200837138 九、發明說明： 【發明所屬之技術領域】 本發明係有關輻射可硬化組成物，特別可用於棬料_ 覆。 【先前技術】 捲料塗覆機塗覆各種類型各種型式的金屬捲料。捲# 塗覆係於構製組合前以高速塗覆金屬的連續及高度自動& 製程。該製程係由下列數個步驟所組成。金屬捲料經過_ 捲且金屬捲料的頂面和底面以機械及化學方式清潔來去P余 油、油脂及污物。於清潔後，可施用化學前處理至該片料， 來提升防蝕性及塗料黏著性。然後，條料直接移動至乾燥 烤爐，隨後進入塗覆單元。於已經施用塗料後，條料再度 移動入乾燥烤爐內，隨後經冷卻且再度捲取供出貨。經過 預先塗覆之片料係用於金屬加工業。因此，多個金屬物件 於使用時或組裝時未經塗覆或塗塗料，反而首先係呈捲料 的平坦備料供應，然後成型、切割、以及組裝成爲期望的 物件。結果，於幾乎全部情況下的關鍵標準係可將經塗覆 的條料後成型或彎曲。後成型通常係藉高速加工設備進 行’其中金屬彎曲極爲苛刻。金屬必須爲可撓性才可進行 後成型或彎曲而未造成斷裂而仍然維持黏著。整個系統表 示金屬於某些情況下，保護性鋅層、前處理層、及塗料層 也可達.到高度防蝕性。例如化學耐性及應變耐性等基本性 質維持相當重要，而且用於某些用途，也要求例如濕度測 試耐性及滅菌測試耐性等性質。 200837138 輻射可硬化系統極爲適合捲料塗覆；基材平坦，線性 速度高’可解決環保議題，例如溶劑的使用議題，需要的 能量及地板空間比其它塗覆技術所需的硬化烤爐更少。 但至目前爲止，輻射可硬化塗覆組成物特別爲紫外光 調配物未曾廣用於捲繞塗覆用途。典型之紫外光調配物包 含（甲基）丙烯酸化寡聚物及反應性稀釋劑，當硬化時，形 成具有諸如耐化學性、耐刮擦性、及表面硬度等良好性質 之高度交聯塗覆層。此種高度交聯密度也與薄膜之有限可 撓性和收縮性有關，因而限制薄膜的黏著於金屬基材上。 當試圖找出此等苛刻要求的解決之道時，經常受限於需降 低分子量來達成合理的黏度，以及於交聯間需要實質分子 量來達成所需硬化塗層之可能性。 用於捲料塗覆用途，此處高度可撓性爲後成型操作所 必須，典型的紫外光調配物並不適合。US 2002/0132059 A1 說明使用可光聚合塗覆組成物用於經過盤捲之金屬片料之 塗層之原理。於施用塗層至此處所述經盤捲之金屬片料之 方法中，金屬片料首先經清潔，然後經前處理，隨後施用 塗覆組成物。 於該專利申請案並未揭示特定之可光聚合組成物。但 並非全部包含不飽和寡聚物之可光聚合塗覆組成物當用於 捲料塗覆製程時皆可獲得滿意的結果。 發明人今日發現極爲適合用於可光聚合組成物之新穎 輻射可硬化寡聚物。 200837138 【發明內容】 因此本發明係有關一種輻射可硬化組成物，包含至少 一種具有玻璃轉換溫度Tc及/或熔點Tm低於3 〇 〇c之輻射可 硬化募聚物，該寡聚物係經由一種或多種具有玻璃轉換溫 度Tc及/或熔點Tm低於3(rc之羧基官能基聚酯（a)反應獲 得，且該聚酯係得自於就酸成分總量而言，係由7 5莫耳％ 至100莫耳％至少一種含4個至14個碳原子之直鏈飽和脂肪 族二殘酸’及任選地由〇至25莫耳％至少另一種脂肪族、環 月曰族及方香族多殘酸；以及就醇成分之總量而言，由2 5莫 耳％至100莫耳％至少一種分支鏈脂肪族二醇，以及任選地 由0至75莫耳％至少另一種脂肪族或環脂族多元醇，與一種 或多種（甲基）丙烯酸化一環氧化物（bl)及/或一種或多種多 環氧化物（b2)及一種或多種α，Θ -不飽和羧酸反應獲得。 【實施方式】 本發明中，須了解「（甲基）丙烯醯基」一詞係涵蓋丙 烯醯基及甲基丙烯醯基化合物或衍生物及其混合物。 輻射可硬化寡聚物通常具有數目平均分子量至少 600，較佳至少800，及更佳至少1000。通常輻射可硬化寡 聚物具有數目平均分子量不超過10000,較佳不超過7000, 及最佳不超過5000。 輻射可硬化寡聚物根據ASTM D3418，以加熱梯度爲每 分種20°C，藉差動掃描量熱術測得玻璃轉換溫度Τ。及/或 溶點Tm係低於20°C。輻射可硬化寡聚物更佳具有玻璃轉換 溫度T。及/或熔點Tm係低於0°C。 200837138 本發明使用之輻射可硬化寡聚物係得自羧基官能基聚 酯。羧基官能基聚酯一詞表示包含自由態通常爲端末 -COOH(竣基）基團之聚酯。竣基官會g基聚酯通常具有酸値爲 10至340毫克K0H/克（mgKQH/g)。本發明使用之聚酯較佳 具有酸値至少爲20，更佳至少爲25，及最佳至少爲30。本 發明使用之聚酯較佳具有酸値不超過250 mg K〇H/g，更佳 不超過190 mg K〇H/g，且最佳不超過80 mg KOH/g。 羧基官能基聚酯也可經由羥基官能基聚酯與環狀酐反 應獲得。 羥基官能基聚酯表示於本發明中，聚酯有自由態羥基 且通常爲端末羥基，通常具有羥基値爲10至340 mg KOH/g 〇本發明使用之羥基官能基聚酯較佳具有羥基價爲 25 至 250 mg K〇H/g，更佳爲 30 至 190 mg K〇H/g。 本發明使用之羧基官能基聚酯及/或羥基官能基聚酯 係由包含一種或多種多元酸之酸成分與包含一種或多種多 元醇之醇成分反應獲得。且該聚酯係得自於就酸成分總量 而言，係由75莫耳％至100莫耳％至少一種含4個至14個 碳原子之直鏈飽和脂肪族二羧酸，及任選地由0至25莫耳 %至少另一種脂肪族、環脂族及/或芳香族多羧酸；以及就 醇成分之總量而言，由25莫耳％至100莫耳％至少一種分 支鏈脂肪族二醇，以及任選地由0至75莫耳％至少另一種 脂肪族或環脂族多元醇。 包含於本發明使用之聚酯之含4個至1 4個碳原子之直 鏈飽和脂肪族二羧酸較佳係選自於丁二酸、己二酸、戊二 200837138 酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、十 一烷二酸、十三烷二酸、十四烷二酸及其酐類，可單獨使 用或呈混合物使用。直鏈飽和脂肪族二酸最佳爲己二酸。 聚酯中視需要可包含的另一種多羧酸通常係選自於二 羧酸及/或其酐類，更特別係選自於反丁烯二酸、順丁烯二 酸、酞酐、間苯二甲酸、對苯二申酸、1，4-環己二羧酸、1，3-環己二羧酸、1,2-環己二羧酸，可單獨使用或呈混合物使 用。聚酯也可爲經由相對於酸成分總量，摻混高達1 5莫耳 %含至少三個羧酸基之多元酸或其酐類，諸如偏苯三酸、均 苯四酸及其酐類或其混合物所得之分支聚酯。 聚酯更佳係得自相對於酸成分總量，85至1 〇〇莫耳％， 最佳95至100莫耳％含4個至14個碳原子之直鏈飽和脂肪 族二羧酸。 替代使用多羧酸或除了使用多羧酸之外，可使用相對 應之酐類、酯類或其混合物用於製備聚酯。 用於聚酯之分支鏈脂肪族二醇較佳係選自於丙二醇、 新戊二醇、1-甲基-1,3-丙二醇、2-甲基-1,3-丙二醇、2-丁基 -2-乙基-1,3-丙二醇、新戊二醇之羥基特戊酸酯及其混合 物。分支鏈脂肪族二醇最佳爲新戊二醇。 其它視需要可包含於聚酯之脂肪族多元醇或環脂族多 元醇通常係選自於二官能多元醇、三官能多元醇及/或四官 能多元醇。二醇較佳係選自於乙二醇、1，3-丙二醇、1，4-丁 二醇、1,5-戊二醇、1，6-己二醇、1，7-庚二醇、1，8-辛二醇、 1，9-壬二醇、1，1〇-癸二醇、1，14-十四烷二醇、1，16-十六烷 200837138 二醇、1，4 -環己二醇、1，4-環己烷二甲醇、氫化雙酚a及其 混合物。也可使用聚伸院基二醇類，諸如二乙二醇及三乙 二醇及二丙二醇及三丙二醇。二醇更佳爲脂肪族二醇，特 別爲包含2至12個碳原子之烷基二醇。聚酯也可爲分支聚 酯，相對於醇總量摻混高達30莫耳％含3個或更多個醇基 之多元醇，較佳爲三官能多元醇及四官能多元醇，諸如三 羥甲基丙烷、二·三羥甲基丙烷、三羥甲基乙烷、季戊四醇 及其混合物。 本發明使用之聚酯更佳係得自於，相對於醇成分總 量，由45至100莫耳％分支鏈脂肪族二醇，由0至55莫耳 %另一種脂肪族二醇，以及由〇至30莫耳％三官能多元醇 及/或四官能多元醇。 本發明使用之羧基官能基聚酯通常具有數目平均分子 量Mn由4 00至9 800。聚酯較佳具有Mn至少爲600，更佳 至少爲800及最佳至少爲1〇〇〇。聚酯較佳具有Mn不超過 6800，更佳不超過4800及最佳不超過4500° 本發明中，數目平均分子量Mn可由下式求出200837138 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a radiation hardenable composition, particularly for use in coatings. [Prior Art] A coil coater coats various types of various types of metal coils. Volume # Coating is a continuous and highly automated & process that coats metal at high speed before the composition is combined. The process consists of the following steps. The metal coil passes through the _ coil and the top and bottom surfaces of the metal coil are mechanically and chemically cleaned to remove residual oil, grease and dirt. After cleaning, chemical pretreatment can be applied to the sheet to improve corrosion resistance and paint adhesion. The strip is then moved directly to the drying oven and then into the coating unit. After the coating has been applied, the strip is again moved into the drying oven and then cooled and re-rolled for shipment. The pre-coated sheets are used in the metalworking industry. Therefore, a plurality of metal objects are not coated or coated at the time of use or assembly, but instead are first supplied as a flat stock of the coil, and then formed, cut, and assembled into a desired article. As a result, the key criteria in almost all cases can be post-formed or bent of the coated strip. Post-forming is usually done by high-speed processing equipment, where metal bending is extremely demanding. The metal must be flexible before it can be post-formed or bent without causing breakage while still maintaining adhesion. The entire system indicates that in some cases, the protective zinc layer, pretreatment layer, and coating layer are also accessible to a high degree of corrosion resistance. For example, basic properties such as chemical resistance and strain resistance are important, and for certain applications, properties such as humidity test tolerance and sterilization test resistance are also required. 200837138 Radiation hardenable system is ideal for coil coating; flat substrate with high linear velocity' can solve environmental issues, such as the use of solvents, requiring less energy and floor space than other hardening ovens required for other coating technologies . However, up to now, radiation hardenable coating compositions, particularly ultraviolet light formulations, have not been widely used for winding coating applications. Typical ultraviolet light formulations comprise (meth)acrylated oligomers and reactive diluents which, when hardened, form highly crosslinked coatings having good properties such as chemical resistance, scratch resistance, and surface hardness. Floor. This high degree of crosslink density is also associated with the limited flexibility and shrinkage of the film, thereby limiting the adhesion of the film to the metal substrate. When attempting to find a solution to such demanding requirements, it is often limited by the need to reduce the molecular weight to achieve a reasonable viscosity, and the need for substantial molecular weight between the crosslinks to achieve the desired hardened coating. For coil coating applications where high flexibility is required for post-forming operations, typical UV formulations are not suitable. US 2002/0132059 A1 describes the principle of using a photopolymerizable coating composition for coating a coiled metal flake. In the method of applying a coating to the coiled metal flakes herein, the metal flakes are first cleaned and then pretreated, followed by application of the coating composition. Specific photopolymerizable compositions are not disclosed in this patent application. However, not all of the photopolymerizable coating compositions comprising unsaturated oligomers provide satisfactory results when used in a roll coating process. The inventors have found today a novel radiation hardenable oligomer that is highly suitable for use in photopolymerizable compositions. 200837138 SUMMARY OF THE INVENTION Accordingly, the present invention is directed to a radiation hardenable composition comprising at least one radiation hardenable polymer having a glass transition temperature Tc and/or a melting point Tm of less than 3 〇〇c, the oligomer being via One or more obtained by reacting a carboxy-functional polyester (a) having a glass transition temperature Tc and/or a melting point Tm of less than 3 (rc), and the polyester is derived from the total amount of the acid component, 7 5 Mole% to 100% by mole of at least one linear saturated aliphatic diresor acid having 4 to 14 carbon atoms' and optionally from 〇 to 25 mol% at least another aliphatic, Cyclosporin and a fragrant aromatic acid; and, in terms of the total amount of the alcohol component, from 2 5 mol% to 100 mol% of at least one branched chain aliphatic diol, and optionally from 0 to 75 mol% at least another An aliphatic or cycloaliphatic polyol with one or more (meth)acrylated monoepoxides (bl) and/or one or more polyepoxides (b2) and one or more alpha, fluorene-unsaturated carboxylic acids The acid reaction is obtained. [Embodiment] In the present invention, it is necessary to understand "(meth) propylene. The term "base" encompasses both acryl-based and methacryl-based compounds or derivatives and mixtures thereof. The radiation-hardenable oligomers generally have a number average molecular weight of at least 600, preferably at least 800, and more preferably at least 1000. The hardenable oligomer has a number average molecular weight of not more than 10,000, preferably not more than 7,000, and most preferably not more than 5000. The radiation hardenable oligomer is heated according to ASTM D3418 with a heating gradient of 20 ° C per minute. Scanning calorimetry measures the glass transition temperature Τ and/or the melting point Tm is less than 20° C. The radiation-hardenable oligomer preferably has a glass transition temperature T. and/or the melting point Tm is less than 0° C. 200837138 The radiation-hardenable oligomer used in the present invention is derived from a carboxyl functional polyester. The term carboxyl functional polyester means a polyester comprising a free-form, usually terminal-COOH (fluorenyl) group. The g-based polyester typically has an acid hydrazine of from 10 to 340 mg K0H/g (mgKQH/g). The polyester used in the present invention preferably has an acid hydrazine of at least 20, more preferably at least 25, and most preferably at least 30. The polyester used in the present invention preferably has a sourness of not more than 250 Mg K〇H/g, more preferably not more than 190 mg K〇H/g, and most preferably not more than 80 mg KOH/g. The carboxyl functional polyester can also be obtained by reacting a hydroxy functional polyester with a cyclic anhydride. The hydroxy-functional polyester is represented in the present invention. The polyester has a free hydroxyl group and is usually a terminal hydroxyl group, and usually has a hydroxyanthracene of 10 to 340 mg KOH/g. The hydroxy-functional polyester used in the present invention preferably has a hydroxyl group value. It is 25 to 250 mg K〇H/g, more preferably 30 to 190 mg K〇H/g. The carboxyl functional polyester and/or hydroxy functional polyester used in the present invention is composed of one or more polybasic acids. The acid component is obtained by reacting with an alcohol component comprising one or more polyols. And the polyester is derived from 75 mol% to 100 mol% of at least one linear saturated aliphatic dicarboxylic acid having 4 to 14 carbon atoms in terms of the total amount of the acid component, and optionally From 0 to 25 mol% of at least one other aliphatic, cycloaliphatic and/or aromatic polycarboxylic acid; and from 25 mol% to 100 mol% of at least one branched chain in terms of the total amount of the alcohol component Aliphatic diol, and optionally from 0 to 75 mole percent of at least one other aliphatic or cycloaliphatic polyol. The linear saturated aliphatic dicarboxylic acid having 4 to 14 carbon atoms contained in the polyester used in the present invention is preferably selected from the group consisting of succinic acid, adipic acid, glutaric acid 200837138 acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, undecanedioic acid, tridecanedioic acid, tetradecanedioic acid and anhydrides thereof may be used singly or as a mixture. The linear saturated aliphatic diacid is preferably adipic acid. Another polycarboxylic acid which may optionally be included in the polyester is usually selected from the group consisting of dicarboxylic acids and/or anhydrides thereof, more particularly selected from the group consisting of fumaric acid, maleic acid, phthalic anhydride, and isophthalic acid. Dicarboxylic acid, p-benzoic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid may be used singly or as a mixture. The polyester may also be a polybasic acid or an anhydride thereof containing at least three carboxylic acid groups, such as trimellitic acid, pyromellitic acid, and anhydride thereof, by blending up to 15 mol% with respect to the total amount of the acid component. Branched polyester obtained by or a mixture thereof. More preferably, the polyester is derived from a linear saturated aliphatic dicarboxylic acid having from 4 to 14 carbon atoms, preferably from 85 to 1% by mole based on the total amount of the acid component. Instead of or in addition to the polycarboxylic acid, the corresponding anhydrides, esters or mixtures thereof can be used for the preparation of the polyester. The branched chain aliphatic diol for polyester is preferably selected from the group consisting of propylene glycol, neopentyl glycol, 1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl 2-Ethyl-1,3-propanediol, hydroxypivalate of neopentyl glycol, and mixtures thereof. The branched aliphatic diol is preferably neopentyl glycol. Other aliphatic or cycloaliphatic polyols which may optionally be included in the polyester are generally selected from the group consisting of difunctional polyols, trifunctional polyols and/or tetrafunctional polyols. The diol is preferably selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,1 -anthracenediol, 1,14-tetradecanediol, 1,16-hexadecane 200837138 diol, 1,4 - Cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol a, and mixtures thereof. Poly-based glycols such as diethylene glycol and triethylene glycol, and dipropylene glycol and tripropylene glycol can also be used. The diol is more preferably an aliphatic diol, particularly an alkyl diol having 2 to 12 carbon atoms. The polyester may also be a branched polyester, which is blended with up to 30 mol% of a polyol having 3 or more alcohol groups, preferably a trifunctional polyol and a tetrafunctional polyol such as trishydroxyl with respect to the total amount of the alcohol. Methylpropane, ditrimethylolpropane, trimethylolethane, pentaerythritol, and mixtures thereof. The polyester used in the present invention is more preferably derived from 45 to 100 mol% branched aliphatic diol, from 0 to 55 mol% of another aliphatic diol, and by weight of the total alcohol component. 〇 to 30 mol% trifunctional polyol and / or tetrafunctional polyol. The carboxyl functional polyester used in the present invention generally has a number average molecular weight Mn of from 4 to 9 800. The polyester preferably has a Mn of at least 600, more preferably at least 800 and most preferably at least 1 Torr. The polyester preferably has a Mn of not more than 6,800, more preferably not more than 4,800 and most preferably not more than 4,500. In the present invention, the number average molecular weight Mn can be obtained by the following formula
Σ (Mac)}^ Σ — MhzD j k Σ + Σ~ Πη2〇 I ^ 其中：i及k分別係指聚酯合成中使用的不同多元酸及不同 多元醇，Ma。表示多元酸之重量（克），Mb表示聚酯合成中使 用之多元醇重量（克），ru。及nb分別爲聚酯合成中使用之多 元酸及多元醇之莫耳數’ “^。及nH2°分別爲聚醋合成中所 -10- 200837138 產生之水之重量克數及莫耳數。 於特殊情況下，其中使用由羥基官能基聚酯與環狀酐 反應所得之羧基官能基聚酯，羧基官能基聚酯之分子量可 由羥基官能基聚酯之數目平均分子量及酐之分子量求出， 計算時須考慮酐及羥基官能基聚酯之相對用量及其羥基 本發明使用之聚酯較佳爲非晶形聚酯。本發明中，非 晶形聚酯一詞表示一種聚酯其實質上並未顯示結晶化，且 以加熱梯度爲每分鐘20°C，根據ASTM D3418，藉差動掃 描量熱術測定並未呈現熔點。聚酯更佳具有以加熱梯度爲 每分鐘20°C，根據ASTM D3418，藉差動掃描量熱術測定 具有玻璃轉換溫度T。由-120°C至25°C。聚酯於25°C較佳爲 液體。 當使用由羥基官能基聚酯與環狀酐反應所得之羧基官 能基聚酯時，此種環狀酐較佳具有通式（I):Σ (Mac)}^ Σ — MhzD j k Σ + Σ~ Πη2〇 I ^ where: i and k refer to the different polyacids and different polyols used in the synthesis of polyester, Ma. Indicates the weight (gram) of the polybasic acid, and Mb represents the weight (gram) of the polyol used in the synthesis of the polyester, ru. And nb are the number of moles of polybasic acid and polyol used in the synthesis of polyester, respectively, and nH2° are the weight of water and the number of moles of water produced by the polymer in the synthesis of -10-200837138. In a special case, wherein a carboxyl functional polyester obtained by reacting a hydroxy-functional polyester with a cyclic anhydride is used, the molecular weight of the carboxy-functional polyester can be determined from the number average molecular weight of the hydroxy-functional polyester and the molecular weight of the anhydride, The relative amount of the anhydride and the hydroxy-functional polyester and its hydroxyl group must be considered. The polyester used in the present invention is preferably an amorphous polyester. In the present invention, the term amorphous polyester means a polyester which does not substantially show Crystallization, with a heating gradient of 20 ° C per minute, according to ASTM D3418, does not exhibit a melting point by differential scanning calorimetry. The polyester preferably has a heating gradient of 20 ° C per minute, according to ASTM D3418, according to ASTM D3418, Differential scanning calorimetry has a glass transition temperature T from -120 ° C to 25 ° C. The polyester is preferably liquid at 25 ° C. When using a reaction between a hydroxy-functional polyester and a cyclic anhydride When a carboxyl functional polyester Preferred type of cyclic anhydrides having the general formula (I):
其中R表示伸芳基、伸環烷基、伸烷基或伸烯基，R可帶 有烷基、烯基、-COOH及/或其它酐基。酐之實例包括酞酐、 六氫鄰苯二甲酸酐、戊二酐、丁二酐、十二烯基丁二酐、 順丁烯二酐、偏苯三酸酐、均苯四酸酐。較佳酐類爲其中 R爲經以包含5個至20個碳原子之嫌基鍵取代之伸芳基（更 佳爲伸苯基）或伸烷基（更佳爲伸乙基）。也可使用酐之混合 -11- 200837138 物。 用於由羥基官能基聚酯製備羧基官能基聚酯之酐數量 通常相對於每批當量聚酯中所存在之-OH基團，用於由羥 基官能基聚酯製備羧基官能基聚酯之酐用量通常至少爲 0.8 p莫耳，較佳至少〇·9 p莫耳及更佳至少0.95 p莫耳酐。 相對於p當量之聚酯之-OH，酐之用量通常至多爲1.2 p莫 耳，較佳至多爲1.1 P莫耳及最佳至多爲1.Op莫耳。 由羥基官能基聚酯及酐製備羧基官能基聚酯可原位進 行，而於進一步與環氧化物反應前無需分離羧基官能基聚 酯。 根據本發明之第一變化例，輻射可硬化寡聚物爲羧基 官能基聚酯與一種或多種（甲基）丙烯酸化一環氧化物之反 應產物。於此種情況下，較佳係使用羧基官能基聚酯及（甲 基）丙烯酸化一環氧化物之相對量，故由一種或多種（甲基） 丙烯酸化一環氧化物所提供之環氧化物當量數y係等於或 大於由羧基官能基聚酯所提供之-C00H基團數X。較佳 y = x。當y係大於X時，較佳以至少（y-χ)之量，更佳（y-x) 之量將至少一種-不飽和羧酸也添加至羧基官能基聚 酯之反應混合物。（甲基）丙烯酸化一環氧化物一詞係表示 包含一個環氧基以及一個或多個（甲基）丙烯酸基之化合 物。有用之（甲基）丙烯酸化一環氧化物之實例爲環氧丙基 (甲基）丙烯酸酯類，諸如丙烯酸環氧丙酯、甲基丙烯酸環 氧丙酯、4-羥基丁基丙烯酸酯環氧丙醚、雙酚-Α二環氧丙 醚一丙烯酸酯。（甲基）丙烯酸化一環氧化物類較佳係選自 -12- 200837138 於丙烯酸環氧丙酯及甲基丙烯酸環氧丙酯。 根據本發明之第二且較佳變化例，輻射可硬化寡聚物 爲羧基官能基聚酯與至少一種多環氧化物以及至少一種 α, /3 -不飽和羧酸之反應產物。於此種情況下，較佳係使用 相對量之聚酯、多環氧化物及不飽和羧酸，因此，對由聚 酯所提供之X當量-COOH基團而言，存在有至少ζ當量多 環氧化物，及至少（ζ-χ)當量α，/3-不飽和竣酸。於本發明之 此種變化中，ζ較佳至少爲1.5 X，更佳至少爲2 X。ζ通常 不超過20 X，較佳不超過15 X。當ζ係大於2 X時，過量 多環氧化物與α，/3 -不飽和竣酸反應，於原位形成不飽和多 環氧化物衍生物。 多環氧化物一詞表示包含至少兩個環氧官能基之任一 種化合物。多環氧化物通常係選自於芳香族多元醇或脂肪 族多元醇之環氧丙醚、芳香族多元酸或脂肪族多元酸之環 氧丙酯、或選自於環脂族多環氧化物。較佳爲芳香族多元 醇或脂肪族多元醇之二環氧丙醚、芳香族多元酸或脂肪族 多元酸之二環氧丙酯、或選自於環脂族二環氧化物’諸如 雙酚-Α之二環氧丙醚、雙酚-F之二環氧丙醚、聚（環氧乙烷 共聚-環氧丙烷）之二環氧丙醚（商品名DER 736)、聚環氧丙 烷之二環氧丙醚（商品名DER 732)、己二醇之二環氧丙醚（商 品名ΝΡΕΚ-051)、丁二醇之二環氧丙醚（商品名亞拉待 (Araldite) D Υ 02 6 SP)、亞油酸二元體之二環氧丙醚（商品名 愛里希斯（Erisys) GS-120)、纖維素氧化物（celloxide) 20 81。特佳爲雙酚-A之二環氧丙醚、聚（環氧乙烷共聚-環氧 -13- 200837138 丙烷）之二環氧丙醚、聚丙二醇之二環氧丙醚、丁二醇之二 環氧丙醚。 a，；S -不飽和錢酸較佳係選自於丙嫌酸及甲基丙嫌 酸，最佳係選自於丙烯酸。本發明之第二變化例中之a，冷-不飽和羧酸之用量較佳爲（z-x)當量，其中z爲多環氧化物 當量，X爲羧基官能化聚酯之-COOH當量。 於本發明之此第二變化例中，較佳係經由於多環氧化 物之前、或至少與多環氧化物同時，經由添加a，/3 -不飽和 羧酸至羧基官能化聚酯，來製備輻射可硬化寡聚物。 根據本發明之第三變化例，輻射可硬化寡聚物係由一 種或多種羧基官能基聚酯U)與一種或多種（甲基）丙烯酸化 一環氧化物，以及與一種或多種多環氧化物及/或一種或多 種α，/3 -不飽和羧酸反應獲得。 羧基化聚酯與環氧化物之反應通常係於一種或多種催 化劑存在下進行。於反應中或反應後，可添加一種或多種 聚合抑制劑。 根據本發明之輻射可硬化寡聚物可就此製備，但有可 於非反應性稀釋劑存在下製備。非反應性稀釋劑一詞表示 反應期間不會與羧基官能基聚酯、環氧化物及/或不飽和羧 酸反應之化合物。根據較佳實施例，於輻射可硬化寡聚物 之合成期間、合成結束時及/或合成之後，添加至少一種輻 射可硬化非反應性稀釋劑至輻射可硬化寡聚物。 根據本發明之輻射可硬化組成物通常含有至少5 %，較 佳至少10%，更佳至少15%及最佳至少25%重量比輻射可硬 -14- 200837138 化寡聚物。輻射可硬化寡聚物之含量通常不超過可硬 成物之95 %重量比，且較佳不超過80%重量比。 根據本發明之輻射可硬化組成物除了一種或多種 可硬化寡聚物之外，較佳含有至少一種輻射可硬化 劑。此種稀釋劑較佳爲可共聚合烯屬不飽和單體，更 一官能基或多官能基（甲基）丙烯酸酯單體。可共聚合 屬不飽和單體表示通常於光聚合條件下，特別藉照光 可與輻射可硬化寡聚物共聚合的單體。較佳可共聚烯 飽和單體爲包含至少一個（甲基）丙烯酸基且較佳不超 個（甲基）丙烯酸之一官能基及多官能基（甲基）丙烯醯 (甲基）丙烯酸酯。適當單體之實例包括丙烯酸辛基癸 丙烯酸月桂酯、丙烯酸苯氧基乙酯、丙烯酸異莰酯^、 酸苯基環氧丙醚、丙烯酸環狀三羥甲基丙烷甲醛、胺 酸正丁基、丙烯醯氧基乙酯、丙烯酸四氫糠酯、丙烯 味啉、一丙烯酸丁二醇酯、丙烯酸二氫二環戊二烯酯 烯酸與脂肪族羧酸如新癸酸之環氧丙酯之反應產物及 合物。最佳稀釋劑爲丙烯酸苯氧基乙酯、丙烯酸異莰 胺基甲酸正丁基丙烯醯氧基乙酯、丙烯酸四氫糠酯、 醯基味啉，丙烯酸與脂肪族羧酸如新癸酸之環氧丙酯 應產物及其混合物。存在於輻射可硬化組成物中之輻 硬化稀釋劑之含量通常爲0至95 %重量比，更佳爲5至 重量比，又更佳爲10至40 %重量比。 輻射可硬化組成物較佳ISO 1 205 8測定，於25 °C 黏度爲 100 至 8000 mPa.s，較佳爲 1500 至 3500 mPa.s 化組 輻射 稀釋 佳爲 之烯 ，而 屬不 過 6 胺及 酯、 丙烯 基甲 醯基 ，丙 其混 酯、 丙烯 之反 射可 75% 具有 -15- 200837138 根據本發明之方法所使用之輻射可硬化組成物通常也 含有至少一種抑制劑。抑制劑包括但非限於氫醌、甲苯基 氫醌、一甲基醚氫醌、第三丁基氫醌、二-第三丁基氫醌、 2,6·二-第三丁基-4-甲酚（BHT)、啡噻阱。抑制劑用量通常 係由0至0.5 %重量比。 輻射可硬化組成物也包含至少一種光化學引發劑及/ 或化學引發劑，其可引發輻射可硬化寡聚物以及任選地其 中所存在之其它輻射可硬化化合物之聚合反應。光化學引 發劑（也稱作爲光引發劑）爲藉吸光典型爲吸收紫外光而可 產生基團之化合物。光引發劑較佳爲自由基光引發劑。 當於紫外光下硬化時，以包含至少一種光引發劑之可 硬化組成物爲佳。組成物中之光引發劑或化學引發劑含量 較佳爲0.01 wt%至5 wt%。 另外，組成物可於無引發劑存在下硬化，特別藉電子 束輻射硬化。 輻射可硬化組成物也含有一種或多種黏著促進劑。黏 著促進劑之含量通常係占〇至20%重量比。較佳係使用2% 至15%重量比之黏著促進劑。 根據本發明之輻射可硬化組成物也包含顏料、著色劑 及/或添加劑，諸如多官能（甲基）丙烯酸化化合物、傳導性 顏料、分散劑、流動改性劑、滑脫劑、阻燃劑、紫外光保 護劑。添加劑含量較佳係不超過1 〇 %重量比。 根據本發明之輻射可硬化組成物較佳爲實質上不含水 及被視爲揮發性有機溶劑（VOC)之有機溶劑。如此，根據本 -16- 200837138 發明之組成物通常被視爲1 00%固體（固化後）輻射可硬化組 成物，其於隨後之硬化期間無需蒸發去除水或溶劑。 根據本發明之輻射可硬化組成物允許獲得有良好化學 及溶劑耐性、耐刮性、及表面硬度，連同改良之可撓性、 黏著性以及彎折及快速變形時之斷裂耐性，以及具有改良 之防蝕性之塗層。塗層具有可撓性與表面性質間之改良之 平衡。輻射可硬化組成物也具有改良之耐熱性，且顯示良 好之電絕緣性質。此等性質讓其適合用於大量應用用途， 諸如於金屬、塑膠及玻璃等基材上之塗層用途。根據本發 明組成物適合用於大量用途，諸如金屬塗覆、捲料塗覆及 裝置，特別係用作爲農業及建築設備、家電之塗層、管路 塗層、建築物塗覆、線料塗覆諸如銅線塗覆、汽車用途， 特別係作爲汽車再光整的底漆以及金屬罐塗層。輻射可硬 化組成物也可用於諸如於模具內部裝飾等熱成型用途。該 組成物也適合用於製造電套筒及玻璃層合物。組成物特別 可用於塗覆可撓性基材，諸如包裝材料及塑膠。輻射可硬 化組成物也可用於調配紫外光可硬化之網板墨水，呈現高 度可撓性及耐衝擊性。 因此本發明亦係關於使用如前文說明之組成物用於塗 覆用途’特別係用於製備經塗覆物件之方法，包含該物件 以前文說明之組成物塗覆之步驟。 發現輻射可硬化組成物特別適合用於金屬塗覆及捲料 塗覆用途。因此本發明也係關於其用於金屬塗覆特別爲捲 料塗覆用途’更特別係關於一種製備經塗覆之金屬片捲料 -17- 200837138 之方法，包含下列步驟： (1) 將盤捲的金屬片料解捲； (2) 以包含如前文說明之至少一種輻射可硬化寡聚物 之可硬化組成物塗覆該金屬片料； (3) 硬化該組成物；以及 (4) 再度盤捲塗覆後之金屬片料。 金屬片料通常係選自於冷輥鋼（有或無前處理）、熱輥 鋼（有或無前處理）、不銹鋼、經過鋅處理之鋼（有或無前處 理），諸如電鍍鋅鋼以及熱浸鍍鋅鋼、鋁（有或無前處理）以 及熱浸錫。 於本發明方法中，金屬片料之解捲以及再度盤捲可藉 任一種適當手段進行。於根據本發明之方法中，解捲的金 屬片料可於使用輻射可硬化組成物之前接受任一種適當處 理。解捲之金屬片料通常經清潔來去除保護油層。於清潔 後’也施用化學前處理至該片料來加強防蝕性及塗層黏著 性。 於根據本發明之方法中，輻射可硬化組成物可藉任一 種適當手段諸如浸塗、噴塗、靜電塗覆、膜塗、簾塗、真 空施用、輥塗等來施用於預塗覆之物件，特別係施用於金 屬片料。較佳係藉輥塗施用。輻射可硬化組成物施用至物 件’特別係施用至金屬片料可於任何適當溫度，諸如室溫 或更高溫，例如經由加熱金屬片料、輥塗機及/或可硬化組 成物進行。 於使用輻射可硬化組成物塗覆該物件或金屬片料後， -18- 200837138 組成物經硬化。硬化亦即聚合反應可藉熟諳技藝人士眾所 周知之任一種適當手段諸如熱硬化或照光硬化進行。照光 硬化可使用紫外光或游離輻射諸如γ射線、X射線或電子束 進行。於根據本發明之方法中，以電子束且特別爲紫外光 輻射爲佳。 於可硬化組成物硬化後，經塗覆後的金屬片料可即刻 再度盤捲，或可施用一層或多層額外塗層隨後再度盤捲； 或再度盤捲後之經塗覆之金屬片料可移動至另一條塗覆生 產線，於該處施用一層或多層額外塗層。於根據本發明之 方法中，可重複步驟（2)及（3)來以如前文定義之兩種或多種 輻射可硬化組成物塗覆金屬片料。於此種情況下，輻射可 硬化組成物可爲相同或相異。 根據本發明之方法允許獲得塗覆物件，特別有較少量 溶劑或甚至未使用溶劑之金屬捲料，如此可降低火災風 險，節省能量使用，無需去除或循環利用溶劑，以及生產 線上空間節省（無需乾燥烤爐）。 根據本發明之方法允許獲得塗覆物件，特別爲金屬片 料，其具有改良之化學耐性及溶劑耐性、耐刮性及表面硬 度，連同改良之可撓性、黏著性以及對彎折及快速變形時 的斷裂耐性，且具有改良之防鈾性，因而讓該金屬片料特 別適合用於後成型。塗層具有改良之可撓性與表面性質間 之改良之平衡。 根據本發明之方法當鋅層沈積於金屬表面上後’於鍍 鋅生產線上或電鍍鋅生產線上施用可硬化底劑時，允許避 -19- 200837138 免部分或全部本方法之下列步驟：於鍍鋅生產線上或電鍍 鋅生產線上再度盤捲之前將條料上油、化學清潔、化學前 處理、以及施用傳統底劑於塗覆生產線。化學前處理經常 係使用Cr VI進行鉻酸化，使用根據本發明方法將允許解 決此種環保議題。根據本發明方法允許獲得有良好防鈾性 之經塗覆之金屬捲料，即使未使用金屬之化學前處理例如 鉻酸化反應仍可獲得。 本發明進一步係有關使用輻射可硬化組成物來製造電 套筒塗層，以及有關製備電套筒塗層之方法，其中套筒， 較佳爲玻璃纖維製造之套筒經塗覆以及/或浸漬以如前文 說明之輻射可硬化組成物。於塗覆及/或浸漬後，輻射可硬 化組成物係諸如前文說明硬化。此套筒可用來包圍電線或 電線束，故獲得絕緣耐熱之電纜線。 後文實例說明本發明但非限制性。除非另行指示，否 則實例中所述份數爲份數重量比。 製備例1 :羥基官能基聚酯PE1 : 於連接有加熱夾套且裝配有攪拌器之2升反應器內， 加入5 1 3克新戊二醇及646克己二酸。反應混合物於氮流 下經攪拌及漸進加熱至2 1 5 °C，藉蒸餾去除水。當酸値達到 約 50 mg KOH/g時，於大氣壓下添加 0.20克法斯凱特 (FAS CAT) 4 102(錫催化劑），反應混合物又於21 5°C加熱， 於減壓下去除水，直到酸値低於1 mg KOH/g。聚酯爲具有 羥基値56 mg KOH/g之透明液體；其平均分子量爲約2000。 製備例2 :羥基聚酯PE2 : -20- 200837138 聚酯係根據製備例1所述方法製備，但使 丁二醇，272克新戊二醇及670克己二酸。聚 値56 mg KOH/g之透明液體；其平均分子量〕 製備例3 :羧基聚酯PE3 : 於連接有加熱夾套且裝配有攪拌器之7 加入2023克新戊二醇（NPG)及3518克己二酸 於氮流下經攪拌及漸進加熱至2 1 5 °C，藉蒸飽 値達到約50 mg KOH/g時，於大氣壓下添加 特（FAS CAT) 4 102，反應混合物又於215°C加 去除水，直到酸値低於1 mg KOH/g。聚酯爲具 K〇H/g之透明液體；其平均分子量爲約2000 實例1 :輻射可硬化寡聚物之製備 2504克聚酯PE1、371克鄰苯二甲酸酐、 鉻催化劑（AMC-2)置於裝配有攪動器、液體添 計之反應瓶內。混合物於1 1 5 °C加熱，於此： 時。加入180克丙烯酸、2.88克氫醌HQ及 之混合物，反應混合物經攪拌且於1 03 °C維ί 然後逐滴添加926克雙酚-Α之二環氧丙 反應混合物，使得溫度不超過120°C，且反 1 l〇°C，攪拌至酸値低於2.5 mg KOH/g ’及 0.1%。 獲得具有黏度（錐與板黏度，ISO 3219於 mPas之產物。 實例2 : 用 223 克 1，4-酯爲具有羥基 爲約2000 。 升反應器內， 。反應混合物 去除水。當酸 1.25克法斯凱 熱，於減壓下 -有酸値56 mg 〇 及10克辛酸 加漏斗及溫度 昆度維持2小 5.96 克 AMC-2 ί 1小時。 醚（BADGE)至 應混合物又於 環氧基値低於 6〇〇C )爲 90300 -21- 200837138 重複實例1，但連同丙烯酸添加1 749克丙烯三異莰酯 (IBOA)至反應混合物。獲得黏度（錐與板黏度，ISO 3219於 25°C )爲 55 700 mPas 之產物。 另外，反應結束時，冷卻至80°C後，IB0A添加至反應 混合物。獲得具有黏度（錐與板黏度，ISO 3219於25°C )爲 5 3 200 mPas 之產物。 實例3 : 使用下列數量，根據實例2之程序合成寡聚物：626 克聚酯PE 2、93克鄰苯二甲酸酐、45克丙烯酸、23 2克 BADGE、3.99 克 AMC-2、0.72 克 HQ 及 271 克 IB0A。獲得 具有黏度（錐與板黏度，ISO 3219於60°C )爲7 800 mPas之 產物。 實例4 : 470克聚酯PE3及0.48克MeHQ置於裝配有攪動器、 液體添加漏斗及溫度計之反應瓶內。反應混合物加熱至 103°C，34克丙烯酸、1.45克AMC-2及290克IB0A之混合 物添加至反應器。溫度於1 〇3 °C維持1小時，然後將174 克BADGE逐滴添加至反應混合物，讓溫度不超過120 °C ; 反應混合物進一步於 ll〇°C加熱至酸値係低於 2.5 mg K〇H/g，及環氧基値係低於0.1% 〇獲得具有黏度（錐與板黏 度，ISO 3219 於 25 °C)爲 37300 mPas 之產物。 實例5 : 使用626克聚酯PE1替代聚酯PE2，根據實例3所述 程序合成寡聚物。獲得具有黏度（錐與板黏度，ISO 3219於 -22- 200837138 60°C)爲 32000 mPas 之產物。 實例6 : 使用下列數量，根據實例2之程序合成寡聚物：260 克聚酯PE 1、38克鄰苯二甲酸酐、129克丙烯酸、386克 BADGE、2.26 克 AMC-2、0.65 克 BHT 及 350 克 IBOA。獲得 具有黏度（錐與板黏度，ISO 3219於60 °C)爲700 mPas之產 物。 實例7 : 使用29 0克苯氧基乙基丙烯酸酯替代IB0A，根據實例 4所述程序合成寡聚物。獲得具有黏度（錐與板黏度，ISO 3219 於 60°C)爲 21000 mPas 之產物。 比較例8R : 丙烯酸化聚酯之製備如下：於連接至裝配有攬拌器之 油浴之1升雙夾套反應器內，加入400克聚酯PE1，31.7 克丙烯酸；14.2克對甲苯磺酸（PTSA)、2 8 8克甲苯、0.73 克Cu2〇、0.55克甲基氫醌（MeHQ)及0.73克TNPP。反應混 合物於氧氣流下加熱至回流（11 5_ 120°C )。藉共沸蒸餾去除 水。當不再蒸餾出水時，添加0.6克MeHQ及0.36克TNPP， 於減壓下蒸餾去除甲苯。聚酯丙烯酸酯具有於60°C之黏度 爲 1544 mPa.s (霍普樂（HOppler)，ISO 12058 於 6(TC)。 比較例9R ·· 丙烯酸化聚酯係如同比較例7R製備，但使用400克聚 酯PE 2。聚酯丙烯酸酯具有於60°C之黏度爲8 9 8 mPa.s (霍 普樂，ISO 1 205 8 於 60t：)。 -23- 200837138 實例10至19及比較例20R至23R ·· 紫外光可硬化調配物係經由混合製備： 90份分別於實例2至5、7、比較例8R及9R所得之產 物或市售樹月旨EBECRYL® 629及EBECRYL® 3213 5份黏著促進劑（EBECRYL® 171) 3份光弓丨發劑（ADDITOL® CPK) 2份光引發劑（TPO-L) 紫外光調配物係利用1 0微米桿塗機塗覆於熱浸鍍鋅 鋼（實例10至14及比較例22R及23R)或鉻酸化電鍍鋅鋼（實 例15至19及比較例20R至21R)，暴露於來自於120瓦/ 厘米非聚焦中壓汞蒸氣燈之紫外光輻射來獲得不沾黏之薄 膜。 試樣經測試溶劑耐性（ECCA ΤΙ 1)、交叉畫線黏著性 (ISO 2409)、彎折時之黏著性及耐斷裂性（T彎折測試EN 13 523-7)、快速變形時之黏著性及耐斷裂性（反向衝擊， ISO/DIS 6272-ASTM D 27 94)以及於緩慢牽伸變形時之黏著 性（ISO 1 5 20)。 實例24及25 : 紫外光可硬化調配物係經由混合製備： 45份於實例1所得產物 45份苯氧基乙基丙烯酸酯（EBECRYL® 114) 5份黏著促進劑（EBECRYL® 171) 3份光弓丨發齊!I (ADDITOL® CPK) 2份光引發劑（TP0-L) -24- 200837138 紫外光調配物係利用1 0微米桿塗機塗覆於熱浸鍍鋅 鋼（實例24)或鉻酸化電鍍鋅鋼（實例25)，經硬化及如實例 1 0評估。 實例26及27 : 紫外光可硬化調配物係經由混合製備： 43.2份於實例1所得產物 46.8份丙烯酸異莰酯 5份黏著促進劑（EBECRYL⑧171) 3份光弓丨發齊II (ADDITOL® CPK) 2份光引發劑（TPO-L) 紫外光調配物係利用1 0微米桿塗機塗覆於熱浸鍍鋅 鋼（實例26)或鉻酸化電鍍鋅鋼（實例27)，經硬化及如實例 1 0評估。 -25- 200837138 所得結果示於下表 /Wherein R represents an extended aryl group, a cycloalkyl group, an alkylene group or an alkenyl group, and R may have an alkyl group, an alkenyl group, a -COOH group and/or other anhydride groups. Examples of the anhydride include phthalic anhydride, hexahydrophthalic anhydride, glutaric anhydride, succinic anhydride, dodecenyl dianhydride, maleic anhydride, trimellitic anhydride, and pyromellitic anhydride. Preferred anhydrides are those wherein R is an extended aryl group (more preferably a phenyl group) or an alkyl group (more preferably an ethyl group) substituted with a stilbene group having 5 to 20 carbon atoms. Mixtures of anhydrides -11- 200837138 can also be used. The amount of anhydride used to prepare the carboxy-functional polyester from the hydroxy-functional polyester is typically used to prepare the anhydride of the carboxy-functional polyester from the hydroxy-functional polyester relative to the -OH group present in each batch of equivalent polyester. The amount is usually at least 0.8 pmol, preferably at least 〇9 pmol and more preferably at least 0.95 pmol. The anhydride is usually used in an amount of up to 1.2 pmol, preferably at most 1.1 Pmol and most preferably at most 1.0 mol, relative to the p-equivalent polyester. The preparation of the carboxy functional polyester from the hydroxy functional polyester and anhydride can be carried out in situ without the need to separate the carboxy functional polyester prior to further reaction with the epoxide. According to a first variant of the invention, the radiation-hardenable oligomer is the reaction product of a carboxy-functional polyester with one or more (meth)acrylated epoxides. In this case, it is preferred to use the relative amounts of the carboxyl functional polyester and the (meth)acrylated monoepoxide, so that the epoxide equivalent is provided by one or more (meth)acrylated monoepoxides. The number y is equal to or greater than the number X of the -C00H groups provided by the carboxy-functional polyester. Preferably y = x. When the y system is greater than X, it is preferred to add at least one-unsaturated carboxylic acid to the reaction mixture of the carboxy-functional polyester in an amount of at least (y-χ), more preferably (y-x). The term (meth)acrylated epoxide means a compound comprising an epoxy group and one or more (meth)acrylic groups. Examples of useful (meth)acrylated monoepoxides are epoxypropyl (meth)acrylates such as glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate epoxy Dipropyl ether, bisphenol-indole diglycidyl ether monoacrylate. The (meth)acrylated monoepoxide is preferably selected from the group consisting of -12-200837138 in glycidyl acrylate and glycidyl methacrylate. According to a second and preferred variant of the invention, the radiation-hardenable oligomer is the reaction product of a carboxy-functional polyester with at least one polyepoxide and at least one α,/3-unsaturated carboxylic acid. In this case, it is preferred to use a relative amount of the polyester, polyepoxide, and unsaturated carboxylic acid, and therefore, for the X equivalent-COOH group provided by the polyester, there is at least an equivalent of more than ζ. Epoxide, and at least (ζ-χ) equivalent α, /3-unsaturated tannic acid. In such variations of the invention, the enthalpy is preferably at least 1.5 X, more preferably at least 2 X. ζ usually does not exceed 20 X, preferably does not exceed 15 X. When the lanthanide is greater than 2 X, the excess polyepoxide reacts with the α,/3-unsaturated decanoic acid to form an unsaturated polyepoxide derivative in situ. The term polyepoxide means any compound containing at least two epoxy functional groups. The polyepoxide is usually selected from the group consisting of a glycidyl ether of an aromatic polyol or an aliphatic polyol, a glycidyl ester of an aromatic polybasic acid or an aliphatic polybasic acid, or a cycloaliphatic polyepoxide. . It is preferably a diglycidyl ether of an aromatic polyol or an aliphatic polyol, a diglycidyl ester of an aromatic polybasic acid or an aliphatic polybasic acid, or a cycloaliphatic diepoxide such as bisphenol. - bis-glycidyl ether, bisphenol-F diglycidyl ether, poly(ethylene oxide copolymerized-propylene oxide) diglycidyl ether (trade name DER 736), polypropylene oxide Diglycidyl ether (trade name DER 732), diglycidyl ether of hexanediol (trade name: 051-051), diglycidyl ether of butanediol (trade name: Araldite D Υ 02 6 SP), diglycidyl ether of linoleic acid binary (trade name Erisys GS-120), cellulose oxide (celloxide) 20 81. Particularly preferred are bisphenol-A diglycidyl ether, poly(ethylene oxide copolymer-epoxy-13-200837138 propane) diglycidyl ether, polypropylene glycol diglycidyl ether, butylene glycol Diglycidyl ether. Preferably, the S-unsaturated acid is selected from the group consisting of a acrylic acid and a methacrylic acid, preferably selected from the group consisting of acrylic acid. In the second variation of the present invention, a, the amount of the cold-unsaturated carboxylic acid is preferably (z-x) equivalent, wherein z is a polyepoxide equivalent, and X is a -COOH equivalent of the carboxyl functional polyester. In this second variant of the invention, it is preferred to pass the addition of the a, /3-unsaturated carboxylic acid to the carboxyl functionalized polyester, either before the polyepoxide or at least simultaneously with the polyepoxide. A radiation hardenable oligomer is prepared. According to a third variant of the invention, the radiation-hardenable oligomer consists of one or more carboxyl-functional polyesters U) with one or more (meth)acrylated monoepoxides, and with one or more polyepoxides And/or one or more α,/3-unsaturated carboxylic acids are obtained by reaction. The reaction of the carboxylated polyester with the epoxide is typically carried out in the presence of one or more catalysts. One or more polymerization inhibitors may be added during or after the reaction. The radiation-hardenable oligomer according to the present invention can be prepared as such, but can be prepared in the presence of a non-reactive diluent. The term non-reactive diluent means a compound which does not react with a carboxyl functional polyester, an epoxide and/or an unsaturated carboxylic acid during the reaction. According to a preferred embodiment, at least one radiation-hardenable non-reactive diluent is added to the radiation-hardenable oligomer during the synthesis of the radiation-hardenable oligomer, at the end of the synthesis, and/or after the synthesis. The radiation-hardenable composition according to the present invention usually contains at least 5%, preferably at least 10%, more preferably at least 15% and most preferably at least 25% by weight of the radiation-hardenable -14-200837138 oligo. The radiation hardenable oligomer is usually present in an amount not exceeding 95% by weight of the hardenable material, and preferably not more than 80% by weight. The radiation-hardenable composition according to the present invention preferably contains at least one radiation hardenable agent in addition to one or more hardenable oligomers. Such a diluent is preferably a copolymerizable ethylenically unsaturated monomer, a more functional or polyfunctional (meth) acrylate monomer. The copolymerizable unsaturated monomer means a monomer which is usually copolymerized with a radiation hardenable oligomer under photopolymerization conditions, particularly by light. Preferably, the copolymerizable ethylenically saturated monomer is a functional group containing at least one (meth)acrylic group and preferably not more than one (meth)acrylic acid and a polyfunctional (meth)acrylonitrile (meth)acrylate. Examples of suitable monomers include octyl acrylate, lauryl acrylate, phenoxy acrylate, isodecyl acrylate, acid phenyl epoxidized propyl ether, acrylic trimethylolpropane formaldehyde, n-butyl amide. , propylene methoxyethyl ester, tetrahydrofurfuryl acrylate, acryl porphyrin, butylene glycol acrylate, dihydrodicyclopentadienyl acrylate acid and aliphatic carboxylic acid such as glyoxylate of neodecanoic acid Reaction product and compound. The most preferred diluents are phenoxyethyl acrylate, n-butyl propylene isopropenyl acrylate, tetrahydrofurfuryl acrylate, decyl porphyrin, acrylic acid and aliphatic carboxylic acid such as neodecanoic acid. Glycidyl ester products and mixtures thereof. The content of the radiation hardening diluent present in the radiation hardenable composition is usually from 0 to 95% by weight, more preferably from 5 to weight, still more preferably from 10 to 40% by weight. The radiation hardenable composition is preferably determined according to ISO 1 205 8 and has a viscosity of from 100 to 8000 mPa.s at 25 ° C, preferably from 1500 to 3500 mPa.s, and the radiation is preferably a olefin, but is not a 6 amine. The ester, propylene methyl thiol, propylene mixed ester, propylene reflection can be 75% having -15-200837138 The radiation hardenable composition used in accordance with the method of the present invention typically also contains at least one inhibitor. Inhibitors include, but are not limited to, hydroquinone, tolylhydroquinone, monomethylhydroquinone, tert-butylhydroquinone, di-t-butylhydroquinone, 2,6·di-t-butyl-4- Cresol (BHT), morphine trap. The amount of the inhibitor is usually from 0 to 0.5% by weight. The radiation hardenable composition also comprises at least one photochemical initiator and/or chemical initiator which initiates the polymerization of the radiation hardenable oligomer and optionally other radiation hardenable compounds present therein. A photochemical initiator (also referred to as a photoinitiator) is a compound which absorbs ultraviolet light to generate a group by absorption. The photoinitiator is preferably a free radical photoinitiator. When hardened under ultraviolet light, a hardenable composition comprising at least one photoinitiator is preferred. The photoinitiator or chemical initiator content in the composition is preferably from 0.01 wt% to 5 wt%. Further, the composition can be hardened in the absence of an initiator, particularly by electron beam radiation. The radiation hardenable composition also contains one or more adhesion promoters. The adhesion promoter is usually present in an amount of up to 20% by weight. It is preferred to use an adhesion promoter in an amount of from 2% to 15% by weight. The radiation hardenable composition according to the invention also comprises pigments, colorants and/or additives, such as polyfunctional (meth)acrylated compounds, conductive pigments, dispersants, flow modifiers, slip agents, flame retardants , UV protection agent. The additive content is preferably not more than 1% by weight. The radiation-hardenable composition according to the present invention is preferably an organic solvent which is substantially free of water and is regarded as a volatile organic solvent (VOC). Thus, the composition according to the invention of the present invention is generally regarded as a 100% solids (after curing) radiation hardenable composition which does not require evaporation to remove water or solvent during subsequent hardening. The radiation hardenable composition according to the present invention allows for good chemical and solvent resistance, scratch resistance, and surface hardness, together with improved flexibility, adhesion, and fracture resistance during bending and rapid deformation, and improved Anti-corrosive coating. The coating has an improved balance between flexibility and surface properties. The radiation hardenable composition also has improved heat resistance and exhibits good electrical insulating properties. These properties make them suitable for a wide range of applications, such as coatings on substrates such as metals, plastics and glass. The composition according to the invention is suitable for use in a wide range of applications, such as metal coating, coil coating and apparatus, in particular as agricultural and construction equipment, coatings for home appliances, pipe coatings, building coatings, wire coatings. Covering such as copper wire coating, automotive applications, especially as a primer for automotive refinishing and metal can coating. The radiation hardenable composition can also be used for thermoforming applications such as mold interior decoration. The composition is also suitable for use in the manufacture of electrical sleeves and glass laminates. The composition is particularly useful for coating flexible substrates such as packaging materials and plastics. The radiation hardenable composition can also be used to formulate UV-curable stencil inks for high flexibility and impact resistance. Accordingly, the present invention is also directed to a method of using a composition as described above for coating purposes, particularly for preparing a coated article, comprising the step of coating the composition as previously described. Radiation hardenable compositions have been found to be particularly suitable for metal coating and coil coating applications. The invention is therefore also directed to its use in metal coating, in particular for coil coating applications, more particularly in relation to a method for preparing coated sheet metal coils -17-200837138, comprising the following steps: (1) Rolling the sheet metal unwinding; (2) coating the sheet metal with a hardenable composition comprising at least one radiation-hardenable oligomer as previously described; (3) hardening the composition; and (4) re-applying Coiled coated metal flakes. Sheet metal is usually selected from cold rolled steel (with or without pretreatment), hot rolled steel (with or without pretreatment), stainless steel, zinc treated steel (with or without pretreatment), such as electrogalvanized steel and Hot dip galvanized steel, aluminum (with or without pretreatment) and hot dip tin. In the process of the present invention, unwinding of the sheet metal material and rewinding may be carried out by any suitable means. In the method according to the invention, the unwound metal flakes may be subjected to any suitable treatment prior to use of the radiation curable composition. The unwound metal flakes are typically cleaned to remove the protective oil layer. Chemical cleaning is also applied to the sheet after cleaning to enhance corrosion resistance and coating adhesion. In the method according to the present invention, the radiation hardenable composition may be applied to the precoated article by any suitable means such as dip coating, spray coating, electrostatic coating, film coating, curtain coating, vacuum application, roll coating, or the like. In particular, it is applied to a metal flake. It is preferably applied by roll coating. Application of the radiation hardenable composition to the article', particularly to the metal flakes, can be carried out at any suitable temperature, such as room temperature or elevated temperature, e.g., via heating of the metal flakes, roll coater, and/or hardenable composition. After coating the article or sheet of metal with a radiation hardenable composition, the composition of -18-200837138 is hardened. The hardening, i.e., the polymerization, can be carried out by any suitable means known to those skilled in the art, such as thermal hardening or photohardening. Photohardening can be carried out using ultraviolet light or free radiation such as gamma rays, X-rays or electron beams. In the method according to the invention, it is preferred to use an electron beam and in particular ultraviolet radiation. After the hardenable composition is hardened, the coated metal flakes may be re-rolled immediately, or one or more additional coatings may be applied and then re-rolled; or the coated metal flakes after re-rolling may be Move to another coating line where one or more additional coatings are applied. In the method according to the present invention, steps (2) and (3) may be repeated to coat the metal flakes with two or more radiation hardenable compositions as defined above. In this case, the radiation hardenable compositions may be the same or different. The method according to the invention allows to obtain coated articles, in particular metal coils with a lower amount of solvent or even no solvent, which reduces the risk of fire, saves energy usage, eliminates the need to remove or recycle the solvent, and saves space on the production line ( No need to dry the oven). The method according to the invention allows to obtain coated articles, in particular metal flakes, which have improved chemical and solvent resistance, scratch resistance and surface hardness, together with improved flexibility, adhesion and resistance to bending and rapid deformation The fracture resistance at the time and the improved uranium resistance make the sheet metal particularly suitable for post-forming. The coating has an improved balance between improved flexibility and surface properties. According to the method of the present invention, when a hardenable primer is applied to a galvanizing line or an electrogalvanizing line after the zinc layer is deposited on the metal surface, the following steps of the method are allowed to be avoided from -19-200837138: plating The strip is oiled, chemically cleaned, chemically pretreated, and conventional primer applied to the coating line prior to re-winding on the zinc line or on the electrogalvanized line. Chemical pretreatment is often carried out using Cr VI for chromation, and the use of the method according to the invention will allow for the resolution of such environmental issues. The process according to the invention allows to obtain coated metal coils having good uranium resistance, even though chemical pretreatments such as chromic acidation without the use of metals are still available. The invention further relates to the use of a radiation hardenable composition for the manufacture of an electrical sleeve coating, and to a method of making an electrical sleeve coating, wherein a sleeve, preferably a sleeve made of fiberglass, is coated and/or impregnated. The radiation hardenable composition is as described above. After coating and/or impregnation, the radiation hardenable composition is hardened as previously described. This sleeve can be used to surround a wire or a bundle of wires, so that an insulated and heat-resistant cable is obtained. The following examples illustrate the invention but are not limiting. Unless otherwise indicated, the parts stated in the examples are parts by weight. Preparation Example 1: Hydroxy-functional polyester PE1: In a 2-liter reactor to which a heating jacket was attached and equipped with a stirrer, 51 g of neopentyl glycol and 646 g of adipic acid were added. The reaction mixture was stirred and gradually heated to 2 15 ° C under a nitrogen stream to remove water by distillation. When the acid hydrazine reaches about 50 mg KOH/g, 0.20 g of Fasquet (FAS CAT) 4 102 (tin catalyst) is added under atmospheric pressure, and the reaction mixture is heated again at 21 5 ° C, and the water is removed under reduced pressure until The acid bismuth is less than 1 mg KOH/g. The polyester was a clear liquid having hydroxyhydrazine 56 mg KOH/g; its average molecular weight was about 2,000. Preparation Example 2: Hydroxypolyester PE2: -20- 200837138 A polyester was prepared according to the method described in Preparation Example 1, except that butanediol, 272 g of neopentyl glycol and 670 g of adipic acid were used. Polyfluorene 56 mg KOH/g transparent liquid; average molecular weight thereof] Preparation Example 3: Carboxyl polyester PE3: 7 with a heating jacket and equipped with a stirrer, adding 2023 g of neopentyl glycol (NPG) and 3,518 g The diacid is stirred and gradually heated to 2 15 ° C under nitrogen flow. When steaming saturates to about 50 mg KOH/g, special (FAS CAT) 4 102 is added under atmospheric pressure, and the reaction mixture is further added at 215 ° C. Remove water until the acid mash is below 1 mg KOH/g. The polyester is a transparent liquid with K〇H/g; its average molecular weight is about 2000. Example 1: Preparation of radiation hardenable oligomers 2504 g of polyester PE1, 371 g of phthalic anhydride, chromium catalyst (AMC-2) ) placed in a reaction bottle equipped with an agitator and a liquid meter. The mixture was heated at 1 15 ° C, at this time. 180 g of acrylic acid, 2.88 g of hydroquinone HQ and a mixture thereof were added, and the reaction mixture was stirred at 1300 ° C, and then 926 g of a bisphenol-oxime diglycidyl reaction mixture was added dropwise so that the temperature did not exceed 120°. C, and reverse 1 l 〇 ° C, stirred until the acid mash is less than 2.5 mg KOH / g ' and 0.1%. Obtained a product with viscosity (cone and plate viscosity, ISO 3219 at mPas. Example 2: using 223 g of 1,4-ester with a hydroxyl group of about 2000. Inside the reactor, the reaction mixture removes water. When acid 1.25 g method Skager, under reduced pressure - with acid 値 56 mg 〇 and 10 g octanoic acid plus funnel and temperature 昆 maintain 2 small 5.96 g AMC-2 ί 1 hour. Ether (BADGE) to the mixture and epoxy oxime Example 6 was repeated below 90 ° C) for 90300 -21 - 200837138, but 1 749 grams of propylene triisodecyl ester (IBOA) was added to the reaction mixture along with acrylic acid. Viscosity (cone and plate viscosity, ISO 3219 at 25 ° C) was obtained as a product of 55 700 mPas. Further, at the end of the reaction, after cooling to 80 ° C, IBOA was added to the reaction mixture. A product having a viscosity (cone and plate viscosity, ISO 3219 at 25 ° C) of 5 3 200 mPas was obtained. Example 3: The oligomer was synthesized according to the procedure of Example 2 using the following amounts: 626 g of polyester PE 2, 93 g of phthalic anhydride, 45 g of acrylic acid, 23 2 g of BADGE, 3.99 g of AMC-2, 0.72 g of HQ And 271 grams of IB0A. A product having a viscosity (cone and plate viscosity, ISO 3219 at 60 ° C) of 7 800 mPas was obtained. Example 4: 470 grams of polyester PE3 and 0.48 grams of MeHQ were placed in a reaction vial equipped with an agitator, liquid addition funnel and thermometer. The reaction mixture was heated to 103 ° C and a mixture of 34 g of acrylic acid, 1.45 g of AMC-2 and 290 g of IB0A was added to the reactor. The temperature was maintained at 1 〇 3 ° C for 1 hour, then 174 grams of BADGE was added dropwise to the reaction mixture at a temperature not exceeding 120 ° C. The reaction mixture was further heated at ll ° ° C until the acid lanthanide was less than 2.5 mg K 〇 H/g, and the epoxy oxime system is less than 0.1%. A product having a viscosity (cone and plate viscosity, ISO 3219 at 25 ° C) of 37,300 mPas is obtained. Example 5: An oligomer was synthesized according to the procedure described in Example 3, using 626 grams of polyester PE1 in place of polyester PE2. A product having a viscosity (cone and plate viscosity, ISO 3219 at -22-200837138 60 ° C) of 32000 mPas was obtained. Example 6: The oligomer was synthesized according to the procedure of Example 2 using the following amounts: 260 g of polyester PE 1, 38 g of phthalic anhydride, 129 g of acrylic acid, 386 g of BADGE, 2.26 g of AMC-2, 0.65 g of BHT and 350 grams of IBOA. A product having a viscosity (cone and plate viscosity, ISO 3219 at 60 ° C) of 700 mPas was obtained. Example 7: An oligomer was synthesized according to the procedure described in Example 4, using 290 g of phenoxyethyl acrylate in place of IB0A. A product having a viscosity (cone and plate viscosity, ISO 3219 at 60 ° C) of 21,000 mPas was obtained. Comparative Example 8R: The acrylated polyester was prepared as follows: 400 g of polyester PE1, 31.7 g of acrylic acid; and 14.2 g of p-toluenesulfonic acid were placed in a 1 liter double jacketed reactor connected to an oil bath equipped with a stirrer. (PTSA), 2 8 8 g of toluene, 0.73 g of Cu 2 ruthenium, 0.55 g of methylhydroquinone (MeHQ), and 0.73 g of TNPP. The reaction mixture was heated to reflux (11 5 - 120 ° C) under a stream of oxygen. The water is removed by azeotropic distillation. When water was no longer distilled, 0.6 g of MeHQ and 0.36 g of TNPP were added, and toluene was distilled off under reduced pressure. The polyester acrylate had a viscosity at 60 ° C of 1544 mPa·s (HOppler, ISO 12058 to 6 (TC). Comparative Example 9R · · Acrylate polyester was prepared as in Comparative Example 7R, but used 400 g of polyester PE 2. The polyester acrylate has a viscosity at 60 ° C of 8 9 8 mPa.s (Hopper, ISO 1 205 8 at 60 t:). -23- 200837138 Examples 10 to 19 and comparative examples 20R to 23R ·· UV curable formulation is prepared by mixing: 90 parts of the products obtained in Examples 2 to 5, 7, and 8R and 9R, respectively, or 5 parts of the commercially available tree EBECRYL® 629 and EBECRYL® 3213 Adhesion Promoter (EBECRYL® 171) 3 parts of light bow hair styling agent (ADDITOL® CPK) 2 parts photoinitiator (TPO-L) UV light application is applied to hot dip galvanized steel using a 10 micron rod coater (Examples 10 to 14 and Comparative Examples 22R and 23R) or chromated electrogalvanized steel (Examples 15 to 19 and Comparative Examples 20R to 21R) exposed to ultraviolet radiation from a 120 W/cm unfocused medium pressure mercury vapor lamp To obtain a non-stick film. Samples tested for solvent resistance (ECCA ΤΙ 1), cross-hatching (ISO 2409), adhesion during bending Fracture resistance (T-bend test EN 13 523-7), adhesion during rapid deformation and fracture resistance (reverse impact, ISO/DIS 6272-ASTM D 27 94) and adhesion during slow draft deformation (ISO 1 5 20). Examples 24 and 25: Ultraviolet hardenable formulations were prepared by mixing: 45 parts of the product obtained in Example 1 45 parts of phenoxyethyl acrylate (EBECRYL® 114) 5 parts of adhesion promoter ( EBECRYL® 171) 3 parts of light bow ! !! I (ADDITOL® CPK) 2 parts of photoinitiator (TP0-L) -24- 200837138 UV formulation is coated on hot dip coating with a 10 micron bar coater Zinc steel (Example 24) or chromated electrogalvanized steel (Example 25), hardened and evaluated as in Example 10. Examples 26 and 27: UV light hardenable formulations were prepared by mixing: 43.2 parts of the product obtained in Example 1 46.8 Isodecyl acrylate 5 parts adhesion promoter (EBECRYL8171) 3 parts ADDITOL® CPK 2 parts photoinitiator (TPO-L) UV coating is coated with a 10 micron bar coater For hot dip galvanized steel (Example 26) or chromed electrogalvanized steel (Example 27), hardened and evaluated as in Example 10. -25- 2008 The results obtained in 37138 are shown in the table below /
如上述可得到比較結果’根據本發明之寡聚物允許獲 得塗覆層，其同時具有改良之化學及溶劑耐性連同改良之 可撓性、於彎折及快速變形之黏者性及耐斷裂性。 -26- 200837138 實例2 8 : 經由混合1 00份實例7所得產物及5份光引發劑製備 紫外光可硬化調配物。 實例2 9 : 紫外光可硬化調配物係經由將80份實例7所得產物， 20份重量比丙烯醯氧基味啉及5份光引發劑混合而製備。 以實例28及29之調配物製備可自行豎立之薄膜，測 試其機械耐性及熱耐性，且與由市售可撓性環氧基丙烯酸 /酯（EBECRYL® 3708)所得薄膜作比較。表中結果顯示根據本 發明之組成物顯示較佳機械性質及熱性質，因而特別適合 用作爲電套筒之塗層。 實例 伸長率 強度mPa.s 楊氏模量mPa.s 190°C之重量耗損之後 30曰後 60曰後 28 128% 2.1 3.9 29% 49% 29 183% 11.9 43.9 57% EBECRYL⑧ 3708 73% 8.7 14.6 58% 66% 【圖式簡單說明】 Μ 〇 【元件符號說明】 無 。 -27-The comparison results can be obtained as described above. 'The oligomer according to the present invention allows obtaining a coating layer having both improved chemical and solvent resistance together with improved flexibility, adhesion and fracture resistance in bending and rapid deformation. . -26- 200837138 Example 2 8: An ultraviolet light hardenable formulation was prepared by mixing 100 parts of the product obtained in Example 7 and 5 parts of a photoinitiator. Example 2 9: An ultraviolet light hardenable formulation was prepared by mixing 80 parts of the product obtained in Example 7, 20 parts by weight of propylene oxy morpholine and 5 parts of a photoinitiator. Films which were self-erecting were prepared from the formulations of Examples 28 and 29, tested for mechanical and thermal resistance, and compared to films obtained from commercially available flexible epoxy acrylates (EBECRYL® 3708). The results in the table show that the composition according to the present invention exhibits superior mechanical properties and thermal properties and is therefore particularly suitable for use as a coating for an electrical sleeve. Example Elongation Strength mPa.s Young's Modulus mPa.s Weight Loss at 190 °C After 30 曰 After 60 曰 28 128% 2.1 3.9 29% 49% 29 183% 11.9 43.9 57% EBECRYL8 3708 73% 8.7 14.6 58 % 66% [Simple description of the drawing] Μ 〇 [Component symbol description] None. -27-