TWI378964B - - Google Patents

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^/8964 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種丙烯酸溶膠組合物’詳細地，其係關 於一種於焚燒時並不產生氯化氫氣體或戴奥辛，儲存穩定 性良好，即使於較低溫度下亦可使其硬化，而且對於塗膜 基材之接著性或塗膜之耐寒性及塗膜強度係優異之丙稀酸 溶膠組合物。 【先前技術】 現在，工業上廣為應用之塑膠溶膠，係將具有特別調整 之粒徑及粒度分佈之聚合物粒子與填充劑一同均質分散於 可塑劑中而形成之液狀或糊狀黏稠組合物。其次，藉由將 該塑膠溶膠塗敷於基材上，且給予適合之加工溫度，而形 成強勒之塗膜》 作為上述聚合物粒子’通常較多使用氯化乙烯均聚物、 或氯化乙烯與醋酸乙烯之共聚物等聚氣乙烯系共聚物。使 用如此之聚氯乙烯系之聚合物粒子之塑膠溶膠，其於室溫 中之長期儲存穩定性良好，塗膜亦柔軟且耐久性優異，故 而廣為應用於鋼板包覆、衣料、建材、曰用品、雜貨、汽 車零部件等之領域中。 然而，聚氣化乙烯系塑膠溶膠被熱或光分解，產生氯化 氫氣體《此處所產生之氣化氫氣體，具有成為破壞臭氧層 之原因物質之基礎’或成為酸雨之原因，或於焚燒時加速 焚燒爐之損害等問題’進而擔心其因焚燒條件可能會產生 戴舆辛，故而就安全衛生或環境污染方面而言並非較好。 107025.doc 1378964 因此業者現期待出現一種可替代該聚氯乙烯系塑膠溶朦 之塑膠溶膠。 作為可替代聚氯乙烯系塑膠溶膠之塑膠溶膠，於專利文 獻1中揭示有一種包含丙烯酸酯聚合物及有機可塑劑之塑 朦溶勝；但該塑膠溶膠具有儲存穩定性及成膜性不充分之 缺點β 又，於專利文獻2中，揭示有一種塑膠溶膠，其中並未 包含含有曱基丙烯酸甲酯聚合物或共聚物、可塑劑、填充 劑、嵌段化聚胺基甲酸酯及聚胺而形成之聚氯乙烯；但於 塗膜之加工溫度為較低溫度之情形時，該塑膠溶膠並未進 行胺基曱酸酯樹脂之硬化反應，故而所獲得之塗膜之性能 並不充分’進而若放置於35。(：左右時，則於1〜2天内即可 凝膠化，故而並不實用。 進而，於專利文獻3中，提出有一種含有丙烯酸聚合物 微粒子、嵌段型胺基曱酸酯樹脂、固態肼系硬化劑、可塑 劑及填充劑之丙烯酸溶膠；於專利文獻4中，提出有一種 含有丙烯酸聚合物微粒子、可塑劑、填充劑、谈段型胺農 甲酸酯樹脂、硬化劑及發泡劑之防音底塗層用丙稀酸溶 膠。但’該等丙烯酸溶膠亦具有與基材之密著性不充分， 或尤其是於低溫下柔軟性不充分等缺點。 進而’於專利文獻5中’提出有一種於將内核-外殼型丙 烯酸樹脂粒子及填充劑分散入可塑劑而成之塑膠溶膠中， 添加嵌段化胺基曱酸酯或嵌段化異氰酸酯及潛在性硬化劑 而成之熱硬化性組合物；於專利文獻6中，提出有一種於 107025.doc 1378964 將丙烯酸樹脂粒子及填充劑分散入可塑劑而成之塑膠溶膠 中，添加嵌段化胺基甲酸酯或嵌段化異氰酸酯及常溫下為 固態粒狀之融點為6〇。〇以上、於4(rc以下不溶解於可塑劑 之潛在性硬化劑而成之熱硬化性組合物。但，該等熱硬化 性組合物亦係於黏度穩定性、接著性等方面尚不滿意者。 又，於專利文獻7中，提出有一種含有丙烯酸聚合物微 粒子、嵌&amp;裝胺基甲酸酯、聚胺化合物、苯盼樹脂、可塑 劑及填充劑之丙烯酸溶膠組合物；於專利文獻8中，提出 有一種含有自丙烯酸聚合物微粒子、多元醇及二異氰酸酯 的二聚體所獲得之嵌段聚胺基曱酸酯、可塑劑及填充劑之 丙烯酸溶膠組合物。但，該等丙烯酸溶膠組合物亦係於黏 度穩定性等方面尚不滿意者。 [專利文獻1]日本專利特公昭55-161 77號公報 [專利文獻2]日本專利特公昭63-66861號公報 [專利文獻3]曰本專利特開2001-329135號公報 [專利文獻4]日本專利特開2001-329208號公報 [專利文獻5]國際公開第01/88009A1號案 [專利文獻6]國際公開第〇 1 /88011A1號案 [專利文獻7]曰本專利特開2004-5 1948號公報 [專利文獻8]國際公開第〇3/1 02077號案 [發明所欲解決之問題] 本發明係鑒於上述現狀而成者，其目的在於提供一種於 焚燒時並不產生氣化氫氣體或戴奥辛，儲存穩定性良好並 且即使於較低溫度下亦可使其硬化，而且對於塗膜基材之 107025.doc 1378964 接著〖生或塗膜之耐寒性、及塗膜強度優異之丙烯酸溶膠 組合物。 【發明内容】 本發明者等進行積極研究之結果是，發現可提供一種丙 婦酸溶膠組合物，&amp;而完成本發明；上述丙烯酸溶膠組合 物，係藉由於含有丙烯酸聚合物微粒子'嵌段聚胺基甲酸 酯等之丙烯酸溶膠組合物中，使其含有聚胺化合物及酸性 填酸酯化合物’而改善如上所述之問題者。 即’本發明係提供一種丙烯酸溶膠組合物者，其特徵在 於.含有（a)丙烯酸聚合物微粒子、嵌段聚胺基甲酸 酯、（c)聚胺化合物、（d)酸性磷酸酯化合物、（e)可塑劑及 ⑴填充劑。 【實施方式】 以下’就本發明之丙烯酸溶膠組合物加以詳細說明。 以下首先就（a)丙烯酸聚合物微粒子加以說明。 作為本發明中所使用之（a)成分.即丙烯酸聚合物微粒子， 可使用於丙烯酸溶膠組合物中通常使用之聚合物，例如可 使用自丙烯酸烷基酯、甲基丙烯酸烷基酯等中選擇之單體 之均聚物或共聚物。至於該單體，具體可列舉：丙烯酸甲 酉曰、丙稀酸乙酯、丙烯酸正丙酯、丙稀酸異丙酯、丙烯酸 正丁醋、丙烯酸異丁酯、丙烯酸第二丁酯、丙烯酸第三丁 酿、丙烯酸環己酯、丙烯酸苄酯 '甲基丙烯酸甲酯、曱基 丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、曱 基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第二丁 I07025.doc 曰+甲基丙烯酸第三丁酯、曱基丙烯酸環己酯及曱基丙烯 酸苄酼等。又，作為共聚合成分，亦可使用苯乙烯、α-曱 基球乙稀等。 作為（a)丙烯酸聚合物微粒子，較好的是使用包含内核部 及外殼部之内核-外殼型丙烯酸聚合物微粒子。於使用内 核外殼型丙烯酸聚合物微粒子來調製丙烯酸溶膠組合物 月升/時具有可進一步提高丙稀酸溶膠組合物之健存穩 定性，且進一步抑制塗敷時之黏度上升或加熱硬化後之滲 出產生之優點。 進而，於將（a)丙烯酸聚合物微粒子製成内核_外殼型之 情形時’較好的是，以可塑劑親和性聚合物構成内核部， 、可2齊j非親和性聚合物構成外殼部。缺乏與可塑劑之相 洛性之外殼部的聚合物，藉由覆蓋與可塑劑具有相溶性之 内核。Ρ ίΐ)抑制於儲存中丙烯酸溶膠組合物之黏度上升， 且進-步提高儲存穩n X，藉由將如此之外殼部之聚 合物加熱至適當溫纟’而具有與可塑劑之相溶性，故而加 熱硬化後不產生渗出。 至於上述内核部’較好的是含有50質量％以上之自甲基 丙烯酸丁酯基丙烯酸正丁醋)、甲基丙烯酸異丁… 基丙烯酸乙醋中選擇的甲基丙烯酸醋單體之均聚物及共聚 物中之至；一種。如此般，可藉由將内核部之成分設為與 可塑劑相洛性較高纟，而抑制加熱硬化後滲出之產生。尤 其疋’就賦予塗膜以柔軟性之觀點而t，較好的是將甲基 丙烯&amp; 丁酉曰與甲基丙烯酸異丁酯之共聚物作為内核部成分 J07025.doc 1378964 之主體。 其又’上述外殼部，較好的是含有5〇質量％以上之，自甲 醋及甲基丙焊酸节醋中選擇的甲基丙婦 均聚物及共聚物，以及該等甲基丙稀酸醋單體與笨乙 共聚合成分之共聚物中之至少-種。如此般，可藉由 ::殼部之成分設為與可塑劑之相溶性為較低者，而抑制 2中丙料溶膠組合物之黏度上升，進—步提高其儲存 穩定性。尤其是，就進一步提高 /徒同儲存穩疋性之觀點而言， 較好的是將甲基㈣酸Μ聚合物料外殼 體。 作為本發明中所使用之内核-外殼型丙稀酸聚合物微粒 子’例如可列舉：揭示於曰本專利特開平6-172734號公 報、曰本專利特開2001_329135號公報、曰本專利特開 2001-329208號公報、國際公開第〇1/88〇〇9號案等中之= 核-外殼型丙稀酸樹脂微粒子等。 進而，上述内核部與上述外殼部之聚合物比（前者/後 者）’其較好的是自質量比25/75〜7〇/3〇之範圍内加以選 擇。於内核部少於滿足上述範圍之量之情形時，與滿足上 述範圍之情形相比’加熱硬化後產生滲出之可能性増加。 又，於外殼部少於滿足上述範圍之量之情形時，與滿足上 述範圍之情形相比，外殼部對内核部之覆蓋有時變得不充 分，具有影響儲存穩定性之可能性。 又，⑷丙烯酸聚合物微粒子’就塗膜強度、儲存穩定性 等觀點而言，較好的是分子量（以質量平均分；旦 一 丁里表示）為 107025.doc 11 1378964 10萬〜數100萬者，就對於可塑劑之擴散性或儲存穩定性之 觀點而言’較好的是使用平均粒子徑為0.1〜10 μιη之範圍 者。 其次，以下說明（b)嵌段聚胺基甲酸酯。 作為本發明中所使用之（b)成分之嵌段聚胺基甲酸酯， 可藉由下述方式獲得：使用嵌段劑，將聚異氰酸酯與聚醚 ^几醇或聚酯多元醇等α_多元酵反應所獲得之聚胺基甲酸 醋進行嵌段反應。 至於上述聚異氰酸酯，可列舉：丙烷_丨，2_二異氰酸酯、 ,一甲基丁烧_2,3_—異氰酸酯、2~甲基戊烧-2,4-二異氰 酸酯、辛烷_3,6_二異氰酸酯、3,3_二硝基戊烷-〗，5_二異氰 酸酯、辛烷-1，6·二異氰酸酯、Μ•六亞甲基二異氰酸酯 (HDI)、三曱基六亞曱基二異氰酸酯、離胺酸二異氰酸 酯、甲苯二異氰酸酿（TDI)、苯二甲基二異氰酸酯、間四 甲基苯二甲基二異氰酸酯、異佛爾酮二異氰酸酯（3_異氰酸 酷甲基·3,5,5-三甲基環己基異氰酸酯）、丨^或丨’肛雙（異氛 酸酯甲基）環己烷、二苯基曱烷-4,4，-二異氰酸酯（Mm)、二 環己基曱烷-4,4·-二異氰酸酯（氫化MDI)、氫化甲苯二異氮 西文i旨等二異氰酸酷及s亥等之混合物。該等聚異氰酸酿，亦 可係經由三聚合而成之異三聚氰體。 此處，聚異氰酸酯之異三聚氰體，其可藉由下述方式獲 得：例如於乙酸甲酯、乙酸乙酯、乙酸丁酉t、 曰 τ丞乙基 酮、二噁烷等惰性溶劑中，或鄰苯二甲酸二乙酿、鄰笨— 曱酸二丁酯、鄰苯二甲酸二（2-乙基已基）酯、燒基之护原 107025.doc 12 1378964 :數為7〜11(以下記作C7〜c&quot;)之混合烷基鄰苯二甲酸酯、 郴苯一甲酸苄丁酯'鄰苯二甲酸己醇苄酯等鄰苯二甲酸 酯，三甲酚磷酸酯、三苯基磷酸S旨等磷酸酯，己二酸二 (乙基己基）西日等己二酸醋或者C7〜C】】之混合院基偏苯三 甲酉夂S曰等偏苯二甲酸醋等之可塑劑中，使用眾所周知之觸 媒，例如··三級胺、四級錄化合物曼尼希⑽㈣叫 鹼、脂肪酸之鹼金屬鹽、醇鹽等’而藉由已知之方法進行 發性之溶劑中進行聚合反應者，最好是最終 ^ 弗點溶劑、例如可塑劑進行溶劑置換處理者。 作為可用於製造（b)嵌段； 醇，較好的是使用多-酿 上述聚驗多元 1ΛΛ 疋使用夕7^酵之聚烷基己二醇（分子量 100〜5500左右）加成物。 （刀子里 丁至：上述多元醇，例如可列舉··乙二醇、丙二醇、14 丁二酵、新戊二醇等脂肪族二元 ’- 烷、1，2,3-丁烷三醇、12 —知二舍基異戊 _ 岭，，戍燒三醇、2-甲美丨9 3ρ 三醇、2-甲基_2,3,心丁燒三醇、 ：·，，3-丙燒 2 3 4 Λ' 基-1，2,3-丁烷三醇、 2,3,4-戍烷二醇、2,3,4•己烷三醇、 醇、2,4- _甲其丙基_3,4,5-庚烷三 —甲基-2,3,4-戊烷三醇、五 ^丁炫三醇、1，2,4•戊炫三醇、三二二甘油、 醇；赤藻糖醇、異戊四醇、 工等二兀 烷四醇、1 2 3 5以 ，，，4_戍烷四醇、2,3,4,5-己 側金訂醇；^ 已貌四醇等四元醇； 側金益化_、***㈣、木糖醇 和， 甘露醇、艾杜糖醇等六元醇等· ’山梨糖酵' 元醇，尤其好的是丙二醇、丙/中，較好的是2〜4 107025.doc •13- 望藉!可_述方式製造:以成為所期 成於相關之多=又常用方法將碳數為2〜4之氧化歸加 如可列舉:氧：二氧 使用氧化丙稀。“丙烯、氧化丁烯，尤其好的是 夕又’至於可用於製造（b)嵌段聚胺基甲酸S旨之上述聚醋 二醇’例如可列舉：自聚幾酸及多元醇而製造之先前眾 周知之聚酷、或自内醯胺類而獲得之聚酯等。 至於上述聚緩酸，例如可使用：苯三甲酸、己二酸、琥 站酸、辛二酸、癸二酸、草酸、甲基己二酸、戊二酸、庚 馱壬一^、鄰苯二甲酸、對苯二甲酸、間苯二甲酸、 硫代二丙酸、馬來酸、富馬酸、檸康酸、衣㈣，或屬於 該等之任意之適當之鲮酸。 至於上述多元醇’例如可使用：乙二醇、丙二醇、M_ 丁一醇I，3 丁 一醇、1，5-戊二醇、1,6-己二醇、雙（羥甲 基氣己烷）、二乙二醇、2,2-二甲基丙二醇、U3,6_己三 醇、二羥甲基丙烷、異戊四醇、山梨糖醇、丙三醇、或屬 於該等之任意之適當之多元醇。此外，作為聚羥基化合 物，亦可使用聚四亞甲基二醇、聚己内酯二醇等。 構成（b)嵌段聚胺基曱酸酯之聚胺基甲酸酯，例如可藉 由使如上所述之聚醚多元醇、聚酯多元醇、該等…多元醇 之混合物，或於s玄等中進一步混合入蓖麻油等含〇Η基之 縮水甘油酯類混合物等之聚羥基化合物，與上述聚異氰酸 醋反應而獲得。 107025.doc 14 1378964 於獲得上述聚胺基甲酸酯時’上述聚異氰酸酯與α•多元 醇等多輕基化合物之莫耳比（前者/後者），通常是 1.5〜3.5/1 ’較好的是2.0〜3.0/1。又，預聚物（聚胺基曱酸 酯）之NCO%，通常是1-20%，較好的是2〜15%β</ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; It can also be hardened at a lower temperature, and is an acrylic sol composition excellent in adhesion to a coating film substrate or cold resistance of a coating film and coating film strength. [Prior Art] Nowadays, the plastisol widely used in the industry is a liquid or pasty viscous combination which is formed by uniformly dispersing polymer particles having a specially adjusted particle size and particle size distribution together with a filler in a plasticizer. Things. Next, the plastisol is applied to a substrate, and a suitable processing temperature is applied to form a coating film of the strong ray. As the polymer particles, a chlorinated ethylene homopolymer or chlorination is usually used. A polyethylene-based copolymer such as a copolymer of ethylene and vinyl acetate. A plastisol using such a polyvinyl chloride-based polymer particle is excellent in long-term storage stability at room temperature, and has a soft coating film and excellent durability. Therefore, it is widely used for steel sheet coating, clothing, building materials, and enamel. In the fields of supplies, groceries, auto parts, etc. However, the gasified ethylene-based plastisol is decomposed by heat or light to generate hydrogen chloride gas, "the hydrogenated gas produced here, which has the basis of the substance that causes the destruction of the ozone layer" or causes acid rain, or accelerates incineration when incinerated. The problem of damage to the furnace, and further concerns that it may cause Daisyxin due to incineration conditions, is not good in terms of safety and hygiene or environmental pollution. 107025.doc 1378964 Therefore, the industry is now expecting a plastic sol that can replace the polyvinyl chloride-based plastic solution. As a plastisol which can replace a polyvinyl chloride-based plastisol, Patent Document 1 discloses that a plastic sol containing an acrylate polymer and an organic plasticizer is dissolved; however, the plastisol has insufficient storage stability and film forming property. Disadvantages β Further, in Patent Document 2, there is disclosed a plastisol which does not contain a methyl methacrylate polymer or copolymer, a plasticizer, a filler, a blocked urethane, and a poly Polyvinyl chloride formed by amine; however, when the processing temperature of the coating film is lower, the plastisol is not subjected to the hardening reaction of the amine phthalate resin, so the performance of the obtained coating film is insufficient. 'And if placed at 35. (In the case of the right and left, it is gelatinized in 1 to 2 days, and therefore it is not practical. Further, in Patent Document 3, there is proposed a method comprising an acrylic polymer microparticle, a block type amino phthalate resin, and a solid state. Acrylic sol of lanthanide hardener, plasticizer and filler; in Patent Document 4, there is proposed a acrylate polymer microparticle, a plasticizer, a filler, a sulfonate amine acrylate resin, a hardener, and a foaming agent. An acrylic sol is used for the sound-proof primer layer of the agent. However, the acrylic sols have disadvantages such as insufficient adhesion to the substrate, or insufficient flexibility at low temperatures, etc. Further, in Patent Document 5 'Proposed that there is a heat in which a core-shell type acrylic resin particle and a filler are dispersed in a plasticizer, and a block of amino phthalate or block isocyanate and a latent hardener are added. A sclerosing composition; in Patent Document 6, a plastisol is prepared by dispersing acrylic resin particles and a filler into a plasticizer in 107025.doc 1378964, and adding a blocked amine group The ester or blocked isocyanate is a thermosetting composition having a melting point of 6 Å at room temperature and having a melting point of 4 ( or more, which is not dissolved in a latent curing agent of a plasticizer. The thermosetting composition is also unsatisfactory in terms of viscosity stability, adhesion, etc. Further, Patent Document 7 proposes an acrylic polymer microparticle, an embedded &amp; urethane, and a poly An acrylic sol composition of an amine compound, a benzene resin, a plasticizer, and a filler; and Patent Document 8 proposes a block polyamine obtained from a dimer of an acrylic polymer microparticle, a polyol, and a diisocyanate. The acryl sol composition of a phthalic acid ester, a plasticizer, and a filler. However, these acryl sol compositions are not satisfactory in terms of viscosity stability, etc. [Patent Document 1] Japanese Patent Publication No. Sho 55-161 77 [Patent Document 2] Japanese Patent Publication No. 2001-329135 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-329208 (Patent Document 5) country [Patent Document 6] International Publication No. 1/88011A1 [Patent Document 7] Japanese Patent Laid-Open No. 2004-5 1948 [Patent Document 8] International Publication No. 3/1 Case No. 02077 [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide a hydrogenation gas or dioxin which does not generate gas during incineration, has good storage stability and is even at a lower temperature. In the present invention, the inventors of the present invention conducted active research, and the acrylic sol composition which is excellent in the cold resistance of the raw film or the coating film and the coating film strength. As a result, it has been found that a propylene sol composition can be provided, and the above acryl sol composition is obtained by an acrylic sol composition containing an acrylic polymer microparticle 'block urethane or the like. Among them, the polyamine compound and the acidic acid ester compound are contained to improve the problems as described above. That is, the present invention provides an acrylic sol composition characterized by comprising (a) acrylic polymer microparticles, a block polyurethane, (c) a polyamine compound, (d) an acid phosphate compound, (e) a plasticizer and (1) a filler. [Embodiment] Hereinafter, the acrylic sol composition of the present invention will be described in detail. Hereinafter, (a) acrylic polymer microparticles will be described first. As the component (a) used in the present invention, that is, the acrylic polymer microparticles, the polymer which is usually used in the acrylic sol composition can be selected, for example, from an alkyl acrylate or an alkyl methacrylate. A homopolymer or copolymer of the monomers. Specific examples of the monomer include: formazan acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, second butyl acrylate, and acrylic acid. Tributyl, cyclohexyl acrylate, benzyl acrylate 'methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid Butyl ester, methacrylic acid second butyl I07025.doc 曰 + third butyl methacrylate, cyclohexyl methacrylate and benzhydryl phthalate. Further, as the copolymerization component, styrene, α-mercapto spheroidal or the like can also be used. As the (a) acrylic polymer microparticles, it is preferred to use core-shell type acrylic polymer microparticles including a core portion and a shell portion. The use of the core-shell type acrylic polymer microparticles to prepare the acrylic sol composition at a monthly rise/time can further improve the storage stability of the acrylic sol composition, and further suppress the increase in viscosity during coating or the exudation after heat hardening. The advantages that arise. Further, in the case where (a) the acrylic polymer microparticles are made into a core-shell type, it is preferable that the core portion is formed of a plasticizer affinity polymer, and the shell portion can be formed of a non-affinitive polymer. . A polymer lacking the outer shell portion of the plasticizer by covering the core which is compatible with the plasticizer.抑制 ΐ ΐ 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制 抑制Therefore, no bleeding occurs after heat hardening. As for the above-mentioned core portion, it is preferable to homogenize the methacrylic acid acrylate monomer selected from the group consisting of 50% by mass or more of butyl methacrylate butyl acrylate and methacrylic acid butyl acrylate. Among the materials and copolymers; one. In this manner, it is possible to suppress the occurrence of bleeding after heat hardening by setting the composition of the core portion to be higher than that of the plasticizer. In particular, the coating film is imparted with flexibility. From the viewpoint of flexibility, a copolymer of methyl propylene &amp; butyl hydrazine and isobutyl methacrylate is preferred as the core component J07025.doc 1378964. Further, the above-mentioned outer shell portion preferably contains more than 5% by mass of methyl methacrylate homopolymer and copolymer selected from methyl vinegar and methyl propylene solder vinegar, and the methyl propyl acrylate. At least one of a copolymer of a dilute vinegar monomer and a stupid ethyl copolymer component. In this manner, the viscosity of the second propylene sol composition can be suppressed by increasing the compatibility of the component of the shell portion with the plasticizer, and the storage stability can be further improved. In particular, in terms of further improving/consistent storage stability, it is preferred to use a methyl (tetra) phosphonium polymer material outer shell. The core-shell type acrylic polymer microparticles used in the present invention are disclosed, for example, in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. -329208, International Publication No. 1/88〇〇9, etc. = nuclear-shell type acryl resin fine particles. Further, it is preferable that the ratio of the polymer (the former/the latter) of the core portion to the outer shell portion is selected from the range of the mass ratio of 25/75 to 7 Å / 3 Torr. In the case where the core portion is less than the amount satisfying the above range, the possibility of occurrence of bleeding after heat hardening is increased as compared with the case where the above range is satisfied. Further, when the outer casing portion is less than the amount satisfying the above range, the outer casing portion may be insufficiently covered by the outer core portion as compared with the case where the above-described range is satisfied, and the storage stability may be affected. Further, (4) the acrylic polymer microparticles are preferably in terms of coating film strength, storage stability, etc., and the molecular weight (in terms of mass average fraction; Dan Dingli) is 107025.doc 11 1378964 100,000 to several million It is preferable that the average particle diameter is in the range of 0.1 to 10 μm from the viewpoint of the diffusibility or storage stability of the plasticizer. Next, the (b) block polyurethane is explained below. The block polyurethane which is the component (b) used in the present invention can be obtained by using a block agent, a polyisocyanate, a polyether or a polyester polyol, or the like. The polyamidoformate obtained by the multi-fermentation reaction is subjected to a block reaction. As the above polyisocyanate, propane_丨, 2_diisocyanate, monomethylbutane-2,3_-isocyanate, 2-methylpentyl-2,4-diisocyanate, octane_3,6 may be mentioned. _Diisocyanate, 3,3-dinitropentane-, 5-diisocyanate, octane-1,6. diisocyanate, hexamethylene diisocyanate (HDI), tridecyl hexamethylene Diisocyanate, diazonic acid diisocyanate, toluene diisocyanate (TDI), benzodimethyl diisocyanate, m-tetramethyl benzyl diisocyanate, isophorone diisocyanate (3 - isocyanate Methyl 3,5,5-trimethylcyclohexyl isocyanate), 丨^ or 丨' anal (isocyanate methyl)cyclohexane, diphenyldecane-4,4,-diisocyanate ( Mm), a mixture of dicyclohexyldecane-4,4·-diisocyanate (hydrogenated MDI), hydrogenated toluene diisoazide, etc., such as diisocyanate and shai. The polyisocyanate may also be a heterotriocyanide formed by tripolymerization. Here, the isomeric cyanuric polyisocyanate can be obtained by, for example, in an inert solvent such as methyl acetate, ethyl acetate, butyl hydrazine t-butoxide, decanoyl ketone or dioxane. Or diethyl phthalate brewing, o-brown - dibutyl phthalate, di(2-ethylhexyl) phthalate, base of the base 107025.doc 12 1378964: the number is 7~11 ( Hereinafter, it is referred to as a mixed alkyl phthalate of C7 to c&quot;, a phthalic acid ester such as benzyl butyrate benzyl butyl phthalate, tributyl phosphate, and triphenyl benzene. Phosphoric acid S, such as a phosphate, adipic acid di(ethylhexyl), adipic acid or adipic acid vinegar or C7~C] mixed mixed with a phthalic acid, phthalic acid, etc. In the agent, a well-known catalyst is used, for example, a tertiary amine, a quaternary compound Mannich (10) (four) is called an alkali, an alkali metal salt of a fatty acid, an alkoxide, etc., and is carried out in a solvent by a known method. The polymerization reactor is preferably a solvent-substituted solvent, such as a plasticizer, for solvent replacement treatment. As the alcohol (4), it is preferred to use the poly-alkyl diol (molecular weight of about 100 to 5,500) as an adduct. (Knife to the above-mentioned polyol, for example, an aliphatic binary '-alkane, 1,2,3-butanetriol, such as ethylene glycol, propylene glycol, 14 dibutyl glycol, and neopentyl glycol, 12—Knowledge bis-isolated _ ling, 戍 三 triol, 2-methyl hydrazine 9 3 ρ triol, 2-methyl _2, 3, butyl triol, :·,, 3-propane 2 3 4 Λ' keet-1,2,3-butane triol, 2,3,4-decanediol, 2,3,4 hexane triol, alcohol, 2,4- _ 甲甲Base_3,4,5-heptane tri-methyl-2,3,4-pentanetriol, pentaerythritol, 1,2,4·pentanetriol, tridipylene glycol, alcohol; Alcohol, pentaerythritol, dioxane tetraol, 1 2 3 5 , , , 4 - decane tetraol, 2,3,4,5-hexyl gold-based alcohol; Tetrahydric alcohols such as alcohol; flavonoids _, arabic (tetra), xylitol, hexitols such as mannitol and iditol, etc., 'sorbitan', especially propylene glycol, propylene/medium, It is better to use 2~4 107025.doc •13- hope to borrow! It can be manufactured according to the method: in order to become the relevant ones, the common method is to add the oxidation number of 2~4. Oxygen: use of dioxane Acrylonitrile. "Propylene, butylene oxide, especially good, as well as the above-mentioned polyester diol which can be used for the production of (b) block polyamino carboxylic acid S, for example, self-polymerization and polybasic A polyester or the like obtained by alcohol, or a polyester obtained from an internal amide. For the above polyacid, for example, benzenetricarboxylic acid, adipic acid, arachidonic acid, suberic acid, Azelaic acid, oxalic acid, methyl adipic acid, glutaric acid, heptanoic acid, phthalic acid, terephthalic acid, isophthalic acid, thiodipropionic acid, maleic acid, fumaric acid , citraconic acid, clothing (4), or any suitable citric acid of any of the above. For the above polyols, for example, ethylene glycol, propylene glycol, M-butanol I, 3 butanol, 1,5- Pentandiol, 1,6-hexanediol, bis(hydroxymethylhexane), diethylene glycol, 2,2-dimethylpropanediol, U3,6-hexanetriol, dimethylolpropane, Isopenicol, sorbitol, glycerol, or any suitable polyol of any of these. Further, as the polyhydroxy compound, polytetramethylene glycol can also be used. Caprolactone diol, etc. The polyurethane constituting the (b) block polyamino phthalate, for example, by polyether polyol, polyester polyol, etc. as described above A mixture of alcohols or a polyhydroxy compound such as a glycidyl ester-containing mixture such as castor oil or the like, which is obtained by reacting with the above-mentioned polyisocyanuric acid vinegar, is obtained by the reaction of the above-mentioned polyisocyanate. 107025.doc 14 1378964 In the above-mentioned polyurethane, the molar ratio (the former/the latter) of the above polyisocyanate and the poly-based compound such as α-polyol is usually 1.5 to 3.5/1 ', preferably 2.0 to 3.0/1. Further, the NCO% of the prepolymer (polyaminophthalic acid ester) is usually from 1 to 20%, preferably from 2 to 15%.

上述聚胺基甲酸酯，可藉由通常之方法獲得。至於反應 溫度，通常是40〜140°C，較好的*6O〜13〇0C。於進行胺基 甲酸8曰預t物生成反應時，為促進反應，亦可使用眾所周 知之胺基曱酸酯聚合用觸媒，例如二丁基錫二月桂酸酯、 錫正辛酸酯、錫辛酸酯、辛酸鉛、環烷酸鉛、辛酸鋅等有 機金屬化合物，二乙二胺，三乙胺等第三胺系化合物。 作為上述聚胺基甲酸酯，較好的是自聚醚多元醇及二莫 氰酸酯而獲得者；作為上述聚醚多元醇，當使用三官能幻 上之聚醚多元醇、尤其是使用甘油三（聚丙二醇）時，因德 得與基材之密著性為進-步優異之丙稀酸溶膠組合物，: 而為尤，、好又作為上述二異氰酸酯，就與基材之密著The above polyurethane can be obtained by a usual method. As for the reaction temperature, it is usually 40 to 140 ° C, preferably *6O to 13 〇 0C. In order to promote the reaction, a well-known catalyst for the polymerization of an amino phthalate such as dibutyltin dilaurate, tin n-octanoate, or octanoic acid may be used to promote the reaction. An organometallic compound such as ester, lead octoate, lead naphthenate or zinc octoate, or a third amine compound such as diethylenediamine or triethylamine. As the above-mentioned polyurethane, it is preferably obtained from a polyether polyol and a diocyanate; as the above polyether polyol, when a trifunctional polyether polyol is used, especially In the case of glycerol triglyceride (polypropylene glycol), the adhesion between the indene and the substrate is an excellent acrylic acid sol composition, which is particularly good as the above diisocyanate. the

性之觀點而言’較好的是六亞甲基二異氰酸酿、甲苯二異 氰酸自旨。 (b)嵌段聚胺基甲酸酷，俾以故讲此女丨μ θ你以嵌段化劑將上述聚胺基 酸醋進行嵌段反應而獲得者，5β， 〇又付有，至於上述嵌段化劑，例如 列舉：丙二酸二酯(丙二酸二乙酯等)、乙醯丙酮、乙醯 酸醋(乙酿乙隨乙醋等)等活性亞甲基化合物；丙酮肪、 基乙基酮肟（ΜΕΚ肟）、甲其显丁甘π , τ丞呉丁基酮肟（ΜΙΒκ肟）、曱基 厢等辟化合物；曱醇、己醒 匕％ 丙醇、丁醇、戊醇、辛醇 2_乙基己§?·、異壬醇 ' 辟奸妒楚 更月曰知專—元醇或該等之異構體 107025.doc 1378964 τ丞二醇、乙二醇、二乙二醇、三乙二醇、丁二醇、二乙 二醇丁醚等二醇衍生物；二環己基胺等胺化合物；苯酚、 曱酚、乙基笨酚、正丙基苯酚、異丙基笨酚、丁基苯酚， 第三丁基苯酚、辛基苯酚、壬基苯酚、十二烷基苯酚、環 己基笨酚 '氣苯酚、溴笨酚、間苯二酚、鄰苯二酚、對苯 一酚、雙酚A、雙酚S'雙酚F、萘酚等苯酚類；ε_己内酯 等。 ·From the viewpoint of the nature, hexamethylene diisocyanate and toluene diisocyanate are preferred. (b) Block polyaminocarboxylic acid is so cool, so that the 丨μ θ you get the above-mentioned polyamino acid vinegar block reaction with a blocker, 5β, 〇 added, as for the above Examples of the blocking agent include active methylene compounds such as malonic acid diester (diethyl malonate, etc.), acetamidine acetone, acetic acid vinegar (ethylene b, vinegar, etc.); Base ethyl ketone oxime (ΜΕΚ肟), 甲其丁甘 π, τ丞呉 butyl ketone oxime (ΜΙΒκ肟), 曱基 compartment and other compounds; sterol, awake 匕% propanol, butanol, pentane Alcohol, octanol 2_ethylhex§?, isodecyl alcohol's 辟 更 更 更 更 元 元 元 元 元 元 元 元 元 元 元 元 元 元 元 元 元 元 元 元 元 107 107 107 107 107 107 107 107 107 107 107 107 107 107 a glycol derivative such as ethylene glycol, triethylene glycol, butanediol or diethylene glycol butyl ether; an amine compound such as dicyclohexylamine; phenol, indophenol, ethyl phenol, n-propyl phenol, and isopropyl Phenolic phenol, butyl phenol, tert-butyl phenol, octyl phenol, nonyl phenol, dodecyl phenol, cyclohexyl phenol phenol, bromo phenol, resorcinol, catechol, Benzene Phenol, bisphenol A, bisphenol S' bisphenol F, naphthol and other phenols; ε_caprolactone. ·

用以獲得（b)嵌段聚胺基曱酸酯之嵌段化反應，可藉由 眾所周知之反應方法進行。上述嵌段化劑之添加量，相對 於游離之異氰酸酯基，通常是丨〜2當量，較好的是1.5 當量。 上述聚胺基曱酸酯之嵌段化反應，通常採用於聚胺基甲 酸酯之聚合之最終反應中添加上述嵌段化劑之方法，但即 使於任意階段添加上述嵌段化劑使其反應，均可獲得⑻嵌 段聚胺基甲酸醋。The block reaction for obtaining the (b) block polyamino phthalate can be carried out by a well-known reaction method. The amount of the above blocking agent to be added is usually 丨2 to 2 equivalents, preferably 1.5 equivalents based on the free isocyanate group. The blocking reaction of the above polyamino phthalic acid ester is usually carried out by adding the above-mentioned blocking agent to the final reaction of polymerization of the polyurethane, but the above-mentioned blocking agent is added at any stage. In the reaction, (8) block polyamino carboxylic acid vinegar can be obtained.

作為上述嵌段化劑之添加方法，可採用於規定之聚合結 束夺添加、或於聚合初期添加、或於聚合初期添加一部分 7聚合結束時添加殘餘部分等之方法，但較好的是於聚合 結束時添加。於此情形時，作為規定之聚合結束時之標 準則以異氰酸酯％(例如，可藉由揭示於「聚胺基甲酸 酯：稹書店，昭和35年發行，第21頁之方法測定）為基準 厂可於添加上述嵌段化劑時之反應溫度，通常是 50 150C，較好的是6〇〜12〇&lt;5(：。反應時間通常是1〜7小時 左右於反應_，亦V添加上述幕所周知之胺基甲酸酿聚 107025.doc 1378964 合用觸媒來促進反應。又，於反應時，可添加任意量之下 述可塑劑。 於本發明之丙烯酸溶膠組合物中，作為（b)嵌段聚胺基 甲酸酯之添加量，於（a)丙烯酸聚合物微粒子與（b)嵌段聚 胺基甲酸酯之質量比（前者/後者）中，較好的是 90/10〜15/8 5’尤其好的是90/10〜5 0/50。於（b)喪段聚胺基 曱酸醋之添加量少於滿足上述範圍之量之情形時，與滿足 上述範圍之情形相比，有時與塗膜基材之接著性、或者塗 膜之耐寒性及塗膜強度並不充分。又，於（b)嵌段聚胺基甲 酸酯之添加量多於滿足上述範圍之量之情形時，與滿足上 述範圍之情形相比，有時經調製之丙烯酸溶膠組合物之黏 度上升，可能會給塗敷時之操作性造成影響。 其次，以下說明（c)聚胺化合物。 作為本發明中所使用之（C)聚胺化合物，例如可列舉：乙 一胺、一乙二胺、三伸乙基四胺、四伸乙基五胺、聚氧丙 烯一胺，聚氧丙烯三胺，二胺基丙烷等脂肪族多胺； 異佛爾酮二胺、二胺基環己烷、孟烯二胺 (menthenediamine) '雙（4-胺基曱基二環己基）曱烷、二 胺基二環己基甲烷、雙（胺基曱基）環己烷、N_胺基乙基哌 嗪、3,9-雙（3-胺基丙基）_2,4,8，1〇-四氧雜螺（55)十一烷等 脂環族多胺；間苯二胺、對苯二胺、甲苯_2,4_二胺、曱 苯-2,6-二胺、均三曱苯·2,4·二胺、均三曱苯_2,6_二胺、 3,5-二乙基曱苯_2,4_二胺、3,5_二乙基甲苯_2,6_二胺等單 核多胺；亞聯苯基二胺、4,4_二胺基二苯基甲烷、2,5-亞 107025.doc •17· 1378964 条·基二胺 ^ η jr ^ ，6-亞秦基二胺等芳香族多胺；以縮水甘油醚 s丙綿晴將該等聚胺化合物進行加成改質而成，或以羧酸 物進行醯胺改質而成之改質多胺等。 該等之聚胺化合物中，當使用自脂肪族多胺或脂環族多 胺及聚縮水甘油化合物中所獲得之改質胺時，可獲得保存 穩疋丨生更為優異之丙烯酸溶膠組合物，故而為較好。 至於可提供上述改質多胺之聚縮水甘油化合物，例如可 列舉，對苯二酚、間苯二酚、鄰苯二酚、間苯三酚等單核 夕元笨酚化合物之聚縮水甘油趟化合物；二經基萘、聯苯 酚、亞甲基雙酚（雙酚F)、亞甲基雙（鄰甲酚）、亞乙基雙 酚、異亞丙基雙酚（雙酚A)、異亞丙基雙（鄰曱酚）、四溴雙 酚A、丨’3-雙（4-羥基枯烯基苯）、1，4-雙（4-羥基枯烯基笨）、 1，1，3-三（4·羥基苯基）丁烷、u，2,2·四（4·羥基苯基）乙烷、 硫代雙酚、磺基雙酚、氧基雙酚、酚醛樹脂、正甲酚醛樹 月旨、乙基酚醛樹脂、丁基酚醛樹脂、辛基酚醛樹脂、間笨 二酚酚醛樹脂、雙酚A酚醛樹脂、雙酚!：酚醛樹脂、萜二酚 等多核多元笨酚化合物之聚縮水甘油醚化合物；上述單核 多元苯酚化合物或多核多元苯酚化合物之環氧乙院及/或 環氧丙烧加成物之聚縮水甘油_化合物；上述單核夕_ — 酚化合物之氬化物之聚縮水甘油醚化合物；乙二醇、 _ • y ，丨丨 醇、丁二醇、己二醇、聚乙二醇、硫代二甘醇、丙三醇、 三羥曱基丙烷、異戊四醇、山梨糖醇、雙酚A_環氧乙烷力 成物、二環戊二烯二甲醇等多元醇類之聚縮水甘油醚；馬 來酸、富馬酸、衣康酸、琥珀酸、戊二酸、辛二酸、己_ 107025.doc · 18 · 1378964 酸、壬二酸、癸二酸、二聚酸、三聚酸、鄰苯二甲酸、間 苯二甲酸、對苯二甲酸、偏苯三甲酸、均苯三甲酸、均苯 :甲酸、四氫鄰苯二甲酸、六氫鄰笨二甲酸、甲橋四氫鄰 苯二甲酸等之脂肪族、芳香族或脂環族多驗基酸之縮水甘The method of adding the above-mentioned blocking agent may be carried out by adding a predetermined polymerization or adding it at the initial stage of polymerization, or adding a part of the polymerization at the beginning of the polymerization, and adding a residual portion at the end of the polymerization, but it is preferred to carry out the polymerization. Add at the end. In this case, the standard at the end of the predetermined polymerization is based on the isocyanate% (for example, it can be determined by the method disclosed in "Polyurethane: 稹书店, Showa 35, issued, page 21"). The reaction temperature at which the above blocker can be added is usually 50 150 C, preferably 6 〇 12 12 Torr (5: The reaction time is usually about 1 to 7 hours in the reaction _, also V added The above-mentioned urethane-based polyglycolic acid 107025.doc 1378964 is used in combination with a catalyst to promote the reaction. Further, in the reaction, any amount of the following plasticizer may be added. In the acrylic sol composition of the present invention, as (b) The amount of the block polyurethane to be added is preferably 90/10 in the mass ratio of the (a) acrylic polymer microparticles to the (b) block polyurethanes (the former/the latter). ～15/8 5' particularly preferably 90/10~5 0/50. When (b) the amount of polyamine phthalic acid vinegar added is less than the amount satisfying the above range, and the above range is satisfied. In contrast, sometimes the adhesion to the coating substrate, or the cold resistance of the coating film and the film strength are not Further, when the amount of the (b) block polyurethane is more than the amount satisfying the above range, the viscosity of the prepared acrylic sol composition may be sometimes compared with the case where the above range is satisfied. When it is raised, it may affect the operability at the time of coating. Next, the (c) polyamine compound will be described below. As the polyamine compound (C) used in the present invention, for example, ethylamine and ethylenediamine may be mentioned. , an aliphatic polyamine such as tri-ethyltetramine, tetra-ethylpentamine, polyoxypropylene-amine, polyoxypropylene triamine, diaminopropane; isophorone diamine, diaminocyclohexane Mentenediamine 'bis(4-aminomercaptodicyclohexyl)decane, diaminodicyclohexylmethane, bis(aminomercapto)cyclohexane, N-aminoethylpiper Alicyclic polyamines such as azine, 3,9-bis(3-aminopropyl)_2,4,8,1〇-tetraoxaspiro(55)undecane; m-phenylenediamine, p-phenylenediamine , toluene 2,4-diamine, toluene-2,6-diamine, mesitylene, 2,4.diamine, mesitylene, 2,6-diamine, 3,5-diethyl Base Benzene 2,4-diamine, 3,5-diethyltoluene_2,6_ Mononuclear polyamine such as amine; biphenylene diamine, 4,4-diaminodiphenylmethane, 2,5-sub107025.doc •17·1378964·diamine^ η jr ^ ,6- An aromatic polyamine such as a benzylidene diamine; a modified polyamine obtained by adding or modifying the polyamine compound with a glycidyl ether or a carboxylic acid; Among these polyamine compounds, when a modified amine obtained from an aliphatic polyamine or an alicyclic polyamine and a polyglycidyl compound is used, an acrylic sol which is more excellent in preservation and stability can be obtained. The composition is therefore preferred. As the polyglycidyl compound which can provide the above modified polyamine, for example, polyglycidyl hydrazide of a mononuclear phenol compound such as hydroquinone, resorcin, catechol or phloroglucin can be mentioned. Compound; dipyridyl, biphenol, methylene bisphenol (bisphenol F), methylene bis (o-cresol), ethylene bisphenol, isopropylidene bisphenol (bisphenol A), Propylene bis(o-nonylphenol), tetrabromobisphenol A, 丨'3-bis(4-hydroxycumenylbenzene), 1,4-bis(4-hydroxycumenyl), 1,1, 3-tris(4-hydroxyphenyl)butane, u,2,2·tetrakis(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenolic resin, orthodontic Phenolic resin, ethyl phenolic resin, butyl phenolic resin, octyl phenolic resin, stilbene phenolic resin, bisphenol A phenolic resin, bisphenol!: polynuclear polyphenols such as phenolic resin and stilbene Polyglycidyl ether compound; polyglycidyl compound of the above-mentioned mononuclear polyphenol compound or polynuclear polyphenol compound, epoxy epoxide and/or propylene propylene oxide adduct; Nuclear _ _ PEG compound condensate polyglycidyl ether compound; ethylene glycol, _ • y, sterol, butanediol, hexanediol, polyethylene glycol, thiodiglycol, glycerol , polyglycidyl ether of polyhydric alcohols such as trihydroxymethyl propane, isovaerythritol, sorbitol, bisphenol A_ethylene oxide, dicyclopentadiene dimethanol, etc.; maleic acid, rich Horse acid, itaconic acid, succinic acid, glutaric acid, suberic acid, _107025.doc · 18 · 1378964 acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, Isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, homobenzene: fats such as formic acid, tetrahydrophthalic acid, hexahydro-o-dicarboxylic acid, and methionine Family, aromatic or alicyclic polyhydric acid

油醋類及甲基丙稀酸縮水甘油龍之均聚物或共聚物；Ν，Ν· 二縮水甘油基苯胺、雙（4-(Ν-甲基_Ν_縮水甘油基胺基）苯 基）甲烷等具有縮水甘油基胺基之環氧化合物；乙烯基環 己烯二環氧化物、二環戊烷二烯二環氧化物、環氧環 己基甲基-3,4-環氧基環己烷甲酸酯、3,4_環氧曱基環己 基甲基-6-曱基環己烷曱酸酯、雙（3,4_環氧·6_甲基環己基 曱基）己二酸等環狀烯烴化合物之環氧化物；環氧化聚 二烯、環氧化苯乙烯-丁二烯共聚物等環氧化共軛二烯聚 合物’三縮水甘油異三聚氰酸酯等雜環化合物。又，該等 聚縮水甘油化合物，可係藉由末端異氰酸酯之預聚物使其Homopolymer or copolymer of oil vinegar and methacrylic acid glycidol; hydrazine, hydrazine, diglycidyl aniline, bis(4-(fluorene-methyl-hydrazine-glycidylamino)phenyl An epoxy compound having a glycidylamine group such as methane; a vinylcyclohexene diepoxide, a dicyclopentadiene diepoxide, an epoxycyclohexylmethyl-3,4-epoxy ring Hexane formate, 3,4-epoxydecylcyclohexylmethyl-6-fluorenylcyclohexane decanoate, bis(3,4-epoxy-6-methylcyclohexylfluorenyl) hexane An epoxide such as a cyclic olefin compound such as an acid; a heterocyclic compound such as an epoxidized polydiene, an epoxidized styrene-butadiene copolymer or the like, an epoxidized conjugated diene polymer, a triglycidyl isocyanurate or the like. . Further, the polyglycidyl compound can be made by a prepolymer of a terminal isocyanate.

進行内。卩父聯者.。g亥專聚水甘油基化合物中，較好的是 使用雙酚A型或F型環氧樹脂。 自脂肪族多胺、脂環族多胺等聚胺化合物及聚縮水甘油 基化合物中製造改質聚胺之方法，並未加以特別限制，但 可藉由下述方式而容易地製造：以相對於1莫耳聚胺化合 物為0.5〜1.8當量之比例，使用聚縮水甘油基化合物，根據 需要可使用溶劑’於100〜200°C下進行脫水反應，進而進 行減壓脫水反應（及脫溶劑）》 又’作為改質聚胺，亦可使用將上述聚胺化合物以苯紛 類及醛類進行改質而成者》至於該苯酚類，例如可列舉： 107025.doc •19· 1378964 :齡、甲I乙基苯紛、正丙基苯龄、異丙基笨盼、丁基 本酚、第三丁基苯酚、辛基笨酚、壬基苯酚、十二烷基苯 酚、環己墓笨酚、氣酚、溴酚、間苯二酚、鄰苯二酚、對 苯二齡、雙紛A、雙齡S、雙，、萘齡、或該等苯盼類之 多聚物。至於該醛類，可列舉：曱醛等。In progress. Father-in-law. Among the g Hai polyglycol-based compounds, it is preferred to use a bisphenol A type or F type epoxy resin. The method for producing a modified polyamine from a polyamine compound such as an aliphatic polyamine or an alicyclic polyamine and a polyglycidyl compound is not particularly limited, but can be easily produced by the following means: In a ratio of 0.5 to 1.8 equivalents per 1 mol of the polyamine compound, a polyglycidyl compound is used, and if necessary, a dehydration reaction can be carried out using a solvent '100 to 200 ° C, and then decompression under reduced pressure (and desolvation) Further, as a modified polyamine, it is also possible to use the above polyamine compound to be modified with benzene and aldehydes. For the phenol, for example, 107025.doc • 19· 1378964: age, A, ethyl benzene, n-propyl benzene, isopropyl, butyl phenol, tert-butyl phenol, octyl phenol, nonyl phenol, dodecyl phenol, cyclohexyl phenol, Polyphenols, bromophenols, resorcinols, catechols, biphenyl ages, doubles A, double ages S, doubles, naphthalene ages, or polymers of such benzophenones. As the aldehyde, furfural or the like can be mentioned.

自上述聚胺化合物、苯酚類及醛類製造改質聚胺之方 法，並未加以限定，可藉由下述方式而容易地製造：例 如’以相對於1莫耳聚胺化合物，為〇i〜12莫耳苯紛類及 0.5〜3莫耳醛類之比例加以使用，根據需要可使用溶劑， 於50〜2000。(：下進行脫水反應，進而進行減壓脫水反應（及 脫溶劑）。 於本發明之丙烯酸溶膠組合物中，較好的是，以相對於 每100質量份之（a)丙烯酸溶膠聚合物微粒子為0·01〜10質量 份' 尤其為0.05〜5質量份之比例添加（c)聚胺化合物。 其次’以下說明（d)酸性磷酸酯化合物。The method for producing a modified polyamine from the above polyamine compound, phenol, and aldehyde is not limited, and can be easily produced by, for example, 'with respect to 1 mol of the polyamine compound, 〇i Use a ratio of ~12 moles of benzene and 0.5 to 3 moles, and use solvents as needed, 50~2000. (: a dehydration reaction is carried out, and a dehydration reaction under reduced pressure (and a solvent removal) is carried out. In the acrylic sol composition of the present invention, it is preferred to use (a) acrylic acid sol polymer microparticles per 100 parts by mass. The (0) polyamine compound is added in an amount of from 0. 01 to 10 parts by mass, particularly from 0.05 to 5 parts by mass. Next, the acidic phosphate compound (d) will be described below.

本發明中所使用之（d)酸性磷酸酯化合物，係分子中具 有至少一個以上P_〇H基之磷酸酯化合物，例如可列舉： 正磷酸、偏磷酸、焦磷酸、亞磷酸、聚磷酸、膦酸、曱烷 膦酸、苯膦酸、1-羥基乙烷-1，1-二膦酸、膦酸.等磷酸之烷 基酯、稀基酯或烧基部分取代之酯。作為該部分酯中之燒 基，可列舉：曱基、乙基、丙基、丁基、己基、辛基、異 辛基、2 -乙基己基、癸基、十二炫基、十四烧基、十五燒 基等。至於該部分酯中之稀基，可列舉1稀丙基、辛場 基、癸烯基、十八烯基等。至於該酯之部分取代烷基，可 107025.doc -20- 1378964 列舉· 2-羥基乙基' 2-羥基丙基、2-羥基丁基、2_羥基_2· 苯基乙基等之羥基烷基；2-羥基·3-曱氧基丙基、2_羥基_3· 丁氧基丙基、2-羥基-3-辛氧基丙基、2_羥基_3十八烷基矽 氧烷基丙基、2-羥基-3-苯氧基丙基、2_羥基_3_甲苯氧基丙 基、24基·3·辛基苯氧基丙基等之烧氧基或芳氧基經基烧 基；2-(3-甲氧基-2-經基丙氧基）乙基、2·(3 丁氧基_2超基 丙氧基）乙基、2-(3-苯氧基_2·羥基丙氧基）乙基、2_(3_曱苯 氧基-2-經基丙氧基）乙基等之烧氧基或芳氧基經基烧氧基 烷基等具有羥基及/或醚鍵之烷基等。該等之烧基、烯基 及取代烧基’較好的是’碳原子數為㈣，尤其好的是 1 〜1 0 〇 ’當使用小於500當量之 可進一步提高丙烯酸溶 又，作為（d)酸性磷酸酯化合物 P_〇H、尤其疋50〜300當量者時， 膠組合物之保存穩定性，故而為較好。 ―於本發明之稀丙基溶膠組合物中，較好的是，以相對於 每100質里伤之（a)丙烯酸聚合物微粒子為〇 〇〇卜1〇質量 如尤八好的疋0.01〜5質量份之比例添加（d)酸性磷酸酯化 合物β 至於本發明中所使用 吓偬用之（e)可塑劑，可使用於先前聚氯乙 稀系塑膠溶膠中所你用夕I姻杰丨 叮便用之叮塑劑’例如可使用：鄰苯二甲 酸二異壬基酯、鄰！ 一田缺__ μ 本—曱8文一-(2-乙基己基）酯、鄰苯二甲 酸二異癸基醋、鄰絮__田滅 本一甲酉文丁基卞基酯等之苯二曱酸系可 塑劑；己二酸二（2'乙基己基）醋、己二酸二正癸基醋、壬 二酸二（2·乙基己基㈣、癸二酸二丁基醉、癸二酸二（2-乙 107025.doc 21 · 1378964 發泡劑’可使用藉由加熱而產生氣體之類型之發泡劑，具 體可使用偶氤二甲醯胺、偶氮雙曱醯胺等偶氮系發泡劑 等。作為上述稀釋劑，例如可使用二甲苯、礦物質松節油 等溶劑等。作為上述紫外線吸收劑，可使用笨幷***系、 一苯甲酮系、三嗪系等之紫外線吸收劑。作為該等添加劑 之添加量，可根據添加劑之種類等適當加以選擇，較好的 疋相對於每100質量份之（a)成分，其合計小於1〇〇質量份。 Φ 又，本發明之丙烯酸溶膠組合物之調製方法，並無特別 限制，可使用先前之慣用於調製塑膠溶膠之方法。例如， 使用眾所周知之混合機，充分混合攪拌（a)丙烯酸聚合物微 粒子、（b)嵌段聚胺基曱酸酯、（c)聚胺化合物、（d)酸性磷 酸酿化合物、（e)可塑劑、⑺填充劑、（g)苯酚化合物及/或 羧氧化合物、其他添加劑，藉此可調製本發明之丙烯酸溶 膠組合物。作為混合機，可使用行星式混合機、捏合機、 顆粒攪拌機、滾筒等。 • 本發明之丙烯酸溶膠組合物，可藉由先前眾所周知之塗 裝方法，即刷毛塗裝、滾筒塗裝、空氣噴塗塗裝、無空氣 喷塗塗裝等進行塗敷。並且，可藉由於塗敷本發明之丙稀 酸溶，後將其加熱，而形成塗膜。作為加熱方法，亦可採 用通吊之方法，例如可使用熱風循環乾燥爐等進行加熱。 本發明之丙烯酸溶膠組合物，除可應用於塗料、墨水、 接著劑、黏著劑、密封劑等以外，尚可應用於雜貨、玩 具、工業零件、電氣零件等之成型品。例如，若應用於 、·氏布等，則可成為人造皮革、塗敷物、壁紙、衣料、防 107025.doc •24- 1378964 水薄層等；若適用於金屬板’則可成為抗蝕性金屬板。 實施例 以下，採用實施例就本發明之丙烯酸溶膠組合物加以具 體說明。 [製造例-1]嵌段聚胺基曱酸酯之製造i 投入785 g甘油二（聚丙二醇）（分子量4〇〇〇)，於 100〜110 C、3〇 mmHg條件下進行i小時減壓脫水反應。將 其冷卻至60C ’添加1〇3 g曱苯二異氰酸酯，於氮氣環境 下、於90〜10O°C下反應4小時《其次，冷卻至6〇它，滴入 112 g二環己基胺，於90〜100°C下進行i小時熟成反應，進 而於100〜110°C、30 mmHg條件下進行1小時脫氣反應。 藉由紅外吸收光谱可確認於2660 cm-〗處之NCO之吸收完 全消失，即獲得嵌段聚胺基甲酸酯（BU-1&gt;。 [製造例-2]嵌段聚胺基甲酸酯之製造2 除將112 g二環己基胺換成55 g甲基酮肟以外，其餘與製 造例-1相樣地製造嵌段聚胺基曱酸酯（BU-2)。 [製造例-3]嵌段聚胺基曱酸酯之製造3 於添加曱苯二異氰酸酯之前，除添加1 g構酸乙酯[單/二 (莫耳比）=1/1，P-OH當量93]以外，其餘與製造例-1同樣 地製造嵌段聚胺基甲酸酯（BU-3)。 [製造例_4]嵌段聚胺基曱酸酯之製造4 投入408 g二異壬基鄰苯二曱酸酯、481 g甘油三（聚丙二 醇）（分子量4000)，於100〜110°C、30 mmHg條件下進行1小 時減壓脫水反應。將其冷卻至80°C，添加97 g二環己基甲 107025.doc •25- 1378964 烷-4,4’-二異氰酸酯（氫化MDI)及0.025 g二丁基錫二月桂酸 酯，於氮氣環境下、於90~100°C下反應4小時。又，冷卻 至60°C ’滴入34 g甲基乙基酮肟，於90〜100。(：下進行i小時 熟成反應。 藉由紅外吸收光譜可確認於2660 cnT1處之NCO之吸收完 全消失，即獲得嵌段胺基曱酸酯（BU-4)。 [製造例-5]改質聚胺之製造1 投入399 g異佛爾酮二胺，一面於其中分批添加476 g ADEKA RESIN EP-4100E(旭電化工業公司（株）製；雙齡A 型環氧樹脂、環氧當量為190)—面升溫至l〇(TC，進而於 100〜150°C下熟成2小時。 於其中，於15 0〜18(TC下分批添加140 g MP-800K(旭有 機材工業公司（株）製造；苯酚樹脂），熟成1小時後，進而 添加35 g癸二酸’於1 70~180°C、30〜50 mmHg條件下進行1 小時減壓脫水。以微粉碎機將其粉碎至3〇 μιη以下，取 出，獲得改質聚胺（ΗΡΑ-1)。 [製造例-6]改質聚胺之製造2 投入225 g ι，2-二胺基丙烷、89 g甲苯及89 kg異丙醇， 於 70~95°C下分批添加 571 g ADEKARESIN EP-4901E(旭電 化工業公司（株）製；雙酚F型環氧樹脂），於95~i〇〇°C下熟 成1小時後，於155-165°C、40〜60 mmHg條件下進行1小時 減壓脫溶劑處理。 於其中，於155〜165。(：下分批添加254 g MP-800K，於 15 5〜165它、40〜6〇1111111^條件下進行1小時減壓脫水處 107025.doc •26· 1378964 理。以微粉碎機將其粉碎至3 Ο μπι以下，取出，獲得改質 聚胺（ΗΡΑ-2)。 [製造例-7]改質聚胺之製造3 投入225 g 1,2-二胺基丙院、89 g甲苯及89 kg異丙醇， 於 70 〜95°C 下分批添加 571 g ADEKA RESIN EP-4901E(旭電 化工業（株式）製；雙齡F型環氧樹脂），於95〜1〇〇 下熟成1 小時後，於155〜165°C、40〜60 mmHg條件下進行1小時減 壓下之脫溶劑處理。 於其中’於155~165°C下分批添加254 g MIGHTYACE(音 澤）G -15 0(YASUHARA CHEMICAL公司製造；莊-苯驗共 聚物）’於155〜165°C、40-60 mmHg條件下進行1小時減屋 脫水處理。利用微粉碎機將其粉碎至30 μιη以下，取出， 獲得改質聚胺（ΗΡΑ-3)。 [製造例-8]改質聚胺之製造4 才又入300 g本基一曱苯基乙院及360 g 1,3 -二胺基環己 烧’ 一面於其中分批添加360 g ADEKA RESIN EP-4100E(旭電化工業（株式）製造；雙酚a型環氧樹脂，環氧 當量190)—面將其升溫至1〇〇。〇，進而於1〇〇〜15〇。〇下熟成2 小時，獲得改質聚胺（HPA-4)。 [實施例1〜6以及比較例1〜2] 以表1所示之比例，添加丙烯酸聚合物微粒子、上述所 獲得之嵌段聚胺基甲酸酯等，藉由混煉機將其混合分散， 分別獲得實施例1〜6以及比較例1〜2之丙烯酸溶膠組合物。 &lt;評估方法及結果&gt; 107025.doc •27- 1378964 關於上述實施例1〜6及比較例1、2之丙烯酸溶膠組合 物刀别以以下方法评估黏度穩定性、接著性及塗媒強 度。該專之結果示於表1。 (1) 黏度穩定性 使用B型旋轉黏度計，於溫度25°C下測定丙烯酸溶膠組 合物之初期黏度。其後，將丙烯酸溶膠組合物置於密封容 器内，保持於溫度4〇。〇，分別經過4、7、1 〇天後，冷卻至 25 C ’同樣地測定黏度，算出自初期開始之黏度變化率。 (2) 接著性 於10〇χ25χ1.〇 „1111電鍍塗裝鋼板之端部塗敷丙烯酸溶膠 組合物’以接著部之厚度成為3 mm之方式，將間隔物夾住 而將其壓著。於該狀態下，於13(TC下焚燒2〇分鐘後，取 出間隔物，以50 mm/min之拉伸速度於剪斷方向拉伸，觀 察破壞狀態，根據下述評估標準評估接著性。 〇:凝集破壞 x ·界面破壞 (3) 塗膜強度 將丙烯酸溶膠組合物塗敷於可離型板上至2 mm厚度， 於130°C下焚燒20分鐘製作成薄層後，以啞鈴2號型沖切該 薄層。將該啞鈐分別於23°C、0°C及-20°C下，以50 mm/min 之拉伸速度將其拉伸，測定斷裂時之強度（MPa)及伸展率 (%)。又，亦測定上述薄層之拉伸斷裂強度（MPa)。 107025.doc •28· 1378964 [表i] 實施例 比較例 1 2 3 4 5 6 1 2 添 加 f 量 AR·1 300 300 300 300 300 300 300 300 BU-1 RIJ-2 45 45 45 - - _ 45 45 - - - 45 - - - - — BU-3 - - - 45 - - - BU-4 - - - - 45 - - HPA-1 5 - - 5 5 _ 5 - HPA-2 - 5 - - - - - - HPA-3 - 5 - - - - HPA-4 DINP*2 磷酸乙酯 - - - - - 5 - 350 350 350 350 350 350 350 350 3 3 3 3 3 3 - - ------- CaCO, 300 300 300 300 300 300 300 300 性 能 試 驗 黏度變 化率(％) 4C lc 40 天後 5 5 5 5 5 5 10 3 天後 10 15 20 8 5 6 30 3 °〇χ10天後 15 20 30 13 10 6 固 化 5 接著性 〇 o o o 〇 o Ο X 塗 膜 強 度 割裂 強度 (MPa) 23 °C 1.71 1.68 1.65 1.52 1.69 1.44 1.70 0.73 o°c 2.92 2.88 2.73 2.30 2.89 2.12 2.90 1.07 -20°C 4.72 4.55 4.41 4.41 4.69 4.08 4.68 2.75 伸展 率(％) 23〇C 461 451 450 430 460 630 460 550 0°C 199 202 193 211 201 320 198 278 -20°C 109 89 88 74 105 188 107 132 拉伸 斷裂 (MPa) 23〇C 10.1 11.9 10.0 11.3 10.5 12.2 10.3 6.8 0°C 27.3 29.8 26.0 27.9 27.1 33.8 27.0 18.0 -20 V 37.5 37.3 36.2 36.8 37.4 43.2 37.7 22.6 * 1 ) AR :内核部係以曱基丙烯酸丁酯與甲基丙烯酸異丁酯 之共聚物為主體，外殼部係以曱基丙稀酸曱酯聚合物 為主體之内核-外殼型丙烯酸聚合物微粒子 *2) DINP :鄰苯二甲酸二異壬酯 107025.doc •29· ^/8964 如表1所表明，包含丙烯酸聚合物微粒子、嵌段聚胺基 甲酸s旨、可塑劑及填充劑之丙烯酸溶膠組合物，係塗膜之 接著性不充分’而且即使與塗膜強度相關亦並不充分者 (比較例2)。除此之外’含有聚胺化合物而成之丙烯酸溶膠 組合物’發現其塗膜強度增加但黏度穩定性不良（比較例 1)。 相對於此，含有丙烯酸聚合物微粒子、嵌段聚胺基甲酸 酯、聚胺化合物、酸性磷酸酯、可塑劑及填充劑之本發明 之丙烯酸溶膠組合物，可形成黏度穩定性優異、塗膜之接 著性良好且強韌之塗膜（實施例^6)。 [產業上之可利用性] 本發明之丙烯酸溶膠組合物，於焚燒時並不產生氣化氫 氣體或戴奥辛’其儲存穩定性優異，且即使於較低溫度下 亦可使其硬化，進而對於塗膜基材之接著性或塗膜之耐寒 性及塗膜強度優異，從而廣泛應用於密封材料、塗層材 料、日用品等之中。 I07025.doc 30-The (d) acidic phosphate compound used in the present invention is a phosphate compound having at least one P_〇H group in the molecule, and examples thereof include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, and polyphosphoric acid. An alkyl ester, a dilute ester or a burnt-substituted ester of a phosphonic acid, a decylphosphonic acid, a phenylphosphonic acid, a 1-hydroxyethane-1,1-diphosphonic acid, a phosphonic acid or the like. Examples of the alkyl group in the partial ester include a mercapto group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a decyl group, a decyl group, and a tetradecene. Base, fifteen bases, etc. As the dilute group in the partial ester, 1 propyl group, octyl group, decyl group, octadecenyl group and the like can be given. As for the partially substituted alkyl group of the ester, 107025.doc -20- 1378964 exemplifies a hydroxyl group such as 2-hydroxyethyl '2-hydroxypropyl group, 2-hydroxybutyl group, 2-hydroxyl-2 phenylethyl group or the like. Alkyl; 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 2-hydroxy-3-octyloxypropyl, 2-hydroxy-3-octadecyloxy Alkoxy or aryloxy groups such as alkylpropyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methyloxypropyl, 24-yl-3-octylphenoxypropyl Base-based; 2-(3-methoxy-2-p-propoxy)ethyl, 2·(3-butoxy-2-superpropyloxy)ethyl, 2-(3-phenoxy) An alkoxy group or an aryloxy group having a hydroxyl group such as a base hydroxypropoxy)ethyl group, a 2-(3-benzophenoxy-2-phenylpropoxy)ethyl group or the like And/or an alkyl group of an ether bond. The alkyl group, the alkenyl group and the substituted alkyl group are preferably 'the number of carbon atoms is (4), particularly preferably 1 to 10 〇'. When less than 500 equivalents are used, the acrylic acid can be further improved, as (d) When the acid phosphate compound P_〇H, especially 50 to 300 equivalents, the storage stability of the gel composition is preferred. In the dilute sol composition of the present invention, it is preferred that the (a) acrylic polymer microparticles are inferior to the mass of the acrylic polymer particles per 100 masses. Adding (d) acidic phosphate compound β in proportion to 5 parts by mass. As for the (e) plasticizer used in the present invention, it can be used in the prior polyvinyl chloride plastisol. For the use of plasticizers for sputum, for example: diisodecyl phthalate, adjacent!一田缺__ μ 本—曱8 文一-(2-ethylhexyl) ester, diisodecyl phthalate phthalate, o-fragment __ Tian Benben, methionine butyl decyl ester, etc. Benzoyl phthalate plasticizer; di(2'ethylhexyl) acetonate adipate, di-n-decyl oxalate adipate, adipic acid di(2-ethylhexyl (tetra), dibutyl phthalate Azelaic acid di(2-ethyl 107025.doc 21 · 1378964 foaming agent' may use a foaming agent of a type which generates a gas by heating, and specifically, decyl dimethylamine, azobisguanamine, etc. may be used. An azo-based foaming agent, etc. As the diluent, for example, a solvent such as xylene or mineral turpentine or the like can be used. As the ultraviolet absorber, a chopper triazole system, a benzophenone system, a triazine system, or the like can be used. The amount of the additives to be added may be appropriately selected depending on the type of the additive, etc., and the total amount of the lanthanum is less than 1 part by mass per 100 parts by mass of the component (a). The method for preparing the acrylic sol composition of the present invention is not particularly limited, and may be used to prepare a plastic solution. a method of gluing, for example, using well-known mixers, thoroughly mixing and stirring (a) acrylic polymer microparticles, (b) block polyamino phthalate, (c) polyamine compound, (d) acidic phosphoric acid compound, (e) a plasticizer, (7) a filler, (g) a phenol compound and/or a carboxyoxy compound, and other additives, whereby the acrylic sol composition of the present invention can be prepared. As a mixer, a planetary mixer or a kneader can be used. , a particle mixer, a roller, etc. • The acrylic sol composition of the present invention can be applied by a previously known coating method, namely, brush coating, roller coating, air spray coating, airless spray coating, and the like. Further, the coating film can be formed by applying the acrylic acid solution of the present invention and heating it, and the heating method can be carried out by a hanging method, for example, by using a hot air circulation drying furnace or the like. The acrylic sol composition of the invention can be applied to groceries, toys, industrial parts, electrical zeros, besides coatings, inks, adhesives, adhesives, sealants, and the like. For example, if it is applied to a cloth, such as a cloth, it can be an artificial leather, a coated object, a wallpaper, a clothing, a protective layer of 107025.doc •24-1378964, and the like; It can be a corrosion-resistant metal plate. EXAMPLES Hereinafter, the acrylic sol composition of the present invention will be specifically described by way of examples. [Production Example-1] Production of block polyamino phthalate i Put 785 g of glycerin II ( Polypropylene glycol) (molecular weight 4 〇〇〇), under a condition of 100 to 110 C, 3 〇 mmHg for 1 hour under reduced pressure dehydration reaction. Cool it to 60 C 'add 1 〇 3 g of benzene diisocyanate under nitrogen atmosphere Reacting at 90 to 10 ° C for 4 hours. Secondly, cooling to 6 Torr, dropping 112 g of dicyclohexylamine, and performing i-hour ripening reaction at 90 to 100 ° C, and further at 100 to 110 ° C, The degassing reaction was carried out for 1 hour under conditions of 30 mmHg. It was confirmed by infrared absorption spectroscopy that the absorption of NCO at 2660 cm- was completely disappeared, that is, a block polyurethane was obtained (BU-1). [Production Example-2] Block Polyurethane Production 2 A block polyamino phthalate (BU-2) was produced in the same manner as in Production Example-1 except that 112 g of dicyclohexylamine was replaced by 55 g of methyl ketoxime. [Production Example-3 Production of block polyamino phthalate 3 Before adding benzene phenyl diisocyanate, except adding 1 g of ethyl ethate [single/di (mole ratio) = 1/1, P-OH equivalent 93] The block polyurethane (BU-3) was produced in the same manner as in Production Example-1. [Production Example 4] Production of Block Polyaminophthalate 4 Input 408 g of diisodecyl phthalate Phthalate ester, 481 g of glycerol tris(polypropylene glycol) (molecular weight: 4000), dehydration reaction under reduced pressure for 1 hour at 100 to 110 ° C, 30 mmHg. Cooling to 80 ° C, adding 97 g of dicyclohexyl A 107025.doc • 25- 1378964 alk-4,4'-diisocyanate (hydrogenated MDI) and 0.025 g of dibutyltin dilaurate, reacted under nitrogen at 90-100 ° C for 4 hours. Up to 60 ° C 'Drip into 34 g A Ethyl ketoxime, 90 to 100. (: i hour ripening reaction. It can be confirmed by infrared absorption spectroscopy that the absorption of NCO at 2660 cnT1 completely disappears, that is, block amino phthalate (BU-4) is obtained. [Production Example-5] Manufacture of modified polyamine 1 Into 399 g of isophorone diamine, 476 g of ADEKA RESIN EP-4100E (manufactured by Asahi Kasei Kogyo Co., Ltd.; A type epoxy resin, epoxy equivalent is 190) - the surface temperature is raised to l〇 (TC, and then matured at 100~150 ° C for 2 hours. Among them, 15 0~18 (140 g MP is added in batches under TC) -800K (manufactured by Asahi Organic Materials Co., Ltd.; phenol resin), after 1 hour of aging, further adding 35 g of sebacic acid at 1 70 to 180 ° C, 30 to 50 mmHg for 1 hour under reduced pressure dehydration This was pulverized to 3 μm μη or less with a fine pulverizer, and taken out to obtain a modified polyamine (ΗΡΑ-1). [Manufacturing Example-6] Production of modified polyamine 2 Input of 225 g of ι,2-diamino group Propane, 89 g of toluene and 89 kg of isopropanol, 571 g of ADEKARESIN EP-4901E (made by Asahi Kasei Kogyo Co., Ltd.; bisphenol F type epoxy tree) was added in portions at 70-95 °C. ), After at ~ 95 ° C i〇〇 aging for 1 hour, at 155-165 ° C, 40~60 mmHg for 1 hour removal of the solvent under reduced pressure. Therein at 155~165. (: Add 254 g MP-800K in batches, under 15 5~165, 40~6〇1111111^ for 1 hour under reduced pressure dehydration 107025.doc •26· 1378964. Smash it with a micro-grinder To 3 Ο μπι or less, take out and obtain modified polyamine (ΗΡΑ-2). [Manufacturing Example-7] Manufacture of modified polyamine 3 Inject 225 g of 1,2-diaminopropylamine, 89 g of toluene and 89 Kg isopropyl alcohol, 571 g ADEKA RESIN EP-4901E (made by Asahi Kasei Co., Ltd.; double age F-type epoxy resin) was added in batches at 70 to 95 ° C, and cooked at 95 ° 1 1 for 1 hour. Thereafter, the solvent removal treatment under reduced pressure for 1 hour was carried out at 155 to 165 ° C under 40 to 60 mmHg. Among them, 254 g of MIGHTYACE G -15 0 was added in portions at 155 to 165 ° C. (manufactured by YASUHARA CHEMICAL Co., Ltd.; Zhuang-Benzene Copolymer) was subjected to dehydration treatment at 155 to 165 ° C and 40-60 mmHg for 1 hour, and was pulverized to 30 μm or less by a micro-pulverizer, and taken out to obtain Modified polyamine (ΗΡΑ-3). [Manufacturing Example-8] Modification of polyamine production 4 Only 300 g of the base of a phenyl phenyl group and 360 g of 1,3 -diaminocyclohexane one side Among them, 360 g ADEKA RESIN EP-4100E (made by Asahi Kasei Co., Ltd.; bisphenol a type epoxy resin, epoxy equivalent 190) was added in batches to raise the temperature to 1 〇〇. 〜15〇. The modified polyamine (HPA-4) was obtained by submerging for 2 hours. [Examples 1 to 6 and Comparative Examples 1 to 2] The acrylic polymer microparticles and the above were added in the ratios shown in Table 1. The obtained block urethane or the like was mixed and dispersed by a kneader to obtain the acryl sol compositions of Examples 1 to 6 and Comparative Examples 1 and 2, respectively. <Evaluation Method and Results> 107025 .doc • 27-1378964 The viscosity stability, adhesion, and coating strength of the acrylic sol composition blades of the above Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated by the following methods. The results are shown in Table 1. (1) Viscosity stability The initial viscosity of the acrylic sol composition was measured at a temperature of 25 ° C using a B-type rotational viscometer. Thereafter, the acrylic sol composition was placed in a sealed container and kept at a temperature of 4 Torr. After 4, 7 and 1 day, cool to 25 C ' The viscosity is calculated from the initial viscosity change rate. (2) The adhesive is applied to the end of the 1111 electroplated coated steel sheet, and the thickness of the adhesive portion is 3 mm. The spacer is clamped and pressed against it. In this state, after incineration for 2 minutes at 13 (TC), the spacer was taken out, stretched in the shearing direction at a tensile speed of 50 mm/min, and the state of destruction was observed, and the adhesion was evaluated according to the following evaluation criteria. : Aggregation damage x · Interface damage (3) Film strength The acrylic sol composition was applied to a release liner to a thickness of 2 mm, and was incinerated at 130 ° C for 20 minutes to form a thin layer. The thin layer was die-cut. The matte was stretched at 23 ° C, 0 ° C and -20 ° C at a tensile speed of 50 mm / min, and the strength (MPa) and elongation at break were measured. Rate (%). Further, the tensile breaking strength (MPa) of the above thin layer was also measured. 107025.doc • 28· 1378964 [Table i] Example Comparative Example 1 2 3 4 5 6 1 2 Adding the amount of AR·1 300 300 300 300 300 300 300 300 BU-1 RIJ-2 45 45 45 - - _ 45 45 - - - 45 - - - - - BU-3 - - - 45 - - - BU-4 - - - - 45 - - HPA-1 5 - - 5 5 _ 5 - HPA-2 - 5 - - - - - - HPA-3 - 5 - - - - HPA-4 DINP*2 Ethyl Phosphate - - - - - 5 - 350 350 350 350 350 350 350 350 3 3 3 3 3 3 - - ------- CaCO, 300 300 300 300 300 300 300 300 Performance test viscosity change rate (%) 4C lc 40 days after 5 5 5 5 5 5 10 3 days after 10 15 20 8 5 6 30 3 ° 〇χ 10 days after 15 20 30 13 10 6 curing 5 Next 〇ooo 〇o Ο X Film strength splitting strength (MPa) 23 °C 1.71 1.68 1.65 1.52 1.69 1.44 1.70 0.73 o°c 2.92 2.88 2.73 2.30 2.89 2.12 2.90 1.07 -20°C 4.72 4.55 4.41 4.41 4.69 4.08 4.68 2.75 Extensibility (%) 23〇C 461 451 450 430 460 630 460 550 0°C 199 202 193 211 201 320 198 278 -20°C 109 89 88 74 105 188 107 132 Tensile fracture (MPa) 23〇C 10.1 11.9 10.0 11.3 10.5 12.2 10.3 6.8 0°C 27.3 29.8 26.0 27.9 27.1 33.8 27.0 18.0 -20 V 37.5 37.3 36.2 36.8 37.4 43.2 37.7 22.6 * 1 ) AR: The core part is butyl methacrylate and isobutyl methacrylate. The copolymer is mainly composed of a core-shell type acrylic polymer microparticles mainly composed of a mercapto acrylate polymer*2) DINP: diisodecyl phthalate 107025.doc •29· ^/ 8964 as shown in Table 1, containing acrylic polymer microparticles, block polymerization S purpose carbamic acid, plasticizer, and filler of acrylic sol composition, the coating system is then insufficient 'and even if the film strength is also related to insufficient persons (Comparative Example 2). In addition, the 'acryl sol composition containing a polyamine compound' was found to have an increased coating film strength but poor viscosity stability (Comparative Example 1). On the other hand, the acrylic sol composition of the present invention containing an acrylic polymer microparticle, a block polyurethane, a polyamine compound, an acid phosphate, a plasticizer, and a filler can form an excellent viscosity stability and a coating film. A coating film having good adhesion and strength (Example ^6). [Industrial Applicability] The acrylic sol composition of the present invention does not generate hydrogenated gas or dioxin at the time of incineration, and has excellent storage stability, and can be hardened even at a lower temperature, and further The adhesiveness of the coating film substrate or the cold resistance of the coating film and the coating film strength are excellent, and are widely used in sealing materials, coating materials, daily necessities, and the like. I07025.doc 30-

Claims (1)

第094142671號專利申請案 中文申請專利範圍替換本(101年7月) ι〇Η日|正替換頁 十、申請專利範圍： &quot; 1· 一種丙烯睃溶膠組合物，其特徵在於：烯酸叙 合物微粒子、（b)嵌段聚胺基甲酸酯、（c)聚胺化合物、 (d)酸性磷酸酯化合物、（e)可塑劑及（f)填充劑；且 (d)酸性磷睃酯化合物之P-〇H當量為500以下。 2.如請求項1之丙烯酸溶膠組合物，其中（a)丙烯酸聚合物 微粒子與（b)嵌段聚胺基甲酸酯之質量比（前者/後者）為 90/10〜15/85。 3·如請求項1或2之丙烯酸溶膠聚合物，其中（a)丙烯酸聚合 物微粒子係包含内核部及外殼部之内核-外殼型。 4. 如請求項1之丙烯酸溶膠組合物，其中（b)嵌段聚胺基甲 酸酯係自聚醚多元醇及二異氰酸酯獲得。 5. 如請求項4之丙烯酸溶膠組合物，其中上述聚醚多元醇 係具有三官能以上之聚醚多元醇。 6. 如請求項5之丙烯酸溶膠組合物，其中上述具有三官能 以上之聚醚多元醇係甘油三（聚丙二醇）》 7. 如請求項1之丙烯酸溶膠組合物，其中（b)嵌段聚胺基曱 酸酯係將二環己胺或曱基酮肟作為嵌段化劑而獲得。 8. 如請求項1之丙烯酸溶膠組合物，其中（c)聚胺化合物係 自脂肪族多胺或脂環族多胺及聚縮水甘油化合物所獲得 之改質聚胺。 9. 如請求項8之丙烯酸溶膠組合物，其中上述脂肪族多胺 或脂環族多胺係選自異佛爾酮二胺、1，3-二胺基環己烷 及丨，2-二胺基丙烷中之至少一種。 I07025-1010713.doc 1378964 ----- ——( 年月日修正替換頁 101 7 10. 如請求項8或9之丙婦酸溶膠組合物，其中上述聚縮水甘 油化合物係雙酚A型或F型環氧樹脂。 11. 如請求項1之丙稀酸溶膠組合物，其中（d)酸性麟酸酯化 合物係選自酸性填酸烧酿化合物中之至少一種。 12·如請求項1之丙烯酸溶膠組合物，其中（e)可塑劑係選自 苯二甲酸系可塑劑中之至少一種。 13.如請求項1之丙烯酸溶膠組合物，其中進而包含（g)選自 苯紛化合物及叛酸化合物中之至少一種。 107025-10l0713.docPatent Application No. 094,142, 671, filed, filed, filed, filed, filed, filed, filed, filed, filed filed filed filed filed filed filed filed Microparticles, (b) block polyurethane, (c) polyamine compound, (d) acid phosphate compound, (e) plasticizer and (f) filler; and (d) acidic phosphonium The ester compound has a P-〇H equivalent of 500 or less. 2. The acrylic sol composition of claim 1, wherein the mass ratio of the (a) acrylic polymer microparticles to the (b) block polyurethanes (the former/the latter) is 90/10 to 15/85. 3. The acrylic sol polymer according to claim 1 or 2, wherein the (a) acrylic polymer microparticles comprise a core-shell type of a core portion and a shell portion. 4. The acrylic sol composition of claim 1, wherein (b) the block polyurethane is obtained from a polyether polyol and a diisocyanate. 5. The acrylic sol composition of claim 4, wherein the polyether polyol has a trifunctional or higher polyether polyol. 6. The acrylic sol composition of claim 5, wherein the above polyether polyol having a trifunctional or higher polyglycerol is glycerol triol (polypropylene glycol). 7. The acrylic sol composition of claim 1, wherein (b) block polymerization The amino phthalate is obtained by using dicyclohexylamine or decyl ketoxime as a blocking agent. 8. The acrylic sol composition of claim 1, wherein (c) the polyamine compound is a modified polyamine obtained from an aliphatic polyamine or an alicyclic polyamine and a polyglycidyl compound. 9. The acrylic sol composition of claim 8, wherein the above aliphatic polyamine or alicyclic polyamine is selected from the group consisting of isophorone diamine, 1,3-diaminocyclohexane, and hydrazine, 2-di At least one of aminopropanes. I07025-1010713.doc 1378964 ----- ——(年月日日修正单页 101 7 10. The propylene glycol sol composition according to claim 8 or 9, wherein the polyglycidyl compound is bisphenol A or The F-type epoxy resin. The acrylic acid sol composition of claim 1, wherein the (d) acidic sulphate compound is at least one selected from the group consisting of acidic acid-filling compounds. The acrylic sol composition, wherein the (e) plasticizer is at least one selected from the group consisting of the phthalic acid plasticizers. The acrylic sol composition of claim 1, which further comprises (g) a compound selected from the group consisting of a benzene compound and a rebel At least one of the acid compounds. 107025-10l0713.doc