ratio of the isocyanide compound phase from the H9 substance to the isocyanate compound; ^ri 99:1 (w / w) ratio, preferably the compound relative to the epoxy Resin compound::) two most; cyanate lysate, storage stability and curing „ 8〇·20 and &quot;·1 (, because of small, smaller particle size needs compromise depends on the addition of the godson Large acid, sample: two = amount of material 'such as polyfunctional isotope borrowed:: == 4 after the particle formation reaction is completed 'unblocked some particles and then separated after the 'fresh soluble μ net. This masterbatch 9〇 %(,, the total weight of the preferred oxygen resin The reference range is from 5 to about the total weight of the liquid epoxy resin ~f 4 base # in the range of about 2G to 70 (10) / w. "Epoxy resin such as 曰月漆娘氧氧. In an embodiment State φ, &amp; , ,, _ is mechanically dispersed in epoxy =:=: = 24 201120085 Rolling mill blending. In another embodiment, after the packaging process is completed, stop heating and stirring' and An epoxy resin is added to the dispersion. The mixture is again disturbed, enough to uniformly disperse the epoxy resin in the dispersion. Then, the solvent is removed by vacuum distillation or the like so that the total solid content is about 6〇黾1〇. 〇% (W/W), preferably about 70 to 100% (w/w), and most preferably about 8 to 1% (w/w). The particles are then further dispersed in an epoxy resin. It is used in a technique well known to those skilled in the art, such as a three-roll mill, or the like. 隹Another continuous application mode, Nakata, a long-awaited 烕 烕 民 q q = = = = = = bath to 100% (w /w) solid content. The solid particles are then added to the epoxy resin and the particles are dispersed in the epoxy tree In the art, a technique well known to those skilled in the art, such as a three-roll mill, or the like is used. In the _ state, '#reactions are formed after the particles are separated by filtration and particles. Fresh solvent is used. The starting material adhered to the surface of the particles is washed away. The epoxy resin is then added to the solid particles and the steps are dispersed 'used in the art, as is well known in the art, such as a three-roll mill, or the like. It is potentially beneficial to a variety of applications, including tantalum, composites, molding compounds, anisotropic conductive film (ACF), two-machine array ACF, non-conductive adhesive film (NCF), coating, ', bottom material, error-free solder, etc. The details of the present invention will be illustrated by the following non-limiting example 25 201120085. EXAMPLES Examples of forming unencapsulated core particles: Example 1, unpackaged core particles were synthesized from 2-mercaptoimidazole, DGEBA, and HyPoxTM RK 84(1). Commercially available materials HyPox RK84 [a commercially available material of CVC Thermoset Specialties, a mixture of bisphenol A epoxy resin and its adduct with CTBN (Fig. 5)] was used as a dispersion stabilizer. A three-necked round bottom flask with a pTFE fluoropolymerized half-moon overhead stirrer, reflux condenser, addition funnel and argon inlet was added to 0.93 g of CTBN-epoxy resin adduct, ι·64 g (0.02 mole) 2-曱Imidazole and 48 g of 4-mercapto-2-pentanone (oxime). The reactor was placed at 80. (: bath, and argon gas is blown in. After 39 hours, 3 39 grams (0.019

當置）DER™ 332(Dow Chemical 公司之產品）與 3.4 克 MIBK ，溶液歷時20分鐘以液滴方式添加，之後反應係在氬氣氣 氛:以300 rpm攪拌6小時。形成白色乳狀分散物。從反 ，器釋出分散物、離心、用MIBK洗滌、並蒸發至乾以獲 付3.6克(60.4%產率）的產物。一小滴的分散物被稀釋塗在 玻螭片上’在室溫於真空中乾燥。 將乾燥後之樣品滅鑛-層薄薄的黃金，並使用臟咖 S-2460N掃描式電子驗鏡取得掃描電子顯微照片。 、和 HyPoxTMRK 84(2) 實施例2’從2-曱基咪唑、Dgeba 合成未封裝核粒子。 26 201120085 從 CVC Thermoset Specialties HyPoxTMRK 84 分離的 CTBN-環氧樹脂加成物係被使用作為分散穩定劑。材料溶 解在曱基乙基酮中獲得加成物，接著以甲醇沉澱，並重複 此過程兩次。未封裝核粒子2係合成自0.51克的CTBN-環氧樹脂加成物，1.63克(0.02 mole)的2-甲基。米嗤，3.51 克(〇.〇2當量）的DERTM332和51克MIBK，使用實施例1 之過程’以獲得4.4克(78%產率）的粒子。 實施例3，從2-曱基咪唑、DGEBA、和HyPoxTMRA 1340(3)合成未封裝的核粒子。 市售材料 HyPox RA1340 [CVC Thermoset Specialties 之市售材料，雙酚A之環氧丙基醚及其與CTBN之加成物 之混合物（圖6)]被用作為分散穩定劑。微囊核3是合成自 1.15克上述CTBN-環氧樹脂加成物，1.64克(0.02 mole)的 2-甲基咪唑’ 2.87克(0.0164當量）的DERTM332和51克 MIBK ’使用實施例1之過程，以獲得1.2克(21.2%產率） 的粒子。 實施例4 ’從2-曱基咪唑、DGEBA、和HyPoxTMRA 1340(4)合成未封裝核粒子。 從 CVC Thermoset Specialties HyPoxTMRA 1340 分離的 CTBN-i展氧樹脂加成物係被使用作為分散穩定劑。材料溶 解在曱基乙基酮中獲得加成物，接著以曱醇沉澱，並重複 此過程兩次。未封裝核粒子4係合成自0.53克的CTBN- 27 201120085 加成物’ h65克(0_〇2 mole)2-甲基哞唑，3.5克(0.02當量) 的DERTM332和51克MIBK，使用實施例1之過程，以獲 得2.6克(45.9%產率）的粒子。 貫施例5,從2-乙基-4-曱基咪唑、DGEBA、和HyPoxTM RK 84(5)合成未封裴核粒子。 未封製核粒子S係合成自0.57克實施例2之CTBN-環氧樹脂加成物、2.20克(〇.〇2 m〇le)2-乙基-4-曱基咪唑、 3.5克(〇.〇2當量）的dertm332和63克MIBK，使用實施例 1之過程，以獲得0.7克（11.2%產率）粒子。 實施例6 ’從2-甲基咪唑、DGEBA、和HyPoxTMRA 1340(6)合成未封装核粒子。 未封裝核粒子6係合成自0.26克實施例4之CTBN-樣氧樹脂加成物、1.64克(〇.〇2 mole)2-甲基咪唑、3.5克(0.02 當量)的DERTM332和50克MIBK，使用實施例1之過程， 以獲得1·6克(26.9%產率)粒子。 實施例7,從2-乙基·4_曱基咪唑、DGEBA、和HyPoxTM RK 84(7)合成未封裝的核粒子。 未封裝的核粒子7係合成自0.57克的實施例2之 CTBN-環氧樹脂加成物、2.20克(0.02 mole)2-乙基-4-曱基 °米唾、3.5克(〇·〇2當量）的DERTM332和56克MIBK，使用 實施例1之過程。且反應是在氬氣氣氛下以300 rpm攪拌 28 201120085 16·5小時’以獲得2.5克(40%產率）的粒子。 實施例8,從2-曱基咪唑、DGEBA、和HyPoxTM RK 84(8) 合成未封裝的核粒子。 微囊核8係合成自0.52克的實施例2之CTBN-環氧樹 脂加成物、1.64克(〇 02 m〇le)2-曱基咪唑、3.5克(0.02當量） 的DERTM332和51克MIBK，使用實施例1之過程。且反 應是在氬氣氣氛下以300 rpm攪拌16小時，以獲得4.0克 (71%產率）的粒子。 實施例9 ’從2-曱基咪唑、DGEBA、和HyPox™ RK 84(9) 合成未封裝的核粒子。 未封裝的核粒子9係合成自0..52克的實施例2之 CTBN-環氧樹脂加成物、1.64克(0.02 mole)2-曱基咪唑、3.5 克(0·02當量）的DERTM332和52克MIBK，使用實施例1 之過程。且反應是在氬氣氣氛下以1〇〇〇 rpm攪拌6小時， 以獲得4.18克(74%產率）的粒子。 貫施例10，從2-曱基咪唑、DGEBA、和HyPoxTM RK 84(10)合成未封裝的核粒子。When DERTM 332 (product of Dow Chemical) was placed with 3.4 g of MIBK, the solution was added dropwise in 20 minutes, after which the reaction was carried out in an argon atmosphere at 600 rpm for 6 hours. A white milky dispersion is formed. The dispersion was released from the apparatus, centrifuged, washed with MIBK, and evaporated to dryness to afford 3.6 g (60.4% yield) of product. A small droplet of the dispersion was diluted on a glass plate and dried in vacuo at room temperature. The dried sample was mined - a thin layer of gold, and a scanning electron micrograph was taken using a dirty coffee S-2460N scanning electron inspection. And HyPoxTM RK 84 (2) Example 2' Synthesis of unencapsulated core particles from 2-mercaptoimidazole, Dgeba. 26 201120085 CTBN-epoxy resin adducts isolated from CVC Thermoset Specialties HyPoxTM RK 84 are used as dispersion stabilizers. The material was dissolved in mercaptoethyl ketone to obtain an adduct, followed by precipitation with methanol, and the procedure was repeated twice. The unencapsulated core particles 2 were synthesized from 0.51 g of CTBN-epoxy resin adduct and 1.63 g (0.02 mole) of 2-methyl. Rice bran, 3.51 g (〇.〇2 equivalent) of DERTM 332 and 51 g of MIBK, using the procedure of Example 1 to obtain 4.4 g (78% yield) of particles. Example 3, unpackaged core particles were synthesized from 2-mercaptoimidazole, DGEBA, and HyPoxTMRA 1340(3). Commercially available material HyPox RA1340 [a commercially available material of CVC Thermoset Specialties, a mixture of epoxidized propyl ether of bisphenol A and its adduct with CTBN (Fig. 6)] was used as a dispersion stabilizer. Microcapsule core 3 is synthesized from 1.15 g of the above CTBN-epoxy resin adduct, 1.64 g (0.02 mole) of 2-methylimidazole ' 2.87 g (0.0164 equivalent) of DERTM 332 and 51 g of MIBK 'using Example 1 The procedure was carried out to obtain 1.2 g (21.2% yield) of particles. Example 4 'Unpackaged core particles were synthesized from 2-mercaptoimidazole, DGEBA, and HyPoxTMRA 1340 (4). A CTBN-i oxygenation resin adduct isolated from CVC Thermoset Specialties HyPoxTM RA 1340 was used as a dispersion stabilizer. The material was dissolved in mercaptoethyl ketone to obtain an adduct, followed by precipitation with decyl alcohol, and the procedure was repeated twice. The unencapsulated core particle 4 was synthesized from 0.53 g of CTBN- 27 201120085 adduct 'h65 g (0_〇2 mole) 2-methylcarbazole, 3.5 g (0.02 equivalent) of DERTM 332 and 51 g of MIBK, using The procedure of Example 1 gave 2.6 grams (45.9% yield) of particles. Example 5, unblocked nucleus particles were synthesized from 2-ethyl-4-mercaptoimidazole, DGEBA, and HyPoxTM RK 84 (5). The unsealed core particle S was synthesized from 0.57 g of the CTBN-epoxy resin adduct of Example 2, 2.20 g of 乙基.〇2 m〇le 2-ethyl-4-mercaptoimidazole, 3.5 g (〇) .2 equivalents of dertm332 and 63 grams of MIBK, using the procedure of Example 1 to obtain 0.7 grams (11.2% yield) of particles. Example 6 'Unpackaged core particles were synthesized from 2-methylimidazole, DGEBA, and HyPoxTMRA 1340 (6). The unencapsulated core particles 6 were synthesized from 0.26 g of the CTBN-like oxygen resin adduct of Example 4, 1.64 g of 2-methylimidazole, 3.5 g (0.02 equivalent) of DERTM 332 and 50 g of MIBK. Using the procedure of Example 1, a 1.6 g (26.9% yield) particle was obtained. Example 7, unpackaged core particles were synthesized from 2-ethyl-4-imidazole, DGEBA, and HyPoxTM RK 84 (7). The unencapsulated core particles 7 were synthesized from 0.57 g of the CTBN-epoxy resin adduct of Example 2, 2.20 g (0.02 mole) of 2-ethyl-4-indolyl sate, 3.5 g (〇·〇) The procedure of Example 1 was used for 2 equivalents of DERTM 332 and 56 grams of MIBK. And the reaction was stirred at 300 rpm under an argon atmosphere for 28 2011 2008 5 16.5 hours to obtain 2.5 g (40% yield) of particles. Example 8, synthesis of unencapsulated core particles from 2-mercaptoimidazole, DGEBA, and HyPoxTM RK 84(8). The microcapsule core 8 was synthesized from 0.52 g of the CTBN-epoxy resin adduct of Example 2, 1.64 g (〇02 m〇le) 2-mercaptoimidazole, 3.5 g (0.02 equivalent) of DERTM 332 and 51 g of MIBK. The procedure of Example 1 was used. And the reaction was stirred at 300 rpm for 16 hours under an argon atmosphere to obtain 4.0 g (71% yield) of particles. Example 9 'Unpackaged core particles were synthesized from 2-mercaptoimidazole, DGEBA, and HyPoxTM RK 84(9). The unencapsulated core particles 9 were synthesized from 0..52 g of the CTBN-epoxy resin adduct of Example 2, 1.64 g (0.02 mole) of 2-mercaptoimidazole, and 3.5 g (0.022 equivalent) of DERTM332. The procedure of Example 1 was used with 52 grams of MIBK. And the reaction was stirred at 1 rpm for 6 hours under an argon atmosphere to obtain 4.18 g (74% yield) of particles. Example 10, unpackaged core particles were synthesized from 2-mercaptoimidazole, DGEBA, and HyPoxTM RK 84 (10).

未封襞的核粒子10係合成自〇·52克的實施例2之 CTBN-環氧樹脂加成物，1.64克(0.02 mole)2-曱基咪唑和 37.3克4-甲基_2_戊酮(MIBK)。該反應器被置於80t浴， 並吹入氩氣。經過1小時後，3·5克(〇.〇2當量）DERTM 29 201120085 332(Dow Chemical公司之產品）與3.5克MIBK之溶液歷時 15分鐘以液滴方式添加，之後反應係在氬氣氣氛下以1〇〇〇 rpm攪拌1小時。之後’歷時丨小時以液滴方式添加1〇克 之庚烷。反應續以1000 rpm攪拌4小時。形成白色乳狀分 散物。從反應器釋出分散物、離心、用MIBK洗滌，並蒸 發至乾，以獲得2.1克(37%產率）的乾粒子。 實施例11，從2·曱基咪唑、DGEBA、和HyPoxTMRK 84(11)合成未封農核粒子。 未封裝核粒子11係合成自0.52克的實施例2之CTBN-環氧樹脂加成物，L64克(〇 〇2 m〇le)2_f基咪唑，和37 3 克甲基-2-戊酮(MIBK)。該反應器被置於8〇»c浴，並吹 入氬虱。經過1小時後，3_5克(〇.〇2當量)DER™ 332(D〇W Chemical公司之產品）與3 5克M[BK之溶液歷時Μ分鐘 以液滴方式添加，之後反應係在氬氣氣氛下以1麵rpm擾 拌1時。之後，歷時1小時以液滴方式添加3克之庚烷。 7 x 1000 rpm攪拌4小時。形成白色乳狀分散物。從 ^釋出分散物、離^、用mibk洗〉條，並蒸發至乾， 以纹仵3·〇克(53%產率）的乾粒子。 未封裝核粒子12係合成自 環氧樹脂加成物、1.64克(〇.〇2】The unsealed core particle 10 was synthesized from 52 g of the CTBN-epoxy resin adduct of Example 2, 1.64 g (0.02 mole) of 2-mercaptoimidazole and 37.3 g of 4-methyl-2-indole Ketone (MIBK). The reactor was placed in an 80 t bath and argon gas was blown in. After 1 hour, 3.5 gram (〇.〇2 equivalent) DERTM 29 201120085 332 (product of Dow Chemical) and 3.5 g of MIBK solution were added in droplets over 15 minutes, after which the reaction was carried out under an argon atmosphere. Stir at 1 rpm for 1 hour. Thereafter, 1 gram of heptane was added in droplets over a period of hours. The reaction was continued for 4 hours at 1000 rpm. A white milky dispersion is formed. The dispersion was released from the reactor, centrifuged, washed with MIBK, and evaporated to dryness to obtain 2.1 g (37% yield) of dry particles. Example 11, synthesis of unsealed agricultural core particles from 2· mercapthylimid, DGEBA, and HyPoxTM RK 84 (11). The unencapsulated core particles 11 were synthesized from 0.52 g of the CTBN-epoxy resin adduct of Example 2, L64 g (〇〇2 m〇le) 2_f-based imidazole, and 37 3 g of methyl-2-pentanone ( MIBK). The reactor was placed in a 8 〇»c bath and argon was blown. After 1 hour, 3_5 g (〇.〇2 equivalent) of DERTM 332 (product of D〇W Chemical Co., Ltd.) and 35 g of M[BK solution were added in droplets over a period of minutes, after which the reaction was carried out in argon. In the atmosphere, the mixture was stirred at 1 rpm for 1 hour. Thereafter, 3 g of heptane was added in droplets over 1 hour. Stir at 7 x 1000 rpm for 4 hours. A white milky dispersion is formed. The dispersion was released from the dispersion, separated from the mixture, washed with mibk, and evaporated to dryness to obtain dry particles of 仵3·〇克 (53% yield). Unencapsulated core particle 12 is synthesized from epoxy resin adduct, 1.64 g (〇.〇2)

從2-甲基咪唑、DGEBA、和HyP〇xTM RK 貫施例12，從2-甲其 84(12)合絲龍核粒 丨1.05克的實施例2之CTBN-mole)2-曱基咪唑、3.5 克(0.02 201120085 當I)的DERTM332和51克MIBK，使用實施例1之過程。 反應在氬氣氣氛下以1〇〇〇 rpm攪拌6小時’以獲得4.4克 (71%產率）粒子。 貫施例13，從2-甲基咪唑、DGEBA、和HyPox™ RK 84(13)合成未封裝核粒子。 二頸圓底燒瓶具有PTFE氟聚合半月形頂置式攪拌 裔、迴流冷凝器、加料漏斗及氬氣入口。於該燒瓶加入〇 52 克的實施例2之CTBN-環氧樹脂加成物、164克(〇 〇2 m〇le)2-甲基味唑、5.1克庚烷和42.3克4-曱基-2-戊酮 (MIBK)。該反應器被置於80。(：浴，並吹入氬氣。經過1小 日ΐ後 ’ 3.5 克(〇.〇2 當量)dertm332(Dow Chemical 公司之產 品）與3.6克MIBK之溶液歷時15分鐘以液滴方式添加，之 後反應係在氬氣氣氛下以1〇〇〇rpm攪拌6小時。形成白色 乳狀分散物。從反應器釋出分散物、離心、用MIBK洗滌， 並蒸叙至乾，以獲得3.4克(60%產率）粒子。 貝施例14，從2-曱基咪唾、DGEBA、“純化” HyPoxTM RK 84(14)合成未封裝核粒子。 具有ΡΉΈ氟聚合半月形頂置式麟器、迴流冷凝器、 加料漏斗及氬氣入口之三頸圓底燒瓶加入〇·52克的實施例 2之CTBN環氧樹脂加成物、1.64克(0.02 mole)2_曱基咪 坐5.1克牙46.8克庚烧4-甲基-2-戊嗣(MIBK)。該反應器 被置於80°C浴，並吹入氬氣，於3〇〇rpm攪拌i小時。3 5 31 201120085 克(0·02 當量)DERTM 332(D〇w Chemical 公司之產品）與 3 5 克MIBK之溶液歷時15分鐘以液滴方式添加，之後反應係 在氮氣氣氛下以300 rpm攪拌1小時並續以1〇〇〇 rpm攪拌 5小時。形成白色乳狀分散物。從反應器釋出分散物、離 心、用ΜΐβΚ洗滌’並蒸發至乾，以獲得3.2克(57%產率) 的粒子。 實施例15，從2-曱基咪唑、DGEBA、和HyPoxTM RK 84(15)合成未封裝核粒子。 未封裝的核粒子(15)係合成自0.51克的實施例2之 CTBN_環氧樹脂加成物、1.64克(0.02mole)2-曱基咪唑、3.5 克(〇.〇2當量）的dertm332、15 3克庚烷和34克⑽服， 使用實施例13之過程。反應在氬氣氣氛下以i〇〇〇 rpm攪 拌ό小時’以獲得4·5克(8〇%產率）的粒子。 實施例16，從2-曱基咪唑、DGEBA、和HyPox™ RK 84(16)合成未封裝核粒子。 未封裝核粒子16係合成自0.52克的實施例2之CTBN-環氧樹脂加成物、1.64克(0.02 mole)2-甲基咪唑、3.5克(0.02 當量）的DERTM332、2.6克庚烷和49克MIBK，使用實施 例13之過程。反應在氬氣氣氛下以1000 rpm授拌6小時， 以獲得2.4克(42.4%產率）的粒子。From Example 2 of 2-methylimidazole, DGEBA, and HyP〇xTM RK, 1.05 g of CTBN-mole) 2-mercaptoimidazole of Example 2 from 2-methyl-84(12) The procedure of Example 1 was used with 3.5 grams (0.02 201120085 when I) of DERTM 332 and 51 grams of MIBK. The reaction was stirred at 1 rpm for 6 hours under an argon atmosphere to obtain 4.4 g (71% yield) of particles. According to Example 13, unencapsulated core particles were synthesized from 2-methylimidazole, DGEBA, and HyPoxTM RK 84 (13). The two-necked round bottom flask has a PTFE fluoropolymerized half-moon top stirrer, a reflux condenser, an addition funnel, and an argon inlet. To the flask was added 52 g of the CTBN-epoxy resin adduct of Example 2, 164 g of 〇〇2 m〇le 2-methylisoxazole, 5.1 g of heptane and 42.3 g of 4-mercapto- 2-pentanone (MIBK). The reactor was placed at 80. (: bath, and argon is blown in. After 1 day, '3.5 g (〇.〇2 equivalent) dertm332 (product of Dow Chemical)) and 3.6 g of MIBK solution are added in droplets for 15 minutes, after which The reaction was stirred at 1 rpm for 6 hours under an argon atmosphere to form a white milky dispersion. The dispersion was discharged from the reactor, centrifuged, washed with MIBK, and evaporated to dryness to obtain 3.4 g (60 % yield) particles. Shell Example 14, synthesizing unencapsulated core particles from 2-mercaptopurine, DGEBA, "purified" HyPoxTM RK 84 (14). Fluorine-polymerized half-moon shaped overhead reactor, reflux condenser The addition of a funnel and an argon inlet to the three-necked round bottom flask was carried out by adding 52 g of the CTBN epoxy resin adduct of Example 2, and 1.64 g (0.02 mole) of 2 曱 咪 咪 坐 5.1 5.1 5.1 4-methyl-2-pentanthene (MIBK). The reactor was placed in a bath at 80 ° C and blown with argon and stirred at 3 rpm for 1 hour. 3 5 31 201120085 g (0·02 eq) DERTM 332 (product of D〇w Chemical Co., Ltd.) and 35 g of MIBK solution were added in droplets over 15 minutes, after which the reaction was carried out under a nitrogen atmosphere at 3 Stir at 00 rpm for 1 hour and continue to stir at 1 rpm for 5 hours to form a white milky dispersion. Disperse the dispersion from the reactor, centrifuge, wash with ΜΐβΚ and evaporate to dryness to obtain 3.2 g (57%) Yield. Particles. Example 15. Synthesis of unencapsulated core particles from 2-mercaptoimidazole, DGEBA, and HyPoxTM RK 84 (15). Unencapsulated core particles (15) were synthesized from 0.51 g of Example 2 CTBN_epoxy resin adduct, 1.64 g (0.02 mole) 2-mercaptoimidazole, 3.5 g (〇.〇2 equivalent) of dertm332, 15 3 g of heptane and 34 g (10), using the procedure of Example 13 The reaction was stirred under an argon atmosphere at 〇〇〇 rpm for 'hours' to obtain 4.5 gram (8% yield) of particles. Example 16, from 2-mercaptoimidazole, DGEBA, and HyPoxTM RK 84 (16) Synthesis of unencapsulated core particles. Unencapsulated core particles 16 were synthesized from 0.52 g of the CTBN-epoxy resin adduct of Example 2, 1.64 g (0.02 mole) of 2-methylimidazole, 3.5 g (0.02 Equivalent) DERTM 332, 2.6 g heptane and 49 g MIBK, using the procedure of Example 13. The reaction was stirred at 1000 rpm for 6 hours under an argon atmosphere to obtain 2.4 g (42.4%). Rate) particles.

實施例17，從2-曱基咪唑、DGEBA、和HyPox™ RK 32 201120085 84(17)合成未封裝核粒子。 未封裝核粒子17係合成自0.52克的實施例2之CTBN-環氧樹脂加成物、1.64克(0.02 mole)2-曱基咪唑、3.5克(〇.〇2 當I)的DERTM332、10.2克庚烷和41克MIBK，使用實施 例13之過程。反應在氬氣氣氛下以1000 rpm攪拌6小時， 以獲得3.9克(69%產率）的粒子。 實施例18 ’從2-曱基咪唑、DGEBA、和HyPox™ RK 84(18)合成未封裝核粒子。 具有PTFE氟聚合半月形頂置式攪拌器、迴流冷凝器、 加料漏斗及氬氣入口之三頸圓底燒瓶加入〇 52克的實施例 2之CTBN環氧樹脂加成物、1.64克(0.02 mole)2-曱基味唾 和47.3克4-甲基_2-戊酮(MIBK)。該反應器被置於8〇。(：浴， 並吹入氬氣。於300 rpm攪拌1小時後，3 5克（〇 〇2當Example 17, synthesis of unpackaged core particles from 2-mercaptoimidazole, DGEBA, and HyPoxTM RK 32 201120085 84(17). The unencapsulated core particles 17 were synthesized from 0.52 g of the CTBN-epoxy resin adduct of Example 2, 1.64 g (0.02 mole) of 2-mercaptoimidazole, 3.5 g (〇.〇2 when I) of DERTM 332, 10.2. The procedure of Example 13 was used for kepeptane and 41 g of MIBK. The reaction was stirred at 1000 rpm for 6 hours under an argon atmosphere to obtain 3.9 g (69% yield) of particles. Example 18 'Unpackaged core particles were synthesized from 2-mercaptoimidazole, DGEBA, and HyPoxTM RK 84 (18). A three-necked round bottom flask with a PTFE fluoropolymerized half-moon overhead stirrer, reflux condenser, addition funnel and argon inlet was added to 52 g of the CTBN epoxy resin adduct of Example 2, 1.64 g (0.02 mole). 2-曱-based saliva and 47.3 g of 4-methyl-2-pentanone (MIBK). The reactor was placed at 8 Torr. (: bath, and blow in argon. After stirring at 300 rpm for 1 hour, 3 5 g (〇 〇 2 when

罝)DER μ 332(D〇w Chemical 公司之產品）與 3.5 克 MIBK 之溶液歷時15分鐘以液滴方式添加，之後反應係在氬氣氣 氛下以300 rPm攪拌1小時並續以1〇〇〇 rpm攪拌5小時。 开&gt; 成白色乳狀分散物。從反應器釋出分散物、離心、用Mibk 洗滌’並蒸發至乾，以獲得4.53克(80%產率）的粒子。 實施例19 ’從2-甲基咪唑、DGEBA、和HyP〇xTMRK 84(19)合成未封裝核粒子。 未封裝核粒子19係合成自0.51克的實施例2之CTBN-環氧樹脂加成物、1.64克(0.02 mole)2-甲基咪唑、3.5克(〇.〇2 33 201120085 當量）的DER™332和51克MIBK，使用實施例13之過程。 反應在氯氣氣氛下以1500 rpm撥拌6小時，以獲得4.05 克(71.5 %產率）的粒子。 實施例20，從2-甲基咪唑、DGEBA、和HyPoxTM RK 84(20)合成未封裝核粒子。 未封裝核粒子20係合成自0.52克的實施例2之CTBN-環氧樹脂加成物、1.64克(〇.〇2 mole)2-曱基咪唑、3.5克(0.02 當量）的DER™332、7.6克庚烷和43克MIBK，使用實施 例Π之過程。反應在氬氣氣氛下以1〇〇〇rpin攪拌6小時， 以獲得4.05克(71.5%產率）的粒子。 實施例21，從2-曱基咪唑、DGEBA.、和HyPoxTMRK 84(2Ό合成未封裝核粒子。 未封裝核粒子21係合成自0.51克的實施例2之CTBN-環氧樹脂加成物'1.65克(0.02 mole)2-曱基咪唑、3.5克(0.02 當量）的DERTM332、7.6克庚烷和.43克MIBK，使用實施 例13之過程。反應在氬氣氣氛下以1〇〇〇rpm攪拌16小時， 以獲得3.6克(64%產率）的粒子。 實施例22，從2-曱基咪唑、DGEBA、和HyPoxTM RK 84(22)合成未賴核粒子。 畑未封裝核粒子2 2係合成自〇. 51克的實施例2之C T B N -%氧樹脂加成物 、1.64 克(0.02 mole)2-甲基咪唑、3.85 克 34 201120085 (〇.=當量）的DER™332、7 6克庚烧和43克匪κ，使 用貝施例13之過程。反應在氬氣氣氛下以㈨rpm攪拌6 小時則又知4.95克(82.3%產率）的粒子。一小滴的分散 物被MIBK稀釋’塗在上，在室溫於真空中乾燥。 將乾燥後，樣品濺鍍一層薄薄的黃金，並使用肠咖 S-2働N掃描式電子顯微鏡取得掃描電子顯微照片（圖工和 圖2)。 貫施例23 ’從2-曱基咪唑、DGEBA、和HyPox™ RK 84(23)合成未封裝核粒子。 未封裝核粒子23係合成自〇·5ΐ克的實施例2之CTBN-環氧樹脂加成物、1_64克(0.02 m〇le)2-曱基咪唑、3.85克 (0.〇22當量）的DER™332、7.6克庚烷和42克的MIBK， 使用λ施例13之過程。反應在氬氣氣氛下以1〇〇〇印爪授 拌16小時，以獲得4.49克(74,7%產率）的粒子。 未封裝核粒子的封裝實例： 實施例24 ’從2-曱基咪唑、DGEBA、HyPox™ RK 84、 和MDI(24)封裝粒子。 微囊核係合成自0.52克的實施例2之CTBN-環氧樹脂 加成物、1·64克(0.02 mole)2-甲基咪唑、3.85克(0.022當量) 的DERTM332、7.6克庚烷和42克的MIBK，使用實施例 13之過程。反應在氬氣氣氛下以1〇〇〇 rpm攪拌6小時。一 小滴的分散物被MIBK稀釋，塗在玻璃片上，在室溫於真 35 201120085 空中乾燥。將乾燥後之樣品賊_層薄薄的黃金，並使用 Hitachi S-2460N掃描式電子顯微鏡取得掃描電子顯微照 片。封裝之開始係藉由添加156克（〇〇125當量）4,4，_亞 甲雙（笨基異氰酸醋），最常見的被稱為Mm，和141克 MIBK ’在110分鐘過財滴加，之後反應在氬氣氣氛下在 1〇〇〇 rpm攪拌15小時。一小滴的分散物被乾燥，且其紅外 光譜(FT-IR)顯示異氰酸酯基團完全轉化。確認所有的異氰 酸酯已消耗後，一小滴的分散物被MIBK稀釋，塗在玻璃 片上，在室溫於真空中乾燥。將乾燥後之樣品濺鑛一層薄 溥的汽金，並使用Hitachi S-2460N掃描式電子顯微鏡取得 掃描電子顯微照片（圖3和圖4)。 實施例25 ’從2-曱基咪唑、DGEBA、HyPoxTM RK 84、 MDI和4,4’-亞甲雙（N，N-環氧丙基苯胺）（25)合成微囊。 微囊核係合成自0.51克的實施例2之CTBN-環氧樹脂 加成物、1.64 克（0.02 mole) 2-甲基咪唑、3.85 克（0.022 當量）的DER™332、7.6克庚烷和42克的MIBK，使用實 施例13之過程。反應在氬氣氣氛下以1000 rpm攪拌6小 時。封裴之開始係藉由添加1.4克（0.0112當量）MDI，0.16 克（0.00038當量）4,4，-亞曱雙（N，N-環氧丙基苯胺），和 14.1克MIBK，在110分鐘過程中滴加，之後反應在氬氣 氣氛下在1000 rpm攪拌15小時。一小滴的分散物被乾燥， 且其紅外光譜顯示異氰酸酯基團完全轉化。 36 201120085 實施例26 ’從2-曱基咪唑、DGEBA、HyPoxTM RK 84、 和MDI(26)合成微囊。 微囊核係合成自0.52克的實施例2之CTBN-環氧樹脂 加成物、I.64克(〇.〇2 m〇ie)2_曱基咪唑、3⑽克(〇 〇22當量) 的DER™332、7.6克庚烷和42克的MIBK，使用實施例 13之過私。反應在氬氣氣氛下以叩爪攪拌6 ^、時。封 裂之開始係藉由添加157克（〇.〇125當量）Mm，和141 克MIBK，在90分鐘過程中滴加，之後反應在氬氣氣氛下 在1000 rpm攪拌15小時。一小滴的分散物被乾燥，且其 紅外光譜顯示異氰酸酯基圑完全轉化。 實施例27 ’從2-曱基咪唑、DGEBA、HyPoxTM RK 84 的MDI和4,4’-亞曱雙(N，N-環氧丙基苯胺)(27)合成微囊。 微囊核係合成自〇·52克的實施例2之CTBN-環氧樹脂 力口成物、1.64克(〇.〇2 mole)2-曱基咪唑、3_85克(0.022當量） 的DERTM332、7.6克庚烷和43克MIBK，使用實施例13 之過程。反應在氬氣氣氛下以1000 rpm攪拌6小時。封裝 之開始係藉由添加2.8克（0.0223當量）的MDI(Sigma Aldrich公司的產品），0.35克(0.0033當量)4,4，-亞曱雙(Ν,Ν-壤氧丙基苯胺)和14.1克MIBK的溶液，在240分鐘過程中 滴加’之後反應在氬氣氣氛下在1000 rpm攪拌15小時。 實施例28 ’從2-曱基咪唑、DGEBA、HyPox™ RK 84、 MDI、和4,4’-亞甲雙(N，N_環氧丙基苯胺)(28)合成微囊。 37 201120085 具有PTFE氟聚合半月形頂置式攪拌器、迴流冷凝器、 加料漏斗及氬氣入口之三頸圓底燒瓶加入1.03克的實施例 2之CTBN-環氧樹脂加成物、3.28克(0.04 mole)2-甲基°米 唑、15_2克庚烷和76克4-甲基-2«·戊酮(MIBK)。該反應器 被置於80°C浴，並吹入氬氣。於1小時後，7.7克(0.044 當量)DER™ 332(Dow Chemical 公司之產品）與 7.7 克 MIBK 之溶液歷時40分鐘以液滴方式添加，之後反應係在氬氣氣 氛下以1000卬m攪拌6小時。形成白色乳狀分散物。一小 滴的分散物被稀釋，塗在玻璃片上，在室溫於真空中乾燥。 將乾燥後之樣品賤鑛一層薄薄的黃金，並取得掃描電子顯 微照片。封裝之開始係藉由添加2.8克(0.0223當量)MDI， 0.32克(0.003當量)4,4’-亞曱雙(N，N-環氧丙基苯胺），和28.2 克MIBK之溶液，在240分鐘過程中滴加，之後反應在氬 氣氣氛下在1000 rpm擾拌12.5小時。 實施例 29,從 2-曱基咪唑、DGEBA、HyPox丁MRK 84L、 Desmodur®W'和4,4’-亞曱雙(N，N-環氧丙基苯胺)(29)合成 微囊。 具有PTFE氟聚合半月形頂置式攪拌器、迴流冷凝器、 加料漏斗及氬氣入口之三頸圓底燒瓶加入2.09克的實施例 2之CTBN-環氧樹脂加成物、6.56克(0.08 mole)2-曱基p米唾 和183克4-甲基-2-戊酮(MIBK)。該反應器被置於80°C浴， 並吹入氬氣。於1小時後，15.4克(0.088當量）的DER™332 (二環氧丙基醚雙酚(DGEBA)購自Dow Chemical公司）和 38 201120085 18·7克的MIBK之溶液歷時1小時以液滴方式添加，之後 反應係在氬氣氣氛下以1000 rpm授拌6小時。形成白色乳 狀分散物。粒子受到重力而沉澱，藉由傾析去除上清液。 這些粒子被重新分散在]V1IBK中。殘餘分散物被過濾、通過 小型孔徑膜過濾器。這些粒子被重新分散在MIBK中，然 後過濾通過30/zm孔徑過濾器，以移除大尺寸粒子和黏聚 物。數滴所產生之分散物被乾燥，以金濺鍍，載入掃描電 子顯微鏡(SEM)。其顯微照片顯示粒子都有足夠品質允許繼 續進行到封裝步驟。分散物之固體含量測定為9 84% (w/w)。總分散物之產量為84.4克。 具有PTFE氟聚合半月形頂置式擾拌器、迴流冷凝器、 加料漏斗及氬氣入口之三頸圓底燒瓶加入0.83克的實施例 2之CTBN-環氧樹脂加成物ι〇·3克的MIBK，及經純化 過的分散物。δ亥反應器被置於80°C浴，並吹入1氣。對此 歷時1小時以液滴方式添加17克庚烧。封裝之開始係藉由 添加1.9克(0.0145當量)Desmodur®W(液體脂環二異氰酸 酉旨，購自 Bayer MaterialScience 公司），〇 19 克（〇〇〇2 當 量)4,4’-亞甲雙(N，N-環氧丙基苯胺），和18.9克MIBK之溶 液，在4小時過程中滴加，之後反應在氬氣氣氛下在1〇〇〇 rpm攪拌12.5小時。 實施例30(預示性）’合成由兩殼材料所組成之微囊 具有PTFE氟聚合半月形頂置式擾拌器、迴流冷凝器、 加料漏斗及氬氣入口之三頸圓底燒瓶加入2.09克的實施例 39 201120085 2之CTBN-環氧樹脂加成物、6.56克(0.08 mole)2-曱基〇米π坐 和183克4-甲基-2-戊酮(ΜΙΒΚ)。該反應器被置於8(TC浴， 並吹入氬氣。經過1小時，15.4克(0.088當量）的DER™332 (Dow Chemical公司之產品）和18.7克MIBK之溶液歷時1 小時以液滴方式添加，之後反應係在氬氣氣氛下以1〇〇〇 rpm攪拌6小時。形成白色乳狀分散物。粒子受到重力而 沉澱，藉由傾析去除上清液。這些粒子被重新分散在MIBK 中。殘餘分散物被過濾通過小型孔徑膜過濾器。這些粒子 被重新分散在MIBK中，然後過濾通過30/zm孔徑過濾 器’以移除大尺寸粒子和黏聚物。 具有PTFE氟聚合半月形頂置式攪拌器、迴流冷凝器、 加料漏斗及氬氣入口之三頸圓底燒瓶加入0.83克的實施例 2之CTBN-環氧樹脂加成物，10.3克的MIBK，及經純化 過的分散物。該反應器被置於80°C浴，並吹入氬氣。對此 歷時1小時以液滴方式添加17克庚烧。封裝之開始係藉由 添力σ 1.9 克（0.0145 當量）Desmodur®W(Bayer Material Science公司之產品），0.19克(0.002當量)4,4，-亞曱雙(n，N-環氧丙基苯胺），和18.9克MIBK之溶液，在4小時過程中 滴加’之後反應在氬氣氣氛下在1000 i：pm攢;拌12.5小時。 第二殼層之形成是藉由添加1.9克（0.0145當 量）Desmodur®W(Bayer MaterialSdence 公司之產品），019 克(0.002當量)4,4’-亞甲雙(N，N-環氧丙基苯胺），和18.9克 MIBK之溶液，在4小時過程中滴加，之後反應在氬氣氣 氛下在1000 rpm攪拌12.5小時。 201120085 貝施例31 (預示性）’合成由兩殼材料所組成之微囊， 其中最外層殼材料是由環氧樹脂相容材料所組成。 具有PTFE氟聚合半月形頂置式攪拌器、迴流冷凝器、 加料漏斗及氬氣入口之三頸圓底燒瓶加入2 〇9克的實施例 2之CTBN•環氧樹脂加成物、6.56克(0.08mole)2-甲基η米唆 和183克4-甲基-2-戊酮(ΜΙΒΚ)。該反應器被置於8〇t浴， 並吹入氬氣。經過1小時，15·4克(0.088當量）的DERTM332 (Dow Chemical公司之產品）和18.7克MIBK之溶液歷時1 小時以液滴方式添加，之後反應係在氬氣氣氛下以1〇〇〇 rpm攪拌6小時。形成白色乳狀分散物。粒子受到重力而 沉澱，藉由傾析去除上清液。這些粒子被重新分散在 中。殘餘分散物被過濾通過小型孔徑膜過濾器。這些粒子 被重新分散在MIBK中，然後過濾通過30/zm孔徑過濾 裔’以移除大尺寸粒子和黏聚物。 具有PTFE氟聚合半月形頂置式攪拌器、迴流冷凝器、 加料漏斗及氬氣入口之三頸圓底燒瓶加入0.83克的實施例 2之CTBN-環氧樹脂加成物’ 10.3克的MIBK，及經純化 過的分散物。該反應器被置於80°C浴，並吹入氬氣。對此 歷時1小時以液滴方式添加17克庚烷。第一殼層封裝之開 始係藉由添加1.9克（0.0145當量）Desmodur®W(Bayer MaterialScience 公司之產品），0.19 克（0.002 當量）4,4，-亞甲 雙(N，N-環氧丙基苯胺），和18.9克MIBK之溶液，在4小 時過程中滴加，之後反應在氬氣氣氛下在1〇〇〇 rpin攪拌 12.5小時。 41 201120085 第二殼層之形成是藉由添加1.9克（〇.〇145當 量）Desmodur®W(Bayer MaterialScience 公司之產品），1 9 克 CVC Thermoset Materials HyPoxTM RA1340，和 18 9 克 MIBK之溶液，在4小時過程中滴加，之後反應在氬氣氣 氛下在1000 i*pm擾拌12.5小時。 實施例32(預示性）’合成由兩殼材料所組成之微囊， 其中最外層殼材料是由環氧樹脂相容材料所組成。 具有PTFE氟聚合半月形頂置式攪拌器、迴流冷凝器、 加料漏斗及氬氣入口之三頸圓底燒瓶加入2 〇9克的實施例 2之CTBN·環氧樹脂加成物、6.56克(0.08m〇le)2_曱基〇米哇 和183克4-曱基-2-戊酮(ΜΙΒΚ)。該反應器被置於8〇t：浴， 並吹入氬氣。經過1小時，15.4克（0.088當量）的Dertm332 (Dow Chemical公司之產品)和18.7克奶驭之溶液歷時i 小時以液滴方式添加，之後反應係在氬氣氣氛下以1〇〇〇 rpm攪拌6小時。形成白色乳狀分散物。粒子受到重力而 沉澱，藉由傾析去除上清液。這些粒子被重新分散在MffiK 中。殘餘分散物被過濾通過小型孔徑膜過濾器。這些粒子 ，重新分散在MIBK中，然後過濾通過3〇/Zm孔彳;過濾 器以移除大尺寸粒子和黏聚物。 具有PTFE氟聚合半月形頂置式攪拌器、迴流冷凝器、 加料漏斗及氬氣人口之三頸圓底燒瓶加人G 83克的實施例 2之CTBN-環氧樹脂加成物，1〇 3克的MmK，及經純化 過的分散物。該反應器被置於肋它浴，並吹入氬氣。對此 42 201120085 歷時1小時以液滴方式添加17克庚烧。封裝之開始係藉由 添加 1.9 克（0.0145 當量）的 Desmodur®W(Bayer Material Science公司之產品）’ 0.19克(0.002當量)4,4，-亞甲雙(Ν,Ν-環氧丙基苯胺)和18.9克ΜΙΒΚ之溶液，在4小時過程中滴 加’之後反應在氬氣氣氛下在1〇〇〇 rpm攪拌12.5小時。 第二殼層之形成是藉由添加1.9克（0.0145當量）的罝) DER μ 332 (product of D〇w Chemical Co., Ltd.) and 3.5 g of MIBK solution were added in droplets over 15 minutes, after which the reaction was stirred at 300 rPm for 1 hour under an argon atmosphere and continued for 1 hour. Stir at rpm for 5 hours. Open &gt; into a white milky dispersion. The dispersion was released from the reactor, centrifuged, washed with Mib' and evaporated to dryness to obtain 4.53 g (80% yield) of particles. Example 19 'Unpackaged core particles were synthesized from 2-methylimidazole, DGEBA, and HyP〇xTMRK 84 (19). The unpackaged core particles 19 were synthesized from 0.51 g of the CTBN-epoxy resin adduct of Example 2, 1.64 g (0.02 mole) of 2-methylimidazole, and 3.5 g (〇.〇2 33 201120085 equivalent) of DERTM. The procedure of Example 13 was used for 332 and 51 g of MIBK. The reaction was stirred at 1500 rpm for 6 hours under a chlorine atmosphere to obtain 4.05 g (71.5% yield) of particles. Example 20, unpackaged core particles were synthesized from 2-methylimidazole, DGEBA, and HyPoxTM RK 84 (20). The unpackaged core particles 20 were synthesized from 0.52 g of the CTBN-epoxy resin adduct of Example 2, 1.64 g of 2-mercaptoimidazole, 3.5 g (0.02 equivalent) of DERTM 332, 7.6 g heptane and 43 g MIBK were used in the procedure of Example 。. The reaction was stirred at 1 〇〇〇rpin for 6 hours under an argon atmosphere to obtain 4.05 g (71.5% yield) of particles. Example 21, from 2-mercaptoimidazole, DGEBA., and HyPoxTM RK 84 (2Ό synthetic unencapsulated core particles. Unencapsulated core particle 21 was synthesized from 0.51 g of the CTBN-epoxy resin adduct of Example 2 '1.65克 (0.02 mole) 2-mercaptoimidazole, 3.5 g (0.02 equivalent) of DERTM 332, 7.6 g heptane and .43 g MIBK, using the procedure of Example 13. The reaction was stirred at 1 rpm under an argon atmosphere. 16 hours, to obtain 3.6 grams (64% yield) of particles. Example 22, synthesis of non-core particles from 2-mercaptoimidazole, DGEBA, and HyPoxTM RK 84 (22). Synthetic from 〇. 51 g of CTBN -% oxy-resin adduct of Example 2, 1.64 g (0.02 mole) of 2-methylimidazole, 3.85 g of 34 201120085 (〇.= equivalent) of DERTM 332, 7 6 g Geng and 43 g of 匪, using the procedure of Example 13. The reaction was stirred at (9) rpm for 6 hours under an argon atmosphere, and 4.95 g (82.3% yield) of particles were also known. A small droplet of the dispersion was diluted by MIBK. 'Coated on and dried in vacuum at room temperature. After drying, the sample was sputtered with a thin layer of gold and taken using a bowel S-2働N scanning electron microscope. Scanning electron micrographs (Fig. 2 and Fig. 2). Example 23 'Synthesis of unencapsulated core particles from 2-mercaptoimidazole, DGEBA, and HyPoxTM RK 84 (23). Unencapsulated core particles 23 synthesized from 〇 5 gram of the CTBN-epoxy resin adduct of Example 2, 1 to 64 grams (0.02 m〇le) of 2-mercaptoimidazole, 3.85 g (0.22 equivalents) of DERTM 332, 7.6 g of heptane and 42 g of MIBK, using the procedure of λ Example 13. The reaction was stirred for 16 hours under a argon atmosphere with 1 〇〇〇 of the paws to obtain 4.49 g (74,7% yield) of particles. Package Example: Example 24 'Package of particles from 2-mercaptoimidazole, DGEBA, HyPoxTM RK 84, and MDI (24). Microcapsule core was synthesized from 0.52 g of CTBN-epoxy resin addition of Example 2. 1, 1.6 g (0.02 mole) of 2-methylimidazole, 3.85 g (0.022 equivalent) of DERTM 332, 7.6 g of heptane and 42 g of MIBK, using the procedure of Example 13. The reaction was carried out under an argon atmosphere. Stir at rpm for 6 hours. A small drop of the dispersion was diluted with MIBK, applied to a glass slide, and dried in the air at room temperature on true 35 201120085. The dried sample thief _ thin layer of gold Scanning electron micrographs were taken using a Hitachi S-2460N scanning electron microscope. The package begins by adding 156 grams (〇〇125 equivalents) of 4,4,_methylene double (stupyl isocyanate), the most common known as Mm, and 141 grams of MIBK' in the 110 minutes. After the dropwise addition, the reaction was stirred at 1 rpm for 15 hours under an argon atmosphere. A small droplet of the dispersion was dried and its infrared spectrum (FT-IR) showed complete conversion of the isocyanate groups. After confirming that all of the isocyanate has been consumed, a small droplet of the dispersion is diluted with MIBK, applied to a glass slide, and dried in vacuum at room temperature. The dried sample was splashed with a thin layer of vapor and a scanning electron micrograph was taken using a Hitachi S-2460N scanning electron microscope (Figs. 3 and 4). Example 25 'Microcapsules were synthesized from 2-mercaptoimidazole, DGEBA, HyPoxTM RK 84, MDI and 4,4'-methylenebis(N,N-epoxypropylaniline) (25). The microcapsule core was synthesized from 0.51 g of the CTBN-epoxy resin adduct of Example 2, 1.64 g (0.02 mole) of 2-methylimidazole, 3.85 g (0.022 equivalent) of DERTM 332, 7.6 g of heptane and For the 42 g of MIBK, the procedure of Example 13 was used. The reaction was stirred at 1000 rpm for 6 hours under an argon atmosphere. The start of the seal was carried out by adding 1.4 g (0.0112 equivalent) of MDI, 0.16 g (0.00038 equivalent) of 4,4,-arylene bis(N,N-epoxypropylaniline), and 14.1 g of MIBK in 110 minutes. The mixture was added dropwise, and the reaction was stirred at 1000 rpm for 15 hours under an argon atmosphere. A small droplet of the dispersion was dried and its infrared spectrum showed complete conversion of the isocyanate groups. 36 201120085 Example 26 'Microcapsules were synthesized from 2-mercaptoimidazole, DGEBA, HyPoxTM RK 84, and MDI (26). The microcapsule core was synthesized from 0.52 g of the CTBN-epoxy resin adduct of Example 2, I.64 g (〇.〇2 m〇ie) 2_mercaptoimidazole, 3 (10) g (〇〇22 equivalent) DERTM 332, 7.6 grams of heptane and 42 grams of MIBK were used in the privacy of Example 13. The reaction was stirred at 6 ^ with a paw under an argon atmosphere. The initiation of the cleavage was carried out by adding 157 g (〇.〇125 eq.) of Mm, and 141 g of MIBK over a period of 90 minutes, after which the reaction was stirred at 1000 rpm for 15 hours under an argon atmosphere. A small droplet of the dispersion was dried and its infrared spectrum showed complete conversion of the isocyanate group. Example 27 'Microcapsules were synthesized from 2-mercaptoimidazole, DGEBA, HyPoxTM RK 84 MDI and 4,4'-arylene bis(N,N-epoxypropylaniline) (27). The microcapsule core was synthesized from 52 g of the CTBN-epoxy resin of Example 2, 1.64 g of 2-mercaptoimidazole, 3 to 85 g (0.022 equivalent) of DERTM 332, 7.6. The procedure of Example 13 was used for kepeptane and 43 g of MIBK. The reaction was stirred at 1000 rpm for 6 hours under an argon atmosphere. The package was started by adding 2.8 g (0.0223 equivalents) of MDI (product of Sigma Aldrich), 0.35 g (0.0033 equivalents) of 4,4,-arylene (Ν, Ν-Lv propyl aniline) and 14.1. The solution of gram MIBK was added dropwise during the course of 240 minutes, after which the reaction was stirred at 1000 rpm for 15 hours under an argon atmosphere. Example 28 'Microcapsules were synthesized from 2-mercaptoimidazole, DGEBA, HyPoxTM RK 84, MDI, and 4,4'-methylenebis(N,N-epoxypropylaniline) (28). 37 201120085 A three-necked round bottom flask with a PTFE fluoropolymerized half-moon overhead stirrer, reflux condenser, addition funnel and argon inlet was charged with 1.03 g of the CTBN-epoxy resin adduct of Example 2, 3.28 g (0.04). Mole) 2-methyl-pyromazole, 15-2 g heptane and 76 g 4-methyl-2«-pentanone (MIBK). The reactor was placed in a bath at 80 ° C and argon gas was blown in. After 1 hour, 7.7 g (0.044 equivalent) of DERTM 332 (product of Dow Chemical Co.) and 7.7 g of MIBK were added dropwise in 40 minutes, after which the reaction was stirred at 1000 μm under an argon atmosphere. hour. A white milky dispersion is formed. A small amount of the dispersion was diluted, applied to a glass slide, and dried in a vacuum at room temperature. The dried sample is mined with a thin layer of gold and a scanning electron micrograph is taken. The package was started by adding 2.8 g (0.0223 equivalents) of MDI, 0.32 g (0.003 equivalents) of 4,4'-arylene bis(N,N-epoxypropylaniline), and 28.2 g of MIBK solution at 240 It was added dropwise during the minute, and then the reaction was spoiled at 1000 rpm for 12.5 hours under an argon atmosphere. Example 29 Synthesis of microcapsules from 2-mercaptoimidazole, DGEBA, HyPox-butyl MRK 84L, Desmodur® W' and 4,4'-arylene bis(N,N-epoxypropylaniline) (29). A three-necked round bottom flask with a PTFE fluoropolymerized half-moon overhead stirrer, reflux condenser, addition funnel and argon inlet was charged with 2.09 g of the CTBN-epoxy resin adduct of Example 2, 6.56 g (0.08 mole). 2-mercapto p-saliva and 183 g 4-methyl-2-pentanone (MIBK). The reactor was placed in a bath at 80 ° C and argon gas was blown in. After 1 hour, 15.4 g (0.088 equivalents) of DERTM 332 (diepoxypropyl ether bisphenol (DGEBA) from Dow Chemical) and 38 201120085 18·7 g of MIBK solution were taken for 1 hour to droplets. The mode was added, after which the reaction was stirred at 1000 rpm for 6 hours under an argon atmosphere. A white milky dispersion is formed. The particles are precipitated by gravity and the supernatant is removed by decantation. These particles are redispersed in the [V1IBK]. The residual dispersion was filtered through a small pore size membrane filter. The particles were redispersed in MIBK and then filtered through a 30/zm pore size filter to remove large size particles and cohesives. The dispersion produced by the droplets was dried, sputtered with gold, and loaded into a scanning electron microscope (SEM). Its photomicrograph shows that the particles are of sufficient quality to allow for the encapsulation step. The solids content of the dispersion was determined to be 9 84% (w/w). The total dispersion yield was 84.4 grams. A three-necked round bottom flask with a PTFE fluoropolymerized half-moon top-mounted scrambler, reflux condenser, addition funnel and argon inlet was charged with 0.83 g of the CTBN-epoxy resin adduct of Example 2, ι·3 g. MIBK, and purified dispersion. The δH reactor was placed in a bath at 80 ° C and blown into a gas. For this, 17 g of heptane was added in droplets over 1 hour. The package was started by adding 1.9 g (0.0145 equivalents) of Desmodur® W (liquid alicyclic diisocyanate, available from Bayer MaterialScience), 〇19 g (〇〇〇2 eq.) 4,4'- A solution of methyl bis(N,N-epoxypropylaniline) and 18.9 g of MIBK was added dropwise over a period of 4 hours, after which the reaction was stirred at 1 rpm for 12.5 hours under an argon atmosphere. Example 30 (predictive) 'Synthesis of a microcapsule composed of a two-shell material having a PTFE fluoropolymerized half-moon overhead scrambler, a reflux condenser, an addition funnel, and an argon inlet three-necked round bottom flask was added to 2.09 g. Example 39 CTBN-epoxy resin adduct of 201120085 2, 6.56 g (0.08 mole) of 2-mercapto quinone π sitting and 183 g of 4-methyl-2-pentanone (oxime). The reactor was placed in a 8 (TC bath and blown with argon. After 1 hour, 15.4 g (0.088 equivalents) of DERTM 332 (product of Dow Chemical) and 18.7 g of MIBK were treated as droplets over 1 hour. The mode was added, after which the reaction was stirred at 1 rpm for 6 hours under an argon atmosphere to form a white milky dispersion. The particles were precipitated by gravity, and the supernatant was removed by decantation. These particles were redispersed in MIBK. The residual dispersion was filtered through a small pore size membrane filter. The particles were redispersed in MIBK and then filtered through a 30/zm pore size filter to remove large size particles and binders. A three-necked round bottom flask with overhead stirrer, reflux condenser, addition funnel and argon inlet was charged with 0.83 g of the CTBN-epoxy resin adduct of Example 2, 10.3 g of MIBK, and the purified dispersion. The reactor was placed in a bath at 80 ° C and argon gas was blown in. This was added dropwise 17 g of heptane in 1 hour. The beginning of the encapsulation was by adding force σ 1.9 g (0.0145 eq.) Desmodur® W (Bayer Material Science Product), 0.19 g (0.002 equivalent) of 4,4,-arylene bis(n,N-epoxypropyl aniline), and 18.9 g of MIBK solution, added dropwise during 4 hours 'after reaction in argon atmosphere The next shell was formed at 1000 i:pm; 12.5 hours. The second shell was formed by adding 1.9 g (0.0145 equivalent) of Desmodur® W (product of Bayer MaterialSdence), 019 g (0.002 equivalent) 4,4'- A solution of methylene bis(N,N-epoxypropyl aniline) and 18.9 g of MIBK was added dropwise over a period of 4 hours, after which the reaction was stirred at 1000 rpm for 12.5 hours under an argon atmosphere. Predictive) 'Synthesis of microcapsules composed of two shell materials, wherein the outermost shell material is composed of epoxy resin compatible material. PTFE fluoropolymerized half moon overhead stirrer, reflux condenser, addition funnel and argon A three-necked round bottom flask with a gas inlet was charged with 2 〇 9 g of the CTBN• epoxy resin adduct of Example 2, 6.56 g (0.08 mole) of 2-methyl η methane and 183 g of 4-methyl-2- Pentanone (ΜΙΒΚ). The reactor was placed in a 8 Torr bath and argon was blown in. After 1 hour, 5.4 g (0.088 equivalent) of DERTM 33 A solution of 2 (product of Dow Chemical Co., Ltd.) and 18.7 g of MIBK was added dropwise in 1 hour, and then the reaction was stirred at 1 rpm for 6 hours under an argon atmosphere to form a white emulsion dispersion. Precipitate by gravity, and the supernatant was removed by decantation. These particles are redistributed in the middle. The residual dispersion was filtered through a small pore size membrane filter. These particles were redispersed in MIBK and then filtered through a 30/zm pore size filter to remove large size particles and cohesives. A three-necked round bottom flask having a PTFE fluoropolymerized half-moon overhead stirrer, a reflux condenser, an addition funnel, and an argon inlet was charged with 0.83 g of the CTBN-epoxy resin adduct of Example 2, 10.3 g of MIBK, and The purified dispersion. The reactor was placed in a bath at 80 ° C and argon gas was blown in. For this, 17 g of heptane was added dropwise in 1 hour. The first shell package was started by adding 1.9 grams (0.0145 equivalents) of Desmodur® W (product of Bayer MaterialScience), 0.19 grams (0.002 equivalents) of 4,4,-methylene bis (N, N-epoxy propylene). A solution of phenylaniline) and 18.9 g of MIBK was added dropwise over a period of 4 hours, after which the reaction was stirred at 1 〇〇〇rpin for 12.5 hours under an argon atmosphere. 41 201120085 The second shell was formed by adding 1.9 g (〇.〇145 equivalent) Desmodur® W (product of Bayer MaterialScience), 19 g CVC Thermoset Materials HyPoxTM RA1340, and 18 9 g MIBK solution. The addition was carried out during 4 hours, after which the reaction was spoiled at 1000 i*pm for 12.5 hours under an argon atmosphere. Example 32 (Prophetic) 'Synthesis is a microcapsule composed of a two-shell material, wherein the outermost shell material is composed of an epoxy compatible material. A three-necked round bottom flask with a PTFE fluoropolymerized half-moon overhead stirrer, reflux condenser, addition funnel and argon inlet was added to 2 〇 9 g of the CTBN·epoxy resin adduct of Example 2, 6.56 g (0.08). M〇le) 2_曱基〇米哇 and 183 grams of 4-mercapto-2-pentanone (ΜΙΒΚ). The reactor was placed in a 8 Torr bath and argon gas was blown in. After 1 hour, 15.4 g (0.088 equivalent) of Dertm332 (product of Dow Chemical Co.) and 18.7 g of milk thistle were added in droplets over a period of 1 hour, after which the reaction was stirred at 1 rpm under an argon atmosphere. 6 hours. A white milky dispersion is formed. The particles are precipitated by gravity, and the supernatant is removed by decantation. These particles are redispersed in MffiK. The residual dispersion was filtered through a small pore size membrane filter. These particles are redispersed in MIBK and then filtered through a 3 Å/Zm pore enthalpy; a filter to remove large size particles and cohesives. A three-necked round bottom flask with a PTFE fluoropolymerized half-moon overhead stirrer, reflux condenser, addition funnel and argon population plus a G 83 gram of CTBN-epoxy resin adduct of Example 2, 1 〇 3 g MmK, and purified dispersion. The reactor was placed in a rib bath and argon gas was blown. For this, 42 201120085, 17 grams of heptane was added in droplets over 1 hour. The package was started by adding 1.9 g (0.0145 eq.) of Desmodur® W (product of Bayer Material Science) '0.19 g (0.002 eq.) 4,4,-methylenebis(indole, oxime-epoxypropylaniline) And 18.9 g of a solution of hydrazine, which was added dropwise during 4 hours, after which the reaction was stirred at 1 rpm for 12.5 hours under an argon atmosphere. The second shell was formed by adding 1.9 grams (0.0145 equivalents)

Desmodur®W(Bayer MaterialScience 公司的產品），1·9 克Desmodur® W (product of Bayer MaterialScience), 1.9 g

Toagosei的GP-3〇l接枝聚丙烯酸酯，〇 19克(〇 〇〇2當量) 4,4’-亞曱雙(N，N-環氧丙基笨胺），和18.9克MIBK 之溶液， 在4小時過程中滴加，之後反應在氬氣氣氛下在1〇〇〇rpm 攪拌12.5小時。 母粒製備之實例： 實施例33，從實施例24粒子製備母粒 實施例24粒子之分散物在贼真空條件下蒸發，以 獲得育色固體’用臼和杵研磨，並加人雙齡A之二環氧丙 基醚，以粒子相對於環氧樹脂比率35:65(w/w)。混合物使 用二輥軋機分散20分鐘，取得奶油狀黃色分散物。 實施例34，從實施例28粒子製備母粒 在室溫下，1〇克的雙酚A之二環氧丙基醚加入到實施 例28之反應混合物，其中含有分散的粒子，並授拌3小時。 在31°C真錄態下去除料丨至隨含量86%(w/w)。自此 移除12.86克’並和額外的7 9〇克的雙紛A的二環氧丙基 43 201120085 醚混合。混合物進一步使用三輥軋機處理3分鐘，以獲得 奶油狀黃色分散物。 性能測試結果： 針對耐溶劑性試驗，製備了結合粒子、雙紛A的二環 氧丙基醚和MIBK之混合物’比率為4:50:46(w/w)。然後 混合物放置在40°C油浴及目視觀察黏度之改變。結果如下 表丨°幾等分的上述混合物被塗在玻璃片形成薄膜並於室 '服在真空中乾燥。使用TA Instruments Q10的差示掃描量熱 ，獲彳于DSC執跡’使用之溫度範圍為3〇至25〇c»c，升溫速 率5°C/分鐘，並於氮氣氣氛下進行。結果如下表！。 耐溶劑性和DSC結果： 粒子Toagosei's GP-3〇l grafted polyacrylate, 19 g (〇〇〇2 equivalent) of 4,4'-arylene bis(N,N-epoxypropyl strepamine), and 18.9 g of MIBK solution It was added dropwise during 4 hours, after which the reaction was stirred at 1 rpm for 12.5 hours under an argon atmosphere. Example of Masterbatch Preparation: Example 33, Preparation of Masterbatch from Example 24 Particles The dispersion of the particles of Example 24 was evaporated under vacuum in a thief to obtain a coloring solid 'grinded with hydrazine and hydrazine, and added to a double age A Di-epoxypropyl ether, in a ratio of particles to epoxy resin of 35:65 (w/w). The mixture was dispersed by a two-roll mill for 20 minutes to obtain a creamy yellow dispersion. Example 34, Preparation of Masterbatch from Example 28 Particles At room temperature, 1 gram of diglycidyl ether of bisphenol A was added to the reaction mixture of Example 28, containing dispersed particles, and mixing 3 hour. The crucible was removed to a content of 86% (w/w) at a true recording state of 31 °C. From this time, 12.86 g was removed and mixed with an additional 7 9 g of di-di-A diepoxypropyl 43 201120085 ether. The mixture was further treated with a three-roll mill for 3 minutes to obtain a creamy yellow dispersion. Performance test results: For the solvent resistance test, a mixture of particles, a mixture of dicyclooxypropyl ether and MIBK was prepared at a ratio of 4:50:46 (w/w). The mixture was then placed in a 40 ° C oil bath and the change in viscosity was visually observed. The results are as follows. The above mixture, which is aliquoted, is applied to a glass sheet to form a film and dried in a chamber under vacuum. Using a differential scanning calorimetry of TA Instruments Q10, the temperature range used was from 3 Å to 25 〇 c»c, and the rate of temperature rise was 5 ° C / min, and was carried out under a nitrogen atmosphere. The results are as follows! . Solvent resistance and DSC results: Particles

耐溶劑性 凝膠時間 (小時） DSC Tpeak ΔΗ (放熱，°c) (焦耳/克） 105 297 119 330 124 307 142 ~~—---— 200 124 &quot;-^- 218 對所 已&gt; …、特疋具體實施型態描述本發明的細節， 44 201120085 屬技術領域中具有通常知識者而言，不悖離下列申請專利 範圍之精神和範圍所進行的各種變化和修舞將是明顯的。 【圖式簡單說明】 圖1係顯示以兩保護殼材料封裝之核材料。在改良潛 伏性硬化劑相容性狀況下，保護殼2之組成物係經選擇以 包括環氧樹脂相容材料’而殼1之組成物係僅基於其阻隔 性能來選擇。 圖2是包括2-甲基咪唑、雙酚A(DGEBA)之二環氧丙 基鱗、以及從 CVC Thermoset Materials HyP〇xTM RX84 分 離出的CTBN-環氧樹脂加成物之球形核粒子之電子顯微照 片。 圖3是包括2-曱基咪嗤、雙驗A(DGEBA)之二環氧丙 基鱗、以及從 CVC Thermoset Materials HyP〇xTM RK84 分 離出的CTBN-環氧樹脂加成物之球形核粒子之電子顯微照 片’其中核粒子係以4,4’-亞曱雙（苯基異氰酸酯）(MDI)封 裝。 圖4是包括2-曱基咪唑、雙酚A(DGEBA)之二環氧丙 基醚、以及從 CVC Thermoset Materials HyPox™ RK84 分 離出的CTBN-環氧樹脂加成物之球形單一核粒子之電子顯 微照片。 圖5是CTBN-環氧樹脂加成物（c)的化學結構，羥基官 能化環氧樹脂（b)(如 CVC Thermoset Specialties HyPox RK84)係與CTBN(a) —起被用於合成。剩餘未反應之環氧樹 45 201120085 脂(b)在用作分散劑之(c)之前移除。 圖6是CTBN-環氧樹脂加成物(e)的化學結構，雙酚A 之二環氧丙基醚(d)(如 CVC Thermoset Specialties HyPox RA1340)係與CTBN(a)—起被用於合成。 【主要元件符號說明】 無 46Solvent-resistant gel time (hours) DSC Tpeak ΔΗ (exothermic, °c) (Joules/gram) 105 297 119 330 124 307 142 ~~----200 124 &quot;-^- 218 Pairs &gt; The details of the present invention are described in the detailed description of the present invention. 44 201120085 It is obvious to those of ordinary skill in the art that various changes and variations will be made without departing from the spirit and scope of the following claims. . BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a nuclear material encapsulated in two protective shell materials. In the case of improved latent hardener compatibility, the composition of the protective shell 2 is selected to include an epoxy compatible material' and the composition of the shell 1 is selected based solely on its barrier properties. 2 is an electron of a spherical core particle including a 2-methylimidazole, a bisphenol A (DGEBA) diepoxypropyl scale, and a CTBN-epoxy resin adduct separated from CVC Thermoset Materials HyP〇xTM RX84. micrograph. Figure 3 is a spherical nucleus of a CTBN-epoxy resin adduct separated from CVC Thermoset Materials HyP〇xTM RK84, including 2-mercaptopurine, double-test A (DGEBA) diepoxypropyl scales. Electron micrograph 'where the core particles are encapsulated in 4,4'-arylene bis(phenyl isocyanate) (MDI). Figure 4 is an electron of a spherical mononuclear particle comprising 2-mercaptoimidazole, bisphenol A (DGEBA) diepoxypropyl ether, and CTBN-epoxy resin adduct isolated from CVC Thermoset Materials HyPoxTM RK84 micrograph. Figure 5 is a chemical structure of the CTBN-epoxy resin adduct (c), and a hydroxyl functional epoxy resin (b) (e.g., CVC Thermoset Specialties HyPox RK84) is used in combination with CTBN (a). Remaining unreacted epoxy tree 45 201120085 The fat (b) is removed before it is used as a dispersing agent (c). Figure 6 is the chemical structure of the CTBN-epoxy resin adduct (e), and the diglycidyl ether of bisphenol A (d) (such as CVC Thermoset Specialties HyPox RA1340) is used together with CTBN(a). synthesis. [Main component symbol description] None 46

Claims (1)

201120085 七 申請專利範圍： .一種環氧樹脂之固化劑，其係包括下列各者之反應 物： 〜 0)胺，及 (b)環氧樹脂，以及 (C)彈性體-環氧樹脂加成物。 2·如申請專利範圍第1項之固化劑，其中該固化劑包含 下列各者之反應產物： (a)胺，及 碾軋樹脂 (c)羧基-封端之丁二烯_丙烯腈(CTBN)·環氧相 脂加成物。 3. 5. 5. =申請專鄕圍第2項之固化劑，其中該CTBN之 3量約為12-35重量％。 ； =凊專利範圍第2項之固化劑，其中該固化劑被开 =分散物之核相且粒子係被封裝在聚合物殼中。 利範圍第4項之固化劑，其中係藉由該粒」 氣酸酷之反〜步進方式形成二㈣ 化劑，其中係額外地心 =rr進方式形成二或更;:=化… 4子與多官能異氰_旨及多官能環氧樹脂相容t 201120085 物之反應而以步進方式形成二或更多之聚合物殼。 8. 如申請專利範圍第4項之固化劑，其中係額外地藉由 該粒子與多官能異氰酸酯及多官能環氧樹脂化合物及 環氧樹脂相容化合物之反應而以步進方式形成二或更 多之聚合物殼。 9. 一種包含環氧樹脂及固化劑之組成物，其中該固化劑 係下列各者之反應產物： (a) 胺，及 (b) 環氧樹脂，以及 (c) 彈性體-環氧樹脂加成物。 10. 如申請專利範圍第9項之組成物，其中該固化劑係下 列各者之反應產物： (a) .胺，及 (b) 環氧樹脂，以及 (c) 羧基-封端之丁二烯-丙烯腈（CTBN)-環氧樹 脂加成物。 11. 如申請專利範圍第10項之組成物，其中該CTBN之腈 含量約為12-35重量％。 12. —種藉由環氧樹脂黏著劑而黏貼至基板之電子組件， 其中該環氧樹脂黏著劑包含由下列各者之反應產物之 固化劑： (a) 胺，及 (b) 環氧樹脂，以及 (c) 彈性體-環氧樹脂加成物。 48 201120085 13. 如申請專利範圍第12項之電子組件，其中該電子組件 係構成電路板之一部分。 14. 如申請專利範圍第12項之電子組件，其中該電子組件 係藉由該環氧樹脂黏著劑而整合至基板之積體電路晶 片。 15. 如申請專利範圍第12項之電子組件，其中該電子組件 係藉由環氧樹脂黏著劑而黏貼至基板之半導體元件。 16. —種固定陣列之ACF，其包含以預定模式分散於黏著 劑膜中之金粒子，該黏著劑膜包含環氧樹脂黏著劑及 固化劑，其中該固化劑是胺、環氧樹脂、彈性體-環氧 樹脂加成物之反應產物。 17. 如申請專利範圍第16項之ACF，其中該組成物係經調 配以用於作為包含受保護的酚化合物之高Tg單組分 模塑料，其中該受保護的酚化合物包含芳基環氧丙基 碳酸醋基團。 18. 如申請專利範圍第Π項之ACF，其中該組成物係經調 配以用於作為片狀模塑料(SMC)、塊狀模塑料(BMC)、 或團狀模塑料(DMC)。 19. 如申請專利範圍第12項之電子組件，其中該電子組件 係形成電子顯示器。 49201120085 Seven patent application scope: An epoxy resin curing agent, which includes the following reactants: ~ 0) amine, and (b) epoxy resin, and (C) elastomer-epoxy resin addition Things. 2. The curing agent of claim 1, wherein the curing agent comprises the reaction product of: (a) an amine, and a rolling resin (c) a carboxyl-terminated butadiene-acrylonitrile (CTBN) ) · Epoxy phase fat adduct. 3. 5. 5. = Apply for the curing agent of item 2, wherein the amount of the CTBN is about 12-35 wt%. The curing agent of claim 2, wherein the curing agent is opened = the core phase of the dispersion and the particle system is encapsulated in the polymer shell. The curing agent of item 4 of the present invention, wherein the bismuth is formed by the sulphuric acid and the reverse stepping method, wherein the additional centroid=rr is formed into two or more;:==4 The polymer is formed in a stepwise manner with two or more polymer shells in accordance with the reaction of the polyfunctional isocyanide and the multifunctional epoxy resin. 8. The curing agent according to claim 4, wherein the curing agent is additionally formed in a stepwise manner by reacting the particles with a polyfunctional isocyanate and a polyfunctional epoxy resin compound and an epoxy resin compatible compound. More polymer shells. 9. A composition comprising an epoxy resin and a curing agent, wherein the curing agent is a reaction product of: (a) an amine, and (b) an epoxy resin, and (c) an elastomer-epoxy resin. Adult. 10. The composition of claim 9, wherein the curing agent is a reaction product of: (a) an amine, and (b) an epoxy resin, and (c) a carboxyl group-terminated dibutyl group Alkene-acrylonitrile (CTBN)-epoxy resin adduct. 11. The composition of claim 10, wherein the CTBN has a nitrile content of from about 12% to about 35% by weight. 12. An electronic component adhered to a substrate by an epoxy adhesive, wherein the epoxy adhesive comprises a curing agent of a reaction product of: (a) an amine, and (b) an epoxy resin And (c) an elastomer-epoxy resin adduct. 48 201120085 13. The electronic component of claim 12, wherein the electronic component forms part of a circuit board. 14. The electronic component of claim 12, wherein the electronic component is integrated into the integrated circuit chip of the substrate by the epoxy adhesive. 15. The electronic component of claim 12, wherein the electronic component is adhered to the semiconductor component of the substrate by an epoxy adhesive. 16. A fixed array of ACF comprising gold particles dispersed in a film in a predetermined pattern, the adhesive film comprising an epoxy resin adhesive and a curing agent, wherein the curing agent is an amine, an epoxy resin, and an elastic agent The reaction product of a bulk-epoxy resin adduct. 17. The ACF of claim 16, wherein the composition is formulated for use as a high Tg one-component molding compound comprising a protected phenolic compound, wherein the protected phenolic compound comprises an aryl epoxy Propyl carbonate group. 18. The ACF of claim 3, wherein the composition is formulated for use as a sheet molding compound (SMC), a bulk molding compound (BMC), or a bulk molding compound (DMC). 19. The electronic component of claim 12, wherein the electronic component forms an electronic display. 49
TW099118990A 2009-06-12 2010-06-11 Latent hardener for epoxy resin composition TWI425023B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US18654709P 2009-06-12 2009-06-12
US12/497,040 US8044154B2 (en) 2009-06-12 2009-07-02 Latent hardener for epoxy compositions
US31319910P 2010-03-12 2010-03-12
US12/762,892 US8067484B2 (en) 2010-03-12 2010-04-19 Latent hardener with improved barrier properties and compatibility

Publications (2)

Publication Number Publication Date
TW201120085A true TW201120085A (en) 2011-06-16
TWI425023B TWI425023B (en) 2014-02-01

Family

ID=45045033

Family Applications (1)

Application Number Title Priority Date Filing Date
TW099118990A TWI425023B (en) 2009-06-12 2010-06-11 Latent hardener for epoxy resin composition

Country Status (4)

Country Link
JP (1) JP2012529555A (en)
KR (1) KR101385077B1 (en)
CN (1) CN102459394B (en)
TW (1) TWI425023B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019078044A1 (en) * 2017-10-18 2019-04-25 株式会社スリーボンド Thermally conductive resin composition, cured object, and heat radiation method
TWI715978B (en) * 2019-05-15 2021-01-11 洽興營造有限公司 Environmental protection full polyurea nuclear waste barrel
JP7455950B2 (en) 2019-07-12 2024-03-26 サムヤン コーポレイション Anhydrous sugar alcohol-alkylene glycol compositions, anhydrous sugar alcohol-based urethane modified polyol compositions, and their use for epoxy resin compositions
CN117362590B (en) * 2023-11-01 2024-05-07 湖北泊瑞高分子材料有限公司 Hyperbranched flexible waterborne epoxy resin curing agent and preparation method thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5649780A (en) * 1979-09-29 1981-05-06 Nitto Electric Ind Co Ltd Resin molded bondable article
JPS62273224A (en) * 1986-05-21 1987-11-27 Asahi Denka Kogyo Kk Epoxy resin curable composition
DE19845607A1 (en) * 1998-10-06 2000-04-20 Henkel Teroson Gmbh Impact-resistant epoxy resin compositions
EP1852452A1 (en) * 2005-02-23 2007-11-07 Asahi Kasei Chemicals Corporation Latent hardener for epoxy resin and epoxy resin composition
US20070095475A1 (en) * 2005-11-01 2007-05-03 L&L Products, Inc. Adhesive material and method of using same
US20070270515A1 (en) * 2006-05-19 2007-11-22 Zephyros, Inc. Toughened polymeric material and method of forming and using same
JP5430059B2 (en) * 2007-11-08 2014-02-26 株式会社Ａｄｅｋａ Method for producing latent curing agent for powdery epoxy resin, latent curing agent for powdery epoxy resin obtained by the method, and composition for curable epoxy resin using the same
JP2008115400A (en) * 2007-12-10 2008-05-22 Hitachi Chem Co Ltd Adhesive for connecting circuit members
JP4492692B2 (en) * 2007-12-17 2010-06-30 日立化成工業株式会社 Adhesive film for connecting circuit members
JP2010150362A (en) * 2008-12-25 2010-07-08 Sumitomo Electric Ind Ltd Film adhesive and anisotropically conductive adhesive

Also Published As

Publication number Publication date
JP2012529555A (en) 2012-11-22
TWI425023B (en) 2014-02-01
KR20120046158A (en) 2012-05-09
CN102459394A (en) 2012-05-16
KR101385077B1 (en) 2014-04-24
CN102459394B (en) 2015-01-21

Similar Documents

Publication Publication Date Title
US8481612B2 (en) Latent hardener with improved barrier properties and compatibility
CN101128502B (en) Latent curing agent for epoxy resin and epoxy resin composition
TWI247764B (en) Capsulated curing agent and composition
JP5158088B2 (en) Microcapsule type latent curing agent for epoxy resin and method for producing the same, and one-part epoxy resin composition and cured product thereof
CN102414241A (en) Imidazole compound-containing microcapsulated composition, curable composition using same, and masterbatch type curing agent
CN101595152B (en) latent curing agent
TW201035133A (en) Vinyl polymer powder, curable resin, composition and cured product
US8044154B2 (en) Latent hardener for epoxy compositions
JP2010053353A (en) Microcapsule type latent curing agent for epoxy resin and method for producing the same, one-part epoxy resin composition, cured product of epoxy resin, adhesive, film for bonding, conductive material, and anisotropically conductive material
CN107001567A (en) It is used as the polyester prepolyer of the impact modifier in epoxy preparation
CN102227457A (en) Curing accelerator for epoxy resin composition and one-pack type thermosetting epoxy resin composition
TW201120085A (en) Latent hardener for epoxy compositions
JP5045896B2 (en) Latent curing agent for epoxy resin and method for producing the same
TW200908166A (en) Adhesive for electronic component, semiconductor chip stacking method, and semiconductor device
JP6702534B2 (en) Epoxy resin composition
JP3270774B2 (en) Latent curing agent for spherical epoxy resin and method for producing the same
CN108219691A (en) Photocurable resin composition and electronic component-use sealant
JP3031897B2 (en) Epoxy resin cured product and curing method for obtaining the same
JPH08337633A (en) Microcapsule type curing agent or curing accelerator, epoxy resin composition containing the same, curing method and cured epoxy resin
CN102143987B (en) Heat-cured epoxy resin composition
JP6168005B2 (en) Electrical parts
WO2017166188A1 (en) A latent curing accelerator composition and a one-part curable adhesive composition comprising the same
JP2013053228A (en) Curing agent for epoxy resin, and microcapsule-type curing agent for epoxy resin
TW200306992A (en) Thermosetting resin composition and semiconductor device obtained with the same
JP2013053230A (en) Epoxy resin composition, and pasty composition and film composition using the same

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees