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TW200950878A - Microcapsule and curable resin composition containing microcapsule - Google Patents

Microcapsule and curable resin composition containing microcapsule Download PDF

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Publication number
TW200950878A
TW200950878A TW98104973A TW98104973A TW200950878A TW 200950878 A TW200950878 A TW 200950878A TW 98104973 A TW98104973 A TW 98104973A TW 98104973 A TW98104973 A TW 98104973A TW 200950878 A TW200950878 A TW 200950878A
Authority
TW
Taiwan
Prior art keywords
component
compound
curable resin
group
acrylate
Prior art date
Application number
TW98104973A
Other languages
Chinese (zh)
Inventor
Hironori Suzuki
Hitoshi Mafune
Original Assignee
Three Bond Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Three Bond Co Ltd filed Critical Three Bond Co Ltd
Publication of TW200950878A publication Critical patent/TW200950878A/en

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Classifications

    • 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
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
    • 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)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is a microcapsule of a liquid amine compound, which can be easily produced, while having stable quality. The microcapsule of a liquid amine compound has both storage stability and handleability during when mixed with a curable resin and used as a curing agent or a curing accelerator. The microcapsule is composed of the components (A)-(C) described below, and the component (B) serves as a capsule carrier onto which the component (A) is adsorbed. A coating film is formed by reacting the component (C) with the component (A) present on the surface of the component (B). Component (A): a liquid amine compound having an acid dissociation constant (pKa) of not less than 8.0 or an organic acid salt thereof Component (B): porous fine particles capable of adsorbing the component (A) Component (C): an acid anhydride

Description

200950878 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種含有最適合之液狀的胺化合物作爲 . 硬化性樹脂的硬化劑或硬化促進劑之微膠囊及含有微膠囊 之硬化性樹脂組成物。 【先前技術】 ® —般，使用於黏著劑、密封劑、塗佈劑等用途之以環 氧樹脂爲首的熱硬化性樹脂組成物中，係添加有用作爲交 聯、硬化反應之成份的硬化劑，以及用以提升硬化性之成 份的硬化促進劑。尤其，爲了形成爲單液而具有隱性之硬 化劑或硬化促進劑，爲人所知者有環氧加成化合物、有機 磷系化合物、有機胺系化合物、咪唑衍生物系化合物等。 尤其是有機胺系化合物，乃適合用作爲液狀的硬化劑或硬 化促進劑。 ® 環氧加成化合物，一般係使用將以雙酚A型環氧樹脂 等爲代表之環氧樹脂與胺化合物反應至中途階段的反應生 成物。環氧樹脂的硬化劑或硬化促進劑，爲人所知有使用 將環氧加成化合物進行微粉碎之粉體。於JP7-5708B中， 係揭示有一種在環氧加成化合物的粉體中，於表面使環氧 樹脂反應而形成殼層之手法，但該製程較爲繁瑣，於製造 時必須要求相當高的精度。此外，由於成爲核心之粉體以 加成有環氧樹脂之胺化合物，所以胺的反應性已降低，形 成殻層時必須花費較長時間。這些環氧加成化合物，一般 -5- 200950878 其反應性較高且容易處理，但因成份構成的不同，可能有 無法充分硬化而無法獲得滿足的硬化物特性之情形。此外 ’此環氧加成化合物，當捏合於具有環氧基之化合物時， 容易顯現出被視爲來自硬化劑表面的胺構造之流動減黏性 (黏流性），由於性狀的緣故，會對處理性造成影響，所 以必須限制其添加量。當然，當添加量較少時，亦會產生 硬化性降低之問題點。 有機磷系化合物，當用作爲以酚類酚醛樹脂使環氧樹 脂硬化時之觸媒爲有用，但由於爲固形，而具有不易分散 之缺點’爲了提升分散性，可使用微粉末狀，但作爲分散 方法仍不充分’此外，在此方法中，無法賦予觸媒的隱性 。液狀的有機胺系化合物或咪唑衍生物系化合物，較多係 使用爲環氧樹脂或酚類樹脂的硬化劑或觸媒，但較多者均 具有獨特的臭氣或毒性，且當添加觸媒時，使用期限極短 。再者，爲固形時乃具有不易分散等問題點。關於使用期 限可藉由構成爲特殊的咪唑鹽而具有某種程度的隱性。亦 即’可在觸媒能顯現溫度以下，進行對原料的分散步驟、 捏合步驟、成型步驟，並且在觸媒能顯現溫度以下，進行 交聯步驟。然而，該效果不完全，亦具有硬化效果較慢之 缺點。 胺系硬化劑/硬化促進劑，爲人所知者有式（1 )所表 示的DBU ( 1,8-二氮雜雙環[5.4.0]十一 -7-烯）、式（2) 所表示的DBN(1,5-二氮雜雙環[4.3.0]壬-5-烯）之化合物 。DBU、DBN爲有機化合物中顯現出最強的驗基性當中之 200950878 泛的 硬化 一’藉由該強驗基性、安定性及相對於有機溶劑之廣 溶解性’在藉由環氧樹脂等的胺化合物使硬化進行之 系中’可用作爲硬化促進劑。200950878 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a microcapsule containing a most suitable liquid amine compound as a hardening agent or a hardening accelerator for a curable resin, and a curable resin containing microcapsules. Composition. [Prior Art] A thermosetting resin composition containing an epoxy resin, such as an adhesive, a sealant, or a coating agent, is added to a hardening component which is useful as a crosslinking and hardening reaction. And a hardening accelerator for enhancing the hardenability component. In particular, in order to form a hardening agent or a curing accelerator which is a single liquid, an epoxy addition compound, an organic phosphorus compound, an organic amine compound, an imidazole derivative compound or the like is known. In particular, an organic amine compound is suitable as a liquid hardener or a hardening accelerator. ® Epoxy Addition Compounds are generally used as reaction products in which an epoxy resin represented by a bisphenol A type epoxy resin or the like is reacted with an amine compound to an intermediate stage. A hardener or a hardening accelerator for an epoxy resin is known to be a powder obtained by finely pulverizing an epoxy addition compound. In JP 7-5708B, there is disclosed a method in which an epoxy resin is reacted on a surface to form a shell layer in a powder of an epoxy addition compound, but the process is cumbersome and must be required to be relatively high in manufacturing. Precision. Further, since the core powder is added to form an amine compound having an epoxy resin, the reactivity of the amine is lowered, and it takes a long time to form the shell layer. These epoxy addition compounds are generally highly reactive and easy to handle, but depending on the composition of the components, there may be cases where the cured properties are not sufficiently hardened to obtain satisfactory properties. Further, 'this epoxy addition compound, when kneaded to a compound having an epoxy group, tends to exhibit flow decarburization (viscous flow) which is regarded as an amine structure derived from the surface of the hardener, due to the trait, It has an impact on handling, so it is necessary to limit the amount of addition. Of course, when the amount of addition is small, there is also a problem that the hardenability is lowered. The organophosphorus compound is useful as a catalyst for curing an epoxy resin with a phenolic phenol resin, but has a disadvantage of being difficult to disperse because it is solid. 'In order to improve dispersibility, a fine powder may be used, but The dispersion method is still insufficient. Further, in this method, the recessivity of the catalyst cannot be imparted. A liquid organic amine compound or an imidazole derivative compound is often used as a curing agent or a catalyst for an epoxy resin or a phenol resin, but most of them have a unique odor or toxicity, and when added, In the case of media, the period of use is extremely short. Furthermore, when it is solid, it has problems such as difficulty in dispersion. The use period can be somewhat recessive by being constituted as a special imidazolium salt. That is, the crosslinking step, the kneading step, and the molding step of the raw material can be carried out at a temperature below the temperature at which the catalyst can be expressed, and the crosslinking step can be carried out at a temperature below the catalyst. However, this effect is incomplete and has the disadvantage of a slower hardening effect. An amine-based hardener/hardening accelerator is known as DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) represented by formula (1), and formula (2) A compound of DBN (1,5-diazabicyclo[4.3.0]non-5-ene) represented. DBU and DBN are among the strongest testers in organic compounds. The hardening of 200950878 is based on the strong basicity, stability and wide solubility with respect to organic solvents. The amine compound can be used as a hardening accelerator in the system in which hardening is carried out.

當將以DBU或DBN爲典型例之強鹼基性化合物 爲硬化性樹脂組成物的硬化劑/硬化促進劑時，雖然 鹼基性的強度使硬化反應極迅速地進行，但僅單純地 〇 化性樹脂混合者，不易維持保存性，而難以使用於作 或處理性優良之單液型的硬化性樹脂組成物。 因此，就將硬化性樹脂組成物中的保存性賦予至 或DBN等之目的，至目前爲止已進行將DBU或DBN 微膠囊化之硏究。JP 1 -287131A係例示一種藉由介面 法、介面聚合法、液中硬化覆膜法等將DBU等之液 化合物予以微膠囊化之手法。此類一般的膠囊化手法 於至少使用水、溶劑的至少一種，並且在使胺化合物 之相容系中進行反應’所以難以取得均一的微膠囊。 D B N、D B U對水或溶劑的相容性極高，所以在依據前 用作 因其 與硬 業性 DBU 予以 沉澱 狀胺 ，由 溶解 尤其 述手 200950878 法所進行之膠囊化中，非常難以在高良率下取得均一的微 膠囊。再者，在這些一般的膠囊化手法中，由於伴隨著用 以合成膠囊之加熱及長時間的攪拌，即使形成膠囊，亦具 有液狀胺化合物從微膠囊中溶解出之問題。 另一方面，JP7-32366A 、 JP2001-55473A 及 JP8-1 5 75 70A中，係報告一種將可成爲硬化促進劑之成份吸收 至微粒子中來予以微膠囊化之技術。前兩者中，僅單純使 可成爲硬化促進劑之成份吸收至微粒子中，並藉由微弱刺 ⑬ 激而容易溶解出膠囊內容物。因此，存在有僅與硬化性樹 脂混合即容易產生硬化反應之問題，而僅是將成爲液狀的 硬化促進劑之成份形成爲固形狀使處理性變得容易而已。 再者，在JP8-157570A中，係採取一種在使包含DBU 之胺系觸媒撐持於微粒粉末後，將固形成份塗佈於此微粒 粉末的表面而藉此將微粒粉末予以膠囊化之手法。然而， 在此方法中，只不過以固形成份來塗佈表面，所以容易因 熱或機械性刺激等影響，使固形成份被破壞，而無法獲得 〇 安定的微膠囊。 【發明內容】 (發明之目的） 藉由上述技術所製造之液狀胺化合物的微膠囊’難以 達到品質的安定化。此外，當與硬化性樹脂混合而用作爲 硬化劑/硬化促進劑時，無法同時兼具處理性與保存安定 性，所以在此用途上並不具耐用性。目前爲止，尙未創作 -8- 200950878 出可滿足這些特性之實際上的微膠囊之殼體成份與殼體成 形方法。 本發明之目的在於解決上述問題點’而提供一種能夠 . 以簡單且品質變動度較低之方式，將以DBU或DBN爲首 之液狀胺化合物予以微膠囊化，並且在用作爲硬化性樹脂 的硬化劑或硬化促進劑時可顯現出安定性，結果可形成保 存安定性優良之單液型的硬化性樹脂組成物之微膠囊的製 ❿ 造技術。 (發明之摘要） 本發明之第1型態爲一種微膠囊，係以下列（A )〜（ C)成份爲構成成份，使（B)成份吸收（A)成份，並且 使（C)成份與存在於該（B)成份的表面上之（A)成份 反應而形成覆膜所成， (A) 成份：酸解離常數（pKa)爲8.0以上之液狀的 〇 胺化合物或其有機酸鹽 (B) 成份：多孔質微粒子粉 (C )成份：酸酐。 本發明之第2型態爲前述微膠囊，其中前述（A)成 份係由從DBU、DBN、三伸乙二胺、以這些化合物爲主骨 幹之衍生物及這些化合物的有機酸鹽中所選出之至少1種 所形成。 本發明之第3型態爲前述微膠囊，其中前述（C)成 份爲含有可塑劑之酸酐。 -9- 200950878 本發明之第4型態爲一種硬化性樹脂組成物，其特徵 係由含有前述微膠囊作爲硬化劑或硬化促進劑之硬化性樹 脂所形成。 在此，所謂硬化性樹脂，是指於1個分子內具有1個 以上的環氧基、環硫基、異氰酸酯基、乙烯基般之具有反 應性的官能基之化合物。 本發明之第5型態爲前述硬化性樹脂組成物，其中前 述硬化性樹脂係由從具有環氧基之化合物、具有環硫基之 © 化合物、具有異氰酸酯基之化合物以及具有乙烯基之化合 物中所選出之至少1種所形成。 本發明之第6型態爲前述硬化性樹脂組成物，其中前 述第4型態的硬化性樹脂，係由從具有環氧基之化合物及 具有環硫基之化合物中所選出之至少1種硬化性樹脂所形 成，並且使用從聚胺化合物、聚酚化合物、聚硫醇化合物 或酸酐中所選出之至少1種作爲硬化劑，使用前述微膠囊 作爲硬化促進劑而成。 〇 發明之效果： 藉由將本發明之微膠囊用作爲硬化性樹脂的硬化劑/ 硬化促進劑，可提供同時兼具保存安定性與硬化性之硬化 性樹脂組成物。 【實施方式】 以下說明本發明的詳細內容。本發明的（A )成份’ -10- 200950878 爲酸解離常數（pKa ) 8 · 0以上之液狀的胺化合物。在此， 所謂的酸解離常數，爲用以定量地表示酸的強度之指標之 一，係以從酸釋出質子之解離反應的平衡常數（Ka)之負 , 的常用對數所表示。pKa之値愈大，係表示爲愈強的鹼基 〇 本發明中所能夠使用之（A )成份，只要是pKa爲 8.0以上之液狀胺化合物，則無特別限定，例如有DBU ( O pKal2.7) 、DBN(pKal2.5)、二鄰甲苯胍（Diorthotolyl Guanidine) (pKal0.8)、月桂胺（pKalO.6)、二苯胍（ pKalO.l )、二苯甲基胺（pKa9.7 )、三伸乙二胺（ pKa8.8)等。尤其是DBU、DBN、三伸乙二胺，其親核性 較強，容易與後述的（C)成份反應而形成膠囊的殼層部 ，因此，較理想爲單獨使用DBU、DBN、三伸乙二胺或這 些化合物的衍生物，或是將DBU、DBN、三伸乙二胺用作 爲羧酸、磺酸、酚類等之有機酸的鹽。 ® 當使用pKa小於8.0之液狀胺化合物，在形成膠囊覆 膜之步驟中，無法迅速地進行與作爲（C)成份的酸酐之 反應，若不加熱則無法使反應進行。另一方面，當維持在 高溫狀態時，（A)成份會從吸收（A)成份之多孔質微 粒子粉（B)成份中漏出，所以無法形成安定的膠囊覆膜 ，當將該膠囊調配於硬化性樹脂組成物時，保存安定性會 產生問題。 本發明中所能夠使用之（B )成份，只要爲可吸收前 述（A )成份之多孔質微粒子粉，則無特別限定。該平均 -11 - 200950878 粒徑較理想爲20μπι以下。材質的具體例子有碳黑、膠態 二氧化矽、發煙二氧化矽、濕式二氧化矽；鎂、鈣、鋇等 之矽酸鹽、銅、鋅、鋁、鈦、錫、鐵、鈷、鎳等之氧化物 或但化物等的多孔質無機微粒子粉。尤其理想爲平均粒徑 | 2 0μιη以下的多孔質二氧化矽粉。多孔質二氧化矽粉的市 售品，例如有Godball (二氧化矽製的球狀粉、中空球狀 粉）（鈴木油脂工業株式會社製）、Mizuka Ace (矽酸製 的不定形粉）（水澤化學工業株式會社製）等，可因應用 © 途來適當地選擇粒徑等。當多孔質微粒子的平均粒徑超過 2 Ομιη時，由於將本發明之膠囊與硬化性樹脂混合時黏度 變得過高，使硬化性樹脂組成物的塗佈性降低，此外，於 保存中亦有容易產生分離·沉降之疑慮。 本發明之（Β )成份的多孔質微粒子粉之吸收性的指 標，在JIS-K-5 101所規定之吸油量的測定中，較理想爲位 於50〜500ml/100g的範圍。 在此，本發明中使用（B)成份的目的，係用以使前 © 述（A)成份虛擬地固化。 本發明中所能夠使用之（C)成份，只要是在室溫中 爲液狀，且可藉由（A)成份進行聚合而形成覆膜之酸酐 ，則無特別限定。例如有十二烯琥珀酸酐、聚壬二酸酐、 六氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、甲基四氫鄰苯二 甲酸酐、甲基內次甲基四氫苯酸酐、偏苯三甲酸酐、苯均 四酸酐、二苯甲酮四羧酸酐、四溴鄰苯二甲酸酐等之具有 1個以上的羧酸酐基之化合物。以具有此功能的酸酐爲主 -12- 200950878 成份之商品的具體例子，有曰立化成株式會社製的HN-2200 ' HN-2000、HN-5500、MHAC-P或是新日本理化株式 會社製的 Rikacid ΤΗ、ΗΤ-ΙΑ、HH、MH-700、MH-700G . 、HNA-100、TMEG-S ' TMEG-100、TMEG-200、TMEG- 500、TMEG-600、TMTA-C、TMA-15、DDSA、HF-08、SA 、DSDA、TMEG-100、TDA-100、BT-100 或是大日本油墨 化學工業株式會社製的 EPICLON B-570、B-650、B-4400 © 等。即使是室溫下爲固體之酸酐，亦可在室溫下溶解於液 體的酸酐，而在室溫下爲液體之狀態來使用。 作爲能夠與強鹼基之前述（A)成份在室溫下短時間 進行反應而形成膠囊的殼體之化合物，對本發明爲不可或 缺者，爲上述所代表的酸酐，藉由組合前述（A)成份與 (C)成份，可達成本發明之目的。亦即，於本發明中， 在吸收前述（A)成份之（B)成份的多孔質微粒子粉的表 面上，該（A)成份殘留，當使（C)成份與殘留於該表面 © 之（A)成份接觸時，兩者會進行反應而藉此在成爲膠囊 的撐體之（B)成份的表面上形成膠囊殻體。 前述（C)成份，可藉由使用含有可塑劑之酸酐來控 制膠囊的脆度。亦即，藉由增加可塑劑的量，可使膠囊變 脆，藉由減少可塑劑的量，可使膠囊變硬。在此所能夠使 用之可塑劑，較理想爲容易與酸酐相溶之可塑劑，尤其理 想爲鄰苯二甲酸酯系、己二酸酯系、聚酯系等之可塑劑。 (C)成份中可塑劑的含有量，相對於（C)成份1〇〇重量 份，可塑劑較理想爲0.1 ~50重量份。 -13- 200950878 接著說明用以形成膠囊之具體手法。首先藉由攪拌機 等，將過剩量的液狀（A)成份與（B)成份混合使（A) 成份充分地吸收於（B)成份。由於此時可能會產生吸收 熱，當發熱時，可放置冷卻至室溫爲止。如此，使（A) . 成份充分地吸收於（B)成份的多孔部。接著從該混合物 中，使吸收（A)成份之（B)成份單離。此單離，例如可 將洗淨用溶劑添加於該混合物中並加以攪拌後，藉由吸引 過濾等來過濾固形份，藉由熱風乾燥爐等使溶劑揮發並回 〇 收該粉體而藉此進行。結束一連串的步驟後之（B)成份 ，不僅在內部，在表面上（A)成份亦殘留。接著將該（B )成份添加於（C)成份的液相中並藉由攪拌機等加以混 合，藉此進行（A)成份與（C)成份的反應。藉此，殘留 於（B )成份的表面之（A )成份與（C )成份反應而形成 覆膜。藉由此覆膜的形成，可使存在於（B)成份的內部 之（A)成份殘留。然後從該混合物中使微膠囊單離。此 單離，例如可將洗淨用溶劑添加於該混合物中並加以攪拌 C) 後，藉由吸引過濾等來過濾固形份，藉由熱風乾燥爐等使 溶劑揮發並回收固形份而藉此進行。此固形份爲微膠囊化 後之液狀的胺化合物。 關於前述（A)成份及（C)成份形成膠囊覆膜之機制 尙未完全分析出，但可考量爲存在於作爲膠囊撐體的多孔 質微粒子粉上之前述（A)成份，亦即pKa爲8.0以上之 強鹼基的液狀胺化合物使酸酐開環，所生成之羧基陰離子 與其他的（C)成份反應，進行高分子化而成爲下列式（3 -14- 200950878When a strong base compound having a typical example of DBU or DBN is used as a curing agent/hardening accelerator for a curable resin composition, although the base strength is such that the hardening reaction proceeds extremely rapidly, it is simply deuterated. The resin mixture is difficult to maintain the preservability, and it is difficult to use it as a single-liquid type curable resin composition which is excellent in handling or handling property. Therefore, the storage property in the curable resin composition is imparted to DBN or the like, and so far, micro-encapsulation of DBU or DBN has been carried out. JP 1 -287131A exemplifies a method of microencapsulating a liquid compound such as DBU by an interface method, an interface polymerization method, a liquid hardening film method, or the like. Such a general encapsulation method uses at least one of water and a solvent, and reacts in a compatible system of an amine compound. Therefore, it is difficult to obtain uniform microcapsules. DBN and DBU have high compatibility with water or solvent, so it is very difficult to use in the encapsulation of the hard-working DBU before the basis of the precipitation. A uniform microcapsule is obtained at a rate. Further, in these general encapsulation methods, there is a problem that the liquid amine compound is dissolved from the microcapsules even if the capsule is formed by heating with a synthetic capsule and stirring for a long period of time. On the other hand, JP 7-32366A, JP2001-55473A, and JP8-1 5 75 70A report a technique of microencapsulating a component which can be a hardening accelerator into microparticles. In the former two, only the component which can be a hardening accelerator is absorbed into the fine particles, and the contents of the capsule are easily dissolved by the weak thorns. Therefore, there is a problem that the curing reaction is likely to occur only when it is mixed with the curable resin, and the composition of the liquid hardening accelerator is formed into a solid shape to facilitate handling. Further, in JP 8-157570 A, a method in which an amine-based catalyst containing DBU is supported on a fine particle powder and a solid component is applied to the surface of the fine particle powder to encapsulate the fine particle powder is employed. However, in this method, the surface is applied only by the solid component, so that the solid component is easily broken by thermal or mechanical stimuli, and the microcapsules which are stable in the ruthenium cannot be obtained. SUMMARY OF THE INVENTION (Object of the Invention) The microcapsules of the liquid amine compound produced by the above technique are difficult to achieve quality stabilization. Further, when it is used as a curing agent/hardening accelerator in combination with a curable resin, it cannot simultaneously have both handleability and storage stability, and therefore has no durability in this application. So far, it has not been created -8- 200950878 to form a practical microcapsule shell component and shell forming method that can satisfy these characteristics. An object of the present invention is to solve the above problems and to provide a liquid amine compound such as DBU or DBN which can be microencapsulated in a simple manner and with low quality variation, and is used as a curable resin. When the curing agent or the curing accelerator is used, stability can be exhibited, and as a result, a microcapsule of a single-liquid type curable resin composition excellent in stability can be formed. (Summary of the Invention) The first aspect of the present invention is a microcapsule comprising the following components (A) to (C) as a constituent component, (B) component absorbing (A) component, and (C) component The component (A) present on the surface of the component (B) reacts to form a film, and the component (A) is a liquid guanamine compound having an acid dissociation constant (pKa) of 8.0 or higher or an organic acid salt thereof ( B) Ingredients: Porous microparticle powder (C) Ingredients: Anhydride. The second aspect of the present invention is the above microcapsule, wherein the component (A) is selected from DBU, DBN, triethylenediamine, a derivative of these compounds as a main backbone, and an organic acid salt of these compounds. At least one of them is formed. The third aspect of the present invention is the aforementioned microcapsule, wherein the component (C) is an acid anhydride-containing acid anhydride. -9- 200950878 The fourth aspect of the present invention is a curable resin composition characterized by comprising a curable resin containing the microcapsule as a curing agent or a curing accelerator. Here, the term "curable resin" refers to a compound having one or more functional groups such as an epoxy group, an epoxy group, an isocyanate group or a vinyl group in one molecule. The fifth aspect of the present invention is the curable resin composition, wherein the curable resin is derived from a compound having an epoxy group, a compound having an episulfide group, a compound having an isocyanate group, and a compound having a vinyl group. At least one selected one is formed. The sixth aspect of the present invention is the curable resin composition, wherein the fourth type of curable resin is at least one type selected from the group consisting of a compound having an epoxy group and a compound having an epoxy group. The resin is formed, and at least one selected from the group consisting of a polyamine compound, a polyphenol compound, a polythiol compound, and an acid anhydride is used as a curing agent, and the above microcapsules are used as a curing accelerator.效果 Effect of the Invention: The microcapsule of the present invention is used as a curing agent/hardening accelerator for a curable resin, and a curable resin composition having both storage stability and curability can be provided. [Embodiment] The details of the present invention will be described below. The component (A) of the present invention '-10-200950878 is a liquid amine compound having an acid dissociation constant (pKa) of 8·0 or more. Here, the so-called acid dissociation constant is one of the indexes for quantitatively indicating the strength of the acid, and is expressed by a common logarithm of the equilibrium constant (Ka) of the dissociation reaction for releasing protons from the acid. The larger the pKa, the stronger the base is. The component (A) which can be used in the present invention is not particularly limited as long as it is a liquid amine compound having a pKa of 8.0 or more, for example, DBU (O pKal2) .7), DBN (pKal2.5), Diorthotolyl Guanidine (pKal0.8), laurylamine (pKalO.6), diphenylguanidine (pKalO.l), benzhydrylamine (pKa9. 7), triethylene glycol diamine (pKa8.8) and the like. In particular, DBU, DBN, and triethylenediamine have strong nucleophilicity and are easily reacted with the component (C) described later to form a shell portion of the capsule. Therefore, it is preferable to use DBU, DBN, and Sansei B alone. A diamine or a derivative of these compounds, or a salt of an organic acid such as a carboxylic acid, a sulfonic acid or a phenol, using DBU, DBN or triethylenediamine. ® When a liquid amine compound having a pKa of less than 8.0 is used, in the step of forming a capsule film, the reaction with the acid anhydride as the component (C) cannot be carried out rapidly, and the reaction cannot proceed without heating. On the other hand, when the temperature is maintained at a high temperature, the component (A) leaks from the component of the porous fine particle powder (B) which absorbs the component (A), so that a stable capsule film cannot be formed, and when the capsule is formulated for hardening When the resin composition is used, there are problems in preserving stability. The component (B) which can be used in the present invention is not particularly limited as long as it is a porous fine particle powder which can absorb the component (A). The average -11 - 200950878 particle size is preferably 20 μm or less. Specific examples of the material are carbon black, colloidal cerium oxide, fumed cerium oxide, wet cerium oxide; magnesium, calcium, barium, etc. citrate, copper, zinc, aluminum, titanium, tin, iron, cobalt A porous inorganic fine particle powder such as an oxide or a compound of nickel or the like. In particular, a porous cerium oxide powder having an average particle diameter of 2 0 μm or less is preferable. Commercial products of the porous cerium oxide powder include, for example, Godball (spherical powder made of cerium oxide, hollow spherical powder) (made by Suzuki Oil & Fats Co., Ltd.), and Mizuka Ace (unshaped powder made of citric acid) ( The water quality can be appropriately selected depending on the application. When the average particle diameter of the porous fine particles exceeds 2 μm, the viscosity of the curable resin composition is lowered when the capsule of the present invention is mixed with the curable resin, and the coating property of the curable resin composition is lowered. It is easy to cause doubts about separation and settlement. The index of absorbability of the porous fine particle powder of the (Β) component of the present invention is preferably in the range of 50 to 500 ml/100 g in the measurement of the oil absorption amount prescribed in JIS-K-5101. Here, the purpose of using the component (B) in the present invention is to cure the composition of the former (A) virtually. The component (C) which can be used in the present invention is not particularly limited as long as it is liquid at room temperature and can be formed by polymerization of the component (A) to form an acid anhydride of a film. For example, dodecene succinic anhydride, polysebacic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl endomethyltetrahydrophthalic anhydride, A compound having one or more carboxylic anhydride groups such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, or tetrabromophthalic anhydride. For example, HN-2200 'HN-2000, HN-5500, MHAC-P, manufactured by Nippori Chemical Co., Ltd., manufactured by Higashi Kasei Co., Ltd., is a product of the product having the function of the acid anhydride of the -12-200950878. Rikacid ΤΗ, ΗΤ-ΙΑ, HH, MH-700, MH-700G . , HNA-100, TMEG-S ' TMEG-100, TMEG-200, TMEG- 500, TMEG-600, TMTA-C, TMA-15 DDSA, HF-08, SA, DSDA, TMEG-100, TDA-100, BT-100 or EPICLON B-570, B-650, B-4400 © manufactured by Dainippon Ink and Chemicals. Even if it is a solid acid anhydride at room temperature, it can be used in a state of being liquid at room temperature in an acid anhydride at room temperature. A compound which is capable of reacting with the above-mentioned component (A) of a strong base at a room temperature for a short period of time to form a capsule, and which is indispensable to the present invention, is an acid anhydride represented by the above-mentioned (A) The ingredients and (C) ingredients can be used for the purpose of the invention. That is, in the present invention, on the surface of the porous fine particle powder which absorbs the component (B) of the above component (A), the component (A) remains, and when the component (C) remains and remains on the surface ( A) When the components are in contact, the two react to form a capsule shell on the surface of the component (B) which is the support of the capsule. In the above component (C), the brittleness of the capsule can be controlled by using an acid anhydride containing a plasticizer. That is, the capsule can be made brittle by increasing the amount of the plasticizer, and the capsule can be hardened by reducing the amount of the plasticizer. The plasticizer which can be used herein is preferably a plasticizer which is easily compatible with an acid anhydride, and is particularly preferably a plasticizer such as a phthalate type, an adipate type or a polyester type. The content of the plasticizer in the component (C) is preferably 0.1 to 50 parts by weight based on 1 part by weight of the component (C). -13- 200950878 Next, a specific method for forming a capsule will be described. First, an excess amount of the liquid (A) component and the component (B) are mixed by a stirrer or the like to sufficiently absorb the component (A) into the component (B). Since absorption heat may be generated at this time, when it is heated, it can be left to cool to room temperature. Thus, the component (A) is sufficiently absorbed into the porous portion of the component (B). Next, from the mixture, the component (B) of the absorbing (A) component is separated. In this detachment, for example, a solvent for washing can be added to the mixture and stirred, and then the solid content can be filtered by suction filtration or the like, and the solvent can be volatilized by a hot air drying oven or the like to recover the powder. get on. The component (B) after the end of a series of steps is not only internal but also on the surface (A). Then, the component (B) is added to the liquid phase of the component (C) and mixed by a stirrer or the like to carry out the reaction of the component (A) with the component (C). Thereby, the component (A) remaining on the surface of the component (B) reacts with the component (C) to form a film. By the formation of the film, the component (A) existing in the inside of the component (B) can be left. The microcapsules are then detached from the mixture. In this separation, for example, a solvent for washing can be added to the mixture and stirred (C), and then the solid content can be filtered by suction filtration or the like, and the solvent can be volatilized by a hot air drying oven or the like to recover the solid content. . This solid portion is a liquid amine compound after microencapsulation. The mechanism for forming the capsule film by the above-mentioned (A) component and (C) component is not completely analyzed, but it can be considered as the above-mentioned (A) component present in the porous fine particle powder as a capsule support, that is, pKa is The liquid amine compound having a strong base of 8.0 or higher causes the acid anhydride to ring-open, and the resulting carboxyl anion reacts with other (C) components to polymerize and becomes the following formula (3 -14-200950878)

(R!及R2係分別獨立地表示來自（c )成份的各酸酐 φ 之烴基） 如下列式（4 )般之具有環氧基之化合物、如下列式 (5)般之具有環硫基之化合物、具有異氰酸酯基之化合 物、以及具有乙烯基之化合物等，由於是以胺化合物作爲 硬化劑或硬化促進劑進行反應之化合物，所以（A )成份 之胺化合物，相對於前述硬化性樹脂可用作爲硬化劑或硬 化促進劑。其結果爲，本發明之微膠囊，相對於硬化性樹 脂可用作爲具有隱性之硬化劑或硬化促進劑。硬化性樹脂 ©，是指於各分子內具有1個以上之以環氧基、環硫基、異 氰酸酯基、乙烯基爲典型例之反應性官能基之化合物，只 要是符合此條件者’其種類或分子量並無特別限定，此外 ，尙可在分子內同時具有其他官能基。(R! and R2 each independently represent a hydrocarbon group of each acid anhydride φ derived from the component (c)) a compound having an epoxy group as in the following formula (4), having an alkylthio group as in the following formula (5) A compound, a compound having an isocyanate group, a compound having a vinyl group, or the like, a compound which reacts with an amine compound as a curing agent or a curing accelerator, and an amine compound of the component (A) can be used as the curable resin. Hardener or hardening accelerator. As a result, the microcapsule of the present invention can be used as a recessive hardener or a hardening accelerator with respect to a curable resin. The curable resin is a compound having one or more reactive functional groups each having an epoxy group, an epoxy group, an isocyanate group or a vinyl group as a typical example in each molecule, and any one that satisfies the above conditions The molecular weight is not particularly limited, and in addition, hydrazine may have other functional groups in the molecule at the same time.

15- 200950878 本發明的較佳型態中，當使用具有環氧基之化合物、 具有環硫基之化合物、具有異氰酸酯基之化合物作爲硬化 性樹脂時，（B )成份可用作爲硬化劑。該機制爲，（B ) 成份中的胺化合物成爲陰離子而具有使環氧基等之反應性 官能基彼此進行開環聚合之功能。另一方面，當具有環氧 基之化合物或具有環硫基之化合物，一同與聚胺化合物、 聚酚化合物、聚硫醇化合物、酸酐組合而用作爲硬化劑時 ’前述胺化合物可用作爲硬化促進劑。該機制爲，前述胺 化合物使聚胺化合物、聚酚化合物等的活性氫遊離，並使 這些與複數個環氧基或環硫基反應。再者，對於具有乙烯 基之化合物，前述胺化合物可用作爲用以進行陰離子聚合 之硬化劑使用，並藉由與有機過氧化物組合，可作爲硬化 促進劑使用於自由基聚合。該機制爲，胺化合物促進有機 過氧化物的分解而容易產生自由基群。 具有環氧基之化合物，一般而言有稱爲環氧樹脂之所 知的化合物，例如有藉由表氯醇與雙酚類等的多價酚類或 多價醇類之縮合所製得者，具體例子有雙酚A型、溴化雙 酚A型、加氫雙酚A型、雙酚F型、雙酚S型、雙酚AF 型、聯苯型、萘型、芴型、酚醛型、酚類酚醛型、鄰甲酚 酚醛型、三（羥苯基）甲烷型、四酚基乙烷型等之縮水甘 油醚型環氧樹脂。其他例如有藉由表氯醇與鄰苯二甲酸衍 生物或脂肪酸等的羧酸之縮合所製得之縮水甘油酯型環氧 樹脂；藉由表氯醇與胺類 '氰尿酸類、乙內醯脲類之反應 -16- 200950878 所製得之縮水甘油胺型環氧樹脂；以及以其他種種 行改質之環氧樹脂，但不限定於此。 具有環硫基之化合物，較多爲刊物或專利文獻 爲噻喃（Thiirane)者。具有環硫基之化合物的具 有2,2-雙（4- (2,3-環硫丙氧基）苯基）丙烷、雙 2,3-環硫丙氧基）苯基）甲烷、1，6-二（2,3-環硫丙 萘、1，1，1-三-(4- (2,3-環硫丙氧基）苯基）乙烷、 ® (4-(2，3-環硫丙氧基）環己基）丙烷、雙（4-(2 丙氧基）環己基）甲烷、1,1,1-三-(4- (2,3-環硫 )環己基）乙烷、1,5-戊二醇的（2,3-環硫環己基 1,6-己二醇的二（3,4-環硫辛基）醚等，但不限定於 具有異氰酸酯基之化合物的具體例子，芳香族 酸酯有2，4-甲苯二異氰酸酯、2，6-甲苯二異氰酸酯 二苯甲烷二異氰酸酯、2,4’-二苯甲烷二異氰酸酯、 苯甲烷二異氰酸酯、聚伸苯聚伸甲聚異氰酸酯、1: © 異氰酸酯、1,4-萘二異氰酸酯、對伸苯二異氰酸酯 苯二異氰酸酯、鄰二甲苯二異氰酸酯、間二甲苯二 酯，脂肪族二異氰酸酯有四伸甲二異氰酸酯、六伸 氰酸酯、2-甲基-1,5-戊烷二異氰酸酯等。此外，脂 異氰酸酯有1-甲基環己烷-2,4-二異氰酸酯、異佛爾 氰酸酯、二環己甲烷-4,4’-二異氰酸酯等，但不限 〇 具有乙烯基之化合物，較理想爲具有丙烯酸基 丙烯酸基或乙烯醚基之化合物。具有丙烯酸基、甲 方法進 中記載 體例子 (4-( 氧基） 2,2-雙 ,3-環硫 丙氧基 )醚、 此。 二異氰 、4,4’-2,2’-二 ，5-萘二 、間伸 異氰酸 甲二異 環族二 酮二異 定於此 、甲基 基丙烯 -17- 200950878 酸基或乙烯醚基之化合物，有單官能、2官能、3官能、 多官能的單體或低聚物，有藉由胺化合物使單體或低聚物 進行陰離子聚合反應而成爲高分子化之情況，以及藉由有 機過氧化物與胺化合物產生自由基群，進行自由基聚合反 應而成爲高分子化之情況（以下將丙烯酸與甲基丙烯酸合 稱爲（甲基）丙烯酸）。 具有（甲基）丙烯酸基之單官能化合物，例如有（甲 基）丙烯酸十二烷酯、（甲基）丙烯酸十八烷酯、（甲基 © )丙烯酸四氫糠酯、己內酯改質（甲基）丙烯酸四氫糠酯 、（甲基）丙烯酸環己酯、（甲基）丙烯酸二環戊酯、（ 甲基）丙烯酸異莰酯、（甲基）丙烯酸苯甲酯、（甲基） 丙烯酸苯酯、（甲基）丙烯酸苯氧乙酯、（甲基）丙烯酸 苯氧二乙二醇酯、（甲基）丙烯酸苯氧四乙二醇酯、（甲 基）丙烯酸壬基苯氧乙酯、（甲基）丙烯酸壬基苯氧四乙 二醇酯、（甲基）丙烯酸甲氧二乙二醇酯、（甲基）丙烯 酸乙氧二乙二醇酯、（甲基）丙烯酸酯、（甲基）丙烯酸 〇 丁氧乙酯、（甲基）丙烯酸丁氧三乙二醇酯、（甲基）丙 烯酸2-乙基己基聚乙二醇酯、（甲基）丙烯酸壬基苯基聚 丙二醇酯、（甲基）丙烯酸甲氧二丙二醇酯、（甲基）丙 烯酸縮水甘油酯、（甲基）丙烯酸酯、（甲基）丙烯酸2-羥乙酯、（甲基）丙烯酸2-羥丙酯、（甲基）丙烯酸甘油 酯、（甲基）丙烯酸聚乙二醇酯、（甲基）丙烯酸聚丙二 醇酯、表氯醇（以下略稱爲ECH )改質（甲基）丙烯酸丁 酯、ECH改質（甲基）丙烯酸苯氧酯、環氧乙烷（以下略 -18- 200950878 稱爲EO)改質（甲基）丙烯酸鄰苯二甲酸酯、EO改 甲基）丙烯酸琥珀酸酯、己內酯改質（甲基）丙烯酸 乙酯、（甲基）丙烯酸Ν,Ν-二甲基胺乙酯、（甲基） 酸Ν，Ν-二乙基胺乙酯、（甲基）丙烯酸嗎啉酯、ΕΟ (甲基）丙烯酸磷酸酯等，但不限定於此。 二官能化合物，例如有二（甲基）丙烯酸1,3-丁 酯、二（甲基）丙烯酸1，4-丁二醇酯、二（甲基）丙 Φ 新戊二醇酯、二（甲基）丙烯酸1，6-己二醇酯、二（ )丙烯酸乙二醇酯、二（甲基）丙烯酸聚乙二醇酯、 甲基）丙烯酸丙二醇酯、二（甲基）丙烯酸三丙二醇 ΕΟ改質二（甲基）丙烯酸新戊二醇酯、環氧丙烷（ 略稱爲ΡΟ)改質二（甲基）丙烯酸新戊二醇酯、二 基）丙烯酸雙酚Α酯、ΕΟ改質二（甲基）丙烯酸雙 酯、EC Η改質二（甲基）丙烯酸雙酚a酯、EO改質 甲基）丙烯酸雙酚S酯、二丙烯酸羥基三甲基乙酸酯 ® 二醇酯、己內酯改質二丙烯酸羥基三甲基乙酸酯新戊 酯、羥基三甲基乙酸酯新戊二醇改質二（甲基）丙烯 羥甲丙烷酯、十八烷改質二（甲基）丙烯酸新戊四醇 二丙烯酸二環戊酯、EO改質二（甲基）丙烯酸二環 、異氰尿酸二（甲基）丙烯醯酯等，但不限定於此。 三官能化合物，例如有三（甲基）丙烯酸三羥甲 酯、三（甲基）丙烯酸新戊四醇酯、EO改質三（甲 丙烯酸三羥甲丙烷酯' PO改質三（甲基）丙烯酸三 丙烷酯、ECH改質三（甲基）丙烯酸三羥甲丙烷酯、15-200950878 In a preferred embodiment of the invention, when a compound having an epoxy group, a compound having an epoxy group, or a compound having an isocyanate group is used as the curable resin, the component (B) can be used as a hardener. This mechanism is such that the amine compound in the component (B) becomes an anion and has a function of ring-opening polymerization of reactive functional groups such as an epoxy group. On the other hand, when a compound having an epoxy group or a compound having an episulfide group is used together with a polyamine compound, a polyphenol compound, a polythiol compound, or an acid anhydride as a hardener, the aforementioned amine compound can be used as a hardening accelerator. Agent. This mechanism is such that the amine compound liberates the active hydrogen of the polyamine compound, the polyphenol compound, and the like, and reacts these with a plurality of epoxy groups or episulfide groups. Further, as the compound having a vinyl group, the above amine compound can be used as a curing agent for anionic polymerization, and can be used as a curing accelerator for radical polymerization by being combined with an organic peroxide. This mechanism is such that an amine compound promotes decomposition of an organic peroxide and is liable to generate a radical group. A compound having an epoxy group generally has a known compound called an epoxy resin, and is obtained, for example, by condensation of epichlorohydrin with a polyvalent phenol or a polyvalent alcohol such as a bisphenol. Specific examples include bisphenol A type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, anthraquinone type, and phenol type A glycidyl ether type epoxy resin such as a phenolic novolac type, an o-cresol novolac type, a tris(hydroxyphenyl)methane type or a tetraphenol ethane type. Other examples include a glycidyl ester type epoxy resin obtained by condensation of epichlorohydrin with a phthalic acid derivative or a carboxylic acid such as a fatty acid; and epichlorohydrin and an amine 'cyanuric acid, B Reaction of guanidinium - a glycidylamine type epoxy resin obtained by the use of -1650878; and an epoxy resin modified by other various types, but is not limited thereto. Compounds having an episulfide group, mostly published or patented as Thiirane. a compound having an episulfide group having 2,2-bis(4-(2,3-cyclosulfoxy)phenyl)propane, bis 2,3-cyclothiopropoxy)phenyl)methane, 1, 6-bis(2,3-epoxythiolane, 1,1,1-tri-(4-(2,3-cyclosulfoxy)phenyl)ethane, ® (4-(2,3- Cyclopropyloxy)cyclohexyl)propane, bis(4-(2propyloxy)cyclohexyl)methane, 1,1,1-tris-(4-(2,3-cyclosulfanyl)cyclohexyl)ethane And 1,5-pentanediol (2,3-epoxythiocyclohexyl 1,6-hexanediol bis(3,4-cyclothiooctyl)ether, etc., but not limited to compounds having an isocyanate group Specific examples of the aromatic acid ester include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, phenylmethane diisocyanate, and polyphenylene stretching. Polyisocyanate, 1: isocyanate, 1,4-naphthalene diisocyanate, p-phenylene diisocyanate phenyl diisocyanate, o-xylene diisocyanate, m-xylylene diester, aliphatic diisocyanate tetra-n-diisocyanate, six Cyanate ester, 2-methyl-1,5-pentane diisocyanate, etc. The aliphatic isocyanate is 1-methylcyclohexane-2,4-diisocyanate, isophortanate, dicyclohexylmethane-4,4'-diisocyanate, etc., but is not limited to a compound having a vinyl group. It is preferably a compound having an acryl-based acryl group or a vinyl ether group, and has an acryl-based group and a method of the invention (4-(oxy) 2,2-bis, 3-cyclothiopropoxy)ether. Diisocyanate, 4,4'-2,2'-di, 5-naphthalene, meta-isocyanuric diisocyclodiketone diisodine, here, methyl propylene -17- 200950878 acid group or a vinyl ether group-containing compound having a monofunctional, bifunctional, trifunctional or polyfunctional monomer or oligomer, and having an anion polymerization reaction of a monomer or an oligomer by an amine compound to be polymerized. And a radical group generated by an organic peroxide and an amine compound, and a radical polymerization reaction is carried out to form a polymerized product (hereinafter, acrylic acid and methacrylic acid are collectively referred to as (meth)acrylic acid). Acrylic based monofunctional compound, for example, dodecane (meth)acrylate , octadecyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone modified tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate, (methyl) Dicyclopentyl acrylate, isodecyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy (meth) acrylate Ethylene glycol ester, phenoxytetramethylene (meth)acrylate, nonylphenoxyethyl (meth)acrylate, nonylphenoxytetramethylene (meth)acrylate, (meth)acrylic acid Methoxydiethylene glycol ester, ethoxydiethylene glycol (meth)acrylate, (meth) acrylate, butoxy oxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate Ester, 2-ethylhexyl polyethylene glycol (meth)acrylate, nonylphenyl polypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, glycidyl (meth)acrylate , (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-(meth) acrylate Propyl ester, glyceryl (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, epichlorohydrin (hereinafter abbreviated as ECH) modified butyl (meth)acrylate ECH modified phenoxy (meth) acrylate, ethylene oxide (hereinafter referred to as -18-200950878 called EO) modified (meth) phthalate phthalate, EO modified methyl) acrylic succinic acid Ester, caprolactone modified ethyl (meth) acrylate, bismuth (meth) acrylate, hydrazine-dimethylamine ethyl ester, bismuth (methyl) hydrazine, hydrazine-diethylamine ethyl ester, (methyl The morpholinic acid acrylate or fluorene (meth) acrylate phosphate is not limited thereto. Difunctional compounds, for example, 1,3-butyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, di(methyl)propane Φ neopentyl glycol ester, di(a) 1,6-hexanediol, bis(ethylene acrylate), polyethylene glycol di(meth)acrylate, propylene glycol methyl methacrylate, tampering of tripropylene glycol di(meth)acrylate Neopentyl glycol di(meth)acrylate, propylene oxide (abbreviated as hydrazine) modified neopentyl glycol di(meth)acrylate, bisphenol decyl acrylate, hydrazine modified Methyl) acrylate diester, EC Η modified di(meth) acrylate bisphenolate, EO modified methyl acrylate bisphenol S ester, hydroxy trimethyl acetate di acrylate diol ester, Ester-modified hydroxytrimethyl acetate diamyl acetate, hydroxytrimethyl acetate neopentyl glycol modified di(meth) propylene hydroxypropyl propane ester, octadecyl modified di(methyl) Dipentyl pentyl acrylate, dicyclopentanyl acrylate, EO modified di(meth)acrylic acid bicyclo, isocyanuric acid di(meth) decyl methacrylate But are not limited thereto. Trifunctional compounds such as trimethylol (meth)acrylate, neopentyl tris(meth)acrylate, EO modified tris (trimethylolpropane acrylate) PO modified tris(meth)acrylic acid Tripropane ester, ECH modified trimethylolpropane tris(meth)acrylate,

莺（ 2-羥 改實 烯酸 酯、 以下 (甲 酚A 二（ 新戊 二醇 酸三 酯、 戊酯 丙烷 基） 羥甲 ECH -19- 200950878 改質三（甲基）丙烯酸甘油酯、異氰尿酸三（丙烯醯氧基 乙基）酯等，但不限定於此。 多官能化合物，例如有四（甲基）丙烯酸二（三羥甲 丙烷）酯、四（甲基）丙烯酸新戊四醇酯、五（甲基）丙 烯酸二新戊四醇羥酯、烷基改質五丙烯酸二新戊四醇酯、 六（甲基）丙烯酸二新戊四醇酯、己內酯改質六（甲基） 丙烯酸二新戊四醇酯等，但不限定於此。 低聚物例如有雙酚A型、酚醛型、多價醇型、多質子 © 酸型、聚丁二烯型的（甲基）丙烯酸環氧酯；聚酯型、聚 醚型的（甲基）丙烯酸胺甲酸酯等，但不限定於此。 具有乙烯基之化合物，例如有乙二醇二乙烯醚、1，3-丙二醇二乙烯醚、丙二醇二乙烯醚、1，4-丁二醇二乙烯醚 、1,3-丁二醇二乙烯醚、1，2·丁二醇二乙烯醚、2,3-丁二醇 二乙烯醚、1-甲基-1，3-丙二醇二乙烯醚、2-甲基-1,3-丙二 醇二乙烯醚、2-甲基-1,2-丙二醇二乙烯醚、1，5-戊二醇二 乙烯醚、1,6-己二醇二乙烯醚、環己烷-1,4-二醇二乙烯醚 © 、環己烷-1,4-二甲醇二乙烯醚、對二甲苯二醇二乙烯醚、 二乙二醇二乙烯醚、三乙二醇二乙烯醚、四乙二醇二乙烯 醚、聚乙二醇二乙烯醚、二丙二醇二乙烯醚、三丙二醇二 乙烯醚、四丙二醇二乙烯醚、聚丙二醇二乙烯醚、乙二醇 丙二醇共聚物二乙烯醚等，但不限定於此。 使前述（甲基）丙烯酸化合物進行自由基聚合時所使 用之前述有機過氧化物的具體例子，有過氧化丁酮、過氧 化環己酮、過氧化3,3,5 -三甲基環己酮、過氧化甲基環己 -20- 200950878 酮、過氧化乙醯乙酸甲酯、過氧化乙醯丙酮等之過氧化酮 類等；1,1-雙（三級丁基過氧基）-3,3,5-三甲基環己烷、 1.1- 雙（三級丁基過氧基）環己烷、2,2-雙（三級丁基過 氧基）辛烷、正丁基-4,4-雙（三級丁基過氧基）戊酸酯、 2.2- 雙（三級丁基過氧基）丁烷等之過氧化縮酮類等：三 級丁基氫過氧化物、異丙苯氫過氧化物、二異丙苯氫過氧 化物、對孟烷氫過氧化物、2,5-二甲基己烷-2,5-二氫過氧 ❹ 化物、1，1，3,3-四甲基丁基氫過氧化物等之氫過氧化物類 :過氧化二（三級丁基）、過氧化三級丁基異丙苯、過氧 化二異丙苯、α，α:’-雙（三級丁基過氧基間異丙基）苯、 2.5- 二甲基-2,5-二（三級丁基過氧基）己烷、2,5-二甲基- 2.5- 二（三級丁基過氧基）己烷-3等之過氧化二烷基類； 過氧化乙醯、過氧化異丁醯、過氧化辛醯、過氧化癸醯、 過氧化十二醯、過氧化3,5,5-三甲基己醯、過氧化琥珀酸 、過氧化苯甲醯、過氧化2，4-二環苯甲醯、過氧化間甲苯 ® 甲醯等之過氧化二醯類；過氧二碳酸二異丙酯、過氧二碳 酸二2-乙基己酯、過氧二碳酸二正丙酯、過氧二碳酸雙_ (4-三級丁基環己基）酯、過氧二碳酸二（十四基）酯、 過氧二碳酸二2-乙氧乙酯、過氧二碳酸二甲氧異丙酯、過 氧二碳酸二（3-甲基-3-甲氧丁基）酯、過氧二碳酸二丙烯 酯等之過氧二碳酸酯類；過氧醋酸三級丁酯、過氧異丁三 級丁酯、過氧異丁酸三級丁酯、過氧新癸酸三級丁酯、過 氧新癸酸異苯酯、過氧2-乙基己酸三級丁酯、過氧3,5,5_ 三甲基己酸三級丁酯、過氧十二酸三級丁酯、過氧苯甲酸 -21 - 200950878 三級丁酯、過氧異苯二甲酸二三級丁酯、2，5-二甲基-2，5-二（苯甲醯過氧基）己烷、過氧順丁烯二酸三級丁酯、過 氧異丙基碳酸三級丁酯、過氧辛酸異苯酯、過氧酸三級丁 酯、過氧新癸酸三級己酯、過氧異丁酸三級己酯、過氧新 己酸三級丁酯、過氧新己酸三級己酯、過氧新己酸異苯酯 等之過氧酯類；以及過氧化乙醯環己磺醯、過氧丙烯碳酸 二級丁醋等，但不限定於此。 相對於上述所舉出之各種硬化性樹脂，可將本發明之 微膠囊用作爲硬化劑或硬化促進劑，尤其相對於具有環氧 基之化合物或具有環硫基之化合物，適合用作爲硬化促進 劑。此時，作爲使具有環氧基之化合物、具有環硫基之化 合物硬化之硬化劑，於本發明中尤其理想者，爲與於分子 內具有2個以上的胺基之聚胺化合物、於分子內具有2個 以上的酚基之聚酚化合物、於分子內具有2個以上的硫醇 基之聚硫醇化合物、或是酸酐倂用。 所倂用之前述聚胺化合物的具體例，有二伸乙三胺、 三伸乙二胺、間二甲苯二胺、異佛爾酮二胺、1,3-雙胺甲 基環己烷、二胺二苯甲烷、間伸苯二胺、二胺二苯颯、二 氰二醯胺、有機酸二醯肼、呱啶等，但不限定於此。 前述聚酚化合物的具體例，有酚、烷基酚等之酚類與 甲醛、與對甲醛等的醛類反應而製得之酚醛型酚類樹脂、 以及這些的改質酚類酚醛樹脂之ZILOG型酚類樹脂、二 環戊二烯型酚類樹脂、多官能酚類樹脂等之多價酚等，但 不限定於此。較理想爲室溫下爲液狀之聚酚化合物。 -22- 200950878 前述聚硫醇化合物的具體例，有3-甲氧丁基3-氫 丙酸酯、2-乙基己基3-氫硫基丙酸酯、十三基3-氫硫 酸酯、三羥甲丙烷三硫丙酸酯、新戊四醇四硫丙酸酯 基硫甘醇酸酯、2_乙基己基硫甘醇酸酯、乙二醇雙硫 酸酯、1，4-丁二醇雙硫甘醇酸酯、三羥甲丙烷三硫甘 酯、新戊四醇四硫甘醇酸酯、二（氫硫基乙基）醚、 院硫醇、I -己院硫醇、環己硫醇、1，4 -丁院二硫醇、 〇 硫基2-丁醇、r-氫硫基丙基三甲氧矽烷、苯硫醇、 基硫醇、1，3,5-三氫硫基甲基苯、1,3,5-三氫硫基弓 2,4,6_三甲基苯、末端含有硫醇基之聚醚、末端含有 基之聚硫醚、藉由環氧化合物與硫化氫的反應所製得 醇化合物、藉由聚硫醇化合物與環氧化合物的反應所 之末端具有硫醇基之硫醇化合物等，但不限定於此。 前述酸酐的具體例，有十二烯琥珀酸酐、聚壬二 、六氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、甲基四氫 © 二甲酸酐、甲基內次甲基四氫苯酸酐、偏苯三甲酸酐 均四酸酐、二苯甲酮四羧酸酐、四溴鄰苯二甲酸酐、 酸酐等，但不限定於此。此外，可使用於1個分子中 2個以上的酸酐骨幹之聚合物型的酸酐，具體而言有 會社 Kuraray 製的 LIR403、LIR410 或是 Daicel 化學 株式會社製的VEMA等。 本發明之硬化性樹脂組成物中之本發明的微膠囊 ，爲微膠囊中的胺化合物可發揮硬化劑或硬化促進劑 能之有效量，與先前技術的使用量相同，可因應使用 硫基 基丙 、甲 甘醇 醇酸 1-丁 3 -氫 苯甲 3基_ 硫醇 之硫 製得 酸酐 鄰苯 、苯 氯茵 具有 株式 工業 的量 的功 目的 -23- 200950878 來適當地決定。一般而言，相對於反應性官能基100質量 份，本發明之微膠囊可添加0.1〜50質量份。 本發明之硬化性樹脂組成物中，可在不損及本發明的 特性之範圍內，適當地調配顏料、染料等的著色劑、金屬 粉、碳酸鈣、滑石、二氧化矽、氧化鋁、羥化鋁等之無機 充塡劑、難燃劑、有機充塡劑、可塑劑、防氧化劑、消泡 劑、矽烷系偶合劑、勻整劑、流變控制劑、溶劑等添加劑 。藉由這些的添加，可製得樹脂強度·接著強度·作業性 © •保存性等爲優良之組成物及其硬化物。 以下係揭示實施例而更詳細地說明本發明，但本發明 並不限定於這些實施例。 實施例 [實施例1] 第一步驟 將DBU(San-Apro株式會社製）200g與B-6C (鈴木 〇 油脂工業株式會社製之多孔質·中空二氧化矽型式）l〇〇g 放入至燒杯中攪拌30分鐘。由於在吸收時會發熱，所以 在攪拌後放置2小時而冷卻至室溫。添加300g的丁酮（ 以下稱爲MEK)攪拌30分鐘。藉由No_3的濾紙，在有限 會社桐山製作所製的漏斗（通稱爲桐山漏斗）中進行吸引 過濾’將未被吸收之剩餘的DBU與用於洗淨所添加之 MEK予以過濾。使過濾物在托盤上薄薄地擴散，藉由熱風 乾燥爐進行4〇°C X2小時的乾燥。（以下將在第一步驟中 -24- 200950878 經處理後的粉體稱爲處理完畢的粉體） 第二步驟 將3或4-甲基-l，2,3,6-四氫鄰苯二甲酸酐（NH-2200R 曰立化成工業株式會社製）200g添加於處理完畢的粉體 1 〇〇g中攪拌30分鐘。攪拌結束後，添加3 00g的MEK再 攪拌30分鐘。藉由ν〇·3的濾紙在桐山漏斗中進行吸引過 Φ 濃。使過濾物在托盤上薄薄地擴散，藉由熱風乾燥爐進行 40°C χ2小時的乾燥。 [實施例2、實施例3、比較例！] 係使用第1表所示之DBN、三伸乙二胺、N-甲基嗎啉 作爲胺化合物來取代D B U，除此之外，其他以與實施例1 相同的處方進行膠囊的調製。 第1表 號碼 三級胺化合物 酸解離常數（pKa) 實施例1 DBU 12.5 實施例2 DBN 12.7 實施例3 三伸乙二胺 8.8 比較例1 N-甲基嗎啉 7.5 [比較例2〜1 5 ] IS於使吸收至多孔質微粉末之液狀胺化合物隱性化之 $ & ’係進行下列3種方法。各種方法所使用之原料係記 «Mg 2表°第2表的原料爲取代實施例丨中的酸酐而使 用之原料。 25· 200950878 (1) 係使用在室溫下與液狀胺於短時間內進行硬化 反應之化合物來取代相當於（C)成份之酸酐，並與殘留 於（B)成份表面之液狀胺化合物反應而形成覆膜之隱性 化方法（比較例2〜10 ) (2) 藉由與胺化合物進行配位反應之有基金屬錯合 物來進行處理，藉此降低胺化合物的活性之隱性化方法（ 比較例1 1 ~ 1 2 ) (3) 使用蠟等之非反應系的材料形成覆膜以進行物 理性遮蔽之藉由乾式混合法所進行的機械性隱性化方法（ 比較例13〜15)。此方法中，膠囊材料由於直接以固體方 式投入，所以未使用溶劑。市售的裝置，例如可使用 Hosokawa Micron株式會社的AMS系列，或是株式會社奈 良機械製作所的HYBRIDIZER系列等。 200950878 第2表 號碼 隱化原料 原料 原料製造商 原料名稱 比例(％) 比較例2 環氧樹脂 大日本油墨化學工業株式會社 HP-4032D 100 比較例3 異氰酸酯樹脂 曰本Polyurethane工業株式會社 Millionate MR-200 100 比較例4 丙烯酸樹脂 共榮社化學株式會社 環氧樹脂A3002 100 比較例5 甲基丙烯酸樹脂 共榮社化學株式會社 環氧樹脂M3002 100 比較例6 聚硫醇(酯型） Japan Epoxy Resin 株式會社 jER Cure 0X40 100 比較例7 環氧樹脂 大日本油墨化學工業株式會社 Epiclon EXA-835LV 66 聚硫醇(酯型） Japan Epoxy Resin 株式會社 jER Cure 〇X40 34 比較例8 環氧棚旨 大曰本油墨化學工業株式會社 HP-4032D 66 聚硫醇(酯型） Japan Epoxy Resin 株式會社 jERCure 〇X40 34 比較例9 丙烯酸樹脂 共榮社化學株式會社 環氧樹脂A3002 50 聚硫醇(酯型） Japan Epoxy Resin 株式會社 jER Cure 〇X40 50 比較例10 丙烯酸樹脂 共榮社化學株式會社 環氧樹脂A3002 95 有機過氧化物 曰本油脂株式會社 過異丙苯H-80 5 比較例11 有機鈦化合物 Matsumoto Fine Chemical 株式會社 Orgatix TC-750 100 比較例12 有機銷化合物 Matsumoto Fine Chemical 株式會社 Orgatix ZC-580 100 比較例13 脂肪族羧酸(滑劑） 東京化成工業株式會社 硬脂酸 100 比較例14 蠟 曰本精蠟株式會社 LUVAX-1266 100 比較例15 萜樹脂 Yasuhara 株式 YP Resin YP-90L 100 [比較例2〜10] 第一步驟 將DBU200g與B-6C100g放入至燒杯中攪拌30分鐘 。由於在吸收時會發熱，所以在攪拌後放置2小時而冷卻 至室溫。添加300g的ME K攪拌30分鐘。藉由No.3的瀘 紙，在桐山漏斗中進行吸引過濾，將未被吸收之剩餘的 DBU與用於洗淨所添加之MEK予以過瀘。使過濾物在托 盤上薄薄地擴散，藉由熱風乾燥爐進行40°C x2小時的乾 -27- 200950878 燥。 第二步驟 將比較例2〜1 〇所使用之原料200g添加於處理完畢的 粉體l〇〇g中攪拌30分鐘。攪拌結束後，添加3 00g的 MEK再攪拌30分鐘。藉由No .3的濾紙在桐山漏斗中進行 吸引過濾。使過濾物在托盤上薄薄地擴散，藉由熱風乾燥 爐進行40°C x2小時的乾燥。 ◎ [比較例1 1~12] 第一步驟 將DBU200g與B-6C100g放入至燒杯中攪拌30分鐘 。由於在吸收時會發熱，所以在攪拌後放置2小時而冷卻 至室溫。添加300g的MEK攪拌30分鐘。藉由Νο·3的濾 紙，在桐山漏斗中進行吸引過濾，將未被吸收之剩餘的 DBU與用於洗淨所添加之ΜΕΚ予以過濾。使過濾物在托 〇 盤上薄薄地擴散，藉由熱風乾燥爐進行40°C Χ2小時的乾 燥。 第二步驟 將比較例11及12所使用之原料50g添加於處理完畢 的粉體l〇〇g中攪拌30分鐘。攪拌結束後，添加300g的 MEK再攪拌30分鐘。藉由No.3的濾紙在桐山漏斗中進行 吸引過濾。使過濾物在托盤上薄薄地擴散，藉由熱風乾燥 -28- 200950878 爐進行40°C x2小時的乾燥。 [比較例1 3〜1 5 ] 第一步驟 將DBU200g與B-6C100g放入至燒杯中攪拌30分鐘 。由於在吸收時會發熱’所以在攪拌後放置2小時而冷卻 至室溫。添加300g的MEK攪拌30分鐘。藉由Ν〇·3的濾 ❹ 紙，在桐山漏斗中進行吸引過濾’將未被吸收之剩餘的 DBU與用於洗淨所添加之ΜΕΚ予以過濾。使過濾物在托 盤上薄薄地擴散，藉由熱風乾燥爐進行40 °Cx2小時的乾 燥。 第二步驟 藉由奈良機械製作所株式會社製的hybridization SYSTEM NHS-0型進行乾式膠囊化處理。將比較例13〜15 〇 所使用之原料i〇g添加於處理完畢的粉體i〇g中，並以 9700m/s進行1分鐘的處理。將處理品予以刮取而回收。 [第二步驟的狀態] 在實施例及比較例的第二步驟中，以目視來確認隱性 化處理的狀態。當在處理中反應進行使黏度增加而失去流 動性時，設定爲不合格（NG)，當具有流動性時，設定 爲合格（OK)。試驗結果係表示於第3表之「第二步驟 的狀態」。（以下，第二步驟的狀態係依據此方法） -29- 200950878 [初期保存性] 以雙酚型環氧樹脂（EPICLON EXA-83 5 LV大日本油 墨化學工業株式會社製）100重量份與聚硫醇化合物之 jER XURE QX40 ( Japan Epoxy Resin 株式會社製）50 重 量份的混合物作爲檢定液，來確認膠囊化的有無。當將 DBU添加於環氧樹脂與聚硫醇化合物的混合物時，會急遽 發熱而瞬間硬化，因此，可將實施例及比較例中所調製之 © 粉體添加於前述檢定液中，並目視來確認之後的狀態，並 判定合格與否。評估條件係設定爲相對於檢定液3 0重量 份，實施例1 ~ 3及比較例4、5、1 0、1 1、1 3、14、1 5中 係分別添加5重量份並進行攪拌，在靜置於25 °C時，於1 小時以內反應進行使黏度增加而失去流動性時，設定爲不 合格（NG )，當具有流動性時，設定爲合格（OK )。試 驗結果係表示於第3表之「初期保存性」。在「第二步驟 的狀態」中爲NG者，係以「_」來表示。（以下，初期 〇 保存性係依據此方法） [保存性] 對於初期保存性中具有1小時以上的保存安定性之實 施例1 ~3及比較例1 1、1 3，接著再確認2 5 °C下的保存安 定性。於每1天確認是否產生膠體化直到經過5天爲止。 膠體化，是指藉由EHD型黏度計所測定之超過黏度測定 邊限爲止之時間（天）。在控制溫度25 °C、測定時間3分 -30- 200950878 鐘、錐形轉子1°23’xR24的條件下進行測定’測定邊限相 當於lOOPa. s。試驗結果係表示於第3表之「保存性」。 在「第二步驟的狀態」與「初期保存性」中爲NG者’係 以「-」來表示。（以下，保存性係依據此方法）莺 (2-hydroxy-modified acrylate, the following (cresol A (neopentyl glycol triester, amyl ester propane) hydroxymethyl ECH -19- 200950878 modified tris (meth) acrylate, different Although triiso(acryloxyethyl) cyanurate or the like is not limited thereto. Polyfunctional compounds such as di(trimethylolpropane) tetra(meth)acrylate and neopentyl tetra(meth)acrylate Alcohol ester, bishydroxypentaerythritol penta(meth)acrylate, alkyl modified ditylar pentaerythritol pentaacrylate, dipentaerythritol hexa(meth)acrylate, modified caprolactone Methyl) dipentaerythritol acrylate, etc., but is not limited thereto. Examples of the oligomer include bisphenol A type, phenol type, polyvalent alcohol type, polyprotonated acid type, and polybutadiene type (A) Butyl acrylate acrylate; polyester, polyether (meth) acrylate urethane, etc., but is not limited thereto. Compounds having a vinyl group, for example, ethylene glycol divinyl ether, 1, 3 -propylene glycol divinyl ether, propylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,3-butanediol divinyl ether, 1,2 · Butanediol divinyl ether, 2,3-butanediol divinyl ether, 1-methyl-1,3-propanediol divinyl ether, 2-methyl-1,3-propanediol divinyl ether, 2-A 1,2-propanediol divinyl ether, 1,5-pentanediol divinyl ether, 1,6-hexanediol divinyl ether, cyclohexane-1,4-diol divinyl ether ©, cyclohexyl Alkane-1,4-dimethanol divinyl ether, p-xylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol Although not limited to vinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol divinyl ether, polypropylene glycol divinyl ether, ethylene glycol propylene glycol copolymer divinyl ether, etc., the above (meth) Specific examples of the organic peroxide used in the radical polymerization of the acrylic compound include butanone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methyl peroxide. Cyclohexene-20- 200950878 ketone, methyl acetoxyacetate, acetone peroxide, etc.; 1,1-bis(tertiary butylperoxy)-3,3,5- Trimethyl ring Alkane, 1.1-bis(tertiary butylperoxy)cyclohexane, 2,2-bis(tertiary butylperoxy)octane, n-butyl-4,4-bis(tributyl) Peroxy ketals such as oxy) valerate, 2.2-bis(tertiary butylperoxy)butane, etc.: tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropyl Benzene hydroperoxide, p-menthan hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxy ruthenium, 1,1,3,3-tetramethylbutyl hydrogen Hydroperoxides such as oxides: di(tertiary butyl peroxide), tributyl cumene peroxide, dicumyl peroxide, α, α: '-bis (tributyl) Oxy-m-isopropyl)benzene, 2.5-dimethyl-2,5-di(tri-butylperoxy)hexane, 2,5-dimethyl-2.5-di(tri-butylperoxy) Peroxydialkyl peroxides such as hexane-3; acetamidine peroxide, isobutyl sulfoxide, octanoic peroxide, cerium peroxide, cerium peroxide, peroxidation 3,5,5- Trimethylhexyl pentoxide, peroxy succinic acid, benzammonium peroxide, 2,4-dicyclic benzamidine peroxide, m-toluene peroxide, formazan, etc. Dioxins per pass; diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-(4-tert-butylcyclohexane) peroxydicarbonate Hexyl) ester, di(tetradecyl)peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-peroxydicarbonate) Peroxydicarbonate such as 3-methoxybutyl) ester or dipropylene peroxydicarbonate; tertiary butyl peroxyacetate, butyl peroxy isobutylate, tertiary butyl peroxyisobutyrate Ester, tertiary butyl peroxy neodecanoate, isophenyl peroxy neodecanoate, tertiary butyl peroxy 2-ethylhexanoate, tertiary butyl peroxy 3,5,5-trimethylhexanoate , tert-butyl peroxydodecanoate, peroxybenzoic acid-21 - 200950878 tertiary butyl ester, di-tert-butyl peroxy isophthalate, 2,5-dimethyl-2,5-di ( Benzoyl peroxy)hexane, peroxybutyl maleate, tertiary butyl peroxy isopropyl carbonate, isophenyl peroxyoctanoate, tertiary butyl peroxyacid, peroxygen Tertiary neodecanoate, tertiary hexyl peroxyisobutyrate, tertiary butyl peroxy neohexanoate Peroxyesters such as peroxy neohexanoic acid hexyl hexanoate and peroxyisohexyl hexanoate; and ethoxylated hexamethylene sulfonate, peroxypropylene carbonate secondary vinegar, etc., but are not limited thereto . The microcapsules of the present invention can be used as a curing agent or a curing accelerator with respect to the various curable resins described above, and are particularly suitable for use as a curing accelerator with respect to a compound having an epoxy group or a compound having an epoxy group. Agent. In this case, as a curing agent which hardens a compound having an epoxy group or a compound having an epoxy group, it is particularly preferable in the present invention to be a polyamine compound having two or more amine groups in the molecule, and a molecule. A polyphenol compound having two or more phenol groups in the polymer, a polythiol compound having two or more thiol groups in the molecule, or an acid anhydride. Specific examples of the polyamine compound to be used include diethylenetriamine, triethylenediamine, m-xylenediamine, isophoronediamine, and 1,3-diaminemethylcyclohexane. Diamine diphenylmethane, meta-phenylenediamine, diamine diphenyl hydrazine, dicyandiamide, organic acid diterpene, acridine, etc., but is not limited thereto. Specific examples of the polyphenol compound include a phenolic phenolic resin obtained by reacting a phenol such as a phenol or an alkylphenol with formaldehyde, an aldehyde which reacts with formaldehyde, and the ZILOG of the modified phenolic phenol resin. The polyphenols such as a phenol resin, a dicyclopentadiene type phenol resin, and a polyfunctional phenol resin are not limited thereto. It is preferably a polyphenol compound which is liquid at room temperature. -22- 200950878 Specific examples of the above polythiol compound include 3-methoxybutyl 3-hydropropionate, 2-ethylhexyl 3-hydrothiopropionate, and thirteenth 3-hydrosulfate. Trimethylolpropane trithiopropionate, neopentyl alcohol tetrathiopropionate thioglycolate, 2-ethylhexyl thioglycolate, ethylene glycol disulfate, 1,4-butane Alcohol dithioglycolate, trimethylolpropane trithiolate, neopentyl alcohol tetrathioglycolate, bis(hydrothioethyl)ether, thiol, I-hexyl thiol, ring Hexyl mercaptan, 1,4 -butyl dithiol, decyl 2-butanol, r-hydrothiopropyltrimethoxy decane, benzene thiol, thiol, 1,3,5-trihydrogen Methylbenzene, 1,3,5-trihydrothio- 2,4,6-trimethylbenzene, a polyether having a thiol group at the end, a polythioether having a terminal group, and an epoxy compound The reaction of hydrogen sulfide produces an alcohol compound, a thiol compound having a thiol group at the terminal of the reaction between the polythiol compound and the epoxy compound, but is not limited thereto. Specific examples of the acid anhydride include dodecene succinic anhydride, polyfluorene dim, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methyl endomethyltetrahydrogen. The phthalic anhydride, trimellitic anhydride, tetracarboxylic anhydride, benzophenone tetracarboxylic anhydride, tetrabromophthalic anhydride, acid anhydride, and the like are not limited thereto. Further, a polymer type acid anhydride which can be used for two or more acid anhydride backbones in one molecule may be, for example, LIR403 or LIR410 manufactured by Kuraray Co., Ltd. or VEMA manufactured by Daicel Chemical Co., Ltd., or the like. The microcapsule of the present invention in the curable resin composition of the present invention is an amine compound in the microcapsule which can exert an effective amount of a hardener or a hardening accelerator, and is the same as the amount used in the prior art, and can be used in accordance with the sulfur group. The sulphuric acid of propylene, methylglycolic acid, 1-butane, 3-hydrogen benzoyl yl, thiol, sulphuric acid, phthalic acid, phthalic acid, phthalic acid, phthalic acid In general, the microcapsules of the present invention may be added in an amount of 0.1 to 50 parts by mass based on 100 parts by mass of the reactive functional group. In the curable resin composition of the present invention, a coloring agent such as a pigment or a dye, metal powder, calcium carbonate, talc, cerium oxide, aluminum oxide, or hydroxy group can be appropriately formulated within a range that does not impair the characteristics of the present invention. An additive such as an inorganic filling agent, a flame retardant, an organic filling agent, a plasticizer, an antioxidant, an antifoaming agent, a decane coupling agent, a leveling agent, a rheology control agent, a solvent, and the like. By the addition of these, it is possible to obtain a resin composition, a bonding strength, and an workability. The present invention will now be described in more detail by way of examples, but the invention is not limited thereto. [Example 1] In the first step, 200 g of DBU (manufactured by San-Apro Co., Ltd.) and B-6C (porous and hollow ceria type) manufactured by Suzuki Oil & Fats Co., Ltd. Stir in the beaker for 30 minutes. Since it generates heat during absorption, it was allowed to stand for 2 hours after stirring and cooled to room temperature. 300 g of methyl ethyl ketone (hereinafter referred to as MEK) was added and stirred for 30 minutes. The filter paper of No. 3 was used for suction filtration in a funnel manufactured by Kaneko Kogyo Co., Ltd. (commonly known as Kiriyama Funnel). The remaining DBU that was not absorbed and the MEK used for washing were filtered. The filtrate was allowed to spread thinly on the tray, and dried by a hot air drying oven at 4 ° C for 2 hours. (The powder which has been treated in the first step -24-200950878 is referred to as the processed powder.) The second step is 3 or 4-methyl-l,2,3,6-tetrahydroortylene 200 g of the acid anhydride (NH-2200R manufactured by Konica Chemicals Co., Ltd.) was added to the treated powder 1 〇〇g and stirred for 30 minutes. After the completion of the stirring, 300 g of MEK was added and stirred for another 30 minutes. The φ 〇 3 filter paper was used to attract Φ in the Tongshan funnel. The filtrate was allowed to spread thinly on the tray, and dried by a hot air drying oven at 40 ° C for 2 hours. [Example 2, Example 3, Comparative Example! The capsules were prepared in the same manner as in Example 1 except that DBN, triethylenediamine, and N-methylmorpholine shown in Table 1 were used as the amine compound instead of D B U. Table 1 No. Amino acid compound acid dissociation constant (pKa) Example 1 DBU 12.5 Example 2 DBN 12.7 Example 3 Triethylenediamine 8.8 Comparative Example 1 N-methylmorpholine 7.5 [Comparative Example 2 to 1 5 The IS is subjected to the following three methods in which the liquid amine compound absorbed into the porous fine powder is recessed. The raw materials used in the various methods are «Mg 2 Tables. The raw materials of the second table are the raw materials used in place of the acid anhydrides in the examples. 25· 200950878 (1) A compound which is equivalent to the acid anhydride of the component (C) and a liquid amine compound remaining on the surface of the component (B) is replaced with a compound which is subjected to a hardening reaction with a liquid amine at a room temperature for a short period of time. Recessive method for forming a film by reaction (Comparative Examples 2 to 10) (2) Treatment by a complex metal complex compound which is coordinated with an amine compound, thereby reducing the recessive activity of the amine compound (Comparative Example 1 1 to 1 2 ) (3) A mechanical recessive method by a dry mixing method in which a film is formed by using a non-reactive material such as wax to physically shield (Comparative Example 13) ~15). In this method, since the capsule material is directly charged in a solid form, no solvent is used. For the commercially available device, for example, the AMS series of Hosokawa Micron Co., Ltd., or the HYBRIDIZER series of Nara Machinery Manufacturing Co., Ltd., or the like can be used. 200950878 The second table number is concealed raw material raw material raw material manufacturer raw material name ratio (%) Comparative Example 2 Epoxy resin Dainippon Ink Chemical Industry Co., Ltd. HP-4032D 100 Comparative Example 3 Isocyanate resin Sakamoto Polyurethane Industrial Co., Ltd. Millionate MR-200 100 Comparative Example 4 Acrylic Resin Co., Ltd. Epoxy Resin A3002 100 Comparative Example 5 Methacrylic Resin Kyoei Chemical Co., Ltd. Epoxy Resin M3002 100 Comparative Example 6 Polythiol (ester type) Japan Epoxy Resin Co., Ltd. jER Cure 0X40 100 Comparative Example 7 Epoxy Resin Japan Electrochemical Industry Co., Ltd. Epiclon EXA-835LV 66 Polythiol (ester type) Japan Epoxy Resin Co., Ltd. jER Cure 〇X40 34 Comparative Example 8 Epoxy shed Chemical Industry Co., Ltd. HP-4032D 66 Polythiol (ester type) Japan Epoxy Resin Co., Ltd. jERCure 〇X40 34 Comparative Example 9 Acrylic Resin Kyoei Chemical Co., Ltd. Epoxy Resin A3002 50 Polythiol (ester type) Japan Epoxy Resin JER Cure 〇X40 50 Comparative Example 10 Acrylic Resin Co., Ltd. Epoxy Resin A3002 95 Organic Peroxide Emu Oil Co., Ltd. Performylbenzene H-80 5 Comparative Example 11 Organic Titanium Compound Matsumoto Fine Chemical Co., Ltd. Orgatix TC-750 100 Comparative Example 12 Organic Compound Compound Matsumoto Fine Chemical Co., Ltd. Orgatix ZC-580 100 Comparative Example 13 Aliphatic carboxylic acid (slip agent) Tokyo Chemical Industry Co., Ltd. Stearic acid 100 Comparative Example 14 Wax 曰本精蜡股份有限公司 LUVAX-1266 100 Comparative Example 15 萜 resin Yasuhara strain YP Resin YP- 90L 100 [Comparative Examples 2 to 10] In the first step, DBU 200g and B-6C100g were placed in a beaker and stirred for 30 minutes. Since it generates heat during absorption, it was allowed to stand for 2 hours after stirring and cooled to room temperature. Add 300 g of ME K and stir for 30 minutes. The suction paper was filtered in the Kiriyama funnel by the No. 3 crepe paper, and the remaining DBU which was not absorbed was passed over with the MEK used for washing. The filtrate was allowed to spread thinly on the tray, and dried at 40 ° C for x 2 hours by a hot air drying oven. Second step 200 g of the raw materials used in Comparative Examples 2 to 1 were added to the treated powder 10 g for 30 minutes. After the stirring was completed, 300 g of MEK was added and stirred for another 30 minutes. The suction filter was carried out in a Kiriyama funnel by a No. 3 filter paper. The filtrate was allowed to spread thinly on the tray, and dried at 40 ° C for x 2 hours by a hot air drying oven. ◎ [Comparative Example 1 1~12] First step DBU200g and B-6C100g were placed in a beaker and stirred for 30 minutes. Since it generates heat during absorption, it was allowed to stand for 2 hours after stirring and cooled to room temperature. Add 300 g of MEK and stir for 30 minutes. The filter paper of Νο·3 was subjected to suction filtration in the Kiriyama funnel, and the remaining DBU which was not absorbed was filtered with the ruthenium added for washing. The filtrate was allowed to spread thinly on the tray, and dried by a hot air drying oven at 40 ° C for 2 hours. Second step 50 g of the raw materials used in Comparative Examples 11 and 12 were added to the treated powder 10 g for 30 minutes. After the completion of the stirring, 300 g of MEK was added and stirred for further 30 minutes. The filter paper of No. 3 was subjected to suction filtration in a Kiriyama funnel. The filtrate was allowed to spread thinly on the tray and dried by hot air drying at -28-200950878 in a furnace at 40 ° C for 2 hours. [Comparative Example 1 3 to 1 5] First step DBU200g and B-6C100g were placed in a beaker and stirred for 30 minutes. Since it generates heat during absorption, it was allowed to stand for 2 hours after stirring and cooled to room temperature. Add 300 g of MEK and stir for 30 minutes. The suction filtration was carried out in the Kiriyama funnel by the filter paper of Ν〇3, and the remaining DBU which was not absorbed was filtered with the ruthenium added for washing. The filtrate was allowed to spread thinly on the tray, and dried by a hot air drying oven at 40 ° C for 2 hours. Second step Dry-encapsulation treatment was carried out by a hybridization system NHS-0 type manufactured by Nara Machinery Co., Ltd. The raw materials i〇g used in Comparative Examples 13 to 15 添加 were added to the treated powder i〇g, and treated at 9700 m/s for 1 minute. The treated product is scraped and recovered. [State of Second Step] In the second step of the embodiment and the comparative example, the state of the recessive processing was visually confirmed. When the reaction proceeds during the treatment to increase the viscosity and lose the fluidity, it is set to fail (NG), and when it has fluidity, it is set to pass (OK). The test results are shown in the "state of the second step" in the third table. (In the following, the state of the second step is based on this method) -29- 200950878 [Initial preservability] 100 parts by weight of bisphenol type epoxy resin (EPICLON EXA-83 5 LV Dainippon Ink and Chemicals Co., Ltd.) A mixture of 50 parts by weight of a thiol compound, jER XURE QX40 (manufactured by Japan Epoxy Resin Co., Ltd.), was used as a test solution to confirm the presence or absence of encapsulation. When DBU is added to a mixture of an epoxy resin and a polythiol compound, it is rapidly heated and instantly hardened. Therefore, the © powder prepared in the examples and the comparative examples can be added to the above-mentioned test solution, and visually observed. Confirm the status afterwards and judge whether it is qualified or not. The evaluation conditions were set to 30 parts by weight with respect to the assay liquid, and 5 parts by weight of each of Examples 1 to 3 and Comparative Examples 4, 5, 10, 1 1 , 1 3, 14, and 15 were added and stirred. When the reaction was carried out at 25 ° C for 1 hour or less to increase the viscosity and the fluidity was lost, it was set to be unacceptable (NG), and when it had fluidity, it was set to pass (OK). The test results are shown in the "initial preservation" of Table 3. In the "state of the second step", the NG is indicated by "_". (Hereinafter, the initial storage stability is based on this method.) [Storage property] Examples 1 to 3 and Comparative Examples 1 and 1 3 having a storage stability of 1 hour or more in the initial storage property, and then confirming 2 5 ° Preservation stability under C. It was confirmed every 1 day whether or not gelation occurred until 5 days passed. Colloidalization refers to the time (days) measured by the EHD type viscometer that exceeds the viscosity measurement margin. The measurement was carried out under the conditions of a control temperature of 25 ° C, a measurement time of 3 minutes -30 to 200950878, and a conical rotor of 1° 23' x R24. The measurement margin was equivalent to 100 Pa·s. The test results are shown in the "preservation" of Table 3. In the "state of the second step" and "initial preservation", the NG person is indicated by "-". (Here, the preservation is based on this method)

第3表 號碼 第二步驟的狀態 檢定液試驗（放置於25。〇 初期保存性 保存性 實施例1 ΟΚ ΟΚ 5天 實施例2 ΟΚ ΟΚ 5天 實施例3 ΟΚ ΟΚ 4天 比較例1 NG — — 比較例2 NG — — 比較例3 NG — — 比較例4 ΟΚ NG — 比較例5 ΟΚ NG — 比較例ό NG — — 比較例7 NG — — 比較例8 NG — — 比較例9 NG — — 比較例1〇 ΟΚ NG — 比較例11 ΟΚ ΟΚ 1天 比較例12 NG — — 比較例13 ΟΚ ΟΚ 1天 比較例Η ΟΚ NG 一 比較例15 ΟΚ NG — 從第3表的結果中可得知’以酸酐進行處理者，其保 存性最佳。第1圖及第2圖係分別顯示確認未處理的B-6C及實施例1的表面狀態之電子顯微鏡照片。第2圖中 具有部分固著之部分’可確認出在二氧化矽粉的表面存在 -31 - 200950878 有樹脂層。 係對添加可與酸酐相容之可塑劑時’以及將酸酐取代 爲其他化合物時進行保存性的確認。係使用實施例1所使 用之NH-2200R與新採用的4-甲基六氫鄰苯二甲酸酐（ Rikacid MH-700新日本理化株式會社製）作爲酸酐，使用 雙（2-乙基己基）癸二酸酯（SANSOCIZER DOS新日本理 化株式會社製）作爲可塑劑，並依據添加量來確認保存性 。試驗結果係表示於第4表。此可推測爲當使用可塑劑時 ，酸酐的覆膜軟化而容易使膠囊被破壞之故。藉由調節可 塑劑的添加量，可控制膠囊的破壞容易度，因此，可控制 當用作爲硬化性樹脂組成物的硬化成份時之硬化性樹脂的 硬化性。 [實施例4〜8] 第一步驟 將DBU200g與B-6C100g放入至燒杯中攪拌30分鐘 。由於在吸收時會發熱，所以在攪拌後放置2小時而冷卻 至室溫。添加300g的MEK攪拌30分鐘。藉由No.3的濾 紙，在有限會社桐山製作所製的桐山漏斗中進行吸引過濾 ，將未被吸收之剩餘的DBU與用於洗淨所添加之MEK予 以過濾。使過濾物在托盤上薄薄地擴散，藉由熱風乾燥爐 進行40°C x2小時的乾燥。 第二步驟 -32- 200950878 依循第4表，將混合有NH-2200R或Rikacid MH-700 單體與酸酐與作爲可塑劑的SANSOCIZER DOS者200g， 添加於處理完畢的粉體l〇〇g中攪拌30分鐘。攪拌結束後 ，添加3 00g的MEK再攪拌30分鐘。藉由No.3的濾紙在 桐山漏斗中進行吸引過濾。使過濾物在托盤上薄薄地擴散 ，藉由熱風乾燥爐進行40°C x2小時的乾燥。 第4表 號碼 膠囊化原料 第二步驟 檢定液試驗(放置 :於 25。〇 酸酐(A) 可塑劑(B) 比例(A:B) 的狀態 初期保存性 保存性 實施例1 100 ： 0 OK OK 5天 實施例4 HN-2200R 50 ： 50 OK OK 4天 實施例5 10 ： 90 OK OK 2天 實施例6 DOS 100 : 0 OK OK 5天 實施例7 Rikacid MH-700 50 ： 50 OK OK 4天 實施例8 10 ： 90 OK OK 3天 [實施例9〜17] φ 係製造出以在實施例1、實施例4、實施例5中所製 造之微膠囊作爲硬化促進劑之硬化性樹脂組成物。使用 EPICLON EXA-835LV作爲具有環氧基之化合物，使用 jER XURE QX40作爲聚硫醇化合物，使用MEH-8005 (明 和化成株式會社製）作爲聚酚化合物，使用Rikacid MH-700 作 爲酸酐 ，並依循第 5 表進 行調配 。於攪拌機 中將各 調配物攪拌15分鐘，而調製出硬化性樹脂組成物。 [比較例16~18] 係使用 EPICLON EXA-83 5 LV，jER XURE QX40，並 -33- 200950878 使用環氧加成型化合物的 Amicure-PN-23J (味之素 Fine Techno株式會社）、Fujicure-FXE-1000 (富士化成工業 株式會社）、Novacure-HX-3921HP (旭化成 Chemicals 株 式會社）作爲硬化促進劑，依循第6表進行調配。於攪拌 機中將各調配物攪拌15分鐘，調製出硬化性樹脂組成物 [硬化性確認] © 於下列條件下藉由流變儀來確認90°C與120°C的硬化 動作。對於實施例9〜17、比較例16〜1 8，係從未硬化的狀 態開始至硬化結束且黏度不再變化爲止進行測定，黏度不 再變化之時間（分鐘），係整理顯示於第7表。 流變儀的規格 製造商：REOLOGICA 社製 VAR-50 測定條件：P r e s h a r e : 1 0 ( 1 / s ) 3 0 秒間The third test is the state test liquid test in the second step (placed at 25. Initial storage preservative stability Example 1 ΟΚ ΟΚ 5 days Example 2 ΟΚ ΟΚ 5 days Example 3 ΟΚ ΟΚ 4 days Comparative Example 1 NG – Comparative Example 2 NG - Comparative Example 3 NG - Comparative Example 4 ΟΚ NG - Comparative Example 5 ΟΚ NG - Comparative Example NG NG - Comparative Example 7 NG - Comparative Example 8 NG - Comparative Example 9 NG - Comparative Example 1〇ΟΚ NG - Comparative Example 11 ΟΚ ΟΚ 1 day Comparative Example 12 NG - Comparative Example 13 ΟΚ ΟΚ 1 day comparative example ΟΚ NG 1 Comparative Example 15 ΟΚ NG - From the results of Table 3, it is known that The storage is best, and the first and second graphs respectively show electron micrographs confirming the surface state of untreated B-6C and Example 1. In Fig. 2, there is a partially fixed portion. It was confirmed that a resin layer was present on the surface of the cerium oxide powder - when the plasticizer compatible with the acid anhydride was added, and when the acid anhydride was substituted with another compound, the storage stability was confirmed. 1 NH-2200R used and 4-methylhexahydrophthalic anhydride ( Rikacid MH-700, manufactured by Nippon Chemical Co., Ltd.), which is newly used, as an acid anhydride, using bis(2-ethylhexyl) sebacate (SANSOCIZER) As a plasticizer, DOS New Japan Chemicals Co., Ltd. confirmed the storage stability based on the amount of addition. The test results are shown in Table 4. It is presumed that when a plasticizer is used, the film of the acid anhydride softens and the capsule is easily The reason for the destruction is that the degree of destruction of the capsule can be controlled by adjusting the amount of the plasticizer added, and therefore, the curability of the curable resin when used as a hardening component of the curable resin composition can be controlled. [Example 4~ 8] In the first step, DBU200g and B-6C100g were placed in a beaker and stirred for 30 minutes. Since they were heated during absorption, they were allowed to stand for 2 hours after stirring and cooled to room temperature. 300 g of MEK was added and stirred for 30 minutes. The filter paper of No. 3 was suction-filtered in the Kiriyama funnel manufactured by the limited company, Kiriyama Seisakusho Co., Ltd., and the remaining DBU that was not absorbed and the MEK used for washing were filtered. The filter was thin on the tray. Diffusion, drying at 40 ° C for x 2 hours by hot air drying oven. Second step -32 - 200950878 According to the fourth table, the NH-2200R or Rikacid MH-700 monomer and anhydride are mixed with SANSOCIZER as a plasticizer. 200 g of DOS was added to the treated powder l〇〇g for 30 minutes. After the stirring was completed, 300 g of MEK was added and stirred for another 30 minutes. The suction filter was carried out in a Kiriyama funnel by a No. 3 filter paper. The filtrate was allowed to spread thinly on the tray, and dried at 40 ° C for x 2 hours by a hot air drying oven. The fourth table number encapsulation material second step test solution test (placement: at 25. phthalic anhydride (A) plasticizer (B) ratio (A: B) state initial storage stability storage example 1 100 : 0 OK OK 5 days Example 4 HN-2200R 50 : 50 OK OK 4 days Example 5 10 : 90 OK OK 2 days Example 6 DOS 100 : 0 OK OK 5 days Example 7 Rikacid MH-700 50 : 50 OK OK 4 days Example 8 10 : 90 OK OK for 3 days [Examples 9 to 17] φ was used to produce a curable resin composition using the microcapsules produced in Example 1, Example 4, and Example 5 as a hardening accelerator. Using EPICLON EXA-835LV as a compound having an epoxy group, jER XURE QX40 as a polythiol compound, MEH-8005 (manufactured by Megumi Kasei Co., Ltd.) as a polyphenol compound, and Rikacid MH-700 as an acid anhydride, and using The formulation was adjusted in Table 5. The formulations were stirred in a blender for 15 minutes to prepare a curable resin composition. [Comparative Examples 16 to 18] EPICLON EXA-83 5 LV, jER XURE QX40, and -33- were used. 200950878 Amicu using epoxy addition compounds Re-PN-23J (Ajinomoto Fine Techno Co., Ltd.), Fujikure-FXE-1000 (Fuji Chemical Industry Co., Ltd.), and Novacure-HX-3921HP (Asahi Kasei Chemicals Co., Ltd.) as a hardening accelerator, according to Table 6 Each of the formulations was stirred for 15 minutes in a stirrer to prepare a curable resin composition [cursibility confirmation]. The curing operation at 90 ° C and 120 ° C was confirmed by a rheometer under the following conditions. 9 to 17 and Comparative Examples 16 to 18, which were measured from the unhardened state until the end of curing and the viscosity did not change, and the time (minutes) at which the viscosity did not change was shown in Table 7. Specification of the manufacturer: REOLOGICA VAR-50 Determination conditions: P reshare : 1 0 ( 1 / s ) 3 0 seconds

Geometry : P25 ◎ 間隙：1 m m 測定模式：振盪應變控制 應變：0.0 1 頻率數：1Hz [切變黏著力確認] 將以MEK進行洗淨後之1.6x25x 1 00mm的SPCC-SD 鋼板2片，以將組成物塗佈於重疊2.5x10mm的範圍之面 -34- 200950878 上之方式予以貼合，於設定在120 °C之熱風乾燥爐中硬化 60分鐘後，自然冷卻至25 °C爲止。之後藉由萬能拉伸試 驗機，以拉伸速度1 〇mm/min進行測定。詳細內容係依循 JIS K 6850。藉由此方法對實施例9〜17及比較例16〜18進 行測定，測定結果係整理於第7表。Geometry : P25 ◎ Clearance: 1 mm Measurement mode: Oscillation strain control strain: 0.0 1 Frequency number: 1 Hz [Tensile adhesion confirmation] Two pieces of 1.6x25x 1 00mm SPCC-SD steel plate to be washed with MEK to The composition was applied by being applied to a surface of the range of -34 to 200950878 which was overlapped in the range of 2.5 x 10 mm, and was cured in a hot air drying oven set at 120 ° C for 60 minutes, and then naturally cooled to 25 ° C. Thereafter, the measurement was carried out at a tensile speed of 1 〇 mm/min by a universal tensile tester. The details are based on JIS K 6850. The examples 9 to 17 and the comparative examples 16 to 18 were measured by this method, and the measurement results were summarized in the seventh table.

第5表 原料 實施例 9 實施例 10 實施例 11 實施例 12 實施例 13 實施例 14 實施例 15 實施例 16 實施例 17 EXA- 835LV 2.0 2.0 2.0 2.0 2.0 2.0 1.5 1.5 1.5 QX40 1.0 1.0 1.0 MEH-8005 1.0 1.0 1.0 MH-700 1.5 1.5 1.5 實施例1 0.5 0.5 0.5 實施例4 0.5 0.5 0.5 實施例5 0.5 0.5 0.5 合計 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 第6表 原料 比較例16 比較例17 比較例18 EXA-835LV 2.0 2.0 2.0 QX40 1.0 1.0 1.0 PN-23J 0.5 FXE-1000 0.5 HX-3921HP 0.5 合計 3.5 3.5 3.5 -35- 200950878 第7表 號碼 硬化體劑 90。。環境氣(。〇 120。。環境氣(。〇 保存性 切變黏著力(MPa) 實施例9 實施例1 24 8 5天 21 實施例10 實施例4 20 8 3天 23 實施例11 實施例5 7 5 2天 23 實施例12 實施例1 200 30 5天 23 實施例13 實施例4 150 25 5天 25 實施例14 實施例5 120 20 3天 25 實施例15 實施例1 95 20 5天 22 實施例16 實施例4 85 20 4天 25 實施例17 實施例5 80 17 3天 26 比較例16 PN-23J 20 5 3天 15 比較例17 FXE-1000 29 9 4天 15 比較例18 HX-3921HP 34 13 5天 13 [實施例18〜20] 係製造出以在實施例1中所製造之微膠囊作爲硬化劑 之硬化性樹脂組成物。硬化性樹脂，係使用加氫雙酚A型 Epikote YL700 7 ( Japan Epoxy Resin 株式會社製）作爲具 有環氧基之化合物’或是 Millionate MR-200 (日本 Polyurethane工業株式會社製）作爲具有異氰酸酯基之化 合物，或是四甲基丙烯酸新戊四醇酯（Light Acrylate PE-4A共榮社化學株式會社製）作爲具有丙烯酸基之化合物 ，並依循第7表進行調配。於攪拌機中將各調配物攪拌15 分鐘，而調製出硬化性樹脂組成物。 [實施例21] 係製造出以在實施例1中所製造之微膠囊作爲硬化促 -36- 200950878 進劑之硬化性樹脂組成物。硬化性樹脂，係使用二丙烯酸 二經甲二環癸醋（Light Acrylate DCP-Α共榮社化學株式 會社製）與三級丁基過氧基-2-乙基己基碳酸酯（Perbutyl E日油株式會社製），並依循第8表進行調配。於攪拌機 中將各調配物攪拌15分鐘，而調製出硬化性樹脂組成物 〇 與前述硬化性確認相同，藉由流變儀來確認90 °C與 O 120°C的硬化動作。該結果係顯示於第9表。 第8表 原料 實施例18 實施例19 實施例20 實施例21 Epikote YL7007 3.0 Millionate MR-200 3.0 Light Acrylate PE-4A 3.0 Light Acrylate DCP-A 3.0 過異丙苯E 0.005 實施例1 0.05 0.05 0.05 0.05 合計 3.50 3.50 3.50 3.55 ❹ 第9表 號碼 微膠囊 90°C環境氣(。〇 120。。環境氣rc) 保存性 實施例18 實施例1 39 12 5天 實施例19 實施例1 45 6 4天 實施例20 實施例1 85 15 5天 實施例21 實施例1 未硬化 5 5天 雖然因硬化劑種類的不同使反應性有所不同，但一般 而言，即使是反應性較低的硬化劑之聚酚化合物或酸酐’ 若將本發明之微膠囊用作爲硬化促進劑，則亦可在9〇t>c的 -37- 200950878 低溫下進行硬化。此外，亦可確認出藉由使用可塑劑而更 進一步提升反應性。此手法中’雖然同時會產生保存性的 降低，但商業上亦可進行低溫保存而成爲控制反應性之有 效的手法。再者，可確認出本發明之微膠囊同時兼具與環 氧加成型化合物匹敵之保存性’使用其之樹脂組成物中’ 亦可顯現出強韌的切變黏著力。因此可確認出’包含本發 明之微膠囊的硬化性樹脂組成物，爲能夠顯現來自微膠囊 化後之強鹼基性的液狀胺化合物之優良的反應性，並且兼 © 具良好的保存性之硬化性樹脂組成物。 產業上之可利用性： 本發明之微膠囊，藉由用作爲硬化性樹脂的硬化劑或 硬化促進劑，可調製出同時兼具反應性與保存性之硬化性 樹脂組成物。此類硬化性樹脂組成物，在半導體裝置的製 造中所使用之安裝用底部塡充劑及散熱用樹脂組成物，以 及導電性樹脂組成物等之廣泛領域中，可用作爲同時兼具 Θ 保存安定性與反應性之硬化性樹脂組成物。 【圖式簡單說明】 第1圖係顯示本發明之用作爲（B)成份的多孔質中 空二氧化矽粉之掃描型電子顯微鏡照片。 第2圖係顯示本發明中所製得的微膠囊之掃描型電子 顯微鏡照片的一例。 -38-5th Table Material Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 EXA-835LV 2.0 2.0 2.0 2.0 2.0 2.0 1.5 1.5 1.5 QX40 1.0 1.0 1.0 MEH-8005 1.0 1.0 1.0 MH-700 1.5 1.5 1.5 Example 1 0.5 0.5 0.5 Example 4 0.5 0.5 0.5 Example 5 0.5 0.5 0.5 Total 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Table 6 Raw material Comparative Example 16 Comparative Example 17 Comparative Example 18 EXA-835LV 2.0 2.0 2.0 QX40 1.0 1.0 1.0 PN-23J 0.5 FXE-1000 0.5 HX-3921HP 0.5 Total 3.5 3.5 3.5 -35- 200950878 Table 7 No. Hardener 90. . Ambient gas (. 〇 120. Ambient gas (. 〇 Preservative shear adhesion (MPa) Example 9 Example 1 24 8 5 days 21 Example 10 Example 4 20 8 3 days 23 Example 11 Example 5 7 5 2 days 23 Example 12 Example 1 200 30 5 days 23 Example 13 Example 4 150 25 5 days 25 Example 14 Example 5 120 20 3 days 25 Example 15 Example 1 95 20 5 days 22 Implementation Example 16 Example 4 85 20 4 days 25 Example 17 Example 5 80 17 3 days 26 Comparative Example 16 PN-23J 20 5 3 days 15 Comparative Example 17 FXE-1000 29 9 4 days 15 Comparative Example 18 HX-3921HP 34 13 5 days 13 [Examples 18 to 20] A curable resin composition obtained by using the microcapsules produced in Example 1 as a curing agent was produced. The curable resin was a hydrogenated bisphenol A type Epikote YL700 7 . (made by Japan Epoxy Resin Co., Ltd.) as a compound having an epoxy group or a Millionate MR-200 (manufactured by Japan Polyurethane Industries Co., Ltd.) as a compound having an isocyanate group or a neopentyl glycol tetramethacrylate (Light) Acrylate PE-4A Kyoritsu Chemical Co., Ltd.) as having acrylic acid The compound was formulated according to the seventh table. The formulations were stirred for 15 minutes in a blender to prepare a curable resin composition. [Example 21] Microcapsules manufactured in Example 1 were produced. It is a hardening resin composition of the hardening-36-200950878. The curable resin is a two-butyl butyl diacetate (Light Acrylate DCP-manufactured by Kyoeisha Chemical Co., Ltd.) and a tertiary butyl group. Peroxy-2-ethylhexyl carbonate (manufactured by Perbutyl E Nippon Oil Co., Ltd.) was prepared according to the eighth table. The formulations were stirred in a blender for 15 minutes to prepare a curable resin composition. The hardenability was confirmed to be the same, and the hardening operation at 90 ° C and O 120 ° C was confirmed by a rheometer. The results are shown in Table 9. Table 8 Raw material Example 18 Example 19 Example 20 Example 21 Epikote YL7007 3.0 Millionate MR-200 3.0 Light Acrylate PE-4A 3.0 Light Acrylate DCP-A 3.0 Percumene E 0.005 Example 1 0.05 0.05 0.05 0.05 Total 3.50 3.50 3.50 3.55 ❹ Table 9 Air bladder 90 ° C environment (. 〇 120. . Ambient gas rc) Preservative Example 18 Example 1 39 12 5 days Example 19 Example 1 45 6 4 days Example 20 Example 1 85 15 5 days Example 21 Example 1 Unhardened 5 5 days although hardened The difference in the kind of the agent makes the reactivity different, but in general, even the polyphenol compound or acid anhydride of the less reactive hardener can be used in the case of using the microcapsule of the present invention as a hardening accelerator. 〇t>c-37- 200950878 Hardening at low temperatures. Further, it was confirmed that the reactivity was further improved by using a plasticizer. In this method, although there is a decrease in preservative property at the same time, it is also commercially feasible to perform cryopreservation as an effective method for controlling reactivity. Further, it has been confirmed that the microcapsules of the present invention have both a preservative property comparable to that of an epoxy compounding compound, and a resin composition using the same can exhibit a strong shear adhesive strength. Therefore, it has been confirmed that the curable resin composition containing the microcapsule of the present invention is excellent in reactivity with a liquid amine compound capable of exhibiting strong base properties after microencapsulation, and has good preservation properties. A curable resin composition. Industrial Applicability: The microcapsule of the present invention can be prepared by using a curing agent or a curing accelerator as a curable resin to form a curable resin composition having both reactivity and preservability. Such a curable resin composition can be used as a combination of a bottom charge for mounting a semiconductor device and a resin composition for heat dissipation, and a conductive resin composition. Sexual and reactive curable resin composition. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a scanning electron micrograph showing a porous hollow ceria powder used as the component (B) of the present invention. Fig. 2 is a view showing an example of a scanning electron microscope photograph of the microcapsules obtained in the present invention. -38-

Claims (1)

200950878 七、申請專利範圍： l ~種微膠囊，其特徵爲： 係以下列（A ) ~ ( C )成份爲構成成份，使（B )成 份吸收（A)成份，並且使（C)成份與存在於該（B)成 份的表面上之（A)成份反應而形成覆膜所成， (A)成份：酸解離常數（pKa)爲8.0以上之液狀的 胺化合物或其有機酸鹽 © ( B)成份：多孔質微粒子粉 (c)成份：酸酐。 2·如申請專利範圍第1項之微膠囊，其中（A )成份 係由從1，8-二氮雜雙環[5.4.0]十一 -7-烯、1，5-二氮雜雙環 [4.3.0]壬-5-烯、三伸乙二胺、這些化合物的衍生物或這些 化合物的有機酸鹽所組成之群組中所選出之至少1種所形 成。 3. 如申請專利範圍第1項之微膠囊，其中（C )成份 ® 爲含有可塑劑之酸酐。 4. —種硬化性樹脂組成物，其特徵係由含有申請專 利範圍第1項之微膠囊作爲硬化劑或硬化促進劑之硬化性 樹脂所形成。 5 .如申請專利範圍第4項之硬化性樹脂組成物，其 中硬化性樹脂係由從具有環氧基之化合物、具有環硫基之 化合物、具有異氰酸酯基之化合物以及具有乙烯基之化合 物中所選出之至少1種所形成。 6.如申請專利範圍第4項之硬化性樹脂組成物，其 -39- 200950878 中硬化性樹脂組成物，係由從具有環氧基之化合物及具有 環硫基之化合物中所選出之至少1種所形成，並且使用從 聚胺化合物、聚酚化合物、聚硫醇化合物或酸酐中所選出 之至少1種作爲硬化劑’使用該微膠囊作爲硬化促進劑而 成。200950878 VII. Patent application scope: l ~ kinds of microcapsules, which are characterized by the following components (A) ~ (C) as components, so that (B) component absorbs (A) component, and (C) component The component (A) which is present on the surface of the component (B) reacts to form a film, and the component (A): a liquid amine compound having an acid dissociation constant (pKa) of 8.0 or higher or an organic acid salt thereof ( B) Ingredients: Porous microparticle powder (c) Ingredients: Anhydride. 2. The microcapsules of claim 1 wherein the component (A) is derived from 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[ 4.3.0] at least one selected from the group consisting of an indole-5-ene, a triethylenediamine, a derivative of these compounds, or an organic acid salt of these compounds. 3. For the microcapsules of claim 1, the component (C) is an acid anhydride containing a plasticizer. 4. A curable resin composition characterized by comprising a curable resin containing a microcapsule of the first item of the patent application range as a curing agent or a curing accelerator. 5. The curable resin composition of claim 4, wherein the curable resin is derived from a compound having an epoxy group, a compound having an epoxy group, a compound having an isocyanate group, and a compound having a vinyl group. At least one selected is formed. 6. The curable resin composition of claim 4, wherein the curable resin composition of -39-200950878 is at least 1 selected from the group consisting of a compound having an epoxy group and a compound having an epoxy group. The microcapsules are formed as a hardening accelerator using at least one selected from the group consisting of polyamine compounds, polyphenol compounds, polythiol compounds, and acid anhydrides. -40- 200950878 四、指定代表圖： ，(一）、本案指定代表圊為：無 (二）、本代表圖之元件代表符號簡單說明：無-40- 200950878 IV. Designated representative map: , (1), the designated representative of the case is: None (2), the representative symbol of the representative figure is a simple description: None 200950878 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無200950878 V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none
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