TW201202175A - Polyamide curing agent composition - Google Patents
Polyamide curing agent composition Download PDFInfo
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- TW201202175A TW201202175A TW100111215A TW100111215A TW201202175A TW 201202175 A TW201202175 A TW 201202175A TW 100111215 A TW100111215 A TW 100111215A TW 100111215 A TW100111215 A TW 100111215A TW 201202175 A TW201202175 A TW 201202175A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/502—Polyalkylene polyamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
- C08L77/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- Epoxy Resins (AREA)
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Abstract
Description
201202175 四、 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:無。 五、 本案若有化學式時,請揭示最能顯示發明特徵的化學 無。 子工 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種聚醯胺硬化劑組合物。 本發明之聚酿胺硬化劑組合物係使用成為塗料、接著 劑、地板用材料用途等之所使用之環氧樹脂之硬化性組合 物。 【先前技術】 聚酿胺樹脂組合物係一般以多元酸和聚胺化合物,作 為原料’在加熱下,於胺基和羧基之間,進行脫水縮合, 進行醯胺鍵之形成和聚合物鏈之延伸而進行合成。具體地 說’向來知道:以己二酸、二聚物酸等之二元酸或多元酸 和乙烯二胺、二乙烯三胺等之聚胺類,作為起始原料,藉 由醯胺鍵而連結兩構成單位之樹脂等(例如參考專利文獻 1)。在此’二聚物酸係具有豐富之反應性而成為在工業上 得到之最高分子量之二元酸。 在這些聚醯胺樹脂組合物中’由二聚物酸而衍生之聚 201202175 酿胺係成為強勒而顯示柔軟性’並且,具有良好之接著性 能,因此,作為接著劑、油墨、表面塗敷劑或環氧樹脂硬 化劑係練合於環氧樹脂,或者是作為金屬、㈣、陶究等 之表面塗敷用係使用在二液反應型接著劑等。 在聚醯胺樹脂組合物之製造,I用二乙烯三胺 (_ '三乙烯四胺(_、四乙烯五胺(ΤΕΡΑ)、五乙烯 六胺(ΡΕΗΑ)等之聚乙烯胺,但是’在商業上最普通使用之 聚乙烯胺係ΤΕΤΑ。 4疋來自於&知之二乙稀四胺之聚醯胺硬化劑係在 其低溫硬化性,具有課題。 此外,在近年來,在風力發電用渦輪機等之塗料領域, 比起ΤΕΤΑ基底之聚醯胺硬化劑,還更加要求可撓性變高之 聚醯胺硬化劑。這個係因為在同一領域,渦輪機之彎曲變 大,和飛來物之接觸等之問題呈顯著化,要求更加不剝離 之塗膜之緣故。 因此,提議使用三乙烯四胺和具有哌嗪環之聚胺之混 合組合物之聚醯胺硬化劑(例如參考專利文獻2)。根據同 一公報内容,因得到之聚醯胺硬化劑係可以減少相對於聚 醯胺硬化劑之環氧樹脂量,藉此降低系統之黏度,而得到 更加短之塗膜硬化時間以及耐撞擊性呈良好之塗膜。 仁疋5己載於同一公報之聚醯胺硬化劑係有比起單獨 地使用三乙烯四胺之狀態塗膜之抗拉強度有更加地降低之 傾向發生’難說是一定也適合在要求同等於三乙烯四胺之 同樣性能之領域。此外,活性氫之當量變大,聚醯胺/環 201202175 難說是適合於要求高度耐水性 氧樹脂之比率變高,因此 之用途。 此外,三乙烯四胺(TETA)係限定原料供應量,比起其 他之聚乙稀聚胺,價格比較高,目此,在聚酿胺硬化劑之 製造中,要求相對等丽,能夠更加安定供應經濟實惠的 替代成分。 於是,作為替代三乙烯四胺(TETA)2聚胺成分係提 議.使用包3 N—3 —胺基丙基乙稀二胺、ν,ν,—雙(3 — 胺基丙基)乙稀二胺、Ν,Ν,Ν,一三(3一胺基丙基)乙烯二 胺、Ν,Ν,Ν , Ν —四(3—胺基丙基)乙烯二胺之混合物之 聚醯胺硬化劑(例如參考專利文獻3)。根據同一公報,比 起ΤΕΤΑ ’還得到更加短之塗膜硬化時間。 但疋’藉由記載於同一公報之聚醯胺硬化劑而造成之 環氧樹脂硬化物係比起習知之聚醯胺硬化劑,可撓性更 差’因此’特別是在要求可撓性之塗料用途,不可以說是 容易取代ΤΕΤΑ。 【先前技術文獻】 【專利文獻】 【專利文獻1】美國專利第2450940號說明書 【專利文獻2】曰本特開平^-228672號公報 【專利文獻3】日本特開2〇〇8_ 7?76號公報 【發明内容】 【發明所欲解決之課題】 4 201202175 本發明係有鑑於前述之背景技術而完成的,其目的係 提供一種可以替代來自於一般最為使用之三乙烯四胺之聚 酿胺硬化劑且非來自於三乙烯四胺的聚醯胺硬化劑組合 物。 具體地說,φζ供(1)比起來自於三乙烯四胺之聚酿胺硬 化劑而顯示良好之可撓性及儲存安定性之非來自於三乙烯 四胺的聚醯胺硬化劑組合物,或者是(2)顯示同等於來自三 乙烯四胺之聚醯胺硬化劑之可撓性及耐水性且顯示更加良 好之硬化性能和儲存安;t性之非來自於三乙稀四胺的聚酿 胺硬化劑組合物。 【用以解決課題之手段】 本發明人們係就聚醯胺硬化劑組合物,全心重複地進 行檢討’結果’以致於完成本發明。 也就是說,本發明係關於正如以下顯示之聚醯胺硬化 劑組合物以及使用該聚醯胺硬化劑組合物而得到之環氧樹 脂硬化物。 [Π· —種聚醯胺硬化劑組合物,其特徵在於:含有由 二乙晞三胺(al)和藉著下列之化學式: H2N^^P NH2 ⑴ (在化學式中,η係表示3以上之數字〇所表示之每卜分 子之氮原子數為5以上之胺化合物(a2)來組成之群組而: 出之化合物以)、每丨分子之氮原子 双马4以下且活性氫數 201202175 為2或3之胺化合物(B)以及包含二聚物酸之成分(c)之反 應生成物並且[化合物(A)和化合物(B)之合計莫爾數]/ [成分(c)之二聚物酸換算之莫爾數]為2/1〜4/3之範圍 且化合物(A)和化合物(B)之莫爾數比(a/^為9〇/1〇〜15 /85之範圍的反應生成物。 [2 ]:前述[1 ]記載之聚醯胺硬化劑組合物,係化合物 (A)為四乙烯五胺、五乙烯六胺、六乙烯七胺、聚乙烯聚胺、 或者是這些之混合物。 [3 ].刚述[1 ]或[2 ]記載之聚醯胺硬化劑組合物係化合 物⑻為N-胺基乙基娘嗪、派噪、二乙烤三胺之部分N甲 基化物、N:N—二甲基胺基丙基胺、或者是這些之混合物。 [4 ].則述[1 ]至[3 ]中任一項所記載之聚醯胺硬化劑組 。物係化合物(A)和化合物⑻之莫爾數比(a/b)為9〇/1〇 〜40/60之範圍。 項所記載之聚醯胺硬化劑組 之莫爾數比(A/B)為85/ 15 [5]:前述[1]至[3]中任一 合物係化合物(A)和化合物(B) 〜50/ 50之範圍。 記載之聚酿胺硬化劑組 全量而含有70〜95重 [6]:前述[1]至[5]中任一項所 合物係成分(c)為相對於成分(c)之 量%之二聚物酸。 ▲ [7].種%氧樹脂硬化物係前述[1 ]至[6]中任-項所 記載之聚醯胺硬化劑缸人4 ^ 』且α物和壞氧樹脂發生反應而得到。 ]^述[7 ] °己載之環氧樹脂硬化物係聚醯胺硬化劑 、,且合物中之胺氫原子相對 子於%氧樹脂中之環氧基之莫爾數 6 201202175 比為1. 5/1〜1/1. 5之範圍。 [9]:前述[7]或[8]記載之環氧樹脂硬化物係環氧樹月t 為雙齡A型環氧樹脂、雙盼F型環氧樹脂、雙紛心型環‘ 樹脂、雙續型環氧樹脂、甲㈣搭型環氧樹脂、或者 是這些之混合物。 【發明效果】 本發明之聚酿胺硬化劑組合物係比起來自於一般大多 使用之三乙烯四胺之聚醢胺硬化劑而顯示良好之性能。 例如包含二乙烯三胺(al )來作為化合物(A)之本發明 之聚醯胺硬化劑組合物係比起來自於習知之三乙烯四胺之 聚醯胺硬化劑而顯示良好之可撓性及儲存安定性。於是, 了以適合使用在要求高度之可撓性之塗料領域。 此外,包含藉由前述之化學式(1)所表示之每丨分子之 氮原子數為5以上之胺化合物(32)來作為化合物(A)之本 發明之聚醯胺硬化劑組合物係顯示同等於來自習知之三乙 烯四胺之聚醯胺硬化劑之可撓性及耐水性,顯示更加良好 之硬化性能和儲存安定性❹此外,也可以改善成為來自於 S知之二乙烯四胺之聚酿胺硬化劑之缺點之低溫硬化性。 【實施方式】 本發明之聚醯胺硬化劑組合物’其特徵在於:含有由 二乙烯三胺(al)和藉著下列之化學式(丨): 201202175 1)201202175 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical that best shows the characteristics of the invention. WORKING STATEMENT: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyamine hardener composition. The polystyrene curing agent composition of the present invention is a curable composition of an epoxy resin used as a coating material, a binder, a floor material or the like. [Prior Art] The polyacrylamide resin composition is generally obtained by using a polybasic acid and a polyamine compound as a raw material 'dehydration condensation between an amine group and a carboxyl group under heating to form a guanamine bond and a polymer chain. Extend and synthesize. Specifically, it has been known that a dibasic acid or a polybasic acid such as adipic acid or a dimer acid, and a polyamine such as ethylene diamine or diethylene triamine are used as a starting material by a guanamine bond. A resin or the like that connects the two constituent units (for example, refer to Patent Document 1). Here, the dimer acid has a rich reactivity and is a dibasic acid having the highest molecular weight which is industrially obtained. In these polyamide resin compositions, '201202175-derived amine derived from a dimer acid becomes strong and exhibits flexibility' and has good adhesion properties, and therefore, as an adhesive, ink, surface coating The agent or the epoxy resin hardener is applied to an epoxy resin, or is used as a two-liquid reaction type adhesive for surface coating such as metal, (4), or ceramics. In the manufacture of the polyamide resin composition, I use diethylenetriamine (_', triethylenetetramine (-, tetraethylene pentamine (oxime), pentaethylene hexamine, oxime), etc., but Polyvinylamine-based oxime which is the most commonly used commercially. 4 醯 Polyamide curing agent derived from & known diethylenetetramine has a problem in low-temperature curability, and has been used in recent years for wind power generation. In the field of coatings such as turbines, it is more desirable to use a polyamide hardener which is more flexible than a base rubber. This is because in the same field, the curvature of the turbine becomes larger, and the fly is The problem of contact, etc., is remarkable, and it is required to use a coating film which does not peel more. Therefore, it is proposed to use a polyamine hardener which is a mixed composition of triethylenetetramine and a polyamine having a piperazine ring (for example, refer to Patent Document 2) According to the same publication, the obtained polyamine hardener can reduce the amount of epoxy resin relative to the polyamide hardener, thereby reducing the viscosity of the system, and obtaining a shorter film hardening time and impact resistance. Sex A good coating film. The polybenzamine hardener which is contained in the same publication has a tendency to decrease more than the tensile strength of the coating film using triethylenetetramine alone. It is suitable for the field which is equivalent to the same performance as triethylenetetramine. In addition, the equivalent of active hydrogen becomes large, and polyamine/ring 201202175 is difficult to say that it is suitable for the requirement that the ratio of highly water-resistant oxygen resin becomes high, and therefore it is used. Triethylenetetramine (TETA) is a limited supply of raw materials, which is relatively expensive compared to other polyethylene polyamines. Therefore, in the manufacture of polyamine hardeners, it is required to be relatively stable and more stable. An economical alternative ingredient. Thus, as a substitute for triethylenetetramine (TETA) 2 polyamine component is proposed. Use 3 N-3 aminopropyl ethylene diamine, ν, ν, - bis (3-amine Propyldiamine, hydrazine, hydrazine, hydrazine, tris(3-aminopropyl)ethylenediamine, hydrazine, hydrazine, hydrazine, hydrazine-tetrakis(3-aminopropyl)ethylenediamine A polyamine hardener of a mixture (for example, refer to Patent Document 3). According to the same publication, a shorter film hardening time is obtained than ΤΕΤΑ'. However, the epoxy resin cured by the polyamine hardener described in the same publication is harder than the conventional polyamine. The agent is more inferior in flexibility. Therefore, it is not particularly easy to replace the ruthenium in the case of a coating material requiring flexibility. [Prior Art Document] [Patent Document] [Patent Document 1] US Patent No. 2,450,940 [Patent Document 3] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2-7-76. [Invention] [Problems to be Solved by the Invention] 4 201202175 The present invention has been made in view of the foregoing. The object of the prior art is to provide a polyamine hardener composition which can be substituted for the polystyrene hardener from the most commonly used triethylenetetramine and which is not derived from triethylenetetramine. Specifically, φ ζ (1) is a polyamine sclerosant composition which is not derived from triethylenetetramine, which exhibits good flexibility and storage stability compared to a polyamine-derived melamine curing agent derived from triethylenetetramine. Or (2) shows the flexibility and water resistance equivalent to the polyamine amine hardener from triethylenetetramine and shows better hardening properties and storage safety; t is not derived from triethylenetetramine A polyamine hardener composition. [Means for Solving the Problem] The inventors of the present invention thoroughly reviewed the 'results' with respect to the polyamine hardener composition to complete the present invention. That is, the present invention relates to a polyamine hardener composition as shown below and an epoxy resin cured product obtained by using the polyamine hardener composition. [Π·- a polybenzamine hardener composition characterized by containing: diethylamine (al) and the following chemical formula: H2N^^P NH2 (1) (in the chemical formula, η represents 3 or more The number 〇 represents the group of amine compounds (a2) having a nitrogen atom number of 5 or more per molecule: the compound is obtained, the nitrogen atom of each molecule is below 4 and the active hydrogen number is 201202175 The reaction product of the amine compound (B) of 2 or 3 and the component (c) containing the dimer acid and [the total number of moles of the compound (A) and the compound (B)] / [component (c) The molar number in terms of polymer acid] is in the range of 2/1 to 4/3 and the molar ratio of the compound (A) to the compound (B) (a/^ is in the range of 9 〇/1 〇 15 15 /85) [2] The polyamine hardener composition according to the above [1], wherein the compound (A) is tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptaamine, polyethylene polyamine, or It is a mixture of these. [3]. The polyamine hardener composition according to [1] or [2] is a compound (8) which is a part of N-aminoethyl azine, a noise, and a di-baked triamine. N A The carbamide hardening agent group according to any one of [1] to [3], wherein the polyamine amine hardener group according to any one of [1] to [3]. The molar ratio (a/b) of the compound (A) and the compound (8) is in the range of 9 Å / 1 Torr to 40 / 60. The molar ratio of the polyamine hardener group described in the item (A/B) And 85/15 [5]: the range of the compound (A) and the compound (B) to 50/50 of any one of the above [1] to [3]. The polyamine-containing hardener group described above contains the entire amount. 70 to 95 weight [6]: The component (c) according to any one of the above [1] to [5] is a dimer acid in an amount of % relative to the component (c). ▲ [7]. The oxy-hardened resin is obtained by reacting the α-form and the bad-oxygen resin in the polyamine curing agent cylinder according to any one of the above [1] to [6]. [7] ° 5/1〜1 The ratio of the molar ratio of the epoxy group of the epoxy resin to the epoxy group in the % oxygen resin 6 201202175 is 1. 5/1~1 [1]: The hardened epoxy resin described in [7] or [8] above is a double-aged type A epoxy tree. a fat, a double-confident F-type epoxy resin, a double-hearted ring type resin, a double-stranded epoxy resin, a nail-type epoxy resin, or a mixture of these. [Effect of the invention] The polyamine hardening of the present invention The composition exhibits good performance compared to a polyamine hardener derived from triethylenetetramine which is generally used in general. For example, the polyamine of the present invention containing diethylenetriamine (al) as the compound (A) The hardener composition exhibits good flexibility and storage stability compared to the polyamine hardener from the conventional triethylenetetramine. Thus, it is suitable for use in the field of coatings which require a high degree of flexibility. In addition, the polyamine lubricant hardener composition of the present invention containing the amine compound (32) having a nitrogen atom number of 5 or more per molecule represented by the above chemical formula (1) is equivalent to the compound (A). The flexibility and water resistance of the polyamidamine hardener from the conventional triethylenetetramine show more excellent hardening properties and storage stability. In addition, it can also be improved as a blend of ethylene glycol from S. Low temperature hardenability of the disadvantages of amine hardeners. [Embodiment] The polyamine hardener composition of the present invention is characterized by containing a diethylenetriamine (al) and by the following chemical formula (丨): 201202175 1)
NH (在化學式中,n係表示3以上之數字。)所表示之每】分 子之氮原子數為5以上之胺化合物(&2)來組成之群組而選 出之化合物U)、每1分子之氮原子數為4以下且活性氫數 為2或3之胺化合物(B)以及包含二聚物酸之成分(c)之反 應生成物並且[化合物(A)和化合物(⑺之合計莫爾數]/ [成分(c)之二聚物酸換算之莫爾數]為2/1〜4/3之範圍 且化合物(A)和化合物(B)之莫爾數比(A/B)為9〇/ι〇〜ΐ5 /85之範圍的反應生成物。 …在本發明,使用於化合物⑴之二乙稀三胺(al)係例如 可乂藉由1,2-—氯乙院和氨發生反應而進行合成,可以 藉由進行蒸館精製而得到成為單一化合物。此外,也可以 使用市面販賣品。 -料,使用於化合物⑴且藉由前述之化學式⑴所表 =之母1分子之氮原子數為5以上之胺化合物U2)係例如 以藉由1,2_二氣乙烷和氨發生反應而進行合成。作 此種胺化合物係具體地例舉四乙稀五胺、五乙烯六胺^ 乙烯七胺、聚乙烯聚胺等。NH (in the chemical formula, n is a number of 3 or more.) The compound U), each of which is selected from the group consisting of an amine compound having a nitrogen atom number of 5 or more. An amine compound (B) having a molecular number of nitrogen atoms of 4 or less and an active hydrogen number of 2 or 3, and a reaction product of the component (c) containing a dimer acid and [the total of the compound (A) and the compound ((7)) The number of moles] / [the number of moles of the dimer acid of the component (c)] is in the range of 2/1 to 4/3 and the molar ratio of the compound (A) to the compound (B) (A/B) a reaction product in the range of 9 〇/ι〇~ΐ5 /85. In the present invention, the diethylenetriamine (al) used in the compound (1) can be, for example, a 1,2-chloroethane and Ammonia is reacted and synthesized, and it can be obtained as a single compound by steaming. Further, a commercially available product can be used. The material is used in the compound (1) and the mother 1 molecule represented by the above chemical formula (1) The amine compound U2) having a nitrogen atom number of 5 or more is synthesized by, for example, reacting with 1,2-dioxaethane and ammonia. Specific examples of such an amine compound include tetraethylene pentamine, pentaethylene hexamine, ethylene heptaamine, and polyethylene polyamine.
作為化合物(A )得可M ,人、 〈」係了以早獨地使用這些化合物,也可以 ,,且σ這些化合物而使 & 在廷些當中,最好是二乙烯三胺、 ’、胺、六乙烯七胺、或者是這些之混合物。 舉基::化合物⑻係並無特別限定’但是,列 胺基乙基η底嗪、娘。表、 瓜秦、二乙烯三胺之部分Ν—甲基化 8 201202175 物、或者A N'甲基乙烯二胺、N-乙基乙烯二胺、N—異 丙基乙烯二胺、N一甲基胺基丙基胺、n,n—二甲基胺基丙 基胺N’N— —乙基胺基丙基胺、乙烯二胺(EDA)之單體或 - N甲基化物、牛脂胺(例如以丨,3 _二胺基丙院作為 鹼胺’在1位之胺基,鍵結2個之Ci6或Ci8之烷基而成為 3級胺基等。)等。 作為化合物(B)係可以單獨地使用這些化合物,並且, ^可以組合而使用。在這些當中’最好是二乙燁三胺之部 分N-甲基化物、N_胺基乙基派嗓"辰噪、Μ—二甲基 胺基丙基胺、或者是這些之混合物。 作為對於二乙烯三胺呈部分地進行N_甲基化之方法 係並無特別限定,但是’適合列舉例如制^來作為N 一甲基化劑之方法。 在像這樣得狀N-甲基化體,成為先驅體之二乙稀 =胺内之鍵結於氮原子之活性氫科(在以下,有將鍵結於 分子内之氮原子之活性氫原子來稱為「胺基氫原子」之狀 也發生。)進行甲基化之比例係最好是4〇%〜之範圍。 在本發明,化合物(A)和化合物(B)之混合比率(A/b) 係ΘΟ/ΙΟ、”/85(莫爾數比)之範圍,但是,最好是㈣ /10〜40/ 60(莫爾數比)之範圍,更加理想是85/15〜5〇 /50(莫爾數比)之範圍。 在本發明,使用於成分(C)之所謂「二聚物酸」係表示 聚合不飽和脂肪酸而進行二聚之酸,包含其醋。 作為在二聚物酸之合成來使用之不飽和脂肪酸係列舉 201202175 例如單官能性不飽和脂肪酸。具體地說,適合例舉硬脂酸、 標櫚酸、油酸、亞油酸、列寧酸或這些之混合物、或者是 妥爾油脂肪酸、大豆脂肪酸、菜種油脂肪酸、綿籽脂肪酸 等。最佳之不飽和脂肪酸係妥爾油脂肪酸(以油酸和亞油 酸,作為主成分^)。 此外’作為二聚物酸之原料係除了前述之不飽和脂肪 酸以外’還可以使用其酯。作為不飽和脂肪酸之酯係適合 列舉例如前述之單官能性不飽和脂肪酸之低級烷基酯。具 體地例舉前述之單官能性不飽和脂肪酸之甲基酯、乙基 醋、η —丙基酯、叔丁基酯等。這些係可以單獨地使用,並 且,也可以併用2種以上。作為二聚物酸之原料係在併用 不飽和脂肪酸之酯之狀態下,得到二聚物酸之酯。 二聚物酸係一般藉由在加壓下,聚合前述之原料而進 行調製。在此,聚合反應係最好是進行於高酸強度之路易 斯酸型或布朗斯台德酸型觸媒之存在下。此外,在不飽和 脂肪酸之酯作為原料之狀態下,還藉由經過水解製程而得 到二聚物酸。 以像這樣得到之二聚物酸來作為主成分之反應液係通 常包含二聚物酸或者是聚合度更加高之酸,並且,還含有 未反應之不飽和脂肪酸或副生成之支化脂肪酸等之單體成 分。因此,藉由蒸餾而除去這些單體成分之大部分。作為 蒸館係並無特職定,但是,最好是進行減壓㈣。還可 以氫化該反應液,藉此而減低生成物之不飽和度及著色。 此外,還可以藉由對於蒸館之殘㈣進行分子蒸館而進行 10 201202175 精製。此外,反應液中之二聚物酸和三聚物酸以及聚合度 更加高之酸之比率係配合聚合條件、精製條件以及成為原 料之不飽和脂肪酸等而進行變動。 在本發明,可以使用像這樣得到之反應生成物,來作 為成刀(c)。成分(〇係通常包含二聚物酸、三聚物酸聚 合度更加高之酸等之多官能性脂肪酸或其酯。 分(C)之全量而最好是含有70重量%〜95重量%之二聚物 酸。此外’最好是含有3重量%〜3。重量%之三聚物酸以及 聚合度更加高之酸(包含這些之3旨)。此外’作為殘留部係 可以含有原料之不飽和脂肪酸或者是配合需要而含有其他 之單官能性㈣或多官能性_。作為成分(c)係特別適人 將使用含有70重量%以上之油酸或其低級燒基酷之單官妒 性不飽和脂肪酸而得到者予以使用,來作為原肖。月11 為了作用成為環氧樹脂之硬化劑,因此,必須存在末 ㈣基,所以,化合物⑴、化合物⑻和成分(c)係[化人 換⑻之合計莫爾數],[成分(C)之二聚物酸 換算之莫爾數]通常為2/1〜4/3之士办丨& ’ 4’3之比例而進行反應。可 乂藉由這些比例成為4/3以上而、南痒仏袖 ^ θ Μ度地調節反應物之分 子罝,可以得到作為目的之聚刀 液能业物tL M W,上D物’來成為 液態狀物此外,可以藉由比率成為2/!以下而防… 之胺化合物未發生反應來殘留。 此外,作為化合物(B)係在 M田甘 使用對於一乙烯三胺呈部分 地進仃N—甲基化而得到之組 抑又狀態下,胺化合物之 11 201202175 合計莫爾數係根據對於二乙烯三胺呈部分地進行N_曱基 化而得到之組合物之平均分子量,來進行計算。 此外,成分(c)之二聚物酸換算之莫爾數係由成分 之酸價來計算,算出成為平均2官能酸。 化合物(A)、化合物(B)和成分(C)之反應係通常在常壓 下、120〜280t、最好是18〇〜250t之溫度範圍,進行加 熱而進行反應。此外,A 了防止生成物之著色,因此,有 利於進行在氮氣等之惰性氣體氣氛下。 反應時間係由於反應溫度或使用之原料種類而受到左 右,無法-概地決定,但是,通常為2〜5小時程度而就充 刀。此外’最好是在反應結束前,以減壓狀態,來進行適 ,之時間熟化。隨著反應之進行而提高反應液之點度,但 疋,即使是在反應結束後,也並無固化反應生成物,即使 是室溫’也容易由反應用容器,來移送至保存容器。此外, 可以配合需要而在反應結切,添加甲苯、:甲笨、醇等 之溶媒。 本發明之聚醯胺硬化劑組合物係含有像這樣得到之 應生成物。 本發明之聚醯胺硬化劑組合物係可以包含芳香族炉 合物、脂肪族烴化合物、嗤、酮、醚、醇等之溶媒:: 溶媒係最好是甲笨、-甲甘 ' 本—甲本專。聚醯胺硬化劑組合物中 溶媒含有量係最好是〇〜6〇舌旦^阁 a ou重量%之範圍’更加理相是 40重量%之範圍。 〜 此外,可以在本發明 > 取t Λ , 73之聚醯胺硬化劑組合物,還含 12 201202175 其他之多官能性胺。作為此種多官能性胺係並無特別限 定’但是’列舉例如乙烯二胺、二乙烯三胺、三乙烯四胺、 四乙稀五胺、分子量更加高之聚乙稀胺、派嗪'間苯樓二 甲基二胺、異佛爾酮二胺、3, 3’ _二甲基一4, 4’ 一二胺 基二環己基甲烷、4,4,一二胺基二環己基甲烷、2, 4,一 一胺基二環己基甲烧、U —二胺基丙烧、1,3 —二胺基丙 烧、1,4—二胺基丁烷、二胺基戊烷、16_二胺基己 烷、雙一(3 —胺基丙基)胺、N,N,_雙—(3 —胺基丙基) 一 1,2~二胺基乙烷、1,2 —二胺基環己烷、1,3 —二胺基環 己烷、1’ 4一二胺基環己烷、聚氧烷撐聚胺(例如Jef “⑴丨⑽ D-230 ^ Jeffamine D-400 > Jeffamine D-2000 ^ Jeffamine D-4000 ' jeffamine T_4〇3)等。 设有,就本發 w刊倒畑π 1。初.wu ^ u 本發明之環氧樹脂硬化物係藉由反應本發明之聚醯胺 更化劑組合物和環氧樹脂而形成。就本發明之聚酿胺硬化 劑組合物和環氧樹脂之反應而言,並無特別限定,作是, =藉由混合·接觸這些而形成硬化物。也可以配合需要 而施行加熱處理,強制地進行硬化。 I特別5ΐ用於本發明之環氧樹脂硬化物之環氧樹脂係並 := …但是,列舉例如每1分子含有2以上之12 環化之聚環氧化合物,具體地例舉㈣" 氧樹脂:多官二環:樹脂、環氧㈣樹脂、脂環式環 樹脂係可以使用匕^ 、演化環氧樹脂等。這些環氧 使用無溶媒者,也可以使用藉由溶媒而稀釋h 13 201202175 在本發明,纟發明《聚醯胺硬化劑組合物和環氧 係[本發明之聚醯胺硬化劑組合物中之胺氫原子]/产月旨 樹脂中之環氧基]通常為U/1〜1八5(莫爾數比:)之 範圍、最好是[2/卜(莫爾數比)之範圍而進 應。可以藉由像這樣而發揮良好之環氧樹脂之硬化物性。 在本發明,在形成環氧樹脂硬化物之際,除了本發明 之聚醯胺硬化劑組合物以外,還可以併用向來習知之硬化 促進劑。作為此種硬化促進劑係並無特別限定,但是 如有機酸化合物、醇化合物、苯酚、叔胺、羥基胺以外: 還列舉類似於這些之化合物。即使是在這些當中,作為特 別有用之硬化促進劑係也列舉苯㉝、壬基_ H、雙 ,A、水楊酸、二甲基胺基甲基苯酴、雙(二f基胺基甲幻 笨酚、三(二甲基胺基甲基)苯酚等。 土 此外,在本發明,在形成環氧樹脂硬化物之際可以 使用向來I知之可塑劑。作為此種可塑劑係並無特別限 定,但是’適合列舉节醇、壬基笨酚之各種之笨二 等。 此外,在本發明,在形成環氧樹脂硬化物之際,可以 使用溶媒、填充劑、顏料、顏料分散劑、流變修飾劑、觸 變劑、流動化及平滑化輔助劑、消泡劑等。作為適當之溶 媒係列舉例如芳香族烴化合物、脂肪族烴化合物、酯、酮、 、醇等。 實施例 藉由以下之參考例和實施例而還更加詳細地說明本發 14 201202175 明’但是,本發明係並非限定於這些而進行解釋。 此外,反應生成物之分析係藉由以下之方法而進行。 <反應生成物之分析> (1) 氣體色譜分析 分析柱:DB — 5(Agi lent技術公司製、長度30m '薄膜 厚度 2.5em、内徑 0.32mm) 柱溫度:6(TC + 1(TC/分鐘升溫+ 280°C/15分鐘。 (2) 核磁共振(NMR)分析(4- NMR) 使用Gemini — 200型核磁共振裝置(varian公司製)而 進行。 就環氧樹脂硬化物而言’塗膜之硬化速度和物性測定 之評價係正如以下而實施。 <薄膜硬化時間之評價> 對於環氧樹脂組合物,使用英吋塗佈器而將7 6微米之 潤濕膜厚度之塗膜’適用於玻璃面板(25cmx2cmx〇. 2cm)。 使用低溫恒溫恒濕機(Espec公司製、商品名稱:pL_ 3κ), 在溫度25t、相對濕度50%之一定條件,於硬化後,使用 RC型乾燥定時塗佈器(塗佈測試器公司製)而進行測定。藉 由以該測定來顯示之2次線狀痕跡消失時間(Hr.)而評價 硬化性。 <塗膜之抗拉強度及可撓性之評價> 對於環氧樹脂組合物,使用間隙調整成為2〇〇微米之 刮刀而均勻地塗佈於聚丙烯薄膜(2〇cmx4〇cmx〇. 2顏)之 上,使用低溫恒溫恒濕機(Espec公司製、商品名稱:pL_ 15 201202175 進行48小 3 Κ ) ’在溫度2 5 C、相對濕度5 0 %之一定條件, 時之乾燥·硬化。 然後,使用抗拉試驗用之哑鈐型沖切器(JISK 6259 2 號型啞鈐狀)而製作測試片。使用平行夾緊鎖而將測試片, 安裝於TENSILON萬能試驗機(〇rientec公司製、商β名 稱:RTM500) ’以30mm/min之速度,來進行拉引,測定樣 本片之最大抗拉強度(kgf/mm2)。同時,藉由定規而計測 在測試片之破斷時之標線間距離(初期為4〇mm),測定在破 斷時之抗拉延伸率判斷抗拉延伸率(%)越大而塗膜之 可撓性越高。 <硬化塗膜之耐水性評價> 在調溫成為40°C之水槽來浸潰1日及7日硬化後之塗 膜24小時之後,藉由目視而評價塗膜之狀態變化。結果係 藉由以下之4階段而進行評價。 ◎:優良(無變化);〇:良好;△:稍微不良;χ :不 良(發生塗膜表面之膨脹及變形、塗膜之變色)。 〈儲存安定性之評價> 將5成之二聚物酸•聚醯胺胺縮合物,放入至恒溫機 (楠本化成公司製、商品名稱:HIFLEX FL4050),冷卻至一 20 C為止而保持}小時。然後,提高恒溫機之溫度至, 在維持1小時之後’藉由目視而調查二聚物酸•聚醯胺胺 縮合物之狀態。同樣地’提高溫度至20、25、30、35、40、 50、60 ' 70 ' 80、i〇〇°c,在保持i小時後,分別藉由目視 而調查聚醯胺之狀態。將二聚物酸.聚醯胺胺縮合物成為 16 201202175 液體狀之溫度,定義成為「液體壯外、、ra ώ 收體狀化溫度」。液體狀化溫 度越低而二聚物酸•聚酿胺胺縮合物之結晶性越低,判斷 聚醯胺硬化劑組合物之儲存安定性呈良好。 製造例1 一乙稀二胺之部分Ν —曱基化 在1〇o〇ml之附有授拌機之高壓銷内,裝入二乙稀三胺 2〇〇g(TGSGH公司製、商品名稱:順)、水iQQg及觸媒pd -C(附載5%)之2· Gg。在密閉高壓鋼而進行氫取代之後, 於授拌下,升溫至⑽為止。接著,在高壓鋼内,以壓 力3MPa來導入氫,並且,妓7 ,。士 ^經過7小時而藉由幫浦來供應 37%曱醛水溶液314g。在進扞!,丨、拄夕热/ 你m仃i小時之熟化反應後,進行 冷卻而取出反應液。 在使用蒸餾裝置而由反應液來餾除水之後,於減壓 下:得到生成物236g。對於該生成物來進行氣體色譜分析 及1H-NMR分析,結果,相對於鍵結在二乙婦三胺之氣原 子之氫基而變換40%來成為甲基([甲基]/[氫原子]=4〇/ 60(莫爾數比))。於是,該生成物之每1分子之平均之活性 氫數系3。 此外,得到之胺化合物之組成係DETA/單甲基體/二 甲基體/四甲基體/五甲基體=7 7/25 MM 7/231 /7.6/l.〇(GC 面積比)。 在以下,將對於在本製造例來得到之二乙稀三胺呈部 分地進行N—甲基化而得到之組合物,稱為「DETA-2M」。 製造例2乙烯二胺之部分3 —胺基丙基化 在1公升之反應容器’加入236g之乙烯二胺而加熱至 17 201202175 6 0 C。在該混合物,經過2小時而加入41 7g之丙烯腈。在 結束丙烯腈之追加後,還在6〇〇c,維持2小時之反應。 在1公升之間歇式反應器’加入在前製程來形成之生 成物500g,並且,還裝入100g之異丙醇和7 58之RaneyC〇 觸媒。在反應谷器内進行氮取代而驅逐出空氣之後,以 5. 5MPa之氫來充滿,接著,加熱至。反應器之壓力 維持在5. 5MPa ’溫度維持在12〇°C而進行1小時之反應。 反應器係冷卻至室溫為止’藉由過濾而得到除去固態 成分之反應液。藉著由反應液,來減壓餾除異丙醇和低沸 點成分,而得到682g之生成物。對於該生成物來進行氣體 色譜分析及1Η — NMR分析,結果,在鍵結於乙烯二胺之氮 原子之氫基中,50%係取代成為胺基丙基。此外,得到之生 成物之組成係單胺基丙基取代體/雙胺基丙基取代體/三 胺基丙基取代體/四胺基丙基取代體= 7/8〇/11//2(gc 面積比)。 在以下’將對於在本製造例來得到之乙稀二胺呈部分 地進行3 —胺基丙基化而得到之組合物,稱為「apeda」。 實施例1. 在1000ml之玻璃容器,加入包含單體酸7重量%和三 聚物酸14重量%之Cu不飽和脂肪酸之二聚物酸之組合物 [成野食品工業公司製、商品名稱:Tsunodime216、酸價: 193. 6mgKOH/ g、適合於成分(C)。]之l〇〇g,並且,還進 行攪拌同時緩慢地加入21. 4g之二乙烯三胺(TOSOH公司製) 和6. 7g之N-胺基乙基略嗪[TOSOH公司製;適合於化合物 18 201202175 (B)。]而使得[化合物(A)和化合物(B)之合計莫爾數]/ [成 分(C)之二聚物酸換算之莫爾數]成為3/2。提高攪拌速度 至150rpm,在氮氣氛下、2〇(TC,加熱4小時,藉由蒸餾 而除去6.2g之水。此外,在2〇〇。(:、10mmHg,進行i小時 之反應。 接著,冷卻反應用容器至1〇(rc為止,在加入甲苯來 進们·攪拌而作為均勻之甲笨溶液來成為固態成分濃度7〇 重量%之後,冷卻至室溫為止。在此得到之反應生成$ (二 聚物酸•聚醯胺胺縮合物)係琥珀色,在不包含 下之活性氩當量係227。 ,田A X 〜米孔埘脂(油化 SHELL環氧公司製、商品名稱:邮⑽ι〇〇ι、環氧告量 474之㈣A型環氧樹脂)而成為重敝環氧樹脂:液 32重讀,u 68重量份之比例,來添加得到之二聚物酸· 聚酿胺胺縮合物之甲苯溶液,使用刮勺,於室溫下, 5分鐘之剪斷搜拌。在此,[本發明之聚酿胺硬化 中之胺氫原子[環氧樹脂中之環氧基]係l/i(莫爾數 比)。將按照前述之評價方法 、 測定之結果,顯示於表卜 Μ膜之硬化逮度和物性 實施例2〜實施例9以及比較例1〜比較例15 其餘1及表2所顯示之種類和量之原料以外, 及表2。 I施例1而實施。將其結果—併顯示於表i 19 201202175 〔I<】 比較例5 〇 〇 1 1 <N1 CO CO 00 s' ί 1 \ CO σ> eo (Nl CO CO CD 00 iri t- 〇 s s i比較例4 § 1 1 卜 卜· 1 CO ύ 1 1 CO C<1 CO σ> CO ΙΛ LT) oo ci CO oo s |比較例3 | g 1 1 Ο 1 呀 1 1 (Μ \ ΙΓ> C<i CO CO CO oo CO in* t- to ΟΪ g I比較例2 | ο ο 1 1 CO ΟΟ 1 oo s 1 1 c<j \ CO 呀 CO "•CP CO CO CO m in CO o* o g 比較例1 ο 1 1 1 t t- 03 CO 1 1 CO CvJ c3 CO CO Lfi 卜 s 實施例9 ο cd 1 卜 cd CO LTJ 1 1 1 60/40 1 CM \ CO £ <NI oo CO CM CO 卜 ιΛ s o CO :實施例8 g Γ ΟΟ 1 CO LD 一 1 1 1 70/30 1 <M CO 寸 CO CO CO ο cd CM oo σ> 另 實施例71 g 1 1 LT5 1 1 1 80/20 1 ζα CO CO <>a C<l C<1 eo oo CO 呀 CO CO oo o CO 實施例6 ο ο cd 1 CO 1 1 1 1 60/40 1 CO \ <N1 CO CO ο CO c=> CM o 另 實施例5 | ο ο 卜 οό 1 »-Η ο 1 1 1 1 70/30 1 CN1 \ 00 兮 CO CO CO CO 05 ιτί o σ> o ΙΛ οα Li施例4 I g Ξ CO CO 1 1 1 1 1 60/40 1 CM \ CO CO CM Cvl (NI CO oo ς〇 CO in o g ΙΛ eo |實施例3 I g 卜 〇d CO o 1 1 1 1 1 70/30 1 CO \ ΙΛ c3 CO 05 o 05 ID* CNI LT5 00 實施例2 I ο ο 03 00 CO 1 1 1 1 1 80/20 1 \ CO o CO 呀 oo 宕 實施例1 | g 寸 C<1 1 卜 cd 1 1 1 1 80/20 1 C<I c- C〇3 CvJ <N1 CO oo CO CD ς〇 (Nl o 05 LT3 CM 3 Ί 二乙烯三胺 DETA-2M N-胺基乙基哌嗪 专 三乙烯四胺 APEDA 胺A/胺B(莫爾數比) 胺(A+B)/二聚物酸(C)(莫爾數比) 活性氫當量 聚醯胺胺硬化劑添加重量份數(pbw) 環氧樹脂添加重量份數(pbw) 硬化性(Hr.) 塗膜強度[抗拉強度(kgf/mm2)] 可撓性[抗拉延伸率00] 液態化溫度(°c) c CQ S /<**N ^ 3 s 物性 評價As the compound (A), it is possible to use these compounds in advance, and it is also possible to use these compounds as a compound of σ, and it is preferable to use diethylenetriamine, ', An amine, hexaethylene heptaamine, or a mixture of these. Base: The compound (8) is not particularly limited. However, it is an alkylaminoethyl azine. Table, part of guanidine, diethylenetriamine Ν-methylation 8 201202175, or A N' methyl ethylene diamine, N-ethyl ethylene diamine, N-isopropyl ethylene diamine, N-A Aminopropylamine, n,n-dimethylaminopropylamine N'N-ethylaminopropylamine, ethylenediamine (EDA) monomer or -N methylate, tallow amine (For example, 3, 3 _ diaminopropyl propyl as an alkali amine 'in the amino group at the 1-position, two alkyl groups of Ci6 or Ci8 are bonded to form a tertiary amino group, etc.). These compounds can be used singly as the compound (B), and can be used in combination. Among these, 'preferably, a part of diethylenetriamine, N-methylate, N-aminoethylpyrene" chen, dimethyl-dimethylaminopropylamine, or a mixture thereof. The method for partially performing N-methylation of diethylenetriamine is not particularly limited, and 'for example, a method for producing an N-methylating agent is exemplified. In the case of the N-methylated body thus obtained, it becomes a precursor of diethylene = the active hydrogen group bonded to the nitrogen atom in the amine (hereinafter, there is an active hydrogen atom which bonds the nitrogen atom bonded to the molecule) The term "amino-based hydrogen atom" also occurs. The ratio of methylation is preferably in the range of 4% by weight. In the present invention, the mixing ratio (A/b) of the compound (A) and the compound (B) is in the range of ΘΟ/ΙΟ, "/85 (moire ratio), but preferably (four) /10 to 40/60 The range of (the molar ratio) is more preferably in the range of 85/15 to 5 〇/50 (moire ratio). In the present invention, the so-called "dimer acid" used in the component (C) means polymerization. An acid that is dimerized with an unsaturated fatty acid, including its vinegar. As a series of unsaturated fatty acids used in the synthesis of dimer acids, 201202175, for example, monofunctional unsaturated fatty acids. Specifically, it is preferably exemplified by stearic acid, palmitic acid, oleic acid, linoleic acid, linonic acid or a mixture thereof, or a tall oil fatty acid, a soybean fatty acid, a vegetable oil fatty acid, a cottonseed fatty acid or the like. The most preferred unsaturated fatty acid is tall oil fatty acid (using oleic acid and linoleic acid as the main component ^). Further, as the raw material of the dimer acid, in addition to the aforementioned unsaturated fatty acid, an ester thereof can also be used. As the ester of the unsaturated fatty acid, for example, a lower alkyl ester of the above-mentioned monofunctional unsaturated fatty acid is exemplified. Specific examples thereof include methyl esters of the above-mentioned monofunctional unsaturated fatty acids, ethyl vinegar, η-propyl ester, tert-butyl ester and the like. These systems may be used singly or in combination of two or more. As a raw material of the dimer acid, an ester of a dimer acid is obtained in a state in which an ester of an unsaturated fatty acid is used in combination. The dimer acid system is generally prepared by polymerizing the aforementioned raw materials under pressure. Here, the polymerization reaction is preferably carried out in the presence of a Lewis acid type or a Bronsted acid type catalyst having a high acid strength. Further, in the state in which an ester of an unsaturated fatty acid is used as a raw material, a dimer acid is obtained by a hydrolysis process. The reaction liquid system containing the dimer acid obtained in this manner as a main component usually contains a dimer acid or an acid having a higher degree of polymerization, and further contains an unreacted unsaturated fatty acid or a by-produced branched fatty acid. The monomer component. Therefore, most of these monomer components are removed by distillation. There is no special job as a steaming hall, but it is best to carry out decompression (4). It is also possible to hydrogenate the reaction liquid, thereby reducing the degree of unsaturation and coloration of the product. In addition, it is also possible to carry out the purification of 10 201202175 by performing molecular vaporization on the residue (four) of the steaming hall. Further, the ratio of the dimer acid and the trimer acid in the reaction liquid and the acid having a higher degree of polymerization are varied depending on the polymerization conditions, the purification conditions, and the unsaturated fatty acid which is a raw material. In the present invention, the reaction product obtained in this manner can be used as the forming tool (c). The component (the oxime system usually contains a polyfunctional fatty acid such as a dimer acid or a trimer acid having a higher degree of polymerization, or an ester thereof. The total amount of the component (C) is preferably 70% by weight to 95% by weight. A dimer acid. Further, it is preferable to contain 3% by weight to 3% by weight of a trimer acid and an acid having a higher degree of polymerization (including these three). Further, the residue may contain raw materials. Saturated fatty acids or other monofunctional (tetra) or polyfunctional _ as needed for the compounding. As component (c), it is particularly suitable for people to use oleic acid containing 70% by weight or more of oleic acid or its lower sulphur base. The unsaturated fatty acid is used as a raw material. In order to function as a hardener for epoxy resin, the terminal (tetra) group is required. Therefore, the compound (1), the compound (8), and the component (c) are The total number of moles of (8) is changed, and the number of moles of the dimer acid in the component (C) is usually 2/1 to 4/3, and the reaction is carried out at a ratio of '4'3. It is possible to adjust the reaction by using these ratios to be 4/3 or more and the south itch sleeve θ Μ The molecular enthalpy of the object can be obtained as the target poly-slurry liquid material tL MW, and the upper D object is made into a liquid substance. Further, the amine compound which is prevented from reacting by the ratio of 2/! In addition, as the compound (B) is used in M-Tangan, the group of the amine compound is partially N-methylated, and the amine compound 11 201202175 is combined with the Mohr number. The diethylenetriamine is calculated by partially calculating the average molecular weight of the composition obtained by N-thiolation. In addition, the molar number of the dimer acid converted to the component (c) is calculated from the acid value of the component. Calculated as an average bifunctional acid. The reaction system of the compound (A), the compound (B) and the component (C) is usually heated under normal pressure at a temperature of from 120 to 280 Torr, preferably from 18 Torr to 250 Torr. In addition, A prevents the formation of the color of the product, and therefore it is advantageous to carry out the reaction in an inert gas atmosphere such as nitrogen gas. The reaction time is affected by the reaction temperature or the type of the raw material to be used, and it cannot be determined generally. Usually, the knife is filled for 2 to 5 hours. In addition, it is preferable to carry out the curing in a reduced pressure state before the end of the reaction. The reaction liquid is increased as the reaction proceeds, but 疋Even after the completion of the reaction, there is no curing reaction product, and even at room temperature, it is easily transferred from the reaction container to the storage container. Further, it can be cut in the reaction as needed, and toluene is added. The polyamine hardener composition of the present invention contains the product to be obtained as described above. The polyamine hardener composition of the present invention may contain an aromatic compound and an aliphatic hydrocarbon compound. Solvents such as hydrazine, ketone, ether, alcohol, etc.: The solvent system is preferably a stupid, - 甲甘' Ben-A. The solvent content of the polyamine hardener composition is preferably in the range of 〇 〇 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Further, in the present invention, the polyamine hardener composition of t Λ , 73 may be further contained, and 12 201202175 other polyfunctional amines are further contained. The polyfunctional amine system is not particularly limited, but includes, for example, ethylene diamine, diethylene triamine, triethylenetetramine, tetraethylene pentamine, a higher molecular weight polyamine, and a pyridinium. Benzene dimethyl diamine, isophorone diamine, 3, 3' _ dimethyl-4, 4' monodiaminodicyclohexylmethane, 4,4, monodiaminodicyclohexylmethane, 2, 4, monoaminodicyclohexylmethyl, U-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, diaminopentane, 16_ Diaminohexane, bis(3-aminopropyl)amine, N,N,_bis-(3-aminopropyl)-1,2-diaminoethane, 1,2-diamine Cyclohexane, 1,3-diaminocyclohexane, 1'4-diaminocyclohexane, polyoxyalkylene polyamine (eg Jef "(1) 丨 (10) D-230 ^ Jeffamine D-400 > Jeffamine D-2000 ^ Jeffamine D-4000 ' jeffamine T_4 〇 3), etc. is provided, the present invention is inverted π 1 . Initial wu ^ u The epoxy resin cured according to the present invention is reacted by the present invention Formed by a polyamine modifier composition and an epoxy resin. The reaction between the brewing amine hardener composition and the epoxy resin is not particularly limited, and the cured product is formed by mixing and contacting them. The heat treatment may be carried out as necessary, and the curing may be forcibly performed. In particular, the epoxy resin used in the cured epoxy resin of the present invention is: = ... However, for example, 12 or more cyclized polyepoxy compounds are contained per molecule, and specifically, (4) " Oxygen resin: Multi-static two-ring: resin, epoxy (tetra) resin, alicyclic ring resin can use 匕^, evolved epoxy resin, etc. These epoxys use no solvent, can also be diluted by solvent h 13 201202175 in this According to the invention, the "polyamine hardener composition and the epoxy system [the amine hydrogen atom in the polyamine hardener composition of the present invention] / the epoxy group in the resin) are usually U/1~ The range of 1 8.5 (Mohr number ratio:) is preferably in the range of [2/b (moire ratio). It is possible to exert good cured properties of the epoxy resin by this. Invention, in addition to the present invention, in forming an epoxy resin cured product In addition to the guanamine hardener composition, a conventional hardening accelerator may be used in combination. The curing accelerator is not particularly limited, but examples of the organic acid compound, the alcohol compound, the phenol, the tertiary amine, and the hydroxylamine are also listed. Compounds similar to these. Even among these, particularly useful hardening accelerators are benzene 33, mercapto _ H, bis, A, salicylic acid, dimethylaminomethyl benzoquinone, bis ( Further, in the present invention, in the case of forming an epoxy resin cured product, a plasticizer known per se can be used. The plasticizer is not particularly limited, but is exemplified by various types of phenolic alcohols and sulfhydryl phenols. Further, in the present invention, a solvent, a filler, a pigment, a pigment dispersant, a rheology modifier, a thixotropic agent, a fluidization and smoothing aid, an antifoaming agent, etc. may be used in forming the cured epoxy resin. . Examples of suitable solvents include aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, esters, ketones, and alcohols. EXAMPLES The present invention will be described in more detail by the following Reference Examples and Examples. However, the present invention is not limited thereto. Further, the analysis of the reaction product was carried out by the following method. <Analysis of reaction product> (1) Gas chromatography analysis column: DB-5 (manufactured by Agilent Technology Co., Ltd., length 30 m 'film thickness 2.5 em, inner diameter 0.32 mm) Column temperature: 6 (TC + 1 ( TC/min temperature rise + 280 ° C / 15 minutes. (2) Nuclear magnetic resonance (NMR) analysis (4-NMR) was carried out using a Gemini-200 nuclear magnetic resonance apparatus (manufactured by Varian Co., Ltd.). 'Evaluation of the hardening speed and physical property measurement of the coating film was carried out as follows. <Evaluation of film hardening time> For the epoxy resin composition, a wet film thickness of 76 μm was used using an inch coater. The coating film is applied to a glass panel (25 cm x 2 cm x 〇. 2 cm). Using a low temperature constant temperature and humidity machine (manufactured by Espec, trade name: pL_3κ), after a certain temperature of 25t and a relative humidity of 50%, after curing, RC is used. The measurement was carried out by a dry-time coating applicator (manufactured by Coating Tester Co., Ltd.), and the curability was evaluated by the secondary linear disappearance time (Hr.) displayed by the measurement. <The tensile strength of the coating film. And evaluation of flexibility> for the epoxy resin composition, A doctor blade having a gap of 2 μm was uniformly applied to a polypropylene film (2〇cmx4〇cmx〇. 2), and a low temperature constant temperature and humidity machine (manufactured by Espec Co., Ltd., trade name: pL_ 15 201202175) was used. Perform 48 small 3 Κ ) ' Drying and hardening at a temperature of 2 5 C and a relative humidity of 50%. Then, use a dull-type die-cutting device for tensile test (JISK 6259 No. 2 dumb type) A test piece was prepared. The test piece was attached to a TENSILON universal testing machine (manufactured by 〇rientec Co., Ltd., name: RTM500) using a parallel clamping lock to pull at a speed of 30 mm/min to measure the sample. The maximum tensile strength (kgf/mm2) of the sheet. At the same time, the distance between the markings at the time of breaking of the test piece (initial 4 〇mm) was measured by a gauge, and the tensile elongation at break was determined. The tensile elongation (%) is larger and the flexibility of the coating film is higher. <Evaluation of water resistance of the cured coating film> After the temperature is 40 ° C, the sink is immersed for 1 day and 7 days after hardening. After 24 hours of coating, the state change of the coating film was evaluated by visual observation. Evaluation was carried out in the following four stages: ◎: Excellent (no change); 〇: Good; △: Slightly poor; χ: Poor (expansion and deformation of the surface of the coating film, discoloration of the coating film). Evaluation of storage stability > 50% of the dimer acid/polyamine amine condensate was placed in a thermostat (manufactured by Kanamoto Kasei Co., Ltd., trade name: HIFLEX FL4050), and cooled to 20 C for > hour. Then, the temperature of the thermostat was raised until the state of the dimer acid/polyamidoamine condensate was investigated by visual observation after maintaining for 1 hour. Similarly, the temperature was raised to 20, 25, 30, 35, 40, 50, 60' 70 '80, i 〇〇 °c, and after holding for i hours, the state of the polyamide was investigated by visual observation. The dimer acid. Polyamine amine condensate is defined as the liquid temperature of 16 201202175, and is defined as "liquid sturdy, ra ώ 收 体 temperature". The lower the liquidification temperature and the lower the crystallinity of the dimer acid/polyamine amine condensate, the better the storage stability of the polyamine hardener composition was judged. Production Example 1 Part of the ethylene diamine - thiol group was placed in a high pressure pin of a 1 〇 〇 ml with a blender, and charged with diethylenetriamine 2 〇〇g (manufactured by TGSGH Co., Ltd., trade name : 顺), water iQQg and catalyst pd -C (with 5%) 2 G G. After the high-pressure steel was sealed and replaced with hydrogen, the mixture was heated to (10). Next, in the high-pressure steel, hydrogen was introduced at a pressure of 3 MPa, and 妓7. After 7 hours, 314 g of a 37% aqueous solution of furfural was supplied by a pump. In advance! After the aging reaction of 丨, 拄 热 / / / 仃 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时 小时After distilling off water from the reaction liquid using a distillation apparatus, 236 g of a product was obtained under reduced pressure. Gas chromatographic analysis and 1H-NMR analysis of the product were carried out, and as a result, 40% was converted to a methyl group ([methyl]/[hydrogen atom] with respect to a hydrogen group bonded to a gas atom of diethylenetriamine. ]=4〇/ 60 (Mor number ratio)). Thus, the average number of active hydrogens per molecule of the product is 3. Further, the composition of the obtained amine compound is DETA / monomethyl / dimethyl / tetramethyl / pentamethyl = 7 7 / 25 MM 7 / 231 / 7.6 / l. 〇 (GC area ratio) . In the following, the composition obtained by partially N-methylating the diethylenetriamine obtained in the present production example is referred to as "DETA-2M". Production Example 2 Part 3 of ethylene diamine - Aminopropylation In 236 liters of a reaction vessel, 236 g of ethylene diamine was added and heated to 17 201202175 6 0 C. In the mixture, 41 7 g of acrylonitrile was added over 2 hours. After the addition of acrylonitrile was completed, the reaction was maintained at 6 ° C for 2 hours. In a 1 liter batch reactor, 500 g of the product formed by the previous process was added, and 100 g of isopropyl alcohol and 7 58 of Raney C catalyst were further charged. After nitrogen substitution in the reaction vessel to expel the air, it was filled with 5. 5 MPa of hydrogen, and then heated to. The pressure of the reactor was maintained at 5. 5 MPa. The temperature was maintained at 12 ° C for 1 hour. The reactor was cooled to room temperature, and a reaction liquid for removing a solid component was obtained by filtration. Isopropanol and a low boiling point component were distilled off under reduced pressure from the reaction liquid to obtain 682 g of a product. Gas chromatography analysis and 1 NMR analysis of the product showed that 50% of the hydrogen groups bonded to the nitrogen atom of the ethylene diamine were substituted with an aminopropyl group. Further, the composition of the obtained product is a monoaminopropyl substituent/diaminopropyl substituent/triaminopropyl substituent/tetraaminopropyl substituent = 7/8〇/11//2 (gc area ratio). In the following, a composition obtained by partially performing 3-aminopropylation of the ethylene diamine obtained in the present production example is referred to as "apeda". Example 1. A composition of a dimer acid containing 5% by weight of a monomeric acid and 14% by weight of a trimeric acid of a Cu-unsaturated fatty acid in a 1000 ml glass container [manufactured by Nagano Food Industry Co., Ltd., trade name: Tsunodime 216, acid value: 193. 6 mgKOH / g, suitable for the component (C). l之g, and, while stirring, slowly added 21. 4 g of diethylenetriamine (manufactured by TOSOH Co., Ltd.) and 6.7 g of N-aminoethylamine (TOSOH); suitable for compounds 18 201202175 (B). ] [Mor number of the total of the compound (A) and the compound (B)] / [the number of moles of the dimer acid of the component (C)] is 3/2. The stirring speed was increased to 150 rpm, and 6.2 g of water was removed by distillation under nitrogen atmosphere for 2 hours (TC, heating for 4 hours. Further, at 2 Torr. (:, 10 mmHg, the reaction was carried out for 1 hour. Next, The reactor for the reaction was cooled to 1 Torr (rc), and the mixture was stirred and added as a homogeneous solution to a solid concentration of 7 〇% by weight, and then cooled to room temperature. (Dimer acid/polyamidoamine condensate) is amber, and does not contain the active argon equivalent system 227. , Field AX ~ rice pore blush (oiled SHELL epoxy company, trade name: postal (10) ι 〇〇ι, Epoxy 474 (4) A type epoxy resin) and become a heavy epoxy resin: liquid 32 reread, u 68 parts by weight, to add the obtained dimer acid · polyamine amine condensate The toluene solution was cut and mixed at room temperature for 5 minutes using a spatula. Here, [the amine hydrogen atom in the hardening of the polyamine of the present invention [epoxy group in the epoxy resin] is l/ i (moire ratio). It will be displayed in the table according to the above evaluation method and the result of the measurement. Film hardening arrest and physical properties Example 2 to Example 9 and Comparative Example 1 to Comparative Example 15 Other than the materials of the types and amounts shown in the remaining 1 and Table 2, and Table 2, Example 1 was carried out. Results—and shown in Table i 19 201202175 [I<] Comparative Example 5 〇〇1 1 <N1 CO CO 00 s' ί 1 \ CO σ> eo (Nl CO CO CD 00 iri t- 〇ssi Comparative Example 4 § 1 1 Bub·1 CO ύ 1 1 CO C<1 CO σ> CO ΙΛ LT) oo ci CO oo s |Comparative Example 3 | g 1 1 Ο 1 呀1 1 (Μ \ ΙΓ>C<i CO CO CO Oo CO in* t- to ΟΪ g I Comparative Example 2 | ο ο 1 1 CO ΟΟ 1 oo s 1 1 c<j \ CO 呀 CO "•CP CO CO CO m in CO o* og Comparative Example 1 ο 1 1 1 t t- 03 CO 1 1 CO CvJ c3 CO CO Lfi s Example 9 ο cd 1 cd CO LTJ 1 1 1 60/40 1 CM \ CO £ <NI oo CO CM CO 卜Λ so CO : Example 8 g Γ ΟΟ 1 CO LD -1 1 1 70/30 1 <M CO 寸 CO CO CO ο cd CM oo σ> Another Example 71 g 1 1 LT5 1 1 1 80/20 1 ζα CO CO < ;>a C<l C<1 eo oo CO 呀CO CO oo o CO Example 6 ο ο cd 1 CO 1 1 1 1 60/40 1 CO \ <N 1 CO CO ο CO c=> CM o Another embodiment 5 | ο ο οοό 1 »-Η ο 1 1 1 1 70/30 1 CN1 \ 00 兮CO CO CO CO 05 ιτί o σ> o ΙΛ οα Li Example 4 I g Ξ CO CO 1 1 1 1 1 60/40 1 CM \ CO CO CM Cvl (NI CO oo ς〇CO in og ΙΛ eo | Example 3 I g 〇 d CO o 1 1 1 1 1 70/30 1 CO \ ΙΛ c3 CO 05 o 05 ID* CNI LT5 00 Example 2 I ο ο 03 00 CO 1 1 1 1 1 80/20 1 \ CO o CO oo oo 宕 Example 1 | g inch C< 1 1 cd 1 1 1 1 80/20 1 C<I c- C〇3 CvJ <N1 CO oo CO CD ς〇(Nl o 05 LT3 CM 3 Ί Diethylenetriamine DETA-2M N-Amino B Piperazine-specific triethylenetetramine APEDA Amine A/amine B (moire ratio) Amine (A+B)/dimer acid (C) (Mohr number ratio) Active hydrogen equivalent polyamine amine hardener added Parts by weight (pbw) Epoxy resin added parts by weight (pbw) Hardenability (Hr.) Film strength [tensile strength (kgf/mm2)] Flexibility [tensile elongation 00] Liquidification temperature (° c) c CQ S /<**N ^ 3 s physical property evaluation
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〔{NIS CD <〇 T—^ 1 1 1 1 1 38.2 1 3/2 〇〇 LO Μ < LTD Csl LO 卜 CD oi 〇 〇 LO C<l ο ◦ ,丨— 1 < cd 1 1 1 oa cd 1 1 3/2 CO 03 CO ① LO c>a cd LO —叫 ο 〇> τ™4 18.7 1 1 1 卜 寸· 1 1 3/2 CNI 卜 CO CO CO CNI cd LO Ί 1 i ◦ CO CD o τ·· < oa 1 1 1 τ^Η CO 1 1 3/2 CO oo 呀 CO CD CO CO cd LO t—H oo LO o o 1 1 o CNI 〇6 1 1 0/100 3/2 CNI σ> CO LO 1 1 < CO 呀 τ—Η o o 1 1 33.5 1 1 1 0/100 3/2 CT) t—H 卜 Q CO 寸 CZ5 卜 ο Τ 1 < 〇 CO o cz> 卜 oi 1 i 1 〇 CNI 卜 cd 1 1 10/90 3/2 CO LO LO 呀 LO CO P ( LO CO Q· ο ο ι 1 i 〇 CO Q o 卜 CN) 1 oa cz> CO 1 1 1 10/90 3/2 CD CO LO 呀 LO ① OO 呀 o LO ο CD CO o o τ_·Η 卜 oi CD o CO 1 1 1 1 10/90 3/2 CO o- 〇〇 卜 CO CO CO as 寸 o CD CNI 导 o CZ5 i丨丨H oo ζό CNI 1 1 1 1 1 100/0 3/2 05 cx> CNI r-H 卜 LO cd LO t-H LO LO LO CNI 二聚物酸(C)n(g) 二乙烯三胺 DETA-2M N-胺基乙基哌嗪 1 旅嗪 三乙烯四胺 APEDA 胺A/胺B(莫爾數比) 胺(A+B)/二聚物酸(C)(莫爾數比) 活性氫當量 聚醯胺胺硬化劑添加重量份數(pbw) 環氧樹脂添加重量份數(pbw) 硬化性(Hr.) 1-1 /*> <M ε ε \ <+H b〇 娥 4 缌 Μ 可撓性[抗拉延伸率00] 液態化溫度(°c) PO 材料 物性 評價 ^^φ:(雄 q 裝 〇^硪肊^铤|〇〇令命)¥013^ 咔噠伞:(鍥 Μ 裝roMqY<M®-<^^)w2-VI3a ^^々/ηοβοι^^ι^θ^ο'^,^^,^^^ο^^-ν,^'ξ-^ομ^ ϋ^<<#Η05。如歃铖:(HO^E9.CO6I:蛱键,9I33.spocnsi :镩砰05。柩)潜荽鉍4(1 201202175 正如由實施例1〜實施例9而明確地顯示:藉由本發 明之聚醯胺硬化劑組合物而調冑之塗膜係抗拉延伸率及抗 拉強度,比起使用來自於三乙稀四胺之硬化劑組合物之狀 態(比較例1),還顯示大約2倍〜大約3倍之抗拉延伸率。 於疋,得知在使用本發明之聚醢胺硬化劑組合物之狀態 下比起來自於一乙烯四胺之硬化劑組合物(比較例1 ), 還顯示更加良好之可撓性,可以適合使用於特別是要求可 撓性之塗料(例如風力發電用渦輪機之塗料)之用途。此 外,本發明之聚醯胺硬化劑組合物係比起來自於三乙烯四 胺之硬化劑組合物(比較例υ,還具有更加良好之儲存安 定性。此外,本發明之聚醯胺硬化劑組合物係使用二乙烯 三胺,來作為聚乙烯胺,因此,比起三乙稀四胺,還具有 更加良好之供應安定性。 另一方面,正如比較例2〜比較例5所示,在併用三 乙烯四胺和具有哌嗪環之化合物之狀態下,得到之塗膜係 顯著地降低抗拉強度,因此,不容易說是具有實用性。 另一方面,正如比較例6所示,在不包含化合物(Β) 之反應生成物之狀態下,得到之塗膜係抗拉延伸率比起三 乙烯四胺,僅增加大約丨.5倍’不容易說是賦予充分之可 撓性。 另一方面,正如比較例7〜比較例11所示,在化合物 (Α)和化合物(Β)之莫爾數比脫離15/85而包含過 剩之化合物(Β)之狀態下,即使是抗拉延伸率出現大約2倍 〜3倍,也極端地降低抗拉強度,因此,不容易說是具有 22 201202175 實用性。 另一方面,正如比較例12〜比較例14所示,在使用 每1刀子之活性氫數為6之三乙烯四胺來取代化合物(B) 之狀態下’抗拉延伸率比起比較例i,僅增加大約1. 5倍, 不容易說是賦予充分之可撓性。此外,比較例12〜比較例 14之二乙烯三胺/三乙烯四胺之莫爾數比係分別成為⑽ /20、70/ 30、60/ 40。 此外,正如比較例丨5所示,在使用apeda之狀態下, 塗膜變脆而失去柔軟性,結果,比起來自於三乙稀四胺之 聚醯胺硬化劑組合物(比較例n,抗拉延伸率和抗拉強度 一起惡化,不容易說是具有實用性。 實施例10 在1000ml之玻璃容器,加入包含單體酸7重量%和三 聚物I 14重量%之Cu不飽和脂肪酸之二聚物酸之組合物 [筑野食工業公司製、商品名稱:、酸價: 193.6mgKOH/g、適合於成分(Ch ]之1〇〇g,並且,還進 仃攪拌同時緩慢地加入41.8g之四乙烯五胺(T〇s〇H公司[{NIS CD <〇T—^ 1 1 1 1 1 38.2 1 3/2 〇〇LO Μ < LTD Csl LO 卜 CD oi 〇〇LO C<l ο ◦ ,丨— 1 < cd 1 1 1 Oa cd 1 1 3/2 CO 03 CO 1 LO c>a cd LO —called ο 〇> τTM4 18.7 1 1 1 Bu inch · 1 1 3/2 CNI Bu CO CO CO CNI cd LO Ί 1 i ◦ CO CD o τ·· < oa 1 1 1 τ^Η CO 1 1 3/2 CO oo 呀CO CD CO CO cd LO t—H oo LO oo 1 1 o CNI 〇6 1 1 0/100 3/2 CNI σ> CO LO 1 1 < CO 呀τ—Η oo 1 1 33.5 1 1 1 0/100 3/2 CT) t—H 卜 Q CO inch CZ5 οο Τ 1 < 〇CO o cz> 1 i 1 〇CNI cd 1 1 10/90 3/2 CO LO LO 呀LO CO P ( LO CO Q· ο ο ι 1 i 〇CO Q o 卜CN) 1 oa cz> CO 1 1 1 10/90 3/2 CD CO LO 呀LO 1 OO 呀o LO ο CD CO oo τ_·Η Bu oi CD o CO 1 1 1 1 10/90 3/2 CO o- 〇〇 CO CO CO CO as inch o CD CNI Guide o CZ5 i丨丨H oo ζό CNI 1 1 1 1 1 100/0 3/2 05 cx> CNI rH 卜 LO cd LO tH LO LO LO CNI Dimer acid (C) n (g) Diethylene triamine DETA -2M N-Aminoethylpiperazine 1 pilazine triethylenetetramine APEDA A/Amine B (Mohr number ratio) Amine (A+B)/dimer acid (C) (Mohr number ratio) Active hydrogen equivalent polyamine amine hardener Adding parts by weight (pbw) Epoxy resin addition Parts by weight (pbw) Hardenability (Hr.) 1-1 /*><M ε ε \ <+H b〇娥4 缌Μ Flexibility [Tensile elongation 00] Liquidification temperature (° c) PO material physical property evaluation ^^φ: (雄q 装〇^硪肊^铤|〇〇令命)¥013^ 咔哒 umbrella: (锲Μ 装roMqY<M®-<^^)w2-VI3a ^ ^々/ηοβοι^^ι^θ^ο'^,^^,^^^ο^^-ν,^'ξ-^ομ^ ϋ^<<#Η05. For example: (HO^E9.CO6I: 蛱 bond, 9I33.spocnsi: 镩砰05. 柩) 荽铋 4 (1 201202175 As clearly shown from Example 1 to Example 9: by the present invention The tensile elongation and tensile strength of the coating film tuned by the guanamine hardener composition are also about 2 times higher than the state of using the hardener composition derived from triethylenetetramine (Comparative Example 1). ~ about 3 times tensile elongation. It is known that in the state of using the polyamine hardener composition of the present invention, compared with the hardener composition derived from ethylenetetramine (Comparative Example 1), It exhibits more excellent flexibility and can be suitably used for applications in which a coating material requiring flexibility (for example, a coating for a wind turbine) is used. Further, the polyamine hardener composition of the present invention is derived from three A hardener composition of ethylene tetraamine (comparatively, it has a better storage stability. Further, the polyamine hardener composition of the present invention uses diethylenetriamine as a polyvinylamine, and therefore, Triethylenetetramine, also has a better supply of safety On the other hand, as shown in Comparative Example 2 to Comparative Example 5, in the state in which triethylenetetramine and a compound having a piperazine ring are used in combination, the obtained coating film system remarkably lowers the tensile strength, and therefore, it is not easy. On the other hand, as shown in Comparative Example 6, in the state where the reaction product of the compound (Β) is not contained, the tensile elongation of the obtained coating film is increased only by triethylenetetramine. It is not easy to say that it is sufficient flexibility. On the other hand, as shown in Comparative Example 7 to Comparative Example 11, the molar ratio of the compound (Α) and the compound (Β) is separated by 15/. In the state of 85 and containing excess compound (Β), even if the tensile elongation is about 2 to 3 times, the tensile strength is extremely lowered, so it is not easy to say that it has the practicality of 22 201202175. As shown in Comparative Example 12 to Comparative Example 14, in the state in which the compound (B) was replaced with the triethylenetetramine having an active hydrogen number of 6 per knive, the tensile elongation was increased only by comparison with Comparative Example i. About 1.5 times, it is not easy to say that it is given adequately Further, the molar ratios of diethylenetriamine/triethylenetetramine of Comparative Example 12 to Comparative Example 14 were (10) / 20, 70 / 30, and 60 / 40, respectively. It is shown that in the state in which apeda is used, the coating film becomes brittle and loses flexibility, and as a result, it is compared with a polyamine hardener composition derived from triethylenetetramine (Comparative Example n, tensile elongation and tensile strength) It is not easy to say that it is practical. Example 10 A 1000 ml glass container was charged with a composition of a dimer acid containing 7% by weight of a monomeric acid and 14% by weight of a terpolymer I of a Cu-unsaturated fatty acid. Manufactured by the company, the product name: acid value: 193.6mgKOH/g, suitable for the component (Ch) of 1〇〇g, and, while stirring, slowly adding 41.8g of tetraethylenepentamine (T〇) s〇H company
製)[適合於化合物(A)。]和5. 〇g之N-胺基乙基哌嗪(T〇s〇H △司製)[適合於化合物(B)。]而使得[化合物(九)和化合物 (B)之合計莫爾數]/ [成分(c)之二聚物酸換算之莫爾數] 成為3/2。 在120 C進行加熱,進行攪拌而直到呈完全地成為均 勻為止。提问攪拌速度至15〇rpm,在氮氣氛下、2〇〇。匸, 加熱4小時,藉由蒸餾而除去6. 2g之水。此外,在2〇〇。〇、 23 201202175 lOmmHg,進行i小時之反應。接著’冷卻反應用容器至ι〇〇 °C為止,在加入甲苯來進行攪拌而作為均勻之甲苯溶液來 成為固態成分濃度70重量。/。之後,冷卻至室溫為止\在此 得到之反應生成物(二聚物酸•聚醯胺胺縮合物)係琥珀 色在不包含甲本之狀態下之活性氫當量係167。、 相對於以甲苯來稀釋環氧當量474之環氧樹脂(油化 SHELL環氧公司製、商品名稱:Epik〇te 1〇〇1、環氧米量 m之㈣A型環氧樹脂)而成為7〇重量%之環氧樹月^液 74重量份,以26重量份之比例’來添加得到之二聚物酸· 聚醯胺胺縮合物之甲苯溶液,作為聚醯胺硬化齊“且人物 使用刮勺,於室溫下,進行5分鐘之剪斷授拌。在此。本 發明之聚醯胺硬化劑組合物中之胺氫原子]/[環 之環氧基]係1 / 1 (莫爾數比)。將 ’f月曰中 肝筏照則述之評價 進行塗膜之硬化速度和物性測定 / 〜、、·°禾,顯不於表3 實施例1G〜實施例18、比較例16〜比較例35 ° 除了使用表1及表2所顯示之種無…及參考例 種頬和量之原料以冰 八餘係相同於實施例i而實施。將其結果—併顯, 及表4。此外,顯示於表3及表 .’、不;表3 及表4中之所謂「S—ρΕΗΑ於 指還對於在乙稀胺類之製造製程來得到 」係 (ΡΕΗΑ)蒸餾殘渣,進行篆館 G烯六胺 丁丄餾而得到之重質 (T0S0H公司製)。其特徵在 奴之是合物 子之氣原子數變多。 刀子量大於peha,w 24 201202175 〔5 參考例 〇 LO 1 CO oa 1 寸 c<i 1 50/50 I 3/2 C<1 CvJ C<1 eo 〇〇 C£) CO LO* C^ o ΙΛ 05 △/〇 5 -£ g 1 1 1 1 cvi CO CD oo 一 C<1 1 Lj/2. 05 CO CN3 呀 CO CO CO OO LO c— c> CO ο △/〇 g -£ g ^-1 1 1 1 1 卜 卜· 1 CD 男’ 1 1 3/2 1 g CO CO 0¾ CO LO LO 00 o CO 00 〇/◎ S 比較例 18 Ο Ο 1 1 1 1 寸 ο 1 s' 1 L.3/2 1 ΙΛ OJ <NI (SI CO 00 CO 寸 LO c— o ΙΛ Cft △/〇 g Ο ο 1 1 1 1 CD oi 1 oo 々· (NJ 1 L3/2 1 却 C<J 寸 CO CO CO LO in CO o Ο △/〇 比較例 16 g 1 1 1 1 1 卜 03 CO 1 |—3^2一」 CO ① LD* 卜 ©/© s ο ο 1 1 t- cd 卜 cd 1 1 50/50 1 _3—/2」 s 05 CO 口 〇 ΙΛ 卜 05 CO s 實施例; 17 i § *~Η 1 CO 寸’ 1 1 呀 CO CO LO 1 1 70/30 1 丨——3/2—— | O CO (N1 寸 卜 OO 寸* L〇 CO 却 ο 呀 省2 Ο ο »«Η 00 1 1 1 o 一 1 1 85/15 1 .3/2_| CO CO CD <N1 寸 卜 05 寸· in CO 寸 ο c<] ίΚ ο ο 1 呀 [>· CO t-~ to 1 1 1 50/50 1 3/2 1 s Csl CT5 (Nl 口 C— 呀’ OO oo CO ο ο ο 1 CO 1 o 。’ 1 1 1 70/30 1 3/2 CO CT) 一 CO 写 琮2 4¾ g 1 a-i 4 CO CO l 1 1 1 60/40 1 3/2 LO ς〇 CO C<1 CO in in oo ο 苳 %: Ο ο 1 〇〇 1 CNI ο 1 1 70/30 1 丨 3/2 1 in LO 1Λ CO LO OO ΙΛ ο 實施例 11 ο ο 00 1 in .丨 I 1 85/15 1 1 3/2 1 05 ΙΛ UO C<J LO 0¾ — CO 5 遨2 ο ο 〇〇 1 o Ln 1 1 1 85/15 1 1 3/2 1 £ CO C<J i 寸 o LT) 卜 5 二聚物酸(C)u(g) 四乙烯五胺 五乙烯六胺 S-PEHA DETA-2M N-胺基乙基哌嗪 哌嗪 I 三乙烯四胺 胺A/胺B(莫爾數比) 胺(A + B)/二聚物酸(C)(莫爾數比) Φ1 聚醯胺胺硬化劑添加重量份數(pbw) 環氧樹脂添加重量份數(pbw) 硬化性(Hr.) 1 1 ΐ ε \ M-l &〇 澳 4 娥 瑶 可挽性[抗拉延伸率«)] 硬化塗膜之耐水性(1/7日硬化) 液態化溫度rc) -< CO S /-s 1 材料 物性 評價() is suitable for compound (A). And N. Aminoethylpiperazine (manufactured by T〇s〇H △) of 〇g [suitable for compound (B). ] [Mor number of the compound (9) and the compound (B) in total] / [the number of moles of the dimer acid in the component (c)] is 3/2. The mixture was heated at 120 C and stirred until it became completely uniform. Ask the stirring speed to 15 rpm and 2 在 under a nitrogen atmosphere. 2克的水。 By 匸, the water was removed by distillation to remove 6. 2g of water. Also, at 2 〇〇. 〇, 23 201202175 lOmmHg, the reaction for i hours. Then, the reaction vessel was cooled to ι ° C, and toluene was added thereto, followed by stirring to obtain a homogeneous toluene solution to have a solid concentration of 70% by weight. /. Thereafter, the reaction product (dimer acid/polyammine amine condensate) obtained here is cooled to room temperature, and the active hydrogen equivalent system 167 in the state in which amber is not contained is amber. It is 7 with respect to an epoxy resin (an oil-made SHELL epoxy company, trade name: Epik〇te 1〇〇1, epoxy rice amount (4) A-type epoxy resin) diluted with toluene. 74% by weight of the epoxy tree liquid 74 parts by weight, added in a ratio of 26 parts by weight 'to the obtained toluene solution of the dimer acid · polyamine amine condensate, as a polyamine hardened" and used by the character The spatula is subjected to shearing and mixing for 5 minutes at room temperature. Here, the amine hydrogen atom in the polyamine hardener composition of the present invention] / [cyclo-epoxy group] is 1 / 1 (Mo尔数比). The evaluation of the curing speed and physical properties of the coating film in the evaluation of the liver 筏 ' f 〜 〜 〜 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 16~Comparative Example 35 ° Except that the materials shown in Tables 1 and 2 are used, and the raw materials of the reference examples and amounts are the same as in Example i, the results are as follows. 4. In addition, it is shown in Table 3 and Table. ', No; Table 3 and Table 4, the so-called "S-ρΕΗΑ refers to the manufacture of ethylene amines. To obtain "system (ΡΕΗΑ) distillation residue, a seal alkenyl Hall G hexamine butoxy Shang of heavy distillate obtained (T0S0H Corporation). It is characterized by a large number of gas atoms in the slave. The amount of knife is greater than peha, w 24 201202175 [5 Reference example 1LO 1 CO oa 1 inch c<i 1 50/50 I 3/2 C<1 CvJ C<1 eo 〇〇C£) CO LO* C^ o ΙΛ 05 △/〇5 -£ g 1 1 1 1 cvi CO CD oo a C<1 1 Lj/2. 05 CO CN3 呀CO CO CO OO LO c- c> CO ο △/〇g -£ g ^-1 1 1 1 1 Bub·1 CD Male' 1 1 3/2 1 g CO CO 03⁄4 CO LO LO 00 o CO 00 〇/◎ S Comparative Example 18 Ο Ο 1 1 1 1 inch ο 1 s' 1 L.3 /2 1 ΙΛ OJ <NI (SI CO 00 CO inch LO c- o ΙΛ Cft △/〇g Ο ο 1 1 1 1 CD oi 1 oo 々· (NJ 1 L3/2 1 but C<J inch CO CO CO LO in CO o △ △/〇Comparative example 16 g 1 1 1 1 1 Bu 03 CO 1 |—3^2 一” CO 1 LD* 卜©/© s ο ο 1 1 t- cd 卜 cd 1 1 50 /50 1 _3—/2” s 05 CO 〇ΙΛ 05 05 CO s Example; 17 i § *~Η 1 CO inch ' 1 1 呀 CO CO LO 1 1 70/30 1 丨——3/2— — | O CO (N1 inch OO inch* L〇CO ο 呀 province 2 Ο ο »«Η 00 1 1 1 o 1 1 85/15 1 .3/2_| CO CO CD <N1 inch Inch · in CO inch ο c<] ίΚ ο ο 1 呀[>· CO t- ~ to 1 1 1 50/50 1 3/2 1 s Csl CT5 (Nl port C- 呀 ' OO oo CO ο ο ο 1 CO 1 o .' 1 1 1 70/30 1 3/2 CO CT) One CO Write 43 2 43⁄4 g 1 ai 4 CO CO l 1 1 1 60/40 1 3/2 LO ς〇CO C<1 CO in in oo ο 苳%: Ο ο 1 〇〇1 CNI ο 1 1 70/30 1丨3/2 1 in LO 1Λ CO LO OO ΙΛ ο Example 11 ο ο 00 1 in .丨I 1 85/15 1 1 3/2 1 05 ΙΛ UO C<J LO 03⁄4 — CO 5 遨2 ο ο 〇 〇1 o Ln 1 1 1 85/15 1 1 3/2 1 £ CO C<J i inch o LT) Bu 5 Dimer acid (C) u(g) Tetraethylene pentamine pentaethylene hexamine S-PEHA DETA-2M N-Aminoethylpiperazine piperazine I triethylenetetramine A/amine B (moire ratio) amine (A + B) / dimer acid (C) (moire ratio) Φ1 Polyammine amine hardener added parts by weight (pbw) Epoxy resin added parts by weight (pbw) Hardenability (Hr.) 1 1 ΐ ε \ Ml & 〇 4 4 娥 可 可 可 [ [ tensile elongation «)] Water resistance of hardened film (1/7 day hardening) Liquidification temperature rc) -< CO S /-s 1 Material property evaluation
ηο-^φ:(筚川发o-rqKfB-φ 命)wz-g3a5t{I!?<-3Hosol 嫦*I: sis«:loM ,#«,^«^10^®-N,VH3d—s,slHC$10^-,^T«-10B(z ΪΙΙ!?·<3輙 τηε=伞貶柘:(Hop曰 9_ε6Ι :蛱湓 ' 9T<NliIP0cnsE-:练蟀05<柜)磁者鉍U(I 201202175 〔i】 £ 〇 I 1 1 1 1 | 38.2 | 1 1 3/2 1 〇〇 ΙΛ Η ΙΛ (Μ CO οό o O 1 〇/◎ 1 in C<1 〇 ◦ 05 1 1 |13,4 J 1 1 1 3/2 1 〇 CO (Μ CO CO £ 00 oo 寸 (Nl Δ/Ο ο 比較例 33 〇 〇 1 CO 1 1 1 〇 〇〇* 1 t 1 3/2 呀 OO 00 Csl gv3 ο ιή 05 »—1 CO CO 1〇/◎ 写 g oo 1 1 1 1 〇 1 1 丨 3/2 1 CO CO LO LO Oi oo 03 〇/◎ 1 ο 比較例 31 ο ο 1 ! 1 σ> 〇〇 1 1 I o/ioo | 1 3/2 I Cvj 05 CO Oi m CO o o »—H Χ/Δ jj g Τ«·Η 1 1 LD c6 CO 1 1 1 | o/ioo | 丨 3/2 I 05 § o g Χ/Δ 另 比較例 29 g 1 1 卜 CO 0¾ eo 1 t 1 1 5/95 | 1 3/2 I Oi ς〇 in LO ΙΛ lD 守 卜 CO o g ^4 1 χ/Δ 1 5 Λ3 ο 1 CsJ CO 1 Oi ψ—^ CO 1 1 1 I 5/95 1 3/2 | in 00 m ΙΛ un Lf5 卜 ς〇 O χ/Δ 1 宕 比較例 27 ο ΙΛ oi 1 1 σ> eo 1 1 1 1 5/95 | 1 3/2 1 g CD in CO m o s χ/Δ 1 5 £ g 1 口 卜 1 1 1 1 95/5 | 1 3/2 | o OJ s g ο Lft 03 ς〇 1 ◎/◎ 1 ο A3 g 1 g t 卜 f 1 1 1 95/5 | 1 3/2 | 寸 CO Cv〇 CNi CD L〇 05 1 ◎/◎ ι ο £ g r- co 兮 1 卜 1 1 1 1 95/5 | 1 3/3 | CO in ^J· CO CO LiS 05 Lft CNi 丨◎/◎ I 写 比較例 23 o 1 1 OO 1 1 i 1 | 100/0 | 1 3/2 I m *-« s § 05 CO t- oi 呀 1 ◎/◎ I ο 5 £ g 1 1 63.3 1 1 1 1 1 1 | 100/0 | 1 3/2 | 03 C<I C<i 05 卜 CO <N1 (NI CM 1 ◎/◎ 1 5 g σι 1 1 l 1 1 | loo/o | 1 3/2 | <NI CO CSJ LTS 〇 oi <M CM 1 ◎/◎ I Ο 二聚物酸(C)”(g) 四乙烯五胺 五乙烯六胺 S-PEHA N-胺基乙基哌嗪 旅°秦 二乙烯三胺 APEDA 胺A/胺B(莫_數比) 胺(A+B)/二聚物酸(C)(莫爾數比) 活性氣當量 聚酲胺胺硬化劑添加重量份數(pbw) 環氧樹脂添加重量份數(pbw) 硬化性(Hr.) ΐ \ M-h b〇 m 娥 n 可撓性[抗拉延伸率00] 硬化塗膜之耐水性(1/7日硬化) 液態化溫度(°c) *< CQ 铤 ^ 材料 物性 評價 05。噠^: (siM#foqJ.硪 ¢^淫— εφ^)να3α.νΗο-^φ:(筚川发o-rqKfB-φ命)wz-g3a5t{I!?<-3Hosol 嫦*I: sis«:loM ,#«,^«^10^®-N,VH3d— s,slHC$10^-,^T«-10B(z ΪΙΙ!?·<3輙τηε=Umbrella: (Hop曰9_ε6Ι :蛱湓' 9T<NliIP0cnsE-: Practice 05< cabinet) Magnetic 铋U(I 201202175 [i] £ 〇I 1 1 1 1 | 38.2 | 1 1 3/2 1 〇〇ΙΛ Η ΙΛ (Μ CO οό o O 1 〇/◎ 1 in C<1 〇◦ 05 1 1 |13 , 4 J 1 1 1 3/2 1 〇CO (Μ CO CO £ 00 oo 寸 (Nl Δ/Ο ο Comparative Example 33 〇〇1 CO 1 1 1 〇〇〇* 1 t 1 3/2 呀 OO 00 Csl Gv3 ο ιή 05 »—1 CO CO 1〇/◎ Write g oo 1 1 1 1 〇1 1 丨3/2 1 CO CO LO LO Oi oo 03 〇/◎ 1 ο Comparative Example 31 ο ο 1 ! 1 σ> 〇〇1 1 I o/ioo | 1 3/2 I Cvj 05 CO Oi m CO oo »—H Χ/Δ jj g Τ«·Η 1 1 LD c6 CO 1 1 1 | o/ioo | 丨3/2 I 05 § og Χ/Δ Another comparative example 29 g 1 1 Bu CO 03⁄4 eo 1 t 1 1 5/95 | 1 3/2 I Oi ς〇in LO ΙΛ lD 守卜 CO og ^4 1 χ/Δ 1 5 Λ3 ο 1 CsJ CO 1 Oi ψ—^ CO 1 1 1 I 5/95 1 3/2 | in 00 m ΙΛ un Lf5 ς〇 O χ/Δ 1 宕 comparison Example 27 ο ΙΛ oi 1 1 σ> eo 1 1 1 1 5/95 | 1 3/2 1 g CD in CO mos χ/Δ 1 5 £ g 1 mouth 1 1 1 1 95/5 | 1 3/2 o OJ sg ο Lft 03 ς〇1 ◎/◎ 1 ο A3 g 1 gt 卜 f 1 1 1 95/5 | 1 3/2 | Inch CO Cv〇CNi CD L〇05 1 ◎/◎ ι ο £ g R- co 兮1 卜1 1 1 1 95/5 | 1 3/3 | CO in ^J· CO CO LiS 05 Lft CNi 丨◎/◎ I Write Comparative Example 23 o 1 1 OO 1 1 i 1 | 100/ 0 | 1 3/2 I m *-« s § 05 CO t- oi 呀 1 ◎/◎ I ο 5 £ g 1 1 63.3 1 1 1 1 1 1 | 100/0 | 1 3/2 | 03 C< I C<i 05 卜CO <N1 (NI CM 1 ◎/◎ 1 5 g σι 1 1 l 1 1 | loo/o | 1 3/2 | <NI CO CSJ LTS 〇oi <M CM 1 ◎ /◎ I Ο Dimer acid (C)" (g) Tetraethylene pentamine pentaethylene hexamine S-PEHA N-aminoethyl piperazine bridging Qin diethylene triamine APEDA Amine A / amine B (Mo _ Amount ratio) Amine (A+B)/dimer acid (C) (Mohr number ratio) Active gas equivalent polyamine amine hardener Adding parts by weight (pbw) Epoxy resin added parts by weight (pbw) Hardening (Hr.) ΐ \ Mh b〇m 娥n flexibility [tensile elongation 00] water resistance of hardened film (1/7 Daily hardening) liquefaction temperature (°c) *< CQ 铤 ^ Material Physical property evaluation 05.哒^: (siM#foqJ.硪 ¢^淫— εφ^)να3α.ν
i^I!r<<Hosol _ 伽:淫W愛ΟΜ ,#«,#.杳硪Ot^-N , VH30.—S , si^^lolr ,甾叫费 Ο0(ζ «π<·4嫉 TOSB 如&-试:(Η38®9Έ61 :筚恕,9IZ3.SPO 目 si :铢W05·柩)^«ftiM(I 201202175 正如由實施例10〜實施例 J 18而明確地顯示··藉由本 發明之聚醯胺硬化劑組合物而造 峰取之塗膜硬化時間係更加 迅速於來自於標準使用之=7祕 更用之一乙烯四胺之聚醯胺硬化劑組合 物(比較例16)。於是,藉由本發 霄月而仲知可以成為迅速之 低溫硬化性,提高塗膜之生產性。 此外,藉由本發明之聚醒胺硬化劑組合物而調製之塗 膜係抗拉延伸率及抗拉強度, 守%术目於二乙稀四胺之 聚醯胺硬化劑組合物。於是, J以藉由本發明而實現同等 於三乙烯四胺之可撓性、塗膜強度可以提供塗料所要求 之充分之塗膜可撓性。 此外’本發明之聚醢胺硬化劑址合物係可以維持同等 於來自於三乙稀四胺之聚酿胺硬化劑之同等之耐水性。此 外,得知本發明之聚酿胺硬化劑組合物係比起來自於三乙 烯四胺之硬化劑組合物(比較例16),還具有更加良好之儲 存安定性。 另一方面’正如比較例17〜比較例20所示,在併用 三乙烤四胺和具有娘嗓環之化合物之狀態下,塗膜之硬化 時間係比起本發明’還更加長。此外,得到之塗膜係降低 抗拉強度,耐水性係比起本發明,還更加差。 此外,正如比較例21〜比較例26所示在不包含化 合物(B)之反應生成物之狀態或者是化合物⑴和化合物⑻ 之莫爾數比脫離90/10而包含過剩之化合物⑴之狀態 下,得到之塗媒係抗拉延伸率變小,可撓性係比起來自於 三乙烯四胺之聚酿胺硬化劑組合物(比較例丨),還更加差。 27 201202175 此外’正如比較例2 7〜比較例31所示,在化合物(a ) 和化合物(B)之莫爾數比脫離15/85而包含過剩之化合物 (B)之狀態或者是不包含化合物(A)之反應生成物之狀態 下’塗膜之抗拉強度係比起來自於三乙稀四胺之聚酿胺硬 化劑組合物(比較例1 ),還更加極端地降低,無法得到充 分之強度。 此外,正如比較例32〜比較例34所示,在不包含化 合物(B)之反應生成物之狀態下,比起來自於三乙烯四胺之 聚醯胺硬化劑組合物,得到之塗膜之抗拉延伸率變小,可 撓性變差。 此外,正如比較例35所示,在使用APEDA之狀態下, 塗膜變脆而失去柔軟性,結果,比起來自於三乙烯四胺之 聚醯胺硬化劑組合物(比較例丨),抗拉延伸率和抗拉強产 一起惡化,不容易說是具有實用性。 此外,參考例係使用四乙烯五胺(T〇s〇H公司製)來作 為化合物(A)’使用N-胺基乙基哌嗪(T〇s〇H公司製)來作為 化合物(B),使用Tsunodime216(商品名稱、筑野食品工業 公司製)和三乙烯四胺(T0S0H公司製)之反應生成物來作‘ 成分(C)之例子。理解在參考例之反應生成物,添加作為原 料之多量之三乙烯四胺係無助於塗膜硬化時間之縮短或得 到之塗膜抗拉強度、耐水性之提升。 【產業上之可利用性】 本發明之聚醯胺硬化劑組合物係比起來自於一般大多 28 201202175 使用之三乙烯四胺之聚醯胺硬化劑,還_示更加良好之性 能’例如適合使用在塗料領域。 此外’在此,引用西元2010年3月31 q甲請之曰本 專利申請案2010—082141號以及西元2010年3月31日申 請之日本專利申請案2〇10_ 082!42號之說明書、申請專利 範圍和發明摘要之全部内容,放入作為本發明 姐- < 說明書之 【圖式簡單說明】 無。 【主要元件符號說明】 無。 29i^I!r<<Hosol _ 伽: 淫W爱ΟΜ,#«,#.杳硪Ot^-N , VH30.—S , si^^lolr , 甾叫费Ο0(ζ «π<·4嫉TOSB as &-test: (Η38®9Έ61: 筚, 9IZ3.SPO 目si: 铢W05·柩)^«ftiM(I 201202175 as shown by Example 10 to Example J 18 The hardening time of the coating film obtained by the polyamine hardener composition of the present invention is more rapid than that of the polyamidamine hardener composition which is one of the ethylene tetraamines which is used in standard use (Comparative Example 16). Therefore, it is known that it can be rapidly low-temperature hardenability and improve the productivity of the coating film by the present invention. Further, the coating film tensile elongation prepared by the polyamine amine hardener composition of the present invention is obtained. And the tensile strength, the % of the polyamidamine hardener composition of the diethylenetetramine. Thus, J can provide the coating equivalent to the flexibility of the triethylenetetramine by the present invention, and the coating film strength can be provided. The required coating film is flexible. In addition, the polyamine hardener site of the present invention can maintain the same concentration as that from triethylenetetramine. The equivalent water resistance of the amine hardener. Further, it is known that the polystyrene hardener composition of the present invention has a better storage stability than the hardener composition derived from triethylenetetramine (Comparative Example 16). On the other hand, as shown in Comparative Example 17 to Comparative Example 20, the curing time of the coating film was further longer than that of the present invention in the state in which triethyltetramine and a compound having a ring of a gynecological ring were used in combination. In addition, the obtained coating film is reduced in tensile strength, and the water resistance is further inferior to that of the present invention. Further, as shown in Comparative Example 21 to Comparative Example 26, the reaction product is not contained in the compound (B) or In the state in which the molar ratio of the compound (1) and the compound (8) is 90/10 or more and the excess compound (1) is contained, the obtained coating medium tensile elongation becomes small, and the flexibility is derived from triethylenetetramine. The polyamine hardener composition (comparative example) was even worse. 27 201202175 Further, as shown in Comparative Example 2 7 to Comparative Example 31, the molar ratio of the compound (a) and the compound (B) was 15 /85 and contains excess compound (B) In the state of the reaction product which does not contain the reaction product of the compound (A), the tensile strength of the coating film is more than that of the polystyrene hardener composition (Comparative Example 1) derived from triethylenetetramine. In the state which does not contain the reaction product of the compound (B), it is compared with the polyamine which is derived from triethylenetetramine, as shown in the comparative example 32 to the comparative example 34. In the hardener composition, the tensile elongation of the obtained coating film was small, and the flexibility was deteriorated. Further, as shown in Comparative Example 35, in the state in which APEDA was used, the coating film became brittle and lost flexibility, and as a result, Compared with the polyamine hardener composition (comparative example) derived from triethylenetetramine, the tensile elongation and the tensile strength are deteriorated together, and it is not easy to say that it is practical. Further, in the reference example, tetraethylenepentamine (manufactured by T〇s〇H Co., Ltd.) was used as the compound (A)' using N-aminoethylpiperazine (manufactured by T〇s〇H Co., Ltd.) as the compound (B). The reaction product of Tsunodime 216 (trade name, manufactured by Chikuno Food Industry Co., Ltd.) and triethylenetetramine (manufactured by Tosoh Corporation) was used as an example of the component (C). It is understood that the reaction product of the reference example, the addition of a large amount of triethylenetetramine as a raw material does not contribute to the shortening of the hardening time of the coating film or the improvement of the tensile strength and water resistance of the coating film. [Industrial Applicability] The polyamine hardener composition of the present invention exhibits better performance than the polyamine hardener derived from triethylenetetramine which is generally used in 201202175. Used in the field of coatings. In addition, the description and application of Japanese Patent Application No. 2〇10_082!42, which was filed on March 31, 2010, and the Japanese Patent Application No. 2010-082141, filed on March 31, 2010 The entire scope of the patent and the summary of the invention are incorporated in the specification of the present invention. [Main component symbol description] None. 29
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JP2014095027A (en) * | 2012-11-08 | 2014-05-22 | Tosoh Corp | Amine composition for epoxy curing agent |
ES2964342T3 (en) * | 2014-05-14 | 2024-04-05 | Huntsman Advanced Mat Americas Llc | Multifunctional polyamides for protective coatings |
CN104448244A (en) * | 2014-11-30 | 2015-03-25 | 桂林理工大学 | Preparation method of low-temperature epoxy resin curing agent |
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