TW201008971A - Microcapsule-type latent curing agent for epoxy resin and process for production thereof, and one-pack-type epoxy resin composition and cured product thereof - Google Patents

Microcapsule-type latent curing agent for epoxy resin and process for production thereof, and one-pack-type epoxy resin composition and cured product thereof Download PDF

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TW201008971A
TW201008971A TW097136142A TW97136142A TW201008971A TW 201008971 A TW201008971 A TW 201008971A TW 097136142 A TW097136142 A TW 097136142A TW 97136142 A TW97136142 A TW 97136142A TW 201008971 A TW201008971 A TW 201008971A
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Taiwan
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epoxy resin
microcapsule
curing agent
type
latent curing
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TW097136142A
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Chinese (zh)
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Shigeaki Funyuu
Yutaka Okada
Yoshii Morishita
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Hitachi Chemical Co Ltd
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    • 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
    • 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
    • C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Disclosed is a microcapsule-type latent curing agent comprising a core and a capsule that sheathes the core. In the microcapsule-type curing agent, the core comprises an amine adduct and the capsule comprises a reaction product of an isocyanate with a compound having an active hydrogen group and/or water. At least a part of the reaction product is bound to the core through the reaction with the amine adduct.

Description

201008971 九、發明說明 【發明所屬之技術領域】 本發明係關於環氧樹脂用微膠囊型潛在性硬化劑及其 製造方法，以及一液性環氧樹脂組成物及環氧樹脂硬化 物。 【先前技術】 & 環氧樹脂，其硬化物因在機械特性、電特性、熱特 性、耐藥品性、黏著性等方面具有優越的性能，被廣泛利 - 用於塗料、電器電子用絕緣材料、黏著劑等用途。現在一 • 般被使用之樹脂組成物較多在使用時將環氧樹脂與硬化劑 之二液混合，也就是所謂的二液性者。 二液性環氧樹脂組成物在室溫下可硬化，但另一方面 來看，環氧樹脂與硬化劑必須分別保管，依據需要將兩者 計量混合後使用，其保管或操作係爲煩雜。此外，因其可 使用時間有所限制，並無法預先大量混合，調製頻繁度變 多，無法免於效率降低。 以解決如此之二液性環氧樹脂組成物之問題爲目的， 至此有許多的一液性環氧樹脂組成物被提案。例如有，將 如二氰胺、bf3 -胺錯合物、胺鹽及改性咪唑化合物之潛 在性硬化劑與環氧樹脂相配合者。 又，使粉末狀胺化合物之表面與異氰酸酯反應，使胺 化合物之表面不活性化且賦予硬化劑潛在性之討論正在進 行（專利文獻1〜5)。更且，藉由使粉末狀胺化合物於環 201008971 氧樹脂中與異氰酸酯反應膠囊化後之微膠囊型硬化劑也被 提案著（專利文獻6〜8 )。例如專利文獻6中，藉由將作 爲核心之胺系硬化劑於環氧樹脂中分散，添加異氰酸酯及 水形成殻層之方法所得之母料（materbatch)型硬化劑被 揭示著。作爲其它方法’有混合環氧樹脂與胺系硬化劑， 立即冷凍使反應之進行停止之方法、將胺系硬化劑微膠囊 化之方法、使硬化劑吸附於分子篩之方法。 專利文獻1 :特公昭58-55970號公報 專利文獻2 :特開昭59-27914號公報 專利文獻3 :特開昭59-59720號公報 專利文獻4 :歐洲專利申請公開第1 93068號說明書 專利文獻5:特開昭61-190521號公報 專利文獻6:特開平1-70523號公報 專利文獻7 :特開2004-269721號公報 專利文獻8 :特開2005-344046號公報 【發明內容】 [發明所欲解決之問題] 但，以往之潛在性硬化劑之場合，儲藏安定性優良者 其硬化性爲低，硬化必須爲高溫或長時間。另一方面，硬 化性優良者其儲藏安定性爲低，例必須儲藏於-20 °C低溫 下。例，配合二氰胺（dicyandiamide)之一液性環氧樹脂 組成物，雖在常溫保存下有6個月以上之儲藏安定性，但 硬化溫度必須爲1 70 °C以上。爲使此硬化溫度降低若倂用 -6- 201008971 硬化促進劑，就可在例如1 3 0 °C〜1 5 0 °c硬化。但，因此種 情況在室溫下之儲藏安定性爲不充分，除了不得已使用低 溫下之儲藏外，同時也縮短適用期（Pot Life )。其結 果，二氰胺的潛在性則無法充分地活用。製造膜狀成形品 或浸泡環氧樹脂組成物於基材中之製品時所用之環氧樹脂 組成物，雖使用包含溶劑或反應性稀釋劑等之配合品之情 況爲多，若使用相關配合品以往之潛在性硬化劑其儲藏安 0 定性則極端性下降。因此，於實質上將配合品作爲二液性 有其必要性，其改善也被要求著。 如專利文獻3般，藉由封鎖胺化合物之表面官能基之 方法中，作爲一液性環氧樹脂組成物爲之必要特性，特別 係儲藏安定性此點未必充分。又，實際去使用一液性環氧 樹脂組成物時，其均勻性也爲重要。因此，一般而言，以 輥與其他之裝置將粉末狀之硬化劑使其均勻地分散於環氧 樹脂中係爲必要。但，就算使用專利文獻1〜4中所揭示 Φ 之任一方法，伴隨著此室溫下之分散操作因機械性剪斷力 使已生成之惰性表面層被破壞，其結果爲也有著無法得到 可容忍的實際運用之充分的儲藏安定性之問題。 另一方面，若藉由上述之冷凍、微膠嚢化或分子篩之 方法，雖可得到比較良好的儲藏安定性，但在性能面，特 別係硬化物特性不足，幾乎完全沒有被實用化則爲其現 狀。 如上述，可同時有高硬化性與優良儲藏安定性之一液 性環氧樹脂組成物被強烈地要求著。特別係近年來，爲提 201008971 升電子材料用途中之生產性，對於一液性樹脂組成物，其 硬化特性及儲藏安定性之更向上提升被要求著。 於此，本發明以提供使一液性環氧樹脂組成物之低溫 硬化性與優良儲藏安定性可同時倂存之硬化劑及其製造方 法爲目的。又，本發明以提供使用本發明的硬化劑之一液 性環氧樹脂組成物及其硬化物爲其目的。 [用以解決課題之手段] 以另一面來看，本發明係，有關於具有核心及將此被 覆之膠囊之微膠囊型潛在性硬化劑。有關於本發明之微膠 囊型硬化劑中，核心含有胺加成物，膠囊爲含有異氰酸酯 與具有活性氫基之化合物及/或與水之反應生成物。反應 生成物中至少一部份藉由與胺加成物反應鍵結於核心。關 於本發明之微膠囊型硬化劑，爲使環氧樹脂硬化而使用。 關於本發明之微膠襄型潛在性硬化劑亦可爲粉末狀。 藉由關於本發明之微膠囊型硬化劑，可使一液性環氧 樹脂組成物之低溫硬化性於優良安定性同時倂存。 爲使藉由本發明之效果更爲顯著，上述核心以含有以 質量比5 0〜1 0 0 %之胺加成物爲佳。 膠囊之比例爲，以該當微膠囊型潛在性硬化劑之全質 量作爲基準以5〜80質量％爲佳。經此，可使低溫安定性 及儲藏安定性於更髙之程度同時倂存。 膠囊之比例亦可爲40〜80質量％。藉此，潛在性硬化 劑可有非常良好之儲藏安定性及耐溶劑性。又，也可更進 -8 - 201008971 一步達成優良之低溫硬化性。因此，例如就算將潛在性硬 化劑與溶劑混合，長時間放置時，不會有因溶劑使微膠囊 型潛在性硬化劑之核心成份溶析一事，可維持其低溫硬化 性。 膠囊之比例亦可爲15〜40質量％。藉此，潛在性硬化 劑有更良好之儲藏安定性及耐溶劑性，可具有更良好之低 溫硬化性，於非常高之程度下可同時持有此些特性。因 @ 此，例如將潛在型硬化劑與環氧樹脂混合，就算係在40 t 左右之加熱狀態下放置一星期，而不會有與環氧樹脂之反 應進行而黏度上升，導至喪失其低溫硬化特性一事，可使 其顯現良好之儲藏安定性與良好之低溫硬化性。 膠囊之比例亦可爲5〜1 5質量％。藉此，潛在性硬化 劑同時有非常良好之低溫硬化性，同時也有更良好之儲藏 安定性與耐溶劑性。 以另一面來看，本發明係關於環氧樹脂用微膠囊型潛 〇 在性硬化劑之製造方法。本發明之製造方法係具備有藉由 被包含於核心之胺加成物與異氰酸酯與具有活性氫基之化 合物及/或與水在分散媒中反應，形成被覆該核心之膠囊 之步驟。本發明之製造方法亦可更具備有從反應後之混合 物中取出具有核心及膠襄之粉末狀之微膠囊型潛在性硬化 劑之步驟。 依據上述本發明之製造方法，將可一邊抑制使一液性 環氧樹脂組成物之低溫硬化性與優秀之儲藏安定性同時成 立之微膠囊型硬化劑之特性的偏差，一邊可得。本發明之 -9- 201008971 微膠囊型潛在性硬化劑亦可爲可藉由上述本發明之製造方 法所得者。 更可以另一面來看，本發明係關於一液性環氧樹脂組 成物。本發明之一液性環氧樹脂組成物含有上述本發明之 環氧樹脂用微膠囊型潛在性硬化劑與環氧樹脂。 本發明之一液性環氧樹脂組成物，具有低溫硬化性與 優良之儲藏安定性。 @ 環氧樹脂用微膠囊型潛在性硬化劑，亦可爲於環氧樹 脂中被加熱處理者。本發明之一液性環氧樹脂組成物，相 對於環氧樹脂及微膠囊型潛在性硬化劑之合計量100質量 份，以含有5〜70質量份之微膠囊型潛在性硬化劑爲佳。 更可以另一面來看，本發明係關於環氧樹脂組成物之 硬化物。本發明之硬化物，係藉由加熱上述本發明之一液 性環氧樹脂組成物而硬化形成。本發明之硬化物，在電特 性（絕緣性）之面極爲優秀。 [發明之效果] 藉由本發明之微膠囊型硬化劑，可使一液性環氧樹脂 組成物之低溫硬化性與優良之儲藏安定性同時成立。因 此，本發明之微膠囊型硬化劑適合用於提升電子材料用途 等中之生產性。 本發明之粉末狀微膠囊型潛在性硬化劑，在以下之面 也具有優良之作用效果。 (1)因爲係粉末狀，從硬化特性或硬化物之物性等 -10- 201008971 方面思考，可使配合目的之環氧樹脂容易地均勻分散。 又，環氧樹脂組成物中之硬化劑配合比之自由度也爲高。 (2) 因爲膠囊部分可容易控制，配合其目的，可容 易達成具有良好硬化特性或良好之儲藏安定性之潛在性硬 化劑。 (3) 因爲一液性環氧樹脂組成物可容易製造，改良 其使用時之作業性，又可得到製品的高可靠性。 0 本發明之微膠囊型潛在性硬化劑，就算經由於調製一 液型環氧樹脂組成物時所附加之機械性剪斷力，也具有其 性能變化爲少之作用效果。 依據上述本發明之製造方法，將一邊抑制使一液性環 氧樹脂組成物之低溫硬化性與優秀之儲藏安定性同時成立 之微膠囊型硬化劑之特性的偏差，一邊可得。在將粉末狀 胺化合物於環氧樹脂中與異氛酸酯反應之以往的製造方式 的場合中’例如爲增加提升低溫硬化性作爲其目的之微膠 φ 囊型潛在性硬化劑之量，在環氧樹脂中添加大量之粉末狀 月安化合物係爲必要。粉末狀胺化合物之量若變多，因其黏 度會變高’均勻地進行膠囊化反應則會變爲困難。其結 果’生產單位間的特性之誤差將變大，製品之不良率提 高’膠囊形成之程度成不足將會無法取得充分之儲藏安定 性°又’爲提高硬化特性，若以與環氧樹脂之反應性爲高 之成份作爲核心材料使用，在環氧樹脂中進行硬化反應， 也有無法合成具有充分特性之潛在性硬化劑之問題。藉由 本#日月2製造方法，因可抑制造成黏度上升的原因的核心 -11 - 201008971 與環氧樹脂之反應，及異氰酸酯與水與環氧樹脂之反應， 可得到高流動性之一液性環氧樹脂。從此些點可看出，本 發明之製造方法與以往之方法相比較具有有利之效果。 藉由本發明之微膠囊型潛在性硬化劑之製造方法，與 將環氧樹脂中之爲硬化劑之粉末狀胺化合物配合後形成殻 之方法相比較，因硬化反硬或黏度上升爲少，更可容易使 其均勻地進行反應。其結果，生產單位間之特性誤差變 @ 小。又，副生成物的除去也爲容易。更進一步，也無必要 依每個所組合之環氧樹脂種類分別製造其硬化劑，作業效 率良好，環氧樹脂的選擇幅度也爲寬廣。 以往之母料型硬化劑的黏度高，達成環氧樹脂組成物 之足夠的流動性尤爲困難，藉由本發明，可得到具有充分 流動性之一液性環氧樹脂組成物。近年，特別係電子領域 中，爲提升對應電路之高密度化或連接可靠性，作爲連接 材料之一所使用之一液性環氧樹脂組成物，從進行充塡至 φ 狹小的縫間到具有高度流動性而變的更爲重要。 於環氧樹脂中添加異氰酸酯及水於粉末狀胺係硬化劑 之表面上將殻形成之方法的場合，因容易產生經由異氰酸 酯與水之反應而生成之1級胺與環氧樹脂反應之副反應， 生成物的再現性將難以取得。又，因硬化劑可經由與特定 之環氧樹脂的配合物（母料）之狀態下取得，也有配合的 自由度遭限制等問題。本發明在解決此些問題上也爲有 利。 活用如以上之效果，本發明之微膠囊型潛在性硬化劑 -12- 201008971 及一液性環氧樹脂組成物，可利用於廣泛的領域用途。例 如作爲黏著劑，於汽車領域中之大燈、油箱之黏著、引擎 罩等之反折邊緣部份之黏著、車體及車頂部份之鋼版的結 合，於電機領域中之喇叭磁鐵之黏著、發動機線圈之浸含 及黏著、磁帶頭、電池箱之黏著、螢光燈安定器之黏著， 於電子領域中之鋼模黏結用黏著劑、1C晶片密封劑、晶片 覆膜材料、晶片底座材料、印刷基材之黏著劑、薄膜黏著 Φ 劑、非等方導電性薄膜、非等方導電性漿等之用途中可使 用本發明之一液性環氧樹脂組成物。作爲其它用途，於塗 料領域中，可舉出粉體塗料、焊阻綠漆油墨、導電性塗料 等。又，電氣絕緣材料、積層構造體等中也可使用本發 明。特別係近年來，於電子材料用途中爲提升生產性，對 於一液性樹脂組成物，其硬化特性及儲藏安定性之更向上 提升則被要求著。 〇 【實施方式】 以下詳細說明本發明之適宜實施型態。但，本發明並 不受以下之實施型態所限定。 本實施型態之微膠囊型潛在性硬化劑，具有粒子狀之 核心及包覆此核心之膠囊。膠囊爲包覆核心表面之至少一 部份之膜。 核心係含有胺加成物作爲主成份。更具體而言，核心 之通常以質量比爲含有5 0〜1 0 0 %，以6 0〜1 0 0 %之胺加成 物爲佳。如胺加成物之質量比未滿50%，其硬化特性及儲 -13- 201008971 藏安定性則有變爲比較難以倂存之傾向。 胺加成物爲經由環氧樹脂與胺化合物反應所得，爲具 有胺基之化合物。 爲得到胺加成物所使用之環氧樹脂，可使用單環氧化 合物及多價環氧化合物任一種或彼些之混合物。作爲單環 氧化合物，例如，可舉出丁基縮水甘油醚、已基縮水甘油 醚、苯基縮水甘油醚、烯丙基縮水甘油醚、對-tert-丁基 φ 苯基縮水甘油醚、環氧乙烷、環氧丙烷、對二甲苯基縮水 甘油醚、乙酸縮水甘油酯、丁酸縮水甘油酯、己酸縮水甘 油酯及苯甲酸縮水甘油酯。作爲多價環氧化合物可列舉， 將雙酚A、雙酚F、雙酚AD、雙酚S、四甲基雙酚A、四 甲基雙酚F、四甲基雙酚AD、四甲基雙酚S、四溴雙酚A 及四氯雙酚A、四氟雙酚A等之雙酚類縮水甘油化所得之 雙酚型環氧樹脂；雙酚、二羥基萘、9,9-bis ( 4-羥基苯 基）弗等之其它的2價酚類將其縮水甘油化所得之環氧樹 籲 脂；1，1，1-三（4-羥基苯基）甲烷、4,4- ( 1- ( 4- ( 1- ( 4-羥基苯基）-1-甲基乙基）苯基）亞乙基）雙酚等之三酚類 將其縮水甘油化所得之環氧樹脂；將1，1，2,2,-四（4-羥基 苯基）乙烷等之四酚類縮水甘油化所得之環氧樹脂；將酚 酚醛清漆、甲酚酚醛清漆、雙酚A酚醛清漆、溴化酚酚醛 清漆溴化雙酚A酚醛清漆等之酚醛清漆類縮水甘油化所得 之酚醛清漆型環氧樹脂；多價醇類縮水甘油化所得之環氧 樹脂、將甘油或聚乙二醇等之多價醇等縮水甘油化所得之 脂肪族醚型環氧樹脂；將P-氧化安息香酸、/S -氧化萘甲 -14- 201008971 酸等之氫氧羧酸縮水甘油化所得之醚酯型環氧樹 鄰苯二甲酸、對苯二甲酸之聚羧酸縮水甘油化所 環氧樹脂；4,4-二胺二苯甲烷或m-胺苯等之胺化 水甘油化物或三縮水甘油異三聚氰酸酯等之胺型 等之縮水甘油型環氧樹脂與3,4-環氧環己基甲基 氧環己烷羧酸酯等之脂環族環氧化物。 作爲環氧樹脂，因可提高環氧樹脂組成物之 φ 性，以多價環氧化合物爲佳。因多價環氧化合物 物之生產爲壓倒性的高，以縮水甘油型環氧樹脂 硬化物之黏著性或耐熱性良好，多價環氧化合物 類之縮水甘油化物爲較佳、雙酚型環氧樹脂更佳 以將雙酚A縮水甘油化後之環氧樹脂的雙酚A 脂及將雙酚F縮水甘油化後之環氧樹脂的雙酚F 脂爲佳，此些之中以雙酚A型環氧樹脂爲最佳。 樹脂亦可單獨或合倂使用。 φ 爲得到胺加成物所用之胺化合物，理想爲， 胺基及/或有二級胺基但無三級胺基之化合物與 及有活性氫基之化合物。作爲一級胺基及/或有 但無三級胺基之化合物，例如，甲胺、乙胺、 胺、乙二胺、丙二胺、六甲基二胺、二乙三胺 胺、乙醇胺、丙醇胺、環己胺、異佛酮二胺、苯 胺、二胺二苯甲烷及二胺苯楓之第一胺類、以及 二乙胺、二丙胺、二丁胺、二戊胺、二己胺、二 二乙醇胺、二丙醇胺、二環己胺、哌啶、哌啶 脂；將如 得之酯型 合物之縮 環氧樹脂 一3’，4’-環 儲藏安定 以胺化合 爲佳。因 以多價酚 。特別係 型環氧樹 型環氧樹 此些環氧 選自一級 三級胺基 二級胺基 丙胺、丁 、三乙四 胺、甲苯 二甲胺、 甲醇胺、 酮、二苯 -15- 201008971 胺、苯甲胺及苯乙胺之第二胺類可舉出。 具有三級胺基及活性氫基之化合物中，作爲活性氫基 可列舉一級胺基、二級胺基、羥基、硫醇基、羧酸及氫化 基（hydrazido )。作爲三級胺基及具有活性氫基之化合 物，例如可舉出，2-二甲胺基乙醇、1-甲基-2-二甲胺基乙 醇、卜苯氧基甲基-2-二甲胺基乙醇、2-二乙胺乙醇、1-丁 氧基甲基-2-二甲胺乙醇、甲基二乙醇胺、三乙醇胺及N-〇 冷-羥基甲基嗎啉等之胺醇類；2-(二甲胺甲基）酚及 2,4,6-三（二甲胺甲基）酚之胺酚類；2-甲基咪唑、2-乙 基-4-甲基咪唑、2-十一基咪唑、2-十七基咪唑、2-苯基咪 唑、1-胺乙基-2-甲基咪唑、1-(2-羥基-3-苯氧基丙基）· 2-甲基咪唑、1-(2-羥基-3-苯氧基丙基）-2·乙基-4-甲基 咪唑、1-(2-羥基-3-丁氧基丙基）-2-甲基咪唑及1-(2-羥基-3-丁氧基丙基）-2-乙基-4-甲基咪唑之咪唑類；1-(2-羥基-3-苯氧基丙基）-2-苯基咪唑啉、1-(2-羥基-3-® 丁氧基丙基）-2-甲基咪唑啉、2-甲基咪唑啉、2，4-二甲基 咪唑啉、2-乙基咪唑啉、2-乙基-4-甲基咪唑啉、2-苯甲基 咪唑啉、2 -苯基咪唑啉、2- (〇 -甲苯基）-咪唑啉、四伸甲 基-雙-咪唑啉、1，1，3-三甲基·1，4-四伸甲基-雙-咪唑啉、 1，3,3-三甲基-1，4-四伸甲基-雙-咪唑啉、1，1，3-三甲基_1，4-四伸甲基-雙-4-甲基咪唑啉、1,2-伸苯基-雙-咪唑啉、丨，3· 伸苯基-雙-咪唑啉、1，4·伸苯基-雙-咪唑啉、1，4-伸苯基· 雙-4-甲基咪唑啉之咪唑啉類；二甲胺基丙胺、二乙胺基丙 胺、二丙胺基丙胺、二丁胺基丙胺、二甲胺基乙胺、二乙 -16- 201008971 胺基乙胺、二丙胺基乙胺、二丁胺基乙胺、Ν·甲基哌嗪、 Ν-胺乙基哌嗪及二乙胺基乙基哌嗪之三級胺基胺類；2-二 乙胺基乙硫醇、2-锍苯咪唑、2-锍苯噻唑、2-毓吡啶及4-巯吡啶之胺基硫醇類；Ν，Ν-二甲胺基安息香酸、Ν,Ν-二甲 基甘胺酸、菸鹼酸、異菸鹼酸及甲基吡啶之胺基羧酸類； Ν，Ν-氫化二甲基甘胺酸、氫化菸鹼酸及氫化異菸鹼酸之氫 化胺類。 φ 胺化合物，因其儲藏安定性與硬化性之平衡良好，以 具有三級胺基及活性氫基之化合物爲佳。其中，以咪唑類 爲較佳、以2-甲基咪唑及2-乙基-4-甲基咪唑爲更佳。[Technical Field] The present invention relates to a microcapsule latent curing agent for an epoxy resin, a method for producing the same, and a one-part epoxy resin composition and an epoxy resin hardened material. [Prior Art] & Epoxy resin, which has excellent properties due to its mechanical properties, electrical properties, thermal properties, chemical resistance, adhesion, etc., is widely used - for insulating materials for coatings, electrical and electronic applications. , adhesives and other uses. Nowadays, the resin composition used in general is mixed with the epoxy resin and the hardener at the time of use, which is also called a two-liquidity. The two-component epoxy resin composition can be cured at room temperature, but on the other hand, the epoxy resin and the hardener must be separately stored, and the two can be metered and mixed as needed, and the storage or operation thereof is troublesome. In addition, because of the limited time available for use, it is not possible to mix in advance, and the frequency of modulation is increased, so that efficiency cannot be reduced. In order to solve the problem of such a two-component epoxy resin composition, many one-liquid epoxy resin compositions have been proposed so far. For example, a latent hardener such as dicyandiamide, a bf3-amine complex, an amine salt, and a modified imidazole compound may be blended with an epoxy resin. Further, the surface of the powdered amine compound is reacted with an isocyanate to deactivate the surface of the amine compound and the potential of the curing agent is imparted (Patent Documents 1 to 5). Further, a microcapsule-type curing agent which is obtained by reacting a powdery amine compound with an isocyanate in an oxygen resin of the ring 201008971 has also been proposed (Patent Documents 6 to 8). For example, in Patent Document 6, a materbatch type hardener obtained by dispersing an amine-based curing agent as a core in an epoxy resin and adding an isocyanate and water to form a shell layer is disclosed. As another method, there is a method of mixing a epoxy resin and an amine-based curing agent, freezing the reaction immediately, and a method of microencapsulating the amine-based curing agent and a method of adsorbing the curing agent to the molecular sieve. [Patent Document 1] Japanese Patent Application Laid-Open No. Hei 59-59970-A. Patent Publication No. JP-A-59-59 Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2005-344. Problem to be solved] However, in the case of the conventional latent curing agent, the storage stability is low, and the hardening property is low, and the hardening must be high temperature or long time. On the other hand, those having excellent hardenability have low storage stability, and must be stored at a low temperature of -20 °C. For example, a liquid epoxy resin composition containing one of dicyandiamide has a storage stability of 6 months or more at room temperature, but the curing temperature must be 1 70 °C or more. In order to lower the hardening temperature, if the hardening accelerator is used, the hardening accelerator can be hardened at, for example, 1 30 ° C to 150 ° C. However, in this case, the storage stability at room temperature is insufficient, except that the storage at a low temperature must be used, and the pot life is also shortened. As a result, the potential of dicyandiamide cannot be fully utilized. When the film-formed product or the epoxy resin composition used for immersing the epoxy resin composition in the substrate is used, the use of a compound containing a solvent or a reactive diluent is often used. In the past, the potential hardeners were extremely volatile when stored in a safe state. Therefore, it is necessary to substantially use the compound as a two-liquid property, and improvement is also required. As in the case of Patent Document 3, in the method of blocking the surface functional group of the amine compound, it is not necessarily sufficient as a one-component epoxy resin composition, which is particularly essential for storage stability. Further, when a one-liquid epoxy resin composition is actually used, uniformity is also important. Therefore, in general, it is necessary to uniformly disperse a powdery hardener in an epoxy resin by a roll and other means. However, even if any of the methods disclosed in Patent Documents 1 to 4 is used, the generated inert surface layer is destroyed by the mechanical shearing force accompanying the dispersion operation at room temperature, and as a result, it is impossible to obtain The problem of adequate storage stability that can be tolerated in practical use. On the other hand, if the above-mentioned method of freezing, micro-gelling or molecular sieve is used, although relatively good storage stability can be obtained, in the performance surface, in particular, the properties of the cured product are insufficient, and almost no practical use is obtained. Its current status. As described above, a liquid epoxy resin composition which can simultaneously have high hardenability and excellent storage stability is strongly required. In particular, in recent years, in order to improve the productivity of the use of 201008971 liters of electronic materials, it is required to improve the hardening characteristics and storage stability of the one-liquid resin composition. Here, the present invention has an object of providing a curing agent which can simultaneously store low-temperature hardenability and excellent storage stability of a one-part epoxy resin composition, and a method for producing the same. Further, the present invention has an object of providing a liquid epoxy resin composition using one of the hardeners of the present invention and a cured product thereof. [Means for Solving the Problem] On the other hand, the present invention relates to a microcapsule-type latent curing agent having a core and a capsule to be coated. In the microcapsule-type hardener of the present invention, the core contains an amine adduct, and the capsule is a reaction product containing an isocyanate and a compound having an active hydrogen group and/or with water. At least a portion of the reaction product is bonded to the core by reaction with an amine adduct. The microcapsule-type hardener of the present invention is used to harden an epoxy resin. The microcapsule type latent hardener of the present invention may also be in the form of a powder. According to the microcapsule-type hardener of the present invention, the low-temperature curability of the one-liquid epoxy resin composition can be prevented from being deteriorated while maintaining excellent stability. In order to make the effect by the present invention more remarkable, the core preferably contains an amine adduct having a mass ratio of 50 to 100%. The ratio of the capsules is preferably from 5 to 80% by mass based on the total mass of the microcapsule-type latent curing agent. As a result, the low-temperature stability and the storage stability can be simultaneously stored at a higher level. The ratio of the capsules may also be 40 to 80% by mass. Thereby, the latent hardener can have very good storage stability and solvent resistance. Also, you can also enter -8 - 201008971 to achieve excellent low temperature hardening. Therefore, for example, even if a latent hardening agent is mixed with a solvent, when it is left for a long period of time, the core component of the microcapsule latent curing agent is not eluted by the solvent, and the low-temperature hardening property can be maintained. The ratio of the capsules may also be 15 to 40% by mass. Thereby, the latent hardener has better storage stability and solvent resistance, can have better low-temperature hardening property, and can hold such characteristics at a very high level. Because @, for example, the latent hardener is mixed with the epoxy resin, even if it is left in a heated state of about 40 t for one week, without the reaction with the epoxy resin, the viscosity rises, leading to the loss of its low temperature. The hardening property allows it to exhibit good storage stability and good low temperature hardenability. The ratio of the capsules may also be 5 to 15% by mass. Thereby, the latent hardener has a very good low-temperature hardening property, and also has better storage stability and solvent resistance. On the other hand, the present invention relates to a method for producing a microcapsule-type latent curing agent for an epoxy resin. The production method of the present invention comprises the step of forming a capsule covering the core by reacting an amine adduct contained in the core with a compound having an isocyanate and an active hydrogen group and/or reacting with water in a dispersion medium. The production method of the present invention may further comprise a step of taking out a microcapsule-type latent curing agent having a core and a capsule powder from the mixture after the reaction. According to the production method of the present invention, it is possible to obtain a variation in the properties of the microcapsule-type curing agent which simultaneously establishes the low-temperature curability of the one-liquid epoxy resin composition and the excellent storage stability. The -9-201008971 microcapsule type latent curing agent of the present invention may also be obtained by the above-described production method of the present invention. On the other hand, the present invention relates to a one-component epoxy resin composition. The liquid epoxy resin composition of the present invention contains the above-mentioned microcapsule latent curing agent for epoxy resin of the present invention and an epoxy resin. The liquid epoxy resin composition of the present invention has low-temperature hardenability and excellent storage stability. @ Microcapsule latent hardener for epoxy resin, or heat treated in epoxy resin. The liquid epoxy resin composition of the present invention preferably contains 5 to 70 parts by mass of a microcapsule-type latent curing agent, based on 100 parts by mass of the total amount of the epoxy resin and the microcapsule latent curing agent. On the other hand, the present invention relates to a cured product of an epoxy resin composition. The cured product of the present invention is formed by heating the above-mentioned liquid epoxy resin composition of the present invention. The cured product of the present invention is excellent in electrical properties (insulating properties). [Effect of the Invention] The microcapsule-type curing agent of the present invention can simultaneously satisfy the low-temperature curability of the one-liquid epoxy resin composition and the excellent storage stability. Therefore, the microcapsule-type hardener of the present invention is suitable for improving productivity in use of electronic materials and the like. The powdery microcapsule latent curing agent of the present invention also has an excellent effect in the following aspects. (1) Since it is in the form of a powder, it is considered that the epoxy resin for the purpose of mixing can be easily and uniformly dispersed from the viewpoint of the hardening property, the physical properties of the cured product, and the like. Further, the degree of freedom of the hardener mixing ratio in the epoxy resin composition is also high. (2) Since the capsule portion can be easily controlled, it is easy to achieve a potential hardening agent having good hardening properties or good storage stability. (3) Since the one-liquid epoxy resin composition can be easily manufactured, the workability at the time of use can be improved, and the high reliability of the product can be obtained. The microcapsule-type latent curing agent of the present invention has an effect of less variation in performance even when mechanical shearing force is added to the composition of the one-liquid epoxy resin composition. According to the production method of the present invention, it is possible to obtain a variation in the properties of the microcapsule-type curing agent which simultaneously forms the low-temperature curability of the one-liquid epoxy resin composition and the excellent storage stability. In the case of a conventional production method in which a powdery amine compound is reacted with an isomeric acid ester in an epoxy resin, for example, an amount of a microcapsule φ capsule type latent curing agent which is used for the purpose of increasing low-temperature hardenability is improved. It is necessary to add a large amount of powdered hyacinth compound to the epoxy resin. When the amount of the powdery amine compound is increased, the viscosity thereof becomes high. It becomes difficult to carry out the encapsulation reaction uniformly. As a result, the error of the characteristics between the production units will become large, and the defective rate of the product will be improved. 'The degree of formation of the capsule will be insufficient to obtain sufficient storage stability. Moreover, to improve the hardening characteristics, A component having a high reactivity is used as a core material, and a hardening reaction is carried out in an epoxy resin, and there is also a problem that a latent hardener having sufficient characteristics cannot be synthesized. According to the manufacturing method of the #日月2, the reaction of the core -11 - 201008971 with the epoxy resin and the reaction of the isocyanate with water and the epoxy resin can be suppressed, thereby obtaining a liquidity of high fluidity. Epoxy resin. As can be seen from this point, the manufacturing method of the present invention has an advantageous effect as compared with the conventional method. According to the method for producing a microcapsule-type latent curing agent of the present invention, compared with the method of forming a shell by mixing a powdery amine compound which is a hardener in an epoxy resin, the hardening or hardening is less, and the viscosity is less. It is easy to carry out the reaction uniformly. As a result, the characteristic error between production units becomes smaller. Moreover, it is also easy to remove by-products. Further, it is not necessary to separately manufacture the hardener according to each type of epoxy resin to be combined, and the work efficiency is good, and the selection range of the epoxy resin is also wide. The conventional masterbatch type hardener has a high viscosity, and it is particularly difficult to achieve sufficient fluidity of the epoxy resin composition. According to the present invention, a liquid epoxy resin composition having sufficient fluidity can be obtained. In recent years, in the field of electronics, in order to increase the density of the corresponding circuit or the reliability of the connection, one of the liquid epoxy resins used as one of the connecting materials is from the filling to the narrow gap of φ to It is more important to change from high liquidity. When a method of forming a shell on the surface of a powdery amine-based hardener by adding isocyanate and water to an epoxy resin, a side reaction of a primary amine and an epoxy resin which are formed by reaction of an isocyanate with water is easily generated. The reproducibility of the product will be difficult to obtain. Further, since the curing agent can be obtained in a state of being mixed with a specific epoxy resin (masterbatch), there is also a problem that the degree of freedom of cooperation is limited. The present invention is also advantageous in solving such problems. By using the above effects, the microcapsule latent curing agent -12-201008971 and the one-liquid epoxy resin composition of the present invention can be utilized in a wide range of fields. For example, as an adhesive, the combination of the headlights in the automobile field, the adhesion of the fuel tank, the adhesion of the reflexed edge portion of the hood, the steel plate of the car body and the top part of the car, the horn magnet in the motor field Adhesion, impregnation and adhesion of engine coils, adhesion of tape heads, battery cases, adhesion of fluorescent lamp stabilizers, adhesives for steel mold bonding in the field of electronics, 1C wafer sealant, wafer coating material, wafer base A liquid epoxy resin composition of the present invention can be used for the use of a material, an adhesive for a printed substrate, a film adhesive Φ agent, an unequal conductive film, an unequal conductive paste, or the like. As other applications, powder coating materials, welding resist green paint inks, and conductive paints can be mentioned in the field of coating. Further, the present invention can also be used in an electrical insulating material, a laminated structure or the like. In particular, in recent years, in order to improve productivity in the use of electronic materials, it is required to further improve the hardening characteristics and storage stability of the one-liquid resin composition.实施 Embodiments Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited by the following embodiments. The microcapsule latent curing agent of the present embodiment has a particulate core and a capsule covering the core. The capsule is a film that covers at least a portion of the core surface. The core contains an amine adduct as a main component. More specifically, the core is usually a mass ratio of 50 to 100%, and preferably 60 to 100% of the amine adduct. If the mass ratio of the amine adduct is less than 50%, the hardening characteristics and storage stability of the alloy may become more difficult to survive. The amine adduct is obtained by reacting an epoxy resin with an amine compound and is a compound having an amine group. To obtain an epoxy resin used for the amine adduct, any one of a monoepoxide and a polyvalent epoxy compound or a mixture thereof may be used. Examples of the monoepoxy compound include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, p-tert-butyl φ phenyl glycidyl ether, and a ring. Oxyethane, propylene oxide, p-xylylene glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexanoate and glycidyl benzoate. Examples of the polyvalent epoxy compound include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, and tetramethyl group. Bisphenol type epoxy resin obtained by glycidation of bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, etc.; bisphenol, dihydroxynaphthalene, 9,9-bis An epoxy resin obtained by glycidation of other divalent phenols such as 4-hydroxyphenyl); 1,1,1-tris(4-hydroxyphenyl)methane, 4,4- ( Epoxy resin obtained by glycidation of a trisphenol such as 1-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene) bisphenol; Epoxy resin obtained by glycidation of tetraphenols such as 1,2,2,-tetrakis(4-hydroxyphenyl)ethane; phenol novolac, cresol novolac, bisphenol A novolac, bromination A novolak type epoxy resin obtained by glycidation of a phenol novolac brominated bisphenol A phenol varnish, etc.; an epoxy resin obtained by glycidation of a polyvalent alcohol, a glycerin or a polyethylene glycol, etc. Fat obtained by glycidation of valence alcohol Group ether epoxy resin; ether ester type epoxy phthalic acid, p-benzoic acid obtained by glycidylation of hydroxy carboxylic acid such as P-oxidized benzoic acid, /S-oxidized naphthalene-14-201008971 acid An epoxy resin of polycarboxylic acid glycidylation of formic acid; an amine type such as aminated hydroglyceride or triglycidyl isocyanurate such as 4,4-diamine diphenylmethane or m-amine benzene; An alicyclic epoxide such as a glycidyl epoxy resin and a 3,4-epoxycyclohexylmethyloxycyclohexanecarboxylate. As the epoxy resin, a polyvalent epoxy compound is preferable because the φ property of the epoxy resin composition can be improved. Since the production of the polyvalent epoxy compound is overwhelming, the adhesion or heat resistance of the cured product of the glycidyl epoxy resin is good, and the glycidyl compound of the polyvalent epoxy compound is preferred, and the bisphenol ring is preferred. The oxy resin is preferably a bisphenol A ester of an epoxy resin obtained by glycidylating bisphenol A and a bisphenol F ester of an epoxy resin obtained by glycidylating bisphenol F, among which bisphenol is used. Type A epoxy resin is the best. The resin can also be used singly or in combination. φ is an amine compound used for obtaining an amine adduct, and is preferably an amine group and/or a compound having a secondary amino group but no tertiary amino group and a compound having an active hydrogen group. a compound which is a primary amine group and/or has a tertiary amine group, for example, methylamine, ethylamine, amine, ethylenediamine, propylenediamine, hexamethyldiamine, diethylenetriamine, ethanolamine, and C Alkanolamine, cyclohexylamine, isophoronediamine, aniline, diamine diphenylmethane and diamine benzene, the first amine, and diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine , diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidine; it is preferred to store the 3', 4'-ring of the epoxy resin of the obtained ester compound with an amine combination. . Because of the multi-valent phenol. Specially-type epoxy tree-type epoxy tree. These epoxy resins are selected from the group consisting of primary tertiary amino-based secondary aminopropylamine, butyl, triethylenetetramine, toluenedimethylamine, methanolamine, ketone, diphenyl-15-201008971 A second amine of an amine, benzylamine or phenethylamine can be mentioned. Among the compounds having a tertiary amino group and an active hydrogen group, examples of the active hydrogen group include a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, a carboxylic acid, and a hydrazido. Examples of the tertiary amino group and the compound having an active hydrogen group include 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, and phenoxymethyl-2-dimethyl. Amine alcohols such as aminoethanol, 2-diethylamine ethanol, 1-butoxymethyl-2-dimethylamine ethanol, methyldiethanolamine, triethanolamine, and N-hydrazine-hydroxymethylmorpholine; 2-(dimethylaminomethyl)phenol and amine phenols of 2,4,6-tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- Eldecyl imidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-methyl Imidazole, 1-(2-hydroxy-3-phenoxypropyl)-2.ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole And imidazoles of 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole; 1-(2-hydroxy-3-phenoxypropyl)-2-benzene Imidazoline, 1-(2-hydroxy-3-)butyloxypropyl)-2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethylimidazole Porphyrin, 2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-phenylimidazole , 2-(〇-tolyl)-imidazoline, tetra-extension methyl-bis-imidazoline, 1,1,3-trimethyl·1,4-tetramethyl-bis-imidazoline, 1,3 ,3-trimethyl-1,4-tetramethyl-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethyl-bis-4-methylimidazoline, 1 , 2-phenylene-bis-imidazoline, anthracene, 3·phenyl-bis-imidazoline, 1,4·phenyl-bis-imidazoline, 1,4-phenylene·bis-4- Imidazoline of methyl imidazoline; dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethyl-16-201008971 aminoethylamine, Tertiary amine amines of dipropylaminoethylamine, dibutylaminoethylamine, hydrazine methyl piperazine, hydrazine-amine ethylpiperazine and diethylaminoethylpiperazine; 2-diethylamino Ethyl mercaptan, 2-indolylbenzazole, 2-indolyl benzothiazole, 2-indolyl pyridine and 4-indolyl amide thiol; hydrazine, hydrazine-dimethylamino benzoic acid, hydrazine, hydrazine-dimethyl Aminocarboxylic acids of glycine, nicotinic acid, isonicotinic acid and picoline; hydrogenated amines of hydrazine, hydrazine-hydrogenated dimethylglycine, hydrogenated nicotinic acid and hydrogenated isonicotinic acid. The φ amine compound is preferably a compound having a tertiary amino group and an active hydrogen group because of a good balance between storage stability and hardenability. Among them, imidazoles are preferred, and 2-methylimidazole and 2-ethyl-4-methylimidazole are more preferred.

核心，除了胺加成物外亦可含有1種或2種以上之其 他成份。藉由加入其他成份，可賦予所希望的特性。例 如，爲可使更低溫或更短時間下的硬化，比起胺加成物， 可核心含有與環氧樹脂的反應性爲高之化合物或硬化劑 等。亦可預先在硬化物中添加必要之添加劑。 φ 其他成份，以常溫（25°C )下爲固體狀爲滿意。40°C 下爲固體狀爲加，60 °C下爲固體狀則更佳。於常溫下若使 用液體成份則難以膠囊化，有一液性環氧樹脂組成物之儲 藏安定性降低等之傾向。 胺加成物與其他成份，以在核心中均勻混合爲加。作 爲實現均勻混合之方法，有胺加成物與其他成份同時加熱 熔解，充分混合後，冷卻至常溫後粉碎之方法，或將任一 方加熱熔解，接著分散於他方，形成均勻分散物，冷卻至 常溫後粉碎之方法。 -17- 201008971 核心爲具有0.1〜50// m之平均粒徑之粒子狀爲佳。 核心之平均粒徑以0.5〜10/zm爲較佳，更佳爲0.5〜5 /zm。核心平均粒徑若不滿O.lvm，有硬化性與儲藏安定 性難以同時存在之傾向。又，核心平均粒徑若爲50/zm以 下，較可容易得到均質之硬化物。上述平均粒徑係指中 徑。核心平均粒徑可用雷射回繞式粒度分佈測定裝置進行 測定。 @ 核心之形狀並無特別限制，球狀、不規則型皆可，爲 令環氧樹脂低黏度化，以球狀爲佳。在此的球狀係指，除 了正圓外，也包含不規則型之角帶有圓型。 微膠囊型潛在性硬化劑，例如，可藉由具備以下步驟 之製造方法可得；藉由被含於核心之胺加成物與異氰酸酯 與具有活性氫基之化合物及/或水於反散媒中反應，形成 膠囊將核心包覆之步驟，與從反應後之混合物中取出具有 核心及膠囊之微膠囊型硬化劑之步驟。 φ 異氰酸酯以具有一個以上之異氰酸酯基，較佳爲2個 以上之異氰酸酯基之化合物爲佳。作爲理想之異氰酸酯，The core may contain one or more other components in addition to the amine adduct. By adding other ingredients, the desired characteristics can be imparted. For example, in order to make the hardening at a lower temperature or a shorter time, the core may contain a compound having a higher reactivity with the epoxy resin or a hardener than the amine adduct. It is also possible to add necessary additives to the hardened material in advance. φ Other ingredients are satisfactory at normal temperature (25 ° C). It is solid at 40 ° C and more preferably solid at 60 ° C. When a liquid component is used at normal temperature, it is difficult to be encapsulated, and the stability of storage of a liquid epoxy resin composition tends to be lowered. The amine adduct is mixed with other ingredients to be uniformly mixed in the core. As a method for achieving uniform mixing, an amine adduct is simultaneously heated and melted with other components, thoroughly mixed, cooled to room temperature and then pulverized, or melted by either side, and then dispersed to form a uniform dispersion, and cooled to The method of pulverizing after normal temperature. -17- 201008971 The core is preferably a particle having an average particle diameter of 0.1 to 50/m. The average particle diameter of the core is preferably 0.5 to 10/zm, more preferably 0.5 to 5/zm. If the core average particle size is less than O.lvm, it is difficult to have both hardenability and storage stability. Further, if the core average particle diameter is 50/zm or less, a homogeneous cured product can be easily obtained. The above average particle diameter refers to the median diameter. The core average particle diameter can be measured by a laser rewind type particle size distribution measuring apparatus. @ The shape of the core is not particularly limited. It is spherical or irregular. The epoxy resin is low in viscosity and preferably spherical. Here, the spherical shape refers to a circular shape including an irregular shape in addition to a perfect circle. The microcapsule-type latent hardener can be obtained, for example, by a production method having the following steps; by the amine-containing adduct and the isocyanate and the compound having an active hydrogen group and/or water in the anti-distribution medium The reaction is carried out to form a step of coating the core with a capsule, and a step of removing the microcapsule-type hardener having a core and a capsule from the mixture after the reaction. The φ isocyanate is preferably a compound having one or more isocyanate groups, preferably two or more isocyanate groups. As an ideal isocyanate,

異氰酸酯、低分子三異氰酸酯及聚異氰酸酯。脂肪族二異 氰酸酯之例，可舉出伸乙基二異氰酸酯、伸丙基二異氰酸 酯、伸丁基二異氰酸酯、六伸甲基二異氰酸酯及三甲基六 伸甲基二異氰酸酯。脂環式二異氰酸酯之例，可舉出異佛 酮二異氰酸酯、4-4’·二環己基甲烷二異氰酸酯、降莰烷二 異氣酸酯、1,4-異氰酸酯基環己烷、1，3-雙（異氰酸基甲 -18- 201008971 基）環己烷及1，3-雙（2-異氰酸基丙基-2基）·環丙烷。 芳香族二異氰酸酯之例，可舉出伸丙基二異氰酸酯、4,4’ 二苯甲烷二異氰酸酯、二甲苯二異氰酸酯及1，5-萘二異氰 酸酯。低分子三異氰酸酯，可舉例1，6,11-十一烷三異氰 酸酯、1，8-二異氰酸酯-4-異氰酸酯甲基辛烷、1，3,6-六伸 甲基三異氰酸酯、2,6-二異氰酸基已酸-2-異氰酸基乙基、 2,6-二異氰酸基己酸-1-甲基-2-異氰酸酯乙基之脂肪族三異 @ 氰酸酯化合物、三環己基甲烷三異氰酸酯及雙環庚烷三異 氟酸酯等之脂環式三異氰酸酯化合物、三苯甲烷三異氰酸 酯、三（異氰酸酯苯）硫代磷酸鹽等之芳香族三異氰酸酯 化合物。聚異氰酸酯，可列舉聚伸甲基聚苯聚異氰酸酯或 上述二異氰酸酯、經低分子三異氰酸酯所衍生之聚異氰酸 酯。上述經由二異氰酸酯、三異氰酸酯所衍生之聚異氰酸 酯、有異三聚氰酸酯型聚異氰酸酯、縮二脲型聚異氰酸 酯、胺基甲酸乙酯型聚異氰酸酯、脲基甲酸酯型聚異氰酸 φ 酯及碳二醯胺型聚異氰酸酯等。此些異氰酸酯可單獨或2 種以上使用。 藉由具有胺加成物之活性氫基及異氰酸酯之反應，胺 加成物與異氰酸酯結合，於核心表面形成由生成物所成之 被膜。然後，於反應系中藉由具有活性氫基之化合物及/ 或水之存在，含有此些與異氰酸酯之反應生成物之被膜而 成長，形成膠囊。包含於膠囊之反應生成物中之至少一部 份，藉由與經異氰酸酯與胺加成物之反應所生成之胺基甲 酸乙酯結合而鍵結於核心。藉由使用如此般被膜成長後之 -19- 201008971 微膠囊型潛在性硬化劑，認爲可得到一液性環氧樹脂組成 物之充分之儲藏安定性。 微膠囊型潛在性硬化劑中，膠囊（惰性膜）之比爲， 以微膠囊型潛在性硬化劑之全體質量作爲基準以5〜80質 量％爲佳。膠囊之比爲依據所期望之用途及目的，40〜80 質量％、1 5〜4 0質量％或也可爲5〜1 5質量％。 膠囊之比爲，例如，於核心之部份選擇性溶解之溶劑 @ 中，使質量Ml微膠囊型潛在性硬化劑分散，測量此時之 未溶解之固形分之質量M2，可藉由下述式：膠囊之比 (質量％ )=( M2/Ml) xl 00可求得算出膠囊之比的方 法。作爲使核心選擇性溶解之溶劑，例如可使用甲醇。 爲使形成膠囊所使用之化合物之活性氫基，可列舉一 級胺基、二級胺基、羥基、硫醇基、羧酸及醯肼基。以於 一分子中具有一個以上之活性氫基之化合物即可，以使用 於一分子中具有二以上之活性氫基之化合物爲佳。藉由使 φ 用具有二以上之活性氫基之化合物，可製造核心表面之被 膜可有效率地成長，且儲藏安定性爲特佳之微膠囊型潛在 性硬化劑。具有活性氫基之化合物，可使用單獨一種或二 種以上之組合。 膠囊形成之反應，可在分散媒中分散有核心之反應液 中進行。反應以在構成核心之成份（特別係胺加成物）之 溶點或軟化點以下之溫度進行爲佳。 分散媒之沸點以1氣壓下150°C以下爲佳。若分散媒 之沸點爲150 °C以上，有從反應液中變成難以除去分散媒 -20- 201008971 之傾向。又，分散媒之黏度以25t下lOOOmPa· 佳。若分散媒之黏度爲l〇〇〇mPa· s以上，均勻 S困難’所得之微膠囊型潛在性硬化劑爲之凝結 性則有顯著降低之可能性。從同樣的觀點來看， 散媒之沸點爲50〜120°C，分散媒之黏度爲0.2〜 5 ° 分散媒以不具有會與活性氫基或胺加成物反 Φ 基等之取代基爲佳。此些取代基具有阻礙膠囊形 之可能性。作爲適當之分散媒之具體例爲，可舉 (沸點 80.7°C、黏度 0.898mPa· s: 25°c )及己 6 9〇C、黏度 0.299mPa· s: 25°C )。 膠囊形成後，從含有微膠囊型潛在性硬化劑 等之混合物中，去除分散媒。在分散媒中，雖有 異氰酸酯或副生成物、水及/或具有活性氫基之 留之情況，可從分散媒中之殘留物中分離取出微 φ 在性硬化劑。若未反應物包含於微膠囊型潛在 中，則有儲藏安定性降低之可能性。 分散媒之去除方法並無特別限制，以可同時 媒與未反應之異氟酸酯或副生成物、水及具有活 化合物等之殘留物爲佳。理想之方法可舉出濾過 濾過等去除分散媒後，洗淨微膠囊型潛在性硬化 洗淨之方法並無特別限制，濾過後，可使用不溶 型潛在性硬化劑之溶劑洗淨。作爲溶劑亦可使用 同種之物。藉由洗淨，可去除附著於微膠囊型潛 s以下爲 之反應將 其硬化特 較佳之分 -1 OmP a · 應之環氧 成之反應 出環己烷 烷（沸點 及分散媒 未反應之 化合物殘 膠囊型潛 性硬化劑 去除分散 性氫基之 法。藉由 劑爲佳。 解微膠囊 與分散媒 在性硬化 -21 - 201008971 劑表面上之未反應之化合物。經濾過之微膠囊型潛在性硬 化劑，經乾燥成爲粉末狀。乾燥之方法並無特別限制，以 核心之熔點或軟化點以下之溫度下進行乾燥爲佳。作爲此 種方法可舉出減壓乾燥。粉末狀之微膠囊型潛在性硬化 劑，於一液性環氧樹脂組成物中，因配合廣泛之種類，可 容易適用之。 於環氧樹脂中進行膠囊化之方法之情況，因有未反應 0 之異氰酸酯或副生成物、水及/或具有活性氫基之化合物 殘留於一液型環氧樹脂組成物中之結果，而儲藏安定性降 低。又，若將粉末狀之胺加成物粒子添加於高濃度環氧樹 脂中，則黏度顯著提高，無法均勻反應，生產單位間之特 性之差變大，也產生膠囊化反應本身無法進行等之問題。 爲提高反應性，添加了與環氧樹脂反應性高之化合物於核 心，或使用反應性高之環氧樹脂作爲分散媒進行膠囊化， 核心與環氧樹脂之反應會優先進行，微膠囊型潛在性硬化 φ 劑或一液性環氧樹脂組成物之製造則變爲困難。 膠囊形成之反應，如果必較亦可進行2次以上。此 時，至少一次，胺加成物與異氰酸酯與具有活性氫基之化 合物及/或與水進行反應即可，除此之外，使用選自從異 氰酸酯與具有活性氫基之化合物及/或水之任一方進行反 應亦可。從抑制製造成本之觀點，膠囊形成之反應以5次 以下爲佳，更佳爲3次以下。 本實施型態之一液性環氧樹脂組成物含有微膠囊型潛 在性硬化劑與環氧樹脂。微膠囊型潛在性硬化劑之量並無 -22- 201008971 特別限制，通常，相對於環氧樹脂及微膠囊型潛在性硬化 劑之合計量之1〇〇質量份，爲5〜70質量份左右。若此量 未滿5質量份，環氧樹脂有無法充分硬化之傾向，或硬化 時需要有長時間之傾向，若超過70質量份，有環氧樹脂 組成物之流動性降低之傾向》 作爲一液性環氧樹脂組成物所用之環氧樹脂，以具有 平均2個以上之環氧基之環氧化合物可理想地使用。具體 0 而言，雙酚A、雙酚F、雙酚AD、雙酚S、四甲基雙酚 A、四甲基雙酚F、四甲基雙酚AD、四甲基雙酚S、四溴 雙酚A、四氯雙酚A及四氟雙酚A等之雙酚類使其縮水甘 油化所得之雙酚型環氧樹脂；雙酚、二羥基萘及9,9-雙 (4-羥苯基）蕗等之其他之2價酚類使其縮水甘油化所得 之環氧樹脂；1，1，1-三（4-羥苯基）甲烷及4,4-(1-(4-(1-(4-羥苯基）-1-甲基乙基）苯基）亞乙基）雙酚等之 三雙酚類使其縮水甘油化所得之環氧樹脂；1，1，2,2-四（4-Φ 羥苯基）乙烷等之四酚類使其縮水甘油化所得之環氧樹 月旨；酚酚醛清漆、甲酚酚醛清漆、雙酚A酚醛清漆、溴化 酚酚醛清漆及溴化雙酚A酚醛清漆等之酚醛清漆類使其縮 水甘油化所得之酚醛型環氧樹脂等；使多價酚類縮水甘油 化所得之環氧樹脂、丙三醇或聚乙二醇等之多價醇類使其 縮水甘油化所得之脂肪族醚型環氧樹脂；p-氧化安息香 酸、/3-氧化萘甲酸等之羥基羧酸使其縮水甘油化所得之 醚酯型環氧樹脂；酞酸、對酞酸之聚羧酸使其縮水甘油化 所得之酯型環氧樹脂；4,4-二胺二苯甲烷或m-胺基酚等之 -23- 201008971 胺化合物之縮水甘油化物或三縮水甘油異三聚氰酯等之胺 型環氧樹脂等之縮水甘油型環氧樹脂與，3,4-環氧環己基 甲基-3’，4’-環氧環己烷羧酸酯等之脂環族環氧化物等可被 舉出。作爲環氧樹脂之其他例，有胺基甲酸乙酯改性環氧 樹脂、橡膠改性環氧樹脂、酸醇改性環氧樹脂等之改性環 氧樹脂。此些環氧樹脂可單獨使用或亦可2種以上倂用。 一液性環氧樹脂組成物，可加入微膠囊型潛在性硬化 劑’更亦可含有選自酸酐類、酚類、醯肼類及狐類所成群 之至少一種之硬化劑。又’一液性環氧樹脂組成物，依據 期望，亦可含有增量劑、補強材料、塡充材料、導電微粒 子、顏料、有機溶劑、反應性稀釋劑、非反應性稀釋劑、 樹脂類、結晶性醇類、偶合劑等。 作爲塡充劑之例，例如，可舉出煤焦油、玻璃纖維、 石棉纖維、硼纖維、碳纖維、纖維素、聚乙烯粉、聚丙稀 粉、石英粉、礦物性矽酸鹽、雲母、石棉粉、板岩粉、高 嶺土、氧化鋁三水和物、氫氧化鋁、白堊粉、石膏、碳酸 鈣、三氧化銻、聚環氧丙烷、二氧化矽、氣溶膠、鋅鋇 白、重晶石、二氧化鈦、碳黑、石墨、碳奈米管、芙樂 烯、氧化鐵、金、銀、鋁粉、鐵粉、奈米尺寸之金屬結 晶、金屬間化合物等。此些之任一皆可依據其用途有效使 用。 作爲導電微粒子之例，可舉出，焊料粒子、鎳粒子、 奈米尺寸之金屬結晶、金屬表面上被覆其他金屬之粒子、 銅與銀之傾斜粒子等的金屬粒子、或如、苯乙烯樹脂、胺 -24- 201008971 基甲酸乙酯樹脂、三聚氰胺樹脂、環氧樹脂、丙烯酸樹 脂、酣樹脂、苯乙烯-丁二烯樹脂等之樹脂粒子上使其被 覆金、鎳、銀、銅、焊料等之導電性薄膜之粒子等。 作爲有機溶劑，例如，可舉出甲苯、二甲苯、甲基乙 基酮、甲基異丁基酮、醋酸乙酯及醋酸丁酯。 作爲反應性稀釋劑，例如，可舉出丁基環氧丙基醚、 N，N’-環氧丙基-〇_鄰甲苯胺、苯基環氧丙基醚、氧化苯乙 φ 烯、乙二醇二環氧丙基醚、丙二醇二環氧丙基醚及1,6-己 烷二醇二環氧丙基醚。作爲非反應性稀釋劑，例如，可舉 出’二辛基酞酸酯、二丁基酞酸酯、二辛基己二酸鹽及石 油系溶劑。 作爲樹脂，例如，可舉出聚酯樹脂，聚胺基甲酸乙酯 樹脂、丙烯酸樹脂、聚醚樹脂、三聚氰胺樹脂及苯氧樹 脂。 作爲結晶性醇，例如，可舉出1，2 -環己烷二醇、1，3 -φ 環己烷二醇、1，4·環己烷二醇、季戊四醇、葡萄糖醇、蔗 糖及三羥甲基丙烷。 一液性環氧樹脂組成物，理想爲，可藉由具備有微膠 囊型潛在性硬化劑與環氧樹脂混合後之混合物中將微膠囊 型潛在性硬化劑分散之步驟，與將分散後之微膠囊型潛在 性硬化劑加熱處理之步驟之製造方法所得。 藉由使用混合器或輥機將微膠囊型潛在性硬化劑與環 氧樹脂之混合物攪拌，可將微膠囊型潛在性硬化劑分散於 環氧樹脂中。 -25- 201008971 藉由將環氧樹脂中之微膠囊型潛在性硬化劑加熱處 理，因環氧樹脂被拉入膠囊內，更提升儲藏安定性。加熱 處理的溫度’以比常溫（25 °C )高及比構成核心之胺加成 物之融點或軟化點以下爲佳。比常溫還低之情況，有提升 儲藏安定性效果變小之傾向。比胺加成物之融點或軟化點 高之情況’因與環氧樹脂之反應，硬化物之特性容易減 低。以生產觀點來看，處理時間以5分到72小時爲佳。 φ 本實施形態之一液性環氧樹脂組成物係藉由加熱硬化 而形成硬化物。一液性環氧樹脂組成物，除了黏著劑及/ 或接合用膠、接合用膜以外，也可有效用於導電材料、異 向性導電材料、絕緣材料、密封材料、塗層材料、塗料組 成物、預浸體、熱傳導性材料。 實施例 以下，舉出實施例更具體地說明關於本發明。但，本 φ 發明並不限定於此些例。 (檢討1) 1-1.胺加成物粒子之合成 胺加成物粒子1 將具備有冷卻管、等壓分液漏斗、攪拌裝置之3000 mL之三口可拆式燒瓶中加入2 -甲基咪哩288g於1-丁醇 與甲苯以1/1 (wt/wt)混合之溶液824.2g中，一邊攪 拌一邊以油浴加熱至80 °C使2 -甲基咪哩溶解。接著，將 -26- 201008971 雙酚 A型環氧樹脂（環氧當量173 g/eq，水解性氯量 0.01重量％) 946g溶解於以1-丁醇與甲苯以1/1 ( wt/ wt)混合之溶液3 00g中，使用等壓分液漏斗將該溶液於 9 0分中滴下。滴完後，於8 0 °C加熱5小時。其後升溫至 18(TC，使裝置內部之最終壓力減壓成爲lOmmHg以下。 壓力成爲lOmmHg以下後，進而藉由於減壓下進行2小時 加熱以餾去溶劑，得到暗紅褐色之黏稠液體。將此黏稠液 體冷卻至室溫而得到暗紅褐色之固體狀胺加成物。以氣流 式粉碎機將此胺加成物粉碎，得到平均粒子徑1.96ym之 胺加成物粒子1。 胺加成物粒子2 除將雙酚A型環氧樹脂變更爲雙酚F型環氧樹脂（環 氧當量160g/eq，水解性氯量爲0.007重量％) 874g以 外，以與胺加成物粒1同樣之方法進行，得到平均粒徑 〇 之胺加成物粒子2。 1 一 2.微膠囊型潛在性硬化劑之合成 微膠囊型潛在性硬化劑1 將具備有冷卻管、熱電對、攪拌裝置之5 OOmL之三口 可拆式燒瓶中加入45.0g之胺加成物粒子1與171.0g之環 己烷，加熱至40°C，加入水1 .2g。攪拌10分鐘後，加入 4,4’-二苯基甲烷二異氰酸酯3.0g，在40°C下使其反應2 小時。接著升溫至50°C使其反應6小時。反應結束後，將 -27- 201008971 分散液過濾，將回收之粉末以加熱至5 0 °C之環己烷洗淨。 在lOmmHg以下之壓力下進行24小時的減壓乾燥從所得 之粉末中去除溶劑，而得到微膠囊型潛在性硬化劑1。 微膠囊型潛在性硬化劑2 除了將胺加成物粒子2代替胺加成物粒子1使用外， 其他與實施例1同樣進行，得到微膠囊型潛在性硬化劑 參 2。 微膠囊型潛在性硬化劑3 (微膠囊型潛在性硬化劑1之再 膠囊化） 將具備有冷卻管、熱電對、攪拌裝置之5 00mL之三口 可拆式燒瓶中加入146.3g之甲苯與2.5g之4,4’-二苯基甲 烷二異氰酸酯，以油浴加熱至5 (TC。接著加入15. Og之微 膠囊型潛在性硬化劑（F ) 1，在50 °C下使其反應3小 〇 時。反應結束後，將分散液過濾，將回收之粉末以加熱至 50°C之甲苯洗淨。在lOmmHg以下之壓力下進行24小時 的減壓乾燥從所得之粉末中去除溶劑，而得到微膠囊型潛 在性硬化劑3。 微膠囊型潛在性硬化劑4 (添加乙二醇） 將具備有冷卻管、熱電對、攪拌裝置之5OOmL之三口 可拆式燒瓶中加入45.0g之胺加成物粒子1與171.0g之環 己烷，加熱至40 °C。接著加入甲伸苯基二異氰酸酯2.Og -28- 201008971 以4(TC加熱2小時。進而升溫至5(TC，將乙二醇1 2 3.〇g以 6小時均勻加入。反應結束後，將分散液過濾’將回收之 粉末以加熱至5(TC之環己烷洗淨。在lOmmHg以下之壓力 下進行24小時的減壓乾燥從所得之粉末中去除溶劑’而 得到微膠囊型潛在性硬化劑4。 微膠囊型潛在性硬化劑6 φ 將具備有冷卻管、熱電對、攪拌裝置之500mL之三口 可拆式燒瓶中加入45. Og之胺加成物粒子1與171. Og之環 己烷，加熱至40°C後，加水1.2g。攪拌10分鐘後，加入 3.〇g之聚合 MDI (日本 Polyurethane公司製、商品名 Millionate MR-200 )在4(TC下反應2小時。接著升溫至 5 〇°C使其反應6小時。反應結束後，將分散液過濾，將回 收之粉末以加熱至50°C之環己烷洗淨。在lOmmHg以下之 壓力下進行24小時的減壓乾燥從所得之粉末中去除溶 • 劑，而得到微膠囊型潛在性硬化劑6。 -29- 1 - 3. 一液性環氧樹脂組成物之調製 2 實施例1〜3 3 將33g之微膠囊型潛在性硬化劑1、2或3與67g之 雙酚F型環氧樹脂（環氧當量160g/eq，水解性氯量 0.007重量％ )配合而得到實施例1〜3之一液性環氧樹脂 組成物。 201008971 實施例4 將33g之微膠囊型潛在性硬化劑4與67g之雙酸A型 環氧樹脂（環氧當量173g/eq，水解性氯量〇·(π重量％) 配合而得到一液性環氧樹脂組成物。 實施例5 將45g之微膠囊型潛在性硬化劑3與55g之雙酌F型 0 環氧樹脂（環氧當量160g/eq，水解性氯量〇_007重量 %)配合而得到一液性環氧樹脂組成物。 實施例6 將35g之微膠囊型潛在性硬化劑3與25g之雙酚A型 環氧樹脂（環氧當量160g/eq，水解性氯量〇.0〇7重量 % ) 、40g之間苯二酚二環氧丙基醚（環氧當量117g/ eq，水解性氯量0.7重量％ )配合而得到一液性環氧樹脂 _ 組成物。 實施例7 將33g之微膠囊型潛在性硬化劑1加入於具備有冷卻 管、熱電對、攪拌裝置之三口可拆式燒瓶中，加入67g之 雙酚F型環氧樹脂（環氧當量16〇g/ eq，水解性氯量 0 · 0 0 7重量％ ) ’在5 0 °C下攪拌24小時，得到一液性環氧 樹脂組成物。 -30- 201008971 實施例8 除使用微膠囊型潛在性硬化劑2代替微膠囊型潛在性 硬化劑1外，與實施例7同樣實施，得到一液性環氧樹脂 組成物。 1 - 4.微膠囊型潛在性硬化劑之特性評價 實施例1〜8之一液性環氧樹脂組成物之硬化特性及 0 儲藏安定性與胺加成物粒子1，2之平均粒徑使用以下之方 法進行評價。總結其結果示於表1。 硬化特性 關於一液性環氧樹脂組成物使用Perkin-Elmer公司製 DSC7變差式熱量表、升溫速度1〇 °c / min、測定溫度範 圍30 °C〜3 00 °C、測定在氮氣雰圍下之效果特性。若由來 自硬化發熱之峰値之最大溫度未滿11 5 t則判定爲 〇 「AA」’ 1 15°c以上不滿120°C則判定爲「A」，12〇r以 上不滿 13 0 °c則判定爲「B」，1 3 0。(：以上則判定爲 「C」。由來自硬化發熱之峰値最高點溫度越低，意指樹 脂組成物具有優良之低溫硬化性。 儲藏安定性 於一液性環氧樹脂組成物中加入同重量之雙酚A型環 氧樹脂（環氧當量173/eq，水解性氯量〇.〇1重量％)， 保管於40°C之恆溫槽。使用E型黏度計測定一液性環氧 -31 - 201008971 樹脂組成物在25 °C下初期及於30日後之黏度。藉由從初 期開始30日後之黏度增加率判定其儲藏安定性。黏度測 定係使用3° (角度）之圓錐黏度計，黏度爲3〜40Pa*s 時lOrpm、黏度爲40〜200Pa· s時2.5rpm、黏度爲200〜 lOOOPa· s時爲0.5rpm之回轉數下進行。30日後之黏度 增加率爲25%以下則判定爲「AA」、50%以下則判定爲 「A」、100%未滿則判定爲「B」、100%以上則判定爲 φ 「C」。 平均粒徑 胺加成物之平均粒徑使用Malvern公司製之雷射回析 式粒度分佈測定裝置（Mastersizer2000:乾式測定裝置 Scir〇cco2000 )進行3次測定。將此時之50%徑（中點 徑）之平均値作爲平均粒徑。 以下，準備了比較例所用之微膠囊型潛在性硬化劑及 φ —液性環氧樹脂組成物。 微膠囊型潛在性硬化劑5之合成 將具備有冷卻管、熱電對、攪拌裝置之三口可拆式燒 瓶中加入45.0g之胺加成物粒子1與171.〇g之環己烷，加 熱至40t後，攪拌1〇分鐘。其後’加入3.〇g之4,4’_二 苯基甲烷二異氰酸酯在4 0。(：下使其反應2小時。接著升溫 至5 (TC使其反應6小時。反應結束後’將分散液過爐’將 回收之粉末以加熱至5 0°C之環己烷洗淨。在l〇mmHg以下 -32- 201008971 之壓力下進行24小時的減壓乾燥從所得之粉末中去除溶 劑，而得到微膠囊型潛在性硬化劑5。 比較例1 將33g之微膠囊型潛在性硬化劑5與67g之雙酚F型 環氧樹脂（環氧當量16〇g/ eq，水解性氯量0.007重量 %)配合而得到一液性環氧樹脂組成物。 ❹ 比較例2 將具備有冷卻管、熱電對、攪拌裝置之三口可拆式燒 瓶中加入45g之胺加成物粒子1與55g之雙酚A型環氧樹 月旨（環氧當量173g/eq，水解性氯量〇.〇1重量％)，加熱 至40°C後’加水〇.5g。攪拌1〇分後，加入4.0g之4,4’-二苯基甲烷二異氰酸酯在4〇°C下加熱2小時。接著升溫至 5 0°C加熱6小時中，於燒杯中進行硬化反應，無法得到一 φ 液性環氧樹脂組成物。 比較例3 將具備有冷卻管、熱電對、攪拌裝置之三口可拆式燒 瓶中加入33g之胺加成物粒子1與67g之雙酚A型環氧樹 脂（環氧當量173g/eq，水解性氯量〇.〇1重量％)，加熱 至40°C後，加水〇.5g。攪拌1〇分後，加入4 〇g之4,4，_ 二苯基甲烷二異氰酸酯在40。(：下加熱2小時。接著升溫至 5 0°C加熱6小時中’得到〜液性環氧樹脂組成物。 -33- 201008971 比較例1、3之一液性環氧樹脂組成物之硬化特性及 儲藏安定性與微膠囊型潛在性硬化劑5以如上述同樣之方 法進行評價。 生產單位間之特性偏差的比較 關於實施例1、3與比較例1的環氧樹脂組成物，自 微膠囊型潛在性硬化劑的合成到樹脂組成物之調製重複5 φ 次同樣之實驗，檢討其初期黏度的偏差。實施例1的一液 型環氧樹脂組成物中，將初期黏度的最大値除以最小値其 商値爲1.3，以最小値黏度爲1時之標準偏差0.012之誤 差爲至少良好。實施例3之一液性環氧樹脂組成物中，將 初期黏度的最大値除以最小値其商値爲1.2，以最小値黏 度爲1之標準偏差0.00 7之偏差爲至少良好。另一方面， 比較例3之一液性環氧樹脂組成物中’將初期黏度的最大 値除以最小値其商値爲3 _ 6 ’以最小値黏度爲1之標準偏 φ 差0·78之偏差爲大。 將以上之評價結果整理如表1所示。 -34- 201008971 [表1] 實施例 比較例 1 2 3 4 5 6 7 8 1 2 3 胺加成物粒子 1 2 1 1 1 1 1 1 1 1 1 (No.) 膠囊形成 MDI, MDI, MDI, TDI, MDI, MDI, MDI, MDI, MDI MDI, MDI, 用原料 水 水 水 EG 水 水 水 水 水 水 微膠囊型潛 1 2 3 4 3 3 1 2 5 在性硬化劑 [33] [33] [33] [33] [45] [35] P3] [33] [33] [45] [33] [質量份] 環氧樹脂 BisF BisF BisF BisF BisF BisF BisF BisF BisF BisA BisA [質量份] \67] [671 f671 [67] [551 P5] Μ [671 [67] [551 [67] - - - - Res [40] - - - - - 於環氧樹脂中 4ητ m 無 無 ^irr. m 4ttt 热 有 有 無 • 之加熱處理 硬化特性 AA AA A A AA AA A A AA 合成 B 儲藏安定性 A A AA A A AA AA AA C 不可 A 生產單位間 良好 良好 不良 特性偏差Isocyanate, low molecular weight triisocyanate and polyisocyanate. Examples of the aliphatic diisocyanate include ethyl diisocyanate, propyl diisocyanate, butyl diisocyanate, hexamethylene diisocyanate, and trimethyl hexamethylene diisocyanate. Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4-4'-dicyclohexylmethane diisocyanate, norbornane diisophthalate, 1,4-isocyanate cyclohexane, 1, 3-bis(isocyanatomethyl-18-201008971) cyclohexane and 1,3-bis(2-isocyanatopropyl-2yl)·cyclopropane. Examples of the aromatic diisocyanate include propyl diisocyanate, 4,4' diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. Low molecular weight triisocyanate, which may, for example, be 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene monoisocyanate, 2,6 -diisocyanatohexanoic acid-2-isocyanatoethyl, 2,6-diisocyanatohexanoic acid-1-methyl-2-isocyanate ethyl, aliphatic triiso@ cyanate compound An alicyclic triisocyanate compound such as tricyclohexylmethane triisocyanate or bicycloheptane triisofluoride, an aromatic triisocyanate compound such as triphenylmethane triisocyanate or tris(isocyanate benzene) thiophosphate. The polyisocyanate may, for example, be a poly(methyl polyphenylene polyisocyanate) or a polyisocyanate derived from a low molecular weight triisocyanate. The above polyisocyanate derived from diisocyanate or triisocyanate, polyisocyanate type polyisocyanate, biuret type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate φ ester and carbon diamine type polyisocyanate. These isocyanates may be used alone or in combination of two or more. By reacting an active hydrogen group and an isocyanate having an amine adduct, the amine adduct is bonded to the isocyanate to form a film formed of the product on the core surface. Then, in the reaction system, the film of the reaction product of the isocyanate is grown by the presence of the compound having an active hydrogen group and/or water to form a capsule. At least a portion of the reaction product contained in the capsule is bonded to the core by binding to ethyl carbamate formed by the reaction of the isocyanate with the amine adduct. By using the -19-201008971 microcapsule latent curing agent which has been grown as such a film, it is considered that sufficient storage stability of the one-liquid epoxy resin composition can be obtained. In the microcapsule latent curing agent, the ratio of the capsule (inert film) is preferably 5 to 80% by mass based on the total mass of the microcapsule latent curing agent. The ratio of the capsules is 40 to 80% by mass, 15 to 40% by mass, or 5 to 15% by mass, depending on the intended use and purpose. The ratio of the capsules is, for example, a solvent M in the core which is selectively dissolved, and the mass M1 microcapsule-type latent hardener is dispersed, and the mass M2 of the undissolved solid fraction at this time is measured by the following Formula: Capsule ratio (% by mass) = (M2/Ml) xl 00 A method for calculating the ratio of capsules can be obtained. As a solvent which selectively dissolves a core, methanol can be used, for example. The active hydrogen group of the compound used for forming the capsule may, for example, be a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, a carboxylic acid or a thiol group. For the compound having one or more active hydrogen groups in one molecule, it is preferred to use a compound having two or more active hydrogen groups in one molecule. By using φ with a compound having two or more active hydrogen groups, it is possible to produce a microcapsule-type latent curing agent which can efficiently grow a film on the core surface and has excellent storage stability. The compound having an active hydrogen group may be used alone or in combination of two or more. The reaction of forming the capsule can be carried out by dispersing the core reaction liquid in a dispersion medium. The reaction is preferably carried out at a temperature below the melting point or softening point of the constituents of the core (particularly the amine adduct). The boiling point of the dispersing medium is preferably 150 ° C or less at 1 atm. When the boiling point of the dispersion medium is 150 °C or more, it tends to be difficult to remove the dispersion medium -20-201008971 from the reaction liquid. Further, the viscosity of the dispersion medium is preferably 1000 mPa at 25 tons. If the viscosity of the dispersion medium is l〇〇〇mPa·s or more, the microcapsule latent curing agent obtained by uniform S difficulty is significantly reduced in cohesiveness. From the same point of view, the boiling point of the solvent is 50 to 120 ° C, and the viscosity of the dispersing medium is 0.2 to 5 °. The dispersing medium has a substituent which does not have an anti-Φ group with an active hydrogen group or an amine adduct. good. These substituents have the potential to hinder the shape of the capsule. Specific examples of the appropriate dispersing medium include (boiling point: 80.7 ° C, viscosity: 0.898 mPa·s: 25 ° C) and hexamethylene hexachloride, viscosity: 0.299 mPa·s: 25 ° C). After the capsule is formed, the dispersion medium is removed from a mixture containing a microcapsule-type latent curing agent or the like. In the dispersion medium, although the isocyanate or by-product, water, and/or the active hydrogen group remain, the micro φ intrinsic curing agent can be separated from the residue in the dispersion medium. If the unreacted material is contained in the microcapsule type, there is a possibility that the storage stability is lowered. The method for removing the dispersion medium is not particularly limited, and it is preferred to use a medium and an unreacted isofluoride or by-product, water, and a residue having a living compound. The preferred method is a method of washing the microcapsule type latent hardening after removing the dispersion medium by filtration or the like. The method of washing the microcapsule type latent hardening is not particularly limited, and after the filtration, it can be washed with a solvent of an insoluble latent curing agent. The same kind of substance can also be used as the solvent. By washing, the reaction which is adhered to the microcapsule type latent s can be removed, and the epoxy group is preferably cured to a cyclopentane (the boiling point and the dispersion medium are not reacted). The compound residual capsule type latent hardener removes the dispersive hydrogen group. The agent is preferred. The microcapsule and the dispersion medium are unreacted on the surface of the hardening-21 - 201008971. The filtered microcapsule type The latent curing agent is dried to be in a powder form, and the drying method is not particularly limited, and drying is preferably carried out at a temperature lower than the melting point or softening point of the core. As such a method, drying under reduced pressure may be mentioned. Capsule-type latent hardener, which can be easily applied to a liquid epoxy resin composition due to a wide range of types. In the case of encapsulation in epoxy resin, there is an unreacted isocyanate or The by-product, water, and/or the compound having an active hydrogen group remain as a result of the one-pack epoxy resin composition, and the storage stability is lowered. Further, if the powdery amine is added to the pellet When added to a high-concentration epoxy resin, the viscosity is remarkably improved, the reaction cannot be uniformly performed, and the difference in characteristics between the production units becomes large, and the problem that the encapsulation reaction itself cannot be performed is also caused. In order to improve the reactivity, an epoxy resin is added. The compound with high reactivity of the resin is encapsulated at the core or by using a highly reactive epoxy resin as a dispersing medium. The reaction between the core and the epoxy resin takes precedence, and the microcapsule-type latent hardening agent or one-liquid epoxy The production of the resin composition becomes difficult. The reaction of forming the capsule may be carried out twice or more if necessary. At this time, at least once, the amine adduct and the isocyanate and the compound having an active hydrogen group and/or with water are carried out. In addition, the reaction may be carried out by using one selected from the group consisting of an isocyanate and a compound having an active hydrogen group and/or water. From the viewpoint of suppressing the production cost, the reaction for forming a capsule is preferably 5 or less. More preferably, it is 3 times or less. One of the liquid epoxy resin compositions of this embodiment contains a microcapsule type latent hardener and an epoxy resin. The amount of the hardener is not particularly limited to -22-201008971, and is usually about 5 to 70 parts by mass based on 1 part by mass of the total amount of the epoxy resin and the microcapsule latent curing agent. When the amount is 5 parts by mass, the epoxy resin tends to be insufficiently hardened, or it tends to have a long time when hardened, and if it exceeds 70 parts by mass, the fluidity of the epoxy resin composition tends to decrease. The epoxy resin used for the resin composition is preferably used as an epoxy compound having an average of two or more epoxy groups. Specifically, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and tetra are used. Bisphenols such as methyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, and tetrafluorobisphenol A a bisphenol type epoxy resin obtained by glycidation; an epoxy obtained by glycidation of bisphenol, dihydroxynaphthalene, and other divalent phenols such as 9,9-bis(4-hydroxyphenyl)anthracene Resin; 1,1,1-tris(4-hydroxyphenyl)methane and 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl) Ethyl) bisphenol Epoxy resin obtained by glycidation of bisphenols; epoxy resin obtained by glycidation of tetraphenols such as 1,1,2,2-tetrakis(4-Φhydroxyphenyl)ethane A phenolic epoxy resin obtained by glycidation of a phenol novolak, a cresol novolak, a bisphenol A novolac, a brominated phenol novolac, and a brominated bisphenol A novolac; An aliphatic ether type epoxy resin obtained by glycidylating an epoxy resin obtained by glycidylation of a polyvalent phenol, a polyvalent alcohol such as glycerin or polyethylene glycol; p-oxidized benzoic acid, / An ether ester type epoxy resin obtained by glycidylation of a hydroxycarboxylic acid such as oxidized naphthoic acid; an ester type epoxy resin obtained by glycidylation of a carboxylic acid or a polycarboxylic acid of citric acid; 4, 4 a glycidyl type epoxy resin such as a diamine diphenylmethane or an m-aminophenol such as an amine type epoxy resin such as a glycidyl compound of an amine compound or a triglycidyl isocyanurate. An alicyclic epoxide such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate or the like may be Out. As another example of the epoxy resin, there are modified epoxy resins such as a urethane modified epoxy resin, a rubber modified epoxy resin, and an acid alcohol modified epoxy resin. These epoxy resins may be used singly or in combination of two or more. The one-liquid epoxy resin composition may be added to the microcapsule-type latent curing agent, and may further contain at least one selected from the group consisting of an acid anhydride, a phenol, a steroid, and a fox. Further, a liquid epoxy resin composition may also contain an extender, a reinforcing material, a chelating material, conductive fine particles, a pigment, an organic solvent, a reactive diluent, a non-reactive diluent, a resin, or the like according to expectations. Crystalline alcohols, coupling agents, and the like. Examples of the chelating agent include coal tar, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral citrate, mica, asbestos powder. , slate powder, kaolin, alumina trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, polypropylene oxide, cerium oxide, aerosol, zinc lanthanum, barite, Titanium dioxide, carbon black, graphite, carbon nanotubes, fluffene, iron oxide, gold, silver, aluminum powder, iron powder, metal crystals of nanometer size, intermetallic compounds, and the like. Any of these can be effectively used depending on its purpose. Examples of the conductive fine particles include solder particles, nickel particles, metal crystals having a nanometer size, metal particles coated with other metals on the surface of the metal, and inclined particles such as copper and silver, or a styrene resin. Amine-24-201008971 Resin particles such as urethane resin, melamine resin, epoxy resin, acrylic resin, enamel resin, styrene-butadiene resin, etc. are coated with gold, nickel, silver, copper, solder, etc. Particles of conductive film, etc. The organic solvent may, for example, be toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate or butyl acetate. Examples of the reactive diluent include butyl epoxidized propyl ether, N, N'-epoxypropyl-fluorene-o-toluidine, phenylepoxypropyl ether, styrene oxide, and B. Diol diglycidyl ether, propylene glycol diepoxypropyl ether and 1,6-hexanediol diepoxypropyl ether. The non-reactive diluent may, for example, be 'dioctyl decanoate, dibutyl phthalate, dioctyl adipate or a petroleum solvent. The resin may, for example, be a polyester resin, a polyurethane resin, an acrylic resin, a polyether resin, a melamine resin or a phenoxy resin. Examples of the crystalline alcohol include 1,2-cyclohexanediol, 1,3-φ cyclohexanediol, 1,4·cyclohexanediol, pentaerythritol, glucose alcohol, sucrose, and trishydroxyl. Methyl propane. A liquid epoxy resin composition, which is preferably a step of dispersing a microcapsule-type latent hardener in a mixture having a microcapsule-type latent hardener and an epoxy resin, and dispersing A method of producing a microcapsule-type latent hardener for heat treatment. The microcapsule-type latent hardener can be dispersed in the epoxy resin by stirring the mixture of the microcapsule-type latent hardener and the epoxy resin using a mixer or a roller. -25- 201008971 By heat-treating the microcapsule-type latent hardener in the epoxy resin, the epoxy resin is pulled into the capsule to enhance the storage stability. The temperature of the heat treatment is preferably higher than the normal temperature (25 ° C) and lower than the melting point or softening point of the amine-containing adduct constituting the core. When it is lower than normal temperature, there is a tendency to improve the stability of storage stability. When the melting point or softening point of the amine adduct is higher, the characteristics of the cured product are easily reduced by the reaction with the epoxy resin. From a production point of view, the processing time is preferably from 5 minutes to 72 hours. φ The liquid epoxy resin composition of the present embodiment is cured by heat to form a cured product. The one-component epoxy resin composition can be effectively used for conductive materials, anisotropic conductive materials, insulating materials, sealing materials, coating materials, and coating compositions in addition to adhesives and/or bonding adhesives and bonding films. Materials, prepregs, thermally conductive materials. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. (Review 1) 1-1. Amine Adduct Particles of Amine Adduct Particles 1 A 3-mL separable flask equipped with a cooling tube, an isocratic separatory funnel, and a stirring device was added to a 2-methyl group. 288 g of butyl alcohol was dissolved in 824.2 g of a solution of 1-butanol and toluene mixed at 1/1 (wt/wt), and heated to 80 ° C in an oil bath while stirring to dissolve 2-methylimidazole. Next, 946-201008971 bisphenol A type epoxy resin (epoxy equivalent 173 g/eq, hydrolyzable chlorine amount 0.01% by weight) 946g was dissolved in 1-butanol and toluene at 1/1 (wt/wt) The solution was added dropwise to 90% using an isocratic separatory funnel in a mixed solution of 300 g. After the completion of the dropwise addition, it was heated at 80 ° C for 5 hours. Thereafter, the temperature was raised to 18 (TC, and the final pressure inside the apparatus was reduced to 10 mmHg or less. After the pressure became 10 mmHg or less, the solvent was distilled off by heating for 2 hours under reduced pressure to obtain a dark red-brown viscous liquid. The viscous liquid was cooled to room temperature to obtain a dark reddish brown solid amine adduct. The amine adduct was pulverized by a jet mill to obtain an amine adduct particle 1 having an average particle diameter of 1.96 ym. 2 In the same manner as the amine addition pellet 1 except that the bisphenol A epoxy resin was changed to bisphenol F epoxy resin (epoxy equivalent 160 g/eq, hydrolyzable chlorine amount was 0.007% by weight) 874 g. The amine adduct particles 2 having an average particle diameter of 〇 are obtained. 1 - 2. Microcapsule-type latent hardener synthetic microcapsule latent curing agent 1 will be provided with a cooling tube, a thermoelectric pair, and a stirring device of 500 mL 45.0 g of amine adduct particles 1 and 171.0 g of cyclohexane were added to the three separable flasks, heated to 40 ° C, and water was added to 1.2 g. After stirring for 10 minutes, 4,4'-diphenyl was added. 3.0 g of methane diisocyanate, reacted at 40 ° C for 2 small Then, the mixture was heated to 50 ° C for 6 hours. After the reaction was completed, the dispersion of -27-201008971 was filtered, and the recovered powder was washed with cyclohexane heated to 50 ° C. Under a pressure of 10 mmHg or less. The solvent was removed from the obtained powder under reduced pressure drying for 24 hours to obtain a microcapsule-type latent curing agent 1. Microcapsule-type latent curing agent 2 Except that the amine adduct particle 2 was used instead of the amine adduct particle 1 In the same manner as in Example 1, the microcapsule-type latent curing agent 2 was obtained. The microcapsule latent curing agent 3 (recapsuleping of the microcapsule latent curing agent 1) will be provided with a cooling tube and a thermoelectric device. To a stirred tank of 5 00 mL of a three-necked separable flask was charged with 146.3 g of toluene and 2.5 g of 4,4'-diphenylmethane diisocyanate, and heated to 5 (TC) in an oil bath. The microcapsule latent curing agent (F) 1 is reacted at 50 ° C for 3 hours. After the reaction is completed, the dispersion is filtered, and the recovered powder is washed with toluene heated to 50 ° C. 24 hours of reduced pressure drying under a pressure of less than 10 mmHg The solvent is removed from the obtained powder to obtain a microcapsule-type latent curing agent 3. The microcapsule latent curing agent 4 (addition of ethylene glycol) will have a detachable type of 5OOmL with a cooling tube, a thermoelectric pair, and a stirring device. 45.0 g of the amine adduct particles 1 and 171.0 g of cyclohexane were added to the flask, and the mixture was heated to 40 ° C. Then, methyl phenyl diisocyanate 2. Og -28 - 201008971 was added to heat 4 (TC for 2 hours. The temperature was raised to 5 (TC, and ethylene glycol 1 2 3. 〇g was uniformly added over 6 hours. After the completion of the reaction, the dispersion was filtered. The recovered powder was heated to 5 (the cyclohexane of TC was washed. The solvent was removed from the obtained powder under reduced pressure for 24 hours under a pressure of 10 mmHg or less) to obtain a microparticle. Og of the amine adduct particles 1 and 171. The capsule-type latent hardener is used. The microcapsule-type latent hardener 6 φ is provided with a cooling tube, a thermocouple, and a stirring device in a 500 mL three-neck separable flask. Og cyclohexane, after heating to 40 ° C, add 1.2 g of water. After stirring for 10 minutes, add 3. 〇g of polymeric MDI (manufactured by Japan Polyurethane Co., Ltd., trade name Millionate MR-200) at 4 (TC) After 2 hours, the mixture was heated to 5 ° C for 6 hours. After the reaction was completed, the dispersion was filtered, and the recovered powder was washed with cyclohexane heated to 50 ° C. Under a pressure of 10 mmHg or less 24 An hourly vacuum drying removes the solvent from the obtained powder to obtain a microcapsule-type latent curing agent 6. -29- 1 - 3. Preparation of a liquid epoxy resin composition 2 Examples 1 to 3 3 33g of microcapsule-type latent hardener 1, 2 or 3 and 67g of bisphenol F An epoxy resin (epoxy equivalent 160 g/eq, hydrolyzable chlorine amount: 0.007 wt%) was blended to obtain a liquid epoxy resin composition of Examples 1 to 3. 201008971 Example 4 33 g of microcapsule type latent hardening The agent 4 was mixed with 67 g of a diacid A type epoxy resin (epoxy equivalent: 173 g/eq, hydrolyzable chlorine amount 〇 (π% by weight) to obtain a one-liquid epoxy resin composition. Example 5 The capsule type latent curing agent 3 was blended with 55 g of a double-type F type 0 epoxy resin (epoxy equivalent 160 g/eq, hydrolyzable chlorine amount 〇 007% by weight) to obtain a one-liquid epoxy resin composition. 6 35g of microcapsule latent curing agent 3 and 25g of bisphenol A epoxy resin (epoxy equivalent 160g / eq, hydrolyzable chlorine amount 〇.0 〇 7 wt%), 40g of benzenediol II The epoxy propyl ether (epoxy equivalent: 117 g/eq, hydrolyzable chlorine amount: 0.7% by weight) was blended to obtain a one-part epoxy resin _ composition. Example 7 33 g of the microcapsule-type latent curing agent 1 was added thereto. 67g of bisphenol F-type epoxy resin (epoxy) in a three-piece detachable flask with cooling tube, thermoelectric pair and stirring device The amount is 16 〇g / eq, and the amount of hydrolyzable chlorine is 0 · 0 0 7 wt%) 'The mixture is stirred at 50 ° C for 24 hours to obtain a one-part epoxy resin composition. -30- 201008971 Example 8 The capsule type latent curing agent 2 was used in the same manner as in Example 7 except that the microcapsule latent curing agent 1 was used, and a liquid epoxy resin composition was obtained. 1 - 4. Evaluation of characteristics of the microcapsule latent curing agent The hardening characteristics of the liquid epoxy resin composition of Examples 1 to 8 and the storage stability of the amine and the average particle diameter of the amine adduct particles 1, 2 were evaluated by the following methods. The results are summarized in Table 1. Hardening characteristics The liquid-liquid epoxy resin composition was subjected to a DSC7 differential heat meter manufactured by Perkin-Elmer Co., Ltd., a heating rate of 1 〇 ° C / min, a measurement temperature range of 30 ° C to 300 ° C, and a nitrogen atmosphere. The effect characteristics. If the maximum temperature from the peak of the hardening heat is less than 11 5 t, it is judged as AA "AA"' 1 15 °c or more and 120 °C is judged as "A", 12 〇r or more is less than 13 0 °c. The judgment is "B", 1 3 0. (: The above is judged as "C". The lower the temperature from the peak of the peak of the hardening heat, the lower the temperature of the resin composition means that the resin composition has excellent low-temperature hardenability. The storage stability is added to the one-liquid epoxy resin composition. The weight of the bisphenol A type epoxy resin (epoxy equivalent 173 / eq, hydrolyzable chlorine amount 〇 〇 1% by weight), stored in a thermostat at 40 ° C. One-component epoxy was measured using an E-type viscometer - 31 - 201008971 The viscosity of the resin composition at the initial and after 30 days at 25 ° C. The storage stability was determined by the viscosity increase rate after 30 days from the initial stage. The viscosity was measured using a 3° (angle) cone viscometer. The viscosity is 3 to 40 Pa*s at 10 rpm, the viscosity is 40 to 200 Pa·s at 2.5 rpm, and the viscosity is 200 to 100 OA·s at 0.5 rpm. The viscosity increase rate after 30 days is 25% or less. "A" is 50% or less, "A" is judged as "B" when 100% or less, and φ "C" is judged as 100% or more. The average particle size of the average particle size amine adduct is Malvern. Laser-reviewed particle size distribution measuring device (Mastersizer2000: dry test) The apparatus Scir〇cco2000) was measured three times. The average enthalpy of the 50% diameter (midpoint diameter) at this time was taken as the average particle diameter. Hereinafter, the microcapsule-type latent curing agent used in the comparative example and φ-liquid property were prepared. Epoxy resin composition. Synthesis of microcapsule latent hardener 5 will be added to a three-disconnected flask with a cooling tube, thermoelectric pair and stirring device, and 45.0 g of amine adduct particles 1 and 171. After cyclohexane, after heating to 40 t, it was stirred for 1 hr. After that, 4 g of 4,4'-diphenylmethane diisocyanate was added to the mixture at 4: (the reaction was allowed to proceed for 2 hours. 5 (TC was allowed to react for 6 hours. After the end of the reaction, 'the dispersion was passed through the furnace'. The recovered powder was washed with cyclohexane heated to 50 ° C. Under the pressure of -32-201008971 below l〇mmHg The solvent was removed from the obtained powder under reduced pressure drying for 24 hours to obtain a microcapsule-type latent curing agent 5. Comparative Example 1 33 g of a microcapsule-type latent hardener 5 and 67 g of a bisphenol F-type epoxy resin ( Epoxy equivalent of 16 〇g / eq, hydrolyzable chlorine amount of 0.007 wt%) to obtain a liquid epoxy tree Fat composition. ❹ Comparative Example 2 45 g of amine adduct particles 1 and 55 g of bisphenol A type epoxy resin were added to a three-neck separable flask equipped with a cooling tube, a thermoelectric pair, and a stirring device. Equivalent to 173 g / eq, hydrolyzable chlorine amount 〇 〇 1% by weight), heated to 40 ° C, 'add water 〇. 5g. After stirring for 1 〇, add 4.0g of 4,4'-diphenylmethane diisocyanate Heat at 4 ° C for 2 hours. Then, the temperature was raised to 50 ° C for 6 hours, and the hardening reaction was carried out in a beaker to obtain a liquid chemical epoxy resin composition. Comparative Example 3 33 g of amine adduct particles 1 and 67 g of bisphenol A type epoxy resin (epoxy equivalent 173 g/eq, hydrolyzability) were placed in a three-neck separable flask equipped with a cooling tube, a thermoelectric pair, and a stirring device. Chlorine amount 〇 〇 1% by weight), after heating to 40 ° C, add water. 5g. After stirring for 1 minute, 4 4g of 4,4,_diphenylmethane diisocyanate was added at 40. (: heating for 2 hours. Then heating to 50 ° C for 6 hours to obtain ~ liquid epoxy resin composition. -33- 201008971 The hardening properties of one of the liquid epoxy resin compositions of Comparative Examples 1 and 3. And the storage stability and the microcapsule-type latent curing agent 5 were evaluated in the same manner as above. Comparison of characteristic deviations between production units The epoxy resin compositions of Examples 1, 3 and Comparative Example 1, from microcapsules The synthesis of the latent curing agent to the resin composition was repeated 5 φ times in the same experiment, and the initial viscosity deviation was examined. In the one-liquid epoxy resin composition of Example 1, the maximum viscosity of the initial viscosity was divided by The minimum 値 is 1.3, and the error of the standard deviation of 0.012 with a minimum 値 viscosity of 1 is at least good. In a liquid epoxy resin composition of Example 3, the maximum enthalpy of the initial viscosity is divided by the minimum 値The discount is 1.2, and the deviation of the standard deviation of 0.007 with a minimum 値 viscosity of 1 is at least good. On the other hand, in the liquid epoxy resin composition of Comparative Example 3, the maximum enthalpy of the initial viscosity is divided by the minimum 値. Its business is 3 _ 6 'The deviation of the standard deviation φ difference of 0·78 with a minimum 値 viscosity of 1 is large. The above evaluation results are shown in Table 1. -34- 201008971 [Table 1] Example Comparative Example 1 2 3 4 5 6 7 8 1 2 3 Amine adduct particles 1 2 1 1 1 1 1 1 1 1 1 (No.) Capsules form MDI, MDI, MDI, TDI, MDI, MDI, MDI, MDI, MDI MDI, MDI, Raw material water water EG water water water water water microcapsule type latent 1 2 3 4 3 3 1 2 5 in sexual hardener [33] [33] [33] [33] [45] [35] P3] [ 33] [33] [45] [33] [Mass] Epoxy BisF BisF BisF BisF BisF BisF BisF BisF BisF BisA BisA [Mass] [67] [671 f671 [67] [551 P5] Μ [671 [ 67] [551 [67] - - - - Res [40] - - - - - 4ητ m in epoxy resin no ^irr. m 4ttt Heat or not • Heat treatment hardening characteristics AA AA AA AA AA AA AA Synthetic B Storage stability AA AA AA AA AA AA C Non-A Deviation of good good characteristics between production units

BisF:雙酚F型環氧樹脂(環氧當量160g/eq·冰解性氯量0.007wt%) BisA:雙酚A型環氧樹脂(環氧當量173g/eq.冰解性氯量O.Olwt%) Res:間苯二酣二環氧丙基醚(環氧當量117g/eq.,水解性氯量〇.7wt%) MDI:4,4’-二苯甲烷二異氰酸酯 TDI:二異氰酸甲苯酯 EG:乙二醇 從表1所示結果可明顯得知，藉由使用本發明之微膠 囊型潛在性硬化劑，確認可得到具有充分低溫硬化特性及 優良儲藏安定性之一液性環氧樹脂組成物。 實施例9 -35- 201008971 將30g之微膠囊型潛在性硬化性1與50g之雙酣A型 環氧樹脂（環氧當量173g/eq.,水解性氯量〇.〇1質量％) 與20g之雙酚F型環氧樹脂（環氧當量16〇g/eq·,水解性 氯量0· 007質量％ )配合，得到實施例9之一液性環氧樹 脂組成物。 實施例1 0、1 1 將30g之微膠囊型潛在性硬化性3或6與50g之雙酚 F型環氧樹脂（環氧當量160g/eq.，水解性氯量0.007質 量％)與20g之雙酚A型環氧樹脂（環氧當量173g/eq·, 水解性氯量〇·〇1質量％ )配合，得到實施例10、1 1之一 液性環氧樹脂組成物。 比較例4 將具備有冷卻管、熱電對、攪拌裝置之三口可拆式燒 瓶中加入30g之胺加成物粒子1與50g之雙酚Α型環氧樹 脂（環氧當量173g/eq，水解性氯量〇.〇1質量％)與20g 之雙酚F型環氧樹脂（環氧當量160g/ eq，水解性氯量 0.007質量％)，加熱至4〇t後，加水〇.5g。攪拌1〇分 後，加入3.0g之4,4，-二苯基甲烷二異氰酸酯在40°C下加 熱2小時。接著升溫至5 0。(：加熱6小時中，得到一液性環 氧樹脂組成物。 比較例5 -36- 201008971 將具備有冷卻管、熱電對、攪拌裝置之三口可拆式燒 瓶中加入30g之胺加成物粒子1與50g之雙酚F型環氧樹 月旨（環氧當量160g/ eq，水解性氯量0.007質量％ )與 2〇g之雙酚A型環氧樹脂（環氧當量173g/eq，水解性氯 量0.01質量％)，加熱至40°C後，加水（K5g。攪拌10分 後，加入 3.0g 之 Polymeric MDI (日本 POLYURETHANE 公司製、商品名：Millionate MR-200)在40°C下加熱2小 φ 時。接著升溫至50°C加熱6小時中，得到一液性環氧樹脂 組成物。 [表2] 實施例 比較例 9 10 11 4 5 胺加成物粒子(No·) 1 1 1 1 1 膠囊形成用原料 MDI，水 PMDI,水 MDI，水 MDI，水 PMDI，水 微膝囊型潛在性硬化 1 6 3 - - 劑(No·)[質量份] Γ301 [30] Γ301 胺加成物粒子 - - 1 1 (No.)[質量份] Γ301 「301 環氧樹脂 BisA BisF BisF BisA BisF [質量份] Γ5〇1 [501 「501 Γ501 [501 BisF BisA BisA BisF BisA [201 P〇l Γ201 『201 『201 於環氧樹脂中之 加熱處理 無 M J l \N -fnrr llll JWS - 硬化特性 A AA B C B 儲藏安定性 AA A AA A B 黏度(Pa · s) 29 23 24 168 128BisF: bisphenol F type epoxy resin (epoxy equivalent 160g / eq · ice solution chlorine amount 0.007wt%) BisA: bisphenol A type epoxy resin (epoxy equivalent 173g / eq. ice solution chlorine amount O. Olwt%) Res: isophthalene diepoxypropyl ether (epoxy equivalent: 117 g/eq., hydrolyzable chlorine amount: 7% by weight) MDI: 4,4'-diphenylmethane diisocyanate TDI: diisocyanate Acid toluene EG: Ethylene glycol It is apparent from the results shown in Table 1 that by using the microcapsule-type latent curing agent of the present invention, it is confirmed that one liquid property having sufficient low-temperature hardening property and excellent storage stability can be obtained. Epoxy resin composition. Example 9 -35- 201008971 30 g of microcapsule type latent curing 1 and 50 g of biguanide type A epoxy resin (epoxy equivalent: 173 g/eq., hydrolyzable chlorine amount 〇.1% by mass) and 20 g A bisphenol F-type epoxy resin (epoxy equivalent 16 〇g/eq·, hydrolyzable chlorine amount 0·007% by mass) was blended to obtain a liquid epoxy resin composition of Example 9. Example 1 0, 1 1 30 g of microcapsule-type latent curing 3 or 6 and 50 g of bisphenol F-type epoxy resin (epoxy equivalent 160 g/eq., hydrolyzable chlorine amount 0.007 mass%) and 20 g of A bisphenol A type epoxy resin (epoxy equivalent: 173 g/eq·, hydrolyzable chlorine amount 〇·〇1% by mass) was blended to obtain a liquid epoxy resin composition of Examples 10 and 11. Comparative Example 4 30 g of amine adduct particles 1 and 50 g of bisphenol fluorene type epoxy resin (epoxy equivalent 173 g/eq, hydrolyzability) were placed in a three-neck separable flask equipped with a cooling tube, a thermoelectric pair, and a stirring device. Chlorine amount 〇 〇 1% by mass) and 20 g of bisphenol F type epoxy resin (epoxy equivalent 160 g / eq, hydrolyzable chlorine amount 0.007 mass%), and after heating to 4 Torr, 5 g of water was added. After stirring for 1 minute, 3.0 g of 4,4,-diphenylmethane diisocyanate was added and heated at 40 ° C for 2 hours. Then the temperature is raised to 50. (: A liquid epoxy resin composition was obtained by heating for 6 hours. Comparative Example 5 - 36 - 201008971 30 g of amine adduct particles were added to a three-piece separable flask equipped with a cooling tube, a thermoelectric pair, and a stirring device. 1 and 50 g of bisphenol F-type epoxy resin (epoxy equivalent 160 g / eq, hydrolyzable chlorine amount 0.007 mass%) and 2 g of bisphenol A type epoxy resin (epoxy equivalent 173 g / eq, hydrolysis The amount of chlorine was 0.01% by mass), and after heating to 40 ° C, water (K5g was added. After stirring for 10 minutes, 3.0 g of Polymeric MDI (manufactured by Nippon POLYURETHANE Co., Ltd., trade name: Millionate MR-200) was added and heated at 40 ° C. 2 small φ. Then, the temperature was raised to 50 ° C for 6 hours to obtain a one-liquid epoxy resin composition. [Table 2] Example Comparative Example 9 10 11 4 5 Amine adduct particles (No) 1 1 1 1 1 Raw material for capsule formation MDI, water PMDI, water MDI, water MDI, water PMDI, water micro-knee-type latent curing 1 6 3 - -agent (No) [mass] Γ 301 [30] Γ 301 Amine plus Adult particles - - 1 1 (No.) [Mass] Γ 301 "301 Epoxy BisA BisF BisF BisA BisF [Mass] Γ5〇1 [501 "5 01 Γ501 [501 BisF BisA BisA BisF BisA [201 P〇l Γ201 『201 『201 Heat treatment in epoxy resin without MJ l \N -fnrr llll JWS - Hardening characteristics A AA BCB Storage stability AA A AA AB Viscosity (Pa · s) 29 23 24 168 128

BisF:雙酚F型環氧樹脂隳氧當量160g/eq.冰解性氯量0.007wt%)BisF: bisphenol F type epoxy resin 隳 oxygen equivalent 160g / eq. ice solution chlorine amount 0.007wt%)

BisA:雙酚A型環氧樹脂谭氧當量173g/eq.,水解性氯量O.Olwt%) PMDI: Polymeric MDI(日本 URETHANE 公司製，商品名:Millionate MR200) MDI:4,4’-二苯甲烷二異氰酸酯 -37- 201008971 如表2所示結果可明顯得知，藉由使用本發明之微膠 囊型潛在性硬化劑，確認了不只可得到充分之低溫硬化特 性及優良儲藏安定性，與同樣組成之環氧樹脂相比較時， 可達成比胺加成物粒子更低之黏度，即可達成更高之流動 性。 (檢討2) φ 2—1.胺加成物粒子之合成 胺加成物粒子3 將具備有冷卻管、等壓分液漏斗、攪拌裝置之3 000 mL之三口可拆式燒瓶中加入2-甲基咪唑336.4g於1-丁醇 與甲苯以1/ 1 ( wt/ wt)混合之溶液824.2g中，一邊攪 拌一邊以油浴加熱至8(TC使2·甲基咪唑溶解。接著，將 雙酚A型環氧樹脂（環氧當量173 g/eq，水解性氯量 0.01質量％) 94 5_8g溶解於以1-丁醇與甲苯以1/1( wt/ 〇 Wt)混合之溶液3 00g中，使用等壓分液漏斗將該溶液於 90分鐘滴下。滴完後，於80 °C加熱5小時。其後升溫至 . 180°C，使裝置內部之最終壓力減壓成爲lOmmHg以下。 壓力成爲lOrnmHg以下後，進而藉由於減壓下進行2小時 加熱以餾去溶劑，得到暗紅褐色之黏稠液體。將此黏稠液 體冷卻至室溫而得到暗紅褐色之固體狀胺加成物。以氣流 式粉碎機將此胺加成物粉碎，得到平均粒子徑2.50/zm之 胺加成物粒子3。 -38- 201008971 胺加成物粒子4 除將雙酚A型環氧樹脂變更爲雙酚f型環氧樹脂（環 氧當量160g/eq’水解性氯量爲0007質量％) 874g以 外，以與胺加成物粒1同樣之方法進行，得到平均粒徑 3.14/zm之胺加成物粒子4。 2- 2.微膠囊型潛在性硬化劑之合成 φ 微膠囊型潛在性硬化劑7 將具備有冷卻管' 熱電對、攪拌裝置之之三口可拆式 燒瓶中加入45.0g之胺加成物粒子1與171.Og之環己烷， 加熱至40°C ’加入水l.lg。攪拌10分鐘後，加入4,4，-二 苯基甲烷二異氰酸酯6.Og，在40 °C下使其反應2小時。 接著升溫至50°C使其反應6小時。反應結束後，將分散液 過濾，將回收之粉末以加熱至50 °C之環己烷洗淨。在 lOmmHg以下之壓力下進行24小時的減壓乾燥從所得之粉 β 末中去除溶劑，而得到粉末狀微膠囊型潛在性硬化劑7。 所得之微膠襄型潛在性硬化劑7之中膠囊的比例爲1 4質 . 量 〇/〇。 微膠囊型潛在性硬化劑8 將具備有冷卻管、熱電對、攪拌裝置之5 OOmL之三口 可拆式燒瓶中加入45.0g之胺加成物粒子1與171.0g之環 己烷，加熱至40°C，加入水l.lg。接著，加入4,4，-二苯 基甲烷二異氰酸酯3.0g’在40°C下使其反應2小時。接 -39- 201008971 著升溫至50°C使其反應6小時。反應結束後，將分散液過 濾，將回收之粉末以甲苯洗淨。在lOmmHg以下之壓力下 進行24小時的減壓乾燥從所得之粉末中去除溶劑，而得 到粉末狀微膠囊型潛在性硬化劑8。所得之微膠囊型潛在 性硬化劑8之中膠囊的比例爲9質量％。 微膠囊型潛在性硬化劑9 〇 將具備有冷卻管、熱電對、攪拌裝置之之三口可拆式 燒瓶中加入45.Og之胺加成物粒子2與171. Og之環己烷， 加熱至40°C，加入水l.lg。攪拌10分鐘後，加入4,4’-二 苯基甲烷二異氰酸酯6. Og，在40 °C下使其反應2小時。 接著升溫至50°C使其反應6小時。反應結束後，將分散液 過濾，將回收之粉末以加熱至5(TC之環己烷洗淨。在 lOmmHg以下之壓力下進行24小時的減壓乾燥從所得之粉 末中去除溶劑，而得到粉末狀微膠囊型潛在性硬化劑9。 © 所得之微膠囊型潛在性硬化劑9之中膠囊的比例爲15質 量％。 微膠囊型潛在性硬化劑10 (微膠囊型潛在性硬化劑7之再 膠囊化） 將具備有冷卻管、熱電對、攪拌裝置之5 00mL之三口 可拆式燒瓶中加入146.3g之甲苯與3.7g之4，4，-二苯基甲 烷二異氰酸酯，以油浴加熱至5 (TC，接著加入15.0g之微 膠囊型潛在性硬化劑7，在501：下使其反應3小時。反應 -40- 201008971 結束後，將分散液過濾，將回收之粉末以加熱至5 0°C之甲 苯洗淨。在lOmmHg以下之壓力下進行24小時的減壓乾 燥從所得之粉末中去除溶劑，而得到粉末狀微膠囊型潛在 性硬化劑10。所得之微膠囊型潛在性硬化劑10之中膠囊 的比例爲4 5質量％。 微膠囊型潛在性硬化劑11 (微膠囊型潛在性硬化劑7之再 0 膠囊化） 將具備有冷卻管、熱電對、攪拌裝置之5 OOmL之三口 可拆式燒瓶中加入146.3g之甲苯與1.8g之4,4’-二苯基甲 烷二異氰酸酯，以油浴加熱至5 0°C，接著加入15. 〇g之微 膠囊型潛在性硬化劑7，在50°C下使其反應3小時。反應 結束後，將分散液過濾，將回收之粉末以加熱至50°C之甲 苯洗淨。在lOmmHg以下之壓力下進行24小時的減壓乾 燥從所得之粉末中去除溶劑，而得到粉末狀微膠囊型潛在 性硬化劑1 1。所得之微膠囊型潛在性硬化劑1 1之中膠囊 的比例爲2 8質量％。 2 - 3. —液性環氧樹脂組成物之調製 實施例1 2〜1 6 將微膠囊型潛在性硬化劑7〜11各自33g與雙酚F型 環氧樹脂（環氧當量16〇g/eq，水解性氯量0.007質量 % ) 67g配合，得到實施例1 2〜1 6之一液性環氧樹脂組成 201008971 實施例17 將33g之微膠囊型潛在性硬化劑ι〇與雙酚a型環氧 樹脂（環氧當量173g/eq，水解性氯量〇.(π質量％) 67g 配合，得到實施例1 7之一液性環氧樹脂組成物。 實施例18 ❷ 將33g之微膠嚢型潛在性硬化劑1〇與萘型環氧樹脂 (環氧當量142g/eq，水解性氯量0.017質量67g配 合，得到實施例1 8之一液性環氧樹脂組成物。 實施例19 將35g之微膠囊型潛在性硬化劑1〇與雙酚ρ型環氧 樹脂（環氧當量160g/eq，水解性氯量〇.〇〇7質量％) 25g 與間苯二酣二環氧丙基醚（環氧當量117g/eq，水解性氯 〇 量〇·7質量％) 40g配合，得到實施例19之一液性環氧樹 脂組成物。 2 — 4.爲比較用之微膠囊型潛在性硬化劑及一液性環氧樹 脂組成物 微膠囊型潛在性硬化劑1 2之合成 將具備有冷卻管、熱電對、攪拌裝置之三口可拆式燒 瓶中加入45.0g之胺加成物粒子1與171.0g之環己烷，加 熱至40 °C，攪拌10分鐘。其後，加入4,4’-二苯基甲烷二 -42- 201008971 異氰酸酯l.〇g，在40°C下使其反應2小時。接著升溫至 5 0°C使其反應6小時。反應結束後，將分散液過濾，將回 收之粉末以加熱至50°C之環己烷洗淨。在lOmmHg以下之 壓力下進行24小時的減壓乾燥從所得之粉末中去除溶 劑，而得到微膠囊型潛在性硬化劑12。所得之微膠囊型潛 在性硬化劑1 2之中膠囊的比例爲3質量％。 0 比較例6 將33g之微膠嚢型潛在性硬化劑12與雙酚F型環氧 樹脂（環氧當量160g/eq，水解性氯量0.007質量％) 67g 配合，得到比較例6之一液性環氧樹脂組成物。 比較例7 將具備有冷卻管、熱電對、攪拌裝置之三口可拆式燒 瓶中加入45.0g之胺加成物粒子1與55g之雙酚A型環氧 〇 樹脂（環氧當量173g/eq，水解性氯量0.01質量％)，加 熱至4〇°C後，加水0.5g。攪拌10分後，加入4.0g之 4,4’-二苯基甲烷二異氰酸酯在40 °C下加熱2小時。接著 升溫至50 °C加熱6小時中，於燒杯中進行硬化反應，無法 得到一液性環氧樹脂組成物。 比較例8 將具備有冷卻管、熱電對、攪拌裝置之三口可拆式燒 瓶中加入45g之胺加成物粒子1與55g之雙酚F型環氧樹 -43- 201008971 脂（環氧當量160g/eq，水解性氯量〇_〇〇7質量％)，於 燒杯中進行硬化反應，無法得到一液性環氧樹脂組成物。 2- 5.微膠囊型潛在性硬化劑之特性評價 實施例及比較例之一液性環氧樹脂之硬化特性及儲藏 安定性與胺加成物粒子3、4之平均粒徑用以下之方法進 行評價。整合其結果如表3所示。 參 硬化特性 對於一液性環氧樹脂組成物，使用Perkin-Elmer公司 製DSC7示差熱量計在昇溫速度l〇°C/min，測定溫度範 圍30°C〜3 00 °C，氮雰圍下測定其硬化特性。若源自硬化 發熱之峰値最大點溫度爲未滿1 1 0 °C則判定爲「AA」， 110°C以上125°C未滿則判定爲「A」，125°C以上130°C未 滿則判定爲「B」，1 3 5 °C以上則判定爲「C」。 ❿ 儲藏安定性 依照與檢討1的場合相同之測定條件及基準，測定環 氧樹脂組成物之儲藏安定性與安加成物之平均粒徑。 膠襄之比例 將充分量之甲醇加於微膠囊型潛在性硬化劑所調製之 分散液藉由在室溫下攪拌6小時，使微膠囊型潛在性硬化 劑之中之源自胺加成物粒子之部份溶解於甲醇。將分散液 -44- 201008971 濾過’將濾過物以5 0 °C以下之溫度乾燥，完全去除甲醇。 計量乾燥後之濾過物重量。將相對於濾過物之重量之微膠 囊型環氧樹脂用硬化劑全體重量比例看作爲膠囊之比例。 耐溶劑性 使用以甲苯/醋酸乙酯=1/1 (wt/wt)作爲溶劑， 使一液性環氧樹脂組成物/溶劑=15g/3.5g之混合物保持 ❹ 於40 °C之水浴中，觀察此時之混合物之黏度變化。若到無 流動性之時間爲〇〜3小時則判定爲「C」，3〜6小時則 判定爲「B」，6〜1 0小時則判定爲「A」、1 0小時以上則 判定爲「AA」。 -45- 201008971 [表3]BisA: bisphenol A type epoxy resin tantalum equivalent 173g/eq., hydrolyzable chlorine amount O.Olwt%) PMDI: Polymeric MDI (made by Japan URETHANE company, trade name: Millionate MR200) MDI: 4,4'- Phenylmethane diisocyanate-37-201008971 As apparent from the results shown in Table 2, it was confirmed that not only sufficient low-temperature hardening property and excellent storage stability were obtained by using the microcapsule latent curing agent of the present invention, When the epoxy resin of the same composition is compared, a lower viscosity than the amine adduct particles can be achieved, and a higher fluidity can be achieved. (Review 2) φ 2 -1. Amine adduct particles 3 of an amine adduct particle. Add 3 to a 3 000 mL three-piece separable flask equipped with a cooling tube, an isocratic separatory funnel, and a stirring device. 336.4 g of methyl imidazole in 824.2 g of a solution of 1-butanol and toluene mixed at 1/1 (wt/wt), and heated to 8 (TC to dissolve 2·methylimidazole) while stirring. Bisphenol A type epoxy resin (epoxy equivalent: 173 g/eq, hydrolyzable chlorine amount: 0.01% by mass) 94 5_8 g dissolved in a solution of 1-butanol and toluene mixed at 1/1 (wt/〇Wt) 300 g The solution was dropped over 90 minutes using an isocratic separatory funnel, and after heating, it was heated at 80 ° C for 5 hours, and then heated to 180 ° C to reduce the final pressure inside the apparatus to 10 mmHg or less. After it became lOrnmHg or less, the solvent was distilled off under reduced pressure for 2 hours to obtain a dark reddish brown viscous liquid. The viscous liquid was cooled to room temperature to obtain a dark reddish brown solid amine adduct. The amine adduct was pulverized by a pulverizer to obtain an amine adduct particle 3 having an average particle diameter of 2.50 / zm. -38 - 2010089 71 Amine adduct particles 4 In addition to changing the bisphenol A type epoxy resin to a bisphenol f type epoxy resin (epoxy equivalent 160 g / eq 'hydrolyzable chlorine amount is 0007% by mass) 874 g, addition to amine The particle 1 is obtained in the same manner to obtain an amine adduct particle 4 having an average particle diameter of 3.14 / zm. 2- 2. Synthesis of a microcapsule latent hardener φ Microcapsule latent hardener 7 will have a cooling tube Add 45.0 g of amine adduct particles 1 and 171.0 g of cyclohexane to the three separable flasks of the thermoelectric pair and stirrer, and heat to 40 ° C. Add water l.lg. After stirring for 10 minutes, 4.Og of 4,4,-diphenylmethane diisocyanate was added, and the reaction was carried out for 2 hours at 40 ° C. Then, the mixture was heated to 50 ° C for 6 hours. After the reaction was completed, the dispersion was filtered and recovered. The powder was washed with cyclohexane heated to 50 ° C. The solvent was removed from the obtained powder β at a pressure of less than 10 mmHg for 24 hours to obtain a powdery microcapsule latent hardener 7 The ratio of the capsules in the obtained microcapsule type latent hardener 7 is 14 mass. 〇/〇. Microcapsule type In the hardening agent 8, 45.0 g of the amine adduct particle 1 and 171.0 g of cyclohexane were placed in a 500-neck separable flask equipped with a cooling tube, a thermoelectric pair, and a stirring device, and heated to 40 ° C. Water l.lg was added, and then, 4,4,-diphenylmethane diisocyanate 3.0 g' was added and reacted at 40 ° C for 2 hours. The temperature was raised to 50 ° C for 6 hours from -39 to 201008971. . After completion of the reaction, the dispersion was filtered, and the recovered powder was washed with toluene. The solvent was removed from the obtained powder under reduced pressure of 10 mmHg or less for 24 hours to obtain a powdery microcapsule-type latent curing agent 8. The ratio of the capsules in the obtained microcapsule-type latent curing agent 8 was 9% by mass. The microcapsule type latent hardener 9 〇 will be provided with a cooling tube, a thermoelectric pair, a stirring device, and a detachable flask containing 45.Og of the amine adduct particles 2 and 171. Og of cyclohexane, heated to At 40 ° C, water l.lg was added. After stirring for 10 minutes, 6. Og of 4,4'-diphenylmethane diisocyanate was added and allowed to react at 40 ° C for 2 hours. Then, the temperature was raised to 50 ° C to carry out a reaction for 6 hours. After the completion of the reaction, the dispersion was filtered, and the recovered powder was washed with 5 TC of cyclohexane. The solvent was removed from the obtained powder by drying under reduced pressure at a pressure of 10 mmHg or less for 24 hours to obtain a powder. Microcapsule type latent hardener 9. © The obtained microcapsule type latent hardener 9 has a ratio of capsules of 15% by mass. Microcapsule type latent hardener 10 (microcapsule type latent hardener 7) Encapsulation) Add a solution of 146.3 g of toluene and 3.7 g of 4,4,-diphenylmethane diisocyanate in a 500-neck separable flask equipped with a cooling tube, a thermocouple, and a stirring device, and heat in an oil bath. 5 (TC, followed by the addition of 15.0 g of microcapsule-type latent hardener 7 and allowed to react for 3 hours at 501: After the reaction -40 - 201008971, the dispersion was filtered, and the recovered powder was heated to 50. The toluene was washed at ° C. The solvent was removed from the obtained powder under reduced pressure of 10 mmHg or less for 24 hours to obtain a powdery microcapsule latent curing agent 10. The resulting microcapsule latent curing agent Among the 10 capsules The example is 45 mass%. The microcapsule type latent curing agent 11 (the microcapsule type latent curing agent 7 is further encapsulated). The three-piece detachable flask having a cooling tube, a thermoelectric pair, and a stirring device of 500 OOmL is provided. Adding 146.3 g of toluene and 1.8 g of 4,4'-diphenylmethane diisocyanate, heating to 50 ° C in an oil bath, followed by adding 15. 〇g of microcapsule-type latent hardener 7, at 50 The reaction mixture was allowed to react for 3 hours at ° C. After the completion of the reaction, the dispersion was filtered, and the recovered powder was washed with toluene heated to 50 ° C. The pressure was dried under reduced pressure of 10 mmHg for 24 hours from the obtained powder. The solvent was removed to obtain a powdery microcapsule-type latent hardener 11. The ratio of the capsule of the obtained microcapsule-type latent hardener 1 was 28% by mass. 2 - 3. - Liquid epoxy resin Preparation Example of Composition 1 2 to 1 6 33 g of microcapsule-type latent curing agents 7 to 11 and bisphenol F-type epoxy resin (epoxy equivalent 16 〇g/eq, hydrolyzable chlorine amount 0.007 mass%) 67g was compounded to obtain a liquid epoxy resin composition of Example 1 2~1 6 201008971 Example 17 33 g of the microcapsule-type latent curing agent ι〇 was combined with a bisphenol a-type epoxy resin (epoxy equivalent: 173 g/eq, hydrolyzable chlorine amount (. (π% by mass) 67 g to obtain a liquid property of Example 17. Epoxy resin composition. Example 18 33 33 g of a microcapsule type latent curing agent 1 〇 and a naphthalene type epoxy resin (epoxy equivalent 142 g/eq, hydrolyzable chlorine amount 0.017 mass 67 g), and Example 1 was obtained. 8 one-liquid epoxy resin composition. Example 19 35 g of microcapsule-type latent curing agent 1 〇 and bisphenol p-type epoxy resin (epoxy equivalent 160 g / eq, hydrolyzable chlorine amount 〇. 〇〇 7 mass%) 25 g of a liquid epoxy resin composition of Example 19 was obtained by blending 40 g with m-xylylene diepoxypropyl ether (epoxy equivalent: 117 g/eq, hydrolyzable chloranilium 7 7 mass%) Things. 2 — 4. For the comparison, the microcapsule latent hardener and the one-liquid epoxy resin composition microcapsule latent hardener 1 2 will be equipped with three sets of cooling tube, thermoelectric pair and stirring device. 45.0 g of the amine adduct particles 1 and 171.0 g of cyclohexane were placed in a flask, and the mixture was heated to 40 ° C and stirred for 10 minutes. Thereafter, 4,4'-diphenylmethane di-42-201008971 isocyanate 1.5 g was added, and the mixture was reacted at 40 ° C for 2 hours. Then, the temperature was raised to 50 ° C and allowed to react for 6 hours. After completion of the reaction, the dispersion was filtered, and the recovered powder was washed with cyclohexane heated to 50 °C. The solvent was removed from the obtained powder under reduced pressure of 10 mmHg or less for 24 hours to obtain a microcapsule-type latent curing agent 12. The ratio of the capsule in the obtained microcapsule-type latent hardener 1 2 was 3% by mass. 0 Comparative Example 6 33 g of a microcapsule type latent curing agent 12 and 67 g of a bisphenol F type epoxy resin (epoxy equivalent 160 g/eq, hydrolyzable chlorine amount 0.007 mass%) were mixed to obtain a liquid of Comparative Example 6. Epoxy resin composition. Comparative Example 7 45.0 g of an amine adduct particle 1 and 55 g of a bisphenol A type epoxy resin (epoxy equivalent 173 g/eq,) were placed in a three-necked separable flask equipped with a cooling tube, a thermoelectric pair, and a stirring device. The amount of hydrolyzable chlorine was 0.01% by mass), and after heating to 4 ° C, 0.5 g of water was added. After stirring for 10 minutes, 4.0 g of 4,4'-diphenylmethane diisocyanate was added and heated at 40 ° C for 2 hours. Subsequently, the temperature was raised to 50 ° C for 6 hours, and the hardening reaction was carried out in a beaker to obtain a one-liquid epoxy resin composition. Comparative Example 8 A three-neck separable flask equipped with a cooling tube, a thermoelectric pair, and a stirring device was charged with 45 g of an amine adduct particle 1 and 55 g of a bisphenol F-type epoxy tree-43-201008971 (epoxy equivalent 160 g) /eq, hydrolyzable chlorine amount 〇 _ 〇〇 7 mass%), and hardening reaction was carried out in a beaker, and a one-liquid epoxy resin composition could not be obtained. 2-5. Characterization of microcapsule-type latent curing agent The hardening property and storage stability of the liquid epoxy resin and the average particle diameter of the amine adduct particles 3 and 4 of the examples and comparative examples were as follows. Conduct an evaluation. The results of the integration are shown in Table 3. For the one-component epoxy resin composition, a DSC7 differential calorimeter manufactured by Perkin-Elmer Co., Ltd. was used at a temperature rising rate of 10 ° C/min, and a temperature range of 30 ° C to 300 ° C was measured under nitrogen atmosphere. Hardening properties. If the peak temperature from the peak of hardening heat is less than 1 10 °C, it is judged as "AA", and when it is less than 110 °C, it is judged as "A", and 125 °C or more is 130 °C. When it is full, it is judged as "B", and when it is 1 3 5 °C or more, it is judged as "C".储藏 Storage stability The storage stability of the epoxy resin composition and the average particle diameter of the ampoule were measured in accordance with the same measurement conditions and criteria as in the case of the review 1. The proportion of the gum is a sufficient amount of methanol added to the dispersion prepared by the microcapsule latent hardener to obtain an amine adduct from the microcapsule latent hardener by stirring at room temperature for 6 hours. Part of the particles are dissolved in methanol. The dispersion was filtered through -44 - 201008971. The filtrate was dried at a temperature below 50 ° C to completely remove methanol. The weight of the filtrate after drying was measured. The weight ratio of the microcapsule-type epoxy resin hardener to the weight of the filtrate was regarded as the ratio of the capsule. For solvent resistance, a mixture of one-liquid epoxy resin composition/solvent=15 g/3.5 g was kept in a water bath at 40 ° C using toluene/ethyl acetate = 1/1 (wt/wt) as a solvent. Observe the viscosity change of the mixture at this time. If the time until no fluidity is 〇~3 hours, it is judged as "C", 3~6 hours is judged as "B", and 6~10 hours is judged as "A", and if it is 10 hours or more, it is judged as "". AA". -45- 201008971 [Table 3]

實方 m 比較例 12 13 14 15 16 17 18 19 6 7 8 胺加成物粒子 (No.) 3 3 4 3 3 3 3 3 3 3 3 微膠囊型潛在性 7 8 9 10 11 10 10 10 12 - 硬化劑(No.) [質量份] [33] [33] [33] [33] [33] P3] [33] P5] P3] [45] [45] 膠囊之比例 [質量％] 14 9 15 45 28 45 45 45 3 - - 環氧樹脂 BisF BisF BisF BisF BisF BisA Nap BisF BisF BisA BisF [質量份] [671 [671 『671 [671 [671 [67] [67] [251 [67] @5] [551 - - - - - - - Res [40] - - 硬化特性 AA AA AA A AA B AA AA AA 合成 合成 儲藏安定性 A A A AA AA AA AA AA C 不可 不可 耐溶劑性 B - - AA A - - - C 從上述實驗結果也可確認，藉由本發明，可得到同時 具有低溫硬化特性及儲藏安定性之環氧樹脂用粉末狀微膠 囊型潛在性硬化劑及製造方法以及一液性環氧樹脂組成 物。 -46 -Real m Comparative Example 12 13 14 15 16 17 18 19 6 7 8 Amine adduct particles (No.) 3 3 4 3 3 3 3 3 3 3 3 Microcapsule type potential 7 8 9 10 11 10 10 10 12 - Hardener (No.) [Mass] [33] [33] [33] [33] [33] P3] [33] P5] P3] [45] [45] Capsule ratio [% by mass] 14 9 15 45 28 45 45 45 3 - - Epoxy BisF BisF BisF BisF BisF BisA Nap BisF BisF BisA BisF [Mass] [671 [671 『671 [671 [671 [67] [67] [251 [67] @5 ] [551 - - - - - - - Res [40] - - Hardening characteristics AA AA AA A AA B AA AA AA Synthetic synthetic storage stability AAA AA AA AA AA AA C Not solvent resistant B - - AA A - - - C From the above experimental results, it was confirmed that the powdery microcapsule-type latent curing agent for epoxy resin having both low-temperature hardening property and storage stability can be obtained by the present invention, and a one-component epoxy resin can be obtained. Composition. -46 -

Claims (1)

201008971 十、申請專利範面 1. 一種環氧樹脂用微膠囊型潛在性硬化劑，其特^ 爲， 具有核心及將此被覆之膠囊， 該核心包含胺加成物， 該膠囊包含異氰酸酯與具有活性氫基之化合物及 與水的反應生成物，該反應生成物中至少一部份係經由 Θ 該胺加成物之反應鍵結於該核心。 2. 如申請專利範圍第1項記載之環氧樹脂用微膠囊型 潛在性硬化劑，其中該核心包含以質量比5 0〜1 00%之該 胺加成物。 3. 如申請專利範圍第1項記載之環氧樹脂用微膠囊型 潛在性硬化劑，其係爲粉末狀。 4. 如申請專利範圍第1項記載之環氧樹脂用微膠囊型 潛在性硬化劑，其中該膠囊之比例，以該微膠囊型潛在性 ® 硬化劑之全質量爲基準係爲5〜80質量％。 5. 如申請專利範圍第1項記載之環氧樹脂用微膠囊型 . 潛在性硬化劑，其中該膠囊之比例，以該微膠襄型潛在性 硬化劑之全質量爲基準係爲40〜80質量％。 6. 如申請專利範圍第1項記載之環氧樹脂用微膠囊型 潛在性硬化劑，其中該膠囊之比例，以該微膠囊型潛在性 硬化劑之全質量爲基準係爲15〜40質量％。 7. 如申請專利範圍第1項記載之環氧樹脂用微膠囊型 潛在性硬化劑，其中該膠囊之比例，以該微膠囊型潛在性 -47- 201008971 硬化劑之全質量爲基準係爲5〜15質量％。 8. —種環氧樹脂用微膠囊型潛在性硬化劑之製造方 法，其特徵爲，具備藉由使被包含於核心中之胺加成物與 異氰酸酯與具有活性氫基之化合物及/或水在分散媒中反 應，形成被覆該核心之膠嚢之步驟。 9. 如申請專利範圍第8項記載之製造方法，更具備有 從反應後之混合物中取出具有核心及膠囊之粉末狀之微膠 〇 囊型潛在性硬化劑之步驟。 10. —種環氧樹脂用微膠囊型潛在性硬化劑，其特徵 爲可經由申請專利範圍第8項記載之製造方法而得。 11. 一種一液性環氧樹脂組成物，其特徵爲含有如申 請專利範圍第1〜7項及第10項中任一項記載之環氧樹脂 用微膠囊型潛在性硬化劑及環氧樹脂。 1 2.如申請專利範圍第1 1項記載之一液性環氧樹脂組 成物，其中該環氧樹脂用微膠嚢型潛在性硬化劑係於該環 〇 氧樹脂中經加熱處理者。 13如申請專利範圍第11項記載之一液性環氧樹脂組 .成物，其中爲，相對於該環氧樹脂及該微膠囊型潛在性硬 . 化劑之合計量1〇〇質量份含有該微膠囊型潛在性硬化劑5 〜70質量份。 14.一種硬化物，其特徵爲使申請專利範圍第11項記 載之一液性環氧樹脂組成物加熱而硬化所形成。 -48- 201008971 無 • · 明 說 單 簡 號 Λ ..表 為代 圖件 表元 代之 定圖 指表 :案代 圖本本 表、、 代\ 定一二 指CC 七 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無201008971 X. Patent application 1. A microcapsule latent hardener for epoxy resin, which has a core and a coated capsule, the core comprising an amine adduct, the capsule comprising isocyanate and having An active hydrogen group-containing compound and a reaction product with water, at least a portion of which is bonded to the core via a reaction of the amine adduct. 2. The microcapsule-type latent curing agent for epoxy resins according to claim 1, wherein the core contains the amine adduct in a mass ratio of 50 to 100%. 3. The microcapsule-type latent curing agent for epoxy resins according to the first aspect of the invention, which is in the form of a powder. 4. The microcapsule latent curing agent for epoxy resin according to item 1 of the patent application, wherein the ratio of the capsule is 5 to 80 by mass based on the total mass of the microcapsule latent® hardener %. 5. The microcapsule type epoxy resin type of the epoxy resin according to the first aspect of the patent application, wherein the ratio of the capsule is 40 to 80 based on the total mass of the microcapsule type latent hardener. quality%. 6. The microcapsule latent curing agent for epoxy resin according to claim 1, wherein the ratio of the capsule is 15 to 40% by mass based on the total mass of the microcapsule latent curing agent. . 7. The microcapsule-type latent curing agent for epoxy resin according to claim 1, wherein the ratio of the capsule is 5 based on the total mass of the microcapsule-potential-47-201008971 hardener. ~15% by mass. 8. A method for producing a microcapsule latent curing agent for an epoxy resin, comprising: an amine adduct contained in a core and an isocyanate and a compound having an active hydrogen group and/or water The reaction is carried out in a dispersion medium to form a step of coating the core of the capsule. 9. The method of claim 8, further comprising the step of removing the powdered microcapsule-type latent curing agent having a core and a capsule from the reacted mixture. A microcapsule latent curing agent for epoxy resins, which is characterized in that it can be obtained by the production method described in claim 8 of the patent application. A one-component epoxy resin composition comprising the microcapsule latent curing agent for epoxy resin and epoxy resin according to any one of claims 1 to 7 and 10 . A liquid epoxy resin composition according to any one of claims 1 to 11, wherein the epoxy resin is a microcapsule type latent curing agent which is heated in the epoxy resin. A liquid epoxy resin composition according to claim 11, wherein the total amount of the epoxy resin and the microcapsule-type latent hardening agent is 1 part by mass. The microcapsule type latent curing agent is 5 to 70 parts by mass. A cured product which is characterized in that one of the liquid epoxy resin compositions described in claim 11 of the patent application is heated and hardened. -48- 201008971 无• · Ming said single simple number Λ.. Table is the map of the generation of map elements on behalf of the map: the table of the generation of the map, the generation of the first and second refers to CC seven eight, if the case has a chemical formula , please reveal the chemical formula that best shows the characteristics of the invention: none
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