201002778 六、發明說明： 【發明戶斤屬之技術領域3 發明領域 本發明係關於一種製造環氧熱固性樹脂的方法。更特 別的是，本發明係關於一種使用具有一級羥基官能性的線 性聚酯種類來製造增韌的環氧熱固性樹脂的方法。 發明背景 以環氧樹脂為主的組成物已熟知且為熱固性材料，其 已廣泛使用在例如電機工程、汽車工程及建造應用中。在 這些應用當中，有模塑組成物、液體及粉末塗佈物、狀層 壓板、黏著劑、陶器製造組成物及其類似物。環氧樹脂系 • 統通常具有非常高的硬度及挺度、好的黏附力及絕緣能 力、腐银保護性且亦有好的对熱及化學性。但是，這些系 統之缺點為其經硬化的產物會缺乏韌度。 隨著改善此缺點之目標，已經描述出廣泛多種用於環 ' 氧樹脂系統的添加劑。例如，ΕΡ-Α 2 392 348揭示出包含微 粒熱塑性塑膠(諸如，聚砜)之環氧樹脂系統，其據宣稱具有 改良的韌度。 ΕΡ-Α 2 373 440描述出從芳香族環氧化合物、胺硬化 劑、包含反應性基團（諸如胺終端）或聚醚砜的芳香族熱塑性 寡聚物及亦高分子量乳化劑所製得之增韌環氧樹脂混合物。 美國專利7,329,711揭示出包含二種特定的聚亞芳基醚 颯和充填劑及添加劑之環氧組成物。已主張這些組成物具 3 201002778 有經改良的透明度與比較好或經改良的衝擊強度。 今敏⑽)Y·專k的應用聚合物科學期刊、J〇urnal 却冲W 尸o(ymer 5W⑼ce)(90(l2) ’ 3384-3389，2003，約翰 威利及宋斯公司（John Wiley & Sons Inc·))揭示出以每百份 4-24份的芳香族聚酯來增韌之雙酚A型環氧樹脂。 新（Shin)S.等人的應席求合與存學期办（78(14)， 2464-2473 ’ 2000 ’約翰威利及宋斯公司）揭示出使用芳香族 聚酯來增韌一雙酚Α/二胺基二苯基曱烷環氧系統。 飯島（Lijima)T·等人的應席衮合场存學期办(43(3)， 463-74，199卜約翰威利及宋斯公司）揭示出一組藉由酞酸 或異酜酸與烷二醇之反應所製備的芳香族聚酯，其使 用來減低經曱基六氫酞酸酐硬化的雙酚Α/二縮水甘油醚環 氧樹脂之易碎性。 另一種在技藝中熟知的方法為將一橡膠似物質包合進 入環氧系統中。此方法之實施例包括將一羧基終端的丁二 稀丙烯(CTBN)液體橡膠或一核殼型橡膠(CSR)併入環氧系 統中。 因此’不幸的是，雖然已知有一些改良熱固性環氧樹 脂之衝擊強度（即’ “增韌，，)的方法，許多方法確實如此會犧 牲壞氧樹脂的其它性質。特別值得注意的是，許多添加劑 會降低該樹脂之玻螭轉換溫度(Tg)，此將大大減低該樹脂用 於電機工程應用之實用性。此亦會因黏度增加及/或造成團 水物屯成’然後難以被分散而妨礙該樹脂的加工能力。因 此’在技藝中仍然需要找出其它用來增韌熱固性環氧樹脂 4 201002778 之工具及方法。 I：發明内容3 發明概要 因此，在一個觀點中，本發明提供一種環氧樹脂組成 物，其包含一環氧樹脂及一有效量具有一級羥基官能性之 液體或結晶線性共聚酯。 在另一個觀點中，本發明提供一種製備環氧樹脂組成 物的方法，其包括將一有效量具有一級羥基官能性之液體 或結晶線性共聚酯併入環氧樹脂中。 【實施方式3 較佳實施例之詳細說明 本發明之組成物顯示出改良當硬化時的衝擊強度（該 性質更口語地指為“韌度”），如與沒有本發明的增韌劑之相 ' 同環氧組成物比較。此所謂的增韌劑為一種有效量具有一 級羥基官能性的液體或結晶線性共聚酯，其併入該預硬化 的調配物中在該調配物硬化後產生第二相晶疇。 * 由熟諳者已知之特別合適的環氧樹脂以多官能基的 醇、酚、環脂族羧酸、芳香族胺或胺基酚與表氯醇之反應 產物為主。幾個非為限制的具體實例包括例如雙酚A二縮水 甘油醚、雙盼F二縮水甘油_、間苯二紛二縮水甘油醚及對 -胺基酚的三縮水甘油基醚。由熟諳者已知之其它合適的環 氧樹脂包括表氣醇與鄰-曱酚及各別的酚酚醛清漆之反應 產物。亦可使用二或更多種環氧樹脂之混合物。 本發明之關鍵特徵為在硬化前將一有效量至少一種經 5 201002778 選擇具有一級羥基官能性的結晶或液體線性共聚酯併入該 環氧樹脂。在某些非為限制的具體實例中，此線性共聚酯 可描述如為具有Tg(根據德國標準化協會（German Institute 〇f Standardization)-“DIN”-53765 測量）範圍從約-20°C 至約 ~60°C。再者，在非為限制的具體實例中’該結晶線性共聚 _可定義為具有熔融黏度範圍從約0.5至約15巴斯卡-秒（巴 -杪)(如根據德國標準化協會的DIN EN ISO 3219: 1993，在 8〇°C下使用平行板方法來測量）；或使用相同方法如在130 °C下測量，其範圍從約0.3至約4巴-秒。該液體線性共聚酯 通常具有熔融黏度範圍從約2至約11巴斯卡-秒（巴-秒），如 根據德國標準化協會的DINENIS0 3219 : 1993 ’在80°C下 使用平行板方法測量。再者，該結晶線性共聚酯的特徵可 為其^(根據DIN 53765測量）從約3〇°C及約150°C ;在其它 非為限制的具體實例中，從約40°C至約120°C ;及在又其它 非為限制的具體實例中，從約50°C至約l〇〇°C。 在某些非為限制的具體實例中，該線性共聚酯可具有 羥基數目（毫克的KOH/克’如根據DIN 53240-2測量)從約15 至約50。該羥基數目從約18至約40較佳。該線性共聚酯之 官能性範圍可從2至8，從2至4更佳及2最佳。如於上述提 到，此為一級羥基官能性。 合適於製造在本發明中有用的線性共聚酯之方法可例 如在G.歐泰爾（〇ertel)的衮蜃差严鑀葙手滞（第2版，漢蛇 (Hanser)出版商）之描述中找到。在非為限制的具體實例 中，這些包括藉由線性二羧酸與線性二羥基化合物之縮聚 6 201002778 作用所製造的線性共聚酯。其它可能的製備途徑可包括線 性二羧酸氣化物與線性二羥基化合物之反應，及使用線性 二羥基化合物與該線性二羧酸的酯之轉酯基作用。 在這些製備方法中，線性二羧酸與線性二羥基化合物 之縮聚作用特別方便。例如，可使用合適的線性二叛酸， 及在非為限制的具體實例中，其包括在伸烷基中具有2至20 個碳原子（約6至約15個碳原子較佳）的線性脂肪族二羧酸。 這些線性二酸與線性二羥基化合物（具有從約2至約20個碳 原子的線性雙醇較佳，具有從約6至約15個碳原子的雙醇較 佳）反應。該二酸實質上無任何乙烯不飽和基團（即，碳碳雙 鍵)較佳。這些酸包括例如脂肪族二羧酸，諸如戊二酸、琥 珀酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一 烷二酸、十二烷二酸；及環脂肪族二羧酸，諸如1,3-及1,4-環己烷二羧酸；及其組合。通常來說，芳香族二羧酸不合 適於使用在本發明中，因為對具有當量至少約1,000的那些 來說，其熔點太高，高於約180°C。 在本發明中有用的二及多官能基醇之實施例有乙二 醇、二伸乙甘醇、三甘醇、丙二醇、二丙二醇、1,3-丙二醇、 1,2-丁 二醇、1,4-丁 二醇、1,6-己二醇、1,9-壬二醇、1,10-癸二醇、1,12-十二烷二醇、新戊二醇及其混合物。 藉由線性二羧酸與線性二羥基化合物之縮聚作用所製 備的聚酯從二酸及二醇製得較佳，如此該酸加醇之重覆單 元總共具有至少約9個碳原子；及總共從約10至約30個碳原 子更佳。 201002778 用來製得該二酸/二醇線性共聚酯之製備方法已由技 藝人士熟知。此可商業購得的共聚酯之實施例有由愛逢尼 克工業（Evonik Industries)以戴那扣（DYNACOLL)TM 7381之 商品名出售之具有分子量約3500及Tm為65°C的線性共聚 酯；及其它相關產物，諸如描述在發表名稱為“戴那扣 7000，可濕氣硬化的熱熔融黏著劑及密封膠用之構建塊系 統”之工藝傳單中。較佳的產物有戴那扣tm 72〇〇及7300系 列。來自其它供應者的類似化合物亦對本發明有用。 可合適地使用具有至少2個羥基的醇來進行包括聚酯 與醇之轉酯基作用的製備方法。較佳的醇具有2至4個羥 基。用來製造此聚合物的方法已在技藝中熟知。參見例如， G.歐泰爾的衮蜃差f鑀藉手眾（第2版，漢蛇出版商）。 在某些非為限制的具體實例中，在本發明中有用的線 性共聚酯可與一或多種安定劑結合。此可包括防止或減低 水解的產物。此等產物的實施例有可從萊因化學萊瑙有限 公司（Rhein Chemie Rheinau GMBH)購得之史大巴坡 (STABAPOL)tm添加劑。 該線性共聚酯以一有效量使用在本發明中，即，其量 可產生較堅韌的環氧樹脂熱固性（即，後硬化）組成物。根據 ASTM D-5045(標題“塑膠材料的平面應變斷裂韌度及應變 貪b量釋放速率之標準測試方法”），藉由在最後硬化材料上 測6式衝擊強度來測量此增勃效應。在某些想要的具體實例 中，此量亦在產生想要的增韌所需要之最小量處或接近最 小1處，同時其不會干擾該樹脂的任何其它性質至不能接 201002778 受或不想要的程度。 通常來說，該線性共聚酯之量範圍因此可從1至約50體 積百分比（以該總組成物的體積為準）’但是’在液體塗佈組 成物之實例中，其不包括任何溶劑的體積。在許多較佳但 是非為限制的具體實例中，該線性共聚酯之量範圍可從2至 約40體積百分比。更佳的是，該線性共聚酯的量範圍可從2 至約30體積百分比。最佳的是，該線性共聚酯之量範圍可 從2至約20體積百分比。甚至更佳的是，該線性共聚物之量 範圍可從約1至約10體積百分比。在某些非為限制的具體實 例中，已經發現僅約6體積百分比的量可在增韌該環氧樹脂 熱固性組成物上有效。 本發明之環氧樹脂組成物亦可包括添加劑，諸如觸 媒、其它硬化劑、其它樹脂；充填劑，諸如^夕礦石、重晶 石、雲母、長石、滑石及碳酸鈣；染料、顏料，諸如二氧 化鈦、碳黑、氧化鐵類、氧化鉻及有機顏料；觸變劑、光 起始劑、潛含型光起始劑、潛含型觸媒、抑制劑、流動改 質劑、加速劑、乾燥添加劑、界面活性劑、黏附力促進劑、 流動性控制劑、安定劑、增動劑、阻燃劑、輔助加工的稀 釋劑、其它增韌劑、加速劑；及該組成物之製造、應用或 適當性能所需要的任何其它物質。通常來說，該選擇性添 加劑的量可從0至約70體積百分比。熟習該項技術者將察覺 這些添加劑的效應及選擇，其適當使用已在熟諳操作技藝 之人士中有充分考慮。 本發明的線性共聚酯可以該線性共聚酯在與硬化劑接 9 201002778 觸前已良好分散或溶解在環氧樹脂中之此方式引進調配物 中。該線性共聚酯亦可加入至已經包含多種其它添加劑的 環氧樹脂配料或系統。已發現有數種併入線性共聚酯的方 法，其包括例如在周溫或低於或等於約70°C的其它溫度 下，於充分攪動已熔化的共聚酯下傾注或注入該環氧樹脂 (含或不含其它添加劑）中。然後，可一起加熱該環氧樹脂與 線性共聚酯直到獲得一均勻的混合物。在此時，然後可冷 卻該混合物同時持續攪動。在另一個且非為限制的具體實 例中，亦可僅在該環氧樹脂與該硬化劑接觸前，將該線性 共聚酯直接注入該環氧樹脂混合頭中，因此，幾乎同時將 其分散或溶解在包含該環氧樹脂與其它組分之摻合物中。 依該初始環氧樹脂的黏性而定，包含該線性共聚酯之 組成物可具有對實際使用來說太高的黏度。在此例子中， 可實行地包括改質劑，諸如在環氧樹脂技藝中熟知的環氧 樹脂反應性稀釋劑。這樣做的時候，應該考慮的是將反應 性環氧樹脂稀釋劑引進最後硬化的熱固性環氧樹脂中可造 成不想要的效應，諸如不想要的Tg降低。 一旦已經合適地結合全部組分（除了硬化劑外）以形成 一環氧樹脂組成物時，該組成物可經硬化（即，藉由讓該環 氧樹脂組成物與硬化劑接觸而硬化）以形成最後環氧熱固 性樹脂組成物。該硬化劑可選自於任何通常由熟習該項技 術者已知如為可有效打開環氧環以便能夠聚合及交聯者。 在本發明中有用的硬化劑之實施例包括酐、含盼化合物、 胺、其組合及其類似物。可在EP-A 2 373 440(其全文以參 10 201002778 考之方式併入本文）中找到於本發明中有用的其它硬化 劑。典型來說’環氣樹脂對硬化劑之當量比率範圍可從約 5 : 1至約1 : 1 ’但是亦可於特定應用中使用在此範圍外變 化的比率。 在某些特別但是非為限制的具體實例中，.最後的環氧 樹脂熱固性組成物可具有改良的韌度（如由於此上述討論 的ASTM D-5045所定義）。在某些非為限制的具體實例中， 此韌度可改良至少約25百分比；在其它非為限制的具體實 ' 例中，至少約35百分比；及在又其它非為限制的具體實例 中，甚至較大的百分比。 S根據ASTM D-5045測試時，本發明之組成物顯示出 在初度上增加至少25百分比，如與不包含具有一級經基官 能性的液體或結晶線性共聚酯之同等組成物比較；及在韌 度上顯示出增加至少35百分比較佳。 與缺乏本發明之線性共聚酯的相同調配物比較，在某 些非為限制的具體實例中，Tg的降低量範圍可從; ' 及在其它非為限制的具體實例中，從〇。(：至15。(：；根據astm D 3418-03，聚合物的轉換溫度、熔化焓及結晶度使用示差 掃描卡計及標準測試方法測試。 本發明之環氧樹脂熱固性組成物可在多種應用中有 用。此等應用包括(但不限於)模塑組成物、塗佈物(諸如粉 末、液體及粉末/液體塗佈物）、電機工程應用（諸如陶器製 造化合物）、結構複合材料及建造及機械應用（諸如黏著劑、 狀層壓板)及其類似物。 11 201002778 於此上述的描述想要為共通且不想要包含本發明之全 部可能的具體實例。類似地，於此下列之實施例僅提供闡 明且不想要以任何方式定義或限制本發明。熟習該項技術 者將從本發明如於本文所揭示的專利說明書及/或實施之 考量中明瞭，而完整察覺出在該申請專利範圍的範圍内之 其它具體實例。此其它具體實例可包括特定的環氧樹脂、 硬化劑及線性共聚酯之選擇；添加劑及輔助劑之選擇；混 合及反應條件、容器及進行方法；性能及選擇性；產物及 副產物之鑑定；及其類似物；且熟習該項技術者將了解此 些可在到此為止所附加的申請專利範圍之範圍内變化。 實施例 原料 D.E.RJM 383為一種以雙酚A為主的液體環氧樹脂，其 具有181克/當量的環氧化合物當量且可從道化學公司（Dow Chemical Company)購得。 六氫酞酸酐可從西格瑪-亞得富有限公司（Sigma-Aldrich Inc.)購得。 1,2-二胺基環己烷可從西格瑪-亞得富有限公司購得。 使用2-乙基-4-曱基咪唑作為硬化無水環氧調配物之觸 媒且其可從西格瑪-亞得富有限公司購得。 測試飾板之製備 在由“U”形、1/8英吋厚的鋁間隔器所組成之模具中製 得測試飾板，其中該間隔器位於二片都歐弗意爾 (DUOFOIL)™鋁間且壓緊在二片6”χ6”χ0·5”鋼板間。（都歐 12 201002778201002778 VI. Description of the Invention: [Technical Field of Invention] 3 Field of the Invention The present invention relates to a method of producing an epoxy thermosetting resin. More particularly, the present invention relates to a process for making a toughened epoxy thermoset resin using a linear polyester species having a primary hydroxyl functionality. BACKGROUND OF THE INVENTION Epoxy based compositions are well known and are thermoset materials which have been widely used in, for example, electrical engineering, automotive engineering, and construction applications. Among these applications are molding compositions, liquid and powder coatings, laminates, adhesives, pottery manufacturing compositions, and the like. Epoxy resin systems generally have very high hardness and stiffness, good adhesion and insulation, rosin protection and good thermal and chemical properties. However, the disadvantage of these systems is that their hardened products lack toughness. Along with the goal of improving this disadvantage, a wide variety of additives for the ring oxy-resin system have been described. For example, ΕΡ-Α 2 392 348 discloses an epoxy resin system comprising a particulate thermoplastic such as polysulfone, which is claimed to have improved toughness. ΕΡ-Α 2 373 440 describes an aromatic epoxy compound, an amine hardener, an aromatic thermoplastic oligomer comprising a reactive group (such as an amine terminal) or polyethersulfone, and also a high molecular weight emulsifier. Toughened epoxy resin mixture. U.S. Patent No. 7,329,711 discloses an epoxy composition comprising two specific polyarylene ether oximes and fillers and additives. These compositions have been claimed 3 201002778 with improved transparency and better or improved impact strength. Jin Min (10)) Y·Special application of polymer science journal, J〇urnal but C corpse o (ymer 5W (9) ce) (90 (l2) ' 3384-3389, 2003, John Wiley & Songs (John Wiley & Sons Inc.)) reveals a bisphenol A type epoxy resin that is toughened with 4 to 24 parts of aromatic polyester per 100 parts. Shin S. et al.'s pleading and semester office (78(14), 2464-2473 '2000 'John Willy and Songs) revealed the use of aromatic polyester to toughen bisphenol Α/Diaminodiphenyldecane epoxy system. The appointment of Lijima T. et al. (43 (3), 463-74, 199, John Willy and Songs) reveals a group of citrate or isophthalic acid. The aromatic polyester prepared by the reaction of an alkanediol is used to reduce the friability of the bisphenol hydrazine/diglycidyl ether epoxy resin hardened by fluorenyl hexahydrophthalic anhydride. Another method well known in the art is the incorporation of a rubbery substance into the epoxy system. An embodiment of this method involves incorporating a carboxyl terminated butyl propylene (CTBN) liquid rubber or a core shell rubber (CSR) into an epoxy system. Therefore, 'unfortunately, although some methods to improve the impact strength of thermosetting epoxy resins (ie, 'toughening,') are known, many methods do sacrifice other properties of the bad oxygen resin. Many additives reduce the glass transition temperature (Tg) of the resin, which greatly reduces the utility of the resin for electrical engineering applications. This will also increase the viscosity and/or cause the water to become 'and then difficult to be dispersed. This hinders the processing ability of the resin. Therefore, it is still necessary in the art to find other tools and methods for toughening the thermosetting epoxy resin 4 201002778. I: SUMMARY OF THE INVENTION Summary of the Invention Accordingly, in one aspect, the present invention provides An epoxy resin composition comprising an epoxy resin and an effective amount of a liquid or crystalline linear copolyester having a primary hydroxyl functionality. In another aspect, the present invention provides a method of preparing an epoxy resin composition, It comprises incorporating an effective amount of a liquid having a primary hydroxyl functionality or a crystalline linear copolyester into an epoxy resin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The composition of the present invention exhibits an improved impact strength when hardened (this property is more simply referred to as "toughness"), such as a phase with the toughening agent of the present invention. This so-called toughening agent is an effective amount of a liquid or crystalline linear copolyester having a primary hydroxyl functionality which is incorporated into the pre-cured formulation to produce a second phase domain after the formulation has hardened. Particularly suitable epoxy resins known to the skilled person are mainly reactive products of polyfunctional alcohols, phenols, cycloaliphatic carboxylic acids, aromatic amines or aminophenols with epichlorohydrin. Several non-limiting specificities Examples include, for example, bisphenol A diglycidyl ether, dip F diglycidyl, isophthalic diglycidyl ether, and triglycidyl ether of p-aminophenol. Other suitable epoxides known to those skilled in the art. The resin includes a reaction product of a surface alcohol and o-nonanol and a respective phenol novolak. A mixture of two or more epoxy resins may also be used. A key feature of the present invention is that an effective amount is at least one prior to hardening. Selected by 5 201002778 A crystalline or liquid linear copolyester having a primary hydroxyl functionality is incorporated into the epoxy resin. In certain non-limiting specific examples, this linear copolyester can be described as having a Tg (according to the German Institute for Standardization (German Institute) 〇f Standardization) - "DIN" - 53765 measurement) ranges from about -20 ° C to about ~ 60 ° C. Furthermore, in the non-limiting example, 'the crystalline linear copolymerization _ can be defined as having a melt viscosity range From about 0.5 to about 15 Baska-seconds (as measured according to DIN EN ISO 3219: 1993 of the German Standards Institute, using the parallel plate method at 8 ° C); or using the same method as in Measured at 130 ° C, which ranges from about 0.3 to about 4 bar-seconds. The liquid linear copolyester typically has a melt viscosity ranging from about 2 to about 11 Baska-seconds (bar-seconds), as standardized according to Germany. Association of DINENIS0 3219: 1993 'Measured at 80 ° C using the parallel plate method. Furthermore, the crystalline linear copolyester may be characterized by its (as measured according to DIN 53765) from about 3 ° C and about 150 ° C; in other non-limiting embodiments, from about 40 ° C to about 120 ° C; and in still other non-limiting examples, from about 50 ° C to about 10 ° C. In certain non-limiting embodiments, the linear copolyester may have a number of hydroxyl groups (mg of KOH per gram 'as measured according to DIN 53240-2) from about 15 to about 50. Preferably, the number of hydroxyl groups is from about 18 to about 40. The functionality of the linear copolyester can range from 2 to 8, more preferably from 2 to 4 and 2 is optimal. As mentioned above, this is a primary hydroxyl functionality. A method suitable for the manufacture of a linear copolyester useful in the present invention can be, for example, at G. Otel (衮蜃ertel), which is a stagnation (2nd edition, Hanser publisher). Found in the description. In a non-limiting embodiment, these include linear copolyesters produced by the action of polycondensation of a linear dicarboxylic acid with a linear dihydroxy compound 6 201002778. Other possible routes of preparation may include the reaction of a linear dicarboxylic acid vapor with a linear dihydroxy compound and the transesterification of a linear dihydroxy compound with an ester of the linear dicarboxylic acid. In these preparation methods, the polycondensation of a linear dicarboxylic acid and a linear dihydroxy compound is particularly convenient. For example, a suitable linear ditoponic acid can be used, and in a non-limiting embodiment, it includes a linear fat having from 2 to 20 carbon atoms (preferably from about 6 to about 15 carbon atoms) in the alkylene group. Group dicarboxylic acid. These linear diacids are reacted with a linear dihydroxy compound (preferably a linear diol having from about 2 to about 20 carbon atoms, preferably having a diol having from about 6 to about 15 carbon atoms). The diacid is substantially free of any ethylenically unsaturated groups (i.e., carbon-carbon double bonds). These acids include, for example, aliphatic dicarboxylic acids such as glutaric acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; And cycloaliphatic dicarboxylic acids such as 1,3- and 1,4-cyclohexanedicarboxylic acids; and combinations thereof. In general, aromatic dicarboxylic acids are not suitable for use in the present invention because for those having an equivalent weight of at least about 1,000, the melting point is too high, above about 180 °C. Examples of the di- and polyfunctional alcohols useful in the present invention are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 1 4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-nonanediol, 1,12-dodecanediol, neopentyl glycol, and mixtures thereof. The polyester prepared by the polycondensation of a linear dicarboxylic acid and a linear dihydroxy compound is preferably prepared from a diacid and a diol, such that the acid-alcoholic repeating unit has a total of at least about 9 carbon atoms; More preferably from about 10 to about 30 carbon atoms. 201002778 A process for the preparation of the diacid/diol linear copolyester is well known to those skilled in the art. An example of such a commercially available copolyester is a linear copolymer having a molecular weight of about 3,500 and a Tm of 65 ° C sold under the trade name DYNACOLLTM 7381 by Evonik Industries. Ester; and other related products, such as those described in the process leaflet entitled "Dana buckle 7000, moisture-curable hot melt adhesive and building block system for sealants". Preferred products are the Tna 72 and 7300 series. Similar compounds from other suppliers are also useful in the present invention. A preparation method comprising a transesterification of a polyester with an alcohol can be suitably carried out using an alcohol having at least 2 hydroxyl groups. Preferred alcohols have from 2 to 4 hydroxyl groups. Methods for making such polymers are well known in the art. See, for example, G. Otell's 衮蜃 鑀 鑀 ( 第 (2nd edition, Han snake publisher). In certain non-limiting embodiments, the linear copolyesters useful in the present invention can be combined with one or more stabilizers. This may include preventing or reducing the product of hydrolysis. Examples of such products are the STABAPOL tm additive available from Rhein Chemie Rheinau GMBH. The linear copolyester is used in the present invention in an effective amount, i.e., in an amount that produces a tougher epoxy thermoset (i.e., post harden) composition. According to ASTM D-5045 (Title "Standard Test Method for Plane Strain Fracture Toughness and Strain Rate of Plastic Material"), this increase is measured by measuring the impact strength of Type 6 on the final hardened material. In some specific embodiments desired, this amount is also at or near the minimum required to produce the desired toughening, while it does not interfere with any other properties of the resin until it is unable to accept 201002778. The extent of the need. Generally, the amount of linear copolyester can therefore range from 1 to about 50 volume percent (based on the volume of the total composition) 'but' in the example of a liquid coating composition, which does not include any solvent volume of. In many preferred, but not limiting, specific embodiments, the amount of linear copolyester can range from 2 to about 40 volume percent. More preferably, the linear copolyester can range from 2 to about 30 volume percent. Most preferably, the amount of linear copolyester can range from 2 to about 20 volume percent. Even more preferably, the linear copolymer can range from about 1 to about 10 volume percent. In certain non-limiting specific examples, it has been found that only about 6 volume percent can be effective in toughening the epoxy thermoset composition. The epoxy resin composition of the present invention may also include additives such as a catalyst, other hardeners, other resins; fillers such as eucalyptus, barite, mica, feldspar, talc, and calcium carbonate; dyes, pigments, such as Titanium dioxide, carbon black, iron oxides, chromium oxide and organic pigments; thixotropic agents, photoinitiators, latent photoinitiators, latent catalysts, inhibitors, flow modifiers, accelerators, drying Additives, surfactants, adhesion promoters, flow control agents, stabilizers, extenders, flame retardants, auxiliary processing diluents, other toughening agents, accelerators; and the manufacture, application or Any other substance required for proper performance. Generally, the amount of the selective additive can range from 0 to about 70 volume percent. Those skilled in the art will be aware of the effects and choices of these additives, and their proper use is well considered among those skilled in the art of operation. The linear copolyester of the present invention can be incorporated into the formulation in such a manner that the linear copolyester is well dispersed or dissolved in the epoxy resin prior to contact with the hardener. The linear copolyester can also be added to epoxy resin formulations or systems that already contain a variety of other additives. Several methods of incorporating linear copolyesters have been discovered which include, for example, pouring or injecting the epoxy resin under a sufficient agitation of the molten copolyester at ambient temperature or other temperatures less than or equal to about 70 °C. (with or without other additives). The epoxy resin can then be heated together with the linear copolyester until a homogeneous mixture is obtained. At this point, the mixture can then be cooled while continuing to agitate. In another and non-limiting embodiment, the linear copolyester may be directly injected into the epoxy mixing head only before the epoxy resin is contacted with the hardener, thereby dispersing it almost simultaneously. Or dissolved in a blend comprising the epoxy resin and other components. Depending on the viscosity of the initial epoxy resin, the composition comprising the linear copolyester may have a viscosity that is too high for practical use. In this example, modifiers such as epoxy reactive diluents well known in the art of epoxy resins are exemplarily included. In doing so, it should be considered that the introduction of reactive epoxy resin diluent into the final hardened thermosetting epoxy resin can cause undesirable effects such as unwanted Tg reduction. Once all of the components (other than the hardener) have been suitably combined to form an epoxy resin composition, the composition can be cured (ie, hardened by contacting the epoxy resin composition with the hardener). A final epoxy thermosetting resin composition is formed. The hardener may be selected from any of those conventionally known to those skilled in the art as being effective to open the epoxy ring to enable polymerization and crosslinking. Examples of hardeners useful in the present invention include anhydrides, trypan compounds, amines, combinations thereof, and the like. Other hardeners useful in the present invention can be found in EP-A 2 373 440, the entire disclosure of which is incorporated herein by reference. Typically, the equivalent ratio of the cycloolefin resin to the hardener may range from about 5:1 to about 1:1, but the ratio outside the range may also be used in a particular application. In certain specific, but not limiting, specific examples, the final epoxy thermoset composition can have improved toughness (as defined by ASTM D-5045 discussed above). In certain non-limiting embodiments, the tenacity may be modified by at least about 25 percent; in other non-limiting specific embodiments, at least about 35 percent; and in yet other non-limiting embodiments, Even a larger percentage. When tested according to ASTM D-5045, the compositions of the present invention exhibit an increase of at least 25 percent initially, as compared to equivalent compositions that do not comprise a liquid or crystalline linear copolyester having a primary radical functionality; It is preferred to increase the toughness by at least 35 percent. In contrast to the same formulations lacking the linear copolyesters of the present invention, in certain non-limiting specific examples, the amount of Tg reduction can range from; and in other non-limiting specific examples, from hydrazine. (: to 15. (:; According to astm D 3418-03, the conversion temperature, melting enthalpy and crystallinity of the polymer are tested using a differential scanning card meter and a standard test method. The epoxy thermosetting composition of the present invention can be used in various applications. Useful in such applications, including but not limited to molding compositions, coatings (such as powders, liquids, and powder/liquid coatings), electrical engineering applications (such as pottery manufacturing compounds), structural composites, and construction and Mechanical applications (such as adhesives, laminates) and the like. 11 201002778 The above description is intended to be common and not intended to encompass all possible embodiments of the invention. Similarly, the following embodiments are only The invention is set forth and is not intended to be in any way of limitation or limitation of the scope of the invention. Other specific examples within the scope. Other specific examples may include selection of specific epoxy resins, hardeners, and linear copolyesters; additives and supplements Selection of agents; mixing and reaction conditions, containers and methods of conduct; performance and selectivity; identification of products and by-products; and their analogues; and those skilled in the art will be aware of such applications that may be added to date Examples vary within the scope of the patent. Example Materials DERJM 383 is a liquid epoxide based on bisphenol A having an epoxy equivalent of 181 grams per equivalent and is commercially available from Dow Chemical Company. Hexahydrophthalic anhydride is commercially available from Sigma-Aldrich Inc. 1,2-diaminocyclohexane is commercially available from Sigma-Afford Co., Ltd. Ethyl-4-mercaptoimidazole is used as a catalyst for hardening anhydrous epoxy formulations and is commercially available from Sigma-Adelphi Co., Ltd. The test plaques are prepared in a "U" shape, 1/8 inch thick. A test panel is produced in a mold consisting of an aluminum spacer, wherein the spacer is located between two sheets of DUOFOILTM aluminum and is pressed between two sheets of 6"χ6"χ0·5" steel sheets. (Duo 12 201002778
间隔⑽傾注調配物。根據在調配物部分中所提供的硬化 計劃表來硬化該調配物。在加熱計劃表結束時，在從模具 弗意爾™為勾而得電子設備(Gould Electronics)之商 名）。遵循該間隔器的内部尺寸，❹—透明以 移出該硬化的飾板前將飾板冷卻至4〇t。The formulation was poured at intervals (10). The formulation is hardened according to the hardening schedule provided in the formulation section. At the end of the heating schedule, the name of the electronic device (Gould Electronics) is obtained from the mold. Following the internal dimensions of the spacer, ❹-transparently cools the fascia to 4 〇t before removing the hardened plaque.
比較例A 在此比較例中，如下製備一經六氫酞酸酐硬化的環氧 熱固性樹脂之對照飾板： 在250毫升圓底燒瓶中，於7〇。〇下一起混合D e r, 383(56.0克，〇·3〇94當量）與六氫酞酸酐(42 9克，〇 2787當 量），直到該混合物變均勻。將2_乙基_4_曱基咪唑觸媒（1克) % s進入δ亥調配物中。將該調配物傾入4盘司的玻璃廣口瓶 中，然後在2500rpm下離心3分鐘。在離心後，將該調配物 傾入模具中及在100。(3下硬化約丨小時，然後在195乞下2小時。 實施例1-5 在這些實施例中，如下製備一經六氫酞酸酐硬化包含 線性共聚酯的環氧熱固性樹脂之飾板： 結合已經預先加熱至6〇。〇的D.E.R. 383(53.2克，0.2939 菖里）與線性共聚醋（5克）’然後使用加熱燈加熱同在報磨機 13 201002778 上混合直到獲得均勻的混合物。將此混合物之溫度調整至 7〇°C。加入六氫酞酸酐(40.8克，0.2646當量）且授拌直到該 混合物均勻。加入2-乙基-4-甲基咪唑觸媒（1克）。將該調配 物傾入4盎司的玻璃廣口瓶中，然後在2500l_pm下離心3分 鐘。在離心後，將該調配物傾入模具中以形成飾板及在1〇(rc 下硬化約1小時’然後在195°C下2小時。根據ASTM D-5045 來測試飾板。結果顯示在表1中。 表1-以六氫酞酸酐硬化的D.E.R. 383 實施例 線性共聚酯 Klc*(百萬巴-公尺05) 韋刃度增加的大約°/。，相料协斜日3 比較例A 無 0.6356 實施例1 5%戴那扣7381(結晶> U048 74 實施例2 5%戴那扣7380(結晶） 1-2410 95 實施例3 5%戴那扣7230(液體） 0.8007 26 實施例4 5%戴那扣7250(液體> 1.1740 85 實施例5 5%戴那扣7111(非晶相> 0.6022 0 *使用ASTM D-5045測量；較高的KIc值指示出較堅韌的系統。Comparative Example A In this comparative example, a control plaque of a hexahydrophthalic anhydride-hardened epoxy thermosetting resin was prepared as follows: in a 250 ml round bottom flask, at 7 Torr. Together, er, 383 (56.0 g, 〇·3 〇 94 eq.) and hexahydrophthalic anhydride (42 9 g, 〇 2787 metric) were mixed together until the mixture became homogeneous. The 2_ethyl_4_mercaptoimidazole catalyst (1 g) % s was introduced into the delta formulation. The formulation was poured into a four-panel glass jar and centrifuged at 2500 rpm for 3 minutes. After centrifugation, the formulation was poured into a mold and at 100. (3 under hardening for about 丨 hours, then 2 hours at 195 Torr.) Examples 1-5 In these examples, a plaque of an epoxy thermosetting resin comprising a linear copolyester was cured by hexahydrophthalic anhydride: It has been preheated to 6 〇. DER 383 (53.2 g, 0.2939 菖) and linear copolymer vinegar (5 g) are then mixed with a heating lamp and mixed with the grinder 13 201002778 until a homogeneous mixture is obtained. The temperature of the mixture was adjusted to 7 ° C. Hexahydrophthalic anhydride (40.8 g, 0.2646 equivalents) was added and the mixture was stirred until the mixture was homogeneous. 2-ethyl-4-methylimidazole catalyst (1 g) was added. The formulation was poured into a 4 ounce glass jar and then centrifuged at 2500 pm for 3 minutes. After centrifugation, the formulation was poured into a mold to form a plaque and hardened at 1 〇 (rc for about 1 hour). 2 hours at 195 ° C. The plaques were tested according to ASTM D-5045. The results are shown in Table 1. Table 1 - DER 383 hardened with hexahydrophthalic anhydride Example Linear copolyester Klc* (million bars - Metric 05) Increased edge degree increases by approximately °/., phase contrast X 3 comparison A No 0.6356 Example 1 5% Dai Na buckle 7381 (crystallization > U048 74 Example 2 5% Dai Na 7380 (crystal) 1-2410 95 Example 3 5% Dai Na buckle 7230 (liquid) 0.8007 26 Example 4 5% wear buckle 7250 (liquid > 1.1740 85 Example 5 5% wear buckle 7111 (amorphous phase > 0.6022 0 * measured using ASTM D-5045; a higher kAc value indicates a tougher system.
比較例B 在此比較例中，如下製備一經1，2-二胺基環己烷硬化的 環氧熱固性樹脂之對照飾板： 在250毫升圓底燒瓶中，於70°C下一起混合D.E.R. 383(86.4克，0.4773當量）與1,2-二胺基環己烧（13.6克， 0.4772當量），直到該混合物變均勻。將該調配物傾入4盎司 的玻璃廣口瓶中’然後在15〇〇rpm下離心3分鐘；或在黏性 顯示出相當高的實例中，在2500rpm下離心該樣品5分鐘。 在離心後’將該調配物傾入模具中及在l〇〇〇C下硬化約1小 時’然後在195°C下2小時。 實施例6-9 在這些實施例中，如下融合一經1,2-二胺環己烷硬化包 14 201002778 含線性共聚酯的環氧熱固性樹脂之飾板： 結合已經預先加熱至60°C的D.E.R. 383(82.1克，0.4536 當量）與線性共聚酯（5克），然後使用加熱燈加熱同時在輥磨 機上混合直到獲得均句的混合物。將溫度調整至70°C。加 入1，2-二胺基環己烷（12_9克，0.4526當量）並攪拌直到混合 物均勻。將該調配物傾入4盎司的玻璃廣口瓶中，然後在 25OOrpm下離心3分鐘。在離心後，將該調配物傾入模具中 且如在比較例A及實施例1-5中般製備、硬化及測試飾板。 測試結果顯示在表2中。 表2-以1,2-二胺環己烷硬化的D.E.R. 383 實施例 線性共聚酯 Klc*(百萬巴-公尺°_5) 韌度增加的大約％，相對於對照 比較例B 無 0.6005 - 實施例6 5%戴那扣738〗(結晶） 0.8066 34 實施例7 5%戴那扣7380(結晶} 0.8494 41 實施例8 5%戴那扣7390(結晶） 0.9290 55 實施例9 5%戴那扣7250(液體） 0.7738 29 *使用ASTM D-5045測量；較高的Klc值指示出較堅韌的系統。 I：圖式簡單說明3 (無） 【主要元件符號說明】 (無） 15Comparative Example B In this comparative example, a control plaque of a 1,2-diaminocyclohexane-cured epoxy thermosetting resin was prepared as follows: DER 383 was mixed together at 70 ° C in a 250 ml round bottom flask. (86.4 g, 0.4773 equivalent) and 1,2-diaminocyclohexane (13.6 g, 0.4772 equivalent) until the mixture became homogeneous. The formulation was poured into a 4 ounce glass jar' and then centrifuged at 15 rpm for 3 minutes; or in the case where the viscosity showed a relatively high, the sample was centrifuged at 2500 rpm for 5 minutes. After centrifugation, the formulation was poured into a mold and hardened at 1 ° C for about 1 hour and then at 195 ° C for 2 hours. EXAMPLES 6-9 In these examples, a 1,2-diamine cyclohexane hardening package was fused as follows: 14 201002778 A plaque of an epoxy thermosetting resin containing a linear copolyester: the combination has been previously heated to 60 ° C DER 383 (82.1 g, 0.4536 eq.) and linear copolyester (5 g) were then heated using a heat lamp while mixing on a roller mill until a homogeneous mixture was obtained. The temperature was adjusted to 70 °C. 1,2-Diaminocyclohexane (12-9 g, 0.4526 equivalent) was added and stirred until the mixture was homogeneous. The formulation was poured into a 4 ounce glass jar and centrifuged for 3 minutes at 25OO rpm. After centrifugation, the formulation was poured into a mold and the plaques were prepared, hardened and tested as in Comparative Example A and Examples 1-5. The test results are shown in Table 2. Table 2 - DER 383 hardened with 1,2-diamine cyclohexane Example Linear copolyester Klc* (million bar-meter °_5) Approximate increase in toughness, compared to control Comparative Example B No. 0.6005 - Example 6 5% wear buckle 738 (crystallization) 0.8066 34 Example 7 5% wear buckle 7380 (crystal) 0.8494 41 Example 8 5% wear buckle 7390 (crystal) 0.9290 55 Example 9 5% wear That buckle 7250 (liquid) 0.7738 29 *Measured using ASTM D-5045; higher Klc value indicates a tougher system I: Simple description of the diagram 3 (none) [Main component symbol description] (none) 15