TW200916496A - Curing agent for epoxy resin and curing agent composition for epoxy resin - Google Patents

Abstract

Disclosed is a curing agent for epoxy resin which is represented by the following general formula (1) or (2). (1) (2) (In the formulae, R1 and R5 each represents a hydrogen atom, an optionally substituted alkyl group having 1-6 carbon atoms or an optionally substituted aryl group having 1-12 carbon atoms; R2 represents a hydrogen atom or an optionally substituted alkyl group having 1-6 carbon atoms; R3 and R4 independently represent a hydrogen atom or a group represented by the following general formula (3): (3) (wherein R1 and R2 are as define above) or the following general formula (4): (4) ; and n represents an integer of 1-3.)

Description

200916496 九、發明說明： 【發明所屬之技術領域】 二發明係關於一種新型之環氧樹脂用硬化劑、及包切 辰乳樹脂用硬化劑之環氧樹脂用硬化劑組合物。 ^ 【先前技術】 已知環氧樹脂之硬化物具有機械特性、電氣特性、 雷耐化學性及黏接性等優良之性質，從而用於塗料Γ電 絕緣材料'黏接劑等範圍廣泛之用途中。為了確 ::良好之作業效率，適合使用單成分性之環氧樹脂組合 六另h方面’先前公知之單成分性環氧樹脂组合物中，儲 存穩疋性優良者通常硬化性較 時間的硬化處理。低，故而必須進行高溫或長 “另t面，硬化性較高者通f儲存穩定性較低，必須於 歹’如-20 C左右之低溫條件下儲存。 '、 言’調配有二氰二胺之環氧樹脂組合物於常溫條 ^⑽個月以上的儲存穩定性，但為了硬化而必須進 以上之尚溫處理，從而導致硬化性較低。若 實現硬化處理溫度之降低而使用硬化促進劑，則可於:3〇 二左右下進行硬化，但會產生常溫條件下之儲存穩定 低而必須於低溫條件下儲存的問題。 /於上述問題’為了實現硬化性與儲存穩定性之兼顧， 提出有以特定之殼包覆由胺系硬化劑所形成之核的 所謂微膠囊型硬化劑(例如參照專利文獻1}。 132805.doc 200916496 該專利文獻1中揭示了單成分沾 产 早成刀性裱氧樹脂組合物用母 型硬化劑，其含有··包含由特 母枓 形成之核、及由該胺化合物與環氧樹脂之反應產物所形： 之殼的硬化劑；以及環氧樹脂。 成 [專利文獻1]曰本專利特開平〗_7〇523號公報 【發明内容】 [發明所欲解決之問題] 然而，近年來，尤其於電子機器領域中，⑴為了 電路之高密度化或連接可靠性 、 ^, θ 之徒间，（2)為了為移動機器 之麵置化而使料純㈣之㈣，⑺為了大幅度改 產性等要求，而對可料連接材料或密封材料之— 分性環氧樹脂組合物要求不損及儲存穩定性、可進 條件下且短時間之硬化的更高硬化性。 -’皿 因此’本發明之目的在於提供—種可進行低溫條件下且 紐時間之硬化處理的環氧樹脂用硬化劑。 進而’本發明之目的在於提供—種不僅具有優良之低溫 2性及短時間硬化性’並且兼具良好之儲存穩定性及耐 之微膠囊型環氧樹脂用硬化劑、母料型環氧樹脂 用硬化劑組合物及單成分性調配組合物。 [解決問題之技術手段] 本發明者等人針對上述先前技術之課題而反覆進行專心 ==果發現：以特定結構式所表示之環氧樹脂用硬化 Η I不出優良之低溫硬化性及短時間硬化性。 又發現：使上述環氧樹脂硬化劑分散於環氧樹脂中而成 132805.doc 200916496 之母料型環氧樹月旨用硬化劑組合物可解決上述課題。 進而發現：使包含含有上述環氧樹脂硬化劑之核⑹與 含有特定化合物之反應產物且包覆上述核⑹之殼⑻的微 膠囊型環氧樹脂用硬化劑分散於環氧樹脂中而成之母料型 環氧樹脂用硬化㈣合物’可進—步改善儲存穩定性及耐 填充料性。 即’本發明係如以下所示。 ⑴一種環氧樹脂用硬化劑’其係由下述通式⑴或⑺表 示： [化1]200916496 IX. Description of the Invention: [Technical Field of the Invention] The second invention relates to a novel hardener for an epoxy resin and a hardener composition for an epoxy resin for a hardener for a diced resin. ^ [Prior Art] It is known that the cured epoxy resin has excellent properties such as mechanical properties, electrical properties, chemical resistance and adhesion, and is used for a wide range of applications such as coatings and electrical insulating materials. in. In order to confirm: good working efficiency, it is suitable to use one-component epoxy resin combination. In the previously known single-component epoxy resin composition, those with good storage stability are usually hardenable and hardened over time. deal with. Low, it is necessary to carry out high temperature or long "other t-face, higher hardenability, lower storage stability, must be stored under low temperature conditions such as -20 C. ', 言' is equipped with dicyandiamide The epoxy resin composition of the amine has a storage stability at room temperature for more than 10 months, but it is necessary to carry out the above-mentioned temperature treatment for hardening, thereby causing low hardenability. If hardening treatment temperature is lowered, hardening promotion is used. The agent can be hardened at about 3 Torr, but it has a problem that the storage under normal temperature conditions is stable and low, and must be stored under low temperature conditions. / In order to achieve the combination of hardenability and storage stability, A so-called microcapsule-type hardener in which a core formed of an amine-based curing agent is coated with a specific shell has been proposed (for example, see Patent Document 1). 132805.doc 200916496 This patent document 1 discloses a single-component dip early-formed knife. a mother-type hardener for a cerium-oxygen resin composition, comprising: a core formed of a special mother 枓, and a hardener of a shell formed by the reaction product of the amine compound and the epoxy resin; and an epoxy [Patent Document 1] Japanese Patent Laid-Open Publication No. _7〇523A SUMMARY OF INVENTION [Problems to be Solved by the Invention] However, in recent years, particularly in the field of electronic equipment, (1) in order to increase the density of circuits Or connection reliability, ^, θ, (2) in order to surface the mobile machine to make the material pure (four) (four), (7) in order to greatly change the production requirements, etc., for the material connection material or sealing material The fractional epoxy resin composition is required to have higher hardenability without impairing storage stability, hardening under conditions and for a short period of time. - 'The dish therefore' is intended to provide a low temperature condition And a hardening agent for epoxy resin which is hardened at the time of the present invention. Further, the object of the present invention is to provide a microcapsule which not only has excellent low temperature properties and short-time hardenability, but also has good storage stability and resistance. A hardener for a type of epoxy resin, a hardener composition for a masterbatch type epoxy resin, and a one-component compounding composition. [Technical means for solving the problem] The inventors of the present invention have objected to the problems of the prior art described above. Concentration == fruit discovery: Hardening enamel for epoxy resin represented by a specific structural formula I does not exhibit excellent low-temperature hardening property and short-time hardenability. It has also been found that the above epoxy resin hardener is dispersed in epoxy resin. The above-mentioned problem can be solved by forming a masterbatch type epoxy resin composition for curing agent of 132805.doc 200916496. Further, it has been found that a core (6) containing the above-mentioned epoxy resin hardener and a reaction product containing a specific compound are coated and coated. The hardener (tetra) compound of the master batch type epoxy resin in which the microcapsule type epoxy resin of the shell (8) of the core (6) is dispersed in the epoxy resin can further improve storage stability and filler resistance. That is, the present invention is as follows. (1) A curing agent for an epoxy resin, which is represented by the following general formula (1) or (7):

其中，上述式⑴、⑺中’ R丨、Rs表示氫原子、 、 了經取 代之碳數為1〜6的烷基或可經取代之碳數為丨〜12的芳爲 R2表示虱原子或可經取代之碳數為1〜6的烧基。 下述通式（3)或下述通式 R3及R4分別獨立地表示氫原子、 (4)所表示之基： 132805.doc 200916496 [化3]In the above formulas (1) and (7), 'R丨, Rs represents a hydrogen atom, a substituted alkyl group having 1 to 6 carbon atoms or a substituted aryl group having a carbon number of 丨~12 is R2 represents a halogen atom or A calcined group having a carbon number of 1 to 6 which may be substituted. The following general formula (3) or the following general formulas R3 and R4 each independently represent a hydrogen atom and the group represented by (4): 132805.doc 200916496 [Chemical 3]

式（3)中’ R^r2與上述同義； [化4]'R^r2 in the formula (3) is synonymous with the above; [Chemical 4]

—-CHj-ljJH'-CHz—OH 〇H ⑷。 再者’上述式（1)、（2)中，n表示1〜3之整數。 [2] 如上述項[1]之環氧樹脂用硬化劑，其中環氧樹脂用硬 化劑係由上述通式（1)表示，且式中之R5為氫原子。 [3] 一種微膠囊型環氧樹脂用硬化劑，其具備包含如上述項 [1]或[2]之環氧樹脂用硬化劑之核（c)、及包覆該核（c)之殼 (s) ’該殼（s)包含上述核（c)與環氧樹脂（A1)之反應物、及/ 或異氰酸酯化合物與活性氫化合物之反應物。 [4] 如上述項[3]之微膠囊型環氧樹脂用硬化劑，其中上述 殼（s)具有：吸收波數為163〇〜168〇 cm-i之紅外線的脲配位 ()及收波數為丨680〜1 725 cm-1之紅外線的縮二脲配位 基（y)、及吸收波數為1730〜1755 cm-i之紅外線的胺基甲酸 酯配位基（z)。 [5] 132805.doc 200916496 、種母料型環氧樹脂用硬化劑組合物，其係將如上 ^^=氧樹脂用硬化劑及/或如上述項[3]或[4]之微夥 中而成 [6] 々氧樹脂用硬化财的至少—種分散於環氧樹 中而成。 ^ :種單成分性調配組合物，其包含如上述項[5]之母料 型核氧樹脂用硬化劑組合物及環氧樹脂（A3)。 ' [發明之效果] 猎由本發明，可提供—種低溫硬化性及短時間硬化性優 良之環氧樹脂用硬化劑。進而可提供-種不僅具有優良之 低溫硬化性及短時間硬化性’並且兼具良好之儲存穩定性 ,耐填充料性之微膠囊型環氧樹脂用硬化劑、母料型環氧 樹脂用硬化劑組合物及單成分性調配組合物。 ' 【實施方式】 以下詳細說明用以實施本發明之最佳形態(以下稱作本 實施形態）。再者，本發明並不限於以下之本實施形態， 可於其要旨之範圍内加以各種變形而實施。 (%氧樹脂用硬化劑） 本實施形態之環氧樹脂用硬化劑係由下述通式⑴或——CHj-ljJH'-CHz—OH 〇H (4). Further, in the above formulas (1) and (2), n represents an integer of 1 to 3. [2] The hardener for an epoxy resin according to the above item [1], wherein the hardener for the epoxy resin is represented by the above formula (1), and wherein R5 in the formula is a hydrogen atom. [3] A microcapsule-type epoxy resin hardener comprising a core (c) comprising a hardener for an epoxy resin according to the above item [1] or [2], and a shell covering the core (c) (s) 'The shell (s) comprises a reactant of the core (c) and the epoxy resin (A1), and/or a reaction product of an isocyanate compound and an active hydrogen compound. [4] The microcapsule-type epoxy resin hardener according to the above item [3], wherein the shell (s) has a urea coordination () of an infrared ray having a wavenumber of 163 〇 to 168 〇cm-i. The biuret ligand (y) having an infrared number of 丨680 to 1 725 cm-1 and the urethane ligand (z) having an infrared ray having an absorption number of 1730 to 1755 cm-i. [5] 132805.doc 200916496, a masterbatch type epoxy resin hardener composition, which is to be used as a hardener for oxygen resin and/or a micro-combination as in the above item [3] or [4] [6] The epoxy resin is formed by dispersing at least one kind of hardening property in an epoxy tree. A single-component compounding composition comprising the master batch type hardener composition for a core oxygen resin and the epoxy resin (A3) according to the above item [5]. [Effect of the Invention] According to the present invention, it is possible to provide a curing agent for an epoxy resin which is excellent in low-temperature curability and short-time hardenability. Further, it is possible to provide a hardener for a microcapsule type epoxy resin which is excellent not only excellent in low-temperature hardening property and short-time hardenability, but also has good storage stability and filler properties, and a hardener for a masterbatch type epoxy resin. Composition and single component formulation. [Embodiment] Hereinafter, the best mode for carrying out the invention (hereinafter referred to as the present embodiment) will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention. (% hardener for oxygen resin) The hardener for epoxy resin according to the present embodiment is represented by the following formula (1) or

表示。 JSaid. J

[化5][Chemical 5]

⑴ 132805.doc 200916496 [化6](1) 132805.doc 200916496 [Chem. 6]

⑵ 、其:’上述式⑴、⑺中，R】、r5表示氫原子、可 代之碳數為1〜6的烷基或可經取代之碳數為丨〜丨）的芳茂 R2表示氫原子或可經取代之碳數為1〜6的烷基。 A。 下述通式（3)或下述通式 R·3及I分別獨立地表示氫原子 (4)所表示之基。 [化7](2) In the above formula (1), (7), R], r5 represents a hydrogen atom, may be substituted with an alkyl group having 1 to 6 carbon atoms, or the substituted carbon number is 丨~丨), and R2 represents hydrogen. An atom or an alkyl group which may be substituted with a carbon number of 1 to 6. A. The following general formula (3) or the following general formulas R·3 and I each independently represent a group represented by a hydrogen atom (4). [Chemistry 7]

⑶ 式（3)中，心及尺2與上述同義。 [化8](3) In the formula (3), the heart and the ruler 2 are synonymous with the above. [化8]

——CH2-<pH-〇H2—OH OH ⑷ 再者’上述式（1)、（2)中，η表示1〜3之整數。 上述通式（1)或（2)中，&所表示之可經取代之碳數為1〜6 的烷基的「烷基」表示碳數為丨〜6、較好的是卜3之直鏠狀 或支鏈狀的烷基。例如可列舉：甲基、乙基、丙基、異内 基、丁基、異丁基、第二丁基、第三丁基、戊基、己基 4 ’較好的疋曱基、乙基，更好的是甲基。 132805.doc -11 · 200916496 上述通式⑴或（2)中，作為Rl所表示之可經取代之碳數 為1〜12的芳基的「芳基」，例如可列舉苯基、萘基等，較 好的是苯基。 上述通式⑴或（2)中，作為r2所表示之可經取代之碳數 為1〜6的烧基的「絲」’可列舉與上述中所定義的&所表- CH2-<pH-〇H2-OH OH (4) Further, in the above formulas (1) and (2), η represents an integer of 1 to 3. In the above formula (1) or (2), the "alkyl group" of the alkyl group having 1 to 6 carbon atoms which may be substituted by & represents a carbon number of 丨6, preferably 3 Straight or branched alkyl. For example, a methyl group, an ethyl group, a propyl group, an isoendyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group 4'- preferably a mercapto group, and an ethyl group are exemplified. More preferred is methyl. 132805.doc -11 - 200916496 In the above formula (1) or (2), examples of the "aryl group" of the aryl group having 1 to 12 carbon atoms which may be substituted by R1 include a phenyl group, a naphthyl group and the like. Preferred is phenyl. In the above formula (1) or (2), the "silk" of the alkyl group having 1 to 6 carbon atoms which may be substituted as represented by r2 may be exemplified by &

示之烷基相同之烷基。作為R2,較好的是氫原子、甲基， 更好的是氫原子。 A 上述通式（1)或（2)中，作為Rs所表示之可經取代之碳數 為1〜6的烷基的「烷基」，可列舉與上述中所定義之烷基相 同之烷基。作為Rs，較好的是氫原子 '甲基，更好的是氫 原子。 & 上述R!、R2、R3、R4、Rs所表示之可經取代之碳數為 1〜6的烷基及碳數為卜12的芳基亦可於可取代之位置上經 一個或兩個以上之取代基取代。作為該取代基，可列舉： 齒素原子（例如氟原子、氯原子、漠原子）、碳數為丨〜6的 烷基（例如曱基、乙基、丙基、異丙基、丁基、異丁基、 第二丁基、第三丁基、戊基、己基）、芳基（例如苯基、萘 基）、芳烷基（例如节基、苯乙基）、烷氧基（例如曱氧基Y 乙氧基）等。 上述式（1)、（2)中，n表示^3之整數，較好的是i。 作為本實施形態之環氧樹脂罔硬化劑，可列舉：相對於 硬化劑整體，而含有較好的是50〜100質量％、更好的是 60〜100質量％、進而好的是7〇〜100質量％的下述通式⑺: (6)所表示之化合物者。 一 132805.doc -12- 200916496 [化9] ΝγΝ RiAn alkyl group having the same alkyl group. As R2, a hydrogen atom, a methyl group, and more preferably a hydrogen atom are preferred. In the above formula (1) or (2), the "alkyl group" of the alkyl group having 1 to 6 carbon atoms which may be substituted as represented by Rs may, for example, be the same as the alkyl group defined in the above. base. As Rs, a hydrogen atom 'methyl group is preferred, and a hydrogen atom is more preferred. & The above-mentioned R!, R2, R3, R4, and Rs may be substituted with an alkyl group having 1 to 6 carbon atoms and an aryl group having a carbon number of 12, or may be substituted at one or two positions. More than one substituent is substituted. Examples of the substituent include a dentate atom (for example, a fluorine atom, a chlorine atom, and a desert atom), and an alkyl group having a carbon number of 丨6 (for example, an anthracenyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group). Isobutyl, second butyl, tert-butyl, pentyl, hexyl), aryl (eg phenyl, naphthyl), aralkyl (eg, benzyl, phenethyl), alkoxy (eg hydrazine) Oxyl Y ethoxy) and the like. In the above formulae (1) and (2), n represents an integer of ^3, and preferably i. The epoxy resin lanthanum hardener of the present embodiment is preferably contained in an amount of from 50 to 100% by mass, more preferably from 60 to 100% by mass, even more preferably from 7 to 5% by weight based on the entire curing agent. 100% by mass of the compound represented by the following formula (7): (6). A 132805.doc -12- 200916496 [Chemical 9] ΝγΝ Ri

-ch2-ch—ch2 OH ,r2 2-CH—CH2— OH T Ri ⑸ [化 10]-ch2-ch-ch2 OH ,r2 2-CH-CH2— OH T Ri (5) [Chem. 10]

OHOH

Rs ⑹ Ν-ϊγ^Ν—CH2-CH—CH2~ ,r2 ^^CH^oh-cHj-N7 Y OH J R1 上述通式（5)、（6)中 所定義者相同。 1 ' 係與上述式⑴、（2)中 上述環氧樹脂用硬化劑可以 ， 之例中，可藉由將味_ 去製造’通式（5) 化而成之環氧樹脂，於適：红^己院加以縮水甘油 造；通式⑹之例中，可二=中加熱，使其反應而製 ^ 將咪唑類與將二羥基環己基加Rs (6) Ν-ϊγ^Ν—CH2-CH—CH2~ , r2 ^^CH^oh-cHj-N7 Y OH J R1 The same as defined in the above formulas (5) and (6). 1 ' is the above-mentioned hardening agent for epoxy resins in the above formulas (1) and (2). In the example, the epoxy resin obtained by the method (5) can be produced by using the scent: Red ^ ancex is made of glycidol; in the example of general formula (6), it can be heated by two = medium reaction to make imidazoles and dihydroxycyclohexyl

Lj 縮水甘油“成之環氧樹脂於適#之 反應而製造。 … 、亡述通式(5)之例中，具體而言可藉由一面向將咪唑類 以浴劑稀釋而成之味唾溶液中，添加將二經基苯加以縮水 甘油：而成之環氧樹脂的溶液(以下亦稱作環氧樹脂溶 面使其反應，其後，進而使其反應固定時間而製 il： ° ' 'v 作為咪唑類，例如可列舉：咪唑、2-甲基咪唑、2_乙 基4-甲基咪唑、2_十一烷基咪唑、2_十七烷基咪唑、2-苯 132805.doc -13 - 200916496 基咪。坐、1_胺基乙基_2_甲基 T丞♦唑 ' 丨-(2-羥基-3-苯氧基丙 基）-2-甲基口米哇、1 _(2_經其3笑氧Α Μ觳基-3-本乳基丙基）_2_乙基-4_ 咪0坐、1-(2 -經基-3 -丁盞萁系甘、 土 丁巩基丙基）_2_甲基咪唑、羥Lj glycidol is produced by the reaction of epoxy resin into a suitable one. In the case of the general formula (5), specifically, it can be diluted by a bath for imidazole. In the solution, a solution of an epoxy resin obtained by adding glycidol to diphenylbenzene (hereinafter also referred to as an epoxy resin surface to be reacted, and then reacting for a fixed period of time to prepare il: ° ' 'v as an imidazole, for example, imidazole, 2-methylimidazole, 2-ethyl 4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-benzene 132805.doc -13 - 200916496 KIMI. Sit, 1_Aminoethyl 2 -methyl T 丞 ♦ azole ' 丨-(2-hydroxy-3-phenoxypropyl)-2-methyl-mimi, 1 _(2_ via its 3 laughter oxime Μ觳 -3--3-mercaptopropyl)_2_ethyl-4_ 咪 0 sit, 1-(2-trans-yl-3-butanthene, tertidine Propyl)_2_methylimidazole, hydroxy

基-3 _ 丁氧基丙基）· 2 -乙基_ 4 -审Dik I AA 丞4甲基咪唑等。尤其就兼具良好 之低溫硬化性與儲存穩定性之顴 心蜆點而S，較好的是咪唑、 2-甲基咪唑、2-苯基咪唑，更好的是2_曱基咪唑。 上述味哇類與將二羥基苯加以缩 Λ縮水甘油化而成之環氧樹 月曰的比例並無特別限制’較好的是咪哇類/將二經基苯加 以縮水甘油化而成之環氧樹脂(莫耳比)=05〜20,更好的。 是1.0〜1.2。若上述比例在2相τ，則存在硬化劑之 性變得良好之傾向’若在〇.5以上，則存在硬化劑之破璃 轉移溫度Tg降低，低溫硬化性變得良好之傾向。 用於上述反應中之溶劑若為—定程度地溶解起始原料， 且並不阻礙反應者’則並無特別限制。例如可列舉：苯、 曱苯、二曱苯、環己烷、礦油精、石腦油等烴類；丙酮、 i. 甲基乙基酮、曱基異丁基酮等網類 ^只，G毆乙酯、乙酸正丁 酯、丙二醇單曱醚乙酸酯等酯類；甲醇、異丙醇、 醇、丁基溶纖劑、丁基卡必醇等醇類 _ ^ 吁蝴，G —醇皁甲醚、乙 二醇單***、乙二醇單丁醚、丙二醇 并早T醚、丙二醇單乙 醚、丙二醇單丙醚等醚類；水等。 /、灯的疋丙二醇單甲 醚、丙二醇單*** '乙二醇單 J ^忒荨溶劑可單獨使 用，亦可併用兩種以上。 對反應溫度、反應時間、稀釋濃度並無特別限制，、雨 常，將10〜100質量。/〇之濃度的環氧樹脂溶液，於π〜^ A V/ V/ 132805.doc •14- 200916496 左右之溫度下以10〜1 8 0分鐘添加至p米π坐溶液中，使其反應 (第1反應），其後，於50〜200 t左右之溫度下使其反應 10〜180分鐘即可（第2反應）。 本實施形態中，下述方法由於目標環氧樹脂用硬化劑的Base-3 _butoxypropyl)· 2 -ethyl _ 4 -Dik I AA 丞4 methylimidazole and the like. In particular, it is preferable to have good low-temperature hardenability and storage stability, and preferably, imidazole, 2-methylimidazole, 2-phenylimidazole, and more preferably 2-mercaptoimidazole. There is no particular limitation on the ratio of the above-mentioned savory type to the glycidyl sulphate which is obtained by condensing and dihydrating dihydroxybenzene. It is preferred that the imiline/diphenylbenzene is glycidylated. Epoxy resin (mole ratio) = 0 to 20, better. It is 1.0 to 1.2. When the ratio is in the two-phase τ, the properties of the curing agent tend to be good. When the content is 5% or more, the glass transition temperature Tg of the curing agent is lowered, and the low-temperature curing property tends to be good. The solvent used in the above reaction is not particularly limited as long as it dissolves the starting material to a certain extent and does not hinder the reaction. Examples thereof include hydrocarbons such as benzene, toluene, diphenylbenzene, cyclohexane, mineral spirits, and naphtha; and nets such as acetone, i. methyl ethyl ketone, and mercaptoisobutyl ketone. Esters such as G 殴 ethyl ester, n-butyl acetate, propylene glycol monoterpene ether acetate; alcohols such as methanol, isopropanol, alcohol, butyl cellosolve, butyl carbitol, etc. _ ^ 蝴, G - alcohol soap Ethers such as methyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol and early T ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether; water, and the like. /, propylene glycol monomethyl ether of the lamp, propylene glycol monoethyl ether 'ethylene glycol single J ^ 忒荨 solvent may be used singly or in combination of two or more. The reaction temperature, the reaction time, and the dilution concentration are not particularly limited, and rain is usually 10 to 100 mass. / Epoxy resin solution at a concentration of 〇 ~ ^ AV / V / 132805.doc • 14- 200916496 at a temperature of 10~18 0 minutes added to the p m π sitting solution to make the reaction (the first 1 reaction), and thereafter, the reaction is carried out at a temperature of about 50 to 200 t for 10 to 180 minutes (second reaction). In the present embodiment, the following method is due to the target epoxy resin hardener.

Tg降低，低溫硬化性變得良好而尤佳：將5〇〜9〇質量％之 濃度之環氧樹脂溶液，於70〜1〇〇〇c&右之溫度下以6〇〜12〇 分鐘添加至咪唑溶液中，使其反應（第丨反應），其後，將溶The Tg is lowered, and the low-temperature hardening property is good, and it is particularly preferable to add an epoxy resin solution having a concentration of 5 〇 to 9 〇 mass% at a temperature of 70 〇〇〇 1 〇〇〇 c & In the imidazole solution, the reaction is carried out (the third reaction), after which it will be dissolved.

劑餾去，進而於150〜19(TC左右之溫度下使其反應6〇〜12〇 分鐘（第2反應）。 進仃上述（第2反應）後，於減壓下將未反應之咪唑類餾 去’藉此可獲得本實施形態之環氧樹脂用硬化劑。 曰=提高與所硬化之環氧樹脂的相容性為目的、及/或以 提冋硬化速度為目@ ’亦可於本實施形態之環氧樹脂用硬 化劑中摻合人其他咪錢性環氧樹脂、胺改性環氧樹脂、 胺加成物等。 於本實施形態之環复谢m λ 氣Μ月曰用硬化劑中摻合入咪唑改性環 氧樹脂、胺改性環惫抖 h w s曰、胺加成物，係加熱為軟化點以 if M ^ m 進仃。混合形態可根據最終目標之 衣乳树月曰用硬化劑而適 散狀態等。 選擇相谷«、分散狀態、微分 於此情形時， 上述咪唑化合物 物。 作為環氧樹脂 作為咪唑改性環氧樹脂’例如可應用自 中選擇之咪唑與下述環氧樹脂之反應產 4々可列舉：將雙酚A、雙酚F、雙酚 132805.doc 200916496 AD、雙酚s '四曱基雙酚A、四曱基雙酚F、四甲基雙酚 AD、四甲基雙酚s、四溴雙酚八、四氣雙酚a、四氟雙酚a 等雙酚類加以縮水甘油化而成之雙酚型環氧樹脂，將聯苯 酚、二羥基萘、二羥基苯、9,9_雙（4_羥基苯基）第等其他 二酚類加以縮水甘油化而成之環氧樹脂，將^-三（心羥 基苯基）甲烷、^4-(1-(4-(1-(4-羥基苯基）-1-曱基乙基）苯 基）亞乙基）雙酚等三酚類加以縮水甘油化而成之環氧樹 月曰將丨，1，2,2，·® (4-羥基苯基）乙烷等四酚類加以縮水甘油 化而成之娘氧樹脂，將苯酚酚醛清漆、甲酚酚醛清漆、雙 盼A㈣清漆、漠化⑽祕清漆、溴化雙齡杨駿清$ 等^清漆類加以縮水甘油化而成之酚搭清漆型環氧樹脂 ^將=盼類加以縮水甘油化而成之環氧樹脂；將甘油或聚 $一酵等多元醇加以縮水甘油化而成之脂肪族_型環氧樹 I ;將對經基苯甲酸、^經基萘甲酸等經基賴加以縮 7 =油，而成之_醋型環氧樹脂；將鄰苯二曱酸、對苯二 4 4等彡疋缓酸加以縮水甘油化而&之醋型環氧樹脂； 二胺基—本基Τ院或間胺基苯盼等胺化合物之縮水甘 水甘t、或異氛尿酸三縮水甘油醋等胺型環氧樹脂等之縮 …環氧樹脂，或3,4_環氧環己基甲基_3，，4，-環氧環 %甲S夂酯等脂環族環氧化物等。 組：铷 & 了可提向後述之母料型環氧樹脂用硬化劑 而叙储存穩定性，較好的是將多紛類加以縮水甘油化 之環氧^樹脂’更好的是將雙紛類加以縮水甘油化而成 衣月曰，進而好的是將雙龄A加以縮水甘油化而成之 132805.doc -16- 200916496 環氧樹脂、將雙酚！?加以 ^縮水甘油化而成之環氧樹脂，進 好的是將雙酚八加以縮水甘油化而成之環氧樹脂。 作為胺改性環氧樹脂，可應用自下述胺化合物中選擇之 胺與自上述環氧樹脂中選擇之環氧樹脂的反應產物。 等作為上《’可列舉：脂肪族胺、脂環式胺、芳香族胺 作為脂肪族胺，例如可· J列舉.甲胺、乙胺、丙胺、丁 胺、二丁胺等烷基胺； 胺丙一胺、丁二胺、己二胺 等燒一胺；二伸乙三胗 一 二伸乙四胺、四伸乙五胺等多伸 烧基多胺；聚氧丙二胺、咿备7 #松 聚氧乙一胺荨聚氧伸烷基聚胺 等。 作為脂環式胺，例如可 J列舉.J衣丙胺、環丁胺、環戊 胺、環己胺、異佛爾酮二胺等。 作為芳香族胺，例如可料：苯胺、甲苯胺1胺、蔡 胺、二胺基二苯基甲燒、二胺基二苯基硬等。 ' 作為上述胺加成物，例如 J歹!舉下述（b-Ι)成分與（b_2)成 分之反應物。 (b-υι自由敌酸化合物'績酸化合物、脲化合物、異 氰酸醋化合物、及與下述異氰酸醋化合物中所記載之(A1; 成分相同之環氧樹脂所組成之群中的一種或兩種 合物。 (b-2) ·胺化合物。 作為上述（b-Ι)中之雜酸^卜人& 一 又歿鲛化合物，例如可列舉：丁二酸、 己^一酸、癸二酸、鄰贫-田 鄰本一甲酸、二聚酸等。作為磺酸化合 132805.doc 200916496 物’例如可列舉：甲石黃酸、 脈化合物，例如可列舉.脲、Λ 等。作為 脲、第三丁基脲等似… 二甲基脲、乙基 r肪族1 氛酸醋化合物，例如可列舉： 曰肪族一異㈣酿、脂環式二異氰酸醋、芳香族二 酯、脂肪族三異氰酸酯、聚異氰酸酯等。 " 一：為上述脂肪族二異氰酸醋’例如可列舉：二異氰酸乙 一s日、一異氰酸丙二酯、二異氰酸丁二酯、二里 酯、二異氰酸三甲基己二酯等。 、 一 述脂環式二異氰酸酯，例如可列舉：異佛爾酮二 ”文酯Μ -一蜋己基甲烷二異氰酸酯、降褚烷二異氰 酸S曰、1，4-異氰酸酯基環己烷、込夂雙(異氰酸酯基曱基) 環己烷、1，3-雙（2·異氰酸酯基丙基·2_基）_環己烷等。土 作為上述芳香族二異氰酸酯，例如可列舉：甲苯二異氰 酸酿、4’二苯基甲烷二異氰酸醋、二甲苯二異氰酸醋、 1，5-萘二異氰酸酯等。The solvent is distilled off, and further reacted at 150 to 19 (about TC for 6 Torr to 12 Torr (second reaction). After the above (second reaction), the unreacted imidazole is decompressed under reduced pressure. The epoxy resin hardener of the present embodiment can be obtained by distillation. 曰 = the purpose of improving the compatibility with the cured epoxy resin, and/or the lifting hardening speed is as follows. In the hardener for epoxy resin of the present embodiment, a human other epoxy resin, an amine-modified epoxy resin, an amine adduct or the like is blended in the epoxy resin of the present embodiment. The hardener is blended with an imidazole-modified epoxy resin, an amine-modified ring, a hws曰, an amine adduct, and is heated to a softening point with an if M ^ m. The mixed form can be based on the final target of the latex tree. The ruthenium is in a state of dispersing with a hardener, etc. When the phase is selected, the state of dispersion is dispersed, and the above-mentioned imidazole compound is used as the epoxy resin as the imidazole-modified epoxy resin, for example, an imidazole selected from the group can be used. The reaction with the following epoxy resin produces 4 々 can be cited: bisphenol A, bisphenol F Bisphenol 132805.doc 200916496 AD, bisphenol s 'tetradecyl bisphenol A, tetradecyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol s, tetrabromobisphenol VIII, four gas double a bisphenol type epoxy resin obtained by glycidylating a bisphenol such as phenol a or tetrafluorobisphenol a, which comprises biphenol, dihydroxynaphthalene, dihydroxybenzene, 9,9-bis(4-hydroxyphenyl) An epoxy resin obtained by glycidylation of the other diphenols, which is ^-tris(hydroxyphenyl)methane, ^4-(1-(4-(1-(4-hydroxyphenyl))-1 - Ethylene phthalocyanine, such as decylethyl)phenyl)ethylidene) bisphenol, which is glycidylated, is 1,2,2,·(4-hydroxyphenyl) A phenolic phenolic varnish, a cresol novolac, a smear A (four) varnish, a desertification (10) secret varnish, a brominated double-aged Yang Junqing, etc. A phenolic varnish-type epoxy resin which is made of phenolic epoxidized epoxy resin; an epoxy resin obtained by glycidylation of a glycerin or a polyhydric alcohol such as polyglycerol Tree I; Acid, phthalic acid, etc., which are reduced by 7 to oil, to form a vinegar-type epoxy resin; glycidylation of phthalic acid such as phthalic acid or p-phenylene 4 4 ; vinegar-type epoxy resin; diamine-based brothel or m-aminobenzamine and other amine compounds, such as water-reducing ganshui t, or iso-uric acid triglycidyl vinegar and other amine-type epoxy resin... An epoxy resin, or an alicyclic epoxide such as 3,4-epoxycyclohexylmethyl-3,4,-epoxycyclomethylsulfonyl ester, etc. Group: 铷& can be mentioned later The masterbatch type epoxy resin is used for the storage stability of the hardener, and it is preferable to use a polyglycidyl epoxy resin which is more versatile. Furthermore, it is good to reduce the glycation of two-year-old A. 132805.doc -16- 200916496 Epoxy resin, bisphenol! The epoxy resin obtained by glycidation is preferably an epoxy resin obtained by glycidylating bisphenol eight. As the amine-modified epoxy resin, a reaction product of an amine selected from the following amine compounds and an epoxy resin selected from the above epoxy resins can be used. As the above, 'exemplified: an aliphatic amine, an alicyclic amine, an aromatic amine as an aliphatic amine, for example, an alkylamine such as methylamine, ethylamine, propylamine, butylamine or dibutylamine; Amine-amine, butanediamine, hexamethylenediamine, etc.; a diamine, an ethylenediamine, a tetraethyleneamine, a tetraamethyleneamine, etc.; a polyoxypropylenediamine, a preparation 7 #松聚氧乙一胺荨 polyoxyalkylene alkylamine and the like. Examples of the alicyclic amine include J-propylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine. The aromatic amine may, for example, be aniline, toluidine 1 amine, ceamine, diaminodiphenylmethane or diaminodiphenyl hard. As the above amine adduct, for example, J反应! is a reaction product of the following (b-Ι) component and (b_2) component. (b-υι free ester acid compound 'acidic acid compound, urea compound, isocyanate compound, and the group consisting of the following epoxy resin in the isocyanate compound (A1; One or two compounds. (b-2) - Amine compound. As the above-mentioned (b-Ι), the hetero-acids of the above-mentioned (b-Ι) can be exemplified by succinic acid and hexamic acid. The azelaic acid, the o-poor, the phthalic acid, the dimer acid, and the like. Examples of the sulfonate compound 132805.doc 200916496 include, for example, a naphthoic acid or a pulse compound, and examples thereof include urea and hydrazine. Examples of the urea, the third butyl urea, etc., such as dimethyl urea and ethyl aryl 1 amic acid vinegar, are exemplified by: 曰 aliphatic one different (four) brewing, alicyclic diisocyanate, aromatic a diester, an aliphatic triisocyanate, a polyisocyanate, etc. " One: the above-mentioned aliphatic diisocyanate vines, for example, ethyl disocyanate, propylene diisocyanate, diisocyanate Butadiene ester, dilacide, trimethyl hexane diisocyanate, etc., an alicyclic diisocyanate, for example Listed: isophorone bis- oxime oxime - monohexyl methane diisocyanate, decane diisocyanate S oxime, 1,4-isocyanate cyclohexane, bismuth (isocyanate fluorenyl) cyclohexane Alkane, 1,3-bis(2.isocyanatepropyl-2-yl)-cyclohexane, etc. As the aromatic diisocyanate, for example, toluene diisocyanate, 4' diphenylmethane Diisocyanate vinegar, xylene diisocyanate vinegar, 1,5-naphthalene diisocyanate, and the like.

作為上述脂肪族三異氰酸酯，例如可列舉：丨，3,6_三異 氰酸醋基甲基己烷、2,6_二異氰酸酿基己酸_2_異氰酸酯基 乙酯等。 作為上述聚異氰酸酯，例如可列舉：聚亞甲基聚苯基聚 異氰酸酯、或由上述各種二異氰酸酯化合物所衍生之各種 聚異氰酸酯。作為上述聚異氰酸酯，可包含異氰尿酸醋型 聚異氰酸酯、縮二脲型聚異氰酸酯、胺基曱酸酯型聚異氰 酸酯、脲基曱酸酯型聚異氰酸酯、碳二醯亞胺型聚異氰酸 酯等中之任一者。 132805.doc •18· 200916496 另一方面’作為上述（b-2)之胺化合物’例如可列舉：下 述（b-2-l) 、 （b-2-2)。 (b-2-l):具有至少一個一級胺基及/或二級胺基，彳曰不 具有三級胺基之化合物。 (b-2-2):具有至少一個三級胺基與至少—個活性氯美之 化合物。 作為上述（b-2-l)成分，例如可列舉： 胺、丁胺、乙二胺、丙二胺' 己二胺、二伸？ 一 r G二胺、三伸 乙四胺、乙醇胺、丙醇胺、環己胺、異佛爾酮二胺、苯 胺、甲苯胺、二胺基二苯基曱烷、二胺基二苯基硬等不具 有三級胺基之第一胺類；二曱胺、二乙胺、二丙胺、 胺、二戊胺、二己胺、二甲醇胺、二乙醇胺、_ 町哎—丙醇胺、 二環己胺、哌啶、哌啶酮、二苯胺、苯基曱胺、笨艽乙〜 等不具有三級胺基之第二胺類。該等可單獨使用，亦可广 用兩種以上。 作為上述（b-2-2)成分之活性氫基，例如可列舉·一 .一級胺 基、一級胺基、經基、硫醇基、缓酸、醯肼某。 作為上述（b-2-2)之具體例’可列舉：2_二曱美胺義 醇、1-甲基-2-二曱基胺基乙醇、^苯氧基甲基二曱 基乙醇、2 -二乙基胺基乙Sf*、1-丁氧某甲其ο 乳基甲基_2·二曱基胺基 乙酵、甲基二乙醇胺…醇胺H經基乙基 胺基醇類；2-(二甲基胺基甲基）苯酚、24 6_ = ， L ( —*甲基胺 基甲基）苯酚等胺基苯酚類；咪唑、2_甲基味唾、2 4-甲基咪。坐、2_十一烷基咪。坐、2_十七烷基咪2乙笨基義 132805.doc •19· 200916496 味峻、！-胺基乙基-2-甲基咪。坐、W2_經基_3_苯氧基丙基）_ 2-甲基咪唑、^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、丨_(2_羥基-3· 丁氧基丙基）-2-乙基-4-曱基咪唑等咪唑類；丨_(2羥基_3_苯 氧基丙基）-2-苯基咪唑啉、^(2·羥基_3_ 丁氧基丙基）_2_曱 基咪唑啉、2-甲基咪唑啉、2,4-二曱基咪唑啉、2_乙基咪 唑啉、2-乙基_4_甲基咪唑啉、2_节基咪唑啉、2_苯基味唑 啉、2-(鄰曱苯基）_咪唑啉、四亞曱基_雙_咪唑啉、丨，丨％三 甲基-1，4-四亞甲基-雙_咪唑啉、三曱基_i，4四亞甲 基-雙-咪唑啉、1，1，3-三甲基_ι，4-四亞甲基_雙_4_曱基咪唑 啉、1，3,3-三甲基-1，4-四亞甲基-雙_4_甲基咪唑啉、12_伸 苯基-雙-咪唑啉、1，3-伸苯基-雙-咪唑啉、丨，4_伸苯基_雙_ 咪唑啉、1，4-伸苯基-雙-4-甲基咪唑啉等咪唑啉類；二曱 基胺基丙基胺、二乙基胺基丙基胺、二丙基胺基丙基胺、 二丁基胺基丙基胺、二曱基胺基乙基胺、二乙基胺基乙基 胺、一丙基胺基乙基胺、二丁基胺基乙基胺、N_曱基旅 唤、N-胺基乙基哌嗪、二乙基胺基乙基哌嗪等三級胺基胺 類，2-二甲基胺基乙硫醇、2-疏基苯并咪唾、2-疏基苯并 噻唑、2-毓基吡啶、4-毓基吡啶等胺基硫醇類；N，N_二曱 基胺基苯甲酸、N，N-二曱基甘胺酸、菸鹼酸、異菸鹼酸、 °比啶甲酸等胺基羧酸類；N，N-二甲基甘胺酸醯肼、菸鹼酸 醯肼、異菸鹼酸醯肼等胺基醯肼類。該等可單獨使用，亦 可併用兩種以上。 本實施形態之環氧樹脂用硬化劑之玻璃轉移溫度（Tg)較 132805.doc •20· 200916496 好的是40〜100T：，更好的是5〇〜8〇。〇,進而好的是5〇〜7〇 若Tg在100〇C以下，則存在可獲得優良之低溫硬化性及 短時間硬化性之傾向，若在4(rc以上，則存在後述之母料 型環氧樹脂用硬化劑組合物的儲存穩定性可提高之傾向。 此處，Tg係指利用示差掃描熱析儀，以1〇t/分鐘之升溫 速度而於0°c〜20(TC之範圍内所測定之值。 '皿 r 作為本實施形態之環氧樹脂用硬化劑的固體狀（軟化點 以上）之形態，可列舉塊狀、顆粒狀、粉末狀等，較好的 是顆粒狀或粉末狀，進而好的是粉末狀。 於此情形時，所謂粉末狀，係指具有較好的是〇1〜5〇 μηι、更好的是0.5〜10 μηι之平均粒徑者。若平均粒徑在〇 1 μιη以上，則存在短時間硬化性優良之傾向，若在5〇 以 下，則存在可獲得均質之硬化物之傾向。此處，所謂平均 粒徑，係指以光散射法所測定之中值粒徑。又，其形狀並 1.; I特別限制，可為球狀、不定形中之任-者，就後述之單 成分性調配組合物的低黏度化觀點而言，較好的是球狀。 此處，所謂球狀，係指亦包含圓球狀及其以外之不定形的 角帶有圓形之形狀。 (微膠囊型環氧樹脂用硬化劑） 本實施形態之微膠囊型環氧樹腊用硬化劑係具有下述結 構者由環氧樹脂用硬化劑所形成之核（c)由下述核（c)與 環氧樹脂（A1)之反應物、及/或異氰酸酯化合物與活性氫化 合物之反應物即殼（S)所包覆。此處，作為環氧樹月旨用硬 132805.doc -21 - 200916496 化劑之形態，較好的是上述粉末狀的形態。 作為上述環氧樹脂（A1)，例如可列舉：將㈣A、雙盼 F又驗AD、雙紛s、四甲基雙盼a、四甲基雙舒、四甲 基雙盼AD、四甲基雙盼s、四漠雙紛A、四氣雙盼A、四 氟又酚A等又酚類加以縮水甘油化而成之雙酚型環氧樹 月日’將耳什本紛、二經基萘 '二經基苯、9,9-雙（4-經基笨 基)苐等其他—酚類加以縮水甘油化而成之環氧樹脂，將 二(―4_經基苯基）曱烧、4,4_(1(4_(1_(4_經基苯基）小甲 ^乙基）苯基）亞乙基）雙齡等三龄類加以縮水甘油化而成之 %氧樹脂’將13,2,2.四（4_經基苯基）乙燒等四紛類加以縮 水甘油化而成之環氧樹脂，將苯㈣料漆、甲盼祕清 漆、雙紛A㈣清漆、演化苯盼㈣清漆、漠化雙齡麵 酸清漆等祕清漆類加㈣水甘油化Μ之㈣清漆型環 氧樹脂等將多紛類加以縮水甘油化而成之環氧樹脂；將甘 油或聚乙二醇等多元醇加以縮水甘油化而成之脂肪朗型 壤乳樹脂；將對經基苯甲酸卞經基萘甲酸等經基㈣ 加以縮水甘油化而成之醚酿型環氧樹脂；將鄰苯二曱酸、 ，苯二甲酸等聚羧酸加以縮水甘油化而成之醋型環氧樹 月曰’ 4’4_二胺基二苯基甲院或間胺基苯料胺化合物之縮 由化物4異氰尿酸二縮水甘油醋等胺型環氧樹脂等 之，水甘油基型環氧樹脂’或3,4·環氧環己基甲基-… 氧環己烷甲酸酯等脂環族環氧化物等。 ，仏 該等之中’為了可提高後述之母料型環氧樹脂用 組合物的儲存穩定性，較好的是將多_加以縮水甘油1 132805.doc -22- 200916496 而成之環氧樹脂，更好的是將雙盼類加以縮水甘油化而成 ，樹脂’㉟而好的是將雙盼八加以縮水甘油化而成之 環氧樹脂'將雙㈣加以縮水甘油化而成之環氧樹脂進 而更好的是將雙紛人加以縮水甘油化而成之環氧樹脂。 作為異氰酸酯化合物，若為於丨分子中具有一個以上、 較好的是兩個以上之異氰酸醋基的化合物，則並無特別限 制。例如可列舉：脂肪族二異氰酸酯、Examples of the aliphatic triisocyanate include hydrazine, 3,6-triisocyanatoacetate methylhexane, and 2,6-diisocyanuric acid caproic acid 2-isoisocyanate ethyl ester. The polyisocyanate may, for example, be a polymethylene polyphenyl polyisocyanate or various polyisocyanates derived from the above various diisocyanate compounds. The polyisocyanate may include a polyisocyanurate type polyisocyanate, a biuret type polyisocyanate, an amino phthalate type polyisocyanate, a urea phthalate type polyisocyanate, a carbodiimide type polyisocyanate, or the like. Either. 132805.doc • 18· 200916496 On the other hand, 'the amine compound of the above (b-2)' is exemplified by the following (b-2-l) and (b-2-2). (b-2-l): a compound having at least one primary amino group and/or secondary amine group and having no tertiary amino group. (b-2-2): a compound having at least one tertiary amino group and at least one active chlorine. Examples of the component (b-2-l) include an amine, butylamine, ethylenediamine, propylenediamine hexamethylenediamine, and a di-extension. a r G diamine, triethylene glycol tetraamine, ethanolamine, propanolamine, cyclohexylamine, isophorone diamine, aniline, toluidine, diaminodiphenyl decane, diaminodiphenyl hard a first amine having no tertiary amino group; diamine, diethylamine, dipropylamine, amine, diamylamine, dihexylamine, dimethanolamine, diethanolamine, _ 哎-propanolamine, two A second amine having no tertiary amino group, such as cyclohexylamine, piperidine, piperidone, diphenylamine, phenylguanamine, alum, and the like. These may be used singly or in combination of two or more. Examples of the active hydrogen group of the above (b-2-2) component include a primary amino group, a primary amino group, a trans group, a thiol group, a tempering acid, and a hydrazine. Specific examples of the above (b-2-2) include 2-dimethanol, 1-methyl-2-didecylaminoethanol, and phenoxymethyldidecylethanol. 2-diethylaminoethyl Sf*, 1-butoxy-methylpyryl lactylmethyl-2·didecylaminoethanol, methyldiethanolamine, alcoholamine H,ylethylamino alcohol ; 2-(dimethylaminomethyl)phenol, 24 6_ = , L (-*methylaminomethyl)phenol and other aminophenols; imidazole, 2-methyl-salt, 2- 4-methyl mum. Sitting, 2_ eleven alkyl. Sitting, 2_heptadecyl 2, B, and idiom 132805.doc •19· 200916496 Wei Jun,! - Aminoethyl-2-methylimid. Sit, W2_trans-based _3_phenoxypropyl)-2-methylimidazole, ^2-hydroxy-3-phenoxypropyl)_2-ethyl_4·methylimidazole 1_(2-hydroxyl Imidazoles such as 3-butoxypropyl)-2-methylimidazole, 丨_(2-hydroxy-3.butyloxypropyl)-2-ethyl-4-mercaptoimidazole; 丨_(2 Hydroxy_3_phenoxypropyl)-2-phenylimidazoline, ^(2.hydroxy-3-phenylbutoxypropyl)_2-mercaptoimidazoline, 2-methylimidazoline, 2,4-di Mercapto imidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2-membered imidazoline, 2-phenylisoxazoline, 2-(o-phenylphenyl)-imidazoline , tetrakisinyl-bis-imidazoline, anthracene, 丨% trimethyl-1,4-tetramethylene-bis-imidazoline, tridecyl _i, 4 tetramethylene-bis-imidazoline, 1,1,3-trimethyl-ι,4-tetramethylene_bis-4-mercaptoimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4 _Methylimidazoline, 12-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, anthracene, 4-phenylene-bis-imidazoline, 1,4-phenylene -Imidazolines such as bis-4-methylimidazoline; dinonylaminopropylamine, diethylaminopropylamine, dipropylaminopropyl , Dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, monopropylaminoethylamine, dibutylaminoethylamine, N-fluorenyl Tertiary, N-aminoethylpiperazine, diethylaminoethylpiperazine and other tertiary amino amines, 2-dimethylaminoethanethiol, 2-sulfobenzopyrene, 2 -Aminothiols such as thiobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine; N,N-didecylaminobenzoic acid, N,N-dimercaptoglycine, nicotine An acid carboxylic acid such as an acid, an isonicotinic acid or a pyridine carboxylic acid; an amine quinone such as an anthracene N,N-dimethylglycolate, bismuth nicotinic acid or an isonicotinic acid hydrazine. These may be used singly or in combination of two or more. The glass transition temperature (Tg) of the hardener for epoxy resin of the present embodiment is preferably 40 to 100 T: more preferably, it is 5 to 8 Torr, as compared with 132805.doc • 20·200916496. Further, it is preferably 5 〇 to 7 〇. If the Tg is 100 〇C or less, excellent low-temperature curing property and short-time curing property tend to be obtained. When 4 (rc or more, the master batch type described later exists The storage stability of the hardener composition for epoxy resin may be improved. Here, Tg means a range of 0 ° c to 20 (TC range) at a temperature increase rate of 1 〇 t / minute using a differential scanning calorimeter. The value measured in the inside. The dish r is a solid form (above the softening point) of the curing agent for an epoxy resin of the present embodiment, and examples thereof include a bulk form, a granular form, a powder form, and the like, and preferably a granular form or In the case of a powder, it is preferably a powder. In this case, the term "powdered" means having an average particle diameter of preferably from 1 to 5 μm, more preferably from 0.5 to 10 μηι. When the diameter is 〇1 μm or more, the curability is excellent in a short period of time, and if it is 5 Å or less, a homogeneous cured product tends to be obtained. Here, the average particle diameter is measured by a light scattering method. Median particle size. Also, its shape and 1.; I special restrictions, can be the ball In the case of the low-viscosity of the single-component composition to be described later, it is preferably spherical. Here, the spherical shape also includes a spherical shape and the like. The amorphous shape has a circular shape. (The microcapsule-type epoxy resin hardener) The microcapsule-type epoxy resin wax hardener of this embodiment has the following structure. The formed core (c) is coated with a reactant of the following core (c) and epoxy resin (A1), and/or a shell (S) which is a reaction product of an isocyanate compound and an active hydrogen compound. The epoxy resin is preferably in the form of a hard agent. The epoxy resin (A1) is exemplified by (4) A, double expectation F, and the like. AD, double s, tetramethyl bis, a tetramethyl bis, tetramethyl bis, AD, tetramethyl bis s, four desert bis, A, four gas double A, tetrafluoro phenol A The bisphenol-type epoxy tree formed by the glycidation of phenols is the same as that of the bisphenol-based phthalocyanine dimercaptobenzene, 9,9-bis (4- Styrene), etc. Other epoxy resins which have been glycidylated by phenols, which are calcined with bis(-4_pyridylphenyl), 4,4_(1(4_(1_(4_)-phenylphenyl) ) small methyl ethyl) phenyl) ethylene) three-year-old three-year-old type of glycidolated % oxygen resin '13, 2, 2. four (4_ mercaptophenyl) ethyl bromide, etc. Four kinds of epoxy resin obtained by glycidation, benzene (four) paint, nail varnish, double A (four) varnish, evolution benzene (four) varnish, desertified double-age acid varnish and other secret varnish plus (four) water (4) varnish-type epoxy resin, etc., which are obtained by glycidylation of a plurality of kinds of epoxy resins; and a fat-type breast milk resin obtained by glycidylating a polyhydric alcohol such as glycerin or polyethylene glycol; An ether-brewed epoxy resin obtained by glycidylation of hydrazinobenzoic acid via a naphthoic acid or the like via a base (tetra); a vinegar obtained by glycidylating a polycarboxylic acid such as phthalic acid or phthalic acid Type Epoxy Tree Moonworm '4'4_Diaminodiphenylcarbamate or m-Aminobenzeneamine Compound Reducing Compound 4 Isocyanuric Acid Diglycidyl Acetate and Other Amine Epoxy Tree Etc., glycidyl type epoxy resins' or 3,4-epoxycyclohexyl methyl - oxo ... cyclohexanecarboxylic acid ester and alicyclic epoxides. In order to improve the storage stability of the composition for a masterbatch type epoxy resin to be described later, it is preferred to use an epoxy resin obtained by adding glycidol 1 132805.doc -22- 200916496. It is better to glycidylate the double-presence type, and the resin '35 is preferably an epoxy resin obtained by glycidylating the double-headed eight. The epoxy obtained by glycidylating the double (four) Further, the resin is more preferably an epoxy resin obtained by glycidylating a mixture of people. The isocyanate compound is not particularly limited as long as it has one or more, preferably two or more, isocyanate groups in the ruthenium molecule. For example, an aliphatic diisocyanate can be mentioned,

-、芳香族二異氮酸醋、低分子三異氛酸二一異氛:: 等。 作為脂肪族二異氰酸酯’可列舉：二異氰酸乙二酿、二 異氰酸丙二s旨、二異氰酸丁二酿、二異氰酸丨，6-己二醋、 二異氰酸三曱基己二酯等。 作為脂環式二異氰酸酯，可列舉：異佛爾酮二異氰酸 酉曰4,4 - 一環己基甲烧一異氰酸S旨、降福院二異氰酸酷、 1’4-異氰酸酯基環己烧、1，3 -雙（異氰酸酯基甲基）_環己 烧、1，3-雙（2-異氰酸酯基丙基-2-基）-環己烧等。 作為芳香族二異氰酸酯，可列舉：甲苯二異氰酸酯、 4,4'·二苯基甲烷二異氰酸酯、二甲苯二異氰酸酯、1,5-萘 一異亂酸酷等。 作為低分子三異氰酸酯，可列舉：丨_十一烧三異氰 酸酯、1，8-二異氰酸酯基-4-異氰酸酯基甲基辛烷、三異氰 酸1，3,6-己三酯、2,6-二異氰酸酯基己酸-2-異氰酸酯基乙 5旨、2,6-二異氰酸酯基己酸_1_甲基—2-異氰酸酯基乙酯等脂 肪族三異氰酸酯化合物’三環己基甲烷三異氰酸酯、二環 132805.doc •23· 200916496 庚烧二異氰酸醋等脂環式三異氰酸酯化合物，三苯基甲尸 一異氰曰、二（異氰酸s旨基苯基）硫代鱗酸g旨等芳香族二 異氰酸酯化合物等。 作為聚異氰酸s旨，可列舉：聚亞甲基聚苯基聚異氛酸醋 或自上述二異氰酸酯、低分子三異氰酸酯所衍生之聚異氰 酸酯等。 ' 作為自上述二異氰酸醋、三異氰酸s旨所衍生之聚里氛酸 醋’可列I :異氰尿酸醋型聚異氰酸醋、縮二脲型聚異氰 酸酯、胺基甲酸酯型聚異氰酸酯、脲基甲酸酯型聚異氰酸 酿、碳二醯亞胺型聚異氰酸酯等。 上述各種異氰酸酯化合物可單猸 . j早獨使用，亦可併用兩種以 作為上述活性氫化合物，例如可列舉：水、於1分子中 有個以上《級及/或二級胺基之化合物、於1分子中 具有一個以上之羥基的化合物 寺尤其好的疋水、於1分 千中，、有一個以上之羥基的化合物。 作為上述於1分子中具有— 之化人你 s 個以上之一級及/或二級胺基 之化合物，可列舉：脂肪族 作為脂肪族胺，例如可列夹曰广、方香族胺等。 胺、二丁胺等烧基胺；乙胺舉.甲胺、乙胺、丙胺、丁 等烷—脸.„ 一胺、丙二胺、丁二胺、己二胺 哥况一胺，二伸乙三胺、三 烷A客吐 甲u四胺、四伸乙五胺等多伸 沉基夕胺；聚氧丙二胺、 收寸夕 等。 Α 乙二胺等聚氧伸烷基聚胺 作為脂環式胺，例如可 .環丙胺、環丁胺、環戊 132805.doc -24- 200916496 胺、環己胺、異佛爾酮二胺等。 作為芳香族胺，例如可列舉：苯胺、甲苯胺、节胺、萘 胺、二胺基二苯基甲燒、二胺基二苯基石風等。 作為於1分子中呈古 _ /、有個以上之羥基的化合物，可列 舉：醇化合物或紛化合物等。 作為醇化合物，例如可列舉. ^a举.甲％、丙酵、丁醇、戊 醇、己醇、庚醇、辛酸 _ . . 辛％、壬醇、癸醇、十-烷醇、月桂 醉、十二烷醇、硬脂醇、_ 一十烷私、烯丙醇、巴豆醇、炔 丙醇、環戊醇、環己醇、y 卞醇肉桂醇.、乙二醇單曱醚、 乙二醇單***、乙二醇單乙 _ ， 一 6 一醇早丁_等一元醇 類，乙二醇、聚乙二醇、 _ ^ 丙—醇、聚丙二醇、1，3 -丁二 醇、1，4- 丁 一醇、氫化雙盼a、ία _ γ 又埘Α新戊一醇、甘油、三_甲 基丙烷、季戊四醇等多元醇類等。 又，藉由在1分子中具有一 個以上ί畏乳基的化合物與在1 分子中具有一個以上羥其、％ ^ " 土羧基、一級或二級胺基、酼基 之化合物的反應而獲得之於 又侍之於1分子中具有兩個以上二級羥 基的化合物，亦例示為多元醇類。 該等醇化合物亦可為第一' 、 乐一或第二醇中之任一者。 作為酚化合物，例如可 竿，石炭酸、甲酚、二甲苯 紛、香芹酚、瑞香草酚、芡 一 π酚專早酚類；鄰苯二酚、間苯 一酚、對苯二酚、雙酚Α、 一 又酚F鄰本二酚、間苯三酚等 多紛類等。 作為上述於1分子中旦古 „ a, 甲具有一個以上羥基的化合物，較好 的疋多讀類或多紛類等，更好的是多元醇類。 132805.doc -25- 200916496 上述中所說明之活性氫化合物 卿j早獨使用，亦可併用兩 檀以上。 本實施形態之膠囊型環梟满 衣氧枒月曰用硬化劑可以任一種方法 製造’例如可藉由將上述環 衣巩树月日用硬化劑、異氰酸酯化 5物、及活性氫化合物添 芏衣軋樹脂（Α1)中進行混合， 使其反應而製造。 異鼠Sa化合物之量並無特別卩卩$丨 ^ 热符別限制，相對於1 00質量份 之環氧樹脂用硬化劑，較奸的β0 # ，^ 奴好的疋1〜25質量份，更好的是 3〜20質量份。 活性氫化合物之量並盔牲 w …将別限制，相對於100質量份之 環氧樹脂用硬化劑，較好的 子乂灯的疋0〜1〇質量份，更好的是 〇.5〜5質量份。 環氧樹脂（A 1)之量並益特別pp "，、特別限制，相對於100質量份之 環氧樹脂用硬化劑，較好的早 罕乂好的疋0〜30質量份，更好的是 0.1〜10質量份。 對反應溫度、反應時間亦益g % p ^ J "、、符別限制，通常於5〜60。(：左 ^之溫度下使其反應(U〜72小時即可，尤其是使反應溫度 二45<： 1使&應時間為1〜24小時’由於存在後述之母 料型環氧樹脂用硬化劑組合物 切 < 保存穩定性可提高的傾 向，故而較好。 又’上述反應亦可視需要而於特定分散媒中進行。作為 / 刀散媒，可列舉：溶劑、塑化劑、樹脂類等。 作為上述溶劑’例如可列舉：苯、甲笨、二甲苯 '環己 院、礦油精、石腦油等和翻.系 4類，丙酮 '曱基乙基酮、曱基異 132805.doc •26- 200916496 丁基酮等酮類；乙酸乙 正丁酯、丙二醇單甲基 喊乙酸酯等酯類；曱醇、里 異丙％、正丁醇、丁基溶纖劑、 丁基卡必醇等醇類；水等。 作為上述塑化劑，例如可 w τ列舉.鄰苯二甲酸二丁酯、鄰 本一甲酸二(2_乙基己基)醋等鄰苯二甲酸二ι系；己二酸 - (2-乙基己基)醋等脂肪族二元酸I系；麟酸三甲 磷酸三酯系；聚乙二醇酯等二醇酯系等。 作為上述樹脂類，例如可列舉：聚矽氧樹脂類、環氧樹 脂類、酚樹脂類等。 又，亦可將環氧樹脂⑷）自身用作分散媒。於此情形 時’用於殼形成反應中之環氧樹脂（Α1)亦可為與後述之母 料型環氧樹脂用硬化劑組合物中之環氧樹脂（Α2)相同 氧樹脂。 又，上述咸（S)較好的是具有：吸收波數為ΐ63〇〜ΐ68〇 cm·1之紅外線的脲配位基（χ)、吸收波數為丨68〇〜丨η， 之紅外線的縮二脲配位基（y)、及吸收波數為〜 cm·丨之紅外線的胺基甲酸醋配位基⑻。其原因在於存在如 下傾向，可獲得後述之母料型環氧樹脂組合物的儲存穩定 性可提高，且針對機械剪力而具有較高之耐性的母料型環 氧樹脂用硬化劑組合物。 配位基（X)與縮二脲配位基（y)之吸收波長可使用傅立 葉變換式紅外分光光度計（亦稱作fT_ir)進行測定。 又，可使用顯微FT-IR來測定脲配位基（χ)、縮二脲配位 基（y)是否存在於殻（s)中。 132805.doc •27· 200916496 上述脲配位基（x)及上述縮二脲配位基⑺係藉由異氮酸 醋化合物與活性氫化合物之反應而生成之配位基。 於殼（s)中’相對於環氧樹脂用硬化劑，腺配位基⑻較 好的是具有1〜1_ meq/kg、更好的是1()〜则叫/kg之範 圍的濃度。 若脲配位基（x)之濃度在1叫/kg以上，則存在可獲得針 對機械剪力而具有較高耐性之母料型環氧樹脂用硬化劑組 合物之傾向；若在1000 meq/kg以下，則存在可獲得具有 優良硬化性的母料型環氧樹脂用硬化劑組合物之傾向。 於殼⑻中，相對於環氧樹脂用硬化劑，縮二脲配位基 (y)較好的是具有i〜i_ meq/kg、更好的是lG〜細咖他 之範圍的濃度。 若縮一脲配位基（y)之濃度在i meq/kg以上，則存在可獲 知·針對機械剪力而具有較高耐性之母料型環氧樹脂用硬化 劑組合物之傾向；若在1〇〇〇 meq/kg以下則存在可獲得-, aromatic diisoxan acid vinegar, low molecular triisosuccinic acid two different atmosphere:: and so on. Examples of the aliphatic diisocyanate include ethyl diisocyanate, diisocyanate, diisocyanate, diisocyanate, 6-hexane diacetate, and diisocyanate. Tridecyl hexane diester and the like. Examples of the alicyclic diisocyanate include isophorone diisocyanate 4,4-cyclohexylmethyl sulphide monoisocyanate S, thafuyuan diisocyanate, and 1'4-isocyanate group. Cyclohexene, 1,3 -bis(isocyanatemethyl)-cyclohexane, 1,3-bis(2-isocyanatepropyl-2-yl)-cyclohexane or the like. Examples of the aromatic diisocyanate include toluene diisocyanate, 4,4′·diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene-isochaic acid. The low molecular weight triisocyanate may, for example, be cerium-ytterbium triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, triisocyanato 1,3,6-hexanetriester, 2, An aliphatic triisocyanate compound such as 6-diisocyanate caproic acid-2-isocyanate group 5, 2,6-diisocyanate caproic acid-1-methyl-2-isocyanatoethyl ester, etc. Tricyclohexylmethane triisocyanate , Erhuan 132805.doc •23· 200916496 alicyclic triisocyanate compound such as heptane diisocyanate, triphenylcarbamate, isocyanide, bis(isocyanatosylphenyl)thiosulphonate g is an aromatic diisocyanate compound or the like. Examples of the polyisocyanate include polymethylene polyphenyl polyisophthalic acid vinegar or polyisocyanate derived from the above diisocyanate or low molecular triisocyanate. 'As a polylactic acid vinegar derived from the above-mentioned diisocyanate vinegar and triisocyanate s' can be listed as I: isocyanuric acid vinegar type polyisocyanate, biuret type polyisocyanate, amine group A An acid ester type polyisocyanate, an allophanate type polyisocyanate, a carbodiimide type polyisocyanate, etc. The above-mentioned various isocyanate compounds may be used alone or in combination as the above-mentioned active hydrogen compound, and examples thereof include water, a compound having one or more "grade and/or secondary amine groups in one molecule, A compound having one or more hydroxyl groups in one molecule is particularly excellent in hydrophobic water, in one thousand, and one or more hydroxyl groups. Examples of the compound having one or more of the above-mentioned and/or secondary amine groups in one molecule include an aliphatic group as an aliphatic amine, and examples thereof include an anthracene group and a fragrant aromatic amine. Amine, dibutylamine and the like alkylamine; ethylamine. methylamine, ethylamine, propylamine, butyl and other alkane-face. „monoamine, propylenediamine, butanediamine, hexamethylenediamine, amine Ethylene triamine, trioxane A, tepto-tetramine, tetra-amethylene pentamine, etc.; polyoxypropylene diamine, octagonal, etc. 聚 Ethylene diamine and other polyoxyalkylene polyamines Examples of the alicyclic amine include cyclopropylamine, cyclobutylamine, cyclopentane 132805.doc-24-200916496 amine, cyclohexylamine, isophoronediamine, etc. Examples of the aromatic amine include aniline. Toluidine, amide, naphthylamine, diaminodiphenylmethane, diaminodiphenyl stone, etc. As a compound which has an ancient _ /, more than one hydroxyl group in one molecule, an alcohol compound is mentioned Or a compound, etc. As the alcohol compound, for example, a. A., propylene glycol, butanol, pentanol, hexanol, heptanol, octanoic acid _.. octyl, decyl alcohol, decyl alcohol, ten- Alkanol, lauryl drunk, dodecanol, stearyl alcohol, _ decadecanol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, y sterol cinnamyl alcohol, ethylene glycol Monoterpene ether Ethylene glycol monoethyl ether, ethylene glycol monoethyl _, hexa-ol alcohol, etc. monohydric alcohol, ethylene glycol, polyethylene glycol, _ ^ propanol, polypropylene glycol, 1,3-butanediol , 1,4-butanol, hydrogenated bis, a, ία γ, neopentyl alcohol, glycerol, trimethylpropane, pentaerythritol, etc., and one by one molecule The above-mentioned lacquer-based compound is obtained by reacting a compound having one or more hydroxy groups, % ^ " earth carboxyl group, primary or secondary amine group, fluorenyl group in one molecule, and is further provided in one molecule. The compounds of two or more secondary hydroxyl groups are also exemplified as polyols. The alcohol compounds may also be any of the first ', the first or the second alcohol. As the phenolic compound, for example, barium, carbolic acid, Phenol, xylene, carvacrol, thymol, quinone phenol, early phenols; catechol, m-benzene phenol, hydroquinone, bisphenol oxime, phenol phenol F , such as phloroglucinol, etc. As a compound having one or more hydroxyl groups in one molecule, Cloth to read the class or the like divergent, more preferably polyhydric alcohol. 132805.doc -25- 200916496 The active hydrogen compound described above is used alone, and it is also possible to use two or more sandals. The capsule type ring-shaped full-coating agent for the cerium lanthanum lanthanum can be produced by any one of the methods of the present invention. For example, the above-mentioned ring-shaped hardening agent, the isocyanate compound, and the active hydrogen compound can be added. The resin (Α1) is mixed and reacted to produce. The amount of the compound of the squirrel Sa is not particularly limited to 丨 丨 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 热 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂More preferably, it is 3 to 20 parts by mass. The amount of the active hydrogen compound is not limited, and is preferably 〇0 to 1 〇 by mass, more preferably 〇.5~, relative to 100 parts by mass of the hardener for the epoxy resin. 5 parts by mass. The amount of epoxy resin (A 1 ) is particularly limited to pp ", and is particularly limited. It is preferably from 0 to 30 parts by mass, preferably from 0 to 30 parts by mass, relative to 100 parts by mass of the hardener for epoxy resin. It is 0.1 to 10 parts by mass. The reaction temperature and reaction time are also limited to g % p ^ J ", and the tolerance is usually 5 to 60. (: The reaction is carried out at the temperature of the left ^ (U ~ 72 hours, especially the reaction temperature of 2 45 <: 1 and & should be 1 to 24 hours) due to the presence of the masterbatch type epoxy resin described later It is preferable that the curing agent composition is cut and the storage stability is improved. Further, the above reaction may be carried out in a specific dispersion medium as needed. Examples of the solvent include a solvent, a plasticizer, and a resin. As the above-mentioned solvent, for example, benzene, methyl bromide, xylene, cyclohexyl, mineral spirits, naphtha, etc., and turmeric type 4, acetone 'mercaptoethyl ketone, fluorenyl 132805 .doc •26- 200916496 Ketones such as butyl ketone; esters such as ethyl n-butyl acetate, propylene glycol monomethyl ketone acetate; sterol, isopropylidene, n-butanol, butyl cellosolve, butyl card Alcohols such as alcohol; water, etc. As the plasticizer, for example, dibutyl phthalate or phthalic acid di-(2-ethylhexyl) vinegar can be used. Aliphatic acid-dicarboxylic acid, such as adipic acid-(2-ethylhexyl) vinegar; tribasic acid triglyceride; polyethylene glycol ester Examples of the above-mentioned resins include polyfluorene resins, epoxy resins, phenol resins, etc. Further, the epoxy resin (4)) itself can be used as a dispersion medium. The epoxy resin (Α1) used in the shell formation reaction may be the same oxygen resin as the epoxy resin (Α2) in the hardener composition for a master batch type epoxy resin to be described later. It is preferred to have a urea ligand having an infrared ray having an absorption wave number of ΐ63〇~ΐ68〇cm·1, and a diuret ligand having an absorption wave number of 丨68〇~丨η. (y) and the amino carboxylic acid valence ligand (8) having an infrared ray having an absorption wave number of ～cm·丨. The reason for this is that the storage stability of the master batch type epoxy resin composition to be described later can be improved. And a hardener composition for a master batch type epoxy resin having high resistance to mechanical shear. The absorption wavelength of the ligand (X) and the biuret ligand (y) can be Fourier transform infrared Spectrophotometer (also known as fT_ir) for measurement. Also, microscopic FT-IR can be used for measurement. Whether the urea ligand (χ) and the biuret ligand (y) are present in the shell (s) 132805.doc •27· 200916496 The above urea ligand (x) and the above biuret ligand (7) A ligand formed by the reaction of an isophthalic acid vinegar compound with an active hydrogen compound. In the shell (s), the adenine ligand (8) preferably has a 1-1 relative to the epoxy resin hardener. Meq/kg, more preferably 1 () ~ is called / kg range concentration. If the urea ligand (x) concentration is above 1 / kg, there is a higher available for mechanical shear The tendency of the hardener composition for a masterbatch type epoxy resin which is resistant; when it is 1000 meq/kg or less, the master batch type epoxy resin hardener composition which has excellent hardening property tends to be obtained. In the shell (8), the biuret ligand (y) is preferably a concentration of i~i_ meq/kg, more preferably in the range of lG to fine coffee, relative to the hardener for epoxy resin. When the concentration of the monourea ligand (y) is at least iq/kg, there is a tendency to obtain a masterbatch type epoxy resin hardener composition which is highly resistant to mechanical shearing force; Available below 1〇〇〇meq/kg

具有優良硬化性的母料型環氧樹脂用硬化劑組合物之傾 向。 進而，於殼（S)中，除了上述配位基（4及配位基⑺以 外，較好的是具有吸收波數為173〇〜1755 cm—!之紅外線的 胺基甲駄S曰配位基（z)。配位基（z)之吸收波長可使用FT_ir 進行測定，且可使用顯微ft_ir來測定配位基（z)是否存在 於殼（S)中。 上述胺基甲酸醋配位基係藉由異氰酸酯化合物與於1 分子中具有一個以上羥基的化合物之反應而生成之配位 132805.doc -28· 200916496 基。 於上述殼⑻中，相對於環氧樹赌用硬化劑，胺基尹酸 醋配位基⑷較好的是具有卜細、更好的是5〜觸 meq/kg之範圍的濃度。 若胺基甲酸酯配位基㈡之濃度在i meq/kg以上，則存在 可獲得針對機械剪力而具有較高耐性之母料型環氧樹脂用 硬化劑組合物之傾向；若在細以下，則存在可獲 得具有優良硬化性的母料型環氧樹脂用硬化劑組合物之傾 向。 脲配位基（X)、縮二脲配位基（y)及胺基甲酸酯配位基（Z) 之濃度可藉由公知方法來測定，例如可應用上述專利文獻 1(曰本專利特開平卜705?]號公報）中所揭示之方法。 將形成本實施形態之環氧樹脂用硬化劑的微粒子即核 (c)加以包覆之殼（s)之厚度較好的是平均層厚為5〜丨 πm ’更好的是5〇〜7〇〇 nm。 右设（S)之平均層厚在5 nm以上，則存在可獲得優良健 存穩疋性之傾向；若在1000 nm以下，則存在可獲得在實 用上充分之硬化性之傾向。 殼（S)之厚度可藉由穿透式電子顯微鏡進行測定。再 者’先前-般認為，殼之厚度越厚’通常儲存穩定性越增 加’另-方面硬化性越降低。然而，使用本實施形態之環 氧樹脂用硬化劑來形成核時，確認即使殼之厚度增厚，亦 可抑硬化性之降低。 (母料型環氧樹脂用硬化劑組合物） 132805.doc •29- 200916496 本實施形態之母料刑 衣氧樹脂用硬化劑組合物係將上述 環氧樹脂用硬化劑及/或微膝囊型環氧樹脂用硬化劑中之 至少一種分散於環氧樹脂(Α2)中而成之組合物。 作為上述環氧樹脂（Α2)，可應用與上述環氧樹脂⑷）中 所例不者相同之環氧樹脂。 尤其為了可提高使用母料型環氧樹脂料化劑組合物而 成之調配物的硬化性，較好的是將雙盼Α、雙射加以縮水 甘油化而成之雙_環氧樹脂；將二μ基萘、二經基苯加 以縮水甘油化而成之規急掛 虱樹知。該專樹脂可單獨使用，亦 可併用兩種以上。 體 的 上 向 向 相對於本實施形態之母料型環氧樹脂用硬化劑組合物整 ，上述環氧樹脂（A2)之含量較好的是1〇〜9〇f量％，更好 是5〇〜85質量％。若環氧樹脂(A2)之含量❹質”。以 ’則存在組合物之黏度適度降低，作業性可提高之傾 ，若在90質量％以下’則存在可獲得優良硬化性之傾 相對於本只把形態之母料型環氧樹脂用組合物整 體’環氧樹脂用硬化劑及/或微膠囊型環氧樹脂用硬化： ,含量較好的是H)〜90質量％，更好的是15~5〇質量。心若 :氧樹脂用硬化劑及/或微膠囊型環氧樹脂用硬化劑之： 夏在10質量％以上’則存在可獲得優良硬化性之傾向，= 在9〇質量％以下，則存在硬化物之财熱性優良之傾向右 作為製造本實施形態之母料型環氧樹脂用硬化劑 的方法，可列舉：例如使用三報研磨機等，使上述料 132805.doc •30· 200916496 脂用硬化劑及/或㈣囊型環氧樹㈣硬化劑 樹脂（A2)中之方法；或將環氧樹脂（A2)作為分散媒而=氧 環氧樹脂用硬化劑之包覆反應’獲得微膠囊型環氧仃 硬，劑之同時，獲得母料型環氧樹脂用硬化劑組合物= 法等。尤其是後者方法存在生產性可提高之傾向 好。 吨孝父 本實施开之母料型環氧樹脂用硬化劑組合物係由環 樹脂用硬化劑及/或微膠囊型環氧樹脂用硬化劑與環： 脂（A2)所構成，亦可於不損及本發明之效果的範圍内含有 其他成分。於此情形時，相料組合物整體，其他成分之 含量較好的是未滿3〇質量％。 作為可於母料型環氧樹脂用硬化劑組合物中所含有之其 他成刀{列如可列舉：增量劑、增強劑、填充劑、導電微 粒子、顏料、有機㈣彳、反應性稀釋劑、非反應性稀釋 劑' 樹脂類、結晶性醇、偶合劑等。 作為增量劑，例如可列舉：碳酸鈣、氧化鋅、黏土、滑 石一氧化鈦、二氧化矽等無機填充料，或聚酯樹脂、聚 胺基甲S“日树脂、丙烯酸系樹脂、聚醚樹脂、三聚氰胺樹 月曰或胺基甲馱ga改性環氧樹脂、橡膠改性環氧樹脂、醇酸 改性環氧樹脂等改性環氧樹脂等之塑膠微粒子。 π為1強劑，可列舉：玻璃纖維、石棉纖維、硼纖維、 & H ^化1呂纖維、碳化石夕纖維、陶究纖維、聚I纖 維、聚醯胺纖維、芳族聚醯胺纖維、纖維素、石英粉、礦 物I·生矽馱鹽、雲母、石棉粉、板岩粉、高嶺土、氧化鋁三 132805.doc -31 · 200916496 水合物、氫氧化鋁、白堊粉、石膏、碳酸鈣、三氧化二 銻、氣化聚趟（PENTON)、二氧化石夕、二氧化鈦、碳黑、 石墨、碳奈米管、富勒烯、氧化鐵等。 作為填充劑，例如可列舉··煤焦油、玻璃纖維、石棉纖 維、硼纖維、碳纖維、纖維素、聚乙烯粉、聚丙烯粉、石 英粉、礦物性矽酸鹽、雲母、石棉粉、板岩粉、高嶺土、 氧化鋁二水合物、氫氧化鋁、白堊粉、石膏、碳酸鈣、三The orientation of the hardener composition for a masterbatch type epoxy resin having excellent hardenability. Further, in the shell (S), in addition to the above ligand (4 and the ligand (7), it is preferred to have an amine group of the infrared group having an absorption wave number of 173 Å to 1755 cm. Base (z). The absorption wavelength of the ligand (z) can be determined using FT_ir, and the microscopic ft_ir can be used to determine whether the ligand (z) is present in the shell (S). The base is a complex formed by the reaction of an isocyanate compound with a compound having one or more hydroxyl groups in one molecule. 132805.doc -28· 200916496. In the above shell (8), an amine relative to an epoxy smelt hardener The base acid vinegar ligand (4) is preferably a concentration which is finer, more preferably in the range of 5 to meq/kg. If the concentration of the urethane ligand (2) is above i meq/kg, There is a tendency that a masterbatch type epoxy resin hardener composition having high resistance to mechanical shearing force can be obtained; if it is finer or less, there is a hardening of a master batch type epoxy resin which can obtain excellent hardenability. The tendency of the composition. Urea ligand (X), biuret ligand (y) and amide formic acid The concentration of the ligand (Z) can be measured by a known method, and for example, the method disclosed in the above-mentioned Patent Document 1 (Japanese Patent Laid-Open No. 705--------- The thickness of the shell (s) coated with the fine particles of the hardener for the resin, that is, the core (c) is preferably an average layer thickness of 5 to 丨πm', more preferably 5 〇 to 7 〇〇 nm. When the average layer thickness is 5 nm or more, there is a tendency to obtain excellent storage stability; if it is 1000 nm or less, there is a tendency to obtain practically sufficient hardenability. The thickness of the shell (S) may be The measurement was carried out by a transmission electron microscope. In addition, it is considered that the thicker the thickness of the shell is, the more the storage stability is increased, and the hardening property is further lowered. However, the epoxy resin of the present embodiment is used. When a hardener is used to form a core, it is confirmed that even if the thickness of the shell is increased, the hardenability can be lowered. (Masterbatch type epoxy resin hardener composition) 132805.doc • 29- 200916496 The parental punishment of this embodiment The epoxy resin hardener composition is the above epoxy tree A composition obtained by dispersing at least one of a hardener and/or a hardener for a micro-kappa-type epoxy resin in an epoxy resin (Α2). As the above epoxy resin (Α2), the epoxy resin described above can be used. The epoxy resin which is not the same as the resin (4)). In particular, in order to improve the hardenability of the formulation obtained by using the master batch type epoxy resin materializing agent composition, it is preferred to use a double-epoxy resin obtained by glycidylation of double-injection and double-shot; It is known that the bis-naphthyl and naphthylbenzenes are glycidylated. The resin may be used singly or in combination of two or more. The upward direction of the body is the same as that of the master batch type epoxy resin hardener composition of the present embodiment, and the content of the epoxy resin (A2) is preferably 1% to 9% by weight, more preferably 5 parts by weight. 〇 ~85 mass%. If the content of the epoxy resin (A2) is ruthenium, "the viscosity of the composition is appropriately lowered, and the workability can be improved. If it is 90% by mass or less", there is a tendency to obtain excellent hardenability relative to the present. Only the composition of the masterbatch type epoxy resin as a whole is hardened with a hardener for epoxy resin and/or a microcapsule type epoxy resin: the content is preferably H) to 90% by mass, more preferably 15~5〇 quality. Xin Ruo: Hardener for oxygen resin and/or hardener for microcapsule epoxy resin: Summer at 10% by mass or more, there is a tendency to obtain excellent hardenability, = 9 mass % or less, the cured product is excellent in the heat of the cured material. The method of producing the hardener for the master batch type epoxy resin of the present embodiment is, for example, using a three-stage polishing machine or the like to make the above material 132805.doc • 30· 200916496 Hardener and/or (4) encapsulated epoxy tree (4) hardener resin (A2); or epoxy resin (A2) as dispersion medium = epoxy resin hardener The reaction 'obtains the microcapsule type epoxy oxime hard, while obtaining Masterbatch type epoxy resin hardener composition = method, etc. In particular, the latter method has a tendency to improve productivity. Tons of the father's masterbatch type epoxy resin hardener composition is a ring resin. It is composed of a hardener and/or a microcapsule-type epoxy resin hardener and a ring: fat (A2), and may contain other components within a range that does not impair the effects of the present invention. In this case, a combination of materials The content of the other components is preferably less than 3% by mass. The other forming tools which can be contained in the hardener composition for the master batch type epoxy resin are listed as: Agent, filler, conductive fine particles, pigment, organic (tetra) hydrazine, reactive diluent, non-reactive diluent 'resin, crystalline alcohol, coupling agent, etc. Examples of the extender include calcium carbonate and zinc oxide. , clay, talc, titanium oxide, cerium oxide and other inorganic fillers, or polyester resin, polyamine-based S "daily resin, acrylic resin, polyether resin, melamine tree guanidine or aminomethyl hydrazine ga modified Epoxy resin, rubber modification Plastic microparticles such as epoxy resin, alkyd modified epoxy resin and other modified epoxy resins. π is a strong agent, which can be exemplified by glass fiber, asbestos fiber, boron fiber, & H ^1 1 Lu fiber, carbonized stone fiber, ceramic fiber, poly I fiber, polyamide fiber, aromatic polyamine Fiber, cellulose, quartz powder, mineral I·salt salt, mica, asbestos powder, slate powder, kaolin, alumina III 132805.doc -31 · 200916496 hydrate, aluminum hydroxide, chalk powder, gypsum, carbonic acid Calcium, antimony trioxide, gasified polyfluorene (PENTON), dioxide dioxide, titanium dioxide, carbon black, graphite, carbon nanotubes, fullerenes, iron oxide, and the like. Examples of the filler include coal tar, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral citrate, mica, asbestos powder, and slate. Powder, kaolin, alumina dihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, three

氧化一銻、氣化聚醚、二氧化矽、氣溶膠、鋅鋇白、重晶 石、一虱化鈦、碳黑、石墨、碳奈米管、富勒烯、氧化 线金銀紹杯、鐵粉、奈米級之金屬結晶、金屬間化 合物等’該等均可根據母料型環氧樹脂用硬化劑組合物之 用途而有效使用。 微粒子，係藉由機械粉碎法、化學還原法、電 解法冑化法中之任—種方法而獲得之金屬粒子，可列 +銀金、翻、把等責金屬粒子，銅、銅合金、錄、 鐵、銘等非貴金屬知4 … 、'广，銀_銅合金、銀-鈀合金、銀-錫合 金銀-鋅合金、銀-錄入a 、0金、銀-鎳合金等銀合金。 作為顏料’可列舉：φ 一 銘酸銘、二氧化鈦、碳 ：4 土、奴酸鈣、氧化路、 酮基W娘瑞：、：機顏料，州_、[二 陰丹士林、-Η黃、異《相、酞菁、 一 7秦4有機顏料。 作為有機溶劑，例如 酮、甲基異丁基網、乙酸〜甲本-甲本、甲基乙基 作為反應性稀釋劑，例Λ；乙酸丁醋等。 例如可列舉：丁基縮水甘油醚、 132805.doc -32· 200916496 N，N'-縮水甘油基鄰曱笨胺 烯 '乙二醇二縮水甘油_ 二醇二縮水甘油醚等。 笨基縮水甘油醚、氧化笨乙 丙一酵二縮水甘油謎、1,6-己 作為非反應性稀釋#丨，, 邵釋知丨例如可列舉：鄰苯二甲酸二辛 酯'鄰苯二甲酸二丁酯、P_ 己一酸一辛酯、石油系溶劑等。 作為樹知類’例如可列舉：聚醋樹脂、聚胺基曱酸輯樹 脂、丙烯酸系樹脂、聚_脂、三聚氰胺樹脂或胺基甲酸 醋改性環氧樹脂、橡膠改性環氧樹脂、醇酸改性環氧樹脂 等改性環氧樹脂等。 作為結晶性醇，例如可列舉：U2_環己二醇、^-環己 一醇、1，4_環己二醇、季戊四醇、山梨糖醇、蔗糖、三羥 曱基丙烷等。 作為偶合劑，例如可列舉：甲基三甲氧基料、苯基三 乙氧基矽烷、3-縮水甘油氧基丙基曱基二乙氧基矽烷、3_ 胺基丙基三甲氧基石夕烧、N•苯基_3_胺基丙基甲氧基石夕烧 等矽烷偶合劑等。 (單成分性調配組合物） 本實施形態之單成分性調配組合物係於環氧樹脂（A 3)中 混合上述母料型環氧樹脂用硬化㈣合物而叙組合物。 作為上述環氧樹脂（A3)，可制與上述環氧樹脂（ai)中 所例示者相同之環氧樹脂。 母料型環氧樹脂用硬化劑組合物與環氧樹月旨⑽之混合 =係考慮硬化性或硬化物特性而進行確定。相對於1〇〇質 里伤之被氧樹脂（A3)，母料型環氧樹脂用硬化劑組合物較 132805.doc -33- 200916496 :的疋1〜200質量份，更好的是ι〇〜ι〇〇質量份，進而好的 :20 80質里份。若母料型環氧樹脂用硬化劑組合物之含 里在1質量份以上，則存在可獲得在實用上充分之硬化 性，若在200質量份以了，則存在環氧樹脂用硬化劑不會 为布不均’獲得平衡性良好之硬化性之傾向。 本實把㈣之單成分性調配組合物亦可視需要而含有選 自酸肝類@類、醯肼類及胍類巾之至少—種其他硬化 劑。 作為酸酐類，例如可列舉：鄰苯二甲酸酐、偏笨三酸 酐、均苯四曱酸酐、六氫鄰苯二曱酸酐、四氫鄰笨二曱酸 酐、3-氯鄰苯二甲酸酐、4'氣鄰苯二甲酸酐、二苯甲酮四 曱酸酐、丁二酸酐、甲基丁二酸酐、二曱基丁二酸酐、二 氣丁一酸酐、曱基耐地酸酐、十二烷基丁二酸酐、氣菌酸 肝、順丁烯二酸酐等。 作為酚類，例如可列舉：苯酚酚醛清漆、甲酚酚醛清 漆、雙酚A酚醛清漆等。 作為醯肼類，例如可列舉：丁二酸二醯肼、己二酸二醯 肼鄰本一甲酸_醯肼、間笨二曱酸二醯肼、對苯二曱酸 二醯肼、對羥基苯甲酸醢肼、水楊酸醯肼、苯基胺基丙酸 酿肼、順丁烯二酸二醯肼等。 作為胍類，例如可列舉：二氰二胺、曱基胍、乙基胍、 丙基胍、丁基胍、二曱基胍、三曱基胍、苯基胍、二苯基 脈、甲笨曱醯胍等。 作為上述其他硬化劑的具體例，可使用以四氫鄰苯二曱 132805.doc 34- 200916496 酸酐為主成分之HN-2200(曰立化成工業（股）製造）等。再 者，本實施形態中所謂「主成分」，係指特定成分於基質 成分中所占之比例較好的是50質量％以上，更好的是7〇質 量％以上，亦包括100質量。/。之情形。 相對於本實施形怨之單成分性調配组合物整體，上述其 他硬化劑之含量較好的是(^丨〜妁質量％，更好的是丨〜”質 量％。若上述其他硬化劑的含量在1質量％以上，則存在獲 得優良硬化性之傾向；若在9〇質量％以下’則存在硬化物 之Tg增高，故而耐熱性可提高之傾向。 本實施形態之單成分性調配組合物中，亦可視需要而包 含增量劑、增強劑、填充劑、導電微粒子、顏料、有機溶 劑、反應性稀釋劑、韭Θ u ^ 非反應性稀釋劑、樹脂類、結晶性 醇、偶合劑等其他添加劑或添加成分。 作為增量劑，例如可列舉：碳酸舞、氧化鋅、黏土、滑 石、二氧化鈦、二氧化石夕等無機填充料，或 胺基甲酿护搞I·押 相'月日 ^ 版基甲W樹月曰、丙婦酸系樹脂、聚麵 脂或胺基甲酸酯改性環氧槲# 一聚氰胺枒 改性環㈣Μ 改性環氧樹脂、醇酸 ^ 9改性環氧樹脂等之塑膠微粒子。 作為增強劑，可列與.& β t 山址 T J舉.玻璃纖維、石棉纖維、硼㈣Oxidation monomethane, vaporized polyether, cerium oxide, aerosol, zinc lanthanum, barite, titanium hydride, carbon black, graphite, carbon nanotubes, fullerenes, oxidized gold and silver cups, iron Powder, nano metal crystals, intermetallic compounds, etc. can be effectively used depending on the use of the masterbatch type epoxy resin hardener composition. The microparticles are metal particles obtained by any of the mechanical pulverization method, the chemical reduction method, and the electrolytic smelting method, and can be listed as + silver gold, turned, and the like, metal particles, copper, copper alloy, recorded Non-precious metals such as iron, iron, etc. 4, 'Guang, silver_copper alloy, silver-palladium alloy, silver-tin alloy silver-zinc alloy, silver-into silver alloy such as a, 0 gold, silver-nickel alloy. As a pigment, it can be exemplified by: φ 一铭酸铭, titanium dioxide, carbon: 4 earth, calcium citrate, oxidation road, ketone W Niangrui:: machine pigment, state _, [two yin danslin, - Η yellow , different "phase, turnip, a 7 Qin 4 organic pigments. As the organic solvent, for example, a ketone, a methyl isobutyl network, an acetic acid ~ a methyl group - a methyl group, a methyl ethyl group as a reactive diluent, for example, a butyl acetate or the like. For example, butyl glycidyl ether, 132805.doc-32·200916496 N, N'-glycidyl o-nonylaminol 'ethylene glycol diglycidyl diol diol diglycidyl ether, etc. are mentioned. Stupid glycidyl ether, oxidized stupid ethylene-propanoid diglycidide mystery, 1,6-hex as a non-reactive dilution #丨,, 邵释知丨, for example, dioctyl phthalate 'phthalic acid II Butyl ester, P_hexamic acid monooctyl ester, petroleum solvent, and the like. Examples of the tree are as follows: a polyester resin, a polyamine phthalic acid resin, an acrylic resin, a poly-lipid, a melamine resin or a urethane modified epoxy resin, a rubber-modified epoxy resin, and an alcohol. Modified epoxy resin such as acid-modified epoxy resin. Examples of the crystalline alcohol include U2_cyclohexanediol, ?-cyclohexanol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, trihydroxypyridylpropane, and the like. Examples of the coupling agent include methyltrimethoxylate, phenyltriethoxydecane, 3-glycidoxypropylmercaptodiethoxydecane, and 3-aminopropyltrimethoxyxanthine. A decane coupling agent such as N•phenyl_3_aminopropyl methoxy oxysulphate or the like. (Single-component compounding composition) The one-component compounding composition of the present embodiment is a composition obtained by mixing the above-mentioned masterbatch type epoxy resin hardening (tetra) compound in an epoxy resin (A3). As the epoxy resin (A3), an epoxy resin similar to that exemplified in the above epoxy resin (ai) can be obtained. The mixture of the hardener composition for the master batch type epoxy resin and the epoxy resin (10) is determined in consideration of the curability or the properties of the cured product. Compared with the epoxy resin (A3) which is damaged by 1 enamel, the hardener composition for the master batch type epoxy resin is more than 1 to 200 parts by mass of 132805.doc -33-200916496: more preferably ι〇 ~ ι 〇〇 mass, and then good: 20 80 quality. When the content of the hardener composition for the master batch type epoxy resin is 1 part by mass or more, practically sufficient hardenability can be obtained, and if it is 200 parts by mass, the hardener for epoxy resin is not present. It will be a tendency to obtain a well-balanced hardenability for uneven cloth. The one-component compounding composition of (4) may also contain at least one other hardener selected from the group consisting of acid livers, scorpions and scorpion towels, as needed. Examples of the acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and 3-chlorophthalic anhydride. 4' gas phthalic anhydride, benzophenone tetraphthalic anhydride, succinic anhydride, methyl succinic anhydride, dimercaptosuccinic anhydride, di-succinic anhydride, mercapto-resistance, dodecyl Succinic anhydride, gas bacteria liver, maleic anhydride, and the like. Examples of the phenols include phenol novolac, cresol novolac, and bisphenol A novolac. Examples of the hydrazines include diterpene succinate, diammonium adipate-formic acid hydrazine, diammonium dihydrazide, diterpene terephthalate, p-hydroxyl Bismuth benzoate, strontium salicylate, phenylaminopropionic acid bismuth, diammonium maleate, and the like. Examples of the hydrazines include dicyandiamide, decyl hydrazine, ethyl hydrazine, propyl hydrazine, butyl hydrazine, dimercapto fluorene, trimethyl hydrazine, phenyl hydrazine, diphenyl vein, and stupid. Hey. As a specific example of the above-mentioned other hardening agent, HN-2200 (manufactured by Toray Chemical Industries Co., Ltd.) containing tetrahydrophthalic phthalocyanine 132805.doc 34-200916496 anhydride as a main component can be used. In the present embodiment, the term "main component" means that the proportion of the specific component in the matrix component is preferably 50% by mass or more, more preferably 7% by mass or more, and 100% by mass. /. The situation. The content of the above other hardeners is preferably (% 丨 妁 妁 mass %, more preferably 丨 〜 质量 % by mass) with respect to the single component composition of the present invention. When the amount is 1% by mass or more, the curing property tends to be excellent, and when it is 9% by mass or less, the Tg of the cured product increases, and the heat resistance tends to be improved. The one-component compounding composition of the present embodiment is preferable. Also, if necessary, extenders, reinforcing agents, fillers, conductive fine particles, pigments, organic solvents, reactive diluents, 韭Θ u ^ non-reactive diluents, resins, crystalline alcohols, coupling agents, etc. Additives or added components. As the extender, for example, an inorganic filler such as carbonic acid dance, zinc oxide, clay, talc, titanium dioxide, or sulphur dioxide, or an amine-based stalker I. Version of the base of the company W tree 曰 曰, propyl acrylate resin, poly-fat or urethane modified epoxy 槲 # melamine 桠 modified ring (four) 改性 modified epoxy resin, alkyd ^ 9 modified Plastic resin such as epoxy resin Sub as the reinforcing agent, it can be listed with &. Β t T J Hill address held glass fibers, asbestos fibers, boron (iv).

奴纖維、氧化_維、碳切纖維、:I 維、聚醯胺_绝 写无纖維、聚酯纖 胺纖、准、芳族聚醯 物性石夕酸鹽、雲母、石棉粉、板岩粉纖=土石英粉 '礙 水合物、氫氧化叙、白昼粉、石膏Γ 氧化銘三 録、氯化聚H 膏、碳_、三氧化二 喊一乳化石夕、二氧化鈦、碳黑、石墨 132805.doc •35· 200916496 米官、富勒烯、氧化鐵等。 作為填充劑，例如可 維、，、碳纖維、纖維素璃 央叔、礦物性矽酸鹽 石 氧化鋁_ k人仏 石棉私、板岩粉、高嶺土、 減銘二水合物、氫氧化銘 氧化二録、氣化聚麵、二氣广如、石膏、三 石'二氧化鈦、石炭里Γ石黑夕、氣溶谬、辞钥白、重晶 鐵、金、銀, i、碳奈米管、富勒烯、氧化 ^ 銀、鋁粉、鐵龄、太 合物等。 π未級之金屬結晶、金屬間化 作為導電微粒子，#鹑 ^ 猎由機械粉碎法、化學還原法、電 解法、霧化法中之任Hu ^ ^ 舉：銀、 法而獲得之金屬粒子，可列 鐵、銘等非責金屬也早；屬粒子，銅、銅合金、錄、 金、銀-鋅Λ 鋼合金、銀妨金、銀-锡合 作σ ’、銀-鎮合金、銀-鎳合金等銀合金。 作為顏料，可列與· 銘酸姑、二氧化1:高嶺土、碳㈣、氧化鉻、 酮基吡咯幷 碳黑等無機顏料，喹吖啶酮、茈、二 陰丹士林、…：㈣、啥琳黃、異物酮、献菁、 杯一 $嗪等有機顏料。 作為有機溶劑，例如可 + _ 酮、甲基異丁其_、 +本—甲笨、甲基乙基 、土 、乙酸乙酯、乙酸丁酯等。 作為反應性稀釋劑 如5列中.丁基縮水甘油醚' Κ甘油基鄰甲笑 — 煉 、本基縮水甘油醚、氧化苯乙 烯乙二醇乳 二醇二縮水甘油喊等。@-醇-縮水甘油_、1，己 132805.doc -36 - 200916496 作為非反應性稀七， 醋、鄰苯二甲酸二丁劑’例如可㈣：鄰苯二甲酸二辛 作為樹脂類，例二二二酸：辛醋、石油系溶劑等。 可列舉.聚酯樹脂、聚胺基甲酸酯樹 月曰、丙烯酸樹脂、¥ 1 改性^ μ ,峻樹月曰、三聚氰胺樹脂或胺基甲酸酯 ?文f生ί衣氣樹脂、橡腹 >文性％氧樹脂、醇酸改性環氧樹脂等 改性環氧樹脂等。 j刊辦舶寻 作為結晶性醇，办丨 〇可列舉：工，2-環己二醇、1，3-環己 一醇、1，4-壤己二醇、 甲基丙烧。 $戊四龄、山梨糖醇、蔗糖、三經 作為偶合劑，例如 舉.甲基二甲氧基石夕炫、苯基三 土矽烷、3:縮水甘油氧基丙基甲基二乙氧基矽烷、3· 等二二二甲氧基⑪燒、Nm胺基丙基甲氧基石夕烧 4矽烷偶合劑等。 Θ相對於早成分性調配組合物整體，較好的是於0.1〜90質 、更好的是1〜85f量％之範圍内包含上述其他添加劑 或加成分。 本實施形態之單成分性調配組合物例如可用作黏接劑、 接合用糊料、接合描 _ , _ ^ 膜、異向導電性材料、導電性材料、 絕緣材料、密封材、塗佈材、塗料組合物、預浸料、执傳 導性材料等’尤其是耐溶劑性及耐機械剪力性優良，故而 尤其可用作密封材料、異向導電性材料。 上述黏接劑、接合用糊料、及接合用料㈣液狀黏接 劑、騰狀黏接劑、及點B | ,JL. ^ 及黏日日材專。作為膜狀黏接劑之製造方 f例如可使用日本專利特開昭62_141〇83號、或曰本專 132805.doc -37- 200916496 利特開平05-295329號等中所記载 秋<万法。具體而言，贺 備使固形環氧樹脂、液狀環氧樹 ^ t 曰進而固形胺基甲酸酯 樹月日以成為50質量％之方式溶解..、曰 鮮此合.分散於甲笨中而成 之溶液。製備於該溶液中添加. 能夕抑士、 刀刀政30質量％之本實施形 早成》性調配組合物而成之清漆。將該清漆例如塗佈 於厚度為50 μπι之剝離用聚對笨二甲酸乙二醋基材上以 使將甲苯乾燥後厚度成為3〇 由使曱苯乾燥，獲得 於吊溫下為惰性、且與由力勒 月藉由加熱而由潛在性硬化劑之作用來 發揮黏接性之接合用薄膜。 作為異向導電性材料，例 播_ J列舉異向導電性膜、異向 導電性糊料等，作為導雷性# 导生材枓’例如可列舉導電性膜、 導電性糊料等。該等材料例 j如了猎由曰本專利特開平〇1_ Π 3 4 8 0號中所記載之方法夹制1 戰万忐來衣造。例如可藉由下述方式來 在上述接°用膜之製造中，製備清漆時將導電性材 ^或異向導電性材料混合.分散，塗佈於㈣ 實施乾燥。 作為上述導電性材料或異向導電性材料即導電粒子，可 使用：焊錫粒子、链4 凰h .....不米級之金屬結晶 '以其他金 ,y 子、銅與銀之傾斜粒子等金屬粒子， 或例如以金、錄、相 . pt ^ 八 銅、焊錫等導電性薄膜對苯乙烯樹 月曰 '胺基甲酸酯樹脂、二枣 ._ —私氘胺知知、％氧樹脂、丙烯酸 糸树脂、酚樹脂、贫 黄A 乙烯-丁二烯樹脂等樹脂粒子加以包 姑1又而s，導電粒子係1〜20 μιη左右之 求形微粒子。作為葡+ ’、成膜枯之基材，例如可使用聚酯、聚 132805.doc -38- 200916496 乙烯、聚醯亞胺、聚四氟乙烯等。 作為絕緣材料，可列與g * 絕緣黏接臈可使用上^人、絕緣黏接糊料等。 使用上述接合用膜而獲得。又， 封材料以外，藓由嚿艰μ、+、比 除了使用密 曰D周配上述填充劑中的絕緣性填右南 得絕緣黏接糊料。 、y而獲 等密2可用作固形密封材、液狀密封材、膜狀密封材 =i狀密封材可用作底部填充材、灌注材、壩材等。作 口何之^方法，例如可應用日本專利特開平s 43661號、日本專利特開2隊226675料中記載 電子零件之密封.含浸用成形材料的製造方法之方法f更 具體而言’係藉由添加雙紛A型環氧樹脂、作為硬化劑例 ，酸酐硬化劑的甲基六氫鄰苯二甲酸野、進而球狀炼融二 ?化矽粉末，加以均勻地混合，向其中添加本實施形態之 早成分性調配組合物，加以均勻地混合而獲得密封材料。 作為塗佈材，例如可用作電子材料之塗佈材、印刷電路 板之覆蓋用保護層材、印刷基板之層間絕緣用樹脂組合物 等。作為塗佈用材料之製造方法，例如可應用曰本專利特 公平4-6116號、曰本專利特開平7_3〇4931號'日本專利特 開平8-64960號、日本專利特開2〇〇3_246838號等中所記載 之方法。具體而言’係自填充劑選定二氧化矽等，將其作 為填充料而調配入雙酚A型環氧樹脂、苯氧基樹脂、橡膠 改性環氧樹脂等中’進而調配入本實施形態之單成分性調 配組合物，以MEK(methyl ethyl ketone，曱基乙基酮）來製 備50%之溶液。將其以50 μηι之厚度塗佈於聚醯亞胺薄膜 132805.doc -39· 200916496 上，重疊銅泊’於6〇〜15〇t：下實施層|，使該層壓薄板於 180〜2〇G°C下加熱硬化，藉此而獲得由環氧樹脂組合物漆 佈層間之積層板。 a 作為塗料組合物之製造方法’例如可應用日本專利特開 平1 1-323247號、日本專利特開Moy ΐ3 1〇3號等中所記二 之方法》具體而言’係於雙紛A型環氧樹脂中調配入二氧 化鈦/月石等，添加作為混合溶劑的(甲基異丁基 酮V二甲苯之1 : 1混合溶劑，進行攪拌、混合，製成： 劑。向其中添加本實施形態之單成分性調配組合物，使其 均勻地分散，藉此而獲得塗料組合物。 八 作為預浸料之製造方法，例如可應用曰本專利特開平 〇9-71633號、W〇98/4侧號等中所記載之方法可藉由將 本實施形態之單成分性調配組合物含浸於增強基材中，進 行加熱而製心再者，作為所含浸之清漆之溶劑，可列舉 曱基乙基酮、丙酮、乙基溶纖劑、甲醇、乙醇、異丙醇 等，杈好的是該等溶劑並不殘存於預浸料中。再者，增強 基材之種類並無特別限制’例如可列舉：·氏、玻璃布：玻 璃不織布、芳族聚醯胺布、液晶聚合物等。樹脂組合物分 與增強基材之比例亦無特別限制，通常較好的是以預浸料 中之樹脂分成為20〜80質量％之方式進行製備。 作為熱傳導性材料之製造方法，例如可應用日本專利特 開平06-⑽44號、日本專利特開平1〇_2374職、日本專 利特開2000-3987號等中所記载之方法。更加具體而言， 係調配作為熱硬化性樹脂之環氧樹脂、作為硬化劑之苯驗 132805.doc -40· 200916496 酚醛清漆硬化劑、進而作為熱傳導填充料之石墨粉末，進 打均勻混練。向其中調配人本實施形態之單成分性調配組 合物’藉此而獲得熱傳導性樹脂糊料。 [實施例] 以下，列舉具體實施例來對本發明加以詳細說明。再 者，只要無特別說明，實施例及比較例中之「份」或 「％」則為質量基準。 (測定方法） ‘ 實施例、比較例中之物性等的測定方法係如以下所示。 (1) 玻璃轉移溫度（Tg) 使用 DSC(differential scanning calorimeter，示差掃描熱 析儀），以l〇t /分鐘之升溫速度來測定環氧樹脂用硬化劑 之Tg(JIS K 7121 DSC法）。該溫度越低，則判斷低溫硬化 性越優良。 (2) DSC頂點溫度 〇 使用DSC(示差掃描熱析儀），以101/分鐘之升溫速度進 行測定。將發熱之峰值溫度作為DSC頂點溫度。該溫度越 低’則判斷低溫硬化性越優良。 (3) 凝膠化時間 對於直至利用依據JIS c_6521之凝膠化試驗機來實施的 凝膠化為止之時間，以如下方式加以測定，進行評價。 即，將凝膠板保持為130t，於該板上載置〇4 mL之單成 分性調配組合物的樣品，載置後以攪拌棒進行攪拌，測定 直至不再拉絲為止之時間（直至凝膠化為止之時間（秒乃。 132805.doc -41 - 200916496 該時間越短，則判斷短時間硬化性越優良。 (4) 黏度變化 於40 C之溫度下放置！週，藉由3型黏度計（東機產業公 司製造之BH型）來測定其前後之樣品黏度。根據放置前後 之黏度測定值，由下式求得黏度變化（倍）。 (黏度變化（倍）)=(放置後黏度）/(放置前黏度） 黏度變化越接近1，則判斷儲存穩定性越優良。 (5) 耐填充料性 將以三輥研磨機混練3 〇份之單成分性調配組合物與7 〇份 之粒徑為7 μηι之二氧化矽填充料而獲得之調配物，於25t>c 之溫度下放置1日，藉由3型黏度計（東機產業公司製造之 BH型）來測定其前後之樣品黏度。根據放置前後之黏度測 定值，由下式求得黏度變化（倍）。 (黏度變化（倍）)=(放置後黏度放置前黏度） 黏度變化越接近1，則判斷耐填充料性越優良。 (6) 殼（S)之紅外線吸收特性 自下述[母料型環氧樹脂用硬化劑組合物]段落中所記載 之母料型裱氧樹脂硬化劑組合物中分離出膠囊膜即殼 (S) ’調查紅外線吸收特性。 首先，使用二甲苯對母料型環氧樹脂用硬化劑組合物反 覆進行清洗與過濾，將環氧樹脂完全地去除。 繼而，使用環己烷反覆進行清洗與過濾，將二曱笨完全 地去除。 其後，將環己烷過濾分離，於40〇c之溫度下實施乾燥處 132805.doc -42- 200916496 理將環己燒完全地去除，自产 人物中八施山 料里環氧樹脂用硬化劑組 口物中分離出微膠囊型環氧樹脂硬化齊卜 使用曱醇對所分離之微 — 展t%氧樹脂用硬化劑反覆進 仃 洗與過濾，直至環負 衣軋树知硬化劑消失，於40。〇之溫度 下貝施真空乾燥，將甲醇完全 王地去除’自微膠囊型環氧樹 脂用硬化劑中分離出膠囊膜即殼（S)。 對於藉由上述步驟所獲得之膠囊膜，使用日本分光（股） 公司製造之FT/IR-6100，測定紅外吸收光譜。 (結構分析） 使用 LC-MS(Liquid Chromatograph/Mass Spectrometer， 液相層析儀/質譜儀），對將二羥基苯加以縮水甘油化而成 之環氧樹脂與2-甲基咪唑之反應產物進行結構分析。 (1)條件Slave fiber, oxidation_dimensional, carbon cut fiber,: I dimension, polyamidamine _ absolutely fiber-free, polyester fibrin fiber, quasi-aromatic polyglycolic acid, mica, asbestos powder, slate powder Fiber = soil quartz powder 'hydrate hydrate, hydrazine hydrate, white peony powder, gypsum Γ oxidized Ming Sanlu, chlorinated poly H paste, carbon _, three oxidation two shouting emulsified Shi Xi, titanium dioxide, carbon black, graphite 132805. Doc •35· 200916496 Mian, fullerenes, iron oxide, etc. As a filler, for example, Kewei,,, carbon fiber, cellulose saponin, mineral strontium aluminate _ k 仏 asbestos private, slate powder, kaolin, minus Ming dihydrate, oxidized oxidized two records , gasification, surface, two gas, such as gypsum, three stone 'titanium dioxide, carbon charcoal, black stone, gas soluble sputum, reciprocal white, heavy crystal iron, gold, silver, i, carbon nanotubes, fullerenes , oxidation ^ silver, aluminum powder, iron age, too compound and so on. π ungraded metal crystallization, intermetallicization as conductive microparticles, #鹑^ Hunting by mechanical pulverization method, chemical reduction method, electrolysis method, atomization method, any of the metal particles obtained by silver, method, Can be listed iron, Ming and other non-responsible metals are also early; is a particle, copper, copper alloy, recorded, gold, silver-zinc bismuth steel alloy, silver, gold, silver-tin cooperation σ ', silver-alloy, silver-nickel A silver alloy such as an alloy. As a pigment, it can be listed as an inorganic pigment such as kaolin, dioxane 1: kaolin, carbon (tetra), chromium oxide, ketopyrrole carbon black, quinacridone, anthracene, dioxin, ...: (4) Organic pigments such as 啥琳黄, foreign body ketone, jingjing, and cup of az. The organic solvent may, for example, be ketone, methyl isobutyl ketone, methyl benzoate, methyl ethyl, earth, ethyl acetate or butyl acetate. As a reactive diluent, for example, butyl glycidyl ether in the 5th column, Κ glyceryl phthalate, condensate, thioglycidyl ether, oxyethylene glycol diol diol diglycidyl, etc. @-alcohol-glycidol _, 1, has 132805.doc -36 - 200916496 as a non-reactive thin seven, vinegar, dibutyl phthalate 'for example, (four): dioctyl phthalate as a resin, for example Didic acid: vinegar, petroleum solvent, etc. For example, polyester resin, polyurethane eucalyptus, acrylic resin, ¥ 1 modified ^ μ, sapphire, melamine resin or urethane? Abdominal > modified epoxy resin such as a phenolic resin or an alkyd-modified epoxy resin. As a crystalline alcohol, it can be exemplified by work, 2-cyclohexanediol, 1,3-cyclohexanol, 1,4-phosphoranediol, and methylpropane.乙四龄, sorbitol, sucrose, and tripartite as coupling agents, for example, methyl dimethoxy zeshi, phenyl trioxane, 3: glycidoxypropyl methyl diethoxy decane 3, etc. Dididimethoxy 11-burning, Nm-aminopropyl methoxy sulphur-burning 4 decane coupling agent, and the like. The ruthenium preferably contains the above-mentioned other additives or added components in a range of from 0.1 to 90% by mass, more preferably from 1 to 85% by weight, based on the total amount of the composition of the early component. The one-component compounding composition of the present embodiment can be used, for example, as an adhesive, a bonding paste, a bonding film, a film, an anisotropic conductive material, a conductive material, an insulating material, a sealing material, and a coating material. The coating composition, the prepreg, the conductive material, and the like are particularly excellent in solvent resistance and mechanical shear resistance, and thus are particularly useful as a sealing material or an anisotropic conductive material. The above-mentioned adhesive, bonding paste, and bonding materials (4) liquid adhesive, entangled adhesive, and point B |, JL. ^ and sticky Japanese materials. As the manufacturer of the film-like adhesive, for example, Japanese Patent Laid-Open No. 62-141 No. 83, or Japanese Patent No. 132805. doc-37-200916496, Japanese Patent Laid-Open No. Hei 05-295329, and the like can be used. law. Specifically, the preparation is such that the solid epoxy resin, the liquid epoxy resin, and the solid urethane tree are dissolved in a manner of 50% by mass on the day of the month. a solution made in the middle. The preparation is added to the solution. The embodiment of the present invention is a varnish made of a composition of 30% by mass. The varnish is applied, for example, to a polyethylene terephthalate substrate for peeling having a thickness of 50 μm to dry the toluene to a thickness of 3 Å. The benzene is dried to obtain inertness at a hanging temperature. A film for bonding which exhibits adhesiveness by the action of a latent curing agent by heating. As the anisotropic conductive material, an anisotropic conductive film or an anisotropic conductive paste is exemplified as the conductive material, and a conductive film or a conductive paste is used as the conductive material. Examples of such materials are as follows: 猎 曰 曰 专利 专利 专利 专利 专利 专利 专利 专利 专利 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 For example, in the production of the film for the above-mentioned film, the conductive material or the anisotropic conductive material may be mixed and dispersed, and applied to (4) to be dried. As the conductive material or the conductive material which is an anisotropic conductive material, it is possible to use: solder particles, a chain of metal, a metal crystal of a non-meter grade, and other inclined particles of gold, y, copper and silver. Or a metal particle, or a conductive film such as gold, ruthenium, phase, pt ^ octa-copper, solder, etc., for the styrene tree ruthenium urethane resin, two dates. _ 氘 氘 知 know, % oxygen A resin particle such as a resin, an acrylic resin, a phenol resin, or a yellow-depleted ethylene-butadiene resin is used to form a microparticle of about 1 to 20 μm. As the substrate of the Portuguese + ', the film is dried, for example, polyester, poly 132805.doc -38 - 200916496 ethylene, polyimide, polytetrafluoroethylene or the like can be used. As an insulating material, it can be listed as g* insulating bonding, and can be used as a soldering paste or the like. It is obtained using the above film for bonding. In addition, in addition to the sealing material, 藓 μ μ, 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 y and get the same density 2 can be used as solid sealing material, liquid sealing material, film sealing material = i-shaped sealing material can be used as underfill, potting material, dam material, etc. For example, the method of manufacturing the electronic component is described in Japanese Patent Laid-Open No. s43661, Japanese Patent Laid-Open No. 2, No. 226675, and the method of manufacturing the impregnated molding material is more specifically Adding a double-type A-type epoxy resin, as a curing agent, an acid anhydride curing agent, methyl hexahydrophthalic acid, and then spherically smelting the cerium oxide powder, uniformly mixing them, and adding the present embodiment thereto The compositions are formulated in an early form and uniformly mixed to obtain a sealing material. The coating material can be used, for example, as a coating material for an electronic material, a protective layer for covering a printed circuit board, a resin composition for interlayer insulation of a printed substrate, or the like. As a manufacturing method of a coating material, for example, the patent application Japanese Patent Publication No. Hei 4-6116, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. 8-64960, Japanese Patent Laid-Open No. Hei 8-64960 The method described in the above. Specifically, 'the cerium oxide or the like is selected from the filler, and it is blended into a bisphenol A type epoxy resin, a phenoxy resin, a rubber-modified epoxy resin, etc. as a filler, and is further blended into this embodiment. The one-component compounding composition was prepared by using MEK (methyl ethyl ketone, mercapto ethyl ketone) to prepare a 50% solution. Applying it to the polyimide film 132805.doc-39·200916496 with a thickness of 50 μηι, and superposing the copper layer 'under 6〇~15〇t: layer|layer, the laminated sheet is 180~2 The laminate was heat-hardened at 〇G°C, thereby obtaining a laminate between the varnish layers of the epoxy resin composition. a method for producing a coating composition, for example, a method described in Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei No. Hei. In the epoxy resin, a titanium oxide/moonstone or the like is added, and a mixed solvent of (methyl isobutyl ketone V xylene) as a mixed solvent is added, and the mixture is stirred and mixed to prepare a solvent. The embodiment is added thereto. The composition of the composition is uniformly dispersed to obtain a coating composition. VIII. As a manufacturing method of the prepreg, for example, the patent application Japanese Patent Laid-Open No. Hei 9-71633, W〇98/4 The method described in the side number or the like can be obtained by impregnating the one-component compounding composition of the present embodiment with a reinforcing substrate and heating it to form a core. The solvent of the varnish to be impregnated can be exemplified. Ketone, acetone, ethyl cellosolve, methanol, ethanol, isopropanol, etc., preferably, the solvents do not remain in the prepreg. Further, the type of the reinforcing substrate is not particularly limited 'for example Can be listed: · ·, glass cloth: glass The woven fabric, the aromatic polyamide cloth, the liquid crystal polymer, etc. The ratio of the resin composition to the reinforcing substrate is also not particularly limited, and it is usually preferred that the resin component in the prepreg be 20 to 80% by mass. In the method of producing the heat conductive material, for example, a method described in Japanese Patent Laid-Open No. Hei 06-(10) No. 44, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. 2000-3987, and the like. More specifically, an epoxy resin as a thermosetting resin, a benzene test 132805.doc-40·200916496 novolac hardener as a curing agent, and a graphite powder as a heat conductive filler are blended and uniformly kneaded. The one-component compounding composition of the present embodiment is blended to obtain a thermally conductive resin paste. [Examples] Hereinafter, the present invention will be described in detail with reference to specific examples. The "parts" or "%" in the examples and the comparative examples are the masses. (Measurement method) 'The measurement methods of the physical properties in the examples and the comparative examples are as follows. (1) Glass transition temperature (Tg) Using a DSC (differential scanning calorimeter), the Tg of the hardener for epoxy resin is measured at a heating rate of l〇t / min (JIS K 7121 DSC method) The lower the temperature, the better the low-temperature hardenability is judged. (2) The DSC apex temperature is measured by a DSC (differential scanning calorimeter) at a temperature increase rate of 101/min. The peak temperature of the heat is taken as the DSC peak temperature. The lower the temperature, the better the low-temperature hardening property is judged. (3) The gelation time is measured as follows until the gelation is performed by the gelation tester according to JIS c_6521. Evaluation. That is, the gel plate was kept at 130 t, and a sample of 4 mL of the one-component compounding composition was placed on the plate, and after stirring, the sample was stirred with a stirring bar, and the time until the wire was no longer drawn (until gelation) was measured. The time until the second (132805.doc -41 - 200916496) The shorter the time, the better the short-term hardenability. (4) The viscosity change is placed at a temperature of 40 C! Week, with a type 3 viscometer ( The viscosity of the sample before and after the BH type manufactured by Toki Sangyo Co., Ltd. is determined according to the viscosity measurement value before and after the placement, and the viscosity change (times) is obtained by the following formula (viscosity change (times)) = (viscosity after placement) / (Pre-stack viscosity) The closer the viscosity change is to 1, the better the storage stability is judged. (5) The filler-resistant property will be mixed with a three-roll mill with a three-component single-component formulation and a particle size of 7 parts. The formulation obtained for the 7 μηι cerium oxide filler was placed at a temperature of 25 t > c for 1 day, and the sample viscosity before and after the measurement was measured by a 3 type viscosity meter (BH type manufactured by Toki Sangyo Co., Ltd.). According to the viscosity measurement value before and after placement, The viscosity change (times) is obtained by the formula (viscosity change (times)) = (viscosity before leaving the viscosity after placement) The closer the viscosity change is to 1, the better the filler resistance is judged. (6) The infrared absorption of the shell (S) In the masterbatch type epoxy resin hardener composition described in the following section [Binder type epoxy resin hardener composition], the shell film (S), which is a capsule film, was investigated to investigate the infrared absorption characteristics. The masterbatch type epoxy resin hardener composition is repeatedly washed and filtered with xylene to completely remove the epoxy resin. Then, the cyclohexane is repeatedly washed and filtered to completely remove the ruthenium. After that, the cyclohexane was separated by filtration, and the drying was carried out at a temperature of 40 〇c. 132805.doc -42-200916496 The cyclohexan was completely removed, and the self-produced character was used as an epoxy resin hardener in the ba Shishan material. The microcapsule-type epoxy resin is separated from the mouth of the group and hardened by using the decyl alcohol to repeatedly wash and filter the separated micro-enhanced t% oxygen resin with a hardener until the ring-shaped sclerosing agent disappears. At 40. Under the temperature Vacuum drying, completely removes methanol from the 'small capsule type epoxy resin hardener to separate the capsule film, ie the shell (S). For the capsule film obtained by the above steps, use the Japan Spectrophotonics Co., Ltd. FT/IR-6100 manufactured, measuring infrared absorption spectrum. (Structural analysis) Using a LC-MS (Liquid Chromatograph/Mass Spectrometer, liquid chromatography/mass spectrometer), glycidylation of dihydroxybenzene Structural analysis of the reaction product of epoxy resin and 2-methylimidazole. (1) Conditions

製備樣品之曱醇溶液（10 mg/mL)，供給於LC-MS測定。 LC 裝置 Agilent，1100 系歹ij 管柱 GL Sciences Inc.，Inertsil ODS-3(2.1 mml.D.x 150 mm)A sample of the sterol solution (10 mg/mL) was prepared and supplied for LC-MS measurement. LC unit Agilent, 1100 series 歹 管 column GL Sciences Inc., Inertsil ODS-3 (2.1 mml.D.x 150 mm)

管柱溫度 40°C 流速 0.2 mL/min 檢測 UV 280 nm 移動相 A=甲醇 B=乙腈 C=水：0.1%三乙胺，以甲酸將1^值調整為3.2 132805.doc -43 - 200916496 梯度 [表1] 時間（分鐘） A % B% rc% 0 5 5 90 30 50 50 0 注入量 2 pL MS 裝置 Thermo Electron > LCQ 離子化 APCI 模式 正離子 掃描範圍 m/z為 50~2000 (2)結果 UV 280 nm檢測下之層析圖的主要波峰（Area% : 10%以 上）的面積值等示於下述表2中。 [表2] 波峰 RT(min) 波峰面積 面積（％) 1 2.245 3804.4 26.7 2 5.262 4281.4 30.1 3 8.322 2604.9 18.3 各波峰中之主要檢測離子（m/z)係如下所示 波峰 1 387.4 [M+H] + 波峰 2 387.4 [M+H] + 波峰3 381.5 [M+H]+ ' 249.3 [M+H] + 根據上述結果所推定之結構示於下述中。 132805.doc 44· 200916496 波峰1及波峰2 [化 11]Column temperature 40 ° C Flow rate 0.2 mL / min Detection UV 280 nm Mobile phase A = methanol B = acetonitrile C = water: 0.1% triethylamine, adjusted for 1^ value with formic acid to 3.2 132805.doc -43 - 200916496 Gradient [Table 1] Time (minutes) A % B% rc% 0 5 5 90 30 50 50 0 Injection amount 2 pL MS device Thermo Electron > LCQ ionization APCI mode positive ion scanning range m/z is 50~2000 (2 As a result, the area values of the main peaks (Area%: 10% or more) of the chromatogram under the UV 280 nm detection are shown in Table 2 below. [Table 2] Peak RT (min) Peak area (%) 1 2.245 3804.4 26.7 2 5.262 4281.4 30.1 3 8.322 2604.9 18.3 The main detection ion (m/z) in each peak is as follows: 1 387.4 [M+H ] + crest 2 387.4 [M+H] + crest 3 381.5 [M+H]+ ' 249.3 [M+H] + The structure estimated from the above results is shown below. 132805.doc 44· 200916496 Crest 1 and Crest 2 [Chem. 11]

此處，推定於波峄2所檢測之化合物為波峰1之異構物。 波峰3 [化 12]Here, it is estimated that the compound detected in the wave 2 is an isomer of the peak 1. Crest 3 [Chemistry 12]

[化 13][Chem. 13]

ch3Ch3

[環氧樹脂用硬化劑] (實施例1〜3) 以下述表3中所示之調配比（環氧基/胺基之當量比），將 對二經基苯加以縮水甘油化而成之環氧樹脂（PTI JAPAN製 造：RDGE-H，環氧當量為120 g/當量）的80%丙二醇單甲 132805.doc •45- 200916496 醚溶液，於80芄下以2小時添加至咪唑類之3〇%丙二醇單 甲醚溶液中，使其反應。 上述添加後，進而於8(TC下使其反應1小時。其後，將 溶劑即丙二醇單甲謎加熱館去，於1 8 〇。〇下進而使其反應2 小時。 上述反應後’於減壓下將未反應之咪唑類餾去，獲得環 氧樹脂用硬化劑c -1〜c - 3。 上述環氧樹脂用硬化劑（c-1〜c-3)於25°C下均為固體狀。 測定各環氧樹脂用硬化劑之玻璃轉移溫度（Tg)，結果示於 下述表3中。 (實施例4) 使用將2,6-二經基甲苯加以縮水甘油化而成之環氧樹 脂，來代替將二羥基苯加以縮水甘油化而成之環氧樹脂。 其他條件與實施例丨相同，獲得實施例4之環氧樹脂用硬化 劑c-4。所獲得之環氧樹脂用硬化劑於25。〇下為固體狀。 測疋各環氧樹脂用硬化劑之Tg ’結果示於下述表3中。 (實施例5) 使用將1 ’2-二羥基環己烷加以縮水甘油化而成之環氧樹 脂，來代替將二羥基苯加以縮水甘油化而成之環氧樹脂。 其他條件與實施例3相同，獲得實施例5之環氧樹脂用硬化 劑c-5。所獲得之環氧樹脂用硬化劑於25 t下為固體狀。 測疋各％氧樹脂用硬化劑之Tg，結果示於下述表3中。 (比較例1、2) 使用將雙酚A加以縮水甘油化而成之環氧樹脂，來代替 132805.doc •46· 200916496 鲁/土本加以縮水甘油化而成之環氧樹脂。其他條件與 她例2相@，獲得比較例i、2之環氧樹脂用硬化劑μ、 e_7。所獲得之環氧樹脂用硬化劑於抓下均為固體狀。 測定各環氧樹脂用硬化劑之Tg，結果示於下述表3中。 (比較例3) 使用將雙酚八加以縮水甘油化而成之環氧樹脂，來代替 將二羥基苯加以縮水甘油化而成之環氧樹脂，除此以外， 以與實施例i相同之方式’獲得比較例3之環氧樹脂用硬化 劑c-8。所獲传之環氧樹脂用硬化劑於25 ^下為固體狀。 測定環氧樹脂用硬化劑之Tg，結果示於下述表3中。 (比較例4) 使用聚丙二醇二縮水甘油醚，來代替將二羥基苯加以縮 水甘油化而成之環氧樹脂。其他條件與實施例丨相同，獲 得比較例4之環氧樹脂用硬化劑c_9。所獲得之環氧樹脂用 硬化劑於25t下為固體狀。測定環氧樹脂用硬化劑之， 結果示於下述表3中。 132805.doc -47· 200916496 [表3] 實施例 比較例 1 2 3 4 5 1 2 3 4 環氧樹脂用硬化劑 c-1 c-2 c-3 c-4 c-5 c_6 c-7 c-8 c-9 原料之 調配比 (環氧基 /胺基之 當量比） 環 氧 樹 脂 將二羥基 苯加以縮 水甘油化 而成之環 氧樹脂 1.0 1.0 1.0 將 2,6-二 羥基曱苯 加以縮水 甘油彳匕而 成之環氧 樹脂 1.0 將 1，2-二 羥基環己 烧加以縮 7jC甘油而 成之環氧 樹脂 1.0 將雙酚A 加以縮水 甘油彳匕而 成之環氧 樹脂 1.0 1.0 1.0 聚丙二醇 二縮水甘 油醚 1.0 咪 σ坐 類 咪。坐 1.2 1.2 1.4 0.9 2-曱基咪 U坐 1.2 0.7 1.2 2-苯基咪 口坐 1.2 1.2 Tg(°C) 51.5 55.0 59.8 58.3 56.1 67.1 64.6 61.0 52.3 132805.doc -48- 200916496 如=3所示，實施例1〜5與比較例i〜3相比，Tg較低，可 本只施形態之環氧樹脂用硬化劑的低溫硬化性優良。 對比較例1、2進行比較，則比較例2中，2_甲基咪 嗤的調配比多於環氧基，故而環氧樹脂用硬化劑之分子量 變小’ Tg降低。 [母料型環氧樹脂用硬化劑組合物] (實施例6〜1 〇)[Hardifying Agent for Epoxy Resin] (Examples 1 to 3) The dibutyl benzene was glycidylated by the compounding ratio (equivalent ratio of epoxy group/amine group) shown in Table 3 below. Epoxy resin (manufactured by PTI JAPAN: RDGE-H, epoxy equivalent 120 g/eq) 80% propylene glycol monomethyl 132805.doc • 45- 200916496 ether solution, added to the imidazole at 80 Torr for 2 hours 〇% propylene glycol monomethyl ether solution, let it react. After the above addition, the reaction was further carried out at 8 (TC) for 1 hour. Thereafter, the solvent, i.e., the propylene glycol monocarbone, was heated to a temperature of 18 Torr. The reaction was further carried out for 2 hours. The unreacted imidazole is distilled off under pressure to obtain a hardener c-1~c-3 for epoxy resin. The above hardener for epoxy resin (c-1 to c-3) is solid at 25 ° C. The glass transition temperature (Tg) of the curing agent for each epoxy resin was measured, and the results are shown in the following Table 3. (Example 4) A ring obtained by glycidylating 2,6-di-transmethylbenzene An epoxy resin obtained by glycidating dihydroxybenzene was used instead of the epoxy resin. Other conditions were the same as in Example ,, and the epoxy resin hardener c-4 of Example 4 was obtained. The hardener was solid at 25. The solids were measured. The results of measuring the Tg of each of the epoxy resin hardeners are shown in Table 3 below. (Example 5) Using 1 '2-dihydroxycyclohexane to shrink A glycerin-formed epoxy resin instead of an epoxy resin obtained by glycidylating dihydroxybenzene. Other conditions and implementation In the same manner as in Example 3, the hardener c-5 for epoxy resin of Example 5 was obtained. The obtained hardener for epoxy resin was solid at 25 t. The Tg of each hardener for oxygen resin was measured, and the results were shown. It is shown in the following Table 3. (Comparative Examples 1 and 2) An epoxy resin obtained by glycidylating bisphenol A was used instead of 132805.doc • 46· 200916496 Lu/Graft was glycidylated Epoxy resin. Other conditions were the same as in Example 2, and the hardeners μ and e_7 for epoxy resins of Comparative Examples i and 2 were obtained. The obtained hardener for epoxy resin was solid under grasping. The Tg of the hardener for oxygen resin is shown in the following Table 3. (Comparative Example 3) An epoxy resin obtained by glycidylating bisphenol eight is used instead of glycidolating dihydroxybenzene. In the same manner as in Example i, the epoxy resin hardener c-8 of Comparative Example 3 was obtained in the same manner as in Example i. The obtained epoxy resin hardener was solid at 25 ^. The Tg of the hardener for epoxy resin was measured, and the results are shown in the following Table 3. (Comparative Example 4) Using polypropylene glycol II A glyceryl ether was used instead of the epoxy resin obtained by glycidylating dihydroxybenzene. Other conditions were the same as in Example ,, and the hardener c_9 for epoxy resin of Comparative Example 4 was obtained. The agent was a solid at 25 t. The epoxy resin hardener was measured, and the results are shown in the following Table 3. 132805.doc -47· 200916496 [Table 3] Example Comparative Example 1 2 3 4 5 1 2 3 4 Epoxy resin hardener c-1 c-2 c-3 c-4 c-5 c_6 c-7 c-8 c-9 raw material ratio (equivalent ratio of epoxy/amine groups) Epoxy resin obtained by glycidation of dihydroxybenzene 1.0 1.0 1.0 Epoxy resin obtained by adding 2,6-dihydroxyanthracene to glycidol 1.0 Reducing 1,2-dihydroxycyclohexane to 7jC Epoxy resin made of glycerin 1.0 Epoxy resin obtained by adding bisphenol A to glycidol 1.0 1.0 1.0 Polypropylene glycol diglycidyl ether 1.0 M. Sit 1.2 1.2 1.4 0.9 2-曱基咪U sit 1.2 0.7 1.2 2-phenyl ip mouth 1.2 1.2 Tg (°C) 51.5 55.0 59.8 58.3 56.1 67.1 64.6 61.0 52.3 132805.doc -48- 200916496 as shown in =3 In Examples 1 to 5, compared with Comparative Examples i to 3, the Tg was low, and the curing agent for an epoxy resin of the present embodiment was excellent in low-temperature curability. Comparing Comparative Examples 1 and 2, in Comparative Example 2, since the mixing ratio of 2-methylimidazole was more than that of the epoxy group, the molecular weight of the curing agent for epoxy resin became smaller, and the Tg decreased. [Masterbatch type epoxy resin hardener composition] (Examples 6 to 1 〇)

、述方式製成之環氧樹脂用硬化劑c-l〜c-5加以粉碎 (於25C下為固體狀），以使平均粒徑成為2.4,。 字* 0身量伤之該粉碎物、15質量份之水、及7質量份 之甲本—異氣酸§旨’添加至則質量份之將雙紛A加以縮水 甘油化而成之環氧樹脂中，於4〇。〇下一面搜掉一面使其反 應3小％。其後’於⑽下進行8小時的殼形成反應，獲得 母料型環氧樹脂用硬化劑組合物Η -1〜Η - 5。 按照上述（6)之殼（s)的紅外線吸收特性之項目中所記載 之步驟’自母料型環氧樹脂用硬化劑H-H5中分離出 膠囊型環氧樹脂用硬化劑，進而自其中進行勝囊膜即殼 ()之FT IR測疋，結果確認：於任一微膠囊型環氧樹 硬化劑中均具有：吸收波數為測〜刪之紅奇 脲配位基⑻、吸收波數為168Q〜m5⑽·】之紅外墙_ 腺配位基⑺、及吸收波數W ^之紅外線= 基甲酸酯配位基（z)。 '胺 (比較例5〜8) 使用以上述方式製成之環氧樹月旨用硬化劑c-6〜c-9，- 错由 132805.doc -49- 200916496 與實施例6〜1 0相同之方法 組合物Η-6〜Η-9。 獲得母料型環氧樹脂用硬化劑 [單成分性調配組合物] (實施例11〜15)The epoxy resin prepared by the above method was pulverized (solid in 25C) with a curing agent c-l to c-5 so as to have an average particle diameter of 2.4. Word * 0 The amount of the crushed material, 15 parts by mass of water, and 7 parts by mass of the base - isogastric acid § The purpose of adding to the mass part of the double A is glycidylated In the resin, at 4 〇. The next side of the squat is to search for one side and make it a small 3%. Thereafter, a shell formation reaction was carried out for 8 hours under (10) to obtain a hardener composition Η -1 to Η - 5 for a master batch type epoxy resin. According to the procedure described in the item of infrared absorption characteristics of the shell (s) of the above (6), the curing agent for the capsule type epoxy resin is separated from the hardener H-H5 for the master batch type epoxy resin, and further The FT IR test of the shell film (the shell) was carried out, and it was confirmed that in any of the microcapsule-type epoxy tree hardeners, the absorption wave number was determined by the red-urea complex (8), and the absorption wave was measured. The number is 168Q~m5(10)·] of the infrared wall _ gland ligand (7), and the absorption wave number W ^ of the infrared = urethane ligand (z). 'Amine (Comparative Examples 5 to 8) The epoxy resin sclerosing agent c-6 to c-9 prepared in the above manner was used, and the error was the same as that of Examples 6 to 1 0 by 132805.doc -49-200916496. The method composition is Η-6~Η-9. Hardener for masterbatch type epoxy resin [single-component compounding composition] (Examples 11 to 15)

將30質量份之以上述方式製成之母料型環氧樹脂用硬化 劑組合物Η-1〜Η-5，與1〇〇質量份之雙酚Α型環氧樹脂（旭化 成化學公司製造，AER 2603，環氧當量為12〇 g/Eq)、及 1〇〇質量份之以四氫鄰苯二甲酸奸為主成分的hn_2200(日 立化成工業（股）製造）混合，獲得單成分性調配組合物 1 〜1-5。 對該等單成分性調配組合物進行上述（2)DSC頂點溫度、 (3)凝膠化時間、（4)黏度變化、（5)耐填充料性之各個物性 評價，結果示於下述表4中。 (比較例9〜12) 使用以上述方式製成之母料型環氧樹脂用硬化劑組合物 H-6〜H-9，以與實施例11〜15相同之方式’獲得單成分性調 配組合物1-6〜1-9。對該等單成分性調配組合物進行上述 (2)〜(5)之各個物性評價，結果示於下述表4中。 132805.doc -50- 200916496 [表4] 實施例 比較例 11 12 13 14 15 9 10 11 12 組合物 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 評價 DSC 頂點溫度(°c) 142 145 147 148 141 157 150 145 143 凝膠化時間 @130°C (分鐘） 2.1 2.6 2.8 2.9 2.7 4.4 3.3 3.2 2.9 黏度變化(倍） 1.2 1.2 1.1 1.1 1.2 1.1 1.3 1.3 1.9 耐填充料性(倍） 1.3 1.2 1.2 1.2 1.3 1.5 1.8 1.8 5.0 如表4所示’實施例丨丨〜丨5之單成分性調配組合物由於使 用本實施形態之母料型環氧樹脂用硬化劑組合物，故而低 溫及短時間硬化性優良，儲存穩定性、耐填充料性亦於實 用上充分良好。 比較例9之單成分性調配組合物的儲存穩定性與實施例 之組合物大致為同等程度，然而在低溫及短時間硬化性以 及耐填充料性方面不良，未獲得在實用上良好之特性。 比較例1〇、U之單成分性調配組合物的儲存穩定性盥實 施例U〜15之組合物大致為同等程度，然而低溫及短時Γ 硬化性稱稍遜色，尤其是 ’ 1 實用上良好之特性。 ⑴大為過色，未獲得在 :較例12之單成分性調配組合物的 與實施例…15之組合物大致為㈣好㈣硬化性 性與耐填充料性大為遜色 …、、而儲存穩定 未獲侍在實用上良好之特性。 132805.doc •51 · 200916496 本申請案係依據2007年7月5曰在曰本專利廳所申請之曰 本專利申請案（曰本專利特願2〇〇7_177261)，其内容作為參 照而編入本申請案中。 [產業上之可利用性] 本發明之環氧樹脂用硬化劑、及使用該環氧樹脂用硬化 诏之組合物不會損及電子機器構 德尨# — ω 兀/、疋移動機器等之 储存％疋性，故可於產業上用作要求具 ^ ra ,L 另低溫且短時間下 之硬化性的連接材料、密封材料。 132805.doc 52.30 parts by mass of the master batch type epoxy resin hardener composition Η-1 to Η-5 prepared in the above manner, and 1 〇〇 part by mass of bisphenol oxime type epoxy resin (Asahi Kasei Chemical Co., Ltd., AER 2603, an epoxy equivalent of 12〇g/Eq), and 1 part by mass of hn_2200 (manufactured by Hitachi Chemical Co., Ltd.) containing tetrahydrophthalic acid as a main component, and obtaining a one-component blending Composition 1 to 1-5. The physical properties of the above-mentioned (2) DSC apex temperature, (3) gelation time, (4) viscosity change, and (5) filler-resistant property were evaluated for the one-component compounding composition, and the results are shown in the following table. 4 in. (Comparative Examples 9 to 12) Using the hardener compositions H-6 to H-9 for the master batch type epoxy resin prepared in the above manner, a single component blending combination was obtained in the same manner as in Examples 11 to 15. 1-6~1-9. The physical properties of the above (2) to (5) were evaluated for the one-component compounding compositions, and the results are shown in Table 4 below. 132805.doc -50- 200916496 [Table 4] Example Comparative Example 11 12 13 14 15 9 10 11 12 Composition 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 Evaluation of DSC apex temperature (°c) 142 145 147 148 141 157 150 145 143 Gelation time @130°C (minutes) 2.1 2.6 2.8 2.9 2.7 4.4 3.3 3.2 2.9 Viscosity change (times) 1.2 1.2 1.1 1.1 1.2 1.1 1.3 1.3 1.9 Filling resistance (times) 1.3 1.2 1.2 1.2 1.3 1.5 1.8 1.8 5.0 As shown in Table 4, the single-component formulation of the examples 丨丨~丨5 is used as the masterbatch type ring of this embodiment. Since the hardener composition for an oxy resin is excellent in low temperature and short-time hardening property, storage stability and filler-resistance are also excellent in practical use. The storage stability of the one-component composition of Comparative Example 9 was approximately the same as that of the composition of the examples. However, it was inferior in low-temperature and short-time hardenability and filler-resistance, and practically good characteristics were not obtained. Comparative Example 1 Storage stability of the one-component formulation of U. The compositions of Examples U to 15 were approximately the same, but the low temperature and short-term Γ hardenability were slightly inferior, especially '1 practically good. Characteristics. (1) It is largely over-colored, and it is not obtained: the composition of the single-component composition of Comparative Example 12 and the composition of Example 15 are substantially (four) good (4) hardenability and filler resistance are inferior... Stabilization has not been given a practically good feature. 132805.doc •51 · 200916496 This application is based on the patent application filed on July 5, 2007 in the Patent Office (Japanese Patent Application No. 2〇〇7_177261), the contents of which are incorporated herein by reference. In the application. [Industrial Applicability] The curing agent for an epoxy resin of the present invention and the composition for using the hardened crucible for the epoxy resin do not impair the electronic device structure, such as the #ω 兀/, 疋 mobile device, etc. Since it is stored in %, it can be used industrially as a connecting material or sealing material which requires a low temperature and a low-hardening property in a short time. 132805.doc 52.

Claims (1)

200916496 十、申請專利範圍： 1. 一氆環氧樹脂用硬化劑，其係由下述通式⑴或⑺表 示： [化1]200916496 X. Patent application scope: 1. A hardener for epoxy resin, which is represented by the following formula (1) or (7): [Chemical 1] [化2][Chemical 2] ⑵ (式中’IW5表示氫原子、可經取代之 基或可經取代之碳數為卜12的芳基 為1韻 經取代之碳數< 衣不虱原子或可 双马1〜6的烷基；R3&R4分別鉬— 原子、下述通式（3)所表Μ基：，立地表示氮 [化3](2) (In the formula, 'IW5 represents a hydrogen atom, a substitutable group or a substitutable carbon number is 12, and the aryl group is a carbon number substituted by 1 rhyme< a non-anthracene atom or a double horse 1 to 6 Alkyl; R3&R4, respectively, a molybdenum-atom, a sulfhydryl group represented by the following formula (3): a standpoint indicating nitrogen [Chemical 3] ⑶ 界上述同義） 或下述通式(4)所表示之基: [化4] 132805.doc 200916496 —CH2-<pH—CH2—OH ⑶ ⑷ ;n表示l〜3之整數）。 2. 如請求項1之環氧樹脂用硬化劑，其中環氧樹脂用硬化 劑係由上述通式（1)表示，且式中之R5為氫原子。 3. 種微膠囊型環氧樹脂用硬化劑，其具備包含如上述請 求項1或2之環氧樹脂用硬化劑之核（c)、以及 包覆該核（C)之殼（s)，並且 該殼（s)包含上述核（c)與環氧樹脂（A1)之反應物、及/ 或異氰酸酯化合物與活性氫化合物之反應物。 4·如請求項3之微膠囊型環氧樹脂用硬化劑，其中 上述殼（S)具有： 吸收波數為1630〜1680 cm-1之紅外線的脲配位基（χ)、 吸收波數為1 680〜1 725 cm·1之紅外線的縮二脲配位基 (y)、以及 吸收波數為1730〜1755 cm·1之紅外線的胺基甲酸醋配 位基（z)。 5. 種母料型環氧樹脂用硬化劑組合物，其係將如上述請 求項1或2之環氧樹脂用硬化劑及/或如上述請求項3或4之 微膠囊型環氧樹脂用硬化劑中的至少一種分散於環氧樹 脂（A2)中而成。 ' 6. 種單成分性調配組合物，其包含如上述請求項5之母 '料型環氧樹脂用硬化劑組合物及環氧樹脂（A3)。 132805.doc 200916496 七、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：(3) The above-mentioned synonymous) or a group represented by the following formula (4): [Chem. 4] 132805.doc 200916496 - CH2-<pH-CH2-OH (3) (4); n represents an integer of 1 to 3). 2. The hardener for epoxy resin according to claim 1, wherein the hardener for epoxy resin is represented by the above formula (1), and R5 in the formula is a hydrogen atom. 3. A microcapsule-type epoxy resin hardener comprising a core (c) comprising the hardener for epoxy resin according to claim 1 or 2, and a shell (s) covering the core (C), Further, the shell (s) comprises a reactant of the core (c) and the epoxy resin (A1), and/or a reactant of an isocyanate compound and an active hydrogen compound. 4. The microcapsule-type epoxy resin hardener according to claim 3, wherein the shell (S) has: a urea ligand (χ) having an infrared ray having a wavenumber of 1630 to 1680 cm-1, and an absorption wave number of A biuret ligand (y) of an infrared ray of 1 680 to 1 725 cm·1, and an amino carboxylic acid valence ligand (z) having an infrared ray having an absorption number of 1730 to 1755 cm·1. A masterbatch type epoxy resin hardener composition which is a hardener for an epoxy resin according to the above claim 1 or 2 and/or a microcapsule type epoxy resin according to the above claim 3 or 4. At least one of the hardeners is dispersed in the epoxy resin (A2). 6. A one-component compounding composition comprising the masterbatch type epoxy resin hardener composition and epoxy resin (A3) according to the above-mentioned claim 5. 132805.doc 200916496 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 132805.doc132805.doc